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(Properties
PreparationofAldehydes andKetones
1
Oxidation reactions 1 Hydrolysis of Geminal Dihalides 1 Hydration of Alkynes 1 Reactions with Acid Derivatives and Nitriles 1 Reaction with Carboxylic Acids 1 Reaction with Thioacetals
From Alcohols via PCC From Alkenes via Ozonolysis From Glycols via Periodic Acid Cleavage
RCH 2 OH R 2 CHOH R'CH R' R C OH CH 2 OH HIO
4
PCC PCC
R R
C H O C O R C O R' + H C H O R
CR 2
ozonolysis
R' C H + R O R C O
Hydration of Alkynes
x
Rosenmundcatalyst
O R C H
C Cl O
(R') 2CuLi
whereR'canbealkyl,aryl,orvinyl
H+ H 2O
C R' O
2
C N Al(ibu) H
C H O
H /H2 O
RLi
+
RCOO Li +RH R R C
+ O Li
RCOO Li RLi R R R R
+ O Li
O Li+ OH OH
O Li OH OH
H 2O
R R R
( H 2O )
C R O
X X
HC S H
H 2S H 2C B F
3
S C R
S
(ath acetal) io
H
2X
S C R
S L i
R H 'C
S C R
S + iX L C 2R H ' C 2R H '
HC g l (
C H H 2/ H 3O / HC S H H 2 2C
2O
S H )
C O
Characteristic Reactions of Characteristic Reactions of Aldehydes and Ketones Aldehydes and Ketones
y
Reduction reactions
Alcohol formation y Alkane formation
y
R R
C H O C H O
CH 2OH CH 2OH
reduction
x Alkane formation
3 Clemmensen
H 2O R H+
Oxidation of Aromatic Aldehydes/Ketones to Benzoic acid derivatives 3 Haloform reaction of methyl carbonyls 3 Periodic acid cleavage of vicinal dials/diketones
H or Ar
Ag(NH3)2 (Tollensreagent)
RCOOH (ArCOOH)
O H KMnO 4orK2Cr 2O 7 R X2
COOH
HCX 3 + RCOO
H H 2O R R' R R' R C C
OH OR"
ketal cyanohydrin R C N G
R R
C O C O
R' G
(H 2 O)
R'
Aldol Condensation
5 Self
vs. Crossed
Claisen Condensation
5 Self
H R RCH 2 C OH CH C H O
2 RCH 2 C H O
RCH 2
C H + R' C H O O
OH orH
H R R' C CH C H OH O
Claisen Condensations
x
R'O C OR' + R" C OR' R'OH O O C O (CH 2)4 R'O C OR' R'OH O R'O C OR' R'OH O
O R
R'O
R'O
C O
(CH 2)5
ReformatskyReaction ReformatskyReaction
R C H + Br CH 2 C OR' O R O
1. Zn/ benzene 2.H3O
+
H R C CH 2 C OR' OH R R C CH 2 C OR' OH O O
C R + Br CH 2 C OR' O O
Wittig Reaction
Phosphonium salt formation Ylide formation Alkene formation
RCH 2X +Ph 3P + Ph 3P R' R' +
SN 2
+ Ph 3 P
phosphoniumsalt
CH 2 R X
NaH
+ Ph 3 P
ylide
C O
CHR PPh 3 +
+ R Ph 3 P O
Malonic Ester Synthesis x Acetoacetic Ester Synthesis x Stork Enamine Synthesis x Michael Addition / Conjugate Addition
CH 2R C2H 5O C CH C OC 2 H 5 O O CH 2 R HO C CH C OH O O
H /H2O
strongheat
Acylation/Hydrolysis/Decarboxylation
C2H 5O C CH 2 C OC 2H 5 O Na+ O NaOC 2H 5 C2H 5OH O R C X Na+ C2H 5O C CH C OC 2H 5 O O
C2H 5O C CH C OC 2H 5 (NaX) O O
C2H 5O C CH C OC 2H 5 O O C R O HO C CH C OH O O C R O
C2H 5O C CH C OC 2H 5 O O C R O
H +/H2O
HO C CH C OH strongheat O O C R O
R C CH 3 + 2 CO 2 O
CH 3 C CH
C OC 2H 5 O
RCH 2X (NaX)
H /H 2O
CH 3 C CH 2 CH 2R O
Na + CH 3 C CH O O C C CH O O C C CH O R C OH O R C OC 2H 5 O C OC 2H 5 O
CH 3 C CH C OC 2H 5 O
CH 3
CH 3
CH 3
O C strongheat C CH C OH ( CO 2 ) O O
CH 3 C CH 2 C R O O
H
2
(H 2 O )
R'
C H NR 2 ( H )
+
(an aminol )
R'
C H NR 2
+
R'
C H NR 2
(anenamine)
R'
C H NR 2
+
C H NR 2
+
CH 2 R" R' C C H NR 2
+
hydrolysis
CH 2 R" R' C C H + R 2 NH O
H (H 2 O ) R' C
C H NR 2 ( H+ )
R'
C H NR 2
(adisguisedcarbanion) O R' C C H NR 2
+
(anenamine) C C R" C H NR 2
+
R" C X
R'
O R'
C C
R" C H NR 2
+
O hydrolysis R'
C C
R" C H + R 2 NH O
ConjugateAdditionto , UnsaturatedSystems
O Nu + C C C O Nu C C C H
+
O Nu C C C O Nu C C C H
Michael Addition
Michael Donors
CH (COOR)
malonicester
2
C C
C C O
(Michaeldonor)
CH
COOR C R' O
H 2O
C C
CH C O
Michael Addition
Robinson Annulation
O C C C O
OR ROH
C O C C O H 3C C O
C C
OR
O C H 3C
ROH
C Michael C product
Michaeldonor Michaelacceptor
O C C
C C C O C C HO
H 2O
O C
C C C O C C
Aldol
O O C H 2C
C C C O C C
H 2C
Nu directaddition H O C C C Nu conjugateaddition
Directaddition 4 ( )