methyl 2-chloro-2-(2'-ethylcyclopropylidene)acetate | 89879-06-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2-chloro-2-(2'-ethylcyclopropylidene)acetate
• 英文别名: Methyl chloro(2-ethylcyclopropylidene)acetate；methyl 2-chloro-2-(2-ethylcyclopropylidene)acetate
• CAS: 89879-06-1
• 化学式: C₈H₁₁ClO₂
• 分子量: 174.627
• InChiKey: OIWXEIFGCRISBE-UHFFFAOYSA-N

物化性质

• 沸点：
  222.5±13.0 °C(Predicted)
• 密度：
  1.183±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 2-chloro-2-(2'-ethylcyclopropylidene)acetate 在 titanium(IV) isopropylate 、 盐酸 作用下， 以 二氯甲烷 为溶剂， 生成 8-chloro-1-ethyl-5-phenyl-4-thia-6-azaspiro[2.5]oct-5-en-7-one
  参考文献：
  名称：

  A New and Efficient Access to Thiazoline-4-carboxylates and Cysteine Derivatives Incorporating Cyclopropyl Groups

  摘要：

  Under basic conditions (NaHCO3, MeCN), thiocarboxamides 2, including NN-thioureas, cleanly undergo Michael addition onto 2-chloro-2-cyclopropylideneacetates 1, attacking through the sulfur, and this is followed by an intramolecular substitution to afford 5-spirocyclopropane-annelated thiazoline-4-carboxylates 4 in 37-92% yields. The thiazolines 4 are cysteine derivatives that possess a cyclopropyl or substituted cyclopropyl group in place of the gem-dimethyl-substituted beta -carbon atom of penicillamine; they can be hydrolyzed to the hydrochloride salt of the amino acid 5 by heating in acid. Under acidic conditions (CH2Cl2, HCl), the Michael adducts 7 of thioamides 2 onto 1 are formed in high to virtually quantitative yields. When treated with NaHCO3 in MeCN, the adducts 7 cyclize to thiazolinecarboxylates 4 (51-82%), but in the presence of Ti(OiPr)(4) they form spirocyclopropane-annelated thiazinones 8 (19-88%).

  DOI：

  10.1002/1099-0690(200108)2001:16<3025::aid-ejoc3025>3.0.co;2-k
• 作为产物：
  描述：

  1-氯-2-乙基-1-(1,2,2-三氯乙烯基)环丙烷 在 氢氧化钾 、 Lewatit SPC 118 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 methyl 2-chloro-2-(2'-ethylcyclopropylidene)acetate
  参考文献：
  名称：

  A Convenient General Access to Methyl 2-Chloro-2-cyclopropylidenacetates, Reactive Michael Acceptors and Cycloaddends

  摘要：

  1-chloro-1-(三氯乙烯基)环丙烷 1 与氢氧化钾/甲醇或甲氧基钠/甲醇反应，生成三甲基 2-氯-2-环丙烯基正乙酸酯 7，通过酸处理可以定量转化为相应的酯 8。这些甲基 2-氯-2-环丙烯基乙酸酯 8 是高度反应性的迈克尔受体，能与软亲核试剂如噻吩酯、二级胺、叠氮、氰化物和二甲基铜锂发生 1,4-加成。然而，反应性受到环丙烷环上取代基的影响，无取代基的化合物 8j 与噻吩酯的反应速率比四甲基衍生物 8a 快 86 倍，而后者的反应性又是甲基 3,3-二甲基丙烯酸酯 16 的 2.5 倍。化合物 8j 是在 [2+2] 和 [2+4] 环加成中均具有相当反应性的环加成体。

  DOI：

  10.1055/s-1988-27456

文献信息

• A New and Efficient Access to Oxazoline-5-carboxylates and Amino Acid Derivatives with Cyclopropyl Groups¹
  作者：Marcus W. Nötzel、Markus Tamm、Thomas Labahn、Mathias Noltemeyer、Mazen Es-Sayed、Armin de Meijere

  DOI：10.1021/jo990170y

  日期：2000.6.1
• Diastereoselective Synthesis of Alkylcyclopropane‐Annelated Methyl 2‐Iminoimidazolidinecarboxylates
  作者：Marcus W. Nötzel、Daniel Frank、Thomas Labahn、Jörg Magull、Armin de Meijere

  DOI：10.1002/ejoc.200801205

  日期：2009.4

  AbstractCyclopropane‐ and alkylcyclopropane‐annelated methyl imidazolidinecarboxylates 5 are formed from unsubstituted 1‐H and from 2′‐substituted methyl 2‐chloro‐2‐cyclopropylideneacetates (1‐R) and N,N′,N″‐triarylguanidines (2) in a domino process consisting of a Michael addition and an immediately ensuing ring closure by intramolecular nucleophilic substitution in moderate to very good yields (30–95 %, 8 examples). The products 5 with alkyl substituents on the spirocyclopropane moiety are formed diastereoselectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• A New and Efficient Access to Thiazoline-4-carboxylates and Cysteine Derivatives Incorporating Cyclopropyl Groups
  作者：Marcus W. Nötzel、Thomas Labahn、Mazen Es-Sayed、Armin de Meijere

  DOI：10.1002/1099-0690(200108)2001:16<3025::aid-ejoc3025>3.0.co;2-k

  日期：2001.8

  Under basic conditions (NaHCO3, MeCN), thiocarboxamides 2, including NN-thioureas, cleanly undergo Michael addition onto 2-chloro-2-cyclopropylideneacetates 1, attacking through the sulfur, and this is followed by an intramolecular substitution to afford 5-spirocyclopropane-annelated thiazoline-4-carboxylates 4 in 37-92% yields. The thiazolines 4 are cysteine derivatives that possess a cyclopropyl or substituted cyclopropyl group in place of the gem-dimethyl-substituted beta -carbon atom of penicillamine; they can be hydrolyzed to the hydrochloride salt of the amino acid 5 by heating in acid. Under acidic conditions (CH2Cl2, HCl), the Michael adducts 7 of thioamides 2 onto 1 are formed in high to virtually quantitative yields. When treated with NaHCO3 in MeCN, the adducts 7 cyclize to thiazolinecarboxylates 4 (51-82%), but in the presence of Ti(OiPr)(4) they form spirocyclopropane-annelated thiazinones 8 (19-88%).
• A Convenient General Access to Methyl 2-Chloro-2-cyclopropylidenacetates, Reactive Michael Acceptors and Cycloaddends
  作者：Thomas Liese、Stephan Teichmann、Armin de Meijere

  DOI：10.1055/s-1988-27456

  日期：——

  The reaction of 1-chloro-1-(trichlorovinyl)cyclopropanes 1 with potassium hydroxide/methanol or sodium methoxide/methanol yields trimethyl 2-chloro-2-cyclopropylidenorthoacetates 7, which can be quantitatively converted to the corresponding esters 8 by acid treatment. The methyl 2-chloro-2-cyclopropylidenacetates 8 are highly reactive Michael acceptors, which readily undergo 1,4-addition with soft nucleophiles such as thiophenolate, secondary amines, azide, cyanide, and lithium dimethylcuprate. The reactivity, however, is influenced by substituents on the cyclopropane ring, the unsubstituted compound 8j reacting 86 times faster with thiophenolate than the tetramethyl derivative 8a, which in turn is 2.5 times as reactive as methyl 3,3-dimethylacrylate 16. Compound 8j is a reasonably reactive cycloaddend in both [2+2]- and [2+4]-cycloadditions.

  1-chloro-1-(三氯乙烯基)环丙烷 1 与氢氧化钾/甲醇或甲氧基钠/甲醇反应，生成三甲基 2-氯-2-环丙烯基正乙酸酯 7，通过酸处理可以定量转化为相应的酯 8。这些甲基 2-氯-2-环丙烯基乙酸酯 8 是高度反应性的迈克尔受体，能与软亲核试剂如噻吩酯、二级胺、叠氮、氰化物和二甲基铜锂发生 1,4-加成。然而，反应性受到环丙烷环上取代基的影响，无取代基的化合物 8j 与噻吩酯的反应速率比四甲基衍生物 8a 快 86 倍，而后者的反应性又是甲基 3,3-二甲基丙烯酸酯 16 的 2.5 倍。化合物 8j 是在 [2+2] 和 [2+4] 环加成中均具有相当反应性的环加成体。