有机人名反应(4)PPT课件

Ritter Reaction
R C N H
H NR
O
H RCN
R
H2O N
N
R
OH H
Robinson Annulation
Rosenmund Reduction
O
Cl
H2, Pd-BaSO4
140-150 oC
O
Cl
H2, Pd-BaSO4 xylene, 140 oC
A c 2O O
R1
R2
N
R3
R2
O R1
N
R3
-H R2
O
O R1
N
R3
O
O
R1
R2
N
R3
Reformatsky Reaction
O
O
R 1
R 2
+ B r
O E t
Zn O
OEt ZnBr
Z n
O H O R 1
R 2
O E t
+ ZnB rX
HX ZnBr2 + ZnX2
OZnBr O R1
O H
Mitsunobu Reaction
O H R 1 R 2
E t O O C N N C O O E t P P h 3 , N u
N u R 1 R 2
EtO O C N N C O O Et
PPh3 N uH
N u
R 1
+OP P h 3 +E t O O CNN C O O E t
R 2
K H 2O
O R C N + C
S
Lieben Iodoform Reaction
O
1 ) N a IO
R
C H 3
2 ) N a O H 3 ) H C l
O
R
+ O H
C H I3
N a I O
I 2 + N a O H
H 2O
O
R
C I3
+ N aO H
O H
O +
R O H
C I3
Mannich Reaction
68%
பைடு நூலகம்
O TiCl3 + LiAlH4 THF, reflux
12% Bomse, D. S.; Morton, T. H. Tetrahedron Letters 1975, 781.
Meerwein-Ponndorf-Verley Reaction
O +
R R '
O H A l [ O C H ( C H 3 ) 2 ] 3
R 3
O R 4
O
R
H
N a o r M g (H g )
R
O
cold conc. H2SO4 H
R
OH
H
R
H HO
H R
R
O
hot diluted H2SO4
H
R
H
Polonovski Reaction
R 2
O R 1
N
R 3
A c 2 O R2 = Ar
O
O
R 1 N
R 3
+ R 2
H
H 2O 2
O
R 1
R 2
T iC l3 (D M E )1 .5 Z n / C u
R 1 R 2
R 2 +
R 1
O Ti
Ti(0)
Zn/ Cu TiCl3(DME)1.5
LAH (LiAlH4) lithiumaluminiumhydride
Ti O
R1
R2
Ti Ti
O R1
R2
O R2
R1
O TiCl3 + LiAlH4 THF, reflux
R2
OEt
Riley Oxidation
O
R' R
SeO2
R=H ,C H 3 ,a lk yl, a ro m a tice ta l
O
O R
R' + S e + H 2 O
OH
R' R
SeO2
OH
Se O
O
R' R
HO Se O
O R'
H R
s o l v e n t :a l c o h o l ; a c e t i c a c i d ; a c e t i c a n h y d r i d e ; b e n z e n e ; x y l e n e ; d i o x a n e ; a n d w a t e r
*O s O 4 , c is- , o t h e r s ,tra n s-
O
oxidant: H2O2,
OOH
te rt s o l v e n t : - b u t a n o l ,e t h e r ,a c e t o n e ,
H 2 O - m e t h a n o l ,a c e t i c a c i d
O H +
R R '
O
A l[O C H (C H 3 )2 ]3
H 2O
R
R' O
H
O Al [O C H (C H 3)2]2
R
H
R'
O
O
Al
[OCH(CH3)2]2
R
H
R'
O
O
Al[OCH(CH3)2]2
Peterson Reaction
O
R 3
S iR 3
R 1
+ R 2
M
O H R 1
O
HHCl
+
N
+ HCHO
R1
R2
H
N
OH
R1
R2
+ HCl
+
HCHO
O
R2 N R1
-H
O OH
R1
R1 O H +H -H2O
N R2
+H2O -H
N R2
R2 N
H
R1
Milas Hydroxylation
H 2 O 2 , O o C c a t.
H O
c a t . = V 2 O 5 , M o O 3 , C r O 3 , S e O 2 , O s O 4
R 3 R 2
S iR 3
OM R1
R3 R2
S iR 3
base acid
OH R1
R3 R2
SiR3
O SiR3 R1
R2
R3
R 1
R 3
R 2 + R3SiOH
Pfitzner-Moffatt Oxidation
DM SO , dim ethylsulfoxide O
S
O H
DCC, dicylcohexylcarbodiim ide R
HH
E tO O CNNC O O E t D E A Dd ie th y la z o d ic a rb o x y la te
O H +
O O H
EtOOC N NCOOEt EtOOC N NCOOEt HH
PPh3
O PPh3
O O
yield: 65%
McMurry Reaction
Leuckart Reaction
O R R '
O N H 4 O C H
NH3
HO
NH2
R
R'
-H2O
N H 2
+ CO2
R R '
HCOOH
NH
R
R'
Letts Nitrile Synthesis
K S C N R C O O H
R C N + C O 2 + K H S
SCN
O R
S CN + OH
R '
NCN
D M S O D C C , H
O + SM e2
R R '
H NCN H
O
S
H
CH2
R
OS
R
R'
CH3
OH
R'
O
NCN
+
HH
base
H R
R'
CH3 OS
CH3
Pinacol Rearrangement
R 1 R 2
H O
O H R 4
R 3
R1 R2
H 2O
H
O
H
R4 R3
H
R 1 R 2