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

HRID 1375272

Reaktionsgleichung

Reaktionsgleichung von HRID 1375272
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]

Komponenten

9

Edukt 4

HCID 24287Tin tetrachlorideHCID 158872882,2-Dimethyl-4(tol4-yl)-chrom-3-en-6-al2×HCID 57037360Ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate2×HCID 178418339Butyllithium

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 6344DichloromethaneLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-22bbaf0b658a47038d2ea7fe59c7d773
Quelldatensatz
uspto-grants-2007_01
Patentnummer
US07166726B2

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