Triethylamine → Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo [d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl ester

HRID 270457ノート

反応式

HRID 270457 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH:13]=[CH:14][C:15]([C:17]#[C:18][C:19]([CH3:22])([OH:21])[CH3:20])=[CH:16][C:11]=3[S:10][N:9]=2)=[CH:4][CH:3]=1.[Li+].CCC[CH2-].C(N(CC)CC)C.[CH2:35]([O:37][P:38](Cl)([O:40][CH2:41][CH3:42])=[O:39])[CH3:36]>C1COCC1.CCCCCC.O>[CH2:35]([O:37][P:38](=[O:39])([O:40][CH2:41][CH3:42])[O:21][C:19]([CH3:22])([CH3:20])[C:18]#[C:17][C:15]1[CH:14]=[CH:13][C:12]2[C:8]([C:5]3[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][CH:6]=3)=[N:9][S:10][C:11]=2[CH:16]=1)[CH3:36]

参加物

8

反応物 4

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 61028n-Butyl lithiumHCID 223138854-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-2-methyl-but-3-yn-2-ol

生成物 1

HCID 69289237Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo [d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl ester収率 33%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒

反応条件

温度
0 °C

実験手順

200 mg (0.54 mmol) 4-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-2-methyl-but-3-yn-2-ol in 2 ml THF were treated with 36 μl (5.6 mmol) 1.6 M N-Butyllithium in hexane at −78° C. for 30 min. 112 μl (0.81 mmol, 1.5 eq) Triethylamine in 0.5 ml THF and 117 μl (0.8 mmol, 1.5 eq) Diethylchlorophosphate in 0.5 ml THF were added and the solution was stirred at −78° C. over night and at 0° C. for 4 h. Water was added, and the inorganic phase was extracted with EtOAc, the combined organic phases were washed with brine and dried over Na2SO4. Column chromatography on silica gel with hexane:EtOAc 3:1 gave 90 mg (33%) Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo[d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl ester as yellow semisolid, MS: 508 (MH+, 1Br).

後処理

  1. extractionthe inorganic phase was extracted with EtOAc
  2. washthe combined organic phases were washed with brine
  3. dry with materialdried over Na2SO4

出典と根拠

ORDレコード
ord-e83b355ebd0d4ccc94882547bd1e0227
出典データセット
uspto-grants-2008_11
特許番号
US07449483B2

反応ノート

読み込み中…