4-methyl-2-(toluene-4-sulfonyloxy)-cycloheptatrienone | 72271-67-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-methyl-2-(toluene-4-sulfonyloxy)-cycloheptatrienone
• 英文别名: 4-Methyl-2-(toluol-4-sulfonyloxy)-cycloheptatrienon；(3-Methyl-7-oxocyclohepta-1,3,5-trien-1-yl) 4-methylbenzenesulfonate
• CAS: 72271-67-1
• 化学式: C₁₅H₁₄O₄S
• 分子量: 290.34
• InChiKey: ATBVRLLGVYVQAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-methyl-2-(toluene-4-sulfonyloxy)-cycloheptatrienone 在 platinum(IV) oxide 、 甲烷 咪唑 、 氢氧化钾 、 lithium aluminium tetrahydride 、 乙酸乙烯酯 、 Amano Lipase PS 、 4 A molecular sieve 、 氢气 、 sodium methylate 、 sodium ethanolate 、 sodium hydride 作用下， 以 甲醇 、 乙醚 、 乙醇 为溶剂， 200.0 ℃ 、101.33 kPa 条件下， 反应 30.71h， 生成 [(2S)-2-[(1S,2S,5S)-2-hydroxy-5-methylcyclohept-3-en-1-yl]propyl] acetate
  参考文献：
  名称：

  A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα)-3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2H- cyclohepta[b]furan-2-one, (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1β-ol, and (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1-one. Possible Common Synthetic Intermediates for Pseudoguaianolides, 4,5-Secopseudoguaianolides, Guaianolides, 4,5-Secoguaianolides, and Octalactins

  摘要：

  The catalytic hydrogenation of ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b] (6), which was derived regioselectively from 4-methyltropolone (1) in four steps in 62% overall yield, gave (3a alpha,8a alpha)-ethyl 8 beta-hydroxy-6 beta-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3 alpha-carboxylate (8b) in 45% yield. It is noteworthy that four asymmetric centers newly introduced on the seven-membered ring of 8b were controlled to be syn-oriented by the single operation. The latter was transformed to (3a alpha,8a alpha)-3 alpha,6 beta-dimethyl-3,3a,4,5,6,8a-hexahydro-2H-cyclohepta[b]furan-2-one (17a) in 77% overall yield in five steps, Reduction of 17a with LiAlH4 gave (+/-)-7 beta-(2-hydroxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (22), whose enantioselective acetylation was achieved by vinyl acetate in the presence of Lipase PS to give (+)-7 beta-(2-acetoxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (24) in 48% yield (93% ee) or in 52% yield (77% ee) and (-)-22 in 52% yield (70% ee) or 44% yield (89% ee). Oxidation of (+)-24 with MnO2 gave (-)-7 beta-(2-acetoxy-1 alpha-methyl ethyl)-4 beta-methyl-2-cyclohepten-1-one (-)-(25). Similarly, acetylation of (-)-22 followed by oxidation of resulting (-)-24 gave (+)-25.

  DOI：

  10.1021/jo971529q
• 作为产物：
  描述：

  (6-Iodo-3-methyl-7-oxocyclohepta-1,3,5-trien-1-yl) 4-methylbenzenesulfonate 在 palladium on activated charcoal 氢气 、 sodium acetate 作用下， 以 甲醇 为溶剂， 反应 1.33h， 以89%的产率得到4-methyl-2-(toluene-4-sulfonyloxy)-cycloheptatrienone
  参考文献：
  名称：

  A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα)-3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2H- cyclohepta[b]furan-2-one, (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1β-ol, and (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1-one. Possible Common Synthetic Intermediates for Pseudoguaianolides, 4,5-Secopseudoguaianolides, Guaianolides, 4,5-Secoguaianolides, and Octalactins

  摘要：

  The catalytic hydrogenation of ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b] (6), which was derived regioselectively from 4-methyltropolone (1) in four steps in 62% overall yield, gave (3a alpha,8a alpha)-ethyl 8 beta-hydroxy-6 beta-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3 alpha-carboxylate (8b) in 45% yield. It is noteworthy that four asymmetric centers newly introduced on the seven-membered ring of 8b were controlled to be syn-oriented by the single operation. The latter was transformed to (3a alpha,8a alpha)-3 alpha,6 beta-dimethyl-3,3a,4,5,6,8a-hexahydro-2H-cyclohepta[b]furan-2-one (17a) in 77% overall yield in five steps, Reduction of 17a with LiAlH4 gave (+/-)-7 beta-(2-hydroxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (22), whose enantioselective acetylation was achieved by vinyl acetate in the presence of Lipase PS to give (+)-7 beta-(2-acetoxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (24) in 48% yield (93% ee) or in 52% yield (77% ee) and (-)-22 in 52% yield (70% ee) or 44% yield (89% ee). Oxidation of (+)-24 with MnO2 gave (-)-7 beta-(2-acetoxy-1 alpha-methyl ethyl)-4 beta-methyl-2-cyclohepten-1-one (-)-(25). Similarly, acetylation of (-)-22 followed by oxidation of resulting (-)-24 gave (+)-25.

  DOI：

  10.1021/jo971529q

文献信息

• Reactions of 2-Tosyloxy- and 2-Chlorotropones with Hydrazine, Methylhydrazine, and Phenylhydrazine
  作者：Kimiaki Imafuku、Katsuya Kamachi、Yasunori Matsuda、Hisashi Matsumura

  DOI：10.1246/bcsj.52.2447

  日期：1979.8

  hydrazine, methylhydrazine, and phenylhydrazine gave 2-hydrazinotropones, 2-(α-methylhydrazino)-tropones, and 2-(β-phenylhydrazino)tropones, respectively. All the reactions are normal substitution at C-2 position of the tropone ring. No cine reaction was observed. The reactivity of hydrazines decreases in the order: NH2NH2>CH3NHNH2>>PhNHNH2.

  2-tosyloxytropones 或 2-chlorotropones 与肼、甲基肼和苯肼的反应分别产生 2-hydrazinotropones、2-(α-methylhydrazino)-tropones 和 2-(β-phenylhydrazino)tropones。所有反应都是在托酮环的 C-2 位进行正常取代。没有观察到电影反应。肼的反应性按以下顺序降低：NH2NH2>CH3NHNH2>>PhNHNH2。
• A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2<i>H</i>-cyclohepta[<i>b</i>]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα)-3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2<i>H</i>- cyclohepta[<i>b</i>]furan-2-one, (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1β-ol, and (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1-one. Possible Common Synthetic Intermediates for Pseudoguaianolides, 4,5-Secopseudoguaianolides, Guaianolides, 4,5-Secoguaianolides, and Octalactins
  作者：Fumito Shimoma、Haruhiko Kusaka、Katsuaki Wada、Hidenori Azami、Masafumi Yasunami、Toshio Suzuki、Hisahiro Hagiwara、Masayoshi Ando

  DOI：10.1021/jo971529q

  日期：1998.2.1

  The catalytic hydrogenation of ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b] (6), which was derived regioselectively from 4-methyltropolone (1) in four steps in 62% overall yield, gave (3a alpha,8a alpha)-ethyl 8 beta-hydroxy-6 beta-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3 alpha-carboxylate (8b) in 45% yield. It is noteworthy that four asymmetric centers newly introduced on the seven-membered ring of 8b were controlled to be syn-oriented by the single operation. The latter was transformed to (3a alpha,8a alpha)-3 alpha,6 beta-dimethyl-3,3a,4,5,6,8a-hexahydro-2H-cyclohepta[b]furan-2-one (17a) in 77% overall yield in five steps, Reduction of 17a with LiAlH4 gave (+/-)-7 beta-(2-hydroxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (22), whose enantioselective acetylation was achieved by vinyl acetate in the presence of Lipase PS to give (+)-7 beta-(2-acetoxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (24) in 48% yield (93% ee) or in 52% yield (77% ee) and (-)-22 in 52% yield (70% ee) or 44% yield (89% ee). Oxidation of (+)-24 with MnO2 gave (-)-7 beta-(2-acetoxy-1 alpha-methyl ethyl)-4 beta-methyl-2-cyclohepten-1-one (-)-(25). Similarly, acetylation of (-)-22 followed by oxidation of resulting (-)-24 gave (+)-25.