The present invention relates to novel, herbicidal phenyliminothiadiazabicyclononanone derivatives, a process for their preparation, compositions which contain these compounds, and their use for combating weeds, especially in crops of useful plants, in particular cereals, rice, maize and soya, or for inhibiting plant growth.

Herbicidal phenyliminothiadiazabicyclononanone derivatives are disclosed e.g. in EP-A-0 238 711, EP-A-0 273 417, EP-A-0 312 064 and in Japanese Laid-Open Application Hei 1-186894. These derivatives have differing substituents on the phenyl ring.

Novel phenyliminothiadiazabicyclononanone derivatives having good herbicidal properties have now been found.

The present invention therefore relates to the compounds of the formula I

in which

M is hydrogen, an alkali metal or alkaline earth metal cation or an ammonium cation,

A is C ₂ -C ₆ alkylene,

R _j is chlorine or bromine, and

R ₂ is hydrogen or fluorine.

In the formulae I of the phenyliminothiadiazabicyclononanone derivatives according to the invention, suitable alkylene groups can be straight-chain or branched alkylene groups, for example ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene and n-hexylene radicals, and the branched isomers thereof.

Among alkali metal and alkaline earth metal cations, those of lithium, sodium, potassium, magnesium or calcium are especially to be emphasized, but in particular those of sodium or potassium.

Suitable ammonium cations are derived e.g. from primary, secondary and tertiary aliphatic and aromatic amines, such as methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine; heterocyclic amines, e.g. pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, N-methylmorpholine, N-methylthiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, e.g. anilines, methoxyanilines, ethoxyanilines, o, m or p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- or p-chloroanilines.

Other suitable ammonium cations are derived from quaternary ammonium bases and are, in general, the cations of haloammonium salts, e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.

The possible presence of at least one asymmetric carbon atom in the compounds of the formula I has the effect that the compounds can occur either as optically active individual isomers or in the form of racemic mixtures. In the present invention, the active compounds of the formula I are to be understood as meaning both the pure optical antipodes and the racemates.

Preferred compounds of the formula la

are those in which A, R _j and R ₂ are defined under formula I.

Among these, particularly preferred compounds are those in which R _j is chlorine and R ₂ is fluorine.

Likewise particularly preferred compounds of the formula la are those in which A is C ₂ -C ₄ alkylene, R _j is chlorine and R ₂ is fluorine.

Very particularly preferred compounds among these are those in which A is the group

CH ₃ c ₂ H ₅

— CH— or — CH— .

The process according to the invention for the preparation of the compounds of the formula I is carried out in analogy to known processes, as described e.g. in EP-A-0 312 064 and EP-A-0468 924, and comprises converting a compound of the formula II

using thiophosgene under customary conditions to the isothiocyanate of the formula III

and subsequently reacting this with hexahydropyridazine of the formula V

to give the compound of the formula IV

where, in the compounds of the formulae II, III and IV, M, A, R _j and R ₂ are as defined under formula I, and then allowing the resulting compound of the formula IV to react with phosgene, diphosgene (trichloromethyl chloroformate) or triphosgene (bis(trichloromethyl) carbonate) to give the compound of the formula I.

This preparation process is illustrated in greater detail by way of example in the following reaction scheme.

Reaction scheme:

The isothiocyanate of the formula III is obtained in a manner known per se by reacting the corresponding amine of the formula II with thiophosgene. Processes of this type are described, for example, in EP-A-0 304 920, pages 53 and 55; EP-A-0 312 064, page 11, last section and page 12, lines 12-18; and EP-A-0468 924, page 21, lines 29-47, page 22, Example H2, and page 27, Example H17.

The compound of the formula IV is obtained in a manner known per se by reacting the isothiocyanate of the formula III with hexahydropyridazine of the formula V. Reactions of this type are described, for example, in EP-A-0 312 064, page 11, last section, page 12, lines 19-24; EP-A-0468 924, page 16, last section and page 17, first section, page 19, lines 42-46 and page 22, Example H3.

The cyclization of the hexahydropyridazinylthiocarbonylamino derivative of the formula IV can expediently be carried out using phosgene, diphosgene (trichloromethyl

chloroformate) or triphosgene (bis(trichloromethyl) carbonate) in an inert solvent at low temperatures, preferably 0 to 50°C, particularly preferably at 0 to 15°C. Cyclizations of this type are described, for example, in EP-A-0312 064, page 11, lines 1-40 and Preparation Examples 1 to 5 on pages 13 and 14; and EP-A-0468 924, page 19, lines 47-51, page 23, Example H4 and page 28, Example H19.

The intermediates of the formulae III and IV are novel and were specifically developed for the synthesis of the compounds of the formula I. They therefore also form a subject of the present invention.

The preparation of the starting compound of the formula II is carried out by customary processes, such as described, for example, in Beilsteins Handbuch der Organischen Chemie (Beilstein's Handbook of Organic Chemistry), 4th edition, E III 6, page 1019; E IV 6, page 1542, and references cited there; and also in Boll. Chim. Farm. 102 (8), 522-540 (1963).

The hexahydropyridazine of the formula V is known or can be prepared analogously to processes known from the literature, for example Bull. Soc. Chim. France 1957, 704; EP-A-0 304 920, pages 9-11 (Schemes 2-4); and EP-A-0468 924, page 19, last section, page 20, first section and page 28, Example H18.

The final product of the formula I can be isolated in the customary manner by carefully concentrating and or evaporating the solvent in vacuo and purified by recrystallizing or triturating the solid residue in solvents in which it does not readily dissolve, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

Suitable application methods for use, according to the invention, of the compounds of the formula I or compositions comprising these are all those customary in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques, for example the controlled release of active ingredient. To this end, the active ingredient in solution is absorbed on mineral granular supports or polymerized granules (urea/formaldehyde) and dried.

If desired, a coating can additionally be applied (coated granules), which enables the active ingredient to be delivered in metered form over a certain period.

The compounds of the formula I can be employed in unchanged form, i.e. as they are obtained in the synthesis, but they are preferably processed in the customary manner using the auxiliaries conventional in formulation technology, e.g. to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusting agents, granules or microcapsules. The application processes such as spraying, atomizing, dusting, wetting, scattering or watering are chosen accordingly, like the nature of the compositions, the desired targets and the given conditions.

The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I or at least one active ingredient of the formula I and, if desired, one or more solid or liquid additives, are produced in a known manner, e.g. by intimately mixing and/or grinding the active compounds with the additives, e.g. solvents or solid carriers. Additionally, surface-active compounds (surfactants) can also be used in the production of the formulations.

Possible solvents are: aromatic hydrocarbons, in particular the fractions C ₈ to C _p , such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ethers, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and their esters, such as rapeseed, castor or soya bean oil; and if desired also silicone oils.

Solid carriers used, e.g. for dusting agents and dispersible powders, are as a rule ground natural minerals, such as calcites, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, highly disperse silicic acid or highly disperse absorbent polymers can also be added. Possible granulated, absorptive granular supports are porous types, e.g. pumice, brick dust, sepiolite or bentonite, and possible non-sorptive support materials are e.g. calcite or sand. Moreover, a multiplicity of pregranulated materials of inorganic or organic nature such as, in particular, dolomite or comminuted plant remains can be used.

Depending on the type of active ingredient of the formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning

surfactant mixtures.

Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Soaps which may be mentioned are the alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids (C _{] 0} -C ₂₂ ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut or tallow oil. The fatty acid methyl tauride salts may also be mentioned.

More frequently, however, so-called synthetic surfactants are used, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates as a rule are present as alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts and contain an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a fatty alcohol sulfate mixture prepared from natural fatty acids. Included here are also the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having 8-22 C atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid-formaldehyde condensation product.

Appropriate phosphates, e.g. salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids are also suitable.

Possible non-ionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts of polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene

glycol having 1 to 10 carbon atoms in the alkyl chain and containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The said compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of non-ionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglcyol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylenesorbitan trioleate are also suitable.

The cationic surfactants are primarily quaternary ammonium salts which, as N substituents, contain at least one alkyl radical having 8 to 22 C atoms and, as further substituents, contain lower, free or halogenated alkyl or benzyl radicals or lower hydroxyalkyl radicals. The salts are preferably present as halides, methylsulfates or ethyl- sulfates, e.g. the stearyltrimethylammonium chloride or the benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants conventional in formulation technology, which can also be used in the compositions according to the invention, are described inter alia in the following publications:

- "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.

- M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

- Dr. Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981.

The herbicidal preparations as a rule contain 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient of the formula I, 1 to 99 % of a solid or liquid formulation auxiliary and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.

While rather concentrated compositions are preferred as commercial products, the end user as a rule uses dilute compositions.

The compositions can also contain further additives such as stabilizers, e.g. from free or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients for achieving specific effects.

In particular, preferred formulations are composed as follows: (% = per cent by weight)

Emulsifiable concentrates: Active ingredient: 1 to 90 %, preferably 5 to 50 % Surface-active agent: 5 to 30 %, preferably 10 to 20 % Solvent: 15 to 94 %, preferably 70 to 85 %

Dusts:

Active ingredient: 0.1 to 50 %, preferably 0.1 to 1 %

Solid carrier: 99.9 to 90 , preferably 99.9 to 99 %

Suspension concentrates:

A Accttiivvee ingredient: 5 to 75 %, preferably 10 to 50 %

Water: 94 to 24 %, preferably 88 to 30 %

Surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powder: Active ingredient: 0.5 to 90 %, preferably 1 to 80 % Surface-active agent: 0.5 to 20 %, preferably 1 to 15 % Solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules: Active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % Solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The active ingredients of the formula I are as a rule successfully employed at application rates of 0.001 to 2 kg/ha, in particular 0.005 to 1 kg/ha. The dosage necessary for the desired effect can be determined by tests. It is dependent on the type of action, the development stage of the crop plant and of the weed and on the application (site, time, process) and, limited by these parameters, can vary within wide ranges.

The compounds of the formula I are distinguished by selective herbicidal properties which give them an excellent capacity for use in crops of useful plants, in particular in cereals, rice, maize and soya.

Crops are also understood as meaning those which have been made tolerant to herbicides or herbicide classes by conventional cultural or recombinant DNA methods.

The following examples illustrate the invention further, without restricting it.

Preparation examples:

Example HI : 2-| l-(2-Chloro-4-fluoro-5-isothiocyanatop enylthio) | butyric acid (Intermediate)

A suspension of 39.0 g of 2-[l-(5-amino-2-chloro-4-fluorophenylthio)] butyric acid in 100 ml of ethylene chloride is added in portions with stirring at room temperature to a mixture of 29.6 g of calcium carbonate, 14.8 ml of thiophosgene in 200 ml of ethylene chloride and 200 ml of water. After stirring at room temperature for 6 hours, the reaction mixture is treated with 200 ml of water and 400 ml of ethyl acetate and rendered acidic using 2 N hydrochloric acid. The organic phase is separated off and dried over sodium sulfate. After evaporating, 31.0 g of the desired 2-| l-(2-chloro-4-fluoro-5- isothiocyanatophenylthio)Jbutyric acid having a melting point of 104-107°C are obtained.

Example H2: 2-ri-r2-Chloro-4-fluoro-5-(l-hexahvdropyridazinylthiocarbony lamino)- phenylthiollbutyric acid(Intermediate)

COOH

A solution of 12.5 g of 2-[l-(2-chloro-4-fluoro-5-isothiocyanatophenylthio)] butyric acid in 100 ml of ethylene chloride is added dropwise with stirring at room temperature to a solution of 5.0 g of hexahydropyridazine in 100 ml of alcohol. After stirring at room temperature for 3 hours, the reaction mixture is evaporated in vacuo. 1 1.0 g of 2-[l-[2-chloro-4-fluoro-5-(l-hexahydropyridazinylthiocarbony lamino)phenylthio|lbutyric acid having a melting point of 164- 165°C are obtained.

Example H3: 9-[4-Chloro-2-fluoro-5-(l-oxycarbonylpropylthio)phenyliminol - 8-thia-l,6-diazabicyclo[4.3.01nonan-7-one

A solution of 7.8 g of 2-[l-[2-chloro-4-fluoro-5-(l-hexahydropyridazinylthio- carbonylamino)phenylthio]]butyric acid in 100 ml of ethylene chloride is added dropwise with stirring at 0-5°C to 20 ml of a 20 % phosgene solution in toluene. The reaction mixture is subsequently stirred at room temperature for 6 hours and then poured into ice water. The organic phase is separated off and dried over sodium sulfate. After evaporating in vacuo, 15.0 g of 9-[4-chloro-2-fluoro-5-(l-oxycarbonylpropylthio)phenyliminoJ - 8-thia-l,6-diazabicyclo[4.3.0]nonan-7-one having a melting point of 146- 148°C are obtained.

The compounds of the formula I compiled in Table 1 can be prepared in an analogous manner.

Table 1: Compounds of the formula la

Cpd. No. R, Physical data

CH ₃

1.037 Br -CH-

By reaction with e.g. alkali metal or alkaline earth metal hydroxides, primary, secondar}' or tertiary amines and quaternary ammonium bases, these compounds can be converted into the corresponding compounds in which M is an alkali metal or alkaline earth metal cation or an ammonium cation.

Table 2: Compounds of the formula lb

C ₂ H ₅

Cpd. No. R ₂ M Physical data

2.001 F Na 2.002 H Na

2.003 HoN O

2.004 H H ₉ N o 2.005 F Li

Physical data

_!

Cpd. No. R ₂ M Physical data

2.048 H N

AA

2.049 H H ₂ N s

Table 3: Compounds of the formula Ic

Cpd. No. R ₂ M Physical data

3.001 F Na

3.002 H Na

3.003 F H ₂ N o

Cpd. No. R ₂ M Physical data

Cpd. No. R ₂ M Physical data

3.046 F HC≡C-CH ₂ NH ₃ 3.047 H HC≡C-CH ₂ NH ₃

3.048 H ₂ N

3.049 H HoN S

Formulation examples for active ingredients of the formula I (% = per cent by weight)

Fl. Emulsion concentrate a) b) c) d)

Active ingredient as in

Tables 1-3

Calcium dodecylbenzenesulfonate

Castor oil polyglycol ether

(36molofEO)

Octylphenol polyglycol ether 4% 2%

(7-8molofEO)

Cyclohexanone 109. 209?

Aromatic hydrocarbon mixture 85% 78% 55 % 16%

C ₉ -C ₁₂

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d)

Active ingredient as in Tables 1-3 5 % 10 % 50 % 90 %

Dipropylene glycol methyl ether 20% 20% Polyethylene glycol MW 400 20%. 10%

N-Methyl-2-pyrrolidone 30% 10% Aromatic hydrocarbon mixture 75% 60% ₉ -C] ₂

The solutions are suitable for application in the form of very small drops.

F3. Wettable powder a) b) c) d)

Active ingredient as in

Tables 1-3 5% 25% 50% 80%

Sodium lignosulfonate 4% - 3%

Sodium laurylsulfate 2% 3% - 4%

Sodium diisobutylnaphthalene- sulfonate 6% 5% 6%

Octylphenol polyglycol ether 1% 2%

(7-8molofEO)

Highly disperse silicic acid 1% 3% 5% 10%

Kaolin 88% 62% 35%

The active ingredient is well mixed with the additives and well ground in a suitable mill. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c)

Active ingredient as in Tables 1-3 0.1 % 5 % 15 % Highly disperse silicic acid 0.9 % 2 % 2 % Inorg. carrier 99.0 % 93 % 83 % ( 0.1- 1 mm) e.g. CaCO ₃ or SiO ₂

The active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is then evaporated in vacuo.

F5. Coated granules a) b) c)

Active ingredient as in Tables 1-3 0.1 % 5 % 15 %

Polyethylene glycol MW 200 1.0 % 2 % 3 %

Highly disperse silicic acid 0.9 % 1 % 2 %

Inorg. carrier 98.0 % 92 % 80 % (00.1 - 1 mm) e.g. CaCO ₃ or SiO ₂

The finely ground active ingredient is uniformly applied in a mixer to the carrier material moistened with polyethylene glycol. Dust-free coated granules are obtained in this manner.

F6. Extruder granules a) b) c) d)

Active ingredient as in

Tables 1-3

Sodium lignosulfonate

Carboxymethylcellulose

Kaolin

The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and then dried in a stream of air.

F7. Dusting agent a) b) c)

Active ingredient as in Tables 1-3 0.1 % 1 % 5 %

Talc 39.9 % 49 % 35 %

Kaolin 60.0 % 50 % 60 %

Ready-to-apply dusting agents are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill.

F8. Suspension concentrate a) b) c) d)

Active ingredient as in

Tables 1-3

Ethylene glycol

Nonylphenol polyglycol ether

(15 mol of EO)

Sodium lignosulfonate

Carboxymethylcellulose

37% aqueous formaldehyde solution

Silicone oil emulsion

Water

The finely ground active ingredient is intimately mixed with the additives. A suspension concentrate is thus obtained from which suspensions of any desired concentration can be prepared by diluting with water.

Biological examples

Example B 1 : Post-emergence herbicidal action (contact herbicide)

Monocotyledonous and dicotyledonous test plants are raised in a greenhouse in plastic pots containing standard soil and sprayed at the 4- to 6-leaf stage with an aqueous suspension of the test substances of the formula I, prepared from a 25 % wettable powder (Example F3, b)), corresponding to a dosage of 2 kg of AITha (500 1 of water/ha). Cultivation of the test plants is then continued in the greenhouse under optimum conditions. After a test period of about 18 days, the test is assessed using a 9-stage marking scale (1 = complete damage, 9 = no action). Assessment marks of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.

Test plants: Sinapis, Solanum, Ipomoea, Stellaria.

The compounds of Tables 1-3 show potent herbicidal action in this test.

Examples of the good herbicidal action are shown in Table B 1.

Table B 1 : Post-emergence action:

Test plants: Sinapis Solanum Ipomoea Stellaria

Active ingredient

No.

1.002 1 1 1 1

1.004 1 1 1 1

The same results are obtained if the compounds of the formula I are formulated as in Examples Fl, F2 and F4 to F8.