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Calcium Hydroxide → HCID 54547805, 화합물

HRID 1870541
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HRID 1870541 반응식
[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]
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참가 물질

5

반응물 3

HCID 6093208Calcium HydroxideHCID 10902235Acetic acid, chloro(diethoxyphosphinyl)-, 1,1-dimethylethyl ester2회HCID 18696623HCID 18696623, 화합물

생성물 1

HCID 54547805HCID 54547805, 화합물수율 50.8%

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매2회

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온도
60 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-381afd52fdf14f9da3a80bbefa389035
출처 데이터셋
uspto-grants-2000_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06096895

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