United States Patent (1) 11 Patent Number: 4,594,424 Iwata et al. (45) Date of Patent: Jun. 10, 1986 54 5-MERCAPTO-1,2,3-THIADIAZOLES COMPOSTION AND PROCESS FOR FOREIGN PATENT DOCUMENTS PREPARING THE SAME 103840A 3/1984 European Pat. Off. 2601700 7/1976 Fed. Rep. of Germany ...... 548/164 75) Inventors: Fumio Iwata; Takato Nakamura; 23974 3/1978 Japan. 001 1977 1/1982 Japan ................................... 548/127 Tadakazu Sakata, all of Ube, Japan 51271 3/1984 Japan. 39884 3/1984 Japan. 73) Assignee: UBE Industries, Ltd., Ube, Japan 95282 6/1984 Japan. (21) Appl. No.: 629,360 Primary Examiner-Maurice J. Welsh Assistant Examiner-Garnette D. Draper Attorney, Agent, or Firm-Frishauf, Holtz, Goodman & 22 Filed: Jul. 10, 1984 Woodward (30) Foreign Application Priority Data 57 ABSTRACT Jul. 12, 1983 (JP) Japan ................................ 58-125592 There is disclosed a 5-mercapto-1,2,3-thiadiazoles com position comprising a 5-mercapto-1,2,3-thiadiazole 51) Int. Cl."............................................ C07D 285/06 combined with (A) one or more compounds selected 52 U.S. C. .................................................... 548/127 from the group consisting of water, an alcohol, an aro 58) Field of Search ......................................... 548/127 matic hydrocarbon and a halogenated hydrocarbon and (B) a halide of an alkali metal and process for preparing 56) References Cited the same. U.S. PATENT DOCUMENTS Said composition can remarkably reduce the explosive ness of a 5-mercapto-1,2,3-thiadiazole to make its han 4,012,382 3/1977 Bouzard et al. ..................... 548/127 dling easy and to make it usable for various applications 4,113,733 9/1978 Kruger ............ 260/306.8 with a sense of security, for example, for manufacturing 4,340,742 7/1982 Kruger ..... ... 548/127 4,380,639 4/1983 Crenshaw et al. ... 548/135 pharmaceuticals and agricultural chemicals. 4,454,336 6/1984 Curran et al. ....... ... 548/127 4,540,794 9/1985 Sakai et al. .......................... 548/127 19 Claims, No Drawings 4,594,424 . 1. 2 In the present invention, there may advantageously 5-MERCAPTO-1,2,3-THADIAZOLES be used a saturated aliphatic alcohol, preferably a lower COMPOSITION AND PROCESS FOR PREPARING alcohol having 1 to 4 carbon atoms such as methyl THE SAME alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alco hol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol This invention relates to a 5-mercapto for the alcohol in the compound of (A); a loweralkyl 1,2,3thiadiazoles composition having reduced the ex benzene such as benzene, toluene, ethylbenzene, xylene, plosiveness of 5-mercapto-1,2,3-thiadiazoles (1,2,3- mesitylene for the aromatic hydrocarbon; and methy thiadiazole-5thiols) and a process for preparing the lene chloride, chloroform, carbon tetrachloride and the Sale. O like for the halogenated hydrocarbon. The compound A 5-mercapto-1,2,3-thiadiazole is a chemical material of (A) may be used in single or in combination of two or having a wide application and has an important applica more kinds thereof. Among the compound of (A), tion as an intermediate, particularly for pharmaceuti water and/or a saturated aliphatic alcohol may espe cals, agricultural chemicals and so on. cially preferably be used. However, since a 5-mercapto-1,2,3-thiadiazole is ex 15 As the halides of an alkali metal in the compound of plosive, that there is a high possibility that it causes an (B), there may advantageously be used a chloride and a unexpected accident during manufacturing, storage and bromide such as sodium chloride, potassium chloride, transportation thereof. Hence, it is a compound accom sodium bromide and potassium bromide. The halide of panied by difficulties in the handling. Therefore, there an alkali metal may also be used in single or in combina has conventionally been a disadvantage that serious 20 tion of two or more kinds thereof, and among the halide attention should necessarily be paid in the handling of an alkali metal, sodium chloride and potassium chlo thereof and that the compound could not be used for ride may preferably be used. various applications with a sense of security. In the preparation of the 5-mercapto-1,2,3- In view of such circumstances, the present inventors thiadiazoles composition according to the present in have made extensive studies for the purpose of reducing 25 vention, a method may be used in which, a 5-mercapto remarkably the explosiveness of a 5-mercapto-1,2,3,- 1,2,3-thiadiazole is once isolated from the manufactur thiadiazole to make its handling easy and to make it ing step of the 5-mercapto-1,2,3-thiadiazole to obtain usable for various applications with a sense of security. the same followed by combining the compound of (A) As a result, the present inventors have found that the and the compound of (B); and may also be prepared by purpose can be attained by combining a 5mercapto 30 a method in which the 5-mercapto-1,2,3-thiadiazole is 1,2,3-thiadiazole with a specific compound or com not isolated from the manufacturing step followed by pounds so that it can be used without any difficulty for combining the compound of (A) and the compound of various applications, for example, for manufacturing (B). The time, means and so on for combining the com pharmaceuticals and agricultural chemicals, and have pound of (A) and the compound of (B) are not particu accomplished the present invention. 35 larly limited and the 5-mercapto-1,2,3-thiadiazoles com This invention relates to a 5-mercapto-1,2,3- position according to the present invention may be thiadiazoles composition having reduced the explosive prepared by any method. Further, the 5-mercapto-1,2,3- ness of a 5-mercapto-1,2,3-thiadiazole comprising a thiadiazole to be used for manufacturing the composi 5-mercapto-1,2,3-thiadiazole combined with (A) one or tion according to this invention may be any one pre more compounds selected from the group consisting of 40 pared by any method. water, an alcohol, an aromatic hydrocarbon and a halo As the method for preparing the 5-mercapto-1,2,3- genated hydrocarbon and (B) a halide of an alkali metal, thiadiazole to be used in the present invention, there and a process for preparing the same. may be mentioned, for example, a method in which a In the present specification, the term "5-mercapto trihaloacetaldehyde and a hydrazine are subjected to 1,2,3-thiadiazole' includes, needless to say, a 5-mercap 45 condensation reaction in a solvent, followed by the to-1,2,3-thiadiazole and its salt of an alkali metal such as reaction of the resulting reaction product with a sulfide, sodium salt, potassium salt and the like as well as its a hydrosulfide and a combination of a base and hydro hydrate and so on. gen sulfide (see Japanese Unexamined Patent Publica The amounts of the compound of (A) and the com tions No. 95282/1984 and No. 51271/1984); a method pound of (B) to be combined with the 5-mercapto-1,2,3- 50 and subsequent optional addition of a halogen to the thiadiazole may freely be varied depending upon the resulting reaction mixture (see Japanese Patent Applica purpose of use of the 5-mercapto-1,2,3-thiadiazole. tion No. 167577/1983) in which a trihaloacetaldehyde However, in order to make a composition which has and a carboalkoxyhydrazine or a dithiocarboalkoxyhy sufficiently low explosiveness for the use of many drazine are subjected to reaction in a solvent, followed chemical reactions, the content in the composition of 55 by the reaction of the resulting product with a sulfide, a the compound of (A) is typically 5 to 25% by weight, hydrosulfide and a combination of hydrogen sulfide and preferably 10 to 20% by weight, and the content of the a base (see Japanese Patent Application No. compound of (B) is 10 to 30% by weight, preferably 15 157234/1983); a method disclosed in Japanese Unexam to 25% by weight. If the contents of the compound of ined Patent Publication No. 398.84/1984; a method dis (A) and the compound of (B) are excessively high, there 60 closed in Japanese Unexamined Patent Publication No. sometimes are difficulties in using the 5-mercapto-1,2,3- 23974/1978; and a method disclosed in J. Heterocyclic thiadiazole for the same applications as mentioned Chem. 15, 1295 (1978); a method disclosed in Tetrahe above, and if the contents thereof are excessively low, dron Letters, 26, 2398(1973). the reduction of the explosiveness sometimes becomes As a concrete example for a method of manufacturing insufficient. Therefore, it is desirable that the contents 65 the 5-mercapto-1,2,3-thiadiazoles composition accord of the compound of (A) and the compound of (B) to be ing to the present invention, there may be mentioned, combined with the 5-mercapto-1,2,3-thiadiazole should for example, a method which comprises mixing a 5-mer be within the range mentioned above. capto-1,2,3-thiadiazole and a halide of an alkali metal of 4,594,424 3 4. the compound of (B), subsequently adding an excess fohydrazide, p-xylenesulfohydrazide and the like; a amount of the compound of (A), condensing the mix hydrazine compound having an alkyl sulfonyl group ture to remove the excess amount of the compound of such as methanesulfohydrazide, ethanesulfohydrazide (A) by evaporation to dryness. This method, however, and the like; and a hydrazine compound having a ni is accompanied by danger of explosion during the oper trosubstituted aryl group such as 2,4-dinitrophenylhy ation such as condensation and evaporation to dryness.