34510697 Loi Giai Cac Bai Tap 2

Bi tp Ha hc hu c i hc

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CHNG I: AMIN V MUI IAZONI 1.1/ Vit cng thc cu to cc hp cht c tn sau: a/ Isopentylamin b/ Metylbutylamin c/ Isobutylimetylamin d/ 2Metyl1,5iaminpetan e/ N,Nimetylanilin f/ mPhenyleniamin 1.2/ Gi tn cc hp cht sau:

1.3/ Vit cu trc electron v cu trc khng gian ca etylmetylamin 1.4/ Vit s iu ch amin t: a/ Etanol v NH3 c mt AlCl3 b/ Etyliodua vi NH3 1.5/ Lp s tng hp anilin, axit sunfanilic v mphenyleniamin t benzen Gii: Tng hp anilin:

Tng hp axit sunfanilic:

Tng hp m phenyleniamin

1.6/ Lp s iu ch cc cht sau khng ln amin khc bc: a/ 3Metyl2aminobutan t anken c cng mch cacbon b/ Butylamin t axit butyric c/ Benzylamin t benzylclorua, t axit phenylaxetic d/ pcloanilin t clobenzen

HNO3H2SO4

NO2

Fe, HCl

NH3Cl

NaOH

NH2

NH2H2SO4

NH3.HSO4 NH3

SO3

150 Co

(axit sunfanilic)

HNO3H2SO4

NO2

NO2

Fe, HCl

NH3.Cl

NH3.ClNaOH

NH2

NH2

CH3 CH CH3NH2

CH3 CH2 NH CH3 CH3 CH NCH3

CH2 CH3CH3

a/ b/ c/

(C2H5)4NOH (CH3CH2CH2)2NH2Cld/ e/ f/ NH2H2N

CH3NH2

NH CH3 NHg/ h/ i/



Gii: a/

b/

c/ T benzylclorua

T axit phenylaxetic

d/

1.7/ Vit phng trnh phn ng ca npropylamin v anilin vi a/ axit clohiric b/ axetylclorua c/ anhiritaxetic d/ etylclorua e/ natrinitrit v axit clohiric So snh kh nng phn ng ca 2 cht trn trong mi cp phn ng 1.8/ So snh tnh baz ca cc cht trong cc dy sau v gii thch: a/ nC4H9NH2; (C2H5)2NH; C2H5NHCH3; CH3CONHCH2CH3 b/ C6H5NH2; C2H5NHCH3; C2H5NHC6H5; CH3NH2. c/ C6H5NH2; pClC6H4NH2; pO2NC6H4NH2; pH2NC6H4NH2 1.9/ Vit phn ng iazo ha nhng hp cht sau vi NaNO2 trong dung dch HCl a/ pToluiin b/ pcloanilin c/ pnitroanilin Vi nhng amin thm coa tnh baz yu nh pnitroanilin; 2,4initroanilin th phi tin hnh iazo ha nh th no?

CH3 CHCH3

CH CH2 CH3 CHCH3

CH CH3OH

H2O H

[O] CH3 CHCH3

CO

CH3

H2N OH CH3 CHCH3

CN

CH3OH

[H] CH3 CHCH3

C CH3NH2

CH3CH2CH2COOHLiAlH4 CH3(CH2)3OH [O] CH3(CH2)2CHO

H2N OH CH3(CH2)2CH N OH CH3(CH2)3NH2[H]

H2N OH C6H5 CH N OH [H] C6H5 CH2 NH2

C6H5 CH2 COOHPCl5 C6H5 CH2 C Cl

O

NH3 C6H5 CH2 C NH2OBr2, NaOH C6H5 CH2 NH2

ClHNO3H2SO4

Cl

NO2

Fe, HCl

Cl

NH3Cl

NaOH

Cl

NH2

C6H5 CH2ClH2O, OH C6H5 CH2OH [O] C6H5 CHO



1.10/ Vit phng trnh phn ng to thnh chu mu azo t cc cht sau dng lm hp phn iazo v azo: Hp phn iazo Hp phn azo Anilin N,Nimetylanilin pToluiin Phenol Axit sunfanilic Anilin Axit sunfanilic Naphtol 1.11/ Hp cht c thnh phn C5H13N tan trong axit, khi tc dng vi CH3I, sau vi AgOH to thnh hp cht C8H21ON. Cht ny b nhit phn to thnh trimetylamin v 2metylbut1en. Xc nh cng thc cu to ca cht u v vit cc phng trnh phn ng minh ho. Gii: Theo gi thit th cht u phi l amin bc 1 v khi phn ng vi CH3I, sau vi AgOH th s nguyn t C tng ln 3 n v. Nh vy cht u c dng C5H11NH2 C8H11ON phi c dng C5H11N+(CH3)3.OH. Theo gi thit v kt qu trn, khi nhit phn th :

V vy amin ban u phi c cng thc cu to l

1.12/ Amin c cng thc phn t C6H15N, khi tc dng vi HNO2 s tch ra nit v ancol C6H14O. Thu phn sn phm ozonit ca anken to thnh do loi nc ca ancol trn thu c axetanehit v etylmetylxeton. Xc nh cng thc cu to ca amin trn v vit cc phng trnh phn ng minh ho. Gii: Theo gi thit, t sn phm oznphn ta co th suy ra cng thc cu to ca anken l:

M anken li c to thnh t phn ng tch nc ca ancol C6H14O nn ancol phi c cng thc cu to l:

Amin ban u phn ng vi HNO2 to ra ancol nn l amin bc 1, t c th suy ra cng thc cu to ca amin l:

C5H11N(CH3)3.OH (CH3)3N CH3 CH2 C CH2CH3

+

CH3 CH2 CHCH3

CH2 NH2 hoc CH3 CH2 CNH2

CH3CH3 (Tch theo Hoffman)

CH CCH3 CH2CH3

CH3

CH2CH3 C CH2CH3

CH3 hoc CH3OH

CHOH

CHCH3

CH2 CH3

CH2CH3 C CH2CH3

CH3 hoc CH3NH2

CHNH2

CHCH3

CH2 CH3



1.13/ Hp cht c cng thc phn t C8H11N, tc dng vi HNO2 to thnh ancol C8H10O. Oxi ha ancol ny trong iu kin thch hp thu c axit terephtalic. Xc nh cng thc cu to ca cht u v vit cc phng trnh phn ng minh ho. Gii: Axit terephtalic c cng thc cu to l:

Axit ny l sn phm oxi ha ancol n chc nn ancol phi c cng thc cu to l:

Amin ban u phn ng vi HNO2 to ra ancol nn l amin bc 1, t c th suy ra cng thc cu to ca amin l:

1.14/ Hon thnh cc s phn ng sau:

Gii: a/

b/

COOHHOOC

CH2OHH3C

CH2NH2H3C

HNO2 PCl5 KCNCH3 CH NH2CH3

A B C D[H]a/

c/ C6H5NH2 A B C DCH3COCl HNO3

H2SO4HNO3H2SO4

thu phn

CH3 CH NH2CH3

HNO2+ CH3 CH OHCH3 (A)

N2 H2O+ +

CH3 CH OHCH3

PCl5+ CH3 CH ClCH3

POCl3 HCl+ +(B)

CH3 CH ClCH3

KCN CH3 CH CNCH3

KCl+(C)

+

CH3 CH CNCH3

[H]+ 4 CH3 CH CH2CH3

NH2(D)

CH3 CH CH2BrCH3

KCN CH3 CH CH2CH3

CN KCl+(A)

+

KCNCH3 CH CH2BrCH3

A B C D NaancolCHCl3 [H]b/ KOH



c/

1.15/ T benzen hoc toluen, hy lp s iu ch cc cht sau qua giai on to mui iazoni: a/ mFloclobenzen b/ 1,3,5Tribrombenzen c/ Axit isophtalic d/ mToluiin Gii: a/

HNO3C6H6 C6H5NO2 m ClC6H4NO2 m ClC6H4NH3Cl m ClC6H4NH2Cl2Fe

ZnHCl

KOH

[H]+ 4 CH3 CH CH2CH3

CH2 NH2(B)

CH3 CH CH2CH3

CN Naancol

CH3 CH (CH2)2CH3

NH2 CHCl3 KOH+ + CH3 CH (CH2)2CH3

N C3 3KCl H2O3+ +(C)

CH3 CH (CH2)2CH3

N C [H]4+ CH3 CH (CH2)2CH3

NH CH3(D)

NH2

CH3COCl+

NHCOCH3

HCl+(A)

NHCOCH3

HNO3H2SO4+

NHCOCH3O2N

NO2

H2O+

(B)2 2

NHCOCH3O2N

NO2

HNO3+ H2SO4

NHCOCH3O2N

NO2

NO2H2O+

(C)

NHCOCH3O2N

NO2

NO2H2O+

NH2O2N

NO2

NO2CH3COOH+

(D)



b/

c/

d/

1.16/ T benzen, hy lp s tng hp 2,4,5trinitroanilin bng 2 phng php Gii: Phng php 1:

[m ClC6H4 N N]BF4 m ClC6H4FNaNO2HBF4phn ng Schiemann

to

HNO3C6H6 C6H5NO2 C6H5NH3Cl C6H5NH2 ZnHClKOH ddBr2

NH2

Br

Br

Br

N

Br

Br

Br

N.Cl

Br

Br

Br

NaNO2 HCl

C2H5OH khan

HNO3 ZnHClC6H5CH3 C6H5COOH m O2NC6H4COOH m HOOCC6H4NH3Cl

[O]

KOH NaNO2 HClNH2

COOH

N

COOH

N.Cl CN

COOHKCN H2O

H+ COOH

COOH

CH3 CH3

NO2

CH3

NH2

CH3

NHCOCH3

CH3

NHCOCH3NO2

HNO3H2SO4

1. Fe/HCl2. KOH

CH3COCl HNO3H2SO4

thu phn

CH3

NH2NO2

CH3

NNO2

N.Cl

CH3

NO2

CH3

NH2

NaNO2 HCl

C2H5OH khan

1. Fe/HCl2. KOH

Cl2Fe

Cl

HNO3H2SO4

ClNO2

NO2

NH2NO2

NO2

NH3

NH3ClNO2

NO2

HCl

HNO3H2SO4

NH3ClNO2

NO2O2N

KOH

NH2NO2

NO2O2N



Phng php 2:

1.17/ Lp s tng hp ra cht ng ho hc c tn thng thng l saccarin t toluen v cc tc nhn v c cn thit khc:

Gii:

Saccarin ngt gp 500 ln ng ma.

HNO3H2SO4

NO2

NO2

(NH4)2SNH2

NO2

CH3COClNHCOCH3

NO2

HNO3H2SO4

NHCOCH3

NO2NO2

O2NNH2

O2N

NO2NO2

thu phn

NH2CO

SO2(Saccarin)

NH2CO

SO2

CH3

HOSO2Cl

CH3SO2Cl

CH3SO2NH2

NH3NaOHKMnO4

COONaSO2NH2

HCl



CHNG II: HP CHT D VNG 2.1/ Gi tn cc hp cht sau:

2.2/ Vit cng thc cu to ca nhng cht sau: a/ 2,5imetylfuran b/ 2Bromthiophen c/ 2,5imetylpirol d/ 2Aminopiriin e/ Piriinsunfoaxit 2.3/ So snh tnh baz trong dy sau v gii thch

Hp cht K hiu pKa Piriin A 5,2 2aminopiriin B 6,9 3aminopiriin C 6,1 4aminopiriin D 9,2 2metylpiriin E 6,9 3metylpiriin F 5,7 Piperiin G 8,3

2.4/ Hy iu ch cc cht sau bng cch ung nng hp cht 1,4icacbonyl vi cc tc nhn v c thch hp (phng php thng dng iu ch d vng 5 cnh). a/ 3,4imetylfuran b/ 2,5imetylthiophen c/ 2,3imetylpirol Gii: a/

b/

c/

NH COOHO CH3 S COCH3

N

NO2

N CH3 N

SO3H

a/ b/ c/

d/ e/ f/

CH3 CH CHCH CH

CH3

O O

CH3 C CC C

CH3H

OHOHH

O

CH3H3CP2O5H2O

2,3-imetylbutanial ienol 3,4-imetylfuran

CH2 CH2C CCH3 CH3O O

P2S5H2O

ienol

HC CHC CCH3OHOH

CH3 S CH3CH3

hexan-2,5-ion 2,5-imetylthiophen

CH2 CHC CH CH3O O

CH3

ienol

HC CC CHOHOH

CH3CH3

NH CH3

CH3

3-metyl-4-oxopentanal 2,3-imetylpirol

(NH4)2CO3



2.5/ T piriin v cc ng phn picolin, hy iu ch: a/ 3aminopiriin (bng 2 phng php) b/ 3xianopiriin (bng 2 phng php) c/ 2 xianopiriin. Gii: a/ Phng php 1:

Phng php 2:

b/ Phng php 1:

Phng php 2:

c/ 2aminopiriin khng iazo ha theo cch thng thng v khng th chuyn thnh hp cht xiano. Khi , nhm xiano c iu ch t amit l tt nht.

2.6/ Khi cho etylaxeto axetat, fomanehit v hiroxylamin ung nng vi nhau trong khng kh, ngi ta thu c mt piriin th vi hiu sut cao. l hp cht no? Vai tr ca hiroxylamin?

Nu thay bng ietyl malonat th phn ng c xy ra tng t nh trn khng? Ti sao?

Gii: etylaxeto axetat c cng thc cu to l:

N

HNO3H2SO4 N

NO2 ZnHCl N

NH3.Cl

N

NH2OH

N

CH3 KMnO4H +

1/2/ N

COOH SO2ClN

COCl

NH3N

CONH2 Br2, NaOH

N

NH2

N

NH2

N

N N.ClNaNO2 HCl

Cu2(CN)2N

CN

N

CONH2

N

CNP2O5H2O

N CH3

KMnO4H +

1/2/ N COOH

SO2ClN COCl

NH3N CN

P2O5H2O

NH3

N CONH2

CH2 COOC2H5CCH3O



Trong hp cht ny th nguyn t H trong nhm CH2 tng i linh ng do c 2 nhm ht electron. V vy, n d dng tham gia phn ng vi CH2=O:

Hiroxylamin c vai tr tng t nh NH3, dng ngng t hp cht icacbonyl to d vng ca nit:

2.7/ Hy tng hp 2metoxifuran t metylfuroat v cc tc nhn cn thit khc. Gii: Furan l d vng 5 cnh in hnh v khng ging piriin, n khng tip nhn phn ng th nucleofin. Tuy nhin, hoalogen c th th c nu c nhm th lm bn hp cht trung gian do tc dng ht electron nh COOH hay COOR


Gii: a/

H3C

C2H5OOC

O

H

CH2O CH2

H3C

C2H5OOC

O CH3

COOC2H5

OCH3

COOC2H5

O

H

H2O

N

COOC2H5C2H5OOC

CH3CH3OH

NH2 OH to

N CH3CH3

COOC2H5C2H5OOC

O COOCH3Br2

O COOCH3BrCH3ONaCH3OH O COOCH3CH3O

OH1/Cu, quinolin, to2/ OCH3O

COOHNH2 ClCH2COOH

HCl A B Cto

H2OCO2 C8H7ON (D)a/

COOH

NH2ClCH2COOH HCl+

COOH

NH CH2COOH(A)+

H2/Ni

H3O PCl5

P2O5 Pd

A

B

C D

E F G

to

+to

CH2Cl

OCH3OCH3

KCNb/

D



b/

COOH

NH CH2COOH+t

oH2OCH

C

NHCOOH

O

(B)

+CHC

NHCOOH

O

CH2C

NH

O

CO2(C)

CH2C

NH

O

chuyn v CHC

NH

OH

(D)CH2Cl

OCH3OCH3

KCN+

CH2CN

OCH3OCH3

KCl+

(A)

CH2CN

OCH3OCH3

+

(A)

H2 Ni

CH2

OCH3OCH3

CH2 NH2

2

(B)

CH2CN

OCH3OCH3

H3O+

CH2COOH

OCH3OCH3

NH4+H2O+

(C)

PCl5

CH2COOH

OCH3OCH3

++

CH2COCl

OCH3OCH3

POCl3 HCl+

(D)



2.9/ T piriin v cc cht bo bt k, hy lp s tng hp cc cht sau: a/ 2pirion b/ 2(2aminoetyl)piriin Gii:

2.10/ T fufuran v cc cht v c cn thit khc, hy lp s iu ch: a/ Etyl5brom2furoat b/ 1,2,5tribrompentan Gii: a/

b/

+

(D)(B)

CH3OOCH3

NH2

O CCl

CH2 OCH3

OCH3 CH3ONHC

CH2 OCH3

OCH3OCH3O

(E)

P2O5 CH3ON

CH2 OCH3

OCH3

CH3OCH3O

NHC

CH2 OCH3

OCH3OCH3O

(F)

H3ON OH

b/ PCl3N Cl

NaCH(COOC2H5)2N CH(COOC2H5)2

1/ OH2/

O CHO O COOH[O] C2H5OH

H2SO4 O COOC2H5Br2

O COOC2H5Br

O CHOH2Ni O CH2OH

HBrCH2Br

Br Br

Pdto

CH3ON

CH2 OCH3

OCH3

CH3OCH3O

CH3O

N

CH2 OCH3

OCH3

(G)papaverin

NC2H5O

N OC2H5

H3ON OH

a/

N CH2COOHSO2Cl

N CH2COClNH3

N CH2CONH2

LiAlH4N CH2CH2NH2



2.11/ Indol v nhiu dn xut ca n c iu ch t phenylhirazon. l nhng phng php tng hp theo Fischer. Vit phng trnh phn ng iu ch iodol t phenylhirazon ca axit pyruvic (CH3COCOOH). Gii: Theo phn ng Fischer:

2.12/ Pirol b kh bng Zn trong CH3COOH thnh pirolin c cng thc phn t C4H7N a/ Vit 2 cng thc cu to c th c ca pirolin. b/ Chn ng phn ng tho mn iu kin sau: Khi ozon phn s thu c C4H7O4N (X). X c th c tng hp t 2 mol axit monocloaxetic v 1 mol NH3. Gii:

Khi ozon phn th: ng phn A cho sn phm l: HOOCCH2CH2NHCOOH (C) ng phn B cho sn phm l: HOOCCH2NHCH2COOH (D). Ch c D mi c to thnh t 2 mol axit monocloaxetic v 1 mol NH3 theo phn ng sau:

Vy dng phn cn tm l (B). 2.13/

NH NH2 O CCH3

COOH+ NH N C COOHCH3

H2O+

phenylhirazon ca axit pyruvic

NH N C COOHCH3

ZnCl2N

COOH

H

+

axit indol-2-cacboxylic

NCOOH

H

to

NH

CO2+

indol

H2+

Cng 1, 2

Cng 1, 4Zn/HAcN H

N H

N H

2,3-ihiropirol (A)

2,5-ihiropirol (B)

NH3 CH2 COOHClCH2HOOC Cl + + HOOC CH2 NH CH2 COOH



a/ Piriin c b ankyl ha theo FridellCrafs hay khng? Ti sao? b/ T piriin, hy iu ch 2nbutylpiperiin. Gii: a/ Phn ng th electrofin ca piriin tng t nh dn xut b ng ha nhn benzen. Phn ng th electrofin nh nitro ha, sunfo ha, halogen ha di iu kin khc nghit hn, ng thi piriin khng tham gia phn ng FridelsCrafts. b/

NLiC4H9

N C4H9 N C4H9LiHH2Ni



CHNG III: GLUXIT 3.1/ V 2 cu dng gh ca metylDiopyranoz c cng thc Fischer di y. Cu dng no c nng lng thp hn? V sao?

Gii:

Trong 2 cu dng trn th cu dng 1C bn hn v cc nhm OH u c lin kt e. 3.2/ Diopyranoz, trong dung dch axit long to ra mt cch nhanh chng mt glicozit trung gian. Trong phn ng ny, nhm OH C1 v C6 phn ng vi nhau (hnh di). V cu dng gh thch hp ca Diopyranoz v dng glicozit trung gian c to thnh trn. Ti sao phn ng tng t ca hay Dglucopyranoz li km hn nhiu.

Gii: C 2 cu dng gh ca Diopyranoz nh sau:

Trong 2 cu dang trn th ch c cu dng 1C mi c th to c glicozit trung gian v c kh nng to thnh vng 5 cnh t 1 lin kt a C1 v C6. DGlucopyranoz c 4 cu dng gh nh sau: Trong 4 cu dng ca DGlucopyranoz ch c 1 cu dng 1C mi c kh nng to glicozit, trong khi cu dng ny li l cu dng km bn nht trong 4 cu dng. V vy kh nng phn ng ca DGlucopyranoz km hn nhiu so vi Diopyranoz.

OH

HH

CH2OH

OCH3H

HOHO OH

HO

H

H

HOCH3

OH

OH

OHH H

CH2OH

Cu dng 1C Cu dng C1

OCH3HHHOOHHHHO

HCH2OH

O

HHOHHOOHHHHO

HCH2OH

O

HHHOOHHHHO

HCH2

OOH2O

H

OH

HH

CH2OH

HH

HOHO OH

OHO

H

H

HH

OH

OH

OHH OH

CH2OH

Cu dng 1C Cu dng C1

OH

HH

CH2HH

HOHO OH

O

Glicozit trung gian

OOH

OHOH

CH2OH

OHH

HH H

HO

HO

HO

OHOH

H

H

HH H

CH2OH

Cu dng 1C Cu dng C1



3.3/ a/ S quay h bin l g? b/ Nhng thc nghim no chng t c s quay h bin? c/ Cc metylglucozit c quay h bin khng? Gii thch? d/ Khi metyl ha Dglucoz bng ru metylic c mt hiro clorua thu c 2 sn phm l Dmetylglucozit v Dmetylglucozit. Hai sn phm ny thuc loi ng phn no ca nhau? Dng cng thc Fischer v Haworth biu din. 3.4/ T Dglucoz, hy lp s tng hp cc cht sau y: a/ metylDglucoz b/ 2,3,4,6tetrametylDglucoz c/ 2,3,4,6tetraaxetylDglucopyranozyl bromua d/ pentaaxetylDgluconitrin. Gii: a/

3.5/ Cht ng A c cng thc phn t C6H12O6. T A tin hnh tng hp theo phng php KilianiFischer thu c 2 heptoz c cng thc phn t C7H14O7 l B v C. Dglucoz cng tin hnh nh trn v cng thu c 2 heptoz c cng thc phn t C7H14O7 l E v F. B v E b oxi ha vi HNO3 cho cng 1 axit khng quang hot, c cng thc C7H12O9. Xc nh cng thc cu to ca A, B, C, E, F.

OOH

OHOH

CH2OH

HH

HH H

OHO

HO

HO

OHH

H

H

HH OH

CH2OH

Cu dng 1C Cu dng C1

D-Glucoz + CH3OH HCl khan metyl-D-glucoz

D-Glucoz + (CH3)2SO4 pentametyl-D-glucozNaOH H2OHCl Sn phmb/D-Glucoz + (CH3CO)2O HBr khanpentaaxetyl-D-glucoz Sn phmCH3COOHc/

D-Glucoz + (CH3CO)2Od/ H2N OH CH3ONa H C NOH C N (Sn phm)OCOCH3HHCH3COOOCOCH3HOCOCH3H

CH2OCOCH3



3.6/ Gi tn v vit phng trnh phn ng iu ch ozazon t cc monosaccarit sau y:

Vit phng trnh phn ng ca 1 trong 3 cht trn vi dung dch AgNO3/NH3; Cu(OH)2 nhit thng; Cu(OH)2 un nng; dung dch nc brom. Gii: (A) l Dglucoz; (B) l manoz; (C) l galactoz 3.7/ Hon thnh s phn ng sau:

Gii:

3.8/ Khi cho Dglucoz tc dng vi H2 c Ni lm xc tc thu c Dsobit (ru 6 ln ru). Khi cho Dglucoz tc dng vi HNO3 thu c axit glucaric (axit 2 ln). Tm cc ng phn cht u v cht cui. Biu din cc cht theo cng thc chiu Fischer v xc nh cu hnh tuyt i ca tng nguyn t cacbon. Gii:

CHOOHHHHOOHHOHH

CH2OH

CHOHHOHHOOHHOHH

CH2OH

CHOOHHHHOHHOOHH

CH2OH(A) (B) (C)

OCH2OH

CH3IKOH

1/2/

A B CNH2OHHCl lo nga/

OCH2OH

CH3OHHCl khan E F

(CH3)2SO4 NaOH

b/

OCH2OH

OH

OHOHHO

D-glucopyranoz

CH3IKOH

1/2/

HCl (l)a/

OCH2OCH3

OCH3

OCH3OCH3CH3O

OCH2OCH3

OCH3

OCH3OHCH3O

OHCH2OCH3

OCH3

OCH3CH3O

CHONH2OH

COCH3HHCH3OOCH3HOHH

CH2OH

NOH

OCH2OH

OHHOOH

HO

D-antropyranoz

b/O

CH2OH

OCH3HOOH

HOO

CH2OCH3

OCH3CH3OOCH3

CH3OCH3OHHCl khan

(CH3)2SO4 NaOH

COOHOHHHHOOHHOHH

COOH

CHOOHHHHOOHHOHH

CH2OH

CH2OHOHHHHOOHHOHH

CH2OH

HNO3 H2Ni

axit glucaric (2R,3S,4R,5R)-glucoz sobit



Glucoz c 4C* vi 2 u mch l 2 nhm th khc nhau, khng c s i xng phn t nn c 24 ng phn quang hc. (8 dy thuc D v 8 thuc dy L). Sobit v axit glucaric vn c 4C* (chn), nhng 2 u li c 2 nhm th ging nhau nn c s lng ng phn quang hc nh nhau: S ng phn hot ng qiang hc l 2(n1) (Vi n=4, l s chn) S ng phn khng hot ng quang hc l 2(n2)/2 Vy tng s ng phn quang hc l 2(n1) + 2(n2)/2 = 10 3.9/ Nh nhng phn ng no c th thc hin c nhng bin i sau:

Gii: a/ Dng phng php KilianiFischer

CHOOHHHHOHHOOHH

CH2OHD-galactoz

COHHHHOHHOOHH

CH2OH

N

xianhirin

CHHOHHOHHOOHH

CH2OH

N

xianhirin

H2O H

H2O H

H2O

H2O

COOHOHHHHOHHOOHH

CH2OH

COOHHHOHHOHHOOHH

CH2OH

COHHHHOHOHH

CH2OH

O

O

lacton

Na/Hg

Na/Hg

CHOHHOHHOHHOOHH

CH2OHD-taloz

CHHOHHOHOHH

CH2OH

O

O

lacton

CHOHHOHHOOHH

CH2OH

HCN

b/ Dng phng php ca Wohl

CHOOHHHHOHHOOHH

CH2OH

CHOHHOHHOOHH

CH2OH

a/ b/

CHOHHOOHHHHOHHO

CH2OH

CHOOHHHHOHHO

CH2OH

CHOCC OHHC HHOC HHOCH2OH

HHO

L-glucoz

NH2OH

CH=NCC OHHC HHOC HHOCH2OH

HHOOH

oxim

CCC HAcC AcHC AcHCH2OH

HAcN

(CH3CO)2OH2O

CCC OHHC HHOC HHOCH2OH

HHON

CH3ONaCHCl3

CH3ONaCHOC OHHC HHOC HHOCH2OH

NaCNCH3OH



3.10/ Vit cng thc Haworth v cng thc cu dng cho cc isaccarit sau: a/ 6(Dglucopyranozito)Dglucopyranoz b/ 4(Dgalactopyranozito)Dglucopyranoz c/ 4(Dallopyranozito)Lantropyranoz d/ 6(Dgalactopyranozito)Dfructofuranoz 3.11/ thit lp cu trc ton phn ca mt isaccarit phi bit: a/ Dng monosaccarit hp phn b/ Dng vng cho mi monosaccarit trong isaccarit (furanoz hay pyranoz) c/ V tr monosaccarit ny so vi monosaccarit kia d/ Cu hnh anome ( hay ) ca lin kt . Hy ly v d minh ho cho nhng iu kin trn. 3.12/ Saccaroz cn c tn l 2(Dglucopyranozito)fructofuranozit. a/ Hy biu din cng thc theo Haworth v cu dng ca saccaroz. b/ Khi thu phn Saccaroz thu c nhng sn phm g? c/ Ly cc sn phm thu phn trn cho tc dng vi phenylhirazin d s thu c nhng sn phm g? Vit phng trnh phn ng. 3.13/ Trong mt ma c mt cht ng l (+)rafinoz c cng thc phn t l C18H32O16. Khi thu phn n bng axit thu c cc sn phm l Dfructoz, Dgalactoz v Dglucoz. Khi thu phn bng men galactozia cho galactoz v saccaroz. Khi thu phn bng men invecta (men thu phn saccaroz) cho Dfructoz v isaccarit melebioz. Khi metyl ha ri thu phn cho cc sn phm l: 1,3,4,6tetraOmetylDfructoz; 2,3,4,6tetraOmetylDgalactoz v 2,3,4triOmetylDglucoz. T cc d kin trn, hy lp lun suy ra cu to ca rafinoz. Gii: ng (+)rafinoz c cng thc phn t l C18H32O16. Khi thu phn n bng axit thu c cc sn phm l Dfructoz, Dgalactoz v Dglucoz chng t n l mt trisaccarit c to thnh t 3 phn t monosaccarit ni trn. Khi metyl ha ri thu phn cho cc sn phm l: 1,3,4,6tetraOmetylDfructoz; 2,3,4,6tetraOmetylDgalactoz v 2,3,4triOmetylDglucoz.



Chng t phn t c cc lin kt glucozit ti cc v tr C s 2 ca Dfructoz; C s 1 ca Dgalactoz v C s 1; 6 ca Dglucoz. V vy phn t glucoz phi nm gia. Khi thu phn bng men galactozia cho galactoz v saccaroz chng t lin kt glucozit c to thnh t C s 1 ca Dgalactoz vi C s 6 ca Dglucoz. T suy ra mt lin kt glucozit cn li phi c to thnh t C s 1 ca Dglucoz phi lin kt vi C s 2 ca frutoz, iu ny hon ton ph hp vi vic thu phn bng men invecta (men thu phn saccaroz) cho Dfructoz v isaccarit melebioz. Vy t ta c th suy ra cu to ca rafinoz nh di y:

3.14/ Trong mt ong c mt cht ng khng c tnh kh l melexitoz c cng thc phn t l C18H32O16. Khi thu phn hon ton cho Dfructoz v Dglucoz. Khi thu phn khng hon ton cho Dglucoz v isaccarit turanoz. Khi thu phn bng men khc cho saccaroz Khi metyl ha ri thu phn cho cc sn phm l: 1,4,6triOmetylDfructoz v 2 phn t 2,3,4,6tetraOmetylDglucoz T cc d kin trn, hy lp lun suy ra cu to ca melexitoz. Gii: ng melexitoz c cng thc phn t C18H32O16, khi thu phn cho Dfructoz v Dglucoz chng t n l mt trisaccarit c to thnh t 2 monosaccarit ni trn. Khi metyl ha ri thu phn cho cc sn phm l 1,4,6triOmetylDfructoz v 2 phn t 2,3,4,6tetraOmetylDglucoz, chng t phn t Dfructoz to 2 lin kt glucozit C s 2 v s 3 vi 2 phn t Dglucoz. Mi phn t glucoz u to lin kt glucozit C s 1. Khi thu phn khng hon ton cho Dglucoz v isaccarit turanoz. Khi thu phn bng men khc cho saccaroz chng t 2 phn t Dglucoz u dng Dglucoz.

OOH

OH

CH2OH

OCH2OH

OO

CH2

HO O

OH

OH

OH

OH

HO

Cu to ca rafinoz

HOH2C



Vy t ta c th suy ra cu to ca melexitoz nh di y:

Cu to ca melexitoz

O

OH

CH2OH

OCH2OH

HO OOH

OH

OCH2OH

OHOH

HO

O

HOH2C



CHNG IV: AMINOAXITPROTEIN 4.1/ Tm cc ng phn aminoaxit c cng thc phn t C4H9O2N (ch vit vi nhm amin bc nht). Gi tn chng theo danh php IUPAC. Ch r cc ng phn hot ng quang hc v biu din tng cp i quang bng cng thc chiu Fischer. 4.2/ tng hp cc aminoaxit, ngi ta chn mt anehit tc dng vi axit malonic trong dung dch amoniacru. Da trn phng php ny, hy tng hp axit aminovaleric. Gii:

4.3/ Lp s tng hp L(+)alanin t L()serin:

Gii:

4.4/ Hai ng phn A v B c cng thc phn t C9H11O2N, chng u tan c trong axit v kim. Khi A v B tc dng vi NaNO2 trong HCl thu c 2 cht tng ng A/ v B/ u c cng thc C9H10O3, trong ch c B/ c tnh quang hot. Khi un nng A/ v B/ u thu c mt cht c cng thc phn t C9H8O2. Khi oxi ha tip cht ny th thu c axit terephtalic v CO2. Hy xc nh cng thc cu to ca A, B v vit cng thc Fischer ca cp i quang. Gii: Hp cht c cng thc phn t C9H8O2 (X), khi oxi ha thu c axit terephtalic v CO2 nn X phi c cng thc cu to l:

X c to thnh t A/ v B/, ng thi B/ c tnh quang hot nn cng thc cu to ca A/ v B/ l:

CH3 CH2 CHNH2

CH(COOH)2 CO2 CH3 CH2 CHNH2

CH2COOH

CH3 CH2 CHONH3 CH3 CH2 CH OH

NH2

H CH(COOH)2

COOHHH2N

CH2OH

COOHHH2N

CH3L-(-)-serin L-(+)-alanin

COOHHH2N

CH2OH

COOHHH2N

CH3L-(-)-serin L-(+)-alanin

CH3OH HCl

COOCH3HH3N

CH2OH

PCl5COOCH3

HH3NCH2Cl

1/ NaOH2/ H2, to

COOH (X)CHCH2

COOHCH2CH2HO COOHCHCH3OH(A') (B')

*



T gi thit v kt qu trn, ta c th suy ra cng thc cu to ca A v B l:

Cng thc chiu Fischer cp i quang ca B nh sau:

4.5/ Tin hnh Naxetyl ha cc aminoaxit c th dn n sn phm vng gi l 5oxazolon hay azlacton theo phn ng sau:

Hy vit c ch cho s hnh thnh azlacton trong iu kin . Gii:

4.6/ tng hp aminoaxit, trc ht c th cho glyxin tc dng vi anhirit axetic thu c 5oxazolon hay azlacton (C4H5O2N). Sn phm ngng t ny phn ng vi anehit trong mi trng baz cho mt dn xut d b thu phn ha, hiro ha v

COOHCH2CH2H2N COOHCHCH3NH2(A) (B)

*

HH2NCH3

COOH

H NH2CH3

COOH

(S) (R)

(CH3CO)2O H2N CH COOHR

CH3COONa+O

CN O

R

H3C

(CH3CO)2O H2N CH COOR

CH3COONa+ CH3COOHO

C

N

R O

CH3

H O

OOH

C

NC

R O

CH3OH

O

C

NC

R O

CH3



thu phn thu c mt aminoaxit RCH2CH(NH2)COOH t anehit l RCHO (S thu phn ch n thun l cng nc, sau axit axetic c to ra). Theo cch trn, hy vit cc phn ng to thnh phenylalanin. Gii: Trc ht to sn phm azlacton nh bi (4.5) nh sau:

Azlacton ny c nhm CH2 vi 2 nguyn t H linh ng (nhm metylen linh ng) nn d ngng t croton ha vi anehit to ni i C=C:

4.7/ Hy vit cc giai on c bn tng hp peptit t aminoaxit. Ly v d minh ho cho mi giai on. 4.8/ Vit cng thc cu to ca cc peptit sau: a/ GlyLysPheCysAlaNH2. b/ TreIleMetLeuNH2. 4.9/ S thoi phn peptit theo Edman l phng php phan tch cho aminoaxit c lin kt cui m khng ph hu mch peptit cn li. Peptit u c x l vi phenylisothioxianat C6H5N=C=S, tip theo cho phn ng vi axit to phenylthiohiantoin v mt peptit vi phn cn li t hn mt aminoaxit. Hy vit cc giai on c th ca phng php ny. Gii: Phng php Edman: Phn tch nhm amin cui mch Cho peptit tc dng vi phenyl isothioxianat, khi nhm NH2 t do s phn ng, sau thu phn vi hiroclorua trong dung mi hu c, khi lin kt peptit vn c bo ton v ch c aminoaxit th b phn ct dng vng phenylthiohiantoin. Tch ly sn phm v phn tch bng sc k. Qu trnh tip tc n khi phn ct hon ton peptit.

O

C

NC

O

CH3

O

C

NC

O

CH3

Ph CHOH2O

O

C

NC

O

CH3

CHPh

H2H2O

1/2/ Ph CH2 CH COOHNH2

N C SPh

NH2CHC

RO

NHCHRC O

NHCHC

RO

NHCHRC O

CNH

S

Ph

HClNH2CHRC O C N

CN

C

Ph

SO

HR

H

+

Phenylthiohiantoin



4.10/ T cc cht protein thc vt, ngi ta tch ra c mt cht Y c cng thc phn t C5H10O3N2. Kt qu nghin cu chng t rng Y c cha 1 nhm amino. Khi un nng Y vi dung dch kim thy gii phng NH3 v to thnh mui ca axitaminoicacboxylic c cng thc phn t C3H5(NH2)(COOH)2. Khi tin hnh phn ng thoi phn Hoffman dn xut axetyl ca Y ri thu phn s to ra axit ,iaminobutyric. T cc d kin trn, hay suy ra cng thc cu to ca Y v vit phng trnh phn ng minh ho. Gii: Khi tin hnh phn ng thoi phn Hoffman dn xut axetyl ca Y ri thu phn s to ra axit ,iaminobutyric, chng t dn xut axetyl ca Y phi c cng thc cu to nh sau:

T kt qu trn v gi thit chng t cng thc cu to ca Y nh sau:

Phng trnh phn ng: T vit 4.11/ Xc nh cng thc cu to ca cht c cng thc phn t C3H7O2N v cc d kin sau: C tnh cht lng tnh. Khi phn ng vi HNO2 tch ra nit. Khi tc dng vi etanol to thnh hp cht C5H11O2N. Khi un nng n to thnh hp cht C6H10O2N2. Gii: p s:

4.12/ Xc nh cng thc cu to ca cht c cng thc phn t C5H11O2N v cc d kin sau: C tnh cht lng tnh. Tc dng vi etanol to thnh hp cht c cng thc phn t C7H15O2N. Khi ung nng s tch ra NH3 v chuyn thnh hp cht m khi oxi ha n s to thnh axeton v axit oxalic. Gii: p s:

HOOC CHNHCOCH3

CH2 CH2 C NH2O

HOOC CHNH2

CH2 CH2 C NH2O

(Glutamin)

CH3 CH COOHNH2

C CH2 COOHCH3CH3

NH2



4.13/ Lp s iu ch: a/ Valin t isobutanol b/ Alanin t etilen c/ Axit3aminopropanoic t axetilen Gii: a/ S dng phng php Stricker


Gii:

A1 A2 A3 A4 A5CH3 CH CHOCH3

HCN NH3 HCllo ng

PCl5 (CH3CO)2Oa/

thu phnCH2 CH2HOCl KCN NH3C1 C2 C3 C4 C5HBrc/KCNHBr D1 D2 D3CH3 CH CH COOH 4[H]d/

B1 B2 B3 B4CH2 CH CH2 COOH HBr HClNH32b/ un nng

CH3 CHCH3

CH2 OH CH3 CHCH3

CHO CH3 CHCH3

CH CNNH2

H2O, H CH3 CHCH3

CH COOHNH2

[O] HCN,NH3

CH CH CH2 CH Cl CH2 CH CN CH2 CNCH2BrHCl KCN HBrperoxitc/

CH2 CNCH2H2N CH2 COOHCH2H2NNH3 H2O, H

(A1) (A2)

CH3 CH CHOCH3

HCN NH3 HCllo ng

a/ CH3 CH CHCH3 OH

CN CH3 CH CHCH3 NH2

CN

(A3) (A4) (A5)

(CH3CO)2OCH3 CH CHCH3 NH2

COOH PCl5 CH3 CH CHCH3 NH2

COCl CH3 CH CHCH3 NHCOCH3

COCl

CH2 CH2HOH CH3 CH2OH

CH3 CHOb/[O] HCN,NH3 CH3 CH

NH2CN

H2O, H CH3 CHNH2

COOH



b/

CH2 CH2HOCl CH2 CH2OH Cl

CH2 CH2OH CN

KCN HBr CH2 CH2Br CN

CH2 CH2NH2 CN

thu phn CH2 CH2NH2 COOH

c/ NH3

(B1) (B2)CH2 CH CH2 COOH HBr CH3 CH

BrCH2 COOH

NH32 CH3 CHNH2

CH2 COONH4

(B3) (B4)HCl un nngCH3 CH

NH2CH2 COOH CH3 CH CH COOH

KCNHBr(D1)

CH3 CH CH COOHd/ CH3 CHBr

CH2 COOH

(D2) (D3)4[H]CH3 CH

CNCH2 COOH CH2 CH

CH3CH2 COOHH2N



CHNG V: POLIME 5.1/ Trnh by c ch trng hp stiren khi dng xc tc khc nhau l: a/ Benzoylperoxit b/ AlCl3 + HCl c/ KNH2 5.2/ Hy gii thch ti sao khi polime ha propen theo c ch cation li cho polime c s sp xp u ui l ch yu m khng phi l u u hoc ui ui. 5.3/ Nhng cht no c th cho vo caosu thin nhin to ra lin kt ngang? Hy ly mt vi v d minh ho cho phn ng xy ra. Gii: C th c 3 loi cht cho thm vo cao su to lin kt ngang 1/ Dng lu hunh nguyn t

S ni mch xy ra nguyn t H so vi ni i hoc cng lu hunh vo ni i to mng khng gian. 2/ Lu ha bng hp cht cho lu hunh (Khng phi l lu hunh nguyn t) Ankylphenol polisunfit iisopropyl xantogenisunfit ibutyl xantogenisunfit imocfolinyl isunfit Cc hp cht ny khi un nng s sinh ra cc hp cht trung gian c cha lu hunh, cc hp cht trung gian ny s tn cng vo ni i ca mch polime trong iu kin nhit cao ri khu mch polime nh cc lin kt ngang.

C CH CH2CH2CH3

Sx C CH CHCH2CH3 SH

+x-1S

mch cao su thin nhin

Sx

C CH CHCH2CH3 SH

C CH CHCH2CH3

SH+ ZnO

H2O

C CH CHCH2CH3

S

C CH CHCH2CH3 S

ZnZnS

C CH CHCH2CH3

S

C CH CHCH2CH3 S

CH2 CCH3

SHCH2 CH2

CH2 CCH3

SCH2 CH2

CH2 CS

CH3CH2 CH2

CH2 CCH3

CH2 CH2

CH2 CS

CH3CH2 CH2



3/ Lu ha khng bng lu hunh hay hp cht cha lu hunh. l nhng hp cht d phn tch thnh gc t do v cc hp cht hu c 2 chc. i vi cao su thin nhin hay s dng icumel peroxit, pcrezolcn i vi cao su tng hp th hay dng hiro peroxit, icumel peroxit, ch peroxit Cch to lin lit ngang nh sau: u tin l tch hiro t mch i phn t ca caosu. Hiro b tch ra nhm metylen so vi lien kt i. N to thnh gc t do trong i mch, ri cc i ch lin kt trc tip vi nhau to thnh lin kt CC. V d vi caosubunaS

Ngoi 3 phng php nu trn, i vi caosu tng hp cn c th un nng trc tip nhit 200OC trong vng 12 gi trong mi trng khng c oxi cng to lin kt ngang CC. ng thi cng c th dng tia (vi ngun Co60) cng to lin kt ngang CC. 5.4/ Cho cc monome sau y, hy vit cc phng trnh phn ng trng hp iu ch polime tng ng. Gi tn cc polime . a/ Butaien1,3 b/ Isopren c/ Propilen d/ Acrylonitrin e/ Clopren f/ Metylmetacrylat g/ Stiren h/ vinylclorua i/ Teflon k/ Etilen l/ Acrylamit m/ Axit acrylic 5.5/ T than , vi, nc, nc bin; hy lp s tng hp cc polime sau:

5.6/ Vit phng trnh phn ng to thnh polime t cc monome sau: a/ Phenol v fomanehit b/ Etylenglicol v axit terephtalic c/ Ure v fomanehit d/ Hexametylen iamin v axit aipic e/ H2N(CH2)6NH2 v ClCO(CH2)10COCl f/ H2N(CH2)6NH2 v O=C=N(CH2)4N=C=O Cc phn ng trn thuc loi phn ng trng hp hay trng ngng.

CH2 CH CH2C6H5

CH CH CH2 CH2 CH CHC6H5

CH CH CH2peroxit, to

CH2 CH CH CH CH CH2C6H5

CH2 CH CH CH CH CH2C6H5

CH2 CH CHC6H5

CH CH CH2CH2 CH CHC6H5

CH CH CH2

CH2 CH ;C6H5

CH2 CH ;Cl

CH2 CH ;OH

CH CH CH2CH2 ; CH C CH2CH2 ;Cl



5.7/ Trnh by c ch ca phn ng trng hp gc. Cc yu t nh hng n tc phn ng v khi lng phn t ca polime. 5.8/ Hy tm cch tng hp mt polieste v mt poliamit t anhirit sucxinic v cc tc nhn thch hp khc.

Gii:

5.9/ Mt nilon c iu ch t xiclohexanon bng cch x l vi hiroxylamin, sau cho vo axit mnh. Monome c polime ho nhit trn 250OC v c bit c mt t nc. Vit cc phn ng xy ra. Gii:

Phn ng to polime l phn ng trng hp m vng vi xc tc l mt t nc. 5.10/ V mt l thuyt, c th c bao nhiu ng phn polibutaien, bao gm c ng phn cu to v ng phn cu hnh. Gii: cis1,4polibutaien trans1,4 polibutaien isotactic1,2 polibutaien syniotactic1,2 polibutaien atactic1,2 polibutaien S kt hp bt k ca dn 1,2 vi dng 1,4 5.11/ Stiren c polime ha nhanh chng khi un nng vi s c mt ca peroxit. Vit c ch cho giai on pht trin mch. Gii thch ti sao phenylaxetilen khng b polime ha trong iu kin tng t. Gii: Phenylaxetilen khng b polime ha trong iu kin tng t v gc to thnh l

C CHC6H5 R

O OOanhirit sucxinic

O OOHO CH2 CH2 OH O CH2 CH2 O C CH2

OCH2 C ]OH

OH[+

O OOH2N (CH2)6 NH2 NH CH2 CH2 NH C CH2

OCH2 C ]OH

OH[+

NHO

[ CO

(CH2)5 NH ] n caprolactam nilon-6 hay t caprolactam

O

H2N OHH2O

N OH

chuyn v Beckmann



Gc loi vinyl km bn hn so vi gc loi ankyl, v vy gc ny pht trin mch khng tt. 5.12/ Khi nghin cu cu to ca caosu thin nhin, ngi ta tin hnh ozonphn. S ozon phn s cho nhng sn phm chnh no? Bit rng n c thnh phn phn t l (C5H8)n hay:[CH2C(CH3)=CHCH2]n Kt qu phn tch Rnghen cho thy caosu thin nhin c cu hnh cis. Hy v mt on mch phn t caosu . Gii: Khi ozon phn thu c sn phm chnh l anehit levulinic:

CH3 C CH2O

CH2 CHO

(Theo kt qu nghin cu ca Harit t nm 1905) Ngoi ra cn thu dc mt s sn pm ph vi lng nh nh:HCHO, CH3CHO, CH3COCHO chng t mch polime l mch h (Stauiger1922) vi nhm cui mch l: CH3CH= v CH2=C(CH3)CH=CH2. Ngoi ra cn c anehit sucxinic OHCCH2CH2CHO chng t c mt lngnh isopren c s kt hp 4-4 (uiui) vi nhau. 5.13/ Tm cc phng php tng hp cc polime sau:

Gii: 1/ Vinilon

2/ Polipropilen

CH2 CH ][OH

CH2 CH ][CH3

CH2 CH2 S[ ]n n n

CH2 CH ][OH

nCH2 CH ][

OCOCH3n

+ nNaOH to nCH3COONa+

CH2 CH ][OH

nCH2 CH ][

ONan

+ nHOH to + nNaOH

CH2 CH ][OH

2n+ nHOHto + nRCHO

OO]CH2[

R

n

CH2 CH ][CH3

nnCH2 CHCH3

Tr.h

CH2 CH ][CH3

nCH2 CH ][

CNn + [H]

LiAlH4, H2O nNH3+

CH2 CH ][CH3

nCHCH3

ClCH2Cl + 2nNa + 2nNaCl



3/ Polietylenthioglicol

5.14/ Phng trnh Carothers: Cch thit lp, ngha. im to gel l g? Khi no th phn ng trng ngng cn bng khng to c im gel?

CH2 CH CH[CH3

CH2 ]CH3

Tr.hCH3nCH3 n

CH2 CH2 S[ ]nCH2 SCH2 Tr.hn

CH2 CH2 S[ ]nCH2 CH2 ClnCl nNa2S+ + 2nNaCl

CH2 CH2 S[ ]nCH2 CH2 SHnHS nH2S+

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