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Bi tp Ha Hc nng cao chuyn Hu C Trang: 1***********************************************************************************************************************************************

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -Cu 1:Streptimidon l mt loi cht khng sinh c cng thc nh sau:

a. M t cc trung tm lp th caStreptimidon bng k hiu E, Z v R, S.b. Streptimidon c bao nhiu ng phn lp th, trong c bao nhiu ng phn enan v

bao nhiu ng phn dia.Cu 2: So snh v gii thch:

a. Nhit si ca cc cht sau: xyclopentan, tetrahirofuran v piroliin.b. mnh tnh baz ca: imetylamin, piperiin v piriin

Cu 3: Cht ()Nicotin l mt loi ankaloit c trong thuc l v c th c tng hp theo cch sau:

(1) Axit nicotinic (3-pyridincacboxylic) + SO2Cl2o

t nicotinyl clorua (C6H4ONCl)(2) Nicotinyl clorua + C2H5OCH2CH2CdCl G (C11H15ON2), mt xeton(3) G + NH3

o2H , xc tc, t H (C11H18ON2)

(4) H + HBrot I (C9H12N2) + etyl bromua

(5) I + CH3I, NaOH ()nicotin (C10H14N2)Xc nh cu trc ca ()nicotin v hon thnh cc phng trnh phn ng trn.

Cu 4: Cht hu c (Y)c loi bm m tng hp trong ma giao phi. (Y) cng c th c tnghp theo cch di y. Hy cho bit tn gi ca hp cht ny v hon thnh cc phng trnh phn ngxy ra:

(1) Hept-1-in + LiNH2 S (C7H11Li)

(2) S + 1-clo-3-brompropan T (C10H17Cl)(3) T + Mg, sau cho sn phm ln lt tc dng vi n-C10H21CHO, H+ U (C21H40O)(4) U + H2 xc tc Lindlar V (C21H42O)(5) V + CrO3 Y ( C21H40O)

Cu 5:Styryllacton c phn lp t thc vt c cng thc (hnh di).O

O

O

HO1

2

3

456

7

8

9

Vit cng thc cu dng cc cp ng phn i quang v gi tn styryllacton theo danh php IUPAC.

Hng dn giiHp cht:O

O

O

HO1

2

3

456

7

8

9

Tn: 8-hiroxi-7-phenyl-2,6-ioxabixiclo[3.3.1]nonan-3-onCng thc cu dng:

9 9

O

O

O

1

234

5 6 7

8OH

C6H51

23 4

567

8HO

H5C6 O

O

O

O

O

1

23

4

567

8 9HO

H5C6 O O

O

O

1

23

4

5 67

89OH

C6H5

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Phan Cng Huy 2009 - [email protected]

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Cu 6: Dng mi tn cong ch r c ch chuyn 7-ehirocholesterol (I) thnh vitamin D3 (II) v cho bitcu dng bn ca n. Bit trong cng thc di y: R l: -CH(CH3)-(CH2)3-CH(CH3)2

HO

R

(I) HO

R

(II

)

Hng dn gii:R

HO

H

CH2

HO

R

R

HO

as

to

HO

RCu dng bn: S-trans

2.

Cu 7: Hp cht A (C10H18O) c phn lp t mt loi tinh du Vit Nam. A khng lm mt munc brom v dung dch thuc tm long, cng khng tc dng vi hiro c xc tc niken, nhng li tc

dng vi axit clohiric m c sinh ra 1-clo-4-(1-clo-1-metyletyl)-1-metylxiclohexan.1. Hy xut cu trc ca A.2. Hp cht B (C10H20O2 ) c trong mt loi tinh du Nam M. T B c th tng hp c A bng

cch un nng vi axit.a. Vit cng thc cu to v gi tn B.b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng

tng hp A.3. Hp cht B thng c iu ch t C (2,6,6-trimetylbixiclo[3.1.1] hept-2-en) c trong du

thng. Dng cng thc cu to, vit phng trnh phn ng v ch r cc lin kt ca C b t ra.4. Trong cy long no c hp cht D tn l 1,7,7-trimetylbixiclo[2.2.1]heptan-2-on (hay l campho).

Vit s cc phn ng tng hp D t C v cho bit c ch ca giai on u.5. V cu to ha hc, cc hp cht A, B, C v D trn c c im g chung nht? Minh ha vn

tt c im trn cc cng thc cu to ca chng.

Hng dn gii:1. Xc nh cng tc cu trc ca A(C10H18O) 2 =- A khng lm mt mu dung dch nc brom v dung dch thuc tm long chng t trong A

khng c ni i hay ni ba;- A khng tc dng vi hiro trn cht xc tc niken chng t trong A khng c nhm chc

cacbonyl;- A tc dng vi axit clohiric m c sinh ra 1-clo-4-(1-clo-1-metyletyl)-1-metylxiclohexan,

trong A c vng no v c lin kt ete.

=> Suy ra cng thc cu trc ca A

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Cu dng bn

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O

CH3CH3

CH3

CH3

H3CCH3

O

OO

B (C10H20O2) A (C10H18O)- H2O2. a.

Suy ra B l mt iol c b khung cacbon nh A

H+

H2OA

OH

OH

B

Gi tn B: 1-hiroxi-4-(-1-hiroxi-1-metyletyl)-1-metylxiclohexan

b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng.

C 2 dng trans v cis ca B u cu dng gh bn vng, tuy vy cu dng gh khng th tham giang vng m phi i qua dng thuyn km bn. Dng thuyn s tham gia phn ng SN1 ni phn t.

Cis-BA

OHOH HOOH

HO

H+ O

H+

H+

(+)OH

(+)

(+)

Trans-BA

OH

OH OH

OH

(+)OH

H+ O

H+

OH

3. Lin kt ca C b t cc ng chm chm:

H+

2 H2O

OH

OH

+

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HCl

D

H+

(+)chuyn v

H2O O

OHOCl

(+)

Cl-

4.

C

5. c im chung nht v cu to ho hc: mi phn t gm 2 n v isopren (hoc isopentan) ni vinhau.

Cu 8: Sau khi x l hn hp li ng hoc v tru c cha pentozan (C 5H8O4)n vi dung dch axit clohiric 12%ri tin hnh chng ct, nhn c cht lng A (C5H4O2) mu vng c mi thm. Cho A phn ng vi KOH riaxit ha th nhn c B (C5H4O3) v C (C5H6O2).

a. Vit phng trnh phn ng thu phn pentozan to thnh A v cng thc ca A, B, C.b. Vit phng trnh phn ng ca B tc dng vi C khi c xc tc axit.c. Hy trnh by iu kin nitro ho A nhn c D (C5H3NO4).

d. Vit phng trnh phn ng ca D tc dng vi: (I) ; (II).

(II)

NH-N

O

OH2N

(I)

S

NH

S

O

Hng dn gii:

1. Trong li ng v v tru c cha pentozan,khi un nng vi dung dch HCl 12% chuyn thnhpentoz ri tch nc cho fufurol

A C

2

OCHO

(C5H8O4)n HCl 12%CHO

(CHOH)3

CH2OH

- 3H2O

A(C5H4O2)

OCHO

KOH

OCH2OH

OCOOK

B

H3O+

OCOOK

OCOOH

H+b.

OCOOH +

OCH2OH

OCOOCH2

O

c. nitro ho A cn phi bo v nhm anehit bng (CH3CO)2O

(CH3CO)2O

OCH(OCOCH3)2

OCHO

Thc hin phn ng nitro ho, sau thu phn phc hi nhm CHO*****************************************************************************************************************************


Chuyn v

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H3O+

O

CH(OCOCH3)2 CHOO

O2NO

CH(OCOCH3)2O2NHNO3

D

d. Phn ng ca D vi I v II

D I

CHOOO2NN

ONH

OH2N

CHOO2N N N

ONH

O

II S

NH

S

O

CHOO

O2N CHO

O2NS

NH

S

O

Cu 9: Geniposit (hnh di) l mt hp cht c tch ra t qu dnh dnh. Thu phn geniposit sinh rahai sn phm l genipin v D-glucoz. Genipin tham gia phn ng to mu vi gelatin (y l c s phthin du vn tay trong k thut hnh s). Hy vit s phn ng to genipin v phn ng ca genipin vimt aminoaxit gii thch hin tng trn.

O

O

O

OH

HO

HO

HOH2C

COOCH3

CH2OH

Hng dn gii:Phn ng thu phn geniposit thu c genipin v D-glucoz

O

HOH2C O

COOCH3

O

HOH2C O

COOCH3

O

CH2OH

OH

HO

HO

H

HO

HO

O+

OH

OH

OH

Gelatin (c trong da) cu to t cc polipeptit, ly i din l mt aminoaxit nh glyxin, ta c phngtrnh:

+O

HOH2C O

COOCH3

H

H2N-CH2-COOH N-CH2-COOH

HOH2C O

COOCH3

H

sn phm c mu pht hin du vn tay trong k thut hnh s.Cu 10:Ngi ta phn lp c mt tetrapeptit (peptit A) t prothrombin ngi. Cu to ca peptit Ac tin hnh xc nh nh sau:a. Bng phng php Edman th nhn c trnh t aminoaxit ca peptit A l Leu-Glu-Glu-Val.

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b. tip tc xc nh cu to, ngi ta tin hnh in di trn giy pH 6,5 peptit A v mt peptit tnghp B (cng c trnh t aminoaxit l Leu-Glu-Glu-Val) th li nhn c qung ng di chuynkhng ging nhau, c th nh hnh di y:

Peptit A

Peptit B

0 1 2 3 n v dic. Khi thu phn hai peptit A v B bng HCl 6N 110oC, th c A v B u cho Leu(1), Glu(2), Val(1) ; nhngkhi thu phn bng kim th peptit B choLeu(1), Glu(2), Val(1) cn peptit A cho Leu(1), X(2), Val(1).Hy gii thch cc kt qu thc nghim xc nh cu to ca X v gi tn X theo danh phpIUPAC.

Hng dn gii:1. Xc nh cu trc ca X- Phng php Edman thc hin pH thp,bit c trnh t l Leu-Glu-Glu-Val.- in di pH 6,5 cho thy peptit A dch chuyn nhanh hn v pha cc dng(+), chng t A c in

tch m ln hn B,tnh axit ca A ln hn B.

- Khi thu phn trong mi trng HCl 6N 110oC th c A v B u thu c Leu(1), Glu(2) v Val(1).- Kt hp vi phng php Edman trn cho thy cc qu trnh ny thc hin mi trng axit mnh,

pH thp. pH thp phn t X b ecacboxyl ha, loi CO2 mt i 1 nhm COOH.- Khi thu phn bng kim peptit A to ra Leu(1),X(2) v Val(1),trong mi trng kim khng c qutrnh decacboxyl ho nn nhn c X(2).- Kt hp cc kt qu trh nghim cho thy X c thm 1 nhm COOH so vi Glu tc l khi loi 1 nhm

COO th X chuyn thnh Glu.X

CO2CH2 CH COOH

NH2

CH2HOOC

HOOC CH2 CHCH

NH2COOH

COOHX :Vy

Gi tn: Axit 3-aminopropan-1,1,3-tricacboxylicCu 11: Vit s phn ng oxi ha D-glucoz to thnh axit anonic v axit anaric, cng thcHaworth cc mono v i -lacton ca chng v gi tn cc lacton y.

Hng dn gii:

CHO

HO

OH

CH2OH

Br2 H2O

CH2OH

CH2OH

OH

OH

OHOH

OHHOHO

COOH

COOH

COOH

HNO3

OH

OH

OH

OH

HO

OH

O

C

O

O

OH

CH2OH

OH

OO

axit gluconic D- -gluconolacton

1,4-lacton caaxit glucaric

O

O

OH

OH

COOHOH

OO

OH

OH

3,6-lactoncaaxit glucaric1,4:3,6-dilactoncaaxit glucaric

COOHOH

OOHOOH

O

Cu 12:Cho s o phan ng:

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2,5

1,7

Vy X l:

3,6-lacton ca axit glucaric

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CH3C=O

C3H7

C2H5 H1. C6H5MgBr

2. H2OB

HBracC

(A)

a. Viet c che phan ng va cong thc cau tao cac san pham.b. Goi ten cac cau hnh cua B v C theo danh phap R, S.

Cu 13: Hay giai thch s hnh thanh nhanh chong 2,4,6-Br3C6H2NH2 (C) khi cho

p-H2N-C6H4-SO3H (A) hoac p-O2N-C6H4-COOH (D) tng tac vi dung dch ncbrom.Cu 14:Lam the nao thc hien chuyen hoa sau vi hieu suat tot nhat:

NH2

C

O

NH2

Cu 15: Hon thnh cc phng trnh phn ng sau:

a. CH3COCH3 + 2 EtOOC-COOEt NaOEt, HOEt E 30H O ,t+

F (C7H4O6, i xng)

b. CH3COCH2COOEt + CH2=CH-CHO NaOEt, HOEt G (C9H12O3)

c. CH3COCH2COCH3 + H2N-NH2 0t H (C5H8N2)

d. EtOOCCH2COOEt + 2CH2=CH-COOEt NaOEt, HOEt I NaOEt, HOEt K (C15H22O7)

e. EtOOCCH2COOEt + H2N-CO-NH2 0t L (C4H4N2O3)

Cu 16: Ancaloit c cha h vng piroliziin c gi l ancaloit piroliziin.

N Piroliziin

C khong 100 ancaloit piroliziin khc nhau c phn lp, trong cretronexin ln u tin c tch ra t thc vt vo nm 1909, nhng mi n nm1962 mi c tng hp trong phng th nghim theo s sau:

D

BrCH2COOEt, Na2CO3F (C10H15O4N)

KOEt H2, Pt

H(C10H17O4N)

1. H2O, OH-, t

0

2. H+I (C

8H

11O

3N)

E (C6H10O2NCl)

B (C14H21O7N) C (C11H17O5N)1. H2O, OH

-, t0

2. HCl

NaBH41. HCl

2. HOEt, HClD

G

EtOOC(CH2)2NHCOOEt + ietyl fumarat A (C16H27O8N)NaOEtNa

O

O

N COOEt

3. H2O

HO

G

NO

COOEtH

p

1. HOEt, H+

2. LiAlH4, THF

HO

N

HCH2OH

a. Hy vit cng thc cu trc ca A, B, C, E, F, H, I.b. Hy cho bit cc hp cht trung gian c hnh thnh khi chuyn t F sang Gc. Sn phm cui cng ca s trn c quang hot khng?

Cu 17: Reserpin l mt ancaloit c trong r cy ba gc, c dng cha bnhhuyt p cao. Cch y gn na th k Woodward tng hp ton phn

reserpin. Mt s giai on u ca cng trnh tng hp hu c ny nh sau:

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p-Benzoquinon (C6H4O2) + Axit (E)-penta-2,4-ienoic (1) A (C11H10O4)

4NaBH (2) B (C11H12O4) 6 5C H COOOH (3) C (C11H12O5) 3 2(CH CO) O (4) D (C11H10O4)

a. Vit phng trnh phn ng (1) v cng thc cu to ca A.b. L thuyt v thc nghim u cho bit A (sn phm chnh) sinh ra trong phn

ng (1) c t nht 2 nguyn t C* k nhau gi cu hnh S v cc nguyn t H C* u v tr syn i vi nhau. Hy vit cng thc lp th ca A.

c. Trong phn ng (1), ngoi cht A cn c th sinh ra my ng phn cu hnh?Ti sao? Dng cc k hiu lp th phn bit cc ng phn .d. B l sn phm chnh ca phn ng (2), khi un nh B vi anhirit axetic thu -

c lacton vi hiu sut cao. Vit cng thc cu to v cng thc lp th ca B;Gii thch. Dng cng thc cu trc vit s cc phn ng (3) v (4).

Cu 18: Hy thc hin dy chuyn ho sau:2-Metylpropanal + piperiin 0H ,t+ C9H17N MeCOCl C11H20ONCl

+

2H O,H MeCOCMe2CHOCu 19:T mt loi thc vt ngi ta tch c cht A (C10H12O2). A phn ng vidd NaOH to thnh cht B (C10H11O2Na). B phn ng vi CH3I cho cht C

(C10H11O(OCH3)) v NaI. Hi ca C phn ng vi H2 nh cht xc tc Ni chocht D (C10H13O(OCH3)). D phn ng vi dd KMnO4 trong H2SO4 to thnh axit3,4-imetoxibenzoic c cng thc 3,4-(CH3O)2C6H2COOH v axit axetic.1. Vit cng thc cu to ca A, B, C: bit rng A, B, C khng c ng phn

cis-trans, cc cng thc trong ngoc n trn v cng thc phn t.2. Vit phng trnh cc phn ng xy ra.Cu 20:Hp cht A (C18H18O2Br2) phn ng c vi dd NaOH nng. Cho hn hp sauphn ng tc dng vi dd axit v c long, thu c B (C9H9O2Br) v C (C9H11OBr).- Oxi ho B hoc C u thu c axit para-brom-benzoic.- Oxi ho trong iu kin thch hp C chuyn thnh B.

- T B thc hin chuyn ho theo s sau: B

Cl ,as2

D

oddNaOH,t

E

ddHCl

Go2 4H SO ,170 CH

(D cha 1 nguyn t Clo trong phn t, H c ng phn Cis-trans. Cc sn phmD, E, G, H u l sn phm chnh)

a. Vit cng thc cu to ca A, B, C, D, E, G, H v vit cc phng trnh phnng xy ra.

b. So snh nhit nng chy ca B v C. Gii thch.Cu 21: Hp cht hu c A c cng thc phn t C7H9N. Cho A phn ng vi C2H5Br(d), sau vi NaOH thu c hp cht B c cng thc phn t C11H17N. Nu cngcho A phn ng vi C2H5Br nhng c xc tc AlCl3 (khan) th to ra hp cht C c cngcng thc phn t vi B (C11H17N). Cho A phn ng vi H2SO4 (c) 180oC to hpcht D c cng thc phn t C7H9O6S2N, sau khi ch ho D vi NaOH 300oC ri viHCl s cho sn phm E (E c phn ng mu vi FeCl3). Mt khc, nu cho A phnng vi NaNO2 trong HCl 5oC, ri cho phn ng vi -naphtol trong dung dchNaOH th thu c sn phm c mu G.Xc nh cng thc cu to ca A, B, C, D, E, G v vit cc phng trnh phn ng(nu c) minh ho.Cu 22: Amyglain (k hiu l A) c cng thc phn t C20H27O11N l mt isaccaritthin nhin khng c tnh kh, ch cha lin kt -glicozit.- Khi thu phn A bng dung dch axit long th thu c glucoz v hp cht B

(C7H6O) lm mt mu nc brom.

- Khi un A vi dung dch axit c th thu c glucoz v hp cht C (C8H8O3).Oxi ho C bng dung dch KMnO4 ri axit ho th thu c D (C7H6O2) khng lmmt mu dung dch nc brom.

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- Cho A tc dng vi CH3I ly d (mi trng kim), thu phn (mi trng axit), richo cc sn phm tc dng vi HIO4 (d) th thu c 2,3,4,6-tetra-O-metylglucoz; 2,3-imetoxibutanial v metoxietanal.a. Hy xc nh cng thc cu to ca A, B, C, D.b. Hy gii thch s to thnh B khi thu phn A. Hp cht C c quang hot

khng? V sao?Cu 23: Epiclohidrin la mot epoxit, nguyen lieu chnh e che tao nha epoxidung lam keo dan kim loai, knh, sanh s. Epiclohidrin phan ng viC6H5MgBr tao thanh C6H5CH2CH(OH)CH2Cl.a. Xac nh cong thc cau tao cua epiclohidrin.b. Viet cac phng trnh phan ng khi cho epiclhidrin tac dung vi ru

etylic, dung dch NH3 va khi epiclohidrin b thuy phan trong moi trngkiem.

c. e ieu che nha epoxi, ngi ta un nong epiclohidrin vi bisphenol-A.Viet phng trnh phan ng. Bisphenol-A l (2,2-bis-[p-hidroxiphenyl] propan.

d. Khi tron nha epoxi noi tren vi mot amin a chc v du nh viN(CH2CH2NH2)3 th se thu c polime mang khong gian. Giai thch.

Cu 24:Axit fumaric v axit maleic c cc hng s phn li nc 1 (k1), nc 2 (k2).

Hy so snh cc cp hng s phn li tng ng ca hai axit ny v gii thch.Cu 25: Cho cc ancol sau: p-CH3-C6H4-CH2OH , p-CH3O-C6H4-CH2OH, p-CN-C6H4-CH2OH vp-Cl-C6H4-CH2OH..So snh kh nng phn ng ca cc ancol vi HBr v gii thch.Cu 26: Oxi ho hirocacbon thm A (C8H10) bng oxi c xc tc coban axetat cho sn phm B. Cht Bc th tham gia phn ng: vi dung dch NaHCO3 gii phng kh CO2; vi etanol (d) to thnh D ; unnng B vi dung dch NH3 to thnh E. Thu phn E to thnh G, un nng G nhit khong 1600C tothnh F. Mt khc, khi cho Bphn ng vi kh NH3 (d) cng to thnh F.Hy vit cc cng thc cu to ca A, B, D, G, E v F.Cu 27: Hp cht 2,2,4-trimetylpentan (A) c sn xut vi quy m ln bng phng php tng hpxc tc t C4H8 (X) vi C4H10 (Y). A cng c th c iu ch t X theo hai bc: th nht, khi c xc

tc axit v c, X to thnh Z v Q;th hai, hiro ho Q v Z.a. Vit cc phng trnh phn ng minh ha v tn cc hp cht X, Y, Z, Q theo danh php IUPAC.b. Ozon phn Z v Q s to thnh 4 hp cht, trong c axeton v fomanehit, vit c ch phn ng.

Cu 28: Cho s cc phn ng sau:

HCHO H2O

OH

OH-A B

NaCN

DMFC

O ClD1 + D2 + E (sn phm ph)

Hy vit cng thc cu to ca A, B, C, D1,D2 v E. Bit E c cng thc phn t C19H22O5N2.Cu 29: HSCH2CH(NH2)COOH (xistein) c ccpKa: 1,96; 8,18; 10,28. Cc cht tng ng vi n lHOCH2CH(NH2)COOH (serin), HSeCH2CH(NH2)COOH (selenoxistein), C3H7NO5S (axit xisteic).a. Hy xc nh cu hnh R/S i vi serin v axit xisteic.b. Hy qui kt cc gi trpKa cho tng nhm chc trong phn t xistein. Vit cng thc ca xisteinkhi pH = 1,5 v 5,5.c. Sp xp 4 amino axit trn theo th t tng dn gi tr pHI v gii thch s sp xp .Cu 30: Thy phn hon ton mt nonapeptit X thu cArg, Ala, Met, Ser, Lys, Phe2, Val, v Ile. Sdng phn ng ca X vi 2,4-initroflobenzen xc nh c Ala. Thu phn X vi trypsin thu c

pentapeptit (Lys, Met, Ser, Ala, Phe), ipeptit (Arg, Ile) v ipeptit (Val, Phe). Thu phn X vi BrCNdn n s to thnh mt tripeptit (Ser, Ala, Met) v mt hexapeptit. Thu phn vi cacboxypeptiaza cX v hexapeptit u cho Val. Xc nh th t cc amino axit trong X.Cu 31: Vit cc phng trnh phn ng thu phn metyl--D-galactofuranozit (A) v metyl--D-sobofuranozit(B) trong mi trng axit. (soboz: 2-xetohexoz; cu hnh C3 ca n v ca galactoz khc nhau).

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Cu 32: Arabinopyranoz (D-anopentoz c cu hnh 2S, 3R, 4R) c chuyn ha nh sau:

Ara (C5H10O5) B CCH3OH/H

+HIO4

H2O/H+Br2/H2O

1. LiAlH4

2. H2OD

E

H2O/H+

HOCH2-CH2OHHOCH2-CHO +

HOCH2-COOHCHO-COOH + V cu trc ca B, C, D v E.Cu 33: Hp cht A (C4H6O3) quang hot, khng tham gia phn ng trng bc, tc dng vi anhirit

axetic to ra dn xut monoaxetat. Khi un nng vi metanol, A chuyn thnh cht B (C5H10O4). Di tcdng ca axit v c long, B cho metanol v C (C4H8O4). C tc dng vi anhirit axetic to ra dn xuttriaxetat, tc dng vi NaBH4 tora D (C4H10O4) khng quang hot. C tham gia phn ng trng bc tothnh axit cacboxylic E (C4H8O5). X l amit ca E bng dung dch long natri hipoclorit to ra D-(+)-glyxeranehit (C3H6O3) v amoniac. V cu trc ca A, B, C, D v E.Cu 34: Xc nh cc cht t A n G v hon thnh cc phng trnh phn ng trong chui bin hasau:

KMnO4

(c nng) H2/Pt 1. CH3MgCl

C10H16 (G) Metyl xiclopentan 2. H3O+H2SO4(un nng)

C10H18O (F)3

1.Mg,ete HBr

5 92.

3. H O

C H Br(E)+

Xiclopentanon 6 5C H COOOH C5H8O (C)

Cu 35: Gii thch:a. Ti sao phn ng sau khng dng tng hp tert-butyl propyl ete.CH3CH2CH2ONa + (CH3)3CBr (CH3)3COCH2CH2CH3

Natri propoxit tert-butyl bromua tert-butyl propyl ete.b. Sn phm chnh ca phn ng ny l g.c. Hy ngh phng php tng hp tert-butyl propyl ete tt hn.

Cu 36: Hy sp xp dy cc cht sau theo th t tng dn tnh baz v gii thch: CO(NH2)2 ;

(CH3)4NOH ; CH3CH3CH3NH2 ; CH2=CHCH2NH2, p-CH3C6H5NH2 ; C6H5NH2 ; p-NO2C6H5NH2.Cu 37: Khi un nng 2-metylxiclohexan-1,3-ion vi but-3-en-2on trong dung dch kim ngi ta thuc mt hp cht hu c (sn phm chnh) c cng thc C 11H14O2. Hy vit cng thc cu to ca sn

phm ny v gii thch qu trnh to ra nCu 38: Gii thch ti sao 1,2-imetylxiclohexen ch phn ng cng trans vi HBr trong dung mi khng

phn cc nhng li cho phn ng cng cis v trans vi HBr trong mi trng axit. Cho bit cu trc casn phm.Cu 39:Qu trnh phn li ca mt aminoaxit n gin nh glyxin nh sau (b qua proton)

+ -3 2

+ -3 2 2 2

2 2

NH CH COO

NH CH COOH (B) NH CH COO

(A) NH CH COOH (C)(B')

1. Vit phng trnh biu th mi quan h gia cc hng s cn bng2. Tnh im ng in pHI ca glyxin bit: pK1 = 2,35 ; pK2 = 9,783. Biu th mi quan h gia:

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o o3 2 4 2 4

3

1.CH MgCl H SO ,t H SO ,t

6 12 6 10 6 122. H OC H O(A) C H (B) C H O(D)

+

K11 K22

K21K12

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Bai tap Hoa Hoc nang cao chuyen e Hu CTrang: 11************************************************************************************************************************************************

a. K1 vi K11 v K22b. K2 vi K21 v K22

Cu 40: Hp cht thin nhin X c cng thc phn t C7H14O6 l mt cht khng c tnh kh v khng tng phn ha c. Thy phn X bng HCl long thu c cht Y (C6H12O6) l mt monosaccarit ctnh kh. Oxi ha Y bng HNO3 long, nng thu c mt iaxit M (C6H10O8) khng c tnh quang hot.Lm gim mch ca monosaccarit Y chuyn nhm CH(OH)CHO thnh nhm CHO (thoi phnRuff) th thu c monosaccarit Z (C5H10O5). Z b oxi ha bi HNO3 long, nng cho iaxit N (C5H8O7)

c tnh quang hot. Cho X tc dng vi CH3Br trong mi trng baz sinh ra P. Cht P tc dng vi dungdch HCl long to ra Q ; cht hu cQ b oxi ha bi HNO3 long, nng thu c hn hp sn phmtrong c axit 2,3-imetoxibutanioic v axit 2,3-imetoxipropanoic.Xc nh X, Y, Z, M, NCu 41: Xt phn ng th: RCl OH ROH Cl + + c biu thc tc phn ng l: v = k[RCl] hocv k[RCl][OH ]=

a. Cho mt v d c th v RCl trong mi trng hp, gii thchb. S dung mi gii ca tert-Butyl bromua trong axit axetic xy ra theo c ch nh sau:

3 3 3 3

3 3 3 3 3 3

(CH ) CBr (CH ) C Br (1)

(CH ) C CH COO (CH ) COCOCH (2)

+

+

+

+

Hy gii thch ti sao, khi tng hm lng Natriaxetat th khng lm tng tc phn ng.Cu 42: imetyl ha iso-butilen (X) trong dung dch H2SO4 60% thu c hp cht A mch h c cngthc phn t l C8H16. Hiro ha A thu c B l 2,2,4-trimetylpentan. Nu dng Y l iso-butan tc dngvi X cng thu c B khi c xc tc HF

a. Vit cc phng trnh phn ng xy rab. Trnh by c ch phn ng X A v Y Bc. Thnh phn % ca B trong xng gi l g? ng dng ca B trong xng?

Cu 43: Hp cht A c CTPT C4H8O3 quang hot, tan tt trong nc to dung dch c mi trng axit.Khi b t nng A to ra cht B c CTPT C4H6O2 khng quang hot, t tan trong nc (dung dch c mitrng axit). B phn ng vi KMnO4 d hn A. Khi b oxi ha bng dung dch axit cromic long th cht

A bin thnh cht lng C c CTPT l C3H6O. Bit C c nhit si thp, khng lm mt mu dung dchKMnO4 nhng phn ng vi I2 trong NaOH to ra kt ta mu vng.Xc nh CTCT ca A, B, C v vit cc phng trnh phn ng xy ra.Cu 44:Hp cht A (C18H18O2Br2) phn ng c vi dung dch NaOH nng. Cho hn hp sau phn ngtc dng vi dung dch axit v c long thu c cht B (C9H9O2Br) v C ( C9H11OBr). Oxi ha B hoc Cu thu c axit p-Brombenzoic. Oxi ha C trong iu kin thch hp s chuyn thnh B. T B thc

hin chuyn ha sau: ( ) 2 4( )2 o oH SOCl ,as dd HCl

t 170 CB D E G H dd NaOH

Bit D cha mt nguyn t Clo trong phn t. Cc sn phm ghi trn s u l sn phm chnhVit CTCT ca A, B, C, D, E, F, G, H v vit cc phng trnh phn ng xy ra. G, H c ng phn hnhhc khng. So snh nhit nng chy ca B v C. Gii thch

Cu 45: Khi cho amoniac phn ng cng vi axetanehit thu c sn phm khng bn A, sn phm nyd b tch nc thnh B. B d dng trime ha cho sn phm C l triazin. Mt khc nu cho amoniacngng t vi fomanehit s thu c sn phm D (urotropin) c CTPT l C6H12N4. Cht D c kh nngtc dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht n mnh c dngtrong i chin th gii th II theo s : C6H12N4 + 3HNO3 E + 3HCHO + NH3.Xc nh A, B, C, D, E v vit cc phng trnh phn ng xy ra.Cu 46: Tch hn hp cc cht sau: hexan-2-on ; hexan-3-on ; axit fomic ; axit trietylaxetic

Cu 47: Vit cc phng trnh phn ng theo s sau: C (etilen glicol iaxetat)

2HCHOoP, t ,xt A 2

H ,xt B D (poliete)

E 2O ,xt F (axit a chc) 2( )Ca(OH) G

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cd

d

Trng ngng

+X

+ CuO, to

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Cu 48: Khi cho PVC tc dng vi Zn trong ru th tch ra c ZnCl 2 v thu c polime c cha20,82% clo. Polime khng cha ni i v khng c tnh do nh PVC. Kt qu trn cho bit g v cuto ca polime mi thu c. Tnh % mc xch vinyl clorua b tch clo bi Zn.Cu 49: X l - halogen xeton vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gil phn ng Favorski. - cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mtCH3ONa trong ete. Hy xc nh c ch ca phn ng ny.

Cu 50: Vit s iu ch cc cht sau y:a. 1,2,3 tribrmbenzen t axtilen v cc ho cht cn thit khc.

b. Axit m toluic t benzen v cc ho cht cn thit khc.Cu 51: Hy ngh c ch phn ng kh nc (H+) ca

a. Butan1ol to (trans)but 2enb. 3,3imetylbutan2ol to 2,3imtylbut 2en

Cu 52: Hon thnh cc s :

a. Tm A, B, C v hon thnh s sau:34 2 H OHIO ddBr Metyl glucopiranozit A B C

+

b. Tm cc cht A, B, C, D, E, F v vit cc phng trnh phn ng xy ra theo s sau:Na2Cr2O4

2 2

o3

Cl ,1mol H O

FeCl t ,PBenzen A B

(1 mol)

E Fe/HCl F

Cu 53: Hp cht hu c A c cng thc phn t dng CxHyOz trong oxi chim 29,0909% v khilng. Bit A c th phn ng vi dung dch NaOH vi t l 1:2, phn ng vi Br2 theo t l 1:3. Xc nhcng thc phn t v cng thc cu to ca A.Cu 54: So snh tnh baz ca cc cht sau v gii thch: CH3NH2, NH3, (CH3)2NH, C2H5NH2, C6H5NH2,(C6H5)2NH, NaOH, C2H5ONaCu 55: Vit cng thc cu to ca cc cht hu c c tn gi sau:

a. Spiro-[3,4]-oct-1-enb. (R)-3-clobut-1-en

Cu 56:Inden co cong thc phan t C9H8 co cac tnh chat sau:- Lam nhat mau dung dch nc brom, dung dch nc thuoc tm.- Hap thu nhanh 1 mol H2 tao thanh Indan (C9H10).- Tac dung vi H2 d (xt Ni, t0) tao hp chat C9H16.- B oxi hoa bi KMnO4/H2SO4 tao axit Phtalic

Xac nh Cong thc cau tao cua Inden. Viet cac phng trnh phan ng

xay ra.Cu 57: So sanh kha nang phan ng the electrophin cua Naphtalen viBenzen. So sanh kha nang phan ng (co giai thch) the electrophin vtr va v tr cua naphtalen. Viet cac phng trnh phan ng ieu chera cac dan xuat initronaphtalen va axit naphtalenisunfonic t naphtalen.Cu 58:Oxi ho 150 mg amiloz bi NaIO4 thu c 0,0045 mmol axit fomic.

a. Tnh s lng trung bnh cc gc glucoz trong phn t amiloz; bit rngkhi oxi ho 1 mol amiloz bng NaIO4, s gc glucoz u mch to ra 1 molaxit fomic, s gc glucoz cui mch to ra 2 mol axit fomic.

b. Vit s cc phng trnh phn ng xy ra.Cu 59: T CH4, cc cht v c, xc tc v cc iu kin phn ng cn thit, vit s iu ch cc chthu c sau: PPM, PVA, DDT

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O

ClCOOCH3

NaClCH3ONaete

HNO3

1:1

C D

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Cu 60:Vit s cc phng trnh phn ng chuyn D-glucoz thnh L-gulozc cng thc di

Cu 61:Hp cht A (C5H11O2N) l mt cht lng quang hot. Kh A bng H2 c xc tcNi s c B (C5H13N) quang hot. Cho B tc dng vi axit HNO2 thu c hn hp gmancol C quang hot v ancol tert-amylic (2-metyl-2-butanol). Xc nh cng thccu to ca A. Dng cng thc cu to, vit phng trnh cc phn ng to thnh B,C v ancol tert-amylic t A.Cu 62: Hp cht A (C5H9OBr) khi tc dng vi dung dch it trong kim to kt tamu vng.A tc dng vi dung dch NaOH to ra 2 xeton B v C cng c cng thc phn t

C5H8O. B, C u khng lm mt mu dung dch kalipemanganat lnh, ch c Bto kt ta mu vng vi dung dch it trong kim. Cho B tc dng vi CH3MgBr rivi H2O th c D (C6H12O). D tc dng vi HBr to ra hai ng phn cu to E v Fc cng thc phn t C6H11Br trong ch c E lm mt mu dung dch kalipemanganat lnh. Dng cng thc cu to, vit s phn ng t A to thnh B,C, D, E, F. Vit tn A v D theo danh php IUPAC.Cu 63: Monosaccarit A (t l glicoz A) c tn l (2S,3R , 4S , 5R)-2,3,4,5,6-pentahiroxihexanal. Khi un nng ti 1000C, A b tch nc sinh ra sn phm B ctn l 1,6anhiroglicopiranoz. Dglucoz khng tham gia phn ng ny. T A cth nhn c cc sn phm E (C5H10O5) v G (C5H8O7) theo s phn ng:

ABr

2H2O C CaCO

3 HNO3 GEDH

2O

2

a. Vit cng thc Fis ca A v B.b. A tn ti 4 dng gh (D-glicopiranoz). Vit cng thc ca cc dng v cho

bit dng no bn hn c?c. Dng cng thc cu dng biu din phn ng chuyn ho A thnh B. V sao D-

glucoz khng tham gia phn ng tch nc nh A?d. Vit cng thc cu trc ca E v G. Hy cho bit chng c tnh quang hot hay

khng?Cu 64: 2-(1-Hiroxipentyl)xiclopentanon (A) l cht trung gian trong qu trnh

tng hp mt cht dng lm hng liu l metyl (3-oxo-2-pentylxiclopentyl)axetat(B).1. Vit cng thc cu to ca A v s cc phn ng tng hp A t axit aipic

(hay axit hexanioic) vi cc cht khng vng v cc cht v c khc.2. Vit cng thc cu to ca B v s cc phn ng tng hp B t A v cc ho

cht cn thit khc.3. B c tt c bao nhiu ng phn cu hnh? Hy vit cng thc lp th ca

ng phn c cu hnh ton l R.4. pK ca este metyl ca glyxin l 7,70. y cng l gi tr ca K12. Tnh ba hng s cn bng cn li.5. Trong mi trng trung tnh th glyxin tn ti di dng ion lng cc hay phn t trung tnh, v sao.Cu 65 :Hat oc sam co oc to ten la coniin. Coniin co khoi lng phant bang 127 .v.C, cha 75,60% C, 13,38% H theo khoi lng. Coniinlamxanh quy tm am, khong lam mat mau dung dch Br2/CCl4 cung

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CHO

HHO

OHH

HHO

CH2OH

H OH

L-galuz

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khong lam mat mau dung dch thuoc tm. Khi ehidro hoa coniin th thuc chat A (C8H11N). Khi oxi hoa A th thu c mot hp chat d vong B cocong thc C5H4N-COOH.Biet rang trong ca hai phan ng tren khong co s ong hay m vongva phan t coniin khong co C bac ba.a. Xac nh cong thc cau tao cua coniin va cho biet bac amin cua

coniin A, B . V sao khoi lng phan t cua coniin, cua A, B eu la so

le.b. e tach lay coniin t hat oc sam vi hieu suat va o tinh khiet

cao nen chiet vi dung moi nao sau ay (co giai thch) : Nc, ruetylic, dung dch NaOH, dung dch HCl.

Cau 66: Hp chat A (C5H9OBr) khi tac dung vi Iod trong moi trng kiemtao ket tua mau vang. A tac dung vi dung dch NaOH tao ra hai xeton Bva C co cung cong thc phan t la C5H8O. (B) va (C) eu khong lammat mau dung dch KMnO4 lanh, ch co B tao ket tua mau vang khitac dung vi Iod trong moi trng kiem. Cho B tac dung vi CH3MgBr roivi nc th thu c D (C6H12O). D tac dung vi HBr tao ra 2 ong phan

cau tao E va F co cong thc phan t C6H11Br trong o ch co E lammat mau dung dch KMnO4 lanh. Dung CTCT, viet s o phan ng t Atao thanh B, C, D, E, F. Viet ten A va D theo danh phap IUPAC.

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