DE2460823C3 - 2,4-dioxo-1A3,4-tetrahydro-striazinium salts - Google Patents

Description

wherein

R ', R ²

and R ^{3 are} identical or different and represent optionally substituted, straight-chain or branched alkyl, alkenyl or cycloalkyl "'radicals or optionally substituted aryl radicals and

X represents chlorine or bromine.

2. Process for the preparation of the 2,4-dioxo-. 1,2,3,4-tetrahydro-s-triazinium salts according to claim 1, characterized in that 2,4-dioxo-hexahydro-s-triazines of the general Formula II

R ^:

R '

(II)

wherein

R ¹ , R ² and R ^{1 have} the meanings given in claim I, chlorinated or brominated in a manner known per se.

The invention relates to 2,4-dioxo-l, 2.i, 4-tetrahydro-1-lria / iniumsil / e. as well as a method / ti of their production.

The connections according to the invention are marked by the general formula I.

K \

Hi

t'lck Ii ■ mI-t '.I ¹ IM hin Ic π μ πι I π im II μι ι' -ν ¹ Ih ¹ I ir 11 '.ill- ^ l il ·> 11 Il IH'['ι' , ι'ι ¹ 1 ti Ik Γ 11 IlT <M Il '\ ΚΊ / * · * · ΓΙ & -Μ ι.' Mk-. I \ lkt || \! ¹ IlI. Ί (\ ι lli, llk \ ll < ir ! '(Ld flit optionally substituted aryl radicals and
X represents chlorine or bromine.

As alkyl radicals, for example, saturated aliphatic resins with up to 18 carbon atoms are preferred with 1 to 4 carbon atoms are possible. For example, the following residues may be mentioned:

Methyl, ethyl, propyl, isopropyl, butyl,

Isobutyl and tertiary butyl;

the methyl radical is particularly preferred.

The alkenyl radicals are one or more times, preferably monounsaturated aliphatic radicals with up to 10 carbon atoms, preferably 2 to 5 carbon atoms in question. For example, the following residues may be mentioned:

Vinyl, allyl, and the isomeric propenyl,
Butenyl and pentenyl residues.
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;

Cyclopentyl and is particularly preferred

the cyclohexyl radical.

The phenyl or naphthyl radicals are preferred as aryl radicals.

As substituents by which the alkyl, alkenyl, cycloalkyl or aryl radicals can be substituted, are for example:

Halogens such as fluorine. Chlorine, bromine or iodine.
preferably fluorine and chlorine;
straight-chain or branched alkane radicals with 1 to 4 carbon atoms, which are optionally monosubstituted or polysubstituted by halogen, preferably methyl. Chloromethyl and trifluoromethyl radical;
the nitrile group;

possibly '. by lower alcohols, preferably with 1 to 4 carbon atoms esterified carboxyl groups, preferably the carboxymethyl or carboxyethyl ester groups, hydroxyl groups. Alkoxy groups with single straight-chain or branched alkane radical with 1 to 4 carbon atoms, preferably the Methoyy- or the Äthoxvgrtippc or an optionally substituted tor Aryliest, preferably the l'hcnvlrcsl

Examples of compounds of general I formula I are the derivatives of the following 2.4 dioxo-1.2. ! .4 tetrahydro-s Iria / inium · ι hlondc or bromide called:

.). ·> Irmiothvl. !, ■ "> l) iath> l) methvl,

Dm si! "TuA'vl i meihvl.

I) iiiν ihvl) isnprupvi.

I Ί> Μΐ |) ΐιιρ \ Ι I iiK'ilnl

ΟιΙημιζ, Ι! tiRilnl l. "> Dtmcllnl! phiMivl.

l) i (i tiiflh.ir.iH'tlnlpluMivl) i nu'll'vl.
l'hrir I). ") iliiiK'ilnl.
(i Ir 11 Ii nu üK'ltnl |> lun \ l)!. "><limi'th \ l
(i 1 111 Ii H κ HH ¹ I In I 4 ι h Ii 11 mIkmivI) I ₁ ") ilinn-tln I.

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

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

l.S-dicyclopentyl-B-methyl-,

l.S-di-tert-butylO-methyl-,

l.S-diallyl-S-methyl-,!, S-di-n-butyl-S-methyl-,

1,5-di-isobutyl-3-methyl-,

!, S-Di-n-propylO-methyl-,

l, 5-di (4-methoxybenzyl) -3-methyl-,

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

l.S-distearylO-methyl- and

t.S-Di-dodecylO-methyl-,

2,4-Dioxo-1,2,3,4-tetrahydro-s-triazinium chloride

or bromide.

Furthermore, a process for the preparation of the above-mentioned 2,4-dioxo-1,2,3,4-tetrahydro-s-triazinium salts according to the invention was provided found, which is characterized in that 2,4-dioxo-hexahydro-s-triazine of the general formula II

^! —N

N H.

(II)

N Il

wherein R ¹ . R ² and R ^{1 have} the aforementioned meanings, chlorinated or brominated in a manner known per se.

As such Malogeniea.ngsmii-.jl for the inventive Process, elemental chlorine or bromine can be used. Of course you can finally compounds which split off chlorine or bromine under the reaction conditions can also be used.

CII ₁ N

Cl

Such compounds are in particular sulfuryl chloride, sodium hypochlorite or sodium hypobromite, tert. Butyl hypochlorite, N-bromosuccinimide or sodium dichlorocyanuric acid.

The reaction according to the inventive process is generally carried out at temperatures of 0 to 100 ⁰ C ₁ is preferably at 20 to 50 ° C.

Those used as a starting product 2,4-Dioxo-hexahydro-s-triazine of the general Γογ-mel Il are new.

You can do this by putting in the 1, 3 and 5 positions appropriately substituted biurets made with formaldehyde in the presence of acidic catalysts will.

The corresponding halogenating agent is generally obtained for the process according to the invention to 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 2,4-dioxo-hexahydros-triazine.

In some cases it has also proven advantageous to carry out the process according to the invention in the presence to be carried out by suitable inert solvents. Lower solvents can be used, for example aliphatic chlorohydrocarbons 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 inventive method for the preparation of 2,4-dioxo-1,2,3,4-tetrahydro-s-triazinium salts should based on the conversion of 2,4-dioxo-hexahydro-1,3,5-trimethyl-s-triazine with bromine to form 2,4-dioxo-1,2,3,4-tetrahydro-1,3,5-trimethyl-s-triazinium bromide can be explained in more detail by the following reaction scheme:

CII,

11> -N

\ / Mir, »C MN S-Il Hr + 1IHr

N Ή ^S / - N

YlL "'' \ ll.

The practical implementation of the invention Procedure can / .. IJ. take place as follows:

The 2,4-dioxo-hexahydroviria / .in is dissolved or suspended in a solution and the halogenating agent is slowly added. The reaction can be carried out at temperatures from 0 ° C. to K) OC. preferably from 20 ° C. to 50 ° C., if the reaction temperature rises too sharply, this can be prevented by cooling. The reaction is generally over after 1 to 5 hours. Then the 2.4-Di-OXo-1,2, J, 4 -letrahydro-s-lrinziniiini-salt is added in the usual Worse (lurch ΠίιπίΐίοΜ. Filling di reh / uj?: Ibi! are insoluble, or by ind I, vaccinate iso- In ¹ It- l.'ie reaction products kimnen sometimes clenicn t.iiL's halogen or more of Keaktmnslosiuig v. contain piece tied. digestion NLCR I Imknslallisiei cn, z. Ii.. ms Mkiihaben like Isnpn ipain il. be d.inn de h.ilo L'enlreic'i Vei Ιήιι <Ιμμι.η'Π ciiialtcn

Those obtainable by the perfect method 2,4-Dioxo-1,2,3,4-tetrahydro-s-iriazinium sal / .c can be used as valuable / wiping products by combining these compounds with aromatics brings about an aromatic substitution for reaction. The resulting aminals can in an are hydrolyzed in a known manner, the hydrolysis product in question being the one used for the reaction Aroma! with an aldehyde group as a substituent. Km essential advantage of this .synthetic pathway can be seen in the fact that it becomes ermiijilifhl in the counter salt / at hour of the technology, in aromatics, which a free amino lip as a further sub-term have, in direct reaction, the aldehyde group to introduce

Using the triazinium salts according to the invention as The starting connection is • I-Aceulaminosalicylaldehu! in a simple way ιιικ! mil significantly improved Yields than according to the prior art (see A.A.

Goldberg et al. Soc. [London] 1954, 2641) accessible. 4-AcetylaminosaIicylaldehyd is a known starting component for the 3- (l, 2,3-triazo! -l-yl) -7-amino-coumarin known as optical brightener, which can be synthesized from 4-acetylaminosalicylaldehyde in a manner known per se by this compound is methylated on the free hydroxyl group by reaction with dimethyl sulfate and that at the same time obtained methoxy derivative with 1.2.3 triazol-1-ylacetonitrile heated in ethanol as a solvent in the presence of catalytic amounts of pyridine and thereby he retained methine compound by heating in a suspension of anhydrous AlCl] in benzene into the desired Coumarin derivative transferred. In an analogous manner, by means of the triazinium salts according to the invention via the easily accessible substituted benzaldehydes or naphthaldehydes also analogous as optical brighteners known coumarir derwate (cf. DE-PS 12 96 121) are synthesized. The triazinium salts according to the invention are therefore valuable ones Exit material! for the synthesis of these cumin derivatives represent.

example 1

2,4-Dioxo-1,2,3,4-tetrahydro-1,3.5-trimethyls-triazinium bromide

15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3,5-dimethylstriazine are dissolved in 30 ml of methylene chloride and 24 g (0.15 mol) of bromine are added dropwise. By cooling thereby maintaining the temperature between 20 ^C C and 30 ⁰ C. After a few minutes the product precipitates addition of bromine to the 2.4-dioxo-1,2.3.4-tetrahydro-l, 3,5-trimethyl-s-triazinium -bromide in the form of orange crystals. They are filtered off with suction and recrystallized from isopropanol. You get; 20 g (85%) 2,4-dioxo-1,3,4-tetrahydro-1,3,5-trimethyls-triazinium bromide as white crystals which melt at 217 ° C.

Analysis CHi ₁₁ BrNjO.- (236):

Calculated: 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-trimethyls-triazinium bromide

15.7 g (0.1 mol) of 2,4-dioxo-hcxahydro-l, 3.5-triazine-trimethyls ir are introduced 30 ml of isopropanol and treated dropwise with 16 g (0.1 mol) of bromine. The temperature is maintained at 20 ° C. to 30 ° C. After a few minutes, cm of orange-colored precipitate is formed. The mixture is stirred for a further 30 minutes and then heated to the boil. After a short time, a white suspension has formed. After cooling and suctioning off, 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-trimet hy I-s-triaziniiim bromide

15.7 g (0.1 mol) 2.4-l) ioxo-hexahydro-1,3,5-trimethyls-tria / yne are dissolved in 30 ml of dioxane and, while cooling, 24 g (0.15 mol) of bromine are added dropwise. The orange-colored precipitate which has separated out is filtered off with suction, and the i'iltrai is evaporated. AK residue leaves a yellow-brown oil. which when mixed in isopropanol / u orange crystals egg ^ tarrt. The combined precipitates are boiled up in isopropanol, and 2 g (89%) of the compound described in Example 1 are obtained.

Example 4

2.4-Dioxo-1,2,3,4-tetrahydro-1,3,5-trimelhyls-triazinium bromide

15.7 g (0.1 mol) of 2,4-dioxo-hexahydro-1,3.5-trimethyls-tnazine are dissolved in 30 ml of pyridine, and 16 g (0.1 mol) of bromine are added dropwise. After the exothermic reaction has ended (approx. 10 min), the dark solution obtained is evaporated and the residue that remains is boiled up in isopropanol. One erhall thereby 15g (63 ⁰ to) of the same compound as in Example. 1

Example 5

2,4-Dioxo-1,2.3.4-tetrahydro-1.5-diet ^! -
3-methyl-s-trijzinium bromide

18.5 g (0.1 mol) 2.4-dioxo-hexah> dro-1.5-diälhy! - 3-methyl-s-triazine are dissolved in 20 ml of methylene chloride and replaced dropwise with 24 g (0.15 mol) of bromine. The temperature is kept at 20 ° to 30 ° C. by occasional cooling. After a few minutes it falls an orange precipitate. F.r is suctioned off and unikristallisicrt from isopropanol. You get 23 g (87%) 2.4-dioxo-1.2.3.4-tetrahydro-1.5-dieth> l-3-methyl-s-triaz.inium bromide vom Schmelz punk ι 198 C.

Analysis CH ^ BrN ₁ O (264):

Calculated: C 36.4. H 5.3. N 15.9;
found: C 36.3. Il 5.3. N 15.5.

Example 6

2.4-Dioxo-1,2.3.4-tetrahydro-1.5-di-cloht; \ yl-3-niQtIiyl-s-iriazinium-bror, .id

29.3 g (0.1 mol) of 2,4-dioxo-hexyhydro-1,5-dicyclohexyl-3-methyl-s-triazine are placed in 40 ml of methylene chloride and added dropwise with 24 g (0.15 mol) of bromine. After cooling, the temperature is kept at 20 ° C. to 30 ° C. The resulting orange-red precipitate is filtered off with suction and crystallized from isopropanol. 25 g (67%) of 2,4-dioxo-1.2. IA tetrahydro-1.5-dicyclic are obtained <rhexyl-3-methyl -st riazinium bromide with a melting point of 250 C.

Analysis C, \> J! RN, O.> (372)

Calculated:
found:

C 51.6. Il 6.9. N 11.3:
C 51.6. Il 6.9. N 11.3.

(3 e i s ρ ι e 1 7

2.4-Dioxo-1.2.3.4-tetrahydro-1.5-rlin.ethyl
3-isoprop> ls-triazitium bromide

I8. ^r ) g (') .l mol) 2.4-Dio \ o-hexahydro-1.5-dimcth \ l-3-isopn. p \ I s ti Ki / ni λ earth dissolved in 20 ml methyl chloride and add dropwise with 24 g (0.15 Mol) bromine '■ replaced. After an hour, the fancy orange

colored precipitations abcsauj. "and au ·. Im iimkrisiiillisicr-. Man crh; ilt. '> g ('">'>) i

1.2.3.4-tetrahydro 1.5-dimet Ir. i ι ■ - <ι;> r < > ρ-. 1 mum liromid vom Schmei / pim · ι 212 2 M ι

.prupav.i is! iikI (I, then vaccinates .las Mclln I back; d mi Vaktiiin cn; You get the same connection \ mc in example l'i

analysis

(264):

Calculated: (3h, 4, II Vi. N LiM; found: C 3fi.2. Il ~>. I. N 1 h.O.

Example M

2,4-Dioxo-1,2,3,4-tetrahydro-1.5-diisoproopy I. 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 ver with 24 g (0.15 mol) of bromine dropwise puts. The temperature is kept at 20 ° C. by cooling to JO C. After an hour, the orange-

IfIlLJt-Mt. liH.UCI.1V.IHUg ti U £ K. Λ (1 U £ I UHU tt IfS I SO μ M f Jf ii [IU I redissolved. Ib g ('35 ¹ Vu) 2,4-dioxo-l is obtained .2.3.4-tctrahydro-1 .S-diisopropyl ^ -inethy ls-triazmium bromide as white crystals that melt at 210 - 212 C.

Analysis CuI 1, .. BrN, O- (292):

Calculated: C 41.1, 116.2. N 14.4; found: C 41.3. Il d.i. N 14.2.

Example 9

2.4-I) io> o-1.2,3.4-tetrahydro-1.5-dibenzy I-J-methyl-s-tria / iniiini brom id

30.9 g (0.1 mol) of 2,4-dioxo-hexahydro-1,5-dibenzyl-J-methyl-s-triazine are placed in 40 ml of methylene chloride and with cooling with 24 g (0.1 mol) of bromine offset. The yellow crystals which precipitated out were touched in isopropsnol. They go into solution, and after a few minutes the solution becomes colorless. On cooling, white crystals separate ah. After this Suction gives 21 g (53%) of 2,4-dioxo-1,2.3,4-tetrahydro-1,5-dibenzyl-3-methyl-s-triazinium bromide from the melting point.

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

Example 10

2.4-Dioxo-1.2,3,4-tetrahydro-3.5-trimethyls-triazinium-chloride

15.7 g (0.1 mol) 2, ^/) -Dioxo-hevi: iydro-1,3,5-trimethyls-triazine are dissolved in 50 ml of water, and 7 g (0.1 mol) of chlorine are slowly introduced into this solution. By occasional cooling, the temperature is maintained at 25 - 30 ^c C. Then, the aqueous solution is concentrated by evaporation in a vacuum and thereby obtains 18 g (94%) of 2,4-dioxo-

I ^ J ^ -tetrahydro-lJ.S-trimethyl-s-triazinium-chloride as white crystals that are highly hygroscopic.

Example 11

2.4-Dioxo- UJ ^ -t

s-triazinium chloride

15.7 g (0.1 mol) 2,4-dioxo-hexahydro-1,3.5-trimethyls-triazine are dissolved in 30 ml of methylene chloride, and 13.4 g (0.1 mol) of sulfuryl chloride are added dropwise. The mixture is then stirred until the evolution of gas has ended

I) ι

P ■: I I 2

. '. ι DioMi I., ¹ . i.4-tetrahydro-1.3,5 · tnmethyI ·
s-triazinuim-i hloi ld

"). 7 g (» ι. 'Mol) 2.4-DioKo-hexahydro- l.j. ") irmietlul s-tnnzin are dissolved in 50 ml of methanol with 17 mercury (0.1 mol Nalriumdichlorcyanuräure added and stirred. At the precipitated cyanuric acid is then filtered off with suction and the filtrate is evaporated. The one at fjtidamp The residue that remains is digested with water. After renewed filtration to remove the residual Licher cyanuric acid an aqueous solution of the same compound as in Example 10 is obtained.

Example 13

Use of 2,4-dioxo-1,2,3,4-tetnihydro-1,3,5-trimethyl-s-triazinium bromide

(available according to example 1)
for the production of 4-aminosalicvaldehyde

23.6 g (0.1 mol) of 2,4-dioxo-1,2,3,4-tetrhydro-1,3,5-trimethyl-s-triazinium bromide are dissolved in 50 ml of water and treated with 10.9 g (0.1 mol) of m-aminopheno! offset. A clear solution has emerged after a few minutes. You wi.d mixed with 8 g sodium bicarbonate. Included fall 25 g (89%) 2,4-dioxo-hexahydro-1.3.5-trimeth \ 1-6- (2-hydroxy-4-aminophenyl) -s-triazine as white crystals (melting point: 240 ^ C).

CIL N

CIL

-N

Ml

CiL

113 ε (0.4 mol) of the 2,4-dioxo-hexahydro- 1.3,5-trimethyl-6- (2-hydroxy-4-a mi nopheny I) -s-triazine are in a solution of 120 g of potassium hydroxide in 640 ml of n-butanol for 3 hours at 11OC ge stirs. It is then cooled and suctioned off. 67 g (96%) of 4-aminosalicylaldehyde are obtained as the potassium salt. Simply by stirring this salt in 150 ml of acetic anhydride at room temperature and then Boiling in water gives 4-acetylaminosalicylaldehyde with a melting point of 186 ° C.

The 2,4-dioxo hexahydros-triazines used as starting materials for the process according to the invention can be represented as follows:

2,4-Dioxo-hexahydro-13.5-tnmethyl-s-triazine

145 g (1 mol) of 1,3.5-trimethyl-biuret and 30 g of paraformaldehyde are added together with 5 ml of cone. ^C hydrochloric acid for 5 hours at 70 C heated. The liquid contents of the flask are then poured onto a drying tray and recrystallized from cyclohexane after they have solidified. 154 g (98%) of 2,4-dioxo-hexahydro-1,3.5-trimethyl-s-triazine with a melting point of 88 ⁼ -90 ° C. were obtained in an analogous manner

from 1,5-diethyl-3-methyi-biuret and paraformaldehyde 2,4-Dioxo-hexahydro-l, 5-diethyl-3-methvl-s-triazine as a colorless oil,

• in ". I.")) n vciohexvi- S-melh \ I biuret and i'ara, his i, '~> Di isnpi (isl i inethyl-biuiel and Para

f <> i Miaklehs d at HHI (, '■! I) ιον> -Ικ-χϋΙινιΙπι-1. "> iurnuilclctnd br 'KI (I (m (icgcrnviirl mim gasfor

(licvL'lohcxvl- 3-mclhvl s lri; i / in, ils / iihfliissiges () \. iiiijiimh ('lilorw, isscrsloll das IA- Πιομι-hcxaliyclro-

from I, "vDiriH'iiiyl i-isopropyl-biiircl and l'araforni!."> dusoprupvl -) mettnl-s -Irin / in as brown oil,

; ilili: liul liui I (K) i'C 2.4-Di (IXO licxaliuliu-i. ") -lime .ills l, VI) iben / \ l- J-nuMhyl-biurct and Pnrnform-

ih> l i-isopnipyl-s iria / m as lingering crystals muh alilierend the 2.4 l) n> \ (i-he \, ihydro-1, ") ■; .. beii / yl-

Seliuid / punkl "> J - "> 4 (,! -Methyl s Ina / in as a yellow viscous oil

Claims (1)

Patent claims: 1. 2,4-Dioxo-1,2,3,4-teirahydro-s-triazinium salts of the general formula I. R ¹ -N R ^: -N X "