5-[1-Adamantan-1-yl-1-triisopropylsilanyloxy-meth-(E)-ylidene]-3,3-diphenyl-4-(2,4,6-trimethyl-phenyl)-4,5-dihydro-3H-[1,2,4]diazaphosphole | 162931-68-2

• 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: 5-[1-Adamantan-1-yl-1-triisopropylsilanyloxy-meth-(E)-ylidene]-3,3-diphenyl-4-(2,4,6-trimethyl-phenyl)-4,5-dihydro-3H-[1,2,4]diazaphosphole
• 英文别名: [(E)-1-adamantyl-[5,5-diphenyl-4-(2,4,6-trimethylphenyl)-1,2,4-diazaphosphol-3-ylidene]methoxy]-tri(propan-2-yl)silane
• CAS: 162931-68-2
• 化学式: C₄₃H₅₇N₂OPSi
• 分子量: 676.998
• InChiKey: JKSKHTNHWGROFC-CDJCAARLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.66
• 重原子数：
  48
• 可旋转键数：
  9
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  34
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-[1-Adamantan-1-yl-1-triisopropylsilanyloxy-meth-(E)-ylidene]-3,3-diphenyl-4-(2,4,6-trimethyl-phenyl)-4,5-dihydro-3H-[1,2,4]diazaphosphole 以 乙醚 为溶剂， 反应 1.0h， 以66%的产率得到1-(1-adamantyl)-2-[diphenylmethyleneamino(2,4,6-trimethylphenyl)phosphino]-2-[(triisopropylsilyl)imino]ethan-1-one
  参考文献：
  名称：

  Photochemical Isomerizations of 5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-Phosphapyrazolines): (5→4) Ring Contraction Generates Azomethineimine Dipoles

  摘要：

  UV irradiation of the title compounds 1a-d results not in extrusion of molecular nitrogen, but in a skeletal rearrangement generating amino(imidoyl)phosphanes 2a-c from 1a-c and 2-hydrazinobenzo[b]phosphole 4 from 1d. The first step in these isomerizations is an unprecedented (5-->4) ring contraction of 1 to form the semicyclic azomethineimine dipoles 10 incorporating a 1,2,3-diazaphosphetidine ring. Dipoles 10a-c, but not 10d, can be observed by NMR spectroscopy after brief irradiation of the precursors. Furthermore, they could be trapped by [3+2] cycloaddition reaction with dimethyl acetylenedicarboxylate to give the bicyclic 1,2,3-diazaphosphetidines 12a-c, and, in the case of 10a and 10c, also the dihydrophospholes 13a,c resulting from a second [3+2] cycloaddition.

  DOI：

  10.1002/(sici)1521-3765(19980515)4:5<903::aid-chem903>3.0.co;2-j
• 作为产物：
  描述：

  mesityldiphenylmethylenephoshine 、 2-(1-adamantyl)-1-diazo-1-(triisopropylsilyl)-2-ethanone 以 二氯甲烷 为溶剂， 反应 16.0h， 以77%的产率得到5-[1-Adamantan-1-yl-1-triisopropylsilanyloxy-meth-(E)-ylidene]-3,3-diphenyl-4-(2,4,6-trimethyl-phenyl)-4,5-dihydro-3H-[1,2,4]diazaphosphole
  参考文献：
  名称：

  合成5-亚甲基-4,5-二氢-3- ħ -1,2,4-（λ 3）-diazaphospholes从α-甲硅烷基- α-重氮酮和phosphaalkenes

  摘要：

  5亚烷基-4,5-二氢-3- ħ -1,2,4-（λ 3）-diazaphospholes（II）发生来自不同，不同取代的phosphaalkenes和之间的[3 + 2]环加成反应2甲硅烷氧基-1-在与α-甲硅烷基-α-二氮杂酮的热平衡中少量存在的重氮烯烃。环加成产物4a-g，6a，b，e，f和8具有足够的热稳定性，可以被分离。在其他情况下，甲硅烷基迁移（环-C→N或O→N）导致N-甲硅烷基-1,2,4-二氮杂磷烯异构体。

  DOI：

  10.1016/0040-4020(96)00541-8

文献信息

• Synthesis of alkylidenephosphiranes by extrusion of nitrogen from 3-alkylidene-4,5-dihydro-3H-1,2,4-diazaphospholes
  作者：Berthold Manz、Gerhard Maas

  DOI：10.1039/c39950000025

  日期：——

  The 3-alkylidene-4,5-dihydro-3H-1,2,4-diazaphospholes 4, obtained from diphenylmethylene(mesityl) phosphine 3 and silyl diazo ketones 1, undergo thermal extrusion of nitrogen to form alkenyl phosphines 7 and alkylidenephosphiranes 8; the structures of these products have been established by single crystal X-ray structure analyses.

  由二苯基亚甲基（甲磺酰基）膦3和甲硅烷基重氮酮1获得的3-亚烷基-4,5-二氢-3 H -1,2,4-二氮杂磷4经受氮的热挤出以形成烯基膦7和亚烷基膦基8 ; 这些产品的结构已通过单晶X射线结构分析确定。
• Synthesis of 5-alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes from α-silyl-α-diazoketones and phosphaalkenes
  作者：Berthold Manz、Gerhard Maas

  DOI：10.1016/0040-4020(96)00541-8

  日期：1996.7

  5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (II) arise from a [3+2] cycloaddition reaction between various, differently substituted phosphaalkenes and 2-siloxy-1-diazoalkenes that are present to a minor extent in a thermal equilibrium with α-silyl-α-diazoketones. The cycloaddition products 4a-g,6a,b,e,f, and 8 are sufficiently thermally stable to be isolated. In other cases, silyl group migration

  5亚烷基-4,5-二氢-3- ħ -1,2,4-（λ 3）-diazaphospholes（II）发生来自不同，不同取代的phosphaalkenes和之间的[3 + 2]环加成反应2甲硅烷氧基-1-在与α-甲硅烷基-α-二氮杂酮的热平衡中少量存在的重氮烯烃。环加成产物4a-g，6a，b，e，f和8具有足够的热稳定性，可以被分离。在其他情况下，甲硅烷基迁移（环-C→N或O→N）导致N-甲硅烷基-1,2,4-二氮杂磷烯异构体。
• Photochemical Isomerizations of 5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-Phosphapyrazolines): (5→4) Ring Contraction Generates Azomethineimine Dipoles
  作者：Berthold Manz、Jochen Kerth、Gerhard Maas

  DOI：10.1002/(sici)1521-3765(19980515)4:5<903::aid-chem903>3.0.co;2-j

  日期：——

  UV irradiation of the title compounds 1a-d results not in extrusion of molecular nitrogen, but in a skeletal rearrangement generating amino(imidoyl)phosphanes 2a-c from 1a-c and 2-hydrazinobenzo[b]phosphole 4 from 1d. The first step in these isomerizations is an unprecedented (5-->4) ring contraction of 1 to form the semicyclic azomethineimine dipoles 10 incorporating a 1,2,3-diazaphosphetidine ring. Dipoles 10a-c, but not 10d, can be observed by NMR spectroscopy after brief irradiation of the precursors. Furthermore, they could be trapped by [3+2] cycloaddition reaction with dimethyl acetylenedicarboxylate to give the bicyclic 1,2,3-diazaphosphetidines 12a-c, and, in the case of 10a and 10c, also the dihydrophospholes 13a,c resulting from a second [3+2] cycloaddition.