P(H)(Ph)(n-decyl) | 124717-87-9

• 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: P(H)(Ph)(n-decyl)
• 英文别名: Decyl(phenyl)phosphane
• CAS: 124717-87-9
• 化学式: C₁₆H₂₇P
• 分子量: 250.364
• InChiKey: NLPOGRKLJFCDBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  CpIr(ethylene)₂ 、 P(H)(Ph)(n-decyl) 在 I₂ 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到(η-cyclopentadienyl)Ir(P(H)(Ph)(n-decyl))I2
  参考文献：
  名称：

  三氢化铱配合物的结构和光谱表征：质子-质子交换耦合的证据

  摘要：

  中性铱二氢化物 {eta}-C{sub 5}H{sub 5}Ir(L)H{sub 2} 与 HBF{sub 4} {times} Et{sub 2}O 的质子化得到阳离子三氢化物配合物形成 (({eta}-C{sub 5}H{sub 5})Ir(L)H{sub 3})BF{sub 4}（L = 各种膦和亚磷酸酯配体）。氢化物区阳离子的{sup 1}H NMR谱在低温下显示AB{sub 2}X自旋系统（X = {sup 31}P），其简化为AB{sub 2}自旋系统{sup 1}H({sup 31}P) 光谱。J{sub AB} 的值通过计算机拟合观察到的光谱得出的值非常大，范围从 61 到 1,565 Hz。通常，J{sub AB} 与配体 L 的碱度成反比。 J{sub AB} 值与温度密切相关，在 150-200 K 的温度范围内迅速增加。由于 A/B 位点交换的开始，耦合常数尚未在高于

  DOI：

  10.1021/ja00159a001

文献信息

• Phosphorus substituted metallocene compounds for olefin polymerization
  申请人：Voskoboynikov Z. Alexander

  公开号：US20050239980A1

  公开（公告）日：2005-10-27

  This invention relates to a metallocene compounds represented by formula: wherein M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide metal atom, or actinide metal atom; E is an indenyl ligand that is substituted with a PR 2 group in the two position of the indenyl ligand, where each R is, independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl substituent, and additionally, E may be substituted with 0, 1, 2, 3, 4, 5 or 6 R n where each R n is, independently, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituent, and optionally, two or more adjacent R n substituents may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent; A is a substituted or unsubstituted cyclopentadienyl ligand, a substituted or unsubstituted heterocyclopentadienyl ligand, a substituted or unsubstituted indenyl ligand, a substituted or unsubstituted heteroindenyl ligand, a substituted or unsubstituted fluorenyl ligand, a substituted or unsubstituted heterofluorenyl ligand, or other mono-anionic ligand, or A may, independently, be defined as E or as X; each X is, independently, an univalent anionic ligand, or both X are joined and bound to the metal atom to form a metallocycle ring, or both X join to form a chelating ligand, a diene ligand, or an alkylidene ligand.

  本发明涉及一种由以下公式表示的金属茂化合物：其中M是3、4、5或6族过渡金属原子、镧系金属原子或锕系金属原子；E是一个在茂环的2位被PR2基取代的茚烯配体，其中每个R都是独立的，可以是一个碳氢化合物、取代的碳氢化合物、卤代碳氢化合物或取代的卤代碳氢化合物基团，此外，E可以被0、1、2、3、4、5或6个Rn取代，其中每个Rn都是独立的，可以是一个碳氢化合物、取代的碳氢化合物、卤代碳氢化合物、取代的卤代碳氢化合物、硅基碳氢化合物、取代的硅基碳氢化合物、锗基碳氢化合物或取代的锗基碳氢化合物基团，而且，两个或更多相邻的Rn取代基团可以结合在一起形成取代或未取代的饱和、部分不饱和或芳香环或多环取代基团；A是一个取代或未取代的环戊二烯基配体、取代或未取代的杂环戊二烯基配体、取代或未取代的茚烯配体、取代或未取代的杂茚烯配体、取代或未取代的芴基配体、取代或未取代的杂芴基配体或其他单阴离子配体，或者A可以独立地被定义为E或X；每个X都是独立的一价阴离子配体，或者两个X结合并与金属原子结合形成金属环烷基，或两个X结合形成螯合配体、二烯配体或烷基亚胺配体。
• Process for the oligomerization of ethylene
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046329A1

  公开（公告）日：1982-02-24

  Ethylene is oligomerized by contacting ethylene under oligomerization conditions with a nickel ylide defined by the following Formula I: wherein R1, R2, R3, R4, R5, R6, R7 and R8 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbons atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; and a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; provided that at least one, preferably from about one to about four, of each of R1, to R8 is a sulfonato group (-SO3-) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus, arsenic or antimony, preferably phosphorus. This process is characterized by a relatively high reaction rate at low temperatures and pressures and results in the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.

  在低聚条件下，将乙烯与下式 I 所定义的镍酰亚胺接触，可使乙烯低聚： 其中 R1、R2、R3、R4、R5、R6、R7 和 R8 要么是相同的成员，要么是不同的成员，它们选自由氢、具有约 1 至约 24 个碳原子（最好是约 1 至约 10 个碳原子）的烷基、具有约 6 至约 20 个碳原子（最好是约 6 至约 10 个碳原子）的芳基组成的组；具有约 2 至约 30 个碳原子，最好是约 2 至约 20 个碳原子的烯基； 具有约 3 至约 40 个碳原子，最好是约 3 至约 30 个碳原子的环烷基； 具有约 6 至约 40 个碳原子，最好是约 6 至约 30 个碳原子的芳基和烷芳基；从氟、氯、溴和碘（最好是氯）组成的组中选出的卤素基；羟基；烷氧基或芳氧基；以及烃基，如上文所定义的，带有卤素、羟基或烷氧基或芳氧基的烃基；R1至R8中至少有一个，最好是约一个至约四个，是磺酸基（-SO3-）或带有磺酸基的烷基、芳基、烯基、环烷基、芳基或烷芳基；M是硫或氧，最好是氧；E是磷、砷、锑或氮，最好是磷；F是磷、砷或锑，最好是磷。该工艺的特点是在低温低压下反应速度相对较快，可生产出比例相对较高的理想三聚体、四聚体、五聚体和更高的烯烃产品。
• Nickel ylides
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046331A2

  公开（公告）日：1982-02-24

  A new group of nickel ylides is provided that is highly active at relatively low operating temperatures and pressures in the oligomerization of ethylene. The compounds can be defined by the following Formula I: wherein R1, R2, R3, R4, R5, R6, R7 and R8 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbons atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; and a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; provided that at least one, preferably from about one to about four, of each of R1 to R8 is a sulfonato group (-SO3-) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus, arsenic or antimony, preferably phosphorus.

  本研究提供了一组新的镍酰化物，在相对较低的工作温度和压力下，它们在乙烯的低聚过程中具有很高的活性。这些化合物可以用下式 I 来定义： 其中 R1、R2、R3、R4、R5、R6、R7 和 R8 要么是相同的成员，要么是不同的成员，它们选自氢、具有约 1 至约 24 个碳原子的烷基，最好是具有约 1 至约 10 个碳原子的烷基；具有约 6 至约 20 个碳原子的芳基，最好是具有约 6 至约 10 个碳原子的芳基；具有约 2 至约 30 个碳原子，最好是约 2 至约 20 个碳原子的烯基； 具有约 3 至约 40 个碳原子，最好是约 3 至约 30 个碳原子的环烷基； 具有约 6 至约 40 个碳原子，最好是约 6 至约 30 个碳原子的芳基和烷芳基；从氟、氯、溴和碘（最好是氯）组成的组中选出的卤素基；羟基；烷氧基或芳氧基；以及烃基，如上文所定义的，带有卤素、羟基或烷氧基或芳氧基的烃基；条件是 R1 至 R8 中至少有一个（最好是约一个至约四个）是磺酸基（-SO3-）或带有磺酸基的 烷基、芳基、烯基、环烷基、芳基或烷芳基；M 是硫或氧，最好是氧；E 是磷、砷、锑或氮，最好是磷；F 是磷、砷或锑，最好是磷。
• Process for the oligomerization of ethylene in methanol
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046328A1

  公开（公告）日：1982-02-24

  Ethylene is oligomerized by reacting ethylene in methanol under oligomerization conditions in contact with a nickel ylide defined by the following Formula I: wherein R,, R2, R3, R4, Rs, R6, R7 and Ra are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbons atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; and a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; provided that at least one, preferably from about one to about four, of each of R, to Rs is a sulfonato group (-SO3- ) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus; arsernic or antimony, preferably phosphorus. There is thus obtained a reaction product containing (A) a methanol phase having dissolved therein the nickel ylide catalyst and (B) an alpha olefin phase. These two phases are then separated from each other to recover the alpha olefin phase. The use of methanol as the solvent medium causes the reaction product to resolve itself into two phases, an upper phase containing most of the oligomer product and a lower methanol phase carrying the catalyst dissolved therein. This permits easy separation of the product from the reaction mixture and also permits effective recycle of methanol with dissolved catalyst. The product obtained contains normal alpha olefins having from about four to about 100 carbon atoms, generally from about four to about 50 carbon atoms.

  在低聚条件下，乙烯在甲醇中与由下式 I 定义的镍酰亚胺发生反应，从而使乙烯低聚： 其中 R、R2、R3、R4、Rs、R6、R7 和 Ra 是相同或不同的成员，选自氢、具有约 1 至约 24 个碳原子（最好是约 1 至约 10 个碳原子）的烷基、具有约 6 至约 20 个碳原子（最好是约 6 至约 10 个碳原子）的芳基组成的组；具有约 2 至约 30 个碳原子，最好是约 2 至约 20 个碳原子的烯基； 具有约 3 至约 40 个碳原子，最好是约 3 至约 30 个碳原子的环烷基； 具有约 6 至约 40 个碳原子，最好是约 6 至约 30 个碳原子的芳基和烷芳基；从氟、氯、溴和碘（最好是氯）组成的组中选出的卤素基；羟基；烷氧基或芳氧基；以及烃基，如上文所定义的，带有卤素、羟基或烷氧基或芳氧基的烃基；条件是 R、Rs 至 Rs 中至少有一个（最好是约一个至约四个）是磺酰基（-SO3-）或带有磺酰基的 烷基、芳基、烯基、环烷基、芳基或烷芳基；M 是硫或氧，最好是氧；E 是磷、砷、锑或氮，最好是磷；F 是磷、砷或锑，最好是磷。这样就得到了一种反应产物，其中包含（A）甲醇相（其中溶解了镍催化剂）和（B）α-烯烃相。然后将这两相分离，回收α-烯烃相。使用甲醇作为溶剂介质可使反应产物分解成两相，上相含有大部分低聚物产物，下相为甲醇相，其中溶解有催化剂。这样就可以很容易地从反应混合物中分离出产物，还可以有效地回收甲醇和溶解的催化剂。得到的产品含有碳原子数从 4 个到 100 个不等的普通α-烯烃，碳原子数一般从 4 个到 50 个不等。
• Process for the preparation of nickel ylides containing sulfonated group V ligands
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046330A2

  公开（公告）日：1982-02-24

  A process is provided for preparing nickel ylides wich are themselves novel compounds defined by the following Formula I: wherein R,, R2, R3, R4, R5, R6, R7 and R8 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbon atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; and a sulfonato group (-SO3-) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; provided that at least one sulfonato group is located in R4, Rs and R. and at least one of R4, Rs and R6 is aryl; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus, arsenic or antimony, preferably phosphorus. The process comprises sulfonating a ligand defined by the following formula: and then reacting the resulting sulfonated ligand with (1) a zero valent nickel compound and (2) a ylide defined by the following formula: wherein R1, R2, R3, R4, R5, R6, R7, R8, E, F and M are as defined above, provided that at least one of R4, R5 and R6 is an aryl group.

  本发明提供了一种制备镍酰化物的工艺，镍酰化物本身是由下式 I 定义的新型化合物： 其中 R、R2、R3、R4、R5、R6、R7 和 R8 要么是相同的成员，要么是不同的成员，它们选自由氢、具有约 1 至约 24 个碳原子，最好是约 1 至约 10 个碳原子的烷基；具有约 6 至约 20 个碳原子，最好是约 6 至约 10 个碳原子的芳基；具有约 2 至约 30 个碳原子，最好是约 2 至约 20 个碳原子的烯基；具有约 3 至约 40 个碳原子，最好是约 3 至约 30 个碳原子的环烷基；具有约 6 至约 40 个碳原子（最好是约 6 至约 30 个碳原子）的芳基和烷芳基； 选自氟、氯、溴和碘（最好是氯）组成的组的卤素基；羟基；烷氧基或芳氧基；烃基，如上文定义的烃基，带有卤素、羟基或烷氧基或芳氧基；以及磺酸基（-SO3-）或带有磺酸基的烷基、芳基、烯基、环烷基、芳基或烷芳基；条件是至少一个磺酸基位于 R4、Rs 和 R.M是硫或氧，最好是氧；E是磷、砷、锑或氮，最好是磷；F是磷、砷或锑，最好是磷。该工艺包括磺化下式定义的配体： 然后将得到的磺化配体与(1)零价镍化合物和(2)下式定义的酰亚胺反应： 其中 R1、R2、R3、R4、R5、R6、R7、R8、E、F 和 M 如上定义，条件是 R4、R5 和 R6 中至少有一个是芳基。