Picoline sulfonation

In 1965, Breslow and Chipman discovered that zinc or nickel ion complexes of (E)-2-pyridinecarbaldehyde oxime (5) are remarkably active catalyst for the hydrolysis of 8-acetoxyquinoline 5-sulfonate l2). Some years later, Sigman and Jorgensen showed that the zinc ion complex of N-(2-hydroxyethyl)ethylenediamine (3) is very active in the transesterification from p-nitrophenyl picolinate (7)13). In the latter case, noteworthy is a change of the reaction mode at the aminolysis in the absence of zinc ion to the alcoholysis in the presence of zinc ion. Thus, the zinc ion in the complex greatly enhances the nucleophilic activity of the hydroxy group of 3. In search for more powerful complexes for the release of p-nitrophenol from 7, we examined the activities of the metal ion complexes of ligand 2-72 14,15). 

Interference with T4 absorption Cholestyramine, chromium picolinate, colestipol, ciprofloxacin, proton pump inhibitors, sucralfate, sodium polystyrene sulfonate, raloxifene, sevelamer hydrochloride, aluminum hydroxide, ferrous sulfate, calcium carbonate, bran, soy, coffee. 

Sulfonation of pyridine affords the 3-sulfonic acid in 70% yield, but vigorous conditions (H2S04-S03, 230°C) and HgS04 catalyst are required (90AHC(47)310). The picolines form -sulfonic acids similarly. Sulfonation of pyridine at 360°C gives a considerable amount of the 4-sulfonic acid. Heating the 3-sulfonic acid at this temperature produces a similar result presumably, thermodynamic control takes over. 

Mixed complex formation kinetics between LnEDTA and L, where L stands for 5-sulfosalicylate [74], 8-hydroxy quinoline-5 sulfonate and picolinate [75] were studied and two pathways namely acid-dependent and acid-independent pathways have been identified. The overall reaction stoichiometry may be written as... 

The values for the rate constant 0 are nearly the same for the mixed complexes when L = picolinate, sulfosalicylate and 8-oxyquinoline-5-sulfonate indicating and hence it appears that they fit Model 1 (i.e.) Diebler-Eigen mechanism involving a dissociative pathway. This is true in the case of lighter lanthanides. In the case of heavier lanthanides,... 

For reactivity of complexes of pyridine, 2-picoline, and 2,6-lutidine with S03, see Floyd, D. M. Fritz, A. W. Pluscec, J. Weaver, E. R. Cimarusti, C. M. Monobactams. Preparation of (S)-3-Amino-2-oxoazetidine-l-sulfonic Acids from L-a-Amino-p-hydroxy Acids via Their Hydroxam-ic Esters. J. Org. Chem. 1982, 47,5160. 

Fig. 3-130. Separation of alkali metals on a surface-sulfonated polyvinyl resin. - Separator column ION 200 eluent 0.002 mol/ L picolinic acid, pH 2.0 flow rate 2.6 mL/min detection direct conductivity.

Alkyl-substituted pyridines show some peculiarities. Thus, sulfonation of 2-, 3- and 4-picoline always produces the 5-sulfonic acid ... 

In yet another useful modification of this chemistry, Squibb chemists [34] devised a method for cyclization of 3-hydroxyvaline as required for the synthesis of the orally active monosulfactam tigemonam. Cyclization of the tertiary alcohol under typically employed conditions was problematic. Mitsunobu cyclization of 44 gave lactam 45 in poor yield along with an unprecedented rearrangement product 46 [35]. Mesylation was nonselective, but 0-sulfonation with picoline S03 complex followed by base treatment afforded 45 in 58% yield after recrystallization via the intermediacy of the derived sulfate. 

Finally comments are necessary on a general feature of the polyelectrolyte catalysis. As stated in the introductory part, high molecular weight compounds are more efficient in accelerating chemical reactions under appropriate conditions. It should be noted that this statement is not always justified. For example, polyvinylpyridine is less efficient than 4-picoline in enhancing the solvolysis of dinitrophenyl acetate [62], whereas this polymer is extremely efficient compared to 4-picoline for the solvolysis of 5-nitro-4-acetoxysalicylic acid. Imidazole was 50 times more efficient than polyvinylimidazole in the formation of N-acyl compounds of p-nitrophenyl acetate in dimethylformamide [63]. In the hydrolyses of butylacetate and propyl-acetate, dodecyl benzenesulfonic acid was 6 and 3 times more eflScient than polystyrene sulfonate, respectively [64]. 

Mercapto derivatives derived from 5-amino-2-picolinic acid (X-183) and S-aminonicotinic acid (X-184) are obtained by diazotization in the presence of sulfur and sodium sulfide. The thiols can be converted to the corresponding sulfonic acids with permanganate. ... 

Polymer-supported tetrabromooxomolybdate(V) was claimed to be a heterogeneous catalyst for alcohol oxidations with TBHP . However, it seems likely that molybdenum is leached from the surface and the observed catalysis may be, at least partially, homogeneous in nature. The same applies to Cr(III) and Ce(IV) catalysts supported on a perfluorinated sulfonic acid resin (Nafion K) which catalyze the oxidation of alcohols with TBHP . Similarly, vanadium-pillared montmorillonite clay (V-PILC) ° and a zeolite-encapsulated vanadium picolinate complex were shown to catalyze... 

During preparation of polyelectrolytes from poly(4-vinyl-pyridine) (P-4-VP) and alkyl halides, some puzzling phenomena were observed by Coleman and Fuoss. These authors found quaternization of pyridine, 4-picoline and 4-isopropylpyridine with n-butyl bromide in tetramethylene sulfone followed normal second-order kinetics. Similar results were reported by Hinshelwood and coworkersfor the reaction of pyridine and alkyl halides. However, on quaternization of poly(4-vinylpyridine) under the same conditions, they observed... 

Figure 28 Electrokinetic separation of the niacin derivatives in the presence of SDS. Conditions applied voltage, 15 kV sample injection, injected by raising the positive end of the capillary about 4 cm higher than the other end capillary, a polyimide-coated fused-silica (70 cm X 50 xm i.d.) micellar solution, 0.15 M SDS in 0.02 M borate-0.01 M KOH (pH 9.1) detection wavelength, 210 nm. 1, Isonicotinic acid hydrazide 2, Nam 3, pyri-dine-3-methanol 4, 6-AN 5, MNA 6, pyridine-3-aldehyde 7, pyridine 8, 3-acetylpyri-dine 9, thionicotinamide 10, NiA 11, pyridine-3-sulfonic acid 12, P-picoline 13, nicotinic acid ethyl ester. (From Ref. 71.)...

The transformation from arenes into phenol acetates can be achieved with hypervalent iodine compounds (such as phenyliodonium acetate, PhI(OAc)2), with chromates, or under aerobic conditions. Ligands, like picolinic acids, stabilize the intermediate palladium(IV) salts. In the presence of Lewis acids or silver salts, biaryl formation takes place. The influence of different directing groups has recently been reviewed. For example, diaryl sulfones or sulfoxides having at least one heteroaryl attached can be oxidized to the corresponding aryl acetates (Scheme 5-194, Experimental Procedure below). ... 

Na-dichromate dihydrate added portionwise with stirring at 20-30° during ca. 0.5 hr. to a soln. of 3-picoline-4-sulfonic acid 1-oxide in coned. H2SO4, and allowed to react for 12 hrs. at the same temp. 3-carboxypyridine-4-sulfonic acid 1-oxide. Y 50-60%. - Direct oxidation of 3-picoline-4-sulfonic acid instead of its N-oxide gave poor results. J. Delarge, Farmaco, Ed. Sci. 22, 99 (1967). 

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