methyl 3-carbomethoxy-5-hexynoate | 99474-28-9

• 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 3-carbomethoxy-5-hexynoate
• 英文别名: Methyl-3-carbomethoxy-5-hexynoate；dimethyl 2-prop-2-ynylbutanedioate
• CAS: 99474-28-9
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: LMZYIHHFZFMPMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-carbomethoxy-5-hexynoate 在 sodium methylate 作用下， 反应 102.5h， 生成 methyl 3-carbomethoxy-4-(1'-hydroxy-4',9'-dimethoxy-2'-phenanthryl)butanoate
  参考文献：
  名称：

  Metal-Catalyzed Cyclopropene Rearrangements for Benzannulation: Evaluation of an Anthraquinone Synthesis Pathway and Reevaluation of the Parallel Approach via Carbene-Chromium Complexes

  摘要：

  The reaction of 3-arylcyclopropenes with Cr(CO)(6) and Mo(CO)(6) produces naphthols, in an example of metal-promoted benzannulation. Substituents at C-3 (in addition to aryl) have a strong effect on the success of the process: 3-H derivatives are generally effective, but the yields decrease for 3-alkyl derivatives as the size of the alkyl group increases. The 3,3-diphenyl and 3-cyano derivatives are unreactive. The mechanism is postulated to involve metal-complexed vinyl carbene units, parallel with the benzannulation reaction involving arylcarbene complexes with alkynes. The regioselectivity has been probed with various unsymmetrically 1,2-disubstituted 3-arylcyclopropenes. The results suggest a simple correlation with steric size, consistent with initial cleavage of the cyclopropene sigma bond bearing the smaller substituent. The result of this regioselectivity is a product structure showing a substituent arrangement opposite to that from the carbene-chromium approach; the smaller substituent of the cyclopropyl double bond ends up adjacent to the phenol OH in the product. Catalytic activity at low efficiency was observed, using a Mo(CO)a catalyst. However, the use of Mo(CO)(6) also promotes formation of indenes as significant byproducts at the expense of naphthalenes. Attempts to use the arylcyclopropene rearrangement to convert a 3-(1,4-dimethoxy-2-naphthyl)cyclopropene to an anthraquinone skeleton produced instead a phenanthrene via an unusual substitution for a methoxy substituent. A related example previously reported to produce anthraquinones via the naphthylcarbene-chromium/ alkyne reaction was shown to be in error; the correct structure is again a phenanthrone, and the product is exactly parallel with that observed in the cyclopropene rearrangement. A naphthoquinone substituted with a cyclopropene at C-2 does provide the first example of metal-promoted benzannulation to give an anthraquinone.

  DOI：

  10.1021/ja00095a014
• 作为产物：
  描述：

  3-acetyl-3-carbomethoxy-5-hexynoic acid methylester 在 氢氧化钾 、 水 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 5.0h， 生成 methyl 3-carbomethoxy-5-hexynoate
  参考文献：
  名称：

  碳配体作为蒽环素-synthons-ii °：铬介导的炔烃，卡宾和一氧化碳的环加成：在蒽环素的环b合成中的应用

  摘要：

  Cr配位的炔烃，卡宾和羰基配体的环加成为蒽环素骨架提供了一条可变的路线。正式全合成4-脱甲氧基十二烷酮（1）的关键步骤是基于羰基-卡宾配合物15（用作CD环合成子）与炔烃9的反应，从而导致环B的形成。

  DOI：

  10.1016/s0040-4020(01)91419-x

文献信息

• Metal carbene chelates: stable reactive intermediates in cycloaddition reactions
  作者：Karl Heinz Dötz、Michael Popall、Gerhard Müller

  DOI：10.1016/0022-328x(87)80038-4

  日期：1987.11

  additional donor group affords stable five-membered metal carbene chelates. Olefin-chelated metallacycles are obtained via aminolysis of alkoxy carbene complexes using allylamine. Heteroatom metal carbene chelates are accessible from ortho-lithiated methoxyarenes in a two-step process involving a sequential nucleophile/electrophile addition to metal carbonyls followed by thermal decarbonylation. Both

  在卡宾γ位带有杂原子或CC键的羰基卡宾络合物易于脱羰。额外的供体基团的配合提供了稳定的五元金属卡宾螯合物。通过烯丙基胺通过烷氧基卡宾配合物的氨解获得烯烃螯合的金属环。杂原子金属卡宾螯合物可从邻位获得-锂化甲氧基芳烃的过程分为两步，涉及向金属羰基化合物中依次添加亲核试剂/亲电子试剂，然后进行热脱羰作用。两种类型的化合物已通过X射线分析进行了系统研究。氧杂金属环化合物的特征是长的金属与氧的键。在卡宾环化反应中利用了易于开环的方法，在该反应中，现在可以将配体偶联与金属模板上空位配位位点的产生分开。该策略的范围由蒽环素的两种方法证明：环B或C可以由1,4-二甲氧基-2-萘基卡宾或茴香基卡宾合成子形成。
• The direct electrochemical synthesis of 2,2′-bipyridine adducts of organomagnesium halides, and of salts of organodihalogenomagnesium(II) anions
  作者：Peter C. Hayes、Akhtar Osman、Narace Seudeal、Dennis G. Tuck

  DOI：10.1016/0022-328x(85)80197-2

  日期：1985.8

  The electrochemical oxidation of magnesium into acetonitrile solutions containing alkyl or aryl halides (RX) and 2,2′-bipyridine (bipy) yields the neutral adducts RMgX · bipy. With α,ω-dihalides XR′X, the products are the corresponding R′Mg2X2 · 2bipy compounds. The preparation proceeds equally well with either aryl or alkyl compounds, and with chlorides, bromides, or iodides, but the resultant adducts

  将镁电化学氧化为含有烷基或芳基卤化物（RX）和2,2'-联吡啶（bipy）的乙腈溶液，得到中性加合物RMgX·bipy。对于α，ω-二卤化物XR'X，产物是相应的R'Mg 2 X 2 ·2bipy化合物。不论是用芳基化合物还是烷基化合物，以及使用氯化物，溴化物或碘化物，制备过程均能很好地进行，但是所得加合物除了用矿物酸消除烷烃外，没有表现出格利雅试剂的典型反应。用含有RX和R解决方案' 4 NX，电化学氧化产物是盐R' 4 N [RMGX 2 ·CH 3 CN]，其也缺乏典型的格氏试剂的化学反应。
• Doetz, Karl Heinz; Popall, Michael, Chemische Berichte, 1988, vol. 121, p. 665 - 672
  作者：Doetz, Karl Heinz、Popall, Michael

  DOI：——

  日期：——
• DOETZ, K. -H.
  作者：DOETZ, K. -H.

  DOI：——

  日期：——
• DOTZ, KARL HEINZ;POPALL, MICHAEL;MULLER, GERHARD, J. ORGANOMET. CHEM., 334,(1987) N 1-2, 57-75
  作者：DOTZ, KARL HEINZ、POPALL, MICHAEL、MULLER, GERHARD

  DOI：——

  日期：——