Textile optical brighteners

Agent: Michel Lordonnois, 82, rue de ia Justice, 91-Montgeron.

Optical lightening agent.

72) invention ¢ 30) Conventional priority:

(32) (33) (3?) Patent application filed in the Federal Republic of Germany on July 2, 1968, No. P 17 70 773.2 in the name of the applicant.

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22269

Optical lightening agents are known from the class of 1,3-diarylpyrazoline compounds suitable for the optical lightening of wool and synthetic fibers, especially polyamide fibers. The disadvantage of these lightening agents however lies in the fact that they are relatively poorly fixed on the fibers of chemically modified or crosslinked cellulose or on mixed fabrics of polymer fibers and of cellulose and that they thus produce only a weak improvement of whiteness »

When, for the lightening of such a fibrous material or of the textiles made therefrom, use is made of the lighteners known, of the b is-triazinyl-stilbene-disulfonic acid type, it is found that in the post-treatment of the textile article washed with a cationic brightening agent, a more or less pronounced extinction of the fluorescence takes place. to give textiles a soft and pleasant touch ”

The applicant has set itself the objective of developing an optical lightening agent which eliminates the drawbacks mentioned above "

The subject of the invention is an optical lightening agent characterized by the formula:

^—î +

<img file="FR2012166A1_D0001.tif" />

in which the various symbols have the following meaning:

X = -SO₂NH₂ , -S0₂R, -SO₂-OR, -COOR, -CONH₂ , —CN, -CF₃ , halogen, OR, R, X '= halogen, OR, R, / R / R / R

Y = —CONR '(CH_) -NR, —CONR' (CH_) NR '(CH „) —NR, -COO (CHj -NR”, n \_R„2 n 2 n \_RI, 2 n \_R1,

R /

- (CHL) -NR,

R

BAD OFUGüNAL

Y '= H, R or an unsubstituted phenyl residue,

Z = H or Y,

Z '= H or R,

R = alkyl residue having 1 to 4 carbon atoms,

R '= H or R, b9 22269

R = R or - (CH ^^ CH ^ H, n = 2, 3 or 4,

AT^- = an anion of an acid "

Of particular interest are the optical brighteners of for5 mule

<img file="FR2012166A1_D0002.tif" />

VS

N i

<img file="FR2012166A1_D0003.tif" />

<img file="FR2012166A1_D0004.tif" />

NOT

-In which symbols

X = -SO_NH, -COOR, -COI'ÎH,, _{/ R}_ZR. _{/ R}

Y = -COÎÎR '(CH ,.) -HR, = CQNR' (CH,) ÎÎR '(CH-) NR ”or -COO (CH_) N — R”? not \_R„2 n 2 n \_R„2 n \_R„

R = an alkyl residue having 1 to 3 carbon atoms,

R '= H or R,

R = R or (CHp ^ CH ^ H, n = 2 or 3,

A ~ = a halide, acetate or alkylsulphate ion or the equivalent of a polyvalent acid; for example sulfuric, phosphoric, oxalic and citric acid "

D

For the preparation of Ί ^ -Δ ^ —diarylpyrazolines substituted in position 4 and 5 or respectively 4 or 5 by quaternary ammonium groups, the preparation of the corresponding tertiary amines is first necessary; these tertiary amines can be converted by the usual methods into quaternary salts "z 2

With a view to the preparation of diaryl-Δ -pyrazolines substituted by tertiary amino groups in position 4 and 5 or in position 4 or 5, it is envisaged, in particular, the reaction of derivatives containing tertiary amino groups of acrylic acid, fumaric or maleic with substituted α-halobenzaldehyde-phenyl-hydrazones »Suitable derivatives of acrylic, fumaric and maleic acid are, for example, the amides and esters of the following formula:

H

HC = CH - C - N - ² ! l

O ^&lt;CH2&gt;3

H ..

<img file="FR2012166A1_D0005.tif" />

BAD ORIGINAL

22269

CH_O / 3! 2 2 \ 'o ch₃

HC ³ \

HH

N - (CH-L · -O-Ç-C = C- Ç- O- (CH _) - - M

H₃C, CHCH^H3^VS\ H HH /^CH3

- &lt;Oî₂⁾3 - N - C ~ C = C - C - N - (CH₂)₃ - NOT

HjCT â O ^CH3

In addition, it is possible to use the amides or esters of acrylic, fumaric or maleic acid of diethylene triamine or of its methylated products, of triethanolamine, tripropanolamine and of N-hydroxyethyl-N, N'-trimethyl-ethylene diamine "

The reaction of the aforementioned amides or esters with the substituted α-halobenzaldehyde-phenylhydrazones takes place with ease in the presence of an acid acceptor in the sense of a 1,3-dipolar cycloaddition, in this case the derivative d hydrazone being intermediate transposed into a diphenyl nitrilimine. Suitable acid acceptors are, for example, primary, secondary and, in particular, tertiary aliphatic or cycloaliphatic amines or alternatively alkali or alkaline earth metal carbonates, hydrogen carbonates or hydroxides.

The α-halogenated derivative of substituted benzaldehyde-phenylhydrazone can be obtained in known manner from the corresponding hydrazone, by halogenation, for example with phosphorus pentachloride.

K following reaction course s

<img file="FR2012166A1_D0006.tif" />

BAD ORIGINAL

22269

20(2166

Z '

<img file="FR2012166A1_D0007.tif" />

where the symbols X and Y correspond to the groups X and Y but, contrary to these, they do not contain quaternary nitrogen atoms.

The reaction of the amide or of the ester with the halogenated hydrazone is advantageously carried out hot, in the presence of a solvent, in this case tetrahydrofuran giving particularly satisfaction.

Then, the substituted diarylpyrazoline can be quaternized in a known manner, for this it is possible to use the usual quaternizing agents such as alkyl halides, dialkoyl sulfates or hydrochlorides, the hydrocarbon residues of which contain 1 to 4, preferably 1 to 3 carbon atoms.

The optical lightening agents in accordance with the invention are suitable for lightening textiles and other articles made of cellulose, regenerated cellulose and synthetic fibers, in particular also those of finished or crosslinked cellulose and mixed fabrics of cellulose and polypropylene fibers.

For the last species of fibers mentioned, no suitable lightening agent has hitherto been known.

The lighteners can be used alone or in combination with washing agents for textiles. Of particular importance is the fact that textiles treated with the lighteners according to the invention or washed with a washing agent containing them can be rinsed subsequently with a common cationic brightening agent, without downgrading the degree of whiteness. .

Example: To a cooled solution (+ 1 ° C) of 46.8 g (0.25 mole) of phertylhydrazine-sulfonic acid- (4) -amide- (3) in 250 cm of anhydrous dimethylformamide, dropwise added drop, with stirring and cooling,

21.8 g (0.125 mole) of p-chlorobenzoyl chloride. Then the mixture is stirred again for three quarters of an hour at + 2 ° C. and, after elimination of the ice bath, it is then stirred for three hours at room temperature. .

After having removed the solvent by vacuum distillation, the original bad is taken again x

b9 22269 ⁵ 2012166 crystalline paste in 500 cm of water to remove the hydrazine hydrochloride and the insoluble p-chloro-p-benzoyl-phenyl-hydrazine-sulfonamide is filtered off with suction, washed twice with cold water and, after drying, it is recrystallized twice from approximately 3.5 liters of ethanol (melting point 267 ° centigrade).

34.1 g (0.105 mole) of finely pulverized p-chloro-p-benzoyl-phenyl-hydrazine-sulfonamide and 26.6 g (0.128 mole) of pentachloride are heated to boiling under reflux with stirring for 22 hours. phosphorus in 400 cm of anhydrous methylene chloride protected from humidity. In the suspension is then introduced, with stirring, 42.6 g of phenol, obtaining in a short time, with a strong simultaneous release of hydrochloric acid, a clear solution which. soon becomes cloudy due to crystal separation. After crystallization in an ice bath, the crystals are filtered off with suction and washed twice with cold methylene chloride. After recrystallization from acetone with addition of water, 1-p-chloro-benzo- (2-p-sulfonamidophenyl-hydrazine) chloride is obtained in the form of colorless crystals.

(Melting point 218-219 ° C).

A 27.6 g (0.08 mole) of the abovementioned compound and 37.4 g (0.24 mole) of dimethylaminopropylamide of acrylic acid which has been stabilized with 1 g of hy3, -x droquinone, in 280 cm of anhydrous tetrahydrofuran, 16.0 g (0.16 mole) of triethylamine are added dropwise. After boiling for one hour at reflux, the mixture is cooled and then, after separation by filtration of the triethylammonium chloride, the solution is concentrated by evaporation under vacuum, it is taken up in hot acetone and water is added to it. 'to the formation of a disorder. The cry precipitating rates of cold N-dimethylaminopropylamide of 1-p-sulfonami acid, 2 do-phenyl-3-p-chlorophenyl-A -pyrazoline-carboxylic acid (5) are recrystallized twice from ethanol. 6.8 g (0.0147 mole) of this compound are dissolved

3 in 100 cm of methanol and 9.4 g (0.074 mole) = 7.2 cm of dimethyl sulfate are added. This solution is heated with stirring to 40 ° C for three and a half hours. Then it is cooled in an ice bath, the precipitated crystals are filtered with suction and then washed with a little methanol. After double recrystallization from methanol, the methosulfate of N-trimethylammonium-propylamide of lp-sulfonamidophenyl-3-p-chlorophenylΔ -pyrazoline-carboxylic acid- (5) is obtained in the form of colorless crystals melting at 177 ° C. an amount of 7.8 g.

Pieces of cotton, viscose and acetate rayon linen treated with this lightening agent, as well as, moreover, cotton items with synthetic or cross-linked resin finish, as well as a mixed cotton and polypropylene fiber fabric (Meraklon brand), have a pure white appearance.

b9 222b9