反応例 10.3 アルコールとアルデヒドの酸化反応

第二級アルコールからケトンの生成

Cl

OH

Cl Cl

ONa2Cr2O7

H2SO4, H2O68~75%

J.B. Conant, O.R. Quayle, Org. Synth., Coll. Vol. 1, 211 (1941).

Cl

OH OCrO3, H2SO4

H2O, acetone

92~96%

E.J. Eisenbraun,

Org. Synth., Coll. Vol. 5, 310 (1973).

OHHO OOCrO3, H2SO4

aq. CH2Cl2, 0 ˚CG.H. Rasmusson, et al.,

Org. Synth., Coll. Vol. 5, 324!(1973).39~50%

CH3

OH

CH3CH3

Na2Cr2O7

H2SO4, H2O

CH3

O

CH3CH383~85%

L.T. Sandborn,

Org. Synth., Coll. Vol. 1, 340 (1941).

Ph CO2H

OH

Ph CO2H

O

aq. NaOH, –3 ˚CB.B. Corson, et al., Org. Synth., Coll. Vol. 1, 241 (1941).

KMnO4

CO2Et

OH

CH3 CH3 CO2Et

Oaq. HaH2PO4 J.W. Cornforth,

Org. Synth., Coll. Vol. 4, 467 (1963).pet. ether

51~54%

KMnO4

HO

C8H17

O

C8H17

dihydrocholesterol

Na2Cr2O7

H2SO4, HOAc

H2O, C6H683~84%

W.F. Bruice, Org. Synth., Coll. Vol. 2, 139 (1943).

HO

C8H17

O

C8H17

Ocholesterol

Na2Cr2O7

HOAc, C6H6

39~40%

L.F. Fieser, Org. Synth., Coll. Vol. 4, 189 (1963).

HO

C8H17

!

O

C8H17

cholesterol

(a) (t-BuO)3Al, acetone, benzene

(b) (i-PrO)3Al, cyclohexanone toluene

(a) 70~81%

(b) 81~93%

(a) R.V. Oppenauer, Org. Synth., Coll. Vol. 3, 207 (1955).

(b) J.F. Eastham, R. Teranishi, Org. Synth., Coll. Vol. 4, 192 (1963).

HO

C8H17

BrBr

Zn

O

C8H17

O

C8H17

(CO2H)2

HO

C8H17

O

C8H17

BrBr

cholesterol

Br2, HOAc,NaOAc, Et2O

Zn, Et2O

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

Na2Cr2O7

(81% from cholesterol)(71% from cholesterol) (68% from cholesterol)

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

HOAc

OH OCrO3, H2SO4

H2O, acetone

J. Meinwald, J. Crandall, W.E. Hymans, Org. Synth., Coll. Vol. 5, 866 (1973).

OH

CH2OH

O

OHH+, H2O

100 ˚C

!"#$

CrO3, (CO2H)2

H2O, 10~15 ˚C

31~35% (from cyclopropylmethanol)

M. Krumpolc, J. Rocek, Org. Synth., Coll. Vol. 7, 114 (1990).

第一級アルコールからカルボン酸の生成

OHNa2Cr2O7

H2SO4, H2OO

O

41~47%

G.R. Robertson, Org. Synth., Coll. Vol. 1, 138 (1941).

OH OH

CH3

CuCr2O4/BaCr2O4

200 ̊ CO

CH3

O

90~95%

R.I. Longley, Jr., W.S. Emerson, Org. Synth., Coll. Vol. 4, 677 (1963).

CH3(CH2)4 C

F

CH2Br

H

CH3(CH2)4 C

F

CH2OAc

H

!CH3(CH2)4 C

F

CH2OAc

H

CH3(CH2)4 C

F

CO2H

H

NaOAc, NaI

(SN2: NaI catalyst)

HOAc, 50 ˚C

F.H. Dean, J.H. Amin, F.L.M. Pattiso, Org. Synth., Coll. Vol. 5, 580 (1973).

78~94%

63~78%DMF

HNO3

第一級アルコールからアルデヒドの生成

K2Cr2O7

H2SO4, H2O

C.D. Hurd, R.N. Meinert,

Org. Synth., Coll. Vol. 2, 541 (1943).

H

O

OHOH !

46~49%

!"#$%&'()*+,-./012

H CH2OH H CHOCrO3, H2SO4

H2O, 5 ̊ CJ.C. Sauer,

Org. Synth., Coll. Vol. 4, 813 (1963).35~41%

CH2OH

C6H11N C NC6H11

CHO

pyridine, CF3CO2H

DMSO, benzene

J.G. Moffatt, Org. Synth., Coll. Vol. 5, 242 (1973).

(Moffatt!!"#

CH2Cl2CH3(CH2)8–CH2OH CH3(CH2)8–CHO

CrO3·(pyridine)2

R.W. Ratcliffe, Org. Synth., Coll. Vol. 6, 373 (1988).

63~66%

CH3(CH2)5–CH2OH CH3(CH2)5–CHO

CrO3·(pyridine)2

CH2Cl2, 25 ̊ C

J.C. Collins, W.W. Hess, Org. Synth., Coll. Vol. 6, 644 (1988).

70~84%

OH H

O

N O

(cat.)

KBr (cat.)aq. NaOCl (pH 9.5), CH2Cl2

0~15 ̊ C 82~84%

P.L. Anelli, F. Montanari, S. Quici,

Org. Synth., Coll. Vol. 8, 367 (1993).

アルデヒドからカルボン酸の生成

H

OKMnO4

OH

O

H2SO4, H2O

85~90%

J.R. Ruhoff, Org. Synth., Coll. Vol. 2, 315 (1943).

O

O

CHO

KMnO4

O

O

CO2HH2O, 75 ˚C

78~84%

R.L. Shriner, E.C. Kleiderer,

Org. Synth., Coll. Vol. 2, 358 (1943).

H

O

HCl

Cl H

O

HNO3

Cl H

O

Cl OH

O

–15 ~ –10 ̊ C

60~65%

C. Moureu, R. Chaux,

Org. Synth., Coll. Vol. 1, 166 (1941).

CHO

HO

OMe

NaOH, H2O

Ag2O, 55 ˚C

HCl, H2O

CO2H

HO

OMe

vanillin

1)

2)

I.A. Pearl,

Org. Synth., Coll. Vol. 4, 972 (1963).90~97%

S

CHO

Ag2O

NaOH, H2O S

CO2H

E. Campaigne, W.M. LeSuer, Org. Synth., Coll. Vol. 4, 919 (1963).

95~97%

O CHO

O2,

NaOH, H2O

Cu2O, Ag2O

H2SO4O CO2H

1)

2)

R.J. Harrisson, M. Moyle, Org. Synth., Coll. Vol. 4, 493 (1963).

86~90%

CHOO

NaClO3V2O5 (cat.)

HO2CCO2H

H2O, 75 ̊ C50~58%

N.A. Milas, Org. Synth., Coll. Vol. 2, 302 (1943).

ジオールとα－ヒドロキシケトンの酸化と開裂

C C

OHOH

HIO4 or Pb(OAc)4O O+

t-Bu-O2CCO2-t-Bu

OH

OH

Pb(OAc)4

benzene H CO2-t-Bu

O

77~87%

F.J. Wolf, J. Weijlard,

Org. Synth., Coll. Vol. 4, 124 (1963).

O

OSiMe3

O

OSiMe3

OHH5IO6

H

O

OH

OOH

O

OSiMe3

OH

THF, 25 ˚C

1) LDA, THF, –78 ˚C

2)

B. Bal, C.T. Buse, K. Smith, Org. Synth., Coll. Vol. 7, 185 (1990).

!"#$%#&'(

(CH2)8

O

OH

Cu(OAc)2, MeOH(CH2)8

O

Oaq. HOAc, !

88~89%

A.T. Blomquist, A. Goldstein,

Org. Synth., Coll. Vol. 4, 838 (1963).