17.10 reaction with primary amines: imines
DESCRIPTION
17.10 Reaction with Primary Amines: Imines. Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage. Acetal formation Imine formation Compounds related to imines Enamines The Wittig reaction. - PowerPoint PPT PresentationTRANSCRIPT
17.1017.10
Reaction with Primary Amines:Reaction with Primary Amines:
IminesImines
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
CC OOHH22NN
RR
HHNN HH
RR
a carbinolaminea carbinolamine
NN
RR
CC + + HH22OO(imine)(imine)
CC OO••••
++•••• ••••••••
••••
••••
••••
Imine (Schiff's Base) FormationImine (Schiff's Base) Formation
CHCH33NNHH22CHCH
OO
++
CH=CH=NNCHCH33 + + HH22OO
N-N-Benzylidenemethylamine (70%)Benzylidenemethylamine (70%)
ExampleExample
CHCH33NNHH22CHCH
OO
++
CH=CH=NNCHCH33 + + HH22OO
N-N-Benzylidenemethylamine (70%)Benzylidenemethylamine (70%)
CHCH
OHOH
NNHHCHCH33
ExampleExample
(CH(CH33))22CHCHCHCH22NNHH22OO ++
+ + HH22OO
N-N-Cyclohexylideneisobutylamine Cyclohexylideneisobutylamine (79%)(79%)
NNCHCH22CH(CHCH(CH33))22
ExampleExample
(CH(CH33))22CHCHCHCH22NNHH22OO ++
+ + HH22OO
N-N-Cyclohexylideneisobutylamine Cyclohexylideneisobutylamine (79%)(79%)
NNCHCH22CH(CHCH(CH33))22
OHOH
NNHHCHCH22CH(CHCH(CH33))22
ExampleExample
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
Reaction with Derivatives of AmmoniaReaction with Derivatives of Ammonia
HH22NN GG ++ RR22CC OO RR22CC NNGG ++ HH22OO
Reaction with Derivatives of AmmoniaReaction with Derivatives of Ammonia
HH22NN GG ++ RR22CC OO RR22CC NNGG ++ HH22OO
HH22NN OHOH RR22CC NNOHOH
hydroxylaminehydroxylamine oximeoxime
CHCH33(CH(CH22))55CHCH + H+ H22NNOHOH
OO
CHCH33(CH(CH22))55CHCH + H+ H22OO
NNOHOH
(81-93%)(81-93%)
ExampleExample
Reaction with Derivatives of AmmoniaReaction with Derivatives of Ammonia
HH22NN GG ++ RR22CC OO RR22CC NNGG ++ HH22OO
HH22NN OHOH RR22CC NNOHOH
hydroxylaminehydroxylamine oximeoxime
HH22NN NHNH22 RR22CC NNNHNH22
hydrazinehydrazine hydrazonehydrazone
etc.etc.
+ H+ H22NNNHNH22
+ H+ H22OO
(73%)(73%)
ExampleExample
OO
CC
NNNHNH22
CC
CCHCCH33 + H+ H22NNNHNH
+ H+ H22OO
ExampleExample
OO
CCHCCH33
NNNHNH
phenylhydrazinephenylhydrazine
a phenylhydrazone (87-91%)a phenylhydrazone (87-91%)
CHCH33(CH(CH22))99CCHCCH33
OO
HH22NNNHCNHNHCNH22
OO
HH22OOCHCH33(CH(CH22))99CCHCCH33
NNNHCNHNHCNH22
OO
++
++
ExampleExample
semicarbazidesemicarbazide
a semicarbazone (93%)a semicarbazone (93%)
17.11Reaction with Secondary Amines:
Enamines
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
Some reactions of aldehydes and ketones progressSome reactions of aldehydes and ketones progressbeyond the nucleophilic addition stagebeyond the nucleophilic addition stage
Acetal formationAcetal formation
Imine formationImine formation
Compounds related to iminesCompounds related to imines
EnaminesEnamines
The Wittig reactionThe Wittig reaction
RR22NNHH••••
++ HH22OO
(enamine)(enamine)
CC••••RR22NN
CC
Enamine FormationEnamine Formation
CC••••OORR22NN HH
HH CC
•••• ••••CC OO
••••
HH CC
••••
++
(heat in benzene)(heat in benzene)
ExampleExample
OO
NNNNHH
(80-90%)(80-90%)
++
(heat in benzene)(heat in benzene)
viavia
ExampleExample
OO
NNNNHH
OHOHN