反応例 13.1 ハロアルカンの求核置換反応（SN2反応）...反応例 13.1...

反応例 13.1 ハロアルカンの求核置換反応（SN2反応）

シアノ化

+ KCN!"#$%&'(

+ KBrCH3(CH2)10CH2Br CH3(CH2)10CH2CN

J.R. Ruhoff, Organic Syntheses, Coll. Vol. 2, 292 (1943).

HOCH2CH2Cl + NaCN HOCH2CH2CN NaCl+

45-50 °C

!79-80%

E.C. Kendall, B. McKenzie, Organic Syntheses, Coll. Vol. 1, 256 (1941).

CH3CH2OCH2CH2Br NaCN+

!"#$%&'

140 °C

CH3CH2OCH2CH2CN

52-58%

NaBr+

G.C. Harrison, H. Diehl, Organic Syntheses, Coll. Vol. 3, 557 (1955).

C6H5CH2Cl NaCN C6H5CH2CN + NaCl

!-"#$%&'()80-90%

+

R. Adams, A.F. Thal, Organic Syntheses, Coll. Vol. 1, 107 (1941).

CH3

CH3

H3C

CH2Cl

NaCN+

!"#$%&'

100 °C

CH3

CH3

H3C

CH2CN

NaCl+

89-93%

R.C. Fuson, N. Robjohn, Organic Syntheses, Coll. Vol. 3, 557 (1955).

BrCH2CH2CH2Br + 2 NaCN NCCH2CH2CH2CN + 2 NaBr

!"#$%&'

()77-86%

C.S. Marvel, E.M. McColm, Organic Syntheses, Coll. Vol. 1, 536(1941).

ClCH2CH2CH2Br KCN ClCH2CH2CH2CN+ KBr

!-"#$%&'()40-47%

+

C.F.H. Allen, Organic Syntheses, Coll. Vol. 1, 156 (1941).

CH2=CHCH2Br CuCN CH2=CHCH2CN + CuBr

80-84%!"

+

J.V. Supniewski, P.L. Salzberg, Organic Syntheses, Coll. Vol. 1, 46 (1941).

O

CH2Cl

+

!

10 °C"#$

NCCH2CH(OH)CH2CN

54-62%

KCl KOH+ +

O

CH2Cl

NC

O

NC

Cl

O

NCCN

O

NC CN

2 KCN

–

–

–

–

（エポキシドの開環から反応が進んでいる．）

Organic Syntheses, Coll. Vol. 5, 614.

炭素求核剤（エノラートイオンのアルキル化は 17章を見よ）

S

S!"#n-C4H9Li$#%&'()*+',-./

0"#Cl(CH2)3Br

1"#n-C4H9Li S

S

65-84% Organic Syntheses, Coll. Vol. 6, 316.

ClCH2CH2CH2CN

!"#NaOH$%&'()*

+"#,$%&'()*COOH

74-79%-),./0


C6H5CHBrCCHBrC6H5

O

!"##$%&

N(CH2CH3)3

O

C6H5 C6H5

44%

'(


O O

BrH2C CH2Cl

KNH2, NH3

!"#$%-50 °C

55-70%

O O


窒素求核剤

CH3CHBrCO2H CH3CH(NH2)CO2H NH4Br+

65-70%

!"#$%"&

'()*+,-

W.C. Tobie, G.B. Ayres, Organic Syntheses, Coll. Vol. 1, 23 (1941).

CH3(CH2)3CHBrCO2H50-55 °C, 20-30!"

+ NH4Br

62-67%

CH3(CH2)3CH(NH2)CO2H#$%&'$(

C.S. Marvel, V. du Vigneaud, Organic Syntheses, Coll. Vol. 1, 48 (1941).

BrCH2CH2SO3Na

!"#$%"&'(

+ NH3 H2NCH2CH2SO3H NaBr+


C6H5CH2Cl + C6H5NH2!"90-95 °C

85-87%

C6H5CH2NHC6H5

NaHCO3


C6H5CH2Cl NH

O

O

+ NCH2C6H5

O

O

K2CO3

190 °C

72-79%


CH2Br

CH2Br

+

SO2NH2

CH3

60-70 °C

!"!#$%&'(')*+,N SO2 CH3

75-84%

+ H2 +

2 NaH

2 NaBr


C6H5CH2Br +

NH

KOH

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

N

CH2C6H5


NH3+Cl-Cl

N

N2

NH

75%


Cl O O ClC6H5CH2NH2+

120 °C NH

O O NH

C6H5C6H5

85-95%

NH

O O NH

C6H5C6H5

N

O O

N

O O

PhPh

I O O I+

Na2CO3, NaI

!"#$#%&'()*


C6H5CH2N

O

O NCH2CH3

NCH2CH3

I O O I+

K2CO3

!"#$#%&'(

C6H5CH2N

O

O N

CH2CH3

N

CH2CH3

O

O


CH2=CH CO2Me

BrCH3 NaN3

CH2=CH CO2Me

N3CH3

!"#$%&'(

F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, 4th ed., Kluwer Academic/Plenum Publihers,

Part B, p. 151.

B. B. Snider, J. V. Duncia, J. Org. Chem., 46, 3223 (1981).

CH3(CH2)3CH2ICH3CH2OCH2CH2OCH2CH2OH, H2O

NaN3CH3(CH2)3CH2N3

84%

F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, 4th ed., Kluwer Academic/Plenum Publihers,

Part B, p. 151.

酸素求核剤

H3CC CHCH2Cl

Cl

!"# Na2CO3$%&

'(H3CC CHCH2OH

Cl

63% Organic Syntheses, Coll. Vol. 4, 128.

OH

H

H

Cl

NaOHO

!

70-73%

NaCl+

O

H

H

Cl

OHO

H

H

ClO

H

H

–

H–


CH2ClCHOHCH2ClNaOH O

C CH2ClH2C

H

NaCl+

!"#$40-45 °C, 4%&

76-81%


KOHCCl H

CH2OH

CH3

OH

CH3!" 20-30 °C

65-70%


C6H5OH + BrCH2CH2CH2Br C6H5OCH2CH2CH2Br + NaBrNaOH

!"#$1.3%&'( 84-85%


K2CO3PhCH2Cl +

OH

CH3

NO2!"!#$%&'(')*+,

90 °C

OCH2C6H5

CH3

NO2

90%


NO2

CH2Cl

+

!"#$%

NO2

CH2OCCH3

NaCl+

89-93%

CH3CO2Na

O


BrCH2(CH2)9CO2H

O

O

79-83%

K2CO3

!"#$%$&'()

100 °C


O

O

OH

OH

O

O

O

O

O

O

Cl

O

Cl

O

+

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

KOH

38-44%


O

O

O

O

O

OCl

O

Cl

OH

OH

+!"#$%

&'

NaOH

39-48%


硫黄求核剤

(CH3)2CHBr + KSCN!"#$%&'(

(CH3)2CHSCN KBr+


CH3C(O)CH2Cl + CH3SNa!"#$%

74-76%

CH3C(O)CH2SCH3

5 °C&'( Organic Syntheses, Coll. Vol. 6, 601.

CH2=CHCH2Br

S

N

HS+N(CH2CH3)3

!"#$%&'#()*

S

N

CH2=CHCH2S


CH2Cl2 + 2 C6H5SHN(CH2CH3)3

!"##$%&

25 °C

SC6H5H2C

SC6H5


C6H5SH C6H5SCH2CH2Br!"#CH3CH2ONa, CH3CH2OH

$"#BrCH2CH2Br

C6H5SCH2CH2BrCH3CH2ONa, CH3CH2OH

%&C6H5SCH=CH2

50-65%


!"#$%&'(+BrCH2CH2Br HSCH2CH2SH

2 NaOCH2CH3

S

S

2 NaBr+

55-60%


HSCH2CH2CH2SH + 2 ClCH2CH2OHCH3CH2ONa, CH3CH2OH

!"OH HO

SS

71-82%

+ 2 (H2N)2C=S

BrCH2CH2CH2Br+

#$ %&'(!"

)$ KOH*+,(!"

53%

-*-./012324567

55-60 °C

58-62%

OH HO

SS

SH HS

SS

SH HS

SS

S S

SS2 Cs2CO3


HSCH2CH2SH+ClC(O)CH2Cl

S

S ON(CH2CH3)3

!"##$%&

0-10 °C

60%


N(CH2CH3)3CH3C(O)CHBrCH3 + CH3CH2CH2C(O)SH

!"#$%&'CH3C(O)CHCH3

SC(O)CH2CH2CH3

98-100%


!"

C6H5CH2Cl + Na2S#$%&'()*

C6H5CH2SCH2C6H5 2 NaCl+

80% Organic Syntheses, Coll. Vol. 6, 404.

2 HOCH2CH2Cl Na2S+

90-95 °C

!HOCH2CH2SCH2CH2OH 2 NaCl+

79-86%


BrCH2CH2NH2•HBr H2NCH2CH2SO3H 2 NaBr+

!" Na2SO3#$%

&"$'(68-73%


(CH3)2CHBr + Na2S2O3!-"#$%&

'(

(CH3)2CH S SO3Na NaBr+


リン求核剤

BuLi

Ph3P CH2Et2O

O

!

Ph3P+CH3 Br

–

CH2

G. Wittig, U. Schoelkopf, Org. Synth., Coll. Vol. 5, 751 (1973).

CH3Br + Ph3P!"#$%&'

99%

35~40%

(Wittig )*+

CH3I + (i-PrO)3P (i-PrO)2PCH3

O

+ i-PrI

A.H. Ford-Moore, B.J. Perry, Org. Synth., Coll. Vol. 4, 325 (1963).

reflux, 1 h85~90%

ハロゲン化物の交換

CH3(CH2)4CH2Br + KFHOCH2CH2OH

160-170 °C

CH3(CH2)4CH2F + KBr

40-45%


(CH3)3SiCH2CH2CH2ClNaI

!"#$%&'(CH3)3SiCH2CH2CH2I


反応例 13.1 ハロアルカンの求核置換反応（SN2反応）...反応例 13.1...

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