E-3-formylcrotononitrile | 78843-78-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: E-3-formylcrotononitrile
• 英文别名: methyl (E)-3-formylbut-2-enenitrile；3-methyl-4-oxobut-2-enenitrile；3-methyl-4-oxo-2-butenenitrile；trans-3-formylbut-2-enenitrile；(e)-3-Formylbut-2-enenitrile；(E)-3-methyl-4-oxobut-2-enenitrile
• CAS: 78843-78-4
• 化学式: C₅H₅NO
• 分子量: 95.1008
• InChiKey: XCOOSSPISDTMHL-GORDUTHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  E-3-formylcrotononitrile 生成 (2E)-4-hydroxy-3-methylbut-2-enenitrile
  参考文献：
  名称：

  CHEN, SHI-CHOW;MACTAGGART, J. M.

  摘要：

  DOI：
• 作为产物：
  描述：

  (E)-4,4-Dimethoxy-3-methylbut-2-ene-1-nitrile 生成 E-3-formylcrotononitrile
  参考文献：
  名称：

  CHEN, SHI-CHOW;MACTAGGART, J. M.

  摘要：

  DOI：

文献信息

• Preparation of (all-E)- and (11Z)-12-Haloretinals and (11Z,13Z)- and (13Z)-14-Haloretinals by the C15 + C5 Route ? Exploring the Possibility of Preparing any Retinoid Rationally Chemically Modified at any Position in the Conjugated Tail
  作者：Yajie Wang、Johan Lugtenburg

  DOI：10.1002/ejoc.200400488

  日期：2004.12

  that many more retinals chemically modified at the 12-position could be prepared in this manner. Selectfluor®, a good reagent for introducing a fluorine atom by electrophilic substitution, does not give the 12-fluororetinal system. However, 14-fluororetinal is simply available by reaction of the anion with Selectfluor®. Cl, Br and I atoms were also introduced at the 14-position of retinal both in the

  在本文中，我们描述了如何通过亲电取代以简单的方式制备化学修饰的叶立德。随后的 Horner-Emmons 反应可以得到 (all-E)- 和 (11Z)-12-chloro-、-12-bromo- 和 -12-iodoretal。可以预期，以这种方式可以制备更多在 12 位进行化学修饰的视黄醛。Selectfluor® 是一种通过亲电取代引入氟原子的良好试剂，不会产生 12-氟视黄醛系统。然而，14-氟视黄醛可通过阴离子与 Selectfluor® 的反应轻松获得。Cl、Br 和 I 原子也以 (11Z,13Z)- 和 (13Z)-异构形式引入视黄醛的 14 位。这种策略可以扩展到整个范围的亲电取代反应。我们还开发了一种制备 4-羟基取代的 Horner-Emmons 衍生物的新方法，该方法可以通过与（二乙氨基）三氟化硫 (DAST) 反应转化为 4-氟衍生物。该系统可以简单地转化为 (all-E)-
• Retinoids and related compounds. Part 26. Synthesis of (11Z)-8,18-propano- and methano-retinals and conformational study of the rhodopsin chromophore†
  作者：Akimori Wada、Masako Tsutsumi、Yuka Inatomi、Hiroo Imai、Yoshinori Shichida、Masayoshi Ito

  DOI：10.1039/b104394n

  日期：——

  In order to clarify the conformation of the chromophore in rhodopsin, especially the effect of the torsional angle around the C6–C7 single bond on the CD spectrum, 8,18-propano- and methano-retinal 4 and 5 were prepared via the palladium-catalyzed coupling reaction of vinyl triflates derived from bicyclic ketones 10 and 27 with methyl (E)-3-(trimethylstannyl)but-2-enoate. In a binding experiment with bovine opsin, retinal analogs 4 and 5 afforded the new rhodopsin analogs. Although the opsin shifts of these pigments were similar to that of the native rhodopsin, CD spectra exhibited the characteristic feature owing to the locked structures of retinal analogs. This fact strongly indicates that the CD spectra were significantly influenced by the torsional angles around the 6–7 and 8–9 single bonds of the chromophore in the protein.

  为了弄清视网膜素中发色团的构象，特别是围绕 C6-C7 单键的扭转角对 CD 光谱的影响，我们通过钯催化双环酮 10 和 27 衍生的乙烯基三甲酸酯与 (E)-3-(trimethylstannyl)but-2-enoate 甲酯的偶联反应，制备了 8,18-丙基和甲基视网膜素 4 和 5。在与牛视网膜蛋白的结合实验中，视网膜类似物 4 和 5 得到了新的视网膜蛋白类似物。虽然这些色素的视紫红质偏移与原生视紫红质相似，但由于视网膜类似物的锁定结构，它们的 CD 光谱呈现出特有的特征。这一事实有力地表明，CD 光谱受到蛋白质中发色团 6-7 和 8-9 单键周围扭转角的显著影响。
• Synthesis of 11Z-8,18-Propano- and Methano-Retinals and Their Interaction with Bovine Opsin.
  作者：Akimori WADA、Masako TSUTSUMI、Yuka INATOMI、Hiroo IMAI、Yoshinori SHICHIDA、Masayoshi ITO

  DOI：10.1248/cpb.43.1419

  日期：——

  In order to clarify the conformation of chromophore in rhodopsin, especially the torsional angle around the C6-C7 single bond, 8, 18-propano- and methano-retinals were prepared from 2, 2-dimethylcyclohexanone via the palladium-catalyzed coupling reaction of vinyl triflates with methyl E-3-trimethylstannyl-2-butenoate, and their interaction with bovine opsin was investigated.

  为了阐明视紫红质中发色团的构象，特别是C6-C7单键周围的扭转角，通过钯催化的乙烯基偶联反应，以2, 2-二甲基环己酮为原料制备了8, 18-丙醇和亚甲基视黄醛。研究了 E-3-三甲基甲锡烷基-2-丁烯酸甲酯与三氟甲磺酸酯的相互作用，以及它们与牛视蛋白的相互作用。
• Process for the preparation of trans-3-formylbut-2-enenitrile
  申请人：Alberta Research Council

  公开号：US04361702A1

  公开（公告）日：1982-11-30

  A process is provided for the preparation of trans-3-formylbut-2-enenitrile (V), a key intermediate in the synthetic pathway leading to trans-zeatin (I) and dihydrozeatin (II), both of which are naturally occurring cytokinins. The process involves a base catalyzed condensation of a dialkyl or cyclic acetal of pyruvaldehyde (III) with acetonitrile to yield the corresponding dialkyl or cyclic acetal of 3-formylbut-2-enenitrile (IV). The reaction proceeds regioselectively to form the favored trans-isomer in good yield. The .alpha.,.beta.-unsaturated nitrile thus formed is hydrolyzed under acidic conditions to yield trans-3-formylbut-2-enenitrile (V), which can be easily distilled without contamination of the cis-isomer. The trans-3-formylbut-2-enenitrile can be selectively or exhaustively reduced to form either trans-3-hydroxymethylbut-2-enylamine (VI) or 3-hydroxymethylbutylamine (VII), which compounds can be condensed with 6-chloropurine (IX) by known methods to form trans-zeatin or dihydrozeatin respectively.

  本发明提供了一种制备转-3-甲酰基丁-2-烯基腈(V)的方法，它是合成转赤霉素(I)和二氢赤霉素(II)的关键中间体，这两种物质都是天然植物激素。该方法涉及用碱催化的方式将丙酮腈与丙酮醛的二烷基或环状缩醛(III)缩合，得到相应的3-甲酰基丁-2-烯基腈的二烷基或环状缩醛(IV)。反应以高产率选择性形成偏爱的反式异构体。因此形成的α，β-不饱和腈在酸性条件下水解，得到转-3-甲酰基丁-2-烯基腈(V)，可以轻松地蒸馏而不会受到顺式异构体的污染。转-3-甲酰基丁-2-烯基腈可以被选择性或彻底还原，形成转-3-羟甲基丁-2-烯基胺(VI)或3-羟甲基丁基胺(VII)，这些化合物可以通过已知的方法与6-氯嘌呤(IX)缩合，分别形成转赤霉素或二氢赤霉素。
• Process for producing branched aldehydes
  申请人：Kuraray Co., Ltd.

  公开号：US05932761A1

  公开（公告）日：1999-08-03

  It is provided a process for industrially advantageously producing a branched aldehyde represented by the formula; ##STR1## \x9bwherein Y represents an acyl group of two or more carbon atoms; and X represents an acyloxymethyl group represented by --CH.sub.2 OY' (where Y' represents an acyl group of two or more carbon atoms), cyano group or an alkoxycarbonyl group! which is useful as an intermediate for pharmaceuticals and agricultural chemicals, comprising subjecting an olefinic compound represented by the following formula; ##STR2## (wherein Y and X are the same as defined above), to the reaction with hydrogen and carbon monoxide in the presence of a rhodium compound and a tertiary organic phosphorus compound with an electronic parameter (.upsilon.-value) of 2080 to 2090 cm.sup.-1 or with a steric parameter (.theta.-value) of 150 to 180.degree..

  本发明提供了一种工业上有利的生产分支醛的方法，所述分支醛由以下式子表示：##STR1## 其中，Y表示2个或更多碳原子的酰基；X表示代表--CH.sub.2 OY'（其中Y'表示2个或更多碳原子的酰基）、氰基或烷氧羰基的酰氧甲基，该方法适用于制药和农药中间体的制备，包括将以下式子表示的烯烃化合物##STR2##（其中Y和X的定义同上）与氢气和一氧化碳在铑化合物和具有电子参数（.upsilon.-value）为2080至2090 cm.sup.-1或具有立体参数（.theta.-value）为150至180度的三级有机磷化合物存在下反应。