DE1594832C - - Google Patents

Description

The invention relates to the use of special heterocyclic, ethylene double bonds containing Compounds as optical brighteners. The compounds to be used according to the invention are characterized by the fact that they follow the general formula

(1)

- rw = γη - ρ \>

- ™ ^ / -X ^ f Λ

Of preferred importance are those triazine derivatives, that of the general formula

B ₁ -CH = CH

IO -CH = CH-B ₁

(3)

correspond, where a is a hydrogen atom, a halogen atom, a methyl group or the methoxy group, Z ₁ and / or Z _{2 are} a ring member = CH - or = N- and α is a hydrogen atom, a phenyl radical or a radical in the series

20th

R '"- C

C -R ₂ -CH = CH -R

N N

R '"

(2)

B,

and in which B ₁ denotes a phenyl or diphenyl _{radical and B 2} denotes a hydrogen atom, a phenyl radical or an alkyl group having 1 to 4 carbon atoms and phenyl radicals an alkyl group containing 1 to 4 carbon atoms, halogen or a methoxy group.

Interesting compounds of the triazine series can also be represented by the formula

25 A ₇ -C CA ₅

I Il

N N

30th

35

represents, where I) at least one radical α is different from hydrogen or phenyl and the meaning has one of the other radicals indicated for ο, and where II) phenyl or naphthyl radicals still 1 to 3 alkyl groups, 1 to 2 halogen atoms, an alkoxy group, a carboxylic acid, carboxylic acid ester or May contain carboxamide group.

The definition under II) is to be understood as a supplement to the definition of the symbol α; d. i.e. that for the symbol α such substituents as mentioned under II) can also stand, provided α does not exist already means a substituent as it is primarily defined for this symbol.

In the case of s-triazine derivatives, the compounds to be used according to the invention can by the general formula -

■ V /

A ₇
are reproduced, where A _{6 is} a remainder of the series

-CH = CH-

(4a)

CH = CH

(4c)

55

60 A ₇ denotes a phenyl, diphenylyl radical or a radical A _6.

The general formula (1) also includes pyridine and pyrimidine derivatives, where for in the case of pyridine derivatives, those of the formula

V,

are circumscribed, where in this formula R "'is an organic radical bonded to the triazine ring by a benzene ring, R _{2 is to} be emphasized in the 1,4-position 65 and where in this formula V ₁ , to the triazine ring and the —CH = - Group bound benzene radical and R denotes an aromatic radical.

V ₂ or V _{3 represent} hydrogen, a styryl or p-phenylstyryl radical, but at least one radical V is different from hydrogen.

Among the pyrimidine derivatives are those of the general formula

W-CH = CH

CH = CH-W

emphasized, where W is a phenyl, diphenyl, 1-naphthyl or 2-naphthyl radical.

In these compound types listed under the formulas (1) to (6) are alkyl groups In principle, long-chain alkyl groups are also possible, but in most cases there are practically up to 8 carbon atoms containing alkyl groups, preferably containing 1 to 4 carbon atoms and especially branched chain, into consideration.

Although even with alkoxy groups higher members, i. H. Containing 4 and more carbon atoms as well Polyalkyleneoxy groups are possible, comes the alkoxy groups containing 1 to 4 carbon atoms the predominantly practical importance. Among the halogens mentioned, chlorine is particularly Interest. In principle, all esterification components are possible for the carboxylic ester groups, In practice, only alkyl esters with 1 to 18 carbon atoms and the benzyl ester are usually of interest. the Carboxamide groups can be either “free” or as mono- or di-substituted groups are present. Of predominant importance among the substituted representatives are the alkyl and aryl amides with up to 18 carbon atoms as well as cyclic amides (ζ. B. of the morpholide type). Under the The term "free acids" is of course also to be considered to include their salts. 45 ·

Those characterized in the foregoing to be used according to the invention for optical brightening processes In principle, connections can be made by various methods.

A particularly advantageous process for the preparation of compounds of the formula (1) consists in that one compounds of the formula

H CH ₃

H -

CH ₃ -

(7)

- H
-CH

Have meaning and the wording

- H
-CH ₃

means that either a hydrogen atom or a methyl group can be present at this point, at least however, a methyl group is present throughout the molecule in the presence of a strongly basic one Reacts alkali compound with a Schifischen base, the reaction medium being a strongly polar, neutral one until basic organic solvent is to be used that I) free of atoms - in particular Hydrogen atoms - which can be replaced by alkali metal, and II) should be practically anhydrous, and in the case of using alkali metal hydroxides as the strongly basic alkali compound, these Alkali hydroxides may have a water content of up to 25%.

As starting materials according to the above formula (7), for. B. can be used:

A. Compounds of Formula

55

R '"

where R '"is, for example, a monocyclic benzene radical and X is a hydrogen atom, a chlorine atom, a methoxy group or a methyl group.
B. Compounds of the formula

wherein X ₀ , X ₁ , X ₂ , X ₁ 'and X _{2 are} methyl groups or hydrogen atoms.
C. Compounds of the formulas

H -
H, C-J \ =

60

3

a a

wherein the symbols a, Z ₁ and Z ₂ are those given above

CH,

(10)

Η -

H ₃ C-,

Ar -CH = N-C (tertiary) - (13)

see bases of aromatic aldehydes with anilines, i.e. aromatic aldehyde-aniles. Such anile correspond for example the general formula

(14)

IO

Η -

H ₃ C- ^ =

In these above formulas, phenyl radicals can also contain further substituents from the series alkyl (especially with 1 to 4 carbon atoms), halogen (especially chlorine) or alkoxy (especially with 1 to 4 carbon atoms); furthermore, the indication -

H-1

35

also here that either a hydrogen atom or a methyl group, but at least in the entire molecule a methyl group.

The Schiff base to be used as the second reactant in this manufacturing process must - as goes without saying - be free of reactive methyl groups, z. B. those in p-position to the azomethine grouping. The Schiff bases in question represent the (well-known) Condensation products of aldehydes of aromatic character with primary amines (aliphatic, aromatic or heterocyclic nature), the amino group of which is bonded to a tertiary carbon atom, . Compounds of this type can accordingly be used as azomethine compounds of the formula

55

be written, where Ar is an aromatic radical. It can be either a both of the components required to build the Schiff bases (aldehyde and amine) still exist contain further substituents - subject to the above restriction. As the amine, in particular Aniline residue is split off during the reaction and ■ is no longer present in the end product, this is the case here Presence of substituents generally not indicated and uninteresting. But it can anyway Substituents that do not interfere or hinder the implementation, e.g. B. Chlorine atoms. Of preferred interest are ship

where k and 1 can be identical or different and are hydrogen atoms, chlorine atoms or methoxy groups and h is chlorine or, preferably, hydrogen. Adjacent k and 1 together can also form an - O - CH ₂ - O - group. Another important variant of aromatic anilene corresponds to the formula

20th

= CH— Ar '

(15)

where h (as above) represents a hydrogen atom or chlorine atom and Ar 'represents a naphthyl or diphenyl radical means. Mono-aldehydes suitable for the construction of these Schiff bases are, for example called: Aldehydes of the benzene series such as benzaldehyde or its halogenated, such as mono- and dichloro analogues, alkoxybenzaldehydes such as p-methoxy-benzaldehyde, alkylated benzaldehydes, provided they do not contain p-methyl groups, such as toluyl, Xylyl or cumoyl aldehydes, methylenedioxy-benzaldehyde (Piperonal), 4-dimethylaminobenzaldehyde, 4 - diethylamino - benzaldehyde, diphenyl - aldehyde; Naphthalene series aldehydes such as α- and / S-naphthaldehyde.

Suitable amines are, for example, the anilines, naphthylamines or, as aliphatic representatives, the called tertiary butylamine.

The compounds of general formula (7) become strong with the aldehydanils in the presence of a polar, neutral to alkaline organic solvent implemented, which is free of atoms, in particular Hydrogen atoms, which can be replaced by alkali metals. As such a solvent Dimethylformamide is preferred.

A strongly basic alkali compound is still required for the reaction. Strongly basic alkali compounds are to be understood as meaning those compounds of the alkali metals, including ammonium, which have a base strength of at least approximately that of lithium hydroxide. According to this, compounds of Li, Na, K, Rb, Cs or ammonium of the alcoholate, hydroxide, amide, hydride, sulfide or strongly basic ion exchanger type can be used. It is advantageous to use potassium compounds of the composition KOC ^ ₁ H _2n ,.! ■ (16),

wherein m is an integer from 1 to 6, such as. B. potassium hydroxide or potassium tertiary butoxide. In the case of alkali alcoholates, alkali amides (and hydrides), a practically anhydrous medium must be used, while with alkali hydroxides a water content of up to 25% (e.g. water of crystallization) is permitted. In the case of potassium hydroxide, a water content of up to about 10% has proven to be expedient. As examples of other usable alkali

R "'- C

CH = CH-R

R '"

+ 2AlCl ₃
70 to 130 ° C

anhydrous
(Π)

compounds are sodium methylate, rubidium hydroxide and cesium hydroxide. Of course it is also possible to work with mixtures of such bases.

The compounds of the general formula (7) are expediently reacted with the aldehydaniles in equivalent amounts, so that there is no substantial excess of any component. Of the alkali compound is used with advantage at least the equivalent amount, ie at least 1 mole of a compound with z. B. a KO group to 1 mole of aldehydanil. When using potassium hydroxide, 4 to 8 times the amount is preferably used. The reaction can generally be carried out at temperatures ranging between about 10 and 15O ⁰ C. If alcoholates are used as the potassium compound in the reaction, no heat supply is generally necessary. The procedure is, for example, that the aldehyde aniline is added to the mixture of the compound of the formula (1), the solvent and the potassium alcoholate, advantageously with stirring and with the exclusion of air, at a temperature between 15 and 30 ^° C., whereupon the reaction takes place without further ado with a slight increase in temperature. When using potassium hydroxide, it is often necessary to work at a higher temperature. For example, the reaction mixture increases slowly 30 to 100 ⁰ C. and then for some time eg. B. ^l / ₂ to 2 hours, held at this temperature door. the end products can be worked up by customary methods known per se from the reaction mixture.

Another process for the preparation of such triazinyl-stilbene compounds consists essentially in that in an anhydrous medium with the help of Friedel-Crafts catalysts, such as aluminum chloride - or better still aluminum chloride and thionyl chloride - in a molecular ratio of 1: 2 stilbene-4-carboxylic acid halides, in particular chlorides, optionally in the presence of inert non- to weakly polar organic solvents, such as. B. o-dichlorobenzene or tetrachlorethylene, at temperatures in the vicinity of the boiling point of the reaction mixture, ie about 70 to 130 ⁰ C, with corresponding aromatic nitriles R '"- C = N (R"' as defined above) is reacted (see. Reports , 89, 223 [1956]). It is advantageous to work with an excess of aromatic nitrile, which at the same time serves as a solvent. The intermediate products formed are, if necessary after previous isolation, at temperatures of about 30 to 130 ⁰ C with ammonium chloride (cf. J. Chem. Soc. [1941], pp. 278 to 282) or, more appropriately, with gaseous ammonia, treated. This reaction sequence can be z. B. for the preparation of compounds of formula (2) are shown schematically as follows:

R '"- C

CH = CH-R

30 to 130 ⁰ C

NH ₃

AlCIf

R "'- C

60

65

CH = CH-R

(2)

The optical brighteners of the composition described at the outset are in dissolved or finely divided form Have a more or less pronounced fluorescence. You can use optical brightening the most varied of high molecular weight or low molecular weight organic materials or organic Materials containing substances are used.

For this purpose, for example, without the following list being in any way restrictive on this should be expressed the following groups before organic materials, as far as an optical Lightening of the same comes into consideration, called:

I. Synthetic organic high molecular materials:

a) Polymerization products based on at least one polymerizable carbon-carbon double bond containing organic compounds, d. H. their homo- or copolymers and their aftertreatment products such as crosslinking, grafting or Degradation products, polymer blends, etc., for which examples may be mentioned: polymers based on (^ -unsaturated carboxylic acids, especially acrylic compounds (such as Acrylic esters, acrylic acids, acrylonitrile, acrylamides and their derivatives or their methacrylic analogs), of olefin hydrocarbons (such as ethylene, propylene, isobutylene, styrenes, dienes, like especially butadiene, isoprene, d. H. including rubbers and rubber-like polymers, also so-called ABS polymers), polymers based on vinyl and vinylidene compounds (such as vinyl esters, vinyl chloride, vinyl sulfonic acid, vinyl ether, vinyl alcohol, Vinylidene chloride, vinyl carbazole) of halogenated hydrocarbons (chloroprene, highly halogenated Ethylenes), of unsaturated aldehydes and ketones (e.g. acrolein etc.), of allyl compounds etc., graft polymerisation products (e.g. by grafting on vinyl monomers), Crosslinking products (for example by means of bifunctional or multifunctional crosslinkers such as divinylbenzene, multifunctional allyl compounds or bis-acrylic compounds or by partial Degradation (hydrolysis, depolymerization) or modification of reactive groups (e.g. esterification, -Etherification, halogenation, self-crosslinking) are available,

209 63S / .163

b) other polymerization products such as ζ. Β. through Ring opening available, e.g. B. polyamides of the polycaprolactam type, also formaldehyde polymers or polymers that are available both via polyaddition and polycondensation are, such as polyethers, polythioethers, polyacetals, thioplasts,

c) Polycondensation products or precondensates based on bifunctional or polyfunctional compounds with condensable groups, their homo- and mixed condensation products and products post-treatment, for which examples include: polyester, saturated (e.g. polyethylene terephthalate) or unsaturated (e.g. maleic acid-dialcohol polycondensates and their crosslinking products with polymerizable Vinyl monomers), unbranched and branched (also based on higher alcohols, such as Alkyd resins);

Polyamides (e.g. hexamethylenediamine adipate), maleinate resins, melamine resins, phenolic resins (novolaks)! Aniline resins, furan resins, carbamide resins or their precondensates and those built in a similar way Products, polycarbonates, silicone resins and others.

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

II. Semi-synthetic organic materials such as

z. B. cellulose esters or mixed esters (acetate, propionate), nitrocellulose, cellulose ether, regenerated cellulose (Viscose, copper ammonia cellulose) or their aftertreatment products, casein plastics.

III. Natural organic materials of animal or vegetable origin, for example Base of cellulose or proteins, such as wool, cotton, silk, raffia, jute, hemp, fur and hair, Leather, wood masses in finely divided form, natural resins (such as rosin, especially lacquer resins), furthermore Rubber, gutta-percha, balata, as well as their aftertreatment and Modification products (e.g. through hardening, crosslinking or grafting), degradation products (e.g. by hydrolysis, depolymerization), obtainable by modifying reactive groups Products (e.g. by acylation, halogenation, crosslinking, etc.). . .

The organic materials under consideration can be in the most varied of processing states (Raw materials, semi-finished products or finished products) and aggregate states are available. You can once in the form of the most varied of shaped structures, d. H. so z. B. predominantly three-dimensionally extended bodies, such as blocks, plates, profiles, pipes, injection moldings or the most varied Workpieces, chips or granulates, foams; predominantly two-dimensional Bodies such as films, foils, lacquers, tapes, coatings, impregnations and coatings or predominantly one-dimensional bodies, such as threads, fibers, flakes, bristles, wires. The said On the other hand, materials can also be in the most varied of homogeneous states in unshaped states and inhomogeneous forms of distribution and states of aggregation exist, e.g. B. as powder, solutions, Emulsions, dispersions, latices (examples: lacquer solutions, polymer dispersions), sols, gels, putties, Pastes, waxes, adhesives and fillers.

Fiber materials can be, for example, as endless threads, staple fibers, flakes, hanks, textile Threads, yarns, twisted threads, nonwovens, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as paper and cardboard or paper pulps.

The compounds to be used according to the invention are also of importance for the treatment of textile organic materials, in particular textile fabrics. If fibers, which can be present as staple fibers or continuous fibers, in the form of strands, woven fabrics, knitted fabrics, fleece ", flocked substrates or composites, are to be optically brightened according to the invention, this is advantageously done in an aqueous medium, in which the compounds in question are finely divided If necessary, dispersants can be added during the treatment, such as, for example, soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphen oils, cellulose, sulfite waste liquor or condensation products of optionally alkylated naphthalenesulfonic acids with formaldehyde It is advisable to work in a neutral, weakly alkaline or acidic bath It is also advantageous if the treatment is carried out at elevated temperatures of about 50 to 100 ^° C., for example at the boiling point of the bath or near it (about 90 ^° C.) For the finishing according to the invention, lo Solutions in organic solvents into consideration.

The optical brightening agents to be used according to the invention can also be added to the materials before or are added or incorporated during their deformation.

They can be used, for example, in the production of films, foils, tapes or moldings add to the molding compound or injection molding compound or dissolve in the spinning compound before spinning, disperse or otherwise ensure a homogeneous fine distribution. The optical brighteners can also the starting substances, reaction mixtures or intermediate products for the production of full or semi-synthetic organic materials are added, so also before or during the chemical Implementation, for example in the case of a polycondensation (including precondensates), in the case of a polymerization (including prepolymers) or a polyaddition.

The optical brighteners can of course also be used wherever organic Materials of the type indicated above combined with inorganic materials in some form (typical examples: detergents, white pigments in organic substances).

The optically brightening substances are characterized by particularly good heat resistance and lightfastness and migration resistance.

The amount of the optical brighteners to be used according to the invention, based on what is to be optically brightened Material can vary within wide limits. Even with very small amounts, in certain cases z. B. those of 0.001 percent by weight, a clear and durable effect can be achieved. It however, amounts of up to about 0.5 percent by weight and more can also be used. For the most practical concerns are preferably amounts between 0.01 and 0.2 percent by weight of Interest.

The compounds serving as lightening agents can also be used, for example, as follows:

12th

a) In mixtures with dyes or 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", antioxidants, light stabilizers, heat stabilizers, chemical bleaches or as an additive to bleach baths.

c) In a mixture with crosslinkers, finishing agents such as starch or synthetically accessible finishes. The products according to the invention can advantageously also be used to achieve a crease-resistant Equipment used in the fleet can be added.

d) In combination with detergents. The detergents and brightening agents can be the ones to be used Wash baths are added separately. It is also beneficial to use detergents, which contain the whitening agents mixed in. Soaps, for example, are suitable as detergents, Sulphonate detergent salts, such as B. of sulfonated on the 2-carbon atom by higher Alkyl radicals substituted benzimidazoles, also salts of monocarboxylic acid ester ^ of 4-sulfophthalic acid with higher fatty alcohols, also salts of fatty alcohol sulfonates, alkylarylsulfonic acids or condensation products of higher fatty acids with aliphatic oxy or aminosulfonic acids. Furthermore, non-ionic Detergents are used, e.g. B. polyglycol ethers, which differ from ethylene oxide and derive higher fatty alcohols, alkylphenols or fatty amines.

e) In combination with polymeric carrier materials (polymerization, polycondensation or polyaddition products) in which the brighteners are incorporated in dissolved or dispersed form, if appropriate, along with other substances, e.g. B. for coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles, fleece, paper, leather.

As additives to a wide variety of industrial products to make them more marketable or to avoid disadvantages in usability, e.g. B. as an additive to glues, adhesives, toothpastes, paints, etc.
If the lightening process is combined with other treatment or refinement methods, the combined treatment is advantageously carried out with the help of suitable permanent preparations. Such preparations are characterized in that they contain optically brightening compounds of the general formula given at the outset, as well as dispersants, detergents, carriers, dyes, pigments or finishing agents.

When treating a variety of fiber substrates, e.g. B. of polyester fibers, with the brighteners to be used according to the invention one proceeds appropriately such that'man these fibers with the aqueous dispersions of the whitening agent at temperatures below 75 ° C, for. B. impregnated at room temperature and subjected to a dry heat treatment at temperatures above 100 ⁰ C, whereby it is generally recommended that the fiber material beforehand at a moderately elevated temperature, for. B. at least 60 to about. 100 ° C to dry. 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 treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out immediately one after the other or combined in a single operation.

It is already known from French patent specification 1,345,260, triazine derivatives as optical brightening agents to use. These compounds differ from those to be used according to the invention Compounds not only because of their different chemical structure (triazine ring, containing a Pyrene or anthracene radical and two non-aromatic radicals), but also by a much smaller one Oscillator strength. The compounds to be used according to the invention are accordingly distinguished a much higher yield.

In the tables below:

Column I.
Column II
Column III
Column IV

Formula number.
Structural elements.
Crude yield in%.

Recrystallization medium, the same with those listed below Numbers are designated:

1 = water,

2 = ethanol,

3 = dioxane,

4 = dimethylformamide,

5 = tetrachlorethylene,

6 = chlorobenzene,

7 = o-dichlorobenzene,.

8 = trichlorobenzene,

9 = toluene,

10 = η-hexane,

11 = xylene. '.

Column V = color of the purified reaction product, the same with the following listed numbers was denoted:

1 = colorless,

2 = almost colorless,

3 = pale green,

4 = light green,

5 = pale yellow,

6 = light yellow,

7 = yellow, I.

8 = pale greenish yellow,

9 = light greenish yellow,
10 = greenish yellow.

Column VI = "Melting point (uncorrected) in ⁰ C.

Column VII = molecular formula and analysis data

(upper line calculated, lower line found).

Manufacturing regulations

A. 10.8 g of 2,4-diphenyl-6- [4'-methylphenyl (1 ')] - 1,3,5-triazine the formula

and 7.05 g of 4'-methoxybenzaniline are in 200 ml of anhydrous dimethylformamide with the exclusion of

Air stirred and. all at once with 11.2 g of potassium tertiary butylate offset. The color of the reaction mixture changes immediately from light beige to blue-violet around, and the temperature rises a few degrees C over the course of 2 minutes. One stirs one another hour without external heating, the temperature falling again somewhat. After that will be 400 ml of water are added dropwise at 10 to 15 ° C., the reaction mixture is suction filtered and neutralized with water

washed.

Now the moist suction filter is dissolved in 120 ml of dimethylformamide in the heat, with 25 ml 10% hydrochloric acid and after a few minutes with 120 ml of water and cooled to about 10 ° C.

After suction filtering, washing with water and methanol and subsequent drying, about 14.7 g, corresponding to 100% of theory, of 2,4-diphenyl-6- [4 "-methoxystilbenyl- (4 ')] - 1,3,5-triazine the formula

CH = CH-

OCH ₃

obtained in the form of a yellow powder with a melting point of 243.5 to 246.5 ° C. After chromatography in tetrachlorethylene on activated aluminum oxide and recrystallization from dioxane-ethanol Pale greenish yellow, matted needles with a melting point of 235.5 ° C were obtained.

Analysis: C ₃₀ H ₂₃ ON ₃ (441.51).

Calculated ... C 81.61, H 5.25, N 9.52;
found .... C 81.70, H 5.38, N 9.45.

B. 11.7 g of 2,4,6- [4'-methylphenyl- (1 ')] - 1,3,5-triazine the formula

H, C

"(20)

CH,

and 18.1 g of benzalaniline are dissolved in 350 ml of anhydrous dimethylformamide with the exclusion of air stirred and all at once with 28.0 g of potassium tertiary butoxide offset. The color of the reaction mixture immediately changes from pale yellow to purple, and the The temperature rises by about 10 ° C over the course of 5 minutes. The mixture is stirred for a further IV2 hours without external heating afterwards, whereby the temperature drops again. Then 350 ml of water at 10 to 20 ° C is added dropwise, the reaction product is suction filtered and washed neutral with water.

Now the moist suction filter is dissolved in 500 ml of dimethylformamide in the heat, with 50 ml of 10% strength Hydrochloric acid and then mixed with 500 ml of water. It is cooled to about 10 ° C, suction filtered, washed first with water, then with methanol and dry.

15 16

About 20.4 g, corresponding to "99.5% of theory", of 2,4,6-tri- [stilbenyl- (4 ')] - 1,3,5-triazine of the formula are obtained

CH = CH-

(21)

in the form of light yellow, very fine needles that melt at 251 to 254 ° C. After four recrystallization from tetrachlorethylene with the help of bleaching earth, light, greenish yellow needles are made from Melting point 275 to 277 ° C obtained.

Analysis: C ₄₅ H ₃₃ N ₃ (615.78).

Calculated ... C 87.77, H 5.40, N 6.82; found .... C 87.56, H 5.50, N 6.96.

If 21.1 g of 4'-methoxybenzalaniline are used instead of the 18.1 g of benzalaniline, about 22.7 g are obtained. corresponding to 96.6% of theory, 2,4,6-tri- [4 "-methoxy-stilbenyl- (4 ')] - 1,3,5-triazine of the formula

OCH,

(22)

■ OCH,

in the form of a yellow powder of melting point 263.5 to 265 ° C. After chromatography in o-dichlorobenzene of activated alumina and recrystallizing twice from tetrachlorethylene are obtained 300 ⁰ C yellow, very fine needles of melting point.

Analysis: C ₄₈ H ₃₉ O ₃ N ₃ (705.82). ■ Calculated ... C 81.68, H 5.57, N 5.95; found .... C 81.53, H 5.51, N 5.87.

C. 11.7 g of 2,4,6-tri- [4'-methylphenyl- (l ')] - 1,3,5-triazine of formula (20), 18.1 g of benzalaniline and 12.6 g Potassium hydroxide powder with a water content of about 10% is dissolved in 300 ml of dimethylformamide stirred in the absence of air, after a few minutes a dark blue color develops. Man if the temperature increases to 90 ° C. over the course of an hour, stirring is continued for 40 minutes at this temperature and then cools down to about 10 ° C. 100 ml of water and 150 ml of 10% strength are then added one after the other at 10 to 20 ° C Hydrochloric acid and a further 250 ml of water were added dropwise. The precipitated reaction product is suction filtered with Washed neutral with water and removed from a by-product by further washing with methanol

209 645/163

Friday. After drying, about 19.7 g, corresponding to 96.2% of theory, of 2,4,6-tri- [stilbenyl- (4 ')] - 1,3,5-triazine are obtained of formula (21) in the form of a yellow powder which melts at 262 to 267 ° C. After Chromatograph in tetrachlorethylene on activated aluminum oxide and then three times Recrystallization from tetrachlorethylene turns into light, greenish yellow matted needles with a melting point 293 to 293.5 ° C obtained.

Analysis: C ₄₅ H ₃₃ N ₃ (615.78).

Calculated ... C 87.77, H 5.40, N 6.82; found .... C 87.55, H 5.55, N 6.98.

If instead of the 18.1 g of benzalaniline, 25.73 g of diphenyl- (4) -aldehyde-anil are used and the reaction is carried out for 30 minutes at 60 ° C., 2,4,6-tri- [4 "-phenyl-stilbenyl- (4 ')] - 1,3,5-triazine is obtained the formula

CH = CH

Yield: 93.1% of theory. Greenish yellow crystals from o-dichlorobenzene. Melting point: 361 to 362 ° C.

Analysis: Q ₃ H ₄₅ N ₃ (844.67):

Calculated ... C 89.65, H 5.37, N 4.98; found .... C 89.74, H 5.28, N 5.10.

The following stilbenyl-1,3,5-triazine derivatives can be prepared in a similar manner:

The compound obtained from 2,4,6-tri- [4'-methylphenyl- (r)] - 1,3,5-triazine of the formula (20) and 4'-chlorobenzalaniline the formula

CH = CH

CH = CH-

Yield: 94.0% of theory.

Light yellow, very fine tetrachlorethylene needles.

Melting point: 315 to 317 ° C. ' Analysis: C ₄₅ H ₃₀ N ₃ Cl ₃ (719.12).

Calculated ... C 75.16, H 4.21, N 5.84; found .... C 75.17, H 4.22, N 6.00.

19 20

From 2,4-diphenyl-6- [4'-methylphenyl- (r)] -1, 3,5-triazine of the formula (18) and diphenyl- (4) -aldehyde-anil the Compound of formula

Yield: 98.5% of theory. Analysis: C ₃₅ H ₂₅ N ₃ (487.57).

Light yellow, very fine tetrachlorethylene needles. Calculated ... C 86.21, H 5.17, N 8.62;

Melting point: 284 to 285 ° C. . Found C 86.35, H 5.28, N 8.54.

From 2,4,6-tri- [2 ', 4'-dimethylphenyl- (l')] - 1,3,5-triazine of the formula

H, C

H, C

and diphenyl- (4) -aldehyde-anil the compound of the formula

H ₃ C *

H, C-

Yield: 100% of theory.

Yellow, very fine needles made of xylene.

Melting point: 162 to 162.5 ° C.

Analysis: C ₆₆ H ₅₁ N ₃ (886.16).

Calculated .... C 89.46, H 5.80, N 4.74;
found .... C 89.16, H 5.83, N 4.68.

22nd

D. 16.87 g of 2,4-di- [4'-methylphenyl- (1 ')] - 6-phenyl-1,3,5-triazine the formula

H, C

and 50 g of potassium hydroxide powder with a water content of about 10% are stirred in 400 ml of dimethylformamide with the exclusion of air, a purple color appearing after a few minutes. The temperature is brought in the course of 30 minutes at 60 ⁰ C, stirred for 30 minutes at this temperature and subsequently cooled to .Raumtemperatur. Now 50 ml of water and 500 ml of 10% hydrochloric acid are added dropwise one after the other. The precipitated reaction product is suction filtered, washed neutral with water and freed from a by-product by further washing with 300 ml of methanol. After drying, about .24.8 g, corresponding to 96.6% of theory, of 2,4-di- [stilbenyl- (4 ')] - 6-phenyl-1,3,5-triazine [melting point: 218 to 218.5 ° C], 18.1 g of benzalaniline 15 of the formula

-CH = CH

CH = CH-

(29)

as a light yellow powder. After chromatography in tetrachlorethylene on activated. Alumina and Recrystallization from tetrachlorethylene produces almost colorless crystals with a melting point of 241 to 241.5 ° C receive.

Analysis: C ₃₇ H ₂₇ N ₃ (513.61).

Calculated ... C 86.52, H 5.30, N 8.18; found .... 'C 86.46, H 5.03, N 7.99.

The 1,3,5-triazine derivatives of the formula shown in the table below can be prepared in a similar manner

B ₁ - CH = CH

getting produced.

CH = CH-B ₁

■ B ₂

III

IV

VI

VII

CH ₃

-C-CH ₃ CH ₃

97.0

94.3

94.9

9/10

230.5 to 231

240.5 to 241

351 to 352.5

C ₄₁ H ₃₅ N ₃

C 86.43, H 6.19, N 7.38, C 86.33, H 6.08, N 7.56

C ₄₃ H ₃₁ N ₃

C 87.58, H 5.30, N 7.13, C 87.44, H 5.55, N 7.13

C ₄₉ H ₃₅ N ₃

C 88.39, H 5.30, N 6.31, C 88.33, H 5.43, N 6.28

continuation

I. B ₁ II B ₂ III IV ν 325 VI. 328 VII. N 5.82
N 5.80 CH ₃ Q ₃ H ₄₃ N ₃ 33 -C-CH ₃
CH ₃ 98.0 3/2 10 359 until 360 C 88.18, H 6.00,
C 88.37, H 6.28, N 5.66
N 5.73 C ₅₅ H ₃₉ N ₃ 34 "Ο" 91.7 7th 2 until C 89.04, H 5.30,
C 88.08, H 5.51,

E. 6.42 g of 4- [4'-methyl-phenyl- (r)] - 2,6-diphenyl- In a similar way, 4- [4'-methyl-

pyridine of the formula "20 phenyl- (r)] - 2,6-diphenyl-pyridine of the formula (35)

from 4-phenyl-2,6-di- [4'-methyl-phenyl- (r)] - pyridine of the formula CH ₃

(35)

25th

30th

H, C

3.7 g benzalaniline and 10 g potassium hydroxide powder

With a water content of about 10%, 150 ml of dimethylformamide are stirred into 35 and from 2,4,6-tri- [4'-methyl-phenyl- (r)] -pyridine with the exclusion of air. The temperature is brought to 60 ° C. over the course of 30 minutes, a purple coloration occurring. The mixture is subsequently stirred at 60 to 65 ^° C. for 30 minutes and the reaction mixture is then cooled to room temperature. 150 ml of water and 150 ml of 10% hydrochloric acid are then added dropwise one after the other, with cooling. The precipitated reaction product is suction filtered, washed with plenty of cold water and 400 ml of methanol and dried. About 4.9 g, corresponding to 59.8% of theory, of 4- [stilbenyl- (4 ')] - 2,6-diphenylpyridine of the formula are obtained

the stilbenyl-pyridine derivatives listed in the table below the formula

= CH-

(36)

in the form of a pale yellow powder which melts ^{at 168 to 170 ° C.} Recrystallization three times from dioxane-ethanol, with the aid of activated charcoal, gives colorless, very fine crystals with a melting point of 177.5 to 178 ° C.

Analysis: C ₃₁ H ₂₃ N (409.50).

Calculated ... C 90.92, H 5.66, N 3.42; found .... C 90.98, H 5.84, N 3.35.

55

60

65

getting produced.

209 635/163

25th

I. V ₁ II
V ₂ - V ₃ III IV ν VI • 370 to 371 -C ₃₇ H ₂₇ N VII N
N 2.88
2.87 . 39 H -CH = CH H 84.5 4th 1 275 to 275.5 C 91.51,
C 91.27, I!) H 5.60,
H 5.46, Λ . Λ / 194.5 to 195 Q ₉ H ₂₉ N N
N 2.74
2.67 40 -CH = CH H -CH = CH 77.1 10/11 2 256 to 257 C 91.55,
C 91.56, 'Λ Λ H 5.71,
H 5.89, IN THE 347 to 350 C ₅₁ H ₃₇ N N
N 2.11
1.96 41 -CH = CH
ι H -CH = CH 86.6 4th 5 C 92.27,
C 92.11, Λ H 5.62,
H 5.80, T τ A. χ / ι ι * C ₄₇ H ₃₅ N N
N 2.28
2.24 42 -CH = CH -CH = CH -CH = CH 93.8 5 2 C 91.97,
C 92.06, Λ Λ ■ Λ H 5.75, ·
H 5.84, I Ij Λ / Λ / Q ₅ H ₄₇ N N
N 1.66
1.73 43 -CH = CH -CH = CH -CH = CH
ι 96.3 7/4 5 C 92.71,
C 92.73, A. A. H 5.63,
H 5.86, T τ I Il Λ A. A. Λ / ■ \ / KJ

F. 5.84 g of 2,4,6-tri- [4'-methyl-phenyl- (1 ')] -pyrimidine of the formula

H, C

9.1 g benzalaniline and 25 g potassium hydroxide powder with a water content of about 10% are in 300 ml

28

Dimethylformamide implemented according to the information in Example 30. About 9.9 g are obtained, corresponding to 79.5% of theory, 2,4,6-tri- [stilbenyl- (4 ')] - pyrimidine of the formula

CH = CH-

N CH

in the form of a light yellow powder. After three recrystallization from xylene, with the aid of Fuller's earth, about 4.1 g, corresponding to 33% of theory, will be light greenish yellow, very fine needles from Melting point 247 to 248 ° C.

Analysis: C ₄₆ H ₃₄ N ₂ (614.79).

Calculated ... C 89.87, H 5.57, N 4.56;
found .... C 89.89, H 5.63, N 4.68.

Similarly, from 2,4,6-tri- [4'-methylphenyl- (1 ')] - pyrimidine of the formula (44), those in the following Table listed stilbenyl-pyrimidine derivatives of the formula

W-HC = CH

getting produced.

CH = CH-W

I. II
W. III IV V 345.5 VI VII N 3.32
N 3.24 C ₆₄ H ₄₆ N ₂ 46 97.5 7/4 10 288 to 347.5 C 91.18, H 5.50,
C 91.16, H 5.62, N 3.66
N 3.46 281 C ₅₈ H ₄₀ N ₂ N 3.66
N 3.50. 47 <^> 97.4 5/11 7th to 288.5 C 91.07, H 5.27,
C 91.05, H 5.38, 48 100 7th 6th to 281.5 C 91.07, H 5.27,
C 90.86, H 5.30,

G. 12.1 g of stilbene carbonic acid chloride and 17.56 g p-Tolunitrile in 200 ml of dry o-dichlorobenzene stirred. 6.6 g of anhydrous aluminum chloride are added and the temperature is brought to the Reaction mixture after the exothermic reaction has subsided to 115 ° C. Now are still 5.3 g of ammonium chloride were added and the mixture was stirred at 115 ° C. for 20 hours. After cooling it will the reaction mixture discharged into a lot of cold water, washed neutral, with steam from Freed o-dichlorobenzene and an insoluble by-product by boiling with 1500 ml of dimethylformamide removed. The filtrate is diluted with 1000 ml of water, cooled to room temperature and suction filtered and dries. About 12.8 g, corresponding to 58.6% of theory, are obtained, 2,4 - di - [4 '- methylphenyl- (1')] - 6-stilbenyl- (4 ") - 1,3,5-triazine the formula

CH = CH-

(49)

30th

in the form of a pale yellow powder that melts at 233-234 ° C. After recrystallizing twice from dioxane water, with the help of activated carbon, colorless, very fine crystals of Melting point 245 to 246 ° C obtained.

Analysis: C ₃₁ H ₂₅ N ₃ (439.53).

Calculated ... C 84.71, H 5.73, N 9.56;
Found ... C 84.58, H 5.87, N 9.82.

Similarly, the stilbenyl-1,3,5-triazine derivative of the formula

(50)

example 1

Is padded at room temperature (about 2O ⁰ C) a polyester fabric with an aqueous dispersion containing, per liter, 2 g of one of the compounds of formulas (19), (21), (24), (25), (29), (30) to (34), (39), (41), (43), (45) and (46) to (48) and 1 g of an adduct of about 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol, and dries at about

100 ^° C. The dry material is then subjected to a heat treatment at 150 to 220 ^° C., which takes from 2 minutes to a few seconds, depending on the temperature. The material treated in this way has a significantly whiter appearance than the untreated material.

Example 2

100 parts of polyester granules made from terephthalic acid ethylene glycol polyester become intimately with 0.05 parts of one of the stilbene derivatives of the formulas (19), (21), (24), (25), (29), (30) to (34), (29), (41), (43), (45) and (46) to (48) mixed and melted at 285 ° C with stirring. After the spinning mass has been spun out through conventional spinnerets, it is strongly lightened Obtain polyester fibers.

You can use the above-mentioned compounds before or during the polycondensation to Add polyester to the starting materials.

Example 3

10,000 parts of a polyamide in chip form prepared in a known manner from hexamethylenediamine adipate are mixed with 30 parts of titanium dioxide (rutile modification) and 2 parts of the compound of the formulas (19), (21), (24), (25), (29), (30) to (34), (39), (41), (43), (45), (46) to (48) or (50) mixed in a roller jar for 12 hours. The chips treated in this way are ^{melted in a kettle heated to 300 to 310 °} C. with UI or diphenyl vapor, after the atmospheric oxygen has been displaced by superheated steam, and stirred for half an hour. The melt is then pressed out through a spinneret under a nitrogen pressure of 5 atmospheres and the filament spun and cooled in this way is wound onto a spinning bobbin. The resulting threads show an excellent lightening effect.

Claims (2)

Patent claims:
1. Use of connections I — Γ.ΤΤ = CH = CH OC ₂ H ₅ being represented. Yield: 54.1% of theory. Light yellow, finely crystalline powder from dimethylformamide-water. Melting point: 190 to 190.5 ⁰ C. Analysis: C ₃₂ H ₂₅ O ₂ N ₃ (483.54). Calculated ... C 79.48, H 5.21, N 8.69; - found ... C 79.54, H 5.50, N 8.56. 65 a a where a represents a hydrogen atom, a halogen atom, is a methyl group or the methoxy group, Z ₁ and / or Z _{2 are} a ring member = CH - or = N - and α is a hydrogen atom, a pheny radical or a radical in the series -CH = CH IO represents, where I) at least one radical α is different from hydrogen or phenyl and has the meaning of one of the other radicals given for α, and where II) phenyl or Naphthyl radicals also 1 to 3 alkyl groups, 1 to 2 halogen atoms, an alkoxy group, a carboxamide group may contain as optical brightening agents. 2. Use according to claim 1 of compounds of the general formula A ₇ -C CA ₅ A, where A _{6 is} a residue of the series * ^ -CH = CH CH = CH A ₇ denotes a phenyl, diphenylyl radical or a radical A _6.