10,11-Dihydro-5-methyl-5H-dibenzophosphepin | 72978-05-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 10,11-Dihydro-5-methyl-5H-dibenzophosphepin
• 英文别名: 5-methyl-10,11-dihydro-5H-dibenzo[b,f]phosphepine；11-Methyl-5,6-dihydrobenzo[b][1]benzophosphepine
• CAS: 72978-05-3
• 化学式: C₁₅H₁₅P
• 分子量: 226.258
• InChiKey: DFSHLIUOEXFESU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  10,11-Dihydro-5-methyl-5H-dibenzophosphepin 在 双氧水 作用下， 以 乙醇 为溶剂， 生成 10,11-dihydro-5-methyl-5H-dibezophosphepin 5-oxide
  参考文献：
  名称：

  10,11-二氢二苯并[ b，f ]磷平体系的某些季衍生物的化学性质。碱性水解的动力学，甜菜碱的分解，以及与其他salts盐的比较

  摘要：

  10,11-二氢-5-甲基-5-苯基二苯并[ b，f ]碘化吡啶鎓（1; R = Ph）的碱性水解作用是环外苯基的裂解，其分解速度比环的快五十倍-打开，水解5，5-二甲基类似物（1； R ＝ Me）。这些七元环盐与无环盐[PMePh 3 ] [I]和[PMe 2 Ph 2的水解速率数据和活化能的比较] [I]表示存在“七元环效应”，这可能是由于中间三角-双锥体膦烷中的赤道位置环优先占据的缘故。这些七元环盐的水解过程比相关的五元环盐的水解过程进行得慢得多，这表明减轻磷烷形成时的环应变对七元环化合物的重要性不大。衍生自10，11-二氢-5-苯基二苯并[ b，f ]磷平和氧化苯乙烯的甜菜碱（9）在回流的乙醇中分解形成苯乙烯和相关的环状氧化膦（5； R = Ph）；与衍生自三苯基膦的相应甜菜碱的反应相反，没有形成重排产物。

  DOI：

  10.1039/p19790002326
• 作为产物：
  描述：

  甲基二氯膦 、 2,2'-二溴联苄 生成 10,11-Dihydro-5-methyl-5H-dibenzophosphepin
  参考文献：
  名称：

  10,11-二氢二苯并[ b，f ]磷平体系的某些季衍生物的化学性质。碱性水解的动力学，甜菜碱的分解，以及与其他salts盐的比较

  摘要：

  10,11-二氢-5-甲基-5-苯基二苯并[ b，f ]碘化吡啶鎓（1; R = Ph）的碱性水解作用是环外苯基的裂解，其分解速度比环的快五十倍-打开，水解5，5-二甲基类似物（1； R ＝ Me）。这些七元环盐与无环盐[PMePh 3 ] [I]和[PMe 2 Ph 2的水解速率数据和活化能的比较] [I]表示存在“七元环效应”，这可能是由于中间三角-双锥体膦烷中的赤道位置环优先占据的缘故。这些七元环盐的水解过程比相关的五元环盐的水解过程进行得慢得多，这表明减轻磷烷形成时的环应变对七元环化合物的重要性不大。衍生自10，11-二氢-5-苯基二苯并[ b，f ]磷平和氧化苯乙烯的甜菜碱（9）在回流的乙醇中分解形成苯乙烯和相关的环状氧化膦（5； R = Ph）；与衍生自三苯基膦的相应甜菜碱的反应相反，没有形成重排产物。

  DOI：

  10.1039/p19790002326

文献信息

• PHOSPHACYCLE-CONTAINING LIGAND FOR CHROMIUM COMPLEX AND OLEFIN OLIGOMERISATION CATALYST THEREFROM
  申请人：DOW GLOBAL TECHNOLOGIES LLC

  公开号：EP3453452A2

  公开（公告）日：2019-03-13

  The present invention relates to a composition comprising a phosphacycle-containing ligating compound represented as: wherein: P is phosphorus; X1 is phosphorus; each of R1 and R2 is independently a substituted or unsubstituted hydrocarbon derivative, a substituted or unsubstituted heterohydrocarbon derivative, or a substituted or unsubstituted heteroatom group having from one to 50 non-hydrogen atoms; m is 1; R1 and R2 are linked together to form a divalent moiety represented as which together with P forms a cyclic structure (phosphacycle) containing from 3 to 10 ring atoms; each of R3 and R4 is independently hydrogen, halogen, a substituted or unsubstituted hydrocarbon derivative, a substituted or unsubstituted heterohydrocarbon derivative, or a substituted or unsubstituted heteroatom group having from one to 50 non-hydrogen atoms; R3 and R4 are optionally linked together to form a divalent moiety represented as wherein the optional character of the linkage is depicted by a dashed connection, which together with X1 forms a cyclic structure containing from 3 to 10 ring atoms; Y is a divalent linking group [L(R5)q]p between P and X1 containing from one to 50 non-hydrogen atoms; [L(R5)q]p is represented by: wherein each L is independently selected from the group consisting of nitrogen; p is an integer number from 1 to 6; R5 is independently hydrogen, halogen, substituted or unsubstituted hydrocarbon derivative, substituted or unsubstituted heterohydrocarbon derivative, or a substituted or unsubstituted heteroatom group; q is 0, 1, or 2; provided that the [L]p subunit of the divalent linking group [L(R5)q]p does not comprise an amidine (N-C=N) group; further provided that in at least one phosphacycle of the phosphacycle-containing ligating compound, both atoms directly bonded to P or X1 are sp3 hybridized; still further provided that one or two phosphacycles comprising P, R1, and R2, or comprising X1, R3, and R4, contain no P-N, P-O, or P-S bonds within the ring part of the phosphacycle; two R5 groups attached to the same L atom may be optionally linked together to form a cyclic structure that contains from 3 to 10 ring atoms; from two to ten independently selected ligating compounds may be optionally linked together via their respective independently selected Y, R1, R2, R3, R4 or R5 groups to form a poly(ligating compound) species, and wherein the composition is not 8-aza -1-phosphatricylo[3.3.0.02,6]octane.

  本发明涉及一种组合物，该组合物包含以下列形式表示的含磷酸环的连接化合物： 其中 P为磷； X1为磷； R1和R2各自独立地为取代或未取代的烃衍生物、取代或未取代的杂烃衍生物、或取代或未取代的烃衍生物。 R1和R2各自独立地为取代或未取代的烃衍生物、取代或未取代的杂烃衍生物、或具有1至50个非氢原子的取代或未取代的杂原子基团；m为1；R1和R2连接在一起形成二价分子，表示为 R3和R4各自独立地为氢、卤素、取代或未取代的烃衍生物、取代或未取代的杂烃衍生物或具有 1 至 50 个非氢原子的取代或未取代的杂原子基团；R3和R4可选择连接在一起，形成一个二价分子，表示为 其中连接的任选特征用虚线连接表示，它与 X1 一起形成包含 3 至 10 个环原子的环状结构；Y 是 P 和 X1 之间的二价连接基团[L(R5)q]p，包含 1 至 50 个非氢原子。 Y 是 P 和 X1 之间的二价连接基团[L(R5)q]p，含有 1 至 50 个非氢原子；[L(R5)q]p 表示为 其中每个 L 独立地选自氮组成的组；p 是 1 至 6 的整数；R5 独立地是氢、卤素、取代或未取代的烃衍生物、取代或未取代的杂烃衍生物或取代或未取代的杂原子基团；q是0、1或2；条件是二价连接基团[L(R5)q]p的[L]p亚基不包括脒（N-C=N）基团；进一步条件是在含磷酸环连接化合物的至少一个磷酸环中，与P或X1直接结合的两个原子都是sp3杂化的；还需进一步说明的是，由 P、R1 和 R2 组成或由 X1、R3 和 R4 组成的一个或两个磷脂环在磷脂环的环部分内不包含 P-N、P-O 或 P-S 键；连接到同一个 L 原子上的两个 R5 基团可任选连接在一起，形成包含 3 至 10 个环原子的环状结构；两个至十个独立选择的配位化合物可通过各自独立选择的 Y、R1、R2、R3、R4 或 R5 基团有选择地连接在一起，形成多配位化合物，其中组合物不是 8-aza -1-phosphatricylo[3.3.0.02,6]辛烷。
• CHROMIUM COMPLEX WITH A PHOSPHACYCLE-CONTAINING LIGAND AND OLEFIN OLIGOMERISATION CATALYST THEREFROM
  申请人：Dow Global Technologies LLC

  公开号：EP3653299A1

  公开（公告）日：2020-05-20

  The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound.

  本发明涉及使用催化剂体系将烯烃（如乙烯）低聚为高碳烯烃（如 1-己烯和 1-辛烯的混合物）的过程，该催化剂体系包括 a) 铬源 b) 一种或多种活化剂和 c) 含磷环配位化合物。
• OLEFIN OLIGOMERIZATION PROCESS WITH A CATALYST COMPRISING A CHROMIUM COMPLEX WITH A PHOSPHACYCLE-CONTAINING LIGAND
  申请人：Dow Global Technologies LLC

  公开号：EP3653300A1

  公开（公告）日：2020-05-20

  The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound.

  本发明涉及使用催化剂体系将烯烃（如乙烯）低聚为高碳烯烃（如 1-己烯和 1-辛烯的混合物）的过程，该催化剂体系包括 a) 铬源 b) 一种或多种活化剂和 c) 含磷环配位化合物。
• CHIRAL LIGANDS
  申请人：Pfaltz Andreas

  公开号：US20110275826A1

  公开（公告）日：2011-11-10

  Chiral compounds of the formula (1), which are optically pure or highly optically enriched in which R 0 is C 1 -C 12 -alkyl which is unsubstituted or substituted by 1 to 2 C 1 -C 4 -alkoxy; cyclo-pentyl or cyclohexyl, which is unsubstituted or substituted by 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; or benzyl, phenyl or naphtyl which is unsubstituted or substituted by 1 to 3 C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -fluoroalkyl or C 1 -C 4 -fluoroalkoxy, F or Cl, or R 0 is —CR 5 R 6 OH or —CR 5 R 6 OSi(C 1 -C 8 -alkyl) 3 wherein R 5 and R 6 are independently selected from the group consisting of H, unsubstituted C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, unsubstituted C 4 -C 8 cyclo alkyl, substituted C 4 -C 8 cyclo alkyl, unsubstituted aryl, substituted aryl or wherein R 5 and R 6 can form an unsubstituted 5-6 membered aliphatic carbocycle or a substituted 5-6 membered aliphatic carbocycle, each of R 1 and R′ 1 independently is hydrogen or has the meaning of R 0 whereby R 1 , R′ 1 and R 0 can be same or different, R 2 and R 3 are independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and each of both R 4 is C 1 -C 6 -alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, or both R 4 together form an aliphatic C 4 -C 6 carbocycle. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reaction, particularly hydrogenations.
• The chemistry of some quaternary derivatives of the 10,11-dihydrodibenzo[b,f]phosphepin system. The kinetics of alkaline hydrolysis, and products of betaine collapse, and a comparison with other phosphonium salts
  作者：David W. Allen、Barrie G. Hutley、A. Christopher Oades

  DOI：10.1039/p19790002326

  日期：——

  five-membered-ring salts, indicating that relief of ring strain on phosphorane formation is of little importance for the seven-membered-ring compounds. The betaine (9) derived from 10,11-dihydro-5-phenyldibenzo[b,f]phosphepin and styrene oxide collapses in refluxing ethanol to form styrene and the related cyclic phosphine oxide (5; R = Ph); no rearrangement products are formed, in contrast to the reactions of

  10,11-二氢-5-甲基-5-苯基二苯并[ b，f ]碘化吡啶鎓（1; R = Ph）的碱性水解作用是环外苯基的裂解，其分解速度比环的快五十倍-打开，水解5，5-二甲基类似物（1； R ＝ Me）。这些七元环盐与无环盐[PMePh 3 ] [I]和[PMe 2 Ph 2的水解速率数据和活化能的比较] [I]表示存在“七元环效应”，这可能是由于中间三角-双锥体膦烷中的赤道位置环优先占据的缘故。这些七元环盐的水解过程比相关的五元环盐的水解过程进行得慢得多，这表明减轻磷烷形成时的环应变对七元环化合物的重要性不大。衍生自10，11-二氢-5-苯基二苯并[ b，f ]磷平和氧化苯乙烯的甜菜碱（9）在回流的乙醇中分解形成苯乙烯和相关的环状氧化膦（5； R = Ph）；与衍生自三苯基膦的相应甜菜碱的反应相反，没有形成重排产物。