Carbon Tetrachloride → Triphenylphosphine Oxide

HRID 4821

반응식

HRID 4821 반응식
[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](O)=[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[CH2:17][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

참가 물질

9

반응물 5

HCID 5943Carbon Tetrachloride2회HCID 11776Triphenylphosphine2회HCID 24758Sodium hydrideHCID 930741-Methyl-3-pyrrolidinolHCID 6057633,5-Dichloroisonicotinic acid

생성물 2

HCID 13097Triphenylphosphine OxideHCID 867408316-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[4,3-f]-1,4-oxazepin

시약·촉매·용매 2

HCID 6228Dimethylformamide용매2회HCID 8471Triethylamine용매

반응 조건

온도
60 °C

실험 절차

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 increments 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.

후처리

  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 increments 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

출처 및 근거

ORD 기록
ord-93749aa381254392b61d61749772cb78
출처 데이터셋
uspto-grants-1988_02
특허 번호
US04727152

연결된 노트

불러오는 중…