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二苯基氯化膦

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二苯基氯化膦
IUPAC名
Diphenylphosphinous chloride
別名 氯化二苯基膦
識別
CAS號 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
性質
化學式 C12H10ClP
莫耳質量 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 反應
溶解性 易溶於四氫呋喃,和反應
危險性
GHS危險性符號
《全球化學品統一分類和標籤制度》(簡稱「GHS」)中腐蝕性物質的標籤圖案《全球化學品統一分類和標籤制度》(簡稱「GHS」)中有害物質的標籤圖案
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。

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]

合成

[編輯]

二苯基氯化膦在工業上可由三氯化磷反應得到。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

三苯基膦三氯化磷的反應也能得到產物:

PCl3 + 2 PPh3 → 2 Ph2PCl

二苯基氧化膦乙醯氯四氫呋喃中反應,也能得到二苯基氯化膦。[5]

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(如苯硫磷英語EPN (insecticide))、塑料穩定劑(Sandostab P-EPQ)、鹵素化合物催化劑、阻燃劑(環膦醯羧酸酐)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

它和過量的氫化鋁鋰反應,可以得到二苯基膦[11]

4 Ph2PCl + LiAlH4 → 4 Ph2PH + LiCl + AlCl3

以上兩種二苯基膦化合物都可用於合成其它有機膦配體。[12][13]

參考文獻

[編輯]
  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.