GURCZYŃSKI, M.

POŁTOWICZ, J.

TOMASIK, P.

English

Periodica Polytechnica (Budapest University of Technology and Economics)

OXIDATION OF METHYLPYRIDINES WITH SOME ARGENTOUSCOMPOUNDS M. GURCZYNSKI, J. POLTOWICZ* and P. TOMASIK** Institute of Technology of Agricultural Production, The Hugon Kollataj Academy of Agriculture in Cracow, Department in Rzesz6w, Poland Received March 20, 1983 Presented by Prof. Dr. E. PUNGDR Summary The applicability in syntheses of the oxidation of picolines, lutidines and sym-collidine with argentous sulfate and argentous oxide was investigated. Reaction of these pyridine bases carried out in autoclaves resulted in precipitation of silver powder usually with excellent yield in every case. Methyl groups ofmethylpyridines are oxidized partly to carboxylic groups which are removed under the experimental conditions to form pyridine or lower methylpyridines, respectively. However, principally tars are formed. Introduction In our recent patents [1-3J and papers [4-6J we presented results of the reaction of copper sulfate with pyridine and its methyl homologues. In all reactions carried out at elevated temperature in steel vessels copper powder precipitates and pyridine bases undergo well defined oxidation processes. Thus pyridine, all the 3-picoline and 3,5-lutidine form corresponding I-H-pyridine-2-one-s in an assumedly intramolecular reaction of the relevant O"-coordination compounds. Methylpyridines bearing methyl groups in the IY. and/or y-positions of the pyridine ring undergo oxidation predominantly to carboxylic acids which decarboxylate under reaction conditions. this turns the overall process into a demethylation of pyridine bases. Our attempts to carry out similar oxidations of pyridine and its methyl derivatives with argentous salts [7J have revealed powdered metal silver to precipitate. The much lower selectivity of the reaction accompanied by a significantly higher yield of precipitated silver in comparison with the yield of precipitated copper in former experiments with copper sulfate allow to assume '" Institute of Catalysis, Polish Academy of Sciences, Cracow, Poland ** Department of Chemistry and Physics, The Hugon Koll~taj Academy of Agriculture, Cracow, Poland 3* 200 GURCZYNSKJ. M. et al. both a different course and mechanism of such oxidations. At the same time the applicability of the reaction with argentous compounds in syntheses attracts attention. The results of our investigation into this problem are presented in this paper. Thus, both argentous sulfate and oxide are subject to the reaction with pyridine, all three isomeric picolines, 2,3-, 2,4-, 2,6- and 3,S-lutidines and 2,4,6-collidine. Experimental A pyridine base, the argentous compound and water were heated to the elevated temperature in a 5 x 10- 2 dm3 steel autoclave with glass lining. The amounts of reagents and the reaction conditions are specified in Tables I and lI. The powder precipitated at the bottom of the autoclave was separated with a centrifuge, washed with distilled water and dried. Its identity was proven by the reaction with ammonium hydroxide followed by the oxidation with potassium chromate (positive reaction for argentous oxide and negative for metal silver). The isolation of the products of reaction of pyridine origin was carried out following the procedure described earlier [6]. Chromatographic quantitative analysis of their benzene extracts was carried out using a CHROM-5 apparatus (Czechoslovakia) with 1 x 4 X 10- 3 m TENAX GC column. The temperature was programmed (8.S x 10- 2 K/s) in the range of 403-433 K. The flow rate of nitrogen was 2.S x 10- 4 dm3/s. The lack of pyridinols and I-H -pyridones was postulated after negative reaction with ferric chloride carried out on fractions of particular reaction mixtures. Results and discussion The experiments carried out with argentous compounds have revealed essential differences in the course of the reactions in comparison with similar reactions of the bases studied with cupric sulfate. Contrary to the complex of copper sulfate with pyridine which reacted to I-H-pyridine-2-one, sulfur dioxide and copper powder, the complex of argentous sulfate with pyridine appeared to be entirely passive to both elevated temperature and pressure. These reaction conditions which are suitable for the transformation of cupric complexes with 3-picoline and 3,5-lutidine into I-H-3- and S-methylpyridine-2-one-s as well as I-H-3,S-dimethylpyridine-2-one, respectively, and copper powder caused in every case precipitation of silver powder from the relevant argentous complexes but pyridones were not formed. In the case of reactions with copper sulfate it has been found that copper powder was formed directly from the complexes and its amount was dependent Table I ReslIlts oI the Reaction (?f Pyridine Bases with Aryelllolls SlIljate Products Base Ag 2S04 , 1-1 20, Temp., Reaction g cm 3 K time, h Ag Ag20 Demethylated Compounds, Yield, % '" "/ mg /0 mg /0 2-Picoline 2 3 423 1 21 1.5 248 17.9 2 87 6.3 207 13.0 4 531 38.4 40 2.7 6 746 53.9 38 2.4 453 6 1.378 99.6 3 0.2 pyridine, 1.22% <;) ~ 0.33 3 453 8 211 92.3 9 3.3 I::> 0.03 3 453 8 20 95.7 0 0.0 :>.. ~ 0.05 10 453 8 34 99.4 0 0.0 <;) 0.025 to 453 8 15 86.7 5.2 <-: <;) ." ~ 3-Picoline 2 3 423 4 45 3.2 95 6.0 t'1 6 36 2.6 13 0.8 ~ 453 6 131 9.5 200 12.6 pyridine, 0.82~, ;::: .." ;;; 4-Picoline 2 3 453 8 1.382 99.7 5 0.3 pyridine, 0.94% t3 >: ~ 2,3-Lutidine 2 3 453 6 1.317 95.1 8 0.5 pyridine, 0.39%, 2-picoline, traces 2,4-Lutidine 2 3 423 4 146 10.6 196 12.3 453 8 1326 95.8 6 0.4 pyridine, 0.46%, 2-picoline, 0.49~~ 2,6-Lutidine 2 3 453 6 1329 96.1 55 3.7 pyridinc, 0.25%, 2-picoline, traces 3,5-Lutidine 2 3 453 6 149 10.8 224 15.1 pyftdine, 0.31 % 2,4,6-Collidine 2 3 423 4 65 4.7 168 11.3 6 227 16.4 127 8.5 453 6 1371 99.0 6 0.4 pyridinc, 0.52%, 2,4-lutidinc, O.2~%; ,--> 2 202 Base 2-Picoline 3-Picoline 4-Picoline 2,3-Lutidine 2,4-Lutidine 2,6-Lutidine 3,5-Lutidine 2,4,6-Collidine GURCZYNSKI. M. et al. Table II Reaction of Pyridine Bases with Argentous Oxidea) Metallic Silver precipitated g % 1.302 0.899 1.264 1.337 1.335 1.276 0.830 1.327 93.2 64.4 90.5 95.7 95.6 91.4 59.4 95.0 Products of demethylation, % pyridine, 0.63% pyridine, 0.41% pyridine, 0.41 % pyridine, 0.33%, 2-picoline, traces pyridine, 0.29%, 2-picoline, 0.15% pyridine, 0.18%, 2-picoline, traces pyridine, 0,31% pyridine, 0.26%, 2-picoline, 0.13%, 2,4-1utidine, 1.97%,2,6-lutidine, O. 24% .) 3 X 10- 3 kg of each pyridine base, 3 x 10- 3 dm3 of water and 1.5 x 10- 3 kg ofargentous oxide were reacted in every case at 423 K for 4 h. on the reaction time. Present studies on the behaviour of complexes with argentous sulfate show that silver powder is formed indirectly from the corresponding complexes. In the first stage of the reaction, argentous oxide precipitates which quite readily oxidizes methylpyridines. This has been also proven by the experiments run with methylpyridines and argentous oxide instead of argentous sulfate. The results of the reactions are shown in Tables I and 11. The oxidizing ability of argentous oxide depends on the pH of the medium. In acidic medium resulting from the reactions run with silver sulfate the rate of oxidation is reduced. Further differences noted between the behaviour of cupric and argentous complexes are related to the transformation of the ligands. Only minute amounts of demethylated products are formed from argentous complexes contrary to cupric complexes. Unidentified tarryproducts containing -CH=CH- bonds as proven by IR spectra (VCH=CH in the region of 1620 cm -1) are principal products. Methylpyridines exhibit evident selectivity towards oxidation with cupric ion. a-Methyl groups are most readily oxidized followed by the y- and f3-methyl groups. The yield of precipitated silver powder points to the lower selectivity of these groups toward the oxidation with argentous compounds. Simultaneously, the pathway of the oxidation favours the formation of tars. This fact can be interpreted in terms of the ability of the proton abstraction from the methyl group by argentous oxide in an intermolecular process and the addition of carbanion to pyridine aldehydes formed in parallel. Finkelstein and Elderfield [8] did not observe such reactions in the case of the oxidation of2-picoline with argentous acetate in glacial acetic acid. Pyridine, but not tars and silver powder have been the only reaction products identified, because the solvent prevented OXIDATION OF METHYLPvIiIi>JNES 203 the formation of argentous oxide in the course of the reaction. Some complications of the reactions studied in this paper could be anticipated in view of the results patented by Pearlman [9]. This author has shown that some aromatic carboxylic acids, among them both nicotinic and isonicotinic acid, are hydroxylated by argentous oxide in the positions vicinal to the carboxylic group. The latter are decarboxylated in this one-step reaction. Any possibility ofthe hydroxylation ofthe pyridine ring in the course of our experiments may be ruled out on the basis of the analysis of the IR spectra of the tarry products (lack of bands in the region of 3200-3500 cm;-l) and a negative spot test with ferric chloride for the hydroxy group. As a conclusion, the reaction under study can be solely useful for the precipitation of metal silver from aqueous solutions of its sulfate and suspensions of its oxide. References 1. TOMASIK, P.-DWORAKOWSKA, R.-WOSZCZYK, A.: Polish Pat. 94 889 (1978). 2. TOMASIK, P.-WOSZCZYK, A.: Polish Pat. 95 820 (1978). 3. TOMASIK, P.-WOSZCZYK, A.: Polish Pat. 102246 (1978). 4. WOSZCZYK, A.-ToMASIK, P.: Chem. Stosow., 22, 155 (1978). 5. TOMASIK, P.-WOSZCZYK, A.: Tetrahedron Letts., 2193 (1977). 6. TOMASIK, P.-WOSZCZYK, A.-ABRAMOVITCH, R. A.: J. Heterocycl. Chem., 16, 1283 (1979). 7. TOMASIK, P.-DWORAKOW~KA, R.-WOSZCZYK, A.: Polish Pat. 94 840 (1978). 8. FINKELSTEIN, J.-ELDERFIELD, R. c.: J. Org. Chem., 4, 365 (1939). 9. PEARLMAN, M. B.: U. S. Pat. 2,764,587 (1956). Marek GURCZYNSKI M. Sc. Cwiklinskiej Street, 2, 35959 Rzesz6w, Poland Jan POLTOWICZ M. Sc. Niezapominajek Street, 30239 Cracow, Poland Prof. Dr. habil. Piotr TOMASIK Mickiewicza Ave., 24/28, 30 059 Cracow, Poland 

OXIDATION OF METHYLPYRIDINES WITH SOME ARGENTOUS COMPOUNDS

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OXIDATION OF METHYLPYRIDINES WITH SOME ARGENTOUS COMPOUNDS

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