DE611398C - Process for the production of solid diazonium sulfates - Google Patents

Description

Process for the production of solid diazonium sulfates It has been found that an advantageous process for the preparation of solid diazonium sulfates is the one mixtures of acid sulfates diazotizable aromatic amines with water-binding Metal sulfates in organic, hydroxyl-free liquids that do not mix with water are miscible and in which the diazonium sulfates in question are sparingly soluble, diazotized with nitrous acid or its derivatives suitable for diazotization and the resulting mixtures of metal sulfates and diazonium sulfates from the liquid separates. These diazonium sulfates can be added to commercially available diazo salt preparations for Dyeing purposes are processed.

It is known e.g. B. by French patent 7: 27: 293, Salts of aromatic amines in solution or suspension of hydroxyl-free organic Diazotize liquids. Here the products fall when using such hydroxyl-free organic liquids that are immiscible with water, easily greasy, stick to the walls of the vessel and are difficult to handle, so that this method of working with the properties of solid diazo salts on a larger scale can hardly be carried out. The greasy texture in which the diazonium sulfates fail in this known procedure, also causes slightly undiazotized Sulphate of the base in question surrounded by the greasy diazonium sulphate and the Diazotization is withdrawn, so that then an inadequate yield of diazonium salt and a product is obtained which consists of significant amounts of insoluble components from non-diazotized amine or from diazoamino bodies, contains and therefore colored is inferior.

The present process used as a starting material for diazotization aromatic amines in organic liquids that are immiscible with water, Mixtures of the acid sulphates of the amines with a water-binding metal sulphate, the sulfates of the amines and their mixture with metal sulfates also in the relevant organic liquid made from aromatic amine, sulfuric acid and: metal sulfate can be avoided by adding water-binding metal sulfates great disadvantage of the greasy precipitation of the diazonium sulfates and achieved in the Usually better yields of more soluble diazonium salts than the known processes.

The new way of working is based on the knowledge that becoming greasy the diazonium sulfate deposits and the associated disadvantages of the known The process is effected by the water formed during the reaction. According to the general equation according to which, for example, an alkyl nitrite is used as a nitrous acid derivative and in which R is a monovalent aromatic Radical, Me. A metal, x is the number i or 2 and y is a number less than the number of water molecules bound in the fully crystalline water-containing metal sulfate, mean. RNH.,. H2 S 04 -j- Alkyl # N 02 -J- Met S 04. y H2 0 - RN2. S O4 H -f- Alkyl # O H -E- Mex S O4 # yH2 0 + x H2 0 is the water-binding metal sulfate involved in the overall reaction and binds that to the greasy nature of the after Diazonium sulfates causing water that can be produced by the known processes.

As water-binding metal sulfates, for. B. in whole or in part dehydrated sodium, magnesium, zinc or aluminum sulfate or alum with advantage be used.

The diazotization can be carried out by nitrous acid and all of its for diazotization suitable derivatives, such as aashydride, ester, nitrosyl chloride or nitrosyl sulfuric acid, be effected.

The following examples explain the process: Example i 2o, 5 parts of finely powdered acid sulphate of p-toluidine are intimately mixed with 25 parts of partially dehydrated aluminum sulphate of approximate composition A12 (S04) 3-9H20 and added to zoo parts of toluene. 8.2 parts of ethyl nitrite are introduced into this suspension at 5 to 10 °. After the addition has ended, the temperature is slowly increased to 25 ° to 30 ° and the mixture is stirred for a further hour. The acidic sulphate of the base gradually changes into the acidic diazonium sulphate during the entire process, without smearing in the slightest or clumping. The product is filtered off, washed with toluene and dried at 30 to 35 °.

Example 2 '23.6 parts of acid sulfate of o-nitroaniline are with Ground 25 parts of anhydrous sodium sulfate and added to 250 parts of ligroin. 2.9 parts of amyl nitrite are slowly added dropwise at 5 to 10 ° to this suspension. To complete the conversion into the diazonium sulfate, 1 hour at 25 Stirred up to 30 °. The filtered and dried product can be further processed will.

Example 3 22.55 parts of finely powdered acid sulfate of o-chloroaniline turn with 25 parts partially watered aluminum sulfate ground and in 2oo parts carbon tetrachloride registered. 8.2 parts of ethyl nitrite are introduced into this suspension at 5 to 10 °. The conversion of the acid sulphate into the diazonium sulphate is carried out by one hour Stirring at 25 to 30 ° completes what happens without any smearing is going. The product is filtered off, dried and processed further using a diazo salt preparation.

Example q.

23.6 parts of acid sulphate vono-Ntitraniline are partially dehydrated with 25 parts Zinc sulfate of the composition Zn S04 - 1 HZ 0 ground and ligroin in 250 parts registered. At 5 to 10 °, 8.5 parts of nitrogen trioxide are slowly added to this suspension initiated. When the introduction is complete, the mixture is subsequently stirred at 30 ° for 1 hour. Then the diazonium sulfate is filtered, washed with ligroin and kept at a gentle temperature dried.

Example s In the submitted 25 parts of chlorobenzene are at 5 to 10 ° 8.2 parts of ethyl nitrite initiated. This solution is slowly added in portions an intimate mixture of 26 parts of finely powdered acid sulphate of 5-dichloroaniline with 25 parts of dehydrated sodium sulfate. The conversion into the diazonium sulfate is completed by heating for about one hour to 25 to 30 °. The diazonium sulfate is then finished as in Example 2.

Example 6 26.6 parts of acid sulphate of 5-nitro-2-amino-i-methoxybenzene are ground with 25 parts of partially dehydrated aluminum sulfate and in zoo parts Tetrachloroethane registered. An ice-cold suspension is added to this suspension at 5 ° Run in solution of 8.2 parts of ethyl nitrite in 100 parts of tetrachloroethane. One stirs for complete conversion into the diazonium sulfate for one hour at 30 ° and filtered the white crystalline powder, which can be prepared in the usual way can.

Example 7 23.6 parts of acid sulphate of o-nitroaniline are mixed with 25 Ground parts of partially dehydrated aluminum sulfate and stirred into 250 parts of toluene. In this suspension 7.8 parts of nitrosyl chloride are obtained with good cooling initiated. After the run-in has ended, the mixture is subsequently stirred at 25 ° to 30 ° for 1 hour. That filtered and dried salt is prepared as usual.

Example 8 24. Parts of finely powdered acid sulfate of 5-chloro-2-amiuo-i-methylbenzene are mixed with 25 parts of partially dehydrated aluminum sulfate and divided into 25o parts Tetrachloroethane registered. 8.2 parts of ethyl nitrite are then added to this suspension initiated, and it is stirred at 25 to 30 ° for about 1 hour. The transformation in the diazonium sulfate goes on without any smear formation. That after filtering and drying, the white, readily soluble in water diazonium sulfate is in finished in the usual way.

Example 9 13.8 parts of o-nitroaniline are partially dehydrated with 25 parts. Ground aluminum sulfate and added chlorobenzene to 250 parts. To do this, drips one at 5 to 10 ° a solution of 14 parts of nitrosylsulfuric acid in 17 parts about 88 percent sulfuric acid. After stirring at 30 ° for one hour, the mixture is filtered and dried. The diazonium sulfate preparation is easily and completely soluble in water.

Example 10 23.6 parts of acid sulphate of m-nitroaniline are mixed with 30 parts partially dehydrated magnesium sulphate with the approximate composition Mg Sao - 2 H20 and registered in 250 parts of toluene. 7.8 parts of nitrosyl chloride are added to this suspension initiated. After stirring at 30 ° for one hour, the mixture is filtered and the diazonium sulfate preparation finished as usual.

Example ii 25 parts of acid sulfate of 3-nitro- [-aminoi-methylbenzene] are ground with 25 parts of partially dehydrated aluminum sulfate and 25o parts with carbon tetrachloride slurried. 8.2 parts of ethyl nitrite are introduced into this suspension at 5 to roll, and stirring is continued at 30 ° for 1 hour. The diazonium sulphate that works without smearing forms, is filtered off.

Example 12 13.8 parts of o-nitroaniline are partially dehydrated with 25 parts Milled aluminum sulfate and introduced into 25o parts of nitrobenzene, the o-nitroaniline slowly goes into solution. By carefully adding 9.8 parts anhydrous With vigorous stirring, sulfuric acid becomes o-nitroaniline in the form of acid sulphate deposited in fine distribution with the aluminum sulfate. In this suspension which must be very finely divided, now 8.2 parts of ethyl nitrite at 5 to 10 ° initiated, and the procedure is continued as in example i i.

Example 13 32.3 parts of acid sulfate of o-aminoazotoluene are with 25 parts of partially dehydrated alum of the approximate composition K2 A12 (S04) 4 - 9H20 ground and added to 25o parts carbon tetrachloride. By initiating of 8.2 parts of ethyl nitrite at 5 to 10 ° the acid sulfate is in the Diazoniumsul £ at convicted. After stirring at 3o to 35 ° for one hour, the mixture is filtered and the gray-brown Diazonium sulfate dried at low temperature.

Claims (1)

PATENT CLAIM: Process for the production of solid diazonium sulfates, consisting in that one diazotizable aromatic mixtures of acidic sulfates Amines and water-binding metal sulfates in organic, hydroxyl-free liquids, which are immiscible with water and in which the relevant diazonium sulfates are sparingly soluble, diazotized and the resulting mixtures of metal sulfates and Separates diazonium sulfates from the liquid.