(dichloromethyl)phosphonic dichloride | 29941-08-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (dichloromethyl)phosphonic dichloride
• 英文别名: dichloromethyl phosphonic dichloride；dichloromethylphosphonic dichloride；dichloromethyl-phosphonic acid dichloride；Dichlormethyl-phosphonsaeure-dichlorid；dichloro-methane-phosphonic acid dichloride；dichloromethane-phosphonic acid dichloride；Phosphonic dichloride, (dichloromethyl)-；dichloro(dichlorophosphoryl)methane
• CAS: 29941-08-0
• 化学式: CHCl₄OP
• 分子量: 201.804
• InChiKey: BKNIHVRMZADYLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (dichloromethyl)phosphonic dichloride 在 氨 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以50%的产率得到P-dichloromethylphosphonic diamide
  参考文献：
  名称：

  Synthesis and Herbicidal Activities ofO-MethylP-(Dichloromethyl)phosphonamidates and Diamides

  摘要：

  制备并筛选了 11 种新的 O-甲基对（二氯甲基）氨基膦酸酯和 10 种相应的二酰胺，并筛选了它们的植物生长抑制和除草活性。讨论了这两个系列化合物的结构活性关系。

  DOI：

  10.1080/00021369.1983.10865642
• 作为产物：
  描述：

  (二氯甲基)亚膦酸二氯化物 在 air 作用下， 以90%的产率得到(dichloromethyl)phosphonic dichloride
  参考文献：
  名称：

  Prishchenko, A. A.; Gromov, A. V.; Kadyko, M. I., Journal of general chemistry of the USSR, 1984, vol. 54, # 11, p. 2250 - 2262

  摘要：

  DOI：

文献信息

• Primary α-dichloromethylphosphine; a precursor of unhindered C-chlorophosphaethylene and synthetic equivalent of phospha-acetylene
  作者：J. C. Guillemin、M. Le Guennec、J. M. Denis

  DOI：10.1039/c39890000988

  日期：——

  α-Dichlorophosphine (3), easily obtained by chemoselective phosphonate reduction, is a precursor of the unhindered C-chlorophosphaethylene (4) and a synthetic equivalent of the phospha-acetylene (5).

  α -Dichlorophosphine（3）中，由化学选择性还原膦容易得到，是不受阻碍的前体Ç -chlorophosphaethylene（4）和磷-乙炔（的合成等价物5）。
• Free Radical Reaction of α-Haloalkylphosphonates with Alkenes and Alkynes: A New Approach to Modified Phosphonates
  作者：Piotr Bałczewski、Marian Mikołajczyk

  DOI：10.1055/s-1995-3914

  日期：1995.4

  A new approach to the synthesis of phosphonates 3 functionalized in the α- and γ-phosphonate positions by alkyl, ethoxy, butoxy, acetoxy, acetyl and cyanide groups and allylphosphonate 6 is described. It is based on the radical reaction of α-halosubstituted phosphonates 1 (X=Cl, Br, I) with the terminally unsubstituted alkenes 2 (1-heptene, ethoxyethene, butoxyethene, acetoxyethene, acrylonitrile, methyl vinyl ketone) and alkyne 5 (hept-1-yne). The reaction involving the tin hydride method (Bu3SnH(AlBN) was more effective with alkenes than with alkynes (40-72% versus 20-30%). With electron-rich alkenes, chloro- and bromomethylphosphonates 1 (X=Cl, Br) gave higher yields than iodomethylphosphonate 1 (X=I). Diethyl methylphosphonate 4, as a reduction product of 1, accompanied 3 and 6 in the above reactions. The yield of 4 could be reduced by optimizing the reaction conditions.

  本文介绍了一种在δ-和δ-膦酸位置上由烷基、乙氧基、丁氧基、乙酰氧基、乙酰基和氰基官能化的膦酸盐 3 以及烯丙基膦酸盐 6 合成的新方法。它基于δ-半取代膦酸盐 1（X=Cl、Br、I）与末端未取代的烯 2（1-庚烯、乙氧基乙烯、丁氧基乙烯、乙酰氧基乙烯、丙烯腈、甲基乙烯基酮）和炔 5（庚-1-炔）的自由基反应。采用氢化锡法（Bu3SnH(AlBN)）进行的反应对烯烃比对炔烃更有效（分别为 40-72% 和 20-30%）。对于电子丰富的烯烃，氯甲基和溴甲基膦酸盐 1（X=Cl、Br）的产率高于碘甲基膦酸盐 1（X=I）。甲基膦酸二乙酯 4 作为 1 的还原产物，与 3 和 6 一起参与上述反应。通过优化反应条件，可以降低 4 的产率。
• Organische Phosphorverbindungen 42. Einige Reaktionen von Bis-(dialkoxyphosphonyl-methyl)-O-alkylphosphinaten und Tris-(dialkoxyphosphonyl-methyl)-phosphinoxiden [1]
  作者：Ludwig Maier

  DOI：10.1002/hlca.19700530748

  日期：——

  The metallation of alkyl bis-(dialkyloxyphosphonyl-methyl)-phosphinates (I) and tris-(dialkyloxyphosphonyl-methyl)-phosphine oxides (II) proceeds quantitatively with Na, K, or NaH in inert organic solvents. Alkylation of these metallated derivatives is effected with alkyl halides. In addition to the mono-alkylated products, the di-alkylated and the non-alkylated products are formed also.

  烷基双-（二烷氧基膦酰基-甲基）-次膦酸酯（I）和三-（二烷氧基膦酰基-甲基）-膦氧化物（II）的金属化反应是在惰性有机溶剂中用Na，K或NaH进行的。这些金属化衍生物的烷基化是通过卤代烷进行的。除了单烷基化的产物外，还形成了二烷基化和非烷基化的产物。
• Preparation of
  申请人：Bayer Aktiengesellschaft

  公开号：US04296241A1

  公开（公告）日：1981-10-20

  A process for the preparation of a 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid or derivative of the formula ##STR1## in which R is hydrogen, alkali metal, ammonium, an equivalent of an alkaline earth metal, alkyl, or a radical customary in the alcohol part of pyrethroids, comprising reacting a 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid derivative of the formula ##STR2## with a dichloromethane derivative of the formula ##STR3## in which R.sup.1 and R.sup.2 each independently is alkyl, phenyl, alkoxy or phenoxy, or together are alkanediyl or alkanedioxy, in the presence of a base at a temperature between about -50.degree. and +50.degree. C. The products are intermediates for the preparation of esters of pyrethroid-like insecticidal activity.

  一种制备式为##STR1##的3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷-1-羧酸或其衍生物的方法，其中R是氢、碱金属、铵盐、碱土金属的等当量、烷基或杀虫剂中醇部分常用的基团，包括在碱的存在下，将式为##STR2##的3-甲酰基-2,2-二甲基环丙烷-1-羧酸衍生物与式为##STR3##的二氯甲烷衍生物反应，其中R.sup.1和R.sup.2各自独立地是烷基、苯基、烷氧基或苯氧基，或者一起是烷二基或烷二氧基，在温度在-50℃到+50℃之间。产物是制备类拟除虫菊酯的中间体。
• Process for the preparation of 1,1-dichloroalkenes
  申请人：Bayer Aktiengesellschaft

  公开号：US04342704A1

  公开（公告）日：1982-08-03

  A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl or aryl radical, and R.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aralkenyl or aryl radical, or cycloalkyl which is optionally substituted by halogen, alkyl, alkanoyl, carbamoyl, cyano or phenyl, or R.sup.1 and R.sup.2 together form a hydrocarbon chain which is optionally branched and/or optionally contains a fused benzene ring, comprising reacting an aldehyde or ketone of the formula ##STR2## with a dichloromethane-phosphonic acid ester of the formula ##STR3## in which R.sup.3 each independently is alkyl or phenyl or the two radicals R.sup.3 together are alkanediyl, in the presence of a base at a temperature between about -50.degree. and +50.degree. C. Preferably either the base is metered into a mixture of the aldehyde or ketone and phosphonic acid ester or the ester is added to a mixture of the base and aldehyde or ketone.

  一种制备式为##STR1##的1,1-二氯烯烃的方法，其中R.sup.1是氢或可选择取代的烷基、烯基、炔基、芳基烷基或芳基基团，R.sup.2是可选择取代的烷基、烯基、炔基、芳基烷基、芳基烯基或芳基基团，或者是可选择取代的环烷基，其中该环烷基可以被卤素、烷基、烷酰基、氨基甲酰基、氰基或苯基取代，或者R.sup.1和R.sup.2共同形成一个可选择分支或可选择包含融合苯环的碳氢链，包括在碱存在下，在约-50℃到+50℃之间的温度下，将式为##STR2##的醛或酮与式为##STR3##的二氯甲磷酸酯反应，其中R.sup.3各自独立地是烷基或苯基，或两个基团R.sup.3共同是烷二基基团。优选地，碱被计量地加入到醛或酮和膦酸酯的混合物中，或者膦酸酯被加入到碱和醛或酮的混合物中。