Tin tetrachloride → Ethyl 4-[2,2-dimethyl-4-(tol-4-yl)-benzo(1,2-g)-chrom-3-en-7-yl]benzoate

HRID 1862741

반응식

HRID 1862741 반응식
C(OP([C:9](OC)(OC)[CH2:10][CH2:11][C:12]1[CH:22]=[CH:21][C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:14][CH:13]=1)(OCC)=O)C.[Li]CCCC.[CH3:32][C:33]1([CH3:52])[CH:42]=[C:41]([C:43]2[CH:48]=[CH:47][C:46]([CH3:49])=[CH:45][CH:44]=2)[C:40]2[C:35](=[CH:36][CH:37]=[C:38]([CH:50]=O)[CH:39]=2)[O:34]1.Cl[Sn](Cl)(Cl)Cl>C1COCC1.CCCCCC.C(OCC)(=O)C.ClCCl>[CH2:19]([O:18][C:16](=[O:17])[C:15]1[CH:14]=[CH:13][C:12]([C:11]2[CH:50]=[CH:38][C:37]3[CH:36]=[C:35]4[C:40]([C:41]([C:43]5[CH:48]=[CH:47][C:46]([CH3:49])=[CH:45][CH:44]=5)=[CH:42][C:33]([CH3:52])([CH3:32])[O:34]4)=[CH:39][C:9]=3[CH:10]=2)=[CH:22][CH:21]=1)[CH3:20]

참가 물질

9

반응물 4

HCID 24287Tin tetrachlorideHCID 158872882,2-Dimethyl-4(tol4-yl)-chrom-3-en-6-al2회HCID 57037360Ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate2회HCID 178418339Butyllithium

생성물 1

HCID 9933376Ethyl 4-[2,2-dimethyl-4-(tol-4-yl)-benzo(1,2-g)-chrom-3-en-7-yl]benzoate

시약·촉매·용매 4

HCID 6344Dichloromethane용매2회HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

실험 절차

To a cold (−78° C.) solution of ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate (Compound D, 1.4 g, 3.6 mmol) in THF (9 mL) was added n-BuLi in hexane (1.6 M solution, 2.8 mL). The mixture was gradually warmed to ambient temperature over 30 minutes and stirred for 5 minutes. To this mixture was added 2,2-dimethyl-4(tol-4-yl)-chrom-3-en-6-al (Compound Q, 260 mg, 0.93 mmol) in THF (1 mL) at ambient temperature and the mixture was stirred for 5 hours. The reaction mixture was diluted with ethyl acetate (100 mL) and washed with brine (10 mL) dried and the solvent was removed by evaporation. The residual material was subjected to flash chromatography on silicagel to obtain the E and Z olefinic compounds, which were dissolved in dichloromethane (5 mL) and cooled to −50° C. A solution of SnCl4 in dichloromethane (150 mg in 0.7 mL) was added to the olefinic compounds. The reaction mixture was gradually warmed to −10° C. over 3 hours and then quenched with methanol and water. The reaction mixture was diluted with ethyl acetate (100 mL). The organic layer was washed with brine and dried. Solvent was removed under reduced pressure and the residue purified by chromatography on silicagel to afford the title compound as a white solid.

후처리

  1. stirringthe mixture was stirred for 5 hours
  2. washwashed with brine (10 mL)
  3. customdried
  4. customthe solvent was removed by evaporation
  5. customto obtain the E and Z olefinic compounds, which
  6. temperaturecooled to −50° C
  7. temperatureThe reaction mixture was gradually warmed to −10° C. over 3 hours
  8. customquenched with methanol and water
  9. additionThe reaction mixture was diluted with ethyl acetate (100 mL)
  10. washThe organic layer was washed with brine
  11. customdried
  12. customSolvent was removed under reduced pressure
  13. customthe residue purified by chromatography on silicagel

출처 및 근거

ORD 기록
ord-b8146d5137a04378862097ad6bd50725
출처 데이터셋
uspto-grants-2003_03
특허 번호
US06538149B1

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