DE2525637A1 - DISTILBENYL OXDIAZOLE - Google Patents

Description

C'PA

CLBA-GElGY AG, Basel, Switzerland V ^ NL. ^ i V mJL. I V> I

Case 1-9452 / -

Germany

Distilbenyl-oxdiazoles

The present invention relates to distilbenyl-oxdiazoles, a process for their preparation and their use as optical brightening agents for high molecular weight organic materials,

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^R 2 ^ The inventive \ = / - { ■ - T Distilbenyl-oxdiazoles speak the formula -N (D ^R l H H ^R 1
\ I jjp V CH = CH- < SO ₃ M SO ₃ M

R, hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl, cyano,

Carboxy or carbalkoxy with 2 to 6 carbon atoms, R ₂ hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine,

R- hydrogen or alkyl having 1 to 4 carbon atoms and M is a hydrogen, alkali metal, alkaline earth metal, ammonium

or amine salt ion
mean.

"Carboxy" and "Sulfo ¹ " are to be understood as meaning the radicals -COOM or -SO-M, where M stands for hydrogen or a salt-forming cation. Salt-forming cations M are generally those of alkaline earth metals, for example calcium and barium or magnesium, and in particular alkali metals, for example sodium or potassium, but also ammonium or amine salt ions of cyclic amines, such as pyridine, morpholine and piperidine, optionally substituted by alkyl or hydroxyalkyl having 1 to 4 carbon atoms Hydrogen in particular

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Potassium and the sodium cation.

The compounds of the formula deserve special mention

(2) R [ _H H

cH = CH- / V ^ Vf VcH = CH-

N N '

SO ₃ M SO ₃ M

R'-j is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl,

Cyano, carboxy or carbomethoxy,

and R ¹ 2 hydrogen, chlorine or alkyl with 1 to 4 carbon atoms /

R'o hydrogen or methyl

as well as the compounds of the formula

(3) H H

> M. S. .. _ N ₁ t> II

CH =

I = CH- (V / V / 7-CH = CH-N N

wherein

R "^ hydrogen, methyl, ethyl, methoxy, chlorine, sulfo, cyano,

Carboxy or carbomethoxy and
R " ₂ denotes hydrogen, chlorine, methyl or ethyl.

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Compounds of particular practical interest are those of the formula

(4)

CH = CH -

-CH = CH

N N

tv "I

^R l

SO ₃ M ₁

wherein

R " ¹ , hydrogen, chlorine or sulfo, R ¹ " 2 hydrogen or chlorine and M, a hydrogen, sodium or potassium ion

mean

and those of the formula (5)

CH = CH-

worm

R "", hydrogen, alkyl with 1 to carbon atoms, alkoxy with

1 to 4 carbon atoms or chlorine, M, _s is a hydrogen, sodium or potassium ion and η the number 1 or 2.

The present invention also relates to a

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drive for the preparation of the compounds of the formulas (1) to (5).

The process according to the invention for the preparation of the compounds of the formula

SO ₃ M

R, hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, suIfo, sulfophenyl, cyano, Carboxy or carbalkoxy with 2 to 6 carbon atoms,

R2 is hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine,

Ro is hydrogen or alkyl having 1 to 4 carbon atoms and

M is a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion

mean,

is characterized in that one mole of a compound of the formula

'"■■ OrVO- ··

N N

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with 2 moles of a compound of the formula

implements, whereby

R ,, R ₉ , Ro and M have the meanings given above and

one of the symbols Z and Z _{9 is} an O = CH group and the other is one of the groupings of the formula

(8a) -CH,

■ po- _V]

0-V _n

O (8b) -CH ₂ POV ₁

*1

(8e) -CH

and

(8d)

-CH

PV ₁

mean in which

V-j is an optionally further substituted alkyl radical, preferably one with up to 6 carbon atoms, an aryl radical, preferably phenyl radical, a cycloalkyl radical, preferably represents a cyclohexyl radical or an aralkyl radical, preferably a benzyl radical.

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Compounds of the formulas (2) to (5) are obtained in a completely analogous manner by reacting a compound of formula

C Il

O.

C-

Il

with a compound of the formula

(9) H.

^R 2 R ₃

respectively

SO ₃ M

(10)

Z "-

SO ₃ M

respectively,

(11) H.

■ Rj ¹

respectively.

(12)

where in the formulas (6) and (9) to (12) the substituents

M _1, M ₁ , Z ₁ and Z _{2 have} the meanings given above.

^{1 day 1} R "R" TJ ¹ "O"»D" H

2'3'1> ^k 2 '1 ^J 2'

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In the preferred embodiment of the aforementioned production process, Z- ^ represents a radical of the formulas (8a) to (8d), in particular (8a), and accordingly Z _{2 represents} the O = CH group.

The compounds of the formulas (6) to (12) required as starting materials can in analogy to per se known processes are produced.

The manufacturing process is advantageously carried out in inert solvents. As examples of this be hydrocarbons such as toluene and xylene or alcohols such as methanol, ethanol, isopropanol, butanol, Glycols, glycol ethers, such as 2-methoxyethanol, hexanols, cyclohexanol and cyclooctanol, also ethers such as diisopropyl ether, tetrahydrofuran and dioxane and dimethyl sulfoxide, Called formamide and N-methylpyrrolidone. Particularly suitable are polar organic solvents such as dimethylformamide and dimethyl sulfoxide. Also in aqueous solution some of the conversions can be carried out.

The temperature at which the reaction is carried out can vary within wide limits. she is determined

α) by the resistance of the solvent used towards the respondents, in particular to the strongly basic alkali compounds,

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β) by the reactivity of the condensation partners and

γ) through the effectiveness of the solvent / base combination as a condensing agent.

In practice, temperatures between about 10 and 100 ° C are generally considered, in particular, when dimethylformamide or diraethylsulfoxide are used as solvents. The preferred temperature range is 20 to 60 ° C. However, higher temperatures can also be used under certain circumstances, if this is desirable to save time, or a less active, but cheaper condensing agent should be used; In principle, therefore, reaction temperatures are also in the range from 10 to 180.degree possible.

As a strongly basic alkali metal compounds, especially the hydroxides, amides and alcoholates (preferably those of primary 1 to 4 carbon atoms containing alcohols) are of the alkali metals into consideration, wherein for economic reasons, those of lithium, sodium and potassium of vorwiegendem interest. In principle, however, and in special cases, alkali metal sulfides and carbonates, aryl alkali compounds such as phenyl-lithium, or strongly basic amines (including ammonium bases, such as trialkylammonium hydroxides) can be successfully used.

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The novel compounds defined above show one more in a dissolved or finely divided state or less pronounced fluorescence. You can optically brighten a wide variety of synthetic, semi-synthetic or natural organic materials or substances containing such organic materials included.

For this purpose, for example, without any restriction being expressed by the following overview should be, the following groups of organic materials, as far as an optical brightening of the same in Considered, called:

I. Synthetic organic high molecular materials:

a) Polymerization products based on at least one polymerizable carbon-carbon double bond containing organic compounds, i.e. their homo- or copolymers and their aftertreatment products such as Crosslinking, grafting or degradation products, polymer blends or more reactive by modification Products obtained in groups, for example polymers based on cc, ß-unsaturated carboxylic acids or derivatives such carboxylic acids, especially acrylic compounds (such as acrylic esters, acrylic acid, acrylonitrile, acrylic

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amides and their derivatives or their methacrylic analogues), of olefin hydrocarbons (such as ethylene, propylene, Styrenes or dienes, also so-called ABS polymers). Polymers based on vinyl and vinylidene compounds (such as vinyl chloride, vinyl alcohol, vinylidene chloride),

b) Polymerization products obtainable by ring opening, e.g. polyamides of the polycaprolactam type, also polymers that are available both via polyaddition and polycondensation, such as polyethers or polyacetals,

c) Polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable Groups, their homo- and mixed condensation products and products of the aftertreatment, such as Polyesters, especially saturated (e.g. ethylene glycol terephthalic acid polyester) or unsaturated (e.g. maleic acid dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers), unbranched as well as branched (also based on higher alcohols, such as alkyd resins), polyesters, polyamides (e.g. hexamethylenediamine adipate), Maleinate resins, melamine resins, their precondensates and analogues, polycarbonates, silicones,

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d) Polyaddition products such as polyurethanes (crosslinked and uncrosslinked), epoxy resins.

II. Semi-synthetic organic materials, e.g. cellulose esters of various degrees of esterification (so-called 2 1/2 acetate, triacetate) or cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their aftertreatment products, casein plastics.

III. Natural organic materials of animal or vegetable origin, for example based of cellulose or proteins such as cotton, wool, linen, silk, natural lacquer resins, starch, casein.

The organic materials to be optically brightened can have a wide variety of processing states (Raw materials, semi-finished products or finished products). They can, on the other hand, take the form of the most diverse shaped structures exist, i.e., for example, as predominantly three-dimensionally extended bodies such as plates, Profiles, Spritzgussformling.e, various types of workpieces, chips, granulates or foams, also as predominantly two-dimensional bodies such as films, foils, varnishes, coatings, impregnations and coatings or as predominantly one-dimensional bodies such as threads, fibers, flakes, wires. The said materials

B 0 9 B B 1/1 Π 9 1

can on the other hand also in unformed states in the a wide variety of homogeneous or inhomogeneous forms of distribution, such as powder, solutions, emulsions, dispersions, Latices, pastes or waxes are present.

Fiber materials can for example be endless Threads (stretched or undrawn), staple fibers, flakes, hanks, textile threads, yarns, twisted threads, nonwovens, Felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as Papers, cardboard or paper pulp are present.

The compounds to be used according to the invention is important for the treatment of organic textiles Materials, in particular textile fabrics. If fibers, which as staple fibers or filaments, in the form of strands, woven fabrics, knitted fabrics, fleeces, flocked Substrates or composites can be present, are optically brightened according to the invention, this is done advantageously in an aqueous medium, in which the compounds in question are in finely divided form (suspensions, so-called Microdispersions, possibly solutions) are present. If necessary, dispersing, Stabilizers, wetting agents and other auxiliaries are added.

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Depending on the type of brightener compound used, it may prove beneficial to use neutral or alkaline or acidic baths. The treatment is usually carried out at temperatures of around 20 up to 140 ° C, for example at the boiling point of the bath or in the vicinity (about 90 ° C) carried out. For the inventive finishing of textile substrates come also solutions or emulsions in organic solvents into consideration, as is the case in dyeing practice in the so-called solvent dyeing (foulard thermofixing application, Exhaust dyeing process in dyeing machines) is practiced.

The new optical brightening agents according to the present Invention can also be added to or incorporated into the materials before or during their deformation. For example, they can be used in the production of films, foils (e.g. rolling in polyvinyl chloride in the Heat) or moldings of the molding compound or injection molding compound.

If the shaping of fully or semi-synthetic organic materials by spinning processes or spinning masses takes place, the optical brighteners can be applied using the following methods:

Addition to the starting substances (e.g. monomers) or intermediate products (e.g. precondensates, prepolymers),

50 9881/109 1

i.e. before or during the polymerization, polycondensation or polyaddition,

Powdering on polymer chips or granulates for spinning masses,

Bath coloring of polymer chips or granulates for spinning masses,

dosed addition to spinning melts or spinning solutions, application to tow before drawing.

- The new optical brightening agents according to the present one Invention can, for example, also be used in the following forms of application:

a) Mixtures with dyes (shading)

or pigments (coloring or especially e.g. white pigments) or as an additive to dye baths, printing, etching or reserve pastes. Also for the post-treatment of dyeings, Printing or etching.

b) In mixtures with so-called "carriers", wetting agents, Plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaching agents (Chlorite bleach, bleach bath additives).

c) In a mixture with crosslinkers, finishing agents (e.g. starch or synthetic finishes) as well as in combination with the most diverse textile finishing processes, in particular

5 0 9 3 8 1/1 0 9 1

- JLo -

Special synthetic resin finishes (e.g. crease-proof finishes such as ^M wash-and-wear "," Permanent-press "," no-iron "), furthermore flame-proof, soft handle, dirt removal (" anti-soiling ") or antistatic finishes or antimicrobial finishes,

d) Incorporation of the optical brightening agents into polymeric carrier materials (polymerization, polycondensation or polyaddition products) in dissolved or dispersed form Form for use e.g. in coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles, Fleece, paper, leather,

e) as additives to so-called "master batches",

f) as additives to a wide variety of industrial products in order to make them more marketable (e.g. Aspect improvement of soaps, detergents, pigments),

g) in combination with other, optically brightening substances,

h) in spin bath preparations, i.e. as additives to spinning baths, such as those used to improve lubricity the further processing of synthetic fibers can be used, or from a special bath before drawing the fiber,

i) As scintillators, for various photographic purposes Kind, such as for electrophotographic reproduction or supersensitization, for optical brightening photographic layers, optionally in combination with

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White pigments such as TiO ~.

If the whitening process is carried out with textile treatment or ennobling methods combined, the combined treatment can be advantageously used in many cases corresponding stable preparations are made which contain the optically brightening compounds in such a concentration contain that the desired lightening effect is achieved.

In certain cases, the brighteners are brought to their full effect by a post-treatment. This can represent, for example, a chemical (eg acid treatment), a thermal (eg heat) or a combined chemical / thermal treatment. For example, when optically brightening a number of fiber substrates, e.g. Room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100.degree. C. , it being generally advisable to dry the fiber material beforehand at a moderately elevated temperature, for example at least 60 to about 130.degree. The heat treatment in the dry state is then advantageously carried out at temperatures between 120 and 225 ° C., for example by heating

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in a drying chamber, by ironing in the specified temperature range or by treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out one after the other or combined in a single operation.

The amount of the new optical brighteners to be used according to the invention, based on that to be optically brightened Material can vary within wide limits. Even with very small amounts, in certain cases e.g. those of 0.0001 percent by weight, a clearer and more durable effect can be achieved. But it can also Amounts up to about 0.8 percent by weight and optionally up to about 2 percent by weight are used. For most practical concerns are preferably in amounts between 0.0005 and 0.5 weight percent.

The new optical brightening agents are also particularly suitable as additives for washing baths or for commercial and household detergents, which can be added in various ways. They are useful for washing baths in the form of their solutions in water or organic solvents or in finely divided form as aqueous Dispersions added. For household or commercial detergents, they are advantageous in any phase of the Manufacturing process of detergents, e.g. the so-called

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"slurry" before atomizing the washing powder or at the Preparation of liquid detergent combinations, added. The addition can be in the form of a solution or dispersion in water or other solvents as well as without auxiliaries as a dry brightener powder. You can For example, mix, knead or grind the lightening agent with the washing-active substances and finish Mix in washing powder. However, they can also be dissolved or predispersed and sprayed onto the finished detergent will.

The known mixtures of active washing substances, such as, for example, soap, are used as detergents of schnitzel and powder, synthetics, soluble salts of sulfonic acid half esters of higher fatty alcohols, higher and / or polyalkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters medium to higher alcohols, fatty acid acylaminoalkyl or aminoaryl glycerol sulfonates, phosphoric acid esters of fatty alcohols etc. in question. So-called "builders" include, for example, alkali poly- and polymetaphosphates, Alkali pyrophosphates, alkali salts of carboxymethyl cellulose and other "soil redeposition inhibitors", furthermore Alkali silicates, alkali carbonates, alkali borates, alkali perborates, nitrilotriacetic acid, ethylenediaminetetraacetic acid, Foam stabilizers such as alkanolamides of higher fat

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acids, into consideration. Furthermore, in the detergents, for example be included:

Antistatic agents, greasy skin protectants such as lanolin, enzymes, antimicrobials, perfumes and dyes.

The new optical brighteners have the particular advantage that they can also be used in the presence of active such as hypochlorite, are effective and without significant loss of the effects in washing baths with non-ionic detergents, e.g. alkylphenol polyglycol ethers can be used köxmen,

The compounds according to the invention are added in amounts of 0.005 to 1% or more, based on the weight of the liquid or powdery, finished detergent. Waschflottenj which contain the amounts of the claimed optical brighteners specified, impart beiis washing of textiles made of cellulose fibers, polyamide fibers, highly refined cellulose fiber, polyester fibers _^} wool etc. a brilliant appearance in daylight. «

The washing treatment is carried out, for example, as follows:

The specified textiles are used during 1 to 30 Minutes at 20 to 1 € 0 ° C in a washing bath that 1 to 10 g / kg of a built-up, composite detergent

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and 0.05 to VL> based on the weight of the detergent containing the lightening agent claimed. The liquor ratio can be 1: 3 to 1:50. After washing, it is rinsed and dried as usual. The washing bath can contain 0.2 g / l active chlorine (eg as hypochlorite) or 0.1 to 2 g / l sodium perborate as a bleach additive.

Unless otherwise stated, percentages in the examples are always percentages by weight. Enamel and Unless otherwise noted, boiling points are uncorrected.

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example 1

To a solution of 13.0 g of the compound of the formula

_W / ^ ^ ° _W ^OC 2 ^H 5

(101) P-CH ^ / VC C- ( V-CH P

/ ² \ / Il Il \ /

/ \ = / II II = \ H ₅ C ₂ O «« OC ₂ H ₅

and 12.2 g of 4-methylbenzaldehyde-3-sulfosa \ ire (sodium salt) in 150 ml of dimethyl sulfoxide, while stirring well and passing nitrogen over, 20 g of a 15% solution of sodium methylate in methanol are added dropwise over the course of about 5 minutes, the temperature of 20 ° C rises to 37 ° C. The mixture is then stirred for a further hour at 40 to 45 ° C., the reaction mixture is poured into 1.3 liters of water at 70 ° C., clarified by filtration, one liter of alcohol is added to the clear solution at 70 ° C. and 65 g of sodium chloride are slowly added. The product which has crystallized out is filtered off with suction after cooling and recrystallized from a mixture of 400 ml of water and 400 ml of alcohol. 7.2 g of the compound of the formula are obtained in this way

(102) H-C-f ^ -CH = CH

NaO ₃ S "" SO ₃ Na

as light yellow crystal powder.

S098S1 / 1031

- 23 -

The compound of the formula (101) can be obtained as follows:

To a solution of 74 g of the oxdiazole of the formula

HoC- (^ C
3 X ^ / "

and 0.5 g of dibenzoyl peroxide in 2000 ml of carbon tetrachloride are stirred and irradiated with a UV lamp 105.5 g of N-bromosuccinimide and 2.5 g of dibenzoyl peroxide at about 75 ° C in portions within about 30 minutes entered. Then it is refluxed for about 5 hours. After cooling, the crystallized Product sucked off, washed with a little alcohol and then with about 10 liters of hot water. After drying of the residue at 80 ° to 85 ° C. under reduced pressure, 81.3 g of the compound of the formula are obtained

(104) BrCH ₂ -

Melting point: 218 to 219 ° C.

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81.0 g of the compound (104) are added in portions with thorough stirring within about 30 minutes about 135 ° C registered in 400 ml of triethyl phosphite. The mixture is then stirred for about 4 hours at 145 ° C., with Ethyl bromide distilled off. After cooling, the product which has crystallized out is filtered off with suction with a little n-hexane washed and dried under vacuum at 50 to 55 ° C. This gives 85.9 g of compound (101) with a melting point 107 to 109 ° C.

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Example 2

To a suspension of 6.2 sodium methylate (content 96.0%) in 200 ml of dimethylformamide is added under good Stirring and passing nitrogen over a homogeneous mixture of 26.1 g of the compound of the form] (101) and 33.4 g of disodium salt of benzaldehyde-2,4-disulfonic acids (content: .92.7%) at 40 to 45 ° C entered in portions within about 15 minutes. Then another 3 hours at 40 Stirred up to 45 ° C. The reaction mixture is evaporated to dryness under vacuum, the residue in 350 ml yellow boiling water, mixed with 1050 ml of alcohol, hot-clarified by filtration, cooled and the product crystallized out suction filtered and dried at 100 to 110 ° C under vacuum.

16.7 g of the compound of the formula are obtained in this way

(105) NaOoS- / VcH = CH- / V-C

SO ₃ Na

SO ₃ Na "" NaO ₃ S

as light yellow crystal powder.

In a manner similar to that described above, the compounds listed in the table below can be prepared in the form of their potassium, sodium or specified salts.

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CH = CH

^L 2 ^R l

II

N-

Il

-N

CH = CH

Tabel

formula
No. ^R l R ₂ R ₃ ^R 4 106 SO3H H H ι
H 107 H SO ₃ H H H 108 H H SO ₃ H H 109 SO3H H H SO ₃ H 110 Cl H H SO ₃ H 111 H SO ₃ H Cl H 112 SO3H H Cl H 113 SO ₃ H H H Cl 114 Cl H Cl SO ₃ H 115 H Cl Cl SO ₃ H 116 CH ₃ H H SO ₃ H 117 H CH ₃ H SO ₃ H 118 CH ₃ H CH ₃ SO ₃ H 119 CH ₃ SO ₃ H Ή CH ₃

5 0 9 8 8 1/10 91

formula
No. ^R l R ₂ R ₃ ^R 4 120 CH ₃ SO ₃ H CH ₃ CH ₃ 121 CH ₃ CH ₃ CH ₃ SO ₃ H 122 CH ₂ -CH ₃ H CH ₂ -CH ₃ SO ₃ H 123 H Cl CH ₃ SO ₃ H 124 H SO ₃ H CH ₃ O H 125 CH ₃ O H H SO ₃ H 126 CH ₃ O CH ₃ O H SO ₃ H 127 SO ₃ H H CN H 128 SO ₃ H H COOH H 129 SO ₃ H H COOCH ₃ H 130 H H H 131 H H Ov-O H

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example

Bleached cotton fabric is washed in a liquor ratio of 1:20 for 15 minutes in a 50 ° C warm liquor which contains the following additives per liter:

0.004 g of one of the brighteners of the formulas (102) or (106) 0.25 g of active chlorine (Javel lye) 4 g of a washing powder of the following composition

15.00 % dodecylbenzenesulfonate

10.00 % sodium lauryl sulfonate

40.00 % sodium tripolyphosphate

25.75 % sodium sulfate anhydrous 7.00 % sodium metasilicate 2.00 % carboxymethyl cellulose 0.25 % ethylenediaminetetraacetic acid.

The cotton fabric is only introduced into the bath 15 minutes after the washing bath at 50 ° C. has been prepared. After spilling and drying, the fabric has a good lightening effect with good chlorine fastness.

The washing powder of the composition given above can also contain the brightener of the formulas given above directly incorporated.

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Example 4

A polyamide fiber fabric (Perlon) is placed in a bath at a liquor ratio of 1:40 at 60 ° C. on the weight of the fabric) 0.05% of a brightener of the formula

or (105)
(102), (105) / and 1 g of 80% acetic acid and 0.25 g of an adduct of 30 to 35 moles of ethylene oxide with one mole of technical stearyl alcohol per liter. The mixture is heated to boiling temperature within 30 minutes and kept at the boil for 30 minutes. A good lightening effect is obtained after rinsing and drying.

It is used instead of the fabric made of polyamide-6 one made of polyamide-66 (nylon) leads to similar lightening effects.

Finally, work can also be carried out under high-temperature conditions, e.g. for 30 minutes at 130 ° C. For this type of application, an addition of 3 g / l hydrosulphite is recommended.

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Example 5

10,000 g of a polyamide produced in a known manner from hexamethylenediamine adipate in the form of chips are made with 30 g of titanium (rutile modification) and

(10 3) or (106) 5 g of the compound of the formula (102), / L mixed in a roller for 12 hours. The chips treated in this way are melted in a kettle heated to 300 to 310 ° C. with oil or diphenyl vapor, after the atmospheric oxygen has been displaced by steam, and stirred for half an hour. The melt is then pressed out through a spinneret under a nitrogen pressure of 5 AtU and the filament spun in this way is wound onto a spinning bobbin. The resulting threads show a good lightening effect.

If a polyamide made from ß-caprolactam is used instead of a polyamide made from hexamethylenediamine adipate produced polyamide, this leads to similarly good results.

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Example 6

Bleached cotton fabric is washed in a liquor ratio of 1:20 for 30 minutes at 95 ° C. The laundry contains the following additives per liter:

0.004 g of the whitening agent of formula (102) or (106)

g of a washing powder of the following composition: 40.0% soap flakes
15.0 % sodium tripolyphosphate

8.0 % sodium perborate

1.0% magnesium silicate
11.0 % sodium metasilicate (9 H ₂ O) 24.6% soda, calc.

0.4% ethylenediaminetetraacetic acid.

After rinsing and drying, the cotton fabric has a good lightening effect.

0 9 8 8 1/10

Claims (1)

Claims J R ₂ \ Distilbenyl-oxdiazoles the Form 1 (1) ^R A H P VCH = CH- (V ₁ ^ ^{v r} ~ VcH \ = μ / X = J | i
SOM ^N - H ^R l SO ₃ M R, hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl, cyano, Carboxy or carbalkoxy with 2 to 6 carbon atoms, R ₂ hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine, Ro is hydrogen or alkyl having 1 to 4 carbon atoms and M is a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion
mean. 2. Distilbenyl-oxdiazoles according to claim 1 of the formula ¹ '■ H CH-CH -ν ^ ■■; , CH = CH- / Y / S- / Y ™ - ™ - / ¹ ^ * SO ₃ M 5 0 9 8 B 1/1 0 9 1 R ¹ , hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl, cyano, carboxy or carbomethoxy, R ^f "is hydrogen, chlorine or alkyl with 1 to 4 carbon atoms, R ¹ -, hydrogen or methyl
mean and
M has the meaning given in claim 1. 3. Distilbenyl-oxdiazole according to Claim 2 of the formula (3) H H SO ₃ M ^{N W} SO ₃ M R ", hydrogen, methyl, ethyl, methoxy, chlorine, sulfo, cyano, Carboxy or carbomethoxy and R " _{2 are} hydrogen, chlorine, methyl or ethyl and
M has the meaning given in claim 2. 4. Distilbenyl-oxdiazoles according to Claim 3 of the formula 5098B 1/1091 SO ₃ M ₁ worm R ' ¹ ^ hydrogen, chlorine or sulfo, R ¹¹¹ ^ hydrogen or chlorine and M, a hydrogen, sodium, or potassium ion mean. Distilbenyl-oxdiazoles according to Claim 1 of the formula (RV ") 1 '2-n CH = CH- (SO ₃ M ₁ ) / V-CH = CH- / J (SO ₃ M ₁ ) wherein R "" is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine, M, a hydrogen, sodium or potassium ion and η the number 1 or 2
mean. 6098 8 1/1091 6. Process for the preparation of distilbenyl-oxdiazoles
the formula (1) R ₂ \
< Γ H \ = 0 ^ H ^R 3 " γ- CH = CH - < ί f \
N - N -CH = CH - κμ
SO ₃ M. Λ J "" Λ wor in R, hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl, cyano, Carboxy or carbalkoxy with 2 to 6 carbon atoms,
R «hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine, Ro is hydrogen or alkyl having 1 to 4 carbon atoms and
M is a hydrogen, alkali metal, alkaline earth metal, Animoniuir: - or amine salt ion
mean, characterized in that one mole of a compound of
formula < ⁶ > / r \ ο / r \ N N 50988 1/1091 with 2 moles of a compound of the formula R ₂ SO ₃ M implements, whereby R ¹ -jj Ro j Ro and M have the above meaning and one of the symbols Z and Z "is an O = CH group and the other is one of the groupings in the formulas O 1 (8a) -CH ₂ POV ₁ 0 - V, (8b) -CH ₂ PO-V, (8c) -CH ₂ PV ₁ and (8d) -CH = PV _n mean in which V-j is an optionally further substituted alkyl radical, a Aryl radical, a cycloalkyl radical or an aralkyl radical represents. 50 98 8 1/1091 7. The method according to claim 6 for the preparation of distilbenyl-oxdiazoles of the formula SO ₃ M wherein R ¹ , hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, chlorine, sulfo, sulfophenyl, Cyano, carboxy or carbomethoxy, R * 2 is hydrogen, chlorine or alkyl with 1 to 4 carbon atoms, R'ο is hydrogen or methyl
mean and M has the meaning given in claim 6, characterized in that 1 mol of a compound of formula N N with 2 moles of a compound of the formula 509881/1091 (9) H * ί SO ₃ M implements, whereby R ', R' ₂ , R'o and M the above and Z ₁ and Z ^ have the meaning given in claim 6 to have. 8. The method according to claim 7 for the production of Distilbenyl-oxdiazoles of the "formula = CH- / V / S ₁ - / R '^ hydrogen, methyl, ethyl, methoxy, chlorine, sulfo, cyano, Carboxy or carbomethoxy and R " _{2 are} hydrogen, chlorine, methyl or ethyl and M has the meaning given in claim 7, characterized in that 1 mol of a compound of formula 509881/1091 (5) C C H β N N with 2 moles of a compound of the formula (10) SO ₃ M implements, whereby R ",, R" "and M the above and Ζ-, and have the meaning given in claim 7. 9. The method according to claim 8 for the preparation of distilbenyl-oxdiazoles of the formula (4) «If I CH = CH - < whin = N N SO ₃ M ₁ worm R " ¹ , hydrogen, chlorine or sulfo, R" ¹ "hydrogen or chlorine and M, a hydrogen, sodium or potassium ion mean, 5098 8 1/1091 characterized in that one mole of a compound of the formula (5) .0. N- with 2 moles of a compound of the formula (ID R "' respectively, SO ₃ M ₁ implements, whereby R ¹¹¹ I, R ¹¹ 'o and M-, the above meaning and Z, and Z2 have the meaning given in claim 8, 10. The method according to claim 8 for the production of Distilbenyl-oxdiazoles of the formula (SO ₃ M ₁ ) 509881/1091 R ^mi , hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or chlorine, Μ-, a hydrogen, sodium or potassium ion and η the number 1 or 2
mean, characterized in that one mole of a compound of the formula W Ii ι - N N with 2 moles of a compound of the formula < ^S0 ₃ Vn implements, whereby R ⁿ "ij M, and η the above and Z, and Z ^ have the meaning given in claim 6. 509881/1091 11. A method for the optical brightening of organic materials, characterized in that the optically Materials to be brightened incorporated distilbenyl-oxdiazoles of the formula defined in claim 1 or optically Applying materials to be lightened on the surface. 12. The method according to claim 11 for optical brightening of polyamides and cellulose as organic material. 509881/1091