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United States Patent 19 (1) 3,759,932 Gavin Et Al

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United States Patent 19 (1) 3,759,932 Gavin Et Al United States Patent 19 (1) 3,759,932 Gavin et al. 45 Sept. 18, 1973 54 METHOD FOR PREPARING 58 Field of Search.............................. 260/294.8 G MERCAPTOPYRIDNES USING ALKALI METAL POLYSULFIDES (56) References Cited UNITED STATES PATENTS 75 Inventors: David F. Gavin, Cheshire; Maurice A. Raymond, Northford, both of 1,753,658 4/1930 Kochendoerfer............ 260/294.8 G Conn. OTHER PUBLICATIONS 73 Assignee: Olin Corporation, New Haven, Jones, J. Chem. Soc., London, Pages 3610-13, 1958 Conn. Primary Examiner-Alan L. Rotman 22 Filed: Aug. 25, 1972 Attorney-Eugene Zagarella, Jr. et al. 21 Appl. No.: 283,862 57 ABSTRACT Related U.S. Application Data This invention relates to an improved and economical 63 Continuation-in-part of Ser. No. 33,517, April 30, method for preparing mercaptopyridines by reaction of 1970, abandoned. selected halosubstituted pyridines with an alkali metal polysulfide. 52) U.S. Cl........................... 260/294.8 G, 424/263 51 Int. Cl............................................. C07d 31150 13 Claims, No Drawings 3,759,932 2 METHOD FOR PREPARING MERCAPTOPYRONES USNG ALKAL METAL This result, wherein high yields are obtained, is espe POLYSULFDES cially surprising since an attempt to prepare mercap topyridine using sodium sulfide (NaS9HO) resulted This application is a continuation-in-part of copend in only trace amounts of the desired product (See Ex ing application Ser. No. 33,517, filed Apr. 30, 1970, ample VII). now abandoned. The alkali metal polysulfide solution used in the This invention relates to an improved, economical method of this invention may generally be obtained by method for the preparation of mercaptopyridines in ex combining desired amounts of alkali metal sulfide and ceptionally high yields. More particularly this invention O sulfur in solution and the formulation of the polysulfide relates to the reaction of selected halosubstituted pyri will vary depending on such amounts. Additional dines with an alkali metal polysulfide followed by acidi meethods for obtaining the desired alkali metal polysul fication, digestion and neutralization to form the re fides are disclosed in “Polysulfide Polymers' by E. M. spective mercapto compounds. Fettes and J. S. Jorczak in J.Industrial and Engineering The compounds prepared by the method of this in 15 Chem., Vol. 42, 1950, pp. 2217-2218. vention and derivatives thereof, are well known for It is further noted that the extremely valuable dithi their utility as fungicides and bactericides as for exam opyridine derivatives, which have several well-known ple, shown in U.S. Pat. No. 2,686,786 (Tables I and II); uses, can be formed directly from the resulting mercap as a preservative in a wide variety of products as for ex topyridine product by the well-known step of oxidizing ample, shown in U.S. Pat. No. 2,742,393 and U.S. Pat. 20 said mercaptopyridine compound as shown in U.S. Pat. No. 3,236,733 discloses various metal salts of pyridine No. 2,742,476. It is further noted that this preparation thiones used in detergent compositions and in hair may be formed in situ without isolating the mercap shampoo for combatting dandruff. Similar properties topyridine compound. are shown for the dithio derivatives of mercaptopyri The starting materials suitable for use in this inven dine as shown for example in U.S. Pat. No. 2,742,476. 25 tion are any of the substituted aza-aromatic compounds Previous methods for preparing mercaptopyridines and more particularly, the substituted pyridines of the include: 1) the reaction of 2-chloropyridine with thio formula: R urea in ethanol to produce 2-mercaptopyridine (R. A. N Jones, J.Chem.Soc. 1958, 3610); 2) reaction of 2 chloropyridine with sodium hydrosulfide in propylene 30 Xin glycol to produce 2-mercaptopyridine (Bernard Miller, NN/ J.Am...Chem...Soc. 84, 403, 1962); 3) reaction of 4 (I) pyridylpyridinium chloride with HS to produce 4 where each X is an independently selected halogen mercaptopyridine; and 4) reaction of the N-oxide of group e.g., chlorine, bromine, fluorine and iodine, pref halopyridine with an alkali metal sulfide or hydrosul 35 erably chlorine, bromine and iodine; R is hydrogen, fide (U.S. Pat. No. 2,686,786). U.S. Pat. No. 1,753,658 alkyl and more particularly lower alkyl of 1 to 4 carbon broadly discloses the preparation of mercaptopyridine atoms e.g., methyl, propyl and butyl, or amino and compounds using metal sulfides such as potassium hy preferably hydrogen; and m is an integer of 1 to 5. The drogen sulfide in a manner shown in U.S. Pat. No. N-oxides and the acid salts of any of the above com 2,686,786 noted previously. While the patent does 40 pounds may also be used as starting materials. Addi broadly indicate that the disulfide may be used, there tionally compounds of the above formula (I) contain is no suggestion of using polysulfides as defined herein ing more than one of the noted substituents as well as particularly the preferred embodiments. More signifi other substituents such as phenyl, nitro and alkoxy cantly, there is no teaching of how the disulfide may be groups may also be used. Reference to the substituted used in this reaction and clearly there is no suggestion 45 pyridines (I) in the specification and claims is intended of the technique as disclosed in this application to include compounds containing such substituents as wherein following reaction, the mixture is acidified, di well as the N-oxides and acid salts thereof. It is further gested and neutralized. noted that while more than one halogen group may be The above methods are considered economically un used and while such halogens may be attached to any attractive because generally they do not result in very 50 position on the pyridine ring, it is preferable that such high yields of pure product and additionally often in halogens be attached at the 2, 4 and 6 positions since volve detailed and expensive work-up and recovery op better yields and faster reaction rates generally result erations. when using such positions. Now it has been found that selected substituted de Illustrative of the starting materials of formula (I) are rivatives of mercaptopyridine can be conveniently and 55 the following: 2-chloropyridine, 2-bromopyridine, 2 economically provided in exceptionally high yield in an iodopyridine, 4-chloropyridine, 2-chloro-3-picoline, integrated process by reacting select halosubstituted 3-fluoro-4-picoline, 2-chloro-3-ethylpyridine, pyridines with an alkali metal polysulfide and then 2-chloro-4-propylpyridine, 6-chloro-2- acidifying, digesting and neutralizing as shown by the isobutylpyridine, 2-bromo-3-picoline, 2-bromo-4- following equation wherein for example, 2 60 ethylpyridine, 2-bromo-4-propylpyridine, 6-bromo-2- chloropyridine is reacted with sodium polysulfide: propylpyridine, 2-chloro-3-aminopyridine, 2-chloro-5- H2O -- Na2S -- xS --> Vé-Cl 3,759,932 3 4. aminopyridine, 2-amino-5-bromopyridine, 2-amino-5- lar conditions of the system being utilized. Generally iodopyridine, 2,3-dichloropyridine, 2,4- the reaction time will vary from 1 to 30 hours depend dichloropyridine, 2,5-dichloropyridine, 2,5- ing on temperature and autogenous pressure condi dibromopyridine, 2,5-diiodopyridine, 2-bromo-5- tions. chloropyridine, 2,6-difluoropyridine, 2,3,5- During acidification, H.S gas is evolved and sulfur is tribromopyridine, 2,3,4,5-tetrachloropyridine, penta precipitated and recovered. The acidifying agent may chloropyridine and pentabromopyridine. Further illus be any suitable acid such as the non-oxidizing mineral trations of compounds having the above designated for acids, e.g., HCl and HSO and non-oxidizing organic mula are disclosed in “The Chemistry of Heterocyclic acids and the amount used must be at least sufficient to Compounds,' edited by Arnold Weissberger, Part 2, 10 adjust the pH of the reaction mixture below the isoelec Chapter VI, Halopyridines, Holly E. Mertel and Chap tric point and preferably below 1.0. ter IV, Pyridine-N-Oxides, Elliot N. Shaw, 1961, Inter The digestion step which follows acidification is es science Publishers, N.Y. sential in that the pyridine polysulfides and/or polyhy The polysulfides which may be used in the method of drosulfides are broken down with the formation of the this invention are any of the alkali metal polysulfides 15 acid salt of mercaptopyridine and the precipitation of and more particularly alkali metal polysulfides of the sulfur. This step may be carried out at temperatures of formula: from about ambient to the reflux temperature with the MS, wherein M is an alkali metal and more particu preferred range being 60' to 70° C. and the time will larly sodium, potassium and lithium, preferably sodium vary widely and digestion will generally be continued and potassium and more preferably sodium and x is an until sulfur is no longer precipitated. The importance average number of from about 2 to about 8, preferably of this step cannot be overlooked because when com from about 3 to about 8 and more preferably from parative experiments were run, a significant decrease in about 4 to about 8. It is noted that although the polysul yield was noted when the digestion step was not uti fides of this formula wherein x is about 2 may be used, lized. surprisingly high yields resulted when using the pre 25 Following acidification and digestion, the pH of the ferred amounts wherein x is from about 3 to about 8 or solution is then adjusted to about the isoelectric point from about 4 to about 8. with the addition of any suitable base to neutralize the The polysulfides of this invention may be prepared in acid salt of the mercaptopyridine thereby liberating various ways as noted previously on pages 3 and 4.
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