FR2802771A1 - New isocyanate-, anhydride- or epoxy-functionalized biocidal compounds, useful for grafting onto substrates, e.g. wood, to provide biocidal, e.g. insecticidal or fungicidal, activity - Google Patents

Abstract

Functionalized derivatives (I) of biocidal compounds, carrying an isocyanate, anhydride or epoxide group, are new. Functionalized biocidal compound derivatives (I) of formulae OCN-R-NH-CO-X-A (IA), Anh-R'-CO-X-A (IB) and Ep-R'-CH(OH)-X-A (IC) are new. R, R' = organic fragments; Anh = anhydride group; Ep = epoxide group; -X-A = residue of a parent biocidal compound A-XH (II). Independent claims are included for: (i) the preparation of (I); (ii) the production of substrates having biocidal activity, by contacting a substrate having functions reactive with isocyanate, anhydride or epoxy groups with (I), so that the biocidal molecule becomes covalently attached to the substrate; and (iii) substrates covalently grafted with (I).

Description

 BIOCIDAL COMPOUNDS, <B> <U> AND </ U> </ B> </ B> </ B> The present invention relates to novel biocidal compounds, more specifically reactive biocidal compounds having either an isocyanate group, an anhydride group, or an epoxide group, process for their preparation and a method for grafting these compounds. compounds on a substrate, in order to give this substrate biocidal properties, in particular antifungal properties.

The technical field of the invention is that of biocidal compounds and, more particularly, that of the protection of a substrate against bacteria, insects and other parasites, especially against fungi, using such biocides.

Certain substrates and, in particular, cellulosic compounds, such as wood, are in particular subjected to attack by fungi, in particular when these compounds are used outside and / or under favorable conditions for the growth of fungi. fungal microorganisms.

The fungicidal agents used for the treatment of cellulosic substrates, such as wood or others, are generally used by surface treatment or impregnation, incorporated into formulations, such as liquid solvents, gases and / or supports. solid. There is then the problem of leaching fungicidal agents, which occurs over time.

The same problem arises in the case of other compounds, in particular biocides, used for the treatment of substrates, in particular, for the treatment of cellulosic substrates, such as wood.

There is therefore a need for compounds, in particular, compounds having a biocidal activity, especially a fungicidal activity, which can, inter alia, maintain their activity over a long period of time, when applied to these substrates, such as cellulosic substrates, such as wood, which do not undergo a leaching process and which ensure a homogeneous treatment at the surface and in the depth of the substrate.

The object of the present invention is to provide compounds which meet, inter alia, all the needs indicated above; which do not present the defects, disadvantages and disadvantages of the compounds of the prior art and which solve the problems of the prior art.

dans lesquelles R et R' sont des fragments organiques, Anh représente un groupe anhydride, Ep représente un groupe époxyde, et -X-A est un résidu issu d'une molécule de formule A-XH (II), présentant une activité biocide. This and other objects are achieved according to the invention by a biocidal compound of formula (I), (Ia) or (Ib) OCN-R-NH-CO-XA (I) or. Anh-R '-CO-XA (I bis) or

in which R and R 'are organic moieties, Anh is an anhydride group, Ep is an epoxide group, and -XA is a residue derived from a molecule of formula A-XH (II), exhibiting biocidal activity.

It will be noted that the new biocidal compounds according to the invention have, in their structure, an available reactive group: namely, an isocyanate group or an anhydride group, which enables them to bind covalently, in particular to the hydroxyl groups, a substrate, in particular a cellulosic substrate, to give them a biocidal activity, for example fungicidal, antifungal, generally via the residue -XA.

Moreover, it was not obvious that compounds, such as those of formula (I), (Ia) or (Ib), although comprising in their molecule a residue derived from a molecule with biocidal activity, exhibit themselves a biocidal activity. In other words, it is surprising that the biocidal activity of the molecules of formula (II) is not affected by their incorporation as a residue -XA in the compounds (I), (I bis) or (I ter) according to the invention. Indeed, and as is recalled below, in the description of the process for preparing the compounds (I), (Ia) and (Ib), the latter have, surprisingly, a biocidal activity, even though the -XH function of the molecule (II), known for its biocidal activity, is consumed during the synthesis of the product (I), (I bis) or (I ter). One can think, and it is in fact often the case, that the function -XH of this molecule (II) participates in the biocidal activity or even be solely responsible for the latter. It could therefore be supposed that the transformation of this -XH function into another group, such as ester or urethane, inevitably leads to the disappearance or at least the very strong decrease in the biocidal activity. However, it is not in the compounds of the invention (I), (Ia) or (I ter), which is extremely surprising.

The compounds according to the invention thus go against a prejudice, and triumph of this prejudice by their excellent biocidal properties preserving or even improving those of the molecules of formula (II).

In addition, the synthesis of these compounds is simple to implement and it uses only known reagents, low cost, and proven reactions.

In formulas (I), (Ia) and (Ib), R and R 'are preferably organic carbon moieties.

R and R 'may therefore be chosen from aromatic cyclic fragments, such as 1,4-phenylene, aliphatic moieties, such as alkylene groups, preferably from 1 to 15 carbon atoms [(-CH2) n-] mixed aliphatic and aromatic moieties, such as benzyl groups, and all other pointing structures between reactive functions, such as oligoethers, for example (- (CH2-CH2-O) -) with n = 1 to 12 or the oligoesters, etc.

The molecule of formula A-XH is chosen from molecules having insecticidal and / or fungicidal and / or bactericidal activity.

The XH group is selected from the reactive groups having a labile hydrogen.

 XH will therefore preferably be selected from hydroxyl, amine and carboxylic acid groups (-OH: -NH2, -COOH). The preferred group is the hydroxyl group -OH-. As a result, X is preferably -O: -N; or -C0-0-.

Such molecules, including a labile hydrogen group such as a hydroxyl group and having this activity, are known to those skilled in this field of the art.

The group A will therefore be generally selected from groups comprising a phenyl and / or triazole ring derived from molecules with biocidal activity.

More preferably, the group A is derived from fungicidal compounds, comprising a triazole ring, such as cyproconazole and tebuconazole or alternatively a biphenyl type group, such as 2-phenylphenol.

c'est-à-dire que le groupe A a la formule

tandis que le tébuconazole répond à la formule suivante

Le groupe A est alors le radical de formule

Le groupe A peut aussi être issu des composés de la famille du 2-phénylphénol et répondre ainsi à la formule suivante

L'invention concerne également un procédé de préparation des composés biocides de formule (I) ou (I bis) ou (I ter), ci-dessus, dans lequel on fait réagir un composé de formule (II) A-XH (II) dans laquelle A-X a la signification déjà donnée ci-dessus, avec un composé de formule (IX) OCN-R-NCO (IX) ou un composé de formule (IX bis) . Such compounds are described, for example, in the US-A-5 <B> 691,363, </ b>, in the description of the year can <B></B> reParter. Cyproconazole has the following formula

that is, group A has the formula

while tebuconazole has the following formula

Group A is then the radical of formula

Group A can also be derived from compounds of the 2-phenylphenol family and thus respond to the following formula

The invention also relates to a process for preparing the biocidal compounds of formula (I) or (Ia) or (Ib), above, in which a compound of formula (II) A-XH (II) is reacted. in which AX has the meaning already given above, with a compound of formula (IX) OCN-R-NCO (IX) or a compound of formula (IXa).

tels que définis plus haut. Anh-R'-Anh (IX bis) or a compound of formula (IX ter) Ep-R'-Ep in which Anh, Ep, R and R 'have the meaning already given above, to give a compound of formula (I) or a compound of formula (Ia) OCN-R-NH-CO-A (I) Anh-R'-CO-XA (Ia) or a compound of formula (Ib)

as defined above.

The compounds of formula (II) have already been mentioned above. The preferred compounds are 2-phenylphenol (or 2-hydroxybiphenyl) (VIII), tebuconazole, i.e. (a- [2- (4-chlorophenyl) ethyl] -a- [1, 1- dimethylethyl) -1H-1,2,4-triazole-1-ethanol) or cyproconazole, that is to say (α- (4-chlorophenyl) -α- (1-cyclopropenylethyl) -1H-1 , 2,4-triazole-1-ethanol).

Parmi les composé dianhydrides de formule (IX bis), on peut citer, de manière préférée, le dianhydride de l'acide 1,2,4,5-benzènetétracarboxylique. Among the isocyanate compounds of formula (IX), there may be mentioned, preferably, 1,4-phenylene diisocyanate, the formula of which is

Among the dianhydride compounds of formula (IXa), there may be mentioned, preferably, the 1,2,4,5-benzenetetracarboxylic acid dianhydride.

The reaction of the biocidal compound of formula (II) with the isocyanate compound of formula (IX) or the dianhydride compound of formula (IX bis) or the diepoxide compound of formula (IX ter) is generally carried out in a solvent generally chosen from dichloromethane, tetrahydrofuran, pyridine and N, N'-dimethylformamide.

The reaction is generally carried out at reflux of solvent, that is to say at a temperature close to its boiling point.

The temperature of the reaction will therefore generally be 60 to 70 ° C. and the duration of the reaction will generally be from 2 to 5 hours.

The reaction is generally carried out under an inert atmosphere, for example nitrogen or argon. The reaction is generally carried out in the presence of a catalyst chosen from dibutyltin laurate (DBTL) and N, N'-4 dimethylaminopyridine.

Si le composé de formule (II) est la cyproconazole (IV), alors le procédé de préparation du composé selon l'invention peut être représenté par l'équation suivante

Le procédé de préparation selon l'invention est tout à fait analogue, dans le cas où le composé de formule (II) est la tébuconazole (VI). At the end of the reaction, the product obtained (I) (I a) or (I ter) is generally crystallized, for example by adding an immiscible solvent, such as hexane, and then separated, for example by filtration under vacuum and then generally dried, for example in the oven, for a period of 24 to 48 hours. In the case of a compound of formula (II), which is 2-hydroxybiphenyl, the process for preparing the compound according to the invention can be represented by the following equation

If the compound of formula (II) is cyproconazole (IV), then the process for preparing the compound according to the invention can be represented by the following equation

The preparation process according to the invention is entirely analogous, in the case where the compound of formula (II) is tebuconazole (VI).

In the above formulas, R is preferably 1,4-phenylene.

le a-(4-chlorophényl)-a-(1-cyclopropényléthyl)-1H- 1,2,4-triazole-N-(4-phénylène-isocyanato)-uréthane ; le a-[2-(4-chlorophényl)éthyl]-a-[1,1-dimëthyléthyl)- 1H-1,2,4-triazole-N-(4-phénylène-isocyanato)-uréthane. The compounds of formula (I) or (Ia), still preferred, according to the invention, will therefore be the following compounds: the compound of formula

α- (4-chlorophenyl) -α- (1-cyclopropenylethyl) -1H-1,2,4-triazole-N- (4-phenylene-isocyanato) -urethane; α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-N- (4-phenylene-isocyanato) -urethane.

The new compounds of formula (I) or (Ia) or (I ter) have, as such, a biocidal activity, for example antifungal activity.

As already mentioned above, this fact is totally surprising. In fact, it was absolutely not possible to predict that a compound of formula (II), well known for its biocidal activity, would actually give, after reaction with a compound of formula (IX) or (IX bis) or ( IX ter) a compound (I) or (Ia) or (I ter) having likewise a similar biocidal activity.

If, in addition, the biocidal activity of the starting compound is due to the function -XH, which is consumed during the reaction carried out in the process of the invention, the fact that the final compound (I) or (I bis) or (I ter) has a biocidal activity, even though, the function, which gave it these properties, disappeared during its synthesis is even more surprising.

Thus when reacting 2-hydroxybiphenyl (orthophenylphenol), whose biocidal activity is, it seems, due to the hydroxyl group with a dianhydride, the final compound (Ia) has, surprisingly, an excellent biocidal activity, whereas it should have, on the contrary, expected that it disappears, precisely because of the disappearance, consumption, of the hydroxide group during the reaction.

The compounds (I), (Ia) or (I ter) can be used directly as a biocide under conditions which can be easily determined by those skilled in the art, in particular as regards carriers, diluents, concentrations, doses, mode of application, etc., to be used.

The invention therefore relates to the use of the compounds of formula (I), (Ia) or (Ib) as a biocide, and the biocidal compositions comprising these compounds of formula (I), (Ia) or ( I ter).

These compositions can be solid, liquid, gaseous, with, for example, a suitable carrier or diluent.

However, because the compounds of formula (I), (Ia) or (Ib) have the fundamental characteristic of having in their structure an isocyanate or anhydride or epoxide reactive group, they will preferably be used to prepare a grafted substrate having a biocidal activity, for example a fungicidal agent, since said isocyanate or anhydride or epoxide reactive group is capable of readily covalently bonding to a substrate having reactive functions, for example hydroxyl functions.

The invention thus further relates to a process for the preparation of a substrate provided with a biocidal activity (or grafting method), wherein a substrate comprising reactive functional groups capable of reacting with the isocyanate or anhydride group or epoxide, is brought into contact with the biocidal compound of formula (I), (Ia) or (Ib), in which R, R ', X, A, Ep and Anh have the meaning already given above, by means of a substrate is obtained which is covalently bound to molecules exhibiting biocidal activity.

During this process, a covalent bond is thus created because of the reaction between the reactive functions of the substrate, such as wood and the isocyanate functions, and a substrate is obtained, to which a molecule is grafted, provided with a group (A) conferring on said substrate biocidal properties.

The grafting of the molecule of compound (I), (Ia) or (Ib), is perfectly directed and controlled.

Fastening, with a satisfactory yield, molecules (I), (Ia) or (I ter) on the substrate.

According to the invention, the isocyanate group or the anhydride group or the reactive epoxide group of the compound (I) or of the compound (Ia) or of the compound (I ter) and the residue -XA are preferably arranged on each side. else of the fragment R or R ', for example in the para position around a benzene ring, said fragment preferably having, in this case, the advantage of not being deformed.

The grafting according to the invention, of a molecule (I), (I bis) or (I ter) biocidal activity on a substrate, is not only possible, but is done in excellent conditions, preserving the activity biocide of the grafted molecule, activity that is fully transmitted to the substrate.

Indeed, the amount of molecule with active principle (that is to say of molecule (I) or (I bis) or (I ter), the term active ingredient designating, in fact, the residue XA), setting work is weak, much lower than that of an impregnation treatment; as in any grafting, there is no leaching of the molecule active principle, since it is bonded to the substrate via covalent bonds, furthermore, we obtain a grafting with a very high yield, and a small proportion of molecules (I) or (Ia) or (Ib) with active ingredient (A) not used. The grafting and the amount of grafted molecules are perfectly controlled, this grafting is carried out uniformly throughout the substrate, both on the surface and generally in the entire volume of C * elui-ci.

However, it is possible that the molecules of formula (I) or (Ia) or (I ter) have a substantial molecular size and that this prevents their good diffusion into the substrate. However, in this case, the process allows the efficient treatment of surface substrates or highly porous substrates, particularly paper which is a very open medium.

The grafting process according to the invention does not in any way harm the other properties of the substrate, whether it be the physical, chemical or other mechanical properties; in other words, the substrate is not damaged and, in particular, the external appearance of the substrate is not stressed and the mechanical properties are not degraded.

The grafting method according to the invention is simple, easy to implement and inexpensive, it is indeed not necessary to perform heavy operations of organic synthesis to achieve the grafting on the substrate, such as the wood or to synthesize complex reagents; all the chemicals necessary for the process are generally commercially available and of low cost. The invention further relates to a graft substrate to which a molecule of formula (I) or (Ia) or (Ib) is covalently bonded.

The grafting process is described in more detail in the following.

The substrate, treated according to the invention, is a substrate comprising reactive functions.

The reactive functions of the substrate are generally chosen from hydroxyl functions, anhydride functions and epoxide functions. The preferred functions are the hydroxyl functions.

The substrate may be chosen from all the substrates having reactive functions, mentioned above, so that the substrate may be chosen from cellulose-based products, paper, cardboard, wood, cork, organic polymers, plastics, natural, artificial or synthetic textiles, such as cotton, wool, polyvinyl alcohol fibers), mineral substrates such as glass.

However, the preferred substrate is wood, in which case the reactive functions are hydroxyl functions.

Hydroxyl functions -OH are, in fact, carried by the essential constituents of wood, such as cellulose, hemicellulose and lignin.

In the grafting method according to the invention, the substrate is brought into contact with a reactive compound of formula (I) or (Ia) or (Ib) in which A, X, R, R ', Ep and Anh have already defined above. The isocyanate group of the compound (I) or the anhydride group of the compound (Ia) or the epoxide group of the compound (I ter) will react with a reactive function of the substrate to create a covalent bond.

The bond established between the substrate and the compound (I) will be, for example, a urethane bond, when the reactive function of the substrate is a hydroxyl function, while the bond between the substrate and the compound (I) will be an ester bond, when the reactive function of the substrate is an anhydride function and an ether bond, when the reactive function of the substrate is an epoxide function.

According to the invention, the isocyanate group or the anhydride group or the epoxide group, and only the isocyanate group or the anhydride group or the epoxide group of the compound (I) or (Ia) or (I ter) react with a single function reactive substrate and all other reactive groups, optionally present in the molecule (I) or (Ia) or (I ter), especially in the residue A, remain available, for example to give the desired activity to the substrate, and do not react with the reactive functions of the substrate.

The biocidal property that said active molecule AH, via the X-A residue, is capable of conferring on the substrate, such as wood, is generally selected from bactericidal, fungicidal, insecticidal and protective properties against various parasites.

According to the invention, the substrate is not altered or damaged by the grafting process, that is to say that the properties, other than those that one wishes to confer or modify, are not degraded: for example the appearance and mechanical properties are not affected.

The bringing into contact of the active compound of formula (I) or (Ia) or (Ib) with the substrate can be carried out in any suitable manner, but it is preferably carried out by placing the substrate in a solution of said compound of formula (I), (Ia) or (I ter), for example by immersing in such a solution.

The solvent may be any suitable organic solvent, but is preferably selected from N, N'-dimethylformamide (DMF), pyridine, or tetrahydrofuran.

The reaction is generally carried out in the presence of a catalyst, such as dibutyltin dilaurate.

The solvent, such as pyridine, may also act as a blowing agent.

The concentration of the molecule (I) in this solution is generally from 1 to 2 mol / l. The amount of molecule (I) used is very small and, in any case, much less than that used, during impregnation.

The reaction is generally carried out with stirring, at a temperature generally of 70 to 80 ° C., for a duration ranging from 24 to 32 hours.

Once the reaction is complete, the substrate is generally washed at a temperature, for example 40-70 C, with a solvent, such as tetrahydrofuran, for a period of generally 24 to 48 hours.

Then, the washed substrate is generally dried, for example under vacuum, in the oven for a period of 24 to 48 hours.

X est de préférence -0-. The geometrical configuration of the molecule (I), with biocide active ingredient on the substrate, such as wood, is as follows

X is preferably -O-.

X est, de préférence, -0-. For example, the grafted substrate has the following formula, in the case of wood and a R group which is 1,4-phenylene.

X is preferably -O-.

Par exemple, le substrat greffé répond à la formule suivante, dans le cas du bois et d'un groupe R', qui est un groupe issu du dianhydride de l'acide 1,2,4,5-benzènetétracarboxylique.

-X- est, de préférence, -0-. The molecule (Ia) will give a grafted substrate of formula

For example, the grafted substrate corresponds to the following formula, in the case of wood and a group R ', which is a group derived from the dianhydride of 1,2,4,5-benzenetetracarboxylic acid.

-X- is preferably -O-.

But, -X-A can have the meaning already given above.

It is generally advantageous to use, during the contacting, a swelling agent, chosen from pyridine, and dimethylformamide (DMF), this blowing agent has, for example, the property of opening the structure of the wood. to facilitate reagent access to wood constituents, such as cellulose, hemicellulose and lignin.

The process of. grafting according to the invention is particularly applicable to the field of wood preservation, vis-à-vis different types of aggression, depending on the molecules with active ingredient that are used. Thus, for wood kept outside, being part, for example, cladding, windows, frames, doors, gates, stakes, poles, garden furniture, etc., we can choose any type of biocides, such as bactericides , fungicides, and insecticides, as active ingredient molecules for protecting wood from the elements.

For applications in the building, where the wood is part of frames, furniture, stairs, floors, etc., it is relevant to choose insecticides, as molecules with active ingredient.

In addition, the process has been validated on old wood, whether it is dry wood or waterlogged wood.

Another possible, but more marginal, use of the invention is therefore to treat wooden cultural heritage objects to make them, for example, more resistant to biological attacks by fungi, insects and bacteria. .

In addition to the field of wood, the grafting process according to the invention can also find application in the field of the food industry, in order to confer biocidal and, in particular, fungicidal properties, on packaging and packaging, for example cardboard, paper, plastic, or other, or surfaces of the devices used in production.

The grafting process according to the invention can also be applied in the medical field, in view of conferring biocidal properties, in particular to textiles used in this sector, for blouses, sheets, etc.

In general, the biocides, in particular the fungicides used, protect the container by the formation of biological barriers, they do not pollute because, according to the invention, they are bound by covalent bonds which prevent their leaching. .

The invention will now be described with reference to the following examples, given by way of illustration and not limitation.

<U> Example 1 </ U> <U> Preparation of the compound of formula </ U> (XIV) 5 g of 2-hydroxybiphenyl in solution in 40 ml of Tetrahydroduran (THF) are added dropwise, in 15 - 30 minutes. minutes, to a stirred solution of 40 ml of THF containing 6.73 g of 1,2,4,5-benzenetetracarboxylic acid dianhydride and 0.18 g of 4-N, N-dimethylaminopyridine of dibutyltin laurate (DBTL) the mixture is refluxed with the solvent (Teb = 65 ° C.).

<U>Exemple 2</U> <U>Préparation du (a-(4-chlorophényl)-a-(1-</U> cyclopropényléthyl)-1H-1,2,4-triazole-N-(4-phénylène- isocyanato)-uréthane) <U>(2)</U> On place une solution de 4,71 g de 1,4-phénylène diisocyanate dans 40 ml de tétrahydrofuranne (THF) et 2 gouttes de DBTL, dans un bicol de 250 ml, muni d'un agitateur magnétique, d'un réfrigérant et d'un thermomètre. On ajoute goutte à goutte une solution de 5 g de cyproconazole dans 40 ml de THF. Le mélange est ensuite chauffé à reflux du solvant, pendant 1 heure. Après refroidissement à température ambiante, on cristallise le produit de réaction par dilution dans de l'hexane ; une fois filtré, il est alors séché au four Büchi , à 90 C, pendant 24 heures. The reaction is carried out in a controlled humidity chamber under an inert atmosphere (nitrogen) for 5 hours. After the reaction is complete, the mixture is diluted with hexane and the reaction product, thus crystallized, is recovered by filtration. The latter is then dried in the Buchi oven under vacuum at 90 ° C. for 24 hours.

<U> Example 2 </ U><U> Preparation of (α- (4-chlorophenyl) -α- (1 - </ U> cyclopropenylethyl) -1H-1,2,4-triazole-N- (4-) phenylene-isocyanato) -urethane) <U> (2) </ U> A solution of 4.71 g of 1,4-phenylene diisocyanate in 40 ml of tetrahydrofuran (THF) and 2 drops of DBTL is placed in a bicolor. 250 ml, equipped with a magnetic stirrer, a condenser and a thermometer. A solution of 5 g of cyproconazole in 40 ml of THF is added dropwise. The mixture is then heated under reflux of the solvent for 1 hour. After cooling to room temperature, the reaction product is crystallized by dilution in hexane; once filtered, it is then dried in the Buchi oven at 90 ° C. for 24 hours.

<U> Example 3 </ U> <U> Demonstration of the activity </ U> <U> antifungal of the products prepared in Examples 1 </ U> <U> and 2 ((1) and (2 The 10 target strains were isolated from the wood: Myrothecium verrucaria - Trichoderma Viride - Chaetomium Globusum - Phanerochaete Chrysosporium - Oxysporus Sp.

- Coprinus Cinereus - Coprinus Micaceus - Trametes Sp.

- Gloeophyllum Trabeum - Pleurotus Ostreatus The product to be tested ((1), (2)), dissolved in dimethylsulfoxide (DMSO), is added to a medium with malt extract (2%), agar at $ 1.5 , sterilized, for final concentrations of between 0.01 nM and 1 nM.

The media thus obtained are distributed in Petri dishes 90 mm in diameter. For each product concentration, a central implant of each of the target strains is made; incubation continues at 22-25 C under daylight. The diameters of the colonies obtained are measured over a period of 14 days.

The observation of a total absence of growth allows the estimation of the minimum concentration necessary for the manifestation of the antifungal activity of the tested product.

The biological results effectively show antifungal activity of the products prepared in Examples 1 and 2.

<U> Example 4 </ U> <U> Example of Grafting on Paper </ U> WHATMAN 5 g of tebuconazole in solution in 40 ml of pyridine are added dropwise in 15 - 30 minutes in a stirred solution of 40 ml of pyridine containing 2.60 g of 1,4-phenylene diisocyanate [1/1] at 65 ° C. The reaction is continued under a nitrogen atmosphere for 1 hour, after which time 0.21 g of paper is added. WHATMAN composed of 99.9 cellulose. The grafting reaction is carried out for 2 hours at 80 ° C. The filter paper is then passed to the sodium hydroxide for 48 hours and then dried in a Buchi oven, under vacuum, for 48 hours. <U> Example 5 </ U> <U> Example of grafting on a sample of </ U> <U> wood </ U> The operation is carried out in two steps. 5 g of tebuconazole in solution in 40 ml of pyridine are added to a stirred solution of 40 ml of pyridine containing 2.60 g of 1,4-phenylene diisocyanate at 70 ° C. The reaction is continued under a nitrogen atmosphere for 1 hour. , time after which is introduced into the reactor a sample of wood (Scots pine) size 1.5 x 0.5 x 2 cm3, previously dried. The grafting reaction of the biocidal product on the -OH functions of the wood is carried out at 80 ° C. for 24 hours at 3 days. The sample is then passed to the soybean for 48 hours and then oven-dried in a vacuum oven for 48 hours.

The biological tests carried out on the products of Examples 4 and 5 show, like Examples 1 and 2, antifungal activity of the products prepared.

Claims (3)

1. A biocidal compound of formula (I), (Ia) or (I ter) OCN-R-NH-CO-XA (I) or Anh-R'-CO-XA (Ia) or in which R and R 'are organic moieties, Anh represents an anhydride group, Ep represents an epoxide group, and -XA is a residue derived from a molecule of formula A-XH (II), exhibiting biocidal activity. The compound of claim 1, wherein the R and R 'moieties are organic carbon moieties selected from aromatic cyclic moieties; aliphatic fragments mixed aromatic and aliphatic fragments; and all other bridging structures between reactive functions. The compound of claim 2, wherein R and R 'are selected from 1,4-phenylene moieties, alkylene moieties, benzyl group, oligoesters and oligoethers. 4. A compound according to any one of claims 1 to 3, wherein XH is selected from reactive groups having a labile hydrogen. The compound of claim 4, wherein X is -O-, -N-, or -C0-O-. 6. A compound according to any one of claims 1 to 5, wherein -X-A is a residue derived from a molecule selected from the molecules having insecticidal and / or fungicidal and / or bactericidal activity. 7. A compound according to any one of claims 1 to 6, wherein the group A is selected from groups comprising a phenyl and / or triazole ring, derived from biocidal molecules. 8. A compound according to claim 7, wherein the group A is the group of formula (V) the molecule of formula (II) being cyproconazole. 9. Compound according to claim 7, wherein the group A is the group of formula (VII) the molecule of formula (II) being tebuconazole. 10. A compound according to claim 7, wherein the group A is the group of formula following the molecule of formula (II) being 2-phenylphenol. 11. Compound of formula (Ia) which is the compound of formula 12. Compound of formula (I) which is α- (4-chlorophenyl) -α- (1-cyclopropenylethyl) -1H-1,2,4- triazole-N- (4-isocyanato-phenylene) -uréthane. A compound of formula (I) which is α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-N- (4-phenylene) isocyanato) -uréthane. 14. Use of a compound of formula (I), (Ia) or (Ib) according to any one of claims 1 to 13 as a biocide. 15. Biocidal composition comprising the compound of formula (I), (Ia) or (Ib) according to any one of claims 1 to 13. 16. Process for the preparation of a biocidal compound of formula (I), ( I a) or (I ter) according to any one of claims 1 to 13, wherein a compound of formula (II) A-XH (II) is reacted with a compound of formula (IX). OCN-R-NCO (IX); or a compound of formula (IX bis) Anh-R'-Anh (IX bis) or a compound of formula (IX ter) Ep-R'-Ep (IX ter) to give a compound of formula (I) OCN-R -NHCO-XA (I); or a compound of formula (Ia) Anh-R'-CO-XA (Ia) or a compound of formula (Ib) 17. The process according to claim 16, wherein the compound of formula (II) is chosen among 2-phenylphenol, tebuconazole and cyproconazole. 18. Process according to any one of claims 16 and 17, in which the compound of formula (IX) is 1,4-phenylene diisocyanate, and the compound of formula (IXa) is the dianhydride of acid 1, 2,4,5-benzenetetracarboxylic. 19. A process according to any one of claims 16 to 18, wherein the reaction is carried out in a solvent selected from dichloromethane, tetrahydrofuran, pyridine and N, N'-dimethylformamide. 20. The method of claim 17, wherein the reaction is carried out at reflux of solvent for a period of 2 to 5 hours. 21. A process according to any one of claims 16 to 20, wherein the reaction is carried out in the presence of a catalyst selected from dibutyltin laurate, and N, N'-4, diemethylaminopyridine. A process for preparing a substrate provided with a biocidal activity, wherein a substrate, comprising reactive functions capable of reacting with the isocyanate group or the anhydride group or the epoxide group, is contacted with the biocidal compound of formula (I) or (Ia) or (Ib), according to any one of claims 1 to 15, whereby a substrate is obtained, to which are covalently bound molecules having a biocidal activity. 23. The method of claim 22, wherein said reactive functions of the substrate are selected from hydroxyl functions, anhydride functions, and epoxide functions. 24. A method according to any one of claims 22 and 23, wherein the substrate is selected from wood, cellulose-based products, such as paper, cardboard, wood, cork, plastics and polymers. organic, natural, artificial and synthetic textiles, such as cotton, wool, polyvinyl alcohol, and mineral substrates, such as glass. 25. A method according to any one of claims 22 to 24, wherein the contacting of the substrate, comprising reactive functions, is carried out in the presence of a blowing agent. 26. The method of claim 22, wherein said blowing agent is selected from pyridine, and dimethylformamide (DMF). 27. The graft substrate covalently bound to biocidal compounds of formula (I), (Ia) or (Ib) according to any one of claims 1 to 13. 28. Grafted substrate according to claim 27, the formula of which is the next one     29. graft substrate according to claim 27, the formula of which is the following

    30. Grafted substrate according to claim 27, the formula of which is the following

    31. Grafted substrate according to claim 27, the formula of which is as follows