(+)-(1S,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester | 67968-42-7

• 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: (+)-(1S,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester
• 英文别名: (1S,3S)-3-formyl-2,2-dimethylcyclopropanecarboxylic acid methyl ester；biocartol methyl ester；biocartol methylester；rel-Methyl (1R,3S)-3-formyl-2,2-dimethylcyclopropanecarboxylate；methyl (1S,3R)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate
• CAS: 67968-42-7
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: KVSRWNPBUMDYOQ-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(1S,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.08h， 以82%的产率得到(1S,3R)-3-formyl-2,2-dimethylcyclopropanecarboxylic acid methyl ester
  参考文献：
  名称：

  Synthesis of All Stereoisomers of the Norchrysanthemic Acid Methyl Ester

  摘要：

  Syntheses of eight stereoisomers of methyl norchrysanthemate, (1R)-trans-(Z)-isomer and (1R)-trans-(E)-isomer from (IR)-trans-chrysanthemic acid, and other six isomers from (+)-3-carene, are described.

  DOI：

  10.1081/scc-120028630
• 作为产物：
  描述：

  (+)-4α-acetyl-2-carene 在 苯基溴化硒 、 双氧水 、 sodium hydride 、 臭氧 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 生成 (+)-(1S,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester
  参考文献：
  名称：

  A new synthesis of caronaldehyde from (+)-4?-acetyl-2-carene

  摘要：

  DOI：

  10.1007/bf01168112

文献信息

• Modified Julia Fluoroolefination:  Selective Preparation of Fluoroalkenoates
  作者：Emmanuel Pfund、Cyril Lebargy、Jacques Rouden、Thierry Lequeux

  DOI：10.1021/jo070994c

  日期：2007.10.1

  The modified Julia olefination reaction has been applied to develop a stereoselective synthesis of fluoroalkenoate derivatives from a fluorobenzothiazolyl sulfone and aldehydes or a ketone. The olefination reaction can be achieved by using a variety of bases. DBU and DBU in the presence of MgBr2 were found to be the most efficient systems to prepare either (Z)- or (E)-alkenoates in moderate to excellent

  改性的朱莉娅烯化反应已用于开发从氟苯并噻唑基砜和醛或酮的氟代链烯酸酯衍生物的立体选择性合成。可以通过使用多种碱来实现烯化反应。发现在MgBr 2存在下，DBU和DBU是制备中度至优异的立体选择性的（Z）-或（E）-链烯酸酯的最有效系统。
• Stereoselective formation of (Z)-2-fluoroalkenoates via Julia–Kocienski reaction of aldehydes with pyrimidinyl-fluorosulfones
  作者：Florent Larnaud、Emmanuel Pfund、Bruno Linclau、Thierry Lequeux

  DOI：10.1016/j.tet.2014.06.081

  日期：2014.9

  This sulfone allowed the preparation of Z-fluoroalkenoates with very high stereoselectivity from both aromatic and aliphatic aldehydes. The nature of the heterocycle on the course of the Julia–Kocienski reaction is discussed.

  从嘧啶基氟砜报道了氟代链烯酸酯的选择性合成。该砜允许由芳族和脂族醛两者制备具有非常高的立体选择性的Z-氟代链烯酸酯。讨论了Julia-Kocienski反应过程中杂环的性质。
• Oxabicyclo 3.1.0 hexanes useful in the production of cyclopropanecarboxylate insecticides and intermediate compounds
  申请人：FMC Corporation

  公开号：EP0003666A1

  公开（公告）日：1979-08-22

  The invention provides compounds of the formulae: in which R is hydrogen or CX3. each X, which is the same as or different from the other, is a chlorine or bromine atom, R' is lower alkyl or lower alkoxy, R2 is hydrogen, lower alkoxycarbonyl or lower alkanoyl, and R3 is hydrogen or lower alkoxycarbonyl. The compounds of Formula III are made by intramolecular carbenoid cyclization of compounds of Formula II; the compounds of Formula II are made from compounds of Formula I, e.g. by treatment with azide followed by a base; the compounds of Formula I are prepared by reacting an alcohol of formula: with a hydrazone. Those compounds of Formula I in which R is CX3 can be converted to a compound of the formula: in which the carboxy and dihalovinyl groups are cis with respect to each other, which are insecticidal, by treatment with certain metals in selected solvents.

  本发明提供了以下式子的化合物： 其中R为氢或CX3.与之相同或不同的各X为氯原子或溴原子，R'为低级烷基或低级烷氧基，R2为氢、低级烷氧羰基或低级烷酰基，R3为氢或低级烷氧羰基。 式 III 的化合物是通过式 II 的化合物的分子内类碳环化反应制得的；式 II 的化合物是由式 I 的化合物制得的，例如先用叠氮化物处理，再用碱处理；式 I 的化合物是通过式......的醇与腙反应制备的： 与腙反应制得。 其中 R 为 CX3 的式 I 化合物可转化为式： 其中羧基和二卤乙烯基互为顺式基团的化合物，可通过在选定溶剂中使用某些金属进行处理而获得杀虫效果。
• Novel trihaloethyl carbonate derivatives and a process for their production
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0016504A2

  公开（公告）日：1980-10-01

  Process for the preparation of novel trihalomethyl carbonates of the general formula: wherein R1 represents an optionally-substituted cyclopropyl or an optionally-substituted alkyl group, R1 a methyl group or a hydrogen atom or R1 and R2, together with the carbon atom to which they are attached jointly form a cycloalkyl group, each Hal is a chlorine or bromine atom and M represents an alkali metal atom, wherein a carbonyl compound of the general formula: wherein R1 and R have the same meaning as in formula I, is reacted under substantially anhydrous conditions with a trihaloacetate of the general formula: wherein Hal and M have the above-mentioned meaning, in the presence of a highly polar, aprotic inert solvent. The trihalomethyl carbonates are useful as intermediates in the manufacture of pyrethroid insecticides.

  通式如下的新型三卤甲基碳酸盐的制备工艺 其中 R1 代表任选取代的环丙基或任选取代的烷基，R1 代表甲基或氢原子，或 R1 和 R2 连同它们所连接的碳原子共同形成环烷基，每个 Hal 代表氯原子或溴原子，M 代表碱金属原子，其中通式如下的羰基化合物 式中 R1 和 R 的含义与式 I 相同，在基本无水条件下与通式为 其中 Hal 和 M 具有上述含义，在高极性、钝性惰性溶剂存在下进行反应。三卤甲基碳酸盐可用作生产拟除虫菊酯杀虫剂的中间体。
• Process for the preparation of dihalovinyl compounds
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0016505A1

  公开（公告）日：1980-10-01

  Process for the preparation of a dihalovinyl compounds of the general formula: wherein R' represents an optionally-substituted cyclopropyl group or an optionally-substituted alkyl group, R2 a methyl group or a hydrogen atom or R' and R2, together with the carbon atom to which they are attached jointly form a cycloalkyl group, and each Hal stands for a chlorine or bromine atom, characterised in that a trihalomethyl compound of the general formula: wherein R', R2 and Hal have the same meaning as in formula I and X represents a group -PQ2, -CO-OR or-SO2-R4 wherein Q represents a halogen atom and R3 and R4 both represent an optionally-substituted alkyl group, is contacted with zinc and an alkanoic acid with up to 5 carbon atoms per molecule: The dihalovinyl compounds are intermediates in the manufacture of pyrethroid insecticides.

  通式如下的二卤乙烯基化合物的制备工艺 其中 R'代表任选取代的环丙基或任选取代的烷基，R2 代表甲基或氢原子或 R'和 R2 与它们所连接的碳原子共同形成环烷基，每个 Hal 代表一个氯原子或溴原子，其特征在于通式的三卤甲基化合物 其中 R'、R2 和 Hal 的含义与式 I 相同，X 代表基团-PQ2、-CO-OR 或-SO2-R4，其中 Q 代表卤素原子，R3 和 R4 均代表任选取代的烷基：二卤乙烯基化合物是生产拟除虫菊酯杀虫剂的中间体。