反応例 15.1 アルケンとアルキンへの 求 電子付加

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 CH

CH

CH

CH

3SiCl H₂O

C CH

CH

CH

Cl CH

+ HCl

98%

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

(CH

)

CCH CH

AcOH

(CH

)

CCHCH

Cl

(CH

)

CCHCH

OAc

(CH

)

CCHCH

(CH

)

CCH(CH

)

Cl

(CH

)

CCH(CH

)

+ HCl

+ +

+ +

1,2-!"#$%

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

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

KI, H

PO

80 ˚C, 3 h

I H. Stone, H. Shechter,

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

88~90%

ROH

酸触媒水和反応

O

HCl. H

O

O OH H

H

O

HO CHO

G.F. Woods,

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

74~79%

アルコールの付加

O

OH

Me Me

CH

Cl

O

OCMe

+

BF

·OEt

, H

PO

86%

androstanolone

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

O OH

TsOH

O O

CO

Me

O O

CO

Me

HO O OMe

+

78~92%

1) EtMgBr

2) ClCO₂Me H⁺ / MeOH

60~65%

+

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

PhOH, MeOH

H

SO

MeOH

OMe h!

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

52~53%

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

RCO

H

CH

C CH

CO

H CO

H

H₂SO₄

CH

CO

C(CH

)

CO

C(CH

)

+

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

HCO

H

!

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

CH

+ Hg(OAc)

OH CH

H HgOAc H

O

Et

O

OH CH

NaBH

H

O, Et

O NaOH

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

CO

Me

MeOH

1) KBr 2) Br₂

MeO CO

Me NH

MeO CO

Me Br

1) HBr 2) NH₃

MeO CO

Me HgOAc

2) NH₃ 1) NaOH/H₂O

HO CO

Me NH

dl-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

(CH

)

C CHCH

(CH

)

CH CH CH

BH

(CH

)

CH CH CH

B (CH

)

CH

CH

(CH

)

OH (CH

)

CHCHCH

OH

2

2

+ 65~75%

disiamylborane

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

THF

[(CH₃)₂CHCH]₂BH

CH₃

OH

1)

2) NaOH, H₂O₂

1) Li, EtNH₂, Me₂NH 2) H₂O

+

+

82% 18%

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

CH

BH₃, THF

CH

BH

NaBO₃•4H₂O H₂O

CH

OH

(+)-!-pinene

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

CH

BH₃, THF

CH

BH

CH

CO

Me

CH

CO

Me HO

(–)-!-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

COCH

OH HgO, H

SO

, H

O

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, H

SO

, H

O

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 Br ₂ , CCl ₄

0 °C _96~98%

J. R. Johnson, W. L. McEwen, Org. Synth., Coll. Vol. 1, 521 (1941).

Br Br

, EtOH Br

CCl

–5 to –1 °C _95%

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

HO

C

CO

H HO

C

CO

H Br

Br

, H

O Br

!

72~84%

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

reflux

Ph CH CH C OCH

CH

O

CCl₄, 0 °C

Ph Br

Br

OCH

CH

O

83~85%

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

Ph CH CH C CH

O

CCl₄, dark

Ph Br

Br

CH

O

52~57%

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

OAc

EtOH

Br Br

OAc Br

H

O Br

OEt OEt 62~64%

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

OAc

CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₄ Br Br OAc Br ₂

CCl ₄

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

Ph Ph

EtOH

Ph

Br Br

Ph

EtOH

Ph Ph

77~81% 66~69%

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

Ph Ph

NBS H₂O, DMSO

H

Br H OH

Ph Ph

80~90%

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

O O

Br₂

O O

Br H Br

H

CHCl₃

O

CO

H 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).

CH

(CH

)

(CH

)

CO

H

Br2

CH

(CH

)

(CH

)

CO

H CH

(CH

)

(CH

)

CO

H

Br Br

Br Br

glycerol

2) NaOH, EtOH

!"

linoleic acid

#$%&'()

*+,$-./0123(

1) Zn, HCl, EtOH

3) H₂SO₄

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

CH

CH

CH CHCH

CH CHCH

CH CH(CH

)

CO

H

CH

CH

CH CHCH

CH CHCH

CH CH(CH

)

CO

H Br Br Br Br Br Br

CH

CH

CH CHCH

CH CHCH

CH CH(CH

)

CO

H

Br₂ Et₂O

!"#$%&'()*+

1) Zn, HCl, EtOH 2) NaOH, EtOH 3) H₂SO₄

linolenic acid ,-./0+1

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

HO

C

H

HO

C

H

Br Br

Br₂, AcOH NaOAc, Et₂O

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

CH

(CH

)

CH CH(CH

)

CO

CH

(CH

)

CO

H CH

(CH

)

CH

(CH

)

CH CH(CH

)

CO

CH

Br Br

methyl oleate

1) KOH, MeOH 2) HCl

33~42%

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

CH

(CH

)

CH CH(CH

)

CO

H

Et₂O

CH

(CH

)

CH CH(CH

)

CO

H Br Br

(CH

)

CO

H CH

(CH

)

oleic acid

1) NaNH₂ 2) HCl

52~62%

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

(CH

)

CO

H

0 °C

(CH

)

CO

H

Br

Br (CH

)

CO

H

1) NaNH₂ 2) HCl

38~49%

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

O CH

CH

O CH

CH

Br

, CHCl

CH

Cl

, –65 °C

Br

Br

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

O O

Br

Br Br

Br

, Et

O Br –78 °C

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

O O Cl Cl

, Et

O Cl

–30 to –10 °C

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

O

O

C(CH

)

(CH

)

C

Cl

CH

CO

H

O

O

C(CH

)

(CH

)

C 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).

CH

CH CHCHO CH

CHO OH

Cl

!

C C CHO Cl Cl H Cl CH

CH

CH CCHO Cl

Cl₂, H₂O

Cl₂

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

HOCl

OH

AcOH, H₂O

Cl

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

+ Br

+

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

–60 ˚C 80~75 20~25

25 ˚C 25 75

CS

CHCl

CCl

hexane

Br

H Br Br

+ Br

1,4-!"

–15 ˚C

+

52 48 1,2-!"

55 45 50 50 54 46

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).

CH₃NO₂

H

Cl

H Cl

+ HCl

25 ˚C

96%

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).

CH

NO

D Cl

D Cl

+ 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 35.0

AcOH

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