CS246351B1 - From 1,3,5-trimethylbenzenesulphonic acid derived compounds and method of their preparation - Google Patents

Description

The invention relates to diazonium compounds derived from

1,3,5-trimethylbenzenesulfonic acids having the moiety -NO ₂ , -NH-γcyl or -NH-SO 6 -aryl in the molecule, and a process for their preparation by diazotization of the corresponding primary amines.

Said diazonium compounds are a group of novel substances which have not been described in the literature

The present invention provides diazonium compounds of formula I

acids with one to three benzene rings or heterocyclic rings containing nitrogen and the process

their preparation consisting in that of the amines.

NH ₂

CH-2 246 3S1 wherein X and Y are as defined above and Me is a cation, acts with diazotizing agents, optionally in the presence of diazotation aids.

Diazotization uses derivatives of 2-amino-1,3,5-trimethylbenzene-4-sulfonic acid respectively. sulfonates substituted in the 6-position with e.g. N-racylamino such as acetylamino, benzoylamino, nitro- or dinitrobenzoylamino, or -NH-SO ₂ -aryl such as NHSO ₂ -, -, NHSO ₂ -, CH ₂ , or nitro.

Among the diazotizing agents, all common compounds such as nitrites, organic nitrites (preferably ethyl or amyl nitrite), nitrous gases, but also less common agents such as NO ⁺ (FBNO ₂ ) - or NO ⁺ BF 2 - complexes can be used. Hydrotropic agents such as toluenesulfonates, xylensulfonates, indonsulfonates, tetrahydronaphthalenesulfonates, surfactants such as formaldehyde condensates with naphthalenesulfonic acids, ligninsulfonates and the like are suitable to facilitate diazotization.

In diazotization, the compounds of the general formula IIa and IIa can be used. IIb is mixed with water and an acid such as hydrogen chloride, sulfuric acid, hydrobromic acid, perchloric acid, acetic acid and the like, followed by the addition of a diazotizing agent. Since most of the compounds of formula (IIa) are - in the form of inner salts - poorly soluble in an acidic medium, it is advantageous to carry out diazotization in an indirect manner, i.e. by preparing aqueous solutions of salts of formula (IIb) e.g. of formula (IIIa) is mixed with aqueous alkali, the diazotizing agent is added to the solutions and the resulting mixture is introduced into a mineral or strong organic acid. The temperature is maintained at 5 to 15 ° C during diazotization, but it is also possible to work at 30 to 40 ° C since the sulfo group present in the diazonium compound molecule stabilizes these.

The obtained diazonium compounds can be used for the preparation of azo dyes and possibly other semi-finished products.

246 351

The following examples illustrate embodiments of the invention. Example 1

To a sample of 300 ml of water was added 95.8 g of 81.4% 4-nitromesidine-6-sulfonic acid (0.3 mol) and dissolved with 109 ml of sodium hydroxide solution (c / NaOH) = 2.5 mol / l. such that the pH is 7 to 7.5. Dilute the solution with approx. 60 ml of water to a volume of 520 ml (150 g / l) and then dispense it uniformly together with 120 ml of sodium nitrite solution with a concentration of / / NaNO 2 / ^a = 2.5 mol / l / 0.3 mol (during 1 hour with efficient stirring into the flask * 180 ml of hydrochloric acid at a concentration of δ (HCl) = 5 moles (1 / 0.9 moles), 800 g of ice and 800 ml of H ₂ 0. The temperature should be between 5 and 10 ° C and the reaction mixture must consistently exhibit a positive conjugate reaction. At the end of the dosing, there should be an excess of sodium nitrite in the reaction mixture, otherwise another solution is dosed to a positive reaction on iodo-starch papers. After stirring for half an hour, the possible excess of NaNO ₂ is blunted and the chiazo of 4-nitromesidine-6-sulfonic acid obtained in quantitative yield as a yellow suspension of 0.124 mol / l can be further processed.

Example 2

From 81.7 g of 100% 2-amino-4- (N-acetylamino) -1,3,5-trimethylbenzene-6-sulfonic acid (0.3 mol) with about 350 ml of water and about 115 ml of sodium hydroxide solution with a concentration of / (NaOH) = = 2.5 mol / l, prepare a solution with a concentration of 150 g / l / volume of 545 ml / a, having a pH greater than 7.5, which is metered into well with 180 ml of hydrochloric acid concentration of £ (HCl) = = 5 moles (1) (0.9 moles) and 1 000 g of crushed ice together with 120 ml of sodium nitrite solution with a concentration of / (NaNO 2) = 2.5 moles (1 / 0.3 moles) so that the temperature does not exceed 10 ° C. Typically, 30 min is sufficient for dosing and the reaction mixture is treated in the same manner as in Example 1. The yellow solution obtained contains 2-amino-4- (N-acetylamino) -1,3,5-trimethylbenzene-6-sulfonic acid diazonium salt at a concentration of 0.174 mol / l (1725 ml volume).

Example 3

15 ml of hydrochloric acid with a concentration of c (HCl) = 5 moles (1) 0.075 moles, 60 g of ice and 60 ml of water are added to the flask »

248 3S1 proportionally dosed with 10 ml of sodium nitrite solution with a concentration of 2.5 (Na / K) = 2.5 mol (1) 0.025 mol) and 64 ml of an aqueous solution of 2-amino-4- (4-methylbenzanesulfonamido) -1,3,5 trimethylbenzene-6-sulfonic acid, prepared by dissolving 19.7 g of 48.3% paste (0.025 mol) in 34 ml of water with 9.5 ml of 2.5M sodium hydroxide solution (NaOH). The temperature is kept below 5 ° C and after stirring for half an hour, any excess NaNO ₂ is blunted with a sulfemic acid solution. Liazo is obtained in the form of a yellow suspension of about 200 ml (concentration 0.125 mol / l).

In the same manner as described in Example 2, diazonium salts characterized by Formula I can be prepared when the following starting compounds are used

Example Starting amine Structural formula of a diazonium salt

2-amino-4- (N-benzoyl)

CH 1 H -1,3,5-trimethylbenzene-6-sulfonic acid

NO

2-Amino-4-N- (3-nitro) -benzoylamino-1,3,5-

2-amino-4-N- (3,5-di- ₊ nitro) -benzoylamino-N-N

1,3,5-trimethylbenzene-6-sulfonic acid

NO,

SO

248 3S1

The structure of all the diazonium salts mentioned in the examples was verified by constitution analysis after their synthesis with passive components.

Claims (2)

1.Diazonium compounds of general formula (1) -SO ₂ - @ - _CH3, formyl, acetyl, acyl derived from aromatic carboxylic acids with ^ one to three benzene rings or heterocyclic carboxylic acids having 5 or 6 membered ring containing 1 to 3 heteroatoms such as oxygen, sulfur or nitrogen, in which case when Y is oxygen, X is not hydrogen. 2. A process for the preparation of the diazonium compounds of the above-mentioned formula (I), characterized in that the amines of the general formula (IIa) and (IIa) are reacted with a compound of formula (II). (IIb) wherein X and Y are as defined above and Me is a cation, is treated with diazotizing agents, and preferably amines as defined by formulas IIa and IIa, respectively. 1b, mixed with water, a basic agent capable of forming an aqueous solution with a pH greater than 7, and a selected diazotreating agent, then adding the mixture to an inorganic or organic acid and maintaining the pH of the reaction mixture below 4, optionally in the presence of diazotation aids . Printed by Moravian Printing Works,