(3-chloro-3-methyl-2-butylidene)isopropylamine | 81171-34-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (3-chloro-3-methyl-2-butylidene)isopropylamine
• CAS: 81171-34-8
• 化学式: C₈H₁₆ClN
• 分子量: 161.675
• InChiKey: NPUBYWKZXRGPQP-JXMROGBWSA-N

物化性质

• 沸点：
  42-45 °C(Press: 11 Torr)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (3-chloro-3-methyl-2-butylidene)isopropylamine 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 N-isopropylpivalamide
  参考文献：
  名称：

  α-氯酮亚胺的Favorskii型重排

  摘要：

  报道了α-一氯酮亚胺的Favorskii型重排的第一个例子。在Favorskii条件下，中间体环丙基亚胺的区域特异性开口与环丙烷的开口平行。

  DOI：

  10.1016/s0040-4039(01)90454-x
• 作为产物：
  描述：

  3-氯-3-甲基丁酮 、 异丙胺 在 四氯化钛 作用下， 生成 (3-chloro-3-methyl-2-butylidene)isopropylamine
  参考文献：
  名称：

  Rearrangement of 4-(1-Haloalkyl)- and 4-(2-Haloalkyl)-2-azetidinones into Methyl ω-Alkylaminopentenoates via Transient Aziridines and Azetidines

  摘要：

  The synthesis of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones was investigated with use of the Staudinger reaction between in situ generated ketenes and alpha-haloimines or beta-haloimines. This new class of functionalized 2-azetidinones was further evaluated for its potential use as intermediates in the synthesis of highly functionalized compounds. The reaction of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones with sodium methoxide in methanol yielded ring-opened products, i.e., methyl 2-alkoxy-4-(alkylamino)pentenoate and methyl 5-(alkylamino)pentenoate, respectively. Further attention was paid in detail to the reaction mechanism involved in this peculiar transformation. It was proven that these reactions proceeded via intermediate aziridines or azetidines.

  DOI：

  10.1021/jo040161b

文献信息

• Syntheses and Reactions of 1-Amino-2,2-dialkylcyclopropane-1-carbonitriles and -carboxamides – Potential Precursors of ACC Derivatives
  作者：Wim Aelterman、Kourosch Abbaspour Tehrani、Wim Coppens、Tom Huybrechts、Norbert De Kimpe、Dirk Tourwé、Jean-Paul Declercq

  DOI：10.1002/(sici)1099-0690(199901)1999:1<239::aid-ejoc239>3.0.co;2-z

  日期：1999.1

  product. Various new cis- and trans-1-(teri-butylamino)-2-benzyl- 2-methylcyclopropane-carbonitriles and the corresponding cyclopropanecarboxamides have been synthesized, with focus on the isolation of the pure stereoisomeric cyclopropanecarboxamides. The relative configuration of the stereoisomers was established by X-ray crystallographic analysis of one of the model compounds. A new route to the latter

  2-氨基-4-氯-3,3-二甲基丁腈与叔丁醇钾在THF中的直接环化得到1-氨基-2,2-二甲基环丙烷-1-腈和二聚产物。已经合成了各种新的顺式和反式 1-(叔丁基氨基)-2-苄基-2-甲基环丙烷甲腈和相应的环丙烷甲酰胺，重点是纯立体异构环丙甲酰胺的分离。立体异构体的相对构型是通过一种模型化合物的 X 射线晶体学分析建立的。通过 1-甲氧基环丙胺与氰化钾的反应，开发了获得后者官能化环丙烷的新途径。报道了通过 Favorskii 衍生的中间体将 1-氨基环丙烷-1-腈重排为氮杂环丁烷和恶嗪衍生物的一些显着重排。
• New synthesis of N-alkyl 2,2-dialkylcyclopropylamines viaα-chloro imines
  作者：Norbert De Kimpe、Pascal Brunet、Roland Verhé、Niceas Schamp

  DOI：10.1039/c39880000825

  日期：——

  2,2-Dialkylcyclopropylamines have been prepared by a new synthetic method involving cyclopropanation of α-chloro imines and reductive demethoxylation of the resulting 1-methoxycyclopropylamines.

  已经通过一种新的合成方法制备了2，2-二烷基环丙胺，该方法包括α-氯亚胺的环丙烷化和所得的1-甲氧基环丙胺的还原性脱甲氧基化。
• Organometallic reactions of α-haloimines as a useful tool in organic synthesis
  作者：Norbert de Kimpe、Bart de Corte、Roland Verhe、Laurent de Buyck、Niceas Schamp

  DOI：10.1016/s0040-4039(01)80111-8

  日期：1984.1

  The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles.

  有机金属试剂（例如烷基锂，铜酸盐和烷基铜）与α-卤代亚胺的反应选择性地产生了多种合成上有用的反应，包括与1,4-二亚胺的偶联，同系物和杂环的产生。
• A novel synthesis of α-cyanoaziridines
  作者：Norbert De Kimpe、Luc Moëns、Roland Verhé、Laruent De Buyck、Niceas Schamp

  DOI：10.1039/c39820000019

  日期：——

  A new route to α-cyanoaziridines has been developed by reaction of α-chloroketimines with potassium cyanide in methanol, which involves nucleophilic addition and subsequent intramolecular nucleophilic substitution.

  通过α-氯代酮亚胺与氰化钾在甲醇中的反应，已开发出一种新的α-氰基氮丙啶路线，该过程涉及亲核加成和随后的分子内亲核取代。
• Unusual ring opening of a Cyclopropylideneamine derivative during a favorskii-type rearrangement of α-Chloroketimines
  作者：Norbert De Kimpe、Mariana Palamareva、Paul Sulmon、Roland Verhe、Laurent De Buyck、Niceas Schamp、Jean-Paul Declerco、Bernard Tinant、Maurice Van Meerssche

  DOI：10.1016/s0040-4020(01)87403-2

  日期：1986.1

  3-dehydrochlorination affording intermediate cyclopropylideneamines (N-analogues of cyclopropanones), which “dimerize” in an unusual way. This mechanism entails a “normal” opening as well as an “abnormal” opening of incipient cyclopropylideneamine adducts. This rearrangement represents an example of the scarcely reported abnormal opening of functionalized cyclopropylamines.

  N-（3-氯-3-甲基-2-丁叉）胺（即α-氯代酮亚胺）与二异丙基氨基化锂在四氢呋喃中的反应导致意外的反应，导致2-（N-烷基亚氨基）-3,3-二甲基-1-异丙基-5-（2-甲基亚丙基）吡咯烷具有良好的收率。用Favorskii型1，3-脱氯化氢来解释反应机理，得到中间体环丙叉亚胺（环丙烷的N-类似物），其以不寻常的方式“二聚”。这种机理需要初始的环丙二烯胺加合物的“正常”开口和“异常”开口。这种重排代表了很少报道的官能化环丙胺异常打开的例子。