DE2460823A1 - Triazinium salts useful as intermediates in coumarin prodn - being esp 2,4-dioxo- 1,2,34-tetrahydro-1,3,5-5-triazinium salts - Google Patents

Abstract

2,3,4-tetrahydro-1, 3,5-s-triazinium salts of formula (I) are new: (where n is 1 or 2; R1 R2 and R3 are opt. substd. alkyl, alkenyl, cycloalkyl or aryl; if n = 2, R4 can be opt. substd. alkyl, alkenyl cycloalkyl or aryl, and if n = 1, R4 can also be H; and X is Cl or Br). Pref. alkyl gps. contain =18C; alkenyl gps. are mono- or poly-unsatd. aliphatic 2-10C gps., 5-12C cycloalkyl and aryl gps. may be Ph or naphthyl. Pref. substits are halogens, 1-4C alkyl, nitrile, carboxylate, OH, 1-4C alkoxy or opt. substd. aryl gps.). They are pref. prepared by halogenating 2,4-dioxo-hexahydro-1,3,5-triazines. (I) can be used as intermediates in prodn. of coumarin derivs. used as optical brighteners, and for introducing an aldehyde gp. into aromatics contg. a free amino gp. substit. Thus, (I) can react with 4-aminophenol to form aminal which can be hydrolysed to 4-aminosalicyl aldehyde, which can be converted to 4-acetylaminosalicyl aldehyde, known as starting material for 3-(1')-triazolyl-(1',2',3') -7-amino-coumarin.

Description

New triazinium salts The invention relates to new 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-s-triazinium salts, and a method for their production.

The new compounds are characterized by the general formula I. wherein n stands for 1 or 2, R1, R2 and R3 are identical or different and can stand for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, R4 for the case that n is the same 2, for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, in the event that n is 1, in addition to the aforementioned radicals, X can also stand for hydrogen, X for chlorine or bromine stands.

Examples of alkyl radicals are saturated aliphatic radicals with up to 18 carbon atoms, preferably with 1 to 4 carbon atoms. For example, the following radicals may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, Isobutyl and tertiary butyl; the methyl radical is particularly preferred.

The alkenyl radicals are mono- or multiply, preferably monounsaturated aliphatic radicals with 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms in question.

The following radicals may be mentioned as examples: vinyl, allyl, and also the isomeric propenyl, butenyl and pentenyl radicals. The allyl radical is particularly preferred.

Cycloalkyl radicals 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: the cyclopentyl, the cyclohexyl, the cycloheptyl, the cyclooctyl, the cyclononyl and the cyclododecyl radical; is particularly preferred the cyclopentyl and the cyclohexyl radical.

The phenyl or naphthyl radicals are preferred as aryl radicals.

As substituents through which the alkyl, alkenyl, cycloalkyl or Aryl radicals may be substituted, for example: Halogens, such as Fluorine, chlorine, bromine or iodine, preferably fluorine and chlorine; straight or branched chain Alkane radicals with 1 to 4 carbon atoms, which are optionally substituted by halogen or are polysubstituted, preferably the methyl, chloromethyl and trifluoromethyl radical; the nitrile group; optionally by lower alcohols, preferably with 1 to 4 Carbon atoms esterified carboxyl groups, preferably the carboxymethyl or Carboxyethyl ester group, hydroxyl groups, alkoxy groups with a 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.

Examples of compounds of the general formula I are the Derivatives of the following 2,4-dioxo-1,2,3,4-tetrahydros-triazinium chlorides or bromides named: 1,3,5-trimethyl-, 1,5-diethyl-3-methyl-, 1,5-dicyclohexyl-3-methyl-, 1,5-dimethyl-3-isopropyl-, 1,5-diisopropyl-3-methyl-, 1,5-dibenzyl-3-methyl-, 1,3,5-trimethyl-6-ethyl-, 1,3,5-trimethyl-6-isopropyl-, 1,3,5-trimethyl-6-phenyl-, 1,3,5-trimethyl-6- (4-chlorophenyl) -, 1,3,5-trimethyl-6- (2,4-dichlorophenyl, 1,5-dimethyl-3-phenyl-, 1,5-di (3-trifluoromethylphenyl) -3-methyl-, 1,3,5-trimethyl-6-chloromethyl-, 1-phenyl-3,5-dimethyl-, 1- (3-trifluoromethyl-phenyl) -3,5-dimethyl-, 1- (3-trifluoromethyl-4-chlorophenyl) -3,5-dimethyl-, 1,3,5-trimethyl-6-naphthyl- (1) -, 1,5-di (carbomethoxymethyl) 3-methyl-, 1,5-di (cyanomethyl) -3-methyl-, 1,3,5-trimethyl-6- (4-nitrophenyl) -, 1,5-dicyclopentyl-3-methyl-, 1,5-di-tert-butyl-3-methyl-, 1,5-diallyl -3-methyl-, 1,5-di-n-butyl-3-methyl-, 1,5-di-ieobutyl-3-methyl-, 1,5-di-n-propyl-3-methyl-, 1,3, 5-trimethyl-6 (4-fluorophenyl) -, 1,5-di (4-methoxybenzyl) -3-methyl-, 1,5-di (carboethoxy-methyl) -3-methyl-, 5-I) istearyl-3-methyl-, 1,5-i-dodecyl-3-methyl-, 1,3,5-trimethyl-6- (4-methylphenyl) -, 1,3,5-trimethyl-6 (4-cyanophenyl) -, and 1,3,5,6-tetramethyl-2,4-dioxo-1,2,3,4-tetrahydro-s-triazinium chloride or bromide.

A process for the preparation of the new 2,4-dioxo-1, 2,3,4-tetrahydro-1, 3,5-s-triazinium salts of the general formula I was also used wherein n stands for 1 or 2, R1, R2 and R3 are identical or different and can stand for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, R4 for the case that n is 2, for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and if n is 1, in addition to the aforementioned radicals, X can also be hydrogen, X is chlorine or bromine can be found, which is characterized in that 2,4-dioxohexahydro-1,3,5-triazines of the general formula II in which n, R1, R2, R3 and R4 have the aforementioned meaning, halogenated.

The halogenating agent for the process according to the invention can be elementary Halogen, especially chlorine or bromine are used. Of course you can also compounds which split off chlorine or bromine under the reaction conditions, can be used. Such compounds are, in particular, sulfuryl chloride and sodium hypochlorite or sodium hypobromide, tert. Butyl hypochlorite, N-bromosuccinimide or sodium dichlorocyanuric acid.

The reaction according to the process according to the invention is generally carried out at temperatures from 0 to 1000C, preferably at 20 to 50 ° C.

The 2,4-dioxo-hexahydro-1,3,5-triazines used as starting material of the general formula II, in which n is 1 or 2, R1, R2 and R3 are the same oder verscheiden.sindund for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or optionally for one substituted aryl radical and, R4 for the case that n is equal to 2, for an optionally substituted straight-chain or branched one Alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted one Aryl radical and, in the event that n is 1, in addition to the aforementioned radicals can also stand for hydrogen are new.

As starting materials according to the general formula II are for example named: 1,3,5-trimethyl-, 1,5-diethyl-3-methyl-, 1,5-dicyclohexyl-3-methyl-, 1 , 5-dimethyl-3-isopropyl-, 1,5-diisopropyl-3-methyl-, 1,5-dibenzyl-3-methyl-, 1, 3, 5-trimethyl-6-ethyl-, 1,3, 5-trimethyl-6-isopropyl-, 1,3,5-trimethyl-6-phenyl-, 1,3,5-trimethyl-6- (4-chlorophenyl) -, 1,3,5-trimethyl-6- (2,4-dichlorophenyl-, 1,5-dimethyl-3-phenyl-, 1,5-di (3-trifluoromethylphenyl) -3-methyl-, 1,3,5-trimethyl-6-chloromethyl-, 1-phenyl-3,5-dimethyl-, 1- (3-trifluoromethyl-phenyl) -3, 5-dimethyl-, 1- (3-trifluoromethyl-4-chlorophenyl) -3,5-dimethyl-, 1,3,5-trimethyl-6-naphthyl- (l) -, 1,5-di (carbomethoxymethyl) -3-methyl-, 1,5-di (cyanomethyl) -3-methyl-, 1,3, 5-trimethyl-6- (4-nitrophenyl) -, 1,5-dicyclopentyl-3-methyl-, 1,5-di-tert. -butyl-3-methyl-, 1,5-diallyl-3-methyl-, 1,5-di-n-butyl-3-methyl-, 1,5-di-isobutyl-3-methyl-, 1, 5-1) i-n-propyl-3-methyl-, 1,3,5-trimethyl-6 (4-fluorophenyl) -, 1,5-di (4-methoxybenzyl) -3-ynethyl-, 1,5-di (carboethoxy-methyl) -methyl-, 1,5-listearyl-3-methyl-, 1,5-di-dodecyl-3-methyl-, 1,3,5-trimethyl-6- (4-methylphenyl) -, 1,3,5-trimethyl-6 (4-cyanophenyl) -, and 1,3,5,6-tetramethyl-2,4-dioxo- hexahydro-s-triazine.

The 2,4-dioxo-hexahydro-1,3,5-triazines used as starting materials of the general formula II can by reacting in the 1-, 3- and 5-positions accordingly substituted biurets made with aldehydes in the presence of acidic catalysts will.

The halogenating agent is generally used for the process of the invention based on the 2,4-dioxo-hexahydro-1,3,5-triazine used in equivalent amounts or in excess, for example up to about 2 moles per mole of 2,5-dioxo-hexahydro-1, -3,5-triazine.

In some cases it has also been found to be beneficial to use the To carry out the process according to the invention in the presence of suitable inert solvents. Examples of solvents are lower aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform and carbon tetrachloride, lower aliphatic Alcohols such as methanol, ethanol, n- and iso-propanol, etc., ethers such as diethyl ether, Tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons, pyridine or water in question.

The process according to the invention for the preparation of 2,4-dioxo-1, 2,3,4-tetrahydro-1, 3,5-triazinium salts is said to be based on the reaction of 2, 4-I) ioxo-hexahydro-1 3, 5-trimethyl -triazine with bromine to 2,4-Diqxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-triazinium bromide can be explained in more detail by the following reaction scheme: The process according to the invention can be carried out in practice as follows: the 2,4-dioxo-hexahydro-1,3,5-triazine is dissolved or suspended in a solvent and the halogenating agent is slowly added. The reaction can be carried out at temperatures from OOC to 10,000, preferably from 200.degree. C. to 500.degree. An excessive increase in the reaction temperature can be prevented by cooling. The reaction is generally over after 1 to 5 hours. Then the 2,4-dioxo-1, 2,3'4-tetrahydro-1, 3,5-triazinium salt in the usual way by filtration, precipitation by adding a non-polar solvent in which the salts are insoluble, or by evaporation of the Reaction solution isolated. The reaction products can sometimes contain elemental halogen more or less firmly bound. The halogen-free compounds are then obtained by digestion or recrystallization, for example from alcohols such as isopropanol. Of course, the salts obtainable by the process according to the invention, which have chloride or bromide as anions, can be converted into the corresponding iodides, fluorides, sulfates, tetrafluoroborates, chlorates in a manner known per se by reaction with NaI, KF, Na2S04, tetrafluoroboric acid, KCl 03 or sodium acetate or acetates are transferred.

The 2,4-dioxo-1,2, D, 4-tetrahydro-1,3,5-triazinium salts obtainable by the process according to the invention can be used as valuable intermediates by adding these compounds reacts with aromatics in the sense of aromatic substitution. The one with it aminals formed can be hydrolyzed in a manner known per se, with as the hydrolysis product, the aromatic in question used for the reaction with a Aldehyde group remains as a substituent. A major advantage of this synthetic route can be seen in the fact that, in contrast to the state of the art, it is made possible in aromatics which have a free amino group as a further substituent, introduce the aldehyde group in direct reaction.

Using the triazinium salts according to the invention as the starting compound becomes 4Acetylaminosalioylaldehyd in a simple manner and with significantly improved Yields than according to the prior art (see A.A. Goldberg et al Soc. (London) 1954, 2641). 4-acetylaminosalicylaldehyde is a known starting component for 3- (1 ') - triazolyl- (1', 2 ', 3') - 7-amino-coumarin, known as an optical brightener which is synthesized from 4-acetylaminosalicylaldehyde in a manner known per se can be made by adding this compound to the free hydroxyl group by reaction methylated with dimethyl sulfate and the methoxy derivative obtained with 1,2.3-triazolyl-1-acetonitrile heated in ethanol as a solvent in the presence of catalytic amounts of pyridine and the methine compound obtained thereby -by heating in a suspension of anhydrous AlCl3 is converted into the desired coumarin derivative in benzene, in an analogous manner by means of the triazinium salts according to the invention via the easily accessible ones substituted benzaldehydes or naphthaldehydes also analogues as optical brighteners known coumarin derivatives (see DT-PS 1 296 121) are synthesized. The invention Triazinium salts are therefore a valuable starting material for the synthesis of these Coumarin derivatives.

Example 1 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide.

15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazine become dissolved in 30 ml of methylene chloride and treated dropwise with 24 g (0.15 mol) of bromine. The temperature is kept between 200 C and 30 ° C by cooling. After a few The addition product of bromine with the 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide separates within minutes in the form of orange crystals. They are aspirated and put in isopropanol recrystallized. 20 g (85%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide are obtained as white crystals melting at 2170 C.

Analysis C01110BrN302 (Bon, O2 (236) Calc .: C 30.6 H 4.2 N 17.8 Found: C 30.9 H 4.4 N 17.8 Example 2 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide 15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazine are dissolved in 30 ml of isopropanol submitted and added dropwise with 16 g (0.1 mol) of bromine. By cooling you hold the temperature at 20 ° C to 30 ° C. After a few minutes, an orange will drop Precipitation from. The mixture is stirred for a further 30 minutes and then heated to the boil. To A white suspension has formed in a short time. After cooling and vacuuming 17 g (72%) of the same compound as in Example 1 are obtained.

Example 3 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide 15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1h3,5-trimethyl-s-triazine are dissolved in 30 ml of dioxane dissolved and added dropwise with cooling with 24 g (0.15 mol) of bromine. The unusual one The orange-colored precipitate is filtered off with suction and the filtrate is evaporated. as The residue is a yellow-red oil which turns orange when stirred in isopropanol Crystals solidified.

The combined precipitates are boiled in isopropanol and 21 g (89%) of the compound described in Example 1 are obtained.

Example 4 2,4-Dioxo-1,2,394-tetrahydro-1,3,5-trimethyl-s-triazinium bromide.

15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazine become dissolved in 30 ml of pyridine and added dropwise with 16 g (0.1 mol) of bromine. To The resulting dark solution becomes the end of the exothermic reaction (approx. 10 min.) evaporated and the remaining residue boiled in isopropanol.

This gives 15 g (63%) of the same compound as in the example 1.

Example 5 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-diethyl-3-methyl-s-triazinium bromide 18.5 g (0.1 mol) of 2,4-dioxo-hexahydro-l, 5-diethyl-3-methyl-s-triazine are in 20 ml of methylene chloride dissolved and added dropwise with 24 g (0.15 mol) of bromine. By Occasional cooling, the temperature is kept at 200 to 30 ° C. After a few An orange-colored precipitate separates out for minutes. It is suctioned off and made from isopropanol recrystallized. 23 g (87%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-diethyl-3-methyl-s are obtained triazinium bromide with a melting point of 198 ° C.

Analysis C8H14BrN302 (264) Calc .: C 36.4 H 5.3 N 15.9 Found: C 36.3 II 5.3 N 15.5 Example 6 2,4-Dioxo-1x2x3s4-tetrahydro-1b5-di-cyclohexyl-3-methyl-striazinium bromide 29.3 g (0.1 mol) of 2,4-dioxo-hexyhydro-1,5-dicyclohexyl-3-methyls-triazine are in Submitted 4Q ml of methylene chloride and treated dropwise with 24 g (0.15 mol) of bromine. The temperature is kept at 20 ° C. to 30 ° C. by cooling. The orange-red which has precipitated out Precipitate is filtered off with suction and recrystallized from isopropanol. You get 25 g (67%) 2,4-dioxo-1,2,3,4-tetrahydro-1,5-di-cyclohexyl-3-methyl-s-triazinium bromide with a melting point of 250 ° C.

Analysis: C1H2BrF 02 (372) Calculated: C 51.6 H 6.9 N 11.3 Found: C 51.6 H 6.9 N 11.3 Example 7 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-dimethyl-3-isopropyl-striazinium bromide 18.5 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-dimethyl-3-isopropyls-triazine are in Dissolved 20 ml of methylene chloride and added dropwise with 24 g (0.15 mol) of bromine. After one hour, the orange-colored precipitate which has separated out 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 - 2140 C.

Analysis C8II1413rN302 (264) Calcd .: C 36.4 H 5.3 N 15.9 Found: C 36.2 H 5.3 N 16.0 Example 8 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-diisopropyl-3-methyl-s-triazinium bromide 21.3 g (0.1 mol) of 2,4-dioxo-hexahydro-1, 5-diisopropyl-3-methyls-triazine are in Dissolved 30 ml of methylene chloride and added dropwise with 24 g (0.15 mol) of bromine. The temperature is kept at 200 to 30 ° C. by cooling. After an hour it will the orange-colored precipitate formed is suctioned off and redissolved from isopropanol. 16 g (55%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-diisopropyl-3-methyl-s-triazinium bromide are obtained as white crystals melting at 210-21,200.

Analysis: C1OHX8BrN302 (292) Calcd .: C 41.1 H 6.2 N 14.4 Found: C 41.3 H 6.1 N 14.2 Example 9 2,4-Dioxo-1,2,3,4-tetrahydro-1,5-dibenzyl-3-methyl-s-triazinium bromide 30.9 g (0.1 mol) of 2,4-dioxo-hexahydro-1, 5-dibenzyl-3-methyl-striazine are in 40 ml of methylene chloride and mixed with 24 g (0.1 mol) of bromine with cooling. The yellow crystals which have precipitated out are mixed in isopropanol. you go in solution and after a few minutes the solution becomes colorless. Divide as it cools white crystals appear. After suctioning off, 21 g (53%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,5-dlbenzyl-3-methyl-s-triazinium bromide are obtained from melting point analysis: C18H18BrN3 ° 2 (388) calc .: C 55.5 II 4.6 N 10.8 found: C 55.3 H 5.0 N 10.6 Example 10 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6-ethyl-s-triazinium bromide 18.5 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6-ethyls-triazine are in 20 ml of methylene chloride oxidized as in Example 1 with 24 g (0.15 mol) of bromine. The unusual one orange-yellow precipitate is dissolved in acetone. The solution becomes discolored and after a short time white crystals separate. After the suction one obtains 14 g (53%) 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6-ethyl-s-triazinium bromide from melting point 210-2110C.

Analysis: C8H1413rN302 (264) Calculated: C 36.4 H 5.3 N 15.9 Found: C 36.6 H 5.2 N 15.9 Example 11 2,4-Dioxo-1x2t3t4-tetrahydro-1,3,5-trimethyl-6-isopropyls-triazinium bromide 19.9 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6-isopropyl-s-triazine dissolved in 40 ml of methylene chloride and treated with 24 g (0.15 mol) of bromine. The received The brown-red solution is heated to the boil. Red crystals separate out in the process. They are suctioned off and redissolved from isopropanol. 16 g (58%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6-isopropyl-5-triazinium bromide are obtained as white crystals that melt at 1960-1980C.

Example 12 Bis-6z62- (2,4-dioxo-1,2x3,4-tetrahydro-lh3h5-trimethyl-s-triazinium bromide) methane 32.6 g (0.1 mol) of bis-6,6 '(2,4-dioxo-hexahydro-l, T, 5-trimethyls-triazine) methane are dissolved in 100 ml of methylene chloride as in Example 1 with 24 g ( 0.15 mol) of bromine implemented. After recrystallization from isopropanol, 30 g (74%) of white crystals of bis-6,6 '- (2,4-dioxo-l, 2,3,4-tetrahydro-l, 3, 5-trimethyl-striazinium bromide) are obtained -methane, which melts at 2160-2180 C.

Analysis: C13H21Br2N6O4 (485) Calcd .: C 32.2 H 4.3 N 17.3 Found: C 32.3 H 4.1 N 17.2 Example 13 2,4-Dioxo-1,2,3w4-tetrahydro-12325-trimethyl-6-phenyl-s-triazinium bromide 23.3 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6-phenyls-triazine are in Submitted 100 ml of methylene chloride and oxidized with 24 g (0.15 mol) of bromine at 20 to 300C. The mixture is then heated to the boil for 1 hour and then the orange-red which has precipitated out is sucked off Precipitation from. 19 g (61%) of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6-phenyl-s-triazinium bromide are obtained as orange-red crystals, which after dissolving from methanol / acetonitrile at 192 ° - Melting 195 ° C.

Example 14 2,4-Dioxo-1,22324-tetrahydro-123,5-trimethyl-6- (4-chlorophenyl) -s-triazinium bromide 92 grams (0.35 moles) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (4-chlorophenyl) -s-triazine are placed in 50 ml of methylene chloride and added dropwise with 84 g (0.52 mol) of bromine offset. The reaction is strongly exothermic. The temperature is maintained by cooling between 200C and 3 «> C. After 3 hours, the resulting orange-colored precipitate is suctioned off and boiled in methanol.

76 g (63%) of 2-4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6- (4-chlorophenyl) -s-triazinium bromide are obtained from melting point 1890-1910C0 Example 15 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6- (2,4-dichlorophenyl) -s-triazinium bromide 30.3 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (2,4-dichlorophenyl) -s-triazine are suspended in 30 ml of methylene chloride and added dropwise with 24 g (0.15 mol) Bromine added. The reaction is slightly exothermic. A brown-red solution is created from which an orange-colored product precipitates after 5 hours. Receives after suction 22 g (58 50) of orange-red crystals of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-6- (2,4-dichlorophenyl ) -s-triazinium bromide 'which after boiling in methanol at 2120 - 2130 C under Melt decomposition.

Example 16 1,4-bis- [6,6 '- (2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-s-triazinium bromide-benzene 38.8 g (0.1 mol) of 1,4-bis- (6,6 '- (2,4-dioxo-hexahydro-1,3,5-striazine) benzene are placed in 100 ml of methylene chloride and mixed with 24 g ( 0.15 mol) of bromine is oxidized. After 3 hours, an orange-colored product has precipitated. It is filtered off with suction and boiled in isopropanol. 46 g (84%) 1,4-bis- (6,6 '- (2,4- Dioxo-1,2,3,4-tetrahydro-1,3,5-s-triazinium bromide) benzene with a melting point of 183 ° - 1850C.

Example 17 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium chloride 15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-striazine are dissolved in 50 ml of water solved. 7 g (0.1 mol) of chlorine are slowly passed into this solution. By the occasional When cooling, the temperature is kept at 25-30 ° C. Then the aqueous is evaporated Solution in a vacuum and thereby receives 18 g (94%) 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-s-triazinium chloride as white crystals that are highly hygroscopic.

Example 18 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium chloride 15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-striazine are dissolved in 30 ml of methylene chloride dissolved and treated dropwise with 13.4 g (0.1 mol) sulfuryl chloride. One stirs after until the evolution of gas has ended and then the methylene chloride evaporates in the Vacuum a. The same compound as in Example 17 is obtained.

Example 19 2,4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium chloride 15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-trimethyl-striazine are dissolved in 50 ml of methanol 17.8 g (0.1 mol) of sodium dichlorocyanuric acid were added and the mixture was stirred. Afterward the precipitated cyanuric acid is suctioned off and the filtrate evaporated. The residue that remains on evaporation is digested with water. After again Filtration to remove residual cyanuric acid gives an aqueous solution same compound as in Example 17.

Example 20 Use of 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-striazinium bromide (obtainable according to Example 1) for the preparation of 4-amino salicylaldehyde 23.6 g (0.1 Mol) 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyls-triazinium bromide are dissolved in 50 ml of water and mixed with 10.9 g (0.1 mol) of m-aminophenol. A clear solution has emerged after a few minutes. It is mixed with 8 g of sodium bicarbonate. 25 g (89%) of 2,4-dioxohexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-aminophenyl) -B-triazine precipitate as white crystals (melting point: 2400 ° C.).

113 g (0.4 mol) of the 2,4-dioxo-hexahydro-1,3,5-trimethyl-6 (2-hydroxy-4-aminophenyl) -s-triazine thus obtained are in a solution of 120 g of potassium hydroxide in 640 ml of n-butanol for 3 hours ilO0C stirred. It is then cooled and suctioned off. 67 g (96%) are obtained 4-aminosalicylaldehyde 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 with a melting point of 18600.

Example 21 The starting materials for the process according to the invention 2,4-Dioxo-hexahydro-s-triazines used can be represented as follows: 2.4-Dioxo-hexahydro-1.3.5-s-triazine 145 g (1 mol) 1,3,5-trimethyl-biuret and 30 g paraformaldehyde are added together with 5 ml conc. Hydrochloric acid heated to 700C for 5 hours. The liquid contents of the flask are then poured onto a drying tray and afterwards recrystallized from cyclohexane after solidification. 154 g (98%) of 2,4-dioxo-hexahydro-1,3,5-s-triazine are obtained with a melting point of 880-9 ° C.

In an analogous manner, 1,5-diethyl-3-methyl-biuret and paraformaldehyde were obtained 294-Dioxo-hexahydro-1,5-diethyl-3-methyl-s-triazine as a colorless oil from 1,5-dicyclohexyl-3-methyl-biuret and paraformaldehyde at 1000 C 2,4-dioxo-hexahydro-1,5-dicyclohexyl-3-methyl-s-triazine as a viscous oil from 1,5-dimethyl-3-isopropyl-biuret and paraformaldehyde 1000 C 2'4-dioxo-hexahydro-1,5-dimethyl-3-isopropyl-s-triazine as white crystals with a melting point of 530-540 ° C. from 1,5-di-isopropyl-3-methyl-biuret and paraiormaldehyde at 100 ° C in the presence of gaseous hydrogen chloride the 2,4-dioxo-hexahydro-1, 5-diisopropyl-3-methyl-s-triazine as a brown oil from 1,5-dibenzyl-3-methyl-biuret and paraformaldehyde 2,4-dioxo-hexahydro-1, 5-dibenzyl-3-methyl-s-triazine as yellow viscous oil from 1,7,5-trimethyl-biuret and propionaldehyde 2,4-Dioxahexahydro-1,7,5-trimethyl-6-ethyl-s-triazine as a yellow oil from 1,3,5-trimethyl-biuret and isobutyraldehyde is 2,4-dioxohexahydro-1,3,5-trimethyl-6-isopropyl-s-triazine bis-6,6 '- (2,4-dioxo-hexahydro-1,3,5-trimethyl-s- triazine) methane 2,4-Dioxohexahydro-1,3,5-trimethyl-6-phenyl-s-triazine as a yellow oil from 1,3'5-trimethyl-biuret and benzaldehyde as white crystals with a melting point of 110 ° C from 1,3,5-trimethyl-biuret and 4-chlorobenzaldehyde the 2,4-dioxohexahydro-1,3,5-trimethyl-6- (4-chlorophenyl) -s-triazine of melting point 960-980C (white crystals) from 1,3,5-trimethyl-biuret and 2,4-dichlorobenzaldehyde the 2,4-dioxo-hexahydro-1,3,5-trimethyl-6- (2,4-dichlorophenyl) -triazine as white Crystals with a melting point of 900-920C from 1,3,5-trimethyl-biuret and terephthalaldehyde 1,4-bis- (6,6'- [2,4-dioxo-hexahydro-1,3,5-s-triazine)] benzene as white crystals with a melting point of> 2500 C

Claims (4)

Claims: 1. Compounds of the general formula I wherein n stands for 1 or 2, R1, R2 and R3 are identical or different and can stand for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, R4 for the case that n is equal to 2, for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, if n is 1, additionally n of the aforementioned radicals can also stand for hydrogen, X for chlorine or bromine. 2. Compounds according to claim 1, characterized in that the alkyl radicals saturated aliphatic radicals with up to 18 carbon atoms, as alkenyl radicals mono- or polyunsaturated aliphatic radicals with 2 to 10 carbon atoms, as cycloalkyl radicals those with 5 to 12 carbon atoms and as aryl radicals of Phenyl or naphthyl radical. 3. Compounds according to claim 1 and 2, characterized in that as substituents by which the alkyl, alkenyl, cycloalkyl or aryl radicals are substituted can be halogens such as fluorine, chlorine, bromine or iodine, straight-chain or branched Alkane radicals with 1 to 4 carbon atoms, the nitrile group, optionally through lower alcohols, esterified carboxyl groups, hydroxyl groups, alkoxy groups with a straight-chain or branched alkane radical with 1 to 4 carbon atoms or an optionally substituted aryl radical. 4. Process for the preparation of the new 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-triazinium salts of the general formula I. wherein n stands for 1 or 2, R1, R2 and R3 are identical or different and can stand for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, R4 for the case that n is 2, for an optionally substituted straight-chain or branched alkyl, alkenyl or cycloalkyl radical, or for an optionally substituted aryl radical and, if n is 1, in addition to the aforementioned radicals can also be hydrogen, x can be chlorine or bromine can be characterized in that 2,4-dioxo-hexahydro-1,3,5-triazines of the general formula II in which n, R1, R2, R3 and R4 have the aforementioned meaning, halogenated.