(E)-(2-ethoxy-3-ethoxycarbonylallylidene)triphenylphosphorane | 145822-68-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-(2-ethoxy-3-ethoxycarbonylallylidene)triphenylphosphorane
• 英文别名: (E)-[2-ethoxy-3-(ethoxycarbonyl)-2-propenylidene]triphenylphosphorane；ethyl (E)-3-ethoxy-4-(triphenyl-lambda5-phosphanylidene)but-2-enoate；ethyl (E)-3-ethoxy-4-(triphenyl-λ5-phosphanylidene)but-2-enoate
• CAS: 145822-68-0
• 化学式: C₂₆H₂₇O₃P
• 分子量: 418.472
• InChiKey: DYDASETXHJTSJR-LSDHQDQOSA-N

物化性质

• 沸点：
  560.8±60.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-(2-ethoxy-3-ethoxycarbonylallylidene)triphenylphosphorane 在 sodium tetrahydroborate 、 氢溴酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 ethyl 2-(5-methylfuran-2-yl)acetate
  参考文献：
  名称：

  A Facile Synthesis of 5-Substituted 2-Furyl-, 2-Thienyl- and 2-Pyrrolylacetates by Cyclodehydration of g-Functionalized a,b-Unsaturated Ketones

  摘要：

  DOI：

  10.3987/com-99-s141
• 作为产物：
  描述：

  ethyl (E)-4-bromo-3-ethoxy-2-butenoate 在 sodium hydroxide 作用下， 以 苯 为溶剂， 反应 46.0h， 生成 (E)-(2-ethoxy-3-ethoxycarbonylallylidene)triphenylphosphorane
  参考文献：
  名称：

  Allylidenetriphenylphosphorane as a bifunctional reagent: synthesis of cyclopentenones and .alpha.,.beta.-unsaturated ketones with [3-(alkoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphorane

  摘要：

  When (3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene) triphenylphosphorane (6) was allowed to react with cu-bromo ketones 8a-d in dichloromethane in the presence of Cs2CO3 at room temperature, a [3 + 2] annulation occurred and led to the formation of the corresponding 2-ethoxycyclopentadienes 9a-d in excellent yields. Similarly, bromo thioester 8g underwent the annulation to give 4-(ethylthio)-cyclopentadiene 9g. Secondary bromides 2-bromo-3-pentanone and 2-bromocyclohexanone also afforded tetrasubstituted cyclopentadienes 9e and 9f in moderate yields when 2 equiv of 6 was used. The annulation is believed to proceed through a sequence involving a stepwise alkylation at the gamma position of 6 and an intramolecular Wittig reaction because of the fact that intermediate 11 was isolated. The resulting 2-ethoxycyclopentadienes 9a-g were converted quantitatively into the corresponding cyclopentenones 10a-g upon mild acid treatment. Furthermore, allylidenetriphenylphosphorane underwent a carbon elongation at both ends of the three-carbon unit via an alkylation-Wittig reaction sequence. (3-(tert-Butoxycarbonyl)-2-ethoxy-2-propenylidene)triphenylphosphorane (7) reacted first with alkyl halides and then with aldehydes in the presence of Cs2CO3 to give enol ethers 23a-f, which were converted into alpha,beta-unsaturated ketones 20, 21, and 25c-f by hydrolysis of the enol ether and then decarboxylation. In this way, shogaol (29), the pungent principle component of ginger, was conveniently synthesized starting from 2-methoxy-4-methylphenol.

  DOI：

  10.1021/jo00080a019

文献信息

• Synthesis and Reactions of Ethyl 6-Aryl-3-ethoxy-6-oxo-2,4-hexadienoates.
  作者：Yasuhiro TANAKA、Tomikazu KAWANO、Saiful Md. ISLAM、Hiroyasu NISHIOKA、Minoru HATANAKA、Ikuo UEDA

  DOI：10.1248/cpb.44.885

  日期：——

  Biologically interesting ethyl 6-aryl-3-ethoxy-6-oxo-2, 4-hexadienoates (1) have been prepared by the Witting reaction of [3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphoranes (3a and 3b) and -arsorane (3c) with glyoxal monohydrates (5) and by oxidation of 6-aryl-3-ethoxy-6-hydroxy-2, 4-hexadienoate (9) with activated manganese (IV) oxide supported by silica. Reaction of 1a with 3c gave 3-(4-chlorobenzoyl)-1, 2-trans (and cis)-bis(1-ethoxy-2-ethoxycarbonylethenyl)cyclopropanes (6 and 7). When 1a was treated with a 1 : 5 mixture of concentrated HCl and tetrahydrofuran at room temperature, 3-hydroxy-6-oxo-2, 4-hexadienoate (10a) was obtained in 46% yield. Treatment of 1b with trifluoroacetic acid gave 5, 6-dihydro-2H-pyran-2-one (12) in 53% yield together with 10b in 28% yield. When 1a was treated with 1N ethanolic potassium hydroxide, 12 and 2H-pyran derivative (13) were obtained in 33% and 28% yields, respectively. Reaction of 1a with ammonium hydroxide and primary amines in the presence of a proton acid gave 2-oxo-1, 2, 5, 6-tetrahydropyridines (14) in good yields. The mechanism of the formation of 6, 12, 13, and 14 is discussed.

  通过[3-(乙氧羰基)-2-乙氧-2-丙烯叉基]三苯基膦烷(3a和3b)和胂烷(3c)与水合乙二醛(5)的Witting反应以及6-芳基-3-乙氧基-6-羟基-2,4-己二烯酸乙酯(9)与负载于二氧化硅上的活性二氧化锰氧化反应，已经制备了生物学上有趣的乙基6-芳基-3-乙氧基-6-氧-2,4-己二烯酸酯(1)。1a与3c反应得到3-(4-氯苯甲酰基)-1,2-反式(和顺式)-双(1-乙氧基-2-乙氧羰乙烯基)环丙烷(6和7)。当1a在室温下与浓盐酸和四氢呋喃的1:5混合物处理时，以46%的产率得到3-羟基-6-氧-2,4-己二烯酸酯(10a)。将1b与三氟乙酸处理，得到5,6-二氢-2H-吡喃-2-酮(12)，产率为53%，同时得到10b，产率为28%。当1a与乙醇钾的1N溶液处理时，分别以33%和28%的产率得到12和2H-吡喃衍生物(13)。在质子酸存在下，1a与氨水和一级胺反应，以良好的产率得到2-氧-1,2,5,6-四氢吡啶(14)。讨论了6、12、13和14的形成机制。
• Reaction of trisubstituted alkenes with iron porphyrin carbenes: facile synthesis of tetrasubstituted dienes and cyclopentadienes
  作者：Peng Wang、Saihu Liao、Sunewang R. Wang、Run-Duo Gao、Yong Tang

  DOI：10.1039/c3cc44092c

  日期：——

  The unprecedented reaction of trisubstituted alkenes with iron porphyrin carbenes has been successfully developed. Both multiply substituted 1,3-butadiene and cyclopentadiene products are readily accessible with high efficiency and selectivity in good yields.

  已经成功开发了三取代烯烃与卟啉铁甲酸酯的空前反应。多取代的1，3-丁二烯和环戊二烯产物都容易以高产率和高效率和选择性地获得。
• Convenient synthesis of substituted cyclopentenones via [3 + 2] annulation of allylidenetriphenylphosphorane with 1,2-diacylethylenes: application to synthesis of (±)-methyl dehydrojasmonate
  作者：Yuichiro Himeda、Yasuhiro Tanaka、Ikuo Ueda、Minoru Hatanaka

  DOI：10.1039/a709296b

  日期：——

  (3-Alkoxycarbonyl-2-ethoxyprop-2-enylidene)triphenylphosphoranes 1 and 2 undergo [3 + 2] annulation with 1,2-diacylethylenes 3 to give 2-ethoxycyclopentadienes 6 as mixtures of the 1,3- and 1,4-diene. The mixtures are conveniently converted upon mild acid treatment into cyclopentenones 7 in a single form. Annulation of phosphorane 1 with acylmethylenemalonates 10 affords cyclopenta-1,3-dienes 11 in

  （3-烷氧基羰基-2-乙氧基丙-2-烯基）三苯基膦酸酯与1，2-二丙烯基乙烯3进行[3 + 2]环化反应，得到2-乙氧基环戊二烯6，为1,3-和1,4-的混合物二烯。混合物经温和酸处理后方便地转化为单一形式的环戊烯酮7。膦烷1与酰基亚甲基丙二酸酯10的环化以高度区域选择性的方式提供环戊-1,3-二烯11，其易于以优异的产率转化为取代的环戊烯12。磷烷1也用1，2-酰基乙炔14进行环化，得到富叶烯15，其转变成外亚甲基环戊烯酮16。此外，描述了环化在（±）-甲基脱氢茉莉酮酸酯的合成中的应用。
• Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit
  作者：Minoru Hatanaka、Ritsuo Imashiro、Ikuo Ueda

  DOI：10.1246/cl.1992.2253

  日期：1992.11

  3-Alkoxycarbonyl-2-ethoxy-2-propenylidenetriphenylphosphorane reacts in turn with alkyl halides and aldehydes in the presence of base via a one-pot procedure to give moderate to good yields of conjugated enol ethers. Hydrolysis of the conjugated enol ethers and subsequent decarboxylation provide a novel route to α,β-unsaturated ketones.

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。
• Intramolecular Diels–Alder reaction of 1-ethoxycarbonyl-4-alkenylcyclopentadienes
  作者：Yuichiro Himeda、Kazuhisa Hiratani、Minoru Hatanaka、Ikuo Ueda

  DOI：10.1039/c39920001684

  日期：——

  4-(But-3-enyl)- and 4-(pent-4-enyl)-1-ethoxycarbonyl-2-ethoxycyclopentadiene, prepared from allylidenetriphenylphosphorane and α-haloketones, underwent a regioselective intramolecular Diels–Alder reaction to give two types of the functionalized tricyclic products depending on the linking carbon-chain length.

  4-(But-3-enyl)- 和 4-(pent-4-enyl)-1-ethoxycarbonyl-2-ethoxycyclopentadiene, 由烯丙基三苯基正膦和 α-卤代酮制备，经过区域选择性分子内 DielsâªAlder 反应得到两个官能化三环产物的类型取决于连接碳链的长度。