二乙基(3,4-dimethoxybenzylidene)丙二酸酯 | 15818-13-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 中文名称: 二乙基(3,4-dimethoxybenzylidene)丙二酸酯
• 英文名称: diethyl 2-(3,4-dimethoxybenzylidene)malonate
• 英文别名: diethyl 3,4-dimethoxybenzalmalonate；2-(3,4-Dimethoxy-benzyliden)-malonsaeure-diethylester；(3,4-Dimethoxy-benzyliden)-malonsaeure-diethylester；diethyl 2-[(3,4-dimethoxyphenyl)methylidene]propanedioate
• CAS: 15818-13-0
• 化学式: C₁₆H₂₀O₆
• 分子量: 308.331
• InChiKey: FASDMQRNYJBJQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  二乙基(3,4-dimethoxybenzylidene)丙二酸酯 在 palladium on activated charcoal 盐酸 、 氢气 、 三乙胺 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 60.0 ℃ 、275.79 kPa 条件下， 生成 4-(3,4-Dimethoxyphenyl)-2-pyrrolidone
  参考文献：
  名称：

  Inhibition of cyclic adenosine-3',5'-monophosphate phosphodiesterase from vascular smooth muscle by rolipram analogs

  摘要：

  Rolipram [(R,S)-4-[3-(cyclopentyloxy)-4-methoxyphenyl]-2-pyrrolidone] has been shown to inhibit selectively the cAMP phosphodiesterase (PDE) of vascular smooth muscle. In order to further explore the structural requirements for selective PDE inhibition, we synthesized a series of rolipram derivatives differently substituted either at the pyrrolidinone or at the aromatic ring. Among these compounds, rolipram was the most active compound. Semirigid analogues were prepared and used for an evaluation of the active conformation of rolipram. Structural comparison with two other potent and chemically different smooth muscle cAMP-PDE inhibitors, trequinsin and Ro 20-1724, allows us to propose a first topological model of the smooth muscle cAMP-PDE pharmacophore.

  DOI：

  10.1021/jm00127a009
• 作为产物：
  描述：

  1-(3,4-二甲氧基苯基)-N-苯基-甲亚胺 、 丙二酸二乙酯 在 哌啶 作用下， 以 苯 为溶剂， 以90%的产率得到二乙基(3,4-dimethoxybenzylidene)丙二酸酯
  参考文献：
  名称：

  Manrao, M. R.; Kaur, Baljit; Sharma, R. C., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1982, vol. 21, # 11, p. 1059 - 1060

  摘要：

  DOI：

文献信息

• Accessing Dihydro-1,2-oxazine via Cloke–Wilson-Type Annulation of Cyclopropyl Carbonyls: Application toward the Diastereoselective Synthesis of Pyrrolo[1,2-<i>b</i>][1,2]oxazine
  作者：Pankaj Kumar、Rakesh Kumar、Prabal Banerjee

  DOI：10.1021/acs.joc.0c00531

  日期：2020.5.15

  A convenient additive-free synthesis of dihydro-4H-1,2-oxazines via a Cloke-Wilson-type ring expansion of the aryl-substituted cyclopropane carbaldehydes with the hydroxylamine salt is introduced. Comparatively less active cyclopropyl ketones also follow a similar protocol if supplemented by catalytic p-toluene sulfonic acid monohydrate. The transformation is performed in an open-to-air flask as it

  通过芳基取代的环丙烷甲醛与羟胺盐的Cloke-Wilson型扩环，方便地合成了二氢-4H-1,2-恶嗪。如果由催化对甲苯磺酸一水合物补充，则活性相对较低的环丙基酮也遵循类似的方案。由于它对空气/水分的敏感性可以忽略不计，因此在露天烧瓶中进行转化。当二氢-4H-1,2-恶嗪与环丙烷二酯进行环加成反应时，可以很容易地配制出有价值的六氢-2H-吡咯并[1,2-b] [1,2]恶嗪衍生物。这种两步策略的级联一锅法变体可提供最终产品相当的总产量。
• Process for the preparation of carboxylic acids and derivatives of them
  申请人：BIOGAL GYOGYSZERGYAR

  公开号：EP0578850A1

  公开（公告）日：1994-01-19

  The subject matter of the invention is a process for the preparation of carboxylic acids and derivatives of them of the general formula wherein Rmeans hydrogen, or a C₁₋₄alkyl or a (C₁₋₅alkoxy)carbonyl group, R₁is as defined in claim 1, R₇stands for hydrogen or a C₁₋₇alkyl group and R₈means hydrogen or a carboxyl group, by reacting a 1,3-dioxane-4,6-dione derivative of the general formula wherein R₉stands for a C₁₋₄alkyl group or a phenyl group, optionally monosubstituted by halogen and R₁₀stands for hydrogen or a C₁₋₅alkyl group or R₉ and R₁₀together form a pentamethylene group, and an aldehyde or ketone of the general formula in the presence of formic acid and of [a] amine(s) and, if desired, of an alcohol of the general formula         R₇ - OH   VI, wherein R₇is a C₁₋₇alkyl group, at a temperature of 20 to 140°C,    and/or reducing an unsaturated 1,3-dioxane-4,6-dione derivative of the general formula    and/or a 1,3-dioxane-4,6-dione derivative of the general formula with formic acid in the presence of [a] amine(s) and, if desired, of an alcohol as above defined.

  本发明的主题是一种用于制备通式为的羧酸及其衍生物的过程    其中 R表示氢，或C₁₋₄烷基或(C₁₋₅烷氧基)甲酰基， R₁如权利要求1中定义， R₇代表氢或C₁₋₇烷基团和 R₈表示氢或羧酸基， 通过将通式为的1,3-二氧杂环己烷-4,6-二酮衍生物与醛或酮反应    其中 R₉代表C₁₋₄烷基或苯基，可选地由卤素单取代 R₁₀代表氢或C₁₋₅烷基或 R₉和R₁₀共同形成一个戊烷基， 在甲酸和[a]胺的存在下，如果需要，还可以在上述定义的醇的存在下，          R₇ - OH         VI,    其中 R₇是C₁₋₇烷基， 在20至140°C的温度下，     和/或 将通式的不饱和1,3-二氧杂环己烷-4,6-二酮衍生物还原     和/或 通式为的1,3-二氧杂环己烷-4,6-二酮衍生物 与甲酸在[a]胺的存在下，如果需要，还可以在上述定义的醇的存在下。
• Lewis Acid-Catalyzed [3+2] Cycloaddition of Donor-Acceptor Cyclopropanes and Enamines: Enantioselective Synthesis of Nitrogen-Functionalized Cyclopentane Derivatives
  作者：Kamal Verma、Prabal Banerjee

  DOI：10.1002/adsc.201600221

  日期：2016.6.30

  efficient method for the synthesis of nitrogen‐functionalized cyclopentane derivatives via [3+2] cycloaddition of enamines with donor‐acceptor cyclopropanes in the presence of catalytic amounts of various Lewis acids at room temperature has been developed; furthermore, the corresponding β‐amino acid was synthesized by monodecarboxylation and hydrogenolysis. An enantioenriched synthesis of nitrogen‐functionalized

  在室温下催化量的各种路易斯酸存在下，开发了一种简单有效的方法，可通过烯胺与供体-受体环丙烷的[3 + 2]环加成反应，合成氮官能化的环戊烷衍生物；此外，通过单脱羧和氢解合成了相应的β-氨基酸。通过外消旋给体-受体环丙烷的动态动力学不对称转化，对氮官能化的环戊烷衍生物进行了对映体富集合成，采用铜络合物[Cu（OTf）2 - L1 ]作为催化剂，对映体比例高达8：1。
• Lewis Acid Catalyzed Annulation of Cyclopropane Carbaldehydes and Aryl Hydrazines: Construction of Tetrahydropyridazines and Application Toward a One-Pot Synthesis of Hexahydropyrrolo[1,2-<i>b</i>]pyridazines
  作者：Raghunath Dey、Pankaj Kumar、Prabal Banerjee

  DOI：10.1021/acs.joc.8b00332

  日期：2018.5.18

  In this report, a facile synthesis of tetrahydropyridazines via a Lewis acid catalyzed annulation reaction of cyclopropane carbaldehydes and aryl hydrazines has been demonstrated. Moreover, the generated tetrahydropyridazine further participated in a cycloaddition reaction with donor–acceptor cyclopropanes to furnish hexahydropyrrolo[1,2-b]pyridazines. We also performed these two steps in one pot in

  在该报告中，已经证明了通过路易斯酸催化的环丙烷甲醛和芳基肼的环合反应可轻松合成四氢哒嗪。此外，生成的四氢哒嗪进一步与供体-受体环丙烷一起参与环加成反应，提供六氢吡咯并[1,2- b ]哒嗪。我们还在一个锅中以连续的方式执行了这两个步骤。另外，六氢吡咯并[1,2- b ]哒嗪的单脱羧反应得到了良好的收率。
• Substituent and Lewis Acid Promoted Dual Behavior of Epoxides towards [3+2]-Annulation Reactions with Donor-Acceptor Cyclopropanes: Synthesis of Substituted Cyclopentane and Tetrahydrofuran
  作者：Ashok Kumar Pandey、Rohit Kumar Varshnaya、Prabal Banerjee

  DOI：10.1002/ejoc.201601549

  日期：2017.3.27

  substituents present in both reacting partners produced different products. The C-attack gave functionalized cyclopentane derivatives while the O-attack furnished tetrahydrofuran derivatives via [3+2]-annulation reactions. Moreover, to increase the utility of our method, synthesized diasteriomeric cyclopentane derivatives were converted into synthetically useful cyclopentene and cyclopentanone analog.

  取代基和路易斯酸促进从环氧化物生成官能化烯醇化物。烯醇化物对供体-受体环丙烷的不同攻击，即 C-攻击或 O-攻击，取决于两个反应伙伴中存在的取代基，产生不同的产物。C-攻击产生官能化的环戊烷衍生物，而O-攻击通过[3+2]-环化反应提供四氢呋喃衍生物。此外，为了提高我们方法的实用性，合成的非对映环戊烷衍生物被转化为合成有用的环戊烯和环戊酮类似物。