DE2045796A1 - v Triazolylcumanne - Google Patents

Description

The present invention relates to new ones in the 3-position by a mononuclear, aromatic carbo- or heterocyclic group substituted coumarins, which in 7-position a v-Triazolyl group, to which a 1,1-dialkylindane radical in 4,5-position is fused. The invention also relates to the use of these compounds for optical brightening of organic materials such as polyesters, then the material brightened with it and a process for producing the Links.

3-phenylcoumarins, which have a v - triazolyl (2) group in the 7-position which is substituted with a tetramethylene group or an ο, ^ - phenylmethylene or -ethylene group, are already known as optical brighteners. They have a low intrinsic color and fluoresce intensely in daylight blue-violet to violet and are more lightfast than other known brighteners with a similar structure.

It has now been found in a further development of this invention that v-triazolylcoumarins of the formula I

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(D

wherein R ₁ and R _{2 represent} alkyl groups of 1 to 6 carbon atoms and

Y for a mononuclear, with the coumarin ring in Conjugated carbo- or heterocyclic aryl group

stand and the Cuiriarinrest and the benzene nucleus Λ still through Kalogen, lower alkyl and alkoxy groups may be substituted can, a class with a surprisingly high and brilliant whitening effect represents, and at the same time the lightfastness is still significantly greater than in the case of the known compounds mentioned. Since the new compounds are also less volatile, they are particularly suitable for lightening organic materials, that are exposed to higher temperatures, such as spinning pulps.

The inventive v-triazoles of the formula I form colorless to yellowish crystalline substances. Ionic substituted products show in water or polar organic Solvents, compounds without ionogenic groups show yellow, intense blue to violet fluorescence in organic solvents. The new coumarin compounds. give yellowed organic material in small quantities,

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to which she is incorporated or to which she is incorporated using conventional methods are applied according to conventional methods, a pure white

Aspect in daylight and are therefore valuable optical Brightener.

Compounds of the formula I, in which Y is optionally substituted by halogen, such as fluorine, chlorine or bromine, or an alkyl group with 1-4 carbon atoms substituted phenyl group, in particular compounds of the formula II

(II)

wherein R _{1 and R 2 represent} alkyl groups having 1 to 6 carbon atoms, in particular methyl groups, and R represents hydrogen, halogen or an alkyl group

with 1 to 4 carbon atoms

stand and the benzene nucleus A by halogen or alkyl groups may be substituted with 1 to 4 carbon atoms, preferably those in which A is unsubstituted or by chlorine or the methyl group is substituted and R denotes hydrogen, chlorine or the methyl group.

The mononuclear, carbo- or heterocyclic aryl group Y is preferably the phenyl group .

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BAD ORlQINAI.

The compounds are used for the optical brightening of organic materials. Depending on the substituents they are particularly suitable for certain substrates. she are used for the optical brightening of high molecular weight, hydrophobic, organic material, especially for brightening synthetic organic Polyplastcii, especially in the Spinning mass, i.e. plastics obtainable through polymerization, e.g. polycondensation or polyaddition, such as polyolefins, e.g. polyethylene or polypropylene, also polyvinyl chloride, but above all polyesters, especially polyesters aromatic polycarboxylic acids with polyhydric alcohols, such as polyterephthalic acid glycol esters, synthetic polyamides, such as nylon-6 and nylon-66, but also cellulose esters, such as Cellulose acetates.

The high molecular weight hydrophobic organic material is optically brightened, for example, by incorporating small amounts of optical brighteners according to the invention, preferably 0.001 to 1% based on the material to be brightened, with tr. The brighteners can be worked into the plastics, for example dissolved in plasticizers such as dioctyl phthalate, or together with stabilizers such as dibutyltin dilaurate or sodium pentaoctyl tripolyphosphate, or together with pigments such as titanium dioxide. Depending on the type of material to be lightened, the catch-up can also be in the monomers

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before polymerisation, in the polyr.erene mass or together: r. ~ <? n be dissolved with the polymer in a solvent. That Material previously treated in this way will then be known per se Processes such as calendering, pressing, extrusion, coating, casting and, above all, spinning and stretching, into the desired brought its final shape. The brighteners can also be incorporated into finishes, for example in finishes for Textile fibers such as polyvinyl alcohol, or in resins or resin precondensates such as methylol compounds of ethylene urea, which are used for textile treatment.

High molecular organic material can also be lightened in the form of fibers. To lighten these fiber materials it is advantageous to use an aqueous dispersion of v-triazoles of the formula I according to the invention. The brightener dispersion here preferably has a content of 0.005-0.5 % of v-triazole according to the invention, based on the fiber material. Besides, the dispersion auxiliaries * substances, such as dispersing agents, for example condensation products of 10 to 18, carbon atoms Direction fatty alcohols or alkyl phenols containing 15 to 25 mols of ethylene oxide, or condensation products of 16 to 18 carbon atom having Direction AlkyljTiono- or polyamines containing at least 10 moles of ethylene oxide, organic acids such as Formic, oxalic or acetic acid, detergents, swelling agents such as di- or trichlorobenzene, wetting agents such as sulfosuccinic acid alkyl esters, bleaching agents such as sodium chloride, peroxides or hydrosulfites,

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as well as, if necessary, whitening agents of other classes, such as e.g. cellulose-affine derivatives of stilbene.

The lightening of the fiber material takes place riding the aqueous brightener entv.-hedron in exhaust process, at temperatures of preferably 30 to 150 ⁰ C, or by padding. In the latter case, the Y7are is impregnated with, for example, a 0.2-0.5% brightener dispersion and finished, for example, by dry or moist heat treatment, for example by steaming at 2 atm. or, after drying, by briefly dry heating to 180-220 °, with the fabric optionally also being heat-set at the same time. The derai't treated fiber material is finally rinsed and dried.

According to the invention, optically brightened high molecular weight, organic material, in particular synthetic fiber material lightened by the exhaust process, has a pleasing, pure white, blue-violet to bluish fluorescent appearance.

According to the invention, the new brighteners can be prepared by adding an oxime of the formula III

(III)

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with. a Cu; r; ._ rinylhyurazine of the formula IV

(IV)

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in weakly acidic medium to the corresponding Oxi ~ hydraxon v ^ ceU / Ct: and this with the aid of a condensation device in a; Vcrbinciur ^ · the formula I converted. In the formulas, R, and R " Alkyl groups with 1 to 6 carbon atoms, Y is a mononuclear, carbo- or heterocyclic aryl group conjugated to the coumarin ring. The benzene nucleus A and the Cuir.arin ring can still by halogen, lower alkyl and or or Alkoxy groups may be substituted.

It is advantageous to work in the first stage in an acetic acid medium at an elevated temperature. As a condensing agent In the second stage, protonic acids or acid anhydrides are used, with the exclusion of water and optionally with heating is condensed.

As an example of ring-closing protonic acids, the hydrohalic acids are primarily mentioned as being effective Acid anhydrides the inorganic anhydrides phosphorus pentoxide and sulfur trioxide, the mixed inorganic-organic anhydrides, such as the alkanoyl and aroyi, alkylsulfonyl and Aryl sulfonyl halides, for example acctyl chloride, benzoyl chloride, Toluenesulfochloride, as well as the purely organic anhydrides, such as acetic anhydride, benzoic anhydride, also the mixed anhydride of formic acid and acetic acid.

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The condensation can be carried out in the presence of organic solvents which are inert under the reaction conditions. High-boiling hydrocarbons and caloric hydrocarbons are suitable as such, for example chlorobenzene, dichlorobenzene, X) ¹ IoIe; Inert slightly or more strongly basic solvents can also be used, for example dimethyl formamide, dirr.cthy! acetamide, or pyridine, picolines, quinolines. Depending on the substituents of the oxime hydrazones, the ring closure can be brought about by simply letting the reaction mixture stand or by heating it. Koirurien as a reaction temperature between room temperature and 25O ⁰ C, preferably from 200 ⁰ C, in question, Some zeitigt the presence of basic catalysts such as anhydrous alkali metal or alkaline earth metal salts of organic acids, for example sodium or potassium acetate, favorable results with respect to yield and purity of the final products.

In a modification of the production process described, the initially formed oxime hydrazone can be mixed with an oxidizing agent iii a v-triazole oxide of the formula V

transferred and this then with nascent hydrogen to a Compound of formula I can be reduced.

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The oxidative ring closure can be brought about by the action of the most varied of oxidizing agents; this is the · Work in oxidation resistant LÜsungsi-v ¹ 'SHAKE recommended. In acidic, for example acetic acid, solution are bichro: .-; ate or hydrogen peroxide, useful oxidizing agents; in basic solvents such as pyridine or pyridine-water mixtures, potassium ferricyanide, for example, is suitable. The generally applicable and therefore preferred method consists in the oxidation with copper (II) sulfate in pyridine water. It is not necessary to use stiichiometric amounts of copper because the monovalent copper formed during the reaction can be continuously converted back into the divalent stage during the reaction by blowing in air or oxygen.

For the reduction of the triazole oxides to the triazoles known methods, reduction with base metals and acids such as zinc dust in acetic acid or acetic acid-water mixtures is advantageous chosen. However, salts of reducing acids of sulfur or phosphorus can also be used for the reduction.

The oxime of the formula III used as starting material can be prepared in a known manner by condensation of a / 3, / J-dialkyl acrylic acid with a benzene using AlClo as Condensation agent and subsequent oximation of the indanone formed are produced.

In the following examples the temperatures are given in degrees Celsius.

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example 1

A solution of 30.0 g of 1,1-dimethyl-2-oxiniino-indan-3-one and of 50.0 g of 3-phenyl-7-hydrazinocuniarin in 350 ml Ethylene glycol monomethyl ether is mixed with 120 ml of 50 7_iger Acetic acid acidified and stirred at 60-70 ° for 12 hours. The ct-oximinoliydrazone crystallizes in the form of red-brown Crystals out. After all 3-phenyl-7-hydrazinocoumarin has been consumed, the condensation product is suctioned off, washed with alcohol and dried.

20.0 g of the ct-oximinohydrazone thus obtained are refluxed with 20.0 g of anhydrous potassium acetate in 200 ml of acetic anhydride for 5 hours. Which When the reaction mixture is cooled, the precipitating crystal mass is filtered off with suction, with ethyl alcohol, hot water and washed again with ethyl alcohol. The brightener is obtained by recrystallization from toluene and from methyl ethyl ketone the formula

with a melting point of 195 ° in the form of light yellow crystals, which dissolve in chlorobenzene with an intense blue-violet fluorescence. The compound is able to brighten organic material such as polyester fibers brilliantly.

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ORIGINAL

In the same way, if instead of 3-phenyl-7-hydrazinocoumarin equivalent amounts of 3- (4-methylphenyl) -7-hydrazinocoumarin or 3- (4-chlorophenyl) -7-hydrazinocoumarin are used, the following brighteners are made with similar properties:

M.p. 231-232 "

CH ₃ CH ₃

M.p. 217-219 "

Example 2

In front of the optical brightener according to Example 1, an approximately 0.1% dispersion is prepared by diluting 10 g of a 10% sand grind with 1000 ml of water and adding 2 g of di-noctyl sodium sulfosuccinate. A polyester fabric is padded with this dispersion at 20 ° (squeeze effect 50-607 = “roller pressure 30 kg / cm ² , speed 3 m / inch). The fabric is dried at 60 ° for 20 minutes.

The dry tissue is then bc-.i. For 30 seconds Fixed at 200 °.

The fabric treated in this way shows a clear lightening effect fect. - 101 /, / ν? g 9

Example 3

0.2 g of di-n-octylr sodium sulfosuccinate are added to 80 ml of water and 0.2 g of alkyl polyglycol ether added.

The optical brightener according to Example 1 is a Solution prepared by adding ir. To 10 g of the brightener in 1000 r.l Dimethylformamide dissolves = staircase solution I.

From the optical brightener of the formula

SO. Ka

(HOCH ₂ CH ₂ ) Λ} -, - N _/ _ / , - ^ N_-N (CH CH CH)

^{1 ll} ι / \\ _ HN_ / y_CH = CH- / \ _KH_ /% ^{l L}

C _r H ^ =

\ _KH_ / = ' N

SO ₃ Na

A solution is prepared by adding 20 g to 1000 ml of water solves = stainm solution II.

10 ml each of the stock solutions I and II are added to the solution described above. A pre-bleached polyester BaunrA-Oll-Gev.-ebe (67:33 parts mixed, squeeze effect 50-60%, roller pressure 30 kg / cm ² , speed 3 m / back) is padded with this dispersion.

The fabric is dried at 60 ° for 20 minutes. The dry tissue is then fixed at 200 ° for 30 seconds. The fabric treated in this way shows a clear lightening effect.

A fabric consisting of 50 parts of polyester and 50 parts of cotton is lightened in the same way.

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Example 4

To 290 ml of water, 0.3 ml of alkyl polyglycol ether and 0.15 ml of trichlorobenzene was added as a carrier. From the optical brightener genas ε example 1 a solution is made, ir.de ^: 1 g of the brightener in 1000 ml of AethylenglykolrrofiOTnethylätzher solves. 4.5 ml of this stock solution are added to the one described above Solution. This aqueous dispersion containing the brightener is heated to 60 °. Then you give a 15 g heavy polyester fabric into the solution. One increases the f

Temperature within 15 - 20 minutes to 130 ° and left at this temperature for 3.0 minutes. Then one pre-cools within: 10 - 15 minutes to 60 °. J) the fabric is then rinsed in running cold water for 2 minutes and at 60 ° for 20 minutes dried. The dry tissue is then 30 seconds heat set at 200 °.

The fabric treated in this way shows a clear lightening effect.

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Example 5

1000 parts of polyester granulate made of polyterephthalic acid ethylene glycol are intimately mixed with 0.25 parts of the optical brightener according to Example 1 and then spun into threads under nitrogen from an extruder at a temperature of 265-285 ° in a known manner through a spinneret. The polyester threads obtained in this way are brightly lightened.

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Example 6

In an E de Is pale autoclave equipped with a stirrer, a gas inlet crocodile, a vacuum device, a descending cooler and a heating jacket, 388 g of benzene-1, A-dicarboxylic acid are added. ester, 300 g of 1,2-ethanediol and 0.4 g of antimony oxide, while blowing nitrogen through it, heated to 200 ° outside temperature and kept at this temperature for 3 hours. 4 g of the optical brightener according to Example 1, dissolved in 40 g of 1,2-ethanediol, carefully introduced into the autoclave after the temperature has been lowered to 190 °. After the addition is complete, the temperature is increased to 285 "outside temperature within one hour, 1,2-ethanediol distilling off. A vacuum is then applied to the autoclave, the pressure is slowly reduced to 0.2 torr and the condensation is brought to an end under these conditions for 3 hours. While g of these operations is well stirred. The liquid condensation polymer is then pressed out through the bocene nozzle with nitrogen. The resulting polymer can be used to produce monofilaments that have a brilliant white aspect.

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BeisDiel 7

2 g of the optical brightener would be used in Example 1 dissolved in 40 ml of N-ethyl-pyrrolidine. You pour the solution in 960 ml of tetrachlorethylene. With this solution you plop down at 20 ° a polyester fabric and squeezes this at a speed of 10 m / min, between rollers with a Pressure from 30 kg / cm ^ to 80%, based on the weight of the goods, away. The padded fabric is for one minute at 60 ° dried and then heat-set for 30 seconds at 200 °.

The polyester material treated in this way shows a high and brilliant white.

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Claims (12)

Claims -IJ coumarin compounds of the formula I © -rvrrr * (I) "1 wherein R. and R2 represent alkyl groups with 1 to 6 carbon atoms and Y stands for a mononuclear carbo- or heterocyclic conjugation with the coumarin ring Ary! Group stand, and the coumarin residue as well as the benzene nucleus A still by halogen, lower alkyl and / or alkoxy groups can be substituted. 2. Coumarin compounds of the formula I ₁ wherein R-. and R2 ^ Mean methyl groups. 3. Coumarin compounds of the formula II where R | and R2 for alkyl groups with 1 to 6 carbon atoms and R for hydrogen, halogen or an alkyl group - _{Λ A} 'RAD ORIGINAL 1098U / 2269 20A5796 with 1 to 4 carbon atoms and the benzene nucleus A may be substituted by halogen or alkyl groups having 1 to 4 carbon atoms. 4. Coumarin compounds of the formula II in which A is unsubstituted, R is hydrogen and R ^ and R _{2 are} methyl groups. 5. Coumarin compounds of the formula II in which R is chlorine or the methyl group. 6. Coumarin compounds of the formula II in which A is substituted by chlorine or a methyl group. 7. Use of the coumarin compounds of the formula I for the optical brightening of organic materials. 8. Use of the coumarin compounds of the formula II for the optical brightening of organic materials. 9. Use according to claim 7 or 8 for the optical brightening of synthetic fibers. 10. Use according to claim 9 for the optical brightening of polyester fibers. BAD OR * 1098ΊΑ / 2269 11. Use according to claim 7 or 8 cum optical Lightening of polyester pulp. 12. Process for the preparation of coumarin compounds of Formula I, characterized in that an oxime of the formula III AA KOH (III) '2 with a coumarin hydrazine of the formula IV which can still be substituted in the coumarin residue, converts in an acidic medium to the corresponding oxime hydrazone and this converted into a compound of the formula I with the aid of a condensing agent, 13. Modification of the method according to claim 12, characterized in that that the initially formed Oximliydrazone ir.it an oxidizing agent into a v-triazole oxide of the formula V. (V) Transferred and this with nascent hydrogen to a compound of formula I reduced. 12/31 Le / mb / 8/11/197O 109314/2269 BATH ORIGINAL