1-chloro-1E,3-butadiene | 16503-25-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 1-chloro-1E,3-butadiene
• 英文别名: 1-Chlorobuta-1,3-diene；(1E)-1-chlorobuta-1,3-diene
• CAS: 16503-25-6
• 化学式: C₄H₅Cl
• 分子量: 88.5367
• InChiKey: PCPYTNCQOSFKGG-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-chloro-1E,3-butadiene 在 二氧化硫 作用下， 反应 12.0h， 以13%的产率得到2-chloro-2,5-dihydrothiophene-1,1-dioxide
  参考文献：
  名称：

  Competition between Hetero-Diels−Alder and Cheletropic Addition of Sulfur Dioxide. Theoretical and Experimental Substituent Effects on the Relative Stability of 3,6-Dihydro-1,2-oxathiin-2-oxides (Sultines) and 2,5-Dihydrothiophene-1,1-dioxides (Sulfolenes). Anomeric Effects in Sultine and 6-Substituted Derivatives

  摘要：

  At low temperature and in the presence of CF3COOH, SO2 undergoes Diels-Alder additions with (E)-1-acetoxybutadiene (8d) giving a 1:10 mixture of diastereomeric 6-acetoxysultines (9d + 10d). The Van't Hoff plot for equilibria 8d + SO2 reversible arrow 9d + 10d led to Delta H-r = -7.0 +/- 0.3 kcal/mol, Delta S-r = -42 +/- 3 cal . mol(-1) . K-1. At 20 degrees C, 8d underwent a slow cheletropic addition with SO2 giving 2-acetoxysulfolene (11d, Delta Hr congruent to -11.5 kcal/mol), the structure of which was established by single-crystal X-ray diffraction studies. (E)-Chloro (8e) and (E)-bromobutadiene (8f) did not undergo Diels-Alder additions with SO2, even in the presence of protic or Lewis acid promoters. Low yields of 2-chloro- (11e) and 8-bromosulfolene (11f) were obtained at 20 degrees C. The structure of 11e was confirmed by single-crystal X-ray diffraction. The potential energy hypersurfaces of the Diels-Alder and cheletropic additions of SO2 to butadiene (8a), (E)-piperilene (8b), (E)-1-methoxy- (8c), (E)-1-acetoxy- (8d), and (E)-1-chlorobutadiene (8e) were studied by ab initio quantum calculations at the MP2/6-31G* level. In agreement with the experiment, 6-substituted sultines 9X and 10X were less stable than the corresponding 2-substituted sulfolenes 11X for X = Me, OAc, Cl. With X = OMe, the two diastereomeric 6-methoxysultines (9c, 10c) and 8-methoxysulfolene (11c) were calculated to have similar stabilities. This is attributed to a stabilizing thermodynamic anomeric effect or gem-sulfinate/methoxy disubstitution effect in 9c, 10c. Such effects were not detected for sulfinate/acetoxy (9d, 10d) and sulfinate/chloro (9e, 10e) disubstitutions. The relative instability of 8-acetoxy- (11d) and 2-chlorosulfolene (11e) compared with their cycloaddents is attributed to repulsive interactions between the SO2 moieties and the 2-substituents. The Alder endo mode of [4 + 2] cycloaddition of SO2 is predicted to be faster than the "anti-Alder mode" of additions for dienes 8X, X = Me, OMe, OAc, Cl. The resulting diastereomeric sultines 9X and 10X, respectively, exist as equilibria (energy barrier: ca. 5-6 kcal/mol) of two conformers 9X reversible arrow 9X, 10X reversible arrow 10X. In general, the conformers 9X, 10X with pseudoaxial S=O group are preferred (conformational anomeric effect of the sulfinate moiety). Repulsive interactions between pseudoaxial S=O and polar cis-6-substituents (e.g.: X = OMe, OAc) in 9X may render conformers 9X (with the S-O and 6-X groups in pseudoequatorial positions) as stable as conformers 9X. The calculations predict the existence of conformational anomeric effects of 2-3 kcal/mol for the gem-sulfinate/methoxy (9c, 10'c) and gem-sulfinate/acetoxy disubstitution (9d, 10'd).

  DOI：

  10.1021/jo981679g
• 作为产物：
  描述：

  1,4-戊二烯-3-醇 在 盐酸 、 水 作用下， 以 正戊烷 为溶剂， 反应 1.0h， 生成 1-chloro-1E,3-butadiene
  参考文献：
  名称：

  通过镍催化的丙烯和烯烃的氢催化氰化裂解环丙烷环

  摘要：

  描述了由丙二烯的碳-碳双键的加氢镍化反应，然后环丙烷裂解引起的镍催化的氢氰化反应。最初的氢镍化步骤强烈影响产物中观察到的区域和立体化学，并且烯丙基和亚甲基环丙烷的反应平稳，促进了环丙烷的裂解。相反，用亚乙烯基环丙烷没有观察到这种裂解，因为最初的加氢镍化作用不能为裂解环丙烷提供合适的中间体。

  DOI：

  10.1002/adsc.201601400

文献信息

• Intramolecular Diels−Alder Reaction of Chiral Silatrienes: Synthesis of 4a,7,8,8a-Tetrahydro-4-silaisochroman-1-ones
  作者：Paulo J. Coelho、Luis Blanco

  DOI：10.1002/1099-0690(200009)2000:17<3039::aid-ejoc3039>3.0.co;2-x

  日期：2000.9

  Intramolecular Diels−Alder reactions of chiral 2-silahexa-3,5-dienyl α,β-unsaturated esters have been found to afford tetrahydro-4-silaisochroman-1-ones in moderate yields. The best diastereoselectivity was achieved in the reaction of silatriene 8c, in which methyl and triisopropylsilyloxymethyl groups are attached to the silicon atom, with an acrylate as the dienophile under EtAlCl2-catalyzed conditions

  已发现手性 2-silahexa-3,5-二烯基 α,β-不饱和酯的分子内 Diels-Alder 反应以中等产率提供四氢-4-silaisochroman-1-ones。最好的非对映选择性是在硅三烯 8c 的反应中实现的，其中甲基和三异丙基甲硅烷氧基甲基连接到硅原子上，丙烯酸酯作为在 EtAlCl2 催化条件下的亲二烯体。
• Die Pyrolyse von (+)-Verbenen
  作者：Alan F. Thomas、B. Willhalm、G. Ohloff

  DOI：10.1002/hlca.19690520510

  日期：——

  The pyrolysis of verbenene has been found to give rise to 39% of isobutenylcyclohexa-1,3-diene (3), 29% of o-mentha-1 (7),5,8-triene (2) together with two double bond-isomers (4 and 5) of the cyclohexadiene (3). The structures were proved by catalytic reduction to the saturated hydrocarbons, and isobutenylcyclohexa-1,3-diene was synthesized from 2,3-dihydrobenzaldehyde.

  已发现马鞭草的热解可产生39％的异丁烯基环己-1,3-二烯（3），29％的o -mentha-1（7），5,8-三烯（2）和两个双键-环己二烯（3）的-异构体（4和5）。通过催化还原成饱和烃证明了结构，并由2,3-二氢苯甲醛合成了异丁烯基环己-1,3-二烯。
• Transition metal catalyzed reactions of diazoesters
  作者：A.J. Anciaux、A. Demonceau、A.F. Noels、R. Warin、A.J. Hubert、P. Teyssié

  DOI：10.1016/s0040-4020(01)91934-9

  日期：——

  of carbenes generated by catalyzed decomposition of diazoesters in the presence of Rh, Pd and Cu catalysts can be controlled to some extent by selecting proper reaction parameters. For a particular diene, the regioselectivity depends both on the catalyst and on the nature of the double-bond (conjugation, substitution).

  在Rh，Pd和Cu催化剂存在下，通过重氮催化催化重氮酸酯分解生成的卡宾的环加成反应，多烯环丙烷化的区域选择性可以在一定程度上控制。对于特定的二烯，区域选择性既取决于催化剂又取决于双键的性质（共轭，取代）。
• New process for the preparation of 1,3,5-undecatrienes
  申请人：Oril S.A.

  公开号：US04652692A1

  公开（公告）日：1987-03-24

  Process for the preparation of 1,3,5-undecatrienes, characterized in that an organometallic 1-heptenyl compound is reacted with a (E)-1,3-butadiene derivative. Manufacture of 1,3,5-undecatrienes that can be used in the perfumes and flavorings industry.

  制备1,3,5-十一烯的过程，其特点在于将一个有机金属化合物1-庚烯基与(E)-1,3-丁二烯衍生物反应。制备可用于香水和调味品行业的1,3,5-十一烯。
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  作者：

  DOI：——

  日期：——

表征谱图