DD261086A5 - HERBICIDAL COMPOSITION - Google Patents

Abstract

The invention relates to herbicidal compositions. According to the invention, novel herbicidal compositions are prepared which contain as active ingredient triazolesulphonamides of the formula and their salts, in which the substituents have the meaning given in the description. The compositions of the invention are applicable to selective weed control in agriculture. Formula (I)

Description

Herbicidal composition Field of application of the invention

The invention relates to a herbicidal composition for use in agriculture for selective weed control in crops.

Characteristic of the known state of the art

No information is available on which compounds have hitherto been used for selective weed control in crops,

Aim of the invention

The aim of the invention is to provide novel compositions with strong herbicidal activity which can be used for selective weed control in crops of useful plants,

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties that are suitable as active ingredient in herbicidal compositions for use in selective weed control in agriculture.

According to the invention, the active ingredient in the novel herbicidal

2 + 3 ziden compositions Triazolsulfonamide with the formula

and their salts are used, in which

R is hydrogen or a substituted or unsubstituted alkyl, alkenyl »alkynyl ,. Cycloalkyl, aryl, aralkyl, acyl, alkoxycarbonyl, aminocarbonyl, sulfonyl or a heterocyclic group;

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

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

R is hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl. Azyl, alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, aralkyl or a group represented by the formula:

(A)

1 2 wherein R and R are as defined above.

12 4

If R, R or R represent or contain an alkyl group, this is preferably a group with 1 "to 6 carbon atoms, in particular with 1 to 4 carbon atoms.

12 4 ge group, which can be represented by R, R and R are u. a. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. If desired, the alkyl group may be substituted, for example by one or more halogen atoms, e.g. For example, fluorine, chlorine or bromine, alkoxy or alkylthio groups having 1 to 4 carbon atoms, for. Methoxy, ethoxy or methylthio groups, or acyloxy groups of 2 to 5 carbon atoms. Special

1 2 games for substituted ones. Alkyl groups which can be represented by R, R and R are u. a. Chloromethyl, bromomethyl, dichloromethyl and trifluoromethyl. also

p can advantageously be methoxy group, ethoxy group, n-propoxy group, methylthio group, hydroxymethyl, methoxymethyl, ethoxymethyl, methoxyethyl, sthoxyethyl or acetoxymethyl.

12 4-

When R, R or R represents an alkenyl or alkynyl group, this group preferably has 2 to 6 carbon atoms, for example vinyl, allyl or propargyl. Each of these alkenyl or alkynyl groups is preferably unsubstituted.

When R is a cycloalkyl, it is preferably one having 5 to 7 carbon atoms, especially cyclopentyl or cyclohexyl.

12 4

When R, R or R represents an acyl or alkoxycarbonyl group or an alkyl-substituted aminocarbonyl or sulfonyl group, each alkyl moiety preferably corresponds to the description above. The acyl group may, if desired, be an aroyl or heteroaroyl group, preferably a benzoyl or 2-thieno group. Particularly preferred aryl and alkoxy carbonyl groups include acetyl and methoxy carbonyl.

13 4

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

When R is or contains an aryl group, it is preferably a phenyl group which is desirably unsubstituted but which is substituted by one or more halogen atoms or alkyl or alkoxy groups having from 1 to 4 carbon atoms, especially methyl or methoxy groups, especially 3,5- may be disubstituted.

When R is aryl, it is preferably phenyl which is desirably unsubstituted but may be substituted by one or more halogen atoms or alkyl or alkoxy groups of from 1 to 4 carbon atoms, especially methyl or methoxy groups.

When R 1 is or contains an aryl group, this group is preferably phenyl, which is desirably substituted

is, for example, by one or more halogen atoms (eg I ¹ IuOr, chlorine or bromine), nitro groups, cyano groups, substituted or unsubstituted amino or amido groups (for example alkylamino, dialkylamino, azylaraino, alkylamido). or dialkylamido groups, especially those in which the alkyl moiety has from 1 to 4 carbon atoms), optionally substituted alkyl, alkoxy or alkylthio groups having from 1 to 4 carbon atoms (eg methyl, ethyl, methoxy, bthoxy, methylthio or ethylthio ), Alkoxy carbonyl groups having 2 to 5 carbon atoms, or alkylsulfinyl or alkylsulfonyl groups having 1 to 4 carbon atoms.

When R, R or R represents a heterocyclic group, this group is preferably a monocyclic group having 5 or 6 ring atoms containing at least one nitrogen, oxygen or sulfur atom and which may be naturally substituted, e.g. By one or more halogen atoms, hydroxy group, hitro groups, cyano groups, optionally substituted amino or amido groups (e.g., alkyl of 1 to 4 carbon atoms), alkyl, alkoxy or alkylthio groups of 1 to 4 carbon atoms, acyl or alkoxy carbonyl groups having 2 to 5 carbon atoms or alkylsulfinyl or alkylsulfonyl groups having 1 to 4 carbon atoms. Among the possible heterocyclic groups are of course the Η-oxides of the corresponding heterocyclic compounds,

•1

Heterocyclic groups which may be represented by R include substituted or unsubstituted pyridinyl, pyrimidinyl, piperidinyl, pyrazinyl, quinoxalinyl, morpholinyl, triazinyl, thienyl, benzoxazolyl, thiadiazolyl and ω-amino groups.

Among the most preferred heterocyclic groups, the

2 can be represented by R, include pyrrol-1-yl _a and 2,5-dimethylpyrrol-1-yl.

2 When R represents a halo group, it is preferably a fluoro, chloro or bromo group.

When R represents a substituted amino group, it is preferably an alkylamino or dialkylamino group in which each alkyl moiety has from 1 to 4 carbon atoms and may be further substituted, e.g. B. by alkoxy groups having 1 to 4 carbon atoms. Particularly preferred of these groups include methylamido, ethylamino, methoxytn <3-ethylamino, ethoxymethylamino and dimethylamino groups.

When R represents a heterocyclic or benzo-heterocyclic group, it is preferably a benzothienyl or benzoxazolyl group, although it may be, for example, a thiazolyl, isoxazolyl, pyridinyl, piperidinyl, triazolyl, benzothiazolyl or quinolinyl group represented by one or more Alkyl or alkoxy groups having 1 to 4 carbon atoms may be substituted.

R is preferably hydrogen, alkyl of 1 to 6 carbon atoms, phenyl (which is desirably unsubstituted but substituted by one or more halogen atoms or alkyl or alkoxy groups of 1 to 4 carbon atoms, especially methyl or methoxy groups, especially 3.5 or a monocyclic heterocyclic compound having 5 or 6 ring atoms which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms, cyano groups, amino

groups (which may be unsubstituted or substituted, for example by methyl or ethyl), halogen atoms or alkylsulfinyl or alkylsulfonyl groups having from 1 to 4 carbon atoms may be substituted. Among the preferred groups which can be represented by R are hydrogen, methyl, ethyl, n-propyl, η-butyl, phenyl, 3,5-dimethylphenyl and substituted or unsubstituted pyrimidin-2-yl, 1,3,5-Sriazine -2-yl and 1,2,4-triazin-3-yl groups, especially 4-methylpyrimidin-2-yl, 4-methozypyrimidin-2-yl, 4,6-dimethylpyrimidin-2-yl, 4,6-diraethoxypyrimidine -2-yl, 4,6-dichloropyrimidin-2-yl, 4-methyl-6-chloropyrimidin-2-yl, 4-methyl-6-methylaminopyrimidin-2-yl, 4-methyl-6-aminopyrimidin-2-yl , 4-Methyl-6-dimethylaminopyrimidin-2-yl, 4-chloro-6-methoxypyrimidin-2-yl, 4-methyl-5-chloro-6-methoxypyrimidin-2-yl, 4-methyl-6-methozypyrimidine-2 -yl, 4,6-dimethoxy-1,3,5-triazin-2-yl, 4-chloro-6-methyl-1,3,5-triazin-2-yl, 4-chloro-6-methoxy-1 , 3j5-triazin-2-yl, 4-methoxy-6-methyl-1,3,5-triazin-2-yl, 4-methylamino-6-methoxy-1,3,5-triazin-2-yl and 4 -Hethylaraino-6-chloro-1,3,5-triazin-2-yl.

R is preferably hydrogen, halo, cyano, alkyl or alkoxy group having 1 to β carbon atoms (which is substituted by one or more halogen atoms, hydroxy groups, alkoxy groups having 1 to 4 carbon atoms or acyloxy groups having 2 to 5 carbon atoms or is unsubstituted), alkoxycarbonyl having 2 to "5 carbon atoms, amino group, alkylamino group having 1 to 4 carbon atoms, monocyclic heterocyclic compound having 5 or β ring atoms which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl groups having 1 to 4 carbon atoms.

Among the most preferred groups by. R can be represented by hydrogen, chloro, bromo, cyano, methyl, ethyl, n-propyl, n-btuyl, s-butyl, hydroxymethyl, methoxymethyl, ethoxymethyl, methoxyethyl, acetoxymethyl, methoxy, sthoxy, methoxy carbonyl, amino , Methylamino, ethylamino, pyrrol-1-yl, and 2,5-dimethylpyrrol-1-yl.

R preferably represents a phenyl group represented by one or more halogen atoms, nitro groups, cyano groups or alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms (which in turn may be substituted by one or more halogen atoms) or alkoxycarbonyne groups having 2 to 6 Carbon atoms (especially 2-substituted, 2,6-disubstituted, 2,3,5-trisubstituted, 2,3,6-trisubstituted or 2,3,5,6-tetrasubstituted).

One of the particular groups which may be represented by R · ^ include 2-5 IuOrophenyl ^1, 2-chlorophenyl, 2-bromophenyl, 2-Zyanophenyl, 2-methylphenyl, 2-methoxyphenyl _2-v Methyltiophenyl, 2-trifluoromethylphenyl, 2 -Methosycarbonylphenyl, 2-ethoxycarbonylphenyl, 3-I ¹ IuOrOPhenyl, 2-difluoromethoxyphenyl, 2,3-difluorophenyl, 2,5-difluorophenyl, 2,6-dimethylphenyl, 2,3,5,6-tetrafluorophenyl, 2-methyl-6 methoxycarbonylphenyl, 2-fluoro-6-methoxycarbonylphenyl and especially 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-dibromoephenyl, 2-methyl-6-nitrophenyl, 2-chloro-6-methylphenyl, 2-I 1-chloro-6-methoxycarbonylphenyl, 2-chloro-6-methoxycarbonyloxy, 2,6-dichloro-3-methylphenyl or 2-chloro-6-fluorophenyl.

R 1 is preferably hydrogen, methyl, acetyl, benzoyl, methylsulfonyl, methoxycarbonyl, dimethylcarbamoyl or benzyl.

Particularly preferred compounds after the addition are those of the following examples, with particular mention being made of:

H- (2,6-difluorophenyl) -t (pyrimidin-2-yl) -5-tnethyl-1,2,4-triazole-3-sulfonamide;

H- (2,6-Dichloro-3-methylphenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triaζο1-3-sulfonamide;

H- (2-methyl-6-nitrophenyl) -1- (pyrimidin-2-yl) -5-niethyl-1,2,4-triazole-3-sulfonamide;

K- (2,6-difluorophenyl) -1- (4,6-dimethylpyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide;

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

H- (2,6-difluorophenyl) -1 - (- 4-methylpyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide;

H- (2,6-Difluorophenyl) -1- (4-methoxy-6-methylpyrimidin-2-yl) 5-methyl-1,2,4-triazole-3-sulfonamide;

H- (2,6-dichlorophenyl) -1- (4: 6-dimethoxy-1,3,5-triazine-2-yl) 5-methyl-1,2,4-triazole-3-sulfonamide;

H- (2,6-dichlorophenyl) -1- (4,6-dimethylpyrimino-2-yl) -1,2,4-triazole-3-su.lfamide;

H- (2,6-Dichlorophenyl) -1- (4,6-dimethylpyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide;

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

N- (2, β-dichloro © phenyl) -5- (2,5-dimethyl-pyrrol-1-yl) -1,2,4-triazole-3-sulfonamide;

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

N- (2, ö-dichloro-S-methylphenyl) -1- (4,6-dimethylpyr ± midin-2-yl) * 1,2,4-triazole-3-sulfonamide;

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

N- (2,6-dichloro-3-methylphenyl) -5-amino-1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1,2,4-triazole-3 suKonamid.

In another aspect of the invention, the invention provides a process for the preparation of a triazolesulphonamide of the formula I according to which a triazolesulphonyl halide of the formula:

E ¹

N N

LX cn)

_R 2 N

12

wherein R and R are as defined above and Hal is halogen, in the presence of a base, is reacted with an amine of the formula R - 'r'tIH, wherein R and R are as defined above to give the desired compound.

The reaction is advantageously carried out "at a temperature between -10 ° and 100 ° C, in particular between -10 ° and 25 ° σ, most preferably at room temperature.

The base is preferably an organic base, in particular a tertiary organic base, for example pyridine, Έ , K-dimethylaniline or triethylamine or an excess of the amine RRlH. The reaction can be catalyzed by certain tertiary organic bases, for example by the dimethylaminopyridine. When R is an acyl group, the base used is preferably a strong base, for example, sodium hydride, and the reaction is advantageously carried out in a suitable aprotic solvent, e.g. Eg tetrahydrofuran, carried out «

If desired, the reaction conditions may be adjusted to produce compounds of formula .1 in which R represents a group of formula A. When such compounds are desired, it is advantageous to use at least 2 moles of the sulfonyl halide to use with the formula II per mole of amine. Alternatively, the compounds of formula I in which R represents a group of formula A may be selected from the corresponding compounds.

* 4

are prepared with the formula I in which R represents hydrogen, by their reaction with another SUlfonyXhalid of the formula II in the presence of a strong base. In such a case, for example, the base may be sodium hydride which may be dissolved in a suitable solvent, e.g. For example, tetrahydrofuran is used.

The compounds of formula II, in turn, can be prepared by the reaction of a compound of the formula:

JL JL cm)

R ^ ^ ^i! SR

12

wherein R and R are as defined above and R represents hydrogen, alkenyl, acyl or aralkyl, with the appropriate halogen or sulfury1-halide in a suitable solvent to give the desired compound.

The reaction is desirably cooled to less than ambient temperature, e.g. B. to a temperature of 5 ° C or less executed.

The compounds of the formula III in which R 1 represents hydrogen can in turn be prepared by an esterification. in which an alkanoylthiosemicarbazide having the formula:

R ¹ S ₂ II

R ^ CO - Έ - KH - C - HH ₂ (IV)

12

wherein R and R are as defined above, cyclized in the presence of a base to give the desired compound.

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

The base used may be, for example, a carbonate, for. B. sodium carbonate.

The compounds of formula III wherein R is not hydrogen may each be selected from the corresponding compounds.

fertilize, in which R is hydrogen, by the known methods, such as alkylation or acylation, are prepared.

The compounds of formula III may also be interchanged with other known methods to obtain any desired starting material for this formula. For example, when R is a protecting group, e.g. B.

12

Benzyl, the compounds wherein R or R is hydrogen can be converted to the corresponding compounds wherein R or R is not hydrogen by the known anion coupling methods.

The compounds of formula IV can be prepared by acylating the corresponding thiosemicarbazides of the formula

1 1

R HH.HH.CS.HH ₂ where R is as defined above

be prepared by the known methods.

The compounds of the formula I can also be interchanged with one another by the known methods. For example, the compounds of formula I wherein R is not hydrogen may generally be prepared from the corresponding compounds of formula I wherein R is hydrogen by reacting with a halide of formula R Hal in the presence of a base, for example of sodium hydride, halo-carbonate or pyridine.

The compounds of formula I in which R represents a group of formula A may be hydrolyzed under suitable conditions to produce the corresponding compounds in which R is hydrogen.

The compounds of formula I in which R is not hydrogen can be prepared from the corresponding compounds of formula I in which R is hydrogen by reacting with a suitable electrophile (for example a compound of formula R ¹ Hal, R ¹ SO ₂ CH ^ or R ¹ SO ₂ P-ToIuen) are prepared. if that is desired, in the presence of a base such as sodium hydride, Kaliumkarbonyt, triethylamine or 1,8-Diazobizyklo (5,4,0) undek- 7-en at room temperature or with heating and in a suitable solvent, for. B. dimethylformamide, tetrahydrofuran or dimethosyethane ·

Carboxyl groups present in the compounds of formula I may be esterified, existing ester or ilyl groups may be hydrolyzed to give the corresponding acids, and cyano or ester groups may be converted to amido or substituted amino groups. These as well as numerous other transformations can be carried out by methods known to those skilled in the art, and various examples of "such transformations" are given below.

The compounds of formula I are herbicidally active against a wide range of broad-leaved and grassy weeds, but are comparatively safe for certain crop species. They can therefore be used as selective herbicides, especially in the control of a number of weeds in cereals or other crops , z. As wheat, barley, corn, soybeans, oilseed rape, cotton or sunflower.

In another aspect, the compound provides a herbicidal composition consisting of one or more compounds of the invention, together with a suitable

Neten carrier agents and / or surface active agents.

The compositions typically contain from 0.01% to 99% by weight of the present compositions and are normally prepared first as concentrates containing from 0.5% to 99% by weight, preferably 0.5% to 85% by weight in particular from 10 to 50% by weight of the "compounds." These solubilates are diluted, if necessary, to the point to be treated prior to application, so that the active ingredient constitutes from 0.01 to 5% by weight of the applied composition ,

The carrier may be water, in this Pail may also be an organic solvent, but which is not usually used. Flowable suspension concentrate may be prepared by grinding the compound with water, a wetting agent and a suspending agent, e.g. Xanthan gum.

Alternatively, the carrier may be a water-immiscible organic solvent, e.g. B. a hydrocarbon having a boiling range of 130 ° - 270 ° C, z. B. xylene, in which the compound is dissolved or brought to suspension. An emulsifiable concentrate containing a water-immiscible solvent may be prepared with a surfactant so that the concentrate acts as a self-emulsifiable oil when admixed with water.

Alternatively, the carrier may be a water-miscible organic solvent, e.g. For example, 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, MethylformaUd or dimethylformamide.

Alternatively, the carrier may be a pesticide which may be finely divided or granulated. Examples of suitable solid carriers are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers , The carrier may be of natural or synthetic origin, or it may be a modified natural material.

Wettable powders which are soluble or dispersible in water may be prepared by mixing the compound in particulate form with a particulate carrier or by spraying the molten compound onto the particulate carrier, admixing a wetting agent and dispersant, and finely grinding the entire powder mixture.

An aerosol composition can be prepared by mixing the compound with a propellant, e.g. As a polyhalogenated alkane, such as Dichlorofluoromethan, and advantageously with a solvent.

The term "surfactant" is used broadly and also includes agents which are variously referred to as emulsifiers, dispersants and wetting agents. Such agents are well known in the art.

Surfactants used may include anionic surfactants, for example mono- or diesters of phosphoric acid with fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulfates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethylene oxide.

ι \ j ο

xylated alkylphenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates such as alkyl benzene sulfonate or lower alkyl naphthalene sulfonates, salts of sulfonated uraphthalene formaldehyde condensates, salts of sulfonated phenol formaldehyde condensates or more complex sulfonates such as amide sulfonates, e.g. As the sulfonated condensation product of oleic acid and H-methyltattrin, or the Dialkylsulfosukzinate, z. B _{e is} the sodium sulfonate of dioctyl succinate.

The surface-active agents may also be nonionic agents, for example condensation products or fatty acid esters, pettalcohols, peteamic acid amides or alkyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. For example, sorbitan acid esters, condensation products of such esters with ethylene oxide, for example polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylene glycols such as 2,4,7,9-tetramethyl-5-deoxy-4,7-diol or ethoxylated acetylene glycols.

The surfactants may also be cationic agents, for example alkyl- and / or aryl-substituted quaternary ammonium compounds such as ketyltrimethylammonium bromide or ethoxylated tertiary fatty amines.

Preferred surfactants include ethoxylated fatty alcohol sulfates, lignosulfonates, alkylarylsulfonates, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, potassium oleoyl-1-methyltauride, dialkylsulfosuccinates, alkylphenol ethoxylates and fatty alkyl ethoxylates.

The present active compounds, in particular those of the examples below, and especially the above

Examples given may be mixed with another pesticide, for example B * a herbicide, fungicide or insecticide, or a plant growth regulator, in particular another herbicide, eg. B * trietazine, linuron, MCPA, di-chloroprop, osoxaben, diflufenican · metolachlor, fluometuron, oxafluorfen, fomesafen, bentazone, prometryn, norflürazone, clomazone, EPTC, imazaquin and especially isoproturon, methabenzothiazuron * trifluralin, doxynil, bromoxynil, benazoline, mecoprop , Fluroxypyr ,, Alachlor, Azifluorfen, Lactofen, Metribuzin and Pendimethalin »

The present compounds may be applied to plants * on the soil, land or water surfaces, and more particularly to a site where a crop is to grow or grow. The compounds are active both before and after formation.

Embodiment """_

The invention is illustrated by the following examples in which the following symbols are used: Me = methyl, Etβ ethyl, Pr β propyl, Bu = butyl and PH = phenyl,

Production Example A:

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

(a) 1-Sutvryl-1-phenylthiosemicarbazide

A stirred mixture of 1-phenylthiosemicarbazide (30 g) and

Butyric anhydride (31> 2 g) in toluene (250 ml) was heated for two hours under reflux * After cooling, the crude product was filtered as a white powder "melting point 219 ° - 221 ⁰ CU

A suspension of the product from step (a) (40g) in aqueous 10% sodium carbonate solution (200ml) was heated at reflux for 2 hours. The resulting clear, yellow solution was cooled and acidified with concentrated hydrochloric acid, giving a greyish white precipitate. This was filtered off and recrystallised from ethanol to give the desired product (33 g) as white needles, mp 142-143 ° C

^(C) LRI & § ^n; zl ~ FP5 £ 2P2i = lj. Zx ^ z

Chlorine gas was bubbled through a stirred suspension of the product of step (b) (20g) in 60% aqueous acetic acid (200ml) at -5 ° C for 90 minutes. The white gum was filtered off, washed with ice-cold water and dried to give the desired product as a white powder (25 g).

(d) K- (2,6-Difluorophenyl) -1-phenyl-5-n-propyl-1,2,4-tria-

Dq's product from Example A, step (c) (4g) was added in portions to a stirred solution of 2,6-difluoroaniline {3, β g) and 4-dimethylaminopyridine (0.2g) in dry pyridine (25ml). After 18 hours at 25 ° C, most of the pyridine was removed in vacuo. The residue was dissolved in 1 M sodium hydroxide solution (70 mL) and was treated with ethyl acetate (2 χ 30 mL). The aqueous layer was acidified with concentrated hydrochloric acid and the solid was filtered off and recrystallised from toluene to give 3.1 g of the desired product, m.p. 148- 150 ° C.

Examples A2 to A102;

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

KS R ¹ R ² Ir (Ph substituted :) Melting point ( ⁰ C) A2 Ph me 2,6-dii ¹ 170 - 172 A3 Ph me 2,6-diCl, 3-Me 188 - 189 A4 Ph et 2,6-diP 168 - 170 A5 Ph n-Pr 2 ~ F 129 - 131 A6 Ph n-Pr 3-F 146 - 148 A7 Ph n-Pr 2-Cl 122-124 A8 Ph n-Pr 2,3-diP 122-124 A9 Ph n-Pr 2,4-diP 138-140 A10 Ph n-Pr 2.6 -diMe 174 - 175 A11 Ph n-Pr 2-01, 6-Me 173 - 174 Al 2 Ph n-Pr 3-01, 2-Me 138-140 A13 Ph n-Pr 2,6-diCl, 3-Me 189-192 A14 Ph n-Pr ' 2,3,5,6-tetra- ¹ 118 - Ί19 A15 Ph i-Pr 2,5-diP 136 - 137 A16 Ph i-Pr 2.6 -diF 157-158 A17 Ph i-Pr 2,6-Dicl 201 - 202 A18 Ph i-Pr 2-Cl, 6-Me 189-190 A19 Bra i-Pr 2,6-diCl, 3-Me 195-196 A20 Ph n-Bu 2-F 142 - 143 A21 Ph ' n-Bu 2,6-dii ¹ $ 16-170 A22 Ph n-Bu 2-Me, 6-ITO ₂ 136 - 137 A23 Ph n-Bu 2,6-diol, 3-Me 167-168 A24 Ph i-Bu 2-i ¹ 137 - 138 A25 Ph i-Bu 2,6-diP 155-156 A26 Ph t-Bu 2, .6 -diF 210-211

R ¹ R ² R ³ (PK substituted :) Melting point ( ⁰ C)

A27 Pb t-Bu 2-Cl, 6-Me 194-195

A28 Ph Ph 2 Cl 182-185

A29 Ph Ph 2 MeO 162

A30 Ph Ph 2 GOOEt 113-114

A31 Ph Ph 4 GOOEt 184-186

A32 Ph Ph 2 Cl, 6-Me 185-188

A33 i-Pr Me 2-Me 164-166

A34 i-Pr Me 2 COOEt 113-115

A35 i-Pr Et 2-Cl, 6-Me 170-173

A36 i-Pr Ph 2,6-diP. 172-173

A37 i-Pr Ph 2 Cl, 6-Me 185-186

A38 i-Pr 2-ClPh 2,6-diP 216-211

A39 i-Pr 2-GlPh 2 → 01, 6-Me 202 - 203

A40 Ph H 2,6-diP 186-188

A41 Ph H 2,6-diCl, 3-Me 145-147

A42 Ph Me 2-Cl, 6-Me 142-143

A43. Ph Me 2-01, 6-P 185-187

A44 Ph Et2,6-diCl, 3-Me 190-192

A45 Ph Et 2-Cl, 6-Me 139-141

A46 Ph n-Pr 2-01, 6-F 151-153

A47 Ph-PrPentaP 123-124

A48 Ph n-Bu 2-Cl, 6-SMe 157-158 *

A49 Ph n -Bu ₂ OCHP ₂ 114-115

A50 Ph t-Bu 2,6-diol 194-195

A51 GF Ph. ₃ 2,6-diP 159-163

A52 Ph CP ₃ 2,6-diCl 236-239

A53 Ph CH ₂ OMe 2,6-diP 130-132

M R ¹ R ² R ³ (Ph substituted :) Melting point ( ⁰ C)

A54 2-Pyriridinyl Me 2,6-d.iP 209-211

A55 2-Pyrimidinyl Me 2-Cl, 6-Me 224 -

R ² R ³ (Ph substituted :) Climax point ( ⁰ C)

A56 2-pyrimidinyl me 2-Cl, 6-J? .217 -. 219 A57 2-pyrimidinyl me 2-Cl 145 - 147 A58 2-pyrimidinyl me 2-Me, 6-COOMe 165 - 167 A59 2-pyrimidinyl me 2-Cl, 6-SMe 206-208 Α6θ 2-pyrimidinyl me 2.6 -diBr 230-232 A61 2-pyrimidinyl me 2-CF ₃ 163 - 165 A62 2-pyrimidinyl et 2.6 -diF 213 - 215 A63 4,6-Dimehtyl- 2-pyrimidinyl me 2,6-dii ¹ 228-230 A64 4,6-dimethyl 2-pyrimidinyl me 2-Gl 124-126 A65 4,6-dimethyl 2-pyrimidinyl me 2-Gl, -6Me 208-210 A66 4-methoxy-2- pyrimidinyl me 2,6-dii ¹ 164-166 A67 4-methyl-2 ~ pyrimidinyl me 2,6-dii ¹ 203 - 205 A68 me Ph 2,6-diP 165-166 A69 Me. Ph 2,6-diCl, 3-Me 92 - 93 R ¹ R ² R- ⁵ (Ph substituted: ) Melting point ( ⁰ G)

2-NO ₂ Ph 2 -IiO ₂ Ph

A70 Me 2,6-diFPh A71 Me

A72 Me

A73 Pll Br

A74 i-Pr Me

A75 i-Prn-Pr A76 i-Prn-Pr A77 Me n-Bu A78 Me n-Bu A79 Me n-Bu

2,6-diP 2,6-diol ¹

2,6-diCl, 3-Me, 2,6-diI, ¹ 2-Cl, 6-Me 2-G ¹ , 6-Me. · 2,6-diCl, 3-Me ₂ -OCH ₂

2,6-diCl, 3-Me 2,6-diF

197 195 233 155 197 178

198 196 234 157 198 179

187-188

133-134

186 - 187

159 - 160

1 6 1 O 8 β

r (Ph substituted :) melting point ( ⁰ C)

ASO PhCH ₂ Me 2,6-diS ¹ 159 - 162 A81 H Me 2,6-dii ¹ 241 - 243 A82 3-nitropyne ridin-2-yl Me 26, -diJ ¹ 158-160 A83 Me i-Pr 2-COOEt. 113-115 A84 Me i-Pr 2-0N 164-166 A85 Et i-Pr 2-01, 3-Me 170 - 173 A86 Ph COOMe 2.6 -diF 160 - 162 A87 Ph MeCOOCH ₂ 2,6-dii ¹ 142 - 144 A88 Ph HIGH ₂ 2,6-diP 147-149 A89 Ph MeCO 2,6-diP 140 - 141 A90 H Me 2,6-diCl, 3-Me 229 - 231 A91 4-methyl-2-Me 2-01, 6-Me 176 - 178 pyrimidinyl A92 4-MeO-6-Me-Me 2,6-diB ¹ 19Θ - 200 2-pyrimid.inyl A93 5-01-4-MeO- 6-Me-2-pyridine midinyl Me 2,6-diB ¹ 194-195 Δ94 4-methoxy-2- pyrimidinyl Me 2,6-dii ¹ 194-195 A95 4,6-dimethyl 2-pyrimidinyl H 2-Cl, 6-E 232 - 233 A96 Ph MeO 2,6-diP 189-190 A98 Ph MfcO 2-COOM; «, 6-Me 171 - 172 A98 PhOH 2-COOMe, 6-Me 251 - 252 A99 2-pyrimidi nyl H 2-Cl, 6-P 246-248 A100 Ph Me 2-MeO 155-156 A101 PhOH 2,6-dii ¹ 239-242

The following compound of formula I in which R 1 is allyl was also prepared by an analogous method to that in Example A:

R ¹ R ²

R ³ (Ph substituted :) melting point

A102 PH PH - HO - 141

Production Example B:

N- (2-bromophenyl) -1-phenyl-5-propyl-1,2,4-triazole-3-sulfonamide (example of compound B1)

To a cold solution (0 ° C) of the product from step (c) (2.95g) in dichloromethane (4ml) was added with stirring a solution of 2-bromoaniline (1.89g) in pyridine (12ml). The reaction mixture was stirred at 0 ° C for 30 minutes. Then, the mixture was stirred at room temperature for further 4 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 dilute hydrochloric acid (20 o, 100 ml) and then with water (30 ml) and dried over magnesium sulfate. After removal of the solvent, an orange oil was obtained which crystallized on trituration with diethyl ether to give orange crystals (3.7 g). These were recrystallized from ethanol to give 2.5 g of the desired product as white crystals, mp 119 ° -121 ° C.

Production Example C:

N- (2,6-dichloro-3-methylphenyl) -5-methyl-1- (2-pyrimidinyl) -1,2,4-triazole-3-sulfonamide (Compound C1)

A suspension of sodium hydride (8.7 g) in dry tetra-

S. O.

Hydrofuran (400 ml) was stirred at 25 ° C and 1L-acetyl-2,6-dichloro-3-methylaniline (50.4 g) was added portionwise. After stirring for 15 minutes 5-methyl-1 ~ (2-pyrimidinyl) -1 ^^ - triazole-S-sulfonyl chloride (30 g) was added, which had been prepared by an analogous method to that in Example 4, time of addition 5 minutes. The mixture was stirred at 25 ° C for 18 hours and the solvent was removed in vacuo. The residue was treated with 1M-sodium hydroxide solution (500 ml) with stirring for 5 minutes and then extracted with ethyl acetate (500 ml). The ethyl acetate layer was reextracted with 1M sodium hydroxide solution (300 ml). The combined aqueous phases were acidified with concentrated hydrochloric acid and the solid was filtered off. Recrystallization from acetonitrile gave 38 g of the desired product, mp 214-216 ° C.

Examples C2 to C1t:

The following compounds of formula I wherein R is Y / oxygen were prepared by analogous methods to those in Example C:

U = R ¹ R ² R x ³ (Ph subst. :) melting point ( ⁰ C) C2 Ph me 2-Me, 6-ΝΘ ₂ 193-195 C3 2-pyrimidinyl me 2,6-Dicl 223 - 225 C4 4-pyrimidinyl me 2-Me ,. 6-WO ₂ 191-193 C5 4,6-dimethyl 2-pyrimidnyl me 2,6-Dicl 248 - 249 C6 4,6-dimethyl - 2-pyrimidinyl M.E 2-Me, 6-WO ₂ 195-196 CT 4,6-Diraethoxy- me 2,6-Dicl 195-197

1,3,5-triazin-2-yl

£. η ι υ

BS R ¹ R ² R ³ (Ph subst .:) Melting point ( ⁰ C)

C8 4-methyl-2-

pyrimidinyl. Me 2,6-diCl 201-202 C9 4-methyl-2-

pyrimidinyl Me 2-Me, 6-IJO ₂ 183-184 G10 4-methyl-2-

pyrimidinyl Me 2,6-diCl, 3-He 204-205

The following compound of formula I, wherein R 1 represents hydrogen, was also prepared by an analogous method to that in Example C:

R ¹ R ² R ³ 'melting point ( ⁰ C)

011 Ph Me 3-Hitropyrimidin-2-yl 175-176

Production Example D:

2,6-D.ichloro-H, H-bis (1-phenyl-5-n-propyl-i, 2,4-triazol-3-

sulfonyl) aniline (compound Di)

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

Example D2:

The compound which corresponds to that of Example D, in which R ³ is 2,3,4,5,6-pentafluorophenyl, was prepared by an analogous method to that of Example D

2 * 1 OB

represents, melting point 139 ° - HO ⁰ C.

Production Example E:

H- (2,6-dichlorophenyl) -5-ethyl-1-phenyl-1,2,4-triazol-3-

sulfonamide (Example of compound Ξ1)

5-Ethyl-1-phenyl-1,2,4-triazole-3-sulfonyl chloride (2.7 g), prepared by an analogous method to Example A, was added to a stirred solution of 2,6-dichloroaniline (1.8 g) and 4-dimethylaminopyridine (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 4M-sodium hydroxide solution (25 ml) at 80 ° C for one hour and then filtered. The filtered solid was washed with warm water, the filtrate was acidified with concentrated hydrochloric acid, and the product was recrystallized from ethanol to give 1.2 g of the recovered product, mp 185-187 ° C.

Examples Ξ2 to Ξ7:

The following compounds of formula I wherein R 1 is hydrogen were prepared by analogous methods to those in Example E:

K2 R ¹ R ² R ³ (Ph substituted :) Melting point ( ⁰ C)

Ξ2 Ph Me 2,6-diCl 200-201

Ξ3 Ph n-Pr 2,6-diBr 194-196.

Ξ4 Ph H 2,6-diCl 185-187

Ξ5 Ph ·n-Pr 2,6-diCl 192-194

£. b \ u 8

IiS R ¹ R ² R ³ (Ph substituted :) Melting point ( ⁰ C)

Phβ Ph B-Pr 2-Me, 6-NO ₂ 151-153 E7 Pll n-Pr 2,3-diMe, 6-NO ₂ 147-149

Production Example P:

H- (2,6-Difluorophenyl) -1- (4, 6-dimethyl-a-pyrimiilinyl) -5- methyl-1,2,4-triazole-3-sulfonamide (Compound J ¹ D

IT- (2,6-difluorophenyl) -5-methyl-i, 2,4-triazole-3-sulfonamide (5g) (Compound A81) was dissolved in portions of a suspension of sodium hydride (1.37 g in 80% suspension in oil) in dry dimethylformamide (40 ml). The mixture was stirred at 25 ° C for 30 minutes, 4,6-dimethyl-2-chloropyrimidine (2p * 6 g) was added, and the mixture was then 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 diol / dichloromethane). The product was recrystallized from ethanol to give 0.8 g of the desired product, m.p. 228-230 ° C, which was identical to that of Example A62.

Example e ff2 to P20;

ρ The following compounds of formula I where R

Methyl is, R ^ is 2,6-difluorophenyl and R ^ "is hydrogen, were prepared by analogous methods to those in Example P:

£. η ι υ ο - 30 -

S2 R ¹ melting point ( ⁰ C)

F2 2-chloropyrimidin-4-yl 183-185

Ρ3 "3-ethyl-1,2,4-thiadiazol-5-yl 180-181

14 pyrazinyl. .201-203? 5 4- (2-hydroxyethyl) -6-morpholino-

1,3,5-triazin-2-yl 176-178

¥ β 5-Iitropyridin-2-yl 201-203

F7 2,4-dinitrophenyl 171-173

]? 7 7-chloroquinoxalin-2-yl 192-195

F9 4-methanesulfonylphenyl 215-217

JB ¹ IO 3-phenyl-1,2,4-thiadiazol-5-yl 244-246

F11 Benzoxazol-2-yl 210-212

The following compound of formula I, Toei which R is methyl, R is 2,6-dichlorophenyl and R is hydrogen, was also prepared by an analogous method to that in Example TP :

HS R melting point ( ⁰ C)

ΙΊ2 benzoxyzol-2-yl 212-214

ρ The following compounds of formula I in which R and R are hydrogen and R 2 is chloro-6-methylphenyl were also prepared by an analogous method to that in Example f :

I R ¹ melting point ( ⁰ C)

Fl3 2,6-dimethoxybenzoyl 204-207

F14 thien-2-ylcarbonyl 233-234

FI5 K-isopropyl-N- (4-methylphenyl) - 193-194

carbamoyl P16 N-isopropyl-Li (4-isopropylphenyl) -

karbamoyl 165-166

£ 6 IU Ö δ

ΪΒ R ¹ melting point ( ⁰ C)

Fl 7 N-isopropyl-N- (4-chlorophenyl) -181-183

karbamoyl

P18 N-methyl-N-phenylcarbamoyl 184-186

Fl 9 2,2-dimethylpropanoylmethyl 177-179

2 The following compound of formula I, wherein R and

4 3

R 'are hydrogen and R 2 is ethoxy-carbonyl phenyl, was also prepared by an analogous method to that in Example P:

H ⁰ = R ¹ melting point ( ⁰ G)

F20 N, I-diisopropylcarbamoyl 88.5-90

Production Example G:

N-Benzoyl-IT- (2,6-difluoro-phenyl) -5-methyl-i - (2-pyrimidinyl) -

1,2,4-triazole-3-sulfonamide (compound G1)

A suspension of N- (2,6-difluoro-phenyl) -5-methyl-1- (2-pyrimidinyl) -1,2,4-triazole-3-sulfonamide (1.5 g) (compound A54) and anhydrous potassium carbonate ( 0.59g) in dry acetone (50ml) was heated at reflux for 30 minutes. A solution of benzoyl chloride (0.6 g) in acetone (50 ml) was added and the mixture was refluxed for a further 2 hours. Then the mixture was allowed to stand for 18 hours

ο ^/ at 25 C, it was then heated, filtered and evaporated it · The resulting solid material was recrystallized from acetonitrile and erga 1.05 g of the desired product, mp 218 ° - 221 ° C.

& Ό ι UOO

Examples G2 to G7:

The following compounds of formula I wherein R is 2-pyrimidinyl, R ^{2 is} methyl and R 1 is 2,6-difluorophenyl were prepared by analogous methods to those in Example G:

Melting point (C)

193-1995 195-197 158-160 140 142 142 205 205 174

Examples H1 - H23;

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

^R G2 me G3 MeCO G4 PhCH ₂ G5 allyl G6 MeSO ₂ O G7 COOMe

IIaE R ¹ R ² R ³ Melting point ( ⁰ C) H1 Ph me Thiazol-2-yl 221 - 222 H2 Ph me Benzothiazol-2-yl 266 - 267 H3 Ph me 6-Methoxy-quinolin-8-yl 146-147 H4 Ph me 5-Meth§ "lisoxazol-3-yl 181 - 182 H5 Ph n-Pr piperidino 106-108 H6 Ph n-Pr 3-methylpyridine-2-yl 160 - 162 Ξ7 Ph n-Bu 4H-1,2,4-triazole-4-yl 175 - 176 H8 Ph n-Bu Isoquinolin-5-yl 259 - 260 H9 Ph me 4,6-dimethyl-2-pyrimidinyl 192-193 H10 Ph me 6-Methosychinolin-8-yl 146-147

218 - 219 280 - 282 180 - 181

2 * 1 08

- 33 -

W R ¹ R ² R ³ melting point ( ⁰ G)

H11 Ph Me 5-methylisoxazol-3-yl 181-182

H12 Ph n -Bu 1,2,4-triazol-4-yl 175-176

H13 Pu Me 5-Methyl-1, .3,4-thalia-2-yl 235-236

HH Pll Me 4 ~ methyl thiazolyl

H15 Ph Me, 4,5-dime% ylthia-olyl

H16 Ph Me 6-nitroquinolin-5-yl

H17 Pll Me 4 ~ Zyano-3-methylthioiso-

thiazol-5-yl 184-185

H18 Ph Me 5-methylthio-1,2,4-triazole

3-yl 152-153 H19 Pll Me 5- (3-chlorophenyl) -1-methyl-

1,2,4-triazol-3-yl 224-225

H20 Ph Me quinoline-5-yl 188-189 H21 Ph Me 5-methyl-1-phenyl _1,2,4-e

triazol-3-yl "227-228

H22 Ph Me 5-ethyl-1-phenyl-1,2,4-

triazol-3-yl 173-174

H23 Ph Me 1 _s 2,4-triazol-4-yl> 320

Production Example I

H- (2,6-Dichlorophenyl) -1- (4,6-dimethylpyrimidin-2-yl) -1,2,4

triazole-3-sulfonamide

K- (2,6-dichlorophenyl) -1,2,4-triazole-3-sulfonamide (2.051 g) was added for 1 h at 125 ° with 1.82 g of 2-p-toluenesulfonyl-4-6-dimethylpyrimidine Presence of 1,8-diazabicyclo (5.4 * 0) undek-7-ene (2.128 g) in dimethylformamide (35 ml). As the solvent was distilled, the residue was poured into a mixture of water (80 ml) and hydrochloric acid 111 (20 ml) and then filtered. This crude product was chromatographed on silica gel.

£ ο υ υ - 34 -

using methylene chloride / methanol 95/5) as the eluent, giving 2.2 g of the desired product, mp 274-275 ° C.

Examples 12 to 146;

2 The following compounds of formula I in which R and R are both hydrogen and R is pyrimidin-2-yl or pyrimidin-2-yl which is further substituted as indicated were prepared by analogous methods to those in Examples A and / or I produced:

M R is substituted R (Ph substituted) Melting point ( ⁰ C)

12 4,6-diMe 2,6-diCl, 3-Me 255-256

13-2-Cl, 6-Me 204-205

14 4,6-diMe .2-01, 6-Me 261-262 1-5-2,6-dii ¹ 231-232

16 4,6-diMe 2,6-ddJ ¹ 208-209

17 - 2-CT ₃ 196

18 4,6-diMe 2-CF ₃ 227

19 4,6-diMe 2-COOEt, 6-Me 154-156

110-2-COOEt, 6-Me 189

111-2,6-diCl 265-266

112 4-Me 2,6-diCl 190

113 4-Me 2-CT ₃ 174-175 II4-2-COOMe, 6-Me 198-200

115 4,6-diMe 2-COOMe, 6-Me 187

116 4-Me 2,6-diP 199-201

117 - 2,6-diCl, 3-Me I96-198

118 4-Me 2,6-diCl, 3-Me 201-203

119 - 2-01 179 - 180

120 4,6-diMe 2-Cl 198-99

R is substituted R (Pll substituted) Melting point (C)

121 - 2-Me, 6-KO ₂ 227 - 228 122 4,6-diMe 2-Me, 6-HO ₂ 221 - 222 123 4,6-diMeO 2,6-Dicl 255 - 260 124 4,6-diMeO 2,6-diS ¹ 205-208 125 4,6-diMeO 2-COOMe, 6-Me 144 - 145 126 4,6-diMeO 2-COOEt, 6-Me 161 127 4-MeO 2-COOSt, 6-Me 144 - 145 128 4-MeO 2-Me, 6-ITO ₂ 196-197 129 4-MeO 2-Cl, 6-Me 188 - 189 ' 130 4-MeO 2,6-diS ¹ 204-205 131 4-Me 2-Cl, 6-Me 178 - 179 132 4-Me 2-Cl 124-125 133 4-Me 2-Me, 6-NO ₂ 176 134 4-Me, 6-Mee 2-CP ₃ 222 - 223 135 4,6-diMe 4-Br, 2,6-diCl 106-108 136 4-MeO, 6-Me 2,6-Dicl 234-242 137 4-Cl, 6-Me 2,6-D ij? , 182 - 183 138 4,6-diMee 2-CT 168-169 139 4,6-diMeO 2,6-diCl, 3-Me 249-250 140 4,6-diMeO 2-Cl, 6-Me 253 - 254 141 4,6-diMeO 2-Me, 6-WO ₂ 196-197

The following compounds of formula I wherein R

4 1

and R are both hydrogen and R is pyrimidin-2-yl or pyrimidin-2-yl, which is further substituted in the manner indicated, were also prepared by analogous methods to those in Examples A and / or I:

R is substituted R

Melting point (C)

142 4,6-diMe

143 -

Haphth-1-yl-1-naphth-1-yl

249 - 250 174 - 175

Si R ¹ substituted R ³ melting point ( ⁰ C)

144 4-Me ITaphth-1-yl 184-185

145 4,6-diMeO naphth-1-yl 211-212

The following compounds of formula I in which R and R are both hydrogen and R is 4,6-bis-methylthio-1,3,5-triazin-2-yl were also analyzed by a method analogous to that of Examples A and B / or I produced:

B R ³ (Ph substituted :) Melting point ( ⁰ C)

146 2,6-diF 254-256

Production Example J1:

H- (2,6-B-chlorophenyl) -1-acetyl-5-amino-i, 2,4-triazole-3- sulfonamide

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 benzyl chloride (44.3 g) was added. added "the mixture was stirred overnight and then filtered · D _a s ethanol was evaporated and the residue was recrystallized from ethyl acetate to give 64.97 g of the desired product, mp 104 ° C,

(b) i-acetyl-S-amino- ^ -benzylthio-i, 2,4-triazole

SS SS SS SS STSS Si SS &"™ SS Sa ZS SS SS SS SS SS SS SS SS S! SSSS SSSSSSSSSSäSSSSeSaSSS · SSSiSSSSSS SS

Azetyl chloride (12.57g) in methylene chloride (30ml) was added to the product from step (a) (39g) and triethylamine (25ml) in methylene chloride (300ml) at 0 ° C and the mixture was stirred at room temperature Stirred for 30 min. Then it was treated with 1U sodium hydroxide (160 ml) and extracted with methylene chloride. The product was dried from ethyl

2 A 1 O

Acetate recrystallized, giving 33 g of the desired product, mp 146 ° C.

The product of step (b) was added to the suspension in one liter of a mixture of water and glacial acetic acid (1: 1) and chlorine was introduced at a temperature of -10 ° C. over a period of 2 hours, the temperature being below 0 ° The product was washed with a minimum of water and pentane, then dried, giving

74.5 S of the desired product, m.p. 166-168 ° C.

(d) N- (2,6-dichlorophenyl) -1-acetyl-5-amino-1,2,4-triaZol-3-sulfonamidopyridinium salts

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 off, washed with a little pyridine and ether and dried in vacuo to give 53.6 g of the desired product, m.p. 213-215 ° C.

Production Example J2: H- (2 "6-dichlorophenyl)" 5-amino-1,2,4-triazole-3-sulfonamide

The product of Example J1 (53.6 g) was mixed with 2N sodium hydroxide solution (200 ml) and stirred at room temperature for 10 minutes. Under cooling with ice, the pH was lowered to 5 with 2N hydrochloric acid. The product was filtered off, washed with a little water and ether and dried in vacuo, giving 35.4 g of the desired product, m.p. 265 ° -267 ° C.

Production Example J3:

N- (2, β-dichlorophenyl) -5-methylamino-i, 2,4-triazole-3-sulfone

amide

3-Benzylthio-5-methylamino-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 triethanolamine hydrochloride was filtered off and the filtrate was concentrated to give 13 g of the desired crude product.

The product from step (a) (13.4 g) was dissolved in glacial acetic acid (50 ml) and water (50 ml) added. Chlorine was passed through this mixture at -10 ° C for 3ton 30 minutes, whereupon the product was filtered off, washed with a little water and dried in vacuo to give 4.45 g of the desired product.

(c) U- (2,6-dichlorophenyl) -5-methylamino-1,2,4-triazole-3

The product from step (b) (4.34g) was added with stirring 2,6-dichloroaniline (3.24g) in pyridine (30ml) and the mixture was stirred at 50 ° C for 8 hours. After removal of the pyridine, the residue was dissolved in sodium hydroxide solution (50 ml) and extracted with ethyl acetate (50 ml). The aqueous phase was acidified with 2N hydrochloric acid to a pH of 4 to 5, cooled and the product was filtered off, washed with a little water and

which gave 3.49 g of the desired product, mp 285-287 ° C

Production Example J4:

Ethyl 3- (2,6-dichlorophenylsulfamoyl) -5-methylamino-i, 2,4-

triazole-1-carboxylate ___ «_______,

The product from Example J3 (2.24 g) was mixed with acetonitrile (100 ml) and potassium carbonate (0.52 g) and ethylchloroforraate (0.8 ml) was added with stirring. The mixture was then refluxed for 5 hours , filtered hot, the portrait concentrated and the residue triturated with ether · The product was filtered and dried in vacuo, which at a temperature of 70 ° C during drying 2.65 g of the desired product, mp 202 ° - 2O ³ ° C. revealed.

Production Example J5:

H ^ o ^-dichlorophenyl -UjS-dimethylpyrrole-i-yl) - , 2,4- triazole-3-sulfonamide

The product of Example J2 (6.16 g) was refluxed with hexane-2,5-dione (9.13 g) in ethanol (150 ml) and acetic acid (2 ml) for 12 hours Solvent and excess deceton, the residue was chromatographed over silica gel with hexane / ethyl acetate to give 2.9 g of the desired product, m.p. 107-108 ° C.

Production Example J6:

K- (2,3-dichlorophenyl) -5- (2,5-dimethylpyrrol-1-yl) -1,2,4- triazole-3-sulfonamide

The product of Example J1 (c) (4.49 g) was treated with 2,3-diisocyanate.

086

chloroaniline (3.24g) in dry pyridine (75ml) under nitrogen for 5h at 70 ° C. The pyridine was then removed and the residue was dried under high vacuum. Then, the crude product was 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 as the eluent, giving 4.4 g of the desired product, mp 185 ° C.

Examples J7 to J27:

The following compounds of formula I, wherein R ^

Is hydrogen and R is pyrrol-1-yl, substituted in the manner indicated, were prepared by analogous methods to those of Examples.J1 to J5:

KS R ¹ R ² subst. R ³ (Ph subst. :)

Melting point ( ⁰ C)

J6 H J7 H J8 H J9 H J10 H J11 H J12 H J12 H J13 H J14 H

J15 H J16 H J17 H J18 H

2,5-diMe 3,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5 -diMe 2,5-diMe 2,5-diMe 2,5-diMe 2,5-diMe

2,3-DICL

2-Cl, 6-Me

2,6-diCl, 3-Me

2,6-diP

2.6 -diMe

2-CP ₃

2-Cl

ρ ent al?

2-MeO

2,4-DICL

2,5-DICL

2-Cl, 6-J ¹ 2-i ¹

185 170 196 185 186 189 184

84

153 208 154 159 144

186 193

R ¹

2 3

R subst. R (Ph subst. :)

Melting point (C)

J19 H 2 5 -diMe 2-Cl, 5-Me 211 J20 H 2 5 -diMe 2,5-diI 164 J21 H . - 2-Cl, 6-F 176 J22 H MD 2-CJ · 70 J23 H ma 2,6-Dicl 230 J24 t-Bu - 2,6-Dicl 210 J25 t-Bu - 2,6-diCl, 3-Me 155

The following compounds of formula I wherein R

ρ is hydrogen and R is pyrrol-1-yl, substituted in the manner indicated, were also prepared by analogous methods to those of Examples J1 to J5:

R-

Melting point (C)

J26H 2,5-diMe 2-C00Me-3-thienyl 144 J27 H 2,5-diMe 1-haphthyl 207

Production Example K1:

H- (2,6-Difiuorophenyl) -5-methylamino-i-phenyl-1,2,4-triazole

3-sulfonamide

(a) ^ SS ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

5-Amino-3-benzylthio-1-phenyl-1,2,4-triazole (45 g) was added to the suspension in acetic anhydride (31 ml) and formic acid (16.09 ml) and the mixture was allowed to stand for one hour 80 C stirred. The solvents were then removed and the residue was recrystallized from ethyl acetate to give 35.4 g of the desired product, mp 94 ° C

c ο ι υ ö

The product of step (a) (31 g) was (19.6 g) "mixed with dioxane (200 ml) and 96% sodium borohydride at room _temperature, and with vigorous stirring, acetic acid (30 ml) was added" The mixture was stirred at Stirred at 100 ° C for 2 hours, then 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, giving 21.4 g of the desired product.

(c) 5-Methylamino-1-phenol-1 _A 2 _A 4-triazole-3-sulfonyl chloride

32 iSS SS SS SS SS SS SiS -S SS SSj SSSS SSS w ^ b SS ISA SS SS SS hb ma SSSS> SS ^ * -. S5> ^ 2 2S> SS ^ ϊ2 SSi! SS SS SjSSSi SS> SS SS i ^ SS ^ S <SSSS> SS SSSSj SS SS SS SS SS SS ^^ 5

The product from step (b) (21 g) was added to the suspension in a mixture of water (50 ml) and acetic acid (50 ml). Chlorine was bubbled into the mixture at a temperature between -10 ° and 0 ° C. and the product was extracted with ethyl acetate The oily product was chromatographed on silica gel using hexane / ethyl acetate to give 15 g of the desired product.

(d) S- (2,6-Difluorophenyl) -5-methylamino-1-phenyl-1,2,4-triazole-3-sulfonamide

ssssssssssssssss sssssssssssssssssssssssssssssssssssssssssssss

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

· · 6 i o 8

Production Example K2:

IT- (2,6-dichlorophenyl) -5-amino-i - (4,6-dimethylpyrimidin-2 ~ 1,2,4-triazole-3-sulfonamide _ι

5-Amino-3-mercapto-1,2,4-triazole (40.36g) in ethanol (450ml) was treated at room temperature with solid sodium hydroxide (13.9g) and benzyl chloride (44%) was added dropwise. The solution was stirred overnight, filtered and the residue recrystallised from ethyl acetate and dried to give 64.97 g of the desired product, mp 104 ° C.

(Td) 1-acetyl-g-amigo-1-benzylthioyl _A 4-triazole

Acetyl chloride (12.57 g) in methylene chloride (30 ml) was added to the product from step (a) (30 g) in triethylamine (25 ml) and methylene chloride (300 ml) at 0 ° C and the mixture was allowed to stand for 30 minutes touched. Then, 1N-sodium hydroxide was added, and the solution was extracted with methylene chloride. After drying and recrystallization from ethyl acetate gave 33 g of the desired product, mp 146 ° σ.

(c) 1-Acetyl-5-amino-1,2,4-triazole-3-sulfonyl chloride

The product from step (b) (112 g) was added to the suspension in a 1: 1 mixture of water and acetic acid, and chlorine was passed through this suspension at -10 ° C. over 2 hours. The product was filtered off , washed with a little water and pentane and then dried, giving 74.5 g of the desired product, m.p. 166 ° -168 ° C.

£ h \ UO Ό

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

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

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

The product from step (d) (53.6 g) was dissolved in 2N sodium hydroxide (200 ml) and stirred at room temperature for 10 minutes. The solution was then brought to pH 5 with 2N hydrochloric acid and the product was filtered off, washed with a little water / ether and ether and then dried in vacuo to give 35.4 g of the desired product, mp 265 ° - 267 ° C.

(f) N- (2,6-dichlorophenyl) -5-amino-i- (4,6-dimethylpyrimidine)

The product from step (e) (2.15 g) was dissolved in dimethylformamide (35 ml) and 2-p-tosyl-4,6-dimethylpyrimidih (1.82 g) at 120 ° C for 4 hours and in the presence of 1 , 8-Diazabicyclo (5.4.0) undek-7-ene (2.128 g). After removal of the solvents, the residue was stirred with 1N hydrochloric acid (100 ml) and the product was filtered off. It was then chromatographed on silica gel using methylene chloride / methanol (95: 5) to give 2.1 g of the desired product, m.p. 306-312 ° C.

Examples E3 to K72;

The following compounds of formula I in which R is hydrogen were prepared by analogous methods to those in Examples K1 and K2:

R (Ph substituted: ') Melting point ( ⁰ C)

K3 Ph NH ₂ 2,6-diCl NHBt 2,6-diCl, 3-Me > 26O K4 Ph NH ₂ 2-01, 6-F NHEt 2,6-dlCl 257 K5 Ph NH ₂ 2,6-diCl, 3-Me NHBt 2,6-diI 248 K6 Ph NH ₂ 2-Cl, 6-Me NHMe 2,6-diCl, 3-Me 226 K7 Ph NH ₉ 2,6-diJ ¹ NHMe 2,6-diCl 218 K8 4-Meph ΝΗ ~ 2-01, 6-1 N (CHO) Me 2.6 dB ¹ 232 K9 4-MePh NH ₂ 2,6-difl, 3-Me Pyrrol-1-yl 2,6-di-Cl 236 K10 4-MePh NH 2,6-diS ¹ Pyrrol-1-yl 2,6-diF 240 K11 4-MePhNH ₂ 2,6-diCl Pyrrol-1-yl 2-Cl, 6- ¥ 260 K12 2-MePh NH ₂ 2,6-diP N = CHOMe 2,6-diCl 194 K13 2-MePh NH ₉ 2,6-diCl N = CHOEt 2,6-diCl 155 K14 Ph 5-diMePE NH ₂ 2,6-diCl 176 K15 Ph 5-diMePh NH ₂ 2,6-diP 168 K16 Ph 5-diMePh NHEt 2,6-dii ¹ 135 - 137 K17 Ph 125 - 127 K18 Ph 132-134 K19 Ph 176 - 177 K20 Ph 208 - 209 K21 Ph 157-158 K22 Ph 190-191 K23 Ph 196 K24 Ph 145 - 146 K25 3, 233-234 K26 3, 194-195 K27 3, 199 - 200

(Ph subst.) Melting point ( ⁰ C)

K28 3,5-DiMePh HHEt 2.6 -diF 2-Cl, 6-F 2,6-Dicl 199 - 200 K29 3,5-DiMePh HHEt 2,6-diCl, 3-Me 2-Cl, 6-F 2,6-diMe, 3-Me 160-161 K30 3,5-DiMePh HHEt 2,6-Dicl 2,6-diCl, 3-Me 155 - 157 K31 3,5-diMePh pyrrol-1-yl 2,6-diF 226-227 K32 3,5 diMeph HH ₂ 2.6 -diF 169 - 170 K33 3,5-DiMePh HHEt 169 - 170 K34 4,6-dimethyl-HH ₂ 309 - 313 pyrimidin-2-yl 2,6-diCl, 3i ^ e K35 4,6-dimethyl-HH ₂ > 250 pyrimidin-2-yl 2,6-Dicl K36 4,6-dimethoxy- 2,6-diCl, 3-Me 1,3,5-triaHH ₂ 2.6 -diF 236-237 zin-2-yl 2-Cl, 6-F K37 Pyrimidin-2-yl HH ₂ 2-Cl, 6-Me 286-290 K38 Pyrimidin-2-yl HH ₂ 2-CF ₃ 250 - 254 K39 Pyrimidin-2-yl HH ₂ 289 - 294 K40 Pyrimidin-2-yl HH ₂ 2-Cl, 6-Me 272-280 K41 Pyrimidin-2-yl HH ₂ 260-264 K42- 4,6-dimethyl-HH ₂ 2.6 -diF 250 - 251 pyrimidin-2-yl K43 4,6-dimethyl-HH ₂ 272 - 273 Pyrimidin-2-yl 2-Cl, 6-Me K44 4,6-dimethyl-HH ₂ oxy-1,3,5-triazine "2-yl 213-214 oxy-1,3,3-TRIA Pyridin-2-yl HH zin-z-yl Pyridin-2-yl HH ₂ K45 4,5-dimeth-HH ₂ 227 - 228 ' K46 280 - 282 K47 236

K48 pyridin-2-yl K49 pyridin-2-yl

HH

, 6-diBr-Cl, 6-F

279 254

282 262

ö ι υ S §

Ή? (Ph subst. :) melting point ( ⁰ C)

K50 Pyridin-2-yl m ₂ 2-Cl, 6-Me 2-CP ₃ 246 - 253 K51 Pyridin-2-yl 2-CP ₃ . 2,6-Dicl, 231-236 K52 Pyrimidin-2-yl Pyrrol-1-yl 2-Cl , 6-Me 169. K53 Pyrimidin-2-yl NH ₂ 2,6-Dicl 218 - 219 K54 4-Methylpyrimi- M ₂ 3-Me. 264 din-2-yl 2,6-diP K55 4-Methylpyrimi- NH ₂ 295 din-2-yl 2,6-DLCL K56 4-Methylparimi- HH ₂ 270 - 275 din-2-yl 2,6-diP 857 4,6-Dimeth.oxy- NH ₂ 246 - 249 pyrimidin-2-yl 2,6-diP K58 4 , 6-dimethoxy M ₂ 248 pyrimidin-2-yl 2,6-Dicl K59 4,6-Mmethyl- MeNH 268 - 270 pyriffiidin-2-yl 2,6-diP K60 4S6-Dimetliyl- MeNH 243-245 pyrimidin-2-yl 2,6-Dicl K61 4,6-DFrom ^ tIiOXy- mehh 221 - 222 pyrimidin-2-yl 2,6-Dicl K62 4,6-dimethoxy- MeNH 221 - 223 Pyrimidin-2-yl 2,6-diP K63 4,6-dimethyl EtNH 242 - 243 pyrimidin-2-yl 2,6-Dicl, K64 4,6-dimethyl EtNH 223 - 224 pyrimidin-2-yl 2-CP ₃ K65 4,6-Diemthoxy- NH ₂ 3-Me 277 - 288 pyrimidin-2-yl 2-CP ₃ £ 66 4,6-Dimehtozy- HH ₂ 237-238 pyrimidin-2-yl K67 Pyrimidin-1-yl NH ₂ 230 - 231

RR ² R ³ (Ph subs-b. :) melting point ( ⁰ C)

K68 pyridin-2-yl HH ₂ 2,6-diF 289-291 K69 pyrimidin-2-yl HH ₂ 2,6-diBr 292-298 K70 pyriraidin-2-yl pyrrol-1-yl 2,6-diF 148 - 156

The following compounds of formula I in which R is hydrogen were also prepared by analogous methods to those in Examples K1 and K2:

PR ¹ R ² R ³ melting point ( ⁰ C)

K71 4,6-Dimethylpy-HH ₂ -Haphth-1-yl 287-288

rimidin-2-yl K72 pyrimidin-2-yl HH ₂ haphth-1-yl 242-243

Production of intermediates:

The following examples refer to various intermediates in the preparation of compounds having the formula Preparation Example for Intermediates 1 is an alternative method for the preparation of a compound of formula II from a compound of formula III which is substituted for the method in Preparation Example A, step (c ), can be applied. The other intermediate preparation examples are for the exchange of compounds of formula III to provide correspondingly substituted starting materials for the processes of Example A, step (c), as well as for the preparation of intermediates 1 or analogous processes.

"/ M U 8

Preparation Example for Intermediates 1% of 1- (4 _S 6-dimethoxy-1,3,5-triazin-2-yl) -5-methyl-1,2,4-triazol-3-sulfonyl chloride

A solution of 3-benzylthio-1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -5-methyl-1,2,4-triazole (6 g) of dichloromethane (60 ml). was treated with silica gel (14g) 60-120 mesh, and water (2.8g). While stirring, sulfuryl chloride (10.6ml) in gichloromethane (12ml) was added dropwise while the temperature was maintained for 2 hours 5 ° C was held. The silica gel was filtered off, washed with dichloromethane (150 ml) and ethyl acetate (100 ml), and the combined washings 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 give 3. g of the desired product.

Preparation of Intermediates 2: 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 with n-butyllithium (1.05 equiv.) At -70 ° C. The solution was added Cyanogen bromide (1.98 g) was added rapidly, the mixture was allowed to warm to room temperature, then quenched with ethanol, the volatiles were removed in vacuo, and the crude The product was chromatographed on silica using dichloromethane as the eluent to give 4.3 g of the desired product as a yellow oil.

Preparation of Intermediates 3: 5-Methanesulfonyl-1- (pyrimidin-2-yl) -1,2,4-triazole-3-sulfo

A solution of NytriumhydroxLd (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 benzyltriethylammonium chloride (1 g ), with stirring and cooling to 15 ° - 20 ° G added. To this mixture was added methyl iodide (56.8 g) and stirred at room temperature for a further 24 hours. The dichloromethane phase was separated, washed twice with water, dried over magnesium sulfate and drained to give 94% crude product, which was from toluene was recrystallized to give 80.7 g of the desired product, m.p. 80 ° to 82 ° C.

(b) 3-Benzylthio-5-methylthio-1- (pyrimidin-2-yl) -1,2,4-triazole_

The product of step (a) was treated in an amount of 50 g with 2-chloropyrimidine (24.4 g) in an analogous manner to that in Example P, which, after chromatographic separation of the two products, yielded 23.6 g of the desired product revealed.

(c) 5-Methanesulfonyl-1- (pyrimidin-2-yl) -1,2,4-triazole-3-aliquot _; 2-chloride _;

Chlorine gas was bubbled into a suspension of the product of step (b) (8g) in water (45ml) and acetic acid (45ml) at -5 ° to 0G with stirring until 9.9g was absorbed. The mixture was then stirred for a further 10 minutes at -5.degree. To 0.degree.

16 1 OBS

was filtered before. The product was washed in aqueous acetic acid (1: 1), water, petroleum ether with a boiling range of 40-60 ° C and finally in ether. Drying gave 6.3 g of a crude product, which was recrystallized from ethyl acetate and acetonitrile, and 3 , 1 g of the desired product, mp 214 ° - 217 ° C, gave.

Synthesis Example of Intermediates 4: 5 ~ Chloro ~ 1 ~ (pyrimidin ~ 2-yl) ~ 1,2,4-triazole-3-sulfonic chloride

3,5-bis (benzylthio) -1,2,4-triazole (50g), 2-chloropyrimidine (18.3g) and potassium carbonate (22.1g) were dissolved in dimethylformamide (200ml) for 12 hours heated at 100 ° C. After addition to ice-water, the product was extracted into dichloromethane (wweimal). The dichloromethane solution was washed with water (three times), dried over magnesium sulfate, and drained to leave 64.4 g of the title crude compound. Recrystallization from methanol gave 39 g of the desired product, mp 86 ° -88 ° C.

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

Chlorine was bubbled into a suspension of the product of step (a) (10g) in water (50ml) and acetic acid (50ml) at -5 ° to 0 ° G until 15g were absorbed. The mixture was then stirred at -5 ° to -10 ° C for 15 minutes and then filtered. The white precipitate was washed with cold aqueous acetic acid (1: 1), water and petroleum ether with a boiling range of 40 ° -60 ° C washed, which gave 7.6 g of the crude product. This solid was treated with reflux in ethyl acetate (300 ml) for 2 h 30 min. The remaining white by-product was filtered off and the solution

was drained in vacuo. The residue was warmed with ether (100 ml), filtered through silica gel and reduced to 10 ml in volume. Cooling in the sis gave the desired product as a solid, which was extracted to give 2.2 g, mp 98 ° -101 ° C.

Synthesis Example of Intermediates 5: 3 BBnzylthio-5-methoxy-1-phenyl-1,2,4-triazole

-i, 2,4-triazole (15 g) in dichloromethane (60 ml) was treated with trimethyloxonium tetrafluoroborate (15.7 g) and allowed to stand at room temperature for 18 hours. The reaction mixture was poured into water (200 ml) and the aqueous layer was washed with dichloromethane (2 × 100 ml). The dried organic layer was evaporated and then purified by column chromatography (silica / petrol: ether) to give 8.1 g of the desired product.

Preparation Example of Intermediates 6: 5-Acetoxy-1-phenyl-1,2,4-triazole-3-sulfonyl chloride

(a) 1 -thethoxy-carbony.l-1 -phenstbhio s emicarbazide

SS SSlS SS SS SS 52 SSS3 S3 «ZS 2Sa! SZS SSjüSISi ^ SMtSS! SHZ SS SS SSSI 2 »SS SS SSSS S HSS! SS SS SS SS SS S3

A mixture of 1-phenylthiosemicarbazide (25 g), ethanol (180 ml) and ethyl chloroformate (17 ml) was heated with reflux and stirring for 30 minutes. The Qaish was cooled to room temperature and the precipitate was filtered off, washed with ethanol and then ether, yielding 28.9 g of the desired product.

The product from step (a) (28.9 g) was treated with a solution of sodium hydroxide (7.5 g) in water (150 ml).

V »V / Q

The suspension was heated with stirring and stirring for 45 minutes and then cooled to 25 ° C. The pH of the solution was adjusted to 1.0 with concentrated hydrochloric acid and the resulting solid was filtered off and washed with water, which was 20, 2 g of the desired product.

The product from step (b) (20g), ethanol (300ml) and sodium hydroxide (5g) was stirred together for 10 minutes. Benzyl chloride (12.3ml) was added and the mixture refluxed with stirring for 24 hours heated. 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 give 21.75 g of the desired product.

2z4zo

₌ Jp.heny.1-1. _X 2 _A 4-triazole

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

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

A suspension of the product of step (d) (10g) in glacial acetic acid (20ml) and water (39ml) was stirred at -5 ° C. Chlorine gas was bubbled through the stirred solution for 40 minutes, then water (200 ml) was added. The solid was filtered off, washed with water and air-dried.

2 6

dried, yielding 6.3 g of the desired product.

The subsequent reaction of this compound with 2,6-difluoroaniline in the same manner as in Example A and the hydrolysis of the acetoxy group in the work-up of the product gives Έ- (2,6-difluorophenyl) -5-h.hydroxy -1-phenyl-1,2,4-triazole-3-sulfonamide.

Preparation of Intermediates 7: 3-Benzylthio-5-bromo-4-phenyl-1,2,4-triazole

n-Butyllithium (50 ml) was added dropwise to a stirred. Solution of 3-benzylthio-i-phenyl-i, 2,4-triazole (31.8 g) in dry tetrahydrofuran (200 ml) at -70 ° C. Bromine (19 x g) was added and the reaction mixture was allowed to warm to room temperature whereupon it was quenched with water. After washing with brine, the organic phase was dried and evaporated, yielding a yellow oil. Purification by chromatography on silica with dichloromethane and petroleum ether gave the desired product as a pale yellow oil.

The corresponding compounds in which the substituent at position 5 was methoxy-carbonyl, acetyl and hydroxymethyl were electrophilized by analogous methods using methylchloroformate, Ν, ΙΓ-dimethylazetamide and IT-IT-dimethylformamide, respectively, followed by reduction by sodium borohydride , manufactured.

Composition Example 1;

Sin water-soluble powder concentrate with one equivalent of 80 % active acid was prepared from the following ingredients:

Ί 6 \ 0 8

% W / w

Compound of Example A54, K ⁺ salt 94.8 Heosyl (silica) 2.7

Arkopon T (sodium N-methyltauride) 2.5

Analogous compositions were also prepared which had an active acid equivalent of 20, 40 and 60% w / w. and in which the compounds of the other examples mentioned above were used.

Composition Example 2;

The following components became a 7.5%. aqueous Lösungszusammensetzung prepared:

g / l

Compound from example 01 75.0

Potassium hydroxide (85 % pellets) 12,4

H-methylpyrrolidone 506.7

Water sufficient amount

Analogous compositions were also prepared containing 60 g / l and 75 g / l of the compounds of the other examples mentioned above, in particular the compound of Example C4.

Composition Example 3

From the following ingredients, a 10% aqueous solution was prepared:

2 6 10-8 *

g / l

Compound from Example A63 100.0

Potassium hydroxide (1M) 263.1

Water sufficient amount

Analogous compositions were also prepared containing 5 % and 10 % of the compounds of the other examples listed above.

Herbicidal Example A (before formation);

Seeds of the weed species listed below were sown in anodized aluminum vessels 19 cm long, 9.5 cm wide and 6 cm deep containing sterilized sandy loam soil. They were watered and then sprayed with the compounds of the examples below, which were carried out as a solution / suspension in a volume ratio of 1: 1 in acetone and with the wetting agent polyoxyethylene (20 Wl) mono laurate solution (2 g / l).

The concentration of each test compound and the application volume were calculated to achieve the desired rate of application of the compound in 450 l / ha. After 3 to 4 weeks of growth in a controlled environment room (20 ° C, 75-95 % relative humidity, 14 hours / day artificial lighting) the plants were visually assessed for their herbicidal action.

All deviations from an untreated control plant were rated according to an index where 0 s no effect, 1 = 1 - 24 % effect, 2 = 25 - 69 % effect, 3 = 70 - 89 % effect and 4 = 90 - 100 % effect · In the following table the following letters are used for the designation of the

Plant species used:

a - P ο Iy gonurn la pa thif ο! ium To - Galium aparine ( Labweed ^ c - Chrysanthemum segetum (Yellow Spooky Flower) d - Alopecurua myosuroides (Black Grass) e - Elymus repens (Common Wheatgrass) £ - Avena fatua (Wild Oat) g - Abutilon theophrasti h - Cyperus rotundus (Crimson sedge) i - Pharitia purpurea (Crimson) j - Echinochloa crus-galli k - Setaria viridis (Green fox tail) 1 - Solanum nigrum (Black nightshade)

The following results were determined;

Ex. lig / ha a b C d e f G H i D k 1 Δ2 1.0 4 4 4 Third 2; 0 4 4 4 3 2 4 A3 1.0 0 4 4 0 0 0 2 0 0 0 3 4 A4 1.0 2 3 3 0 0 0 2 1 1 2 1 3 A6 1.0 2 2 3 0 0 0 0 0 0 2 2 4 A9 1.0 2 2 0 2 2 0 0 0 0 0 2 4 A18 1.0 2 0 0 2 0 2 0 0 0 1 4 4 A19 1.0 3 3 4 0 0 2 0 0 0 2 0 0 A25 2.5 4 3 2 2 2 0 0 0 2 0 0 A43 1.0 4 4 4 2 0 1 4 3 3 0 0 4 A44 1.0 0 4 4 0 2 0 2 0 0 0 0 2 A53 1.0 4 4 4 2 0 0 3 4 0 2 4 - A54 1.0 4 4 4 3 4 1 4 4 4 3 2 - A55 1.0 4 4 4 2 2 0 4 4 ' 4 3 4 4 A 56 1.0 4 4 4 2 2 2 4 _. 4 3 3 _

Ex. kg / fata a b C d e f S ii i 0 k 1 A57 0.5 2 2 4 1 0 0 2 3 3 0 0 4 A63 0.5 4 4 4 4 4 4 0 0 0 4 0 3 A65 0.5 3 4 4 4 4 3 4 4 4 2 4 4 B1 2.5 4 4 4 2 2 0 2 2 2 0 4 C1 1.0 4 4 4 2 2 0 4 4 4 2 0 - C2 1.0 4 4 4 0 2 0 4 4 2 2 0 - 03 1.0 4 4 4 2 2 0 4 4 4 3 2 - C4 1.0 4 4 4 3 2 2 4 - 4 4 4 4 C5 0.5 4 4 4 4 4 3 4 4 4 4 4 4 C6 0.5 3 4 4 3 4 3 4 4 4 0 4 4 E2 1.0 4 4 4 0 0 0 2 0 0 0 4

E3 1,0 2 4 4 0 0 0 1 00 0 02 E4 1,0 244000222.003

Herbic Example B (after formation):

Seeds of the plant species listed below were sown in anodized aluminum vessels 19 cm long, 9.5 cm wide and 6 cm deep containing sterilized sandy loam soil. They were then watered and placed in a controlled environment room (20 ° G, 75-95 % relative humidity, 14 hours / day artificial lighting). Fourteen to 21 days after sowing (depending on the species, but usually when most plants had 2 to 3 true leaves), the seedlings were foliage sprayed with the compounds of the examples below, which were used as solution / suspension in the Volume ratio of 1: 1 in acetone and the wetting agent polyoxyethylene (20 mol) Monolauratlosung (2 g / l) were prepared.

The concentration of each test compound was calculated

The desired rate of application of the compound was achieved in 450 l per ha. After 2-3 weeks in the controlled environment room, the plants were visually assessed for their herbicidal response.

All differences to an untreated control plant were rated according to an index where 0 = no effect, 1 = 1 - 24 % effect, 2 = 25 - 69 % effect, 3 = 70 - 89 % effect and 4 = 90 - 100 % effect , In the table below, the following letters have been used to designate the plant species:

a - Polygonum lapathifoliutn

b - Galium aparine (labweed)

c - Chrysanthemum segetum d. Alopecurus myosuroides e - Elymus repens (Common Wheatgrass)

^f ~ Avena fatua (wild oats)

g - Abutilon theophrasti

h - Cyperus rotundus (Purple Sedge) i - Pharibtis purpurea (Purple Morning Glory).

D - Echinochloa crus-galli

k - Setaria viridis (Green Foxtail) 1 - Solanum nigrum (Black Solanum )

The following results were achieved:

Ex. kg / ha a b C d e f G H i CJ. k 1 A2 1.0 3 4 4 2 0 2 4 1 2 2 0 3 A4 1.0 OJ 3 3 0 0 0 2 1 1 OJ 1 3 A43 1.0 2 3 3 2 0 0 3 0 2 2 1 4 A53 1.0 1 4 2 2 0 1 1 1 2 3 2 4

- βο -

Ex. Taj / ha a t> c d e f g

A54 1 , 0 1.0 3 4 3 2 2 2 4 0 2 1 2 2 A55 1.0 2 4 3 2 2 3 4 0 2 2 1 3 A56 0.5 3 4 4 2 2 2 4 0 2 2 1 3 A63 0.5 1 4 1 4 4 3 3 2 2 0 2 3 A65 1.0 1 4 2 4 2 3 3 2 1 2 2 2 01 1.0 0 4 4 2 0 3 3 2 3 1 1 2 02 2 4 2 0 0 1 3 - 1 1 2 2 4

03 1.0 -4 42 2 140 2 21

04 1.0 332 2-2231 222

05 2.5 "2 4 · 3 3 2 3 3 2 1 1 2

06 0.5 243 -2 223222 $

1,02 1.0 33 33222022 1

Claims (7)

claim A herbicidal composition, characterized in that it contains between 0.5 and 85% by weight of one or more triazole sulphonamides having the formula: SO ₂ NR ³ R ⁴
and their salts, in which R represents hydrogen or substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, acyl, alkoxycarbonyl, aminocarbonyl, sulfonyl or a heterocyclic group; R is hydrogen, halo, cyano, hydroxy, mercapto, a substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, acyl, alkoxycarbonyl, aminocarbonyl, aryl or Represents amino group or a heterocyclic group! R is a substituted or unsubstituted heterocyclic, benzheterocyclic. Aryl or aralkyl group represents and R represents hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl, acyl, alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, aralkyl or a group having the formula: (A) 1 2
wherein R and R are as defined above in association with a suitable carrier and / or surfactant. 2. A herbicidal composition according to claim 1, characterized in that R is hydrogen, alkyl having 1 to 6 carbon atoms, acyl or alkoxycarbonyl, wherein the Alky! Component has 1 to 4 carbon atoms, phenyl, by one or more halogen atoms or alkyl or Or monocyclic heterocyclic compound having 5 or 6 ring atoms which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms, Cyano groups, amino groups (which may be unsubstituted or substituted by methyl or ethyl), halogen atoms or alkylsulfinyl or alkylsulfonyl groups having 1 bid 4 carbon atoms. 3. A herbicidal composition according to claim 2, characterized in that R is hydrogen, methyl, ethyl, n-propyl, η-butyl, phenyl, 3,5-dimethylphenyl, 4-methylpyrimidin-2-yl, 4-methozypyrimidin-2-yl , 4,6-Dimethylpyrimidin-2-yl, 4 »6-dimethoxypyrimidin-2-yl, 4» 6-dichloropyrimidin-2-yl, 4-methyl-6-methylaminopyrimidin-2-yl, 4-methyl-6-aminopyrimidine -2-yl, 4-methyl-6-dimethylaminopyrimidin-2-yl, 4-chloro-6-methylpyrimidin-2-yl, 4-chloro 6-methoxypyrimidin-2-yl, ^
midin-2-yl, 4-methyl-6-methoxypyrimidin-2-yl, 4,6-dimethoxy-1,3,5-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-methylamino 6-metlaoxy-1,3,5-triazin-2-yl or 4-methylamino-6-chloro-1,3,5-triazian-2-yl. The herbicidal composition according to any one of claims 1 to 2
3, characterized in that R is hydrogen, halogen, cyano group, amino group, alkylamino group having 1 to 4 carbon atoms, an alkyl or alkoxy group having 1 to 6 carbon atoms (unsubstituted or by one or more halogen atoms, hydroxy groups, alkoxy groups having 1 to 4 carbon atoms or acyloxy groups having 2 to 5 carbon atoms), alkoxy carbonyl having 2 to 4 carbon atoms or a monocyclic heterocyclic compound having 5 or β ring atoms which contains at least one nitrogen atom and which is unsubstituted or substituted by one or more alkyl groups having 1 to 4 carbon atoms , 5. A herbicidal composition according to claim 4, characterized characterizes RY / oxygen, chloro, bromo, cyano, methyl, ethyl, n -propyl, n-butyl, s -butyl, hydroxymethyl, methoxymethyl, ethoxymethyl, methoxyethyl, acetoxymethyl, methoxy, sthoxy, hethoxycarbonyl, amino, methylamino, ethylamino , Pyrrol-1-yl or 2,5-dimethylpyrrol-1-yl. 6. A herbicidal composition according to any one of claims 1 to 3
5, characterized in that R represents a pheny! .- 64 - which is substituted by one or more halogen atoms, nitro groups, cyano groups or alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms which in turn may be substituted by one or more halogen atoms, or alkoxy carbonyl groups having 2 to 6 carbon atoms. 7. A herbicidal composition according to claim 6, characterized in that R 2-fluorophenyl, 2-chlorophenyl, 2-Brotnophenyl, 2-cyanophenyl, 2-methylphenyl, 2-methoxyphenyl, 2-methylthiophenyl, 2-Trifluorojaethylphenyl, 2-Methosykarbonylphenyl, 2 -Sthoxykarbonylphenyl, 3-5 ¹ IuOrO-phenyl, 2-Difluoromethoxyphenyl, 2,3-difluorophenyl, 2,5-difluorophenyl, 2,6-dimethylphenyl, 2,3,5,6-tetrafluorophenyl, 2-methyl-6-πlethoxykarbonylphenyl , 2-fluoro-6-methoxycarbonylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 2-methyl-6-nitrophenyl, 2-chloro-6-methylphenyl, 2-pluoro-6-methoxycarbonylphenyl . , · 2-chloro-6-methoxycarbonylphenyl, 2, S-dichloro-S-methylphenyl or 2-chloro-6-fluorophenyl 8. A herbicidal composition according to any one of claims 1 to 7, characterized in that R represents hydrogen, methyl, acetyl, benzoyl, methylsulfonyl, methosycarbonyl, Dime thylkarbamoyl or benzyl · A herbicidal composition according to claim 1, characterized in that the triazolesulphonamide is one of the following compounds: U- (2,6-difluorophenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide; N- (2,6-dichloro-3-methylphenyl) -1- (pyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide; ι \ O -i N- (2-Me-chyl-6-nitrophenyl) -1 - (pyrimidin-2-yl) -5-methyl 1,2,4-triazol-3-sulfonaraid; ·% * N- (2,6-difluorophenyl) -1- (4,6-dimethylpyrimidin ~ 2-yl) -5-methyl-1,2,4-triazole-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-trxazol-3-sulfonamide; H-. (2, β-difluorophenyl) -1- (4-methoxy-6-methylpyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide; K- (2,6-Dichlorophenyl) -1- (4,6 ~ dimethoxy-1,3,5-triazin-2-yl) -S-methyl-1,2,4-triazole-3-sulfonamide; N- (2,6-Dichlorophenyl) -1- (4,6-dimethylpyrimidin-2-yl) -1,2,4-triazole-3-sulfonamide; N- (2,6-dichlorophenyl) -1- (4,6-dinethylpyrimidin-2-yl) 5-methyl-1,2,4-triazole-3-sulfonamide; N- (2-methyl-6-nitrophenyl) -1- (4,6-dimethyl-pyrimidin-2-yl) -5-methyl-1,2,4-triazole-3-sulfonamide; N- (2,6-dichlorophenyl) -5-C2,5-dimethylpyrr-0I-I-yl) -1,2,4-triazole-f3-sulfonaraid; N- (2,6-difluorophenyl) -5- (2,5-dimethyl-pyrrol-1-yl) -1,2,4-triazole-3-sulfonamide; N- (2,6-dichloro-3-methylphenyl) -1- (4,6-dimethylpyrimidin-2-yl) -1,2,4-triazole-3-sulfonamide; N- (2,6-dichlorophenyl) -5-amino-1- (4,6-dimethylpyrimidin-2-yl) -1,2,4-triazole-3-sulfonamide or N- (2,6-dichloro-3 -methylphenyl) -5-amino-1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1,2,4-triazole-3-sulfonamide. 10. A process for the preparation of a Triazolsulfonamids of the formula I as defined in claim 1, characterized in that a Triazolsulfonylhalid having the formula: - V. ν υ ο Ν ' (II) rl R ² ₂ 1 2 wherein R and R are as defined in claim 1 and Hai Is halogen, reacting in the presence of a base with an amine having the formula R R% H, wherein R and R are as defined in claim 1, to give the desired compound.