Methyl 7-oxo-2-octynoate | 136401-39-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl 7-oxo-2-octynoate
• 英文别名: Methyl 7-oxooct-2-ynoate
• CAS: 136401-39-3
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: OFPWZYSSORHADJ-UHFFFAOYSA-N

物化性质

• 沸点：
  286.0±23.0 °C(Predicted)
• 密度：
  1.044±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 7-oxo-2-octynoate 以 甲醇 、 甲苯 、 苯 为溶剂， 反应 3.5h， 生成 1-Methyl-4-methylene-4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one
  参考文献：
  名称：

  N-[1-甲基-6-(甲氧基羰基)-5-己炔基]甲胺N-氧化物的意外热重排

  摘要：

  N-[1-Methyl-6-(甲氧基羰基)-5-hexynylidene]methylamine N-oxide，一种酮硝酮，由 7-oxooct-2-ynoate 甲酯和 N-甲基羟胺热重排成两种异构双环化合物反应制备而不是预期的分子内 [3+2] 环加合物。醛硝酮、N-[6-(甲氧基羰基)-5-己炔基]甲胺N-氧化物也提供相应的重排产物。

  DOI：

  10.1246/cl.1991.1333
• 作为产物：
  描述：

  5-氯-2-戊酮 在 盐酸 、 六甲基磷酰三胺 、 正丁基锂 、 乙二胺 作用下， 以 四氢呋喃 为溶剂， 反应 14.83h， 生成 Methyl 7-oxo-2-octynoate
  参考文献：
  名称：

  Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol

  摘要：

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.

  DOI：

  10.1021/jo00085a036

文献信息

• Intramolecular [3+2] nitrone-alkyne cycloaddition
  作者：Han-Young Kang、Yong Seo Cho、Hun Yeong Koh、Moon Ho Chang

  DOI：10.1016/0040-4039(91)85084-i

  日期：1991.6

  It is demonstrated that the [3+2] cycloaddition of a nitrone to an alkyne is facile when the length of the tether connecting the two reacting sites is appropriate. The resulting [3+2] cycloaddition products, isoxazolidines can be further converted to 3-hydroxy-3-pyrrolin-2-ones and alpha-keto-beta, gamma-unsaturated esters by reductive and oxidative cleavage, respectively.
• Novel Routes to Chiral 2-Alkoxy-5-/6- methoxycarbonylmethylidenepyrrolidines/-piperidines
  作者：Olivier David、Sandrine Calvet、François Chau、Corinne Vanucci-Bacqué、Marie-Claude Fargeau-Bellassoued、Gérard Lhommet

  DOI：10.1021/jo049961c

  日期：2004.4.1

  We report the results of a study aimed at the diastereoselective synthesis of chiral 2-alkoxy-5-/6-methoxy-carbonylmethylidenepyrrolidines/-piperidines by condensation of chiral amines onto omega-oxo alkynoates and omega-oxo beta-keto esters.
• Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol
  作者：Ge Hyeong Lee、Eun Bok Choi、Eun Lee、Chwang Siek Pak

  DOI：10.1021/jo00085a036

  日期：1994.3

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.
• Unexpected Thermal Rearrangement of<i>N</i>-[1-Methyl-6-(methoxycarbonyl)-5-hexynylidene]methylamine<i>N</i>-Oxide
  作者：Han-Young Kang、Yong Seo Cho、Hun Yeong Koh、Moon Ho Chang

  DOI：10.1246/cl.1991.1333

  日期：1991.8

  prepared from the reaction between methyl 7-oxooct-2-ynoate and N-methylhydroxylamine rearranged thermally into two isomeric bicyclic compounds instead of the expected intramolecular [3+2] cycloadduct. Also an aldonitrone, N-[6-(methoxycarbonyl)-5-hexynylidene]methylamine N-oxide provided the corresponding rearranged product.

  N-[1-Methyl-6-(甲氧基羰基)-5-hexynylidene]methylamine N-oxide，一种酮硝酮，由 7-oxooct-2-ynoate 甲酯和 N-甲基羟胺热重排成两种异构双环化合物反应制备而不是预期的分子内 [3+2] 环加合物。醛硝酮、N-[6-(甲氧基羰基)-5-己炔基]甲胺N-氧化物也提供相应的重排产物。