二苯基氯化膦
化合物
二苯基氯化膦是一種有機磷化合物,化學式為(C6H5)2PCl,可簡寫為Ph2PCl。它是無色油狀液體,具有大蒜氣味,ppb級別的濃度即可被檢測到。它容易和很多親核試劑(如水)反應,並易被空氣氧化。它在有機合成中用於引入Ph2P基團。[3]
二苯基氯化膦 | |
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IUPAC名 Diphenylphosphinous chloride | |
別名 | 氯化二苯基膦 |
識別 | |
CAS號 | 1079-66-9 ![]() |
PubChem | 66180 |
ChemSpider | 59567 |
SMILES |
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InChI |
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InChIKey | XGRJZXREYAXTGV-UHFFFAOYAM |
性質 | |
化學式 | C12H10ClP |
摩爾質量 | 220.64 g·mol⁻¹ |
外觀 | 無色至淺黃色液體 |
密度 | 1.2295 g·cm−3(15 °C)[1] |
熔點 | 15—16 °C(288—289 K)[2] |
沸點 | 320 ˚C |
溶解性(水) | 反應 |
溶解性 | 易溶於苯、四氫呋喃、醚,和醇反應 |
危險性 | |
GHS危險性符號![]() ![]() | |
GHS提示詞 | 危險 |
H-術語 | H290, H302, H314, H318, H412 |
P-術語 | P234, P260, P264, P270, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P330 |
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。 |
合成
編輯二苯基氯化膦在工業上可由苯和三氯化磷反應得到。反應在600 °C的高溫發生,先生成苯基二氯化膦和HCl,然後二氯化物在氣相經重分配反應得到二苯基氯化膦。[3][4]
- 2 PhPCl2 → Ph2PCl + PCl3
- PCl3 + 2 PPh3 → 2 Ph2PCl
反應
編輯二苯基氯化膦遇水分解。它可以被過氧化氫氧化,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
它和甲醇反應,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、碘化亞銅催化下於甲苯中加熱反應,得到2-吡啶基乙炔基二苯基膦。[9]
用途
編輯二苯基氯化膦可用於合成其它膦類化合物,一種方法是使用格氏試劑:[4]
- Ph2PCl + MgRX → Ph2PR + MgClX
反應中生成的膦可進一步用於殺蟲劑(如苯硫磷)、塑料穩定劑(Sandostab P-EPQ)、鹵素化合物催化劑、阻燃劑(環膦酰羧酸酐)及紫外線硬化塗料體系(用於牙科材料)的合成,這使Ph2PCl成為重要的反應中間體。[3][4]
二苯基膦基化合物前體
編輯二苯基氯化膦可用作二苯基膦基化合物合成的前體,它和金屬鈉在1,4-二氧六環中回流反應,可以製得二苯基膦基鈉。[10]
- Ph2PCl + 2 Na → Ph2PNa + NaCl
- 4 Ph2PCl + LiAlH4 → 4 Ph2PH + LiCl + AlCl3
參考文獻
編輯- ^ 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.