Ethyl diphenylphosphinite → 2-(Diphenylphosphinylmethyl)-4'-fluoro-3,5,3'-trimethylbiphenyl

HRID 323568

反応式

HRID 323568 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:15]=[C:14]([CH3:16])[CH:13]=[C:12]([CH3:17])[C:9]=2[CH2:10]Cl)=[CH:4][C:3]=1[CH3:18].C([O:21][P:22]([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)C>>[C:23]1([P:22]([CH2:10][C:9]2[C:12]([CH3:17])=[CH:13][C:14]([CH3:16])=[CH:15][C:8]=2[C:5]2[CH:6]=[CH:7][C:2]([F:1])=[C:3]([CH3:18])[CH:4]=2)([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[O:21])[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1

参加物

3

反応物 2

HCID 69754Ethyl diphenylphosphiniteHCID 133169812-(4-Fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl chloride

生成物 1

HCID 154316922-(Diphenylphosphinylmethyl)-4'-fluoro-3,5,3'-trimethylbiphenyl

反応条件

温度
150 °C

実験手順

2.90 grams (12 mmol) of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzaldehyde (prepared according to Stokker, Journ. Med. Chem., Vol. 29 p.170, 1986) was reduced with 0.454 grams (12 mmol) of sodium borohydride in ethanol (20 mL) at 0° C. The reaction was stirred 1 hr, quenched with aqueous ammonium chloride and the mixture extracted with ether. The organic portion was dried (MgSO4) and concentrated to give 2.90 grams of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl alcohol as an oil which solidified on standing. The crude solid was treated with 1.31 nL of thionyl chloride and heated on a steam bath for 1 hour. After cooling to room temperature, the crude mixture was taken up in water and extracted with ether. The ether was washed with water and dried(MgSO4), and concentrated to give an oily residue which was purified by silica gel chromatography (25% methylene chloride/75% hexane) to give 2.70 grams (85.6%) of 2-(4-fluoro-3-methylphenyl)4,6-dimethylbenzyl chloride as a solid. 2.06 grams (7.84 mmol) of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl chloride was treated with ethyldiphenylphosphinite (2.08 grams, 9.01 mmol) and heated to 150° C. for 3 hrs. After cooling to room temperature, the crude mixture was purified by silicagel chromatography (10% acetone/90% methylene chloride) and the appropriate fractions concentrated and recrystallized from ether/hexane to provide the above-titled compound. MP 109-111° C.

後処理

  1. temperatureAfter cooling to room temperature
  2. customthe crude mixture was purified by silicagel chromatography (10% acetone/90% methylene chloride)
  3. concentrationthe appropriate fractions concentrated
  4. customrecrystallized from ether/hexane

出典と根拠

ORDレコード
ord-8577c4569973478cba92645e4f05523c
出典データセット
uspto-grants-2001_04
特許番号
US06214809B1

関連ノート

読み込み中…