bis(1-methyl-propyl)-phenyl-phosphine | 7650-80-8

• 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: bis(1-methyl-propyl)-phenyl-phosphine
• 英文别名: Di-sec.-butyl-phenylphosphin；Di-sek-butyl-phenyl-phosphin；Di(butan-2-yl)-phenylphosphane
• CAS: 7650-80-8
• 化学式: C₁₄H₂₃P
• 分子量: 222.31
• InChiKey: CEVQOEXTVWAKST-UHFFFAOYSA-N

物化性质

• 沸点：
  108-109 °C(Press: 3 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  溴乙烷 、 bis(1-methyl-propyl)-phenyl-phosphine 以 苯 为溶剂， 生成 Ethyl-di-sek.-butyl-phenyl-phosphonium
  参考文献：
  名称：

  Grim,S.O. et al., Zeitschrift fur Naturforschung. Teil B. Anorganische Chemie, organische Chemie, Biochemie, Biophysik, Biologie, 1971, vol. 26b, p. 184 - 190

  摘要：

  DOI：
• 作为产物：
  描述：

  sec-BuMgBr 、 苯基二氯化磷 生成 bis(1-methyl-propyl)-phenyl-phosphine
  参考文献：
  名称：

  Group contributions to phosphorus-31 chemical shifts of tertiary phosphines

  摘要：

  DOI：

  10.1021/jo01278a059

文献信息

• 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 ylide ligands with a sulfonated group V component
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046332A2

  公开（公告）日：1982-02-24

  A process is provided for preparing nickel ylides which are themselves novel compounds 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 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 of R,, R2 and R3 is a sulfonato group or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl, as defined above, 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. The process comprises reacting a ligand defined by the following formula: with an alpha-substituted ketone or aldehyde or an alpha-substituted thioketone or thioaldehyde defined by the following formula: to obtain the metal salt defined by the following Formula II: wherein R1, R2, R3, R7, R8, F and M are as defined above and X is a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, a tosyl group (a tolune sulfonate group), or an acetate group. This metal salt is reacted with a base to obtain the novel ylide defined by the following Formula III: wherein R1, R2, R3, R7, R8, F and M are as defined above. This ylide is then reacted with (1) a zero valent nickel compound and (2) a ligand having the formula: wherein R4, R5, R6 and E are as defined above.

  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 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；卤素基，选自由氟、氯、溴和碘（最好是氯）组成的组；羟基；烷氧基或芳氧基；烃基，如上文所定义，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、芳烷基或烷芳基；条件是 R、R2 和 R3 中至少有一个是磺酸基或如上定义的带有磺酸基的烷基、芳基、 烯基、环烷基、芳烷基或烷芳基；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。该工艺包括将下式定义的配体与α-取代的酮反应： 与下式定义的α-取代酮或醛或α-取代噻酮或硫代醛反应，得到下式定义的金属盐： 得到下式 II 所定义的金属盐： 其中 R1、R2、R3、R7、R8、F 和 M 如上定义，X 是选自氟、氯、溴和碘（最好是氯和溴）、甲苯磺酰基或乙酸酯基的卤素基。这种金属盐与碱反应，可得到下式 III 所定义的新型矢量： 其中 R1、R2、R3、R7、R8、F 和 M 如上定义。然后将该锂盐与 (1) 一种零价镍化合物和 (2) 一种配体反应，配体的式为 其中 R4、R5、R6 和 E 如上定义。
• Process for the preparation of nickel ylides containing directly sulfonated ylide ligands
  申请人：GULF RESEARCH & DEVELOPMENT COMPANY

  公开号：EP0046628A2

  公开（公告）日：1982-03-03

  A process is provided for preparing nickel ylides which are themselves novel compounds defined by the following Formula I wherein Ri, R2, R3, and R7 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; R4, R5 and R6 are either alike or different members selected from the group consisting of a hydrocarbyl group as defined above, a sulfonato group (-SO3-) or a sulfonated hydrocarbyl 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. The process comprises sulfonating a metal ylide defined by the following Formula II: to obtain the sulfonated ylide defined by the following Formula III: wherein R1, R2, R3, R7, F and M are as defined above. The sulfonated ylide is reacted with a base to obtain the metal ylide defined by the following Formula IV: wherein R1, R2, R3, R7, F and M are as defined above and A is the cationic portion of the base used. This ylide is then reacted with (1) a zero valent nickel compound and (2) a ligand having the formula: wherein R4, R5, R6 and E are as defined above.

  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 Ri、R2、R3 和 R7 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；卤素基，选自由氟、氯、溴和碘（最好是氯）组成的组；羟基；烷氧基或芳氧基；以及烃基，如上文所定义，带有卤素、羟基或烷氧基或芳氧基；R4、R5 和 R6 是相同或不同的成员，选自上文定义的烃基，磺酸基（-SO3-）或 磺化烃基组成的组；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 II.定义的金属惰性金属，以获得磺化惰性金属： 得到由下式 III.定义的磺酸化醯胺 其中 R1、R2、R3、R7、F 和 M 如上定义。磺化醯胺与碱反应，得到下式 IV 所定义的金属醯胺： 其中 R1、R2、R3、R7、F 和 M 如上定义，A 为所用碱的阳离子部分。然后将这种锂与 (1) 一种零价镍化合物和 (2) 一种配体反应，配体的式为 其中 R4、R5、R6 和 E 如上定义。