monoethyl prenylidenemalonate | 135788-37-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: monoethyl prenylidenemalonate
• CAS: 135788-37-3
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: CENPOKFTHFXRNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.53
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  63.6
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-甲基-2-丁烯醛 、 monoethyl prenylidenemalonate 在 哌啶 作用下， 以 苯 为溶剂， 反应 54.0h， 以55%的产率得到ethyl 6-(2'-methyl-1'-propenyl)-4-methyl-1,3-cyclohexadienecarboxylate
  参考文献：
  名称：

  Mechanism of cyclocondensation of isoprenoid acyclic ?,?-enals with monoethyl malonate under the conditions of the Knoevenagel reaction

  摘要：

  It was shown that the formation of the di- and trisubstituted derivatives of 1.3-cyclohexadiene-1-carboxylic acid during the condensation of 3-methyl-2-butenal, citral, and farnesal with monoethyl malonate in the presence of secondary amines takes place through the enamines corresponding to these aldehydes, which add to the monoesters of the respective alkenylidenemalonic acids (the "normal" products of the Knoevenagel reaction) by a mechanism of [4 + 2]-cycloaddition. The free carboxyl group in the dienophile is required for the spontaneous transformation of the intermediate [4 + 2]-cycloadducts into the derivatives of cyclohexadiene-1-carboxylic acid in which the catalyst of the process (the secondary amine) is regenerated.

  DOI：

  10.1007/bf00961358
• 作为产物：
  描述：

  2-[3-Methyl-but-2-en-(Z)-ylidene]-malonic acid tert-butyl ester ethyl ester 在 三氟乙酸 作用下， 反应 3.0h， 以8.4%的产率得到monoethyl prenylidenemalonate
  参考文献：
  名称：

  Mechanism of cyclocondensation of isoprenoid acyclic ?,?-enals with monoethyl malonate under the conditions of the Knoevenagel reaction

  摘要：

  It was shown that the formation of the di- and trisubstituted derivatives of 1.3-cyclohexadiene-1-carboxylic acid during the condensation of 3-methyl-2-butenal, citral, and farnesal with monoethyl malonate in the presence of secondary amines takes place through the enamines corresponding to these aldehydes, which add to the monoesters of the respective alkenylidenemalonic acids (the "normal" products of the Knoevenagel reaction) by a mechanism of [4 + 2]-cycloaddition. The free carboxyl group in the dienophile is required for the spontaneous transformation of the intermediate [4 + 2]-cycloadducts into the derivatives of cyclohexadiene-1-carboxylic acid in which the catalyst of the process (the secondary amine) is regenerated.

  DOI：

  10.1007/bf00961358

文献信息

• Catalytic asymmetric synthesis of polysubstituted cyclohexa-1,3-dienes from ?-branched ?,?-alkenals
  作者：A. G. Nigmatov、E. P. Serebryakov

  DOI：10.1007/bf01435793

  日期：1996.3

  °C to give optically active esters of 4,6-disubstituted cyclohexa-1,3-diene-l-carboxylic acids in moderate (10–43 %) yields. The enantiomeric purity of the products formed from the lint two types of acidic ylidenemalonates varies from 28 to 68 % and is higher than that observed in the case of related alkylidenemalonates. Under similar conditions cyclohexylideneacetaldehyde affords optically active derivatives

  摘要 3-甲基-和3-苯基丁-2-烯醛在苯或THF中（S）-脯氨醇（0.1当量）存在下与亚烯基、芳基亚甲基-和亚烷基丙二酸的酸性单酯在-10至+反应22 °C 以中等 (10–43%) 的产率得到 4,6-二取代的环六-1,3-二烯-1-羧酸的旋光酯。由棉绒两种类型的酸性亚亚丙二酸酯形成的产物的对映体纯度在 28% 至 68% 之间变化，并且高于在相关亚烷基丙二酸酯的情况下观察到的纯度。在类似的条件下，亚环己基乙醛得到 1,5,6,7,8,8a-六氢萘的旋光衍生物，为顺式和反式异构体的混合物。
• Catalytic asymmetric synthesis of 6-substituted derivatives of 1,3-cyclohexadienecarboxylic acid
  作者：A. G. Nigmatov、E. P. Serebryakov

  DOI：10.1007/bf00700021

  日期：1993.1