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A Convenient, Selective Synthesis of Bis[2,4‐bis(trifluoromethyl)phenyl]phosphane Derivatives Starting from 1,3‐Bis(trifluoromethyl)benzene
Author(s) -
Hoge Berthold,
Kurscheid Boris,
Peuker Sebastian,
Tyrra Wieland,
Fischer Hendrik T. M.
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700140
Subject(s) - trifluoromethyl , chemistry , medicinal chemistry , benzene , monoclinic crystal system , yield (engineering) , triclinic crystal system , derivative (finance) , phenyl group , stereochemistry , crystal structure , crystallography , organic chemistry , halogen , materials science , metallurgy , alkyl , economics , financial economics
The reaction of the sterically shielded phosphane derivative, dichlorodiethylaminophosphane, Cl 2 PNEt 2 , with an excess of a mixture of 2,6‐bis(trifluoromethyl) and 2,4‐bis(trifluoromethyl)phenyl lithium gives bis[2,4‐bis(trifluoromethyl)phenyl]diethylaminophosphane, [2,4‐(CF 3 ) 2 C 6 H 3 ] 2 PNEt 2 , in 72 % yield as a colourless solid, while 2,6‐bis(trifluoromethyl)phenyl lithium remains unchanged in solution. The amino derivative crystallizes in the monoclinic space group P2 1 /c ( a 869.2(1), b 1857.4(1), c 1357.6(1) pm, β 100.57(4)°, Z = 4). Treatment of [2,4‐(CF 3 ) 2 C 6 H 3 ] 2 PNEt 2 in CHCl 3 solution with conc. HCl allows the synthesis of [2,4‐(CF 3 ) 2 C 6 H 3 )] 2 PCl. [2,4‐(CF 3 ) 2 C 6 H 3 ] 2 PCl reacts with H 2 O in THF solution with quantitative formation of the corresponding secondary phosphane oxide. To obtain bis[2,4‐bis(trifluoromethyl)phenyl]phosphinic acid, [2,4‐(CF 3 ) 2 C 6 H 3 ] 2 P(O)OH, quantitatively, a CHCl 3 solution of [2,4‐(CF 3 ) 2 C 6 H 3 ] 2 P(O)H, has to be stirred in an NO 2 atmosphere. The phosphinic acid crystallizes is the triclinic space group $\rm P{\bar 1}$ ( a 754.2(1), b 927.6(2), c 1305.5(2) pm, α 85.11(2)°, β 75.45(1)°, γ 79.99(2)°, Z = 2). From the reaction of the phosphinic acid with either elemental sodium or with cyanide salts, the corresponding phosphinate salts are obtained in an almost quantitatively yield.