Cac Bai Tap Luyen Tap Ve Hoan Thanh So Do Bien Hoa (1)

7/29/2019 Cac Bai Tap Luyen Tap Ve Hoan Thanh So Do Bien Hoa (1)

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OH

COOHNH(CH3CO)2O

A

AlCl3B

Br2 (CHCl3)

C D

E

LiAlH4

H2/Pd-C

Salbutamol

TRNG I HC S PHM H NI

THPT CHUYN CHUYN : HON THNH S BIN HO- THHC

DNH CHO HC SINH I TUYN CHNH THC

Cu 1: Hon thnh s :

NO

NO

Toluen

Cl2

FeCl3

F

SO2Cl2, AIBN

10 h, heatG

C7H7Cl

+ H

J

Butan-2-on

+ HCHO + K

J +

a salt, can not be isolated

MHCl

Clobutinol-hydrochlorid

HCl

N

(L)

(L)


2/23

Cu 2: Hon thnh s sau:

Cu 3:Hon thnh s :

O

COOH

+ ZnBrCH2COOC2H51.

2. H+, H2O

A

(C14H22O3 )

H+, H2O,

- C2H5OH, -H2O

B

(C12

H16

O2

)

isomerisation

C

(C12H16O2)

a derivate of benzene

C2H5OH/H++

D

(C14H20O2)

LiAlH4E

(C12H18O)

HBrF

(C12H17Br)

+ CH3CH(COOC2H5)2

-

Na+

G

(C20H30O4)

1. ester cleavage

2. decarboxilation

SOCl2

H

(C15H21OCl)

AlCl3

I

(C15H20O)

NaBH4

(C15H22O)

J+S, heat

cadaline

carvone

OH

A1. O3

2. H2O2/H+

BI2, OH

-

CHI3

CKMnO4

hotE

H2

D

H2SO4H2

GH2

H

HBr

F

limonene

cat

cat

cat

+

m t d n xu t c a benzen

ng phn ho

1. thu phn este

2. cacboyxyl ho


3/23

1.

cat: ngha l xc tc.

2. Tm cc cation sau y.

Cu 4: Hon thnh s :

OH OH

H+

K+-H2O

L+cyclisation

M+?

?


4/23

OH

COOEt

COOEt

PBr3A (C10H21Br)

NaOEt

in EtOH

+ A

2. H+,

B (C12H24O2)

B + SOCl2 C

+ C2H5OH

D (C14H28O2)

D

LiAlH4E

PBr3F (C12H25Br)

F + Mg G

EtOOC-(CH2)5CHOH

Zn/HCl

I J

dann H+, H2O

CrO3I

K

Ether

1. OH-, H2O

1. OH-, H2O

2. H+

dann: sau vi

Cu 5: Hon thnh s :

COOC2H

5

COOC2H

5

Cl

OO

+

?

A B

KOH/H2O1.

2. HAc, in EtOH (C6H10O2)- CO2

LiAlH4

1. TsCl/Pyridin

2. NaCN/DMSO

+ CH3MgI1.

2. H+/H2O (C6H12O)(C8H14O)

MCPBA

(C7H11N)

(C8H14O2)H+

unstable intermediate(C8H16O3)

via cyclisation

CDE

F

O

COOEt COOEt

OH

COOEt

OH

O

OH

OO

yeast, sugar

H2O 1

2

LDA

CH3I

CrO3

MCPBA

Baeyer-Villinger

oxidation

G(C9H14O4)

LiAlH4

H(C7H16O3)

a triol

+

PC

J

+H+,

(-)-frontalin

PC

KL M N

ng vngthng qua m t ch t trung gian


5/23

yeast: ln men.

Frontalin:

Cu 6: Hon thnh s :

O

O 12

3

45

6

7

8


6/23

Cu 7: Hon thnh:


7/23

Cu 8: Hon thnh:

Cu 9: Hon thnh:


8/23

Cu 10: Hon thnh:


9/23

LI GII CHUYN Hon thnh s . THHC


10/23

Cu 1:

A: 2 bp

B: 4 bp C: 3 bp

D: 3 bp

E: 2 bp

7.2. Mechanism: SN2 1 bp

7.3.Allocation 5 bp

7.4. R-salbutamol: 2 bp

7.5. Structures F to N

CH

CH

CH

OH

C

H2

OHCH

OH

CH

2

NH

CH3

CH3

CH3

OOH

O

O

OOH

OH

O

OOH

OH

O

Br

OOH

OH

O

N

OH

OH

OH

N

4.40

4.60

4.60

4.60

6.8-7.3

6.8-7.3

6.8-7.3

4.40

4.601.05

1.05

1.052.5

NH

OH

OH

OH H


11/23

F: 2 bp

G: 2 bp H: 2 bp

Mg

J: 2 bp K: 2 bp

M: 4 bp

N: 2 bp

7.6. Name of the reaction: Mannich 1bp

7.7. Mechanism: SE1bp

7.8. Mechanism: SR 1bp

7.9. chiral centres 2 bp

7.10. Stereoisomers:4 1bp Relationship: enantiomers/diastereomers 2 bp

Cu 2:

ClOH

N

**

Cl

Cl

Cl

Cl

MgCl

NH

ClO

N

MgCl+

ClOH

NH+

Cl-


12/23

A: 1, 5 bp B: 2 bp C: 1 bp D: 1 bp

E: 1 bp F: 1 bp G: 2 bp H: 1 bp

I: 2 bp J: 1 bp

Cu 3:

7.1. Strucutres A to H

A: 1 bp B: 1.5 bp C: 2 bp D: 2 bp

E: 1 bp F: 1.5 bp G: 1bp H: 1bp

7.2. stereo descriptors geraniol: E- 1 bp nerol: Z-

OH

CH2COOC

2H

5

CHCOOH CH2COOH COOC

2H

5

OH Br

COOC2H5

COOC2H5

ClOC

O OH

O

OH

O

O

OH

O

OH

OH

OHBr


13/23

OH

1 bp

7.3. structur of K +

1.5 bp

7.3. structur of L+

1.5 bp

7.3. structur of M+

2 bp

7.3. formulae + H2O -H+

1 bp

7.4. centre

1 bp

7.5. N 1

bp

7.5. O 1

bp

OH2+

+

+

*

OH

OH

O


14/23

7.6. mechanism 3 bp

Cu 4:

7.1. Name: 10-Methyloctadecansure 1 bp

7.2. configuration formula: 1 bp

7.3. A

1 bp

7.3. B

3 bp

OH

+

++ H2O

- H+

O

OH

Br

O

OH


15/23

7.3. C

1 bp

7.3. D

1 bp

7.3. E

2 bp

7.3. F

1 bp

7.3. G

1 bp

7.3. H

2 bp

O

Cl

O

O

OH

Br

MgBr

O

OOH


16/23

7.3. I

1 bp

7.3. J

2 bp

Cu 5:

Frontalin a pheromone of the bark beetle

6.1. Which substance is referred to in the case of the question mark above the arrow in the first step o

the synthesis?

strong base, e.g. NaOEt 1bp

6.2. Find the structures of the compoundsA, B, C, D, E, F and the unstable intermediate.

6.3. Determine the number of stereogenic centres in frontalin and mark them with * in the formula in thbox. How many stereoisomers has frontalin?

A 2bp B 2bp C 2bp

O

OO

O

O

COOEt

COOEtCOOH OH


17/23

D 3bp E 3bp F 1.5bp

Unstable intermediate 1.5bp frontalin: 1bp

stereoisomeres: 2 1bp

6.4. Attach the signals which are marked with a, b and c to the respective protons in frontalin. Thereb

combine the letters with the numbers of the C-atoms where the hydrogen-atoms which create th

signal, are bound to.

a: 2 H at C7 1bp b: 6 H at C2. C3. C4 1bp c: 6 H at C1. C5 1bp

6.6. Give the IUPAC-name of (-)-frontalin.

(1S. 5R)-1.5-Dimethyl-6.8-dioxa-bicyclo[3.2.1]octan 3bp

6.7. Determine the absolute configuration at C1 and C2 in the -hydroxyester.

(1R. 2S) 2bp

6.8. Find the structures of the compounds G, H,J, L, M and N.

G 1bp H 3bp

CN

OO

O

O

OH

OH

OO

* *

O

COOEt

O

O

COOEt


18/23

J 2bp L 2bp

M 2bp N 1bp

Cu 6:

OHOH

OH

OOHC

O

OH

O

O O

OO


19/23

Cu 7:

Cu 8:


20/23


21/23

Cu 9:


22/23

Cu 10:


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Cac Bai Tap Luyen Tap Ve Hoan Thanh So Do Bien Hoa (1)

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