Metal free bleaching composition

Abstract

The present invention relates to the use of a composition comprising specific a-amino-ketones, H.sub.2O.sub.2, a H.sub.2O.sub.2 precursor or a peracid and optionally an activator as a bleaching mixture for textile materials or dishes either manually or in an automatic washing machine or dish washer. Further aspects of the invention are the composition comprising specific a-aminoketones and H.sub.2O.sub.2, a H.sub.2O.sub.2 precursor or a peracid and a process for bleaching of stains or of soiling on textile materials or dishes in the context of a washing process either manually or in an automatic washing machine or dish washer. Also aspects of the invention are detergent formulations comprising such a composition and novel compounds.

Claims

1. A process for the bleaching of stains or of soiling on textile materials or dishes in the context of a washing process or by the direct application of a stain remover comprising treating a textile material or dishes in an aqueous medium either by hand or in an automatic washing machine or dishwasher, at a pH between 7 and 11, together with a mixture comprising a) H.sub.2O.sub.2, a precursor of H.sub.2O.sub.2, or a peracid and b) a compound of formula (3) ##STR00137## wherein R.sub.1 is SCH.sub.3, S(O.sub.2)CH.sub.3, H, CH.sub.3, S(O)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup.; or a compound of formula (4) ##STR00138## wherein R.sub.1 is H, CH.sub.3, SCH.sub.3, S(O)CH.sub.3 , S(O.sub.2)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup.; or a compound of formula (5) ##STR00139## wherein R.sub.1 is SCH.sub.3, S(O.sub.2)CH.sub.3, H, CH.sub.3, S(O)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup.; or a compound of formula (6) ##STR00140## wherein R.sub.1 =SCH.sub.3, S(O)CH.sub.3, S(O.sub.2)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup.; or a compound of formula (7) ##STR00141## wherein R.sub.1 =H, S(O)CH.sub.3, S(O.sub.2)CH.sub.3, (CH.sub.3)(CH.sub.3CH.sub.2)S.sup.+BF.sub.4.sup., (CH.sub.3).sub.2S.sup.+BF.sub.4.sup., (CH.sub.3).sub.2S.sup.+PF.sub.6.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup.; wherein the mixture is free of metal complexes, and wherein component a) is present in an amount of from 2 parts to 90 parts by weight and component b) is present in an amount of from 0.02 parts to 20 parts by weight; the sum being 100 parts.

2. The process according to claim 1 wherein component a) comprises a precursor of H.sub.2O.sub.2 and a bleach activator.

3. The process according to claim 1 wherein component b) is a compound of formula (3) ##STR00142## wherein R.sub.1 is SCH.sub.3, S(O.sub.2)CH.sub.3, H, CH.sub.3, S(O)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup..

4. The process according to claim 1 wherein component b is a compound of formula (4) ##STR00143## wherein R.sub.1 is H, CH.sub.3, SCH.sub.3, S(O)CH.sub.3 , S(O.sub.2)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup..

5. The process according to claim 1 wherein component b is a compound of formula (5) ##STR00144## wherein R.sub.1 is SCH.sub.3, S(O.sub.2)CH.sub.3, H, CH.sub.3, S(O)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup..

6. The process according to claim 1 wherein component b is a compound of formula (6) ##STR00145## wherein R.sub.1 =SCH.sub.3, S(O)CH.sub.3, S(O.sub.2)CH.sub.3, (CH.sub.3).sub.2S.sup.+BF.sub.4.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup..

7. The process according to claim 1 wherein component b is a compound of formula (7) ##STR00146## wherein R.sub.1 =H, S(O)CH.sub.3, S(O.sub.2)CH.sub.3, (CH.sub.3)(CH.sub.3CH.sub.2)S.sup.+BF.sub.4.sup., (CH.sub.3).sub.2S.sup.+BF.sub.4.sup., (CH.sub.3).sub.2S.sup.+PF.sub.6.sup. or (CH.sub.3).sub.2S.sup.+(CH.sub.3O)S(O.sub.2)O.sup..

Description

PREPARATION EXAMPLES

(1) Compound 1

(2) 2-Methyl-1-(4-methylsulfanylphenyl)-2-morpholino-propan-1-one: The title compound is commercially available under the trade name Irgacure 907 [CAS 71868-10-5].

(3) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.53 (s, 3H), 2.56-2.59 (m, 4H), 3.68-3.71 (m, 4H), 7.21-7.24 (m, d-like, 2H), 8.50-8.53 (m, d-like, 2H).

(4) Compound 2

(5) 2-Methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ium-4-yl-propan-1-one tetrafluoroborate: Tetrafluoroboric acid (54% in diethyl ether; 1.47 g, 9 mmol) is slowly added to an ice-cooled solution of 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholino-propan-1-one (2.29 g, 8.2 mmol) in diethyl ether (65 ml). The resulting suspension is stirred for two hours and then filtered. The filter cake is washed with diethyl ether and dried to afford the title compound as a white solid (3 g).

(6) .sup.1H-NMR (300 MHz, CD.sub.3OD), [ppm]: 1.75 (broad s, 6H), 2.46 (s, 3H), 3.21 (broad s, 4H), 3.85 (broad s, 2H), 4.00 (broad s, 2H), 7.27-7.29 (m, d-like, 2H), 7.86 (broad s, 2H).

(7) Compound 3

(8) 2-Methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ium-4-yl-propan-1-one chloride: Hydrochloric acid (32% in water; 0.57 g, 5 mmol) is added to a warm solution of 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholino-propan-1-one (1.4 g, 5 mmol) in n-propanol (15 ml). The resulting mixture is stirred one hour and then concentrated on a rotary evaporator to afford the title compound as a white solid (1.58 g).

(9) .sup.1H-NMR (300 MHz, DMSO-d.sub.6), [ppm]: 1.83 (broad s, 6H), 2.55 (s, 3H), 3.33 (broad s, 4H), 4.01 (broad s, 4H), 7.36-7.39 (m, d-like, 2H), 7.90 (broad s, 2H), 10.73 (broad s, 1H).

(10) Compound 4

(11) 1-(4-Butylsulfanylphenyl)-2-methyl-2-morpholino-propan-1-one: The title compound is synthesized according to the published procedure (EP 88050 A2).

(12) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.97 (t, J=7.35 Hz; 3H), 1.32 (s, 6H), 1.46-1.55 (m, 2H), 1.68-1.75 (m, 2H), 2.57-2.60 (m, 4H), 3.00-3.03 (m, t-like, 2H), 3.69-3.72 (m, 4H), 7.25-7.27 (m, d-like, 2H), 8.49-8.51 (m, d-like, 2H).

(13) GLC/MS (pos. CI), m/z (%): found 322.12 (100); calcd. for C.sub.18H.sub.27NO.sub.2S: 321.

(14) Compound 5

(15) 2-Methyl-1-(4-methylsulfinylphenyl)-2-morpholino-propan-1-one: 3-Chloroper-oxybenzoic acid (70%; 0.84 g, 3.41 mmol), dissolved in dichloromethane (10 ml), is slowly added to an ice-cooled solution of 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholino-propan-1-one (0.95 g, 3.4 mmol) in dichloromethane (10 ml). The reaction mixture is stirred for 2.5 hours and then filtered. The filtrate is washed with sodium hydroxide (2 mol/L in water), the organic phase separated off and the solvent evaporated on a rotary evaporator to afford the title compound as slightly yellow oil which solidified upon storage in a refrigerator (1.06 g).

(16) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.33 (s, 6H), 2.57-2.60 (m, 4H), 2.77 (s, 3H), 3.68-3.71 (m, 4H), 7.68-7.71 (m, d-like, 2H), 8.68-8.71 (m, d-like, 2H).

(17) LC/MS (pos. APCI), m/z (area %): found 296.0 (99); calcd. for C.sub.15H.sub.21NO.sub.3S: 295.

(18) Compound 6

(19) 2-Methyl-1-(4-methylsulfonylphenyl)-2-morpholino-propan-1-one: 1-(4-Fluoro-phenyl)-2-methyl-2-morpholin-4-yl-propan-1-one (prepared according to DE19753655; 5 g, 19.9 mmol) is dissolved in DMSO (25 ml) followed by the addition of sodium methanesulfinate (12.08 g, 118.3 mmol). The reaction mixture is brought to 140 C. and stirred for 30 hours, affording an orange suspension. The mixture is poured on toluene/water, the organic phase separated off, washed with water, dried over magnesium sulfate and the solvent evaporated under reduced pressure to yield a solid (5.5 g). Re-crystallization from methanol afforded the title compound (4.4 g).

(20) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.33 (s, 6H), 2.57-2.60 (m, 4H), 3.09 (s, 3H), 3.69-3.72 (m, 4H), 7.98-8.01 (m, d-like, 2H), 8.69-8.72 (m, d-like, 2H).

(21) GLC/MS (pos. CI), m/z (%): found 312 (100); calcd. for C.sub.15H.sub.21NO.sub.4S: 311.

(22) Compound 7

(23) 2-Methyl-2-morpholino-1-phenyl-propan-1-one: The title compound is synthesized according to the published procedure (Calvin L. Stevens, Charles Hung Chang J. Org. Chem. 1962, 27, 4392).

(24) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.35 (s, 6H), 2.60-2.62 (m, 4H), 3.71-3.73 (m, 4H), 7.41-7.45 (m, 2H), 7.52-7.56 (m, 1H), 8.55 (m, d-like, 2H).

(25) GLC/MS (pos. CI), m/z (%): found 234.04 (100); calcd. for C.sub.14H.sub.19NO.sub.2: 233.

(26) Compound 8

(27) 2-[4-(2-Methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfanylacetic acid chloride: A solution of methyl 2-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfanylacetate (prepared as described below; 1.15 g, 3.4 mmol) in hydrochloric acid (2 mol/L in water; 10 g) is stirred at 25 C. overnight. The reaction mixture is filtered and the filtrate extracted with diethylether. The aqueous phase is separated off and concentrated on a rotary evaporator to afford the title compound as a yellow solid (1.2 g).

(28) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 1.75 (s, 6H), 3.28-3.37 (m, 4H), 3.88 (s, 2H), 3.91-3.97 (m, 2H), 4.08-4.12 (m, 2H), 7.34-7.37 (m, d-like, 2H), 7.75-7.78 (m, d-like, 2H).

(29) LC/MS (pos. APCI), m/z (area %): found 324.15 (83); calcd. for C.sub.16H.sub.21NO.sub.4SxH.sup.+: 324.

(30) Methyl 2-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfanylacetate: N,N-Diisopropylethylamine (98%; 1.27 g, 9.6 mmol), methyl mercaptoacetate (99%; 0.47 g, 4.38 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.2 g, 0.22 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (97%; 0.25 g, 0.42 mmol) were added to a solution of 1-(4-bromophenyl)-2-methyl-2-morpholino-propan-1-one (prepared as described below; 1.36 g, 4.36 mmol) in 1,4-dioxane (9 ml). The solution is brought to reflux and stirred for 21 hours. The reaction mixture is cooled to 25 C., diluted with diethylether and then extracted with hydrochloric acid (2 mol/L in water). The aqueous phase is separated off, cooled with ice and then basified by slow addition of sodium hydroxide (2 mol/L in water). The precipitate is filtered off, the filter cake washed with water and dried in a vacuum oven. The resulting solid is washed with diethylether to afford, after drying, the title compound as an orange solid (1.2 g).

(31) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.55-2.58 (m, 4H), 3.67-3.70 (m, 4H), 3.75 (s, 2H), 3.76 (s, 3H), 7.32-7.35 (m, d-like, 2H), 8.49-8.52 (m, d-like, 2H).

(32) GLC/MS (pos. CI), m/z (%): found 338.09 (100); calcd. for C.sub.17H.sub.23NO.sub.4S: 337.

(33) 1-(4-Bromophenyl)-2-methyl-2-morpholino-propan-1-one: 2-(4-Bromo-phenyl)-2-methoxy-3,3-dimethyl-oxirane (prepared as described below; 192 g, 0.75 mol) is added to morpholine (203 g, 2.33 mol). The resulting mixture is brought to 130 C. and stirred for 21 hours. The reaction mixture is evaporated under reduced pressure to afford a dark red oil (228 g) which is taken up in toluene (200 ml), filtered and washed with HCl (16% in water). The organic phase is separated off and the solvent evaporated under reduced pressure to afford the title compound (154 g).

(34) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 1.31 (s, 6H), 2.55-2.58 (m, 4H), 3.67-3.70 (m, 4H), 7.54-7.57 (m, d-like, 2H), 8.43-8.46 (m, d-like, 2H).

(35) GLC/MS (pos. CI), m/z (%): found 312 (100), 314 (ca. 95); calcd. for C.sub.14H.sub.18(.sup.79Br)NO.sub.2: 311, for C.sub.14H.sub.18(.sup.81Br)NO.sub.2: 313.

(36) 2-(4-Bromophenyl)-2-methoxy-3,3-dimethyl-oxirane: 2-Bromo-1-(4-bromo-phenyl)-2-methyl-propan-1-one (prepared as described below; 208 g, 0.68 mol), dissolved in a mixture of chlorobenzene (180 ml) and methanol (100 ml), is slowly added to sodium methylate (30% in methanol; 125 g, 0.69 mol) while keeping the reaction temperature below 20 C. After 1.5 hours, precipitated sodium bromide is filtered off and the filtrate evaporated under reduced pressure to afford the title compound (192 g) which is used without further purification.

(37) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 1.00 (s, 3H), 1.53 (s, 3H), 3.20 (s, 3H), 7.16-7.35 (m, 2H; additional signals due to the presence of residual chlorobenzene), 7.52 (d, J=9 Hz, 2H).

(38) 2-Bromo-1-(4-bromophenyl)-2-methyl-propan-1-one: 1-(4-bromophenyl)-2-methyl-propan-1-one (prepared according to Gonzalo Blay et al, Tetrahedron 2001, 57, 1075) is brominated in chlorobenzene with bromine (1 eq) in the presence of chlorosulfonic acid at room temperature. The title compound is obtained as a yellow oil (208 g; still containing some chlorobenzene) and is used without further purification.

(39) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 2.02 (s, 6H), 7.27-7.34 (m, chlorobenzene), 7.58 (d, J=9 Hz, 2H), 8.03 (d, J=9 Hz, 2H).

(40) Compound 9

(41) 1-[4-(2-Hydroxyethylsulfanyl)phenyl]-2-methyl-2-morpholino-propan-1-one: The title compound is synthesized according to the published procedure (EP88050 A2).

(42) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.55-2.59 (m, 4H), 3.20-3.24 (m, t-like, 2H), 3.68-3.71 (m, 4H), 3.83-3.87 (m, t-like, 2H), 7.32-7.34 (m, d-like, 2H), 8.49-8.52 (m, d-like, 2H).

(43) GLC/MS (pos. CI), m/z (%): found 310 (100); calcd. for C.sub.16H.sub.23NO.sub.3S: 309.

(44) Compound 10

(45) 1-[4-(2-Hydroxyethylsulfinyl)phenyl]-2-methyl-2-morpholino-propan-1-one: The title compound is synthesized from compound 9 according to the procedure described for the preparation of compound 5.

(46) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.33 (s, 3H), 1.34 (s, 3H), 2.57-2.60 (m, 4H), 2.87-2.94 (m, 1H), 3.07 (ca., broad s, 1H), 3.20-3.29 (m, 1H), 3.68-3.72 (m, 4H), 4.03-4.10 (m, 1H), 4.16-4.24 (m, 1H), 7.68-7.71 (m, d-like, 2H), 8.69-8.72 (m, d-like, 2H).

(47) GLC/MS (pos. CI), m/z (%): found 326 (100); calcd. for C.sub.16H.sub.23NO.sub.4S: 325.

(48) Compound 11

(49) 1-[4-(2-Hydroxyethoxy)phenyl]-2-methyl-2-morpholino-propan-1-one: The title compound is synthesized according to the published procedure (WO9621167 and EP88050).

(50) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.04 (ca., broad s, 1H), 2.56-2.59 (m, 4H), 3.68-3.71 (m, 4H), 3.98-4.01 (m, t-like, 2H), 4.14-4.17 (m, t-like, 2H), 6.90-6.93 (m, d-like, 2H), 8.58-8.61 (m, d-like, 2H).

(51) GLC/MS (pos. CI), m/z (%): found 294.04 (100); calcd. for C.sub.16H.sub.23NO.sub.4: 293.

(52) Compound 12

(53) 3-[4-(2-methyl-2-morpholino-propanoyl)phenyl]propanoic acid: The title compound is prepared by hydrolysis of methyl 3-[4-(2-methyl-2-morpholino-propanoyl)phenyl]propanoate (prepared as described below).

(54) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.56-2.59 (m, 4H), 2.69-2.74 (m, t-like, 2H), 2.98-3.03 (m, t-like, 2H), 3.68-3.71 (m, 4H), 5.84 (ca., broad s, 1H), 7.24-7.27 (m, d-like, 2H), 8.47-8.50 (m, d-like, 2H).

(55) MS (pos. APCI), m/z (%): found 306.13 (100); calcd. C.sub.17H.sub.23NO.sub.4: 305.

(56) 3-[4-(2-methyl-2-morpholino-propanoyl)phenyl]propanoate: The title compound is prepared according to the method described for the preparation of 1-(4-bromophenyl)-2-methyl-2-morpholino-propan-1-one from bromobenzene, but using ethyl 3-phenylpropanoate instead.

(57) Compound 13

(58) ##STR00024##

(59) Ethyl-methyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium tetrafluoroborate: Triethyloxonium tetrafluoroborate (97%; 0.45 g, 0.0023 mol), dissolved in dichloromethane (2 ml), is slowly added to a solution of 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholinopropan-1-one (0.73 g, 0.0026 mol) in dichloromethane (6 ml) and the reaction mixture kept stirring for 5 hours at 25 C. Methanol (5 drops) is added and the resulting solution evaporated to dryness. The oily residue (1.2 g) is dissolved in acetone and then slowly added to stirred diethylether. Supernatants are decanted off and the precipitated oil dried on an oil pump to afford the title compound as a yellow solid (assay 90% by .sup.1H-NMR; 1.0 g).

(60) .sup.1H-NMR (300 MHz, CD.sub.3CN), [ppm]: 1.30-1.35 (m, t-like, 3H), 1.33 (s, 6H), 2.56 (broad s, 4H), 3.20 (s, 3H), 3.52-3.70 (m, 2H), 3.64 (broad s, 4H), 7.95-7.97 (m, d-like, 2H), 8.71-8.73 (m, d-like, 2H);

(61) MS (pos./neg. ESI), m/z (%): found 308.1 (100)/87.0 (100); calcd. for [C.sub.17H.sub.26NO.sub.2S].sup.+/[BF.sub.4].sup.: 308/87.

(62) Compound 14

(63) ##STR00025##

(64) 2-(Bis(2-methoxyethyl)amino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and bis(2-methoxyethyl)amine (6.4 equivalents) according to the preparation of compound 21 (160 C., 50 hours). Yellow liquid;

(65) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.30 (s, 6H), 2.50 (s, 3H), 2.70-2.74 (m, t-like, 4H), 3.27 (s, 6H), 3.35-3.37 (m, t-like, 4H), 7.17-7.21 (m, d-like, 2H), 8.42-8.45 (m, d-like, 2H);

(66) MS (CI), m/z (%): found 326 (100; MH.sup.+); calcd. for C.sub.17H.sub.27NO.sub.3S: 325.

(67) Compound 15

(68) ##STR00026##

(69) 2-Dimethylamino-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and dimethylamine (4 equivalents) according to the preparation of compound 21 (150 C., 24 hours). Yellow liquid;

(70) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.28 (s, 6H), 2.27 (s, 6H), 2.52 (s, 3H), 7.20-7.22 (m, d-like, 2H), 8.45-8.48 (m, d-like, 2H);

(71) MS (CI), m/z (%): found 238 (100; MH.sup.+); calcd. for C.sub.13H.sub.19NOS: 237.

(72) Compound 16

(73) ##STR00027##

(74) 2-(Dibutylamino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and dibutylamine (4 equivalents) according to the preparation of compound 21 (ambient pressure, reflux, 160 hours). Yellow liquid;

(75) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: (ca.) 0.8-0.85 (m, t-like, 6H), 1.15-1.22 (m, 4H), 1.3 (s, 6H), 1.4-1.5 (m, 4H), 2.4-2.47 (m, 4H), 2.5 (s, 3H), 7.21-7.25 (m, d-like, 2H), 8.45-8.51 (m, d-like, 2H);

(76) MS (CI), m/z (%): found 322 (100; MH.sup.+); calcd. for C.sub.19H.sub.31NOS: 321.

(77) Compound 17

(78) ##STR00028##

(79) 2-Diethylamino-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and dietylamine (4 equivalents) according to the preparation of compound 21 (150 C., 15 hours). Orange liquid;

(80) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.04-1.09 (m, t-like, 6H), 1.33 (s, 6H), 2.54 (s, 3H), 2.54-2.62 (m, q-like, 4H), 7.21-7.24 (m, d-like, 2H), 8.54-8.57 (m, d-like, 2H);

(81) MS (CI), m/z (%): found 266 (100; MH.sup.+); calcd. for C.sub.15H.sub.23NOS: 265.

(82) Compound 18

(83) ##STR00029##

(84) c) (4-Methylsulfanylphenyl)-(1-morpholinocyclohexyl)methanone: The title compound is prepared from 1-methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane (prepared as described below) and morpholine (4 equivalents) according to the preparation of compound 21 (ambient pressure, reflux, 96 hours). Yellowish solid;

(85) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.04-1.34 (m, 3H), 1.50-1.63 (m, 5H), 2.19-2.23 (m, 2H), 2.53 (s, 3H), 2.67-2.70 (m, 4H), 3.71-3.74 (m, 4H), 7.21-7.24 (m, d-like, 2H), 8.32-8.35 (m, d-like, 2H);

(86) MS (CI), m/z (%): found 320 (100; MH.sup.+); calcd. for C.sub.18H.sub.25NO.sub.2S: 319.

(87) b) 1-methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane: Sodium methoxide (30% in methanol; 19.8 g, 0.11 mol) is slowly added to a solution of (1-bromocyclohexyl)-(4-methylsulfanylphenyl)methanone (prepared as described below; 98%, 31.9 g, 0.1 mol) in methanol (15 ml) and the reaction mixture stirred overnight at 25 C. Toluene and water are added, the organic phase split off and washed with water. Evaporation of the organic phase affords the title compound (25.6 g). Yellowish liquid;

(88) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.14-1.34 (m, 3H), 1.39-1.68 (m, 4H), 1.76-1.88 (m, 2H), 1.94-2.01 (m, 1H), 2.52 (s, 3H), 3.21 (s, 3H), 7.25-7.28 (m, d-like, 2H), 7.39-7.41 (m, d-like, 2H);

(89) MS (CI), m/z (%): found 265 (80; MH.sup.+); calcd. for C.sub.15H.sub.20O.sub.2S: 264.

(90) a) (1-Bromocyclohexyl)-(4-methylsulfanylphenyl)methanone: Bromine (99%; 43.1 g, 0.267 mol) is slowly added at 19 C. to a suspension of cyclohexyl-(4-methylsulfanylphenyl)methanone (prepared according to U.S. Pat. No. 6,180,651; 63.3 g, 0.270 mol) in dichloroethane (200 ml) and the reaction mixture stirred overnight whilst bubbling some nitrogen below liquid level in order to constantly remove hydrogen bromide. The resulting solution is evaporated to dryness to afford the title compound (86.8 g). Orange liquid;

(91) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.35-1.45 (m, 1H), 1.49-1.59 (m, 3H), 1.75-1.89 (m, 2H), 2.15-2.23 (m, 2H), 2.32-2.39 (m, 2H), 2.53 (s, 3H), 7.23 (m, d-like, 2H), 8.06-8.08 (m, d-like, 2H);

(92) MS (CI), m/z (%): found 313 (90); calcd. for C.sub.14H.sub.17BrOS: 313.

(93) Compound 19

(94) ##STR00030##

(95) b) (1-Diethylaminocyclohexyl)-(4-methylsulfinylphenyl)methanone: The title compound is prepared from (1-diethylaminocyclohexyl)-(4-methylsulfanylphenyl)methanone (prepared as described below) and 3-chloroperoxybenzoic acid (1 equivalent) according to the preparation of compound 22 (reaction overnight; no further 3-chloroperoxybenzoic acid added and no post reaction). Orange liquid;

(96) .sup.1H-NMR (400 MHz, CDCl.sub.3), [ppm]: 1.08-1.11 (m, t-like, 6H), 1.14-1.27 (m, 3H), 1.51-1.61 (m, 5H), 2.23-2.26 (m, 2H), 2.68-2.74 (m, q-like, 4H), 2.77 (s, 3H), 7.65-7.67 (m, d-like, 2H), 8.53-8.55 (m, d-like, 2H);

(97) MS (CI), m/z (%): found 322 (100; MH.sup.+); calcd. for C.sub.18H.sub.27NO.sub.2S: 321.

(98) a) (1-Diethylaminocyclohexyl)-(4-methylsulfanylphenyl)methanone: The title compound is prepared from 1-methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane (intermediate for the preparation of compound 18) and dietylamine (5.5 equivalents) according to the preparation of compound 21 (150 C., 72 hours). Orange liquid;

(99) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.06-1.11 (m, t-like, 6H), 1.16-1.36 (m, 3H), 1.47-1.60 (m, 5H), 2.25-2.29 (m, 2H), 2.52 (s, 3H), 2.64-2.72 (m, q-like, 4H), 7.20-7.22 (m, d-like, 2H), 8.37-8.40 (m, d-like, 2H);

(100) MS (CI), m/z (%): found 306 (100; MH.sup.+); calcd. for C.sub.18H.sub.27NOS: 305.

(101) Compound 20

(102) Diethyl-[2-(4-methoxyphenyl)-2-oxo-ethyl]ammonium chloride: Hydrochloric acid (1 mol/L in water; 8 ml, 8 mmol) is added to a dispersion of 2-diethylamino-1-(4-methoxyphenyl)-ethanone (prepared as described below; 88%; 2 g, 7.9 mmol) in water (8 ml). The resulting mixture is stirred at 25 C. for 20 minutes, filtered over a plug of hyflo and the filtrate evaporated on a rotary evaporator to afford the title compound as a viscous, brownish oil (1.3 g). The .sup.1H-NMR spectrum (300 MHz, DMSO-d.sub.6) corresponds to the structure of compound 20.

(103) 2-Diethylamino-1-(4-methoxyphenyl)ethanone: 2-Bromo-1-(4-methoxy-phenyl)ethanone (2.35 g, 10.3 mmol), dissolved in diethyl ether (10 ml), is slowly added to a solution of diethylamine (99%; 1.47 g, 19.9 mmol) in diethylether (8 ml). The reaction mixture is brought to reflux and stirred for 6 hours. The resulting suspension is cooled to 25 C., filtered and the filtrate evaporated on a rotary evaporator to afford the title compound as an orange oil (2.25 g).

(104) .sup.1H-NMR (300 MHz, DMSO-d.sub.6), [ppm]: 0.93-0.98 (m, t-like, 6H), 2.51-2.58 (m, q-like, 4H), 3.77 (s, 2H), 3.83 (s, 3H), 7.00-7.02 (m, d-like, 2H), 7.99-8.01 (m, d-like, 2H).

(105) GLC/MS (pos. CI), m/z (%): found 222 (100); calcd. for C.sub.13H.sub.19NO.sub.2: 221.

(106) Compound 21

(107) ##STR00031##

(108) (4-Methylsulfanylphenyl)-(1-pyrrolidin-1-ylcyclohexyl)methanone: 1-Methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane (intermediate for the preparation of compound 18; 7 g, 0.0265 mol) and pyrrolidine (99%; 7.6 g, 0.1069 mol) are stirred together for 24 hours in an autoclave at 140 C. The autoclave is cooled down to 25 C., unloaded and excess pyrrolidine distilled off. Aqueous hydrochloric acid (2 mol/L; 20 ml) is added to the residue (8.1 g) and the resulting mixture extracted with diethylether. The aqueous phase is split off, basified by addition of conc. aqueous sodium hydroxide solution and extracted with diethylether. The organic phase is split off, dried over K.sub.2CO.sub.3, filtered and evaporated. Column chromatography (silica, hexane/ethylacetate) of the residue (6.6 g) affords the title compound as a yellow oil (3.2 g).

(109) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.07-1.32 (m, 3H), 1.51-1.62 (m, 5H), 1.74 (broad s, 4H), 2.25-2.29 (m, d-like, 2H), 2.52 (s, 3H), 2.73 (broad s, 4H), 7.20-7.22 (m, d-like, 2H), 8.21-8.24 (m, d-like, 2H);

(110) MS (CI), m/z (%): found 304 (100; MH.sup.+); calcd. for C.sub.18H.sub.25NOS: 303.

(111) Compound 22

(112) ##STR00032##

(113) (4-Methylsulfinylphenyl)-(1-pyrrolidin-1-ylcyclohexyl)methanone: 3-Chloroperoxybenzoic acid (77%; 1.59 g, 0.0071 mol), dissolved in dichloromethane (15 ml), is slowly added to an ice-cooled solution of (4-methylsulfanylphenyl)-(1-pyrrolidin-1-ylcyclohexyl)methanone (compound 21; 2.15 g, 0.0071 mol) in dichloromethane (10 ml). The ice bath is removed and the reaction mixture stirred overnight. Another 3-chloroperoxybenzoic acid (77%; 0.24 g, 0.0011 mol) is added and the reaction mixture stirred for an additional 40 hours at 25 C. The resulting solution is sequentially washed with an aqueous solution of sodium hydroxide (2 mol/L) and brine, dried over MgSO.sub.4, filtrated and then evaporated to dryness. Column chromatography (silica; hexane/ethylacetate) of the residue affords the title compound as a yellow solid.

(114) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.10-1.29 (m, 3H), 1.53-1.62 (m, 5H), 1.76 (broad s, 4H), 2.21-2.24 (m, d-like, 2H), 2.73 (broad s, 4H), 2.76 (s, 3H), 7.64-7.66 (m, d-like, 2H), 8.35-8.37 (m, d-like, 2H);

(115) MS (CI), m/z (%): found 320 (100; MH.sup.+); calcd. for C.sub.18H.sub.25NO.sub.2S: 319.

(116) Compound 23

(117) ##STR00033##

(118) c) (4-methylsulfonylphenyl)-(1-pyrrolidin-1-ylcyclohexyl)methanone: The title compound is prepared from 2-methoxy-2-(4-methylsulfonylphenyl)-1-oxaspiro[2.5]octane (prepared as described below) and pyrrolidine (4 equivalents) according to the preparation of compound 21 (140 C., 48 hours). Yellow solid;

(119) .sup.1H-NMR (400 MHz, CDCl.sub.3), [ppm]: 1.14-1.22 (m, 3H), 1.54-1.66 (m, 5H), 1.74-1.81 (m, 4H), 2.18-2.22 (m, 2H), 2.72-2.75 (m, 4H), 3.09 (s, 3H), 7.95-7.97 (m, d-like, 2H), 8.36-8.38 (m, d-like, 2H);

(120) MS (CI), m/z (%): found 336 (100; MH.sup.+); calcd. for C.sub.18H.sub.25NO.sub.3S: 335.

(121) b) 2-Methoxy-2-(4-methylsulfonylphenyl)-1-oxaspiro[2.5]octane: The title compound is prepared from (1-bromocyclohexyl)-(4-methylsulfonylphenyl)methanone (prepared as described below) and sodium methoxide according to the method described for the preparation of 2-methoxy-2-(4-methylsulfanylphenyl)-1-oxaspiro[2.5]octane (intermediate for the preparation of compound 18). Orange solid;

(122) .sup.1H-NMR (400 MHz, CDCl.sub.3), [ppm]: 1.08-1.13 (m, 1H), 1.17-1.34 (m, 2H), 1.39-1.68 (m, 4H), 1.76-1.87 (m, 2H), 1.94-2.00 (m, 1H), 3.11 (s, 3H), 3.21 (s, 3H), 7.69-7.71 (m, d-like, 2H), 7.97-7.99 (m, d-like, 2H);

(123) MS (CI), m/z (%): found 297 (100; MH.sup.+); calcd. for C.sub.15H.sub.20O.sub.4S: 296.

(124) a) (1-Bromocyclohexyl)-(4-methylsulfonylphenyl)methanone: 3-Chloroperoxybenzoic acid (77%; 19.6 g, 0.0875 mol), dissolved in dichloromethane (120 ml), is slowly added to an ice-cooled solution of (1-bromocyclohexyl)-(4-methylsulfanylphenyl)methanone (intermediate for the preparation of compound 18; 13.4 g, 0.0428 mol) in dichloromethane (80 ml). The ice bath is removed and the reaction mixture stirred for 6 hours at 25 C. The resulting suspension is filtered and the filtrate washed with sodium carbonate solution (2 mol/L). The organic phase is split off, dried over MgSat, filtered and evaporated to dryness to afford the title compound (15.6 g) as a yellow solid.

(125) .sup.1H-NMR (400 MHz, CDCl.sub.3), [ppm]: 1.38-1.46 (m, 1H), 1.50-1.65 (m, 3H), 1.77-1.88 (m, 2H), 2.14-2.19 (m, 2H), 2.28-2.34 (m, 2H), 3.11 (s, 3H), 8.01-8.03 (m, d-like, 2H), 8.21-8.23 (m, d-like, 2H);

(126) LC/MS (pos. APCI), m/z (area %): found 344.8 (93); calcd. for C.sub.14H.sub.17BrO.sub.3S: 345.

(127) Compound 24

(128) ##STR00034##

(129) 2-(Ethyl(methyl)amino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and N-ethylmethylamine (3 equivalents) according to the preparation of compound 21 (150 C., 48 hours). Yellow liquid;

(130) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.99 (t, J=7.05 Hz, 3H), 1.29 (s, 6H), 2.26 (s, 3H), 2.40 (q, J=7.05 Hz, 2H), 2.53 (s, 3H), 7.21-7.24 (m, d-like, 2H), 8.50-8.53 (m, d-like, 2H);

(131) MS (CI), m/z (%): found 252 (100; MH.sup.+); calcd. for C.sub.14H.sub.21NOS: 251.

(132) Compound 25

(133) ##STR00035##

(134) Dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium methyl sulfate: Dimethyl sulfate (99%; 24.5 g, 0.1923 mol) is slowly added at 25 C. to a solution of 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholino-propan-1-one (5.4 g, 0.0193 mol) in acetonitrile (50 ml) containing water (0.35 g, 0.0194 mol). The reaction mixture is brought to 60 C. and stirred overnight. After cooling down to 25 C. toluene (40 ml) is added and the resulting dispersion allowed to settle. Supernatants are decanted and the remaining oil dried to afford the title compound (10.48 g). Yellow oil;

(135) Elemental analysis (S and N only, %): found S 19.0, N 2.83, corresponding to a molar ratio S/N=2.9/1; calcd. S 18.6, N 2.71, corresponding to a molar ratio S/N=3/1;

(136) MS (pos./neg. ESI), m/z (%): found 294.0 (100; M-H.sup.+)/111.0 (100); calcd. for [C.sub.16H.sub.25NO.sub.2S]+/[CH.sub.3O.sub.4S].sup.: 295/111.

(137) Compound 26

(138) ##STR00036##

(139) Dimethyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium methyl sulfate: Dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium methyl sulfate (compound 25; 4.5 g, 0.0087 mol) is dissolved in an aqueous solution of sodium hydroxide (2 mol/L; 5 g, ca. 0.0093 mol). The resulting solution (pH ca. 4.5) is brought to pH 9.0 by portion wise addition of solid sodium carbonate (ca. 0.3 g) and then stirred at 25 C. for 30 minutes. Extraction with dichloromethane and evaporation of the organic solvent affords the title compound as a yellow solid (2.39 g).

(140) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 2.55-2.58 (m, 4H), 3.55 (s, 6H), 3.69-3.72 (m, 4H), 3.70 (s, 3H), 8.16-8.19 (m, d-like, 2H), 8.76-8.79 (m, d-like, 2H);

(141) MS (pos./neg. ESI), m/z (%): found 294.1 (100)/111.1 (100); calcd. for [C.sub.16H.sub.24NO.sub.2S].sup.+/[CH.sub.3O.sub.4S].sup.: 294/111.

(142) Compound 27

(143) ##STR00037##

(144) Dimethyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium hexafluorophosphate: Sodium hexafluorophosphate (98%; 5.21 g, 0.0304 mol), dissolved in water (16 ml), is slowly added to a solution of dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium methyl sulfate (compound 25; 5.25 g, 0.0101 mol) in water (47 ml). The resulting solution (pH ca. 0.8) is brought to pH 9.2 by portion wise addition of an aqueous solution of sodium carbonate (2 mol/L; ca. 19.3 g). The precipitate is filtered, washed with water and dried to afford the title compound as a yellow solid (3.26 g).

(145) .sup.1H-NMR (400 MHz, CD.sub.3CN), [ppm]: 1.32 (s, 6H), 2.55-2.57 (m, 4H), 3.19 (s, 6H), 3.63-3.65 (m, 4H), 7.97-7.99 (m, d-like, 2H), 8.71-8.73 (m, d-like, 2H);

(146) MS (pos./neg. ESI), m/z (%): found 294.1 (100)/145.1 (100); calcd. for [C.sub.16H.sub.24NO.sub.2S].sup.+/[PF.sub.6].sup.: 294/145.

(147) Compound 28

(148) ##STR00038##

(149) Dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium tetrafluoroborate: Dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium methyl sulfate (compound 25; 5.18 g, 0.01 mol) is dissolved in an aqueous solution of sodium hydroxide (2 mol/L; 5.4 g, ca. 0.01 mol). The resulting solution (pH ca. 4.6) is brought to pH 10.0 by portion wise addition of solid sodium carbonate (ca. 0.95 g) followed by the addition of a solution of sodium tetrafluoroborate (98%; 2.24 g, 0.02 mol) in water (9 ml). The precipitate is filtered, washed with water and dried to afford the title compound as a yellow solid (2.65 g).

(150) .sup.1H-NMR (400 MHz, CD.sub.3CN), [ppm]: 1.32 (s, 6H), 2.55-2.58 (m, 4H), 3.21 (s, 6H), 3.63-3.67 (m, 4H), 7.98-8.01 (m, d-like, 2H), 8.71-8.74 (m, d-like, 2H);

(151) MS (pos./neg. ESI), m/z (%): found 294 (100)/87 (100); calcd. for [C.sub.16H.sub.24NO.sub.2S].sup.+/[BF.sub.4].sup.: 294/87.

(152) Compound 29

(153) ##STR00039##

(154) 2-Methyl-1-(4-methylsulfanylphenyl)-2-(1-piperidyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and piperidine according to EP88050A2. Yellowish solid;

(155) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.29 (s, 6H), 1.46-1.51 (m, 2H), 1.51-1.59 (m, 4H), 2.49-2.52 (m, 4H), 2.54 (s, 3H), 7.22-7.25 (m, d-like, 2H), 8.57-8.60 (m, d-like, 2H);

(156) MS (CI), m/z (%): found 278 (100; MH.sup.+); calcd. for C.sub.16H.sub.23NOS: 277.

(157) Compound 30

(158) ##STR00040##

(159) 2-Methyl-2-(methyl(propyl)amino)-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and N-methylpropylamine (3 equivalents) according to the preparation of compound 21 (150 C., 22 hours). Yellow liquid;

(160) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.82 (t, J=7.4 Hz, 3H), 1.30 (s, 6H), 1.40-1.52 (m, sextet-like, 2H), 2.22 (s, 3H), 2.31-2.36 (m, t-like, 2H), 2.53 (s, 3H), 7.20-7.23 (m, d-like, 2H), 8.49-8.51 (m, d-like, 2H);

(161) MS (CI), m/z (%): found 266 (100; MH.sup.+); calcd. for C.sub.15H.sub.23NOS: 265.

(162) Compound 31

(163) ##STR00041##

(164) 2-(Isopropyl(methyl)amino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and N-isopropylmethylamine (3 equivalents) according to the preparation of compound 21 (150 C., 23 hours). Yellow liquid;

(165) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.99 (d, J=6.4 Hz, 6H), 1.34 (s, 6H), 2.24 (s, 3H), 2.53 (s, 3H), 3.03 (septet, J=6.4 Hz, 1H), 7.20-7.23 (m, d-like, 2H), 8.40-8.43 (m, d-like, 2H);

(166) MS (CI), m/z (%): found 266 (100; MH.sup.+); calcd. for C.sub.15H.sub.23NOS: 265.

(167) Compound 32

(168) ##STR00042##

(169) 2-(Ethyl(propyl)amino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and N-ethylpropylamine (3 equivalents) according to the preparation of compound 21 (150 C., 70 hours). Yellow liquid;

(170) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.82 (t, J=7.4 Hz, 3H), 1.03 (t, J=7.1 Hz, 3H), 1.33 (s, 6H), 1.47-1.60 (m, sextet-like, 2H), 2.43-2.48 (m, 2H), 2.52-2.59 (m, 2H), 2.53 (s, 3H), 7.21-7.23 (m, d-like, 2H), 8.53-8.55 (m, d-like, 2H);

(171) MS (CI), m/z (%): found 280 (100; MH.sup.+); calcd. for C.sub.16H.sub.25NOS: 279.

(172) Compound 33

(173) ##STR00043##

(174) 2-(Dipropylamino)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and dipropylamine (3 equivalents) according to the preparation of compound 21 (150 C., 45 hours). Yellow liquid;

(175) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.79 (t, J=7.4 Hz, 6H), 1.33 (s, 6H), 1.43-1.56 (m, sextet-like, 4H), 2.40-2.45 (m, 4H), 2.53 (s, 3H), 7.21-7.23 (m, d-like, 2H), 8.51-8.54 (m, d-like, 2H);

(176) MS (CI), m/z (%): found 294 (100; MH.sup.+); calcd. for C.sub.17H.sub.27NOS: 293.

(177) Compound 34

(178) ##STR00044##

(179) (4-Methylsulfanylphenyl)-[1-(1-piperidyl)cyclohexyl]methanone: The title compound is prepared from 1-methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane (intermediate for the preparation of compound 18) and piperidine (4 equivalents) according to the preparation of compound 21 (150 C., 22 hours). Brownish oil;

(180) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.06-1.16 (m, 1H), 1.20-1.35 (m, 2H), 1.42-1.52 (m, 2H), 1.52-1.61 (m, 9H), 2.14-2.18 (m, 2H), 2.53 (s, 3H), 2.61-2.64 (m, 4H), 7.20-7.23 (m, d-like, 2H), 8.39-8.41 (m, d-like, 2H);

(181) MS (CI), m/z (%): found 318 (100; MH.sup.+); calcd. for C.sub.19H.sub.27NOS: 317.

(182) Compound 35

(183) ##STR00045##

(184) [4-(2-Dimethylamino-2-methyl-propanoyl)phenyl]-trimethyl-ammonium tetrafluoroborate: Dimethyl sulfate (99%; 26.7 g, 0.21 mol) is slowly added at 25 C. to a solution of 2-dimethylamino-1-(4-dimethylaminophenyl)-2-methyl-propan-1-one (prepared according to EP138754A2; 4.96 g, 0.021 mol) in acetonitrile (50 ml) containing water (0.38 g, 0.021 mol), the reaction mixture stirred at 25 C. for ca. 40 hours and the resulting suspension filtered. Toluene (50 ml) is added to the filtrate and supernatants decanted. The remaining oil (6.8 g) is dried and re-dissolved in water (6.8 ml). The resulting solution (pH ca. 0.3) is brought to pH 9.2 by portion wise addition of an aqueous solution of sodium carbonate (2 mol/L; ca. 5.5 g) followed by the addition of a solution of sodium tetrafluoroborate (98%; 4.24 g, 0.0378 mol) in water (8 ml). The resulting suspension (pH ca. 8.3) is brought again to pH 9.2 by further addition of solid sodium carbonate (2.5 g). The precipitate is filtered, washed with water and dried to afford the title compound as a yellow solid (1.8 g).

(185) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 1.29 (s, 6H), 2.16 (s, 6H), 3.56 (s, 9H), 7.80-7.83 (m, d-like, 2H), 8.00-8.02 (m, d-like, 2H);

(186) MS (pos./neg. ESI), m/z (%): found 249 (100)/87 (100); calcd. for [C.sub.15H.sub.25N.sub.2O]+/[BF.sub.4].sup.: 249/87.

(187) Compound 36

(188) ##STR00046##

(189) 2-(Azepan-1-yl)-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfanylphenyl)oxirane (prepared according to EP88050A2) and hexamethyleneimine (4 equivalents) according to the preparation of compound 21 (ambient pressure, 140 C., 18 hours). Brownish liquid;

(190) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.32 (s, 6H), 1.48-1.64 (m, 8H), 2.54 (s, 3H), 2.62-2.65 (m, t-like, 4H), 7.22-7.23 (m, d-like, 2H), 8.53-8.56 (m, d-like, 2H);

(191) MS (CI), m/z (%): found 293 (100; MH.sub.2.sup.+); calcd. for C.sub.17H.sub.25NOS: 291.

(192) Compound 37

(193) ##STR00047##

(194) 2-(Azepan-1-yl)-2-methyl-1-(4-methylsulfonylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfonylphenyl)oxirane (intermediate for the preparation of compound 41) and hexamethyleneimine (4 equivalents) according to the preparation of compound 21 (ambient pressure, reflux, overnight). Yellow solid;

(195) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.34 (s, 6H), 1.48-1.64 (m, 8H), 2.63-2.67 (m, t-like, 4H), 3.11 (s, 3H), 7.99-8.02 (m, d-like, 2H), 8.75-8.78 (m, d-like, 2H);

(196) MS (CI), m/z (%): found 324.2 (100; MH.sup.+); calcd. for C.sub.17H.sub.25NO.sub.3S: 323.

(197) Compound 40

(198) ##STR00048##

(199) 2-Methyl-1-(4-methylsulfinylphenyl)-2-(1-piperidyl)propan-1-one: The title compound is prepared from 2-methyl-1-(4-methylsulfanylphenyl)-2-(1-piperidyl)propan-1-one (compound 29) and 3-chloroperoxybenzoic acid (1 equivalent) according to the preparation of compound 22 (reaction overnight; no further 3-chloroperoxybenzoic acid added and no post reaction). Slightly yellow solid;

(200) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.307 (s, 3H), 1.311 (s, 3H), 1.43-1.60 (m, 6H), 2.50-2.54 (m, t-like, 4H), 2.78 (s, 3H), 7.67-7.70 (m, d-like, 2H), 8.75-8.78 (m, d-like, 2H);

(201) MS (CI), m/z (%): found 294 (100; MH.sup.+); calcd. for C.sub.16H.sub.23NO.sub.2S: 293.

(202) Compound 41

(203) ##STR00049##

(204) d) 2-Methyl-1-(4-methylsulfonylphenyl)-2-(1-piperidyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfonylphenyl)oxirane (prepared as described below) and piperidine (4 equivalents) according to the preparation of compound 21 (ambient pressure, reflux, overnight). Beige solid;

(205) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.31 (s, 6H), 1.45-1.64 (m, 6H), 2.50-2.53 (m, 4H), 3.11 (s, 3H), 7.98-8.01 (m, d-like, 2H), 8.77-8.80 (m, d-like, 2H);

(206) MS (CI), m/z (%): found 310 (100; MH.sup.+); calcd. for C.sub.16H.sub.23NO.sub.3S: 309.

(207) c) 2-Methoxy-3,3-dimethyl-2-(4-methylsulfonylphenyl)oxirane: The title compound is prepared from 2-bromo-2-methyl-1-(4-methylsulfonylphenyl)propan-1-one (prepared as described below) and sodium methoxide according to the method described for the preparation of 2-methoxy-2-(4-methylsulfanylphenyl)-1-oxaspiro[2.5]octane (intermediate for the preparation of compound 18). Yellow to orange solid;

(208) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.02 (s, 3H), 1.57 (s, 3H), 3.11 (s, 3H), 3.22 (s, 3H), 7.68-7.71 (m, d-like, 2H), 7.97-8.00 (m, d-like, 2H);

(209) MS (CI), m/z (%): found 257 (100; MH.sup.+); calcd. for C.sub.12H.sub.16O.sub.4S: 256.

(210) b) 2-Bromo-2-methyl-1-(4-methylsulfonylphenyl)propan-1-one: The title compound is prepared from 2-bromo-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one (prepared as described below) and 3-chloroperoxybenzoic acid according to the method described for the preparation of (1-bromocyclohexyl)-(4-methylsulfonylphenyl)methanone (intermediate for the preparation of compound 23). White solid;

(211) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 2.05 (s, 6H), 3.11 (s, 3H), 8.03-8.05 (m, d-like, 2H), 8.26-8.29 (m, d-like, 2H);

(212) MS (CI), m/z (%): found 305 (100); calcd. for C.sub.11H.sub.13BrO.sub.3S: 305.

(213) a) 2-Bromo-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one: The title compound is prepared from 2-methyl-1-(4-methylsulfanylphenyl)propan-1-one (prepared according to e.g. Tetrahedron 2003, 59, 7915-7920) and bromine according to the method described for the preparation of (1-bromocyclohexyl)-(4-methylsulfanylphenyl)methanone (intermediate for the preparation of compound 18). Orange liquid;

(214) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 2.05 (s, 6H), 2.55 (s, 3H), 7.25-7.28 (m, d-like, 2H), 8.13-8.16 (m, d-like, 2H);

(215) MS (CI), m/z (%): found 274.9 (100; MH.sup.+); calcd. for C.sub.11H.sub.13BrOS: 273.

(216) Compound 42

(217) ##STR00050##

(218) Dimethyl-[4-(2-methyl-2-piperidin-1-ium-1-yl-propanoyl)phenyl]sulfonium methyl sulfate: The title compound is prepared from 2-methyl-1-(4-methylsulfanylphenyl)-2-(1-piperidyl)propan-1-one (compound 29), water and dimethyl sulphate according to the preparation of compound 25. Orange liquid;

(219) MS (pos./neg. ESI), m/z (%): found 292.0 (40; M-H.sup.+)/111.0 (100); calcd. for [C.sub.17H.sub.27NOS].sup.+/[CH.sub.3O.sub.4S].sup.: 293/111.

(220) Compound 43

(221) ##STR00051##

(222) Dimethyl-[4-[2-methyl-2-(1-piperidyl)propanoyl]phenyl]sulfonium methyl sulfate: The title compound is prepared from dimethyl-[4-(2-methyl-2-piperidin-1-ium-1-yl-propanoyl)phenyl]sulfonium methyl sulfate (compound 42) according to the preparation of compound 26. Yellow solid;

(223) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 1.22 (s, 6H), 1.29-1.49 (m, 6H), 2.39-2.48 (m, 4H), 3.19 (s, 6H), 3.64 (s, 3H), 7.91-7.94 (m, d-like, 2H), 8.36-8.38 (m, d-like, 2H);

(224) MS (pos./neg. ESI), m/z (%): found 292.1 (30)/111.1 (100); calcd. for [C.sub.17H.sub.26NOS].sup.+/[CH.sub.3O.sub.4S].sup.: 292/111.

(225) Compound 44

(226) ##STR00052##

(227) Dimethyl-[4-[2-methyl-2-(1-piperidyl)propanoyl]phenyl]sulfonium tetrafluoroborate: A suspension of dimethyl-[4-[2-methyl-2-(1-piperidyl)propanoyl]phenyl]sulfonium methyl sulfate (compound 43; 1.0 g, 0.0025 mol) in water (5.6 ml) is brought to pH 2.9 by portion wise addition of aqueous hydrochloric acid (4 mol/L) followed by the addition of a solution of sodium tetrafluoroborate (0.45 g, 0.0041 mol) in water (0.45 g). The resulting solution is brought to pH 9 by portion wise addition of aqueous sodium carbonate solution (2 mol/L). Filtration and drying of the filter-cake affords the title compound (0.76 g). Yellow solid;

(228) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 1.24 (s, 6H), 1.29-1.39 (m, 2H), 1.39-1.49 (m, 4H), 2.42-2.50 (m, 4H), 3.18 (s, 6H), 7.90-7.93 (m, d-like, 2H), 8.32-8.35 (m, d-like, 2H);

(229) MS (pos./neg. ESI), m/z (%): found 292 (30)/87 (100); calcd. for [C.sub.17H.sub.26NOS]+/[BF.sub.4].sup.: 292/87.

(230) Compound 45

(231) ##STR00053##

(232) 2-Diethylamino-2-methyl-1-(4-methylsulfinylphenyl)propan-1-one: The title compound is prepared from 2-diethylamino-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one (compound

(233) 17) and 3-chloroperoxybenzoic acid (1 equivalent) according to the preparation of compound 22 (reaction overnight; no further 3-chloroperoxybenzoic acid added and no post reaction). Yellow liquid;

(234) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.05 (t, J=7.1 Hz, 6H), 1.35 (s, 6H), 2.58 (q, J=7.1 Hz, 4H), 2.77 (s, 3H), 7.66-7.69 (m, d-like, 2H), 8.71-8.73 (m, d-like, 2H);

(235) MS (CI), m/z (%): found 282 (100; MH.sup.+); calcd. C.sub.15H.sub.23NO.sub.2S: 281.

(236) Compound 46

(237) ##STR00054##

(238) 2-Diethylamino-2-methyl-1-(4-methylsulfonylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfonylphenyl)oxirane (intermediate for the preparation of compound 41) and diethylamine (4 equivalents) according to the preparation of compound 21 (150 C., 44 hours). Yellow solid;

(239) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.06 (t, J=7.1 Hz, 6H), 1.35 (s, 6H), 2.59 (q, J=7.1 Hz, 4H), 3.1 (s, 3H), 7.97-8.00 (m, d-like, 2H), 8.73-8.76 (m, d-like, 2H);

(240) MS (CI), m/z (%): found 298.1 (100; MH.sup.+); calcd. for C.sub.15H.sub.23NO.sub.3S: 297.

(241) Compound 47

(242) ##STR00055##

(243) [2-(4-Dimethylsulfoniophenyl)-1,1-dimethyl-2-oxo-ethyl]-diethyl-ammonium methyl sulfate:

(244) The title compound is prepared from 2-diethylamino-2-methyl-1-(4-methylsulfanylphenyl)propan-1-one (compound 17), water and dimethyl sulphate according to the preparation of compound 25. Red brown liquid;

(245) MS (pos./neg. ESI), m/z (%): found 280 (25; M-H.sup.+)/111.0 (100); calcd. for [C.sub.16H.sub.27NOS]+/[CH.sub.3O.sub.4S].sup.: 281/111;

(246) Compound 48

(247) ##STR00056##

(248) [4-(2-Diethylamino-2-methyl-propanoyl)phenyl]-dimethyl-sulfonium methyl sulfate: [2-(4-Dimethylsulfoniophenyl)-1,1-dimethyl-2-oxo-ethyl]-diethyl-ammonium methyl sulfate (compound 47; 16 g, 0.0318 mol) is dissolved in water (16 ml), the pH of the acidic solution (pH ca. 0.1) brought to pH 9.0 by portion wise addition of an aqueous solution of sodium carbonate (2 mol/L; ca. 27.1 g) and the resulting opaque solution stirred at 25 C. for 30 minutes. Extraction with dichloromethane and evaporation of the organic solvent affords the title compound as a yellow solid (8.44 g). Yellow solid;

(249) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 0.91 (t, J=7.1 Hz, 6H), 1.29 (s, 6H), 2.52 (q, J=7.1 Hz, 4H), 3.20 (s, 6H), 3.64 (s, 3H), 7.92-7.95 (m, d-like, 2H), 8.37-8.40 (m, d-like, 2H);

(250) MS (pos./neg. ESI), m/z (%): found 280 (100)/111.1 (100); calcd. for [C.sub.16H.sub.26NOS].sup.+/[CH.sub.3O.sub.4S].sup.: 280/111.

(251) Compound 49

(252) ##STR00057##

(253) [4-(2-Diethylamino-2-methyl-propanoyl)phenyl]-dimethyl-sulfonium tetrafluoroborate: Sodium tetrafluoroborate (98%; 7.1 g, 0.0634 mol), dissolved in water (7.1 g), is added to a solution of [2-(4-dimethylsulfoniophenyl)-1,1-dimethyl-2-oxo-ethyl]-diethyl-ammonium methyl sulfate (compound 47; 16 g, 0.0318 mol) in water (16 ml). The resulting slightly opaque solution (pH ca. 1.2) is stirred at 25 C. for one hour and then the pH brought to 9.0 by portion wise addition of an aqueous solution of sodium carbonate (2 mol/L; ca. 31.3 g). The resulting suspension is stirred at 25 C. for 15 minutes, filtered and the filter-cake dried to afford the title compound (7.31 g). Yellow solid;

(254) .sup.1H-NMR (300 MHz, D.sub.2O), [ppm]: 0.92 (t, J=7.0 Hz, 6H), 1.30 (s, 6H), 2.54 (q, J=7.0 Hz, 4H), 3.19 (s, 6H), 7.91-7.94 (m, d-like, 2H), 8.35-8.37 (m, d-like, 2H);

(255) MS (pos./neg. ESI), m/z (%): found 280 (100)/87 (100); calcd. for [C.sub.16H.sub.26NOS].sup.+/[BF.sub.4].sup.: 280/87.

(256) Compound 50

(257) ##STR00058##

(258) 2-Diethylamino-2-methyl-1-phenyl-propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-phenyl-oxirane (prepared according to FR1447116) and diethylamine (4 equivalents) according to the preparation of compound 21 (150 C., 44 hours). Yellow orange liquid;

(259) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.07 (t, J=7.1 Hz, 6H), 1.35 (s, 6H), 2.60 (q, J=7.1 Hz, 4H), 7.38-7.43 (m, 2H), 7.48-7.53 (m, 1H), 8.56-8.59 (m, 2H);

(260) MS (CI), m/z (%): found 220.15 (100; MH.sup.+); calcd. for C.sub.14H.sub.21NO: 219.

(261) Compound 52

(262) ##STR00059##

(263) b) 2-Diethylamino-2-methyl-1-(p-tolyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(p-tolyl)oxirane (prepared as described below) and diethylamine (4 equivalents) according to the preparation of compound 21 (150 C., 48 hours). Yellowish liquid;

(264) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.07 (t, J=5.4 Hz, 6H), 1.34 (s, 6H), 2.41 (s, 3H), 2.60 (q, J=5.4 Hz, 4H), 7.21 (d, J=6.3 Hz, 2H), 8.51 (d, J=6.3 Hz, 2H);

(265) MS (CI), m/z (%): found 234.2 (100; MH.sup.+); calcd. for C.sub.15H.sub.23NO: 233.

(266) a) 2-Methoxy-3,3-dimethyl-2-(p-tolyl)oxirane: The title compound is prepared from 2-bromo-2-methyl-1-(p-tolyl)propan-1-one (prepared according to Journal of Organic Chemistry 1956, 21, 1120-1123) and sodium methoxide according to the preparation of 1-methoxy-1-(4-methylsulfanylphenyl)-2-oxaspiro[2.5]octane (intermediate for the preparation of compound 18). Colourless liquid;

(267) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.03 (s, 3H), 1.56 (s, 3H), 2.39 (s, 3H), 3.22 (s, 3H), 7.21 (d, J=6.3 Hz, 2H), 7.36 (d, J=6.3 Hz, 2H).

(268) Compound 54

(269) ##STR00060##

(270) 2-(Dipropylamino)-2-methyl-1-(4-methylsulfonylphenyl)propan-1-one: The title compound is prepared from 2-methoxy-3,3-dimethyl-2-(4-methylsulfonylphenyl)oxirane (intermediate for the preparation of compound 41) and dipropylamine (4 equivalents) according to the preparation of compound 21 (first ambient pressure, reflux, 44 hours and then pressure, 150 C., 24 hours). Yellow liquid;

(271) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 0.79 (t, J=7.3 Hz, 6H), 1.34 (s, 6H), 1.42-1.55 (m, sextet-like, 4H), 2.41-2.47 (m, 4H), 3.10 (s, 3H), 7.97-7.80 (m, d-like, 2H), 8.70-8.73 (m, d-like, 2H);

(272) MS (CI), m/z (%): found 327.2 (100; MH.sub.2.sup.+); calcd. for C.sub.17H.sub.27NO.sub.3S: 325.

(273) Compound 55

(274) ##STR00061##

(275) (1-Diethylaminocyclohexyl)-(4-methylsulfonylphenyl)methanone: The title compound is prepared from 2-methoxy-2-(4-methylsulfonylphenyl)-1-oxaspiro[2.5]octane (intermediate for the preparation of compound 23) and diethylamine (4 equivalents) according to the preparation of compound 21 (150 C., 44 hours). Yellow solid;

(276) .sup.1H-NMR (300 MHz, CDCl.sub.3), [ppm]: 1.10 (t, J=7.1 Hz, 6H), ca. 1.13-1.29 (m, 3H), 1.49-1.67 (m, 5H), 2.20-2.24 (m, d-like, 2H), 2.72 (q, J=7.1 Hz, 4H), 3.1 (s, 3H), 7.95-7.98 (m, d-like, 2H), 8.53-8.56 (m, d-like, 2H);

(277) MS (CI), m/z (%): found 338.18 (100; MH.sup.+); calcd. for C.sub.18H.sub.27NO.sub.3S: 337.

APPLICATION EXAMPLES

(278) Solution Bleach

(279) A solution of 213 M Morin, 5 mM Peracetic acid and 20 mol/l of the respective catalyst is prepared in 25 mmol/l carbonate buffer. The decay of the morin absorption is followed at 398 nm at 20 C. over time using a spectrophotometer. The time necessary to reach 50% of the initial morin absorption (t) is given in the following table for each compound. Without the addition of catalyst (per acetic acid alone) t is 30 minutes. This value serves as the reference.

(280) TABLE-US-00001 TABLE 1 -Aminoketon t [Minuten] Compound 1 4.5 Compound 2 6.5 Compound 3 5.5 Compound 4 5.3 Compound 5 3.5 Compound 6 3 Compound 7 8.1 Compound 8 8.3

(281) Compound 1-8 prove to catalyze the per acetic acid oxidation of morin.

(282) Stain Bleachin1:

(283) 1.5 mM per acetic acid are added to 50 mM carbonate and phosphate buffer containing of different pH-values. 10 g bleached cotton and 0.8 g BC01 Tee (CFT) are washed with this buffer solution for 45 minutes at 30 C. Following the wash the textiles are rinsed with running tap water, spin dried and dried at 50 C. The lightness (Y) of the BC01 Tea fabric is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process. The higher the Y the more effective is the bleach. In a second experiment 200 mol/l of compound 20 was added. The following table gives the Y values at different pH-values.

(284) TABLE-US-00002 TABLE 2 pH 6 pH 7 pH 7.9 pH 8.3 pH 9.5 pH 9.9 pH 10.3 Per acetic acid 8.2 9.6 11 10.8 9.8 8.1 7.1 Compound 20 0 10 14 17.2 15.8 13.7 12.1 11.2

(285) Compound 20 significantly boosts the per acetic acid bleach even at pH values >9.0.

(286) Stain Bleaching2:

(287) 1.5 mM per acetic acid are added to 50 mM carbonate and phosphate buffer containing of different pH-values. 10 g bleached cotton and 0.8 g BC01 Tee (CFT) are washed with this buffer solution for 45 minutes at 30 C. Following the wash the textiles are rinsed with running tap water, spin dried and dried at 50 C. The lightness (Y) of the BC03 Tea fabric is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process. The higher the Y the more effective is the bleach.

(288) In the following experiments 25 mol/l of different aminoketones are added. The following table gives the Y values at different pH-values.

(289) TABLE-US-00003 TABLE 3 pH 6 pH 7 pH 8.1 pH 8.5 pH 9 pH 10 Per acetic acid 8.3 9.8 10.8 9.8 9.9 7.9 + compound 1 9.4 13.1 14.7 12.6 12.3 9.6 + compound 5 9.6 13 14.9 12.5 11.9 9.7 + compound 6 9.6 13.1 15.4 13.1 12.7 10.1 + compound 7 9.6 12.7 15.1 13 11.8 8.9

(290) The -aminoketones exhibit a clearly enhanced per acetic acid bleach performance.

(291) Stain Bleaching3:

(292) 20 g bleached cotton and 1.0 g BC01 tea (CFT) are washed in a wash liquor containing 5.6 g ECE98 standard detergent (ex WFK), 1.5 mmol/l per acetic acid, pH 9.8 for 45 minutes at 30 C. The lightness (Y) of the BC01 tea fabric is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process. The higher the Y the more effective is the bleach. In this example 12.5, 25, 50, 100 mol/l of different aminoketones are added.

(293) TABLE-US-00004 TABLE 4 Y -aminoketone (BC01 Tee) at different concentrations 12.5 M 25 M 50 M 100 M Per Acetic Acid, no catalyst 9.6 Compound 20 11 13 Compound 7 11.4 12.9 14.1 15.9 Compound 2 10.4 11.3 12.3 15.6 Compound 1 10.8 11.9 13.5 15.4 Compound 4 10.4 10.6 11.6 13.4 Compound 5 12.1 13.4 15 17.3 Compound 6 11.8 13 14.8 16.4 Compound 9 12 12 14 16.1 Compound 10 11.9 13.5 15.3 17.6 Compound 8 0 11.1 12.3 13.9 15.6 Compound 11 10.1 10.7 11.6 12.6 Compound 12 10.9 11.2 12.8 14.5

(294) All -Aminoketones used in this experiment clearly boost the bleach performance of per acetic acid.

(295) Stain Bleaching4:

(296) 20 g bleached cotton and 1.0 g BC01 tea (CFT) are washed in a wash liquor containing 5.6 g ECE98 standard detergent (ex WFK), 1.5 mmol/l per acetic acid, pH 9.8 for 45 minutes at 30 C. The lightness (Y) of the BC01 tea fabric is measured before and after the wash the difference of both Y values (Y) is a measure for the effectiveness of the bleach process. The results given in Table 5 are the difference of the Y of the peracetic acid plus catalyst and the Y of the peracetic acid alone (Y). Every value higher than zero indicates catalytic activity.

(297) In this example 12.5, 25, 50, 100 mol/l of different aminoketones are added.

(298) TABLE-US-00005 TABLE 5 Y -aminoketone (BC01 Tee) at different concentrations 12.5 M 25 M 50 M 100 M Comparative Experiment 1 0 0.9 1.1 2.4 Comparative Experiment 2 0 1.4 2.3 3.7 Compound 1 1.3 2.4 4.0 5.9 Compound 5 2.1 3.4 5.0 7.3 Compound 6 2.3 3.5 5.3 6.9 Compound 13 2.2 3.9 5.6 7.9 Compound 14 1.6 2.3 3.9 6.1 Compound 15 0 2.3 3.2 4.9 6.9 Compound 16 0.5 1.0 3.0 6.1 Compound 17 3.2 6.4 9.3 12.9 Compound 18 1.5 2.6 4.3 6.2 Compound 19 1.7 2.5 4.5 6.9 Compound 21 2.2 3.9 6.0 8.5 Compound 22 1.9 3.6 5.8 8.6 Compound 23 2.8 4.4 7.5 10.1 Compound 24 3.1 5.2 7.8 10.8 Compound 25 1.0 2.4 3.1 5.0 Compound 26 00 1.9 3.5 5.2 6.5 Compound 27 01 2.5 3.5 5.8 7.8 Compound 28 02 1.5 3.9 4.7 8.0 Compound 29 03 1.9 3.5 6.3 8.7 Compound 30 04 1.8 2.8 6.4 8.7 Compound 31 05 2.3 4.8 7 10.9 Compound 32 06 1.2 3.3 6.8 11.1 Compound 33 07 2.8 5.5 8.7 12.9 Compound 34 08 1.2 1.6 3 6.1 Compound 35 09 1.1 2.6 3.3 7.3 Compound 36 0 5.8 9.2 13.2 17.5 Compound 37 7.5 11.2 16.2 20.0 Compound 40 4.6 7.1 10.0 12.6 Compound 41 4.3 7.0 10.0 12.6 Compound 42 3.0 5.2 7.4 10.8 Compound 43 3.3 5.2 7.0 10.5 Compound 44 3.4 5.8 8.8 12.3 Compound 45 4.9 7.8 12.0 15.6 Compound 46 4.9 8.4 11.9 16.1 Compound 47 3.9 6.2 9.9 13.9 Compound 48 0 5 7.7 11.6 15.3 Compound 49 5.2 7.8 11.9 15.2 Compound 50 3 5.3 8.1 13.1 Compound 52 1.5 2.7 5.2 8.9 Compound 54 3.2 6.5 9.8 14.3 Compound 55 0.8 1.4 2.9 5.3

(299) All -aminoketones used in this experiment clearly boost the bleach performance of per acetic acid.

(300) Influence of Light

(301) The same experiments as described above carried out without 1.5 mM peracetic acid do not result in a Y value different from zero. This indicates that light induced radical formation can not be responsible for the bleach effect.

(302) A) Multistain Bleach Sodium Percarbonate/TAED

(303) 40 g bleach cotton fabric, BC01, tea, BC02 coffee, BC03 tea, and CS12 black currant stained cotton (0.4 g each) ex CFT are washed with a wash liquor containing: 4.7 g/l ECE98 standard detergent (WFK), 138 mg sodium per carbonate (SPC) and 30 mg Tetraacetylethylenediamine (TAED) for 60 minutes at 30 C. with and without 100 mol/l of compound 1. The pH of the wash liquor is adjusted to pH 9.9 with 1M HCl. The lightness (Y) of the stained fabrics is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process. The higher the Y the more effective is the bleach.

(304) TABLE-US-00006 TABLE 6 (Y) Values BC01 BC02 BC03 CS12 SPC/TAED 9.0 7.1 7.8 51.8 SPC/TAED + 15.5 14.1 11.3 55.9 compound 1

(305) The resulting Y values indicate a catalytic effect of compound 1 on all stains tested.

(306) B) Multistain Bleach Sodium Percarbonate/TAED

(307) 40 g bleached cotton fabric, BC01, tea, BC02 coffee, BC03 tea, and CS12 black currant stained cotton (0.5 g each) ex CFT are washed with 250 ml wash liquor containing: 4.7 g/l ECE98 standard detergent (WFK), 165 mg sodium per carbonate (SPC) and 30 mg Tetraacetylethylenediamine (TAED) for 60 minutes at 30 C. with and without 80 mol/l of catalyst. The pH of the wash liquor is adjusted to pH 10.1 with 1M HCl. The lightness (Y) of the stained fabrics is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process.

(308) The results given in Table 7 are the difference of the Y of SPC+TAED plus catalyst and the Y of SPC+TAED alone (Y). Every value higher than zero indicates catalytic activity.

(309) TABLE-US-00007 TABLE 7 (Y) Values BC01 BC02 BC03 CS12 3.0 3.9 2.8 2.7 0.1 1.1 0.7 2.5

(310) The resulting Y values indicate a catalytic effect of the catalysts tested

(311) C) Multistain Bleach Sodium Percarbonate/DOBA

(312) 40 g bleached cotton fabric, BC01, tea, BC02 coffee, BC03 tea, and BC04 curry stained cotton (0.5 g each) ex CFT are washed with 250 ml wash liquor containing: 4.7 g/l ECE98 standard detergent (WFK), 165 mg sodium per carbonate (SPC) and 36 mg Dodecanoyloxybenzoic acid (DOBA) for 60 minutes at 30 C. with and without 80 mol/l of catalyst. The pH of the wash liquor is adjusted to pH 10.1 with 1M HCl. The lightness (Y) of the stained fabrics is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process.

(313) The results given in Table 8 are the difference of the Y of SPC+TAED plus catalyst and the Y of SPC+TAED alone (Y). Every value higher than zero indicates catalytic activity.

(314) TABLE-US-00008 TABLE 8 Y Values BC01 BC02 BC03 BC04 5.4 5.3 0.8 7.5

(315) The resulting Y values indicate a catalytic effect of the catalyst tested

(316) D) Multistain BleachMultiple Washes

(317) 10 g bleached cotton fabric, BC01 tea and BC02 coffee stained cotton (0.5 g each) ex CFT are washed in three subsequent washes with 250 ml wash liquor containing: 3 g/l ECE98 standard detergent (WFK), 42 mg sodium per carbonate (SPC) and 9 mg Dodecanoyloxybenzoic acid (DOBA) or Tetraacetylethylenediamine (TAED) for 20 minutes at 20 C. with and without 20 mol/l of catalyst. The pH of the wash liquor is adjusted to pH 9.8 with 1M HCl. The lightness (Y) of the stained fabrics is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process.

(318) The results given in Table 9 are the difference of the Y of SPC+DOBA or TAED plus catalyst and the Y of SPC+DOBA or TAED alone (Y). Every value higher than zero indicates catalytic activity.

(319) TABLE-US-00009 TABLE 9 Y Values BC01 BC02 1.2 2.0 0 4.1 4.5

(320) The resulting Y values after the 3.sup.rd wash indicate a catalytic effect of the catalyst tested with both bleach activators used

(321) E) Multistain Bleach Sodium Percarbonate/NOBS

(322) 40 g bleached cotton fabric, BC01, tea, BC02 coffee stained cotton (0.5 g each) ex CFT are washed with 250 ml wash liquor containing: 4.7 g/l ECE98 standard detergent (WFK), 165 mg sodium per carbonate (SPC) and 39 mg Nonyloxybenzolsulfonic acid (NOBS) for 60 minutes at 30 C. with and without 80 mol/l of catalyst. The pH of the wash liquor is adjusted to pH 10.1 with 1M HCl. The lightness (Y) of the stained fabrics is measured before and after the wash, the difference of both Y values (Y) is a measure for the effectiveness of the bleach process.

(323) The results given in Table 10 are the difference of the Y of SPC+TAED plus catalyst and the Y of SPC+TAED alone (Y). Every value higher than zero indicates catalytic activity.

(324) TABLE-US-00010 TABLE 10 Y Values BC01 BC02 3.2 2.7 1.4 0.5

(325) The resulting Y values indicate a catalytic effect of the catalyst tested (100%).

(326) F) Low Temperature Stain Bleaching:

(327) 20 g bleached cotton and 0.5 g BC01 tea (CFT) are washed in 100 ml 25 mM Carbonate buffer pH 9.6 containing 14 mg Tetraacetylethylenediamine (TAED) and 6.5 mM Hydrogen-peroxide (H.sub.2O.sub.2) and 100 M Hydroxyethylenediphosphonate (HEDP) for 45 minutes at 10 C., with and without 30 M of catalyst. The lightness (Y) of the BC01 tea fabric is measured before and after the wash the difference of both Y values (Y) is a measure for the effectiveness of the bleach process.

(328) The results given in Table 11 are the difference of the Y of the TAED/H.sub.2O.sub.2 plus catalyst and the Y of the TAED/H.sub.2O.sub.2 alone (Y). Every value higher than zero indicates catalytic activity.

(329) TABLE-US-00011 TABLE 11 Y Values BC01 5.7 6.9 7.5 6.4

(330) The resulting Y values indicate a catalytic effect of the catalyst tested.