反応例 15.1 アルケンとアルキンへの求電子付加

ハロゲン化水素の付加

HCl

Cl

R.A. Pacaud< C.F.H. Allen, Org. Synth., Coll. Vol. 2, 336 (1943).

5~10 ˚C

76~86%

C CH2

CH3CH2

CH3 Me3SiCl

H2O

C CH3

CH3CH2

Cl

CH3+ HCl

98%

P. Boudjouk, B.-K. Kim, B.-H. Han, J. Chem. Educ., 74, 1223 (1997).

(CH3)3CCH CH2AcOH

(CH3)3CCHCH3

Cl

(CH3)3CCHCH3

OAc

(CH3)3CCHCH3

(CH3)2CCH(CH3)2

Cl

(CH3)2CCH(CH3)2+ HCl

+ +

+ +

1,2-!"#$%

35~40% 15~20% 40~50%

R. C. Fahey, C. A. McPherson, J. Am. Chem. Soc., 91, 3865 (1969).

KI, H3PO4

80 ˚C, 3 h

IH. Stone, H. Shechter,

Org. Synth., Coll. Vol. 4, 543 (1963).

88~90% ROHの付加（プロトン付加） 酸触媒水和反応

O

HCl. H2O

O OH

H+

H2O

HOCHO

G.F. Woods,

Org. Synth., Coll. Vol. 3, 470 (1955).

74~79%

アルコールの付加

O

OH

Me

Me

CH2Cl2

O

OCMe3

+

BF3·OEt2, H3PO4

86%

androstanolone

R.E. Ireland, T.H. O'Neil, G.L. Tolman, Org. Synth., Coll. Vol. 7, 66 (1990).

O OH

TsOH

O O

CO2Me

O O

CO2Me

HO O OMe

+

78~92%

1) EtMgBr

2) ClCO2MeH+ / MeOH

60~65%

+

R. A. Earl, L. B. Townsend, Org. Synth., Coll. Vol. 7, 334(1990).

PhOH, MeOH

H2SO4

MeOH

OMe

h!

F.P. Tise, P.J. Kropp, Org. Synth., Coll. Vol. 7, 304 (1990).

52~53%

!"#$%&'()*+,-./0123456789(+)-limonene

RCO2Hの付加

CH3

C CH2

CO2H

CO2H

H2SO4

CH3

CO2C(CH3)3

CO2C(CH3)3

+

A. L. McCloskey, et al., Org. Synth., Coll. Vol. 4, 261(1963).

HCO2H!

O H

O

+ (exo)

90.5~92.5%

D. C. Kleinfelter, P. von R. Schleyer, Org. Synth., Coll. Vol. 5, 852 (1973).

BF3·Et2O

AcOH

OAc OAc+

( ca. 90 : 10 )

52~56%

J. Meinwald, J. Crandall, W. E. Hymans, Org. Synth., Coll. Vol. 5, 863 (1973).

オキシ水銀化

CH3

+ Hg(OAc)2

OH

CH3H

HgOAc

H2O

Et2O

OH

CH3NaBH4

H2O, Et2ONaOH

J. M. Jerkunica, T. G. Traylor, Org. Synth., Coll. Vol. 6, 766 (1988).

CO2MeHg(OAc)2

MeOH

1) KBr

2) Br2

MeOCO2Me

NH2

MeOCO2Me

Br

1) HBr

2) NH3

MeOCO2Me

HgOAc

2) NH3

1) NaOH/H2O

HOCO2Me

NH2dl-serine

30~40% overall yield

81~86%

H. E. Carter, H. D. West,

Org. Synth., Coll. Vol. 3, 774 (1955).

ヒドロホウ素化

(CH3)2C CHCH3

BH3, THF(CH3)2CH CH

CH3

BHCH3(CH2)5CH CH2

(CH3)2CH CH

CH3

B (CH2)7CH3

NaOH, H2O2

CH3(CH2)7OH (CH3)2CHCHCH3

OH

2

2

+

65~75%

disiamylborane

H. Kono, J. Hooz, Org. Synth., Coll. Vol. 6, 919 (1988).

THF

[(CH3)2CHCH]2BH

CH3 OH1)

2) NaOH, H2O2

1) Li, EtNH2, Me2NH

2) H2O

+

+

82% 18%

E. M. Kaiser, R. A. Benkeser, Org. Synth., Coll. Vol. 6, 852 (1988).

CH3

BH3, THF

CH3

BHNaBO3•4H2O

H2O

CH3

OH

2(+)-!-pinene

G. W. Kabalka, J. T. Maddox, T. Shoup, K. R. Bowers, Org. Synth., Coll. Vol. 9, 522 (1998).

CH3

BH3, THF

CH3

BH

CH2CO2Me

CH2CO2Me

HO

2

(–)-!-pinene

J. J. Partridge, N. K. Chadha, M. R. Uskokovoc, Org. Synth., Coll. Vol. 7, 339 (1990).

アルキンの水和反応

C CH

OH

COCH3

OHHgO, H2SO4, H2O

60 ̊ C

65~67%

G.W. Stacy, R.A. Mikulec, Org. Synth., Coll. Vol. 4, 13 (1963).

Me

Me

OH

Me

HO

Me!

O

OHHO

Me

Me

Me

Me

O

HO

Me

Me

Me

Me

O

O

Me

Me

Me

Me

HgO, H2SO4, H2O

M.S. Newman, W.R. Reichle, Org. Synth., Coll. Vol. 5, 1024 (1973).

76~82%

+

ハロゲンの付加

Br Br Br

Br

Br2, CCl4

0 °C 96~98% J. R. Johnson, W. L. McEwen, Org. Synth., Coll. Vol. 1, 521 (1941).

Br

BrBr2, EtOH

CCl4–5 to –1 °C 95%

H. R. Snyder, L. A. Brooks, Org. Synth., Coll. Vol. 2, 171 (1943).

HO2CCO2H

HO2CCO2H

Br

BrBr2, H2O

!

72~84%

H. S. Rhinesmith, Org. Synth., Coll. Vol. 2, 177 (1943).

reflux

Ph CH CH C OCH2CH3

OBr2

CCl4, 0 °CPh

Br

Br

OCH2CH3

O

83~85% T. W. Abbott, D. Althousen, Org. Synth., Coll. Vol. 2, 270 (1943).

Ph CH CH C CH3

OBr2

CCl4, darkPh

Br

Br

CH3

O

52~57% N. H. Cromwell, R. Benson, Org. Synth., Coll. Vol. 3, 105 (1955).

OAc Br2

EtOH

Br

Br

OAcBr

H

OBr

OEt

OEt

62~64%

S. M. McElvain, D. Kundiger, Org. Synth., Coll. Vol. 3, 123 (1955).

OAcCH3(CH2)4BrCH3(CH2)4

Br OAc

Br2

CCl4 P. Z. Bedoukian, Org. Synth., Coll. Vol. 3, 127 (1955).

PhPh

Br2

EtOHPh

Br

Br

Ph KOH

EtOH

PhPh

77~81%66~69%

L.I. Smith, M. M. Falkof, Org. Synth., Coll. Vol. 3, 350 (1955).

PhPh

NBS

H2O, DMSOH

Br H

OH

PhPh

80~90%

A.W. Langman, D.R. Dalton, Org. Synth., Coll. Vol. 6, 184 (1988).

O O

Br2

O O

Br

BrH

HCHCl3 O

CO2H

70%

1) KOH, EtOH

2) HCl, H2O

82~88%

R. C. Fuson, J. W. Kneisley, E. W. Kaiser, Org. Synth., Coll. Vol. 3, 209 (1955).

CH3(CH2)4(CH2)7CO2H

Br2

CH3(CH2)4 (CH2)7CO2H

CH3(CH2)4 (CH2)7CO2H

Br

Br

Br

Brglycerol

2) NaOH, EtOH

!"

linoleic acid

#$%&'()

*+,$-./0123(

1) Zn, HCl, EtOH

3) H2SO4 J. W. McCutcheon, Org. Synth., Coll. Vol. 3, 526 (1955).

CH3CH2CH CHCH2CH CHCH2CH CH(CH2)7CO2H

CH3CH2CH CHCH2CH CHCH2CH CH(CH2)7CO2H

Br Br Br BrBr Br

CH3CH2CH CHCH2CH CHCH2CH CH(CH2)7CO2H

Br2

Et2O!"#$%&'()*+

1) Zn, HCl, EtOH

2) NaOH, EtOH

3) H2SO4linolenic acid,-./0+1

J. W. McCutcheon, Org. Synth., Coll. Vol. 3, 531 (1955).

HO

C8H17

HO

C8H17

BrBr

Br2, AcOH

NaOAc, Et2O

L. F. Fieser, Org. Synth., Coll. Vol. 4, 195 (1963).

CH3(CH2)7CH CH(CH2)7CO2CH3Br2

(CH2)7CO2HCH3(CH2)7

CH3(CH2)7CH CH(CH2)7CO2CH3

Br Br

methyl oleate1) KOH, MeOH

2) HCl33~42%

H. Adkins, R. E. Burks, Jr, Org. Synth., Coll. Vol. 3, 785 (1955).

CH3(CH2)7CH CH(CH2)7CO2HBr2

Et2OCH3(CH2)7CH CH(CH2)7CO2H

Br Br

(CH2)7CO2HCH3(CH2)7

oleic acid1) NaNH2

2) HCl

52~62% N. A. Khan, F. E. Deatherage, J. B. Brown, Org. Synth., Coll. Vol. 4, 851 (1963).

(CH2)8CO2HBr2, Et2O

0 °C(CH2)8CO2H

Br

Br (CH2)8CO2H1) NaNH2

2) HCl38~49%

N. A. Khan, Org. Synth., Coll. Vol. 4, 969 (1963).

O

CH3

CH3

O

CH3

CH3

Br2, CHCl3

CH2Cl2, –65 °C

Br

Br

L. A. Paquette, J. H. Barrett, Org. Synth., Coll. Vol. 5, 467 (1973).

O O

Br

Br Br

BrBr2, Et2O

–78 °C

E. Vogel, W. Klug, A. Breuer, Org. Synth., Coll. Vol. 6, 862 (1988).

O O Cl

ClCl2, Et2O

–30 to –10 °C

R. Paul, O. Riobé, M. Maumy, Org. Synth., Coll. Vol. 6, 675 (1988).

O

O

C(CH3)3

(CH3)3C

Cl2

CH3CO2H

O

O

C(CH3)3

(CH3)3C Cl

Cl

W. Weyler, Jr, W. G. Duncan, M. B. Liewen, H. W. Moore, Org. Synth., Coll. Vol. 6, 210 (1988).

OH

Cl

70~73%

HgCl2, NaOH

Cl2, HNO3, H2O

G.H. Coleman, H.F. Johnstone, Org. Synth., Coll. Vol. 1, 158 (1941).

CH3CH CHCHO CH3

CHO

OH

Cl

!

C C CHO

Cl

Cl

H

Cl

CH3

CH3CH CCHO

Cl

Cl2, H2O

Cl2

G.A. Ropp, W.E. Creig, V. Raaen, Org. Synth., Coll. Vol. 4, 130 (1963).

HOClOH

ClAcOH, H2O

H.B. Donahoe, C.A. Vanderwerf, Org. Synth., Coll. Vol. 4, 157 (1963).

共役ジエンへの求電子付加

Br

Br

Br Br+ Br2

+

1,2-!" 1,4-!"

–60 ̊ C 80~75 20~25

25 ̊ C 25 75

CS2

CHCl3

CCl4

hexane

Br

HBr

Br+ Br2

1,4-!"–15 ˚C

+

4852

1,2-!"

4555

5050

4654

L.F. Hatch, P.D. Gardner, R.E. Gilbert, J. Am. Chem. Soc., 81, 5943 (1959).

Br

Br

H H+ HBr

+

1,2-!" 1,4-!"

#$ 90 10

40 ̊ C 15 85

M.S. Kharasch, E.T. Margolis, F.A. Mayo, J. Org. Chem., 1, 393 (1936).

CH3NO2H

Cl

HCl

+ HCl

25 C̊96%

Y. Pocker, K.D. Stevens, J.J. Champoux, J. Am. Chem. Soc., 91, 4199 (1969).

Cl

HCl, 0 °C

R. B. Moffett, Org. Synth., Coll. Vol. 4, 238 (1963).

CH3NO2

D

Cl

DCl

+ DCl +

solvent temp./˚C

0

25

71.5 28.5

67.7 32.3

pentane –78 77.7 22.3

25 63.8 36.2

1,2-!" 1,4-!"

25 65.0 35.0AcOH

J.E. Nordlander, P.O. Owuor, J.E. Haky, J. Am. Chem. Soc., 101, 1288 (1979).