Textile optical brighteners

SWEDEN

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PATENTS AND REGISTRATION OFFICE

PUBLISHING POSITION No. 360 361 Intel c 07 d 49/10

Patent Application. No. 7902/69 Received on 4 VI 19 ^ 9

Validity Day, 4 VI 19 ^ 9

Ans. generally available on 3 I 197θ

Ans. published and the pamphlet published on 24 IX 1973

Priority requested from 2 VII 1968 (Federal Republic of Germany DT, 17 70 775)

HENKEL &amp; GIE GMBH, DÖSSELDOHF, FEDERAL REPUBLIC OF GERMANY DT Inventor »HJ Krause and M Dohr, DUsseldorf-Holthausen Agents» L Brann

Optical brightener

Whiteners belonging to the class constituted by 1,3-diarylpyrazoline compounds are known which are suitable for optical bleaching of wool and synthetic fibers, especially polyamide fibers. The disadvantage of these brightening agents, however, is that they have relatively poor affinity for chemically transformed and resp. cross-linked cellulose or to blend fabrics of polymer fibers and cellulose, thereby providing only a slight improvement of the white value. Are used for bleaching such a fiber material or the known fabrics of the known bis-triazinyl-style benz disulfonic acid type whitening agents, it is found that upon finishing the washed textile goods with a cationic stripping agent, a more or less strong fluorescence quenching occurs. However, such finishing is desirable in many cases, especially in household laundry, to give the textiles a pleasantly soft grip.

The object of the present invention is to provide an optical brightener which eliminates the disadvantages described above.

The object of the invention is an optical brightener, which is characterized by having the formula:

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_ZR. R wherein Y = -CONR '(CH 2) -N - R, -CONR * (CH 2) NR * (CH 2) -N - R or \ R^{n 4 n} \ rh

-COO (CEL) -N - R, wherein: ^{2 n} Xr «

R = an alkyl group having 1-3 carbon atoms,

R '= H or R,

R = R or (CH ~), CH_O0H, n - l. 2 n = 2 or 3 »as well

A “= a halide, acetate or alkyl sulfate ion or an equivalent of a polyhydric acid, e.g. sulfuric, phosphorus, oxalic or citric acid.

For the preparation of the 5-position diaryl-Δ-pyrazolines substituted with tertiary amino groups, particular reaction is to the reaction of derivatives of acrylic, fumaric or maleic acid containing tertiary amino groups with substituted α-halo benzaldehyde phenylhydrazones. Suitable derivatives of acrylic, fumaric and maleic acid are e.g. the amides and the esters with

hrs

H, C = CH - C - N - (CH ^z il ^On 3 the following formulas:

_t/^CH3

CH 3,

hrs₂C - CH / CH (CHJ. - &lt; ³²2, 'CH

H, C ^d N - (CH 2). - O "/ 2

CH

C

II o

o (CH₂) fr ·

CH, C_S Η Η H / CH ^d N- (CH,) - N - C'- C = C - C - N (CH,) - fr _c^{z 3} 4 ö ^{3 ScH};

41st dl

...................

Furthermore, as the starting material, the acrylic, fumar or maleic acid amides and the like can be used. the esters of diethylenetriamine and its methylation products, triethanolamine, tripropanolamine and N-hydroxyethylNjN'-trimethylethylenediamine.

The reaction of the above-mentioned amides, respectively. Esters with the substituted α-halo-benzaldehyde-phenylhydrazones are readily present in the presence of an acid acceptor by means of a 1,3-dipolar cycloaddition, the hydrazone derivative being intermediately rearranged into a diphenylnitrilimine. Suitable acid acceptors are e.g. aliphatic or cycloaliphatic primary, secondary and especially tertiary amines or, or also carbonates, hydrogen carbonates or hydroxides of alkali and hydroxides respectively. alkaline earth metals.

The α-halogen derivative of the substituted benzaldehyde-phenylhydrazone can be obtained in known manner from the corresponding hydrazone by halogenation, e.g. with phosphorus pentachloride. Thus, the following reaction procedure applies:

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wherein the symbols X 'and Y correspond to the groups X and Y but, in contrast, do not contain any quaternary nitrogen atoms.

'4 • The turnover of amide and resp. The ester with the halogenated hydrazone is suitably heated in the presence of a solvent, varvic. in tetrahydrofuran has been found to be particularly suitable.

Subsequently, the substituted diarylpyrazoline can be quaternized in known manner, using conventional quaternization agents, e.g. alkyl halides, dialkyl sulfates or chlorohydrin, the hydrocarbon groups of which contain 1-4, preferably 1-3 carbon atoms.

The optical brighteners according to the invention are suitable for bleaching textiles and other articles of cellulose, cellulose regenerated and synthetic fibers, especially, however, of those of appr.

cross-linked cellulose as well as cellulose and polypropylene blends. ✓ fibers. For the latter fiber types, no suitable whitening agent has so far been known. The whitening agents can be used separately or in combination with textile detergents. Of particular importance is the fact that those treated with the whitening agents according to the invention, respectively. with a detergent-containing detergent, the washed fabrics can be rinsed off with a conventional cationic detergent without any decrease in the white value.

The invention is further illustrated by the following examples, i

Example.

To a cooled solution (+ 1 ° C) of 46.8 g (0.25 mole) of phenylhydro-; zinsulfonic acid (4) amide (3) in 250 ml of anhydrous dimethylformamide was added with stirring and cooling 21.8 g (0.125 mol) of p-chlorobenzoyl chloride dropwise. Then the solution was stirred at + 2 ° C for 3/4 hour and further stirred for 3 hours at room temperature after. removal of the ice bath.

After distilling off the solvent in vacuo, the crystal porridge was taken up in 500 ml of water to remove the hydrochloric acid hydrazine, and the insoluble p-chloro-P-benzoyl-phenylhydrazine-sulfonic acid amide was suctioned, washed twice with cold water, and recrystallized twice from drying. about 3.5 liters of ethanol. The melting point of the resulting product was 267 ° C.

34.1 g (0.105 mole) of the finely powdered p-chloro-p-benzoylphenylhydrazine sulfonic acid amide and 26.6 g (0.12 $ mole) of phosphorus pentachloride were refluxed in 400 ml of anhydrous methylene chloride for 22 hours, excluding moisture and with stirring. Then, with stirring, 42.6 g of phenol were added to the suspension, giving a clear solution for a short period of time under vigorous hydrochloric hydrogen, which, however, soon became cloudy due to crystallisation. After crystallization in an ice bath, the crystals were sealed and washed twice with cold methylene chloride. After recrystallization from acetone under t. Addition of water yielded lp-chlorobenzene (2-p-sulfonamide phenylhydrazine) chloride in the form of colorless crystals. Its melting point was 218219 ° C.

27.6 g (0.08 mole) of the above compound and 37.4 g (0.24 mole) of acrylic acid dimethylaminopropylamide stabilized with 1 g of hydroquinone were added in 280 ml of anhydrous tetrahydrofuran with 16.0 g (0). 16 moles of triethylamine dropwise. After 1 hour of reflux, the solution was cooled and evaporated in vacuo after filtering off the triethylammonium chloride, after which the product was taken up in hot acetone and added with water until. clouding occurred. The cold precipitated crystals of 1β-sulfonamidophenyl-3-β-chlorophenyl-A²-pyrazoline-carboxylic acid (5) -Ndimethylamine-propylamide was recrystallized twice from ethanol. 6.8 g (0.0147 mol) of this compound was dissolved in 100 ml of methanol and added with 9.4 g (0.074 mol) = 7.2 ml of dimethyl sulfate. This solution was heated for 3.5 hours at 40 ° C with stirring. Then the solution was cooled in an ice bath and the precipitated crystals were aspirated and washed with a small amount of methanol. After recrystallisation twice from methanol p

1p-sulfonaroidophenyl-3-p-chlorophenyl-α-pyrazoline-carboxylic acid (5) -N-trimethylammonium propylamide methosulfate was obtained in the form of colorless crystals having a melting point of 177 ° θ and in an amount of 7.8 g.

With this Whitening treated laundry made of cotton, the viscous art side and acefcatrayon, further by artificial resin accented and resp. cross-linked. cotton and a blend of cotton and polypropylene fiber (Meraklon®) showed a pure white appearance.

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