Terephthalaldehyde → 4-[3-oxo-3-((1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-propenyl]-benzaldehyde

HRID 2261439노트

반응식

HRID 2261439 반응식
[CH3:1][C:2]1([CH3:15])[C@@H:4]2[CH2:5][C:6]3[C:10]([C@H:3]12)=[C:9]([CH3:11])[S:8][C:7]=3[C:12](=[O:14])[CH3:13].[CH:16](=O)[C:17]1[CH:24]=[CH:23][C:20]([CH:21]=[O:22])=[CH:19][CH:18]=1>C(O)C.Cl.C(O)(C)C.C(OCC)C>[O:14]=[C:12]([C:7]1[S:8][C:9]([CH3:11])=[C:10]2[C:6]=1[CH2:5][C@H:4]1[C:2]([CH3:15])([CH3:1])[C@H:3]12)[CH:13]=[CH:16][C:17]1[CH:24]=[CH:23][C:20]([CH:21]=[O:22])=[CH:19][CH:18]=1

참가 물질

7

반응물 2

HCID 12173TerephthalaldehydeHCID 59380608(1aS,5aR)-1-(1,1,2-Trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanone

생성물 1

HCID 866225074-[3-oxo-3-((1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-propenyl]-benzaldehyde수율 36.7%

시약·촉매·용매 4

HCID 313Hydrochloric Acid용매2회HCID 702Ethanol용매HCID 3283Diethyl Ether용매HCID 3776Isopropanol용매2회

실험 절차

A solution of (1aS,5aR)-1-(1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanone (600 mg, 2.72 mmol) and terephthalaldehyde (913 mg, 6.81 mmol) in ethanol (10 mL) and approx. 6 N HCl in isopropanol (6 mL) is stirred at rt for 16 h. Further 6 N HCl in isopropanol (5 mL) is added and stirring of the dark solution is continued at rt for 24 h. The reaction mixture is diluted with diethyl ether (150 mL) and washed with sat. aq. NaHCO3 solution followed by water. The organic phase is dried over MgSO4 and evaporated. The crude product is purified by CC on silica gel eluting with heptane:EA 4:1 to give 4-[3-oxo-3-((1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-propenyl]-benzaldehyde (336 mg) as a yellow powder; LC-MS: tR=1.14 min, [M+1]+=337.29; 1H NMR (CDCl3): δ 10.04 (s, 1H), 7.94-7.89 (m, 2H), 7.80-7.71 (m, 3H), 7.30 (d, J=15.8 Hz, 1H), 3.14 (dd, J=5.9, 18.8 Hz, 1H), 2.95 (d, J=18.8 Hz, 1H), 2.44 (s, 3H), 2.00-1.91 (m, 2H), 1.15 (s, 3H), 0.75 (s, 3H).

후처리

  1. washwashed with sat. aq. NaHCO3 solution
  2. dry with materialThe organic phase is dried over MgSO4
  3. customevaporated
  4. customThe crude product is purified by CC on silica gel eluting with heptane:EA 4:1

출처 및 근거

ORD 기록
ord-2daeffce134f435eb5790997c7606e57
출처 데이터셋
uspto-grants-2010_12
특허 번호
US07846964B2

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