A PROCESS FOR THE PREPARATION OF AN AZIDOSULPHONYLBENZOIC ACID

Abstract: The invention relates to a process for the preparation of an azidosulphonylbenzoic acid which comprises reacting a water-­ soluble salt of a chlorosulphonylbenzoic acid with hydrazine (N₂H₄) in an aqueous medium, reacting the obtained hydrazino­ sulphonylbenzoic acid salt with nitrous acid in the same aqueous medium, acidifying the resulting aqueous solution comprising the azidosulphonylbenzoic acid salt, to precipitate the azidosul­ phonylbenzoic acid and separating the azidosulphonylbenzoic acid. The process is a one-pot process, which differs from a known process in that the intermediate, being the hydrazino­ sulphonylbenzoic acid salt, is not isolated.

Description: The invention relates to a process for the preparation of an azidosulphonylbenzoic acid, to the azidosulphonylbenzoic acid so prepared and to its use as a carboxylation agent in elastomers. From "Houben-Weyl, Methoden der Organischen Chemie, IX", page 653 it is known to prepare azidosulphonylbenzenes either by reacting chlorosulphonylbenzenes with sodiumazide or by reacting hydrazinosulphonylbenzenes with sodiumnitrite. It is further known from J. Chem. Soc. (C), 1968, pages 11-16, to prepare azidosulphonylbenzoic acids by reacting the chlorosulphonyl­ benzoic acids with hydrazine hydrate in ethanol or dioxan at a low temperature, e.g. 0 °C. After cautions acidification and generally recrystallization the corresponding hydrazinosulphonyl benzoic acids are obtained as crystals, which decompose at their melting point. The hydrazinosulphonylbenzoic acids are converted into the corresponding azidosulphonylbenzoic acids. Dis­ advantages in the process for preparing azidosulphonylbenzoic acids are the use of an organic solvent, e.g. ethanol or dioxan, the isolation of the hydrazide intermediate with re­ crystallization, the two step process and molar excess of hydrazine. A disadvantage of the use of sodiumazide is the limited availability and the expensiveness of the sodiumazide. It is the object of the present invention to have a much simpler process for the preparation of azidosulphonylbenzoic acids. The invention relates to a process for the preparation of an azidosulphonylbenzoic acid which comprises reacting a water-­ soluble salt of a chlorosulphonylbenzoic acid with hydrazine (N₂H₄) in an aqueous medium, reacting the obtained hydrazino­ sulphonylbenzoic acid salt with nitrous acid in the same aqueous medium, acidifying the resulting aqueous solution comprising the azidosulphonylbenzoic acid salt, to precipitate the azido­ sulphonylbenzoic acid and separating the azidosulphonylbenzoic acid. It has been found, that the process according to the invention is much more economical than the two-step process. The chlorosulphonylbenzoic acids which may be used as starting compounds in the process according to the invention have the general formula wherein the -COOH group is situated ortho, meta or para with respect to the -SO₂Cl group, X is an alkyl-, alkoxy-, nitro-, carboxyl-, ester-, halogen- or hydroxygroup and n is 0, 1, 2, 3 or 4. The starting compounds may thus be chlorosulphonylbenzoic acids, which contain only one -COOH group (in ortho, meta or para-position v.a.v the -SO₂Cl group) or they may have been substituted at the other remaining positions by the above-­ mentioned groups. They may be substituted by a different group at a different position. The starting compounds are all considered to be derived from benzoic acid. The alkyl- or alkoxygroup may preferably have from 1 to 20 carbon atoms and may be linear or branched. The ester group is preferably group, wherein R is a lower alkyl group of from 1 to 4 carbon atoms. The starting compounds can also comprise more than one -COOH group. The most preferred starting compound is 3-chlorosulphonylbenzoic acid. Preferred starting compounds are further the methyl-, methoxy-, hydroxy-, chloro- and bromo­ derivatives of 3-chlorosulphonylbenzoic acid. The water-soluble salt of the chlorosulphonylbenzoic acid is preferably an ammonium salt or an alkalimetal salt, more preferably the sodium or potassium salt. The water-soluble salt is obtained by dissolving the chlorosulphonylbenzoic acid in water in the presence of sodium- or potassium carbonate or sodium- or potassium bicarbonate or borate. Sodiumbicarbonate is preferred and may be present together with the other reaction component, namely the hydrazine, generally present in the form of hydrazine-hydrate. The chlorosulphonyl benzoic acid may be added in small portions or dropwise to the aqueous solution of hydrazine-hydrate and sodiumbicarbonate. The temperature during the reaction is generally low, e.g. below 25 °C. The obtained hydrazinosulphonylbenzoic acid salt is then reacted with nitrous acid, which latter compound is generally prepared in situ by reacting sodiumnitrite with a strong acid, such as hydrogen chloride or sulfuric acid. The sodiumnitrite can be added in one portion to the obtained aqueous solution of hydrazinosulphonyl­ benzoic acid salt. In order to release the nitrous acid, the strong acid is added in small portions or dropwise to the aqueous solution. The reaction temperature is generally between 0 ° and 15 °C. After acidification of the solution to pH2 to 3, the resulting azidosulphonylbenzoic acid is precipitated. The compound is separated from the solution and if desired washed and dried, preferably at room temperature in vacuum. The starting compound 3-chlorosulphonylbenzoic acid may be obtained by reacting 3 mol chlorosulfonic acid with 1 mol benzoylchloride according to the reaction equation The azidosulphonylbenzoic acids, especially the 3-azido­ sulphonylbenzoic acid, are suitable as carboxylation agent for the preparation of carboxylated elastomers. An example of the latter is ethene-propene rubber, which easily reacts with the azidosulphonylbenzoic acid at a temperature of about 190 °C to 210 °C. Example In an Erlenmeyer glass are brought 1,5 litres of water, 1 mol hydrazine.hydrate (as an 80 %w solution in water) and 2 mol NaHCO₃. To this mixture is added in small portions 1 mol 3-chlorosulphonylbenzoic acid under stirring at a temperature of 5 °C. The resulting solution is stirred further for 2h at a temperature of 5 °C. The 1,1 mol NaNO₂ is added to the solution and subsequently in 2h 2,1 mol HCl (HCl/H₂O, 1/1) is added to the solution. The temperature is maintained at 5 °C, while holding the glass in an ice bath. After acidifying the solution with HCl to a pH of about 2 to 3 the 3-azidosulphonylbenzoic acid precipitates. The precipitate is washed with water and dried at 20 °C in vacuum. There is obtained 0.85 mol 3-azidosulphonylbenzoic acid (melting point 122-127 °C under decomposition), with infrared absorption 2160 cm⁻¹ and 1690 cm⁻¹. Yield is 85%.

Claims: 1. A process for the preparation of an azidosulphonylbenzoic acid which comprises reacting a water-soluble salt of a chloro­ sulphonylbenzoic acid with hydrazine (N₂H₄) in an aqueous medium, reacting the obtained hydrazinosulphonylbenzoic acid salt with nitrous acid in the same aqueous medium, acidifying the resulting aqueous solution comprising the azidosulphonyl­ benzoic acid salt, to precipitate the azidosulphonylbenzoic acid and separating the azidosulphonylbenzoic acid. 2. A process as claimed in claim 1, wherein the chloro­ sulphonylbenzoic acid has the general formula wherein the COOH group is situated ortho, meta or para with respect to the -SO₂Cl group, X is an alkyl-, alkoxy, nitro-, carboxyl-, ester-, halogen-, or hydroxy-group and n is 0, 1, 2, 3 or 4. 3. A process as claimed in claim 1 or 2, wherein the acid is 3-chlorosulphonylbenzoic acid. 4. A process as claimed in any one of the claims 1-3, wherein the water-soluble salt of the chlorosulphonylbenzoic acid is an alkali metal salt or ammonium salt. 5. A process as claimed in claim 4, wherein the alkali metal salt is the sodium or potassium salt. 6. A process as claimed in any one of the claims 1-5 wherein the water-soluble salt of the chlorosulphonylbenzoic acid is obtained by dissolving the chlorosulphonylbenzoic acid in water in the presence of sodium- or potassium carbonate or -bi­ carbonate. 7. A process as claimed in any one of the claims 1-6, wherein the nitrous acid is prepared in situ by reacting sodium nitrite with a strong acid. 8. A process as claimed in claim 7, wherein the strong acid is hydrogenchloride or sulphuric acid. 9. A process as claimed in claim 7 or 8, wherein the strong acid is added dropwise to the reaction solution, while releasing the nitrous acid slowly in the reaction solution. 10. A process as claimed in claim 9, wherein the reaction temperature is between 0° and 15 °C. 11. A process for the preparation of carboxylated elastomers which comprises reacting an elastomer with an azidosulphonyl­ benzoic acid, prepared by means of a process as claimed in any one of the claims 1 to 10.

Inventors: UDDING, ANNE CATHARINUS
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1986
Main classification: C07C143
IPC codes: C08F8, C07C303, C07C311, C07C301, C07C67, C08C19