PL170956B1 - Substituted and heterocyclic phtalides - Google Patents

Abstract

Herbicide containing acceptable in agriculture, thinners, agents surfactants and other additives, characterized by having a salt of formula 10 wherein Yi is halogen atom, alkyl or alkoxy group, each of which is substituted with 1 to 6 halogen atoms; Y3 is hydrogen or halogen and X is hydroxy and Y is hydrogen, or X and Y together are = O and AM + is ammonium.

Description

The present invention relates to an agricultural herbicide.

EP 0 461 079 discloses herbicidal compounds of formula 1 in which the ring system A is selected from a phenyl or naphthyl group, a pyridyl group which may be fused by its side (b) or (c) to a benzene ring , a pyridyl N-tine or pyrazinyl-N-tine group, a pyrimidinyl group, a pyrazinyl group, a 3- or 4-5 synnyl group or a 2-quinoxalinyl group, and a five-membered heteroaromatic ring containing oxygen, sulfur or nitrogen as a heteroatom or heteroatomy, the ring being this may be fused to the benzene ring or may contain nitrogen as a further heteroatom.

R is cyano, formyl, CX1X2X3, ketone-forming group, carboxyl group which may be free acid or ester or salt form, thiocarboxyl group which may be free acid or ester, a carbamoyl group or a mono-or di-substituted carbamoyl group, a hydroxyalkyl group, a hydroxybenzyl group, a group of the formula -CH = NOH, -CH = NO- lower alkyl, a -CH2-OC (O) - group that bridges adjacent ring carbon atoms A or ring C of formula 2.

The substituents Y1, Y2 and Y3 are attached to carbon atoms and each independently represents hydrogen, halogen, hydroxy, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylsulfonyloxy, dialkylsulfamoyloxy, alkylsulfonyl, alkylsulfinylthio, alkenylthio, alkenylthio, alkynylthiohylthio, each of which may in turn be substituted with 1-6 halogen atoms; dialkoxymethyl, conjugated alkoxy, hydroxyalkyl, carboxyl, acyl, acylalkyl, acyloxy, acyloxyalkyl, trialkylsilyloxy, trialkylsilyl, cyano, nitro, amino or

170,956 substituted amino, aminosulfonyl; cycloalkyl, aryl, aralkyl, aralkenyl, aralkynyl, aryloxy, aralkoxy, arylsulfonyl, arylsulfinyl, aryl or aralkylthio, each of which may be substituted with one, two or three substituents selected from halogen, alkyl, nitro, alkoxyalkyl cyano, alkylthio, acyl, amine or substituted amine; a group of formula 3 in which R 'is hydrogen, lower alkyl or lower alkoxy; or Yi and R together with the adjacent carbon atoms form a bridge of formula 4, 5, 6, in which E is direct bonds or a single, two or three-membered bonding group with members selected from methylene group, substituted methylene group, group of formula 7 and oxygen atom; or Yii Y2 together with adjacent carbon atoms form a three-five membered bridge consisting of members selected from methylene group, substituted methylene group, formula 8, 9, 14, oxygen and 15, each of Wi, W2, W3, W4 and W5 are independently CH, CR3 or nitrogen; W 6 is NH, oxygen, sulfur, a group of formula 9, 8 or 16; Z is a two or three membered bridge containing members selected from a methylene group, a substituted methylene group, a group of formula 8, 9, 16, 17, -N =, an oxygen atom and a group of formula 17; R1 and R2 are each independently hydrogen, halogen, C1-4alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio, each of which may in turn be substituted with 1 to 6 halogen atoms; cycloalkyl, heterocycloalkoxy, aryloxy, aralkoxy or aralkylthio, each of which may be substituted with one, two or three substituents selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, substituted amino, amino or substituted amino; aminoxy group, substituted aminoxy group, iminoxy group substituted iminoxy group; amino, substituted amino, amide, substituted amide, alkylsulfonylmethyl, cyano, nitro, or Formula 18 wherein Y4 is hydrogen, lower alkyl, lower alkoxy, hydroxy, or unsubstituted or substituted phenyl.

R4 is the group specified for Y1 except for the carbon atom.

X and Y are each independently hydrogen, hydroxy, halogen, chan, alkyl, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, hydroxyalkyl, haloalkyl, acyl, acyloxy, carbamoyl, caramoyloxy, alkylthio, alkylsulfinyl, or alkylsulfonyloxy; aryl, aryloxy, aryl-S (O) _p , aralkyl, aralkoxy, aralko-S (O) p, arylsulfonyloxy, each of which may in turn be substituted with one, two or three substituents selected from halogen, alkyl, haloalkyl, alkoxy , haloalkoxy, nitro, cyano, alkylthio, acyl, amino substituted amino, or together form = O, = S, = Nh, = NOR12, or = CRbR14; or X and R together may form a bridge of formula 19, 20 or 21, wherein the corbonyl group is attached to A and R2 is hydrogen, hydroxy, alkyl, haloalkyl, alkoxyalkyl, alkoxy, aralkoxy, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl group or a group as defined further below for R7.

p is 0.1 or 2. Χ1, Χ2 and Χ3 are each independently hydrogen, hydroxy, alkoxy, alkylthio, hydroxyalkyl or hydroxybenzyl with at least one of Χ1, Χ2 and Χ3 being a group other than hydrogen; or Χ3 is hydrogen and Χ1 and Χ2 together form a four or five membered bridge containing members selected from -O (CH2) _n , O- groups of formula 22 and S (CH2) n, S- groups.

R12 represents a hydrogen atom or an alkyl group, R13 and R14 each independently represent a hydrogen atom, an alkyl group or a halogen atom, m is 1 or 2, n is

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0, 1 or 2 and n 'is 2 or 3 with the proviso that when R is a carboxyl group in free ester or salt form and X and Y together are = O, one of the rings A and B contains a heteroatom.

It is known from the referenced European description that when R is a carboxyl group in the form of a salt, the salt is preferably formed with an alkali metal, an alkaline earth metal, an optionally substituted ammonium cation, a trisulfonium cation, a trailkyl sulfoxonium or a phosphonium cation, especially an alkali metal cation. such as a Li or Na cation, or an alkaline earth metal cation, for example a Ca or Mg cation; an ammonium cation, a substituted ammonium cation such as a C 1 -alkylammonium cation, a di-C 1 -alkylammonium cation, a tri-C 1 -alkylammonium cation, a tetra-C 1 -ammonium cation, a (C 1 -alkoxyalkyl) ammonium cation, a (hydroxy-C 1 -alkyl) ammonium cation ; with a phosphonium cation; with a tri (C 1 -alkyl) sulfoxonium cation.

It has surprisingly been found that the ammonium salts of some of the compounds of formula I have particularly desirable, selective herbicidal properties. Although the ammonium salts of formula 10 are included in formula 1, they are not mentioned in EP 0 481 079. The herbicidal properties of the compound of formula 10 are clearly and surprisingly enhanced compared to those of the compounds described in EP 0 481 079. These properties are selective and could in no way be predictable, since ammonium compounds are generally known to have less effective properties because they are less stable. The ammonium salts of the formula (10) surprisingly have a stronger selective effect compared to the compounds disclosed in the questionable European patent.

According to the invention, the herbicide containing agriculturally acceptable diluents, surfactants and other additives is characterized in that it contains as active ingredient a salt of formula 10, wherein Y1 is halogen, alkyl or alkoxy, each of which is substituted with 1 to 6 halogen atoms; Y3 is hydrogen or halogen and X is hydroxy and Y is hydrogen, or X and Y together are = 0 and AM + is ammonium. Preferred salts are the ammonium salts of formula wherein Y1 is halogen or alkoxy and X and Y together are = O.

The ammonium cation used to form the ammonium salt is an ammonium (NH4 +) cation, a substituted ammonium cation such as a C1-alkyl ammonium ^^^, di-C1-alkylammonium, tri-C1-; dkylammonium, tetra-dialkylammonium, (C1-alkoxy) 2: C1-10) ammonium, (hydroxy-C1-alkoxyalkyl) ammonium or (hydroxyalkyl) ammonium.

Preferred ammonium cations are C13 and di-C1-3alkylammonium, e.g. dimethylammonium, isopropylammonium and diisopropylammonium.

Furthermore, the composition according to the invention comprises isopropylammonium 2,5-Djchioro-6> - [(4A-dimethoxy-2-pyrimidyrlyl) carbonyl] besoate.

In a preferred embodiment, the agrochemical composition comprises from 0.01 to 90% by weight of the ammonium salt of Formula 10 and up to 20% by weight of surfactant in association with an agriculturally acceptable diluent.

The compounds of formula 10 used in the composition according to the invention can be prepared as follows:

a) by reacting a compound of formula 11, wherein Y1 and Y3 are as defined above, with a compound of formula 12, wherein R1 is as defined above, and R21 is a metsulfonium group or a halogen atom to give the corresponding compound of formula 10p, then hydrolyzing a compound of formula 10p to the corresponding compound in which the CN group is replaced with a hydroxyl group (10p ') and treating said compound with an appropriate amine to obtain the desired ammonium salt;

b) by reacting a compound of formula 13 with a compound of formula 12 to form a compound of formula 10q wherein Y1 and Y3 are as defined above,

Oxidizing a compound of formula 10q to afford the corresponding compound (10p '), and treating this compound with an appropriate amine to generate the desired ammonium salt. In order to demonstrate the selective biological properties of the ammonium salts of formula 10 with respect to the compounds disclosed in EP-A-0461079, the compounds No. 481 and 534 listed in Table 1 and the compound No. 228 listed in EP-A-0 are compared in an exemplary herbicide test. 461 079 (p. 33). The test is carried out in a greenhouse.

The active ingredients are dissolved in acetone and diluted to a sprayable concentration with a 1: 1 mixture of acetone and water containing 0.25% surfactant. The diluted spray suspension is applied to the plants after emergence (23 monocotyledonous and dicotyledonous weeds and 3 useful crops) in the monocotyledonous and double-leafed stages in a linear spraying chamber, using 0.01 kg of active ingredient per 1 ha.

These plants are kept in a greenhouse for 21 days under a 16-hour light period and evaluated. The test results are presented in four groups as a percentage of their control, namely the groups: arable crops, yellow hazel sedge (cyperus escułentus) and the mean of all monocotyledonous and dicotyledonous plants in the test.

The results in percent of control are summarized below.

Relationship Crops Cyperus Monocots Dicotyledons 481 0 92 63 86 534 0 95 75 90 228 0 58 53 77

Compounds 481 and 534 had selective control (greater than 85%) of sedge and dicotyledonous weeds, control (greater than 60%) of monocotyledonous weeds, and control (greater than 90%) of cyperus which significantly exceeded the percent control of these weeds by Compound 228.

Thus, these results clearly show that the ammonium salts used in the compositions according to the invention show a much better herbicidal action compared to the known compounds disclosed in EP 0 461 079.

The results of the comparative tests carried out showed the particular effectiveness of the compounds according to the invention in controlling "cyperus", showing an over 60% increase in the control of these plants. At the same time, these studies confirmed that these compounds are much more useful for destroying monocotyledonous and dicotyledonous weeds. It is particularly noteworthy that an efficacy of in excess of 80% was achieved with dicotyledonous weeds, which was not the case with the known compounds. On the other hand, the nearly 100 percent cyperus control achieved is a unique achievement of the present invention considering that the prior art compounds only achieved an efficacy of just over 50%. It should be emphasized here that the selective action of the ammonium salts could not be predicted from the general knowledge of the prior art. It is known that ammonium salts are less stable salts with weaker action, and therefore their lower effectiveness should be expected. Surprisingly, the ammonium salts of the formula 10 according to the invention have selective properties and greatly exceed their efficacy of the salts disclosed in EP 0 461 079. These new, surprising properties of the ammonium salts are also of great importance in environmental protection, as they require an application rate for weed control. at least 20% less, and moreover, they biodegrade faster and therefore do not cause environmental pollution. Additionally, the grace period is shorter from the moment of application to the next harvest date. Consequently, the risk of these compounds remaining in the harvested crop is significantly reduced.

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The ammonium salts of formula 10 have a herbicidal effect as observed after their pre- and post-emergence application to weeds or their locus.

The term herbicide or herbicide refers to an active ingredient or effect that modifies plant growth due to plant growth regulating or phytotoxic properties so as to retard plant growth or damage the plant sufficiently to kill it.

The application of the ammonium salts of formula 10 is carried out according to a conventional method to the weeds or their locus with a herbicidally effective amount of the compound, usually from 10 g to 10 kg / ha.

The compounds according to the invention may be applied to both broadleaf and grass weeds in pre and post emergence application. The compounds may also show selectivity in a variety of crops and are therefore suitable for controlling weeds in crops such as corn, cotton, wheat, soybeans and rice.

The optimal use of the ammonium salts of formula 10 is readily determined by those skilled in the art using routine tests such as the greenhouse test and the little half test. It is dependent on the compound used, the effect desired (the phytotoxic effect requires a higher dose than the plant growth regulating effect), the treatment conditions and the like. In general, satisfactory phytotoxic effects are obtained when the ammonium salt of the formula 10 is applied at a rate of 0.01 to 5.0 kg / ha, preferably 0.025 to 2.5 kg per hectare, in particular 0.05 to 1.0 kg per hectare.

The ammonium salts of formula 10 may be conveniently combined with other herbicides to control spectrum weeds. Examples of herbicides that can be combined with the compound of the invention include compounds selected from carbamates, thiocarbamates, chloroacetamides, dinitroanilines, benzoic acids, glycerin ethers, pyridazinones, semicarbazones, uracils and ureas for broad spectrum weed control.

The ammonium salts of Formula 10 are conveniently employed as herbicides in conjunction with agriculturally acceptable diluents. Such compositions also fall within the scope of the invention. In addition to the ammonium salts of the formula 10, they can also contain other active agents, such as herbicides or compounds with antidote, fungicidal, insecticidal or insect attracting properties. They may be used in solid or liquid form, e.g. in the form of a wetting powder or a soluble powder with the incorporation of conventional diluents. Such compositions may be prepared in a conventional manner, e.g. by mixing the active ingredient with a diluent and optionally other formulation ingredients such as surfactants.

Agricultural acceptable additives may be used in the herbicidal compositions to improve the performance of the active ingredient and to reduce, for example, foam, caking and corrosion.

The term diluent as used herein means any liquid or solid agriculturally acceptable material which can be added to the active ingredient to be converted into a simpler or improved form for application, use or desired potency, respectively. It can be, for example, talc, kaolin, diatomaceous earth, xylene or water.

The term surfactant as used herein means an agriculturally acceptable material that imparts emulsifiability, flowability, wetting, dispersibility or other surface modifying properties. Examples of surfactants are sodium lignosulfonate and sodium lauryl sulfate.

In particular, spray-applied formulations such as water-dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g., formaldehyde naphthylene sulfonate condensation product, ethoxylated alkylphenol and ethoxylated fatty alcohol.

In general, the formulations contain from 0.01 to 90% by weight of active ingredient and up to 20% by weight of an agriculturally acceptable surfactant,

The active principle is at least one ammonium salt of formula 10 or mixtures thereof with other active ingredients. Concentrate forms of the compositions generally contain from about 2 to 90%, preferably from about 5 to 70% by weight of active agent. Direct application forms or preparations may, for example, contain from 0.01 to 20% by weight of active ingredient.

Table - compound of formula 23

Bind- zek Y 1 Y 3 R X IN 1 V 2 IN 3 IN 4 R 1 temp, melting (° C) 461 2-OH 3 5-Cl -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 190-201 479 2-Cl 5-Cl -COOH = O N CH C-OH 3 N -OCH 3 H N + (iCH) salt 2 3 7 2 160-162 480 2-Cl 5-Cl -COOH = O N CH C-OH 3 N -OCH 3 H N + (CH) salt 2 3 2 152-154 481 2-Cl 5-Cl -COOH = O N CH C-OH N -OCH 3 H N + and CH salt 3 3 7 184-186 502 2-Cl H. -COOH = O N CH C-OH N -OCH 3 HH salt 4 157-160 503 2-Cl H. -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 136-139 504 2-Cl H. -COOH = O N CH C-OH 3 N -OCH 3 H N + (CH) salt 2 3 2 163-165 528 2-Cl 5-F -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 174-176 (decomposition) 531 2-Cl 5-Cl -COOH = O N CH C-OH N -OCH 3 H N + C H OH salt 3 2 4 81-83 532 2-Cl H. -COOH = O N CH C-OH N -OCH DGA salt gura (NMR) 533 2-Cl 5-CH 3 -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 156-151 534 2-Cl 5-OH 3 -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 182-184 535 2-CH 3 5-F -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 161-162 536 2-CH 3 5-Cl -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 164-165 537 2-Cl 4-Cl -COOH = O N CH C-OH 3 N -OCH 3 H N + and CH salt 3 3 7 150-151 H N + C H OC H 3 2 4 2 OH is 4 known as diglycolamide (DGA)

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The subject of the invention is illustrated in the following examples. In these examples, any compound described in the table is used as the active ingredient for the preparation of the herbicidal composition.

Example I. Obtaining dust. 10 parts of the compound No. 481 and 90 parts of talcum powder are mixed in a grinding mixer and comminuted until a dust with high compression plasticity and the required particle size is formed. This dust is suitable for direct application to weed areas.

Example II. Preparation of a wettable powder. 25 parts of compound No. 481 are mixed and ground with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulfonate, 3 parts of sodium lignosulfonate and 45 parts of ground kaolin, until a particle size of about 5 microns is obtained. The obtained wettable powder is diluted with water.

Example III. Preparation of an emulsifiable concentrate (EC). 13.37 parts of the compound No. 534 are mixed in a beaker with 1.43 parts of Toximul 360A (which is a mixture of anionic and nonionic surfactants, mainly consisting of anionic agents), 5.61 parts of Toximul 360B (which is a mixture of anionic surfactants). and non-ionic surfactants, consisting primarily of non-ionics), 23.79 parts dimethylformamide and 55.8 parts Tenneco 500-100 (being essentially a mixture of alkyl aromatics such as xylene and ethylbenzene) until a slurry is obtained. The resulting concentrate is diluted with water before use.

PATTERN 2 PATTERN 3

-C-O -C-O-E -C-N-EII l and II i

SOOR ₂

MODEL 5

MODEL 6

MODEL 4

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I I I

R ₂ ^hr 4

PATTERN 7 PATTERN 8 PATTERN 9

PATTERN 10

PATTERN 10p

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oh ₃ ^N \ oh ₃

MODEL 12

Y ₃

MODEL 13

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—Ν— i - s - - c— 1 Łl Η (He 0 MODEL 11 MODEL 15 MODEL 16

s -Ο- Yó 0 1 ΙΙ II (0) n 0 -C-0- MODEL 17 PATTERN 18 MODEL 19

0 0 II —C - N- -0C (CH1) m0 II 1 II -c-s- r ₂ 0 MODEL 20 PATTERN 21 MODEL 22

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Publishing Department of the UP RP. Circulation of 90 copies

Price PLN 4.00

Claims (7)

Patent claims A herbicide containing agriculturally acceptable diluents, surfactants and other additives containing a salt of formula 10 wherein Y 1 is halogen, alkyl or alkoxy each substituted with 1 to 6 halogen atoms ; Y3 is hydrogen or halogen and X is hydroxy and Y is hydrogen, or X and Y together are = O and AM + is ammonium. 2. The agent according to claim The process of claim 1, wherein Y1 represents a halogen atom or an alkoxy group and X and Y together represent = O 3. The agent according to claim A cation according to claim 1 or 2, characterized in that the cation is an ammonium (NH4 ⁺ ) cation, a mono-, di-, tri- or tetra-C1-5alkylammonium cation, a cation (C15alkoxyalkylamKnic), a rmonium cation (hydroxy -Cyalkoxyalkyl)) or a cation ( hydroxy-C 1 -alkyl 4 -imonic. 4. The agent according to claim 1 3. The process of claim 3, wherein the cation is a C13 or diC-alkylammonium cation. 5. The agent according to claim 1 The process of claim 1 or 4, characterized in that it contains dimethylammonium, isopropylammonium or diisopropylammonium salt. 6. The agent according to p. The process of claim 1, comprising isopropylammonium 2,5-Dichloro-6 - [(4,6-dimethoxy-6-pyrimidinyl] carbonyl} benzoate. 7. The agent according to p. A surfactant according to any of the preceding claims, comprising from 0.01 to 90% by weight of the ammonium salt of formula 10 and up to 20% by weight of surfactant in association with an agriculturally acceptable diluent.