phenyl (chloromethyl)(isothiocyanato)thiophosphinate | 136398-79-3

• 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: phenyl (chloromethyl)(isothiocyanato)thiophosphinate
• 英文别名: O-phenylchloromethylisothiocyanatothiophosphonate；O-phenyl (chloromethyl)phosphonoisothiocyanatidothioate；Chloromethyl-(isothiocyanato)phenoxyphosphine sulfide；chloromethyl-isothiocyanato-phenoxy-sulfanylidene-λ5-phosphane
• CAS: 136398-79-3
• 化学式: C₈H₇ClNOPS₂
• 分子量: 263.708
• InChiKey: CRGVLNFTQFBTKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  85.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  phenyl (chloromethyl)(isothiocyanato)thiophosphinate 在 氨 、 三乙胺 作用下， 以 苯 为溶剂， 反应 3.0h， 以88%的产率得到5-amino-2-thioxo-2-phenoxy-1-aza-4-thia-2-phosphol-1-ine
  参考文献：
  名称：

  Kamalov, R. M.; Khailova, N. A.; Gazikasheva, A. A., Doklady Chemistry, 1991, vol. 316, # 4-6, p. 49 - 53

  摘要：

  DOI：
• 作为产物：
  描述：

  potassium thioacyanate 、 o-phenyl (chloromethyl)phosphonochloridothioate 以 乙腈 为溶剂， 以51%的产率得到phenyl (chloromethyl)(isothiocyanato)thiophosphinate
  参考文献：
  名称：

  Kamalov, R. M.; Khailova, N. A.; Gazikasheva, A. A., Doklady Chemistry, 1991, vol. 316, # 4-6, p. 49 - 53

  摘要：

  DOI：

文献信息

• Reaction of chloromethyliso(thio)cyanato(thio)phosphonates(-phosphinates) with phenol, ethanol, and thiols
  作者：N. A. Khailova、R. Kh. Bagautdinova、A. A. Shaimardanova、N. E. Krepysheva、M. A. Pudovik、G. A. Chmutova、N. M. Azancheev、R. Z. Musin、A. N. Pudovik

  DOI：10.1007/s11176-005-0006-7

  日期：2004.9

  (Chloromethyl)isocyanatophosphonates(-phosphinates) take up phenol to form carbamates whose β-cleavage gives rise to phenyl (chloromethyl)phosphonates(-phosphinates). (Chloromethyl)(thio)phosphinic-(phosphonic) isothiocyanates react with phenol at 20°C in the absence of catalyst to afford phenyl phosphinates(-phosphonates). (Alkylsulfanyl)carbamates formed by addition of thiols to (chloromethyl)iso(thio)cyanastophosphonates(-phosphinates) under the action of an equimolar amount of triethylamine undergo cyclization into 1,3,4-oxaza(thiaza)phospholines.

  氯甲基异氰酸磷酸酯（膦酸酯）与酚反应生成氨基甲酸酯，其β-断裂产生苯基氯甲基磷酸酯（膦酸酯）。氯甲基硫代磷酸（膦酸）异硫氰酸酯在无催化剂下于20°C与酚反应生成苯基膦酸酯（磷酸酯）。在三乙胺等摩尔量的作用下，硫醇与氯甲基异（硫）氰酸磷酸酯（膦酸酯）加成形成的烷硫基氨基甲酸酯发生环化生成1,3,4-氧杂（硫杂）磷杂环。
• An Experimental and Theoretical Study of Intramolecular Cyclization of Phosphorylated Thioureas
  作者：V. V. Zverev、G. A. Chmutova、M. A. Pudovik、N. A. Khailova、R. Kh. Bagautdinova、N. M. Azancheev、I. A. Litvinov、O. N. Kataeva、A. N. Pudovik

  DOI：10.1007/s11176-005-0232-z

  日期：2005.3

  New 1,3,2-thiazaphospholines were prepared, and their steric and electronic structures were examined. The steric and electronic structure of N-[(O-methyl)chloromethylthiophosphoryl]thiourea and the pathways of their intramolecular cyclization and rearrangement were studied by ab initio and semiempirical methods. The influence exerted by the conformational factors in thiourea and in the anion formed from it under the conditions of base catalysis on the direction of the reactions involving these species was revealed, and the structure of intermediate complexes and the final products was determined.

  制备了新的 1,3,2-噻唑磷醇，并研究了它们的立体结构和电子结构。利用 ab initio 和半经验方法研究了 N-[(O-甲基)氯甲基硫代磷酸基]硫脲的立体结构和电子结构及其分子内环化和重排的途径。揭示了在碱催化条件下，硫脲及其形成的阴离子中的构象因素对涉及这些物种的反应方向的影响，并确定了中间复合物和最终产物的结构。
• Reaction of Phosphoric (Phosphonic) Acids Amides with Chloromethyliso(thio)cyanatophosphonates (-phosphinates). Synthesis of 1,3,4-Oxaza(thiaza)phospholines
  作者：N. A. Khailova、A. A. Shaimardanova、M. A. Pudovik、N. M. Aznacheev、A. N. Pudovik

  DOI：10.1007/s11178-006-0006-z

  日期：2005.11

  Addition of phosphoric (phosphonic) acids amides to chloromethyliso(thio)cyanatophosphonates (-phosphinates) gave rise to diphosphorylated ureas or thioureas that under effect of bases underwent cyclization into 1,3,4-oxaza(thiaza)phospholines.

  将磷酸（膦酸）酰胺添加到氯甲基异（硫）氰基膦酸盐（-膦酸盐）中会产生二磷酸化的脲类或硫脲类化合物，在碱的作用下环化成 1,3,4-氧氮杂（硫杂）膦脂。
• Development of the Synthesis Methods of Polyheterophosphacyclanes with Endocyclic P-C Bond on the Basis of Functionalized Alkylphosphonates (-Phosphinates)
  作者：Mikhael A. Pudovik、Natalia A. Khailova、Roza Kh. Bagautdinova、Svetlana A. Terent'eva、Ludmila K. Kibardina、Olga N. Kataeva、Vladimir A. Alfonsov

  DOI：10.1080/10426500701761151

  日期：2008.1.14

  We developed a new approach to the synthesis of saturated and unsaturated phosphoruselementocontaining heterocycles was developed; we based it on the addition reactions of various proton nucleophiles (amines, silylamines, alcoholes, mercaptanes, aminoalkylphosphonates, phosphines, CH-acides, etc.) to the halogenmethylphosphonylated isocyanates or isothiocyanates. Intermediate compounds of these reactions

  我们开发了一种合成饱和和不饱和含磷元素杂环的新方法；我们基于各种质子亲核试剂（胺、甲硅烷胺、醇、硫醇、氨基烷基膦酸酯、膦、CH-​​酸等）与卤甲基膦酰化异氰酸酯或异硫氰酸酯的加成反应。这些反应的中间化合物（磷酸化脲、硫脲、氨基甲酸酯、硫脲烷、酰胺等）很容易转化为含磷的环状结构。
• Reaction of O-phenylchloromethylisothiocyanatothiophosphonate with silylated carbamide
  作者：A. M. Pudovik、R. Kh. Bagautdinova

  DOI：10.1134/s107036320808029x

  日期：2008.8

  N'-diethylcarbamide II [4] at heating. We succeeded in performing only the reaction between compounds I and II giving phospholine IV as a final product. In the reaction considered in the first stage the addition product III was formed that during the process suffered cyclization into IV as a result of intramolecular interaction of chloromethyl and thiocarbonyl groups with elimination of trimethylchlorosilane

  已知甲硅烷基胺和硅氮烷很容易添加到有机异氰酸酯中，从而生成 N-甲硅烷基化尿素 [1]。磷酸化异氰酸酯和异硫氰酸酯与甲硅烷基化胺的反应产生相应的含磷和含硅尿素 [2]。P(III) 酸的线性和环状异氰酸酯与甲硅烷基胺的反应发生在异氰酸酯基团被二乙氨基一取代 [3]。没有关于磷酸化异（硫）氰酸酯与脲及其甲硅烷基化衍生物反应机会的公开数据。我们研究了 O-苯基氯甲基异氰酸基膦酸酯和 O-苯基氯甲基异硫氰酸基硫代膦酸酯 I 与 N-苯基N',N'-二乙基脲和 N-苯基-N-三甲基甲硅烷基 N,N'-二乙基脲 II [4] 在加热时的一些反应。我们成功地仅进行了化合物 I 和 II 之间的反应，得到了磷化氢 IV 作为最终产物。在第一阶段考虑的反应中，由于氯甲基和硫代羰基的分子内相互作用以及三甲基氯硅烷的消除，形成了加成产物 III，该产物在该过程中环化为 IV。DOI: 10.1134/S107036320808029X