KR790001934B1 - Process for preparation of new amidoxime derivatives - Google Patents

Abstract

Amidoxime derivs. (I, R =H, Ph, C1-4 alkyl; R1 = H, metal atom, C1-4 alkyl ; Ar = halogen atom, OH, C1-4 alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, CF3) were prepd. by the reaction of II(Y = halogen atom) with amidoximes (III) in water-org. -mixed solvent at 20OC-80OC in the presence of alkaline condensation agent such as NaOH, KOH, tetraalkylammonium hydroxide. About 50 I having auxin-like activity at 1-100 g/ha and herbicidal activity at 0.5-10kg/ha were prepd.

Description

Preparation of Novel Amidoxime Derivatives

The present invention relates to a method for producing a novel amidoxime derivative represented by the following general formula (I).

In the general formula (I),

R represents a hydrogen atom or an alkyl group or phenyl group containing 1 to 4 carbon atoms,

R ₁ represents a hydrogen atom or an alkyl group or metal atom containing 1 to 4 carbon atoms,

Ar is a halogen atom and the following groups: an alkyl group containing 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group containing 1 to 4 carbon atoms in the alkyl group portion, and an alkyl group portion containing 1 to 4 carbon atoms Alkylthio group, alkylsulfinyl group in which the alkyl group moiety contains 1 to 4 carbon atoms, alkylsulfonyl group in which the alkyl group moiety contains 1 to 4 carbon atoms, trifluoromethyl group, trifluoromethoxy group, trifluoromethylthio group , Alkoxycarbonyl group containing 1 to 4 carbon atoms in carboxyl group, alkyl group, nitro group, amino group, alkylamino group containing 1 to 4 carbon atoms in alkyl group, each alkyl group containing 1 to 4 carbon atoms Alkylamino group, acylamino group in which acyl group moiety contains 1 to 4 carbon atoms, alkoxycarbonylamino group in which alkyl group moiety contains 1 to 4 carbon atoms, azi Group, an alkanoyl group containing 1 to 4 carbon atoms, a diphenylsulfamoyl group each alkyl moiety containing 1 to 4 carbon atoms, etc. represents a phenyl group substituted by 1 to 3 substituents selected from the same or different Or; Or a halogen atom, an alkyl group containing 1 to 4 carbon atoms, an alkoxy group containing 1 to 4 carbon atoms, and an alkoxy group containing 1 to 4 carbon atoms, containing an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom at position 5; An alkyl hetero group containing four carbon atoms or an aromatic group vent is optionally substituted by a phenylalkyl group containing 1 to 4 carbon atoms.

According to this invention, the product of general formula (I) can be obtained by either of the following methods.

1) Reaction of the compound represented by the following general formula (II) with the amidoxime represented by the following general formula (III)

Wherein R and R ₁ are as defined above, Y represents a halogen atom and Ar is as defined above.

The reaction is generally carried out in a water-soluble organic solvent such as ethanol and water or a mixture of dimethylformamide and water in the presence of an alkaline condensate such as sodium hydroxide, potassium hydroxide or tetraalkylammonium hydroxide at temperatures between 20 and 80 ° C. Do it.

The product of formula (III) may be prepared by the reaction of hydroxylamine with a nitrile represented by formula (IV).

Ar-CN (Ⅳ)

(In the formula, Ar has the same meaning as the foregoing.)

This reaction is generally carried out in an organic solvent such as water-soluble ethanol at a temperature between 20 and 80 ° C.

2) Reaction of the compound represented by the following general formula (V) with the imino ether salt represented by the following general formula (VI)

(Wherein R, R ₁ and Ar are as defined above and HA represents hydrochloric acid (HCl) or fluoroboric acid (HBF ₄ )).

This reaction is generally carried out in a basic organic solvent such as pyridine at a temperature of about 20 ° C.

The salt of the imino-ether represented by the general formula (VI) is a reaction between a solution of hydrogen chloride dissolved in ethanol and a nitrile of the general formula (IV) or triethyloxonium fluoroborate (meerwine salt) and the following general formula It can manufacture by reaction with the amide represented by (iii).

Ar-CONH ₂

Wherein Ar is as defined above.

3) Reaction of the compound represented by the following general formula (VII) with the compound represented by general formula R <_1> (OH) (VII)

(Wherein Ar, R and R ₁ are as defined in the general formula (I).)

This reaction is carried out by heating the compound of formula (VII) at a temperature of about 60 ° C. in the presence of alcohol and then evaporating the alcohol under reduced pressure.

The compound of general formula (I) in which R ₁ represents a hydrogen atom can be obtained by saponifying the compound of general formula (I) in which R ₁ represents an alkyl group containing 1 to 4 carbon atoms.

This reaction is generally carried out in an organic solvent such as methanol or ethanol at a temperature of about 20 ° C. in the presence of a base such as sodium hydroxide or potassium hydroxide.

The product of the general formula (I) in which the Ar group represents a phenyl group substituted with at least one alkylsulfinyl group can be obtained from the compound of the general formula (I) in which the Ar represents a phenyl group substituted with at least one alkylthio group by oxidizing an alkylthio group. have.

This oxidation can be carried out by dissolving the subcompound to be oxidized at room temperature in acetone and adding a 30% concentration (weight / volume) hydrogen peroxide solution to this solution.

The compounds according to the invention exhibit significant properties which are particularly useful in the agricultural sector.

If the compound is used at a dosage of between 1 and 100 g per hectare of water, the compound exhibits particularly useful phytohormonal properties. In this case, they have an auxin action similar to those of indolyl acetate or phenoxyacetate derivatives. These compounds are useful for helping the fruit of certain plants (tomatoes), to prevent the fall of leaves or fruits, or to increase the formation of roots.

If the compound is used at a dosage of between 0.5 and 10 kg / ha, the product according to the invention is herbicidal, in particular herbicidal in pre- and post-sowing treatment of dicotyledonous plants.

In practical use, the compounds according to the invention are rarely used on their own, but instead are used in the form of agricultural compositions which also form the subject of the invention. The composition generally includes, in addition to the active ingredient according to the present invention, a carrier and / or surfactant which can be used for agriculture in combination with the active ingredient. The content of the active ingredient in the composition is in the range of 0.005 to 95% by weight.

As used herein, the term "carrier" refers to an organic or inorganic, natural or synthetic material that is compatible with the active ingredient to facilitate its use in plants, seeds or soil, and to facilitate its transportation or handling. it means. Examples of this carrier include solids (clay, natural or synthetic silicates, resins, waxes, solid fertilizers, etc.) or fluids (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons or liquefied gases).

Examples of surfactants include emulsifiers, dispersants or wetting agents, each of which is ionic or nonionic. Examples thereof include salts of polyacrylic acid and lignin sulfonic acid and condensates of ethylene oxide with aliphatic alcohols, fatty acids or aliphatic amines.

The compositions according to the invention can be formulated in the form of hydrating agents, dusting agents, solutions, emulsifiers, emulsions, suspensions, suspension aerosols and granules.

Hydrating agent is usually 20 to 95% by weight of active ingredient and 0 to 5% by weight of wetting agent, 3 to 10% by weight, 0 to 10% by weight of one or more stabilizers and / or other additives (e.g. Or anti-cake agents, dyes, and the like).

An example of a composition of a hydrating agent is shown below, where the percentages are by weight.

Active ingredient (compound of general formula I) 50%

Calcium Lignosulfate (Decoagulant) 5%

Isopropylnaphthalenesulfonate (wetting agent) 1%

Silica Anti-Cake Agent 5%

Filler Kaolin 39%

Spraying agents are usually formulated with spraying agents having a composition similar to that of the hydrating agent, but without the use of dispersants, which are increased to supplemental solid carriers at the time of use, and are usually obtained as compositions containing 0.5 to 10% by weight of active ingredient.

Emulsifiers that can be used for spraying are usually solvents, 10 to 50% by weight / volume of cosolvent, active ingredient, 2 to 20% by volume / volume of emulsifier and suitable additives (e.g. stabilizers, penetrants, corrosion inhibitors, dyes and adhesives) 0 to 20% by weight of the volume).

An example of the composition of an emulsifier is shown below, where the amount is expressed in g / l.

Active ingredient (compound of formula I) 400 g / l

Dodecylbenzenesulfonate 24g / ℓ

(Ethylene oxide) 16 g / l nonylphenol oxyethylated with 10 molecules

Cyclohexanone 200 g / l

Aromatic solvent about 1ℓ

Suspensions, which may also be used for spraying, are formulated to give a stable fluid product which does not precipitate, which typically comprises 10 to 75% by weight of active ingredient, 0.5 to 15% by weight of surfactant, and precipitation inhibitors (e.g., protective cloaks and thixotropic agents). ) 0.1 to 10% by weight, 0 to 10% by weight of suitable additives (e.g. anti-foams, corrosion inhibitors, stabilizers, penetrants and adhesives) and carriers, containing water or organic liquids which are substantially insoluble in active ingredients and precipitated Any organic solid or inorganic salt may be dissolved in the carrier to help prevent or as a cold-resistant agent for water.

Compositions obtained by dilution of the hydrating or emulsifying agents according to the invention with water, such as aqueous dispersions and emulsions, also fall within the general scope of the invention. These emulsions are of "water-in-oil" type or "oil-in-water" type and have a dark concentration such as mayonnaise.

For the so-called "lowest volume" use, spray liquids such as fine droplet solutions in organic solvents are obtained by containing 70-95% of the active ingredient.

The composition according to the present invention may contain, as other components, known active ingredients with, for example, protective colloids, adhesives or weight agents, thixotropic agents, stabilizers or metal ion sequestrants and insecticides, in particular pesticides or fungicides.

The following examples are intended to illustrate the invention in detail, and do not limit the scope of the invention.

Example 1

Preparation of 0-ethoxycarbonyl-methyl-thiophene-2-carboxamidoxime

The method used here is the second method mentioned in the present invention.

A mixture of ethylthiophene-2-carboximidate hydrochloride (140 g) and ethylamino-oxyacetate hydrochloride (104 g) in pyridine (2, 350 cc) was stirred at a temperature of about 20 ° C for 1 hour. Pyridine was evaporated under reduced pressure (2 mmHg) at a temperature of about 30 ° C., then the residue was dissolved in ethyl acetate (1 L), the pyridine hydrochloride formed was filtered off and washed with ethyl acetate (2 × 500 cc) It was. The filtrate was washed with water (500 cc total), decanted, dried over sodium sulphate and bleached with grenade. After filtration, the solvent was evaporated at 30 ° C. under reduced pressure (20 mmHg) to obtain a clear oil, which crystallized when titrated in isopropyl ether (100 cc). After filtration and isolation, the mixture was dried to obtain 0-ethoxycarbonyl-methyl-thiophene-2-carboxamidoxim (150.7 g) with a melting point of 58 ° C. After recrystallization with isopropyl ether (3.3 parts), a pure product was obtained, which was white crystalline and had a melting point of 62 ° C.

[Examples 2 to 47]

According to the same method as in Example 1, the following product was obtained using a suitable raw material.

Example 48

Preparation of 0- (1-carboxymethyl) thiophene-2-carboxamidoxime

The method used in this example is the first of the methods mentioned in the present invention.

A suspension obtained from bromoacetic acid (29.4 g) and 0.99 N ethanol sodium hydroxide solution (213 cc) was extracted with thiophene-2-carboxamidoxime (30 g) and 0.99 N ethanol sodium hydroxide solution (213 cc) over 5 minutes. To the mixture was added and the batch was stirred for 16 hours. Ethanol was evaporated under reduced pressure (20 mmHg) at a temperature between 20-30 ° C. The obtained crystals were dissolved in ethyl acetate (210 cc), filtered off, washed with ether (2 × 100 cc) and dried at a temperature of about 20 ° C. under reduced pressure (20 mmHg). The white crystals thus obtained were dissolved in water (390 cc), sodium chloride (40 g) was added, and citric acid (15 g) was added to make the solution completely. The precipitate formed was filtered off, washed and dried to give 0-carboxymethylthiophene-2-carboxamidoxim (15.65 g) having a melting point of 130 ° C. After the mother liquor was saturated again with sodium chloride, it was carried out in the manner described above to obtain a second compound of 0-carboxymethylthiophene-2-carboxoxamidoxime having a melting point of 130 ° C. After recrystallization with water, a pure product having a melting point of 131 ° C. was obtained.

Example 49

Suspension obtained from a mixture of α-bromobutyric acid (16.7 g) and 0.97 N ethanol sodium hydroxide solution (103 cc) from thiophene-2-carboxamidoxime (14.2 g) and 0.97 N ethanol sodium hydroxide solution (103 cc) Was added. According to the method described in Example 48, sodium (14.1 g) having 0- (1-carboxycockpropyl) -thiophene-2-carboxamidoxim having a melting point of 246 占 폚 was obtained.

Example 50

Preparation of compounds in which R ₁ corresponds to general formula (I) by saponifying compounds wherein R ₁ is an alkyl group

0.1 N sodium hydroxide solution (1,250 cc) was added to a solution of 0-ethoxycarbonylmethyl-thiophene-2-carboxamidoxim (22.8 g) dissolved in ethanol (220 cc). The suspension thus formed was stirred for 40 hours at a temperature of about 20 ° C., and the resulting solution was separated by filtration through a Supercel and neutralized by adding a prescribed hydrochloric acid solution (125 cc). The mixture was concentrated to 2/3 of its volume under reduced pressure at a temperature of about 50 ° C. and then extracted with methylene chloride (1,100 cc total). The organic extract was dried over calcined magnesium sulfate and bleached with bleached charcoal. After filtration, the solvent was evaporated under reduced pressure (20 mmHg) to obtain 0-carboxymethyl-thiophene-2-carboxaminosim (7 g) having a melting point of 120 ° C. The mother liquor was extracted with ethyl acetate (total 750 cc) and then treated as above to obtain an additional amount of product (9.1 g) with a melting point of 129 ° C.

After recrystallization from water, a 0-carboxymethylthiophene-2-carboxamidoxime having a melting point of 131 ° C was obtained. This compound has already been described in Example 48 herein, where it was obtained by a different method.

Example 51

Preparation of 0-butoxycarbonylmethyl-thiophene-2-carboxamidoxime

The method used in this example is the third method mentioned in the present invention.

A mixture of 0-chloroformylmethyl-thiophene-2-carboxamidoxim hydrochloride (13 g) and n-butanol (65 cc) was heated at 60 ° C. for 4 hours. The alcohol was evaporated under reduced pressure (20 mmHg) at a temperature of about 40 ° C., then the residue was dissolved in a solution of sodium bicarbonate (7.7 g) dissolved in water (130 cc), and the organics were extracted with ethyl acetate (3 × 130 cc). It was. The organic extract was washed with water (2 × 50 cc) and dried over sodium sulfate. After evaporation of the solvent under reduced pressure (20 mmHg) at a temperature of about 40 ° C. after filtration, 0-butoxycarbonylmethyl-thiophene-2-carboxamidoxim (13 g) was obtained in oil form. After dissolving in cyclohexane (100 cc), the product crystallizes. It was filtered and dried at a temperature of about 25 ° C. under reduced pressure (1 mmHg). 0-butoxycarbonylmethyl-thiophene-2-carboxamidoxime (12.3 g) having a melting point of 31 ° C. was obtained.

Example 52

0-methoxycarbonylmethyl having a melting point of 82 ° C using 0-chloroformylmethyl-thiophene-2-carboxamidoximhydrochloride (15 g) and ethanol (100 cc) according to the above-described example. -Thiophene-2-carboxamidoxim (10.7 g) was obtained.

Example 53

This example describes a method for preparing 0-ethoxycarbonylmethyl-3-methylsulfinyl-benzamidoxime from the compound described in Example 13 by oxidizing a methylthio substituent attached to a phenyl group with a methylsulfinyl substituent. It is.

A 30% concentration (weight / volume) solution of hydrogen peroxide (2.1 cc) was added to a solution of 0-ethoxycarbonylmethyl-3-methylthio-benzamidoxim (5.03 g) dissolved in acetone (100 cc), This mixture was left for 7 days. The solvent was evaporated under reduced pressure (20 mmHg) at a temperature between about 30 ° C. and the residue was then dissolved with methylene chloride (50 cc) and (20 cc). The organic layer was decanted and dried over sodium sulfate. After filtration, the solvent was evaporated to give an oil (5 g), which was chromatographed with a column containing silica (50 g). Elution with methylene chloride afforded unreacted 0-ethoxycarbonylmethyl-3-methylthio-benzamidoxim (0.9 g), followed by 0-ethoxycarbonylmethyl-3-methylsulphate with a melting point of 58 ° C. Pinilbenzamidosim (3.5 g) was obtained. After recrystallization from a mixture of isopropyl ether (25 cc) and ethanol (5 cc), a pure product having a melting point of 90 ° C. was obtained.

Example 54

0-ethoxycarbonylmethyl- in which a condensate of ethylene oxide and octylphenol (10 parts) was dissolved in a mixture of toluene and acetophenone (65 parts) in the same ratio at a rate of 10 molecules of ethylene oxide per molecule of octyl phenol. To a solution of thiophene-2-carboxamidoxim (25 parts). This solution was diluted with water and used at a rate of 100 cc of this solution per 100 liters of water.

The plant hormone effect of the product according to the invention was demonstrated by the following test method.

1) the fruit of tomato

One drop (0.05 cc) of a solution or suspension of the compound to be tested was used for the ovary of the castrated flowers of the tomato plant. The percentage of fruit formed after observation for 5 days was compared.

When used in this way, at a concentration of 10 mg / L, the compound of Example 1 showed 100% deletion, but the comparative showed 0% deletion.

The fruit formed did not have spots.

2) propagation of tomato leaves

The third and fourth leaves were removed from 5 to 6 leaf tomato stems (breed Marmande). The leaf tip of each leaf was immersed 2-3 cm deep into the solution to be tested in the test tube.

On the eighth day after the experiment, the number of roots formed on the leaf stems of the treated leaves was counted and their shape was observed. When used in this way, at a concentration of 1 mg / l, the products of Examples 1, 5 and 41 formed 100% thick, rooted leaves with multiple roots, while roots in the case of control leaf The formation of the leaves with leaves was zero. At the same concentration, the product of Example 45 formed 100% of the rooted leaves but few short and thick roots.

3) fall of leaf

This experiment was done on Coleus. The ground formed by the sections of the stem with two leaf tips was immersed in the solution of the product to be tested. Leaf stems were removed from the stems at regular time intervals.

For the control plants, leaf stems were separated after 2 days.

When the product of Example 3 was used at a concentration of 100 mg / l, no part separation was observed after one week from the start of the experiment.

The herbicidal properties of the compounds of general formula (I) were demonstrated in the following manner.

Seeds of different varieties, such as wheat (Triticum sativum), lentils (Lens culinaris), radishes (Raphanus sativus), beets (Beta vulgaris) and slender grasses (Alopecurus agrestis), clean soil 1/3, plant soil 1 / About 30 seeds per pot were sown in a plastic powder (capacity, 180 cc) filled with a mixture of 3 and 1/3 of the sand. Compounds of each concentration were used in two pollen of wheat and four pollen of other species.

For the purpose of post-sowing treatment, sowing was carried out in the greenhouse one week before the start of the experiment, and the young plants of the next stage were treated.

Wheat and Honeyweed: 3 leaves

Lentils: 3 leaves

Beet and Beet: Leaves of Two Well-Developed Cotyledons

This treatment was carried out by spraying a solution or suspension of the product and placing each pot on a planter counter. 1 cc of solution was used for each pot.

Doses of the compound to be tested are 1 and 8 or 10 kg / hr.

In the pre-sowing test, the seeding surface of the powder was dried and then covered with the same soil mixture to a depth of 1 cm, watered twice in a flowerpot twice daily, and in the post-sowing test, the treated young plants were dried. The soil mixture was immersed in the bottom of the pot in a tray of water.

In both cases, pots were kept daily for 17 hours in the greenhouse (22-24 ° C., 70-80% relative humidity) at the same height of the plant under artificial backing of 5,000-6, 000 lux.

Three weeks after the start of treatment, the number of plants in each pot was counted and their height was measured.

The results are expressed in percentage relative to the comparative plant.

The results are summarized in the following table.

Claims (1)

A novel compound represented by the following general formula (I) characterized by reacting a compound represented by the following general formula (II) with an amidoxime family represented by the following general formula (III) at a temperature of 20 ° C to 80 ° C. Preparation of Amidoxime Derivatives.

Where R represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, or a phenyl group, R ₁ represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, or a metal atom, Ar is a halogen atom and the following groups: an alkyl group containing 1 to 4 carbon atoms, a hydroxy group, an alkoxy group containing 1 to 4 carbon atoms in the alkyl group portion, and an alkyl tea containing 1 to 4 carbon atoms in the alkyl group portion Alkyl sulfinyl groups containing 1 to 4 carbon atoms in alkyl groups, alkyl sulfonyl groups containing 1 to 4 carbon atoms in alkyl groups, trifluoromethyl groups, trifluoromethoxy groups, trifluoromethylthio groups, Carboxyl group, alkoxycarbonyl group containing 1 to 4 carbon atoms in the alkyl group, nitro group, amino group, alkylamino group containing 1 to 4 carbon atoms in the alkyl group, dialkyl containing 1 to 4 carbon atoms in each alkyl group Amino group, Acylamino group in which acyl group part contains 1-4 carbon atoms, Alkoxycarbonylamino group in which alkyl group part contains 1-4 carbon atoms, Ac Potassium, an alkanoyl group containing 1 to 4 carbon atoms, each alkyl group moiety represents a phenyl group substituted by the same or different 1 to 3 substituents selected from dialkylsulfamoyl groups containing 1 to 4 carbon atoms Or a halogen atom, an alkyl group containing 1 to 4 carbon atoms, an alkyl group containing 1 to 4 carbon atoms, an alkoxy group containing 1 to 4 carbon atoms, or an alkyl group portion as a hetero atom at the 5th position; An alkylthio group or alkyl group moiety containing 1 to 4 carbon atoms represents an aromatic heterocyclic group optionally substituted by a phenylalkyl group containing 1 to 4 carbon atoms.