LU80050A1 - NOVEL AMIDOXIMES DERIVATIVES, THEIR PREPARATION AND PHYTOHORMONAL COMPOSITION AND HERBICIDES CONTAINING THEM - Google Patents

Description

f ·. ^ - ·

The main patent application No. 75 * 766 - 'relates to new derivatives of amidoximes of general formula:

R

N - O - CH - COOR.

1.

5 AT - -, (D

•. nh2 their preparation, the compositions containing them and the treatments using these compositions.

In the general formula (I), R represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms or phenyl, represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, or a metal atom,

Ar represents a phenyl radical substituted by 1 to 3 substituents,. identical or different, chosen from halogen atoms and radicals: alkyl containing 1 to 4 carbon atoms, hydroxy, alkyloxy of which the alkyl part contains 1 to 4 carbon atoms, alkylthio of which the alkyl part contains 1 to 4 carbon atoms, alkylsulfinyl 'of which the alkyl part contains 1 to 4 carbon atoms, alkylsulphonyl of which the alkyl part contains 1 to 4 carbon atoms, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, carboxy, alkyloxycarbonyl of the alkyl part contains 1 with 4 carbon atoms, nitro, amino, alkylamino, the alkyl part of which contains 1 to 4 carbon atoms, dialcoylanino, each alkyl part of which contains 1 to 4 carbon atoms, acylamino, of which the acyl part contains 1 to 4 atoms carbon, alkyloxycarbonylamino of which \ the alkyl part contains 1 to 4 carbon atoms, azido, alkanoyl ('i containing 1 to 4 carbon atoms, sulfamoyl optionally substituted on nitrogen' by one or two groü pes alkyl of which each alkyl part contains 1 to 4 carbon atoms, or phenyl / or a heterocyclic aromatic radical with 5 members which contains as hetero-atom an atom of oxygen, sulfur or nitrogen and is optionally substituted for it by a halogen atom, an alkyl radical containing 1 to 4 carbon atoms, an alkyl radical of which the alkyl part contains 1 to 4 carbon atoms, an alkylthio radical of which the alkyl part contains 1 to 4 carbon atoms , a phenylalkyl radical in which the alkyl part contains 1 to 4 carbon atoms. and which is itself optionally substituted.

According to the invention, - products of general formula (I) can be obtained according to one / of the following methods: ·. j jf '(Ji'.

f 2

The present patent application for addition to the main patent No. 75 * 766 relates to new amidoxime derivatives. according to the general formula I cited above.

It also relates to the preparation of these compounds and to the compositions containing them.

The compounds according to the present application correspond to the general formula:

_ _ R

25 '

^ ^ N - 0 - CH - A

___-, formula II

it \ NH2. in which: R represents a hydrogen atom or an alkyl radical containing from I to 4 carbon atoms. · & A represents a cyano group or a radical of general formula: - CO - N ^ 1 R2 in which Rj and R2 *, identical or different, each represent a hydrogen atom {an alkyl radical containing from I to 4 atoms carbon, an optionally substituted phenyl radical, or an amino radical itself optionally substituted.

• - When R represents an alkyl radical, the / compounds according to formula II exist in two forms optically? / / ο / "/ j '/ 1' -...... - - / * c" 3 mistletoe isomers are also included in the present invention.

The present application preferably relates to the compounds corresponding to the general formula:

x.N - 0 - CEL - A

^ - (T formula III

\ nh2 in which: 10 A represents a cyano radical or a radical of general formula: - CO - N --— * 1. 'in which, R ^. and R2, identical or different, each represents a hydrogen atom, an alkyl radical containing from 1 to 4 carbon atoms, a phenyl radical, or an amino radical itself optionally substituted by one or two radicals, identical or different , chosen from alkyl radicals containing from I to 4 carbon atoms or the phenyl radical. The compounds according to the present application show remarkable properties which make them particularly useful in the agricultural field.

When used in doses between 0.1 and 100 g / hl of water, they exhibit phytohormonal properties similar to those of indolylacetic acid and derivatives of phenoxyacetic acids. They are mainly useful for promoting the fruiting of certain plants (toiaates), preventing the fall of leaves or fruits or even increasing the formation of roots.

When used at doses of between 0.5 and 10 kg / ha, the compounds according to the present application show herbicidal properties, in particular on dicotyledons both in pre and post-emergence.

The compounds according to the invention can be prepared according to several methods which are also the subject of the present application. The compounds according to formula II for these. ^ Rt A represents a group - C0‘- can be obtained according to a

process known per se, by action of ammonia or of an amine, of general formula NH Rj R2, in which R ^ and R2 have the same signiA

(• l Λη rfHû rl an o la f 1 TT piiv un r \ rv • Ρηντητι 1 ο / vano v * a Τλ / /. * - 4

• R

q ^ N-O-CH-B formula IV

./SV, X

I "ΙΓ ^ nh2 5 optionally in the form of hydrochloride" In formula IV, "R has the same meaning as in formula II and B represents either a radical - CO - 0 - R ^, in which R ^ represents an alkyl radical containing from I to 4 carbon atoms, ie a radical-COCl '.

When B represents a --CO - 0 - R3 radical, the reaction is carried out at a temperature of between 15 ° C. and about 100 ° C., optionally £> us pressure, either in an organic solvent medium, for example in alcoholic solution or * hydroalcoholic, or in the absence of solvent when the reagents are liquid under the conditions of the reaction. .15 The preparation of the compounds corresponding to formula IV, for which B represents a radical - CO - O ~ R ^, has been described in the main application No .75 · 7δ6 ~,

When B represents a radical -C0-C1, the reaction is carried out by reacting the hydrochloride of compound 20 of formula IV with the compound of formula NH R R3, at a temperature between 15 and 50 ° C approximately, ie in a solvent medium inert, in the absence of solvent when the reactants are liquid under the reaction conditions.

\ The compounds of formula IV, for which B

25- ^ represents a radical -CO Cl, can be obtained according to the conventional processes for the preparation of acid chlorides, from the corresponding acids, the preparation of which has been described in, 1 main application No -75 "-766 2 - The compounds according to formula II, for which A represents a cyano radical, can be obtained according to a process known per se, by reacting an amidoxime of general formula:

-OH

i —H— 35 ‘U_ [X NH? on a nitrile halogeno of general formula;

R

i / Y - CH - CM / in which ^ R has the same meaning as in formula II 4 '5 Y represents a halogen atom, in the presence of an alkaline condensing agent such as a quaternary ammonium hydroxide , sodium hydroxide or potassium hydroxide, in a hydroorganic solvent medium such as a dimethylformamide / water mixture, at a temperature which can vary from approximately 5 ° C. to 80 ° C.

The following examples illustrate the invention without, however, limiting it.

Example I: Preparation of O-carbamovlmethvl-.

. thiophene carboxamidoxime-2 10 (compound I)

A solution of 20 g of O-ethoxycarbonylmethyl-thiophene carboxamidoxime-2 in 200 cm of inethanol is saturated with ammonia, keeping at a temperature below 40 ° C. The mixture is then allowed to stir for 16 15 hours then the solvent is distilled under reduced pressure (20 mm of mercury) at a temperature in the region of 35 ° C.

3

The residue is taken up in 100 cm of water, the crystals 3 are filtered and washed with water (3 x 50 cm) and dried at a temperature in the region of 40 ° C.

II g of O-carbamoylmethylthiophene carboxamidoxime-2, melting at 199 ° C., is thus obtained. After recrystallization from acetonitrile, the pure product melts at 199 ° C.

Example 2 Preparation of O-hvdrazinocarbonvl-methvl-thiophene carboxamidoxime-2 (compound 2) 3 To 200 cm of hydrazine hydrate, heated to 95 ° C., a solution of 20 g 3 ^ ethoxycarbonylmethyl-thiophene carboxamidoxime-2 in 200 cm of ethanol, and the reaction mixture is maintained at a temperature between 85 ° C and 95 ° C for 1 hour.

* 'Then concentrated under reduced pressure (20 mm of mercury then 1 mm of mercury) at a temperature close to 60 ° C to remove the ethanol and the majority of the hydra- 3 / zine hydrate, then take up the residue with 200 cm of water, filter the ^ / Y 35 crystals and wash them with 3 times 50 cm 3 of water. / // / Ί iJf '6 ·

After 16 hours of rest, the mother leagues provide a second stream of white crystals which are collected 3 by filtration, washed with 2 times 10 cm of water.

The two jets are combined and dried together.

5 This gives 10 g of O-hydrazinocarbonylmethyl-thiophene carboxamidoxime-2. After recrystallization from 20 parts of acetonitrile, the product melts at 156 ° C.

Example 3

By operating in the same manner as in Example 2, 10 from suitable raw materials, the following compounds were prepared: · „,„ -, ^ Point de N® compose Formula Yield fusj_on {oC)

15 ‘NH

A ^ 2 3 dd> rC - 49.5% 120 * - * ^ N0CH2C0N (CH3) 2 s, / ^ 2

/ Ve V

.20 4 || ^ NOCH2CONHCH3 64.0% 153 \ .........-! ----- \ s / NH2 5 ζ Yc ^ 49.5% 169 x 1! _1 ^ NO-CH2-CO ~ NH-NH ~ C6H j »» 25 __: ___

Example 4: Preparation of O-anilinocarbonvl-

methvl-thiophene-carboxamidoxime-2 P

(compound n ° 6) 3. ..

To 30 cm of aniline, 10.2 g of O-chloroformylmethyl- * thiophene-carboxamidoxime-2 hydrochloride are added in small portions at a time, and the reaction mixture is left to stand for several hours. 150 cm L of ether are added and the precipitate of aniline hydrochloride is filtered. It is washed with 2 x 50 cm of ether. / / 35 The filtrate is concentrated under reduced pressure // - 7.

(20 rem of mercury) at a temperature close to 30 ° C and then under a pressure of 1 mm of mercury at a temperature of 90 ° C.

10.9 g of O-anilinocarbonyl-.methylthiophene carboxamidoxime-2 are thus obtained in the form of an oil which slowly sets in mass.

3

After recrystallization from 20 cm of acetonitrile, the pure product melts at 123 ° C.

Example 5

By operating as in Example 4, from 10 suitable raw materials, the O- (N, N dimethyl hydrazino-carbonyl-methyl) thiophene 'carboxamidoxiii ^ 2 (compound No 7) was prepared.

Melting point 139eC Yield 40%

Example 6: Preparation of * 0-cvanomethyl-15 'thiophene carboxamidoxime-2 (compound No. 8)

14.2 g of thiophenecarboxamidoxime-2 3 are added to 84.2 cm of a 17.5% aqueous solution of tetraethyl ammonium hydroxide. After 5 hours at a temperature in the region of 20 ° C., the mixture is evaporated. water under reduced pressure (1 mm of mercury) at a temperature close to 25 ° C., then the residue obtained is redissolved in 100 cm 1 of dimethylformamide.

It is cooled to a temperature in the region of 5 ° C. and 11.3 is poured. g of chloroacetonitrile and allowed to return to a temperature in the region of 20 ° C. After 16 hours, about 70 cm of dimethylformamide are distilled under reduced pressure (1 mm of mercury) at a temperature in the region of 25 ° C., then 100 cm of water are added. After having allowed to stir for 2 hours, the crystals are filtered, the 3 washed with water (3 times 20 cm) and dried; these crystals are dissolved in 150 cm 3 of ethyl acetate, discolored in animal black ‘and dried over calcined magnesium sulfate.

After filtration and evaporation of the solvent, 10.1 g of O-cyanomethyl-thiophene carboxamidoxime-2, melting at 96 ° C., are obtained. / 35 ’After recrystallization from methanol, the '/ / # / 8 pure crystals melt at 96 ° C.

, Example 7: phytohormonal activity To a solution of 25 parts of the active ingredient to be tested in 65 parts of a mixture in equal parts of toluene and acetophenone, 10 parts of a condensed oxide product are added. ethylene and octylphenol at the rate of 10 molecules of ethylene oxide per molecule of octylphenol. The solution is used after dilution with water, at the desired concentration.

10 1 - Cuttings of tomato leaves

The second and third leaves are taken from Marmande tomato stems with 5 to 6 leaves.

The petiole of each leaf is immersed for a length of 2 to 3 cm in the test solution contained in a test tube. Eight days 15 after the start of the test, the percentage of rooted leaves and the average number of roots per rooted leaf are evaluated.

Concentration in 0 /. Average number of active substances. „Roots per leaf mg / liter scraped 20 ---- Control 0 50 5 0.01 100 10 compound- η» 1 0> 1__loo. 20_ 0.01 '100 15

Compound n ° 2 Λ, * * 0.1 100 15 0.01 50 5 sw

Compound n ° 5, ^ 0.1 100 8 0.01 100 '45 30 Compound n »8 0 (1 85 8 2 - Fruiting of tomatoes

The solutions to be studied are sprayed onto

the first and second floral bouquets of J tomato stems

35 variety Marmande, when 2 to 3 flowers of each bouquet are on // 9 the point of hatching. Before the treatment, there are on each * bouquet the number of flower buds. All the other bouquets which then form on the treated plants are eliminated as they appear. One month after the treatment, the number of fruits formed is counted and compared with the results obtained on controls treated with an aqueous solution containing the same wetting agent.

Concentration Total number of fruits in g / hl ~ —r— ~ z — 77-7 — ttt— x loo 10 Number of flowers treated Witness ’0 30

Compound # 1 3 80

Compound # 2 3 80 15

Compound # 3 3 40

Example 8: Herbicidal activity A solution or dispersion of the active material having the following composition is used: 20 - active material to be tested ........................ ..... 400 mg - acetone (solvent) ................................... 5 ml - sorbitol monooleate oxyethylated to 20 moles of ethylene oxide (wetting agent) ........................ 50 mg - distilled water containing 0.1 % of the condensation product of 10 moles of ethylene oxide with one mole of octylphenol .................... qs; 40 ml

This solution or dispersion is then diluted with distilled water to obtain the desired concentration,

Seeds of different species: wheat 30 (Triticum sativum), lentil (Lens culinarls), radish (Raphanus sativus), sugar beet (Beta vulgaris) and wild grass (Alopecurus agrestis) are sown in pots of plastic material. than 180 cm containing 6 cm high a mixture of 1/3 of loam, 1/3 of potting soil and 1/3 of river sand / 35 at a rate of about 30 seeds per pot. For each concentration of product, use 2 pots of wheat and four pots of other species.

For post-emergence treatment, sowing is carried out in the greenhouse one week before the start of the test so that the seedlings are at the following stage at the time of treatment: - wheat and vulpin: 3 leaves - lentils: 3 leaves - beetroot and radish: 2 well-developed cotyledon leaves.

The treatment is carried out by spraying the solution or the suspension of the product, the pots being placed on a pot turner. Each pot receives 1 cm ^ of the solution. The doses of the product to be studied are 1 and 8 Kg / ha.

In pre-emergence, the taught surface of the pots is allowed to dry then it is covered over 1 cm in height with the same earthy mixture. Twice a day, the pots are sprayed with water.

In post-emergence, the treated seedlings are left to dry. The earthy mixture is moistened by placing the base of the 20 ‘pots in a tray containing water.

In both cases, the pots are kept in the greenhouse (22 to 24 ° C - relative humidity 70 to 80%) under artificial lighting providing 5000 to 6000 lux at plant level for 17 consecutive hours per day. '25 Three weeks after at the start of the treatment, the seedlings are counted in each pot and their height is measured.

The results are expressed in percentages of destruction relative to the control.

The results are collated in Table 30 below. Percentages equal respectively to 0 and 100%) indicate that there is respectively selectivity and complete destruction // of the species considered. ~ /// if / "/ /, 11.

. Pre-emergence Post-emergence No. Dose ^ Len- Ra- Bette- Vul- Len- Ra- Bette- Vul-

Comp.sé Kg / ha 'tille dis rave pin tille dis Rave pin 5 ~~ 1 1 30 100 40 50 50 0 60 0 O 0 8 70 100 100 100 75 0 100 60 25 25'

2 1 30 100 60 50 75 0 50 0.0 O

8 70 100 100 90 100 0 lOO 60 25 25 10 3 10 000 00 000 0 * 8 30 100 O 50 80 0 OOO 0 5 1 30 100 0 80 75 0 O 0 0 50 8 50 100 100 100 90 0 70 100 70 50

15 1 20 100 30 100 50 0 0 0 0 O

6 8 60 100 100 100 100 O 70 20 100 25? 1 20 100 30 80 50 O 0 0 0 0 8 30 100 100 100 75 0 70 0 O 0 20 8 1 20 100 80 80 75 0 100 20 0 20 8 75 100 100 100 100 0 100 30 O 40

For their use in practice, the compounds according to the invention are rarely used alone, but in the form of agricultural compositions which are also the subject of the present application.

These compositions generally comprise, in addition to the active material according to the invention, a support and / or a surfactant compatible with the active material and usable in agriculture. In these compositions, the content of active product 30 'can be between 0.005 and 95% by weight, the term “support” within the meaning of the present description designates a material, organic or mineral, natural or synthetic, with which the material active is associated to facilitate its application on the plant, on seeds or on the soil, or its transport, or its handling. The support can be ////, fi ·. 12 solid (clays, natural or synthetic silicates, resins, waxes, solid fertilizers ...) or fluid (water, alcohols, ketones, petroleum fraction, chlorinated hydrocarbons, liquefied gases).

The surfactant can be an emulsifying, dispersing or wetting agent, each of which may be ionic or non-ionic. Mention may be made, for example, of salts of polyacrylic acids, of lignin sulfonic acids, of condensates of ethylene oxide on fatty alcohols, fatty acids or fatty amines.

The compositions according to the invention can be prepared in the form of wettable powders, powders, for dusting, solutions, emulsifiable concentrates, emulsions, suspended concentrates and aerosols.

Wettable powders are usually prepared so that they contain from 20 to 95% by weight of active ingredient and they usually contain, in addition to a solid support, from 0 to 5% of wetting agent, from 3 to 10 % by weight of a dispersing agent and when necessary, from 0 to 10% by weight of one or more stabilizers and / or other additives, such as penetrating agents, adhesives or anti-caking agents, dyes, etc ...

As an example, here is the composition of a wettable powder, the percentages being expressed by weight: - active material (compound n ° l) ................... ............ 50% - calcium lignosulfate (deflocculant) ...................... 5% 25 - isopropylnaphthalene sulfonate ( wetting) .................. 1% - anti-clumping silica ......................... ............... 5% - charge (kaolin) ............................ .................. 39¾.

The dusting powders are usually prepared in the form of a dust concentrate having a composition similar to that of a wettable powder, but without dispersing agent, and they are diluted at the place of use using an additional amount of solid support so that a composition usually containing 0.5 to 10% by weight of active material is obtained. / 35 The applicable emulsifiable concentrates eviJ / • J 13 spray usually contain, in addition to the solvent and, when necessary, a co-solvent, from 10 to 50% by weight / volume of active material, from 2 to 20% by weight / volume of suitable additives, such as stabilizers, penetrating agents, corrosion inhibitors and dyes and adhesives.

As an example, here is the composition of an emulsifiable concentrate, the quantities being expressed in g / 1: - active material (compound n ° 2) ................. ...... 400 g / 1 - dodecylbenzene sulfonate ................. t .......... 24 g / 1 10 - nonylphenol oxyethylated at 10 molecules ..., ............ 16 g / 1 '~ "- cyclohexanone .... ................... .............. 200 g / 1 - aromatic solvent ............................. qs 1 litre

The suspended concentrates, also applicable for spraying, are prepared in such a way as to obtain a stable, non-settling fluid product and they usually contain from 10 to 75% by weight of active material, from 0.5 to 15%. by weight of surfactants, from 0.1 to 10% by weight of anti-sediment agents such as protective colloids and thixotropic agents, from 0 to 10% by weight of suitable additives, such as foams, corrosion inhibitors, stabilizers, penetrating agents and adhesives, and as a carrier, water or an organic liquid in which the active ingredient is substantially insoluble? certain organic solids or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze for water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable layer or an emulsifiable concentrate according to the invention, are also included in the general context of the present invention. These emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

For a so-called "very low volume" application / with a spray in very fine droplets, solutions are prepared, / 35 in organic solvents containing from 70 to 95% ^ 4 // ,, 14 • active material.

The compositions according to the invention may contain other ingredients, for example protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants as well as other known active ingredients 1 with pesticidal properties, in particular insecticides or / fungicides. - /// "_ · Ψ" ". i. ·

Claims (9)

15 'I - Compounds derived from the compounds according to claim I of, the main denande n ° 75 * 766 characterized in that they correspond to the general formula: ‘-, 0. Ci: - A Il ir ^ c''m2 in which: R represents a hydrogen atom or an alkyl radical containing from I to 4 carbon atoms, XO A represents a cyano group or a radical of general formula î * ·. - CO - N '' "a in which, R ^ and R2 / identical or different, each represent a hydrogen atom, an alkyl radical containing from 1 to Λ carbon atoms, an optionally substituted phenyl radical, or a radical amino itself optionally substituted. 2. Compounds according to claim I, characterized in that they correspond to the general formula î 20 .S. N - O - CH „- A y_if ^ nh2 in which: 25. represents a cyano radical or a radical of general formula: - CO - N ^ r ^ R2 in which, R ^. and Rj, identical or different, each represent a hydrogen atom, an alkyl radical containing from I ^ 30 carbon atoms, a phenyl radical, or an amino radical itself optionally substituted by one or two radicals chosen from - alkyl radicals containing from 1 to 4 carbon atoms and the »phenyl radical. · 3. Process for the preparation of the compounds according to claim R 35. for which A represents a radical - CO - N "“ I, R and ^ p I 2 having the same meaning as in claim I, characterized in that reacts a compound of general formula *, / HN ^ I in which RT and have the same meaning as preceded] / - * * '16 ment, on a compound of general formula: RS' '• \ / N - O - CH - BI -f'C 5 _l | XNH2 in which R has the same meaning as in claim I and B represents either a radical - CO - 0 - R ^ in which represents an alkyl radical containing from I to 4 carbon atoms or · a radical - CO Cl, or on a hydrochloride of this compound 10 4 - Process according to claim 3, characterized in that n react a compound of general formula HN I in which R_ and R- ^ · ρ X Δ *. ^ 2 have the same meaning as in claim I on a compound of general formula: R 15. N-0-CH-C0-0-R, ^ \ C 3! J_If Vnh2 wherein R has the same meaning as in claim I and represents an alkyl radical containing from I to 4 carbon atoms. 5. Method according to claim 3, characterized in that R is reacted with a compound of general formula HN ^ I, in which R ^ and R ^ 2 have the same meaning as in claim I, on a compound of general formula: 25 .R ^ SN - O - CH - CO - Cl IJ_jf Cv "NH2, HCl in which R has the same meaning as in claim I 30 6 ** Process for the preparation of the compounds according to claim I for which A represents a CN radical, characterized in that a compound of general formula: S yU - OH - ". CK", 4 is reacted on a halo nitrile of general formula: {// R / '^ I / Y - CH - CN 17 <, * in which R has the same meaning as in claim I. and Y represents a halogen atom, operating in hydro organic medium, in the presence of an alkaline condensing agent. 7. phytohormonal and herbicidal composition characterized in that it contains as active material at least one compound according to claim I, in combination with at least one inert support and / or a surfactant for agricultural use. 8. Composition according to claim 7, characterized in that its active material content is between 0.005 and 95% by weight. 9. A method of herbicide or phytohormonal treatment characterized in that the crops are treated with a composition according to <any of claims 7 and 8. Drawings: boards - -JL. pages of which .......... Ä ...... cover page ...... A / f ...... description pages .......... 3 ... pegss of claims ..................... short description Luxembourg, le fâ-Le mapré ^ taire: // \ IP Ί 9 ~ 4P '» * "..