DE2306050A1 - PHENOXYBENZOXAZOLE COMPOUNDS - Google Patents

Description

Oasis I-8025 / =

Germany CLBA-GEIGYAG, CH-4002 Basel

Phenoxybenzoxazole compounds

The present invention relates to new phenoxybenzoxazoles, their use as optical brightening agents for organic materials, as well as processes for their production.

The compounds according to the invention correspond to the formula

3.09834 / 1163

CLBA-GEIGY AQ

wherein R, hydrogen, chlorine, bromine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 4 carbon atoms, optionally with methyl substituted cyclopentyl or cyclohexyl or optionally in the benzene nucleus with fluorine, chlorine, bromine, alkyl with 1 to A carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenylalkyl with 1 to 4 carbon atoms in the alkyl part, .. Rp hydrogen, chlorine, bromine, alkyl with 1 to 8 carbon atoms or alkoxy with 1 to 4 carbon atoms or in o-position to each other R, and R _? together a fused-on benzene residue, tetramethylene, trimethylene or methylenedioxy, R ^. Hydrogen, chlorine or alkyl having 1 to 4 carbon atoms and R ₂ , hydrogen, chlorine, alkyl having 1 to 4 carbon atoms, A is a radical of the formula

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CIBA-GEIGYAG .- J, _

■ wherein R ^, R _23, R ^ and R ^ have the meaning given, a radical of the formula

(ib) hT \ -ch = ch- <TC- x ₂

^X 3

wherein X, hydrogen, fluorine, chlorine, bromine, alkyl with 1 to 12 carbon atoms, optionally with methyl substituted cyclopentyl or cyclohexyl, optionally with fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenyl, Cyano, carboxyl, carbalkoxy with 2 to 12 carbon atoms, a sulfo group or their salts, a sulfonamide group optionally substituted on the nitrogen with one or two alkyl radicals with 1 to 4 carbon atoms, an alkyl sulfonate group with 1 to 4 carbon atoms or an alkylsulfonyl radical with 1 to 4 carbon atoms X ₂ Hydrogen, fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms, a sulfo group or their salts or X in the o-position to one another, and X ₂ together is a fused-on benzene ring, tetramethylene or trimethylene X, hydrogen, chlorine or alkyl with 1 to 4 carbon atoms or a radical of the formula

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CIBA-GEtIBY AG

(lc)

wherein X ₁ ^ hydrogen, fluorine, chlorine, bromine, alkyl with 1 to 12 carbon atoms, optionally with methyl substituted cyclopentyl or cyclohexyl, optionally with fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenyl X represents hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms or X ₂ in the o-position to one another, and X together represent a fused-on benzene ring. \

In the foreground of interest are the. Stilbylbenzoxazoles, i.e. compounds of the formula

CH = CH

wherein the X and R symbols are each those given above Have meaning. - °

The compounds of the formula (2) can be classified according to aspects such as their preferred use, their application or the process for their production

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divide into different groups. Such groups are encompassed e.g. by the following formulas:

CH = CH

X, X ^ ₃ X ₁ -, R ,, R ^, R and have meanings;

the one given above

wherein X, - hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 12 carbon atoms, cyclohexyl ,. Phenyl, X "hydrogen, chlorine, alkyl with 1 to k carbon atoms or in o-position to one another .. Xg and X" together form a fused benzene ring, R hydrogen, chlorine, alkyl with 1 to 8 carbon atoms, benzyl, 2-phenylpropyl (2) or cyclohexyl, R / - denotes hydrogen, chlorine or alkyl with 1 to 4 carbon atoms and R ₇ denotes hydrogen, chlorine or alkyl with 1 to 4 carbon atoms;

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CIBA-GEIGY AG

(SO ₃ M) _n

(5)

< ^X 8> 2-n

where Xo is hydrogen, chlorine or alkyl having 1 to 4 carbon atoms, M is hydrogen, alkali metal or ammonium, η is the number 1 or 2 and R _{5 has the} given meaning.

and R "the front

(SO ₃ M) _n

< ^X 9> 2-n

in which Xg is hydrogen or chlorine and M, η and have the meaning given;

(7)

CH = CH

wherein X _ carboxyl, carbalkoxy having 2 to 9 carbon atoms or cyano and Xg, R, Rg and R "represent have given meaning; .

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CIBA-GEIGY AQ

wherein X, q, Rr, Rg and R _{7 have} the meaning given, and

CH = CH

wherein X ,, carboxyl, carbalkoxy having 2 to 5 carbon atoms or cyano., Rg represent hydrogen or alkyl having 1 to 4 carbon atoms and Xg the meaning given Has. -

Further preferred 6-phenoxy-benzoxazole derivatives correspond to the formula

(10) ll

where A ^ is a radical of the formula

HC CH

(10a) _ _c c ~

»Ν

R ₁

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or a residue of the formula

represent and _/ R ^, Rg and Xg have the meaning given above.

Within the framework of formulas (I) ₃ (2). and O) those compounds are preferred in which PU ^^ is hydrogen and in particular those * in which, in addition to the radical Rl, at least one of the X and at least one of the R symbols is hydrogen =

Of the compounds of the formulas (4), (5) * (7) - and (8), those of particular practical interest are in which at least one of the R symbols stands for hydrogen.

The compounds according to the invention of the formulas given can be prepared in analogy to known ones Establish methods. -

To prepare a compound of the formula .. '.. (I), in which A is a radical of the formula (Ia), furan- _2J 5-dicarboxylic acid or its reactive functional acid derivatives, for example acid chlorides with two moles of a compound of the formula

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CIBA-GEIGY AG

(H)

implement, in which the R symbols have the meaning given. This conversion is expediently carried out at higher

Temperatures, for example at 150 to 220 C, preferably in the presence of a catalyst such as boric acid.

In a corresponding manner for the preparation of compounds of the formula (I), in which A is a radical of Part formulas (Ib) or (ic) denotes one mole of a compound the formula

(12)

CH = CH

COOH

where the X symbols have the meaning given and the carboxylic acid group can be functionally modified, for example in the acid chloride with one mole of a Compound of formula (11) implemented.

Compounds of the formula (2) can also be prepared by the anil synthesis. Here you set a compound of the formula obtained, for example, according to the process described above

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CIBA-GEIGY AG - IO -

.which the R-Syiribole have the meaning given, with a marine base of the formula

CH-

to, in which the X symbols have the meanings given above and Y is hydrogen or chlorine, the reaction preferably in dimethylformamide as the reaction medium and in the presence of a "strongly basic" alkali compound is carried out; . .

Strongly basic alkali compounds are those compounds of the alkali metals (I. main group of Periodic Table of the Elements) including ammonium, which has a base strength of at least have about that of lithium hydroxide. According to this, compounds of lithium, sodium, rubidium, Cesium or ammonium of the type, for example, of alcoholates, hydroxides, amides, hydrides, sulfides or be strongly basic ion exchangers. More advantageous-

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is used wisely (especially when mild reaction conditions with regard to the reaction temperature are indicated appear) potassium compounds of the composition

KOC τ H ₀ ,, • x-1 2x-l ^J

where χ represents an integer from 1 to 6, such as potassium hydroxide or potassium tert. butylate. In case of Alkali alcoholates, alkali amides (and hydrides) is to work here in practically anhydrous medium while in the case of alkali hydroxides, water contents of up to 25% (e.g. water of crystallization) are permitted. In the case of potassium hydroxide a water content of up to about 157 ° has proven to be expedient. Usable as examples of others Alkali compounds may be mentioned;

Katriummethylatj sodium hydroxide, sodium amide, lithium amide, Lithium hydroxide, rubidium hydroxide or cesium hydroxide. It is of course also possible to use mixtures of these Working bases.

The compounds of the formula are useful (14) brought into reaction with the aldehydaniles in equivalent amounts, so that no essential component There is excess. At least the equivalent of the alkali compound is advantageously used Amount, i.e. at least 1 mole of a compound with e.g. a KO group per 1 mole of aldehydanil. At the

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2306O50

Turning potassium hydroxide is preferably used 4 to 8 times the amount.

The implementation according to the invention can generally carried out at temperatures in the range between 10 and 150 C. will. If potassium alcoholates are used in the reaction, the reaction often succeeds at room temperature, in which case no external heat supply is necessary. When using potassium hydroxide it is mostly necessary to work at elevated temperature. For example, the reaction mixture is slowly increasing 50 to 100 C and then heated for some time, e.g. 1/2 to 2 hours, held at this temperature. The end products can be extracted from the reaction mixture according to the usual methods known methods are worked up.

Another way to get to compounds of the formula (2) is that one compounds of the Formula (12) with halogenating agents such as N-bromosuccihimide or elemental chlorine in the compounds of the formula.

(15)

halogen

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CIBA-GElGY AG _ χ ^ _

transferred, this then with a trialkylphospb.it, e.g. Trimethyl or triethyl phosphite into the phosphonates of the formula

(16) (AlkylO) ₂ P - CH ₂ - /

transferred, which with aldehydes of the formula

^X l

V VCHO

condensed in the presence of strongly basic alkali compounds to form compounds of the formula (2).

This process is particularly useful for the preparation of compounds of formula (2) and below Formulas shown in which X substituents represent electron-withdrawing Substituents such as the sulfo-, carboxyl, Carbalkoxy or cyano group.

The m-phenoxy-o-aminophenols of the formula (11) are produced according to known processes. For example, a p-chloronitrobenzene of the formula is used

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wherein R, has the meaning given, · with a phenolate the formula

" ^L l

NaO

wherein R,, R «and R ~ have the meaning given above have become a p-phenoxynitrobenzene of the formula

around, and then leads this by heating with potassium hydroxide in powder form with mechanical mixing and with the addition of molecular oxygen to temperatures' of over 70 ° C into a compound of the formula

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CIBA-GEIGYAG - 15 -

above. The addition of acid turns a compound of the formula (20) obtain the corresponding free o-hydroxy-nitro compound, which is then reduced by reduction (e.g. by means of catalytic Itydration, using sodium dithionite, etc.) in a compound of formula (11) is converted.

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

ι "i

or substances containing such organic materials can be used.

\ This purpose include for example, without having to be expressed by the following survey of any limitation, the following groups of organic materials, insofar as optical brightening thereof is contemplated mentioned:

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I, synthetic organic high molecular materials:

a) Polymerization products based on at least one polymerizable Organic compounds containing carbon-carbon double bonds, i.e. their homo- or copolymers as well as their aftertreatment products such as crosslinking, grafting or degradation products, Polymer blends or products obtained by modifying reactive groups, for example polymers based on cc, ß-unsaturated carboxylic acids or derivatives of such carboxylic acids, especially of acrylic compounds (such as aryl esters, acrylic acid, acrylonitrile, acrylamides and their derivatives or their methacrylic analogs), 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 which can be obtained by opening the ring, for example polyamides of the polycaprolactam type, and also polymers which are obtainable both via polyaddition and polycondensation, such as polyethers or polyacetals, ■ ^; _:

c) polycondensation products or precondensates Basic bi- or polyfunctional compounds with condensable Groups, their homo- and mixed condensation products and post-treatment products, such as

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wise polyesters, especially saturated ones. (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, 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 animal

or of vegetable origin, for example based on 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). On the other hand, they can be in the form of the various

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most formed structures exist, i.e. for example., .. as mainly three-dimensionally extended bodies like plates, Profiles, injection moldings, various types of workpieces, chips, granulates or foams, furthermore than predominantly two-dimensional bodies such as films, foils, lacquers, oats, impregnations and coatings or as a predominantly one-dimensional body like threads, fibers, flakes, wires. On the other hand, the said materials can also be used in the unshaped states The most varied of homogeneous or inhomogeneous forms of distribution, such as powders, solutions, emulsions, dispersions, latices, pastes or waxes. ί Fiber materials can be, for example, as endless Threads (drawn or undrawn), staple fibers, Flakes, hanks, textile threads, yarns, twisted threads, nonwovens, Felts, wadding, flocking structures or as textiles Woven or textile composite materials, knitted fabrics and as paper, paperboard or paper pulp are present. !

! The compounds to be used according to the invention are, inter alia, 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, according to the invention are optically brightened, this happens

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advantageously in an aqueous medium, in which the relevant Compounds in finely divided form (suspensions, so-called microdispersions, possibly solutions) are present. If appropriate, dispersants, stabilizers, wetting agents and other auxiliaries can be added during the treatment will.

Depending on the type of brightener compound used, it may prove advantageous to work in a neutral or alkaline or acid bath. The treatment is usually carried out at temperatures of 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 (padding thermosetting application, exhaust dyeing process in dyeing machines)
is practiced.

^! . The optical brightening agents according to the present invention can also be added to or incorporated into the materials before or during their deformation. They can be used, for example, 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.

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Cl BA.G EtGY Ad.

- 20 ^ ^l ■■ 2308050

Provided that the shaping takes place fully * or semi-synthetic organic materials by S pinny he propelled en * or spinning about ¹ -massen, the optical brightener can be appllziert by the following methods:

- Addition to the starting substances (ζ.Β »monomers) or,! Intermediate products ( e.g.» precondensates \ prepolymer) ■, ie before or during the polymerization j polycondensation or polyaddition,

- Powdering on polymer chips or granules for Spinning masses,

- Bath coloring of polymer chips or granulates for spinning masses,

- dosed addition to spinning melts or spinning solutions, . ^. Applied to tow before stretching.

¹ The optical brightening agents according to the

gender invention can also be used, for example, in the following Application forms are used:

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 aftertreatment of dyeings, prints or etching prints; . "'

b) in mixtures with so-called "carriers", wetting agents, Plasticizers, swelling agents, antioxidants, light

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- 21 -

Protective agents, heat stabilizers, chemical bleaching agents (chlorite bleach, bleaching bath additives);

c) in a mixture with crosslinkers, finishing agents (e.g. starch or synthetic finishes) as well as in combination with a wide variety of textile finishing processes, especially synthetic resin finishes (e.g. crease-proof finishes like "wash-and-wear", "permanent-press", "no-iron"), furthermore Flame-resistant, soft-touch, anti-soiling or antistatic equipment or antimicrobial equipment;

d) Incorporation of the optical brightening agents into polymeric carrier materials (polymerization, polycondensation or polyaddition products) in dissolved or dispersed form for use e.g. in coating, impregnation or Binders (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 for the further processing of synthetic fibers can be used

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- 22 - 23Q605Q

the one that comes from a special bath before stretching- :, the fiber; ^

i) as scintillators, photographic for various purposes Type, e.g. for electrophotographic reproduction, for optical brightening of photographic layers, possibly in combination with white pigments, such as e.g. TiO ^ or supersensitization.

If the whitening process is carried out with textile treatment or finishing methods combined, so can the combined In many cases, treatment is advantageously carried out with the aid of appropriate permanent preparations which the optically brightening compounds in such concentration contain that the desired lightening effect is achieved. ; In certain cases. The brighteners are through > a follow-up treatment brought full effect. This can for example a chemical (e.g. acid treatment), a thermal (e.g. heat) or a combined chemical / thermal Represent treatment. This is how one proceeds, for example, with the optical brightening of a number of fiber substrates, e.g. of polyester fibers, with the inventive Brightening them appropriately in such a way that they can be Fibers with the aqueous dispersions (possibly also solutions) of the lightening agents at temperatures below 75 ° C, e.g. at room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ° C,

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it is generally recommended that fiber material to dry beforehand at a moderately elevated temperature, e.g. at at least 60 to about 130 ° C. The heat treatment in The dry state is then advantageously carried out at temperatures between 120 and 225 ° C., for example by heating in a drying chamber, by ironing in the specified temperature range or by treating 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 compounds according to the invention, based on the material to be optically brightened, in wide limits fluctuate. 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. However, quantities of up to about 0.8 percent by weight can also be used and optionally up to about 2 percent by weight are used. For most practical issues are preferably amounts between 0.0005 and 0.5 percent by weight of interest.

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

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Solvents or finely divided as aqueous Dispersions added. For household or commercial detergents they are advantageous in any phase of the detergent manufacturing process, z..B. the so-called "Slurry" before atomizing the washing powder or during preparation 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 use the lightening agents, for example, with the detergent substances mix, knead or grind and then finish Mix in washing powder. However, they can also be resolved or predispersed to be sprayed onto the finished "detergent.

The detergents used are the known mixtures of active washing substances such as soap in the form of chips and powder, synthetics, soluble salts of sulfonic acid half-esters of higher fatty alcohols, higher and / or poly-alkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminooxyalkyl or -amlyceramines. Organophosphate of fatty alcohols in question _o As builders as _r-called "Builders" are, for example. Alkali poly and poly metaphosphates, alkali pyrophosphates, alkali metal salts of carboxymethyl cellulose and other "soil redeposition inhibitors", furthermore

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Alkali silicates, alkali carbonates, alkali borates, alkali perborates, nitrilotriacetic acid, ethylenediaminotetraacetic acid, Foam stabilizers such as alkanolamides of higher fatty acids into consideration. Furthermore, in the detergents, for example be included:

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

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

The compounds according to the invention are added in amounts of 0.005 to VL or more, based on the weight of the liquid or powdery, finished detergent. Washing liquors which contain the stated amounts of the claimed optical brighteners give a brilliant aspect in daylight when washing textiles made of cellulose fibers, polyamide fibers, highly refined cellulose fibers, polyester fibers or wool.

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

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The specified textiles are treated for 1 to 30 minutes at 20 to 100 ° C in a washing bath that 1 to 10 g / kg of a built-up, composite detergent and 0.05 to 1%, based on the detergent weight, Contains the notified brightening agent. The liquor ratio can be 1: 3 to 1:50. After washing, it is rinsed and dried as usual. The washing bath can be used as a bleach additive Contains 0.2 g / l active chlorine (e.g. as hypochlorite) or 0.1 to 2 g / l sodium perborate.

In the examples, unless otherwise stated, parts are always parts by weight and percentages are always Weight percent. Unless otherwise noted, melting and boiling points are uncorrected. The temperatures are given in degrees Celsius.

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example 1

4.1 g of 5-pheivylthiophene-2-carboxylic acid are in 20 ml of trichlorobenzene in the presence of 0.2 ml of dimethylformamide with 10 ml of thionyl chloride at 94 ° C in the acid chloride convicted. After distilling off the excess Thionyl chloride is allowed to cool in vacuo, 4.02 g of 2-hydroxy-4-phenoxyaniline are added at 30 ° C. and the mixture is heated in a stream of nitrogen to 210 ° C., during which hydrogen chloride escapes. After adding 0.5 g of boric anhydride, the mixture is heated within from 2 hours to 215 ° C, with water and a little dichlorobenzene distill off. Chromatography on aluminum oxide activity I according to Brockmann with methylene chloride as Eluent gives 7.0 g (94.7% of theory) of the compound of the formula

HC
(21)

as pale yellow crystals with a melting point of 130 to 132 ° C. Recrystallization from perchlorethylene and benzene gives pale yellow crystals with a melting point of 131 to 133 ° C. C ₂₃ H ₁₅ O ₂ NS

Calculated: C 74.78 H 4.09 N 3.79 S 8.68 Found: C 74.73 H 4.30 N 3.84 S 8.80

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The amino phenol used is 4-phenoxy-nitröbenzol prepared from iZ-Hy by reduction with Kätriumdithiöiiit in-the manner described in Example 2 »Färb-solvent crystals by sublimation in Hochvakuumi melting point 123.5 to 125 ^east G, ·,

calculated: G 71.62 H 5.51 N found ₅ 96 * G * 71 36 H, 5.54 N 7 _ä OE7

If one replaces the Phenyithiophericaroic acid by the equivalent amount of furan-2,5-diacid is obtained the bisbe.nzöxazöl of the formula

HG

as pale yellow crystals with a melting point of 203 to 204 ° C. ^C 3O ^H 18 ° 5 ^N 2 calculated: found:

C 74.07 H 3.73 N 5.76 C 74.43 H 3.79 N 5.88

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In the same way as described in Example 1, the in
the following Tables I and II listed compounds of the
Formulas (25) and (57) can be prepared.

Table I.

formula
No ^W l V ^W 3 H Z ^v i ■
^V 2 24 H H H H H H H 25th H H H ^H H " H 26th H H H H H H -CH,
5 27 H H H H Cl CH H ! 28 H H H H H Cl H ■ 29 H H Cl H H H . 50 H H Cl H H H H 51 H H CH,
5 H H H H 52 H H OH, H CH, H 55 OH, H H H H H H 54 H Cl Cl H H H H 55 H H OCH Cl H H H 56 Cl H H H H H

Cl H -CH

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r " HTJ CIS

\\ jtl Uli
tt Il

CC, C- ^ ¹

ν ν

• o>

ο-

I.
!Formula
j No.
1 j ^v i
: ■ ^V 2 . V ■ Z 58 :
. ■ H- "■ H
- -C (CHj) ₅ H 59 H H -CH ₅ H 40 H CH; H H 41 CH H Cl Cl 42 H- H H 45 Cl H Cl. - H 44 Cl H H H 45 H H ■ '· H H

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Example 2

6.4 g of 4-phenylstilbene-4 '-carboxylic acid chloride and 5.14 g of the aminophenol of the formula

C (CH ₃ )

are in 50 ml of trichlorobenzene in the presence of 0.2 g of boric anhydride heated to 210 ° G within about 5 hours, the reaction mass allowed to cool to 70 ° C and diluted with 50 ml carbon tetrachloride. After cooling to 25 ° C is suction filtered, washed with ethanol and im Vacuum dried at 100 ° C. 8.05 g (78.5% the theory) of the compound of the formula

(kl)

/ ■ "V / Λ

CH = CH

C (CH ₃ ).

as pale yellow crystals with a melting point of 266 to 268 ° C. Recrystallization from tetrachlorethylene gives pale yellow Crystals with a melting point of 282 to 284 ° C.

C ₃₇ H ₃₁ O ₂ N

calculated: found:

C 85.19 C 85.01

H 5.99 H 6.24

N 2.69, N 2.71.

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. - ' ~ m ~ 23OiOlO

Bas as Äusgangsmatoeriäl veiwiindete itaino; ph © nOl '' is produced as follows:. :,

254 g of 4 "t" butylphenol value with 88 g of potassium oxylpulviäa: heated to 140 ° C * * Λ "OjS 'g freshly fallen" copper. And 78.8 g of 4-tälömitröbenzol swept - and "from 140 to 145 ^ € gerülatj hlM all barrels are distilled off * Then? 8 _S B g 4-Chlö3ffiitröbeftzöl are added and on. 160 ° C until the water wash is finished. Mari diluted with 1> 5 l of water and, 50 ffll SöXigör Matriümhy solution, j nutseht waseht neutral with water and tröclaiet in vacuo at 45 to 5 NC ^east 0. This gives 269 g of the compound of formula

as beige crystals with a melting point of 55 to 57 ^b C; ~ ^K '~ """~ Recrystallization from methanol gives almost" colorless crystals with a melting point of 60 to 60.5 ° G ^.?: -TI ⁱ :: 5;

■ i

Calculated: C 70, SB H 6, ^ 2 N 5.16 found: C 71.00 H 6.25 N 5.45 x. -

71 g of this product are with 840 g'89% Potash hydroxide powder for 17 hours at 70 ° G in one heatable ball mill ground in an air stream. The powder is then taken up in 4 ί water, "sucked, washed with water,

309 ^ 14/1113.

then with methylene chloride to remove the unreacted 'Starting material, dissolves the still moist potassium salt of the formula

in 2 liters of hot water, filtered to clarify and acidified strongly with hydrochloric acid. After cooling down you can see that precipitated nitrophenol of the formula

^N OH

washes with water and dries at 45 ° C in a vacuum.

Yield: 43.1 g of melting point 72 to 74 ° G.

A sample distilled for analysis (bp _0- , 141 ° C) melts

at 77 to 79 ° C.

C ₁₆ H ₁₇ O ₄ N _:

Calculated: C 66.88 H 5.96 N 4.88 found: C 67.1 H 5.9 N 5.0.

43 g of the nitrophenol are dissolved in 1 liter of water and 150 ml of 30% sodium hydroxide solution at 75 ° C., with 110 g Sodium dithionite decolorized, the solution adjusted to p "7.5 with hydrochloric acid, the white crystals sucked up with water washed and dried at 45 ° C in a vacuum. You get

309834/1163

36.2 g of the aminophenol of the formula

(50) (H ₃ C) ₃ C

as an almost colorless powder with a melting point of 141 to 143 ° C. Sublimation in a vacuum gives colorless crystals with a melting point 145 to 146 ° C.

Calculated: C 74.68 H 7.44 N-5.44 Found: C 74.77 H 7.46 N 5.45.

30 9834/1 163

2306Q50

Example 3

A 38 ° G solution of 6.02 g of the compound

the formula

and 5.63 g of the anil of the formula

5.0 g of 90% potassium hydroxide powder are added to 100 ml of dimethylformamide in a stream of nitrogen. The solution immediately turns purple and within 10 minutes the compound of the formula separates under heating to 44 ° C

as a fine crystalline precipitate. After a further 15 minutes, it is diluted with 400 ml of methanol, suction filtered, washed and dried. 6.4 g of pale yellow powder with a melting point of 275 to 276 ° C. are obtained. Recrystallization from chlorobenzene using fuller's earth provides greenish yellow crystals with a melting point of 281 to 283 ° C.

3Q983 4/1163

calculated; C 85.14 ft 4.98 N 3.01 " ¹ ^ '" ^ found: ■ C 84.99; H 4.94; K 3.17. _r ; _; .

BenzöiCazöl veneered as the starting material · '

we df ο 1 g ^ end erma s; s s _v er'hal. t en: y ~ - ^

ί 3 'ξ j] JJ // ^ \ __ -1 · ^ r.-r-i

■ "* - ■ *" 0 ~ \ Pt ο * Ll -ΪΑir * f ~ InA ^ lI ^- Sr ¹ In! 7ri · ^^ ίίνιι-Α ^ / y P ¹

£ v J ^ * V / CL ¹ T. i. JC— L · 11 "Jl U / Iw-Li. C ^ v vJ \ ^> O d- li J- C ^« * J £ - * £ - Ϊ—.

phenoxyaniline and 1 g of boric acid are ill 40 ml of trichlorobenzene heated to 210 ° C. over the course of 4 hours and the cleaved off for a further 2 hours while distilling off Water and about half of the solvent heated to a final temperature of 223 ° C at 130 ° C all solvent removed, the residue in 100 ml of carbon tetrachloride added and aluminum oxide of the activity Inach Brockmann with Tetraehlox-kbhienstöff methylene chloride 1: 1 as eluent chromatographed, 33.9 g (70.6% of theory) of the compound are obtained formula

as colorless crystals with a melting point of 99 to 1O4 ° C.

Crystallization from benzene gives colorless crystals of melting point 102 to 102.5 ^0C. -

Calculated:, - C 79.71 H 5.02 'N 4.65 found: C 79.92 " ^: H 5.57 N 4.80.

309834/1163

OR! G! IS! AL [NSPECTED.

If, instead of the described anil of diphenyl-4-aldehyde, the corresponding aldehydesniles are used, the stilbenes of the formula are obtained in a similar yield

(55)

CH = CH

Yellowish crystals of tetrachlorethylene. Melting point: 167 to 168 ° C.

Calculated: C 83.27 H 4.92 N 3.66 found: C 83.27 H 4.93 N 3.64.

(56).

CH I
CH

I.
CH

CH = CH

Yellowish crystals of tetrachlorethylene. Melting point:

178 to 180 ° C.

C ₃₀ H ₂₅ O ₂ N

Calculated: C 83.50 H 5.84 N 3.25 found: C 83.02 H 5.86 N 3.19.

309834/1 163

(57)

CH = CH-

y ¹

Greenish pale yellow crystals of tetrachlorethylene. Melting point: 210 to 212 ° C.

Calculated: C 84.80 H 4.82 N 3.19

found: G 84.54 H 4.85 N. 3 ₃ O2

309834/1163

Example 4

In the same way as described in Examples 2 or 3, the in the following Table III listed compounds of the formula

(58)

CH = CH

getting produced.

4/1163

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309834/1163

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309834/1163

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309834/1163

2308050

example

4.37 g (0.01 mol) of the phosphonate of the formula .0

II (97) (H ₅ C ₂ O) -P-

are with 3 * 65 g (0.011 mol) of benzaldehyde-2,4-disulfonic acid disodium salt with a content of 92.7% in 100 ml of dimethylformamide with the aid of 3g of sodium methylate during Reacted for 5 hours at 43 to 45 ° C. After cooling down is diluted with 200 ml of methanol, freed from insoluble material by filtration, the filtrate with activated charcoal discolored and evaporated to dryness. The residue will boiled in 100 ml dimethylformamide, of undissolved parts filtered off, the filtrate evaporated in vacuo, dissolved in 12 ml of water at room temperature, with 10 ml.konz. Hydrochloric acid precipitated and heated to the boil until the yellow Precipitate crystallizes. After suction filtering, washing with 5% hydrochloric acid and drying in vacuo at 90 ° C. 2.5 g (55.6% of theory) of the compound of the formula.

( ₉ 8)

70.0 t. 33

309834/1163

as a yellow powder. ^C 27 ^H 23 ° 10 ^NS 2

calculated: found:

C 55.50 C 55.4 H 3.97 N 2.39 S 10.96 H 3.7 N 2.7 S 11.0

The compounds of the formulas below can be prepared in an analogous manner.

(99)

CH = CH

(100) HO ₃ S.

- / V

CH = CH

(101)

CH = CH

HO ₃ S

(102)

-CH = CH

SO ₃ H

70.0i.335 30983 h / 1163

(105)

(104)

Cl

The phosphonate of the formula (97) used as the starting material is obtained as follows: 12.04. g (0.04 mol) of the benzoxazole of the formula

(51)

are in 160 ml carbon tetrachloride with 7.88 g (0.044 Mol) N-bromosuccinimide in the presence of 0 * 2 g of dibenzoyl peroxide stirred under irradiation with ultraviolet light for 16 hours at reflux temperature. After filtering off of the succinimide and evaporation of the filtrate for 15.0 g (99% of theory) of the crude compound of the formula are obtained dry

309834/1163

(105) Br-CH ₂

as a yellowish powder with a melting point of 114 to 116 ° C. Recrystallization from three times the amount. Carbon tetrachloride yields colorless crystals with a melting point of up to 125 ° C.
C ₂₀ H ₁₄ O ₂ NBr

Calculated: C 63.18 H 3.71 0 8.42 N 3.68 Br 21.01 Found: C 62.99 H 3.84 0 8.52 N 3.70 Br 20.95

8.7 g (0.023 mol) of the bromide described above werden.mit 5 g (0.03 mol) of triachide phosphite 134 ° C heated, the elimination of ethyl bromide begins. Heat further within about 30 minutes until the development of ethyl bromide comes to a standstill at a final temperature of 162 ° C. After cooling, dilute with hexane, horse-drawn carriage, washing with hexane and drying, 9.3 g (93% of theory) of the phosphonate of the formula are obtained

as yellowish crystals with a melting point of 98 to 99 ° C.

309834/1 163

Example 6

4.37 g of the phosphonate of the formula (74) (O ₃ Ol mol) and 1.31 g (0.01 mol) of 4-cyanobenzaldehyde are dissolved in 100 ml of dimethylformamide, and 3.0 g of sodium methylate are added to the solution. The violet solution is stirred for 5 hours at 43 to 45 ° C, then diluted with 100 ml of methanol, the yellow precipitate is suction filtered, washed with methanol and dried in vacuo at 70 ° C. 3.2 g (77.4% the theory) of the compound of the formula

(106) NC-e J- CH = CH

as a yellow powder which melts at about 200 ° G "blurred. ⁷ recrystallization from tetrachlorethylene provides bright 'light yellow crystals of melting point 202-203 ° G.

^C 28 ^H 18 ° 2 ^N 2 -

Calculated: C '81, 14 H 4.38 N 6.76 found: C 80.00. H 4.41 N 6.64.

The compounds of the following formulas can be prepared in an analogous way:

30 9 834/1163

(107)

CH = CH

- 49 -

* N

ι — ο

CN

(108)

rv

CH = CH

CN

V y ^ ^

(109) H ₃ COOC

JH

(110)

, N

CH,

(CH ₂ )

₂ ) ~

I (111) CH-CH ₂ OOC- / '\ -

CH = CH

^C 2 ^H 5 = J \

(112) H ₂₅ C ₁₂ OOC

CH

cN

30983A / 1163

Example 7

In the same way as described in Example 5 or 6, the compounds of the formula listed in Table IV below can be used
U

(115) U

'2 ^u l

getting produced.

V,

3 09 8 34/118 3

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309834/1163

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309834/1163

Example 8

A polyester fabric (e.g. "Dacron") is padded at room temperature with an aqueous dispersion which per liter 2 g of a compound of formula (21), (22) or (106) and 1 g of an adduct of about 8 moles of ethylene oxide to 1 mole of p-tert. Contains octylphenol, and dries at about 100 ° C. The dry material is then subjected to a heat treatment at 150 to 220 ° C, which Depending on the temperature, takes 2 minutes to a few seconds. The material treated in this way is much whiter Appearance than the untreated material.

309834/1163

-.54 "-

Example 9 "" '

Bleached fabric made of polyamide staple fiber (nylon spun) is made with a liquor ratio of 1:30. V7ä * while treated for 30 minutes at 90 to 95 ° C in a bath, which is "to the fiber material, based" 0 _s l% of a compound of formula (21) or (22) and 1% contains 40% acetic acid. After Rinsing and drying shows the fabric treated in this way a strong lightening,

3QS83 4/11 β 3

Example 10

A fabric made of polyvinyl chloride fibers ("Thermovyl") is padded at room temperature (about 20 ° C.) an aqueous dispersion containing 1 to 2 g of the compound of the formula (21) and 1 g of an addition product per liter contains from about 35 moles of ethylene oxide to 1 mole of octadecyl alcohol and dries at about 70 ° C. The dry The material is then subjected to a heat treatment at 100 ° C. for 3 minutes. The treated like that Fabric made from polyvinyl chloride fibers has a significantly higher whiteness content than an untreated fabric made from polyvinyl chloride fibers.

3098 34/1163

Example 11

A fabric made of cellulose acetate is in the liquor ratio 1:30 to 1:40 at 50 ° C placed in an aqueous bath containing 0.15% of the compound of formula (22), calculated on the fiber material. You bring the temperature of the treatment bath to 90 to 95 ° C and holds for 30 to 45 minutes at this temperature. To rinsing and drying results in a good lightening • effect. -

309834 / ^ 163

Example 12

In a polyurethane coating compound

13.3 g of isocyanate-modified polyester

26.7 g of ethyl acetate

2 g reaction accelerator and

2 g of polyfunctional isocyanate as crosslinker

will

1.5 g of a matting agent, 1 g of titanium dioxide (rutile modification) and

0.05 g of a compound of the formula (47), (55), (55), (56) or (57) -

stirred in. This mixture is left to stand for 2 hours and then spread with a doctor blade or a film drawing rod on a cotton fabric (wet film thickness 1 mm). Thereafter is dried at room temperature for 24 hours. The fabric coated in this way has a strong optical appearance Lightening effect of good lightfastness.

309834/1163

Example 13

100 parts of polyester granules made from polyterephthalic acid methylene glycol ester are intimately mixed with 0.05 parts of the compound of the formula (23), (22), (4?), (55), 05) or (57) and at 285 ° C melted with stirring-. After spinning the spinning mass through conventional spinnerets, strongly lightened polyester fibers are obtained. The compounds mentioned can also be added to the starting materials before or during the polycondensation to form the polyester, '.

Example . 14th

10000 parts of a polyamide produced in a known manner from hexamethylenediamine adipate in chip form are mixed with 30 parts of titanium dioxide (rutile modification) and 10 parts of the compound of formula (21), (22), (47), (53)> (50 or (57) in a "roller vessel" for 12 hours mixed. The chips treated in this way are placed in a boiler heated to 300 to 310 ° C with oil or diphenyl vapor, after displacing the oxygen in the air with superheated steam, melted and held for half an hour touched. The melt is then placed under nitrogen pressure of 5 atmospheres through a spinneret and the cooled filament spun in this way is wound onto a spinning bobbin. The resulting threads show an excellent heat-setting-resistant lightening effect of good washing and lightfastness.

309834/1163

. Example 15

10 ¹ 000 parts of a 6-caprolactam produced in a known manner. Polyamides in Schnitzel form -wercfen with 30 parts of titanium dioxide (rutile modification) and 2 parts of the compound of the formula. (21), (22), (4?), X53), (56) or (57) in a roller vessel during Mixed for 12 hours. The chips treated in this way are, after displacing the atmospheric oxygen, melted in a kettle heated to 270 ° C. and stirred for half an hour. The melt is then pressed out through a spinneret under a nitrogen pressure of 5 atmospheres and the cooled filament is wound onto a spinning bobbin. The resulting threads show an excellent heat-setting-resistant lightening effect of good washing and lightfastness.

3098 3 4 / 11GS

Example 16

100 g of "Fiber-Grade" polypropylene become intimate mixed with 0.8 g of the compound of the formula (21), (22), (47), (53), (56) or (57) and at 280 to 290 ° C melted while stirring. The melt is produced by conventional spinning nozzles according to known Schraelz spinning processes spun out and drawn. It will be strongly lightened Polypropylenfaserη obtained.

309834/1163

Example 17

An intimate mixture of 1ΘΟ parts of polyvinyl chloride, 3 parts of stabilizer (Ädvastat BD 100; Bä / Gd complex), 2 parts of titanium dioxide, 59 parts of dibetyl phthalate and 0.01 to 0.2 parts of one of the compounds of the formulas (22), (5 ?), (55), (56) or (57) is rolled out on a calender at 150 to 155 ° C to form a film. The ^so-i: wonnene opaque polyvinyl chloride sheet having a higher whiteness vzesentlich as a film which does not contain the optical brightener.

Example 18

j 100 parts of polystyrene and 0.1 part of one of the compounds of the formulas (21), (22), (47), (53), (55), (56) or (57) are melted with the exclusion of air for 20 minutes at 210 ° C. in a tube 1 cm in diameter. After cooling, an optically brightened polystyrene mass of good lightfastness is obtained.

309834/1163

-Example 19

. : Leached cotton is in the liquor ratio 1:30 for 30 minutes in a 60 ° G warm liquor washed, which contains the following additives per liter:

0.032 g of the creamer of the formula (980 1 g of active chlorine (Javel lye) 4 g of a washing powder of the following composition: ■

15.00 % decylbenzenesulfonate

10.00% sodium lauryl sulfonate 40.00% sodium tripolyphosphate. 25.75 % sodium sulphate anhydrous <7.00 % sodium metasilicate 2.00 % carboxymethyl cellulose _: 0.25% ethylenediaminetetraacetic acid.

After rinsing and drying, the fabric looks strong Lightening effect of good acid and chlorine fastness.

The washing powder of the composition given above may also contain the brightener of the formula (98) directly incorporated.

; - You also get a strong lightening effect, if you carry out the washing process for 30 minutes at 20 ° C.

309834/1163 V.

Example 20

A polyamide fiber fabric (Perlon) is introduced in Flottenverh'ältnis 1:40 at 60 ° C in a bath containing (based on the fabric weight) 0.1% of the brightener of the formula (98) and per liter 1 g 807 _o acetic acid and Contains 0.25 g of an addition product of 30 to 35 moles of ethylene oxide with one mole of technical stearyl alcohol. The mixture is heated to boiling temperature within 30 minutes and kept at the boil for 30 minutes. After rinsing and drying, a strong lightening effect with good lightfastness is obtained.

If one uses a fabric made of polyamide-66 (nylon) instead of the fabric made of polyamide-6, one gets too similar good lightening effects.

Finally, it is also possible to work under HT conditions, e.g. for 30 minutes at 130 ° C. For this For the type of application, an addition of 3 g / l hydrosulfite to the liquor is recommended.

309834/1163

Claims (1)

Claims 1. Phenoxy-benzoxazole compounds of the formula wherein R, hydrogen, chlorine, bromine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 4 carbon atoms, optionally with methyl substituted cyolopentyl or cyclohexyl or optionally in the benzene nucleus with fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms or. Alkoxy, substituted with 1 to 4 carbon atoms, phenylalkyl with 1 to 4. Carbon atoms in the alkyl part, R ₂ hydrogen, chlorine, bromine, alkyl with 1 to 8 carbon atoms, alkoxy with 1 to 4 carbon atoms or R in the o-position to one another, and Rp, _ together a fused-on benzene radical, tetramethylene, trimethylene or methylenedioxy, R -, hydrogen, chlorine or alkyl with 1 to 4 carbon atoms. And% hydrogen, chlorine or alkyl with 1 to 12 carbon atoms, A is a radical of the formula. wherein R ₁ , R _p , R and R ^ have the meaning given above, or a radical of the formula where Ί. Hydrogen, fluorine, chlorine, bromine, alkyl with 1 to 12 carbon atoms, optionally substituted with methyl cyclopentyl or cyclohexyl, optionally with fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenyl, cyano, carboxyl , Carbalkoxy with 2 to 12 carbon atoms, a sulfo group or its salts, a sulfonamide group optionally substituted on nitrogen with one or two alkyl radicals with 1 to 4 carbon atoms, an alkyl sulfonate group with 1 to 4 carbon atoms or an alkylsulfonyl radical with 1 to 4 carbon atoms Xp hydrogen, fluorine , Chlorine, bromine, alkyl having 1 to 4 carbon atoms, a sulfonic group or their 309834/116 Salts or X and X in p-position to one another together a fused-on Benzqlring ;, TetFamethyl qder fPpimetnylen ,, X-. Wasserstpff ;, Sfrlpr- P.d.ey Alkyl Pit 1 to 4 Kohleng ^ QffatGiroeR bedßufeeri odep a remainder of the? Eo.rmel ^ where X | i Wasg.epgtoffj Fluer ^ Ciilop ^ Βφοτη ,, Aljiyl with | fejs men ^ possibly mi ^. ^ with pm, Alky ^ with 1 bn.s A 1 to 4 IColilenstpffa ^ Gmgfi su Alkoxy yli Xv | to 4-KQhlenstQffatoiijen .qder.in p-position zyeii | other ste | i.pnd§ X ^ ujid Xp- together with one} _ ankQndens_ierteil ring mean ^ represent. - S. ... gtilbyrbenzQxazqle gladly phend-the Fprtnel- X, R- _# R _gi R and R ₁ ^ PUpb, Ij, corresponding in the have given meaning. 5. stilbylbenzoxazole according to claim 1, accordingly the formula Ri CH = CH wherein X. ,, X ₁ ,, X, -, R ,, Rp, R, and R ₁ , have the meaning given in claim 1. 4. stilbylbenzoxazole according to claim 1, accordingly the formula CH = where Xg is hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 12 carbon atoms, cyclohexyl or phenyl, X _{7 is} hydrogen, chlorine, alkyl having 1 to 4 carbon atoms or Xg and X _{7 are} in the o-position to one another, together a fused benzene ring, R is hydrogen , Chlorine, alkyl with 1 to 8 carbon atoms, benzyl, 2-phenyl-propyl- (2) or cyclohexyl, Rg hydrogen, chlorine or alkyl with 1 to 4 carbon atoms and R ₇ hydrogen, chlorine or 309834/1163 ./ι Alkyl with 1 to 4 carbon atoms mean. 5. Stilbylbenzoxazole according to claim 1, accordingly the formula ⁿ VV _{cn == CH} _ / - v _n ^ χ = / < ^X 8> 2-n where X _{n is} hydrogen. Chlorine or alkyl of 1 to 4 carbons substance atoms M hydrogen, alkali metal or ammonium, η is the number 1 or 2, R is hydrogen, chlorine, alkyl with Benzyl, 2-phenylpropyl- (2) / 1 to 8 carbon atoms / or cyclohexyl, IV hydrogen, Chlorine or alkyl with 1 to 4 carbon atoms and R " Mean hydrogen, chlorine or alkyl having 1 to 4 carbon atoms. Jo. ■ Stilbylbenzoxazole according to claim 1, corresponding to the formula - ^ ν CH = CH 3098 ^ 4/1 where X _{q is} hydrogen or chlorine, M is hydrogen, alkali metal or ammonium, η is the number 1 or 2 and Rg is hydrogen, chlorine or alkyl having 1 to 4 carbon atoms. 7. Stilbylbenzoxazole geraäss claim 1, accordingly the formula CH = CH where X "is hydrogen, chlorine or alkyl with 1 to 4 carbon atoms and XQ is carboxyl, carbalkoxy with 2 to 9 carbon atoms or cyano, Rr is hydrogen, chlorine, alkyl with 1 to 8 carbon atoms, benzyl, 2-phenylpropyl- (2) or C3 ⁷ clohexyl, R 1 denotes hydrogen, chlorine or alkyl with 1 to 4 carbon atoms and R ₇ denotes hydrogen, chlorine or alkyl with 1 to 4 carbon atoms. 8. stilbylbenzoxazole according to claim 1, accordingly the formula 3Q9834 / 1163 rän ^ L ₁ L, B _rJ R / r · and B ₁ - the % indicated in the claim ^ bgn to have... qhend dßr formula Stiltralbenzoxaziols according to claim I ₃ corresponding WQV.in Xq Wasserstolfl, GfrLpE pdpr; Alkyl piit 1 iils # ? ■■ '- "-i. -.1- λ ^. - ¹ - Q"-' ■ ι-- '- ■ - ■■■ · "· -: ■ ' ·· ■ ■■» * ^J ~ ^ l - * ■■ "ji '■ - * -ii - ■ - * -> -i- * - 5-ΐ> ■ -"4-.' V * · -J-- ^ "- - / - - ■ * - ί ■; - · ■ - * - -! ■■ i · "- 'j * ' - * 'Λ stpEfatptiign, X ,, Garti-pxyl, Oa.r.balkpx ^ iriii; 2 to § sfcafEatpraen odpr, Gyanp and B ₀ Wagseü.sfcpßf. pder A'lkyj with I big I KgtLlg ^ sfcqlfatpmgn b, gd | ut; fn. - 10. S-EngnpxFrtlgn ^ pxazplc; according to An§p.r, uph -L, enfc- wpri ^ Bp. Bo mass ^ s ^ pff ¹ qdev, AIk nd A, §i ^ en. Best of; .Eq Alk.yl K} it _: 3 _f to § KphlgpylpEopjpl- ^ 3 | pdgr ^ qloti ^ qß., ± $ 1 to | Kphlg | i | tQ | Sa ^ pmgri (10a) -c in which R ₁ - and R "have the meaning given, or a radical of the formula * 7orin Xg for hydrogen, chlorine or alkyl with 1 to 4 carbon atoms stands mean. 11. A method for the optical brightening of organic materials, in particular cotton, polyamides, polyester, polypropylene, polyvinyl chloride, polystyrene, polyurethanes and cellulose acetates, characterized in that these materials, based on the weight of the material to be brightened, 0.0001 to 2%, preferably 0.0005 to 0.5 $ 6-phenoxy-benzoxazole according to claims 1-10 incorporated or applied to the surface thereof. 12.Organic material, especially cotton, polyamides, polyester, polypropylene, polyvinyl chloride, polystyrene, Polyurethane or Ccllulor: eaeetate containing 30 98.-34/1 16: 3 0.0001 to 2.% _} preferably 0.0005 to Q>, b% based on the weight of the material to be treated 6-phenoxy-benzoxazole according to claims 1 to 10, 13 · Detergent characterized by a content of 0.005 '· to 1 ^ of a β-phenoxy-benzoxazole compound according to claim 5 or 6. '. ■ ' 30983A / 1163