二苯基氯化膦

二苯基氯化膦是一种有机磷化合物，化学式为(C6H5)2PCl，可简写为Ph2PCl。它是无色油状液体，具有大蒜气味，ppb级别的浓度即可被检测到。它容易和很多亲核试剂（如水）反应，并易被空气氧化。它在有机合成中用于引入Ph2P基团。 二苯基氯化膦在工业上可由苯和三氯化磷反应得到。反应在600 °C的高温发生，先生成苯基二氯化膦和HCl，然后二氯化物在气相经重分配反应得到二苯基氯化膦。 2 PhPCl2 → Ph2PCl + PCl3 以三苯基膦和三氯化磷的反应也能得到产物： PCl3 + 2 PPh3 → 2 Ph2PCl 二苯基氧化膦和乙酰氯在四氢呋喃中反应，也能得到二苯基氯化膦。 二苯基氯化膦遇水分解。它可以被过氧化氢氧化，生成二苯基膦酸。它可以被五氟氯化硫氧化，得到二苯基三氟化磷；它被氯氧化得到二苯基三氯化磷： Ph2PCl + Cl2 → Ph2PCl3 它和甲醇反应，生成二苯基甲氧基膦。它和2-乙炔基吡啶在三乙胺存在下、碘化亚铜催化下于甲苯中加热反应，得到2-吡啶基乙炔基二苯基膦。 二苯基氯化膦可用于合成其它膦类化合物，一种方法是使用格氏试剂： Ph2PCl + MgRX → Ph2PR + MgClX 反应中生成的膦可进一步用于杀虫剂（如苯硫磷（英语：EPN (insecticide)））、塑料稳定剂（Sandostab P-EPQ）、卤素化合物催化剂、阻燃剂（环膦酰羧酸酐）及紫外线硬化涂料体系（用于牙科材料）的合成，这使Ph2PCl成为重要的反应中间体。 二苯基氯化膦可用作二苯基膦基化合物合成的前体，它和金属钠在1,4-二氧六环中回流反应，可以制得二苯基膦基钠。 Ph2PCl + 2 Na → Ph2PNa + NaCl 它和过量的氢化铝锂反应，可以得到二苯基膦。 4 Ph2PCl + LiAlH4 → 4 Ph2PH + LiCl + AlCl3 以上两种二苯基膦化合物都可用于合成其它有机膦配体。 Arbuzov, A. Isomerization Processes of Some Phosphorous Compounds. I. Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1911. 42: 395-420. ISSN: 0372-9877. Horner, Leopold; Beck, Peter; Toscano, Vicente G. Phosphorus organic compounds. XXVIII. Diarylchlorophosphines from aryldichlorophosphines by disproportionation. Chemische Berichte, 1961. 94. 2122-2125. ISSN: 0009-2940. Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8 Svara, J.; Weferling, N.; Hofmann, T. "Phosphorus Compounds, Organic," In 'Ullmann's Encyclopedia of Industrial Chemistry, 7th ed.; Wiley-VCH: 2008; doi:10.1002/14356007.a19_545.pub2; Accessed: February 18, 2008. Zhang, Jian-Qiu; Yang, Shangdong; Han, Li-Biao. Facial conversion of secondary phosphine oxides R1R2P(O)H to chlorophosphines R1R2PCl by acetyl chloride. Tetrahedron Letters. 2020, 61 (10): 151556. ISSN 0040-4039. doi:10.1016/j.tetlet.2019.151556.  Fraser, C.J.W.; McCartney, M.E.; Sharp, D.W.A.; Winfield, J.M. Oxidative fluorination of substituted phosphines with sulphur chloride pentafluoride. Journal of Inorganic and Nuclear Chemistry. 1972, 34 (4): 1455–1456. ISSN 0022-1902. doi:10.1016/0022-1902(72)80347-6.  Bermann, Manfred; Van Wazer, John R. μ-Nitride-bis[amidodiphenylphosphorus]​(1+) chloride. Inorganic Syntheses', 1974. 15: 199-202. ISSN: 0073-8077. Błocka, Aleksandra; Woźnicki, Paweł; Stankevič, Marek; Chaładaj, Wojciech. Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides. RSC Advances. 2019, 9 (68): 40152–40167. ISSN 2046-2069. doi:10.1039/C9RA08002C.  Guo, Jiami; Mao, Chenlu; Deng, Bin; Ye, Liyi; Yin, Yingwu; Gao, Yuxing; Tu, Song. Azobisisobutyronitrile-Initiated Oxidative C–H Functionalization of Simple Alcohols with Diaryl(arylethynyl)phosphine Oxides: A Metal-Free Approach toward Hydroxymethyl Benzo[b]phosphole Oxides and 6H-Indeno[2,1-b]phosphindole 5-Oxide Derivatives. The Journal of Organic Chemistry. 2020, 85 (10): 6359–6371. ISSN 0022-3263. doi:10.1021/acs.joc.0c00118.  Roy, Jackson W; Thomson, RJ; MacKay.m.f, . The Stereochemistry of Organometallic Compounds. XXV. The Stereochemistry of Displacements of Secondary Methanesulfonate and p-Toluene-sulfonate esters by Diphenylphosphide Ions. X-ray Crystal Structure of (5α-Cholestan-3α-yl)diphenylphosphine Oxide. Australian Journal of Chemistry. 1985, 38 (1): 111–18. doi:10.1071/CH9850111.  Stepanova, Valeria A.; Dunina, Valery V.; Smoliakova, Irina P. Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide. Organometallics. 2009, 28 (22): 6546–6558. doi:10.1021/om9005615.  Xu, Qihai; Kwon, Ohyun. 1,2-Bis(diphenylphosphino)​methane. e-EROS Encyclopedia of Reagents for Organic Synthesis. pp 1-4. ISBN 978-0-470-84289-8. Kissel, Alexander A.; Mahrova, Tatyana V.; Lyubov, Dmitry M.; Cherkasov, Anton V.; Fukin, Georgy K.; Trifonov, Alexander A.; Del Rosal, Iker; Maron, Laurent. Metallacyclic yttrium alkyl and hydrido complexes: synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination. Dalton Transactions. 2015, 44 (27): 12137–12148. ISSN 1477-9226. doi:10.1039/C5DT00129C.