14 Hoa Hoc Huu Co (PHU) PDF

B CNG THNG TRNG CAO NG CNG NGHIP TUY HA KHOA CNG NGH - MI TRNG
------
TRN VN THM
Bi ging:
Organic Chemistry
NH2 N N N N H H OH
Guanine
O NH N O
HO O H
Uracil
N HO H H O OH
-
O H H OH NH2 N N
Cytosine
Adenine
H NH OH N O
-
N O O
NH2 O H H OH O H
P O
-
O H H
P O-
H H OH
OH
H OH
Tuy Ha, nm 2007
http://hhud.tvu.edu.vn
Ho hc hu c - phn mc lc
Trang 1
PHN MC LC
Trang Chng 1: I CNG V HO HC HU C 1.1. Hp cht hu c v ho hc hu c 1.2. Phng php tch v tinh ch cht hu c 1.3. Phn tch nguyn t v thit lp cng thc phn t 1.4. Lin kt trong ho hc hu c Chng 2: CC HIN TNG NG PHN TRONG HA HU C 2.1. ng phn cu to 2.2. ng phn lp th Chng 3: S TC DNG TNG H CC NGUYN T TRONG PHN T 3.1. Hiu ng cm ng 3.2. Hiu ng lin hp 3.3. Hiu ng siu lin hp 3.4. Hiu ng khng gian Chng 4: PHN NG HU C 4.1. Mt s khi nim chung 4.2. c im ca phn ng hu c 4.3. Phn ng th trong ho hc hu c 4.4. Phn ng tch loi trong ho hc hu c 4.5. Phn ng cng hp trong ho hc hu c Chng 5: HIROCACBON 5.1. Hirocacbon no 4 6 8 10 16 16 17 24 24 26 29 30 32 32 32 34 36 39 42 42
http://www.ebook.edu.vn
Trang 2
5.2. Hirocacbon khng no 5.3. Hirocacbon thm Chng 6: HP CHT HU C N CHC V A CHC 6.1. Dn xut halogen 6.2. Hp cht c nguyn t 6.3. Ancol v phenol 6.4. Anehit v xeton (hp cht cacbonyl) 6.5. Axit cacboxylic v dn xut 6.6. Amin Chng 7: HP CHT TP CHC 7.1. Hiroxiaxit 7.2. Gluxit 7.3. Aminoaxit 7.4. Protein Chng 8: HP CHT D VNG 8.1. Khi nim 8.2. D vng 5 cnh mt d t 8.3. D vng 6 cnh mt d t - Piriin THC HNH Bi 1- Phn tch nguyn t trong HCHC Bi 2- Hiro cacbon Bi 3- Dn xut halogen ca hirocacbon
50 67 77 77 85 90 102 110 124 130 130 131 140 141 145 145 147 149 152 152 154 161
Trang 3
Bi 4- Ancol phenol ete Bi 5- Anehit xeton Bi 6- Axit cacboxylic v dn xut
165 170 175
Chng 1: i cng v ho hc hu c
Trang 4
Chng 1: I CNG V HO HC HU C
1.1. Hp cht hu c v ho hc hu c 1.1.1. Khi nim v hp cht hu c v ho hc hu c Cacbon l mt nguyn t ho hc rt c bit: cc nguyn t C c th kt hp vi nhau v vi nguyn t ca nguyn t khc to nn khong 10 triu hp cht khc nhau, y l nhng hp cht ca cacbon. Trong khi , cc nguyn t ho hc cn li trong BTH ch c th to nn chng 1 triu hp cht khng cha cacbon. Nhng hp cht ca C (tr CO, CO2, cc mui cacbonat, ...) c gi l hp cht hu c. Ngnh ho hc chuyn nghin cu cc hp cht hu c, tc l cc hp cht cha cacbon, c gi l ngnh ho hc hu c. 1.1.2. Lc s pht trin ngnh ho hc hu c Loi ngi bit iu ch v s dng cc sn phm hu c dng khng tinh khit hoc hn hp t rt lu (ng ma, gim, phm nhum, tinh du, ...), song mi ti gia th k XVIII mi tch c t thc vt v ng vt mt s hp cht hu c tng i tinh khit (axit citric, axit tactric, ure, ...) u th k XIX ho hc hu c tch ra t ho hc ni chung, v tr thnh mt ngnh khoa hc c lp. Ngi ta gi ho hc hu c (Beczeliuyt, 1806) v hi ch c cc cht hu c thin nhin tn ti trong c th ng vt v thc vt. V th, thi by gi xut hin mt quan nim duy tm gi l thuyt lc sng, theo cc cht hu c ch c th sinh ra trong c th sng nh mt lc huyn b no . Quan nim ny ch tn ti c vi chc nm, v b bc b bi cng trnh tng hp hng lot hp cht hu c xut pht t cc cht hu c khc hoc cc cht v c, nh tng hp axit oxalic (1824), ure (1828), cht bo (1854), .... Cng vi nhng thnh tu v tng hp hu c, t gia th k XIX hnh thnh thuyt cu to ho hc (1861) v quan nim u tin v ho hc lp th (1874). Bc sang th k XX, trong ho hc hu c hnh thnh thuyt electron v cu trc phn t v khi u thi k pht trin mnh m cng nghip hu c (nhin liu, dc phm, phm nhum, polime, ...). Sau chin tranh th gii th hai, cng vi s pht trin v bo ca ho hc lp th, cc thuyt electron v cu trc phn t v c ch phn ng. S thm nhp ca ton hc, c hc, vt l hc, ... vo ho hc hu c v s thm nhp su mnh ca ho hc hu c vo cc ngnh sinh hc, y dc, nng nghip, ... v c bit l s pht trin cc phng php vt l nghin cu cht hu c cng vi cc php phn tch v tng hp hu c hin i. Hin nay hoa shc hu c ang thi k pht trin mnh m nht v c vai tr quan trng trong mi ngnh kinh t quc dn. Cc cht hu c c mt khp ni, ngoi c th sng ta gp cht hu c trong thc phm, dc phm, phm nhum, cht do, si t, cao su, m phm, bt git, cht phng tr dch hi, cht kch thch tng trng, thuc n, nhin liu, .... Trong th gii quanh ta, u u cng c bng dng hp cht hu c.
Trang 5
Nh c ho hc hu c ngi ta mi hiu c su sc cc cht to nn c th sng v bn cht qui trnh din ra trong c th sng. V vy, ho hc hu c l c s ca cc ngnh ho hc trung gian nh ho sinh, ho dc, .... Ho hc hu c khng cn l mn hc m t thun tu nh trc y, m t lu tr thnh mt mn hc suy lun, va c l thuyt va c thc nghim. 1.1.3. Phn loi hp cht hu c C th phn loi hp cht hu c theo hai cch chnh sau y: a) Phn loi thnh H C v dn xut ca H C H C l nhng hp cht hu c c cu to bi hai nguyn t H v C. Cc dn xut ca H C cha trong phn t khng nhng C v H m cn c c nhng nguyn t khc nh O, N, S, .... l nhng hchc c nhm chc. Nhm chc l nhm nguyn t (or: nguyn t) quyt nh tnh cht ho hc c trng ca c dy hp cht c cng loi nhm chc trong phn t (gi l chc ho hc). Khi phn t ch c mt nhm chc duy nht ta gi l hp cht hu c n chc. Th d: C2H5OH, CH3CHO, CH3COOH, ... Khi phn t c hai hay nhiu nhm chc ng nht ta gi l hp cht hu c a chc. Th d: (COOH)2, CH2OH CHOH CH2OH, ... Khi phn t c hai hay nhiu nhm chc khc ta gi l hp cht hu c tp chc chc. Th d: NH2CH2-COOH, CH2OH (CHOH)4 CHO, ... b) Phn loi theo mch C H C v dn xut ca chng u c th c phn loi theo mch C (mch h, mch vng, mch no, mch khng no, ...) Cc hp cht hu c
Hp cht mch h (hp cht khng vng)
Hp cht mch vng (hp cht vng)
Hp cht no
(mch C ch c LK n)
Hp cht khng no
(mch C c LK bi)
Hp cht ng vng
(trong vng ch c C)
Hp cht d vng
(Trong vng ngoi C cn c O, N, S, ...)
Vng no Vng khng no Vng thm
D vng no D vng khng no D vng thm
Chng 1: i cng v ho hc hu c 1.1.4. Ngun hp cht hu c
Trang 6
Trong thin nhin: c nhiu ngun hp cht hu c rt phong ph. l, du m v kh thin nhin (ch yu l cc H C), than (cung cp nha than cha H C thm, phenol, ...), cc sn phm ng - thc vt (cung cp gluxit, lipit, protein, ...) Trong phng th nghim v trong cng nghip: ngi ta c th tng hp hng triu hp cht hu c khc nhau, xut pht t cc cht hu c v v c, trong c nhiu sn phm cng nghip c ssn xut trn c s cc ngun nguyn liu thin nhin nu trn. 1.2. Phng php tch v tinh ch cht hu c Hu ht cc cht trong thin nhin hay mi iu ch trong phng th nghim u trng thi hn hp vi thnh phn khc nhau. kho st cu trc v tnh cht ca mt cht hu c bng thc nghim v s dng trong thc tin ngi ta phi tch cht ra khi hn hp, nhm tinh ch n thnh mt cht tinh khit hay cht nguyn cht. 1.2.1. Cc phng php thng thng a) Chit Ngi ta dng mt dung mi thch hp (nh ete, benzen, nc, ...) c kh nng ho tan tt cht hu c cn tch t mt hn hp lng hoc rn vi cht khc sang dung dch trong dung mi . Sau khi ui dung mi ra khi dung dch ta s thu c cht cn tch.
Th d: khi iu ch C6H5NH2 bng phng php kh C6H5NO2 c mt phn nh anilin tan trong nc. tch anilin ra khi nc, ngi ta cho ete vo v lc k, anilin d tan trong ete hn nc s chuyn sang ete. Tch anilin/ete ra khi v dui ete i ta s thu c anilin.
Hin nay c rt nhng dng c cho php chit lin tc. b) Kt tinh Phng php ny da vo s khc nhau v tan ca cc cht (ch yu l cc cht rn) trong dung mi thch hp, v s khc nhau v tan ca mt cht trong mt dung mi nhit khc nhau. Ngi ta ho tan mt hn hp rn trong mt dung mi thch hp bng cch un nng v lc, sau lc nng loi b tp cht khng tan ri lm lnh. Khi y cht t tan hn s tch ra trc dng tinh th sch v c ly ra bng cch lc.
Th d: axit benzoic l cht rn tan nhiu trong nc nng v rt t tan trong nc ngui. tinh ch ngi ta un axit ny trong nc c dung dch bo ho nng, ddem lc nng, ri ngui cc tinh th axit tinh khit hn s tch ra.
c) Chng ct Phng php ny da trn s khc nhau v nhit si ca cc cht khc nhau mt p sut nht nh. Ngi ta dng nhit (un nng) chuyn hn hp cht lng sang pha hi v thu cht lng khong nhit thch hp bng cch cho hi ngng t. C ba kiu chng ct thng dng: Chng ct thng: Khi tch mt cht lng c nhit si khng cao ra khi cc cht khc c nhit si khc xa ta c th chng ct bng cch on gin nht gi l chng ct
Trang 7
thng. Th d, un si nc sinh hot trong bnh, nc s bc thnh hi, dn hi qua b phn lm lnh hi nc ngng t thnh nc tinh khit hn, cn li trong bnh l cc cht kh bay hi. Chng ct phn on: Phng php ny dng tch hn hp lng gm cc cht c nhit si cch xa nhau khng nhiu lm, nh mt dng c gi l ct ct phn on gn lin hoc lp thm vo bnh cng ct. Cht no c nhit si thp hn s bay hi trc ri ngng t ri ly ring ra, tip theo n cht no c nhit si cao hn. Th d, hn hp gm benzen v toluen trong bnh c lp ct ct phn on, benzen s bay hi v thot ra trc, sau n toluen. i vi cht c nhit si cao v d phn hu nhit si ca n, ngi ta chng ct di p sut thp h nhit si v trnh s phn hu. Chng ct bng cch cho li cun theo hi nc: C nhng cht hu c nhit si rt cao v rt t tan trong nc, song c th c chng ct dng hn hp vi hi nc nhit si ca nc.
Cch tin hnh: cho mt dng hi nc nng i qua hn hp cc cht cn tch ra, hi nc s lm cho mt vi thnh phn ca hn hp bay hi theo hi nc. Th d, chng ct anilin, tinh du thc vt, ...
1.2.2. Phng php sc k Nguyn tc: hn hp cc cht cn tch v dung mi c dng lm pha ng th lng hoc kh. Pha ng thng xuyn tip xc vi pha tnh l mt cht rn c din tch b mt rt ln, hoc mt cht lng trng ln b mt cht rn, khin cho cc thnh phn ca hn hp c tc chuyn dch khc nhau s tch ra khi nhau. Phn loi: ta phn bit hai loi chnh l sc k hp ph v sc k phn b. a) Sc k hp ph Da theo s khc nhau v h s hp ph ca cc cht. Pha tnh l mt cht rn, pha ng l cht lng hoc cht kh. Sc k hp ph c th c cc dng sc k ct, sc k lp mng, sc k kh. b) Sc k phn b Pha tnh l cht lng, pha ng l cht lng hoc cht kh. Sc k phn b c th l sc k ct, sc k lp mng, sc k kh. Sc k ct: thng gp l loi m pha tnh l cht rn nh alumin (Al2O3), silicagen (SIO2.nH2O) c t trong mt ng thng ng (ct), pha ng l dung dch cha hn hp cn tch trong dung mi thch hp. Sc k giy: thng pha tnh l nc ng v trn giy. Sc k lp mng: pha tnh l lp mng cht hp ph nh silicagen trng trn mt bn thu tinh hoc bng nhm, pha ng l dung dch cha hn hp cn tch c a vo bng cch nhng hoc nh git, cht lng di chuyn nh tc dng mao dn. Sc k kh: Pha ng l mt cht kh, cn pha tnh c th l cht rn hoc cht lng.
Trang 8
1.3. Phn tch nguyn t v thit lp cng thc phn t 1.3.1. Phn tch nh tnh nguyn t Phn tch nh tnh nguyn t nhm xc nh cc loi nguyn t c mt trong hp cht hu c. Nguyn tc chung l chuyn cc nguyn t trong hp cht cn kho st thnh nhng cht v c n gin ri nhn ra cc sn phm ny da vo nhng tnh cht c trng ca chng. a) Xc nh C v H un nng cht hu c vi CuO (cht oxy ha) chuyn C thnh CO2 v H thnh H2O, ri nhn bit CO2 bng nc vi trong (to kt ta trng CaCO3) v nhn bit H2O bng CuSO4 khan (mu trng chuyn thnh mu xanh ca CuSO4.5H2O) [C]hchc + [H]hchc + CO2 5H2O b) Xc nh N un nng hp cht hu c vi Na s xinh ra NaCN. nhn ra ion CN- ta cho thm Fe2+ v Fe3+ ri axit ho nh, nu c CN- s sinh ra kt ta mu xanh m rt c trng ca Fe4[Fe(CN)6]3: Na + [C] + [N] + + 2CuO CuO
CO2
+ +
2Cu Cu + H2O
H2O
Ca(OH)2 CaCO3 CuSO4
CuSO4.5H2O
NaCN
[Fe(CN)6]4-
hp cht hu c Fe2+ 4Fe3+ + + 6CN-
3[Fe(CN)6]4-
Fe4[Fe(CN)6]3
c) Xc nh halogen t mt bng giy lc tm cht hu c c cha Hal v ancol etylic (nhin liu) s sinh ra HX. Ta nhn bit HX bng dd AgNO3 (sinh ra kt ta AgX) sau xc nhn AgX bng dd NH3 (ho tan kt ta): [X]hchc HX AgX + + + [H]hchc or ancol AgNO3 3NH3 +
HX
AgX +
H2O HNO3
[Ag(NH3)2]OHtan + NH4X
1.3.2. Phn tch nh lng nguyn t Phn tch nh lng nhm xc nh thnh phn % v khi lng ca cc nguyn t trong hp cht hu c. Nguyn tc chung l chuyn hon ton cc nguyn t trong mt lng cn nht nh ca cht hu c thnh cc cht v c n gin, sau xc nh khi lng (hoc th tch i
Trang 9
vi cht kh) c sn phm , ri tnh thnh phn % cc nguyn t. a) nh khi lng C v H Nung nng mt lng cn chnh xc a gam hp cht hu c vi CuO d trong dng kh O2. Kh CO2 v hi nc sinh ra c hp th hon ton v ring r bi nhng bnh cha cc cht hp th thch hp c cn trc v sau khi th nghim. Gi s trong th nghim sinh ra
mCO2 v
mH 2O , ta tnh:
mC = 12 mCO2 44 12 mCO2 44 a 100 mH = 2 m H 2O 18 2 mCO2 18 a 100
%C =
%H =
b) nh lng N un nng mt lng cn chnh xc a gam hp cht hu c vi CuO d trong dng kh CO2 chuyn ht N trong hp cht thnh kh N2 v dn vo nit k (dng c o kh nit) cha trong dd KOH m c ( hp th CO2 v H2O). Gi s thu c V ml kh N2, o nhit t, p sut kh quyn p, p sut hi nc bo ho f, ta tnh c :
mN2 =
28 1 p f V 22400 760 1 + t 273 mN 2 a 100
%N =
c) nh lng halogen Sau khi phn hu mu cht hu c chng hn bng oxi hay axit nitric bc khi, cc halogen c chuyn thnh AgX nh lng. d) nh lng oxi Thng thng hm lng oxi trong mt hp cht hu c c xc nh trc tip bng cch ly 100% tr i tng s % ca cc nguyn t khc c trong hp cht. tuy vy, khi cn thit cng c th xc nh trc tip bng cch chuyn oxi trong mu thnh CO ri nh lng CO da theo phn ng: 5CO + I2O5
5CO2 +
I2
1.3.3. Xc nh phn t khi i vi cc cht kh hoc cht lng d bay, ta c th xc nh t khi d ca cht so vi mt kh n gin no (th d: H2, N2, khng kh, ...) ri tnh khi lng phn t:
dA =
B
MA MB
Trang 10
i vi cht rn hoc cht lng khng bay hi: da vo phng php nghim lnh v phng php nghim si:
M =k
g1 1000 g 2 t
Php nghim lnh c dng rng ri hn php nghim si. 1.3.4. Thit lp cng thc phn t Gi s hp cht hu c c CTPT l CxHyOzNt Lp cng thc n gin nht: x : y : z : t =
mC mH mO mN : : : 12 1 16 14
Lp cng thc phn t da vo khi lng cc nguyn t:
y 16 z 14t M 12 x = = = = mC mH mO mN a
Lp cng thc phn t da vo phn trm cc nguyn t:
12 x y 16 z 14t M = = = = %C % H %O % N 100
Th d: t chy hon ton 0,44 gam mt hp cht hu c A, sn phm chy c hp thu hon ton vo bnh 1 ng P2O5, v bnh 2 ng dung dch KOH. Sau th nghim thy khi lng bnh 1 tng 0,36g v bnh 2 tng 0,88. a) Xc nh CTn gin nht ca A? b) Xc nh CTCT ng ca A, bit phn ng ht vi 0,05 mol A cn dng 250ml dung dch NaOH 0,2M v A c kh nng tham gia phn ng trng gng. 1.4. Lin kt trong ho hc hu c 1.4.1. Lin kt xch ma () v lin kt pi () Lin kt ho hc quan trng v ph bin nht trong hp cht hu c l lin kt cng ho tr. Lin kt ny c hnh thnh bng s xen ph cc obitan nguyn t (AO) to nn obitan phn t (MO) chung cho c hai nguyn t tham gia lin kt. C hai kiu xen ph chnh: a) Xen ph trc MO c trc i xng trng vi trc ni hai ht nhn nguyn t lin kt:
s - s (xichma)
p - p (xichma)
s - p (xichma)
Hnh 1.1: Obitan l nhng MO bn vng, c gi l MO . Lin kt cng ho tr c hnh thnh bng s xen ph trc nh trn c gi l lin kt xch ma. Lin kt tng i bn, hai nguyn t ni vi nhau ch bng lin kt thi th c kh
Trang 11
nng quay quanh trc lin kt m khng lm mt s xun ph (th d: CH3 CH3), do c kh nng xut hin cu dng hp cht hu c. b) Xen ph bn Vng xen ph nm hai bn tc ni hai ht nhn nguyn t lin kt nn MO tng i km bn. l MO , v lin kt tng ng l lin kt . So vi lin kt xch ma th lin kt pi km bn. Hai nguyn t ni vi nhau bng lin kt pi (v mt lin kt xch ma) khng th quay quanh trc ni hai ht nhn c v nh th s vi phm s xen ph cc i ca hai AO. Do , c kh nng xut hin ng phn hnh hc cc hp cht c ni i: C = C, C = N, ...
p-p
Hnh 1.2: Obitan pi 1.4.2. S lai ho obitan v cc lin kt n, i, ba trng thi c bn nguyn t C c cu hnh electron: 1s 2 s 2 p x 2 p y trng thi lin kt nng lng cao, mt electron 2s chuyn ch sang obitan cn trng 2pz, do C* c cu hnh: 1s 2s 2 p x 2 p y 2 p z
2 1 1 1 1 2 2 1 1
Khi y c s t hp gia obitan 2s vi mt s obitan 2p, gi l s lai ho obitan. Cc obitan mi hnh thnh c gi l obitan lai ho. Cacbon c 3 kiu lai ho: a) Lai ho sp3 (hay lai ho t din) Lai hoa sp3: Mot obitan 2s lai hoa vi 3 obitan 2p tao thanh 4 obitan lai hoa sp3 giong het nhau. Bon obitan nay hng ti 4 nh cua hnh t dien mat eu, tao thanh goc gia cac obitan lai hoa la 109028/ (hnh 1.3)
+ + -
+ + + + 109o28/ Hnh 1.3: S lai hoa sp3 -
sp3
Cac obitan sp3 se xen phu truc vi AO cua cac nguyen t khac tao thanh nhng lien ket .
Chng 1: i cng v ho hc hu c Th du:
Trang 12
CH4
C2H6
Hnh 1.4: Cc obitan trong phn t CH4 v C2H6 b) Lai ho sp2 (hay lai ho tam gic) Lai hoa sp2: Mot obitan 2s lai hoa vi 2 obitan 2p tao thanh 3 obitan lai hoa sp2 giong het nhau. Ba obitan nay hng ti 3 nh cua tam giac eu, hnh thanh goc gia cac obitan lai hoa bang 1200 (hnh 1.5).
+ + + +
+ -
+ 120o sp2
Hnh 1.5: S lai ho sp2

Cc obitan sp2 s xen ph trc vi obitan ca cc nguyn t khc to thnh cc lin kt xch ma. Cn li mt obitan 2p cha lai ho c trc thng gc vi mt phng cha 3 obitan lai ho sp2 s dng xen ph bn vi obitan 2p ca nguyn t khc to thnh lin kt pi (th d hnh 1.6).
(a)
(b)
Hnh 1.6: S hnh thnh lin kt xch ma (a) v lin kt pi (b) trong phn t C2H4 c) Lai ho sp (hay lai ho ng thng) Lai hoa sp: Mot obitan 2s lai hoa vi 1 obitan 2p tao thanh 2 obitan lai hoa sp giong het nhau. Hai obitan nay nam tren mot ng thang tao thanh goc gia hai obitan lai hoa bang 1800
Chng 1: i cng v ho hc hu c (hnh 1.7).

2s
Trang 13
sp 2p
sp
180O
Hnh 1.7: S lai ho sp
Cc obitan sp s xen ph trc vi obitan ca hai nguyn t khc to thnh hai lin kt xch ma. Cn li hai obitan cha lai ho 2p c trc i xng thng gc vi nhau v cng thng gc vi trc i xng chung ca hai obitan lai ho sp, s dng xen ph bn vi obitan cha lai ho ca nguyn t khc to nn nhng lin kt pi. Th d:
180o H C C H 180o H H
a)
b)
Hnh 1.8: S hnh thnh lin kt xch ma (a) v lin kt p (b) ca C2H2 1.4.3. Lin kt hiro a) Khi nim
Lin kt hiro l lin kt c hnh thnh gia mt nguyn t H tham gia lin kt cng ho tr vi mt nguyn t khc cng d tham gia lin kt cng ho tr v cn cha cp electron t do. Th d: lin kt hiro c hnh thnh gia phn t H2O
H O ... H H O ... H H O ... H H O H
iu kin hnh thnh lin kt hiro: l LKCHT X H cha nguyn t H phi phn cc mnh, nguyn t H mang mt phn mang in tch dng (+), cn nguyn t th hai Y phi c cp e t do mang mt phn in tch m (-) v c m in ln hn.
+
LKCHT phn cc
H Y
Lin kt hiro
y X cng nh Y thng l O, N, F. Lin kt X H cng phn cc v kh nng nhng electron ca Y cng ln th lin kt hiro cng bn vng.
b) Phn loi lin kt hiro
Lin kt hiro lin phn t: l lin kt gia X H v Y thuc v hai phn t ring r (ging nhau hoc khc nhau). Th d:
O ... H O C O H ... O
Trang 14
O ... H C2H5
O C2H5
O ... H C6H5
O CH3
CH3
CH3
Lin kt hiro ni phn t: l lin kt gia X H v Y ca mt phn t. Th d:

H CH2 CH2 O H O O H F
c) S nh hng ca lin kt hiro n tnh cht ca hp cht hu c
Lin kt hiro lin phn t lm tng mnh nhit si v nhit nng chy so vi nhng cht c phn t khi tng ng m khng c lin kt hiro hoc ch c lin kt hiro ni phn t. Th d: Hp cht CH3 CH2 OH CH3 O CH3 CH3 SH p-NO2 C6H4 OH o-NO2 C6H4 OH M 46 46 48 139 139 ts (oC) 78 -24 6 tnc (oC) 114 44
S hnh thnh lin kt hiro gia cht tan v dung mi lm tng mnh tan trong dung mi . Nhm chc c kh nng to lin kt hiro vi dung mi cng tng th tan ca cht cng ln, tri li gc H C cng ln tan ca cht cng nh. Th d: Hp cht CH3 CH2 OH N C4H9 OH n C6H13 OH C6H12O6 (glucoz) n C6H14 CH3 COOH HCOOCH3 M 46 74 102 180 86 60 60 tan (g/100g H2O)
7,4 0,6 83 0,01
30
Ch rng ngoi lin kt hiro ra, gia cc phn t hp cht hu c cn c th c cc lc lin kt yu nh lc ht lng cc gi cc phn t phn cc, lc Vandecvan, ...
Chng 1: i cng v ho hc hu c BI TP
Trang 15
1.1. Hy nu nh ngha: cht hu c, ho hc hu c, H C, gc H C, gc t do, dn xut ca hirocacbon. 1.2. Cho cc cng thc sau y: CH3Cl (A); COCl2 (B); CaC2 (C); C2H6 (D); C6H6 (E); CH3COOH (F); CH3 C+H CH3 (G); H2C2O4 (H); CH3 CH2*(I). Hy ch r hchc, H C, nhm chc? 1.3. Nguyn tc chung ca php phn tch ho hc cc nguyn t trong hchc l g? Minh ho bng hai th d c th ? 1.4. Adrenalin l mt hocmon. Trn 18,3 mg adrenalin vi bt CuO (ly d) ri nung nng th thu c 1,27 ml kh nit (o 270C v 750 mmHg). Nu t chy hon ton cng adrenalin lng trn nh vy trong oxi th thu c 39,6 mg CO2 v 11,7 mg H2O. Tm thnh phn % cc nguyn t trong adrenalin ? 1.5. C mt cht hu c khn gtinh khit ly t ngun thin nhin. Hy nu cc bc thc nghim v tnh ton thit lp CTPT ca hp cht ? 1.6. Phn tch nh lng 10,5 mg hp cht hu c A (cha C, H, O) thu c 30,8 mg CO2 v 4,5 mg H2O. Ho tan 1,03g A trong 50 gam benzen ri xc nh nhit si ca dung dch thy ts=80,3560C, trong khi benzen nguyn cht c ts = 80,10C. xc nh CTPT ca A, bit hng s nghim si trong trng hp ny l 2,61. 1.7. Hy nu nguyn tc ca mt vi phng php tinh ch hchc: cht rn v cht lng? 1.8. Hp cht hu c A c khi lng phn t nh hn khi lng phn t ca benzen ch cha 4 nguyn t C, H, O, N, trong hiro 9,09% nit 18,18% t chy 7,7 gam cht A thu c 4,928 lt kh CO2 o 27,30C, 1atm v A tc dng vi dung dch NaOH. Cho bit cng thc cu to c th c ca A? 1.9. Cht X cha cc nguyn t C, H, O trong hiro chim 2,439% v khi lng. Khi t chy X u thu c s mol nc bng s mol mi cht chy, bit 1 mol X phn ng va ht vi 2,0 mol Ag2O trong dung dch amoniac. Xc nh cng thc cu to ca X? 1.10. t chy hon ta 4,5 gam cht hu c A (gm C, H, O) thu c 3,36 lt CO2 (ktc) v a) Xc nh CTPT ca cht A? b) A c ng phn th nht l X tc dng vi Na2CO3 gii phng CO2, ng phn th hai l Y tc dng vi dd NaOH to ra ru metylic v ng phn th 3 l Z va tc dng vi Na v va c phn ng trng gng. Xc nh CTCT ca X, Y v Z. 1.11. Bn cht ca lin kt CHT l g? Hy trnh by bng hnh v theo quan nim hin i s 2,7 gam H2O. T khi ca Z so vi H2 bng 30.
hnh thnh cc lin kt cng ho tr trong mi phn t sau y: CH3 CH3 ; CH2 = CH2 ; CH CH ; CH2 = CH CH = CH2 v C6H6 1.12. Bn cht ca lin kt hiro l g? Nu th d minh ho. Trnh by bng CTCT lin kt hiro gia cc phn t trong trng hp: metanol, axit axetic, dd phenol trong etanol.
Chng 2: Cc hin tng ng phn trong ha hu c
Trang 16
Chng 2: CC HIN TNG NG PHN TRONG HA HU C

Cc hin tng ng phn gn lin vi cu to v cu trc khng gian ca phn t. y l mt hin tng rt ph bin trong ha hc hu c. Nh c hin tng ng phn ny m s cc hp cht hu c tng ln rt nhiu. Cc cht gi l ng phn vi nhau l nhng cht c cng cng thc nguyn, nhng khc nhau v CTCT v tnh cht. Ngy nay ngi ta bit rt nhiu hin tng ng phn. phn bit v s dng c th chia ra lm hai dng biu din: ng phn cu to (ng phn mt phng) ng phn lp th (ng phn cu trc) 2.1. ng phn cu to 2.1.1. ng phn v mch cacbon ng phn v mch C l ng phn v cch sp xp mch C theo cc trt t cu to khc nhau, dn n tnh cht khc nhau. V d: C4H10 (butan) c cc ng phn sau:
CH3 - CH2 - CH2 - CH3 n-butan CH3 - CH - CH3 CH3 iso-butan
2.1.2. ng phn v v tr nhm chc ng phn v v tr nhm chc l nhng ng phn c cng nhm chc, ch khc nhau v v tr nhm chc trn mch C. V d: ancol C3H7OH c hai ng phn v nhm chc sau:
CH3 - CH2 - CH2 - OH propanol-1 CH3 - CH - CH3 OH propanol-2
Hay: C6H4CH3OH c cc ng phn v v tr nhm OH sau:

CH3 OH o-cresol CH3 OH m-cresol CH3
OH p-cresol
2.1.3. ng phn v chc hu c Nhm chc l nhm c trng cho tnh cht ha hc ca hp cht. ng phn v chc hu c l ng phn to ra cc nhm chc khc nhau ca hp cht c cng thnh phn. V chc ancol v ete: V chc axit v este: CH3 CH2 OH v CH3 O CH3 CH3COOH v HCOOCH3
V chc andehit, xeton v ru: CH3 CH2 CHO ; CH3 CO CH3 ; CH2 = CH CH2 OH.
Trang 17
V bc ca nhm chc: CH3 CH2 CH2 NH2 ; CH3 NH CH2 CH3

CH3 N CH3 CH3
2.1.4. ng phn h bin (tautome) ng phn h bin l ng phn ca hai cht c cng thnh phn nhng khc nhau v cu to. Hai cht ny trng thi chuyn ha ln nhau:
O CH3 - C - CH2 - C - CH3 O O axetyl xeton CH3 - C = CH - C - CH3 OH 2-hodroxyl-2-pentenon
Chuyn ha ny c gi l h bin xeton anol. Ngoi ra trong hu c cn gp nhiu dng h bin khc.
Nitroso - oximino Amido - imidol CH - N = O NH - C = O C = N - OH N = C - OH
Nguyn nhn gy ra ng phn h bin l do s chuyn ch ca nguyn t H trn cc trung tm O, N, 2.2. ng phn lp th 2.2.1. ng phn hnh hc (ng phn Cis Trans) Cc ng phn khc nhau v v tr cc nhm th I vI mt phng lin kt i, hoc i vi mt phng ca vng (i vi hp cht c cu to vng)
H C=C Cl Cl Cl Cis-1,2-dicloeten H H C=C H CH3 CH3 H CH3 trans-1,2-dicloeten Cis-1,2-dimetyl xiclohexan Trans-1,2-dimetyl xiclohexan Cl
CH3
iu kin c ng phn hnh hc: Phn t phi cha lin kt i hoc vng kn. Cc nguyn t C c cha lin kt i v vng kn phi lin kt vi hai nguyn t hoc 2 nhm th c bn cht khc nhau. Khi hai nhm th cng pha ta c dng ng phn cis, hai nhm th khc pha cho dng ng phn trans. ng phn cis v trans khc nhau v tnh cht vt l. Nhit nng chy ca cis thp hn trans, nhng nhit si ca cis li cao hn nhit ca trans. V d, diphenyl butadien c 3 ng phn:

C6 H 5 C=C H H trans - trans C=C C6H5
Trang 18
H H
C6 H 5 C=C H H
H C6 H5 C=C H H C6H5
H C=C
H C6 H5 H
C=C cis - cis
trans - cis
S ng phn ca phn t c n ni i tnh theo cng thc: N = 2n-1 + 2p-1 N l s chn th p = 2.2.2. ng phn cu dng Nh chng 1 v lin kt ha hc trnh by lin kt c c ch xen ph cc obitan lai ha dc theo trc ni hai tm ht nhn. V vy, cc nguyn t hay nhm nguyn t c kh nng quay quanh lin kt ny m lin kt vn tn ti. Do n ng khng gian, do khong cch thay i ca cc nguyn t, nhm nguyn t khc nhau khi quay quanh lin kt th nng tng tc thay i. Nng lng tiu tn quay khong 4 kcal/mol nh hn rt nhiu so vi cc nng lng khc. Mi trng thi ca nguyn t, nhm nguyn t trong khng gian c dng hnh th xc nh v nng lng tng tc nht nh. Dng hnh th ny gi l cu dng. Cc cu dng hnh thnh khi quay quanh lin kt xch ma c nng lng khng khc nhau lm, kh tch ra ring c. Trong v s v tr trong khng gian, c mt s v tr trong khng gian m cc nguyn t, nhm nguyn t c khong cch xa nhau nht v tng tc nhau s nh nht. Cu dng to thnh trong trng thi ny s bn nht. iu kin bnh thng cc phn t thng tn ti cu dng ny. biu din cc cu dng trn mt phng m th hin c cu trc khng giam 3 chiu. Vic lm ny khng n gin vi cc phn t c nhiu nguyn t. V vy, phi c mt hnh thc biu din tng trng khc. Sau y minh ha mt s cch biu din n gin cu dng phn t. Biu din theo phi cnh: Cu dng ca buttan
n n +1 , n l s l th: p = 2 2
CH3 C H H
CH3 H C CH3 C H H H CH3 H H CH3 C H C H
H C CH3 C H H CH3
CH3 C H H
Theo Newman, nt m th hin lin kt hng ra ngoi t giy trc mt ngi quan st,
Trang 19
nt thng biu din lin kt nm trn t giy, nt chm chm nm pha sau t giy.
CH3 H H CH3 H H
H3C CH3 H H
Biu din theo Newman cu dng ca butan. a) ng phn cu dng mch h Metan c cu trc mt t din u, gc lin kt 109028, di lin kt C H bng 1,1A0. N c cu hnh xc nh v khng c ng phn cu dng. Etan l cht u tin ca ankan c kh nng tn ti ng phn cu dng. Khi nhm metyl ca etan quay quanh lin kt xchma 3600, cc v tr nguyn t H trong phn t cng thay i, th nng tng tc ca chng cng thay i theo. S bin thin th nng tng tc (nng lng tng tc) ca nguyn t H khi nhm CH3 quay t 0 3600 c biu din trn hnh 3.1:
HH
HH
H H
kcal/mol
H H
H H
60
120
180
240
300
360
Hnh 2.1: Gin th nng Phn tch cu dng ca metan trn gin nhn thy cc v tr gc quay 600, 1200, 3000 tong ng vi cu dng c nng lng tng tc cc tiu. l cu dng xen k (cu dng trng). Cc hp cht kiu X3C CX3 u c gin th nng tng t nh etan. Nhng i vi butan v xut hin hai nhm th ln CH3 so vi nguyn t H, cho nn gin th nng tng tc c dng khc, khng n iu nh etan, R rng tng tc ca nhm CH3 vI H s khc tng tc ca CH3 vi CH3 bn cnh v tng tc ca H vi H. Cho nn khi quay vng 0 3600 butan c th hnh thnh cc cu dng c trng nh hnh 2.1. Butan khc vi etan c hai dng bn: cu dng ng vi nng lng cc tiu s (1) v (3),
Trang 20
(5), cu dng (1) gi l cu dng i (anti) v cu dng lch (gaucher) s (3). Ring cu dng lch phi v cu dng lch tri (3) v (5).
CH3 CH3 CH3 CH3 CH3 (2) (3) (4) (5) CH3 CH3 H C 3 CH3 CH3
CH3 (1)
H 3C (6)
kcal/mol
(4)
(2)
(6)
(1)
(3)
(5)
60
120
180
240
300
360
Hnh 2.2: Gin th nng ca butan nhit 300 K butan tn ti cu dng (1) khong 2/3 v khong 1/3 cu dng (3) v (5). S cu dng ca phn t c n lin kt nh trn c th c 3n cu dng khc nhau. b) ng phn cu dng mch vng giI thch mt s mch vng bn v mt s mch vng khng bn Bayer a ra thuyt cng vng. Vng c gc bng 109o28 l vng chun, vng bn. Cc vng c gc cng lch vi vng chun c sc cng vng ln v km bn. Gc ha tr c tnh theo cng thc:
0
180(n 2) , trong n l s cnh mch vng. 2
lch c tnh theo cng thc:
1090 28 x , trong x l gc ha tr ca vng. 2
Theo thuyt Bayer vng 5 cnh v 6 cnh c lch nh v sc cng vng nh, l vng bn nht. Cc vng ln hn v nh hn vng 5 v 6 c sc cng vng ln km bn. Nhng thc t cng c nhiu vng ln c tnh bn cao. V sau Sahse, Mohz, Pitre cho rng cc mch vng 6 cnh v ln hn 6 cnh khng c cu dng phng m c cu dng khng gian, ngha l cc nguyn t H v cc nguyn t C khng
Trang 21
nm trn mt mt phng. Do chng y nhau to ra cu dng c th nng tng tc nh nht v ng thi cng to ra cu trc bn c gc gn bng vi gc chun 109028. Th d vng 6 cnh xyclo hexan c mt cu s cu dng in hnh nh hnh 2.3:
H H H H H H H H(e) H H H H H H(a) H H H H H H(e) H (a)H
Dng thuyn (cu dng C)

H H H H H H (He) H(a) H H H
Dng gh (cu dng Z)

H(a) H(e) H H
Dng gh
H H H H H H H H HH
Dng xon
HH
Dng thuyn
Dng na gh
Hnh 2.3: Cc cu dng ca xyclo hexan nhit bnh thng phn t xyclo hexan c gn 990 tn ti dng gh. Cu dng gh c nng lng nh v bn hn cu dng thuyn. Nguyn t H v tr equatorial (e) l v tr thun li v mt khng gian v nng lng, cho nn cc nhm th u c xu hng nh hng hoc chuyn v tr v equatorial (e). Th d, metyl xyclohexan nhit bnh thng gn 95% nhm metyl v tr (e) v khong 5% v tr axial (a). Trong trng hp mch vng c hai nhm th: nh vng 6 cnh s c cc ng phn Cis v Trans nh sau: Cis: ea, ae: v tr 1,2 ea, ae: v tr 1,4 aa, ae: v tr 1,3 2.2.3. ng phn quang hc Trans: aa, ae v tr 1,2 ee, aa v tr 1,4 ae, ae v tr 1,3
Chng 2: Cc hin tng ng phn trong ha hu c a) Cht hot ng quang hc c C i xng
Trang 22
iu kin xut hin ng phn quang hc l cc cht c phn t cu trc bt i xng trong c th bt i xng phn t hoc c nguyn t C bt i xng. hnh dung v C bt i xng ta nhc lI thuyt ho lp th ca Lben v Vanhp v cu trc metan. Theo hai ng phn t metan c cu trc khng gian trong 4 nguyn t H phn trn 4 nh ca t din u v trung tm ca t din l nguyn t C, hc ho tr (HCH) bng 109028. Thuyt ny cn gi l thuyt cacbon t din.
H H Hnh 3.8: Cau dang hnh hoc cua phan t CH4 theo thuyet lai hoa. H
Hnh 2.4: Cu trc dn xut ca metan
Nu thay 4 nguyn t H trong CH4 bng 4 nhm th a, b, c, d khc nhau th nguyn t C ny c gi l nguyn t C bt I, k hiu l C*. Vic biu din cc ng phn quang hc bng hnh t din nh trn mt phng khng phi trng hp no cng thun li v vy nm 1891, E.Fischer ngh s dng cng thc chiu phng thay cho cc cng thc t din. Tu thuc vo vic chn cnh t din l cnh nm ngang v quay v pha ngi quan st m c th c cng thc chiu khc nhau.
a a b c d d c b c a
d b
Hnh 2.5: Cng thc chiu thng ca Fischer b) ng phn quang hc (cc dng cu hnh) Nh ni trn, phn t c cu trc bt i xng u c kh nng to ra ng phn quang hc. Trc ht chng ta lm quen vi trng hp n gin c mt C* l axit lactic:
H CH3 C* OH
Axit ny c hai i quang (hai cht nghch quang) l ng phn quay phi, k hiu l (d) hoc (+) gc quay theo chiu kim ng h v ng phn quay tri, k hiu l l hoc (-), gc quay ngc chiu kim ng h. Xem hnh 2.6, hai i quang ny (hai cu hnh) chng rt ging nhau nhng khng th xem chng kht ln nhau c, chng i xng nhau nh vt v nh trong gng, nh bn tay tri v bn tay phi. Chng l hai ng phn quang hc c tnh cht l ho ging nhau, ch khc nhau kh
COOH
Trang 23
nng lm quay mt phng phn cc nh sng ca mt sang phi, mt sang tri v khc nhau v hot ng sinh vt.
COOH COOH COOH COOH
hay: H H CH3 OH HO H CH3 CH3
OH
HO
CH3 Gng
Hnh 2.6: Cu hnh ca axit lactic Mt cp nghch quang nh hnh 2.6 c gc quay v tr s tuyt i bng nhau nhng khc nhau v du. Hn hp 50% ng phn quay phi v 50% ng phn quay tri cng mt phn t bt i gi l hn hp Raxemic (bin th raxemic). D nhin hn hp raxemic c tr s quay cc bng khng. Cc hp cht propadiol-1,2, andehit glyxeric l cht c mt C* v cng c mt cp i quang nh axit lactic. BI TP 2.1. Vit cng thc cu trc cc ng phn hnh hc (nu c) trong mi trng hp sau: (A): CH3 CH = CH CH3 (B): (CH3)2 CH = CH CH3 (C): CH3 CH = CH C6H5 (D): CH3 C C CH3 (E): CH3 CH = CH CH = CH CH3 (F): CH3 CH = CH COOH (G): 1,1-imetyl xiclohexan (H): 1,2-imetyl xiclohexan
2.2. Khi qut v iu kin cn v c ng phn hnh hc? 2.3. Nguyn t cacbon bt i l g? iu kin xut hin ng phn quang hc l g? Nu th d minh ho? 2.4. Cht no di y c th c ng phn quang hc? S lng ng phn l bao nhiu? (A): CH3 CHBr CH3 (B): CH3 CHBr CH2 CH3 (C): CH3 CHBr CHBr CH3 etan. (D): CH3 CHOH COOH (E): HOOC CH2 CHNH2 COOH (G): HOOC CHOH CHOH COOH
2.5. Cu dng l g? Vit cng thc cu dng bn ca etan; propan; butan; isopentan; 1,2-iclo
Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 24
Chng 3: S TC DNG TNG H CC NGUYN T TRONG PHN T Cc lin kt cng ho tr trong phn t cc cht hu c b thay i nhiu so vi lc chng mi c hnh thnh. l do cc nguyn t, nhm nguyn t trong phn t lun lun tc dng tng h ln nhau sp xp li mt in t trong cc lin kt, to ra mt phn t c cu trc thch ng vi thnh phn khc nhau to ra n. Cc tnh cht l ho, kh nng phn ng ho hc ca mI hp cht hu c u b nh hng mnh bi tc dng tng h ny. Ngi ta bit c s tc dng tng h nh qua cc hiu ng: hiu ng cm ng, hiu ng lin hp (cng hng), hiu ng siu lin hp, Sau y chng ta ln lt nghin cu cc hiu ng tc dng tng h trong ni phn t cc hp cht hu c. 3.1. Hiu ng cm ng Hiu ng cm ng l s tc dng tng h cc nguyn t, nhm nguyn t trong phn t cc hp cht H Cno hoc H - Ckhng no khng lin hp gy ra. Hp cht H C khng no c lin kt pi lin hp vi lin kt xch ma s tc dng tng h trong h ny phc tp, cho nn tm ra mt s qui lut tc dng cm ng ta ch xt trong h hp cht H C no v cha no khng lin hp. Trc ht ta i xt mt s th d sau: CH3 CH2 CH2 CH3 : n butan HCOOH c pKa = 3,7 ; CH3 COOH c pKa = 4,7; C2H5 COOH c pKa = 4,9
HO CH2 COOH c pKa = 3,0;
Cl CH2 COOH c pKa = 2,9.
Trong phn t butan ch c hai nguyn t C v H. Hai nguyn t ny c m in gn bng nhau. Cho nn cc lin kt xchma trong phn t hu nh khng phn cc. Nguyn t H khng gy ra hiu ng. Ngi ta ly hiu ng ca H bng khng so snh vi cc trng hp. Cc th d trn khi thay th nguyn t H axit fomic bng nhm nguyn t khc s nhn cc axit c axit khc nhau. Thay H bng nhm -CH3 v C2H5. Tnh axit gim so vi axit fomic. Theo l thuyt in t nhm CH3 v C2H5 khng phi l nhm y in t ho tr ra khi mnh v pha nhm COOH, lm cho lin kt O H gim s phn cc so vi nhm O H trong HCOOH. H kh phn ly ra nn tnh axit gim.
H H C H C O O H H H C H H C H C O O H
pKa ca axit propionic ln hn pKa ca axit axetic. iu ny chng t nhm etyl y mnh hn nhm metyl. Hai axit cui cng trong phn t c nguyn t Oxy v Clo l hai nguyn t c m in

ln. Chng c kh nng ht cc in t lin kt khc v mnh. Do cp in t lin kt O H b lch v pha Oxy nhiu hn, lin kt O H tr nn phn cc mnh hn so vi axit fomic, S phn ly H mnh hn nn axit tng ln. Qua cc th d chng ta c th tm ra mt s quy lut tc dng tng h trong phn t nh sau:
3.1.1. Khi nim hiu ng cm ng

Hiu ng cm ng: l s tc dng ca cc nguyn t, nhm nguyn t c m in ln lm chuyn dch in t lin kt xch ma, gy ra s phn cc phn t. Hay ni cch khc s tc dng tng h gy ra t mt trung tm nguyn t hoc nhm nguyn t c m in ln truyn i dc theo mch cacbon, lm nh hng n cc nguyn t, nhm nguyn t khc trong phn t gi l tc dng cm ng, gy ra hiu ng cm ng.
3.1.2. Phn loi hiu ng cm ng

Hiu ng cm ng ca nguyn t hay nhm nguyn t c th c gi tr dng hoc m v k hiu bng ch I. Du tr (-I) dng ch hiu ng cm ng gy ra bi nguyn t hay nhm nguyn t ht in t, gi l hiu ng cm ng m. Ngc li, nguyn t hay nhm nguyn t gy ra hiu ng bng cch nhng (y) in t, th l hiu ng cm ng dng (+I). Chiu chuyn dch mt in t theo hiu ng cm ng c m t theo bng mi tn thng:
C +
//
C +
C +
X c m in ln v trung tm gy ra hiu ng cm ng: dng cm ng c biu th bng mi tn dc theo lin kt.
+ > +/ > +// , chiu ca tc
S phn cc cm ng c m t trn lun lun c sn trong phn t v n do cc yu t cu trc trong phn t gy ra. l s phn cc tnh (Is). Bn cnh , cn c s phn cc ng do hiu ng cm ng ng (I). Tuy nhin lin kt xch ma l nhng lin kt bn, cho nn ta t gp hiu ng I v trong thc t ngi ta thng dng v hiu hiu ng v phng din tnh thi. Cc nhm nguyn t gy ra hiu ng cm ng m (-I) l nhng nguyn t, nhm nguyn t c m in ln, l cc ion dng c kh nng ht cc in t lin kt xch ma v pha mnh. Th d: (-I): CN > NO2 > F > Cl > Br > I > OCH3 > C6H5 Hiu ng cm ng dng (+I) gm cc gc ankyl, cc iion m, c kh nng y in t lin kt khi mnh. Th d: (+I): (CH3)3 > (CH3)2CH > CH3CH2 > CH3 > H
3.1.3. c im ca hiu ng cm ng
Hiu ng cm ng pht sinh v truyn i dc theo lin kt xch ma tng i nhanh, nhng yu dn v tt i cng nhanh, ch qua 4, 5 lin kt xch ma hu nh mt i.
Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 26 3.2. Hiu ng lin hp 3.2.1. nh ngha
Khc vi hiu ng cm ng, hiu ng lin hp th hin nhng phn t c h thng lin kt pi v xch ma lin hp. Ngha l trong c lin kt pi lun phin lin kt xch ma v h lin hp m rng. N gm nhng phn t c nguyn t hoc nhm nguyn t c cp in t khng lin kt (:) lin kt trc tip vi h lin hp. Cp in t ny s lin kt vi lin kt pi ca h lin hp v h lin hp ny c ko di thm, n c gi l h lin hp m rng. Th d:
CH2 = CH - CH = CH2 butadien-1,3
CH2 = C - CH = CH2 CH3 isopren
CH2 = CH - Cl vinyl clorua
benzen
cyclohexandien OH
napthalen NH2
N p-quinon phenol piridin anilin
c im ca h lin hp: khng c lin kt xch ma v lin kt pi thun tu. Cc in t
pi trong h lin hp khng nh c mt ch, chng c gii to trong ton h. Cc in t pi khng thuc mt nguyn t cacbon no. Chng c kh nng phn ng cao hn in t pi trong olefin mc d h lin hp v mt nng lng bn hn h khng lin hp. th hin chiu ca dch chuyn in t pi, cng nh s phn b lI m in t pi trong h c th dng hai cch sau:
Biu din bng mi tn cong:
CH2 = CH - Cl CH2 = CH - CH = CH2 O :OH :NH2 C-H
Biu din bng phng php cng hng (mesome): Phng php ny da vo c im
ca h lin hp cc in t pi khng nh c ti mt ch, cho nn kh dng mt cng thc c in no th hin c y trng thi thc ca h. Phng php cng hng cho rng mt phn

t ca h lin hp phi c biu din t nht hai cng thc c in tr ln (cn gi l cng thc gii hn hay cng thc cng hng) cng thc thc l cng thc trung gian gia cc cng thc .
CH2 = CH - CH = CH2
CH 2 - CH = CH - CH 2
CH 2 = CH - CH - CH 2
Phng php ny c p dng nhiu gii thch c ch phn ng. Trong phn ny ta ch s dng phng php mi tn cng tin li hn.
3.2.2. Hiu ng lin hp
Cc quy lut tc dng tng h trong h lin hp c nhiu im khc quy lut tc dng cm ng trong h khng lin hp. Nhiu trng hp khng th gii thch c nu ch s dng mt hiu ng cm ng. Hai th d sau y phn no cho thy s khc nhau .
Th d 1:
R - CHO + CH3 - CHO R - CH = CH - CHO + H2O (1) R - CH = CH - CH = CH - CH = CH - CHO + H2O (2)
R - CHO + CH3 - CH = CH - CH =CH - CHO
Mc d, trung tm gy hiu ng l nhm CHO trong trng hp (1) gn nhm CH3, trng hp (2) cch nhm CH3 bn nguyn t C, nhng hiu ng tc dng khng gim, (th hin kh nng phn ng (1) v (2) nh nhau). Hiu ng cm ng khong cch xa nh vy xem nh khng cn tc dng.
Th d 2:
H COOH Ka = 6,27.10-5 Ka = 7,20.10-5 Ka = 10,0.10-5
COOH
Cl
COOH
Br
COOH
Ka = 10,0.10-5
Thay H axit benzoic bng cc nguyn t F, Cl, Br. Tnh axit u tng ln. iu ny c th dng hiu ng cm ng gi thch c. V F, Cl, Br c m in ln ko cc in t lin kt v pha mnh lm cho lin kt phn cc, do axit tng ln so vI axit benzoic.
O F C O H
Nhng mnh ca tnh axit li tng ngc li so vi quy lut tc dng cm ng, axit p-flo

benzoic l axit mnh nht, y yu hn axit p-brom benzoic. Nh vy trong h lin hp ngoi hiu ng cm ng cn c hiu ng khc l hiu ng lin hp.
.. F
O C .O . H
Hiu ng lin hp c th hiu iu l s tc dng tng h ca cc nguyn t, nhm nguyn t trong h lin hp lm chuyn dch cc in t lin kt pi gy ra s phn cc phn t. Hiu ng lin hp cng c hiu ng lin hp tnh v ng. Khi mt phn t cha ni i lin hp tham gia phn ng cng vi hiu ng lin hp tnh c thng xuyn s xut hin hiu ng lin hp ng. N biu hin bng s phn b li mt in t m hiu ng tnh phn b. Khi phn t trng thi bnh thng hiu ng ng khng tot ra. Trong h ch c lin kt xch ma bn vng, hiu ng cm ng ng khng ng k c th b qua, nhng trong h lin hp pi, hiu ng ng ng vai tr quan trng gii thch c ch phn ng. Hiu ng lin hp gm hai loi l hiu ng lin hp dng (+C) v hiu ng lin hp m (-C) (ch C: conjugation). Hiu ng +C: gm cc nguyn t, nhm nguyn t c cp in t khng lin kt (:) s gy ra hiu ng lin hp dng: Trong chu k v phn nhm theo chiu tng ca in tch ht nhn, hiu ng lin hp dng s gim. F > Cl > Br > I NH2 > OH > F OR > SR > SeR Cc nguyn t v nhm nguyn t ny cho hiu ng +C v cm ng (-I) ngc chiu nhau. Hiu ng lin hp m (-C): gm cc nguyn t, nhm nguyn t cho C thng l nhng nhm c lin kt pi.
.. HO
O C .O . H
NO2, COOH, CHO, CONH, C N, COR, -SO3H. Trong : C = O > C = NR > C = CR2 NO2 > CN > CHO > COOH Cc nhm ny c hiu ng C v hiu ng I cng chiu nhau, trng hp ny hiu ng c tng cng. Cng nh hiu ng cm ng, hiu ng lin hp mnh nhng nguyn t c m in ln, nhm nguyn t c m in mnh hn s chi phi chiu ca hiu ng.
CH3 - O - CH = CH2 +C -C +C
NO2 -C -C
NH2 +C
c im ca hiu ng lin hp: Hiu ng lin hp xut hin nhanh, lan truyn trong h cng nhanh v gim khng ng k khi mch ko di (xa trung tm gy hiu ng).
Hiu ng lin hp cn ph thuc vo yu t tp th, khi h gim tnh cht lin hp (cu to phng) th hiu ng lin hp cng gim theo. N khng c hiu lc khi h mt tnh cht ng phng.
3.3. Hiu ng siu lin hp

y l hiu ng c bit, c th ni l trng hp ring, trng hp m rng ca h lin hp theo kiu . Hiu ng ny ch cho trng hp lin kt CH cch lin kt mt lin kt (hiu ng cm ng - , lin hp - , n - , siu lin hp - ). Th d:
H H C H
H CH3 C H CH CH2 CH3
H CH CH2 H C H
H C H C O H H
H C O H H C H
H C H
Trng hp cc iion dng cng cacboni cng c tc dng nh ni i :

H H C H C H
CH3
C H
C+
y ch c lin kt C H c vit tch ri ra nh trn mI tham gia tc dng siu lin hp vi in t pi. Obitan nguyn t H cng mt lc xen ph vI obitan ca C lin kt v obitan pi. Cc in t lin kt tng tc vi in t pi gy ra hiu ng siu lin hp. C th biu din s tc dng siu lin hp nh sau:

H CH CH2 H C H C O H H H C N H C H + C
H H C H
H C H
Kt qu tng tc lin hp ny di lin kt CC gn lin kt pi ngn hn trng hp bnh thng v c bit l hiro CH tr nn linh ng th hin trong cc phn ng ancol ho v cc phn ng khc. chng minh s c mt tng tc gy ra hiu ng siu lin hp chng ta phn tch mt s th d sau: CH3 CH = CH C2H5 + HCl Theo hiu ng cm ng nhm C2H5 cho hiu ng +I mnh hn nhm CH3 v vy sn phm cng hp l: CH3 CH = CH C2H5 + HCl CH3 CH2 CHCl C2H5 Nhng thc nghim nhn c nhm CH3 > C2H5 nn: CH3 CH = CH C2H5 + HCl CH3 CHCl CH2 C2H5 Nh vy, cc nhm ankyl khi gn lin kt pi gy ra hiu ng siu lin hp ngc li hiu ng cm ng.
3.4. Hiu ng khng gian

Nguyn nhn gy ra hu ng khng gian l do kch thc cc nhm th ln nh hng nhau. Kch thc cc nhm, cc ion ln cng knh cn tr cc tc nhn kh tip cn nhau, kh to thnh trng thi chuyn tip trong phn ng. c bit, cc phn ng xy ra v tr octo ca nhn benzen, nh hng khng gian cc nhm th chng nhng gy kh khn v tr th vo octo m cn lm mt tnh cu to phng nhm th vi nhn benzen. Do , phn ng nhn benzen thay i.
CH3 N CH3 + IC2H5 (1) N + IC2H5
(2)
Phn ng (1) thc hin kh hn phn ng (2) do mhm CH3 n ng khng gian CH3.
Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 31 BI TP

3.1. Hiu ng cm ng l g? Nu c im quan trng nht ca hiu ng cm ng ? 3.2. a) Sp cc nguyn t v nhm nguyn t theo chiu tng dn ca hiu ng cm ng m trong mi dy sau y: F ; Cl ; Br ; I OH ; NH2 ; F b) Sp cc nhm nguyn t theo chiu tng dn ca hiu ng cm ng m trong dy sau y: CH3 ; C(CH3)3 ; CH2CH3 ; CH(CH3)2.
3.3. Hiu ng lin hp l g? Nu c im quan trng nht ca hiu ng lin hp? 3.4. a) Sp xp theo chiu tng dn ca hiu ng +C trong mi dy sau y: F ; Cl ; Br ; I OH ; NH2 ; F b) Sp xp theo chiu tng dn ca hiu ng -C trong mi dy sau y: >C = O ; >C = NH ; >C = CH2 3.5. Cho ba hp cht cha oxi: CH3OH; C6H5OH; HCOOH. Hy cho bit nguyn nhn ca tnh axit trong mi trng hp sau. So snh tnh axit ca ba cht . Gii thch? 3.6. Cho ba hp cht cha nit: NH3; CH3NH2 ; C6H5NH2. So snh tnh baz ca ba cht . Gii thch? 3.7. Gii thch ti sao khi cho HCl tc dng vi penten-2 sinh ra ch yu 2-clopentan?
Chng 4: Phn ng hu c
Trang 32
Chng 4: PHN NG HU C
4.1. Mt s khi nim chung Nh chng ta thng ni phn ng ho hc l qu trnh bin i cht ny thnh cht khc, trong c qu trnh ph v lin kt c to ra lin kt mi. Qu trnh ph v lin kt c c th to ra ion, to ra gc t do.
. A + . B AB A
+
Cc phn ng phn cc, cc ion, cc gc t do tc dng cc cht khc to ra cht mi. Phn ng ho hc c s tham gia ca gc t do gi phn ng theo gc t do. Cc gc t do c nng lng ln, thi gian tn ti ngn, c kh nng cho phn ng cao. Cc hp cht hyro peroxit v peroxit d phn hu cho gc t do. Phn ng ho hc c s tham gia ca cc ion gi phn ng ion. Tc nhn tng tc A+ gi l tc nhn i in t. Tc nhn B- gi l tc nhn i nhn. Tc nhn i nhn cng l mt baz ca Lewis, tc nhn i in t l mt axit ca Lewis. Trong phn ng oxy ho kh c th xem tc nhn i nhn l cht kh, cn tc nhn i in t nhn in t ca tc nhn i nhn nn c th xem l cht oxy ho. Nh vy cc phn ng ho hc: phn ng cng hp, phn ng th, phn ng tch loi, c th xy ra theo c ch gc t do, hoc c ch ion. Phn ng theo c ch ion c c ch i in t v c ch i nhn. Tu thuc vo s lng cc phn t hoc ion, tham gia vo giai on quyt nh tc phn ng m c loi phn ng n phn t, lng phn t hoc nhiu phn t. Trong phn ng ho hu c, cc cht tham gia phn ng c th thc hin trng thi hi, trng thi lng, trng thi rn c dung mi ha tan hoc khng dung mi ho tan. 4.2. c im ca phn ng hu c Phn ng ho hc hu c khng nhng c nhiu v s lng, rt phc tp v v c ch m cn c nhng c im ring sau y: - Phn ng xy ra thng l chm. - Phn ng xy ra qua nhiu giai on (phn ng ni tip). - Phn ng xy ra song song nhau (phn ng cnh tranh sinh ra sn phm ph). Phn ng hu c thng xy ra khng qua giai on phn ly ra ion, m qua giai on to ra trng thi trung gian gi l trng thi phc hot ng hay trng thi chuyn tip ri sau to ra cht mi. Bng con ng qua trng thi chuyn tip phn ng tiu tn nng lng t hn nhiu so vi phn ly ra ion. 4.2.1. Tc phn ng Cc phn ng ho hc xy ra mt giai on nh: aA + bB eE
Chng 4: Phn ng hu c
Trang 33
Vn tc ca phn ng c xc inh: v = k[A]a [B]b. Phn ng bc a i vi A, bc b i vi B v bc ca phn ng l (a+b). Cc phn ng qua nhiu giai on vic tnh vn tc tr nn phc tp hn. Trng hp ny c th tnh gn ng l b qua cc giai on phn ng nhanh, giai on chm nht l giai on quyt nh tc phn ng. 4.2.2. Phn ng cnh tranh c im c bit trong phn ng hu c l mt trong cc cht nh nhau phn ng xy ra nhiu hng khc nhau cho sn phm chnh v sn phm ph (phn ng song song nhau). Th d: Cht A ng thi phn ng vi cht B v D (hoc cng mt cht B nhng v tr khc nhau trong phn t): A A + + B D
K1 E
K2 G
i vi phn ng mt chiu, c cng bc phn ng th tng quan gia sn phm E v G to thnh khng i trong qu trnh phn ng. T l ny l thc o hot tnh tng tc ca B v D i vi A.
[E ] = K1 [G ] K 2
4.2.3. Trng thi chuyn tip Thuyt va chm: mun phn ng ho hc xy ra cc cht tham gia phn ng phI va chm nhau. Ngi ta tnh c s va chm gia hai phn t trong 1 giy th tch 1cm3 v 150C khong 1014 va chm. Nu mi va chm u xy ra phn ng th tc phn ng rt ln. Thc s khng phi va chm no cng xy ra phn ng. Cc va chm gy ra phn ng ch i vi phn t c nng lng cao, nng lng mi va chm u sinh ra cht mi. Nng lng ny c gi l nng lng hot ho. Nghin cu v vn ny Arenius a ra phng trnh xc nh s ph thuc hng s vn tc phn ng: K = p.z. e Vi:
E RT
K l hng s vn tc z l s va chm (vn tc phn ng t l thun vi z) E l nng lng hot ho p l tc nhn xc sut, tc nhn lp th. N cho bit s khc nhau gia tc thc
v tc tnh theo l thuyt (p = 10-1 10-3). Vic tnh yu t xc sut p khng n gin, v vy thuyt va chm b hn ch p dng cho nhiu phn ng. Thuyt trng thi chuyn tip ra i. y l thuyt c gi tr trong vic gii quyt cc c ch phn ng ho hc.
Chng 4: Phn ng hu c
Trang 34
Xt phn ng ho hc: A + BC AB + C Mun phn ng ho hc xy ra, trc ht BC phi phn ly thnh B v C. Sau B kt hp vi A to ra AB. Phn ng thc hin bng con ng ny phi tiu tn nng lng ln phn ly BC thnh B + C. Nng lng ny xa vi nng lng thc t cn thit to ra phn t AB. Theo Hayle London Ingold phn ng xy ra khng qua giai on BC phn ly thnh B v C, m BC cng A to ra trng thi chuyn tip, trng thi ny A...B...C cng nm trn mt trng thi m bo nng lng tng tc nh nht. C th biu din thuyt trng thi chuyn tip p dung cho kh nng phn ng h 3 trung tm nh A + BC l: A + BC A...B...C AB + C i vi h c 4 trung tm AB + CD AC + BD c th biu din trng thi chuyn tip:
A B
C D
A B
C D
A B
C D
trng thi chuyn tip

4.3. Phn ng th trong ho hc hu c 4.3.1. Khi nim
Phn ng th k hiu bng ch S (xut pht t Substitution c ngha l s thay th) l phn ng trong mt nguyn t hay nhm nguyn t trong phn t c thay th bng nguyn t hay nhm nguyn t khc. Th d: CH4 + Cl2 +
CH3Cl + HCl
NaOH
CH3 Cl
CH3 OH + NaCl
Phn ng trng ngng thc cht l nhng phn ng th ni tip nhau. Phn ng th l phn ng rt ph bin trong ho hc hu c, l phn ng c nghin cu k v rt lu i, ... Tu thuc vo bn cht tng loi tc nhn tng tc m c th chia cc loi phn ng sau:
4.3.2. C ch phn ng th a) Phn ng th theo c ch gc t do
R + R , R ,, R , R + R ,,
Cc gc t do c to thnh c th do tc dng nhit hoc nh sng, v d: Cc hydro peroxyt, peroxyt:
t R O O H R O+ O H
0
t R O O R, R O+ R , O
0
hv Cl2 Cl + Cl
Chng 4: Phn ng hu c
Trang 35
Cc phn ng halogen ho ankan, phn ng ankyl halogenua vi kim loi, ... l nhng phn ng th theo gc t do.
R Cl + Mg R + Mg Cl R Cl + Mg Cl R + MgCl2
R Cl R + Mg R Mg + R MgCl + R
Phn ng clo ho: R H + Cl2

hv Cl2 Cl + Cl
hv RCl + HCl
R H + Cl R + HCl
R + Cl2 RCl + Cl
b) Phn ng th theo c ch i in t
Phn ng th i in t c k hiu l SE ( S E , S E l phn ng n phn t hay lng phn t). S tng qut: R+ + R/(-)R//(+)
R/ R + R//+
+
Th d:
CH3 ... CH3 CH3 I + CH3 Na Na ... I
+ -
CH3
CH3
+
NaI
4.3.3. Phn ng th i nhn vo nguyn t C no
Phn ng th i nhn ch yu tp trung vo nguyn t C bo ho v phn ng th H nhn benzen ngho in t. S chung: R(-) (R:) + R/ - R//
R// R + R/(-) (R/:)
Vi R (-) (R:): l cc anion, cc hp cht c cp in t t do (:) nh Cl-, Br-, I-, OH-, RO-, RS-, CN-, ROH, RCOO-, NH3, RNH2. Cn R/ - R// l cc ankyl halogen, ru, ete, este, hp cht diazo, cc ankyl sunphat. Th d: CH3 CH2 CH2 Cl + OH- CH3 CH2 CH2 OH + ClC2H5 O C2H5 + HBr C2H5OH + C2H5Br
c) Phn ng th theo c ch nucleophin (SN)
Phn ng th nucleophin c hai c ch: c ch n phn t ( S N ) v lng phn t ( S N ).

Phn ng th n phn t ( S N )
1
Chng 4: Phn ng hu c
Trang 36
Th d:
CH3 CH3 C CH3 C ch: CH3 CH3 CH3 Cl Cl + OH
CH3
CH3
C CH3
OH + Cl
+ C
CH3
cham
CH3
C+ CH3
+ Cl
CH3 CH3 C+ CH3

nhanh
CH3
CH3 + OH
CH3
CH3 CH3 C CH3 OH
nhanh
HO
CH3 CH3
CH3
Giai on u l giai on ion ha to ra ion, giai on ny thng chm, cho nn tc ion ho cng l tc ca phn ng. Giai on hai c tnh cht ion tng tc nn c thc hin nhanh. Trc khi thc hin giai on hai ion cacboni trung tm s chuyn t trng thi t din sang trng thi mt phng bn hn. Nh vy nhm OH c xc sut tn cng vo hai pha nh nhau.
Phn ng th lng phn t ( S N )

Th d: CH3 Cl + OHC ch:
H OH- + H C+ H Cl H H
CH3OH + Cl-
HO-
Cl
H HO C H +
Cl -
H H (TTCT Giai on chm nht l giai on to thnh) TTCT c s tham gia ca CH3Cl v ion OH-. Theo thuyt TTCT, ba trung tm phn ng OH, C v Cl TTCT phi nm trn mt ng thng. l iu kin m bo nng lng tiu tn cho phn ng cc tiu. Khi lin kt OH v C t n hng ro nng lng chuyn tip th Cl tch ra khi C.
4.4. Phn ng tch loi trong ho hc hu c 4.4.1. Khi nim

Phn ng tch loi k hiu bng ch E (xut pht t Elimination c ngha l s tch b) l phn ng lm cho hai nguyn t hay nhm nguyn t b tch ra khi mt phn t m khng c nguyn t hay nhm nguyn t no thay th vo.
Chng 4: Phn ng hu c
Trang 37
Th d: CH3 CH3 C2H5OH
CH2 = CH2 + H2
CH2 = CH2 + H2O
Crackinh thc cht l phn ng tch loi. Phn ng tch loi c th xy ra vi hai nhm tch ra cng mt nguyn t C hoc khc nguyn t C. Sn phm tch loi c th l hp cht khng no, hoc hp cht vng. Trong phn ng ng vng c phn ng ng vng kiu Dikman (hai nhm tch loi khng cnh tranh) Trong phn ng ng vng thng thc hin bng s tch loi, nhng c ch phn ng tch loi kiu ng vng nhiu trng hp theo c ch th ni phn t. Cc phn ng ng vng thng gp:
CH2Br H2C CH2Br

1,3-dibrom propan
CH2 + 2Na
(or: Zn/ROH)
H2C CH2
Xyclo propan
+ 2NaBr
ng vng to nhm poxy:

CH2 Cl CH OH CH2 OH CH2 O CH CH2 OH + HCl
..... Phn ng tch loi c gi tr l phn ng tch loi to ra olefin, ankin. y l phn chnh ca chng trnh. Trc ht dn chng mt s phn ng tch loi to ra ni i thng gp trong ho hu c.
CH H
CH2 X
CH2 OH
CH2
+H2O
CH
CH2
HX
CH H
H+
CH
CH2
H2O
CH H
CH
CH2
H2SO4
OSO3H
4.4.2. C ch phn ng tch loi a) Phn ng tch loi n phn t (E1)
Chng 4: Phn ng hu c
CH3 CH3 CH2 C CH3 CH3 CH3 CH2 C
+
CH3 Cl
cham
Trang 38
CH3
CH2
+ C CH3
Cl
nhanh
CH3
CH
C CH3
CH3
H+
CH3
CH3 CH3 C CH3

cham
CH3 OH + H
+ nhanh
CH3
H H
CH3 CH3 C+ CH3 + H2O
CH3 CH3 C CH2 +
nhanh
CH3
H+
Hai phn ng trn vit theo c ch loi n phn t. Giai on to ra cation cacboni l giai on chm nht, nn l giai on quyt nh tc phn ng. Vai tr ca dung mi phn cc i vi phn ng tch loi l sonvat ho, to kh nng cho cht phn ly ra ion. Dung mi cng phn cc, phn ng tch loi E1 xy ra nhanh v thun li.
b) C ch phn ng tch loi lng phn t

Ging nh phn ng th thi chuyn tip.
R HO + R CH2 CH2 Cl HO-... H ... C
(TTCT) -H2O
2 , phn ng tch loi E2 cng tri qua giai on to thnh trng SN
C+... Cl H H
CH
CH2
Cl-
Theo ch ch tch loi trn H+ v Cl- tch ra cng mt lc. Thc nghim xc nhn tc phn ng ph thuc vo tc nhn tch loi (OH-). Phn ng tch loi E2 khng nhng ph thuc vo nng tc nhn i nhn m cn ph thuc vo sc i nhn v baz ca n, ... Nng tng ln, tnh baz tng ln phn ng tch loi E2 xy ra cng nhanh. Phn ng tch loi E2 r rng theo c ch cn ph thuc vo cu trc phn t cht tch loi. Yu t cu trc y ch yu ph thuc vo bc C c H tch loi ra. Bc C cng ln nh hng yu t khng gian cng mnh, tc nhn i nhn cng kh tip cn H+, kh hnh thnh trng
Chng 4: Phn ng hu c
Trang 39
thi chuyn tip. Hng tch loi E2 b hn ch hoc thay i. Cc tc nhn i nhn thng gp trong phn ng tch loi E2: H2O, CH3COO-, C6H5O-, OH-, CH3O-, NH2-, CO32-. Trong tc nhn baz mnh RO-, OH-, NH2- d dng loi proton cho phn ng E2. Cc nhm chc trong phn t tch loi c kh nng tch theo E2: R3N+, R3P+, R3S+, -SO2R, X-, OSO2R, RCOO-. Trong d tch nht l R3N+, R3P+, R3S+ cn X- cn tc nhn baz mnh mi tch c.
4.4.3. S cnh tranh phn ng tch loi v th

C ch phn ng th v tch loi c nhng im ging nhau. Trong phn ng th bao gi cng km theo phn ng tch loi v ngc li. T l sn phm th v tch loi ph thuc vo nhiu yu t. Phn ng th n phn t SN1 v tch loi n phn t E1 u qua giai on to thnh ion cacboni. Khi tng nhm th ankyl s tng kh nng tch loi E1 hn th SN1. R CH2 CH2 X < R CH2 CHR1 X < R CH2 CR1R2 X i vi phn ng tch loi theo c ch SN2 v E2 cng vy, vic tng nhm th ankyl s tng phn ng E2 hn SN2.
4.5. Phn ng cng hp trong ho hc hu c 4.5.1. Khi nim

Phn ng cng c k hiu l bng ch A (xut pht t Addition c ngha l s cng hp) l phn ng trong c hai phn t kt hp vi nhau to thnh phn t mi. Phn ng trng hp c bn cht l phn ng cng hp nhiu ln. Trong phn ng hu c thng gp cc dng phn ng cng hp sau: R CH = CH2 + Cl2 R C CH + 2Cl2
O R C H + NaHSO3 CH3
R CHCl CH2Cl R CCl2 CHCl2

ONa C H SO3H
CH3
CH O
CH2
NH3
CH3
CH OH
CH2 NH2
Lin kt pi l lin kt giu nng lng, c kh nng phn ng kh mnh di tc dng mi trng bn ngoi hoc do cc hiu ng ni phn t. Cc nhm th gy hiu ng in t lm gim hoc tng mt in t lin kt pi dn n s tng phn cc ca n. Trng hp cc hiu ng lm tng mt in t lin kt pi, lin kt pi s tng hot ho tc dng vi nhiu i nhn i in t. Trng hp ny chnh in t pi l tc nhn i nhn, mt baz mnh.
Chng 4: Phn ng hu c
Trang 40
Trong trng hp ngc li nhm th gy hiu ng lm gim mt in t pi lin kt pi th kh nng cng hp i in t s gim, c xu hng cng hp i nhn. Ring lin kt ba nh axetylen c kh nng cng hp i nhn ln i in t. Mt s tc nhn i nhn mnh RO-, RCOO- trong mi trng baz, axetylen cng hp i nhn. Phn ng cng hp c 3 c ch: cng hp i nhn, i in t v gc t do.
4.5.2. C ch ca phn ng cng hp a) Phn ng cng hp i in t vo lin kt i C = C

Th d:
CH2 CH2 + Cl Cl
nhanh
CH2 Cl+ Cl-
CH2
cham
CH2 Cl
CH2 + Cl -
phc
CH2 Cl
CH2
Cl + Cl CH2 CH2 Cl
Phn ng cng hp vo ni i C = C theo c ch i in t cn phi c mt ca dung mi phn cc hoc xc tc nh xc tc Lewis lm cho lin kt pi d phn cc v tc nhn cng hp phn cc (Cl2). Nh s phn cc trc nn gai on to phc nhanh. Qu trnh phc ph v lin kt to ra ion l qu trnh kh v chm. V vy tc phn ng cng hp c xc nh l gia on ph v lin kt pi to ra ion. Hn na tc nhn i in t s cng hp vo trc v c cng hp vo giai on quyt nh ny. Cho nn phn ng cng hp vo ni i C = C l phn ng cng hp i in t.
C ch phn ng: c ch AE
C
-
X+
Y-
cham
C Y X
+ Y-
C X
+ Y-
nhanh
C X
b) Phn ng cng hp i nhn vo lin kt i C = O

Nhm cacbonyl c kh nng cng hp rt nhiu cht (H2, HCN, NaHSO3, H2O, NH2-OH, RMgX, ...). Kh nng cng hp c nhiu ca nhm cacbonyl l do nguyn t O c m in ln lm cho lin kt pi b phn cc mnh v pha O
C
+
Chng 4: Phn ng hu c
Trang 41
To ra hai trung tm: 1 trung tm dng (C+) v mt trung tm m (O-). Trung tm dng s tng tc vi tc nhn i nhn, trung tm m s tng tc vi tc nhn i in t. Trong phn cc ng ho hc trung tm dng c vai tr quyt nh cho giai on u ca cng hp i nhn.
C ch phn ng: c ch AN
R1 R2 R1 R2 OC Y + X+
nhanh
O +
X+
Y-
cham
R1 R2
OC Y OX + X+
R1 R2
C Y
Th d:
CH3 H CH3 C H CN
-
CH3 H+ CN cham
OC + H+ CN
C O-
O +
H CH3 + H+
nhanh
OH C CN
BI TP
4.1. C ch phn ng l g? Hy minh ho bng c ch phn ng sau: a) CH4 + Cl2
CH3Cl
Br2 HBr
HCl
b) CH2 = CH2 + c) CH2 = CH2 +
CH2Br - CH2Br CH3 - CH2Br
d) CH3 CHO + NaHSO3
Chng 5: Hirocacbon
Trang 42
Chng 5: HIRO CACBON

5.1. HIROCACBON NO Hirocacbon no l nhng H C m trong phn t ca chng ch c nguyn t Csp3, cho nn phn t ch c lin kt n. Phn loi: gm hai loi H C no mch h (ankan) v H C no mch vng (xicloankan) 5.1.1. Cu trc phn t a) i vi ankan Phn t ankan ch c nhng nguyn t C sp3 vi gc ho tr 109028/, do mch C thng ziczac v tn ti ch yu dng xen k, v l nhng dng bn (hnh 5.1)
H H H H CH3 - CH3 H H H H H CH3 -CH2 - CH3 CH3 H H CH3 H H CH3 anti H H H H H syn CH3 CH3 H
CH3 -CH2 - CH2 - CH3
Hnh 5.1: Cu dng xen k ca mt s dng ankan b) i vi xicloankan Xiclopropan v xiclobutan l nhng vng km bn. Do gc (CCC) b p nhiu so vi gc bnh thng (109028/), lin kt C C trong phn t xiclopropan chng hn c hnh thnh bng cch xen ph mt bn, chnh v vy lin kt ny km bn. Ngoi ra, nu nhn theo trc dc lin kt C C ta thy cc nguyn t H v tr che khut nhau, yu t cng gp phn lm cho vng km bn. Xiclopentan v xiclohexan l nhng vng bn. Vng xiclohexan c dng gh nn gc lin kt t din vn c bo m cn cc nguyn t H lun lun v tr xen k. Dng thuyn tuy vn m bo gc lin kt, song c mt nguyn t H v tr che khut (hnh 5.2) nn dng thuyn khng bn.
H H H H H H(e) H H H H H H(a) H H H H H H (a)H H(e) H
Chng 5: Hirocacbon
H H H
Trang 43
H(a) H(e) H H HH
HH
Dng thuyn
Dng gh Hnh 5.2: Cu dng ca xiclohexan 5.1.2. Tnh cht vt l
Gia cc phn t ankan ch c lc ht vandevan nn cc cht u dy ng ng l nhng cht kh (t metan n butan), nhng cht sau l lng (t C5 n C19) hoc rn (t C20 tr ln). Ni chung, khi phn t khi ca ankan tng th nhit si v nhit nng chy cng tng theo (bng 5.1). S phn nhnh lm cho nhit si gim i. Bng 5.1: Hng s vt l ca mt s ankan CTPT CH4 C2H6 C3H8 Mtan Etan Propan n butan C4H10 Iso butan n- pentan C5H12 2 metyl butan (iso pentan) 2,2 imetyl propan (iso pentan) C8H18 n - octan C10H22 n decan C20H42 n - icosan -159 -130 -160 -57 -30 37 -10 36 28 9,5 126 174 343 0,603 0,626 0,620 0,703 0,730 0,778 Tn
0 t nc
t s0
-162 -89 -42 -0,5
d 0,415 0,561 0,585 0,600
-183 -183 -188 -138
Cc ankan u khng tan trong nc (hoc t tan). Ngc li chng d tan trong nhiu dung mi hu c, ho tan c cht bo. 5.1.3. Tnh cht ho hc So vi mt s hp cht hu c khc, ankan c kh nng phn ng rt km. iu kin
Chng 5: Hirocacbon
Trang 44
thng, ankan khng tc dng vi axit, baz, cht oxi ho, kim loi hot ng, ... v th ankan l mt parafin (t ting Latin parum affinis c ngha l i lc) Cc phn ng ho hc ca ankan thng ch xy ra khi un nng, khi chiu sng hoc c mt cc cht khi mo v xc tc v hu ht theo c ch ng ly. a) Phn ng th hiro bng halogen Phn ng ch xy ra vi clo hoc brom, trong iu kin chiu sng, it khng phn ng, cn flo gy ra phn ng n. S phn ng: Th d:
CH4 metyl
+ Cl2 - HCl
RH
+ X2
hv R X + HX
CH3Cl
+ Cl2 - HCl
CH2Cl2
+ Cl2 - HCl
CHCl3
+ Cl2 - HCl
CCl4
metyl clorua
metylenclorua
clorofom cacbon tetraclorua
C ch phn ng: C ch th gc t do SR - Khi mo phn ng: - Pht trin mch: X* R* + +
2X* X2
hv
RH XX
R* + HX
R X + X*
X* li tip tc phn ng vi R H nh trn, qu trnh c lp li n ln (nu RH l CH4 n10000) - Giai on tc mch theo cc hng sau: X* R* R* + + + X* X* R*
X2 R X
R R
Kh nng phn ng v hng phn ng: Khi halogen ho cc ng ng ca etan c th sinh ra mt hn hp dn xut monohalogen ca nhau. Th d:
+ Cl2 CH3 hv -HCl CH3 CH2 Cl CH3 CH CH3 (B) CH2Cl (A)
CH3
CH2
T l % cc sn phm ph thuc vo s lng ni cc nguyn t H cng mt loi, tc l lin kt vi nguyn t C bc i (bc I, bc II hay bc III) v ph thuc kh nng phn ng ri ca nguyn t H cacbon bc i . Thc nghim cho thy ri ca phn ng 1000C nh sau:
Chng 5: Hirocacbon
Trang 45
CI H Clo ho Brom ho 1 1
CII H 4,3 82
CIII H 7 1600
Ta thy bc ca C cng cao th kh nng phn ng ca H cng ln v C bc cng cao s cho gc t do bc cao bn hn. S khc nhau v ri trong phn ng brom ho r rt hn trong phn ng clo ho. Gia t l % ai ca sn phm th vi ni v ri c mi quan h n sau:
ai (%) =
100 ri ni ni ri
Trong th d v clo ho propan trn nI = 6; nII = 2; rI = 1; rII = 4,3. p dng biu thc trn ta tnh c: Sn phm A: aI(%) 41% Sn phm B: aII 59%
Phn ng ca xicloankan vi halogen: Xiclohexan, xiclopentan, ... tc dng vi halogen tng t ankan, ngha l cho sn phm th. Th d:
hv
Br2
Br +
HBr
Tuy nhin, xicloprpan li tham gia phn ng cng - m vng, v vng ny km bn. Th d:
+ Br2
CCl4
Br
CH2
CH2
CH2
Br
Ngoi phn ng cng brom, xiclopropan cn d dng cng hiro, HBr, H2SO4, ....
b) Phn ng tc dng nhit ehiro ho hay l tch H2: Khi un nng ankan c mch ngn vi xc tc (Cr2O3, Cu, Pt, ...)
xy ra phnng tch H2 to thnh H C khng no. Th d:
CH3
CH3
xt, t0
CH2
CH2 +
H2
Khi nhit phn CH4, tu thuc iu kin phn ng c th thu c mui than hoc axetylen:
CH4 2CH4
xt, 10000
C HC
2H2 CH + 3H2
1400 - 15000
Chng 5: Hirocacbon
Trang 46
Phn ng tch H2 nhng ankan c 5 7 C trong mch chnh c th dn ti s ng vng hoc xa hn na l thm ho. Th d:
H2 C H2C H2C CH3 CH2 CH3

xt, t0
- H2
xt, t0 - 3H2
Crackinh: l qu trnh b gy mch C ca ankan to ra mt hn hp nhng anken v ankan
c mch C ngn hn. Qu trnh ny xy ra nh tc dng n thun ca nhit (500 7000C) gi l crackinh nhit, hoc nh cht xc tc nhi thp hn (450 5000C) gil crackinh xc tc. Th d:
C4H10
CH4 C2H6
+ +
C3H6 C2H4
c) Phn ng oxi ho Oxi ho hon ton: t chy trong khng kh
Khi c tia la t v oxi, ankan v xicloankan c th chy hon ton sinh ra CO2, H2O v to nhit mnh: CnH2n+2 +
3n + 1 t0 O2 nCO2 + (n+1)H2O 2
3n t0 O2 nCO2 + nH2O 2
CnH2n +
Phn ng chy ankan c dng rng ri trong cng nghip v i sng.

Oxi ho khng hon ton: Tu theo iu kin phn ng, ankan b oxi ho khng hon ton cho
nhng sn phm khc nhau trong cng nghip. Oxi ho metan:

200 at, 300oC, Cu
HCHO CO2 C + +
H2O 2H2
CH4
+ O2 (kk)
Ni, 5000C
thieu oxi
2H2O
Oxi ha butan:
CH3 CH2 CH2 CH3
+ O2 (kk) Mn2+
2CH3
COOH
Chng 5: Hirocacbon
Oxi ho ankan cao:
R1 R2 Oxi ho xiclohexan:
Trang 47
CH2 CH2
+ O2 (kk) Mn2+
R1 + R2
COOH COOH
OH
ZnO, to + O2 (40at) 150oC + O2 , NO xiclohexanon
5.1.4. Phng php iu ch a) Phng php tng mch cacbon T cacbon oxyt v hiro c xc tc Fe, Co, Ni
Hn hp CO v H2 cho i qua nhit 2000C v p sut kh quyn c cht xc tc st, coban cho hn hp ankan nCO + (2n + 1) H2 CnH2n + 2 + nH2O
2000 C , Fe ,Co
Phn ng Wurtz Fittig (Php 1855)
y l phn ng tng hp quan trng iu ch H C loi no i t ankyl halogenua v natri kim loi.
R R X + 2Na + R/ X R R/ R R/ R/ + 2NaX
V d: 2C2H5I + 2Na C ch phn ng:
C2H5 C2H5 + 2NaI

2C2H5I
2Na
2 C2 H 5
2NaI
2 C2 H 5
C2H5 C2H5
Nh vy c ch gc gii thch s tn to thnh sn phm chnh v ph.

Phn ng tng hp Kolbe (c 1849): in phn dd mui Na ca axit cacboxylic
Chng 5: Hirocacbon
Trang 48
2RCOONa
+ 2H2O
dpdd R R + 2CO2 + 2NaOH + H2
b) Phng php gi nguyn mch cacbon Phn ng kh ru bng axit HI m c 80% 180 2000C: Phn ng tin hnh qua hai
giai on: ROH + HI RI + H2O RI + HI RH + I2
i khi thm vo phn ng mt t phtpho eer c tc dng to ra HI bit lng HI a vo phn ng: 3I2 PI3 + + 2P
2PI3 H2PO3 + 3HI
3H2O
Phn ng kh H C khng no bng H2 c xc tc:
R CH = CH R/ + H2 R C C R/ + 2H2
Ni ,t R CH2 CH2 R/
0
Ni ,t R CH2 CH2 R/
0
c) Phng php gim mch cacbon
Khi ct khan mui kim hoc kim th ca axit cacboxylic vi vi ti xt s thu c H C c mch C gim i mt nguyn t so vi axit cacboxylic. R COONa + NaOH
CaO ,t 0
RH
CaO ,t 0
Na2CO3 + Na2CO3
Th d: CH3 COONa + NaOH

5.1.5. ng dng
CH4
- Dng lm nhin liu (CH4 dng trong n x hn, ct kim loi). - Dng lm du bi trn. - Dng lm dung mi. - tng hp nhiu cht hu c khc: CH3Cl, CH2Cl2, CCl4, CF2Cl2, - c bit t CH4 iu ch c nhiu cht khc nhau: hn hp CO + H2, amoniac, CH CH, ru metylic, anehit fomic
Chng 5: Hirocacbon
Trang 49
BI TP
Cu 5.1: Vit CTCT v gi tn cc ankan c CTPT C5H12, C6H14 v xicloankan C5H10. Dng s la
m ch r bc ca nguyn t C v gi tn CTCT tng ng.
Cu 5.2: C bao nhiu gc t do tng ng vi cng thc C4 H 9 . So snh bn tng i ca
cc gc t do?
Cu 5.3: Cho n-butan phn ng vi clo theo t l 1:1 c chiu sng ta c hn hp 2 sn phm
hu c v mt cht kh A. a) Vit phng trnh phn ng v c ch phn ng. b) So snh khi lng hai sn phm hu c, bit rng mt nguyn t H CII c kh nng phn ng co hn 3 ln so vi mt nguyn t H CI.
Chng 5: Hirocacbon 5.2. HIRO CACBON KHNG NO
Trang 50
Hirocacbon khng no l nhng H C c cha lin kt i hoc lin kt ba, hoc c lin kt i v lin kt ba trong phn t. Ta phn bit H C c mt ni i (anken CnH2n n 2), nhiu ni i (polien), mt ni ba (ankin CnH2n-2 n 2), nhiu ni ba (poliin), c ni i ln ni ba (ankenin). Ngoi ra c nhng H C khng no mch vng, nh xicloanken, ....
5.2.1. Cu trc phn t a) Anken
Phn t anken c lin kt i, l tp hp ca mt lin kt v mt lin kt .

Lien ket pi: do hai obitan p xen phu ben vi nhau tao nen
C
Lien ket xchma: do hai obitan lai hoa sp2 xen phu vi nhau tao nen
V d phn t etilen c 6 nguyn t (2C v 4H), tt c u nm trn 1 mt phng cha trc ca 5 lin kt . di ca lin kt C C l 1,34A0 (trong khi ca etan l 1,54A0) gc lin kt (HCC v HCH gn bng 1200). Nng lng lin kt i C = C bng 616 kJ/mol, nh hn nhiu so vi nng lng ca hai lin kt n C C (2 x 348 = 696 kJ/mol). iu chng t nng lng ca lin kt pi nh hn so vi lin kt xchma, do lien kt pi km bn.
H H
H hay H
H H
H H
Hnh 5.3: S hnh thnh lin kt pi ca etilen

Nguyn t C sp 2 c m in ln hn C sp3 . Hai nguyn t C sp 2 lin kt vi nhau khng th quay t do c, do , c th xut hin ng phn hnh hc nu mi nguyn t C sp 2 ni vi hai nguyn t hoc nhm nguyn t khc nhau.
b) Ankadien
Ankadien hoc olephin l nhng H C trong phn t cha hai li kt i. Cng thc chung CnH2n-2 (n 2) Phn loi: tu thuc vo v tr ca lin kt i trong phn t m ngi ta chia ra lm 3 loi:
Chng 5: Hirocacbon
Trang 51
Loi ankadien c ni i bit lp: loi ny c cng thc chung:

C C (CH2)n C C
V d: n = 1: CH2 = CH CH2 CH2 CH = CH2 (hexadien 1,5)
Loi ankadien c ni i tip cn nhau (lin nhau): loi ny c cng thc chung:
R1 C C C R2
V d: CH2 = C = CH2 alen (propadien 1,5)
Loi ankadien c ni i lin hp: loi ny c cng thc chung:

R1 CH CH CH CH R2
V d: CH2 = CH CH = CH2 (butadien 1,3)
CH2
C CH3
CH
CH2
2 - metyl butadien - 1,3 (isopren)
Cu trc phn t: butadien 1,3
Trong phn t butadien 1,3 tt c 10 nguyn t (4C v 6H) v 9 lin kt (3 C C v 6 C H) u nm trn mt mt phng v to nn nhng gc lin kt 1200. Cc obitan p khng nhng xen ph bn vi nhau to thnh lin kt gia C1 vi C2 v C3 vi C4 m cn xen ph gia C2 vi C3 do xut hin obitan bao trm tt c bn nguyn t C (h.5.4)
H H H H H H a) H b) H H H H H
Hnh 5.3: S xen ph cc AOp (a) to thnh lin kt chung cho ton phn t butadien (b)
Hin tng xen ph obitan nh trn gi l lin hp, v do butandien 1,3 l 1 ien lin hp. Ankadien lin hp cng c cc cu dng khc nhau v cng c ng phn hnh hc, nu nguyn t C sp2 u mch ni vi hai nguyn t hoc nhm nguyn t khc nhau. Th d: CH3 CH = CH CH = CH2 c hai ng phn hnh hc
Chng 5: Hirocacbon
Trang 52
CH3 CH = CH CH = CH C2H5 c 4 ng phn hnh hc
c) Ankin
Ankin l lo hirocabon mch h, trong phn t ca chng c lin kt ba. Cng thc phn t CnH2n-2 (n2) Phn t cha mt lin kt ba, l tp hp ca lin kt (do hai AOsp to nn) v hai lin kt (do 4 AO2p xen ph nhau).
180o H C C H 180o H H
a)
b)
Hnh 5.4: S hnh thnh lin kt xch ma (a) v lin kt p (b) ca C2H2
di lin kt C C ch bng 1,2A0 (ngn hn C = C). Lin kt Csp- H phn cc mnh hn
Csp2 H v m in ca C sp Csp2 .
Nng lng lin kt ba bng 813 kJ/mol, nh hn nhiu so vi nng lng ca 3 lin kt n (3 x 348 = 1044 kJ/mol); iu cng chng t lin kt pi linh ng.
5.2.2. Tnh cht vt l

Hirocacbon khngno c nhiu tnh cht vt l nh nhit si, nhit nng chy, t khi, tnh tan, ... tng t H C no c cng s nguyn t C v cng b khung C (xem bng 5.2)
Bng 5.2: Hng s vt l ca mt s hirocacbon khng no

CTPT C2H4 C3H6 Etylen CH2 = CH2 Propen CH3 CH = CH2 Buten 1: CH2 = CH CH2 CH3 Trans butan - 2 C4H8 Cis butan - 2 Butadien 1,3 Isopren C5H8 Pentadien 1,3 Tn
0 t nc
t s0
-105 -48 -6 1 4 -4,5 34 42
d 0,566 0,609 0,630 0,660 0,644 0,646 0,681 0,683
-169 -185 -185 -106 -139 -109 -120 -88
C4H6
Chng 5: Hirocacbon
Trang 53
Pentadien 1,4 C2H2 C3H4 axetylen Propin Butin - 1 C4H6 Butin - 2
-148 -82 -103 -122 -24
26 -84 -223 8,6 27
0,659 0,650 0,694
5.2.3. Tnh cht ho hc

S c mt ca lin kt pi trong phn t lm cho H C khng no c kh nng phn ng cao hn H- C no. Chnh ni i v ni ba l nhng trung tm phn ng c coi l nhm chc.
5.2.3.1. Phn ng cng H2 trn b mt xc tc kim loi

Nhng phn ng ny ta nhit v ch xy ra khi c cht xc tc nh Ni, Pt, Pd, ...
CH2
CH
CH2
CH
H2
CH2
Ni
CH3
CH2
H2 Ni
CH3
CH3 CH3
H2 Pb-PbCO3
CH3 CH2 CH CH CH2 + H2

Ni -120c
CH2
45%
CH
CH2 CH2 CH3
CH3 CH3
CH
48%
CH
Ni H2
CH2
6%
CH2
5.2.3.2. Phn ng cng electrophin a) Anken S phn ng:

Y C
-
X+
Y-
C X
X Y : H X ; H OH ; HO SO3H; Br Br ; ...
C ch phn ng: c ch AE
Chng 5: Hirocacbon
Trang 54
X+
Y-
cham
C Y X
+ Y-
C X
+ Y-
nhanh
C X
Hng ca phn ng:
Phn ng cng mt tc nhn khng i xng (nh HCl, H2SO4, HOH, ...) vo mot anken khng i xng s u tin theo hng to thnh cacbocation trung gian bn hn (quy tc Maccpnhicp). Th d:
CH3 CH3 CH CH2 + HBr - BrCH3
CH
ben hn
(+)
CH3
(+)
+ Br-
CH3
95%
CH Br CH2
5%
CH3
CH2
kem ben
CH2
Br-
CH3
CH2 Br
Kh nng phn ng ca anken:
Khi thay th nguyn t H trong etylen bng nhm y electron (CH3, C2H5, ...) mt electron ni i s tng ln v cacbocation sinh ra cng bn hn do phn ng cng cng xy ra d dng hn. Tri li, nhm th ht electron s lm gim mt electron v cacbocation sinh ra cng km bn, do phn ng cng xy ra kh khn hn. V vy, ta c trnh t v kh nng phn ng nh sau: CH2 = CHCOOH < CH2 = CHCl < CH2 = CH2 < CH2 = CHCH3 < CH2 = C(CH3)2
Kh nng phn ng ca HX vo anken:
Phn ng cng HX vo anken s d dng nu HX c tnh cht mnh v X(-) c tnh nucleophin cao. V vy, kh nng phn ng ca HX gim dn theo trnh t: HI > HBr > HCl > HF
b) Ankin Phn ng cng: gm hai giai on
- Giai on 1: Chuyn ni ba thnh ni i - Giai on 2: Chuyn ni i thnh ni n Phn ng cng halogen v HX vo ankin cng tng t phn ng ca anken v c ch phn ng, hng ca phn ng v nh hng ca nhm th n kh nng phn ng. So vi anken, th ankin c kh nng phn ng thp hn i cht.
Chng 5: Hirocacbon
Trang 55
CH3 C CH > CH CH > CH C COOH CH2 = CH2 > CH CH

c) Ankaien
Ankaien c th cng halogen v HX to ra hn hp gm sn phm cng 1,2 v cng 1,4. Tu theo tc nhn phn ng v nhit m mt sn phm no s chim t l cao hn. Th d:
(1,2) Br2 400 (1,4)
CH2 Br CH2 Br
CH Br CH
CH
CH2 CH2 Br
20%
CH2
CH
CH
CH2
CH
80%
5.2.3.3. Phn ng cng ng vng
CH2 CH CH CH2
cis-butadien Etylen
H2 C CH2 + CH2
2000C
CH CH C H2
CH2 CH2
Xiclohexen
5.2.3.4. Phn ng trng hp
Trng hp l qu trnh cng hp lin tip nhiu phn t nh ging nhau hay tng t nhau to thnh phn t c phn t khi ln (cao phn t). Cht u tham gia trng hp gi l monome, trong phn t monome thng phi c lin kp. Sn phm thu c l polime cha n mt xch c bn sinh ra t n phn t monome. Nu n = 2 10 polime c gi l oligome bao gm ime (n=2), trime (n=3), .... n l h s trng hp hay trng hp
a) Anken
Cc anken v dn xut c cng thc chung CH2 = CH R tng i d trng hp iu kin nhit v p sut nht nh c mt ca cht xc tc, sinh ra polime tng ng. Th d:
n CH2 CH2
TlCl4, Al(C2H5)3 2-3 at
CH2
CH2
Etylen
Polietylen (PE)
n CH CH3
CH2
Propilen
xt, p, toC
CH CH3
CH2
n
Polipropilen (PP)
Chng 5: Hirocacbon b) Ankaien
Trang 56
Cc ankaien lin hp v n gin nh butadien, isopren, ... c th tham gia phn ng trng hp to thnh polime dng lm cao su. Th d:
nCH2 CH CH CH2
TlCl4, Al(C2H5)3 2-3 at
CH2
CH
Cis
CH
CH2
Butadien
Polibutadien
c) Ankin
- Nh hp
2CH CH
Cu2Cl2
CH2
CH
CH
- Tam hp
3CH
CH
6000C C
- a hp
nCH
CH
2500C
Cu
(CH)n
Cupren
CH3 3CH3 C CH
toC xt
CH3
CH3
5.2.3.5. Phn ng th a) Anken

nhit cao (500 600oC) mt s anken u dy ng ng c th tham gia phn ng th bi clo. Th d:
CH2
Etilen
CH2 + Cl2
500oC
CH2
Vinylclorua
CH + HCl Cl
CH2
Etilen
CH2 + Cl2
CCl4 0 -20oC
CH2 Cl
CH2 Cl
CH2 CH CH2 + HCl Cl
CH3
CH
CH2 + Cl2
500oC
Chng 5: Hirocacbon
CCl4 0 -20oC
Trang 57
CH3
CH
CH2 + Cl2
CH2 Cl
CH Cl
CH3
b) Ankin - Th bng kim loi kim

2R C CH + 2Na
1500C
2R
CNa + H2
- Th bng cc kim loi khc: Cu, Ag

2R C CH + Ag2O
ddNH3
2R
CAg + H2O
CH
CH
2 Ag(NH3)2 OH
(+) (-)
AgC
CAg + 4NH3 + 2H2O

trang nga
CH
CuCl
ddNH3
C-Cu + HCl
5.2.3.6. Phn ng oxy ho a) Oxy ho khng hon ton Tc dng ca dung dch KMnO4
Dung dch KMnO4 long ngui b mt mu bi cc H C khng no, nh c th phn bit vi H C no. Dung dch KMnO4 m c v nng oxi ho mnh lm t mnh lin kt kp sinh ra hn hp axit cacboxylic hoc xeton hoc c hai, tu theo mc th ca nguyn t C khng no. i vi anken ta c s sau:
R C R1 C R2
KMnO4
R C R1 O + R2 C O OH
Th d:
C2H5 C CH3 C C2H5
KMnO4
C2H5
C O
CH3 +
C2H5
C O
OH
H
3- metylhexen-3
Butanon-2
Axit propanoic
Tc dng ca Ozon (O3):
Tc dng ca ozon, sau khi kh bng Zn, s phn ng ca anken:
Chng 5: Hirocacbon
http://www.ebook.edu.vn O C R1 O
ozonit
Trang 58
R C R1
anken
R2 C H
+ O3
cong
O C
R2 H
R
Zn
kh
C R1
xeton
O +
R2
C O
andehit
Th d:
C2H5 C CH3 C C2H5
+ O3
C2H5 CH3
O C O
O C
C2H5 H
Zn kh
H
3- metylhexen-3
cong
C2H5
C O
CH3 + C2H5
Propanal
C O
ozonit
Butanon-2
Oxi ho nh bng oxi khng kh:
Oxi ho nh bng oxi khng kh trn h xc tc PdCl2 Cu2Cl2. Phn ng ny c dng trong cng nghip sn xut anehit axetic t etylen:
2CH2 CH2 + O2
PdCl2-Cu2Cl2 100oC
2CH3
CHO
5.2.4. Phng php iu ch 5.2.4.1. iu ch anken a) Tch nc ra khi ancol
un nng ancol vi axit mnh nh vi axit sunfuric hoc axit photphoric, axit s tng tc vi ancol trc ht to este (este v c) sau este b phn hu cho anken theo s sau:
R CH2 CH2OH + H2SO4 nong R
un
CH2
SO3H + H2O
CH2
SO3H
CH
CH2 + H2SO4
Th d: ung nng ancol etylic vi H2SO4 c nhit trn 170oC s thu c etylen
CH3 CH2 H CH2OH + HO CH2 OSO3H
170oC
SO3H CH2 +
CH3 H2SO4
CH2
SO3H + H2O
CH2
b) Tch HX t cc dn xut halogen
Cc dn xut monohalogen no, c bit l dn xut bc ba khi tng tc vi dung dch baz mnh nh KOH, NaOH trong ancol v un nng s b tch mt phn t HX cho anken tng ng. Cc dn xut halogen bc hai b tch HX kh hn dn xut bc 3 v kh hn c cc dn xut bc nht.
Chng 5: Hirocacbon
Trang 59
So snh kh nng tch HX ca cc dn xut clo, brom, it, flo nhn thy dn xut it d b tch HX hn c sau n brom, clo v kh nht HF.
CH3 R C X CH3
ru KOH
C CH3
CH2
HX
c) i t dn xut ihalogen
Tng tc gia dn xut ihalogen c 2 halogen nh vo 2 C lin tip nhau vi bt km trong dung dch axit axetic, s tch hai halogen to ra anken.
R1 CH X CH X R2 + Zn R CH CH R2 + ZnX2
d) ecacbonyl ho axit cha no
Khi un nng cc axit cha no, nhm cacboxyl b tch ra d hn cc axit no.
CH
CH
COOH
toC
CH
CH2 + CO2
axit xinnamic
Stiren
e) ehiro ho ankan
Trong cng nghip cc anken thng iu ch bng cch ehiro ho ankan di tc dng ca xc tc CrO3 45oC.
5.2.4.2. iu ch ankadien a) iu ch butadien 1,3
- T ru etylic:
2C2H5OH
Al2O3 450-500oC
CH2 = CH - CH - CH2 + 2H2O + H2
- T n-butan v buten
CH3 CH3 CH2 CH2 CH2 CH CH3 CH2
Al2O3 500-600oC
CH2
CH
CH
CH2
- T axetylen
2CH CH
Cu2Cl2
CH2 CH2
CH
t0,
CH
Pd + H2
CH
CH
CH2
Chng 5: Hirocacbon b) iu ch isopren
Trang 60
- Tch hiro khi hirocacbon no Phn ng xy ra 600oC, xc tc Cr2O3 + Al2O3, p sut thp. CH3 CH CH3 - T axeton: CH CH3 CH2 C CH3 CH CH2 + 2H2
OH CH3 C O OH CH3 CH CH3 C CH

+ H2 t0, Pd
CH3 + CH
CH
NaNH2
CH3
CH CH3
CH
OH CH3 CH CH3
-H2O
CH
CH2
CH3
CH CH3
CH
CH2
5.2.4.3. iu ch ankin a) iu ch axetylen:

- Thu phn canxi cacbua: CaC2
CaC2 CaC2 + + 2H2O 2HCl C2H2 + Ca(OH)2 C2H2 + CaCl2
- Piroly metan 1400 15000C

2CH4
1400 - 15000
HC
CH
3H2
b) iu ch dy ng ng axetylen:
- T dn xut i halogen
R CH Br CH2 Br OHR C CH + 2HBr
- T ng ng ca axetylen:
CH CNa + RI R C CH + NaI
5.2.4.5. ng dng
Chng 5: Hirocacbon a) ng dng anken
Trang 61
Dng sn xut ru, cc dn xut halogen v cc cht khc. trng hp polime: polietilen, poliprpilen. Etilen cn c dng lm qu mau chn.
b) ng dng ca ankin
Ch c axetilen c nhiu ng dng quan trng. thp sng (kh t n). Dng trong n x hn, ct kim loi. Dng tng hp nhiu cht hu c khc nhau: anehit axetic, cao su tng hp (policlopren), cc cht do v cc dung mi,
5.2.5. Khi nim v tecpen

Tecpen theo ngha hp l tn gi mt nhm H C a s khng no, thng gp trong gii thc vt, nht l trong tinh du tho mc (cc tinh du thng, s, cam, hoa hng, ...). Nhng H C ny c cng thc chung (C5H8)n (n2). Mch cacbon d h hay vng, dng nh do isopren C5H8 kt hp vi nhau theo kiu u ni vi ui ti thnh. Cc dn xut cha oxi ca tecpen (ancol, anehit, xeton, este, ...) c gi l tecpenoit. Tecpenoit cng rt ph bin trong cc loi tinh du tho mc v thng c tm quan trng ln hn chnh H Ctecpen. Trong thc t ngi ta thng dng khi nim tecpen cho c tecpen thc th (H C) v tecpenoit (dn xut cha oxi ca tecpen) Tecpen c phn loi theo n nh sau: n=2 n=3 n=4 n=6 n=8 monotecpen sesquitecpen itecpen tritecpen tetratecpen (hp cht C10) (hp cht C15) (hp cht C20) (hp cht C30) (hp cht C40)
Cao su thin nhin c coi l politecpen cao phn t.
5.2.5.1. Monotecpen
Mntecpen c th c cu trc mch h hoc mch vng (n vng hoc a vng). Chng l nhng cht lng hoc cht rn c mi thm c trng. Monotecpen tham gia cc phn ng ca nhm chc (nu c) v phn ng theo c ch gc H C. Mt s tecpen c dng lm dc phm, pha ch nc hoa, tng hp hu c, ... Sau y l mt s tecpen quan trng.
a) Hirocacbon tecpen
Chng 5: Hirocacbon
CH3
Trang 62
CH2
CH3
CH2 CH3 Miaxen CH3 CH3 Linomen CH2
CH3 CH3
- Pinen (Tinh dau thong)
(Tinh dau cay nguyet que) (Tinh dau cam, chanh, thong)
b) Ancol tecpen
CH3 CH2OH
CH3
CH3
CH2OH OH CH3 CH3 Geraniol (Tinh dau hoa hong, sa)

c) Anehit v xeton tecpen
CH3 O CHO CH3 CH3 CH3 CH3 Xitronelal (Tinh dau sa) Campho (long nao) CH3 Menton (Tinh dau bac ha) O CH3 CH3 CH3
CH3
CH3
CH3 Metol
CH3
Xit ronelol (Tinh dau hoa hong, sa)
(Tinh dau bac ha)
5.2.5.2. Cc loi tecpen khc a) Sesquitecpen (hp cht C15): C cu trc mch h hoc mch vng:
Chng 5: Hirocacbon
CH3
CH3 CH3
Trang 63
CH3 CH3 CH3 - Cadinen CH3 CH3 Bisabolen
CH3 CH3 CH3
CH3
CH2OH
Fanesol
b) itecpen (hp cht C20)

Quan trng nht l C20H39OH (trong thnh phn phn t clorophin di dng este) v retinol hay vitamin A C20H29OH (trong du gan c, lng trng, ...)
CH3 - CH - CH2 - CH2 CH3
CH2 - CH - CH2 - CH2 CH3

Phitol
CH2 - C = CH - CH2OH CH3
CH3
CH3
CH3
CH3 CH2OH
CH3
Retinol
Trong mt ngi, nh c enzim thch hp, retinol tham gia qu trnh chuyn ho qua li (oxi ho, ng phn ha, ...) vi hai dng andehit tng ng l politrans-retinal v 11-cis-retinal:
CH3 CH3 CH3 CH3 CH2OH CH3
Politrans-Retinol
CH3
CH3
CH3
CH3
CH3
11-cis-Retinol
CH3 CHO
c) Tetratecpen (hp cht C40)

Ph bin nht trong s cc tetratecpen l nhng carotenoit. l nhng sc t c mu vng n , rt ph bin trong gii thc vt (v c ng vt), bao gm hn 60 cht, m quan
Chng 5: Hirocacbon
trng nht l licopen v caroten.
Trang 64
Licopen C40H56 l st t mu ca c c chua:

CH3 CH3 CH3 CH3 CH3
CH3
Licopenl
CH3
CH3
CH3
CH3
Caroten C40H56 sc t mu da cam trong c c rt , qa gc, ... c cu trc gn ging licopen, ch khc nhau ch c hai vng 6 cnh hai u. Trong thin nhin c 3 dng caroten l
, , ; chng khc nhau v v tr ca ni i trong vng. ng phn chim t l cao nht

(85%):
CH3 CH3 CH3 CH3 CH3
CH3
Caropenl
CH3
CH3
CH3
Caropen cn c gi l provitamin A v di tc dng ca enzim carotenaza c trong gan, mi phn t caroten c chuyn thnh hai phn tr vitamin A.
5.2.6. Khi nim v Steroit

Steroit l nhng hp cht thin nhin, trong phn t c cha khung pehiro xiclopentanophenantren:
C A B
Thuc vo nhm steroit l cc sterol, axit mt, hocmon sinh dc v cc cht c ng v thc vt. Sterol thuc nhm cc ancol a vng, rt ph bin trong c th ng vtv thc vt. Sterol ng vt c cha 27 nguyn t C trong phn t, cn sterol thc vt c cha 28 hay 29 nguyn t cacbon trong phn t. Sterol quan trng v c bin sm nht l cholesterol (cholestorin), C27H45OH. N c trong hu ht cc b phn ca c th ng vt, nhng c bit c lng ln trong tu sng v trong no:
Chng 5: Hirocacbon
21
Trang 65
CH3
18
22 20 23
24 25
CH3
13 14
CH3
26
27 19
CH3
10
11
12
17 16 15
CH3
2 3
1 5 4
9 8 6 7
HO
Cholesterol
Cholesterol c phn lp ln u tin t si mt (1775) v l thnh phn chnh ca si mt. Cholestrol l mt ancol bc hai, kt tinh hnh kim. Ecgosterol (ecgosterin), C28H43OH c phn lp t nm men. Khi chiu sng bng tia t ngoi, ecgosterol ng phn ho thnh vitamin D2 hay canxipherol. Trong phn ng chuyn ho ny,vng B ca ecgosterol b m lin kt C9 C10, ng thi to lin kt i gia cc nguyn t C10 v C19.
CH3
18 21 22 20 23 27 19 24 25
CH3
13 14
CH3
26
CH3 CH3
CH3 CH3
CH3
10
11
12
17 16 15
CH3 CH2 H HO
Vitamin D2
2 3
1 5 4
9 8 6 7
H
Ecgosterol
HO
Nh vy ecgosterol l provitamin D2. Vitamin D3 c to thnh t 7-ehirchlesterol. Vitamin D c nhiu trong du gan c, lng trng, ... Trong nhm cc vitamin D. Vitamin D2 v D3 l quan trng nht. vitamin D cn thit cho mi ngi. Thiu vitamin D, tr em thng b ci xng, ngi ln b nhuyn xng. Axit mt: gm mt nhm cc axit c cu to gn vi sterol v c tch ra t mt. Th d, cc axit cholic, eoxicholic v lichlic, ... c trong mt ca ngi v ng vt c sng. Axit mt c vai tr sinh l quan trng, c kh nng nh twong ho v lm d dng cho qu trnh tiu ho v ng ho m.
Chng 5: Hirocacbon
CH3 OH CH3
CH3 OH COOH CH3 CH3
Trang 66
COOH
CH3
HO
OH Axitcholic
HO Axit dexicholic
Cc hocmon steroit, c phn lp t tuyn sinh dc v v tuyn thng thn; cc hocmon ny c vai tr c bit quan trng, nh iu ho cc qu trnh trao i cht, pht trin, sinh sn v lo ho. Tu thuc vo tc dng sinh hc, ngi ta chia hocmon steroit thnh hocmon sinh dc v hocmon coticoit. Hocmon sinh dc: c phn lp t tuyn sinh dc. Hocmon sinh dc n estron c phn lp ln u tin bi Butenan (Butenand 1929), cn hocmon sinh dc nam testosteron oc phn lp nm 1935.
CH3
CH3 CH3
OH
H HO Estron O
H Testosteron
Vic pht trin ho hc cc steroit dn ti tng hp qui m cng nghip cc h steroit quan trng nht.
Chng 5: Hirocacbon 5.3. HIROCACBON THM
Trang 67
Hirocacbon thm l nhng H C mch vng cha no nhng c tnh cht rt c trng khng ging cc H C khng no trn, tnh cht c gi l tnh thm. Benzen C6H6 l H C thm tiu biu v quan trng nht v vng ny c mt trong tt c cc H C thm c vng benzen m ta gi l aren. Th d:
CH3
Benzen
Toluen
Naphtalen
Ngoi ra cn c mt s hp cht thm khc li cha nhng vng thm khc.
5.3.1. Cu trc phn t benzen v khi nim v vng thm

Benzen c cu trc phn t C6H6 ng vi cng thc chung CnH2n-6 (n6). Theo cng thc ny th dng nh benzen l hp cht rt khng no. Thc t benzen l hp cht vng rt bn, c th cng H2 mt cch khng d dng (so vi etylen, hexadien 1,3, ....) to thnh xiclohexan. Song li th hin tnh cht ca mt hp cht no, nh khng tc dng vi nc brm v dung dch KMnO4 long, d tham gia phn ng th vi brm, axit nitric, ... khi c mt cht xc tc, ... c tnh c gi l tnh thm. Cc kt qu kho st cu trc phn t benzen bng phng php ho hc v phng php vt l cho thy benzen c vng su cnh u v phng, tt cc cc gc CCC u bng 1200, tt c cc lin kt CC u bng 1,39 A0 (di hn lin kt C = C trong etylen v ngn hn lin kt CC trong etan). Theo Kekule (1865) th benzen l vng su cnh c ba lin kt i v ba lin n xen k nhau. Cng thc ny khng gii thch c tnh thm v c im hnh hc ca benzen.
CT: Kekule Theo quan im hin nay: benzen c 6 nguyn t C sp2 , mi nguyn t s dng ba obitan sp2 to ra 3 lin kt vi 2 C sp2 v mt H.
H H
120o 120o 120o
H H
Chng 5: Hirocacbon
Trang 68
Hnh 5.7: cc lin kt xch ma trong phn t bezen. Cn li obitan 2p c trc thng gc vi mt phng cha cc lin kt xch ma th xen ph bn vi obitan 2p ca hai nguyn t C bn cnh to thnh obitan phn t pi, tc l to lin kt khp vng (hnh 5.8)
H H
hay
H H
H Hnh 5.8: Lin kt pi trong phn t benzen
biu din vng benzen trn mt phng giy ta c th dng cng thc Kekule (a) vi cch hiu ni dung mi trn. Hoc cng thc vng i xng (b).
(a)
(b)
Vng benzen l mtt vng thm in hnh. Nhng vng khc cng c th c coi l vng thm, nu tho mn iu kin sau y: a) Vng c cu trc phng v phi c h thng lin hp khp kn: Nhng vng khng nht thit ch do C to nn m c th do nguyn t ca cc nguyn t khc. Th d:
Benzen
N Piridin
O Furan Naphtalen
b) H lin hp khp kn c s electron hoc p cp i u vi tng s k=4n+2 (n= 1, 2, 3, 4, ....). Th d: k = 2 (hay n= 0) C3H7 + C3H7 C6H5 2+ C3H7 C6H5 C6H5 C6H5
V vy, nhng vng sau y khng phi l vng thm, nn khng bn hoc km bn:
Chng 5: Hirocacbon
Trang 69
H H
k=4
k = 10 (khong phang)
5.3.2. Tnh cht vt l
Aren l nhng cht lng hoc rn khn gtan trongnc, tan trong cc H C khc v nhiu dung mi hu c. Cc aren lng u nh hn nc. Hng s vt l ca mt s aren c trnh by bng 5.3:
Bng 5.3 Hng s vt l ca mt s hirocacbon thm Hp cht Benzen Toluen C6H6 C6H5 CH3 Cng thc
0 t nc
t s0
80 111 136 152 144 139 138 182 218 340
d 0,879 0,867 0,867 0,862 0,880 0,864 0,861 0,997 1,145 1,250
5,5 -95 -95 -96 -25 -48 13 -2 80 217
Etyl bezen C6H5 C2H5 Cumen o-Xilen m-Xilen p-Xilen Stiren Naphtalen Antraxen C6H5 CH(CH3)2 1,2-C6H4(CH3)2 1,3-C6H4(CH3)2 1,4-C6H4(CH3)2 C6H5 CH = CH2 C10H8 C14H10
Benzen c tnh cht ho hc c trng l phn ng th electrophin, cn nhng phn ng cng v phn ng oxi ho ch xy ra trong iu kin khc nghit. Cc ng ng ca benzen cng tham gia cc phn ng th nhn thm, ngoi ra cn cc phn ng nhm ankyl, nh th hiro v oxi ho.
5.3.3.1. Phn ng th electrophin nhn thm a) S phn ng
Ar H + Z E
xt
Ar
HZ
Chng 5: Hirocacbon
Trang 70
Vi:
Ar: gc thm Z E: c th l Br Br (xt), HO NO2, HO SO3H, HO C3H7, ...
Th d:
+ Br2
Fe
Br
HBr
+ HO
NO2
H2SO4
NO2
H2O
+ HO
SO3H
SO3
SO3H +
H2O
b) C ch phn ng
Nh c cht xc tc thch hp, tc nhn phn ng Z E cho ta ion E(+) (hoc mt dng tng t), ion ny tn cng vng benzen ch no giu mt electron hn, theo s sau:
H + E(+) Benzen
cham
E
nhanh
+
Phc pi
+ (San pham the)
H(+)
Th d 1: C ch phn ng brm ho benzen:
2Fe
3Br2
2FeBr3
Br Br + FeBr3
Br ...Br Fe Br3 hoc Br [FeBr4 ]

H Br Br
nhanh cham
(+)
()
+ Br(+) Benzen
+
Phc pi
H(+)
(San pham the)
FeBr4
(-)
H(+)
FeBr3
+ HBr
Th d 2: C ch phn ng nitro ho benzen:
H2SO4 HO
H(+)
HSO4 H
(-)
NO2 + H(+)
O H
NO2
H2O + NO2
(+)
Chng 5: Hirocacbon
H + NO2(+)
Benzen cham
NO2
Trang 71
NO2 +
(San pham the)
+
Phc pi
nhanh
H(+)
c) Quy lut th vng benzen

Quy lut th trong nhn benzen nghin cu v gii thch kh nng nh hng v kh nng phn ng ca cc nhm th c sn trong nhn. Quy lut ny gm 4 im sau:
Nhm th loi I: Nhm th loi I nh hng nhm th sau vo v tr octo v para. Dn xut
meta to thnh khng ng k. Khi trong nhn tn ti nhm th loi I (tr halogen) th phn ng th xy ra d dng hn. Ta ni nhm th loi I lm cho nhn hot ho. Nhm th loi I thuc nhm th no (khn gb oxi ho, khng kt hp vi hiro). Nhng nhm th loi I:
O-, OH, OR, NH2, NRH, NR2, NHCOR, CH3, C2H5, ..., C6H5, F, Cl, Br, I
OH + NO2(+)
Phenol
OH + NO2
OH NO2
Nhm th loi II: nh hng nhm th sau vo v tr meta. Dn xut octo v para to thnh
khng ng k. Nhm th loi II lm cho nhn th ng ho. Nhm th loi II thuc nhm th khng no (d b hiro ho, kt hp vi hiro). Nhm th loi II l:
R C O , -CHO, -CN, -CCl3, -COOH, -SO3H, -COOR, -COCl, CONH2, -NH3, NH2R, NO2, ...
+ +
NO2 + SO3
Phenol
OH SO3H
Nhm th trung gian: nh hng nhm th sau vo 3 v tr octo, para v meta. Nhng nhm
th trung gian l:
CH2F, CH2NO2, CH2-CH2-NO2, NO, ....
- Nu trong nhn benzen tn ti hai nhm th cng loi: th nhm th no mnh hn quyt nh hng nhm th sau vo nhn benzen. Nhm th loi I: O- > NR2 > NRH > NH2 > OH > OR > X > R Nhm th loi II: NR3+ > COOH > SO3H > NO2
Chng 5: Hirocacbon
Trang 72
NH2
NH2
(+)
NH2
(+)
N(CH3)2
+ NO2 NO2
(+)
N(CH3)2 & NO2
(+)
N(CH3)2
NH2 CH3 + Cl(+)

- H+
NH2 CH3 Cl & Cl
NH2 CH3
- Nu trong nhn benzen tn ti hai nhm th khc loi: th nhm th loi I quyt nh hng nhm th sau vo nhn.
CH3 NO2 + NO2 NO2
(+)
CH3 NO2 + NO2
CH3 NO2
Gii thch quy lut th trong nhn benzen:
Theo thuyt in t gii thch s nh hng v kh nng phn ng ca hp cht H C thm c cha nhm th bng s chuyn dch in t (do hiu ng C v I) ca phn t trng thi tnh v trng thi ng. S chuyn dch in t ny l do cc nhm th gy nn. Yu t tnh: Nhm th loi I (tr halogen) l nhng nhm th aayr in t, lm giu
mt in t trong nhn benzen c bit v tr o v p. Phn ng th v vy d xy ra hn. Ta ni nhm th loi mt lm cho nhn hot ho:
CH3 OH NH2
Nhm th loi II: l nhng nhm th ht electron, lm ngho mt in tch trong nhn c bit v tr o, p. Phn ng th xy ra kh hn so vi benzen khng c nhm th. Tc nhn Z+ s tn cng vo v tr meta l ni mt electron giu tng i hn so vi cc v tr kia (o, p). Nhm th loi II lm th ng ho nhn.
CH3 COOH NO2 CH3 N CH3
Chng 5: Hirocacbon
Trang 73
Yu t ng: Gii thch s nh hng v kh nng phn ng ca cc nhm th da vo c s ca hiu ng nhit ( bn ca sn phm phc . Tc nhn Z+ s tn cng vo v tr no m phc to thnh c nng lng b nht. Nhm th loi I trng thi ng cng th hin kh nng cho in t, v vy nhng phc to thnh c nng lng bn nht. Nhm th loi I trng thi ng cng th hin kh nng cho in t, v vy nhng phc to thnh lin hp vi nhm th (o, p) s c n b mt in t (mt in t hao ht do tc nhn Z+ ly ra) lm cho phc trng thi nh phn t trung ho. Nng lng to phc b, phc d to thnh. iu gii thch v sao nhm th loi I nh hng nhm th sau vo v tr o v p. Nhm th loi II trng thi ng cng ht in t. V vy, khi gii to in tch dng ca tc nhn NO2+ 3 v tr o, p, m khng c nhm th tham gia, ngha l khng c s n b in t t nhm th vo nhn m c th ngc li lm cho nhn tch in dng nhiu hn cc v tr o, p. Nh vy, yu t ng khng gii thch c s nh hng ca nhm th loi II vo v tr meta.
5.3.3.2. Phn ng cng
Phn ng cng vo vng benzen c th xy ra, song tng i kh khn.

a) Cng hiro
Ni 150oC
+ 3H2
Ch : xiclohexen c phn ng nhanh, ngay nhit phng

Ni
+ H2
b) Cng clo
Cl Cl + 3Cl2
as
Cl
Cl Cl
Cl
Sn phm sinh ra c tn 1,2,3,4,5,6-hexacloxiclohexan. C 8 ng phn lp th, trong cc ng phn lp th ch c ng phn c hot tnh tr su rt cao. Trong mt thi gian di ng phn ny c dng lm thuc tr su, tr mui di cc tn gi hexacloran, 666, lindan, .... Phn ng cng theo c ch:
Chng 5: Hirocacbon
Trang 74
H + Cl* Benzen
5.3.3.3. Phn ng oxy ho a) Phn ng oxy ho khng hon ton
Cl
Cl2
H Cl H Cl
Cl
...
Cl Cl Cl
Cl Cl
Benzen khng phn ng cao vi dung dch KMnO4, nhng nhit cao c v c mt cht xc tc V2O5 benzen b oxy ho thnh anehit maleic. Phn ng xy ra: O + Benzen
b) Phn ng chy
9 2
O2
V2O5 450 - 500oC
O O
+ 2H2O + 2CO2
Benzen v cc ng ng ca n chy trong khng kh vi ngn la mu vng v thng c mi en. Nu c oxi, phn ng oxi ho s xy ra hon ton: C6H6 +
15 2 O2 6CO2 + 3H2O ; H = 3350 kJ/mol
5.3.3.4. Cc phn ng mch nhnh ca ankylbenzen a) Halogen ho mch nhnh
Khi chiu sng v un nng, clo v brm c th th hiro nhnh ankyl mt cch d dng, nht l v tr (do nh hng ca vng benzen). Th d:
CH3 + Br2
as, toC
CH2Br + HBr
CH2
CH3
as, toC
CH Br
CH3 +
HBr
b) Oxy ho mch nhnh
V tr ca ankylbenzen rt hot ng i vi cht oxy ho mnh nh KMnO4 hoc K2Cr2O7 trong mi trng axit H2SO4. Th d:
CH3
KMnO4 toC
COOK
H(+)
COOH
Nu v tr khng cn H th phn ng xy ra kh khn hn.
Chng 5: Hirocacbon 5.3.4. Phng php iu ch
Trang 75
a) Ngun ch yu hp cht H C thm l du m, sn phm crcking du v t nha than . Hp cht thm c tch ra t nha than hoc du la bng cch chng ct phn on. Cc phn ca nha than : - Du nh (si 80 170oC, hiu sut 3 5%) cha benzen, toluen, xilen v mt t etyl benzen, ... - Du trung bnh (phn si 170 240oC, hiu sut 10%) ch yu l phenol, crezol v naphtalen. - Du nng (phn si 240 270oC, hiu sut 10 15%) cha naphtanlen, crezol, iphenyl, antraxen v mt t quinolin. - Du antraxen hay du xanh (phn si 360oC, hiu sut 20%) cha antraxen, ... - Phn cn b gi tc l hc in (hiu sut 5 6%) dng lm nha tri ng. Du m cha nhiu H C thm ch yu l benzen v cc ng ng ca n. Tch H C khi H C no bng cch dng SO2 lng -60oC ch tan H C thm.
b) iu ch benzen
- T axetylen: 3CH - T paraphin Phn ng thm ho paraphin to thnh hp cht H C thm c mt xc tc Pt, Pd, Cr2O3 c tm ra cng mt lc bi nhiu tc gi: Kazan, Plate, Mondap, Kamusep.
n - hexan
Pt, 300oC
CH
6000C C
- Chng kh mui axit benzoic:
COONa + NaOH
c) iu ch dy ng ng ca benzen
CaO, toC
Na2CO3
- Phn ng Wurts Fitting: ng ng ca benzen c th iu ch c bng cch cho Na kim loi tc dng vi halogen thm v thng trong mi trng ete khan:
Br + 2Na + Br C2H5 ete khan
C2H5 + 2NaBr
- Phn ng Friede Crabt: Cc ng ng ca benzen c th iu ch bng cch ankyl ho benzen c AlCl3 lm xc tc.
Chng 5: Hirocacbon
CH3 + CH3Cl
AlCl3
Trang 76
HCl
- T paraphin:
CH3 CH CH3 CH2 CH2 CH CH3 CH3
Pt, 300oC
CH3
CH3
- T propin:
CH3 3CH3 C CH
toC xt
CH3
CH3
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn
Trang 77
Chng 6: HP CHT HU C N CHC V A CHC

6.1. Dn xut halogen 6.1.1. Khi nim chung Khi thay th mt hoc vi nguyn t H trong phn t cc H C bng cc nguyn t halogen s thu c cc hp cht hu c cha halogen, gi l dn xut halogen. Cng thc tng qut c dng sau: R X (vii R: gc H C, X: halogen) Can c vo c im cu to trong phn t c th phn loi cc dn xut halogen theo nhiu cch khc nhau: - Da vo bn cht ca halogen: c 4 loi dn xut halogen (dn xut florua, clorua, bromua, itua) - Da vo bn cht mch C trong phn t: dn xut halogen no, dn xut halogen khng no, dn xut halogen vng no, dn xut halogen thm, .... - Da vo s lng nguyn t halogen: dn xut monohalogen v dn xut polihalogen (ihalogen, trihalogen, ..., polihalogen) Danh php: - Tn thng thng: c tn gc H C (R) ri thm tn halogen tng ng - Tn quc t IUPAC: V tr ca hal tn hal + tn ca H C tng ng. Bng 6.1: Danh php ca mt s dn xut hal Cng thc CH3 Cl C2H5 Cl CH3 CH2 CH2 I
CH3 CH CH3
Danh php thng thng Metyl clorua Etyl clorua n propyl iotua izo propyl iotua
Danh php quc t Clo metan Clo etan 1 - it propan 2 it propan
I
C6H5 Br CH2 = CH Cl 6.1.2. Tnh cht vt l Tnh cht vtl ca cc dn xut hal ph thuc vo thnh phn v cu to ca gc H C cng nh vo hal. Cc ankyl halogenua c khi lng phn t thp l nhng cht kh, trung bnh l cht lng, cao l cht rn. Cc dn xut hal u l hp cht cng ho tr nn thc t khng tan trong nc, chng tan trong dung mi hu c v bn thn dn xut hal cng l dung mi hu c tt. Bng 6.2 dn ra tnh Phenyl bromua Vinyl clorua Brom benzen Clo eten
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn cht vt l ca mt s dn xut hal. Bng 6.2: Hng s vt l ca mt s dn xut halogen CTPT CH3 Cl CH3 Br CH3 I C2H5 Cl CH3 CH2 CH2 Cl CH2 = CH Cl CH2 = CH CH2 Cl C6H5 Cl C6H5 Br CHCl3 CCl4 6.1.3. iu ch dn xut hal a) Tc dng trc tip hal vi H C tng ng Th d: - Halogen ho anken CH3 CH2 CH3 - Halogen ho anken CH3 CH = CH2 CH2 = CH2 + Br2 + Cl2
as CH3 CHCl CH3 + HCl
Trang 78
Tn Clometan (metyl clorua) Brom metan It metan Clo etan 1 clo propan Vinyl clorua (cl eten) 3-clo propen - 1 Clo benzen Brom benzen Clorofom Cacbon tetraclorua
0 t nc
t s0
d 0,920 1,932 2,280 0,898 0,890 0,911 0,938 1,107 1,499 1,500 1,600
-97,00 -23,70 -93,00 -66,00 -139,0 -122,8 4,600 42,30 12,00 47,20
-154,0 -14,00 -136,0 -45,20 -30,60 -63,50 -22,90 45,70 132,0 155,1 61,20 77,00
CH3 CHBr CH2Br
+ Cl2 CH2 = CH Cl + HCl

300 0 C
- Halogen ho H C thm
Br2
as
Fe
Br
HBr
C6H6
b) i t ancol
3Cl2 C6H6Cl6
Khi un nng ancol vi HX (HCl, HBr, HI) c mt ca xc tc ZnCl2, ancol s chuyn ha
Trang 79
d dng thnh dn xut hal tng ng. R OH + HX

ZnCl 2 R X + H2O ZnCl 2 C2H5 Cl + H2O
Th d: C2H5 OH
c) Cng HX vo anken
+ HCl
R CH = CH2 + HX
R CHX CH3 CH3 CHBr CH3
Th d: CH3 CH = CH2 + HBr

6.1.4. Tnh cht ho hc Bn cht ca lin kt C X
Trung tm phn ng ca dn xut hal l lin kt C X. Do X > C, nn lin kt C X l lin kt cng ho tr phn cc:
C
Kh nng phn ng ca cc dn xut hal
Kh nng phn ng ca cc dn xut hal , trc ht ph thuc vo bn cht ca lin kt cc hal. Tu theo bn cht ca hal, kh nng phn ng ca dn xut hal c sp xp nh sau: R I > R Br > R Cl > R F Nh vy dn xut it l hot ng nht, loi km nht l dn xut flo. iu ny c gii thch l do phn cc ln ca lin kt C I ln nht so vi cc lin kt C X khc. Mt khc kh nng lin kt ca cc dn xut hal cn ph thuc vo c im ca gc H C lin kt vi hal. ng v mt ny, cc dn xut hal c th c chia thnh 3 loi: - Loi c kh nng phn ng cao: gm cc dn xut hal, trong nguyn t hal nh vi nguyn t C b cnh nguyn t C mang ni i, hoc vi nguyn t C cnh nhn thm. Th d:
CH2
CH
Alyl clorua
CH2
Cl
CH2
benzyl clorua
Cl
- Loi c kh nng phn ng trung bnh: gm cc ankyl v xicloankyl hal. Th d

CH3 CH Cl
2-clo propan Metyl clorua xiclophenyl
CH3
CH2
Cl
- Loi c kh nng phn ng km gm cc ankenyl v aryl halogenua, trong hal ni trc tip vi Csp2. Kh nng phn ct lin kt C X gim v trong phn t cn c hiu ng lin hp +C ca cp electron p ca hal vi electron pi ca lin kt i hoc vi h thng electron pi ca nhn thm. Th d:
Trang 80
CH2
CH
.. Cl
Clobenzen
.. Cl
Vinyl clorua
Nhng phn ng quan trng ca dn xut hal l th, tch v tc dng vi kim loi. Ngoi ra, cc hp cht cn c th tham gia phn ng gc H C (th nhn thm, cng vo gc khng no, ...)
6.1.4.1. Phn ng th
Phn ng th nguyn t hal trong dn xut hal xy ra ch yu theo c ch SN. R X + KOH R X + R1ONa R X + 2NH3 d R X + KCN
R OH + KX R O R1 + NaX
R NH2 + NH4X R CN + KX
R X + R1COONa Th d: CH3 Cl + KOH
R1COOR
+ NaX
CH3 OH + KCl C2H5 O CH3 + NaCl C2H5 NH2 + NH4Br
C2H5 Cl + CH3ONa C2H5 Br + 2NH3 d C2H5 I + KCN
C2H5 CN + KI CH3COOC2H5
X(-) + NaCl
C2H5 Cl + CH3COONa S din ra nh sau: Y(-) + RX
R Y +
Tc nhn nucleophin Y(-) c th gi l anion hay phn tu trung ho c cp e t do mt nguyn t Cl-, Br-, I-, OH-, CN-, H3N:, .... Nguyn t hay nhm nguyn t X b thay th l nhm ht e (-Cl, -Br, -I, -OH, -NR3, -SR2, ...) Tu theo s phn t tham gia vo giai on quyt nh tc phn ng, ta phn bit phn ng th rng:
2 1 SN v SN . Cc kt qu kho st bng thc nghim cng nh l thuyt u i n kt lun
bc ca gc ankyl R cng cao th kh nng tham gia phn ng SN cng gim, trong
2
khi kh nng phn ng SN cng tng.

1
Th d 1: phn ng th theo c ch SN :
1
Trang 81
CH3 CH3 C CH3 C ch:

CH3 CH3 C
+
CH3 Cl + OH
CH3
C CH3
OH + Cl
CH3 Clcham
CH3
C+ CH3
+ Cl -
CH3
CH3 CH3 C
+ nhanh
CH3 + C CH3
CH3 + OH
CH3
CH3 CH3 C CH3 OH
nhanh
HO
CH3 CH3
CH3
Th d 2: Phn ng th lng phn t SN

2
CH3 Cl + OHC ch:
CH3OH + Cl-
H OH- + H C
+
H C H (TTCT)
+
Cl
HO-
Cl
H HO C H H +
Cl -
6.1.4.2. Phn ng tch HX

Khi un nng dn xut hal vi dung dch kim trong etanol s xy ra phn ng tch HX to thnh H C khng no. Th d: CH3 CH2 Br
KOH,ancol CH2 = CH2 + HBr
c im cu to ca dn xut hal c nh hng r rt n kh nng phn ng tch. i vi cc dn xut hal c cng gc R, nhng c hal khc nhau th kh nng tch theo trt t sau: R I > R Br > R Cl > R F Phn ng tch cc dn xut hal bc 1 thng ch to ra mt olephin, trong khi cc dn xut hal bc 2 v bc 3 tng ng c th tham gia phn ng tch theo hai hoc ba hng khc nhau, to ra hai hoc ba olephin ng phn khc nhau. Hng chnh ca nhng phn ng tch HX tun theo qui tc chung gi l qui tc Zaixep:
Trong phn ung tch nucleophin, hal b tch ra cng vi H nguyn t C c bc tng i cao hn, to ra olefin c tng i nhiu nhm th hn hai nguyn t C mang ni i.
Th d:

CH3 CH3 CH2 CH Br CH3
KOH etanol
Trang 82
CH3 + HBr
CH
81%
CH
CH3
CH2
CH
19%
CH2 +
HBr
6.1.3.3. Phn ng vi kim loi

Dn xut hal phn ng vi kim loi to thnh hp cht c kim: C2H5 Br C2H5 Br + + 2Li Mg
etekhan C2H5 Li + LiBr etekhan C2H5 Mg Br
Vi kim loi natri ta thu c ankan (phn ng Wurtz): 2C2H5 Br + 2Na

etekhan C2H5 C2H5 + 2NaBr
Phn ng xy ra:
2C2H5Br
2Na
2 C2 H5
2NaBr
2 C2 H5
C2H5 C2H5
Kh nng tch theo trt t sau: R I > R Br > R Cl > R F
6.1.5. Gii thiu cc cht tiu biu a) Metyl clorua, CH3Cl

L cht kh khng mu, c th iu ch cng vi cc dn xut clo khc ca metan bng cch clo ho trc tip H C ny. CH4 + Cl2
as CH3 Cl + HCl
Metyl clorua tinh khit c th c iu ch bng cch cho ancol metylic tc dng vi HCl p sut cao. CH3 OH + HCl
p,cao CH3 Cl + H2O
ng dng: CH3Cl c dng lm cht sinh hn cho t lnh, lm dung mi v tc nhn metyl ha.
b) Vinyl clorua, CH2 = CH Cl

Vinyl clorua l cht kh, c iu ch bng chc cng HClkh vo axetylen hay clo ho etylen: CH2 = CH2 + Cl2 CH2 = CH Cl + HCl
300 0 C 120 0 C,Cu Cl
2 2 CH CH + HCl CH2 = CH Cl
Di tc dng ca cht khi mo, vinyl clorua trng hp theo c ch gc t do to thnh polivinyl clorua (PVC):
Trang 83
n CH2
CH Cl
CH2
CH Cl
n
ng dng: Dng lm vi gi da, vt liu cch in, ...

c) Clo benzen, C6H5 Cl
Clo benzen l cht lng, c ieefu ch bng cch clo ho trc tip benzen:
+ Cl2
Fe
Cl
+ HCl
ng dng: dng tng hp phenol, anilin v nht l dng sn xut thc tr su DDT:
Cl
Clobenzen
CHO + CCl3
Cloral
Cl
Cl
CH Cl3
(DDT)
Cl + H2O
BI TP 6.1: Gi tn hp cht sau theo danh php IUPAC:
a) CH3
CH2
CH CH3
CH2
CH Cl
CH3
b) I Cl CH3 c)
I
Br
Br
6.2: un nng mi dn xut sau y vi dung dch NaOH m c trong nc.
a) CH3 CH2 Cl b) (CH3)2CH Cl c) (CH3)3C Cl Hy vit phng trnh phn ng v so snh tc phn ng.
6.3: Ngi ta chuyn ho hp cht A c CTPT C4H9Br theo s :
KOH, etanol (1)
B C D
KOH loang, nc (2) Mg, ete khan (3)
B l sn phm chnh v c cu hnh trans.
Trang 84
a) Vit CTCT ca A, B, C, D. b) Cho bit (1) v (2) thuc loi phn ng no? (cng, th, tch).
6.4: T C2H5Br v cc ho cht cn thit, vit ptp iu ch cc ancol sau:
a) CH3 CH2 CH2 OH b) CH3 CH2 CH(OH) CH3 c) (CH3)2 C(OH) CH2 CH3
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.2. Hp cht c nguyn t
Trang 85
C nguyn t l ngnh ho hc cc hchc ca hu ht cc nguyn t trong BTH tr cc nguyn t hu c (oganogen) c in nh H, O, N, S, cc hal. Trong phn t ca hp cht c nguyn t, nguyn t ca cc nguyn t lin kt trc tip vi nguyn t cacbon. Phn ln cc nguyn t trong BTH l kim loi cho nn hn na cc hp cht c nguyn t l hp cht c kim. Gia kim loi v phi kim khng c gii hn r rng, tuy vy ngi ta vn chia hp cht c nguyn t ra thnh c kim v c phi kim.
6.2.1. Hp cht c magie
Nhiu kim loi nh cc kim loi kim Li, Na, K; cc kim loi nhm II nh Mg, Ca; kim loi nhm III nh Al; nhm IV nh Sn, Pb v cc kim loi chuyn tip nh Zn, Cd, Hg, ... c th to thnh cc hp cht c kim tng ng. Cc gc hu c lin kt vi kim loi c th l ankyl, ankenyl, ankinyl hoc aryl. Cc hp cht c kim c gi theo tn gc H C vi tn kim loi v hal.
C2H5Na
etyl natri
CH3MgBr
metyl magie bromua
C6H5HgCl
phenyl thuyngan clorua
6.2.1.1. iu ch
- T ankyl halogenua: cho kim loi tc dng vi dn xut alkyl halogenua trong mi trng ete khan (trnh thu phn) RX RX 3R X + 2Li + Mg + 2Al
ete,khan R Li + LiX ete,khan R MgX ete,khan R AlX2 + R2AlX
- Tc dng kim loi vi cc hp cht c kim c sn: Cc kim loi nng hot ng yu khng tc dng trc tip vi cc hp cht hal, song hp kim ca chng vi kim loi Na th cho phn ng vi hiu sut cao. 2CH3 I
6.2.1.2. Ho tnh
+ Hg(Na)
CH3 Hg CH3 + 2NaI
Hp cht c magie thuc loi c kh nng phn ng cao, lin kt C Mg d t ra tham gia nhiu loi phn ng khc nhau:
a) Phn ng vi hp cht c H linh ng
S chung:
H A +
Th d:
R Mg X
R H + A MgX
Nc: H OH Ancol: H OR1
+ +
RMgX RMgX
R H + HO MgX
R H + R1O MgX
Trang 86
Amin: Axit:
H NHR1 H OCOR1
+ +
RMgX RMgX
R H + R1NH MgX R H + R1COO MgX
Da trn c s cc phn ng trn, ngi ta a ra phng php dng metyl magie ioua CH3MgI nh tnh v nh lng H linh ng trong cc hp cht hu c theo th tch kh metan thot ra: H OH + CH3MgX
CH4 + HO MgX
Phng php ny c th dng o m cc dung mi.

b) Phn ng cng vi hp cht cacbonyl v nitrin
Hp cht magie cng hp d dng vo cc lin kt bi phn cc nh C = O (hay C N) hnh thnh ra cc lin kt C C mi. Cacbanion R- tn cng vo C+ ca nhm C = O (hoc C N) v Mg2+ kt hp vi nguyn t O (hay N) mang in tch m, sau thu phn tip theo cho sn phm. S chung ca phn ng cng vi hp cht cacbonyl nh sau:
R1 R2 Magie ancolat c thu phn thnh ancol: R1 C O R C R2 OMgX
Magie ancolat
XMgR
R1 R C R2 OMgX + H2O R
R1 C R2
Ancol
OH
XMgOH
Nu R1 = R2 = H ta c fomandehit HCHO v sn phm ca phn ng l ancol bc mt, R CH2OH. Ny R1 hoc R2 = H ta c mt andehit ng ng ca HCHO l R1 CHO v sn phm ca phn ng l mt ancol bc hai, R CH(OH) R2. Nu R1 v R2 u l gc H C, ta c xeton R1 CO R2 v sn phm ca phn ung l mt ancol bc ba (RR1R2) OH.
6.2.2. Hp cht c phtpho

Hp cht c phi kim c nghin cu nhiu v c ng dng thc t rng ri l hp cht c photpho. N c dng lm thuc tr su c hiu lc cao, lm thuc cha bnh, cc hp cht cao phn t khng chy, cht ph gia du nhn, cht tuyn ni qung,.... Cc hp cht c photpho c chia thnh hai nhm: - Hp cht c lin kt C P, gm cc ankyl (aryl) photphin; cc ankyl (aryl) th ca axit photphin, axit photphon, axit photphonic, axit photphoric v cc photphinoxit.
Trang 87
- Hp cht c lin kt gin tip ca C vi P: C O P gm dn xut ca axit photphorow, axit photphoric.
6.2.2.1. Hp cht c photpho c lin kt C P

Trong s cc hp cht c lin kt C P, ng ch hp cht trong , photpho to 5 lin kt cng ho tr ng nht.
Th d 1: pentaphenylphotphoran (Wittig, 1949):

C6H5 P C6H5 C6H5 C6H5 C6H5
c tnh: tan trong dung mi hu c v khng tan trong nc, c nhit nng chy thp.
Th d 2: Ngoi ra cng cn phi k n cc dn xut c cha nhm chc ca axit ankyl

photphonic, chng hn nh:
OH HO P O
OH C CH3
OH P O OH
1-hidroxi etylidenphotphonic
c tnh: c kh nng to phc bn vi cc nguyn t kim th, chuyn tip v him.

6.2.2.2. Hp cht c photpho c lin kt C O P
Thuc vo loi hp cht ny l cc dn xut ca axit photphor v axit photphoric. Este hon ton ca axit photphor nhn c khi cho ancol tc dng vi photpho triclorua vi s c mt ca baz hay ancolat:
3C2H5 OH + PCl3
bazo
C2H5O P C2H5O C2H5O P C2H5O PCl3 Cl

Dietyclophotphit
C2H5
trietyl photphit
Cn etyl este hon ton ca axit photphoric (trietyl photphat) thu c bng cch cho ancol etylic tc dng vi photphotriclorua vi s c mt ca baz hoc natri etylat. Khi thu phn trietyl este ca axit photphoric bng mt lng NaOH va s thu c natri ietylphotphat:

O P C2H5O
-C2H5OH
Trang 88
C2H5O 3C2H5 OH + POCl3

-3HCl
O
+NaOH
C2H5
trimetyl photphat
C2H5O P C2H5O ONa

Natri dietylcltphat
Nhiu hp cht c photpho loi ny c hot tnh sinh l mnh, do chng c ng dng rng ri lm cht phng tr dch hi, nht l trong lnh vc cht tr su. u im ca chng so vi cc dn xut hal (hexacloran, DDT, ...) l b phn hu tng i nhanh, do t gy nhim mi trng, c tnh chn lc cao. Chng c th tiu dit cn trng gy hi m khng nh hng n cc sinh vt c ch khc.
6.2.2.3. Mt s hp cht tr su c phtpho a) Vophatoc [o,o imetyl o-(4-nitrophenyl) photphothioat]
y l cht rn c nhit nng chy 420C, dit nhiu loi cn trng gy hi, bo v cy trng nh la, ng, ma, cafe, bng, rau, ...
CH3O CTCT: CH3O S P O NO2
Vophatoc (metyl parathion)
c tnh: rt c, c xp vo nhm ho cht bo v thc vt ch c dng hn ch. Thi gian ngng phun thuc trc khi thu hoch 20 ngy. Thuc gii c Vophatoc: atropin, PAM, ...
b) Parathion [o,o ietyl o-(4-nitrophenyl) photphothioat]
y l cht rn c nhit chp chy 1740C, dit nhiu loi cn trng gy hi, tc dng mnh hn vophatoc.
C2H5O CTCT: C2H5O
S P O NO2
Parathion (thiophot)
c tnh: Parathion thuc loi cht rt c nguy him, ch c dng hn ch. Thuc gii c Parathion: atropin, PAM, ...
c) ipterex
L cht rn, nhit nng chy khong 81 820C, dit nhiu loi cn trng gy hi, bo v cy trng nh la, ng, ma, cc loi qu d rng, c bit chng cn trng 2 cnh nh bn, rui, gin, b cht, rp ging, ....
Trang 89
CH3O CTCT: CH3O
O P
OH CH CCl3
Dipterex Clorophot)
c tnh: ipterex thuc loi cht c.

c) Tuban, Sarin, Soman
y l nhng loi cht c m c quc x sn xut dng trong chin tranh th gii th hai, nhng m mu ca chng cha kp thc hin th chng b ng minh nh bi.
N CTCT:
C P
O OC2H5
CH3 P F
Sarin
O OCH(CH3)2
CH3 P F
O CH3 O
Soman
(CH3)2N
Tabun
CH CH3
C CH3
CH3
c tnh: gy hi thn kinh.

BI TP 6.5: Xut pht t n propyl magie bromua v nhng ho cht cn thit khc, hy iu ch cc hp
cht sau y bng phn ng Grignard (Victor Grignard, 1900: R X + Mg R MgX)

ete,khan
a) 2-metyl pentanol 2 b) 4-metyl pentanol 1 c) Ru n-butylic

6.6: i t cc dn xut hal c s nguyn t C t hn hay bng ba v nhng ho cht cn thit
khc, hy iu ch cc hp cht di y:
a) CH3 CH CH3 b) CH3 CH2 CH2OH OH C CH3 CH3 c) CH3 CH2 OH C C2H5 CH2 CH3
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.3. Ancol v phenol 6.3.1. Khi nim chung
Trang 90
Khi thay th nguyn t H trong phn t H C bng nhm hiroxyl (hay hiroxi) OH ta c nhng dn xut hiroxyl, gi l ancol (ru) hoc phenol tu theo bn cht ca gc H C ni vi nhm hiroxi. Phenol khc vi ancol ch trong phn t phenol nhm OH lin kt trc tip vi vng thm, cn trong phn t ancol nhm OH c th lin kt vi mt gc no, gc khng no hay mch nhnh ca vng thm. Th d:
OH H OH
Ancol no (Xiclo hexanol)
CH2
CH
Ancol no (R. alylic)
CH2OH
CH2OH
Ancol thom R. benzylic
Da vo s nhm hiroxi c trong phn t, c th phn bit monophenol, iphenol, ... poliphenol hoc monoamcol (monol), iol, ... v poliol. Th d:
OH CH3
Monophenol (m-Crezol)
OH
OH
HO OH
Diphenol (Hidrquinol)
OH
Triphenol (Phlorogluxinol)
CH3
OH
CH2 OH
CH2 OH
CH2 OH
CH OH
CH2 OH
Monoancol (metanol)
Diol (Etylenglicol)
Triol (Propatriol - 1,2,3)
i vi ancol ngi ta cn phn bit ancol bc 1, bc 2 v ancol bc 3 tu theo nhm OH lin kt vi C bc 1 hay 2 hay 3. Th d:
CH3 C2H5 OH CH3 CH CH3
(Propanol-2)
CH3
CH3
(2-metyl Propanol-2)
Ancol b-1 (etanol)
OH Ancol b-2
OH Ancol b-3
6.3.2. Tnh cht vt l
Khi so snh tnh cht vt l ca ancol v phenol vi cc H C v nhiu dn xut khc c khi lng phn t tng ng, ta thy c nhiu im khc bit, nht l cc cht u dy ng ng. Chng hn ancol v phenol c nhit si v nhit nng chy cao hn rt nhiu: Hp cht M C2H5OH 46 CH3 O CH3 46 CH3 CH2 CH3 44
Trang 91
ts(oC) tnc(oC)
78 114
-25 -140
-42 -189
S d c s khc bit nh trn l do cc phn t ancol v phenol kt hp vi nhau bng nhng lin kt hiro (biu din bng ng chm):
R O : . . .H
. . .H
R O : . . .H O : . . .H R R O:
Ancol v phenol cng c th to lin kt vi H vi nc:

R
. . .H
O: ... O : . . .H
l nguyn nhn ch yu lm cho ancol d tan trong nc (CH3OH, C2H5OH, C3H7OH tan v hn trong nc). Khi s nguyn t C trong phn t tng ln, tan trong nc gim rt nhanh v phn gc H C k nc tng ln. Lin kt O H phenol phn cc mnh hn ancol. Do , phnol to lin kt hiro mnh hn ancol, th hin ch phenol c nhit si cao hn v tan trong nc ln hn. Phenol khc vi ancol cao l tan tt trong dd kim, c kh nng tch ra khi dd kim khi tc dng vi CO2. 6.3.3. Tnh cht ho hc Trong phn t ancol v phenol, nhm chc c trng c vai tr quyt nh n tnh cht ca phn t l nhm OH. V oxi c m in ln hn C v H, cc lin kt C O v O H phn cc mnh v pha oxi. Tu theo c im cu to ca gc H C, s phn cc ca lin kt C O c th tng hoc gim, khi phn cc ca lin kt O H cng bin i theo nhng hng ngc li. Ni cch khc C O cng t phn cc th O H cng phn cc mnh v ngc li. Th d: Trong phenol, nhm OH ni vi Csp2 ca nhn thm, cp ep trn Oxi lin hp vi e ca nhn, khin proton ca nhm OH d tch ra v cc phenol c tnh axit. Mt khc, do c hiu ng lin hp p - ny m mt e ca nhn thm c tng thm v phenol d tip nhn phn ng th electrophin hn so vi benzen.
:O
6.3.3.1. i vi ancol
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn a) Phn ng lin kt O H
Trang 92
S to thnh ancolat Do s phn cc ca lin kt O H (O H), cc ancol c th tch proton to thnh ion
ancolat. Ni chung, cc ancol l nhng axit yu (yu hn nc). Th d: pKa (CH3OH) = 16 Tnh axit ph thuc vo cu to R, tnh axit tng khi gc R ht n t (hiu ng I), gim khi R y in t (+I). So snh tnh linh ng ca H trong nhm OH gia ancol cc bc ta c: Ancol bc I > Ancol bc II > Ancol bc III Ancol c th phn ng vi kim loi kim (Na, K, ...) km mnh lit hn so vi nc, gii phng ra H2 v to thnh ancolat kim loi:
2R
OH
2Na
2R
ONa
Natri ancolat
H2
Cc ancolat l nhng cht rn d tan trong etanol to ra dung dch ancolat trong etanol c tnh baz mnh. V ancol l nhng axit yu nn cc ancolat nht l ancolat kim loi kim rt d b thu phn:
R ONa + H2O R OH + NaOH
Natri ancolat Ancolat
S to thnh este: ancol c th tc dng vi axit cacboxylic, c mt cht xc tc axit to
thnh este:
R1COOH C ch phn ng: + R2OH
H2SO4 toC
R1COOR2
H2O
OH R1 C O + H+ R1 C
+
OH OH
OH
R2OH
R1 R2
C O+
OH H
-H2O
O R1 Th d:
CH3COOH + C2H5OH
H2SO4 toC
C OR2
R1
C OR2
OH
CH3COOC2H5
Etyl axetat (90%)
H2O
Phn ng nu c tnh thun nghch. Hng s cn bng:
K CB =
[CH3COOC2H5 ] [H2O] = 4 [CH3COOH] [C2H5OH]
Trang 93
Hiu sut phn ng t khong 66% to thnh este. Ancol cng tc dng vi axit v c to thnh este v c:
OR ROH + H2SO4
-H2O
ROSO2OH
ROH -H2O
O2S
OR
CH3OH +
H2SO4
-H2O
CH3OSO2OH
Metyl sunfat
CH3OH -H2O
OCH3 O2S OCH3
Dimetyl sunfat
b) Phn ng lin kt C O
S to thnh halogenua ankyl:
Khi ru tc dng vi HX ta thu c RX:
OH
H2O
Phn ng to thnh R X t HX v ru l phn ng thun nghch xy ra vi tc ln khi c mt ca ca axit v c hoc khi dng tha HX. Kh nng phn ng: HI > HBr > HCl > HF Ancol bc I > bc II > bc III C th dng halogenua photpho (PX5, PX3) to thnh R X:
R R1 OH CH OH R3 R1 C R2 OH + PCl5 R1 + PCl5 R2 + PCl5 R Cl R1 + POCl3 + HCl CH Cl R3 C R2 Cl + POCl3 + HCl R2 + POCl3 + HCl
ehyrat ho ancol:
Phn ng loi nc t ancol xy ra khi un nng ancol c H2SO4 c lm xc tc. C hai trng hp:
- Loi nc gia hai phn t ancol to ete: khi un nng ancol 1400C v c mt
H2SO4 c, ancol c th phn ng vi nhau to thnh ete. Th d:

2R OH
H2SO4 140oC H2SO4 140oC
O
Ete
+ +
H2O H2O
2C2H5OH
C2H5OC2H5
Dietyl ete (80%)
- Loi nc ni phn t to thnh olefin: khi un nng ancol 1700C v c mt H2SO4

c th ancol s tch nc (tun theo quy tc Maccopnhicop) to thnh olefin:
Trang 94
R1
CH H
CH OH
R2
H2SO4 170oC
R1
CH
CH
R2
H2O
Phn ng loi nc ancol to thnh anken c th xy ra khi cho hi ancol i qua xc tc Al2O3 3750C:
R1
CH H
CH OH
R2
Al2O3 375oC
R1
CH
CH
R2
H2O
c) Phn ng oxy ho v ehir ho ancol
Phn ng oxy ha:

Ancol c th b oxy ho di tc dng ca nhng cht oxy ha mnh nh hn hp (K2-
Cr2O7 + H2SO4 v K2MnO4 + H2SO4) trong qu trnh oxh thng hng vo nguyn t C lin kt vi nhm OH. Tu theo cu to ca ancol m sn phm thu c khc nhau.
R R1 CH2OH CH OH R2 R
OXH
CHO R1 C O
OXH
R
OXH
COOH R1COOH + R2COOH
R2
i vi ancol bc III: trong ancol bc 3 nguyn t C mang nhm OH khng cn H do chng rt kh b oxh. Trng hp dng cht oxh mnh s cho ra hn hp xton v axit:
CH3 CH3 C CH3 OH

oxh
CH3
C CH3
CH2
CH3
C O
CH3 + HCOOH
Kh nng phn ng: Ancol bc I > ancol bc II > ancol bc III Tu theo bc C m cho sn phm oxy ha khc nhau. V vy c th s dng phn ng ny phn nh cu to cc hchc.
Phn ng hiro ha:

Khi cho hi ancol i qua kim loi Cu nung nng 200 300oC th t ancol bc I thu c
anehit, ancol bc II thu c xeton. Cn ancol bc III khng cho phn ng tng t, m li loi nc to anken: Ancol bc I:
Ancol b-II:
R CH2OH
R1 CH OH
Cu R CHO + H2
R2
Cu 200 - 300oC
R1
C O
R2
Xeton
H2

R2 Ancol b-III: R1 C OH CH2 R3
Cu 200 - 300oC
Trang 95
R2 R1 C CH R3 + H2O
Cc phn ng ny c dng phn bit 3 loi ancol.
6.3.3.2. i vi Phenol a) Ho tnh ca nhm OH
Tnh axit:
Phenol c tnh axit mnh hn ancol nn c kh nng to mui vi Na hoc NaOH:
OH 2 + 2Na 2
ONa + H2
Natri phenolat
OH + NaOH
ONa + H2O
Natri phenolat
Phenol khc vi ancol cao l tan tt trong dd kim, c kh nng tch ra khi dd kim khi tc dng vi CO2.
ONa + CO2 + H2O OH +
Phenol
NaHCO3
Natri phenolat
Khi so snh gi tr pKa ca phenol v cc phenol th ta d thy rng, nhm th ht e lm tng axit ca nhm OH v ngi li:
OH OH OH
pKa = 9,98
NO2 pKa = 7,15
CH3 pKa = 10,14
Phn ng to ete:
i vi phenol s phn ct lin kt C O xy ra kh hn ancol nn ete ca phenol c iu ch bng cch cho phenolat natri tc dng vi ankyl halogenua, iankyl sunfat, ...
C6H5ONa
C6H5ONa
+
+
R
CH3
I
I
ROC6H5
NaI
+ NaI
CH3OC6H5
Metoxibenzen (anisol)
Phn ng to este:
Khng th este ho trc tip phenol bng axit cacboxylic c xc tc nh ancol m mun to este ngi ta cho phenolat tc dng vi cc anhyrit axit hu c. Th d:

ONa + R C O Cl
Trang 96
C O
R + NaCl
Phn ng to aryl halogenua:

OH 2 + PCl5 2 Cl + POCl3 + H2O
b) Ho tnh ca nhn benzen

Phenol cha nhm OH l nhm th loi mt, nn n s nh hng nhm th sau vo v tr o, p v lm cho nhn hot ho hn.
Halogen ha:
Clo ho phenol s nhn c hn hp o, p - clo phenol. Tip tc clo ho s nhn c
2,4-iclo phenol v cui cng l 2,4,6-triclo phenol:
OH
Cl2 AlCl3
OH Cl &
OH
Cl2 AlCl3
OH Cl Cl
Cl2 AlCl3
OH Cl Cl Cl
Cl
Phenolat hot tnh cao hn phenol phn t, v vy cho dd nc brom v dd phenolat natri tc dng vi nhau cho kt ta trng ngay tc khc:
ONa + 3Br2 Br Br ONa Br + 3HBr
2,4,6- tribrom phenol
Nitro ho:
Nitro ho phenol bng HNO3 long thu c o,p-nitro phenol. Tip tc nitro ha s thu
c initro v trinitro phenol (axit picric):

OH
HNO3 H2SO4
OH
HNO3 H2SO4
OH NO2 NO2
HNO3 H2SO4
OH NO2 NO2
2,4,6- trinitro phenol
NO2
NO2
c) Phn ng ngng t
Phenol d dng tham gia phn ng ngng t vi andehit v axit.
Ngng t vi anehit fomic:

Khi c mt ca xc tc axit hoc kim, phenol s tham gia phn ng vi HCHO cho nha

phenol focmanehit:
Trang 97
OH n + nHCHO
OH CH2
n
nH2O
Nha phenol focmanehit bn vi axit v baz nn c dng lm cht cch in trong ngnh in my v v tuyn in.
Ngng t vi anhyrit phtalic:

OH O C C O
Anhydric phtalic
OH
2HO
C
-H2O
C O
Phenolphtalein
Trong mi trng kim phenolphtalein to thnh mui v cho mu :

OH OH OH
C C O
Phenol phtalein
+ OH-H2O
C C O O
Mau o
6.3.4. Phng php iu ch 6.3.4.1. iu ch ancol a) Thu phn dn xut halogen

Cc ankyl halogenua (R X) tham gia phn ng thu phn cho cc ancol c s C tng ng vi s C ca gc H C:
HOH
OH
HX
Phn ng thu phn trc tip dn xut halogen l phn ng thun nghch. phn ng xy ra d dng cho ancol hiu sut cao ta thng cho tc dng dn xut hal vi AgOH:
R X + AgOH R OH + AgX
Nguyn t hal trong R X cng linh ng th phn ng thu phn cng d dng xy ra. V vy, kh nng phn ng ca R X nh sau: R I > R Br > R Cl > R F
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn b) Thu phn este trong mi trng kim
R1COOR2 + NaOH
toC
Trang 98
R2
OH
R1COONa
c) Kh andehit v xeton
R
R1
CHO
C O
+
R2
H2
+
Ni toC
R
Ni toC
CH2OH
R1 CH OH R2
H2
d) i t dn xut c kim
R1 R C R2 OMgX + H2O R R1 C R2
Ancol
OH
XMgOH
e) Hirat ho olefin
Tu theo cu to ca olefin, khi hirat ho c th thu c ancol c bc khc nhau. Etylen cho ancol bc I, cn ng ng ca etylen cho ancol bc II hay bc III:
CH2 CH2 + H 2O
H+
CH3
H+
CH2
OH
CH
CH2
OH
CH OH
CH3
OH R1 C R2 CH2 + H OH
H+
C R2
CH3
6.3.4.2. iu ch phenol a) Chng khan than

Chng khan than 170 2700C thu c phenol. loi b tp cht khc nhau nh naphtalen ngi ta em ch ho vi kim thu c natri phenolat. Sau bm kh CO2 vo chuyn ho thnh phenol. ONa + CO2 + H2O OH + NaHCO3
b) Thu phn dn xut halogen
C6H6
+ Cl2 Fe
C6H5Cl
+NaOHac t 0cao, p cao
C6H5OH
c) Phn ng tan chy kim

Cho tan chy kim vi dn xut sunfonic axit thm ta nhn c phenol:
SO3H
H2SO4 + NaOH 250 - 350oC
Trang 99
OH
d) Trong cng nghip

Hin nay ngi ta hay dng phng php oxi ha cumen (iso-propylbenzen), v c hai sn phm ca phn ng (phenol v xeton) u quan trng i vi cng nghip ho hc:
CH3 CH3 C H CH3

O2 (OH-) Cumen
CH3 C O H
H2SO4 65oC Cumen hidropeoxit Phenol
OH + CH3 C O CH3
6.3.5. Hp cht tiu biu a) Metanol
L cht lng khng mu, d chy v rt c. Ung mt lng nh metanol (10 ml) cng c th lm m mt, vi s lng ln hn c th gy t vong. T lu metanol c sn xut bng cch chng ct khan g. Ngay nay ngi ta sn xut metanol ch yu t hh cacbon monoxit v H2 vi s c mt ca cht xc tc ZnO Cr2O3 300oC v 200 atm:
200 atm, 300oC ZnO-Cr2O3
CO
2H2
CH3OH
ng dng: dng sn xut HCHO v tert-Butyl metyl ete (MTBE) thay th tetra etyl ch lm ph gia chng n cho xng:
CH3 CH3 C CH3
2-metyl propen
CH2
CH3OH
H2SO4
CH3
C CH3
OCH3
tert-butyl metyl ete (MTBE)
b) Etanol
c iu ch trong cng nghip bng cch ln men ru C6H12O6 hoc hirat ho etylen vi s c mt ca xc tc nh P2O5, V2O5, t st c x l: C6H12O6
LMR 2C2H5OH + 2CO2
CH2
CH2
H2O
100 - 300 atm 300oC
CH3
CH2
OH
ng dng: c dng pha ru ung, iu ch butadien trong sn xut cao su tng hp. etanol 90% - 95% c dng ch yu trong cng nghip sn, vecni, pha ch hng liu, dc phm.
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn c) Ancol benzylic: C6H5 CH2OH
Trang 100
L ancol thm n gin nht, c trng thi t do v di dng cc este trong tinh du hoa nhi v cc hoa khc. ng dng: n c dng trong cng nghip hng liu sn xut nc hoa.
d) Phenyl etanol: C6H5 CH2 CH2 OH
Thnh phn chnh ca tinh du hoa hng. ng dng: c dng sn xut nc hoa.
e) Phenol
L cht kt tinh khng mu, nng chy 410C, si 182oC. Trong khng kh phenol b oxy ha, lc u c mu hng nht, sau tm thm li. Kh tan trong nc lnh, tan nhiu trong nc nng. Tan trong ancol, ete v benzen theo bt c t l no. Phenol c gy bng da, phenol cho vi st (III) mu tm c trng. ng dng: phenol l sn phm trung gian quan trng ca cng nghip tng hp hu c, dng sn xut nha phenol focmandehit, t si tng hp (capron, nilon), tng hp phm nhum, dc phm, cc cht dit c, ...
f) Cc naphtol
Quan trong nht l -naphtol (hay 1-naphtol) v -naphtol (hay 2-naphtol)

OH OH
-naphtol (t0nc=960C, ts = 2880C)
-naphtol (t0nc=1220C, ts = 2940C)
ng dng: dng trong cng nghip sn xut phm nhum.
g) ioxin: 2,3,7,8-tetracloibenzo-p-ioxin
Cht dit c 2,4,5-T (axit 2,4,5-triclo phenoxi axetic) c iu ch bng cch un nng 2,4,5-triclo phenol vi axit cloaxetic v NaOH, ri x l tip theo bng axit long:
Cl
6 5 1
OH + Cl CH2 Cl
Axit cloaxetic
Cl COOH Cl
6 5 1
OCH2
2
COOH
Cl
4 3
4 3
Cl
2,4,5-triclophenol
Axit 2,4,5-triclophenoxiaxetic
Sn phm ca phn ng ny l cht c 2,3,7,8-tetracloibenzo-p-ioxin, thng gi tc l ioxin

6 5 1
Trang 101
Cl Cl
6 5 1
OCH2
2
COOH
San phan chnh
OH + Cl CH2 Cl
Axit cloaxetic
Cl COOH
4 3
Cl
Axit 2,4,5-triclophenoxiaxetic
Cl
4 3
Cl
Cl
San pham phu
2,4,5-triclophenol
Cl
O
2,3,7,8-tetraclodibenzo-p-dioxin
Cl
Cht dit c 2,4,5-T lun lun c ln mt lng rt nh ioxin. ioxin b phn hu rt chm nn n tch lu dn trn ng rung v gy nhim mi trng. Do , t lu ngi ta khng dng 2,4,5-T lm cht dit c na. Cc th nghim trn c s sc vt cho thy ioxin l mt trong nhng cht c nht m ngi ta bit c. Th trn chut, ioxin c hn strichnin 2000 ln v c hn natri xianua khong 150.000 ln. Trong cuc chin tranh Vit Nam qun di M ri mt lng ln cht lm rng l mu da cam, cn gi l cht c mu da cam (gm ch yu l 2,4,5-T) c cha 2ppm ioxin.
BI TP 6.7: So snh xiclohexanol v phenol v cu trc phn t v tnh cht ho hc. 6.8: Vit phng trnh phn ng xy ra khi cho phenol, ru benzylic ring r tc dng ln lt
vi: Na, NaOH, HBr, Br2 (nc). Gii thch?
6.9: T t n v cc cht v c cn thit vit phng trnh phn ng iu ch:

a) Phenol, ru benzylic b) Nha phenol focmandehit c) CH3COOC6H5, CH3COOCH2C6H5 d) 2,4,5-T
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.4. Andehit v xeton 6.4.1. Khi nim chung
Trang 102
Hp cht cacbonyl l nhng hp cht hu c c cha nhm chc (C=O) ho tr hai gi l nhm cacbonyl Nu nhm cacbonyl lin kt vi mt gc H C v mt nguyn t H ta c andehit. Nu nhm cacbonyl lin kt vi hai gc H C ta c xeton:
R1
R2
O Andehit
O Xeton
Cc hp cht cacbonyl cn c chia thnh nhiu loi khc nhau tu thuc vo s lng nhm cacbonyl v bn cht ca gc H C trong phn t. Theo s lng nhm cacbonyl trong phn t ta phn bit hp cht: Monocacbonyl: CH3CHO, CH3COCH3, ... icacbonyl: HOC CHO, CH3COCH2COCH3, ... Theo bn chtgc H C ta c hp cht: Cacbonyl no: xiclohaxancacboxandehit C6H11 CHO, ietyl xeton C2H5COC2H5 Cacbonyl khng no: acrolein CH2 = CH CHO, .... Cacbonuy thm: C6H5 CHO, axetophenon C6H5 CO CH3, ...
6.4.2. Tnh cht vt l

Khc vi ancol, trong phn t andehit v xeton khng c nguyn t H linh ng, cho nn chng tn ti trng thi khng cng kt (v khng c lin kt hiro) v c nhit si thp hn ng k so vi cc ancol tng ng. Andehit fomic l cht kh iu kin thng, cc andehit tip theo l cht lng, cn andehit cao l cht rn. Xeton v cc cht tip theo l cht lng, xeton cao l cht rn. Andehit thp v xeton thp tan trong nc, andehit v xeton cao t tan trong nc. Cc andehit thp c mi thm.

Andehit v xeton l nhng hp cht c kh nng phn ng cao do c cha nhm cacbonyl phn cc mnh.
C O
S phn cc mnh nhm cacbonyl gy ra kh nng phn ng cao ca nhm cacbonyl trong andehit v xeton c bit l phn ng cng. Mt khc s phn cc ca nhm cacbonyl lm phn cc lin kt C H trong gc H C mch thng lm cho cc H c bit v tr C tr nn linh ng hn nn d tham gia phn ng th.
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.4.2.1. Phn ng ca nhm cacbonyl a) Phn ng cng H2 (kh, hiro ha)
Trang 103
Phn ng xy ra ph v LK i ca nhm cacbonyl chuyn thnh lin kt n. Andehit chuyn thnh ru bc mt, xeton chuyn thnh ru bc hai:
R C H O + H2
Ni, toC
CH2OH
Ar C H R1 C R2 Ar C CH3 O + H2
Ni, toC Ni, toC
H2
Ni, toC
Ar
CH2OH
H2
R1
CH OH
R2
Ar
CH OH
CH3
b) Cng hiroxianua (HCN)

Phn ng to thnh hiroxynitrin (xyanhirin) l sn phm trung gian quan trng trong tng hp hiroxiaxit v aminoaxit:
R C H R1 R2 O + HCN
OH-
CH OH CN
CN
HCN
OH-
R1
C OH
R2
Ar C H
c) Cng vi bisunfitnatri
O +
HCN
OH-
Ar
CH OH
CN
Andehit v xeton (ch c loi R CO CH3) cng vi bisunfitnatri to thnh hp cht bisunfit kt ta:
R C H O + HSO3Na R CH OH SO2ONa
Trang 104
Ar C H
R C CH3 O + HOSO2Na R
O +
HSO3Na
Ar
CH
OH
SO2ONa
OH C CH3 OSO2Na
ng dng ca phn ng ny tch v tinh ch cc andehit

d) Cng hp vi hp cht c magi
Phn ng ny quan trng v dng phn bit cc ru. Sau khi thu phn, t focmandehit cho ru bc 1, t andehit khc cho ru bc 2 v t xeton cho ru bc 3:
O H C H
Andehit formic
OMgX + RMgX H CH R
OMgX + R2MgX R1 CH R2
H2O H 2O
OH R CH2OH + Mg
Ru bac I
X
OH
O R1 C H
R1
CH OH
R2 + Mg X
Andehit khac
Ru bac II
R1 R2
R1 C O
Xeton
R1 OMgX
Magie ancolat H2O
OH OH + Mg X
XMgR
C R2
C R2
Ru bac III
e) Cng vi ru:
Andehit cng vi ru to thnh hemiaxetal:
O R1 C H + R2OH R1 CH
OH OR2
Andehit
Hemiaxetal
un nng andehit vi ru trong mi trng axit sn phm to ra axetal: O R1 C H

Andehit
OR2 + 2R2OH R1 CH + H2O OR2

axetal
Xeton cng cho sn phm tng t nh axetal gi l xetal nhng khng thu c bng cch tc dng trc tip vi ru m bng cch tc dng vi este octofomiat ankyl:

OR R1 C O R2 + H C OR OR
H2SO4
Trang 105
OR R1 C OR R2 + RCOOH
Axetal v xetal d thu phn trong mi trng axit, bn trong mi trng kim.
f) Cng hp vi amoniac:
Andehit cng vi amoniac to thnh andehit amoniac:

R C O H + NH3 R CH OH NH2
Andehit amoniac d loi nc v trng hp (tam hp) cho ra hp cht d vng:

H N
R R CH OH NH2
-H2O
CH
NH
CH HN
CH NH
CH R
g) Phn ng trng hp:
Phn ng ny ch c trng cho loi andehit bo. Andehit thm v xeton khc khng cho phn ng trng hp. Trng hp andehit xy ra khi c xc tc axit v c nh clohydric. Chng hn andehit fomic, trng thi kh trng hp thnh trioxit vng trioximetylen:
O 3HCHO H2C O C H2 CH2 O
Trioximetylen
trng thi dd 40% andehit fomic trng hp cho polime c cu to thng polioximetylen hay polifomandehit: (n+1) HCHO + H2O
6.4.3.2. Phn ng ca gc: a) Phn ng th vi s tham gia ca nguyn t H v tr C:
HOCH2 (OCH2)n OH
CH3 CHO + 3I2
+NaOH CI3 CHO CHI3 (Iodofom) + HCOONa
Phn ng ny c dng tng hp cc halofom (clorofom, bromofom, Ioofom) v dng xc nh s c mt ca cc nhm CH3CO- v CH3CHOH- trong cc phn t hu c. Nguyn t H C ca xeton cng d b clo ho v brom ho:
CH3 C O CH3 + Br2 CH3 C O CH2Br + HBr
Bromaxeton
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn b) Phn ng canizaro:
Trang 106
i vi cc andehit khng c H C nh andehit fomic, benzoic c kh nng tham gia phn ng oxi ho kh trong mi trng kim mnh: 2HCHO + NaOH
H2O CH3OH + HCOONa H2O C6H5 CH2OH + C6H5 COONa
2C6H5 CHO + NaOH
c) Phn ng th vo nhn benzen:
Nhm andehit hay nhm cacbonyl l nhm th loi II, nhm nh hng nhm th tip theo vo v tr meta v lm th ng ho nhn benzen:
CHO + HNO3
H2SO4
CHO + H2O NO2
6.4.3.3. Phn ng oxy ha
Andehit v xeton b oxi ha khc nhau. Andehit rt d b oxi ha ngay c vi tc nhn oxi ho yu nh ddAgNO3/ddNH3 hay Cu(OH)2
H R C andehit + Ag2O O
dd AgNO3 to
O
NH3
H + 2Ag trang
R axit
C O
Hay: R CHO + 2[Ag(NH3)2]OH

H R C + O 2Cu(OH)2 to
R COONH4 + 2Ag + 3NH3 + H2O

O R C axit O H + Cu2O + 2H2O o
c bit:
H C + Ag2O andehit fomic O H
dd AgNO3 o t
O
NH3
H + 2Ag trang
,t 0
C axit fomic O
ddAgNO3 NH
3 CO2 + H2O + 2Ag Nu d AgNO3 th: HCOOH + Ag2O
H H C + 2Cu(OH)2 O
to
O H C axit fomic
t
H + Cu2O + 2H2O o gach
Nu d Cu(OH)2 th: HCOOH + 2Cu(OH)2 CO2 + 3H2O + Cu2O Phn ng oxi ha bng phc bc amoniac cn c dng trng gng, trng phch nc. Andehit ni chung d b oxi ho khi tip xc vi khng kh, d chuyn thnh axit. Khc vi
Trang 107
andehit, xeton ch b oxy ha khi un nng vi oxi ha mnh v phn t b c ra hai bn nhm cacbonyl to thnh hn hp cc axit cacboxylic.
6.4.4. Phng php iu ch a) ehidro ho v oxy ho ancol
Khi hidro ho ancol c xc tc Cu ta thu c andehit hoc xeton tng ng: S :

R R1 CH2OH CH OH
toC
OXH
R
OXH
CHO R1 C O
+ H 2O R2 + H 2O
R2
H R C O + Cu + H 2O
Hay: R
CH 2 OH + CuO
V d: H CH3 C H2O H + C uO
toC
CH3
C O
+ C u + H 2O
b) Nhit phn mui ca axit cacboxylic (Piria, 1856) hoc axit cacboxylic
i vi mui:
Khi chng khan mui canxi hoc mui bari ca axit cacboxylic ta c hp cht cacbonyl theo s sau: (R COO)2Ca Hoc: (R COO)2Ca
300 C R CO R + CaCO3
0
+ (R/ COO)2Ca 2R CO R/
3000 C
+ 2CaCO3
Sn phm ph l: R CO R v R/ CO R/ Nu (R COO)2Ca + (H COO)2Ca 2R CHO

3000 C
+ 2CaCO3
Sn phm ph l: R CO R
i vi axit: Ngi ta cho hi axit i qua nhit hn 300oC c xc tc MnO thu c: 2R COOH
MnO,300 C R CO R + CO2 + H2O
0
Trng hp hn hp axit khi phn ng cho xeton: R COOH + R/ COOH R CO R/ + CO2 + H2O
MnO,3000 C
V mt trong cc axit l axit fomic cho andehit: R COOH + H COOH R CHO + CO2 + H2O
MnO,3000 C
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn c) iu ch t dn xut c Magi:
Trang 108
Cho hp cht c kim (thuc th Grinhe) tc dng vi dn xut axit fomic to thnh andehit, vi dn xut ca axit khc, to thnh xeton: R MgBr + HCOONa R MgBr + HCOOC2H5 R MgBr + R/ COCl
d) Thu phn cc axetylen
R CHO + NaBr + MgO
R CHO + C2H5MgBr R CO R/ + ClMgBr
Axetylen v cc ng ng ca n khi tc dng vi nc c xc tc HgSO4 cho andehit hoc xeton: CH CH + HOH

HgSO4 CH3 CHO
4 R C CH + HOH R CO CH3
HgSO
e) iu ch xeton thm (phn ng Friedel Craft)
Khi c xc tc AlCl3, benzen p vi clorua axit hay andehit to ra xeton:

+ R C O
f) Tng hp andehit thm theo Gateman - Cc:
Cl
AlCl3
C O
+ HCl
Cho H C thm tc dng vi hn hp kh CO + HCl c AlCl3 xc tc v Cu2Cl2 xc tc ta s thu c andehit thm: + CO + HCl
AlCl3 Cu2Cl2
CHO
HCl
6.4.5. Gii thiu cc cht tiu biu a) Fomandehit, HCHO:
c to thnh vi lng rt nh khi t chy khng hon ton nhiu cht hu c nh g, ng, H C, ... V vy, trong khi bp thng c cht t fomandehit, gp phn lm cho khi bp c tnh st trng. Trong cng nghip, fomandehit c iu ch t metanol hoc metan. Dung dch HCHO 30 - 40% trong nc c gi l fomon hay fomalin. Fomandehit l cht kh , c mi xc; fomadehit c, dng ty u, st trng. Bo qun cc mu gii phu.
b) Benzandehit, C6H5 CHO
C trong du hnh nhn v ht o, mn, ... di dng glicozit gi l aminalin. Thuphn amialin s c banzandehit.
Trang 109
Trong cng nghip, benzandehit c iu ch t benzylien clorua (thu phn bng kim), benzyl clorua, ... Benzandehit l cht lng khng mu, si 180oC, c mi thm c trng. Benzandehit c dng tng hp cht mu v cht thm. Vanilin l dn xut ca benzandehit:
CHO
OCH3 OH
4-hidroxi - 3 - metoxibenzandehit (Vanilin)
c) Axeton, CH3 CO CH3
c iu ch trong cng nghip theo nhiu cch khc nhau: ct khan g, ct khan canxi axetat, nhit phn axit axetic, ... ng ch l phng php i t axetylen v nc, vi s c mt ca cht xc tc ZnO 4000C. 2C2H2 + 3H2O CH3 CO CH3 + CO2 + 2H2
ZnO,400o C
Axeton l cht lng khng mu, si 56,5oC, tan v hn trong nc, udngf lm dung mi trong tng hp hu c, trong sn xut t nhn to, gelantin ho nitrat xenluloz trong ssn xut thuc sng khng khi. BI TP Cho s chuyn ha sau:
+ H2 (Ni)
(1)
+HBr
(2)
+Mg(ete)
(3)
C
(4)
+HCHO
CH3COCH2CH3
+HCN
(6)
+H2O, HCl
(7)
D
(5)
+HCl
+NaHSO3
(8)
+H2O, HCl
(9)
a) Vit s phn ng b) Vit c ch phn ng (6)
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.5. Axit cacboxylic v dn xut 6.5.1. Axit cacboxylic 6.5.1.1. Khi nim chung a) Khi nim
Trang 110
Axit hu c (cn gi l axit cacboxylic l nhng hp cht c mt hay nhiu nhm cacboxyl (-COOH) lin kt vi nguyn t C hoc H. Cng thc tng qut: R(COOH)n R c th l H hay gc hirocacbon. - R = O, n = 2 axit oxalic: HOOC - COOH
- Nu R l gc hirocacbon cha no, ta c axit cha no. - Nu R c nhm chc khc cha axit, ta c axit tp chc. Axit no mt ln axit c cng thc tng qut: CnH2n+1 COOH hay CTPT: CmH2mO2.
b) Cu to
Trong nhm COOH:
O C O H
Do nguyn t O ht mnh cp electron lin kt ca lin kt i C = O lm tng phn cc ca lin kt O - H. Nguyn t H tr nn linh ng, d tch ra. Do vy tnh axit y th hin mnh hn nhiu so vi phenol.
nh hng ca gc R n nhm - COOH:
- Nu R l gc ankyl c hiu ng cm ng +I (y electron) th lm gim tnh axit. Gc R cng ln hay bc cng cao. +I cng ln, th tnh axit cng yu. V d: Tnh axit gim dn trong dy sau.
CH3 COOH C2H5 COOH CH3 CH CH3 COOH
- Nu trong gc R c nhm th gy hiu ng cm ng -I (nh F > Cl > Br > I hay NO2 > F > Cl > OH) th lm tng tnh axit. V d: Tnh axit tng theo dy sau.
Trang 111
CH3
COOH
CH2 Br
COOH
CH2 Cl
COOH
- Nu trong gc R c lin kt bi nh C = C gy ra hiu ng I cng lm tng tnh axit: V d:

CH2 CH COOH CH3 CH2 CH2 COOH
- Nu c 2 nhm -COOH trong 1 phn t, do nh hng ln nhau nn cng lm tng tnh axit.
nh hng ca nhm -COOH n gc R:
Nhm -COOH ht electron gy ra hiu ng -I lm cho H nh C v tr tr nn linh ng, d b th. V d: C H2 C H2 C H2 COOH

CH3 CH2 COOH + Cl2
as

CH3
CH Cl
COOH
c) Cch gi tn
Tn thng dng:
Thng bt ngun t tn ngun nguyn liu u tin dng tch c axit. V d Axit fomic (axit kin), axit axetic (axit gim)
Danh php quc t:
Tn axit = Tn hirocacbon tng ng +oic. CH3 - CH2 - COOH : propanoic CH2 = CH - CH2 - COOH : butenoic.
6.5.1.2. Tnh cht vt l a) Tnh cht vt l ca axit no, mch h mt ln axit (CnH2n+1 - COOH)
Ba cht u dy ng ng l cht lng, c v chua, tan v hn trong nc, in li yu trong dung dch. Nhng cht sau l cht lng, ri cht rn, tan gim dn. Nhit si tng dn theo n. Gia cc phn t axit cng xy ra hin tng lin hp phn t do lin kt hiro.

O...H R C O H...O O C R
Trang 112
Do , axit c nhit si cao hn anehit v ru tng ng
b) i vi iaxit
L nhng cht tinh th, tan c trong nc, tan gim khi s nguyn t C tng. V d: Axit oxalic HOOC COOH. L cht tinh th, thng dng C2H2O4.2H2O, Khi un nng d b mt CO2.
6.5.1.3. Tnh cht ho hc

V hnh thc, nhm COOH l t hp ca nhm CO v nhm OH. Hai nhm ny nh hng ln nhau rt mnh, ch yu v c s lin hp gia obitan ca nhm C = O v obitan n ca nhm OH. Kt qa l lin kt O H axit yu hn ancol v in tch dng + nguyn t cacbon cacbonyl c gi tr nh hn andehit tng ng. Ngoi ra, ngi ta cn thy nh hng gia nhm C=O v gc H C gp cc hp cht cacbonyl:
O C O .. H
Phn ng ha hc ca axit cacboxylic gm 4 loi chnh: Phn ng lm t lin kt O H Phn ng vo nhm C= O Phn ng cacboxyl ho Phn ng gc H C
a) Phn ng lm t lin O H. S phn ly axit

Trong dung dch nc in li ra ion H+ (H3O+) theo cn bng: O R C O .. H + H2O R C O O + H3O+
R cng nhiu C, axit in li cng yu. Nu so snh vi ancol, ta thy axit monocacboxylic phn li mnh hn nhiu.
Lm giy qu (axit yu). Phn ng trung ho

R COOH + NaOH
R COONa + H2O
Trang 113
2R COOH + CaO
(R COO)2Ca + H2O
Ho tan kim loi ng trc H trong dy Bktp.

2R COOH + Mg
(R COO)2Mg + H2
y mnh axit yu hn ra khi mui:

2R COOH + CaCO3
(R COO)2Ca + CO2 + H2O
b) Phn ng cng v th nhm cacboxylic
Phn ng th nhm OH to thnh este

Cho axit tc dng vi ru to thnh este.
R1COOH C6H5COOH
+ +
R2OH CH3OH
R1COOR2 +
H2O H2O
C6H5COOCH3 +
Phn ng to thnh halogen axit

Axit phn ng vi halogenua photpho (PX5, PX3) hay thionylclorua SOCl2 to thnh halogen axit trong nhm OH c thay th bng hal: 3R COOH + PCl3 3R COCl R COOH + PCl5 R COOH + SOCl2 V d: C6H5 COOH + PCl5 + H3PO3
R COCl + POCl3 + HCl R COCl + HCl + SO2 C6H5 COCl + POCl3 + HCl
Phn ng to thnh anhyrit

Khi un nng axit c P2O5 s xy ra loi nc gia hai phn t axit to thnh anhyrit l sn phm th nhm OH bng gc R COO-:
O R C O O R C O
Phn ng to thnh amit
O R H H
P2O5
C O + H2O
C O
Anhidrit
Cho tc dng axit vi amoniac to thnh mui amon. Nhit phn mui amon ca axit s loi nc to thnh amit l sn phm th OH ca axit bng nhm NH2:
Trang 114
R COOH + NH3 V d: C6H5 COOH + NH3
t C R COONH4 R CONH2 + H2O t C C6H5 COONH4 C6H5 CONH2 + H2O

o
c) Phn ng cacboxyl ho (loi nhm cacboxyl)
Nhit phn hay in phn mui ca axit bo hoc thm s loi CO2 ca nhm cacboxyl to thnh H C hay andehit v xeton: R COOH + NaOH (R COO)2Ca
d) Phn ng gc hirocacbon
t oC toC
RH +
Na2CO3
R CO R + CaCO3
i vi axit bo, do nh hng ca nhm cacboxyl l nhm ht in t gy ra hiu ng -I lm cho H nh C v tr tr nn linh ng, d b th. V d: C H2 C H2 C H2 COOH
CH3 CH2 COOH + Cl2
as

CH3
CH Cl
COOH
i vi gc H C thm th nhm th COOH (nhm th loi II) s nh hng nhm th tip theo vo v tr meta. Nhm COOH lm cho nhn th ng ha:
COOH + Cl2
Fe
COOH +
axit m-clo benzoic
HCl
Cl
6.5.1.4. Phng php iu ch a) Oxy ha ancol, andehit cho axit cng s cacbon
[O ] [O ] R CH2OH R CHO R COOH
V d: C6H5 CH2OH
[O ] [O ] C6H5 CHO C6H5 COOH
b) Oxi ho cc hirocacbon
Oxi ho hirocacbon no bng O2 ca khng kh vi cht xc tc (cc mui Cu2+, Mn2+, Cr3+,) P = 7 - 20 atm v un nng s thu c axit bo c t 10 -20 nguyn t C trong phn t.
c) Thy phn dn xut trihalogen
R CCl3 + 3NaOH
d) Tng hp qua nitril
kb R C(OH)3 R - COOH
Tc dng dn xut monohalogen vi xyanua kali cho nitril:
Trang 115
R Cl + KCN
R C N + KCl R COOH + NH3
Thu phn ntin cho axit: R C N + 2H2O
e) Tng hp t hp cht c magie
Cho tc udngj dn xut hal vi Mg trong ete khan s to thnh hp cht c magi. Dn xut c magi tc dng vi kh CO2 to thnh sn phm cng ri thu phn cho axit tng 1 C so vi dn xut hal ban u: R Br + Mg
ete R MgBr
+ H2O R COOMgBr R COOH + BrMgOH
RMgBr + O = C = O
6.5.1.5. Gii thiu mt s axit cacboxylic tiu biu a) Axit fomic, H - COOH
L cht lng, khng mu, tan nhiu trong nc, c mi xc, nhit si = 100,5oC. Trong phn t c nhm chc anehit -CHO nn c tnh kh mnh ca anehit. Axit fomic c trong nc kin, trong mt s tri cy, trong m hi ng vt. iu ch: c th iu ch t CO v NaOH (cho CO i qua kim nng) CO + NaOH
t C HCOONa
o
HCOONa + H2SO4(long)
HCOOH + NaHSO4
Axit fomic c dng lm cht kh trong ngnh nhum, tng hp cc hp cht hu c khc.
b) Axit axetic, CH3 - COOH
L cht lng, khng mu, tan nhiu trong nc, c mi chua, xc, nhit si = 118,5oC. Dung dch 5 - 8% l gim n. iu ch: ngoi cc phng php chung, axit axetic cn c iu ch bng nhng cch sau. + i t axetilen. + Cho ru etylic ln men gim. + Chng kh g: trong lp nc c 10% CH3COOH. Trung ho bng vi thnh (CH3COO)2Ca. Tch mui ra ri ch ho bng H2SO4 thu axit axetic. Axit axetic c dng trong cng nghip thc phm, trong cng nghip dc phm v k ngh sn xut cht do v t nhn to.
c) Axit bo c KLPT ln
Quan trng nht l C15H31COOH C17H35COOH
Trang 116
(axit panmitic)
(axit stearic)
C hai u c cu to mch thng, khng phn nhnh. L nhng cht rn nh sp, khng mu. Khng tan trong nc nhng tan nhiu trong dung mi hu c. Phn ng vi kim v tan trong dung dch kim. Mui ca cc axit ny vi Mg v kim loi kim th (Ca, Ba, ) khng tan trong nc.
d) Axit oxalic, HOOC - COOH
L cht tinh th, thng dng C2H2O4.2H2O. Khi un nng d b mt CO2: HOOC COOH HCOOH + CO2
t0
D b oxi ho: 5HOOC COOH + 2KMnO4 + 3H2SO4
10CO2 + K2SO4 + 2MnSO4 + 8H2O
Axit oxalic c dng lm cht kh v nh phn KMnO4. - iu ch 2HCOONa

400 C NaOOC COONa
o
NaOOC COONa + 2HCl
HOOC COOH + 2NaCl
e) Axit aipic, HOOC - (CH2)4 - COOH
Dng sn xut nha tng hp (amit), si tng hp (nilon) iu ch: Oxi ha xiclohexan (ly t du m).
f) Axit acrilic, CH2 = CH - COOH
L cht lng khng mu, mi xc, tan v hn trong nc, tan nhiu trong ru, ete. Este ca axit acrilic dng sn xut cht do. L cht lng khng mu, tan c trong nc, ru, ete. Este ca n vi ru metylic c trng hp ch to thu tinh hu c (plexiglat).
g) Axit sorbic, CH3 - CH = CH - CH = CH - COOH
Cht tinh th mu trng, t tan trong nc. Dng bo qun thc phm. h) Axit oleic, CH3 (CH2)7 CH = CH (CH2)7 - COOH L cht lng nh du. C trong du ng, thc vt di dng este vi glixerin, c bit c ti 80% trong du oliu. Phn ng vi hiro to thnh axit stearic. Mui oleat ca Na, K dng lm x phng git. Cc oleat ca Ca, Mg khng tan trong nc.
6.5.2. Dn xut ca axit cacboxylic
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn 6.5.2.1. Khi nim chung
Trang 117
Khi thay th OH nhm cacboxyl ca cacboxylic bng nhng nhm th khc nhau ta c dn xut nhm chc ca axit cacboxylic:
R C O OH R C O Y
Tu theo bn cht ca nhm th Y ta c:

Halogenua axit (hay axyl halogenua): R COX
Th d: CH3 COCl (axetyl clorua) ; C6H5 COCl (benzoyl clorua)

Anhidrit axit:
R C O O C O R
Th d:
CH3 C O O C O CH3 C6H5 C O O C O C6H5
anhidrit axetic
anhidrit bezoic
Este: R COOR/ Amit: R CONH2
Th d: axetamit: CH3 CONH2; benzamit: C6H5 CONH2 Cc dn xut nu trn u c gc chung l R CO - gi l axyl:
H-COFomyl
CH3-COaxetyl
CH3CH2-COpropionyl
C6H5-CObenzoyl
Dn xut nhm chc ca axit cacboxylic cn l nhng sn phm th nguyn t O trong nhm cacboxyl, th d axit hiroxamic:
C NH
OH
Hoc sn phm th c nguyn t oxi ln nhm OH trong nhm cacboxyl, th d nitrin: RCN
6.5.2.2. Tnh cht ha hc
Cc dn xut ca axit cacboxylic c mt s phn ng chung sau y:

a) Phn ng thu phn
Trang 118
Cc dn xut axit d b thu phn, hi li axit cacboxylic, nht l khi c mt xc tc axit hoc baz. Cc halogenua axit v anhirit thu phn nhanh, khng cn xc tc: R COY + H2O
H hayOH R COOH + HY
+
Y c th l: Hal, OR, NH2, OCOR. Kh nng phn ng ca cc dn xut ca axit cacboxylic gim theo th t: R COCl > R COOCO R > R COOR/ > RCONH2 Cc phn ng thu phn u theo mt quy tc chung, trn c s gii thch c ch phn ng thu phn este. Thu phn l qu trnh thun nghch ca phn ng este ha. Qu trnh thu phn c th c xc tc bng axit hoc baz. Vai tr ca axit l proton ho este, to iu kin cho tc nhn nucleophin (HOH) d dng tn cng vo nhm C=O, sinh ra sn phm cng khng bn, sn phm ny chuyn ho ngay thnh axit v ancol:
R1 C O
OH2 C O O H
(+) (+)
OR2 + H(+)
R1
C O
O(+) H
R2
O + R1 H
..
R2
R1
C
(--)
O H
(+)
R2
R1
C O
(+)
O H
H + R2OH
Trang thai trung gian

(+)
R1
C O
O H
R1
C O
(+)
a xitcacboxylic
Tt c cc giai on trong s phn ng trn u l thun nghch; v vy axit v c va xc tc cho qu trnh thu phn li va xc tc cho qu trnh este ha. Trong phn ng thu phn nh xc tc baz, ion hiroxyl HO- ng vai tr mt tc nhn nucleophin, s tn cng vo nhm C=O ca este. trng thi trung gian sinh ra c th tr v trng thi u hay chuyn thnh axit v anion ancolat theo nhng qu trnh thun nghch. Nhng ion ny l baz rt mnh, n tc dng rt nhanh v bt thun nghch vi axit, cho nn ton b phn ng thu phn l bt thun nghch. Do , khng th thc hin trong mi trng kim:
Trang 119
OH H O + R1
(--)
C O
R2
R1
C
(--)
R2
R1
C O
H + R2O
(--)
Trang thai trung gian
R1
C O
H + R2O
(--)
R1
C O
O(--) + R2OH
2 . Phn t Nhng phn ng thu phn trn u l nhng phn ng lng phn t kiu SN
este (v phn t axit trong qu trnh este ha) b phn ct lin kt axyl oxi:
R1 C O O R2
b) Phn ng vi hp cht c kim
Cc dn xut ca axit u c th phn ng vi hp cht c kim (RMgX, RLi), giai on quyt nh l s tn cng ca R2 vo cacbon cacbonyl:
R1 C Y Y = Cl; OR; RCO2 O + R2 MgX R1 Y C R2 OMgX
Phn ng khng ngng giai on ny m tip tc cho n khi to thnh ancol bc ba

c) Phn ng oxy ha
Clo axit, anhirit v este c th b kh bng liti nhm hirua to thnh ancol bc mt: R COY Th d: R CONH2
1.LiAlH4 ;2.H ,H2O R CH2OH 1.LiAlH4 ;2.H ,H2O R CH2 NH2
+ +
6.5.3. Axit mono v iaxitcacboxylic a) Axit khng no n chc
Axit khng no l nng axit cha ni ooi C = C hoc ni ba C C trong phn t. Axit cacboxylic khngno c mt ni i c cng thc chung: CnH2n-1COOH. loi n gin nht l axit acrylic: CH2 = CH COOH. Ngoi ng phn v mch C, v v tr lin kt bi, axit khng no cn c ng phn hnh hc cis trans. Th d:
Trang 120
CH3 H
H C C COOH
Axit crotonic (trans)
CH3 H
COOH C C H
Axit crotonic (cis)
Cc axit khng n c y tnh cht ca tt c cc tnh cht ca nhm cacboxyl nh axit no v c tnh cht ca ni i hay ni ba nh trong anken, ankin. Do nh hng ca ni ooi C = C v ni ba C C c hiu ng I, axit khng no c tnh axit mnh hn axit no tng ng. Ni i cng gn nhm COOH, hiu ng I cng tng, do axit cng mnh. Tuy vy, nu ni i v tr , i vi nhm cacboxyl th ngoi hiu ng I cn c hiu ng lin hp +C:
C C C OH Hiu ng +C lm gim tnh axit, do axit , khng no tuy mnh hn axit no tng ng, nhng khng mnh bng ng phn , khng no. Axit khng no c th cng tc nhn electrophin vo ni i C = C, phn ng ngc vi quy tc Maccopnhicop v theo kiu cng hp 1,4: CH2 = CH COOH + HBr O
CHBr CH2 COOH

sp chnh CH - CH - COOH 2 sp phu
CH2 = CH - COOH + HBr
Br H CH2 - CH - COOH H Br
Axit khng no v este ca n c kh nng trng hp , chng hn axit acrylic trng hp cho poliacrylic:
trung hp
n CH2 = CH
COOH
- CH2 - CH COOH
n
nCH2 = CH COOC2H5
Trung hp
- CH2 - CH COOC2H5 n
b) Axit icacboxylic
Khi nim: l loi axit c hai nhm cacboxylic hai u mch cacbon.
Trang 121
Axit icacboxylic khng no c trng nht l axit etylen-1,2-iaxitcacboxylic HCOO CH = CH COOH Tn ti hai dng ng phn hnh hc:
H C HOOC C
H COOH
Axit maleic (cis) (oc)
H C HOOC
(Khong oc)
COOH C H
Axit maleic (trans)
Axit amelic khng c trong t nhin, n c iu ch bng cch oxy ha benzen hoc oxy ho hn hp n-buten. Ngoi ra cn c mt s iaxit thng gp:
COOH CH2 COOH
Axit maloic
COOH (CH2)2 COOH

Axit sucxinic
COOH (CH2)4 COOH

Axit adipic
COOH COOH
COOH
COOH
COOH
Axit o-phtalic Axit m-phtalic
COOH
Axit p-phtalic
Tnh cht:
Tnh cht iaxit tng t nh monoaxxit, song do trong phn t ca n c cha hai nhm COOH nn cc phn ng thng xy ra theo hai giai on:
COOH COOH
K1 =3,8.10-2
COOCOOH + H+
K2 =1,85.10-5
COO+ COOH+
Axit hai chc c tnh axit cao hn axit n chc do nh hng ca hai nhm cacboxyl vi nhau (c hiu ng m). Trong axit bo, axit oxalic l axit mnh nht, nu mch gia hai nhm cacboxyl tng ln th tnh axit gim dn. - Phn ng ca este malonat: v c nhm CH2 gia hai nhm COOH nn H ca n linh ng. Ngi ta dng n tng hp nhiu hp cht hu c khc.
6.5.4. Lipit
Lipit l tn gi chung bao gm cc cht bo v cc cht tng t cht bo gi l lipoit. Cc cht lipit li chia thnh nhiu nhm nh nh photphatit, xerebrozit, sp.
Chng 6: Hp cht hu c n chc v a chc http://www.ebook.edu.vn a) Cht bo
Trang 122
Cht bo (ngun gc ng vt, thc vt) l este ca glixerin vi axit bo (axit hu c mt ln axit mch thng, khi lng phn t ln). Cc cht bo c gi chung l glixerit. Cng thc tng qut ca cht bo. CH2 OCOR1
- CTCT: CH
OCOR2
Vi:R1, R2, R3 la goc H - C
CH2 OCOR3
Neu R1, R2, R3 la goc H - C
no: m (TT ran) khong no: dau (TT long)
Mt s axit bo thng gp. Axit panmitic: C15H31 COOH Axit stearic: C17H35 COOH Axit oleic: C17H33 COOH (c mt ni i) Hai axit sau y c nhiu ni i cng thng gp trong du: Axit linoleic: C17H31 COOH (c hai ni i) Axit linolenoic: C17H29 COOH (c ba ni i) Thng gp cc glixerit pha tp. V d:
CH2 OCOC15H31 CH OCOC17H33
CH2 OCOC17H35 Trong cht bo, ngoi este ca glixerin vi axit bo cn c mt lng nh axit dng t do c c trng bi ch s axit.
Ch s axit ca mt cht bo l s miligam KOH cn thit trung ho axit t do trong mt gam cht bo. V d: Mt cht bo c ch s axit bng 9 (Ngha l trung ho 1 gam cht bo cn 9 mg
KOH)
Tnh cht ca cht bo:

- Phn ng thu phn: Cht bo t tan trong nc nn khng b thu phn bi nc lnh hay nc si. thu phn cht bo phi un nng trong nc p sut cao (25atm) t n nhit cao (220oC):

CH2 OCOR1 CH OCOR2 + 3H2O
+ H t0
Trang 123
CH2 OH CH OH
R1COOH
+ R2COOH
R3COOH Cac axit beo
CH2 OCOR3
CH2 OH Glixerin
C th dng axit v c (axit sunfuric long) tng tc phn ng thu phn. Axit bo khng tan trong nc, c tch ra. - Phn ng x phng ho: Nu cht bo vi kim
CH2 OCOR1 CH OCOR2 + 3NaOH

t0
CH2 OH CH OH
R1COONa
+ R2COONa
R3COONa Xa phong
CH2 OCOR3
CH2 OH Glixerin
Cc mui to thnh l x phng tan trong dung dch. Khi thm NaCl vo hn hp phn ng, x phng s ni ln thnh lp, ng c. Glixerin tan trong dung dch c tch bng cch chng phn on. - Phn ng cng ca glixerit cha no, bin du thnh m. Quan trng nht l phn ng cng hiro (s hiro ho) bin glixerit cha no (du) thnh glixerit no (m).
V d:
CH2 OCOC17H33 CH OCOC17H33 + 3H2

Ni,t
0
CH2 OCOC17H35 CH OCOC17H35
CH2 OCOC17H33 Glixeryl trioleat
CH2 OCOC17H35 Glixeryl tristearat
- Cc glixerit cha no d b oxi ho ch ni i. Lm mt mu dung dch KMnO4. B oxi ho bi oxi ca khng kh.
b) Sp
Sp c thnh phn ch yu l este ca axit monocacboxxylic no hay khng no vi cc ancol n chc, trong phn ln lag axit v ancol c s C chn (C16 C36). Ngoi ra, sp cn cha cc axit v ancol t do v c H C na. Trong cc cht ph km theo ssp, ng ch l stearin v cc cht mu loi carotenoit. Sp thc vt l nhng lp mng trn l, qa, thn, lm cht bo v, ngn nga vi khun c hi v s mt nc.
Trang 124
Sp ng vt, trc ht k n sp c voi, sp ong. Sp c c trong du c voi, thnh phn ch yu l este xetyl panmitat C15H31COOC16H33. Sp ong c cha este ca ancol C24 C34 v cc axit cao, th d este mirtixyl panmitat C15H31COOC31H63, ...
c) X phng v cht git ra
Ngoi x phng thng, hin nay ngi ta cn dng nhiu loi cht ty ra tng hp khc nhau. cng l nhng cht hot ng b mt, thuc my loi sau. - Nhng cht ty ra sinh ion (iongen) Phn t gm gc hirocacbon R v nhm phn cc. Ngoi loi R - COONa, cn c nhng cht hot ng b mt nh ion phc tp.
V d:
Cc ankyl sunfat: R - O - SO3Na
(R c > 11C)
Cc ankyl sunfonat: R - SO3Na, iu ch bng cch.
H + HO
SO2
OH
SO2
OH
NaOH
SO3Na
(R c 10 - 20 nguyn t C) Cc ankyl aryl sunfonat:

R C6H4 SO3Na
Nhng cht hot ng b mt nh cation phc tp. V d :
C18H37NH3
Cl
C16H33(CH3)3N
Cl
Nhng cht ty ra khng sinh ion Phn t cha gc R khng phn cc v cc nhm phn cc nh -OH, -O- (ete). V d:
OH + nCH2 O
CH2
CH2
CH2
OH
R : c th c ti 18C, n : c th bng 6 - 30 tu theo cng dng. Cc cht ty ra trn vn gi c tc dng ty ra c trong mi trng axit v nc cng.
6.6. Amin 6.6.1. Khi nim v amin
Amin l dn xut ca NH3 khi thay th mt hay nhiu nguyn t H bng gc hirocacbon.
Trang 125
Cng c th xem amin nh dn xut ca hirocacbon khi thay th nguyn t H bng nhm NH2. Phn loi: bc ca amin: Amin bc mt: R NH2 Amin bc hai: R NH R/ Amin b.3 R1 N R3 Ty theo s nhm NH2 ta c monoamin, iamin, V d:
CH3 NH2 NH2 CH2 CH2 NH2
R2
Etylamin
Etyldiamin
Trong phn t amin (ging trong phn t NH3), nguyn t N c 1 cp electron khng phn chia.
H R N: H ; R1 H N: R2 ; R1 R2 N: R3
V th amin c kh nng kt hp proton (H+), th hin tnh baz. Nu R l gc no mch h, c khuynh hng y electron, lm tng in tch m N, lm
+ tng kh nng kt hp H , ngha l lm tng tnh baz. Amin bc cao c tnh baz mnh hn amin
bc thp.
Nu R l nhn benzen, c khuynh hng ht electron, ngc li lm gim tnh baz ca amin (tnh baz yu hn NH3)
6.6.2. Tnh cht vt l a) Cc amin mch h: Nhng cht n gin nht (CH3 - NH2, C2H5 - NH2) l nhng cht kh,
tan nhiu trong nc, c mi c trng ging NH3. Khi khi lng phn t tng dn, cc amin chuyn dn sang lng v rn, tan trong nc cng gim dn.
V d.
Cht : Nhit si CH3CH2, (CH3)2NH, C2H5NH2, C2H4(NH2)2
-6,3oC
+6,9oC
+16,6oC
+116,5oC
b) Cc amin thm: l nhng cht lng hoc cht tinh th, c nhit si cao, mi c trng, t
tan trong nc.

Ni chung amin l nhng baz yu, c phn ng tng t NH3. a) Tnh baz

- Cc amin mch h tan c trong nc cho dung dch c tnh baz. C2H5 NH2 + H2O Do lm qu c mu xanh.
Trang 126
C2H5 NH3+ + OH-
- Anilin (C6H5 - NH2) v cc amin thm khc do tan t trong nc, khng lm xanh giy qu. - Phn ng vi axit to thnh mui. R NH2 + HCl
R NH3Cl
+ NH3Cl
NH2 + HCl
Cc mui ca amin l cht tinh th, tan nhiu trong nc. Khi cho cc mui ny tc dng vi kim mnh li gii phng amin.
+ ClNH 3 + NaOH NH2 + NaCl + H O 2
b) Cc iamin: Cc iamin c th tham gia phn ng trng ngng vi cc iaxit to thnh polime. c) Amin thm: - Nhm NH2 c nh hng hot ho nhn thm v nh hng th vo v tr o-, p-.
V d:
NH2 + 3Br2 Br Br NH2 Br tr + 3HBr
- Do nh hng ca nhm NH2, tnh bn ca nhn benzen gim xung, d b oxi ho (v d bng hn hp K2Cr2O7 + H2SO4) cho nhiu sn phm khc nhau. V d:
NH2 + 2(O)
K2Cr2O7 H2SO4
O + NH3 O
6.6.4. Phng php iu ch
a) Kh hp cht nitro bng hiro mi sinh: R NO2 + 6[H]

Fe + HCl R NH2 + 2H2O
b) Phn ng gia NH3 vi R - X (X = Cl, Br, I)
Trang 127
R I + 2NH3
R NH2 + NH4I
NH2 + R2 I R1 NH R2 + NH4I
Phn ng c th tip tc cho amin bc cao: NH3 + R1
c) Phng php Sabatie R OH + NH3

350 R NH2 + H2O
oC
6.6.5. Gii thiu mt s amin
a) Metylamin CH3 - NH2 L cht kh, c mi ging NH3, tan nhiu trong nc, trong ru v ete. b) Etylamin C2H5 - NH2 L cht kh (nhit si bng 16,6oC), tan v hn trong nc, tan c trong ru, ete. c) Hecxametyliamin H2N - (CH2)6 - NH2: L cht tinh th, nhit si = 42oC. c dng ch nha tng hp poliamit, si tng hp. d) Anilin C6H5 - NH2: L cht lng nh du, nhit si = 184,4oC. c, c mi c trng. t tan trong nc nhng tan tt trong axit do to thnh mui. trong khng kh b oxi ho c mu vng ri mu nu. Dng sn xut thuc nhum. e) Toluin CH3 - C6H4 - NH2 Dng ortho v meta l cht lng. Dng para l cht kt tinh. iu ch bng cch kh nitrotoluen.
6.6.6. Mui iazo thm a) Khi nim
Hp cht iazo c cng thc chung C6H5N2X Trong X l: Cl-, HSO4-, NH3-, OH-, -OMe, ... Cng thc cu to c hai dng cu tao: C6H5 N = N X (1):hp cht iazo tht ; C6H5 N+ N X- (2): mui iazo
Thc t chng minh rng hp cht iazo c tnh dn in. N l mt mui amonium bc 4. in tch dng ion iazon nguyn t N ni vi gc phenyl (cng thc 2). Cng thc c in ca hp cht iazoni (cng thc 1) khng phn nh c c tnh mui ca hpc cht ny.
b) iu ch
Hp cht iazo thm c iu ch bng cch iazo ha hp cht amin thm bng axit nit v axit v c khc nh HCl, H2SO4 0 40C.
Trang 128
C6H5 NH2
c) Ho tnh
+ HNO2 + HCl
04 C C6H5 N+ NCl0
Hp cht iazo thuc loi hp cht hu c c kh nng hot ng ho hc ln nht. T hp cht iazo ta c th iu ch hu ht cc hp cht thm khc ch tr andehit v xeton thm. Cc phn ng ca hp cht iazo c th chia lm hai loi:
Phn ng thot nit
- Phn ng thu phn: iazo ho amin bc 1 nhit thp (0 40C) ta nhn c dd mui iazonium. Khi nu nng dd (50 800C) hoc un si th quan st thy nit thot ra mnh lit v ta thu c phenol. C6H5 N2Cl + H2O
50 80 C C6H5 OH + N2 + HCl
0
- Th nhm iazo bng H: Cho dd mui iazo tc dng vi mt s hp cht c tnh kh s xy ra phn ng thay th nhm iazo bng H. Th d: C6H5 N2Cl + C2H5 OH
CH3COONa C6H6 + N2 + CH3CHO + HCl
- Th nhm iazo bng nhm alkoxyl (-OR): un nng ru vi hp cht iazo cho ta ete C6H5 N2Cl + CH3 OH
tC C6H5 O CH3 + N2 + HCl
0
- Th nhm iazo bng xyanua: Cho dd mui iazo tc dng vi CuCN thu c hp cht nitrin: C6H5 N2Cl + CuCN
C6H5 CN + N2 + CuCl
- Th nhm iazo bng halogen: Khi un nng dd mui iazo vi KI s thu c iod benzen: C6H5 N2Cl + KI
C6H5 I + N2 + KCl
- Th nhm iazo bng nhn benzen: ch ho mui iazo bng NaOH hoc CH3COONa vi hp cht H C thm th s thu c hp cht iaryl: C6H5 N = N OCOCH3 + C6H6 C6H5 C6H5
Phn ng khng thot nit:
+ N2 + CH3COOH
- Phn ng ghp azo: mui iazo d dng phn ng vi phenol, amin thm v cc dn xut ca chng 0 50C to thnh hp cht hyroxyazo v aminoazo: C6H5 N2Cl + C6H5 OH C6H5 N N C6H4 OH + HCl
NaOH
p-hyroxy azobenzen
Trang 129
- Phn ng to hp cht d vng iazo aminobenzen: mt s amin bc 1 v bc 2 ngng t vi hp cht iazo ti nguyn t N, m khng nguyn t C vng benzen nh amin bc 3, to thnh hp cht iazo aminobenzen:
N NCl + NH2
CH3COOH
NH
NH2
iazo aminobenzen - Kh thnh hirazin: kh mui iazo bng NaHSO3, sau thu phn s nhn c phenyl hyrazin: C6H5 N2Cl + 2NaHSO3 + 2H2O C6H5 NH NHH2 + 2NaHSO4 + HCl phenyl hyrazin
1000 C
BI TP
Vit y cc phng trnh phn ng theo s sau:

H2O t oC
D E F
C6H6
HNO3 H2SO4
Fe HCl
NaNO2+HCl toC
C6H5N(CH3)2
Chng 7: Hp cht hu c tp chc
Trang 130
Chng 7: HP CHT HU C TP CHC

7.1. Hiroxiaxit Hp cht tp chc: Trong phn t c nhiu nhm chc khc nhau. V d: cc aminoaxit H2N - R - COOH, HO - CH2 - CH2 - CHO, Cc hiroxiaxit c chia lm hai nhm ln: cc hp cht c cha nhm hiroxi ni vi mch khng vng hay vi mch nhnh ca vng thm v cc hp cht c cha nhm hiroxi ni trc tip vi vng thm (hay axit phenolcacboxylic) 7.1.1. Hiroxiaxit dy bo Nhiu hiroxiaxit c trong thin nhin v c gi theo tn thng thng. Axit glicolic c trong thnh phn nc p cy ma. Axit lactic ln u tin c phn lp t sa chua. Nhiu hiroxiaxit quan trng l axit icacboxylic, nh axit malic c trong nc p tri cy, axit tactric c trong cn ru vang.
CH2 OH
COOH
axit glicolic
CH3
CH OH
COOH
axit lactic
HOOC
axit malic
CH2
CH OH
COOH
HOOC
CH OH
CH OH
COOH
axit tactric
a s cc hiroxiaxit u c C* trong phn t, nn tn ti ng phn quang hc. a) Tnh cht ho hc Tu thu vo v tr ca nhm OH, cc hiroxiaxit d dng mt nc, to thnh hp cht hon ton khc nhau: Khi un nng, hai phn t -hiroxiaxit d dng mt nc to thnh este vng c gi l lactit:
OH CH3 CH COOH HO
axit lactic
HOOC CH CH3 CH3 CH
O CO
lactit
CO CH O CH3 + 2H2O
Lactit l cht rn kt tinh, un si vi nc v c mt ca axit hay kim n b x phng ha v to thnh hiroxiaxit ban u.
b) Phng php iu ch
Cc -hiroxiaxit thng c iu ch bng cch thu phn -halogenaxit hoc thu phn hp cht xianhirin. Th d:
CH3
CH2
COOH
+ Cl2
CH3
CH Cl
COOH
+NaOH
CH3
CH OH
COOH

+HCN
+HCl 100oC
Trang 131
C6H5
CHO
C6H5
CH OH
CN
C6H5
CH OH
COOH
7.1.2. Hiroxiaxit dy thm

Hiroxit dy thm tiu biu v quan trng nht l axit salixylic (axit 2-hiroxi benzoic). N tn ti trong thin nhin di dng este trong thnh phn ca mt s tinh du. iu ch: t natri phenolat v CO2 nhit 120 1400C theo phn ng:
ONa + CO2 OH COONa
+HCl
OH COOH
axit salixylic
Axit salixilic c nhiu ng dng, dng lm iu ch cht thm, lm cht kh trng trong y hc, di dng natri salixylat lm cht bo qun thc phm. Dn xut axetyl ca axit salixylic c gi l aspirin, l mt loi thuc gim st v gim au thn kinh tt:
OH COOH CH3COCl
O O C
CH3 + HCl
COOH
axit salixylic
axit axetylsalixylic (Aspirin)
7.2. Gluxit
Gluxit (saccarit) l cc polihiroxiandehit v polihiroxixeton. Gluxit l tn gi mt loi hp cht hu c rt ph bin trong c th sinh vt Cng thc phn t Cn(H2O)m. Cc cht gluxit c phn lm 3 loi.
monosaccarit glucoz fructoz saccaroz mantoz tinh bot xenluloz
Gluxit
disaccarit
polisaccarit
- Monosaccarrit l nhng gluxit n gin nht, khng b thu phn thnh nhng gluxit n gin
hn. V d: glucoz, fructoz (C6H12O6), riboz (C5H10O5)

- Oligosaccarit l nhng sn phm ngng t t 2 n 10 phn t monosaccarit vi s tch bt
nc. Quan trng nht l cc isaccarit hay ioz c cng thc chung C12H22O11. Cc isaccarit ny b thu phn to thnh 2 phn t monosaccarit. V d thu phn saccaroz.

+
Trang 132
C12H22O11
H2O
H C6H12O6 + C6H12O6
- Polisaccarit l nhng hp cht cao phn t. Khi b thy phn, polisaccarit to thnh mt s ln
phn t monosaccarit. (C6H10O5)n + nH2O

H nC6H12O6
+
V d: Tinh bt, xenluloz, glicogen u c cng thc chung l (C6H10O5)n. 7.2.1. Monosaccarit
a) Khi nim, phn loi v cu trc Monosaccarit l nhng gluxit khng th thu phn c. Tu thuc vo nhm C=O nm di dng andehit hay xeton, cc monosaccarit c phn chia thnh andoz (c nhm andehit) v xetoz (c nhm xeton) Cng thc phn t: C6H12O6 Cng thc cu to:
CH2 - CH - CH - CH - CH - C - H OH OH OH
andoz
CH2 - CH - CH - CH - C - CH2 OH OH OH OH O OH
OH
OH
Xetoz
Tu theo s nguyn t cacbon trong phn t, monosaccarit (anoz v xetoz) c gi l trioz (3C), tetroz (4C), pentoz (5C), hexoz (6C), heptoz (7C). Nhng monosaccarit quan trng u l hexoz v sau l pentoz. V d: glucoz, frutoz, Ngoi ng phn cu to (anoz v xetoz), monossaccarit cn c ng phn khng gian gi l ng phn quang hc, mi ng phn khng gian li c tn ring.
Cu to dng mch h ca glucoz.

- Glucoz tham gia phn ng trng bc v kh c Cu2+, do vy phn t phi c nhm chc anehit (-CH = O). - Glucoz tc dng vi (CH3CO)2O sinh ra pentaeste C6H7O(OCOCH3)5, chng t trong phn t c 5 nhm -OH; cc nhm -OH c th to phc cht mu xanh lam khi tc dng vi Cu(OH)2 (tng t nh glixerin). - T cc kt qu thc nghim, ngi ta thy rng glucoz l mt pentahiroxi anehit c mch thng khng phn nhnh.
CH2 - CH - CH - CH - CH - C - H OH OH OH OH OH O
Trang 133
Do s phn b khc nhau ca cc nhm -OH trong khng gian, glucoz c nhiu ng phn khng gian. Glucoz thin nhin, c gi l D-glucoz (c nhm -OH ti C5 bn phi) phn bit vi mt ng phn iu ch trong phng th nghim l L-glucoz (nhm -O bn tri). Cng thc cu trc nh sau:
CHO H HO H H OH H OH OH CH2OH D-Glucozo

Cu trc dng mch vng ca glucoz
CHO HO H HO OH H OH H H CH2OH L -Glucozo
Ngoi dng mch h, glucoz cn c cc dng mch vng 6 cnh hoc 5 cnh. Glucoz vng 6 cnh c gi l glucopiranoz v vng ny c dng ca d vng piran, cn vng 5 cnh c gi l glucofuranoz v c dng d vng furan.
CH2OH H HO H OH H H OH CH2OH O OH H H OH H H OH HO H O OH H
Glucopiranozo
Glucofuranozo
Glucopiranoz bn hn rt nhiu so vi glucofuranz.
Cu trc phn t fructoz

Fructoz trong thin nhin c gi l D-fructoz, c cng thc cu trc.
OH CH2 OH CH OH CH OH CH C O CH2 OH
b) Tnh cht vt l - trng thi t nhin
Monosaccarit l nhng cht khng mu, c v ngt, d tan trong nc, khng tan trong dung mi hu c, c kh nng lm quay mt phng nh sng phn cc sang phi v hoc sang tri.
Trang 134
Trong thin nhin, glucoz c trong hu ht cc b phn c th thc vt: r, l, hoa v nht l trong qu chnh. Glucoz cng c trong c th ngi, ng vt. Fructoz trng thi t do trong qu cy, mt ong. V ngt ca mt ong ch yu do fructoz.
c) Tnh cht ho hc Phn ng ca nhm anehit - CH = O
Phn ng oxi ho nhm chc anehit thnh nhm chc axit. Khi glucoz tr thnh axit gluconic. + Phn ng trng gng.
CH2 - CH - CHO + Ag2O OH OH
4
AgNO3 o NH3
CH2 - CH - COOH + 2Ag OH OH

4
glucoz
axit gluconic
+ Phn ng vi Cu(OH)2 (trong mi trng kim)

CH2 - CH - CHO + Cu(OH)2 OH OH
4
CH2 - CH - COOH + 2H2O + Cu2O OH OH

4
glucoz
axit gluconic
(mu gch) + Phn ng oxi ho trong mi trng trung tnh v axit, v d bng HOBr: CH2OH (CHOH)4 CHO + HOBr CH2OH (CHOH)4 COOH + HBr + Phn ng kh nhm -CHO to ra ru 6 ln ru.
CH2 - CH - CHO + Ag2O Ni o

t
CH2 - CH - CH2 OH OH
sobit
4
OH
OH
OH
glucoz
Phn ng ca cc nhm -OH
- Phn ng vi Cu(OH)2 cho dung dch mu xanh lam.
CH2 - OH CH - OH 2 CH - OH CH - OH CH - OH CHO + Cu(OH)2
CH2 - OH CH - OH CH - OH CH - O CH - O CHO Cu H H
HO - CH2 HO - CH HO - CH O - CH O - CH CHO + 2H2O
Trang 135
- To este c cha 5 gc axit mt ln axit. V d glucoz phn ng vi axit axetic CH3COOH to thnh pentaaxetyl glucoz :
CH2 - OH CH - OH CH - OH + 5CH COOH 3 CH - OH CH - OH CHO
H+ o
CH2 - OCOCH3 CH - OCOCH3

t
CH - OCOCH3 CH - OCOCH3 CH - OCOCH3 CHO
+ 5H2O
Phn ng ca glucoz dng vng:

Nhm OH nguyn tr C1 trong phn t glucoz dng vng linh ng hn cc nhm OH khc nn d dng to ete vi cc phn t ru khc (v d vi CH3OH) to thnh glucozit:
CH2OH H HO H OH H H OH CH2OH O H OH + HO
HCl
O OH H OH O R + H2O
H HO
H OH H
Phn ng ln men
Di tc dng ca cc cht xc tc men do vi sinh vt tit ra, cht ng b phn tch thnh cc sn phm khc. Cc cht men khc nhau gy ra nhng qu trnh ln men khc nhau.
V d:
- Ln men etylic to thnh ru etylic.
C6H12O6 LM ru 2C2H5OH + 2CO2

- Ln men butyric to thnh axit butyric: C6H12O6
LM:butylric CH3 CH2 CH2 COOH + 2H2 + 2CO2
- Ln men lactic to thnh axit lactic:
C6H12O6
glucoz
LM lactic
2CH3 - CH - COOH OH
axit lactic
d) iu ch
Trang 136
- Qu trnh quang hp ca cy xanh di tc dng ca bc x mt tri, to thnh glucoz v
cc monosaccarit khc: 6CO2 + 6H2O

qh C6H12O6 + 6O2
- Thu phn i, polisaccarit c trong thin nhin (nh saccaroz, tinh bt, xenluloz) di tc
dng ca axit v c hay men.

C12H22O11 + H 2O
Axit, toC
C6H12O6 + C6H12O6
Glucoz fructoz
(C6H10O5)n +
nH2O
Axit, toC
nC6H12O6
Glucoz
- Trng hp anehit fomic
6HCHO
7.2.2. isaccarit
Ca( OH)2 C6H12O6
isaccarit l loi gluxit phc tp hn, khi thu phn cho hai phn t monosaccarit. Nhng monosaccarit tiu biu v quan trng l saccaroz, mantoz, lactoz u c cng thc phn t C12H22O11.
a) Tnh cht vt l
Tt c cc isaccarit u l nhng cht khng mu, kt tinh c v tan tt trong nc.

b) Tnh cht ha hc Phn ng thu phn
C12H22O11 + H 2O
Axit, toC
C6H12O6 + C6H12O6
Glucoz fructoz
C12H22O11 + H2O
Mantoz
Axit, t
2C6H12O6
Glucoz
Phn ng ca nhm anehit

- Saccaroz khng c nhm chc anehit nn khng tham gia phn ng trng gng v phn ng vi Cu(OH)2. - Mantoz v lactoz khi ho tan trong dung dch chuyn mt phn sang dng tautome c nhm chc anehit nn c phn ng trng gng v phn ng vi Cu(OH)2.
Phn ng vi hiroxit kim loi (tc dng vi Cu(OH)2) v tham gia phn ng to ete v
este (phn ng ca ru nhiu ln ru).
c) iu ch
Cc isaccarit c iu ch t cc ngun nguyn liu thin nhin. V d Saccaroz ly t ma, c ci ng.
Trang 137
Saccaroz trong ma tc dng vi sa vi to thnh dung dch canxi saccarat trong sut. Khi sc CO2 vo dung dch canxi saccarat li to thnh saccaroz:
C12H22O11 + Ca(OH)2 + H2O

CO2 + C12H22O11.CaO.2H2O
C12H22O11.CaO.2H2O
Canxi saccarat
C12H22O11 + CaCO3 + 2H2O
Mantoz l cht ng ch yu trong mch nha (ng mch nha). N l sn phm ca s thu phn tinh bt. Lactoz c trong sa ngi, ng vt (v vy cn c tn l ng sa). Ngoi ra cng tm thy c lactoz trong thc vt.
7.2.3. Polisaccarit
Polisaccarit l nhng gluxit c cu thnh bi nhiu n v monosaccarit ni vi nhau bng nhng lin kt glicozit. Nhng polisaccarit thng gp: tinh bt, xenluloz,
7.2.3.1. Tinh bt (C6H10O5)n a) Cu to:

Tinh bt l hn hp cc polisaccarit (C6H10O5)n, khc nhau v s n v cu trc ca chui polime. Tinh bt c trong c v ht nhiu loi cy. Cc phn t tinh bt gm 2 loi: - Loi amiloz cu to t chui polime khng phn nhnh gm cc mt xch a- glucoz mch vng vi n vo khong 200 400 v c khi ti 1000. Gia 2 mt xch l mt cu oxi ni nguyn t C1 ca gc th 1 vi nguyn t C4 ca gc th 2. Cu oxi ny c gi l lin kt a-1, 4 glicozit.
CH2OH H CH2OH O OH H H OH H H OH O
OH O.
. . .O
OH H
H OH
..
- Loi amilopectin: Chui polime c s phn nhnh, h s n t 600 - 6000. S hnh thnh mch nhnh l do lin kt a - 1,6 glicozit, c biu din nh sau:
Trang 138
CH2OH H
OH
. . .O
OH H
H OH
O CH2 H H OH H H OH O
OH O.
. . .O
..
T l amiloz v amilopectin thay i tu theo tng loi tinh bt, amiloz thng chim 20% v amilopectin chim khong 80%.
b) Tnh cht vt l
Tinh bt cu to t nhng ht nh c hnh dng v kch thc khc nhau, phn ngoi ca ht tinh bt cu to t amilopectin, phn bn trong cu to t amiloz. Cc ht tinh bt khng tan trong nc lnh. Trong nc nng ht b phng ln ri v thnh dung dch keo gi l h tinh bt.
c) Tnh cht ho hc
- H tinh bt + dung dch iot dung dch mu xanh. - Tinh bt khng tham gia cc phn ng kh (phn ng trng gng v vi Cu2+) v trong phn t khng c chc anehit. - Phn ng thu phn tinh bt thnh glucoz xy ra khi un nng vi xc tc axit v c long hoc nh cc enzim, phng trnh tng qut:
(C6H10O5)n + nH2O
Axit, toC
nC6H12O6
Glucoz
d) S to thnh tinh bt t CO2 v H2O
Nng lng mt tri c l cy hp th, chuyn qua cc sc t: clorofin (mu xanh lc), carotin (mu da cam), xantofin (mu vng) v dng thc hin qu trnh quang hp.
e) ng dng ca tinh bt
- Lm lng thc cho ngi v ng vt. - iu ch glucoz. - iu ch mch nha. - iu ch ru etylic
Trang 139
- H vi.
7.2.3.2. Xenluloz (C6H10O5)n a) Cu to phn t
Khc vi tinh bt, cu to phn t ca xenluloz c nhng c im sau: - n rt ln ( t 6000 12000 ). - Chui polime ca xenluloz l mch thng khng phn nhn, v vy n to thnh si (si bng, si gai, si ay) trong cc chui polime c xp theo cng mt phng v xut hin lc tng tc gia cc chui . - Mi mt xch (1 mt xch glucoz) c 3 nhm OH, trong 1 nhm chc ru bc 1 v 2 nhm chc ru bc 2. nhn mnh c im ny, ngi ta thng vit cng thc phn t ca xenluloz nh sau:
C6H7O2(OH)3
b) Tnh cht vt l
Xenluloz l cht rn, khng mi, khng c v, c dng si, c tnh thm nc. Xenluloz khng tan trong nc, ete, ru nhng tan trong mt s dung mi c bit nh dung dch Sveze gm Cu(OH)2 trong NH3 c, dung dch H2SO4 c.
c) Tnh cht ho hc
- Bn hn tinh bt (khng to mu xanh vi iot) - To thnh este

H2SO4,
C7H6O2(OH)3
+ 3nHNO3
to
C6H7O2(NO2)3
+ 3nH2O
Xenluloz trinitrat (Piroxylin)
Trinitroxenluloz l cht n mnh, c dng lm thuc sng khng khi. Khi este ho khng hon ton s thu c mono, initroxenluloz dng ch sn, lm phim, keo dn, - Phn ng to thnh xenluloz iaxetat v xenluloz triaxetat. Cc cht trn c iu ch bng phn ng gia xenluloz v anhirit axetic c H2SO4 xc tc: Xenluloz axetat khng d chy nh xenluloz nitrat, c dng ch t nhn to, nha, sn.
Trang 140
- Khi ch ho vi kim c (NaOH) xenluloz b phng ln thnh xenluloz kim l sn phm th khng hon ton. Xenluloz kim khi ch ho vi CS2 to thnh xenluloz xantogenat Xenluloz xantogenat ho tan trong dung dch kim long thnh dung dch rt nht gi l visco. Khi p visco chy qua l nh vo dung dch axit s thu c si xenluloz hirat, l t visco. - Phn ng thu phn xenluloz. Xenluloz kh b thu phn hn tinh bt. Phi un nng lu vi axit v c long p sut cao, xenluloz thu phn hon ton thu c glucoz:
(C6H10O5)n + nH2O
Axit, toC
nC6H12O6
Glucoz
d) Xenluloz trong t nhin - ng dng

- Xenluloz c nhiu trong si bng (98%), si ay, gaiTrong g c khong 50% xenluloz. - Xenluloz c dng lm giy, lm vi, si, t nhn to (v d t visco), thuc sng khng khi, cht do (xenluloit), sn, sn xut ru etylic.
7.3. Aminoaxit 7.3.1. Khi nim v aminoaxit

Aminoaxit l hp cht hu c tp chc, c cha c nhm -NH2 (baz) v nhm -COOH (axit) trong phn t. Cng thc tng qut : (NH2)x - R - (COOH)y C th coi aminoaxit l dn xut th NH2 vo nguyn t H gc R ca axit cacboxylic, khi nhm NH2 c th nh vo nhng v tr khc nhau (, , ,) trn mch C.
C C C COOH
Cc aminoaxit c trong cc cht anbumin t nhin u l -aminoaxit. C nhng aminoaxit trong s nhm NH2 v s nhm COOH khng bng nhau. Tnh axit - baz ca aminoaxit tu thuc vo s nhm ca mi loi.
7.3.2. Tnh cht vt l

Cc aminoaxit u l nhng cht tinh th, nng chy nhit tng i cao ng thi b phn hu. Phn ln u tan trong nc, t tan trong dung mi hu c.

a) Va c tnh axit, va c tnh baz - Trong dung dch t ion ho thnh lng cc:
(+)
Trang 141
H2N
COOH
H3N
COO(-)
- To mui vi c axit v kim:

NH2 - CH2 - COOH + NaOH NH2 - CH2 - COONa + H2O
H2N
COOH + HCl
H3N Cl
(-)
(+)
COOH
- Phn ng este ho vi ru.

NH2-CH2-COOH + C2H5OH
+ H
NH2-CH2-COOC2H5+ H2O
b) Phn ng trng ngng to polipeptit
- Trng ngng gia 2 phn t to ipeptit.

2H2N R COOH H 2O + H 2N CH2 C O N CH2 COOH
H LK peptit
- Trng ngng to ra polipeptit

- NH - CH2 - C O
nNH2 - CH2 - COOH
+ nH2O n
Cc polipeptit thng gp trong thin nhin (protein)

7.3.4. iu ch
a) Thu phn cc cht protein thin nhin Protein b) Tng hp - T dn xut halogen ca axit.
CH3 R Br COOH + 2NH3 CH3 R NH2 COOH + NH4Br
H2O
t Cc aminoaxit
0
- Tng hp nh vi sinh vt.

7.4. Protein 7.4.1. Thnh phn - cu to
- Thnh phn nguyn t ca protein gm c: C, H, O, N, S v c P, Fe, I, Cu. - Protein l nhng polime thin nhin cu to t cc phn t aminoaxit trng ngng vi nhau. - S to thnh protein t cc aminoaxit xy ra theo 3 giai on.
Trang 142
+ Giai on 1: To thnh chui polipeptit nh s hnh thnh cc lin kt peptit. + Giai on 2: Hnh thnh cu trc khng gian dng xon (nh l xo) ca chui polipeptit nh cc lin kt hiro gia nhm C=O ca vng ny vi nhm - NH - ca vng tip theo.
C O. . . H N
dng xon, gc R hng ra pha ngoi. + Giai on 3 cc chui polipeptit dng xon cun li thnh cun nh s hnh thnh lin kt ho hc gia cc nhm chc cn li trong gc aminoaxit ca chui polipeptit. Vi cch cu to nh vy t hn 20 aminoaxit to thnh hng ngn cht protein khc nhau v thnh phn, cu to trong mi c th sinh vt. Mi phn t protein vi cu hnh khng gian xc nh, vi nhm chc bn ngoi hnh xon mang nhng hot tnh sinh hc khc nhau v thc hin nhng chc nng khc nhau trong hot ng sng ca c th.
7.4.2. Tnh cht a) Cc protein khc nhau to thnh nhng cun khc nhau: C 2 dng chnh.
- Hnh si: nh t tm, lng, tc. - Hnh cu: Nh anbumin ca lng trng trng, huyt thanh, sa.
b) Tnh tan: rt khc nhau
- C cht hon ton khng tan trong nc (nh protein ca da, sng, tc) - C protein tan c trong nc to dung dch keo hoc tan trong dung dch mui long. Tnh tan ca mt s protein c tnh thun nghch: nu tng nng mui th protein kt ta, nu gim nng mui protein tan.
c) Hin tng bin tnh ca protein
Khi b un nng hay do tc dng ca mui kim loi nng hoc ca axit (HNO3, CH3COOH), protein b kt ta (ng t) km theo hin tng bin tnh. Khi , cc lin kt hiro, lin kt mui amoni, lin kt isunfua, lin kt este b ph hu v lm mt hot tnh sinh hc c trng ca protein.
d) Tnh lng tnh ca protein
V trong phn t protein cn c nhm - NH2 v - COOH t do nn c tnh baz v tnh axit tu thuc vo s lng nhm no chim u th. Trong dung dch, protein c th bin thnh ion lng cc
+
H3N - R - COO-.
Khi tng s in tch dng v in tch m ca ion lng cc bng khng th protein c gi l trng thi ng in.
e) Thu phn protein
2 Protein 2 cc aminoaxit cc poli peptit 2 cc peptit
+ H O,H+
+ H O,H+
+H O
f) Phn ng c mu ca protein
Trang 143
Tng t peptit v aminoaxit, protein tham gia phn ng cho mu. - Phn ng biure: Cho protein tc dng vi mui ng (CuSO4) trong mi trng kim cho mu tm do s to thnh phc cht ca ng (II) vi hai nhm peptit. - Phn ng xantoproteinic: Cho HNO3 m c vo protein s xut hin mu vng. Nguyn nhn do phn ng nitro ho vng benzen cc gc aminoaxit to thnh cc hp cht nitro dng thm c mu vng.
7.4.3. Phn loi protein
Gm 2 nhm chnh:
a) Protein n gin: ch cu to t cc aminoaxit, khi thu phn hu nh khng to thnh cc sn
phm khc. Cc protein n gin li c chia thnh nhiu nhm nh. V d: - Anbumin: Gm mt s protein tan trong nc, khng kt ta bi dung dch NaCl bo ho nhng kt ta bi (NH4)2SO4 bo ho. ng t khi un nng. C trong lng trng trng, sa. - Globulin: Khng tan trong nc, tan trong dung dch mui long, ng t khi un nng. C trong sa, trng. - Prolamin: Khng tan trong nc, khng ng t khi un si. C trong la m,ng. - Gluein: Protein thc vt tan trong dung dch kim long. C trong thc go. - Histon: Tan trong nc v dung dch axit long. - Protamin: L protein n gin nht. Tan trong nc, axit long v kim. Khng ng t khi un nng.
b) Cc protein phc tp: Cu to t protein v cc thnh phn khc khng phi protein. Khi thu
phn, ngoi aminoaxit cn c cc thnh phn khc nh hiratcacbon, axit photphoric. Protein phc tp c chia thnh nhiu nhm. - Photphoprotein: c cha axit photphoric. - Nucleoprotein: trong thnh phn c axit nucleic. C trong nhn t bo ng, thc vt. - Chromoprotein: c trong thnh phn ca mu. - Glucoprotein: trong thnh phn c hiratcacbon. - Lipoprotein: trong thnh phn c cht bo.
7.7.4. S chuyn ho protein trong c th
Protein l mt thnh phn quan trng nht trong thc n ca ngi v ng vt ti to cc t bo, cc cht men, cc kch thch t, xy dng t bo mi v cung cp nng lng. Khi tiu ho, u tin protein b thu phn (do tc dng ca men) thnh cc polipeptit (trong d dy) ri thnh aminoaxit (trong mt) v c hp th vo mu ri chuyn n cc m t bo ca c th. Phn ch yu ca aminoaxit ny li c tng hp thnh protein ca c th. Mt phn khc tng hp cc hp cht khc cha nit nh axit nucleic, kch thch tMt phn b phn hu v b oxi ho cung cp nng lng cho c th.
Trang 144
ng thi vi qu trnh tng hp, trong c th lun xy ra qu trnh phn hu protein qua cc giai on to thnh polipeptit, aminoaxit ri cc sn phm xa hn, nh NH3, ure O = C(NH2)2 to thnh CO2, ncQu trnh tng hp protein tiu th nng lng, qu trnh phn hu protein gii phng nng lng.
7.4.5. ng dng ca protein
- Dng lm thc n cho ngi v ng vt. - Dng trong cng nghip dt, giy dp, lm keo dn. - Mt s protein dng ch to cht do (nh cazein ca sa).
Chng 8: Hp cht d vng
Trang 145
Chng 8: HP CHT D VNG

8.1. Khi nim Hp cht d vng l nhng hp cht hu c c vng kn trong phn t, nhng trong vng ngoi C ra cn c mt vi nguyn t ca nguyn t khc c gi l d t. Nhng hp cht d vng quan trng thng cha cc d t l nit, oxi v lu hunh. Tuy vy, ngi ta cng cn gp cc d vng cha d nguyn t selen, telu, photpho, silic v cc nguyn t khc. Trong chng ny chng ta ch xt ch yu cc hp cht d vng 5 v 6 cnh c cha d t, c th l furan, pirol, thiophen v piridin:
H-C H - C5
4
C-H
H-C H - C5
C-H
H-C H - C5
C-H
H C HC 5 HC6
4 3
CH CH
O ..1 Furan
..
C-H
N1 H Pirol
..
C-H
S ..1 Thiophen
..
C-H
Piridin
N ..
Cc d vng 5 cnh nh furan, pirol v thiophen c th coi nh nhng dn xut ca xiclopentadien trong nhm metylen CH2 c th thay th bng d t O, NH v S. Nu trong cc d vng 5 cnh trn, mt nhm CH c thay th bng mt d t N ta s c nhng d vng 2 d t l oxazol v isooxazol; thiazol v isothiazol; imidazol v pirazol:
H C HC
H C CH HC
H C
N CH & HC
H C
H C N
O Furan H C HC H C CH S Thiophan HC
O Oxazol H C N CH S Thiazol & HC
O Isoxazol H C H C N S Isothiazol
H C HC N H
H C CH HC
H C
N CH & HC
H C
H C N N H
Pirol
N H Imidazol
Tip theo nu i t pirazol, ta thay th mt nhm CH = bng mt d t nit N = th ba ta s c cc triazol:
Trang 146
H C HC
N HC
H C
N N H 1,2,3- Triazol
N N H 1,2,4- Triazol
Nu mt d t nit th t N = th cho mt nhm CH = ta c mt tetrazol:

N HC N
N N H 1,2,3,4- Tetrazol Ngi ta thng dng ui ol hay ole cho tn cc vng 5 cnh, ch l khng nn nhm vi ui ol dnh cho nhm OH ca ancol. Ngoi cc d vng 5 cnh, ngi ta cng bit cc d vng 6 cnh c mt d t, hai, ba, bn d t. Piridin l d vng 6 cnh mt d t N. Ngi ta thng coi d vng piridin nh mt nhn benzen c hnh lc gic u vi 6 cnh trn cng mt mt phng, trong mt nhm CH = c thay th bng mt nguyn t nit N =:
H C HC 5 HC6
4 3
CH CH hay: N
Piridin
N ..
Nu mt nhm CH = th hai trong vng piridin c thay th bng mt d t nit ta s c nhng iazin: N N N N Piridin N Piridazin
(o-diazin)
N Pirimidin
(m-diazin)
N Pirazin
(p-diazin)
Nu nhm CH = th ba trong nhn benzen c thay th bng mt d t nit N = th ba, ta s c nhng triazin:
N N N N 1,2,3- Triazin N N 1,2,4- Triazin N N 1,3,5- Triazin N
Trang 147
Theo l thuyt ta phi c 3 ng phn triazin nh trn y, nhng trong thc t ch mi bit c mt s hp cht ca chng m thi. Ngoi ra, ngi ta cng bit c hp cht d vng 7 cnh mt d t:
Azepin N H
8.2. D vng 5 cnh mt d t 8.2.1. Tnh thm
Cc d vng 5 cnh biu l tnh thm l do s lin hp ca h lc t thm. Th d trong d vng pirol, s hnh thnh h lc t thm l do s lin hp ca 4 electron pi vi mt cp electron cha s dng ca nit. i vi d vng furan v thiophen cng vy:
. .
..
hay:
N H
.. N H
hay: N H
8.2.2. Ho tnh ca cc hp cht d vng 5 cnh a) Phn ng th electrophin trong pirol
i vi pirol th s th electrophin ch yu vo v tr 2, v cng cn ch l c th nitro ha, sunfo ha vng pirol nhng ch trong mi trng phn ng khng c axit, bi v nu c axit th pirol s b trng hp. Mt khc pirol c th tip nhn phn ng halogen ha v axyl ho m khng cn xc tc. Tuy vy, nu trong phn t pirol m c cha nhm th ht electron (nhm NO2 v COOH) th lc kh nng phn ng s km hn pirol khng c nhm th v i hi phi c xc tc phn ng mi xy ra:
CH3COO NO2 (CH3CO)2O, 5oC
NO2 N H
2-nitro pirol
SO3, piridin, 90oC
N H
(CH3CO)2O, 250oC
SO3H N H
COCH3 N H
Trang 148
b) Phn ng th electrophin trong furan
V kh nng phn ng th furan tng t pirol, nhng c phn mnh hn pirol. KHi clo ha furan -40oC c th dn ti 2-clofuran v 2,5-iclofuran:
(-) (+) CH3COO NO2
NO2 O
SO3, piridin 2-nitrofuran
SO3H O
(CH3CO)2O, BF3
COCH3 O
c) Phn ng th electrophin trong thiophen
Kh nng phn ng ca thiophen km hn furan v pirol (nht l khi tc dng vi cc axit mnh) do n c th tip nhn phn ng nitro ha, sunfo ha trong iu kin axit cao. Clo ha thiophen dn ti hn hp phc tp ca cc sn phm tng hp, nhng brom ha v it ha c th dn ti s to thnh 2-brom v 2-iotthiophen:
(-) (+) CH3COO NO2 (CH3CO)2O
NO2 S
2-nitrothiophen
H2SO4
SO3H S
Br2, benzen
Br S
d) Phn ng cng hp theo inx An (Diels Alder)
Trong s cc d vng thm 5 cnh, ch c furan c c tnh lin hp ien, ngha l c th tham gia vo phn ng cng 1,4:
C=O O
Furan
CH HC O HC CH CH CH
C=O O C=O
O C=O
Anhidrit maleic
Trang 149
e) Phn ng chuyn ha ln nhau gia cc d vng 5 cnh m d t (Iurep, 1936)

nhit khong 300oC, vi s c mt ca cht xc tc Al2O3, s xy ra phn ng sau:
NH3 H2O
N H
NH3 H2S
H2S
H2O
8.2.3. iu ch a) Furan: Decacboxyl ha axit furoic

- CO2
CHO O O
COOH O
b) Pirol
iu ch t axetylen v NH3
CH CH H N H H CH CH
Al2O3 450oC
8.3. D vng 6 cnh mt d t - Piriin 8.3.1. Cu trc ca piriin

Cu trc ca piriin lm ta nh li cu trc ca benzen. Tt c cc lin kt C C nm trn mt mt phng, c di ging nhau 1,39A0 ( di lin kt ca C C l 1,54A0 v C = C l 1,34A0). Hai lin kt C N cng c di ging nhau 1,37A0 (ngn hn di ca lin kt n CN l 1,4A0 v di hn lin kt C = N l 1,28A0).
4 5 3
N
1
Cc thng s ca phn t piriin v bn thm c bit ca n ni ln s gii to 6 electron p - (ca 5 nguyn t C v ca N).
8.3.2. Tnh cht ca piriin
Trang 150
Da trn c s cu trc ca piriin, ta c th d on c tnh cht ca n. Phn nhn tham gia phn ng th (th electrophin v th nucleophin) v nguyn t N c nh hng r rt n cc phn ng ny. Ngoi ra, piriin tc dng nh mt baz hoc tc nhn nucleophin. Cc phn ng ny do nit trc tip tham gia phn ng v c gy do cp electron cha s dng ca n.
a) Phn ng th electrophin
Phn ng th electrophin trong nhn piriin thc hin rt kh khn, phn th do tc dng v hot ha ca d t ln nhn, phn th do trong mi trng axit, khi nitro ha v sunfo ha, vng cn b hot ha do to thnh ion piriin. Cng v vy m iu kin thc hin phn ng th kht khe, v a s trng hp cho hiu sut thp:
KNO3 - H2SO4 H2SO4 370oC
NO2 N(+) H
N(+) H Br
Br2
300oC
SO3, H2SO4, HgSO4 220oC, 24h
SO3H
N(+) H
N
300
Br2 - 500oC
N
b) Phn ng th nucleophin
Br
Phn ng th quan trng nht trong nhn piriin l phn ng th nucleophin. Piriin c th c amin ha (bng natri amiua khi un nng), hyroxyl ha (vi tc dng ca KOH), cng nh ankyl ha v aryl ha:
1. Na(+)NH2(-), 100oC 2. H2O
2 - Aminopiridin KOH 320oC, O
NH2
2 - Hidroxipiridin
OH
N H
Piridon
N
110oC, toluen
+ N C6H5
2 - Phenylpiridin
LiH
n - C4H9Li 100oC
+ N
2 - n - Butylpiridin
LiH
C4H9-n
Trang 151
BI TP
8.1: Hp cht d vng l g ? Trnh by s phn loi hp cht d vng km theo cc th d minh
ho?
8.2:Vit cng thc cu to ca cc d vng furan, thiophen, pirol v piriin. V sao nhng d vng
ny c tnh thm? c im chung v cu to ca hp cht thm l g?
8.3: So snh ho tnh ca pirol, piriin v benzen ?
Phn 2: Thc hnh Ha hu c
Trang 152
Bi 1:
PHN TCH NH TNH NGUYN T TRONG HP CHT HU C
1.1. XC NH CACBON V HYRO BNG PHNG PHP OXI HA Ha cht: Sacaroz (hoc axit benzoic), bt CuO, dung dch bo ha Ca(OH)2, Ba(OH)2,CuSO4 khan bt. Trn u 0,2 -0,3g saccaroz vi 1 2g CuO trn mt knh hoc giy. Cho hn hp vo ng nghim kh. Cho tip thm khong 1 g CuO trn mt knh hoc giy. Cho hn hp vo ng nghim kh. Cho tip thm khong 1g Cuo ph kn hn hp. Phn trn ca ng nghim c dn mt nhm bng, rc ln nhm bng mt t CuSO4 khan. Lp dng c nh hnh 1. un nng ng nghim cha hn hp phn ng, lc u un nh nhng ton b ng nghim, sau un mnh phn c hn hp phn ng.
?
1. Nu nguyn tc phn tch nh tnh cc nguyn t trong hp cht hu c. 2. Nhng hin tng g xy ra trong c hai ng nghim? Gii thch? 3. Vit cc phng trnh phn ng xy ra. 1.2. XC NH NIT Ha cht: Ure (khan), axetamid, Na, dung dch FeSO4 1%, dung dch FeCl3 1%, dung dch HCl c, dung dch HCl 10%, hn hp vi-xut (rn), C2H5OH 960. a. Trng hp ring: Hp cht c N lin kt trc tip vi C v H. Trn u khong 0.1g ure v 1 g vi xut ri cho vo ng nghim kh. un nng ng nghim. Nhn xt kt qu th nghim bng 3 cch sau: Ngi mi kh thot ra ming ng nghim. t mu giy qu thm t trn ming ng nghim. a mu a thu tinh c tm dung dch HCl c vo ming ng nghim.
b. Trng hp chung Ly khong 0.5g ure (hoc hp cht hu c khc c N nh anilin, axetamit) v chia thnh 2 phn bng nhau. Phn th nht c cho vo y ng nghim kh. Cho tip vo mt mu Na ( c co sch lp ngoi v p kh gia hai mnh giy lc). Phn ure cn li cho tip vo ng nghim ph kn mu Na. un nng (cn thn) ng nghim trn n cn cho n khi y ng nghim nng . ngui, nh t t vo ng nghim khong 1mL ancol etylic phn hu Na cn d. Cho thm 2 mL nc ct, khuy u, lc hn hp thu ly dung dch trong. Nh 2-3 git dung dch FeSO4 1% v 1-2 git dung dch FeCl3 1% vo dung dch va thu c. Quan st mu sc kt ta:
Trang 153
Axit ha hn hp bng vi git dung dch HCl 10 % cho n khi xut hin mu xanh da tri.
?
1. Vit cc phng trnh phn ng ha hc xy ra. 2. Nhng kt ta no c to ra khi cho cc mui st vo dung dch lc?
1.3. XC NH LU HUNH Ha cht: Axit sunfanilic hoc thioure, Na, dung dch Pb(CH3COO)2 2%, dung dch NaOH 10%, dung dch HCl 10%. Tin hnh phn hu hp cht cha lu hunh bng cch nung nng vi Na nh phn b ca th nghim 2. Lc nhiu ln ly dung dch trong. Chia dung dch va lc thnh hai phn lm cc th nghim tip theo. a. Ly mt ng nghim khc c 0.5mL dung dch Pb(CH3COO)2 2%, nh t t vo tng git dung dch NaOH 10% cho n khi ha tan ht ch hidroxit (va sinh ra). Rt dung dch mui ch va thu c vo dung dch lc trn (Phn th nht) Quan st hin tng xy ra: b. Nh t t tng git dung dch HCl 10% vo phn dung dch lc cn li. Nhn xt mi c trng ca kh thot ra.
?
Nhng hin tng g xy ra th nghim a v b ? Gii thch bng phng trnh phn
ng ho hc. 1.4. XC NH HALOGEN Ha cht: Cloroform (hoc dicloetan, clobenzen, brombenzen, idofom), dung dch AgNO3 1%, dung dch NH3, ancoletylic. Dng c: Dy ng, phu thu tinh. Phng php 1: Ly mt si dy ng nh un thnh nhng vng l xo nh v buc vo u a thu tinh. t dy ng trn ngn la n cn ti khi khng cn ngn la mu xanh ca tp cht. Nhng dy ng vo hp cht hu c c cha halogen, em t trn ngn la n cn, Nhn xt mu c trng ca ngn la. Phng php 2: ly mt mnh giy nh, tm ancol etylic v nh thm my git hp cht hu c c cha halogen (cht lng hoc dung dch trong etanol). ng thi chun b mt phu thu tinh, nh vo thnh pha trong ca phu my git dung dch AgNO3 1%, p phu ln pha trn mnh giy ri t chy giy. Nhn xt hin tng xy ra thnh phu. Sau nh ln thnh pha trong ca phu my git dung dch NH3
?
Tip tc theo di hin tng xy ra. Phn tch qu trnh tin hnh th nghim tm halogen theo phng php 1 v 2. Vit
phng trnh phn ng.
Trang 154
Bi 2:
HIRO CACBON
2.1. HIRO CACBON NO a) iu ch v tnh cht ca metan Ha cht: Natri acetat khan, vi xut khan (hn hp NaOH rn v CaO), nc brm bo ha, dung dch KmnO4 rt long, dung dch Na2Co3 5%. TN1: iu ch v t chy Mtan Cho vo ng nghim kh c nt v ng dn kh cong (hnh 1) khong 4-5g hn hp natri acetat khan v vi xut (theo t l 1 phn mui, 2 phn vi xt v khi lng) c nghin nh v trn u trong ci x. Kp ng nghim trn gi st v un nng bng ngn la n cn. Lc u un nng nh ton b ng nghim, sau un nng mnh phn c hn hp phn ng. u tin khng kh trong ng nghim thot ra, tip theo l kh metan. t kh mtan u ng dn kh (*). Nhn xt m ngn la. a np chn s chm vo ngn la ca metan ang chy. Quan st mu sc ca np chn s trc vsau th nghim. Lng kh mtan cn li lm cc th nghim tip theo.
?
1. Cho bit mu ngn la do Mtan chy. Ti sao trn np chn s (ca th nghim trn)
khng xut hin vt mui en? 2. Vit cc phng trnh phn ng iu ch v t chy mtan. TN2: Tng tc ca Metan vi nc brom v dung dch kali permanganat Trong khi chun b th nghim iu ch Metan cng chun b sn hai ng nghim sau: ng 1 cha 2mL nc brom, ng th hai cha 2mL dung dch KMnO4 long v 1mL dung dch Na2CO3 5%. Sau th nghim t chy dn kh mtan cn li vo ng nghim cha nc brom trong khong 1 pht. Nhn xt xem nc brom c b mt mu khng ? a ng dn kh metan vo ng nghim chab dung dch KMnO4. Quan st mu ca dung dch.
?
nhit phng metan c phn ng vi nc brom hoc dung dch KMnO4 khng?
b) Phn ng brom ha hidrocacbon no Ha cht: n-Hexan hoc hn hp hidrocacbon no* (th d ete du ho c nhit si khong 60-700C), dung dch Br2 5% trong CCl4, dung dch NH3 25%. Rt vo ng nghim kh khong 1 ml hidrocacbon no. Nh thm vi git dung dch Br2 5% trong CCl4. Lc nh hn hp phn ng. Quan st mu ca dung dch Br2. un hn hn hp trong ni nc nng. Theo di kt qu th nghim bng cc cch sau:
Trang 155
Quan st s i mu ca dung dch Br2 a mu giy qu xanh tm t vo ming ng nghim a u a thu tinh tm dung dch NH3 vo ming ng nghim.
1. Nu nhng hin tng xy ra khi cho brom tc dng vi hirocacbon no 2. iu kin xy ra phn ng brom ho hidrocacbon no? c) Tc dng ca kali permaganat vi hiro cacbon no Ha cht: Hirocacbon no lng (xem th nghim 2.2), dung dch Na2CO3 5%, dung dch Cho vo ng nghim khong 0.5mL hirocacbo no, 0.5ml dung dch Na2CO3 5%, sau nh thm vi git dung dch KMnO4 1% v lc u. Quan st mu sc ca dung dch KMnO4.
?
Kt lun g c rt ra t kt qu th nghim?
d) Tc dng ca axit sunfuric vi hirocacbon no Ha cht: Hirocacbon no lng (xem th nghim 2.2), axit sunfuric c. Cho vo ng nghim kh khong 0,5ml hirocacbon lng, 0,5 ml H2SO4 c. Lc nh hn hp trong khong 2 3 pht. Theo di mu sc v nhit ca hn hp. e) Tc dng ca axit nitric vi hirocacbon no Ha cht: Hidrocacbon lng (xem th nghim 2.2 ), HNO3 c. Cho khong 0,5mL. Lc nh hn hp trong khong 2 3 pht. yn v quan st hn hp phn ng.
?
Kt lun g c rt ra r kt qu th nghim cho hidrocacbon no tc dng vi H2SO4 c
v HNO3 c nhit phng? 2.2. HIDROCACBON KHNG NO a) iu ch etilen Ha cht: Ancol etylic 960, axit sufuric c, vi xt, ct sch hoc s xp (ht nh). Cho 2ml ancol etylic vo ng nghim kh, cn thn nh thm tng git 4ml H2SO4 c ng thi lc u. Cho vo hn hp vi ht ct hoc vi vin s xp. Kp ng nghim vo gi v lp ng dn kh c ni vi ng ng vi xt. un nng cn thn hn hp phn ng v khng cho hn hp tro sang ng cha vi xt. Nhn xt mu ca hn hp phn ng. t kh etylen u ng dn kh. nhn xt mu ngn la. a np chn s chm vo ngn la etylen ang chy. Quan st mu ca np chn s trc v sau th nghim. Lng kh etylen cn li lm cc th nghim tip theo.
Trang 156
1. Ti sao phi cho thm ct hoc s xp vo hn hp phn ng? 2. Ti sao phi ni ng dn kh vi ng ng vi xt? 3. Vit cc phng trnh phn ng xy ra? b) Phn ng cng brom vo etylen Ha cht: Dung dch nc brom bo ha. Cho 1ml dung dch nc brom bo ha vo ng nghim. Dn kh etilrn vo nc brom. Quan st s bin i mu ca dung dch. c) Phn ng oxiha etilen bng dung dch kali permanganat Ha cht: Dung dch KMnO4 2%, dung dch Na2CO3 10% Cho 2ml dung dch KMnO4 2% v 0,5ml dung dch Na2CO3 10% vo ng nghim. Dn kh etilen vo hn hp. Qu8an st s bin i mu ca dung dch. Kt lun no c rt ra t cc kt qu ca th nghim 3.2 v 3.3? Vit cc phong trnh phn ng xy ra. d) iu ch axetilen Ha cht: Canxi cacbua Cho vo ng nghim vi vin canxi cacbua. Rt nhanh khong 1ml nc vo ng nghim v y nhanh bng nt c ng dn kh vi u vut nhn. t kh axetilen u ng dn kh. Nhn xt mu ngn la. a np chn s chm vo ngn la. Quan st mu ca np chn s trc v sau th nghim. So snh vi th nghim t chy metan v etilen.
?
1. Vit phng trnh phn ng iu ch axetilen t canxi cacbua v phng trnh t chy ca axetilen (chy hon ton v khng hon ton). 2. Kh sinh ra trong qu trnh t chy axetilen c mi kh ngi. Gii thch. e) Phn ng cng brom vo axetilen Ha cht: Dung dch nc brom bo ha. Cho 1ml dung dch nc brom bo ha vo ng nghim (chun b sn ngay khi lp dng c iu ch axetilen. Dn kh axetilen vo dung dch bng ng dn kh cong hnh 3.3). Nhn xt qu trnh bin i mu ca nc brom. f) Phn ng oxi ha acxetilen bng dung dch permaganat Ha cht: Dung dch KMnO4 1%, dung dch Na2CO3 10%
Trang 157
Cho 1ml dung dch KMnO4 1% v 1ml dung dch Na2CO3 10% v o ng nghim. Dn kh C2H2 vo hn hp. Quan st mu ca dung dch.
?
Nu nhng kt lun c rt ra t kt qu ca cc th nghim 3.5 v 3.6. Vit cc phng
trnh phn ng. g) Phn ng to thnh bc axerilua Ha cht: Dung dch AgNO3 1%, dung dch NH3 5% Cho 2ml dung dch AgNO3 1% vo ng nghim. Nh thm tng git dung dch NH3 5% cho n khi ha tan hon ton kt ta Ag2O (va c sinh ra). Dn kh axetilen vo hn hp. Quan st s xut hin kt ta bc axetilua v mu sc kt ta. Lc ly kt ta bc axetilua, ra kt ta bng lng nh nc, p kt ta trong t giy lc. Nung nng cn thn kt ta trn tm li aming bng n cn hoc bp in (cn thn! Cn bo v mt). Theo di qu trnh phn hu v nhng ting n nh ca bc axetilua. Giy lc v nhng vt bc axetilua cn li c cho vo cc nc. Cho thm mt lng nh axit clohidric c hoc axit nitric c (khong th tch nc trong cc). h) Phn ng to thnh ng (I) axetilua Ha cht: ng (I) clorua, dung dch NH3 c. iu ch dung dch phc [Cu(NH3)2]Cl Lc 1g mui CuCl vi 1,5 2,0ml dung dch NH3 c pha long hn hp bi 10ml nc. lng kt ta, gn ly dung dch khng mu lm th nghim.
?
Nu dung dch nhm mu xanh (do c lm ion Cu2+) th un nh dung dch, ng thi nh
vo tng git dung dch hidroxilamin clohidrat 1% ( hoc hidroxilamin sunfat 1%) cho ti khi dung dch tr thnh khng mu. Hydroxylamin l cht kh: 4Cu2+ + 2 H2NOH 4Cu+ + 4 H+ + N2O + H2O Cho 2 ml dung dch phc [Cu(NH3)2]Cl vo ng nghim v dn dng kh axetlen vo dung dch. Quan st qu trnh xut hin kt ta ng axetilua v mu sc ca kt ta. Sau th nghim ng acetilua c phn gii bng cch nh vo kt ta vi git HCl c hoc HNO3 c.
?
1. Nhng kt lun g c rt ra t kt qu th nghim to ra bc v ng axetilua? Vit cc phng trnh phn ng. 2. Ti sao phi cho dung dch axit vo kt ta ng v bc axetilua? Vit cc phng trnh phn ng.
Phn 2: Thc hnh Ha hu c 2.3. HIDROCACBON THM
Trang 158
a) Phn ng oxi ha benzen v toluen Ha cht: Benzen (tinh khit), toluen, dung dch KMnO4 5%, dung dch H2SO4 2N. Cho vo hai ng nghim, mi ng 1ml dung dch KMnO4 5% v 1ml dung dch H2SO4 2N. Cho tip vo ng th nht 0,5ml benzen, ng th hai 0,5ml Toluen. C hai ng nghim c y nt c ng thu tinh thng ng. Lc nh v un nng c hai ng nghim trn ni nc. Quan st hin tng( mu, kt ta) xy ra trong c hai ng nghim.
?
Nu mc ch ca th nghm. Gii thch nguyn nhn s khc nhau v tnh cht ca benzen v toluen i vi kalipermanganat. Vit phng trnh phn ng. b) Phn ng brom ha benzen v toluen Ha cht: Benzen (tinh khit), dung dch brom trong cacbon tetraclorua (t l 1:5 theo th tch). Bt st. a. Ly hai ng nghim kh, cho 1ml benzen vo ng th nht v 1 ml toluen vo ng th hai. Cho tip vo mi ng 1mldung dch brom ri lc u. Chia dung dch trong mi ng thnh hai phn bng nhau. Phn th nht c t trn gi. Phn th hai un nng n si nh (nn y ng nghim bng nt c lp ng thu tinh thng ng) trn ni nc ri t vo gi. Quan st v so snh mu dung dch ca phn th nht v phn th hai ca tng hidrocacbon. b. Cho mt nhm bt st (bng ht u xanh), 1ml benzen v 1ml dung dch brom vo ng nghim kh. Lc nh v un nng hn hp n si nh trn ni nc. Khi hn hp ang si a mnh giy qu xanh tm t vo ming ng nghim. Quan st s bin i mu ca dung dch v mu ca mnh giy qu.
?
1. Nu mc ch ca th nghim. 2. Nu v gii thch cc hin tng xy ra. Vit cc phng trnh phn ng. 3. Vai tr ca bt st? C th thay bt st bng cht no?
c) Phn ng nitro ha benzen Ha cht: Benzen, axit sunfuric (D=1,84 g/ml), axit nitric (D=1,4 g/ml). Dng c: cc thu tinh 50ml. Rt t t 2ml axit sufuric vo ng nghim (hoc bnh cu nh) cha sn 1,5ml axit nitric v lm lnh trong chu nc. Nh t t 1ml benzen vo hn hp axit ng thi lc mnh ng nghim trong chu nc. Sau khi lc lin tc hn hp trong vng 6-10 pht rt t t hn hp vo cc cha 20 -30 ml nc lnh. Dng a thu tinh khuy u hn hp, sau yn. Quan
Trang 159
st qu trnh phn lp ca hn hp! Nhn xt mu v mi thm c trng (mi hnh nhn) ca lp cht hu c ( di) c cha nitro benzen.
?
1. Vai tr ca axit sunfuric trong phn ng nitro ha? Vit phng trnh phn ng to ra nitro benzen bng hn hp nitro ha. 2. Ti sao phi lm lnh hn hp phn ng (to ra nitro benzen)? d) Phn ng sunfo ha benzen v toluen Ha cht: Benzen, toluen, axit sunfuric c (D=1,84 g/ml). Dng c: ng nghim c nt lp vi ng thu tinh thng, cc thu tinh 50ml. Cho 0,5ml benzen vo ng nghim th nht, 0,5ml toluen vo ng nghim th hai. Cho tip vo mi ng 2ml axit sunfuric. C hai ng nghim c y bng nt c ng thu tinh thng ng v un nng trn ni nc si, ng thi lc u. Theo di qu trnh ha tan dn cc cht trong hn hp. Tip tc un nng n khi c hn hp ng nht. ngui. Tng hn hp c rt vo mt cc ring cha sn 20ml nc. Nhn xt kh nng ha tan ca hn hp phn ng trong nc.
?
1. c im ca phn ng sunfo ha hidrocacbon thm ?Vit phng trnh phn ng sunfo
ha benen v toluen bng axit sunfuric. 2. Gii thch ti sao hn hp sn phm phn ng tan c trong nc. e) Phn ng nitro ha naphtalen Ha cht: Naphtalen (bt) axit nitric c (D=1,4 g/ml) Dng c: Cc thu tinh nh. Cho 0,5g naphtalen (dng bt) vo ng nghim cha sn 2ml axitnitric c. Lc hn hp nhit phng . Nhn xt s bin i mu ca hn hp! un nng hn hp trn ni nuc si v lc nh cho n khi ha tan ht naphtalen. Rt hn hp vo cc cha 10ml nc lnh. Quan st mu sc ca cc tinh th alpha-nitronaphtalen. Lc ly sn phm. Ra kt ta bng nc.
?
1. Ti sao khi nitro ha nitro naphtalen khng cn cho thm axit sunfuric? Vit phng trnh
phn ng to ra alpha-nitronaphtalen. 2. Ti sao khi nitro ha nitro naphtalen bng axitnitric c khng thu c betanitronaphtalen. f) Phn ng sunfo ha naphtalen Ha cht: Naphtalen (bt), axit sunfuric c. TN1: Axit - naphtalensunfonic
Trang 160
Cho 1g naphtalen vo ng nghim v un trn ngn la n cn cho naphtalen nng chy. Sau khi ngui, cho thm 1ml axit sunfurcic c vo ng nghim. un nng cn thn hn hp trn n cn v lc u, n khi to ra cht lng ng nht; Lm lnh cht lng, cho thm 2-3 ml nc v un nng nh. Khi ngui axit - naphtalensunfonic t t kt ta xung (khng c kt ta khi cho nhiu nc). TN2: Axit - naphtalensunfonic Cho 1g naphtalen v 1ml v axit sunfuric c vo ng nghim. un nng hn hp trn ni nc si trong khong 10 15 pht cho n khi naphtalen tan ht. Lm ngui v cn thn rt 2 3ml nc vo hn hp. Nhn xt kh nng tan ca axit - naphtalensunfonic trong nc.
?
Nu s khc nhau c bn v iu kin phn ng to ra axit - v - naphtalensunfonic. Vit phng trnh phn ng.
Trang 161
Bi 3:
DN XUT HALOGEN CA HIROCACBON
3.1. IU CH ETYL BROMUA Ha cht: Ancol etylic, axit sunfuric c, kali bromua (dng bt). Cho 1,5ml ancol etylic v 1ml nc vo ng nghim (1). t ng nghim vo chu nc lnh, nh t t tng git 1,5ml H2SO4 c vo dung dch ancol ng thi lc u. Lm lnh hn hp ti nhit phng, cho tip 1,5g KBr vo hn hp. Lp dng c nh (hnh v). ng nghim hng (ng 2) cha 1ml nc v vi vin nc .
un nng hn hp phn ng, lc u un nh, sau un nng n si. Quan st nhng git cht lng t t lng xung y ng nghim hng. Ngng un khi thy lng cht lng trong bnh hng khng tng. Dng pipet ly 1 git cht lng y ng nghim hng . Nh git cht lng cha 1ml nc vi vin nc v vi vin nc . un nng hn hp phn ng, lc u un nh, sau un nng n si. Quan st nhng git cht lng t t lng xung y ng nghim hng. Ngng un khi thy lng cht lng trong bnh hng khng tng. Dng pipet ly mt git y ng nghim hng. Nh git cht lng ln si dy ng (un thnh nhng vng l xo nh v c t nng trn ngn la n cn) v a ngn dy ng vo ngn la n cn. Nhn xt mu ngn la.
?
1. Ti sao phi a thm nc vo hn hp phn ng ? 2. Vit phng trnh phn ng iu ch etyl bromua t ancol etylic. Nu nhng phng php dng chuyn dch cn bng phn ng sang pha tng hiu sut etyl bromua. 3. Nhng phn ng ph xy ra trong qu trnh iu ch etyl bromua? 3.2. IU CH ETYL CLORUA Ha cht: Alcol etylic, axit sunfuric c, natri clorua (dng bt). Cho vo ng nghim 2ml ancol etylic, 1ml H2SO4 c v 0.1g natri clorua. y ng nghim bng nt c lp ng thu tinh thng v u vut nhn (H5). Lc nh, un hn hp phn ng trn ngn la n cn (cn thn! hn hp d b tro). t kh etyl clorua ts = 12,40C thot ra u ng dn kh. Quan st mu ngn la.

?
Trang 162
Vit cc phng trnh phn ng iu ch etylclorua t ancol etylic, natriclorua v axit
sunfuric. Gii thch mu c trng ca ngn la khi tetyl clorua. 3.3. IU CH IODOFOM T RU ETYLIC V ACETON Ha cht: Ru etylic, axeton, dung dch KI bo ha I2, dung dch NaOH 2N. a) iu ch iodofom t ru etylic Cho vo ng nghim 0.5ml ru etylic 1.5ml dung dch KI bo ha iod v 1.5ml dung dch NaOH 2N. Lc u ng nghim v un nh (khng c un si!) cho n khi dung dch xut hin kt ta vn c. Lm lnh ng nghim bng nc lnh. Quan st mu cht kt ta. b) iu ch iodofom t axeton Cho vo ng nghim 2ml dung dch KI bo ha I2 v 2ml dung dch NaOH 2N. Rt 0.5ml dung dch axeton vo hn hp trn v lc nh. Quan st mu ca cht kt ta.
?
1. Vit phng trnh phn ng iu ch iodofom t ru etylic v aceton. 2. Ti sao khng c un si hn hp phn ng. 3. Cho bit c im cu to ca cc hp cht c kh nng phn ng vi I2 to ra iodofom. 3.4. IU CH BROMOFOM T AXETON Ha cht: Axeton, brom, dung dch NaOH 10% Cho 1.5ml axeton, 3ml dung dch NaOH 10% v 10 git Br2 (Cn thn!bLm trong t ht) vo ng nghim. Lc nh hn hp. Quan st dung dch phn ng (mu sc, trng thi) Gn b lp nc trn, ly si dy ng nhng vo phn cn li ca y ng nghim ri a vo ngn la n cn (lm tng t th nghim 5 chng 1). Nhn xt mu ngn la.
?
1. Vit phng trnh phn ng iu ch bromofom t axeton. 2. Nhn xt v tan ca bromofom trong nc v so snh khi lng ring ca bromofom vi nc. Gii thch. 3.5. IU CH BROM BENZEN Ha cht: Benzen, brom, st (bt), vi xt, dung dch NaOH 2N Th nghim c tin hnh trong t ht, dng c theo hnh 6. Cho vo ng nghim kh mt t bt st, 1ml benzen v 0.5ml brom. Ming ng nghim c y ngay bng nt c ng dn kh cong. u cui ca ng dn kh ni vi ng hp th.Lc u ng nghim.Quan st hin tng xy ra trong ng nghim (mu ca dung dch, bt kh).
Trang 163
Sau khi khng cn bt kh tch ra, t ng nghim vo ni nc nng (60 700C) khong 2 pht. a ng nghim ra khi nc nng, lm lnh. Lc hn hp sn phmvi dung dch NaOH cho n khi dung dch khng cn mu brom. Lp nc trn c ht bng pipet. Lp cht lng cn li cha brom benzen. C th s b nhn ra brombenzen nh phn ng xc nh nh tnh brom (tng t th nghim 5 chng 1).
?
1. Vit phng trnh phn ng iu ch brmbenzen t benzen 2. Ti sao phi lp ng hp th kh vo ng nghim phn ng? 3. Ti so phi un nng hn hp phn ng trong ni nc nng ? 3.6. PHN NG CA DN XUT HALOGEN VI DUNG DCH KIM Ha cht: Dn xut halogen mch h (C2H5Br, C2H5Cl), dung dch NaOH 10% (trong nc, khng ln ion halogen), dung dch HNO3 20%, dung dch AgNO3 1%. Cho 0.5ml dn xut halogen v 2-3 ml nc ct vo ng nghim ri lc u. hn hp tch thnh 2 lp, gn b lp nc trn sang ng nghim khc cha sn vi git AgNO3. Nu thy c kt ta bc halogenua, tip tc tin hnh nh trn n khi th nc ra khng cn ion halogen. Sau cho 2 ml dung dch NaOH 10% vo ng nghim cha dn xut halogen. Lc nhv un hn hp phn ng n si. ngui, gn lp nc trn sang ng nghim khc, axit ha lp nc ny bng HNO3 20% v nh thm vi git dung dch AgNO3. Nhn xt hin tng xy ra.
?
1. Nu mc ch ca th nghim. 2. Gii thch qu trnh tin hnh th nghim. 3. Vit cc phng trnh phn ng xy ra. 4. Nu d kin kt qu th nghim thu c khi thay dung dch NaOH trong nc bng dung dch NaOH trong ancol. 3.7. PHN NG CLOROFORM VI DUNG DCH KIM Ha cht: Cloroform, dung dch NaOH 10%(trong nc, khng ln ion halogen), dung dch HNO3 20%, dung dch dung dch Amoniac 10%, dung dch KMnO4 1%. Cho 1ml CHCl3 ra sch ionhalogen (xem th nghim 5.6) v 3ml dung dch NaOH 10% vo ng nghim. Lc u v cn thn un si hn hp. Lm lnh hn hp phn ng, gn ly phn dung dch trong pha trn ri chia thnh 3 phn: Phn th nht c axit ha bng HNO3, sau nh thm vi git dung dch AgNO3 1%. Nhn xt hin tng xy ra.
Trang 164
Cho 1ml dung dch bc amoniacat vo phn th hai v un nng nh. Quan st hin tng kt ta bm vo thnh ng nghim.
1. Nu mc ch ca th nghim. 2. Gii thch qu trnh tin hnh th nghim 3. Vit cc phng trnh phn ng xy ra. 3.8. KH NNG PHN NG CA NGUYN T HALOGEN LIN KT VI NHN THM Ha cht: Clobenze hoc brombenzen, dung dch NaOH 10% (trong nc, khng ln halogen), dung dch HNO3 10%, dung dch AgNO3 1%. Cho 0.5ml clobenzen loi ht halogen (xem th nghim 5.6) v 1- 2ml dung dch NaOH 10% vo ng nghim. Lc u v un hn hp n si. Lm lnh hn hp, gn ly phn dung dch pha trn. Axit ha phn bng dung dch HNO3 20%, nh thm 1-2 git dung dch AgNO3 1%. Quan st xem c hin tung kt ta hay khng?
?
1. Nu mc ch ca th nghim 2. T kt qu th nghim hy rt ra nhn xt v kh nng phn ng ca dn xut halogen thm. Gii thch.
3.9. KH NNG CA PHN NG CA NGUYN T HALOGEN LIN KT VI MCH BN CA NHN THM. Ha cht: Benzyl clorua, dung dch NaOH 10% (trong nc, khng ln ion halogen), dung dch HNO3 20%, dung dch AgNO3 1%. a/ Cho 0.5ml benzyl clorua loi ht ion halogen (xem th nghim 3.6) v 1-2ml dung dch NaOH 10% vo ng nghim. Lc u v un cn thn hn hp n si. Lm lnh hn hp ri gn ly phn dung dch trong pha trn. Axit ho phn dung dch va gn c bng HNO3 20% v nh thm vo 1-2 git dung dch AgNO3 1%. Quan st hin tung xy ra. b/ Cho 0.5ml enzyl clorua loi ht ion halogen, v 1-2ml nc ct vo ng nghim. Lc u v un cn thn hn hp n si. Lm lnh hn hp, gn ly phn dung dch trong trn. Nh vo phn dung dch trong 1-2git dung dch AgNO3 1%. Quan st hin tung xy ra.
?
1. Nu mc ch ca th nghim. 2. T cc kt qu th nghim phn a/ v b/ hy rt ra nhn xt v kh nng phn ng ca ca dn xut halogen c nguyn t halogen lin kt vi mch ben ca nhn thm. Gii thch. 3. Vit cc phng trnh phn ng xy ra.
Trang 165
Bi 4: ANCOL 4.1. IU CH ANCOL ETYLIC TUYT I Ha cht: Ancol etylic 960, CuSO4.
PHENOL ETE
Cho 1g CuSO4 vo chn s, un nng chn s cho n khi c CuSO4 khan (c mu trng). ngui. Cho CuSO4 khan v 2-3 ml ancol etylic 960 vo ng nghim kh. Lc u hn hp v un nng nh ng nghim. Nhn xt s thay i mu ca CuSO4. Gn ancol etylic tuyt i sang ng nghim kh lm th nghim 6.2. 4.2. PHN NG CA ANCOL ETYLIC VI NATRI Ha cht: Ancol etylic tuyt i, natri kim loi, phenolphtalein (dung dch 1% trong ancol etylic). Cho mt mu Na (bng ht u xanh nh) c co sch (lp oxit) vo ng nghim kh cha sn 2ml ancol etylic khan. Bt ming ng nghim bng ngn tay ci. Khi phn ng kt thc, a ming ng nghim li gn ngn la n cn v b ngn tay bt ming ng nghim ra. Kt ta trng cn li trong ng nghim c ha tan bng 0.5 1.0ml nc ct. Nh vo ming ng nghim mt vi git phenolphtalein. Nhn xt cc hin tng xy ra trong qu trinnh2 th nghim.
?
1. Nu mc ch ca th nghim 2. Ti sao phi dng ancol etylic tuyt i 3. Vit cc phng trnh phn ng xy ra.
4.3. OXI HA ANCOL ETYLIC BNG NG (II) OXIT Ha cht: Ancol etylic, dy ng (un thnh vng xon), dung dch axit fucsinsunfur (thuc th Sip). Cho 0.5 1.0ml ancol etylic vo ng nghim kh. Nung nng si dy ng (phn vng xon) trn ngn la n cn cho ti khi to ra lp ng (II) oxit mu en. Nhng ngay si dy ng ang cn nng vo ng nghim cha ancol etylic. Quan st s bin mu ca si dy ng. Lp li qu trnh trn vi ln. Nh vo ng nghim 5-6 git dung dch axit sunfur. Quan st s thay i mu ca dung dch (xem th nghim v phn ng mu andehit, chng VII).
?
1. Gii thch qu trnh tin hnh th nghm v cc hin tng xy ra. 2. Vit cc phng trnh phn ng xy ra.
Trang 166
4.4. OXI HA ANCOL ETYLIC BNG DUNG DCH KALI PERMANGANAT Ha cht: Ancol etylic, dung dch KMnO4 0.1N, dung dch H2SO4 2N , dung dch axit fucsinsunfur (thuc th Sip). Cho 1ml ancol etylic, 1ml dung dch KMnO4 0.1N v 1ml dung dch H2SO4 2N vo ng nghi. un nng nh ng nghim trn ngn la n cn (un nng nh trnh ru, c bit sn phm sinh ra d bay hi) v quan st s thay i mu ca dung dch. Nu dung dch vn cn mu tm hng th thm vo vi tinh th natri sunfit hoc tinh th natri hidrosunfit. Sau khi hn hp phn ng mt mu hon ton, nh vo 5- 6 git dung dch axit fucsinsunfur. Quan st mu ca hn hp.
?
1. Gii thch s bin i mu ca dung dch trong qu trnh th nghim. 2. Vit cc phng trnh phn ng xy ra.
4.5. PHN NG CA ANCOL VI THUC TH LUCA Ha cht: Ancol n-propylic, ancol iso propylic, ancol tert-butylic, thuc th Luca (ZnCl2 trong HCl c). Cho vo ng nghim kh, mi ng nghim 0.5ml mt trong cc ancol sau ancol n-propylic, ancol iso propylic, ancol tert-butylic. Cho tip vo mi ng 1.5ml thuc th Luca. Lc u hn hp, sau yn trn gi ng nghim khong 2-3 pht. Quan st hin tng phn lp, c) xy ra trong 3 ng nghim.
?
1. Nu mc ch ca th nghim 2. Nhn xt g c rt ra t kt qu th nghim? Vit phng trnh phn ng. 3. Trong phn ng vi thuc th Luca, ancol th hin tnh cht g (axit hay baz) ?
4.6. PHN NG CA ETYLENGLYCOL V GLIXERIN VI NG (II) HIDROXIT Ha cht: Etylenglycol, glixerin, ancol etylic, dung dch CuSO4 2%, dung dch NaOH 10%, dung dch HCl 10%. Chun b ba ng nghim, cho vo mi ng 3-4 git dung dch CuSO4 2% v 2-3ml dung dch NaOH 10%. Lc nh. Tip tc nh vo ng th nht 2-3 git etylenglycol, ng th hai 2-3 git glixerin, ng th 3 2-3 git ancol etylic. Lc nh c 3 ng nghim v quan st cc hin tng (mu sc dung dch, kt ta) xy ra. Sau thm vo 3 ng nghim tng git dung dch HCl v quan st cc hin tng (mu sc dung dch.) xy ra.
?
1. Nu mc ch ca th nghim. 2. Vit cc phng trnh phn ng xy ra. 3. Cho bit mi trng ( axit hay baz) ca phn ng giaetylenglycol hoc glyxerin vi ng (II) hidroxit?
Trang 167
4.7. PHN NG EHYDRAT HA GLIXERIN Ha cht: Glixerin, kali hoc natri hidrosufat khan, dung dch axit fucsinsunfur. Cho khong 1g kali hydrosunfat khan vo ng nghim kh v nh thm vo 5-6 git glixerin. un nng mnh ng nghim v t mt mnh nh giy lc c tm dung dch axit fucsinsunfur ln ming ng nghim. Nhn xt mi c trngca sn phm v quan st s xut hin mu ca mnh giy lc.
?
1. Vai tr ca kalihydrosunfat khan v axit fucsinsunfur trong th nghim? 2. Vit cc phng trnh phn ng xy ra. 4.8. IU CH DIETYLETE (ETE ETYLIC) Ha cht: Ancol etylic, H2SO4 c. Cho 1ml ancol etylic vo ng nghim kh, cho tip tng git t t tng git H2SO4 c (1ml) v lc u. un hn hp cn thn n si nh. a ng nghim ra xa ngun nhit v nh t t 5-10 git ancol etylic theo thnh ng nghim vo hn hp ang nng. Nhn xt mi c trng ca dietyl ete bay ra. Sau y ng nghim bng nt c ng dn kh vut nh u pha trn. Tip tc un nng cn thn hn hp v dng que dim chy t ete thot ra t ng dn kh. Nhn xt mu ngn la chy ca ete.
?
1. Ti sao cn nh thm ancol etylic vo hn hp ancol etylic v axit sunfuric? 2. Vit cc phng trnh phn ng xy ra. 3. Ngn la chy ca dietyl ete sng hn ngn la chy ca ancol etylic. Gii thch. 4.9. NHN BIT PEOXIT TRONG DIETYL ETE Ha cht: Dietyl ete ( bo qun lu), dung dch KI 1% (khng ln I2), dung dch h tinh bt Cho vo ng nghim 1ml dietyl ete, 1ml KI 1% v 0.5% dung dch H2SO4 10%. Lc nh ng nghim. Nhn xt mu ca dung dch. Nh thm 2 git dung dch h tinh bt 0.5% vo hn hp v lc nh. Tip tc quan st mu ca dung dch.
?
1. Khi lu trong khng kh, c bit c chiu sng, dietyl ete b oxi ha bi oxi khng kh
to ra hp chthidropeoxit. Vit phng trnh phn ng oxi ha dietyl ete bi oxi khng kh. 2. M t cc hin tng xy ra v vit phng trinh phn ng ca hidropeoxit vi KI trong mi trng axit. 4.10. PHN NG CA PHENOL VI NATRI HIDROXIT V MUI NATRI CACBONAT
Trang 168
Ha cht: Dung dch bo ha phenol trong nc, dung dch NaOH 2N, dung dch Na2CO3 2N, dung dch NaHO3 2N, dung dch HCl 2N. a/ Cho 1ml dung dch phenol vo ng nghim v cho thm t t tng git dung dch NaOH 2N n khi c dung dch trong sut. Chia hn hp thnh hai phn lm tip cc th nghim sau: Cho t t tng git dung dch HCl vo phn th nht, lc nh v quan st hin tng xy ra. Dn lung kh CO2 d vo phn th hai. Quan st hin tng xy ra.
b/ Cho vo hai ng nghim,mi ng 1mL dung dch phenol bo ha trong khi lc nh thm vo ng th nht 1ml dung dch Na2CO3 2N v vo ng th hai 1ml dung dch NaHCO3 2N. Theo di hin tng xy ra c hai ng nghim.
?
1. Nu mc ch ca th nghim 2. Nhng nhn xt c rt ra t cc kt qu th nghim? 3. Vit cc phng trnh phn ng xy ra.
4.11. PHN NG CA CC PHENOL VI ST (III) CLORUA Ha cht: Dung dch phenol 5%, dung dch m-crezol 5%, dung dch p-crezol 5%, dung dch FeCl3 5%, ancol etylic, dung dich HCl 2N. Cho vo 3 ng nghim, mi ng mt ml dung dch ca mt trong cc cht sau: phenol 5%, m-crezol 5%, p-crezol 5%. Cho tip vo mi ng mt git dung dch FeCl3 1% v lc nh. Nhn xt s i mu ca cc dung dch. Mi dung dch c chia thnh 2 phn. Nh t t tng git ancol etylic vo phn th nht v dung dch HCl 2N vo phn th hai cho n khi dung dch mt mu. 4.12. PHN NG BROM HA PHENOL Ha cht: Dung dch phenol 5%, dung dch bo ha brom trong nc Cho 0.5ml dung dch phenol vo ng nghim v nh tip tng git dung dch nc brom, ng thi lc nh dung dch cho n khi xut hin kt ta. Tip tc nh tht d nc brom vo dung dch. Nhn xt s bin i mu sc ca dung dch.
?
1. Nu nc ch ca th nghim 2. Vit cc phng trnh phn ng xy ra. 3. T kt qu ca th nghim hy rt ra kt lun v kh nng phn ng th ca phenol. Gii thch. 4.13. IU CH AXIT PICRIC (2,4,6 - TRINITROPHENOL)
Trang 169
Ha cht: Phenol, axit sunfuric c, axit nitric c (D = 1.5 g/ml) Cho 0.5g phenol v 1.5ml H2SO4 c vo ng nghim, sau un nng hn hp thu c cht lng ng nht. Rt cn thn hn hp lng c lm ngui sang ng nghim khc c cha sn 2ml nc lnh. Nh t t axit nitric c vo hn hp v lc u. Dung dch nhm mu ti. un nng hn hp trn ni nc nng trong vng 15 pht. Sau khi lm lnh em pha long bng mt th tch nc tng ng. Axit picric kt ta dng tinh th mu vng.
?
1. i ch axit picric ngi ta phi tin hnh phn ng sunfo ha trc phn ng itro ha. Gii thch. 2. Vit cc phng trnh phn ng xy ra.
4.14. IU CH PHENOLPHTALEIN Ha cht: Phenol, anhydric phtalic, axit sunfuric c (D = 1,84g/ml), dung dch NaOH 2N, dung dch HCl 2N. Cho 0.05 0.1 g anhydric phtalic (nghin nh) 0.1 0.2g phenol v 3-4 git H2SO4 c vo ng nghim kh. un nng hn hp n nng chy (hn hp nhum mu ti) trn ngn la n cn trong vng 2 3 pht. Lm ngui hn hp, rt vo 5-6ml nc. un nng nh ng nghim sn phm mau tan. Ly mt git dung dch nh trn t giy lc. Sau khi git dung dch thm ht vo giy, em nh thm vo gia vt thm 1 git dung dch kim. Nhn xt mu ca vt thm trn giy lc. Nh ln vt thm c mu 1 git dung dch HCl. Nh tip vo 1 git dung dch kim. Theo di s bin i mu trn vt thm.
?
1. Vit phng trnh phn ng iu ch phenolphtalein 2. Gii thch hin tng bin i mu ca phenolphtalein trong mi trng baz v mi trng axit.
Trang 170
Bi 5: ANEHIT 5.1. IU CH AXETANDEHIT T AXETILEN
XETON
Ha cht: Cnxi cacbua (t n), thu ngn oxit, axit sunfuric c, dung dch axit fucsinsunfur. Cho vo bnh cu 1 (hnh v ) vi vin canxi cacbua. Cho vo ng nghim (2) khong 0.1g HgO. Rt vo ng nghim (3) khong 1 2 ml nc lnh v vi vin nc nh.
Sau khi chun b xong mi lp dng c nh hnh v. H thng ng dn kh phi tht kn. t ng nghim (2) trong cc nc nng (nhit khong 80 900C v duy tr nhit ny trong sut thi gian th nghim). t ng nghim (3) trong cc nc . T phu nh git (6) nh tng git nc lnh xung bnh cu vi tc va phi c th m c tng bt kh axetilen i sang ng nghim (2) trong thi gian 10 pht. Nhn xt hin tng xy ra ng nghim (2). Axetandehit (t0si : 20.80C) c dng kh axetilen d cun theo sang ng nghim (3) v tan vo nc lnh. Nh vo ng nghim (3) vi git dung dch axit fucsinsunfur. Theo di mu ca dung dch trong ng nghim (3).
?
1. Vit cc phng trnh phn ng xy ra. 2. Phn ng cng nc vo axetilen xy ra ng nghim no? Cht xc tc ca phn ng? Ti sao phi t ng nghim 3 trong cc nc ?
5.2. IU CH ACETON T CANXI ACETAT Ha cht: Canxi acetat khan (nghin nh thnh bt), dung dch NaOH 10%, dung dch HCl 10%, iot tinh th. Cho canxi acetat khan vo ng nghim kh (lng canxi acetat chim khong chiu cao ng nghim). y ng nghim bng nt c ng dn kh cong. u cui ca ng dn kh nhng vo ng nghim hng cha sn 1 1.5ml H2O (xem hnh 1, chng I). un nng nh ton b ng nghim, sau tp trung un nng phn cha canxi acetat trong khong 5-7 pht. Nhn xt s tng th tch ca dung dch trong ng nghim hng. Cho vi tinh th iot vo dung dch trong ng nghim hng lc u v cho thm tng git dung dch NaOH 10% cho n khi mt mu iot. Theo di hin tng kt ta trong dung dch.
Trang 171
Sau khi lm lnh ng nghim cha hn hp phn ng ban u, nh vo 1 2 ml dung dch HCl 10%. Theo di hin tng si bt kh.
?
1. Vit phng trnh phn ng iu ch axeton tcanxi axeta.t 2. Ti sao c s tng th tch dung dch trong ng nghim hng? 3. Mc ch ca th nghim cho iot v dung dch NaOH vo dung dch trong ng nghim hng cho dung dch HCl vo ng nghim cha hn hp phn ng ban u? 5.3. PHN NG MU CA ANDEHIT VI AXIT Ha cht: Dung dch fomendehit 40%,dung dch axetandehid 20%, dung dch axit fucsinsunfur, dung dch HCl c. Dung dch axit fucsinsunfur c iu ch bng cch ha tan 0.2g fucsin (rosanilin) trong 200ml nc ct v cho thm vi ml dung dch nc bo ha kh SO2 (hoc 2g NaHSO3 v 2ml dung dch HCl c). Nu sau 15 20 pht m dung dch khng mt mu th cho thm mt t tha hot tnh, lc cho n khi mt m, sau lc b than hot tnh.. Thuc th c gi trong bnh kn, trnh nh sng. Lng d ca SO4 trong thuc th cng t, thuc th cng nhy. Cho vo hai ng nghim, mi ng hai git dung dch axit fucsinsunfur. Nh vo ng nghim th nht 5 git dung dch axetandehit 20%. Nhn xt hin tng xut hin mu c hai ng nghim.
?
1. Bn cht ca phn ng mu gia andehit vi axit fucsinsunfur? Ti sao cc xeton khng c phn ng vi axit fucsinsunfur. 2. Gii thch cc kt qu th nghim. 5.4. PHN NG OXI HA ANDEHIT BNG HP CHT PHC CA BC (THUC TH TOLEN) Ha cht: Dung dch fomandehit 5% (hoc dung dch axetandehit), dung dch AgNO3 1%, dung dch NaOH 10%, dung dch NH3 5%. Cc ng nghim dng trong th nghim ny phi ra tht sch bng cch nh vo my git dung dch kim un nng nh, trng u, sau i v trng ng nghim bng nc ct. Cho vo ng nghim ( ra sch) 1ml dung dch AgNO3 1%, lc ng nghim v nh thm t t tng git NH3 5% cho n khi va ha tan kt ta bc oxit (thuc th Tolen s km nhy nu cho d dung dch NH3). Nh vi git dung dch fomandehit vo dung dch thuc th Tolen. un nng hn hp vi pht trn ni nc nng 60-700C. Quan st lp bc kim loi bm trn thnh ng nghim (i khi bc kim loi tch ra dng kt ta v nh hnh mu en).
Trang 172
Tin hnh th nghim tng t vi axetandehit.

?
1. Vit cc phng trnh phn ng xy ra. 2. Ti sao cn ra sch ng nghim bng dung dch kim trc khi tin hnh th nghim? 5.5. PHN NG OXI HA ANDEHIT BNG NG (II) HIDROXIT Ha cht: Dung dch fomendehit 5%, dung dch NaOH 10%, dung dch CuSO4 2%. Cho 1ml dung dch fomandehit 5% v 1ml dung dch NaOH 10% vo ng nghim. Lc hn hp v nh t t tng git CuSO4 2% cho n khi xut hin huyn ph. un nng phn trn ca hn hp trn ngn la n cn cho n si, cn phn di ca hn hp so snh. Quan st hin tng bin i t mu xanh nht (ca huyn ph) sang mu vng (ca kt ta) ri mu (ca kt ta).
?
1. Vit phng trnh phn ng oxi ha andehit fomic n axit fomic bi ng (II) hidroxit. 2. Nhng hp cht no (ca ng) c mu xanh nht, mu vng, mu ? 5.6. PHN NG OXI HA ANDEHIT BNG THUC TH FELING Ha cht: Dung dch fomandehit 5%, dung dch thuc th feling. Thuc th feling l hn hp ca dung dch feling A v feling B. Feling A: Ho tan 34.6g CuSO4.5H2O trong 500ml nc. Feling B: Ho tan 173g mui natrikali tactrat, 70g NaOH trong 500ml nc. Khi cn lm th nghim, ngi ta trn hai th tch bng nhau ca dung dch Feling A v B s c dung dch xanh thm, gi l thuc th Feling. Cho 1ml dung dch thuc th Feling v 1-2 git dung dch fomadehit vo ng nghim. un nng nh hn hp trn ngn la n cn. Quan st hin tng xy ra trong hn hp.
?
1. Vit phng trnh phn ng xy ra khi trn Feling A vi Feling B. 2. Vit phng trnh phn ng oxi ha andehit fomic bng thuc th Feling to ra axit fomic. 3. Dng thuc th Feling oxi ho andehit thun li hn dng ng (II) hidroxit. Gii thch. 5.7. PHN NG CA AXETON V ANDEHID BENZOIC VI NATRI HIDROSUNFIT. Ho cht: Axeton, andehit benzoic, dung dch bo ha NaHSO3, dung dch HCl 10%, dung dch Na2CO3 10% .
Trang 173
a/ Rt 3ml dung dch bo ha NaHSO3 vo ng nghim. Lc mnh v cho tip 1ml axeton vo dung dch cha NaHSO3. Hn hp to nhit. t ng nghim trong cc nc v quan st s xut hin kt ta tinh th trong ng nghim. Nu hin tng kt ta xy ra chm th c th khi mo kt ta bng cch dng a thu tinh c nh vo thnh ng nghim (ch c dung dch). Lc ly kt ta tinh th. Chia thnh hai phn v cho vo hai ng nghim. Rt vo phn th nht 1ml dung dch HCl 10%, vo phn th hai 1ml dung dch Na2CO3 10%. un nng nh c hai ng nghim v nhn xt mi bay ln (cn thn khi ngi mi). b/ Rt 0.5ml benzoic, 2ml dung dch bo ha NaHSO3 vo ng nghim v lc mnh. Mi c trng ca andehit benzoic dn dn bin mt v sn phm to ra dng tinh th. Tip tc lc hn hp ti khi lng kt ta khng tng ln. Rt 6-8ml nc vo hn hp v t ng nghim vo ni nc nng. Quan st hin tng xy ra (lng kt ta, mi).
1. Nu mc ch ca th nghim. 2. Vit cc phng trnh phn ng xy ra. 3. Nu thay oxeton trong th nghim trn bng metyletylxeton hoc dietylxeton th phn cng c xy ra khng?
5.8. PHN NG TO 2,4-DINITROPHENYLHIDRAZON CA BENZANDEHIT V AXETON Ha cht: Benzandehit, axeton, dung dch 2,4 dinitro phenyl hydrazin hidroclorua. Cho vo ng nghim 1-2m dung dch 2,4-dinitrophenylhidrazin v 1-2 git benzandehit. Lc nh hn hp. Theo di hin tng xy ra(kt ta, mu). Lc v ra kt ta bng nc, sy kh sn phm dng cho th nghim 7.14 Tin hnh th nghim tng t i vi axeton.
?
1. Vit cc phng trnh phn ng xy ra. 2. Ti sao phi dng 2,4-dinitrophenylhidrazin dng mui vi axit clohidric? 5.9. PHN NG TO RA SEMICACBAZON CA AXETON Ha cht: Axeton, semicacbazit hidroclorua, kali axxetat. Ha tan 0.5g semicacbazit hidroclorua trong 2ml nc sau cho tip 0.2m axeton v 0.4g kali axxetat. y ng nghim bng nt v lc mnh hn hp trong 2-3 pht. y ng nghim bng nt v lc mnh hn hp trong 2-3 pht. t ng nghim vo cc nc lnh v quan st s xut hin kt ta.
?
1. Ti sao phi a thm kali axxetat vo hn hp phn ng? 2. Vit cc phng trnh phn ng xy ra.
Trang 174
5.10. PHN NG NGNG T ANDOL V CROTON CA ANDEHIT AXETIC Ha cht: Andehit axetic, dung dch NaOH 10%. Rt 3ml dung dch NaOH 10% vo ng nghim. Cho thm 5-6 git andehit axetic v un nng nh hn hp. Lc u phn ng to ra andol (c mi d chu), sau andol chuyn thnh andehit crotonic (c mi kh chu, cn cn thn khi ngi mi). Khi tip tc un nng lu hn, cht lng chuyn thnh nha mu nu.
?
1. Vit cc phng trnh phn ng ngn t ca andehit axetic. 2. Ti sao khi un nng lu, cht lng chuyn thnh nha. 5.11. PHN NG CA ANDEHIT BENZOIC VI DUNG DCH KIM (Phn ng Kanizaro - Tisenco) Ha cht: Andehit benzoic, dung dch KOH 10% (trong ancoletylic, va mi pha), kali bicromat (bt) axit sunfuric c. Rt 5ml dung dch KOH 10% (trong ancol etylic) vo 1ml andehit benzoic trong ng nghim v lc u. Hn hp pht nhit v xut hin khi ng c cc tinh th sn phm (tinh kali banzoat). Lc ly phn kt ta tinh th, ri chuyn vo ng nghim. Cho thm vo 4-5ml nc, lc cho tan ht kt ta, ri rt thm 1ml dung dch HCl long. Theo di s xut hin kt ta. Chuyn phn dung dch lc (sau khi lc ly phn kali benzoat trn phu) vo ng nghim v un trong ni nc si lm bay hi phn ln ancol etylic. Cho 1-2ml nc, mt t bt kali bicromat v 1ml axit sunfuric c vo phn cn li trong ng nghim. un hn hp n si trn ngn la n cn. Nhn xt mi ca hn hp.
?
1. Vit cc phng trnh phn ng xy ra. 2. Ti sao phi dng dung dch kim trong ancol etylic? 3. Cho bit c im cu to phn t ca cc andehit c kh nng tham gia phn ng Kanizaro Tisenco.
Trang 175
Bi 6:
AXIT CACBOXYLIC V DN XUT
6.1. TNH CHT AXIT CA AXIT CACBOXYLIC Ha cht: Dung dch CH3COOH 10%, axit axetic kt tinh, dung dch Na2CO3 10%, Mg (bt), dung dch Metyl da cam, dung dch qu xanh, dung dch phenolphtalein 1% (trong ancol etylic). a/ Nh vo ba ng nghim, mi ng 1 -2 git dung dch CH3COOH 10%. Thm vo ng th nht 1 git metyl da cam, ng th hai mt git qu xanh, ng th ba mt git phenolphtalein. Theo di s bin i mu trong c ba ng nghim. b/ cho thm mt t Magi bt (bng ht u xanh). y ng nghim bng nt c ng dn kh thng, u pha trn c vut nh (xem hnh 5). a u que dim ang chy vo u vut nh ca ng dn kh. Quan st hin tng bng chy ca ngn la. c/ Cho khong 0.1 0.2 gam CuO vo ng nghim. Rt tip vo 2 3ml axit axetic v un nh hn hp trn ngn la n cn. Quan st mu ca dung dch. d/ Rt 1 2 ml axit axetic kt tinh vo ng nghim cha sn 1 2ml dung dch Na2SO3 10%. a que dim ang chy vo ming ng nghim. Quan st hin tng xy ra trong dung dch v ngn la u que dim.
?
1. Nu cc hin tng xy ra trong qu trnh th nghim v gii thch. 2. Vit cc phng trnh phn ng xy ra 3. Nhng kt lun no c rt ra t cc kt qu th nghim. 6.2. PHN NG OXI HA AXIT FOMIC Ha cht: Axit formic, dung dch NaOH 10%, dung dch AgNO3 1%, dung dch NH3 5%, dung dch H2SO4 10%, dung dch KMnO4 5%, dung dch nc vi trong. a/ Oxi ha axit fomic bng thuc th Tolen Cho vo ng nghim th nht 1 2 ml dung dch AgNO3 1%, cho tip khong 1 2 git dung dch NaOH 10% ti khi thy xut hin kt ta. Nh thm tng git dung dch NH3 5% va ha tan kt ta. Cho vo ng nghim th hai 0.5ml axit fomic, nh thm tng git dung dch NaOH 10% cho ti khi t mi trng trung tnh (th bng giy qu trung tnh). Rt hn hp trong ng nghim hai vo hn hp trong ng nghim mt. un nng hn hp phn ng trong ni nc nng 60 700C. Nhn xt hin tng xy ra trong ng nghim. b/ Oxi ha axit fomic bng dung dch kali permanganat
Trang 176
Cho 0.5ml axit fomic, 0.5ml dung dch H2SO4 10%, v 1ml dung dch KMnO4 5% vo ng nghim. y ng nghim bng nt c ng dn kh cong, u cui ca ng dn kh nhng vo ng nghim cha sn 2ml dung dch nc vi trong. un nng ng nghim cha hn hp phn ng. Quan st hin tng xy ra trong ng nghim cha hn hp phn ng v ng nghim cha nc vi trong.
1. Nu mc ch ca th nghim. 2. Nu cc hin tng xy ra trong qu trnh th nghim. 3. Vit cc phng trnh phn ng xy ra.
6.3. PHN NG OXI HA AXIT OXALIC Ha cht: Dung dch axit oxalic bo ha, dung dch KMnO4 5%, dung dch H2SO4 10%, dung dch nc vi trong. Cho vo ng nghim 3 4ml dung dch KMnO4 5%, 1 2ml dung dch H2SO4 10% v 1ml dung dch axitoxalic bo ha. y ng nghim bng nt c ng dn kh cong. u cui ca ng dn kh c dn vo ng nghim khc cha sn 1 2 ml dung dch nc vi trong. un nng cn thn hn hp phn ng. Nhn xt s bin i mu trong ng nghim cha nc vi trong.
?
1. Nu mc ch ca th nghim. 2. Nu cc hin tng xy ra trong qu trnh th nghim v vit cc phng trnh phn ng.
6.4. TNH CHT CA AXIT OLEIC Ha cht: Axit oleic, nc brom bo ha, dung dch KMnO4 2%, dung dch Na2CO3 10%. a/ Phn ng ca axit oleic vi nc brom Cho vo ng nghim khong 0.5ml axit oleic v 2ml nc brom. Lc mnh hn hp. Theo di s bin i mu ca nc brom. b/ Phn ng ca axit oleic vi dung dch kali permanganat Cho khong 0.5ml axit oleic, 1ml dung dch KMnO4 5% v 1ml dung dch Na2CO3 10% vo ng nghim. Lc mnh hn hp. Quan st s bin i mu ca dung dch kali pemanganat.
?
1. Nu mc ch ca cc th nghim. 2. Vit cc phng trnh phn ng xy ra.
6.5. IU CH V THU PHN AXETAT Ho cht: Dung dch Natri axetat 10%, dung dch st (III) clorua 3%. Nh 2 -3 git dung dch CH3COONa 10% vo ng nghim, nh thm vi git dung dch FeCl3 3%. Dung dch nhm mu sm ca hp cht phc (tan trong dung dch).
Trang 177
un si dung dch. Hp cht phc ca st b thu phn, to ra mui baz ca st dng kt ta bng mu nu .
?
1. Vit phng trnh phn ng iu ch v thu phn st (III) axetat. 2. Nu mt s ng dng ca phn ng thu phn st (III) axetat. 6.6. IU CH ETYL AXETAT Ha cht: Ancol etylic, axit axetic kt tinh, axit sunfuric c, dung dch natri clorua bo ha. Cho vo ng nghim th nht (kh) 2ml ancol etylic, 2ml axit axetic kt tinh v 2 git axit sunfuric c. Cho vo ng nghim th hai (kh) lng ancol etylic, 2ml axit axetic kt tinh tng t nh ng nghim th nht. Lin tc lc u hai ng nghim v ng thi un nng 8 10 pht trong ni nc nng 65 70 C (khng c un si phn ng!) Sau lm lnh c hai ng nghim. Rt vo mi ng 3 4 mldung dch natri clorua bo ha. Theo di s phn lp cht lng v so snh lng cht lng lp trn trong c hai ng nghim.
?
0
1. Cho bit vai tr ca axit sunfuric trong th nghim iu ch este. 2. Etyl axetat hu nh khng sinh ra khi cho qu d axitsunfuric vo hn hp phn ng. Gii thch. 3. Vit phng trnh phn ng iu ch ety axetat tancol etylic v axit axetic. 4. Ti sao phi cho dung dch natriclorua bo ha vo hn hp sn phm? Este nm lp trn hay lp di? Ti sao? 6.7. PHN NG THU PHN ESTE Ha cht: Etyl axetat, dung dch H2SO4 20%, dung dch NaOH 30%. Cho vo 3 ng nghim, mi ng cha 2ml etyl axetat. Cho thm vo ng th nht 1ml nc, ng th hai 1ml dung dch H2SO4 20%, ng th ba 1ml dung dch NaOH 30%. Lc u c 3 ng nghim, ng thi un nng 5 10 pht trong ni nc nng 65 750C. Sau khi ngng un, so snh lp este cn li trong c ba ng nghim.
1. Nu mc ch ca th nghim. 2. Vit phng tnh phn ng thu phn ety axetat trong ba mi tng phn ng. 3. Nhng nhn xt no c rt ra t cc kt qu th nghim?

14 Hoa Hoc Huu Co (PHU) PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

14 Hoa Hoc Huu Co (PHU) PDF

Uploaded by

Copyright:

Available Formats

B CNG THNG TRNG CAO NG CNG NGHIP TUY HA KHOA CNG NGH - MI TRNG

Tuy Ha, nm 2007

Bi 4- Ancol phenol ete Bi 5- Anehit xeton Bi 6- Axit cacboxylic v dn xut

165 170 175

Hp cht mch h (hp cht khng vng)

Hp cht mch vng (hp cht vng)

Vng no Vng khng no Vng thm

D vng no D vng khng no D vng thm

Chng 1: i cng v ho hc hu c 1.1.4. Ngun hp cht hu c

Ca(OH)2 CaCO3 CuSO4

hp cht hu c Fe2+ 4Fe3+ + + 6CN-

28 1 p f V 22400 760 1 + t 273 mN 2 a 100

Lp cng thc phn t da vo khi lng cc nguyn t:

+ + + + 109o28/ Hnh 1.3: S lai hoa sp3 -

Chng 1: i cng v ho hc hu c Th du:

Hnh 1.5: S lai ho sp2

Chng 1: i cng v ho hc hu c (hnh 1.7).

Hnh 1.7: S lai ho sp

Lin kt hiro ni phn t: l lin kt gia X H v Y ca mt phn t. Th d:

c) S nh hng ca lin kt hiro n tnh cht ca hp cht hu c

7,4 0,6 83 0,01

Chng 2: Cc hin tng ng phn trong ha hu c

Chng 2: CC HIN TNG NG PHN TRONG HA HU C

Hay: C6H4CH3OH c cc ng phn v v tr nhm OH sau:

Chng 2: Cc hin tng ng phn trong ha hu c

V bc ca nhm chc: CH3 CH2 CH2 NH2 ; CH3 NH CH2 CH3

Chng 2: Cc hin tng ng phn trong ha hu c

C=C cis - cis

CH3 H C CH3 C H H H CH3 H H CH3 C H C H

Chng 2: Cc hin tng ng phn trong ha hu c

Chng 2: Cc hin tng ng phn trong ha hu c

180(n 2) , trong n l s cnh mch vng. 2

lch c tnh theo cng thc:

1090 28 x , trong x l gc ha tr ca vng. 2

Chng 2: Cc hin tng ng phn trong ha hu c

Dng thuyn (cu dng C)

Dng gh (cu dng Z)

Chng 2: Cc hin tng ng phn trong ha hu c a) Cht hot ng quang hc c C i xng

Hnh 2.4: Cu trc dn xut ca metan

Chng 2: Cc hin tng ng phn trong ha hu c

hay: H H CH3 OH HO H CH3 CH3

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 24

HO CH2 COOH c pKa = 3,0;

Cl CH2 COOH c pKa = 2,9.

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 25

3.1.1. Khi nim hiu ng cm ng

3.1.2. Phn loi hiu ng cm ng

X c m in ln v trung tm gy ra hiu ng cm ng: dng cm ng c biu th bng mi tn dc theo lin kt.

+ > +/ > +// , chiu ca tc

CH2 = CH - CH = CH2 butadien-1,3

CH2 = C - CH = CH2 CH3 isopren

CH2 = CH - Cl vinyl clorua

N p-quinon phenol piridin anilin

c im ca h lin hp: khng c lin kt xch ma v lin kt pi thun tu. Cc in t

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 27

R - CHO + CH3 - CH = CH - CH =CH - CHO

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 28

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 29

3.3. Hiu ng siu lin hp

Trng hp cc iion dng cng cacboni cng c tc dng nh ni i :

Chng 3: S tc dng tng h cc nguyn t trong phn t http://www.ebook.edu.vn Trang 30

3.4. Hiu ng khng gian

CH3 N CH3 + IC2H5 (1) N + IC2H5