10 Hoa - Huu - Co

o Hng Cng http://hoahocsp.
tk 1
Chng 1
C S HA I CNG
1.1. HA HU C CHT HU C
1.1.1. c im v s pht trin ca ho hc hu c.
i tng nghin cu ca ho hc l nhng cht ho hc ring bit v s bin i ca
chng. Mt lnh vc c bn ca ho hc l ho hc hu c nghin cu cc hp cht ca cacbon
vi cc nghin t khc, ch yu l hp cht ca cacbon vi Hyr, Oxi, Nit, Phtpho, Lu
hunh v Halogen.
Nhiu hp cht hu c c con ngi bit rt lu nh: dm (axit axetic lng), mt s
thuc nhum, ru etylic, cc hp cht axit oxalic, axit xitric, axit tactric v mt s baz hu c
(cc ancaloit) c tch t ng thc vt vo cui th k th 18 v u th k th 19. Thi
im ny cng c tnh l thi im u ca mn ho hc hu c.
th k th 18 v th k th 19, ngi ta cho rng ho hc ca th gii cc cht SNG
khc vi th gii ho hc ca cc cht cht, l c th sng c cu to t nhng hp cht c
bit do mt ngoi lc sng (Tri, Cha, Pht) to nn m cc cht bn thn con ngi
khng th tng hp c. Nhng nhng pht hin th k 19 cho thy rng tt c cc hp cht
cu to nn c th ng vt v thc vt u c thnh phn ging nhau ph v s khc bit
gia ho hc ng vt v thc vt. Hai lnh vc nghin cu ny st nhp vo nhau v hnh
thnh mn ho hc hu c. Nh bc hc Thy in Berceluyci (1779-1848) c rt nhiu
cng trong lnh vc st nhp ny. Sau ng, nh bc hc Lavuaze, bng nhng phng php
phn tch nh lng pht hin c mt s nguyn t mi, xc nh c nguyn t lng
ca nhiu nguyn t, t nn mng cho hin tng ng phn. Nh ho hc c Beler bng
phn ng thu phn hp cht ixianua (v c) thu c axit oxalic (hu c) nm 1824 v t
xinaoxit amoni (v c) thu c ur (hu c) nm 1828 ph v s phn bit gia hp cht
v c v hu c. iu ny cng chng minh rng cc hp cht hu c c th thu nhn c
bng con ng tng hp m khng cn s tham gia ca mt ngoi lc huyn b no c. iu
c khng nh bng cc cng trnh ca Buttlerp tng hp cc hp cht ng t
formalin (1861), Faray thu nhn c bezen (1825), Zinin tng hp c anilin t nitrobezen
(1842) v t anilin thu nhn c cc hp cht mu vo nhng nm 50 ca th k 19. Cng
vo nhng nm ny Gmelin a ra nh ngha ho hc hu c l ho hc cc hp cht
cacbon v n ti n ngy nay.
1.1.2. Cu to ca cc hp cht hu c.
o Hng Cng http://hoahocsp.tk 2
T nh ngha trn y xut hin mt vn ln l ti sao t hng trm nguyn t bit
ch c cacbon to thnh nhiu hp cht nh vy?
Th nht: do hin tng ng phn c Berceluyci pht hin cho tt c cc cht ho
hc m c bit l cht hu c c th tn ti nhiu hp cht khc nhau c cng thnh phn
nguyn t, cng phn t lng nhng khc nhau v cu to. V d: C
20
H
42
c 366.319 hp cht
khc nhau, C
30
H
62
tn ti 4.111.846.768 hp cht khc nhau.
Th hai: do hin tng ng ng - tn ti cc hp cht ho hc m thnh phn ca mi
cht ch khc nhau bi mt nhm CH
2
(mtylen).
Th 3: do hin tng ng cp - cc hp cht c cu to cng mt s nguyn t
cacbon nh nhau nhng hp cht sau c t hn hp cht trc 2 nguyn t Hyr (tan C
2
H
6
,
tylen C
2
H
4
, axetylen C
2
H
2
).
Vy ti sao cc hp cht hu c li tn ti di cc dng ng ng, ng phn?
Trong cc thuyt a ra gii thch vn ny ca nhiu nh bc hc thuc nhiu th
h khc nhau c th lu mt vi gi thit sau y:
Thuyt kiu ca Zerar cc hp cht c phn b theo cc kiu H
2
O, HCl, H
3
N, H
2
.
y ch cn thay th hyr ca cc kiu bng phn gc hu c th ta s thu c cc hp cht
khc nhau.
V d:

H
H
O
CH
3
H
O
C
2
H
5
H
O
C
2
H
3
O
H
O
nc
mtanol tanol axit axetic

H
Cl
CH
3
Cl
C
2
H
5
Cl
C
2
H
3
O
Cl
hyrclorua mtylclorua tylclorua axtylclorua

CH
3
H
H
H
C
2
H
5
H
C
2
H
3
O
H
hyro mtan tan axtanhyt
Nm 1851, Viliamxn a ra thuyt raical ca nhiu nguyn t - tc l cc raical c
kh nng thay th 2 hoc nhiu hyr trong cc kiu.
V d: axit aminaxtic l kiu H
2
O v NH
3
H
C
2
H
3
O
O
H
H
N
c bit quan trng l kiu mtan ca Kkuk
H
H
H
H
C
Kkul s dng khi nim ho tr ca nh ho hc Anh Frankland cho nguyn t
cacbon 1857. T vic cng nhn nguyn t cacbon c ho tr 4, Kkul i n kt lun l
nguyn t cacbon c kh nng lin kt vi nhau.
V d: tan c th vit:
H
H
H
C
CH
3
Nh vy cacbon lin kt vi nhau to thnh cc mch di ngn khc nhau.
Mt trong nhng ng gp quan trng cho thuyt cu to cc hp cht hu c l
thuyt cu to ca Buttlrp (1861): bn cht ho hc ca mt phn t ca mt cht c xc
nh bi bn cht cc nguyn t c hp thnh, bi s lng ca chng v bi cu to ho
hc. T ni dung ca thuyt ta c th rt ra cc kt lun sau:
1. Cc nguyn t trong phn t khng phi sp xp hn n, v trt t, chng kt hp
vi nhau theo mt trt t xc nh, theo ng ho tr ca chng.
2. Tnh cht ca cc cht khng nhng ph thuc vo thnh phn nguyn t, vo s
lng nguyn t ca cc nguyn t m cn ph thuc vo cu to ho hc ca chng na.
3. Cu to ca cc cht c th xc nh c khi nghin cu tnh cht ca chng. Cu
to ho hc ca mi cht c th biu th bng mt cng thc ho hc nht nh gi l cng thc
cu to.
Thuyt cu to Buttlrp chnh l nn tng cho s pht trin ca ho hc hu c t nm
1861 n nay. Bng cc phng php ho hc ngi ta xc nh c cu to ca nhiu hp
cht khc nhau. Ngy nay, tuy cc phng php ho hc vn cn c ng dng trong thc t
nhng xut hin cc phng php vt l nh khi ph, ph cng hng t nhn, ph in
tgip cho cc nh ho hc xc nh nhanh chng v chnh xc cu to ca cc hp cht ho
hc.
Tm li, s hnh thnh khi lng khng l cc hp cht hu c l do kh nng to
thnh dy ng ng, ng phn, kh nng to thnh nhng mch di (c th ni l v tn), kh
nng to lin kt bn vng vi cc tc nhn electronphin (nh hyr), vi tc nhn nucleophin
(nh halogen, xy, Lu hunh, Nit..) ca nguyn t cacbon.
1.1.3. Cc phng php biu din trong ho hc hu c.
Nh ta bit ho hc v c nghin cu ch yu cc hp cht phn cc v cc lin kt
ho hc phn cc. Tri li ho hc hu c nghin cu ch yu cc hp cht khng phn cc v
cc lin kt khng phn cc. Thuyt in ly trong nhng nm u ca th k 20 t nn tng
cho l thuyt cu to ion ca cc mui v cc cht in ly. S pht minh electron v cc nh
lut nh lng ca qu trnh in ly l c s cho thuyt ho tr in t. Theo cc thuyt ny
mt hp cht in ly c cu to t cation v anion. Cation l nguyn t kim loi b mt in
t, cn anion l nguyn t khc nhn thm in t. L thuyt ny c Kosel ng dng cho
nhiu hp cht v nhiu qu trnh trong ho hc v c (1917). Mt khc Kosel cng nhn thy
rng, i vi cc cht khng phn cc nh H
2
, O
2
, N
2
, hyrcacbon th thuyt in ly khng
thch hp m phi tm kim nhng thuyt ho hc khc. iu c Luit gii thch bng
lin kt cng ho tr (1916) c to thnh do cp in t gp chung gia cc nguyn t. Theo
Luit, lin kt gia cc cht khng phn cc c biu din nh sau:
H H H C
H
H
H H C
H
H H
C H
H
H C
H
H H
C
H
O H
H
2
CH
4
C
2
H
6
CH
3
CH
2
OH
y cp in t c th thay th bng gch ngang (-). Do cc hp cht lin kt i
hay lin kt ba c th biu din:
H C
H
C H
H
hoc C C
H
H
H
H
H C C H
hoc H C C H
1.1.4. Phn loi cc hp cht hu c.
Cc hp cht hu c c phn loi theo cu to ca chng, c trng bi cc lin kt
gia cc nguyn t cacbon vi nhau. Cc hp cht c cha cc nguyn t khng phi l cacbon
c xem nh dn xut ca hyrcacbon m trong nguyn t hyr c thay th cc
nguyn t khc. Tt c cc hp cht hu c c chia lm 2 nhm ln: cc hp cht mch h
v cc hp cht mch vng.
Cc hp cht mch h l nhng hp cht bo:
Mch thng khng phn nhnh (normal).
H C C C C C
H H H H H
H
H H H H H
H C C C C C
H H H H H
C
H H H H H
C C H
H
H
H
H
H
H
n-pentan n-ctan

Mch phn nhnh:
C
H
H
H
C
CH
3
CH
3
C
H
H
H
nepentan
C
H
H
H C
H
CH
3
C
H
C
H
H
H
H
izpentan

Cc hp cht khng no (cha ni i, ni ba):
C H
H
C
H
C
H
C H
H
CH
3
CH
2
C CH
butaien-1,3
butin-1
Cc hp cht vng gm:
Vng ring bit-ch c nguyn t cacbon tham gia ng vng:
C
C C C C
C C C C
C
C
C C
C C
C
D vng-cc nguyn t tham gia ng vng ngoi nguyn t cacbon cn c cc nguyn
t khng phi l cacbon nh Oxi, NitCng tng t nh cc hp cht mch h, cc hp cht
mch vng cng c vng khng no cha ni i hoc ni ba. c bit, mt trong nhng vng
khng no rt quan trng l loi vng thm-vng cha 6 nguyn t c ba ni i lin hp ca
cacbon hoc cacbon vi cc nguyn t d t.
N N
Naphtalen
Kinlin
Benzen
Piriin

Trong loi hp cht thm ny cn c loi vng 5 nguyn t cha 2 ni iv mt nguyn
t d t cha cp in t t do:
Pirol Furan Tiphen
N
H
O S
1.1.5. Cch gi tn cc hp cht hu c .
Trong ho hc hu c cho n nay tn ti nhiu cch gi tn khc nhau. gi cc dy
ng ng ca hyrcacbon, ngi ta thng s dng tn gi ca cc hp cht n gin nht.
V d hyrcacbon dy mtan, hyrcacbon dy tylen, hyrcacbon dy axtylenTt c cc
hp cht hu c khc cn li c xem nh l dn xut ca hyrcacbon. gi tn cc hp
cht hu c ring bit, thng s dng cc danh php: danh php thng thng, danh php Gi-
ne-v (1892), danh php IUC (International Union Chemistry) 1950, danh php IUPAC
(International Union of Pure and Applied Chemistry) 1957
A. Danh php thng thng:
Gi tn cc hp cht theo lch s thu nhn c, theo ngun gc ca nguyn liu ban
u, theo phng php tng hpV d: kh m (t m), axit focmic (focmic-kin), vanilin
(vani-cy vani)Nhiu cht c gi tn ca nh bc hc thu nhn c n. V d xton
Micler, hyrcacbon TitibabinMt s tn gi thng thng c s dng rt rng ri trong h
thng tn gi th gii. V d tn gi ca dy ng ng ankan t C
5
tr i c phn gc l s m
h latinh cng thm ui an (pentan, hexan, heptan) nhng 4 hp cht u (mtan, tan,
propan, butan) li l tn gi thng thng v phn gc khng phi l s m h latinh.
B. Danh php IUPAC:
Gi tn cc hp cht mch h:
1. Gi tn 4 hp cht u ca hyrcacbon no l: mtan, tan, propan, butan. Gi tn
cc hp cht tip theo ca dy ny bng phn gc l s m h latinh cng ui an: pentan,
hexan, heptan, octan, nnan, kanTn gi chung ca hyrcacbon mch thng no l ankan.
2. Cc raical (phn gc) c ho tr I c to thnh t hyrcacbon no mch h bng
cch tch i mt nguyn t hyr u mch c gi tn bng cch thay ui-an bng ui
yl.
Vd: CH
3
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CH
2
CH
2
CH
2
-
Pentan Pentyl
CH
3
-CH
2
-C
7
H
14
-CH
3
CH
3
-CH
2
-C
7
H
14
-CH
2
-
kan kyl
3. Mch di nht c nh s t u ny n u kia bng ch s latinh sao cho v tr
cc nhm mch nhnh c tng cc ch s l nh nht. Trng hp khi nh s t u ny n
u kia m thu c mt s dy ch s ca cc nhm mch nhnh khc nhau th phi sp xp
chng li theo th t tng dn. Dy c tng cc ch s nh nht c xem l dy c ch s u
nh nht.
V d:
CH
3
CH
2
CH CH
2
CH
3
CH
3

CH
3
CH CH
2
CH
2
CH
3
CH
3
3-mtylpentan 2-mtylpentan
(khng c 4-mtylpentan)

CH
3
CH CH
2
CH CH CH
3
CH
3
CH
3
CH
3
2,3,5-trimtylhexan(khng c 2,4,5-trimtylhexan)

CH
3
CH
2
CH
2
CH
2
CH
CH
3
CH
3
CH
2
CH
2
CH
3
CH
2
CH
2
CH
5-mtyl-4-prpylnonan
(khng c 5-mtyl-6-prpylnonan)

4. Cc phn gc (raical phn nhnh ho tr 1) c gi tn bng cch
thm vo mch thng khng phn nhnh di nht ankyl (bt u t pha c ho tr t do s 1) tn
gi cc mch nhnh.
V d: CH
3
CH
2
CH
2
CH
2
CH(CH
3
)- CH
3
CH
2
CH
2
CH(CH
3
)CH
2
-
1-mtylpentyl 2-mtylpentyl
Mt s nhm gi tt nh sau:
(CH
3
)
2
CH- (CH
3
)
2
CHCH
2
- CH
3
CH
2
CH(CH
3
)- (CH
3
)
3
C-
Izprpyl izbutyl secbutyl tecbutyl
(CH
3
)
2
CHCH
2
CH
2
- (CH
3
)
3
C-CH
2
- CH
3
CH
2
C(CH
3
)
2
-
Izpentyl nopentyl tecpentyl
5. Nu c 2 nhm mch nhnh khc nhau tr ln th c th gi chng theo th t ch ci
hoc theo phc tp ca nhm ( ln khng gian ca nhm).
V d: Theo vn ch ci:
CH
3
CH
2
CH
2
CH CH CH
2
CH
3
C
2
H
5
CH
3

Hai nhm tyl (C
2
H
5
) v mtyl (CH
3
) th ch E ng trc ch M nn gi l 4-tyl-3-
mtylheptan.
Theo phc tp ca nhm:
Nhm c s nguyn t cacbon nhiu phc tp hn nhm c s nguyn t cacbon t:
(CH
3
)
3
C- < CH
3
CH
2
CH
2
CH
2
CH
2
-
Nhm ph c ch s nh, t phc tp nhm c ch s ln:
CH
3
CH
2
CH(CH
3
)CH(C
2
H
5
)CH
2
- < CH
3
CH
2
CH(C
2
H
5
)CH(CH
3
)CH
2
-
Gc no nh hn gc khng no:
CH
3
CH
2
CH
2
- < CH
3
CH=CH-
Gc c ch s v tr khng no nh s nh hn v tr ln:
CH
3
CH=CH- < CH
2
=CH-CH
2
-
6. Khi c mt nhiu nhm th ging nhau ta dng cc tip u ng: i-(2), tri-(3), ttra-
(4), penta-(5), hexa-(6), hepta-(7)V d:
CH
3
CH
2
C(CH
3
)
2
CH
2
CH
3
c l 3,3-imtylpentan.
7. Cc hp cht khng no c mt ni i, gi tn bng cch thay ui an bng ui en,
2 ni i thnh aien, 3 ni i thnh atrienTn gi chung cho cc hp cht l anken,
ankaien, ankatrien
V d: Hp cht CH
3
CH
2
CH
2
CH=CH-CH
3
gi l 2-hexen
CH
3
CH=CHCH
2
CH=CH
2
gi l 1,4-hexaien
Ch : CH
2
=CH
2
tylen v : CH
2
=C=CH
2
allen khng theo h thng danh php IUPAC.
Bng cch chuyn i tng t nh vy gi cc hp cht cha ni 3: c 1 ni 3 th
i ui an thnh ui in, c 2 ni 3 th i thnh ui aiin, c 3 ni 3 th i thnh
atriin
Tn gi axtylen l danh php thng thng nn n khng thay i theo quy lut trn.
Cc gc anken c ho tr I c gi bng cch thm vo phn ui t -enyl, -
ienylcn cc gc ankin c ho tr I th thm vo ui inyl, -iinyl
V d:
CH
3
CH CH CH
3
CH CH CH
2
HC C HC C CH
2
1-prpenyl 2-butenyl tinyl 2-prpinyl

8. Gi tn cc hp cht vng tng t nh cc hp cht mch h c thm tip u ng
xyclo-.
V d:
CH
2
CH
2
CH
2
CH
2
CH
2
CH
xyclprpan xyclhexan xyclhexyl xyclprpyl
C
C
CH
2
CH
2
CH
2
CH
2
H
2
H
2
C
C
CH
2
CH
2
CH
CH
2
H
2
H
2
1.2. CHT TINH KHIT
Khi nim v cht nguyn cht (mt cht n gin hay mt hp cht) l nhng cht c
cu to t nhng phn t ging nhau. Nhng trong thc t kh c th thu nhn c nhng cht
nh vy, do cc nh ho hc hu c tnh rng nhng cht c cha 99% cht hu c c gi
l cht ho hc tinh khit. nh gi tinh khit ca cc cht, thng dng cc phng php
vt l nh nhit nng chy, nhit ng c, nhit si p sut nht nh, ch s khc
x, quay cc, cc loi quang ph
1.2.1. Cc phng php thu nhn cht tinh khit.
1.2.1.1. Phng php kt tinh.
y l phng php quan trng nht tinh ch cc cht rn. Ta ho tan n mc bo
ho sn phm th trong mt dung mi thch hp nhit cao, lc nng dung dch khi cc
thnh phn khng ho tan ri ngui v nh th l hp cht s kt tinh li di dng tinh khit
hn.
a. La chn dung mi: trong dung mi c la chn hp cht phi t tan nhit thp
nhng tan tt khi un nng cn cc tp cht nu tan cng nhiu th cng tt. Theo kinh nghim,
thng mt cht c ho tan tt trong dung mi c cu trc ho hc tng t vi n, nht l
i vi cc hp cht c cu trc n gin. V d: cc hyrcacbon tan tt trong cc dung mi
thuc loi hyrcacbon, te, cn cc anehyt, phnol, ancol, axit cacbxylic tan tt trong H
2
O,
ancolTt nhin dung mi c la chn khng c lm thay i cht ho tan v mt ho
hc.
b. Cch tin hnh: trc ht ta un nng hp cht cn kt tinh trong mt lng dung mi
khng ho tan lng cht , sau ta un si dung mi v qua sinh hn cn thn cho
thm dung mi vo cho n khi ho tan hon ton cht kt tinh trong dung mi dang si. Lc
nng dung dch, lm lnh s thu c cht rn tinh khit hn.
1.2.1.2. Phng php chng ct.
Chng ct l phng php tch v tinh ch quan trng nht i vi cc cht lng. Trong
trng hp chng ct n gin, ta cung cp nhit cho mt cht lng n khi cht si v hi
ngng t c to thnh trong mt ng sinh hn. Hng ly cht lng ta c cht lng
chng ct tinh khit hn. V trong trng hp ny ch c mt tng (tc l hi) chuyn ng
nn ta gi l chng ct cng dng hay chng ct n gin. Ngc li nu c mt phn hi c
ngng t chy ngc li vi dng hi v li nh vo bnh ang si ta gi l chng ct ngc
dng (cn gi l chng luyn rectification).
a. Chng ct n gin: Tin hnh chng ct n gin hp l hn c l khi nhit si
vo khong 40-150
o
C ( cao hn 150
0
C cc cht hu c d b phn hu, thp hn 40
0
C d b
mt mt nhiu). V vy cc cht lng si cao hn 150
0
C phi tin hnh chng ct di chn
khng.
Chng ct n gin ch thch hp vi cc hn hp lng gm cc cu t c nhit si
khc xa nhau.
Ch khi tin hnh phi iu chnh sao cho tc chng ct trong mt giy khng qu 1
n 2 git ri xung bnh hng. Khi chng ct phi lp ng cong cho qu trnh si- tc l v
ng biu din s thay i nhit vi lng cht lng chng ct c T= f(x) ml.
b. Chng ct phn on (tinh ct): Trng hp ny p dng khi chng ct n gin
khng tch c hn hp ra khi nhau (thng l khi hiu s im si ca cc cht nh hn
80
0
C). Khi tin hnh bng phng php ny trong ct chng ct pha di c nhit cao
hn pha trn nn hi c nhit cao i t di ln truyn nhit cho cht lng ngng t t
trn xung, lm cho mt phn cu t d bay hi trong cht lng b ngng t li, tip tc bay hi
ln 2, ln 3cn mt phn cu t kh bay hi trong pha hi b ngng t thnh lng v tip tc
i xung gn di ct ct. Kt qu ca qu trnh lp li nhiu ln nh vy cho ta thu c cht
lng ct ra tinh khit hn v cht lng cn li trong bnh ct cng tinh khit hn.
c. Chng ct li cun bng hi nc: Nu hai hp cht khng ho tan vo nhau th p
sut hi ca chng khng nh hng n nhau. Ta c:
f
A
= p
A
v p = p
A
+ p
B

f
B
= p
B
Trong f
A
, f
B
l p sut ring phn ca A, B.
p
A
, p
B
l p sut hi bo ho ca A, B tinh khit cng nhit T
0
C.
Mt cht si nhit m p sut hi ca n cn bng vi p sut hi ca kh quyn.
Nh vy nu ta un hai cht lng khng ho tan vo nhau th hn hp s si nhit m
tng p sut hi ca 2 cht lng bng p sut kh quyn. iu c ngha l im si ca hn
hp nh vy bao gi cng thp hn im si ca cu t c im si thp nht. Trong thc t
thng dng cht lng th 2 l nc, v vy chng ct hn hp nh vy c th tin hnh
nhit thp hn 100
0
C. Tt nhin nc khng c trn ln v tc dng vi cht cn chng
ct.
Cch tin hnh: Ta dn hi nc c to ra t mt bnh bng kim loi hoc thu tinh
vo y ca bnh ct hnh cu. Trc cn un dung dch cn chng ct cho ti gn si tr
lc cho qu trnh ct. Bnh thu sn phm s thu c hai lp cht lng (nc v cht cn tinh
ch) c tch ra bng phng php gn hoc bng xiphng. Ni chung ta chng ct n khi
no cht lng ct khng cn tch thnh hai lp na. i vi cht lng c nhit si cao c th
thay nc bng tylen hoc glyxrin.
1.2.1.3. Phng php thng hoa.
Phng php thng hoa l phng php m trong ngi ta lm bc hi cc cht rn v
sau ngui chng c th ngng t trc tip li di dng cht rn m khng phi lm nng
chy chng.
1.2.1.4. Chit.
Chit l vic chuyn mt cht dng ho tan hay dng huyn ph t mt tng ny sang
mt tng khc.
a. Chit cc cht rn: V d chit ng ra khi ma hoc c ci ng. Trong phng
php chit n gin mt ln, ta un nng hp cht cn thit vi dung mi trong mt bnh cu c
sinh hn hi lu, lc nng hoc lng cho trong ri tch cc phn ring ra khi nhau. Trong
phng php chit n gin nhiu ln, ngi ta lp i lp li nhiu ln nh m t trn.
b. Chit cht lng, chit cc dung dch huyn ph: Ta cho dung dch nc hoc huyn
ph nc chit vo mt phu chit v cho thm dung mi chit vi khong 1/5 n 1/3 th
tch cht lng vo phu. ng kn nt phu chit v lc mnh mt s ln, sau yn,
dung dch phn thnh 2 lp v tch ly lp dung mi. Theo kinh nghim th dng t dung mi v
chit nhiu ln c li hn l chit mt ln vi c lng dung mi chit.
1.2.1.5. Sc k.
Phng php sc k do nh bc hc ngi Nga Svet ln u tin a ra v ngy nay n
c ng dng rt rng ri trong nhiu lnh vc thc t. Phng php sc k gm c cc dng:
sc k giy, sc k ct, sc k lp mng, sc k kh.
a. Sc k giy: y l loi sc k phn b m trong tng ng l hn hp cht cn
tch v tng tnh l nc (hoc dung mi khc nh du silicol, du parafin, du ha) tm ln
giy (xenlul). Ta cho cht ln mt im nht nh trn mt giy (im xut pht), khi tng
ng chy qua, cc cht c tch ra. Ta tin hnh sc k giy trong mt bnh kn m khng
gian c bo ho vi tt c cc cu t ca h dung mi c s dng.
h1
h2
h3
H

i lng c trng cho v tr ca cc hp cht sau khi tch l tr s R
f
(ratio of front):
khong cch t im xut pht n trung tm vt cht(h)
khong cch t im xut pht n tuyn dung mi (H)
R
f
=

b. Sc k ct: Ta cho cht mang (xit silic xp, silicagen, bt xenlul) c tm tng tnh
vo ct, sau ho tan hn hp cht cn tch trong tng ng v cho ln u ct. Sau khi
dung dch thm vo ct, ta ra vi nhng lng tng ng khc nhau. Ta thu sn phm tch
vo nhng bnh hng khc nhau, lm bay hi ht dung mi v thu ly sn phm tinh khit.
c. Sc k lp mng: y l loi sc k hp ph m trong ta s dng mt ct h di
dng mt hp cht hp ph mng c tri ln mt tm knh. Thng dng nhng tm knh c
(50 x 200mm, 200 x 200mm) lp cht hp ph (silicagen, xt nhm trn t st). Cch
tin hnh sc k lp mng ging nh sc k giy trn y.
d. Sc k kh: y l mt phng php hin i c hiu lc cao m trong hn hp
cht c phn b gia tng tnh (lng) v mt kh tr v vic vn chuyn c tin hnh
trong tng kh. Phng php ch gii hn cho nhng cht d bc hi m khng b phn hu
nhit cao hay trong khi phn hu cho nhng sn phm xc nh di th hi.
Nguyn tc hot ng ca mt my sc k kh: tng tnh (parafin, cc iankyl phtalat,
cc polyglycol) c tm trn mt vt liu mang th rn (xt silic, t st) c t
trong ct tch (ng knh ct khc nhau khong t 6mm n 0,25m). Di mt th hiu p
sut khng i, mt lung kh (hyr, hli, nit, agon, xt cacbon) chy qua ct tch v hn
hp cht cn tch vo u ct c a vo lung kh ny. Dng kh mang cht chy qua ct v
trong qu trnh cc cht c tch ra khi nhau, c o v c ghi nhn bng mt h
thng pht hin thch hp.
My pht hin
Cht cn tch a vo
Kh mang
Kh quyn
Thit b hng
T
n
g

t
n
h
My t ghi
S mt my sc k kh.
1.3. Cng thc phn t ca cc cht hu c .
tin hnh xc nh cng thc phn t ca mt cht hu c ta cn phi:
1. Phn tch nh tnh cc nguyn t - tc l xc nh nhng nguyn t no cu to nn
phn t.
2. Phn tch nh lng cc nguyn t - tc l xc nh s lng cc nguyn t ca cc
nguyn t cu to nn phn t v lp cng thc n gin ca phn t.
3. Xc nh phn t lng ca phn t - lp cng thc ng ca phn t.
1.3.1. Phn tch nh tnh cc nguyn t.
a. Pht hin cacbon v hyr: S c mt ca cacbon v hyr c pht hin bng phn
ng t chy hp cht hu c vi xt ng.
(C, H) + CuO------
t
----- Cu + CO
2
+ H
2
O
CO
2
thot ra trong phn ng c pht hin bng Ba(OH)
2
cho kt ta BaCO
3
mu trng,
cn H
2
O c pht hin bng CuSO
4
cho hp cht CuSO
4
.5H
2
O c mu xanh.
b. Pht hin Nit: Nu trong hp cht c cha Nit th khi t chy n s ta mi kht
ging nh mi tc chy hoc un vi vi ti xt s ngi thy mi amniac bay ra. Mt phng
php tt hn l un nng chy mu hp cht cn xc nh vi natri kim loi. Nu phn ng xy
ra th s to thnh mui natri xyanua.
Nh vo dung dch ca mui ny mt vi git ca dung dch mui st II v st III, un ti
si v sau khi lm lnh axit ho bng dung dch HCl. Nu c kt ta xanh ph (xanh p-ruyt-
x) th chng t hp cht c nit.
Na (C,N) NaCN
2NaCN FeSO
4
Fe(CN)
2
Na
2
SO
4
Na
4
[Fe(CN)
6
]
Fe
4
[Fe(CN)
6
] 12NaCl
4NaCN
FeCl
3
4
+
+ +
+ +
+ Fe(CN)
2
Na
4
[Fe(CN)
6
]
xanh ph
HCl
Pht hin halogen: Dng dy ng mng t trn ngn la cho n khi ht ngn la mu
xanh, sau cho mt lng nh mu cht ln u dy ng v t tip. Nu ngn la li xut
hin mu xanh th chng t hp cht c halogen. Ta cng c th pht hin halogen bng cch
un nng chy mu cht vi natri kim loi.
(C, H, X) Na NaX +

Pht hin ion X
-
bng Ag
+
cho kt ta AgX.
1.3.2. Phn tch nh lng cc nguyn t.
Nguyn tc chung: t chy hon ton mt lng c cn chnh xc ca mt hp
cht hu c tinh khit vi mt lng d CuO khan. Cacbon v hyr s chuyn hon ton thnh
kh cacbonic v nc. Dng mt lng xy kh ui ht sn phm t chy vo nhng ng
hp th ring bit: ng ng clorua canxi khan hp th hi nc, cn ng ng hyrxit kali
hp thu kh CO
2
. Hai ng ny c cn chnh xc t trc v sau khi th nghim. Hiu s
gia hai ln cn s cho bit khi lng nc v kh CO
2
c to thnh, t c th tnh ra
c hyr v cacbon. Ngy nay ngi ta dng my xc nh nguyn t ca Libis-Pregli.
O
2
hp th H
2
O
hp th CO
2
cha NO
hp th CO
2
v H
2
O
mu cht
ngng t H
2
O
My phn tch nguyn t Libis-Pregli
chuyn NO thnh HNO
3
, cn cho vo bnh cha KMnO
4
v H
2
SO
4
m c. Ta cng
c th dng my phn tch ny nh lng halogen.
nh lng nit c th dng cc phng php sau y:
a. Phng php Dumas-Pregli: trong phng php ny, ngi ta t chy hon ton mt
cht hu c c cn chnh xc vi CuO d trong mt dng kh cacbonic. xt nit to
thnh c kh bng Cu kim loi v N
2
gii phng c dn vo nit k xc nh th tch.
Bit th tch kh nit, p sut v nhit ca kh c th tnh c lng nit ca hp cht.
b. Phng php Kien-an (Kjeldahl): Mt cht hu c c cn chnh xc, c un
vi axit sunfuric m c c mt t mui thu ngn lm xc tc. Trong phn ng ny nit s
chuyn ho thnh mui amni sunfat, sau un vi dung dch kim mnh s gii phng NH
3
.
Cho NH
3
vo mt lng axit d c chun . Sau khi nh lng phn axit d khng b
trung ho bi NH
3
s tnh ra c lng NH
3
t suy ra khi lng nit.
(C, H, N) H
2
SO
4
() (NH
4
)
2
SO
4
HO
-
NH
3
+ +
+ +
. . .
(NH
4
)
2
SO
4
. . .
c. nh lng xy: xy kh nh lng trc tip nn thng ngi ta nh lng cc
nguyn t khc trc ri ly hiu s gia 100% vi tng s phn trm ca cc nguyn t tm
thy.
1.3.3. Xc nh phn t lng.
C nhiu cch khc nhau xc nh phn t lng ca hp cht nhng thng hay dng
t khi hi ca cht hu c cn xc nh so vi khng kh:
M= 29D (D- t khi hi ca cht hu c so vi khng kh)
Ngi ta cng thng dng phng php khi lng ring ca Dumas bng cch o th
tch ca mt lng kh bit trc mt nhit v p sut xc nh, t c th tnh ra
phn t lng ca n.
1.3.4. Lp cng thc phn t.
lp cng thc phn t ca mt hp cht hu c thng phi:
1. Tnh khi lng cc nguyn t ra phn trm.
2. Chia thnh phn phn trm cc nguyn t cho khi lng nguyn t ca chng bit
s nguyn t gam ca mi nguyn t.
3. Thit lp t l s lng cc nguyn t ca cc nguyn t bng cch chia cho s nh
nht.
4. Lp cng thc phn t n gin.
5. Lp cng thc ng ca phn t bng cch i chiu vi phn t lng ca n.
1.4. CU TRC PHN T CA HP CHT HU C
1.4.1. ng phn cu to.
Nu hai hoc nhiu hp cht khc nhau c cng cng thc phn t nhng c mt s tnh
cht vt l hoc ho hc khc nhau th ngi ta gi chng l cc hp cht ng phn ca nhau.
ng phn cu to l loi ng phn m trong cu to ca chng c s khc nhau v
th t lin kt gia cc nguyn t vi nhau. Ngi ta cn gi ng phn ny l ng phn lin
kt.
V d: Hp cht hyrcacbon C
4
H
10
c th tn ti di hai dng ng phn cu to sau
y:
H C
H
H
C
H
H
C C
H
H
H
H
H
H C
H
H
C
H
C
C
H
H
H
H
H
H
v
Hyrcacbon C
5
H
12
tn ti di 3 dng ng phn cu to:
H C
H
H
C
H
H
C C
H
H
H
H
C
H
H
H
H C
H
H
C
H
H
C
H
CH
3
C
H
H
H
H C
H
H
C
CH
3
CH
3
C
H
H
H

Khi s lng ca nguyn t cacbon trong phn t hyrcacbon tng ln th s lng cc
ng phn cu to tng rt nhanh. V d C
6
c 5 ng phn, C
7
-9, C
8
-18, C
20
-366 319, C
40
-
62.491.178.805.831 ng phn.
Mt loi ng phn cu to khc xut hin khi phn t ca cc hp cht hyrcacbon c
cha cc lin kt bi. V d hp cht hyrcacbon C
4
H
8
tn ti di 2 dng ng phn sau:
H C
H
H
C
H
H
C C
H H
H H C C C C H
H
H
H H H
H
v
1.4.2. ng phn lp th.
ng phn lp th l nhng hp cht c cng thnh phn cu to nhng khc nhau v s
phn b khng gian ca cc nguyn t hoc nhm nguyn t trong phn t. Hin nay ngi ta
chia ng phn lp th thnh 3 loi: ng phn quang hc,ng phn hnh hc, ng phn cu
dng da vo c im cu trc khng gian cng nh cc tnh cht l ho khc nhau ca chng.
1.4.2.1. ng phn quang hc.
ng phn quang hc l nhng hp cht c mt hay nhiu trung tm vt (cacbon bt i
xng, mt phn ca phn t) khng trng vi nh. C hai loi ng phn quang hc l ng
phn quang hc i quang v ng phn quang hc khng i quang.
a. ng phn quang hc i quang: ng phn quang hc i quang l 2 cht c thnh
phn ging nhau, ch khc nhau mt tnh cht l mt phng phn cc ca nh sng phn cc
quay i nhng gc c tr s ging nhau nhng ngc chiu nhau (chiu quay sang phi c k
hiu bng du +, chiu quay sang tri bng du -) v 2 ng phn nh vy vi nhau to thnh
mt cp i quang.
Trng hp trung tm bt i l nguyn t cacbon bt i xng (k hiu l
*
C) - tc l
nguyn t cacbon lin kt vi 4 nhm th hon ton khc nhau. Mt phn t c cha mt
nguyn t
*
C c th tn ti di 2 dng ng phn: 1 quay phi v 1 quay tri i xng vi
nhau nh vt v nh qua gng nhng khng th chng kht ln nhau c, tng t nh 2
chic giy ca mt i giy hoc bn tay phi v bn tay tri. V d m hnh t din ca axit (-)-
lactic v (+)-lactic sau y:
COOH
OH
CH
3
COOH
HO
CH
3
H H
mt phng gng

Cp i quang trn y ca axit lactic c biu din bng m hnh khng gian nhng
i vi nhng phn t phc tp th s dng phng php ny khng thun tin. V vy Fish
ngh mt phng php biu din khng gian ca cc ng phn quang hc trn mt phng
gi l cng thc chiu Fish. c cng thc chiu Fish, ta t m hnh t din ca phn t
sao cho nguyn t cacbon bt i xng nm trong mt phng giy, cc lin kt
*
C-b v
*
C- c
nm trong mt phng nm ngang hng t mt phng giy n ngi quan st. Cc lin kt
*
C-
a v
*
C- d nm trong mt phng thng ng hng ra xa ngi quan st.

a
c
b
d
b
c
d
aa
M hnh t din ca *Cabcd Cng thc chiu Fish ca *Cabcd
Chiu cc lin kt xung mt phng giy, ta s c cng thc chiu Fish. Axit lactic trn
y c biu din di dng cng thc chiu Fish nh sau:
COOH
H OH
CH
3
COOH
H HO
CH
3

i vi mt cht quang hot, ngi ta thng dng quay cc ring [] c trng
cho n. [] c th c gi tr m hoc dng khc nhau ty theo cht quang hot lm quay mt
phng ca nh sang phn cc v bn phi hoc bn tri.
b. ng phn quang hc khng i quang: ng phn quang hc khng i quang l
nhng ng phn lp th ca nhau theo ngha chung nhng chng khng phi l nhng ng
phn vt-nh ca nhau. ng phn quang hc khng i quang c th xut hin trong mt s
trng hp sau:
1. Cc t hp bt k ca mt dng i quang ca cp i quang ny vi cc dng i
quang ca nhng cp i quang kia (trng hp ca cc hp cht c t hai cp i quang tr
ln). V d 3-phenylbutanol-2 c ng phn I v II l mt cp i quang, III v IV l mt cp
i quang khc. Cn cc t hp ca I vi III hoc IV, II vi III hoc V l nhng ng phn
quang hc khng i quang ca nhau.
CH
3
H OH
H C
6
H
5
CH
3
CH
3
HO H
H H
5
C
6
CH
3
CH
3
H OH
H H
5
C
6
CH
3
CH
3
HO H
H C
6
H
5
CH
3
[ ] = -0,69 [ ] = +30,9 [ ] = -30,2 [ ] = +0,68
2. Cc ng phn mz: Chng l nhng ng phn lp th m phn t ca chng c
cha 2 hoc nhiu trung tm bt i xng nhng gia hai na ca chng c s i xng vt-
nh, do quay cc ca chng b trit tiu khin cho ng phn mz khng quang hot. V
d axit tactric cha hai nguyn t
*
C (ging nhau) c mt cp i quang v mt ng phn
mz c biu din bng cng thc chiu Fish nh sau:
COOH
HO H
H OH
COOH
COOH
H OH
HO H
COOH
COOH
H OH
H OH
COOH
Cp i quang ng phn mz

c. Bin th Raxmic: Bin th Raxmic l hn hp gm cc lng bng nhau ca ng
phn quay phi v ng phn quay tri. N c quay cc ring bng 0 v c k hiu l ().
1.4.2.2. ng phn hnh hc.
ng phn hnh hc l ng phn lp th gy nn bi s phn b khng gian khc nhau
ca nguyn t hay nhm nguyn t xung quanh phn cng nhc ca phn t. Phn cng nhc
c th l mt ni i, 1vng hoc 1 phn vng trong xyclankan
1. Trng hp phn cng nhc trong phn t l mt ni i ta c cc loi ng phn:
a. ng phn cis-trans xut hin cc ni i C-C khi c hai nguyn t hoc nhm
nguyn t nm cng pha hoc khc pha ca mt phng .
C C
b b
a a
C C
b
a
b
a
ng phn cis
ng phn trans

V d: 1, 2-icloten c 2 ng phn sau y:
C C
Cl
H
Cl
H
C C
Cl
H Cl
H
cis-icloten trans-icloten

ng phn syn-anti cng l ng phn cis-trans nhng chng c xut hin cc
hp cht c ni i gia nguyn t cacbon vi mt nguyn t d t hoc gia cc d t vi nhau.
C N
H
5
C
6
H
CH
3
N N
H
5
C
6
C
6
H
5
N N
H
5
C
6
C
6
H
5
C N
H
5
C
6
H CH
3
syn
anti
syn
anti

b. Trng hp phn cng nhc ca phn t l mt ni n hoc mt phn vng trong cc
hp cht vng. V d: axt mtylxyclppanic c ng phn cis v trans nh sau:
H H
COOH CH
3
H CH
COOH H
3
cis
trans

Tng t nh vy hp cht 1, 3-imtylxyclhexan c 2 ng phn:
CH
CH
3
3
CH
CH
3
3
cis
trans

1.4.2.3. ng phn cu dng.
ng phn cu dng l ng phn lp th ng ca cc phn t hu c c phn bit
nhau bi s phn b khng gian ca cc nguyn t hoc nhm nguyn t trong cng mt cu
hnh. S chuyn ho tng h gia cc ng phn cu dng c thc hin bi s quay quanh
cc lin kt n hoc s b gp ca cc phn vng.
ng phn cu dng quay xut hin cc hp cht mch h khi c s quay ca cc
nguyn t xung quanh trc ca mt hay nhiu lin kt n m khng lm t lin kt ny.
biu din cc ng phn cu dng, ngi ta thng dng cng thc phi cnh, hoc cng thc
chiu Niumen.
Theo cch biu din phi cnh, lin kt gia hai nguyn t cacbon hng theo ng
cho t tri qua phi, ng k vch dng ch cc lin kt nm trong mt phng giy, ng
gch song song nhn dn ch cc lien kt hng v pha di mt phng giy, ng m hnh
tam gic ch cc lin kt hng v pha trn mt phng giy.
a
b
c
a
b
a
b
c
a
b
d
d
Trong cng thc chiu Niumen, phn t c nhn dc theo lin kt C-C (ngha l trc
lin kt ny trc giao vi mt phng giy).
a
b c
a
b
d
Nh vy hai nguyn t ny hon ton che khut nhau v ngi ta biu din chng bng
mt vng trn chung (thc t l hai vng trn chng kht ln nhau). Cc lin kt v cc nhm
th ni vi cc nguyn t cacbon c chiu ln mt phng vung gc vi trc ni hai nguyn
t cacbon (mt phng giy). phn bit hai h thng cc lin kt ni vi cc nguyn t cacbon
th nht v th hai, ngi ta ko di cc lin kt ca cc nhm th vi cc nguyn t cacbon
gn n tm ca ng trn, cn cc lin kt ca cc nguyn t vi nguyn t cacbon xa th
ch gp ng trn m thi.
V d: tan hai nhm mtyl c th quay xung quanh lin kt n C-C khin cho phn t
c th c v s cu dng khc nhau trong c hai cu dng ti hn. Mt cu dng c th nng
cao nht ng vi gc quay ca nhm mtyl l 120
0
, 240
0
, 360
0
gi l cu dng che khut II,
IV, VI (th nng cao nht do 3 cp hyr i din nhau nht v gn nhau nht nn y nhau
mnh nht), v mt cu dng c th nng thp nht ng vi cc gc quay ca nhm mtyl l
60
0
, 180
0
v 300
0
gi l cu dng xen k I, III, V (c th nng thp nht do 3 cp hyr nm v
tr cch xa nhau nht nn y nhau yu nht).

H
H
H
H
H

H
H
H
H

H
H
H
H
H
H
H
H
H
H
H
H

H
H
H
H
H
H
H
H
H
H
H
H
H
H

H
I II III IV
V
VI

S bin i th nng khi nhm mtyl quay mt vng t 0 n 360
0
c biu din trn
gin sau (phn t mtan tri qua 3 cu dng che khut khng khc bit nhau v 3 cu dng
xen k ng nht nhau hng ro th nng lp li 3 ln). Nh vy cu dng xen k c th nng
thp nht nn l dng bn nht. Trng hp mtan dy cc cu dng I, III, V c th nng thp
nht do chng bn nht, dy cc cu dng II, IV, VI c th nng cao nht nn t bn nht.
300 360
I
II
III
IV
V
VI
60 120 180 240
E(Kcal/mol)
gc quay
o
Gin nng lng ca tan

1.5. LIN KT HO HC.
1.5.1. Cc loi lin kt ho hc.
S pht trin ca l thuyt v lin kt ho hc - tc l lc gi cc nguyn t li vi nhau
trong phn t c chia lm hai thi k: thi trc nm 1926 v t cho n nay. Nm 1926,
nh bc hc Kosen a ra thuyt lin kt ion v nh bc hc Luit a ra thuyt lin kt
cng ho tr. Ni dung ca hai l thuyt c th tm tt nh sau:
Trong nguyn t ht nhn mang in tch dng c bao quanh bi cc in t phn b
thnh cc lp khc nhau. Trn mi lp c s in t nht nh: 2 in t trn lp th nht, 8
in t trn lp th hai, 8 hoc 18 trn lp th 3S to thnh hp cht l kt qu to thnh
lp in t bo ho (ging kh tr) ca cc nguyn t trong phn t. Lin kt ion xut hin do
kt qu ca s chuyn dch electron. V:d qu trnh to thnh hp cht LiF.
Li
Li
+
-e
Li + e Li
+
F
F
-
+e
F + e F
-
Do lc ht tnh in dn n to thnh LiF.
Lin kt cng ho tr c hnh thnh bng i in t gp chung. V d: s to thnh
phn t hyr, mi nguyn t hyr c 1 in t nn khi to thnh phn t 2 nguyn t gp
chung cc in t li lm y lp in t cho nhau.
+ H H H H
Tng t:
+ F F F F
H + H F F

1.5.2. Thuyt c hc lng t.
Nm 1926, nh bc hc Schrodinger a ra thuyt c hc lng t c biu din
di dng mt phng trnh ton hc v s ph thuc ca s chuyn ng ca cc in t vo
nng lng ca n. Phng trnh ny gi l phng trnh sng (electron khng nhng mang
tnh cht ht m cn mang tnh cht sng). Phng tnh sng rt phc tp khng th cho kt qu
chnh xc nn phi dng phng trnh gn ng gi l hm s sng. Hm sng no cho gi tr
nng lng cng thp hm sng cng ng. Tuy mang tnh cht gn ng song thuyt c hc
lng t gii thch c nhiu hin tng c bit l s to thnh phn t v nguyn t.
1.5.3. Ocbitan nguyn t.
Phng trnh sng khng cho php xc nh chnh xc v tr ca in t trong mt thi
im nht nh, tc v qu o chuyn ng ca n nhng cho php xc nh xc sut tm
thy in t mt thi im xc nh. n v khng gian m xc sut tm thy in t l
ln nht gi l ocbitan. C nhiu ocbotan sp xp xung quanh ht nhn khc nhau, c hnh dng
v kch thc khc nhau. Dng ocbitan ca in t c xc nh bi nng lng ca n.
thun tin ngi ta biu din in t di dng cc m my (ging nh tm nh b m). Hnh
dng ca m my chnh l hnh dng ca ocbitan. Cc m my ny khng ng nht. Ocbitan
c nng lng thp nht l 1s-ocbitan.
1s-obitan

Ocbitan khng c gii hn xc nh v xc sut tm thy in t rt xa ht nhn vn
c. Trong gii hn biu din hnh trn c ngha l xc sut tm in t l 95%.
Tip theo 1s-ocbitan l 2s-ocbitan c mc nng lng cao hn do lc lin kt tnh in
gia ht nhn v electron yu hn. Cc ocbitan tip theo l 3s-ocbitan, 2p-ocbitan: P
x
, P
y
, P
z

2p
x
x
2p
y
y
2p
z
z
Cc ocbitan 2p

S phn b in t trn cc ocbitan tun theo nhiu nguyn l khc nhau, c bit
nguyn l ngoi tr Pauli c ngha rt ln. Theo nguyn l ny trn mt ocbitan xc nh ch
c th c ti a l 2 electron vi iu kin chng c s lng t spin i nhau.
I.5.4. Ocbitan nguyn t.
Trong phn t cng nh trong cc nguyn t ring bit cc electron chim cc ocbitan
tng ng vi cc quy tc phn b chng, ch khc ocbitan phn t c nhiu ht nhn. s
dng phng trnh sng trn y cho ocbitan phn t ngi ta a ra 2 iu cho php:
a. Mi mt cp in t ch nh v (gii hn) xung quanh hai ht nhn nguyn t
b. Dng cc ocbitan ca cc electron nh v v s sp xp ca chng ph thuc vo
dng v s sp xp cc ocbitan nguyn t to nn phn t
I.5.5. Lin kt cng ho tr.
to lin kt cng ho tr ocbitan ca nguyn t ny phi xen ph ocbitan ca nguyn
t kia v mi mt ocbitan phi c 1 electron. y xy ra s phi hp 2 ocbitan nguyn t to
thnh mt ocbitan lin kt. Hai electron trn ocbitan lin kt phi c s lng t spin i nhau.
Mi mt nguyn t nm trn ocbitan lin kt chung ny cng c xem nh chng thuc v ca
c hai ht nhn nguyn t. V d s to thnh phn t H
2
t 2 nguyn t hiro. y mi
nguyn t hiro c mt electron chim mt ocbitan 1s. to thnh lin kt 2 ht nhn nguyn
t phi tin ti gn nhau sao cho cc ocbitan nguyn t xen ph nhau. Phn t H
2
bn vng nht
l khi khong cch gia 2 ht nhn nguyn t l 0,74A
0
. Khong cch ny c gi l di
kin kt.
H H H H
H H
1s 1s
ocbitan lin kt

Ti khong cch r = 0,74 A
0
t hp nng lng ca s xen ph cc electron ca phn t
hyr v s y nhau gia cc ht nhn nguyn t l nh nht.
(eV )
(A
o
)
S ph thuc ca nng lng in t trong
phn t H vo khong cch hai ht nhn
2

1.5.6. Cc phng php tnh gn ng trong lin kt cng ho tr.
gii phng trnh sng cho phn t ngi ta a ra hai phng php gii gn
ng.
(1)-Khi xa lc ht gia cc phn t mang in tch tri du l ch yu, khi gn lc y l
ch yu.
(2)-Lun lun y nhau nn khng th to thnh lin kt bn vng c.
a. Phng php s ho tr
Trong phng php ny cc electron c spin i nhau ca hai nguyn t khc nhau A v
B c th ghp i li to thnh lin kt cng ho tr lng electron. Khi to thnh lin kt gia
A v B, ta khng th phn bit c electron I ca A vi electron II ca B. m t iu
ngi ta thng dng cng thc gii hn.
V d:
A c ( AI) v A ( AII)
B c ( BI) v B ( BII)
AIBII v AIIBI
(
1
) (
2
)
Theo cng thc ny trng thi thc ca phn t phi l ci g trung gian gia (1) v
(2). Do ta c:
1
=
I
A
.
II
B
v
2
=
II
A
.
I
B

- l hm sng ocbitan nguyn t .
Phng trnh thc ca ocbitan nguyn t s l:
= C
1
1
+ C
2
2

Phng php s ho tr dng lm c s ton hc cho quan nim v s cu to cng
hng cc cu to. V d benzen c th biu din bng hai cng thc I v II ca Kkul v ba
cng thc III, IV, V ca ioa.
I
II III
IV
V

Do phng trnh thc ca benzen s l:
= C
1
(
1
+
2
) + C
2
(
III
+
IV
+
V
)
Cc h s C
1
, C
2
c gi tr sao cho nng lng ng vi hm s l cc tiu.
b. Phng php ocbitan.
Phng php ocbitan dng hm sng ca tng electron trong trng bao gm cc ht
nhn v electron cn li.
= C
1

1
+ C
2

2
+ .+ C
3

3
= C
i

I

Xt lin kt ho hc theo phng php ocbitan phn t thc cht l m t s phn b
electron trong phn t theo ocbitan ca n theo cc nguyn l cho nguyn t ch khc l ocbitan
nguyn t c nhiu trung tm ht nhn. V d ocbitan nguyn t hyr c hai trung tm ht
nhn. Trong trng hp ny nghim ca phng trnh sng gii ra phi c hai nghim ng vi
nhng trng thi khc nhau ca phn t. Trng thi th nht ng vi s ht nhau c nng lng
thp hn nng lng ca nguyn t l trng thi ocbitan phn t lin kt:
lk
= C
1

1
+ C
2

2

ocbitan lin kt mt gp electron gia hai ht nhn l ln nht, tri li ocbitan
phn lin kt l bng 0.
H
H
+
-
+
H H
obitan lin kt
obitan phn lin kt
obitan lin kt
obitan phn lin kt
H
1s
H
1s
+
i vi nhng h c nhiu trung tm v nhiu electron vic gii phng trnh sng s
dn n nhiu nghim ng vi nhng trng thi nng lng khc nhau.
1.5.7. S xen ph v s lai ho.
a. S xen ph.
Lin kt cng ho tr c hnh thnh l do s xen ph ca cc ocbitan nguyn t thnh
cc ocbitan phn t lin kt. Ocbitan phn t lin kt cng bn v nng lng thot ra khi hnh
thnh ocbitan cng ln nu vng xen ph ocbitan cng ln. Khuynh hng ca s xen
ph l tin ti cc i. Mun cho cc ocbitan nguyn t tng tc c hiu lc vi nhau thnh
ocbitan phn t chng phi tho mn 3 iu kin sau y:
1- Nng lng ca chng gn bng nhau.
2- S xen ph mc ln.
3- Chng phi c cng mt kiu i xng vi trc ni hai nhn nguyn t.
Xt iu kin 3 ta c th xen ph:
- Hai ocbitan s
- Mt ocbitan s vi mt ocbitan p no c trc i xng trng vi trc ni hai ht
nhn.
- Hai ocbitan p c trc i xng song song vi nhau (cng p
x
, p
y
hoc p
z
)
S xen ph c th theo trc hay bn trc ni gia hai ht nhn nguyn t.
Theo trc:
+
-
+
-
+
-
+ -
+
s
p
Ocbitan lin kt c trc i xng l ng thng ni gia hai ht nhn v c gi l
ocbitan . Lin kt cng ho tr c hnh thnh gi l lin kt . S xen ph xy ra tng t
nh vy i vi trng hp ocbitan p + p.
+
-
+
-
- +
-
+
+
- + -
p p
S xen ph bn trc:
II
+
-
+
-
+
-
-
+
+
-
+
p
p
II
II
*
S xen ph bn trc s to thnh ocbitan v lin kt .
V ocbitan khng c tnh i xng i vi trc hai ht nhn m ch i xng vi mt
phng nt cha 2 trc nn lin kt t bn, d phn cc ho. Mt khc cn tr s quay t
do ca nguyn t hay nhm nguyn t xung quanh trc lin kt (do s quay s vi phm nguyn
l cc i). l nguyn nhn lm xut hin cc ng phn hnh hc.
b. S lai ho.
Ph hp vi nguyn l xen ph cc i, tng hiu lc ca s lin kt, cc ocbitan
tham gia xen ph c th b lai ho. Ni dung ca s lai ho c th tm tt trong trng hp hnh
thnh CH
4
nh sau:
Cacbon C
6
-1s
2
2s
2
2p
2

s
2
1 p
2
2 s
2
2
Theo s ho tr trn y th ccbon c ho tr 2 do nu kt hp vi nguyn t hyr
th phi to thnh hp cht CH
2
. Th nhng trong phn t mtan, cacbon c ho tr 4. iu
c gii thch rng: c mt electron ca ocbitan 2s chuyn qua ocbitan p cn trng.
s
2
1 p
3
2 s
1
2
Kt qu to thnh 4 in t c thn v do c th hp vi 4 nguyn t hyr to thnh
CH
4
. Nh vy c th nhn thy rng cacbon s to thnh 3 lin kt c cng mt loi lin kt ca
cc ocbitan p v mt lin kt ca ocbitan s. Nhng thc t 4 lin kt ca CH
4
hon ton ging
nhau. iu c gii thch bi s lai ho ca cc ocbitan-tc l s t hp lai to thnh nhng
ocbitan c dng khc vi ocbitan ban u c kh nng xen ph cao hn do lin kt hnh
thnh bn vng hn. Thc vy cc kt qu tnh ton cho thy rng:
1- Ocbitan lai to tt nht c hng xen ph cao hn ocbitan s hoc ocbitan p.
2- 4 ocbitan lai to tt nht c hng xen ph cao hn hon ton ng nht vi nhau.
3- Cc ocbitan ny hng n gc ca mt t din u- tc l s sp xp m trong
cc ocbitan nm v tr cch xa nhau nht. S lai ho ny gi l lai ho t din. Gc
lai ho trong trng hp ny l 109
0
28
.

lai ha sp
3
s
2
1 sp
3
s
2
1 p
3
2 s
1
2
S lai ho sp
3
c th biu din nh sau:
+
1
3
2
s
p sp
3

x
y
z
s + 3p
sp
3
lai ha
Cc kt qu tnh ton cho thy rng nu coi kh nng xen ph ca ocbitan s l 1 th
ocbitan p l 3 v ocbitan lai ho sp
3
l 2. Trong phn t mtan cng nh cc ng ng ca n,
ocbitan lai to sp
3
ca cacbon xen ph vi ocbitan 1s ca hyr to thnh lin kt (C-H).
cc ng ng ca mtan 2 ocbitan sp
3
ca hai nguyn t cacbon bn cnh nhau to thnh lin
kt (C-C). V gc ho tr ca nguyn t cacbon sp
3
l 109
0
28
nn mch cacbon trong phn t

ankan l ng gp khc khc hnh ziczc.

H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH CH CH CH CH CH CH
4 3 3 3 2 2 3

Kiu lai ho th hai l s tng hp 1 ocbitan s vi 2 ocbitan p to thnh 3 ocbitan sp
2
(lai
to tam gic hoc lai ho phng). Trc i xng ca 3 ocbitan sp
2
nm trn mt mt phng to
thnh gc 120
0
. Kh nng xen ph tng i ca ocbitan sp
2
l 1,99.
x
y
+
+
+
s + 2p
sp
2

lai ha sp
2
s
2
1 sp
2
p
1
2
s
2
1 p
3
2 s
1
2
Trong phn t tylen cc ocbitan sp
2
tham gia xen ph to nn 5 lin kt c trc nm
trong mt mt phng. Cn li 2 ocbitan p thun khit cha lai to xen ph bn nhau to thnh
lin kt .
H
H
H
H
C C
H
H
H
H
Kiu lai ha sp-t hp ca mt ocbitan s v mt ocbitan p gp trong cc phn t c ni 3
vi kh nng xen ph l 1,93 v gc to bi trc i xng ca 2 ocbitan l 180
0
(kiu lai ho
ng thng).
+
+
- +
-
+
-
sp
s + p

lai ha sp
s
2
1 p
3
2 s
1
2
s
2
1 sp p
2
2

Trong phn t axtylen, cc ocbitan lai ho sp xen ph ln nhau v vi ocbitan hyr
(1s) to thnh 3 lin kt m trc lin kt cng nm trn mt \ng thng, cn li 4 ocbitan p
thun khit chng s xen ph bn nhau tng i mt to nn 2 lin kt .
Cc lin kt ca axtylen.
H C C H

H H
C C
H C H C
1.5.8. Mt s c tnh ca lin kt cng ho tr .
a. Nng lng lin kt.
Nng lng lin kt A-B l s nng lng thot ra khi hnh thnh lin kt t hai
nguyn t A v B hay hai gc t do A
.
v B
.
. cng chnh l nng lng cn thit lm t
lin kt A-B thnh 2 nguyn t hoc 2 gc t do. Tuy vy nng lng lin kt ch nhng gi tr
trung bnh gn ng ca nng lng phn ly. V d khi dng khi nim nng lng lin kt ta
gi thit rng tt c cc lin kt C-H chng hn trong ankan l nh nhau. Thc ra nng lng
cn thit lm t lin kt C-H th nht trong mtan chng hn khng phi bng nng
lng cn thit phn cp hon ton phn t ny thnh cacbon v hyr, cng khng phi
bng nng lng lm t C-H trong tan, prpan, bezenNng lng lin kt ca C=C v CC
khng ln gp i hay gp ba ca C-C.
b. S phn cc.
Trong lin kt cng ho tr cp electron lin kt hay ocbitan phn t lin kt ch c
phn b tht u gia hai nguyn t v mmen lng cc bng 0 khi no hai nguyn t hon
ton ng nht nh h A-A: Cl-Cl, H-H, H
3
C-CH
3
Trong trng hp hai nguyn t lin kt
vi nhau khng ng nht h A-B: H-Cl, CH
3
-Clcp electron lin kt s lch i t nhiu v
pha mt nguyn t no c m in ln hn v do lin kt c mmen lng cc khc 0
( 0).
A B
A A
A B
H A-A H A-B
H
A=B
A B

S phn cc khng nhng c th xy ra lin kt m cn xy ra c lin kt , h
A=B hoc AB, v d H
2
C=O, -CN
m t s phn cc ca lin kt cng ho tr ngi ta thng dng mi tn thng cho
lin kt v mi tn cong cho lin kt (chiu mi tn l chiu chuyn dch ca cc electron).
H
3
C Cl H
3
C Cl
+

-
hoc
hoc H
3
C Cl
+

-
hoc H
2
C O H
2
C O
- +

+

-
H
2
C O hoc
1.6. L THUYT V S CHUYN DCH ELECTRON TRONG PHN T CC
HP CHT HU C.
1.6.1. Hiu ng cm ng.
a. nh ngha v phn loi.
Xt hai phn t prpan v n-prpylclorua.
H C C C H
H
H
H
H
H
H
H C
3
H
H
C
1
H
H
C
2
H
H
Cl
+ +

+
Khc vi prpan, prpylclorua c nguyn t clo vi m in ln do lin kt C
1
-Cl
b phn cc v kt qu clo mang mt phn in tch m v C
I
mang mt phn in tch dng.
V C
1
c mt in tch dng nh nn lin kt C
1
-C
2
b phn cc v pha C
1
, n lt C
3
-C
2

li cng b phn cc v pha C
2
. S phn cc khng nhng xy ra lin kt C-C m cn c
lin kt C-H. Kt qu l phn t b phn cc v xut hin mt mmen lng cc, cn hyr th
tr nn linh ng hn (so vi hyr prpan). Dng phn cc ny gi l phn cc cm ng hay
hiu ng cm ng.
Vy bn cht ca vn hiu ng cm ng l s phn cc cc lin kt lan truyn theo
mch cc lin kt do s khc nhau v m in. Ngi ta k hiu hiu ng cm ng I

(Inductive Effect). Hiu ng cm ng c th gy ra bi nguyn t hay nhm nguyn t ht
electron gi l hiu ng cm ng m (-I), nguyn t hay nhm nguyn t nhng electron gi l
hiu ng cm ng dng (+I). Chiu chuyn dch electron c m t bng mi tn.
Y C C H C X
(+I) (I=0) (-I)

b. Quy lut v hiu ng cm ng ca nguyn t v nhm nguyn t.
Phn tch nhng d kin v hiu ng cm ng nhng nguyn t hay nhm nguyn t
khc nhau ngi ta rt ra mt s quy lut sau:
1. Cc nhm mang in tch dng c hiu ng -I, cc nhm mang in tch m c hiu
ng +I. V d: -N
+
R
3
l nhm I mnh cn O
-
l nhm +I mnh.
2. Nu cc nguyn t ca cng cc nguyn t cng mt chu k nh hay phn nhm
chnh trong h thng tun hon u c hiu ng I th hiu ng cng ln khi nguyn t tng
ng cng v pha bn phi chu k hoc cng pha trn phn nhm chnh.
F > Cl > Br > I
F > OR > NR
2

3. Cc nhm ankyl lun lun c hiu ng +I, hiu ng tng theo bc ca nhm:
CH
3
< CH
3
CH
2
< CH(CH
3
)
2
< C(CH
3
)
3

4. Trng thi lai to ca cacbon c I bin i:
C
sp
> C
sp2
> C
sp3
tc l RCC- > C
6
H
5
- > R
2
C=CR-
c. c im ca hiu ng cm ng.
c im ni bt ca hiu ng cm ng I
l gim rt nhanh khi ko di mch truyn nh

hng.V d nh hng ca clo n lc ca axt butyric nh sau:
Ka.10
5
1,5 3,0 8,9
139,0
CH
3
CH
2
CH
2
COOH
CHCOOH
CH
2
CH
3
Cl

CHCH
2
COOH
CH
3
Cl

Cl CH
2
CH
2
CH
2
COOH
Theo kt qu ca bng trn y th clo v tr lm tng lc axit ln 87 ln, v tr
lm tng 6 ln, v tr lm tng 2 ln.
1.6.2. Hiu ng lin hp.
a. nh ngha v phn loi.
xt hiu ng lin hp ta xt phn t n gin c h cc lin kt lin hp l butaien.
Tng t nh trong phn t tylen, cc nguyn t cacbon trong phn t butaien u trng
thi lai ho sp
2
v h thng cc lin kt l mt h phng. Mi nguyn t cacbon cn li mt
ocbitan p thun khit xen ph vi nhau to thnh 4 ocbitan phn t khc nhau I, II, III, IV.
Cc tnh ton c lng t cho thy rng ocbitan phn t IV c nng lng thp nht ( bao trm
c 4 nguyn t cacbon gi l ocbitan gii to hay khng khu tr). H phn t c ocbitan gii to
nh butaien gi l h lin hp. H lin hp thng gp , p v ,
V d:
C C C C
CH
2
CH CH CH
2
H mch h ,
C C X
H lin hp ,
p
CH
2
C Cl
H mch vng ,
I
II
III
IV
Bnh thng phn t butaien c gii ta nh IV. Nu thay mt nguyn t hyr CH
2

bng CH=O chng hn th do c tnh phn cc sn c ca nhm CHO s lm cho mt
electron chuyn ng dch mt phn v pha n lm cho ton b phn t b phn cc.
CH
2
CH CH CH
2
CH
2
CH CH CH CH O

Ta ni y c hiu ng lin hp v nhm CHO gy hiu ng lin hp (k hiu l C).
Nhm CHO lm chuyn dch mt electron v pha n nn c hiu ng lin hp m (-C).
Ngc li, nu nguyn t hay nhm nguyn t lm mt electron chuyn dch t pha n n
cacbon th n c hiu ng lin hp dng (+C).
Vy hiu ng lin hp l hiu ng electron truyn trn h lin hp gy nn s phn cc
h electron trn .
b. Quan h gia cu to ca nhm th vi hiu ng lin hp.
Hiu ng lin hp c 3 loi:
1. Cc nhm +C: Cc nhm ny ni chung u c cp electron cha s dng hay
electron d:
-O
-
, -S
-
, -OH, -SH, -NH
2
, -NR
2
, -NHCOCH
3
, -F, -Cl, -Br.
ng ch l hu ht cc nhm c hiu ng +C ng thi c hiu ng I mc khc
nhau. V vy trong trng hp c th cn phn bit nh hng ca mi loi. V d: CH
3
O- l
nhm y electron ni chung v c khi ni ring v nh hng lin hp v +C > -I.
CH CH CH CH
2
CH
3
O
+C
-I

Tri li clo l nhm ht electron ni chung v +C< -I.
CH
2
CH CH CH Cl
-I
+C
i vi cc nguyn t hay nhm nguyn t c cng hiu ng lin hp +C th: nguyn t
mang in m c hiu ng +C mnh hn nguyn t tng t khng mang in.
O
-

> -OR
-S
-
> - SR
Trong mt chu k nguyn t cng bn phi th +C cng yu:
-NR
2
> -OR > -F
Trong mt phn nhm chnh lc +C gim t trn xung di:
-F > -Cl > -Br > -I
-OR > -SR > -SeR
2. Cc nhm C: a s cc nhm ny l nhng nhm khng no:
-NO
2
, -CN, -CHO, -COR, -COOH, -CONH
2

Thng cc nhm C c c hiu ng I.
Cc nhm -C=Z c lc C ph thuc vo Z ( nu Z cng bn phi chu k th lc C
cng ln):
C O C NR C CR
2
Nhm mang in tch dng c C ln hn khng mang in:
C NR C NR
2
+
3. Cc nhm c hiu ng C vi du khng c nh.
Loi ny thng l nguyn t hoc nhm nguyn t cha no nh: vinyl, phenylV
d: trong phn t nitrbenzen v anilin phenyl, c th biu hin hiu ng +C hay C ty theo
nhm nguyn t gn vi phenyl l -NO
2
(nhm C) hay NH
2
(nhm +C).
O
2
N
-C +C
H
2
N
+C -C

c im ca hiu ng lin hp: n thay i tng i t khi ko di mch cc lin kt
lin hp. Hiu ng lin hp ch c hiu lc mnh trn h lin hp phng (tc l cc ocbitan p
thun khit phi c trc song song vi nhau).
N N
X
X
H , p phng H , p khng phng

1.7. MT S PHNG PHP VT L THNG DNG TRONG HO HC HU
C
xc nh cng thc cu to ca mt hp cht hu c, trong phn trc ta xem xt
cc phng php tinh ch cc hp cht, xc nh thnh phn v khi lng cc nguyn t c
trong mt phn t. Ngy nay xc nh cu to ca mt hp cht hu c nhanh hn v chnh
xc hn, ngi ta dng cc phng php vt l nh khi ph, quang ph hng ngoi, ph cng
hng t ht nhn
1.7.1. Khi ph.
Nu ta bn ph phn t ca mt hp cht hu c bng mt dng electron c nng lng
trung bnh (20-70 electron-vn) th cc phn t s b ion ho v ph v thnh nhiu mnh khc
nhau, trong c mt s mnh l ion dng. T l khi lng ca mi loi ion vi din tch
(m/e) chnh l khi lng ca ion. V d nu ta bn ph phn t nopentan:
C
CH
3
H
3
C CH
3
CH
3

M
+
(C
5
H
12
)
+
M
1
+
(C
4
H
9
)
+
M
2
+
(C
3
H
5
)
+
M
3
+
(C
2
H
5
)
+
M
4
+
(C
2
H
3
)
+

m/e 72 57 41 29 27
Nu cho dng cc ion dng ny vo mt t trng hng vung gc vi hng ca t
trng th cc ion c t l m/e khc nhau nn di tc dng ca t trng s b lch i khi
hng ban u nhng qu o khc nhau. Tn hiu thay i ny ca cc ion s c mt b
phn ghi t ng ghi li v cho ta ph khi lng ca hp cht cn xc nh m trong mi
loi ion s c th hin bng mt pic ring bit c cng ng vi i lng m/e. Pic c bn
c cng tng i ln nht M
+
tng ng vi phn t lng ca phn t. Tuy nhin nhiu
khi pic M
+
l mt pic c cng tng i yu. V d khi ph ca nopentan, M
+
ng vi
phn t lng ca phn t c cng tng i yu, cn M
+
ng vi phn t lng ca
butanhytc cng tng i ln nht.
M
+
M
1
+
M
2
+
M
3
+
M
4
+
10 20 30 40 50 60 70 80 90 100 110 120 130 140
25
50
75
100
0
I / I
0
(%)
Ph khi lng ca nopentan
10 20 30 40 50 60 70 80 90 100 110 120 130 140 0
I / I
0
(%)
20
40
60
80
100
M
+
= 72
57(M-CH )
3

+
43(M-CHO)
+
29(CHO)
+
15(CH )
3

+
Ph khi lng ca butanhyt
1.7.2. Quang ph hp ph.
a. Quang ph in t.
Chng ta bit mt s bc x in t nh nh sang thng, nh sng cc tm, hng
ngoi, tia Rngen, sng rai
xa
c s
p.quay
p.dao ng
gn
gn xa
Hng ngoi
T ngoi
p.electron
Tia X
Tia

cm
-1
10 10
3
5.10
3
10
4
10
6
Tt c cc loi sng trn y u c mt tc truyn sng l 3.10
10
cm/s v tn s =
c/ trong c l tc truyn sng, l di sng (cm).
Khi mt chm tia sng in t gp phi mt vt no th n c th xuyn qua, cng c
th b hp th li ph thuc vo tn s ca sng v cu to ca vt th. Ta bit rng, bc x in
t l mt dng nng lng, do khi phn t hp th bc x in t th n c cung cp
thm mt nng lng E= E
1
-E
0
= h = hc/.
Nng lng E c phn t hp th, c th gy ra s dao ng, s quay ca cc nguyn
t trong phn t hoc bc chuyn electron n mt mc nng lng cao hn. Tn s bc x
m mt phn t nht nh c th hp thu ph thuc vo trng thi dao ng hay trng thi
quay ca cc nguyn t cu to nn phn t.
Vy ph ca mt hp cht l th cho php xc nh phn no ca bc x in t b hp
th (hay i qua) vt th mt tn s nht nh. N mang tnh cht c trng cho cu to ca
cht.
b. Quang ph hng ngoi.
Trong ho hc hu c, ph hng ngoi c ngha rt ln xc nh cu to ca hp
cht.
Phn t lun lun dao ng. Nu dao ng lm thay i di cc lin kt th ngi ta
ni l dao ng ho tr, cn nu thay i gc lin kt th ngi ta gi l dao ng bin
dng.
Gi s phn t c n nguyn t, vy c 3n bc t do trong 3 bc dng xc nh
chuyn ng tnh tin, 3 bc dng xc nh chuyn ng quay v cn li 3n-6 bc l dao
ng t do (phn t thng hng, c 3n-5 bc dao ng t do v ch c hai bc chuyn ng
quay). V d phn t H
2
O c n=3 do 3.3-6=3 bc dao ng t do.
a
b
c
a,b - dao ng ha tr c - dao ng bin dng

S thay i dao ng t do ca phn t c gy c gy ra bi s hp th trong vng
hng ngoi. ch ra v tr hp th trong vng ngoi, c th s dng di sng hay tn s
(thng hay dng tn s c biu th bng n v s sng cm
-1
)
Ph hng ngoi c gi tr xc nh nhng nguyn t hay nhm nguyn t no c
(hoc khng) trong phn t.
Bng tn s hp th ca mt s nhm trong ph hng ngoi.
Lin kt Loi hp cht Tn s cm
-1

C-H
C-H
C-H
C-C
Ankan
Anken
Ankin
Anken
2850-2960
3020-3080
3300-3340
1640-1680
C-C
C-O
O-H
Ankin
Anhyt, xton
Ancol
2100-2260
1690-1760
3610-3640
1.7.3. Ph cng hng t ht nhn (CTN).
Ht ca mt s nguyn t ging nh electron c spin. Theo tnh ton ca c hc lng t
th s spin ca ht nhn nguyn t c th phn thnh:
I=0
12
C,
16
O,
28
Si
I=1/2
1
H,
3
H,
13
C,
19
F,
31
P
I=1
2
H,
14
N
I=3/2
1
B,
35
Cl,
37
Cl
I= c nhng gi tr cao hn.
V cc ht nhn nguyn t l nhng phn mang in tch nn nhng ht nhn c I0 khi
quay quanh trc ca n s sinh ra mt mmen t . Cc ht nhn c mmen t I=0 khng c tn
hiu cng hng t nhn. Cc ht nhn c I>1/2 cho cc tn hiu cng hng t nhn rt phc
tp nn t s dng. Ch c cc ht nhn c I=1/2 thun tin cho CTN. c bit trong ho hc
hu, thng s dng ph cng hng t ht nhn ca proton (CTP) v proton c hu ht trong
cc hp cht hu c.
Nu t proton trong t trng H
0
, theo nh lut c hc lng t mmen t ca proton
c th c 2I+1 nh hng, tc l 2.1/2 +1 = 2:
- Mt nh hng theo t trng H
0
(m= +1/2)
- Mt ng hng i lp vi t trng H
0
(m= -1/2)
iu c ngha l proton trong t trng H
0
c xp trn 2 mc nng lng: E
1
= +
.H
0
E
2
= -H
0

Nh vy chuyn hng i lp vi t trng theo hng vi t trng cn phi c
mt nng lng E= E
1
-E
2
= 2.H
0
.
Thay = h/4 (trong hng s c trng cho mi ht nhn, h l hng s Plng).
C-H
C=C
CH
3
CH
2
C-H
Ta c: E = hH
0
/2 (E ch ph thuc vo H
0
)
Mt khc theo nh lut hp th, s cng hng ch xy ra khi:
E = h
Suy ra: h= hH
0
/2 do = H
0
/2
l tn s m ti xy ra cng hng.
Nguyn tc hot ng ca mt my CHP nh sau:
My ghi dao ng
My t ghi
B khuych i
B to sng
A M Hp cht A M
Trong thc t c th thu nhn ph CHP bng hai cch:
1- C nh t trng H
0
v lm thay i tn s ca trng in t.
2- C nh tn s v lm thay i H
0
(phng php ny thng hay s dng hn).
Nu tt c xy ra n gin nh trnh by trn y th tt c mi prton ca cc phn t
ca cc cht hu c u hp th mt H
0
nht nh v ph cng hng prton ch c mt vch.
Nhng t c mt cng H
0
(cng hiu dng) th do mt in tch bao quanh
cc proton khc nhau nn cn phi tc dng ln mi mt proton mt t trng H (cng tc
dng) khc nhau.
Nh vy mt tn s xc nh cc proton u hp th mt cng hiu dng nh
nhau nhng khc nhau v cng tc dng H. Chnh s khc nhau nay cho php thu nhn ph
CHP thnh nhng dy pic hp th c trng cho s bao bc ca cc electron xung quanh
proton.

Ph CHP cho ta thng tin cn thit xc nh cu to ca phn t sau y:
1- S lng cc tn hiu cng hng ch ra c bao nhiu loi proton khc nhau trong
phn t.
I/I
0
H
V d: CH
3
-CH
2
-Cl CH
3
CHCl-CH
3
CH
3
-CH
2
-CH
2
-Cl
a b a b a a b c
(2 tn hiu) (2 tn hiu) (3 tn hiu)
2- V tr tn hiu cng hng ch ra thng tin v s bao bc ca electron xung quanh
proton. V tr ny c nh gi bng khong cch gia tn hiu ca nhng nhm ht nhn c
kho st v tn hiu ca cht lm chun. i lng c gi l chuyn dch ho hc.
chuyn dch ho hc c o bng n v phn triu (pt). Cht lm chun thng chn l
ttramtylsilan (TMS) v TMS ch c mt vch hp v vch ny xa cc tn hiu cng hng
prton khc. Hin nay trong ho hc tn ti hai loi thang o o chuyn dch ho hc v
lin h vi nhau theo =10 +
Trong v d di y chuyn dch ho hc ca CH
3
l 0,9pt; -CH
2
l 1,3pt; -CH l
1,5pt c vit nh sau: ph CHP, , pt. 0,9(CH
3
); 1,3(CH
2
); 1,5(CH).
3- Cng (din tch ca pic) ch ra s lng ca proton mi loi trong phn t.
Thng cng ny c ch ra trn ph CHP bng ng bc thang v mi bc ca n t l
vi din tch ca tn hiu.V d trong ph CHP ca p-tecbutyltoluen sau y c s lng proton
a l 9 tng ng vi 18mm, proton b l 3 tng ng vi 6mm, proton c l 4 tng ng vi
8mm.
CH
CH
2
CH
3
TMS
1
2 3 4 0
4- S phn chia tn hiu thnh cc vch ch ra nh hng ca cc proton xung quanh n
proton kho st do s tng tc spin-spin. V d trong ph CHP ca etylbrmua tn hiu cng
hng ca nhm CH
3
l 3 vch, cn ca CH
2
l 4 vch.
Xt nhm CH
3
ta thy proton ca n b nh hng bi nhm CH
2
. Trong t trng
proton CH
2
c th nh hng:
-1/2 + (-1/2) = -1
-1/2 +1/2 -1/2 +1/2 = 0
+1/2 +1/2 = 1
H
0

Do nh hng ca proton CH
2
nh trn nn proton nhm CH
3
b phn thnh 3 vch theo
t l 1:2:1.
Xt proton CH
2
ta thy n b nh hng ca nhm CH
3
. Trong t trng ca CH
3
n c
th nh hng:
H
0
Do nh hng ca nhm CH
3
nn proton ca nhm CH
2
b phn thnh 4 vch theo t l
1:3:3:1.
Khong cch gia cc vch k nhau ca mt tp hp c o bng Hz gi l hng s
tng tc spin-spin J. Hng s ny c trng cho s tng tc gia cc nhm nguyn t trong
ph CHP.
1.8. PHN LOI CC PHN NG TRONG HO HC HU C.
Cc phn ng hu c phn loi bng nhiu cch khc nhau: theo tin trnh phn ng, theo
phng thc sp xp li lin kt v theo s cc phn t tham gia vo bc quyt nh tc
phn ng.
1.8.1. Theo tin trnh phn ng.
a. Cc phn ng cng hp (k hiu l A t ch addition tc l cng hp).
V d:
C C + Br Br C
Br
C
Br
R NH
2
H
+
R NH
3
+
+

b. Cc phn ng tch loi (k hiu l E t ch Elimination tc l tch)
V d:
C
H
C
OH
C C + H
2
O
c. Cc phn ng th (k hiu l S t ch Substitution tc l th).
V d:
R X Y
-
R Y X
-
+ +
R H Cl Cl R Cl HCl + +
1.8.2. Theo phng thc sp xp li lin kt.
a. Cc phn ng gc.
y l loi phn ng m trong mt s giai on ca phn ng xut hin nhng
sn phm (hay sn phm trung gian) c mt in t khng lin kt. Thng cc gc t do c
to thnh do s phn ct ng ly.
V d:
A B A
.
+ B
.
Cl Cl 2Cl
.
RO OR 2RO
.

b. Cc phn ng phn cc hay phn ng ion.
Trong nhng phn ng ny cc lin kt c tch ra hay to thnh bng mt cch bt i
xng, tc l cp lin kt c mt bn gi li hoc do mt bn ca lin kt mang . Thng
cp lin kt in t c to thnh do s phn ct d ly.
V d:
A
+
B
-
+ A B
H Cl H
+
Cl
-
+
Ta phn bit nhng phn ng i nhn N (Nucleophin) v nhng phn ng i in t E
(Electronphin). Theo qui nh bao gi cng cn c vo tc nhn phn ng (reagent) xc nh
xem mt phn ng l i nhn hay i in t. Nhng cng ging nh phn ng xi hokh i
nhn v i in t l hai mt ca mt qu trnh gn b vi nhau cho nn nhiu khi gi mt cu
t tham gia phn ng l tc nhn hay l hp cht (substrat) ch l iu kin tu . Thng th
cht c cu trc t phc tp l tc nhn, cn cht c cu trc phc tp l cht nn. V d trong
phn ng cng triankylamin vi boriflorua th triankylamin l tc nhn i nhn cn boriflorua l
tc nhn i in t.
N
R
R
R
B F
F
i nhn
F
i in t
N
R
R
R
B F
F
F
Cc tc nhn i nhn thng l:
- Cc ion c in tch m, cc hp cht c cp in t t do, cc hp cht c lin kt bi
hoc cc hp cht thm.
Cc tc nhn i in t thng l:
- Cc ion c in tch dng, cc hp cht c v in t cha hon chnh (Axit Liut), cc
hp cht axtylen, cc hp cht c nhm cacbnyl, cc halogen.
1.8.3 Theo s cc phn t tham gia bc quyt nh tc phn ng.
1, Cc phn ng n phn t
2, Cc phn ng lng phn t
3, Cc phn ng c s phn t cao hn
CU HI N TP V BI TP CHNG 1
1.1. Bn cht v c im lin kt cng ha tr.
1.2. nh ngha hin tng ng phn lp th, phn loi ng phn lp th
1.3. iu kin cn v c ng phn hnh hc. Cch gi tn cc ng phn hnh hc.
1.4. iu kin cn v c ng phn quang hc. Cch gi tn cc ng phn quang hc.
1.5. Bn cht v c im ca hiu ng cm ng v hiu ng lin hp.
1.6. Vit cng thc cc ng phn hnh hc c th c v gi tn cc ng phn , ng vi cc
cng thc cu to sau:
CH
3
CH CH
2
Cl CH CH Br
CH
3
CH CH C
2
H
5
CH
3
CH
CH
3
CH C
CH
3
C
2
H
5
a.
b.
c.
d.
1.7. Trong cc hp cht sau, hp cht no c tnh quang hot.
CH
3
CH CH
3
OH
CH
3
C
Cl
H
CH
2
CH
3
CH
3
CH
CH
3
C
H
Br
CH
3
CH
3
CH
CH
3
C
OH
CH
3
CH
2
CH
2
CH
3
CH
3
C
H
CH
2
CH
2
CH
3
CH
2
CH
2
CH
3
a. b. c.
d. e.
1.8. Vit cng thc cc ng phn lp th ca cc hp cht sau y v cho bit loi ng phn.
CH
3
CH CH CH CH CH
3
CH
2
CH CH
2
CH
2
CH CH
2
CH
3
CH CH CH
3
Br Br
C
6
H
5
N N C
6
H
5
CH
3
CH CH CH
CH
3
COOH
a. b.
c. d. e.
1.9. Trong cc hp cht sau, hp cht no c hiu ng lin hp.
CH
2
CH CH CH
2
CH
3
CH C CH
2
CH
3
CH CH CH O
CH
3
C NH
2
O
CH
2
CH CH
2
CH CH
2
a. b.
c. d. e.
1.10. Sp xp cc hp cht sau theo th t tng dn tnh axit.
ClCH
2
CH
2
COOH, FCH
2
CH
2
COOH, BrCH
2
CH
2
COOH
NO
2
COOH, COOH, COOH CH
3
O
a.
b.
TI LIU THAM KHO CA BI TP CHNG 1
[1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp
ha hc hu c.
[2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni.
[3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut,
H Ni.
[4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H
Ni.
[5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.
Chng 2
HYRCACBON NO
(ANKAN)
Cc hp cht hu c ch c cha 2 nguyn t hyr v cacbon c gi l hyrcacbon.
Da vo s cu to khc nhau, cc hyrcacbon c chia lm hai loi chnh: hp cht khng
thm v hp cht thm. Cc hp cht khng thm c chia thnh ankan, anken, ankin v cc
hp cht mch vng tng ng ca chng (xyclankan, xyclanken, xiclankin).
2.1. Dy ng ng, ng phn.
Hp cht n gin nht ca ankan l CH
4
. N c cu to t din (nguyn t cacbon c
ocbitan lai to sp
3
, gc lin kt l 109
0
28
, di lin kt l 1,09 A
0
).
Cc hp cht tip theo l tan, prpan, butangi l cc hp cht ng ng ca ankan:
CH
4
, CH
3
-CH
3
, CH
3
-CH
2
-CH
3
, CH
3
-CH
2
-CH
2
-CH
3

Dy hp cht m trong thnh phn phn t ca hp cht tip theo khc vi thnh phn
phn t ca hp cht trc mt n v cu to nht nh gi l dy ng ng. Cc hp cht
ca dy gi l cht ng ng.
Nh vy cc hp cht ankan to thnh dy ng ng ankan m trong hai hp cht k
nhau khc nhau bi mt n v cu to l CH
2
. T ta suy ra cng thc tng qut ca ankan
l: C
n
H
2n+2
.
Cng vi s tng ln ca s lng nguyn t cacbon trong phn t s lm tng s lng
nhng kh nng phn b khc nhau ca cc nguyn t cacbon dn n s to thnh cc ng
phn khc nhau.
V d: pentan c 3 ng phn, hecxan c 5 ng phn, heptan c 9 ng phn, kan c
75 ng phn, kzan (C
20
H
42
) c 366.319 ng phn.
Pentan (C
5
H
12
)
C C C C C C C C C
C
C
C
C
C
C
n-pentan izpentan neopentan
2.2. Danh php
Cc hyrcacbon c gi tn thao cc danh php nh trnh by phn i cng
(1.1.5).
2.3. Tnh cht vt l.
Lc lin kt phn t gm 2 loi: lc tc dng lng cc v lc Van-ec-van.
Lc tc dng lng cc c gy ra bi s ht nhau ca u mang in tch dng ca
phn t phn cc ny vi u m ca phn t kia. (v d nh trong phn t HCl).
+ -
- +

Trong trng hp hp cht khng phn cc, s phn b ca in tch l i xng (v d
CH
4
) do tng cc mmen phn cc bng 0. Nhng mt khc in tch lun lun chuyn
ng, v vy mt thi im xc nh no s phn b ca chng thay i do lm xut
hin mt s phn cc nh. Chnh s phn cc tc thi ny lm nh hng n s phn b ca
cc in t trong phn t CH
4
khc. Kt qu lm phn t phn cc cm ng. S phn cc ny
to ra lc lin kt cc phn t li vi nhau. Lc chnh l lc Van-ec-van. Lc ny c hiu
lc trong mt khong cch ngn v ch gia cc phn t tip xc vi nhau, tc l gia cc b
mt ca cc phn t. V vy phn t cng ln, tc l b mt ca cc phn t cng ln th lc
cng mnh. Thc nghim chng minh rng, nhit si v nhit nng chy ca ankan
tng theo chiu tng ca s nguyn t cacbon c trong phn t.
Bng tnh cht vt l ca mt s ankan.
Nu biu din s ph thuc cu nhit nng chy ca cc hyrcacbon no mch thng
vo s nguyn t cacbon c trong phn t th ta s thu c th hnh rng ca.
Hp cht Cng thc phn t t
0
nc
t
0
s
d
g/ml

Mtan
tan
Prpan
n-butan
n-pentan
n-hecxan
n-heptan
n-octan
n-nonan
n-kan
CH
4
CH
3
CH
3

CH
3
CH
2
CH
3
CH
3
(CH
2
)
2
CH
3
CH
3
(CH
2
)
3
CH
3
CH
3
(CH
2
)
4
CH
3
CH
3
(CH
2
)
5
CH
3
CH
3
(CH
2
)
6
CH
3
CH
3
(CH
2
)
7
CH
3
CH
3
(CH
2
)
8
CH
3

-183
-172
-187
-138
-135
-95
-90
-57
-54
-31
-162
-88,5
-42
0
36
69
89
126
151
174
0,625
0,659
0,684
0,703
0,718
0,730
Theo quy tc kinh nghim, tr mt s ankan thp nu mch ca phn t tng thm mt
nguyn t cacbon th nhit si ca ankan tng ln 20-30
0
C.
Trn thc t 4 ankan u l nhng cht kh, 13 ankan tip theo (t C
5
n C
17
) l cht
lng, t ankan C
18
tr i l cht rn.
Ankan khng phn cc nn tan tt trong dung mi khng phn cc.
T trng ca cc ankan tng ln khi phn t lng tng nhng khng qu 0, 8 g/ml. iu
c ngha l ankan nh hn nc.
2.4. CC PHNG PHP IU CH.
Thng cc phng php iu ch cc hp cht hu c c chia lm 2 loi: phng
php cng nghip v phng php phng th nghim. Hai phng php ny c nhng im
khc nhau sau y:
Phng php cng nghip thng thu nhn mt khi lng hp cht ln vi gi thp
trong khi phng th nghim cn tng hp mt vi trm gam, mt vi gam hoc t hn, khng
quan tm n gi c v thi gian cn thit tng hp.
Phng php cng nghip s dng cc hp cht khng ch dng tinh khit m c dng
hn hp nhiu cht, cn trong phng th nghim lun lun i hi phi dng tinh khit.
Phng php cng nghip thng chn cch thu nhn hp cht sao cho thun li v vic
vn dng cc dy chuyn cng ngh v thit b. V vy thng phng php cng nghip ch c
ngha vi cch thu nhn mt hp cht nht nh. Tri li phng php phng th nghim quan
tm n vic s dng cho c mt lot hp cht cng loi vi nhau.
2.4.1. Phng php cng nghip.
a. Ngun thu nhn chnh ca ankan l du m v kh thin nhin. S thi ra hng triu
nm ca cc tng a cht chuyn ho cc hp cht hu c phc tp ca ng thc vt thnh
hn hp ankan c thnh phn t 1 n 30, 40 nguyn t cacbon. Thng kh thin nhin ch
cha nhng ankan nh (c phn t lng nh) ch yu l CH
4
. Du m c thnh phn ankan
phc tp hn. Bng phng php chng ct du m, ngi ta tch cc loi ankan ra khi nhau,
c ng dng rng ri trong i sng, cng nghip. Cc ankan l cht kh c s dng lm
-200
-150
-100
-50
0
50
1 3 5 7 9 11 13 15 17 19
S nguyn t C
N
h
i
n
g

c
h
y
nhin liu t. Cc ankan l cht lng c s dng lm nhin liu cho ng c dt trong, cc
ankan cao hn dng du (luille) dng bi trn. Cc ankan rn nh parafin dng lm nn
C H
n 2n+2
cracking
C H
m 2m+2
C H
+
n-m 2(n-m)

b. Phng php tng hp t xyt cacbon CO.
Cho hn hp xyt cacbon vi hyr nhit 250
0
C v p sut thng i qua xc tc
kim loi hay Co.
CO n (2n-1)H
2
C H
n 2n-2
nH
2
O + +
2.4.2. Phng php phng th nghim.
a. Tng hp mtan t cacbua nhm.
Al
4
C
3
12H
2
O Al(OH)
3
CH
4 + + 4
3

T sunfua cacbon
CS
2
CH
4
Cu
2
S + H
2
S 2 + Cu 8 + 4

T axtat natri (phng php kim nng chy)
CH
3
COONa NaOH CH
4
Na
2
CO
3 +
+

b. Tng hp tan: phn ng Vuyc.
CH
3
Cl
CH
3
CH
3 2 + Na 2
NaCl 2 +
Phn ng Knbe: in phn mui axtat. Ti ant anion CH
3
COO
-
b phng in tch
thnh raical CH
3
COO
.
v b phn hu thnh CO
2
v tan.
CH
3
COO
.
CH
3
CH
3
CO
2 2
+

c. Tng hp cc ankan cao hn.
Kh ho cc dn xut ankylhalogenua.
RX + Mg

RMgX
H
2
O

RH
( RMgX l tc nhn Grinha)

CH
3
CH
3
CHBrCH
3
Mg
CH
3
CH
2
CHMgBrCH
3
H
2
O
CH
3
CH
2
CH
2
CH
3
sec-butylbrmua
n-butan

Kh bng kim loi trong mi trng axt.
CH
3
CH
2
CHBrCH
3
Zn/H
+
CH
3
CH
2
CH
2
CH
3
RX + Zn + H

RH + Zn
+2

+ X
- +

Kh bng axt iic nhit cao.
RX + 2HI
CH
3
CH
2
CH
2
CH
2
CH
2
Cl

+ 2HI CH
3
CH
2
CH
2
CH
2
CH
3
+ HX + I
2
RH + HX + I
2
d. Hyr ho anken.
C H C H
n
2n 2n+2 n
H
2
/Ni
Trong tt c cc phng php trn y, phng php hyr ho cc anken c ngha
nht v: phn ng tin hnh n gin (khuy trn mt anken vi hyr mt p sut va phi
v mt lng xc tc nh, ta s thu c mt ankan c khung cacbon ging nh anken ban
u). Mt khc ngun nguyn liu anken r, d thu nhn bng nhiu phng php khc nhau.
Kh ho cc ankylhalogenua bng tc nhn Grinha l phn ng th trc tip nguyn t
halogen bng hyr. Ankan thu c cng gi nguyn khung cacbon ban u. y cng l
phng php c ngha thc t ln v cc alkylhalogenua d dng thu nhn t cc hp cht
khc. Tuy nhin trong trng hp yu cu iu ch mt cht no m c th s dng c c
2 phng php th nn chn phng php hyr ho anken v n n gin hn v c hiu sut
phn ng cao hn. Phn ng Vuyc ch c ngha dng iu ch cc ankan i xng.
V d:
CH
3
CH
2
Br CH
3
CH
2
CH
2
CH
3
Na
2
CH
3
Br CH
3
CH
3
Na
2
Trong trng hp dng iu ch cacbon bt i xng th phn ng Vuyc t c ngha
v to thnh mt hn hp sn phm do lm tng thm khi lng cht ban u v lm phc
tp qu trnh tch sn phm.
V d:
+ 2Na +

+ Na R
1
X R
2
X R
1
R
2
R
2
X 2 R
2
R
2
2 R
1
X R
1
R
1
(sn phm ph)
(sn phm ph)
C ch ca phn ng Vuyc cho n nay vn cha c chng minh nhng trong c
hai giai on c bn l:
RX + 2Na RNa + NaX
RNa + RX R-R + NaX

2.5. TNH CHT HO HC.
Ankan trc y gi l parafin (t ch latinh parumaffinis tc l i lc ho hc yu)
ni ln rng kh nng phn ng ca chng yu. Ankan khng c kh nng kt hp vi hyr nn
c gi l hyrcacbon no. Ankan khng phn ng trc tip vi clo, brm iu kin thng,
ch b oxy ho bi cc tc nhn oxy ha mnh nhit cao nh KMnO
4
.
Cc phn ng ca ankan.
1- Phn ng halogen ha.
R C H X
2
+
R C X HX +
t
0
C
3- Phn ng vi iazmtan v kten.
R C H +
CH
2
N
2
iazmtan
CH
2
=C=O
kten
as
R C CH
2
H +
(N
2
hay CO)
3- Phn ng t chy.
CO
2
O
2
C H
+ n 2n+2
3n+1
1
n
H
2
O (n+1) +
4- Phn ng crcking.
C H
n 2n+2
cracking
C H
m 2m+2
C H
+
n-m 2(n-m)

5- Phn ng sunfnic ho:
R C H HO SO
3
H + R C SO
3
H H
2
O +
6- Phn ng sunfclo ho:
R C H SO
2
Cl
2
R C SO
2
Cl HCl
+
+
+
7- Phn ng nitr ho:
+ R C NO
2
H
2
O
+ R C H HO NO
2
2.5.1. Phn ng halogen ho.
a. Trc ht ta nghin cu phn ng clo ho mtan.
Hn hp kh mtan v clo di tc dng ca nh sng hoc nhit (250-400
0
C) th
chng s tc dng mnh lit vi nhau to thnh phn t mtylclorua. Mtylclorua c th tip tc
tham gia phn ng clo ho to thnh mtylenclorua. Phn ng c th tip tc xy ra v to thnh
triclomtan (clorofoc) hoc ttraclomtan (cacbon ttraclorua).
CH
4
CH
3
Cl CH
2
Cl
2
CHCl
3
CCl
4
Cl
2
Cl
2
Cl
2
Cl
2
as as as
as

V vy hiu r phn ng ta phi lm sng t my vn sau:
Mtan v clo khng tc dng vi nhau trong bng ti nhit thng. Phn ng d
dng xy ra trong bng ti nhit 250
0
C hoc nhit thng khi c chiu sng. Nu
phn ng c khi mo bng nh sng th c hng ngn phn t mtylclorua c to thnh
khi phn ng hp th mt phton nh sng. Khi c mt lng nh oxy s lm gim tc phn
ng i mt thi gian. Thi gian ny ph thuc vo lng oxy c trong phn ng.
gii thch ph hp vi cc vn t ra trn y, ngi ta ngh mt c ch
tng qut cho phn ng clo ho mtan nh sau:
Cl
2
t C
0
Cl
.
2
CH
4
Cl
.
+ HCl CH
3
.
+
Cl
.
CH
3
.
Cl
2
+ CH
3
Cl +
tip theo (2), (3), (2), (3)...

Qu trnh vit phn ng ho hc theo tng giai on xy ra gi l c ch phn ng. Loi
c ch trn y gi l c ch gc. giai on (1) xy ra s ph v phn t clo thnh cc gc t
do cn mt nng lng ph v lin kt. Nng lng c cung cp bng s un nng hoc
chiu sng. Gc t do Cl
.
cng ging nh cc gc t do khc c kh nng phn ng rt mnh v
do n tm cch kt hp vi mt electron lm y lp 8 in t ca mnh. t c iu
gc Cl
.
cn phi va chm vi cc nguyn t hoc cc phn t khc. S va chm vi cc gc
t do Cl
.
khc c xc sut rt nh v rng nng ca chng to thnh mt thi im bt k
rt t. S va chm vi phn t clo ch dn n s thay i mt gc t do ny bng mt gc t do
khc m thi.
Cl
.
Cl
.
Cl Cl Cl Cl + +

V vy ch c s va chm vi phn t mtan mi dn n vic to thnh mt gc t do
mi (giai on 2).
Gc mtyl CH
3
.
mi sinh ra cng tng t nh gc clo trc y tm cch lm y lp 8
in t ca mnh bng s va chm vi cc phn t hoc nguyn t khc. S va chm cng ch c
ngha vi phn t clo v mi to thnh mtylclorua v Cl
.
(giai on 3). Gc t do clo mi sinh
ra ny li tham gia vo phn ng (2), tip theo l phn ng (3). Qu trnh ny c lp i lp
li nhiu ln to thnh nhiu phn t mtylclorua.
Tuy nhin cc phn t trn y xy ra khng phi l vnh cu v rng tuy s va chm ca
cc gc t do vi nhau rt t nhng vn c th xy ra v do dn n s mt i cc gc t do:
Cl
.
Cl
.
Cl Cl +
CH
3
.
+
CH
3
CH
3
.
CH
3
Cl
.
+ CH
3
.
CH
3
Cl
Nu trong phn ng c mt oxy th:
CH
3
.
O
2
+ CH
3
OO
.

Gc t do CH
3
OO
.
C kh nng phn ng thp hn nhiu so vi gc CH
3
.
nn lm cho
tc phn ng chm li. Hp cht c kh nng lm cho phn ng b chm li hoc lm dng
phn ng ngay c khi vi mt lng rt nh gi l cht c ch. Trong v d trn y oxy l cht
c ch CH
3
OO
.
l gc c ch.
iu cui cng chng ta cn phi gii thch l ti sao thu c mt hn hp nhiu sn
phm v c th khng ch phn ng thu c mt sn phm duy nht l mtylclorua hay
khng?
thi gian u ca phn ng, mtan tc dng vi clo to thnh mtylclorua (I). Theo
thi gian khi lng mtan bt dn v mtylclorua tng ln do mtylclorua s tham gia cnh
tranh vi mtan trong phn ng clo ho. Khi nng ca mtylclorua ln hn nng mtan th
clo s tc dng nhiu hn vi mtylclorua, II tr thnh ch yu. Tng t nh vy s xy ra cc
phn ng III, IV. V vy sn phm ca phn ng l mt hn hp 4 dn xut ankylhalogenua. C
th khng ch phn ng ch to ra mt sn phm ch yu l mtylclorua bng cch cho d
mtan. Trong trng hp ny lng mtan lun lun nhiu hn mtylclorua v do s hn ch
c phn ng II.
b. Phn ng dy chuyn.
Phn ng gia mtan v clo trn y ngi ta gi l phn ng dy chuyn tc l phn
ng xy ra qua nhiu giai on m trong giai on ny lm sinh ra nhng trung tm c kh
nng phn ng mnh gy ra phn ng ca giai on tip theo. y cng l phn ng c
trng cho cc hp cht ankan ni chung.
X
.
RH R
.
+ + HX
R
.
X
2
+ RX + X
.
R
.
+
X
.
X
.
+ X
2
X
.
R
.
+ RX
R
.
R-R
tip theo (1), (2), (3)...
(2)
(3)
Giai on pht
trin mch
Giai on
tt mch
(4)
(5)
(6)
X
2
250-400 C
0
2X
.
(1)
Giai on to gc
Trn gin nng lng ca phn ng clo ho mtan ta nhn thy rng E
2
, E
3
c ngha
l trong hai phn ng pht trin mch, phn ng (2) xy ra chm hn nhiu so vi (3) do
phn ng (2) c tnh cht quyt nh tc phn ng.
E
3

E
2

CH
4
+Cl
.

CH
3
.
+ Cl
2
CH
3
Cl+ Cl
.
E
tin trnh phn ng
trng thi chuyn tip
c. nh hng phn ng halogen ho.
Xt cc phn ng halogen ho cc hp cht sau:
CH
4
Cl
.
CH
3
.
Cl
2
CH
3
Cl
Cl
.
CH
3
CH
3
CH
3
CH
2
.
Cl
2
CH
3
CH
2
Cl
CH
3
CH CH
2
H
H
CH
3
CH
2
CH
2
.
CH
3
CH
2
CH
2
Cl
CH
3
CHClCH
3
gc n-prpyl
n-prpylclorua
gc izpropyl izpropylclorua
CH
3
CHCH
3
.
Cl
.
Cl
.
Cl
2
Cl
2
Trong phn ng ca prpan vi clo, gc prpyl c to thnh khi tch i mt hyr bc
I, izprpyl c to thnh khi tch hyr bc II. Ta nhn thy rng trong phn t prpan c 6
hyr bc I v 2 hyr bc II nn xc sut va chm ca Cl
.
vi cc loi hyr ny l 6:2 (hay
3:1) c ngha l sn phm n-prpylclorua: izprpylclorua l 3:1. Nhng trong thc t t l thu
c l 1:1 (45:55). Ngha l izprpylclorua c to thnh vo khong 3 ln nhiu hn l
n-prpylclorua. iu ch c th gii thch bng nng lng hot ho E
a
(E
a
dng tch
hyr bc II nh hn rt nhiu so vi hyr bc I). Bng s kho st tng t ngi ta i n
kt lun rng kh nng tham gia phn ng halogen ho ca cc nguyn t hyr bin i theo
dy sau:
Hyr bc I < Hyr bc II < Hyr bc III
nhit phng t l vo khong 5,0:3,8:1,0. T l ny cho php tin on t l cc
sn phm sinh ra trong mt phn ng clo ho.
V du:
CH
3
CH
2
CH
2
CH
3
Cl
2
/as
CH
3
CH
2
CH
2
CH
2
Cl CH
3
CH
2
CHClCH
3
n-butylclorua izbutylclorua
+
Ta c t l sn phm:
n-butylclorua
izbutylclorua
=
s hyr bc I
s hyr bc II
kh nng phn ng hyro bc I
kh nng phn ng hyro bc II
=
6
4
1,0
3,8
= =
28% 6
72% 15,2

Kh nng tham gia phn ng ca hyr vi brm xy ra theo t l hyr bc I : hyr
bc II : hyr bc III = 1600 : 82 : 1
S d kh nng tham gia phn ng ca cc loi hyr trong phn ng halogen ho
thay i nh trn l v do nh hng ca hiu ng +I ca cc nhm ankyl nn dn n bn
ca cc raical bin i nh sau:
CH
3
C
CH
3
CH
3
.
CH
3
C
CH
3
H
.
CH
3
C
H
H
.
H C
H
H
.
c. S xut hin nguyn t cacbon bt i xng.
Trong phn ng clo ho n-butan c sn phm thu c sec-butylclorua c nguyn t C
2

bt i, nhng thc nghim chng minh rng sec-butylclorua l mt hp cht khng quang hot.
iu c gii thch rng giai on (2) gc Cl
.
tch i mt nguyn t hyr bc II to thnh
sec-butylclorua. Nguyn t cacbon trong gc t do c ocbitan lai to sp
2
. Giai on tip theo
to thnh lin kt C-Cl clo c th tn cng c t hai pha ca mt phng cha ocbitan lai to sp
2
.
V xc sut tn cng vo hai pha ca mt phng nh nhau nn to thnh mt s lng bng
nhau cc sn phm quay phi v quay tri, do gc quay ca nh sng phn cc trit tiu ln
nhau nn hn hp sn phm thu c khng quang hot. Ngi ta gi hn hp ny l bin th
Raxmic.
H
3
C
C
2
H
5
H
Cl
2
a
b
CH
3
C
2
H
5
H
Cl
H
Cl
H
3
C
C
2
H
5
CH
3
C
2
H
5
Cl
H Cl H
CH
3
C
2
H
5
Vy hn hp Raxmic tc l hn hp mt s lng bng nhau ca ng phn quang hc
quay phi v quay tri. Phn ng to thnh hn hp Raxmic gi l phn ng Raxmic ho.
2.5.2. Mtylen ho.
Mtylen c to thnh trong phn ng phn tch cc hp cht iazmtan hoc xten
di tc dng ca nhit:
t C
0
CH
2
C O CH
2
CO +
t C
0
CH
2
N
+
N
-
CH
2
N
2
+
Mtylen c tnh hot ng ho hc mnh v do tham gia phn ng mtylen ho:
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3

CH
3
CH
2
CH
2
CH(CH
3
)
2
CH
3
CH
2
CHCH
2
CH
3
CH
3
CH
3
CH
2
CH
2
CH
2
CH
3
CH
2
N
2
t C
0
n-hecxan
2-mtylpentan
3-mtylpentan
CH
3
CH
2
CH
2
CH
3
CH
2
C O
t C
0
CH
3
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
CHCH
3
CH
3
+
2.5.3. Phn ng t chy.
Phn ng ankan vi xy to thnh CO
2
v nc cng vi s gii phng mt nng lng
ln thng c s dng thu nng lng. Cho n nay c ch ca phn ng ny cha c
chng minh nhng chc chn rng y l phn ng dy chuyn c ch gc. Mt trong nhng
ng dng rt quan trng ca phn ng ny l dng nhit t chy cc hyrcacbon chy cc
ng c t trong. Vic s dng cc ng c p sut cao c ngha rt ln nhng lm xut
hin mt kh khn: nhin liu trong xylanh thng t n nhng thi im cha cn thit nn
lm gim sc my. khc phc iu ny ngi ta khc phc bng hai phng php:
1- Chn nhng hyrcacbon thch hp lm nhin liu ng c.
2- Cho thm hp cht ttramtyl ch vo nhin liu.
Theo phng php th nht ngi ta phn loi rng hyrcacbon tt nht lm
nhin liu ng c l hp cht izoctan.
CH
3
C(CH
3
)
2
CH
2
CH(CH
3
)
2

2,2,4-trimtylpentan (izoctan)
Ngi ta quy nh izoctan c ch s octan l 100. Hp cht c ch s octan km nht l
n-heptan (bng 0). Ch s octan ca nhin liu tng ln rt mnh khi cho thm mt lng
ttratyl ch.
2.1. Gi tn ankan theo danh php thng thng v danh php IUPAC.
2.2. Cc phng php iu ch ankan.
2.3. Nhng tnh cht ha hc quan trng ca ankan.
2.4. Vit phng trnh phn ng iu ch cc ankan sau y:
a. n-Butan
b. iz-pentan
2.5. Khi Clo ha cc ankan sau y trong iu kin c nh sng xc tc s thu c nhng dn
xut mono Clo g?
a. n-Propan
b. Iz-butan
Tnh hiu sut cc sn phm trong mi trng hp, gi s kh nng phn ng ca cc
nguyn t hiro cacbon bc I, bc II, bc III tng ng vi: 1:3:5
2.6. Gi tn theo danh php quc t cc hp cht sau y:
CH
3
CH
2
CH
C
2
H
5
CH
CH
3
CH
2
CH
3
CH
3
CH
2
CH
CH
3
CH
C
2
H
5
CH
3
CH
3
C
CH
3
CH
3
CH
2
CH
CH CH
3
CH
2
CH
3
CH
2
CH
CH
3
CH
2
CH
3
CH
3
CH
2
C
C
2
H
5
CH
2
CH
3
C
2
H
5
a. b.
c. d.
2.7. Cho bit cc sn phm ph trong phn ng iu ch n-pentan t n-propyl ioua v etyl
ioua theo phng php tng hp WURTZ (Vuyc).
ha hc hu c.
H Ni.
Ni.
Chng 3
ANKEN
Anken l loi hyrcacbon c s lng nguyn t hyr trong phn t t hn trong
ankan tng ng l hai nguyn t. V n c kh nng cng hp vi hyr nn c gi l
hyrcacbon cha no. Cng thc tng qut ca anken l C
n
H
2n
.
3.1. CU TO V NG PHN CA ANKEN.
3.1.1. Cu to.
Cu to n gin nht ca dy anken l tylen C
2
H
4
, trong phn t tylen 2 nguyn t
cacbon u c ocbitan lai to l sp
2
. Cc ocbitan lai to ny xen ph vi ocbitan s ca hyr vo
vi nhau to thnh 5 lin kt nm trong mt mt phng. Mi nguyn t cacbon cn li mt
in t t do xen ph vi nhau to thnh lin kt (2 m my in t nm pha trn v pha
di ca mt phng cha lin kt ).
C C
H
H
H
H
H
H
H
H
C
1,34A
C
0
1,09A
0
117,5
0
121
0

Hp cht tip theo l prpen C
3
H
6
c cu to l CH
3
-CH=CH
2
.
Tip theo l butylen c mt s cu to:
CH
3
CH
2
CH CH
2
CH
3
CH CH CH
3
CH
3
C CH
2
CH
3
buten-1 buten-2 izbuten
Hp cht buten-2 c th vit di 2 dng ng phn hnh hc:
C C
H H
CH
3
H
3
C
C C
H
H
CH
3
H
3
C
cis-buten-2 trans-buten-2

3.1.2. ng phn hnh hc.
ng phn hnh hc l loi ng phn xut hin do s cn tr quay t do ca cc nguyn
t xung quanh lin kt i C=C. Ngi ta k hiu cc ng phn c hai nhm th hoc hai
nguyn t ging nhau nm v cng mt pha cu mt phng l ng phn cis, nu nm khc
pha l ng phn trans.
Tt nhin s cn tr quay xung quanh lin kt i i vi cc nguyn t cacbon ca
anken no cng c th nhng ng phn hnh hc ch xut hin khi no cc nhm th cc
nguyn t cacbon ni i khc nhau.
V d:
C C
H H
H
3
C
H
C C
H
H H
C
2
H
5
CH
3
C C
H
H CH
3
Khng c ng phn hnh hc
C C
H H
Cl Cl
C C
H
H
Cl
Cl
cis-icloten trans-icloten
c im ca cc ng phn hnh hc l chng c cc tnh cht vt l khc nhau, c cc
tnh cht ho hc tng t nhau v cng mt loi hp cht nhng mc tham gia cc phn ng
ho hc ca chng khc nhau v c cu to hnh hc khc nhau.
3.2. CCH GI TN.
3.2.1. Danh php thng thng.
Ging nh ankan, cc hp cht anken n gin nhiu khi c gi bng cc tn gi thng
thng nh: tylen, prpylen, butylenHp cht butylen phn bit nhau bi cc tin t ,
iz-. Cc ng phn hnh hc nh ni trn phn bit nhau bng cis hoc trans. Nhng cch
gi ny b hn ch khi dng gi tn cc anken phc tp.
3.2.2. Danh php IUPAC.
1- Mch chnh c chn l mch di nht c cha ni i cacbon-cacbon. Hp cht cn
gi c xem nh l dn xut cu mch chnh m cc nguyn t hyr c thay th bng
cc nhm th khc nhau. Tn gi ca mch chnh (ten, prpen, buten, penten) c to
thnh bng cch i ui an ca ankan tng ng thnh ui en.
2- nh s mch chnh sao cho v tr ni i l nh nht (ly s u ca nguyn t
cacbon ni i).
3- Gi tn cc nhm th cng vi cc ch ca n trc tn gi ca mch chnh.
V d:
CH
3
C
CH
3
CH
3
CH CH
2
CH
3
CH
CH
3
CH CH CH
3
3,3-imtylbuten-1 4-mtylpenten-2

3.2.3. Tnh cht vt l.
Tng t nh ankan, anken khng ho tan hoc rt t ho tan trong nc nhng tan tt
trong cc dung mi khng phn cc nh benzen, te, CCl
4
Chng c t trng nh hn nc.
Nhit si ca cc anken tng t nh ankan, c tng thm mt nguyn t cacbon trong mch
th nhit si tng ln 20-30
0
C.
Bng mt s tnh cht vt l ca anken.
Tn gi Cng thc T
0
C T
nc
0
C D
tylen
Prpylen
Buten-1
Penten-1
Hexen-1
Hepten-1
Octen-1
Nonen-1
ken-1
CH
2
=CH
2

CH
2
=CH-CH
3
CH
2
=CHCH
2
CH
3
CH
2
=CH(CH
2
)
2
CH
3
CH
2
=CH(CH
2
)
3
CH
3
CH
2
=CH(CH
2
)
4
CH
3
CH
2
=CH(CH
2
)
5
CH
3
CH
2
=CH(CH
2
)
6
CH
3
CH
2
=CH(CH
2
)
7
CH
3
-102
-48
-6,5
30
63,5
93
132,5
146
171
-169
-185
-138
-119
-104
-87
0,648
0,675
0,698
0,716
0,731
0,743
Nu ankan hon ton khng phn cc th anken tu thuc vo cu to hnh hc ca n c
th phn cc.
H H
Cl Cl
C C
= 0
C C
H
H
Cl
Cl
0

Trong cng nghip anken c iu ch bng phng php crcking du m.
C H
n 2n+2
cracking
C H
m 2m+2
C H
+
n-m 2(n-m)

Cc anken c s nguyn t cacbon nh hn 5 c th thu nhn c di dng tinh khit
bng cch chng ct phn on.
3.4.2. Phng php tng hp.
1- Tch loi ankylhalogenua.
C C
H X
KOH/ancol
C C
CH
3
CH
2
CH
2
CH
2
Cl
KOH/ancol
CH
3
CH
2
CH CH
2

CH
3
CH
2
CHCH
3
Cl
KOH/ancol
CH
3
CH
2
CH CH
2
CH
3
CH CHCH
3 +
2- hyrat ancol.
C
H
C
OH
H
2
SO
4
()
C C
H
2
O +
CH
3
CH
2
CH
2
CH
2
OH
H
+
CH
3
CH CHCH
3
CH
3
CH
2
CH CH
2 +
CH
2
CH
2
OH OH
H
2
SO
4
()
CH
2
CH
2
H
2
O +
3. Tch loi alkylihalogenua.
C C
X X
Zn
C C ZnX
2 +
+
V d:
CH
3
CH CHCH
3
Br Br
Zn
CH
3
CH CH CH
3
ZnBr
2 +

4. Kh ho cc ankin.
R C C R
C C
H H
R R
C C
H
H
R
R
sn phm cis
sn phm trans
H
2
/Ni(Pd, Pt)
Na (Li)/NH
3

Trong cc phng php trn y 2 phng php quan trng nht l tch loi
ankylhalogenua v hyrat ancol. Tt nhin c 2 phng php u c mt hn ch ln l hydr
c th b tch c 2 nguyn t cacbon cnh cacbon mang nhm halogen nn sn phm ca phn
ng khng tinh khit.
3.4.3. Phn ng tch loi.
a. Phn ng tch loi n phn t E1.
Trong phn ng E1 tc phn ng c quyt nh bc to thnh cacbcation.
H C C X X
-
H C C
+
+ C C HX +

V d:

(CH
3
)
2
C CH
3
OH
H
+
CH
3
C
+
CH
3
CH
3
+ (CH
3
)
2
C CH
3
OH
2
+
(CH
3
)
2
C CH
2
H
+
+

b. Phn ng tch lng phn t E2.
Trong phn ng E2 hp cht baz tham gia trng thi chuyn tip tn cng vo mt
nguyn t hyr cacbon.
Y
-
H C C X C C X
-
HY + + Y....H....C....C....X
-
-
+
c. nh hng ca bc lin kt v cu trc khng gian ni chung ti hng ca phn ng
tch loi.
Trong phn ng tch loi cc hp cht m nhm th X thuc cc nguyn t cacbon bc II
hoc bc III, phn ng c th xy ra theo 2 hng sau:
CH
3
CH CHCH
3
H X
CH
3
CH CHCH
3
CH
3
CH
2
CH CH
2
Tch loi Zaixep
Tch loi Hpman
nh hng Zaixep xy ra khi no lfin c to thnh c s lng cc nhm ankyl
nhiu nht gn vo 2 nguyn t cacbonni i. Tri li nh hng Hpman xy ra khi lfin c
s nhm ankyl l nh nht. Thng th cc phn ng E1 to ra ch yu sn phm tch loi
Zaixep.
V d:
CH
3
CH
H
C(CH
3
)
2
OH
H
2
O
H
2
SO
4
-
CH
3
CH C(CH
3
)
CH
3
CH
2
C CH
2
CH
3
(87,5%)
(12,5%)
3.4.4. Tch loi ankylhalogenua.
Khi c mt ca cc baz mnh vi nng cao phn ng tch loi cc ankylhalogenua
xy ra theo c ch E2.

C
H
C
X
HO
-
C C
H...OH
X
-
-
C C + + X
-
H
2
O
Trng thi chuyn tip

Cc cht thng c dng lm baz l: hyrxyt kim, ancolat kim, cc hp cht
amin.
V d:
CH
3
CH
2
CHCH
3
Br
KOH/ancol
CH
3
CH CHCH
3
CH
3
CH
2
CH CH
2 +
81% 19%
T l cc sn phm anken trong mt phn ng tch loi c u tin theo dy bin i
sau:
R
2
C=CR
2
> R
2
C=CHR > R
2
C=CH
2
> RHC=CHR >RHC=CH
2
> CH
2
=CH
2

3.4.5. Tch loi ancol.
Phn ng tch loi ancol xy ra khi c mt axit v un nng.
C
H
C
OH
C C H
2
O +
H
+
, t C
0
Kh nng tch loi ca ancol bin i:
Ancol bc III > ancol bc II > ancol bc I
a. C ch ca phn ng tch loi ancol.
C C
H
+
C C H
+
+
nhanh
chm
C C
H OH
2
+
C C
H
+
+ H
2
O
C C
H OH
H
+
nhanh
C C
H OH
2
+
b. bn ca cacbcation
Trong phn ng tch loi ancol, anken thu c nhiu khi khng ph hp vi d on
ca c ch phn ng.
V d:
CH
3
CH
2
CH
2
CH
2
OH
H
+
- H
2
O
CH
3
CH CHCH
3
CH
3
CH
2
CH CH
2 +
sn phm chnh
CH
3
CH
2
CHCH
2
OH
CH
3
H
+
- H
2
O
CH
3
CH C CH
3
CH
3
CH
3
CH
2
C CH
2
CH
3
sn phm chnh
CH
3
C
CH
3
CH
3
CH CH
3
OH
H
+
- H
2
O
CH
3
C
CH
3
C
CH
3
CH
3
CH
3
C
CH
3
CH
3
CH CH
2
+
sn phm chnh

S d thu c sn phm ca phn ng tch loi khng ph hp vi d on ca c ch
trong cc phn ng trn y l do ion cacbni t chuyn v to thnh ion cacbni khc bn
hn.
CH
3
CH
2
CHCH
3
+
CH
3
CH CHCH
3
sn phm bn
H
+
-
CH
3
CH
2
CH
2
CH
2
+
H
CH
3
CH
2
CHCH
3
in bc II
+
CH
3
CH
2
CH
2
CH
2
OH
H
+
CH
3
CH
2
CH
2
CH
2
+
in bc I
Tng t nh vy:
in bc I in bc III (bn hn)
CH
3
CH
2
C CH
2
+
CH
3
H
H
CH
3
CH
2
C CH
3
CH
3
+
CH
3
C
CH
3
CH
3
CH CH
3
+ CH
3
CH
3
C
CH
3
CH
CH
3
CH
3
+
in bc II in bc III (bn hn)

3.5. TNH CHT HO HC CA ANKEN
Anken c cha lin kt i giu in t khng bn nn phn ng c trng cho loi hp
cht ny l cng hp electrphin ph v lin kt.
3.5.1. Cc phn ng ca anken.
a. Phn ng cng hp.
1- Cng hyr.
C C H
2
+
Ni
CH CH
CH
3
CH CH
2
H
2
/Ni
CH
3
CH
2
CH
3
2- Cng halogen (X
2
= Cl
2
, Br
2
).
C C X
2
+ C C
X X
CH
3
CH CH
2
Br
2
/CCl
4
CH
3
CH
Br
CHCH
3
Br

3- Cng hyrhalogenua.
C C + C C
H X
HX
CH
3
CH CH
2
+ HI CH
3
CHICH
3

CH
3
CH CH
2
HBr
peroxit
CH
3
CHBrCH
3
CH
3
CH
2
CH
2
Br

4- Cng nc
C C H
2
O
H
+
CH C OH +
CH
3
CH CH
2
H
2
O/H
+
CH
3
CHOHCH
3
5- Cng hyphalogenua
C C X
2
H
2
O + + C C
X OH
HX +
CH
3
CH CH
2
Cl
2
H
2
O + + CH
3
CHOHCH
2
Cl HCl +
6- Hyr bo ho
C C
(BH
3
)
2
C
H
C
BH
2
H
2
O
2
C C
H OH
+
7- Polyme ho
C C n C C
n

8- Cng mtylen
C C
CH
2
N
2
CH
2
=C=O
t C
0 C C
CH
2

9- Phn ng xy ha
C C
KMnO
4
(hoc HCOOOH) C C
OH OH
+
CH
3
CH CH
2
KMnO
4
CH
3
CHOHCH
2
OH
10- Phn ng th
H C C C X
2
X C C C
+
600 C
0
600 C
0
CH
3
CH CH
2
Cl
2
ClCH
2
CH
2
Cl
+

11- Phn ng zn ho.
C C
O
3
C
O O
C
O
C O O C +
+
H
2
O/Zn
CH
3
CH
2
CH CH
2
H
2
O/Zn O
3
CH
3
CH
2
CH O O CH
2 +

CH
3
C CH
2
CH
3
O
3
H
2
O/Zn
CH
3
C O
CH
3
+ O CH
2
3.5.2 C ch phn ng cng hp electrphin.
C ch ca phn ng cng hp electrphin A
E
xy ra theo 2 bc.
C Y C
+
C C + Y X
+ -
C C
Y
+
(1)
(2) C Y C
+
X
-
+ Y C C X
Bc (1) xy ra chm quyt nh tc phn ng.
a. Phn ng cng halogen xy ra trong mi trng tr:
CCl
4
CH
2
CH
2
Br
2
+ CH
2
BrCH
2
Br
CH
3
CH CH
2 + Br
2
CCl
4
CH
3
CHBrCH
2
Br

y l phn ng dng pht hin cc hp cht c cha ni i C=C (lm mt mu
nu ca nc brm).
b. Phn ng cng hp hyrhalogenua
CH
2
CH
2
HI CH
3
CH
2
I +
CH
3
CH CH
2
HI CH
3
CH
2
CH
2
I CH
3
CHI CH
3
+ +
CH
3
C CH
2
CH
3
HI CH
3
CHCH
2
I
CH
3
CH
3
CI
CH
3
CH
3 + +
Kho st mt lng ln cc phn ng cng hp tng t nh trn, Macpnhicp (1869)
a ra quy tc: trong phn ng cng hp electrphin mt axit c prton vo mt lfin,
nguyn t hyr lin kt vi nguyn t cacbon giu hyr nht. Nh ta bit hng ca phn
ng theo c ch A
E
c trnh by trn y ph thuc vo ion cacboni. Do nh hng ca hiu
ng +I nn bn vng ca ion cacboni bin i:
R
3
C
+
R
2
CH
+
RCH
2
+
CH
3
+
Xt phn ng:
CH
3
CH CH
2
HI +
CH
3
CH
2
CH
2
+
in bc mt
CH
3
CHCH
3
in bc hai
+
V bn ca cacbcation bc II ln hn bc I nn sn phm ch yu l:
CH
3
CHCH
3
+
+ I
-
CH
3
CHICH
3

Theo kt qu ca s gii thch trn y, quy tc Macpnhicp c th pht biu tng qut
nh sau: phn ng cng hp electrphin vo lin kt i cacbon-cacbon xy ra theo hng no
to thnh ion cacbni bn vng hn.
Theo quy tc ny th kh nng phn ng ca cc anken vi cc axit bin i:
(CH
3
)
2
C=CH
2
> CH
3
CH=CHCH
3
> CH
3
CH
2
CH=CHCl
hoc: CH
3
CH=CH
2
> CH
2
=CH
2
> CH
2
=CHCl
Do phn ng xy ra qua bc to thnh cacbcation nn s to ra cc sn phm chuyn
v:
CH
3
C
CH
3
CH
3
CH CH
2
H
+
CH
3
C
CH
3
CH
3
CH CH
3
+
Cl
-
CH
3
C
CH
3
CH
3
CH
Cl
CH
3
Nhng mt khc trong phn ng ny cn to ra mt sn phm chuyn v sau y:
CH
3
C
CH
3
CH
3
CH CH
3
+ CH
3
CH
3
C
CH
3
CH
3
CH CH
3
+
Cl
-
CH
3
C
CH
3
CH CH
3
Cl CH
3

c. Phn ng cng halogen.
y l phn ng xy ra theo c ch A
E
2 giai on:
- Giai on 1 nguyn t halogen dng in cng vo ni i to thnh ion cacbni.
- Giai on 2 ion cacbni kt hp vi nguyn t halogen m in.
(1) C C Br Br
+

-
C C
Br
+
C C
Br
+
+ C C
Br
+
C C
Br
+
+ Br
-
C C
Br Br
(2)
Phn t Br
2
bnh thng khng phn cc nhng di nh sng ca trng in t mnh
ca ni i n b phn cc. Hin tng ny gi l s phn cc ho.
Nu phn ng tin hnh trong mi trng c cc anion khc th sn phm to thnh
khng phi duy nht l dn xut ihalogenua v ion cacbni c to thnh c th kt hp vi
cc tc nhn khc c trong mi trng phn ng.
3.5.3. Phn ng cng hp theo c ch gc A
R
.
Khi c mt ca pexit, phn ng cng hp ca hyrbrmua vo anken khng xy ra
theo quy tc Macpnhicp. Kharash v Meo gii thch rng, ay l phn ng cng hp xy ra
theo c ch cng hp gc t do.
(1)
(2)
Phn ng to gc
RO
.
HBr + ROH + Br
.
RO OR RO
.
t C
0
Tip theo(3), (4), (3), (4)...
(3)
(4)
Br
.
C C C
Br
C
.
+
Br
.
C
Br
C
.
HBr + C C
Br H
+
Pht trin mch
Xt phn ng:
CH
3
CH CH
2
HBr
perxit
CH
3
CHCH
2
Br
.
CH
3
CHBrCH
2
.
+
gc bc 2 gc bc 1

Trong phn ng ny gc bc 2 c to thnh s bn hn gc bc 1 nn sn phm ch
yu l prpylbrmua.
Tng t nh vy nu cho anken tc dng vi CCl
4
khi c mt pexit th s xy ra theo
c ch gc nh sau:
(1) RO OR 2RO
.
t C
0
(2)
ROCl + + CCl
3
.
RO
.
Cl CCl
3
.
Tip theo(3), (4), (3), (4)....
R CH CH
2
CCl
3
.
CCl
3
.
Cl CCl
3
+ RCHClCH
2
CCl
3
+
(4)
(3)
RCH CH
2
+ CCl
3
.
R CH CH
2
CCl
3
.
3.5.4. Phn ng xy ho (hyrxyl ho).

C C
KMnO
4
(hoc HCOOOH) C C
OH OH
+
V d:
CH
2
CH
2
KMnO
4
H
2
O + + HOCH
2
CH
2
OH
KOH MnO
2
+
+ 3 3 2
2 2
4
CH
3
CH CH
2
HCOOOH
CH
3
CHOHCH
2
OH

Nu trong iu kin khc nghit (KMnO
4
,un nng) th:
C C C C
OH OH
axit, xton hoc CO
2
V d:
CH
3
CH
2
CH
2
CH CH
2
KMnO
4
t C
0
CH
3
CH
2
CH
2
COOH CO
2
H
2
O + +
CH
3
CH C(CH
3
)
2
KMnO
4
t C
0
CH
3
COOH O C(CH
3
)
2 +
3.5.5. Phn ng th.
Phn ng th nguyn t hyr ca cc nhm alkyl trong phn t anken xy ra nhit
cao hoc c chiu sng bng tia t ngoi trong pha kh.
CH
3
CH CH
2
Cl
2
20 C,
0
CCl
4
400-600 C
0
CH
3
CHClCH
2
Cl
ClCH
2
CH CH
2
HCl +

Tin hnh halogen ho nhiu anken khc nhau, ngi ta i n kt lun rng hyr
vinyl c thay th bng halogen kh khn hn rt nhiu so vi hyr allyl. Nh vy nu kt
hp vi cc kt qu nghin cu trc y ta c dy hot ng ca nguyn t hyr bin i nh
sau:
Allyl > hyr 3
0
> hyr 2
0
> hyr 1
0
> CH
4
> vinyl
3.5.6. Phn ng zn ho.
y l phn ng ph v cc lin kt i cacbon-cacbon ca anken to thnh nhng phn
t nh hn. Phn ng xy ra trong mi trng tr.
C C
O
3
C
O O
C
O
C O O C +
+
H
2
O/Zn
Sn phm to ra l cc anhyt hoc xton. Phn ng thng dng d pht hin s c
mt ca cc ni i trong phn t.
3.1. Gi tn cc anken theo danh php thng thng v danh php IUPAC.
3.2. Cc phng php quan trng iu ch anken.
3.3. c im cu to v kh nng phn ng ca anken.
3.4. Nhng tnh cht ha hc quan trng ca anken.
3.5. Cc qui tc nh hng ca phn ng cng vo anken.
3.6. c tn theo danh php quc t cc cht sau y:
CH
3
CH
CH
3
CH CH CH
3
CH
2
C
C
2
H
5
CH
2
CH
CH
3
C
CH
3
CH
3
CH
3
CH
3
C
CH
3
C
CH
3
CH
CH
CH
2
Cl
Cl
CH
2
CH CH
3
CH
3
CH
2
CH C CH
2
CH
3
a. b.
c. d.
3.7. Vit cng thc cu to cc hp cht sau y v cho bit hp cht no c ng phn lp th:
a. 3-metyl buten-1
b. 4-nitro-3-metyl buten-1
c. 4-(1-bromoetyl)-2,6-dimetyl hepten-2
3.8. Vit cng thc cu to cc sn phm to thnh trong phn ng zn ha cc hp cht sau
y:
a. Buten-1
b. 2,3-dimetyl buten-2
c. 2-metyl propen
3.9. Vit cng thc cu to cc sn phm to thnh trong phn ng oxi ha cc anken sau y
bng KMnO
4
m c un nng:
a. Propen
b. Buten-2
c. 2-metyl propen
3.10. Hon thnh cc s phn ng sau:
a.Butanol-1
Al
2
O
3
300
0
C
X
H
2
SO
4
Y
H
2
O
t
0
C
Z
CH
3
CH
2
CH CH CH
Br Br CH
3
CH
3
Zn
X Y
H
2
O
Z U H
2
O
2
O
3
+ + b.
ha hc hu c.
H Ni.
Ni.
Chng 4
ANKIN V IEN
Cng thc tng qut ca loi hp cht ny l C
n
H
2n-2

4.1. ANKIN.
4.1.1. Cu to v cch gi tn.
a. Cu to.
Hp cht n gin nht ca ankin l axtylen trong cc nguyn t cacbon c ocbitan
lai to sp. Cc ocbitan ny lin kt vi nhau v lin kt vi hyr to thnh 3 lin kt . Mi
nguyn t cacbon cn li 2 in t p t do xen ph vi nhau to thnh 2 lin kt . Cc in t
ca 2 lin kt ny li xen ph vi nhau to thnh mt m my in t ging nh hnh tr bao
bc xung quanh lin kt cacbon-cacbon.
H
H
C C

1,2A
0

Cc ankin cao hn c cu to ging nh axtylen m trong cc nguyn t hyr c
thay th bng cc gc ankyl khc nhau.
b. Cch gi tn.
Cc hp cht ankin thng c gi tn theo 2 cch sau y:
1- Gi tn cc ankin ging nh l dn xut ca axtylen m trong cc nguyn t
hyr c thay th bng cc gc ankyl.
2- Gi tn theo danh php IUPAC bng cch i ui an ca hyrcacbon tng ng
thnh ui in.
V d: H-C C-C
2
H
5
CH
3
-C C-CH
3
CH
3
-C C-CH(CH
3
)
2

tylaxtylen imtylaxtylen mtylizprpylaxtylen
Butin-1 Butin-2 4-mtylpentin-2
Cc ankin l nhng hp cht phn cc yu nn c cc tnh cht vt l gn ging vi
ankan v anken: khng tan hoc rt t tan trong nc, tan tt trong cc dung mi khng phn
cc nh te, benzen, CCl
4
c t trng nh hn nc, nhit si tng ln khi s nguyn t
cacbon trong phn t tng.
5.1.3. Cc phng php iu ch.
a. Cc phng php cng nghip.
Phng php iu ch axtylen:
Than Than cc
vi Vi sng
2000 C
0
CaC
2
H
2
O
C
2
H
2
1.
2- xy ho khng hon ton kh mtan:
CH
4
O
2
HC CH CO H
2
+ + + 10 6 2 2

Axtylen dng hn, ct kim loi (n c gi trong bnh thp c bit bng cch ho
tan trong axton di p sut cao), dng lm nguyn liu cc hp cht khc.
b. Phng php tng hp.
Phng php tch loi:
C
Z
C
W
X Y
C C
Z W
C C
1- hyrhalogen ho cc hp cht ihalogenua.
CH
X
CH
X
KOH
C
X
CH
KOH
C C
V d:
CH
3
CH CH
2
Br Br
KOH/ancol KOH/ancol
CH
3
CH CHBr
C CH CH
3
2- Phn ng axtylua kim loi vi ankylhalogenua bc 1.
C C H
NaNH
2
C C
-
Na
+
RX
C C R

V d:
CH
3
C C
-
Na
+
CH
3
CH
2
Br + CH
3
C C CH
2
CH
3

3- halogen ho ttrahalogenua.
C C
X X
X X
Zn C C +
ZnX
2 + 2 2
V d:
CH
3
CBr CHBr
Br Br
Zn CH
3
C CH +
ZnBr
2 + 2 2
Trong tt c cc phng php nu trn y, phng php iu ch ankin bng phn
ng hyrhalogen ho cc hp cht ihalogen l c ngha nht v cc hp cht ny thng
d iu ch t anken.
4.1.4. Tnh cht ho hc ca ankin.
Tng t nh anken, ankin c m in ln do s c mt ca lin kt nn n c kh
nng tham gia cc phn ng A
E
. Mt khc do mt in t tp trung rt ln gia hai nguyn t
cacbon-cacbon ca ni 3 lm cho lin kt C- H b phn cc mnh nn ankin tham gia mt s
phn ng biu hin tnh axit.
a. Phn ng cng hp A
E
.
C C XY C C
X Y
CX CY
X Y
+
XY

1- Cng hp hyr.
R C C R
C C
R
R
H
H
C C
R H
R H
H
2
/Ni
H
2
/NH
3
sn phm cis
sn phm trans
2- Cng halogen (X
2
= Cl
2
, Br
2
).
C C
X
2
C
X
C
X
C C
X X
X X
X
2
CH
3
C C
Br
2
CH
3
CBr CHBr
Br
2
CH
3
CBr
2
CHBr
2

3- Cng hp hyrhalogenua (HX = HCl, HBr, HI).
C C
HX
CH CX
HX
CH
2
CX
2
CH
3
C CH
HCl
CH
3
CCl CH
2
HCl
CH
3
CCl
2
CH
3

4- Phn ng hyrat ho.
C C H
2
O CH C OH CH
2
C O
+
H
2
SO
4
/HgSO
4
H C C H + H
2
O
H
2
SO
4
/HgSO
4
CH
2
CH OH CH
3
CHO
Axtanhyt
CH
3
C CH
H
2
SO
4
/HgSO
4
H
2
O + CH
3
C
OH
CH
2
CH
3
C
O
CH
3
Axton

b. Cc phn ng th hin tnh axit.
C H Baz + C C
-

1- To thnh axtylua cc kim loi nng ho tr 1.
HC CH Ag C C Ag H
+
+ Ag
+
2
+ 2
CH
3
C CH Cu(NH
3
)
2
+
+ CH
3
C C Cu NH
4
+
NH
3 + +
C CH + C C
-
M
+
M
+
H
+
+
Cc mui axtylua l nhng cht tan trong nc v thng c mu c trng nn c
s dng phn bit cc ankin u mch.
2- Phn ng vi kim loi kim.
C C + Na C C
-
Na
+
H
2 +
NH
3
(CH
3
)
2
CH C CH NaNH
2
NH
3
(CH
3
)
2
CH C C
-
Na
+
+
+
te
Mt trong nhng ng dng ca loi phn ng ny l dng tng hp nhng hp cht
ankin cao hn.
R
1
C C H Na R
1
C C
-
Na
+ R
2
X
+
NH
3
R
1
C C R
2

4.2. HP CHT IEN.
4.2.1. Cu to v cch gi tn.
ien l nhng hp cht hyrcacbon c hai ni i trong phn t v vy n c cu to
tng t nh cc hp cht anken, do vy chng c nhng tnh cht ho hc tng t nh anken.
Tt nhin trong mt vi trng hp n c mt s tnh cht c th cho h phn t c hai ni i.
Cc ien c th c gi tn theo danh php thng thng hoc danh php quc t.
Trong danh php IUPAC, ngi ta gi tn cc ien tng t nh anken, ch khc l i ui
en thnh ui aien cng vi 2 s ch s ch cc v tr cc ni i.
V d: CH
2
=CH-CH=CH
2
CH
2
=CH-CH
2
-CH=CH
2

Butien-1,3 pentaien-1,4
ien c chia lm 3 loi sau y:
C C C C C C C C C C
C C C C C C C C C C C
C C C C C C C C
Loi ien lin hp
Loi khng lin hp
Loi ni i lin tip
,
,
,
4.2.2. Cc phng php iu ch ien.
Thng thng cc phng php iu ch cc ien tng t nh cc phng php dng
iu ch anken. Ngoi ra trong cng nghip iu ch butaien-1,3 dng trong tng hp
cao su nhn to, M ngi ta dng phng php crcking butan, c dng phng php
tch loi butaiol-1,4 cn Lin X dng phng php tng hp t ru tylic.
CH
2
OH
CH
2
CH
2
CH
2
OH
t C, xt
0
CH
2
CH CH CH
2
CH
3
CH
2
CH
2
CH
3
CH
3
CH
2
CH CH
2
CH
3
CH CHCH
3
CH
2
CH CH CH
2
t C, xt
0
t C, xt
0
t C, xt
0
Phng php LBEP tng hp butadien-1,4 t ru tylic nhit 400-500
0
C vi
xc tc MgO-ZnO c dng rng ri Lin X:
C
2
H
5
OH CH
3
CHO H
2
+ 2 2
CH
3
CHO CH
3
CHCH
2
CHO
OH
2
CH
3
CHCH
2
CHO
OH
H
2
/xt
CH
3
CHCH
2
CH
2
OH OH
H
2
O -2
CH
2
CH CH CH
2
4.2.3. Tnh cht.
Tnh cht ca ien ph thuc vo s sp xp ca cc ni i c trong phn t. Nu cc
ni i khng lin hp th n c cc tnh cht tng t nh anken. Nu cc ni i lin hp vi
nhau th n c mt s tnh cht khc vi anken nh sau:
1- Bn hn so vi ng phn khng lin hp.
2- Tham gia phn ng cng hp A
E
1,4.
3- C kh nng tham gia cc phn ng mnh hn so vi ng phn khng lin hp.
a. bn ca ien lin hp.
bn ca cc ien lin hp dc xc nh bng nhit hyr ho cc ien. Kt qu thc
nghim cho thy rng nhit hyr ho ca cc anken dng:
RCH=CH
2

R
2
C=CH
2
, RCH=CHR R
2
C=CHR
30 Kcal/mol 28 Kcal/mol 27Kcal/mol.
Da vo cc s liu trn y ta tnh c nhit hyr ho cho 2 cht:
CH
2
=CH-CH=CH
2
CH
3
-CH=CH-CH=CH
2
Theo tnh ton: (30+30) = 60Kcal/mol. (28+30) = 58Kcal/mol.
Thc nghim: 57Kcal/mol. 54Kcal/mol.
So snh cc kt qu tnh ton theo l thuuyt v thc nghim ta thy rng nhit hyr
ho ca thc nghim thp hn. iu chng t rng cc ien lin hp bn hn so vi cc ien
khng lin hp.
b. Phn ng cng 1, 4.
Nu cho pentaien-1,4 tc dng vi brm trong iu kin thch hp th trc tin ta thu
c 4,5-ibrmpenten-1 v tip theo l dn xut 1,2,4,5-ttrabrmpentan.
CH
2
CH CH
2
CH CH
2
Br
2
CH
2
Br
CH
Br
CH
2
CH CH
2
Br
2
CH
2
Br
CH
Br
CH
2
CH CH
2
Br Br

Cn khi cho butaien-1,3 tc dng vi brm cng trong iu kin th ngoi sn phm
3,4-ibrmbuten-1 ta cn thu c 1,4-ibrmbuten-2. Phn ng cng xy ra tng t di vi
cc ien lin hp khc v vi cc tc nhn khc nhau.
CH
2
CH CH CH
2
CH
2
Br
CH
Br
CH CH
2
CH
2
Br
CH CH CH
2
Br
CH
3
CHClCH CH
2
CH
3
CH CHCH
2
Cl
CH
3
CH
2
CH CH
2
CH
3
CH CHCH
3
Br
2
H
2
/Ni
HCl
+
+
+

S khc nhau v kt qu ca sn phm thu c ca cc phn ng ca pentaien-1,4 v
butaien-1,3 vi brm c gii thch nh sau:
Phn ng cng electrphin xy ra qua bc to thnh ion cacbni:
CH
2
CH CH CH
2
CH
3
CH CH CH
2
+
+
CH
2
CH
2
CH CH
2
H
+
in bc II
in bc I
Theo s phn ng trn y, ion cacbni bc II c to thnh nh nh hng ca hiu
ng +I nn bn hn ion bc I. V vy phn ng xy ra ch yu theo hng to thnh ion bc II.
Mt khc ion bc II ny ch yu tn ti di dng cng hng sau:
CH
3
CH CH CH
2
+
CH
3
CH CH CH
2
+
Giai on tip theo cc anion c th cng hp vo c 2 nguyn t cacbon do to thnh
mt hn hp 2 sn phm.
CH
3
CH CH CH
2
+
X
-
a b
CH
3
CHX CH CH
2
CH
3
CH CHCH
2
X
a
b
sn phm 1,2
sn phm 1,4
Khi kho st phn ng butaien -1, 3 vi HBr ngi ta nhn thy:
CH
2
CH CH CH
2
(80%)
(20%)
CH
3
CH CHCH
2
Br
CH
3
CHBr CH CH
2
CH
3
CHBr CH CH
2
CH
3
CH CHCH
2
Br (20%)
(80%)
40 C
0
HBr, 40 C
0
HBr, -80 C
0
Vy nhit thp sn phm 1,2 u tin hn, tri li nhit cao sn phm 1,4 l ch
yu.
E
Tin trnh phn ng 1,2 Tin trnh phn ng 1,4
1,2
E
a
E
a
1,4
CH
3
CH CH CH
2
+
CH
2
CH CH CH
2
CH
3
CHBr CH CH
2
CH
3
CH CH CH
2
Br
Br
-
H
+
Br
-
Gin nng lng ca phn ng butaien-1,3 vi HBr
4.2.4. Cao su thin nhin v cao su tng hp.
a. Cao su thin nhin.
Cao su thin nhin c khai thc t m ca cc cy thc vt thuc h Hevia. Cy cao su
u tin tm thy nam chu Phi, sau ny c trng Innxia, ng Dng. Ngoi ra m
cao su cn c khai thc mt s loi cy khc nh cy si, cy b cng anh chu u, cao
su c s dng vo u th k 18.
Nhng ngi da l nhng ngi u tin s dng cao su. H ph bc cao su bng
nhng khun t st v sy. Sau khi thu c nhng mu cao su n hi v khng thm nc,
h p v vn khun t st ra thnh mnh v ko cc mnh qua mt l ming bnh to
thnh cc loi bnh ng nc.
nc Anh, ngi ta dng cao su th ho tan vo hyrcacbon ca nha than v thu
c mt dng keo cao su. Ngi ta s dng keo cao su ny ph ln b mt ca vi lm vi
khng thm nc. b mt c ph bng nha cao su khng thm nc, khng b dnh bn,
ngi ta gp i chng li. Loi o ma c hai lp du nh vy do Makintosh lm ra nn c
gi l o mmg t. V sau, khc phc s dnh bn ny ngi ta cho thm cc loi bt khc
nhau. Mt trong nhng loi bt l lu hunh v nh pht hin ra s lu ho cao su.
b. Thu nhn v ch bin cao su.
M cao su thu nhn c t cy cao su c lm ng li bng axit axtic (y l dng
m th). Cao su th c nghin trn my nghin c nhiu rng ca. Trong qu trnh , cao su
th cng c chuyn thnh dng mm mi, do c th trn ln chng vi cc cht ph gia,
cht lu ho (cao su xm c trn thm b hng, cao su trng c trn thm xit titan, cao su
trn thm sunfit antim)
Hnh trm nm sau ca qu trnh nghin cao su, ngi ta mi gii thch c rng: trong
qu trnh , cao su th (C
5
H
8
)
n
vi phn t lng khong 100.000-150.000 di tc dng c
hc b t ra thnh nhng mnh nh hn bng s phn ct ng ly. Cc u mch gc t do
ny kt hp vi xy to thnh pexit v cui cng li kt hp vi nhau to thnh nhng phn t
nh hn. S gim ln ca cc phn t lm tng thm tnh n hi, mm mi ca cao su
to iu kin cho s lu ho hoc trn ln vi cc cht ph gia.
c. Cu to ca cao su thin nhin.
Khi zn ho cao su thin nhin, ngi ta thu c cc kt qu sau:
... CH
2
C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH
2
...
O
3
... CH
2
C
H
3
C
O O
CH
O
CH
2
CH
2
C
H
3
C
O O
CH
O
CH
2
CH
2
C
O O
CH
O
CH
2
...
H
2
O, Zn
CH
2
C O
CH
3
O CH CH
2
CH
2
C
CH
3
O O CH CH
2
CH
2
C O
CH
3
+ + + ...
S c mt ca ni i trong phn t cao su rt quan trng v n cho php tin hnh lu
ho.
...
CH
2
C
S
S
CH
3
CH
S
CH
2
CH
2
C
S
S
CH
3
CH
S
CH
2
...
S
CH CH
2
CH
2
C
CH
3
CH
S
CH
2
...
C
CH
3
CH
2
...
S
S
S
S
...
CH
S
C
CH
3
CH CH
2
CH C
CH
3
CH CH
2
...
...
CH C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH
...
S
...
CH
2
C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH
2
...
...
CH
2
C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH
2
...
+ nS
Cao su lu ho c cu to mng khng gian nn cng hn. Nu lu ho nhiu s c sn
phm l ebnt dng lm cht cch in.
Mt hp cht t nhin gutapetra cng c cng thc phn t ging cao su t nhin
(C
5
H
8
)
n
nhng hai hp cht ny khc nhau v s phn b hnh hc. Cao su t nhin c cu hnh
cis, cn gutapetra c cu hnh trans.
H
3
C
C C
H
2
C
H
CH
2
CH
2
C C
H
3
C
CH
2
H
CH
2
C
H
3
C
C
H
CH
2

Cao su t nhin (ng phn cis)
H
3
C
C C
H
2
C
CH
2
H
H
3
C
C C
H
2
C
CH
2
H H
CH
2
H
2
C
H
3
C
C C
Gutapetra (ng phn trans)
Ti sao cao su c tnh n hi?
Ta bit rng mch cao su c phn t ln. Mt khc do cc nguyn t cacbon c gc lai
to l 109
0
28 cng vi s quay t do ca cc lin kt cacbon-cacbon to thnh v s cu
dng khc nhau nhng v tr ni i trong phn t khng thay i. mt phn t ln, s xp
t ca mch phn t s khng iu ho m rt tu tin v cu dng. Khi ko mch nhng ch
sp xp khng trt t b ko ra lm cho mch cao su b gin. Nu b lc ko, n li tr v trng
thi bnh thng.
d. Cao su tng hp.
Cao su tng hp l polybutaien. thay i tnh cht ca n, cao su tng hp thng s
dng cc phn ng ng trng hp: butaien vi styren, butaien vi acrilnitrin
CH
2
CH CH CH
2
CH
2
CH CH CH
2
CH
2
CH
C
6
H
5
CH
2
CH CH CH
2
...
CH
2
CH CH CH
2
CH
2
CH CH CH
2
CH
2
CH
C
6
H
5
CH
2
CH CH CH
2
...
+ + +
xt
Cao su butaien Styren (Buna S)
4.1. Danh php thng thng v danh php IUPAC i vi ankin.
4.2. Cc phng php iu ch ankin.
4.3. Cc tnh cht ha hc quan trng ca ankin.
4.4. a. Ti sao ankin khng c ng phn hnh hc. Vit ng phn hnh hc ca ankin c 5
cacbon c ni i.
b. Ti sao xiclohexin khng tn ti. Vit ng phn hnh hc ca ankin c 6 cacbon vi
vng 3 cnh.
4.5. Gi tn nhng hp cht sau y theo danh php IUPAC:
CH
3
CH
CH
3
C CH CH
3
CH
2
CH
C
2
H
5
C C CH CH
3
CH
3
Cl CH
2
CH
2
C C CH
3
Br C C CH
2
CH
3
(CH
3
)
3
C C C C(CH
3
)
3
a. b. c.
d. e.

CH
3
C CH CH
3
CH
2
C C CH
2
CH
3
HC C CH
2
CH
2
CH
2
Cl
4.6. Hy dng phng php ha hc phn bit: butan, buten-1, butin-1 v butin-2.
4.7. T axetilen v nhng ha cht cn thit iu ch cc ankin sau:
a. b. c.

4.8. Vit cng thc cu to ca cc hirocacbon c cng thc phn t C
5
H
8.
Gi tn cc ng
phn loi ankadien.
4.9. T buten-1 v cc ha cht cn thit iu ch butadien-1,3.
4.10. Hon thnh s phn ng sau:
CH
2
CH CH CH
2
Br
2 HBr
X Y A B + +
Buten-1
HBr
KOH/ancol
-HBr -2HBr
A B
+
Br
2
X
KOH/ancol
Y
a.
b.

4.11. Mt ankadien c cng thc phn t C
5
H
8
, sau khi zn ha em thu phn znit to
thnh thu c mt trong cc sn phm l:
CH
3
C CH O
O

Hy cho bit cng thc cu to ca ankadien ban u.
4.12. Vit cng thc cu to ca nhng dien c cng thc phn t C
5
H
8
. Gi tn cc ng phn
v ch r cacbon lai ha sp.
4.13. Hai hirocacbon ng phn A v B c cng thc phn t C
6
H
10
u lm mt mu nc
brom v c kh nng tc dng vi ozon. Khi thu phn ozonit to thnh t A cho cho mt phn
t OHCCH
2
CH
2
CHO v hai phn t CH
2
O. Khi thu phn ozonit to thnh t B cho 3 sn
phm: CH
3
CO-CHO, CH
2
O v CH
3
CHO. Xc nh cng thc cu to ca A v B.
ha hc hu c.
H Ni.
Ni.
Chng 5
CC HP CHT HYROCACBON VNG
Cc hp cht m trong cc nguyn t cacbon to vi nhau thnh mch kn gi l cc hp
cht vng.
5.1. CCH GI TN V CC NG PHN.
Cc hp cht vng c gi tn bng cch thm tip u ng xycl.
5.1.1. Cch gi tn cc hp cht n vng (mnxycl).
gi tn cc hp cht n vng, mch chnh c chn l vng xycl sau nh s th
t cc nhm th sao cho tng cc ch s l nh nht. Thng tin li, ngi ta n gin vit
cc nguyn t cacbon v hyr ca vng.
V d:
H
3
C
CH
3
CH
3
1,2,4-trimtylxyclhexan

Trong trng hp phn t ln, mch chnh phc tp th tn gi trn y khng ph hp
nn ngi ta coi vng xycl nh mt nhm th.
V d:
CH
2
C
CH
3
CH
3
CH
OH
CH
3
3,3-imtyl-4-xyclpentylbutanol-2

5.1.2. Cch gi tn cc hp cht a vng (polyxycl).
Thng thng cc hp cht a vng c chia lm cc loi sau:
1- Cc vng ring bit
(CH
2
)
n
2- Cc vng ni vi nhau bi mt lin kt cacbon-cacbon
3- Cc vng c mt nguyn t cacbon chung
4- Cc vng c 2 nguyn t cacbon chung
5- Cc vng c s nguyn t cacbon chung ln hn 2
CH
2
Tn gi ca 2 ging nh trnh by phn trn.
Tt c cc vng cn li c xem nh l hp cht c cu ni. Bt u nh s t mt u
cu ni theo vng ln, tip n vng b hn v cui cng l cc nguyn t cacbon ca cu ni.
Nu cc nguyn t cacbon ca vng cn c cc nhm th th chn sao cho ch s l nh nht.
Gi tn mch chnh ca vng, thm tip u ng bixycl- tip theo l s nguyn t cacbon ca
mi vng t trong du ngoc vung (nguyn t cacbon ca 2 u cu ni khng tnh).
C(CH
3
)
2
CH
3
O
1
2
3
4
5
6
7
1,7,7-trimtyl-bixycl[2,2,1]-heptanon-2
CH
3
1
2
3
4
5
6
7
8
9
10
2-mtyl-bixycl[5,3,0]-kan

5.1.3. ng phn.
ng phn ca mt hp cht vng gm cc loi:
1- ng phn do s thay i cc nguyn t cacbon ca vng.
V d: Hp cht C
5
H
10
c cc ng phn sau y:
CH
3
CH
3
CH
3
2- ng phn do s thay i cu to ca mch nhnh:
V d:
C
2
H
5
CH
3
CH
3
CH
3 C
2
H
5
CHCH
3
H
3
C CH
2
CH
2
CH
3

3- ng phn do s sp xp ca cc nhm th khc nhau cc v tr khc nhau:
V d:
CH
3
CH
3 CH
3
CH
3
R
1
R
2
R
1
R
2 R
1
R
2
4- ng phn hnh hc:
V d:
CH
3
CH
3
CH
3
CH
3
ng phn trans ng phn cis
5- ng phn quang hc xut hin khi trong phn t c cacbon bt i:
V d:
C
R
H
R
C
H
C
O
R
H
C
O
R
H
6- ng phn cu dng:
Gh Thuyn

T du m ta c th thu nhn mt s hp cht vng nh: xyclhecxan,
mtylxyclhecxan, mtylxyclpentan, 1,2-imtylxyclpentan.n Cc dn xut xyclhecxan c
th iu ch bng phn ng hyr ho benzen:
R
Mo
2
O
3
, Al
2
O
3
, 560 C, 21at
0
R
H
2
/Ni,
0
150-200 C, 25at
5.2.2. Phng php tng hp.
tng hp mt hp cht vng thng c 2 giai on:
1- Chuyn ho mt hp cht mch h no thnh mch vng (phn ng ng vng).
2- Chuyn ho mt hp cht vng thu nhn c thnh vng cn thit phi tng hp.
a. Tng hp cc hp cht xyclprpan v xyclbutan.
- T ankylihalogenua
CH
2
CH
2
Br
CH
2
Br
2Na
2NaBr +
CH
2
CH
2
CH
2
Br
CH
2
Br
2Li-Mg
2LiBr 2Mg
+ + +
- Phn ng vi iazmtan
C
C
CH
2
N
2
C
C
N
CH
2
N
C
C
CH
2
N
2
+ +
Cu, t C
0
- Cc hp cht ien-1,3 di tc dng ca tia t ngoi cho xyclbuten
CH
CH
CHR
CHR
h
CH
CH
CHR
CHR

- Phn ng quang ho xyclpentanon
O
h
CO +
b. Tng hp cc hp cht xyclpentan, xyclhecxan hoc ln hn.
- T ankylihalogenua
(CH
2
)
CH
2
Br
CH
2
Br
n
2Li-Mg (CH
2
)
CH
2
CH
2
n
2LiBr 2Mg +
+ +
- T mui canxi icacbxylat
CH
2
CH
2
COO
CH
2
CH
2
COO
Ca
CH
2
CH
2
CH
2
CH
2
C O
t C
0
H
2
/Ni
- T ankan
CH
3
CH
CH
3
CH
2
CH CH
3
CH
3
Pt (300 C)
0
CH
3
H
3
C H
2 +
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
Pt
H
2
+
c. Cc hp cht vng khng no c th iu ch t xyclankan hoc t hp cht thm.
X
H
2
/Ni
X
KOH/ancol
OH
H
2
/Ni
OH
H
+
, t C
0
5.3. TNH CHT VT L V HA HC.
Tng t nh ankan v anken tng ng, cc hp cht vng khng phn cc, c t
trng nh thua nc,c nhit si tng theo chiu tng ca s nguyn t cacbon
5.3.2. Tnh cht ho hc.
a. Tnh cht chung.
Tr mt s phn ng c bit, xyclankan v xyclanken c cc tnh cht tng t nh
ankan v anken.
Phn ng th theo c ch gc ca xyclankan:
Br
2
+ + HBr
h
Br
Cl
2
Cl
HCl + +
h
Cc phn ng cng electrphin ca xyclanken:
O
3
H
2
O/Zn
CH CHCH
3
CH
2
CH
2
CH O O
H
3
C
Br
2
Br
Br
+
1,2-ibrmxyclhecxan
CH
3
+
HI
CH
3
I
1-id-1-mtylxyclpentan
b. Cc phn ng c bit ca xyclprrpan v xyclbutan phn ng th theo c ch gc
c trng cho cc xyclankan k c xyclyprpan v xyclbutan. Nhng mt khc xyclyprpan
v xyclbutan cn tham gia mt s phn ng cng sau y:
CH
3
CH
2
CH
2
CH
3
H
2
/Ni, 120 C
0
Br
2
/CCl
4
HI
Khng c phn ng
Khng c phn ng
CH
3
CH
2
CH
3
BrCH
2
CH
2
CH
2
Br
CH
3
CH
2
CH
2
I
H
2
/Ni, 80 C
0
Br
2
/CCl
4
HI
Nh vy xyclbutan km hot ng ho hc hn nhiu so vi xyclprpan.
c. Thuyt sc cng Maye.
gii thch kh nng tham gia phn ng ca xyclprpan v xyclbutan trn y, nm
1885 gio s Baye Adong trng i hc tng hp Miukhen cho rng tt c cc nguyn t
ca vng u nm trong mt mt phng, do gc ho tr ca xyclprpan l 60
0
, xyclbutan l
90
0
, xyclpentan l 108
0
, xyclhecxan l 120
0
V vy khi to thnh vng, gc t din ca
nguyn t cacbon b xm phm gy ra mt sc cng gi l sc cng Maye. Theo Baye, sc cng
ny cng ln th vng cng t bn, tc l kh nng phn ng cng dn n ph v vng cng
ln. Cng thc ton hc tnh sc cng Baye nh sau:
[] = (109
0
28 - )/2 - gc a din u ca vng
Gi tr sc cng Baye tnh c cho cc xyclankan c n nguyn t cacbon nh sau:
n 3 4 5 6 7 8 9
29
0
44 9
0
44 0
0
44 -5
0
16 -9
0
33 -12
0
46 -36
0
16
Nh vy theo Baye, vng c sc cng ln nht l xyclprpan v cc vng ln. Vng c
sc cng nh nht l xyclpentan. Thc nghim cho thy rng i vi cc vng: xyclprpan,
xyclbutan, xyclpentan sc cng Baye ph hp vi cc tnh cht ca vng. Nhng i vi
xyclhecxan v cc vng ln hn sc cng Baye khng cn ngha. Xyclhecxan c sc cng
ln hn xyclpentan nhng n li rt bn v bn hn c xyclpentan. Ti sao vy? iu ch
c th gii thch rng, trong khi a ra thuyt ca mnh, Baye phm mt sai lm ln l coi
tt c cc nguyn t cu to nn vng u nm trong mt mt phng.
d. Quan nim hin i v cu to ca hp cht vng.
Theo quan nim ngy nay, bn ca mt hp cht vng ph thuc: sc cng Baye (sc
cng gc lin kt), sc cng Fitze (lc tc dng tng h gia cc nguyn t hoc nhm nguyn
t k nhau ca vng) v lc Van-ec-van ca cc nhm khng k nhau. Cc nguyn t cacbon
trong ankan c ocbitan lai to sp
3
do hnh thnh lin kt chng hng cc ocbitan lai ho
ny li vi nhau v c c s xen ph cc i cc gc lin kt phi l gc t din 109
0
28.
60
0
109 28'
0
Nhng trong phn t xyclprpan, gc lin kt khng th l 109
0
28 m l 60
0
, do
nguyn t cacbon khng th hng cc ocbitan lai ho sp
3
thng hng li vi nhau nn s xen
ph s t hn, lin kt s km bn hn. Trong trng hp i vi xyclbutan, gim bt sc
cng mt nguyn t cacbon cn li nn to kh nng xen ph cao hn, vng bn hn.
trnh cc sc cng xyclpentan c cc cu dng thun li, nht l dng phong b v
dng na gh.
Xyclhecxan c cu dng gh, xon, thuyn.
Gh Xon Thuyn

Nu phn t xyclhecxan tn ti di dng cu to gh th trong c hai loi hyr lin
kt khc nhau: 6 lin kt thng gc vi mt phng gh l lin kt axial (a), cn 6 lin kt nm
trong mt phng gh l equatorial (e).
e
a

Chng 6
HP CHT HYRCACBON THM
Cc nh ho hc chia cc loi hp cht hu c thnh 2 loi: hu c bo v hp cht thm
gm c benzen v cc loi hp cht khc c tnh cht tng t nh benzen.
6.1. CU TO CA BENZEN.
Trong tt c cc hp cht hu c, benzen c nghin cu k nht. Benzen c pht
hin t nm 1825 nhng mi dn nm 1931 ngi ta mi ngh c mt cng thc cu to
ph hp v phi 10-15 nm sau cng thc mi c cc nh ho hc chp nhn.
6.1.1. Cng thc phn t, s lng ng phn v cu to ca Kkul
1- Benzen c cng thc phn t C
6
H
6
. Cc phng php phn tch nguyn t xc nh
rng iu hon ton ng. Vi cng thc C
6
H
6
, benzen c th c cc cng thc cu to sau
y:
(IV)
(V)
CH
3
C C C C CH
3
CH
2
CH C C CH CH
2
C
C
C
C
C
C
H
H
H
H
H
H
Cng thc Kkul
(I)
(II) (III)
C
C
C
C
H
H
H
H
H
H C
C
C
C
C
C
C
CH
2
H
H
H
H
Cng thc ioa
Vy cng thc no trn y s ph hp vi benzen?
2- Benzen ch cho mt sn phm th mt ln duy nht l C
6
H
5
X. Tc l nu brm ho
benzen th n s cho sn phm th mt ln duy nht l C
6
H
5
Br, tng t nh vy cng ch thu
c sn phm th mt ln duy nht l C
6
H
5
Cl, C
6
H
5
NO
2
iu chng t rng, trong cu
to ca benzen, 6 nguyn t hyr hon ton tng ng nh nhau, do khi thay th mt
nguyn t hyr no th cng ch cho mt v ch mt sn phm duy nht m thi. Cng thc
cu to V c 2 loi hyr nn sn phm th mt ln c th l 2 sn phm, do V khng th l
cu to ca benzen. Tng t nh vy cc cng thc cu to II v III cng khng ph hp v do
cng thc cu to ca benzen ch c th l I hoc l IV.
b. Benzen cho 3 sn phm th ng phn 2 ln C
6
H
4
X
2
hoc C
6
H
4
XY, tc l ch thu
c 3 sn phm ng phn brm ho 2 ln C
6
H
4
Br
2
hoc 3 sn phm C
6
H
4
NO
2
Cl.
C
C
C
C
C
C
Br
Br
H
H
H
H C
C
C
C
C
C
Br
H
Br
H
H
H C
C
C
C
C
C
Br
H
H
Br
H
H
1,2-ibrmbenzen 1,3-ibrmbenzen 1,4-ibrmbenzen

iu ny chng t rng, cng thc cu to ca benzen khng th l IV m ch c th l I
v nh vy mi c th ph hp vi kt qu thc nghim trn y. Tip tc nghin cu cu to I,
ngi ta nhn thy rng 1,2-ibrmbenzen c 2 cng thc cu to VI v VII ch khc nhau bi
v tr ca brm so vi ni i.
C
C
C
C
C
C
Br
Br
H
H
H
H C
C
C
C
C
C
Br
H
H
H
H
Br
VI VII

V vy Kkul cho rng cng thc cu to tht ca benzen nm gia cng thc VIII v
IX.
C
C
C
C
C
C
H
H
H
H
H
H
C
C
H
H C
C H
H
H
H
C
C
VIII IX

iu c ngha l benzen chng phi l cng thc VIII m cng chng phi l cng
thc IX m l mt cng thc cu to trung gian gia VIII v IX. Cng khng c ngha l benzen
c cu to t cc phn t m trong mt na tng ng vi VIII cn na kia tng ng vi
IX hoc l mi phn t c chuyn ho t VIII qua IX v ngc li. y ch c ngha l tt c
cc phn t hon ton nh nhau v mi mt phn t c cu to trung gian gia VIII v IX.
Mt cng thc phn t c th biu din bng nhiu cng thc cu to m trong ch c
s khc nhau bi s phn b in t (cc ht nhn nguyn t sp xp nh nhau) th ngi ta ni
phn t c kh nng cng hng. Cng thc cu to l cng thc cng hng.
6.1.2. bn ca vng benzen.
Cng thc cu to ca Kkul trn y ph hp vi cc im a, b, c nhng nhiu yu t
khc cng thc cha cp n, c bit l bn vng ca vng benzen. V d thc
nghim cho thy rng, phn ng c trng ca benzen l phn ng th ch khng phi l phn
ng cng, m ng l ra benzen theo cng thc cu to ca Kkul th c th xem nh l
xyclhecxatrien nn n phi d dng tham gia cc phn ng cng hp.
so snh, ngi ta nghin cu phn ng cng hp ca xyclhecxen v benzen vi mt
s tc nhn sau y:
Tc nhn xyclhecxen benzen
KMnO
4
(lnh, long) B oxy ho rt nhanh Khng phn ng
Br
2
/CCl
4
(bng ti) Kt hp rt nhanh Khng phn ng
HI Kt hp nhanh Khng phn ng
H
2
/Ni Kt hp nhanh 25
0
C v
p sut 1,4 at.
Hyr ho chm 100-
200
0
C, 105at.
Trong khi , benzen tham gia tt mt s phn ng th sau y:
C
6
H
6
HONO
2
/H
2
SO
4
HOSO
3
H/SO
3
X
2
/Fe
RCl/AlCl
3
ROCl/AlCl
3
C
6
H
5
SO
3
H H
2
O Sunfonic ha
C
6
H
5
X HX Halgen ha
C
6
H
5
R HCl Ankyl ha
C
6
H
5
COR HCl Axyl ha
C
6
H
5
NO
2
H
2
O Nitr ha
+
+
+
+
+

Cc kt qu nh tnh trn y cho php kt lun rng benzen bn hn rt nhiu so vi
xyclhecxen.
Bng phng php nh lng nhit hyr ho v nhit phn hu, ngi ta cng thu
c kt qu tng t.V d nhit hyr ha thu c bng thc nghim t hn so vi tnh ton
bng l thuyt l 36 Kcal/mol. iu c ngha l benzen bn hn 36 Kcal/mol so vi s tnh
ton cho xyclhecxatrien. Ngi ta gi nng lng ny l nng lng cng hng.
6.1.3. di lin kt ca cacbon-cacbon trong phn t benzen.
di lin kt cacbon-cacbon ca benzen nh nhau v c gi tr vo khong gia
di lin kt v ni i. Phng php nhiu x Rngen xc nh c di lin kt cacbon-
cacbon trong benzen l 1,39A
0
.
6.1.4. Cu to ca benzen di nh sng ca thuyt ocbitan phn t.
Benzen c cu to phng, trong tt c 6 nguyn t cacbon u nm trong mt mt
phng. Vng benzen l mt vng i xng m trong cc nguyn t c ocbitan lai to sp
2
, vi
gc lin kt l 120
0
. Mi nguyn t cacbon cn li mt in t p xen ph vi nhau to thnh
mt h m my in t nm pha trn v pha di mt phng ca vng. Chnh s xen ph
h thng 6 in t p ny li vi nhau to cho vng benzen c tnh bn vng.
H
H
H
H
H
H
6.1.5. Cch biu din vng benzen.
Ngi ta c th biu din vng benzen bng mt trong cc cng thc cu to sau y:
6.1.6. Quy tc (4n+2) ca Huycken.
Ngoi nhng hp cht c cha vng benzen, cn c rt nhiu hp cht khc cng c
gi l hp cht thm, mc d b ngoi chng khng ging benzen. Vy c tnh chung cho tt
c cc hp cht thm l g?
Nu nhn nhn di gc thc nghim, cc hp cht thm phi l nhng hp cht m
phn t ca n phi c tnh khng no ln nhng li khng tham gia cc phn ng cng hp c
trng cho cc hp cht khng no. Tri li d dng tham gia cc phn ng th ging benzen. C
bn cao so vi hyrcacbon tng ng v c cu to phng, c mch vng.
Nu nhn nhn t gc l thuyt, mt hp cht mun l hp cht thm th trong phn t
ca n phi cha h thng in t cng hng nm pha di v pha trn mt phng phn
t. Mt khc s in t phi l (4n+2) in t, tc l cc in t trong phn t phi l 2, 6,
10 chnh l quy tc Huycken. V vy benzen c 6 in t nu n l hp cht thm. Da
vo quy tc Huycken ta xt mt s hp cht sau y:
+
.
+
.
(I)
(II) (III) (IV) (V)
(VI)

Trong cc hp cht trn y ta nhn thy:
(I) - Xyclpentaienyl-cation c 4 in t (khng thm).
(II) - Xyclpentaienyl- raical c 5 in t (khng thm).
(III) - Xyclpentaienyl- anion c 6 in t (hp cht thm).
Tng t nh vy, trong cc cu to (IV), (V), (VI) ch c cation (IV) c 6 in t l
thuc loi hp cht thm.
6.1.7. Cch gi tn cc hp cht ca benzen.
gi mt s ln hp cht ca benzen, ngi ta gi bng cch thm tn gi ca nhm
th vo t benzen.
Cl
Br NO
2
Clobenzen Brmbenzen Nitrbenzen

Mt s hp cht c tn gi ring khng lin quan n nhm th.
Tluen Anilin Phnol Axit benzic Axit benzsunfnic
H
3
C
H
2
N HOOC HO
3
S
HO
Nu trong vng benzen c mt s nhm th th khi gi cn phi gi tn cc v tr nhm
th. gi tn cc dn xut th 2 ln ca benzen th dng 3 tip u ng p- (para), m-(mta), o-
(oct):
Br
Br
Br
Br
Br
Br
o-ibrmbenzen m-ibrmbenzen p-ibrmbenzen

Nu 2 nhm th khc nhau th gi:
p-brmibenzen m-clonitrbenzen o-nitrtluen p-brmphenol
I
Br
NO
2
Cl
CH
3
NO
2
Br
OH
Nu trong vng benzen c hn 2 nhm th th phi nh s:
- Nu c 3 nhm th nh nhau th nh s sao cho tng ca cc ch s l nh nht
Br
Br
Br
Br
Br
Br
Gi: 1,2,4-tribrmbenzen Khng gi: 1,4,6-tribrmbenzen
1
2
3
4
5
6
1
2
3
4
5
6
Nu cc nhm th khc nhau th chn mt nhm th nh s 1 v tip theo l cc nhm
th khc, khi gi tn nhm s 1 khng gi ch s. Trng hp c nhm th no ph hp vi
tn gi ring th xem nh n v tr s 1.
V d:
3-clo-5-brmnitrbenzen 2,6-initrtluen 2-clo-4-nitrphnol
NO
2
Br Cl
CH
3
NO
2
O
2
N
OH
Cl
NO
2
6.2. PHN NG TH ELETRPHIN CA HP CHT THM.
Cc hp cht thm tng t nh benzen do cng hng cc in t ca vng nn lm
tng tnh bn vng. Mt khc, mt in t ln cho php vng thm ng vai tr l 1
ngun in t. V vy n c kh nng tham gia cc phn ng vi tc nhn electrphin.
6.2.1. Mt s phn ng th electrphin S
E
ca cc cht thm.
1- Nitr ho
H
2
SO
4
Ar H HONO
2
Ar NO
2
H
2
O + +

2- Sunfnic ho
Ar H HOSO
3
H + Ar SO
3
H H
2
O +
SO
3
3- Halogen ho
Ar H + X
2
Ar X HX (X
2
= Cl
2
, Br
2
)
Fe
+

4- Ankyl ho Frien-Crap
Ar H RCl
AlCl
3
Ar R HCl + +

5- Axyl ho Frien-Crap
Ar H RCOCl
AlCl
3
Ar COR HCl + +

6- Nitrz ho
Ar H HONO Ar NO H
2
O
+ +

7- iaz ho
Ar
1
H Ar
2
N N X Ar
2
N N Ar
1
HX
+ +

8- Prtn ho
Ar SO
3
H H
+
Ar H H
2
SO
4
H
2
O
+ +
Ar H D
+
Ar D H
+
+ +

6.2.2. C ch chung ca cc phn ng th electrnphin ca benzen.
Phn ng th electrnphin ca cc hp cht thm xy ra theo mt c ch duy nht khng
ph thuc vo s cnh tranh ca cc tc nhn, gm c 2 giai on:
C
6
H
6
Y
+
C
6
H
5
H
Y
+
+
chm
(1)
C
6
H
5
H
Y
+
Z
-
C
6
H
5
Y HZ +
nhanh
+
(2)
Giai on (1) l s tn cng ca tc nhn electrphin vo vng thm to thnh ion
cacbni. Giai on (2) l s tch ion hyr di tc dng ca mt baz to thnh mt sn
phm th. Ngy nay, bng cc phng php vt l hin i, ngi ta nhn thy rng giai
on (1) ca S
E
xy ra qua bc to thnh phc v phc sau y:
phc
Y
H + Z
-
Y
HZ + +
(2)
Y
+
Y
+
+
Y
H +
phc
(1)
Nh vy, c ch ca S
E
giai on (1) tng t nh A
E
l bc to thnh ion cacbni
nhng khc vi A
E
bn ho sn phm bng cch cng thm 1 prtn th S
E
li tch i 1
prtn to thnh h lin hp in t .
6.2.3. Chng minh c ch S
E
.
a. Khi nim v hiu ng ng v.
Nu mt nguyn t bit trong trng thi chuyn tip ca phn ng c lin kt yu hn
so vi trong hp cht th phn ng vi ng v nng hn ca n s xy ra chm hn. S khc
nhau ca tc phn ng gy ra bi cc ng v khc nhau ca mt nguyn t gi l hiu ng
ng v. Hiu ng ng v thng biu hin cc phn ng c phn ct lin kt.
V d:
C H C
-
H Z + Z
-
C . . . H . . . Z +
C D D Z Z
-
+ C . . . D . . . Z
C
-
+

o K
H
v K
D
ngi ta nhn thy rng K
H
/K
D
~5-8, tc l phn ng xy ra vi hyr
nhanh hn khong 5-8 ln so vi tri.
b. Chng minh c ch 2 bc ca S
E
.
Ta ni phn ng S
E
xy ra theo c ch 2 giai on nh trnh by trn y m khng
phi xy ra mt giai on:
C
6
H
6
Y
+
C
6
H
5
Y
H
+
H
+
+ C
6
H
5
Y +
Ti sao vy? V rng nu thay th hyr trong nhn thm bng tri hay triti v sau
tin hnh phn ng S
E
th nhn thy rng tc phn ng khng thay i -tc l khng c hiu
ng ng v. iu c ngha l tc phn ng khng ph thuc vo giai on lm t lin
kt cacbon-hyr. Ngha l tc phn ng ch ph thuc vo giai on (1) to thnh phc
m khng xy ra s t lin kt nn i vi hyr, tri, triti u nh nhau. Nu phn
ng xy ra theo c ch mt giai on th tt nhin phi quan st thy hiu ng ng v v c s
ph v lin kt cacbon-hyr nhng iu khng nhn thy. Tng t nu giai on (2)
ca c ch 2 giai on xy ra chm hn so vi (1) (n quyt nh tc phn ng) th cng phi
quan st thy hiu ng ng v. iu ny cng khng nhn thy. Vy c ch 2 giai on v giai
on (1) quyt nh tc phn ng trn y l ng.
Ta c th nhn thy iu qua s thay i ca gin nng lng phn ng di y
(ng chm chm khng lin tc ch trng hp khi thay th hyr bng tri).
ArH + Y
+
ArY + H
+

E
A
+
Ar
Y
H
Tin trnh phn ng
E
Vy giai on quyt nh tc phn ng l giai on (1) to thnh phc , khng ph
thuc vo hyr hay tri nm v tr tn cng ca nhm th v lin kt cacbon-hyr khng
b ph v.
6.2.4. C ch ca phn ng nitr ho.
Tc nhn electrphin l cation nitrni NO
2
+
c to thnh trong phn ng ca axt
sunfuric v nitric m c.
HONO
2
H
2
SO
4
H
3
O
+
HSO
4
-
NO
2
+
+ 2 2 + +
NO
2
+
NO
2
+
NO
2
H
+ +
chm
HSO
4
-
H
2
SO
4
NO
2
H
+
nhanh
+
NO
2
+
6.2.5. C ch phn ng sunfnic ho.
Tc nhn sunfnic ho thng dng nht l axt sunfuric t 70-100% v lum vi hm
lng SO
3
khc nhau.
H
2
SO
4
HSO
4
-
H
3
O
+
SO
3
2 + +

S
O
O
O
-
+
S
O
O
O
-
+
H
SO
3
-
+ +
H
SO
3
-
+ HSO
4
-
H
2
SO
4
+
SO
3
-
+
H
3
O
+
SO
3
-
SO
3
H
H
2
O + +
Trong cc giai on phn ng trn y, SO
3
khng mang in tch dng nhng n cn
nhiu in t nn ng vai tr l tc nhn electrophin.
6.2.6. C ch phn ng halogen ho.
Cl
FeCl
3 + + + HCl
Cl . . . FeCl
3
Cl
+ -
Cl . . . FeCl
3
Cl
+ -
+
Cl
2
FeCl
3
Cl . . . FeCl
3
Cl
+ -
+
H
Cl
+
FeCl
4
-
Trong phn ng trn c th thay xc tc FeCl
3
bng cc axt Luit khc nh AlCl
3

6.2.7. Phn ng ankyl ho Frien-Crap.
R Cl . . .AlCl
3
- +
R Cl AlCl
3
R Cl . . .AlCl
3
- +
+
+
R Cl . . .AlCl
3
- +
H
R
+
AlCl
4
-
+
R
+ AlCl
3
HCl +
Trong phn ng ny cng c th thay AlCl
3
bng BF
3
, SnCl
2
, HF.
C ch cng xy ra tng t nh vy vi phn ng axyl ho Frien-Crap.
6.3. NH HNG CA NHM TH N PHN NG S
E
.
6.3.1. Phn loi cc nhm th
Tluen cng ging nh benzen, tham gia phn ng S
E
nhng cc sm phm to thnh l
mt hn hp c t l khc nhau. V d trong phn ng sunfnic ho tluen ngi ta thu c
kt qu sau:
H
3
C H
3
C
SO
3
H
SO
3
H
CH
3
CH
3
SO
3
H
H
2
SO
4
/SO
3
+
+
p-tluensunfnic o-tluensunfnic m-tluensunfnic
62% 32% 6%

Nh vy trong sn phm to thnh ch c cc ng phn p- v o- l ch yu cn ng
phn m- khng ng k. Mt khc thc nghim cng cho thy rng, tluen tham gia phn ng
sunfnic ho rt mnh so vi benzen. Nghin cu cc phn ng halogen ho, ankyl ho Frien-
Crap.. ngi ta cng thu c kt qu tng t. iu cho php kt lun rng nhm mtyl
lm tng hot tnh ca vng thm so vi benzen v hng phn ng th S
E
vo cc v tr octo
v para. Ngc li thc nghim cng cho thy rng hp cht nitrbenzen c hot tnh km hn
benzen v hng phn ng th S
E
vo v tr mta.
Nh vy bt k mt nhm th no lin kt vi nhn benzen th s gy nh hng n kh
nng phn ng ca n v quyt nh hng phn ng ca S
E
.
Nhm th m nh hng ca n gy ra lm cho nhn thm tr nn hot ng hn vng
benzen gi l nhm tng hot (nhm th loi 1). Nhm ny ch yu nh hng cc phn ng
th S
E
vo cc v tr o- v p-
Nhm th lm gim tnh hot ng ca vng thm gi l nhm gim hot (nhm th loi
2). Nhm ny ch yu nh hng phn ng th vo v tr m- (tr halogen).
Bng phng php thc nghim, ngi ta xc nh c cc nhm th thuc loi 1 v
loi 2 sau y:
Cc nhm th loi 1 Cc nhm th loi 2
Tng hot mnh:
-NH
2
(-NHR, -NR
2
)
-OH
Tng hot va:
-OCH
3
(-OR)
-NHCOCH
3

-NO
2

-N
+
(CH
3
)
3

-CN
-COOH (COOR)
-SO
3
H
-CHO, -COR
Tng hot yu:
-C
6
H
5

-CH
3
(-R)
Cc nhm gim hot nhng
nh hng oct v para: -F, -
Cl, -Br,-I
6.3.2. Thuyt nh hng.
a. Trng hp th loi 1.
Ta ni rng nhm mtyl hot ho nhn thm v nh hng S
E
vo v tr para v oct.
iu c ngha l nhm mtyl lm cho vng thm tham gia phn ng nhanh hn benzen v
phn ng S
E
xy ra v tr oct v para nhanh hn v tr mta. Ni cch khc nhm mtyl
lm thay i tc phn ng. V tc d phn ng c xc nh bi giai on (1) to thnh
phc nn nghin cu s nh hng, ta c th nghin cu phc to thnh. Phc ca
tluen c th c biu din:
Cc cng thc nh hng ca para.
Y
H
CH
3
+
Y
H
CH
3
+
Y
H
CH
3
+
I II (bn nht) III

Cc cng thc nh hng ca mta
IV V VI
Y
H
CH
3
+
Y
H
CH
3
+
Y
H
CH
3
+
Ch c cu to cng hng II trong 6 cng thc trn y c nguyn t cacbon mang in
tch dng lin kt trc tip vi nhm CH
3
v do n c nhm ny lm bn ho nhiu nht
bi hiu ng +I. iu gii thch rng, phn ng th para xy ra nhanh hn so vi mta.
Kt qu cng thu c tng t khi so snh oct vi mta:
Cc cng thc cng hng ca oct:
Y
H
CH
3
+
Y
H
CH
3
+
Y
H
CH
3
+
VII VIII IX

Cng thc cu to IX bn nht nn phn ng xy ra oct nhanh hn nhiu so vi mta.
b. Trng hp nhm th loi 2.
Cc cng thc cng hng ca ion cacbni ca phn ng th S
E
nitrbenzen c biu
din nh sau: trong cc cng thc th cng thc cu to XI km bn nht (kh c th tn ti)
do nh hng hiu ng I ca nhm NO
2
. Do nh hng para ch c 2 cng thc cng
hng X v XII t hn so vi nh hng mta c 3 cng thc cng hng XIII, XIV v XV
nn phn ng xy ra v tr mta nhanh hn para.
Y
H
NO
2
+
Y
H
NO
2
+
Y
H
NO
2
+
X XI XII
Cc cng thc cng hng nh hng para ca nitrbenzen
NO
2
Y
H
+
NO
2
Y
H
+
NO
2
Y
H
+
XIII XIV XV
Cc cng thc cng hng nh hng mta ca nitrbenzen.
Kt qu thu c tng t khi so snh nh hng oct v mta.
NO
2
H
Y
+
NO
2
H
Y
+
NO
2
H
Y
+
XVI XVII XVIII

Cc cng thc cng hng nh hng oct ca nitrbenzen.
Trong cc cng thc cng hng trn y, cng thc cng hng XVIII khng th tn ti
c nn nh hng mta s xy ra nhanh hn.
c. S dch chuyn in t do hiu ng lin hp.
Trong cc trng hp trn y ta ch xt cc nh hng gy ra do hiu ng cm ng.
i vi cc nhm th NH
2
, -OH s chuyn dch in t gy ra hiu ng lin hp. Sau y l
cc cng thc cng hng ca ion cacbni ca anilin trong phn ng S
E
.
NH
2
Y
H
+
NH
2
Y
H
+
NH
2
Y
H
+
NH
2
Y
H
+
I II III IV

Cc nh hng para.
NH
2
Y
H
+
NH
2
Y
H
+
NH
2
Y
H
+
V VI VII

Cc nh hng mta.
Do s to thnh IV bn vng v c bn ho bi hiu ng lin hp nn nh hng para
u tin hn.
Kt qu cng thu c tng t trong trng hp nh hng oct.
+ NH
2
Y
H
+
NH
2
Y
H
+
NH
2
Y
H
NH
2
Y
H
+
VIII IX X XI

Cc nh hng oct.
d. nh hng ca cc nhm halogen.
Cc nhm halogen l nhm th loi 2 nhng li nh hng para v oct v do hiu ng
+C > -I.
X (X = -F, -Cl, -Br, -I)
6.4. NH HNG TRONG CC HP CHT HAI LN TH.
S c mt ca 2 nhm th trong nhn thm s lm phc tp s nh hng ca phn ng
S
E
. Do ta c th phn thnh cc trng hp sau:
1- Hai nhm th cng nh hng vo mt v tr th nh hng theo chiu mi tn nh
sau:
CH
3
O
2
N
O
2
N
SO
3
H
CN
NHCOCH
3
2- Hai nhm th nh hng khc nhau th theo quy tc:
- nh hng ca nhm hot ho mnh s quyt nh hng ca phn ng S
E
so vi
nhm hot ho yu.
- nh hng ca nhm tng hot s quyt nh hng ca S
E
so vi nhm gim hot.
nh hng thay i theo dy sau:
-NH
2
> -OH > -OCH
3
> -NHCOCH
3
> -C
6
H
5
> -CH
3
> Nhm nh hng mta.
CH
3
HO CH
3
HO
O
2
N
HNO
3
/H
2
SO
4
CH
3
CH
3
CONH
Br
2
/Fe
CH
3
CH
3
CONH
Br
Br
2
/Fe
CHO
HO
CHO
HO
Br
CHO
HO
Br
+
sn phm chnh

6.5. NH HNG V S TNG HP.
Nh nu trn phng php tng hp thng tin hnh sao cho thu nhn c hp
cht tinh khit v cng hn ch c sn phm ph xy ra chng no cng tt chng . V d
trong phn ng sau:
Br
2
/Fe
NO
2
NO
2
Br
Br
2
/Fe
Br Br
NO
2
Br O
2
N
HNO
3
/H
2
SO
4
+
HNO
3
/H
2
SO
4
Trong s phn ng trn y, ta nhn thy rng: mun thu nhn m-brmnitrbenzen
th tin hnh nitr ho trc sau mi brm ho. Tri li, mun c ng phn para hoc oct
th phi tin hnh ngc li. iu cng xy ra tng t trong cc trng hp khc. V d
trong s phn ng sau y, nu mun iu ch m-nitrbenzic axt t tluen th trc ht
phi xy ho ri sau mi tin hnh nitr ho, tri li mun iu ch p- hoc o-nitrbenzic
axt th phi tin hnh ngc li.
CH
3
KMnO
4
COOH COOH
O
2
N
HNO
3
/H
2
SO
4
HNO
3
/H
2
SO
4
K
2
Cr
2
O
7
K
2
Cr
2
O
7
COOH
NO
2
COOH O
2
N
CH
3
NO
2
CH
3
O
2
N +
6.1. Gi tn theo danh php IUPAC cc hp cht sau y:
CH
3
NO
2
C
H
C
H
Cl
Cl
Cl
CH
2
CH
CH
3
CH
2
CH
3
CH
2
CH CH
2
CH CH
2
a. b. c.
d. e.
benzen
tec-butanol
H
2
SO
4
6.2. Sp xp theo th t tng dn hot tnh ca cc hp cht sau y trong phn ng nitro ha:
a. benzen, toluen, clobenzen.
b. axit benzen sunfonic, phenol, p-nitrotoluen.
a. + A
Toluen
Cl
2
FeCl
3
C D + b. +
H
2
SO
4
HNO
3 H
2
O, t
0
C
Toluen + E
H
2
SO
4
F
c.
G

6.4. T benzen hay toluen v cc ha cht cn thit hy iu ch:
a. o-clonitrobenzen v p-clonitrobenzen
b. m-clonitrobenzen
c. 2-clo-4-nitrotoluen
d. axit p-nitrobenzoic
e. 2-brom-4-nitrotoluen
f. 2,6-dibrom-4-nitrotoluen
g. axit 2-nitro-4-brombenzoic
6.5. Trnh by c ch phn ng sunfonic ha mt hirocacbon thm v v gin biu din s
bin i nng lng theo tin trnh phn ng.
ha hc hu c.
H Ni.
Ni.
Chng 7
DN XUT HALOGEN
7.1.CU TO.
Dn xut halogen l nhng hp cht c cng thc R-X (trong R- l nhng nhm
ankyl) v Ar-X ( Ar- l nhm aryl).
1- ankylhalogenua:
V d:
(CH
3
)
3
-Cl CH
2
=CH-CH
2
Br C
6
H
5
CH
2
Cl
Tec-butylclorua Allylbrmua Benzylclorua
CH
2
=CH-Cl CH
2
Br-CH
2
Br CH
2
OH-CH
2
Br
Vinylclorua 1,2-ibrmtan 2-brmtanol
2- arylhalogenua:
V d:
C
6
H
5
Br m-ClC
6
H
4
NO
2
p-IC
6
H
4
CH
3
o-ClC
6
H
4
COOH
Brmbenzen m-clonitrbenzen p-itluen axt o-clobenzic
7.2. CCH GI TN.
Cc dn xut halogen c gi tn nh trnh by chng 1.
7.3. TNH CHT VT L.
Cc dn xut halogen c mt s tnh cht vt l chung sau y:
- Nhit si ca ankylhalogenua cao hn cc ankan tng ng.
- Nhit si tng khi nguyn t lng ca dn xut halogen tng ln: dn xut flo c
nhit si thp nht, dn xut i c nhit si cao nht.
- Phn t ankylhalogenua phn cc nhng khng ho tan trong nc (c th do khng
c kh nng to lin kt hyr) nhng ho tan tt trong dung mi hu c.
- Cc dn xut i, brm v polyclo c t trng nng hn nc.
7.4.1. Cc phng php cng nghip.
Trong cng nghip cc dn xut ankylhalogenua thng c sn xut nhiu nht bng
phng php clo ho trc tip hyrcacbon nhit cao theo c ch gc.
V d:
C
6
H
5
CH
3
C
6
H
5
CH
2
Cl
Cl
2
, 110 C, as
0
CH
2
CH CH
3
Cl
2
, 600 C, as
0
CH
2
CH CH
2
Cl
CH
4
CH
3
Cl CH
2
Cl
2
CHCl
3
CCl
4
Cl
2
, as Cl
2
, as Cl
2
, as Cl
2
, as
Trong cc phn ng thng to thnh mt hn hp sn phm nhng trong cng nghip
ngi ta khng cn tch ra m s dng lun cho sn xut.
Mt s dn xut halogen iu ch bng phng php A
E
.
CH
2
CH
2
Cl
2
/CCl
4
ClCH
2
CH
2
Cl
KOH
CH
2
CHCl
HC CH
HCl
CH
2
CHCl
7.4.2. Cc phng php tng hp.
a. T ancol
V d:
CH
3
CH
2
OH CH
3
CH
2
I
I
2
P +
C
6
H
5
CHOHCH
3
PBr
3
C
6
H
5
CHBrCH
3
CH
3
CH
2
CH
2
OH
HBr
CH
3
CH
2
CH
2
Br
b. Halogen ho.
R H
X
2
,as
R X ( X
2
= Cl
2
, Br
2
) HX +

c. Cng hyrhalogenua v halogen vo anken v ankin.
C C
HX
C
X H
C
(X
2
= Cl
2
, Br
2
) C C
X
2
CX
2
CX
2
(X
2
= Cl
2
, Br
2
) C C C
X X
C
X
2

d. Thay th halogen ln nhau.
R X I
-
R I X
-
+ +

7.5. Tnh cht ho hc.
Trong phn t ankylhalogenua, halogen rt d dng tch ra di dng anion bng cch
thay th bi mt tc nhn c tnh baz mnh hn n:
R X + Z
-
R Z X
-
+

Tc nhn baz c cp in t t do tn cng vo trung tm dng ca phn t thay th
nhm halogen ca nhm hp cht ankylhalogenua. Phn ng loi ny gi l phn ng th
nuclphin S
N
. Mt khc ankylhalogenua cn tham gia phn ng tch loi to thnh cc hp
cht hyrcacbon cha no v mt s phn ng khc.
1- Phn ng tch loi.
C C
H X
KOH
C C HX +
V d:
CH
3
CH
H
CH
2
Cl
KOH
CH
3
CH CH
2
HCl +
2- Phn ng th nuclphin S
N
.
R Z X
-
R OH X
-
Ancol
R OR' X
-
te
R OH HX Ancol
R C C R' X
-
Ankin
R R' NaX Ankan
R I X
-
Ankyliua
R CN X
-
Hp cht nitrin
R'COOR X
-
Este
R NHR' HX Amin bc II
R NH
2
HX Amin bc I
R NR'R' HX Amin bc III
R Ar HX Ankyl ha
+
+
+
+
+
+
+
+
+
+
+
+
+
+
R X
H
2
O
-
C CR'
NaR'
I
-
CN
-
R'COO
-
R'NH
2
R'NHR'
Ar H
OR'
Z
OH
NH
3
3- Tng hp Grinha
R X Mg
te khan
RMgX +
CH
3
CH
2
Cl Mg + CH
3
CH
2
MgCl
te khan
4- Phn ng kh:
- Kh bng kim loi:
R X H
2
R H HX
Ni
+ +
C
4
H
9
Br H
2
Ni
C
4
H
10
HBr + +
- Kh bng ho hc:
R X M R H M
+
X
-
+
+ +
CCl
4
Fe/H
2
O
CHCl
3
H
+
7.6. PHN NG TH NUCLPHIN S
N
.
7.6.1. Phn ng bc I v bc II.
a. Xt phn ng iu ch ru mtylic t mtylbrmua:
CH
3
Br CH
3
OH Br
-
+ +
HO
-

Nu phn ng l kt qu ca s va chm gia cc ion hyrxyl v phn t mtylbrmua
th vn tc phn ng phi ph thuc vo nng ca c hai thnh phn , nn nu tng nng
ca HO
-
hoc CH
3
Br ln hai ln th tc phn ng cng phi tng gp hai ln v ngc li.
Thc nghim xc nhn iu xy ra nn tc ca phn ng trn y l:
v = k [CH
3
Br] [HO
-
] k l hng s
b. Xt phn ng:
(CH
3
)
3
C Br (CH
3
)
3
C OH
Br
-
+ + HO
-

Thc nghim cho thy rng, trong phn ng ny nu tng nng ca (CH
3
)
3
C-Br ln 2
ln th tc ca phn ng tng gp i v nu gim nng (CH
3
)
3
C-Br 2 ln th tc ca
phn ng s gim 2 ln. Tri li, nu tng hoc gim nng HO
-
th tc ca phn ng vn
khng thay i - tc l tc ca phn ng khng ph thuc vo nng ca ion HO
-
. Vy tc
phn ng tec-butylbrmua vi ion HO
-
ch ph thuc vo nng ca (CH
3
)
3
C-Br cho nn
c th vit:
v = k[(CH
3
)
3
C-Br]
Ngi ta ni rng, phn ng ca ru mtylic vi ion HO
-
l phn ng bc II, cn phn
ng tec-butylbrmua vi ion HO
-
l phn ng bc I. Vy ti sao cc phn ng c bc khc nhau
v trong phn ng ca tec-butylbrmua, tc phn ng li khng ph thuc vo nng ca
ion HO
-
? gii thch nhng vn ny ngi ta cho rng phn ng S
N
xy ra theo 2 c
ch khc nhau.
7.6.2. C ch S
N
2.
a. C ch: Phn ng ca mtylbrmua vi ion HO
-
trn y l phn ng bc II v n
c vit di dng c ch nh sau:
HO
-
H C Br
H
H
HO C H
H
H
+ +
Br
-
HO . . . . C . . . . Br
H
H H
- -
Theo nh c ch c trnh by trn y th ch nhng ion HO
-
no va chm vi phn t
mtylbrmua t pha sau (pha ngc vi nguyn t brm) v ch c nhng va chm no t
c nng lng hot ho E
a
cn thit th mi lm tch c ion Br
-
v hnh thnh lin kt C-
OH. Trng thi chuyn tip c cu to m nguyn t cacbon c mt phn no lin kt
vi HO
-
v mt phn no lin kt vi Br
-
. y lin kt C-OH cha c hon ton hnh
thnh v lin kt C-Br cha hon ton b t ra cn cc ion HO
-
v Br
-
c phn b xa nhau
nht, 3 nguyn t hyr v nguyn t cacbon nm trong mt mt phng vi gc lin kt l 120
0
.
Giai on tip theo, in tch m ca HO
-
b gim dn v n chuyn giao in t n to thnh
lin kt C-OH, brm mang theo cp in t v to thnh ion Br
-
.
b. Ho lp th ca phn ng S
N
2.
Thc nghim chng minh rng phn ng S
N
2 xy ra vi s o ngc hon ton cu
hnh. V d khi cho R(-)-2-brmctan tc dng vi NaOH nu trong iu kin ca c ch S
N
2
th s thu c S(-)-ctanol-2. Trong sn phm to thnh ca s nghch o hon ton cu hnh
ny nhm HO
-
nm v tr i nghch vi nhm Br
-
trc y (tng t nh mt ci d che
ma b lt ngc li).
(R)-Brmctan (S)-ctanol-2
H C Br
CH
3
C
6
H
13
NaOH
HO C H
CH
3
C
6
H
13
S o ngc cu hnh cho php kt lun rng trong phn ng S
N
2 tc nhn
nuclphin tn cng t pha i ngc vi nhm halogen.
c. nh hng ca cc nhm th n phn ng S
N
.
Trong phn ng S
N
2 kh nng phn ng ca R-X thay i theo dy sau:
CH
3
X > halogen bc I > halogen bc II > halogen bc III
S bin i trn y gii thch rng, phn ng S
N
2 xy ra mt giai on qua bc hnh
thnh trng thi chuyn tip nn cc yu t in t khng c ngha lm nh hng n tc
phn ng m ch c cc yu t nh hng n s tn cng ca nhm OH vo trung tm phn
ng mi lm thay i tc phn ng.
Ta xt cc trng thi chuyn tip sau y:
H
H
H
. . . . . .
Z X
H
H
. . . . . .
Z X
CH
3
CH
3
CH
3
H
. . . . . .
Z X
CH
3
CH
3
CH
3
. . . . . .
Z X
Mtyl- tyl- Izprpyl- Tec-butyl-

Qua cc trng thi chuyn tip trn y, ta nhn thy rng nu nguyn t hyr trong
nhm mtyl c thay th bi nhiu nhm mtyl th s cn tr khng gian lm nh hng n
s tn cng ca tc nhn Z vo nguyn t cacbon cng tng ln. iu s lm tng nng
lng hot ho ca phn ng tc l lm gim tc phn ng.
Vy tc ca phn ng S
N
2 c quyt nh ch yu bi nh hng ca cc yu t
khng gian.
7.6.3. C ch ca phn ng S
N
1.
a. C ch: C ch ca phn ng S
N
1 xy ra nh sau:
chm
CH
3
C
CH
3
CH
3
Br CH
3
C CH
3
CH
3
+
Br
-
+
CH
3
C CH
3
CH
3
+
HO
-
CH
3
C CH
3
CH
3
OH
nhanh
+
(1)
(2)
y tc phn ng c xc nh bi giai on (1).
b. Ho lp th ca phn ng S
N
1.
Thc nghim chng minh rng, phn ng S
N
1 xy ra vi s raxmic ho. V d: khi
hyrat ho (-)-2-brmctan trong iu kin ca phn ng S
N
1 (nng HO
-
thp) th s thu
c bin th raxmic ()-ctanol-2.
HO
-
, H
2
O
- -C
6
H
13
CHCH
3
Br
(-) C
6
H
13
CHCH
3
OH
+
-
( )
S raxemic ho ca sn phm th S
N
1 c th gii thch nh sau:
Phn ng S
N
1xy ra qua bc to thnh ion cacbni c cu trc phng:
CH
3
H H
13
C
6
+
HO
- a b
HO C H
H
13
C
6
H
3
C
H C OH
C
6
H
13
CH
3
b a
(+)-ctanol-2 (-)-ctanol-2

Do c cu trc phng nn kh nng tn cng ca ion HO
-
vo hai pha ca mt phng
hon ton nh nhau, kt qu to thnh cc lng ng phn quay phi v quay tri nh nhau
(tc l to thnh bin th raxmic).
c. nh hng ca cc nhm th n phn ng S
N
1.
Thc nghim chng minh rng, kh nng phn ng ca R-X trong cc phn ng S
N
1
thay i nh sau:
Allyl > benzyl > R
3
C-X > R
2
CH-X > R-CH
2
-X > CH
3
-X
S thay i kh nng phn ng trn y c th gii thch rng v phn ng xy ra qua
bc hnh thnh ion cacbni nn cc yu t no lm bn ho ion ny s lm cho phn ng xy
ra nhanh hn.
d. Phn ng S
N
1 xy ra vi s chuyn v.
V qua bc to thnh ion cacbni nn phn ng S
N
1 xy ra cng vi s chuyn v.
V d:
CH
3
C
CH
3
CH
3
CH
2
Br
CH
3
C
CH
3
CH
3
CH
2
OC
2
H
5
CH
3
C
CH
3
OC
2
H
5
CH
2
CH
3
CH
3
C CH CH
3
CH
3
C
2
H
5
OH
S 1
N
sn phm chnh
7.1. Gi tn theo danh php IUPAC cc hp cht sau y:
(CH
3
)
3
C CH
Br
CH
2
Br H
2
C C
CH
3
CH
Cl
CH CH CH
2
Cl
(CH
3
)
2
CH CH
2
CH(CH
2
CH
2
Cl)
2
CH
3
CH
2
C
Br
CH
2
Cl
CH(CH
3
)
2
a. b.
c. d.
7.2. Vit phng trnh phn ng ca Toluen vi clo trong cc iu kin sau:
a. Trong iu kin nhit cao v c nh sng xc tc.
b. Trong iu kin c mt bt st v nhit thng.
7.3. Hon thnh cc s phn ng sau y:
xiclohexanol PBr
3
NH
3
+ A B
HO CH
2
(CH
2
)
3
CH
2
OH
PCl
3 Zn
C D
+ + (CH
3
)
3
C Br KOH
CH
3
OH
t
0
C cao
E F
CH
3
CH
2
CH
2
Br NaOCH
3
+
CH
3
OH
G H +
a.
b.
c.
d.

7.4. Vit cng thc cu to cc sn phm to thnh trong phn ng gia cc hp cht sau y:
a. 2-clopropan v natri etylat.
b. 2-brombutan v KOH m c trong ru v un nng.
c. 2-brombutan v dung dch KOH long trong nc nhit thng.
7.5. Hon thnh cc s phn ng tsau y:

C
6
H
5
C
H
CH
3
OH SOCl
2
Pyridin
+ A B C + + a.
Vai tr ca Pyridin trong phn ng trn v c im lp th ca sn phm to thnh?
CH
3
CH
2
O C
O
CH
2
C
O
O CH
2
CH
3
C
2
H
5
I
C
2
H
5
O
-
+ C D + b.
7.6. iu ch cc sn phm sau y:
a. 2-brompropan (izopropyl bromua) t propanol-1.
b. n-propyl bromua t 1,2-dibrompropan.
c. 2-metoxibutan t n-butyl iodua.
ha hc hu c.
H Ni.
Ni.
Chng 8
HP CHT C NGUYN T
Ho hc c nguyn t l ho hc ca cc hp cht hu c vi tt c cc nguyn t. Mt
s lng rt ln cc nguyn t trong bng tun hon l kim loi, do hn mt na cc hp
cht c nguyn t l cc hp cht c kim. l nhng hp cht m trong nguyn t kim loi
lin kt trc tip vi nguyn t cacbon bng lin kt cng ho tr hoc lin kt ion. Cc hp cht
ankyl hoc aryl ca cc nguyn t kim loi kim hoc kim th hot ng mnh: chng d b
phn hu bi axt, nc, ru cho sn phm l hyrcacbon, d b oxy ho bi oxy phn t,
tc dng vi cc hp cht c cha nhm cacbnyl, tham gia nhiu phn ng vi cc hp cht c
cha cc nhm th l oxy, lu hunh, nit
8.1. CC HP CHT C NGUYN T CA KIM LOI KIM.
a. T ankyl- hoc arylhalogenua.
2M RM MX (Ar-), R X + + (1)
RM RX R R MX + +
(2)

Trong phn ng iu ch trn y cn lu rng:
- Phn ng phi tin hnh trong dung mi tr (hecxan, ctan)
- Phn ng vi kim loi Natri khng dng (1) m tip tc (2).
- Phn ng vi Kali thng ch xy ra theo (1).
b. T hp cht c thy ngn.
R
2
Hg Hg + + 2M 2RM

V d:
(CH
3
)
2
Hg + 2Li CH
3
Li 2 + Hg

c. T axtylen
HC CH NaNH
2
Na C CH NH
3
+ +
Na C C Na HC CH NaNH
2
2 + +
NH
3
2

a. Phn ng th hyr bng kim loi
(Ar-), R H R'M (Ar-), R M R'H + +

V d:
CH
3
Na C
6
H
5
CH
3
C
6
H
5
CH
2
Na CH
4
+ +

HC CH C
6
H
5
Na Na C C Na 2 + +
C
6
H
6
2

b. Phn ng trao i thnh hp cht c kim mi.
R X R' Li + R Li R' X +

V d:
C
6
H
5
CH
2
Br C
2
H
5
Li + C
6
H
5
CH
2
Li C
2
H
5
Br +

c. Phn ng cng vo cc hp cht khng no.
(C
6
H
5
)
2
C CH
2
C
4
H
9
Li (C
6
H
5
)
2
C
Li
CH
2
C
4
H
9
+
(Loi phn ng ny dng iu ch cao su tng hp)
V d:
CH
2
C
CH
3
CH CH
2
C
4
H
9
Li C
4
H
9
CH
2
C
CH
3
CH CH
2
Li
+
-
+
C C
H
CH
2
H
3
C
CH
2
C
4
H
9
CH
2
C
H
3
C
C
H
CH
2
Li
+
-
C C
H
CH
2
Li
+
H
3
C
CH
2
C
4
H
9
-
CH
2
C
CH
3
CH CH
2
+
n
C C
H
CH
2
H
3
C
CH
2
C
4
H
9
CH
2
C
H
3
C
C
H
CH
2
-
Li
+
izpren
8.2. CC HP CHT C KIM CA KIM LOI KIM TH.
8.2.1. Hp cht c magi.
Hp cht c magi gm c 2 loi: R
2
Mg v RMgX (tc nhn Grinha).
a. Cc phng php iu ch.
- Cho Magi tc dng vi ankylhalogenua tong ete khan
R X Mg R MgX +

V d:
C
6
H
5
Cl Mg
C
6
H
5
MgCl
+

ClCH
2
CH
2
CH
2
CH
2
Cl 2Mg + ClMg (CH
2
)
4
MgCl

Br C
6
H
4
Br 2Mg
+
BrMg C
6
H
4
MgBr

- T cc hp cht c hyr linh ng
HC CH RMgX HC CMgX RH
+ +

HC CH 2RMgX +
+ XMg C C MgX
2RH

d. Cu to.
Cho n nay, mt trong nhng hp cht c nguyn t quan trng l hp cht c magi
vn cha c xc nh mt cch chi tit nhng ngi ta gi thit rng trong dung mi te hp
cht Grinha tn ti di dng cn bng nh sau:
R MgX 2 R Mg
X
R
X Mg R
2
Mg MgX
2
+
R Mg X
Thng thng ngi ta thng hay vit cng thc cu to ca hp cht Grinha di
dng:
- +
c. Cc phn ng quan trng ca hp cht Grinha.
1- Phn ng vi cc hp cht c hyr linh ng dng H-A.
R MgX
H A
H
2
O
CH
3
OH
RNH
2
RSH
RH
A MgX
HO MgX
CH
3
O MgX
RNH MgX
RS MgX
RH
+
+
RH +
RH +
RH +
Cc phn ng ny thng c s dng xc nh linh ng ca hyr bng cch
so snh lng kh mtan bay ra khi s dng hp cht Grinha l CH
3
MgCl.
2- Cc phn ng vi halogen, xy, lu hunh:
R MgX X
2
R X MgX
2
+ +
R MgX O
2
+ R OOMgX
H
2
O
R OH HO MgX +
R MgX + S RS MgX RSH HO MgX +
H
2
O
3- Phn ng vi dn xut halogen.
R MgX R' X R R' MgX
2 + +
R MgX CdCl
2
R
2
Cd MgX
2
MgCl
2
+ + + 2

4- Cc phn ng vi hp cht cacbnyl.
R MgX HCHO R CH
2
OMgX R CH
2
OH HO MgX + +
H
2
O
ancol bc I
R CH
R'
OH HO MgX +
R MgX R'CHO R CH
R'
OMgX +
H
2
O
ancol bc II

R MgX R' C R''
O
+ R C
R''
R'
OMgX R C
R''
R'
OH HO MgX
H
2
O
+
ancol bc III

R MgX R' COOR''
R C
OR''
R'
OMgX
R C
O
R' R''O MgX
+
+
R C
O
R' R MgX + R C
R'
R
OMgX R C
R'
R
OH HO MgX +
C ch ca phn ng trn y n nay cha c chng minh tht chi tit nhng phn
ng xy ra theo c ch vng c nhiu ngi chp nhn nht.
C O
R
R R'
X
Mg
R'
X Mg
C
O
R
R
R
C
R
R'
O MgX
R' MgX
R
C
R
R'
OH
Mg
OH
X
R' MgX 2
+
+
H
2
O
+
d. Mt s phn ng quan trng khc ca hp cht Grinha.
1- Phn ng vi tylenxit
R MgX H
2
C CH
2
O
R CH
2
CH
2
OMgX
H
2
O
R CH
2
CH
2
OH HO MgX
+ +
2- Phn ng vi ixitcacbon
R MgX CO
2
R COOMgX
H
2
O
R COOH HO MgX
+
+

3- Phn ng vi hp cht nitrin
R MgX R' C N R C
R'
NMgX R C NH
R'
R C R'
O
NH
3 +
H
2
O
+
H
2
O
8.3. CC HP CHT C PHI KIM.
8.3.1. Hp cht c pht pho.
Hp cht c pht pho gm c 2 loi:
1- Loi lin kt P-C trong nguyn t pht pho lin kt vi nguyn t cacbon.
2- Loi cc sn phm ca cc axt v c ca pht pho trong pht pho khng lin kt
trc tip vi nguyn t cacbon m qua mt nguyn t trung tm nh xy, lu hunh, nit
a- Cc hp cht c pht pho loi 1.
Tng t nh phn t amnic NH
3
hp cht pht phua hyr PH
3
l hp cht u ca
dy hp cht ny. Tip theo tu thuc vo s lng s nguyn t hyr trong phn t PH
3
c
thay th m ta c cc hp cht pht phin bc I, bc II, bc III khc nhau. Khc vi cc hp cht
amin, cc hp cht pht phin d b xy ho to thnh cc xit RH
2
P=O, R
2
HP=O, R
3
P=O.
Nu ankyl ho pht phin th s thu c mui phtphoni.
R
3
P RX R
4
P
+
X
-
+

Mt hp cht khc kh quan trng ca loi hp cht ny l cc axt hu c pht pho.
V d:
R P O
H
OH
R P O
H
R
R P O
OH
OH
R P O
R
OH

Cc hp cht pht pho loi 1 c iu ch bng phng php sau:
- Ankyl ho cc pht phin kim loi.
V d:
PH
2
Na RI RPH
2
NaI + +

RPHLi R'Br RR'PH LiBr + +

- Kh cc dn xut clophtphin
RPCl
2
RPH
2

- Cng phtphin vo anken
C
6
H
13
CH CH
2
PH
3
C
6
H
13
CH CH
3
PH
2
+
- Tng hp bng tc nhn Grinha.
3RMgX 3MgXCl PCl
3
R
3
P + +

Cc hp cht pht phin c mt s tnh cht ho hc c trng sau:
- D b zn ho
RPH
2
RH
2
PO
3
O
R
2
PH R
2
HPO
2
O
R
3
P R
3
PO
O
- Ankyl ho thnh mui phtphoni
(CH
3
)
3
P CH
3
I
(CH
3
)
4
P
+
I
-
+

T mui phtphoni c th iu ch phtphinmtylen c ng dng trong tng hp
Vitich nh sau:
(C
6
H
5
)
3
P CHR
2
X C
6
H
5
Li + CR
2
(C
6
H
5
)
3
P

(C
6
H
5
)
3
P
+
CR
2
CR'
2
-
O
(C
6
H
5
)
3
P CR
2
CR'
2
O
O CR'
2
(C
6
H
5
)
3
P CR
2
- +
R
2
C CR'
2
(C
6
H
5
)
3
P O +

b. Cc hp cht c pht pho loi 2.
Loi hp cht ny c th c iu ch bng mt trong cc phng php sau:
RPCl
2
R P(OC
2
H
5
)
2
+ + NaOC
2
H
5
2 NaCl 2

Este ny d b chuyn v di tc dng ca R-X.
R P(OC
2
H
5
)
2
R'I RR'P O
OC
2
H
5
C
2
H
5
I
+ +
R P(OC
2
H
5
)
2
O
R'I RR'P O
OC
2
H
5
C
2
H
5
I
+ +
Tng t nh vy ta c:
P(OC
2
H
5
)
3
C
2
H
5
I
C
2
H
5
P(OC
2
H
5
)
2
O

Cc este ny khi b thu phn th to thnh cc axit tng ng:
R P(OC
2
H
5
)
2
O
R P(OH)
2
O
HX 2 C
2
H
5
X 2 +
+
8.1. T C
2
H
5
MgBr v nhng ho cht cn thit iu ch cc hp cht sau:
CH
3
CH
2
CH
2
OH CH
3
CH
2
CH
2
CH
2
OH
CH
3
CH
2
C
CH
3
C
3
H
7
OH
CH
3
CH
2
C
OH
CH
3
C
2
H
5
(C
2
H
5
)
3
COH a. b. c.
e. d.
CH
3
MgCl C
2
H
5
OH +
C
2
H
5
MgBr + CH
3
NH
2
(CH
3
)
2
CHMgI
1. CO
2
2. H
3
O
+
C
6
H
5
MgBr
1. HCHO
2. H
3
O
+
C
2
H
5
MgBr
1. C
6
H
5
COCl
2. H
3
O
+
a.
b.
c.
d.
e.
8.3. iu ch cc sn phm sau y:
a. xiclopentylcacbinol t xiclopenten.
b. pentanol-3 t propanal.
c. butanal t propanol-1.
8.4. Hp cht A (C
5
H
12
O
2
) c tnh quang hot. Khi cho 0,52 gam A tc dng vi CH
3
MgBr, ta
thu c 112 cm
3
metan trong iu kin tiu chun v hp cht B. Khi cho B tc dng vi CH
3
I
cho ra hp cht C khng c tnh quang hot. Vit tt c nhng cng thc c th c ca A v B.
8.5. Vit phng trnh phn ng ca C
6
H
5
MgBr vi cc cht sau:
a. I
2
b. AgBr c. CH
2
O
d. CH
3
CHO e. CH
3
COCl f. CO
2

ha hc hu c.
H Ni.
Ni.
Chng 9
DN XUT HYRXI CA HYRCACBON
(Ancol v Phnol)
A. ANCOL.
9.1. CU TO, PHN LOI V CCH GI TN.
9.1.1. Cu to.
Ancol l nhng hp cht c cng thc R-OH, trong R- l cc nhm ankyl, ankenyl,
ankinyl, xyclankyl
V d:
(CH
3
)
3
C OH H
2
C CH CH
2
OH Cl CH
2
CH
2
OH
Ancol tec-butylic Ancol allylic Ancol clotylic
CH
2
CH CH
2
OH OH OH
OH CH
2
OH
Glyxrin Ancol xyclhecxylic Ancol benzylic

Tt c cc ancol u c cha nhm OH, l nhm chc quyt nh tnh cht c trng
cho loi hp cht ny.
9.1.2. Phn loi.
Ngi ta phn loi bng nhiu cch khc nhau. Thng thng th da vo s nhm OH
c trong cc phn t ancol phn thnh ancol n chc hoc a chc. Cng rt nhiu khi
ngi ta da vo bc lin kt ca nguyn t cacbon phn loi ancol thnh bc I, bc II, bc
III.
V d:
R CH R'
OH
R CH CH R'
OH OH
R CH CH CH R'
OH OH OH
Ancol n chc Ancol a chc
R CH
2
OH R
2
CH OH R
3
C OH
Ancol 2
0
Ancol 3
0
Ancol 1
0
9.1.3. Cch gi tn.
gi cc ancol ngi ta thng s dng cc danh php sau:
a. Danh php thng thng.
Trong danh php ny ngi ta gi tn ca nhm chc ankyl, ankenyl, ankinyl cng
vi ui ic.
V d:
CH
3
CH
2
OH CH
3
CH CH
3
OH
CH
3
CH
2
C CH
3
CH
3
OH
Ancol tylic Ancol izprpylic Ancol tec-pentylic
b. Tn gi hp l (tn gi cacbinol).
Trong danh php ny ngi ta xem cc ancol nh cc dn xut ca cacbinol CH
3
OH.
V d:
(C
6
H
5
)
3
C OH (C
2
H
5
)
3
C OH
Triphnylcacbinol Tritylcacbinol

c. Danh php IUPAC.
1- Chn mch di nht c cha nhm OH lm mch chnh v coi hp cht phi gi l
dn xut ca mch chnh m trong cc nguyn t hyr c thay th bng cc nhm th.
2- nh s th t mch chnh sao cho nhm OH c ch s l nh nht.
3- Gi tn cc hp cht bng cch tn cc nhm th cng vi cc ch s ca n trc
tn gi ca mch chnh (tn gi ca mch chnh c to thnh bng cch cng thm ui ol
vo tn gi ca cc hp cht hyrcacbon tng ng).
V d:
CH
3
OH CH
3
CH
2
CH CH
2
OH
CH
3
CH
3
CH
OH
CH CH
3
CH
3
Mtanol 2-Mtylbutanol-1 3-Mtylbutanol-2

9.2. TNH CHT VT L.
a. S c mt ca nhm OH trong phn t ancol lm cho phn t phn cc do d ho
tan trong nc. Nhng khi gc R- trong cc phn t tng ln th ho tan ca cc ancol trong
nc gim dn. Trong thc t ch c cc ancol mch thng co 4 n 5 nguyn t cacbon tr
xung l ho tan tt trong nc.
b. Nhit si ca ancol tng khi phn t lng tng ln. Mt khc nhit si ca
ancol cng cao hn nhiu so vi cc hp cht c cng phn t lng vi n.
V d: M t
0
s
C
CH
3
CH
2
CH
2
CH
2
CH
3

72 0 36
CH
3
CH
2
OCH
2
CH
3
74 1,18 35
CH
3
CH
2
CH
2
CH
2
OH 74 1,36 118
CH
3
CH
2
CH
2
Cl 79 2,10 47
Cc kt qu thu nhn c trn y c th gii thch bng 2 yu t:
1- Phn t ancol phn cc mnh do c mmen phn cc ln nn c nhit si cao.
2- Ancol c kh nng to lin kt hyr.
R
O . . . H
. . .H O . . . H
R
O . . . H
R
O . . . H
R
O . . . H
R
O . . .
R

Lin kt hyr l lin kt m trong nguyn t hyr ng vai tr lm cu ni gia 2
nguyn t m in, mt khc mt trong hai nguyn t m in phi c lin kt cng ho tr vi
hyr cn nguyn t kia c lin kt bng lc ht tnh in. to lin kt hyr trong phn
t cn phi c mt cc nguyn t c m in ln hn nh: F, O, N.
Trong ph hng ngoi: - nhm OH ring bit c (OH) = 3620cm
-1
- nhm OH lin kt hyr c (OH) = 3350cm
-1
.
thu nhn ancol trong cng nghip c 2 phng php chnh: hyrat ho cc anken v
ln men, thu phn cc hyrat cacbon.
a. Hyrat ho cc anken.
T phng php crcking du m, ngi ta thu nhn c cc anken c 4 n 5 nguyn
t cacbon, sau d dng chuyn thnh ancol bng phn ng hyrat ho.
V d:
H
2
C CH
2
H
2
O/H
2
SO
4
CH
3
CH
2
OH
H
2
O/H
2
SO
4
CH
3
CH CH
2
CH
3
CHOHCH
3

b. Ln men v thu phn cc hyrat cacbon.
Thu phn ng bng men ru qua 2 giai on chnh: thu phn v chng ct. Cht
lng ru ph thuc vo nguyn liu ban u; nu t ng s thu c C
2
H
5
OH c cht
lng tt, t tinh bt cc loi s c cc sn phm ph. Trong chin tranh th gii th II,
Beisman ngi c dng men vi sinh Clostridum Actobutylicum (20%), axton (30%).
Axton c s dng lm thuc sng khng khi. Phng php ny v sau c s dng sn
xut n-butanol dng cho cng nghip t.
c. Phng php ring dng sn xut mtanol.
CO CH
3
OH + H
2
2
O
2
+ CH
4
2 CH
3
OH 2
100at, 100 C
0
210at
Cr
2
O
3
, ZnO, 300-400 C
0
9.3.2. Phng php tng hp phng th nghim.
a. Hyr bo ho.
C C (BH
3
)
2
C
H
C
BH
2
H
2
O
2
, HO
-
C C
H OH
B(OH)
3 + +
V d:
H
2
O
2
, HO
-
(BH
3
)
2
(CH
3
)
3
C CH CH
2
(CH
3
)
3
C CH
2
CH
2
OH
b. Tng hp Grinha.
Trong phng th nghim ancol c tn hp theo phn ng Grinha nh trnh by trong
phn hp cht c magi.
c. Thu phn ankylhalogenua (xem phn dn xut halogen)
Trong cc phn ng nu trn y, tng hp Grinha l quan trng nht v: cc hp cht
u ca phn ng ny l dn xut halogen thng d tm, phn ng c hiu sut cao, c th tng
hp cc ancol n gin hoc phc tp khc nhau. im hn ch ln nht ca phn ng tng hp
Grinha l ngoi nhm th trc tip tham gia phn ng cc hp cht u khng c cha cc
nhm c cha hyr linh ng nh COOH, -OH, -NH
2
, -SO
3
Hcng nh cc nhm cacbnyl
khng cn thit khc.
d. Phng php thit lp mt phn ng Grinha
Hu ht cc ancol u c th tng hp bng phng php Grinha bng nhng cch t hp
cc tc nhn khc nhau. V vy phi chn con ng tng hp sao cho ti u nht.
V d: hp cht 2-phnylhecxanol-2 c th tng hp bng 2 cch sau y:
CH
3
CH
2
CH
2
CH
2
C CH
3
O
BrMg
+
CH
3
CH
2
CH
2
CH
2
C
CH
3
OH
CH
3
CH
2
CH
2
CH
2
C
CH
3
OH
CH
3
CH
2
CH
2
CH
2
MgBr C CH
3
O
+
(1)
(2)
Trong 2 cch trn y th nn chn (2) v hp cht xton d iu ch hn nhiu so vi
(1).
9.4. TNH CHT HO HC.
Tnh cht ho hc ca ancol c xc nh bi nhm OH c trong phn t. V vy kh
nng c th xy ra cc loi phn ng sau y:
- Phn ng lm ph v lin kt C OH vi s tch i nhm OH.
- Phn ng lm ph v lin kt O H vi s tch i hyr.
Nhm R- ni chung ch c ngha lm nh hng n tc v hng ca phn ng m
thi.
9.4.1. Cc phn ng lm t lin kt C OH.
a. Phn ng vi hyrhalogenua.
R OH HX R X H
2
O + +

Kh nng phn ng ca HX: HI > HBr > HCl
Kh nng phn ng ca ROH: R
3
C-OH >R
2
CH-OH >RCH
2
-OH >CH
3
-OH.
V d:
CH
3
CH CH
3
OH
HBr
CH
3
CH CH
3
Br
CH
3
CH
2
CH
2
CH
2
OH
HCl
CH
3
CH
2
CH
2
CH
2
Cl

b. Phn ng vi trihalogenua pht pho.
R OH PX
3
R X H
3
PO
3
(PX
3
= PBr
3
, PI
3
) + +

V d:
CH
3
CH
2
CH
2
OH
I
2
P +
CH
3
CH
2
CH
2
I
CH
3
CH
2
CH
2
CH
2
OH
PBr
3
CH
3
CH
2
CH
2
CH
2
Br
C
6
H
5
CHCH
3
OH
C
6
H
5
CHCH
3
Br
PBr
3
c. Phn ng tch loi.
C C
H OH
C C H
2
O
H
2
SO
4
+
V d:
OH
Al
2
O
3
, 250 C
0
9.4.2. Phn ng lm t lien kt O-H.
a. Phn ng ca ancol ging nh mt axit vi cc kim loi hot ng mnh.
RO H M RO
-
M
+
H
2 + +

Kh nng phn ng ca RO-H:
CH
3
OH > RCH
2
OH > R
2
CHOH > R
3
C-OH
V du:
(CH
3
)
2
CH OH Al (CH
3
)
2
CH O Al
+3
3
-
H
2
+ +
CH
3
CH
2
OH Na CH
3
CH
2
O
-
Na
+
H
2 + +
b. Phn ng to thnh este (phn ng este ha).
CH
3
CH
2
OH CH
3
COOH CH
3
COOCH
2
CH
3
H
2
O + +
H
+
CH
3
CH
2
OH H
2
SO
4
CH
3
CH
2
OSO
3
H H
2
O
+ +
tylsunfat axit
c. Phn ng xy ha.
R
2
CH OH R
2
C O
Ancol 2
0
KMnO
4
R CH
2
OH
RCHO
KMnO
4
R COOH
Ancol 1
0
Cu, 250 C
0
KMnO
4
R
3
C OH KMnO
4
(trung tnh) Khng phn ng +
Ancol 3
0
V d:
CH
3
CH
2
CH
2
OH CH
3
CH
2
CHO H
2
Cu, 250 C
0
+
OH O
K
2
Cr
2
O
7
CH
3
CH
2
CH
2
CH
2
OH
KMnO
4
CH
3
CH
2
CH
2
COOH
9.4.3. Phn ng vi hyrhalogenua.
y l phn ng xy ra khi cho kh hyrhalogenua i qua ancol hoc un nng ancol
vi axt HX m c.
V d:
(CH
3
)
3
C OH
HCl .
(CH
3
)
3
C Cl
CH
3
CH
2
CH
2
OH CH
3
CH
2
CH
2
Cl
HCl, ZnCl
2
, t C
0
Cc phn ng ca ancol vi hyrhalogenua xy ra theo c ch S
N
1 v S
N
2.
C ch S
N
1:
ROH HX X
-
+ + ROH
2
+
R
+
H
2
O ROH
2
+
+
RX R
+
X
-
+

Phn ng xy ra theo c ch ny vi hu ht cc ancol tr mtanol v cc ancol bc I.
C ch S
N
2:
ROH HX X
-
+ + ROH
2
+
RX X
-
+ ROH
2
+
+ H
2
O X . . . R. . .O H
2
- +
Phn ng xy ra theo c ch ny vi mtanol v cc ancol bc I.
9.4.4. Phn ng xy ho ancol.
a. Khi nim xy ho - kh trong ho hc hu c.
Theo quan nim trc y, xy ho tc l a thm nguyn t xy vo phn t, kh tc
l bt i nguyn t xy.
V d:
RCHO R COOH
O
R CONH
2
LiAlH
4
R CH
2
NH
2

Trong ho hc v c, s xy ho-kh gn lin vi s nhn v cho in t, tri li khi
nim ny khng ph hp vi ho hc hu c v y cacbon lun c ho tr 4. V vy trong ho
hc hu c, ngi ta dng khi nim s xy ho (s phn cc)- tc l s in tch quy c
ca nguyn t tnh c khi gi thit rng phn t gm ton nhng ion tri du (s xy ho c
k hiu l n).
Trong khi nim ny s xy ho c th l m, dng, bng 0. Nguyn t cacbon trong
cc hp cht hu c c s xy ho t -4 n +4.
xc nh s xy ho, ngi ta a ra mt s quy c sau y:
- Tng i s ca tt c cc s xy ho ca phn t bng 0, ca ion bng in tch ion.
- Hai nguyn t ng nht lin kt vi nhau khng lm xut hin s xy ho. S xy
ho ca mi nguyn t trong n cht u bng 0.
- S xy ho ca hyr bng +1 (tr cc hp cht vi kim loi), ca xy bng -2 (tr
cc hp cht pext), ca cc nguyn t kim loi bng ho tr ca n.
Nh vy t khi nim ca s xy ho trn y ta c th nhn thy rng: qu trnh xy
ho l qu trnh lm tng s xy ho cht phn ng (c cht, cht nn) v lm gim s xy
ho tc nhn phn ng, cn qu trnh kh l qu trnh ngc li.
i vi nguyn t cacbon, s kh v s xy ho bin i theo dy sau:
CH
4
RCH
3
CH
3
OH RCH
2
OH HCHO RCHO HCOOH RCOOH CO
2
-4 +4
S xy ha
S kh
b. Phn ng xy ho cc hp cht ancol.
Ancol 2
0
+
Xtn KMnO
4
( CrO
3
, K
2
Cr
2
O
7
, Cu, 200-300 C)
0
dung dch KMnO
4
axit
anhyt
+
Ancol 1
0
Cu, 200-300 C
0

Ancol 3
0
: khng b xy ho trong mi trng kim, trong mi trng axt, trc n b
tch thnh anken sau tu theo iu kin phn ng c th b xy ho thnh xton hoc axt.
9.5. Gii thiu mt s ancol quan trng.
9.5.1. Ru tylic.
Ru tylic c iu ch bng phng php ln men tinh bt, hyrat ha
tylenTrong i sng v cng nghip, n c s dng lm dung mi, lm nguyn liu cht
ban u tng hp, dng cho cng nghip thc phm, dng trong y hc
Ru tylic 95% trong cng nghip trong cng nghip c thu nhn bng phng php
chng ct phn on.
Ru tylic tuyt i 100% c thu nhn bng cch chng ct ng ph (hn hp ng
ph gm 7,5% nc, 18,5% ru, 74% benzen si nhit 64,9
0
C). Nhiu khi ngi ta cn
lm tuyt i ru tylic bng cch un ru tylic 95% vi magi sau em chng ct.
9.5.2. tylenglycol.
a. tylenglycol c iu ch bng cc phng php iu ch ancol thng thng. Di
y l mt s phng php quan trng.
1- Thu phn dn xut halogen
Cl CH
2
CH
2
Cl
Na
2
CO
3
HO CH
2
CH
2
OH + H
2
O 2

2- Thu phn tylenxt.
H
2
C CH
2
O
H
2
O
H
+
HO CH
2
CH
2
OH +
3- Hyrxyl ho cc anken bng KMnO
4
hoc peaxt.
CH
2
CH
2
KMnO
4
RCOOOH
H
2
C CH
2
O
H
2
O, H
+
HO CH
2
CH
2
OH
HO CH
2
CH
2
OH
b. Tnh cht.
tylenglycol c cc tnh cht ging nh ancol thng thng nhng do nh hng ca
nhm OH th 2 nn c tnh axt mnh hn. V vy n c kh nng phn ng vi hyrxit
ng.
CH
2
OH
CH
2
OH
Cu(OH)
2
CH
2
CH
2
HO
HO
CH
2
CH
2
O
O
Cu
O
H
O
H
CH
2
CH
2
+
+
- Phn ng xy ho:
CH
2
CH
2
OH
OH
CHO
CH
2
OH
COOH
CH
2
OH
COOH
CHO
COOH
COOH
O O O O
O
OHC CHO
Glyxal
Axit xalic
- Phn ng hyrat ho:
HO CH
2
CH
2
OH
H
2
SO
4
CH
3
CHO

tylenglycol c ng dng lm dung mi, lm tc nhn phn ng, lm cht truyn
nhit...
9.5.3. Glyxrin.
a. Glyxrin trong cng nghip ch yu iu ch bng phn ng thu phn cc cht bo
trong mi trng kim (phn ng x phng ho). Ngoi ra, ngi ta cn tng hp glyxrin t
prpylen:
CH
2
CH CH
3
Cl
2
, 400 C
0
CH
2
CH CH
2
Cl
CH
2
CH CH
2
Cl Cl OH
Cl
2
, H
2
O
H
2
O
CH
2
CH CH
2
OH OH OH

b. Tnh cht.
Tng t nh tylenglycol, glyxrin tc dng vi hyrxit ng to thnh hp cht
glyxrat ng c mu xanh.
CH
2
CH
CH
2
O
O
OH
Cu
H
O
H
CH
2
CH
CH
2
HO
O
Phn ng to este glyxrin trinitrat.
CH
2
CH CH
2
OH OH OH
CH
2
ONO
2
ONO
2
CH
ONO
2
CH
2
HNO
3
/H
2
SO
4
Glyxrin c rt nhiu ng dng trong thc t nh dng lm cht truyn nhit, lm tc
nhn phn ng, lm mm da, dng sn xut thuc n, dng trong y hc
9.6. MT S PHNG PHP DNG NHN BIT ANCOL
nhn bit ancol c th dng phng php ph hng ngoi:
- Nhm OH ring bit (khng c lin kt hyr) c (OH) = 3620 n 3640cm
-1
.
- Nhm OH c lin kt hyr c (OH) = 3200-3350cm
-1
.
Trong phng php ho hc, ngi ta dng thuc th Luca. l hn hp axt HCl m
c v ZnCl
2
. Phng php ny c th dng phn bit cc ancol bc I, bc II, bc III c s
nguyn t cacbon nh hn 6. Phn ng to thnh ankylclorua khng tan trong hn hp tc nhn,
lm c dung dch phn ng. Ancol bc III tc dng ngay lp tc vi hn hp tc nhn, ancol
bc II s thy phn ng xy ra sau 5 pht cn ancol bc I nhit phng s khng phn ng.
B. PHNOL
9.7. CU TO V CCH GI TN.
9.7.1. Cu to.
Phnol l nhng hp cht c cng thc phn t Ar-OH trong Ar- l nhm phnyl
hoc cc dn xut ca phnyl. Khc vi ancol, trong hp cht phnol nhm OH lin kt trc
tip vi nhn thm.
9.7.2. Cch gi tn.
Cc hp cht phnol c gi tn nh l dn xut, n gin nht ca dy ny l phnol.
OH OH
Cl
OH
NO
2
Phnol m-Clophnol o-Nitrphnol

Mt s hp cht khc c tn gi ring nh sau:
OH
CH
3
OH
OH
OH
OH
OH
OH
OH
(o, m), p-Crzol Catechon Rzcxin Hyrquinon -Naphtol
OH OH OH
HO
Antranol-1 Antranol Phnantrol-4 - Naphtol
9.8. TNH CHT VT L.
Hp cht n gin nht ca dy ny l phnol, t tan trong nc nhit thng. Do c
kh nng to thnh lin kt hyr nn phnol c nhit si cao. Cc hp cht phnol khc hu
nh khng tan trong nc.
9.9. PHNG PHP IU CH.
Mt s lng rt ln phnol c iu ch trong cng nghip bng phng php nh
phng th nghim. Ngoi ra cn c mt s phng php dng iu ch phnol trong cng
nghip nh sau:
a. Chng ct nha than 170-240
0
C thu phnol th. Dung dch phnol sau khi loi
naphtalen cho tc dng vi NaOH thu c phnolat. Tch loi cc cht khng tc dng vi
NaOH c trong dung dch sau cho kh CO
2
d vo chuyn phnolat thnh phnol t do v
chng ct ly phnol.
b. Phn ng nung nng chy benzensufnat natri vi NaOH (phng php kim nng
chy).
C
6
H
5
SO
3
Na NaOH C
6
H
5
OH Na
2
SO
3 + +
SO
3
Na
NaOH
OH
Na
2
SO
3
+ +
c. Phng php thu phn clobenzen.
- Thu phn clobenzen bng hi nc di p sut thch hp nhit cao c xc tc
ng kim loi (phng php Rasic).
C
6
H
6
HCl O
2
C
6
H
5
Cl H
2
O + + +
C
6
H
5
Cl H
2
O C
6
H
5
OH HCl + +
Cu, 425 C
0
- Thu phn bng NaOH nng chy.
C
6
H
5
Cl NaOH C
6
H
5
ONa
HCl
C
6
H
5
OH
360 C, 315at
0
+

d. xy ho tluen hoc cumen (izprpylbenzen).
C
6
H
5
CH
3
O
2
/xt
C
6
H
5
OH
CH CH
3
CH
3
O
2
kk
C
CH
3
CH
3
OOH
H
2
O, H
+
OH
CH
3
C CH
3
O
100 C
0
+
Phng php xy ho cumen l phng php quan trng nht v c hai sn phm to
thnh u c ngha ln s dng trong cng nghip.
9.9.2. Cc phng php tng hp.
a. Thu phn mui iazni.
C
6
H
6
HNO
3
/H
2
SO
4
C
6
H
5
NO
2
C
6
H
5
NH
2
Fe/HCl NaNO
2
/HCl
C
6
H
5
N
2
+
Cl
-
C
6
H
5
N
2
+
Cl
-
H
2
O C
6
H
5
OH N
2
HCl
t C
0
+ + +

b. Phng php kim nng chy cng c s dng trong phng th nghim.
NaOH, 300 C
0
H
2
SO
4
CH
3
C
6
H
4
SO
3
Na p- CH
3
C
6
H
4
ONa p - CH
3
C
6
H
4
OH p -

c. Tng hp phnol bng phn ng th S
N
.
Cl Cl
NO
2
NO
2
OH
NO
2
NO
2
O
2
N
H
+
NaOH
HNO
3
/H
2
SO
4
ONa
NO
2
NO
2
OH
NO
2
NO
2
HNO
3
/H
2
SO
4
Axit picric

9.10. TNH CHT HO HC.
Tng t nh cc hp cht thm, phnol tham gia cc phn ng th electrphin nhng
do hiu ng lin hp , p nn kh nng phn ng ca phnol rt mnh. Mt khc cng do hiu
ng lin hp , p nn lin kt O-H phn cc mnh do phnol biu hin tnh axt ca phnol
mnh hn ancol nhng yu hn axt cacbxylic.
O H
-

+
9.10.1. Cc phn ng biu hin tnh axt.
C
6
H
5
OH H
2
O C
6
H
5
O
-
H
3
O
+
+ +

Nhng nhm ht in t s lm tng tnh axt ca phnol, tri li nhng nhm y in
t s lm gim tnh axt ca phnol.
a. Phn ng to mui phnolat.
C
6
H
5
OH NaOH C
6
H
5
O
-
Na
+
H
2
O
+ +

b. Phn ng to ete (tng hp Williamxn).
C
6
H
5
ONa RX C
6
H
5
O R NaX + +

V d:
C
6
H
5
OH
dd NaOH
C
6
H
5
ONa
C
2
H
5
I
C
6
H
5
O C
2
H
5
C
6
H
5
OH
dd NaOH
O
2
NC
6
H
4
CH
2
Br p- O
2
NC
6
H
4
CH
2
O C
6
H
5
p- +
C
6
H
5
OH Cl CH
2
COOH
dd NaOH
C
6
H
5
O CH
2
COONa +

c. Phn ng to thnh este. Chuyn v Friz.
Ar OH
RCOOH, H
+
RCOCl
(RCO)
2
O
R C
O
O Ar +
V d:
C
6
H
5
OH C
6
H
5
COCl C
6
H
5
O C
O
C
6
H
5 +
NaOH
(CH
3
CO)
2
O
CH
3
COONa
O
2
NC
6
H
4
OH p- O
2
NC
6
H
4
O C
O
CH
3
p-
+
Khi un nng este ca phnol vi AlCl
3
s xy ra s chuyn v nhm axyl n v tr cto
hoc para ca nhn thm. Phn ng ny gi l phn ng chuyn v Friz dng iu ch cc
hp cht hyrxi-xton thm.
V d:
OCOCH
3
H
3
C
OH
H
3
C
COCH
3
OH
H
3
C
COCH
3
AlCl
3
, 165 C
0
20 C
0
AlCl
3
,
C ch:
O
AlCl
2
C
O
R
OH
C
O
R
O AlCl
3
H
C O
R
+ -
-HCl HCl
O
AlCl
3
C R
O
+
-
R C O
+
O AlCl
3
-
+
9.10.2. Cc phn ng th S
E
.
Trong cc phn ng th S
E
, nhm OH l nhm th loi 1 nn n c nh hng ch yu
vo v tr cto v para.
a. Phn ng nitr ho.
OH
OH
NO
2
NO
2
O
2
N
OH
NO
2
OH
NO
2
HNO
3
.
HNO
3
long, 20 C
0
+
b. Phn ng sunfnic ho.
OH
H
2
SO
4
OH
SO
3
H
OH
SO
3
H
15-20 C
0
100 C
0
H
2
SO
4
, 110 C
0
c. Phn ng halogen ho.
OH
Br
2
dd
OH
Br
Br
Br
Nu phn ng xy ra trong dung mi t phn cc s to thnh hn hp sn phm.
OH OH
Br
OH
Br
Br
2
, CS
2
, 0 C
0
+
d. Phn ng ankyl ho Frien-Crap.
OH
CH
3
C
CH
3
CH
3
Cl
HF
HO C CH
3
CH
3
CH
3
+
e. Phn ng axyl ho Frien-Crap.
Phn ng axyl ho cc hp cht phnol c th xy ra trc tip v cng c th xy ra qua
bc to thnh este ri sau chuyn v Friz.
OH
RCOCl
AlCl
3
OH
COR
OH
COR
+ +
OH
H
3
C
O C CH
3
O
H
3
C
AlCl
3
OH
H
3
C
COCH
3
OH
H
3
C
COCH
3
(CH
3
CO)
2
O
25 C
0
165 C
0
g. Phn ng nitrz ho.
OH
CH
3
OH
CH
3
NO
NaNO
2
/H
2
SO
4
h. Phn ng ghp vi mui iazni.
y l phn ng c ng dng nhiu trong ho hc tng hp cc loi thuc nhum, cc
cht ch th mu.
HO N N
+
+
R
HO N N
R
i. Phn ng Konbe.
y l phn ng dng iu ch cc o-hyrxibenzic axt.
ONa
O C O
- - +
OH
COONa
H
+
OH
COOH
+
125 C, 7at
0
k. Phn ng Raim-Timan.
y l phn ng dng iu ch cc anhyt ca cc hp cht thm c cha nhm
OH.
OH
CHCl
3
, NaOH dd
70 C
0
O
-
CHCl
2
O
-
CHO
OH
CHO
HCl
C ch ca phn ng Raim-Timan c th vit nh sau:
HO
-
CHCl
3
H
2
O CCl
3
-
Cl
-
CCl
2
+ + +
O
-
CCl
2
O
H
CCl
2
-
O
-
CHCl
2
+
l. Phn ng ci focmanhyt.
Phn ng ny dng tng hp polyphnolfocmanhyt. Phn ng c th xy ra trong
mi trng kim hoc axt.
OH OH
CH
2
OH
OH
CH
2
OH
C
6
H
5
OH
OH
CH
2
OH
CH
2
CH
2
CH
2
CH
2
HCHO, H
+
HCHO, H
+
9.11. CCH NHN BIT CC HP CHT PHNOL.
nhn bit cc hp cht phnol, ngi ta thng da co tnh axt: phnol c tnh axt
mnh hn nc nhng yu hn axt ccbonic, do nu hp cht khng ho tan trong nc
nhng tan trong dung dch NaOH v khng ho tan trong dung dch bicacbnat natri th c
th l phnol. Cng c khi ngi ta dng phn ng lm mt mu Br
2
hoc dng phn ng vi
mui st III cho mu tm c trng pht hin phnol.
9.12. GII THIU MT S HP CHT PHNOL QUAN TRNG.
9.12.1. Phnol.
Phnol l nguyn liu cng nghip quan trng dng sn xut nha,
phnolfocmanhyt, sn xut axt xalixylic, phm nhumNgoi ra, n cn c dng st
trng, bo qun g, sn xut thuc dit c 2,4-D, thuc tr su
9.12.2. Timol.
Timol (3-hyrrxi-4-izprpyltluen) c nhiu trong cc tinh du, l sn phm chuyn
ho ca cc tecpen trong thc vt. Timol c th tng hp bng phn ng sau:
CH
3
OH
CH
3
CH CH
2
H
+
CH
3
OH
CH CH
3
H
3
C
+
HOC
6
H
4
OH
Timol dc dng lm hng liu, lm cht st trng. Khi tin hnh phn ng hyr
ho timol s thu c mentol.
9.12.3. Catechol.
Catechol (1,2-ihyrxibenzen) c th thu nhn bng cch chng ct nha than hoc
bng phng php tng hp.
o- o- ClC
6
H
4
OH
H
2
O, 190 C
0
Catechol

Trong catechol c 2 nhm OH u tham gia phn ng to thnh hp cht vng:
ONa
ONa
CH
2
Cl
2
COCl
2
O
O
CH
2
O
O
C O
Catechol rt d b oxy ho:
OH
OH
O
O
2Ag 2H
+
+ + +
2Ag
+
Catechol l nguyn liu dng iu ch cc ancalit papaverin, pparin, dng sn
xut gaiancol, rnalin
9.12.4. Rezocxinol.Rezocxinol (1,3-ihyrxibenzen) c iu ch bng cch nung
chy kim vi 1,3-benzenisunfnic axt. Rezocxinol thng tn ti di cc dng:
O
O
H
2
/Pd
OH
OH
O
O
1,3-ixxyclhecxen-4
9.12.5. Hyrquinon.
Hyrquinon (1,4-ihyrrxibenzen) c ng dng rng ri trong k thut lm nh,
lm phim. Phim nh c trng mt lp nh tng AgBr. Khi b chiu sng, mt s ht bc
brmua c hot ho AgBr*. Nu phim chp tip xc vi hyrquinon th cc ht bc
c hot ho s b kh thnh bc kim loi nhanh hn bc brmua cha b hot ho.
OH
OH
2AgBr* 2Ag 2Br
-
2HO
-
O
O
+ + + + +
H
2
O 2
Nu ta dng mt dung dch hin hnh, v d tisunfit natri loi phn AgBr khng b
kh (lu hnh) th cc ht bc mn s phn tn trn phim to thnh mt tm nh tri (m nh).
em tm m nh ny vo my in nh ta s thu c dng nh.
9.1. Gi tn theo danh php quc t cc ru sau y:
CH
3
CH CH
2
CH
2
OH
CH
3
Cl CH
2
CH CH CH CH CH
2
OH
CH
3
C C C
CH
3
OH
CH
2
CH
3
CH
3
CH
2
CH
2
CH
CH(CH
3
)
2
CH
OH
CH CH
3
CH
3
OH
HO
HO
Br
3
C CH
2
CH
2
OH CH
3
CH
CH
3
C
C
2
H
5
OH
CH
CH
3
C
2
H
5
a. b.
c. d. e.
f.
g.
9.2. Vit phng trnh phn ng ca ru n-propylic vi cc cht sau:
a. CH
3
COOH c mt H
2
SO
4

b. H
2
SO
4
c nhit cao
c. K
2
Cr
2
O
7
+ H
2
SO
4
c
d. CH
3
COCl
e. (CH
3
CO)
2
O
9.3. T benzen v cc ha cht thch hp, vit phng trnh phn ng iu ch:
a. p-nitro phenol b. p-izopropyl phenol
c. 2,4-dinitro phenol d. p-metyl phenol
9.4. Sp xp theo th t tng dn tnh axit ca cc hp cht sau y:
CH
3
CH
2
CH
2
OH (CH
3
)
3
COH
NO
2
HO
O
2
N
OH
9.5. Sp xp theo th t tng dn hot tnh ca cc ru sau u vi thuc th Luca:
a. 1-phenyl propanol-1, 1-phenyl propanol-2 v 3-phenyl propanol-1
b. 2-buten-1-ol, 3-buten-1-ol v 3-buten-2-ol
9.6. T etanol v cc ha cht thch hp khc cha ti a 4 nguyn t cacbon iu ch cc hp
cht sau y:
a. propanol-1 b. 2-brom-2-metylhexan
c. propanol-2 d. etyl propionat
e. 2,3-dimetyl butanol-2 f. 1,2-butandiol
ha hc hu c.
H Ni.
Ni.
Chng 10
ETE
10.1 CU TO, PHN LOI V CCH GI TN
te l nhng hp cht c cng thc phn t R-O-R, R-O-Ar hoc Ar-O-Ar.
1- Tn gi ca te c to thnh t tn gi ca 2 nhm lin kt vi nguyn t xy v
ch te.
V d:
C
2
H
5
O C
2
H
5
C
6
H
5
O C
6
H
5
CH
3
O C(CH
3
)
3
itylte iphnylte Mtyltecbutylte

2- Nu mt trong 2 nhm lin kt vi xy khng c tn gi n gin th hp cht c
gi nh dn xut ankxi: CH
3
O- (mtxi), C
2
H
5
O-(txi), C
6
H
5
O-(phnxi)
V d:
CH
3
CH
2
CH
2
CH CH
2
CH
3
OCH
3
HO CH
2
CH
2
OC
2
H
5
3-mtxihecxan
p- C
2
H
5
O C
6
H
4
COOH
p-txibenzic axit 2-txitanol

3- Hp cht n gin nht ca ankylarylte l anizol C
6
H
5
-OCH
3
.
4- Nu te c hai nhm th ging nhau th ngi ta gi l te i xng. nu cc nhm
th khc nhau th l te bt i xng.
10.2. TNH CHT VT L.
Do c im v cu to: gc lin kt C-O-C trong phn t te khng phi l 180
0
nn
mmen lng cc gia 2 lin kt C-O khng trit tiu ln nhau do te phn cc yu.
O
R
R
110
0
Nhng s c mt ca mmen phn cc ny khng nh hng n nhit ca te v vy
te c nhit si gn vi ankan tng ng v thp hn nhiu so vi ancol tng ng. ho
tan ca te thp trong nc tng t nh cc ancol. V d itylte v n-butanol c ho tan
trong nc nh nhau l 8g/100g (HOH). iu c th gii thch bng s lin kt hyr ca
nc vi ancol v te tng t nh nhau.
Trong cng nghip, iu ch mt s te i xng thp ngi ta dng phng php
ehyrat ho gia 2 phn t ancol.
S cnh tranh ca phn ng hyrat ho lng phn t vi phn ng tch loi c
khng ch bng cch khng ch iu kin phn ng. V d tylen c to thnh l sn phm
ch yu khi un nng ru tylic vi axt sunfuric m c nhit 180
0
C, tri li itylte l
sn phm ch yu c to thnh 140
0
C vi lng ru tylic lun lun d.
Phn ng to te xy ra theo c ch S
N
1 v S
N
2

nh sau:
ROH
2
+
ROH
R
+ ROH
R O R
H
+
R O R H
+
+
R O R
H
+
RO
H
R OH
H
+ +
-HOH
+ H
+
R O R
S 1
N
S 2
N
Phng php iu ch trn y ch c ngha i vi cc te i xng. Trong trng
hp dng cc ancol khc nhau, phn ng s to thnh hn hp sn phm. Phng php ny cn
dng iu ch cc te vng vi ru a chc.
CH
2
CH
2
H
2
C CH
2
OH HO
H
2
SO
4
O
Ttrahyrfuran

Phn ng tch loi nc khng xy ra i vi cc hp cht phnol ni chung do hiu
ng lin hp , p ca nhn thm vi xy nn khng c kh nng bn ho ionxni.
Trong phng th nghim iu ch te ch yu ngi ta s dng phng php
Uylimxn.
R X NaOR' R O R' NaX + +
R X NaOAr R O Ar NaX + +

V d:
CH
3
Br NaO C(CH
3
)
3
CH
3
O C(CH
3
)
3 +
C
6
H
5
OH (CH
3
)
2
SO
4
NaOH dd
C
6
H
5
O CH
3
+
BrCH
2
C
6
H
5
NaOH dd
O
2
N C
6
H
4
OH p- O
2
N C
6
H
4
O CH
2
C
6
H
5
p-
+

Phng php uylimxn c th iu ch te i xng, te khng i xng v cc te
thm. Mt khc cng cn lu rng trong phng php ny khng th dng arylhalogenua (tr
trng hp trong nhn thm c cc nhm th ht in t mnh) cho tng hp Uylimxn v
phn ng kh c th xy ra. V d tng hp p-nitrbenzylphnylte ch c th tin hnh theo
s (1) trong 2 s phn ng sau, v theo (2) phn ng s khng th xy ra.
O
2
N C
6
H
4
CH
2
OC
6
H
5
p-
Cl C
6
H
5
p- O
2
N C
6
H
4
CH
2
ONa +
NaO C
6
H
5
O
2
N C
6
H
4
p- CH
2
Cl + (1)
(2)
Trong phng php ny cng khng c s dng cc ankylhalogenua bc III v s xy
ra ch yu l phn ng tch loi.
V d: iu ch tyltecbutylte sau y ch c th tin hnh phn ng theo s (1).
CH
3
CH
2
O C(CH
3
)
3
CH
3
CH
2
Br NaO C(CH
3
)
3 +
(CH
3
)
3
CCl NaO CH
2
CH
3
+
(1)
(2)
10.4.1. Phn ng phn ct te.
te l mt cht tng i tr. N bn vng di tc dng ca kim, tc nhn xy ho v
tc nhn kh. N ch b phn ct bi axt mnh.
V d:
ROR' HX R'OH RX + +
ArOR HX ArOH RX + +
( HX = HI, HBr, HCl)

Cc phn ng phn ct te ch xy ra trong iu kin khc nghit: HX un nng, m
c. Cc axt thng dng l HI v HBr.
V d:
CH
3
CH
2
O CH
2
CH
3
HBr CH
3
CH
2
OH CH
3
CH
2
Br + +
C
6
H
5
O CH
3
HI C
6
H
5
OH CH
3
I + +

Phn ng phn ct te xy ra theo c ch S
N
1 v S
N
2.
Prton ha ROR' H
+
R O R'
H
+
+
Theo S
N
1
R O R'
H
+
R
+
R'OH +
chm
R
+
X
-
RX +
nhanh

Theo S
N
2
R O R'
H
+
X
-
RX R'OH + + X . . . R. . . OR'
R
- +
10.4.2. Chuyn v Claizen.
Khi b un nng n 200
0
C, phnylallylte chuyn thnh o-allylphnol.
OCH
2
CH CH
2
OH
CH
2
CH CH
2
200 C
0
Ngi ta gi phn ng trn y l chuyn v Claizen. Phn ng ny xy ra theo c ch
vng sau y:
OCH
2
CH
CH
2
O
CH
2
CH
H
CH
2
H
OH
CH
2
CH CH
2
Nu cc v tr cto b chim ch th n xy ra v tr para.
OCH
2
CH CH
2
R R
O
R R
CH
2
CH CH
2
OH
R R
CH
2
CH CH
2
t C
0
10.5. MT S TE QUAN TRNG.
10.5.1. te tylic.
te tylic c iu ch t ancoltylic vi xc tc nhm trixt hoc H
2
SO
4
. te tylic l
mt cht lng c mi c trng, nh, d bay hi, d chy. te tylic c dng lm dung mi,
lm cht gy m trong y hc. Khi lu, trong te tylic sinh ra pexit nn khi chng ct rt d
n. te tylic tuyt i c thu nhn bng cch chng ct te vi H
2
SO
4
m c v sau
ng trong bnh thu tinh c cha natri kim loi.
10.5.2. tylenxit.
tylenxit (xiran) trong cng nghip c iu ch bng phn ng xy ho tylen vi
xc tc kim loi.
CH
2
CH
2
O
2
H
2
C CH
2
O
Ag, 250 C
0
+
Trong phng th nghim cc hp cht pxt c th iu ch theo cc phng php sau:
a. T halogenhyrin.
C C C C
X OH
C C
O
H
2
O X
- X
2
, H
2
O
+ +
HO
-
b. xy ho cc anken bng peaxt.
C C C
6
H
5
COOOH C C
O
C
6
H
5
COOH
+ +
O H
tlylenxt l hp cht hot ng mnh nn n rt d tham gia cc phn ng m vng.
a. Phn ng m vng c xc tc bng axt.
C C
+
C C
O
Z
-
C C
Z OH
H
+
V d:
H
2
C CH
2
O
H
2
O
H
+
CH
2
CH
2
OH OH
+
C
2
H
5
OH CH
2
CH
2
OH OC
2
H
5
H
2
C CH
2
O
+
HBr CH
2
CH
2
OH Br
H
2
C CH
2
O
H
+
+
b. Phn ng Grinha.
RMgX H
2
C CH
2
O
RCH
2
CH
2
OMgX RCH
2
CH
2
OH +
V d:
C
2
H
5
MgCl H
2
C CH
2
O
C
2
H
5
CH
2
CH
2
OMgCl C
2
H
5
CH
2
CH
2
OH
+
10.1. Vit cc ng phn ete ca hp cht c cng thc phn t C
5
H
12
O. Gi tn. Ete no quang
hot.
10.2. Vit cng thc cu to cc hp cht sau v gi tn theo IUPAC:
a. metyl etyl ete b. phenyl etyl ete
c. xiclopentyl tec-butyl ete d. m-dietoxybenzen
e. 5-metoxy-2-pentanol f. dibenzyl ete
10.3. Gi tn cc hp cht sau y:
CH
3
O C(CH
3
)
3
C
6
H
5
O C
6
H
5
H
2
C CH O CH
2
CH CH
2
O C
2
H
5
CH
3
CH
2
O CH
2
CH
2
OH
Br OC
2
H
5
a. b.
c. d.
e. f.
10.4. Hon thnh cc phn ng sau y:
CH
3
OH
1. HO
-
2. CH
3
I
p-
C
6
H
5
CH
2
ONa C
6
H
5
CH
2
Br
(CH
3
)
2
CHOCH
3
HBr
CH
3
CH
2
CHO HOCH
2
CH
2
OH
H
+
+
+
+
a.
b.
c.
d.

10.5. Phn bit:
a. p-CH
3
-C
6
H
4
-OH v C
6
H
5
OCH
3
b. di n-propyl ete v n-propyl clorua
c. allyl etyl ete v dietyl ete
10.6. Mt hp cht A (C
9
H
10
O
2
) b thu phn cho focmaldehit v B (C
8
H
10
O
3
), tan d dng
trong baz. Vit nhng cng thc cu to c th c ca A v B.
10.7. n-butyl etyl ete b phn ct bi HBr c nng cho etyl bromua v butyl bromua. Tec-butyl
etyl ete b phn ct bi HBr cho tec-butyl bromua v ru etylic. Vit c ch ca hai phn ng,
tm cht trung gian.
ha hc hu c.
H Ni.
Ni.
Chng 11
ANHYT V XTON.
11.1. CU TO.
Anehyt l nhng hp cht c cng thc phn t l RCHO v xton l RCOR. Gc R-
v R- c th l gc bo hoc thm. Nh vy l c anhyt ln xton u cha nhm C=O nn
ngi ta xem n l loi hp cht cacbnyl. Chnh s c mt ca nhm cacbnyl ny xc nh
nhng tnh cht c bn ca anhyt v xton.
Nhn chung nhiu tnh cht c bn ca anhyt v xton ging nhau nhng s c mt
ca cc nhm th khc nhau bn cnh nhm cacbnyl (trong anhyt l hyr cn trong xton
l R) dn n mt s tnh cht khc nhau gia anhyt v xton:
1- Anhyt d dng b xy ho cn xton b xy ho kh khn hn.
2- Anhyt tham gia phn ng cng nuclphin, loi phn ng c trng cho nhm
cacbnyl mnh hn xton.
Xt v mt cu to ta nhn thy rng nguyn t cacbon ca nhm cacbnyl c trng thi
lai ho sp
2
do n c 3 lin kt vi cc nguyn t khc. Ocbitan p t do cn li ca cacbon
xen ph vi ocbitan p ca xy to thnh lin kt . Nh vy lin kt ca cacbon v xy trong
nhm cacbnyl l lin kt bi. Mt khc do m in khc nhau nn nhm cacbnyl b phn
cc v pha xy.
R
C O
R
120
0
120
0
R
C O
R
- +
11.2. CCH GI TN.
11.2.1. Tn gi ca anhyt.
Tn gi ca cc anhyt c to thnh t tn gi ca cc axt cacbxylic tng ng
bng cch thay t axt bng t anhyt.
Tn gi cc anhyt theo IUPAC c hnh thnh nh sau: mch chnh c tnh l
mch di nht c cha nhm CHO v tn gi ca mch chnh l tn gi ca hyrcacbon
tng ng cng vi ui al. V tr cc nhm th c gi tn cng vi cc ch s m trong
nguyn t cacbon ca nhm cacbnyl c ch s 1. V d:
HCHO CH
3
-CHO CH
3
CH
2
-CHO
Focmanhyt Anhyt axtic Anhyt prpanic
Mtanal tanal Prpanal
(Axtanhyt) (Prpinanhyt)
C
6
H
5
-CHO p-O
2
N-C
6
H
5
-CHO CH
3
CH
2
CH
2
CH(CH
3
)-CHO
Benzanhyt p-Nitrbenzanhyt 2-Mtylpentanal
11.2.2. Xton.
Tn gi thng thng ca hp cht xton n gin nht l axton, tn gi thng thng
ca cc xton bo khc c hnh thnh bng cch gi tn ca 2 nhm th lin tc lin kt vi
nguyn t cacbon cacbnyl cng thm ui xton. Tn gi ca cc xton m nhm cacbnyl
lin kt trc tip vi nhn benzen c ui l phnon.
Tn gi xton theo IUPAC c chon mch chnh l mch di nht, c cha nhm
cacbnyl v gi tn hyrcacbon tng ng cng thm ui on. V tr cc nhm th c nh
s sao cho nhm cacbnyl c ch s l nh nht.
V d:
CH
3
COCH
3
CH
3
CH
2
-CO-CH
3
(CH
3
)
2
CH-CO-CH
3

Axton Mtyltylxton Mtylizprpylxton
Prpanon Butanon-2 3-Mtylbutanon-2
C
6
H
5
-CO-CH
3
C
6
H
5
-CO-CH
2
CH
2
CH
3
C
6
H
5
-CO-C
6
H
5

Axetonphnon n-Butyrophnon Benzophnon
Ngoi ra cn c tn gi theo nhm x (-CO-).
V d: O=CH-CH=O CH
3
-CO-CO-CH
3

1,2-ixtan 2,3-ixbutan
11.3. TNH CHT VT L.
Nh ni trn y, phn t anhyt v xton phn cc nn chng c nhit si cao
hn cc hp cht c cng phn t lng tng ng. Cc phn t anhyt v xton khng c kh
nng to lin kt hyr vi nhau nn chng c nhit si thp hn cc ancol hoc axt
cacbxylic tng ng.
V d: Hp cht M t
0
C
CH
3
CH
2
CH
2
-CHO (Butanal) 72 76
CH
3
-CO-CH
2
CH
3
(Mtyltylxton) 72 80
CH
3
-(CH
2
)
2
-CH
3
(Pentan) 72 36
C
2
H
5
-O-C
2
H
5
(te tylic) 74 34
C
3
H
7
-CH
2
-OH (n-Butanol) 74 118
CH
3
CH
2
-COOH (A.Prpanic) 74 141
Cc anhyt v xton thp ho tan tt trong nc c th do c kh nng to lin kt
hyr vi nc. Anhyt v xton tan tt trong cc dung mi hu c.
11.4. IU CH.
a. iu ch focmanhyt.
Trong cng nghip focmanhyt c iu ch bng 2 phng php sau y:
1- xy ho trc tip CH
4
c xc tc v nhit thch hp
CH
4
O
2
HCHO H
2
O + +
NO, 450-600 C
0
2- xy ho ru mtylic bi khng kh c xc tc
CH
3
OH O
2
HCHO H
2
O
Cu, 500-600 C
+ +
0
Focmanhyt l cht kh thng c s dng trong cng nghip di dng dung dch
(focmalin), dng rn polyme (HCHO)
n
, parafocmanhyt hoc trixan (CH
2
O)
3
.
b. Axtanhyt.
Axtanhyt c iu ch bng phn ng hyrat ho axtylen hoc hyr ho ru
tylic.
HC CH H
2
O
H
2
SO
4
, HgSO
4
CH
3
CH
2
OH
CH
3
CHO
Cu, 250-300 C
+
0
Trong cng nghip axtanhyt ch yu dng iu ch axt axtic.
c. Benzanhyt.
Trong cng nghip benzanhyt c iu ch t tluen bng phn ng clo ho v thu
phn sau y:
C
6
H
5
CH
3
C
6
H
5
CHCl
2
Cl
2
, t C
0
H
2
O, 100 C
0
C
6
H
5
CHO

d. Anhyt xalixylic.
Anhyt xalixylic v mt s anhyt c cha nhm phnol c th iu ch bng phn
ng Raim-Timan nh sau:
CHCl
3
NaOH H
2
O NaCl CCl
2 + + +
C
6
H
5
OH C
6
H
5
ONa
NaOH
NaO C
6
H
4
CHCl
2
o-
NaO C
6
H
4
CHO o-
NaOH CCl
2
o- HO C
6
H
4
CHO
Anhyt xalixylic
HCl
Mt s anhyt thm dng trong cng nghip nc hoa, cng nghip thc phm thng
c iu ch bng phn ng xy ho ni i ca cc hp cht t nhin.
OCH
3
CH CH CH
3
K
2
Cr
2
O
7
, H
2
SO
4
OCH
3
CHO
Anetol ( tinh du hoa hi)

OH
OCH
3
CH
2
CH CH
2
OH
OCH
3
CH CH CH
3
OCOCH
3
OCH
3
CH CH CH
3
(CH
3
CO)
2
O, CH
3
COONa
KOH, 225 C
0
OCOCH
3
OCH
3
CHO
OH
OCH
3
CHO
K
2
Cr
2
O
7
, H
2
SO
4
H
2
O, H
+
, t C
0
Eugenol
Vanilin

Mt s dung mi quan trng nhaxton, tylmtylxton c iu ch bng phn ng
hyr ha ancol.
Cu, 250-300 C
0
CH
3
CH
2
CH(OH) CH
3
CH
3
CH
2
CO CH
3
CH
3
CH(OH)CH
3
CH
3
CO CH
3
Cu, 250-300 C
0
a. Cc phng php tng hp anhyt.
1- xy ho cc ancol 1
0
.
RCH
2
OH
Cu, t C
0
K
2
Cr
2
O
7
RCHO
V d:
CH
3
CH
2
CH
2
CH
2
OH CH
3
CH
2
CH
2
CHO
Cu, 250-300 C
0
2- xy ho cc ankylbenzen.
Ar CH
3
CrO
3
, (CH
3
CO)
2
O
Ar CHCl
2
ArCH(OCOCH
3
)
2
ArCHO
Cl
2
, t C
0
V d:
O
2
NC
6
H
4
CH
3
O
2
NC
6
H
4
CH(OCOCH
3
)
2
O
2
NC
6
H
4
CHO
CrO
3
, (CH
3
CO)
2
O H
2
O, H
2
SO
4
Br C
6
H
4
CH
3
Cl
2
, t C
0
Br C
6
H
4
CH
2
Cl Br C
6
H
4
CHO
CaCO
3
, H
2
O
3- Kh ho cloranhyrit.
RCOCl hoc ArCOCl RCHO hoc ArCHO
H
2
, Pd -
H
2
, Pd/S
BaSO
4
V d:
O
2
N C
6
H
4
COCl p- O
2
N C
6
H
4
CHO p-
H
2
, Pd - BaSO
4
4- Phn ng Raim-Taiman. (Xem phn 9.10.2.).
5- Phng php Gatteman-Kc.
Cl CHO C
6
H
6
C
6
H
5
CHO
AlCl
3
+
CO HCl Cl CHO
(focmyl clorua)
+
b. Cc phng php tng hp xton.
1- xy ho ancol bc II.
R CH(OH) R'
KMnO
4
K
2
Cr
2
O
7
Cu, t C
0
R C
O
R'
V d:
CH
3
CH
2
CH
2
CH(OH) CH
2
CH
3
C
3
H
7
CO C
2
H
5
Cu, 250 C
0
K
2
Cr
2
O
7
, H
2
SO
4
CH
3
CH CH
3
H
3
C
H
OH
CH
3
CH CH
3
H
3
C
O
(-)-Mentol (-)-Menton

2- Axyl ho Frien-Crap.
Ar H R COCl Ar CO R HCl + +
AlCl
3
4- Phn ng ca cloanhyrit vi hp cht c cadimium.
RMgCl CdCl
2
R
2
Cd
R'COCl
ArCOCl
R' CO R hoc Ar CO R +
V d:
C
4
H
9
MgBr
CdCl
2
(C
4
H
9
)
2
Cd
(CH
3
)
2
CH COCl
C
4
H
9
CO CH(CH
3
)
2
CdCl
2 Mg
CH
3
CH
2
CH
2
COCl
CH
3
C
6
H
4
CO CH
2
CH
2
CH
3
m-
CH
3
C
6
H
4
Br m- CH
3
C
6
H
4
MgBr m - ( CH
3
C
6
H
4
)
2
Cd m-
4- cacbxyl ho cc axt cacbxylic hoc dn xut ca chng.
RCOOH
RCH
2
OH
RCOCl
RCHO
LiAlH
4
SOCl
2
-T mui icacbxylat canxi.
(RCOO)
2
Ca hoc RCOO Ca OOCR' R CO
R hoc R
CO R'
t C
0
11.5. TNH CHT HA HC.
11.5.1. Phn ng cng nuclphin.
Phn ng nuclphin ca cc hp cht anhyt v xton xy ra qua hai giai on: giai
on 1 cng tc nhn mang in tch m vo nguyn t cacbon cacbnyl, xy ra chm quyt
nh tc phn ng, giai on 2 bn ho sn phm xy ra nhanh bng cch cng vi phn
mang in tch dng.
C O
R
R
-
+
-
Y X
+
C
R
R
X
O
-
Y
+
, nhanh
chm
C
R
R
X
OY
+
V giai on quyt nh tc phn ng c quyt nh bi s tn cng ca tc nhn
nuclphin nn y l phn ng A
N
.
Anhyt tham gia phn ng A
N
d hn xton v do nh hng ca hiu ng khng gian
v in t n trng thi chuyn tip:
C
R
R
X
O
-

- Nhm th R>H lm cn tr s tn cng ca tc nhn X
-
.
- Nhm th R c hiu ng +I lm gim bn ca trng thi chuyn tip.
1.5.2. Mt s phn ng A
N
ca anhyt v xton.
1- Phn ng xy ho.
- Anhyt:
R
CHO hoc ArCHO
R
COOH hoc ArCOOH
AgNO
3
/NH
4
OH
KMnO
4
K
2
Cr
2
O
7

- Mtylxton:
(Ar), R C CH
3
O
X
2
HO
-
(Ar), R C CX
3
O
(Ar), R C O
-
O
CHX
3 +
V d:
C
2
H
5
CO CH
3
I
2
NaOH
C
2
H
5
COONa CHI
3
+
(CH
3
)
2
C CH CO CH
3
Cl
2
KOH
(CH
3
)
2
C CH COOK CHCl
3
+
2- Phn ng kh.
- Kh thnh ancol:
C O
H
2
, Ni (Pd, Pt)
LiAlH
4
, NaBH
4
CH OH

V d:
C
6
H
5
CO CH
3
C
6
H
5
CHOH CH
3
LiAlH
4
- Kh thnh hyrcacbon.
C O
Zn(Hg), HCl .
H
2
N NH
2
, HO
-
CH
2
(1)
(2)

(1)- Gi l phn ng Klmenxen dng kh cc hp cht khng bn trong mi trng
kim.
(2)- Gi l phn ng Kizne-Vnf dng kh cc hp cht khng bn trong mi
trng axt.
V d:
C
6
H
5
CO CH
2
CH
2
CH
3
C
6
H
5
CH
2
CH
2
CH
2
CH
3
Zn(Hg), HCl .
3- Phn ng Grinha. (Xem phn iu ch cc hp cht ancol).
C O RMgX R C OMgX R C OH +
H
2
O
4- Phn ng to thnh hp cht xianhyrin.
C O CN
- H
+
C CN
OH
+
V d:
CH
3
CHO NaCN
H
2
SO
4
CH
3
CH CN
OH
CH
3
CH COOH
OH
+
H
2
O, HCl
Axit lactic
C
6
H
5
CHO NaCN
H
2
SO
4
C
6
H
5
CH CN
OH
C
6
H
5
CH COOH
OH
+
H
2
O, H
+
Axit Menilic

5- Phn ng cng bisunfit natri.
C O NaHSO
3
C
OH
SO
3
Na +
V d:
C
6
H
5
CHO NaHSO
3
C
6
H
5
CH
OH
SO
3
Na +
CH
3
CH
2
COCH
3
NaHSO
3
CH
3
CH
2
C(OH)
CH
3
SO
3
Na +
Phn ng ny ch xy ra nhng anhyt v xton c hiu ng khng gian nh (ch yu
l cc mtylxton). Sn phm phn ng thu c l nhng cht kt ta v vy ngi ta thng
dng phn ng ny tch cc hp cht cacbnyl ra khi cc hp cht hu c khng phi l
cacbnyl.
+ HSO
3
-
H
+
HO
-
SO
2
H
2
O
SO
3
-
H
2
O
+
+
C O NaHSO
3
C
OH
SO
3
Na +
H
+
C O
6- Phn ng vi cc dn xut ca amnic.
C N OH xim
C N NH
2
Hyrazon
C N NHC
6
H
5
Phnylhyrazon
C N NHCONH
2
Cemicacbazon
Sn phm
H
2
N OH Hyrxylamin

H
2
N NH
2
Hyrazin
H
2
N NHC
6
H
5
Phnylhyrazin
H
2
N NHCONH
2
Cemicacbazit
H
2
N A

C O H
2
N A C N A C
OH
NH A +

V d:
CH
3
CHO H
2
N OH
H
+
CH
3
CH NOH +
C
6
H
5
CHO H
2
N NHC
6
H
5
H
+
C
6
H
5
CH N NHC
6
H
5
+

C ch ca phn ng:
C O
H
+
C OH
+
C
OH
N
H
H
A
+
H
2
N A
H
+
H
3
N A
+
C N A H
2
O H
+
+ +
Phn ng thng xy ra trong mi trng axt ho nhiu, thun li cho phn ng A
N
nhng amin cng b prton ho nn lm gim tnh nuclphin ca tc nhn v ngc li khi pH
cao. Do cc phn ng ca anhyt v xton vi cac dn xut amin thng c mt pH ti u.
V d phn ng ca axton vi hyrxylamin c pH ti u l 5.
Cc phn ng ny thng dng nh tnh anhyt v xton v hp cht cht to thnh
c mu c trng.
7- Phn ng Canizaro.
y l loi phn ng ca cc anhyt khng cha cc -hyr linh hot trong phn t
di tc dng ca kim mnh.
2RCHO HO
-
RCOO
-
RCH
2
OH + +

V d:
2HCHO HCOO
-
+ CH
3
OH
50% NaOCl
(CH
3
)
3
C COO
-
(CH
3
)
3
C CH
2
OH
50% KOH/ancol
(CH
3
)
3
C CHO 2
+
y l loi phn ng xy ra theo c ch 2 giai on:
R CHO HO
-
R CH
OH
O
-
+ (1)
- +
R C O
H
R C O
-
H
OH
R C
H
H
O
-
R C OH
O
RCH
2
OH RCOO
-
+ +
+ H
+
H
+
-
(2)
8- Phn ng vi cc hp cht c nhm mtylen linh ng
Nhng hp cht c nguyn t hyr v tr linh ng c gy ra do hiu ng C tham
gia phn ng vi c hp cht cacbnyl c gi l hp phn mtylen.
R C
H
H
C G
(Hyr linh ng)
( G = O, N...
Phn ng ca hp cht cacbnyl vi hp phn mtylen c th xy ra nh sau:
C
H
C O C O
+
-
+ C
OH
C C O
Phn ng ny gi l cng anol hay anol ho.
V d:
CH
3
CH O H CH
2
CHO + CH
3
CH(OH) CH
2
CHO
HO
-
3-Hyrxibutanal

Tip theo xy ra giai on tch nc, c gi l phn ng ngng t crton hay crton
ho:
CH
3
CH
OH
CH
H
CHO CH
3
CH CH CHO
Anhyt crtnic
H
2
O
H
+
-
Hp cht crton c to thnh tip tc phn ng vi hp phn mtylen, gi l phn
ng Maicsn.
CH
3
CH CH CH O C C O
H
H
H
CH
3
CH CH
2
CHO
CH
2
CHO
+
HO
-
9- Cc phng php nhn bit anhyt v xton.
Ngi ta thng nhn bit cc anhyt v xton bng cc phng php sau y:
- Cho anhyt v xton tc dng vi 2,4-initrphnylhyrazin to kt ta mu vng
hoc mu .
- Phn bit anhyt v xton bng phn ng trng gng- thuc th Tlen,
- Cc mtylxtonc nhn bit bng phn ng halofoc.
- Trong ph hng ngoi, nhm cacbnyl c s sng: (CO) = 1700cm
-1

11.1. Gi tn theo danh php quc t v thng thng (nu c) ca cc hp cht sau:
H
2
C CH CHO OHC CH
2
CH
2
CHO CCl
3
CHO
CH
3
CH
CH
3
C CH
3
O
C
6
H
5
C
O
C
6
H
5
CH
3
C
CH
3
CH C CH
3
O
a. b. c.
d. e. f.
11.2. Vit cng thc cu to ca cc hp cht sau:
a. 3-hidroxi butanal b. 2,4- hexandion
c. izobutyraldehit d. 4-tecbutyl xiclohexanon
11.3. Vit phn ng ca butanal vi:
a. Thuc th Tollens
b. 2,4-dinitro phenylhydrazin
c. Etandiol + HCl
d. LiAlH
4
v tip theo l s trung ha
e. NaOH long v nng.
11.4. Mt hp cht hu c c cng thc phn t C
4
H
8
O c kh nng phn ng natri bisunfit cho
hp cht cng bisunfit, tc dng vi hidroxylamin cho oxim, tc dng vi dung dch AgNO
3
trong NH
3
cho phn ng trng gng v khi b oxi ha cho axit izobutyric. Hy cho bit cng
thc cu to ca hp cht C
4
H
8
O v vit phng trnh phn ng xy ra.
11.5. iu ch:
a. butanon-2 t propanol-2
b. axit -hidroxi--phenyl axetic t benzaldehit
c. 4-metyl-3-pentenon-2 t metyl axetilen
d. 1-metyl-1-phenyl etanol t benzaldehit
11.6. Nhn bit:
a. propanol v propanon
b. pentanon-2 v pentanon-3
c. butanon-2 v 3-butenol-1
11.7. Vit phn ng ca benzaldehit vi cc ha cht sau y:
a. Dung dch HO
-
m c, nng v tip theo l s trung ha.
b. 2,4-dinitro phenylhydrazin + H
+

c. Dung dch NaCN trong nc

ha hc hu c.
H Ni.
Ni.
Chng 12
AXT CACBXYLIC V DN XUT CA N.
A. AXT CACBXYLIC.
12.1. CU TO
Axt cacbxylic l loi hp cht hu c c tnh axt, cha nhm cacbxyl COOH lin
kt vi cc nhm ankyl, ankenyl, aryl
V d: HCOOH CH
3
COOH C
6
H
5
-COOH
Ngi ta phn loi cc axt cacbxylic theo 2 cch:
1- Theo s lng nhm cacbxyl c trong phn t:
- Mncacbxylic axt ch cha mt nhm cacbxyl R-COOH
- icacbxylic axt cha 2 nhm cacbxyl
HOOC-COOH HOOC-CH
2
-COOH
Axt xalic Axt malnic
- Tricacbxylic axt (c 3 nhm -COOH); polycacbxylic c cha n nhm -COOH
2- Theo bn cht gc lin kt vi nhm COOH:
- Axt cacbxylic no: C
n
H
2n+1
COOH
- Axt cacbxylic thm: Ar-COOH.
- Axt cacbxylic khng no: C
n
H
2n-1
COOH.
12.2. CCH GI TN.
12.2.1. Tn gi thng thng.
Tn gi thng thng hay c s dng gi tn cc axt cacbxylic. Cc tn gi ny
thng lin quan n ngun gc thu nhn axt cacbxylic. V d axt focmic (cht gy rt bng
khi b kin cn) v c trong c th kin (kin theo ting Latinh l focmica) nn c tn l focmic.
Axt caprilic CH
3
(CH
2
)
8
COOH c tch ra t m ca con d ci (d ci l caper)
Trong tn gi thng thng, ngi ta cng hay dng tip u ng iz- ch nhm mtyl
phn nhnh u mch.
V d:
CH
3
CH COOH
CH
3
CH
3
CH
CH
3
(CH
2
)n COOH
Axit izbutyric Axit izcacbxylic

nh du cc nhm th trong tn gi thng thng, ngi ta s dng cc ch ci
Hylp , , ,
C C C C COOH

Trong nhiu trng hp ngi ta gi tn ca cc axt nh l dn xut ca axt axtic
(khng thm) v dn xut ca axt benzic (hp cht thm).
12.2.2. Danh php IUPAC.
Trong danh php ny, mch chnh c chn l mch di nht, c cha nhm COOH
v nh s th t ca cc nguyn t cacbon vi nguyn t cacbon ca nhm cacbxyl mang s
1. Gi tn cc axt bng cch gi tn ca hyrcacbon tng ng cng thm ui IC v cc
nhm th cng vi s ch ca n.
V d:
HCOOH CH
3
COOH CH
3
CH
2
COOH CH
3
CH
2
CH
CH
3
COOH
Axit mtanic Axit tanic Axit prpanic Axit 2-mtylbutanic
12.3. TNH CHT VT L.
Phn t axt cacbxylic phn cc v tng t nh ancol n c kh nng to lin kt
hyr gia chng vi nhau v vi cc phn t ca cc hp cht khc. Do tnh ho tan ca cc
axt cacbxylic bo tng t nh cc ancol: cc axt cacbxylic c s nguyn t cacbon C <4
tan tt trong nc; C>5 ch tan mt phn cn C>10 khng tan trong nc. Axt thm n gin
nht l axt benzic hu nh khng tan trong nc.
Cc axt cacbxylic c nhit si cao hn ancol c cng phn t lng tng ng.
V d:
CH
3
CH
2
COOH M=74 t
0
s
C = 141
CH
3
CH
2
CH
2
CH
2
OH M=74 t
0
s
C = 118
S tng ln v nhit si ca cc axt so vi ancol c gy ra bi s lin kt hyr
hoc s sonvat ho.
R C
O . . . H
O H . . . O
O
C R R C
O . . . H
O H . . . O H . . . O
H
O . . . H O
C R
H
a. iu ch axt focmic.
CO + NaOH
200 C, 7at
0
HCOONa
H
+
HCOOH

b. iu ch axt axtic:
HC CH
CH
3
CH
2
OH
H
2
O, HgSO
4
, H
2
SO
4
CH
3
CHO
KMnO
4
CH
3
COOH
Cu, 250-300 C
0
Axt axtic c ngha rt quan trng trong cng nghip. Mt lng ln axt ny thu nhn
bng phng php ln men.
Ngoi ra trong cng nghip, mt ngun nguyn liu rt ln thu nhn axt cacbxylic l
du m thc vt v ng vt cc loi.
c. iu ch axt benzic.
C
6
H
5
CH
3
C
6
H
5
CCl
3
C
6
H
5
COOH
Cl
2
, t C
0
H
2
O, HO
-
Nha than
Du m
chng ct O
2
, V
2
O
5
o-Xylen
HOOC C
6
H
4
COOH
Axit phtalic
o- CH
3
C
6
H
4
CH
3
o-
a. xy ho cc ancol bc I.
R CH
2
OH R COOH
KMnO
4
V d:
CH
3
CH
2
CH(CH
3
) CH
2
OH CH
3
CH
2
CH(CH
3
) COOH
KMnO
4
c. xy ho cc ankylbenzen.
Ar R
KMnO
4
Ar COOH

V d:
KMnO
4
, HO
-
Br C
6
H
4
CH
3
o- Br C
6
H
4
COOH o-
Axit p-nitrbenzic
K
2
Cr
2
O
7
, H
2
SO
4
O
2
N C
6
H
4
CH
3
p- O
2
N C
6
H
4
COOH p-
d. Cacbxyl ho tc nhn Grinha.
(Ar)RX
Mg, te
(Ar)RMgX
CO
2
(Ar)RCOOMgX (Ar)RCOOH
H
+
V d:
C
2
H
5
C(CH
3
)
CH
3
COOH
H
+
C
2
H
5
C(CH
3
)
CH
3
Cl
Mg, te
C
2
H
5
C(CH
3
)
CH
3
MgCl C
2
H
5
C(CH
3
)
CH
3
COOMgCl
CO
2
Axit imtyltylaxtic

C
6
H
5
Br
Mg, te
C
6
H
5
MgBr
CO
2
C
6
H
5
COOMgBr C
6
H
5
COOH
H
+
3- Thu phn cc hp cht nitrin.
R C N H
2
O
H
+
HO
-
RCOOH H
4
N
+
RCOO
-
NH
3
+
+
+
V d:
C
6
H
5
CH
2
Cl
NaCN
C
6
H
5
CH
2
CN C
6
H
5
CH
2
COOH
H
2
SO
4
(70%)
Axit m-tluic
NaCN
H
2
SO
4
(75%)
CH
3
C
6
H
4
Cl m- CH
3
C
6
H
4
CN m- CH
3
C
6
H
4
COOH m-
Axit valric
NaCN H
+
NaOH
C
4
H
9
COOH n- C
4
H
9
Br n- C
4
H
9
CN n- C
4
H
9
COO
-
n-
Trong cc phn ng iu ch nu trn y, phn ng xy ho trc tip thu c axt
gi nguyn khung cacbon. Cc phn ng Grinha hay tng hp nitrin lm tng mch thm mt
nguyn t cacbon.
Tnh cht ho hc ca axt cacbxylic c quyt nh bi nhm cacbxyl COOH c
mt trong phn t. Mt khc nhm COOH c to thnh t nhm CO v nhm OH m 2
nhm ny to hiu ng lin hp , p ln nhau lm cho lin kt O-H phn cc mnh dn n
hyr d tch ra di dng ion H
+
.
C
O
O H

T c im cu to trn y, c th suy ra axt cacbxylic c kh nng tham gia mt s
phn ng sau y:
1- Phn ng lm t lin kt O-H biu hin tnh axt.
C
O
O H

2- Phn ng cng vo nhm cacbnyl lm t lin kt C-OH
C
O
OH

3- Phn ng cacbxyl ho (tch nhm CO
2
).
C
O
O H

4- Phn ng th cc nguyn t hyr linh ng.
R CH
H
COCl
12.5.1. Phn ng lm t lin kt O-H biu hin tnh axt.
RCOOH RCOO
-
H
2
O H
3
O
+
+ +
H
+
RCOO
-
+ RCOOH

V

d:
CH
3
COOH Zn (CH
3
COO)
2
Zn H
2
+ + 2
CH
3
(CH
2
)
10
COOH NaOH CH
3
(CH
2
)
10
COONa H
2
O + +
Axit lauric
C
6
H
5
COOH NaHCO
3
C
6
H
5
COONa CO
2
H
2
O + + +

Hng s axt K
a
ca axt cacbxylic c bc vo khong 10
-4
10
-5
. iu c ngha l
axt cacbxylic rt yu. Kh nng biu hin tnh axt ca n c th so snh vi mt s cht sau
y:
RCOOH > HOH > ROH >HCCH > NH
3
>RH
Cc nhm th khc nhau c mt trong gc R gy nh hng n tnh axt:
- Cc nhm th ht in t s lm tng tnh axt.
- Cc nhm th y in t s lm gim tnh axt.
G C
O
O
- G C
O
O
-
Nhm ht bn ho anion Nhm y gim bn anion.
V d:
CH
3
COOH HCOOH ClCH
2
COOH Cl
2
CHCOOH Cl
3
C COOH
Ka .10
-5
17,7 1,75 136 5530 23200

Cc nhm th v tr gy nh hng ln nht:
Ka .10
-5
CH
3
CH
2
CH
2
COOH CH
3
CH
2
CHCOOH
Cl
CH
3
CHCH
2
COOH
Cl
CH
2
CH
2
CH
2
COOH
Cl
1,52 139 8,9 2,96

Qui lut trn y cng tm thy tng t i vi cc axt thm.
12.5.2. Phn ng cng vo nhm cacbnyl lm t lin kt C-OH
(Z = Cl
-
, RO
-
, NH
2
,...) R CO OH
Z
-
R CO Z

a. Phn ng to thnh cloranhyrat (clorua axit).
R COOH
SOCl
2
PCl
5
PCl
3
+ R COCl
V d:
C
6
H
5
COOH PCl
5
C
6
H
5
COCl POCl
3
HCl +
+ +
100 C
0
SOCl
2
SO
2
HCl
un si
+ + + C
17
H
35
COOH n- C
17
H
35
COCl n-
CH
3
COOH CH
3
COCl
PCl
3
, 50 C
0
b. Phn ng este ho.
RCOOH R'OH
H
+
RCOOR' +
RCOOH
SOCl
2
RCOCl
R'OH
RCOOR'

V d:
C
6
H
5
COOH CH
3
OH
H
+
C
6
H
5
COOCH
3
H
2
O + +
(CH
3
)
3
C COOH
SOCl
2
(CH
3
)
3
C COCl
C
2
H
5
OH
(CH
3
)
3
C COOC
2
H
5

c. Phn ng to thnh amit.
RCOOH
NH
3
RCOONH
4
RCONH
2
un nng
RCOOH
SOCl
2
RCOCl
NH
3
, un nng
RCONH
2
V d:
un nng
CH
3
COOH CH
3
COONH
4
CH
3
CONH
2
NH
3
Axtamit
C
6
H
5
CH
2
COOH
SOCl
2
C
6
H
5
CH
2
COCl
NH
3
C
6
H
5
CH
2
CONH
2
Phnylaxtamit
12.5.3. Phn ng cacbxyl ho.
RCOOH RH CO
2
+
t
0
C
V du:
C
6
H
5
COONa NaOH C
6
H
6
Na
2
CO
3
+ +
CaO, t C
0
O
2
N C
6
H
5
Na
2
CO
3 +
CaO, t C
0
+ NaOH p- O
2
N C
6
H
4
COOH

Nhn chung phng php cacbxyl ho ch c ngha i vi cc axt cacbxylic
thm. i vi cc axt bo phng php ny ch c ngha trong tng hp manlic v tng hp
axtaxt m thi.
V d:
R'CH
2
COOH
CO
2
-
CH
2
COOC
2
H
5
COOC
2
H
5
C
2
H
5
ONa -
CH
COOC
2
H
5
COOC
2
H
5
R'X
CH
COOC
2
H
5
COOC
2
H
5
R'
CH
COOH
COOH
R'

Tng hp manlic cho php iu ch cc dn xut ca axt cacbxylic m trong hyr
c thay th bi cc nhm ankyl khc nhau.
12.5.4. Phn ng th hyr.
a. Halogen ho hyr ca cc axt bo (Phn ng Hen-Fonhac-Zenlinxki).
R CH
H
COOH X
2
P
R CH
X
COOH HX + + (X
2
= Cl
2
, Br
2
)
V d:
Cl
2
, P
CH
3
COOH ClCH
2
COOH Cl
2
CHCOOH Cl
3
C COOH
Cl
2
, P Cl
2
, P
(CH
3
)
2
CH CH
H
COOH
Br
2
, P
(CH
3
)
2
CH CH
Br
COOH
Phn ng ny ch xy ra vi -hyr. Vi -hyr s khng c phn ng xy ra.
C ch ca phn ng:
R CH
H
COOH PX
3
R CH COX
H
POX HX + + +
R CH COX
X
R CH
H
COOH + R CH COX
H
R CH
X
COOH +
R CH COX
H
R CH COX
X
+ X
2
+ HX
P X
2
PX
3
+
Cc hp cht halogenua axt c nhiu ngha trong thc t v qua n c th iu ch
c nhiu hp cht khc nhau nh axt khng no, amin axt, axt a chc
R CH
CN
COOH
R' CH CH COOH
R CH
NH
2
COOH
R CH
OH
COOH
R CH COOH
Br
NaCN
NH
3
d
KOH/ROH (1) HO
-
H
+
(2)
b. Phn ng S
E
nhn thm.
Nhm cacbxyl COOH l nhm th loi 2 nn n c kh nng nh hng mta.
COOH COOH
NO
2
HNO
3
, H
2
SO
4
12.5.5. Phn ng kh
Tc nhn thng dng kh cc axt cacbxylic l LiAlH
4
.
RCOOH RCH
2
OH
LiAlH
4
C ch:
RCOOH LiAlH
4
RCOO
-
Li
+
H
2
AlH
3
+ + +
LiAlH
4
+ R C
O
OLi
R C
H
OLi
OLi
R CH O
R CH O R CH
2
OLi R CH
2
OH + LiAlH
4

V d:
LiAlH
4
CH
3
C
6
H
4
COOH m- CH
3
C
6
H
4
CH
2
OH m-

12.6. CCH NHN BIT AXT CACBXYLIC.
Axt cacbxylic c th nhn bit bng tnh axt ca n: tan trong kim, trong bicacbnat
natri c CO
2
bay ra, hoc bng cc phng php c trng cho cc tnh cht ca axt. Trong ph
hng ngoi, axt cacbxylic c cc s sng c trng sau:
(CO)= 1650-1750 cm
-1
(OH) = 2500-3000cm
-1

B. CC DN XUT CA AXT CACBXYLIC.
12.7. CU TO.
Dn xut cc axt cacbxylic bao gm cloranhyrit, anhyrit, amt v este. Chng l
nhng hp cht m trong nhm OH ca axt c thay th bi Cl, -OCOR, -NH
2
, -OR.
R C
O
OH
R C
O
Cl
R C
O
OCOR
R C
O
NH
2
R C
O
OR'
Axit Cloanhyrit Anhyrit Amit Este

Tt c cc hp cht ny u cha nhm axyl, do cng ging nh cc hp cht khc
chnh nhm nh chc ny quyt nh tnh cht ca cc axt cacbxylic.
R C
O
(Nhm axyl)
12.8. CCH GI TN.
Cc dn xut ca axt cacbxylic c tn gi thng thng v IUPAC tng t nh tn
gi ca cc axt tng ng.
V d:
CH
3
COOH CH
3
COCl (CH
3
CO)
2
O CH
3
CONH
2
CH
3
COOC
2
H
5
Axit axtic
Axit tanic
Axtylclorua
tanylclorua
Anhyrit axtic
Anhyrit tanic
Axtamit
tanamit
tylaxtat
tyltanat

C
6
H
5
COOH C
6
H
5
COCl (C
6
H
5
CO)
2
O C
6
H
5
CONH
2
C
6
H
5
COOC
2
H
5
Axit benzic Benzylclorua Anhyritbenzic Benzamit tylbenzat

12.9. TNH CHT VT L.
S c mt ca nhm cacbnyl CO lm cho tt c dn xut ca axt cacbxylic phn
cc, v vy chng c nhit si gn ging nhit si ca anhyt hoc xton c cng phn
t lng tng ng. Ch c amt c nhit si cao hn v c kh nng to lin kt hyr lin
phn t.
. . . O C
R
N
H
H . . . O C
R
N H . . .
H

Cc dn xut ca axt cacbxylic tan tt trong dung mi hu c v ch c mt s dn
xut c C<5 l tan trong nc.
12.10. PHN NG TH NUCLPHIN CC DN XUT AXT.
Cc hp cht axyl thng c xu hng tham gia phn ng th S
N
m trong cc nhm
OH, -Cl, -OCOR, -NH
2
, -OR c thay th bng mt nhm khc. Phn ng th S
N
y xy
ra d dng hn so vi trng hp phn ng th xy ra i vi cc nhm th lin kt vi nguyn
t cacbon t din.
R C Z
O
W R C O
-
Z
W
R C
O
W Z + +
Z = OH, Cl, OCOR, NH
2
, OR

a. Xt v mt cu to, ging nh anhyt v xton y nhm cacbnyl c ocbitan lai
ho sp
2
, phn cc nn thun li cho s tn cng ca cc tc nhn nuclphin.
C O
Z
R
+
-
0
120
Phn ng xy ra giai on u to thnh trng thi chuyn tip t din nh trong
trng hp i vi anhyt hoc xton nhng trong giai on tip theo thay v bn ho sn
phm bng s kt hp vi prton th xy ra s tch loi nhm Z.
R C R'
O
W R C
R'
W
O
-
H
+
R C
R'
W
OH +
(1) (2)
A
N
R C Z
O
W R C
Z
W
O
-
+
(1) (2)
R C
O
W Z + S
N
b. Phn ng S
N
xy ra cc dn xut ca axt v c th c xc tc bng axt hoc
baz. Trong mi trng baz, nhm OH l mt tc nhn nuclphin mnh, cn trong mi
trng axt prton s prton ho nhm cacbnyl lm gim nng lng hot ho E
a
ca phn
ng.
Thy phn bng baz:
R C
O
Z
HO
-
R C
Z
OH
O
-
R C
O
OH
HO
-
RCOO
-
H
2
O +
Thy phn bng axt:
R C
O
Z R C
OH
Z
+
R C
Z
OH
OH
2
+
RCOOH HZ H
+ H
2
O H
+
+ +
c. Kh nng tham gia phn ng nuclphin ca cc dn xut axt cacbxylic c sp
xp theo dy sau:
R-CO-Cl > R-Cl
R-CO-NH
2
> R-NH
2
R-CO-OR > R-OR
Yu t nh hng n tc phn ng S
N
2 trong cc hp cht R-Z c gy ra bi hiu
ng khng gian (v trng thi chuyn tip nguyn t cacbon c ho tr 5):
W Z
W . . . . . . Z
W Z + +
Tri li trong phn ng S
N
ca cc dn xut axt cacbxylic tc phn ng khng b
nh hng bi hiu ng khng gian m cc yu t xc tin s ph v lin kt s lm tng tc
phn ng v phn ng xy ra qua trng thi chuyn tip t din.
R
O
-
O
R Z
O
R W
W
Z
+
+ W Z
12.1. CLORANHYRIT.
RCOOH
SOCl
2
PCl
5
PCl
3
+ RCOCl
Cloranhyrat tng t nh cc dn xut ca axt cacbxylic tham gia cc phn ng c
trng S
N
. Trong phn ng ny, clo b tch ra di dng ion clo hay HCl. Cloranhyrat l hp
cht c kh nng phn ng mnh nht trong tt c cc dn xut ca axt cacbxylic.
a. Phn ng to thnh axt hoc dn xut ca chng.
RCOCl HZ RCOZ HCl + +

V d:
- Phn ng to thnh axt (phn ng thu phn).
CH
3
COCl H
2
O CH
3
COOH HCl + +
C
6
H
5
COCl H
2
O C
6
H
5
COOH HCl + +

- Phn ng to thnh amt.
CH
3
CH
2
COCl CH
3
CH
2
CONH
2 +
+ NH
4
Cl
NH
4
Cl C
6
H
5
COCl C
6
H
5
CONH
2 + +
NH
3
2
NH
3
2

- Phn ng to thnh este.
CH
3
COCl C
2
H
5
OH CH
3
COOC
2
H
5
HCl + +
C
6
H
5
COCl C
6
H
5
COOC
2
H
5
HCl C
2
H
5
OH + +

b. Phn ng to thnh xton (anxyl ho Frien-Crap).
RCOCl C
6
H
6
AlCl
3
C
6
H
5
COR HCl + +

Phn ng vi hp cht c cadimium.
R'MgX
CdCl
2
R'
2
Cd +
RCOCl
ArCOCl
R CO R'
Ar CO R'

c. Phn ng kh to thnh anhyt.
RCOCl
ArCOCl
H
2
, Pd/BaSO
4
(Pd/S)
RCHO
ArCHO

12.12. ANHYRIT AXIT.
Anhyrit c nhng tnh cht tng t nh cloranhyrat nhng yu hn.
12.12.1. Cc phn ng iu ch.
Trong cc hp cht anhyrit, thng gp v c ngha ln nht l anhyrit axtic. N
c iu ch t xten nh sau:
CH
3
COOH CH
2
C O H
2
O
AlPO
4
, 700 C
0
+
Xten
CH
2
C O CH
3
COOH (CH
3
CO)
2
O +

a. Phn ng to thnh axt v cc dn xut ca n.
(RCO)
2
O HZ RCOZ RCOOH +
+

V d :
- To axt:
(CH
3
CO)
2
O H
2
O CH
3
COOH 2 +

- To amt:
(CH
3
CO)
2
O CH
3
CONH
2
CH
3
COONH
4 + + NH
3
2

- To este:
(CH
3
CO)
2
O CH
3
OH CH
3
COOCH
3
CH
3
COOH + +

c. Phn ng to thnh xton (axyl ho Frien-Crap).
(RCO)
2
O C
6
H
6
R CO C
6
H
5
RCOOH + +
AlCl
3
(CH
3
CO)
2
O CH
3
H
3
C
H
3
C
CH
3
H
3
C
H
3
C
CH
3
CO CH
3
COOH
AlCl
3
+ +
Mzytylen Mtylmzytylxton

12.13. AMIT.
12.13.1. iu ch.
T amnic vi axt cacbxylic hoc vi dn xut ca chng.
a. T cloranhyrat.
RCOCl RCONH
2
NH
4
Cl NH
3
2 + +

V d:
NH
4
Cl NH
3
2 + + Br C
6
H
4
CONH
2
p- p- Br C
6
H
4
COCl

b. T mui amni.
RCOOH NH
3
RCOONH
4
RCONH
2
H
2
O +
t C
0
+

V d:
Axit stearic Stearamit
H
2
O C
17
H
35
COONH
4
n- NH
3
+ + C
17
H
35
COOH n- C
17
H
35
CONH
2
n-
a. Phn ng thu phn.
RCONH
2
H
2
O
H
+
HO
-
RCOOH NH
4
+
RCOO
-
NH
3
+
+
+

V d:
C
6
H
5
CO NH
2
H
2
SO
4
H
2
O C
6
H
5
COOH NH
4
HSO
4
+ + +
CH
3
CH
2
CH
2
CONH
2
NaOH H
2
O CH
3
CH
2
CH
2
COONa NH
3
+ + +

b. Phn ng tch loi Hpman.
RCONH
2
ArCONH
2
OBr
-
RNH
2
ArNH
2
CO
3
-2
Br
-
+ +
y l mt trong nhng phn ng c nhiu thun li, dng iu ch cc amin bc I.
C ch:
+ HO
-
R C
O
N H
Br
R C
O
N
-
Br
H
2
O +
R C
O
N
-
Br
R C
O
N
Br
-
+
R C
O
NH
2
OBr
-
+ R C
O
N H
Br
HO
-
+
R C
O
N
R
R N C O
R N C O + HO
-
2 RNH
2
CO
3
-2
+

12.14.ESTE.
Este l nhng hp cht c cng thc cu to RCOOR. Cc este thng c mi c trng
cho hoa qu chn. V d tylfocmiat c mi ru rum, tylbutyrat c mi da, izamylaxtat c
mi chuiV vy cc este c nhiu ng dng trong cng nghip thc phm.
12.14.1. iu ch.
Cc este thng c iu ch bng phn ng ca ancol hay phnol vi axt hoc dn
xut ca n. Sau y l mt s phng php iu ch quan trng.
a. iu ch este t axt.
RCOOH R'OH RCOOR' H
2
O
H
+
+ +

V d:
CH
3
COOH HOCH
2
C
6
H
5
H
+
CH
3
COOCH
2
C
6
H
5
H
2
O + +

C
6
H
5
COOH HOCH
2
CH(CH
3
)
2
C
6
H
5
COOCH
2
CH(CH
3
)
2
H
+
+
+ H
2
O
izbutylbenzat

c. T cloranhyrat, anhyrit axt.
RCOCl R'OH hoc ArOH RCOOR' hoc RCOOAr +
+ R'OH hoc ArOH RCOOR' hoc RCOOAr (RCO)
2
O
V d:
+
p- p- (CH
3
CO)
2
O
NaOH
CH
3
COO C
6
H
4
NO
2
HO C
6
H
4
NO
2
piriin
C
2
H
5
OH + Br C
6
H
4
COOC
2
H
5
o- Br C
6
H
4
COCl o-
d. Phn ng trao i este.
RCOOR' R"OH RCOOR'' R'OH
H
+
+
+

Trong cc phn ng nu trn y, phn ng tc dng trc tip ancol hoc phnol vi
axt cacbxylic l phn ng thun nghch v vy mun tng hiu sut ca phn ng cn phi
tin hnh trong iu kin khc nghit (c bit i vi phn ng ca phnol) v chuyn hng
phn ng v pha bn phi bng cch tng nng ca mt trong hai cht tham gia phn ng,
tch sn phm ngay trong qu trnh phn ng (este hoc nc), s dng xc tc thch hp
Phng php este ho c ngha ln trong cng nghip. Trong phng th nghim thng s
dng phng php iu ch este t cloranhyrat hoc anhyrit axt.
Este tham gia phn ng th nuclphin c trng cho cc dn xut ca axt cacbxylic
dn n kt qu nhm OR c thay th bi cc nhm OH, -OR hoc NH
2
.
R C
O
OR' Z
-
R C
OR'
O
-
Z R C
O
Z R'O
-
+ +
(Z
-
= HO
-
, R''O
-
, NH
3
)

a. Phn ng to thnh axt v dn xut ca n.
- To thnh axt:
RCOOR' H
2
O
H
+
HO
-
RCOOH R'OH
RCOO
-
R'OH
+
+
+

V d:
C
6
H
5
COOC
2
H
5
H
2
O
C
6
H
5
COOH C
2
H
5
OH
C
6
H
5
COONa C
2
H
5
OH
H
2
SO
4
NaOH
+
+
+

- To thnh amt:
RCOOR' NH
3
RCONH
2
R'OH + +

V d:
CH
3
COOC
2
H
5
NH
3
CH
3
CONH
2
C
2
H
5
OH + +

- To thnh este mi (phn ng trao i este).
RCOOR' R"OH RCOOR'' R'OH
H
+
+
+

V d:
CH
2
CH
OCOR
OCOR'
CH
2
OCOR'
CH
3
OH
H
+
CH
2
OH
CH OH
CH
2
OH
+ +
CH
3
OCOR
CH
3
OCOR'
CH
3
OCOR'

b. Phn ng vi tc nhn Grinha.
RCOOR' 2R'MgX R C
R'
OH
R' +
V d:
C
6
H
5
COOC
2
H
5
C
6
H
5
C
C
6
H
5
C
6
H
5
OH
C
6
H
5
MgBr 2 +
Triphnylcacbinol

c. Kh thnh ancol .
- Kh ho xc tc:
RCOOR' H
2
RCH
2
OH R'OH + +
CuO.CuCr
2
O
4
V d:
(CH
3
)
3
C COOC
2
H
5
H
2
(CH
3
)
3
C CH
2
OH C
2
H
5
OH + +
CuO.CuCr
2
O
4

- Kh ho ho hc :
RCOOR' LiAlH
4
RCH
2
OH R'OH +
te khan, H
+
+
RCOOR' RCH
2
OH R'OH
Na, ancol
+
V d:
CH
3
(CH
2
)
6
COOC
2
H
5
CH
3
(CH
2
)
6
CH
2
OH C
2
H
5
OH +
Na, C
2
H
5
OH
d. Phn ng th -hyr linh ng.
- Phn ng ngng t este (ngng t Claizen).
y l phn ng ca 2 phn t etse vi nhau khi c xc tc natri kim loi hoc natri
ancolat to thnh este axt -xt-cacbxylic.
R C
O
OC
2
H
5
H CH
R'
COOC
2
H
5
NaOC
2
H
5
R C
O
CH
R'
COOC
2
H
5
tylaxtoaxtat
+
V d:
H CH
2
COOC
2
H
5
CH
3
CO CH
2
COOC
2
H
5
CH
3
CO OC
2
H
5 +
C
2
H
5
ONa

- Tng hp malnic.
CH
2
COOC
2
H
5
COOC
2
H
5
C
2
H
5
ONa -
CH
COOC
2
H
5
COOC
2
H
5
RX
CH
COOC
2
H
5
COOC
2
H
5
R
H
2
O, H
+
CH
COOH
COOH
R
t
0
C
RCH
2
COOH CO
2 +
12.14.3. Phn ng thu phn este.
Este ca axt cacbxylic c th b thu phn to thnh axt v ancol hoc phnol bi axt
hoc baz khi un nng.
a. Thu phn bng baz.
S thu phn este bng baz c gy ra bi s tn cng ca tc nhn nuclphin
mnhHO
-
. Phn ng thc t khng thun nghch v anion cacbxylic c bn ho bi s cng
hng nn rt kh phn ng tr li vi ancol.
- C ch:
R C
O
OR'
HO
-
R C
O
-
OH
OR' C R
O
O
- R'OH +
+
(I)
Trong cng thc cng hng (I) trn y in t p ca nguyn t cacon cacbnyl tham
gia xen ph vi in t p ca c 2 nguyn t xi lm tng thm mt in t xen ph cc i
dn n lin kt bn hn nn anion cng bn hn.
- Chng minh c ch phn ng.
1- Phn ng xy ra bi s tn cng ca nhm OH: iu ny c xc nhn bng thc
nghim ng hc, rng y l phn ng bc II v tc ca phn ng ph thuc nng vo
ca c este ln HO
-
:
v = k[RCOOR][HO
-
]
2- Nhm hyrxyl HO
-
c cng vo nguyn t cacbon cacbnyl v tch i ion ancolat
- tc l phn ng xy ra vi s t lin kt gia xy v nhm axyl. iu ny c chng minh
bng 2 cch sau y:
* Phng php ho lp th.
Khi cho benzylclorua tc dng vi ru (+)-sec-butylic quang hot, ngi ta thu c
sec-butylbenzat m trong khng lm thay i cu hnh ca nguyn t cacbon bt i v
khng lm ph v lin kt no ca n.
CO O C
6
H
5
H
C
2
H
5
CH
3
C
6
H
5
CO Cl + O H H
C
2
H
5
CH
3
Khi thu phn este ny bng HO
-
s xy ra 2 kh nng sau:
C
6
H
5
C
O
O
C
2
H
5
CH
3
H
(1)
HO
-
(2)
(1)
C
6
H
5
COOH HO
C
2
H
5
CH
3
H +
(2)
C
6
H
5
COOH + H
C
2
H
5
CH
3
OH
Nu phn ng xy ra theo (1) th ru sec-butylic thu c s khng b i cu hnh v
cc lin kt vi nguyn t cacbon bt i xng khng b ph v.
Nu xy ra theo (2) th ru sec-butylic thu c hoc l b thay i cu hnh hon ton
(nu xy ra phn ng th S
N
2) hoc to ra bin th raxmic (nu xy ra phn ng S
N
1).
Thc nghim chng minh rng ru sec-butylic thu c sau phn ng hon ton
khng thay i cu hnh-ngha l xy ra s t lin kt gia xy v nhm cacbxyl RCO-
OR.
Phng php nh du nguyn t:
Trong phng php ny, ngi ta tin hnh thu phn tylprpanat c nh du bng
O
18
v thu c ru tylic c cha O
18
:
CH
3
CH
2
CO O C
2
H
5
18
HO
-
CH
3
CH
2
COOH C
2
H
5
O H
18
+ +

iu mt ln na chng minh rng trong phn ng thu phn este xy ra s
phn ct lin kt gia nguyn t xy v nhm axyl.
Phn ng cng xy ra tng t i vi cc dn xut khc ca axt cacbxylic.
b. Thu phn bng axt.
RCOOR' H
2
O
H
+
RCOOH R'OH + +

C ch:
R C
OH
OH
OR' H
+
-R'OH -H
+
RCOOH
R C
O
OR'
H
+
H
2
O
R C
OH
OH
2
OR'
+
+ R C
OH
OR'
+
OH
R C
OH
+
Axt v c trong phn ng ny ng vai tr prton ho nguyn t xy ca nhm
cacbnyl lm tng kh nng phn ng nuclphin ca nguyn t cacbon.
12.15. CHT BO.
12.15.1. Cht bo trong t nhin v thnh phn ho hc ca n.
Mt s este thng gp trong t nhin c ngha rt quan trng i vi i sng l
cht bo (dng lng thng gp gi l du): du da, du u phng, du bng, du ng, du
liu, du c(dng sp, m): m heo, m b, m d, m cu
Tt c cc loi este ny u c to thnh t mt gc ru a chc glyxrin vi cc
gc axt cacbxylic khc nhau, do cn c tn gi l cc hp cht glyxrit.
Hu ht cc axt cacbxylic to thnh cht bo l axt mch h cha t 3 n 18 nguyn
t cacbon. Tr 2 loi axt c s l nguyn t cacbon C
3
v C
5
cn li tt c cc axt cu to nn
cht bo u c s nguyn t cacbon l s chn. Ngoi ra cc axt cacbxylic cng c th no,
khng no mt hoc nhiu ni i.
Nh vy thnh phn ca mt cht bo l mt hn hp glyxrit vi nhng t l khc nhau
v chnh cc t l khc nhau c trong thnh phn ca cht bo quyt nh loi cht bo, dng
tn ti v mu sc, mi vca cht bo.
12.15.2. Phn ng thu phn cc cht bo.
Cc cht bo c th thu phn bi axt hoc baz. Nu thu phn bng baz th ngi ta
gi l phn ng x phng ho.
CH
2
OCOR
CH OCOR'
CH
2
OCOR'
NaOH
CH
2
OH
CH OH
CH
2
OH
RCOONa
R'COONa
R'COONa
+
Glyxrin X phng

Nh vy, c x phng ngi ta tin hnh thu phn cc cht bo bng dung dch
kim. c x phng khng mu khi thu phn cn cho thm ru, x phng c mu, c
mi cn cho thm cc cht ph gia nh phm mu, tinh du trnh hi da cn cho thm cc
cht kh trng.
Nu thu phn cc este bng NaOH ta s c x phng cng (rn), cn nu thu phn
bng KOH s thu c x phng mm (x phng nc).
12.1. T dn xut halogen, vit phng trnh phn ng iu ch cc axit sau:
a. Axit propionic
b. Axit izobutyric
c. Axit phenyl axetic
12.2. Sp xp cc hp cht sau y theo th t tng dn tnh axit:
a. CH
3
COOH, CCl
3
COOH, CHCl
2
COOH, CH
2
ClCOOH
b. (CH
3
)
3
C-COOH, (CH
3
)
2
CH-COOH, CH
3
CH
2
COOH, CH
3
COOH
c. C
6
H
5
COOH, p-CH
3
-C
6
H
4
COOH, p-NO
2
-C
6
H
4
COOH
12.3. Gi tn cc hp cht sau theo danh php quc t v tn thng thng (nu c):
CH
3
(CH
2
)
3
COOH CH
3
C
CH
3
CH CH
2
COOH
HOOC C
H
C
H
COOH HOOC C
H
C
H
COOH
CH
3
CH CH
2
C
O
Cl
Cl
CH
3
CH
2
C
O
N
CH
3
CH
3
a. b.
c. d.
e. f.
12.4. iu ch cc hp cht sau:
a. Axit 4-phenyl butanoic t toluen
b. Benzylamin t benzamid
c. Anilin t benzamid
d. butanon-2 t acetonitril
e. Axit benzoic t brombenzen
f. Axit 2,2-dimetyl propanoic t tec-butyl bromua
12.5. Trnh by c ch ca cc phn ng sau y:
R C NH
2
O
Br
2
, HO
-
RNH
2
R C
O
Cl
1. CH
2
N
2
2. Ag
2
O, H
2
O
RCH
2
COOH
R C N
H
3
O
+
RCOOH
a.
b.
c.

12.6. S thu phn trong mi trng axit ca 1-metylpropyl axetat c tnh quang hot xy ra
vi s lu gi cu hnh. Trnh by c ch ca phn ng thu phn trn.
ha hc hu c.
H Ni.
Ni.
Chng 13
AMIN
13.1. CU TO PHN LOI V CCH GI TN.
13.1.1. Cu to.
Amin l cc hp cht c cng thc phn t tng qut: RNH
2
, R
2
NH hoc R
3
N trong
R-ankyl hoc aryl.
V d:
CH
3
NH
2
(CH
3
)
2
NH (CH
3
)
3
N H
2
N CH
2
CH
2
NH
2
Mtylamin imtylamin Trimtylamin tyleniamin
(Amin 1 )
0
(Amin 2 )
0
(Amin 3 )
0
(Amin 1 )
0
(Amin 3 )
0
NH
2
NHCH
3
N(CH
3
)
2
Anilin N-Mtylanilin N,N-imtylanilin
(Amin 1 )
0
(Amin 2 )
0
13.1.2. Phn loi.
Amin c phn thnh bc I, bc II, bc III ph thuc vo s lng cc nhm th lin
kt vi nguyn t nit.
R N
H
H R N R
H
R N R
R
(Amin 2 )
0
(Amin 1 )
0
(Amin 3 )
0
13.1.3. Cch gi tn.
Tn gi ca cc amin bo c hnh thnh bng cch thm ui amin vo tn gi ca
nhm ankyl hoc cc nhm th lin kt vi nhm amin. Trng hp i vi cc amin phc
tp thng ngi ta thm cc tip t amin- (hoc N-mtylamin-, N,N-imtylamin-) vo
tn gi ca mch chnh.
V d:
(CH
3
)
3
C NH
2
CH
3
CH
2
NH CH
3
(CH
3
)
2
N C
2
H
5
Tec-butylamin tylmtylamin imtyltylamin

H
2
N CH
2
CH
2
OH CH
3
NH CH(CH
3
) CH
2
(CH
2
)
3
CH
3
2-amintanol 2-(N-Mtylamin)-heptan

Cc amin thm trong nguyn t hyr lin kt trc tip vi nhn thm thng c
gi nh l dn xut ca anilin. Mui ca cc hp cht ny c gi bng cch thay ui amin
thnh amni (hoc anilin thnh anilini).
V d:
NH
2
Br
Br
Br
N C
2
H
5
CH
3
N(CH
3
)
2
NO
2
CH
3
NH
2
2,4,6-Tribrmanilin N-Mtyl-N-tylanilin p-nitr-N,N-imtylanilin p-Tluin
(C
2
H
5
NH
3
)
2
SO
4
-2
+
(CH
3
)
3
NHNO
3
-
+
C
6
H
5
NH
3
Cl
- +
Sunfat itylamni Nitrat trimtylamni Clorua anilini

13.4. TNH CHT VT L.
Tng t nh amnic, cc amin l nhng hp cht phn cc tr amin bc III v chng
c kh nng to lin kt hyr lin phn t. Amin c nhit si cao hn cc hp cht khng
phn cc c cng phn t lng nhng thp hn nhit si c ancol v axt cacbxylic tng
ng. Amin c kh nng to lin kt hyr vi nc v vy nhng amin thp (c s nguyn t
cacbon nh thua 6) ho tan tt trong nc. Amin t tan trong cc dung mi t phn cc nh ete,
benzen
Mtylamin v tylamin c mi ging amnic. Cc amin cao hn c mi ta mi tanh
ca c. Amin thm l nhng cht c v d b xy ho bi khng kh.
13.5. IU CH.
Mt s amin quan trng c s dng rng ri trong cng nghip iu ch theo cc
phng php sau y:
a. Anilin.
Anilin c iu ch bng cch:
1- Kh ho ho hc hoc kh ho xc tc cc hp cht nitrbenzen.
C
6
H
5
NO
2
Fe, HCl , t
0
C
C
6
H
5
NH
3
Cl
-
+ Na
2
CO
3
C
6
H
5
NH
2
2- Chuyn ho clobenzen bng mnic nhit v p sut cao c xc tc.
C
6
H
5
Cl C
6
H
5
NH
2
NH
3
, CuO, 200 C, 65at
0
b. Mtylamin, imtylamin, trimtylamin.
Cc hp cht ny c iu ch t ru mtanol v amnic c xc tc.
450 C 450 C 450 C
NH
3
CH
3
NH
2
(CH
3
)
2
NH (CH
3
)
3
N
CH
3
OH CH
3
OH CH
3
OH
Al
2
O
3
,
0
Al
2
O
3
,
0
Al
2
O
3
,
0

c. iu ch cc amin bc cao.
Trong cng nghip iu ch cc amin bc cao ngi ta s dng cc phn ng amin
ho cc ankylhalogenua. Ngoi ra mt s amin c s chn cc nguyn t cacbon c th c
iu ch t cc axt bo-sn phm thu phn ca cc cht bo.
H
2
, Ni
RCOOH RCONH
2
R C N R CH
2
NH
2
un nng NH
3
, t
0
C
13.5.2. Cc phng php phng th nghim.
a. Kh ho cc hp cht nitr.
R NH
2
Ar NH
2
H
2
/xt
Kim loi/axit
R NO
2
Ar NO
2

V d:
CH
3
CH
2
CH
2
NO
2
Fe, HCl
CH
3
CH
2
CH
2
NH
2
H
2
, Pd
tyl-p-nitrbenzat tyl-p-aminbenzat
C
2
H
5
OOC C
6
H
4
NO
2
p- C
2
H
5
OOC C
6
H
4
NH
2
p-
Sn, HCl
H
2
N C
6
H
4
NO
2
p-
H
2
N C
6
H
4
NH
2
p-
NH
4
SH
O
2
N C
6
H
4
NO
2
o- O
2
N C
6
H
4
NH
2
o-
O
2
N C
6
H
4
CH CH R
Phng php kh ho cc hp cht nitr ch yu dng iu ch cc hp cht amin
thm. Trng hp trong nhn thm c nhiu nhm NO
2
m ch mun kh mt nhm th
thng s dng tc nhn (NH
4
SH). Phng php ny ch c ngha ln trong trng hp trong
phn t ca hp cht c nhm nitr cn kh khng cha cc nhm th d b kh ho hn. V d
trong phn ng sau y lin kt kp s b kh trc nhm nitr.
H
2
, Ni
o- o-O
2
N C
6
H
4
CH
2
CH
2
R

c. Phn ng ca dn xut halogen vi amnic, vi amin.
NH
3
RX
RNH
2
R
2
NH R
3
N R
4
N
+
X
- RX RX RX
( R- ankyl hoc aryl c nhm th loi II)

V d:
CH
3
COOH
Cl
2
, P
Cl CH
2
COOH H
2
N CH
2
COO
-
NH
4
+ H
+
H
2
N CH
2
COOH
NH
3
C
6
H
5
CH
2
Cl
NH
3
C
6
H
5
CH
2
NH
2
CH
3
Cl
C
6
H
5
CH
2
N(CH
3
)
2

2,4-initrclobenzen N-Mtyl-2,4-initranilin
Cl
NO
2
NO
2
NH
2
NO
2
NO
2
NHCH
3
NO
2
NO
2
NH
3
CH
3
Cl
Phn ng amin ho dn xut halogen xy ra theo c ch th nuclphin m trong
amnic hoc amin l tc nhn nuclphin.
H
3
N R X H
3
N . . . R. . . X
- +
H
3
N R
+
X
-
+ + S 2
N

V vy hp cht amin thu c vi hiu sut ln khi dn xut halogen tham gia phn
ng l bc I. Trong trng hp dn xut halogen l 3
0
th sn phm phn ng ch yu ca phn
ng l sn phm tch loi.
V d:
CH
3
CH
2
CH
2
CH
2
Br CH
3
CH
2
CH
2
CH
2
NH
2
NH
3
S
N
NH
3
(CH
3
)
2
C CH
3
Br
(CH
3
)
2
C CH
2
NH
4
Br
+ E
Nhc im ln nht ca phn ng amin ho theo cch ny l sn phm thu c l
mt hn hp cc hp cht amin vi bc khc nhau.
V d:
(Amin 1 )
0
(Amin 2 )
0
(Amin 3 )
0
(Amin 4 )
0
RX NH
3
RNH
2
+
R
2
NH RX RNH
2
+
R
3
N RX R
2
NH +
R
4
N
+
X
-
RX R
3
N +

V vy hiu sut sn phm ch yu to thnh amin 1
0
, ngi ta phi cho mt lng
NH
3
d rt ln.
c. Kh ho-amin ho.
Phn ng chuyn ho mt s anhyt RCHO v xton RCOR thnh amin di tc dng
ca hyr, amnic, khi c mt ca xc tc kim loi.
C O
NH
3
H
2
Ni
CH NH
2
+ +
RNH
2
CH NHR H
2
Ni
+ +
R
2
NH CH NR
2
Ni
H
2
+ +

V d:
CH
3
CO CH
3
NH
3
H
2
CH
3
CH CH
3
NH
2
+ +
Ni
CH
3
CH
2
CH
2
CHO C
6
H
5
NH
2
H
2
Ni
C
6
H
5
NH CH
2
CH
2
CH
2
CH
3
+ +
CH
3
CHO (CH
3
)
2
NH + + H
2
CH
3
CH
2
N(CH
3
)
2
Ni
Cho n nay c ch ca phn ng ny vn cha c chng minh y nhng c
nhiu gi thit cho rng phn ng xy ra qua bc to thnh hp cht trung gian imin
RCH=NH hoc R
2
C=NH.
RCHO NH
3
H
2
, Ni
RCH
2
NH
2
RCH NH +
R C
O
R' NH
3
H
2
, Ni
R CH
R'
NH
2
+ R C
R'
NH
u im ln nht ca loi phn ng ny l c th iu ch nhng amin 2
0
m bng phn
ng amin ho cc dn xut halogen khng th iu ch c.
V d:
OH
K
2
C
2
O
7
, H
2
SO
4
O NH
2
PBr
3
Br
NH
3
NH
3
H
2
, Ni
Nhc im chnh ca phng php ny l cng to thnh hn hp sn phm amin cc
bc khc nhau do iu ch amin 1
0
phi cho NH
3
d.
d. Kh ho hp cht nitrin.
R CN
H
2
, xt
RCH
2
NH
2

V d:
C
6
H
5
CH
2
Cl NaCN C
6
H
5
CH
2
CN
H
2
, Ni, 140 C
0
+ C
6
H
5
CH
2
CH
2
NH
2
ClCH
2
CH
2
CH
2
CH
2
Cl
NaCN
NC (CH
2
)
4
CN H
2
N (CH
2
)
6
NH
2
H
2
, Ni
Aipnitrin Hecxamtyleniamin

e. Tch loi amt theo Hpman.
OBr
-
CO
3
-2
Br
-
RNH
2
ArNH
2
RCONH
2
ArCONH
2
(Br
2
KOH) +
+ +
g. Tng hp amin 1
0
tinh khit theo phng php Gabrien.
Cc anhyrit mch vng tng t nh anhyrit mch h khi tc dng vi amnic to
thnh amt v nu cho amt un nng th s thu c hp cht imt. u im ca phn ng ny
l cho php gn mt nhm ankyl vo nguyn t nit m thi nn sn phm thu c ch duy
nht l amin 1
0
.
C
O
C
O
NH
NH
3
, un nng un nng
CONH
2
COOH
CONH
2
COONH
4
C
O
C
O
O
NH
3 H
+
C
O
C
O
NH
C
O
C
O
N
-
K
+
C
O
C
O
N R
RX KOH
R NH
2
Qua cc phng php iu ch amin nu trn y ta c th rt ra mt s nhn xt sau:
1- Phng php kh ho cc hp cht nitrin lm tng thm mch cacbon ca phn t hp
cht ban u.
2- Tch loi Hpman, ngc li lm gim mch cacbon.
3- Cc phng php amin ho ankylhalogenua, kh ho-amin ho anhyt hoc xton
u gi nguyn mch cacbon.
13.6. TNH CHT HA HC.
Tt c cc hp cht amin tng t nh amnic, nguyn t nit c cha cp in t
khng phn chia l tc nhn nuclphin trong cc phn ng.
1- Tnh baz-cc phn ng to mui.
R
3
N R
3
NH
+
H
+
+
RNH
2
H
+
RNH
3
+
+
R
2
NH R
2
NH
2
+
H
+
+
V d:
C
6
H
5
NH
2
HCl C
6
H
5
NH
3
Cl
-
+
+
(CH
3
)
2
NH HNO
3
(CH
3
)
2
NH
2
NO
3
-
+
+
2- Phn ng ankyl ho cc amin.
RNH
2
R
2
NH R
3
N R
4
N
+
X
- RX RX RX
ArNH
2
RX RX RX
ArNHR ArNR
2
ArNR
3
X
-
+
3- Phn ng to thnh amit.
RNH
2
R'COCl
ArSO
2
Cl
R' CO NHR
Ar SO
2
NHR
Amin 1
0
Sn phm N-amit
Sn phm N-sunfamit
R
2
NH
R' CO NR
2
Ar SO
2
NR
2
R'COCl
ArSO
2
Cl
Sn phm N,N-amit
Sn phm N,N-sunfamit
Amin 2
0

Cc amin bc 3
0
khng tham gia cc phn ng trn y.
V d:
C
6
H
5
NH
2
C
6
H
5
SO
2
Cl
CH
3
COCl
CH
3
CO NH C
6
H
5
C
6
H
5
SO
2
NH C
6
H
5
Axtanilit
N-Phnylbenzensunfamit

4- Phn ng th ca cc amin thm.
Cc amin thm c cc nhm th -NH
2
, -NHR, -NR
2
v NHCOR l nhng nhm th loi
I nn nh hng cc sn phm th vo v tr ct v para.
V d:
NH
2
NH
2
Br
Br
Br
Br
2
(CH
3
CO)
2
O
NHCOCH
3
NHCOCH
3
Br
H
2
O, H
+
NH
2
Br
Br
2
5- Phn ng vi axt nitr.
Amin thm 1
0
Mui iazni
ArNH
2
HNO
2
/HCl
Ar N N Cl
-
+
RNH
2
R N N Cl
-
+ H
2
O
N
2
HNO
2
/HCl
ROH +
Amin 1
0

Vi amin 1
0
c phn t lng ln hn, khi cho tc dng vi axit nitr (HNO
2
) s to ra
anken.
Ar NHR
HNO
2
/HCl
R
2
NH
Ar NR N O
R
2
N N O
Amin 2
0
Ar NR
2
HNO
2
/HCl
R
3
N
p- R
2
N C
6
H
4
NO
R
3
N N O Cl
-
+
Amin 3
0
6- Phn ng tch loi Hpman.
C
H NR
3
C
+
HO
-
, t
0
C
C C R
3
N H
2
O + +
13.7. CCH NHN BIT AMIN.
Cc amin c th nhn bit bng tnh cht kim ca n, tnh t tan trong nc nhng tan
tt trong axt HCl long v lnh.
- +
phn bit cc amin bc 1
0
, 2
0
, 3
0
ngi ta dng phn ng Kinsberg: cho amin tc
dng vi benzensunfclorua trong dung dch KOH.
khng phn ng tan Amin 3
0
HO
-
C
6
H
5
SO
2
Cl R
3
N + R
3
N
HCl
R
3
NHCl
-
+
Amin 2
0
khng tan
Khng thay i R
2
NH C
6
H
5
SO
2
Cl
HO
-
C
6
H
5
SO
2
NR
2
+
KOH hoc H
+
Amin 1
0
tan khng tan
RNH
2
C
6
H
5
SO
2
Cl C
6
H
5
SO
2
NHR C
6
H
5
SO
2
N
-
K
+
R
H
+
C
6
H
5
SO
2
NHR
KOH
HO
-
+
13.1. Gi tn cc hp cht sau y:
CH
3
CH CH
2
NH
2
CH
3
CH
3
CH
CH
3
CH
2
NH CH
3
CH
3
N
CH
2
CH
2
CH
3
CH
2
CH(CH
3
)
2
H
2
C CH CH
2
NH
2
(CH
3
)
2
NCH
2
CH
2
OH
CH
3
CH
N(CH
3
)
2
CH
2
C N
a. b.
c. d.
e. f.
13.2. Hy sp xp theo th t tng dn tnh baz ca cc hp cht sau:
a. C
2
H
5
NH
2
, NH
3
, (C
2
H
5
)
2
NH, (C
2
H
5
)
3
N
b. C
6
H
5
NHCH
3
, C
6
H
5
NH
2
, C
6
H
5
N(CH
3
)
2
, p-NO
2
-C
6
H
4
NH
2
c. p-CH
3
-C
6
H
4
NH
2
, C
6
H
5
CH
2
NH
2
, (C
6
H
5
)
2
NH, (C
6
H
5
)
3
N
13.3. Vit cng thc cu to ca cc hp cht sau:
a. p-nitro-N-metyl-N-etylanilin b. 3-(N,N-diallylamino)-2-hexanon
c. 4-(N-butyl-N-vinylamino)-2-pentanol d. N,N-diphenyletylendiamin
e. N,N- diphenyletylendiamin f. 1,2-propandiamin
g. Benzyltrimetylamoni Iodua h. Tetrametylamoni Hidroxit
13.4. Vit phng trnh phn ng ca 2-aminobutan vi:
a. HCl b. CH
3
COCl
c. Benzensunfonyl clorua d. NaNO
2
trong dung dch HCl
13.5. Hp cht A (C
5
H
11
NO) khng tan trong dung dch axit hay baz long nhit thng.
Khi un nng A vi dung dch NaOH ta c mt mui B v mt kh C. Khi C tc dng vi
benzensunfonyl clorua cho ra benzensunfonamid khng tan trong baz d. Khi B tc dng vi
HCl to ra D tan d dng trong baz long, D tc dng vi SOCl
2
cho ra E. Khi E phn ng
lng tha NH
3
cho ra G, G phn ng vi Br
2
, NaOH cho ra etylamin. Hy cho bit cng thc
cu to ca cc cht t A ti G.
ha hc hu c.
H Ni.
Ni.
Chng 14
HP CHT D VNG V CC ANKALOIT
A. HP CHT D VNG.
14. NH NGHA.
Hp cht d vng l nhng hp cht c cha trong mch vng ca n hoc mt s nguyn
t ca cc nguyn t khng phi l cacbon (xy, lu hunh, xilen, nit, photpho, silic, ch, thu
ngn). Thng thng trong cc trng hp cht d vng hay gp cc cht d vng c cha
nit, lu hunh v xy.
V d:
N
H
O S N
H
N
Pyrol Furan Thiphen Pyrliin Piriin
N
N
N
N
CH
3
N
H
Quinlin Izquinlin Carbazol Nictin

Trong chng ny chng ta s nghin cu mt s hp cht ca cc h d vng c tnh
thm.
14.2. CC HP CHT D VNG 5 CNH
14.2.1. Cu to ca pirol, furan, tiphen.
Cc hp cht d vng n gin nht 5 cnh l pirol, futan, tiphen.
N
H
O S
I II III

Nu ch xem xt cc cng thc cu to I, II, III ta c th d on cc hp cht ny mang
tnh cht ca h ien lin hp v cc tnh cht ca amin, te v sunfua. Nhng thc nghim
cho thy rng cc hp cht ny c biu hin mt s tnh cht hon ton khc hn vi nhng
d on rt ra t nhng cng thc cu to I, II, III. V d tiphen iu kin bnh thng
khng tham gia phn ng xy ho l phn ng c trng cho cc hp cht sunfua cn pirol li
khng tham gia cc phn ng biu hin tnh baz c trng cho cc hp cht amin. Mt khc
cc hp cht pirol, furan, tiphen v cc dn xut ca n li c kh nng tham gia phn ng
electrphin nh nitr ho, sunf ho, halogen ho k c phn ng ghp iazni. Tt c cc
tnh cht trn c gii thch tho mn rng cc hp cht pirol, furan, tiphen l nhng hp cht
thm v s in t p ca cc hp cht trn y ph hp vi qui tc 4n +2 ca Huycken l 6 in
t. Mi mt nguyn t ca vng k c Ccbon ln nit s dng 3 lin kt ca obitan lai
ho sp
2
lin kt vi nhau. Nh vy mi nguyn t cacbon cn li mt in t p v nguyn t
nit cn li 2 in t p (trong trng hp pirol). S xen ph ca cc in t p ny dn n
hnh thnh m my in t lin kt nm pha trn v nm pha di mt phng ca vng.
Cp in t ca nit trong trng hp ny tham gia xen ph vi h in t p ca cacbon nn
khng cn c kh nng th hin tnh baz na. Tri li mt in t ca vng tng ln nn
lm xut hin cc kh nng tham gia phn ng th electrphin ca pirol.
N
H
H H
Tng t nh vy cc hp cht furan v thiphen cng mang tnh cht ca cc hp cht
thm.
14.2.2. Cc phng php iu ch pirol, furan, tiphen.
Pirol v tiphen c cha mt lng khng ln lm trong nha than . Trong cng
nghip tiphen c iu ch bng phn ng gia butan v lu hunh nhit cao.
CH
3
CH
2
CH
2
CH
3
S
560 C
0
S
H
2
S + +
Pirol c th tng hp bng nhiu cch khc nhau m di y l mt trong cc phng
php .
HC CH 2HCHO HOCH
2
C C CH
2
OH
NH
3
, P
N
H
+
Furan c iu ch bng phng php cacbxyl ho fufurol, sn phm ca qu trnh
thy phn pentza bng HCl.
(C
5
H
8
O
4
)n
H
2
O/H
+
HOCH
2
(CHOH)
3
CHO
O
CHO
O
xt, t
0
C
Pentzan Pentza

Cc hp cht pirol, furan, tiphen cng c th c iu ch bng phng php vng
ho.
V d:
H
3
C C
CH
2
CH
2
C CH
3
O O
P
2
O
5
, t
0
C
O
CH
3
H
3
C
(NH
4
)
2
CO
3
, 100 C
0
P
2
S
5
, t
0
C
N
CH
3
H
3
C
H
S
CH
3
H
3
C
Hecxaion-2,5
14.2.3. Phn ng th electrphin ca pirol, furan, tiphen.
Tng t nh cc hp cht thm pirol, furan, tiphen tham gia cc phn ng nitr ho,
halogen ho, sunfnic hoKh nng tham gia phn ng ca chng mnh hn benzen. Phn
ng thng xy ra vi s u tin nh hng vo v tr 2.
V d:
O O
COCH
3
(CH
3
CO)
2
O
(C
2
H
5
)
2
O BF
3
+
O
SO
3
O
SO
3
H
Piriin
+
N
H
N
H
CHO CHCl
3
KOH + +
N
H
N
H
N N
-
ClN N
+
+
S S
COC
6
H
5
C
6
H
5
COCl
SnCl
4
+
C ch ca cc phn ng trn y xy ra tng t nh phn ng th electrphin vo nhn
thm.
N
H
Y
+
N
H
Y
H
+
N
H
Y
chm
nhanh
+
Trong s c ch ca phn ng trn y ta nhn thy pirol tham gia phn ng th S
E

mnh hn benzen v to thnh phc m trong cc nguyn t u c 8 electron lp ngoi cng
nn bn vng hn so vi phc ca benzen.
N
H
+
Phc ca pirol Phc ca benzen
+
Tng t nh vy ngi ta gii thch kh nng tham gia phn ng S
E
ca furan v
tiphen.
Cc hp cht pirol, furan khi b hyr ho c xc tc s to thnh nhng hp cht d
vng no tng ng-piroliin v ttrahyrfuran. Piroliin v ttrahyrfuran hoc
ttrahyrtiphen biu hin cc tnh cht tng t vi cc loi hp cht ca n: amin bc II, te
hoc sunfua.
N
H
N
H

O O

Ttrahyrfuran l mt dung mi rt quan trng c s dng rng ri trong cng
nghip v trong phng th nghim, c bit l trong cc phn ng kh ho bng Liti nhm
hyrua.
14.3. CC HP CHT D VNG 6 CNH.
14.3.1. Cu to ca piriin.
Trong cc hp cht d vng thm 6 cnh, chng ta tin hnh nghin cu cc hp cht
piriin.
Piriin biu hin tnh cht ca mt hp cht thm-tham gia phn ng th eletrphin.
Trong phn t piriin nguyn t nit tng t nh nguyn t cacbon to thnh lin kt vi
nhau bng 2 ocbitan lai to sp
2
v s dng mt in t p to thnh lin kt . Mi nguyn t
cacbon cn li mt ocbitan sp
2
dng to lin kt vi hyr. Trong khi ocbitan cn li
ca nit c cha 2 in t. Chnh s c mt ca cp in t ny l nguyn nhn dn n piriin
c tnh baz.
N
H H
H
H H

Piriin c th thu nhn bng cch chng ct nha than . Ngoi ra cc hp cht piriin
c th tng hp bng nhiu phng php khc nhau.
V d:
CH
2
CH CHO 2 NH
3
N
CH
3
N
COOH
+
3-Mtylpiriin Axit Nictinic

14.3.3. Tnh cht ho hc ca piriin.
a. Phn ng th S
E

ca piriin.
Trong phn ng loi ny, piriin biu hin tnh cht tng t nh dn xut ca benzen
c nhm gim hot: cc phn ng nitr ho, sunfunic ho, halogen ho xy ra trong iu kin
khc nghit cn phn ng th Frien-Crap th khng xy ra. Phn ng nh hng ch yu vo
v tr .
N
N
Br Br
N
NO
2
N
SO
3
H
N
Br
RX hoc RCOX, AlCl
3
Khng xy ra
HNO
3
/H
2
SO
4
, 300 C
0
H
2
SO
4
, 350 C
0
Br
2
, 300 C
0
+
b. Phn ng th nuclphin ca piriin.
Phn ng loi ny xy ra d dng i vi piriin v ch yu xy ra v tr 2 v 4.
V d:
N
Cl
N
NH
2
NH
3
, 180-200 C
0
N Br N NH
2
NH
3
, 180-200 C
0
Phn ng Titibabin.
N N
H
NH
2
-
N NH
2
NaNH
2
t
0
C
+
c. Phn ng kh piriin.
H
2
, Pt, HCl, 25 C, 3at
0
N N
H
Piperiin

Piriin mang tnh cht ca mt amin bc II. Piriin thng c s dng lm cht xc
tc.
B. ANCALOIT.
14.4. NH NGHA.
Ancaloit l nhng hp cht c hot tnh sinh hc mnh, do n c s dng nhiu
trong i sng, c bit l trong y hc. Ancaloit thc vt thng c trong cy h u, cy thuc
phin. Thng cc ancaloit khng phi cha trong ton thn cy m ch cha mt b phn no
. V d nictin ch c trong l thuc, kinin ch c trong r cy kininMt khc c th ch
mt loi cy nhng cha nhiu ancaloit khc nhau. Ancaloit trong thc vt thng tn ti di
cc mui vi axt hu c. tch cc ancaloit, thng ngi ta x l cc phn ca thn cy c
cha mui ca n bng kim hoc amnic sau tch ancaloit t do bng ete, clorofoc hoc
cc dung mi hu c khc.
Hin nay, ngi ta bit c khong 1000 ancaloit khc nhau nhng vn nhiu hp
cht trong cha c xc nh cng thc cu to.
14.5. PHN LOI CC ANCALOIT.
Ancaloit c phn loi theo s n v vng hyrcacbon c trong phn t c cha
nguyn t nit.
14.5.1. Ancaloit d vng 5 cnh cha mt nguyn t nit.
Hp cht n gin nht ca loi ny l Gigrin.
N
CH
3
CH
2
C
O
CH
3
14.5.2. Ancaloit h 2 vng cha mt nguyn t nit.
y l mt loi ancaloit thng gp trong cc loi cy hoa chm nh pirliin,
gelitrian. Hp cht quan trng nht ca loi ny l platigilin c dng trong y hc lm
dn n mch mu chng cc cn co tht.
N N
CH
3
N
CH
2
O O
C C O C
CHCH
3
CH
2
CH
CH
3
C
OH
CH
3
O
Pirliziin Gelitrian Platigilin

14.5.3. Ancaloit d vng 5 cnh cha haint nit.
i din cho loi hp cht ny l pilcatpin (c trong l cy pilcarpis Jaborandi) dng
cha bnh tng nhn p (thin u thng do s tng p sut mch mu mt).
O O
CH
3
CH
2
CH
2
N
N
CH
3
Pilocarpin

14.5.4. Ancaloit d vng 6 cnh cha mt nguyn t nit.
Ancaloit loi ny ch yu cha mt vng piperiin. V d conin l -prpylpiperiddin,
piperiin l ancaloit ca ht tiu cng l dn xut ca piperiin.
N
H
CH
2
CH
2
CH
3
N O C
O
CH CH CH CH O
O
Conin Piperin

Ancaloit t cy thuc phin gm mocphin v cin.
OH
O
HO
N CH
3
HO
OCH
3
N CH
3

14.1. T axit sucxinic hy iu ch pirol.
14.2. Hy cho bit sn phm phn ng ca piriin vi:
a. HCl b. B(CH
3
)
3
c. CH
3
I d. tec-butyl clorua
14.3. T quinolin v cc ha cht cn thit khc hy iu ch:
a. 8-hiroxiquinolin bng hai phng php.
b. 2-aminoquinolin.
14.4. Hon thnh s phn ng sau:
o-NH
2
C
6
H
4
COOH
ClCH
2
COOH
-HCl
-CO
2
-H
2
O
C
8
H
7
ON
+
A B C (D)
t
0
C
14.5. T 2-metylpiriin v cc ha cht cn thit khc hy iu ch:
a. 2-axetylpiriin
b. 2-vinylpiriin
c. 2-xiclopropylpiriin.
14.6. Piriin c b ankyl ha hoc axyl ha theo Frien-Crap khng?. T piriin hy iu ch 2-
n-butylpiriin v 2-n-butylpiperiin.
14.7. Vit cng thc cu trc v gi tn cc sn phm to thnh khi mononotro ha cc hp
cht sau:
a. 3-nitropyrol b. 3-metoxithiophen
c. 2-axetylthiophen d. 5-metyl-2-metoxithiophen
14.8. So snh tnh baz ca pyriin, pyrol v piperiin.
14.9. Gii thch ti sao anilin c tnh baz yu hn pyriin.
14.10. Vit phn ng ca pyrol vi cc tc nhn sau:
a. HCl b. HNO
3
/H
+

c. CH
3
COOCOCH
3
d. H
2
/Pt
Ni.
Chng 15
GLUXIT
(Hyrat cacbon)
15.1. M U.
Trong l ca cc loi cy xanh, cc phn t ng (+)-gluc c to thnh bi s tc
dng ca 2 hp cht n gin l kh CO
2
v nc. Qu trnh ny gi l s quang hp. N xy ra
bi s xc tc dip lc v ngun nng lng nh sng mt tri. Hng ngn phn t (+)-gluc c
th tp hp li vi nhau to thnh mt phn t ln gi l xenlul. Xenlul chnh l ngun
nguyn liu c bn nht cu to nn c th thc vt. Cc phn t (+)-gluc cng c th kt
hp vi nhau bng mt cch khc to tinh bt lm ngun d tr thc n cho qu trnh pht trin
ca mt th h mi.
Khi cc ng vt n tinh bt hoc xenlul th cc hp cht ny b ph v thnh hp cht
ban u l (+)-gluc. Cc phn t (+)-gluc ny c mu mang n gan v bin i thnh
glicgen (tinh bt ng vt). Trong mt s trng hp cn thit khc glicgen c th chuyn
ho li thnh (+)-gluc. (+)-Gluc cng c mu a n cc t bo v y n b xy ho
thnh kh cacbnic v nc, ng thi gii phng s nng lng m n hp th ca nh sng
mt tri. Mt s lng (+)-gluc chuyn ho thnh m, cn mt s khc lin kt vi cc hp
cht c cha nit to thnh aminaxt sau cc aminaxt lin kt vi nhau to thnh prtin
lm nn tng cho mi hot ng ca s sng.
(+)-Gluc, xenlul, tinh bt v glicgen thuc vo loi hp cht hu c c tn gi lag
gluxit. Cc hp cht gluxit chnh l ngun nguyn liu p ng nhng nhu cu c bn nht ca
con ngi. Chng ta s dng tinh bt lm thc n hoc l di dng ht ng cc, hoc l
di dng c ng vt chuyn thnh tht, m. Chng ta dng qun o c sn xut t
xenlul nh bng, si visc, si axtatc bit trong s pht trin ca th gii vn minh ngy
ny xenlul ng vai tr rt quan trng sn xut giy.
Tm li, ho hc gluxit l mt lnh vc rt th v ca ho hc hu c. N bao gm mt
chu trnh t s quang hot to thnh phn t (+)-gluc t kh cacbnic v nc c xc tc
bi men dip lc v nng lng nh sng mt tri n s chuyn ho ngc li t (+)-gluc
thnh kh cacbnic v nc bi cc loi men c trong c th ng vt v gii phng nng lng
m n hp th ca mt tri. Gia hai qua trnh sinh ho y, c mt nhuim v rt quan trng v
quen thuc ca ho hc l xc nh cc cng thc cu to, nghin cu cc tnh cht v s
chuyn ho ca gluxit thnh cc hp cht khc.
Di y ta s nghin cu mt vi tnh cht c bn ca gluxit lm c s cho qu trnh
nghin cu tip theo v n.
15.2. NH NGHA V PHN LOI.
15.2.1. nh ngha
Gluxit l nhng hp cht polyxyanhyt, polyxyxton hoc cc hp cht khi b thu
phn chuyn ho thnh cc hp cht anhyt hoc xton ni trn. Cc hp cht gluxit m khng
th b thu phn chuyn ho thnh nhng hp cht n gin hn gi l mnsacarit. Cc hp
cht gluxit b thu phn to thnh 2 phn t mnsacarit c gi l isacarit. Nu hp cht khi
b thu phn to thnh mt s ln mnsacarit th c gi l polysacrit.
15.2.2. Phn loi.
Ngi ta phn loi cc mnsacarit nh sau:
Nu phn t mnsacarit c cha mt nhm anhyt th ngi ta gi chng l anza, cn
nu c cha mt nhm xton th gi l xtza. Mt khc cn c vo s nguyn t cacbon c
trong phn t mnsacarit ngi ta gi chng l triza, tetrza, pentza, hecxza.V d khi ni
hp cht anhecxza c ngha l hp cht mnsacarit gm 6 nguyn t cacbon c cha mt
nhm anhyt, cn nu ni xtopentza tc l hp cht gm 5 nguyn t cacbon c cha mt
nhm xton.
Trong thin nhin thng gp cc loi mnsacarit pentza hoc hecxza.
Cc gluxit kh c thuc th Felinh hoc thuc th Tolen gi l nhng ng kh ho.
Tt c cc loi hp cht mnsacarit loi anza hoc xtoza u l nhng ng kh ho. Mt
phn ln cc isacarit l nhng sacar kh ho tr trng hp ng thng (ng n) khng
c kh nng tham gia phn ng kh gi l ng khng kh ho.
15.3. MNSACARIT : (+)-GLUC
Nu ta tnh rng mnsacarit (+)-gluc l mt n v cu trc m t cu to nn tinh
bt, xenlul, glicgen v vai tr quan trng c bit ca n trong sinh hc th gluc l mt
mnsacarit ph bin trong t nhin v do nghin cu cc tnh cht ca n ta c th suy ra
cc tnh cht ca hp cht khc.
(+)-Gluc c cng thc phn t l C
6
H
12
O
6
c xc nh bng phng php phn tch
nguyn t v ph khi lng. Cu to ca n c th d on theo mt s tnh cht sau y:
Phn ng C cha nhm
C
O
CHO
CH
2
OH v OHC
5 nhm -OH
C C C C C C
C C C C C CHO
NH
2
OH
C
6
H
5
NHNH
2
Br
2
, H
2
O
HNO
3
(CH
3
CO)
2
O
H
2
, Ni
HCN H
2
O, HO
-
HI, t
0
C
xim
C
6
H
13
COOH
Phnylhyrazon
(C
5
H
11
O
5
)COOH
HOOC(C
4
H
8
O
4
)COOH
C
6
H
7
O(OCOCH
3
)
5
(CH
3
CO)
2
O
C
6
H
8
(OCOCH
3
)
6
CH
3
(CH
2
)
3
CHICH
3
n-
C
6
H
14
O
6
HI, t
0
C
C
6
H
12
O
6
(+)-Glucza
T kt qu trn y ta c th kt lun rng: (+)-gluc l mt pentaxianhyt khng phn
nhnh cha 6 nguyn t cacbon-tc l anhecxza.
15.4. (-)-FRUCTZA (2-XTHECXZA).
y l loi hp cht xtza ph bin trong cc loi thc vt c bit l trong tri cy. (-)-
Fructza. Kt hp vi gluc to thnh isacarit l thnh phn chnh ca ng thng. Cc
chuyn ho sau y cho php kt lun rng (-)-fructza l mt xton (khng phi anhyt) v
nhm cacbnyl nm nguyn t C
2
tc l 2-xtohecxza.
CH
2
OH
C O
CHOH
CHOH
CHOH
CH
2
OH
CH
2
OH
C(OH)CN
CHOH
CHOH
CHOH
CH
2
OH
CH
2
OH
C(OH)COOH
CHOH
CHOH
CHOH
CH
2
OH
CH
3
CHCOOH
CH
2
CH
2
CH
2
CH
3
HCN
Thy phn HI, t
0
C
Fructza Xianhyrin Axit xicacbxylic Axit 2-mtylcapric

15.5. HO LP TH CA (+)-GLUC.
Cng thc cu to ca gluc nh bit trn y c cha 4 nguyn t cacbon bt i
xng. Cng thc cu to ny c th vit di dng Fish nh sau:
CHO
H OH
HO H
H OH
H OH
CH
2
OH

Vi s lng 4 nguyn t cacbon bt i xng hp cht gluc tn ti di dng 16 ng
phn quang hc (tc l 8 cp i quang). Tt c 16 ng phn quang hc ny n nay c
tch ra di dng cc hp cht tinh khit hoc bng con ng tng hp hoc bng con ng
chit tch t thc vt. Trong s 16 ng phn ny ch c (+)-gluc, (+)-mant v (+)-galact
c tm thy vi nhng lng ln. Mt khc trong 16 ng phn ni trn ch c (+)-gluc
c tm thy ph bin di dng mnsacarit.
15.6. CU HNH CA (+)-GLUC.
Nh ni trn cu hnh ca (+)-gluc c th l mt trong bt k 16 ng phn
nu. Vy cn phi xc nh cng thc cu to no l cu hnh cu to ca (+)-gluc. Nm 1888,
nh bc hc Emin Fish tin hnh nghin cu vn ny v n nm 1891 ng ta cng
nhn cc kt qu thu nhn c rt tt p. Cng chnh nh kt qu ca s nghin cu ny nm
1902 Fish c trao gii thng Nben. Di y l mt s im c bn v ni dung ca
vic chng minh cu hnh (+)-gluc ca Fish.
Do thi by gi cha c phng php chng minh cu hnh bng cu hnh tuyt i nn
Fish cho rng (+)-gluc c th l mt trong 2 ng phn ca mt cp i quang. V vy
n gin hn Fish b i 8 cu hnh c th c ca (+)-gluc m ch nghin cu 8 cng thc
ng phn cn li I-VIII trong nhm OH ca C
5
nm bn phi.
CHO
H OH
HO H
H OH
H OH
CH
2
OH
CHO
H OH
H OH
H OH
H OH
CH
2
OH
CHO
HO H
H OH
H OH
H OH
CH
2
OH
CHO
HO H
HO H
H OH
H OH
CH
2
OH
I II III IV
CHO
H OH
HO H
HO H
H OH
CH
2
OH
CHO
H OH
H OH
HO H
H OH
CH
2
OH
CHO
HO H
H OH
HO H
H OH
CH
2
OH
CHO
HO H
HO H
HO H
H OH
CH
2
OH
V VI VII VIII

Mt khc c s ca qu trnh chng minh l da vo s tng tc gia (+)-gluc v
anpent: (-)-arbin. V vy Fish tin hnh xem xt cu hnh ca anpent. y ng
ch xt 4 cu hnh IX-XII vi nhm OH ca nguyn t cacbon bt i xng di cng nm v
pha bn phi.
CHO
H OH
H OH
H OH
CH
2
OH
CHO
HO H
H OH
H OH
CH
2
OH
CHO
H OH
HO H
H OH
CH
2
OH
CHO
HO H
HO H
H OH
CH
2
OH
IX X XI XII

S chng minh ca Fish nh sau:
1. Khi xy ho (-)-arbin bng axt nitric thu c mt axt icacbxylic quang hot.
Nh trn ni, v nhm OH ca nguyn t cacbon bt i xng di cng trong (-)-arbin
nm pha bn phi cho nn theo kt qu ca phn ng xy ho trn y th nhm OH ca
nguyn t cacbon bt i xng trn cng phi nm v pha bn tri tng t nh X hoc XII
nu khng s thu c sn phm khng quang hot.
COOH
HO H
H OH
COOH
Quang hot
CHO
HO H
H OH
CH
2
OH
X hoc XII
HNO
3
HNO
3
CHO
H OH
H OH
CH
2
OH
COOH
H OH
H OH
COOH
IX hoc XI Hp cht mz(khng quang hot)
2. (-)-Arbin c th chuyn ho thnh (+)-gluc v (+)-mant bng phn ng Kiliani-
Fish. Do (+)-gluc v (+)-mant l nhng ng phn epime-tc l 2 anza thu nhn c
trong kt qu ca mt phn ng tng hp ch khc nhau duy nht v cu to bi cu hnh C
2
. Do
(+)-gluc v (+)-mant c th c cu hnh III v IV hoc VI v VIII.
(+)-Gluc v (+)-Mant: III v IV hoc VII v VIII
HO H
H OH
H OH
CH
2
OH
OH H
CHO
HO H
H OH
H OH
CH
2
OH
H HO
CHO
Na(Hg)
v
(-)-Arbin
X hoc XII
CHO
HO H
H OH
CH
2
OH
HO H
H OH
H OH
CH
2
OH
CN
HO H
H OH
H OH
CH
2
OH
COOH
HO H
H
H OH
CH
2
OH
C O
O
HCN
H
2
O, H
+
3- Khi b xy ho bi HNO
3
c (+)-gluc ln (+)-mant u cho mt sn phm l axt
icacbxylic quang hot. iu c ngha l nhm OH thuc nguyn t C
4
nm bn phi
ging III v IV.
4- xy ho mt hp cht hecxza khc (+)-gluc to thnh mt axt icacbxylic (+)-
sacarit tng t nh xy ho (+)-gluc.
CHO
H OH
HO H
H OH
H OH
CH
2
OH
COOH
H OH
HO H
H OH
H OH
COOH
CH
2
OH
H OH
HO H
H OH
H OH
CHO
HNO
3
HNO
3
III IIIa i quang caV
(+)-Gul

Nh vy (+)-sacarit axt c cu hnh IIIa nn (+)-gluc phi c cu hnh III. Do (+)-
mant c cu hnh IV.
Trong cng thc cu to III, nhm OH thuc nguyn t cacbon bt i xng di cng
nm v pha bn phi nn n c cu hnh D- tc l (+)-gluc c cu hnh D. Hp cht i quang
ca n c cu hnh L.
CHO
OH H
H HO
OH H
OH H
CH
2
OH
CHO
H HO
OH H
H HO
H HO
CH
2
OH
D-(+)-Gluc L-(+)-Gluc

15.7. CU TO DNG VNG CA D-(+)-GLUC.
Cng thc cu to D-(+)-gluc c Fish chng minh trn y tuy tho mn c
nhng tnh cht quan trng ca hp cht pentaxianhyt nhng trong mt s trng hp thc
t sau y khng th gii thch c bng cng thc cu to .
1- D-(+)-Gluc khng tham gia mt s phn ng c trng cho hp cht anhyt. V d
n khng tham gia phn ng vi thuc th Ship (lm mt mu dung dch ixyt lu hunh SO
2

trong 0,025% dung dch fucxin) hoc khng tham gia phn ng vi bisunfit natri.
2- D-(+)-Gluc tn ti di 2 dng ng phn: Mt D-(+)-gluc tinh th (t
nc
=146
0
C) khi
ho tan vo trong nc lc u c quay cc l [] =+112
0
nhng sau gim dn xung cn
+52,7
0
. Mt D-(+)-gluc khc (t
nc
=150
0
) khi tan trong nc c quay cc t +19
0
tng dn ln
n +52,7
0
. ng phn c quay cc cao ngi ta gi l -D-(+)-gluc, v ng phn c
quay cc thp gi l -D-(+)-gluc.
3- D-(+)-Gluc to thnh 2 ng phn mtyl-D-gluczit.
Ta bit rng nu anhyt tc dng vi ancol c xc tc l axt s to thnh hp cht
axtal.
CH O CH
OH
OCH
3
CH
OCH
3
OCH
3
Anhyt Semiaxtal Axtal
CH
3
OH, H
+
CH
3
OH, H
+
Th nhng khi cho D-(+)-gluc tc dng vi mtanol v HCl khng to thnh axetal.
Mt khc hp cht ny khng b thu phn vi nc to thnh anhyt v ancol nh cc hp
cht semiaxtal. Ngoi ra mtyl-D-gluczit c to thnh tn ti di 2 dng ng phn: mt
ng phn c nhit nng chy l 165
0
C vi gc quay cc l +158
0
v mt ng phn khc c
nhit nng chy l 107
0
C vi gc quay cc l 33
0
. Ngi ta gi ng phn th nht l
mtyl--D-gluczit v ng phn th 2 l mtyl--D-gluczit.
Tt c nhng iu c a ra trn y s c gii thch mt cch thch hp nu cng
nhn D-(+)-gluc c cu dng vng.
H C OH
H C OH
HO C H
H C
H C
CH
2
OH
O
OH
1
2
3
4
5
6
IIa
O
OH
H
H
OH
H
OH
H
OH
CH
2
OH
H
1
2
3
4
5
6
O
H
OH
H
OH
H
HO
H
HO
H
CH
2
OH
1
2
3
4
5
6
IIb IIc ( -D-(+)- Gluc)
( -D-(+)- Gluc)
HO C H
H C OH
HO C H
H C OH
H C
CH
2
OH
O
O
OH
H
OH
H
H
OH
H
OH
CH
2
OH
H
1
2
3
4
5
6
O
OH
H
H
OH
H
HO
H
HO
H
CH
2
OH
1
2
3
4
5
6
IIIa IIIb IIIc
D-(+)-Gluc c cu to dng vng nh IIa v IIIa, nu vit chnh xc hn l IIb v IIIb
cn nu tht chnh xc l IIc v IIIc.
D-(+)-Gluc ch c kh nng to thnh hp cht semiaxtal bi v nhm OH ca C
1

tng tc vi nhm OH ca C
5
to thnh cng thc vng.
Tn ti 2 cng thc ng phn ca D-(+)-gluc c gy ra bi cu to vng c thm
mt nguyn t cacbon bt i xng C
*
1
. S khc nhau v cu hnh nguyn t cacbon ny
dn n to thnh cc ng phn.
D-(+)-Gluc ch c th tham gia mt s phn ng c trng cho anhyt nhng khng
tham gia phn ng Ship c th gii thch rng do s tn ti mt lng rt nh (khong 0,5%)
dng anhyt t do nh cng thc I nn khng tham gia cc phn ng cng bisunfit hoc
phn ng Ship.
15.8. ISACARIT.
isacarit l nhng hp cht to nn bi 2 phn t mnsacarit. Di y chng ta s
xem xt mt s isacarit quan trng nh: (+)-mant (ng mch nha), (+)-xenlbi, (+)-lact
(ng sa), (+)-sacar (ng ma v c ci ng).
15.8.1. (+)-Mant.
ng mant c th iu ch bng cch thu phn tinh bt bi dung dch axt hoc bng
phng php ln men trong ru tylic.
Cng thc phn t ca mant l C
12
H
22
O
11
. ng mant tham gia cc phn ng vi
thuc th Tlen, Felinh nn n l ng kh ho. Mant tc dng vi phnylhyrazin to thnh
C
12
H
20
O
9
(=NNHC
6
H
5
)
2
v b xy ho bi nc brm to thnh axt
mantbinic(C
11
H
21
O
10
)COOH. ng mant cng tn ti di 2 dng v vi [] =+168
v +112.
Tt c cc kt qu thu nhn c trn y cho thy rng (+)-mant c cha mt nhm
cacbnyl di dng biaxtal hot ng mnh nh trong cc hp cht mnsacarit. Khi b thu
phn bng dung dch axt hoc bi xc tc men (+)-mant chuyn ho thnh D-(+)-gluc. Do
(+)-mant dc cu to t 2 gc D-(+)-gluc v thuc vo loi hp cht gluczit. T c
th suy ra (+)-mant c cu to sau y:

O
H
H
O
H
OH
H
HO
H
HO
H
O
H
OH
H
OH
HO
H
H
CH
2
OH CH
2
OH
1
2
3
4
5
6
1
4-O-( - D-glucpiranzyl )-D-glucpiranza
15.8.2. Xenlbi.
Xenlul c cng thc phn t l (C
6
H
10
O
5
)
n
. Di tc dng ca axt sunfuric v anhyrit
axtic trong nhiu ngy s xy ra phn ng axtyl ho v thu phn to thnh ctaxtal (+)-
xenlul. Nu thu phn bng kim s thu c (+)-xenlbi.
Xenlbi c cng thc phn t l C
12
H
22
O
11
thuc loi ng kh ho tng t nh (+)-
mant duy ch khc nhau mt im l n b thu phn bi men emuxin ch c tc dng thu
phn cc lin kt -gluczit do c th kt lun rng cc gc D-gluc trong xenlbi kt hp
vi nhau bi lin kt -gluczit ch khng phi -gluczit nh trong mant.
O
H O
H
OH
H
H
HO
HO
H
O
H
H
HO H
H
OH
H
OH
CH
2
OH
CH
2
OH
4-O-( -D- glucpiranzyl )-D-glucpiranza
15.8.3. (+)-Lact.
(+)-Lact c trong thnh phn ca sa khong 5%, c cng thc phn t C
12
H
22
O
11
thuc

loi ng kh ho. Khi b thu phn bi axt t (+)-lact thu c D-(+)-lact v D-(+)-
galac vi lng bng nhau. Do (+)-lact l mt hp cht gluczit c to thnh t D-(+)-
gluc v D-(+)-galact.
O
OH
H
H
H
HO
H
OH
H
O
O
H
H
HO H
H
OH
H
OH
CH
2
OH
CH
2
OH
4-O-( -D-galactpiranzyl )-D-glucpiranza
15.8.4. (+)- Sacar.
(+)- Sacar l ng knh thng dng c sn xut t ng ma hay ng c ci.
(+)- Sacar c cng thc phn t C
12
H
22
O
11
thuc

loi ng khng kh ho c ngha l n
khng c nhm anhyt hoc xton t do. Khi b thu phn bi axt long hoc men invectaza
t (+)- sacar thu c D-(+)-gluc v D-(-)-fruct vi lng nh nhau. Kt hp vi mt s
phng php phn tch vt l khc nhau, ngi ta i n kt lun rng (+)- sacar l hp
cht -D-fructzit v -D-gluczit.
CH
2
OH
O
H
HO H
H
CH
2
OH
CH
2
OH
HO
O
H
OH
H
H HO
H
HO
H
O
(+)-Sacar

15.9. POLYSACARIT.
Polysacarit l nhng hp cht c to thnh t nhiu gc mnsacarit. Tng t nh
cc hp cht isacarit, cc gc mnsacarit trong phn t polysacarit kt hp vi nhau bng lin
kt gluczit v cc lin kt ny b phn hu trong cc phn ng thu phn. Hai hp cht quan
trng nht ca polysacarit trong t nhin l tinh bt v xenlul. Chng c cng thc
(C
6
H
10
O
5
)
n
. y l nhng hp cht c ngha rt quan trng i vi i sng con ngi.
15.9.1. Tinh bt.
Tinh bt cha trong ht v trong c ca thc vt. dng ht, tinh bt khng ho tan
trong nc lnh. Khi b ph hu lp v bc bn ngoi v nghin nh, tinh bt c kh nng n ra
trong nc lnh v to thnh h phn tn keo. Trong nc nng phn ho tan ca tinh bt keo
t li vi nhau to thnh gen h keo. Thng th tinh bt cha khong 20% cht ho tan trong
nc gi l amilpectin. C 2 phn ny u c cng thc (C
6
H
10
O
5
)
n
. Khi b thu phn bi axt
hoc di tc dng ca men, tinh bt bin thnh ectrin (hn hp polysacarit c phn t
lng thp), (+)-mant v cui cng to thnh D-(+)-gluc. C amilza ln amilpectin u
c to thnh t gc D-(+)-gluc nhng ch khc nhau v s lng v dng phn t.
a. Cu to ca amilza.
Khi b thu phn amilza trc ht to thnh hp cht isacarit (+)-mant v sau to
thnh mnsacarit l D-(+)-gluc. iu c ngha l amilza c to thnh t mt lng ln
gc D-(+)-gluc m trong chng kt hp vi nhau bng lin kt -gluczit thuc nguyn t
cacbon C
1
v C
4

CH
2
OH CH
2
OH
O
H
H
HO H
H
OH
H
O
O
H
O
H
HO H
H
OH
H
O O
H
OH
H
H HO
H
H
O
CH
2
OH
Amilza

b. Cu to ca amilpectin.
Amilpectin khi b thu phn cho mt sn phm duy nht isacarit l (+)-mant. Do
tng t nh amilza, amilpectin c to thnh t cc gc D-gluc nhng c cu to phc
tp hn. Bng cc phng php phn tch vt l hin i, ngi ta i n kt lun rng:
amilpectin c cu to phn nhnh cha khong 20-25 gc D-gluc. Cc mch nhnh ny lin
kt vi nhau bng nguyn t xy thuc C
1
vi nguyn t cacbon C
6
.
CH
2
OH
H
CH
2
OH
O
O
H
HO H
H
OH
H
O O
H
OH
H
H HO
H
H
O
O
H
H
HO H
H
2
C
H
OH
H
O O
H
OH
H
H HO
H
O
H
O
CH
2
OH
Amilpectin

15.9.2. Xenlul.
a. Cu to.
Xenlul l thnh phn chnh ca g v cc si t nhin nh si bng, si gai, si
ayXenlul khng tan trong nc. N l loi ng khng kh ho v c phn t lng rt
ln. Khi b thu phn hon ton xenlul cho mt sn phm mnsacarit duy nht l D-(+)-
gluc. Do cho php kt lun rng xenlul cng tng t nh tinh bt c cu to t cc gc
ca D-gluc. Bng cc phng php phn tch hin i, ngi ta kt lun rng khc vi tinh
bt, cc lin kt gluczit trong xenlul l loi lin kt 1-4 .
O
H
H
HO H
H
OH
O
H
O
O
H
H
HO H
H
OH
H
O
H
O
OH
H
H HO
H
H
O
CH
2
OH CH
2
OH
CH
2
OH
Xenlul

b. Cc phn ng ca xenlul.
Xenlul b thu phn bi axt v c to thnh (+)-gluc. Mt khc nu phn t xenlul
cha b ph v th mi mt n v vng c cha 3 nhm OH. Chnh cc nhm ny s tham gia
vo mt s phn ng.
1- Nitrat xenlul.
Xenlul tng t nh cc ancol c kh nng tham gia cc phn ng este ho. Khi n tc
dng vi hn hp axt nitric v sunfuric to thnh nitrat xenlul. Hp cht ny (khi c 3 nhm
OH c thay th bng nhm ONO
2
) c s dng lm thuc sng. Hp cht pirocxilin (khi 2
nhm OH ca xenlul b thay th bi ONO
2
) c s dng sn xut phim nh.
2- Axtat xenlul.
Di tc dng ca axetanhyt, axt axtic v axt sunfuric xenlul chuyn ho thnh
trinitrat xenlul. Cc hp cht axtat xenlul c s dng lm phim nh, lm si dt vi (si
axtat, si t la axtat).
3- T la nhn to v xlfan.
Nu cho ancol tc dng vi iunfua cacbon v dung dch NaOH s thu c hp cht
xantgenat.
RONa S C S RO C
S
SNa
H
+
CS
2
+ + ROH
Xenlul cng tham gia phn ng tng t nh ancol to thnh hp cht xantgenat.
[C
6
H
7
O
2
(OH)
3
]
n
nNaOH + [C
6
H
7
O
2
(OH)
3
.NaOH]
n
nCS
2
(C
6
H
9
O
4
OCS
2
Na)
n
nH
2
O +
Dung dch xantgenat trong kim sau khi c dn qua b cha H
2
SO
4
v ko thnh si
s thu c t nhn to visc. Nu ho do xantgenat bng glyxrin v cn thnh cc mn
mng ta c mng xlfan.
15.1. Cho Glucz tc dng vi HIO
4
s thu c nhng loi hp cht no.
15.2. Hon thnh cc s phn ng sau y:
A
4HIO
4
3HCOOH HCHO
OHC COOH
+ + +
5HIO
4
4HCOOH 2HCHO B
+ +
C 3HIO
4
2HCOOH 2
OHC COOH
+ +
D
+
4HIO
4
4HCOOH
OHC COOH
+

15.3. Vit cng thc cu to ca cc hp cht to thnh khi cho D-(+)-galactz tc dng vi:
a. Hydroxylamin b. Dung dch nc Brm
c. HNO
3
d. HIO
4

e. CH
3
OH/HCl f. NaBH
4

g. Phenyl hyroxylamin h. (CH
3
CO)
2
O
i. CH
3
OH/HCl tip theo dimetyl sunfat/NaOH
j. Dung dch nc Brm tip theo CaCO
3
, tip theo H
2
O
2
/Fe
3+

15.4. Thc hin s chuyn ha sau:
ClCH
2
CHO BrMgC CMgBr OHCCH
2
Cl
A(C
6
H
8
O
2
Cl
2
)
+ +
meso-A KOH B(C
6
H
6
O
2
- Epoxi)
+
B H
2
O/HO
-
+
C(C
6
H
10
O
4
)
C H
2
, Pd/CaCO
3
D(C
6
H
12
O
4
)
+
D KMnO
4
(long, lnh) E (C hai u l C
6
H
14
O
6
)
+
E' +
peaxit focmic
F(C
6
H
14
O
6
) D
+
C Na/NH
3
G(C
6
H
12
O
4
)
+
C KMnO
4
(long, lnh) H(C
6
H
14
O
6
)
+
C
+
peaxit focmic I I'
+
(C hai u l C
6
H
14
O
6
)

15.5. Salixin (C
13
H
18
O
7
), c trong loi cy Salix, b thu phn bi men Emuxin to thnh D-
glucz v Saligenin(C
7
H
8
O
2
). Salixin khng c phn ng vi thuc th Tollen, khi b oxi ha
bi CH
3
COOH to thnh mt hp cht m khi thu phn hp cht ny thu c D-glucz v
Anhyrit Salixilic. Metyl ha Salixin thu c pentametyl Salixin, khi thu phn hp cht ny
to ra sn phm 2,3,4,6-tetra-O-metyl-D-glucz. Xc nh cng thc cu to ca Salixin.
Ni.
Chng 16
AMINAXT V PRTIT.
16.1. MT S KHI NIM M U.
Tn gi prtit bt ngun t ting Latinh proteios c ngha l th nht. Tn gi nh th c
ngha rt thch hp bi v trong tt c cc hp cht ha hc prtit l hp cht quan trng bc
nht to thnh s sng. Prtit khng ch l thnh phn c bn cu to nn cc c quan m
n cn l ngun cung cp mi nhu cu cn thit cho cc hot ng ca s sng.
Di quan im ho hc, prtit l hp cht cao phn t-polyamit c to thnh t cc
mnme -aminaxt. Trong thnh phn ca mt phn t prtit c th c hng trm hoc hng
ngn gc aminaxt. Cho n nay ngi ta mi bit c khong trn 20 loi aminaxt khc
nhau. Nhng s t hp ca cc aminaxt ny rt a dng v phong ph v l c s to nn
cc c quan khc nhau ca ng vt. duy tr s sng v s pht trin, trong cc c th ca
ng vt c ti hng ngn loi prtit khc nhau, mt khc i vi nhng loi ng vt nht nh
c cc c trng ca n.
A. AMINAXT.
16.2. CU TO CA AMINAXT.
Trong bng di y l cng thc cu to v tn gi ca 26 loi aminaxt trong prtit.
Mt s aminaxt c nh du * l nhng hp cht c th khng tng hp c t cc cht ly
t thc n.
Tt c cc aminaxt u l nhng -amincacbxylic axt. Trong 2 trng hp prlin v
xyprlin nhm amin tham gia to thnh vng pirliin. Trong mt s trng hp aminaxt
cn cha thm mt nhm cacbxyl th 2 (v d nh acparagic hay glutamic axt) hoc nhm
cacbnyl nh acogin. Loi aminaxt ny c gi l aminaxt axt. Mt s aminaxt c cha
nhm baz nh lizin, arginin, gistiin c gi l aminaxt baz.
16.3. AMINAXT TNG T NH CC ION LNG CC.
Thng th cc aminaxt c biu din l nhng hp cht c cha nhm amin v
nhm cacbxyl H
2
NCHRCOOH nhng trong thc t mt s tnh cht ho l ca n khng phn
nh ph hp vi cng thc cu to ny.
Bng mt s aminaxit quan trng ca prtit.
Tn gi Vit tt Cng thc
Glyxin Gly
H
3
NCH
2
COO
-
+
(+)-Alanin Ala
CH
3
CHCOO
-
+ NH
3

(+)-Valin Val*
(CH
3
)
2
CHCH
NH
3
COO
-
+

(-)-Leixin Leu*
(CH
3
)
2
CHCH
2
CHCOO
-
+ NH
3

(+)-Izleixin Ile*
CH
3
CH
2
CH(CH
3
)CHCOO
-
+ NH
3

(+)-Asparagic axt Asp
HOOCCH
2
CHCOO
-
+ NH
3

(-)-Aspagin Asp-NH
2

H
2
NCOCH
2
CHCOO
-
+ NH
3

(+)-Glutamic axt Glu
HOOCCH
2
CH
2
CHCOO
-
+ NH
3

(+)-Glutamin Glu-NH
2

H
2
NCOCH
2
CH
2
CHCOO
-
+ NH
3

(+)-Lizin Lys*
H
2
NCH
2
CH
2
CH
2
CH
2
CHCOO
-
+ NH
3

(-)-xilizin Oly
H
2
NCH
2
CHCH
2
CH
2
CHCOO
-
OH NH
3
+

(+)-Arginin Arg*
H
2
NCNHCH
2
CH
2
CH
2
CHCOO
-
NH
2
+ NH
2

(-)-Serin Ser
HOCH
2
CHCOO
-
+ NH
3

(-)-Treonin Tre*
CH
3
CH CHCOO
-
OH NH
3
+

(-)-Cystein Cys
HOCH
2
CHCOO
-
+ NH
3

(-)-Cystin -
OOCCHCH
2
S S CH
2
CHCOO
-
NH
3
NH
3
+ +

(-)-Metionin Met
CH
3
SCH
2
CH
2
CHCOO
-
+ NH
3

(-)-Phenylalanin Phe*
CH
2
CHCOO
-
+ NH
3

(-)-Tyrozin Tyr
HO CH
2
CHCOO
-
+ NH
3

(+)-3,5-ibrmtyrzin
HO
Br
Br
NH
3
CH
2
CHCOO
-
+
(+)-3,5-iityrzin
HO
I
I
NH
3
CH
2
CHCOO
-
+
(-)-Tryptophan Try*
N
H
NH
3
CH
2
CHCOO
-
+
(-)-Prolin Pro
N
COO
-
H H
+
(-)-xiprolin Opr
N
COO
-
H H
HO
+
(-)-Histoin His
N
N
H
NH
3
CH
2
CHCOO
-
+
(+)-Tyroxin
HO
I
I
O
I
I
NH
3
CH
2
CHCOO
-
+
1- Khc vi amin v axt cacbxylic cc aminaxt l nhng hp cht tn ti di nhng
tinh th khng bay hi v nng chy nhit rt cao cng vi s phn hu.
2- Cc aminaxt khng tan trong cc dung mi khng phn cc nh ete, ete du ho,
benzen nhng li tan tt trong nc.
3- Dung dch nc ca aminaxt c mmen lng cc rt cao.
4- Cc hng s axt v baz ca cc nhm COOH v NH
2
ca aminaxt rt nh so vi
cc axt cacbxylic v amin tng ng.
Tt c cc tnh cht khc bit trn y ca aminaxt s c gii thch tho mn khi
biu din cng thc cu to ca cc aminaxt l nhng ion lng cc.
H
3
N CHR COO
-
+
(I)

Theo cu to (I), cc tnh cht vt l nh nhit nng chy, ho tan, mmen lng
cc nh nu cc im 1, 2, 3 trn y s rt ph hp vi mt mui nh vy. Cc hng s
axt v baz cng d dng gii thch v rng trn thc t K
a
c xc nh bi ion amni RNH
3
v K
b
c xc nh bi ion cacbxylat RCOO
-
.
H
3
NCHRCOO
-
+
H
2
O + + H
3
NCHRCOOH HO
-
+
Baz
K =
[H
3
O
+
][H
2
NCHRCOO
-
]
[H
3
NCHRCOO
-
]
+
H
3
NCHRCOO
-
+
H
2
O H
3
O
+
H
2
NCHRCOO
-
+ +
Axit
a
K =
b
[H
3
NCHRCOOH][HO
-
]
+
[H
3
NCHRCOO
-
]
+
Trong thc t tu thuc vo mi trng m cc aminaxt tn ti chng c th chuyn
ho theo s sau:
H
3
N CHR COO
-
+
H
2
NCHRCOO
-
H
3
NCHRCOOH
+
H
+
HO
-
HO
-
H
+
II I III

Qua s chuyn ho ny, ta thy cc ion II v III c cha nhm NH
2
v COOH.
Chnh s tn ti ca cc nhm ny cho php cc aminaxt tham gia mt s phn ng cho
cc hp cht amin v axt cacbxylic.
16.4. IM NG IN CA AMINAXT.
Nu ta cho dung dch aminaxt vo trong mt in trng th ph thuc vo dung dch
c tnh axt hay baz ta s quan st thy cc hin tng khc nhau. Theo s chuyn ho trn
y trong dung dch kim mnh nng ca anion II s ln hn nng ca cation III v do
aminaxt s chuyn dch v pha ant. Tri li trong dung dch axt mnh, nng ca cation
III ln hn anion II v do aminaxt s chuyn dch v pha catt. Nu nh nng ca II v
III bng nhau th lc ta s khng quan st thy mt s chuyn dch no ca aminaxt. Bt k
mt phn t aminaxt no trong iu kin ny cng u tn ti di dng va l cation v do
mi mt s chuyn dch in t no ca mt phn t aminaxt v mt pha in cc s c
b li ngay lp tc bi s chuyn ng ngc li. Nng ion hyr m ti mt phn t
aminaxt nht nh khng b dch chuyn bi tc dng ca in trng c gi l im ng
in ca aminaxt .
16.5. CU HNH CA AMINAXT THIN NHIN.
Nh ta bit cc aminaxt u c cha t nht mt nguyn t cacbon bt i xng (tr
glyxin). Qu trnh nghin cu ho lp th ca cc aminaxt thin nhin ch ra rng chng c
cng mt loi cu hnh v cu hnh ging nh cu hnh L-(-)-glyxeranehyt.
CHO
CH
2
OH
H HO
COO
-
H H
2
N
R
L-(-)-Glyxranhyt L-Aminaxit
16.6. TNG HP CC AMINAXT.
Phng php quan trng nht tng hp cc aminaxt l amin ho cc -halogenaxt
sau y:
1- Phn ng amin ho trc tip -clo v -brmcacbxylic axt.
V d:
CH
3
CH
2
COOH
Br
2
, P
CH
3
CH COOH
Br
NH
3
CH
3
CHCOO
-
+ NH
3
Alanin
CH
2
(COOC
2
H
5
)
2
Na
+-
CH(COOC
2
H
5
)
2
C
6
H
5
CH
2
C(COOC
2
H
5
)
2
H
C
2
H
5
ONa C
6
H
5
CH
2
Cl
KOH, t
0
C HCl
C
6
H
5
CH
2
CH(COOH)
2
Br
2
, te
C
6
H
5
CH
2
C(COOH)
2
Br
C
6
H
5
CH
2
CHCOOH
Br
t
0
C
C
6
H
5
CH
2
CHCOO
-
+ NH
3
Phnylalanin
NH
3
2- Tng hp Gabrien.
N
-
K
+
O
O
ClCH
2
COOC
2
H
5
NCH
2
COOC
2
H
5
O
O
+
Phtalimit kali
tylcloaxtat
Cl
-
COOH
COOH
H
3
NCH
2
COOH
+ HCl, H
2
O
+ +
16.7. CC PHN NG CA AMINAXT.
Phn ng ca aminaxt nhn chung l nhng phn ng ca cc hp cht cha nhm
amin v nhm cacbnyl.
B. PEPTIT.
16.8. NH NGHA, PHN LOI V CU TO.
Peptit l nhng hp cht amit c to thnh do kt qu phn ng ca nhm amin v
nhm cacbnyl ca cc aminaxt vi nhau. Nhm amit NHCO- trong cc hp cht ny
thng c gi l lin kt peptit. Cc hp cht peptit c phn loi thnh mnpeptit,
ipeptit, tripeptitcho n polypeptit ph thuc vo s lng nh hn 10.000 th gi l
polypeptit, cn nu ln hn 10.000 th gi l prtit.
Khi vit cc cng thc ca cc peptit thun tin ngi ta thng dng cc k hiu vit
tt ca cc aminaxt trong nhm amin c quy nh vit pha bn tri v nhm
cacbxyl t do bn phi.
V d:
N
H
H R
C
O
N
H
R
H
C
O
N
H
H R
C
O
H
3
NCH
2
CONHCH
2
COO
-
+
Glyxylglyxin
Gly-Gly (ipeptit)
H
3
NCH
2
CONHCHCONHCHCOO
-
CH
2
C
6
H
5
+
Glyxylalanylphnylalanin
Gly-Ala-Phe (tripeptit)
H
3
NCHCO(NHCHCO) NHCHCOO
-
R R R
n
+
Polypeptit

Cc phng php phn tch ho l v rengen cho thy rng tt c cc nhm amt u nm
trong mt mt phng-tc l nhm cacbnyl nguyn t nit v cc lin kt ca cc nhm ny
nm trong mt mt phng.
16.9. CC PHNG PHP XC NH CU TO CA PEPTIT.
xc nh cu to ca mt hp cht peptit cho cn phi:
1- Xc nh nhng aminaxt no c trong thnh phn phn t ca peptit.
2- C bao nhiu loi aminaxt v s lng mi loi l bao nhiu trong phn t ca
peptit.
3- Cch thc to lin kt ca cc aminaxt trong phn t peptit.
Hp cht peptit trc ht c thu phn bng axt (khng thu phn bng baz v sn
phm to thnh s b raxemic ho) v sau xc nh khi lng ca mi loi aminaxt to
thnh sau phn ng. Phng php tt nht hin nay thng c dng tch cc aminaxt l
sc k. Xc nh c s lng ca mi loi axt ta c th tnh c s mol ca chng v t
suy ra t l ca cc aminaxt c trong phn t peptit-tc l xc nh c cng thc phn t
tng qut. Sau xc nh phn t lng ca phn t peptit bng phng php vt l nh o p
sut thm thu, nhiu x rengenv suy ra cng thc phn t ca peptit.
xc nh cch thc to lin kt ca cc aminaxt trong phn t peptit, ngi ta s
dng kt hp 2 phng php: xc nh nhm cui mch v thu phn tng phn. C nhiu
phng php xc nh nhm cui mch ca peptit. V d phng php ca Sendrer s dng
thnh cng bng cch dng hp cht 2,4-initrbenzen nh sau:
Peptit Peptit c nh du
O
2
N
NO
2
F + H
2
NCHCONHCHCO
R R'
O
2
N
NO
2
NHCHCONHCHCO
R R'
O
2
N
NO
2
NHCHCOOH
R
H
3
NCHCOO
-
R'
+
HCl, t
0
C
Aminaxit khng nh du N-(2,4-initrphnyl)-aminaxit
+
Sau khi tch c N-(2,4-initrphenyl)-aminaxt, tip tc tch ring cc aminaxt v
qua nhn xt, kt lun v s to lin kt ca chng vi nhau.
16.10. TNG HP CC PEPTIT.
Phng php polyme ho cc aminaxt to thnh polypeptit vi phn t lng cao
c ngha trong cng nghip v i sng. Nhng iu ch cc peptit c cu trc tng t
nh peptit t nhin th phng php ny khng thch hp. Do ngi ta tin hnh iu ch cc
peptit bng mt s phng php khc. Vn c tnh cht quyt nh c t ra l phi bo v
cc nhm amin trong qu trnh tng hp. Phi lm sao cho s kt hp ca nhm cacbxyl ca
phn t aminaxt ny vi nhm amin ca phn t aminaxt kia khng xy ra s phn ng
gia cc nhm cacbxyl v amin ca cng mt phn t aminaxt. V d phi lm sao cho khi
iu ch glyxylalanin th khng xy ra phn ng to thnh glyxylglynin. iu c th iu
chnh c nu a thm vo nhm amin mt nhm chc khc c tc dng lm cho kh nng
phn ng ca nhm amin gim i.
V d:
Bo v
nhm amin
To lin
kt peptit
Tch nhm
bo v Q
Q
NHCHCOOH
R
H
3
NCHCOO
-
R
+
Q
NHCHCOCl
R
Q
NHCHCOCl
R
H
3
NCHCOO
-
R'
+
Q
NHCH C NHCHCOOH
R O R'
+
Q
NHCH C NHCHCOOH
R O R'
H
3
NCH C NHCHCOO
-
R O R'
+
Trong phn ng trn y, ngi ta bo v nhm amin ca glyxin bng Q-C
6
H
5
- sau
chuyn nhm glyxin thnh cloranhyrit ri cho phn ng vi alanin. Cc phn ng iu ch
c th vit li di dng y nh sau:
SOCl
2
C
6
H
5
CH
2
O C
O
Cl CO Cl
2
Cl C Cl
O
+
than hot tnh
200 C
0
C
6
H
5
CH
2
OH
C
6
H
5
CH
2
OCOCl H
3
NCH
2
COO
-
+
C
6
H
5
CH
2
OCONHCH
2
COOH +
H
2
,Ni
C
6
H
5
CH
3
CO
2
C
6
H
5
CH
2
OCONHCH
2
CONHCHCOOH
CH
3
C
6
H
5
CH
2
OCONHCH
2
COCl
H
3
NCH(CH
3
)COO
-
+
H
3
NCH
2
CONHCHCOO
-
CH
3
+
+ +
Gly-Ala

C. PRTIT.
16.11. PHN LOI V S BIN TNH CA PRTIT.
16.11.1. Phn loi.
Prtit c phn thnh 2 loi chnh: prtit dng si v prtit dng cu. Prtit dng si
khng tan trong nc, c th ko thnh si. N l c bn to nn cc c ng vt. Cc prtit
ca loi ny v d nh keramin c trong da, tc, xngmizin c trong cc bp c
Prtit dng cu tan trong nc, trong dung dch axt long, baz long hoc cc mui.
Cc prtit ca loi ny ng vai tr iu khin cc hot ng ca s sng nh cc loi men, cc
loi hocmon. V d inxulin c trong d dy, anbumin ca trng, hmglbin ca mu
16.11.2. S bin tnh.
S kt ta khng thun nghch ca prtit gi l s bin tnh. Hin tng ny thng xy
ra di tc dng ca nhit , axt, baz hoc mt s tc nhn khc. V d s kt ta ca trng
l biu hin s bin tnh ca anbumin. S bin tnh ca prtit lm bin i hon ton cc tnh
cht ca prtit v lm mt hn tnh cht sinh hc ca n.
16.11.3. Cu to ca prtit.
Thng ngi ta xem xt cu to ca cc prtit bng cch phn thnh 2 loi. Loi th
nht l cu to m trong cc nguyn t kt hp vi nhau bng lin kt cng ho tr to
thnh cc cu trc khng gian dng vng, dng l hoc dng cu.
1- Loi cu to th nht.
Trong cu to loi ny cc prtit c to thnh t nhng mch peptit-tc l cc gc
aminaxt. Khc vi cc peptit, chng c phn t lng ln hn (trn 10.000) v cu to phc
tp hn.
N
...
H
C
H
R
C
O
N
H
C
H
R'
C
O
N
H
C
H
R'
C
O
N
H
C
H
R
C
O
N
H
C
H
R'
C
O
...
2- Loi cu to th 2.
Cc phng php phn tch vt l hin i cho thy rng trong cu to thuc loi ny cc
prtit thng c lin kt vi nhau bi cc cu ni hyr v c to nn bng cc n v cu
trc lp li ging nhau. Tu thuc vo cu trc ca mch v cu lin kt hyr m cc prtit c
dng khng gian khc nhau. Di y l mt s v d v cu trc ca prtit.
N
H
H R
C
O
N
H
R
H
C
O
N
H
H R
C
O
Dng phng ziczc

N
H
H R
R H
C
O
N
H
C
O
N
H
H
R
C
O
Dng un cong

N
H
O
C
H R
R
H
H R
C
O
H
N
R H
N
H
H
N
O
C
C
O
H R
N
H
C
O
H
N
O
C
R H
Mt phng dng vng


Dng l Dng xon
16.1. a. Khi nim v aminoaxit.
b. Phn loi aminoaxit. Gii thch aminoaxit thay th v khng thay th.
16.2. Trong dung dch axit mnh, aminoaxit c hai nhm axit: NH
3
+
v COOH
a. Nhm no c tnh axit cao hn.
b. Nhm no u tin cho proton khi thm kim vo dung dch. Hp cht no to thnh.
16.3. Trong dung dch kim mnh, aminoaxit tn ti dng NH
2
-
v COO
-
.
a. Nhm no c tnh baz mnh hn.
b. Khi thm axit, nhm no u tin proton ha. Hp cht no to thnh.
16.4. Hp cht A c cng thc phn t C
3
H
7
O
2
N phn ng vi HNO
2
gii phng N
2
, phn ng
vi etanol/HCl cho hp cht C
5
H
11
O
2
N. Khi un nng A cho B c cng thc phn t
C
6
H
10
O
2
N
2
. Xc nh cng thc cu to ca A, vit cc phng trnh phn ng xy ra v gi tn
B.
16.5. Vit cng thc cu to ca cc aminoaxit c cng thc phn t C
4
H
9
NO
2
. Gi tn v ch
r ng phn quang hc.
16.6. Vit phng trnh phn ng tng hp:
a. Leuxin t ru isobutylic
b. Lysin t 1,4-dibrombutan
c. Prolin t axit adipic
16.7. Hp cht A c cng thc phn t C
5
H
11
NO
2
, tan c trong c axit v kim, tc dng vi
etanol to thnh cht C
7
H
15
NO
2
. Khi un nng A s gii phng NH
3
v chuyn thnh cht B m
khi oxi ha s to thnh axeton v axit oxalic. Xc nh cng thc cu to ca A.
16.8. Hai cht ng phn A v B c cng thc phn t C
9
H
11
NO
2
, u tan trong axit v kim.
Khi cho A v B tc dng HNO
2
cho hai hp cht A v B c cng thc phn t C
9
H
10
O
3
, khi
un nng A v B vi axit sunfuric c to thnh C c cng thc phn t C
9
H
8
O
2
ri oxi ha
tip cho axit terephtalic v CO
2
. Xc nh cng thc cu to ca A v B.
Ni.

10 Hoa - Huu - Co

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nn mch cacbon trong phn t

l gim rt nhanh khi ko di mch truyn nh

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