二苯基氯化膦

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
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）
熔点	15—16 °C（288—289 K）
沸点	320 ˚C
溶解性（水）	反应
溶解性	易溶于苯、四氢呋喃、醚，和醇反应
危险性
	GHS危险性符号;
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（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.

[1] Arbuzov, A. Isomerization Processes of Some Phosphorous Compounds. I. Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1911. 42: 395-420. ISSN: 0372-9877.

[Horner-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.

[Quin-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

[Svara-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.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]