4-Chloro-5-methyl-1-(2,4,6-trimethylphenyl)-1,2-dihydrophosphinine 1-oxide | 352463-86-6

• 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: 4-Chloro-5-methyl-1-(2,4,6-trimethylphenyl)-1,2-dihydrophosphinine 1-oxide
• 英文别名: 4-chloro-5-methyl-1-(2,4,6-trimethylphenyl)-2H-1lambda5-phosphinine 1-oxide；4-chloro-5-methyl-1-(2,4,6-trimethylphenyl)-2H-1λ5-phosphinine 1-oxide
• CAS: 352463-86-6
• 化学式: C₁₅H₁₈ClOP
• 分子量: 280.734
• InChiKey: ZMMVMJGIWOJDMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  丁炔二酸二甲酯 、 4-Chloro-5-methyl-1-(2,4,6-trimethylphenyl)-1,2-dihydrophosphinine 1-oxide 生成 7-Chloro-6-methyl-4-(2,4,6-trimethyl-phenyl)-1-oxa-4λ⁵-phospha-spiro[3.5]nona-2,5,7-triene-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  关于芳基膦氧化物与乙炔二羧酸二甲酯的环加成反应

  摘要：

  乙炔二甲酸二甲酯（DMAD）与环状P-（2,4,6-三异丙基苯基）氧化膦的PO部分的[2 + 2]环加成反应具有一般意义，并扩展到环状和脂环族在磷原子上具有不同三烷基苯基取代基的氧化膦。通过半经验量子化学计算研究了[2 + 2]环加成产物的结构

  DOI：

  10.1016/s0040-4039(01)00740-7
• 作为产物：
  描述：

  3-Methyl-1-(2,4,6-trimethylphenyl)-2,5-dihydro-1H-phosphole oxide 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 反应 5.0h， 生成 4-Chloro-5-methyl-1-(2,4,6-trimethylphenyl)-1,2-dihydrophosphinine 1-oxide
  参考文献：
  名称：

  The reaction of 1-(2,4,6-trimethylphenyl)-1,2-dihydrophosphinine 1-oxides with dimethyl acetylenedicarboxylate; a [4+2] or a [2+2] cycloaddition?

  摘要：

  The reaction of dimethyl acetylenedicarboxylate (DMAD) with 3- and 5-methyl-1-aryl-1,2-dihydrophosphinine oxides (6a and 6b, respectively) obtained by the two-step ring enlargement of 2,5-dihydro-1H-phosphole oxide 4 followed different routes. Isomer 6a entered into a [4+2] cycloaddition with DMAD giving, although in low yield, phosphabicyclooctadiene 7, while 6b reacted with the acetylene moiety according to a recently discovered [2+2] protocol to afford spirocyclic oxaphosphete 8. The reaction of isomers 6a and 6b with N-phenylmaleimide under forcing conditions furnished the expected Diels–Alder cycloadducts (10a and 10b, respectively). Hence, depending on the reactant, isomer 6b displayed a dual reactivity.

  DOI：

  10.1039/b010080n

文献信息

• Inverse Wittig reaction of oxaphosphetenes formed by the [2+2] cycloaddition of arylphosphine oxides and dimethyl acetylenedicarboxylate (DMAD)
  作者：Keglevich、Forintos、Koertvelyesi、Toke

  DOI：10.1039/b108675h

  日期：2002.12.17

  The intermediate oxaphosphetenes 2 formed by the novel cycloaddition of the PO group of arylphosphine oxides 1 and the acetylene moiety of DMAD are stabilised by an inverse Wittig reaction to afford the corresponding stabilised phosphonium ylide 3.

  芳基膦氧化物 1 的 PO 基团与 DMAD 的乙炔基团通过新型环加成反应形成的中间肟 2 通过逆维蒂希反应得到稳定，从而得到相应的稳定膦酰亚胺 3。
• New evidence on the structure of the product from the reaction of cyclic 2,4,6-trialkylphenylphosphine oxides with dimethyl acetylenedicarboxylate (DMAD); formed by an inverse Wittig reaction type protocol
  作者：György Keglevich、Tamás Körtvélyesi、Henrietta Forintos、Ágnes Gyöngyvér Vaskó、Izvekov Vladiszlav、László Tőke

  DOI：10.1016/s0040-4020(02)00343-5

  日期：2002.5

  New evidence based on spectroscopy, quantum chemical calculations and reactivity suggest that the spirocyclic oxaphosphetes (5) formed by the [2+2] cycloaddition of the title P-heterocycles (4) and DMAD are intermediates to afford a stabilised phosphonium ylide (6) existing as two conformers (6A and B).

  基于光谱的新证据，量子化学计算和反应性表明，螺oxaphosphetes（5由形成）中的[2 + 2]的标题P-杂环（环加成4）和DMAD是中间体，得到稳定的鏻内鎓盐（6）作为两个构象体（6A和B）存在。
• Efficient Synthesis of 2,8‐Diphosphatricyclo[5.3.1.1^2,6]dodeca‐3,5,9‐triene 2,8‐Dioxides
  作者：János Kovács、Tímea Imre、Krisztina Ludányi、László Toke、György Keglevich

  DOI：10.1081/scc-120028634

  日期：2004.12.31

  The reaction of 1,2-dihydrophosphnine oxides (3a-3d) with tetracyanoethylene (TCNE) did not follow the Diels-Alder protocol, rather the corresponding diphosphatricyclododecatrienes (4a-4d) were formed in good yields. Interaction of the mesityl-dihydrophosphinine oxide (3f) with TCNE resulted in the formation of an alpha-dicyanomethylene derivative (5).