Bleach catalysts

Abstract

The present invention relates to specific acylhydrazone compounds, their use as oxidation catalysts and to a process for removing stains and soil on textiles and hard surfaces. The compounds are substituted with a specific cyclic ammonium group adjacent to the acyl group. Further aspects of the invention are compositions or formulations comprising such compounds.

Claims

1. A method of oxidizing a compound comprising contacting the compound with a catalyst for oxidation reactions wherein the catalyst is at least one compound of formula (1) ##STR00030## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.1-C.sub.28alkoxy, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; or R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are OR.sub.11, NR.sub.11R.sub.12, NO.sub.2 or halogen; or R.sub.1 and R.sub.2, R.sub.2 and R.sub.3 or R.sub.3 and R.sub.4 are linked together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sub.13 and or which may be further fused with other aromatic rings and/or which may be substituted with one or more C.sub.1-C.sub.6akyl groups; R.sub.5 is hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.6 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.7 is a group ##STR00031## each group with an anion A.sup.; k is an integer from 1 to 4; A.sup. is an anion; R.sub.10 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl; R.sub.11, R.sub.12 independently are hydrogen, C.sub.1-C.sub.15alkyl or phenyl; or R.sub.11 and R.sub.12 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further N, O or S atom; and R.sub.13 is hydrogen or C.sub.1-C.sub.18alkyl, together with a peroxide or a peroxide precursor.

2. The method according to claim 1 wherein the at least one compound of formula (1) is further used as catalysts together with O.sub.2and/or air.

3. The method according to claim 1 wherein a bleach activator is present.

4. The method according to claim 1 wherein additionally a metal chelating agent is present.

5. The method according to claim 2 for oxidizing of stains or soiling on textile materials in a washing process or by the direct application of a stain remover or for the cleaning of hard surfaces.

6. The method according to claim 5 wherein a bleach activator is present.

7. The method according to claim 5 wherein additionally a metal chelating agent is present.

8. The method according to claim 6 wherein additionally a metal chelating agent is present.

9. The method of claim 1 wherein, in the compound of formula (1), R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8alkoxy, halogen, OR.sub.11 or NR.sub.11R.sub.12; R.sub.5 is hydrogen or C.sub.1-C.sub.18alkyl; R.sub.6 is hydrogen or C.sub.1-C.sub.18alkyl; R.sub.7 is a group ##STR00032## each group with an anion A.sup.; k is an integer from 1 to 4; A.sup. is Cl.sup., Br.sup., ClO.sub.4.sup., NO.sub.3.sup., HSO.sub.4.sub., BF.sub.4.sup. or PF.sub.6.sup.; R.sub.10 is hydrogen or C.sub.1-C.sub.18alkyl; R.sub.11, R.sub.12 independently are hydrogen, C.sub.1-C.sub.18alkyl or phenyl; and R.sub.13 is hydrogen or C.sub.1-C.sub.4alkyl.

10. The method of claim 1 wherein, in the compound of formula (1), R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, OH, methoxy, halogen or methyl; R.sub.5 is hydrogen or methyl; R.sub.6 is hydrogen or methyl; R.sub.7 is a group ##STR00033## each group with an anion A.sup.; k is an integer from 1 to 2; A.sup. is Cl.sup., Br.sup., ClO.sub.4.sup., NO.sub.3.sup., HSO.sub.4.sub., BF.sub.4.sup. or PF.sub.6.sup.; and R.sub.10 is hydrogen or C.sub.1-C.sub.4alkyl.

11. The method of claim 1 wherein, in the compound of formula (1), R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, OH, or methyl; R.sub.5 is hydrogen; R.sub.6 is hydrogen; R.sub.7 is a group ##STR00034## each group with an anion A.sup.; k is 1; A.sup. is Cl.sup., Br.sup., ClO.sub.4.sup., NO.sub.3.sup., HSO.sub.4.sub., BF.sub.4.sup. or PF.sub.6.sup.; and R.sub.10 is methyl.

12. The method of claim 1 wherein, in the compound of formula (1), R.sub.1, R.sub.2, R.sub.3, R.sub.4 are hydrogen; R.sub.5 is hydrogen; R.sub.6 is hydrogen; R.sub.7 is a group ##STR00035## each group with an anion A.sup.; k is 1; A.sup. is Cl.sup. or Br.sup.; and R.sub.10 is methyl.

13. A method of oxidizing a compound comprising contacting the compound with a catalyst for oxidation reactions wherein the catalyst is at least one compound of formula (1) ##STR00036## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.1-C.sub.28alkoxy, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; or R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are OR.sub.11, NR.sub.11R.sub.12, NO.sub.2 or halogen; or R.sub.1 and R.sub.2, R.sub.2 and R.sub.3 or R.sub.3 and R.sub.4 are linked together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sub.13 and or which may be further fused with other aromatic rings and/or which may be substituted with one or more C.sub.1-C.sub.6akyl groups; R.sub.5 is hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.6 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C .sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C .sub.12cycloheteroalkyl, C.sub.5-C.sub.16mheteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.7 is a group ##STR00037## each group with an anion A.sup.; k is an integer from 1 to 4; A.sup. is an anion; R.sub.10 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl; R.sub.11, R.sub.12 independently are hydrogen, C.sub.1-C.sub.18alkyl or phenyl; or R.sub.11 and R.sub.12 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further N, O or S atom; and R.sub.13 is hydrogen or C.sub.1-C.sub.18alkyl, together with a bleach activator.

14. The method according to claim 13, wherein additionally a metal chelating agent is present.

15. A method of oxidizing a compound comprising contacting the compound with a catalyst for oxidation reactions wherein the catalyst is at least one compound of formula (1) ##STR00038## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.1-C.sub.28alkoxy, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; or R.sub.1, R.sub.2, R.sub.3, R.sub.4 independently from each other are OR.sub.11, NR.sub.11R.sub.12, NO.sub.2 or halogen; or R.sub.1 and R.sub.2, R.sub.2 and R.sub.3 or R.sub.3 and R.sub.4 are linked together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more O, S or NR.sub.13 and or which may be further fused with other aromatic rings and/or which may be substituted with one or more C.sub.1-C.sub.6akyl groups; R.sub.5 is hydrogen, unsubstituted or substituted C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.6 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.4alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy; R.sub.7 is a group ##STR00039## each group with an anion A.sup.; k is an integer from 1 to 4; A.sup. is an anion; R.sub.10 is hydrogen, C.sub.1-C.sub.28alkyl, C.sub.2-C.sub.28alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.9aralkyl, C.sub.3-C.sub.2oheteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.16heteroaralkyl; R.sub.11, R.sub.12 independently are hydrogen, C.sub.1-C.sub.18alkyl or phenyl; or R.sub.11 and R.sub.12 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further N, O or S atom; and R.sub.13 is hydrogen or C.sub.1-C.sub.18alkyl, together with a metal chelating agent.

Description

A) SYNTHESIS EXAMPLES

Example A1

Compound 1A, Precursor

(1) ##STR00018##

ethyl 2-(4-methylmorpholin-4-ium-4-yl)acetate chloride

(2) The title compound is synthesized as described in U.S. Pat. No. 3,398,147.

(3) .sup.1H-NMR (300 MHz, DMSO), [ppm]: 1.25 (t, J=7.2 Hz, 3H), 3.41 (s, 3H), 3.62-3.79 (m, 4H), 3.96-3.99 (m, 4H), 4.24 (q, J=7.2 Hz, 2H), 4.806 (s, 2H).

(4) Compound 101.

(5) ##STR00019##

N-[(2-hydroxyphenyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide chloride

(6) 20.1 g (0.09 mol) of compound 1A are dissolved in 100 ml Ethanol. 9.1 g (0.18 mol) of hydrazine monohydrate are added drop wise at room temperature. A white suspension is obtained at the end of the addition and the reaction mixture is stirred at room temperature for 3 hours. The solid is then quickly filtrated and dried. It is then further suspended in 100 ml ethanol and 11.2 g (0.09 mol) of salicylaldehyde are added drop wise at room temperature. The reaction mixture is stirred at room temperature for 19 hours and is then filtrated. The white solid obtained is dried to give 23.1 g of a mixture of two isomers of compound 101.

(7) .sup.1H-NMR (300 MHz, DMSO), [ppm]: 3.45 (broad s, 3H), 3.60-3.87 (m, 4H), 3.93-4.07 (m, 4H), 4.63 and 4.95 (2 s, 1H), 6.83-7.02 (m, 2H), 7.23-7.33 (m, 1H), 7.60 and 7.79 (2 dd, J.sub.1=1.5 Hz, J.sub.2=7.8 Hz and J.sub.1=1.8 Hz, J.sub.2=8.1 Hz, 1H), 8.42 and 8.64 (2s, 1H), 10.31 and 10.85 (2s, 1H), 12.03 and 13.36 (2s, 1H).

Example A2

Compound 1B, Precursor

(8) ##STR00020##

ethyl 2-(4-methylmorpholin-4-ium-4-yl)acetate bromide

(9) The title compound was synthesized as described in Koumoto, Kazuya; Ochiai, Hirofumi; Sugimoto, Naoki Tetrahedron 2007, 64, 168.

(10) .sup.1H-NMR (300 MHz, DMSO), [ppm]: 1.25 (t, J=7.2 Hz, 3H), 3.40 (s, 3H), 3.60-3.77 (m, 4H), 3.91-4.04 (m, 4H), 4.26 (q, J=7.2 Hz, 2H), 4.74 (s, 2H).

Compound 1C, Precursor

(11) ##STR00021##

2-(4-methylmorpholin-4-ium-4-yl)acetohydrazide bromide

(12) 24.1 g (0.09 mol) of compound 1B are stirred with 100 ml ethanol. 7.7 g (0.15 mol) of hydrazine monohydrate are added drop wise at room temperature. 5 min after the end of the addition, a white solid starts precipitating. The reaction mixture is stirred at room temperature for 5 hours. The solid is then quickly filtrated and dried to give 18.2 g of compound 1C.

(13) .sup.1H-NMR (300 MHz, DMSO), [ppm]: 3.33 (s, 3H), 3.53-3.69 (m, 4H), 3.91-4.00 (m, 4H), 4.21 (s, 2H), 4.54-4.63 (m, 2H), 9.78 (s broad, 1H).

(14) Compound 101B.

(15) ##STR00022##

N-[(2-hydroxyphenyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide bromide

(16) 17.8 g (0.07 mol) of compound 1C are stirred with 100 ml ethanol. 8.7 g (0.07 mol) of salicylaldehyde were added drop wise at room temperature. A thick white suspension is obtained and is stirred at room temperature overnight. The solid is then filtrated and dried to give 23.4 g of a white solid: a mixture of two isomers of compound 101B.

(17) .sup.1H-NMR (300 MHz, DMSO), [ppm]: 3.45 (s, 3H), 3.64-3.87 (m, 4H), 3.94-4.06 (m, 4H), 4.54 and 4.95 (2 s, 1H), 6.85-6.95 (m, 2H), 7.25-7.34 (m, 1H), 7.62 and 7.80 (2 dd, J.sub.1=1.5 Hz, J.sub.2=7.8 Hz and J.sub.1=1.5 Hz, J.sub.2=7.8 Hz, 1H), 8.39 and 8.56 (2s, 1H), 10.08 and 10.75 (broad 2s, 1H), 11.95 and 12.51 (broad 2s, 1H).

(18) Compound 102

(19) ##STR00023##

N-(2-hydroxy-1-naphthyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide chloride

(20) 2-hydroxynaphthaldehyde (98%; 5.08 g, 0.0289 mol) is added at 25 C. to a stirred suspension of 2-(4-methylmorpholin-4-ium-4-yl)acetohydrazide chloride (5.77 g, 0.0275 mol; prepared according to U.S. Pat. No. 3,398,147) in ethanol (50 ml) and the resulting suspension subsequently stirred at 25 C. (overnight) and 50 C. (one hour). The reaction mixture is filtered, the filter cake re-suspended in fresh ethanol (70 ml) and the resulting suspension refluxed (one hour). Warm (45 C.) filtration and drying of the filter cake affords the title compound (7.1 g). Yellow beige solid;

(21) .sup.1H-NMR (400 MHz, DMSO-d.sub.6), [ppm]: 3.48 (s) and 3.50 (s; 3H), 3.65-3.88 (m, 4H), 3.97-4.08 (m, 4H), 4.62 (s) and 5.03 (s; 2H), 7.25-7.27 (m, d-like) and 7.31-7.33 (m, d-like; 1H), 7.37-7.43 (m, 1H), 7.57-7.62 (m, 1H), 7.85-7.87 (m, d-like), 7.89-7.91 (m, d-like) and 7.94-7.96 (m, d-like; 2H), 8.41-8.43 (m, d-like) and 8.80-8.82 (m, d-like; 1H), 8.96 (s) and 9.47 (s; 1H), 10.84 (broad s), 12.07 (broad s), 12.16 (broad s) and 13.54 (broad s; 2H);

(22) LC/MS (pos. ESI), area % (m/z): found 98.6 (328.2). calcd. for C.sub.18H.sub.22N.sub.3O.sub.3: 328.

(23) Elemental analysis (Cl only): found 9.4%. calcd. for C.sub.18ClH.sub.22N.sub.3O.sub.3: 9.7%.

(24) Compound 103

(25) ##STR00024##

N-(2-hydroxy-5-nitro-phenyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide chloride

(26) 2-Hydroxy-5-nitrobenzaldehyde (99%; 5.0 g, 0.0296 mol) is added at 25 C. to a stirred suspension of 2-(4-methylmorpholin-4-ium-4-yl)acetohydrazide chloride (5.91 g, 0.0282 mol; prepared according to U.S. Pat. No. 3,398,147) in ethanol (50 ml) and the resulting suspension subsequently stirred at 25 C. (overnight) and 5 C. (15 minutes). The reaction mixture is filtered and the filter cake dried to afford the title compound (9.9 g). Beige solid;

(27) .sup.1H-NMR (400 MHz, DMSO-d.sub.6), [ppm]: 3.45 (s, 3H), 3.62-3.85 (m, 4H), 3.95-4.06 (m, 4H), 4.59 (s) and 5.01 (s; 2H), 7.21 (d, J=9.1 Hz) and 7.26 (d, J=9.1 Hz; 1H), 8.19 (dd, J=9.1 and 2.9 Hz, 1H), 8.42 (s), 8.57 (d, J=2.9 Hz), 8.59 (d, J=2.9 Hz) and 8.67 (s; 2H), 12.11 (broad s), 12.19 (broad s) and 13.26 (broad s; 2H);

(28) LC/MS (pos. ESI), area % (m/z): found 99.0 (323.2). calcd. for C.sub.14H.sub.19N.sub.4O.sub.5: 323.

(29) Elemental analysis (Cl only): found 9.5%. calcd. for C.sub.14ClH.sub.19N.sub.4O.sub.5: 9.9%.

(30) Compound 104

(31) ##STR00025##

N-(2-hydroxy-5-methoxy-phenyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide chloride

(32) 2-Hydroxy-5-methoxybenzaldehyde (98%; 4.74 g, 0.0305 mol) is added via syringe within two minutes at 25 C. to a stirred suspension of 2-(4-methylmorpholin-4-ium-4-yl)acetohydrazide chloride (6.1 g, 0.0291 mol; prepared according to U.S. Pat. No. 3,398,147) in ethanol (50 ml), resulting in the formation of a voluminous precipitate. The reaction mixture is diluted with ethanol (20 ml) and subsequently stirred at 50 C. (one hour) and 25 C. (overnight). Filtration and drying of the filter cake affords the title compound (9.38 g). Yellowish solid;

(33) .sup.1H-NMR (400 MHz, DMSO-d.sub.6), [ppm]: 3.44 (s, 3H), 3.61-3.62 (m, 1H), 3.69-3.74 (m, 2H), 3.72 (s) and 3.73 (s; 3H), 3.79-3.85 (m, 1H), 3.95-4.05 (m, 4H), 4.58 (broad s) and 4.95 (s; 2H), 6.88-6.94 (m, 2H), 7.15-7.16 (m, d-like) and 7.305-7.310 (m, d-like; 1H), 8.37 (s) and 8.59 (s; 1H), 9.78-9.79 (m, d-like), 10.31 (s), 12.00 (s) and 13.08-13.13 (m, d-like; 2H);

(34) LC/MS (pos. ESI), area % (m/z): found 100.0 (308.2). calcd. for C.sub.15H.sub.22N.sub.3O.sub.4: 308.

(35) Elemental analysis (Cl only): found 10.1%. calcd. for C.sub.15ClH.sub.22N.sub.3O.sub.4: 10.3%.

(36) Compound 105

(37) ##STR00026##

N-(2-hydroxy-3-nitro-phenyl)methyleneamino]-2-(4-methylmorpholin-4-ium-4-yl)acetamide chloride

(38) 2-Hydroxy-3-nitrobenzaldehyde (98%; 4.9 g, 0.0287 mol) is added at 25 C. to a stirred suspension of 2-(4-methylmorpholin-4-ium-4-yl)acetohydrazide chloride (5.73 g, 0.0273 mol; prepared according to U.S. Pat. No. 3,398,147) in ethanol (50 ml). The reaction mixture is brought to 50 C., diluted with ethanol (20 ml), stirred for two hours at 50 C., cooled to 10 C. and filtered. The filter cake is dissolved in refluxing methanol (400 ml), filtered and the clear hot filtrate allowed to cool down. The resulting precipitate is separated off and dried to afford the title compound (7.8 g). Yellow solid;

(39) .sup.1H-NMR (400 MHz, DMSO-d.sub.6), [ppm]: 3.36 (broad s, 1H), 3.45 (s) and 3.46 (s; 3H), 3.62-3.68 (m, 1H), 3.70-3.76 (m, 2H), 3.80-3.86 (m, 1H), 3.95-4.05 (m, 4H), 4.66 (s) and 5.00 (s; 2H), 7.12-7.18 (m, q-like, 1H), 7.97-8.00 (m, dd-like), 8.02-8.05 (m, dd-like), 8.07-8.09 (m, dd-like) and 8.20-8.22 (m, dd-like; 2H), 8.50 (s) and 8.74 (s; 1H), 12.29 (s, 1H);

(40) LC/MS (pos. ESI), area % (m/z): found 100.0 (323.2). calcd. for C.sub.14H.sub.19N.sub.4O.sub.5: 323.

(41) Elemental analysis (Cl only): found 9.0%. calcd. for C.sub.14ClH.sub.19N.sub.4O.sub.5: 9.9%.

(42) Compound 107 (Comparison).

(43) ##STR00027##

[2-[[(2-hydroxyphenyl)methylene]hydrazino]-2-oxo-ethyl]-trimethyl-ammonium chloride

(44) From commercially available (2-hydrazino-2-oxo-ethyl)-trimethyl-ammonium chloride (Girard-T reagent) and salicylaldehyde in ethanol according to the procedure published by V. Leovac et al., Structural Chemistry 2007, 18, 113-119.

B) APPLICATION EXAMPLES (PHOSPHATE CONTAINING DETERGENT)

Application Example B1

Peroxide Bleaching Action in Washing Agents

(45) 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains ECE77 (phosphate builder) standard detergent in a concentration of 4.5 g/l, and 0.92 g/l sodium percarbonate (SPC), 0.176 mg TAED, pH adjusted to pH 10.1. The catalyst concentration is 25 mol/l. The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 30 C. For evaluating the bleaching results, the increase in the lightness DY (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically The higher the Y value, the better the bleach performance

(46) TABLE-US-00001 BC01 BC02 BC03 CS12 No catalyst 10.4 9.4 10.8 49 Reference 15.5 12.9 18.3 51.1 Invention 11.9 9.8 14.2 49.5 Comparison

(47) The results clearly show that compound 101A according to the invention exhibits a significantly higher lightness as compared to the reference compound.

(48) Odor of the Wash Liquors

(49) After the washing experiment the wash liquor containing compound 101A has no scent.

(50) The wash liquor containing the comparative compound 107 exhibits a clear fishy smell, which is highly undesired.

Application Example B2

Peroxide Bleaching, Influence of Sequestrants

(51) 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains AATCC standard detergent in a concentration of 4.5 g/l, and 0.65 g/l sodium percarbonate (SPC), 144 mg TAED, pH adjusted to pH 10.1, tap water. The catalyst concentration is 35 mol/l. The experiments are carried out with 1% active material on weight of detergent of different sequestrants with and without catalyst. Sequestrants used are: citric acid, oxalic acid, methyl-glycine-diacetic acid (MGDA), ethylenediamine-N,N-disuccinic acid (EDDS), 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).

(52) The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 30 C. For evaluating the bleaching results, the increase in the lightness Y (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically. The higher the Y value, the better the bleach performance.

(53) TABLE-US-00002 BC01 BC02 BC03 CS12 TAED Reference 9.0 7.7 8.7 44.3 + EDDS 8.0 6.9 6.9 42.9 + MGDA 8.4 7.3 7.8 42.9 + Oxalic acid 8.5 7 8.2 43.3 + Citic acid 8.4 7.2 7.9 42.5 + HEDP 8.5 7.2 7.6 46.2 + Comp. 101A 13.2 9.5 14.6 43.5 + Comp. 101A + EDDS 15.2 11.6 18.2 49.2 + Comp. 101A + MGDA 15.2 10.7 18.7 47.9 + Comp. 101A + Oxalic acid 14.0 9.6 15.5 44.5 + Comp. 101A + Citric acid 14.9 10.3 17.0 46.5 + Comp. 101A + HEDP 15.1 11.3 17.7 47.6

(54) The results clearly show a synergistic effect of the combination of Comp. 101+sequestrant.

Application Example B3

Peroxide Bleaching, Performance without TAED

(55) 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains AATCC standard detergent in a concentration of 4.3 g/l, and 0.43 g/l sodium percarbonate (SPC), 43 mg HEDP, pH 10.1, tap water. The concentration of Comp. 101 is varied from 7.5-25 M.

(56) Reference 1 contains SPC only, Reference 2 contains SPC+32 mg TAED.

(57) The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 40 C. For evaluating the bleaching results, the increase in the lightness Y (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically. The higher the Y value, the better the bleach performance.

(58) TABLE-US-00003 BC01 BC02 BC03 CS12 Ref. 1 - Det + SPC 9.1 5.9 9.2 43.3 Ref. 2 - Det + SPC + TAED 9.6 7.1 11.3 46.2 Det + SPC + 7.5 M Comp. 101A 10.4 7.2 11.6 46.5 Det + SPC + 10 M Comp. 101A 10.8 7.5 12.1 47.2 Det + SPC + 15 M Comp. 101A 10.9 8.2 13.2 47.9 Det + SPC + 20 M Comp. 101A 11.6 8.6 14.2 48.3 Det + SPC + 25 M Comp. 101A 12.0 8.9 13.7 48.9

(59) The results show that Comp. 101A catalyzes the peroxide bleach and is easily able to exceed the state of the art bleach system SPC/TAED.

Application Example B4, Other Compounds

Peroxide Bleaching, Performance with TAED

(60) 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains AATCC standard detergent in a concentration of 4.7 g/l, and 0.66 g/l sodium percarbonate (SPC), 144 mg/l TAED, 43 mg HEDP, pH 10.1, tap water. The concentration of the different compounds is 20 mol/l.

(61) Reference contains SPC+TAED as bleach system.

(62) The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 30 C. For evaluating the bleaching results, the increase in the lightness Y (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically. The higher the Y value, the better the bleach performance.

(63) TABLE-US-00004 BC01 BC02 BC03 CS12 Reference 8.5 6.9 9.0 46.0 Reference + Comp. 102 12.1 8.8 15.1 47.0 Reference + Comp. 103 10.2 7.5 10.6 47.1 Reference + Comp. 104 10.0 7.1 10.1 45.9 Reference + Comp. 105 9.6 7.0 10.6 48.2

Application Example B5, Other Compounds

Peroxide Bleaching, Performance without TAED

(64) 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains EU base detergent in a concentration of 4.7 g/l, and 0.66 g/l sodium percarbonate (SPC), 43 mg HEDP, pH 10.2, tap water. The concentration of the different compounds is 20 mol/l.

(65) Reference contains SPC as bleach system.

(66) The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 40 C. For evaluating the bleaching results, the increase in the lightness Y (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically. The higher the Y value, the better the bleach performance.

(67) TABLE-US-00005 BC01 BC02 BC03 CS12 Reference 8.1 6.1 8.2 43.4 Reference + Comp. 102 11.7 8.9 15.4 47.8 Reference + Comp. 104 10.7 7.8 12.8 46.1