Hydrochloric Acid → 3,4-Dihydro-4,4,5,8-tetramethyl-2H-1-benzothiopyran-6-carboxaldehyde

HRID 798

반응식

HRID 798 반응식
Br[C:2]1[CH:3]=[C:4]([CH3:15])[C:5]2[S:10][CH2:9][CH2:8][C:7]([CH3:12])([CH3:11])[C:6]=2[C:13]=1[CH3:14].C([Li])CCC.CN(C)[CH:23]=[O:24].Cl>C(OCC)C>[CH3:11][C:7]1([CH3:12])[C:6]2[C:13]([CH3:14])=[C:2]([CH:23]=[O:24])[CH:3]=[C:4]([CH3:15])[C:5]=2[S:10][CH2:9][CH2:8]1

참가 물질

6

반응물 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 129936856-Bromo-3,4-dihydro-4,4,5,8-tetramethyl-2H-1-benzothiopyranHCID 178418339Butyllithium

생성물 1

HCID 196938673,4-Dihydro-4,4,5,8-tetramethyl-2H-1-benzothiopyran-6-carboxaldehyde

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

실험 절차

6-Bromo-3,4-dihydro-4,4,5,8-tetramethyl-2H-1-benzothiopyran (19.8 g, World Patent Application 95/04054) was dissolved in diethyl ether (350 mL) and treated with n-butyllithium (2.5N in hexanes, 42 mL). The mixture was stirred at room temperature for 1 h and then cooled in a dry-ice/acetone bath. Dimethylformamide (16 mL) was added over a period of several minutes and the reaction bath was allowed to warm to -40° C. Hydrochloric acid (1N aqueous, 100 mL) was added and the mixture was allowed to warm to 23° C. The organic phase was separated and washed with saturated aqueous sodium bicarbonate solution (100 mL). The organic phase was dried over magnesium sulfate, filtered, and evaporated under reduced pressure. The residue was subjected to chromatography on silica gel using hexanes/ether (9:1) as eluent to afford the desired compound as a yellow semi-solid (7.7 g). 1H NMR(CDCl3): δ 1.5 (6H), 2.0 (2H), 2.3 (3H), 2.8 (3H), 3.0 (2H), 7.4 (1H), 10.2 (1H).

후처리

  1. temperaturecooled in a dry-ice/acetone bath
  2. temperatureto warm to -40° C
  3. temperatureto warm to 23° C
  4. customThe organic phase was separated
  5. washwashed with saturated aqueous sodium bicarbonate solution (100 mL)
  6. dry with materialThe organic phase was dried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure

출처 및 근거

ORD 기록
ord-415b27028875405d86f41fbc30253639
출처 데이터셋
uspto-grants-1998_03
특허 번호
US05723411

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