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

HRID 1857904

反応式

HRID 1857904 の反応式
[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

参加物

8

反応物 4

HCID 6228DimethylformamideHCID 107374-(Dimethylamino)benzophenoneHCID 24813Phosphorus oxychlorideHCID 178418332HCID 178418332、化合物

生成物 1

HCID 292243n,n-Dimethyl-4-(1-phenylethenyl)aniline収率 29.3%

試薬・触媒・溶媒 3

HCID 111,2-Dichloroethane溶媒2 回HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-f7a9de01c4e4446d809a7a03e3e41208
出典データセット
uspto-grants-2000_11
特許番号
US06150065

関連ノート

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