methyl 2-chloro-2-[2'-(2''-benzyloxyethyl)cyclopropylidene]acetate | 287728-56-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-chloro-2-[2'-(2''-benzyloxyethyl)cyclopropylidene]acetate
• 英文别名: methyl 2-chloro-2-[2'-(2''-benzoxyethyl)-cyclopropylidene]acetate；methyl 2'-benzyloxyethyl-2-chloro-2-cyclopropylideneacetate；methyl [2-(2-benzyloxyethyl)cyclo-propylidene]chloroacetate；Methyl [2-(2-benzyloxyethyl)cyclo-propylidene]chloroacetate；methyl 2-chloro-2-[2-(2-phenylmethoxyethyl)cyclopropylidene]acetate
• CAS: 287728-56-7
• 化学式: C₁₅H₁₇ClO₃
• 分子量: 280.751
• InChiKey: JTWVRDYZKMZHPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  硫代乙酰胺 、 methyl 2-chloro-2-[2'-(2''-benzyloxyethyl)cyclopropylidene]acetate 在 碳酸氢钠 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以77%的产率得到methyl 2'-methylspiro{[2-(2''-benzyloxyethyl)cyclopropane]-1,5'(4'H)-thiazoline}-4'-carboxylate
  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：

  2-(2'-benzyloxyethyl)-1-chloro-1-(trichloroethenyl)cyclopropane 、 钠 、 水 、 甲醇 在 J 、 乙醚 、 10 、 盐酸 、 无水氯化钙 、 silica gel 、 K 作用下， 反应 48.75h， 以gives 24.4 g (47%) of K methyl [2-(2-benzyloxyethyl)cyclo-propylidene]chloroacetate in the form of a pale yellow liquid的产率得到methyl 2-chloro-2-[2'-(2''-benzyloxyethyl)cyclopropylidene]acetate
  参考文献：
  名称：

  Tan-1057 derivatives

  摘要：

  本发明涉及公式（I）的新型天然产物衍生物，其制备过程，包括它们的制药组合物以及它们在治疗人类或动物疾病中的应用：其中R1，D，X，Y和Z如权利要求1所定义。

  公开号：

  US06617332B1

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)