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TT LUYN THI & BI DNG KIN THC NGY MI

18A/88 INH VN T - TP. HI DNG

MC LC
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Phn I. M U ................................................................................................................. 2 I. t vn ....................................................................................................................... 2 II. i tng nghin cu ....................................................................................................2 III. Mc tiu nghin cu .....................................................................................................2 IV. Phng php nghin cu .............................................................................................. 2 Phn II. NI DUNG ............................................................................................................ 3 I. Tng quan l thuyt .......................................................................................................3 1. Hp cht c nguyn t.................................................................................................3 2. Phn ng th nucleophin (SN) ...................................................................................... 5 3. Phn ng cng nucleophin vo nhm cacbonyl (>C=O) .............................................. 6 4. Bo v nhm chc trong tng hp hu c ...................................................................7 II. Tng hp mt s hp cht hu c c nhm chc qua con ng hp cht c nguyn t ........................................................................................................................................ 8 1. Tng hp hirocacbon .................................................................................................8 2. Tng hp cc ancol qua hp cht c nguyn t ......................................................... 10 3. Tng hp cc hp cht cacbonyl qua con ng hp cht c nguyn t .................... 11 III. Phng php gii bi tp tng hp hu c nhiu giai on .................................... 12 1. Phng php gii chung ............................................................................................ 12 2. Bi tp vn dng........................................................................................................ 12 Phn III. KT LUN ........................................................................................................ 30 TI LIU THAM KHO ................................................................................................. 30

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TI LIU LUYN THI & BI DNG KIN THC NM 2011

Phn I. M U
I. t vn
Mc d ra i mun hn cc chuyn ngnh ha hc khc nhng sau hn hai th k ra i ha hc hu c c nhng bc pht trin nhanh chng v ng gp to ln vo tt c cc lnh vc ca i sng sn xut. Ngnh ha hu c khi mi ra i mang ngha l ngnh ha hc nghin cu v nhng hp cht c trong c th sng. Hin nay n mang ngha rng hn l ngnh ha hc nghin cu v cc hp cht ca cacbon (tr CO2, CO, mui cacbonat, xianua, cacbua). Tng hp hu c l mt b phn quan trng ca ha hc hu c, bn thn n c lch s pht trin kh lu di. y l mt lnh vc rng ln v hp dn, li cun c kh nhiu nh khoa hc trn th gii quan tm v nghin cu. Cng vi s pht trin khng ngng ca khoa hc k thut cng nh cc lnh vc khc ca ha hc, ngy cng c nhiu hn cc phng php mi tng hp cc hp cht hu c. Tng hp hu c c th xem l mt nhim v quan trng ca ha hc hu c, n khng nhng to ra nhng hp cht quan trng cho i sng v sn xut, m cn trang b cho ngi hc nhng kin thc l thuyt c bn v phn ng hu c. Mun tng hp thnh cng mt hp cht hu c, cn nm vng tnh cht ha hc ca cc hp cht khc nhau, s chuyn ha gia cc nhm chc ng thi vn dng linh hot vo tng trng hp c th c th t hiu sut cao nht. Hp cht c nguyn t l nhng tc nhn c tnh cht ha hc a dng v kh nng phn ng cao. Xut pht t cc hp cht c nguyn t, ngi ta c th tng hp v iu ch c nhiu hp cht khc nhau. C th ni y l con ng tng hp hu c cho hiu sut ti u nht. Vi nhng l do ti chn ti: ng dng hp cht c nguyn t trong tng hp hu c. Tuy nhin trong gii hn ca mt nin lun ti ny ch trnh by ng dng c bn trong tng hp v iu ch ca mt s hp cht c nguyn t in hnh: C magie, c liti v c photpho.

II. i tng nghin cu


- Tnh cht ha hc ca cc hp cht c nguyn t v ng dng trong tng hp v iu ch hu c. - Phng php gii cc bi tp v tng hp v iu ch hu c. - H thng cu hi v bi tp v tng hp v iu ch hu c.

III. Mc tiu nghin cu


- Gp phn rn luyn kh nng gii cc bi tp tng hp v iu ch hu c bng nhiu con ng khc nhau t bi dng thc yu thch mn hc.

IV. Phng php nghin cu


- Nghin cu c s l thuyt ca ti. - Nghin cu cc ti liu khoa hc c lin quan n ti.
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TT LUYN THI & BI DNG KIN THC NGY MI

18A/88 INH VN T - TP. HI DNG

Phn II. NI DUNG


I. Tng quan l thuyt
1. Hp cht c nguyn t 1.1 Khi nim v phn loi - Hp cht c nguyn t l nhng hp cht m trong phn t c cha lin kt C-E trong E khng phi l cc nguyn t organogen (C, H, O, N, S, Halogen...) - Ty thuc vo bn cht ca nguyn t E trong lin kt C-E m ngi ta phn ra hp cht c kim v hp cht c phi kim. Tuy nhin s phn chia ny khng c mt ranh gii r rt. 1.2 c im cu to v tnh cht chung 1.2.1 Hp cht c kim - Cc hp cht c kim c th c 2 dng cu to khc nhau: R-Me (1) v R-Me-Hal (2) Trong Me l cc nguyn t kim loi, Hal- l cc halogen (Cl, Br, I). Ty thuc vo bn cht ca kim loi, halogen, R- m hp cht c kim c nhng loi lin kt khc nhau: Lin kt C-Me c th l lin kt ion mc no (Me: K, Na, Li, Ca, Mg...) Lin kt C-Me c th l lin kt cng ha tr (Me: Pb, Hg...) - Do bn cht lin kt C-Me trong cc hp cht c kim l khc nhau do cc hp cht c kim c nhng tnh cht vt l v ha hc khc nhau. V mt ha hc cc hp cht c kim th hin 2 tnh cht chnh: Tnh cht baz: Cc hp cht c kim d dng tc dng vi cc hp cht c H linh ng nh: HOH, ROH, HX... Tnh nucleophin: Cc hp cht c kim ng vai tr l mt tc nhn nucleophin mnh. Cc tnh cht ny c s th hin c th tng tc nhn khc nhau. 1.2.2 Hp cht c phi kim - L nhng hp cht hu c m phn t c lin kt C-E (E l cc phi kim P, S, Si...) trong quan trng hp c l hp cht c - photpho v c - silic. 1.3 Mt s hp cht c nguyn t tiu biu 1.3.1 Hp cht c magie - Cc hp cht c magie c cu to kh phc tp, song n gin ngi ta dng cng thc RMgX (R l gc hidrocacbon, X l halogen). - Hp cht c magie c tng hp u tin bi Barbier vo nm 1899. Nm 1900 hc tr ca Barbier l Grignard a ra quy trnh tng hp hp cht c - magie i t dn xut halogen trong mi trng ete khan cho hiu sut cao (Thuc th Grignard). RX + Mg ete RMgX
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TI LIU LUYN THI & BI DNG KIN THC NM 2011

R- c th l gc ankyl bc 1, bc 2 hay gc ankyl bc 3. N cng c th l gc xycloankyl, ankenyl, aryl. ietyl ete khan l dung mi thng s dng trong phn ng iu ch hp cht c magie theo phng php trn, tuy nhin trong trng hp vinyl- v arylclorua th dung mi s dng l THF (tetrahirofuran). - Nh c kh nng phn ng cao v tnh cht ha hc a dng cho nn cc hp cht c-magie c ng dng rng ri trong tng hp v iu ch hu c. - Hai phn ng c bn ca hp cht c-magie l: Phn ng th MgX bi H linh ng v phn ng cng RMgX vo lin kt >C=O trong hp cht cacbonyl. Nhc im c bn ca thuc th Grignard chnh l tnh baz mnh ca n do trong cc phn ng ha hc n d b thy phn bi cc axit yu (HOH, ROH, RNH2) 1.3.2 Hp cht c liti - Hp cht c liti (RLi) c iu ch t dn xut halogen v liti kim loi trong dung mi ete khan hoc hexan. RX + 2Li hexan RLi + LiX - Cc hp cht c liti tham gia cc phn ng tng t hp cht c magie nhng kh nng phn ng cao hn. 1.3.3 Hp cht c ng (Liti iankylcuprat) - Liti iankylcuprat c iu ch t hp cht c liti v mui Cu (I) halogenua: 2RLi + CuX R2CuLi + LiX (X l Cl, Br, I) - R2CuLi (tng i d tan trong nc) l hp cht quan trng trong qu trnh tng hp, iu ch cc hirocacbon bt i xng (Phng php Corey-House). 1.3.4 Hp cht c photpho - Hp cht c photpho l loi hp cht c phi kim c nghin cu nhiu nht v c nhiu ng dng rng ri nht. Ngi ta phn chia hp cht c photpho thnh 2 loi ln: Loi c lin kt C-P v loi c lin kt gin tip P v C qua mt nguyn t khc. Thc t th c hai loi ny u c nhiu ng dng trong thc t. 1.3.5 Mt s hp cht c nguyn t khc. Ngoi nhng hp cht c nguyn t nu trn cn rt nhiu nhng hp cht c nguyn t khc: - Hp cht c Na, K: V c tnh cht v cu to ging vi hp cht c Liti - Hp cht c km: C th c 2 dng RZnR hay RZnX v c iu ch t dn xut halogen v km: R-I + Zn RZnI 2RZnI
Chng khan

RZnR + ZnI2

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TT LUYN THI & BI DNG KIN THC NGY MI

18A/88 INH VN T - TP. HI DNG

V tnh cht ha hc, hp cht c km tng t hp cht c magie nhng kh nng phn ng km hn nhiu ng thi vic iu ch n gp kh nhiu kh khn do n t c s dng trong tng hp hu c hn cc hp cht c-magie. - Hp cht c thy ngn: Nhiu hp cht c thy ngn c iu ch v s dng trong thc t vi hot tnh sinh hc cao. Tuy nhin hp cht c thy ngn rt c. 2. Phn ng th nucleophin (SN) 2.1 C ch SN1 - Qua 2 giai on: Giai on chm: To cacbocation R+ Giai on nhanh: Cacbocation kt hp vi mt tc nhn nucleophin trong hn hp phn ng to ra sn phm. - Ha lp th: Do cu to ca gc cacbocation phng nn a s cc trng hp nu xut pht t hp cht quang hot s thu c mt bin th raxemic. Tuy nhin nu cacbocation sinh ra khng hon ton t do th sn phm sinh ra l bin th raxemic v quay cu hnh mt phn. 2.2 C ch SN2 - L c ch 1 giai on i qua trng thi chuyn tip Y- + R-X [ Y...R...X] Y-R + X- Ha lp th: V phng din khng gian trong phn ng SN2 tc nhn Y- tn cng vo nguyn t C trung tm t pha i din ca X do nu i t dn xut quang hot th sn phm thu c c cu hnh ngc vi dn xut ban u (S quay cu hnh). 2.3 Cc yu t nh hng 2.3.1 nh hng ca gc hidrocacbon (R-) - Cu to ca gc R- c nh hng n phn ng th nucleophin: + Cc gc ankyl c bc cng cao th kh nng phn ng SN1 tng, phn ng SN2 gim. + Cc dn xut anlyl v benzyl thun li cho c c ch SN2 v SN1 + Cc dn xut phenyl v vinyl thng tham gia phn ng th nucleophin kh khn. 2.3.2 nh hng ca nhm b thay th - Kh nng phn ng ca cc dn xut R-X trong phn ng SN1 v SN2 khng ch ph thuc vo cu to ca gc R- m cn ph thuc vo bn cht ca nhm b thay th XV d: I- > Br- > Cl- >> F2.3.3 nh hng ca tc nhn nucleophin - Phn ng xy ra theo c ch SN1 th tc phn ng hu nh khng ph thuc vo nng v bn cht ca tc nhn nucleophin cn theo c ch SN2 th tc phn ng li ph thuc vo nng v lc nucleophin ca tc nhn.
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TI LIU LUYN THI & BI DNG KIN THC NM 2011

2.3.4 nh hng ca dung mi - S nh hng ca dung mi n phn ng th nucleophin l kh phc tp, khi chuyn t dung mi ny qua dung mi khc tc phn ng s thay i v c khi lm thay i c c ch ca phn ng. Tuy nhin trong cc trng hp l tng ngi ta b qua s tng tc ca dung mi. 3. Phn ng cng nucleophin vo nhm cacbonyl (>C=O) 3.1 C ch AN(CO) Phn ng tng qut:

Trong X-Y c th l: HOH, ROH, HCN, HSO3Na, R-MgX... Phn ng din ra qua 2 giai on: - Giai on 1: Y- +

- Giai on 2: 3.2 Ha lp th.

+ X+

- V mt ha lp th, phn ng cng nucleophin vo nhm cacbonyl (trong anehit, xeton) khng c tnh c th v nguyn t C trong nhm cacbonyl dng phng. Nu phn ng cng vo nhm cacbonyl dn ti sn phm c cacbon bt i th phi l bin th raxemic. - Nu nhm >C=O lin kt vi mt nguyn t C bt i th phn ng s u tin to thnh mt ng phn quang hc khng i quang (ng phn ia) theo quy tc Cram Ni dung: Nu mt phn t m trong nhm cacbonyl lin kt trc tip vi mt nguyn t cacbon bt i c ba nhm th vi kch thc khc nhau (Ln L, Trung bnh Tb, Nh N) th trong phn ng cng nucleophin tc nhn Y- s u tin tn cng t pha t b n ng khng gian hn.

R L

Hng chnh

T b N O
- Tuy nhin quy tc Cram khng phi hon ton nghim ng, t l sn phm theo quy tc Cram v ngc quy tc Cram ph thuc vo kch thc khng gian ca cc nhm th trong hp cht cacbonyl cng nh kch thc ca tc nhn nucleophin. xc nh sn phm chnh ca phn ng
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cng nucleophin vo nhm cacbonyl ngi ta s dng m hnh Felkin-Anh. y l m hnh da trn tnh ton l thuyt v ph hp rng ri vi cc kt qu thc nghim. 3.3 Cc yu t nh hng 3.3.1 Hiu ng electron - Trong phn ng cng nucleophin nu in tch trn nguyn t C trung tm cng ln th tc nhn nucleophin cng d tn cng, phn ng cng d xy ra. Nh vy cc nhm th y electron (c hiu ng +I, +C) ni vi nguyn t cacbon-cacbonyl s lm gim in tch dng v kh nng phn ng gim i. Tri li cc nhm th ht electron (c hiu ng -I, -C) c tc dng ngc li ngha l lm tng in tch dng trn nguyn t cacbon-cacbonyl do kh nng phn ng tng ln. V d: CCl3-CHO > HCHO > CH3-CHO > (CH3)2CO 3.3.2 Hiu ng khng gian - Tc nhn nucleophin trong phn ng cng vo nhm cacbonyl thng c kch thc kh cng knh do s c s nh hng ca hiu ng khng gian loi I ti kh nng phn ng. Nu cc nhm th lin kt trc tip vi nguyn t cacbon-cacbonyl c kch thc cng cng knh th s lm cho tc nhn nucleophin kh tn cng vo nguyn t cacbon trung tm hn, mt khc trng thi chuyn tip to thnh km bn do kh nng phn ng gim. 4. Bo v nhm chc trong tng hp hu c 4.1 Khi nim bo v nhm chc trong tng hp hu c - Trong qu trnh tng hp hu c thng xy ra s cn thit phi chuyn ha cc nhm chc ny m khng tc ng ti nhm chc khc trong phn t ngha l cn phi bo v nhm chc ny trong qu trnh chuyn ha nhm chc kia. lm c iu ny ngi ta c th thc hin theo hai cch c bn: Th nht l s dng cc tc nhn chn lc v iu kin phn ng nghim ngt. V d: Dng cht kh l LiAlH4 thay cho H2/Ni kh nhm cacbonyl m khng tc ng ti cc lin kt bi... Cch th hai l tm thi chuyn ha nhm chc cn bo v thnh mt nhm chc khc m n s khng bin i trong sut qu trnh chuyn ha nhm chc cn thit. Cch th hai m ta ang cp ti y chnh l phng php bo v nhm chc trong tng hp hu c, nhm chc c tm thi thay i c gi l nhm bo v. - Nh vy yu cu c bn i vi nhm chc bo v l: + Phi d dng chuyn ha thnh cc nhm chc khc, m nhm chc mi ny c n nh v khng tham gia vo qu trnh phn ng chuyn ha nhm chc cn chuyn ha. + Sau phn ng chuyn ha nhm chc cn thit, nhm bo v li d dng c chuyn li nhm chc c trong iu kin ht sc nh nhng.
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4.2 Bo v nhm ancol - Chuyn ha qua nhm chc ete: Cc ete ni chung bn vng vi hu ht cc tc nhn oxi ha trong mi trng trung tnh v kim. ti to ancol ngi ta thy phn cc ete trong mi trng axit. - Chuyn ha qua nhm este: Cc este tng i bn trong mi trng axit, do n c ng dng trong vic bo v nhm hyroxyl trong qu trnh nitro ha, oxi ha... - Bo v iol: Cc iol c bo v mt cch thun tin v ng thi bng cch chuyn ha thnh axetal hay xetal. ti to ngi ta thy phn cc xetal, axetal trong mi trng axit. 4.3 Bo v nhm chc axit cacboxylic - bo v nhm chc axit ngi ta thng chuyn ha chng thnh nhm chc este khi cho tc dng vi ancol. Ancol thng s dng l metanol v etanol, tuy nhin trong iu kin mi trng axit mnh hay kim th vi cc metyl-, etyleste ny s loi tch chng sau phn ng thng khng c li, khc phc ngi ta s dng ancol tert-butylic v cc tert-butyleste d dng loi b sau phn ng khi tc dng vi cc axit yu. 4.4 Bo v nhm amino - bo v nhm chc amino ngi ta thng chuyn ha nhm amino thnh nhm chc amit Nth bng phn ng axyl ha gia nhm chc amino vi dn xut ca axit cacboxylic. Cc amit Nth d b thy phn nh xc tc OH- hoc H+ v ti to li nhm amino. 4.5 Bo v nhm chc cacbonyl - Bo v nhm chc cacbonyl tt nht l chuyn ha chng thnh axetal hay xetal nh iol m tc nhn thng s dng hn l etylen glicol v cc axetal hay xetal vng bn trong mi trng trung tnh v kim.

II. Tng hp hp cht hu c c nhm chc qua con ng hp cht c nguyn t


1. Tng hp hirocacbon 1.1 Tng hp hirocacbon gia nguyn mch cacbon (phng php Grignard) - iu ch cc hirocacbon t dn xut halogen tng ng vi s cacbon khng i ngi ta s dng phng php Grignard theo s sau: R-X Mg / R-MgX HOH RH + Mg(OH)X ete Phng php ny da trn c s tnh cht baz mnh ca thuc th Grignard. 1.2 Tng hp cc hirocacbon tng mch cacbon 1.2.1 Phng php Wurtz (Vuyc) Trong iu ch hirocacbon, thc hin iu ch cc hirocacbon c mch cacbon di hn i t cc dn xut halogen c s cacbon t hn ngi ta c th s dng phn ng Wurtz.
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2RX + 2Na R-R + 2NaX C th xem thc ra phn ng ban u to thnh hp cht c-natri (R-Na), l mt tc nhn nucleophin mnh n s phn ng vi dn xut halogen to ra hirocacbon. R-X + 2Na R-Na+ + NaX R-Na+ + R-X R-R + NaX Trong trng hp nu dng hn hp 2 dn xut halogen (RX, RX) ta s thu c hn hp gm 3
..

hirocacbon (R-R, R-R, R-R). Nh vy nhc im ca phn ng W u rtz l ch iu ch cho hiu sut cao i vi cc hirocacbon i xng, ngc li i vi cc hirocacbon bt i xng (bt i phn t, R-R trong R # R) thng cho hiu sut thp. 1.2.2 Phng php Corey-Huose
..

Nh ni vic iu ch cc hirocacbon bt i xng bng phn ng W u rtz cho hiu sut khng cao v vy mt trong nhng phng php gip iu ch hirocacbon bt i xng vi hiu sut cao l phn ng Corey-Huose.
X 2R-X 2 Li / 2R-Li CuX R2CuLi R R-R Hexan
'

- Hp cht c ng (Liti iankylcuprat) c cha nguyn t C nucleophin, do giai on cui c th thy l phn ng th nucleophin trong R2Cu- ng vai tr l tc nhn nucleophin. Trong phng php trn, RX thng l cc dn xut halogen bc 1, cn R- trong Liti iankylcuprat c th l gc ankyl hoc aryl. Cc dn xut halogen (R-X) bc 1 cho hiu sut cao cn cc dn xut bc 2, bc 3 cho hiu sut thp mt cch r rt. V d: R-X + (n-C4H9)2CuLi THF n-C4H9-R + n-C4H9Cu + LiX Hiu sut to n-C4H9-R bin i theo R-X nh sau: R-X CH3CH2CH2CH2CH2-Br CH3CH2CH2CHBrCH3 CH3CH2CH2CBr(CH3)2 Hiu sut 98% 12% < 10%

V kh nng phn ng ca cc ankyl halogenua vi Liti iankylcuprat ph hp vi c ch SN2. CH3-X > CH3CH2-X > (CH3)2CH-X > (CH3)3C-X R-I > R-Br> R-Cl >> R-F Tuy nhin v mt c ch ca phn ng nhiu phc tp cha hon ton r rng v khi RX l cc dn xut vinyl hay phenyl th phn ng vn cho hiu sut cao. Nhng d sao th y cng l mt phng php rt tt tng hp cc hirocacbon khng i xng. 1.3 Tng hp anken bng phn ng Wittig
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TI LIU LUYN THI & BI DNG KIN THC NM 2011

- Phn ng Wittig dng iu ch anken i t hp cht cacbonyl (anehit hoc xeton) v hp cht c photpho (Photphoni ylua) RCOR + (C6H5)3P=CRR RRC=CRR + (C6H5)3P=O V c ch ca phn ng kh phc tp nhng c th hnh dung nh sau: u tin, Ylit s kt hp vi nhm cacbonyl to thnh mt hp cht trung gian dng vng 4 cnh gi l oxaphosphetane. Sau , hp cht trung gian ny phn hy to ra anken v triphotphin oxit.

Bc 1:

Bc 2:

2. Tng hp cc ancol qua hp cht c nguyn t 2.1 Tng hp ancol vi hiu sut cao t anken - T anken iu ch 1 ancol c th dng phn ng cng HOH (trc tip) hay cng HX (X l halogen) ri thy phn dn xut halogen thu c. Tuy nhin phng php ny s cho hiu sut khng cao bi v cc phn ng cng HX (HOH, H-Hal) vo anken chy theo c ch AE. giai on 1 c s to thnh cacbocation do trong nhiu trng hp c th xy ra s chuyn v, khi ta s thu c hn hp sn phm. tng hp cc ancol c bc khc nhau vi hiu sut cao ngi ta c th tng hp qua hp cht c nguyn t. 2.1.1 Phn ng oxi thy ngn ha-loi b thy ngn. Phn ng ny dng iu ch cc ancol bc cao vi hiu sut cao t anken m khng sinh ra sn phm chuyn v ging nh phng php hirat ha. Giai on 1: Oxi thy ngn ha R-CH=CH2 + Hg(OAc)2 + H2O THF R-CH(OH)-CH2HgOAc + HOAc Giai on 2: Loi b thy ngn 4R-CH(OH)-CH2HgOAc+NaBH4+4NaOH 4RCH(OH)CH3+NaB(OH)4+4Hg+4NaOAc 2.1.2 Phn ng hirobo ha. - Phn ng hirat ha anken chy theo c ch AE sn phm to thnh tun theo quy tc Maccopnhicop tng qut. Thng thng sn phm thu c l ancol bc cao. Mun c c ancol bc thp ngi ta c th cho anken tc dng vi HBr c mt peroxit ri thy phn dn xut brom thu c. Tuy nhin, cch ny cng cho hiu sut khng cao, mt trong nhng cch c th iu ch ancol bc thp t anken l qua con ng hp cht c-bo.
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Giai on 1: Hirobo ha anken: 6RCH=CH2 + B2H6 2(RCH2CH2)3B Giai on 2: Oxi ha triankyl boran (RCH2CH2)3B + 3H2O2 + NaOH 3RCH2CH2OH + NaB(OH)4 u im ca phng php ny l cho hiu sut cao v tnh chn lc cao, hu nh ta ch thu c ancol bc thp v khng c s chuyn v. 2.2 Tng hp ancol t dn xut halogen v hp cht cacbonyl - Nm 1900 hc tr ca Barbier l Grignard a ra quy trnh tng hp hp cht c - magie i t dn xut halogen trong mi trng ete khan cho hiu sut cao. Da trn tnh cht a dng v kh nng phn ng cao ca hp cht c magie, Grignard v cc cng s tng hp nhiu hp cht hu c khc nhau. Khi cho hp cht c magie tc dng vi cc tc nhn thch hp (Anehit, xeton, este,) ri em cc sn phm thu c thy phn bng axit s thu c cc ancol khc nhau tng ng theo s :
O R-MgX + HCHO RCH2OMgX H RCH2OH (ancol bc 1, s C tng thm 1)
3

R-MgX +

O RCH2CH2OMgX H RCH2CH2OH
3

(Ancol bc 1, s C tng thm 2) R-MgX + RCHO


O H 3

(Ancol bc 2, s C tng thm 2)

R-MgX + RCOR

O H 3

(Ancol bc 3, s C tng thm 3) R-MgX + RCOOR


O H 3

(Ancol bc 3, s C tng thm 3) Trong trng hp nu dng este ca axit fomic ta s thu c ancol bc 2 RCHOHR - C th s dng cc dn xut khc ca axit cacboxylic RCOZ (vi Z l Cl-, -OCOR), trong cc trng hp ta lun thu c ancol bc 3 vi s cacbon tng thm 3. 3. Tng hp cc hp cht cacbonyl qua con ng hp cht c nguyn t 3.1 Tng hp anehit xeton - Thng thng ngi ta thng iu ch anehit xeton bng cch oxi ha nh ancol tng ng bng cc tc nhn oxi ha thch hp. Trong ancol c th c tng hp t c nguyn t. - Trong trng hp xeton c th tng hp bng phn ng ca hp cht nitrin vi hp cht c kim loi sau thy phn sn phm s thu c xeton.
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O R-CN R' MgX R-C=NMgX H R-C=O
3

Trong hp cht nitrin c iu ch bng phn ng tng hp Kolbe. 3.2 Tng hp axit cacboxylic qua hp cht c nguyn t - tng hp cc axit cacboxylic ngi ta c th oxi ha trc tip cc ancol hoc anehit, xeton tng ng vi tc nhn oxi ha thch hp. Ngoi ra ngi ta c th tng hp trc tip axit bng cch cho hp cht c kim tc dng vi CO2 sau em sn phm thy phn sn phm thu c.
O RMgX CO R-COOMgX H RCOOH
2
3

III. Phng php gii bi tp tng hp hu c nhiu giai on


1. Phng php gii chung - Vic tng hp v iu ch hu c l mt cng vic rt kh khn, vic gii quyt cc bi tp v tng hp hu c gip ngi hc nm vng kin thc c bn v ha hc hu c, quan h gia cc nhm chc hu c. Bn cnh i hi ngi hc phi c k nng phn tch v tng hp thnh tho t la chn c con ng tng hp ph hp v u vit nht. C th ni vic gii quyt cc bi tp loi ny gip ngi hc cng hon thin kin thc, k nng mt khc gip gio vin kim tra v nh gi chnh xc kh nng hiu bi v vn dng kin thc lin quan ca ngi hc.

- Thng thng qu trnh gii mt bi tp tng hp hu c nhiu giai on tin hnh qua cc bc:
Bc 1: Xc nh cng thc cu to ca cht ban u v sn phm cn tng hp Bc 2: Xc nh nhm chc v cu to ca cht cn tng hp, xem xt mi quan h vi cht u. Bc 3: Tm cc phng php khc nhau c th dng tng hp trc tip sn phm. Chn phng php hp l nht (tng i t giai on, cho hiu sut cao...) i t cc hp cht trung gian gn gi vi cht ban u. Bc 4: Thc hin quy trnh tng i vi cht trung gian, cho ti khi tip cn cht u. Bc 5: Hon thnh s phn ng (Vit cc phng trnh phn ng nu cn). 2. Bi tp vn dng Bi 1: Thay th cc ch ci A, B, C, D, E, F trong cc s tng hp sau bng cc cng thc thch hp?
O a. A CH MgBr B H Pentan-1-ol [ CH ]
3 2 3
3

O b. C CH CH D H 1-phenylbutan-2-ol MgI
3 2
3

.CO , 2 O c. E Mg / F 1 . H Axit pentanoic ete


2 3

Gii: a. A: HCHO, B: CH3[CH2]3CH2MgBr


PTP: CH3[CH2]3MgBr + HCHO CH3[CH2]3CH2OMgBr CH3[CH2]3CH2OMgBr + H3O+ CH3[CH2]4OH
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b. C: C6H5CH2CHO, D: C6H5CH2CH(OMgI)CH2CH3 PTP: C6H5CH2CHO + CH3CH2MgI C6H5CH2CH(OMgI)CH2CH3 C6H5CH2CH(OMgI)CH2CH3 + H2O C6H5CH2CH(OH)CH2CH3 c. E: CH3CH2CH2CH2X, F: CH3CH2CH2CH2-MgX trong X l Cl, Br, I PTP: CH3CH2CH2CH2X + Mg ete, khan CH3CH2CH2CH2-MgX CH3CH2CH2CH2-MgX + CO2 H CH3CH2CH2CH2COOH O
3

Bi 2: Ch ra ch sai trong s tng hp sau y:


. HCHO 2.H O a. Br-CH2CH2-Br Mg / BrMgCH2-CH2MgBr 1 ; HO[CH2]4OH ete
3

b. R-CCNa Cl [ Br R-CC-[CH2]3-Br NaOH R-CC-[CH2]3-OH CH ]


2 3

c. CH3[CH2]3Cl Li / hexan CH3[CH2]3Li CuBr (CH3[CH2]3)2CuLi CH CH CH CBr (CH )


3 2 2 3 2

CH3CH2CH2CH2C(CH3)2-CH2CH2CH3 Gii: a. Giai on 1 dn xut ihalogen s b tch Br2 to ra etilen b. giai on 1 ankinua s phn ng vi dn xut Brom v dn xut Brom c kh nng phn ng cao hn cc dn xut Clo. c. Liti iankylcuprat phn ng vi dn xut halogen bc 3 cho hiu sut rt thp do vy trong thc t ngi ta khng s dng phn ng ca Liti iankylcuprat vi cc dn xut halogen bc 2, 3 tng hp cc ankan bt i xng. Bi 3: T cc hp cht hu c c s cacbon 2 v cc ha cht v cn thit hy tng hp cc hp cht sau qua con ng hp cht c nguyn t. a. 2-metylbut-2-en Gii: Cch 1:
Na CHCH CHCNa CH I CH3CCH H /, t CH3CH=CH2 HCl CH3-CHCl-CH3 Pd
3
2 o

b. 4-Clo-4-metylpent-2-en

a. 2-metylbut-2-en

H 2 SO 4 .CH 3CHO ; 2. H 2 Mg / CH3CH(MgCl)CH3 1 O (CH3)2CHCH(OH)CH3 (CH3)2C=CHCH3 ete

Cch 2:
,t ,ThO .C CH3COOH t CH3COCH3 1 H MgCl C2H5COH(CH3)2 Al O (CH3)2C=CHCH3 ; 2. H O
2 o o

b. 4-Clo-4-metylpent-2-en
,ThO CH3COOH t CH3COCH3
2 o

Ca(OH)2

to

(CH3COO)2Ca
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Na CHCH CHCNa CH I CH3CCH HBr (), CH3CH=CHBr Mg / 1:1 peoxit ete
3

CH3CH=CHMgBr CH COCH CH3CH=CHCOH(CH3)2 Cl CH3CH=CHC-Cl(CH3)2 / P HO


3 3 2

Bi 4: T etan hy vit 4 s tng hp propan-1-ol? Cho bit cc ha cht v c v iu kin phn ng c . Gii: C1: CH3CH3+Cl2 as CH3CH2Cl +HCl CH3CH2Cl + KOH ancol CH2=CH2+KCl +H2O CH3CH2MgCl +
2 3

CH2=CH2 + 1 O2 Ag , 250 C
2

CH3CH2Cl + Mg ete CH3CH2MgCl

2O H CH3CH2CH2CH2OH + MgOHBr

O CH3CH2CH2CH2OH Al CH3CH2CH=CH2 + H2O .O 2. Zn / H O CH3CH2CH=CH2 1 ; CH3CH2CHO + HCHO


3 2

CH3CH2CHO + H2 Ni, t CH3CH2CH2OH


O C2: CH3CH2MgCl + CO2 H CH3CH2COOH + MgClOH
3

CH3CH2COOH + LiAlH4 + 3H2O CH3CH2CH2OH + LiOH + Al(OH)3 + 2H2


.O C3: CH2=CH2Zn/HOH 2HCHO 1
3

CH3CH2MgCl + HCHO CH3CH2CH2MgCl CH3CH2CH2OMgCl + HOH CH3CH2CH2OH + MgClOH C4: HCHO + H2 Ni.t CH3OH CH3OH + HCl CH3Cl + H2O CH3Cl + Mg ete CH3MgCl CH3MgCl + CH3CH2CH2OMgCl CH3CH2CH2OMgCl + HOH CH3CH2CH2OH + MgClOH Ngoi ra c th s dng cch sau: 2CH2=CH2 + O2 PdCl 2CH3CHO ,CuCl
2 2
o

CH3CHO + CH3MgCl CH3CH(OMgCl)CH3 CH3CH(OMgCl)CH3 + HOH CH3CH(OH)CH3 CH3CH(OH)CH3 H SO CH3CH=CH2 + HOH ,t


2 4 o

6CH3CH=CH2 + B2H6 THF 2 (CH3CH2CH2)3B (CH3CH2CH2)3B + 3H2O2 + NaOH 3CH3CH2CH2OH + NaB(OH)4 Bi 5: Chn cc hp cht cacbonyl v ylit thch hp, vit phng trnh phn ng iu ch cc anken sau? a. 3-metylhept-3-en c. C6H5CH2CH=C(CH2CH3)2

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b. Pent-2-en Gii:

d. 2-xiclopentylien propan

CH3 CH3CH2CH2CH=C< CH CH + (C6H5)3P=O 2 3 CH3 CH3CH2COCH3 + (C6H5)3P=CHCH2CH2CH3 CH3CH2CH2CH=C< + (C6H5)3P=O CH2CH3 b. CH3CH2CHO + (C6H5)3P=CHCH3 CH3CH2CH=CHCH3 + (C6H5)3P=O a. CH3CH2CH2CHO + (C6H5)3P=C< CH3 CH2CH3 Hay: CH3CHO + (C6H5)3P=CHCH2CH3 CH3CH2CH=CHCH3 + (C6H5)3P=O c. (CH3CH2)2CO + (C6H5)3P=CHCH2C6H5 C6H5CH2CH=C(CH2CH3)2 + (C6H5)3P=O Hay: C6H5CH2CHO+(C6H5)3P=C(CH2CH3)2 C6H5CH2CH=C(CH2CH3)2+(C6H5)3P=O d. (CH3)2CO + (C6H5)3P= Hay:
O

(CH3)2C=

+ (C6H5)3P=C(CH3)2 (CH3)2C=

Bi 6: T etanol hy vit cc phng trnh phn ng iu ch 2-brombutan? Gi thit cc ha cht v c v cc iu kin cho y . Gii: Cch 1: CH3CH2OH + Cu + O2 CH3CHO + CuO + H2O 6CH3CH2OH + 2P + 3Br2 6CH3CH2Br + 2H3PO3 CH3CH2Br + Mg ete CH3CH2MgBr CH3CH2MgBr + CH3CHO H CH3CH2CHOHCH3 O
3

6CH3CH2CHOHCH3 + 2P + 3Br2 CH3CH2CHBrCH3 + H3PO3 Cch 2: CH3CH2OH Al O C CH2=CH2 + H2O , 400


2 3 o

2CH2=CH2 + O2 Ag , 250 2 C CH3CH2MgBr +


o 2 3

H CH3CH2CH2CH2OH + Mg2+ + H2O + Br O


3

CH3CH2CH2CH2OH Al O C CH3CH2CH=CH2 + H2O , 400 CH3CH2CH=CH2 + HBr CH3CH2CHBrCH3 Bi 7: T axetilen hy vit cc phng trnh phn ng iu ch 1,2-ibrombutan? Gi thit cc ha cht v c v cc iu kin c . Gii:
, Cch 1: CHCH + H2 Pd / t CH2=CH2 PbCO
3 o

CH2=CH2 + HCl CH3CH2Cl CHCH + Na CHCNa


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CHCNa + CH3CH2Cl CH3CH2CCH


, CH3CH2CCH + H2 Pd / t CH3CH2CH=CH2 PbCO
3 o

CH3CH2CH=CH2 + Br2 CCl CH3CH2CHBrCH2Br


4

Cch 2: CH3CH2Cl + Mg ete CH3CH2MgCl 2CH2=CH2 + O2 Ag , 250 2 C CH3CH2MgCl +


o 2 3 o

H CH3CH2CH2CH2OH + Mg2+ + H2O + Br O


3

CH3CH2CH2CH2OH Al O C CH3CH2CH=CH2 + H2O , 400


CCl CH3CH2CH=CH2 + Br2 CH3CH2CHBrCH2Br
4

PdCl ,CuCl Cch 3: 2CH2=CH2 + O2 2CH3CHO


2 2

OH 2 CH3CHO CH3CH=CHCHO + H2O Ni, t CH3CH=CHCHO + 2H2 CH3CH2CH2CH2OH Al O , 400 C CH3CH2CH2CH2OH CH3CH2CH=CH2+ H2O
2 3 o o

CCl CH3CH2CH=CH2+ Br2 CH3CH2CHBrCH2Br


4

Bi 8: T etilen v cc ha cht v c cn thit hy vit phng trnh phn ng iu ch: a. Axit propanoic Gii: a. CH3CH2COOH Cch1: CH2=CH2 + HCl CH3CH2Cl CH3CH2Cl + Mg ete CH3CH2MgCl CH3CH2MgCl + CO2 CH3CH2COOMgCl CH3CH2COOMgCl + HOH CH3CH2COOH + Mg(OH)Cl Cch 2: CH3CH2Cl + KCN CH3CH2CN + KCl CH3CH2CN + 2HOH CH3CH2COOH + NH3
.O 2. Zn / H O Cch 3: CH2=CH2 1 ; 2HCHO
3 2

b. Axit butanoic

c. Etyl metyl xeton

CH3CH2MgCl + HCHO CH3CH2CH2OMgCl CH3CH2CH2OMgCl + HOH CH3CH2CH2OH + Mg(OH)Cl


O] CH3CH2CH2OH [ CH3CH2COOH

b. CH3CH2CH2COOH Cch 1: 2CH2=CH2 + O2 Ag , 250 2 C CH3CH2MgCl +


H CH3CH2CH2CH2OH + Mg2+ + H2O + Br O
3
o

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O] CH3CH2CH2CH2OH [ CH3CH2CH2COOH
.O 2. Zn / H O Cch 2: CH2=CH2 1 ; 2HCHO
3 2

18A/88 INH VN T - TP. HI DNG

CH3CH2MgCl + HCHO CH3CH2CH2OMgCl CH3CH2CH2OMgCl + HOH CH3CH2CH2OH + Mg(OH)Cl 6CH3CH2CH2OH + 2P + 3Br2 6CH3CH2CH2Br + 2H3PO3 CH3CH2CH2Br + Mg ete CH3CH2CH2MgBr CH3CH2CH2MgBr + CO2 CH3CH2CH2COOMgBr CH3CH2CH2COOMgBr + HOH CH3CH2CH2COOH + Mg(OH)Br c. CH3CH2COCH3 Cch 1: CH2=CH2 + HCl CH3CH2Cl CH3CH2Cl + Mg ete CH3CH2MgCl 2CH2=CH2 + O2 PdCl 2CH3CHO ,CuCl
2 2

CH3CH2MgCl + CH3CHO CH3CH2CH(OMgCl)CH3 CH3CH2CH(OMgCl)CH3 + HOH CH3CH2CH(OH)CH3 + Mg(OH)Cl 3CH3CH2CH(OH)CH3 + 2CrO3 + 6H+ 3CH3CH2COCH3 + 2Cr3+ + 6H2O
.O 2. Zn / H O Cch 2: CH2=CH2 1 ; 2HCHO
3 2

CH3CH2MgCl + HCHO CH3CH2CH2OMgCl CH3CH2CH2OMgCl + HOH CH3CH2CH2OH + Mg(OH)Cl CH3CH2CH2OH + Cu + O2 CH3CH2CHO + CuO + H2O
Ni, t HCHO + H2 CH3OH,
o

CH3OH + HI CH3I + HOH CH3I + Mg ete CH3MgI CH3CH2CHO + CH3MgI CH3CH2CH(OMgCl)CH3 CH3CH2CH(OMgCl)CH3 + HOH CH3CH2CH(OH)CH3 + Mg(OH)Cl 3CH3CH2CH(OH)CH3 + 2CrO3 + 6H+ 3CH3CH2COCH3 + 2Cr3+ + 6H2O Bi 9*: i t hp cht hu c duy nht l etanol, bng phng php tng hp qua hp cht c nguyn t hy lp s tng hp 3,3,5-trimetylheptan-1-ol vi cc tc nhn v c v iu kin phn ng c . Gii: CH3CH2OH SOCl CH3CH2Cl Mg / CH3CH2-MgCl ete
2

Al O , 400 C CH3CH2OH CH2=CH2 O / Ag


2 3

.O 2. Zn / H O , CH2=CH2 1 ; 2HCHO H /t CH3OH HCl CH3Cl Mg / CH3-MgCl ete Ni


3 2
2

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.CH MgCl , . HOH . HCHO 2. HOH O] CH3CH2-MgCl 1 , CH3CH2CH2OH [ CH3CH2CHO 1 2
3

CH3CH2CH(OH)CH3 PCl CH3CH2CHCH3 Mg / CH3CH2CMgCl ete


3

H3O+

Cl
3

CH3

.CH MgCl , . HOH O] CH3CH2CHCH2CH2OH [ CH3CH2CHCH2CHO 1 2

CH3

CH3
3

.CH MgCl , . HOH O] CH3CH2CHCH2CHCH3 [ CH3CH2CHCH2CCH3 1 2

CH3

OH
3

CH3

CH3CH2CHCH2C(CH3)2 PCl CH3CH2CHCH2C(CH3)2 Mg / C2H5CHCH2C(CH3)2 ete CH3


H3O+

OH

CH3

Cl

CH3

MgCl

CH3CH2CHCH2C(CH3)2CH2CH2OH (3,3,5-trimetylheptan-1-ol) CH3

Bi 10: T propan-2-ol hy vit cc phng trnh phn ng iu ch Hex-1-en-5-in. Gi thit cc ha cht v c v iu kin phn ng c . Gii:
,t (CH3)2CH-OH Al O CH3CH=CH2 + H2O
2 3 o

CCl CH3CH=CH2 + Br2 CH3CHBr-CH2Br


4

CH3CHBr-CH2Br + 2NaNH2 CH3CCH + 2NaBr + 2NH3 CH3CCH + Cl2 h ClCH2CCH + HCl CH3CH=CH2 Cl2 h ClCH2CH=CH2 + HCl ClCH2CH=CH2 + 2Li hexan CH2=CHCH2Li + LiCl 2CH2=CHCH2Li + CuI (CH2=CHCH2)2CuLi + LiI (CH2=CHCH2)2CuLi + ClCH2CCH CH2=CHCH2CH2CCH + CH2=CHCH2Cu + LiCl (Hex-1-en-5-in) Bi 11: Hon thnh y cc cht trong s tng hp sau. Vit cc phng trnh phn ng xy ra trong cc giai on ca qu trnh tng hp.
Na a. ancol isopropylic P I X KOH Y HBr Z 2 T / ancol
2

Br . HCHO 2. H O b. 2-metylbutan-1-ol P A1 Mg / B1 1 , C1 ete


2
3

c. 2-metylbut-2-en HBr E Mg / F / peroxit ete C6H5CH2CH2C6H5 d. A CL / B h


2

H3 O+

Mg/ete

(C6H5)2CO H3O+

D H H O
2

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Gii: a. X: (CH3)2CH-I, Y: CH3CH=CH2, Z: (CH3)2CHBr, T: (CH3)2CHCH(CH3)2 PTP: 6(CH3)2CHOH + 2P + 3I2 6(CH3)2CH-I + 2H3PO3
tan (CH3)2CH-I + KOH e ol CH3CH=CH2 + KI + H2O

CH3CH=CH2 + HBr (CH3)2CHBr 2(CH3)2CHBr + 2Na (CH3)2CHCH(CH3)2 (phn ng Wurtz) b.A1:CH3CH2CHCH2Br, B1: CH3CH2CHCH2MgBr, C1:CH3CH2CHCH2CH2OH CH3 CH3 CH3 PTP: 6CH3CH2CH(CH3)CH2OH + 2P + 3Br2 6CH3CH2CH(CH3)CH2Br + 3H3PO3 CH3CH2CH(CH3)CH2Br +Mg ete CH3CH2CH(CH3)CH2MgBr CH3CH2CH(CH3)CH2MgBr + HCHO H CH3CH2CH(CH3)CH2CH2OH+Mg2++ Br O
3

c. E: CH3CHCHBrCH3, F: CH3CHCH(MgBr)CH3, G: CH3CHCH(CH3)CH2CH2OH CH3 CH3 CH3


peroxit PTP: (CH3)2C=CHCH3 + HBr (CH3)2CHCHBrCH3

(CH3)2CHCHBrCH3 + Mg ete (CH3)2CHCH(MgBr)CH3 (CH3)2CHCH(MgBr)CH3 +


H (CH3)2CHCH(CH3)CH2CH2OH + Mg2+ + Br O
3

d. A: C6H5CH3, B: C6H5CH2Cl, C: C6H5CH2MgCl, D: C6H5CH2COH(C6H5)2, H: C6H5CH=C(C6H5)2. PTP: C6H5CH3 + Cl2 h C6H5CH2Cl + HCl C6H5CH2Cl + Mg ete C6H5CH2MgCl C6H5CH2MgCl + (C6H5)2CO H C6H5CH2COH(C6H5)2 + Mg2+ Cl O
3

C6H5CH2COH(C6H5)2 H SO C6H5CH=C(C6H5)2 + H2O ,t


2 4

Bi 12: Vit s iu ch cc hp cht sau t hp cht cho v cc ha cht v c cn thit (Gi thit cc iu kin phn ng cho ). a. Axit hept-2-inoic t propen c. Axit axetylenicacboxylic t axetylen b. Axit 2,5-imety aipic t propen e. nonan-5-on t ancol n-butylic

d. Benzyl metyl cacbinol v etyl metyl cacbinol t toluen v axetylen Gii: a. CH3CH2CH2CH2CC-COOH CH3CH=CH2 Cl / CH2=CHCH2Cl Mg / CH2=CHCH2MgCl ete 500 C
o 2

CH3CH=CH2 HBr CH3CH2CH2Br / peroxit

CH2=CHCH2MgCl

CH3[CH2]3CH=CH2 Br
2

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CH3[CH2]3CHBr-CH2Br NaNH CH3[CH2]3CCH


2

CH2=CHCH2MgCl

C4H9CCMgCl

1.CO2 2.H2O

CH3[CH2]3CC-COOH

b. Axit 2,5-imety aipic


Na CH3CH=CH2 Cl / CH2=CHCH2Cl CH2=CHCH2CH2CH=CH2 2 HBr 500 C
2 o

ete CH3CHBrCH2CH2CHBrCH3 2 Mg CH3CH(MgBr)CH2CH2CH(MgBr)CH3 /

+2CO2 H3O+

HOOC-CHCH2CH2CH-COOH CH3 CH3


1.CO2 2. H2O

c. HOOC-CC-COOH
Na HCCH 2 NaCCNa

HOOC-CC-COOH

d. C6H5CH2CH(OH)CH3 CHCH HOH CH3CHO / Hg C6H5CH3 Cl / C6H5CH2Cl Mg / C6H5CH2MgCl ete h


2
2

1.CH3CHO HOH

C6H5CH2CH(OH)CH3
1.CH3CHO 2.HOH

CH3CH(OH)CH2CH3 (etyl metyl cacbinol) CHCH H / CH2=CH2 HCl CH3CH2Cl Mg / CH3CH2-MgCl ete Pd
2

CH3CH(OH)CH2CH3 e. (n-C4H9)2CO
Mg/ete
Br CH3[CH2]2CH2OH P CH3[CH2]2CH2Br
2

CH3[CH2]2CH2-MgBr
H3 O+

(n-C4H9)2CO

KCN

CH3[CH2]2CH2-CN Bi 13: T metanol hy vit cc phng trnh phn ng iu ch cc hp cht sau: a. Etanol Gii: a. CH3CH2OH CH3OH + HBr CH3Br + HOH CH3Br + Mg ete CH3-MgBr CH3OH + Cu + O2 HCHO + H2O + CuO CH3-MgBr + HCHO H CH3CH2OH + Mg2+ + Br O
3

b. Propan-2-ol

c. Butan-1-ol

d. Etyl metyl cacbinol

b. (CH3)2CH-OH T cc iu kin ban u tng hp c ancol etylic (CH3CH2OH) Cch 1: CH3CH2OH + Cu + O2 CH3CHO + H2O + CuO CH3CHO + CH3-MgBr H (CH3)2CH-OH + Mg2+ + Br O
3

O] Cch 2: CH3CH2OH [ CH3COOH

,t 2CH3COOH ThO CH3COCH3 + CO2 + H2O


2

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18A/88 INH VN T - TP. HI DNG

Hoc: 2CH3COOH + CaCO3 Ca(CH3COO)2 + CO2 + H2O Ca(CH3COO)2 t CH3COCH3 + CaCO3 c. CH3CH2CH2CH2OH T cc iu kin ban u tng hp c ancol etylic (CH3CH2OH) Cch 1: CH3CH2OH + HBr CH3CH2Br + HOH CH3CH2Br + Mg ete CH3CH2-MgBr
Al O , 400 C CH3CH2OH CH2=CH2 + HOH
2 3 o o

CH3COCH3 + H2 Ni, t (CH3)2CH-OH

2CH2=CH2 + O2 Ag , 250 2 C CH3CH2-MgBr +


H CH3CH2CH2CH2OH + Mg2+ + Br O
3

Cch 2: CH3CH2OH + Cu + O2 CH3CHO + H2O + CuO 2CH3CHO OH CH3CH=CHCHO + H2O CH3CH=CHCHO + 2H2 Ni, t CH3CH2CH2CH2OH d. CH3CH2CH(OH)CH3 T cc iu kin ban u tng hp c CH3CH2-MgBr v CH3CHO (theo cu c) Cch 1: CH3CH2-MgBr + CH3CHO
2+ CH3CH2CH(OH)CH3 + Mg + Br H O
3
o

Cch 2: CH3OH + HBr CH3Br + HOH CH3CN + CH3CH2-MgBr H CH3CH2COCH3 O


3

CH3Br + KCN CH3CN + KBr

CH3CH2COCH3 + H2 Ni, t CH3CH2CH(OH)CH3 Bi 14: T cc nguyn liu c sn: Metan, H2O, HCl, Mg cng cc ha cht v c v iu kin c hy lp s phn ng iu ch 4-etylheptan-4-ol. Gii: CH4 O / CH3OH HCl CH3Cl 200 C ,100 atm
2 o

Na CH4 1500/ CHCH CHCNa C LLN

CH3CCH

H2/Pd

CH3CH=CH2 HBr CH3CH2CH2Br Mg / CH3CH2CH2-MgBr / peroxit ete


,t CHCH H Pd CH2=CH2 HCl CH3CH2Cl Mg / CH3CH2-MgCl ete
2 o

CHCH HOH CH3CHO OH CH3CH=CHCHO / Hg


o 2

CH3CH2CH2H2

, O] CH3CH=CHCH(OH)CH2CH2CH3 H /t CH3CH2CH2CH(OH)CH2CH2CH3 [ Ni

CH3CH2CH2COCH2CH2CH3

CH3CH2MgBr 2 H

CH3CH2CH2C(OH)CH2CH2CH3 CH2CH3

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Bi 15: Trong nhiu loi tinh du ngi ta thu c cht 6-metylhept-5-en-2-on. Hy lp vit cc phng trnh phn ng iu ch hp cht ny t metyl 4-oxopentanoat? Gi thit cc ha cht v iu kin c . Gii:
H CH3COCH2CH2COOCH3 + C2H4(OH)2 CH 3-C-CH2CH2COOCH3 + H2O

CH 3-C-CH2CH2COOCH3 + LiAlH4 + 4H2O CH 3-C-CH2CH2CH2OH + CH3OH +


O O O O

LiOH +Al(OH)3 + 3H2

, CH 3-C-CH2CH2CH2OH Cu CH 3-C-CH2CH2CHO + H2 t

CH 3-C-CH2CH2CHO + (C6H5)3P=C(CH3)2 CH 3-C-CH2CH2CH=C(CH3)2


O O O O

+ (C6H5)3PO

O CH 3-C-CH2CH2CH=C(CH3)2 H CH3COCH2CH2CH=C(CH3)2 + C2H4(OH)2


3

Bi 16: Axit cacboxylic A c cng thc phn t l C5H8O2 tn ti di 2 dng ng phn lp th ca nhau l A1 v A2. Ozon phn A thu c axetanehit v axit 2-oxopropanoic. a) Hy xc nh cng thc cu to ca A1 v A2, gi tn mi axit? b) Cho tng ng phn A1 v A2 tc dng vi Cl-Br trong dung mi CCl4. Vit cng thc cu to ca cc sn phm to thnh. Xc nh cu hnh tuyt i ca cc sn phm. c) Hiro ha A1 v A2 (c xc tc thch hp) thu c axit B. Vit cc phng trnh phn ng iu ch B t but-1-en? Gii: a) bt bo ha ca A l ( + v) = 2 Nh vy A c th l mt axit n chc mch vng hay l mt axit mch h n chc cha 1 lin kt i trong phn t. Do A c phn ng ozon phn nn A phi l axit n chc, mch h, khng no. CH3CHO O=C-COOH CH3-CH=C-COOH (A) CH3 CH3

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Vy A1, A2 l cc ng phn hnh hc ca nhau: A1: (2Z)-2-metylbut-2-enoic v A2: (2E)-2-metylbut-2-enoic b) Br H


R

COOH
R

COOH CH3 Cl
S S

(2Z)-2-metylbut-2-enoic + Cl-Br

CH3 Cl

Br H

CH3 COOH Br (2E)-2-metylbut-2-enoic + Cl-Br Cl


R S

CH3 COOH + CH3 H


S R

CH3 H

Br Cl

CH3 c) Axit B: CH3CH2CH(CH3)COOH CH3CH2CH=CH2 + HCl CH3CH2CH(Cl)CH3 CH3CH2CH(Cl)CH3 + Mg ete CH3CH2CH(MgCl)CH3 CH3CH2CH(MgCl)CH3 + CO2 CH3CH2CH(CH3)COOMgCl

CH3

CH3CH2CH(CH3)COOMgCl + HOH CH3CH2CH(CH3)COOH +Mg(OH)Cl Bi 17: T benzen v cc ha cht v c hy lp 3 s phn ng iu ch axit benzoic? Gi thit cc iu kin phn ng c . Gii:
O , 1) C6H6 Br /t C6H5Br Li / C6H5-Li CO C6H5COOLi H C6H5COOH ete Fe
2 o

2) C6H6

CO + HCl AlCl3
3 2 4

O] C6H5CHO [ C6H5COOH
o 2

3) C6H6 HNO/SO C6H5NO2 Sn / HCl C6H5NH2 HNO5 C6H5-NN CuCN H / C


O C6H5-CN H C6H5COOH
3

Bi 18: Khi cho mt ankyl magie bromua X phn ng vi axeton thu c mt ancol bc ba. Thc hin phn ng ehirat ha ancol va thu c, ri sau hiro ha c xc tac th thu c 2metylbutan. Xc nh cng thc cu to ca ankyl magie bromua trn? Vit cc phng trnh phn ng tng hp n t metan v cc ha cht v c cn thit. Gii: Ancol X HOH Anken H 2-metylbutan / xt
2

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Gi thit trong phn ng tch nc to anken khng c s chuyn v lm thay i b khung cacbon th ancol X c mch cacbon tng t 2-metylbutan. Mt khc X l ancol bc III nn X l 2metylbutan-2-ol , CTCT:(CH3)2C(OH)CH2CH3 Kim chng: X tch nc theo c ch E1, giai on 1 to ra cacbocation bc III bn do khng c s chuyn v, nh vy gi thit ban u l ng. Vy ankyl magie bromua cn tm l CH3CH2MgBr iu ch CH3CH2MgBr t metan 2CH4 1500/ CHCH + 3H2 C LLN CHCH + H2 Pd CH2=CH2 BaSO
4
o

CH2=CH2 + HBr CH3CH2Br CH3CH2Br + Mg ete CH3CH2-MgBr Bi 19: T 3-fomylxiclohexanon hy vit cc phng trnh phn ng iu ch 3-fomyl-1metylxiclohexan-1-ol vi cc ha cht v iu kin thch hp. Gii:
O

+ HO-CH2CH2-OH
CHO
O

xt H+
CH O O

CH 3

+ CH3-MgCl
CH O O

ete

O CH O

OMgCl

H3C
CH 3

OH

O CH O

OMgCl

+ H3 O+
CHO

+ Mg2+ + Cl- + C2H4(OH)2

Bi 20: Cho hp cht A tc dng vi metyl magie bromua (d) trong mi trng ete thy thot ra kh metan. Hn hp sn phm sau phn ng em thy phn thu c imety etyl cacbinol ( (CH3)2C(OH)CH2CH3). Xc nh cng thc cu to ca A v vit cc phng trnh phn ng xy ra? Tng hp A t metan qua hp cht c magie? Gii: Khi cho A tc dng vi hp cht CH3MgBr to ra sn phm m sau khi thy phn thu c ancol bc III nn A c th l xeton hoc axit cacboxylic v dn xut (loi tr axit fomic v dn xut ca n).
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18A/88 INH VN T - TP. HI DNG

Mt khc, A tc dng vi hp cht CH3MgBr/ete khan c gii phng kh metan chng t A c H linh ng. Vy A l axit cacboxylic T cng thc ca ancol thu c ta suy ra cng thc ca A l: CH3CH2COOH Phng trnh phn ng xy ra: CH3CH2COOH + CH3MgBr CH3CH2COOMgBr + CH4 CH3CH2COOMgBr + 2CH3MgBr ete (CH3)2C(OMgBr)CH2CH3 (CH3)2C(OMgBr)CH2CH3 + HOH (CH3)2C(OH)CH2CH3 + Mg(OH)Br iu ch A t metan: 2CH4 1500/ CHCH + 3H2 C LLN CHCH + H2 Pd CH2=CH2 BaSO
4
o

CH2=CH2 + HBr CH3CH2Br

CH3CH2Br + Mg ete CH3CH2-MgBr CH3CH2-MgBr + CO2 CH3CH2COOMgBr CH3CH2COOMgBr + HOH CH3CH2COOH + Mg(OH)Br Bi 21: T ancol etylic v cc cht v c cn thit hy thc hin tng hp cc cht sau: a) 3-metylpenta-3-ol c) Butan-1-ol Gii: a) CH3CH2C(OH)CH2CH3 CH3 Cch 1: CH3CH2OH HBr CH3CH2Br Mg / CH3CH2MgBr ete
, O] CH3CH2OH [ CH3CHO OH CH3CH=CHCHO H /t CH3CH2CH2CH2OH Ni
2 o

b) 3-metylbutan-1-ol d) 3-metylpentan-1-ol

,t Al 2 O CH3CH2CH=CH2 3

1. Hg(OAc)2 2. NaBH4/OH-

O] CH3CH2CH(OH)CH3 [

CH3CH2COCH3

1.CH3CH2MgBr 2.HOH

CH3CH2C(OH)CH2CH3 CH3
1.CH3CH2MgBr 2.HOH

O] Cch 2: CH3CH2OH [ CH3COOH C H CH3COOC2H5 OH / H SO


2 5 2 4

CH3CH2C(OH)CH2CH3 CH3 b) (CH3)2CHCH2CH2OH (X) CH3CH2OH Al O C CH2=CH2 Ag , 250 , 400 C


2 3 o o

O] CH3CH2OH [ CH3COOH ThO CH3COCH3 ,t


2

(X)
HOH

Ca(OH)
2

Ca(CH3COO)

to

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c) CH3CH2CH2CH2OH CH3CH2OH HBr CH3CH2Br Mg / CH3CH2MgBr ete CH3CH2OH Al O C CH2=CH2 Ag , 250 , 400 C
2 3 o o

d) CH3CH2CHCH2CH2OH (X) CH3


O] CH3CH2OH [ CH3CHO

1.CH3CH2MgBr 2.HOH

Butan-1-ol

1. CH 2. HOH CH MgBr

CH3CH2CH(OH)CH3 HBr

CH3CH2CH(Br)CH3 Mg / CH3CH2CH(MgBr)CH3 ete Bi 22: Cho phn ng sau:


.CH MgI (CH3)3C-CH-CHO 1 B 2. HOH C
3

(X)
2.HOH

CH3 a) Vit c ch phn ng (1) v cng thc cu to ca B, C? b) Nu thay th nguyn t H trong nhm CHO ln lt bi gc metyl v t-butyl th tc phn ng thay i nh th no? Gii thch. c) Nu hp cht cacbonyl ban u c cu hnh (R) th C c cu hnh nh th no? Gii: a) C ch: + CH3-MgI Chm (CH3)3C-CH-CH-CH3 + [MgI]+ CH3 O-

(CH3)3C-CH-CHO CH3 CH3 O-

(CH3)3C-CH-CH-CH3 + [MgI]+ nhanh (CH3)3C-CH-CH-CH3 (B) CH3 OMgI (C): (CH3)3C-CH-CH-CH3 CH3 OH b) Nu thay th nguyn t H trong nhm CHO ln lt bi cc gc CH3- v (CH3)3C- th tc phn ng gim dn.(H > CH3 > (CH3)3C-) Gii thch: Phn ng cng nucleophin vo lin kt >C=O trong nhm cacbonyl chu nh hng ca hiu ng electron v hiu ng khng gian. Khi thay th H ln lt bi CH3- v (CH3)3C- kch thc cc nhm th tng gy ra hiu ng khng gian loi 1 ngn cn s tn cng ca tc nhn nucleophin vo nguyn t C trong nhm CHO. Mt khc, khi nhm th cng phc tp hiu ng +I cng mnh lm cho in tch + trn nguyn t C trong >C=O gim xung lm cho tc nhn nucleophin kh tn cng hn. V 2 l do nn tc phn ng gim dn theo th t H > CH3 > (CH3)3C- .
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18A/88 INH VN T - TP. HI DNG

c) Nu hp cht ban u c cu hnh R th sn phm to thnh (C) c cu hnh tuyt i l (2R,3R) Cu to ca C:


CH H CH C(CH3)3 H OH

Bi 23: Qua khng qu 5 phn ng (khng tnh phn ng thy phn) hy vit cc phng trnh phn ng iu ch cc cht sau t cc cht cho. Gi thit cc tc nhn v c v iu kin phn ng c . a) 2-phenylpropan-2-ol t toluen v metanol b) Benzyl metyl xeton t toluen v metanol c) Axetophenon t benzen v etanol d) 2-metyl-3-phenylpropan-2-ol t toluen v etanol Gii: a) CH3OH + HBr CH3Br + HOH CH3-Br + Mg ete CH3-MgBr C6H5CH3 + KMnO4 + H2SO4 t C6H5COOH + K2SO4 + MnSO4 + HOH C6H5COOH + SOCl2 C6H5COCl + HCl + SO2 C6H5COCl + CH3-MgBr ete C6H5C(CH3)2 HOH C6H5C(CH3)2 OMgBr b) CH3OH + HBr CH3Br + HOH CH3-Br + Mg ete CH3-MgBr C6H5CH3 + Cl2 askt C6H5CH2Cl + HCl C6H5CH2Cl + KCN C6H5CH2CN + KCl
O C6H5CH2CN + CH3-MgBr ete C6H5CH2C=N-MgBr H C6H5CH2COCH3
3 o

OH

CH3 c) C6H6 + Br2 Fe, t C6H5-Br + HBr CH3CH2OH + Cu + O2 t CH3CHO + CuO + H2O
O CH3CHO + C6H5-MgBr ete C6H5-CH-CH3 H C6H5-CH-CH3
3 o o

C6H5-Br + Mg ete C6H5-MgBr

OMgBr
,t C6H5-CH-CH3 Pt C6H5COCH3 + H2
o

OH

OH
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O] Cch khc: CH3CH2OH [ CH3COOH

CH3COOH + SOCl2 CH3COCl + HCl + SO2 CH3COCl + C6H6 AlCl C6H5COCH3 + HCl
3

d) C6H5CH3 + Cl2 askt C6H5CH2Cl + HCl C6H5CH2Cl + Mg ete C6H5CH2-MgCl 3CH3CH2OH + 2K2Cr2O7 + 8H2SO4 3CH3COOH + 2K2SO4 + 2Cr2(SO4)3 + 11H2O 2CH3COOH ThO CH3COCH3 + CO2 + H2O ,t
2 o

O CH3COCH3 + C6H5CH2-MgCl ete C6H5-C(CH3)2 H C6H5-C(CH3)2


3

OMgCl Bi 24: Vit phng trnh phn ng biu din cc chuyn ha sau: a) CH3CH2CH2OH CH3CH(OH)CH3 b) (CH3)3C-Br (CH3)2CHCH2-OH c) (CH3)2CHCH2CH2OH (CH3)2CHCOCH3 d) CH3CH2CH(OH)CH3 3,4-imetylhexan e) Axetilen Butan-1,4-iol Gii:
, a) CH3CH2CH2OH H SO CH3CH=CH2 + H2O t
2 4 o

OH

CH3CH=CH2 + Hg(OAc) + H2O THF CH3CH(OH)-CH2HgOAc + HOAc 4CH3CH(OH)-CH2HgOAc + NaBH4 + 4NaOH CH3CH(OH)CH3 + 4Hg + NaB(OH)4 + 4NaOAc C th s dng phn ng sau y, tuy nhin cch ny cho hiu sut khng cao
O CH3CH=CH2 + H2O H CH3CH(OH)CH3
3

tan b) (CH3)3C-Br + C2H5ONa e ol (CH3)2C=CH2 + C2H5OH + NaBr

6(CH3)2C=CH2 + B2H6 t 2 ((CH3)2CH-CH2)3B ((CH3)2CH-CH2)3B + + 3H2O2 + NaOH 3(CH3)2CH-CH2OH + NaB(OH)4 Khng thc hin phn ng hp nc isobutilen v sn phm sinh ra ch yu s l ancol bc 3.
, c) (CH3)2CHCH2CH2OH H SO (CH3)2CHCH=CH2 + H2O t
2 4 o

(CH3)2CHCH=CH2 + Hg(OAc)2 + H2O THF (CH3)2CHCH-CH2HgOAc + HOAc OH


O] (CH3)2CHCH-CH2HgOAc NaBH / (CH3)2CHCH-CH3 [ (CH3)2CHCOCH3 OH
4

OH

OH

d) 6CH3CH2CH(OH)CH3 + 2P + 3Br2 6CH3CH2CHBr-CH3 + H3PO3


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18A/88 INH VN T - TP. HI DNG

2CH3CH2CHBr-CH3 + 2Na 3,4-imetylhexan + 2NaBr e) HCCH + 2NaNH2 Na-CC-Na + 2NH3 Na-CC-Na + 2HCHO ete NaOCH2-CC-CH2ONa NaOCH2-CC-CH2ONa + 2H3O+ HOCH2-CC-CH2OH + 2H2O + 2Na+ HOCH2-CC-CH2OH + 2H2 Ni, t HOCH2-CH2-CH2-CH2OH Bi 25: Cho s tng hp sau:
O Axit panmitic LiAlH A HCl B Mg / C Oxiran D H E KMnO / F ete H
4
3 4 o

Hy xc nh cc cht A, B, C, D, E, F trong s v vit cc phng trnh phn ng xy ra? Gi tn F? Gii: CH3-[CH2]14-COOH + LiAlH4 + 3HOH CH3-[CH2]14-CH2OH(A)+LiOH +Al(OH)3 + 2H2 CH3-[CH2]14-CH2OH + HCl CH3-[CH2]14-CH2Cl (B) + H2O CH3-[CH2]14-CH2Cl + Mg ete CH3-[CH2]14-CH2-MgCl (C) CH3-[CH2]14-CH2-MgCl +
ete CH3-[CH2]16-CH2-OMgCl (D)

CH3-[CH2]16-CH2-OMgCl + H3O+ CH3-[CH2]16-CH2-OH (E) + Mg2+ + Cl- + H2O 5CH3-[CH2]16-CH2-OH + 4KMnO4 + 6H2SO4 5CH3-[CH2]16-COOH (F) +2K2SO4 +4MnSO4 +11 H2O F: CH3-[CH2]16-COOH l Axit stearic (Axit octaecanoic)

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TI LIU LUYN THI & BI DNG KIN THC NM 2011

Phn III. KT LUN


Cng vi s pht trin khng ngng ca khoa hc-k thut, ha hc ngy cng xut hin nhiu trong i sng sn xut. Do yu cu m vic tng hp v iu ch hu c ngy cng l nhim v quan trng ca tng hp hu c. V mt l thuyt vic gii quyt cc bi ton v tng hp v iu ch hu c gip ngi hc c th cng c l thuyt c bn v phn ng hu c, tnh cht ca cc hp cht hu c nhm chc. Rn luyn kh nng la chn c h thng, vn dng linh hot cc kin thc c bn v k nng t duy. Sau mt thi gian nghin cu ti bn thn ti thu c mt s kt qu sau: - Tng quan l thuyt v hp cht c ngyn t - Cc phn ng chuyn ha trong tng hp cc hp cht hu c c nhm chc thng qua hp cht c nguyn t. - H thng bi tp vn dng. Mc d rt c gng nhng trong qu trnh thc hin ti ny s khng trnh khi nhng thiu st. Rt mong nhn c s ng gp kin ca cc qu thy c v cc bn ti c hon thin hn.

HOAHOC.ORG NG XUN QUNH 09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - admin@hoahoc.org

TT LUYN THI & BI DNG KIN THC NGY MI

18A/88 INH VN T - TP. HI DNG

TI LIU THAM KHO


1. L Huy Bc, Nguyn Vn Tng (1986), Bi tp ha hu c. NXB Gio dc, H Ni. 2. Nguyn Hu nh, nh Rng (2008), Ha hc hu c 1. NXB Gio dc, H Ni. 3. Nguyn Hu nh (2008), Bi tp ha hc hu c. NXB Gio dc, H Ni. 4. o Vn ch, Triu Qu Hng (2007), Mt s cu hi v bi tp ha hu c. NXB HQG H Ni. 5. nh Rng, ng nh Bch, Nguyn Th Thanh Phong (2008), Ha hc hu c 2. NXB Gio dc, H Ni. 6. Trn Quc Sn, ng Vn Liu (2009), Gio trnh c s ha hc hu c, Tp 1. NXB i hc s phm, H Ni. 7. Trn Quc Sn, ng Vn Liu (2009), Gio trnh c s ha hc hu c, Tp 2. NXB i hc s phm, H Ni. 8. Trn Quc Sn (1979), C s l thuyt ha hc hu c, Tp II. NXB Gio dc, H Ni. 9. Nguyn Minh Tho (2005), Tng hp hu c. NXB HQG H Ni. 10. Ng Th Thun (2008), Ha hc hu c phn bi tp, Tp 2. NXB KH-KT, H Ni.

HOAHOC.ORG NG XUN QUNH 09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - admin@hoahoc.org

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