Acetophenone → 3,3-Diphenylacrolein

HRID 1857903Notes

Reaction equation

HRID 1857903 reaction equation
[C:1]1([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:15](C1C=CC=CC=1)(=[O:17])C.C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O>CN(C)C=O>[C:1]1([C:7]([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)=[CH:8][CH:15]=[O:17])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 7410AcetophenoneHCID 107401,1-Diphenylethylene2×HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chloride

Product 1

HCID 710273,3-Diphenylacrolein

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

First, a Grignard's reagent prepared from methyl chloride and magnesium is reacted with p-amino substituted benzophenone (2), followed by dehydration, to obtain 1,1-diphenylethylene derivative (3). Alternatively, the 1,1-diphenylethylene derivative (3) can be synthesized by reacting a Grignard's reagent, prepared from p-amino substituted bromobenzene, with an acetophenone compound (5), followed by dehydration. Next, a Vilsmeier reagent prepared from phosphorus oxychloride and N,N-dimethylformamide is reacted with the 1,1-diphenylethylene derivative (3) to obtain a 3,3-diphenylacrolein derivative (6). This 3,3-diphenylacrolein derivative (6) which is a mixture of a cis-isomer and a trans-isomer is subjected to a treatment using column chromatography or recrystallization treatment or a combination of these treatments to obtain a 3,3-diphenylacrolein derivative (7) embracing excess trans-isomers. The compound (7) and a diethyl 1,1-diphenylmethyl phosphonate derivative (9) are condensed by a Wittig-Horner reaction to synthesize 1-(p-aminophenyl)-1,4,4-triphenylbutadiene derivative (1) embracing excess tans-isomers (the ratio of trans-isomer≥0.6).

Sources & evidence

ORD record
ord-8d5d4c89f2514603afba2b4eee71eadb
Source dataset
uspto-grants-2000_11
Patent number
US06150065

Reaction notes

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