反応例 10.2 Grignard反応と関連反応...BuLi Me2NCH2CH2NMe2 NMe CH3 Li NMe2 CH3 Ph OH Ph...
Transcript of 反応例 10.2 Grignard反応と関連反応...BuLi Me2NCH2CH2NMe2 NMe CH3 Li NMe2 CH3 Ph OH Ph...
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反応例 10.2 Grignard 反応と関連反応
アルデヒド,ケトンとの反応
ClMg
Et2O
MgClH2C O1)
2) H2SO4/H2O
OH
64~69%
H. Gilman, W.E. Catlin, Org. Synth., Coll. Vol. 1, 188 (1941).
(CH3)2CHBrMg
Et2O(CH3)2CHMgBr
CH3CHO1)
2) H2SO4/H2O
OH
53~54%
N.L. Drake, G.B. Cooke, Org. Synth., Coll. Vol. 2, 408 (1943).
BrClMg
Et2O
MgBrCl CH3CHO1)
2) H2SO4/H2O
ClOH
82.5~88%
C.G. Overberger, J.H. Saunders, R.E. Allen, R. Gander, Org. Synth., Coll. Vol. 3, 200 (1955).
PhCH2MgCl +
Ph Ph
O1) Et2O !
2) H2O
PhOH
Ph Ph
H2SO4/H2O
!
Ph
PhH
Ph
H. Adkins, W. Zartman,
Org. Synth., Coll. Vol. 2, 606 (1943).
54~59%
O
1) PhMgBr/Et2O !
Ac2O
!
Ph
S
Ph
Ph OH
2) HCl/H2O
42~48% 91~94%
250~270 ˚C
30 min
R. Weiss
Org. Synth., Coll. Vol. 3, 729 (1955).
(脱水)
(脱水素)
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有機リチウム化合物
SnPh3PhLi/Et2O Li
O
!
OH1)
2) H2O 70~75%
D. Seyferth, M.A. Weiner, Org. Synth., Coll. Vol. 5, 452 (1973).
N CH3
PhLi/ Et2O
NLi
N
OH1) CH3CHO
2) HCl/H2O
44~50%
L.A. Walter, Org. Synth., Coll. Vol. 5, 452 (1973).
NMe2
CH3
BuLiMe2NCH2CH2NMe2
NMe2
CH3
Li
NMe2
CH3
Ph
OH
Ph
hexane, 25 ˚C
1) Ph2C=O
Et2O, 25 ˚C
2) AcOH49~57%
J.V. Hay, T.M. Harris, Org. Synth., Coll. Vol. 6, 478 (1988).
α,β-不飽和カルボニル化合物への 1,2-付加
CH3CH CHCH
O1) CH3MgCl/Et2O !
CH3CH CHCHCH3
OH
2) NH4Cl/H2O 81~86%
E.R. Coburn, Org. Synth., Coll. Vol. 3, 696 (1955).
Br Mg MgBr Et2O
O
!
Et2O
OH1)
2) H2SO4/H2O
J.C.H. Hwa, H. Sims, Org. Synth., Coll. Vol. 5, 608(1973).
57~59%
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HC CH
H
H
O
THF
HC C–MgBr
HC C–MgBr
THF
H OH
+ EtMgBr
+
2) NH4Cl/H2O
1)
58~69%
L. Skattebøl, E.R.H. Jones, M.C. Whiting, Org. Synth., Coll. Vol. 4, 792(1963).
エステルとの反応
2 CH3CH2CH2CH2MgBr H OEt
O
(CH3CH2CH2CH2)2CHOH+1) Et2O
2) H2SO4/H2O 83~85%
G.H.Coleman, D. Craig, Org. Synth., Coll. Vol. 2, 179 (1943).
MgBr
CH3 OEt
O
! Ph
Ph
Ph Ph
CH3 OH
+1) Et2O
2) NH4Cl/H2O
20% H2SO4 C.F.H. Allen, S. Converse,
Org. Synth., Coll. Vol. 1, 226 (1941).
67~70%
2
MgBr
CH3 OEt
O
Ph3C–OH+
1) Et2O
benzene, !
2) H2SO4/H2O 89~93%
W.E. Bachmann, H.P. Hetzner, Org. Synth., Coll. Vol. 3, 869 (1955).
2
3 C2H5MgBrEtO OEt
O
(C2H5)3C–OH+1) Et2O
2) NH4Cl/H2O82~88%
W.W. Moyer, C.S. Marvel, Org. Synth., Coll. Vol. 2, 602 (1943).
(脱水)
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OOCH3(CH2)4
CH3(CH2)4
OH
OH
CH3 CH31) CH3MgBr/Et2O, !
2) HCl/H2O, benzene
57%
J. Colonge, R. Marey, Org. Synth., Coll. Vol. 4, 601 (1963).
有機アルカリ金属化合物
CH2
CO2Me
CH3
THF
CH2
C
CH3
OH
BuBu
BuBr + 2Li BuLi + LiBr–20 ˚C
2 BuLi +1) THF, –20 ˚C
2) HCl / H2O
80~86%
P.J. Pearce, D.H. Richards, N.F. Scilly, Org. Synth., Coll. Vol. 6, 478 (1988).
CH3CH C
Br
CH3
LiCH3CH C
Li
CH3
CH3 OEt
O
Et2O Et2O
TsOH
Et2O
OH
73~75%
S. Threlkel, J.E. Bercaw, P.F. Seidler, J.M. Stryker,
R.G. Bergman, Org. Synth., Coll. Vol. 8, 505 (1993).
Cl
EtO OEt
O
COH3 +reflux, 2 h
EtOH, H2O
1)
2)
Na, benzene
3
A.A. Morton, J.R. Myles, W.S. Emerson, Org. Synth., Coll. Vol. 3, 831 (1955).
35~40%
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二酸化炭素との反応
R–XMg
R–MgXEt2O
Cl
Cl
(CH3)3C–Cl
Br
R–CO2H
Cl
Br
1) CO2
2) H2SO4/H2O
R–X = !"#72~73%
!"#76~78%
!"#85%
!"#80~85%
H. Gilman, R.H. Kirby, Org. Synth., Coll. Vol. 1, 361 (1941).
R–X = !"#69~70%
S.V. Puntambeker, E.A. Zoellner, Org. Synth., Coll. Vol. 1, 524 (1941).
R–X = !"#68~70%
H. Gilman, N.B.St. John, F. Schlze, Org. Synth., Coll. Vol. 2, 425 (1943).
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有機アルカリ金属化合物
N CH3
PhLi
N CH2LiEt2O N CH2CO2Et
1) CO2
2) HCl/EtOH
3) K2CO3/H2O
R.B. Woodward, E.C. Komfeld, Org. Synth., Coll. Vol. 3, 413 (1955).
35~40%
CH3 C C H CH3 C C Na CH3 C C CO2HNa, NH3 1) CO2, THF, Et2O
2) HCl/H2O 50~59%
J.C. Kauer, M. Brown, Org. Synth., Coll. Vol. 5, 1043 (1973).
アミドとの反応
PhCH2CH2ClMg
PhCH2CH2MgCl
NH
O
THFPhCH2CH2CHO
1)
2) HCl/H2O 66~76%
G.A. Olah, M. Arvanaghi, Org. Synth., Coll. Vol. 7, 451 (1990).
ニトリルとの反応
MeOCH2C NEt2O
PhOMe
NMgBr
! PhOMe
O
PhMgBr +H2SO4/H2O
71~78%
R.B. Moffett, R.L. Shriner, Org. Synth., Coll. Vol. 3, 567 (1955).
C
N
CH3MgI
NMgI
CH3
!
O
CH3
Et2O, !
HCl/H2O
52~59%
J.E. Callen, C.A. Donfeld, G.H. Coleman, Org. Synth., Coll. Vol. 3, 26 (1955).
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PhCNEt2O
NMgBr
Ph
Ph MeOH
!NH
Ph
Ph
PhMgBr +
P.L. Pickard, T.L. Tolbert, Org. Synth., Coll. Vol. 5, 520 (1973).
61~81%
イミンとの反応
O CH3NH2
H2O
NHCH3
NCH3
Et2O
PhCH2MgCl
NCH3 MgCl
benzene
87~97%
91~96%
R.B. Moffett,
Org. Synth., Coll. Vol. 4, 605 (1963).
エポキシドとの反応
CH3(CH2)3MgBrO Et2O
CH3(CH2)5OH+H2SO4/H2O
1)
2)60~62%
E.E. Dreger, Org. Synth., Coll. Vol. 1, 306 (1941).
BrMg
MgBr
O
Et2O
OH
78~90%
1)
2) NH4Cl/H2O
L.S. Hegedus, M.S. Holden, J.M. McKearin, Org. Synth., Coll. Vol. 7, 501 (1990).
PhMgBr O
OH
Ph
+ 1) CuCl/THF, –30 ̊ C
2) (NH4)2SO4/H2O
80%
A. Schwartz, P. Madan, J.K. Whitesell, R.M. Lawrence, Org. Synth., Coll. Vol. 8, 516 (1993).
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オルトエステルとの反応:アセタールとアルデヒドの合成
CH3(CH2)4MgBr + HC(OEt)3
CH3(CH2)4CHO
!
Et2OCH3(CH2)4CH(OEt)2
!"#$%
H2SO4/H2O
45~50%
G.B. Bachman, Org. Synth., Coll. Vol. 2, 323 (1943).
Br
!
!
CHO
MgBr
!
HC(OEt)3
CH(OEt)2
Mg/Et2O
H2SO4/H2O
40~42%
C.A. Dornfeld, G.H. Coleman,
Org. Synth., Coll. Vol. 3, 701 (1955).
Reformatsky 反応
H
O
Ph PhCO2Et
OH
+ BrCH2CO2Et1) Zn, Et2O, benzene, !
2) H2SO4/H2O
61~64%
C.R. Hauser, D.S. Breslow, Org. Synth., Coll. Vol. 3, 408 (1955).
H
O
CH3CHCO2Et
BrOH
CO2Et+1) Zn, benzene, !
2) H2SO4/H2O
K.L. Rinehart, E.G. Perkins, Org. Synth., Coll. Vol. 4, 444 (1963).
CH3CHCO2-s-Bu
Br
CH3(CH2)4 O-s-Bu
OO
CH3
CH3(CH2)4CN +1) Zn, benzene, !
2) H2SO4/H2O50~58%
K.L. Rinehart, Org. Synth., Coll. Vol. 4, 120 (1963).