HU182008B - Herbicide compositions containing 2-chloro-3,5-diiodo-pyridine derivatives as active agents, and process for producing the active agents - Google Patents

Abstract

The compounds of the formula I are new. The substituent in the formula I has the meaning given in Claim 1. The new compounds are prepared by iodination of 2-chloro-4-hydroxypyridine, followed if appropriate by its conversion to the corresponding salts or esters. The new compounds are notable for their good herbicidal action and are used to control unwanted plants. <IMAGE>

Description

FIELD OF THE INVENTION The present invention relates to an herbicide containing a 2-chloro-5,5-diiodopyridine derivative of the general formula (I) and a process for the preparation of the novel pyridine derivatives. In the formula (1) R is hydrogen, an alkali metal or a C 2 -C 18 alkylcarbonyl, C 2 -C 5 haloalkylcarbonyl. C 2 -C 18 alkoxycarbonyl, C 5 -C 5 alkenylcarbonyl, C 4 -C 7 cycloalkylcarbonyl, benzylcarbonyl, styrylcarbonyl, di-C 1 -C 4; alkylcarbamoyl, C 1 -C 4 alkylsulfonyl, p-toluene-1-sulfonyl, or benzoyl optionally substituted with one halogen, one or two chro- or C 1-4 -alkyl.

The alkali metal atom may be, for example, a sodium or potassium atom, preferably a sodium atom. In the groups defined above, the halogen substituent is preferably chlorine or bromine. :

- Preferred compounds of formula (I) are those which are - ^; B is a C 2 -C 10 alkylcarbonyl group, especially a C 2 -C 4 alkylcarbonyl group.

Herbicides containing substituted pyridine compounds are described in U.S. Patent No. 5,859,295.

The novel compounds of formula (I) may be prepared by reacting 2-chloro-4-hydroxypyridine in the 5- and 5-positions with the 2-chloro-3,5-diiodo-4-bridge roxypyridine obtained. in a desired process for the preparation of compounds of formula (I) in which R is converted into a salt or ester in a known manner other than hydrogen;

For iodination, iodine / chlorine or hydrogen iodide and iodine can be used. When iodine / l-chloride is used, the reaction is preferably carried out in acetic acid, aqueous hydrochloric acid or water at elevated temperatures, such as boiling, and in the case of hydroxy iodide and iodine, preferably in aqueous ethanol. Other water-miscible organic solvents may be used in place of ethanol if this is inert under the reaction conditions, such as, for example, acetic acid.

For the preparation of compounds of formula (I) in which R is other than hydrogen, the corresponding compound of formula (I) - H or its salt is preferably esterified by reaction with the appropriate halogen, acid anhydrous or reactive ester. The salts are prepared in known manner.

The compounds of formula (I) are useful as herbicides. Compounds of formula (I) wherein R is hydrogen or an alkali metal are also valuable intermediates for the preparation of herbicides.

The herbicidal activity of the new compounds containing the compounds of the general formula (1) can be applied even in the treatment of leaves and the soil as a total hourly pesticide, while at lower concentrations /> 0.25 kg / ha / treating weed leaves after emergence in cereal plantations.

The new agents may be used, for example, in the form of suspensions, dusts, granules, solutions, emulsions or sprays. The concentration of the active ingredient in the agents may be 90%.

The use concentration is about 0.001 to 5% by weight, preferably 0.005 to 1% by weight. Boxing agents and especially small volume

-2182,008 sex / ULV / use concentration may be higher, about 85 s% -lg.

For the preparation of the compounds, a compound of formula (I) is admixed with auxiliary agents for the formulation of plant protection sex, such as solid or liquid diluents, agents, carriers, surfactant additives, such as wetting and adjuvanting sexes, emulsifying and dexpexing agents.

Examples of solid or liquid diluents are natural or artificial mineral ground, such as silica, kaolin, clay, talc; petroleum fractions; an aromatic or aliphatic hydrocarbon mixture; the surfactant additive may be anionic or nonionic non (flocculant, tackifier, suspending, emulsifying or dispersing agent), such as aloylaminosulfonic acids, alkylnaphthalenesulfonic acids, lignin sulfonic acids and their salts, polyhydric fatty acid esters of polyhydric alcohols, fatty acid pollen / ethylene glycol / esters, alkyl phenols with ethylene oxide adduct, etc. ·

The following examples illustrate the composition of some agents / s uly% -b an / i ----—---- ~ --------— ---- -----—----- --- a / Suspension powder

1/25% 2-chloro-3,5-diiodo-4-acetoxy-1-pyridine,

% colloidal silica gel.

% lgg / lsulfonate / dispersant /% sodium tetrapropylene benzene sulfonate / wetting agent / or

% calcium lignin sulfonate,% colloidal silica,% sodium sulfate,% dlisobutyl naphthalene sodium sulfonate.

b / Emulsion concentrate% 2-chloro-3,5-diiodo-4- (methoxycarbonyloxy) pyridine,

- 25% Shellflol A / Liquid Edge of Aromatic Hydrocarbons /% Ν-Methyl Pyrrolidone *% Emulsogen I 40 / Anlonlactive Emulsifier /.

c / Dusting agent% 2-chloro-5,5-diiodo-4-propionyloxy-pyridine,% talc, 1% methylcellulose.

The a / or b / composition! concentrate is diluted with water to the desired active ingredient concentration before use (0.001-5%).

Agents containing the active compounds of the formula (I), in particular those containing 2-chloro-3,5-diiodo-4-acetoxypyridine, are preferably used in combination with other herbicides. This often results in a more favorable spectrum of action or synergism. In these combination combinations, the agent containing the active compounds of the invention, in particular the above compounds, is 0.03-3182.00ε

-1.0 kg / ha, preferably 0.05-0.3 kg / ha:! and apply the combining partner in the usual dose range of 50-100 U. For example, with some typical agent combinations, the following amounts of active ingredient are applied at a rate of 0.05-0.2 kg / ha of 2-chloro-3,5-diodo-4-pallethoxy-pyridine per hectare:

1.0 kg of 3- (4-chlorophenyl) -1-methyl-1- (1-methylprop-2-yl) urea, or

P, 5 kg of 3- (4-chlorophenyl) -1-methyl-1-methoxycarbamide, or kg of 3- (5-chloro-4-methoxyphenyl) -1,1-dimethylcarbamide, or 0 kg of 3- (3-chloro-4-methylphenyl) -1,1'-dimethylcaxamide, or

2.5 kg of 1-benzothiazole-2-yl-1,3-dimethylurea, or

3.5 kg of 3- (4-isopropylphenyl) -1,1-dimethylurea, or

0.9 kg of 6-tert-butyl-4- (2-methylpropylidene imino) -5-methylthio *

-4,5-dihydro-1,2,4-triazin-5-one, or

P, 9 kg of isobutyl 2- ^[ 4- (4-chlorophenoxy) phenoxy] propionate, or

3. 6 kg of ethyl 2-N-benzoyl-3,4-dichloroanilino-7-proponate, or

3.0 kg of 1,1-dimethyl-3,5-phenylphenylpyrazolium methyl sulfate, or

4.0 kg of 2-chloro-3- (4-chlorophenyl) methylproponate, 'or

3.0 kg of methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propionate, or

A mixture of 3,0 kg of 4-chloro-2-methylphenoxyacetic acid (760 g) and 9-hydroxyfluorene-9-carboxylic acid (240 g) in dimethylamine salts, or

2.4 kg of 2- (4-chloro-2-methylphenoxy) -propionic acid or its salts

2.4 kg of 2- / 2,4-dichlorophenoxy / propionic acid or its salts

D, 8 kg of a mixture of salts of 2,4-dichlorophenoxy-acetic acid and 4-chloro-2-methyl-phenoxy-1-acetic acid in a ratio of l / l, or

0.4 kg of 4-hydroxy-3,5-diiodobenzonitrile, or

0.4 kg of 4-hydroxy-3,5-dibromobenzonitrile or

2.0 kg of 3-isopropyl-2, ₁₁ 5-benzotladlazinone-4 / -2,2-dioxide, or

2.0 kg of 3,5-dibromo-4-hydroxy-benzaldehyde-2,4-dinitrophenyl oxyl, or

2.5 kg of 2- (1-methyl-n-propyl) -4.6-dinitrophenyl acetate or

5.0 kg of 4,6-dinitro-2-tert-butyl-phenol.

The combination partners listed are in different dosages. It can be used. The amount of herbicides acting on grasses can be reduced to 75% of the amount indicated, and the amount of other herbicides to about 50% of the above. In combinations, the amount of the active compounds of the present invention may optionally be simultaneously increased within the limits given above. The combination partners listed above can also be used at desired dosages up to about 50% this week. The active ingredient of the present invention may be simultaneously reduced within the above stated limits.

The following examples illustrate the preparation of the active compounds. Temperature data is given in degrees Oelsius.

Example 1

2-Chloro-3,5-diiodo-4-hydroxy-pyridine

129.5 6/1 molar 2-chloro-4-hydroxypyridine and 203.2 g (0.8 mol) iodine in 1 liter of ethanol were heated with stirring. as | A solution of 70.4 g (0.4 mol) of iodic acid in 200 ml of water is added dropwise at 60-70 °. Then reflux for 3θ minutes, cool and cool the resulting crystalline slurry

182,006 thoroughly drained. It is then washed with ethanol and dried at 100-110 °. Yield: 366 g (96%). The product decomposes above 290 °.

Example 2

2-Chloro-3,5-diiodo-4-acetoxy-pyridine

191 g (0.5 mol) of 2-chloro-3,5-diiodo-4-hydroxypyrldine 400 | It is suspended in ml of acetic anhydride and refluxed for 50 minutes. A wet solution is obtained which is cooled u ·? or 5 liters of water. The precipitated solid was slurried, washed with water and dried at 50-60 ° C. Yield: 192 g (91%). M.p. 127128 ° C, recrystallized from ethanol.

Example 5

2-Chloro-5,5-diodo-4-hydroxy-pyridinedinate 6

381.5 g (1 mol) of 2-chloro-3,5-dodoiodo-4-hydroxypyrldine are added with 2? g / l mol / sodium in 200 ml methanol. Methanol was completely distilled off from the resulting solution with continuous addition of toluene. A colorless powder is formed which is filtered off and dried. The yield is quantitative.

Example 4

2-Chloro-3,5-diiodo-4- / methoxy-carbonyl-oxy / -pyridin

58.1 g (0.1 mole) of 2-chloro-5.5-diiodo-4-hydroxylplridine. Methyl chloroformate (15 g, 0.15 mol) and potassium carbonate (27.6 g, 0.2 mol) in acetonitrile (500 ml) were heated to reflux for 5 hours. After cooling, the reaction mixture was poured into water, extracted with methylene chloride, and the organic phase was partitioned between 1% sodium hydroxide solution and water, dried over sodium sulfate and evaporated. During cooling, the residual oil solidifies to a crystalline mass which can be recrystallized from cyclohexane. Yield 55 g / 82.7% · Melting point 74-75 ·

5 · Example

2-Chloro-5,5-diiodo-4 / N, N-dimethyl-carbamoyloxy / pyridine

The sodium salt (8.1 g, 0.02 mol) of the example is heated at reflux for 20 hours with 4- (2 g, 0.04 mol) dimethylcarbamic acid chloride in toluene (50 ml). The residue was filtered and the cooled solution was partitioned between 0.5 g of sodium hydroxide solution and water and evaporated. The residual oil solidifies by rubbing and can be crystallized from ethyl acetate. Yield: 6 g (64%). 148-149 ° «

Example 6

2-Chloro-5,5-dl-iodo-4-hydroxy-pyrrolidine a / 129.5 β / 1 mol / 2-chloro-4-hydroxy-pyridine and 205.2 g / 0.8 mol / iodine 1.6 of ethanol and 400 ml of 20% sulfuric acid are suspended in with stirring. The reaction mixture was heated to 60 ° C and a solution of 8.6 g of potassium iodate in 200 ml of water was added dropwise over 50 minutes. It is then refluxed for a further 30 minutes, cooled and added dropwise with 20 ml of a saturated aqueous solution of sodium bisulfite.

-5182.008 The suspender is desalted. The xeaclock mixture is then drained, rinsed thoroughly with water and rinsed with a little cold ethanol. Drying at about 100 ° gives 540 g (89%) of 2-chloro-5,5-iodo-9-hydroxypyridine.

b) 129.5 g / l of 2-chloro-4-hydroxy-pyridine are suspended in 4 l of 10% hydrochloric acid. While stirring, a solution of 524 g / 2 mol · (iodine) oxalic acid in 650 ml of 10% hydrochloric acid was added and the mixture was slowly boiled. The reaction mixture is then cooled, the precipitated product is filtered off, washed thoroughly with water and dried at 110 ° C. Yield 520 g (84%).

c / 255 g / 1 mol / iodine is suspended in 1 liter of acetic acid · 71 g of chlorine gas is added to the suspension over 1 hour at room temperature. To the resulting solution was added 129.5 g / l mol 2-chloro-4-hydroxypyridine and heated at 100 for 50 min. The reaction mixture is then cooled, poured into 5 liters of water, drained, rinsed thoroughly with water and dried at 110 ° C. Yield: 540 g (89%) of the title compound.

A mixture of d / 129.5 g / l mol / 2-chloro-4-hydroxypyridine and 255 g / l mol / iodine was suspended in 1 L acetic acid and heated to 600 with stirring. A solution of 50 ml of nitric acid (d &gt; 1.4) and 110 ml of sulfuric acid (d = 1.84) is then added dropwise and the solution is kept at this temperature for 50 minutes. The reaction mixture was poured into 5 liters of water, drained, washed well with water and dried at 110 ° C. Yield 555 g (88%).

The compounds of formula (I) in Table I can be prepared according to the preceding examples.

Table I

Example R melting point 7th n-CJH ^ -CO- 58-60 8th CII, -CH-CH _? CO ch ₅ 55-56 9th ^{n C} 7 ^H 15 ^GO oil 10th η-Ο ₁₇ Η ₃₅ -Ο ° - 61-63 11th CII ₅ -CH = CH-CO- 115-114 12th oi-ch ₂ -ch ₂ -co- 99-100 15th ch CH-co- 98-100 14th Cl ₂ CH-C0- 99-100 15th cyclopean opi1-C0- 95-95 16th cyclohexyl-CO- 95-94 17th fen11-00- 149-151 18th / 4-chlorophenyl / C 0 115-120 19th / 4-me t1-phen i1 / -C0- 158-159 20th / 5-nitro-feni1 / CO 150-151

182 008

Example R Melting point, ^q q

21st / 3,5-dinitrophenyl / CO 146-148 22nd phenyl-CH ₂ -CO- 119-120 25th phenyl-CH = GH-CO- 135-136 24th nC ₅ II ₇ -O-CO- 58-59 25th CH.-CH-O-CO- oh ₅ 147-149 26th CH ₅ / CH ₂ / _12- i ₄ -0-C0- / mixture / oil 27th CH, / CH ₂ / .-CH-CK ₂ -O-CO- c ₂ ^h ₅ oil 28th / c ₂ i ^ / ₂ n-co- 132-135 29th CHyS0 ₂ - 133 30th / 4-me t i1-f en i1 / -S 0 ₂ - 158 31st c ₂ h ₅ -co- 146-147

The activity of herbicides containing the pyridine derivatives of formula (I) as an active ingredient was determined in a greenhouse.

A 0.5 wt% solution of the active ingredient in acetone or methanol was added and 0.5 wt% nonionic emulsifier (isooctylphenol polyethoxyethanol) was added. The solution was diluted appropriately with water. Weeds served as Gallium aparine and 81 days old aiba. The amount of active ingredient required to kill 90% of said weeds was determined (EDqq /) and is given in kg / ha. for example, a similar formulation (A) containing 2-chloro-3,5-oleo-4-acetoxy-6-methylpyrldine known from U.S. Patent No. 5,859,295 was used.

The results are shown in Table II. Table below. The active ingredient is identified by the number of the relevant example and by the number given in Table I.

II. spreadsheet

Sign of active ingredient KD _go / kg / ha / Example 1 0.15 Example 2 0.05 3 · Example 0.14 Example 5 0.23 7 0.11 8th 0.18 9- 0.02 10th 0.25 11th 0.02 12th 0.1 13th 0.3

-7182.008

Sign of active ingredient

ED _go / kg / ha /

14th

15 ·

16th

1718th

19th

20th

21st

22nd

2J.

24th

25th

26th

2731. A

0.25

0.21

0.27

0.02

L>, 06

0.02

0.26

0.29

0.02

0.04

0.02

0.02

0.27

0.03

0.07

0.32

Claims (2)

Patent claims CLAIMS 1. An herbicide formulation wherein the active ingredient is 0.01-90% by weight of a 2-chloro-3,5-diiodopyridine derivative represented by the general formula (I): in which R is hydrogen, an alkali metal or 2-18 azene alkylcarbonyl-. , 2-5 azene atoms halo-alkylene-carbonyl, 2-18 azene-atoms alkoxycarbonyl, 3-5-azene atoms alkenylcarbonyl, 4-7-azene atoms cycloalkylcarbonyl, benzylcarbonyl, aziryl -carbonyl, di (1-4C) alkylene-carbamol or optionally substituted benzoyl substituted with one halogen, one or two nitro, or (1-4C) alkyl, preferably with a natural or artificial mineral. grinds, axomaa carbohydrate ·? gene surfactant, preferably an anionic or nonionic dispersant or emulsifier. 2. The first claim ezerinti herbicide embodiment wherein the compound is 2-chloro-3,5-diiodo-4-acetamido ^contains oxy-pyridine. 3. A process for the preparation of the 2-chloro-3,5-diiodopyridyl derivatives of the general formula (I), in which R is a hydrogen atom, an alkali atom or a C 2-18 alkylcarbonyl group. 2 to 5 carbon atoms haloalkylcarbonyl, 2 to 18 azene atoms alkoxycarbonyl, 3 to 5 azen atoms alkenylcarbonyl, 4 to 7 azen atoms cycloalkylcarbonyl, benzylxoxonyl, azetrylxoxonyl, di / 1-4 azene alkylcarbamoyl, 1-4 azene alkyl azulfonyl, p-toluene azulfonyl, or a benzoyl substituted in each case with halogen, one or two nitroxo groups or one C 1-4 alkyl group. characterized in that the 2-chloro-4-hydroxypyridine is iodinated at the 3-position and then converted to the desired compound of formula (I) wherein R is hydrogen or an ester containing one of the groups defined herein. ---------------------