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 2261439ノート

反応式

HRID 2261439 の反応式
[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

参加物

7

反応物 2

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

生成物 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]-benzaldehyde収率 36.7%

試薬・触媒・溶媒 4

HCID 313Hydrochloric Acid溶媒2 回HCID 702Ethanol溶媒HCID 3283Diethyl Ether溶媒HCID 3776Isopropanol溶媒2 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-2daeffce134f435eb5790997c7606e57
出典データセット
uspto-grants-2010_12
特許番号
US07846964B2

反応ノート

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