CA2076240A1 - Herbicides - Google Patents

Abstract

Abstract Novel herbicides:

Benzothiazolone derivatives of formula I

(I) wherein Y is oxygen or sulfur;
R1 is hydrogen or fluorine; and R2 is hydrogen, C1-C6alkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted C1-C6alkyl, C2-C4alkenyl, or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted C1-C6alkyl;
carboxy-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, halo-C1-C6alkoxycarbonyl-C1-C4-alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C2alkoxy-carbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C5alkyl-aminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl, C1-C4alkylsulfonyl, C3-C6-alkenyloxy-C1-C4alkyl, C1-C8alkylcarbonyl, , , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or C1-C4alkyl;
have good pre- and post-emergence selective herbicidal properties.

Description

Novel herbicides The present invention relates to novel herbicidally active benzothiazolone derivatives, to processes for the preparation thereof, to compositions comprising them as active ingre-dients and to the use thereof for controlling weeds, especially selectively in crops of useful plants.

Herbicidally active benzothiazolone derivatives are known, for example, from US Patent 4 786 310. Novel herbicidally active benzothiazolone derivatives have now been found.

The benzothiazolone derivatives according to the invention have the formula I

~~ ~ s (I) I ~o wherein Y is oxygen or sulfur;
R1 is hydrogen or fluorine; and R2 is hydrogen, C1-C6alkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted Cl-C6alkyl, C2-C4aLl~enyl, or C3-C6alkynyl; C1-C4aL~coxy-C1-C4alkyl, Cl-C4aLlcoxy-Cl-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted C1-C6alkyl;
carboxy-Cl-C4alkyl9 Cl-C6alkoxycarbonyl-CI-C4alkyl, halo-CI-C6aLlcoxycarbonyl-Cl-C4-aLkyl, C1-C4aLkoxy-C1-C2aL~coxycarbonyl-CI-C4alkyl, Cl-C6alkoxycarbonyl-CI-C2alkoxy-carbonyl-Cl-C4alkyl, C3-C6cycloaLkyl-Cl-C2aLkoxycarbonyl-Cl-C4alkyl, Cl-C5aLkyl-aminocarbonyl-Cl-C4aL~cyl, di-Cl-Csalkylaminocarbonyl-CI-C4alkyl, C3-C6cycloaLkyl, Cl-C4aLkylthio-CI-C~,aLkyl, benzyl or halo-substituted benzyl, Cl-C4alkylsulfonyl, C3-C6-alkenyloxy-Cl-C4aLIcyl, Cl-Cgalkylcarbonyl, C1-C4alkYI-COO C

20762~0 Cl-G4alkyl-COC~Cs ~ ~C , Cl-C4alkylthiocarbonyl-Cl-C4alkyl, or the group Il C1 - C4alkyl - S - I - CH - O - C - Cl - C4alkyl o R3 R3 is hydrogen or Cl-C4aL~cyl; and R4 is hydrogen or Cl-C4aL~yl.

The aL~cyl groups appearing in the definition of substituent R2 may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or the isomeric pentyls, hexyl or the isomeric hexyls.
Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and 7-chloroheptyl; preferably trichloromethyl, difluorochloromethyl, tri-fluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.

In the above definitioDs, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Cl-C4alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, isobutylsulfonyl and tert-butyl-sulfonyl.

The C2-C4aL~cenyl radicals may be in the Z-fo~n (cis) or in the E-form (trans) and may be straight-chain or branched. ALIcenyl radicals having a chain length of two or three carbon atoms are preferred. Examples of C2-C4alkenyl radicals are: vinyl, allyl, methallyl, 20762~0 1-methylvinyl and but-2-en- l-yl. Vinyl and allyl are preferred. In halo-substituted C2-C4-alkenyl radicals the individual meanings of halogen are fluorine, chlorine, bromine and iodine. Preferred h~logen atoms that may occur as substituents of C2-C4aL~cenyl radicals are fluorine and chlorine. Preferred halo-substituted C2-C4alkenyl radicals are those having a ehain length of two or three carbon atoms. Espeeially preferred C2-C4aLkenyl radicals mono- to tri-substituted by halogen are 1-ehlorovinyl, 2-ehlorovinyl, 3-fluoroallyl and 4,4,4-trifluorobut-2-en-1-yl. l-Chlorovinyl and 2-ehlorovinyl are very espeeially preferred.

AL~cylthio is, for exarnple, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, see-butylthio and tert-butylthio, preferably methylthio and ethylthio.

The C2-C6aL~ynyl radicals may be straight-ehain or branched. ALIcynyl radicals having a chain length of 2 or 3 carbon atoms are preferred. C2-C6aL~cynyl radicals are, for example, ethynyl, propargyl, 1-propynyl, 3-butynyl, 1-methylpropargyl, 3-pentynyl and 3-hexynyl, with ethynyl and propargyl being especially preferred.

The C3-C6eyeloalkyl groups appearing in the definition of substituent R2 may be substi-tuted or unsubstituted and inelude, for example, eyelopropyl, 2-fluoroeyelopropyl, 2,4-difluoroeyelopropyl, 2-ehloroeyelopropyl, 2,3-dichloroeyclopropyl, 2-methylcyclopropyl, 2-methylthioeyelopropyl, 2,3-dimethyleyelopropyl, 2-methoxyeyelopropyl, eyclobutyl, cyclopent~yl, 3-methyleyclopentyl, 3,4-dimethoxycyclopentyl, cyelohexyl, 3-fluoroeyclo-hexyl, 4-methyleyelohexyl and 4-methylthioeyclohexyl.

Of the compounds of formula I preference is given to those wherein Rl is fluorine, with Y
preferably being oxygen.

Special preference is given to those compounds of formula I wherein R2 is hydrogen, Cl-C4aLIcyl, C2-C4aLIcenyl, or C2-C4alkynyl; halo-substituted Cl-C4alkyl, C2-C4alkenyl, or C3-C4alkynyl; C1-C4aLIcoxy-Cl-C4alkyl, Cl-C4alkoxy-C1-C2alkoxy-C1-C2aL~cyl, 1-phenyl-propen-3-yl, cyano- or C3-C6cyeloaL~cyl-substituted Cl-C4alkyl, benzyl or halo-substituted benzyl, C3-C6alkenyloxy-Cl-C4aL~cyl, Cl-C8aL~ylcarbonyl, C -C4alkyl-COC~O

20762~0 C1-C4alkyl-CO~C~ ~ Cl-C4aLIcylthiocarbonyl-Cl-C4aL~cyl or the group Il Cl - C4alkyl - S - I - CH - O - C- Cl - C4alkyl o R3 R3 is hydrogen or Cl-C4alkyl; and R4 is hydrogen or Cl-C4alkyl.

Special interest is accorded also to compounds of formula I wherein R2 is hydrogen, Cl-C4alkyl, C2-C4alkenyl, or C2-C4alkynyl; halo-substituted Cl-C4alkyl, C2-C4alkenyl, or C3-C4alkynyl; or Cl-C2alkXY-C,-C2alkYI

Very special preference is given to those compounds of forrnula I wherein R2 is hydrogen, Cl-C4alkyl, C2-C4alkenyl, fluoro-substituted Cl-C4alkyl or C2-C4alkenyl.

In a further prominent group of compounds of formula I, R2 is C3-C6cycloalkyl, C3-C6-cycloaLI~yl-substituted Cl-C6alkyl; Cl-C4alkylthio-Cl-C4aLkyl, benzyl, or halo-substituted benzyl, Cl-C4alkylsulfonyl, C3-C6alkenyloxy-Cl-C4alkyl, Cl-C8alkylcarbonyl, C1-C alkyl-COC~O C1-C4alkyl-CO~ RJ

alkylthiocarbonyl-Cl-C4alkyl, or the group Il Cl - C4alkyl - S - C - CH - O - C - Cl - C4alkyl o R3 R3 is hydrogen or Cl-C4aL~cyl; and 20762~0 R4 is hydrogen or Cl-C4allcyl;
special prominence being given to those compounds wherein Y is oxygen, Rl is fluorine and R3 is hydrogen or methyl.

In a very especially preferred group of compounds of formula I, Y is oxygen, R1 is ~luorine and R2 is Cl-C3alkyl, CH2F, CH2CH2F, CH2CH2CH2F, CHF2, allyl, propargyl, 1-methyl-3-propynyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropoxy-carbonylmethyl, 1-(methoxycarbonyl)-ethyl, 1-(ethoxycarbonyl)-ethyl or 1-(isopropoxy-carbonyl)-ethyl.

A preferred individual compound within the scope of formula I is:
~-[3-(1 -methylethyl)-6-fluoro-2(3H)-benzothiazolon-5-yl]-8-thia-1,6-diazabicyclo[4.3.0]-nonan-7-one (Compound No. 1.001).

In a further, especially preferred sub-group of compounds of formula I,R2 is halo-substituted Cl-C6alkyl, C2-C4alkenyl, or C3-C6alkynyl; Cl-C4alkoxy-CI-C4-alkyl, Cl-C4alkoxy-CI-C2alkoxy-C~-C2alkyl, cyano- or C3-C6cycloalkyl-substitutedCl-C6alkyl; carboxy-CI-C4alkyl, C~-C6alkoxycarbonyl-C~-C4alkyl, Cl-C4alkoxy-Cl-C2-alkoxycarbonyl-Cl-C4alkyl, C~-C6alkoxycarbonyl-C~-C2alkoxycarbonyl-C~-C4alkyl, C3-C6cycloalkyl-CI-C2alkoxycarbonyl-Cl-C4alkyl, Cl-Csalkylaminocarbonyl-CI-C4alkyl, di-Cl-Csalkylarninocarbonyl-Cl-C4alkyl, C3-C6cycloalkyl, Cl-C4aLkylthio-CI-C4alkyl, C3-c6alkenyloxy-cl-c4aL~cyls C -C alkyl-COc~o C1-C4alkyl-CO~S , ~ , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group Il Cl - C4alkyl - S - I - I ~ - O - C - Cl - C4alkyl o R3 R1 preferably being fluorine and Y being oxygen.

Of that group special preference is given to those compounds wherein R~ is Cl-C4alkoxy-CI-C4aLlcyl, Cl-C4alkoxy-CI-C2alkoxy-Cl-C2alkyl, cyano-substituted Cl-C6alkyl; carboxy-CI-C4alkyl, Cl-C6alkoxycarbonyl-Cl-C4alkyl, Cl-C4alkoxy-Cl-C2-alkoxycarbonyl-CI-C4alkyl, Cl-C6alkoxycarbonyl-CI-C2alkoxycarbonyl-CI-C4alkyl, C3-C6cycloalkyl-CI-C2alkoxycarbonyl-CI-C4alkyl, Cl-Csalkylaminocarbonyl-Cl-C4alkyl, di-Cl-C5alkylarninocarbonyl-CI-C4alkyl or C3-C6cycloaIkyl, but more especially Cl-C6-alkoxycarbonyl-CI-C4alkyl or Cl-C4alkoxy-CI-C2alkoxycarbonyl-CI-C4alkyl.

The compounds of formula I are prepared by converting an isothiocyanate of formula II
Rl S=C--N ~ S
\=< ,~ (II), NI O

wherein the substituents Rl and R2 are as defined for formula I, with a hexahydro-pyridazine of formula III

,~ NH
~NH (III) into a compound of forrnula IV

Rl N C NH~ S
CNH ~ (IV) which is then reacted with a compound of formula V

CYCl2 (V), 20762~0 wherein Y is oxygen or sulfur, in the presence of a base.

The reaction of the isothiocyanate of formula II with the hexahydropyridazine offormula m is advantageously carried out in an inert solvent at temperatures of from -5C
up to the boiling temperature of the solvent, especially from 0 to +50C, preferably at room temperature. Suitable solvents for this reaction are, for example, toluene, xylene, ethyl acetate and acetonitrile.

The reaction of the compound of formula IV with the compound of formula V is advanta-geously carried out in an inert solvent at low temperatures, preferably at from 0 to +50C, especially at from 0 to +15C. Suitable bases for this reaction are, for example, pyridine, triethyla nine and N,N-dimethylaniline. Suitable solvents are, for example, 1,2-dichloro-ethane, dichloromethane and toluene.

The hexahydropyridazine of formula III used as starting material for the compounds of formula I according to the invention is known from EP-A-0 304 920. The isothiocyanates of formula II and the preparation thereof are described in US Patent 4 828 605.

The processes given above can be carried out analogously to processes known in the literature. The reaction conditions preferred in those processes, such as temperature, molar ratios of the starting materials, reaction procedure, solvent, any reagents which may be necessary, such as acids, basçs, water-binding agents etc., are familiar to the person skilled in the art~

The compounds of formula I are used in unmodified form, as obtainable from the synthesis, or, preferably, together with the adjuvants customarily employed in formulation technology and are therefore formulated in known manner e.g. into emulsifiable concen-trates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, sohlble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended obiectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures comprising thecompound (active ingredient) of formula I and, where appropriate, one or more solid or liquid adjuvants, are p;epared in known manner, e.g. by homogeneously mixing andlor grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, 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 ether; ketones, such as cyclohexanone, isophorone or diacetone alcohol; strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and esters thereof, such as rape oil, castor oil or soybean oil; and, where appropriate, also silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending upon the nature of the compound of formula I to be forrnulated, suitable surface-active compounds are non-ionic, cationic andlor anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be under-stood as comprising mixtures of surfactants.

Both s~called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the al~ali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), 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 oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylaryl 207~240 sulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, aikaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohoUethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene-sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo-aliphatic alcohols, saturated or unsaturatcd fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro-carbon moiety and 6 to 18 carbon atoms in the aL~yl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediarninopolypropylene glycol and aLIcylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain l to 5 ethylene glycol units per propylene glycol unit.

Representative exarnples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or 20762~0 halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi~2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology 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-m, Chemical Publishing Co., New York, 1980-1981.
- Dr. Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981.

The pesticidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I, 1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti-foams, e.~. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

Preferred formulations have especially the following composition (throughout, percentages are by weight) Emulsifiable concentrates:
active ingredient: 1 to 90 %, preferably 5 to 20 %
surface-active agent: 1 to 30 %, preferably 10 to 20 %
liquid carrier: S to 94 %, preferably 70 to 85 %

Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %

20762~0 solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:
active ingredient: S 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 powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier S to 95 %, preferably 15 to 90 %

Granules:
active ingredient: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The compounds of fonnula I are generally used successfully at rates of application of from 0.001 to 4 kg~a, especially from 0.005 to 1 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent upon t'ne type of action, the stage of development of the cultivated plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits.

When used at relatively low rates of application, the compounds of formula I are distin-guished by growth-inhibiting and herbicidal properties, which render them excellently suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, rape, maiæ and rice.

The invention relates also to herbicidal compositions comprising a novel compound of formula I, and to methods of inhibiting plant growth.

Preparation Examples:

Example Pl: Preparation of 2-[6-fluoro-3-(1-methylethyl)-2-benzothiazolon-5-yl-amino-thiocarbonyl] -hexahydropyridazine:
CN C NH~ S
NH I ~0 CH(cH3)2 At a temperature of +5C, a solution of 10.8 g of 6-fluoro-3-(1-methylethyl)-2-benzo-thiazolon-5-yl-isothiocyanate in 150 ml of ethanol is added dropwise to a solution of 3.6 ml of hexahydropyridazine in 50 ml of ethanol. After being stirred for 12 hours at room temperature, the reaction mixture is concentrated by evaporation. Purification by means of silica gel chromatography (ethyl acetate/n-hexane 1:9) yields 6.9 g of 2-[6-fluoro-3-(1-methylethyl)-2-benzothiazolon-5-yl-aminothiocarbonyl]-hexahydropyridazine having a melting point of 198-199C.

Example P2: Preparation of 9-[3-(1-methylethyl)-~fluoro-2(3H)-benzothiazolon-5-yl]-8-thia-l,~diazabicyclo[4.3.0]nonan-7-one (Compound No. 1.001):

CNI ~S F
S ( 1.001 ) I ~o CH(CH3)2 At a temperature of +5C, 7 ml of a 20 % toluene solution of phosgene is added dropwise to a solution of 4.4 g of 2-[6-fluoro-3-(1-methylethyl)-2-benzothiazolon-5-yl-arninothio-carbonyl]-hexahydropyridazine prepared according to Example Pl. After being stirred for one hour, the reaction mixture is poured into ice-water. After separation of the organic phase and drying over sodium sulfate, the solution is concentrated by evaporation.
Chromatographic purification over silica gel (ethyl acetate/n-hexane 1:1) yields 2.9 g of 20762~0 9-[3-(1-methylethyl)-6-fluoro 2(3H)-benzothiazolon-5-yl]-8-thia-1,6-diazabicyclo[4.3.0]-nonan-7-one (Compound No. 1.001) having a melting point of 132-133C.

The compounds of Table 1 can be prepared analogously to the above Example and the preparation processes mentioned in the description:

T~ble 1: Compounds of formula I:

--(N ~ S (I) N~
O

Comp. Rl Y R2 phys. data No.
-1.001 F O (CH3)2CH m.p. 132-133C
1.002 F O H
1.003 F O CH3 1.004 F O C2H5 1.005 F O C3H7 1.006 F O C4Hg 1.007 F O iso-C4Hg 1.008 F O sec-C4Hg 1.009 F O tert-C4Hg 1.010 F O CsHIl 1.011 F O CH3-CH2-CH(CH3)-CH2 1.012 F O CH3-CH2-CH2-CH(CH3) 1.013 F O (C2Hs)2CH
1.014 F O CH3-CH(CH3)-CH(CH3) 1.015 F O CH3-C(CH3)2-CH2 1.016 F O C6Hl3 1.017 F O (C2Hs)2-cH-cH2 1.018 F O (CH3)3-C-CH2-CH2 1.019 F O (CH3~3-C-CH(CH3) 1.020 F O CH3-CH2-CH2-CH2-CH(CH3) 1.021 F O CH3-CH2-CH2-CH(C2Hs) 1.022 F O CH3-CH2-CH2-CH(CH3)-CH2 20762~ 0 Table I (continuation) Comp. Rl Y R2 phys. data No.

1.023 F O CH3-CH2-CH2-C(CH3)2 CH3 - CH2 - CH - CH(CH3)2 1.024 F O
1.025 F O CH3-CH2-CH(CH3)-CH2-cH2 1.026 F O (C2Hs)2(CH3)C
1.027 F O (CH3)2-CH-CH2-CH2-CH2 1.028 F O (CH3)2-CH-CH2-CH(CH3) 1.029 F O CH2=CH
1.030 F O CH2=CH-CH2 1.031 F O CH3-CH=CH-CH2 1.032 F O CH2=C(CH3)-CH2 1.033 F O C6Hs-CH=CH-CH2 1.034 F O HC_C-CH2 1.035 F O CH3-C-C-CH2 1.036 F O HC_C-CH(CH3) 1.037 F O FCH2 1.038 F O F2C~I2 1.039 F O FCH2CH2 1.040 F O CF3CH2 1.041 F O FcH2cH2cH2 1.042 F O ClCH2 1.043 F O BrCH2 1.044 F O Cl3C
1.045 F O F3C
1.046 F O ClCH2CH2 1.047 F O BrCH2CH2 1.048 F O CF3CF3 Cl CH2--1.049 F O >=<
H Cl 1.050 F O ~<CI

20762~0 Table I (continuation) Comp. Rl Y R2 phys. data 1.051 F O H>=<CI

1.052 F O CH2CI >=<H

Cl CH2--1.053 F CH3 H

Cl CH2--1.054 F O H~=<H

Br CH2--1.055 F O H>=<Br 1.056 F O B>=<Br 1.057 F O H>=<sr 1.058 F O CH2Br >=<H

Br CH2--1.059 F CH3 H

Br CH2--1.060 F O H>=<H

1.061 F O IC=-C-CH2 1.062 F O CH3-O-CH2 1.063 F O C2Hs-O-CH2 20762~0 T~ble 1 (continu~tion) Comp. Rl Y R2 phys. d~ta No.

1.064 F O C3H7-O-CH2 1.065 F O C4H9-O-CH2 1.066 F O CH3-O-CH2-CH2 1.067 F O C2H5-O-CH2-CH2 1.068 F O CH3-O-CH2-CH(CH3) 1.069 F O CH3-O-CH2-O-CH2 1.070 F O CH3-O-CH2-CH2-O-CH2 1.071 F O C2Hs-O-CH2-O-CH2 1.072 F O CH3-O-CH2-O-CH2-CH2 1.073 F O C2H5-O-CH2-O-CH2-CH2 1.074 F O C2H5-O-CH2-CH2-O-CH2 1.075 P O C2Hs-O-CH2-CH2-O-CH2-CH2 1.076 F O C6H5-CH=CH-CH2 1.077 F O NC-CH2 1.078 F O NC-CH2-CH2 1.079 F O NC-CH(CH3) m.p. 77-78C
1.080 F O HOOC-CH2 1.081 F O HOOC-CH2-CH2 1.082 F O HOOC-CH(CH3) 1.083 F O HOOC-CH(C2Hs) 1.084 F O HOOC-CH2-CH2-CH2-CH2 1.085 F O CH3OOC-CH2 1.086 F O C2HsOOC-CH2 1.087 F O (CH3)2CH-OOC-CH2 1.088 F O CsHI lOOC-CH2 1.089 F O CH3OOC-CH2-CH2 1.090 F O C2H5OOC-CH2-CH2 1.091 F O (CH3)2CH-OOC-CH2-CH2 1.092 F O CH300C-CH(CH3) 1.093 F O C2H5OOC-CH(CH3) 1.094 F O ClCH2CH2OOC-CH2 1.095 F O FCH2CH200C-CH2 20762~

T~ble I (continu;ltion) Comp. Rl Y R2 phys. d~ta No.
1.096 F O FCH2CH2CH2OOC-CH2 1.097 F O CF3CH2OOC-CH2 1.098 F O CH3O-CH2-CH2OOC-CH2 1.099 F O C2HsOOC-CH(CH3)-OOC-CH2 1.100 F O ~OOC-CH2 1.101 F O C4Hg / O

1.102 F O CH3-S-CH2-CH(CH3) 1.103 F O C2Hs-S-CH2-CH(CH3) resinous 1.104 F O CH3-s-cH2-cH2 1.105 F O C3H7-S-CH2-CH(CH3) 1.106 F O (CH3)2CH-S-CH2-CH(CH3) 1.107 F O C4Hg-S-CH2-CH(CH3) 1.108 F O CsH1l-S-CH2-CH(CH3) 1.109 F O C6H5-CH2 c 1.110 F O ~
~=~ CH2 1 111 F O CH2=CH-CH2-O-CH2 1.112 F O CH3-CO
1.113 F O O~ooc-cH2 1.114 F O ~ OOC-1.115 F O C3H7-S-CO-CH2 1.116 F O CH3-S-CO-CH(CH3)-OOC-CH2 o~ CH2 1.117 F O
~H3 20762~0 Table 1 (continuation) Comp. Rl Y R2 phys. data No.

1.118 F O CH3-SO2 1.119 F O C2Hs-S2 1.120 F O D--CH(CH3) 1.121 F S CH3-CH(CH3) 1.122 F S CH2=CH-CH2 1.123 F S HC--C-CH2 1.124 F S CH2F
1.125 F S C2HsF
1.126 H O CH3 1.127 H O C2H5 1.128 H O (CH3)2-CH
1.129 H O CH2=CH-CH2 1.130 H O CH-C-CH2 1.131 H O CH2=c(cH3)-cH2 1.132 H O CH2F-CH2 1.133 H O CH2F
1.134 H O CH2F-CH2-CH2 1.135 H O CH3-OOC-CH2 1.13~ H O C2Hs-ooc-cH2 1.137 H O CsH1l-OOC-CH2 1.13~ H O CH3-OOC-CH(CH3) 1.139 H O C2Hs-OOC-CH(CH3) 1.140 H O CH2F-CH2-CH2-OOc-cH2 1.141 F O CHFCl-CF2 1.142 F O CF2CI
1.143 F O CF2H-CF2 1.144 F O CHCl=CCl 1.145 F O ~ C2Hs CN

20762~o Tablel(continuation) Comp. Rl Y R2 phys.data No.
1.146 F O - CH-COO- C3H

1.147 F o - CH - COO-C3H7(i) resinous 1.148 F O - CH- COO-C4H

1.149 F o - CH-COO- CH resinous CH3 C2Hs 1.150 F O - CH-COO-CH2- CH n9 1.5819 1.151 F O - CH- CCK}- C - CH3 1.152 . O - CH- COO - CsTI11 nD9 1.5612 1.153 F O - CH- COO- CH2- CH- CH2- CH3 ._T T
CH3 ~3 1.154 F O - CH- COO- CH- CH2- CH2- CH3 ~H3 CH3 .155 F O - CH- COO- CH

Table 1 (continuation) 20762~0 Tablel(continuation) Comp. Rl Y R2 phys.data No.

1.165 F O - CH- COO- C - CH2-CH2-CH3 1.166 F O - CH- COO-CH- CH
I

1.167 F O - CH-COO-CH2-CH2-CH- CH2- CH3 1.168 F O - CH-COO- C - CH2- CH3 1.169 F O - CH-COO- CHr CH2-CH2-CH

1.170 F O CH-COO - CH - CH2-CH

1.171 F O CH-COO- CH2-CH2-O - CH3 m.p.:50-54GC

1.172 F O - CH-COO- CH2- CH2- O-CH2-CH3 m.pnllO-113C

Table 1 (continuation) Comp. Rl Y R2 phys. data No.

1.173 F O --CH--COO--CH2- CH2--O--C3H7 I

1.174 F O --CH--COO--CH2- CH2--O-- CH m.p.: 84-86C

1.17~ F O --CH--COO--CH2- CH2-- C4H9 I

1.176 F O --CH--COO--CH--CH2--O--CH3 I

1.177 F O --CH--COO--CH--CH2--O--CH2CH3 1.178 F O --CH--COO--CH2-CH2--Cl I

1.179 F O --CH--COO--CH2- CH2--F
I
c~3 1.180 F O --CH--COO--CH2- CH2--CH2F
I

1.181 F O --CH--COO--CH2- CF3 I

Table 1 (continuation) Comp. Rl Y R2 phys. data 1.182 F O ~ COO--CH2- COO-CH3 I

1.183 F O --CH--COO--CH2- COO-C2Hs I

1.184 F O --CH--COO--CH--COO-CH3 I

1.185 F O --CH--COO--CH--COO-C2Hs 1.186 F O --CH--COO--CH--COO-CH
I

1.187 F O --CH- COO- CH~

1.188 F O --(~I--C NH--CH3 1.189 F O --CH--C NH--C2Hs 1.190 F O --CH--C-NH - C3H7 20762~0 T~ble 1 (continuation) Nolnp. Rl Y R2 phys. data 1.191 F O --CH--COO--NH--CH

1.192 F O --CH--COO--NH--C4Hg 1.193 F O --CH-COO-N
CH

1.194 F O --CH--CO~\S

1.195 F O --C--COO-H

Cl H3 1.196 F O --C--COO--CH3 (~H3 1.197 F O --C CO~ C2H5 Table 1 (continuation) CNomp. Rl Y R2 phys. data 1.198 F O --C COO--C3H7 1.199 F O --C--COO-C3H7(;

Ci H3 1.200 F O --C--COO-C4Hg 1.201 F O --C--COO--CH
CH3 C2Hs Cl H3 /CH3 1.202 F o --Cl--COO- CH2--CH

1.203 F O --C--COO--C--CH3 Cl H3 1.204 F O --C--COO--CsH

Table I (con~inua~ion) Comp. Rl Y R2 phys. data No.

Cl H3 1.205 F Q --C--COO--CH2--CH--CH2--CH3 1.206 F O --C--COO--CH--CH2- CH2- CH3 Cl H3 /CH2--CH3 1.207 F O --C--COO--CH

Cl H3 1.208 F O --C--COO- CH--CH--CH3 ICH3 Cj H3 1.209 F O --C--COO--CH2--C--CH3 Cl H3 1.210 F O --C--COO--C6HI3 Table 1 (continuation~
Comp. Rl Y R2 phys~ data No.

Cl H3 CH2-CH3 1.211 F O --C--COO-CH2--CH

1.212 F O --C--COO--CH2 CH2--C--CH3 Cl H3 /CH3 1.213 F O --C--COO--CH--C--CH3 Cl H3 1.214 F O --C--COO--CH--CH2- CH2--CH2--CH3 1.215 F O --C--COO--CH--CH2- CH2--CH3 Cl H3 1.216 F O --C--COO--CH2- CH--CH2- CH2- CH3 Table 1 (continu;~tion) Comp. Rl Y R2 phys. d~ta No.

Cl H3 Cl H3 1.217 F O --C--COO- C--CH2- CH2- CH3 Cl H3 /CH3 1.218 F O --C--COO-CH--CH
I

I

1.219 F O --C--COO- CH2- CH2- CH--CH2--CH3 CH3 l H3 1.220 F O --C--COO--C--CH2--CH3 l H3 /CH3 .221 F O --C--COO--CH2- CH2- CHr CH

.222 F O --C--COO--CH--CH2~H

20762~o Table 1 (continuation) Nomp. Rl Y R2 phys. data Cl H3 1.223 F O --C--COO--CH2- CH2- 0--CH3 1.224 F O --C--COO--CH2--CH2- 0 - CH2- CH3 1.225 F O --C--COO--CH2--CH2--0--C3H7 1.226 F O --C--COO--CH2- CH2--O CH

Cl H3 1.227 F O --C--COO--CH2- CH2--0--C4Hg 1.228 F O --C--COO--CH--CH2~ 0--CH3 207624~

Table 1 (con~inua~ion) Comp. Rl Y R2 phys. dat~
No.

Cl H3 1.229 F O --C--COO--CH--CH2--O--CH2CH3 1.230 F O --C--COO--CH2- CH2--Cl 1.231 F O --f co~ CH2- CH2--F

1.232 F O --C--COO--CH2- CH2--CH2F

1.233 F O --C--COO--CH2- CF3 1.234 F O --C ~ CO~ CH2- COO-CH3 Table I (continuation) Nomp. Rl Y R2 phys. data 1 238 F O --C--CO~ CH--COO- CH

1 349 F O --C--COO--CH~

20762~0 Table 1 (continuation) Comp. Rl Y R2 phys. data 1.241 F O --C--C NH--C2Hs 1.242 F O --C C-NH C3H7 1 3 ~ H3 1.243 F O --C--COO--NH--CH

1.244 F O --C--COO--NH--C4H9 l H3 / H3 1.245 F O --C~OO-N

CH3 /\
1.246 F O --C COO~ S

20762~0 Table 1 (continua~ion) Comp. Rl Y R2 phys. data No.

1.247 F O --CH--CH2--COO-H

1.248 F O --CH--CH2--COO--CH3 I

1.249 F O --CH--CH2--COO--C2H5 1.250 F O --CH--CH2--COO--C3H7 I

1.251 F O --CH--CH2--COO-C3H7 (;

1.252 F O --CH--CH2- COO-C4Hg (n 1.253 F O --CH- CH2- COO- CH
CH3 C2Hs 1.254 F O --CH- CH2- COO- CH2--CH

1.255 F O --CH--CH2--COO- C - CH3 20762~0 Table I (continuation) Nomp. Rl Y R2 phys. data -1.256 F O --CH--CH2--COO--CsH~

1.257 F O --CH--CH2--COO- CH2- CH- CH2- CH3 1.258 F O --CH--CH2--COO--CH--CHr CH2- CH3 1.259 F O --CH--CH2--COO- CH

1.260 F O --CH- CH2- CO~ CH--CH--CH3 Cl H3 1.261 F O --CH--CH2--CO~ CH2- C--CH3 1.262 F O --CH--CH2--COO- C6H~3 1.263 F O --CH~ CH2- COO-CH2--CH

20762~0 Table 1 (continuation) Cornp. Rl Y R2 phys. data 1.264 F o - CH CH2- COO - CH2 - CH2- C - CH3 1.265 F O - CH - CH2- COO - CH- C - CH3 1.266 F O - CH- CH2- COO- CH- CHr CH2- CH2- CH3 1.267 F O - CH-CH2- CO0-CH- CH2-CHr CH3 1.268 F O - CH- CH2- COO- CH2-CH- CH2-CH2-CH3 1.269 F O - CH- CH2- COO- C - CH2-CH2-CH3 1.270 F O - CH - CH2- COC~ CH- CH

Table 1 (continua~ion) Comp. Rl Y R2 phys. data No.

1.271 F O --CH- CH2- COO- CH2- CH2- CH- CH2--CH3 1.272 F O --CH--CH2--COO- C--CH2--CH3 1.273 F O --CH--CH2--COO--CH2- CH2- CH2- CH

1.274 F O --CH--CH2 CO~ CH--CH2--CH

1.275 F O --CH--CH2--CO~ CH2- CH2- 0--CH3 1.276 F O --CH- CH2- COO--CH2- CH2- 0 - CH2--CH3 1.277 F O ~ CH--CH2--COO--CH2- CH2--O--C3H7 1.278 F O --CH--CH2--COO CH2--CH2--O CH

20762~0 Table_ (continuation) Comp. Rl Y R2 phys. data No.

1.279 F O --CH--CH2--COO--CH2--CH2-- C
I

1.280 F O --CH CH2--COO--CH--CH2--O--CH3 I

1.281 F O --CH--CH2 COO--CH--CH2--O--CH2CH3 1.282 F O --CH--CH2--COO--CH2--CH2--Cl I

1.283 F O --CH--CH2--CO~ CH2--CH2--F
I

1.284 F O --CH--CH2--CO~ CH2 CH2--CH2F
I

1.285 F O --CH--CH2--COO--CH2- CF3 I

1.286 F O --CH--CH2--CO~ CH2- COO-CH3 I

1.287 F O --CH--CH2--CO~ CH2--COO-C2Hs 2~762~0 Table 1 (con~inuation) Comp. Rl Y R2 phys. data 1.288 F O - CH - CH2- COO-CH- COO-CH3 1.289 F O - CH- CH2- COO-CH- COO-C2Hs ~CH3 1.290 F O - CH - CH2- COO-CH- COC~CH
I
C~3 CH3 CH3 1.291 F O - CH- CH2- COO-CH

1.292 F O - CH-CH2- C NH- CH3 1.293 F O -CH- CH2 C NH- C2H5 1.294 F O - CH-CH2- C-NH C3H7 1.295 F O - CH- CH2 COO-NH- CH

2~762~0 Table 1 (continuation) Comp. Rl Y R2 phys. data No.

1.296 FO --CH--CH2 COO--NH--C4H9 1.297 F O --CH--CH2--COO-N

1.298 F O ~ CH2 CIX~ S

1.299 F O --CH--COO-H

C2Hs 1.300 F O --CH--COO--CH3 m.p. 149-151C
C2Hs 1.301 F O --CH--COO--C2Hs C2Hs 1.302 F O --C~--COO--C3H7 nD19 1.5692 C2Hs 1.303 F O --CH--COO-C3H7(;
C2Hs 1.304 F O --CH--COO-C4H
C2Hs Table 1 (continua~ion) Nomp. Rl Y R2 phys. data . . . _ . . _ ~CH3 1.305 F O - CH-COO- CH resinous C2H5 C2Hs 1.306 F O - CH-COO- CH2 - CH resinous .307 F O - CH-COO-C - CH3 .308 F O - CH-COO - CsH
C2Hs .3~ F O - CH- COO- CH2-CH- CH2-CH3 C2Hs CH3 .310 F O -CH- COO- CH- CH2-CH2-CH3 C2Hs CH3 ~CH2- CH3 1.311 F O - CH-COO-CH
l2HS CH2- CH3 .312 F O - CH-COO-CH-CH- CH3 C2Hs CH3 CH3 Tablel(continua~on) Comp. Rl Y R2 phys.data 1.313 F O - CH-COO- CH2- C - CH3 C2Hs CH3 1.314 F O - CH- COO- C6HI3 1.31~ F O - CH-COO-CH2- CH
C2Hs CH2-CH3 1.316 F O - CH- COO-- CH2 CH2- C - CH3 C2Hs CH3 1.317 F O - CH- COO - CH - C - CH3 C2Hs C~I3 CH3 1.318 F O - CH-COO- CH- CH2- CH2- CH2- CH3 C2Hs CH3 1.319 F O - CH-COO- CH - CH2- CH2- CH3 C2Hs C2Hs 1.320 F O - CH- COO- CH2-CH- CH2-CH2- CH3 C2Hs CH3 Tablel(continuation) Comp. Rl Y R2 phys.data No.

1.321 F O - CH-COO-C - CH2-CH2-CH3 C2Hs CH3 1.322 F O - CH-COO-CH- CH

1.323 F O - CH-COO-CH2-CH2-CH-CH2- CH3 C2Hs CH3 1 ~3 .324 F O - CH-COO- C - CH2-CH3 C2Hs CH2- CH3 .325 F O -CH-COO-CH2-CH2-CH2-CH
C2H5 \CH3 /CH3 .326 F O - CH-COO- CH- CH2-CH
C2Hs CH3 CH3 .327 F O - CH-COO-CH2-CH2-O - CH3 C2Hs 2~762~0 Table 1 ~continuation) Comp. Rl Y R2 phys. data No.

1.328 F O --CH--COO- CH2--CH2- O - CH2- CH3 C2Hs 1.329 F O ~ CH--COO--CH2- CH2--O - C3H7 I

1.330 F O --CH--COO--CH2- CH2--O--CH

C2Hs CH3 1.331 F O --CH--CO~ CH2--CH2--O--C4Hg I

C2Hs 1.332 F O --CH--COO--CH--CH2--O--CH3 I

C2Hs 1.333 F O --CH--CO~ CH--CH2--O--CH2CH3 1.334 F O --CH--COO--CH2- CH2--C1 I

1.335 P O ~ CH--COO--CHr CH2--F
I

C2Hs 20762~0 Table I (continuation) Nomp. Rl Y R2 phys. data -C2Hs 1.337 F O --CH--COO--CH2- CF3 I

C2Hs 1.338 F O --CH--COO--CH2- COO-CH3 I

C2Hs 1.339 F O --CH--COO--CH2- COO-C2Hs C2Hs I

1.340 F O --CH- COO--CH--COO-CH3 C2Hs 1.341 F O --CH- COO--CH--COO-C2Hs C2Hs CH3 /c~3 1.342 F O --CH--COO--CH--CO~ CH
I
C2Hs CH3 CH3 1.343 F O --CH- COO- CH~
C2Hs CH3 20762~0 Table 1 (continuation) Comp. Rl Y R2 phys. data 1.344 F O --CH--C NH--CH3 C2Hs O
1.345 F O --CH--C--NH--C2H5 C2Hs O
1.326 F O --CH--C-NH C3H7 1.347 F O --CH--COO--NH--CH

1.348 F O --CH--COO--NH--C4Hg 1.349 F O --CH-COO-N

1.350 F O --CH--CO~¢S

1.351 F O

1.352 F O

Table 1 (continua~on) Comp. Rl Y R2 phys. data No.

1.353 F O

1.354 F O

1.355 H O

1.356 H O

1.357 H O

1.358 H O ~

1.359 F O - CH - COO - CH3 m.p.143-145C

20762~0 Forrnulation Examples for liquid active ingredients of forrnula I (throu~hout~ percentages are bY wei~ht) 1. Emulsifiable concentrates a) b) c) a compound of Table 1 25 % 40 % 50 %
calcium dodecylben~enesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether (36 mol of ethylene oxide)5 % - -tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12 % 4 %
cyclohexanone - 15 % 20 %
xylene mixture 65 % 25 % 20 %

Emulsions of any desired concentration can be produced from such concentrates bydilution with water.

2. Solutions a) b) c) d) a compound of Table 1 80 % 10 % 5 %95 %
propylene glycol monomethyl ether 20 %
polyethylene glycol (mol. wt. 410) - 70 %
N-methyl-2-pyrrolidone - 20 %
epoxidised coconut oil - - 1% 5 %
benzine (boiling range 160-190C) - - 94 %

The solutions are suitable for application in the form of micro-drops.

3. Granules a) b~ c) d) a compound of Table 1 5 % 10 % 8 %21 %
kaolin 94 % - 79 %54 %
highly dispersed silicic acid 1 % - 13 % 7 %
attapulgite - 90 % - 18 %

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

^ 49 -4. Dusts a) b) a compound of Table 1 2 % 5 %
highlydispersed silicicacid 1% S %
talcum 97 %
kaolin - 90 %

Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation Examples for solid active ingredients of formula I (throughout, percentages are bv weight) 5. Wettablepowders a) b) c) acompoundofTable 1 25 % 50 %75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalene-sulfonate - 6 %10 %
octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 %10 %
kaolin 62 % 27 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

6. Emulsifiable concentrate a compound of Table 1 10 %
octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 %
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (36 mol of e;hylene oxide) 4 %
cyclohexanone 30 %
xylene mixture SO %

Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

7. Dusts a) b) acompoundofTable I 5 %8 %
talcum 95 %
kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.

8. Extruder ~ranules a compound of Table 1 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %

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

9. Coated ~ranules a compound of Table 1 3 %
polyethylçne glycol (mol. wt. 200) 3 %
kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

10. Suspension concentrate a compound of Table 1 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
sodium lignosul~onate 10 %

carboxymethylcellulose 1 %
silicone oil in the forrn of a 75%
aqueous emulsion 1 %
water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

The eompounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants eustomarily employed in formulation technology and are therefore formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the eompositions, the methods of applieation, such as spraying, atomising, dusting, scattering or pouring, are ehosen in accordance with the intended objectives ancl the . . .
prevallmg Clrcumstances.

Biolo~ical Examples:

Example B 1: Pre~mer~ence herbicidal action In a greenhouse, immediately after the test plants have been sown in seed trays, the surface of the soil is treated with an aqueous spray mixture corresponding to a rate of application of 4 kg of active ingredient/hectare. The seed trays are kept in the greenhouse at 22 - 25C and 50 - 70 % relative humidity.

The herbicidal action is evaluated after 3 weeks using a scale of nine ratings (1 = total damage, 9 = no damage) in comparison with an untreated control group.

Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action.
Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants).

In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. For example, compound 1.001 exhibits the following herbicidal action against the tested weeds:

Table B1: Pre-emer ence herbicidal action:

Test plant: Avena Sinapis Setaria Stellaria Compound No.
1.001 Example B2: Pre-emer~ence herbicidal action In a greenhouse, immediately after the test plants have been sown in seed trays, the surface of the soil is treated with an aqueous spray mixture corresponding to a rate of application of 2 kg of active ingredient/hectare. The seed trays are kept in the greenhouse at 22 - 25C and 50 - 70 % relative humidity.

The herbicidal action is evaluated after 3 weeks using a scale of nine ratings ( 1 = total darnage, 9 = no damage) in comparison with an untreated control group.

Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action.

Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants).

In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. Examples of good herbicidal activity are given in Table B2:

Table B2: Pre-emergence herbicidal action:

Test plant: Avena Sinapis Setaria Stellaria ComPound No.
1.008 1 3 1.034 1.036 1.092 1.093 2 1.146 3 1.301 2 2 1 2 1.303 3 Example B3: Post-emer~ence herbicidal action (contact herbicide) A number of weeds, both monocotyledonous and dicotyledonous, are sprayed post-emergence (in the 4- to 6-leaf stage) with an aqueous active ingredient dispersion at a rate of 4 kg of active ingredient/hectare and kept at 24-26C and 45-60 'rO relative humidity.
The herbicidal action is evaluated 15 days after treatment using a scale of nine ratings (1 =
total damage, 9 = no damage) in comparison with an untreated control group.

Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action.
Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants).

In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. For example, compound 1.001 exhibits the following herbicidal action against the tested weeds:

20762~o Table B3. Post-emer ence herbicidal action:

Test plant: Avena Setaria Lolium Solanu~ Sinapis Stellaria Compound No.
1.001 1 2 Example B4: Post-emer~ence herbicidal action (contact herbicide) A number of weeds, both monocotyledonous and dicotyledonous, are sprayed post-emergence (in the 4- to 6-leaf stage) with an aqueous active ingredient dispersion at a rate of 2 kg of active ingredient/hectare and kept at 24-26C and 45-60 % relative humidity.
The herbicidal action is evaluated 15 days after treatment using a scale of nine ratings (1 =
total damage, 9 = no damage) in comparison with an untreated control group.

Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action.
Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants).

In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. Exarnples of good herbicidal achvity are given in Table B4:

Table B4: Post-emer ence herbicidal action:

Test plant: Avena Sinapis Setaria Stellaria ComPo-und No.
1.008 2 4 1.034 1 2 1.036 1.092 1 2 1.093 1 2 1.146 2 1.301 2 2 1.303 3 1 1 2 Example B5: Herbicidal action in wild rice (paddy) The weeds Echinochloa crus galli and Monocharia vag., which occur in water, are sown in plastic beakers (surface area: 60 cm2, volume: 500 ml). After sowing, the beakers are 20762~o - ss -filled with water up to the surface of the soil. 3 days after sowing, the water level is increased to slightly above the soil surface (3-5 mm). Application is effected 3 days after sowing by spraying the beakers with the test compounds. The dosage corresponds to an amount of active ingredient of 4 kg a.i. per hectare. The beakers are then kept in a green-house under optirnum growth conditions for rice weeds, i.e. 25-30C and high humidity.

The tests are evaluated 3 weeks after application. The compounds of Table 1 damage the weeds.

Claims (21)

1. A benzothiazolone derivative of formula I

(I) wherein Y is oxygen or sulfur;
R1 is hydrogen or fluorine; and R2 is hydrogen, C1-C6alkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted Cl-C6alkyl, C2-C4alkenyl, or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted C1-C6alkyl;
carboxy-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, halo-C1-C6alkoxycarbonyl-C1-C4-alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C2alkoxy-carbonyl-C1-C4alkyl,C3-C6cycloalkyl-C1-C2alkoxycarbonyl-C1-C4alkyl,C1-C5alkyl-aminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl, C1-C4alkylsulfonyl, C3-C6-alkenyloxy-C1-C4alkyl, C1-C8alkylcarbonyl, , , , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group ;

R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or C1-C4alkyl.

2. A compound according to claim 1 wherein R1 is fluorine.

3. A compound according to claim 1 wherein R1 is fluorine and Y is oxygen.

4. A compound according to claim 1 wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, or C2-C4alkynyl; halo-substituted C1-C4alkyl, C2-C4alkenyl, or C3-C4alkynyl; C1-C4-alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted C1-C4alkyl, benzyl, or halo-substituted benzyl, C3-C6alkenyl-oxy-C1-C4alkyl, C1-C8alkylcarbonyl, , , , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group ;

R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or C1-C4alkyl.

5. A compound according to claim 1 wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, or C2-C4alkynyl; halo- substituted C1-C4alkyl, C2-C4alkenyl, or C3-C4alkynyl; or C1-C2-alkoxy-C1-C2alkyl.

6. A compound according to claim 1 wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, fluoro-substituted C1-C4alkyl or C2-C4alkenyl.

7. A compound according to claim 1 wherein R2 is C3-C6cycloalkyl, C3-C6cycloalkyl-substituted C1-C6alkyl; C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl C1-C4alkylsulfonyl, C3-C6alkenyloxy-C1-C4alkyl, C1-C8alkylcarbonyl, , , alkylthiocarbonyl-C1-C4alkyl, or the group ;

R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or C1-C4alkyl.

8. A compound according to claim 7 wherein Y is oxygen, R1 is fluorine and R3 ishydrogen or methyl.

9. A compound according to claim 1 wherein Y is oxygen, R1 is fluorine and R2 is C1-C3-alkyl, CH2F, CH2CH2F, CH2CH2CH2F, CHF2, allyl, propargyl, 1-methyl-3-propynyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropoxycarbonylmethyl, 1-(methoxy-carbonyl)-ethyl, 1-(ethoxycarbonyl)-ethyl or 1-(isopropoxycarbonyl)-ethyl.

10. 9-[3-(1-methylethyl)-6-fluoro-2(3H)-benzothiazolon-5-yl]-8-thia-1,6-diazabicyclo-[4.3.0]nonan-7-one according to claim 1.

11. A compound according to claim 1 wherein R2 is halo-substituted C1-C6alkyl, C2-C4-alkenyl, or C3-C6alkynyl; C1-C4aLIcoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-Cl-Cralkyl, cyano- or C3-C6cycloalkyl-substituted C1-C6alkyl; carboxy-C1-C4alkyl, Cl-C6-alkoxycarbonyl-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6aLkoxy-carbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxycarbonyl-C1-C4-alkyl, C1-C5alkylaminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, C3-C6alkenyloxy-C1-C4alkyl, , , , C1-C4-alkylthiocarbonyl-C1-C4alkyl, or the group

12. A compound according to claim 11 wherein R2 is C1-C4alkoxy-C1-C4alkyl, C1-C4-alkoxy-C1-C2alkoxy-C1-C2alkyl, cyano-substituted C1-C6alkyl; carboxy-C1-C4alkyl,C1-C6alkoxycarbonyl-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6-alkoxycarbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxy-carbonyl-C1-C4alkyl, C1-C5alkylaminocarbonyl-C1-C4alkyl, di-C1-C5alkylamino-carbonyl-C1-C4alkyl or C3-C6cycloalkyl.

13. A compound according to claim 12 wherein R2 is C1-C6alkoxycarbonyl-C1-C4alkyl or C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl.

14. A compound according to claim 11 wherein R1 is fluorine and Y is oxygen.

15. A process for the preparation of a compound of formula I

(I) wherein Y is oxygen or sulfur;
R1 is hydrogen or fluorine; and R2 is hydrogen, C1-C6alkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted C1-C6alkyl, C2-C4alkenyl, or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted C1-C6alkyl;
carboxy-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, halo-C1-C6alkoxycarbonyl-C1-C4-alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C2alkoxy-carbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxycarbonyl-Cl-C4alkyl, C1-C5alkyl-aminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl, C1-C4alkylsulfonyl, C3-C6-alkenyloxy-C1-C4alkyl, C1-C8alkylcarbonyl, , , , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or Cl-C4alkyl; which process comprises converting an isothiocyanate of formula II

(II), wherein the substituents R1 and R2 are as defined for formula I, with a hexahydro-pyridazine of formula III

(III) into a compound of formula IV

(IV), which is then reacted with a compound of formula V

CYCl2 (V), wherein Y is oxygen or sulfur, in the presence of a base.

16. A herbicidal and plant growth regulating composition comprising one or more benzo-thiazolone derivatives of formula I according to claim 1.

17. A composition according to claim 16 comprising from 0.1 % to 95 % of a compound of formula I according to claim 1.

18. A method of controlling undesirable plant growth, which comprises applying acompound of formula I according to claim 1, or a composition comprising such a compound according to claim 16, in an effective amount to the plants or to the locus thereof.

19. A method according to claim 18, which comprises applying the active ingredient in an amount of from 0.001 to 4 kg per hectare.

20. A method according to claim 18 for the selective pre- or post-emergence control of weeds in crops of useful plants.

21. A method of inhibiting plant growth, which comprises applying a compound of formula I according to claim 1, or a composition comprising such a compound according to claim 16, in an effective amount to the plants or to the locus thereof.