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Thionyl Chloride → (+)-4,5-dihydro-1-[[hydroxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, phenylmethyl ester

HRID 1757940
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HRID 1757940 반응식
[OH:1][P:2]([CH2:14][C:15]([OH:17])=O)([CH2:4][CH2:5][CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:3].S(Cl)(Cl)=O.Cl.[C:23]1([C:29]2[CH2:33][CH:32]([C:34]([O:36][CH2:37][C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)=[O:35])[NH:31][N:30]=2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.ClC(OC(=O)C(C)(C)C)C(OCC)=O>C(N(CC)CC)C.ClCCl.CN(C)C=O>[OH:1][P:2]([CH2:14][C:15]([N:31]1[CH:32]([C:34]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:35])[CH2:33][C:29]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[N:30]1)=[O:17])([CH2:4][CH2:5][CH2:6][CH2:7][C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)=[O:3]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

8

반응물 4

HCID 24386Thionyl ChlorideHCID 13102401((4-Phenylbutyl)hydroxyphosphoryl)acetic acid2회HCID 13102402Ethyl 2-chloro-2-pivaloyloxyacetateHCID 131712948(+)-4,5-dihydro-3-phenyl-1H-pyrazole-5-carboxylic acid, phenylmethyl ester, hydrochloride

생성물 1

HCID 86738774(+)-4,5-dihydro-1-[[hydroxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, phenylmethyl ester

시약·촉매·용매 3

HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매2회HCID 8471Triethylamine용매

실험 절차

A solution of 10 g. of [hydroxy(4-phenylbutyl)phosphinyl]acetic acid, from part (b), in 40 ml. of dry dichloromethane containing 0.2 ml. of dimethylformamide is heated to reflux temperature. Thionyl chloride (5.1 g.) is added dropwise while maintaining the temperature at reflux. After an additional 30 minutes heating, the solution is cooled to 5° and a solution of 11.6 g. of (+)-4,5-dihydro-3-phenyl-1H-pyrazole-5-carboxylic acid, phenylmethyl ester, hydrochloride (1:1), from part (a), in 50 ml. of dichloromethane is added at once, followed by dropwise addition of 11.9 g. of triethylamine while the temperature is maintained at 5°-10° with cooling. After stirring overnight at ambient temperature, the mixture is washed three times with aqueous hydrochloric acid (1.5 N) and three times with water. The organic solution is dried (MgSO4) and concentrated in vacuo to give (+)-4,5-dihydro-1-[[hydroxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, phenylmethyl ester which can be crystallized from acetone.

후처리

  1. temperatureto reflux temperature
  2. temperaturewhile maintaining the temperature
  3. temperatureat reflux
  4. temperatureAfter an additional 30 minutes heating
  5. temperaturethe solution is cooled to 5°
  6. additionfollowed by dropwise addition of 11.9 g
  7. temperaturewith cooling
  8. washthe mixture is washed three times with aqueous hydrochloric acid (1.5 N) and three times with water
  9. dry with materialThe organic solution is dried (MgSO4)
  10. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-f4301a53468d4adb8c4fabee82167e4d
출처 데이터셋
uspto-grants-1983_02
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04371526

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