Aromatic heterocyclic peroxyacids

Abstract: Nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids having the formula: wherein R represents a hydrogen atom or a straight or branched alkyl, (hetero)cycloalkyl, (hetero)aryl, alkylaryl or arylalkyl group, wherein said groups are optionally substituted, or a carboxylic group or any other substituents non-reactive in the presence of the active oxygen of the peroxycarboxylic group; n is a number selected from 0 and 1; m is a number selected from 1, 2 and 3, and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻ , and wherein the pyridinic ring may in its turn be condensed with at least one further (hetero) aromatic or (hetero)cycloalkylic ring. Also described is their preparation process and their use as bleaching agents.

Description: The present invention relates to organic (poly)peroxy acids which can be referred to as aromatic N-heterocyclic (poly)peroxycarborylic acids, and to the preparation process therefor. More particularly, the present invention relates to aromatic heterocyclic mono- or poly-peroxycarboxylic acids containing nitrogen in the ring and having the formula (I): wherein R represents a hydrogen atom; a carboxylic group or peroxycarboxylic group; an aryl group selected from C₆H₅- and C₆H₅-CH₂-, the aromatic ring thereof being optionally substituted by one or more groups selected from C₁-C₅-alkoxy, COOH, OH, F, Cl, NO₂ or from C₁-C₁₀-alkyl, optionally substituted by 1 to 3 F and/or Cl atoms; a straight or branched (hetero)alkyl containing an overall number of up to 10 carbon atoms and being optionally substituted by at least one substituent selected from the class consisting of F, Cl, OH, NO₂, (C₁-C₅)-alkoxy groups, or by at least one carboxylic or peroxycarboxylic group; a F atom; a Cl atom; an OH or NO₂ group; or a (C₁-C₅)-alkoxy group; the heteroatoms being selected from N and O; and wherein n is a number selected from 0 and 1, preferably 0; m is a number selected from 1, 2 and 3; and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻; and the pyridine ring may in its turn be condensed with at least one further aromatic or heteroaromatic ring to form a quinolinic, isoquinolinic or pyridoindolic group; to a process for their preparation and to their use as bleaching agents. Olah et al., J. Org. Chem. 42 (1977) 32, describe rearrangement reactions of tertiary alkyl (arylalkyl) peroxy esters, the corresponding peroxyacids being discussed as intermediate products. GB-A-858848 refers to the adduct formation between picolinic acid and hydrogen peroxide, however, without the formation of picolinic peroxide. The preparation of isocuinoline-3-percarboxylic acid by reaction of isoquinoline-3-carboxaldehyde with 30% hydrogen peroxide in aceton is disclosed in J. Am. Chem. Soc. 73 (1951) 688. Salts of said acid are not described. The N-hetero-aromatic peroxycarboxylic compounds having the above formula (I) constitute a new class products that are highly interesting from an industrial viewpoint. They, in fact, may find a general use, similarly to that already known for peroxyacids, in the field of plastics (as polymerization starters or as oxidizing agents for olefin epoxidation and hydroxylation), and in many other oxidative processes in the field of fine chemistry. In a more specific way, however, the aromatic N-heterocyclic (poly)peroxycarboxylic acids having the above formula (I) find a particularly efficacious application in the field of bleaching in the detergent industry. The organic peroxyacids aroused an increasing interest in the industrial field, due, among others, to their excellent possibilities for use as bleaching agents in formulations for medium/low temperature washing, and even more widespread due to energy-saving considerations. Therefore a large number of literature references exists concerning an, at present, considerable research activity aiming at finding organic peroxyacid compounds endowed with the necessary requisites of bleaching activity, and, in particular, thermal stability and storage stability or shelf life, these latter requisites being essential for the industrial and widespread application of all such compounds. Therefore, many mono- and di-peroxycarboxylic (aliphatic or carbocyclic) organic peroxyacids are known and used, among others, in the detergent field. Already described peroxycarboxylic acids are, e.g., diperoxydodecanedioic acid, monoperoxyphthalic acid, diperazelaic acid, substituted diperoxyglutaric and adipic acids, etc. Applicants are not aware of any previous aromatic N-heterocyclic (poly)peroxycarboxylic acids having the above formula (I), nor of any process for their preparation. The traditional process contemplates carrying out the oxidation of the substrate (an organic acid, anhydride or ester) with a concentrated solution of hydrogen peroxide, in concentrated H₂SO₄ or CH₃SO₃H. The strong acidity of this reaction medium and the presence in the substrate of a salifiable nitrogen atom of basic character confer on the said substrate a high solubility in the acidic medium. Such high solubility makes it impossible to apply any of the traditional processes for the isolation of the peroxycarboxylic acid derivative which may be formed in the oxidation reaction with hydrogen peroxide, such as by precipitation or extraction methods with organic solvents. Surprisingly, in accordance with the present invention, it has been discovered that the nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids having the formula (I), salified on the nitrogen atom with the HSO₄⁻ or the CH₃SO₃⁻ anion, may be obtained in a stable form by means of a novel process which is also a part of the present invention. One object of the present invention is to provide the nitrogen-containing N-aromatic heterocyclic (poly)peroxycarboxylic acids having the above formula (I). Another object is to provide a simple and cheap process for the preparation of the above peroxycarboxylic acids having the above formula (I), in a per se stable form. A further object is the use of aromatic N-heterocyclic peroxycarboxylic acids having the above formula (I) as bleaching agents in detergent formulations; and especially those destined for low-medium temperature use. These, and still other objects which will become even clearer for those skilled in the art from the following detailed disclosure, are achieved, according to the present invention, by the nitrogen-containing aromatic N-heterocyclic peroxycarboxylic acids having the above formula (I), and by the relevant preparation process, characterized in that a substrate consisting or consisting essentially of an aromatic N-heterocyclic (poly)carboxylic acid containing a nitrogen atom in the ring, and/or its anhydride and/or its lower alkyl esters, corresponding to the desired peroxycarboxylic acids having formula (I), is reacted with concentrated H₂O₂, by operating in a reaction medium selected from concentrated H₂SO₄ and CH₃SO₃H, and in that the peroxycarboxylic acid (I) is then separated from the reaction mixture by the addition of an organic solvent selected from tetrahydrofuran and ethyl acetate. In this way the peroxycarboxylic acids having the formula (I) are obtained, generally as stable solids, salified on their nitrogen atom with the HSO₄⁻ or CH₃SO₃⁻ anion, and recovered from the reaction medium by means of their insolubilization in the reaction medium by the solvent. Described in a somewhat different way, the process according to the present invention consists in the peroxycarboxylation reaction of the substrate consisting or consisting essentially of the (poly)acid, anhydride or ester of the aromatic N-heterocyclic carboxylic acid, corresponding to the desired (poly)peroxycarboxylic acid of formula (I), in an acid medium of concentrated H₂SO₄ or CH₃SO₃H, with H₂O₂ and in the subsequent addition, at the end of the reaction, of a suitable organic solvent, which is not miscible with the desired product by dissolving it, and which is capable , on the contrary , of completely dissolving the acid reaction medium (concentrated H₂SO₄ or CH₃SO₃H), as well as the excess of H₂O₂ with the reaction water. This involves the consequent separation, by insolubilization, of the (poly)peroxycarboxylic acid product having the formula (I), which precipitates, usually, in a stable solid form. The obtained product is then filtered, washed with the solvent, dried, and so forth, according to per se known techniques. As said above, the substrate used as the starting material consists or consists essentially of the aromatic N-heterocyclic (poly)carboxylic acid corresponding to the desired (poly)peroxycarboxylic acid of formula (I); it may furthermore be used e.g. as its corresponding lower straight or branched (C₁-C₅)-alkyl ester or, e.g. in case two adjacent carboxy groups (R = COOH) are present, also the corresponding anhydride may be used. These compounds are per se known, and/or can be prepared according to conventional techniques, and/or are commercially available. Referring to the above formula (I), R is preferably an aryl group or a linear or branched (hetero)alkyl group, containing up to 10 carbon atoms. Said groups may in turn be substituted with one or more atoms or groups, either equal to or different from one another, inert under the reaction conditions under which the preparation takes place, such as F or Cl atoms, OH groups, NO₂ groups and (C₁-C₅)-alkoxy groups. The (hetero)alkyl group may be also substituted by at least one carboxylic or peroxycarboxylic group. As an alternative, R may be a substituent which does not react with the active oxygen of the peroxycarboxylic group, e.g. a carboxylic group or a percarboxylic group, an F atom, a Cl atom, an OH group, an NO₂ group or a (C₁-C₅)-alkoxy group. Finally, the pyridine ring may be condensed with at least one other (hetero) aromatic ring, e.g., in the form of a quinolinic, isoquinolinic, pyridoindolic group. Preferred examples of groups R in formula (I) are: (a) C₁-C₁₀, particularly C₁-C₅-alkyl, e.g. methyl, ethyl, n- or i-propyl, n-, sek-, or i-butyl, pentyl, hexyl, 2-ethylhexyl, octyl and decyl; and such groups substituted by 1 to 3 F and/or Cl atoms, e.g. CFH₂, CF₂H and CF₃; (b) C₁-C₅-alkoxy, the alkyl groups thereof being derived from those mentioned above; (c) COOH, OH, F, Cl, NO₂, (d) C₆H₅, CH₃-C₆H₄, Cl-C₆H₄,C₆H₅-CH₂, the aromatic ring thereof being optionally substituted by one or more groups from classes (a) to (c) above. For m = 2 or 3 the substituents R may be the same or different. As starting alkyl esters of a heterocyclic (poly)carboxylic acid the C₁-C₅-alkyl esters wherein the alkyl groups are those exemplified above are particularly preferred. Starting substrates for obtaining the corresponding aromatic N-heterocyclic peroxycarboxylic acids having the formula (I), are, for exemplary purposes: 4-pyridine-carboxylic acid, 2,4-pyridine-dicarboxylic acid, 3-pyridine-carboxylic acid, 2,3-pyridine-dicarboxylic acid and its anhydride, 2,5-pyridine-dicarboxylic acid, 3,5-pyridine-dicarboxylic acid, 3-pyridine carboxylic-N-oxide acid, the ethyl ester of 4-pyridine-carboxylic acid, 2,6-dihydroxy-4-pyridine-carboxylic acid, 6-methyl-3-pyridine-carboxylic acid, 2-phenyl-4-quinoline carboxylic acid, 6-isobutyl-3-pyridine-carboxylic acid, 5-p-tolyl-4-pyridine-carboxylic acid, 5-benzyl-3-pyridine-carboxylic acid, 6-fluoromethyl-3-pyridine-carboxylic acid, 2-p-chloro-phenyl-4-quinoline-carboxylic acid, pyrido-indole-4-carboxylic acid, 5-chloro-4-pyridine-carboxylic acid, etc. In case R = COOH, preferably in a non-ortho-position with respect to the nitrogen atom , the peroxycarboxylation of R may also be carried out, thus obtaining a product of formula (I) with two or more peroxycarboxylic groups. According to a preferred operating mode, the reaction of peroxycarboxylation of the "aromatic" N-heterocyclic carboxylic acids used as the starting substrates, or of their esters or anhydrides, is carried out by gradually adding H₂O₂, having a concentration within the range of from approximately 70% to approximately 90% by weight, to a solution of the substrate in concentrated H₂SO₄, or in CH₃SO₃H, by maintaining the reaction temperature throughout the reaction course within the range of from 15° to 50°C , depending on the reactivity of the substrate. Otherwise, it has been found advantageous to prepare in advance the salt of the substrate (in the form of an HSO₄⁻ or CH₃SO₃⁻ salt), by processing under the same conditions as shown above, but in the absence of H₂O₂, and then by separating and peroxidizing the thus-obtained salt to a compound of formula (I). The amount of H₂SO₄ or of CH₃SO₃H, determined at a concentration of 100%, is between 5 and 30 moles per mole of substrate, and is preferably between 7 and 10 moles per mole of substrate. The hydrogen peroxide is used in an amount which is in excess with respect to the substrate, and is between 1.4 and 6 moles per mole of substrate, and preferably between 3 and 4 moles per mole of substrate. The reaction time depends on the nature of the substrate, on the operating temperature, and on the end total H₂SO₄/H₂O or CH₃SO₃H/H₂O molar ratio present at the end of the reaction. Said ratio is between 2.5 and 10, and preferably between 3 and 7, by adjusting the various concerned parameters. Reaction times between 30 minutes and 4 hours have been shown to be operative, and generally a reaction time of from 1 hour to 2 hours is sufficient. The amount of tetrahydrofuran or ethyl acetate solvent used is usually not lower than 4 liters/substrate mole, and furthermore, it is added at a temperature not higher than 10°C. The aromatic N-heterocyclic peroxycarboxylic acid products having formula (I) are usually solid at room temperature. They may be especially useful in formulations of detergent compositions, e.g., granular formulations, as bleaching agents in solution over a wide temperature range, owing to their good characteristics of storage stability and thermal stability as obtained. The detergent composition may be formulated according to the usual pertinent techniques, together with other components and/or additives, etc. Moreover, the final reaction mixture, before separation of (poly)peroxycarboxylic acid of formula (I), may be subjected to a phlegmatization process. The present invention is now disclosed in still further detail in the following examples. The products prepared in the examples were characterized by elemental analysis, by determining their content of active oxygen (by iodometric titration), and by using Fourier Transform Infrared Spectroscopy (FT-IR). Example 1 15 g (0.156 mole) of methanesulphonic acid were charged into a beaker, equipped with stirrer, thermometer, and outer bath. The internal temperature was increased to 35°C and 2 g (0.0162 mole) of isonicotinic acid (4-pyridine-carboxylic acid) were added under stirring for 15 minutes. The above temperature was maintained until a complete dissolution of the carboxylic acid was obtained, and then the temperature was lowered to 15°C and 3.3 g of H₂O₂ at 85% (0.0825 mole) were gradually added so that the temperature was maintained lower than 25°C. The temperature was then increased to 40°C and the stirring was continued for 2 hours. The reaction mixture was then poured into 200 ml of ethyl acetate maintained under stirring at 10°C. After a few minutes, the products separated in the crystalline form. The stirring was continued for 1 hour at a temperature between 0° and 10°C. and then the solution was filtered under vacuum over a porous septum. The product was directly washed on the filter with ethyl acetate (30 ml), then with ethyl ether (30 ml). The product was then kept inside a CaCl₂-drier under vacuum and at room temperature for 1 hour. 3.3 g of crystalline 4-pyridine-peroxycarboxylic acid methanesulphonate were obtained having a purity of 92.4% (active oxygen content 6.3%) corresponding to a yield of 80%. The product was purified by keeping it under stirring in anhydrous ethanol (35 ml) for 1 hour at room temperature. Elemental Analysis : Computed for C₇H₉O₆NS : C, 35.74%; H: 3.85%; N: 5.95%; O (active): 6.8%; CH₃SO₃H, 40.85%. Found: C: 35.80%; H: 3.69%; N: 5.84%; O (active): 6.70%; CH₃SO₃H: 40.81%. Melting Point: 98°C (with decomposition). Example 2 2.5 g of 2,4-pyridine-dicarboxylic acid were dissolved in 43.3 g (0.45 mole) of methane sulphonic acid. By operating according to the procedures of Example 1, 3.4 g of H₂O₂ at 85% (0.085 mole) were added and the stirring was continued at 50°C for 2 hours. The reaction mixture was then poured into 900 ml of ethyl acetate and, by operating according to Example 1, 3.2 g of crystalline substantially pure 2-pyridine-carboxy-4-peroxycarboxylic acid methanesulphonate were obtained: yield 77%. Elemental Analysis : Computed for C₈H₉O₈NS : C, 34.40%; H: 3.24%; N: 5.0%; O (active): O: 5.73%; CH₃SO₃H: 34.4%. Found: C: 33.7%; H: 3.17%; N: 4.82%; O (active): 5.73% CH₃SO₃H: 34.10%. The product decomposed at 128°C. Example 3 By operating according to the procedures of Example 1, 1.53 g of nicotinic acid (3-pyridinecarboxylic acid) (0.0122 mole) were dissolved into 12 g of H₂SO₄ at 96% (0.117 mole) and 2.05 g of H₂O₂ at 85% (0.0514 mole) were added, continuing then the stirring at 40°C for 3 1/2 hours. The reaction mixture was then poured into 300 ml of ethyl acetate according to the procedure of Example 1. By operating as above described, 2.5 g of crystalline 3-pyridine-peroxycarboxylic acid sulphate were separated, having a purity of 87% (active oxygen content of 5.86%; theoretically determined value for (C₆H₇O₇NS: 6.74%) and corresponding to a yield of 72%. Elemental Analysis : Computed for C₆H₇O₇NS : C: 30.39%; H: 2.97%; N: 5.90%; O (active): 6.74%; H₂SO₄: 41.36%. Found: C: 30.42%; H: 3.25%; N: 5.98%; O (active): 5.86%; H₂SO₄: 41.42%. Melting Point: 103°C (with decomposition). Example 4 By operating according to the procedures of Example 1, 4.59 g (0.0365 mole) of nicotinic acid (3-pyridinecarboxylic acid) were dissolved into 36 g (0.375 mole) of methanesulphonic acid and 6 g of H₂O₂ at 70% (0.123 mole) were added, continuing then the stirring at 40°C for 2 1/2 hours. The reaction mixture was then poured into 600 ml of tetrahydrofuran according to the procedures of Example 1. By operating as above described, 7.4 g of crystalline 3-pyridineperoxycarboxylic acid methanesulphonate were separated, having a purity of 70.5% (active oxygen content of 4.8% - theoretical value 6.8%) and corresponding to a yield of 60%. The product was purified by keeping it under stirring in anhydrous ethanol (200 ml) for 30 minutes at room temperature. Elemental Analysis : Computed for C₇H₉O₆ NS: C: 35.74%; H: 3.85%;, N: 5.95%; O (active); 6.80%; CH₃SO₃H, 40.85%. Found: C: 35.05%; H: 3.77%; N: 5.85%; O (active); 6.75%; CH₃SO₃H: 40.79%. Melting Point: 90°C (with decomposition). Example 5 By operating according to the procedures of Example 1, 1.49 g (0.01 mole) of the anhydride of 2,3-pyridine-dicarboxylic or quinolinic acid were dissolved into 28 g (0.291 moles) of methanesulphonic acid and then 2.3 g of H₂O₂ at 85% (0.0575 moles) were added, continuing the stirring at 50°C for 2 hours. The reaction mixture was then poured into 500 ml of ethyl acetate according to the procedures of Example 1. By operating as above described, 2 g of crystalline, substantially pure 2-pyridine-carboxy-3-peroxycarboxylic acid methanesulphonate were separated yield : 71%. Elemental Analysis: Computed for C₈H₉O₈NS: C: 34.40%; H: 3.24%; N: 5.0%; O (active); 5.73%; CH₃SO₃H; 34.4%. Found: C: 34.20%; H: 3.34%;, H: 4.86%; O (active); 5.67%; CH₃SO₃H: 34.59%. The product decomposed at 126°C. Example 6 By operating according to the procedures of Example 1, 1.5 g of quinolinic acid (0.0089 moles) were dissolved in 26 g (0.270 moles) of methanesulphonic acid and then 2.5 g of H₂O₂ at 70% (0.0514 moles) were added, continuing then the stirring at 50°C for 4 hours. The reaction mixture was then poured into 500 ml of ethyl acetate by operating according to the procedures of Example 1. By operating then as in Example 5, 1.8 g of crystalline 2-pyridinecarboxy -3-peroxycarboxylic acid methanesulphonate were separated having a purity at 92% (active oxygen content of 5.27%; theoretical computed value for C₈H₉O₈ NS: 5.73%) and corresponding to a yield of 67%. Elemental Analysis : Computed for C₈H₉O₈NS: C: 34.40%; H: 3.24%; N: 4.93%; O (active); 5.72%; CH₃SO₃H, 34.40%. Found: C: 34.06%; H: 3.34%; N: 4.86%; O (active) 5.27%; CH₃SO₃H: 34.59%. Example 7 By operating according to the procedures of Example 1, 2 g (0.0119 moles) of 2,5-pyridine-dicarboxylic acid were dissolved into 34.6 g (0.360 moles) of methanesulphonic acid and 2.7 g of H₂O₂ at 85% (0.0675 moles) were added continuing then the stirring at 47°-48°C for 2 hours. Continuing according to the procedures of Example 1, the reaction mixture was poured into 800 ml of ethyl acetate and 2.9 g of crystalline substantially pure 2-pyridine-carboxy-5-peroxycarboxylic acid methanesulphonate were separated. Yield: 87%. Elemental Analysis : Computed for C₈H₉O₈NS : C: 34.40%; H: 3.24%; N: 5.0%; O (active); 5.73%; CH₃SO₃H, 34.40%. Found: C: 34.21%; H: 3.28%; N: 4.93%; O (active) 5.72%; CH₃SO₃H: 34.70%. Melting Point: 141°C (with decomposition). Example 8 By operating according to the procedures of Example 1, 1.5 g (0.00897 moles) of 3.5-pyridinedicarboxylic acid were dissolved into 26 g (0.270 moles) of methanesulphonic acid and 2.05 g of H₂O₂ at 85% were added, continuing then the stirring at 35°C for 2 1/2 hours. Continuing the reaction according to the procedures of Example 1, the reaction mixture was poured into 600 ml of ethyl acetate and 2.1 g of a crystalline product having an active oxygen content of 9.09% were separated which, in the form of 3,5-pyridine-diperoxycarboxylic acid methanesulphonate, corresponds to a purity of this latter of 83.9%; (theoretical value of the active oxygen computed for C₈H₉O₉ NS: 10.84%) and to a yield of 66.0%. The product decomposed at 87°C. Elemental Analysis C₈H₉O₉ NS: C: 32.54%; H: 3.07%; N: 4.74%; O (active) 10.84%; CH₃SO₃H: 32.5%. Found: C: 32.54%; H: 3.24%; N: 4.74%; O (active); 9.09%; CH₃SO₃H:' 32.80%. Example 9 By operating according to the procedures of Example 1, 1.4 g (0.028 moles) of nicotinic-N-oxide acid were dissolved into 28 g of sulphuric acid at 96% (0.273 moles) and then 4.8 g of H₂O₂ at 85% (0.12 moles) were added, continuing then the stirring at 40°C for 4 hours. Continuing the reaction according to the procedures of Example 1, the reaction mixture was poured into 700 ml of ethyl acetate and 4.4 g of substantially pure 3-pyridine-peroxycarboxylic - N oxide acid sulphate were separated. Elemental Analysis : Computed for C₆H₇O₈NS: C: 28.46%; H: 2.78%; N: 5.53/%; O (active); 6.32%; H₂SO₄: 38.73%. Found: C: 29.06%,; N: 2.91%; N: 5.33%; O (active); 6.31% H₂SO₄, 38.60%. Melting Point: 122°C (with decomposition). Example 10 2.5 g (0.0165 moles) of ethyl isonicotinate were added under stirring at room temperature to 15 g (0.156 moles) of methanesulphonic acid and then, by operating,under conditions such as to not exceed 25° C, 3.3 g of H₂O₂ at 85% (0.0825 moles) were added, The reaction was then continued as in Example 1. 1.2 g of crystalline substantially pure 4-pyridine-peroxycarboxylic acid methanesulphonate were obtained (active oxygen content 6.73%,; theoretical value 6.80%). Yield: 31%. The analysis gave the same results as shown in Example 4. Example 11 By operating according to Example 1, 2 g ( 0.0115 moles) of quinoline-4-carboxylic acid were dissolved into 15 g (0.156 moles) of methanesulphonic acid and then 1.5 g of H₂O₂ at 85% (0.0375 moles) were added, continuing then the stirring at 40°C for 2 1/2 hours. The reaction mixture was then poured into 200 ml of ethyl acetate, according to the procedures of Example 1. By operating as above described, 2.4 g of crystalline quinoline-4-peroxycarboxylic acid methanesulphonate (yellow crystals) having a purity of 95%, and corresponding to a yield of 72%, were obtained. Elemental Analysis : Computed for C₁₁H₁₁O₆ NS: C: 46.31%; H: 3.88%; N: 4.90%; O (active); 5.60%; CH₃SO₃H: 33.68%. Found: C: 46.00%; H: 4.17%; N: 4.35%; O (active); 5.32%; CH₃SO₃H, 33.91%. Melting Point: 102°C (with decomposition). Example 12 By operating according to the procedures of Example 1, 1.6 g (0.0116 moles) of 6-methyl-nicotinic acid were dissolved into 15 g (0.156 moles) of methanesulphonic acid and then 1.5 g of H₂O₂ at 85% (0.0375 moles) were added, continuing then the stirring at 35°C for 3 hours. The reaction mixture was then poured into 200 ml of ethyl acetate, according to the procedures of Example 1. By operating as described above, 1.4 g of crystalline 6-methyl-3-pyridine-peroxycarboxylic acid methanesulphonate having a purity of 95% (active oxygen content of 6.1%) and corresponding to a yield of 46%, were obtained. The product was purified by keeping it under stirring in anhydrous ethanol (15 ml) for 1 hour at room temperature. Elemental Analysis : Computed for C₈H₁₁O₆NS: C: 38.55 %; H: 4.45%; N: 5.62%; O (active): 6.42%; CH₃SO₃H: 38.55%. Found: C: 39.01%; H: 4.66%; N: 5.73%; O (active): 6.42%; CH₃SO₃H: 39.00%. Melting Point: 100°C (with decomposition). Example 13 (Application Example) Bleaching tests were carried out with the novel aromatic N-heterocyclic peroxyacid defined as hydrogen-sulfate of 3-pyridine-peroxycarboxylic acid, as compared to: (a) H 48 (Mg salt of monoperphthalic acid), a commercial peroxyacid known in the detergent art, and manufactured by INTEROX Chemical Ltd., London, U.K. (b) Perborate + perborate activator system, which, as known, develops a peroxyacid (peracetic acid) in situ when both products are dissolved in water and which represents the presently most widely used form for the purpose of obtaining a bleaching action at medium-low temperatures (≦ 60°C) and wherein as the activator, TAED (tetraacetylethylenediamine) was selected, with an amount thereof being used which corresponds to the stoichiometric ratio to the perborate. (c) sodium perborate (NaBO₃.4H₂O) alone. All tests were carried out at the constant temperature of 60°C, with an initial concentration of total active oxygen in the bleaching equal for all products, and equal to 200 mg/1. Process For each test, 500 ml of deionized water, contained in a 1,000 ml flask equipped with a condenser, was heated to a temperature of 60°C and adjusted to a pH value of 9.5 with a few drops of an NaOH solution; then the bleaching product was added with stirring with such amounts thereof being added as shown in the following Table, and immediately thereafter, two cotton specimens of 10 cm x 10 cm stained with standard stains of red wine at EMPA INSTITUTE of St. Gallen (Switzerland), and marked with the "EMPA 114" mark, were added. The system was subsequently kept stirred for 60 minutes and, at the end of this time, the specimens, rinsed under running water, were dried and ironed, and were then submitted to the evaluation of the bleaching effect by means of measurements of whiteness degree by reflectometry. The results are reported in the following Table 1, wherein the data are expressed as Bleaching %, defined as: wherein: A = degree of whiteness (%) of the specimen bleached during the test; B = degree of whiteness (%) of the specimen before the test; C = degree of whiteness (%) of the completely bleached specimen and wherein the degrees of whiteness were measured by means of an Elrepho Zeiss reflectometer, assuming MgO = 100% of whiteness, and using filter N.6 l(λ = 464 nm). The data obtained show that the novel peroxyacid of the present invention has a bleaching power higher than the bleaching power of all the other bleaching agents tested.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, FR, GB, IT, LI, NL, SE Nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids having the formula: wherein R represents a hydrogen atom; a carboxylic group or peroxycarboxylic group; an aryl group selected from C₆H₅- and C₆H₅-CH₂-, the aromatic ring thereof being optionally substituted by one or more groups selected from C₁-C₅-alkoxy, COOH, OH, F, Cl, NO₂ or from C₁-C₁₀-alkyl, optionally substituted by 1 to 3 F and/or Cl atoms; a straight or branched (hetero)alkyl containing an overall number of up to 10 carbon atoms and being optionally substituted by at least one substituent selected from the class consisting of F, Cl, OH, NO₂, (C₁-C₅)-alkoxy groups, or by at least one carboxylic or peroxycarboxylic group; a F atom; a Cl atom; an OH or NO₂ group; or a (C₁-C₅)-alkoxy group; the heteroatoms being selected from N and O; n is a number selected from 0 and 1; m is a number selected from 1, 2 and 3; and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻; and the pyridine ring may in its turn be condensed with at least one further (hetero) aromatic ring to form a quinolinic, isoquinolinic or pyridoindolic group. (Poly)peroxycarboxylic acids according to claim 1, wherein the pyridine ring is a pyridine ring condensed with at least one other (hetero)aromatic ring. A (poly)peroxycarboxylic acid according to any one of claims 1 and 2, i.e. 4-pyridine-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-4-peroxycarborylic acid methanesulphonate, 3-pyridine-peroxycarboxylic acid sulphate and methanesulphonate, 2-pyridine-carboxy-3-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-5-peroxycarboxylic acid methanesulphonate, 3,5-pyridine-diperoxycarboxylic acid methanesulphonate, 3-pyridine-peroxycarboxylic-N-oxide acid sulphate, quinoline-4-peroxycarboxylic acid methanesulphonate, 6-methyl-3-pyridine-peroxycarboxylic acid methanesulphonate. Process for preparing the nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids of any one of claims 1 to 3, characterized in that a substrate selected from a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid and/or its anhydride and/or its alkyl ester corresponding to the desired peroxycarboxylic acid having formula (I) is reacted with concentrated H₂O₂, in a medium selected from concentrated H₂SO₄ and CH₃SO₃H and that the peroxycarboxylic acid (I) is then separated from the reaction mixture by means of the addition of tetrahydrofurane and/or ethyl acetate. Process for preparing the nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids of any one of claims 1 to 3, characterized in that a substrate selected from a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid and/or its anhydride and/or its alkyl ester corresponding to the desired peroxycarboxylic acid having formula (I) is converted to its HSO₄⁻ or CH₃SO₃⁻ salt, said salt is then reacted with H₂O₂ in concentrated H₂SO₄ or CH₃SO₃H, and the thus obtained heterocyclic (poly)peroxycarboxylic acid of formula (I) is then separated by addition of tetrahydrofurane and/or ethyl acetate. Process according to claim 4 or 5, characterized in that the substrate is selected from a straight or branched (C₁-C₅)-alkyl ester of a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid or an anhydride of a nitrogen-containing aromatic heterocyclic dicarboxylic acid corresponding to the desired (poly)peroxycarboxylic acid of formula (I). Process according to any one of claims 4 to 6, characterized in that the substrate is selected from: 4-pyridine-carboxylic acid, 2,4-pyridine-dicarboxylic acid, 3-pyridine-carboxylic acid, 2,3-pyridine-dicarboxylic acid and its anhydride, 2,5-pyridine-dicarboxylic acid, 3,5-pyridine-dicarboxylic acid, 3-pyridine-carboxylic-N-oxide acid, the ethyl ester of 4-pyridine-carboxylic acid, 2,6-dihydroxy-4-pyridine-carboxylic acid, 6-methyl-3-pyridine-carboxylic acid, 2-phenyl-4-quinoline-carboxylic acid, 6-isobutyl-3-pyridine-carboxylic acid, 5-p-tolyl-4-pyridine-carboxylic acid, 5-benzyl-3-pyridine-carboxylic acid, 6-fluoromethyl-3-pyridine-carboxylic acid, 2-p-chloro-phenyl-4-quinoline-carboxylic acid, pyrido-indole-4-carboxylic acid and 5-chloro-4-pyridine-carboxylic acid. Process according to any one of claims 4 to 7, characterized in that the amount of H₂SO₄ or CH₃SO₃H is within the range of from 5 to 30 moles per mole of substrate. Process according to claim 8, characterized in that the amount of H₂SO₄ or CH₃SO₃H is within the range of from 7 to 10 moles per mole of substrate. Process according to any one of claims 4 to 9, characterized in that an amount of hydrogen peroxide is used which is within the range of from 1.4 to 6 moles per mole of substrate. Process according to claim 10, characterized in that an amount of hydrogen peroxide is used which is within the range of from 3 to 4 moles per mole of substrate. Process according to any one of claims 4 to 11, characterized in that the end molar ratio of H₂SO₄ or of CH₃SO₃H to the total H₂O present at reaction end is within the range of from 2.5 to 10. Process according to claim 12, characterized in that the end molar ratio of H₂SO₄ or of CH₃SO₃H to the total H₂O present at reaction end is within the range of from 3 to 7. Process according to any one of claims 4 to 13, characterized in that the amount of tetrahydrofurane and/or of ethyl acetate solvent used is not lower than 4 liters per mole of substrate. Process according to any one of claims 4 to 14, characterized in that the tetrahydrofurane and/or ethyl acetate solvent is added at a temperature not higher than 10 °C. Detergent formulation including as a bleaching agent a heterocyclic aromatic nitrogen-containing (poly)peroxycarboxylic acid of any one of the claims 1 to 3. Claims for the following Contracting State : ES Process for preparing nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids having the formula: wherein R represents a hydrogen atom; a carboxylic group or peroxycarboxylic group; an aryl group selected from C₆H₅- and C₆H₅-CH₂-, the aromatic ring thereof being optionally substituted by one or more groups selected from C₁-C₅-alkoxy, COOH, OH, F, Cl, NO₂ or from C₁-C₁₀-alkyl, optionally substituted by 1 to 3 F and/or Cl atoms; a straight or branched (hetero)alkyl containing an overall number of up to 10 carbon atoms and being optionally substituted by at least one substituent selected from the class consisting of F, Cl, OH, NO₂, (C₁-C₅)-alkoxy groups, or by at least one carboxylic or peroxycarboxylic group; a F atom; a Cl atom; an OH or NO₂ group; or a (C₁-C₅)-alkoxy group; the heteroatoms being selected from N and O; n is a number selected from 0 and 1; m is a number selected from 1, 2 and 3; and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻; and the pyridine ring may in its turn be condensed with at least one further (hetero) aromatic ring to form a quinolinic, isoquinolinic or pyridoindolic group, characterized in that a substrate selected from a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid and/or its anhydride and/or its alkyl ester corresponding to the desired peroxycarboxylic acid having formula (I) is reacted with concentrated H₂O₂, in a medium selected from concentrated H₂SO₄ and CH₃SO₃H and that the peroxycarboxylic acid (I) is then separated from the reaction mixture by means of the addition of tetrahydrofurane and/or ethyl acetate. Process for preparing nitrogen-containing aromatic heterocyclic (poly)peroxycarboxylic acids having the formula: wherein R represents a hydrogen atom; a carboxylic group or peroxycarboxylic group; an aryl group selected from C₆H₅- and C₆H₅-CH₂-, the aromatic ring thereof being optionally substituted by one or more groups selected from C₁-C₅-alkoxy, COOH, OH, F, Cl, NO₂ or from C₁-C₁₀-alkyl, optionally substituted by 1 to 3 F and/or Cl atoms; a straight or branched (hetero)alkyl containing an overall number of up to 10 carbon atoms and being optionally substituted by at least one substituent selected from the class consisting of F, Cl, OH, NO₂, (C₁-C₅)-alkoxy groups, or by at least one carboxylic or peroxycarboxylic group; a F atom; a Cl atom; an OH or NO₂ group; or a (C₁-C₅)-alkoxy group; the heteroatoms being selected from N and O; n is a number selected from 0 and 1; m is a number selected from 1, 2 and 3; and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻; and the pyridine ring may in its turn be condensed with at least one further (hetero) aromatic ring to form a quinolinic, isoquinolinic or pyridoindolic group, characterized in that a substrate selected from a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid and/or its anhydride and/or its alkyl ester corresponidng to the desired peroxycarboxylic acid having formula (I) is converted to its HSO₄⁻ or CH₃SO₃⁻ salt, said salt is then reacted with H₂O₂ in concentrated H₂SO₄ or CH₃SO₃H, and the thus obtained heterocyclic (poly)peroxycarboxylic acid of formula (I) is then separated by addition of tetrahydrofurane and/or ethyl acetate. Process according to any one of the claims 1 and 2, wherein the pyridine ring is a pyridine ring condensed with at least one other (hetero)aromatic ring. Process according to any one of the claims 1 and 2, wherein 4-pyridine-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-4-peroxycarboxylic acid methanesulphonate, 3-pyridine-peroxycarboxylic acid sulphate and methanesulphonate, 2-pyridine-carboxy-3-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-5-peroxacarboxylic acid methanesulphonate, 3,5-pyridine-diperoxycarboxylic acid methanesulphonate, 3-pyridine-peroxycarboxylic-N-oxide acid sulphate, quinoline-4-peroxycarboxylic acid methanesulphonate or 6-methyl-3-pyridine-peroxycarboxylic acid methanesulphonate are prepared. Process according to claim 1 or 2, characterized in that the substrate is selected from a straight or branched (C₁-C₅)-alkyl ester of a nitrogen-containing aromatic heterocyclic (poly)carboxylic acid or an anhydride of a nitrogen-containing aromatic heterocyclic dicarboxylic acid corresponding to the desired (poly)peroxycarboxylic acid of formula (I). Process according to any one of the claims 1 to 5, characterized in that the substrate is selected from: 4-pyridine-carboxylic acid, 2,4-pyridine-dicarboxylic acid, 3-pyridine-carboxylic acid, 2,3-pyridine-dicarboxylic acid and its anhydride, 2,5-pyridine-dicarboxylic acid, 3,5-pyridine-dicarboxylic acid, 3-pyridine-carboxylic acid, 2,6-dihydroxy-4-pyridine-carboxylic acid, 6-methyl-3-pyridine-carboxylic acid, 2-phenyl-4-quinoline-carboxylic acid, 6-isobutyl-3-pyridine-carboxylic acid, 5-p-tolyl-4-pyridine-carboxylic acid, 5-benzyl-3-pyridine-carboxylic acid, 6-fluoromethyl-3-pyridine-carboxylic acid, 2-p-chloro-phenyl-4-quinoline-carboxylic acid, pyrido-indole-4-carboxylic acid and 5-chloro-4-pyridine-carboxylic acid. Process according to any one of the claims 1 to 6, characterized in that the amount of H₂SO₄ or CH₃SO₃H is within the range of from 5 to 30 moles per mole of substrate. Process according to claim 7, characterized in that the amount of H₂SO₄ of CH₃SO₃H is within the range of from 7 to 10 moles per mole of substrate. Process according to any one of the claims 1 to 8, characterized in that an amount of hydrogen peroxide is used which is within the range of from 1.4 to 6 moles per mole of substrate. Process according to claim 9, characterized in that an amount of hydrogen peroxide is used which is within the range of from 3 to 4 moles per mole of substrate. Process according to any one of claims 1 to 10, characterized in that the end molar ratio of H₂SO₄ or of CH₃SO₃H to the total H₂O present at reaction end is within the range of from 2.5 to 10. Process according to claim 11, characterized in that the end molar ratio of H₂SO₄ or of CH₃SO₃H to the total H₂O present at reaction end is within the range of from 3 to 7. Process according to any one of the claims 1 to 12, characterized in that the amount of tetrahydrofurane and/or of ethyl acetate solvent used is not lower than 4 liters per mole of substrate. Process according to any one of the claims 1 to 13, characterized in that the tetrahydrofurane and/or ethyl acetate solvent is added at a temperature not higher than 10°C. Detergent formulation including as a bleaching agent a heterocyclic aromatic nitrogen-containing (poly)peroxycarboxylic acid having the formula: wherein R represents a hydrogen atom; a carboxylic group or peroxycarboxylic group; an aryl group selected from C₆H₅- and C₆H₅-CH₂-, the aromatic ring thereof being optionally substituted by one or more groups selected from C₁-C₅-alkoxy, COOH, OH, F, Cl, NO₂ or from C₁-C₁₀-alkyl, optionally substituted by 1 to 3 F and/or Cl atoms; a straight or branched (hetero)alkyl containing an overall number of up to 10 carbon atoms and being optionally substituted by at least one substituent selected from the class consisting of F, Cl, OH, NO₂, (C₁-C₅)-alkoxy groups, or by at least one carboxylic or peroxycarboxylic group; a F atom; a Cl atom; an OH or NO₂ group; or a (C₁-C₅)-alkoxy group; the heteroatoms being selected from N and O; n is a number selected from 0 and 1; m is a number selected from 1, 2 and 3; and X represents an acidic anion selected from HSO₄⁻ and CH₃SO₃⁻; and the pyridine ring may in its turn be condensed with at least one further (hetero) aromatic ring to form a quinolinic, isoquinolinic or pyridoindolic group. Detergent formulation including as a bleaching agent a heterocyclic aromatic nitrogen-containing (poly)peroxycarboxylic acid as in claim 15, wherein the pyridine ring is a pyridine ring condensed with at least one other (hetero)aromatic ring. Detergent formulation including as a bleaching agent 4-pyridine-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-4-peroxycarboxylic acid methanesulphonate, 3-pyridine-peroxycarboxylic acid sulphate and methanesulphonate, 2-pyridine-carboxy-3-peroxycarboxylic acid methanesulphonate, 2-pyridine-carboxy-5-peroxycarboxylic acid emthanesulphonate, 3,5-pyridine-diperoxycarboxylic acid methanesulphonate, 3-pyridine-peroxycarboxylic-N-oxide acid sulphate, quinoline-4-peroxycarboxylic acid methanesulphonate, 6-methyl-3-pyridine-peroxycarbocylic acid methanesulphonate.

Inventors: CAVALLOTTI CLAUDIO, VENTURELLO CARLO DR, CAVALLOTTI, CLAUDIO, VENTURELLO, CARLO, DR.
Applicants: AUSIMONT SPA, AUSIMONT S.P.A.
Application year: 1988
Main classification: C07D213
IPC codes: C07D213, D06L3, C07D215, C11D7, C11D3