N-SUBSTITUTED 2-(6-HYDROXY-3-OXO-3H-XANTHENE-9-YL)BENZAMIDES AS PHOTOACTIVATORS IN DETERGENTS

Abstract

N-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamides are capable of generating bleach-active species when irradiated with visible light, these species leading to an enhanced bleaching power during the washing of textiles.

Claims

1. A use of N-alkyl-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamides having the general formula (I), ##STR00007## where R is an optionally substituted linear or branched alkyl radical having 8 to 16 C atoms, each R.sup.1 independently is F, Cl, Br or I, and each R.sup.2 independently is H, F, Cl, Br or I, as photobleaching agent to remove stains from textile materials.

2. A washing agent containing N-alkyl-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide of the general formula (I), ##STR00008## where R is an optionally substituted linear or branched alkyl radical having 8 to 16 C atoms, each R.sup.1 independently represents F, Cl, Br or I, and each R.sup.2 independently is H, F, Cl, Br or I.

3. The agent according to claim 2, characterized in that it contains 0.00001 wt. % to 1 wt. %, in particular 0.001 wt. % to 0.1 wt. % N-alkyl substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide of the general formula (I).

4. The agent according to claim 2, characterized in that it is liquid.

5. The agent according to claim 2, characterized in that it does not contain bleach.

6. The agent according to claim 2, characterized in that it is present as a preprepared dosing unit having a water-soluble casing.

7. A method for removing stains from textile materials using N-alkyl substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide of the general formula (I), ##STR00009## where R is an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, each R.sup.1 independently is F, Cl, Br or I, and each R.sup.2 independently is H, F, Cl, Br or I, in an aqueous liquid, which contains the soiled textile materials that are in need of a wash, with irradiation of the aqueous washing liquor with visible light, as photobleaching agent to remove stains from textile materials.

8. The method according to claim 7, characterized in that light in the wavelength range from 400 nm to 600 nm, in particular from 250 nm to 525 nm, is used.

9. The use according to claim 1, characterized in that the N-alkyl-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide of the general formula (I) is used in concentrations in the range from 0.0001 mmol/l to 0.1 mmol/l, in particular from 0.001 mmol/l to 0.01 mmol/l in aqueous washing liquids which are in particular alkaline.

10. The use according to claim 1, characterized in that, in formula (I), the radical R carries substituents selected from-OH, COO.sup.?M.sup.+, SO.sub.3.sup.?M.sup.+, OSO.sub.3.sup.?M.sup.+, N.sup.+(CH.sub.2CH.sub.3).sub.3Hal.sup.? and mixtures thereof, where M.sup.+is a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? is Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be omitted if COO.sup.?, SO.sub.3.sup.?, OSO.sub.3.sup.? and N.sup.+(CH.sub.2CH.sub.3).sub.3 is present in a charge-balancing amount; and/or that all radicals R.sup.1 are the same and are in particular Br and/or in that all radicals R.sup.2 are identical and are in particular H.

11. The method according to claim 7, characterized in that the N-alkyl-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide of the general formula (I) is used in concentrations in the range from 0.0001 mmol/l to 0.1 mmol/l, in particular from 0.001 mmol/l to 0.01 mmol/l in aqueous washing liquids which are in particular alkaline.

12. The agent according to claim 2, characterized in that, in formula (I), the radical R carries substituents selected from-OH, COO.sup.?M.sup.+, SO.sub.3.sup.?M.sup.+, OSO.sub.3.sup.?M.sup.+, N.sup.+(CH.sub.2CH.sub.3).sub.3Hal.sup.? and mixtures thereof, where M.sup.+is a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? is Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be omitted if COO.sup.?, SO.sub.3.sup.?, OSO.sub.3.sup.? and N.sup.+(CH.sub.2CH.sub.3).sub.3 is present in a charge-balancing amount; and/or that all radicals R.sup.1 are the same and are in particular Br and/or in that all radicals R.sup.2 are identical and are in particular H.

13. The method according to claim 7, characterized in that, in formula (I), the radical R carries substituents selected from-OH, COO.sup.?M.sup.+, SO.sub.3.sup.?M.sup.+, OSO.sub.3.sup.?M.sup.+, N.sup.+(CH.sub.2CH.sub.3).sub.3Hal.sup.? and mixtures thereof, where M.sup.+is a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? is Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be omitted if COO.sup.?, SO.sub.3.sup.?, OSO.sub.3.sup.? and N.sup.+(CH.sub.2CH.sub.3).sub.3 is present in a charge-balancing amount; and/or that all radicals R.sup.1 are the same and are in particular Br and/or in that all radicals R.sup.2 are identical and are in particular H.

Description

EXAMPLES

Example 1: Preparation of N-dodecanyl-2-(2,4,5,7-tetrabromo-6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide

[0084] ##STR00006##

[0085] Based on published methods (S. Ficht, L. R?glin, M. Ziehe, D. Breyer, O. Seitz, Direct Carbodiimide-Mediated Conjugation of Carboxylates Using Pyridinium p-Toluenesulfonate and Tertiary Amines as Additives, Synlett 2004, 14, p. 2525-2528; S. M. Bystryak, A. I. Kotel Nikov, G. I. Likhtenshtein, V. I. Nikulin, Luminescence study of intermolecular interactions between excited octadecyleosinamide molecules and solvent molecules in polar and nonpolar solvents, Journal of Applied Spectroscopy 1990, 52, No. 2, p. 158-163), 0.70 g 1-hydroxybenzotriazole (4.30 mmol), 3.24 g pyridinium-p-toluenesulfonate (4.30 mmol), 0.90 g dicyclohexylcarbodiimide (4.30 mmol) and 1.10 g of diisopropylethylamine (8.60 mmol) were added successively with stirring in a round-bottom flask to a mixture of 20 ml of dimethylformamide and 3.00 g of eosin Y (4.30 mmol), After 30 minutes, 0.8 g of 1-dodecylamine (4.3 mmol) was added and the reaction mixture was stirred at room temperature for a further 24 h. The mixture was acidified with dilute aqueous acetic acid and extracted repeatedly with dichloromethane to terminate the reaction. The combined organic phases were dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure. Subsequently, a column chromatography was carried out on silica gel to purify the crude product; solvents acetone/dichloromethane in a mixing ratio of 1:5 This gave N-dodecyl-2-(2,4,5,7-tetrabromo-6-hydroxy-3-oxo-3H-xanthen-9-yl) benzamide (M1) as a white solid with a yield of 42%.

Example 2: Degradation of ?-Carotene

[0086] Using a simplified model reaction, the decolorization of the yellow dye ?-carotene originating from carrot was visualized and characterized using a UV/VIS spectrum. For this purpose, the same volume fractions of a solution of 0.01 mM ?-carotene in chloroform and a solution of 0.0001 mM of the compound M1 prepared in Example 1 were mixed in chloroform and 0.1% diisopropylethylamine in a cuvette, and the cuvette was placed in the Analytik Jena Specord S600 spectrometer. The degradation of the dye ?-carotene was determined with the smallest possible distance between the cuvette and a blue-light-emitting LED lamp (450 nm). The data given in Table 1 below resulted.

TABLE-US-00001 TABLE 1 Degradation of the dye ?-carotene. Absorption Absorption maximum maximum (t = 0 min) (t = 5 min) Degradation Photoactivator [a.u.] [a.u.] [%] . No DIPEA 1.70 1.44 15 , DIPEA only 1.70 1.44 15 M1 + DIPEA 1.70 0.91 47