Calcium Hydroxide → HCID 54547805, compound

HRID 1870541Notes

Reaction equation

HRID 1870541 reaction equation
[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]

Participants

5

Reactant 3

HCID 6093208Calcium HydroxideHCID 10902235Acetic acid, chloro(diethoxyphosphinyl)-, 1,1-dimethylethyl ester2×HCID 18696623HCID 18696623, compound

Product 1

HCID 54547805HCID 54547805, compoundYield 50.8%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
60 °C

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-381afd52fdf14f9da3a80bbefa389035
Source dataset
uspto-grants-2000_08
Patent number
US06096895

Reaction notes

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