2,2-dichloro-4-methyl-1,1,1-trifluoro-hex-4-ene | 73121-81-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: 2,2-dichloro-4-methyl-1,1,1-trifluoro-hex-4-ene
• 英文别名: 2,2-dichloro-5-methyl-1,1,1-trifluorohex-4-ene；5,5-Dichloro-6,6,6-trifluoro-2-methylhex-2-ene
• CAS: 73121-81-0
• 化学式: C₇H₉Cl₂F₃
• 分子量: 221.05
• InChiKey: JRAGTVVQLNANCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  重氮乙酸乙酯 、 2,2-dichloro-4-methyl-1,1,1-trifluoro-hex-4-ene 在 铜 作用下， 以 甲苯 为溶剂， 反应 20.0h， 以27%的产率得到ethyl 3-(2',2'-dichloro-3',3',3'-trifluoropropyl)-2,2-dimethylcyclopropane-1-carboxylate
  参考文献：
  名称：

  环丙烷羧酸酯的不对称合成：衍生自α-氨基酸的铜（II）Schiff碱配合物催化重氮乙酸酯反应

  摘要：

  描述了通过重氮乙酸乙酯与卤代烯烃的催化反应，合成光稳定的拟除虫菊酯杀虫剂的中间体，即环丙烷甲酸酯的不对称合成。使用衍生自1-苯丙氨酸和芳族醛的手性铜（II）Schiff碱配合物作为催化剂，发现光诱导的程度和方向都取决于烯烃。出乎意料的是，在几个反应中，在环丙烷的C（3）而不是C（1）处有明显的立体选择性。这种新颖的选择性模式是根据从金属-卡宾中间体中的卡宾转移来解释的，其中手性配体控制了接近的烯烃的方向。

  DOI：

  10.1016/0022-328x(84)80341-1

文献信息

• Process for the preparation of cyclopropane carboxylic acid esters
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0022608A1

  公开（公告）日：1981-01-21

  3-Halogenoethyl- or propyl-2,2-dimethylcyclopropane carboxylic acid esters, which are intermediates in the preparation of synthetic pyrethroids, are prepared by the reaction of certain halogenopentenes or hexenes with a diazoacetic ester in the presence of a catalyst which is metallic copper or a copper (II) salt, a rhodium (II) salt of a carboxylic acid or a transition metal complex of certain chiral Schiff bases. By the use of the latter class of catalysts the yield of preferred cis IR isomer may be increased relative to the other possible isomers.

  3-卤代乙基-或丙基-2,2-二甲基环丙烷羧酸酯是制备合成拟除虫菊酯的中间体，其制备方法是某些卤代戊烯或己烯与重氮乙酸酯在金属铜或铜（II）盐、羧酸铑（II）盐或某些手性席夫碱的过渡金属络合物催化剂存在下进行反应。与其他可能的异构体相比，使用后一类催化剂可以提高优选顺式红外异构体的产率。
• Chiral compounds and process for their preparation
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0024795A1

  公开（公告）日：1981-03-11

  Chiral Schiff bases, and transition metal complexes thereof, of formula: wherein R', R2 and R3, which may be the same or different, are hydrogen, alkyl, aralkyl, aryl, alkaryl, a substituent containing a hetero atom, or two of R', R2 and R3 together with the pyridine ring form fused system, R4 and R5 which may be the same or different, are hydrogen, lower alkyl, or, where n is 1, may with the pyridine ring to which CR4R6 is attached form a fused system, R8 is hydrogen, alkyl, aralkyl, aryl or alkaryl, n is 0, 1 or 2 and J and K, which may be the same or different, are groups of the formulae: in which C* is an asymmetric carbon atom, and R7 and R8, which may be the same or different, are alkyl, aralkyl, aryl or alkaryl, or in which at least the ring carbon atom to which the iminyl nitrogen atom is attached is asymmetric, at least one of the carbon atoms adjacent the said ring carbon atom bears a hydroxyl group, R9 and R14, which may be the same or different, are hydrogen or lower alkyl, R10 is hydrogen, or lower alkyl, or together with R15 forms a divalent hydrocarbyl group, R" is hydrogen, a sugar residue, or-CH2OR15 in which R'5 is hydrogen, lower alkyl or together with R10 forms a divalent hydrocarbon group, R12 is hydrogen ar-CH2OR16 in which R15 is hydrogen, or a lower alkyl, R13 is hydrogen, OR', or a sugar residue; provided that both R12 and R'3 are not hydrogen, m is 0, 1 or 2, p is 0 or 1 provided that m plus p is 0, 1, 2 or 3. The transition metal is for example copper (II), chromium (II), manganese (II), iron (II), cobalt (II), nickel (II) or palladium (II). The aforesaid complexes may be used as catalysts in the cyclopropanation of olefins by diazoacetates to form insecticide or insecticide precursors.

  式中的手性希夫碱及其过渡金属配合物： 其中 R'、R2 和 R3（可以相同或不同）是氢、烷基、芳烷基、芳基、烷芳基、含杂原子的取代基，或两个 R'、R2 和 R3 与吡啶环一起形成融合体系，R4 和 R5（可以相同或不同）是氢、低级烷基，或当 n 为 1 时，可与 CR4R6 所连接的吡啶环一起形成融合体系、是氢、低级烷基，或当 n 为 1 时，可与连接了 CR4R6 的吡啶环形成一个融合体系，R8 是氢、烷基、芳基、芳烷基或烷芳基，n 是 0、1 或 2，J 和 K（可相同或不同）是式中的基团： 其中 C* 是不对称碳原子，R7 和 R8（可以相同或不同）是烷基、芳基、芳基或烷芳基，或 其中至少与亚氨基氮原子相连的环碳原子是不对称的，与所述环碳原子相邻的碳原子中至少有一个带有羟基，R9 和 R14（可以相同或不同）是氢或低级烷基，R10 是氢或低级烷基、R "是氢、糖残基或-CH2OR15，其中 R'5 是氢、低级烷基或与 R10 一起形成二价烃基，R12 是氢或-CH2OR16，其中 R15 是氢或低级烷基，R13 是氢、OR'或糖残基；只要 R12 和 R'3 都不是氢，m 是 0、1 或 2，p 是 0 或 1，只要 m 加 p 是 0、1、2 或 3。过渡金属例如是铜（II）、铬（II）、锰（II）、铁（II）、钴（II）、镍（II）或钯（II）。上述配合物可用作重氮乙酸酯环丙烷化烯烃的催化剂，以形成杀虫剂或杀虫剂前体。
• Chiral amino-alcohol complexes and process for their preparation
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0024796A1

  公开（公告）日：1981-03-11

  Chiral Schiff bases according to the general formula: and transistion metal complexes thereof, wherein C* is an asymmetric carbon atom, R' and R2, which may be the same or different are alkyl, aralkyl, aryl or alkaryl, R3 is hydrogen, alkyl, aralkyl, aryl or alkaryl, R4 and R5, which may bethe same or different, are hydrogen or lower alkyl or, where n is 1, may with the cyclic ring to which CR4R5 is attached form a fused system, J is a chain of 3 or 4 atoms which may all be carbon atoms or may be a mixture of carbon atoms and one or more hetero atoms which may be the same or different, which chain with the group CK forms an aromatic system, K is nitrogen, =N → 0, or-NH-, L, each of which may be the same or different, represents a substituent attached to a carbon atom in the chain J and is hydrogen, alkyl, aralkyl, alkaryl, aryl or a substituent containing a hetero-atom; or two L's together with the cyclic ring to which they are attached form a fused system, n is 0, 1 or 2, m is the number of carbon atoms in the chain J. The transition metal is for example copper (II), chromium (II), manganese (II), iron (II), cobalt (II) nickel (II) or palladium (II). The aforesaid complexes may be used as catalysts in the cyclopropanation of olefins by diazoacetates to form insecticide or insecticide precursors.

  根据通式的手性希夫碱： 及其反式金属配合物，其中 C* 是不对称碳原子，R'和 R2（可以相同或不同）是烷基、芳基、芳基或烷芳基，R3 是氢、烷基、芳基、芳基或烷芳基，R4 和 R5（可以相同或不同）是氢或低级烷基，或者，当 n 为 1 时，可以与 CR4R5 所连接的环形成融合体系、J 是由 3 个或 4 个原子组成的链，这些原子可以都是碳原子，也可以是碳原子和一个或多个杂原子的混合物，这些原子可以是相同的，也可以是不同的，该链与基团 CK 形成一个芳香族系统，K 是氮，=N → 0，或-NH-，L 每个可以是相同的，也可以是不同的，代表连接到链 J 中一个碳原子上的取代基，是氢、烷基、芳基、烷芳基、芳基或含有杂原子的取代基；或两个 L 与它们所连接的环形成一个融合体系，n 为 0、1 或 2，m 为链 J 中的碳原子数。过渡金属例如是铜（II）、铬（II）、锰（II）、铁（II）、钴（II）、镍（II）或钯（II）。上述配合物可用作重氮乙酸酯环丙烷化烯烃的催化剂，以形成杀虫剂或杀虫剂前体。
• Process for the manufacture of halogenated hydrocarbons
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0022606A1

  公开（公告）日：1981-01-21

  2,2-Dichloro-5-methyl-1,1,1-trifluorohex-4-ene, an intermediate in the synthesis of pyrethroid insecticides, is obtained by continuous distillation, preferably under sub- atmospheric pressure, of a mixture of 5-methyl-2,2,4-tri- chtoro-1,1,1 -triftuorohexane, dimethylformamide and lithium bromide, precipitating the chlorofluorocarbons from the distillate with water and separating the desired product from starting material by a further distillation.

  2,2-二氯-5-甲基-1,1,1-三氟己-4-烯是合成拟除虫菊酯类杀虫剂的中间体，它是通过连续蒸馏（最好是在次大气压下）5-甲基-2,2,4-三氟-1,1,1-三氟己烷、二甲基甲酰胺和溴化锂的混合物而获得、4-三氟-1,1,1-三氟己烷、二甲基甲酰胺和溴化锂的混合物，用水沉淀馏出物中的氯氟化碳，并通过进一步蒸馏从起始原料中分离出所需产物。
• Chiral sugar complexes and process for their preparation
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0024797A1

  公开（公告）日：1981-03-11

  Chiral Schiff bases according to the general formula: and chiral transition metal complexes thereof, wherein at least the carbon atom of the monosaccharide to which the iminyl nitrogen atom is attached is asymmetric, and at least one of the carbon atoms adjacent the aforesaid carbon atom bears a hydroxyl group, R1 and R6 which may be the same or different, are hydrogen or lower alkyl, R2 is hydrogen, or lower alkyl or together with R10 forms a divalent hydrocarbon group, R3 is hydrogen, a sugar residue, or-CH2OR10 in which R10 is hydrogen, lower alkyl or together with R2 forms a divalent hydrocarbon group, R4 is hydrogen or-CH2OR10 in which R10 is hydrogen, or a lower alkyl, R5 is hydrogen, OR1 or a sugar residue, provided that both R4 and R5 are not hydrogen, R7 and R8 which may be the same or different, are hydrogen, or lower alkyl, or where p is 1, may with the cyclic ring to which CR7R8 is attached form a fused system, R8 is hydrogen, alkyl, aralkyl, aryl or alkaryl, J is a chain of 3 or 4 atoms which with the group CK forms an aromatic system, which atoms may be carbon atoms or may be a mixture of carbon and one or more hetero atoms which may be the same or different, K is nitrogen, or =COH, =→O or -NH-, L each of which may be the same or different, represents a substituent attached to a carbon atom in the chain J and is hydrogen, an alkyl group, aralkyl group, aryl, alkaryl or a substituent containing a hetero-atom; or two L's together with cyclic group to which they are attached form a fused system, m is 0 or 1, n is 0,1 or 2, provided that n plus m is 0, 1, 2 or 3, p is 0, 1 or 2 and q is the number of carbon atoms in the chain J. Thetransition metal is for example copper (II), chromium (II), manganese (II), iron (II), cobalt (II), nickel (II) or palladium (II). The aforesaid complexes may be used as catalysts in the cyclopropanation of olefins by diazoacetates to form insecticide or insecticide precursors.

  根据通式的手性希夫碱： 及其手性过渡金属配合物，其中亚氨基氮原子所连接的单糖的至少一个碳原子是不对称的，与上述碳原子相邻的至少一个碳原子带有羟基，R1和R6可以相同或不同，是氢或低级烷基，R2是氢、R3 是氢、糖残基或-CH2OR10，其中 R10 是氢、低级烷基或与 R2 一起形成二价烃基；R4 是氢或-CH2OR10，其中 R10 是氢或低级烷基；R5 是氢、OR1 或糖残基，但 R4 和 R5 都不是氢、R7 和 R8 可以相同或不同，它们是氢、或低级烷基，或当 p 为 1 时，可与 CR7R8 所连接的环形成一个融合系统，R8 是氢、烷基、芳基、芳烷基或烷芳基，J 是 3 或 4 个原子的链，与基团 CK 形成一个芳香系统、其中的原子可以是碳原子，也可以是碳原子和一个或多个杂原子的混合物，杂原子可以是相同的，也可以是不同的；K 是氮，或 =COH、=→O 或 -NH-；L 每个可以是相同的，也可以是不同的，代表连接到链 J 中一个碳原子上的取代基，是氢、烷基、芳基、芳烷基或含有杂原子的取代基；或两个 L 与所连接的环状基团一起形成一个融合体系，m 为 0 或 1，n 为 0、1 或 2，条件是 n 加 m 为 0、1、2 或 3，p 为 0、1 或 2，q 为链 J 中的碳原子数。过渡金属例如为铜（II）、铬（II）、锰（II）、铁（II）、钴（II）、镍（II）或钯（II）。上述配合物可用作重氮乙酸酯环丙烷化烯烃的催化剂，以形成杀虫剂或杀虫剂前体。