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2,118,986 Patented May 31, 1938 UNITED STATES PATENT OFFICE 2,118,986 . SOLID DIAZO SALTS Karl Schnitzspahn and Wilhelm Koch, O?en vbach-on-the-Main, Germany, assignors to Gen eral Aniline Works, Inc., New York, N. Y., a cor poration of Delaware No Drawing. Application November 27, 1936, Se rial No. 113,083. In Germany May 21, 1932 5 Claims. (Cl. 260-69) The present invention relates to new solid diazo salts; more particularly it relates to diazo salts containing a free amino group and corre sponding probably to the general formula: mono-diazotization of the diamines, with mono diazo compounds in a stable form ready for use. These new solid diazonium salts which may be diluted with the usual admixtures and adjusted to the usual commercial form, are of especial 5 value- in the ice color industry. The following examples serve to illustrate the invention, but they are. not intended to limit it whenrein Y stands for halogen, n and p stands f or 10 one of the numbers 1 and 2, and wherein the benzene nucleus may be further substituted. This application is a continuation-in-part of our col-pending U. S. patent application Serial No. 671,590, ?led May 17, 1933 which has matured 15 into Patent 2,067,132. The diazo salts may be obtained by diazotizing unilaterally lA-diaminobenzenes, halogenated thereto, the parts being by weight: (1) 187 parts of 2-bromo-1,4-diaminobenzene 10 are diazotized in 145 parts of sulfuric acid of 78% strength and 2800 parts of water at‘ 10° C. to 15° C. with a solution of 72 parts of sodium nitrite in 300 parts of water. To the diazo solu tion, there are added 740 parts of an aqueous 15 solution of 41% strength of free 1,5-naphthalene disulfonic acid. The 1,-5-naphthalene disulfonate in the nucleus and being free from sulfonic acid or carboxylic acid groups, i. e. by treating the separates in a crystalline form and is worked said 1,4-diaminobenzenes with the quantity of good stability. mineral acid and nitrous acid, necessary for diazotizing one amino group, and by precipitat ing the diazo compounds, thus obtained, in the form of the different kinds of arylsulfonates. Morgan and Cleage (cf. “Journal of the Chem N) 01 ical Society”, 113, (1918), pages 590 and 596) have transformed 2,6-dichloro-lA-diaminoben zene in dry acetone solution into 2,6-dichloroben zene-4-diazo—1-imine by the action of nitrous anhydride. The product, thus obtained, is very unstable. It was not separated in a solid form but, after its formation, it was at once acetylated in the acetone solution and thereby identi?ed. It could not be foreseen that halogenated 1,4 ' diaminobenzenes could be transformed in a up in the usual manner. It possesses a very 20 By rep-lacing 1,5-naphthalenedisulfonic acid by 2,6-naphthalenedisulfonic acid, there is obtained in an analogous manner the corresponding 2,6 naphthalenedisulfonate. (2) 177 parts of 2,6-dichlo-ro-1,4-diaminoben 25 zene are diazotized in 270 parts of hydrochloric acid of 32.1% strength and 3500 parts of water at 10° C. to 15° C. with a solution of 72 parts of sodium nitrite in 300 parts of water. To the diazo solution, there is added a solution of 260 30 parts of the sodium salt of para-chlorobenzene sulfonic acid in 500 parts of water of about 35° C. Thereby, the diazonium-para-chlorobenzenesul fonate separates and is worked up as usual. It corresponds probably to the following formula: smooth reaction into aminodiazonium salts in the presence of mineral acid and it could, fur thermore, not be foreseen whether these mono diazo compounds could easily be precipitated and 40 whether they would be stable enough for being 35 40 used on an industrial scale as dyeing salts. As is known, it is not possible to perform the mono-diazotization of para-phenylenediamine in a technical manner. Biilow (cf. “Berichte der 45 Deutschen Chemischen Gesellschaft”, 29, (1896), page 2285) describes the unilateral diazotization of nitro-para-phenylenediamine; but it could not be concluded from this literature reference that it would be possible to transform halogenated 50 1,4-diaminobenzenes into a mono-diazo com pound. All these diazo salts possess a very good sta bility, even at higher temperatures. It is, there fore, possible to furnish the dyer, for whom it is 55 dif?cult or at least laborious to carry out the It forms a feebly brown powder. In an analogous manner, there may be pre pared, for instance, the chloro-toluene-sulfonate, the benzene-disulfonate, the chlorobenzene-di 45 sulfonate and the alpha-naphthalene-sulfonate. (3) 156.5 parts of 2-chloro-5-methyl-1,4-di aminobenzene are introduced into 1600 parts of Water and 270 parts of hydrochloric acid of 20° Bé. and mono-diazotized by adding a solu 50 tion of 71 parts of sodium nitrite in 150 parts of Water. To the diazo- solution thus obtained there is added a solution of 248 parts of 1,3-nitroben zenesodiumsulfonate in 420 parts of water. The nitrobenzene sulfonic acid mono-diazonium salt 55 2 2,118,986 separates in the form of brownish yellow crystals 1 and 2, Y stands for halogen, Z for one of the and is worked up as usual. In an analogous manner there may be sepa group consisting of hydrogen, halogen and alkyl and R means a member of the group consisting rated the monodiazonium compound of 2-chloro of radicals of the benzene and naphthalene series, being very stable and easily soluble in water. 3. The solid diazo salts corresponding to the general formula: S-methyl-1,4-diaminobenzene with para-chloro benzenesulfonic acid, 1,5-naphthalenedisulfonic acid or 2,6-naphthalene disulfonic acid. The arylsulfonic acid diazonium salts of other halogen-1,4-diaminobenzenes, such as of '210 , chloro-1,4-diaminobenzene, 2,6-dibromo-L4-di aminobenzene, 10 2,5-dichloro-1,4-diaminobenzene or 2-chloro-6-bromo-lA-diaminobenzene may be prepared in a manner analogous to that described 15 in the foregoing examples. We claim: 1. The solid diazo salts corresponding to the general formula: l’ Z 25 I wherein n and 10 stand for one of the numbers 1 and 2, Y stands for halogen, Z for one of the group consisting of hydrogen, halogen and alkyl, and R means a member of the group consisting of radicals of the benzene and naphthalene series, being very stable and easily soluble in water. 2. The solid diazo salts corresponding to the 30 general formula: Y wherein n and 1) stand for one of the numbers 1 and 2, and R means a member of the group consisting of radicals of the benzene and naph thalene series, being very stable and easily soluble in water; 4. The solid diazo salt corresponding to the formula: 20 7 Br SOaH \ HaNONr-SO: being very stable and easily soluble in water. 5. The solid diazo salt corresponding to the formula: 25 01 \ HINQNFSOBGCI 30 01 being very stable and easily soluble in water. 35 1 Z n wherein n and 11 stand for one of the numbers 35 KARL SCHNITZSPAHN. WILHELM KOCH.