2013

()

2
:

___________________

* () 20 100 , 4 3, 5 14, 6
3 . . ()
() , . ,
.
. .
10 : 3511 : 35 (60) .
.
.
.

. .

< >
Ph
Pr
Rf
rt
sec- (s-)
tert- (t-)
THF
TLC
Ts

dimethyl sulfoxide
ethyl
diethyl ether
ethyl acetate
methyl
melting point
methanesulfonyl
normal
nucleophile

DMSO
Et
ether
EtOAc
Me
mp
Ms
nNu

acetyl
acetonitrile
acetic acid
aqueous
boiling point
butyl
benzoyl
dichloromethane
N,N-dimethylformamide

Ac
ACN
AcOH
aq.
bp
Bu
Bz
DCM
DMF

phenyl
propyl
retention factor
room temperature
secondary
tertiary
tetrahydrofuran
thin layer chromatography
p-toluenesulfonyl

< >

1
2
3
4
5
6
7

9 10 11 12 13 14 15 16 17 18

1H

2He

1.0

4.0

3Li
6.9

4Be

5B
10.8

6C
12.0

7N
14.0

8O
16.0

9F
19.0

10Ne

9.0

11Na

12Mg

13Al

14Si

15P

16S

17Cl

18Ar

23.0

24.3

27.0

28.1

31.0

32.1

35.5

39.9

19K
39.1

20Ca

21Sc

23V
50.9

24Cr
52.0

26Fe

27Co

30Zn

31Ga

32Ge

55.8

58.9

63.5

65.4

69.7

72.6

33As
74.9

34Se

54.9

28Ni
58.7

29Cu

45.0

22Ti
47.9

25Mn

40.1

79.0

35Br
79.9

36Kr
83.8

37Rb

38Sr

39Y

40Zr

41Nb

42Mo

43Tc

44Ru

45Rh

46Pd

47Ag

48Cd

49In

50Sn

51Sb

52Te

53I

54Xe

85.5

87.6

88.9

91.2

92.9

95.9

[98]

101.1 102.9 106.4 107.9 112.4 114.8

118.7

121.8

127.6

126.9

131.3

55Cs
56Ba
132.9 137.3

71Lu
72Hf
73Ta
74W
75Re
76Os
77Ir
78Pt
79Au
80Hg
81Tl
175.0 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4

82Pb
207.2

83Bi
209.0

84Po
[209]

85At
[210]

86Rn
[222]

87Fr
[223]

103Lr
[260]

88Ra
[226]

20.2

1
2
3
4
5
6
7

57La
138.9

58Ce
140.1

59Pr
140.9

60Nd
144.2

61Pm

[145]

62Sm
150.4

63Eu
152.0

64Gd
157.3

65Tb
158.9

66Dy
162.5

67Ho
164.9

68Er
167.3

69Tm
168.9

70Yb
173.0

89Ac
[227]

90Th
232.0

91Pa
[231]

92U
238.0

93Np
[237]

94Pu
[244]

95Am

96Cm

98Cf
[251]

99Es
[252]

101Md

102No

[247]

97Bk
[247]

100Fm

[243]

[257]

[258]

[259]

()

1. IUPAC <>
? [5]

3. (conformational isomer) <>

? [5]

< >

< >

IUPAC
.

Cl
H3C

Cl

H3 C

CH3

CH3

CH3
Br
H
H
OH
CH3

(2R,3R)-3-Bromobutan-2-ol

, ,

2. (formal
charge) 1 ? [4]

H3C

H
CH3

2,5-Dimethylhexane
H

H
H

CH3
s-Bu

CH3

CH3

1-Ethyl-2-methylcyclopent-3-ene

H3C

Cl

Cl

CH3
H3C C
CH3

N C O

C N

, ,

()
4. (alkene) A B
.

5. cyclohexene A F
. (,
.)

Cl

HCl
Ph

Ph

m-CPBA

H+
H2O

B
Br2, H2O

NaOH

<>
? [5]

1) OsO4
2) NaHSO3

< >
.

HIO4

(m-CPBA: m-chloroperoxybenzoic acid)

(rearrangement)
.

A F <>
.

B (methyl) 1,3-(shift)

? [5]

.
.

< >

B (optical activity) .

, ,

A D .

B E (diastereomer) .

C F (degree of unsaturation) 1.

, ,

()

6. <> E2 1-methylcyclohexene

8. (alkyne) C5H8

chloroalkane . <>

A C . (, A B

A B

.)

chloroalkane ? [6]
H2

Na/NH3()

C5H8

<>
KOH

Chloroalkane

Lindlar

1) O3

E2

2) H2O

Chloroalkane: 3

Cl

Cl

Cl

<>
? [5]
< >
.

A (vinyl carbanion)

A B (diastereomer) .

C CO2 .

7. -
( Keq > 1) <> , ?
[4]
< >

NH3

HC CH

NaNH2

HC CNa

HC CH

C2H5MgBr

HC CMgBr

HC CLi

HC N

HC CH

LiC N

HC CLi

C2H5OH

HC CH

C2H5OLi

HC CLi

H2C CH2

HC CH

H2C CHLi

C2H6

, ,

()
9. (chiral center)
? [5]

11. (optical activity)

? (, (enantiomer).)
[5]

Ph
HO
HO

HO
N

CH2OH
H
H
CH2OH

OH

POCl3

pyridine

HO

TsOH

Ph

H2, Pd/C

O
OEt

OH

CrO3
H2SO4, H2O

1) O3

10. (stereoisomer)
<> ? [5]
< >
H F

F H

H3C

CH3

H F

Cl

Cl

CH3

H3C

F H

Cl

Cl

HO

HO OH

HO OH

OH

, ,

OH

OH

2) Me2S

()

12. (electrophilic bromination)

<> < >.

13. <> ?
(,
.) [5]

<>

< >
Br
Br+

H+

Cl 1) HNO , H SO
3
2
4

Cl 2) HO

O2N

Cl

Cl

Cl

K2CO3,

< >

Cl
NH2

1) HNO3, H2SO4
2) H2, Pd/C
3) Cl2, FeCl3

<> ,
? [5]

1) EtCl, AlCl3

2) NBS, benzoyl peroxide

3) t-BuOK,

< >
O

NBS =

(transition state) C .

N Br
O

(exergonic reaction).
(rate-determining step)
(A C).

(1 ) R Me R H
.

, ,

()
14. A ? (,
.)
[5]

15. A B C D
. A B ?
(,
.) [5]

Cl
1) AlCl3

Cl

2) NaBH4
Cl

3) NaBH4

Br

2) H2SO4

B
O

Cl

HO

HO

O
H

O
H

OCH3

Cl
O

Cl

OH

Cl

1) CH3MgI (2 )

Cl

Cl

Ph

2) PhCH2Cl, K2CO3

3) TsOH

Cl

1) Br2

HO

Cl

OCH3

HO

O
H

O
OCH3

Cl
Cl

HO

()

16.
<> ? [5]

18.
? (, .)
[6]

< >
Cl AlCl3

(a)

(CH3)3CBr

H2O

(CH3)3COH

+ HBr

HCl

Cl
AlCl3

AlCl3

AlCl4

(b) (CH3)3CBr

C2H5OH

(CH3)3COC2H5 + HBr

OH
Cl

H2O

HCl

OH

Cl

H+

H2O

Cl

H
H2O

H
H

H
O

H3O

, ,

(a)

Cl

? [4]

(a)

Cl

acetone
KI
acetone

17. (a) (b)

(a)

KCl

KCl

KI

OH

(b)

(a)

H3O+

Cl

H+

(b)
O

H3O+

OH

Cl

(a)

Cl

Cl

(b)

Cl

(b)

Br

(b)

OH

O
H

(a)

(a)

(a)

(a)

(b)

(b)

(b)

(a)

(b)

(b)

(b)

(a)

(b)

(b)

(b)

(a)

(a)

(a)

(a)

(b)

(b)

(b)

(a)

(b)

(b)

(b)

(a)

(b)

(b)

(b)

()
19. ?
(,

20. cyclohexanol cyclohexene <>

< >.

.) [6]
<>

OMe

OMe

H2SO4

H2O

2) Zn(Hg), HCl
O

< >

OH

Cl

1) AcCl, AlCl3

() cyclohexanol (40 mL) ,

1) PhMgBr

65 % (15 mL) (dropping funnel)

2) TsCl, pyridine

3) t-BuOK

() (fractional distillation) 90
.

1) O3

() (separatory funnel) ,

2) Me2S

HO

3) LiAlH4

10 % Na2CO3 .

OH

() (beaker) , Na2SO4
(suction filtration) .

1) Hg(OAc)2, H2O
2) NaBH4
3) CrO3, H2SO4, H2O

() , (simple
distillation) 8085 .

1) 9-BBN

OH

? [5]

2) H2O2, NaOH

3) NaBH4
BH
9-BBN =

()

()

()

()

()

*

.