DE2460824C3 - 6-Aryl-2,4-dioxo-hexahydro-s-triazine - Google Patents

Description

R ²

R ²

"V

-N

R ¹ - N

-N

wherein

-N
R ³

R ⁴
/ ^N H

(D

R ¹ -N

wherein

and R ^{3 are} identical or different and represent optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl groups, or an optionally substituted aryl group and

R ^{4 stands} for a mono- or polysubstituted aryl group, where at least one radical promoting electrophilic aromatic substitution must be present as a substituent.
2. Process for making the compounds

according to claim 1, characterized in that 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-triazinium salts of the general formula II

R ²

R ¹ -N

>, - N '

where ^lv

R ¹ , R ^{2 represents} chlorine or bromine and
and R ^{3 are} identical or different and represent optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl groups or optionally substituted aryl groups,

with an aromatic compound of the general formula R ⁴ - H, in which R ^{4 stands} for a mono- or polysubstituted aryl group, where at least one radical promoting electrophilic aromatic substitution must be present as a substituent.

3. Further processing of the compounds according to claim 1 by acidic or basic hydrolysis an aromatic aldehyde of the general formula

Ri-CHO

wherein R ^{4 has} the meaning given in claims 1 and 2.

The invention relates to new 6-aryl-2,4-dioxo-hexahydro-s-triazines which can be obtained by reacting 2,4-dioxo-tetrahydro-1,3,5-triazinium salts and which are aminals of certain aromatic aldehydes, as well as and R ^{3 are} identical or different and represent optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl groups, or represent optionally substituted aryl groups and

R ^{4 stands} for a mono- or polysubstituted aryl group, where at least one radical promoting electrophilic aromatic substitution must be present as a substituent.
Suitable alkyl groups are, for example, saturated aliphatic radicals with 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms. For example, the following residues may be mentioned:

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl; the methyl radical is particularly preferred.

The alkylene groups are single or multiple,

preferably monounsaturated aliphatic radicals

having 2 to 10 carbon atoms, preferably 2 to 5

χ (]]) carbon atoms in question. For example, are

the following remains are called:

Vinyl, allyl and the isomeric propenyl, butenyl and pentenyl radicals. The allyl radical is particularly preferred.

Cycloalkyl groups are those with 5 to 12 carbon atoms, preferably with 5 to 10 carbon atoms, particularly preferably with 5 or 6 carbon atoms in question, for example called:

the cyclopentyl, the cyclohexyl, the cycloheptyl, the cyclooctyl, the cyclononyl and the cyclododecyl radical:

the cyclopentyl and cyclohexyl radicals are particularly preferred.

The phenyl or naphthyl radicals are preferred as aryl groups.

Examples of substituents by which the alkyl, alkenyl, cycloalkyl or aryl groups of the radicals R ¹ , R ² and / or R ³ can be substituted are:

Halogens such as fluorine, chlorine, bromine or iodine, preferably fluorine and chlorine; a straight chain or branched one Alkane radical with 1 to 4 carbon atoms, which is optionally replaced by halogen one or more times is substituted, preferably the methyl, chlorofao methyl and trifluoromethyl resi; the nitrile group; possibly carboxyl groups esterified by lower alcohols, preferably with 1 to 4 carbon atoms, preferably the carboxymethyl or carboxyethyl ester group, hydroxy group, alkoxy group with one (, 5 straight-chain or branched alkane radical with 1 to 4 carbon atoms, preferably the methoxy or the ethoxy group or an optionally substituted aryl radical, preferably the phenyl radical.

Possible substituents by which the aryl group of the radical R ⁶ can be substituted are those mentioned above for the aryl groups of the radicals Ri, R ² and R ³ , as well as an optionally substituted amino group. Substituted amino groups that may be mentioned are the N-alkylamino group and N, N-dialkylamino group with a straight-chain or branched alkane radical with 1 to 4 carbon atoms, for example the N-methylamino group, the N-ethylamino group, the N, N-dimethylamino group and the Ν, Ν- Diethylamino group, as well as the acylamino group with 1 to 4 carbon atoms in the acyl radical The radicals favoring electrophilic aromatic substitution are particularly a straight-chain or branched alkane radical, the hydroxyl group, the alkoxy group and the optionally substituted amino group, preferably the hydroxyl and amino group.

Furthermore, a process for the preparation of the compounds according to the invention of the general Formula I found, which is characterized in that 2,4-dioxo-l, 2,3,4-tetrahydro-l, 3,5-triazinium salts of the general formula II

R ¹ -N

X 'stands for chlorine or bromine and

Ri, R2

and R ^{3 have} the meaning given for the general formula I.

with an aromatic compound of the general formula R ⁴ —H, in which R ^{4 has} the meaning given for the general formula I.

As 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-triazinium salts are for example:

1,3,5-trimethyl-, 1,5-diethyl-3-methyl-,

1, S-dicyclohexyl-S-methyl-,

1, S-dimethyl-S-isopropyl-,

1, S-diisopropyl-S-methyl-,

1, S-dibenzyl-S-methyl-,

1,5-dimethyl-3-phenyl-,

l, 5-di (3-trifluoromethyl-phenyl) -3-methyl-,

l-phenyl-S.S-dimethyl-,

l- (3-trifluoromethyl-phenyl) -3,5-dimethyl-,

l- (3-trifluoromethyl-4-chlorophenyl) -3,5-dimethyl-,

l, 5-di (carbomethoxymethyl) -3-methyl-,

l, 5-di (cyanomethyl) -3-methyl-,

l.S-dicyclopentyl-S-methyl-,

1, S-di-tert-butyl-S-methyl-,

l, 5-diallyl-3-methyl-,

1,5-di-n-butyl-3-methyl-,

l, 5-di-isobutyl-3-methyl-,

l, 5-di-n-propyl-3-methyl-,

l, 5-di (4-methoxybenzyl) -3-methyl-,
l, 5-di (carboethoxy-methy]) -3-methyl-,
1, S-distearyl-S-methyl-,

1,5-di-dodecyl-3-methyl-2,4-dioxo-1,2,3,4-tetrahydro-s-triazinium chloride or bromide.

Preference is given to the aforementioned compounds which are substituted in the 1-, 3- and 5-positions by alkane radicals with 1 to 4 carbon atoms are substituted, particularly preferred is IAS-trimethyl ^ -dioxo-IAS ^ -tetrahydro-s-triazinium bromide or chloride.

Aromatic compounds of the general formula R ⁴ —H are, for example, anilines or phenols, which are optionally substituted one or more times on the aromatic ring by lower alkyl radicals, by halogen or by another hydroxyl or amino group, as well as anilines or phenols, their amino or Hydroxy groups are substituted by lower alkyl or aryl radicals, mentioned, preferred

Aniline, N-methylaniline, N, N-dimethylaniline,
N-ethyl-aniline, Ν, Ν-diethylaniline,

N-acetylaniline, 2-chloroaniline, 2-methylaniline,
Phenol, methoxybenzene, ethoxybenzene,
3-aminophenol, 3-aminomethoxybenzene,
3-acetylaminophenol, 1,3-dihydroxybenzene,
1,2-dihydroxybenzene, 1,3-diaminobenzene,
Naphthol-1, naphthol-2, 1-naphthylamine.
3-aminophenol, 3-aminomethoxybenzene and 3-acetylaminopnenol are particularly preferred.

The reaction according to the process according to the invention takes place depending on the reactivity of the reactants, in particular the aromatic compound, generally at temperatures from ⁰ ° C. to 100 ^° C. The reaction according to the process according to the invention can in principle be carried out with and without a solvent. However, it has proven to be advantageous to carry out the reaction in a solvent. Examples of solvents that may be mentioned are: water, lower aliphatic alcohols such as. B. methanol, ethanol, n- and iso-propanol, nitriles such. B. ■ Ό acetonitrile, propionitrile or benzonitrile, ethers such. B. diethyl ether, tetrahydrofuran and dioxane and pyridine and formamides such. B. formamide, N-methylformamide and dimethylformamide.

In the reaction according to the process according to the invention, hydrogen halide is released, which expediently by adding stoichiometric amounts of a base, such as. B. triethylamine, sodium hydroxide, Sodium carbonate, sodium bicarbonate, is neutralized. The function of the base can of course also optionally by suitable substituents of the aromatic compound, such as. B. Amino groups be taken over, forming the hydrohalide in question.

The inventive method for the preparation of aldehyde derivatives can, for. B. for the implementations of 2,4-dioxo-tetrahydro-1,315-trimethyl-triazinium bromide with a-naphthol or aniline can be explained in more detail by the following reaction schemes:

CH ₃

OH + NaOH

CH ₃

CH ₃ N

CH,

CHj

OH + NaBr

CH ₃ N

CH ₃

-N

CH ₃

Br "+

NH, CH ₃ N

NH, - HBr

The practical implementation of the method according to the invention can, for. B. take place as follows:

The 2,4-dioxo-tetrahydro-1,3,5-triazinium salt is dissolved or suspended in a solvent and gives the aromatic compound and optionally the base added. The reaction time and the reaction temperature depends on the reactivity of the aromatic ' see connection dependent. The aminal thus formed is in the usual way by filtration, precipitation or isolated by evaporating the reaction solution. Are aromatic amines in the reaction used, then the product obtained is the corresponding amine hydrohalides. You can be known in Way, e.g. B. be converted into the free compounds by treatment with sodium bicarbonate.

As aminals which are obtained by the process according to the invention, there may be mentioned, for example:

6- (4-hydroxyphenyl) -,

6- (4-methoxyphenyl) -, 6- (4-aminophenyl) -,

6- (4-methylaminophenyl) -,

6- (4-ethylaminophenyl) -,

6- (4-dimethylaminophenyl) -,

6- (4-diethylaminophenyl) -, 6- (4-acetylaminopheny]) -,

6- (4-Ammo-2-chlorophenyl) -,

6- (4-Amino-2-methy] phenyl) -,

6- (4-amino-2-hydroxyphenyl) -, 6- (4-Amino-2-methoxyphenyl) -, 6- (4-Acetylamino-2-hydroxyphenyl) -, 6- (4-hydroxy-naphthyl) - and

6- (2-hydroxy-naphthyl) -1,3,5-trimethyl-2,4-dioxohexahydro-s-triazine,

furthermore 6- (4-aminophenyl) -,

6- (4-Amino-2-chlorophenyI) - and

6- (4-Amino-2-hydroxyphenyl) -l-methyl-3,5-diethyl-2,4-dioxo-hexahydro-s-triazine,

furthermore 6- (4-methylaminophenyl) -, 6- (4-diethylaminophenyl) - and

6- (4-Amino-2-methoxyphenyl) -1 -methyl-3,5-dicyclohexyl-2,4-dioxo-hexahydro-s-triazine and

furthermore 6- (4-ethylaminophenyl) -, 6- (4-amino-2-hydroxyphenyl) - and

e - ^ - Acetaminophenylj-l-isopropyl-S.S-dimethyl-2,4-dioxo-hexahydro-s-triazine.

The 2,4-dioxotetrahydro-1,3,5-triazinium salts used as starting product for the process according to the invention of the general formula II can be obtained by adding 2,4-dioxohexahydro-1,3,5-triazines of the general formula III

R ¹ -N

(111)

wherein Ri, R ² and R ^{3 have} the aforementioned meaning, halogenated.

For the halogenation, elemental halogen, in particular Find chlorine or bromine use. Of course, connections can also be made among the Reaction conditions split off chlorine or bromine, are used. Such compounds are in particular Sulfuryl chloride, sodium hypochlorite or sodium hypobromide, tert. Butyl hypochlorite, N-bromosuccinimide or sodium dichlorocyanuric acid.

The implementation for the production of the starting products takes place in general. Jinen at temperatures of 0 to 100 ⁰ C, preferably at 20 to 50 C. °

The 2,4-dioxo-hexahydro-l, 3,5-triazines of the general formula III can be prepared by reacting the 1-, 3- and 5-position appropriately substituted biurets with aldehydes in the presence of acidic catalysts getting produced.

so as 2,4-dioxotetrahydro-l, 3,5-triazine, which is preferred are used for halogenation, for example:

1,3,5-trimethyl-, 1,5-diethyl-3-methyl-, lS-dicyclohexyl-S-methyl-,
!, S-dimethyl-S-isopropyl-,

1, S-diisopropyl-S-methyl-,

1, S-dibenzyl-S-methyl-,

l, 5-dimethyl-3-phenyl-,

l, 5-di (3-trifluoromethyl-phenyl) -3-methyl-, l-phenyl-S.S-dimethyl-,

l- (3-trifluoromethyl-phenyl) -3,5-dimethyi-,! - (S-trifluoromethyM-chlorophenylJ-S.S-dimethyl-, l.S-DifcarbomethoxymethyO-S-methyl-, 1,5- di (cyanomethyl) -3-methyl-, l.S-dicyclopentyl-S-methyl-,

1, S-di-terL-butyl-a-methyl-,

!, S-Di-n-butyr-S-methyl-,

ί Ί,

1, S-di-isobutyl-S-methyl-,
1, S-di-n-propyl-S-methyl-,
l, 5-di (4-methoxybenzyl) -3-methyl-, l, 5-di (carboethoxy-methyl) -3-methyl-, lS-distearyl-S-methyl-,
!, S-Di-dodecylO-methyl ^^ - dioxo-hexahydros-triazine.

The production of the 2,4-dioxo-1,3,4-tetrahydro-1,3,5-triazinium salts used as starting material can be based on the implementation of 2,4-dioxo-hexahydro-1,3,5-trimethyl-triazine with bromine to form 2,4-dioxo-1,2,3,4-th trahydro-1,3,5-trimethyl-triazinium bromide can be explained in more detail by the following reaction scheme:

CH ₃ N

CH,

-N '

+ Br,

CH ₃ N

The procedure here is to dissolve or suspend the 2,4-dioxohexahydro-1,3,5-triazine in an inert solvent and slowly add the halogenating agent. The reaction can be carried out at temperatures of 0 ⁰ C to 100 ° C, preferably from 20 ° C to 50 ° C are performed. An excessive increase in the reaction temperature can be prevented by cooling. The reaction is generally over after 1 to 5 hours. The 2,4-dioxole, 2,3,4-tetrahydro-1,3,5-triazinium salt is then isolated in the customary manner by filtration, precipitation by adding a non-polar solvent in which the salts are insoluble, or by evaporating the reaction solution . The reaction products can sometimes contain elemental halogen more or less firmly bound. By digesting or recrystallizing z. B. from alcohols such as isopropanol then the halogen-free

R ¹ -N

subjected to acidic or basic hydrolysis. The aromatic aldehyde formed has the general formula R ⁴ —CHO, where R ^{4 of} course corresponds to R ^{4 of} the aminal used

The acid hydrolysis is generally carried out by reaction with concentrated mineral acid at increased Temperature. In general, this hydrolysis takes place at about 60 to 100 ° C. The mineral acids are for example 80-100% sulfuric or phosphoric acid, as well as concentrated hydrochloric acid

For hydrolysis, the acid is expediently used in excess of the aminal, for example about 5 to 20 mol _; based on the aminal used, where H Br "+ HBr

get ties. Of course, the salts obtainable by the process according to the invention, which have chloride or bromide as anions in a manner known per se by reaction with NaI, KF, Na2SÜ4, tetrafluoroboric acid, KCIO3 or sodium acetate converted into the corresponding iodides, fluorides, sulfates, tetrafluoroborates, chlorates or acetates will.

The compounds according to the invention, which are aminals, can be alkaline or acidic Saponification can be converted into the corresponding aldehydes. Thus, by the method according to the invention enables a new important route for the synthesis of aromatic aldehydes, which is characterized by this is that one obtainable by the process according to the invention aminals of the general Formula I.

the acid at the same time the function of a solvent accepts In general, depending on the temperature door a reaction time of about 5-10 hours for complete hydrolysis required, in addition to the desired aromatic aldehyde continue carbon dioxide and primary amines having the respective substituents R ^1, R ² or R ³ arise. The hydrolysis products can be worked up in a manner known per se. The hydrolysis by means of a concentrated mineral acid, for example for 2,4-dioxohexahydro-1,3,5-trimethyl-6- (4-aminophenyl) -s-triazine as starting material, is explained in more detail by the following reaction scheme:

CH ₃ -N

o + 3HCl + 3H ₂ O

NH, + 2CO ₂ + 3CH ₃ NH ₂ - HCl

CH ₃

The alkaline hydrolysis is generally carried out using water or water

used by reaction with alkali hydroxides or alkali alcohols

alcoholates at elevated temperature. In general, for hydrolysis, the alkali metal hydroxide or the

the hydrolysis takes place at 80 to 150 ° C. As a solution alcoholate, optionally in an excess of 1 to 10

030 235/252

Mol based on the aminal used. In general, depending on the temperature, a reaction time of 2 to 10 hours is required for complete hydrolysis, in which case, in addition to the desired aromatic aldehyde, alkali metal carbonate and primary amines with the relevant substituents R ¹ , R ² or

CH ₁ -N

CH ₃

-N

-N

CH,

/ V

NH ₂ + 4NaOH + H ₂ O

OCH ₃

CH ₃ N

NH,

CH ₃

23.5 g (0.1 mol) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazolum bromide together with 9.3 g

R ³ arise. The hydrolysis products can be worked up in a manner known per se. The hydrolysis by means of alkali hydroxide is explained in more detail for 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (2-methoxy-4-aminophenyl) -s-triazine, for example, by the following reaction scheme:

O
H

NH ₂ + 3CH ₃ NH ₂ + 2Na ₂ CO ₃

OCH ₃

According to the process according to the invention, aromatic aldehydes, which have hitherto only been very difficult were accessible, such as B. 4-Amino-salicylaldehyde (A.A. Goldberg and R.S. Theobald Soc. 1954, 2641). This aldehyde is according to DE-PS 12 96 121 an important intermediate for the production of 3-heterocyclocumarin derivatives, the optical Represent brighteners.

A major advantage of this synthetic route for aromatic aldehydes is that, in contrast to the prior art, it is possible to introduce the aldehyde group in a direct reaction into aromatics which have a free amino group as a further substituent. For example, with the help of this synthetic route 4-acetylaminosalicylaldehyde can be obtained in a simple manner and with significantly improved yields than according to the prior art (cf. AA Goldberg et al. Soc. (London) 1954, 2461). 4-Acetylaminosalicylaldehyde is a known starting component for the 3- (1,2,3-triazol-l-yl) -7-amino-coumarin, which is known as an optical brightener and which can be synthesized from 4-acetylaminosalicylaldehyde in a manner known per se, by methylating this compound on the free hydroxyl group by reaction with dimethyl sulfate and heating the methoxy derivative obtained with 1,2,3-triazolyl-l-acetonitrile in ethanol as a solvent in the presence of catalytic amounts of pyridine and the methine compound obtained by heating in a suspension converted from anhydrous AlCl ₃ in benzene into the desired coumarin derivative. Analogously, by means of the triazinium salts according to the invention, analogous coumarin derivatives known as optical brighteners (cf. DE-PS 12 96 121) can also be synthesized via the easily accessible substituted benzaldehydes or naphthaldehydes. The aminals according to the invention are thus to be regarded as a valuable starting material for the synthesis of these coumarin derivatives.

example 1

2,4-Dioxo-hexyhydro-1,3,5-trimethyl-6 (4-aminophenyl) -s-triazine

(0.1 mol) of aniline in 50 ml of acetonitrile and heated to boiling. After 2 hours you suck the precipitated yellow precipitate. It is dissolved in water and neutralized with a soda solution. Divorce it 19 g (77%) 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (4-aminophenyl) -s-triazine with a melting point of 165 ° to 167 ° C.

Analysis for C ₁₂ H ₁₆ N ₄ O ₂ (248):
Calculated: C 58.1, H 6.4, N 26.6; Found: C 58.3, H 6.1, N 26.5.

Example 2

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (4-dimethylaminophenyl) -s-triazine

CH ₃

CH ₃ N

23.6 g (0.1 mole) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are together with 12.1g (0.1 mol) of dimethylaniline in 50 ml of acetonitrile suspended and stirred at room temperature. A clear solution results, from which after 3 hours a white precipitate precipitates. It is dissolved in water and neutralized with soda solution. 23 g are divorced (83%) 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (4-di-

methylaminopheny]) - s-triazine with a melting point of lirC-113 ° Cab.

Analysis for C ₁₄ H ₂₀ N ₄ O ₂ (276):

Calculated: C 60.8. H 7.7. N 20.3: Found: C 60.6, H 6.9, N 20.3.

Example 3

2,4-Dioxo-hexyhydro-1,3,5-trimethyl-6 (4-diethylaminophenyl) -s-triazine

CH ₃

60 C ₂ H ₅

CH ₃ N

65

23.6 g (0.1 mole) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide will be together with

14.9 g (0.1 mol) of diethylaniline in 50 ml of acetonitrile were stirred. A clear solution results from which a new precipitate separates out after a few hours. It will sucked off and dissolved in water. After neutralization with sodium hydroxide, 24 g (79%) 2,4-di-

oxo-hexahydrO "1,3,5-trimethyl-6 (4-diethylaminophenyl) -s-triazine as white crystals melting at 127-129 ° C.

Analysis for Ci ₆ H ₂₄ N ₄ O ₂ (304):
Calculated: C 63.2, H 7.9, N 18.4;
Found: C 63.1, H 7.6, N 18.5.

Example 4

2,4-Dioxo-hexyhydro-1,3,5-trimethyl-6- (4-N * methylaminophenyl) -s-triazine

CH ₃ -N

NHCH ₃

23.6 g (0.1 mole) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are stirred together with 10.7 g (0.1 mol) of N-methylaniline in 50 ml of acetonitrile. A clear solution results from which a new precipitate separates out after 3 hours. He is sucked off and dissolved in water. When neutralizing with soda solution, 21 g (80%) of 2,4-dioxohexahydro-1,3,5-trimethyl-6 (4-diethylaminophenyl) -s-triazine separate as white crystals melting at 78-80 ° C.

Analysis for Ci ₃ Hi ₈ N ₄ O ₂ (262):

Calculated: C 59.5, H 6.9, N 21.4;
found: C 59.8, H 6.4, N 21.3.

Example 5

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-aminophenyl) -s-triazine

CH ₃ N

NH,

CH ₃

Example 6-

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (3-methyl-4-aminophenyl) -s-triazine

CH ₃ N

CH ₁

CH ₃

CH ₃

23.6 g (0.1 mole) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are together with 10.7 g (0.1 Mo!) o-To! uiden in 50 ml acetonitrile for 5 hours heated to boiling. It is then cooled and the precipitate which has separated out is filtered off with suction. He is in Dissolved water and the aqueous solution is made alkaline (pH 8) with sodium hydroxide solution. Thereby divorce 21 g (80%) 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (3-methyl-4-aminophenyl) -s-triazine as white crystals melting at 151 ° -153 ° C.

Analysis for Ci ₃ Hi ₈ N ₄ O ₂ (262):
Calculated: C 59.5, H 6.9, N 21.4;
found: C 59.3, H 6.9, N 21.2.

Example 7

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (3-chloro-4-aminophenyl) -s-triazine

CH ₃

23.6 g (0.1 mol) of 2,4-dioxo-l, 2,3,4-tetrahydro-l, 3,5-trimethyl-s-triazinium bromide are dissolved in 50 ml of water and mixed with 10.9 g ( 0.1 mol) of m-aminophenol added. After less. A clear solution has emerged in minutes. 8 g of sodium bicarbonate are added to it. 25 g (89%) of ^ -Dioxo-hexahydro-US-trimethyl-6 (2-hydroxy-4-aminophenyl) -s-triazine precipitate as white crystals which, after dissolving in aqueous hydrochloric acid, clear with active -Melt coal and neutralize at 240 ^° C.

Analysis for C ₂ H ₁₆ N ₄ O ₃ · H ₂ O (282):
Calculated: C 51.1, H 6.3, N 19.9;
Found: C 51.1, H 6.2, N 20.1.

CH ₃ -N

Cl

23.6 g (0.1 mol) of 2,4-dioxo-l, 2,3,4-tetrahydro-l, 3,5-trimethyl-s-triazinium bromide are added together with 11.8 g (0.1 mol) stirred for 2 hours at 7O ⁰ C 2-chloroaniline in 30 ml of dimethylformamide. It is then cooled and the precipitated white product is filtered off with suction. It is dissolved in water and the aqueous solution is neutralized with sodium hydroxide. An oil separates out, which solidifies after a few minutes. After suctioning off, 14 g (50%) of 2,4-dioxohexahydrol, 3,5-trimethyl-6 (3-chloro-4-aminophenyl) -s-triazine are obtained as white crystals, which after dissolving from isopropanol at 180 ° - Melting 182 ° C.

Analysis for Ci ₂ Hi ₅ ClN ₄ O ₂ (282.5):
Calculated: C 51.0, H 5.3, N 19.8;
found: C 51.0, H 5.5, N 19.9.

Example 8

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-methoxy-4-aminophenyl) -s-triazine

O CH ₃

CH ₃ N

CH ₃

/ V-NH ₂
OCH ₃

23.6 g (0.1 mol) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are combined with 12.4 g (0.1 mol) of 3 -Amino-1-methoxybenzene stirred in 260 ml of acetonitrile for 6 hours. The precipitate which has separated out is then filtered off with suction and dissolved in water. When the aqueous solution is neutralized with potassium hydroxide solution, 24 g (87%) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (2-methoxy-4-aminophenyl) -s-triazine separate as white crystals from which melt at 203 ° -205 ⁰ C.

Analysis for C ₁₃ Hi ₈ N ₄ O ₃ (278):
Calculated: C 56.1, H 6.5, N 20.1;
Found: C 56.2, H 6.3, N 20.1.

Example 9

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-N-acetylaminophenyl) -s-triazine

CH ₁ N

CH ₃

: —N

CH ₃

—CO-CH ₃

OH

Example 10

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (4-hydroxy-naphthyi) -s-triazine

CH ₃ N

OH

the melt after recrystallising from methanol at 209 ° -211 ⁰ C.

Analysis for Ci ₆ Hi ₇ N ₃ O ₃ (299):

Calculated: C 64.5, H 5.7, N 14.1; Found: C 64.6, H 5.5, N 14.2.

Example 11

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-naphthyl) -s-triazine

HO

CH ₃ N

12 g (0.08 mol) m-acetylaminophenol, 18.8 g (0.8 mol) 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are then stirred together with 8 g (0.08 mol) of triethylamine in 50 ml of acetonitrile for 9 hours the precipitate is filtered off with suction and to remove the triethylaminohydrobromide stirred in water. What remains is 16 g

(65%) 2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-N-acetyl-aminophenyl) -s-triazine as white crystals which do not melt ^{up to 250 ° C.}

Analysis for C ₁₄ Hi ₈ N ₄ O ₄ (306):
Calculated: C 54.9, H 5.9, N 18.3;
Found: C 55.1, H 5.7, N 18.2.

20 23.6 g (0.1 mol) of 2,4-dioxo-l, 2,3,4-tetrahydro-l, 2,3-trimethyl-s-triazinium bromide are added together with 14.4 g (0.1 mol ) Naphthoi- (2) and 10 g (0.1 mol) of triethylamine stirred in 70 ml of acetonitrile for 4 hours. The precipitate formed is filtered off with suction and extracted with water Melt dissolving from methanol at 228 ° to 230 ° C.

Analysis for C ₆ H ₁₇ N ₃ O ₃ :

Calculated: C 64.5, H 5.7, N 14.1; Found: C 64.7, H 5.6, N 14.1.

Example 12

1,3-diamino-4,6-bis (2,4-dioxo-hexahydrol, 3,5-trimethyl-s-triazinyl-6) benzene

45

50

55 Η, Ν

H ₂ N

CH ₃ O CH ₃

60

23.6 g (0.1 mol) of 2,4-dioxo-l, 23,4-tetrahydro-l, 3,5-trimethyl-s-triazinium bromide are used together with 14.4 g (0.1 mol) of naphthol (l) and 10g (O ₁ I mol) of triethylamine were stirred in 80 ml of acetonitrile for 4 hours. The white precipitate is then freed from triethylamine hydrobromide by washing with water and 21 g (70%) of ^ -dioxohexahydro-l ^ .S-trimethyl-6 (4-hydro-naphthyl) -s-triazine are obtained as white crystals, 23, 6g (0.1 mol) 2,4-dioxo-1,3,4-tetrahydro-1,3,5- ^! trimethyl-s-triaziniuiribromide are mixed with 5.4 g (0.05 mol) of m-phenylenediamine in 50 ml of dimethylformamide. A white precipitate is immediately deposited. It is filtered off with suction and stirred in aqueous soda solution. 34 g (81%) of l ^ -diamlrio ^ ebis (2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazinyl-6) benzene are obtained as white crystals that melt above 250 ^{° C.}

Analysis for Ci ₈ H ₂₆ N ₈ O ₄ (1418):
Calculated: C 51.7, H 6.2, N 26.8; Found: C 51.3, H 53, N 26.4.

Example 13

2,4-bis (2,4-dioxo-hixahydro-1,3,5-trimethyls-triazinyl-6) phenol

CH ₃

CH ₃ -N ^ N-CH ₃

23.6 g (0.1 mol) of 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are dissolved in 50 ml of dimethylformamide with 10 g (0.1 mol ) Triethylamine and 5.7 g (0.05 mol) of phenol were stirred at 70 ° C. for 9 hours. The precipitate formed is then filtered off with suction and washed out with water. What remains is 11 g (54%) 2,4-bis (2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazinyl-6) -phenol as white crystals which melt ^{above 250 ° C.}

Analysis for C ₁₈ H ₂₄ N ₆ O ₅ (404):
Calculated: C 53.5, H 5.9, N 20.8; Found: C 53.4, H 5.9, N 20.8.

Example 14

2,4-Dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-aminophenyl) -s-triazine

To a solution of 19.1 g (0.1 mol) of 2,4-dioxol ^ ß ^ -tetrahydro-IAS-trimethyl-s-triazine chloride 10.9 g (0.1 mol) of m-aminophenol are added to ml of water and stir for a few minutes until a clear solution has formed. Then 8 g of sodium bicarbonate are added. It precipitate 24 g (85%) of the same compound as in the example.

Example 15 to 18

The following compounds according to the invention were prepared analogously to Example 1:

15. 2,4-Dioxo-1,2,3,4-tetrahydro-1, 5-diethyl-3-methyls-triazinium bromide and 2-ethyl-6-methyl-aniline give 2,4-dioxo-hexahydro-1, 5-diethyl-3-methyl-6 (3-ethyl-4-amino-5-methyl-phenyl) -s-triazine, melting point: 133 to 135 ^° C. in 76% of the theoretical yield.

16. 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-diisopropyl-3-methyl-s-triazinium bromide and 2,6-dimethyl-aniline give 2,4-dioxo-hexahydro-1, 5-diisopropyl-3-methyl-6 (3,5-dimethyl-4-aminophenyl) -s-triazine, melting point: 156 to 157 ^° C. in 68% of the theoretical yield.

17. 2,4-Dioxo-l, 2,3,4-tetrahydro-1,5-dicyclohexyl-3-methyl-s-triazinium bromide and meta-aminophenol give 2,4-dioxo-hexahydro-1,5-dicyclohexyl- 3-methyl-6 (2-hydroxy-4-amino-phenyl) -s-triazine, melting point above 28O ⁰ C in 89% of the theoretical yield.

18. 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-dimethyl-3-phenyl-s-triazinium bromide and meta-aminophenol give 2,4-dioxo-hexahydro-1,5-dimethyl-3-phenyl-6 (2-hydroxy-4-aminophenyl) -s-triazine, Melting point above 280 ° C. in 93% of the theoretical yield.

Example 19

Further processing of the invention
links

a) 4-aminosalicylaldehyde

113 g (0.4MoI) 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-aminophenyl) -s-triazine are dissolved in a solution of 120 g of potassium hydroxide in 640 ml of n- Butanol stirred at 100 ^° C. for 3 hours. It is then cooled and suctioned off. 67 g (96%) of 4-aminosalicylaldehyde are obtained as the potassium salt. By simply stirring this salt in 150 ml of acetic anhydride at room temperature and subsequent boiling in water, 4-acetylaminosalicylaldehyde has a melting point of 186 ° C. (AA Goldberg and RS Theobald, Soc. 1954, 2641).

b) 4-aminobenzaldehyde

24.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (4-aminophenyl) -s-triazine are dissolved in 100 ml of 37%: ger aqueous hydrochloric acid for 5 hours 100 ⁰ C heated. It is then evaporated to dryness and the residue that remains is taken up in water. The aqueous solution is brought to pH 8 with sodium hydroxide solution and extracted three times with 100 ml of ether each time. After evaporation of the ether, 4-aminobenzaldehyde is obtained with a melting point of 71 ° C.

c) 4-dimethylaminobenzaldehyde

27.5 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (4-dimethylaminophenyl) -s-triazine are heated in 50 ml of 96% sulfuric acid at 80 ° C for 6 hours. The solution is then poured onto ice and made alkaline with sodium hydroxide solution (pH 8 to 9). It separates 4-dimethylaminobenzaldehyde has a melting point of 74 ° C.

d) 4-monomethylaminobenzaldehyde

26.1 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (4-methylaminophenyl) -s-triazine are stirred with 16 g (0.4 mol) of sodium hydroxide in 50 ml of water at 95 ° C. for 8 hours. The cooled solution is used three times extracted with 100 ml of methylene chloride each time. After evaporation of the methylene chloride solution remains 4-methylamino-benzaldehyde with a melting point of 58 ° C.

e) 2-hydroxy-naphthaldehyde

29.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (2-hydroxynaphthyl) -s-triazine are mixed with 20 g (0.5 mol) of sodium hydroxide Stirred in 50 ml of water at 95 ^° C. for 8 hours. The solution is then acidified and 2-hydroxynaphthaldehyde with a melting point of 82 ^° C. is obtained.

Production of starting compounds:

A) Triazinium compounds according to more general
Formula II

a) 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide, which is used as the starting material for Examples 1 to 14 is as is obtained as follows:

15.7 g (0.1 mol) of 2,4-D'ioxo-hexahydro-1,3 ₎ 5-trimethyl-s-triazine are dissolved in 30 ml of methylene chloride and added dropwise with 24 g (0.15 mol) of bromine

030 235/252

In this case, offset by cooling keeping the temperature between 20 ⁰ C and 30 ⁰ C. After a few minutes the addition of bromine to the product separates 2,4-dioxo-1,2,3,4-tetrahydro-l, 3,5- trimetlri-s-triazinium brornide in the form of orange crystals. They are filtered off with suction and recrystallized from isopropanol. 20 g (85%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are obtained as white crystals which at 217 ° Melt C.

Analysis for C ₆ H ₁₀ BrN ₂ O ₂ (236):

Calculated:
found:

C 30.6, H 4.2, N 17.8;
C 30.9, H 4.4, N 17.8.

10

15th

The following triazinium salts can also be used as starting material in an analogous manner will.

Calculated:
found:

C 36.4, H 5.3, N 15.9;
C 36.3, H 5.3, N 15.5.

e) 2,4-Dioxo-l, 2,3,4-tetrahydro-l, 5-diisopropyl-3-methyl-s-triazinium bromide:

21.3 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-diisopropyl-3-methyl-s-triazine are dissolved in 30 ml of methylene chloride, and 24 g (0.15 mol) of bromine are added dropwise cooling maintaining the temperature at 20 ^c C to 30 ⁰ C. After one hour, the orange precipitate formed is filtered off with suction and recrystallized from isopropanol to give 16 g (55%) of 2,4-dioxo-l, 2,3,4-tetrahydro -l, 5-diiso ■ propyl-3-methyl-s-triazinium bromide as white crystals which melt at 210-212 ° C.

Analysis for C ₁₀ H ₁₈ BrN ₃ O ₂ (292):

Calculated:
found:

C 41.1, H 6.2, N 14.4; C 41.3, H 6.1, N 14.2.

b) 2,4-010X0-1,2,3,4-16 ^ 81 ^ 03-1,5 ^ 1311 ^ 1-3-171611 ^ 1-s-triazinium-bromide:

18.5 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-diethyl-3-methyl-s-triazine are dissolved in 20 ml of methylene chloride, and 24 g (0.15 mol) of bromine are added dropwise . By occasional cooling maintaining the temperature at 2O ⁰ C to 30 ⁰ C. After a few minutes an orange precipitate forms. It is filtered off with suction and recrystallized from isopropanol. 23 g (87%) of 2,4-dioxo-1,2,3,4-tetrahydro-1, S-diethyl-S-methyl-s-triazinium bromide with a melting point of 198 ° C. are obtained.

Analysis for C ₈ HuBrN ₃ O ₂ (264):

c) 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-di-cyclohexyl-3-methyl-s-triazinium bromide:

29.3 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-dicyclohexyl-3-methyl-s-triazine are placed in 40 ml of methylene chloride, and 24 g (0.15 mol) of bromine are added dropwise. By cooling you hold the temperature at 20 ° C to 30 ° C. The resulting orange-red precipitate is filtered off with suction and recrystallized from isopropanol. 25 g (67%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-dicyclohexyl-3-methyl-s-iriazinium bromide are obtained from the

Melting point 25O ⁰ C.

Analysis for Ci ₆ HJbBrN ₃ O ₂ (372):

Calculated: C 51.6, H 6.9, N 11.3;
found: C 51.6, H 6.9, N 11.3.

d) 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-dimethyl-3-isopropyl-s-triazinium bromide:

18.5 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-dimethyl-3-isopropyl-s-triazine are dissolved in 20 ml of methylene chloride, and 24 g (0.15 mol) of bromine are added dropwise. After one hour the orange-colored precipitate is filtered off with suction and recrystallized from isopropanol. 20 g (75%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-dimethyl-3-isopropyl-s-triazinium bromide are obtained from melting point 212-214 ° C.

Analysis for C ₈ HuBrN ₃ O ₂ (264):

Calculated: C 36.4, H 5.3, N 15.9;
Found: C 36.2, H 5.3, N 16.0.

40

• 4-3

• 50

60

65

f) 2,4-Dioxo-l ₁ 2,3,4-tetrahydro-l, 5-dibenzyl-3-methyl-s-triazinium bromide:

30.9 g (0.1 mol) 2,4-dioxo-hexahydro-1,5-dibenzyI - /? - methyl-s-triazine are placed in 40 ml of methylene chloride and mixed with 24 g (0.1 mol) of bromine with cooling. The unusual ones yellow crystals are mixed in isopropanol. They go into solution and after a few minutes the solution becomes colorless. White crystals separate out on cooling. Receives after suction 21 g (53%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-dibenzyl-3-methyl-s-triazine bromide from the melting point.

Analysis for Ci ₈ Hi ₈ BrN ₃ O ₂ (388):

Calculated: C 55.5, H 4.6, N 10.8; Found: C 55.3, H 5.0, N 10.6.

B) 2,4-Dioxo-nexahydro-s-triazines of the general formula III

2,4-dioxo-hexahydro-1,3,5-s-triazine

g (1 mol) of 1,3,5-trimethyl-biuret and 30 g of paraformaldehyde are added together with 5 ml of cone. Hydrochloric acid heated to 70 ° C. for 5 hours. The liquid contents of the flask are then poured onto a drying tray and recrystallized from cyclohexane after they have solidified. This gives 154 g (98%) of 2,4-dioxo-hexahydro-l, 3,5-s-triazine of melting point 88 ° -90 ⁰ C. Analogously were obtained:

from l, 5-diethyl-3-methyl-biuret and paraformaldehyde 2,4-dioxo-hexahydro-1,5-diethyl-3-methyl-s-triazine as a colorless oil,
from IS-dicyclohexyl-S-methyl-biuret and paraformaldehyde at 100 ⁰ C 2,4-dioxo-hexahydro-1,5-dicyclohexyl-3-methyl-s-triazine as a viscous oil,

of l, 5-dimethyl-3-isopropyl-biuret and paraformaldehyde at 100 ° C 2,4-dioxo-hexahydro-l, 5-dimethyl-3-isopropyl-s-triazine as white crystals of melting point 53 ° -54 ⁰ C , from 1,5-di-isopropyl-3-methyl-biuret and paraformaldehyde at 100 ⁰ C in the presence of gaseous hydrogen chloride the 2,4-dioxohexahydro-1,5-diisopropy 1-3-methyl-s-triazine as a brown oil ,

from 1,5-dibenzyl-3-methyl-biuret and paraformaldehyde the 2,4-dioxo-hexahydro-1,5-dibenzyl-3-methyl-s-triazine as a yellow viscous oil.

Claims (1)

Patent claims: 1- 6-Aryl-2,4-dioxo-hexahydro-s-triazines of the general formula I.
O a process for the preparation of the corresponding aldehydes. The compounds according to the invention are characterized by the general formula I.