chlorodi(thiophen-2-yl)phosphine | 95581-96-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: chlorodi(thiophen-2-yl)phosphine
• 英文别名: bis(2-thienyl)chlorophosphine；(2-thienyl)2PCl；bis(thien-2-yl)chlorophosphine；InChI=1/C8H6ClPS2/c9-10(7-3-1-5-11-7)8-4-2-6-12-8/h1-6；chloro(dithiophen-2-yl)phosphane
• CAS: 95581-96-7
• 化学式: C₈H₆ClPS₂
• 分子量: 232.694
• InChiKey: SYATVCDGEQMJHG-UHFFFAOYSA-N

物化性质

• 沸点：
  336.7±17.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  chlorodi(thiophen-2-yl)phosphine 在 silver tetrafluoroborate 、 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 、 二氯甲烷-D2 为溶剂， 反应 5.51h， 生成
  参考文献：
  名称：

  Heterocycle-Substituted Phosphinesulfonato Palladium(II) Complexes for Insertion Copolymerization of Methyl Acrylate

  摘要：

  A family of heterocycle-substituted binuclear phosphinesulfonato Pd(II) complexes {[R2P(C6H4SO2O)]PdMeClLi(dmso)}(2) (1a-d-LiCl-dmso: 1a-LiCl-dmso, R = 2-furyl; 1b-LiCl-dmso, R = 2-thienyl; 1c-LiCl-dmso, R = 2-(N-methyl)pyrrolyl; 1d-LiCl-dmso, R = 2-benzofuryl) was synthesized, and the solid-state structures of 1a-c-LiCl-dmso were determined, which revealed various modes of bridging between the two metal fragments. 1a-d-LiCl-dmso further generated either the mononuclear Pd(II) complexes{[kappa P-2,O-R2P(C6H4SO2O)]PdMe(pyr)} (1a-d-pyr) by addition of pyridine or the more labile mononuclear Pd(II) complex {[kappa P-2,O-(2-thienyl)(2)-P(C6H4SO2O)]PdMe(dmso)} (1b-dmso) by chloride abstraction with AgBF4. Stoichiometric methyl acrylate (MA) insertion experiments indicated that, in comparison with the other three substituents, the thienyl-substituted Pd(II) complexes undergo faster insertion of MA in a primary 2,1-fashion, and lb-dmso possesses the fastest insertion rate due to the relative weakly coordinating dmso molecule. All palladium complexes were employed in ethylene polymerization, affording highly linear polyethylene with relatively low molecular weights (M-n = (0.5-7.4) x 10(3)). In addition, under these pressure reactor conditions, the thienyl motif displays the highest activity (order: 1b-dmso > 1b-pyr > 1a-pyr > 1d-pyr > 1c-pyr >> 1a-d-LiCl-dmso). Copolymerization reactions of ethylene and MA further revealed that MA incorporation in the obtained linear copolymers depends moderately on the heterocyclic substituents.

  DOI：

  10.1021/om500400a
• 作为产物：
  描述：

  N-dithiophen-2-ylphosphanyl-N-ethylethanamine 在 盐酸 作用下， 以 正戊烷 为溶剂， 以98%的产率得到chlorodi(thiophen-2-yl)phosphine
  参考文献：
  名称：

  Bis-2-thienyldiethylaminophosphane as a Ligand in Late Transition Metal Complexes and its Transformation to Bis-2-thienylphosphane

  摘要：

  摘要 引入双-2-噻吩基二乙基氨基膦烷 (C4H3S)2PNEt2 (1) 作为后期过渡金属配合物 ([(H3C4S)2PNEt2]nMXmLp)的配体，其中 M = Ni(II)、Au(I)、Cu(I)、Pd(II)、Ir(I)，X = Cl、Br 和 L = NCMe、COD (2-7)。1 与后期过渡金属盐 NiCl2-dme、(Me2S)AuCl、CuCl、PdCl2(PhCN)2 和 [Ir(COD)Cl]2 反应生成络合物 [{(H3C4S)2PNEt2}2 - NiCl2] (2)、(H3C4S)2PNEt2-AuCl](3)、[(H3C4S)2PNEt2-CuCl(CH3CN)]2 (4)、[{(H3C4S)2PNEt2}2 - PdCl2] (5)、[{(H3C4S)2PNEt2}2-PdCl2]2 (6) 和 [(H3C4S)2PNEt2-IrCl(COD)](7)。此外，还报道了将 1 转化为有价值的氯取代起始材料 (H3C4S)2PCl (8) 以及将 8 转化为仲磷烷 (H3C4S)2PH (9) 的相关过程。复合物 2-7 在惰性气体条件下非常稳定，并通过单晶 X 射线研究、核磁共振光谱和元素分析进行了表征。

  DOI：

  10.5560/znb.2014-4138

文献信息

• Visible-Light-Driven Selective Alkenyl C–P Bond Cleavage of Allenylphosphine Oxides
  作者：Kai Wei、Kai Luo、Fang Liu、Lei Wu、Li-Zhu Wu

  DOI：10.1021/acs.orglett.9b00071

  日期：2019.4.5

  irradiation, was developed. This novel protocol involves a highly regioselective radical pathway initiated by singlet oxygen, affording diverse alkynyl phosphinates with good-to-excellent yields. Mechanistic studies and density functional theory calculations suggested an intramolecular process involving phosphorus migration, instead of phosphorus radical formation, at the early stage of the reaction

  开发了一种有效的方法，该方法可通过有机染料和可见光照射实现高选择性烯基C-P键裂解。该新方案涉及由单线态氧引发的高度区域选择性自由基途径，可提供具有良好至优异收率的多种炔基次膦酸酯。机理研究和密度泛函理论计算表明，在反应的早期，涉及磷迁移而不是磷自由基形成的分子内过程。
• Reactivity of Germylene toward Phosphorus-Containing Compounds: Nucleophilic Addition and Tautomerism
  作者：Yile Wu、Liu Leo Liu、Jue Su、Kaili Yan、Tao Wang、Jun Zhu、Xiang Gao、Yuxing Gao、Yufen Zhao

  DOI：10.1021/acs.inorgchem.5b00205

  日期：2015.5.4

  A series of phosphorus-substituted germanium(II) complexes, L1GeR [L1 = CH(CMe)(2,6-iPr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (OnBu)2; 6a, R = OP(S)Ph2; 6b, R = OP(S)(OEt)2], were synthesized through the direct activation of various organic phosphorus compounds by N-heterocyclic ylide-like germylene 1. These compounds were characterized by IR and NMR spectroscopy, and

  一系列磷取代的锗（II）配合物，L 1 GeR [L 1 = CH （CMe）（2,6- i Pr 2 C 6 H 3 N）} 2；2，R = PPh 2 ; 4，R = OPPh 2 ; 5a，R ＝ OP（O）Ph 2；5b，R ＝ OP（O）（O n Bu）2；6a，R ＝ OP（S）Ph 2；R ＝ OP（S）Ph 2。6b，R = OP（S）（OEt）2]，是通过N-杂环叶立德样的亚二甲基亚砜1直接活化各种有机磷化合物而合成的。通过IR和NMR光谱，以及这些化合物进行了表征4，图5a，图6a和6b中，用X射线晶体学进一步研究。有趣的是，1与Ph 2 P（O）H的反应生成的是三配位磷（III）物种L 1 GeOPPh 2（4），而不是预期的异构体产物L 1 GeP（O）Ph 2。反应1用二烷基硫代磷酸和二苯基硫代次膦酸生成的产物6a和6b含有P═S双键而不是P═O双键。
• Ethylene Tetramerization:  A New Route to Produce 1-Octene in Exceptionally High Selectivities
  作者：Annette Bollmann、Kevin Blann、John T. Dixon、Fiona M. Hess、Esna Killian、Hulisani Maumela、David S. McGuinness、David H. Morgan、Arno Neveling、Stefanus Otto、Matthew Overett、Alexandra M. Z. Slawin、Peter Wasserscheid、Sven Kuhlmann

  DOI：10.1021/ja045602n

  日期：2004.11.1

  producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene

  线性 α-烯烃，例如 1-己烯和 1-辛烯，是线性低密度聚乙烯 (LLDPE) 生产中的重要共聚单体。生产 1-己烯和 1-辛烯的传统方法是通过乙烯的低聚反应，这会产生广泛的线性 α-烯烃 (LAO)。虽然存在多种通过乙烯三聚生产 1-己烯的方法，但迄今为止，选择性生产 1-辛烯的类似途径一直难以捉摸。我们现在首次报道了一种前所未有的乙烯四聚反应，该反应使用铝氧烷活化的铬/((R2)2P)2NR1 催化剂体系，以超过 70% 的选择性生产 1-辛烯。
• PHOSPHACYCLE COMPOUND AND PROCESS FOR PRODUCTION THEREOF
  申请人：Dow Global Technologies LLC

  公开号：US20180291048A1

  公开（公告）日：2018-10-11

  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. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

  该发明涉及将烯烃（如乙烯）寡聚化为更高级别的烯烃（如1-己烯和1-辛烯）的方法，使用包括a）铬源b）一个或多个活化剂和c）含有膦环结构的配位化合物的催化剂体系。此外，该发明还涉及一种含有膦环结构的配位化合物和制备该化合物的方法。
• (R)- and (S)-6,6′-dimethyl- and 6,6′-dimethoxy-2,2′-diiodo-1,1′-biphenyls: Versatile intermediates for the synthesis of atropisomeric diphosphine ligands
  作者：Marco Cereghetti、Wolf Arnold、Emil A. Broger、Alain Rageot

  DOI：10.1016/0040-4039(96)01090-8

  日期：1996.7

  Starting from enantiomerically pure 6,6′-dimethyl- or 6,6′-dimethoxy-2,2′-diiodo-1,1′-biphenyls (1a or 1b) a variety of atropisomeric diphosphine ligands of defined axial chirality are directly accessible in good yields: asymmetric diphosphines of type B and the corresponding diphosphines with one (type C) or two (type D) stereogenic phosphorus atoms. Pitfalls of the lithiation/phosphination reaction

  从对映体纯的6,6'-二甲基或6,6'-二甲氧基-2,2'-diiodo-1,1'-联苯（1a或1b）开始，可以直接获得各种具有轴向手性的阻转异构二膦配体收率高：B型不对称二膦和具有一个（C型）或两个（D型）立体磷原子的相应二膦。讨论了锂化/磷化反应的陷阱。通过热差向异构可以减少P-手性非对映异构体的数量。

表征谱图