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二苯基氯化膦

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二苯基氯化膦
IUPAC名
Diphenylphosphinous chloride
别名 氯化二苯基膦
识别
CAS号 1079-66-9  checkY
PubChem 66180
ChemSpider 59567
SMILES
 
  • ClP(c1ccccc1)c2ccccc2
InChI
 
  • 1/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
InChIKey XGRJZXREYAXTGV-UHFFFAOYAM
性质
化学式 C12H10ClP
摩尔质量 220.64 g·mol⁻¹
外观 无色至浅黄色液体
密度 1.2295 g·cm−3(15 °C)[1]
熔点 15—16 °C(288—289 K)[2]
沸点 320 ˚C
溶解性 反应
溶解性 易溶于四氢呋喃,和反应
危险性
GHS危险性符号
《全球化学品统一分类和标签制度》(简称“GHS”)中腐蚀性物质的标签图案《全球化学品统一分类和标签制度》(简称“GHS”)中有害物质的标签图案
GHS提示词 危险
H-术语 H290, H302, H314, H318, H412
P-术语 P234, P260, P264, P270, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P330
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

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。[3]

合成

二苯基氯化膦在工业上可由三氯化磷反应得到。反应在600 °C的高温发生,先生成苯基二氯化膦HCl,然后二氯化物在气相经重分配反应得到二苯基氯化膦。[3][4]

2 PhPCl2 → Ph2PCl + PCl3

三苯基膦三氯化磷的反应也能得到产物:

PCl3 + 2 PPh3 → 2 Ph2PCl

二苯基氧化膦乙酰氯四氢呋喃中反应,也能得到二苯基氯化膦。[5]

反应

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[2]它可以被五氟氯化硫氧化,得到二苯基三氟化磷;[6]它被氧化得到二苯基三氯化磷:[7]

Ph2PCl + Cl2 → Ph2PCl3

它和甲醇反应,生成二苯基甲氧基膦。[8]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。[9]

用途

二苯基氯化膦可用于合成其它类化合物,一种方法是使用格氏试剂[4]

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。[3][4]

二苯基膦基化合物前体

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1,4-二氧六环中回流反应,可以制得二苯基膦基钠。[10]

Ph2PCl + 2 Na → Ph2PNa + NaCl

它和过量的氢化铝锂反应,可以得到二苯基膦[11]

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。[12][13]

参考文献

  1. ^ Arbuzov, A. Isomerization Processes of Some Phosphorous Compounds. I. Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1911. 42: 395-420. ISSN: 0372-9877.
  2. ^ 2.0 2.1 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.
  3. ^ 3.0 3.1 3.2 Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8
  4. ^ 4.0 4.1 4.2 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.
  5. ^ 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. 
  6. ^ 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. 
  7. ^ Bermann, Manfred; Van Wazer, John R. μ-Nitride-bis[amidodiphenylphosphorus]​(1+) chloride. Inorganic Syntheses', 1974. 15: 199-202. ISSN: 0073-8077.
  8. ^ 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. 
  9. ^ 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. 
  10. ^ 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. 
  11. ^ 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. 
  12. ^ 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.
  13. ^ 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.