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)
• 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%).
• Tan-1057 derivatives
  申请人：Bayer Aktiengesellschaft

  公开号：US06617332B1

  公开（公告）日：2003-09-09

  The invention relates to novel natural product derivatives of the formula (I), to processes for their preparation, to pharmaceutical compositions comprising them and to their use in the treatment of disorders in humans or animals: in which R1, D, X, Y and Z are defined as in claim 1.

  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。