hydrochloride of O-(trans-chloroallyl)hydroxylamine

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: hydrochloride of O-(trans-chloroallyl)hydroxylamine
• 英文别名: O-(trans-chloroallyl)hydroxylamine hydrochloride；O-(1-chloroprop-2-enyl)hydroxylamine;hydrochloride
• 化学式: C₃H₆ClNO*ClH
• 分子量: 144.001
• InChiKey: ZVOFDQVDPLYVSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  35.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  顺式-1,3-二氯丙烯 在 盐酸 作用下， 以 水 为溶剂， 生成 hydrochloride of O-(trans-chloroallyl)hydroxylamine
  参考文献：
  名称：

  Hydroxamic acid esters

  摘要：

  化学式为I H.sub.2 NOR.sub.1 (I)的O-取代羟胺，其中R.sub.1为C.sub.1-C.sub.6烷基、C.sub.1-C.sub.6卤代烷基、--CH.sub.2CR.sub.2.dbd.CR.sub.3R.sub.4或--CH.sub.2C.tbd.CR.sub.5; R.sub.2为氢、卤素或甲基; R.sub.3为氢、卤素或甲基; R.sub.4为氢、卤素或甲基; R.sub.5为氢、甲基或乙基，通过在仅略溶于水或根本不溶于水的有机溶剂中，在氢卤酸HX存在下，将化学式为II R.sub.6--CN(II)的腈与化学式为III R.sub.7--OH(III)的醇反应制备而成。其中，R.sub.6为C.sub.1-C.sub.4烷基、苯基或苄基，R.sub.7为C.sub.1-C.sub.5烷基、苄基或C.sub.1-C.sub.4烷氧乙基。将得到的亚胺酯氢卤酸盐的悬浮液(化学式IV)在-3℃至+5℃的温度下，以控制速率加入碳酸盐或氢碳酸盐的水悬浮液中。在温度为-20℃至-5℃的混合物中加入一种羟胺盐的水溶液，混合物升温至室温后分离水相。将得到的化学式V的羟肟酸酯的有机溶剂溶液，先用强碱水溶液处理，然后用化学式VI Y--R.sub.1(VI)的烷基化试剂处理，其中R.sub.1和Y的定义同上，Y为氯、溴、碘或--O--SO.sub.2R.sub.8，R.sub.8为C.sub.1-C.sub.4烷基、C.sub.1-C.sub.4卤代烷基、苯基或苯基取代的C.sub.1-C.sub.4烷基，苯环本身可能单取代、双取代或三取代，取代基为卤素或C.sub.1-C.sub.4烷基，如果R.sub.1为C.sub.1-C.sub.2烷基，则Y为--OSO.sub.2OR.sub.1。反应混合物在室温至反应混合物沸点的温度下反应，O-烷基化反应结束时混合物冷却至室温，分离水相，化学式VII的羟胺醚(其中R.sub.1、R.sub.6和R.sub.7的定义同上)通过与强酸水溶液搅拌水解，分离含有化学式I的O-取代羟胺的盐的水相，必要时通过蒸发水分离得到化学式I的羟胺。

  公开号：

  US04965390A1

文献信息

• Hydroxamic acid esters
  申请人：Ciba-Geigy Corporation

  公开号：US04965390A1

  公开（公告）日：1990-10-23

  O-substituted hydroxylamines of the formula I H.sub.2 NOR.sub.1 (I) in which R.sub.1 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloakyl, --CH.sub.2 CR.sub.2 .dbd.CR.sub.3 R.sub.4 or --CH.sub.2 C.tbd.CR.sub.5 ; R.sub.2 is hydrogen, halogen or methyl; R.sub.3 is hydrogen, halogen or methyl; R.sub.4 is hydrogen, halogen or methyl; and R.sub.5 is hydrogen, methyl or ethyl, are prepared by reacting a nitrile of the formula II R.sub.6 --CN (II) in which R.sub.6 is C.sub.1 -C.sub.4 alkyl, phenyl or benzyl, is reacted with an alcohol of the formula III R.sub.7 --OH (III) in which R.sub.7 is C.sub.1 -C.sub.5 alkyl, benzyl or C.sub.1 -C.sub.4 alkoxyethyl, in an organic solvent which is only sparingly miscible with water or not at all, in the presence of hydrogen halide HX, the suspension obtained of the iminoester hydrohalide of the formula IV ##STR1## in which R.sub.6 and R.sub.7 are as defined above and X is chlorine, bromine or iodine, is added at a controlled rate to an aqueous suspension of a carbonate or hydrogen carbonate at a temperature of from -3.degree. to +5.degree. C., an aqueous solution of a hydroxylamine salt is added to the mixture obtained at a temperature of from -20.degree. to -5.degree. C., the aqueous phase is separated off after the mixture has been warmed to room temperature, the solution obtained of the hydroximic acid ester of the formula V ##STR2## in which R.sub.6 and R.sub.7 are as defined above, in an organic solvent is first treated with an aqueous solution of a strong base and then with an alkylating agent of the formula VI Y--R.sub.1 (VI) in which R.sub.1 is as defined above and Y is chlorine, bromine, iodine or --O--SO.sub.2 R.sub.8, and R.sub.8 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, phenyl or phenyl-substituted C.sub.1 -C.sub.4 alkyl, it being possible for the phenyl ring itself to be monosubstituted, disubstituted or trisubstituted by halogen or C.sub.1 -C.sub.4 alkyl, and Y is alternatively--OSO.sub.2 OR.sub.1 if R.sub.1 is C.sub.1 -C.sub.2 alkyl, at from room temperature to the boiling point of the reaction mixture, the mixture is cooled to room temperature when the O-alkylation is complete, the aqueous phase is separated off, the oxime ether of the formula VII ##STR3## in which R.sub.1, R.sub.6 and R.sub.7 are as defined above, formed is hydrolysed by stirring with an aqueous solution of a strong acid, and the aqueous phase containing the salt of the O-substituted hydroxylamine of the formula I is separated off, and the hydroxylamine of the formula I is isolated, if necessary, by evaporating the water.

  化学式为I H.sub.2 NOR.sub.1 (I)的O-取代羟胺，其中R.sub.1为C.sub.1-C.sub.6烷基、C.sub.1-C.sub.6卤代烷基、--CH.sub.2CR.sub.2.dbd.CR.sub.3R.sub.4或--CH.sub.2C.tbd.CR.sub.5; R.sub.2为氢、卤素或甲基; R.sub.3为氢、卤素或甲基; R.sub.4为氢、卤素或甲基; R.sub.5为氢、甲基或乙基，通过在仅略溶于水或根本不溶于水的有机溶剂中，在氢卤酸HX存在下，将化学式为II R.sub.6--CN(II)的腈与化学式为III R.sub.7--OH(III)的醇反应制备而成。其中，R.sub.6为C.sub.1-C.sub.4烷基、苯基或苄基，R.sub.7为C.sub.1-C.sub.5烷基、苄基或C.sub.1-C.sub.4烷氧乙基。将得到的亚胺酯氢卤酸盐的悬浮液(化学式IV)在-3℃至+5℃的温度下，以控制速率加入碳酸盐或氢碳酸盐的水悬浮液中。在温度为-20℃至-5℃的混合物中加入一种羟胺盐的水溶液，混合物升温至室温后分离水相。将得到的化学式V的羟肟酸酯的有机溶剂溶液，先用强碱水溶液处理，然后用化学式VI Y--R.sub.1(VI)的烷基化试剂处理，其中R.sub.1和Y的定义同上，Y为氯、溴、碘或--O--SO.sub.2R.sub.8，R.sub.8为C.sub.1-C.sub.4烷基、C.sub.1-C.sub.4卤代烷基、苯基或苯基取代的C.sub.1-C.sub.4烷基，苯环本身可能单取代、双取代或三取代，取代基为卤素或C.sub.1-C.sub.4烷基，如果R.sub.1为C.sub.1-C.sub.2烷基，则Y为--OSO.sub.2OR.sub.1。反应混合物在室温至反应混合物沸点的温度下反应，O-烷基化反应结束时混合物冷却至室温，分离水相，化学式VII的羟胺醚(其中R.sub.1、R.sub.6和R.sub.7的定义同上)通过与强酸水溶液搅拌水解，分离含有化学式I的O-取代羟胺的盐的水相，必要时通过蒸发水分离得到化学式I的羟胺。