Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, p. 1794. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001, p. 1875.
Original Russian Text Copyright
2001 by Sharutin, Egorova, Ivanenko, Ettenko.
SHORT
COMMUNICATIONS
New Synthesis of Tetraphenylphosphonium Halides
V. V. Sharutin, I. V. Egorova, T. K. Ivanenko, and E. N. Ettenko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
e-mail: svlad@amur.ru
Received August 15, 2000
A number of methods for preparation of tetraryl-
phosphonium halides are known, the main of which
are based on the reactions of triarylphosphine and
phenyl halide in the presence of aluminum halide and
of triarylphosphine oxide with arylmagnesium halide
followed by subsequent treatment of the reaction mix-
ture with hydrohalic acid [1]. Also, the reaction of
pentaphenylphosphorane with appropriate acid should
be noted [2].
(92%), mp 262 C (published data [1]: mp 265 C; no
depression of the melting point was observed on
mixing with an authentic sample).
Tetraphenylphosphonium bromide (IIIb) was
synthesized in a similar way from compound I and
dibromotriphenylphosphorane. Yield 95%, mp 285 C
(published data [1]: mp 287 C).
REFERENCES
We have developed a new procedure for prepara-
tion of tetraphenylphosphonium halides by reaction
of pentaphenylphosphorane with dihalotriphenylphos-
phoranes. In such a way, using pentaphenylphos-
phorane (I) and dihalides IIa and IIb as starting
compounds, we have synthesized tetraphenylphospho-
nium chloride and bromide IIIa and IIIb in 92 and
95% yield, respectively:
1. Purdela, D. and Vilceanu, R., Chimia Compulsor
Organici ai Fosforului si ai Acizilor lui, Bucuresti:
Acad. Republicii Socialiste Romania, 1965. Translated
under the title Khimiya organicheskikh soedinenii
fosfora, Moscow: Khimiya, 1972, p. 239.
2. Wittig, G. and Rieber, M., Justus Liebigs Ann. Chem.,
1949, vol. 562, pp. 187 192.
3. Sharutin, V.V., Senchurin, V.S., Sharutina, O.K.,
Pakusina, A.P. and Panova, L.P., Russ. J. Gen.Chem.,
1996, vol. 66, no. 10, pp. 1710 1711.
Ph5P + Ph3PHlg2
2Ph4PHlg
4. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
Bel’skii, V.K., Russ. J. Gen. Chem., 1997, vol. 67,
no. 9, pp. 1438 1442.
5. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Bel’skii, V.K., Russ. J. Gen. Chem., 1997, vol. 67,
no. 9, pp. 1443 1448.
Hlg = Cl (a), Br (b).
The reactions were carried out by heating the
reactants in an aromatic hydrocarbon. The process
also occurs at room temperature, but at a lower rate.
6. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., and
Panova, L.P., Russ. J. Gen. Chem., 1998, vol. 68,
no. 2, pp. 318 319.
7. Sharutin, V.V., Sharutina, O.K., Egorova, I.V.,
Senchurin, V.S., Zakharova, A.N., and Bel’skii, V.K.,
Russ. J. Gen. Chem., 1999, vol. 69, no. 9, pp. 1414
1417.
8. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., Khar-
sika, A.N., Lodochnikova, O.A., Gubaidullin, A.T.,
and Litvinov, I.A., Izv. Ross. Akad. Nauk, Ser. Khim.,
1999, no. 12, pp. 2350 2354.
9. Sharutin, V.V., Sharutina, O.K., Tarasova, T.A.,
Kharsika, A.N., and Bel’skii, V.K., Russ. J. Gen.
Chem., 1999, vol. 69, no. 12, pp. 1892 1894.
The synthesis of antimony and bismuth compounds
of the general formula Ar4EX (E = Sb, Bi) by the
same procedure was reported by us in [3 9]. We have
now demonstrated that the arylation of triaryldihalo
derivatives of the 5th Group elements with their
pentaaryl compounds is also applicable to phos-
phorus(V) derivatives.
Tetraphenylphosphonium chloride (IIIa). A mix-
ture of 1 g (2.18 mmol) of pentaphenylphosphorane
cyclohexane solvate, 0.73 g (2.18 mmol) of dichloro-
diphenylphosphorane, and 15 ml of toluene was kept
for 1 h at 90 C. The solvent was distilled off, and
the residue was recrystallized from water. Yield 1.5 g
1070-4280/01/3711-1794$25.00 2001 MAIK Nauka/ Interperiodica