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1,3-Diphenyl-2-propanone → 5-Dimethylamino-1,2-diphenyl-2,4-pentadien-1-one

HRID 426539
Notes
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Reaction equation

HRID 426539 reaction equation
C1(C2C(C3C=CC=CC=3)=CC=CN=2)C=CC=CC=1.[C:19]1([C:25]([CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:26])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(C1C(C2C=CC=CC=2)=CC=CN=1)C1C=CC=CC=1.C1(CC(CC2C=CC=CC=2)=O)C=CC=CC=1.Br.BrCCCN.C(O[CH:78](OCC)[CH:79]=[CH:80][N:81]([CH3:83])[CH3:82])C>CN(C)C=O.[Pd]>[CH3:82][N:81]([CH3:83])[CH:80]=[CH:79][CH:78]=[C:27]([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[C:25]([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)=[O:26]
ParticipantsProcedureSources & evidenceReaction notes

Participants

9

Reactant 6

HCID 75931,3-Diphenyl-2-propanoneHCID 99482-Phenylacetophenone2×HCID 787013-Bromopropylamine hydrobromideHCID 1184762,3-Diphenylpyridine2×HCID 30177982-Benzyl-3-phenylpyridineHCID 538831963,3-Diethoxy-N,N-dimethylprop-1-en-1-amine

Product 1

HCID 540157505-Dimethylamino-1,2-diphenyl-2,4-pentadien-1-one

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

It is known to produce pyridines having aromatic substituents in the 2- and 3-positions from ketones, namely, 2,3-diphenyl pyridine from desoxybenzoin and 2-benzyl-3-phenyl pyridine from 1,3-diphenylacetone. The ketone for this purpose is first converted to the enamine, this reacted with 3-bromo-propylamine hydrobromide in dimethyl formamide to the tetrahydropyridines and these finally dehydrogenated in the presence of palladium catalyst to the pyridines (Org. Chem. Vol. 28 (1963) pages 3468 to 3473). In the case of the production of 2,3-diphenyl pyridine from desoxybenzoin this can also be reacted with 3,3-diethoxy-1-dimethylamino-1-propene to form 5-dimethylamino-1,2-diphenyl-2,4-pentadien-1-one and this reacted with triethyloxonium tetrafluoroborate and further with dimethylamine to 5-dimethylamino-N,N-dimethyl-1,2-diphenyl-2,4-pentadieniminium-tetrafluoroborate and finally this converted into the 2,3-diphenyl pyridine by heating in an ammonium chloride-ammonia solution (Liebigs Ann. Chem. 1975 pages 874 to 900).

Sources & evidence

ORD record
ord-e199db17fb41456781eeba3abb8a745a
Source dataset
uspto-grants-1979_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04169951

Reaction notes

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