Dimethylformamide → n,n-Dimethyl-4-(1-phenylethenyl)aniline

HRID 1857904

Reaktionsgleichung

Reaktionsgleichung von HRID 1857904
[CH3:1]N(C)C=O.P(Cl)(Cl)(Cl)=O.[CH3:11][N:12]([CH3:27])[C:13]1[CH:26]=[CH:25][C:16]([C:17]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=O)=[CH:15][CH:14]=1.C[Mg]Cl>C1(C)C=CC=CC=1.O.ClCCCl>[CH3:11][N:12]([CH3:27])[C:13]1[CH:26]=[CH:25][C:16]([C:17]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH2:1])=[CH:15][CH:14]=1

Komponenten

8

Edukt 4

HCID 6228DimethylformamideHCID 107374-(Dimethylamino)benzophenoneHCID 24813Phosphorus oxychlorideHCID 178418332HCID 178418332, Verbindung

Produkt 1

HCID 292243n,n-Dimethyl-4-(1-phenylethenyl)anilineAusbeute 29,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 111,2-DichloroethaneLösungsmittel2×HCID 962WaterLösungsmittel2×HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

10 ml of 1,2-dichloroethane and 1 ml (12.9 mmol) of N,N-dimethylformamide (DMF) were weighed and placed in a 100 ml reaction flask. To the mixture was gradually added dropwise 1.0 g (6.5 mmol) of phosphorus oxychloride while the mixture was cooled in ice-water. A bath was dismantled and the mixture was stirred for 10 minutes. Then, 5 ml of 1,2-dichloroethane containing 1.3 g (5.8 mmol) of 1-(p-dimethylaminophenyl)-1-phenylethylene (3a) which was synthesized from 4-dimethylaminobenzophenone (2a) and methylmagnesium chloride by using the method described in JP-B No. H7-21646 was added dropwise to the mixture. The resulting mixture was stirred for 3 hours at the same temperature and was then poured into water, which was then neutralized by addition of soda ash. The neutralized solution was heated at 80° C. to carry out a decomposition reaction and the resulting solution was subjected to separatory treatment. The water phase was subjected to an extraction treatment using toluene and the extract was combined with the organic phase. The resulting solution was washed with water and dried/concentrated using magnesium sulfate to obtain 1.4 g of a mixed product (6a) of a cis-isomer and a trans-isomer. The mixed product was recrystallized from a mixed solvent consisting of hexane and toluene to obtain 440 mg of 3-(p-dimethylaminophenyl)-3-phenylacrolein (7a). The yield was 29.3% and the melting point (mp) was 134-136° C. The ratio of trans-isomer measured by H-NMR was 0.98 (the ratio of trans-isomer are hereinafter indicated by a value measured by 1H-NMR). 1H-NMR (only peaks of trans-isomer are described) δ; 3.05 (s, 6H), 6.59(d, J=8.2 Hz, 1H), 6.67(d, J=9.1 Hz, 2H), 7.27(d, J=7.9 Hz, 2H), 7.47(m, 3H), 9.38(d, J=8.2 Hz, 1H). MS (m/z); 251, 234, 223, 207, 178, 165, 145, 121, 102, 91, 77, 42.

Aufarbeitung

  1. customplaced in a 100 ml reaction flask
  2. customA bath was dismantled
  3. additionH7-21646 was added dropwise to the mixture
  4. stirringThe resulting mixture was stirred for 3 hours at the same temperature
  5. additionwas then neutralized by addition of soda ash
  6. customa decomposition reaction
  7. washThe resulting solution was washed with water
  8. concentrationdried/concentrated

Quellen und Nachweise

ORD-Eintrag
ord-f7a9de01c4e4446d809a7a03e3e41208
Quelldatensatz
uspto-grants-2000_11
Patentnummer
US06150065

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