KR0145326B1 - Stabilized organic matter - Google Patents

Abstract

None.

Description

Stabilized organic matter

The present invention relates to organic materials, in particular organic materials such as mineral oils containing 1,2,4-triazole compounds as metal deactivators and / or antioxidants.

According to the invention there is provided a composition comprising at least one compound of the general formula (I) as an organic substance and a metal deactivator and / or an antioxidant:

In the above formula,

X is a general formula

Is the flag of,

R ₁ is C ₁ -C ₂₀ straight or branched chain alkali; C ₅ -C ₁₂ cycloalkyl; benzyl; Phenyl or phenyl substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or nitro, R ₂ is C ₁ -C ₂₀ straight or branched alkyl, C ₂ -with one or more oxygen atoms inserted; C ₂₀ straight or branched alkyl; C ₅ -C ₁₂ cycloalkyl; benzyl; Phenyl or phenyl substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or nitro, n is 3 or 4.

Preferred is R ₁ is C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl, benzyl, phenyl or phenyl substituted by C ₁ -C ₄ alkyl, R ₂ is C ₁ -C ₁₂ alkyl, C _5- A composition as described above, which is C ₇ cycloalkyl, benzyl, phenyl or phenyl substituted by C ₁ -C ₄ alkyl. Especially preferred as R ₂ are C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl or benzyl.

Especially preferred are R ₁ is C ₁ -C ₆ alkyl, phenyl, phenyl substituted by —CH ₃ or —OCH ₃ , R ₂ is C ₄ -C ₆ alkyl, C ₅ alkyl having two oxygen atoms inserted, or Cyclohexyl, a composition as described above.

When R ₁ or R ₂ is C ₁₀ C ₂₀ straight or branched alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl, n-pentyl, n -Hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-icosyl.

C ₂ -C ₂₀ straight or branched alkyl group R ₂ having one or more oxygen atoms inserted therein is, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 1-or 2-methoxybutyl and ethoxyoctadecyl or groups of the general formula —CH ₂ CH ₂ —O—CH ₂ —CH ₂ —O—CH ₃ .

The C ₅ -C ₁₂ cycloalkyl group R ₁ or R ₂ is for example cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl, with cyclohexyl being preferred.

Optionally substituted phenyl group R ₁ or R ₂ is phenyl, chlorophenyl, bromophenyl, methyl-, ethyl-, n-propyl- and N-butylphenyl, methoxy-, ethoxy-, n-propoxy- and n-butoxyphenyl and nitrophenyl, with preference being given to phenyl, pC ₁ -C ₄ alkylphenyls (eg p-methylphenyl) and pC ₁ -C ₄ alkoxyphenyls (eg p-methoxyphenyl).

Preferred as X are groups of the general formula (III) as described above wherein n is 3, and particularly preferred is n is 4.

The compound of general formula (I) is a known compound and can be synthesized by a known method.

A compound of formula (I), ie, a compound of formula (IA), wherein X is a group of formula (II) may be prepared by the method described in British Patent No. 1553199:

Wherein R ₁ and R ₂ have the above meanings.

In this reference, compounds of formula (IA) are defined as halo-ethers ㏊1-CH (R ₁ ) -OR ₂ with R ₁ and R ₂ having the aforementioned meanings and ㏊ 1 represents halogen, in particular bromine or chlorine. It is prepared by reacting 1,2,4-triazole.

British Patent No. 1573199 mentions only the pesticidal action of the general formula (IA) compound. Organic materials heavy metal deactivators and / or their use as antioxidants have not been proposed.

By reacting 1,2,4-triazole with butylvinyl ether in dichloroethane in the presence of orthophosphoric acid, A.M. Org. Khim. Compounds of general formula (IA) and their preparation are disclosed by the methods described in 1980, 16, 2622-3, but only compounds of general formula (IA) and their preparation are disclosed, but only specific compounds of general formula (IA) Can be prepared. Similarly, the method of Tetrabedron, 1985, 41,5955-5963 by the reaction of benzoalaldehyde dimatyl acetal in 1,2-4-triazole in hexane or toluene using p-toluenesulfonic acid as a catalyst. By the other special compound of general formula (IA) can be manufactured.

Bellowszo and neither Valesteros nor did they redefine their use as metal deactivators and / or antioxidants in organic materials for special compounds of general formula (IA).

X is a group of the general formula (II), and the compound of the general formula (I), that is, the compound of the general formula (IB) below is 2,3-dihydrofuran or 3,4-dihydro-2H-pyran and 1,2 It can be prepared by the Cbemiker Zeitung, 1986, 110, 101-8 method of Dalker and Min by reacting the 4-triazole:

Wherein n is 3 or 4.

Plate Daegen Gen Rec1. Trav. General formula (IB) wherein n is 3 by reacting 2-chlorotetrahydrofuran with 1,2,4-triazole in the presence of triethylamine using the Chim, Pays-Bas, 1979, 98, 371-380 method. The compound of can be prepared.

Compounds of general formula (IA) are novel methods of another subject matter of the present invention comprising the condensation of aldehydes of general formula (IV) and alcohols of general formula (V) with 1,2,4-triazole Can be prepared by:

R ₁ -CHO Ⅳ

R ₂ -OH V

Wherein R ₁ and R ₂ are as described above.

Preferred is the method as described above, wherein R ₁ is C ₁ -C ₆ alkyl, C ₅ alkyl or cyclohexyl having two oxygen atoms inserted.

The process of the present invention is conveniently carried out in an inert solvent in the presence of a catalyst at elevated temperatures. Examples of inert solvents are aromatic hydrocarbons such as benzene, toluene, xylene, 1,2,4-trimethylbenzene, mesitylene and cumene. Convenient catalysts are sulfuric acid, phosphoric acid, acid ion-exchange resins (e.g. Amberberst 15), acid clays (e.g. bentonite, montmorillonite and tablephoto), in particular p-toluenesulfonic acid. Preferably, the reaction is carried out while simultaneously removing water formed during the reaction, for example by azeotropic removal.

Examples of aldehyde reactants of general formula (IV) include acetaldehyde, propionaldehyde, isobutyroaldehyde, n-pentaldehyde, benzoaldehyde, 4-methylbenzoaldehyde and 4-methoxybenzoaldehyde. Alcohol reactants of formula (V) include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2- (methoxyethoxy) ethanol and cyclohexanol.

The organic material component of the composition according to the invention may be an organic material which is susceptible to degradation in the presence of metals (eg iron or copper) and / or degradation factors such as oxygen. Examples of these organic materials are mineral oils, synthetic oils, fuels, plastics and other polymers.

Of particular interest are mineral oil-based or synthetic oils such as carboxylic esters, especially lubricants used at 200 ° C. and above.

Examples of carboxyl ester synthetic lubricants include diesters of diacids and monohydric alcohols such as dioctyl sebacate or dinonyl adipate; Or triesters of trimethyl to propane and monohydric acid or mixtures of these acids, such as trimethyl to propane tripellagonite, trimethyl to propane tricaprylate or mixtures thereof; Tetraesters of pentaerythritol and monovalent acids or mixtures of these acids, such as pentaerythritol tetracaprylate; Or complex esters derived from monoacids, diacids, and polyhydric alcohols such as triesters derived from trimethylolpropane, caprylic acid and sesaceic acid; Or a lubricant of a mixture of at least one of these carboxyl esters.

Other synthetic lubricant substrates are for example those described in Schmiermittel-Taschenbuch (Huethig Verlag, Heidelberg 1974), for example phosphates, glycols, polyglycols, polyalkylene glycols and poly-αolefins.

Mineral oil based lubricant bases are preferred.

The fuel can be, for example, known hydrocarbons for internal combustion engines and mixtures thereof, and can be gasoline, diesel fuel and the like.

The composition of the present invention preferably contains 0.001 to 5.0%, more preferably 0.02 to 1.0% by weight of the general formula (I) compound by weight of the organic material.

In addition to the compound of general formula (I), the lubricant composition according to the present invention may contain other additives to improve the operability of the lubricant. These other additives include, for example, other antioxidants (e.g., phenolic antioxidants, amine antioxidants, etc.), other metal deactivators, rust inhibitors, viscosity-index enhancers, pour point inhibitors, dispersants / surfactants, and antiwear additives. .

Compounds of general formula (I), when used alone, exhibit excellent metal deactivation effects when treated metals in contact with organic materials containing metal degradation factors such as sulfur, for example in engine parts made of iron or copper, for example.

However, when the organic material itself is the primary target for deterioration, when used in the presence of trace foreign metals such as iron or copper and or in the presence of oxygen and / or hydroperoxides, the compounds of formula (I) together with other antioxidants It is much more desirable to use.

Examples of Phenolic Antioxidants

1. Alkylated Monophenol

2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-3-butyl-4,6-dimethylphenol, 2,6-di-tertiary -Butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (β-methylcyclohexyl ) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxy Methylphenol and 0-tert-butylphenol.

2. Alkylation Hydroquinone

2,6-di-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone and 2,6-diphenyl-4-octa Large fruit oxyphenol.

3. Hydroxylated Thiodiphenyl Ether

2,2'-thio-bis- (6-3-butyl-4-matylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6- Tert-butyl-3-methylphenol) and 4,4′-thio-bis- (6-tert-butyl-2-methylphenol)

4. Alkylidene-bisphenol

2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2 ′ -Methylene-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2′-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2′- Methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- ( 4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4- or -5-isobutylphenol), 2,2'-methylene-bis -[6-α-methylbenzyl-4-norylphenol], 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis -(2,6-di-tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1'-bis- (5-grade- Butyl-4-hydroxy-2-methylphenol) -butane, 2,6-di- (tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3 -Tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3n-dodecylmercaptobutane, ethylene glycol-bis- [3,3-bis (3'-tert-part) -4'-hydroxyphenyl) -butyrate], bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene and bis- [2- (3'-tert-butyl -2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] -terephthalate.

5. Benzyl Compound

1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethyl-benzene, bis- (3,5-di-tert-butyl 4-hydroxybenzyl) -sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester, bis- (4-tert-butyl-3-hydroxy- 2,6-dimethylbenzyl) dithiol-terephthalate, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5- Tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester And 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester calcium salt.

6. Acylaminophenol

4-hydroxy lauric acid anilide, 4-hydroxy stearic acid anilide, 2,4-bis-octyl mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s Triazine and N- (3,5-el-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester.

7. Monohydric or polyhydric alcohols such as methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl-isocyanurate, tee Esters of odyethylene glycol and bis-hydroxyethyl-oxalic acid diamides with β- (3,5-di-tert-butyl-4-hydroxyphenol) -propionic acid.

8. Monovalent or polyhydric alcohols such as methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-nucleic acid diol, pentaerythritol, neopentylglycol, tris-hydroxyethyl-isocyanurate, tee Esters of odyethylene glycol and di-hydroxyethyl-oxalic acid diamide with β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid.

9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as N, N-bis- (3,5-di-tert-butyl-4-hydroxy Phenylpropionyl) -hexamethylene-diamine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyfanyl propionyl) -hydrazine

Examples of amine antioxidants:

N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-tert-butyl-p-phenyllandiamine, N, N'-bis (1,4-dimethyl-pentyl)- p-phenylenediamine, N, N'-bis (1-ethyl-3-matty-anti) -p-phenyllandiamine, N, N'-bis (1-methyl-anthyl) -p-phenylenediamine, N, N'-disiplohexyl-p-phenyllandiamine, N, N'-dipanyl-p-phenyllandiamine, N, N'- (naphthyl-2-)-p-phenyllandiamine, N- Isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N-(-1-methyl-haptyl) -N ' -Phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenyllandidiamine, 4- (p-toltuene-sulfamido) -diphenylamine, N, N'-dimethyl-N , N′-di-tert-butyl-p-phenyllandiamine, difanylamine, N-allyldipanylamine, 4-isopropoxy-dipanylamine, N-phenyl-1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine (e.g. p, p'-di-tert-octyldiphenylamine), 4-n-butylaminophenol, 4-butyrylamino-phenol, 4- Nona Ilmino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino-phenol, di- (4-methoxy-phenyl) -amine, 2,6-di-tert-butyl-4- Dimethylamino-methyl-phenol, 2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-dia Mino-diphenylmethane, 1,2-di- (phenylamino) -ethane, 1,2-di-[(2-methyl-phenyl) -amino] -ethane, 1,3-di- (phenylamino)- Propane, (0-tolyl) -biguanide, di- [4- (1 ′, 3′-dimethyl-butyl) -phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated And mixtures of dialkylated tert-butyl-tert-octyl-diphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,, 4-benzothiazine, phenothiazine and n- Allylphenothiazine.

Examples of other antioxidants: aliphatic or aromatic phosphides, esters of thiodipropionic acid or thiodiacetic acid, or dithiocarbamic acid or dithiophosphoric acid.

Examples of deactivation systems for metals such as copper: triazoles, benzine derivatives, tolutriazoles and derivatives thereof, 2-mergatobenzoziazoles, 2,5-dimercapto-thiadiazoles, 5,5 ' Methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidene-propylenediamine, salicylaminoguanidine and salts thereof.

Examples of rust inhibitors:

a) organic acids and their esters, metal salts and anhydrides such as N-oleoyl-sarcosine, sorbitan-mono-oleate, ap-naphthenate, alkenylsuccinic acids and their anhydrides such as dodecenyl-succinic acid Anhydride), succinic acid partial esters and amides and 4-nonyl-phenoxy-acetic acid.

b) water-containing compounds, for example:

I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine-salts of organic and inorganic acids, for example fat-soluble alkyl-ammonium carboxylates.

II. Heterocyclic compounds such as substituted imidazolines and oxazolines.

c) phosphorus-containing compounds such as: amine salts of phosphonic acid or partial esters of phosphoric acid, zinc dialkyldithio phosphate.

d) sulfur-containing compounds such as barium-dinonylnaphthalene-n-sulfonate, calcium petroleum sulfonate.

Examples of viscosity-index enhancers: polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers and polyethers.

Examples of pour point inhibitors: polymethacrylates and alkylated naphthalene derivatives.

Examples of dispersants / surfactants: polybutenylsuccinic acid-amide or -imide, polybutenylphosphonic acid derivatives, basic magnesium-, carsum- and barium sulfonate and -phenolate.

Examples of antiwear additives: sulfur- and / or phosphorus- and or halogen-containing compounds such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolylphosphates, paraffin chlorides, alkylsulphides, aryldisulfides and trisulfides, tris Phenyl sorbothionate, diethanolaminomethyl-tolutriazole, di- (2-ethylhexyl) -aminomethyltolutriazole.

When the organic material is an organic material, such as a lubricant composition, which is susceptible to degradation by oxidation, a particularly preferred class of joint-additives for use with the compounds of general formula (I) is phenol or amine type antioxidants, in particular amine type antioxidants. Such as, for example, diphenylamine, octylated diphenylamine, N-phenyl-1-naphthylamine and N- (octylated-phenyl) -1-naphthylamine, together with the compounds of formula (I) It shows a synergistic effect.

The following examples illustrate the invention in more detail.

1. Synthesis of Test Compound

Method A, which is one of two methods, namely known methods involving the reaction of ethers with 1,2,4-triazoles (see above, Dalakker and Belozov); Or a test compound was synthesized by the method (method B) of the present invention comprising the condensation of an aldehyde of formula (IV) and an alcohol of formula (V) with 1,2,4-triazole.

Each general process is as follows:

Method A

1,2,4-triazole (13.8 G; 0.2 mol) is suspended in toluene (200 mL) and the appropriate vinyl ether (0.2 mol) is added with p-toluenesulfonic acid (0.7 g). The mixture is then heated to reflux and kept under reflux for 3 hours. The mixture is cooled to ambient temperature and washed with dilute sodium carbonate solution followed by water and finally dried over anhydrous magnesium sulfate. The dried extract is filtered and the filtrate is evaporated in a rotary evaporator. The crude product thus obtained is purified by vacuum distillation.

Method B

1,2,4-triazole (6.9 g; 0.1 mole) is suspended in toluene (300 mL) and together with p-toluenesulfonic acid (0.7 g) the appropriate aldehyde R ₁ CHO (0.1 mole) and alcohol R ₂ OH (0.1) Mole) is added. The mixture is then heated under reflux while azeotropically removing the water produced during the reaction. After heating at reflux for 10 hours, the mixture is cooled to ambient temperature and the product is isolated by the same treatment process as described in Method A.

The test compounds shown in the table below are prepared using either Method A or B.

[Examples 1 to 5]

ASTM D-130 RNFL Strip Test

A 0.05% or 0.10% solution of the test compound is prepared in a turbine grade enteric oil having a viscosity of 26.2 mm 2 / sec and S-content 0.54% at 40 ° C. with 50 ppm of sulfur dissolved.

The copper strip (60x10x1 mm) is rubbed with a 100 grade silicon carbide grit placed on a cotton moistened with petroleum ether. The rubbed strip is then immediately immersed completely in the preparation solution maintained at 100 ° C. for 2 hours. The strip is then removed, washed with petroleum ether and dried to compare the ASTM D 130 copper strip corrosion standard plot with its color. The results are summarized in the table below:

Grade 1 is a slight discoloration; Grade 2 is moderate discoloration; Grade 3 is dark discoloration; Grade 4 indicates severe corrosion. Letters A, B, C and D are used to represent subtle changes in color within a wide range of values.

The results in the table demonstrate the excellent test results obtained using the compositions according to the invention.

[Examples 6 to 46]

Rolling Cylinder Oxidation Test ASTM D-2272

0.05% of the test compound in a turbine grade mineral oil having a viscosity of 26.2 mm 2 / sec at 40 ° C, a viscosity of 4.8 mm 2 / sec, S-content of 0.54%, which may contain phenolic or amine type antioxidants, or both Prepare a solution.

Record the time it takes for the oxygen pressure in the cylinder to drop below 175 kPa below the maximum pressure.

The results obtained are described in the table below:

Antioxidant Q is a mixture of tert-butylated phenols on the market. Antioxidant R is a commercially available di-tert-octylated diphenylamine. Antioxidant S is a commercially available tert-octyl-phenyl-α-naphthylamine.

The results in the table indicate that the stabilizers of formula (I) impart elevated antioxidant properties to the lubricant compositions of the present invention when used with other amine or phenolic antioxidants.

Unless otherwise stated, all powdered milk powders and parts are by weight.

Claims (9)

Compound 1 or more of the following general formula (I) as a deteriorated organic material and a metal deactivator and an antioxidant selected from the group consisting of lubricants, mineral oils, fuels, plastics and other polymers is 0.001 to 5.0 based on the organic materials. Weight% Composition comprising:

In the above formula, X is a general formula

R ₁ is C ₁ -C ₂₀ straight or branched alkyl; C ₅ -C ₁₂ cycloalkyl; benzyl; Phenyl or phenyl substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or nitro, R ₂ is C ₁ -C ₂₀ straight or branched alkyl, C ₂ -with one or more oxygen atoms inserted; C ₂₀ straight or branched alkyl; C ₅ -C ₁₂ cycloalkyl; benzyl; Phenyl or phenyl substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or nitro, n is 3 or 4. The composition of claim 1 wherein the composition contains from 0.01 to 1.0% by weight of the compound of formula (I), based on the weight of the organic material. The composition of claim 1, wherein the organic material susceptible to degradation further comprises an additive selected from the group consisting of other antioxidants, metal deactivators, rust inhibitors, viscosity index improvers, pour point inhibitors and surfactants. The composition of claim 3 wherein the other antioxidant is an amine antioxidant. The composition of claim 4 wherein the amine antioxidant is selected from the group consisting of diphenylamine, octylated diphenylamine, N-phenyl-1-naphthylamine and N- (octylatedphenyl) -1-naphthylamine. . The compound of claim 1, wherein R 1 is C ₁ -C ₁₂ alkyl; C ₅ -C ₇ cycloalkyl; benzyl; Phenyl or phenyl substituted by C ₁ -C ₄ alkyl or C ₁₀ C ₄ alkoxy, and R ₂ is C ₁ -C ₁₂ alkyl; C ₅ -C ₇ cycloalkyl; benzyl; Phenyl or phenyl substituted by C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. The compound of claim 1, wherein R ₁ is C ₁ -C ₆ alkyl, phenyl; Phenyl substituted by —CH ₃ or —OCH ₃ , and R ₂ is C ₄ -C ₆ alkyl, C ₅ alkyl or cyclohexyl having two oxygen atoms inserted. A process for preparing a compound of formula (IA) comprising the condensation of an aldehyde of formula (IV) and an alcohol of formula (V) with 1,2,4-triazole:

Wherein R ₁ and R ₂ are as defined in claim 1. The compound of claim 8, wherein R ₁ is C ₁ -C ₆ alkyl; Phenyl; Phenyl substituted by -CH ₃ or -OCH ₃ and R ₂ is C ₄ -C ₆ alkyl, C ₅ alkyl or cyclohexyl having two oxygen atoms inserted.