2,4,6-环庚三烯-1-甲酰氯 | 32399-48-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 中文名称: 2,4,6-环庚三烯-1-甲酰氯
• 英文名称: cycloheptatriene-7-carbonyl chloride
• 英文别名: 2,4,6-cycloheptatriene-1-yl carbonyl chloride；1,3,5-cycloheptatriene-7-carbonyl chloride；Cyclohepta-2,4,6-triene-1-carbonyl Chloride
• CAS: 32399-48-7
• 化学式: C₈H₇ClO
• 分子量: 154.596
• InChiKey: PXZATBHOTNVWFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2916209090

反应信息

• 作为反应物：
  描述：

  2,4,6-环庚三烯-1-甲酰氯 在 sodium tetrahydroborate 作用下， 以 甲醇 、 乙醚 、 乙醇 为溶剂， 生成 10α-Hydroxy-tricyclo<3.3.2.0^2.8>-deca-3,6-dien
  参考文献：
  名称：

  合理合成Bullvalene barbaralone及其衍生物；Bullvalone

  摘要：

  从环庚三烯-7-羧酸，通过环庚三烯-7-羰基氯，环庚三烯-7-基重氮甲基酮（B-1），巴巴龙（VI），牛戊酮（V）的七个步骤中，合理合成牛synthesis烯（I） ），9-羟基三环[3.3.2.0 2、8 ] deca-3,6-二烯和9-乙酰氧基三环-[3.3.2.0 2、8 ] deca-3,6-diene（F-4）。讨论主要涉及（a）一种试图从环庚三烯-7-基乙酸（A-1），其代替产生同分异构的三环[5.3.0.0合成bullvalone（V）2，10] -deca-3,5-dien-9-one（A-3）; （b）芭芭拉（V）中的二乙烯基环丙烷重排及其非常快的速率与非循环系统中Cope重排的理论关系；（c）巴拉巴拉烷（VII）的制备及其通量质量；（d）将Bullvalene（I）热重组为顺式-9,10-二氢萘（IX）；（e）制备甲基和苯基布尔瓦伦烯；（f）氘交换Bullvalone（

  DOI：

  10.1016/s0040-4020(01)97904-9
• 作为产物：
  描述：

  2,4,6-环庚三烯-1-甲腈 在 氯化亚砜 、 硫酸 、 水 、 碳酸氢钠 作用下， 以 甲醇 为溶剂， 反应 79.0h， 生成 2,4,6-环庚三烯-1-甲酰氯
  参考文献：
  名称：

  Ion Pair Acidities and Aggregation of Some Amide and Oxazoline Enolates in THF^,

  摘要：

  Equilibrium lithium ion pair acidities at 25 degrees C have been determined in THF for the following acetamides: N,N-dimethyl-(4-biphenylyl)acetamide (1) (19.69), N,N-diethyl-(4-biphenylyl)acetamide (2) (20.30), N,N-dimethyl-diphenylacetamide (3) (20.76), N,N-diethyl-diphenylacetamide (4) (21.99), and 1-(diphenylmethylcarbonyl)pyrrolidine (5) (21.08). These acidity data compare well with those previously reported for the corresponding cesium enolates. Lithium and cesium ion pair acidities in THF are reported for two oxazolines: 2-(4-biphenylylmethyl)oxazoline (6) (Li, 21.53; Cs, 25.49) and (E)-(4S,5R)-2-(4-biphenylylmethyl)-4-methyl-5-phenyloxazoline (7) (Li, 20.10; Cs 24.21). Studies of their acidities over a wide range of concentrations indicate that all of the lithium and cesium enolates of 1-7 are essentially monomeric at concentrations ranging from 10(-8) to 10(-4) M. Traces of dimer were detected for the lithium enolates of amides 1 and 2 and for the cesium enolate of oxazoline 6. Their dimerization constants (M-1) were found to be about 450, 200, and 150, respectively. All of the other lithium and cesium enolate probably form small amounts of dimer, but the dimerization constant of < 100 M-1 is below the limit of precision of our spectroscopic method.

  DOI：

  10.1021/jo981846c

文献信息

• Synthesis and X-ray structure of pentacarbonyl(7-η1 cyclohepta-1,3,5-trienyl) rhenium(i)
  作者：D.Michael Heinekey、William A.G. Graham

  DOI：10.1016/s0022-328x(00)89214-1

  日期：1982.7

  Synthesis by two routes of (7-η1-C7H7)Re(CO)5 (2), the first monohapto-cycloheptatrienyl derivative of a transition metal, is described. The first involves ultraviolet irradiation of the acyl C7H7(CO)Re(CO)5 (1) in acetone at 78°C.

  由（7-η的两条路线合成1 -C 7 ħ 7）的Re（CO）5（2）中，第一monohapto的过渡金属的衍生物-cycloheptatrienyl，进行说明。第一种方法是在78°C下在丙酮中对酰基C 7 H 7（CO）Re（CO）5（1）进行紫外线照射。
• [8+2] Cycloaddition of 8-oxoheptafulvene with cycloheptatrieneFe(CO)3: synthesis of tricarbonyl[(2,3,4,5-η)-11-acetoxy-1H-cyclohept[a]azulene]iron
  作者：Noboru Morita、Ryuji Yokoyama、Toyonobu Asao、Mituhiro Kurita、Shigeru Kikuchi、Shunji Ito

  DOI：10.1016/s0022-328x(01)01240-2

  日期：2002.1

  8-Oxoheptafulvene reacted with cycloheptatrieneFe(CO)3 by [8+2] cycloaddition to give tricyclo[8.5.0.03,9]pentadeca-3,5,7,11,13-pentaene-2-oneFe(CO)3 (3), which easily reacted with another 8-oxoheptafulvene under the reaction conditions to give four products. One of them was a [2+4] cycloadduct (5) having an uncommon norcaradiene structure. Two products were [8+2] cycloadducts (6 and 7) having a γ-lactone

  8-氧庚烯富烯与环庚三烯Fe（CO）3通过[8 + 2]环加成反应生成三环[8.5.0.0 3,9 ] pentadeca-3,5,7,11,13-戊烯-2-oneFe（CO）3（3），其在反应条件下容易与另一种8-氧庚基富烯反应，得到四种产物。其中之一是具有不常见的正二十碳烯结构的[2 + 4]环加合物（5）。两种产物是具有γ-内酯结构的[8 + 2]环加合物（6和7）。剩余的产物是酰化的化合物（4）。随着反应温度的升高，酰化化合物的产率增加。[1：1]环加合物3在三乙胺的存在下也与乙酰氯反应，得到乙酸盐（12），将其用邻氯苯甲酰氧化，得到11-乙酰氧基-1 H-环庚[ a ] azuleneFe（CO）3（15）。
• Preparation of some 2,4,6-cycloheptatriene-1-yl ketones. Strong preference for the norcaradiene isomer in the case of the 2,4,6-cycloheptatriene-1-yl t-butyl ketone
  作者：G. Boche、R. Eiben

  DOI：10.1016/s0040-4039(00)94872-x

  日期：1985.1

  t-Butyl, i-propyl and phenyl 2,4,6-cycloheptatriene-1-yl ketone (=1a},=c},=d}, respectively) have been synthesized. At −139°C, rather unexpectedly, the t-butyl ketone =1a} exists in a 1:1 equilibrium with its norcaradiene isomer =2a}.

  已经合成了叔丁基，异丙基和苯基2,4,6-环庚三烯-1-基酮（分别为= 1a}，= c}，= d}）。在-139℃下，出乎意料的是，叔丁基酮= 1a}与其降冰片烯异构体= 2a}以1：1的平衡存在。
• The 7-Cycloheptatrienylmethyl/7-Norcaradienylmethyl Cation System
  作者：Ivan Pikulik、Ronald F. Childs

  DOI：10.1139/v75-253

  日期：1975.6.15

  Reaction of 7-carbomethoxycycloheptatriene with either BCl₃ or BBr₃ gave a 1:1 complex in which the Lewis acid was complexed to the carbonyl oxygen. The low temperature p.m.r. and u.v. spectra of these zwitterions indicated that they existed almost entirely in the norcaradiene forms 10 and 14, respectively. In contrast, reaction of N,N-dimethyl-1,3,5-cycloheptatriene-7-carboxamide with BCl₃ was found to result in the formation of a mixture of the cycloheptatriene 12 (65%) and norcaradiene 13 (35%). Comparison of the chemical shifts of the cyclopropyl proton resonances of 10 and 14 with model compounds showed that their positions were anomolous, the C₇ protons resonating at much higher and the C₁ and C₆ protons resonating at much lower field than expected and to account for this it is suggested that these norcaradienes are aromatic systems. Both 10 and 14 were thermally unstable and underwent an irreversible rearrangement to form the complex of methyl phenylacetate, the phenylmethylacylium cation and the appropriate counterion, [Formula: see text] respectively. The rate of these rearrangements and the product distribution was found to be dependent upon both the ratio of Lewis acid to ester used and the nature of the Lewis acid.

  7-羰甲氧基环庚三烯与BCl3或BBr3反应形成1:1的络合物，其中Lewis酸与羰基氧形成络合物。这些带电离子的低温PMR和UV光谱表明，它们几乎全部存在于诺卡二烯的形式10和14中。相比之下，N,N-二甲基-1,3,5-环庚三烯-7-羧酰胺与BCl3反应形成环庚三烯12（65％）和诺卡二烯13（35％）的混合物。将10和14的环丙基质子共振化学位移与模型化合物进行比较，发现它们的位置是异常的，C7质子共振远高于预期，而C1和C6质子共振远低于预期。为了解释这一点，建议这些诺卡二烯是芳香性系统。10和14都是热不稳定的，会发生不可逆的重排反应，形成甲基苯乙酸酯的络合物，苯甲基酰离子和适当的反离子[Formula: see text]。这些重排反应的速率和产物分布发现取决于Lewis酸和酯的比例以及Lewis酸的性质。
• Syntheses and Properties of Hepta- and Dibenzopentafulvalene Derivatives Containing 13-, 15-, 17-, and 19-Membered Rings
  作者：Toyonobu Asao、Noboru Morita、J\={u}ro Ojima、Masamitsu Fujiyoshi、Kazuyo Wada、Satoru Hamai

  DOI：10.1246/bcsj.59.1713

  日期：1986.6

  12-dimethylheptaheptadecafulvalene 15, and 7,12-dimethylheptanonadecafulvalene 16 were synthesized by a reaction of 8-oxoheptafulvene 8 with the corresponding bisdehydroannulenones 1–7. Dibenzo derivatives of 5,10-dimethyl-6,8-bisdehydropentatridecafulvalene 23, 10-methyl-6,8-bisdehydro-4,5-benzopentatridecafulvalene 24, 6,8-bisdehydro-4,5:10,11-dibenzopentatridecafulvalene 25, 5,10-dimethylpentapentadecafulvalene

  5,10-Dimethy 1-6,8-bisdehydroheptatridecafulvalene 10, 10-methy 1-6,8-bisdehydro-4,5-benzoheptatridecafulvalene 11, 6,8-bisdehydro-4,5:10,11-dibenzoheptatridecafulvalene 12 ,10-二甲基-6,8-双脱氢七十五富瓦烯 13、5,10,15-三甲基七十五富瓦烯 14、7,12-二甲基七十七富瓦烯 15 和 7,12-二甲基七十七富瓦烯 16 富瓦烯与相应的双氢戊烯 18-氢戊烯 18-氢戊烯 18-富瓦烯反应合成–7. 5,10-二甲基-6,8-双脱氢五十四富瓦烯 23、10-甲基-6,8-双脱氢-4,5-苯并五十三富瓦烯 24、6,8-双脱氢-4,5:10,11-二苯并五十四碳富瓦烯 25 的二苯并衍生物， 5,10-二甲基五十五富瓦烯