LU84241A1 - ISOCYANURATES AND THEIR PREPARATION - Google Patents

Description

r · at 4456/26413 DB / AG - 1 -

CASE III

ISOCYANURATES AND THEIR PREPARATION

The present invention relates to new isocyanurates also called triazinates 1,3,5 v triones 2,4,6.

* The new isocyanurates according to the invention correspond to the general formula: Θ

NOT

0 = c ^ C = 0 p -0 “]

I l (R> a (R ’} b Q

L Jp / n c 4 p (I) in which R denotes an optionally substituted, monovalent or polyvalent hydrocarbon radical; R1 which is different from R denotes an optionally substituted hydrocarbon radical or hydrogen; - Q denotes a group containing a number n of ammonium, phosphonium or arsonium tetrasubstituted functions; * · P is a number at least equal to 1; y a is equal to 1 or to p and b is equal to zero or to p, it being understood that, if a is equal to 1, b is equal to p and that, if b is equal to zero, a is equal to p .

t? - 2 - The invention covers, in particular as new isocyanurates, the compounds corresponding to the following formulas: νΘ v ^ \ o = c c = o r I I (II) * R— —N N-R ’ω L J p / n

II

o L J p νΘ x \ o = c c = o I I Γ n® ~ | (III) -R-N N- Qn \ κ.

0 L J p.

; in which Q denotes a group containing a number n of functions | substituted ammonium, phosphonium or arsonium tetra- 5; | R denotes an optionally substituted hydrocarbon radical! Λ I killed, monovalent or versatile; :? ! R ’denotes an optionally substituted hydrocarbon radical, different from R, or hydrogen; | p is a number equal to or greater than 1; n denotes the number of functions ammonium, phosphonium, ___ ___ · r,> - - 3 -

The isocyanurates of formulas (I), (II) and (III) according to the invention can be converted, in known manner, into mono-, bi- or tri- * substituted molecular isocyanurates of which all the substituents can be identical or different one of otters.

The new isocyanurates of formulas (I), (II) * and (III) according to the invention can be used for various purposes and, in particular, as intermediates in organic synthesis, for example, in the preparation of pharmaceutical products, herbicides, insecticides and disinfectants. The new isocyanurates of formulas (I), (II) and (III) according to the present invention can be used in the preparation of polymers.

The principle of the preparation of molecular isocyanurates, by trimerization of organic isocyanates, in the presence of catalysts, is known. These preparations, which can only lead to molecular heterocyclic compounds, are generally only applicable for the preparation of isocyanurates bearing three identical substituents.

S It is also known to prepare metal salts of isocyanurates by reaction of an organic isocyanate; and a metallic cyanate. Thus, in “US Pat. No. 3,549,630, there is described the preparation of metal salts of symmetrical disubstituted isocyanurates by reaction, in an aprotic solvent, of an organic isocyanate and a metal cyanate; isocyanu- salts - • A _. "I ____. JJ Al | A _ ^ / 4 · - 4 - substituted. This process has, as disadvantages, requiring the use of aprotic solvents whose dielectric constant is greater than 15 at 25 ° C. and only allowing the preparation of symmetrical disubstituted isocyanurate salts from which it is not - - possible, by reaction with an organic halide, to obtain trisubstituted isocyanurates whose three substituents are different.

Also known is the preparation of metal salts of isocyanurates from diaryl-1,3-uretidine-2,4 diones and metal cyanates. This process, described in US Pat. No. 3,625,964, has the disadvantage of only allowing the preparation of isocyanurate salts bearing aromatic substituents in positions 3 and 5; moreover, the preparation of isocyanurate salts carrying different substituents at positions 3 and 5 requires the preparation of asymmetric uretidine-diones which is, in general, difficult and not very selective.

> Another drawback of this process is that, in general, it provides a mixture of isocyanurate salt and molecular isocyanurate. In addition, the process is only carried out in suspension and the choice of solvents which can be used is limited to aprotic solvents whose dielectric constant is greater than 15 to 25 ° C.

In addition to the preparations of molecular isocyanurates, based on the trimerization of isocyanates or on the action of a suitable co-reactant with an isomer salt in the 1,3,5 position from allophanates and d 'organic isocyanates (A. Etienne, G. Lonchambon and J. Roques, CR Acad. Sc., Paris, Series C.283, p. 281, 1976) or from 1,3-aryl-5 bis (dimethyl -amino) -6.6 tri-2,4-dione-2,4 and arylsulfonyl-isocyanate (R. Richter, H. Ulrich, J. Org. Chem. 41 (21), 3409, 1976).

These latter processes have numerous drawbacks: they use expensive raw materials, are only applicable for obtaining certain asymmetric isocyanurates and are often carried out at temperatures and with reaction times which weigh heavily on the economics of these processes. .

The process discovered by the applicant does not have its drawbacks and allows the preparation, under economic conditions, of a multitude of symmetrical or asymmetrical 1,3,5-triones 1,3,5-triones 2,4,6 2,4,6 isocyanurates or triazines 1,3,5 triones 2,4,6 molecular carrying identical or different substituents in positions 1,3 »5.

The economy of the process of the present invention resides in the use as starting materials of oxadiazines 1,3,3 triones 2,4,6 which are easily obtained from inexpensive reagents.

Thus, the present invention also relates to a process for the separation of isocyanurates corresponding to the general formula “ale: - 6 - Θ κ - o = d ^ c = op _ @ ~ i 1 i“. '"Μ], - / \ / ^ LJ p / n * ç L ° JP (IV) in which R denotes an optionally substituted, monovalent or polyvalent hydrocarbon radical; R * which can be the same or different from R denotes an optionally substituted hydrocarbon radical or hydrogen; Q denotes a metal or a group containing a number n of unsubstituted or mono-, bi-, tri- or tetrasubstituted ammonium, phosphonium or arsonium functions; p is a number at least equal to 1; n denotes the number of oxidation of the metal or the number j of ammonium, phosphonium or arsonium functions present in the group Q; a is equal to .1 or to p and b is equal to zero or to p, being

AT

j understood that, if a is equal to 1, b is equal to p and that, I if b is equal to zero, a is equal to p, i ·· I this process consisting in reacting an oxazine 1,3 , 5 i! | trione 2,4,6 corresponding to one or other of the following general formulas J: -Ί Ο o = c c = o

I I

- R- —N N-R ’(V) ^ ·

II

The 0

L J P

m0 / \ o = c c = o

I I

-R-N N. (VI)

VS

L J p in which R, R ’and p have the meanings given above, with a salt cyanate corresponding to the formula Q (NCO) n (VII) in which Q and n have the meanings given above.

The process according to the invention can be illustrated by the following reaction schemes (A) and (B):

Diagram A

0 0 = C ^ 0 = 0 r— _N N-R * + p / n Q (NC0) n -> -

VS

II

I * - 8 - νΘ ^ \ o = c c = o ε I I Γ η © Ί R— - N N-R * Q + ρ C0o \ ^ / 2 C L J ρ / η t I! ο

- L J P

(II)

Scheme B

o = c c = o! ! -R-N N + p / n Q (NCO) -y \ / \ ^ n

VS

• I

(VI) p Γ 0 Ί: ° 1 f ° Γ n © l I - -R-N N Q + p C02 I -ï ^ * - p / n i n 0

(III) P

κ

K

| In these reaction schemes, R, R1, Q, p and n have the meanings indicated above in the definition of ï.

compounds corresponding to the general formula (IV).

As oxadiazines 1,3,5 triones 2,4,6 of formula (V) or (VI), it is preferred to use the oxadiazines 1,3,5 - 9 -

As examples of oxadiazines 1,3,5 triones 2,4,6 useful in the process according to the present invention, mention may be made of 3,5-dimethyl oxadiazine 1,3,5 trione 2,4,6 '; 2 3-methyl-5-benzyl-oxadiazine 1,3,5 trione 2,4,6; . - butyl-3 allyl-5 oxadiazine 1,3,5 trione 2,4,6; U ”benzyl-3 H-5 oxadiazine 1,3,5 trione 2,4,6; 0 3-methyl-5-allyl oxadiazine 1,3,5 trione 2,4,6; 3-propyl-5-acetyl-oxadiazine 1,3,5 trione 2,4,6; (chloro-9-decyl) -3 cyclohexyl-5 oxadiazine 1,3,5 trione 2,4,6; t bis-1,6- (3-methyl-oxadiazine 1,3,5 trione 2,4,6) -hexane of formula: 0 0

A,, A

H, C — N. N (CHp) r N N CH, Μ. M „bis-aa '- (3-allyl-oxadiazine 1,3,5 trione 2,4,6) -p- ^ xylene of formula: 0 0 A jp \ Ά H5C = HC-H5C NN — H9C-U \ V-CH9 NN — CH0-CH = CH ^ 22 2 \ _ / 2 | 2 2 / \ 0Λ Α0Λ 0 0 0 </ 0 ο (XVIII) - 10 - poly (3-methyl-oxadiazines 1,3 »5 triones 2,4,6), polymers formed by a number p of recurring units with the formula: “s.

-CH-CH0- · - Ô

X

| (XIX)

NOT

/ \ o = c c = o

I I

o n-ch *

: S

I and polyoxadiazines 1,3,5 triones 2,4,6, polymers | formed of a number p of recurring units of formula: i i Γ / V Ί o = c c = o - (ch2) 6 - ^^ L (xr)

II

0 or their mixtures.

Oxadiazines 1,3 »5 triones 2,4,6 of formulas | (V) and (VI) can be introduced as is in! the reaction mixture or be produced in solvent l ·!; de la rparii nn nar t.nnt.p mpthndp n.rmrmp. fiptto ρητηΜηοί cnn - 11 - its transformation into isocyanurate is particularly advantageous from the economic point of view. The preparation of lfoxadiazine 1,3 »5 trione 2,4,6 can be carried out, for example, according to a process which is the subject of another patent of the applicant, starting from an organic isocyanate, from a saline cyanate , carbon dioxide and - · a halide or an organic sulphate.

The saline cyanates of formula (VII), which can be used in the process according to the invention, are cyanates of mono-, bi- or trivalent metals or cyanates of ammonium, phosphonium or arsonium, unsubstituted or mono- , bi-, tri- or tetrasubstituted. In these ammonium, phosphonium or arsonium cyanates, Q can be represented - either by the general formula: (R1 R11 R111 Z) n RIV (VIII) in which Z denotes nitrogen, phosphorus and arsenic and R *, R ^ *, R ^ * and R ^, which are identical or different, denote hydrogen or substituted or unsubstituted alkyl, aryl, arylalkyl or heterocyclic radicals; R ^ and

TT

R, taken together, can also represent a% bivalent radical or in which RIV denotes a polyvalent radical - and n is the number of ammonium, phosphonium or arsonium functions present in the group Q of the compound of formula (II) or (III); - either by the general formula: 'R1 R1 - ^ © _RIII — Z © _RIV-- (IX) in in - 12 - in which Z, R * and have the meanings given above, R ^ ** and R * ^ are bivalent radicals' and has the meaning given above.

The preferred salt cyanate depends on the reactivity of the system, the temperature and the possible solvent in which the preparation is carried out.

In most cases, it is advantageous to use as a cyanate salt an alkali or alkaline earth metal cyanate or ammonium cyanates, phosphonium ov> arsonium tetrasubstituted, monovalent or polyvalent or mixtures thereof. Preference is given to sodium cyanate, potassium cyanate and tetrasubstituted, mono- or polyvalent ammonium cyanates or mixtures thereof.

Ammonium, phosphonium or arsonium cyanates can optionally be produced in the preparation liquid, before or during preparation, by any known method.

Examples of ammonium cyanates, phosphonium and arsonium tetrasubstituted which can be used in the process according to the present invention are tetramethylammonium cyanate, tetraethylammonium cyanate, tetrapropylammonium cyanate, tetrabutylammonium cyanate, tetraamylammonium cyanate, of 7 tetrahexylammonium, tricaprylmethylammonium cyanate, 5 benzyltrimethylammonium cyanate, benzyltriethylammonium cyanate, benzylisopropyldime-thylammonium cyanate, benzyltripropylammonium cyanate, phenyltrimethylammonium cyanate, phenyltrimethylammonium cyanate methyltributylphosphonium cyanate, tetra-butylphOSbhOfliUffl cyanate »'CVaTl & te of etraphenylphosphonium, benzyltriethylarsonium cyanate, tetra-propylarsonium cyanate, tetraphenylammonium cyanate, 1,4-tetraphenylammonium cyanate 1,4-dimethyl-1,4-diaza-1,4-bicyclo cyanate (2,2 , 2) octane, cyanate of - bis-1,6- (trimethyl ammonium) hexane, cyanates fixed on an anionic resin of the type AMBERLITE IRA 400 (FLUKA), the ionene of formula: - ^ - (C2 ) 4 - J ~ NCO® ^] (χ)

Jn / 2 l * ionene of formula: CH * CH * I 3 I 3

__ (CH2) 3-®— CH2 —CH2 - NC0®J

CH * CH * ”L J,“ “” where n is between 4 and 40, or their mixtures and their substituted derivatives.

The use of catalysts is not essential in the present process which allows preparations with good yields in fairly short times; catalysts such as CaCl 2 or MgO can, however, be used in specific cases.

It is advantageous that the substances which are fed in the solid state are in the most divided form possible.

The reaction conditions, such as the temperature, the pressure and the solvent in which the reactions take place, as well as the quantitative ratios of the substances to be used, depend to a certain extent on one another and are chosen, the if applicable, depending on the type of substance used and the nature of the desired product.

The quantitative ratio of salt cyanate to oxadiazine 1,3,5,4,4,4,4 can be chosen within wide limits, this ratio being as well stoichiometric as higher or lower than stoichiometry. In general, 0.5 to 2 equivalents of 1,3 * 5 trione 2,4,6 equivalents are used per equivalent of cyanate salt, and preferably 0.8 to 1.2 equivalents of oxadiazine 1, 3 »5 trione 2,4,6 per equivalent of salt cyanate. ^ - 15 -

The process of the present invention, although practicable in the absence of solvent, is preferably carried out in an inert organic solvent which does not interfere with the reaction. *. -

Both non-polar and low-polar organic solvents can be used as well as polar organic solvents. As solvents which can be used in the present invention, there may be mentioned, for example, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, the mixture of cis and trans isomers of 1 , 2-dichlorethylene, o-dichlorobenzene, dioxane, ethyl acetate, dimethoxyethane, tetrahydrofuran, toluene, oc-methylnaphthalene, acetone, methyl ethyl ketone, acetonitrile, propionitrile, benzonitrile, benzyl cyanide, nitrobenzene, nitrotoluene, dimethylformamide, dimethylacetamide, tetramethylurea, N-methylpyrrolidone, 11hexamethylphosphor-triamide, dimethylsulfoxide and their mixtures.

Particularly suitable are chlorinated hydrocarbons, linear or cyclic ethers, ketones and nitriles.

The proportion of solvent depends to a large extent on the type of solvent and the type of quantitative ratio of the other substances. In general, for each part by weight of reagents, up to 50 parts by weight of solvent can be used. In most cases, solvent, preferably 1 to 10 parts by weight of solvent, for one part by weight of reagents.

The preparation of the isocyanurates of formulas (I) to (IV) can be carried out according to the invention at temperatures between approximately -80 ° C. and + 250 ° C.

In most cases, temperatures between -20 ° C and 150 ° C can be used, and more particularly temperatures between 0 ° C and 70 ° C.

It is generally advantageous to work at pressures which are of the order of 0.6 to 4 bars, in particular, at atmospheric pressure; however, higher pressures can also be used. However, if you want to use simple devices, it is advantageous to work at pressures that are not significantly different from ordinary pressure.

The reaction time can vary to a large extent depending on the reactivity of the reactants, the temperature, the nature of the solvent and the possible presence of catalysts. In general, the reaction time is between 0.5 sec. and 24 hours and most often between 1 sec. and 10 a.m.

The isocyanurate yields of formulas (i) to (IV) are generally high and can be greater than 90% after 1 minute of reaction at 25 ° C.

The isocyanurates of formulas (I) to (IV) obtained by the process described above according to the invention can be - 17 - whose substituents in positions 1,3 and 5 can be identical or different.

The present invention therefore also covers s the preparation of triazines 1,3 »5 triones 2,4,6 molecular corresponding to the following general formulas: *

H

NOT

o = c c = o

Il, x R- -K N-R * (XII)

II

0 L J p

H

o = c c = o -Ri L <xiii> c

T II

0 r L J p R »

NOT

0 = C - c = o R— -N N-R * (XIV)

II

n - 18 - or R "

NOT

; / \ o = c c = o w | I (XV) -R-N N- II o L J p

In these formulas (XII) to (XV), R, R * and p have the same meanings as in the compounds of general formulas (I) to (IV), while R "represents an identical, substituted or unsubstituted hydrocarbon radical or different from R and R ",

The symmetric or asymmetric mono- or bi-substituted triazines 1,3,5 triones 2,4,6 corresponding to formulas (XII) and (XIII) can be prepared, according to the invention, by reaction of an acid with a isocyanurate of formula (I) to (IV).

As the acid, any organic or inorganic acid capable of yielding a proton can be used to the triazinates 1,3 ”5 triones 2,4,6 which have basic properties, for example an acid chosen from. 1 * hydrochloric acid, 1 * sulfuric acid, acetic acid, 1 * benzoic acid, 1 * formic acid and oxalic acid. Neutralization can be carried out either in the organic solvent of the preparation, in water, in another solvent or in a mixture of sol— - 19 -

As for the triazines 1,3 »5 triones 2,4,6 tri-substituted symmetrical or asymmetrical corresponding to formulas (XIV) and (XV), they can be prepared, - in accordance with the present invention, by reaction of an isocyanurate of formula (I) to (IV) with an organic halide or sulphate of formula R "Y (XVI) in which R" represents a hydrocarbon radical, substituted or not, identical or different from R and R ', while Y denotes a halogen or a sulfate group.

As examples of organic halides and sulphates which can be used in the present invention, mention may be made of dimethyl sulphate, diethyl sulphate, benzyl chloride, allyl chloride, 1-chloro-but-2-ene, cyclohexyl chloride, methyl chloride, methyl iodide, α-chloro-p-nitrotoluene, 1-chlor ohexane, 1 * a-chloro-p-trif luoromethyltoluene, acetyl chloride, benzoyl chloride, p-toluenesulfonyl chloride, oxalyl chloride, phtalyl chlorides, 1,4-dichlorobutene, Ι'α, α'-dichloro-m-xylene, 1 * α, a1 -dichloro- p-xylene, 1,6-dichlorohexane or their combination and their substituted derivatives, the invention will be described in more detail with the aid of the following examples, intended to illustrate the invention without limiting it.

The examples described have been carried out discontinuously in Grignard type reactors; it is obvious that reactors operating continuously can also be used.

The products obtained were identified by determination of their elementary compositions, potentiometric titration, analysis by I.R. spectroscopy, of nuclear magnetic resonance of and mass spectroscopy.

EXAMPLE 1 The apparatus is a 0.5 1 glass reactor fitted with four openings, equipped with a mechanical stirrer, a reflux condenser, a thermometer and a device allowing the introduction of a liquid.

The temperature is adjusted using a thermostat.

34.0 g of tetraamylammonium cyanate (0.1 mole), 15 ”8 g of dimethyl-3 * 5 oxadiazine 1.3” 5 trione 2.4.6 (0.1 mole) and 250 are introduced into the reactor. ml anhydrous tetrahydrofuran; the initially heterogeneous reaction mixture is left under stirring for 30 minutes at 25 ° C; a release of carbon dioxide is observed.

By evaporation of the solvent under vacuum, 45 g of tetraamylammonium isocyanurate 45 g are obtained.

The purity of the product obtained by simple evaporation of the solvent is very high; washing the solid with carbon tetrachloride to remove the trimethyl 1,3 »5 isocyanurate possibly formed and. - ~ crystallization from a mixture of tetrahydrofuran and petroleum ether does not modify the characteristics of the product.

EXAMPLE 2

The procedure is carried out under the conditions described in Example 1. 23.4 g of 3-methyl-5-benzyl-oxadiazine 1.3.5 trione 2.4.6, 22.8 g of tetrapropylammonium cyanate (0.1 mole) and 250 ml of dichloromethane. The homogeneous reaction mixture is left under stirring for 5 minutes; then the solvent is evaporated. 40.1 g of 3-methyl-5-benzyl isocyanurate of tetrapropylammonium are obtained (yield 96%).

EXAMPLE 3

The procedure is as in Example 2 and to the solution of 3-methyl-5-benzyl-isocyanurate of tetrapropyl ammonium, 7.9 g of acetyl chloride (0.1 mol) are added after 30 minutes of reaction , 3-methyl-5-benzyl-1-acetyl triazine is obtained 1,3,5 trione 2,4,6 with a yield of 95 - - 22 - EXAMPLE 4

The reactor described in Example 1 is used.

To 18.5 g of 1,6-bis (3-methyl-oxadiazine 1,3 ”5 trione 2,4,6) hexane (0.05 mol) in 250 ml of dry dichloromethane, is gradually added over 10 minutes, 28.4 gj of solid tetrabutylammonium cyanate (0.1 mole).

After 20 minutes of reaction with stirring at 25 ° C, the solvent is evaporated; 39.5 g of 1.6-bis (3-methyl-triazinate 1,3 "5 trione 2,4,6) hexane are obtained (yield 93%) EXAMPLE 5

In the reactor described in example 1, 17.2 g of 3-methyl-5-ethyl-oxadiazine 1,3,5 trione 2,4,6 and 250 ml of anhydrous acetonitrile are introduced; 22.8 g of tetrapropylammonium cyanate (0.1 mol) are added thereto.

After 5 minutes of reaction at 25 ° C., 34.2 g of 3-methyl-5-ethyl isocyanurate of tetrapropylammonium is recovered, after evaporation of the solvent (yield 96%).

EXAMPLE 6 7 * 9 g of dimethyl-3,5-oxadiazine 1,3 * 5 trione 2,4,6 (0.1 mole), 250 ml of anhydrous tetrahydrofuran are introduced into the reactor described in Example 1. 21.2 g of tetraphenylarsonium cyanate; the initially heterogeneous reaction mixture is left under stirring at 25 ° C. until the evolution of CO 2 stops. 22.3 g are isolated (yield 84%) of 3,5-dimethyl tetraphenylarsonium isocyanurate.

- 23 - EXAMPLE 7

In the reactor described in 1 * example 1, 0.1 mol of 3-methyl-5-ethyl-oxadiazine-1,3,5 trione 2,4,6 and 250 ml of acetonitrile are introduced; after dissolution of the reagent, 0.1 mol J of tetrabutylphosph onium cyanate is introduced with stirring at 20 ° C. After the end of CO 2 evolution (10 minutes), the 3-methyl-5-ethyl isocyanurate of tetrabutylphosphonium is isolated (yield 97%).

EXAMPLE 8

0.08 mole of finely divided potassium cyanate and 250 ml of dimethyl sulfoxide are introduced into the reactor described in example 1; to this mixture, with stirring at 25 ° C., 0.08 mol of 3,5-dimethyl-oxadiazine 1,3,5 trione 2,4,6 is added. The evolution of CO 2 ceases after 5 minutes; the sparingly soluble product is isolated by filtration and washed with ether. 6 g are isolated (yield 39 of dimethyl-3,5 isocyanurate of potassium, EXAMPLE 9

The polymerization of hexamethylenediisocyanate with carbon dioxide, in the presence of tributylphosphine, was carried out under the conditions used by K, H. Slotta and R. Tschesche * / ~ Ber., 60, 295 (1927) _7 for the preparation of monooxadiazines.

From the polymer obtained, the fraction soluble in tetrahydrofuran was isolated; the polyoxadiazine obtained - 24 - »Ο

II

c OCN - (CH2) 6 —-- (CH2) 6NC0 (XXI) oAoAo L J 5> 8

Is introduced into the reactor described in. Example 1, with stirring and at 25 ° C, 15.7 g of this polyoxadiazine, 250 ml of tetrahydrofuran and 15 g of tetrapropylammonium cyanate.

The reaction product precipitates in less than 5 minutes. After filtration, 22.5 g (81% yield) of a tetrapropylammonium polyisocyanurate, falling into formula (III), having isocyanate functions at the end of the chain, are isolated.

EXAMPLE 10

Is introduced into the reactor described in 1 * example 1, 10 g of 1,6-bis (3-methyl triazinate 1,3,5 trione 2,4,6) tetrapropylammonium hexane prepared as in Example 4 and 100 ml dichloromethane. A solution of hydrochloric acid in the same solvent is then introduced with stirring and at normal temperature.

Until complete neutralization of basic functions.

The reaction product is 1,6-bis (3-methyl-triazine 1,3,5 trione 2,4,6) hexane falling in formula (XII).

The reaction is quantitative.

EXAMPLE 11 "

To a solution of 10 g of 1.5 "bis (3-allyl-triazinate 1,3" 5 trione 2,4,6) of tetrapropylammonium hexane prepared as in Example 4 and 100 ml of anhydrous dichloromethane are added, with stirring and at 25 ° C, 0.03 mole of dimethyl sulfate. The reaction is continued for 30 minutes at normal temperature.

5.2 g (95% yield) of 1,6-bis (3-allyl-5-methyl-triazine 1,3,5 trione 2,4,6) hexane, falling into formula (XIV), are isolated.

EXAMPLE 12

10 g of tetrapropylammonium polyisocyanurate prepared as in Example 9 and 100 ml of methanol are introduced into the reactor described in Example 1. To the suspension is added, with stirring and at normal temperature, a 0.5 M solution of HCl in methanol until all the basic functions are neutralized. Analysis of the product obtained shows that, in addition to the neutralization of the triazinate functions, the transformation also converts the terminal isocyanate functions into methyl urethane. The structure of the final product is as follows: * 0 I! CHjOOCNH - (CH2) 6-N N - (CH ^ -NHCOOCHj ° ^ V ^ 0 (XXII)

H

L J 5.8 -. ——— falling into the formula— (XXII). ------—

Claims (21)

1. As new compounds, the iso-cyanurates corresponding to the following general formula:, -JJ eo = c C = 0 Γ „© Ί (I) II (R) a <R,> JQ NN a LJ / / \ / ^ L -1 p / n C 11 o LJP in which R denotes an optionally substituted, monovalent or polyvalent hydrocarbon radical; R * which is different from R denotes an optionally substituted hydrocarbon radical, or 1 * hydrogen; Q denotes a group containing a number n of tetra-substituted ammonium, phosphonium or arsonium functions; p is a number at least equal to 1; ^ a is equal to 1 or to p and b is equal to zero or to p, it being understood that, if a is equal to 1, b is equal to p and that, if b is equal to zero, a is equal to p . 2 * Isocyanurates according to claim 1, characterized in that they correspond to the following general formulas: - 27 - ^ N0 0 = f 0 (II) R— - N NR »nn © \ / u jj · LJ p / n 0 / LJ p * N © / \ o = cc = o -RN N- Γ _ © Ί ^ 111 ^ QnU il LJ p / n 0 LJ p in which Q denotes a group containing a number n of ammonium, phosphonium functions or tetra-substituted arsonium; R denotes an optionally substituted, monovalent or polyvalent hydrocarbon radical; R * denotes an optionally hydrocarbon radical; substituted, different from R, or hydrogen; <r ‘p is a number equal to or greater than 1; n denotes the number of ammonium, phosphonium or arsonium functions present in the group Q. 3- Process for the preparation of isocyanurates corresponding to the general formula: - 28 - "Θ N 0 = ^ C = 0 pn © n II. (R) a (R,) b QNN LJ / '', I" J, in which R denotes an optionally substituted, monovalent or polyvalent hydrocarbon radical; R * which can be the same or different from R denotes an optionally substituted hydrocarbon radical or hydrogen; Q denotes a metal or a group containing an n number of functions unsubstituted or mono-, bi-, tri- or tetrasubstituted ammonium, phosphonium or arsonium; p is a number at least equal to 1; n denotes the number of * oxidation- of the metal -or the number of ammonium, phosphonium or arsonium functions present in the grouping-Ö; ts · a is equal to 1 or to p and b is. equal to zero or to p, it being understood that, if a is equal to 1, b is equal to p and that, if b is equal to zero, a is equal to p, this process consisting in reacting an oxazine 1,3 »5 trione 2,4,6 corresponding to one or other of the following general formulas: - 29 -Ο o = cc = o 11 (\ R - N N-R '(V) 11 o «5 LJ p Γ ο Ί o = cc = o 11 -RN N. (VI) \ / ^ c 11 J p in which R, R1 and p have the meanings given above, with a salt cyanate corresponding to the formula Q (NCO) n (VII) in which Q and n have the meanings given above. 4. Process according to claim 3, characterized in that 1,3,5 5,4,6,4,6-triones of formula (V) or (VI) are used as oxadiazines 1,3,5 \ triones 2, 4,6 in which the nitrogen atoms located i \ in position 3 and 5 of the ring are not directly linked! to a carbon atom of an aromatic nucleus. \ 5. Method according to claim 4, characterized in that 1,3,5 | are used as oxadiazines | 2,4,6-triones of formula (V) or (VI) dimethyl-3,5-oxa- 1,3,5 trione 2,4,6; tmtyl-3 allyl-5 oxadiazine 1,3,5 trione 2,4,6; benzyl-3 H-5 oxadiazine 1,3,5 trione 2,4,6; 3-methyl-5-allyl oxadiazine 1,3,5 trione 2,4,6; 3-propyl-5-acetyl-oxadiazine 1,3,5 trione 2,4,6; there '(chloro-9-decyl) -3 cyclohexyl-5 oxadiazine 1,3,5 trione y,. 2,4,6; bis-1,6- (3-methyl-oxadiazine 1,3,5 trione 2,4,6) - 'fv hexane of formula: 0 0 A f, A,, H, C — NN— (CHq) / - - NN CH, (XVII) Il 11 A <A> O ^ oA, bis-aa '- (3-allyl oxadiazine 1,3,5 trione 2,4,6) -p-xylene of formula: 0 O A jn ^ · A H2C = HC-H2C — N N-H2C.y / \ VjCH2-N N - CH2-CH = CH2 «Ά. λΛ wm) poly (3-methyl-oxadiazines 1,3,5 triones 2,4,6) ;, polymers formed d, a number p of recurring units of m formula: -ch-ch2- fV Îh, (XIX) A 0 = CC = 0 II 0 N-CH, - 31 - and the polyoxadiazines 1,3,5 triones 2,4,6, polymers formed of a number p of repeating units of formula: 0 / \ 0 = C, C = 0. - - (CH2) 6 — K (XX) ç ^ L o or their mixtures · 6. Method according to any one of claims 3 to 5, characterized in that one uses, as saline cyanate, a cyanate of a mono-, bi-or trivalent metal or an cyanate of ammonium, phosphonium or d 'unsubstituted or mono-, bi-, tri- or tetrasubstituted arsonium. 7. Method according to claim 6, characterized in that a cyanate corresponding to the formula Q (NCO) n (VII) in which the meaning given above and Q denotes a radical of formula ( R1 R11 R111 Z) n RIV (VIII) rt in which Z denotes nitrogen, phosphorus or arsenic and R · * ", R" ^, R ^ "^ and R ^, which are identical or different, denote substituted or unsubstituted hydrogen or alkyl, aryl, arylalkyl or heterocyclic radicals; R ^ and R * 1, taken together, can also represent a radical IV, bivalent or in which R denotes a polyvalent radical and n is the number of ammonium, phospho- vi functions 4 <in> a ·· r "vi i iw ν" ν * ίζ r * r \ vi ^ λ r> I λ Γτν "Λΐ" vi nw avi4- Λ n rsrfin - 32 - 8. Process according to Claim 6, characterized in that a cyanate corresponding to the formula Q (NCO) n (VII) in which the meaning given above and ** Q denotes a radical of formula is used as saline cyanate V »R1 R1 --Z® — R111 - Z © -RIV-- (IX) R11 R11 Jn / 2 X II * in which Z, R and R have the meanings given III IV above, R and R are bivalent radicals and has the meaning given above. 9. Process according to claim 6, characterized in that an alkali metal or alkaline earth cyanate is used as the saline cyanate. 10. Process according to claim 9, characterized in that sodium cyanate or potassium cyanate is used as the saline cyanate. 11. The method of claim 6,! characterized in that tetramethylammonium cyanate, tetraethylammonium cyanate, tetrapropylammonium cyanate, tetrabutylammonium cyanate, tetraamylammonium cyanate, tetrahexylammonium cyanate, cyanate methane cyanate benzyltrimethylammonium, benzyltriethylammonium cyanate, benzyl cyanate -33- isopropyldimethylammonium, benzyl-tripropylammonium cyanate, phenyltrimethylammonium cyanate, phenyltriethylammonium cyanate, • dimethylpiperidium cyanate dimethylpiperidin cyanate , tetrabutylphosphonium cyanate, tetraphenylphosphonium cyanate, benzyl-triethylarsonium cyanate, tetrapropylarsonium cyanate, "> 7 * · tetraphenylarsonium cyanate, 1,4-bis (tri-methylammonium) cyanate, 1,4-dimethyl-diaza-1,4-bicyclo (2,2,2) octane cyanate, bis-1,6- (tri-methylammonium) hexane cyanate, cya nates fixed on an anionic resin of the type AMBERLITE IRA 400 (FLUKA), the ionene of formula: - ^ - (CHA - [NC0 ©] n (x) (LJ n / 2 ί l * ionene of formula: i CH, CH,: I 3 I 3 i --H - (CH2) 3 — H — CH2 —— CH2 - NCO ©; CHj CHj 1 L -ln / 2 <XI> i!; || where n is between 4 and 40,; | or their mixtures and their substituted derivatives,,; îj k B - 34 - 12. Method according to any one of claims 3 to 11, characterized in that a catalyst is used. 13. A method according to any one of claims 3 to 12, characterized in that one uses, w per equivalent of salt cyanate, approximately 0.3 to 2 equivalents * of oxadiazine 1,3,5 trione 2, 4.6 of formula (V) '· or (VI). 14. Method according to claim 13, characterized in that approximately 0.8 to 1.2 equivalent of oxadiazine 1,3,5 trione 2,4,6 of formula (V) is used per equivalent of salt cyanate where does he live). 15. Method according to any one of claims 3 to 14, characterized in that it operates in an inert organic solvent. 16. Method according to claim 15, characterized in that the solvent used is carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlorethane, 1,1-dichlorethane, the mixture of cis and trans isomers 1,2-dichlorethylene, o-dichlorobenzene, dioxane, ethyl acetate, dimethoxyethane, tetrahydrofuran, toluene, * ι ~ 1 'cc-methylnaphthalene, acetone, methyl ethyl ketone, l' acetonitrile, propionitrile, benzonitrile, benzyl cyanide, nitrobenzene, nitrotoluene, dimethylformamide, dimethylacetamide, tetra-methylurea, N-methylpyrrolidone, hexamethylphos-phortriamide, dimethyl sulfoxide and their mixtures. I - 35 - 17. Method according to any one of claims 3 to 16, characterized in that it operates at a temperature between about -80 ° C and + 250 ° C. 18. A method according to claim'17, characterized in that it operates at a temperature between about -20 ° C and + 150 ° C. î, 19. The method of claim 18, characterized in that it operates at a temperature between about 0 ° C and 70 ° C. 20. Process for the preparation of mono- molecular isocyanurates. or bisubstituted corresponding to the following general formulas: H N / \ o = c c = o R -N N — R '(XII) II o L J P l ·. 'H 1 i * I r o = c c = o j II (xiii)! -R-N N-! ^ i II o \ - 36 - in which R, R 'and p have the same meanings as in the compounds of general formulas (I) to (IV), characterized in that an acid is reacted with an isocyanurate of formulas (I) to (IV), 21. Process for the preparation of symmetrical or asymmetrical trisubstituted molecular isocyanurates w corresponding to the formulas (XIV) and (XV): R ”o = cc = o R— -N NR '(XIV) 0 LJ p OR R” o = cc = o II -RN N- (XV) II 0 LJP ^ * in which R, R 'and p have the same meanings as in the compounds of general formulas (I) to (IV), while R "represents a hydrocarbon radical , substituted or not, identical or different from R and R *, characterized in that an isocyanurate of general formulas (I) to (IV) is reacted with an organic halide or sulphate of formula: R "Y (XVI) in which R” represents a hydrocarbon radical, substituted or not, identical or different from R and R *, while Y denotes a halogen or a sulphate group · \ \ ê i