Triazolopyrimidine herbicides.

PREPARATION OF TRIAZOLOPYRIMIDINE DERIVATIVE COMPOUNDS.

DESCRIPTIVE MEMORY

The present invention relates to triazole sufonamides with herbicidal properties, processes for their preparation, and compounds containing them.

According to one aspect the present invention relates to triazole sulfonamides of the formula:

<img file="PT84780B_D0001.tif" />

(I) and salts thereof, where R^The R3 represents hydrogen and R4 represents a group R3 CONHCR4 Cr1-, or R4^The and R2 together represent a chain of the formula

N.

<img file="PT84780B_D0002.tif" />

-C (R³) = NC (R²) = C (R¹) - OR

-C (= Y) -N (R⁶) -C (R²) = C (R¹) - where R¹, R² and R³may be the same or different and each represents hydrogen, hydroxyl, mercapto, halo, cyano, amino, alkylamino, dialkylamino or alkyl, aryl, aralkyl, alkoxy or alkylthio which may be substituted or unsubstituted, Y is oxygen or sulfur and R is hydrogen or a substituted or unsubstituted alkyl or aralkyl group; or R and R together represent -CH = CH -CH = CH- or - (CH₉) where n is 3, 4 or 5; R⁴ represents substituted phenyl or a substituted or unsubstituted aralkyl or heteroalkyl group; and R³ represents hydrogen, acyl, carboxyl, alkoxycarbonyl, alkylsulfonyl, or an alkyl, alkenyl, alkynyl, aryl or aralkyl group which may be substituted or unsubstituted or a group of the formula

R^B

<img file="PT84780B_D0003.tif" />

(A) ab where R and R have the meanings defined above.

ab

Preferably R and R together represent a chain of formula -C (R³) = NC (R²) = C (R¹) -.

3

When R, R or R represents halogen, it is preferably chlorine or bromine.

τ 2 3 5 fi

When R, R, R, R or R ° represents or contains an alkyl group, that group is preferably from 1 to 6 carbon atoms, especially from 1 to 4 carbon atoms.

Preferred unsubstituted specific groups containing alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxy, ethoxy, n-propoxy, methylamino, dimethylamino, methylthio and ethylthio. If desired the alkyl group may be substituted, for example by one or more halogen atoms, for example fluorine, chlorine or bromine, or by alkoxy groups of 1 to 4 carbon atoms, for example methoxy or

<img file="PT84780B_D0004.tif" />

ethoxy. Preferred specific alkyl-containing substituted groups include chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, methoxymethyl and ethoxyethyl.

When R ', F', or R 'represents an aryl or aralkyl group, it is preferably a phenyl group or an aralkyl group of 7 to 10 carbon atoms, especially benzyl, substituted for example by one or more halogen atoms, for example fluorine, chlorine or bromine, nitro groups, cyano groups or alkyl or alkoxy groups of 1 to 4 carbon atoms, for example methyl, ethyl, methoxy or ethoxy groups.

« 12 3

Preferably R, R and R independently of one another represent hydrogen, methyl, ethyl, phenyl, trifluoromethyl, chloro or bromo.

Conveniently when R represents hydroxy or mercapto, the compounds may exist in either keto or enol form or as a balanced mixture of the two.

5

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

When R represents a heteroaryl group, it is preferably a 5- or 6-membered heterocycle which contains one or more nitrogen, oxygen or sulfur atoms. Preferred among these are pyridyl, pyrrole, furyl and thienyl groups.

R preferably represents a phenyl group substituted by one or more halogen atoms (e.g. chlorine, bromine or fluorine), alkyl groups of 1 to 4 carbon atoms (e.g. methyl or ethyl), alkoxy or alkylthio groups of 1 to 4 carbon atoms (e.g. methoxy, ethoxy or methylthio), trifluoromethyl groups, alkoxycarbonyl groups of 2 to 5 carbon atoms (e.g. methoxycarbonyl or ethoxycarbonyl) or nitro groups.

When R represents an alkyl group, it is preferably methyl or ethyl. When, however, it represents an alkenyl or alkynyl group, that group is preferably unsubstituted, and is preferably from 2 to 6 carbon atoms,

<img file="PT84780B_D0005.tif" />

for example vinyl, allyl or propargyl. Preferred acyl, alkoxycarbonyl and alkylsulfonyl groups which R may represent are those wherein the alkyl moiety is 1 to 4 carbon atoms, including formyl, acetyl, propanoyl, methoxycarbonyl, ethoxycarbonyl and methylsulfonyl.

R preferably represents hydrogen.

Preferred salts of the compounds of formula I are alkali metal salts, for example sodium or potassium salts, ammonium salts, trialkylammonium salts, and salts with hetero cyclic bases, for example pyridinium salts.

In a particularly preferred group of compounds of formula I, R and R together represent a chain of formula -C (R 4) = NC (R 4) = C (R 4) R 1 and R 4 each represent hydrogen, methyl, ethyl, phenyl, trifluoromethyl or chloro, R3 is a phenyl group substituted by one or more halogen atoms, alkyl, alkoxy or alkylthio groups of 1 to 4 carbon atoms, trifluoromethyl groups, alkoxycarbonyl groups of 2 to 5 carbon atoms. carbon, or nitro groups, and R is hydrogen.

Especially preferred compounds according to the present invention are those of the examples which we describe below. However, specific mention may be made of N- (2,6-difluorophenyl) -5,7-dimethyl / 1,2,4 / triazolo2,1,5-cpyrimidine-2-sulfonamide and 5- (2-acetamido-1-amine). propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazol-3-sulfonamide.

According to another aspect, the present invention relates to a process for the preparation of a triazole sulfonamide of formula I wherein R^The and R &amp; together represent a chain of formula -C (R) = NC (R) = C (R) - or -c (= Y) -N (rS-C (R4) = C (R · * ·) - where r \ R ?,??, R? and Y have the meanings defined above, wherein a sulfonyl halide of the formula

<img file="PT84780B_D0006.tif" />

(II)

X

<img file="PT84780B_D0007.tif" />

The. fo * where R and R have the meanings previously defined, and

Hal represents halogen, is reacted in the presence of a 454 * base with an amine of the formula wherein R and R have the meanings above to give the desired compound.

The reaction is conveniently carried out at a temperature of from 09 ° C to 100 ° C, for example 0 to 509 ° C, especially at room temperature. It is preferably effected in a suitable solvent, especially pyridine, which may also serve as a base.

The reaction may be catalyzed by a stronger organic base, particularly a tertiary organic base such as 4-dimethylaminopyridine.

The compounds of formula II may in turn be prepared by reacting a compound of formula II.

<img file="PT84780B_D0008.tif" />

(III) where R^The and R^D together represent a chain of the formula -C (R³) = NC (R²) = C (R¹) - or -C (= Y) -N (R⁶) -C (R²) = C (R¹) - where R¹,

R, R, R and Y have the meanings defined above, and R represents hydrogen, alkyl, aryl or aralkyl, with the appropriate halogen or sulfuryl halide in a suitable solvent medium, to give the desired compound.

It is desirable for the reaction to be carried out with cooling to below room temperature, for example at a temperature of -10 ° to 59 ° C.

When a halogen is used, it is convenient to pass it to a solution or suspension of the feedstock in an aqueous medium, for example aqueous acetic acid or hydrochloric acid.

When a sulfuryl halide is employed the reaction is preferably carried out in the presence of wet silica gel, and in a suitable solvent, for example dichloromethane.

• tano.

<img file="PT84780B_D0009.tif" />

· * Cí

The compounds of formula I wherein R b 3 2 1 represents hydrogen and R ° represents R^JCONHCR -CR- may be prepared by a process comprising subjecting the corresponding compounds of formula I, wherein R^The and R ^ together represent -C (R) = NC (R) = C (R) -, acting on a base under mild conditions to give the desired compound.

It is desirable that the base be an inorganic base, especially an alkali metal hydroxide, for example sodium or potassium hydroxide, and is desirable to be employed in aqueous solution.

It is desirable that the reaction be carried out at a temperature of from 09 ° C to 509 ° C, particularly at room temperature. At higher temperature, or under more severe conditions, the reaction proceeds one more step as described below.

The compounds of formula I wherein R^The 10 3 y) I and R^D together represent a chain -C (R^J) = NC (R^z) = C (R 1 - wherein R is different from hydroxyl, mercapto or amino, may alternatively be prepared by a process in which a compound of the formula

<img file="PT84780B_D0010.tif" />

R2COCHR1 '

ΛΛ

ONLY₂NR4R5

2 Wherein R, R, R and R have the meaning defined above, ??? 33 is reacted with an amine of formula R CONH₂wherein R has the meaning defined above to give the desired compound.

The reaction is conveniently carried out by heating a mixture of the reactants, for example at a temperature of 50 ° C to 2009 ° C.

The compounds of formula I wherein R^The fo 3 2 1 and R ° together represent a -C (R^J) = NC (R) = C (R) -, wherein R is hydroxyl, mercapto or amino, may be prepared by reacting a compound of formula IV as defined above with urea, thiourea or guanidine respectively to give the compound. wanted.

<img file="PT84780B_D0011.tif" />

The reaction is conveniently carried out by heating a mixture of the reactants for example at 50 ° C to

2009 Ç.

The compounds of formula IV may in turn be prepared by a process in which a compound of formula I, wherein R represents hydrogen and R represents a group R CONHCR = CR is subjected to an appropriate base under suitable conditions. to give the desired compound.

The base employed is conveniently an alkali metal base, for example an alkaline metal hydroxide, and it is desirable for the reaction to be carried out in a suitable solvent, for example water, and with heating at a temperature of 60 ° C to 100 ° C.

The compounds of formula III wherein R^The and R^B together represent a chain of formula -C (= Y) -NΖΓ Π Ί Ί Π £ (R °) -C (R^z) = C (R) - where Y, R^x, R^Z and R ° have the meanings defined above, are themselves novel compounds which may be prepared from the corresponding compounds wherein R^The is hydrogen and R^D is an R COCHR- group by reaction of those with an isocyanate or isothiocyanate of the formula wherein R and Y are as defined above. In turn these starting materials may be prepared by reacting thios semicarbazide with a compound of the formula:

Z \ (V)

R² —-CH - C00C_OH_ç »! ²⁵

2 wherein R and R are as defined above, reacting the product, if desired, with a compound of the formula RHal, wherein R is as defined above and removing the protecting group by acid.

Salts of the compounds may be prepared; of formula I by reacting them with a suitable base containing. the desired cation, for example the appropriate trialkylamine.

The compounds of formula I may also be

<img file="PT84780B_D0012.tif" />

well be interconverted by methods known per se. For example, compounds of formula I wherein R is other than hydrogen may be prepared from the corresponding compounds and

wherein R is hydrogen by reaction of that compound in the presence of a strong base, for example sodium hydride, with a halide of the formula R Hal.

The carboxyl groups present in the compounds of formula I may be esterified, the ester groups present may be hydrolyzed to the corresponding acids and the cyano or ester groups may be converted to amide or substituted by amide groups. These transformations, like many others, can be carried out by techniques well known to those skilled in the art and various examples of such transformations are described below.

Particular mention may be made of the conversion of compounds of formula I wherein R or R are hydroxyl to the corresponding compounds wherein R is chlorine by reaction of the above compounds with phosphorus oxychloride and subsequent reaction of the chlorine compounds in the formula. the presence of a base with an alcohol, alkanetiol, amine or cyanide to give the corresponding compounds of formula I wherein R represents alkoxy, alkylthio, amino or cyano respectively.

The compounds of formula I have herbicidal activity against a wide range of broadleaf and herbaceous weeds, but are comparatively safe for certain crop species. These compounds can therefore be used as selective herbicides, particularly in combating various weeds of cereal crops and other plants, for example wheat, barley, maize, soybean, rapeseed, cotton and sugar beet.

According to another aspect, the present invention relates to a herbicidal composition comprising one or more compounds of formula I in association with an appropriate carrier and / or surfactant.

The compositions usually contain from 0.01 to 99% by weight of the active compounds and are normally produced. initially used as concentrates containing from 0.5% to 99%, preferably from 0.5 to 85%, and especially from 10 to 50% by weight of the active compounds. These concentrates may be diluted, if necessary, prior to application to the site to be treated such that the active ingredient has a concentration of 0.01 to 5% by weight of the applied formulation.

The carrier may be water, in which case an organic solvent may also be present, although usually not used. A fluidizable concentrated suspension may be formed by grinding the compound with water, a wetting agent and a suspending agent, for example xanthan.

Alternatively the carrier may be a water-immiscible organic solvent, for example a hydrocarbon of 130 to 270 ° C, for example xylene, in which the compound is dissolved or suspended. An emulsifiable concentrate may be formed containing a water immiscible solvent with a surfactant such that the concentrate behaves as a self-emulsifiable oil when mixed with water.

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

Alternatively the carrier may be a solid which may be finely divided or granular. Examples of suitable solids are: limestone, clay, sand, mica, cre, attapulgite, diatomite, perlite, pyiolite, silica, silicate, lynosulfonate and solid fertilizer. The carrier may be of natural or synthetic origin or may be a modified natural material.

They may be prepared by water-soluble or readily dispersible by mixing the particulate compound with a particulate carrier or by spraying the molten compound onto the particulate carrier by mixing a wetting agent, a dispersing agent and finely grinding the reV powder mixture

<img file="PT84780B_D0013.tif" />

Sultant.

An aerosolized composition may be prepared by mixing the compound with a propellant, for example a polyhalogenated alkane such as dichlorofluoromethane, and also conveniently with a solvent.

The term surfactant is used broadly to include various materials such as so-called emulsifying agents, dispersing agents and wetting agents. Such agents are known to those skilled in the art.

Surfactants may include anionic surfactants, for example phosphoric acid monoesters and diesters with a fatty alcohol ethoxylate, or salts thereof, fatty alcohol derived sulfates such as sodium lauryl sulfate, sulfates derived from ethoxylated fatty alcohols, ethoxylated alkylphenyl sulfates, lignin sulfates, petroleum derived sulfonates, alkylaryl derived sulfonates, such as alkyl benzene sulfonates or lower alkyl naphthalene sulfonates, condensed sulfonated naphthalene formaldehyde salts, condensed sulfonated phenolformaldehyde salts or more complex sulfonates such as amide derived sulfonates, for example the oleic acid condensation sulfone product with N-methyl taurine or dialkyl sulfosuccinates, for example dioctyl sodium sulfosuccinate.

Surfactants may also include nonionic agents, for example condensation products, or esters of fatty acids, fatty alcohols, fatty acid amides or ethylene oxide substituted phenols, fatty esters of alcohol ethers. polyhydric acids, for example fatty acid sorbitol esters, ethylene oxide condensation products of these esters, for example polyoxyethylene sorbitol fatty acid esters, block copolymers of ethylene oxide with propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decine-4,7-diol or acetylenic ethoxylate glycols.

Surfactants may also

<img file="PT84780B_D0014.tif" />

may include cationic agents, for example alkyl and / or aryl substituted quaternary ammonium compounds such as cetyl trimethyl ammonium bromide, or ethoxylated tertiary fatty amines.

Surfactants which include sulfates derived from ethoxylated fatty alcohols, sulfinates derived from lignin, alkyl aryl derived sulfonates, condensed naphthalene formaldehyde salts, condensed sulfonated phenolformaldehyde salts, sodium N-methyltaurine oleyl ester, are preferred. dialkyl sulfosuccinates, alkyl phenol ethoxylates and fatty alkyl ethoxylates.

The active compounds of the present invention, especially the compounds prepared according to the following examples and particularly N- (2,6-difluoro-phenyl) -5,7-dimethyl / 1,2,4 / triazolo / 1,5 -c / pyrimidine-2-sulfonamide and 5- (2-acetamido-1-propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazole-3-sulfonamide may be mixed with other pesticides, for example with a herbicide, fungicide or insecticide, or with a plant growth regulator, particularly with another herbicide. Suitable herbicides for admixture include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metolachlor, fluometuron, oxifluorfen, fomesafen, bentazone, prometrine, norflurazon, clomazone, EPTC, imazaquin and especially isoproturon, metabenzinylazole, trifenzinazole, mecoprop, fluroxipir, alachlor, acifluorfen, lactofen, metribuzin and pendimetalin.

The compounds of the present invention may be applied to plants, soil, land or aquatic areas and particularly where there is growing or about to grow crops. The compounds are active in both preemergence and postemergence.

The invention is illustrated by the following Examples, wherein Me = methyl, Et = ethyl and Ph = phenyl.

. Preparative Example A • N- (2-Chlorophenyl) -5,7-dimethyl / 1,2,4,7-triazolo / 1,5-c-pyrimidine-211 X

<img file="PT84780B_D0015.tif" />

sulfonamide (Compound Al)

a) 5,7-Dimethyl Chloride / 1,27-triazolo / 1,5-c / pyrimidine-2-sulfonyl

Chlorine gels were bubbled through a suspension of 5,7-dimethyl / 1,2,4 / triazolo / 1,5-pyrimidine-2-thiol (5.4 g) in water (50 ml) at room temperature. at 5-10 ° C with vigorous stirring for 30 minutes. The solid was filtered off and dissolved in dichloromethane (8 ml). The organic solution was washed with water (10 ml), dried over magnesium sulfate and concentrated under vacuum to give a yellow gummy solid, 2.7 g, which was shown to be the desired product by spectroscopy. .

b) N- (2-chlorophenyl) -5,7-dimethyl / 1,2,4 / triazolo / 1,5-o7-pyrimidine-2-sulfonamide

The solution of sulfonyl chloride (2.7 g) in dichloromethane (10 ml) was slowly added to a stirred solution of 2-chloroaniline (1.54 g) in pyridine (20 ml) at 10-159 ° C. The temperature was kept below 159 ° C. After the addition was complete, the mixture was allowed to return to room temperature and stirred overnight. It was then concentrated in vacuo and 5% hydrochloric acid (15 ml) and ether (10 ml) were added to the residue. The resulting solid was filtered off and flash chromatographed on silica using 1: 1 petroleum ether (m.p. 60-809 ° C) / ethyl acetate as eluent. The desired sulfonamide was obtained as a creamy solid, mp 190-192 ° C, yield 1 g.

Examples A2-A49

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

<td>Ν9.</td><td>Rl</td><td>R2</td><td>R3</td><td>R4 (Ph subst :)</td><td>MP (9 C)</td>

<td>Α2</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diCl</td><td> 279-282</td>

<td>Α3</td><td>H</td><td>Me</td><td>Me</td><td>2-Cl, 6-Me</td><td> 238-239</td>

<td>Α4</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diF</td><td> 229-231</td>

<td>Α5</td><td>H</td><td>Me</td><td>Me</td><td>2-HO₂</td><td> 189-192</td>

<td>Α6</td><td>H</td><td>Me</td><td>Me</td><td>2-CF₃</td><td> 193-195</td>

<td>Α7</td><td>H</td><td>Me</td><td>Me</td><td>2-COOMe</td><td> 180-182</td>

<td>Α8</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diCl, 3-Me</td><td> 242-244</td>

<td>Ά9</td><td>H</td><td>Me</td><td>Me</td><td>2,3-diCl</td><td> 176-178</td>

<td>AIO</td><td>Me</td><td>Me</td><td>Me</td><td>2,6-diCl</td><td> 241-243</td>

<td>All</td><td>Me</td><td>Me</td><td>Me</td><td>2-Cl-6-Me</td><td> 212-214</td>

<td>A12</td><td>Me</td><td>Me</td><td>Me</td><td>2,6-diCl, 3-Me</td><td> 232-234</td>

<td>A13</td><td>Cl</td><td>Me</td><td>Me</td><td>2,6-diF</td><td> 214-216</td>

<td>A14</td><td>H</td><td>Me</td><td>Me</td><td>2-Cl, 6-F</td><td> 253-255</td>

<td>A15</td><td>H</td><td>Me</td><td>Me</td><td>2-Me, 6-NO₂</td><td> 248-250</td>

<td>A16</td><td>Cl</td><td>Me</td><td>H</td><td>2,6-diF</td><td> 235-238</td>

<td>A17</td><td>H</td><td>Me</td><td>Ph</td><td>2,6-diF</td><td> 266-269</td>

<td>A18</td><td>H</td><td>Me</td><td>Me</td><td>2,3,5,6-tetraF</td><td> 236-239</td>

<td>A19</td><td>H</td><td>Ph</td><td>Me</td><td>2,6-diF</td><td> 269-275</td>

<td>A20</td><td>H</td><td>Ph</td><td>Me</td><td>2-Cl, 6-Me</td><td> 272-275</td>

<td>A21</td><td>H</td><td>Me</td><td>Ph</td><td>2-Cl, 6-Me</td><td> 275-276</td>

<td>A22</td><td>H</td><td>cf₃</td><td>Me</td><td>2,6-diF</td><td> 165-167</td>

<td>A23</td><td>Me</td><td>Me</td><td>Me</td><td>2,6-diF</td><td> 220-223</td>

<td>A24</td><td>H</td><td>Me</td><td>Me</td><td>2-Cl, 6-SMe</td><td> 233-235</td>

<td>A25</td><td>H</td><td>Et</td><td>Me</td><td>2,6-diF</td><td> 190-192</td>

<td>A26</td><td>H</td><td>Me</td><td>OH</td><td>2,6-diF</td><td> &gt;350</td>

<td>A27</td><td>H</td><td>Me</td><td>Me</td><td>2-Me, 6-COOMe</td><td> 195-197</td>

<td>A28</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diBr</td><td> 276-278</td>

<td>A29</td><td>H</td><td>H</td><td>Me</td><td>2,6-diF</td><td> 203-205</td>

<td>A30</td><td>Br</td><td>Me</td><td>H</td><td>2,6-diF</td><td> 219-221</td>

<td>A31</td><td>H</td><td>Me</td><td>Me</td><td>2,3-diMe, 6-NO₂</td><td> 177-179</td>

<td>A32</td><td>H</td><td>H</td><td>Me</td><td>2,6-diCl</td><td> 222-224</td>

<td>A33</td><td>H</td><td>Me</td><td>Me</td><td>2-F, 6-COOMe</td><td> 213-215</td>

<td>A34</td><td>H</td><td>H</td><td>Me</td><td>2-Cl, 6-Me</td><td> 218-219</td>

<td>A35</td><td>H</td><td>Me</td><td>Me</td><td>2,5-diMe, 6-COOMe</td><td> 207-209</td>

<td>A36</td><td>H</td><td>Me</td><td>H</td><td>2,6-diF</td><td> 202-204</td>

<td>A37</td><td>H</td><td>Me</td><td>Me</td><td>2-F, 6-COOEt</td><td> 160-163</td>

I

<img file="PT84780B_D0016.tif" />

<td>Ν9.</td><td>Rl</td><td></td><td>R2</td><td>R3</td><td></td><td>R4 (Ph subst :)</td><td>FP (9C)</td>

<td>Α38</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-OCHF₂</td><td> 160-162</td>

<td>Α39</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2,3-diCl-6-NO₂</td><td> 229-234</td>

<td>Α40</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-OMe</td><td> 178-180</td>

<td>Α41</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-CN</td><td> 235-236</td>

<td>Α42</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>3,5-diCl</td><td> 267-269</td>

<td>Α43</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-SO₂NH₂</td><td> 208-210</td>

<td>Α44</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2,6-diMe</td><td> 235-237</td>

<td>Α45</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2,5-diCOOMe</td><td> 176-179</td>

<td>Α46</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2,5-diCl</td><td> 198-201</td>

<td></td><td></td><td></td><td></td><td></td><td> 0</td><td>following compound of</td><td>formula I was</td>

<td>also</td><td colspan="2">prepared</td><td>per</td><td colspan="2">a method</td><td>analogous to that of Example</td><td>THE</td>

<td>N9</td><td>Rl</td><td>R2</td><td colspan="2">R3 R4</td><td>(Ph</td><td>subst :) R5 PF</td><td>. (9C)</td>

<td>A47</td><td>H</td><td>Me</td><td colspan="2">Me 2.6</td><td colspan="2">-diF Me 168</td><td> -170</td>

<td></td><td></td><td></td><td></td><td></td><td>The</td><td>following compounds</td><td>of formula I</td>

<td>on what</td><td colspan="3">4 R represents</td><td colspan="2">2-pyridyl</td><td>was also prepared</td><td>by a method</td>

<td colspan="3">from analog to</td><td colspan="2">Example A:</td><td></td><td></td><td></td>

<td>N9</td><td>Rl</td><td></td><td>R2</td><td>R3</td><td></td><td>R5 PF (9C)</td><td></td>

<td>A48</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>H 246-247</td><td></td>

<td colspan="2">Examples A49</td><td>-A52</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td>The</td><td>following compounds</td><td>of formula I,</td>

<td>on what</td><td colspan="3">5th R represents</td><td colspan="3">a group of formula A where R¹</td><td>2 3 - , R and R are</td>

<td>equals</td><td colspan="6">to the corresponding groups in the remaining part</td><td>of molecule,</td>

<td colspan="3">were prepared</td><td>per</td><td>methods</td><td colspan="2">analogous to those described</td><td>in Example A.</td>

<td>N9</td><td>Rl</td><td></td><td>R2</td><td>R3</td><td></td><td>R4 (Ph subst :)</td><td>FP (9C)</td>

<td>A49</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2,6-diCl, 3-Me</td><td> 278-282</td>

<td>A50</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-Me, 6-NO₂</td><td> 244-246</td>

<td>A51</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-F, 6-COOMe</td><td> 255-257</td>

<td>A52</td><td>H</td><td></td><td>Me</td><td>Me</td><td></td><td>2-F, 6-COOEt</td><td> 259-261</td>

<img file="PT84780B_D0017.tif" />

Preparative Example B

5- (2-Acetamido-1-propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazol-3-sulfonamide (compound B1)

A solution of the product of Example 4 (2.4 g) in 5% aqueous sodium hydroxide solution (20 ml) was stirred at room temperature for 1.5 hours and allowed to stand for a further 18 hours. The solution was acidified to pH = 2 with hydrochloric acid to precipitate a solid. This was filtered off, washed with water (2x10 mL) and ether (2x10 mL) to give 2.1 g of the desired product as a white solid, mp 226-2289 ° C.

Examples B2-B7

The following compounds of formula I,

<td rowspan="3">in gue CR¹-, N9</td><td rowspan="3">_no5th R e were Rl</td><td colspan="4">R^The are hydrogen and κ represents a group R^JCONHCR =</td>

<td rowspan="2">prepared R2</td><td colspan="3">by methods analogous to those of Example B.</td>

<td>R3</td><td>R4 (Ph subst :)</td><td>FP (9C)</td>

<td>B2</td><td>H</td><td>Me</td><td>Me</td><td>2-Cl, 6-Me</td><td> 234-236</td>

<td>B3</td><td>H</td><td>cf₃</td><td>Me</td><td>2,6-diF</td><td> 141-145</td>

<td>B4</td><td>H</td><td>Me</td><td>Me</td><td>2-Cl</td><td> 162-164</td>

<td>B5</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diCl, 3-Me</td><td> 234-235</td>

<td>B6</td><td>H</td><td>Me</td><td>Me</td><td>2,6-diCl</td><td> 282-283</td>

<td>B7</td><td>H</td><td>Me</td><td>Me</td><td>2-Me, 6-NO₂</td><td> 242-245</td>

<td colspan="3">Preparative Example C</td><td></td><td></td><td></td>

<td>N- (2.6-</td><td colspan="2">Difluorophenyl) -5,</td><td>6-di</td><td>-hydro-7-methyl-5-oxo / 1,2</td><td>47-triazole</td>

/ 1,5-pyridine-2-sulfonamide

An aqueous solution of the product of Example 4 (15 g) in 5% sodium hydroxide (25 ml) was refluxed for 4 hours. The solution was then cooled and acidified to pH = 4 with concentrated hydrochloric acid to precipitate a creamy solid. This was filtered off and washed with water and ether to give 11 g of N- (2,6-difluorophenyl) -5- (2-oxopropyl).

<img file="PT84780B_D0018.tif" />

pil) -1Η-1,2,4-triazol-3-sulfonamide, mp 182-1849 ° C.

A homogeneous mixture of the produced sulfonamide (2 g) and urea (10 g) was stirred at 150 ° C for 3 hours, after which the mixture was cooled to 70 ° C and water was added thereto. The solution was acidified to pH = 1 by the addition of concentrated hydrochloric acid to precipitate a solid which was removed by filtration. The solid was extracted with boiling acetonitrile, filtered hot and allowed to cool to give a solid precipitate. This was filtered off to give 0.48 g of the desired product as a white solid, mp 3509 ° C, which was identical to the product of Example 26.

Preparative Example D (a) 5- (2-Methyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazol-3-thiol

Ethyl 2-methyl-1,3-dioxolan-2-ylmethyl) -acetate (43.5 g) was added dropwise to a suspension of thiosemicarbazide (22.8 g) in sodium ethoxide solution ( 6.04 g of sodium in 500 ml of absolute alcohol) at room temperature. The suspension was heated under reflux for 18 hours. After cooling, the solid was removed by filtration and the filtrate concentrated under vacuum. The oily residue was dissolved in water (60 ml), acidified to pH = 5 with acetic acid and concentrated under vacuum. Trituration of the residue with 2-propanol (50 ml) and filtration afforded 11.6 g of the expected product, mp 168-1739 ° C as a white solid.

(b) 3-Benzylthio-5- (2-methyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole

Benzyl chloride (8.07 g) was added dropwise at room temperature to the solution of the product of stage (a) (11.6 g) in sodium ethoxide solution (1.4 g sodium in 100 ml). absolute alcohol content) and the mixture was stirred for 18 hours. The precipitated solid was filtered off and the filtrate was concentrated under vacuum. The resulting oil was partitioned between water (60 ml) and petroleum ether (b.p. 60-80) (50 ml) and the solid filtered off. 13.9 g of the expected product, mp 96-989 ° C, was obtained as a white solid.

(c) 1- (5-Benzylthio-1H-1,2,4-triazol-3-yl) propane-2-one

A suspension of the product of stage (b) (9.9 g) in 1% hydrochloric acid (110 ml) was refluxed for 30 minutes. The mixture was then cooled and the solid removed by filtration. This solid was identified as being of the desired product, 7.6 g, mp 1259 C-1279 C.

Preparative Example E

N-Acetyl-N- (2,6-difluorophenyl) -5,7-dimethyl / 1,2,47triazolo / 1,5-pyrimidine-2-sulfonamide

The product from Example A4 (2 g) was heated under reflux for 2 hours with acetic anhydride (12 ml), after which the reaction mixture was allowed to cool. The precipitated solid was filtered off to give 1.2 g of the expected product, mp 171-1739 ° C.

Preparative Example F

Ethyl chloroformate (1.3 g) from a suspension of the product of Example A4 (2.5 g) in pyridine (13 ml) was added dropwise at 22 ° C and the mixture was stirred at room temperature for 2 days. . After removal of the remaining solid by filtration, the filtrate was acidified with hydrochloric acid and the resulting solid filtered off, washed with dilute ammonia (20 ml) and recrystallized from ethyl acetate to give ethyl acetate. 1.9 g of the expected product, mp 155-1579 ° C.

FORMULATION EXAMPLES

A concentrated formulation was prepared as a 10% suspension from the following ingredients;

X

<img file="PT84780B_D0019.tif" />

<td>Ingredients</td><td> 9/1</td>

<td>Ex A4 Compound</td><td> 100</td>

<td>Pluronic P75</td><td> 30</td>

<td>Polyfon H</td><td> 20</td>

<td>Propylene glycol</td><td> 105</td>

<td>Anti-Foam 1520</td><td> 0,5</td>

<td>Vee R Gum</td><td> 7,5</td>

<td>Kelzan</td><td> 1,0</td>

<td>Formaldehyde (40%)</td><td> 1,0</td>

<td>Water</td><td>up to 1 liter</td>

Similar formulations containing 5, 10, 25, 50, 200 and 500 g / l of the compounds of Examples A1-A53, B1-B7, C, D and E. were also prepared.

USE AS HERBICIDE EXAMPLE A (Preemergence)

Seeds of the weed species listed below were sown on an anodized aluminum tray 19 cm long by 9.5 cm wide and 6 cm deep containing sterile sandy soil. They were moistened and then sprayed with the compounds of the Examples listed below in formulations as a 1: 1 by volume solution or suspension of acetone with polyoxyethyl (20 mol) as wetting agent and monolaurate solution (2 g per liter).

Both the concentration of each test compound and the volume of application were calculated to obtain the desired application rate of the compound at 450 liters per hectare. After 3 to 4 weeks of growth in the environment controlled cab (209 ° C; 75-95% relative humidity; 14 hours per day of artificial lighting) the result of each herbicide application to the plants was visually assessed.

Differences from an untreated comparison trial were assessed according to an index with the following meaning: 0 = no effect, = 1 to 24% effect, 2 = 25 to 69% effect, 3 = 70 to 89% and 4 = 90 to 100% effect. In the table below the following le

- 18 backs were used to designate plant species:

a- Polygonum lapathifolium (pale persicaria) b- Galium aparine (aparina) c- Chrysanthemum segetum (marigold) d- Alopecurus myosuroides (black grass) e- Elymus repens (field grass) f- Avena fatua (wild oats) g - Abutilon threophrasti (fuzzy leaf) h- Cyperus rotunds (purple juniper) i- Pharbitis purpurea (iponeia) j- Echinochloa crus-galli (backyard grass) k- Setaria viridis (green fox tail)

1 ”Solanum nigrum (Moorish Grass)

The following results were obtained:

Ex

22 23

Kg / ha abc

2.5 444

2.5 444

2.5 444

1.0 4 4

1.0 4 4

1.0 444

1.0 332

1.0 444

1.0 234

1.0 242

1.0 243

1.0 444

1.0 4 4 4

1.0 444

1.0 344

1.0 234

1.0 432

1.0 444

1.0 432 of

2

0

4

4

0 3 2

2 3 3

0 0 0 0 0 2 2 3 3

3

2 2 2 2 0 2 0 0 0 f

hi 2k 1

2 2 3

4 4 4 4

4 4 4 4

4 3 4 4

3 2 2 3

4 3 3 4

0 2 2 4

3 3 3

10 0 3

12 0 4

0 0 0 4

3 2 1 4

4 2 2

4 4

2 0 0 4

0 0 0

0 0 0

0 0 4

0 0 2

<img file="PT84780B_D0020.tif" />

<td>Ex</td><td>Kg / ha</td><td>The</td><td>B</td><td>ç</td><td>d</td><td>and</td><td>f</td><td> £</td><td>H</td><td>i</td><td>i</td><td>k</td><td> 1</td>

<td> 24</td><td> 1.0</td><td> 4</td><td> 4</td><td> 4</td><td> 0</td><td> 2</td><td> 0</td><td> 0</td><td> 3</td><td> 0</td><td> 2</td><td> 3</td><td> 3</td>

<td> 25</td><td> 0.5</td><td> 3</td><td> 3</td><td> 4</td><td> 0</td><td> 0</td><td> 0</td><td> 1</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 2</td>

<td> 29</td><td> 0.5</td><td> 3</td><td> 4</td><td> 4</td><td> 2</td><td> 2</td><td> 2</td><td> 4</td><td> 4</td><td> 4</td><td> 2</td><td> 0</td><td> 4</td>

<td> 30</td><td> 0.5</td><td> 2</td><td> 4</td><td> 2</td><td> 2</td><td> 2</td><td> 0</td><td> 2</td><td> 0</td><td> 3</td><td> 0</td><td> 0</td><td> 3</td>

<td> 31</td><td> 0.5</td><td> 2</td><td> 4</td><td> 4</td><td> 2</td><td> 2</td><td> 0</td><td> 4</td><td> 4</td><td> 4</td><td> 3</td><td> 2</td><td> 4</td>

<td> 40</td><td> 1.0</td><td> 3</td><td> 4</td><td> 4</td><td> 0</td><td> 0</td><td> 0</td><td> 2</td><td> 2</td><td> 0</td><td> 0</td><td> 0</td><td> 4</td>

<td> 41</td><td> 0.5</td><td> 4</td><td> 4</td><td> 4</td><td> 2</td><td> 0</td><td> 0</td><td> 4</td><td> 4</td><td> 2</td><td> 3</td><td> 0</td><td> 4</td>

<td>Bl</td><td> 1.0</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 3</td><td> 2</td><td> 4</td><td> 4</td><td> 4</td><td> 3</td><td> 4</td><td></td>

<td>B2</td><td> 1.0</td><td> 4</td><td> 4</td><td> 4</td><td> 0</td><td> 0</td><td> 4</td><td> 3</td><td> 4</td><td> 2</td><td> 4</td><td> 3</td><td> 0</td>

<td>B3</td><td> 1.0</td><td> 4</td><td> 4</td><td> 4</td><td> 2</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 2</td><td> 0</td><td> 0</td><td></td>

<td>B5</td><td> 0.5</td><td> 4</td><td> 4</td><td> 4</td><td> 3</td><td> 0</td><td> 3</td><td> 2</td><td> 0</td><td> 0</td><td> 2</td><td> 4</td><td> 4</td>

<td>B6</td><td> 0.5</td><td> 4</td><td> 4</td><td> 4</td><td> 2</td><td> 3</td><td> 0</td><td> 2</td><td> 4</td><td> 2</td><td> 2</td><td> 0</td><td> 4</td>

<td>B7</td><td> 0.5</td><td> 4</td><td> 4</td><td> 4</td><td> 2</td><td> 2</td><td> 2</td><td> 0</td><td> 3</td><td> 0</td><td> 2</td><td> 2</td><td> 4</td>

USE AS HERBICIDE EXAMPLE B (After Emergency)

Seeds of the weed species listed below were sown on anodized aluminum trays 19 cm long by 9.5 cm wide and 6 cm deep containing sterile sandy soil. They were then wetted and placed in a room with a regulated environment (20 ° C; 75-95% relative humidity; 14 hours per day of artificial lighting). Fourteen or twenty-one days after sowing (depending on species but generally when 2 to 3 true leaves developed on most plants) the young plant leaves were sprayed with the compounds of the Examples listed below in formulations. as a 1: 1 by volume solution or suspension of acetone with polyoxyethylene (20 mol) and monolaurate solution (2 g per liter).

The concentration of each test compound was calculated to give the desired application rate of the compound at 450 l per hectare. After 2 to 3 weeks of growth in the controlled environment cabinet, the result of each herbicide application to the plants was visually assessed.

The differences in relation to

<img file="PT84780B_D0021.tif" />

to an untreated comparison trial were evaluated according to an index with the following meaning: 0 = no effect, 1 = effect 1 to 24%, 2 = effect 25 to 69%, 3 = effect 70 to

89% and 4 = 90 to 100% effect. In the table below the following letters were used to designate plant species:

ri · a- Polygonum lapathifolium (pale persicaria) b- Galium aparina (aparina) c- Chrysanthemum segetum (marigold) d- Alopecurus myosuroides (black grass) e- Elmymus repens (field grass) f- Avena fatua (wild oats) ) g- Abutilon threophrasti (velvet leaf) h- Cyperus rotundus (purple juniper) i- Pharbitis purpurea (morning glory) j- Echinochloa crus-galli (backyard grass) k- Setaria viridis (green fox tail)

1 ”Solanum nigrum (Moorish Grass)

The following results were obtained:

Ex. Kg / ha to

2.5

2.5

2.5

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.0

1.0

0.5

1.0

3

4

4

3

3

3 4

4

4

4

4

4

3

4

4

2

3

3

3

0 2 2 3 2

0

0

2

2

2

2

0

0

0 1 2 2 2 2 2 0 1

1 2 1 0 0 0 2 0 2

2 0 2 0 0 0 0 2 0

3

2

1

0 1 1 4 1

1 2 0 2 0

0

0

0

0 0 3

1 4 4

4

2 1 1 1 1

1 1 1 0 0 1 1

2 2 2 2 1 1 0 0 2

4

4

3

3 2 0 1 2

3

2 0 4

2 2 2 2 2 0 2 0 0

3

<img file="PT84780B_D0022.tif" />