DE3146056A1 - "NEW ORGANOTHIOPHOSPHONIC ACID DERIVATIVES" - Google Patents

Description

• RHONE-POULENC AGROCHIMIE, Lyon / France '

New organothiophosphonic acid derivatives

j ^ j 555 aSi Sä * SS α * η »« bS * S5 S! b SS an Sw SIS SS J2fc SiI * SS Ϊ3 SSp ^ 4v ΐΐ SS5 Sa · £ ιρ Μ »2 ^ 2 ^ j ^ ^ Si S« «ΜΪ ^^ a ib ^ b ι ·? ! ϊΐΐ SbS

description

The present invention relates to new derivatives O-alkyl- and O-aryl-S- (tert-alkyl) -alkyl-thiophosphonates, their preparation, their use as active materials in insecticidal and nematicidal compositions, in particular for protection
of plants, as well as the intermediates of these derivatives.

Certain insecticidal O-alkyl and O-aryl th'iophosphonates are known, especially from US Pat. No. 3 209O2O. However, does not wear of the compounds described in this patent in the formula the S-tert-alkyl group.

It has now been found that compounds of the formula:

R - P. (D

^SR 2

wherein:

R is an alkyl radical with 1 to 8 carbon atoms, a Halo-

■ alkyl radical with 1 to 8 carbon atoms, alkenyl with

• 2 to 8 carbon atoms, haloalkenyl with 2 to 8 carbon atoms, Alkynyl of 2 to 8 carbon atoms

■ or is haloalkynyl with 2 to 8 carbon atoms,

R. an alkyl radical with .1 to 8 carbon atoms or a Aryl radical is and. ■

Rp ■ is a tert-alkyl radical with 4 to 8 carbon atoms,

a broad spectrum of insecticidal and nematicidal activity exhibit. They are of particular interest for the control of Diabrotica sp. due to their excellent effectiveness and residual amount in the soil

One group of preferred compounds has the general formula I, "wherein:

R is an alkyl radical having 1 to 4 carbon atoms, preferably Is methyl or ethyl,

R. is an alkyl group having 1 to 4 carbon atoms Phenyl radical or · a phenyl radical substituted by at least- (and preferably one) one member selected from the group comprising an alkyl radical having 1 to 4 carbon atoms (preferably methyl), alkoxy of 1 to 4 carbon atoms (preferably methoxy), alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms or a chlorine, bromine or fluorine atom, or a nitro or cyano group, or a nitro or Is cyano or trifluoromethyl group,

Rp is a tert-butyl or tert-amyl radical.

The compounds according to the invention can be prepared by processes which are known per se in this field will. These compounds are preferably prepared, starting from an S- (alkyl) -alky 1-thiophosphonic acid halide, 'by. Action of S - (. Tert-alkyl) -alkyl-thiophosphonic acid halide for an alcohol in the presence of

Base according to the following preferred reaction scheme:

^ OR + RtQ ^{H base} ν ^R - ^p C + base. HX

^SR 2

wherein:

R, R ^, and Rp have the meanings given above and

X is a halogen atom, preferably chlorine.

The reaction is preferably carried out at a temperature of about 0 to 100 C in an organic solvent in the presence a tertiary amine or an aqueous base, such as aqueous' sodium hydroxide, carried out or, if the alkali metal alcoholate or wants to obtain alkali phenolate, from alkali metal; salt, as well as sodium.

Suitable organic solvents can be, for example Name benzene, toluene, cyclohexane, butanone-2 or the alcohol itself. ·.

Suitable tertiary amines can be trimethylamine, triethylamine, Name dimethylaniline, diethylaniline and pyridine. '

The intermediate compounds of the formula:

R -

wherein R, R ₂ and X have the meanings given above, and which are part of the present invention, can be prepared by a simple method by direct addition of thiols; to alkylphosphonic acid dihalides are produced.

The synthesis of the S-alkyl-alkylthiophosphonic acid halides is usually carried out according to methods that vary from the direct to ^ would give the thiols to the alkylphosphonic acid halides

I j / ': ": j;. 3U6056

are divorced, because this reaction is from an undesirable one Accompanied side reaction, the two halogen atoms being substituted by the alkylthiol. The ancillary ■ Action presents a particular problem when considering alkyl thiols used.

It "has now been found that the tert-alkylthiols with the Alkylphosphonic acid dichlorides react mildly and the addition of a thiol result in good yields after Scheme:.

y solution χ

_R. P ^ . + HSR ₂ + base ^medium ) R - P ^ + base HX. 0 ■ ^

in which. . ■ ·

R is an alkyl radical with 1 to 8 carbon atoms, halogen. .alkyl with 1 to 8 carbon atoms, alkenyl with 2 to 8 carbon atoms, haloalkenyl with 2 to 8 carbon atoms, Alkynyl having 2 to 8 carbon atoms or Represents haloalkynyl of 2 to 8 carbon atoms; ■. R is preferably an alkyl radical having 1 to 4 carbon atoms, especially methyl or ethyl;

"R / a tert-alkyl radical with 4 to 8 carbon atoms, preferably tertrf-butyl and tert-amyl, is and

X is a halogen atom, preferably chlorine.

As solvents which are suitable for the reaction, "" can be mentioned water and the organic solvents. In the case of water, the base is advantageously a mineral base, such as sodium hydroxide. In the case of organic solvents the base is advantageously a tertiary amine, such as Trimethylamine, triethylamine, pyridine, dimethylaniline or diethylaniline,

Suitable organic solvents include benzene, toluene, cyclohexane, acetone and butanoh-2.

Quite generally, the reaction is carried out at a temperature between about 20 and 100 ^° C.: in fact, the temperature is not critical, provided that it is sufficient for the reaction to proceed in a reasonable yield and not be too stormy. It is preferred to add the. Tertiary amine to the other reactants bei.einer temperature of from about .20 to 30 ⁰ C and then the whole of the reaction medium to a temperature of about 7.0. to 80 C to complete the reaction.

This is usually calculated using a molar ratio substantially equal to the alkylphosphonic acid halide, Thiol and base carried out, however, an excess of about 10 to 20% alkylphosphonic acid halide with respect to the remaining reactants are used. In contrast to do this, a slight excess shot (.5 to 10%) changes the thiol. and base in relation to alkylphosphonic acid dihalide die.Ausbeute not essential.

The following examples explain the preparation of the intermediates of the compounds according to the invention and of the compounds sel ^; bst as well as the insecticides. Properties of the latter. It is clear that all of the compounds described here can also be prepared by processes analogous to those described below.

example 1 S-tert-butyl-ethy1-thiophosphonic acid chloride

5 \

Cl

CH ₃ SC-CH ₀

^C8 3

To a solution of 32.0 g (0.22 mol) of ethylphosphonic acid dichloride 18 g (0.2 mol) of 2-methyl-2-propane-thiol are added to 300 ml of toluene. 22 g (0.22 mol) of triethylamine are added dropwise, with stirring, at the same time as the temperature of the reaction

»· Ν

.; j 3-U6056

- ίο -

is kept at 30 to 35 ° C. during the addition of the amine. The mixture is kept stirring at ambient temperature until the next day held. The amine hydrochloride is filtered off and the toluene solution is concentrated in vacuo 200 ml of hexane are added and the solution is filtered again.

The solvents are removed by stripping in vacuo and the liquid that remains is distilled, the product (25 g = 72.5% yield) is distilled at 72 to 73 ° C. under 0.7 mm Hg. The structure given above is confirmed by NMR proton spectrography in CDCl ₃ with "tetramethylsilane as reference.. -"

• Example 2 · ".. ■ - ■" - ..

Preparation of 0-ethyl-S-tert-butylethyl thiophosphorate

TO a solution of 8.0 g (0.048 mol) of the S-tert-rutyl-ethyl-thiophosphonic acid chloride obtained according to Example 1 in · 50. ml of toluene is given to a solution of sodium ethylate (0.04 mol) in 40 ml of ethanol. The addition is made dropwise and with stirring, keeping the reaction under nitrogen. Stirring is continued until the next day at ambient temperature, then "about 80 % of the solvents are removed in vacuo. 100 ml of toluene are added, and the sodium chloride formed in the reaction is filtered, the toluene is stripped off in vacuo and the remaining liquid is distilled. The product (5.8 g = 69.6% yield) is at 69 to 72 ° C. below mm Hg distilled. ''

The proton NMR analysis of this compound confirms this structure given above. · "

Examples 3 to 6

The procedure is analogous to how. in Example 2 for preparation of the following compounds of the formula:

R-P

whose meaning of the residues and the boiling point are indicated in the following :.

At- · - "boiling point

game RR ^ R ₂ "° C / mm Hg

3 C ₂ H ₅ CH ₃ tert .-Butyl. 64-67 / 0.7 4 C ₂ H ₅ C ₃ H ₇ tert .-Butyl 61-63 / 0.05 5 C ₂ H ₅ (CH ₃ > ₂ Cl I tert .-Butyl ' 42-43 / 0.05 C r tr
D V- ^ rI ₁ ; - C ₂ H ₅ • tert .-Amyl 56-58 / 0.07 Example 7 Manufacturing of O-Pheny1-S-tert-butyl-ethy1-thiophosphonate

To a solution of 5.0 g (0.025 mol) of S-tert-butyl-ethylthiophosphonic acid chloride, obtained according to example 1, and. * ■ · _

of 2.35 g (0.025 mol) of phenol in 20 ml of acetone are added once 2.5 g (0.025 mol) of triethylamine. The mixture becomes un- * ter nitrogen and kept with stirring at ambient temperature. . · ... ". ·

The reaction mixture is diluted with 100 ml of toluene and washed once with a 5% sodium hydroxide solution and twice with water. The solution is dried over anhydrous sodium sulfate and the solvent is removed by stripping in vacuo. The remaining liquid is subjected for 15 minutes to a high vacuum (0.2. Mm "Hg) at 6O ⁰ C., To yield the desired product, whose structure is confirmed by NMR spectrography protons in CDCl-, with ■ Tetramethylsil.an as reference substance will.

Thu! Play ο 8 to 15 '·'

None goes in αηόΐο ^ ', - κ ' il '-. Vw. ί <> \ v / i ^ Im Ι '.' · 1 u \. <) t- ) 7 .vn f ι *. * Position of the following compounds in the formula:

o ^ L

the meaning of the "residues and their boiling points" are given in the following table: '- ^ -'

Example · R. • R ₁ ^R 2 8th " ^C 2 ^H 5 . ο-methyl-phenyl text.-butyl 9 -. C ₂ H ₅ p-chloro-phenyl tert-butyl 10 ^C 2 ^H 5 Phenyl tert-amyl 11 ^C 2 ^H 5 m-trifluoromethyl c. 3 .phenyl ■ tert · AmyI 12th ^C 2 ^H 5 p-fluoro-phenyl tert-amyl. 13th C ₂ H ₅ . p-chloro-phenyl '■ -tert.-amyl. 14 - C ₂ H ₅ o-chloro-phenyl tert-amyl 15 ' ^CH 3 - phenyl tert-amyl Example 16

4.6 g of m-cresol are dissolved in 100 ml of acetone and potassium carbonate is added to. The mixture is stirred at a low temperature held for 30 minutes, then with 7.5 g of S-tert-butylmethyl-thiophosorption acid chloride offset. Stirring is continued until the next day, the medium is filtered and the solvent evaporates. "·.

After adding 100 ml of water, the medium is subjected an extraction with 100 ml of ether. The extract is washed with 5% potassium hydroxide and then with water and finally dried and evaporated to dryness and gives 4.0 g of "O-3-tolyl-S-tert-butyl-m.ethyl.rthiophosphonate. The product is identified by NKR spectrography. Its purity is over 90%. - ". ii

Example 17

Effectiveness test on Diabrotica (Corn root worrtO and Buchens panner. ( Southern army worm)

A) Actual effectiveness on Diabrotica (CRW)

The compound to be tested is in a 1% solution in Acetone or ethanol brought. The mother solution is then with an aqueous solution of Tween-2O to the desired concentration (i.e. 100, 10, -1, 0.1, 0.005 ppm) diluted. 2 ml of this solution are pipetted into a Petri dish of 9 cm, containing two layers of filter paper. Larvae in the second instar are introduced into the dish, which is then is closed. After 2 days (48 hours) exposure counts one the dead and the moribund larvae. The insecticidal activity is initially a contact effect and by steam " and very little by digestion. The results are compiled in Table I.

B) Actual effectiveness on the beech tree (Spodoptera eridania) (SAW) '. ·

.A 1% mother solution of the compound to be tested is prepared in acetone and then to the desired concentration mlt an aqueous solution containing 500 ppm Tween-20,. diluted. Leaves of Lima bean are in dipped the solution and placed it in Petri dishes (100 χ 15 mm), which contain two filter papers moistened with 2 ml of water. Each petri dish contains a sheet and is left open, that the solution dries on the leaf. Five third instar larvae of beech moth caterpillar (Spodoptera eridania) are placed on the 'sheets and' the petri dish finally closed.

The insects are kept at 25 ° C. for 72 hours, after which a mortality count is made. The results are compiled in Table I.

• f t ·. «

• - 14

Table I.

% Mortality

ι CRW 0.0 5 SAW ^ '"'" • ■ • ^ osis in ppm ^ * ^ \ ^ 100. Ο ' ¹ 75 . 500 100 Example No. ^ **** · * »^ '100 1Ö0 2 100 95 - 100 x 100 3 ■ 80 100 - ' 100 90 4th 100 70 100 100. . 15th 5 ίο α 45 90 80 15. .6 100 95 15th 100 50 7th 100 100 40 100 95 8th 100 100 70 100 100 9 10 0 35 85 100 9 5 10 .. 100 100 90 100-80 11 100 100. 55 100 60 12th 95 IQO ■ 15 100. 60 -13 ■ · 100 85 - - 100 75 14th 95 · 100 80 ιβ- 100 ' -. . -

These results show the excellent insecticidal activity of the compounds according to the invention which are used for "combating of numerous types of insects, which are plant parasites are, like beetles (especially Diabrotica sp.) and 'butterflies . (- in particular 'book clamps) can be used. In addition, no phytotoxicity whatsoever was observed on the treated plants in these tests. . ■ -. ■ '

Pur their use in practice are the'er invention Connections not used alone. Most common they are "Part of 7'usarnmenset :: -. Uncjon, which is in the range of the present Invention are, in general, in addition to the active material according to the invention, a carrier and / or a .surfactant that interacts with the active material

3H6056

is compatible, include.

In general, these compositions usually contain from 0.001% to 95% by weight active material. Their surfactant content is generally between 0, 1 and 20% by weight.

The term "carrier" in the context of the present description denotes an organic or mineral, natural or synthetic material with which the active material is associated in order to facilitate its use or its .Transport or its handling. This carrier should therefore be inert and ^{acceptable in:} agriculture. The carrier can be solid (for example clays, natural or synthetic silicates, calcium carbonate or magnesium carbonates, calcium sulfate) or liquid (for example water, alcohols, ketones, ether oxides, esters, aromatic or paraffinic hydrocarbons, halogenated hydrocarbons, petroleum fractions, "liquefied gases, etc." ).

When the carrier is water or a common organic solvent the composition preferably comprises a compound other than the active material, such as, for example a surfactant, pesticide or pesticide (e.g. an insecticide or Fungi '/. id).

The surfactant or surface active agent which is useful in the compositions of the invention can be a wetting, dispersing or emulsifying agent which can be ionic or non-ionic. One can not, for example, _T 'call .ionische such as condensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amides or amines, the alkylphenols, the fatty acid esters of sorbitol, derivatives of sucrose; anionic, such as the salts of lignosulphonic acids, alkyliarylsulphonic acids, alkylsulphosuccinates and sulphosuccinamates, amino acid derivatives, cationic, such as alkylamine or imidazoline acetates; amphoteric, such as alkylbetaines or sulfobetaines. . ·

. In addition to the active material, the carrier and the surfactant or "Surfactants can use the compositions of the invention contain other additives, such as non-surface-active dispersants, peptizers, protective colloids, thickeners, Adhesives that increase resistance to rain, stabilizers, preservatives, Corrosion inhibitors, dyes, sequestering agents ·, anti- ". Foaming agents, anti-clumping agents, "anti-gels, etc."

The compositions according to the invention can be in the form of benet '/. baren Puiverri, powders for atomization, granules, solutions, emulsifiable concentrates, emulsions, suspensions, concentrated or not, and aerosols are produced.

The wettable powders usually contain from 10 to 95% by weight active material, and they usually contain except the active material and an inert carrier from 0 to 5% by weight a wetting agent, from 3 to 10% by weight of a dispersing agent and, if necessary, from 0 to 10% by weight of one or more stabilizers and / or other additives, like penetrants, adhesives, anti-kiumpen agents or dyes.

They are usually produced by premixing the active Materials with a 'solid carrier and the wetting and dispersing agents · ^ This premix is then either equipped with a grinder, for example with pins a puiversichter, or in a grinding mill "Air Jet", the latter device being preferred for low melting point active materials. - .. ". '

As an example, the following is the weight-wise combination. Example of a wettable powder according to the invention: '· ·. ·

17 -

Active material (compound no.1) 30%

Calcium lignosulfonate (deflocculant) 5 %

Sodium isopropyl naphthalene sulfonate (wetting agent) 1%

Anti-Lump Silica · '· 30%

Kaolin 34%

The powders for dusting can be like the wettable powders but without the surfactants or surface-active agents Agents, dispersants, protective colloids, which are unnecessary in these formulations. In this case, the solid support is specially selected to carry out the grinding make it easier to absorb when the active material is liquid and guarantee flow.

The granules and micro-granules, generally with one low content of active material, can be prefabricated and then impregnated or produced in the mass, for example by atomization or extrusion. In the latter case, they need the addition of binders and hygroscopic Products to sicliorzurize their rapid fall in the ground. t.ol Tf π. They generally contain from 0.5 to 25% by weight of active substances Material, from 0 to 10% by weight of additives, such as Stab Hisier 'agents, Slow release modifiers, binders and solvents.

The emulsifiable concentrates contain the active material dissolved in a solvent (generally in an aromatic hydrocarbon) and, if necessary, an auxiliary solvent or co-solvent. to be there. Can be a ketone, an ester, an ether oxide, etc. In general, they contain from 5 to 60 % (w / v) active material, from 2 to 20% (w / v) emulsifiers and can. neri .beispielsweise be prepared by dissolving r OCE active material; in the Iiör; urirjr.ini. I. l.ol "O'lcr in O '""in f <c» ni i .seil .in ;; solvent and fcmuly.ior nu U.CiJ, \ n (' Aw-.tu '..kJ ' Al: w «l * -i ι>, <\ _} which is provided with a good stirrer and a liquid for heating or cooling.

- eat ~,

As an example, the composition of an 'emulsifiable concentrate is given below, the amounts In.g / l expressed are: ''

Active material (compound no. 1) 400 g / l

Alkali dodecylbenzenesulfonate "'.24 g / l

Nqny! Phenol, oxethylated with 10 mol of ethylene oxide 16 g / l

Cyclohexanone ■ 200 g / l aromatic hydrocarbons, make up to 11

The. concentrated suspensions, so-called "flowables", 'the Can also be used for atomization after dilution in water s i n-cl, are produced in such a way that a fluid, stable, non-settling product is preserved. .They usually contain from 10 to 50% by weight of active material, from 0.5 to 15% by weight of surfactants, from 0.5 to 10% by weight of protective colloids or anti-sediment agents, from 0 to 10% various additives, such as anti-foam agents, thickeners, stabilizers, Adhesives, anti-gels, and as a carrier water or an organic liquid in which the active material is contained is insoluble, or a mixture of the two. Certain solid organic materials or mineral salts can be in the carrier be dissolved to delay sedimentation, or as Anti-gel for the water.

These concentrated suspensions can be prepared, for example are made by dispersing the active material, pre-ground in a liquid carrier, which is water, a 'vegetable' ■ Liches or mineral oil or the emulsified mixture of both, containing the auxiliary ingredients, such as viscosity agents, Preservative and anti-gel, then grinding the dispersion in a ball mill.

.Aqueous dispersions and emulsions, for example compositions which have been obtained by using a wettable powder or an emulsifiable concentrate according to the invention .diluted with water are within the general scope of the present invention. These "emulsions" can be of the type

Know-in-oil ocJer of the oil-in-worm type, and never can have a tough consistency like that of a '·' mayonnaise ", Iureine so-called application "with very small volume", with atomization in very fine droplets, one places solutions in organic solvents, which contain 70 to 99% active material.

In addition to the compounds of formula (I), the preparation of these Compounds and the insecticides and / or nematicides, compositions containing these relates to the present invention Invention also a method for controlling the insects, the characterized in that the insects are brought into contact with an effective amount of a compound of the formula (I) brings. This insecticidal treatment can, if desired, be carried out preventively, i.e. before insects are present, by exposing the compound according to the invention to the air Parts of the plants to be protected or applied to the soil or by incorporating the product into the soil.

However, the dose of active material to be used may vary depending on the compound used and the one to be controlled Insect vary. Quite general are dosages of active

4 - 2/3

Material from 10 to 10 g / cm is well suited. When the connections as nematocides .used, they are in do-. Effective at a rate of 0.5 to 5 kg / ha. In difficult cases higher dosages can be used.

Claims (4)

Dr. F. Zumsteln sen. - D, v,%. Ässmarfri «pfyR .: Koenigsberger Dipl.-Phys. R. Holzbauer - Di'pi .'- lrVg. F. Klingseisen * - * Dr. F. Zumsiein jun. PATENTANWÄLTE SOOO Munich 2 ■ BräuhnusstraOe 4 -Telephone, collective no. 330341 Telegremm Zumpat Talax 030970 -1 Case 0519/0521/0525 Patent claims 1. New organophosphonic derivatives of the formula ^R -? V ^SR 2 wherein R is an alkyl radical with 1 to 8 carbon atoms, halogen- ' • alkyl with 1 to 8 carbon atoms ,. Alkenyl with 2 to 8 carbon atoms, haloalkenyl with 2 to 8 carbon atoms. 'atoms, alkynyl with 2 to 8 carbon atoms or ■ is haloalkynyl 'with 2 to 8 carbon atoms, R. an alkyl radical having 1 to 8 carbon atoms or a Aryirest is and · · .. ·. "· Rp "is a tertiary alkyl radical having 4 to 8 carbon atoms. 2. Compound. According to claim 1, characterized in that in the formula R is an alkyl radical having 1 to 4 carbon atoms. 3. Compound according to claims 1 and 2, characterized thereby- ' indicates that in the formula R ^ is an alkyl radical. with 1 to 4 carbon atoms is .. · .4. Compound according to claim 1, characterized in that in the formula R. is substituted by a phenyl radical or phenyl 3K60bö by at least one identical or different substituent, is selected from the group comprising an alkyl radical having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon • atoms ,. Alkylsulfonyl with 1 to 4 carbon atoms, or a chlorine, bromine or fluorine atom, a nitro, cyano, or Trifluoromethyl group. 5. A compound according to any one of claims 1 to 3, characterized in that that in the formula Rp is a tert-butyl or · ■ is tert-amyl radical. . '· 6. A compound according to any one of claims 1, 2 and 5, characterized characterized in that in the formula R is the ethyl radical, R ^ a Alkyl radical with 1 to 3 carbon atoms and R "the tert-butyl- or tert-amyl radical. 7. '. Compound according to one of claims 1, 2 and 4, characterized in that in the formula R the methyl or ethyl radical, - R ^ a phenyl radical or phenyl, substituted by a chlorine or fluorine atom or by "a methyl or methoxy" or Is trifluoromethyl radical, and R _{? Is} the ■ tert-butyl- ^ or tert-amyl radical. ■ . S-. A method for producing a compound according to any one of Claims 1 to 7, characterized in that • n e t that you can use an alkyl thiophosphonic acid halide an alcohol or phenol according to the scheme: _Base> RP ^ 1 ₊ base. HX ^SR 2 wherein X is an Ilalogen atom and the grates; R, R. and .R_ have the meanings entered above, to the reaction. brings: 9. The method according to claim 8, characterized in that an alkyl thiophosphonic acid chloride is reacted. 10. The method according to any one of claims 8 and 9, characterized in that that between 0 and IGO C in an organic solvent in the presence of a tertiary amine or a Mineral base works. . · 11. Insecticidal and / or nematocidal composition, thereby marked as being active. Material contains at least one compound according to one of Claims 1 to 7. 12. Method for protecting plants against insects, thereby . characterized in that a composition according to "claim 11 is used. · 13. New organophosphonic derivatives of the formula Il 2
O wherein R is an alkyl radical with 1 to 8 carbon atoms, haloalkyl. with 1 to 8 carbon atoms, alkenyl with 2 to 8 carbon atoms, haloalkenyl with 2 to 8 carbon atoms. Men, alkynyl with 2 to 8 carbon atoms or haloalkynyl with 2 to 8 carbon atoms, R _? is a tertiary alkyl radical having 4 to 8 carbon atoms and X is a halogen atom. . · ■ '.- 14. A compound according to claim 13, characterized in that in the formula X is a chlorine atom. 15. A compound according to any one of claims 13 and 14, characterized in that in the formula Rp is the tert-butyl or tert-amyIrest is. ' 16. A compound according to any one of claims 13 to 15, characterized ■ characterized in that in the formula R is an alkyl radical having 1 to 4 carbon atoms. 17. A method for the preparation of a compound according to any one of claims 13 to 16, characterized in that "one the reaction: C 4 ^ ₊ HX where the substituents and radicals have the same meanings as above, in a solvent in the presence of a. Base at a temperature between 20 and 100 ° C carries out. 18. The method according to claim 17, characterized in that the solvent is selected an organic solvent from the group comprising benzene, toluene, cyclohexane, Acetone and butanone-2. 19. The method according to claim 18, characterized in that " the base is a tertiary amine selected from the group comprising trimethylamine, triethylamine, pyridine and dimethylaniline and'diethylaniline, is. 20 ... method according to claim 17, characterized in that " the solvent water and the base a mineral acid ■ ■ is.