Perillyl chloride | 127940-66-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Perillyl chloride
• 英文别名: 7-chloro-p-mentha-1,8-diene；7-Chlor-p-mentha-1,8-dien；limonenyl chloride；1-(Chloromethyl)-4-prop-1-en-2-ylcyclohexene
• CAS: 127940-66-3
• 化学式: C₁₀H₁₅Cl
• 分子量: 170.682
• InChiKey: WONQAYATGSHTGI-UHFFFAOYSA-N

物化性质

• 沸点：
  211.7±29.0 °C(Predicted)
• 密度：
  0.971±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  Perillyl chloride 、 lithium hexamethyldisilazane 在 silver(I) iodide 作用下， 生成 N,N-Bis(trimethylsilyl)perilylamine
  参考文献：
  名称：

  Silver iodide mediated amination reaction of allylic chlorides with lithium bis(trimethylsilyl)amide: a new synthetic method of N,N-disilylallylamines via lithium amide argentates

  摘要：

  The nucleophilic substitution reaction of allylic chlorides with lithium bis(trimethylsilyl)amide (1) in the presence of silver halides has been studied in detail. Silver iodide (AgI) was found to be most effective for facilitation of the amination reaction. The reaction of alkyl-substituted allylic chlorides proceeded smoothly in S(N)2 fashion to give N,N-disilylallylamines in high yields when 0.1 or 0.5 equiv of AgI was used as an additive, whereas a stoichiometric amount of AgI was indispensable in the reaction of allylic chlorides having a phenyl group. The reaction of geranyl or neryl chloride proceeded with retention of configuration of the C=C bond to give only one isomer 4 or 5, respectively. The oxygen-containing functional groups and chlorine remained intact during the reaction. The reaction of alpha-silylmetallyl chloride 17 proceeded in an S(N)2' manner to afford (Z)-allylamine 18. So as to disclose the active species in the AgI-mediated reaction, the variable low-temperature C-13 NMR experiments using the mixture of AgI and 1 in THF have been performed. It has been suggested that lithium amide argentates such as (Me3Si)2NAg(I)Li (20) and [(Me3Si)2N]2Ag(I)Li2 (21) are formed in the reaction mixture, and the nucleophilicity and basicity of 1 are controlled by forming these species.

  DOI：

  10.1021/jo00078a024
• 作为产物：
  描述：

  紫苏醇 在 五氯化磷 、 Petroleum ether 作用下， 生成 Perillyl chloride
  参考文献：
  名称：

  Semmler; Zaar, Chemische Berichte, 1911, vol. 44, p. 54,461

  摘要：

  DOI：

文献信息

• CeCl3/NaClO: a safe and efficient reagent for the allylic chlorination of terminal olefins
  作者：F.Javier Moreno-Dorado、Francisco M. Guerra、Francisco L. Manzano、F.Javier Aladro、Zacarı́as D. Jorge、Guillermo M. Massanet

  DOI：10.1016/s0040-4039(03)01630-7

  日期：2003.8

  The preparation of allylic chlorides by reaction of terminal olefins with sodium hypochlorite in the presence of cerium trichloride heptahydrate is described. The scope, limitations and synthetic perspectives of the reaction are discussed.

  描述了通过在三氯化铈七水合物存在下使末端烯烃与次氯酸钠反应来制备烯丙基氯化物。讨论了反应的范围，局限性和合成观点。
• Compounds which inhibit complement and/or suppress immune activity
  申请人：T Cell Sciences, Inc.

  公开号：US05366986A1

  公开（公告）日：1994-11-22

  The present invention is directed to compounds which suppress immune responses and/or selectively inhibit complement. These compounds contain an aromatic ring and are substituted dihydrobenzofurans, spirobenzofuran-2(3H)-cycloalkanes, and their open chain intermediates. The compounds of the present invention, and the phamaceutically acceptable salts thereof, interrupt the proteolytic processing of C5 to bioactive components, exhibit immunosuppressive activites, and have therapeutic utility in the amelioration of disease and disorders mediated by complement and/or immune activity.

  本发明涉及抑制免疫反应和/或选择性抑制补体的化合物。这些化合物含有芳香环，并且是取代二氢苯并呋喃、螺苯并呋喃-2(3H)-环戊烷及其开链中间体。本发明的化合物及其药学上可接受的盐中断C5的蛋白酶加工为生物活性成分，表现出免疫抑制活性，并在改善由补体和/或免疫活性介导的疾病和紊乱方面具有治疗效用。
• Catalytic Allylic Chlorination of Natural Terpenic Olefins Using Supported and Nonsupported Lewis Acid Catalysts
  作者：Ayoub Abdelkader Mekkaoui、Mouhsine Laayati、Hamza Orfi、Larbi El Firdoussi、Soufiane El Houssame

  DOI：10.1155/2020/2563634

  日期：2020.10.22

  convenient method for the allylic chlorination of naturally occurring terpenic olefins was investigated in the presence of different supported and non-supported Lewis acid catalysts. The reaction has been tested on carvone as a model substrate in the presence of sodium hypochlorite as chlorine donor. The scope and limitations of transition metal-based Lewis acid catalysts, stoichiometry, and substrate

  在不同负载型和非负载型路易斯酸催化剂存在下，研究了一种温和方便的天然萜烯烯丙基氯化方法。在作为氯供体的次氯酸钠存在下，在作为模型底物的香芹酮上测试了该反应。评估了基于过渡金属的路易斯酸催化剂、化学计量和底物结构的范围和局限性。在所使用的铁前体中，FeCl3 和 FeCl2 有望成为烯丙基或乙烯基氯化反应的通用方法。在 FeCl3/NaOCl 组合体系存在下检测了各种萜烯。催化氯化在温和条件下进行，反应时间短，显示出高选择性，以良好到极好的收率提供相应的氯化物。
• Facile fragmentation of pinenes using dimethyl sulfoxide activated by phenyl dichlorophosphate or phosphorus oxychloride. Efficient conversion of α-pinene to carvone
  作者：Hsing-Jang Liu、James M Nyangulu

  DOI：10.1016/s0040-4039(01)93456-2

  日期：——

  Treatment of pinenes with dimethyl sulfoxide in the presence of phenyl dichlorophosphate or phosphorus oxychloride resulted in facile fragmentation giving rise to limonene derivatives. The fragmentation reaction serves as a key step in the efficient conversion of α-pinene (1) to carvone (7).

  在苯基二氯磷酸酯或氯氧化磷存在下，用二甲亚砜处理烯，导致裂解容易，从而生成柠檬烯衍生物。裂解反应是α-pine烯（1）有效转化为香芹酮（7）的关键步骤。
• Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds
  作者：Akira Yanagisawa、Shigeki Habaue、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1021/ja00093a010

  日期：1994.7

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).