Carbon Tetrachloride → Triphenylphosphine Oxide

HRID 236163

反応式

HRID 236163 の反応式
[H-].[Na+].[CH3:3][N:4]1[CH2:8][CH2:7][CH:6]([OH:9])[CH2:5]1.Cl[C:11]1[CH:12]=[N:13][CH:14]=[C:15]([Cl:20])[C:16]=1[C:17]([OH:19])=[O:18].[C:21]1([P:27]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(Cl)(Cl)(Cl)[Cl:41]>CN(C)C=O.C(N(CC)CC)C>[Cl:20][C:15]1[C:16]2[C:17](=[O:19])[N:4]([CH3:3])[CH2:5][CH:6]([CH2:7][CH2:8][Cl:41])[O:9][C:11]=2[CH:12]=[N:13][CH:14]=1.[C:34]1([P:27](=[O:18])([C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1

参加物

9

反応物 5

HCID 5943Carbon Tetrachloride2 回HCID 11776Triphenylphosphine2 回HCID 24758Sodium hydrideHCID 930741-Methyl-3-pyrrolidinolHCID 6057633,5-Dichloroisonicotinic acid

生成物 2

HCID 13097Triphenylphosphine OxideHCID 137264086-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[4,3-f]-1,4-oxazepin-5(4H)-one

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒2 回HCID 8471Triethylamine溶媒

反応条件

温度
60 °C

実験手順

To a suspension of 2.1 g (60% in oil, 0.052 mole) of sodium hydride in 125 ml of dimethylformamide heated to 60° C. under a nitrogen gas blanket was added a solution of 2.65 g (0.026 mole) of N-methyl-3-pyrrolidinol and 5.0 g (0.026 mole) of 3,5-dichloropyridine-4-carboxylic acid in 40 ml of dimethylformamide dropwise at such a rate as to maintain 60° C. Subsequent to this addition, the mixture was heated to 75° C. for 3 hr. The solvent was then removed by rotary evaporation (60° C., 5 mm). The entire solid residue was suspended in 150 ml methylene chloride and hydrogen chloride added until a pH of 3 was reached. To the resulting mixture was added 15 g (0.057 mole) of triphenylphosphine and 15 g carbon tetrachloride and the entire mixture heated to reflux. After 1 hr, 7.5 g (0.029 mole) of triphenylphosphine and 7.5 g carbon tetrachloride were added, followed by the same incremental 1 hr later. The reaction was driven to completion by adding 20 ml of triethylamine. The reaction mixture was washed with 6×50 ml of 3N hydrochloric acid, dried over sodium sulfate, filtered and concentrated by rotary evaporation. To the residue was added ethyl acetate, which caused much tarry material to fall out of solution, leaving the desired product and triphenylphosphine oxide in solution. The mixture was chromatographed by column chromatography using silica gel as the stationary phase and ethyl acetate as eluent. Similar fractions were combined and ethyl acetate removed by rotary evaporation, yielding 0.6 g (7%), of white crystals, m.p. 134°-38° C.

後処理

  1. temperatureto maintain 60° C
  2. additionSubsequent to this addition
  3. temperaturethe mixture was heated to 75° C. for 3 hr
  4. customThe solvent was then removed by rotary evaporation (60° C., 5 mm)
  5. additionhydrogen chloride added until a pH of 3
  6. temperaturethe entire mixture heated to reflux
  7. customfollowed by the same incremental 1 hr
  8. washThe reaction mixture was washed with 6×50 ml of 3N hydrochloric acid
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated by rotary evaporation
  12. additionTo the residue was added ethyl acetate, which

出典と根拠

ORDレコード
ord-01bb7b9e351943f7bb1039976450a28f
出典データセット
uspto-grants-1987_02
特許番号
US04642343

関連ノート

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