DE2037854A1 - Whitening agents - Google Patents

Description

The present invention relates to coumarin compounds of the formula

Shark

in which

R ₁ and Rp denote hydrogen, alkyl, cycloalkyl, aralkyl, aryl, cyano, carboxyl, carboxylic acid ester or carboxamide groups, or together form a non-aromatic 5- or 6-membered ring system, and

R represents hydrogen, alkyl or aryl radicals, Hal represents bromine or preferably chlorine, and their manufacture and use as optical brightening agents.

The alkyl radicals R ₁ , R ₂ and R are to be understood as meaning straight-chain or branched, saturated or unsaturated alkyl groups with 1-4 carbon atoms, which are replaced by substituents such as

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Halogen atoms, for example fluorine, chlorine and bromine, hydroxyl groups, Alkoxy groups with 1-4 carbon atoms ,. Alkylcarbonyloxy groups with 1-4 C atoms in the alkyl radical, carboxylic acid groups and alkoxycarbonyl groups with 1-4 carbon atoms in the alkyl radical can be substituted.

Suitable alkyl radicals R ₁ to R- are, for example: methyl, ethyl, ß-hydroxyethyl, ß-acetoxyethyl, 13-chloroethyl 1, carboxyethyl, carbethoxyethyl, ethoxyethyl, n- and iso-propyl, n-, iso- and tert-butyl , isobutenyl, pentyl, hexyl, octyl, decyl, dodecyl.

The aryl radicals R ₁ to R- are to be understood as meaning, in particular, phenyl radicals which can carry one or more substituents, for example fluorine, chlorine, bromine, cyano, alkyl and alkoxy groups with 1-4 carbon atoms, the carboxyl group, alkoxycarbonyl groups 2-5 carbon atoms, alkylsulfonyl groups with 1-4 carbon atoms, phenyl radicals, sulfonic acid groups (including their salts) and sulfonamide groups and sulfonic acid ester groups optionally substituted by lower alkyl radicals.

Examples of such residues are as follows:

Phenyl-, ο-, m- and p-fluorophenyl-, o-, m- and p-chlorophenyl, o-, m- and p-bromophenyl-, o-, m- and p-ethoxycarbonylphenyl-, m- and p-methanesulfonylphenyl-, m- and p-ethanesulfony! phenyl-, p-Benzyloxyphenyl, p-biphenyl radicals.

Suitable cycloalkyl radicals R ^ and R ₂ are, in particular, cyclopentyl and cyclohexyl radicals.

Suitable aralkyl radicals R ₁ and R ₂ are above all benzyl, p-chlorobenzyl, β-phenylethyl and styryl radicals.

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Non-aromatic ring systems fused to the thiazole ring, which R ₁ and R ₂ can also symbolize together with the two carbon atoms of the triazole ring, are in particular cyclopentane and cyclohexane rings, which in turn can be further fused to a benzene ring. The following are examples of these fused systems:

Suitable carboxylic ester groups R ₁ and Rg are, in particular, alkoxycarbonyl groups with 1-4 carbon atoms in the alkoxy group, such as methoxycarbonyl radicals or butoxycarbonyl radicals.

Suitable carboxamide groups R- and Rg are carboxamide groups which are optionally mono- or disubstituted with alkyl radicals having 1-4 carbon atoms. The groups -CONH ₂ , -CONHCK ,, -CONHC ₄ H ₉ , -C0N (CH ₅ > ₂ and -CONCC ^ H ^ may be mentioned as examples.

Particularly preferred coumarin compounds within the framework of the formula I. sin <ä those of the formula

^t 2-Vx

IN

v / V '

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in which R ^, R ' ₂ and R' represent water, optionally substituted by halogen, hydroxyl, alkoxy, alkylcarbonyloxy, carboxyl or alkoxycarbonyl groups or optionally substituted by halogen, cyano, alkyl, alkoxy, carboxyl -, alkoxycarbonyl, alkylsulfonyl, phenyl, sulfonic acid, optionally substituted sulfonamide or sulfonic acid ester groups by alkyl radicals are phenyl radicals; 'and R' and R'p also represent cyclohexyl, benzyl or phenylethyl radicals or the remaining members of a fused-on cyclohexyl - Or form cyclopentyl radicals, the alkyl and alkoxy radicals preferably containing 1-4 carbon atoms and Hal having the abovementioned meaning.

Suitable lightening agents in the context of the formula I are further compounds of the formula

in which R " _{2 stands} for a cyano, carboxyl, carboxylic acid ester or carbonamide group, R" ^ and R "have the same meaning as R'- and R ¹ -. and Hal stands for bromine or preferably chlorine.

The new lightening agents of the formula I are obtained by adding coumarin compounds of the formula

(IV)

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in which R

and R- * has the meaning given above

have, X is hydrogen or hydroxyl and Y is chlorine, bromine or hydrogen,

by treatment with dehydrating agents cyclized at elevated temperatures - optionally in an inert solvent - with elimination of HX, and if Y is hydrogen, then chlorinated or brominated.

Appropriately, those coumarin compounds, which in the context of the compounds of the formula I, the formula II is obtained by using compounds of the formula

Shark

in which R ¹

R ¹

R ^1. , And shark the above-

Have meaning

either directly triazolized by treatment with dehydrating agents or by the action of dehydrating agents first to the corresponding triazole-N-oxides of the formula

= T-R,

Shark

in which R ^, R ' ₂ > ^R
Have meaning
implemented and then reduced.

^and shark the above-

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The coumarin compounds IV and V are dehydrated in a manner known per se by heating with dehydrating agents such as acid anhydrides and acid halides.

Examples are:

Acetic anhydride, propionic anhydride, acetyl chloride, thionyl chloride, sulfuryl chloride and phosphorus pentoxide, the Acetic anhydride is to be regarded as particularly suitable, which either in copious excess or in conjunction with Solvents is used.

Suitable solvents are dimethyl sulfoxide, dimethylformamide, W N-methylpyrrolidone, tetramethylurea, o-dichlorobenzene, etc. Bases such as lithium, sodium or potassium acetate, trimethylamine, triethylamine, dimethylbenzylamine, pyridine or higher pyridine homologues are usually useful.

The temperatures at which the dehydration is carried out can be varied over a wide range. In general one works at temperatures between 40 and 160 C, preferably between 60 and 140 ° C.

The ring closure of the compounds V to the triazole-N-oxides of Formula VI in the presence of dehydrating agents is expediently carried out in those solvents which are listed under those used ™ reaction conditions and are inert towards the selected oxidizing agents, e.g. pyridine, higher pyridine bases, Dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetic acid and their mixtures with water.

Suitable dehydrating agents include mercury (II) oxide, Copper (II) salts such as copper acetate and copper sulfate, complexes Copper (II) salts, lead dioxide, lead tetraacetate, sodium and Potassium dichromate, potassium ferricyanide, hydrogen peroxide,

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Acetoperacid and potassium peroxydisulfate.

A technically preferred embodiment consists in the
Dehydrogenation of compounds of the formula V in pyridine or
Technical pyridine bases with copper (II) salts such as copper acetate or copper sulfate, which can be used in solid form or in aqueous solution, it being possible to blow in air.

This oxidative ring closure is generally carried out at temperatures from about 0 ° C. to 100 ° C., preferably from
20 to 80 ° C.

The subsequent reduction of the triazole-N-oxides VI can for example by zinc dust and zinc amalgam in acetic acid or mineral acid solution or suspension as well from tin gram or tin (II) chloride in mineral acids take place.

The coumarins of the formula (V) required as starting substances can be prepared in a manner known per se by that 4-acetamino-2-hydroxybenzaldehyde or its anil with Pyrazoly / acetic acids of the formula

HOOC-CH ₂ -N

where R, and Ha! have the meaning given above, condensed to 7-acetamino-3- / chloropyrazolyl- (l27-coumarins, then hydrolyzed the acetamino group to the amino group,

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the 7-aniinocoumarins obtained by diazotization and then Reduction converted into the corresponding 7-hydrazinocoumarins and finally this in itself as well known manner with a-Oximinoketonen of the formula

R ₁ -CO-CR ₂ (VIII)

NOH
condensed to the oximinohydrazones of the formula V "

Some of the pyrazolylacetic acids are known. You get it in a manner known per se (cf. German patent application P 19 42 926.6) by chlorination or bromination of the corresponding halogen-free pyrazole acetic acids.

Suitable pyrazole acetic acids (VII) are e.g.

4-chloropyrazolyl- (l) -acetic acid, 3-methyl-4-chloropyrazolyl- (l) -acetic acid, 3-phenyl-4-chloropyrazolyl- (l) -acetic acid, 5-p-tolyl-4-chlorpyrazolyl- (l) -acetic acid, 3-P-AnISy1-4-chloropyrazolyl- (1) acetic acid, 3-p-chlorophenyl-4-chloropyrazolyl- (1) -acetic acid, 3-ethyl-4-chloropyrazolyl- (1) -acetic acid, 2-propyl-4-chloropyrazolyl- (1) -acetic acid and 4-bromopyrazolyl (I) acetic acid .

Suitable compounds (VIII) include? Oximinoacetone, diacetyl monoxime, l-oximino-butanone- (2), 2-0ximino-1-phenyl-butanone- (5), 1,2-diphenyl-l-oximinopropanone- (2), oximinobenzyl-cyclohexyl ketone, l-oximino-4-phenyl-buten- (3) -one- (2), 2-0ximino-pentanone- (3) * 3-0ximino-4-methyl-pentanone- (2), l-oximino-4-methylpenten- (3) -one- (2), 3-0ximino-pentanol- (5) -one- (2), 3-0ximinohexanone- (2), 2-0ximino-5-methyl-hexanone- (5), 2-0ximinoheptanone- (J), 5-0ximino-heptanone- (4), 3-0xamino-octanone- (2), 4-oximino-nonanone- (5) t 3-0ximino-undecanone- (2), 5-oximinotridecanone- (2), Oximinoacetophenone, p-fluorine, p "chlorine and p" bromo-oximonoacetophenone, p-methyl "and p-methoxy-oximinoacetophenone, 2,4- and 3 * 4-dimethyl-oximinoacetophenone, oximinopropiophenone, p-fluorine, p-chlorine and p-bromo-oximinopropiophenone, p-methyl, p-benzyl, p-dimethylbenzyl, p-ethyl and p-tert.-

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Butyl-oximinopropiophenone, p-methoxy- and p-ethoxy-oximinopropiophenone, p-Benzyloxy-oximinopropiophenone, 2,5-dimethyloximinopropiophenone, 2 ~ 0ximino-1,3-diphenylpropanone- (1), 1-oximino-l-phenylacetone, 1-oximino-l-o-, -m- and -p-tolylacetone, 1-oximino-l-o-, -m-, and -p-anisylacetone, 1-oximino-l-o-, -m- and -p-chlorophenylaeeton, 1-oximino-l-m- and -p-cyanophenyl acetone, 1-oximino-l-m- and -p-carbäthoxyphenyl-acetone, 1-oximino-l-m- and-p-methane-sulfonylphenyl-acetone, 1-oximino-1,5-diphenylaoeton, Oximinobutyrophenone, Y-benzoyl-y-oximinobutyric acid-methyl- and ethyl ester, oximinovalerophenone, oximino-1- and -2-propionaphthon, benzil monoxime, tolil monoxime, Anisilmonoxime, oximinocyclopentanone, oximinocyclohexanone, 2-0ximino-indanone- (l), 2-0ximino-tetralone- (l).

The coumarin compounds corresponding to formula III, is advantageously produced by making connections the formula

H ■

R "-— C

_R,. ² \ H JL JL X "^» ^ Hal (IX)

in which R '^, R " ₂ , R", and Hai have the meaning given above,
triazolized by treatment with dehydrating agents.

A preferred embodiment of this dehydration is characterized in that the compounds IX are first converted into the copper complexes with the aid of copper (II) salts and this by heating in the presence of excess complex copper (II) salt solution in the corresponding Converts 7-triazolyl-coumarin compounds.

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Furthermore, lead tetraacetate, for example, is suitable as a dehydrating agent.

The coumarin compounds required as starting compounds of formula IX can be obtained, for example, by using 7-aminocoumarin derivatives the formula

where R, and Hai have the meaning given above, diazotized and with enamines of the formula

R ₀ -CH

^ ti R ₁ -C -NH

wherein R ₁ and Rp have the meaning given above, couples.

The subsequent halogenation of the pyrazole ring of the pyrazolylcoumarin compounds obtained by ring closure of the compounds IV (Y = H) the formula

(XII)

wherein R ₁ , Rp and R have the meaning given at the beginning,

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can be carried out according to methods known per se, e.g. with elemental chlorine or bromine in glacial acetic acid, with hypochlorite or hypobromite in glacial acetic acid, as well as with sulfuryl chloride or phosphorus pentachloride in non-polar solvents, in particular in chlorinated hydrocarbons such as di-, tri- and tetrachloroethane and mono-, di- and trichlorobenzene and their mixtures.

The substituents of the new coumarin compounds of the formulas obtainable by one of the processes mentioned above I to III can of course be further converted in a manner known per se following the full synthesis.

For example, sulfonic acid groups can be introduced into aryl radicals R ₁ to R-, and sulfonic acid groups by subsequent sulfonic acid groups, and sulfonic acid groups present can be converted into sulfonamide and sulfonic acid ester groups in a known manner.

Furthermore, e.g. cyano groups in carboxyl, carbonamide or carboxylic ester groups are converted and carboxyl groups are esterified or amidated.

The new coumarin compounds of the formula (I) are valuable lightening agents. They are suitable for lightening the most diverse Materials, especially for lightening fibers, threads, fabrics, knitted fabrics and foils of synthetic origin especially for lightening materials made of polyesters, polyurethanes, polycarbonates, polyvinyl chloride and polyamide as well for lightening paints made from cellulose esters and nitrocellulose. The compounds (I) containing sulfonic acid groups are suitable It is also used to lighten natural materials such as wool, silk and cellulose as well as regenerated cellulose and cellulose acetates. They can be used in the usual way, for example in the form of aqueous dispersions or solutions or in the form of solutions in indifferent solvents; if desired

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you can use them in combination with detergents or add casting compounds that are used for the production of films or threads. As a result of their high stability, they can, for example, also be added to polyesters when they are produced from the components; Polycondensates can be added after the precondensation or during the polycondensates. The amounts of pyrazolyltriazolylcoumarins required in each case can easily be determined by preliminary tests; In general, amounts of 0.1 Gl - 1% based on the weight of the material to be treated are sufficient. The pyrazolyltrlazolylcoumarins of the formula I are very economical brightening agents; the brightenings achieved are very lightfast and generally have excellent washfastness.

Coumarin compounds of the general formula I, the one or contain several alkyl radicals with 4-12 carbon atoms, are suitable in many cases for the optical brightening of synthetic Fiber materials made from organic solvents. The method is characterized in that the fiber materials with Impregnated dye liquors containing these brighteners and then subjected to a heat treatment.

Compared to those described in Belgian patent 681,962 Show 3-pyrazolyl-7-benzo- and -naphthotriazolyl-coumarins the new coumarin derivatives of the formula (I) substituted by monocyclic triazolyl (2) radicals have a significantly improved drawability on polyester materials; compared to the 5-aryl-7-triazolyl- (2) -coumarins described in Belgian patent specification 695.656, and also compared to the coumarin compounds described in the first-mentioned Belgian patent the chloropyrazolyl-triazolyl- (2) -coumarins of the formula (I) due to stronger, clearer and more brilliant lightening during the thermosol treatment made of polyester materials.

Compared to the constitutionally closest comparable pyrazolylv-triazolylcoumarins of Belgian patent 726,619, the present compounds of the formula I are distinguished improved chlorine or chlorite resistance. Le A 13 205 - 12 -

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example 1

Preparation of 3 - ^ - chloropyrazolyl- (127-7 - / ^ - phenyl-5-

methyl-v-triazolyl- (227-coumarin (1 h).

1.14 kg of pyrazolyl (l) acetic acid are concentrated in 6 liters Mixed with hydrochloric acid. A solution of 324 g of sodium chlorate in 1.35 kg of water is added dropwise at 30.degree Surface and stir for another 30 minutes. You dilute the Mix with ice to 18 liters and suck off the deposited material. After neutral washing the filter cake and Drying at 120 ° C gives 1.068 kg of 4-chloro-pyrazolyl- (l) acetic acid with a melting point of 160 C.

2.04 kg of acetic anhydride, 1.016 kg of 4-acetylaminosalicylidene aniline, 0.41 kg of anhydrous sodium acetate and 0.803 kg of 4-chloro-pyrazolyl- (l) -acetic acid are heated to 145 ° C. for 15 hours. Allowing the temperature of the mixture at 90 ° C fall, the melt mixed with 4 kg of ice and sucks the 20 ^υ C deposited 7-acetylamino-3- _</ ^ after cooling -. Chlorpyrazolyl- (l27-coumarin from The filter cake is washed with 4 kg of acetone After drying, 0.847 kg of 7-acetylamino-3 - ^ - chloro-pyrazolyl- (127-coumarin in the form of brownish crystals with a melting point of 288 - 290 ° C.

92 g of 7-acetylamino-3 - ^? - chloro-pyrazolyl- (l27-coumarin be Stirred in 180 ml of 78% sulfuric acid at 100 ° C. for 1 hour. The mixture is then cooled to 20 ° C., 600 ml of glacial acetic acid are added and the mixture is diazotized at + 16 ° C. with a Solution of 21 g of sodium nitrite in 100 ml of water. After 3 hours, the diazonium salt solution is cooled to 0 ° C. and gives a solution of 136 g of tin (II) chloride in 300 ml concentrated hydrochloric acid. After one hour, the deposited yellow material is filtered off with suction, in 2 liters of water suspended, the suspension is made ammoniacal. To

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suctioning off, washing with water and drying gives 93 S 7-hydrazino-3 - ^ - chloropyrazolyl ~ (l) 7-coumarin vom Melting point 209 ° C (Z.).

93 g of 7-hydrazino-3- ^ f-chloropyrazolyl- (127-coumarin are stirred with 60 g of oximinopropiophenone and 10 ml of 50% acetic acid in 220 ml of methyl glycol for 12 hours at 95 ° C. The bronze-colored precipitated after cooling to 5 ° C. Crystals are filtered off with suction, washed out with 200 ml of methanol and dried. 133 g of oximinopropiophenone-, ^ - (^ - chlorpyrazolyl) -coumarinyl- (7l7-hydrazone in the form of bronze-colored to yellow crystals with a melting point of 2 "Jk- 275 ° G (Z .). 133 g of oximinopropiophenone - / ^ - (^ - chlorpyrazolyl) -coumarinyl- (7}, 7-hydrazone are added dropwise with 40 g of acetic anhydride in 230 ml of pyridine while the temperature is kept at 85 to 90 ° C After stirring for three hours at 85 to 95 ° C., the pulpy reaction mixture is cooled to 10 ° C. and the pale crystals which have separated out are filtered off with suction, washed with 100 ml of methanol, then with 1/2 l of warm 8% hydrochloric acid and finally with 1 liter of water. After drying, 125 g of a light gray crystal powder are obtained, which is boiled for cleaning together with 95 g of fuller's earth for 1 hour in 1.2 l of chlorobenzene. Finally, the chlorine dioxide solution is clarified through a preheated pressure filter, the filtrate is cooled to approx. 0 °, and after standing for several hours, the precipitated crystals are filtered off with suction, washed with 200 ml of cold methanol and dried. III g of 3- ^ 5-chloropyrazolyl- (l] _7-7-Z ² ' ^: "P ^nen y ^{: L} ~ 5- ^metn y ^{] L} ~ v-triazolyl- (227-c ^uma- rin are obtained as a greenish light yellow Crystals that dissolve colorless in dimethylformamide; this solution fluoresces intensely purple-tinged blue when irradiated with UV light at 350 nm.

In an analogous manner, the compounds of the formula (I) listed in the table below under a - t were prepared from 7-hydrazino = -3-chloropyrazolyl-coumarin and the corresponding a-oximinoketones; the compounds u and ν were derived from Y-hydrazino - ^ - O-methyl-i or -phenyl-4- chloropyrazolyl- (l] / - coumarin and the listed oximinoketones

shown. ., j, _

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(D

ro
ο

UI

No.

R.

α-Oximinoketone fluorescent color in DMF (350 rma)

la

CE

OO
CO
CD

ld

If

Ig
lh
Ii
Ik
11

C ₂ H ₅

Ib

lc n-C

CH.

CE ^

CH

CE-

CH,

CE.

H E E E

ⁿ " ^C 10 ^H 21 ^H oximino acetone

E E E E E

strong reddish blue fluorescence

2-oximino "

pentanone- (J)

3-oximino "

heptanone- (4)

2-methy1-3- "

oximinopentanone- (4)

3-oximinotri- "

decanon- (2)

2-oximino-l-strong somewhat reddish blue phenylbutanone- (3) fluorescence

Oximinoaceto- "

phenone

Oximinopropio "

phenone

1-oximino-l- "

phenylacetone

^ -Chlor-oximino- " propiophenone

1-m-cyanophenyl-1- " oximinoacetone

CD OO OO

ro

Io

CH

_r CH.

Ip Iq

Ir Is

It

Iu C ₂ H ₅

Iv C ₂ H ₅

Iw

CH,

cc-Oximinoketone fluorescent color in DMF (350 mi)

1-p-tolyl-loximinoacetone

4-fluoro-oximino
acetophenone

strong, somewhat reddish blue fluorescence

ljjS-di- strong blue fluorescence phenylacetone or
2-oximino-l _{: t} ; 3-diphenylpropanon- (l) ■

Benzil monixime "

Oximinovalerophenon strong somewhat reddish

blue fluorescence

Oximinobenzyl-cyclo- "
hexyl ketone

p-benzyl-oximino- "
propiophenone

2-0xirainoindanone- (l) strong blue fluorescence

2-0ximinopentanone- (3) strong, slightly reddish blue fluorescence

2-0ximinopentanone- (3) "

Oximinobutyrophenone

strong, somewhat reddish blue fluorescence

IV) O GO

Example 1 χ;

16.1 g of 3- _</ ^Pyr> azolyl (l) 7-7 / 5-ethyl-5-raethyl-v-triazolyl (227-coumarin (see FIG. Belgian Patent 726,619, Example 1 d) in 600 ml of glacial acetic acid was dissolved warm and 10 g of bromine were added at about 40 ° C. After standing for 3 hours at 45-50 ° C., half of the glacial acetic acid was distilled off under reduced pressure and the yellow crystals which separated out on cooling were filtered off with suction and made from chlorobenzene 18 g of 3 - ^ - bromopyrazolyl- (1) 7-7- ^ T-ethyl-S-methyl-vtriazolyl- (2) 7-coumarin are obtained as pale green-tinged crystals which show strong, red-tinged blue fluorescence in dimethylformamide to solve.

Example 1 y:

3- ^ Pyrazolyl- (1) 7-7- ^ 5-phenyl-5-methyl-v-triazolyl- (2) 7-coumarin can be used in an analogous manner (cf. BeIg. Patent specification 726.619, Example 1 a) in glacial acetic acid with bromine to give 3- ^ f-bromopyrazolyl- (1) 7-7 - ^ - phenyl-5-methyl-v-triazolyl- (l) 7-coumarin convert, which is present after recrystallization from dimethylformamide in the form of greenish-tinged needles and in dimethylformamide solution strongly reddish blue fluorescent.

Example 2:

a) 27 g of 7-amino-3 - ^? - chlorpyrazolyl- (l) 7-coumarin are in a mixture of 200 ml of glacial acetic acid and 25 ml of concentrated Hydrochloric acid at 0 - 5 ° C with 7 g sodium nitrite in 25 ml water diazotized. The diazo suspension obtained is left at about 10-15 ° C. in a solution of 16 g of β-amino cinnamonitrile drop into 200 ml of 80% alcohol, a pH of 5-6 being obtained by adding aqueous sodium acetate solution last. After the coupling has ended, the orange-brown azo compound is filtered off with suction and washed out with water and dries.

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40 g of the azd dye thus obtained are stirred in 320 ml Pyridine and gradually gives 38 g of copper (II) acetate at 50 ° C added. The mixture is stirred for a further 6 hours at 50 ° C. and 1 hour at 75 ° C., after which most of the pyridine becomes Stripped off in vacuo and the residue is with 300 ml 60 $ aqueous methanol was added. The precipitate formed is filtered off with suction while still hot, dried and extracted with chlorobenzene. The crude product remaining after the extraction agent has evaporated is used for purification Glycol monomethyl ether and then redissolved from dimethylformamide. The kirstalline product is sucked off with cold Washed methanol and dried. 29 * 5 g of greenish white crystals of 3- ^ 4 "-Chlorpyrazolyl- (l) / - 7- are obtained ^ F-phenyl-5-cyano-v-triazolyl- (227-coumarins, which is colorless dissolves in dimethylformamide; this solution fluoresces with a reddish blue tinge on irradiation with UV light of 350 μm.

In an analogous manner, 7-amino-3 - ^ - chlorpyrazolyl- (l} _i 7-coumarin (a - e), or 7-amino-3- ^ 3-phenyl-4-chloropyrazolyl- (l27 "coumarin ( f) the chloropyrazolyl-v-traizolyl-coumarin compounds listed in the table below are prepared.

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Η »

IO

R ₂

R-.

No.

Rr.

I.
H 2 B σ I. CD. OO 2c 00 σ> 2d 00 CO
u> 2e 2f

CB

CH,

COOH

COOC ₂ H ₅

COOC ₂ H ₅

CONH ₂

COOCoH

H H

H H

made from fluorescent paint in DMF (350 my.)

ß-Aminocinnamic acid - somewhat reddish blue nitrile, saponified. fluorescence

ß-amino cinnamic acid "
ethyl ester

ß-aminocrotonic acid violet-blue fluorescence ethyl ester

ß-Aminocinnamic acid amide

ß-aminocrotonic acid ethyl ester

blue fluorescence

some reddish blue fluorescence

Example 3

A fabric made of polyester fibers is placed in a bath with a liquor ratio of 1:40, which contains 1.5 g of sodium oleyl sulfonate per liter, 0.75 g of formic acid and 0.1 g of 3 - ^ - chloropyrazolyl- (1 ^ 7-7 - ^ - phenyl-5-methyl-v-triazolyl- (227-coumarin contains, the preparation of which is described in Example 1. The bath is heated to the boil within 30 minutes and approx Maintained at boiling temperature for 45 minutes, with the tissue is moderately moved. The fabric is then rinsed and dried. It then has an outstandingly brilliant one and strong brightening of excellent light, washing and chlorite fastness.

The brightening thus obtained is stronger and clearer than that in the same way with that in the Belgian patent 681,962 described, next comparable 3 -, / pyrazolyl- (127 ~ 7-naphthotriazolylcoumarin achieved brightening and shows an increased stability against chlorine-containing bleaches in comparison with the pyrazolyl-triazolylcoumarins of Belgian patent 726,619.

Example 4

A fabric made of polyester fibers is padded with an aqueous liquor containing 1 g per liter of one of the compounds listed in Examples 1 or 2 and 3 g of a commercially available dispersant based on fatty alcohol polyglycol ethers. The fabric is then squeezed off to a weight increase of 100 % , then dried and heated to 125 ° C. for 30 minutes. The fabric treated in this way shows a strong clear lightening of high light, wet and chlorite fastness compared to untreated material.

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Example 5

A fabric made of polyester fibers is padded with an aqueous liquor containing 1 g of a commercial dispersant based on fatty alcohol polyglycol ethers, 1 g of a commercial wetting agent based on alkylnaphthalenesulfonic acids, 4 g of alginate thickener and a solution of 1 g of one of the compounds in 20 g triethanolamine, which are listed in Examples 1 or 2. The fabric is then squeezed off to a weight increase of 100 % , then dried, heated to 190 ° C. for 1 minute and then washed hot. Compared to untreated fabric, it shows a very strong and brilliant brightening of excellent light, washing and chlorite fastness.

Compared to those described in Belgian patent specification 695.656 The closest comparable phenyl-triazolyl-coumarins are shown by the pyrazolyl-triazolyl-coumarins according to the invention stronger and clearer highlights; For example, with ^ - / ^ - Chlorpyrazolyl-i127-7- ^ f-phenyl- or -4-p-chlorophenyl-5-methyl-v-triazolyl ~ (227-curnarin (Example 1h or 1k) stronger and more brilliant lightening than with the corresponding 3-phenyl-7 - ^ - phenyl- or -4-pchlorphenyl ~ 5-methyl-v-triazolyl- (227-coumarin (Belgian patent specification 695x656, example 1c or 1d). Compared to the analogous pyrazolyl-v-triazolylcoumarin compounds of the Belgian Patent specification 726,619 (Example 1 a and 1 p) show the present chloropyrazolyl-v-triazolylcoumarin compounds improved stability against chlorine-white bleaching agents under difficult conditions.

Example 6

In a 20 1 stirred autoclave 6 kg of terephthalic acid dimethyl ester and 5 1 of ethylene glycol with 0.05 % zinc acetate and 0 * 05 % (based on terephthalic acid dimethyl ester) of one of the compounds listed in Examples 1 to 2a

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Formula (I) mixed. The autoclave is first heated to 180 ° C. with stirring. The transesterification begins at about 150 ° C; the split off methanol is distilled off.

After 1 hour the temperature is increased to 200 ° C, after a further 45 minutes to 220 ° C. After a total of 2 3/4 hours the transesterification is finished. The total amount of methanol split off is at least 2.4 liters.

The product thus obtained is used for precondensation under nitrogen transferred to an autoclave heated to 275 ° C. During the precondensation, the excess glycol is in passed directly through a cooler and collected. After 45 minutes, a weak vacuum is first applied, which increased to (below) 1 Torr over another 45 minutes will. The stirring speed is reduced. After 2 1/2 The polycondensation has ended for hours. The product obtained then becomes threads with a final titer in a known manner spun from 5O-25 den. The threads obtained have an excellent whiteness with excellent light and light Wet fastness.

Example 7

Yarn made of polyamide 6 is treated for 50 minutes in a liquor ratio of 1:40 at 80-90 ° C. in an aqueous bath containing 0.15 g of the lightening agent of the formula per liter

NaO ^ S

Su ^ v ^ V Γ Ii T VA

Cl

and contains 2 grams of sodium chlorite. After rinsing and drying, the yarn shows a very clear lightening of good lightfastness.

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The whitening agent used was prepared as follows: 10 g of 3 - ^? - chloropyrazolyl- (127-7 - ^ - phenyl-5-methylv-triazolyl- (2] _7-cmmarine (Example 1) are added to 85 ml of concentrated sulfuric acid with stirring 2 Hours kept at 115 ° C. After cooling, the batch is poured into 400 ml of cold water, common salt is added until precipitation is complete and the sulfonic acid which has separated out is filtered off with suction. The filter residue is stirred in 500 ml of hot water and neutralized with sodium hydroxide solution hot solution using adsorption carbon and salt out the sulfonic acid sodium salt by adding sodium chloride. The precipitated product is filtered off with suction, washed with cold 5% sodium chloride solution and dried. The sodium salt of the j5 - ^ - chloropyrazolyl- (1 ^ 7- 7 - ^ - sulfοphenyl-5-methy1-vtriazolyl- (227-c ^u fflsf * 'ins as' light greenish crystal powder (yield 10.2 g), the colorless solution of which in dimethylformamide in UV light has a strong violet-tinged blue fl uoresziert.

Example 8

A fabric made of cellulose acetate fibers is moved in a liquor ratio of 1:40 at 60 ° C for 45 minutes in an aqueous bath that is in the Liter 1 g of sodium oleyl sulfonate, 0.75 g of formic acid and 0.1 g of one of the compounds listed in Examples 1 or 2 of formula (I) contains. The fabric is then rinsed and dried. After this treatment, the material is excellent lightened.

Example 9

In 1 kg of opaque soft polyvinyl chloride 1 g one of the compounds listed in Example 1 incorporated. The material is then brilliantly lightened and shows you clear white tone.

Example 10

In 1 kg of a colorless lacquer made from nitrocellulose or cellulose acetate 0.5 g of one of the compounds listed in Examples 1 and 2 is dissolved. The paint is then on a Thinly spread a colorless background. After drying, the laok layer is brilliantly lightened. Le A 13 205 «23 -

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Example 11

16; 1 s> ^ pyrazolyl- (127-7 - ^ - ethyl-5-methyl-v-triazolyl- (coumarin (see Belgian patent specification 726,619 * Example 1d) are dissolved in 250 ml dichloroethane at 50-35 ° C with 8 g Sulfuryl chloride is added dropwise with stirring. Then the mixture is stirred for a further 3 hours at 50-60 ° C., then the solvent is distilled off under reduced pressure and the separated crude product is recrystallized from chlorobenzene using fuller's earth. 15 g of 3- ^ ^I F- are obtained. Chlorpyrazolyl- (l27-7- ^ F-ethyl-5-methyl-v-triazolyl- (227-coumarin (cf. Example 1b) as greenish white crystals which dissolve in dimethylformamide with a strong reddish blue fluorescence.

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Claims (1)

Claims in which R'- ,, R ' ₂ and R'., for hydrogen, optionally substituted by halogen, hydroxyl, alkoxy, alkylcarbonyloxy, carboxyl or alkoxycarbonyl groups or optionally substituted by halogen, cyano, alkyl, alkoxy, Carboxyl, alkoxycarbonyl, alkylsulfonyl, phenyl, sulfonic acid, optionally sulfonamide or sulfonic acid ester groups substituted by alkyl radicals are phenyl radicals; and R ^ and R ' _{2 are} also cyclohexyl, benzyl or phenylethyl radicals or form the remaining members of a fused-on cyclohexyl or cyclopentyl radical, the alkyl and alkoxy radicals preferably containing 1 - k carbon atoms, and Hal is chlorine Le A 13 205 - 25 - 109886/1833 203785 Coumarin compounds of the formula Hal in which R " _{2 stands} for a cyano, carboxyl, carboxylic acid ester or carbonamide group and R" and R " ₂ for hydrogen, optionally substituted by halogen, hydroxyl, alkoxy, alkylcarbonyloxy, carboxyl or alkoxycarbonyl groups or optionally by Halogen, cyano, alkyl, alkoxy, carboxyl, alkoxycarbonyl, alkylsulphonyl, phenyl, sulphonic acid, sulfonamide or sulphonic acid ester groups optionally substituted by alkyl radicals are phenyl radicals; the alkyl and alkoxy radicals are preferably 1-4 C- Contain atoms, and ⁰ Hal means chlorine. Coumarin compounds of the formula Shark in which Z _{1 is} hydrogen; C 1 -C 4 alkyl radicals; phenyl radicals optionally substituted by halogen, benzyl or sulfo groups; Benzyl radicals or cyclohexyl radicals; ζ for hydrogen; C 1 -C 4 alkyl radicals; phenyl radicals optionally substituted by halogen, cyano or alkyl groups; Carboxyl; Cyan; Carbamoyl or carbalkoxy radicals; Z-, hydrogen, C - ^ - C ^ -alkyl radicals, or denotes the phenyl radical; Z, and Zg together stands for Γ Jf ; and shark means chlorine. ^ fc ^^ CHg Le A 13 205 - 26 - 109886/1833 5.) Coumarin compound of the formula 6.) Coumarin compound of the formula 7.) Coumarin compound of the formula CH 8.) Coumarin compound of the formula Cl 9.) Coumarin compound of the formula Le A 13 205 109886/1833 10) Process for the preparation of new coumarin compounds according to claim 1, characterized in that one coumarin compounds the formula in which R- ,, R ₂ and R ^, have the abovementioned meaning, X is hydrogen or hydroxyl and Y is chlorine, bromine or hydrogen, by treatment with dehydrating agents or dehydrating agents at elevated temperatures - optionally in one inert solvent - cyclized with elimination of HX, and in the event that Y is hydrogen, then chlorinated or brominated. 11) Process for the preparation of new coumarin compounds according to claim 2, characterized in that one compounds the formula in which R ^, R ' ₂ and R' represent hydrogen, alkyl radicals optionally substituted by halogen, hydroxyl, alkoxy, alkylcarbonyloxy, carboxyl or alkoxycarbonyl groups, or optionally substituted by halogen, cyano, alkyl, alkoxy, carboxyl, alkoxycarbonyl -, alkylsulphonyl, phenyl, sulphonic acids are phenyl radicals which are optionally substituted by alkyl radicals or sulfonamide or sulfonoic acid ester groups; and R ¹ , and R ^1,. also mean cyclohexyl, benzyl or phenylethyl radicals or form the remaining members of an attached cyclohexyl or cyclopentyl radical, the alkyl and alkoxy radicals preferably containing 1-4 carbon atoms, and Hal is chlorine,
Le A 13 205 - 28 ψ 109886/1833 either directly by treatment with dehydrating agents triazolized or by the action of dehydrating agents initially to give the corresponding triazole-N-oxides of the formula Shark ■ (VI) in which R ^, R * ₂ ' ^R * 3 ^{and Hal dle} have meaning above,. . implemented and then reduced. 12) Process for the preparation of new coumarin compounds according to claim 3> characterized in that one Compounds of the formula Shark in which R " _{2 stands} for a cyano, carboxyl, carboxylic acid ester or carboxylic acid ester group and R" and R " ₂ for hydrogen, optionally substituted by halogen, hydroxyl, alkoxy, alkylcarbonyloxy, carboxyl or alkoxycarbonyl groups or optionally substituted by alkyl radicals phenyl radicals substituted by halogen, cyano, alkyl, alkoxy, carboxyl, alkoxy carbonyl, alkylsulphonyl, phenyl, sulphonic acid, sulphonamide or sulphonic acid ester groups optionally substituted by alkyl radicals; the alkyl and alkoxy radicals preferably being 1-4 C. -Atoms, contain and shark means chlorine, triazolized by treatment with dehydrating agents Le A 15 205 - 29 - ' 109886/1833 Process for the optical brightening of organic materials, characterized in that coumarin compounds of Claims 1-9 used. Organic materials, lightened with coumarin compounds of claims 1-9 Le A 15 205 - 30 - 109886/1833