1

Chng 1 C S HA I CNG 1.1. HA HU C CHT HU C 1.1.1. c im v s pht trin ca ho hc hu c. i tng nghin cu ca ho hc l nhng cht ho hc ring bit v s bin i ca chng. Mt lnh vc c bn ca ho hc l ho hc hu c nghin cu cc hp cht ca cacbon vi cc nghin t khc, ch yu l hp cht ca cacbon vi Hyr, Oxi, Nit, Phtpho, Lu hunh v Halogen. Nhiu hp cht hu c c con ngi bit rt lu nh: dm (axit axetic lng), mt s thuc nhum, ru etylic, cc hp cht axit oxalic, axit xitric, axit tactric v mt s baz hu c (cc ancaloit) c tch t ng thc vt vo cui th k th 18 v u th k th 19. Thi im ny cng c tnh l thi im u ca mn ho hc hu c. th k th 18 v th k th 19, ngi ta cho rng ho hc ca th gii cc cht SNG khc vi th gii ho hc ca cc cht cht, l c th sng c cu to t nhng hp cht c bit do mt ngoi lc sng (Tri, Cha, Pht) to nn m cc cht bn thn con ngi khng th tng hp c. Nhng nhng pht hin th k 19 cho thy rng tt c cc hp cht cu to nn c th ng vt v thc vt u c thnh phn ging nhau ph v s khc bit gia ho hc ng vt v thc vt. Hai lnh vc nghin cu ny st nhp vo nhau v hnh thnh mn ho hc hu c. Nh bc hc Thy in Berceluyci (1779-1848) c rt nhiu cng trong lnh vc st nhp ny. Sau ng, nh bc hc Lavuaze, bng nhng phng php phn tch nh lng pht hin c mt s nguyn t mi, xc nh c nguyn t lng ca nhiu nguyn t, t nn mng cho hin tng ng phn. Nh ho hc c Beler bng phn ng thu phn hp cht ixianua (v c) thu c axit oxalic (hu c) nm 1824 v t xinaoxit amoni (v c) thu c ur (hu c) nm 1828 ph v s phn bit gia hp cht v c v hu c. iu ny cng chng minh rng cc hp cht hu c c th thu nhn c bng con ng tng hp m khng cn s tham gia ca mt ngoi lc huyn b no c. iu c khng nh bng cc cng trnh ca Buttlerp tng hp cc hp cht ng t formalin (1861), Faray thu nhn c bezen (1825), Zinin tng hp c anilin t nitrobezen (1842) v t anilin thu nhn c cc hp cht mu vo nhng nm 50 ca th k 19. Cng vo nhng nm ny Gmelin a ra nh ngha ho hc hu c l ho hc cc hp cht cacbon v n ti n ngy nay. 1.1.2. Cu to ca cc hp cht hu c.

T nh ngha trn y xut hin mt vn ln l ti sao t hng trm nguyn t bit ch c cacbon to thnh nhiu hp cht nh vy? Th nht: do hin tng ng phn c Berceluyci pht hin cho tt c cc cht ho hc m c bit l cht hu c c th tn ti nhiu hp cht khc nhau c cng thnh phn nguyn t, cng phn t lng nhng khc nhau v cu to. V d: C20H42 c 366.319 hp cht khc nhau, C30H62 tn ti 4.111.846.768 hp cht khc nhau. Th hai: do hin tng ng ng - tn ti cc hp cht ho hc m thnh phn ca mi cht ch khc nhau bi mt nhm CH2 (mtylen). Th 3: do hin tng ng cp - cc hp cht c cu to cng mt s nguyn t cacbon nh nhau nhng hp cht sau c t hn hp cht trc 2 nguyn t Hyr (tan C2H6, tylen C2H4, axetylen C2H2). Vy ti sao cc hp cht hu c li tn ti di cc dng ng ng, ng phn? Trong cc thuyt a ra gii thch vn ny ca nhiu nh bc hc thuc nhiu th h khc nhau c th lu mt vi gi thit sau y: Thuyt kiu ca Zerar cc hp cht c phn b theo cc kiu H2O, HCl, H3N, H2. y ch cn thay th hyr ca cc kiu bng phn gc hu c th ta s thu c cc hp cht khc nhau. V d:
H O H nc CH3 O H mtanol C2H5 O H tanol C2H3O O H axit axetic

CH3

C2H5

C2H3O Cl axtylclorua
C2H3O H axtanhyt

Cl Cl Cl hyrclorua mtylclorua tylclorua

H H hyro CH3 H mtan C2H5 H tan

Nm 1851, Viliamxn a ra thuyt raical ca nhiu nguyn t - tc l cc raical c kh nng thay th 2 hoc nhiu hyr trong cc kiu.

V d: axit aminaxtic l kiu H2O v NH3

H O C2H3O H N H

c bit quan trng l kiu mtan ca Kkuk

H H C H H

Kkul s dng khi nim ho tr ca nh ho hc Anh Frankland cho nguyn t cacbon 1857. T vic cng nhn nguyn t cacbon c ho tr 4, Kkul i n kt lun l nguyn t cacbon c kh nng lin kt vi nhau. V d: tan c th vit:
CH3 H C H H

Nh vy cacbon lin kt vi nhau to thnh cc mch di ngn khc nhau. Mt trong nhng ng gp quan trng cho thuyt cu to cc hp cht hu c l thuyt cu to ca Buttlrp (1861): bn cht ho hc ca mt phn t ca mt cht c xc nh bi bn cht cc nguyn t c hp thnh, bi s lng ca chng v bi cu to ho hc. T ni dung ca thuyt ta c th rt ra cc kt lun sau: 1. 2. 3. cu to. Thuyt cu to Buttlrp chnh l nn tng cho s pht trin ca ho hc hu c t nm 1861 n nay. Bng cc phng php ho hc ngi ta xc nh c cu to ca nhiu hp cht khc nhau. Ngy nay, tuy cc phng php ho hc vn cn c ng dng trong thc t nhng xut hin cc phng php vt l nh khi ph, ph cng hng t nhn, ph in Cc nguyn t trong phn t khng phi sp xp hn n, v trt t, chng kt hp Tnh cht ca cc cht khng nhng ph thuc vo thnh phn nguyn t, vo s Cu to ca cc cht c th xc nh c khi nghin cu tnh cht ca chng. Cu vi nhau theo mt trt t xc nh, theo ng ho tr ca chng. lng nguyn t ca cc nguyn t m cn ph thuc vo cu to ho hc ca chng na. to ho hc ca mi cht c th biu th bng mt cng thc ho hc nht nh gi l cng thc

tgip cho cc nh ho hc xc nh nhanh chng v chnh xc cu to ca cc hp cht ho hc. Tm li, s hnh thnh khi lng khng l cc hp cht hu c l do kh nng to thnh dy ng ng, ng phn, kh nng to thnh nhng mch di (c th ni l v tn), kh nng to lin kt bn vng vi cc tc nhn electronphin (nh hyr), vi tc nhn nucleophin (nh halogen, xy, Lu hunh, Nit..) ca nguyn t cacbon. 1.1.3. Cc phng php biu din trong ho hc hu c. Nh ta bit ho hc v c nghin cu ch yu cc hp cht phn cc v cc lin kt ho hc phn cc. Tri li ho hc hu c nghin cu ch yu cc hp cht khng phn cc v cc lin kt khng phn cc. Thuyt in ly trong nhng nm u ca th k 20 t nn tng cho l thuyt cu to ion ca cc mui v cc cht in ly. S pht minh electron v cc nh lut nh lng ca qu trnh in ly l c s cho thuyt ho tr in t. Theo cc thuyt ny mt hp cht in ly c cu to t cation v anion. Cation l nguyn t kim loi b mt in t, cn anion l nguyn t khc nhn thm in t. L thuyt ny c Kosel ng dng cho nhiu hp cht v nhiu qu trnh trong ho hc v c (1917). Mt khc Kosel cng nhn thy rng, i vi cc cht khng phn cc nh H2, O2, N2, hyrcacbon th thuyt in ly khng thch hp m phi tm kim nhng thuyt ho hc khc. iu c Luit gii thch bng lin kt cng ho tr (1916) c to thnh do cp in t gp chung gia cc nguyn t. Theo Luit, lin kt gia cc cht khng phn cc c biu din nh sau:
H2 H H CH4 H HC H H C2H6 HH HCC H HH CH3CH2OH HH HCC O H HH

y cp in t c th thay th bng gch ngang (-). Do cc hp cht lin kt i hay lin kt ba c th biu din:
H H HC C H H H hoc C C H C C H hoc H C C H H H

1.1.4. Phn loi cc hp cht hu c. Cc hp cht hu c c phn loi theo cu to ca chng, c trng bi cc lin kt gia cc nguyn t cacbon vi nhau. Cc hp cht c cha cc nguyn t khng phi l cacbon c xem nh dn xut ca hyrcacbon m trong nguyn t hyr c thay th cc

nguyn t khc. Tt c cc hp cht hu c c chia lm 2 nhm ln: cc hp cht mch h v cc hp cht mch vng. Cc hp cht mch h l nhng hp cht bo: Mch thng khng phn nhnh (normal).
H H H H H H C C C C n-pentan C H H H H H H H H H H H H H H H C C C C C C C C H H H H H H H H H n-ctan
H H C C H H CH3 H H C C C H H CH3 H nepentan

Mch phn nhnh:

H H H C C

H CH3 H H izpentan

Cc hp cht khng no (cha ni i, ni ba):

H C C C C H H H H H butaien-1,3 CH3CH2 C CH butin-1

Cc hp cht vng gm:

Vng ring bit-ch c nguyn t cacbon tham gia ng vng:

C C C C C C C C C C C C C C C C

D vng-cc nguyn t tham gia ng vng ngoi nguyn t cacbon cn c cc nguyn t khng phi l cacbon nh Oxi, NitCng tng t nh cc hp cht mch h, cc hp cht mch vng cng c vng khng no cha ni i hoc ni ba. c bit, mt trong nhng vng khng no rt quan trng l loi vng thm-vng cha 6 nguyn t c ba ni i lin hp ca cacbon hoc cacbon vi cc nguyn t d t.

Benzen

Naphtalen

N Piriin

N Kinlin

Trong loi hp cht thm ny cn c loi vng 5 nguyn t cha 2 ni iv mt nguyn t d t cha cp in t t do:

N H Pirol

O Furan

S Tiphen

1.1.5. Cch gi tn cc hp cht hu c . Trong ho hc hu c cho n nay tn ti nhiu cch gi tn khc nhau. gi cc dy ng ng ca hyrcacbon, ngi ta thng s dng tn gi ca cc hp cht n gin nht. V d hyrcacbon dy mtan, hyrcacbon dy tylen, hyrcacbon dy axtylenTt c cc hp cht hu c khc cn li c xem nh l dn xut ca hyrcacbon. gi tn cc hp cht hu c ring bit, thng s dng cc danh php: danh php thng thng, danh php Gine-v (1892), danh php IUC (International Union Chemistry) 1950, danh php IUPAC (International Union of Pure and Applied Chemistry) 1957 A. Danh php thng thng: Gi tn cc hp cht theo lch s thu nhn c, theo ngun gc ca nguyn liu ban u, theo phng php tng hpV d: kh m (t m), axit focmic (focmic-kin), vanilin (vani-cy vani)Nhiu cht c gi tn ca nh bc hc thu nhn c n. V d xton Micler, hyrcacbon TitibabinMt s tn gi thng thng c s dng rt rng ri trong h thng tn gi th gii. V d tn gi ca dy ng ng ankan t C5 tr i c phn gc l s m h latinh cng thm ui an (pentan, hexan, heptan) nhng 4 hp cht u (mtan, tan, propan, butan) li l tn gi thng thng v phn gc khng phi l s m h latinh. B. Danh php IUPAC: Gi tn cc hp cht mch h: 1. Gi tn 4 hp cht u ca hyrcacbon no l: mtan, tan, propan, butan. Gi tn cc hp cht tip theo ca dy ny bng phn gc l s m h latinh cng ui an: pentan, hexan, heptan, octan, nnan, kanTn gi chung ca hyrcacbon mch thng no l ankan. 2. yl. Vd: CH3CH2CH2CH2CH3 Pentan CH3-CH2-C7H14-CH3 kan CH3CH2CH2CH2CH2Pentyl CH3-CH2-C7H14-CH2kyl Cc raical (phn gc) c ho tr I c to thnh t hyrcacbon no mch h bng cch tch i mt nguyn t hyr u mch c gi tn bng cch thay ui-an bng ui

3. Mch di nht c nh s t u ny n u kia bng ch s latinh sao cho v tr cc nhm mch nhnh c tng cc ch s l nh nht. Trng hp khi nh s t u ny n u kia m thu c mt s dy ch s ca cc nhm mch nhnh khc nhau th phi sp xp chng li theo th t tng dn. Dy c tng cc ch s nh nht c xem l dy c ch s u nh nht.

V d:
CH3 CH2 CH CH2 CH3 CH3 CH CH2 CH2 CH3 CH3 3-mtylpentan CH3 2-mtylpentan (khng c 4-mtylpentan)
CH3 CH3

CH3 CH CH2 CH CH CH3 CH3 2,3,5-trimtylhexan(khng c 2,4,5-trimtylhexan)

CH3 CH2

CH2 CH2 CH CH CH2 CH2 CH3

CH3 CH2CH2CH3 5-mtyl-4-prpylnonan (khng c 5-mtyl-6-prpylnonan)

4. Cc phn gc (raical phn nhnh ho tr 1) c gi tn bng cch thm vo mch thng khng phn nhnh di nht ankyl (bt u t pha c ho tr t do s 1) tn gi cc mch nhnh. V d: CH3CH2CH2CH2CH(CH3)1-mtylpentyl Mt s nhm gi tt nh sau: (CH3)2CHIzprpyl Izpentyl (CH3)2CHCH2izbutyl (CH3)3C-CH2nopentyl CH3CH2CH(CH3)secbutyl (CH3)3Ctecbutyl CH3CH2C(CH3)2tecpentyl CH3CH2CH2CH(CH3)CH22-mtylpentyl

(CH3)2CHCH2CH2-

5. Nu c 2 nhm mch nhnh khc nhau tr ln th c th gi chng theo th t ch ci hoc theo phc tp ca nhm ( ln khng gian ca nhm). V d: Theo vn ch ci:
CH3 CH2 CH2 CH CH CH2 CH3 C2H5 CH3

Hai nhm tyl (C2H5) v mtyl (CH3) th ch E ng trc ch M nn gi l 4-tyl-3mtylheptan. Theo phc tp ca nhm: Nhm c s nguyn t cacbon nhiu phc tp hn nhm c s nguyn t cacbon t: (CH3)3C- < CH3CH2CH2CH2CH 2Nhm ph c ch s nh, t phc tp nhm c ch s ln: CH3CH2CH(CH3)CH(C2H5)CH2- < CH3CH2CH(C2H5)CH(CH3)CH2Gc no nh hn gc khng no:

CH3CH2CH2- < CH3CH=CHGc c ch s v tr khng no nh s nh hn v tr ln: CH3CH=CH- < CH2=CH-CH26. Khi c mt nhiu nhm th ging nhau ta dng cc tip u ng: i-(2), tri-(3), ttra(4), penta-(5), hexa-(6), hepta-(7)V d: CH3CH2C(CH3)2CH2CH3 c l 3,3-imtylpentan. 7. Cc hp cht khng no c mt ni i, gi tn bng cch thay ui an bng ui en, 2 ni i thnh aien, 3 ni i thnh atrienTn gi chung cho cc hp cht l anken, ankaien, ankatrien V d: Hp cht CH3CH2CH2CH=CH-CH 3 gi l 2-hexen CH3CH=CHCH2CH=CH2 gi l 1,4-hexaien Ch : CH2=CH2 tylen v : CH2=C=CH2 allen khng theo h thng danh php IUPAC. Bng cch chuyn i tng t nh vy gi cc hp cht cha ni 3: c 1 ni 3 th i ui an thnh ui in, c 2 ni 3 th i thnh ui aiin, c 3 ni 3 th i thnh atriin Tn gi axtylen l danh php thng thng nn n khng thay i theo quy lut trn. Cc gc anken c ho tr I c gi bng cch thm vo phn ui t -enyl, ienylcn cc gc ankin c ho tr I th thm vo ui inyl, -iinyl V d:
CH3 CH CH 1-prpenyl CH3 CH CH CH2 2-butenyl HC C tinyl HC C CH2 2-prpinyl

8. Gi tn cc hp cht vng tng t nh cc hp cht mch h c thm tip u ng xyclo-. V d:

CH2 CH2 CH2 CH2 CH2 CH H2C H2C CH2 CH2 H2C H2C CH2 CH

xyclprpan

xyclprpyl

CH2 CH2 xyclhexan

CH2 CH2 xyclhexyl

1.2. CHT TINH KHIT Khi nim v cht nguyn cht (mt cht n gin hay mt hp cht) l nhng cht c cu to t nhng phn t ging nhau. Nhng trong thc t kh c th thu nhn c nhng cht nh vy, do cc nh ho hc hu c tnh rng nhng cht c cha 99% cht hu c c gi l cht ho hc tinh khit. nh gi tinh khit ca cc cht, thng dng cc phng php

vt l nh nhit nng chy, nhit ng c, nhit si p sut nht nh, ch s khc x, quay cc, cc loi quang ph 1.2.1. Cc phng php thu nhn cht tinh khit. 1.2.1.1. Phng php kt tinh. y l phng php quan trng nht tinh ch cc cht rn. Ta ho tan n mc bo ho sn phm th trong mt dung mi thch hp nhit cao, lc nng dung dch khi cc thnh phn khng ho tan ri ngui v nh th l hp cht s kt tinh li di dng tinh khit hn. a. La chn dung mi: trong dung mi c la chn hp cht phi t tan nhit thp nhng tan tt khi un nng cn cc tp cht nu tan cng nhiu th cng tt. Theo kinh nghim, thng mt cht c ho tan tt trong dung mi c cu trc ho hc tng t vi n, nht l i vi cc hp cht c cu trc n gin. V d: cc hyrcacbon tan tt trong cc dung mi thuc loi hyrcacbon, te, cn cc anehyt, phnol, ancol, axit cacbxylic tan tt trong H2O, ancolTt nhin dung mi c la chn khng c lm thay i cht ho tan v mt ho hc. b. Cch tin hnh: trc ht ta un nng hp cht cn kt tinh trong mt lng dung mi khng ho tan lng cht , sau ta un si dung mi v qua sinh hn cn thn cho thm dung mi vo cho n khi ho tan hon ton cht kt tinh trong dung mi dang si. Lc nng dung dch, lm lnh s thu c cht rn tinh khit hn. 1.2.1.2. Phng php chng ct. Chng ct l phng php tch v tinh ch quan trng nht i vi cc cht lng. Trong trng hp chng ct n gin, ta cung cp nhit cho mt cht lng n khi cht si v hi ngng t c to thnh trong mt ng sinh hn. Hng ly cht lng ta c cht lng chng ct tinh khit hn. V trong trng hp ny ch c mt tng (tc l hi) chuyn ng nn ta gi l chng ct cng dng hay chng ct n gin. Ngc li nu c mt phn hi c ngng t chy ngc li vi dng hi v li nh vo bnh ang si ta gi l chng ct ngc dng (cn gi l chng luyn rectification). a. Chng ct n gin: Tin hnh chng ct n gin hp l hn c l khi nhit si vo khong 40-150oC ( cao hn 1500C cc cht hu c d b phn hu, thp hn 400C d b mt mt nhiu). V vy cc cht lng si cao hn 1500C phi tin hnh chng ct di chn khng. Chng ct n gin ch thch hp vi cc hn hp lng gm cc cu t c nhit si khc xa nhau.

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Ch khi tin hnh phi iu chnh sao cho tc chng ct trong mt giy khng qu 1 n 2 git ri xung bnh hng. Khi chng ct phi lp ng cong cho qu trnh si- tc l v ng biu din s thay i nhit vi lng cht lng chng ct c T= f(x) ml. b. Chng ct phn on (tinh ct): Trng hp ny p dng khi chng ct n gin khng tch c hn hp ra khi nhau (thng l khi hiu s im si ca cc cht nh hn 800C). Khi tin hnh bng phng php ny trong ct chng ct pha di c nhit cao hn pha trn nn hi c nhit cao i t di ln truyn nhit cho cht lng ngng t t trn xung, lm cho mt phn cu t d bay hi trong cht lng b ngng t li, tip tc bay hi ln 2, ln 3cn mt phn cu t kh bay hi trong pha hi b ngng t thnh lng v tip tc i xung gn di ct ct. Kt qu ca qu trnh lp li nhiu ln nh vy cho ta thu c cht lng ct ra tinh khit hn v cht lng cn li trong bnh ct cng tinh khit hn. c. Chng ct li cun bng hi nc: Nu hai hp cht khng ho tan vo nhau th p sut hi ca chng khng nh hng n nhau. Ta c: fA = pA v p = pA + pB fB = pB Trong fA, fB l p sut ring phn ca A, B. pA, pB l p sut hi bo ho ca A, B tinh khit cng nhit T0C. Mt cht si nhit m p sut hi ca n cn bng vi p sut hi ca kh quyn. Nh vy nu ta un hai cht lng khng ho tan vo nhau th hn hp s si nhit m tng p sut hi ca 2 cht lng bng p sut kh quyn. iu c ngha l im si ca hn hp nh vy bao gi cng thp hn im si ca cu t c im si thp nht. Trong thc t thng dng cht lng th 2 l nc, v vy chng ct hn hp nh vy c th tin hnh nhit thp hn 1000C. Tt nhin nc khng c trn ln v tc dng vi cht cn chng ct. Cch tin hnh: Ta dn hi nc c to ra t mt bnh bng kim loi hoc thu tinh vo y ca bnh ct hnh cu. Trc cn un dung dch cn chng ct cho ti gn si tr lc cho qu trnh ct. Bnh thu sn phm s thu c hai lp cht lng (nc v cht cn tinh ch) c tch ra bng phng php gn hoc bng xiphng. Ni chung ta chng ct n khi no cht lng ct khng cn tch thnh hai lp na. i vi cht lng c nhit si cao c th thay nc bng tylen hoc glyxrin. 1.2.1.3. Phng php thng hoa.

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Phng php thng hoa l phng php m trong ngi ta lm bc hi cc cht rn v sau ngui chng c th ngng t trc tip li di dng cht rn m khng phi lm nng chy chng. 1.2.1.4. Chit. Chit l vic chuyn mt cht dng ho tan hay dng huyn ph t mt tng ny sang mt tng khc. a. Chit cc cht rn: V d chit ng ra khi ma hoc c ci ng. Trong phng php chit n gin mt ln, ta un nng hp cht cn thit vi dung mi trong mt bnh cu c sinh hn hi lu, lc nng hoc lng cho trong ri tch cc phn ring ra khi nhau. Trong phng php chit n gin nhiu ln, ngi ta lp i lp li nhiu ln nh m t trn. b. Chit cht lng, chit cc dung dch huyn ph: Ta cho dung dch nc hoc huyn ph nc chit vo mt phu chit v cho thm dung mi chit vi khong 1/5 n 1/3 th tch cht lng vo phu. ng kn nt phu chit v lc mnh mt s ln, sau yn, dung dch phn thnh 2 lp v tch ly lp dung mi. Theo kinh nghim th dng t dung mi v chit nhiu ln c li hn l chit mt ln vi c lng dung mi chit. 1.2.1.5. Sc k. Phng php sc k do nh bc hc ngi Nga Svet ln u tin a ra v ngy nay n c ng dng rt rng ri trong nhiu lnh vc thc t. Phng php sc k gm c cc dng: sc k giy, sc k ct, sc k lp mng, sc k kh. a. Sc k giy: y l loi sc k phn b m trong tng ng l hn hp cht cn tch v tng tnh l nc (hoc dung mi khc nh du silicol, du parafin, du ha) tm ln giy (xenlul). Ta cho cht ln mt im nht nh trn mt giy (im xut pht), khi tng ng chy qua, cc cht c tch ra. Ta tin hnh sc k giy trong mt bnh kn m khng gian c bo ho vi tt c cc cu t ca h dung mi c s dng.

h1

h2

h3

i lng c trng cho v tr ca cc hp cht sau khi tch l tr s Rf (ratio of front):

khong cch t im xut pht n trung tm vt cht(h) R= f khong cch t im xut pht n tuyn dung mi (H)

b. Sc k ct: Ta cho cht mang (xit silic xp, silicagen, bt xenlul) c tm tng tnh vo ct, sau ho tan hn hp cht cn tch trong tng ng v cho ln u ct. Sau khi

12

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

Kh mang

Tng tnh

My pht hin

My t ghi

Kh quyn

Thit b hng

S mt my sc k kh. 1.3. Cng thc phn t ca cc cht hu c . tin hnh xc nh cng thc phn t ca mt cht hu c ta cn phi: 1. Phn tch nh tnh cc nguyn t - tc l xc nh nhng nguyn t no cu to nn phn t.

13

2. Phn tch nh lng cc nguyn t - tc l xc nh s lng cc nguyn t ca cc nguyn t cu to nn phn t v lp cng thc n gin ca phn t. 3. Xc nh phn t lng ca phn t - lp cng thc ng ca phn t. 1.3.1. Phn tch nh tnh cc nguyn t. a. Pht hin cacbon v hyr: S c mt ca cacbon v hyr c pht hin bng phn ng t chy hp cht hu c vi xt ng. (C, H) + CuO------t----- Cu + CO2 + H2O CO2 thot ra trong phn ng c pht hin bng Ba(OH)2 cho kt ta BaCO3 mu trng, cn H2O c pht hin bng CuSO4 cho hp cht CuSO4.5H2O c mu xanh. b. Pht hin Nit: Nu trong hp cht c cha Nit th khi t chy n s ta mi kht ging nh mi tc chy hoc un vi vi ti xt s ngi thy mi amniac bay ra. Mt phng php tt hn l un nng chy mu hp cht cn xc nh vi natri kim loi. Nu phn ng xy ra th s to thnh mui natri xyanua. Nh vo dung dch ca mui ny mt vi git ca dung dch mui st II v st III, un ti si v sau khi lm lnh axit ho bng dung dch HCl. Nu c kt ta xanh ph (xanh p-ruytx) th chng t hp cht c nit.
Na + 2NaCN + (C,N) FeSO4 NaCN Fe(CN)2 + Na2SO4 Na4[Fe(CN)6] Fe4[Fe(CN)6] + 12NaCl xanh ph

Fe(CN)2 + 4NaCN Na4[Fe(CN)6] + 4 FeCl3 HCl

Pht hin halogen: Dng dy ng mng t trn ngn la cho n khi ht ngn la mu xanh, sau cho mt lng nh mu cht ln u dy ng v t tip. Nu ngn la li xut hin mu xanh th chng t hp cht c halogen. Ta cng c th pht hin halogen bng cch un nng chy mu cht vi natri kim loi.
(C, H, X)
+

Na

NaX

Pht hin ion X bng Ag cho kt ta AgX. 1.3.2. Phn tch nh lng cc nguyn t. Nguyn tc chung: t chy hon ton mt lng c cn chnh xc ca mt hp cht hu c tinh khit vi mt lng d CuO khan. Cacbon v hyr s chuyn hon ton thnh kh cacbonic v nc. Dng mt lng xy kh ui ht sn phm t chy vo nhng ng hp th ring bit: ng ng clorua canxi khan hp th hi nc, cn ng ng hyrxit kali hp thu kh CO2. Hai ng ny c cn chnh xc t trc v sau khi th nghim. Hiu s

14

gia hai ln cn s cho bit khi lng nc v kh CO2 c to thnh, t c th tnh ra c hyr v cacbon. Ngy nay ngi ta dng my xc nh nguyn t ca Libis-Pregli.

O2 cha NO

hp thCO2

hp th H2O mu cht hp th CO2 v H2O ngng t H2O

My phn tch nguyn t Libis-Pregli chuyn NO thnh HNO3, cn cho vo bnh cha KMnO4 v H2SO4 m c. Ta cng c th dng my phn tch ny nh lng halogen. nh lng nit c th dng cc phng php sau y: a. Phng php Dumas-Pregli: trong phng php ny, ngi ta t chy hon ton mt cht hu c c cn chnh xc vi CuO d trong mt dng kh cacbonic. xt nit to thnh c kh bng Cu kim loi v N2 gii phng c dn vo nit k xc nh th tch. Bit th tch kh nit, p sut v nhit ca kh c th tnh c lng nit ca hp cht. b. Phng php Kien-an (Kjeldahl): Mt cht hu c c cn chnh xc, c un vi axit sunfuric m c c mt t mui thu ngn lm xc tc. Trong phn ng ny nit s chuyn ho thnh mui amni sunfat, sau un vi dung dch kim mnh s gii phng NH3. Cho NH3 vo mt lng axit d c chun . Sau khi nh lng phn axit d khng b trung ho bi NH3 s tnh ra c lng NH3 t suy ra khi lng nit.
(C, H, N) + H2SO4 () + HO(NH4)2SO4 NH3 + ...

(NH4)2SO4

+ ...

c. nh lng xy: xy kh nh lng trc tip nn thng ngi ta nh lng cc nguyn t khc trc ri ly hiu s gia 100% vi tng s phn trm ca cc nguyn t tm thy. 1.3.3. Xc nh phn t lng. C nhiu cch khc nhau xc nh phn t lng ca hp cht nhng thng hay dng t khi hi ca cht hu c cn xc nh so vi khng kh: M= 29D (D- t khi hi ca cht hu c so vi khng kh)

15

Ngi ta cng thng dng phng php khi lng ring ca Dumas bng cch o th tch ca mt lng kh bit trc mt nhit v p sut xc nh, t c th tnh ra phn t lng ca n. 1.3.4. Lp cng thc phn t. lp cng thc phn t ca mt hp cht hu c thng phi: 1. Tnh khi lng cc nguyn t ra phn trm. 2. Chia thnh phn phn trm cc nguyn t cho khi lng nguyn t ca chng bit s nguyn t gam ca mi nguyn t. 3. Thit lp t l s lng cc nguyn t ca cc nguyn t bng cch chia cho s nh nht. 4. Lp cng thc phn t n gin. 5. Lp cng thc ng ca phn t bng cch i chiu vi phn t lng ca n. 1.4. CU TRC PHN T CA HP CHT HU C 1.4.1. ng phn cu to. Nu hai hoc nhiu hp cht khc nhau c cng cng thc phn t nhng c mt s tnh cht vt l hoc ho hc khc nhau th ngi ta gi chng l cc hp cht ng phn ca nhau. ng phn cu to l loi ng phn m trong cu to ca chng c s khc nhau v th t lin kt gia cc nguyn t vi nhau. Ngi ta cn gi ng phn ny l ng phn lin kt. V d: Hp cht hyrcacbon C4H10 c th tn ti di hai dng ng phn cu to sau y:
H H H H H C C C C H v H H H H H H H H C C C H H C H H H H

Hyrcacbon C5H12 tn ti di 3 dng ng phn cu to:

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

H H CH3 H

Khi s lng ca nguyn t cacbon trong phn t hyrcacbon tng ln th s lng cc ng phn cu to tng rt nhanh. V d C6 c 5 ng phn, C7-9, C8-18, C20-366 319, C4062.491.178.805.831 ng phn.

16

Mt loi ng phn cu to khc xut hin khi phn t ca cc hp cht hyrcacbon c cha cc lin kt bi. V d hp cht hyrcacbon C4H8 tn ti di 2 dng ng phn sau:
H H H H H C C C C H H H H H H H v H C H C C C H H

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

H
CH3

OH

HO

H
CH3

mt phng gng

Cp i quang trn y ca axit lactic c biu din bng m hnh khng gian nhng i vi nhng phn t phc tp th s dng phng php ny khng thun tin. V vy Fish

17

ngh mt phng php biu din khng gian ca cc ng phn quang hc trn mt phng gi l cng thc chiu Fish. c cng thc chiu Fish, ta t m hnh t din ca phn t sao cho nguyn t cacbon bt i xng nm trong mt phng giy, cc lin kt *C-b v *C- c nm trong mt phng nm ngang hng t mt phng giy n ngi quan st. Cc lin kt *Ca v *C- d nm trong mt phng thng ng hng ra xa ngi quan st.
a b b d c d a c

M hnh t din ca *Cabcd

Cng thc chiu Fish ca *Cabcd

Chiu cc lin kt xung mt phng giy, ta s c cng thc chiu Fish. Axit lactic trn y c biu din di dng cng thc chiu Fish nh sau:
COOH H OH CH3 HO COOH H CH3

i vi mt cht quang hot, ngi ta thng dng quay cc ring [] c trng cho n. [] c th c gi tr m hoc dng khc nhau ty theo cht quang hot lm quay mt phng ca nh sang phn cc v bn phi hoc bn tri. b. ng phn quang hc khng i quang: ng phn quang hc khng i quang l nhng ng phn lp th ca nhau theo ngha chung nhng chng khng phi l nhng ng phn vt-nh ca nhau. ng phn quang hc khng i quang c th xut hin trong mt s trng hp sau: 1. Cc t hp bt k ca mt dng i quang ca cp i quang ny vi cc dng i quang ca nhng cp i quang kia (trng hp ca cc hp cht c t hai cp i quang tr ln). V d 3-phenylbutanol-2 c ng phn I v II l mt cp i quang, III v IV l mt cp i quang khc. Cn cc t hp ca I vi III hoc IV, II vi III hoc V l nhng ng phn quang hc khng i quang ca nhau.

18

CH3 H H OH C6H5 CH3 [ ] = -0,69 HO H5C6

CH3 H H CH3 [ ] = +0,68 H H5C6

CH3 OH H CH3 [ ] = -30,2 HO H

CH3 H C6H5 CH3 [ ] = +30,9

2. Cc ng phn mz: Chng l nhng ng phn lp th m phn t ca chng c cha 2 hoc nhiu trung tm bt i xng nhng gia hai na ca chng c s i xng vtnh, do quay cc ca chng b trit tiu khin cho ng phn mz khng quang hot. V d axit tactric cha hai nguyn t *C (ging nhau) c mt cp i quang v mt ng phn mz c biu din bng cng thc chiu Fish nh sau:
COOH HO H H OH COOH H HO COOH OH H COOH H H COOH OH OH COOH ng phn mz

Cp i quang

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

a C b C

a b

a C b C

b a

ng phn cis

ng phn trans

V d: 1, 2-icloten c 2 ng phn sau y:

19

Cl C H cis-icloten C

Cl H

Cl C H C

H Cl trans-icloten

ng phn syn-anti cng l ng phn cis-trans nhng chng c xut hin cc hp cht c ni i gia nguyn t cacbon vi mt nguyn t d t hoc gia cc d t vi nhau.
H5C6 C N H syn H CH3 H5C6 C N anti CH3 H5C6 N N syn C6H5 H5C6 N N anti C6H5

b. Trng hp phn cng nhc ca phn t l mt ni n hoc mt phn vng trong cc hp cht vng. V d: axt mtylxyclppanic c ng phn cis v trans nh sau:
CH3 COOH H COOH

cis

CH3

trans

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

CH

CH 3

cis

CH

CH3

trans

1.4.2.3. ng phn cu dng. ng phn cu dng l ng phn lp th ng ca cc phn t hu c c phn bit nhau bi s phn b khng gian ca cc nguyn t hoc nhm nguyn t trong cng mt cu hnh. S chuyn ho tng h gia cc ng phn cu dng c thc hin bi s quay quanh cc lin kt n hoc s b gp ca cc phn vng. ng phn cu dng quay xut hin cc hp cht mch h khi c s quay ca cc nguyn t xung quanh trc ca mt hay nhiu lin kt n m khng lm t lin kt ny. biu din cc ng phn cu dng, ngi ta thng dng cng thc phi cnh, hoc cng thc chiu Niumen. Theo cch biu din phi cnh, lin kt gia hai nguyn t cacbon hng theo ng cho t tri qua phi, ng k vch dng ch cc lin kt nm trong mt phng giy, ng gch song song nhn dn ch cc lien kt hng v pha di mt phng giy, ng m hnh tam gic ch cc lin kt hng v pha trn mt phng giy.

20

d a a c b

b a

d a c b

Trong cng thc chiu Niumen, phn t c nhn dc theo lin kt C-C (ngha l trc lin kt ny trc giao vi mt phng giy).
a d c a b b

Nh vy hai nguyn t ny hon ton che khut nhau v ngi ta biu din chng bng mt vng trn chung (thc t l hai vng trn chng kht ln nhau). Cc lin kt v cc nhm th ni vi cc nguyn t cacbon c chiu ln mt phng vung gc vi trc ni hai nguyn t cacbon (mt phng giy). phn bit hai h thng cc lin kt ni vi cc nguyn t cacbon th nht v th hai, ngi ta ko di cc lin kt ca cc nhm th vi cc nguyn t cacbon gn n tm ca ng trn, cn cc lin kt ca cc nguyn t vi nguyn t cacbon xa th ch gp ng trn m thi. V d: tan hai nhm mtyl c th quay xung quanh lin kt n C-C khin cho phn t c th c v s cu dng khc nhau trong c hai cu dng ti hn. Mt cu dng c th nng cao nht ng vi gc quay ca nhm mtyl l 1200, 2400, 3600 gi l cu dng che khut II, IV, VI (th nng cao nht do 3 cp hyr i din nhau nht v gn nhau nht nn y nhau mnh nht), v mt cu dng c th nng thp nht ng vi cc gc quay ca nhm mtyl l 600, 1800 v 3000 gi l cu dng xen k I, III, V (c th nng thp nht do 3 cp hyr nm v tr cch xa nhau nht nn y nhau yu nht).
H H H H H H H HH HH H H H H H H H HH HH H H H H H H H HH HH

II

III

IV

VI

S bin i th nng khi nhm mtyl quay mt vng t 0 n 3600 c biu din trn gin sau (phn t mtan tri qua 3 cu dng che khut khng khc bit nhau v 3 cu dng xen k ng nht nhau hng ro th nng lp li 3 ln). Nh vy cu dng xen k c th nng thp nht nn l dng bn nht. Trng hp mtan dy cc cu dng I, III, V c th nng thp nht do chng bn nht, dy cc cu dng II, IV, VI c th nng cao nht nn t bn nht.

21

E(Kcal/mol) II IV VI

III

V 360

gc quay o

60 120 180 240 300

Gin nng lng ca tan

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

+e

F-

F + e

F-

Do lc ht tnh in dn n to thnh LiF. Lin kt cng ho tr c hnh thnh bng i in t gp chung. V d: s to thnh phn t hyr, mi nguyn t hyr c 1 in t nn khi to thnh phn t 2 nguyn t gp chung cc in t li lm y lp in t cho nhau.
H + H Tng t: F + F H + F H H F F H F

22

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

1s-obitan

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

23

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

2pz

S phn b in t trn cc ocbitan tun theo nhiu nguyn l khc nhau, c th c ti a l 2 electron vi iu kin chng c s lng t spin i nhau. I.5.4. Ocbitan nguyn t.

c bit

nguyn l ngoi tr Pauli c ngha rt ln. Theo nguyn l ny trn mt ocbitan xc nh ch

Trong phn t cng nh trong cc nguyn t ring bit cc electron chim cc ocbitan tng ng vi cc quy tc phn b chng, ch khc ocbitan phn t c nhiu ht nhn. s dng phng trnh sng trn y cho ocbitan phn t ngi ta a ra 2 iu cho php: a. Mi mt cp in t ch nh v (gii hn) xung quanh hai ht nhn nguyn t b. Dng cc ocbitan ca cc electron nh v v s sp xp ca chng ph thuc vo dng v s sp xp cc ocbitan nguyn t to nn phn t I.5.5. Lin kt cng ho tr. to lin kt cng ho tr ocbitan ca nguyn t ny phi xen ph ocbitan ca nguyn t kia v mi mt ocbitan phi c 1 electron. y xy ra s phi hp 2 ocbitan nguyn t to thnh mt ocbitan lin kt. Hai electron trn ocbitan lin kt phi c s lng t spin i nhau. Mi mt nguyn t nm trn ocbitan lin kt chung ny cng c xem nh chng thuc v ca c hai ht nhn nguyn t. V d s to thnh phn t H2 t 2 nguyn t hiro. y mi nguyn t hiro c mt electron chim mt ocbitan 1s. to thnh lin kt 2 ht nhn nguyn t phi tin ti gn nhau sao cho cc ocbitan nguyn t xen ph nhau. Phn t H2 bn vng nht l khi khong cch gia 2 ht nhn nguyn t l 0,74A0. Khong cch ny c gi l di kin kt.
H 1s
0

H 1s

ocbitan lin kt

Ti khong cch r = 0,74 A t hp nng lng ca s xen ph cc electron ca phn t hyr v s y nhau gia cc ht nhn nguyn t l nh nht.

24
(e V )

o (A )

S p h th u c c a n n g l n g i n t tro n g p h n t H 2 v o k h o n g c c h h a i h t n h n

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

Theo cng thc ny trng thi thc ca phn t phi l ci g trung gian gia (1) v (2). Do ta c: 1 = IA. IIB v 2 = IIA. IB - l hm sng ocbitan nguyn t . Phng trnh thc ca ocbitan nguyn t s l: = C11 + C22 Phng php s ho tr dng lm c s ton hc cho quan nim v s cu to cng hng cc cu to. V d benzen c th biu din bng hai cng thc I v II ca Kkul v ba cng thc III, IV, V ca ioa.

II

III

IV

25

Do phng trnh thc ca benzen s l: = C1(1 + 2) + C2(III + IV + V) Cc h s C1, C2 c gi tr sao cho nng lng ng vi hm s l cc tiu. b. Phng php ocbitan. Phng php ocbitan dng hm sng ca tng electron trong trng bao gm cc ht nhn v electron cn li. = C1 1 + C2 2 + .+ C3 3 = Ci I Xt lin kt ho hc theo phng php ocbitan phn t thc cht l m t s phn b electron trong phn t theo ocbitan ca n theo cc nguyn l cho nguyn t ch khc l ocbitan nguyn t c nhiu trung tm ht nhn. V d ocbitan nguyn t hyr c hai trung tm ht nhn. Trong trng hp ny nghim ca phng trnh sng gii ra phi c hai nghim ng vi nhng trng thi khc nhau ca phn t. Trng thi th nht ng vi s ht nhau c nng lng thp hn nng lng ca nguyn t l trng thi ocbitan phn t lin kt: lk = C1 1 + C2 2 ocbitan lin kt mt gp electron gia hai ht nhn l ln nht, tri li ocbitan phn lin kt l bng 0.
obitan phn lin kt + - H H H 1s + H 1s obitan phn lin kt

H obitan lin kt

obitan lin kt

i vi nhng h c nhiu trung tm v nhiu electron vic gii phng trnh sng s dn n nhiu nghim ng vi nhng trng thi nng lng khc nhau. 1.5.7. S xen ph v s lai ho. a. S xen ph. Lin kt cng ho tr c hnh thnh l do s xen ph ca cc ocbitan nguyn t thnh cc ocbitan phn t lin kt. Ocbitan phn t lin kt cng bn v nng lng thot ra khi hnh thnh ocbitan cng ln nu vng xen ph ocbitan cng ln. Khuynh hng ca s xen ph l tin ti cc i. Mun cho cc ocbitan nguyn t tng tc c hiu lc vi nhau thnh ocbitan phn t chng phi tho mn 3 iu kin sau y: 1- Nng lng ca chng gn bng nhau. 2- S xen ph mc ln. 3- Chng phi c cng mt kiu i xng vi trc ni hai nhn nguyn t.

26

Xt iu kin 3 ta c th xen ph: Hai ocbitan s Mt ocbitan s vi mt ocbitan p no c trc i xng trng vi trc ni hai ht nhn. Hai ocbitan p c trc i xng song song vi nhau (cng px, py hoc pz) S xen ph c th theo trc hay bn trc ni gia hai ht nhn nguyn t. Theo trc:

Ocbitan lin kt c trc i xng l ng thng ni gia hai ht nhn v c gi l ocbitan . Lin kt cng ho tr c hnh thnh gi l lin kt . S xen ph xy ra tng t nh vy i vi trng hp ocbitan p + p.
+ * +

S xen ph bn trc:
II

+ + + p p + II*

+ + II

S xen ph bn trc s to thnh ocbitan v lin kt . V ocbitan khng c tnh i xng i vi trc hai ht nhn m ch i xng vi mt phng nt cha 2 trc nn lin kt t bn, d phn cc ho. Mt khc cn tr s quay t do ca nguyn t hay nhm nguyn t xung quanh trc lin kt (do s quay s vi phm nguyn l cc i). l nguyn nhn lm xut hin cc ng phn hnh hc. b. S lai ho.

27

Ph hp vi nguyn l xen ph cc i, tng hiu lc ca s lin kt, cc ocbitan tham gia xen ph c th b lai ho. Ni dung ca s lai ho c th tm tt trong trng hp hnh thnh CH4 nh sau: Cacbon C6 -1s22s22p2
1s
2 2 2

2s

2p

Theo s ho tr trn y th ccbon c ho tr 2 do nu kt hp vi nguyn t hyr th phi to thnh hp cht CH2. Th nhng trong phn t mtan, cacbon c ho tr 4. iu c gii thch rng: c mt electron ca ocbitan 2s chuyn qua ocbitan p cn trng.
1s
2

2s

2p

Kt qu to thnh 4 in t c thn v do c th hp vi 4 nguyn t hyr to thnh CH4. Nh vy c th nhn thy rng cacbon s to thnh 3 lin kt c cng mt loi lin kt ca cc ocbitan p v mt lin kt ca ocbitan s. Nhng thc t 4 lin kt ca CH4 hon ton ging nhau. iu c gii thch bi s lai ho ca cc ocbitan-tc l s t hp lai to thnh nhng ocbitan c dng khc vi ocbitan ban u c kh nng xen ph cao hn do lin kt hnh thnh bn vng hn. Thc vy cc kt qu tnh ton cho thy rng: 1- Ocbitan lai to tt nht c hng xen ph cao hn ocbitan s hoc ocbitan p. 2- 4 ocbitan lai to tt nht c hng xen ph cao hn hon ton ng nht vi nhau. 3- Cc ocbitan ny hng n gc ca mt t din u- tc l s sp xp m trong cc ocbitan nm v tr cch xa nhau nht. S lai ho ny gi l lai ho t din. Gc lai ho trong trng hp ny l 109028.
1s
2

2s

2p

lai ha sp 1s
2

sp

S lai ho sp3 c th biu din nh sau:

2 sp3

28
y lai ha x z s + 3p sp3

Cc kt qu tnh ton cho thy rng nu coi kh nng xen ph ca ocbitan s l 1 th ocbitan p l 3 v ocbitan lai ho sp3 l 2. Trong phn t mtan cng nh cc ng ng ca n, ocbitan lai to sp3 ca cacbon xen ph vi ocbitan 1s ca hyr to thnh lin kt (C-H). cc ng ng ca mtan 2 ocbitan sp3 ca hai nguyn t cacbon bn cnh nhau to thnh lin kt (C-C). V gc ho tr ca nguyn t cacbon sp3 l 109028 nn mch cacbon trong phn t ankan l ng gp khc khc hnh ziczc.
H
H

H
H H H

H H

H H
H H

H H

CH4

CH CH 3 3

CH CH CH2CH3 3 2

Kiu lai ho th hai l s tng hp 1 ocbitan s vi 2 ocbitan p to thnh 3 ocbitan sp2 (lai to tam gic hoc lai ho phng). Trc i xng ca 3 ocbitan sp2 nm trn mt mt phng to thnh gc 1200. Kh nng xen ph tng i ca ocbitan sp2 l 1,99.

y + x s + 2p
1s
2

+ sp2
2p
3

2s

lai ha sp 1s
2

sp

2p

Trong phn t tylen cc ocbitan sp2 tham gia xen ph to nn 5 lin kt c trc nm trong mt mt phng. Cn li 2 ocbitan p thun khit cha lai to xen ph bn nhau to thnh lin kt .

29

H H

H H

C
H

C
H

Kiu lai ha sp-t hp ca mt ocbitan s v mt ocbitan p gp trong cc phn t c ni 3 vi kh nng xen ph l 1,93 v gc to bi trc i xng ca 2 ocbitan l 1800 (kiu lai ho ng thng).

- sp

s+p
1s
2

2s

2p

lai ha sp 1s
2

sp

2p

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

CH

1.5.8. Mt s c tnh ca lin kt cng ho tr . a. Nng lng lin kt. Nng lng lin kt A-B l s nng lng thot ra khi hnh thnh lin kt t hai nguyn t A v B hay hai gc t do A. v B.. cng chnh l nng lng cn thit lm t lin kt A-B thnh 2 nguyn t hoc 2 gc t do. Tuy vy nng lng lin kt ch nhng gi tr trung bnh gn ng ca nng lng phn ly. V d khi dng khi nim nng lng lin kt ta gi thit rng tt c cc lin kt C-H chng hn trong ankan l nh nhau. Thc ra nng lng

30

cn thit lm t lin kt C-H th nht trong mtan chng hn khng phi bng nng lng cn thit phn cp hon ton phn t ny thnh cacbon v hyr, cng khng phi bng nng lng lm t C-H trong tan, prpan, bezenNng lng lin kt ca C=C v CC khng ln gp i hay gp ba ca C-C. b. S phn cc. Trong lin kt cng ho tr cp electron lin kt hay ocbitan phn t lin kt ch c phn b tht u gia hai nguyn t v mmen lng cc bng 0 khi no hai nguyn t hon ton ng nht nh h A-A: Cl-Cl, H-H, H3C-CH3Trong trng hp hai nguyn t lin kt vi nhau khng ng nht h A-B: H-Cl, CH3-Clcp electron lin kt s lch i t nhiu v pha mt nguyn t no c m in ln hn v do lin kt c mmen lng cc khc 0 ( 0).
A A
A B

H A-A

H A-B H

A=B A B

S phn cc khng nhng c th xy ra lin kt m cn xy ra c lin kt , h A=B hoc AB, v d H2C=O, -CN m t s phn cc ca lin kt cng ho tr ngi ta thng dng mi tn thng cho lin kt v mi tn cong cho lin kt (chiu mi tn l chiu chuyn dch ca cc electron).
H3C Cl hoc H3C
+ + -

Cl hoc H3C
+ -

Cl

H2C O hoc H2C O hoc H2C O

1.6. L THUYT V S CHUYN DCH ELECTRON TRONG PHN T CC HP CHT HU C. 1.6.1. Hiu ng cm ng. a. nh ngha v phn loi. Xt hai phn t prpan v n-prpylclorua.
H H H H C C C H H H H H H
+ C3

H
+ C2

H C1 H
+

Cl

Khc vi prpan, prpylclorua c nguyn t clo vi m in ln do lin kt C1-Cl b phn cc v kt qu clo mang mt phn in tch m v CI mang mt phn in tch dng. V C1 c mt in tch dng nh nn lin kt C1-C2 b phn cc v pha C1, n lt C3-C2

31

li cng b phn cc v pha C2. S phn cc khng nhng xy ra lin kt C-C m cn c lin kt C-H. Kt qu l phn t b phn cc v xut hin mt mmen lng cc, cn hyr th tr nn linh ng hn (so vi hyr prpan). Dng phn cc ny gi l phn cc cm ng hay hiu ng cm ng. Vy bn cht ca vn hiu ng cm ng l s phn cc cc lin kt lan truyn theo mch cc lin kt do s khc nhau v m in. Ngi ta k hiu hiu ng cm ng I (Inductive Effect). Hiu ng cm ng c th gy ra bi nguyn t hay nhm nguyn t ht electron gi l hiu ng cm ng m (-I), nguyn t hay nhm nguyn t nhng electron gi l hiu ng cm ng dng (+I). Chiu chuyn dch electron c m t bng mi tn.
Y (+I) C C (I=0) H C (-I) X

b. Quy lut v hiu ng cm ng ca nguyn t v nhm nguyn t. Phn tch nhng d kin v hiu ng cm ng nhng nguyn t hay nhm nguyn t khc nhau ngi ta rt ra mt s quy lut sau: 1. Cc nhm mang in tch dng c hiu ng -I, cc nhm mang in tch m c hiu ng +I. V d: -N+R3 l nhm I mnh cn O- l nhm +I mnh. 2. Nu cc nguyn t ca cng cc nguyn t cng mt chu k nh hay phn nhm chnh trong h thng tun hon u c hiu ng I th hiu ng cng ln khi nguyn t tng ng cng v pha bn phi chu k hoc cng pha trn phn nhm chnh. F > Cl > Br > I F > OR > NR2 3. Cc nhm ankyl lun lun c hiu ng +I, hiu ng tng theo bc ca nhm: CH3 < CH3CH2 < CH(CH3)2 < C(CH3)3 4. Trng thi lai to ca cacbon c I bin i: Csp > Csp2 > Csp3 tc l RCC- > C6H5- > R2C=CRc. c im ca hiu ng cm ng. c im ni bt ca hiu ng cm ng I l gim rt nhanh khi ko di mch truyn nh hng.V d nh hng ca clo n lc ca axt butyric nh sau:
CH3CH2CH2COOH Cl Ka.105 1,5 CH2CH2CH2COOH Cl 3,0

CHCH2COOH CH3 8,9

Cl

CHCOOH CH2CH3 139,0

Theo kt qu ca bng trn y th clo v tr lm tng lc axit ln 87 ln, v tr lm tng 6 ln, v tr lm tng 2 ln.

32

1.6.2. Hiu ng lin hp. a. nh ngha v phn loi. xt hiu ng lin hp ta xt phn t n gin c h cc lin kt lin hp l butaien. Tng t nh trong phn t tylen, cc nguyn t cacbon trong phn t butaien u trng thi lai ho sp2 v h thng cc lin kt l mt h phng. Mi nguyn t cacbon cn li mt ocbitan p thun khit xen ph vi nhau to thnh 4 ocbitan phn t khc nhau I, II, III, IV. Cc tnh ton c lng t cho thy rng ocbitan phn t IV c nng lng thp nht ( bao trm c 4 nguyn t cacbon gi l ocbitan gii to hay khng khu tr). H phn t c ocbitan gii to nh butaien gi l h lin hp. H lin hp thng gp , p v , V d:
C C C C H mch h , CH2 CH CH CH2 H mch vng , C C X H lin hp CH2 C Cl
IV I II III

,p

Bnh thng phn t butaien c gii ta nh IV. Nu thay mt nguyn t hyr CH2 bng CH=O chng hn th do c tnh phn cc sn c ca nhm CHO s lm cho mt electron chuyn ng dch mt phn v pha n lm cho ton b phn t b phn cc.
CH2 CH CH CH2 CH2 CH CH CH CH O

Ta ni y c hiu ng lin hp v nhm CHO gy hiu ng lin hp (k hiu l C). Nhm CHO lm chuyn dch mt electron v pha n nn c hiu ng lin hp m (-C). Ngc li, nu nguyn t hay nhm nguyn t lm mt electron chuyn dch t pha n n cacbon th n c hiu ng lin hp dng (+C). Vy hiu ng lin hp l hiu ng electron truyn trn h lin hp gy nn s phn cc h electron trn . b. Quan h gia cu to ca nhm th vi hiu ng lin hp. Hiu ng lin hp c 3 loi: 1. Cc nhm +C: Cc nhm ny ni chung u c cp electron cha s dng hay electron d:

-O-, -S-, -OH, -SH, -NH2, -NR2, -NHCOCH3, -F, -Cl, -Br. ng ch l hu ht cc nhm c hiu ng +C ng thi c hiu ng I mc khc nhau. V vy trong trng hp c th cn phn bit nh hng ca mi loi. V d: CH3O- l nhm y electron ni chung v c khi ni ring v nh hng lin hp v +C > -I.
+C CH3O -I CH CH CH CH2

33

Tri li clo l nhm ht electron ni chung v +C< -I.

+C CH2 CH CH CH Cl -I

i vi cc nguyn t hay nhm nguyn t c cng hiu ng lin hp +C th: nguyn t mang in m c hiu ng +C mnh hn nguyn t tng t khng mang in. O- > -OR -S- > - SR Trong mt chu k nguyn t cng bn phi th +C cng yu: -NR2 > -OR > -F Trong mt phn nhm chnh lc +C gim t trn xung di: -F > -Cl > -Br > -I -OR > -SR > -SeR 2. Cc nhm C: a s cc nhm ny l nhng nhm khng no: -NO2, -CN, -CHO, -COR, -COOH, -CONH2 Thng cc nhm C c c hiu ng I. Cc nhm -C=Z c lc C ph thuc vo Z ( nu Z cng bn phi chu k th lc C cng ln):
C O C NR C CR2

Nhm mang in tch dng c C ln hn khng mang in:

C NR2
+

C NR

3. Cc nhm c hiu ng C vi du khng c nh. Loi ny thng l nguyn t hoc nhm nguyn t cha no nh: vinyl, nhm nguyn t gn vi phenyl l -NO2 (nhm C) hay NH2 (nhm +C). phenylV d: trong phn t nitrbenzen v anilin phenyl, c th biu hin hiu ng +C hay C ty theo

34

O2N -C +C

H2N +C -C

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

H , p phng

X H , p khng phng

1.7. MT S PHNG PHP VT L THNG DNG TRONG HO HC HU C xc nh cng thc cu to ca mt hp cht hu c, trong phn trc ta xem xt cc phng php tinh ch cc hp cht, xc nh thnh phn v khi lng cc nguyn t c trong mt phn t. Ngy nay xc nh cu to ca mt hp cht hu c nhanh hn v chnh xc hn, ngi ta dng cc phng php vt l nh khi ph, quang ph hng ngoi, ph cng hng t ht nhn 1.7.1. Khi ph. Nu ta bn ph phn t ca mt hp cht hu c bng mt dng electron c nng lng trung bnh (20-70 electron-vn) th cc phn t s b ion ho v ph v thnh nhiu mnh khc nhau, trong c mt s mnh l ion dng. T l khi lng ca mi loi ion vi din tch (m/e) chnh l khi lng ca ion. V d nu ta bn ph phn t nopentan:
CH3 H3C C CH3 CH3

M (C5H12) m/e 72

M1+(C4H9)+ 57

M2 (C3H5)+ M3+(C2H5)+
+

M4+(C2H3)+ 27

41

29

Nu cho dng cc ion dng ny vo mt t trng hng vung gc vi hng ca t trng th cc ion c t l m/e khc nhau nn di tc dng ca t trng s b lch i khi hng ban u nhng qu o khc nhau. Tn hiu thay i ny ca cc ion s c mt b phn ghi t ng ghi li v cho ta ph khi lng ca hp cht cn xc nh m trong mi

35

loi ion s c th hin bng mt pic ring bit c cng ng vi i lng m/e. Pic c bn c cng tng i ln nht M+ tng ng vi phn t lng ca phn t. Tuy nhin nhiu khi pic M+ l mt pic c cng tng i yu. V d khi ph ca nopentan, M+ ng vi phn t lng ca phn t c cng tng i yu, cn M+ ng vi phn t lng ca butanhytc cng tng i ln nht.
100

I / I0 (%) M1+ M3+

30 40

75 50 25 0 10

M+

M2

M4+
20

50

60

70

80

90 100 110 120 130 140

Ph khi lng ca nopentan

100 80 60 40 20 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

I / I0 (%)
43(M-CHO)+ M = 72 57(M-CH 3)+
+

29(CHO)+ 15(CH 3)+

Ph khi lng ca butanhyt 1.7.2. Quang ph hp ph. a. Quang ph in t. Chng ta bit mt s bc x in t nh nh sang thng, nh sng cc tm, hng ngoi, tia Rngen, sng rai

cm-1

10 xa

3 10

3 5.10 gn

10

106 T ngoi gn xa p.electron Tia X Tia

Hng ngoi c s p.dao ng

p.quay

Tt c cc loi sng trn y u c mt tc truyn sng l 3.1010 cm/s v tn s = c/ trong c l tc truyn sng, l di sng (cm). Khi mt chm tia sng in t gp phi mt vt no th n c th xuyn qua, cng c th b hp th li ph thuc vo tn s ca sng v cu to ca vt th. Ta bit rng, bc x in t l mt dng nng lng, do khi phn t hp th bc x in t th n c cung cp thm mt nng lng E= E1-E0 = h = hc/.

36

Nng lng E c phn t hp th, c th gy ra s dao ng, s quay ca cc nguyn t trong phn t hoc bc chuyn electron n mt mc nng lng cao hn. Tn s bc x m mt phn t nht nh c th hp thu ph thuc vo trng thi dao ng hay trng thi quay ca cc nguyn t cu to nn phn t. Vy ph ca mt hp cht l th cho php xc nh phn no ca bc x in t b hp th (hay i qua) vt th mt tn s nht nh. N mang tnh cht c trng cho cu to ca cht. b. Quang ph hng ngoi. Trong ho hc hu c, ph hng ngoi c ngha rt ln xc nh cu to ca hp cht. Phn t lun lun dao ng. Nu dao ng lm thay i di cc lin kt th ngi ta ni l dao ng ho tr, cn nu thay i gc lin kt th ngi ta gi l dao ng bin dng. Gi s phn t c n nguyn t, vy c 3n bc t do trong 3 bc dng xc nh chuyn ng tnh tin, 3 bc dng xc nh chuyn ng quay v cn li 3n-6 bc l dao ng t do (phn t thng hng, c 3n-5 bc dao ng t do v ch c hai bc chuyn ng quay). V d phn t H2O c n=3 do 3.3-6=3 bc dao ng t do.

a a,b - dao ng ha tr

c c - dao ng bin dng

S thay i dao ng t do ca phn t c gy c gy ra bi s hp th trong vng hng ngoi. ch ra v tr hp th trong vng ngoi, c th s dng di sng hay tn s (thng hay dng tn s c biu th bng n v s sng cm-1) Ph hng ngoi c gi tr xc nh nhng nguyn t hay nhm nguyn t no c (hoc khng) trong phn t. Bng tn s hp th ca mt s nhm trong ph hng ngoi. Lin kt Loi hp cht C-H C-H C-H C-C Ankan Anken Ankin Anken Tn s cm-1 2850-2960 3020-3080 3300-3340 1640-1680

37

C-C C-O O-H

Ankin Anhyt, xton Ancol

2100-2260 1690-1760 3610-3640

CH2 C-H CH3 C=C C-H

1.7.3. Ph cng hng t ht nhn (CTN). Ht ca mt s nguyn t ging nh electron c spin. Theo tnh ton ca c hc lng t th s spin ca ht nhn nguyn t c th phn thnh: I=0 I=1/2 I=1 I=3/2
12 1 2

C,

16 3

O,

28 13

Si
19

H, B,

H, N Cl,

C,

F,

31

H,

14 35

37

Cl

I= c nhng gi tr cao hn. V cc ht nhn nguyn t l nhng phn mang in tch nn nhng ht nhn c I0 khi quay quanh trc ca n s sinh ra mt mmen t . Cc ht nhn c mmen t I=0 khng c tn hiu cng hng t nhn. Cc ht nhn c I>1/2 cho cc tn hiu cng hng t nhn rt phc tp nn t s dng. Ch c cc ht nhn c I=1/2 thun tin cho CTN. c bit trong ho hc hu, thng s dng ph cng hng t ht nhn ca proton (CTP) v proton c hu ht trong cc hp cht hu c. Nu t proton trong t trng H0, theo nh lut c hc lng t mmen t ca proton c th c 2I+1 nh hng, tc l 2.1/2 +1 = 2: Mt nh hng theo t trng H0 (m= +1/2) Mt ng hng i lp vi t trng H0 (m= -1/2)

iu c ngha l proton trong t trng H0 c xp trn 2 mc nng lng: E1= + .H0 E2= -H0 Nh vy chuyn hng i lp vi t trng theo hng vi t trng cn phi c mt nng lng E= E1-E2 = 2.H0. Thay = h/4 (trong hng s c trng cho mi ht nhn, h l hng s Plng).

38

Ta c: E = hH0/2 (E ch ph thuc vo H0) Mt khc theo nh lut hp th, s cng hng ch xy ra khi: E = h Suy ra: h= hH0/2 do = H0/2 l tn s m ti xy ra cng hng. Nguyn tc hot ng ca mt my CHP nh sau:
B khuych i My ghi dao ng M A M Hp cht A My t ghi B to sng

Trong thc t c th thu nhn ph CHP bng hai cch: 1- C nh t trng H0 v lm thay i tn s ca trng in t. 2- C nh tn s v lm thay i H0 (phng php ny thng hay s dng hn). Nu tt c xy ra n gin nh trnh by trn y th tt c mi prton ca cc phn t ca cc cht hu c u hp th mt H0 nht nh v ph cng hng prton ch c mt vch. Nhng t c mt cng H0 (cng hiu dng) th do mt in tch bao quanh cc proton khc nhau nn cn phi tc dng ln mi mt proton mt t trng H (cng tc dng) khc nhau. Nh vy mt tn s xc nh cc proton u hp th mt cng hiu dng nh nhau nhng khc nhau v cng tc dng H. Chnh s khc nhau nay cho php thu nhn ph CHP thnh nhng dy pic hp th c trng cho s bao bc ca cc electron xung quanh proton.
I/I0

Ph CHP cho ta thng tin cn thit xc nh cu to ca phn t sau y: 1- S lng cc tn hiu cng hng ch ra c bao nhiu loi proton khc nhau trong phn t.

39

V d: CH3-CH2-Cl a b (2 tn hiu)

CH3CHCl-CH3 a b a (2 tn hiu)

CH3-CH2-CH2-Cl a b c (3 tn hiu)

2- V tr tn hiu cng hng ch ra thng tin v s bao bc ca electron xung quanh proton. V tr ny c nh gi bng khong cch gia tn hiu ca nhng nhm ht nhn c kho st v tn hiu ca cht lm chun. i lng c gi l chuyn dch ho hc. chuyn dch ho hc c o bng n v phn triu (pt). Cht lm chun thng chn l ttramtylsilan (TMS) v TMS ch c mt vch hp v vch ny xa cc tn hiu cng hng prton khc. Hin nay trong ho hc tn ti hai loi thang o o chuyn dch ho hc v lin h vi nhau theo

=10 +

Trong v d di y chuyn dch ho hc ca CH3 l 0,9pt; -CH2 l 1,3pt; -CH l 1,5pt c vit nh sau: ph CHP, , pt. 0,9(CH3); 1,3(CH2); 1,5(CH).
CH3 CH2 CH TMS

3- Cng (din tch ca pic) ch ra s lng ca proton mi loi trong phn t. Thng cng ny c ch ra trn ph CHP bng ng bc thang v mi bc ca n t l vi din tch ca tn hiu.V d trong ph CHP ca p-tecbutyltoluen sau y c s lng proton a l 9 tng ng vi 18mm, proton b l 3 tng ng vi 6mm, proton c l 4 tng ng vi 8mm.

40

4- S phn chia tn hiu thnh cc vch ch ra nh hng ca cc proton xung quanh n proton kho st do s tng tc spin-spin. V d trong ph CHP ca etylbrmua tn hiu cng hng ca nhm CH3 l 3 vch, cn ca CH2 l 4 vch.

Xt nhm CH3 ta thy proton ca n b nh hng bi nhm CH2. Trong t trng proton CH2 c th nh hng:
-1/2 + (-1/2) = -1 -1/2 +1/2 -1/2 +1/2 = 0

H0 +1/2 +1/2 = 1

Do nh hng ca proton CH2 nh trn nn proton nhm CH3 b phn thnh 3 vch theo t l 1:2:1. Xt proton CH2 ta thy n b nh hng ca nhm CH3. Trong t trng ca CH3 n c th nh hng:

H0

Do nh hng ca nhm CH3 nn proton ca nhm CH2 b phn thnh 4 vch theo t l 1:3:3:1. Khong cch gia cc vch k nhau ca mt tp hp c o bng Hz gi l hng s tng tc spin-spin J. Hng s ny c trng cho s tng tc gia cc nhm nguyn t trong ph CHP.

41

1.8. PHN LOI CC PHN NG TRONG HO HC HU C. Cc phn ng hu c phn loi bng nhiu cch khc nhau: theo tin trnh phn ng, theo phng thc sp xp li lin kt v theo s cc phn t tham gia vo bc quyt nh tc phn ng. 1.8.1. Theo tin trnh phn ng. a. Cc phn ng cng hp (k hiu l A t ch addition tc l cng hp). V d:
Br C C + Br Br C Br C

R NH2 + H

R NH3

b. Cc phn ng tch loi (k hiu l E t ch Elimination tc l tch) V d:

C C H OH C C + H2O

c. Cc phn ng th (k hiu l S t ch Substitution tc l th). V d:

R H R X + Cl + Y
-

Cl

R Cl + R Y + X

HCl
-

1.8.2. Theo phng thc sp xp li lin kt. a. Cc phn ng gc. y l loi phn ng m trong mt s giai on ca phn ng xut hin nhng sn phm (hay sn phm trung gian) c mt in t khng lin kt. Thng cc gc t do c to thnh do s phn ct ng ly. V d:
A B Cl Cl RO OR . . A + B . 2Cl . 2RO

b. Cc phn ng phn cc hay phn ng ion. Trong nhng phn ng ny cc lin kt c tch ra hay to thnh bng mt cch bt i xng, tc l cp lin kt c mt bn gi li hoc do mt bn ca lin kt mang . Thng cp lin kt in t c to thnh do s phn ct d ly.

42

V d:
A B H Cl A+ H
+

+ +

BCl
-

Ta phn bit nhng phn ng i nhn N (Nucleophin) v nhng phn ng i in t E (Electronphin). Theo qui nh bao gi cng cn c vo tc nhn phn ng (reagent) xc nh xem mt phn ng l i nhn hay i in t. Nhng cng ging nh phn ng xi ho- kh i nhn v i in t l hai mt ca mt qu trnh gn b vi nhau cho nn nhiu khi gi mt cu t tham gia phn ng l tc nhn hay l hp cht (substrat) ch l iu kin tu . Thng th cht c cu trc t phc tp l tc nhn, cn cht c cu trc phc tp l cht nn. V d trong phn ng cng triankylamin vi boriflorua th triankylamin l tc nhn i nhn cn boriflorua l tc nhn i in t.
R R N R i nhn B i in t F F F R R N R B F F F

Cc tc nhn i nhn thng l: - Cc ion c in tch m, cc hp cht c cp in t t do, cc hp cht c lin kt bi hoc cc hp cht thm. Cc tc nhn i in t thng l: - Cc ion c in tch dng, cc hp cht c v in t cha hon chnh (Axit Liut), cc hp cht axtylen, cc hp cht c nhm cacbnyl, cc halogen. 1.8.3 Theo s cc phn t tham gia bc quyt nh tc phn ng. 1, Cc phn ng n phn t 2, Cc phn ng lng phn t 3, Cc phn ng c s phn t cao hn

43

CU HI N TP V BI TP CHNG 1 1.1. Bn cht v c im lin kt cng ha tr. 1.2. nh ngha hin tng ng phn lp th, phn loi ng phn lp th 1.3. iu kin cn v c ng phn hnh hc. Cch gi tn cc ng phn hnh hc. 1.4. iu kin cn v c ng phn quang hc. Cch gi tn cc ng phn quang hc. 1.5. Bn cht v c im ca hiu ng cm ng v hiu ng lin hp. 1.6. Vit cng thc cc ng phn hnh hc c th c v gi tn cc ng phn , ng vi cc cng thc cu to sau:
a. CH3 b. CH3 CH CH2 CH CH C2H5 c. Cl d. CH3 CH CH Br CH3 C 2 H5

CH CH C CH3

1.7. Trong cc hp cht sau, hp cht no c tnh quang hot.

Cl a. CH3 CH CH3 OH H d. CH3 C CH2 CH2 CH2 CH3 CH2 CH3 b. CH3 C CH2 H OH e. CH3 CH C CH2 CH2 CH3 CH3 CH3 CH3 c. CH3 CH3 H CH C Br CH3

1.8. Vit cng thc cc ng phn lp th ca cc hp cht sau y v cho bit loi ng phn.
a. CH3 c. CH3 CH CH CH CH CH3 CH CH CH3 Br Br d. C6H5 b. CH2 N N C 6 H5 CH CH2 CH2 CH CH2 e. CH3 CH CH CH COOH CH3
b. CH3 CH CH CH O CH CH CH2

1.9. Trong cc hp cht sau, hp cht no c hiu ng lin hp.

a. CH2 c. CH3 CH CH2 CH C CH CH2 d. CH3 O CH2 C NH2 e. CH2

1.10. Sp xp cc hp cht sau theo th t tng dn tnh axit.

a. ClCH2CH2COOH, FCH2CH2COOH, BrCH2CH2COOH b. NO2 COOH, COOH, CH3O COOH

44

TI LIU THAM KHO CA BI TP CHNG 1 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

45

Chng 2 HYRCACBON NO (ANKAN) Cc hp cht hu c ch c cha 2 nguyn t hyr v cacbon c gi l hyrcacbon. Da vo s cu to khc nhau, cc hyrcacbon c chia lm hai loi chnh: hp cht khng thm v hp cht thm. Cc hp cht khng thm c chia thnh ankan, anken, ankin v cc hp cht mch vng tng ng ca chng (xyclankan, xyclanken, xiclankin). 2.1. Dy ng ng, ng phn. Hp cht n gin nht ca ankan l CH4. N c cu to t din (nguyn t cacbon c ocbitan lai to sp3, gc lin kt l 109028, di lin kt l 1,09 A0). Cc hp cht tip theo l tan, prpan, butangi l cc hp cht ng ng ca ankan: CH4, CH3-CH3, CH3-CH2-CH3, CH3-CH2-CH2-CH3 Dy hp cht m trong thnh phn phn t ca hp cht tip theo khc vi thnh phn phn t ca hp cht trc mt n v cu to nht nh gi l dy ng ng. Cc hp cht ca dy gi l cht ng ng. Nh vy cc hp cht ankan to thnh dy ng ng ankan m trong hai hp cht k nhau khc nhau bi mt n v cu to l CH2. T ta suy ra cng thc tng qut ca ankan l: CnH2n+2. Cng vi s tng ln ca s lng nguyn t cacbon trong phn t s lm tng s lng nhng kh nng phn b khc nhau ca cc nguyn t cacbon dn n s to thnh cc ng phn khc nhau. V d: pentan c 3 ng phn, hecxan c 5 ng phn, heptan c 9 ng phn, kan c 75 ng phn, kzan (C20H42) c 366.319 ng phn. Pentan (C5H12)
C C C C C C C C C C C C C C izpentan C neopentan

n-pentan

2.2. Danh php Cc hyrcacbon c gi tn thao cc danh php nh trnh by phn i cng (1.1.5). 2.3. Tnh cht vt l. Lc lin kt phn t gm 2 loi: lc tc dng lng cc v lc Van-ec-van.

46

Lc tc dng lng cc c gy ra bi s ht nhau ca u mang in tch dng ca phn t phn cc ny vi u m ca phn t kia. (v d nh trong phn t HCl).
+ +

Trong trng hp hp cht khng phn cc, s phn b ca in tch l i xng (v d CH4) do tng cc mmen phn cc bng 0. Nhng mt khc in tch lun lun chuyn ng, v vy mt thi im xc nh no s phn b ca chng thay i do lm xut hin mt s phn cc nh. Chnh s phn cc tc thi ny lm nh hng n s phn b ca cc in t trong phn t CH4 khc. Kt qu lm phn t phn cc cm ng. S phn cc ny to ra lc lin kt cc phn t li vi nhau. Lc chnh l lc Van-ec-van. Lc ny c hiu lc trong mt khong cch ngn v ch gia cc phn t tip xc vi nhau, tc l gia cc b mt ca cc phn t. V vy phn t cng ln, tc l b mt ca cc phn t cng ln th lc cng mnh. Thc nghim chng minh rng, nhit si v nhit nng chy ca ankan tng theo chiu tng ca s nguyn t cacbon c trong phn t. Bng tnh cht vt l ca mt s ankan. Hp cht Mtan tan Prpan n-butan n-pentan n-hecxan n-heptan n-octan n-nonan n-kan Cng thc phn t CH4 CH3CH3 CH3CH2CH3 CH3(CH2)2CH3 CH3(CH2)3CH3 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 t0nc -183 -172 -187 -138 -135 -95 -90 -57 -54 -31 t 0s -162 -88,5 -42 0 36 69 89 126 151 174 0,625 0,659 0,684 0,703 0,718 0,730 dg/ml

Nu biu din s ph thuc cu nhit nng chy ca cc hyrcacbon no mch thng vo s nguyn t cacbon c trong phn t th ta s thu c th hnh rng ca.

47
50 Nhit nng chy 0 1 -50 -100 -150 -200 3 5 S nguyn t C 7 9 11 13 15 17 19

Theo quy tc kinh nghim, tr mt s ankan thp nu mch ca phn t tng thm mt nguyn t cacbon th nhit si ca ankan tng ln 20-300C. Trn thc t 4 ankan u l nhng cht kh, 13 ankan tip theo (t C5 n C17) l cht lng, t ankan C18 tr i l cht rn. Ankan khng phn cc nn tan tt trong dung mi khng phn cc. T trng ca cc ankan tng ln khi phn t lng tng nhng khng qu 0, 8 g/ml. iu c ngha l ankan nh hn nc. 2.4. CC PHNG PHP IU CH. Thng cc phng php iu ch cc hp cht hu c c chia lm 2 loi: phng php cng nghip v phng php phng th nghim. Hai phng php ny c nhng im khc nhau sau y: Phng php cng nghip thng thu nhn mt khi lng hp cht ln vi gi thp trong khi phng th nghim cn tng hp mt vi trm gam, mt vi gam hoc t hn, khng quan tm n gi c v thi gian cn thit tng hp. Phng php cng nghip s dng cc hp cht khng ch dng tinh khit m c dng hn hp nhiu cht, cn trong phng th nghim lun lun i hi phi dng tinh khit. Phng php cng nghip thng chn cch thu nhn hp cht sao cho thun li v vic vn dng cc dy chuyn cng ngh v thit b. V vy thng phng php cng nghip ch c ngha vi cch thu nhn mt hp cht nht nh. Tri li phng php phng th nghim quan tm n vic s dng cho c mt lot hp cht cng loi vi nhau. 2.4.1. Phng php cng nghip. a. Ngun thu nhn chnh ca ankan l du m v kh thin nhin. S thi ra hng triu nm ca cc tng a cht chuyn ho cc hp cht hu c phc tp ca ng thc vt thnh hn hp ankan c thnh phn t 1 n 30, 40 nguyn t cacbon. Thng kh thin nhin ch cha nhng ankan nh (c phn t lng nh) ch yu l CH4. Du m c thnh phn ankan phc tp hn. Bng phng php chng ct du m, ngi ta tch cc loi ankan ra khi nhau, c ng dng rng ri trong i sng, cng nghip. Cc ankan l cht kh c s dng lm

48

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

b. Phng php tng hp t xyt cacbon CO. Cho hn hp xyt cacbon vi hyr nhit 2500C v p sut thng i qua xc tc kim loi hay Co.
n CO + (2n-1)H2 Cn H2n-2 + nH2O

2.4.2. Phng php phng th nghim. a. Tng hp mtan t cacbua nhm.

Al4C3 + 12H2O 4 Al(OH)3 + 3CH4
CH4 + 4 Cu2S
CH4 + Na2CO3

T sunfua cacbon
CS2 + 2 H2S + 8 Cu

T axtat natri (phng php kim nng chy)

CH3COONa + NaOH

b. Tng hp tan: phn ng Vuyc.

2 CH3Cl + 2 Na CH3CH3 + 2 NaCl

Phn ng Knbe: in phn mui axtat. Ti ant anion CH3COO- b phng in tch thnh raical CH3COO. v b phn hu thnh CO2 v tan.
. 2 CH3COO CH3CH3 + CO2

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

RX + Mg RMgX H2O RH ( RMgX l tc nhn Grinha)

CH3CH3CHBrCH3 sec-butylbrmua

Mg

CH3CH2CHMgBrCH3

H2O

CH3CH2CH2CH3 n-butan

Kh bng kim loi trong mi trng axt.

RX + Zn + H
+

RH + Zn

+2

+ X

+ CH3CH2CHBrCH3 Zn/H CH3CH2CH2CH3

Kh bng axt iic nhit cao.

RX + 2HI CH3CH2CH2CH2CH2Cl + 2HI RH + HX + I2 CH3CH2CH2CH2CH3 + HX + I2

49

d. Hyr ho anken.
CnH 2n H2/Ni CnH 2n+2

Trong tt c cc phng php trn y, phng php hyr ho cc anken c ngha nht v: phn ng tin hnh n gin (khuy trn mt anken vi hyr mt p sut va phi v mt lng xc tc nh, ta s thu c mt ankan c khung cacbon ging nh anken ban u). Mt khc ngun nguyn liu anken r, d thu nhn bng nhiu phng php khc nhau. Kh ho cc ankylhalogenua bng tc nhn Grinha l phn ng th trc tip nguyn t halogen bng hyr. Ankan thu c cng gi nguyn khung cacbon ban u. y cng l phng php c ngha thc t ln v cc alkylhalogenua d dng thu nhn t cc hp cht khc. Tuy nhin trong trng hp yu cu iu ch mt cht no m c th s dng c c 2 phng php th nn chn phng php hyr ho anken v n n gin hn v c hiu sut phn ng cao hn. Phn ng Vuyc ch c ngha dng iu ch cc ankan i xng. V d:
Na CH3CH3 2 CH3Br Na 2 CH3CH2Br CH3CH2CH2CH3

Trong trng hp dng iu ch cacbon bt i xng th phn ng Vuyc t c ngha v to thnh mt hn hp sn phm do lm tng thm khi lng cht ban u v lm phc tp qu trnh tch sn phm. V d:
R1X + 2Na + R2X 2 R1X 2 R2X R1 R2 R1 R2 + Na R1 (sn phm ph) R2 (sn phm ph)

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

2.5.

TNH CHT HO HC.

Ankan trc y gi l parafin (t ch latinh parumaffinis tc l i lc ho hc yu) ni ln rng kh nng phn ng ca chng yu. Ankan khng c kh nng kt hp vi hyr nn c gi l hyrcacbon no. Ankan khng phn ng trc tip vi clo, brm iu kin thng, ch b oxy ho bi cc tc nhn oxy ha mnh nhit cao nh KMnO4. Cc phn ng ca ankan. 1- Phn ng halogen ha.

50

C H + X2

tC

C X + HX

3-

Phn ng vi iazmtan v kten.

R C H + CH2N2 iazmtan CH2=C=O kten as R C CH2 H + (N2 hay CO)

3- Phn ng t chy.
C n H2n+2 + 3n+1 O2 1 n CO2 + (n+1) H2O

4- Phn ng crcking.
CnH 2n+2 cracking C H H m 2m+2 + Cn-m 2(n-m)

5- Phn ng sunfnic ho:

R C H + HO SO3H R C SO3H + HO 2

6- Phn ng sunfclo ho:

R C H + SO2 + C l2 R C SO2Cl + HCl

7- Phn ng nitr ho:

R C H + HO NO2 R C NO2 + H2O

2.5.1. Phn ng halogen ho. a. Trc ht ta nghin cu phn ng clo ho mtan. Hn hp kh mtan v clo di tc dng ca nh sng hoc nhit (250-4000C) th chng s tc dng mnh lit vi nhau to thnh phn t mtylclorua. Mtylclorua c th tip tc tham gia phn ng clo ho to thnh mtylenclorua. Phn ng c th tip tc xy ra v to thnh triclomtan (clorofoc) hoc ttraclomtan (cacbon ttraclorua).
Cl2 Cl Cl Cl CH4 as2 CH3Cl as2 CH2Cl2 as2 CHCl3 as CCl4

V vy hiu r phn ng ta phi lm sng t my vn sau: Mtan v clo khng tc dng vi nhau trong bng ti nhit thng. Phn ng d dng xy ra trong bng ti nhit 2500C hoc nhit thng khi c chiu sng. Nu phn ng c khi mo bng nh sng th c hng ngn phn t mtylclorua c to thnh

51

khi phn ng hp th mt phton nh sng. Khi c mt lng nh oxy s lm gim tc phn ng i mt thi gian. Thi gian ny ph thuc vo lng oxy c trong phn ng. gii thch ph hp vi cc vn t ra trn y, ngi ta ngh mt c ch tng qut cho phn ng clo ho mtan nh sau:
Cl2 . CH4 + Cl . CH3 + Cl2 t0C . 2 Cl . CH3 + HCl . CH3Cl + Cl

tip theo (2), (3), (2), (3)...

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

V vy ch c s va chm vi phn t mtan mi dn n vic to thnh mt gc t do mi (giai on 2). Gc mtyl CH3. mi sinh ra cng tng t nh gc clo trc y tm cch lm y lp 8 in t ca mnh bng s va chm vi cc phn t hoc nguyn t khc. S va chm cng ch c ngha vi phn t clo v mi to thnh mtylclorua v Cl. (giai on 3). Gc t do clo mi sinh ra ny li tham gia vo phn ng (2), tip theo l phn ng (3). Qu trnh ny c lp i lp li nhiu ln to thnh nhiu phn t mtylclorua. Tuy nhin cc phn t trn y xy ra khng phi l vnh cu v rng tuy s va chm ca cc gc t do vi nhau rt t nhng vn c th xy ra v do dn n s mt i cc gc t do:
. . Cl + Cl . . CH3 + CH3 . . CH3 + Cl Cl Cl CH3 CH3 CH3 Cl

Nu trong phn ng c mt oxy th:

52

. CH3 + O2

. CH3OO

Gc t do CH3OO. C kh nng phn ng thp hn nhiu so vi gc CH3. nn lm cho tc phn ng chm li. Hp cht c kh nng lm cho phn ng b chm li hoc lm dng phn ng ngay c khi vi mt lng rt nh gi l cht c ch. Trong v d trn y oxy l cht c ch CH3OO. l gc c ch. iu cui cng chng ta cn phi gii thch l ti sao thu c mt hn hp nhiu sn phm v c th khng ch phn ng thu c mt sn phm duy nht l mtylclorua hay khng? thi gian u ca phn ng, mtan tc dng vi clo to thnh mtylclorua (I). Theo thi gian khi lng mtan bt dn v mtylclorua tng ln do mtylclorua s tham gia cnh tranh vi mtan trong phn ng clo ho. Khi nng ca mtylclorua ln hn nng mtan th clo s tc dng nhiu hn vi mtylclorua, II tr thnh ch yu. Tng t nh vy s xy ra cc phn ng III, IV. V vy sn phm ca phn ng l mt hn hp 4 dn xut ankylhalogenua. C th khng ch phn ng ch to ra mt sn phm ch yu l mtylclorua bng cch cho d mtan. Trong trng hp ny lng mtan lun lun nhiu hn mtylclorua v do s hn ch c phn ng II. b. Phn ng dy chuyn. Phn ng gia mtan v clo trn y ngi ta gi l phn ng dy chuyn tc l phn ng xy ra qua nhiu giai on m trong giai on ny lm sinh ra nhng trung tm c kh nng phn ng mnh gy ra phn ng ca giai on tip theo. y cng l phn ng c trng cho cc hp cht ankan ni chung.
250-4000 C . Giai on to gc X2 2X (1) . . R + HX (2) Giai on pht X + RH . . trin mch RX + X (3) R + X2 tip theo (1), (2), (3)... . (4) X2 X + X . . (5) X + R RX . . (6) R-R R + R .

Giai on tt mch

Trn gin nng lng ca phn ng clo ho mtan ta nhn thy rng E2, E3 c ngha l trong hai phn ng pht trin mch, phn ng (2) xy ra chm hn nhiu so vi (3) do phn ng (2) c tnh cht quyt nh tc phn ng.

53
E
trng thi chuyn tip

E2
CH4+Cl. CH3. + Cl2

E3
CH3Cl+ Cl.

tin trnh phn ng

c. nh hng phn ng halogen ho. Xt cc phn ng halogen ho cc hp cht sau:

. . Cl CH4 Cl CH3 2 CH3Cl . . Cl Cl CH3CH3 CH3CH2 2 CH3CH2Cl . Cl CH CH CH . Cl2 CH CH CH Cl 3 2 2 3 2 2 n-prpylclorua gc n-prpyl CH CH2 H . . Cl CH CHCH Cl2 CH CHClCH H 3 3 3 3 gc izpropyl izpropylclorua

CH3

Trong phn ng ca prpan vi clo, gc prpyl c to thnh khi tch i mt hyr bc I, izprpyl c to thnh khi tch hyr bc II. Ta nhn thy rng trong phn t prpan c 6 hyr bc I v 2 hyr bc II nn xc sut va chm ca Cl. vi cc loi hyr ny l 6:2 (hay 3:1) c ngha l sn phm n-prpylclorua: izprpylclorua l 3:1. Nhng trong thc t t l thu c l 1:1 (45:55). Ngha l izprpylclorua c to thnh vo khong 3 ln nhiu hn l n-prpylclorua. iu ch c th gii thch bng nng lng hot ho Ea (Ea dng tch hyr bc II nh hn rt nhiu so vi hyr bc I). Bng s kho st tng t ngi ta i n kt lun rng kh nng tham gia phn ng halogen ho ca cc nguyn t hyr bin i theo dy sau: Hyr bc I < Hyr bc II < Hyr bc III nhit phng t l vo khong 5,0:3,8:1,0. T l ny cho php tin on t l cc sn phm sinh ra trong mt phn ng clo ho. V du:
CH3CH2CH2CH3 Cl2/as CH3CH2CH2CH2Cl n-butylclorua + CH3CH2CHClCH3 izbutylclorua

Ta c t l sn phm:

54 n-butylclorua s hyr bc I kh nng phn ng hyro bc I = izbutylclorua s hyr bc II kh nng phn ng hyro bc II
= 6 1,0 6 28% = = 4 3,8 15,2 72%

Kh nng tham gia phn ng ca hyr vi brm xy ra theo t l hyr bc I : hyr bc II : hyr bc III = 1600 : 82 : 1 S d kh nng tham gia phn ng ca cc loi hyr trong phn ng halogen ho thay i nh trn l v do nh hng ca hiu ng +I ca cc nhm ankyl nn dn n bn ca cc raical bin i nh sau:
CH3 . C CH3 CH3 C. H H CH3 C H . H H C H .

CH3

CH3

c. S xut hin nguyn t cacbon bt i xng. Trong phn ng clo ho n-butan c sn phm thu c sec-butylclorua c nguyn t C2 bt i, nhng thc nghim chng minh rng sec-butylclorua l mt hp cht khng quang hot. iu c gii thch rng giai on (2) gc Cl. tch i mt nguyn t hyr bc II to thnh sec-butylclorua. Nguyn t cacbon trong gc t do c ocbitan lai to sp2. Giai on tip theo to thnh lin kt C-Cl clo c th tn cng c t hai pha ca mt phng cha ocbitan lai to sp2. V xc sut tn cng vo hai pha ca mt phng nh nhau nn to thnh mt s lng bng nhau cc sn phm quay phi v quay tri, do gc quay ca nh sng phn cc trit tiu ln nhau nn hn hp sn phm thu c khng quang hot. Ngi ta gi hn hp ny l bin th Raxmic.
a H3C C2H5 H b Cl2 Cl CH3 H H3C H C2H5 C2H5 Cl Cl C2H5 CH3 H H C2H5 CH3 Cl

Vy hn hp Raxmic tc l hn hp mt s lng bng nhau ca ng phn quang hc quay phi v quay tri. Phn ng to thnh hn hp Raxmic gi l phn ng Raxmic ho. 2.5.2. Mtylen ho. Mtylen c to thnh trong phn ng phn tch cc hp cht iazmtan hoc xten di tc dng ca nhit:

55

CH2 CH2

N N

CH2 + N2 t0C CH C O 2 + CO

t0C

Mtylen c tnh hot ng ho hc mnh v do tham gia phn ng mtylen ho:

CH2N2 tC
0

CH3CH2CH2CH2CH2CH3 n-hecxan CH3CH2CH2CH(CH3)2 2-mtylpentan CH3CH2CHCH2CH3 CH3 CH3CH2CH2CH2CH3 + CH3CH2CHCH3 CH3 3-mtylpentan

CH3CH2CH2CH2CH3

CH3CH2CH2CH3

CH2

C O t0C

2.5.3. Phn ng t chy. Phn ng ankan vi xy to thnh CO2 v nc cng vi s gii phng mt nng lng ln thng c s dng thu nng lng. Cho n nay c ch ca phn ng ny cha c chng minh nhng chc chn rng y l phn ng dy chuyn c ch gc. Mt trong nhng ng dng rt quan trng ca phn ng ny l dng nhit t chy cc hyrcacbon chy cc ng c t trong. Vic s dng cc ng c p sut cao c ngha rt ln nhng lm xut hin mt kh khn: nhin liu trong xylanh thng t n nhng thi im cha cn thit nn lm gim sc my. khc phc iu ny ngi ta khc phc bng hai phng php: 1- Chn nhng hyrcacbon thch hp lm nhin liu ng c. 2- Cho thm hp cht ttramtyl ch vo nhin liu. Theo phng php th nht ngi ta phn loi rng hyrcacbon tt nht lm nhin liu ng c l hp cht izoctan. CH3C(CH3)2CH2CH(CH3)2 2,2,4-trimtylpentan (izoctan) Ngi ta quy nh izoctan c ch s octan l 100. Hp cht c ch s octan km nht l n-heptan (bng 0). Ch s octan ca nhin liu tng ln rt mnh khi cho thm mt lng ttratyl ch.

56 CU HI N TP V BI TP CHNG 2

2.1. Gi tn ankan theo danh php thng thng v danh php IUPAC. 2.2. Cc phng php iu ch ankan. 2.3. Nhng tnh cht ha hc quan trng ca ankan. 2.4. Vit phng trnh phn ng iu ch cc ankan sau y: a. n-Butan b. iz-pentan 2.5. Khi Clo ha cc ankan sau y trong iu kin c nh sng xc tc s thu c nhng dn xut mono Clo g? a. n-Propan b. Iz-butan Tnh hiu sut cc sn phm trong mi trng hp, gi s kh nng phn ng ca cc nguyn t hiro cacbon bc I, bc II, bc III tng ng vi: 1:3:5 2.6. Gi tn theo danh php quc t cc hp cht sau y:
a. CH3 CH2 CH3 c. CH3 C CH2 CH3 CH CH2 CH CH3 CH2 CH3 CH CH2 CH3 CH3 d. CH3 CH2 CH CH CH2 C2H5 CH3 CH3 b. CH3 CH2 CH CH CH3 CH3 C2H5 C 2 H5 C CH2 CH3 C 2 H5

2.7. Cho bit cc sn phm ph trong phn ng iu ch n-pentan t n-propyl ioua v etyl ioua theo phng php tng hp WURTZ (Vuyc). TI LIU THAM KHO CA BI TP CHNG 2 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

57

Chng 3 ANKEN Anken l loi hyrcacbon c s lng nguyn t hyr trong phn t t hn trong ankan tng ng l hai nguyn t. V n c kh nng cng hp vi hyr nn c gi l hyrcacbon cha no. Cng thc tng qut ca anken l CnH2n. 3.1. CU TO V NG PHN CA ANKEN. 3.1.1. Cu to. Cu to n gin nht ca dy anken l tylen C2H4, trong phn t tylen 2 nguyn t cacbon u c ocbitan lai to l sp2. Cc ocbitan lai to ny xen ph vi ocbitan s ca hyr vo vi nhau to thnh 5 lin kt nm trong mt mt phng. Mi nguyn t cacbon cn li mt in t t do xen ph vi nhau to thnh lin kt (2 m my in t nm pha trn v pha di ca mt phng cha lin kt ).
H C H C H H H H 1,09A 0 1,34A C C 121
0 0

H 117,5 H
0

Hp cht tip theo l prpen C3H6 c cu to l CH3-CH=CH2. Tip theo l butylen c mt s cu to:
CH3CH2 CH CH2 CH3 CH CH CH3 buten-2 CH3 C CH2

buten-1

CH3 izbuten

Hp cht buten-2 c th vit di 2 dng ng phn hnh hc:

H C C H H C C H H3C trans-buten-2 CH3

CH3 H3C cis-buten-2

3.1.2. ng phn hnh hc. ng phn hnh hc l loi ng phn xut hin do s cn tr quay t do ca cc nguyn t xung quanh lin kt i C=C. Ngi ta k hiu cc ng phn c hai nhm th hoc hai nguyn t ging nhau nm v cng mt pha cu mt phng l ng phn cis, nu nm khc pha l ng phn trans. Tt nhin s cn tr quay xung quanh lin kt i i vi cc nguyn t cacbon ca anken no cng c th nhng ng phn hnh hc ch xut hin khi no cc nhm th cc nguyn t cacbon ni i khc nhau.

58

V d:
H C H3C C H H H C C2H5 C H H H C H C CH3 CH3

Khng c ng phn hnh hc

H C C H H C C Cl

Cl Cl cis-icloten

H Cl trans-icloten

c im ca cc ng phn hnh hc l chng c cc tnh cht vt l khc nhau, c cc tnh cht ho hc tng t nhau v cng mt loi hp cht nhng mc tham gia cc phn ng ho hc ca chng khc nhau v c cu to hnh hc khc nhau. 3.2. CCH GI TN. 3.2.1. Danh php thng thng. Ging nh ankan, cc hp cht anken n gin nhiu khi c gi bng cc tn gi thng thng nh: tylen, prpylen, butylenHp cht butylen phn bit nhau bi cc tin t , iz-. Cc ng phn hnh hc nh ni trn phn bit nhau bng cis hoc trans. Nhng cch gi ny b hn ch khi dng gi tn cc anken phc tp. 3.2.2. Danh php IUPAC. 1- Mch chnh c chn l mch di nht c cha ni i cacbon-cacbon. Hp cht cn gi c xem nh l dn xut cu mch chnh m cc nguyn t hyr c thay th bng cc nhm th khc nhau. Tn gi ca mch chnh (ten, prpen, buten, penten) c to thnh bng cch i ui an ca ankan tng ng thnh ui en. 2- nh s mch chnh sao cho v tr ni i l nh nht (ly s u ca nguyn t cacbon ni i). 3- Gi tn cc nhm th cng vi cc ch ca n trc tn gi ca mch chnh. V d:
CH3 CH3 C CH CH2 CH3 CH3 3,3-imtylbuten-1 CH3 CH CH CH CH3

4-mtylpenten-2

3.2.3. Tnh cht vt l. Tng t nh ankan, anken khng ho tan hoc rt t ho tan trong nc nhng tan tt trong cc dung mi khng phn cc nh benzen, te, CCl4Chng c t trng nh hn nc.

59

Nhit si ca cc anken tng t nh ankan, c tng thm mt nguyn t cacbon trong mch th nhit si tng ln 20-300C. Bng mt s tnh cht vt l ca anken. Tn gi tylen Prpylen Buten-1 Penten-1 Hexen-1 Hepten-1 Octen-1 Nonen-1 ken-1 th phn cc.
H C C Cl
0

Cng thc CH2=CH2 CH2=CH-CH3 CH2=CHCH2CH3

T0C -102 -48 -6,5

Tnc0C -169 -185

CH2=CH(CH2)2CH3 30 CH2=CH(CH2)3CH3 63,5 CH2=CH(CH2)4CH3 93 CH2=CH(CH2)5CH3 132,5 CH2=CH(CH2)6CH3 146 CH2=CH(CH2)7CH3 171 -87 -138 -119 -104

0,648 0,675 0,698 0,716 0,731 0,743

Nu ankan hon ton khng phn cc th anken tu thuc vo cu to hnh hc ca n c

H Cl

H C C Cl
=0

Cl H

3.4. CC PHNG PHP IU CH. 3.4.1. Phng php cng nghip. Trong cng nghip anken c iu ch bng phng php crcking du m.
CnH 2n+2 cracking C H H m 2m+2 + Cn-m 2(n-m)

Cc anken c s nguyn t cacbon nh hn 5 c th thu nhn c di dng tinh khit bng cch chng ct phn on. 3.4.2. Phng php tng hp. 1- Tch loi ankylhalogenua.
C C H X
CH3CH2CH2CH2Cl KOH/ancol CH3CH2CH CH2

KOH/ancol

C C

60

CH3CH2CHCH3 Cl

KOH/ancol

CH3CH2CH CH2 + CH3CH CHCH3

2- hyrat ancol.
C C H2SO4() C C + H2O

H OH

CH2 OH

CH2 OH

H2SO4() H+

CH2

CH2 + H2O

CH3CH2CH2CH2OH

CH3CH CHCH3 + CH3CH2CH CH2

3. Tch loi alkylihalogenua.

C C + Zn C C + ZnX2

X X

V d:
CH3CH CHCH3 Br Br Zn CH3CH CH CH3 + ZnBr2

4. Kh ho cc ankin.
H2/Ni(Pd, Pt) H R C C R R H Na (Li)/NH3 R C C H H C C R R sn phm trans sn phm cis

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

V d:

61

(CH3)2C CH3 + H+ OH (CH3)2C CH2 + H+

(CH3)2C CH3
+

CH3

C+ CH3 CH3

OH2

b. Phn ng tch lng phn t E2. Trong phn ng E2 hp cht baz tham gia trng thi chuyn tip tn cng vo mt nguyn t hyr cacbon.
Y- + H C C X Y....H ....C....C ....X
-

C C

+ X + HY

c. nh hng ca bc lin kt v cu trc khng gian ni chung ti hng ca phn ng tch loi. Trong phn ng tch loi cc hp cht m nhm th X thuc cc nguyn t cacbon bc II hoc bc III, phn ng c th xy ra theo 2 hng sau:
CH3CH CHCH3 Tch loi Zaixep CH3CH CHCH3 H X CH3CH2CH CH2 Tch loi Hpman

nh hng Zaixep xy ra khi no lfin c to thnh c s lng cc nhm ankyl nhiu nht gn vo 2 nguyn t cacbonni i. Tri li nh hng Hpman xy ra khi lfin c s nhm ankyl l nh nht. Thng th cc phn ng E1 to ra ch yu sn phm tch loi Zaixep. V d:
CH3 CH3 CH C(CH3)2 H2SO4 - H2O OH H CH3 CH C(CH3) CH3 CH2 (87,5%)

C CH2 (12,5%)

3.4.4. Tch loi ankylhalogenua. Khi c mt ca cc baz mnh vi nng cao phn ng tch loi cc ankylhalogenua xy ra theo c ch E2.
X C C H X
-

HO

C C H...OH
Trng thi chuyn tip
-

C C

+ X + H2O

Cc cht thng c dng lm baz l: hyrxyt kim, ancolat kim, cc hp cht amin.

62

V d:
CH3CH2CHCH3 Br KOH/ancol CH3CH CHCH3 + CH3CH2CH CH2 81% 19%

T l cc sn phm anken trong mt phn ng tch loi c u tin theo dy bin i sau: R2C=CR2 > R2C=CHR > R2C=CH2 > RHC=CHR >RHC=CH2 > CH2=CH2 3.4.5. Tch loi ancol. Phn ng tch loi ancol xy ra khi c mt axit v un nng.
C C H+, t0 C C C + H2O

H OH

Kh nng tch loi ca ancol bin i: Ancol bc III > ancol bc II > ancol bc I a. C ch ca phn ng tch loi ancol.
C C H OH C C H +OH2 C C
+

nhanh

C C H +OH2 C C
+

chm

+ H2O

H C C + H
+

nhanh

b. bn ca cacbcation Trong phn ng tch loi ancol, anken thu c nhiu khi khng ph hp vi d on ca c ch phn ng. V d:
CH3CH2CH2CH2OH CH3CH2CHCH2OH CH3 CH3 CH3 C CH3 H CH3CH CHCH3 + CH3CH2CH CH2 - H2O
sn phm chnh
+

H CH3CH C CH3 - H2O CH3

sn phm chnh
+

CH3CH2C CH2 CH3 CH3 C CH CH2 CH3

H CH CH3 CH3 - H2O OH

CH3 C C CH3 + CH3 CH3

sn phm chnh

63

S d thu c sn phm ca phn ng tch loi khng ph hp vi d on ca c ch trong cc phn ng trn y l do ion cacbni t chuyn v to thnh ion cacbni khc bn hn.
CH3CH2CH2CH2OH CH3CH2CH2CH2+ CH3CH2CHCH3
+

CH3CH2CH2CH2+ CH3CH2CHCH3
+

in bc I in bc II

H -H
+

CH3CH CHCH3 sn phm bn

Tng t nh vy:
CH3 CH3CH2 C
+ CH2

CH3 CH3CH2 C
+

CH3

H in bc I CH3 CH3 C CH CH3

+

CH3

in bc III (bn hn) CH3 CH3 CH3 C

+

CH CH3

CH3 in bc II

in bc III (bn hn)

3.5. TNH CHT HO HC CA ANKEN Anken c cha lin kt i giu in t khng bn nn phn ng c trng cho loi hp cht ny l cng hp electrphin ph v lin kt. 3.5.1. Cc phn ng ca anken. a. Phn ng cng hp. 1- Cng hyr.
C C + H2 Ni H2/Ni CH CH CH3CH2CH3

CH3CH CH2

2- Cng halogen (X2 = Cl2, Br2).

C C + X2 Br2/CCl4 C C

X X CH3CH CHCH3 Br Br

CH3CH CH2

3- Cng hyrhalogenua.
C C + HX C C H X
CH3CH CH2 + HI CH3CHICH3

64

CH3CH CH2

HBr peroxit

CH3CHBrCH3 CH3CH2CH2Br

4- Cng nc
C C H+ + H2O CH C OH

CH3CH CH2

H2O/H+ CH3CHOHCH3

5- Cng hyphalogenua
C C + X2 + H2O C C + HX

CH3CH CH2 + Cl2 + H2O

X OH CH3CHOHCH2Cl + HCl

6- Hyr bo ho
C C + (BH3)2 C C H2O2 C C

H BH2

H OH

7- Polyme ho
n C C
CH2N2 C C CH2=C=O

C C

8- Cng mtylen
t 0C C C CH2

9- Phn ng xy ha
C C + KMnO4 (hoc HCOOOH) CH3CH CH2 KMnO4 CH3CHOHCH2OH C C OH OH

10- Phn ng th
H C C C + X2 600 C 600 C
0 0

X C C C ClCH2CH2Cl

CH3CH CH2 + Cl2

11- Phn ng zn ho.

O C C + O3 C O C O H2O/Zn C O+ O C

65

CH3CH2CH CH2

O3 H2O/Zn

CH3CH2CH O + O CH2

H2O/Zn CH3C CH2 O3 CH3C O + O CH2 CH3 CH3

3.5.2 C ch phn ng cng hp electrphin. C ch ca phn ng cng hp electrphin AE xy ra theo 2 bc.

+ -

Y + C C Y C C+ (1)

+ Y X

Y C

C+ + X-

Y C

C X

(2)

Bc (1) xy ra chm quyt nh tc phn ng. a. Phn ng cng halogen xy ra trong mi trng tr:
CH2 CH2 + Br2 CCl4 CH2BrCH2Br CCl4 CH3CHBrCH2Br

CH3CH CH2 + Br2

y l phn ng dng pht hin cc hp cht c cha ni i C=C (lm mt mu nu ca nc brm). b. Phn ng cng hp hyrhalogenua
CH2 CH2 + HI CH3CH2I CH3CH2CH2I + CH3CHI CH3CHCH2I + CH3 CH3 CI CH3 CH3 CH3 CH3CH CH2 + HI CH3 C CH2 + HI

CH3

Kho st mt lng ln cc phn ng cng hp tng t nh trn, Macpnhicp (1869) a ra quy tc: trong phn ng cng hp electrphin mt axit c prton vo mt lfin, nguyn t hyr lin kt vi nguyn t cacbon giu hyr nht. Nh ta bit hng ca phn ng theo c ch AE c trnh by trn y ph thuc vo ion cacboni. Do nh hng ca hiu ng +I nn bn vng ca ion cacboni bin i:
R3C
+

R2CH

RCH2

CH3

Xt phn ng:
CH3CH CH2 + HI CH3CH2CH2+ in bc mt CH3CHCH3
+

in bc hai

66

V bn ca cacbcation bc II ln hn bc I nn sn phm ch yu l:
CH3CHCH3 + I+

CH3CHICH3

Theo kt qu ca s gii thch trn y, quy tc Macpnhicp c th pht biu tng qut nh sau: phn ng cng hp electrphin vo lin kt i cacbon-cacbon xy ra theo hng no to thnh ion cacbni bn vng hn. Theo quy tc ny th kh nng phn ng ca cc anken vi cc axit bin i: (CH3)2C=CH2 > CH3CH=CHCH3 > CH3CH2CH=CHCl hoc: v:
CH3 CH3 C CH3 CH CH2 H
+

CH3CH=CH2 > CH2=CH2 > CH2=CHCl

Do phn ng xy ra qua bc to thnh cacbcation nn s to ra cc sn phm chuyn

CH3 CH3 C
+

CH CH3 Cl CH3

CH3 C CH3 CH CH3 Cl

CH3

Nhng mt khc trong phn ng ny cn to ra mt sn phm chuyn v sau y:

CH3 CH3 C CH CH3 CH3
+

CH3

CH3 CH3

C CH CH3 Cl CH3 + CH3

CH3 C CH CH3 Cl CH3

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

Br + Br
-

Br+ C C C C

C C + Br Br Br

C Br

(1) (2)

Phn t Br2 bnh thng khng phn cc nhng di nh sng ca trng in t mnh ca ni i n b phn cc. Hin tng ny gi l s phn cc ho. Nu phn ng tin hnh trong mi trng c cc anion khc th sn phm to thnh khng phi duy nht l dn xut ihalogenua v ion cacbni c to thnh c th kt hp vi cc tc nhn khc c trong mi trng phn ng. 3.5.3. Phn ng cng hp theo c ch gc AR.

67

Khi c mt ca pexit, phn ng cng hp ca hyrbrmua vo anken khng xy ra theo quy tc Macpnhicp. Kharash v Meo gii thch rng, ay l phn ng cng hp xy ra theo c ch cng hp gc t do.
RO OR . RO + HBr . Br + Pht trin mch C C . Br + HBr C C t0 C . RO (1)

Phn ng to gc

. ROH + Br (2) C C . Br C C Br H (3) . + Br (4)

Tip theo (3), (4), (3), (4)...

Xt phn ng:
. . HBr CH3CH CH2 perxit CH3CHCH2Br + CH3CHBrCH2 gc bc 2 gc bc 1

Trong phn ng ny gc bc 2 c to thnh s bn hn gc bc 1 nn sn phm ch yu l prpylbrmua. Tng t nh vy nu cho anken tc dng vi CCl4 khi c mt pexit th s xy ra theo c ch gc nh sau:
RO OR . RO + Cl CCl3
.CCl + RCH CH2 3

t0 C

. 2RO ROCl + .CCl3

(1) (2)

. R CH CH2CCl3 + Cl CCl3
.

. R CH CH2CCl3

(3)

. RCHClCH2CCl3 + CCl3 (4)

Tip theo (3), (4), (3), (4)....

3.5.4. Phn ng xy ho (hyrxyl ho).

C C + KMnO4 (hoc HCOOOH) C C OH OH

V d:
3 CH2 CH2 + 2 KMnO4 + 4 H2O CH3CH CH2 HCOOOH 3 HOCH2CH2OH + 2 MnO2 + 2 KOH CH3CHOHCH2OH

Nu trong iu kin khc nghit (KMnO4,un nng) th:

68

axit, xton hoc CO2

OH OH

V d:
KMnO4 CH3COOH + O C(CH3)2 t0 C KMnO4 CH3CH2CH2CH CH2 0 CH3CH2CH2COOH + CO2 + H2O t C CH3CH C(CH3)2

3.5.5. Phn ng th. Phn ng th nguyn t hyr ca cc nhm alkyl trong phn t anken xy ra nhit cao hoc c chiu sng bng tia t ngoi trong pha kh.
200 C, CCl4 CH CHClCH Cl 3 2 400-6000 C ClCH CH CH + HCl 2 2

CH3CH CH2

Cl2

Tin hnh halogen ho nhiu anken khc nhau, ngi ta i n kt lun rng hyr vinyl c thay th bng halogen kh khn hn rt nhiu so vi hyr allyl. Nh vy nu kt hp vi cc kt qu nghin cu trc y ta c dy hot ng ca nguyn t hyr bin i nh sau: Allyl > hyr 30 > hyr 20 > hyr 10 > CH4 > vinyl 3.5.6. Phn ng zn ho. y l phn ng ph v cc lin kt i cacbon-cacbon ca anken to thnh nhng phn t nh hn. Phn ng xy ra trong mi trng tr.
O C C + O3 C O C O H2O/Zn C O+ O C

Sn phm to ra l cc anhyt hoc xton. Phn ng thng dng d pht hin s c mt ca cc ni i trong phn t.

69

CU HI N TP V BI TP CHNG 3 3.1. Gi tn cc anken theo danh php thng thng v danh php IUPAC. 3.2. Cc phng php quan trng iu ch anken. 3.3. c im cu to v kh nng phn ng ca anken. 3.4. Nhng tnh cht ha hc quan trng ca anken. 3.5. Cc qui tc nh hng ca phn ng cng vo anken. 3.6. c tn theo danh php quc t cc cht sau y:
CH3 a. CH3 CH CH CH CH3 CH3 CH3 d. CH3 C C CH3 CH CH2 CH Cl CH2 Cl CH CH3 CH3 c. CH2 CH C CH2 CH3 b. CH2 C CH2 C 2 H5 CH C CH3 CH3 CH3

3.7. Vit cng thc cu to cc hp cht sau y v cho bit hp cht no c ng phn lp th: a. 3-metyl buten-1 b. 4-nitro-3-metyl buten-1 c. 4-(1-bromoetyl)-2,6-dimetyl hepten-2 3.8. Vit cng thc cu to cc sn phm to thnh trong phn ng zn ha cc hp cht sau y: a. Buten-1 b. 2,3-dimetyl buten-2 c. 2-metyl propen 3.9. Vit cng thc cu to cc sn phm to thnh trong phn ng oxi ha cc anken sau y bng KMnO4 m c un nng: a. Propen b. Buten-2 c. 2-metyl propen 3.10. Hon thnh cc s phn ng sau:
0 a.Butanol-1 300 C

Al2O3

H2SO4

Y Zn

H2 O t0C X

Z O3 Y H2 O Z
+

b.CH3CH2

CH CH CH CH3 Br Br CH3

H2 O2

70

TI LIU THAM KHO CA BI TP CHNG 3 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

71

Chng 4 ANKIN V IEN Cng thc tng qut ca loi hp cht ny l CnH2n-2 4.1. ANKIN. 4.1.1. Cu to v cch gi tn. a. Cu to. Hp cht n gin nht ca ankin l axtylen trong cc nguyn t cacbon c ocbitan lai to sp. Cc ocbitan ny lin kt vi nhau v lin kt vi hyr to thnh 3 lin kt . Mi nguyn t cacbon cn li 2 in t p t do xen ph vi nhau to thnh 2 lin kt . Cc in t ca 2 lin kt ny li xen ph vi nhau to thnh mt m my in t ging nh hnh tr bao bc xung quanh lin kt cacbon-cacbon.
H C

1,2A

C H

Cc ankin cao hn c cu to ging nh axtylen m trong cc nguyn t hyr c thay th bng cc gc ankyl khc nhau. b. Cch gi tn. Cc hp cht ankin thng c gi tn theo 2 cch sau y: 12Gi tn cc ankin ging nh l dn xut ca axtylen m trong cc nguyn t hyr c thay th bng cc gc ankyl. Gi tn theo danh php IUPAC bng cch i ui an ca hyrcacbon tng ng thnh ui in. V d: H-C C-C2H5 tylaxtylen Butin-1 5.1.2. Tnh cht vt l. Cc ankin l nhng hp cht phn cc yu nn c cc tnh cht vt l gn ging vi ankan v anken: khng tan hoc rt t tan trong nc, tan tt trong cc dung mi khng phn cc nh te, benzen, CCl4c t trng nh hn nc, nhit si tng ln khi s nguyn t cacbon trong phn t tng. 5.1.3. Cc phng php iu ch. a. Cc phng php cng nghip. Phng php iu ch axtylen: CH3-C C-CH3 imtylaxtylen Butin-2 CH3-C C-CH(CH3)2 mtylizprpylaxtylen 4-mtylpentin-2

72

1.

Than vi

Than cc Vi sng

20000 CCaC

H2O

C2H2

2- xy ho khng hon ton kh mtan:

6 CH4 + O2 2 HC CH + 2 CO + 10 H2

Axtylen dng hn, ct kim loi (n c gi trong bnh thp c bit bng cch ho tan trong axton di p sut cao), dng lm nguyn liu cc hp cht khc. b. Phng php tng hp. Phng php tch loi:
Z W C C X Y Z W C C C C

1- hyrhalogen ho cc hp cht ihalogenua.

CH CH X X KOH C CH X
KOH/ancol

KOH

C C

V d:
CH3 CH CH2 KOH/ancol Br Br CH3CH CHBr CH3 C CH

2- Phn ng axtylua kim loi vi ankylhalogenua bc 1. NaNH2 RX C C- Na+ C C H V d:

CH3 C C Na + CH3CH2Br
X X C C + 2 Zn C C
+

C C R

CH3

CH2CH3

3- halogen ho ttrahalogenua.
+ 2 ZnX2

X X

V d:
CH3 CBr Br CHBr + 2 Zn Br CH3 C CH + 2 ZnBr2

Trong tt c cc phng php nu trn y, phng php iu ch ankin bng phn ng hyrhalogen ho cc hp cht ihalogen l c ngha nht v cc hp cht ny thng d iu ch t anken. 4.1.4. Tnh cht ho hc ca ankin.

73

Tng t nh anken, ankin c m in ln do s c mt ca lin kt nn n c kh nng tham gia cc phn ng AE. Mt khc do mt in t tp trung rt ln gia hai nguyn t cacbon-cacbon ca ni 3 lm cho lin kt C- H b phn cc mnh nn ankin tham gia mt s phn ng biu hin tnh axit. a. Phn ng cng hp AE.
X Y C C + XY C C XY X Y CX CY

1- Cng hp hyr.
H2/Ni R C C R H2/NH3 R C C H R C C H R H H sn phm trans R sn phm cis

2- Cng halogen (X2 = Cl2, Br2).

C C CH3 C C Br2 X2 X X C C CBr X2 Br2 X X C C X X CH3 CHBr CH3 CBr2 CHBr2

3- Cng hp hyrhalogenua (HX = HCl, HBr, HI).

C C CH3 C CH HX HCl CH CX CH3 CCl HX CH2 HCl CH2 CH3 CX2 CCl2 CH3

4- Phn ng hyrat ho.

C C + H2O H2SO4/HgSO4 H2SO4/HgSO4 CH C OH CH2 CH3 CH OH C CH2 OH CH2 C O

H C C H + H2O CH3 C CH + H2O

CH3CHO Axtanhyt CH3 C CH3 O Axton

-

H2SO4/HgSO4

b. Cc phn ng th hin tnh axit.

C H + Baz C C

1- To thnh axtylua cc kim loi nng ho tr 1.

74

C HC CH3 C

CH + M+ CH + 2 Ag
+

C Ag CH3

C- M+ + H+ C C C Ag + 2 H+ C
+ Cu + NH4 + NH3

CH + Cu(NH3)2+

Cc mui axtylua l nhng cht tan trong nc v thng c mu c trng nn c s dng phn bit cc ankin u mch. 2- Phn ng vi kim loi kim.
C C + Na (CH3)2CH C CH + NaNH2 NH3 te C C Na + H2
+ (CH3)2CH C C Na + NH3 +

Mt trong nhng ng dng ca loi phn ng ny l dng tng hp nhng hp cht ankin cao hn.
R1 C C H + Na NH3 R1 C C- Na+ R2X R1 C C R2

4.2. HP CHT IEN. 4.2.1. Cu to v cch gi tn. ien l nhng hp cht hyrcacbon c hai ni i trong phn t v vy n c cu to tng t nh cc hp cht anken, do vy chng c nhng tnh cht ho hc tng t nh anken. Tt nhin trong mt vi trng hp n c mt s tnh cht c th cho h phn t c hai ni i. Cc ien c th c gi tn theo danh php thng thng hoc danh php quc t. Trong danh php IUPAC, ngi ta gi tn cc ien tng t nh anken, ch khc l i ui en thnh ui aien cng vi 2 s ch s ch cc v tr cc ni i. V d: CH2=CH-CH=CH2 Butien-1,3 ien c chia lm 3 loi sau y:
C C C C C C C C C , , C C C C C C C C C C
Loi ien lin hp

CH2=CH-CH2-CH=CH2 pentaien-1,4

C C

Loi khng lin hp

C C

Loi ni i lin tip

4.2.2. Cc phng php iu ch ien. Thng thng cc phng php iu ch cc ien tng t nh cc phng php dng iu ch anken. Ngoi ra trong cng nghip iu ch butaien-1,3 dng trong tng hp

75

cao su nhn to, M ngi ta dng phng php crcking butan, c dng phng php tch loi butaiol-1,4 cn Lin X dng phng php tng hp t ru tylic.
CH3CH2CH CH2 CH3CH CHCH3 CH2 OH CH2 CH2 CH2 OH t 0 C, xt CH2 t 0 C, xt t 0 C, xt CH2 CH CH CH2

0 CH3CH2CH2CH3 t C, xt

CH CH CH2

Phng php LBEP tng hp butadien-1,4 t ru tylic nhit 400-5000C vi xc tc MgO-ZnO c dng rng ri Lin X:
2 C2H5OH 2 CH3CHO 2 CH3CHO + H2 CH3CHCH2CHO CH CH CH2

OH -2 H2O H2/xt CH2 CH3CHCH2CHO CH3CHCH2CH2 OH OH OH

4.2.3. Tnh cht. Tnh cht ca ien ph thuc vo s sp xp ca cc ni i c trong phn t. Nu cc ni i khng lin hp th n c cc tnh cht tng t nh anken. Nu cc ni i lin hp vi nhau th n c mt s tnh cht khc vi anken nh sau: 1- Bn hn so vi ng phn khng lin hp. 2- Tham gia phn ng cng hp AE 1,4. 3- C kh nng tham gia cc phn ng mnh hn so vi ng phn khng lin hp. a. bn ca ien lin hp. bn ca cc ien lin hp dc xc nh bng nhit hyr ho cc ien. Kt qu thc nghim cho thy rng nhit hyr ho ca cc anken dng: RCH=CH2 30 Kcal/mol R2C=CH2, RCH=CHR 28 Kcal/mol R2C=CHR 27Kcal/mol. CH3-CH=CH-CH=CH2 (28+30) = 58Kcal/mol. 54Kcal/mol.

Da vo cc s liu trn y ta tnh c nhit hyr ho cho 2 cht: CH2=CH-CH=CH2 Theo tnh ton: Thc nghim: (30+30) = 60Kcal/mol. 57Kcal/mol.

76

So snh cc kt qu tnh ton theo l thuuyt v thc nghim ta thy rng nhit hyr ho ca thc nghim thp hn. iu chng t rng cc ien lin hp bn hn so vi cc ien khng lin hp. b. Phn ng cng 1, 4. Nu cho pentaien-1,4 tc dng vi brm trong iu kin thch hp th trc tin ta thu c 4,5-ibrmpenten-1 v tip theo l dn xut 1,2,4,5-ttrabrmpentan.
CH2 CH CH2 CH CH2 Br2 CH2 Br CH CH2 Br CH CH2 Br2 CH2 Br CH CH2 Br CH CH2 Br Br

Cn khi cho butaien-1,3 tc dng vi brm cng trong iu kin th ngoi sn phm 3,4-ibrmbuten-1 ta cn thu c 1,4-ibrmbuten-2. Phn ng cng xy ra tng t di vi cc ien lin hp khc v vi cc tc nhn khc nhau.
Br2 CH 2 CH2 CH CH CH2 CH CH CH2 + CH2 CH CH CH2

Br Br Br Br HCl CH CHClCH CH + CH CH CHCH Cl 3 2 3 2 H2/Ni CH3CH2CH CH2 + CH3CH CHCH3

S khc nhau v kt qu ca sn phm thu c ca cc phn ng ca pentaien-1,4 v butaien-1,3 vi brm c gii thch nh sau: Phn ng cng electrphin xy ra qua bc to thnh ion cacbni:
H
+

CH3
+

CH CH CH2 in bc II CH CH2 in bc I

CH2

CH CH CH2

CH2CH2

Theo s phn ng trn y, ion cacbni bc II c to thnh nh nh hng ca hiu ng +I nn bn hn ion bc I. V vy phn ng xy ra ch yu theo hng to thnh ion bc II. Mt khc ion bc II ny ch yu tn ti di dng cng hng sau:
CH3 CH CH CH2
+ +

CH3

CH CH CH2

Giai on tip theo cc anion c th cng hp vo c 2 nguyn t cacbon do to thnh mt hn hp 2 sn phm.

+

a CH CHX CH CH sn phm 1,2 3 2 b CH3CH CHCH2X

sn phm 1,4

CH3

CH CH CH2 a X- b

Khi kho st phn ng butaien -1, 3 vi HBr ngi ta nhn thy:

77

HBr, -800 C CH2 CH3CHBr CH CH2 (80%)

(20%)

CH CH CH2HBr, 40 C 40 0 C CH3CHBr CH CH2 (20%)

(80%)

CH3CH CHCH2Br

CH3CH CHCH2Br

Vy nhit thp sn phm 1,2 u tin hn, tri li nhit cao sn phm 1,4 l ch yu.
E

Ea

1,2

Ea

1,4

CH3CHBr

CH CH2 Br CH3

CH2

CH CH CH2 Br CH3 H+ CH CH CH2

CH CH CH2Br

Tin trnh phn ng 1,2

Tin trnh phn ng 1,4

Gin nng lng ca phn ng butaien-1,3 vi HBr 4.2.4. Cao su thin nhin v cao su tng hp. a. Cao su thin nhin. Cao su thin nhin c khai thc t m ca cc cy thc vt thuc h Hevia. Cy cao su u tin tm thy nam chu Phi, sau ny c trng Innxia, ng Dng. Ngoi ra m cao su cn c khai thc mt s loi cy khc nh cy si, cy b cng anh chu u, cao su c s dng vo u th k 18. Nhng ngi da l nhng ngi u tin s dng cao su. H ph bc cao su bng nhng khun t st v sy. Sau khi thu c nhng mu cao su n hi v khng thm nc, h p v vn khun t st ra thnh mnh v ko cc mnh qua mt l ming bnh to thnh cc loi bnh ng nc. nc Anh, ngi ta dng cao su th ho tan vo hyrcacbon ca nha than v thu c mt dng keo cao su. Ngi ta s dng keo cao su ny ph ln b mt ca vi lm vi khng thm nc. b mt c ph bng nha cao su khng thm nc, khng b dnh bn, ngi ta gp i chng li. Loi o ma c hai lp du nh vy do Makintosh lm ra nn c gi l o mmg t. V sau, khc phc s dnh bn ny ngi ta cho thm cc loi bt khc nhau. Mt trong nhng loi bt l lu hunh v nh pht hin ra s lu ho cao su.

78

b. Thu nhn v ch bin cao su. M cao su thu nhn c t cy cao su c lm ng li bng axit axtic (y l dng m th). Cao su th c nghin trn my nghin c nhiu rng ca. Trong qu trnh , cao su th cng c chuyn thnh dng mm mi, do c th trn ln chng vi cc cht ph gia, cht lu ho (cao su xm c trn thm b hng, cao su trng c trn thm xit titan, cao su trn thm sunfit antim) Hnh trm nm sau ca qu trnh nghin cao su, ngi ta mi gii thch c rng: trong qu trnh , cao su th (C5H8)n vi phn t lng khong 100.000-150.000 di tc dng c hc b t ra thnh nhng mnh nh hn bng s phn ct ng ly. Cc u mch gc t do ny kt hp vi xy to thnh pexit v cui cng li kt hp vi nhau to thnh nhng phn t nh hn. S gim ln ca cc phn t lm tng thm tnh n hi, mm mi ca cao su to iu kin cho s lu ho hoc trn ln vi cc cht ph gia. c. Cu to ca cao su thin nhin. Khi zn ho cao su thin nhin, ngi ta thu c cc kt qu sau:
... CH2 C CH CH2 CH2 C CH CH2 CH2 C CH CH2 ... O3

CH3 O O ... CH2 C CH CH2 H3C O CH2

CH3 O O CH2 C CH CH2 H3C O CH2 CH2

CH3 O O C O CH2 C O + ... CH3 CH CH2 ... H2O, Zn

C O + O CH CH2 CH3

C O + O CH CH2 CH3

S c mt ca ni i trong phn t cao su rt quan trng v n cho php tin hnh lu ho.

79

CH3 ... ... CH2 CH2 C CH CH2 C CH CH2 CH3 S S ... CH2 C CH CH2 CH2 CH3 S CH3 S ... CH2 C S S CH3 ... ... CH C CH CH2 S CH C CH CH2 CH3 CH2 CH CH2 CH2 CH2 CH2

CH3 C CH CH2 C CH CH2 CH3 S S C CH CH2 ... CH3 S CH3 S C S S CH3 CH C CH CH2 ... S C CH CH CH3 ... CH CH2 ... ... ... + nS

Cao su lu ho c cu to mng khng gian nn cng hn. Nu lu ho nhiu s c sn phm l ebnt dng lm cht cch in. Mt hp cht t nhin gutapetra cng c cng thc phn t ging cao su t nhin (C5H8)n nhng hai hp cht ny khc nhau v s phn b hnh hc. Cao su t nhin c cu hnh cis, cn gutapetra c cu hnh trans.
H3C H2C H C C CH2 CH2 H3C C C CH2 H H3C CH2 H C C CH2

Cao su t nhin (ng phn cis)

H3C H2C CH2 C C H H3C H2C CH2 C C H H3C H2C CH2 C C H

Gutapetra (ng phn trans) Ti sao cao su c tnh n hi? Ta bit rng mch cao su c phn t ln. Mt khc do cc nguyn t cacbon c gc lai to l 109028 cng vi s quay t do ca cc lin kt cacbon-cacbon to thnh v s cu dng khc nhau nhng v tr ni i trong phn t khng thay i. mt phn t ln, s xp t ca mch phn t s khng iu ho m rt tu tin v cu dng. Khi ko mch nhng ch

80

sp xp khng trt t b ko ra lm cho mch cao su b gin. Nu b lc ko, n li tr v trng thi bnh thng.

d. Cao su tng hp. Cao su tng hp l polybutaien. thay i tnh cht ca n, cao su tng hp thng s dng cc phn ng ng trng hp: butaien vi styren, butaien vi acrilnitrin
CH2 ... CH2 CH CH CH2 + CH2 CH CH CH2 CH2 CH CH CH2 + CH2 CH CH CH2 CH2 CH + CH2 C6H5 CH CH2 C6H5 CH CH CH2 ... CH CH CH2 xt

Cao su butaien Styren (Buna S)

81 CU HI N TP V BI TP CHNG 4

4.1. Danh php thng thng v danh php IUPAC i vi ankin. 4.2. Cc phng php iu ch ankin. 4.3. Cc tnh cht ha hc quan trng ca ankin. 4.4. a. Ti sao ankin khng c ng phn hnh hc. Vit ng phn hnh hc ca ankin c 5 cacbon c ni i. b. Ti sao xiclohexin khng tn ti. Vit ng phn hnh hc ca ankin c 6 cacbon vi vng 3 cnh. 4.5. Gi tn nhng hp cht sau y theo danh php IUPAC:
a. CH3 CH C CH3 d.(CH3)3C C C C(CH3)3 CH b. CH3 CH2 CH C C2H5 e.Cl CH2 C CH CH3 c. Br CH3 CH2 C C CH3 C C CH2 CH3

4.6. Hy dng phng php ha hc phn bit: butan, buten-1, butin-1 v butin-2. 4.7. T axetilen v nhng ha cht cn thit iu ch cc ankin sau:
a. CH3 C CH b. CH3 CH2 C C CH2 CH3 c. HC C CH2 CH2 CH2Cl

4.8. Vit cng thc cu to ca cc hirocacbon c cng thc phn t C5H8. Gi tn cc ng phn loi ankadien. 4.9. T buten-1 v cc ha cht cn thit iu ch butadien-1,3. 4.10. Hon thnh s phn ng sau:
a. CH2 CH CH CH2
+

Br2 A

B HBr B

X Br2

Y X KOH/ancol -2HBr Y

b. Buten-1

HBr

KOH/ancol -HBr

4.11. Mt ankadien c cng thc phn t C5H8, sau khi zn ha em thu phn znit to thnh thu c mt trong cc sn phm l:
CH3 C CH O O

Hy cho bit cng thc cu to ca ankadien ban u. 4.12. Vit cng thc cu to ca nhng dien c cng thc phn t C5H8. Gi tn cc ng phn v ch r cacbon lai ha sp. 4.13. Hai hirocacbon ng phn A v B c cng thc phn t C6H10 u lm mt mu nc brom v c kh nng tc dng vi ozon. Khi thu phn ozonit to thnh t A cho cho mt phn t OHCCH2CH2CHO v hai phn t CH2O. Khi thu phn ozonit to thnh t B cho 3 sn phm: CH3CO-CHO, CH2O v CH3CHO. Xc nh cng thc cu to ca A v B.

82

TI LIU THAM KHO CA BI TP CHNG 4 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

83

Chng 5 CC HP CHT HYROCACBON VNG Cc hp cht m trong cc nguyn t cacbon to vi nhau thnh mch kn gi l cc hp cht vng. 5.1. CCH GI TN V CC NG PHN. Cc hp cht vng c gi tn bng cch thm tip u ng xycl. 5.1.1. Cch gi tn cc hp cht n vng (mnxycl). gi tn cc hp cht n vng, mch chnh c chn l vng xycl sau nh s th t cc nhm th sao cho tng cc ch s l nh nht. Thng tin li, ngi ta n gin vit cc nguyn t cacbon v hyr ca vng. V d:
CH3 H3C CH3

1,2,4-trimtylxyclhexan

Trong trng hp phn t ln, mch chnh phc tp th tn gi trn y khng ph hp nn ngi ta coi vng xycl nh mt nhm th. V d:
CH3 CH2 C CH CH3 CH3 OH 3,3-imtyl-4-xyclpentylbutanol-2

5.1.2. Cch gi tn cc hp cht a vng (polyxycl). Thng thng cc hp cht a vng c chia lm cc loi sau: 1- Cc vng ring bit
(CH2)n

2- Cc vng ni vi nhau bi mt lin kt cacbon-cacbon

3- Cc vng c mt nguyn t cacbon chung

4- Cc vng c 2 nguyn t cacbon chung

84

5- Cc vng c s nguyn t cacbon chung ln hn 2

CH2

Tn gi ca 2 ging nh trnh by phn trn.

Tt c cc vng cn li c xem nh l hp cht c cu ni. Bt u nh s t mt u

cu ni theo vng ln, tip n vng b hn v cui cng l cc nguyn t cacbon ca cu ni. Nu cc nguyn t cacbon ca vng cn c cc nhm th th chn sao cho ch s l nh nht. Gi tn mch chnh ca vng, thm tip u ng bixycl- tip theo l s nguyn t cacbon ca mi vng t trong du ngoc vung (nguyn t cacbon ca 2 u cu ni khng tnh).
5 4 3 1 2 10 6 7 8 9 6 5 7

CH3
1 2 3

C(CH3)2

CH3 4 2-mtyl-bixycl[5,3,0]-kan 1,7,7-trimtyl-bixycl[2,2,1]-heptanon-2

5.1.3. ng phn. ng phn ca mt hp cht vng gm cc loi: 1- ng phn do s thay i cc nguyn t cacbon ca vng. V d: Hp cht C5H10 c cc ng phn sau y:
CH3 CH3 CH3

2- ng phn do s thay i cu to ca mch nhnh: V d:

CH3

CH3

C2H5

C2H5

CH3

H3C

CHCH3

CH2CH2CH3

3- ng phn do s sp xp ca cc nhm th khc nhau cc v tr khc nhau: V d:

R2 CH3 CH3 CH3 CH3 R1 R2 R1 R2 R1

4- ng phn hnh hc:

85

V d:
CH3 CH3 ng phn trans CH3 CH3 ng phn cis

5- ng phn quang hc xut hin khi trong phn t c cacbon bt i: V d:

R C H R C H O C H H R R C O

6- ng phn cu dng:

Gh

Thuyn

5.2. CC PHNG PHP IU CH. 5.2.1. Phng php cng nghip. T du m ta c th thu nhn mt s hp cht vng nh: xyclhecxan, mtylxyclhecxan, mtylxyclpentan, 1,2-imtylxyclpentan.n Cc dn xut xyclhecxan c th iu ch bng phn ng hyr ho benzen:
R R Mo2O3, Al2O3, 560 0 C, 21at H2/Ni, 150-2000 C, 25at

5.2.2. Phng php tng hp. tng hp mt hp cht vng thng c 2 giai on: 1- Chuyn ho mt hp cht mch h no thnh mch vng (phn ng ng vng). 2- Chuyn ho mt hp cht vng thu nhn c thnh vng cn thit phi tng hp. a. Tng hp cc hp cht xyclprpan v xyclbutan. - T ankylihalogenua
CH2 CH2 CH2 CH2Br CH2Br CH2Br CH2Br + 2Li-Mg 2Na + 2NaBr + 2LiBr + 2Mg

- Phn ng vi iazmtan

86

C C

+ CH2N2

C N

N C CH 2

Cu, t0 C C CH2 + N2 C

Cc hp cht ien-1,3 di tc dng ca tia t ngoi cho xyclbuten

CH CHR CH CHR

CH CHR CH CHR

- Phn ng quang ho xyclpentanon

O

+ CO

b. Tng hp cc hp cht xyclpentan, xyclhecxan hoc ln hn. - T ankylihalogenua

CH2Br (CH2) n CH2Br + 2Li-Mg CH2 (CH2) + 2LiBr + 2Mg n CH2

- T mui canxi icacbxylat

CH2 CH2 CH2 CH2 COO COO Ca t 0 C CH2 CH2 CH2 CH2 C O H2/Ni

- T ankan
CH3 CH3 CH CH2 CH3 CH CH3 Pt (3000 C) Pt H3C + H2 CH3 + H2

CH3CH2CH2CH2CH2CH3

c. Cc hp cht vng khng no c th iu ch t xyclankan hoc t hp cht thm.

X H2/Ni OH H2/Ni X KOH/ancol

OH

H+, t0 C

5.3. TNH CHT VT L V HA HC. 5.3.1. Tnh cht vt l. Tng t nh ankan v anken tng ng, cc hp cht vng khng phn cc, trng nh thua nc,c nhit si tng theo chiu tng ca s nguyn t cacbon 5.3.2. Tnh cht ho hc. a. Tnh cht chung. c t

87

Tr mt s phn ng c bit, xyclankan v xyclanken c cc tnh cht tng t nh ankan v anken. Phn ng th theo c ch gc ca xyclankan:
+ Cl2 + Br2

h h

Cl + HCl Br + HBr

Cc phn ng cng electrphin ca xyclanken:

Br + Br2 1,2-ibrmxyclhecxan Br CH3 1-id-1-mtylxyclpentan I H2O/Zn O CH CHCH3 CH2 CH2 CH O

CH3 + HI H3C O3

b. Cc phn ng c bit ca xyclprrpan v xyclbutan phn ng th theo c ch gc c trng cho cc xyclankan k c xyclyprpan v xyclbutan. Nhng mt khc xyclyprpan v xyclbutan cn tham gia mt s phn ng cng sau y:
H2/Ni, 80 0 C Br2/CCl4 HI H2/Ni, 120 C Br2/CCl4 HI
0

CH3CH2CH3 BrCH2CH2CH2Br CH3CH2CH2I CH3CH2CH2CH3 Khng c phn ng Khng c phn ng

Nh vy xyclbutan km hot ng ho hc hn nhiu so vi xyclprpan. c. Thuyt sc cng Maye. gii thch kh nng tham gia phn ng ca xyclprpan v xyclbutan trn y, nm 1885 gio s Baye Adong trng i hc tng hp Miukhen cho rng tt c cc nguyn t ca vng u nm trong mt mt phng, do gc ho tr ca xyclprpan l 600, xyclbutan l 900, xyclpentan l 1080, xyclhecxan l 1200 V vy khi to thnh vng, gc t din ca nguyn t cacbon b xm phm gy ra mt sc cng gi l sc cng Maye. Theo Baye, sc cng ny cng ln th vng cng t bn, tc l kh nng phn ng cng dn n ph v vng cng ln. Cng thc ton hc tnh sc cng Baye nh sau:

88

[] = (109028 - )/2 n 3 29044 4 9044

- gc a din u ca vng 5 0044 6 -5016 7 -9033 8 -12046 9 -36016

Gi tr sc cng Baye tnh c cho cc xyclankan c n nguyn t cacbon nh sau:

Nh vy theo Baye, vng c sc cng ln nht l xyclprpan v cc vng ln. Vng c sc cng nh nht l xyclpentan. Thc nghim cho thy rng i vi cc vng: xyclprpan, xyclbutan, xyclpentan sc cng Baye ph hp vi cc tnh cht ca vng. Nhng i vi xyclhecxan v cc vng ln hn sc cng Baye khng cn ngha. Xyclhecxan c sc cng ln hn xyclpentan nhng n li rt bn v bn hn c xyclpentan. Ti sao vy? iu ch c th gii thch rng, trong khi a ra thuyt ca mnh, Baye phm mt sai lm ln l coi tt c cc nguyn t cu to nn vng u nm trong mt mt phng. d. Quan nim hin i v cu to ca hp cht vng. Theo quan nim ngy nay, bn ca mt hp cht vng ph thuc: sc cng Baye (sc cng gc lin kt), sc cng Fitze (lc tc dng tng h gia cc nguyn t hoc nhm nguyn t k nhau ca vng) v lc Van-ec-van ca cc nhm khng k nhau. Cc nguyn t cacbon trong ankan c ocbitan lai to sp3 do hnh thnh lin kt chng hng cc ocbitan lai ho ny li vi nhau v c c s xen ph cc i cc gc lin kt phi l gc t din 109028.

60

109 28'

Nhng trong phn t xyclprpan, gc lin kt khng th l 109028 m l 600, do nguyn t cacbon khng th hng cc ocbitan lai ho sp3 thng hng li vi nhau nn s xen ph s t hn, lin kt s km bn hn. Trong trng hp i vi xyclbutan, gim bt sc cng mt nguyn t cacbon cn li nn to kh nng xen ph cao hn, vng bn hn.

trnh cc sc cng xyclpentan c cc cu dng thun li, nht l dng phong b v dng na gh.

Xyclhecxan c cu dng gh, xon, thuyn.

89

Gh

Xon

Thuyn

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

e a

90

Chng 6 HP CHT HYRCACBON THM Cc nh ho hc chia cc loi hp cht hu c thnh 2 loi: hu c bo v hp cht thm gm c benzen v cc loi hp cht khc c tnh cht tng t nh benzen. 6.1. CU TO CA BENZEN. Trong tt c cc hp cht hu c, benzen c nghin cu k nht. Benzen c pht hin t nm 1825 nhng mi dn nm 1931 ngi ta mi ngh c mt cng thc cu to ph hp v phi 10-15 nm sau cng thc mi c cc nh ho hc chp nhn. 6.1.1. Cng thc phn t, s lng ng phn v cu to ca Kkul 1- Benzen c cng thc phn t C6H6. Cc phng php phn tch nguyn t xc nh rng iu hon ton ng. Vi cng thc C6H6, benzen c th c cc cng thc cu to sau y:
H H C H C C C C H C H H C H C H C C H C H C H H C H C H C C CH2 C H Cng thc ioa

H Cng thc Kkul (I) CH3 C C C C CH3 (IV)

(III) (II) CH2 CH C C CH CH2 (V)

Vy cng thc no trn y s ph hp vi benzen? 2- Benzen ch cho mt sn phm th mt ln duy nht l C6H5X. Tc l nu brm ho benzen th n s cho sn phm th mt ln duy nht l C6H5Br, tng t nh vy cng ch thu c sn phm th mt ln duy nht l C6H5Cl, C6H5NO2iu chng t rng, trong cu to ca benzen, 6 nguyn t hyr hon ton tng ng nh nhau, do khi thay th mt nguyn t hyr no th cng ch cho mt v ch mt sn phm duy nht m thi. Cng thc cu to V c 2 loi hyr nn sn phm th mt ln c th l 2 sn phm, do V khng th l cu to ca benzen. Tng t nh vy cc cng thc cu to II v III cng khng ph hp v do cng thc cu to ca benzen ch c th l I hoc l IV. b. Benzen cho 3 sn phm th ng phn 2 ln C6H4X2 hoc C6H4XY, tc l ch thu c 3 sn phm ng phn brm ho 2 ln C6H4Br2 hoc 3 sn phm C6H4NO2Cl.

91
Br H C H C C C C Br H C H C Br C C C C H Br H C H C Br C C C C H H

C H

H H Br 1,2-ibrmbenzen 1,3-ibrmbenzen 1,4-ibrmbenzen

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

H C

H H VII VI V vy Kkul cho rng cng thc cu to tht ca benzen nm gia cng thc VIII v

IX.
H H C H C C C H VIII C H C H H C H C H C C H IX C H C H

iu c ngha l benzen chng phi l cng thc VIII m cng chng phi l cng thc IX m l mt cng thc cu to trung gian gia VIII v IX. Cng khng c ngha l benzen c cu to t cc phn t m trong mt na tng ng vi VIII cn na kia tng ng vi IX hoc l mi phn t c chuyn ho t VIII qua IX v ngc li. y ch c ngha l tt c cc phn t hon ton nh nhau v mi mt phn t c cu to trung gian gia VIII v IX. Mt cng thc phn t c th biu din bng nhiu cng thc cu to m trong ch c s khc nhau bi s phn b in t (cc ht nhn nguyn t sp xp nh nhau) th ngi ta ni phn t c kh nng cng hng. Cng thc cu to l cng thc cng hng. 6.1.2. bn ca vng benzen. Cng thc cu to ca Kkul trn y ph hp vi cc im a, b, c nhng nhiu yu t khc cng thc cha cp n, c bit l bn vng ca vng benzen. V d thc

92

nghim cho thy rng, phn ng c trng ca benzen l phn ng th ch khng phi l phn ng cng, m ng l ra benzen theo cng thc cu to ca Kkul th c th xem nh l xyclhecxatrien nn n phi d dng tham gia cc phn ng cng hp. so snh, ngi ta nghin cu phn ng cng hp ca xyclhecxen v benzen vi mt s tc nhn sau y: Tc nhn KMnO4(lnh, long) Br2/CCl4 (bng ti) HI H2/Ni xyclhecxen B oxy ho rt nhanh Kt hp rt nhanh Kt hp nhanh Kt hp nhanh 250C v p sut 1,4 at.
HONO2/H2SO4 HOSO3H/SO3 C6H6 X2/Fe RCl/AlCl3 ROCl/AlCl3 C6H5NO2 + H2O C6H5X C6H5R + HX + HCl

benzen Khng phn ng Khng phn ng Khng phn ng Hyr ho chm 1002000C, 105at.
Nitr ha

Trong khi , benzen tham gia tt mt s phn ng th sau y:

C6H5SO3H + H2O Sunfonic ha Halgen ha Ankyl ha Axyl ha

C6H5COR + HCl

Cc kt qu nh tnh trn y cho php kt lun rng benzen bn hn rt nhiu so vi xyclhecxen. Bng phng php nh lng nhit hyr ho v nhit phn hu, ngi ta cng thu c kt qu tng t.V d nhit hyr ha thu c bng thc nghim t hn so vi tnh ton bng l thuyt l 36 Kcal/mol. iu c ngha l benzen bn hn 36 Kcal/mol so vi s tnh ton cho xyclhecxatrien. Ngi ta gi nng lng ny l nng lng cng hng. 6.1.3. di lin kt ca cacbon-cacbon trong phn t benzen. di lin kt cacbon-cacbon ca benzen nh nhau v c gi tr vo khong gia di lin kt v ni i. Phng php nhiu x Rngen xc nh c di lin kt cacboncacbon trong benzen l 1,39A0. 6.1.4. Cu to ca benzen di nh sng ca thuyt ocbitan phn t. Benzen c cu to phng, trong tt c 6 nguyn t cacbon u nm trong mt mt phng. Vng benzen l mt vng i xng m trong cc nguyn t c ocbitan lai to sp2, vi gc lin kt l 1200. Mi nguyn t cacbon cn li mt in t p xen ph vi nhau to thnh mt h m my in t nm pha trn v pha di mt phng ca vng. Chnh s xen ph h thng 6 in t p ny li vi nhau to cho vng benzen c tnh bn vng.

93

H H H

H H H

6.1.5. Cch biu din vng benzen. Ngi ta c th biu din vng benzen bng mt trong cc cng thc cu to sau y:

6.1.6. Quy tc (4n+2) ca Huycken. Ngoi nhng hp cht c cha vng benzen, cn c rt nhiu hp cht khc cng c gi l hp cht thm, mc d b ngoi chng khng ging benzen. Vy c tnh chung cho tt c cc hp cht thm l g? Nu nhn nhn di gc thc nghim, cc hp cht thm phi l nhng hp cht m phn t ca n phi c tnh khng no ln nhng li khng tham gia cc phn ng cng hp c trng cho cc hp cht khng no. Tri li d dng tham gia cc phn ng th ging benzen. C bn cao so vi hyrcacbon tng ng v c cu to phng, c mch vng. Nu nhn nhn t gc l thuyt, mt hp cht mun l hp cht thm th trong phn t ca n phi cha h thng in t cng hng nm pha di v pha trn mt phng phn t. Mt khc s in t phi l (4n+2) in t, tc l cc in t trong phn t phi l 2, 6, 10 chnh l quy tc Huycken. V vy benzen c 6 in t nu n l hp cht thm. Da vo quy tc Huycken ta xt mt s hp cht sau y:
+

. (II) (III) (IV) (V) (VI)

(I)

Trong cc hp cht trn y ta nhn thy: (I) (II) (III) - Xyclpentaienyl-cation c 4 in t (khng thm). - Xyclpentaienyl- raical c 5 in t (khng thm). - Xyclpentaienyl- anion c 6 in t (hp cht thm).

Tng t nh vy, trong cc cu to (IV), (V), (VI) ch c cation (IV) c 6 in t l thuc loi hp cht thm. 6.1.7. Cch gi tn cc hp cht ca benzen.

94

gi mt s ln hp cht ca benzen, ngi ta gi bng cch thm tn gi ca nhm th vo t benzen.

Cl Br NO2

Clobenzen

Brmbenzen

Nitrbenzen

Mt s hp cht c tn gi ring khng lin quan n nhm th.

H3C H2N HO HOOC HO3S

Tluen

Anilin

Phnol

Axit benzic Axit benzsunfnic

Nu trong vng benzen c mt s nhm th th khi gi cn phi gi tn cc v tr nhm th. gi tn cc dn xut th 2 ln ca benzen th dng 3 tip u ng p- (para), m-(mta), o(oct):
Br Br Br o-ibrmbenzen Br m-ibrmbenzen Br Br p-ibrmbenzen

Nu 2 nhm th khc nhau th gi:

NO2 I CH3 NO2 OH

Cl Br Br p-brmibenzen m-clonitrbenzen o-nitrtluen p-brmphenol

Nu trong vng benzen c hn 2 nhm th th phi nh s: - Nu c 3 nhm th nh nhau th nh s sao cho tng ca cc ch s l nh nht
Br
1 6 5 4 2 3

Br Br
2 3 4 1 6 5

Br

Br Br Gi: 1,2,4-tribrmbenzen Khng gi: 1,4,6-tribrmbenzen

Nu cc nhm th khc nhau th chn mt nhm th nh s 1 v tip theo l cc nhm th khc, khi gi tn nhm s 1 khng gi ch s. Trng hp c nhm th no ph hp vi tn gi ring th xem nh n v tr s 1.

95

V d:
NO2 O2N Br Cl 2,6-initrtluen NO2 2-clo-4-nitrphnol CH3 NO2 OH Cl

3-clo-5-brmnitrbenzen

6.2. PHN NG TH ELETRPHIN CA HP CHT THM. Cc hp cht thm tng t nh benzen do cng hng cc in t ca vng nn lm tng tnh bn vng. Mt khc, mt in t ln cho php vng thm ng vai tr l 1 ngun in t. V vy n c kh nng tham gia cc phn ng vi tc nhn electrphin. 6.2.1. Mt s phn ng th electrphin SE ca cc cht thm. 1- Nitr ho
Ar H + HONO2
H + HOSO3H

H2SO4
SO3

Ar
Ar

NO2 + H2O
SO3H + H2O

2- Sunfnic ho
Ar

3- Halogen ho
Ar H + X2 Fe Ar X + HX (X2 = Cl2, Br2)

4- Ankyl ho Frien-Crap
Ar H + RCl AlCl3 Ar R + HCl

5- Axyl ho Frien-Crap
Ar H + RCOCl H + HONO
N N X

AlCl3

Ar Ar
Ar2

COR + HCl NO + H2O

N N Ar1 + HX

6- Nitrz ho
Ar

7- iaz ho
Ar1 H + Ar2

8- Prtn ho
Ar SO3H + H+ Ar
+ H + D

H2O

Ar Ar

H + H2SO4
+ D + H

6.2.2. C ch chung ca cc phn ng th electrnphin ca benzen. Phn ng th electrnphin ca cc hp cht thm xy ra theo mt c ch duy nht khng ph thuc vo s cnh tranh ca cc tc nhn, gm c 2 giai on:

96

C6H6 C6H5 H Y + - nhanh C6H5 + Z C6H5Y + HZ Y

+ + Y

chm

H (1) (2)

Giai on (1) l s tn cng ca tc nhn electrphin vo vng thm to thnh ion cacbni. Giai on (2) l s tch ion hyr di tc dng ca mt baz to thnh mt sn phm th. Ngy nay, bng cc phng php vt l hin i, ngi ta nhn thy rng giai on (1) ca SE xy ra qua bc to thnh phc v phc sau y:
Y
+ + Y

Y phc

+ phc Y + HZ

(1)

Y + H + Z-

(2)

Nh vy, c ch ca SE giai on (1) tng t nh AE l bc to thnh ion cacbni nhng khc vi AE bn ho sn phm bng cch cng thm 1 prtn th SE li tch i 1 prtn to thnh h lin hp in t . 6.2.3. Chng minh c ch SE. a. Khi nim v hiu ng ng v. Nu mt nguyn t bit trong trng thi chuyn tip ca phn ng c lin kt yu hn so vi trong hp cht th phn ng vi ng v nng hn ca n s xy ra chm hn. S khc nhau ca tc phn ng gy ra bi cc ng v khc nhau ca mt nguyn t gi l hiu ng ng v. Hiu ng ng v thng biu hin cc phn ng c phn ct lin kt. V d:
C H + Z C D + Z

C...H...Z C...D...Z

C- + H C- + D

Z Z

o KH v KD ngi ta nhn thy rng KH/KD ~5-8, tc l phn ng xy ra vi hyr nhanh hn khong 5-8 ln so vi tri. b. Chng minh c ch 2 bc ca SE. Ta ni phn ng SE xy ra theo c ch 2 giai on nh trnh by trn y m khng phi xy ra mt giai on:

97

Y C6H6 + Y+ C6H5 H

+ + C6H5Y + H

Ti sao vy? V rng nu thay th hyr trong nhn thm bng tri hay triti v sau tin hnh phn ng SE th nhn thy rng tc phn ng khng thay i -tc l khng c hiu ng ng v. iu c ngha l tc phn ng khng ph thuc vo giai on lm t lin kt cacbon-hyr. Ngha l tc phn ng ch ph thuc vo giai on (1) to thnh phc m khng xy ra s t lin kt nn i vi hyr, tri, triti u nh nhau. Nu phn ng xy ra theo c ch mt giai on th tt nhin phi quan st thy hiu ng ng v v c s ph v lin kt cacbon-hyr nhng iu khng nhn thy. Tng t nu giai on (2) ca c ch 2 giai on xy ra chm hn so vi (1) (n quyt nh tc phn ng) th cng phi quan st thy hiu ng ng v. iu ny cng khng nhn thy. Vy c ch 2 giai on v giai on (1) quyt nh tc phn ng trn y l ng. Ta c th nhn thy iu qua s thay i ca gin nng lng phn ng di y (ng chm chm khng lin tc ch trng hp khi thay th hyr bng tri).
E

EA ArH + Y+

+ Ar Y H

ArY + H+

Tin trnh phn ng

Vy giai on quyt nh tc phn ng l giai on (1) to thnh phc , khng ph thuc vo hyr hay tri nm v tr tn cng ca nhm th v lin kt cacbon-hyr khng b ph v. 6.2.4. C ch ca phn ng nitr ho. Tc nhn electrphin l cation nitrni NO2+ c to thnh trong phn ng ca axt sunfuric v nitric m c.
HONO2 + 2 H2SO4 + NO2+ NO2 + H + HSO4nhanh H3O+ + 2 HSO4- + NO2+ NO2+ chm NO2 + H2SO4 NO2 + H

98

6.2.5. C ch phn ng sunfnic ho. Tc nhn sunfnic ho thng dng nht l axt sunfuric t 70-100% v lum vi hm lng SO3 khc nhau.
2 H2SO4 H3O+ + HSO4- + SO3

+ H +

O O

H + SO3
-

O O SO3 + H2SO4 SO3H

SO3 + HSO4SO3
+

+ H3O

H2O

Trong cc giai on phn ng trn y, SO3 khng mang in tch dng nhng n cn nhiu in t nn ng vai tr l tc nhn electrophin. 6.2.6. C ch phn ng halogen ho.
Cl2 + FeCl3 + Cl
+

Cl

Cl . . . FeCl3 Cl
+

Cl . . . FeCl3 H
-

Cl . . . FeCl3

Cl + FeCl3 + HCl

FeCl4 +

Cl

Trong phn ng trn c th thay xc tc FeCl3 bng cc axt Luit khc nh AlCl3 6.2.7. Phn ng ankyl ho Frien-Crap.
R + Cl + AlCl3
+ + -

Cl . . .AlCl3
+

Cl . . .AlCl3 H

R R

Cl . . .AlCl3

AlCl4-

+ AlCl3 + HCl

Trong phn ng ny cng c th thay AlCl3 bng BF3, SnCl2, HF. C ch cng xy ra tng t nh vy vi phn ng axyl ho Frien-Crap.

99

6.3. NH HNG CA NHM TH N PHN NG SE. 6.3.1. Phn loi cc nhm th Tluen cng ging nh benzen, tham gia phn ng SE nhng cc sm phm to thnh l mt hn hp c t l khc nhau. V d trong phn ng sunfnic ho tluen ngi ta thu c kt qu sau:
CH3 H3C H3C H2SO4/SO3 SO3H + + CH3

SO3H SO3H p-tluensunfnic o-tluensunfnic m-tluensunfnic 62% 32% 6%

Nh vy trong sn phm to thnh ch c cc ng phn p- v o- l ch yu cn ng phn m- khng ng k. Mt khc thc nghim cng cho thy rng, tluen tham gia phn ng sunfnic ho rt mnh so vi benzen. Nghin cu cc phn ng halogen ho, ankyl ho FrienCrap.. ngi ta cng thu c kt qu tng t. iu cho php kt lun rng nhm mtyl lm tng hot tnh ca vng thm so vi benzen v hng phn ng th SE vo cc v tr octo v para. Ngc li thc nghim cng cho thy rng hp cht nitrbenzen c hot tnh km hn benzen v hng phn ng th SE vo v tr mta. Nh vy bt k mt nhm th no lin kt vi nhn benzen th s gy nh hng n kh nng phn ng ca n v quyt nh hng phn ng ca SE. Nhm th m nh hng ca n gy ra lm cho nhn thm tr nn hot ng hn vng benzen gi l nhm tng hot (nhm th loi 1). Nhm ny ch yu nh hng cc phn ng th SE vo cc v tr o- v pNhm th lm gim tnh hot ng ca vng thm gi l nhm gim hot (nhm th loi 2). Nhm ny ch yu nh hng phn ng th vo v tr m- (tr halogen). Bng phng php thc nghim, ngi ta xc nh c cc nhm th thuc loi 1 v loi 2 sau y: Cc nhm th loi 1 Tng hot mnh: -NH2(-NHR, -NR2) -OH Tng hot va: -OCH3 (-OR) -NHCOCH3 Cc nhm th loi 2 -NO2 -N+(CH3)3 -CN -COOH (COOR) -SO3H -CHO, -COR

100

Tng hot yu: -C6H5 -CH3(-R) 6.3.2. Thuyt nh hng. a. Trng hp th loi 1.

Cc nhm gim hot nhng nh hng oct v para: -F, Cl, -Br,-I

Ta ni rng nhm mtyl hot ho nhn thm v nh hng SE vo v tr para v oct. iu c ngha l nhm mtyl lm cho vng thm tham gia phn ng nhanh hn benzen v phn ng SE xy ra v tr oct v para nhanh hn v tr mta. Ni cch khc nhm mtyl lm thay i tc phn ng. V tc d phn ng c xc nh bi giai on (1) to thnh phc nn nghin cu s nh hng, ta c th nghin cu phc to thnh. Phc ca tluen c th c biu din: Cc cng thc nh hng ca para.
Y H I
+

Y CH3
+

Y CH3 H CH3
+

H II (bn nht)
+

III

Cc cng thc nh hng ca mta

CH3 Y H IV
+

CH3 Y H V

CH3 H VI

Ch c cu to cng hng II trong 6 cng thc trn y c nguyn t cacbon mang in tch dng lin kt trc tip vi nhm CH3 v do n c nhm ny lm bn ho nhiu nht bi hiu ng +I. iu gii thch rng, phn ng th para xy ra nhanh hn so vi mta. Kt qu cng thu c tng t khi so snh oct vi mta: Cc cng thc cng hng ca oct:
+

Y H VII

CH3 H VIII

CH3

Y H IX

CH3

Cng thc cu to IX bn nht nn phn ng xy ra oct nhanh hn nhiu so vi mta. b. Trng hp nhm th loi 2. Cc cng thc cng hng ca ion cacbni ca phn ng th SE nitrbenzen c biu din nh sau: trong cc cng thc th cng thc cu to XI km bn nht (kh c th tn ti)

101

do nh hng hiu ng I ca nhm NO2. Do nh hng para ch c 2 cng thc cng hng X v XII t hn so vi nh hng mta c 3 cng thc cng hng XIII, XIV v XV nn phn ng xy ra v tr mta nhanh hn para.
Y H X
+

Y NO2 H XI
+

Y
+

NO2

NO2
+

XII

Cc cng thc cng hng nh hng para ca nitrbenzen

NO2 Y H XIII
+

NO2 Y H XIV

NO2 H XV

Cc cng thc cng hng nh hng mta ca nitrbenzen. Kt qu thu c tng t khi so snh nh hng oct v mta.
+

NO2
+

NO2 Y H XVII

NO2 Y

Y H XVI

H XVIII

Cc cng thc cng hng nh hng oct ca nitrbenzen. Trong cc cng thc cng hng trn y, cng thc cng hng XVIII khng th tn ti c nn nh hng mta s xy ra nhanh hn. c. S dch chuyn in t do hiu ng lin hp. Trong cc trng hp trn y ta ch xt cc nh hng gy ra do hiu ng cm ng. i vi cc nhm th NH2, -OH s chuyn dch in t gy ra hiu ng lin hp. Sau y l cc cng thc cng hng ca ion cacbni ca anilin trong phn ng SE.
Y H NH2
+

Y
+

Y NH2 H II
+

Y NH2 III H IV

NH2

Cc nh hng para.
+

NH2 Y H V H VI

NH2 Y
+

NH2 H VII

Cc nh hng mta.

102

Do s to thnh IV bn vng v c bn ho bi hiu ng lin hp nn nh hng para u tin hn. Kt qu cng thu c tng t trong trng hp nh hng oct.
+

NH2
+

NH2 Y H IX H X

NH2 Y H XI Y

NH2

Y H VIII

Cc nh hng oct. d. nh hng ca cc nhm halogen. Cc nhm halogen l nhm th loi 2 nhng li nh hng para v oct v do hiu ng +C > -I.
X (X = -F, -Cl, -Br, -I)

6.4. NH HNG TRONG CC HP CHT HAI LN TH. S c mt ca 2 nhm th trong nhn thm s lm phc tp s nh hng ca phn ng SE. Do ta c th phn thnh cc trng hp sau: 1- Hai nhm th cng nh hng vo mt v tr th nh hng theo chiu mi tn nh sau:
O2N O2N CH3 SO3H CN NHCOCH3

2- Hai nhm th nh hng khc nhau th theo quy tc: nh hng ca nhm hot ho mnh s quyt nh hng ca phn ng SE so vi nhm hot ho yu. nh hng ca nhm tng hot s quyt nh hng ca SE so vi nhm gim hot. nh hng thay i theo dy sau: -NH2 > -OH > -OCH3 > -NHCOCH3 > -C6H5 > -CH3 > Nhm nh hng mta.

103

HO

CH3

HNO3/H2SO4

HO O2N

CH3

CH3CONH HO CHO

CH3 Br2/Fe CH3CONH HO Br2/Fe Br HO CHO + Br

CH3

CHO

Br sn phm chnh

6.5. NH HNG V S TNG HP. Nh nu trn phng php tng hp thng tin hnh sao cho thu nhn c hp cht tinh khit v cng hn ch c sn phm ph xy ra chng no cng tt chng . V d trong phn ng sau:
HNO3/H2SO4 NO2 Br2/Fe Br Br2/Fe Br HNO3/H2SO4 NO2 NO2 Br + O2N Br

Trong s phn ng trn y, ta nhn thy rng: mun thu nhn m-brmnitrbenzen th tin hnh nitr ho trc sau mi brm ho. Tri li, mun c ng phn para hoc oct th phi tin hnh ngc li. iu cng xy ra tng t trong cc trng hp khc. V d trong s phn ng sau y, nu mun iu ch m-nitrbenzic axt t tluen th trc ht phi xy ho ri sau mi tin hnh nitr ho, tri li mun iu ch p- hoc o-nitrbenzic axt th phi tin hnh ngc li.

104

O2N KMnO4 CH3 COOH HNO3/H2SO4 COOH

HNO3/H2SO4

CH3 + O2N NO2 K2Cr2O7 COOH O2N NO2

CH3

K2Cr2O7 COOH

105 CU HI N TP V BI TP CHNG 6

6.1. Gi tn theo danh php IUPAC cc hp cht sau y:

CH3 a. NO2 CH2 d. CH CH2 CH CH2 CH2 e. CH CH2 CH3 CH3 b. H C C H c. Cl Cl Cl

6.2. Sp xp theo th t tng dn hot tnh ca cc hp cht sau y trong phn ng nitro ha: a. benzen, toluen, clobenzen. b. axit benzen sunfonic, phenol, p-nitrotoluen. 6.3. Hon thnh cc s phn ng sau:
a. benzen b. Toluen c. Toluen
+ + +

tec-butanol FeCl3 Cl2 H2SO4

H2SO4 C
+

A D HNO3 H2SO4 F H2O, t0C G

6.4. T benzen hay toluen v cc ha cht cn thit hy iu ch: a. o-clonitrobenzen v p-clonitrobenzen b. m-clonitrobenzen c. 2-clo-4-nitrotoluen d. axit p-nitrobenzoic e. 2-brom-4-nitrotoluen f. 2,6-dibrom-4-nitrotoluen g. axit 2-nitro-4-brombenzoic 6.5. Trnh by c ch phn ng sunfonic ha mt hirocacbon thm v v gin biu din s bin i nng lng theo tin trnh phn ng.

106

TI LIU THAM KHO CA BI TP CHNG 6 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

107

Chng 7 DN XUT HALOGEN 7.1.CU TO. Dn xut halogen l nhng hp cht c cng thc R-X (trong R- l nhng nhm ankyl) v Ar-X ( Ar- l nhm aryl). 1- ankylhalogenua: V d: (CH3)3-Cl Tec-butylclorua CH2=CH-Cl Vinylclorua 2- arylhalogenua: V d: C6H5Br Brmbenzen m-ClC6H4NO2 m-clonitrbenzen p-IC6H4CH3 p-itluen o-ClC6H4COOH axt o-clobenzic CH2=CH-CH2Br Allylbrmua CH2Br-CH2Br 1,2-ibrmtan C6H5CH2Cl Benzylclorua CH2OH-CH2Br 2-brmtanol

7.2. CCH GI TN. Cc dn xut halogen c gi tn nh trnh by chng 1. 7.3. TNH CHT VT L. Cc dn xut halogen c mt s tnh cht vt l chung sau y: Nhit si ca ankylhalogenua cao hn cc ankan tng ng. Nhit si tng khi nguyn t lng ca dn xut halogen tng ln: dn xut flo c nhit si thp nht, dn xut i c nhit si cao nht. Phn t ankylhalogenua phn cc nhng khng ho tan trong nc (c th do khng c kh nng to lin kt hyr) nhng ho tan tt trong dung mi hu c. Cc dn xut i, brm v polyclo c t trng nng hn nc. 7.4. CC PHNG PHP IU CH. 7.4.1. Cc phng php cng nghip. Trong cng nghip cc dn xut ankylhalogenua thng c sn xut nhiu nht bng phng php clo ho trc tip hyrcacbon nhit cao theo c ch gc. V d:

108
C6H5CH3 CH2 CH4 Cl2, as CH CH3 CH3Cl Cl2, 110 0 C, as Cl2, 600 C, as CH2Cl2
0

C6H5CH2Cl CH2 CH CH2Cl CHCl3 Cl2, as CCl4 Cl2, as

Cl2, as

Trong cc phn ng thng to thnh mt hn hp sn phm nhng trong cng nghip ngi ta khng cn tch ra m s dng lun cho sn xut. Mt s dn xut halogen iu ch bng phng php AE.
HC CH2 CH CH2 CHCl Cl /CCl4 CH2 2 ClCH2 CH2Cl KOH CH2 HCl

CHCl

7.4.2. Cc phng php tng hp. a. T ancol V d:

CH3CH2CH2OH C6H5CHOHCH3 CH3CH2OH HBr PBr3 P + I2 CH3CH2CH2Br C6H5CHBrCH3 CH3CH2I

b. Halogen ho.
R H X2,as R X + HX ( X2 = Cl2, Br2)

c. Cng hyrhalogenua v halogen vo anken v ankin.

C C HX C C H X C C C C X2 X2 C C X X CX2 CX2 (X2 = Cl2, Br2) (X2 = Cl2, Br2)
I + X

d. Thay th halogen ln nhau.

R X + IR

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

Tc nhn baz c cp in t t do tn cng vo trung tm dng ca phn t thay th nhm halogen ca nhm hp cht ankylhalogenua. Phn ng loi ny gi l phn ng th nuclphin SN. Mt khc ankylhalogenua cn tham gia phn ng tch loi to thnh cc hp cht hyrcacbon cha no v mt s phn ng khc.

109

1- Phn ng tch loi.

C C KOH C C + HX

H X

V d:
CH3CH CH2 KOH H Cl
+ X Ancol + X R OH te + X R OR' Ancol + HX R OH Ankin R C C R' + X Ankan R R' + NaX Ankyliua R I + X + X Hp cht nitrin R CN R'COOR Este + X R NH2 + HX Amin bc I + HX Amin bc II R NHR'

CH3

CH CH2 + HCl

2- Phn ng th nuclphin SN.

Z OH OR' H2O C CR' NaR' R X+ ICNR'COONH3 R'NH2 R'NHR' Ar H R Z

R NR'R' R Ar

+ HX + HX

Amin bc III Ankyl ha

3- Tng hp Grinha
R X + CH3CH2Cl Mg te khan te khan RMgX CH3CH2MgCl

+ Mg

4- Phn ng kh: - Kh bng kim loi:

R X + H2 C4H9Br + H2 Ni Ni R H + HX C4H10 + HBr

- Kh bng ho hc:
R X + M CCl4 H+ Fe/H2O R H + M+ + XCHCl3

7.6. PHN NG TH NUCLPHIN SN. 7.6.1. Phn ng bc I v bc II. a. Xt phn ng iu ch ru mtylic t mtylbrmua:
CH3Br + HO CH3OH + Br

110

Nu phn ng l kt qu ca s va chm gia cc ion hyrxyl v phn t mtylbrmua th vn tc phn ng phi ph thuc vo nng ca c hai thnh phn , nn nu tng nng ca HO- hoc CH3Br ln hai ln th tc phn ng cng phi tng gp hai ln v ngc li. Thc nghim xc nhn iu xy ra nn tc ca phn ng trn y l: v = k [CH3Br] [HO-] k l hng s b. Xt phn ng:
(CH3)3C Br + HO(CH3)3C OH + Br

Thc nghim cho thy rng, trong phn ng ny nu tng nng ca (CH3)3C-Br ln 2 ln th tc ca phn ng tng gp i v nu gim nng (CH3)3C-Br 2 ln th tc ca phn ng s gim 2 ln. Tri li, nu tng hoc gim nng HO- th tc ca phn ng vn khng thay i - tc l tc ca phn ng khng ph thuc vo nng ca ion HO-. Vy tc phn ng tec-butylbrmua vi ion HO- ch ph thuc vo nng ca (CH3)3C-Br cho nn c th vit: v = k[(CH3)3C-Br] Ngi ta ni rng, phn ng ca ru mtylic vi ion HO- l phn ng bc II, cn phn ng tec-butylbrmua vi ion HO- l phn ng bc I. Vy ti sao cc phn ng c bc khc nhau v trong phn ng ca tec-butylbrmua, tc phn ng li khng ph thuc vo nng ca ion HO- ? gii thch nhng vn ny ngi ta cho rng phn ng SN xy ra theo 2 c ch khc nhau. 7.6.2. C ch SN2. a. C ch: Phn ng ca mtylbrmua vi ion HO- trn y l phn ng bc II v n c vit di dng c ch nh sau:
H HO + H H
-

Br

H HO . . . . C . . . . Br H H

H HO
-

H + Br

Theo nh c ch c trnh by trn y th ch nhng ion HO no va chm vi phn t mtylbrmua t pha sau (pha ngc vi nguyn t brm) v ch c nhng va chm no t c nng lng hot ho Ea cn thit th mi lm tch c ion Br- v hnh thnh lin kt COH. Trng thi chuyn tip c cu to m nguyn t cacbon c mt phn no lin kt vi HO- v mt phn no lin kt vi Br-. y lin kt C-OH cha c hon ton hnh thnh v lin kt C-Br cha hon ton b t ra cn cc ion HO- v Br- c phn b xa nhau nht, 3 nguyn t hyr v nguyn t cacbon nm trong mt mt phng vi gc lin kt l 1200.

Giai on tip theo, in tch m ca HO- b gim dn v n chuyn giao in t n to thnh lin kt C-OH, brm mang theo cp in t v to thnh ion Br-. b. Ho lp th ca phn ng SN2. Thc nghim chng minh rng phn ng SN2 xy ra vi s o ngc hon ton cu hnh. V d khi cho R(-)-2-brmctan tc dng vi NaOH nu trong iu kin ca c ch SN2 th s thu c S(-)-ctanol-2. Trong sn phm to thnh ca s nghch o hon ton cu hnh ny nhm HO- nm v tr i nghch vi nhm Br- trc y (tng t nh mt ci d che ma b lt ngc li).
CH3 H C Br NaOH C6H13 (R)-Brmctan CH3 HO C H C6H13 (S)-ctanol-2

111

S o ngc cu hnh cho php kt lun rng trong phn ng SN2 tc nhn nuclphin tn cng t pha i ngc vi nhm halogen. c. nh hng ca cc nhm th n phn ng SN. Trong phn ng SN2 kh nng phn ng ca R-X thay i theo dy sau: CH3X > halogen bc I > halogen bc II > halogen bc III S bin i trn y gii thch rng, phn ng SN2 xy ra mt giai on qua bc hnh thnh trng thi chuyn tip nn cc yu t in t khng c ngha lm nh hng n tc phn ng m ch c cc yu t nh hng n s tn cng ca nhm OH vo trung tm phn ng mi lm thay i tc phn ng. Ta xt cc trng thi chuyn tip sau y:
H Z. . . H MtylH . . .X H Z. . . H tylCH3 . . .X CH3 Z. . . H IzprpylCH3 . . .X CH3 Z. . . CH3 . . .X

CH3 Tec-butyl-

Qua cc trng thi chuyn tip trn y, ta nhn thy rng nu nguyn t hyr trong nhm mtyl c thay th bi nhiu nhm mtyl th s cn tr khng gian lm nh hng n s tn cng ca tc nhn Z vo nguyn t cacbon cng tng ln. iu s lm tng nng lng hot ho ca phn ng tc l lm gim tc phn ng. Vy tc ca phn ng SN2 c quyt nh ch yu bi nh hng ca cc yu t khng gian.

112

7.6.3. C ch ca phn ng SN1. a. C ch: C ch ca phn ng SN1 xy ra nh sau:

CH3 CH3 C Br CH3 CH3 CH3 C CH3
+

CH3 chm CH3 C CH3 + Br+

(1)

CH3 + HO
-

nhanh

CH3

C CH3 (2) OH

y tc phn ng c xc nh bi giai on (1). b. Ho lp th ca phn ng SN1. Thc nghim chng minh rng, phn ng SN1 xy ra vi s raxmic ho. V d: khi hyrat ho (-)-2-brmctan trong iu kin ca phn ng SN1 (nng HO- thp) th s thu c bin th raxmic ()-ctanol-2.
(-) -C6H13CHCH3 Br HO-, H2O (+) -C6H13CHCH3 OH

S raxemic ho ca sn phm th SN1 c th gii thch nh sau: Phn ng SN1xy ra qua bc to thnh ion cacbni c cu trc phng:
a H13C6
+

HOH

H13C6 HO C H H3C (+)-ctanol-2

a CH3

C6H13 H C OH CH3 (-)-ctanol-2

Do c cu trc phng nn kh nng tn cng ca ion HO- vo hai pha ca mt phng hon ton nh nhau, kt qu to thnh cc lng ng phn quay phi v quay tri nh nhau (tc l to thnh bin th raxmic). c. nh hng ca cc nhm th n phn ng SN1. Thc nghim chng minh rng, kh nng phn ng ca R-X trong cc phn ng SN1 thay i nh sau: Allyl > benzyl > R3C-X > R2CH-X > R-CH2-X > CH3-X

113

S thay i kh nng phn ng trn y c th gii thch rng v phn ng xy ra qua bc hnh thnh ion cacbni nn cc yu t no lm bn ho ion ny s lm cho phn ng xy ra nhanh hn. d. Phn ng SN1 xy ra vi s chuyn v. V qua bc to thnh ion cacbni nn phn ng SN1 xy ra cng vi s chuyn v. V d:
CH3 CH3 CH3 CH3 C CH2 Br CH3 C CH2 OC2H5 CH3 CH3 CH3 CH3 C C CH2 CH3 sn phm chnh OC2H5 CH CH3 CH3

C2H5OH S N1

114 CU HI N TP V BI TP CHNG 7

7.1. Gi tn theo danh php IUPAC cc hp cht sau y:

Cl a. (CH3)3C CH CH2 Br Br c. CH3 CH2 C CH2Cl CH(CH3)2 Br b. H2C C CH CH CH CH2Cl CH3 d.(CH3)2CH CH2 CH(CH2 CH2Cl)2

7.2. Vit phng trnh phn ng ca Toluen vi clo trong cc iu kin sau: a. Trong iu kin nhit cao v c nh sng xc tc. b. Trong iu kin c mt bt st v nhit thng. 7.3. Hon thnh cc s phn ng sau y:
a. xiclohexanol b. HO CH2
+

PBr3

NH3 PCl3

B C
+

(CH2)3
+

CH2 OH

Zn F

c. (CH3)3C Br d. CH3CH2CH2Br

KOH
+

CH3OH E t0C cao CH3OH NaOCH3

7.4. Vit cng thc cu to cc sn phm to thnh trong phn ng gia cc hp cht sau y: a. 2-clopropan v natri etylat. b. 2-brombutan v KOH m c trong ru v un nng. c. 2-brombutan v dung dch KOH long trong nc nhit thng. 7.5. Hon thnh cc s phn ng tsau y:
H a. C6H5 C OH CH3
+

SOCl2

Pyridin

Vai tr ca Pyridin trong phn ng trn v c im lp th ca sn phm to thnh?

b.CH3 CH2 O C CH2 C O CH2 CH3 O O
+

C2H5I

C2H5O-

7.6. iu ch cc sn phm sau y: a. 2-brompropan (izopropyl bromua) t propanol-1. b. n-propyl bromua t 1,2-dibrompropan. c. 2-metoxibutan t n-butyl iodua.

115

TI LIU THAM KHO CA BI TP CHNG 7 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

116

Chng 8 HP CHT C NGUYN T Ho hc c nguyn t l ho hc ca cc hp cht hu c vi tt c cc nguyn t. Mt s lng rt ln cc nguyn t trong bng tun hon l kim loi, do hn mt na cc hp cht c nguyn t l cc hp cht c kim. l nhng hp cht m trong nguyn t kim loi lin kt trc tip vi nguyn t cacbon bng lin kt cng ho tr hoc lin kt ion. Cc hp cht ankyl hoc aryl ca cc nguyn t kim loi kim hoc kim th hot ng mnh: chng d b phn hu bi axt, nc, ru cho sn phm l hyrcacbon, d b oxy ho bi oxy phn t, tc dng vi cc hp cht c cha nhm cacbnyl, tham gia nhiu phn ng vi cc hp cht c cha cc nhm th l oxy, lu hunh, nit 8.1. CC HP CHT C NGUYN T CA KIM LOI KIM. 8.1.1. Cc phng php iu ch. a. T ankyl- hoc arylhalogenua.
(Ar-), R X + 2M RM + RX RM + MX R R + MX (1) (2)

Trong phn ng iu ch trn y cn lu rng: Phn ng phi tin hnh trong dung mi tr (hecxan, ctan) Phn ng vi kim loi Natri khng dng (1) m tip tc (2). Phn ng vi Kali thng ch xy ra theo (1).
R2Hg + 2M 2RM + Hg
2 CH3Li + Hg

b. T hp cht c thy ngn. V d:

(CH3)2Hg + 2Li

c. T axtylen
HC HC CH + NaNH2 CH + 2 NaNH2 Na Na C C CH + NH3 C Na + 2 NH3

8.1.2. Tnh cht ho hc. a. Phn ng th hyr bng kim loi

(Ar-), R H + R'M (Ar-), R M + R'H

V d:
CH3Na + C6H5CH3
HC CH + 2 C6H5Na

C6H5CH2Na + CH4
Na C C Na + 2C6H6

b. Phn ng trao i thnh hp cht c kim mi.

R X + R' Li R Li + R' X

117

V d:
C6H5CH2Br + C2H5Li C6H5CH2Li + C2H5Br

c. Phn ng cng vo cc hp cht khng no.

(C6H5)2C CH2 + C4H9Li (C6H5)2C Li CH2C4H9

(Loi phn ng ny dng iu ch cao su tng hp) V d:

CH3 CH2 H3C C C C4H9 CH2 C CH CH2 + C4H9Li H + CH2 CH2Li+
izpren

CH3 C4H9 CH2 H3C C C CH2

+ C CH CH2Li -

CH3 C CH CH2 C4H9 H C C CH2 CH2 C CH2 H3C

H CH2

CH2Li+

H3C

C C CH2 H3C H Li+

CH2 C H

C4H9

8.2. CC HP CHT C KIM CA KIM LOI KIM TH. 8.2.1. Hp cht c magi. Hp cht c magi gm c 2 loi: R2Mg v RMgX (tc nhn Grinha). a. Cc phng php iu ch. Cho Magi tc dng vi ankylhalogenua tong ete khan
R X + Mg R MgX
C6H5MgCl

V d:
C6H5Cl + Mg

ClCH2CH2CH2CH2Cl + 2Mg
Br C6H4 Br + 2Mg

ClMg
BrMg

(CH2)4
C6H4

MgCl

MgBr

T cc hp cht c hyr linh ng

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

d. Cu to. Cho n nay, mt trong nhng hp cht c nguyn t quan trng l hp cht c magi vn cha c xc nh mt cch chi tit nhng ngi ta gi thit rng trong dung mi te hp cht Grinha tn ti di dng cn bng nh sau:
X 2 R MgX R Mg R Mg X R2Mg + MgX2

118

Thng thng ngi ta thng hay vit cng thc cu to ca hp cht Grinha di dng:
-

R Mg

c. Cc phn ng quan trng ca hp cht Grinha. 1- Phn ng vi cc hp cht c hyr linh ng dng H-A.
H A RH H2O RH CH3OH RH RNH2 RH RSH RH + A MgX + HO MgX + CH3O MgX + RNH MgX + RS MgX

R MgX

Cc phn ng ny thng c s dng xc nh linh ng ca hyr bng cch so snh lng kh mtan bay ra khi s dng hp cht Grinha l CH3MgCl. 2- Cc phn ng vi halogen, xy, lu hunh:
R MgX + X2 R MgX + O2 R MgX + S R X + MgX2 H2O R OOMgX R OH + HO MgX HO RSH + HO MgX RS MgX 2
R R' + MgX2 R2Cd + MgX2 + MgCl2

3- Phn ng vi dn xut halogen.

R MgX + R' X 2 R MgX + CdCl2

4- Cc phn ng vi hp cht cacbnyl.

R MgX + HCHO
R MgX + R'CHO

R CH2OMgX
R CH OMgX R'

H2O
H2O

R CH2OH + HO MgX ancol bc I

R CH OH + HO MgX R' ancol bc II R''

R'' R MgX + R' C O R'' R C OMgX R'

OR'' R MgX + R' COOR'' R C OMgX R' R' R MgX + R C R' O R C OMgX R

H2O

C OH + HO MgX

R' ancol bc III

R C R' + R''O MgX O R' R C OH + HO MgX R

119

C ch ca phn ng trn y n nay cha c chng minh tht chi tit nhng phn ng xy ra theo c ch vng c nhiu ngi chp nhn nht.
R C O + 2 R' MgX R R C R O R' Mg R' Mg X X R C R O MgX H2O R C R OH R' + Mg X OH R' + R' MgX

d. Mt s phn ng quan trng khc ca hp cht Grinha. 1- Phn ng vi tylenxit

R MgX + H2C CH2 O R CH2 CH2 OMgX H2O R CH2 CH2 OH + HO MgX

2- Phn ng vi ixitcacbon
R MgX + CO2 R COOMgX
R C NMgX H2O R'

H2O

R COOH + HO MgX
R' + NH3

3- Phn ng vi hp cht nitrin

R MgX + R' C N R C NH H2O R C R' O

8.3. CC HP CHT C PHI KIM. 8.3.1. Hp cht c pht pho. Hp cht c pht pho gm c 2 loi: 1- Loi lin kt P-C trong nguyn t pht pho lin kt vi nguyn t cacbon. 2- Loi cc sn phm ca cc axt v c ca pht pho trong pht pho khng lin kt trc tip vi nguyn t cacbon m qua mt nguyn t trung tm nh xy, lu hunh, nit a- Cc hp cht c pht pho loi 1. Tng t nh phn t amnic NH3 hp cht pht phua hyr PH3 l hp cht u ca dy hp cht ny. Tip theo tu thuc vo s lng s nguyn t hyr trong phn t PH3 c thay th m ta c cc hp cht pht phin bc I, bc II, bc III khc nhau. Khc vi cc hp cht amin, cc hp cht pht phin d b xy ho to thnh cc xit RH2P=O, R2HP=O, R3P=O. Nu ankyl ho pht phin th s thu c mui phtphoni.
R3P + RX R4P+X-

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

H R P OH O R

120 H
P R O R

OH P OH O R

R P OH O

Cc hp cht pht pho loi 1 c iu ch bng phng php sau: - Ankyl ho cc pht phin kim loi. V d:
PH2Na + RI RPH2 + NaI

RPHLi + R'Br

RR'PH + LiBr RPH2 C6H13 CH CH3 PH2

- Kh cc dn xut clophtphin
RPCl2

- Cng phtphin vo anken

C6H13CH CH2 + PH3

- Tng hp bng tc nhn Grinha.

3RMgX + PCl3 R3P + 3MgXCl

Cc hp cht pht phin c mt s tnh cht ho hc c trng sau: - D b zn ho

RPH2 R2PH R3P O O O RH2PO3 R2HPO2 R3PO (CH3)4P+I-

- Ankyl ho thnh mui phtphoni

(CH3)3P + CH3I

T mui phtphoni c th iu ch phtphinmtylen c ng dng trong tng hp Vitich nh sau:

(C6H5)3P CHR2X + C6H5Li (C6H5)3P CR2

(C6H5)3P
-

CR2
+

(C6H5)3P+ CR2
-

(C6H5)3P

CR2

O CR'2

O CR'2 O

O CR'2

R2C CR'2 + (C6H5)3P

b. Cc hp cht c pht pho loi 2. Loi hp cht ny c th c iu ch bng mt trong cc phng php sau:
RPCl2 + 2NaOC2H5 R P(OC2H5)2 + 2NaCl

Este ny d b chuyn v di tc dng ca R-X.

P(OC2H5)2

121 + R'I

RR'P

O + C2H5I

OC2H5 R P(OC2H5)2 + R'I O RR'P O + C2H5I

OC2H5

Tng t nh vy ta c:
P(OC2H5)3 C2H5I C2H5 P(OC2H5)2 O

Cc este ny khi b thu phn th to thnh cc axit tng ng:

R P(OC2H5)2 + 2 HX O R P(OH)2 + 2 C2H5X O

122 CU HI N TP V BI TP CHNG 8

8.1. T C2H5MgBr v nhng ho cht cn thit iu ch cc hp cht sau:

a.CH3CH2CH2OH CH3 OH b.CH3CH2CH2CH2OH c. (C2H5)3COH OH e.CH3CH2 C C2H5 CH3

d.CH3 CH2 C C3H7

8.2. Hon thnh cc s phn ng sau:

a. CH3MgCl b. C2H5MgBr
+ +

C2H5OH CH3NH2

c. (CH3)2CHMgI

1. CO2 2. H3O+ d. C6H5MgBr 1. HCHO 2. H3O+ 1. C6H5COCl e. C2H5MgBr 2. H3O+

8.3. iu ch cc sn phm sau y: a. xiclopentylcacbinol t xiclopenten. b. pentanol-3 t propanal. c. butanal t propanol-1. 8.4. Hp cht A (C5H12O2) c tnh quang hot. Khi cho 0,52 gam A tc dng vi CH3MgBr, ta thu c 112 cm3 metan trong iu kin tiu chun v hp cht B. Khi cho B tc dng vi CH3I cho ra hp cht C khng c tnh quang hot. Vit tt c nhng cng thc c th c ca A v B. 8.5. Vit phng trnh phn ng ca C6H5MgBr vi cc cht sau: a. I2 d. CH3CHO b. AgBr e. CH3COCl c. CH2O f. CO2

TI LIU THAM KHO CA BI TP CHNG 8 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

123

Chng 9 DN XUT HYRXI CA HYRCACBON (Ancol v Phnol) A. ANCOL. 9.1. CU TO, PHN LOI V CCH GI TN. 9.1.1. Cu to. Ancol l nhng hp cht c cng thc R-OH, trong R- l cc nhm ankyl, ankenyl, ankinyl, xyclankyl V d:
(CH3)3C OH Ancol tec-butylic CH2 OH CH CH2 H2C CH CH2OH Ancol allylic OH Ancol xyclhecxylic Cl CH2 CH2 OH Ancol clotylic CH2OH Ancol benzylic

OH OH Glyxrin

Tt c cc ancol u c cha nhm OH, l nhm chc quyt nh tnh cht c trng cho loi hp cht ny. 9.1.2. Phn loi. Ngi ta phn loi bng nhiu cch khc nhau. Thng thng th da vo s nhm OH c trong cc phn t ancol phn thnh ancol n chc hoc a chc. Cng rt nhiu khi ngi ta da vo bc lin kt ca nguyn t cacbon phn loi ancol thnh bc I, bc II, bc III. V d:
R CH2 OH Ancol 10 R CH R' OH Ancol n chc R2CH OH Ancol 20 OH OH R3C OH 0 Ancol 3 R CH CH CH R'

R CH CH R'

OH OH OH Ancol a chc

9.1.3. Cch gi tn. gi cc ancol ngi ta thng s dng cc danh php sau: a. Danh php thng thng. Trong danh php ny ngi ta gi tn ca nhm chc ankyl, ankenyl, ankinyl cng vi ui ic. V d:

124

CH3 CH3CH2OH Ancol tylic CH3 CH CH3 CH3CH2 C CH3 OH Ancol izprpylic OH Ancol tec-pentylic

b. Tn gi hp l (tn gi cacbinol). Trong danh php ny ngi ta xem cc ancol nh cc dn xut ca cacbinol CH3OH. V d:
(C6H5)3C OH Triphnylcacbinol (C2H5)3C OH Tritylcacbinol

c. Danh php IUPAC. 1- Chn mch di nht c cha nhm OH lm mch chnh v coi hp cht phi gi l dn xut ca mch chnh m trong cc nguyn t hyr c thay th bng cc nhm th. 2- nh s th t mch chnh sao cho nhm OH c ch s l nh nht. 3- Gi tn cc hp cht bng cch tn cc nhm th cng vi cc ch s ca n trc tn gi ca mch chnh (tn gi ca mch chnh c to thnh bng cch cng thm ui ol vo tn gi ca cc hp cht hyrcacbon tng ng). V d:
CH3 CH3 OH CH3 CH2 CH CH2 OH CH3 CH3 CH CH CH3 OH 3-Mtylbutanol-2

Mtanol

2-Mtylbutanol-1

9.2. TNH CHT VT L. a. S c mt ca nhm OH trong phn t ancol lm cho phn t phn cc do d ho tan trong nc. Nhng khi gc R- trong cc phn t tng ln th ho tan ca cc ancol trong nc gim dn. Trong thc t ch c cc ancol mch thng co 4 n 5 nguyn t cacbon tr xung l ho tan tt trong nc. b. Nhit si ca ancol tng khi phn t lng tng ln. Mt khc nhit si ca ancol cng cao hn nhiu so vi cc hp cht c cng phn t lng vi n. V d: CH3CH2CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2CH2CH2OH CH3CH2CH2Cl M 72 74 74 79 0 1,18 1,36 2,10 t 0 sC 36 35 118 47

Cc kt qu thu nhn c trn y c th gii thch bng 2 yu t: 1- Phn t ancol phn cc mnh do c mmen phn cc ln nn c nhit si cao.

125

2- Ancol c kh nng to lin kt hyr.

R R R O...H O...H O...H . . .H O...H O...H O... R R R

Lin kt hyr l lin kt m trong nguyn t hyr ng vai tr lm cu ni gia 2 nguyn t m in, mt khc mt trong hai nguyn t m in phi c lin kt cng ho tr vi hyr cn nguyn t kia c lin kt bng lc ht tnh in. to lin kt hyr trong phn t cn phi c mt cc nguyn t c m in ln hn nh: F, O, N. Trong ph hng ngoi: - nhm OH ring bit c (OH) = 3620cm-1 - nhm OH lin kt hyr c (OH) = 3350cm-1. 9.3. CC PHNG PHP IU CH. 9.3.1. Phng php cng nghip. thu nhn ancol trong cng nghip c 2 phng php chnh: hyrat ho cc anken v ln men, thu phn cc hyrat cacbon. a. Hyrat ho cc anken. T phng php crcking du m, ngi ta thu nhn c cc anken c 4 n 5 nguyn t cacbon, sau d dng chuyn thnh ancol bng phn ng hyrat ho. V d:
H2C CH2 CH3CH CH2 H2O/H2SO4 H2O/H2SO4 CH3CH2OH CH3CHOHCH3

b. Ln men v thu phn cc hyrat cacbon. Thu phn ng bng men ru qua 2 giai on chnh: thu phn v chng ct. Cht lng ru ph thuc vo nguyn liu ban u; nu t ng s thu c C2H5OH c cht lng tt, t tinh bt cc loi s c cc sn phm ph. Trong chin tranh th gii th II, Beisman ngi c dng men vi sinh Clostridum Actobutylicum (20%), axton (30%). Axton c s dng lm thuc sng khng khi. Phng php ny v sau c s dng sn xut n-butanol dng cho cng nghip t. c. Phng php ring dng sn xut mtanol.
CO + 2 H2 2CH4 + Cr2O3, ZnO, 300-4000 C CH3OH 210at 100at, 1000 C O2 2CH3OH

9.3.2. Phng php tng hp phng th nghim.

126

a. Hyr bo ho.
C C + (BH3)2 C C H2O2, HO
-

+ B(OH)3

H BH2

H OH

V d:
(CH3)3C CH CH2 (BH3)2 H2O2, HO(CH3)3C CH2 CH2 OH

b. Tng hp Grinha. Trong phng th nghim ancol c tn hp theo phn ng Grinha nh trnh by trong phn hp cht c magi. c. Thu phn ankylhalogenua (xem phn dn xut halogen) Trong cc phn ng nu trn y, tng hp Grinha l quan trng nht v: cc hp cht u ca phn ng ny l dn xut halogen thng d tm, phn ng c hiu sut cao, c th tng hp cc ancol n gin hoc phc tp khc nhau. im hn ch ln nht ca phn ng tng hp Grinha l ngoi nhm th trc tip tham gia phn ng cc hp cht u khng c cha cc nhm c cha hyr linh ng nh COOH, -OH, -NH2, -SO3Hcng nh cc nhm cacbnyl khng cn thit khc. d. Phng php thit lp mt phn ng Grinha Hu ht cc ancol u c th tng hp bng phng php Grinha bng nhng cch t hp cc tc nhn khc nhau. V vy phi chn con ng tng hp sao cho ti u nht. V d: hp cht 2-phnylhecxanol-2 c th tng hp bng 2 cch sau y:
CH3 CH3CH2CH2CH2 C O CH3CH2CH2CH2MgBr + CH3 C O CH3CH2CH2CH2 CH3 + BrMg CH3CH2CH2CH2 C OH CH3 C OH (2) (1)

Trong 2 cch trn y th nn chn (2) v hp cht xton d iu ch hn nhiu so vi (1). 9.4. TNH CHT HO HC. Tnh cht ho hc ca ancol c xc nh bi nhm OH c trong phn t. V vy kh nng c th xy ra cc loi phn ng sau y: Phn ng lm ph v lin kt C OH vi s tch i nhm OH. Phn ng lm ph v lin kt O H vi s tch i hyr.

127

Nhm R- ni chung ch c ngha lm nh hng n tc v hng ca phn ng m thi. 9.4.1. Cc phn ng lm t lin kt C OH. a. Phn ng vi hyrhalogenua.
R OH + HX R X + H2O

Kh nng phn ng ca HX: HI > HBr > HCl Kh nng phn ng ca ROH: R3C-OH >R2CH-OH >RCH2-OH >CH3-OH. V d:
CH3 CH CH3 OH CH3CH2CH2CH2OH HCl HBr CH3 CH CH3 Br CH3CH2CH2CH2Cl

b. Phn ng vi trihalogenua pht pho.

R OH + PX3 R X + H3PO3
PBr3

(PX3 = PBr3, PI3)

V d:
CH3CH2CH2CH2OH C6H5CHCH3 OH CH3CH2CH2OH P + I2 PBr3 CH3CH2CH2CH2Br

C6H5CHCH3 Br CH3CH2CH2I

c. Phn ng tch loi.

C C H OH H2SO4 C C + H2O

V d:
OH Al2O3, 250 0 C

9.4.2. Phn ng lm t lien kt O-H. a. Phn ng ca ancol ging nh mt axit vi cc kim loi hot ng mnh.
RO H + M
- + RO M + H2

Kh nng phn ng ca RO-H: CH3OH > RCH2OH > R2CHOH > R3C-OH V du:

128

CH3CH2OH + Na (CH3)2CH OH + Al

CH3CH2O-Na+ + H2 (CH3)2CH O 3 Al+3 + H2

-

b. Phn ng to thnh este (phn ng este ha).

CH3CH2OH + H2SO4 CH3CH2OH + CH3COOH CH3CH2OSO3H + H2O tylsunfat axit H+ CH3COOCH2CH3 + H2O

c. Phn ng xy ha.
Cu, 2500 C R CH2 OH Ancol 10 KMnO4 R2C O Khng phn ng RCHO KMnO4 KMnO4 R COOH

R2CH OH Ancol 20

R3C OH + KMnO4 (trung tnh) Ancol 30

V d:
CH3CH2CH2OH Cu, 2500 C CH3CH2CHO + H2 CH3CH2CH2COOH O

CH3CH2CH2CH2OH OH

KMnO4

K2Cr2O7

9.4.3. Phn ng vi hyrhalogenua. y l phn ng xy ra khi cho kh hyrhalogenua i qua ancol hoc un nng ancol vi axt HX m c. V d:
CH3CH2CH2OH (CH3)3C OH HCl, ZnCl2, t0 C HCl . CH3CH2CH2Cl Cl

(CH3)3C

Cc phn ng ca ancol vi hyrhalogenua xy ra theo c ch SN1 v SN2. C ch SN1:

ROH + HX ROH2 R+ + X+ ROH2 + X +

R+ + H2O RX

129

Phn ng xy ra theo c ch ny vi hu ht cc ancol tr mtanol v cc ancol bc I. C ch SN2:

ROH + HX X + ROH2
+ +

ROH2 + X
-

X . . . R. . .OH2

RX + H2O

Phn ng xy ra theo c ch ny vi mtanol v cc ancol bc I. 9.4.4. Phn ng xy ho ancol. a. Khi nim xy ho - kh trong ho hc hu c. Theo quan nim trc y, xy ho tc l a thm nguyn t xy vo phn t, kh tc l bt i nguyn t xy. V d:
RCHO R CONH2 O LiAlH4 R COOH R CH2NH2

Trong ho hc v c, s xy ho-kh gn lin vi s nhn v cho in t, tri li khi nim ny khng ph hp vi ho hc hu c v y cacbon lun c ho tr 4. V vy trong ho hc hu c, ngi ta dng khi nim s xy ho (s phn cc)- tc l s in tch quy c ca nguyn t tnh c khi gi thit rng phn t gm ton nhng ion tri du (s xy ho c k hiu l n). Trong khi nim ny s xy ho c th l m, dng, bng 0. Nguyn t cacbon trong cc hp cht hu c c s xy ho t -4 n +4. xc nh s xy ho, ngi ta a ra mt s quy c sau y: - Tng i s ca tt c cc s xy ho ca phn t bng 0, ca ion bng in tch ion. - Hai nguyn t ng nht lin kt vi nhau khng lm xut hin s xy ho. S xy ho ca mi nguyn t trong n cht u bng 0. - S xy ho ca hyr bng +1 (tr cc hp cht vi kim loi), ca xy bng -2 (tr cc hp cht pext), ca cc nguyn t kim loi bng ho tr ca n. Nh vy t khi nim ca s xy ho trn y ta c th nhn thy rng: qu trnh xy ho l qu trnh lm tng s xy ho cht phn ng (c cht, cht nn) v lm gim s xy ho tc nhn phn ng, cn qu trnh kh l qu trnh ngc li. i vi nguyn t cacbon, s kh v s xy ho bin i theo dy sau:
CH4 R CH3 C H3OH R CH2OH HCHO R CHO HCOOH R COOH C O2 +4 -4 S xy ha S kh

130

b. Phn ng xy ho cc hp cht ancol.

Ancol 20 + Ancol 10 +
0

KMnO4 ( CrO3, K2Cr2O7, Cu, 200-300 0 C) dung dch KMnO4 Cu, 200-300 0 C axit anhyt

Xtn

Ancol 3 : khng b xy ho trong mi trng kim, trong mi trng axt, trc n b tch thnh anken sau tu theo iu kin phn ng c th b xy ho thnh xton hoc axt. 9.5. Gii thiu mt s ancol quan trng. 9.5.1. Ru tylic. Ru tylic c iu ch bng phng php ln men tinh bt, hyrat ha tylenTrong i sng v cng nghip, n c s dng lm dung mi, lm nguyn liu cht ban u tng hp, dng cho cng nghip thc phm, dng trong y hc Ru tylic 95% trong cng nghip trong cng nghip c thu nhn bng phng php chng ct phn on. Ru tylic tuyt i 100% c thu nhn bng cch chng ct ng ph (hn hp ng ph gm 7,5% nc, 18,5% ru, 74% benzen si nhit 64,90C). Nhiu khi ngi ta cn lm tuyt i ru tylic bng cch un ru tylic 95% vi magi sau em chng ct. 9.5.2. tylenglycol. a. tylenglycol c iu ch bng cc phng php iu ch ancol thng thng. Di y l mt s phng php quan trng. 1- Thu phn dn xut halogen
Cl CH2 CH2 Cl + 2 H2O Na2CO3 HO CH2 CH2 OH

2- Thu phn tylenxt.

H2C CH2 + H2O O H
+

HO CH2

CH2

OH

3- Hyrxyl ho cc anken bng KMnO4 hoc peaxt.

KMnO4 CH2 CH2 RCOOOH HO CH2 H2C CH2 O CH2 H2O, H OH
+

HO CH2

CH2

OH

b. Tnh cht. tylenglycol c cc tnh cht ging nh ancol thng thng nhng do nh hng ca nhm OH th 2 nn c tnh axt mnh hn. V vy n c kh nng phn ng vi hyrxit ng.

131

CH2 CH2

OH OH

+ Cu(OH)2 +

HO CH2 HO CH2

CH2 CH2

O O

H Cu H

O CH2 O CH2

- Phn ng xy ho:
CH2 CH2 OH OH O CHO CH2OH O O COOH CH2OH OHC CHO Glyxal O COOH CHO O COOH COOH Axit xalic

- Phn ng hyrat ho:

HO CH2 CH2 OH H2SO4 CH3CHO

tylenglycol c ng dng lm dung mi, lm tc nhn phn ng, lm cht truyn nhit... 9.5.3. Glyxrin. a. Glyxrin trong cng nghip ch yu iu ch bng phn ng thu phn cc cht bo trong mi trng kim (phn ng x phng ho). Ngoi ra, ngi ta cn tng hp glyxrin t prpylen:
CH2 H2O
0 CH CH3 Cl2, 400 C CH2

CH CH2 Cl

Cl2, H2O

CH2 OH

CH CH2 Cl Cl

CH2 OH

CH CH2 OH OH

b. Tnh cht. Tng t nh tylenglycol, glyxrin tc dng vi hyrxit ng to thnh hp cht glyxrat ng c mu xanh.
CH2 O CH O CH2 OH H Cu H O CH2 O CH

HO CH2

Phn ng to este glyxrin trinitrat.

CH2 OH CH CH2 HNO3/H2SO4 CH2 ONO2 CH CH2

OH OH

ONO2 ONO2

Glyxrin c rt nhiu ng dng trong thc t nh dng lm cht truyn nhit, lm tc nhn phn ng, lm mm da, dng sn xut thuc n, dng trong y hc

132

9.6. MT S PHNG PHP DNG NHN BIT ANCOL nhn bit ancol c th dng phng php ph hng ngoi: - Nhm OH ring bit (khng c lin kt hyr) c (OH) = 3620 n 3640cm-1. - Nhm OH c lin kt hyr c (OH) = 3200-3350cm-1. Trong phng php ho hc, ngi ta dng thuc th Luca. l hn hp axt HCl m c v ZnCl2. Phng php ny c th dng phn bit cc ancol bc I, bc II, bc III c s nguyn t cacbon nh hn 6. Phn ng to thnh ankylclorua khng tan trong hn hp tc nhn, lm c dung dch phn ng. Ancol bc III tc dng ngay lp tc vi hn hp tc nhn, ancol bc II s thy phn ng xy ra sau 5 pht cn ancol bc I nhit phng s khng phn ng. B. PHNOL 9.7. CU TO V CCH GI TN. 9.7.1. Cu to. Phnol l nhng hp cht c cng thc phn t Ar-OH trong Ar- l nhm phnyl hoc cc dn xut ca phnyl. Khc vi ancol, trong hp cht phnol nhm OH lin kt trc tip vi nhn thm. 9.7.2. Cch gi tn. Cc hp cht phnol c gi tn nh l dn xut, n gin nht ca dy ny l phnol.
OH OH OH NO2 Cl m-Clophnol

Phnol

o-Nitrphnol

Mt s hp cht khc c tn gi ring nh sau:

OH CH3 OH (o, m), p-Crzol Catechon Rzcxin OH Hyrquinon
-Naphtol

OH OH

OH

OH OH

133

OH

OH

OH

HO

- Naphtol

Antranol-1

Antranol

Phnantrol-4

9.8. TNH CHT VT L. Hp cht n gin nht ca dy ny l phnol, t tan trong nc nhit thng. Do c kh nng to thnh lin kt hyr nn phnol c nhit si cao. Cc hp cht phnol khc hu nh khng tan trong nc. 9.9. PHNG PHP IU CH. 9.9.1. Phng php cng nghip. Mt s lng rt ln phnol c iu ch trong cng nghip bng phng php nh phng th nghim. Ngoi ra cn c mt s phng php dng iu ch phnol trong cng nghip nh sau: a. Chng ct nha than 170-2400C thu phnol th. Dung dch phnol sau khi loi naphtalen cho tc dng vi NaOH thu c phnolat. Tch loi cc cht khng tc dng vi NaOH c trong dung dch sau cho kh CO2 d vo chuyn phnolat thnh phnol t do v chng ct ly phnol. b. Phn ng nung nng chy benzensufnat natri vi NaOH (phng php kim nng chy).
C6H5SO3Na + NaOH SO3Na + NaOH C6H5OH + Na2SO3 OH + Na2SO3

c. Phng php thu phn clobenzen. - Thu phn clobenzen bng hi nc di p sut thch hp nhit cao c xc tc ng kim loi (phng php Rasic).
C6H6 + HCl + O2 C6H5Cl + H2O Cu, 4250 C C6H5Cl + H2O C6H5OH + HCl

- Thu phn bng NaOH nng chy.

C6H5Cl + NaOH 360 0 C, 315at C6H5ONa HCl C6H5OH

134

d. xy ho tluen hoc cumen (izprpylbenzen).

C6H5CH3 CH3 O2/xt C6H5OH CH3 CH CH3 CH3 C OOH H2O, H+ 100 0 C OH + CH3 C O CH3

O2 kk

Phng php xy ho cumen l phng php quan trng nht v c hai sn phm to thnh u c ngha ln s dng trong cng nghip. 9.9.2. Cc phng php tng hp. a. Thu phn mui iazni.
C6H6 HNO3/H2SO4
+ -

C6H5NO2

Fe/HCl

C6H5NH2

NaNO2/HCl

C6H5N2 Cl

C6H5N2 Cl

+ H2O

t0C

C6H5OH + N2 + HCl

b. Phng php kim nng chy cng c s dng trong phng th nghim.
p- CH3C6H4SO3Na NaOH, 3000 C p - CH3C6H4ONa H2SO4 p - CH3C6H4OH

c. Tng hp phnol bng phn ng th SN.

Cl HNO3/H2SO4 Cl NO2 NaOH ONa NO2 H+ OH NO2

NO2 O2N

OH

NO2 NO2 HNO3/H2SO4

NO2

NO2 Axit picric

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

135

O H

- +

9.10.1. Cc phn ng biu hin tnh axt.

C6H5OH + H2O
+ C6H5O + H3O

Nhng nhm ht in t s lm tng tnh axt ca phnol, tri li nhng nhm y in t s lm gim tnh axt ca phnol. a. Phn ng to mui phnolat.
C6H5OH + NaOH
- + C6H5O Na + H2O

b. Phn ng to ete (tng hp Williamxn).

C6H5ONa + RX C6H5 O R + NaX

V d:
C6H5OH dd NaOH C6H5ONa C2H5I C6H5 O C2H5 O C6H5

p- O2NC6H4CH2Br + C6H5OH C6H5OH + Cl CH2COOH

dd NaOH

p- O2NC6H4CH2

dd NaOH

C6H5

O CH2COONa

c. Phn ng to thnh este. Chuyn v Friz.

RCOOH, H Ar OH + RCOCl (RCO)2O
+

R C O Ar O
O C O p- O2NC6H4 O C O CH3 C6H5

V d:
C6H5OH + C6H5COCl NaOH C6H5 p- O2NC6H4OH + (CH3CO)2O

CH3COONa

Khi un nng este ca phnol vi AlCl3 s xy ra s chuyn v nhm axyl n v tr cto hoc para ca nhn thm. Phn ng ny gi l phn ng chuyn v Friz dng iu ch cc hp cht hyrxi-xton thm. V d:

136

OH OCOCH3 AlCl3, 165 0 C H3C H3C OH COCH3

AlCl3, 20 0 C H3C COCH3

C ch:
O
+

AlCl3 C R

C O + O AlCl2 O C R HCl

O AlCl3 OH C R O

O + O AlCl3 H C O R -HCl

9.10.2. Cc phn ng th SE. Trong cc phn ng th SE, nhm OH l nhm th loi 1 nn n c nh hng ch yu vo v tr cto v para. a. Phn ng nitr ho.
OH OH HNO3 . O2N NO2

OH HNO3 long, 20 C
0

NO2 NO2 +

OH

NO2

137

b. Phn ng sunfnic ho.

OH OH H2SO4 100 0 C 15-200 C OH SO3H

H2SO4, 110 0 C

SO3H

c. Phn ng halogen ho.

OH Br2 dd Br OH Br

Br

Nu phn ng xy ra trong dung mi t phn cc s to thnh hn hp sn phm.

OH Br2, CS2, 0 0 C OH + Br OH Br

d. Phn ng ankyl ho Frien-Crap.

OH CH3 + CH3 C CH3 Cl HF HO CH3 C CH3 CH3

e. Phn ng axyl ho Frien-Crap. Phn ng axyl ho cc hp cht phnol c th xy ra trc tip v cng c th xy ra qua bc to thnh este ri sau chuyn v Friz.
OH + RCOCl AlCl3 OH COR + COR OH

138

OH 25 0 C OH (CH3CO)2O H3C H3C 165 C H3C

0

O C O

CH3 AlCl3

H3C COCH3 OH COCH3

g. Phn ng nitrz ho.

OH CH3 NaNO2/H2SO4 OH CH3

NO

h. Phn ng ghp vi mui iazni. y l phn ng c ng dng nhiu trong ho hc tng hp cc loi thuc nhum, cc cht ch th mu.
R HO + N N
+

R HO N N

i. Phn ng Konbe. y l phn ng dng iu ch cc o-hyrxibenzic axt.

ONa + O C O
+ - 125 0 C, 7at

OH COONa H
+

OH COOH

k. Phn ng Raim-Timan. y l phn ng dng iu ch cc anhyt ca cc hp cht thm c cha nhm OH.
OH CHCl3, NaOH dd 70 0 C O
-

O CHCl2

OH CHO HCl CHO

139

C ch ca phn ng Raim-Timan c th vit nh sau:

HO + CHCl3 O + CCl2
-

H2O + O

CCl3 H CCl2
-

Cl + O

CCl2
-

CHCl2

l. Phn ng ci focmanhyt. Phn ng ny dng tng hp polyphnolfocmanhyt. Phn ng c th xy ra trong mi trng kim hoc axt.
OH HCHO, H
+

OH CH2OH C6H5OH CH2 CH2 CH2

OH CH2 OH

OH CH2

OH

HCHO, H+

CH2

9.11. CCH NHN BIT CC HP CHT PHNOL. nhn bit cc hp cht phnol, ngi ta thng da co tnh axt: phnol c tnh axt mnh hn nc nhng yu hn axt ccbonic, do nu hp cht khng ho tan trong nc nhng tan trong dung dch NaOH v khng ho tan trong dung dch bicacbnat natri th c th l phnol. Cng c khi ngi ta dng phn ng lm mt mu Br2 hoc dng phn ng vi mui st III cho mu tm c trng pht hin phnol. 9.12. GII THIU MT S HP CHT PHNOL QUAN TRNG. 9.12.1. Phnol. Phnol l nguyn liu cng nghip quan trng dng sn xut nha, phnolfocmanhyt, sn xut axt xalixylic, phm nhumNgoi ra, n cn c dng st trng, bo qun g, sn xut thuc dit c 2,4-D, thuc tr su 9.12.2. Timol. Timol (3-hyrrxi-4-izprpyltluen) c nhiu trong cc tinh du, l sn phm chuyn ho ca cc tecpen trong thc vt. Timol c th tng hp bng phn ng sau:

140

CH3 + OH H3C CH3 CH CH2 H+

CH3

OH CH CH3

Timol dc dng lm hng liu, lm cht st trng. Khi tin hnh phn ng hyr ho timol s thu c mentol. 9.12.3. Catechol. Catechol (1,2-ihyrxibenzen) c th thu nhn bng cch chng ct nha than hoc bng phng php tng hp.
o- ClC6H4OH H2O, 190 0 C o- HOC6H4OH Catechol
O ONa ONa O COCl2 C O O CH2Cl2 CH2 O

Trong catechol c 2 nhm OH u tham gia phn ng to thnh hp cht vng:

Catechol rt d b oxy ho:

OH 2Ag + OH O
+

O + 2Ag + 2H
+

Catechol l nguyn liu dng iu ch cc ancalit papaverin, pparin, dng sn xut gaiancol, rnalin 9.12.4. Rezocxinol.Rezocxinol (1,3-ihyrxibenzen) c iu ch bng cch nung chy kim vi 1,3-benzenisunfnic axt. Rezocxinol thng tn ti di cc dng:
O H2/Pd O OH O 1,3-ixxyclhecxen-4 OH O

141

9.12.5. Hyrquinon. Hyrquinon (1,4-ihyrrxibenzen) c ng dng rng ri trong k thut lm nh, lm phim. Phim nh c trng mt lp nh tng AgBr. Khi b chiu sng, mt s ht bc brmua c hot ho AgBr*. Nu phim chp tip xc vi hyrquinon th cc ht bc c hot ho s b kh thnh bc kim loi nhanh hn bc brmua cha b hot ho.
OH + 2AgBr* + 2HO OH
-

O
+ 2Ag + 2Br + 2 H2O

Nu ta dng mt dung dch hin hnh, v d tisunfit natri loi phn AgBr khng b kh (lu hnh) th cc ht bc mn s phn tn trn phim to thnh mt tm nh tri (m nh). em tm m nh ny vo my in nh ta s thu c dng nh.

142 CU HI N TP V BI TP CHNG 9

9.1. Gi tn theo danh php quc t cc ru sau y:

a. CH3 CH CH2 CH2 OH CH3 C2H5 c.CH3CH C CH C2H5 CH3 OH CH3 HO CH3 f. HO OH g.CH3 C C C CH2 CH3 OH b.Cl CH2 CH CH CH CH CH2 OH OH CH3 d.CH3CH2CH2CH CH CH CH3 e.Br3C CH2CH2OH CH(CH3)2

9.2. Vit phng trnh phn ng ca ru n-propylic vi cc cht sau: a. CH3COOH c mt H2SO4 b. H2SO4 c nhit cao c. K2Cr2O7 + H2SO4 c d. CH3COCl e. (CH3CO)2O 9.3. T benzen v cc ha cht thch hp, vit phng trnh phn ng iu ch: a. p-nitro phenol c. 2,4-dinitro phenol
CH3CH2CH2OH O2N HO NO2 OH

b. p-izopropyl phenol d. p-metyl phenol

(CH3)3COH

9.4. Sp xp theo th t tng dn tnh axit ca cc hp cht sau y:

9.5. Sp xp theo th t tng dn hot tnh ca cc ru sau u vi thuc th Luca: a. 1-phenyl propanol-1, 1-phenyl propanol-2 v 3-phenyl propanol-1 b. 2-buten-1-ol, 3-buten-1-ol v 3-buten-2-ol 9.6. T etanol v cc ha cht thch hp khc cha ti a 4 nguyn t cacbon iu ch cc hp cht sau y: a. propanol-1 c. propanol-2 e. 2,3-dimetyl butanol-2 b. 2-brom-2-metylhexan d. etyl propionat f. 1,2-butandiol

143

TI LIU THAM KHO CA BI TP CHNG 9 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

144

Chng 10 ETE 10.1 CU TO, PHN LOI V CCH GI TN te l nhng hp cht c cng thc phn t R-O-R, R-O-Ar hoc Ar-O-Ar. 1- Tn gi ca te c to thnh t tn gi ca 2 nhm lin kt vi nguyn t xy v ch te. V d:
C2H5 O C2H5 itylte C6H5 O C6H5 iphnylte CH3 O C(CH3)3 Mtyltecbutylte

2- Nu mt trong 2 nhm lin kt vi xy khng c tn gi n gin th hp cht c gi nh dn xut ankxi: CH3O- (mtxi), C2H5O-(txi), C6H5O-(phnxi) V d:
CH3CH2CH2 CH CH2CH3 p- C2H5O C6H4 COOH HO CH2 CH2 OC2H5 OCH3 3-mtxihecxan

p-txibenzic axit

2-txitanol

3- Hp cht n gin nht ca ankylarylte l anizol C6H5-OCH3. 4- Nu te c hai nhm th ging nhau th ngi ta gi l te i xng. nu cc nhm th khc nhau th l te bt i xng. 10.2. TNH CHT VT L. Do c im v cu to: gc lin kt C-O-C trong phn t te khng phi l 1800 nn mmen lng cc gia 2 lin kt C-O khng trit tiu ln nhau do te phn cc yu.
R 110 0 R O

Nhng s c mt ca mmen phn cc ny khng nh hng n nhit ca te v vy te c nhit si gn vi ankan tng ng v thp hn nhiu so vi ancol tng ng. ho tan ca te thp trong nc tng t nh cc ancol. V d itylte v n-butanol c ho tan trong nc nh nhau l 8g/100g (HOH). iu c th gii thch bng s lin kt hyr ca nc vi ancol v te tng t nh nhau. 10.3. CC PHNG PHP IU CH. 10.3.1. Phng php cng nghip. Trong cng nghip, iu ch mt s te i xng thp ngi ta dng phng php ehyrat ho gia 2 phn t ancol.

145

S cnh tranh ca phn ng hyrat ho lng phn t vi phn ng tch loi c khng ch bng cch khng ch iu kin phn ng. V d tylen c to thnh l sn phm ch yu khi un nng ru tylic vi axt sunfuric m c nhit 1800C, tri li itylte l sn phm ch yu c to thnh 1400C vi lng ru tylic lun lun d. Phn ng to te xy ra theo c ch SN1 v SN2 nh sau:
R ROH2
+ +

ROH

R O R H
+

R O R + H
+

SN1
+

ROH RO R OH H H

-HOH

R O R H

R O R + H

SN 2

Phng php iu ch trn y ch c ngha i vi cc te i xng. Trong trng hp dng cc ancol khc nhau, phn ng s to thnh hn hp sn phm. Phng php ny cn dng iu ch cc te vng vi ru a chc.
H2C CH2 OH CH2 HO CH2 H2SO4 O Ttrahyrfuran

Phn ng tch loi nc khng xy ra i vi cc hp cht phnol ni chung do hiu ng lin hp , p ca nhn thm vi xy nn khng c kh nng bn ho ionxni. 10.3.2. Phng php phng th nghim. Trong phng th nghim iu ch te ch yu ngi ta s dng phng php Uylimxn.
R X + NaOR' R X + NaOAr R O R' + NaX R O Ar + NaX
CH3 O C(CH3)3 O CH3 O CH2 C6H5

V d:
CH3Br + NaO C(CH3)3 C6H5OH + (CH3)2SO4 NaOH dd C6H5 p- O2N C6H4 OH + BrCH2

C6H5 NaOH dd p- O2N C6H4

Phng php uylimxn c th iu ch te i xng, te khng i xng v cc te thm. Mt khc cng cn lu rng trong phng php ny khng th dng arylhalogenua (tr trng hp trong nhn thm c cc nhm th ht in t mnh) cho tng hp Uylimxn v phn ng kh c th xy ra. V d tng hp p-nitrbenzylphnylte ch c th tin hnh theo s (1) trong 2 s phn ng sau, v theo (2) phn ng s khng th xy ra.

146

p- O2N C6H4 p- O2N C6H4 CH2 OC6H5 p- O2N C6H4

CH2Cl + NaO C6H5 (1) CH2ONa + Cl C6H5 (2)

Trong phng php ny cng khng c s dng cc ankylhalogenua bc III v s xy ra ch yu l phn ng tch loi. V d: iu ch tyltecbutylte sau y ch c th tin hnh phn ng theo s (1).
CH3CH2 O C(CH3)3 CH3CH2Br + (CH3)3CCl + NaO C(CH3)3 (1) NaO CH2CH3 (2)

10.4. TNH CHT HO HC. 10.4.1. Phn ng phn ct te. te l mt cht tng i tr. N bn vng di tc dng ca kim, tc nhn xy ho v tc nhn kh. N ch b phn ct bi axt mnh. V d:
ROR' + HX R'OH + RX ArOR + HX ArOH + RX ( HX = HI, HBr, HCl)

Cc phn ng phn ct te ch xy ra trong iu kin khc nghit: HX un nng, m c. Cc axt thng dng l HI v HBr. V d:
CH3CH2 C6H5 O CH2CH3 + HBr CH3CH2OH + CH3CH2Br C6H5OH + CH3I
R O R' H
+

O CH3 + HI
+ ROR' + H

Phn ng phn ct te xy ra theo c ch SN1 v SN2.

Prton ha

Theo SN1
R O R' H R + X+ +

chm nhanh

R'OH

RX
+

Theo SN2
R O R' + XH
+

X . . . R. . . OR' R

RX + R'OH

10.4.2. Chuyn v Claizen. Khi b un nng n 2000C, phnylallylte chuyn thnh o-allylphnol.

147

OCH2CH CH2 200 0 C

OH CH2CH CH2

Ngi ta gi phn ng trn y l chuyn v Claizen. Phn ng ny xy ra theo c ch vng sau y:

OCH2CH CH2 O CH2CH CH2 H H OH CH2CH CH2

Nu cc v tr cto b chim ch th n xy ra v tr para.

OCH2CH CH2 R R t0 C R O R CH2CH CH2 CH2CH CH2 R OH R

10.5. MT S TE QUAN TRNG. 10.5.1. te tylic. te tylic c iu ch t ancoltylic vi xc tc nhm trixt hoc H2SO4. te tylic l mt cht lng c mi c trng, nh, d bay hi, d chy. te tylic c dng lm dung mi, lm cht gy m trong y hc. Khi lu, trong te tylic sinh ra pexit nn khi chng ct rt d n. te tylic tuyt i c thu nhn bng cch chng ct te vi H2SO4 m c v sau ng trong bnh thu tinh c cha natri kim loi. 10.5.2. tylenxit. tylenxit (xiran) trong cng nghip c iu ch bng phn ng xy ho tylen vi xc tc kim loi.
CH2 CH2 + O2 Ag, 2500 C H2C CH2 O

Trong phng th nghim cc hp cht pxt c th iu ch theo cc phng php sau: a. T halogenhyrin.
C C X2, H2O C C X OH HOC C O + H2O + X
-

b. xy ho cc anken bng peaxt.

148

C C

+ C6H5COOOH

C C O

+ C6H5COOH

tlylenxt l hp cht hot ng mnh nn n rt d tham gia cc phn ng m vng. a. Phn ng m vng c xc tc bng axt.
C O C H+ C C +O H
H+

C C Z OH

V d:
H2C CH2 O + H2O CH2 OH CH2 OH CH2 OH H
+

H2C CH2 + C2H5OH O H2C CH2 O + HBr

CH2 OC2H5 CH2 Br

CH2 OH

b. Phn ng Grinha.
RMgX + H2C CH2 O RCH2CH2OMgX RCH2CH2OH

V d:
C2H5MgCl + H2C O CH2 C2H5CH2CH2OMgCl C2H5CH2CH2OH

149 CU HI N TP V BI TP CHNG 10

10.1. Vit cc ng phn ete ca hp cht c cng thc phn t C5H12O. Gi tn. Ete no quang hot. 10.2. Vit cng thc cu to cc hp cht sau v gi tn theo IUPAC: a. metyl etyl ete c. xiclopentyl tec-butyl ete e. 5-metoxy-2-pentanol 10.3. Gi tn cc hp cht sau y:
a.C6H5 O C6H5 b.CH3 O C(CH3)3 d. H2C CH O CH2 CH CH2 O C2H5

b. phenyl etyl ete d. m-dietoxybenzen f. dibenzyl ete

c. CH3 CH2 O CH2 CH2OH e. Br OC2H5 f.

10.4. Hon thnh cc phn ng sau y:

a. p- CH3 b.C6H5CH2ONa
+ + OH 1. HO 2. CH3I

C6H5CH2Br HBr
+ HOCH2 CH2OH H

c.(CH3)2CHOCH3 d.CH3CH2CHO
+

10.5. Phn bit: a. p-CH3-C6H4-OH v C6H5OCH3 b. di n-propyl ete v n-propyl clorua c. allyl etyl ete v dietyl ete 10.6. Mt hp cht A (C9H10O2) b thu phn cho focmaldehit v B (C8H10O3), tan d dng trong baz. Vit nhng cng thc cu to c th c ca A v B. 10.7. n-butyl etyl ete b phn ct bi HBr c nng cho etyl bromua v butyl bromua. Tec-butyl etyl ete b phn ct bi HBr cho tec-butyl bromua v ru etylic. Vit c ch ca hai phn ng, tm cht trung gian.

150

TI LIU THAM KHO CA BI TP CHNG 10 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

151

Chng 11 ANHYT V XTON. 11.1. CU TO. Anehyt l nhng hp cht c cng thc phn t l RCHO v xton l RCOR. Gc Rv R- c th l gc bo hoc thm. Nh vy l c anhyt ln xton u cha nhm C=O nn ngi ta xem n l loi hp cht cacbnyl. Chnh s c mt ca nhm cacbnyl ny xc nh nhng tnh cht c bn ca anhyt v xton. Nhn chung nhiu tnh cht c bn ca anhyt v xton ging nhau nhng s c mt ca cc nhm th khc nhau bn cnh nhm cacbnyl (trong anhyt l hyr cn trong xton l R) dn n mt s tnh cht khc nhau gia anhyt v xton: 1- Anhyt d dng b xy ho cn xton b xy ho kh khn hn. 2- Anhyt tham gia phn ng cng nuclphin, loi phn ng c trng cho nhm cacbnyl mnh hn xton. Xt v mt cu to ta nhn thy rng nguyn t cacbon ca nhm cacbnyl c trng thi lai ho sp2 do n c 3 lin kt vi cc nguyn t khc. Ocbitan p t do cn li ca cacbon xen ph vi ocbitan p ca xy to thnh lin kt . Nh vy lin kt ca cacbon v xy trong nhm cacbnyl l lin kt bi. Mt khc do m in khc nhau nn nhm cacbnyl b phn cc v pha xy.
120 R C O R 120 0
0

R + C O R

11.2. CCH GI TN. 11.2.1. Tn gi ca anhyt. Tn gi ca cc anhyt c to thnh t tn gi ca cc axt cacbxylic tng ng bng cch thay t axt bng t anhyt. Tn gi cc anhyt theo IUPAC c hnh thnh nh sau: mch chnh c tnh l mch di nht c cha nhm CHO v tn gi ca mch chnh l tn gi ca hyrcacbon tng ng cng vi ui al. V tr cc nhm th c gi tn cng vi cc ch s m trong nguyn t cacbon ca nhm cacbnyl c ch s 1. V d: HCHO Focmanhyt Mtanal CH3-CHO Anhyt axtic tanal (Axtanhyt) CH3CH2-CHO Anhyt prpanic Prpanal (Prpinanhyt)

152

C6H5-CHO Benzanhyt 11.2.2. Xton.

p-O2N-C6H5-CHO p-Nitrbenzanhyt

CH3CH2CH2CH(CH3)-CHO 2-Mtylpentanal

Tn gi thng thng ca hp cht xton n gin nht l axton, tn gi thng thng ca cc xton bo khc c hnh thnh bng cch gi tn ca 2 nhm th lin tc lin kt vi nguyn t cacbon cacbnyl cng thm ui xton. Tn gi ca cc xton m nhm cacbnyl lin kt trc tip vi nhn benzen c ui l phnon. Tn gi xton theo IUPAC c chon mch chnh l mch di nht, c cha nhm cacbnyl v gi tn hyrcacbon tng ng cng thm ui on. V tr cc nhm th c nh s sao cho nhm cacbnyl c ch s l nh nht. V d: CH3COCH3 Axton Prpanon C6H5-CO-CH3 Axetonphnon V d: O=CH-CH=O 1,2-ixtan 11.3. TNH CHT VT L. Nh ni trn y, phn t anhyt v xton phn cc nn chng c nhit si cao hn cc hp cht c cng phn t lng tng ng. Cc phn t anhyt v xton khng c kh nng to lin kt hyr vi nhau nn chng c nhit si thp hn cc ancol hoc axt cacbxylic tng ng. V d: Hp cht (Butanal) (Mtyltylxton) (Pentan) (te tylic) (n-Butanol) (A.Prpanic) M 72 72 72 74 74 74 t0C 76 80 36 34 118 141 CH3CH2CH2-CHO CH3-CO-CH2CH3 CH3-(CH2)2-CH3 C2H5-O-C2H5 C3H7-CH2-OH CH3CH2-COOH CH3CH2-CO-CH3 Mtyltylxton Butanon-2 C6H5-CO-CH2CH2CH3 n-Butyrophnon CH3-CO-CO-CH3 2,3-ixbutan (CH3)2CH-CO-CH3 Mtylizprpylxton 3-Mtylbutanon-2 C6H5-CO-C6H5 Benzophnon

Ngoi ra cn c tn gi theo nhm x (-CO-).

Cc anhyt v xton thp ho tan tt trong nc c th do c kh nng to lin kt hyr vi nc. Anhyt v xton tan tt trong cc dung mi hu c.

153

11.4. IU CH. 11.4.1. Phng php cng nghip. a. iu ch focmanhyt. Trong cng nghip focmanhyt c iu ch bng 2 phng php sau y: 1- xy ho trc tip CH4 c xc tc v nhit thch hp
CH4 CH3OH + O2 NO, 450-600 C
0 0

HCHO + H2O HCHO + H2O

2- xy ho ru mtylic bi khng kh c xc tc
+ O2 Cu, 500-600 C

Focmanhyt l cht kh thng c s dng trong cng nghip di dng dung dch (focmalin), dng rn polyme (HCHO)n, parafocmanhyt hoc trixan (CH2O)3. b. Axtanhyt. Axtanhyt c iu ch bng phn ng hyrat ho axtylen hoc hyr ho ru tylic.
HC CH + H2O CH3CH2OH H2SO4, HgSO4 Cu, 250-300 C
0

CH3CHO

Trong cng nghip axtanhyt ch yu dng iu ch axt axtic. c. Benzanhyt. Trong cng nghip benzanhyt c iu ch t tluen bng phn ng clo ho v thu phn sau y:
C6H5 CH3 Cl2, t C
0

C6H5CHCl2

H2O, 100 C

C6H5CHO

d. Anhyt xalixylic. Anhyt xalixylic v mt s anhyt c cha nhm phnol c th iu ch bng phn ng Raim-Timan nh sau:
CHCl3 + NaOH CCl2 + NaCl + H2O

CCl2 NaOH o- NaO C6H4 CHCl2 C6H5 ONa C6H5 OH NaOH o- NaO C6H4 CHO HCl o- HO C6H4 CHO Anhyt xalixylic

Mt s anhyt thm dng trong cng nghip nc hoa, cng nghip thc phm thng c iu ch bng phn ng xy ho ni i ca cc hp cht t nhin.

154

OCH3 K2Cr2O7, H2SO4

OCH3

CH CH CH3 Anetol ( tinh du hoa hi)

OH OCH3 KOH, 2250 C OH

CHO
OCOCH3

OCH3 (CH3CO)2O, CH3COONa

OCH3

CH2 CH CH2 Eugenol K2Cr2O7, H2SO4

CH CH CH3 OCOCH3 OCH3 + H2O, H , t0 C

CH CH CH3 OH OCH3

CHO

CHO Vanilin

Mt s dung mi quan trng nhaxton, tylmtylxton c iu ch bng phn ng hyr ha ancol.

CH3CH(OH)CH3 CH3CH2 Cu, 250-300 C
0

CH3
0

CO CH3 CO CH3

CH(OH)

CH3 Cu, 250-300 C CH3CH2

11.4.2. Phng php phng th nghim. a. Cc phng php tng hp anhyt. 1- xy ho cc ancol 10.
Cu, t0 C RCH2OH K2Cr2O7
Cu, 250-300 C
0

RCHO

V d:
CH3CH2CH2CH2OH CH3CH2CH2CHO

2- xy ho cc ankylbenzen.
Cl2, t0 C Ar CH3 Ar CHCl2 ArCHO

CrO3, (CH3CO)2O ArCH(OCOCH ) 3 2

155

V d:
Br C6H4 CH3 Cl2, t C
0

Br

C6H4

CH2Cl

CaCO3, H2O

Br

C6H4

CHO

O2NC6H4CH3

CrO3, (CH3CO)2O

O2NC6H4CH(OCOCH3)2

H2O, H2SO4

O2NC6H4CHO

3- Kh ho cloranhyrit.
RCOCl hoc ArCOCl H2, Pd - BaSO4 RCHO hoc ArCHO H2, Pd/S H2, Pd - BaSO4 p- O N C H 2 6 4 CHO

V d:
p- O2N C6H4 COCl

4- Phn ng Raim-Taiman. (Xem phn 9.10.2.). 5- Phng php Gatteman-Kc.

CO + HCl Cl CHO + C6H6 Cl CHO (focmyl clorua) C6H5 CHO AlCl3

b. Cc phng php tng hp xton. 1- xy ho ancol bc II.

Cu, t C R CH(OH) R' KMnO4 K2Cr2O7
0 0

R C O

R'

V d:
CH3CH2CH2 CH(OH) CH2CH3 Cu, 250 C C3H7 CO C2H5

CH3 H OH H3C CH CH3 (-)-Mentol K2Cr2O7, H2SO4

CH3

O H3C CH CH3 (-)-Menton

2- Axyl ho Frien-Crap.
Ar H + R COCl AlCl3 Ar CO R + HCl

4- Phn ng ca cloanhyrit vi hp cht c cadimium.

RMgCl + CdCl2 R2Cd R'COCl R' ArCOCl CO R hoc Ar CO R

V d:
C4H9 m-CH3 MgBr C6H4 CdCl2 (C4H9)2Cd (CH3)2CH COCl C6H4 MgBr C4H9 CdCl2 CO CH(CH3)2 ( m-CH3 C6H4)2Cd Br Mg

m -CH3 C6H4

CH3CH2CH2COCl m-CH 3

CO CH2CH2CH3

156

4- cacbxyl ho cc axt cacbxylic hoc dn xut ca chng.

LiAlH4 RCOOH SOCl2 RCH2OH RCHO RCOCl

-T mui icacbxylat canxi.

(RCOO)2Ca hoc RCOO Ca OOCR' t 0C R CO R hoc R CO R'

11.5. TNH CHT HA HC. 11.5.1. Phn ng cng nuclphin. Phn ng nuclphin ca cc hp cht anhyt v xton xy ra qua hai giai on: giai on 1 cng tc nhn mang in tch m vo nguyn t cacbon cacbnyl, xy ra chm quyt nh tc phn ng, giai on 2 bn ho sn phm xy ra nhanh bng cch cng vi phn mang in tch dng.
R R C O + Y X
+ -

- chm

R X R X + Y , nhanh C C R OY R O

V giai on quyt nh tc phn ng c quyt nh bi s tn cng ca tc nhn nuclphin nn y l phn ng AN. Anhyt tham gia phn ng AN d hn xton v do nh hng ca hiu ng khng gian v in t n trng thi chuyn tip:
R X C R O-

Nhm th R>H lm cn tr s tn cng ca tc nhn X-. Nhm th R c hiu ng +I lm gim bn ca trng thi chuyn tip.

1.5.2. Mt s phn ng AN ca anhyt v xton. 1- Phn ng xy ho. - Anhyt:

AgNO3/NH4OH R CHO hoc ArCHO KMnO4 K2Cr2O7 R COOH hoc ArCOOH

- Mtylxton:
(Ar), R C O CH3 X2 HO(Ar), R C O CX3 (Ar), R C O- + CHX3 O

157

V d:
C2H5 CO CH3 I2 NaOH C2H5COONa + CHI3 Cl2 (CH3)2C KOH CH COOK + CHCl3

(CH3)2C

CH CO CH3

2- Phn ng kh. - Kh thnh ancol:

C O H2, Ni (Pd, Pt) LiAlH4, NaBH4
LiAlH4

CH OH

V d:
C6H5 CO CH3 C6H5 CHOH CH3

- Kh thnh hyrcacbon.
C O Zn(Hg), HCl . (1) H2N NH2, HO (2) CH2

(1)- Gi l phn ng Klmenxen dng kh cc hp cht khng bn trong mi trng kim. (2)- Gi l phn ng Kizne-Vnf dng kh cc hp cht khng bn trong mi trng axt. V d:
C6H5 CO CH2CH2CH3 Zn(Hg), HCl . C6H5CH2CH2CH2CH3

3- Phn ng Grinha. (Xem phn iu ch cc hp cht ancol).

C O + RMgX R C OMgX H2O R C OH

4- Phn ng to thnh hp cht xianhyrin.

C O + CNH
+

C CN OH

V d:
CH3CHO + NaCN H2SO4 CH3 CH CN OH C6H5CHO + NaCN H2SO4 C6H5 CH CN OH H2O, H+ H2O, HCl CH3 CH COOH OH Axit lactic C6H5 CH COOH OH Axit Menilic

5- Phn ng cng bisunfit natri.

158

OH C O + NaHSO3 C SO3Na

V d:
C6H5CHO + NaHSO3 CH3CH2COCH3 + NaHSO3 C6H5 CH SO3Na C(OH) CH3 SO3Na OH CH3CH2

Phn ng ny ch xy ra nhng anhyt v xton c hiu ng khng gian nh (ch yu l cc mtylxton). Sn phm phn ng thu c l nhng cht kt ta v vy ngi ta thng dng phn ng ny tch cc hp cht cacbnyl ra khi cc hp cht hu c khng phi l cacbnyl.
H+ C O + NaHSO3 C OH SO3Na H
+

SO2 + H2O SO3- + H2O

C O + HSO3 HO-

6- Phn ng vi cc dn xut ca amnic.

C O + H2N A H2N A H2N OH H2N NH2 H2N NHC6H5 Hyrxylamin Hyrazin Phnylhyrazin C NH A OH Sn phm C N OH C N NH2 C N NHC6H5 xim Hyrazon Phnylhyrazon C N A

H2N NHCONH2 Cemicacbazit

C N NHCONH2 Cemicacbazon

V d:
CH3CHO + H2N OH H+ CH3CH NOH H
+

C6H5CHO + H2N NHC6H5

C6H5CH N NHC6H5

C ch ca phn ng:
C O H
+

H C OH H2N A H
+ +

C N+ A OH H H3N A
+

+ C N A + H2O + H

159

Phn ng thng xy ra trong mi trng axt ho nhiu, thun li cho phn ng AN nhng amin cng b prton ho nn lm gim tnh nuclphin ca tc nhn v ngc li khi pH cao. Do cc phn ng ca anhyt v xton vi cac dn xut amin thng c mt pH ti u. V d phn ng ca axton vi hyrxylamin c pH ti u l 5. Cc phn ng ny thng dng nh tnh anhyt v xton v hp cht cht to thnh c mu c trng. 7- Phn ng Canizaro. y l loi phn ng ca cc anhyt khng cha cc -hyr linh hot trong phn t di tc dng ca kim mnh.
2RCHO + HO RCOO + RCH2OH

V d:
2HCHO 2 (CH3)3C CHO 50% NaOCl HCOO- + CH3OH
(CH3)3C COO +

50% KOH/ancol

(CH3)3C CH2OH

y l loi phn ng xy ra theo c ch 2 giai on:

R CHO + HOH R C O OH
-

R CH OOH H

(1)

R C O + H

R C O- + R C OH (2) H +H
+

O - H+ RCOO-

RCH2OH

8- Phn ng vi cc hp cht c nhm mtylen linh ng Nhng hp cht c nguyn t hyr v tr linh ng c gy ra do hiu ng C tham gia phn ng vi c hp cht cacbnyl c gi l hp phn mtylen.
H H (Hyr linh ng) ( G = O, N...

R C C G

Phn ng ca hp cht cacbnyl vi hp phn mtylen c th xy ra nh sau:

C O +
+ -

C C O H

C OH

C O

Phn ng ny gi l cng anol hay anol ho.

160

V d:
CH3CH O + H CH2 CHO HO
-

CH3

CH(OH) CH2 CHO 3-Hyrxibutanal

Tip theo xy ra giai on tch nc, c gi l phn ng ngng t crton hay crton ho:
CH3 CH CH CHO OH H H+ - H2O CH3 CH CH CHO Anhyt crtnic

Hp cht crton c to thnh tip tc phn ng vi hp phn mtylen, gi l phn ng Maicsn.

H CH3 CH CH CH O + H C C O H HO
-

CH3

CH CH2 CH2 CHO

CHO

9- Cc phng php nhn bit anhyt v xton. Ngi ta thng nhn bit cc anhyt v xton bng cc phng php sau y: Cho anhyt v xton tc dng vi 2,4-initrphnylhyrazin to kt ta mu vng hoc mu . Phn bit anhyt v xton bng phn ng trng gng- thuc th Tlen, Cc mtylxtonc nhn bit bng phn ng halofoc. Trong ph hng ngoi, nhm cacbnyl c s sng: (CO) = 1700cm-1

161 CU HI N TP V BI TP CHNG 11

11.1. Gi tn theo danh php quc t v thng thng (nu c) ca cc hp cht sau:
a. H2C CH CHO d. CH3 CH C CH3 CH3 O b.OHC CH2 CH2 CHO O c. CCl3 CH3 CHO O e.C6H5 C C6H5 f. CH3 C CH C CH3

11.2. Vit cng thc cu to ca cc hp cht sau: a. 3-hidroxi butanal c. izobutyraldehit 11.3. Vit phn ng ca butanal vi: a. Thuc th Tollens b. 2,4-dinitro phenylhydrazin c. Etandiol + HCl d. LiAlH4 v tip theo l s trung ha e. NaOH long v nng. 11.4. Mt hp cht hu c c cng thc phn t C4H8O c kh nng phn ng natri bisunfit cho hp cht cng bisunfit, tc dng vi hidroxylamin cho oxim, tc dng vi dung dch AgNO3 trong NH3 cho phn ng trng gng v khi b oxi ha cho axit izobutyric. Hy cho bit cng thc cu to ca hp cht C4H8O v vit phng trnh phn ng xy ra. 11.5. iu ch: a. butanon-2 t propanol-2 b. axit -hidroxi--phenyl axetic t benzaldehit c. 4-metyl-3-pentenon-2 t metyl axetilen d. 1-metyl-1-phenyl etanol t benzaldehit 11.6. Nhn bit: a. propanol v propanon b. pentanon-2 v pentanon-3 c. butanon-2 v 3-butenol-1 11.7. Vit phn ng ca benzaldehit vi cc ha cht sau y: a. Dung dch HO- m c, nng v tip theo l s trung ha. b. 2,4-dinitro phenylhydrazin + H+ c. Dung dch NaCN trong nc b. 2,4- hexandion d. 4-tecbutyl xiclohexanon

162

TI LIU THAM KHO CA BI TP CHNG 11 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

163

Chng 12 AXT CACBXYLIC V DN XUT CA N. A. AXT CACBXYLIC. 12.1. CU TO Axt cacbxylic l loi hp cht hu c c tnh axt, cha nhm cacbxyl COOH lin kt vi cc nhm ankyl, ankenyl, aryl V d: HCOOH CH3COOH C6H5-COOH Ngi ta phn loi cc axt cacbxylic theo 2 cch: 1- Theo s lng nhm cacbxyl c trong phn t: Mncacbxylic axt ch cha mt nhm cacbxyl R-COOH icacbxylic axt cha 2 nhm cacbxyl HOOC-COOH Axt xalic HOOC-CH2-COOH Axt malnic

Tricacbxylic axt (c 3 nhm -COOH); polycacbxylic c cha n nhm -COOH Axt cacbxylic no: CnH2n+1COOH Axt cacbxylic thm: Ar-COOH. Axt cacbxylic khng no: CnH2n-1COOH.

2- Theo bn cht gc lin kt vi nhm COOH:

12.2. CCH GI TN. 12.2.1. Tn gi thng thng. Tn gi thng thng hay c s dng gi tn cc axt cacbxylic. Cc tn gi ny thng lin quan n ngun gc thu nhn axt cacbxylic. V d axt focmic (cht gy rt bng khi b kin cn) v c trong c th kin (kin theo ting Latinh l focmica) nn c tn l focmic. Axt caprilic CH3(CH2)8COOH c tch ra t m ca con d ci (d ci l caper) Trong tn gi thng thng, ngi ta cng hay dng tip u ng iz- ch nhm mtyl phn nhnh u mch. V d:
CH3 CH COOH CH3 CH (CH2)n COOH CH3 Axit izbutyric CH3 Axit izcacbxylic

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

164

C C C C COOH

Trong nhiu trng hp ngi ta gi tn ca cc axt nh l dn xut ca axt axtic (khng thm) v dn xut ca axt benzic (hp cht thm). 12.2.2. Danh php IUPAC. Trong danh php ny, mch chnh c chn l mch di nht, c cha nhm COOH v nh s th t ca cc nguyn t cacbon vi nguyn t cacbon ca nhm cacbxyl mang s 1. Gi tn cc axt bng cch gi tn ca hyrcacbon tng ng cng thm ui IC v cc nhm th cng vi s ch ca n. V d:
HCOOH CH3COOH CH3CH2COOH Axit prpanic CH3CH2 CH COOH CH3 Axit 2-mtylbutanic

Axit mtanic Axit tanic

12.3. TNH CHT VT L. Phn t axt cacbxylic phn cc v tng t nh ancol n c kh nng to lin kt hyr gia chng vi nhau v vi cc phn t ca cc hp cht khc. Do tnh ho tan ca cc axt cacbxylic bo tng t nh cc ancol: cc axt cacbxylic c s nguyn t cacbon C <4 tan tt trong nc; C>5 ch tan mt phn cn C>10 khng tan trong nc. Axt thm n gin nht l axt benzic hu nh khng tan trong nc. Cc axt cacbxylic c nhit si cao hn ancol c cng phn t lng tng ng. V d: CH3CH2COOH CH3CH2CH2CH2OH hoc s sonvat ho.
O... H O R C C R O H...O R C O . . .H O . . . H O C R H O H...O H...O H

M=74 M=74

t0sC = 141 t0sC = 118

S tng ln v nhit si ca cc axt so vi ancol c gy ra bi s lin kt hyr

12.4. CC PHNG PHP IU CH. 12.4.1. Phng php cng nghip. a. iu ch axt focmic.
CO + NaOH 200 0 C, 7at HCOONa H
+

HCOOH

b. iu ch axt axtic:

HC CH

165 H2O, HgSO4, H2SO4

Cu, 250-300 C
0

CH3CH2OH

CH3CHO

KMnO4

CH3COOH

Axt axtic c ngha rt quan trng trong cng nghip. Mt lng ln axt ny thu nhn bng phng php ln men. Ngoi ra trong cng nghip, mt ngun nguyn liu rt ln thu nhn axt cacbxylic l du m thc vt v ng vt cc loi. c. iu ch axt benzic.
C6H5 CH3 Cl2, t C
0

C6H5

CCl3

H2O, HO-

C6H5COOH

Nha than chng ct o- CH3 Du m

C6H4 CH3 o-Xylen

O2, V2O5

o- HOOC C6H4 COOH Axit phtalic

1.4.2. Phng php phng th nghim. a. xy ho cc ancol bc I.

R CH2 OH KMnO4 R COOH

V d:
CH3CH2CH(CH3) CH2 OH KMnO4 CH3CH2CH(CH3) COOH

c. xy ho cc ankylbenzen.
Ar R KMnO4 Ar COOH

V d:
p- O2N C6H4 o-Br C6H4 p- O2N C6H4 COOH Axit p-nitrbenzic KMnO4, HO o-Br C6H4 COOH CH3 CH3 K2Cr2O7, H2SO4

d. Cacbxyl ho tc nhn Grinha.

(Ar)RX Mg, te (Ar)RMgX CO2 (Ar)RCOOMgX H
+

(Ar)RCOOH

V d:
C2H5 H
+

C(CH3) CH3 C2H5

Cl

Mg, te

C2H5

C(CH3) CH3

MgCl

CO2

C2H5

C(CH3) CH3

COOMgCl

C(CH3)

COOH

CH3 Axit imtyltylaxtic

C6H5 Br Mg, te C6H5 MgBr CO2 C6H5 COOMgBr H
+

C6H5

COOH

166

3- Thu phn cc hp cht nitrin.

H R C N + H2O
+

HO-

RCOOH + H4N+ RCOO+ NH3

V d:
C6H5 CH2 Cl NaCN C6H5 n-C4H9 Cl NaCN CN CH2 CN H2SO4 (70%)
n-C4H9COO

C6H5 H+

CH2

COOH

n-C4H9Br NaCN m-CH3 C6H4

NaOH C6H4

m-CH3

CN

H2SO4 (75%)

n-C4H9COOH Axit valric m-CH3 C6H4 COOH Axit m-tluic

Trong cc phn ng iu ch nu trn y, phn ng xy ho trc tip thu c axt gi nguyn khung cacbon. Cc phn ng Grinha hay tng hp nitrin lm tng mch thm mt nguyn t cacbon. 12.5. TNH CHT HO HC. Tnh cht ho hc ca axt cacbxylic c quyt nh bi nhm cacbxyl COOH c mt trong phn t. Mt khc nhm COOH c to thnh t nhm CO v nhm OH m 2 nhm ny to hiu ng lin hp , p ln nhau lm cho lin kt O-H phn cc mnh dn n hyr d tch ra di dng ion H+.
O C O H

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

2- Phn ng cng vo nhm cacbnyl lm t lin kt C-OH O C OH 3- Phn ng cacbxyl ho (tch nhm CO2). O C O H 4- Phn ng th cc nguyn t hyr linh ng.

167 R CH COCl

12.5.1. Phn ng lm t lin kt O-H biu hin tnh axt.

RCOOH + H2O RCOOH RCOO
-

RCOO + H3O + H
+

V d:
2 CH3COOH + Zn (CH3COO)2Zn + H2
+ H2O H2O

CH3(CH2)10COOH + NaOH Axit lauric C6H5 COOH + NaHCO3

CH3(CH2)10COONa C6H5

COONa + CO2 +

Hng s axt Ka ca axt cacbxylic c bc vo khong 10-4 10-5. iu c ngha l axt cacbxylic rt yu. Kh nng biu hin tnh axt ca n c th so snh vi mt s cht sau y: RCOOH > HOH > ROH >HCCH > NH3 >RH Cc nhm th khc nhau c mt trong gc R gy nh hng n tnh axt: Cc nhm th ht in t s lm tng tnh axt. Cc nhm th y in t s lm gim tnh axt.
O G C O G C O O -

Nhm ht bn ho anion V d:

Nhm y gim bn anion.

Ka .10-5

HCOOH 17,7

CH3COOH 1,75

ClCH2COOH 136

Cl2CHCOOH 5530

Cl3C COOH 23200

Cc nhm th v tr gy nh hng ln nht:

CH3CH2CH2COOH CH3CH2CHCOOH Ka .10-5 1,52 Cl 139

CH3CHCH2COOH Cl 8,9

CH2CH2CH2COOH Cl 2,96

Qui lut trn y cng tm thy tng t i vi cc axt thm. 12.5.2. Phn ng cng vo nhm cacbnyl lm t lin kt C-OH
R CO OH Z
-

R CO

(Z = Cl , RO , NH2,...)

a. Phn ng to thnh cloranhyrat (clorua axit).

168

SOCl2 R COOH + PCl5 PCl3 R COCl

V d:
C6H5 COOH
+
0 PCl5 100 C

C6H5

COCl

+ POCl3 + HCl HCl

n-C17H35COOH + SOCl2 CH3COOH

un si

n- C17H35COCl + SO2 + CH3COCl

PCl3, 50 0 C

b. Phn ng este ho.

RCOOH RCOOH + R'OH H+ RCOOR' RCOOR'

SOCl2

RCOCl R'OH

V d:
C6H5COOH + CH3OH (CH3)3C COOH SOCl2 H
+

C6H5COOCH3 + C2H5OH

H2O (CH3)3C COOC2H5

(CH3)3C COCl

c. Phn ng to thnh amit.

RCOOH RCOOH NH3 SOCl2 un nng RCOONH4 RCONH2 NH3, un nng RCOCl RCONH2
un nng NH3

V d:
CH3COOH NH3 CH3COONH4 CH3CONH2 Axtamit C6H5CH2CONH2 Phnylaxtamit

C6H5CH2COOH

SOCl2

C6H5CH2COCl

12.5.3. Phn ng cacbxyl ho.

RCOOH tC
0

RH + CO2

V du:
C6H5COONa p-O2N C6H4 + NaOH C6H6 + Na2CO3 0 COOH + NaOH CaO, t C O2N C6H5 + Na2CO3 CaO, t0 C

Nhn chung phng php cacbxyl ho ch c ngha i vi cc axt cacbxylic thm. i vi cc axt bo phng php ny ch c ngha trong tng hp manlic v tng hp axtaxt m thi.

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V d:
COOC2H5 CH2 COOC2H5 C2H5ONa
-

COOC2H5 CH COOC2H5 R'CH2COOH

R'X

COOC2H5 R' CH COOC2H5 COOH R' CH COOH

- CO2

Tng hp manlic cho php iu ch cc dn xut ca axt cacbxylic m trong hyr c thay th bi cc nhm ankyl khc nhau. 12.5.4. Phn ng th hyr. a. Halogen ho hyr ca cc axt bo (Phn ng Hen-Fonhac-Zenlinxki).
R CH COOH + X2 H P R CH COOH + HX (X2 = Cl2, Br2) X

V d:
CH3COOH Cl2, P ClCH2COOH Cl2, P Br2, P Cl2CHCOOH Cl2, P Cl3C COOH

(CH3)2CH CH COOH H

(CH3)2CH CH COOH Br

Phn ng ny ch xy ra vi -hyr. Vi -hyr s khng c phn ng xy ra. C ch ca phn ng:

P + X2 R CH COOH + PX3 H R CH COX + X2 PX3 R CH COX + POX + HX

H R CH COX + HX R CH COOH + R CH COX X H

H X R CH COX + R CH COOH X H

Cc hp cht halogenua axt c nhiu ngha trong thc t v qua n c th iu ch c nhiu hp cht khc nhau nh axt khng no, amin axt, axt a chc

R CH COOH CN

NaCN

NH3 d

R CH COOH NH2 R CH COOH OH

R CH COOH KOH/ROH (1) HO Br R' CH CH COOH + (2) H

b. Phn ng SE nhn thm. Nhm cacbxyl COOH l nhm th loi 2 nn n c kh nng nh hng mta.

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COOH HNO3, H2SO4

COOH

NO2

12.5.5. Phn ng kh Tc nhn thng dng kh cc axt cacbxylic l LiAlH4.

RCOOH LiAlH4 RCH2OH

C ch:
RCOOH + LiAlH4 O R C + LiAlH4 OLi R CH O + LiAlH4 RCOO-Li+ + H2 + AlH3 OLi R C R CH O H OLi R CH2 OLi R CH2OH

V d:
m-CH3 C6H4 COOH LiAlH4 m-CH3 C6H4 CH2OH

12.6. CCH NHN BIT AXT CACBXYLIC. Axt cacbxylic c th nhn bit bng tnh axt ca n: tan trong kim, trong bicacbnat natri c CO2 bay ra, hoc bng cc phng php c trng cho cc tnh cht ca axt. Trong ph hng ngoi, axt cacbxylic c cc s sng c trng sau: (CO)= 1650-1750 cm-1 12.7. CU TO. Dn xut cc axt cacbxylic bao gm cloranhyrit, anhyrit, amt v este. Chng l nhng hp cht m trong nhm OH ca axt c thay th bi Cl, -OCOR, -NH2, -OR.
O R C OH Axit R C Cl Cloanhyrit O R C OCOR Anhyrit O R C NH2 Amit O R C OR' Este O

(OH) = 2500-3000cm-1

B. CC DN XUT CA AXT CACBXYLIC.

Tt c cc hp cht ny u cha nhm axyl, do cng ging nh cc hp cht khc chnh nhm nh chc ny quyt nh tnh cht ca cc axt cacbxylic.
R C O (Nhm axyl)

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12.8. CCH GI TN. Cc dn xut ca axt cacbxylic c tn gi thng thng v IUPAC tng t nh tn gi ca cc axt tng ng. V d:
CH3COOH Axit axtic CH3COCl (CH3CO)2O CH3CONH2 Axtamit CH3COOC2H5 tylaxtat tyltanat Axtylclorua Anhyrit axtic

Axit tanic tanylclorua Anhyrit tanic tanamit

C6H5COOH C6H5COCl (C6H5CO)2O C6H5CONH2 C6H5COOC2H5 Axit benzic Benzylclorua Anhyritbenzic Benzamit tylbenzat

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

Cc dn xut ca axt cacbxylic tan tt trong dung mi hu c v ch c mt s dn xut c C<5 l tan trong nc. 12.10. PHN NG TH NUCLPHIN CC DN XUT AXT. Cc hp cht axyl thng c xu hng tham gia phn ng th SN m trong cc nhm OH, -Cl, -OCOR, -NH2, -OR c thay th bng mt nhm khc. Phn ng th SN y xy ra d dng hn so vi trng hp phn ng th xy ra i vi cc nhm th lin kt vi nguyn t cacbon t din.
Z R C O Z + W R C OW Z = OH, Cl, OCOR, NH2, OR R C W + O Z

a. Xt v mt cu to, ging nh anhyt v xton y nhm cacbnyl c ocbitan lai ho sp2, phn cc nn thun li cho s tn cng ca cc tc nhn nuclphin.

Z 120
0

C O R

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Phn ng xy ra giai on u to thnh trng thi chuyn tip t din nh trong trng hp i vi anhyt hoc xton nhng trong giai on tip theo thay v bn ho sn phm bng s kt hp vi prton th xy ra s tch loi nhm Z.
R' R C O R C O Z + W R' + W (1) R C OW Z R C O W
-

H (2)

R' R C OH W R C W + O Z SN AN

(1)

(2)

b. Phn ng SN xy ra cc dn xut ca axt v c th c xc tc bng axt hoc baz. Trong mi trng baz, nhm OH l mt tc nhn nuclphin mnh, cn trong mi trng axt prton s prton ho nhm cacbnyl lm gim nng lng hot ho Ea ca phn ng. Thy phn bng baz:
R C O Z HO
-

Z R C O OH
-

C OH O

HO

RCOO + H2O

Thy phn bng axt:

R C O Z H
+

Z R C
+ OH

H2O

C OH2 OH

RCOOH + HZ + H+

c. Kh nng tham gia phn ng nuclphin ca cc dn xut axt cacbxylic c sp xp theo dy sau: R-CO-Cl > R-Cl R-CO-NH2 > R-NH2 R-CO-OR > R-OR Yu t nh hng n tc phn ng SN2 trong cc hp cht R-Z c gy ra bi hiu ng khng gian (v trng thi chuyn tip nguyn t cacbon c ho tr 5):
W... ...Z +

W +

Tri li trong phn ng SN ca cc dn xut axt cacbxylic tc phn ng khng b nh hng bi hiu ng khng gian m cc yu t xc tin s ph v lin kt s lm tng tc phn ng v phn ng xy ra qua trng thi chuyn tip t din.

173

R W + O

Z W

R Z O
-

R O

W + Z

12.1. CLORANHYRIT. 12.11.1. Cc phng php iu ch.

SOCl2 RCOOH + PCl5 PCl3 RCOCl

12.1.2. Tnh cht ho hc. Cloranhyrat tng t nh cc dn xut ca axt cacbxylic tham gia cc phn ng c trng SN. Trong phn ng ny, clo b tch ra di dng ion clo hay HCl. Cloranhyrat l hp cht c kh nng phn ng mnh nht trong tt c cc dn xut ca axt cacbxylic. a. Phn ng to thnh axt hoc dn xut ca chng.
RCOCl + HZ RCOZ + HCl

V d: - Phn ng to thnh axt (phn ng thu phn).

CH3COCl C6H5COCl + H2O + H2O
2 NH3

CH3COOH + HCl C6H5COOH + HCl

CH3CH2CONH2 + NH4Cl C6H5CONH2 + NH4Cl

- Phn ng to thnh amt.

CH3CH2COCl C6H5COCl + + 2 NH3

Phn ng to thnh este.

CH3COCl C6H5COCl + C2H5OH CH3COOC2H5 + C6H5COOC2H5 + HCl HCl + C2H5OH

b. Phn ng to thnh xton (anxyl ho Frien-Crap).

RCOCl + C6H6 AlCl3 C6H5 COR + HCl

Phn ng vi hp cht c cadimium.

R'MgX CdCl2 R'2Cd + RCOCl ArCOCl R CO R' Ar CO R'

c. Phn ng kh to thnh anhyt.

RCOCl H2, Pd/BaSO4 (Pd/S) ArCOCl RCHO ArCHO

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12.12. ANHYRIT AXIT. Anhyrit c nhng tnh cht tng t nh cloranhyrat nhng yu hn. 12.12.1. Cc phn ng iu ch. Trong cc hp cht anhyrit, thng gp v c ngha ln nht l anhyrit axtic. N c iu ch t xten nh sau:
CH3COOH CH2 AlPO4, 700 0 C CH2 C O + H2O Xten CH3COOH (CH3CO)2O

C O +

12.12.2. Tnh cht ho hc. a. Phn ng to thnh axt v cc dn xut ca n.

(RCO)2O + HZ RCOZ + RCOOH

V d : To axt:
(CH3CO)2O + H2O 2 CH3COOH

To amt:
(CH3CO)2O + 2 NH3 CH3CONH2 + CH3COONH4

- To este:
(CH3CO)2O + CH3OH CH3COOCH3 + CH3COOH

c. Phn ng to thnh xton (axyl ho Frien-Crap).

(RCO)2O + C6H6
H3C (CH3CO)2O + H3C Mzytylen CH3 AlCl3

AlCl3

R CO C6H5 + RCOOH
H3C CH3CO CH3 + CH3COOH

H3C Mtylmzytylxton

12.13. AMIT. 12.13.1. iu ch. T amnic vi axt cacbxylic hoc vi dn xut ca chng. a. T cloranhyrat.
RCOCl + 2 NH3 RCONH2 + NH4Cl

V d:
p-Br C6H4 COCl + 2 NH3 p-Br C6H4 CONH2 + NH4Cl

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b. T mui amni.
RCOOH + NH3
0 RCOONH4 t C

RCONH2 + H2O
n-C17H35CONH2 + H2O Stearamit

V d:
n-C17H35COOH + NH3 Axit stearic n- C17H35COONH4

12.13.2. Tnh cht ho hc. a. Phn ng thu phn.

H RCONH2 + H2O
+

RCOOH + NH4 RCOO-

HO-

+ NH3

V d:
C6H5 CO NH2 + H2SO4 + H2O C6H5 COOH + NH4HSO4 CH3CH2CH2CONH2 + NaOH + H2O CH3CH2CH2COONa + NH3

b. Phn ng tch loi Hpman.

RCONH2 ArCONH2 OBr
-

RNH2 ArNH2

-2 + CO3

Br-

y l mt trong nhng phn ng c nhiu thun li, dng iu ch cc amin bc I. C ch:

O R C NH2 O R C N H Br O R C N
-

O + OBr
-

R C N H Br O R C N O Br + N Br
-

HO-

HO-

H2O

R C Br O

R C N R N C O

R N C O
-

+ 2 HO

RNH2 + CO3-2

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

H+

RCOOR' +

H2O

V d:
CH3COOH + HOCH2
C6H5COOH + HOCH2

C6H5

CH3COOCH2

C6H5 + H2O

CH(CH3)2

C6H5COOCH2 CH(CH3)2 + H2O izbutylbenzat

c. T cloranhyrat, anhyrit axt.

RCOCl (RCO)2O + R'OH hoc ArOH + R'OH hoc ArOH
piriin

RCOOR' RCOOR'

hoc RCOOAr hoc RCOOAr

V d:
o-Br C6H4 COCl + C2H5OH o-Br C6H4 COOC2H5 NO2 NO2 NaOH p- CH3COO C6H4

(CH3CO)2O +

p-HO C6H4

d. Phn ng trao i este.

RCOOR' + R"OH H+ RCOOR'' + R'OH

Trong cc phn ng nu trn y, phn ng tc dng trc tip ancol hoc phnol vi axt cacbxylic l phn ng thun nghch v vy mun tng hiu sut ca phn ng cn phi tin hnh trong iu kin khc nghit (c bit i vi phn ng ca phnol) v chuyn hng phn ng v pha bn phi bng cch tng nng ca mt trong hai cht tham gia phn ng, tch sn phm ngay trong qu trnh phn ng (este hoc nc), s dng xc tc thch hp Phng php este ho c ngha ln trong cng nghip. Trong phng th nghim thng s dng phng php iu ch este t cloranhyrat hoc anhyrit axt. 12.14.2. Tnh cht ho hc. Este tham gia phn ng th nuclphin c trng cho cc dn xut ca axt cacbxylic dn n kt qu nhm OR c thay th bi cc nhm OH, -OR hoc NH2.

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O R C OR' O + Z
-

R C

R C O

Z + R'O

OR' (Z- = HO-, R''O-, NH3)

a. Phn ng to thnh axt v dn xut ca n. - To thnh axt:

H RCOOR' + H2O
+ -

RCOOH + RCOO+

R'OH R'OH

HO

V d:
C6H5COOC2H5 + H2O H2SO4 C H COOH + C2H5OH 6 5 NaOH C6H5COONa + C2H5OH
RCONH2 + R'OH

- To thnh amt:
RCOOR' + NH3

V d:
CH3COOC2H5 + NH3
H+

CH3CONH2 + C2H5OH

- To thnh este mi (phn ng trao i este).

RCOOR' + R"OH RCOOR'' + R'OH

V d:
CH2 OCOR CH OCOR' + CH2 OCOR' CH3OH H
+

CH3 CH3 CH3

OCOR OCOR' OCOR'

R'

CH2 OH + CH OH CH2 OH

b. Phn ng vi tc nhn Grinha.

RCOOR' + 2R'MgX R C OH R'

V d:
C6H5 C6H5 COOC2H5 + 2 C6H5 MgBr C6H5 C C6H5 OH Triphnylcacbinol

c. Kh thnh ancol - Kh ho xc tc:

RCOOR' +

H2

CuO.CuCr2O4

RCH2OH +

R'OH

178

V d:
(CH3)3C COOC2H5 + H2 CuO.CuCr2O4 (CH3)3C CH2OH + C2H5OH

- Kh ho ho hc :
RCOOR' Na, ancol LiAlH4 RCH2OH + R'OH RCH2OH + R'OH C2H5OH te khan, H+

RCOOR' +

V d:
CH3(CH2)6COOC2H5 Na, C2H5OH CH3(CH2)6CH2OH +

d. Phn ng th -hyr linh ng. - Phn ng ngng t este (ngng t Claizen). y l phn ng ca 2 phn t etse vi nhau khi c xc tc natri kim loi hoc natri ancolat to thnh este axt -xt-cacbxylic.
R C OC2H5 + O H CH COOC2H5 R' NaOC2H5 R C CH COOC2H5

O R' tylaxtoaxtat

V d:
CH3 CO OC2H5 + H CH2COOC2H5 C2H5ONa CH3 CO CH2COOC2H5

- Tng hp malnic.
COOC2H5 CH2 COOC2H5 H2O, H
+

C2H5ONa

COOC2H5 COOC2H5

CH

RX

COOC2H5 R CH COOC2H5

COOH R CH COOH

tC

RCH2COOH + CO2

12.14.3. Phn ng thu phn este. Este ca axt cacbxylic c th b thu phn to thnh axt v ancol hoc phnol bi axt hoc baz khi un nng. a. Thu phn bng baz. S thu phn este bng baz c gy ra bi s tn cng ca tc nhn nuclphin mnhHO-. Phn ng thc t khng thun nghch v anion cacbxylic c bn ho bi s cng hng nn rt kh phn ng tr li vi ancol. - C ch:

179
O R C OR' + HO
-

OR C OR' OH R C

O + R'OH (I) O

Trong cng thc cng hng (I) trn y in t p ca nguyn t cacon cacbnyl tham gia xen ph vi in t p ca c 2 nguyn t xi lm tng thm mt in t xen ph cc i dn n lin kt bn hn nn anion cng bn hn. - Chng minh c ch phn ng. 1- Phn ng xy ra bi s tn cng ca nhm OH: iu ny c xc nhn bng thc nghim ng hc, rng y l phn ng bc II v tc ca phn ng ph thuc nng vo ca c este ln HO-: v = k[RCOOR][HO-] 2- Nhm hyrxyl HO- c cng vo nguyn t cacbon cacbnyl v tch i ion ancolat - tc l phn ng xy ra vi s t lin kt gia xy v nhm axyl. iu ny c chng minh bng 2 cch sau y: * Phng php ho lp th. Khi cho benzylclorua tc dng vi ru (+)-sec-butylic quang hot, ngi ta thu c sec-butylbenzat m trong khng lm thay i cu hnh ca nguyn t cacbon bt i v khng lm ph v lin kt no ca n.
C2H5 C6H5 CO Cl + H O H CH3 C6H5 CO O C2H5 H CH3

Khi thu phn este ny bng HO- s xy ra 2 kh nng sau:

(1) O C6H5 C O C2H5 H (2) C6H5 COOH + H C2H5 C6H5 COOH + HO H CH3 C2H5 OH CH3

(1) HOCH3 (2)

Nu phn ng xy ra theo (1) th ru sec-butylic thu c s khng b i cu hnh v cc lin kt vi nguyn t cacbon bt i xng khng b ph v. Nu xy ra theo (2) th ru sec-butylic thu c hoc l b thay i cu hnh hon ton (nu xy ra phn ng th SN2) hoc to ra bin th raxmic (nu xy ra phn ng SN1).

180

Thc nghim chng minh rng ru sec-butylic thu c sau phn ng hon ton khng thay i cu hnh-ngha l xy ra s t lin kt gia xy v nhm cacbxyl RCOOR. Phng php nh du nguyn t: Trong phng php ny, ngi ta tin hnh thu phn tylprpanat c nh du bng O18 v thu c ru tylic c cha O18:
CH3CH2 CO O C2H5 +
18

HO

CH3CH2COOH + C2H5

18

O H

iu mt ln na chng minh rng trong phn ng thu phn este xy ra s phn ct lin kt gia nguyn t xy v nhm axyl. Phn ng cng xy ra tng t i vi cc dn xut khc ca axt cacbxylic. b. Thu phn bng axt.
RCOOR' + H2O H+ RCOOH + R'OH

C ch:
O R C OR' OH R C OH -R'OH R HOR'
+

OH + H
+

H2O

OH R C OH2 OR'
+

OR' OH C OH
+

-H

RCOOH

Axt v c trong phn ng ny ng vai tr prton ho nguyn t xy ca nhm cacbnyl lm tng kh nng phn ng nuclphin ca nguyn t cacbon. 12.15. CHT BO. 12.15.1. Cht bo trong t nhin v thnh phn ho hc ca n. Mt s este thng gp trong t nhin c ngha rt quan trng i vi i sng l cht bo (dng lng thng gp gi l du): du da, du u phng, du bng, du ng, du liu, du c(dng sp, m): m heo, m b, m d, m cu Tt c cc loi este ny u c to thnh t mt gc ru a chc glyxrin vi cc gc axt cacbxylic khc nhau, do cn c tn gi l cc hp cht glyxrit. Hu ht cc axt cacbxylic to thnh cht bo l axt mch h cha t 3 n 18 nguyn t cacbon. Tr 2 loi axt c s l nguyn t cacbon C3 v C5 cn li tt c cc axt cu to nn

181

cht bo u c s nguyn t cacbon l s chn. Ngoi ra cc axt cacbxylic cng c th no, khng no mt hoc nhiu ni i. Nh vy thnh phn ca mt cht bo l mt hn hp glyxrit vi nhng t l khc nhau v chnh cc t l khc nhau c trong thnh phn ca cht bo quyt nh loi cht bo, dng tn ti v mu sc, mi vca cht bo. 12.15.2. Phn ng thu phn cc cht bo. Cc cht bo c th thu phn bi axt hoc baz. Nu thu phn bng baz th ngi ta gi l phn ng x phng ho.
CH2 OCOR CH OCOR' CH2 OCOR' NaOH CH2 OH CH OH CH2 OH Glyxrin + RCOONa R'COONa R'COONa X phng

Nh vy, c x phng ngi ta tin hnh thu phn cc cht bo bng dung dch kim. c x phng khng mu khi thu phn cn cho thm ru, x phng c mu, c mi cn cho thm cc cht ph gia nh phm mu, tinh du trnh hi da cn cho thm cc cht kh trng. Nu thu phn cc este bng NaOH ta s c x phng cng (rn), cn nu thu phn bng KOH s thu c x phng mm (x phng nc).

182 CU HI N TP V BI TP CHNG 12

12.1. T dn xut halogen, vit phng trnh phn ng iu ch cc axit sau: a. Axit propionic b. Axit izobutyric c. Axit phenyl axetic 12.2. Sp xp cc hp cht sau y theo th t tng dn tnh axit: a. CH3COOH, CCl3COOH, CHCl2COOH, CH2ClCOOH b. (CH3)3C-COOH, (CH3)2CH-COOH, CH3CH2COOH, CH3COOH c. C6H5COOH, p-CH3-C6H4COOH, p-NO2-C6H4COOH 12.3. Gi tn cc hp cht sau theo danh php quc t v tn thng thng (nu c):
a. CH3(CH2)3COOH b. CH3 C CH CH2COOH CH3 c. HOOC C C COOH H H CH3 e. CH3CH2 C N O CH3 f. CH3 CH CH2 C Cl Cl O H H d.HOOC C C COOH

12.4. iu ch cc hp cht sau: a. Axit 4-phenyl butanoic t toluen b. Benzylamin t benzamid c. Anilin t benzamid d. butanon-2 t acetonitril e. Axit benzoic t brombenzen f. Axit 2,2-dimetyl propanoic t tec-butyl bromua 12.5. Trnh by c ch ca cc phn ng sau y:
a. R C NH2 O b. R C Cl O c. R C N Br2, HORNH2 RCH2COOH

1. CH2N2 2. Ag2O, H2O H3O+ RCOOH

12.6. S thu phn trong mi trng axit ca 1-metylpropyl axetat c tnh quang hot xy ra vi s lu gi cu hnh. Trnh by c ch ca phn ng thu phn trn.

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TI LIU THAM KHO CA BI TP CHNG 12 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni. [5]. Nguyn th Bch Tuyt (1995), Gio trnh ha hu c, Hu.

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Chng 13 AMIN 13.1. CU TO PHN LOI V CCH GI TN. 13.1.1. Cu to. Amin l cc hp cht c cng thc phn t tng qut: RNH2, R2NH hoc R3N trong R-ankyl hoc aryl. V d:
CH3NH2 Mtylamin (Amin 10 ) (CH3)2NH imtylamin (Amin 20 )
NH2

(CH3)3N Trimtylamin (Amin 30 )

NHCH3

H2N CH2 CH2 NH2 tyleniamin (Amin 10 )

N(CH3)2

Anilin (Amin 10 )

N-Mtylanilin (Amin 20 )

N,N-imtylanilin (Amin 30 )

13.1.2. Phn loi. Amin c phn thnh bc I, bc II, bc III ph thuc vo s lng cc nhm th lin kt vi nguyn t nit.
H R N H (Amin 1 )
0

H R N R (Amin 2 )
0

R R N R (Amin 3 0 )

13.1.3. Cch gi tn. Tn gi ca cc amin bo c hnh thnh bng cch thm ui amin vo tn gi ca nhm ankyl hoc cc nhm th lin kt vi nhm amin. Trng hp i vi cc amin phc tp thng ngi ta thm cc tip t amin- (hoc N-mtylamin-, N,N-imtylamin-) vo tn gi ca mch chnh. V d:
(CH3)3C NH2 Tec-butylamin H2N CH2 CH2 OH 2-amintanol CH3CH2 NH CH3 (CH3)2N C2H5 tylmtylamin imtyltylamin CH3 NH CH(CH3) CH2 (CH2)3 CH3 2-(N-Mtylamin)-heptan

Cc amin thm trong nguyn t hyr lin kt trc tip vi nhn thm thng c gi nh l dn xut ca anilin. Mui ca cc hp cht ny c gi bng cch thay ui amin thnh amni (hoc anilin thnh anilini). V d:

185
NH2 Br Br CH3 N C2H5 N(CH3)2 CH3

Br NH2 NO2 2,4,6-Tribrmanilin N-Mtyl-N-tylanilin p-nitr-N,N-imtylanilin p-Tluin

(C2H5NH3)2SO4-2 Sunfat itylamni

(CH3)3NHNO3Nitrat trimtylamni

C6H5NH3ClClorua anilini

13.4. TNH CHT VT L. Tng t nh amnic, cc amin l nhng hp cht phn cc tr amin bc III v chng c kh nng to lin kt hyr lin phn t. Amin c nhit si cao hn cc hp cht khng phn cc c cng phn t lng nhng thp hn nhit si c ancol v axt cacbxylic tng ng. Amin c kh nng to lin kt hyr vi nc v vy nhng amin thp (c s nguyn t cacbon nh thua 6) ho tan tt trong nc. Amin t tan trong cc dung mi t phn cc nh ete, benzen Mtylamin v tylamin c mi ging amnic. Cc amin cao hn c mi ta mi tanh ca c. Amin thm l nhng cht c v d b xy ho bi khng kh. 13.5. IU CH. 13.5.1. Phng php cng nghip. Mt s amin quan trng c s dng rng ri trong cng nghip iu ch theo cc phng php sau y: a. Anilin. Anilin c iu ch bng cch: 1- Kh ho ho hc hoc kh ho xc tc cc hp cht nitrbenzen.
C6H5 NO2 Fe, HCl , t C
0

C6H5NH3Cl-

Na2CO3

C6H5NH2

2- Chuyn ho clobenzen bng mnic nhit v p sut cao c xc tc.

C6H5Cl NH3, CuO, 200 C, 65at
0

C6H5NH2

b. Mtylamin, imtylamin, trimtylamin. Cc hp cht ny c iu ch t ru mtanol v amnic c xc tc.

NH3 CH3OH CH3OH CH3OH CH3NH2 (CH3)2NH (CH3)3N 0 0 Al2O3, 450 C Al2O3, 450 C Al2O3, 450 0 C

c. iu ch cc amin bc cao.

186

Trong cng nghip iu ch cc amin bc cao ngi ta s dng cc phn ng amin ho cc ankylhalogenua. Ngoi ra mt s amin c s chn cc nguyn t cacbon c th c iu ch t cc axt bo-sn phm thu phn ca cc cht bo.
RCOOH NH3, t C
0

RCONH2

un nng

R C N

H2, Ni

R CH2

NH2

13.5.2. Cc phng php phng th nghim. a. Kh ho cc hp cht nitr.

R NO2 Ar NO2 H2/xt Kim loi/axit R NH2 Ar NH2

V d:
p-C2H5OOC C6H4 p-H2N C6H4 o-O2N C6H4 CH3CH2CH2 NO2 NO2 NO2 NO2 H2, Pd p-C2H5OOC C6H4 NH2 NH2 NH2 NH2 tyl-p-nitrbenzat Sn, HCl NH4SH Fe, HCl tyl-p-aminbenzat p-H2N C6H4 o-O2N C6H4 CH3CH2CH2

Phng php kh ho cc hp cht nitr ch yu dng iu ch cc hp cht amin thm. Trng hp trong nhn thm c nhiu nhm NO2 m ch mun kh mt nhm th thng s dng tc nhn (NH4SH). Phng php ny ch c ngha ln trong trng hp trong phn t ca hp cht c nhm nitr cn kh khng cha cc nhm th d b kh ho hn. V d trong phn ng sau y lin kt kp s b kh trc nhm nitr.
o-O2N C6H4 CH CH R H2, Ni o-O2N C6H4 CH2 CH2 R

c. Phn ng ca dn xut halogen vi amnic, vi amin.

NH3 RX RNH2 RX R2NH RX R3N RX ( R- ankyl hoc aryl c nhm th loi II) R4N X
+ -

V d:
CH3COOH Cl2, P Cl CH2COOH NH3 H2N CH2COO NH4
+

H2N CH2COOH

C6H5CH2Cl

NH3

C6H5CH2

NH2

CH3Cl

C6H5CH2

N(CH3)2

187

Cl NO2 NH3

NH2 NO2 CH3Cl

NHCH3 NO2

NO2 2,4-initrclobenzen

NO2

NO2 N-Mtyl-2,4-initranilin

Phn ng amin ho dn xut halogen xy ra theo c ch th nuclphin m trong amnic hoc amin l tc nhn nuclphin.
H3N + R X H3N . . . R. . . X
+
-

H3N R + X-

SN 2

V vy hp cht amin thu c vi hiu sut ln khi dn xut halogen tham gia phn ng l bc I. Trong trng hp dn xut halogen l 30 th sn phm phn ng ch yu ca phn ng l sn phm tch loi. V d:
CH3CH2CH2CH2 (CH3)2C Br CH3 Br NH3 NH3 CH3CH2CH2CH2NH2 SN E

(CH3)2C CH2 + NH4Br

Nhc im ln nht ca phn ng amin ho theo cch ny l sn phm thu c l mt hn hp cc hp cht amin vi bc khc nhau. V d:
RX + NH3 RNH2 R2NH R3N (Amin 1 ) (Amin 2 ) (Amin 3 )
0 0 0 0

RNH2 + RX R2NH + RX R3N + RX

R4N+X- (Amin 4 )

V vy hiu sut sn phm ch yu to thnh amin 10, ngi ta phi cho mt lng NH3 d rt ln. c. Kh ho-amin ho. Phn ng chuyn ho mt s anhyt RCHO v xton RCOR thnh amin di tc dng ca hyr, amnic, khi c mt ca xc tc kim loi.
+ NH3 + H2 C O + RNH2 + H2 + R2NH + H2 Ni Ni Ni CH NH2 CH NHR CH NR2

188

V d:
CH3 CO CH3 + NH3 + H2 Ni CH3 H2 Ni CH3CH2 CH CH3 NH2 CH3CH2CH2CHO + C6H5 CH3CHO + (CH3)2NH NH2 + + H2 Ni C6H5 NH CH2CH2CH2CH3

N(CH3)2

Cho n nay c ch ca phn ng ny vn cha c chng minh y nhng c nhiu gi thit cho rng phn ng xy ra qua bc to thnh hp cht trung gian imin RCH=NH hoc R2C=NH.
RCHO + NH3 R C O R' + NH3 RCH NH R H2, Ni RCH2NH2 R CH NH2 R'

C NH R'

H2, Ni

u im ln nht ca loi phn ng ny l c th iu ch nhng amin 20 m bng phn ng amin ho cc dn xut halogen khng th iu ch c. V d:
K2C2O7, H2SO4 OH PBr3 Br O NH3 H2, Ni NH3 NH2

Nhc im chnh ca phng php ny l cng to thnh hn hp sn phm amin cc bc khc nhau do iu ch amin 10 phi cho NH3 d. d. Kh ho hp cht nitrin.
R CN H2, xt RCH2NH2

V d:
C6H5CH2 Cl + NaCN NC C6H5CH2
0 CN H2, Ni, 140 C C6H5CH2CH2NH2

ClCH2CH2CH2CH2Cl NaCN

(CH2)4 CN Aipnitrin

H2, Ni

H2N (CH2)6 NH2 Hecxamtyleniamin

e. Tch loi amt theo Hpman.

RCONH2 ArCONH2 OBr(Br2 + KOH) RNH2 ArNH2
-2 + CO3 + Br

g. Tng hp amin 10 tinh khit theo phng php Gabrien. Cc anhyrit mch vng tng t nh anhyrit mch h khi tc dng vi amnic to thnh amt v nu cho amt un nng th s thu c hp cht imt. u im ca phn ng ny

189

l cho php gn mt nhm ankyl vo nguyn t nit m thi nn sn phm thu c ch duy nht l amin 10.
O C O C O NH3, un nng C O C NH KOH C O C O O O C NK
- +

NH3

CONH2 COONH4 O C NH

CONH2 COOH

un nng

O C RX C O N R R NH2

Qua cc phng php iu ch amin nu trn y ta c th rt ra mt s nhn xt sau: 1- Phng php kh ho cc hp cht nitrin lm tng thm mch cacbon ca phn t hp cht ban u. 2- Tch loi Hpman, ngc li lm gim mch cacbon. 3- Cc phng php amin ho ankylhalogenua, kh ho-amin ho anhyt hoc xton u gi nguyn mch cacbon. 13.6. TNH CHT HA HC. Tt c cc hp cht amin tng t nh amnic, nguyn t nit c cha cp in t khng phn chia l tc nhn nuclphin trong cc phn ng. 1- Tnh baz-cc phn ng to mui.
RNH2 + R2NH R3N + + H+ H+ H+ RNH3 R2NH2 R3NH
+ + +

V d:
C6H5 NH2 + HCl + HNO3 C6H5
+

NH3Cl

(CH3)2NH

(CH3)2NH2NO3

2- Phn ng ankyl ho cc amin.

190

RNH2 ArNH2

RX RX

R2NH ArNHR

RX RX

R3N

RX

R4N X

+ +

ArNR2 RX

ArNR3X-

3- Phn ng to thnh amit.

R'COCl RNH2 0 Amin 1 R2NH 0 Amin 2
0

R' CO NHR Ar SO2 NHR

Sn phm N-amit Sn phm N-sunfamit Sn phm N,N-amit Sn phm N,N-sunfamit

ArSO2Cl R'COCl ArSO2Cl

R' CO NR2 Ar SO2 NR2

Cc amin bc 3 khng tham gia cc phn ng trn y. V d:

CH3COCl C6H5NH2 C6H5SO2Cl CH3CO NH C6H5 Axtanilit C6H5 SO2 NH C6H5 N-Phnylbenzensunfamit

4- Phn ng th ca cc amin thm. Cc amin thm c cc nhm th -NH2, -NHR, -NR2 v NHCOR l nhng nhm th loi I nn nh hng cc sn phm th vo v tr ct v para. V d:
NH2 NH2 Br Br2 Br

NHCOCH3 Br (CH3CO)2O Br2

NHCOCH3 H2O, H+

NH2

Br

Br

5- Phn ng vi axt nitr.

HNO2/HCl ArNH2 Amin thm 1 0
RNH2 Amin 1 0 HNO2/HCl R N N Cl
+ -

Ar N N ClMui iazni
H2O ROH + N2

anken.

Vi amin 10 c phn t lng ln hn, khi cho tc dng vi axit nitr (HNO2) s to ra

191

Amin 20

Ar

NHR

HNO2/HCl

Ar

NR N O

R2NH Ar R3N NR2 HNO2/HCl

R2N N O p- R2N C6H4 R3N N O Cl+

Amin 30

NO

6- Phn ng tch loi Hpman.

C C HO , t C
0

+ R3N + H2O

H +NR3

13.7. CCH NHN BIT AMIN. Cc amin c th nhn bit bng tnh cht kim ca n, tnh t tan trong nc nhng tan tt trong axt HCl long v lnh.
+

phn bit cc amin bc 10, 20, 30 ngi ta dng phn ng Kinsberg: cho amin tc

dng vi benzensunfclorua trong dung dch KOH.

RNH2 + C6H5SO2Cl Amin 10 R2NH + C6H5SO2Cl 0 Amin 2 R3N + C6H5SO2Cl Amin 3
0

HO-

C6H5SO2NHR

KOH

HO-

C6H5SO2NR2 khng tan R3N HCl

KOH hoc H+

C6H5SO2N-K+ tan R

H+

C6H5SO2NHR khng tan

Khng thay i

HO-

R3NHCltan

khng phn ng

192 CU HI N TP V BI TP CHNG 13

13.1. Gi tn cc hp cht sau y:

a. CH3 CH CH2NH2 CH3 c. H2C CH CH2NH2 b. CH3 CH CH2 NH CH3 CH3 d. (CH3)2NCH2CH2OH

e. CH3 N CH2 CH(CH3)2 f. CH3 CH CH2 C N CH2CH2CH3 N(CH3)2

13.2. Hy sp xp theo th t tng dn tnh baz ca cc hp cht sau: a. C2H5NH2, NH3, (C2H5)2NH, (C2H5)3N b. C6H5NHCH3, C6H5NH2, C6H5N(CH3)2, p-NO2-C6H4NH2 c. p-CH3-C6H4NH2, C6H5CH2NH2, (C6H5)2NH, (C6H5)3N 13.3. Vit cng thc cu to ca cc hp cht sau: a. p-nitro-N-metyl-N-etylanilin c. 4-(N-butyl-N-vinylamino)-2-pentanol e. N,N- diphenyletylendiamin g. Benzyltrimetylamoni Iodua a. HCl c. Benzensunfonyl clorua b. 3-(N,N-diallylamino)-2-hexanon d. N,N-diphenyletylendiamin f. 1,2-propandiamin h. Tetrametylamoni Hidroxit b. CH3COCl d. NaNO2 trong dung dch HCl

13.4. Vit phng trnh phn ng ca 2-aminobutan vi:

13.5. Hp cht A (C5H11NO) khng tan trong dung dch axit hay baz long nhit thng. Khi un nng A vi dung dch NaOH ta c mt mui B v mt kh C. Khi C tc dng vi benzensunfonyl clorua cho ra benzensunfonamid khng tan trong baz d. Khi B tc dng vi HCl to ra D tan d dng trong baz long, D tc dng vi SOCl2 cho ra E. Khi E phn ng lng tha NH3 cho ra G, G phn ng vi Br2, NaOH cho ra etylamin. Hy cho bit cng thc cu to ca cc cht t A ti G. TI LIU THAM KHO CA BI TP CHNG 13 [1]. Chu Phm Ngc Sn, Nguyn Hu Tnh, Nguyn Huy Ngc, L Khc Tch, Bi tp ha hc hu c. [2]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [3]. Thi Don Tnh, Bi tp c s l thuyt ha hu c (2005), Nxb. Khoa hc v K thut, H Ni. [4]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni.

193

Chng 14 HP CHT D VNG V CC ANKALOIT A. HP CHT D VNG. 14. NH NGHA. Hp cht d vng l nhng hp cht c cha trong mch vng ca n hoc mt s nguyn t ca cc nguyn t khng phi l cacbon (xy, lu hunh, xilen, nit, photpho, silic, ch, thu ngn). Thng thng trong cc trng hp cht d vng hay gp cc cht d vng c cha nit, lu hunh v xy. V d:

N H Pyrol

O Furan

S Thiphen

N H Pyrliin

N Piriin N

N Quinlin

N H Carbazol

N Nictin

CH3

Izquinlin

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

N H I

O II

S III

Nu ch xem xt cc cng thc cu to I, II, III ta c th d on cc hp cht ny mang tnh cht ca h ien lin hp v cc tnh cht ca amin, te v sunfua. Nhng thc nghim cho thy rng cc hp cht ny c biu hin mt s tnh cht hon ton khc hn vi nhng d on rt ra t nhng cng thc cu to I, II, III. V d tiphen iu kin bnh thng khng tham gia phn ng xy ho l phn ng c trng cho cc hp cht sunfua cn pirol li khng tham gia cc phn ng biu hin tnh baz c trng cho cc hp cht amin. Mt khc cc hp cht pirol, furan, tiphen v cc dn xut ca n li c kh nng tham gia phn ng electrphin nh nitr ho, sunf ho, halogen ho k c phn ng ghp iazni. Tt c cc

194

tnh cht trn c gii thch tho mn rng cc hp cht pirol, furan, tiphen l nhng hp cht thm v s in t p ca cc hp cht trn y ph hp vi qui tc 4n +2 ca Huycken l 6 in t. Mi mt nguyn t ca vng k c Ccbon ln nit s dng 3 lin kt ca obitan lai ho sp2 lin kt vi nhau. Nh vy mi nguyn t cacbon cn li mt in t p v nguyn t nit cn li 2 in t p (trong trng hp pirol). S xen ph ca cc in t p ny dn n hnh thnh m my in t lin kt nm pha trn v nm pha di mt phng ca vng. Cp in t ca nit trong trng hp ny tham gia xen ph vi h in t p ca cacbon nn khng cn c kh nng th hin tnh baz na. Tri li mt in t ca vng tng ln nn lm xut hin cc kh nng tham gia phn ng th electrphin ca pirol.
H H

N H

Tng t nh vy cc hp cht furan v thiphen cng mang tnh cht ca cc hp cht thm. 14.2.2. Cc phng php iu ch pirol, furan, tiphen. Pirol v tiphen c cha mt lng khng ln lm trong nha than . Trong cng nghip tiphen c iu ch bng phn ng gia butan v lu hunh nhit cao.
CH3CH2CH2CH3 +
0 S 560 C

+ S

H2S

Pirol c th tng hp bng nhiu cch khc nhau m di y l mt trong cc phng php .
HC CH + 2HCHO HOCH2 C C CH2OH NH3, P N H

Furan c iu ch bng phng php cacbxyl ho fufurol, sn phm ca qu trnh thy phn pentza bng HCl.
(C5H8O4)n Pentzan H2O/H
+

HOCH2(CHOH)3CHO Pentza

CHO

xt, t C O

Cc hp cht pirol, furan, tiphen cng c th c iu ch bng phng php vng ho. V d:

195
P2O5, t C CH2 H3C C C CH3 O O Hecxaion-2,5 CH2 P2S5, t0C (NH4)2CO3, 100 0 C
0

H3C H3C H3C

O S N H

CH3 CH3 CH3

14.2.3. Phn ng th electrphin ca pirol, furan, tiphen. Tng t nh cc hp cht thm pirol, furan, tiphen tham gia cc phn ng nitr ho, halogen ho, sunfnic hoKh nng tham gia phn ng ca chng mnh hn benzen. Phn ng thng xy ra vi s u tin nh hng vo v tr 2. V d:
O O + SO3 Piriin O SO3H COCH3

+ (CH3CO)2O

(C2H5)2O BF3 O

+ C6H5COCl
+ ClN N +

SnCl4 S

COC6H5

N H N H

N H

N N

+ KOH + CHCl3

N H

CHO

C ch ca cc phn ng trn y xy ra tng t nh phn ng th electrphin vo nhn thm.

+ Y
+

chm N H
+

Y H

nhanh N H

N H

Trong s c ch ca phn ng trn y ta nhn thy pirol tham gia phn ng th SE mnh hn benzen v to thnh phc m trong cc nguyn t u c 8 electron lp ngoi cng nn bn vng hn so vi phc ca benzen.

196
+ +

N H Phc ca pirol
Phc ca benzen

Tng t nh vy ngi ta gii thch kh nng tham gia phn ng SE ca furan v tiphen. Cc hp cht pirol, furan khi b hyr ho c xc tc s to thnh nhng hp cht d vng no tng ng-piroliin v ttrahyrfuran. Piroliin v ttrahyrfuran hoc ttrahyrtiphen biu hin cc tnh cht tng t vi cc loi hp cht ca n: amin bc II, te hoc sunfua.

N H

N H

Ttrahyrfuran l mt dung mi rt quan trng c s dng rng ri trong cng nghip v trong phng th nghim, c bit l trong cc phn ng kh ho bng Liti nhm hyrua. 14.3. CC HP CHT D VNG 6 CNH. 14.3.1. Cu to ca piriin. Trong cc hp cht d vng thm 6 cnh, chng ta tin hnh nghin cu cc hp cht piriin. Piriin biu hin tnh cht ca mt hp cht thm-tham gia phn ng th eletrphin. Trong phn t piriin nguyn t nit tng t nh nguyn t cacbon to thnh lin kt vi nhau bng 2 ocbitan lai to sp2 v s dng mt in t p to thnh lin kt . Mi nguyn t cacbon cn li mt ocbitan sp2 dng to lin kt vi hyr. Trong khi ocbitan cn li ca nit c cha 2 in t. Chnh s c mt ca cp in t ny l nguyn nhn dn n piriin c tnh baz.
H H H H N H

197

14.3.2. Cc phng php iu ch. Piriin c th thu nhn bng cch chng ct nha than . Ngoi ra cc hp cht piriin c th tng hp bng nhiu phng php khc nhau. V d:
CH3 2 CH2 CH CHO + NH3 N 3-Mtylpiriin N Axit Nictinic COOH

14.3.3. Tnh cht ho hc ca piriin. a. Phn ng th SE ca piriin. Trong phn ng loi ny, piriin biu hin tnh cht tng t nh dn xut ca benzen c nhm gim hot: cc phn ng nitr ho, sunfunic ho, halogen ho xy ra trong iu kin khc nghit cn phn ng th Frien-Crap th khng xy ra. Phn ng nh hng ch yu vo v tr .
HNO3/H2SO4, 300 0 C N H2SO4, 350 0 C Br N NO2

SO3H

Br2, 300 0 C

Br + N

Br

RX hoc RCOX, AlCl3

N Khng xy ra

b. Phn ng th nuclphin ca piriin. Phn ng loi ny xy ra d dng i vi piriin v ch yu xy ra v tr 2 v 4. V d:

NH3, 180-2000 C N Cl Br N NH2 NH2

NH3, 180-2000 C N N

198

Phn ng Titibabin.
+ NaNH2 N t0C N H NH2 N NH2

c. Phn ng kh piriin.
H2, Pt, HCl, 25 0 C, 3at N N H Piperiin

Piriin mang tnh cht ca mt amin bc II. Piriin thng c s dng lm cht xc tc. B. ANCALOIT. 14.4. NH NGHA. Ancaloit l nhng hp cht c hot tnh sinh hc mnh, do n c s dng nhiu trong i sng, c bit l trong y hc. Ancaloit thc vt thng c trong cy h u, cy thuc phin. Thng cc ancaloit khng phi cha trong ton thn cy m ch cha mt b phn no . V d nictin ch c trong l thuc, kinin ch c trong r cy kininMt khc c th ch mt loi cy nhng cha nhiu ancaloit khc nhau. Ancaloit trong thc vt thng tn ti di cc mui vi axt hu c. tch cc ancaloit, thng ngi ta x l cc phn ca thn cy c cha mui ca n bng kim hoc amnic sau tch ancaloit t do bng ete, clorofoc hoc cc dung mi hu c khc. Hin nay, ngi ta bit c khong 1000 ancaloit khc nhau nhng vn nhiu hp cht trong cha c xc nh cng thc cu to. 14.5. PHN LOI CC ANCALOIT. Ancaloit c phn loi theo s n v vng hyrcacbon c trong phn t c cha nguyn t nit. 14.5.1. Ancaloit d vng 5 cnh cha mt nguyn t nit. Hp cht n gin nht ca loi ny l Gigrin.
CH2 C O CH3

N CH3

199

14.5.2. Ancaloit h 2 vng cha mt nguyn t nit. y l mt loi ancaloit thng gp trong cc loi cy hoa chm nh pirliin, gelitrian. Hp cht quan trng nht ca loi ny l platigilin c dng trong y hc lm dn n mch mu chng cc cn co tht.
OH O C C CH2 CHCH3 CH3 N Pirliziin N Gelitrian O N Platigilin CH C CH3 CH3 CH2O C O

14.5.3. Ancaloit d vng 5 cnh cha haint nit. i din cho loi hp cht ny l pilcatpin (c trong l cy pilcarpis Jaborandi) dng cha bnh tng nhn p (thin u thng do s tng p sut mch mu mt).
CH3CH2 O O Pilocarpin CH2 N N CH3

14.5.4. Ancaloit d vng 6 cnh cha mt nguyn t nit. Ancaloit loi ny ch yu cha mt vng piperiin. V d conin l -prpylpiperiddin, piperiin l ancaloit ca ht tiu cng l dn xut ca piperiin.
O N H CH2CH2CH3 Conin N O C O CH CH CH CH Piperin O

Ancaloit t cy thuc phin gm mocphin v cin.

OH O HO N CH3 HO N CH3 OCH3

200 CU HI N TP V BI TP CHNG 14

14.1. T axit sucxinic hy iu ch pirol. 14.2. Hy cho bit sn phm phn ng ca piriin vi: a. HCl b. B(CH3)3 c. CH3I d. tec-butyl clorua 14.3. T quinolin v cc ha cht cn thit khc hy iu ch: a. 8-hiroxiquinolin bng hai phng php. b. 2-aminoquinolin. 14.4. Hon thnh s phn ng sau:
o-NH2C6H4COOH
+

ClCH2COOH -HCl

t0C -H2O

-CO2

C8H7ON (D)

14.5. T 2-metylpiriin v cc ha cht cn thit khc hy iu ch: a. 2-axetylpiriin b. 2-vinylpiriin c. 2-xiclopropylpiriin. 14.6. Piriin c b ankyl ha hoc axyl ha theo Frien-Crap khng?. T piriin hy iu ch 2n-butylpiriin v 2-n-butylpiperiin. 14.7. Vit cng thc cu trc v gi tn cc sn phm to thnh khi mononotro ha cc hp cht sau: a. 3-nitropyrol c. 2-axetylthiophen b. 3-metoxithiophen d. 5-metyl-2-metoxithiophen

14.8. So snh tnh baz ca pyriin, pyrol v piperiin. 14.9. Gii thch ti sao anilin c tnh baz yu hn pyriin. 14.10. Vit phn ng ca pyrol vi cc tc nhn sau: a. HCl c. CH3COOCOCH3 b. HNO3/H+ d. H2/Pt TI LIU THAM KHO CA BI TP CHNG 14 [1]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [2]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni.

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Chng 15 GLUXIT (Hyrat cacbon) 15.1. M U. Trong l ca cc loi cy xanh, cc phn t ng (+)-gluc c to thnh bi s tc dng ca 2 hp cht n gin l kh CO2 v nc. Qu trnh ny gi l s quang hp. N xy ra bi s xc tc dip lc v ngun nng lng nh sng mt tri. Hng ngn phn t (+)-gluc c th tp hp li vi nhau to thnh mt phn t ln gi l xenlul. Xenlul chnh l ngun nguyn liu c bn nht cu to nn c th thc vt. Cc phn t (+)-gluc cng c th kt hp vi nhau bng mt cch khc to tinh bt lm ngun d tr thc n cho qu trnh pht trin ca mt th h mi. Khi cc ng vt n tinh bt hoc xenlul th cc hp cht ny b ph v thnh hp cht ban u l (+)-gluc. Cc phn t (+)-gluc ny c mu mang n gan v bin i thnh glicgen (tinh bt ng vt). Trong mt s trng hp cn thit khc glicgen c th chuyn ho li thnh (+)-gluc. (+)-Gluc cng c mu a n cc t bo v y n b xy ho thnh kh cacbnic v nc, ng thi gii phng s nng lng m n hp th ca nh sng mt tri. Mt s lng (+)-gluc chuyn ho thnh m, cn mt s khc lin kt vi cc hp cht c cha nit to thnh aminaxt sau cc aminaxt lin kt vi nhau to thnh prtin lm nn tng cho mi hot ng ca s sng. (+)-Gluc, xenlul, tinh bt v glicgen thuc vo loi hp cht hu c c tn gi lag gluxit. Cc hp cht gluxit chnh l ngun nguyn liu p ng nhng nhu cu c bn nht ca con ngi. Chng ta s dng tinh bt lm thc n hoc l di dng ht ng cc, hoc l di dng c ng vt chuyn thnh tht, m. Chng ta dng qun o c sn xut t xenlul nh bng, si visc, si axtatc bit trong s pht trin ca th gii vn minh ngy ny xenlul ng vai tr rt quan trng sn xut giy. Tm li, ho hc gluxit l mt lnh vc rt th v ca ho hc hu c. N bao gm mt chu trnh t s quang hot to thnh phn t (+)-gluc t kh cacbnic v nc c xc tc bi men dip lc v nng lng nh sng mt tri n s chuyn ho ngc li t (+)-gluc thnh kh cacbnic v nc bi cc loi men c trong c th ng vt v gii phng nng lng m n hp th ca mt tri. Gia hai qua trnh sinh ho y, c mt nhuim v rt quan trng v quen thuc ca ho hc l xc nh cc cng thc cu to, nghin cu cc tnh cht v s chuyn ho ca gluxit thnh cc hp cht khc.

202

Di y ta s nghin cu mt vi tnh cht c bn ca gluxit lm c s cho qu trnh nghin cu tip theo v n. 15.2. NH NGHA V PHN LOI. 15.2.1. nh ngha Gluxit l nhng hp cht polyxyanhyt, polyxyxton hoc cc hp cht khi b thu phn chuyn ho thnh cc hp cht anhyt hoc xton ni trn. Cc hp cht gluxit m khng th b thu phn chuyn ho thnh nhng hp cht n gin hn gi l mnsacarit. Cc hp cht gluxit b thu phn to thnh 2 phn t mnsacarit c gi l isacarit. Nu hp cht khi b thu phn to thnh mt s ln mnsacarit th c gi l polysacrit. 15.2.2. Phn loi. Ngi ta phn loi cc mnsacarit nh sau: Nu phn t mnsacarit c cha mt nhm anhyt th ngi ta gi chng l anza, cn nu c cha mt nhm xton th gi l xtza. Mt khc cn c vo s nguyn t cacbon c trong phn t mnsacarit ngi ta gi chng l triza, tetrza, pentza, hecxza.V d khi ni hp cht anhecxza c ngha l hp cht mnsacarit gm 6 nguyn t cacbon c cha mt nhm anhyt, cn nu ni xtopentza tc l hp cht gm 5 nguyn t cacbon c cha mt nhm xton. Trong thin nhin thng gp cc loi mnsacarit pentza hoc hecxza. Cc gluxit kh c thuc th Felinh hoc thuc th Tolen gi l nhng ng kh ho. Tt c cc loi hp cht mnsacarit loi anza hoc xtoza u l nhng ng kh ho. Mt phn ln cc isacarit l nhng sacar kh ho tr trng hp ng thng (ng n) khng c kh nng tham gia phn ng kh gi l ng khng kh ho. 15.3. MNSACARIT : (+)-GLUC Nu ta tnh rng mnsacarit (+)-gluc l mt n v cu trc m t cu to nn tinh bt, xenlul, glicgen v vai tr quan trng c bit ca n trong sinh hc th gluc l mt mnsacarit ph bin trong t nhin v do nghin cu cc tnh cht ca n ta c th suy ra cc tnh cht ca hp cht khc. (+)-Gluc c cng thc phn t l C6H12O6 c xc nh bng phng php phn tch nguyn t v ph khi lng. Cu to ca n c th d on theo mt s tnh cht sau y:

203
xim C6H5NHNH2 Phnylhyrazon Br2, H2O (C H O )COOH HNO3 C6H12O6 (+)-Glucza (CH3CO)2O H2, Ni HCN
5 11 5

Phn ng NH2OH

C cha nhm C O CHO CH2OH v OHC 5 nhm -OH

HOOC(C4H8O4)COOH C6H7O(OCOCH3)5 (CH3CO)2O C H (OCOCH ) 6 8 3 6 HI, t C

0 0

C6H14O6

CH3(CH2)3CHICH3

C C

C C

C C

C C

C C

C CHO

H2O, HO HI, t C n-C H COOH 6 13

T kt qu trn y ta c th kt lun rng: (+)-gluc l mt pentaxianhyt khng phn nhnh cha 6 nguyn t cacbon-tc l anhecxza. 15.4. (-)-FRUCTZA (2-XTHECXZA). y l loi hp cht xtza ph bin trong cc loi thc vt c bit l trong tri cy. (-)Fructza. Kt hp vi gluc to thnh isacarit l thnh phn chnh ca ng thng. Cc chuyn ho sau y cho php kt lun rng (-)-fructza l mt xton (khng phi anhyt) v nhm cacbnyl nm nguyn t C2 tc l 2-xtohecxza.
CH2OH C O CHOH CHOH CHOH CH2OH Fructza HCN CH2OH C(OH)CN CHOH CHOH CHOH CH2OH Xianhyrin Thy phn CH2OH C(OH)COOH CHOH CHOH CHOH CH2OH Axit xicacbxylic HI, t0C CH3 CHCOOH CH2 CH2 CH2 CH3 Axit 2-mtylcapric

15.5. HO LP TH CA (+)-GLUC. Cng thc cu to ca gluc nh bit trn y c cha 4 nguyn t cacbon bt i xng. Cng thc cu to ny c th vit di dng Fish nh sau:
CHO H HO H H OH H OH OH CH2OH

Vi s lng 4 nguyn t cacbon bt i xng hp cht gluc tn ti di dng 16 ng phn quang hc (tc l 8 cp i quang). Tt c 16 ng phn quang hc ny n nay c

204

tch ra di dng cc hp cht tinh khit hoc bng con ng tng hp hoc bng con ng chit tch t thc vt. Trong s 16 ng phn ny ch c (+)-gluc, (+)-mant v (+)-galact c tm thy vi nhng lng ln. Mt khc trong 16 ng phn ni trn ch c (+)-gluc c tm thy ph bin di dng mnsacarit. 15.6. CU HNH CA (+)-GLUC. Nh ni trn cu hnh ca (+)-gluc c th l mt trong bt k 16 ng phn nu. Vy cn phi xc nh cng thc cu to no l cu hnh cu to ca (+)-gluc. Nm 1888, nh bc hc Emin Fish tin hnh nghin cu vn ny v n nm 1891 ng ta cng nhn cc kt qu thu nhn c rt tt p. Cng chnh nh kt qu ca s nghin cu ny nm 1902 Fish c trao gii thng Nben. Di y l mt s im c bn v ni dung ca vic chng minh cu hnh (+)-gluc ca Fish. Do thi by gi cha c phng php chng minh cu hnh bng cu hnh tuyt i nn Fish cho rng (+)-gluc c th l mt trong 2 ng phn ca mt cp i quang. V vy n gin hn Fish b i 8 cu hnh c th c ca (+)-gluc m ch nghin cu 8 cng thc ng phn cn li I-VIII trong nhm OH ca C5 nm bn phi.
CHO H H H H OH OH OH OH CH2OH I CHO H H HO H OH OH H OH CH2OH V HO H HO H HO H H H CHO H OH OH OH CH2OH II CHO H OH H OH CH2OH VI H HO HO H H HO H H CHO OH H OH OH CH2OH III CHO OH H H OH CH2OH VII HO HO HO H HO HO H H CHO H H OH OH CH2OH IV CHO H H H OH CH2OH VIII

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

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CHO H H H OH OH OH CH2OH IX HO H H CHO H OH OH CH2OH X H HO H CHO OH H OH CH2OH XI HO HO H CHO H H OH CH2OH XII

S chng minh ca Fish nh sau: 1. Khi xy ho (-)-arbin bng axt nitric thu c mt axt icacbxylic quang hot. Nh trn ni, v nhm OH ca nguyn t cacbon bt i xng di cng trong (-)-arbin nm pha bn phi cho nn theo kt qu ca phn ng xy ho trn y th nhm OH ca nguyn t cacbon bt i xng trn cng phi nm v pha bn tri tng t nh X hoc XII nu khng s thu c sn phm khng quang hot.
CHO HO H H HNO3 OH H OH HO COOH H

CH2OH X hoc XII CHO H H OH HNO3 OH

COOH Quang hot COOH H H OH OH

CH2OH IX hoc XI

COOH Hp cht mz(khng quang hot)

2. (-)-Arbin c th chuyn ho thnh (+)-gluc v (+)-mant bng phn ng KilianiFish. Do (+)-gluc v (+)-mant l nhng ng phn epime-tc l 2 anza thu nhn c trong kt qu ca mt phn ng tng hp ch khc nhau duy nht v cu to bi cu hnh C2. Do (+)-gluc v (+)-mant c th c cu hnh III v IV hoc VI v VIII.

206

CHO HO H H OH HCN HO H H

CN H OH OH CH2OH CHO H Na(Hg) HO H H OH H OH OH CH2OH v HO HO H H

+

COOH HO H H H OH OH CH2OH CHO H H OH OH CH2OH HO H H

C O H O OH CH2OH

H2O, H

CH2OH (-)-Arbin X hoc XII

(+)-Gluc v (+)-Mant: III v IV hoc VII v VIII

3- Khi b xy ho bi HNO3 c (+)-gluc ln (+)-mant u cho mt sn phm l axt icacbxylic quang hot. iu c ngha l nhm OH thuc nguyn t C4 nm bn phi ging III v IV. 4- xy ho mt hp cht hecxza khc (+)-gluc to thnh mt axt icacbxylic (+)sacarit tng t nh xy ho (+)-gluc.
CHO H HO H H III OH H OH OH CH2OH HNO3 H HO H H IIIa COOH OH H OH OH COOH HNO3 H HO H H CH2OH OH H OH OH CHO i quang caV (+)-Gul

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

207

CHO H HO H H OH H OH OH HO H HO HO

CHO H OH H H

CH2OH D-(+)-Gluc

CH2OH L-(+)-Gluc

15.7. CU TO DNG VNG CA D-(+)-GLUC. Cng thc cu to D-(+)-gluc c Fish chng minh trn y tuy tho mn c nhng tnh cht quan trng ca hp cht pentaxianhyt nhng trong mt s trng hp thc t sau y khng th gii thch c bng cng thc cu to . 1- D-(+)-Gluc khng tham gia mt s phn ng c trng cho hp cht anhyt. V d n khng tham gia phn ng vi thuc th Ship (lm mt mu dung dch ixyt lu hunh SO2 trong 0,025% dung dch fucxin) hoc khng tham gia phn ng vi bisunfit natri. 2- D-(+)-Gluc tn ti di 2 dng ng phn: Mt D-(+)-gluc tinh th (tnc=1460C) khi ho tan vo trong nc lc u c quay cc l [] =+1120 nhng sau gim dn xung cn +52,70. Mt D-(+)-gluc khc (tnc=1500) khi tan trong nc c quay cc t +190 tng dn ln n +52,70. ng phn c quay cc cao ngi ta gi l -D-(+)-gluc, v ng phn c quay cc thp gi l -D-(+)-gluc. 3- D-(+)-Gluc to thnh 2 ng phn mtyl-D-gluczit. Ta bit rng nu anhyt tc dng vi ancol c xc tc l axt s to thnh hp cht axtal.
CH O Anhyt CH3OH, H+ CH OCH3 OH Semiaxtal CH3OH, H+ CH OCH3 OCH3 Axtal

Th nhng khi cho D-(+)-gluc tc dng vi mtanol v HCl khng to thnh axetal. Mt khc hp cht ny khng b thu phn vi nc to thnh anhyt v ancol nh cc hp cht semiaxtal. Ngoi ra mtyl-D-gluczit c to thnh tn ti di 2 dng ng phn: mt ng phn c nhit nng chy l 1650C vi gc quay cc l +1580 v mt ng phn khc c nhit nng chy l 1070C vi gc quay cc l 330. Ngi ta gi ng phn th nht l mtyl--D-gluczit v ng phn th 2 l mtyl--D-gluczit. Tt c nhng iu c a ra trn y s c gii thch mt cch thch hp nu cng nhn D-(+)-gluc c cu dng vng.

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H C OH H C OH HO C H H C OH H C
6 5 4 3 2

6CH2OH

H
4

O H
2

H H
1 4

6CH2OH 5

H OH
3

HO HO
3

H
2

O H OH
1

OH O

OH

H H

H IIb

OH

OH

CH2OH IIa
5

( -D-(+)- Gluc) IIc O H

2

HO C H H C OH HO C H H C OH H C CH2OH IIIa O H
4

6CH2OH

H OH
1 4

6 CH2OH 5

H OH
3

HO HO
3

H
2

O OH OH
1

OH

H H

OH IIIb

( -D-(+)- Gluc) IIIc

D-(+)-Gluc c cu to dng vng nh IIa v IIIa, nu vit chnh xc hn l IIb v IIIb cn nu tht chnh xc l IIc v IIIc. D-(+)-Gluc ch c kh nng to thnh hp cht semiaxtal bi v nhm OH ca C1 tng tc vi nhm OH ca C5 to thnh cng thc vng. Tn ti 2 cng thc ng phn ca D-(+)-gluc c gy ra bi cu to vng c thm mt nguyn t cacbon bt i xng C*1. S khc nhau v cu hnh nguyn t cacbon ny dn n to thnh cc ng phn. D-(+)-Gluc ch c th tham gia mt s phn ng c trng cho anhyt nhng khng tham gia phn ng Ship c th gii thch rng do s tn ti mt lng rt nh (khong 0,5%) dng anhyt t do nh cng thc I nn khng tham gia cc phn ng cng bisunfit hoc phn ng Ship. 15.8. ISACARIT. isacarit l nhng hp cht to nn bi 2 phn t mnsacarit. Di y chng ta s xem xt mt s isacarit quan trng nh: (+)-mant (ng mch nha), (+)-xenlbi, (+)-lact (ng sa), (+)-sacar (ng ma v c ci ng). 15.8.1. (+)-Mant. ng mant c th iu ch bng cch thu phn tinh bt bi dung dch axt hoc bng phng php ln men trong ru tylic.

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Cng thc phn t ca mant l C12H22O11. ng mant tham gia cc phn ng vi thuc th Tlen, Felinh nn n l ng kh ho. Mant tc dng vi phnylhyrazin to thnh C12H20O9 v +112. Tt c cc kt qu thu nhn c trn y cho thy rng (+)-mant c cha mt nhm cacbnyl di dng biaxtal hot ng mnh nh trong cc hp cht mnsacarit. Khi b thu phn bng dung dch axt hoc bi xc tc men (+)-mant chuyn ho thnh D-(+)-gluc. Do (+)-mant dc cu to t 2 gc D-(+)-gluc v thuc vo loi hp cht gluczit. T c th suy ra (+)-mant c cu to sau y:
H HO HO H OH CH2OH H H O
1 4 6 CH2OH 5

(=NNHC6H5)2

xy

ho

bi

nc

brm

to

thnh

axt

mantbinic(C11H21O10)COOH. ng mant cng tn ti di 2 dng v vi [] =+168

H
2

O H
1

HO
3

OH

H OH H O 4-O-( - D-glucpiranzyl)-D-glucpiranza

15.8.2. Xenlbi. Xenlul c cng thc phn t l (C6H10O5)n. Di tc dng ca axt sunfuric v anhyrit axtic trong nhiu ngy s xy ra phn ng axtyl ho v thu phn to thnh ctaxtal (+)xenlul. Nu thu phn bng kim s thu c (+)-xenlbi. Xenlbi c cng thc phn t l C12H22O11 thuc loi ng kh ho tng t nh (+)mant duy ch khc nhau mt im l n b thu phn bi men emuxin ch c tc dng thu phn cc lin kt -gluczit do c th kt lun rng cc gc D-gluc trong xenlbi kt hp vi nhau bi lin kt -gluczit ch khng phi -gluczit nh trong mant.
H HO HO H H OH H CH2OH H H OH HO O H H O CH2OH OH H

H 4-O-( -D-glucpiranzyl)-D-glucpiranza

15.8.3. (+)-Lact.

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(+)-Lact c trong thnh phn ca sa khong 5%, c cng thc phn t C12H22O11 thuc loi ng kh ho. Khi b thu phn bi axt t (+)-lact thu c D-(+)-lact v D-(+)galac vi lng bng nhau. Do (+)-lact l mt hp cht gluczit c to thnh t D-(+)gluc v D-(+)-galact.
OH H HO H CH2OH H H O O OH HO H H O CH2OH OH H

OH H H H 4-O-( -D-galactpiranzyl)-D-glucpiranza

15.8.4. (+)- Sacar. (+)- Sacar l ng knh thng dng c sn xut t ng ma hay ng c ci. (+)- Sacar c cng thc phn t C12H22O11 thuc loi ng khng kh ho c ngha l n khng c nhm anhyt hoc xton t do. Khi b thu phn bi axt long hoc men invectaza t (+)- sacar thu c D-(+)-gluc v D-(-)-fruct vi lng nh nhau. Kt hp vi mt s phng php phn tch vt l khc nhau, ngi ta i n kt lun rng (+)- sacar l hp cht -D-fructzit v -D-gluczit.
H HO HO H CH2OH O H H OH

CH2OH H H HO O (+)-Sacar

O HO H

H CH2OH

15.9. POLYSACARIT. Polysacarit l nhng hp cht c to thnh t nhiu gc mnsacarit. Tng t nh cc hp cht isacarit, cc gc mnsacarit trong phn t polysacarit kt hp vi nhau bng lin kt gluczit v cc lin kt ny b phn hu trong cc phn ng thu phn. Hai hp cht quan trng nht ca polysacarit 15.9.1. Tinh bt. Tinh bt cha trong ht v trong c ca thc vt. dng ht, tinh bt khng ho tan trong nc lnh. Khi b ph hu lp v bc bn ngoi v nghin nh, tinh bt c kh nng n ra trong nc lnh v to thnh h phn tn keo. Trong nc nng phn ho tan ca tinh bt keo trong t nhin l tinh bt v xenlul. Chng c cng thc (C6H10O5)n. y l nhng hp cht c ngha rt quan trng i vi i sng con ngi.

211

t li vi nhau to thnh gen h keo. Thng th tinh bt cha khong 20% cht ho tan trong nc gi l amilpectin. C 2 phn ny u c cng thc (C6H10O5)n. Khi b thu phn bi axt hoc di tc dng ca men, tinh bt bin thnh ectrin (hn hp polysacarit c phn t lng thp), (+)-mant v cui cng to thnh D-(+)-gluc. C amilza ln amilpectin u c to thnh t gc D-(+)-gluc nhng ch khc nhau v s lng v dng phn t. a. Cu to ca amilza. Khi b thu phn amilza trc ht to thnh hp cht isacarit (+)-mant v sau to thnh mnsacarit l D-(+)-gluc. iu c ngha l amilza c to thnh t mt lng ln gc D-(+)-gluc m trong chng kt hp vi nhau bng lin kt -gluczit thuc nguyn t cacbon C1 v C4
H O HO H H OH O H Amilza CH2OH H H O H HO CH2OH H H OH O H H O H HO CH2OH H H OH O

O H

b. Cu to ca amilpectin. Amilpectin khi b thu phn cho mt sn phm duy nht isacarit l (+)-mant. Do tng t nh amilza, amilpectin c to thnh t cc gc D-gluc nhng c cu to phc tp hn. Bng cc phng php phn tch vt l hin i, ngi ta i n kt lun rng: amilpectin c cu to phn nhnh cha khong 20-25 gc D-gluc. Cc mch nhnh ny lin kt vi nhau bng nguyn t xy thuc C1 vi nguyn t cacbon C6.
H O HO H H O HO H H OH O H Amilpectin CH2OH H O H HO H OH O H H2C H OH O H O H H CH2OH H H O H HO CH2OH H H OH O

O H

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15.9.2. Xenlul. a. Cu to. Xenlul l thnh phn chnh ca g v cc si t nhin nh si bng, si gai, si ayXenlul khng tan trong nc. N l loi ng khng kh ho v c phn t lng rt ln. Khi b thu phn hon ton xenlul cho mt sn phm mnsacarit duy nht l D-(+)gluc. Do cho php kt lun rng xenlul cng tng t nh tinh bt c cu to t cc gc ca D-gluc. Bng cc phng php phn tch hin i, ngi ta kt lun rng khc vi tinh bt, cc lin kt gluczit trong xenlul l loi lin kt 1-4 .
H O HO H H OH H H CH2OH H H O O OH HO H H O CH2OH Xenlul O HO H H OH H H H CH2OH H

O O

b. Cc phn ng ca xenlul. Xenlul b thu phn bi axt v c to thnh (+)-gluc. Mt khc nu phn t xenlul cha b ph v th mi mt n v vng c cha 3 nhm OH. Chnh cc nhm ny s tham gia vo mt s phn ng. 1- Nitrat xenlul. Xenlul tng t nh cc ancol c kh nng tham gia cc phn ng este ho. Khi n tc dng vi hn hp axt nitric v sunfuric to thnh nitrat xenlul. Hp cht ny (khi c 3 nhm OH c thay th bng nhm ONO2) c s dng lm thuc sng. Hp cht pirocxilin (khi 2 nhm OH ca xenlul b thay th bi ONO2) c s dng sn xut phim nh. 2- Axtat xenlul. Di tc dng ca axetanhyt, axt axtic v axt sunfuric xenlul chuyn ho thnh trinitrat xenlul. Cc hp cht axtat xenlul c s dng lm phim nh, lm si dt vi (si axtat, si t la axtat). 3- T la nhn to v xlfan. Nu cho ancol tc dng vi iunfua cacbon v dung dch NaOH s thu c hp cht xantgenat.
RONa + S C S RO C S SNa H
+

ROH + CS2

Xenlul cng tham gia phn ng tng t nh ancol to thnh hp cht xantgenat.

213

[C6H7O2(OH)3] n + nCS2 (C6H9O4

nNaOH OCS2Na) n +

[C6H7O2(OH)3.NaOH] n nH2O

Dung dch xantgenat trong kim sau khi c dn qua b cha H2SO4 v ko thnh si s thu c t nhn to visc. Nu ho do xantgenat bng glyxrin v cn thnh cc mn mng ta c mng xlfan.

214 CU HI N TP V BI TP CHNG 15

15.1. Cho Glucz tc dng vi HIO4 s thu c nhng loi hp cht no. 15.2. Hon thnh cc s phn ng sau y:
A B C D
+ + + +

4HIO4 5HIO4 3HIO4 4HIO4

3HCOOH 4HCOOH 2HCOOH 4HCOOH

+ + + +

HCHO 2HCHO

OHC COOH

2OHC COOH OHC COOH

15.3. Vit cng thc cu to ca cc hp cht to thnh khi cho D-(+)-galactz tc dng vi: a. Hydroxylamin c. HNO3 e. CH3OH/HCl g. Phenyl hyroxylamin i. CH3OH/HCl tip theo dimetyl sunfat/NaOH j. Dung dch nc Brm tip theo CaCO3, tip theo H2O2/Fe3+ 15.4. Thc hin s chuyn ha sau:
ClCH2CHO meso-A B C D D C C C
+ + + + + + + + +

b. Dung dch nc Brm d. HIO4 f. NaBH4 h. (CH3CO)2O

BrMgC CMgBr

OHCCH2Cl

A(C6H8O2Cl2)

KOH

B(C6H6O2 - Epoxi) C(C6H10O4) D(C6H12O4) E

+

H2O/HOH2, Pd/CaCO3

KMnO4 (long, lnh) peaxit focmic Na/NH3

E'

(C hai u l C6H14O6)

F(C6H14O6) G(C6H12O4) H(C6H14O6) I

+

KMnO4 (long, lnh) peaxit focmic

I' (C hai u l C6H14O6)

15.5. Salixin (C13H18O7), c trong loi cy Salix, b thu phn bi men Emuxin to thnh Dglucz v Saligenin(C7H8O2). Salixin khng c phn ng vi thuc th Tollen, khi b oxi ha bi CH3COOH to thnh mt hp cht m khi thu phn hp cht ny thu c D-glucz v Anhyrit Salixilic. Metyl ha Salixin thu c pentametyl Salixin, khi thu phn hp cht ny to ra sn phm 2,3,4,6-tetra-O-metyl-D-glucz. Xc nh cng thc cu to ca Salixin. TI LIU THAM KHO CA BI TP CHNG 15 [1]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [2]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni.

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Chng 16 AMINAXT V PRTIT. 16.1. MT S KHI NIM M U. Tn gi prtit bt ngun t ting Latinh proteios c ngha l th nht. Tn gi nh th c ngha rt thch hp bi v trong tt c cc hp cht ha hc prtit l hp cht quan trng bc nht to thnh s sng. Prtit khng ch l thnh phn c bn cu to nn cc c quan m n cn l ngun cung cp mi nhu cu cn thit cho cc hot ng ca s sng. Di quan im ho hc, prtit l hp cht cao phn t-polyamit c to thnh t cc mnme -aminaxt. Trong thnh phn ca mt phn t prtit c th c hng trm hoc hng ngn gc aminaxt. Cho n nay ngi ta mi bit c khong trn 20 loi aminaxt khc nhau. Nhng s t hp ca cc aminaxt ny rt a dng v phong ph v l c s to nn cc c quan khc nhau ca ng vt. duy tr s sng v s pht trin, trong cc c th ca ng vt c ti hng ngn loi prtit khc nhau, mt khc i vi nhng loi ng vt nht nh c cc c trng ca n. A. AMINAXT. 16.2. CU TO CA AMINAXT. Trong bng di y l cng thc cu to v tn gi ca 26 loi aminaxt trong prtit. Mt s aminaxt c nh du * l nhng hp cht c th khng tng hp c t cc cht ly t thc n. Tt c cc aminaxt u l nhng -amincacbxylic axt. Trong 2 trng hp prlin v xyprlin nhm amin tham gia to thnh vng pirliin. Trong mt s trng hp aminaxt cn cha thm mt nhm cacbxyl th 2 (v d nh acparagic hay glutamic axt) hoc nhm cacbnyl nh acogin. Loi aminaxt ny c gi l aminaxt axt. Mt s aminaxt c cha nhm baz nh lizin, arginin, gistiin c gi l aminaxt baz. 16.3. AMINAXT TNG T NH CC ION LNG CC. Thng th cc aminaxt c biu din l nhng hp cht c cha nhm amin v nhm cacbxyl H2NCHRCOOH nhng trong thc t mt s tnh cht ho l ca n khng phn nh ph hp vi cng thc cu to ny. Bng mt s aminaxit quan trng ca prtit. Tn gi Glyxin Vit tt
Gly

Cng thc
H3NCH2COO
+ -

216

(+)-Alanin (+)-Valin (-)-Leixin (+)-Izleixin (+)-Asparagic axt (-)-Aspagin (+)-Glutamic axt (+)-Glutamin (+)-Lizin (-)-xilizin (+)-Arginin (-)-Serin (-)-Treonin (-)-Cystein (-)-Cystin (-)-Metionin

Ala Val* Leu* Ile* Asp Asp-NH2 Glu Glu-NH2 Lys* Oly Arg* Ser Tre* Cys

CH3CHCOO+ NH3

(CH3)2CHCH COO+NH3

(CH3)2CHCH2CHCOO+NH3

CH3CH2CH(CH3)CHCOO+NH3

HOOCCH2CHCOO+ NH3

H2NCOCH2CHCOO+ NH3

HOOCCH2CH2CHCOO+NH3

H2NCOCH2CH2CHCOO+NH3

H2NCH2CH2CH2CH2CHCOO+ NH3

H2NCH2CHCH2CH2CHCOOOH
+ NH3

H2NCNHCH2CH2CH2CHCOO+NH2

NH2

HOCH2CHCOO+ NH3

CH3CH CHCOOOH +NH3 HOCH2CHCOO+NH3

OOCCHCH2
+NH3

CH2CHCOO+ NH3
-

Met

CH3SCH2CH2CHCOO
+ NH3

217

(-)-Phenylalanin

Phe*
+NH3

CH2CHCOO

(-)-Tyrozin

Tyr
HO
+NH3

CH2CHCOO

(+)-3,5-ibrmtyrzin
HO

Br CH2CHCOO+NH3

Br

(+)-3,5-iityrzin
HO

I CH2CHCOO+NH3

(-)-Tryptophan

Try*

CH2CHCOO
+NH3

N H

(-)-Prolin

Pro
H N
+

COO H

(-)-xiprolin

Opr

HO H N
+

COOH

(-)-Histoin

His

N N H CH2CHCOO+NH3

(+)-Tyroxin
HO I

I O

I CH2CHCOO
+NH3 -

1- Khc vi amin v axt cacbxylic cc aminaxt l nhng hp cht tn ti di nhng tinh th khng bay hi v nng chy nhit rt cao cng vi s phn hu. 2- Cc aminaxt khng tan trong cc dung mi khng phn cc nh ete, ete du ho, benzen nhng li tan tt trong nc. 3- Dung dch nc ca aminaxt c mmen lng cc rt cao. 4- Cc hng s axt v baz ca cc nhm COOH v NH2 ca aminaxt rt nh so vi cc axt cacbxylic v amin tng ng.

218

Tt c cc tnh cht khc bit trn y ca aminaxt s c gii thch tho mn khi biu din cng thc cu to ca cc aminaxt l nhng ion lng cc.
H3N CHR (I)
+

COO-

Theo cu to (I), cc tnh cht vt l nh nhit nng chy, ho tan, mmen lng cc nh nu cc im 1, 2, 3 trn y s rt ph hp vi mt mui nh vy. Cc hng s axt v baz cng d dng gii thch v rng trn thc t Ka c xc nh bi ion amni RNH3 v Kb c xc nh bi ion cacbxylat RCOO-.
H3NCHRCOO- + Axit Ka = H3NCHRCOO- + Baz Kb =
+ +

H2O
+

H3O+ + H2NCHRCOO-

[H3O+][H2NCHRCOO-] [H3NCHRCOO-] H2O

+

HO- +
-

H3NCHRCOOH

[H3NCHRCOOH][HO ] [H3NCHRCOO ]
+ -

Trong thc t tu thuc vo mi trng m cc aminaxt tn ti chng c th chuyn ho theo s sau:

H2NCHRCOOII H+ HO H3N CHR I
+

COO-

H+ HO

H3NCHRCOOH III

Qua s chuyn ho ny, ta thy cc ion II v III c cha nhm NH2 v COOH. Chnh s tn ti ca cc nhm ny cho php cc aminaxt tham gia mt s phn ng cho cc hp cht amin v axt cacbxylic. 16.4. IM NG IN CA AMINAXT. Nu ta cho dung dch aminaxt vo trong mt in trng th ph thuc vo dung dch c tnh axt hay baz ta s quan st thy cc hin tng khc nhau. Theo s chuyn ho trn y trong dung dch kim mnh nng ca anion II s ln hn nng ca cation III v do aminaxt s chuyn dch v pha ant. Tri li trong dung dch axt mnh, nng ca cation III ln hn anion II v do aminaxt s chuyn dch v pha catt. Nu nh nng ca II v III bng nhau th lc ta s khng quan st thy mt s chuyn dch no ca aminaxt. Bt k mt phn t aminaxt no trong iu kin ny cng u tn ti di dng va l cation v do mi mt s chuyn dch in t no ca mt phn t aminaxt v mt pha in cc s c b li ngay lp tc bi s chuyn ng ngc li. Nng ion hyr m ti mt phn t

219

aminaxt nht nh khng b dch chuyn bi tc dng ca in trng c gi l im ng in ca aminaxt . 16.5. CU HNH CA AMINAXT THIN NHIN. Nh ta bit cc aminaxt u c cha t nht mt nguyn t cacbon bt i xng (tr glyxin). Qu trnh nghin cu ho lp th ca cc aminaxt thin nhin ch ra rng chng c cng mt loi cu hnh v cu hnh ging nh cu hnh L-(-)-glyxeranehyt.
CHO HO H CH2OH L-(-)-Glyxranhyt H2N R L-Aminaxit COO
-

16.6. TNG HP CC AMINAXT. Phng php quan trng nht tng hp cc aminaxt l amin ho cc -halogenaxt sau y: 1- Phn ng amin ho trc tip -clo v -brmcacbxylic axt. V d:
CH3CH2COOH Br2, P CH3 CH COOH Br CH2(COOC2H5)2 KOH, t C HCl tC
0 0

NH3

CH3CHCOO
+NH3 Alanin C6H5CH2Cl

C2H5ONa

Na CH(COOC2H5)2 Br2, te

+-

C6H5CH2

C(COOC2H5)2 H

C6H5CH2CH(COOH)2 NH3

C6H5CH2C(COOH)2
-

Br

C6H5CH2CHCOOH Br

C6H5CH2CHCOO

+NH3 Phnylalanin

2- Tng hp Gabrien.
O N-K+ + ClCH2COOC2H5 tylcloaxtat O Phtalimit kali
HCl, H2O
+

O NCH2COOC2H5 O
COOH Cl- + H3NCH2COOH + COOH

220

16.7. CC PHN NG CA AMINAXT. Phn ng ca aminaxt nhn chung l nhng phn ng ca cc hp cht cha nhm amin v nhm cacbnyl. B. PEPTIT. 16.8. NH NGHA, PHN LOI V CU TO. Peptit l nhng hp cht amit c to thnh do kt qu phn ng ca nhm amin v nhm cacbnyl ca cc aminaxt vi nhau. Nhm amit NHCO- trong cc hp cht ny thng c gi l lin kt peptit. Cc hp cht peptit c phn loi thnh mnpeptit, ipeptit, tripeptitcho n polypeptit ph thuc vo s lng nh hn 10.000 th gi l polypeptit, cn nu ln hn 10.000 th gi l prtit. Khi vit cc cng thc ca cc peptit thun tin ngi ta thng dng cc k hiu vit tt ca cc aminaxt trong nhm amin c quy nh vit pha bn tri v nhm cacbxyl t do bn phi. V d:
H N H
+

O C R N H

H R C O
+

H N H R

O C

H3NCH2CONHCH2COOGlyxylglyxin Gly-Gly (ipeptit)

+

H3NCH2CONHCHCONHCHCOOCH2C6H5 Glyxylalanylphnylalanin Gly-Ala-Phe (tripeptit)

H3NCHCO(NHCHCO) nNHCHCOOR R Polypeptit R

Cc phng php phn tch ho l v rengen cho thy rng tt c cc nhm amt u nm trong mt mt phng-tc l nhm cacbnyl nguyn t nit v cc lin kt ca cc nhm ny nm trong mt mt phng. 16.9. CC PHNG PHP XC NH CU TO CA PEPTIT. xc nh cu to ca mt hp cht peptit cho cn phi: 1- Xc nh nhng aminaxt no c trong thnh phn phn t ca peptit. 2- C bao nhiu loi aminaxt v s lng mi loi l bao nhiu trong phn t ca peptit. 3- Cch thc to lin kt ca cc aminaxt trong phn t peptit.

221

Hp cht peptit trc ht c thu phn bng axt (khng thu phn bng baz v sn phm to thnh s b raxemic ho) v sau xc nh khi lng ca mi loi aminaxt to thnh sau phn ng. Phng php tt nht hin nay thng c dng tch cc aminaxt l sc k. Xc nh c s lng ca mi loi axt ta c th tnh c s mol ca chng v t suy ra t l ca cc aminaxt c trong phn t peptit-tc l xc nh c cng thc phn t tng qut. Sau xc nh phn t lng ca phn t peptit bng phng php vt l nh o p sut thm thu, nhiu x rengenv suy ra cng thc phn t ca peptit. xc nh cch thc to lin kt ca cc aminaxt trong phn t peptit, ngi ta s dng kt hp 2 phng php: xc nh nhm cui mch v thu phn tng phn. C nhiu phng php xc nh nhm cui mch ca peptit. V d phng php ca Sendrer s dng thnh cng bng cch dng hp cht 2,4-initrbenzen nh sau:

O2N

F + H2NCHCONHCHCO R NO2 Peptit NHCHCOOH R + R'

O2N

NHCHCONHCHCO R R' NO2 Peptit c nh du

HCl, t0C

O2N

H3NCHCOOR'

NO2 N-(2,4-initrphnyl)-aminaxit Aminaxit khng nh du

Sau khi tch c N-(2,4-initrphenyl)-aminaxt, tip tc tch ring cc aminaxt v qua nhn xt, kt lun v s to lin kt ca chng vi nhau. 16.10. TNG HP CC PEPTIT. Phng php polyme ho cc aminaxt to thnh polypeptit vi phn t lng cao c ngha trong cng nghip v i sng. Nhng iu ch cc peptit c cu trc tng t nh peptit t nhin th phng php ny khng thch hp. Do ngi ta tin hnh iu ch cc peptit bng mt s phng php khc. Vn c tnh cht quyt nh c t ra l phi bo v cc nhm amin trong qu trnh tng hp. Phi lm sao cho s kt hp ca nhm cacbxyl ca phn t aminaxt ny vi nhm amin ca phn t aminaxt kia khng xy ra s phn ng gia cc nhm cacbxyl v amin ca cng mt phn t aminaxt. V d phi lm sao cho khi iu ch glyxylalanin th khng xy ra phn ng to thnh glyxylglynin. iu c th iu chnh c nu a thm vo nhm amin mt nhm chc khc c tc dng lm cho kh nng phn ng ca nhm amin gim i. V d:

222

H3NCHCOO R

Q NHCHCOOH R
+

Q NHCHCOCl R Q NHCH C NHCHCOOH R

+

Bo v nhm amin To lin kt peptit Tch nhm bo v Q

Q NHCHCOCl + H3NCHCOOR R'

R'
-

Q NHCH C NHCHCOOH R O R'

H3NCH C NHCHCOO R O R'

Trong phn ng trn y, ngi ta bo v nhm amin ca glyxin bng Q-C6H5- sau chuyn nhm glyxin thnh cloranhyrit ri cho phn ng vi alanin. Cc phn ng iu ch c th vit li di dng y nh sau:
CO + Cl2 than hot tnh 200 0 C
+

Cl
-

C O

Cl

C6H5CH2OH

C6H5CH2O C Cl O SOCl2

C6H5CH2OCOCl + H3NCH2COO
+

C6H5CH2OCONHCH2COOH
-

C6H5CH2OCONHCH2COCl H2,Ni
+

H3NCH(CH3)COO

C6H5CH2OCONHCH2CONHCHCOOH CH3 CO2

H3NCH2CONHCHCOO- + C6H5CH3 + CH3 Gly-Ala

C. PRTIT. 16.11. PHN LOI V S BIN TNH CA PRTIT. 16.11.1. Phn loi. Prtit c phn thnh 2 loi chnh: prtit dng si v prtit dng cu. Prtit dng si khng tan trong nc, c th ko thnh si. N l c bn to nn cc c ng vt. Cc prtit ca loi ny v d nh keramin c trong da, tc, xngmizin c trong cc bp c Prtit dng cu tan trong nc, trong dung dch axt long, baz long hoc cc mui. Cc prtit ca loi ny ng vai tr iu khin cc hot ng ca s sng nh cc loi men, cc loi hocmon. V d inxulin c trong d dy, anbumin ca trng, hmglbin ca mu 16.11.2. S bin tnh. S kt ta khng thun nghch ca prtit gi l s bin tnh. Hin tng ny thng xy ra di tc dng ca nhit , axt, baz hoc mt s tc nhn khc. V d s kt ta ca trng l biu hin s bin tnh ca anbumin. S bin tnh ca prtit lm bin i hon ton cc tnh cht ca prtit v lm mt hn tnh cht sinh hc ca n.

223

16.11.3. Cu to ca prtit. Thng ngi ta xem xt cu to ca cc prtit bng cch phn thnh 2 loi. Loi th nht l cu to m trong cc nguyn t kt hp vi nhau bng lin kt cng ho tr to thnh cc cu trc khng gian dng vng, dng l hoc dng cu. 1- Loi cu to th nht. Trong cu to loi ny cc prtit c to thnh t nhng mch peptit-tc l cc gc aminaxt. Khc vi cc peptit, chng c phn t lng ln hn (trn 10.000) v cu to phc tp hn.
H H ... N C R O H H C N C R' O H H C N C R' O H H C N C R O H H C N C C ... R' O

2- Loi cu to th 2. Cc phng php phn tch vt l hin i cho thy rng trong cu to thuc loi ny cc prtit thng c lin kt vi nhau bi cc cu ni hyr v c to nn bng cc n v cu trc lp li ging nhau. Tu thuc vo cu trc ca mch v cu lin kt hyr m cc prtit c dng khng gian khc nhau. Di y l mt s v d v cu trc ca prtit.
H N H R O C N H H R C H N R O C

O H Dng phng ziczc

H N H R C O H N

H N H R

O C

O C H R

Dng un cong

H R C O H N H R N H O C

O C H R

H N C O H C O N

R N H O C

H R N H

Mt phng dng vng

224

Dng l

Dng xon

225 CU HI N TP V BI TP CHNG 16

16.1. a. Khi nim v aminoaxit. b. Phn loi aminoaxit. Gii thch aminoaxit thay th v khng thay th. 16.2. Trong dung dch axit mnh, aminoaxit c hai nhm axit: NH3+ v COOH a. Nhm no c tnh axit cao hn. b. Nhm no u tin cho proton khi thm kim vo dung dch. Hp cht no to thnh. 16.3. Trong dung dch kim mnh, aminoaxit tn ti dng NH2- v COO-. a. Nhm no c tnh baz mnh hn. b. Khi thm axit, nhm no u tin proton ha. Hp cht no to thnh. 16.4. Hp cht A c cng thc phn t C3H7O2N phn ng vi HNO2 gii phng N2, phn ng vi etanol/HCl cho hp cht C5H11O2N. Khi un nng A cho B c cng thc phn t C6H10O2N2. Xc nh cng thc cu to ca A, vit cc phng trnh phn ng xy ra v gi tn B. 16.5. Vit cng thc cu to ca cc aminoaxit c cng thc phn t C4H9NO2. Gi tn v ch r ng phn quang hc. 16.6. Vit phng trnh phn ng tng hp: a. Leuxin t ru isobutylic b. Lysin t 1,4-dibrombutan c. Prolin t axit adipic 16.7. Hp cht A c cng thc phn t C5H11NO2, tan c trong c axit v kim, tc dng vi etanol to thnh cht C7H15NO2. Khi un nng A s gii phng NH3 v chuyn thnh cht B m khi oxi ha s to thnh axeton v axit oxalic. Xc nh cng thc cu to ca A. 16.8. Hai cht ng phn A v B c cng thc phn t C9H11NO2, u tan trong axit v kim. Khi cho A v B tc dng HNO2 cho hai hp cht A v B c cng thc phn t C9H10O3, khi un nng A v B vi axit sunfuric c to thnh C c cng thc phn t C9H8O2 ri oxi ha tip cho axit terephtalic v CO2. Xc nh cng thc cu to ca A v B. TI LIU THAM KHO CA BI TP CHNG 16 [1]. Ng th Thun, Bi tp ha hc hu c (2008), Nxb. Khoa hc v K thut, H Ni. [2]. Thi Don Tnh, Bi tp c s ha hc hu c (2005), Nxb. Khoa hc v K thut, H Ni.