1,4-双(二氯化磷)丁烷 | 28240-71-3

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 烃类卤化物
• 分子结构分类: 有机化合物 - 有机磷化合物 - 烷基卤代膦
• 中文名称: 1,4-双(二氯化磷)丁烷
• 英文名称: 1,4-bis(dichlorophosphino)butane
• 英文别名: dichloro(4-dichlorophosphanylbutyl)phosphane
• CAS: 28240-71-3
• 化学式: C₄H₈Cl₄P₂
• 分子量: 259.867
• InChiKey: AAYRHJHQPDHSJS-UHFFFAOYSA-N

物化性质

• 沸点：
  119-123 °C(Press: 2.5 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2903199000

反应信息

• 作为反应物：
  描述：

  2-甲基噻吩 、 1,4-双(二氯化磷)丁烷 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.0h， 以72%的产率得到
  参考文献：
  名称：

  Steric and electronic factors in the promoting activity of diphosphine ligands in cyclohexene hydrocarbomethoxylation catalyzed by palladium acetate

  摘要：

  Cyclohexene hydrocarbomethoxylation catalyzed by Pd(OAc)(2)-p-toluenesulfonic acid-diphosphine systems has been investigated for a wide range of diphosphine structures and concentrations. The factors controlling the activity of the palladium-containing catalysts include the hydrocarbon moiety of the ligand and the mutual arrangement of the phosphine groups. A comparison between the promoting effects of monophosphine and diphosphine ligands has demonstrated that bridged trans-diphosphines are more efficient in kinetic and concentration terms (TOF and P/Pd ratio, respectively). In particular, the promoting activity of diphosphines is one order of magnitude higher than that of triphenylphosphine, and this effect is attained at 8-65 times lower P/Pd ratios. It is discussed how the catalytic properties of the systems depend on the chelate effect and on the geometric compatibility between the diphosphine structure and the arrangement of vacant s and d orbitals of the palladium center.

  DOI：

  10.1134/s0023158412040076
• 作为产物：
  描述：

  Diethyl Tetramethylenebis(phosphonite) 在 三氯化磷 作用下， 以 乙醚 为溶剂， 生成 1,4-双(二氯化磷)丁烷
  参考文献：
  名称：

  Sander,M., Chemische Berichte, 1962, vol. 95, p. 473 - 482

  摘要：

  DOI：

文献信息

• Preparation of polyfunctional phosphines using zinc organometallics
  作者：Falk Langer、Kurt Püntener、Rainer Stürmer、Paul Knochel

  DOI：10.1016/s0957-4166(97)00027-x

  日期：1997.3

  provides polyfunctional phosphines in good yields. Especially attractive is the hydroboration/boron-zinc exchange sequence which allows the conversion of functionalized olefins into polyfunctional phosphines in a one-pot procedure. Several new chiral phosphines have been prepared starting from readily available chiral olefins (terpenes) and their efficiency in asymmetric hydrogenation reactions has been

  功能化的二有机锌与氯二有机膦的反应以良好的产率提供了多官能的膦。硼氢化/硼锌交换序列特别吸引人，它允许一锅法将官能化的烯烃转化为多官能的膦。从容易获得的手性烯烃（萜烯）开始已经制备了几种新的手性膦，并且已经评估了它们在不对称氢化反应中的效率。
• Enantioselective catalysis, 85
  作者：Henri Brunner、Josef Fürst

  DOI：10.1016/s0040-4020(01)89367-4

  日期：1994.4

  Optically active expanded chelate phosphines were synthesised by reaction of bromotolyl, bromoxylyl and bromodiphenylmethane derivatives with 1,ω-bis(dichlorophosphino)alkanes. The bromotolyl, bromoxylyl and bromodiphenylmethane ethers were obtained from the corresponding bromo(bromomethyl)arenes and the optically active alcohol (−)-borneol.

  光学活性膨胀的螯合膦是通过溴代苄基，溴氧基和溴代二苯甲烷衍生物与1，ω-双（二氯膦基）烷烃反应合成的。从相应的溴（溴甲基）芳烃和旋光性醇（-）-冰片中获得溴代甲苯基，溴代氧基和溴代二苯基甲烷醚。
• A new method for the synthesis of dichlorophosphines
  作者：Alexander N. Tavtorkin、Sofia A. Toloraya、Eduard E. Nifant’ev、Ilya E. Nifant’ev

  DOI：10.1016/j.tetlet.2010.12.048

  日期：2011.2

  A new method for the synthesis of alkyldichlorophosphines by chlorination of alkylphosphines with phosphorus pentachloride under mild conditions is described.

  描述了一种在温和条件下用五氯化磷氯化烷基膦来合成烷基二氯膦的新方法。
• Synthesis of electron-withdrawing butane- and arene-sulfonylamino phosphines and use in rhodium-catalyzed hydroformylationDedicated to the memory of Mohammad Salman Hamdani. Sal worked in our labs at Queens College as an undergraduate student from 1998–2001, and died as part of the rescue effort at the World Trade Center in New York City, September 11, 2001.Electronic supplementary information (ESI) available: details of the syntheses, purification, and NMR and analytical data. See http://www.rsc.org/suppdata/dt/b2/b208089c/
  作者：Matthew P. Magee、Huan-Qiu Li、Oma Morgan、William H. Hersh

  DOI：10.1039/b208089c

  日期：2003.1.29

  Reaction of RSO2N(H)CH2CH2N(H)SO2R [R = Bu (1), 4-nitrobenzene (7), 1-naphthalene (9a), 2-naphthalene (9b)] with PhPCl2 or EtPCl2 gives monodentate phosphorus compounds 2 and 3 (R = Bu, PhP and EtP), and 8 (R = 4-nitrobenzene, PhP), and with Ph2PCl gives the corresponding bidentate phosphine ligands Ph2PN(SO2R)CH2CH2N(SO2R)PPh2 [R = Bu (10), 4-nitrobenzene (11), 1- and 2-naphthalene (12a,b)]; similar reactions of N,N′-(1-butanesulfonyl)-2,2′-diaminobiphenyl (4) give monodentate 5 (PhP) and 6 (EtP) and N,N′-bis(diphenylphosphino)-N,N′-(1-butanesulfonyl)-2,2′-diaminobiphenyl (16). A monodentate analogue of 10 was also prepared, Ph2PN(Et)SO2Bu (14). Diphosphorus compounds with two butanesulfonylamino groups on phosphorus were also prepared from 1 and Cl2P(CH2)nPCl2 (n = 2, 4) to give 19 and 20. Details of the 13C NMR false AA′X systems are reported for 19 and 20. Rhodium-catalyzed hydroformylation reactions were run at 60 and 80 °C, at CO/H2 pressures from 4–11 atm, and in THF, toluene, CH2Cl2, and dioxane. Results show that the highest ratios of linear (n) to branched (iso) aldehydes were obtained with arenesulfonamides (n∶iso > 10) while the bidentate alkanesulfonamide 10 gave a lower n∶iso ratio of 7.2 but the highest rate [k1 = 1.98 h−1, turnover frequency = 1130 mol aldehyde (mol Rh)−1 h−1] in THF at 80 °C. Both the rate and n∶iso ratio for 10 were found to increase with decreasing CO/H2 pressure in THF and in toluene, although the rate change was small for toluene. Both the rate and n∶iso ratio for 10 also increased in CH2Cl2, but this was found not to be due to lower CO/H2 concentrations in solution, on the basis of solubility measurements in THF and CH2Cl2.

  RSO2N(H) N(H)SO2R [R = Bu (1)、4-硝基苯 (7)、1-萘 (9a)、2-萘 (9b)]与 PhPCl2 或 EtPCl2 反应生成单齿磷化合物 2 和 3（R = Bu、PhP 和 EtP）、和 8（R = 4-硝基苯、PhP），而与 Ph2PCl 反应则可得到相应的双齿膦配体 Ph2PN(SO2R) N(SO2R)PPh2[R = Bu (10)、4-硝基苯 (11)、1-和 2-萘 (12a,b)]；N,N′-(1-丁烷磺酰基)-2,2′-二氨基联苯(4)的类似反应可得到单齿 5（PhP）和 6（EtP）以及 N,N′-双（二苯基膦）-N,N′-(1-丁烷磺酰基)-2,2′-二氨基联苯(16)。此外，还制备出了 10 的单齿类似物 Ph2PN(Et)SO2Bu (14)。由 1 和 Cl2P(CH2)nPCl2（n = 2，4）还制备出了磷上带有两个丁烷磺酰胺基团的二磷化合物，得到了 19 和 20。报告了 19 和 20 的 13C NMR 假 AA′X 系统的详细信息。铑催化的加氢甲酰化反应在 60 和 80 °C、4-11 atm 的 CO/H2 压力以及 THF、甲苯、 Cl2 和二噁烷中进行。结果表明，壬磺酰胺（n∶iso > 10）得到的线性（n）醛与支链（iso）醛的比率最高，而双叉烷磺酰胺 10 在 80 ℃ 的 THF 中得到的 n∶iso 比率较低，为 7.2，但速率最高 [k1 = 1.98 h-1，翻转频率 = 1130 摩尔醛（摩尔 Rh）-1 h-1]。在 THF 和甲苯中，10 的速率和 n∶iso 比率都随着 CO/H2 压力的降低而增加，尽管甲苯中的速率变化较小。在 Cl2 中，10 的速率和 n∶iso 比率也有所增加，但根据在 THF 和 Cl2 中的溶解度测量，发现这并不是由于溶液中 CO/H2 浓度降低所致。
• Highly Fluorous Bidentate Phosphines
  作者：George Koutsantonis、Bradley Berven

  DOI：10.1055/s-2008-1067179

  日期：2008.8

  The reaction of tetrachlorodiphosphines [Cl2P(CH2)nPCl2; n = 2-4] with fluorous aromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenol gave a series of fluorous-tagged diphosphines [(p-C6F13C6H4)2P(CH2)nP(C6H4C6F13-p)2; n = 2-4] and a new diphosphonite [(p-C6F13C6H4O)2P(CH2)3P(OC6H4C6F13-p)2]. The improved synthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involved the facile chlorination of the corresponding primary phosphine with triphosgene. Fluorinated diimines RN=C(CH3)C(CH3)=NR, where R = p-C6H4C6F13 or p-C6H4C8F17 have also been prepared, and were found to be air-stable alternatives to the highly air-sensitive phosphorus-containing ligands. All compounds were characterised by a variety of techniques including NMR, IR, MS and microanalysis. The successful reduction of the phosphine-oxides [(p-C6F13C6H4)2P(O)(CH2)nP(O)(C6H4C6F13-p)2; n = 2,3] with phenylsilane is also presented.

  四氯二膦[Cl2P(CH2)nPCl2；n = 2-4]与多氟芳香族前体 4-溴（全氟己基）苯和 4-（全氟己基）苯酚反应，得到一系列多氟标记二膦[(p-C6F13C6H4)2P( )nP(C6H4C6F13-p)2；n = 2-4] 和一种新的二膦酸盐 [(p-C6F13C6H4O)2P( )3P(OC6H4C6F13-p)2]。1,3-双（二氯膦）丙烷（dcpp）的改进合成涉及相应的伯膦与三光气的简单氯化反应。此外，还制备了氟化二亚胺 RN=C(CH3)C( )=NR，其中 R = p-C6H4C6F13 或 p-C6H4C8F17，并发现它们是对空气高度敏感的含磷配体的空气稳定替代品。通过核磁共振、红外光谱、质谱和显微分析等多种技术对所有化合物进行了表征。此外，还介绍了用苯基硅烷成功还原膦氧化物[(p-C6F13C6H4)2P(O)( )nP(O)(C6H4C6F13-p)2；n = 2,3]的过程。