ANTHRACENE-9,10-DIONE DERIVATIVES AS PHOTOACTIVATORS IN DETERGENTS

Abstract

Anthracene-9,10-dione derivatives are capable of producing bleach-active species under irradiation of visible light, which lead to an increase of the bleaching power during the washing of textiles.

Claims

1. A use of alkyloxy-substituted anthracene-9,10-diones of the general formula (I), ##STR00006## in which R.sup.1 and R.sup.2 independently of one another for H, SO.sub.3.sup.?M.sup.+ or an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, with the proviso that at least one of the radicals R.sup.1 or R.sup.2 is an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, X is H or SO.sub.3.sup.?M.sup.+ and M.sup.+ stands for a proton, an alkali metal ion or an ammonium ion or mixtures thereof as photobleach to remove soiling of textile materials.

2. A washing agent comprising alkyloxy-substituted anthracene-9,10-dione of the general formula (I), ##STR00007## in which R.sup.1 and R.sup.2 independently of one another for H, SO.sub.3.sup.?M.sup.+ or an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, with the proviso that at least one of the radicals R.sup.1 or R.sup.2 is an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, X is H or SO.sub.3.sup.?M.sup.+ and M.sup.+ stands for a proton, an alkali metal ion or an ammonium ion or mixtures.

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. %, of alkyloxy-substituted anthracene-9,10-dione 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 any bleaching agents.

6. The agent according to claim 2, characterized in that it is present as a prefabricated dosage unit with a water-soluble coating.

7. A method for removing stains from textile materials using Alkyloxy-substituted anthracene-9,10-diones of the general formula (I), ##STR00008## in which R.sup.1 and R.sup.2 independently of one another for H, SO.sub.3.sup.?M.sup.+ or an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, with the proviso that at least one of the radicals R.sup.1 or R.sup.2 is an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, x is H or SO.sub.3M.sup.? and M.sup.+ is a proton, an alkali metal ion or an ammonium ion or mixtures thereof, in an aqueous washing liquid in which the washing in need of textile materials is located, while irradiating the aqueous washing liquid with visible light.

8. The method according to claim 7, characterized in that light in the wavelength range from 400 nm to 600 nm, in particular from 450 nm to 525 nm, is used.

9. The use according to claim 1, characterized in that the alkyloxy-substituted anthracene-9,10-dione 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 liquor.

10. The use according to claim 1, characterized in that, in formula (I), R.sup.1 and R.sup.2 is independently an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, and/or R.sup.1 and R.sup.2 is substituted and substituents selected from OH, COO.sup.?M, SO.sub.3.sup.?M, OSO.sub.3.sup.?M, N(CH.sub.2CH.sub.3).sub.3Hal.sup.?- and the mixing of which is carried out, wherein M.sup.+ for a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? for Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be missing if COO.sup.?, SO.sub.3.sup.?, and OSO.sub.3.sup.? and N(CH.sub.2CH.sub.3).sub.3 are present in charge-balancing quantity.

11. The method according to claim 7, characterized in that the alkyloxy-substituted anthracene-9,10-dione 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 liquor.

12. The agent according to claim 2, characterized in that, in formula (I), R.sup.1 and R.sup.2 is independently an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, and/or R.sup.1 and R.sup.2 is substituted and substituents selected from OH, COO.sup.?M, SO.sub.3M, OSO.sub.3.sup.?M, N(CH.sub.2CH.sub.3).sub.3Hal.sup.?- and the mixing of which is carried out, wherein M.sup.+ for a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? for Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be missing if COO.sup.?, SO.sub.3.sup.?, and OSO.sub.3.sup.? and N(CH.sub.2CH.sub.3).sub.3 are present in charge-balancing quantity.

13. The method according to claim 7, characterized in that, in formula (I), R.sup.1 and R.sup.2 is independently an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, and/or R.sup.1 and R.sup.2 is substituted and substituents selected from OH, COO.sup.?M, SO.sub.3.sup.?M, OSO.sub.3.sup.?M, N(CH.sub.2CH.sub.3).sub.3Hal.sup.?- and the mixing of which is carried out, wherein M.sup.+ for a proton, an alkali metal ion, an ammonium ion and mixtures thereof and Hal.sup.? for Cl.sup.?, Br.sup.?, J.sup.?, F.sup.? and mixtures thereof and M.sup.+ and Hal.sup.? can also be missing if COO.sup.?, SO.sub.3.sup.?, and OSO.sub.3.sup.? and N(CH.sub.2CH.sub.3).sub.3 are present in charge-balancing quantity.

Description

EXAMPLES

Example 1 Preparation of Substituted Anthracenediones

a) Synthesis of 1.2-bis(octyloxy)anthracene-9,10-dione

[0089] ##STR00005##

[0090] Based on published procedures (X. Chen, K. Ding, L. Jun, Synthesis, identification and application of aldehyde reactive dyes, Dyes and Pigments 2015, 123, 404-412 and Ioannis Drivas, Richard S. Blackburn, Christopher M. Rayner, Natural anthraquinonoid colorants as platform chemicals in the synthesis of sustainable disperse dyes for polyesters, Dyes and Pigments 2011, 88, 7-17) a mixture of 30 ml dimethylacetamide, 2.00 g alizarin (8.30 mmol) and 3.50 g of potassium carbonate (25 mmol) heated to 80? C. and reacted with each other for 30 min. 4.80 g of 1-bromooctane (25 mmol) were then added, and the reaction mixture was stirred for a further 16 h. To terminate the reaction, the mixture was cooled to room temperature and admixed with dimethylacetamide. The mixture was filtered and the residue was washed with dimethylacetamide until a yellow solid was apparent. The residue was then dried under reduced pressure. This gave 1,2-bis(octyloxy)anthracene-9,10-dione (M1) as a yellow solid with a yield of 94%.

b) Preparation of further 1,2-bis(alkyloxy)anthracene-9,10-diones

[0091] Analogously to the procedure described in a), 1,2-bis(decyloxy)anthracene-9,10-dione (M2), 1,2-bis(dodecyloxy)anthracene-9,10-dione (M3) and 1,2-bis(hexadecyloxy)anthracene-9,10-dione (M4) were prepared.

Example 2: Degradation of Lycopene

[0092] Using a simplified model reaction, the decolorization of the red dye lycopene, which comes from tomatoes, was visualized and characterized using a UVNIS spectrum. For this purpose, the same volume parts of a solution of 0.01 mM lycopene in chloroform and a solution of 0.0001 mM in each case of a compound prepared in example 1 in chloroform were mixed in a cuvette and the cuvette was placed in a specord S600 spectrometer, analytik jena, measuring shaft surface 480 nm. With the smallest possible distance between the cuvette and a blue light-emitting LED lamp (450 nm), the kinetics of the degradation of the dye lycopene were determined. The data given in Table 1 below resulted.

TABLE-US-00001 TABLE 1 Degradation of lycopene, pseudo 1st order reaction Absorption Absorption maximum maximum Photo- K t.sub.1/2 (t = 0 min) (t = 5 min) Degradation activator [min.sup.?1] [min] [a.u.] [a.u.] [%] 0.006 107 1.00 0.98 2 M1 0.28 2.5 1.00 0.40 60 M2 0.28 2.5 1.00 0.47 53 M3 0.28 2.5 1.00 0.51 49 M4 0.28 2.5 1.00 0.53 47

Example 3: Degradation of ?-carotene

[0093] Example 2 was repeated using the yellow dye ?-carotene, which comes from carrots among other things, instead of lycopene and a measuring wavelength of 463 nm. The data given in Table 2 below resulted.

TABLE-US-00002 TABLE 2 Degradation of ?-carotene, pseudo 1st order reaction Absorption Absorption maximum maximum Photo- K t.sub.1/2 (t = 0 min) (t = 5 min) Degradation activator [min.sup.?1] [min] [a.u.] [a.u.] [%] 0.027 29 1.00 0.87 13 M1 0.31 2 1.00 0.17 83 M2 0.31 2 1.00 0.20 80 M3 0.31 2 1.00 0.22 78 M4 0.31 2 1.00 0.27 73