PT84872B

Triazole herbicides

Abstract

Herbicidal triazole sulphonamides of the formula: <CHEM> and salts thereof, where: R<1> represents hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, acyl, alkoxycarbonyl, aminocarbonyl, sulphonyl or heterocyclic group; R<2> represents hydrogen, halo, cyano, hydroxy, mercapto, a substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, acyl, alkoxycarbonyl, aminocarbonyl, aryl or amino group, or a heterocyclic group; R<3> represents a substituted or unsubstituted heterocyclic, benzheterocyclic, aryl or aralkyl group; and R<4> represents hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl, acyl, aroyl, alkylsulphonyl, alkoxycarbonyl, aminocarbonyl, aralkyl, or a group of the formula: <CHEM> where R<1> and R<2> are as defined hereinbefore, processes for their preparation and compositions containing them.

PT84872B, drawing sheet 1 — Sheet 1 of 31

Term

Term ended

Expired 15 May 2002, 24.4 years ago.

2 claims: 1 independent, 1 dependent

1
REIVINDICAÇÕES - lâ Processo para triazol-sulfonamida da fórmula:a preparação de uma ou um sal correspondente, em que: R^ representa hidrogénio ou um grupo alquilo, alquenilo, alquinilo, ciclo-alquilo, arilo, araiquilo, acilo, alcoxi-carbonilo, amino-carbonilo, sulfonilo ou heterociclico, substituído ou insubstituidoj R 2 representa hidrogénio, halo, ciano, hidroxi, mercapto, um grupo alquilo, alquenilo, alquinilo, alcoxi, alquiltio, al quil-sulfinilo, alquil-sulfonilo, acilo, alcoxi-carbonilo, amino-carbonilo, arilo ou amino substituido ou insubstitui do R representa um grupo heterociclico, benz-heterociclico, ari lo ou aralquilo substituído ou insubstituído;e R 4 representa hidrogénio, um grupo alquilo, alquenilo, alquinilo, acilo, alquil-sulfonilo, alcoxi-carbonilo, amino-car bonilo ou aralquilo, ou um grupo da fórmula: (A) em que 1 2 ~ R e R sao como definido anteriormente, caracterizado por se fazer reagir um halogeneto de triazol-sulfonilo da férmu- 1 2 ~ R e R sao como definido anteriormente, e (II) Hal representa halogeneo, na presença de uma base, com uma z 3 4. 3 4 ~ amina da formula R^R^NH em que Br e R sao como definido anteriormente para se obter o composto desejado.
2
2â Processo de acordo com a reivindi cação 1, caracterizado por este se desenvolver a uma temperatura compreendida entre -10° e 100°C. - 3* - Processo de acordo com as reivindicações 1 ou 2, caracterizado por a base referida ser uma ba se orgânica terciária ou um excesso da amina r5r4nh. - - Processo de acordo com qualquer das reivindicações 1 a 3, caracterizado por se efectuar na presença de dimetil-amino-piridina como catalizador, - 5â - Processo para a preparação de uma tri-azol-sulfonamida de fórmula I como definida na reivindica ção 1, em que R 4 θ diferente de hidrogénio, caracterizado por se fazer reagir um composto de fórmula I em que R é hidrogénio, na presença de uma base, com um halogeneto de fórmula R 4 Hal. - 6& - Processo para a preparação de uma tri-azol-sulfonamida de fórmula I como definido na reivindica ção 1 em que R^ é hidrogénio, caracterizado por se hidrolizar, um composto de fórmula I em que R 4 representa um grupo de fór mula A, sob condições adequadas. - 7& Processo para a preparação de uma tri-azol-sulfonamida de fórmula I como definido na reivindica ção 1 em que R^ é diferente de hidrogénio, caracterizado por se fazer reagir um composto de fórmula I, em que. é hidrogé nio, com um electrofilo adequado contendo o grupo R.^ desejado. A requerente declara que os primei ros pedidos desta patente foram depositados no Reino Unido em 17 de Maio de 1986, sob o n^. 86/12062 e na República Federal Alemã em 12 de Dezembro de 1986, 5 de Março de 1987 e em 12 de Março de 1987, sob os n2s. P 36 43 021.8, P 37 07 202.1 e -60Ρ 37 08 215.9, respectivamente

Independent claims2

763 paragraphs in 3 sections, as filed

Description

The present invention relates to herbicidal triazole-sulfonamides, the process for their preparation, and the compositions containing them.

In one aspect, the invention provides the triazole-sulfonamides of the formula:

R1

(I) and their salts, where:

represents hydrogen or an alkyl, alkenyl, al

-1 substituted or unsubstituted quinyl, cycloalkyl, aryl, aralkyl, acyl, alkoxycarbonyl, amino-carbonyl, sulfonyl or heterocyclic;

The z

R represents hydrogen, halo, cyano, hydroxy, mercapto, an alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, acyl, alkoxycarbonyl, aminocarbonyl, aryl or substituted or unsubstituted amino group, or an heterocyclic group;

R-, represents a substituted or unsubstituted heterocyclic, benzheterocyclic, aryl or aralkyl group; and

R4 represents hydrogen, alkyl, alkenyl, alkynyl, acyl, alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, aralkyl, or a substituted or unsubstituted group of the formula;

Rx

where 12 * **

R and R have the previous meanings.

When R, R or R represents or contains an alkyl group, that group preferably has between 1 and 6 carbon atoms, especially between 1 and 4 carbon atoms. Preferred specific alkyl or unsubstituted alkyl groups that can be represented by R, R and R, include methyl, ethyl, n-propyl, iso propyl, n-butyl, isobutyl, s-butyl and t-butyl . If desired, the alkyl group can be replaced, for example, by one or more halogen atoms, for example fluorine, chlorine or bromine, by alkoxy or alkylthio groups of 1 to 4 carbon atoms, for example methoxy, ethoxy or methylthio or by acyloxy groups of 2 to 5 carbon atoms. Specific examples of substituted alkyl groups that R, R and R may represent, include chloromethyl, bromo-methyl, dichloro-methyl and tri

fluoro-methyl. In addition, R2 it can advantageously represent methoxy, ethoxy, n-propoxy, methylthio, hydroxymethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl or acetoxymethyl.

When R, R or Γ represents an alkenyl or alkynyl group, that group preferably has between 2 and 6 carbon atoms, for example vinyl, allyl or propargyl. Any of these alkenyl or alkynyl groups is preferably unsubstituted.

When R ^ represents cycloalkyl, it preferably has between 5 and 7 carbon atoms, especially cyclopentyl or cyclohexyl,

When R, R or R represents an acyl or alkoxycarbonyl group, or a substituted alkylaminocarbonyl or sulfonyl group, any of its alkyl parts preferably has the above meanings. If desired, the acyl group can be an aroyl or hetero-aroyl group, especially a benzoyl or 2-thienoyl group. Preferred specific acyl and alkoxycarbonyl groups include acetyl and methoxycarbonyl.

When R, R or R represents an aralkyl group, it is preferably benzyl, which can be substituted by one or more alkyl or alkoxy groups of 1 to 4 carbon atoms, by halogen atoms or by nitro groups.

Ί /.

When R and one has an aryl group, it is preferably a phenyl group that is desirably unsubstituted but that can be substituted, especially

3,5-disubstituted, by one or more halogen atoms or alkyl or alkoxy groups of 1 to 4 carbon atoms, particularly methyl or methoxy groups.

O #

When R represents aryl, it is preferably phenyl which is desirably unsubstituted but which can be replaced by one or more halogen atoms or by alkyl or alkoxy groups of 1 to 4 carbon atoms, particularly the methyl or methoxy groups.

When R ^ is or contains a group

-3aryl, this group is preferably phenyl, which is desirably substituted, for example by one or more halogen atoms (for example fluorine, chlorine or bromine), by nitro groups, by cyano groups, by amino groups or substituted starch or substituted in (for example alkyl-amino, dialkyl-amino, acyl-amino, alkyl-starch or dialkyl-starch groups, especially when the alkyl part has between 1 and 4 carbon atoms), with optionally alkyl, alkoxy or alkylthio groups replaced, from 1 to 4 carbon atoms (for example methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio), by alkoxycarbonyl groups from 2 to 5 carbon atoms or by alkylsulfinyl or alkylsulfonyl groups from 1 to 4 carbon atoms.

When R, R or R represents a heterocyclic group, that group is preferably a monocyclic group of 5 or 6 atoms in the ring which contains at least one nitrogen, oxygen or sulfur atom, which can of course be substituted, for example by one or more halogen atoms, hydroxy groups, nitro groups, cyano groups, optionally substituted amino or starch groups (for example by alkyl of 1 to 4 carbon atoms), alkyl, alkoxy or alkylthio groups of 1 to 4 carbon atoms , acyl or alkoxycarbonyl groups of 2 to 5 carbon atoms, or alkyl sulfonyl or alkyl sulfonyl groups of 1 to 4 carbon atoms. Together with the possible heterocyclic groups, the appropriate heterocycle N-oxides are, of course.

The heterocyclic groups that R3 may represent include substituted or unsubstituted pyridinyl, pyrimidinyl, piperidinyl, pyrazinyl, quinoxalinyl, morpholinyl, triazinyl, thienyl, benzoxazolyl, thiadiazolyl and triazolyl groups.

Preferred heterocyclic groups specific than R2 can represent include pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl.

O

When R represents halo, it is preferably fluorine, chlorine or bromine.

When R represents a substituted amino group, it is preferably an alkylamino group or

-4dialkylamino in which each alkyl part has between 1 and 4 carbon atoms, and can still be replaced, for example, by alkoxy groups of 1 to 4 carbon atoms. Such specific preferred groups are methyl-amino, ethyl-amino, methoxy-methyl-amino, ethoxy-methyl-amino and dimethyl-amino.

When R ^ represents a heterocyclic or benzheterocyclic group, it is preferably a benzothienyl or benzoxazolyl group, although it may also be, for example, a thiazolyl, isoxazolyl, pyridinyl, piperidinyl, triazolyl, benzothiazolyl or quinolinyl group, which can be substituted by one or more alkyl or alkoxy groups of one to four carbon atoms.

it is preferably hydrogen ^ alkyl of 1 to 6 carbon atoms, phenyl (which is desirably unsubstituted but which can be substituted, especially 3,5-disubstituted, by one or more halogen atoms or by alkyl or alkoxy groups of 1 to 4 atoms carbon, particularly methyl or methoxy groups), or mo nocicyclic heterocyclyl of 5 to 6 atoms in the ring which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl groups, alkoxy or alkylthio of 1 to 4 carbon atoms, cyano groups, amino groups (which can be unsubstituted or substituted for example by methyl or ethyl), halogen atoms or alkylsulfinyl or alkylsulfonyl groups of 1 to 4 atoms carbon.

Preferred groups that R * ^ can represent include hydrogen, methyl, ethyl, n-propyl, n-butyl, phenyl, substituted or unsubstituted 3,5-dimethyl-phenyl and pyrimidin-2-yl, groups 1,3, 5-triazin-2-yl and 1,2,4-triazin-3-yl, especially 4-methyl-pyrimidin-2-yl, 4-methoxy-pyrimidin-2-yl, 4,6-dimethyl-pyrimidin-2 -yl, 4,6-dimethoxy-pyrimidin-2-yl, 4,6-dichloro-pyrimidin-2-yl, 4-methyl-6-chloro-pyrimidin-2-yl, 4-methyl-6-methyl-amino -pyrimidin-2-yl, 4-methyl-6-amino-pyrimidin-2-yl, 4-methyl-6-dimethyl-amino-pyrimidin-2-yl, 4-chloro-6-methoxy-pyrimidin-2-yl, 4-methyl -5-chloro-6-methoxy-pyrimidin-2-yl, 4- methyl-6-methoxy-pyrimidin -2-yl, 4,6-dimethoxy-1,5,5-triazin-2-yl, 4-chloro-6-methyl-1,

3,5-triazin-2-yl, 4-chloro-6-methoxy-1,3,5-triazin-2-yl, 4-methoxy-6-methyl-1, 3,5-triazin-2-yl , 4-methyl-amino-6-methoxy-1,3,5-triazin-2-yl and 4-methyl-amino-6-chloro-1,5,5-triazin-2-yl.

The t /

It is preferably hydrogen, halo, cyano, alkyl or alkoxy of 1 to 6 carbon atoms (which is substituted or unsubstituted by one or more halogen atoms, hydroxy groups, alkoxy groups of 1 to 4 carbon atoms , acyloxy groups of 2 to 5 carbon atoms), alkoxycarbonyl of 2 to 5 carbon atoms, amino, alkylamino of 1 to 4 carbon atoms, monocyclic heterocyclyl of 5 to 6 atoms in the ring which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl groups of 1 to 4 carbon atoms. The specific preferred groups that R4 may represent include hydrogen, chlorine, bromine, cyano, methyl, n-propyl, n-butyl, s-butyl, hydroxy-methyl, methoxy-methyl, ethoxy-methyl, methoxy-ethyl, acetoxy-methyl, methoxy, ethoxy, methoxy-carbonyl, amino, methyl-amino, ethyl-amino, pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl.

R preferably represents a phenyl group that is substituted (especially 2-substituted, 2,6-disubstituted, 2,3,5-trisubstituted, 2,3,6-trisubstituted or 2,3,5,6-tetrasubstituted) by one or several halogen atoms, nitro groups, cyano groups or alkyl, alkoxy or alkylthio groups of 1 to 4 carbon atoms (which can also be replaced by one or more halogen atoms) or alkoxycarbonyl groups of 2 to 6 atoms of carbon.

• z

The specific groups that ά can represent include 2-fluoro-phenyl, 2-chloro-phenyl, 2-bromo-phenyl, 2-cyano-phenyl, 2-methyl-phenyl, 2-methoxy-phenyl, 2-methyl-thio- phenyl, 2-trifluoromethyl-phenyl, 2-methoxy-carbonyl-phenyl, 2-ethoxy-carbonyl-phenyl, 3-fluorophenyl, 2-fluorophenyl, 2-difluoromethoxy-phenyl, 2,3-difluorophenyl, 2,5-diflu2 rophenyl , 2,6-dimethyl-phenyl, 2,3,5,6-tetrafluorophenyl, 2-methyl-6-methoxy-carbonyl-phenyl, 2-fluoro-6-methoxy-carbonyl-phenyl, and especially 2,6-difluoro-phenyl, 2,6-dichloro-phenyl,

2,6-dibromo-phenyl, 2-methyl-6-nitrophenyl, 2-chloro-6-methyl-phenyl, 2-fluoro-6-methoxy-carbonyl-phenyl, 2-chloro-6-methoxy-caryl- phenyl, 2,6-dichloro-3-methyl-phenyl or 2-chloro-6-fluorophenyl.

R preferably represents hydrogen, methyl, acetyl, benzoyl, methylsulfonyl, methoxy-carbonyl, dimethyl-carbamoyl or benzyl.

Particularly preferred compounds according to the invention are those of the examples which follow, although a particular reference can be made to the following;

N- (2,6-difluorophenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triaz 01-5-sulfonamide;

N- (2,6-dichloro-3-methyl-phenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triazol-5-sulamonamide;

N- (2-methyl-6-nitrophenyl) -1- (pyridin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonamide;

N- (2,6-difluorophenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -5-methyl-1-1,2,4-triazol-3-sulfonamide;

N- (2,6-dichlorophenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triazole -3-sulfonamide;

N- (2,6-difluorophenyl) -1- (4-methyl-pyrimidin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonamide;

N- (2,6-difluorophenyl) -1- (4-methoxy-6-methyl-pyrimidin-2-yl) -5methyl-1,2,4-triazol-3-sulfonamide;

N- (2,6-dichlorophenyl) -1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonamide;

N- (2,6-dichlorophenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -1,2,4-tri azol-3-sulfonamide;

N- (2,6-dichlorophenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonamide;

N- (2-methyl-6-nitrophenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonamide;

N- (2,6-dichlorophenyl) -5- (2,5-dimethyl-pyrrol-1-yl) -1,2,4-triazole-3-sulfonamide;

N- (2,6-difluorophenyl) -5- (2,5-dimethyl-pyrrol-1-yl) -1,2,4-triaz01-3-sulfonamide;

N- (2,6-dichloro-3-methyl-phenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -1,2,4-triazol-3-sulfonamide;

Ν- (2,6-dichloro-phenyl) -5-amino-1- (4,6-dimethyl-pyrimidin-2-yl) -1,2,4-triazole-3-sulfonamide; and

N- (2,6-dichloro-5-methyl-phenyl) -5-amino-1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1, 2,4 “triazole- 3-sulfonamide.

In another aspect the invention provides a process for the preparation of a wet triazol sulfone of formula I, in which a form triazol sulfonyl halide is reacted

on what

2 * R and R have the previous meanings, and

Hal represents halogen, in the presence of a base, with an amine of the formula R ^ R ^ NH where R ^ and R ^ have the above meanings, to provide the desired compound.

The reaction is conveniently carried out at a temperature between -10 ° C and 100 ° G, particularly between -10 ° 0 and 25 ° C, and conveniently at room temperature.

The base is preferably an organic base, especially a tertiary organic base for example pyridine, Ν, Ν-dimethylaniline or triethylamine, or an ex-

4 amine RR NH. The reaction can be catalyzed by several tertiary organic bases, for example dimethyl-amino-pyridine. When R ^ is an acyl group, the base used is preferably a strong base, for example sodium hydride, and the reaction is conveniently carried out in a suitable aprotic solvent medium, for example tetrahydrofuran.

If desired, the reaction conditions can be adjusted to improve the production of the compounds of formula I where R R represents a group of formula A. When these compounds are desired, it is preferable to use at least

-8 less 2 moles of sulfonyl halide of formula II per mole of amine. Alternatively, compounds of formula I in which it represents a group of formula A can be prepared from the corresponding formula I in which R 4 represents hydrogen by reacting in the presence of a strong base with more sulfonyl halide of formula II. In such a case, the base may for example be sodium hydride in a suitable solvent medium, for example tetrahydrofuran.

Compounds of formula II can be prepared by reacting a compound of formula:

(III) where

R1 and R2 have the previous meanings and

R represents hydrogen, alkenyl, acyl or aralkyl, with the appropriate halogen or sulfonyl halide in a suitable solvent medium to provide the desired compound0 The reaction was desirably carried out with cooling to a temperature below that of the environment, for example to a temperature of 5 ° C or below.

The compounds of formula III in which R represents hydrogen can be prepared by a process in which an alkanoylthio-semicarbazide of formula (IV) is cyclized

R uO - N - NH - 0 - NH2 on what

R1 and R2 have the above meanings, in the presence of a base to provide the desired compound.

Cyclization is preferably carried out by heating the compound of formula IV in water.

The base used can be for example a carbonate, for example sodium carbonate.

Compounds of formula III in which R is other than hydrogen can be prepared from the corresponding compounds in which R is hydrogen by methods known per se, for example, alkylation and acylation.

The compounds of formula III can also be converted to each other by methods known per se in order to provide any desired starting material with that formula. For example, when R is a protecting group, for example benzyl, compounds in which R or R is hydrogen can be converted into the corresponding compounds in which R1, or R4 is different from hydrogen by known anion bonding techniques.

The compounds of formula IV, can be prepared by acylation of the corresponding thio-semicarbazi / 1 1 of those of formula R NH, NH.CS.NH2 where R has the previous meaning, by methods known per se.

The compounds of formula I can also be converted to each other by methods known per se. For example, compounds of formula I in which R ^ is different from hydrogen can generally be prepared from the corresponding compounds of formula I in which R ^ is hydrogen, by reacting in the presence of a base, for example sodium hydride , potassium carbonate or pyridine, with a halide of formula R ^ Hal.

Compounds of formula I where r4 represents a group of formula A can be hydrolyzed under appropriate conditions to provide the corresponding compounds in which R4 is hydrogen.

Compounds of formula I where Ί z Z

R e other than hydrogen can be prepared from the corresponding compounds of formula I in which R? is hydrogen, making it react with an appropriate electrophile (for example one with a formula R ^ Hal, R ^ S020H ^ or R ^ SO ^ p-toluene), if

-10seged in the presence of a base such as sodium hydride, potassium carbonate, triethylamine or 1,8-diaza-bicycles (5.4, 0) undec-7-ene, at room temperature or with heating in a suitable solvent medium , for example dimethylformamide, tetrahydrofuran or dimethoxyethane.

The carboxy groups present in the compounds of formula I can be esterified, the ester or acyl groups present can be hydrolyzed to provide the corresponding acids, and the cyano or ester groups can be converted to starch or substituted starch groups. Such transformations, as well as many others, can be carried out by techniques well known to those skilled in the art, and then several examples of such transformations will be provided.

The compounds of formula I are herbicides active against a wide range of broad leaf weeds, but are relatively safe for different crop species. Therefore they can be used as selective herbicides, particularly in the control of various weeds in cereals and other crops, for example, wheat, barley, corn, soybeans, rapeseed, cotton or sunflower.

In another aspect, the invention provides a herbicidal composition which consists of one or more compounds of the invention in association with a suitable vehicle and / or a surfactant.

The compositions normally contain between 0.01 and 99% by weight of the compounds of the invention, and in general are produced initially in concentrates containing between 0.5 and 99%, preferably between 0.5 and 85%, and especially between 10 and 50% of its weight. If necessary, these concentrates are diluted prior to application to the site to be treated so that the active ingredient is comprised between 0.01 and 5% by weight of the applied formulation.

vehicle may be water, in which case an organic solvent may also be present, although this is normally not used.

A concentrated fluid suspension can be prepared by grinding the compound with water, with a

wetting agent and suspending agent, for example xanthan gum.

Alternatively, the vehicle may be an organic solvent immiscible with water, for example a hydrocarbon whose boiling point is between 130-270 ° C, for example xylene, in which the compound is dissolved or suspended. An emulsifiable concentrate containing a non-water-miscible solvent can be prepared with a surfactant so that the concentrate acts as a self-emulsifiable oil when mixed with water.

Alternatively, the vehicle may be a water-miscible organic solvent, for example 2-methoxy-ethanol, methanol, propylene glycol, di-ethylene glycol, diethylene glycol monoethyl ether, methyl-formamide or dimethyl-formamide.

Alternatively, the vehicle can be a solid, which can be finely divided or granular. Examples of suitable solids are limestone, clays, sand, mica, chalk, atapulgite, diatomite, perlite, sepiolite, silicas, silicates, lino-sulfonates and solid fertilizers. The vehicle may be of natural or synthetic origin and may be modified natural material.

Water-soluble and dispersible wettable powders can be prepared by mixing the particulate compound with a particulate carrier or by spraying molten compound onto the particulate carrier, mixing a wetting agent and a dispersing agent finally by grinding the entire powder mixture .

An aerosol composition can be prepared by mixing the compound with a propellant, for example an alkane halogen, such as dichloro-fluoro-methane, and suitably also with a solvent.

The term “surfactant is used in the broad sense in which it is generically referred to as emulsifying agents, dispersing agents and wetting agents. Such agents are well known. in the specialty.

The surfactants used can include anionic surfactants, for example, mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulphates such as dodecyl -sodium sulphate, fatty alcohol ethoxylated sulphates, alkyl phenol ethoxylated sulphates, lignin sulphates, petroleum sulphonates, alkyl aryl sulphonates such as alkyl benzene sulphonates or (lower alkyl) naphthalene sulphonates, salts of sulphonated naphthalene formaldehyde condensates, sulphonated formaldehyde condensate salts, or more complex sulphonates such as sulphonates of sulphonates. amide, for example the sulphonated condensation product of oleic acid and N-methyl-taurine or the dialkyl sulfo succinates, for example, dioctyl succinate sodium sulfonate.

Surfactants can also include non-ionic agents, for example condensation products of fatty acid esters, fatty alcohols, fatty acid amides or alkyl phenols substituted with ethylene oxide, fatty esters of polyhydric alcohol ethers, for example the sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, for example, sorbitan fatty acid and polyoxyethylene esters, blocking copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decin-4,7-diol, or ethoxylated acetylenic glycols.

Surfactants can also encompass cationic agents, for example substituted quaternary alkyl- and / or aryl-ammonium compounds such as cetyl-trimethyl-ammonium bromide, or ethoxylated tertiary fatty amines.

Preferred surfactants include ethoxylated fatty alcohol sulphates, lignin sulphonate, alkyl-aryl sulphonates, sulphonated naphthalene-formaldehyde condensate salts, sulphonated phenol-formaldehyde condensate salts, oleolyl-N-methyl-tauride sodium, dialkyl sulfo succinate, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.

The active compounds of the present invention, especially those in the examples below, and in particular those specifically identified above, can be mixed with other pesticides, for example a herbicide, fungicide or insecticide, or with a growth regulator from plants, particularly with another herbicide, for example trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluormeturon, oxifluorfer, fomesafen, bentazone, promethin, norflurazon, clomazone, EPTC, imazaquin, and especially isoproturon, meta-benz-thiazuron, trifluralin, ioxynil, bromoxynil, benazoline, mecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin and pendimethalin.

The compounds of the present invention can be applied to plants, soil, terrestrial and aquatic areas, and particularly in a place where a crop is to be grown or to be grown. The compounds are active before and after appearance.

The invention is illustrated by the following examples where Me - methyl, Et = ethyl, Pr = propyl, Bu »butyl and F = phenyl:

Preliminary Example A

N- (2,6-difluorophenyl) -1-phenyl-5-n-propyl-1,2.4-triazol-3-sulfonamide (Compound Al) (a) 1-Butyryl-1-phenyl-thio-semioarbazide

A stirred mixture of 1-phenyl-thio-semicarbazide (30 g) and butyric anhydride (31.2 g) in toluene (250 ml) was heated under reflux for two hours. After cooling, the crude product was filtered as a white powder, mp 219-221 ° C.

(b) 3-Mercapto-1-phenyl-5-propyl-1,2,4-triazole

A suspension of the product from step (a) (40 g) in a 10% aqueous sodium carbonate solution (200 ml) was refluxed for two hours. The light yellow solution obtained was cooled and acidified with concentrated hydrochloric acid to provide an off-white precipitate. It was filtered and recrystallized from ethanol to provide the desired product (33 g), as white needles, mp 142-143 ° 0.

Chlorine was bubbled through a stirred suspension of the product from step (b) (20 g) in 60% aqueous acetic acid (200 ml) for 90 minutes at -5 ° C, Filtered the white solid, washed dry with ice-ice water and dried to provide the desired compound as a white powder (25 g).

(d) N- (2,6-difluorophenyl) -1-phenyl-5-n-propyl-1,2,4-triazole-3-sulfonamide

Several portions of the product of Example A in step (c) (4 g) were added to a stirred solution of 2,6-difluoroaniline (3.6 g) and 4-dimethylamino-pyridine (0.2 g ) in dry pyridine (25 ml). After 18 hours at 25 ° C, most of the pyridine was removed in vacuo. The residue was dissolved in a 1M sodium hydroxide solution (70 ml) and extracted with ethyl acetate (2 x 30 ml). The aqueous layer was acidified with concentrated hydrochloric acid, and the solid was filtered and recrystallized from toluene to provide 3.1 g of the desired product, mp 148-150 ° C.

Examples A2-A 102

The following compounds of formula I were removed in which R4 represents hydrogen by methods analogous to those of Example A:

<td>Ν £.</td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>Mp (° C)</td>

<td>A14</td><td>F</td><td>n-Pr</td><td>2,3,5> 6-tetráF</td><td> 118-119</td>

<td>Nfi.</td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>Federal Police. (° 0)</td>

<td>A50</td><td>F</td><td>Ph</td><td>2-COOEt</td><td> 113-114</td>

<td>A31</td><td>F</td><td>Ph</td><td>4-COOEt</td><td> 184-186</td>

<td>A34</td><td>i-Pr</td><td>Me</td><td>2-COOEt</td><td> 113-115</td>

<td>A47</td><td>F</td><td>i-Pr</td><td>pentaF</td><td> 123-124</td>

<td>Ν2.</td><td>IR</td><td>R2</td><td>R3 (F subst;)</td><td>Pf (° O</td>

<td>M ·</td><td>IR</td><td>R2</td><td>R3 (F subst;)</td><td>mp (° 0)</td>

<td>A54</td><td>2-pyrimidyl</td><td>Me</td><td>2,6-diF</td><td> 209-211</td>

<td>A55</td><td>2-pyrimidyl</td><td>Me</td><td>2-Cl, 6-Me</td><td> 224-226</td>

<td>A56</td><td>2-pyrimidyl</td><td>Me</td><td>2-01.6-F</td><td> 217-219</td>

<td>A57</td><td>2-pyrimidyl</td><td>Me</td><td> 2-01</td><td> 145-147</td>

<td>A58</td><td>2-pyrimidyl</td><td>Me</td><td>2-Me, 6-C00Me</td><td> 165-167</td>

<td>A59</td><td>2-pyrimidyl</td><td>Me</td><td>2-Cl, 6-SMe</td><td> 206-208</td>

<td>A6O</td><td>2-pyrimidyl</td><td>Me</td><td>2,6-diBr</td><td> 230-232</td>

<td>A61</td><td>2-pyrimidyl</td><td>Me</td><td>2-CF, 5</td><td> 163-165</td>

<td>A62</td><td>2-pyrimidyl</td><td>Et</td><td>2,6-diF</td><td> 213-215</td>

<td>A63</td><td>4,6-dimethyl 2-pyrimidyl</td><td>Me</td><td>2,6-diF</td><td> 228-230</td>

<td>A64</td><td>4,6-dimethyl 2-pyrimidyl</td><td>Me</td><td> 2-01</td><td> 124-126</td>

<td>A65</td><td>4,6-dimethyl 2-pyrimidyl</td><td>Me</td><td>2-01,6-Me</td><td> 208-210</td>

<td>A66</td><td>4-methoxy-2- pyrimidyl</td><td>Me</td><td>2,6-diF</td><td> 164-166</td>

<td>A67</td><td>4-methyl-2pyrimidyl</td><td>Me</td><td>2,6-diF</td><td> 203-205</td>

<td>Ν2.</td><td>R1</td><td>R2</td><td>R3 (Substitute P)</td><td>pg, (° c)</td>

<td>Μ ·</td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>Df (° G)</td>

<td>Α70</td><td>Me</td><td>2,6-diFPh</td><td>2,6-diF</td><td> 197-198</td>

<td>Α71</td><td>Me</td><td>2-NOgPh</td><td>2,6-diF</td><td> 195-196</td>

<td>Α82</td><td>3-nitropi ridin-2-il</td><td>Me</td><td>2,6-diP</td><td> 158-160</td>

<td>Α83</td><td>Me</td><td>i-Pr</td><td>2-COOEt</td><td> 115-115</td>

<td>Α86</td><td>Ph</td><td>COOMe</td><td>2,6-diP</td><td> 160-162</td>

<td>Νδ.</td><td>IR</td><td>R2</td><td>R3 (P subst :)</td><td>mp (° 0)</td>

<td>Α91</td><td>4-methyl- -2-pyrimidinyl</td><td>Me</td><td>2-Cl, 6-Me</td><td> 176-178</td>

<td>Α92</td><td>4-MeO-6-Me-2-pi rimidinyl</td><td>Me</td><td>2,6-diF</td><td> 198-200</td>

<td>Α93</td><td>5-01-4-Me0-6-Me-2- -pyrimidinyl</td><td>Me</td><td>2,6-diP</td><td> 194-195</td>

<td>Α94</td><td>4-methoxy -2-pyrimidinyl</td><td>Me</td><td>2,6-diF</td><td> 194-195</td>

<td>Α95</td><td>4,6-dime til-2-pi rimidinyl</td><td>H</td><td>2-01.6-F</td><td> 232-233</td>

<td>Α99</td><td>2-pirimi dinil</td><td>H</td><td>2-Gl, 6-P</td><td> 246-248</td>

<td></td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>• mp · (° o)</td>

following compound of formula I in which R R is also allyl was also prepared by an analogous method

<td colspan="2">go to Example As</td><td rowspan="2">R3 (F subst :)</td><td rowspan="2">mp (° C)</td>

Preliminary Example B

N- (2-bromo-phenyl) -1-phenyl-5-propyl-1,2,4-triazole-3-sulfonamide (Compound Bl)

To a cooled (0 ° C) solution of the product from step (c) (2.85 g) in dichloromethane (4 ml) was added with stirring a solution of 2-bromoaniline (1.89 g) in pyridine ( 12 ml). The reaction mixture was stirred at 0 ° C for 30 minutes. Then the mixture was stirred at room temperature for an additional four days. The product was then partitioned between 100 ml of water and 100 ml of dichloromethane, and the aqueous phase was washed with dichloromethane (100 ml). The organic phases were combined and washed with diluted hydrochloric acid (20%, 100 ml), then with water (30 ml), and dried over magnesium sulfate. Upon removing the solvent, an orange oil was obtained which crystallized upon trituration with diethyl ether to provide orange crystals (3.7 g). These crystals were recrystallized from ethanol to provide 2.5 g of the desired product as white crystals, mp 119-121 ° C.

Preliminary Example C

21Ν- (2,6-dichloro-3-methyl-phenyl) -5-methyl-1- (2-pyrimidinyl) -1, 2t4-triazole-3 "Sulfonamide (Compound Cl)

A suspension of sodium hydride (8.7 g) in dry tetrahydrofuran (400 ml) was stirred at 25 ° C and a single portion of N-acetyl-2,6-dichloro-3-methyl- aniline (50.4 g). After stirring for 15 minutes, 5-methyl-1- (2-pyrimidinyl) -1,2,4-triazole-3-sulfonyl chloride (30 g), prepared by an analogous method, was added over 5 minutes that of Example A. The mixture was stirred at 25 ° C for 18 hours and the solvent was removed in vacuo. The residue was treated with a 1M sodium hydroxide solution (500 ml) for 5 minutes with stirring, and then extracted with ethyl acetate (500 ml). The ethyl acetate layer was extracted again with a 1M sodium hydroxide solution (300 ml). The combined aqueous phases were acidified with concentrated hydrochloric acid and the solid was filtered. Recrystallization from acetonitrile gave 38 g of the desired product, mp 214-216 ° C.

Examples C2-C11

The following compounds of formula I in which it represents hydrogen were prepared by methods analogous to that of Example C:

<td>M ·</td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td> (°0)</td>

<td>C3</td><td>2-pyrimidinyl</td><td>Me</td><td>2,6-diCl</td><td> 223-225</td>

<td>C4</td><td>2-pyrimidinyl</td><td>Me</td><td>2-Me, 6-N02</td><td> 191-193</td>

<td>C5</td><td>4,6-dimethyl-2-pyrimidinyl</td><td>Me</td><td>2,6-diCl</td><td> 248-249</td>

<td>C6</td><td>4,6-dimethyl-2-</td><td>Me</td><td>2-Me, 6-N09</td><td> 195-196</td>

-pyrimidinyl

-22·

<td>Nfi.</td><td>laughs</td><td>R2</td><td>R3 (Substitute F)</td><td>mp (° C)</td>

<td>C7</td><td>4,6-dimethoxy-1,3,5-triazin-2-yl</td><td>Me</td><td>2,6-diCl</td><td> 195-197</td>

<td>C8</td><td>4-methyl-2-pyrimidi- nil</td><td>Me</td><td>2,6-diCl</td><td> 201-202</td>

<td> 09</td><td>4-methyl-2-pyrimidi- nil</td><td>Me</td><td>2-Me, 6-N02</td><td> 183-184</td>

<td>G10</td><td>4-methyl-2-pyrimidi-</td><td>Me</td><td>2, o-diCl, 3-Me</td><td> 204-205</td>

nil

The following compound of formula I was also prepared in which R4 represents hydrogen for a

<td colspan="5">analogous to that of Example C:</td>

<td>Cll</td><td>F</td><td>Me</td><td>3-nitro-pyrimidin-2-yl</td><td> 175-176</td>

Preliminary Example D

2 · 6-Dichloro-NN-bis (1-phenyl-5-n-propyl-1,2,4-triazol-3-sulfonyl) -aniline (Compound Dl)

The product of Example A, step (c) (4 g) was added to a stirred solution of 2,6-dichloroaniline (2.3 g) in pyridine (20 ml) and the mixture was stirred at 25 ° C. ° C for 48 hours. The reaction mixture was poured into water (200 ml) and crystallized. The product was recrystallized from ethyl acetate to provide 3.35 g of the desired product, mp 262-264 ° C.

Example D2

The compound corresponding to that of Example D was prepared with the exception that R represents 2.3.4,

, 5,6-pentafluorophenyl, by a process analogous to that of Example D, mp 139-140 ° C.

Example E Preliminary

N- (2.6-dichlorophenyl) -5-ethyl-1-phenyl-1,2,4-triazole-3-sulfonamide (Compound El)

5-Ethyl-1-phenyl-1,2,4 "triazol-3-sulfonyl chloride (2.7 g), prepared by a method analogous to Example A, was added to a stirred solution of 2.6 -di chloroaniline (1.8 g), and 4-dimethyl-amino-pyridine (0.1 g) in dry pyridine (15 ml). After 48 hours at 25 ° C, most of the pyridine was removed in vacuo, and the residue was dissolved in dichloromethane. The solution was extracted with dilute hydrochloric acid and then evaporated again. The residue was treated with a 4M sodium hydroxide solution (25 ml) at 80 ° C for 1 hour and then filtered. The filtered solid was washed with hot water, the filtrate was acidified with concentrated hydrochloric acid, and the product was recrystallized from ethanol to provide 1.2 g of the desired product, mp 185-187 ° C.

Examples E2-E7

The following compounds of formula I were prepared in which R4 o hydrogen by methods analogous to those of Example E:

<td>N2.</td><td>IR</td><td>R2</td><td>R3 (Substitute F)</td><td>p.í. (° o)</td>

<td>Example</td><td colspan="2">Preliminary F</td><td></td><td></td>

<td rowspan="2"></td><td colspan="3">N- (2,6-difluorophenyl) -1- (4,6-dimethyl-</td><td>-2-pyrimidi-</td>

<td>nil) -5 ·</td><td>-methyl-1,2,4- '</td><td colspan="2">triazole-3-sulfonamide (Compos-</td>

to Pl)

Several portions of N- (2,6-difluorophenyl) -5-methyl-1,2,4-triazole-3-sulfonamide (5 g) (Compound A81) were added to a sodium hydride suspension (1, 37 g in an 80% suspension in oil) in dimethylformamide (40 ml). The mixture was stirred for 30 minutes at 25 ° C, 4,6-dimethyl-2-chloro-pyrimidine (2.6 g) was added, and then the mixture was stirred at 100 ° C for 18 hours. The cooled reaction mixture was poured into water, acidified with glacial acetic acid and then extracted with dichloromethane (3 x 100 ml). The organic phases were dried and evaporated, and the residue was chromatographed (silica / dichloromethane). The product was recrystallized from ethanol to provide 0.8 g of the desired product, mp 228-230 ° C, identical to that of Example A63.

Examples F2-F20

The following compounds of formula I were prepared in which R4 is methyl, R4 is 2,6-difluorophenyl and R4 is hydrogen, by methods analogous to example F:

<td>F2</td><td>2-chloro-pyrimidin-4-yl</td><td> 185-185</td>

<td>F5</td><td>3-ethyl-1,2,4-thiadiazol-5-yl</td><td> 180-181</td>

<td>F4</td><td>pyrazinyl</td><td> 201-205</td>

<td>F5</td><td>4- (2-hydroxy-ethyl) -6-morpholino- -l, 5,5-triazin-2-yl</td><td> 176-178</td>

<td>F6</td><td>5-nitropyridin-2-yl</td><td> 201-205</td>

<td>F7</td><td>2,4-dinitrophenyl</td><td> 171-175</td>

<td>F8</td><td>7-chloro-quinoxalin-2-yl</td><td> 192-195</td>

<td>F9</td><td>4-methanesulfonyl-phenyl</td><td> 215-217</td>

<td>THREAD</td><td>5-yenyl-1,2,4-thiadiaz ol-5-yl</td><td> 244-246</td>

<td>Fll</td><td>benzoxazol-2-yl</td><td> 210-212</td>

The seQ * Z compound of formula I was also prepared in which R4 is methyl, Br is 2,6-dichlorophenyl and is hydrogen, by a method analogous to Example F:

<td> 1*12</td><td>benzoxazol-2-yl</td><td> 212-214</td>

Compounds were also prepared

4 * ** z * 5 # of formula I where R and R are hydrogen and Re

2-chloro-6-methyl-phenyl, by a method analogous to Example Jft

<td>F13</td><td>2,6-dimethoxy-benzoyl</td>

<td>F14</td><td>thien-2-yl-carbonyl</td>

<td>F15</td><td>Ni s opropyl-N- (4-methyl-phenyl) -carbamoyl</td>

<td>F16</td><td>N-is opropyl-N- (4-is opropyl-phenyl) -carbamoyl</td>

<td>F17</td><td>N-isopropyl-N- (4-chlorophenyl) -carbamoyl</td>

<td>F18</td><td>N-methyl-N-phenyl-carbamoyl</td>

<td>F19</td><td>2,2-dimethyl-propanoyl-methyl</td>

Mp, (° C)

204-207

233-234

195-194

165-166

181-183

184-186

177-179

The compound was also prepared if # 2 4 **** * 3 * following formula I in which R and R are hydrogen and R and 2-ethoxycarbonyl-phenyl, by a method analogous to the example

F:

Rf mp (° C)

F20 N, N-diisopropyl carbamoyl 88.5-90

Preliminary Example G

N-Benzoyl-N- (2,6-difluorophenyl) -5-methyl-1- (2-pyrimidinyl) -1.2.4-triazole-3-sulfonamide (Compound Gl)

A suspension of N- (2,6-difluorophenyl) -5-methyl-1- (2-pyrimidinyl) -1,2,4-triazole-3-sulfonamide (1.5 g) was heated at reflux for 30 minutes. (Compound A54) and anhydrous potassium carbonate (0.59 g) in acetone, ca (50 ml). A solution of benzoyl chloride (0.6 g) in acetone (50 ml) was added, and the mixture was refluxed for more than 2 hours. Then the mixture was left to stand

at 25 ° C for 18 hours, after which it is heated, filtered and evaporated. The solid produced was recrystallized from acetonitrile to provide 1.05 g of the desired product, mp 218-221 ° C.

Examples G2-G7

The following compounds of formula I were prepared in which R1 is 2-pyrimidinyl, R2 ó methyl and is 2,6-difluorophenyl, by methods analogous to example Gj

<td>G5</td><td>allyl</td><td> 140-142</td>

<td>G7</td><td>COOMe</td><td> 172-174</td>

<td>Examples H1-H23</td><td></td><td></td>

The following compounds of formula I in which R represents hydrogen were prepared by methods analogous to Example A:

<td>Hl</td><td>Ph</td><td>Me</td><td>thiazol-2-yl</td><td> 221-222</td>

<td>H2</td><td>Ph</td><td>Me</td><td>benzo-thiazol-2-yl</td><td> 266-267</td>

<td>H5</td><td>Ph</td><td>Me</td><td>6-methoxy-quinolin-8-yl</td><td> 146-147</td>

<td>H4</td><td>Ph</td><td>Me</td><td>5-methyl-isoxazol-5-yl</td><td> 181-182</td>

<td>H5</td><td>Ph</td><td>n-Pr</td><td>piperidine</td><td> 106-108</td>

<td>H6</td><td>Ph</td><td>n-Pr</td><td>3-methyl-pyridin-2-yl</td><td> 160-162</td>

<td>H7</td><td>Ph</td><td>n-Bu</td><td>4H-1,2,4-triazol-4-yl</td><td> 175-176</td>

<td>H8</td><td>Ph</td><td>n-Bu</td><td>isoquinolin-5-yl</td><td> 259-260</td>

<td>H9</td><td>Ph</td><td>Me</td><td>4,6-dimethyl-2-pyrimidinyl</td><td> 192-193</td>

<td>H10</td><td>Ph</td><td>Me</td><td>6-methoxy-quinolin-8-yl</td><td> 146-147</td>

<td>Hll</td><td>Ph</td><td>Me</td><td>5-methyl-isoxazol-3-yl</td><td> 181-182</td>

<td>H12</td><td>Ph</td><td>n-Bu</td><td>1,2,4-triazol-4-yl</td><td> 175-176</td>

<td>Hl 3</td><td>Ph</td><td>Me</td><td>5-methyl-1,3,4-thiadiazol-2-yl</td><td> 235-236</td>

<td>H14</td><td>Ph</td><td>Me</td><td>4-methyl-thiazolyl</td><td> 218-219</td>

<td>H15</td><td>Ph</td><td>Me</td><td>4,5-dimethyl-thiazolyl</td><td> 280-282</td>

<td>H16</td><td>Ph</td><td>Me</td><td>6-nitroquinolin-5-yl</td><td> 180-181</td>

<td>H17</td><td>Ph</td><td>Me</td><td>4-οίαηο-3 ^ θϋ1-ϋο-ϊ8θϋ £ zol-5-ϋο</td><td> 184-185</td>

<td>H18</td><td>Ph</td><td>Me</td><td>5-methylthio-1,2,4-thiazol-3-yl</td><td> 152-153</td>

<td>H19</td><td>Ph</td><td>Me</td><td>5- (3-chlorophenyl) -l-methyl- -1,2,4-triazol-3-yl</td><td> 224-225</td>

<td>H20</td><td>Ph</td><td>Me</td><td>guinolin-5-yl</td><td> 188-189</td>

<td>H21</td><td>Ph</td><td>Me</td><td>5-methyl-1-phenyl-1,2,4-tria zol-3-yl</td><td> 227-228</td>

<td>H22</td><td>Ph</td><td>Me</td><td>5-ethyl-1-yenyl-1,2,4-tria- zol-3-yl</td><td> 173-174</td>

<td>H23</td><td>Ph</td><td>Me</td><td>1,2,4-triazol-4-yl</td><td> >320</td>

<td>Example</td><td>i:</td><td>Preliminary</td><td></td><td></td>

-29Ν- (2,6-dichlorophenyl) -1- (4 '6-dimethyl-pyrimidin-2-yl) -1.2,4-triazol-3-sulfonamide

N- (2,6-dichlorophenyl) -1,2,4-triazole-3-sulfonamide (2.051 g) was heated for 1 hour at 125% with 1.82 g of 2-p-toluene sulfonyl-4, 6-dimethyl-pyrimidine, in the presence of 1,8-diazabicyclo (5.4.0) undec-7-ene (2.128 g) in dimethylformamide (55 ml) · After distilling the solvent, the residue was poured into mixture of water (80 ml) and IN hydrochloric acid (20 ml), and then filtered. This crude product was chromatographed on silica gel using methylene chloride / methanol (95/5) as the eluent to provide

2.2 g of desired product, mp 274-275 ° 0.

Examples 12-146

The following compounds of formula I were prepared in which R1 and R4 are both hydrogen and R4 is pyrimidin-2-yl or pyrimidin-2-yl which is subsequently replaced as indicated by methods analogous to those described in the Examples A and / or I:

<td>N2.</td><td>RI subst:</td><td>R3 (Substitute F)</td><td>mp (° 0)</td>

<td> 19</td><td>4,6-diMe</td><td>2-COOEt, 6-Me</td><td> 154-156</td>

<td>Ν2.</td><td>RI substj</td><td>R3 (Έ * replaced)</td><td>Df (° C)</td>

<td> 123</td><td>4,6-diMeO</td><td>2,6-diCl</td><td> 255-260</td>

<td> 124</td><td>4,6-diMeO</td><td>2,6-diF</td><td> 205-208</td>

<td> 125</td><td>4,6-diMeO</td><td>2-C00Me, 6-Me</td><td> 144-145</td>

<td> 126</td><td>4,6-diMeO</td><td>2-C00iÍt, 6-Me</td><td> 161</td>

<td>NS.</td><td>Subst Rl:</td><td>R3 (And Subst :)</td><td>Mp (° C)</td>

<td> 138</td><td>4,6-diMeO</td><td>2-GF 3</td><td> 168-169</td>

<td> 139</td><td>4,6-diMeO</td><td>2,6-diCl, 3-Me</td><td> 249-250</td>

<td> 140</td><td>4,6-diMeO</td><td>2-Cl, 6-Me</td><td> 253-254</td>

<td> 141</td><td>4,6-diMeO</td><td>2-Me, 6-N02</td><td> 196-197</td>

Compounds of, 244, i, formula I were also prepared in which R and R are both hydrogen and R and pyrimidin-2-yl or pyrimidin-2-yl which is subsequently substituted as indicated by methods analogous to examples A and / or Ií

<td>Rfi.</td><td>Subst Rl:</td><td>R3</td><td>mp, (° 0)</td>

<td> 145</td><td>4,6-diMeO</td><td>naft-l-ilo</td><td> 211-212</td>

The following compound of formula I was also prepared in which R1 and R4 are both hydrogen and R4 is 4,6-bismethyl-thio-1,3,5-triazin-2-yl by a method analogous to that of Example A and / or I:

146

R3 (And Subst :)

2,6-diF] 1A ...... C ° o.)

254-256

Preliminary Example J1

Ν- (2,6-dichlorophenyl) -1acyl-5-amino-1,2,4-triazole-3-sulfonamide (a) 5-amino-3-benzylthio-1,2,4-triazole

3-Amino-5-mercapto-1,2,4-triazole (40.36 g) was treated at room temperature with sodium hydroxide (13.9 g) in ethanol (450 ml), and chloride was added benzyl (44.3 g). The mixture was stirred overnight and then filtered. Ethanol was evaporated and the residue was recrystallized from ethyl acetate to provide 64.97 g of the desired product, mp 104 ° C.

(b) 1-ac ethyl-5-amino-3-benzylthio-1,2t4-triazole

Acetyl chloride (12.57 g) in methylene chloride (30 ml) was added to the product from step (a) (30 g) and triethylamine (25 ml) in methylene chloride (300 ml) at 0 ° C ., and the mixture was stirred at room temperature for 30 minutes. Then it was treated with 1N sodium hydroxide (160 ml) and extracted with methylene chloride. After drying, the product was recrystallized from ethyl acetate to provide 33 g of desired product, mp 146 ° C.

The product of step (b) (112 g) was suspended in 1 liter of a mixture of water and glacial acetic acid (1: 1), and chlorine was passed at -10 ° C for a period of 2 hours, keeping the temperature below 0 ° C. The product was boiled with a minimum of water and pentane, and dried to provide 74.5 g of the desired product, mp 166-168 ° C.

(d) N salt,- (2,6-dichlorophenyl) -1-acetyl-5 ~ amino-1,2,4-triazole-3-sulfonamide pyridinium

The product from step (c) (54 g) was treated with 2,6-dichloroaniline (42.63 g) in pyridine (350 ml) and stirred at 60 ° C for 12 hours. After cooling, the product was filtered, washed with a little pyridine and ether, and dried in vacuo to provide 53.6 g of desired product, mp 213-215 ° C.

Preliminary Example J2

N- (2,6-dichlorophenyl) -5-amino-1,2,4-triazole-3-sulfonamide

The product of Example J1 (53.6 g) was mixed with a 2N sodium hydroxide solution (200 ml), and stirred at room temperature for 10 minutes. Upon cooling with air, the mpf was reduced to 5 with 2N. The product was filtered, washed with a little water and ether, and dried in vacuo to provide 35.4 g of the desired product, mp 265-267 ° 0.

Preliminary Example J3

N- (2.6-dichlorophenyl) -5-methyl-amino-1,2,4-triazol-3-sulfonamide (a) 1-acetyl-3-benzylthio-5-methyl-amino-1,2,4-

-triazole

3-Benzylthio-5-methyl-amino-1,2,4-triazole (11.2 g) was dissolved in tetrahydrofuran (70 ml) and triethylamine (5.7 g) was added. Acetyl chloride (4 ml) in tetrahydrofuran (20 ml) was added, and the mixture was stirred at room temperature for 5 hours. The triethylamine hydrochloride was filtered and the filtrate was concentrated to provide 13.4 g of the desired product.

(b) 1-Acetyl-5-methyl-amino-1,2,4- chloride

-triazole-3-sulionyl

The product of step (a) (13.4 g) was dissolved in glacial acetic acid (50 ml), and water (50 ml) was added. Chlorine was passed through this mixture at -10 ° C for 30 minutes, after which the product was filtered, washed with a little water, and dried in vacuo to provide 4.45 g of desired product. .

(c) N- (2,6-dichlorophenyl) -5-methyl-amino-1,2,4-triazole-3-sulfonamide product from step (b) (4.34 g) was added with stirring at 2 ° C, 6-dichloroaniline (3.24 g) in pyridine (30 ml), and the mixture was stirred at 50 ° C for 18 hours. After removing the pyridine, the residue was dissolved in a sodium hydroxide solution (50 ml) and extracted with ethyl acetate (50 ml). The aqueous phase was acidified to pH = 4-5 with 2N hydrochloric acid, cooled, and the product was filtered, washed with a little water and dried to provide 3.49 g of the product. desired product, mp 285-287 ° C.

Preliminary Example J4

Ethyl 3- (2,6-dichloro-phenyl-sulfamoyl) -5-methyl-amino-1,2,4-triazole-1-carboxylate

The product of Example J3 (2.24 g) was mixed with acetonitrile (100 ml) and potassium carbonate (0.52 g), and was added with stirring ethyl chloroformate (0.8 ml). Then the mixture was refluxed for 5 hours, filtered hot, the filtrate was concentrated, and the residue was triturated with ether. The product was filtered and dried in vacuo at 70 ° C to provide 2.65 g of the desired product, mp 202-203 ° 0.

Preliminary Example J5

N- (2,6-dichlorophenyl) -5- (2,5-dimethyl-pyrrol-1-35-yl) -1,2,4-triazole-3-sulfonamide

The product of Example J2 (6.16 g) was refluxed for 12 hours with hexane-2,5-dione (9.13 g) in ethanol (150 ml) and acetic acid (2 ml). After removing the solvents and excess diketone, the residue was chromatographed on silica gel with hexane / ethyl acetate to provide 2.9 g of desired product, mp 107-108 ° C.

Preliminary Example J6

N- (2,3-dichlorophenyl) -5- (2,5-dimethyl-pyrrol-1-yl) -1.2.4-triazole-3-sulfonamide

The product of Example J1 (c) (4.49 g) was stirred with 2,3-dichloroaniline (3.24 g) in dry pyridine (75 ml) under nitrogen for 5 hours at 70 ° C. Then the pyridine was removed and the residue was dried under high vacuum. The crude product was then refluxed with ethanol (150 ml), acetic acid (5 ml) and hexane-2,5-dione (9.13 g) for 8 hours, after which the solvents were removed, and the product was chromatographed on silica gel using ethyl acetate / hexane to provide 4.4 g of the desired product, mp 185 ° C.

Examples J7-J27

The following compounds of formula I were prepared in which R4 is hydrogen and R42 is pyrrol-1-yl substituted as indicated by methods analogous to Examples J1-J5:

<td></td><td>IR</td><td>R2 subst</td><td>R3 (F subst :)</td><td>mp (° C)</td>

<td>J12</td><td>H</td><td>2,5-diMe</td><td>pentaF</td><td> 92</td>

The following compounds of formula I were also prepared in which R3 is hydrogen and R42 represents pyrrol-1-yl substituted as indicated by methods similar to those in Examples J1-J5:

<td>J26</td><td>H</td><td>2,5-diMe</td><td>2-C00Me-3-thienyl</td><td> 144</td>

<td>J27</td><td>H</td><td>2,5-diMe</td><td>1-naphthyl</td><td> 207</td>

Preliminary Kl Example

N- (2.6-difluorophenyl) -5-methyl-amino-1-phenyl-1,2,4-triazol-3-sulfonamide (a) 3-Benzylthio-5-formyl-amino-1-phenyl-1,2, 4-triazole

A suspension of 5-amino-3-benzylthio-1-phenyl-1,2,4-triazole (45 g) in acetic anhydride (31 ml) and formic acid (16.09 ml) was stirred. the mixture for one hour at 80 ° C. Then the solvents were removed and the residue was crystallized from ethyl acetate to provide 35.4 g of desired product, mp 94 ° C.

(b) 3-Benzylthio-5-methyl-amino-1-phenyl-1,2,4-triazole

The product from step (a) (31 g) was mixed with dioxane (200 ml) and 96% sodium borohydride (19.6 g) at room temperature, and acetic acid (30 ml) was added. with vigorous agitation. The mixture was stirred at 100 ° C for 2 hours, after which the solvents were removed and the mixture was carefully added to water. Then the product was extracted with ethyl acetate and chromatographed on silica gel to provide 21.4 g of the desired product.

The product of step (b) (21 g) was suspended in a mixture of water (50 ml) and acetic acid (50 ml). Chlorine was passed through the mixture at a temperature between -10 ° C and 0 ° G, and the product was extracted with ethyl acetate. The oil product was chromatographed on silica gel using hexane / ethyl acetate to provide 15 g of the desired product.

(d) N- (2,6-difluorophenyl) -5-methyl-amino-1-phenyl-1,2,4-triazole-3-sulfonamide

The product of step (c) (3.27 g) was stirred at room temperature for 2 hours, then at 60 ° C for 1 hour and then overnight at room temperature with 2,6-difluoroaniline (2.58 g) in pyridine (20 ml), after which the pyridine was removed, and the residue was chromatographed on silica gel using hexane / ethyl acetate. The product was recrystallized from ethyl acetate to provide 3.5 g of the desired product, mp 180-181 ° C.

Preliminary K2 Example

N- (2,6-dichlorophenyl) -5-amino-l- (4,6-dimethyl-pyrimidin-2-yl) -1,2,4-triazol-3-sulfonamide (a) 5-amino-3- benzylthio-l, 2,4-triazole

5-Amino-3-mercapto-1,2,2,4-triazole (40.36 g) in ethanol (450 ml) was treated at room temperature with solid sodium hydroxide (13.9 g) and added benzyl chloride (44.3 g) is added dropwise · The solution was stirred overnight, filtered, and the residue was recrystallized from ethyl acetate and dried to provide 64.97 g of the desired product, mp 104 ° G.

(b) 1-acetyl-5-amino-3-benzylthio-1,2,4-triazole

Acetyl chloride (12.57 g) in methylene chloride (50 ml) was added to the product from step (a) (50 g) in triethylamine (25 ml) and in methylene chloride (300 ml) at 0 ° C , and the mixture was stirred for 50 minutesand Then 1N sodium hydroxide was added, and the solution was extracted with methylene chloride. Upon drying, and recrystallizing from ethyl acetate, 33 g of the desired product were obtained, mp 146 ° C.

The product of step (b) (112 g) was suspended in a 1: 1 mixture of water and acetic acid, and chlorine was passed through this suspension at -10 ° C for 2 hours. The product was filtered, washed with a little water and pentane, and then dried to provide 74.5 g of the desired product, mp 166-168 ° G.

(d) 1-Acetyl-N- (2.6-dichlorophenyl) -5-amino salt

-1,2,4-triazole-5-sulfonamide pyridinium

The product of step (c) (54 g) was treated with 2,6-dichloroaniline (42.65 g) in pyridine (350 ml), and the mixture was stirred at 60 ° C for 12 hours. After cooling, the product was filtered, washed with a little pyridine and ether, and dried in vacuo to provide 53.6 g of the desired product, mp 213-215 ° C.

(e) N- (2,6-dichlorophenyl) -5-amino-1,2,4-triazole-5-sulfonamide

The product of step (d) (53.6 g) was dissolved in 2N sodium hydroxide (200 ml), and stirred at room temperature for 10 minutes. Then the solution was washed to pH = 5 with 2N hydrochloric acid, and the product was filtered, washed with a little water and ether, and then dried

40 vacuum up to provide 35.4 g of the desired product,

mp 265-267 ° G.

(f) N- (2,6-dichlorophenyl) -5-amino-1- (4.6-dimethyl-pyrimidin-2-yl) -1,2,4-triazole-3-sulfonamide

The product of step (e) (2.15 g) was stirred in dimethylformamide (35 ml) and 2-p-tosyl-4,6-dimethyl-pyrimidine (1.82 g) for 4 hours at 120 ° C, in the presence of 1,8-diazabicyclo (5.4.0) undec-7-ene (2.128 g). After removing the solvents, the residue was stirred in 1N hydrochloric acid (100 ml) and the product was filtered. Then chromatography on silica gel using methylene chloride / methanol (95: 5) to provide 2.1 g of desired product, mp0 306-312 ° C.

Examples K3-K72

The following compounds were prepared

<td colspan="4">of formula I in which R é is hydrogen, by methods as in examples Kl and K2j</td><td>anal</td>

<td>N2.</td><td>IR</td><td>R2</td><td>R3 (F subst;)</td><td>Federal Police</td>

(° C)

<td></td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>mp (° C</td>

<td>K20</td><td>F</td><td>Pirrol-l-ilo</td><td>2,6-diCl</td><td> 208-209</td>

<td>K21</td><td>F</td><td>Pirrol-l-ilo</td><td>2,6-diF</td><td> 157-158</td>

<td>K22</td><td>F</td><td>Pirrol-l-ilo</td><td>2-Cl, 6-F</td><td> 190-191</td>

<td>K23</td><td>F</td><td>N = CHOMe</td><td>2,6-diCl</td><td> 196</td>

<td>K24</td><td>F</td><td>N = CHOEt</td><td>2,6-diCl</td><td> 145-146</td>

<td>K25</td><td>3,5-diMeF</td><td>nh2</td><td>2,6-diCl</td><td> 235-234</td>

<td>K26</td><td>3,5-diMeF</td><td>m2</td><td>2,6-diF</td><td> 194-195</td>

<td>K27</td><td>3,5-diMeF</td><td>nh2</td><td>2,6-diCl, 3-Me</td><td> >230</td>

<td>K28</td><td>3,5-diMeF</td><td>NHEt</td><td>2,6-diF</td><td> 199-200</td>

<td>K29</td><td>3,5-diMeF</td><td>NHEt</td><td>2,6-diCl, 3-Me</td><td> 160-161</td>

<td>K30</td><td>3,5-diMeF</td><td>NHEt</td><td>2,6-diCl</td><td> 155-157</td>

<td>K31</td><td>3,5-diMeF</td><td>Pirrol-l-ilo</td><td>2,6-diF</td><td> 226-227</td>

<td>K32</td><td>3,5-diMeF</td><td>nh2</td><td>2-01.6-F</td><td> 169-170</td>

<td>K33</td><td>3,5-diMeF</td><td>NHEt</td><td>2-Cl, 6-F</td><td> 169-170</td>

til-piri midin-2ilo

<td>K55</td><td>4,6-dimethyl-pyrimidin -2-yl</td><td>nh2</td>

<td>K56</td><td>4,6-dimetho- xi-1,5,5-triazin — 2 — ilo</td><td>NH 2</td>

<td>K57</td><td>Pirimidin- -2-yl</td><td>nh2</td>

<td>K58</td><td>Pirimidin- -2-yl</td><td>NH 2</td>

<td>K59</td><td>Pirimidin- -2-yl</td><td>NH 2</td>

<td>K40</td><td>Pirimidin — 2 — ilo</td><td>NH 2</td>

<td>K41</td><td>Pirimidin- -2-yl</td><td>NH 2</td>

<td>K42</td><td>4,6-dimethyl-pyrimidin -2-yl</td><td>nh2</td>

<td>K45</td><td>4,6-dimethyl-pyrimidin -2-yl</td><td>nh2</td>

Κ44

<td>R5 (F subst :)</td><td>mp, (° 0)</td>

Κ45

4,6-dimetho- NH2 xi-1,3,5-triazin-2-yl —

4,6-dimeto-NH ^ xi-1,5,5-triazin-2 -yl

2,6-diF

215-214

2-Cl, 6-Me

227-228

2,6-diCl

280-282

K46 Piridin-2- NEL

-ilo

<td>NS.</td><td>BI</td><td>B2</td><td>B.3 (Subst.)</td><td>mp (° c)</td>

<td> £47</td><td>Pyridin-2-yl</td><td>nh2</td><td>2,6-diMe, 3-Me</td><td> 236</td>

<td> £48</td><td>Pyridin-2-yl</td><td>m2</td><td>2,6-diBr</td><td> 279-282</td>

<td> £49</td><td>Piridin-2- -ilo</td><td>nh2</td><td>2-01.6-F</td><td> 254-262</td>

<td> £50</td><td>Piridin-2- -ilo</td><td>nh2</td><td>2-Cl, 6-Me</td><td> 246-253</td>

<td> £51</td><td>Pyridin-2-yl</td><td>nh2</td><td>2-CF 5</td><td> 231-236</td>

<td> £52</td><td>Pirimidin- -2-yl</td><td>pyrrole-l-yl</td><td>2-Cl, 6-Me</td><td> 169</td>

<td> £53</td><td>Pirimidin- -2-yl</td><td>NH2</td><td>2-CF, 5</td><td> 218-219</td>

<td>K54</td><td>4-methyl-pi rimidin-2-yl</td><td>nh2</td><td>2,6-diCl, 3-Me</td><td> 264</td>

<td> £55</td><td>4-methyl-pi rimidin-2-yl</td><td>nh2</td><td>2,6-diOl</td><td> 295</td>

<td> £56</td><td>4-methyl-pi rimidin- —2 — ilo</td><td>nh2</td><td>2,6-diF</td><td> 270-275</td>

<td>K57</td><td>4,6-dimet xi-pirimi din-2-ilo</td><td>nh2</td><td>2,6-diCl</td><td> 246-249</td>

<td> £58</td><td>4,6-dimet xi-pirimi din-2-ilo</td><td>nh2</td><td>2,6-diF</td><td> 248</td>

til-piri midin-2-yl

-44'

<td>N2.</td><td>IR</td><td>R2</td><td>R5 (F subst :)</td><td>(° c)</td>

<td>K60</td><td>4,6-dimethyl-pyrim midin-2-yl</td><td>FieNH</td><td>2,6-diCl</td><td> 245-245</td>

<td>K61</td><td>4,6-dimethoxy-pyrimidin-2-yl</td><td>MeNH</td><td>2,6-diF</td><td> 221-222</td>

<td>K62</td><td>4,6-dimethoxy-pyrimidin-2-yl</td><td>MeNH</td><td>2,6-diCl</td><td> 221-223</td>

<td>K63</td><td>4,6-dimethyl-pyrim midin-2-yl</td><td>EtNH</td><td>2,6-diCl</td><td> 242-243</td>

<td>K64</td><td>4,6-dimethyl-pyrim midin-2-yl</td><td>EtNH</td><td>2,6-diF</td><td> 223-224</td>

<td>K65</td><td>4,6-dimethoxy-pyrimidin-2-yl</td><td>HH2</td><td>2,6-diCl, 3-Me</td><td> 277-288</td>

<td>K66</td><td>4,6-dimethoxy-pyrimidin-2-yl</td><td>NH2</td><td>2-CF,</td><td> 237-238</td>

<td>K67</td><td>pyrimidin -2-yl</td><td>nh2</td><td>2-CF5</td><td> 230-231</td>

<td>K68</td><td>pyridin-2-yl</td><td>m2</td><td>2,6-diF</td><td> 289-291</td>

<td>K69</td><td>pyrimidine</td><td></td><td>2,6-diBr</td><td> 292-298</td>

-2-yl

<td>NS.</td><td>IR</td><td>R2</td><td>R3 (F subst :)</td><td>Mp · (° C)</td>

<td>K70</td><td>pyrimidin -2-yl</td><td>pyrrole-l-yl</td><td>2,6-diF</td><td> 148-156</td>

<td colspan="6">The following compounds of formula I where R1 is hydrogen were also prepared by methods analogous to those in examples K1 and K2.</td>

<td>Nfi.</td><td>laughs</td><td>R2</td><td></td><td>R3</td><td>mp, (° C)</td>

<td>K71</td><td>4,6-dimethyl-pyrim midin-2-yl</td><td>nh2</td><td></td><td>naft-l-ilo</td><td> 287-288</td>

<td>K72</td><td>Pirimidin -2-yl</td><td>ke2</td><td></td><td>naft-l-ilo</td><td> 242-243</td>

Preparation of Intermediates

The following examples refer to various intermediates for the preparation of compounds of formula I.

Example I for the preparation of intermediates is an alternative method for the preparation of a compound of formula II from a compound of formula III, which can be used instead of the process of step (c) of preliminary Example A. The other examples of preparation of intermediates are the inter-conversion of compounds of formula III to provide appropriately substituted starting materials, for the processes of step (c) of Example A, Example 1 of Preparation of Intermediates, or processes analogous to Those.

Preparation I of Intermediates

1- (4,6-dimethoxy-1,3,5 ~ triazin-2-yl) -5-46- chloride

-methyl-1,2,4-triazole-3-sulfonyl

A solution of 3-benzyl thio-1- (4,6-dimethoxy-1,5,5-triazin-2-yl) -5-methyl-1,2,4-triazole (6 g) in dichloromethane was treated (60 ml), with silica gel (14 g) of 60-120 mesh and with water (2.8 g). Sulfuryl chloride (10.6 ml) in dichloromethane (12 ml) was added dropwise with stirring, while maintaining the temperature at 5 ° C for 2 hours. The silica gel was filtered, washed with dichloromethane (150 ml) and ethyl acetate (100 ml), and the combined washing products were extracted with water and aqueous sodium bicarbonate. The organic layer was dried and evaporated at 40 ° C in vacuo. The residue was triturated with ether and filtered to provide 3 g of the desired product.

Preparation 2 of Intermediates

3-benzylthio-5-bromo-1-phenyl-1,2,4-triazole

3-Benzylthio-1-phenyl-1,2,4-triazole (5 g) in dry tetrahydrofuran (50 ml) was treated dropwise at -70 ° C with n-butyllithium (1.05 equivalent). The solution was stirred at -70 ° C for 10 minutes and cyanogen bromide (1.98 g) was added rapidly. The mixture was allowed to warm to room temperature and was then quenched with ethanol. Volatile materials were removed in vacuo, and the crude product was chromatographed on silica using dichloromethane to provide 4.3 g of the desired product as a yellow oil.

Preparation 3 of Intermediates

5-Methanesulfonyl-1- (pyrimidin-2-yl) -1.2.4-triazole-3-sulfonyl (a) 3-benzylthio-5-methylthio-1,2,4-triazole chloride

A solution of sodium hydroxide (16 g) in water (60 ml) was added to a suspension of 3-benzylthio-5-mercapto-1,2,4-triazole (89.2 g) in dichloromethane (400 ml) containing benzyl triethyl ammonium chloride (1 g), with stirring and cooling to 15-20 ° C. Methyl iodide (56.8 g) was added to this mixture, and stirring was continued at room temperature for 24 hours. The dichloromethane phase was separated, washed with water twice, dried over sulphate magnesium providing 94 g of the crude product, which was recrystallized from toluene to provide 80.7 g of the desired product, mp 80-82 ° C.

(b) 3-benzylthio-5-methylthio-1- (pyrimidin-2-yl) -1,2,, 4-triazole

The product from step (a) (50 g) was treated with 2-chloro-pyrimidine (24.4 g) by a method analogous to Example F, to provide 23.6 g of the desired product after chromatographic separation of the two products .

Chlorine was bubbled in a suspension of the product from step (b) (8 g) in water (45 ml) and in acetic acid (45 ml) at a temperature between -5 and 0 ° C, with stirring until they were absorbed 9.9 g. Stirring was continued for 10 minutes at a temperature between -5 and 0 ° C before filtering. the product was washed with aqueous acetic acid (1: 2), with water, with 40-60 petroleum ether and finally with ether. Drying provided 6.3 g of the crude product which was recrystallized from ethyl acetate and acetonitrile to provide 3.1 g of the desired product, mp 214-217 ° C.

Preparation 4 of Intermediates

5-oloro-1- (pyrimidin-2-yl) -1,2,4-tri-48azol-3-sulfonyl (a) 3,5-bis (benzylthio) -1- (pyrimidin-2-yl) oloride -1,2,4-triazole

3,5-bis (benzylthio) -1,2,4-triazole (50 g), 2-chloro-pyrimidine (18.3 g) and potassium carbonate (22.1 g) in dimethylformamide (200 ml) were heated ) at 100 ° C for 12 hours. After adding ice-water, the product was extracted with dichloromethane (twice). The dichloromethane solution was washed with water (3 times), dried over magnesium sulfate and left to stand, providing 64.4 g of the title product. Recrystallization from methanol gave 39 g of the desired product, mp 86-88 ° C.

(b) 5-chloro-1- (pyrimidin-2-yl) -1,2,4-triazole-3-sulfonyl chloride

Chlorine was bubbled in a suspension of the product from step (a) (10 g) in water (50 ml) and in acetic acid (50 ml) at a temperature between -5 and 0 ° C until 15 g were absorbed. Then the mixture was stirred for 15 minutes at a temperature between -5 and -10 ° C and filtered. The white precipitate was washed with cold aqueous acetic acid (1: 1), with water and with petroleum ether 40 -60, to provide 7.6 g of the crude product. This solid was heated to reflux in ethyl acetate (300 ml) for 2 hours and 30 minutes. The white residual by-product was filtered, and the solution was dried in vacuo. The residue was heated with ether (100 ml), filtered through diatomaceous earth, and reduced in volume to 10 ml. Cooling with ice provided the desired product as a solid which was filtered to obtain

2.2 g, mp 98-101 ° C.

Preparation 5 of Intermediates

3-benzylthio-5-methoxy-1-phenyl-1,2,4-triazole

3-Benzylthio-5-hydroxy-1-phenyl-1,2,4-triazole (15 g) in dichloromethane (60 ml) was treated with trimethyl-oxonium tetra-fluoro-borate (15.7 g) and it was left to stand for 18 hours at room temperature. The reaction mixture was poured into water (200 ml) and the aqueous layer was washed with dichloromethane (2 x 100 ml). The dry organic layer was evaporated and then purified by column chromatography (silica / petroleum ether: ether), to provide 8.1 g of the desired product.

Preparation 6 of Intermediates

5-acetoxy-1-phenyl-1,2,4-triazol-5-sulfonyl chloride (a) 1-ethoxy-carbonyl-1-phenyl-thio-semicarbazide

A mixture of 1-phenylthio-semicarbazide (25 g), ethanol (180 ml) and ethyl chloroformate (17 ml) was heated under reflux with stirring for 30 minutes. The mixture was cooled to room temperature and the solid was filtered, washed with ethanol and then with ether to provide 28.9 g of the desired product.

(b) 5-hydroxy-1-phenyl-1,2,4-triazole-3-thiol

The product of step (a) (28.9 g) was treated with a solution of sodium hydroxide (7.5 g) in water (150 ml). The suspension was heated to reflux with stirring for 45 minutes and then cooled to 25 ° C. The solution was adjusted to pH 1.0 with concentrated hydrochloric acid and the resulting solid was filtered and washed with water to provide 20.2 g of the desired product, (c) 3-benzylthio-5-hydroxy -l-phenyl-1,2,4-triazole

product of step (b) (20 g) ethanol (300 ml) and sodium hydroxide (5 g) were stirred together for 10 minutes. Benzyl chloride (12.3 ml) was added, and the mixture was heated to reflux with stirring for 24 hours, the solvent was removed in vacuo, and the residue was treated with water. The pH was adjusted to 1.0 with concentrated hydrochloric acid, and the solid was filtered, washed with water and recrystallized from ethanol to provide 21.75 g of the desired product.

(d) 5-acetoxy-3-benzylthio-1-phenyl-1,2,4-triazole

A mixture of the product from step (c) (20 g), toluene (150 ml) and acetyl chloride (12.2 ml) was heated at reflux for 5 hours. Volatile materials were removed in vacuo, and the residue was triturated with ether and filtered. Recrystallization from ethanol provides 19.8 g of the desired product.

(e) 5-Acetoxy-1-phenyl-1,2,4-triazole-3-sulfonyl chloride

A suspension of the product from step (d) (10 g) in glacial acetic acid (20 ml) and in water (30 ml) was stirred at -5 ° C. Chlorine was bubbled through the stirred solution for 40 minutes, and then water (200 ml) was added. The solid was filtered, washed with water and dry air to provide 6.3 g of the desired product.

In a subsequent reaction of this compound with 2,6-difluoroaniline, according to Example A, the acetoxy group of the product in process was hydrolyzed to provide N- (2,6-difluoroenyl) -5-hydroxy-1- phenyl -1,2,4-triazole-3-sulfonamide.

Preparation 7 of Intermediates

3-benzylthio-5-bromo-1-phenyl-1,2,4-triazole

N-Butyl lithium (50 ml) was added dropwise to a stirred solution of 3-benzylthio-1-phenyl-1,2,4-triazole (31.8 g) in dry tetrahydrofuran (200 ml) at -70 ° C. Bromine (19 g) was added and the reaction mixture was allowed to warm to room temperature and quenched with water. After washing with brine, the organic phase was dried and evaporated to provide a yellow oil. Purification by chromatography on silica with chloromethane and petroleum ether gave the desired product as a faint yellow oil.

The corresponding compounds in which the substituent in position 5 was methoxycarbonyl, acetyl and hydroxylmethyl were also prepared by analogous methods using methyl chloroformate, Ν, Ν-dimethyl-acetamide and Ν, Ν-dimethyl-formamide respectively as electophiles , followed by reduction using sodium borohydride.

Formulation Example 1

A water-soluble powder concentrate equivalent to 80% active acid was prepared from the following ingredients:

/.eZP,

Compound of Example A54, K salt+94.8

Neosyl (silica) 2.7 (Sodium N-methyl tauride) 2.5

Similar compositions were also prepared containing compounds from the other examples mentioned above equivalent to active acids at 20, 40 and 60% w / w.

Formulation Example 2

A 7.5% aqueous solution formulation was prepared from the following ingredients:

<td>Compound of Example Cl</td><td> 75.0</td>

<td>Potassium hydroxide (85% granules)</td><td> 12.4</td>

<td>N-methyl-pyrrolidone</td><td> 506.7</td>

<td>Water</td><td>what</td>

Similar formulations were also prepared containing 60 g / liter and 75 g / 1 of the compounds of the other examples mentioned here, particularly the compound of Example 04

Formulation Example 3

A 10% aqueous solution was prepared from the following ingredients:

Compound of Example A63100.0

Potassium hydroxide (1M) 263.1

Water.

Analogous formulations were also prepared containing 5% and 10% of the compounds of other examples referred to herein.

EXAMPLE THE HERBICIDE (Before appearance)

Seeds of the species were sown

of weeds below, in anodized aluminum pots 19 cm long x 9.5 wide x 6 cm high, containing sterilized sandy loam. They showered and. ask with the compounds of the examples which are indicated below to be formulated as a solution / suspension in 1: 1 by volume of acetone with a solution (2 g per liter) of polyoxyethylene monolaurate (20 mol) being the wetting agent.

The concentration of each tested compound and application volume was calculated to provide a desired application rate of the compound at 450 liters per hectare. After 3 and 4 weeks of development in the controlled environment compartment (20 ° C; relative humidity of 75—95%; 14 hours a day of artificial lighting), the herbicidal response of the plants was visually estimated.

All differences from untreated control plants were classified according to an index where 0 = no effect, 1 = an effect of 1-24%, 2 an effect of 25-69%, 3 = an effect of 70 -89% and 4 = 90-100% effect. In the following table, the following letters are used to indicate the plant species:

a - Polygonum lapathifolium (persicaria) b - Galium aparine (aparinas) c - Chrysanthemum segetum (marigold) d - Alopecurus myosuroides (grass) e - Elymus repens (wild wheat) f - Avena fatua (wild oats) g - Abutilon theophrasti (leaves velvet) h - Cyperus rotundus (junça) i “Pharbitis purpurea (ipomeia) j - Echinochloa crus-galli (grass) k - Setaria viridis (foxtail)

- Solanum nigrum (nightshade)

-54The results obtained were the guintess

<td colspan="4">EXAMPLE B HERBICIDE</td><td>(After</td><td> 0</td><td colspan="3">appearance)</td><td></td><td></td><td></td><td></td><td></td>

Seeds of the plant species listed below are sown in anodized aluminum pots, 16 cm long x 9.5 cm x 6 cm deep, containing sterilized sandy loam. They were watered and placed in the controlled room compartment (20 ° C; 75-95% relative humidity; 14 hours per day of artificial lighting). Between 14 and 20 days after sowing (depending on the species but especially when the plants had 2 or 3 leaves developed) the cultures received a foliar spray of the compounds of the examples below, formulated as a 1 solution / suspension: 1 by volume of acetone, the wetting agent being a solution (2 g per liter) of polyoxyethylene monolaurate (20 mol).

The concentration of each tested compound was calculated to provide the desired application rate of the compound at 450 liters per hectare. After two to three weeks of growth in the controlled environment compartment, the herbicidal response of the plants was visually estimated.

All differences from untreated plants were classified according to an index where 0 = no effect, 1 = effect of 1-24%, 2 = effect of 25-69%, 3 = effect of 70-89%, 4 = 90-100% effect. In the following table the plant species are indicated with the following letters:

a - Polygonum lapathifolium (persicaria) b - Galium aparine (aparinas) c - Chr.ysanth.emum segetum (marigold) d - Alopecurus myosuroid.es (grass) and “Elymus repens (wild wheat) f - Avena fatua (wild oats) g - Abutilon theophrasti (velvet leaves) h - Cyperus rotundus (june) i - Pharbitis purpurea (ipomeia) j - Echinochloa crus-galli (grass) k - Setaria viridis (foxtail)

- Solanum nigrum (nightshade)

The results obtained were as follows:

CLAIMS

Contents3

28 members in 18 offices

This recordMember, by publication datePriority claim8 more offices are in the list below

Priority claims16

Priority claims
Document	Office	Kind	Date
8612062	United Kingdom	A	1986-05-17
8612062	United Kingdom	A	1986-05-17
3643021	Germany	A	1986-12-12
3643021	Germany	A	1986-12-12
3707202	Germany	A	1987-03-05
3707202	Germany	A	1987-03-05
3708215	Germany	A	1987-03-12
3708215	Germany	A	1987-03-12
3643021	–	–	–
3707202	–	–	–
3708215	–	–	–
8612062	–	–	–
DE19863643021	–	–	–
DE19873707202	–	–	–
DE19873708215	–	–	–
GB19860012062	–	–	–

Members28

Family members, oldest first
Document	Office	Kind
GB8612062D0	United Kingdom	D0	1986-06-25
DK245087D0	Denmark	D0	1987-05-14
FI872124A0	Finland	A0	1987-05-14
PT84872A	Portugal	A	1987-06-01
ZA873460B	South Africa	B	1987-11-16
DK245087A	Denmark	A	1987-11-18
FI872124A	Finland	A	1987-11-18
FI872124A7	Finland	A7	1987-11-18
EP0246749A2	European Patent Office (EPO)	A2	1987-11-25
AU7300087A	Australia	A	1987-11-26
IL82546A0	Israel	A0	1987-11-30
KR870011127A	Republic of Korea	A	1987-12-21
JPS6322083A	Japan	A	1988-01-29
CN87103542A	China	A	1988-02-03
BR8702527A	Brazil	A	1988-02-23
HUT44135A	Hungary	A	1988-02-29
DE3643021A1	Germany	A1	1988-06-23
EP0246749A3	European Patent Office (EPO)	A3	1988-08-31
DE3707202A1	Germany	A1	1988-09-15
DE3708215A1	Germany	A1	1988-09-22
DD261086A5	German Democratic Republic (until 1990)	A5	1988-10-19
KR890003727A	Republic of Korea	A	1989-04-17
AU583728B2	Australia	B2	1989-05-04
US4889553A	United States of America	A	1989-12-26
PT84872BThis record	Portugal	B	1990-02-08
PH24040A	Philippines	A	1990-02-09
TR24082A	Türkiye	A	1991-03-04
HU204974B	Hungary	B	1992-03-30

Triazole herbicides

Abstract

Term

O

F:

CLAIMS

Priority claims16

Members28

Events

Numbers

Titles2

Classification