(3aR,7aR)-2-benzyl-3a,4,5,6,7,7a-hexahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide | 146098-94-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (3aR,7aR)-2-benzyl-3a,4,5,6,7,7a-hexahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide
• 英文别名: <3aR-(2α,3aα,7aβ)>-2-benzyloctahydro-1,3-dimethyl-1H-1,3,2-benzodiazaphosphole 2-oxide；(3aR,7aR)-2-benzyl-<3a,4,5,6,7,7a-octahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole>-2-oxide；(3aR,7aR)-2-Benzylhexa-3a,4,5,6,7,7a-hexahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole-2-oxide；(3aR,7aR)-2-benzyl-1,3-dimethyl-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 146098-94-4
• 化学式: C₁₅H₂₃N₂OP
• 分子量: 278.334
• InChiKey: AXPSJUZYRFQKEB-HUUCEWRRSA-N

物化性质

• 沸点：
  394.5±35.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,7aR)-2-benzyl-3a,4,5,6,7,7a-hexahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide 在 platinum(IV) oxide 盐酸 、 正丁基锂 、 2,4,6-三异丙基苯磺酰叠氮化物 、 氢气 、 potassium acetate 作用下， 反应 37.5h， 生成 (R)-1-amino-1-phenylmethylphosphonic acid
  参考文献：
  名称：

  Electrophilic Amination and Azidation of Chiral α-Alkyl Phosphonamides: Asymmetric Syntheses of α-Amino α-Alkyl Phosphonic Acids†

  摘要：

  由 N,N′-二甲基 (R,R)-1,2-二氨基环己烷衍生的手性非外消旋δ-烷基膦酰胺的立体选择性亲电胺化反应，具有中等到极好的对映选择性。产物被水解并还原成相应的δ-烷基δ-氨基膦酸。X 射线晶体结构分析证实了不对称诱导的意义。

  DOI：

  10.1055/s-1994-25679
• 作为产物：
  描述：

  (1R,2R)-1,2-diaminocyclohexane 在 sodium hydroxide 、 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 17.5h， 生成 (3aR,7aR)-2-benzyl-3a,4,5,6,7,7a-hexahydro-1,3-dimethyl-1,3,2-benzodiazaphosphole 2-oxide
  参考文献：
  名称：

  α-取代的α-甲基和α-苯基膦酸的不对称合成：手性烷基双环膦酰胺的设计，碳负离子几何形状，反应性和制备方面

  摘要：

  描述了拓扑独特和对映体纯的烷基膦酰胺的设计，制备，结构和光谱分析。在α-乙基和α-苄基膦酰胺的情况下，通过去质子化/氘代/烷基化实验，确定了仲和叔碳负离子的几何形状均为平面。这种系统的立体选择性烷基化以高收率和高非对映选择性进行。水解所得的α，α-烷基膦酰胺，得到具有高对映体纯度的相应的α，α-烷基膦酸。

  DOI：

  10.1016/0040-4020(96)00829-0

文献信息

• Studies in asymmetric olefinations — the synthesis of enantiomerically pure allylidene, alkylidene, and benzylidene cyclohexanes
  作者：Stephen Hanessian、Serge Beaudoin

  DOI：10.1016/0040-4039(93)88008-7

  日期：1992.12

  of alkyl cyclohexanones with topologically unique bicyclic phosphonamides derived from the C2 symmetrical (R,R)- and (S,S)-N,N′-dimethyl 1,2-trans-cyclohexane diamine leads to enantiomerically pure allylidene and benzylidene alkylcyclohexanes.

  用衍生自C 2对称的（R，R）-和（S，S）-N，N'-二甲基1,2-反式环己烷二胺的拓扑独特的双环膦酰胺处理烷基环己酮可产生对映体纯的亚烷基和亚苄基烷基环己烷。
• Photochemistry of axially chiral (arylmethylene)cycloalkanes: a search for suitable photoswitchable liquid crystalline materials
  作者：Robert P. Lemieux、Gary B. Schuster

  DOI：10.1021/jo00053a021

  日期：1993.1

  A series of chiral (arylmethylene)cycloalkanes was synthesized in racemic and optically active form to examine their suitability for incorporation in a liquid crystal-based optical switch. Irradiation of these compounds with UV light leads to their rapid photoracemization and, in some cases, their simultaneous destruction. The absorption spectra and circular dichroism spectra of these optically active compounds were determined. Chiral exciton coupling theory proves to be a good guide for predicting the magnitude of DELTAepsilon and glambda, (the Kuhn anisotropy factor). Addition of the optically active (arylmethylene)cycloalkanes to nematic liquid crystal materials induces cholesteric behavior. The helical twisting power (beta(M)) was determined for each compound, and a limit of 90 mum was established for the detection of a long-pitch cholesteric liquid crystal. Irradiation of the cholesteric liquid crystals formed by addition of the optically active (arylmethylene)cycloalkanes induces the transition to a compensated nematic phase that is readily sensed by optical microscopy.
• A search for photoresolvable mesogens: synthesis and properties of a series of liquid crystalline, axially chiral 1-benzylidene-4-[4'-[(p-alkylphenyl)ethynyl]phenyl]cyclohexanes
  作者：Yifan Zhang、Gary B. Schuster

  DOI：10.1021/jo00086a042

  日期：1994.4

  A series of axially chiral 1-benzylidene-4-[4'-[(p-alkylphenyl)ethynyl] phenyl]cyclohexanes was prepared in racemic form and as optically active mixtures by application of the Hanessian olefination reaction. These compounds have two spectrally overlapping groups which leads to enhanced circular dichroism. And, with appropriate substituents, they form liquid crystal phases when heated above room temperature. The photochemical and material properties of these compounds were studied to assess their suitability for formation of a chiroptical liquid crystal switch. It was found that the Kuhn anisotropy factor (g(lambda)) is too small for this application.
• Photoresolution of an Axially Chiral Bicyclo[3.2.1]octan-3-one: Phototriggers for a Liquid Crystal-Based Optical Switch
  作者：Yifan Zhang、Gary B. Schuster

  DOI：10.1021/jo00127a026

  日期：1995.11

  The axially chiral ketones 8-(phenylmethylene)bicyclo[3.2.1]octan-3-one (1) and 3-(phenylmethylene)bicyclo[3.2,1]octan-8-one (2) were prepared and investigated for suitability as a chiroptical trigger in a liquid crystal-based optical switch. Irradiation of optically active ketone 1 with unpolarized light leads to its efficient photoracemization. Its irradiation with circularly polarized light leads to partial photoresolution with an enantiomeric excess sufficient for it to function as a chiroptical trigger. However, 1 is not sufficiently soluble in ZLI-1167, a nematic liquid crystalline material, to induce a measurable pitch. Ketone 2 is unstable to irradiation and is not suitable for use as a chiroptical trigger.
• 1-Benzylidene-2,3:4,5:6,7-tribenzocyclohepta-2,4,6-trienes: synthesis and photochemistry of a series of optically active potential triggers for physical amplification of a photoresponse in liquid crystalline media
  作者：B. S. Udayakumar、Gary B. Schuster

  DOI：10.1021/jo00067a068

  日期：1993.7