DE2037854C2 - 3- (4-Chloro-1-pyrazolyl) -7-v-triazol-2-yl-coumarin compounds and their use for optical brightening - Google Patents

Description

in which

Hydrogen, Ci-Cr-alkyl, optionally phenyl, benzyl or cyclohexyl substituted by fluorine, chlorine, C-Cv-alkyl CC ₄ -alkoxy, cyano or the sulfonic acid group or salts thereof;

Hydrogen, Ci -C, -alkyl, optionally by fluorine, chlorine, QC-alkyl, Ci-C ₄ -alkoxy, cyano or the sulfonic acid group or their salts substituted phenyl, cyano, carboxyL (Ci-Q-alkoxyJ-carbor.yl , optionally mono- or disubstituted carbonamide by C 1 -C 1 -alkyl radicals, or and R 2 together is a radical of the formula

15th

20th

25th OH

JO

CH ₂

The subject matter of the invention is the subject matter characterized in the claims.

The lightening agents of the formula I according to the invention are obtained by adding coumarin compounds of the formula

in which

Ri, R ₂ and R3 have the meaning given in claim 1.

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

denote and

R _{3 represents} hydrogen, C ₁ -C ₄ alkyl or phenyl

2. Use of the compounds according to claim for the optical brightening of organic Materials.

R ₂ -CR ₁ -C

45 αν)

implemented and then reduced

The coumarin compounds II or III are dehydrated in a manner known per se Heating with water-releasing liquids, such as acid anhydrides and acid halides.

Examples include: acetic anhydride, propionic anhydride, acetyl chloride, thionyl chloride, Sulfuryl chloride and phosphorus pentoxide, the Acetic anhydride is to be regarded as particularly suitable, which is used either in copious excess or in conjunction with solvents.

Suitable solvents are dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, tetramethyl urea, o-dichlorobenzo! i.a. Most of the time it is practical the addition of bases such as luhium, sodium or

Potassium acetate, trimethylamine, triethylamine, dimethyl

benzylamine, pyridine or higher pyridine homologues.

The temperatures at which the dehydration

carried out can be varied over a wide range. In general, temperatures between 40 and 160 ° C., preferably between 60 and 140 ^° C., are used.

By ringing the connections between St. Triazole-N-oxides of the formula IV in the presence of Debydrogenating agents will be useful in such Solvents carried out under the reaction conditions used and against each selected oxidizing agents are inert, such as. B. 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, complex copper (II) salts, lead dioxide, lead tetraacetate, sodium and potassium dichromate, potassium ferricyanide. Hydrogen peroxide, acetoperacid and potassium peroxydisulphate ' ^s

A technically preferred embodiment consists in the dehydrogenation of compounds of the formula III in pyridine or technical pyridine bases with copper (II) salts such as copper acetate or copper sulfate, which in solid Can be used in the form or in an aqueous solution, blowing in air being expedient can.

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

The subsequent reduction ier triazole-N-oxides IV can be carried out, for example, by zinc dust and zinc amalgam in acetic or mineral acid solution or suspension and by tin gram or tin (H) chloride in mineral acids. ^3Ü

The coumarins of the formula HI required as starting substances can be prepared in a manner known per se by mixing 4-acetamino-2-hydroxybenzaldehyde or its anil with pyrazolylacetic acids of the formula ^J5

HOOC-CH ₂ -N

(V)

where Rj and Hai have the meaning given above ■ * ' have, to 7 * acetamino-3- (4-chloro-l-pyrazolyl) -coumarins if the acetamino group is then condensed to the amino group, the 7-aminocoumarins obtained are hydrolyzed by diazotization and subsequent reduction into the corresponding 7-hydrazinocoumarins'> <> and finally this in a manner also known per se with a-oximinoketones of the formula

R ₁ -CO-CR ₂
NOH

(VD

condensed to the oximinohydrazones of the formula III

Some of the pyrazolylacetic acids are known. They are obtained in a manner known per se (cf. DE-PS 19 42 926.6) by chlorination of the corresponding halogen-free pyrazole acetic acids.

The coumarin compounds of the formula I, in which R _{2 stands} for * "a carboxyl group optionally modified according to claim 1, are advantageously prepared by using compounds of the formula

(vn)

triazolized by treatment with dehydrating agents A preferred embodiment of this dehydrogenation is characterized in that the Compounds VH initially converted into the copper complexes with the help of copper (II) salts and these through Heating in the presence of excess complex copper (II) salt solution in the corresponding 7-triazolyl-coumarin compounds converts

Furthermore, for example, BIei (IV) acetate is used as a dehydrating agent suitable

The coumarin compounds required as starting compounds of formula VII are z. B. obtainable by using 7-aminocoumarin drug of the formula

(Vffl)

wherein R ₃ and Hai have the meaning given above, diazotized and with enamines d;? r formula

R ₂ -CH

R ₁ -C-NH ₂

(IX)

wherein R ₁ and R _{2 have} the meaning given above, couples.

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

wherein Ri, R ₂ and R] have the meaning given at the beginning, can be carried out by methods known per se, for. B. with elemental chlorine or bromine in glacial acetic acid, with hypochlorite or hypobromite in glacial acetic acid, and with sulfuryl chloride or phosphorus pentachloride in non-polar solvents, especially in chlorinated hydrocarbons such as di-, tri- and tetrachloroethane and mono-, di- and trichlorobenzene and mixtures thereof.

The substituents of any of the above process mentioned new coumarin compounds of the formula 1 can of course be followed by the full synthesis in a per se known Way to be further transformed. ί

For example, in phenyl radicals R or R2 by subsequent salivation sulfonic acid groups to be introduced.

Furthermore, for example, cyano groups in carboxyl, CarbonamW or carboxylic acid ester groups converted into and carboxyl groups are esterified or amidated accordingly.

The coumarin compounds of the formula (I) are valuable lightening agents. They are suitable for Lightening the most varied of materials, especially for lightening fibers, threads, fabrics, Knitted fabrics and films of synthetic origin, especially for lightening materials made of polyesters, polyurethanes, Polycarbonates, polyvinyl chloride and polyamide as well as for lightening paints made from cellulose esters and nitrocellulose. The compounds (1) containing sulfonic acid groups are also suitable for lightening natural materials such as wool, silk and cellulose as well as regenerated cellulose and cellulose acetates. They can be used in the usual way, e.g. B. in the form of aqueous dispersions or solutions or in the form of solutions in inert solvents; if desired, they can also be used in combination with Use detergents or add casting compounds that are used to manufacture foils or threads. As a result Their high stability, for example, can also be used when they are made from the polyesters Components are added; They can polycondensates after the precondensation or during the Polycondensation can be added. The amounts of pyrazolyltriazolylcoumarins required in each case can easily be determined by preliminary tests; in general, amounts of 0.01-1% based on are sufficient on the weight of the material to be treated. The pyrazolyltriazolylcoumarins of the formula I are very good rich · brightening agents; the lightening achieved are very lightfast and generally have excellent washfastness.

Coumarin compounds of the general formula I ₁ which contain one or more alkyl radicals with 4-12 C atoms are suitable in many cases for the optical brightening of synthetic fiber materials from organic solvents. The process is characterized in that the fiber materials are impregnated with dye liquors which contain these brighteners and then subjected to a heat treatment

Compared to the 3-pyrazolyl-7-benzo- and naphthotriazolyl-coumarins described in Belgian patent specification 6 81 962 show those according to the invention substituted by monocyclic v-triazol-2-yl radicals Coumarin derivatives of the formula (I) have a significantly improved drawability on polyester materials, which is expressed in the higher degree of whiteness of the treated materials compared to the in the Belgian patent 6 95 656 described t> o 3-aryl-7-v-triazol-2-yl-coumarins, as well as opposite the coumarin compounds described in the first-mentioned Belgian patent are distinguished by the Coumarins of the formula (1) according to the invention by stronger, clearer and more brilliant lightening in the * ■> Thermosol treatment made of polyester materials.

Compared to the constitutionally closest comparable 3-pyrazol-l-yl-7-v-triüzol-2-yl-coumarins from the Belgian Patent specification 7 26 619, the present compounds of the formula I are characterized by an improved Chlorine or chlorite resistance from,

Example I.

Preparation of 3- (4-chloro-1-pyrazolyl) -7- (4-phenyl-5-methyl-v-triazol-2-yl) -coumarin

1.14 PyrazoM leg-acetic acid are dissolved in 6 liters of concentrated hydrochloric acid stirred at 30 ⁰ C is added dropwise a solution of 324 g of sodium chlorate in 135 kg of water with the surface and then stirred for a further 30 minutes. The mixture is diluted with ice to 18 liters and the deposited material is filtered off with suction. After the neutral washing the filter cake and drying at 12Q C ^S is obtained 1.068 kg of 4-chloro-l-pyrazol-l-acetic acid of melting point 160 ⁰ 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 -i-chloro-pyrazoI-1-acetic acid are heated to 145 ° C. for 15 hours ⁰ C fall, the melt is covered with 4 kg of ice and sucks off the 7-acetylamino-3- (4-chloro-1-pyrazol-1 yl) coumarin which has separated out after cooling to 20 ° C. The filter cake is washed with 4 kg of acetone. After drying, 0.847 kg 7-acetylamino-3- (4-chloro-l-pyrazolyl) coumarin in the form of brownish small crystals of melting point 288-290 ⁰ C.

92 g 7-acetylamino-3- (4-chIür-l-pyrazolyl) -coumarin be in 180 ml 78% sulfuric acid for 1 hour at 100 ⁰ C the mixture stirred mixture is then cooled to 20 ⁰ C., to 600 ml Glacial acetic acid and diazotized at + 16 ° C with a solution of 21g sodium nitrite in 100 ml water. After 3 hours, the diazonium salt solution is cooled to 0 ° C. and a solution of 136 g of tin (II) chloride in 300 ml of concentrated hydrochloric acid is added. After one hour, the deposited yellow material is filtered off with suction, suspended in 2 liters of water, and the suspension is made ammoniacal. After filtration with suction, washing with water and drying, 93 g of 7-hydrazino-3- (4-chloro-l-pyrazolyl) -coumarin of melting point 209 ⁰ C (Z.).

93 g of 7-hydrazino-3- (4-cnIor-l-pyrazoIyl) coumarin are stirred with 60 g Oximinopropiophenon and 10 ml of 50% acetic acid in 220 ml of methylene glycol for 12 hours at 95 ° C The precipitated after cooling to 5 ⁰ C bronze-colored crystals are filtered off with suction with 200 ml of methanol and dried. 133 g of oximinopropiophenone [3- (4-chloro-l-pyrazolyl) -7'-coumarin] hydrazone are obtained in the form of bronze-colored to yellow crystals with a melting point of 274-275 ° C ( Z.). 133 g of oximonopropiophenone- [3- (4-cb! Or-l-pyrazolyl) -7-coumarinyl] 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 three hours of stirring at 85 to 95 ° C, cool the slurry Rekationsgemisch to 10 ⁰ C. and filtered off with suction the precipitated bright crystals. It is rewashed with 100 ml of methanol, then with 1/2 l of warm 8% hydrochloric acid and finally with 1 l of water. After drying, 125 g of a light gray crystal powder are obtained which, for cleaning, is boiled in 1.21 chlorobenzene for 1 hour together with 95 g of fuller's earth. Finally, the chlorobenzene solution is clarified through a preheated pressure filter, the filtrate is cooled to approx. 0 °, and after standing for several hours, the crystals which have separated out are filtered off with suction and washed with 200 ml

cold methanol and dry them. 113 g of 3- (4-chloro-1-pyrazolyl) -7- (4-phenyl-5-methyl-v-triazol-2-yl -) - coumarin are obtained as greenish pale yellow crystals which dissolve colorless in dimethylformamide; this solution fluoresces on irradiation with UV light of 350 ηιμ intense violet-tinged blue.

In an analogous manner, pyrazolyl-coumarin and the corresponding Λ-oximinoketones were made the compounds of the formula (I) listed in the table below under a-t are prepared; the compounds u and ν were derived from 7-hydrazino-3- [3- (methyl or phenyl) -4-chloro-1-pyrazolylj-coumarin and the listed oximinoketones.

Cl

H CH ₃ H Oximino acetone ! • 'hinrewenifarhe in DMF C ₂ H ₅ CH ₃ H 2-oximino-3-pentanone (350 nvi) la nC ₃ H, C ₂ H ₅ H 3-oximino-4-heptanone strong reddish blue
fluorescence Ib CH ₃ -CH (CH ₃ J ₂ H 2-methyl-3-oximino
4-npntannn the same lc CH ₃ ΓΗ -V ^^ > H 2-oximino-l-phenyl-
3-butanone the same ld the same le strong somewhat reddish
blue fluorescence

^lf

lh CH _;

Ii CH;

Ik CH

11 CH ₃

In the F

In

Io

CH ₃

Cl H

Oximinoacetophenone

the same

Oximinopropiophenone like.

1-oximino-l-phenylacetone desgl.

4-chloro-oximinopropiophenone

1-m-cyanophenyl-1-oximinoacetone

the same

the same

1-p-tolyl-l-oximinoacetone desgl.

4-fluoro-oximi ni>
acetophenone

the same

1-oximino-l ^ niiphenyl-strong blue acetone or 2-oximino fluorescence 1,3-diphenylpropanone- (1)

Benzil monixime

the same

continuation

ίο

No. R,

fl-oximinoketone

Fluorescent color in DMF (350 rrtu)

C ₃ H ₇

CH,

Oximinovalerophenon strong somewhat reddish

blue fluorescence

Oximinobenzyl cyclohexyl ketone

2-oximino-1-indanone

2-oximino-3-nentanone

the same

strong blue
fluorescence

strong, little reddish-blue fluorescence

It CjH,

CH,

2-oximino-3-pentanone

the same

C ₂ H.

Oximinobutyrophenone

strong, somewhat reddish blue fluorescence

Example 2

a) 27 g of 7-amino-3- (4-chloro-l-pyrazolyl) coumarin are diazotized in a mixture of 300 ml of glacial acetic acid and 25 ml of concentrated hydrochloric acid at 0-5 ° C. with 7 g of sodium nitrite in 25 ml of water. The diazo suspension obtained is added dropwise at about 10- 15 ° C into a solution of _r, 16 g / 3 Aminozimtsäui'enitril dripped in 200 ml of 80% alcohol, obtained by addition of aqueous Natriump.cetatlösung a pH of 5 - 6 last sustains. After the coupling has ended, the orange-brown azo compound is filtered off with suction, washed out with water and dried.

40 g of the azo dye thus obtained are diluted in 320 ml of pyridine and 38 g of copper (II) acetate are gradually added at 50 ° C. The mixture is stirred for a further 6 hours at 50 ° C. and 1 hour at 75 ° C., then ₄ -, most of the pyridine is stripped off in vacuo and

300 ml of 60% strength aqueous methanol are added to the residue. The deposited precipitate is Sucked off while still hot, dried and extracted with chlorobenzene. The crude product remaining after the extraction agent has evaporated is used for purification from glycol monomethyl ether and then redissolved from dimethylformamide. The crystalline product is filtered off with suction, washed with cold methanol and dried. 29.5 g of greenish-white crystals are obtained of 3- (4-chloro-1-pyrazolyl) -7- (4-phenyl-5-cyano-v-triazol-2-yl) -coumarins, which dissolves colorless in dimethylformamide; this solution also fluoresces when irradiated UV light of 350 μιη reddish blue.

In an analogous manner, from 7-amino-3- (4-chloro-lpyrazolyl) -coumarin (a - e), or 7-amino-3- (3-phenyI-4-chloro-1-pyrazolyl) -coumarin (f) the coumarin compounds listed in the table below are prepared

Made of

Fluorescent color in DMF (350 ηνμ)

2d CH ₃

COOH

COOC ₂ H ₅ H

COOC ₂ H ₅ H

jg-amino cinnamonitrile,
saponified

jg-amino cinnamic acid ethyiester

jS-aminocrotonic acid ethyl ester

somewhat reddish blue
fluorescence

the same

violet blue
fluorescence

continuation

No.

Made of

Fluorescent color in DMF

(350 ΓΠμ)

2e

CONH ₂

jff-amino cinnamic acid amide blue fluorescence

2f CH ₃ COOC ₂ H ₅

Example 3

A fabric made of polyester fibers is placed in a bath in a liquor ratio of 1:40, which is 1.5 g per liter Sodium oleyl sulfonate, 0.75 g formic acid and 0.1 g 3- (4-chloro-1-pyrazolyl) -7- (4-phenyl-5-methyl-v-triazol-2-yl) -cumann contains, the preparation of which is described in Example i. The bath will take place within 30 minutes heated to boiling and held at boiling temperature for about 45 minutes, the tissue being moderate is moved. The fabric is then rinsed and dried. It then has an excellent brilliant 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 one Next comparable 3- (1-pyrazolyl) -7- (2-naphtho [a] triazolyl) -coumarin described in patent specification 6 81 962 achieved brightening and shows an increased stability against chlorine-containing bleaches in comparison with the Pyrazolyi-triazolylcoumarins of Belgian patent 7 26619.

Example 4

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

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 in the Belgian patent specification 6 95 656 described next comparable phenyltriazolylcoumarins The pyrazolyl-triazolyl-coumarones according to the invention show stronger and clearer AufjS-Aminocrotonsäureäthylester

somewhat reddish blue
fluorescence

brightens; for example, one obtains in this way with 3- (4-chloro-1-pyrazolyl) -7- [4- (phenyl or 4-p-chlorophenyl) -5-methyl-v-triazol-2-yl] -coumarin (Example lh or Ik) stronger and more brilliant brightening than with the corresponding 3-phenyl-7- [4- (phenyl- or 4-p-chlorophenyl) -5-methyl-v-triazol-2-yl] -coumarin (Belgian patent Ö 95 656, example Ic u £ w. Iu). Compared to the analogous pyrazolyl-v-triazolylcoumarin compounds the Belgian patent 7 26 619 (Example la or Ip) 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, 5 μg of dimethyl terephthalate and 51 ethylene glycol are mixed with 0.05% zinc acetate and 0.03% (based on dimethyl terephthalate) of one of the compounds of the formula (I) listed in Examples 1 to 2a. 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 to 200 ° C, after another 45 minutes, at 220 ⁰ C increases by a total of 2 3/4 hours, the transesterification is completed is. The total amount of split off methanol is at least 2.4 I.

The product thus obtained is converted to precondensates under nitrogen in a heated at 275 ⁰ C autoclave. During the precondensation, the excess glycol is passed directly over a cooler and collected. After 45 minutes, a weak vacuum is first applied, which is increased to below 13 mbar (1 Torr) over a further 45 minutes. The stirring speed is reduced. After 2 1/2 hours, the polycondensation is complete. The product obtained is then spun in a known manner into threads with a final denier of 50-25 denier. The threads obtained are outstandingly bright with excellent light and wet fastness.

Example 7

Yarn made of polyamide 6 for 30 minutes at a liquor ratio of 1: 40 at 80-90 ⁰ C in an aqueous bath treats g in a liter of 0.15 whitening agent of the formula

NaO ₃ S

CH

i! nd contains 2 g of sodium chlorite. After rinsing and On drying, the yarn shows a very clear lightening of good lightfastness.

The lightening agent used was prepared as follows: 10 g of 3- (4-chloro-1-pyrazolyl) -7- (4-phenyi-5-methyl-v-triazol-2-yl) -coumarin (Example 1) are in 85 ml ^{concentrated sulfuric acid kept at 115 °} C. for 2 hours with stirring. After cooling, the batch is poured into 400 ml of cold water, table 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. The hot solution is clarified using adsorption charcoal and the sulfonate sodium salt is salted out by adding sodium chloride. The precipitated product is filtered off with suction, washed with cold 5% sodium chloride solution and dried. The sodium salt is obtained

3- (4-chloro-1-pyrazolyl) -7- (4-sulfophenyl-5-methyl-vina ^ ui-2-yi ! -coumarins as a new greenish crystal powder (Yield 10.2 g), its colorless solution in dimethylformamide in UV light strongly violet-tinged blue fluoresces.

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 containing 1 g of sodium oleyl sulfonate, 0.75 g of formic acid and 0.1 g of one of those listed in Examples 1 or 2 per liter Contains compounds of formula (I). The fabric is then rinsed and dried. After this treatment, the material is brilliantly lightened.

Example 9

In 1 kg of opaque soft polyvinyl chloride is applied to the Roller 1 g of one of the compounds listed in Example 1 is incorporated. The material is then brightened excellently and shows a clear shade of white.

Test report

Formula lightener

10

(D

Poiyestergewebe was a liquor ratio of 1: 20 with a liquor containing 0.5 g / l of a commercially available dispersing agent, 1% acetic acid 3O ⁿ / oig and 0.1% (based on fabric weight) of a subsequent brightener contained, 45 minutes at 125 ⁰ C treated.

Remission measurements were carried out on the samples obtained using the Elrepho apparatus (ZEISS). The Berger whiteness was derived from the measured values. Taube, Hunter and Stensby (Soap + Chemical Specialties Vol. 43/7, p. 86 (1967)) certainly.

30th

i, r; = H

₄₀ Ri =

Ri =

BE-PS 6 81 962 Example 1

Example 10

In 1 kg of a colorless lacquer made of nitrocellulose or cellulose acetate, 0.5 g of one of the compounds is added solved, which are given in Examples 1 and 2. The lacquer is then thinly 50 Ic on a colorless substrate crossed out. After drying, the varnish layer is brilliantly lightened

Example 11

16.1 g of 3- (l-pyrazolyl) -7- (4-ethyl-5-methyl-v-triazoi-2-yl) coumarin (cf. Belgian Patent 7 26619, Example Id) are added to 250 ml of dichloroethane 30-35 ⁰ C with 8 g of sulfuryl chloride was added dropwise with stirring. The mixture is then stirred for a further 3 hours at 50-60 ° C., the solvent is then distilled off under reduced pressure and the crude product which has separated out is recrystallized from chlorobenzene using fuller's earth. 15 g of 3- (4-chloro-1-pyrazolyl) -7- (4-ethyl-5-methyl-v-triazol-2-yl) -coumarin (cf. Example Ib) are obtained as greenish white crystals which dissolve in dimethylformamide with strong reddish blue fluorescence.

55

60

65

Ri = H

r; = egg

H ₅ C ₂ O

Id: Rl =

Ri = CH ₃

r; = egg

N-

BE-PS 6 81 962 No. 1.Page 7

H ₅ C

Ν -

ίο

Polyester fabrics were treated as above with a liquor, but 0.5 g / l of a commercially available one Dispersant, 2 g / l of a sodium chlorite solution 5014ig, 1 g / I oxalic acid and 0.15% (based on the weight of the goods) contained one of the following optical brighteners.

The white measurement was carried out as above described.

r; (n) H ₇ C ₃
\
H ₅ C ₂ 7 ^ = H 16 Ij: Ri, Ri = H /
H ₅ C ₂ = C1 N
/ ' N.
[N—
N r; Ik: ( ^N > - Ri N Ri

BE-PS 7 26 619 Example 1 Γ

(iso) H ₇ C

ί, Ν

20 II: Ri =

if: r; =

H ₃ C
Ri, Ri = H

N -

BE-PS 7 26 619 Example 1

H ₃ C

N -

BE-PS 7 26 619 Example Ie

Ri, Ri = H

(! SO) H ₇ C ₃

Im: R; =

30 H ₃ C

N -

N -

Ri = H
Ri = Cl

35

Ri = H
Ri = Cl

Polyester fabrics were impregnated with a liquid, those per liter are 1 g of a commercially available dispersant, 4 g of alginate thickening and 1 g of the following contained optical brightener, squeezed to a weight increase of 80%, dried, Heated to 175 ° C for 20 seconds, rinsed hot and · »-, dried.

The whiteness was determined as above.

As shown in the table below of the whiteness values for a representative selection of optical brighteners As can be seen from the present application, the optical brighteners according to the invention have compared to the closest prior art, surprisingly, always the higher degrees of whiteness.

Whiteness values

Brightener Berger

dove

Hunter Stensby

Ri,

Ii: Ri =

= H

CH ₂ N

N -

BE-PS 7 26 619 Example 1 d,

50

N -

CH ₂ N

R ₂ = H

r; = egg

Wl

Yes 162 178 144 157 Ib 166 183 147 162 Ic 170 188 150 166 Id 151 165 137 150 Ie 156 174 142 158 If 146 164 139 159 Ig 153 170 143 160 You 125 131 118 122 Ii 140 149 128 134 Ij 132 144 125 137 Ik 141 154 131 144 Il 128 138 122 133 in the 141 154 131 143

308 127/11

Claims (1)

Claims; 1, coumarin compounds of the formula IQ X represents hydrogen or hydroxyl and Y means chlorine or hydrogen, by treatment with dehydrating agents elevated temperatures - optionally in an inert solvent - with elimination of HX cyclizes, and in the event that Y is hydrogen is then chlorinated Appropriately, those coumarin compounds, alkyl of the formula I, in which R2 is hydrogen, corresponding alkyl or phenyl is obtained by using compounds of the formula