2,2-dimethylpent-4-enoyl chloride | 39482-46-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 2,2-dimethylpent-4-enoyl chloride
• 英文别名: 2,2-dimethyl-4-pentenoic acid chloride；2,2-dimethyl-4-pentenoyl chloride
• CAS: 39482-46-7
• 化学式: C₇H₁₁ClO
• 分子量: 146.617
• InChiKey: WYKIVLYHNSLTKU-UHFFFAOYSA-N

物化性质

• 沸点：
  153.7±19.0 °C(Predicted)
• 密度：
  0.992±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2916190090

反应信息

• 作为反应物：
  描述：

  2,2-dimethylpent-4-enoyl chloride 在 rhodium(II) acetate dimer 盐酸 、 四氯化锡 、 sodium hydride 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 37.0h， 生成 蕨素 Z
  参考文献：
  名称：

  Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.

  DOI：

  10.1021/jo951371e
• 作为产物：
  描述：

  2,2-二甲基-4-戊酸甲酯 生成 2,2-dimethylpent-4-enoyl chloride
  参考文献：
  名称：

  分子内均质置换7 —不饱和过氧化合物的自由基加成：氧化杂环的合成

  摘要：

  将氢供体溶剂自由基加到过戊-4-烯酸叔丁酯中，得到4-取代的γ-丁内酯，产率为50％或更高。应用于烯丙基叔丁基过氧化物的这种反应已经产生了这些溶剂的2，3-环氧丙烷化。4-甲基-过戊-4-烯酸酯叔丁基，2,2-二甲基-过戊-4-烯酸酯叔丁基和过氧化甲基叔丁基甲基烯丙基也发生了类似的加成消除过程，但对于叔丁基5则失败了。 -甲基-己基-4-烯酸酯和叔丁基-3-甲基-丁-2-烯基过氧化物。

  DOI：

  10.1016/s0040-4020(01)97183-2

文献信息

• Metal-Free, Aerobic Dioxygenation of Alkenes Using Hydroxamic Acids
  作者：Valerie A. Schmidt、Erik J. Alexanian

  DOI：10.1002/anie.201000843

  日期：2010.6.14

  One dioxygenation please, hold the metal: In the presence of either oxygen or air as the sole oxidant and external oxygen atom source, a variety of unsaturated hydroxamic acids afford cyclic hydroxamates that are readily converted into 1,2‐diols, with the potential for high levels of reaction stereocontrol.

  请进行一次双氧合，以固定金属：在氧气或空气作为唯一氧化剂和外部氧原子源的情况下，各种不饱和异羟肟酸提供的环状异羟肟酸酯很容易转化为1,2-二醇，并有可能高水平的反应立体控制。
• Alkene Hydrofunctionalization Using Hydroxamic Acids: A Radical-Mediated Approach to Alkene Hydration
  作者：Benjamin C. Giglio、Erik J. Alexanian

  DOI：10.1021/ol5020202

  日期：2014.8.15

  A radical-mediated approach to alkene hydration is described. The present strategy capitalizes on the unique radical reactivity of hydroxamic acids, which are capable of functioning as both synthetically useful oxygen-centered radical species and suitable hydrogen atom-based donors. This reaction manifold has been applied to both alkene hydrations and tandem alkene–alkene carbocyclization processes

  描述了自由基介导的烯烃水合方法。本策略利用了异羟肟酸的独特的自由基反应性，该异羟肟酸既可以用作合成有用的以氧为中心的自由基物种，又可以用作合适的基于氢原子的供体。该反应歧管已应用于烯烃水合和串联烯烃-烯烃碳环化过程。
• Metal-Free Oxyaminations of Alkenes Using Hydroxamic Acids
  作者：Valerie A. Schmidt、Erik J. Alexanian

  DOI：10.1021/ja204255e

  日期：2011.8.3

  A radical-mediated approach to metal-free alkene oxyamination is described. This method capitalizes on the unique reactivity of the amidoxyl radical in alkene additions to furnish a general difunctionalization using simple diisopropyl azodicarboxylate (DIAD) as a radical trap. This protocol capitalizes on the intramolecular nature of the process, providing single regioisomers in all cases. Difunctionalizations

  描述了一种自由基介导的无金属烯烃氧胺化方法。该方法利用烯烃加成中脒氧基自由基的独特反应性，使用简单的偶氮二甲酸二异丙酯 (DIAD) 作为自由基陷阱提供一般的双官能化。该协议利用该过程的分子内性质，在所有情况下提供单一区域异构体。环状烯烃的双官能化提供了使用当前方法无法获得的具有高立体选择性的反式氧胺化产物，补充了顺式选择性氧胺化过程。
• Condensed diazepinones, processes for preparing them and agents
  申请人：Dr. Karl Thomae GmbH

  公开号：US05610155A1

  公开（公告）日：1997-03-11

  New condensed diazepinones of general formula I ##STR1## wherein B represents one of the divalent groups ##STR2## and X, l, m, n and R.sup.1 to R.sup.7 are as defined herein, as well as the salts thereof with inorganic or organic acids and processes for preparing them. These compounds are useful for improving or normalising arteriosclerotically induced disorders of cerebral blood flow, for treating diseases of the central nervous system, particularly Alzheimer's disease and Parkinson's disease, and as vagal pacemakers for treating bradycardia and bradyarrhythmia, and also for improving memory performance.

  新型缩合二氮杂卓酮，其通式为I ##STR1## 其中B代表下列二价基团之一 ##STR2## X、l、m、n以及R1至R7如本文所定义，以及它们的无机或有机酸的盐和制备这些化合物的方法。这些化合物可用于改善或正常化动脉硬化引起的脑血流障碍，治疗中枢神经系统疾病，特别是阿尔茨海默病和帕金森病，作为迷走神经起搏器治疗心动过缓和心律过缓，以及改善记忆表现。
• Nickel-Catalyzed Aminoxylation of Inert Aliphatic C(sp³)–H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α-Formyl Acid Derivatives
  作者：Chunxia Wang、Luoqiang Zhang、Jingsong You

  DOI：10.1021/acs.orglett.7b00479

  日期：2017.4.7

  Nickel-catalyzed aminoxylation of an unactivated C(sp3)–H bond with a stable nitroxyl radical has been accomplished for the first time to offer various N-alkoxyamine derivatives, which further enables a one-pot approach to α-formyl acid derivatives. The aminoxylation process reported also provides direct evidence for the oxidative addition of a cyclometallic intermediate with a free radical, which

  镍催化未活化的C（sp 3）-H键与稳定的硝酰基自由基的氨氧化反应已首次完成，以提供各种N-烷氧基胺衍生物，这进一步使一锅法制备α-甲酰基酸衍生物成为可能。报道的氨氧化过程也为环金属中间体与自由基的氧化加成提供了直接证据，这对过渡金属催化的惰性C（sp 3）-H键的官能化反应机理的研究很有帮助。