二苯基氯化膦
二苯基氯化膦
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IUPAC名 Diphenylphosphinous chloride
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别名
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氯化二苯基膦
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识别
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CAS号
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1079-66-9 Y
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PubChem
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66180
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ChemSpider
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59567
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SMILES
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InChI
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- 1/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
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InChIKey
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XGRJZXREYAXTGV-UHFFFAOYAM
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性质
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化学式
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C12H10ClP
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摩尔质量
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220.64 g·mol⁻¹
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外观
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无色至浅黄色液体
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密度
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1.2295 g·cm−3(15 °C)[1]
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熔点
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15—16 °C(288—289 K)[2]
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沸点
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320 ˚C
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溶解性(水)
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反应
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溶解性
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易溶于苯、四氢呋喃、醚,和醇反应
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危险性
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GHS危险性符号
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GHS提示词
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危险
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H-术语
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H290, H302, H314, H318, H412
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P-术语
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P234, P260, P264, P270, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P330
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若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。
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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。[3][4]
- 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。[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]它被氯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膦类化合物,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)、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,它和金属钠在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
- ^ Arbuzov, A. Isomerization Processes of Some Phosphorous Compounds. I. Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1911. 42: 395-420. ISSN: 0372-9877.
- ^ 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.
- ^ 3.0 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
- ^ 4.0 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.
- ^ 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.
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