(1) KMnO4, OH-, ∆ (2) H3O+

LiAlH4

(1) LiAlH(Ot-Bu)3, Et2O O SOCl2

(2) H2O R C
Cl

Cr+6 O A. (1) KMnO4, OH-, ∆ (2) H3O+ O

R CH2 OH R C R C
H Β. (1) Ag(NH3)2+ / NH3 (2) H3O+ OH
A. NaBH4
C. (1) Ag2O, OH- (2) H3O+
B. LiAlH4
D. OsO4
E. O
R C O OH
(Bayer-Villager Rxn)
F. Cr+6
O
(1) DIBAL-H, hexane
R C (2) H2O
O R'

(1) DIBAL-H, hexane (1) R'MgBr

OH
R C N
(2) H2O R C H
(2) H3O+
R'
OR" OH
R'OH (Grignard Rxn)
R C H R C H
H+ or OR- ( R may be H )
OR' OR'
(Acetal Rxn)

Copyright © 1998 Karl J. Miller

 OH
O OH
R CH R'
C R C R'
R O R'
R"
O

}
R" C
O OH
Assuming R has greatest A. LiAlH 4 H2CrO4
migaratory aptitude B. NaBH4
H > phenyl > 3° > 2° > 1° > methyl
(1) R"MgBr
(Baeyer-Villager Rxn) (Grignard Rxn)
(2) H3O+

O
(1) O3 AlCl 3 O
C C C
R R' +
(2) Zn, H2O Friedel-Crafts Acylation onto Benzene R C
(where R' is Aryl ) Cl

(1) X2 / NaOH
(1) Li, Et O
R Br (2) Cu I 2 R2 CuLi where R' is CH3
(2) H3O+

O O
R2CuLi
C + CHX3
R C
Cl R OH

A. (1) R'-MgX (2) H3O+ (Grignard Rxn)

R C N

[ ]
H
Β. (1) R'-Li (2) H 3O+ (where R' is CH3 ) HgSO4
R C C H R C C H
H2SO4 / H2O
OH

Copyright © 1998 Karl J. Miller

 O
OH¯/H 2O
R C NHR'R" excess
Cl Pyridine, R'OH ( –Cl¯)
( –NH 2R'R" +Cl¯)
RCOO¯ ( –pyrH +Cl¯)
( –Cl ¯ )

O O
C C NHR'R"
A. SOCl 2 R O R R'OH ( –RCOOH)
(–SO 2, HCl) (–RCOOH)
H2 O
B. PCl 3 ( –H +Cl¯)
(–H 3, PO 3)

C. PCl 5 O
( –POCl 3, C R'
H 2O OH¯/H 2O
HCl) R O NHR'R"
( –R'OH)
( –R'OH)

R'OH, H +
( –H 2O) A. NHR'R", ∆ (–H 2O) *poor
B. NHR'R", DCC O
H + /H 2 O (–N,N'-Dicyclohexylurea) O
C R' OH¯/H 2O
( –R'OH)
N ( –NHR'R") C -
-
R R O
R"
H + /H 2 O
P 4O 10 , ∆
( –NH 2R'R" + )
( –H 2 O)
O
C H 3O + /H 2 O, ∆
OH¯/H 2O
R OH ( –NH 4 +) R C N
( –NH 3 /OH¯ )

A. NaOH (–H 2O)

B. NaHCO 3 (–H 2 O, CO 2 )

Copyright © 1998 Karl J. Miller

 O O
NaN3 ∆ H2O
R C (–NaCl) R C R N C O (–CO 2)
(–N2)
Cl N3

NaN3 A. Na / EtOH
R Br R N N N
EtOH Β. LiAlH 4

(1) R—X
NH3
(2) OH¯

A. (1) LiAlH4 / Et2O

O (2) H2O RNH2
R C
NH2 Β. Br2 , NaOH / H2O
(–CO3¯², 2 NaBr, 2 Na +, 2 H2O)

A. H2 / Ni , 140°C
R* C N
Β. LiAlH4

N OH A. Na / EtOH R*—C = R
R* C H Β. LiAlH4

A. H2 / Catalyst HONO + Cu2O, Cu2+, H2O

Ar NO2 Ar NH2 Ar N2 Ar OH
Β. (1) Fe / HCl ( 0-5°C )
CuCl
(2) OH¯ Ar Cl
CuBr
Ar Br
where "Ar" is Aryl CuCN
Ar C N
H2S, NH3
Ar (NO 2)2 EtOH
Ar (NH2)(NO 2) KI
Ar I
(1) HBrF 4 (2) ∆
Ar F
H3PO2
Ar H

Copyright © 1998 Karl J. Miller

 O O
C C P4
H2C OH ∆ H2C R CH2CO 2H + X2 R CH2CO2H + HX
O + H2O
H2C OH H2C
C C X2 = Cl2 or Br2

O O

O
O O
C
C C
R CH ( CH2 )n COOH H+
(CH2)n
H2C NH2 ∆ H2C
O NH + H2O
OH OH¯, H 2O H2C OH H2C
CH C C
when n=2, a γ-lactone; when n=3, a δ-lactone O
R O

NH2 N
H+ H
C C O + H2O
R CH (CH2 )n COOH
OH¯, H 2O R
(CH2)n
when n=2, a γ-lactam; when n=3, a δ-lactam

Gabriel Synthesis

O O O
(1) KOH NH2NH2 H
N H N R R NH2 + N
(2) R–X EtOH
N
O H
O
O

Copyright © 1998 Karl J. Miller