[A0083]
TRIARYLAMINE-N-OXIDES. I. THE FIRST ATTEMPT OF (4,4´,4´´-TRIMETHYL)TRIPHENYLAMINE-N-OXIDE SYNTHESIS AND DIRECT PROOF OF ITS FORMATION
Vladimir N. Bulavka1, Alexandr E. Gekhman2, Konstantin K. Koshelev1
1Slavich Company, 2 Mendeleev sq.,
Pereslavl-Zalessky, Yaroslavl region, 152020, Russian Federation
E-mail: [email protected]
2N. S. Kurnakov Institute of Inorganic Chemistry RAS, 31 Leninsky Pr.,
Moscow, 117071, Russian Federation
Received: 9 August 2000 / Uploaded: 16 August
Triarylamine-N-oxides are mainly of interest to theoretical organic chemists. The first mention of triphenylamine-N-oxide (I) [1] was an erroneous one. In fact, in the original paper [2] I has not been described. In reference [3] the acetone solution of the I : UO2Cl2 1:1 complex was described without any experimental data for the above mentioned complex or for the ligand preparation. Up to the present time no synthetic procedure for triarylamine-N-oxide preparation were described. Their stability seems to be much lower than the stability of other known amine-N-oxides. In our opinion, (4,4
�,4��-trimethyl)-triphenylamine (II) forms a relatively stable (4,4�,4��-trimethyl)-triphenylamine-N-oxide (III).Earlier, III was mentioned in one patent publication (without any experimental description) together with a wide variety of all known types of amine-N-oxides as useful lubricant additives for the prevention of PH3 formation in phosphorus containing alloys [4].
Oxidation of II dissolved in benzene with a large excess of 50% aqueous hydrogen peroxide leads to the formation of III. A saturation of the reaction mixture with solid potassium chloride and extraction with ethyl acetate gives mixtures of II, III, and (4,4
�,4��-trimethyl)triphenylamine-N-chloride (IV).
II III IV
GC-MS analyses of the so obtained extracts shows a direct proof for the formation of III: 16.91 min, 96.48% II, M+ 287; 18.02 min, 1.98% III, M+ 303; 18.14 min, 1.53% IV, M+ 321 [5].
The fragmentation of III begins with loss of m/z 16 (single oxygen atom) and formation of the 287 m/z fragment. Similarly, IV initially loses a chlorine mass fragment (35 and 37 m/z) and forms the 287 m/z fragment. As 287 is the molecular mass of II, this fragmentation process confirms the chemical structures of III and IV.
The stability of II in solutions is low. The presence of II and III in solution is detectable only immediately after oxidation. After standing of the solution for 1 hour at room temperature no II and III were detected by GC-MS method.
References
1. Chemical Abstracts. 1972-1976 9th Collective Formula Index, p. 9636F. Benzeneamine, N,N-diphenyl-N-oxide [41864-95-3] 79: 35604h.
2. Doklady Acad. Sci. USSR, 1973, 209(6), 1369-1972 (Russian), (Chemical Abstracts 79: 35604h).
3. Kobets, L.V. The energetics of uranylchloride iteraction with neutral oxygen-containing bases. Koord. Khim., 1987, 13(1), 85-91 (Russian).
4. Schulz J. (Rhenus Wilhelm Reiners GmbH & Co.) Schmiermittel sowie Additiv fur die mechanische Bearbeitung eines Werkstoffes. Offen. DE 19535517 (C 10 M 133/02), 27.03.1997; 19535517.2, 25.09.1995. (Germany).
5. Mass-spectra, m/z (%):
II: 287 (100), 271 (5), 257 (1), 194 (1), 180 (10);
III: (M+1)+: 304(27), M+: 303(100), 287(6), 197 (7), 196 (4), 182 (5), 178 (9), 177 (12), 92 (3);
IV: (M+1)+: 324 (10), M+: 323 (33), (M+1)+: 322 (42), M+: 321 (100) (isotopic peaks relative intensity is in accordance with 37Cl : 35Cl =1:3 natural content), 287 (3), 286 (20), 284 (2.5), 272 (17), 271 (68), 269 (2), 254 (2.5), 194 (23), 192 (2), 191 (1.5) 178 (15), 152 (1), 135 (7), 134 (6), 63 (2).
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