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Calcium Hydroxide → HCID 54547805、化合物

HRID 1870541
ノート
印刷プレビュー

反応式

HRID 1870541 の反応式
[Cl:1][CH:2](P(OCC)(OCC)=O)[C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].[OH-].[Ca+2].[OH-].[CH3:21][O:22][C:23]1[N:27]([C:28]2[CH:32]=[CH:31][S:30][C:29]=2[CH:33]=O)[C:26](=[O:35])[N:25]([CH3:36])[N:24]=1>C(OCC)(=O)C>[Cl:1][C:2](=[CH:33][C:29]1[S:30][CH:31]=[CH:32][C:28]=1[N:27]1[C:26](=[O:35])[N:25]([CH3:36])[N:24]=[C:23]1[O:22][CH3:21])[C:3]([O:5][C:6]([CH3:7])([CH3:8])[CH3:9])=[O:4]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 6093208Calcium HydroxideHCID 10902235Acetic acid, chloro(diethoxyphosphinyl)-, 1,1-dimethylethyl ester2 回HCID 18696623HCID 18696623、化合物

生成物 1

HCID 54547805HCID 54547805、化合物収率 50.8%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒2 回

反応条件

温度
60 °C

実験手順

A solution of the title compound of Step C (0.026 g, 0.0009 mol) in ethyl acetate (2 mL) was added to a mixture of calcium hydroxide (0.068 g, 0.0009 mol) and the title compound of Step A (0.220 g, 0.0009 mol) in ethyl acetate (5 mL). The resulting mixture was stirred at 60° C. overnight. Three additional 0.026 g (0.0009 mol) portions of the title compound of Step C were added at 3 h intervals and then the temperature of the mixture was increased to 70° C. and heating was continued overnight. After 40 h of total reaction time, the reaction mixture was poured into ice water and extracted three times with ethyl acetate. The combined organic phase was washed successively with saturated aqueous NaCl and then with a 1/1 mixture of saturated aqueous NaCl and saturated aqueous sodium hydrogen carbonate, dried (Na2SO4), filtered and concentrated to a pale yellow oil. The crude product was purified by flash column chromatography on silica gel to give a preliminary fraction of 0.170 g of the title compound of Step D, a compound of the invention, as a white solid (m.p. 105-115° C.) consisting of a 7:3 ratio of Z- and E-isomers, respectively, followed by a final fraction of 0.04 g of the title compound of Step D, a compound of the invention, as a white solid (m.p. 104° C.) consisting of a 5:1 ratio of Z- and E-isomers, respectively. 1H NMR (300 MHz, CDCl3 : for the Z/E mixture): δ 7.77 and 7.00 (2d,1H total, J=0.8 Hz), 7.62 and 7.46 (2dd,1H total, J=0.8, 5.4 Hz), 7.09 and 6.98 (2dd,1H total, J=0.9, 5.4 Hz), 3.97 (s,3H), 3.45 (s,3H), 1.54 (s,9H).

後処理

  1. temperaturethe temperature of the mixture was increased to 70° C.
  2. temperatureheating
  3. waitwas continued overnight
  4. waitAfter 40 h of total reaction time
  5. extractionextracted three times with ethyl acetate
  6. washThe combined organic phase was washed successively with saturated aqueous NaCl
  7. additionwith a 1/1 mixture of saturated aqueous NaCl and saturated aqueous sodium hydrogen carbonate
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated to a pale yellow oil
  11. customThe crude product was purified by flash column chromatography on silica gel

出典と根拠

ORDレコード
ord-381afd52fdf14f9da3a80bbefa389035
出典データセット
uspto-grants-2000_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06096895

反応ノート

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このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート