BLEACH ACTIVATOR WITH A CATIONIC GROUP AND WASHING OR CLEANING AGENT CONTAINING SAID BLEACH ACTIVATOR

Abstract

The oxidizing and bleaching effect of peroxygen compounds at low temperatures was to be improved. This was substantially achieved through the use of organic peroxoacids under perhydrolysis conditions with compounds which form cationic groups and in which a quaternary nitrogen atom is part of a heterocyclic 5-membered functional group.

Claims

1. A bleach-activating compound of general formula (I), ##STR00004## in which A represents O, S, Se; Z represents an optionally substituted C.sub.1-30 alkylene, C.sub.3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene functional group; X.sup.− represents an anion; Y represents NR.sup.8, O, S, Se; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group; and n represents a number in the range from 0 to 12, wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom in the hydrocarbon functional groups.

2. The bleach-activating compound of claim 1, wherein the anion X.sup.− is selected from the group consisting of chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, and phosphate.

3. The bleach-activating compound of claim 1, wherein in the hydrocarbon functional groups 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by N, O, S and/or Se.

4. The bleach-activating compound of claim 1, wherein the compound of general formula (I) corresponds to general formula (II), ##STR00005## in which R, R.sup.9 and R.sup.10 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group, wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom.

5. A method for washing laundry or a method for cleaning hard surfaces, comprising the method steps of (a) providing an aqueous liquor containing H.sub.2O.sub.2 or an inorganic peroxygen compound which provides H.sub.2O.sub.2 in water and a compound according to general formula (I), ##STR00006## in which A represents O, S, Se; Z represents an optionally substituted C.sub.1-30 alkylene, C.sub.3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene functional group; X.sup.− represents an anion; Y represents NR.sup.8, O, S, Se; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group; and n represents a number in the range from 0 to 12; wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom in the hydrocarbon functional groups, and (b) bringing this liquor into contact with a textile to be washed or a hard surface to be cleaned.

6. The method according to claim 5, wherein the anion X.sup.− is selected from the group consisting of chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, and phosphate.

7. The method according to claim 5, wherein in the hydrocarbon functional groups 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by N, O, S and/or Se.

8. The method according to claim 5, wherein the contact between the aqueous liquor and the textile to be washed or the hard surface to be cleaned is made at temperatures in the range of 20° C. to 40° C.

9. The method according to claim 5, wherein the contact between the aqueous liquor and the textile to be washed or the hard surface to be cleaned is made at temperatures in the range of 20° C. to 30° C.

10. The method according to claim 5, wherein the textile to be washed or the hard surface to be cleaned remains in contact with the aqueous liquor over a period of 20 minutes to 120 minutes.

11. The method according to claim 5, wherein the textile to be washed or the hard surface to be cleaned remains in contact with the aqueous liquor over a period of 30 minutes to 90 minutes.

12. The method according to claim 5, wherein the compound of general formula (I) corresponds to general formula (II), ##STR00007## in which R, R.sup.9 and R.sup.10 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group, wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom.

13. The method according to claim 5, wherein the amounts of H.sub.2O.sub.2 or peroxygen compounds are selected such that the liquor includes 10 ppm to 10% active oxygen.

14. The method according to claim 5, wherein the amount of H.sub.2O.sub.2 or peroxygen compounds are selected such that the liquor includes 50 ppm to 5,000 ppm active oxygen.

15. A washing or cleaning agent containing a compound according to general formula (I), ##STR00008## in which A represents O, S, Se; Z represents an optionally substituted C.sub.1-30 alkylene, C.sub.3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene functional group; X.sup.− represents an anion; Y represents NR.sup.8, O, S, Se; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group; and n represents a number in the range from 0 to 12; wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom in the hydrocarbon functional groups.

16. The washing agent or cleaning agent according to claim 15, wherein the anion X.sup.− is selected from the group consisting of chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate, and phosphate.

17. The washing agent or cleaning agent according to claim 15, wherein in the hydrocarbon functional groups 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by N, O, S and/or Se.

18. The washing agent or cleaning agent according to claim 15, wherein the agent includes 0.01 wt. % to 50 wt. %, of the compound according to general formula (I).

19. The washing agent or cleaning agent according to claim 15, wherein the agent includes 0.1 wt. % to 25 wt. % of the compound according to general formula (I).

20. The washing agent or cleaning agent according to claim 15, wherein the compound of general formula (I) corresponds to general formula (II), ##STR00009## in which R, R.sup.9 and R.sup.10 represent, independently of one another, H, a C.sub.1-30 alkyl, C.sub.3-30 cycloalkyl, aryl, alkylaryl or arylalkyl functional group, wherein 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom, in these functional groups.

Description

EXAMPLES

Example 1

Preparation of Bleach-Enhancing Compounds

[0051] a): Preparation of N,N,N-triethyl-N-(4-((2-oxoazepan-1-yl)carbonyl)phenyl) ethanaminium chloride (not according to the invention) (G. Wang, G. de Aragano Umbuzeiro, J. Aparecida Vendemiatti, A. Caloto de Oliveira, F. Inforcato Vacchi, M. Hussain, P. J. Hauser, H. S. Freeman, D. Hinks, J. Surfact. Deterg. 20 (2017), 277-285; S-H. Lim, N. Ç. Gursoy, P. Hauser, D. Hinks, Color. Technol. 120, (2004), 114-118)

[0052] a) i): A solution of 37.6 g of 4-chloromethyl benzoyl chloride (199 mmol) in 20 ml of toluene was added dropwise to a solution, heated to boiling under reflux in an N.sub.2 atmosphere, of 22.5 g of caprolactam (199 mmol) and 30.4 g of triethylamine (1.5 equivalents) in 250 ml of toluene. The reaction mixture was heated to boiling under reflux with stirring for 6 hours, then allowed to cool to room temperature and filtered. The filtrate was stored in the refrigerator for 12 hours, and the precipitate which had separated out was filtered off, washed with 5% strength aqueous NaHCO.sub.3 solution and dried at 40° C. for 12 hours. 47.6 g (179 mmol; 90%) of 1-((4-(chloromethyl)phenyl)carbonyl)azepan-2-one were obtained as a colorless solid. [0053] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=1.85 (bs, 6H), 2.67-2.73 (m, 2H), 3.94-4.01 (m, 2H), 4.59 (s, 2H), 7.41 (pd, J=8.5 Hz, 2H), 7.53 (pd, J=8.5 Hz, 2H) ppm.

[0054] a) ii): A solution of 24.1 g of triethylamine (240 mmol) in 10 ml of acetonitrile was added dropwise in an N.sub.2 atmosphere to a solution of 60 g of ((4-(chloromethyl)phenyl)carbonyl)azepan-2-one (230 mmol), prepared according to a) i), in 350 ml of acetonitrile and the reaction mixture was heated to boiling under reflux with stirring for 4 hours. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60° C. for 1 hour, then the acetone was removed by filtration and the residue was dried. 58.9 g (161 mmol; 72%) of N,N,N-triethyl-N-(4-((2-oxoazepan-1-yl)carbonyl)phenyl)ethanaminium chloride were obtained as a colorless powder. [0055] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=1.37 (t, J=7.2 Hz, 9H), 1.74-1.85 (bs, 6H), 2.60-2.68 (m, 2H), 3.35 (q, J=7.2 Hz, 6H), 3.92 (bs, 2H), 4.82 (s, 2H), 7.47 (pd, J=8, 4 Hz, 2H), 7.63 (pd, J=8.4 Hz, 2H) ppm.

b) Preparation of 1-methyl-3-(4-((2-oxopyrrolidin-1-yl)carbonyl)benzyl)-1H-imidazol-3-ium chloride

[0056] b) i): A solution of 75.6 g of 4-chloromethyl benzoyl chloride (400 mmol) in 50 ml of toluene was added dropwise to a solution, heated to boiling under reflux in an N.sub.2 atmosphere, of 34.0 g of 2-oxopyrrolidin (400 mmol) and 60.7 g of triethylamine (1.5 equivalents) in 250 ml of toluene. The reaction mixture was heated to boiling under reflux with stirring for 6 hours, then allowed to cool to room temperature and filtered. The filtrate was stored in the refrigerator for 12 hours, and the precipitate which had separated out was filtered off, washed with 5% strength aqueous NaHCO.sub.3 solution and dried at 40° C. for 12 hours. 13.8 g (58 mmol; 29%) of 1-((4-(chloromethyl)phenyl)carbonyl)pyrrolidin-2-one were obtained as a colorless solid. [0057] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=1.75-1.95 (m, 4H, CH.sub.2), 3.60-3.80 (m, 2H, CH.sub.2), 4, 81 (s, 2H, CH.sub.2), 7.41-7.49 (m, 2H, Ar—H), 7.51-7.59 (m, 2H, Ar—H) ppm.

[0058] b) ii) A solution of 4.76 g of 1-methylimidazole (57.8 mmol) in 15 ml of acetonitrile was added dropwise in an N.sub.2 atmosphere to a solution of 13.1 g of 1-((4-(chloromethyl)phenyl)carbonyl)pyrrolidin-2-one (55 mmol), prepared according to b) i), in 60 ml of acetonitrile and the reaction mixture was heated to boiling under reflux with stirring for 4 hours. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 20 ml of acetone were added to the residue, the mixture was heated to 50-60° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally, the residue was dried at 40° C. overnight. 16.8 g (52.2 mmol; 95%) of 1-methyl-3-(4-((2-oxopyrrolidin-1-yl)carbonyl)benzyl)-1H-imidazol-3-ium chloride were obtained as colorless solid. [0059] FTIR (film): =3090, 3007, 1740, 1704, 1661, 1562, 1421, 1359, 1303, 1230, 1188, 1174, 1161, 1021, 738, 625, 534 cm.sup.−1. [0060] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=2.04 (tt, J=7.7 Hz, 7.6 Hz, 2H), 2.53 (t, J=7.9 Hz, 2H), 3.81 (t, J=7.1 Hz, 2H), 3.87 (s, 3H), 5.51 (s, 2H), 7.44 (pd, J=8.3 Hz, 2H), 7.59 (pd, J=8.3 Hz, 2H), 7.76 (t, J=1.8 Hz, 1H), 7.85 (t, J=1.8 Hz, 1H), 9.34 (s, 1H) ppm. [0061] .sup.13C-NMR (100.6 MHz, DMSO-d.sub.6): δ=17.0 (t), 32.6 (t), 35.8 (q), 46.0 (t), 51.1 (t), 122.3 (d), 123.9 (d), 127.4 (d, 2C), 129.0 (d, 2C), 135.0 (s), 136.9 (s), 138.0 (d), 169.2 (s), 174.7 (s). [0062] MS (ESI positive mode, +3.5 kV): 284 ([M−Cl.sup.+].sup.+, 100%).

c) Preparation of 1-methyl-3-(4-((2-oxo-1,3-thiazolidin-3-yl)carbonyl)benzyl)-1H-imidazol-3-ium chloride

[0063] c) i): A solution of 75.6 g of 4-chloromethyl benzoyl chloride (400 mmol) in 50 ml of toluene was added dropwise to a solution, heated to boiling under reflux in an N.sub.2 atmosphere, of 41.3 g of 1,3,thiazolidin-2-one (200 mmol) and 60.7 g of triethylamine (1.5 equivalents) in 450 ml of toluene. The reaction mixture was heated to boiling under reflux with stirring for 6 hours, then allowed to cool to room temperature and filtered. The filtrate was stored in the refrigerator for 12 hours, and the precipitate which had separated out was filtered off, washed with 5% strength aqueous NaHCO.sub.3 solution and dried at 40° C. for 12 hours. 37.6 g (147 mmol; 51%) of 3-((4-(chloromethyl)phenyl)carbonyl)-1,3-thiazolidin-2-one were obtained as a colorless solid. [0064] FTIR (film): =2949, 2892, 1703, 1670, 1611, 1357, 1290, 1224, 1153, 1018, 965, 848, 800, 765, 722, 671, 651, 479 cm.sup.−1. [0065] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.39 (t, J=7.0 Hz, 2H), 4.23 (t, J=7.0 Hz, 2H), 4.60 (s, 2H), 7.43 (pd, J=8.1 Hz, 2H), 7.62 (pd, J=8.5 Hz, 2H) ppm. [0066] .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): δ=25.8 (t), 45.4 (t), 48.3 (t), 128.0 (d, 2C), 129.4 (d, 2C), 133.5 (s), 141.5 (s), 169.1 (s), 172.3 (s).

[0067] c) ii) A solution of 23.8 g of 1-methylimidazole (290 mmol) in 20 ml of acetonitrile was added dropwise in an N.sub.2 atmosphere to a solution of 37.2 g of 3-((4-(chloromethyl)phenyl)carbonyl)-1,3-thiazolidin-2-one (145 mmol), prepared according to c) i), in 200 ml of acetonitrile and the reaction mixture was heated to boiling under reflux with stirring for 4 hours. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally, the residue was dried at 40° C. overnight. 37.2 g (110 mmol; 76%) of 1-methyl-3-(4-((2-oxo-1,3-thiazolidin-3-yl)carbonyl)benzyl)-1H-imidazol-3-ium chloride were obtained as a colorless solid. [0068] FTIR (film): >=3149, 3006, 2944, 2852, 1779, 1697, 1668, 1306, 1284, 1228, 1156, 964, 844, 807, 735, 684, 624, 613, 470 cm.sup.−1. [0069] .sup.1H-NMR (400 MHz, D.sub.2O): δ=3.52 (t, J=7.1 Hz, 2H), 3.97 (s, 3H), 4.27 (t, J=7, 1 Hz, 2H), 5.51 (s, 2H), 7.52 (pd, J=8.4 Hz, 2H), 7.55 (s, 2H), 7.70 (pd, J=8, 4 Hz, 2H), 8.90 (s, 1H) ppm. [0070] .sup.13C-NMR (D.sub.2O, 100.6 MHz): δ=28.6 (t), 38.6 (q), 51.5 (t), 54.9 (t), 125.1 (d), 126.7 (d), 131.0 (d, 2C), 132.1 (d, 2C), 136.9 (s), 139.8 (s), 140.7 (s), 173, 2 (s), 179.1 (s) ppm. [0071] MS (ESI positive mode, +3.5 kV): 302 ([M−Cl.sup.−].sup.+, 100%).

Example 2

Decolorizing Test

[0072] 98 mg of sodium percarbonate and 13.1 mg of TAED or one of the compounds prepared in Examples 1 a), 1 b) and 1 c) were added to a solution, adjusted to pH 10-11 by the addition of NaOH, of 2.5 mg morin in 100 ml of water and stirred at room temperature. The time taken for the yellow color to completely disappear was determined and is shown in Table 1.

TABLE-US-00001 TABLE 1 Time until complete decolorizing Active Duration ingredient [minute] TAED 210 Compound from 130 Example 1 b) Compound from 110 Example 1 c) Compound from 270 Example 1 a)

Example 3

Washing Attempts

[0073] Washing tests were carried out at 30° C. with standardized stains on cotton specified in Table 3, using a washing liquor with 3.8 g/l each of a solid washing agent of the composition specified in Table 2 below, agents M1 and M2 being the compounds according to the invention prepared in Examples 1 b) and c); for comparison, agent V2 contained the non-inventive compound from Example 1 a), and agent V1 did not contain such a compound, but rather the conventional bleach activator TAED. The evaluation was carried out by measuring the color distance according to the L*a*b* values and the Y values calculated therefrom as a measure of the brightness. Table 3 shows the differences in the Y values that resulted after washing between V1 and M1, V1 and M2, and V1 and V2.

TABLE-US-00002 TABLE 2 Composition (wt. %) V1 M1 M2 V2 Na alkylbenzene sulfonate 13 13 13 13 Na fatty alcohol sulfate 3 3 3 3 Na carboxymethylcellulose 3 3 3 3 HEDP-Na4 1 1 1 1 Na polyacrylate 3 3 3 3 Sodium silicate 7 7 7 7 Sodium carbonate 21 21 21 21 Sodium hydrogen carbonate 10 10 10 10 Sodium percarbonate 12 12 12 12 TAED 3.1 — — — Compound from Example 1 b) — 3.1 — — Compound from Example 1 c) — — 3.1 — Compound from Example 1 a) — — — 3.1 Water, sodium sulfate, perfume, dye to make up to 100

TABLE-US-00003 TABLE 3 ΔY values Stain/agent M1 M2 V2 Red wine 5.9 5.8 4.5 Coffee 4.0 2.4 ND Beetroot 2.8 3.0 ND Apple 2.3 1.7 1.0 Blackcurrant 1.2 3.4 ND Cherry juice 2.6 2.7 1.9 [0074] ND: not determined [0075] The brightness values when the active ingredients essential to the invention are used are greater than those which result when the washing agents containing other bleach activators are used.

Example 4

Cleaning Tests

[0076] 0.5 g of a mixture of lactose and ovalbumin (weight ratio 3:1) was stirred in 10 ml of water at room temperature for 10 minutes, then the mixture was freeze-dried, ground in a mortar and heated to 160° C. for 20 minutes. Mixtures of 15 mg in each case of the burnt-on food residue-simulating dirt obtained in this way, 3.75 mg of sodium percarbonate and 0.5 mg of a compound prepared in Example 1 b) or 1 c) in 5 ml of water were heated to 60° C. for 48 hours in a mechanical shaker. After the durations given in Table 4, the dissolution of the artificial dirt was visually evaluated and rated on a scale from 0 (no dissolution) to ++++ (completely dissolved).

TABLE-US-00004 TABLE 4 Dissolving burnt-on dirt Active ingredient/ duration 0.5 h 1 h 2 h 4 h 6 h 24 h 48 h None 0 0 0 0 0 0 0 Compound from + + ++ +++ +++ +++ ++++ Example 1 b) Compound from 0 0 + + + + ++ Example 1 c)