CS38491A2 - 6-aryl-2-substituted derivatives of benzoic acid, method of their production, herbicide and method of undesirable plants killing - Google Patents

Description

The present invention relates to 6-aryl-2-substituted benzoic acid derivatives, to processes for their preparation and to herbicidal compositions containing them.

SUMMARY OF THE INVENTION

The present invention provides 6-aryl-2-substituted benzoic acid derivatives of formula (I)

CO2M

where 2 2

A is oxygen, sulfur, -NR, where R is hydrogen, alkyl, for example methyl or ethyl, -C (O) NH2 or -C (O) -alkyl, for example, -c (o) -ch3, B is - GH-, -GR1- or -N-, R and R1 are each independently alkyl, for example methyl, alkoxy, for example methoxy, halo-alkoxy, for example -OCHF2 or -OCH2CH2Cl, or alkylamino, for example, -N (CH3) R 2 is hydrogen, alkyl, phenyl, nitro, cyano, amino, alkoxycarbonyl or halogen, M is hydrogen, alkyl, alkenyl, alkynyl, phenylalkyl, haloalkyl, cyanoalkyl, alkylthioalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkoxycarbonyllalkyl, carboxyalkyl, di (alkoxycarbonyl) alkyl, dialkylaminocarbonylalkyl, dialkylidenaminoalkyl, alkylthioalkylideneamino, ammonium, optionally substituted alkyl or hydroxyalkyl, alkali metal or alkaline earth metal or phenyl, optionally substituted by nitro, halogen, alkyl, haloalkyl or alkoxy;

Q is a group of formula (II)

wherein X, Y and P are independently hydrogen, halo, such as chloro and fluoro, lower alkyl such as methyl, lower alkoxy, methoxy, cyano, nitro, amino, lower haloalkyl such as trifluoromethyl or difluoromethyl, lower haloalkoxy such as tri -fluoromethoxy or difluoromethoxy, lower alkylthio such as methylthio, lower alkylsulfonyl such as methylsulfonyl, alkylsulfonylamino, alkylsulfonyloxy, arylsulfonyloxy, di (arylsulfonyl) amino, benzylamino, alkylcarbonylamino, aminocarbonylamino a group, an alkoxycarbonyl, an alkylcarbonyloxy group, an alkylsulfonyl-1-amino group, a phenylsulfonylamino group, and a salt of such an acid group, a lower alkenyl such as vinyl or methyl-vinyl, lower alkynyl such as ethinyl non-b ' 3-propyl, lower alkenyloxy, 2-propenyl or lower alkynyloxy, such as propargyloxy, or X and Y are is an alkylenedioxyheterocyclic ring having from 1 to 3 carbon atoms, for example a benzodioxole ring, or Q is an aromatic heterocyclic ring

with 5 or 6 ring atoms from thiophene, furan, pyrrole, pyrazole, isoxazole, isothiazole, imidazole, oxazole, thiazole, oxadiazole, thiadiazole, triazole, tetrazole, pyridine, pyrimidine, pyrazine, pyridazine and triazine with formula A or B

(A) (B) - 4 - where x ', y', W, V, U, X ", Y", w ', V * and Z independently represent a nitrogen, oxygen, sulfur, -CH- or -CR3, where halo is a chloro or bromo atom, lower alkyl such as methyl or isopropyl, lower alkoxy such as methoxy or lower haloalkoxy such as difluoromethoxy. It is often preferred that the alkyl, alkynyl, or alkenyl including hydrocarbon chain of the alkoxy group be lower alkyl of 3 carbon atoms. at a maximum of 6 carbon atoms, preferably 1 to 5 carbon atoms;

The compounds of formula (I) may be used in the compounds of formula (IV)

(IV) wherein A, B, Q, R and R are as defined in formula (I) and T is a precursor or derivative of an acid such as formyl, cyano, methylcarbonyl, dialkoxymethyl, alkoxycarbonyl, aryloxycarbonyl, alkyl or halogen. Depending on the meaning of the symbol T, the compounds of the formula I can be obtained by oxidation of the formyl group, hydrolysis of the cyano group, aryloxycarbonyl group or alkoxycarbonyl group, hydrolysis of the alkoxymethylsubstituent to form an aldehyde which is oxidized to the acid by oxidation of the methylcarbonyl sub-group. by substituting hypohalite or replacing the - 5-halogen atom with alkyllithium followed by carbon dioxide and acid.

Compounds of formula IV wherein T is formyl, cyano, methylcarbonyl, dialkoxymethyl, alkoxycarbonyl, aryloxycarbonyl, -C (O) OH, -C (O) OM or halogen may be prepared by the following reaction:

wherein G is a readily cleavable group such as a chlorine atom or a methylsulfonyl group. Various bases including alkali metal or alkaline earth metal carbonates, hydrides and hydroxides or lower dialkylamines can be used to carry out the reaction. Specific examples are sodium, potassium, lithium or calcium carbonate and hydroxide, sodium, lithium and potassium hydrides, and lithium, sodium or magnesium diisopropylamides.

Oxygen-containing compounds of formula (I) may also be prepared by reacting o-fluorobenzaldehyde, optionally substituted with potassium hydroxide, to give the corresponding optionally substituted salicylaldehyde. Preferably, the substituent is in the 6-position, the preferred product of which is salicylaldehyde optionally substituted at 6. This material is then reacted with an inorganic barium such as potassium carbonate or sodium hydride and an appropriately substituted heterocyclic compound with a readily cleavable group at the 2-heterocyclic ring, for example, a chloro or methylsulfonyl group; -dimethoxy-2-methylsulfonylpyrimidine or 2-chloro-4,6-dimethoxy-1,3,5-triazine to give the corresponding benzaldehyde, for example 2- (1,6-dimethoxypyrimidin-2-yloxy) benzaldehyde or 2- (4,6-dimethoxy-1,3,5-triazin-2-yloxy) benzaldehyde, optionally or substituted at the 6-position. This benzaldehyde oxidizes to form the corresponding benzoic acid.

Compounds of formula (I) with an oxygen or sulfur bridge can be prepared by reacting a benzyl-6-substituted salicylate or anthranilate with sodium hydride and an appropriately substituted heterocyclic compound, for example 4,6-dimethoxy-2-methylsulfonylpyrimidine, to give the corresponding benzoate, e.g. benzyl-6-substituted 2- (4,6-dimethoxypyrimidin-2-yloxy) benzoate or 2- (4,6-dimethoxypyrimidin-2-ylamino) benzoate. This benzoate is converted by hydrogenolysis in the presence of palladium on charcoal to the resulting benzic acid, for example 6-substituted 2- (4,6-dimethoxypyrimidin-2-yloxy) -benzoic acid or 2- (4,6-dimethoxypyrimidine-2) -ylamino) benzoic acid.

The bridged compounds of formula (I) may be prepared by reacting anthranilic acid hydrochloride, optionally substituted in the 6-position with fluoroboric acid and sodium nitrite to give - 7 - the corresponding diazonium salt, 2-carboxy-3- (optional). benzenediazonium tetrafluoroborate. This diazonium salt is reacted with the potassium salt of ethylxanthene to give the corresponding 2- (ethoxy-thiocarbonylthio) benzoic acid optionally substituted in 6. The benzoic acid is then hydrolyzed to give 2-mercaptobenzoic acid, optionally substituted in 6, which is then reacted with sodium hydride and an appropriately substituted heterocyclic compound, for example, 4,6-dimethoxy-2-methylsulfonylpyrimidine to form a benzoic acid-free acid, e.g. -dimethoxypyrimidin-2-ylthio) benzoic, optionally substituted in the 6-position.

Compounds of formula (I) wherein Q is alkyl or phenyl optionally substituted may also be prepared using 2-ethoxycarbonyl-3- (optional) phenyl or alkyl cyclohexen-5-one as an intermediate (Intermediate IIa below) the product has been described by FM Hauser et al., Synthesis, 10, 814 (1980). Obtaining intermediate Ha is described in the following scheme:

Stage I 0 qch2c-h base ch3cch2c-oc2h5

QCH = CHCHO 0 =

- 8

Stage II

The intermediate of formula (IIa) may be prepared by reacting ethyl acetate with propenol, and the propyl phenol or phenylpropenol optionally substituted in the 3-position in the presence of a base as the alkoxide of, for example, sodium ethoxide to form the corresponding ketaldehyde, such as intermediate Ia, which is then cyclized to the corresponding cyclohexenone intermediate Ila by an acid catalyzed reaction. In the case of compounds which contain oxygen, the intermediate of formula (IIa) is oxidized to the corresponding ethyl salicylate, for example ethyl-6- (phenyl or alkyl) optionally substituted salicylate, which is then hydrolyzed in alkaline medium to the corresponding salicylic acid which is then reacting with sodium hydride and an appropriately substituted heterocyclic compound, for example a 4,6-dimethoxy-2-methylsulfonylpyrimidine, to yield the corresponding benzoic acid derivative of formula I, for example 6- (phenyl or alkyl, optionally substituted) henzoic acid. In the preparation of a compound having a bridged atom or amino group, cyclohexenone of formula (IIa) is reacted with phosphorous pentasulfide or ammonia to form the corresponding thioketoester or imino ester to give, for example, 2-ethoxycarbonyl-3- (phenyl or alkyl, n-9 - optionally substituted cyclohex-5-enthion or 2-ethoxycarbonyl-3- (phenyl or alkyl, optionally substituted) -cyclohexenimine. The thioketoester or iminoester is then reacted with an oxidizing agent, for example 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to give the corresponding benzoate or anthranilate, for example ethyl 2-mercapto-6-phenylbenzoate or ethyl 6-phenylanthranilate. The benzoate or anthranilate is then reacted with the hydroxide potassium in the presence of 1,4,7,10,13,16-hexaoxacyclooctane decane to give the corresponding benzoic acid derivative of the formula X, for example; 2-mercapto-6 - (phenyl or alkyl, optionally substituted) benzoic acid or 6- (phenyl or alkyl, optionally substituted) -anthranilic acid. The 6-phenylbenzoic acids obtained, for example 6-phenyl-2- (4,6-dimethoxypyrimidin-2-yloxy) benzoic acid, can be esterified by reacting the halogen-containing acid under alkaline conditions in an appropriate solvent, for example a mixture of triethylamine and acetonitrile sodium bicarbonate and dimethylformamide.

The benzoic ester can also be obtained by reacting the benzoyl halide with an alcohol or phenol.

Benzoic acid can be reacted with a alkyl haloformate such as methyl chloroformate in the presence of a base to provide the mixed anhydride as an intermediate. The anhydride is then reacted with the alcohol or phenol to form an ester.

Alternatively, 6-phenylbenzoic acid can be esterified by reaction with an alcohol or phenol, optionally substituted, for example 4-nitrophenol with a dehydrating agent such as 1,3-dicyclohexylcarbodiimide or N, N * -carbonyldiimidazole in the appropriate solvent, for example methylene chloride. 10 -

6-Phenylbenzoic acid can also be esterified, for example, by a lower alkyl alcohol using a catalyst as catalyst. A number of other proesterification procedures are known in the art.

Alkylideneaminobenzoates can be obtained by the method of Example 9 by reacting 4-nitrophenylbenzoate with ketone oxime in the presence of a base such as potassium carbonate. EXAMPLES Example 1

Process for the preparation of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid (Compound 1)

Step A Synthesis of NC (3-methoxyphenyl) methylene] benzenanimide as an intermediate A stirred solution of 20.0 g, 0.146 mol of 2-methoxybenzaldehyde and 13.7 g, 0.146 mol of aniline is refluxed in 200 ml of toluene and condensed. captures in the Dean-Stark apparatus. The theoretical amount of water is eliminated in about 4 hours. Then, the reaction mixture was evaporated under reduced pressure, and the resulting residue was dried under reduced pressure at 50 ° C for 4 hours to give 30 g of N - [(2-methoxyphenyl) methylene] benzene ine.

Step B Synthesis of bis (γ-acetate-0,0 *) bis [3-methoxy-2 - [(phenylimino) methyl] phenyl-C 1 N] dipalladium as the intermediate 11 - (R 6) -; Under a nitrogen atmosphere, a mixture of 9.3 g (0.044 mol) of Ν-β- (2-methoxyphenyl) methylene] benzenamine and 10.0 g (0.044 mol) of palladium (II) acetate in 125 ml of glacial acetic acid was heated to reflux with stirring for 1 hour. The reaction mixture was then poured into 400 ml of ice-water mixture to precipitate a solid which was filtered off and dried under reduced pressure at 50 ° C for 8 hours to give 15.3 g of bis (β-acetate) -0.0 *) bis [3-ethoxy-2 - [(phenylimino) methyl] phenyl-C, N] diapaladium.

Step C: Ethoxy-6- (trans) -aldehyde intermediate Intermediate 21.0 g (0.08 mmol) of triphenylphosphine was added to a stirred suspension of 15.0 g, 0% under an anhydrous nitrogen atmosphere. Of the product of the preceding step in 200 ml of toluene. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After this time, phenyl magnesium bromide (3.0 M in diethyl ether) (26.6 mL, 0.08 mol) was added via syringe over 5 min. After the addition is complete, the reaction mixture is stirred for 1 hour and 90 ml of 6N aqueous hydrochloric acid solution are added dropwise. After the addition was complete, the reaction mixture was stirred for 1 hour and then filtered. The filtrate was diluted with 200 mL of diethyl ether then washed with saturated aqueous sodium chloride. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure and chromatographed on a silica gel column. The column was eluted with EtOAc and then with a 2: 1 mixture of heptane and methylene chloride. Appropriate fractions were combined and evaporated under reduced pressure to give 1.4 g of 2-methoxy-6-phenylbenzaldehyde.

Step D: Synthesis of 6-phenylsalicylaldehyde as an intermediate

Under nitrogen, a stirred solution of 1.4 g, 0.0064 mol of 2-methoxy-6-phenylbenzaldehyde in 100 ml of methylene-12-chloride was cooled to -78 ° C and then 9.6 ml of 0.0096 mol of 1.0M was added. a solution of boron tribromide in methylene chloride using a syringe. After the addition was complete, the reaction mixture was warmed to room temperature and stirred for 18 hours. After this time, the reaction mixture was diluted with 100 ml of methylene chloride and washed with 200 ml of saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue which was chromatographed on a silica gel column. The column was eluted with heptane / methylene chloride in vacuo of 1: 1. The product containing product was combined and evaporated under reduced pressure to give 0.6 g of 6-phenylsilyl aldehyde. The NMR spectrum was consistent with the expected product structure.

Step E: Synthesis of 4, 6-Chloro-2-methylthiopyrimidine as a Intermediate Product Under nitrogen, a stirred solution of 76.9 g, 0.49 mole of 4,6-dihydroxy-2-methylthiopyrimidine and 190 mL, 2.04 mole of phosphorus oxychloride was heated for 2 hours. temperature of 95 to 100 ° C. After this time, the reaction mixture was cooled to 5 ° C and 250 mL of water was added dropwise over 75 minutes. The mixture was heated to 10 ° C and 500 mL of water was added over 15 minutes. The resulting solid was filtered off and washed with water (2.times.100 ml). The solid was dried to give 84.7 g of 4,6-dichloro-2-methylthiopyrimidine, m.p. 40.5-42.5 ° C. This reaction is repeated several times.

Step F: Synthesis of 4,6-dimethoxy-2-methylthiopyrimidine as intermediate A stirred solution of 162.8 g, 0.832 mol of 4,6-dichloro-2-methylthiopyrimidine in 325 ml of methanol is cooled to 15 ° C and 419 ml are added dropwise. 1.83 moles of sodium methoxide as a 25% solution in methanol at such a rate that the temperature of the reaction mixture does not exceed 20 ° C. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 18 hours. After this time, the reaction mixture was evaporated under reduced pressure and the residue obtained was dissolved in 850 ml of ethyl acetate. The solution was washed with 1 x 500 ml and then with 2 x 200 ml of water and then with 200 ml of saturated aqueous sodium chloride solution. The wash was quenched with water and extracted with 350 mL of ethyl acetate. The extract was washed with 150 mL of saturated aqueous sodium chloride solution. The ethyl acetate layers and extracts were combined and dried over magnesium sulfate. The mixture was filtered and the filtrate was evaporated under reduced pressure to give 155.0 g of 4,6-dimethoxy-2-methylthiopyrimidine which solidified to a solid with temperature. mp 50-52 ° C.

Step G: Synthesis of 4,6-dimethoxy-2-methylsulfonylpyrimidine as an Intermediate A stirred solution of 143.6 g, 0.772 moles of 4,6-dimethoxy-2-methylthiopyrimidine in 460 mL of tetrahydrofuran is cooled to 10 to 15 ° C and then cloudy. a solution of 525.0 g, 0.849 mol of 80% monoperoxiftic acid in the form of magnesium salt hexahydrate in 600 ml of methanol so that the temperature of the reaction mixture is kept below 15 ° C. After the addition is complete, the reaction mixture is cooled and 500 ml is added dropwise. 1M aqueous sodium sulfite solution to distribute excess peroxides in the reaction mixture. After the addition was complete, the reaction mixture was stirred for 15 minutes, then evaporated under reduced pressure, and the residue was stirred in a mixture of 2500 ml of ethyl acetate and 1500 ml of water. The layers were separated and the aqueous layer was extracted with 450 mL of ethyl acetate. The ethyl acetate layers were combined and washed with 500 mL of water, 2 x 350 mL of 20% aqueous potassium carbonate, then 2 x 350 mL of water, and finally 300 mL of saturated aqueous sodium chloride. The organic layer (14) was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give 4,5-dimethoxy-2-methylsulfonylpyrimidine (123.3 g), m.p. 126-127.5 ° C.

Step H: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzaldehyde as an intermediate. Stirred solution of 0.53 g (0.0029 mol) of 6-phenylsalicylaldehyde prepared in step under nitrogen. A.; D, 0.62 g, 0.0029 mol of 4,6-dimethoxy-2-thienylsulfonylpyrimidine, prepared in steps E and G and 0.36 g of 0.0029 mol of potassium carbonate in 15 ml of dimethylformamide 4 h at 85 ° C. After this time, the reaction mixture was poured into 100 ml of water and extracted with 50 ml of ethyl acetate. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a gum which was crystallized from a mixture of carbon tetrachloride and ether, yielding 0.75 g of 2- (4,6-dimethoxyprimidine-2). -yloxy) -6-phenylbenzaldehyde.

Step I: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylhenzoic acid (Compound 1) To a stirred solution of 0.55 g, 0.0016 mol of 2- (4,6-dimethoxypyrimidine-2) -yloxy) -6-phenylbenzaldehyde in 15 ml acetone is added a solution of 0.26 g, 0.0016 mol of permanganate and 0.22 g, 0.0016 mol of sodium phosphate in the form of heptahydrate in 10 ml of water. After the addition was complete, the reaction mixture was stirred for 6 hours. Then 1 ml of saturated aqueous sodium thiosulfate solution was added and the mixture was filtered through a pad of diatomaceous earth. Filtration is repeated and the filtrate is then evaporated under reduced pressure to remove acetone. The concentrate was diluted with 50 mL of water and then extracted with 2 x 50 mL of ethyl acetate. The aqueous layer was acidified to pH 3, added with 10% aqueous hydrochloric acid solution and then extracted again with 3 x 75 mL of ethyl acetate. Combine the extracts and concentrate under reduced pressure to a residue which crystallizes from a mixture of carbon tetrachloride and petroleum ether to give 0.43 g of 2- (4,6-dimethoxyprimidin-2-yloxy) -6-phenylbenzoic acid in two portions. The 1-NMR spectrum was consistent with the proposed structure. Example 2

Synthesis of 2- (4,6-Doxypyrimidin-2-yl) -oxyl-6- (thiophen-2-yl) -benzoic acid (Compound 1a)

Step A: Synthesis of (Thien-2-yl) Magnesium Bromide as a Substitute Under a nitrogen atmosphere, a few ml of anhydrous ethyl ether was charged to a reaction vessel containing 1.8 g of 0.072 mol of magnesium shavings. A few ml of a solution containing 11.7 g (0.072 mol) of 2-bromothiophene in 50 ml of anhydrous diethyl ether was added to the reaction vessel. The iodine crystal is then added to initiate the formation of the Grignard reagent. After the start of the reaction, the 2-bromothiophene solution was added dropwise while stirring at such a rate as to produce a gentle reflux. After the addition was complete, the reaction mixture was further refluxed for 55 minutes. The ether solution of (thien-2-yl) magnesium bromide thus prepared is used as isotonic without isolating the resulting material.

Step B: Synthesis of 2-methoxy-6- (thien-2-yl) benzaldehyde as an intermediate 13.5 g of solution, 0.018 moles bis ([alpha] -acetate-O.0) bisph3 was stirred under nitrogen for approximately 1 hour. ® -Thoxy-2 - [(phenylimino) methylphenyl-C, Nldipaladium, prepared 16 - according to Example 1, Steps A and B) and 18.9 g, 0.072 mole of triphenylphosphine in 250 ml of anhydrous toluene, then in ether solution of (thien-2-yl) magnesium bromide is added over 10 minutes using a syringe. After the addition is complete, the reaction mixture is stirred for 18 hours and then 90 ml of 6N hydrochloric acid solution are added. The reaction mixture is then filtered through a pad of diatomaceous earth. The organic layer was separated and washed with a saturated aqueous sodium chloride solution, then dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure and the residue obtained was subjected to chromatography on a LiVagel. The column was eluted with 50% heptane in methylene chloride. Appropriate fractions were combined and evaporated under reduced pressure to give 2.0 g of 2-methoxy-6- (thien-2-yl) benzaldehyde. The NMR spectrum was consistent with the proposed structure.

Step C: Synthesis of 6- (thien-2-yl) salicylaldehyde as the intermediate The stirred solution of 0.3 g, 0.001 mol of 2-methoxy-6- (thien-2-yl) benzaldehyde and 0.3 g, 0.002, is heated under nitrogen. mole of anhydrous lithium iodide in 10 ml of 2,4,6-trimethylpyridine to reflux for 20 minutes. The reaction mixture was acidified with 6N hydrochloric acid and extracted with diethyl ether and analyzed by gas chromatography for completion of the reaction. The residue of the reaction mixture was then acidified with 6N hydrochloric acid.

Second reaction mixture containing reaction product 1.7 g, 0.0078 mol of 2-methoxy-6- (thien-2-yl) benzaldehyde and 1.7 g, 0.013 mol of anhydrous lithium iodide in 10 ml of 2,4,6-trimethylpyridine It is also acidified with 6N aqueous hydrochloric acid. The two acidified reaction mixtures were combined, extracted with diethyl ether and then with ethyl acetate. - 17 -

The extracts were combined, dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue which was chromatographed on a silica gel column. Elution was carried out with 50% heptane in methylene chloride. Appropriate fractions were collected and evaporated under reduced pressure to give 0.9 g of 6- (thien-2-yl) salicylaldehyde. The NMR spectrum was consistent with the proposed structure.

Step D: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzaldehyde as an intermediate. mole of 6- (thien-2-yl) salicylaldehyde, 0.5 g, 0.004 mole of potassium carbonate and 0.7 g> 0.003 mole of 4,6-dimethoxy-2-methylsulfonylpyrimidine in 10 ml dimethylformamide at 80 g. the reaction mixture is poured into water of an aqueous saturated sodium chloride solution and then extracted with two portions of ethyl acetate. The extracts were combined, dried over magnesium sulfate, and filtered. The filtrate is evaporated under reduced pressure and the residue is dried under high vacuum to solidify. The solid obtained was triturated with cold petroleum ether. The solid was filtered to give 0.9 g of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzaldehyde, m.p. 97.5-101 ° C. consistent with the proposed structure.

Step Et Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzoic acid (Compound 1a) Mixed solution 0.12 g, 0.0004 mol 2- (4.6 -dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzaldehyde in 1.2 ml acetone is cooled in an ice / sodium chloride bath and 1.5 ml of a 0.3 M aqueous potassium permanganate solution is added and 0.15M sodium phosphate heptahydrate. After the addition was complete, the reaction mixture was stirred and cooled for one hour in an ice / chlorine bath. A sample is then taken, which is analyzed by chromatography on a thin layer, which demonstrates that the reaction of the lozenge is complete. The bath was removed and the reaction mixture was not allowed to warm to room temperature where it was stirred for 4.75 hours. At this time, the red color was removed by carefully adding dropwise a saturated aqueous solution of sodium thiosulfate.

To the second reaction mixture containing 0.5 g, 0.002 mol of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzaldehyde and 5.4 ml of an aqueous solution of 0.3M aqueous the permanganate solution! ! and a 0.15 M sodium phosphate solution in the form of heptahydrate in 10 mL of acetone is added a saturated aqueous solution of sodium thiosulfate.

The two reaction mixtures were combined and the mixture was filtered through diatomaceous earth. The filtrate is evaporated under reduced pressure to remove volatile material. The aqueous concentrate is washed with diethyl ether and then acidified to pH 2 by the addition of 6N aqueous hydrochloric acid. It was then extracted with three portions of ethyl acetate. The extracts were combined, dried over magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give 0.6 g of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (thien-2-yl) benzoic acid, m.p. 139-140 ° C. compound 1a from Table 1A. The NMR spectrum was consistent with the proposed structure. Example 3

Synthesis of 2- (4,6-dimethoxypyrimidin-2-ylthio) -6-phenylbenzoic acid

Step A: Synthesis of Ν-Γ (2-methylthiophenyl) methylene] benzeneamine intermediate - 19 - A stirred solution of 22.2 g, 0.146 mol of 2-methylthio-benzaldehyde and 13.7 g, 0.146 mol of aniline is heated to room temperature under reflux and the resulting water is collected in a DeanStark apparatus. After removal of the theoretical water, the reaction mixture was evaporated under reduced pressure to a residue which was dried under reduced pressure at 50 ° C to give N-C (2-methylthiophenyl) methylene] benzenamine.

Step B: Synthesis of bis (U-acetate-0,02) bis [3-methylthio - 2 - [(phenylimino) methyl] phenyl-C, N] dipalladium. ti. Λ J Γ O Cl ^ 4 iS. -and. A stirred mixture of N - [(2-methylthiophenyl) methylene] henzenamine (10.0 g, 0.044 mole) and acetic acid (10.0 g, 0.044 mole) in glacial acetic acid (125 ml) was refluxed under nitrogen for 1 hour under reflux. After this time, the mixture was poured into a mixture of water and ice. The precipitate was collected and dried under reduced pressure at a temperature of 50 ° C to give the final product.

Step C: Synthesis of 2-methylthio-6-phenylbenzaldehyde as a Intermediate Under an anhydrous nitrogen atmosphere, triphenylphosphine (21.0g, 0.08mol) was added to a stirred suspension of the previous step (15.7g, 0.02mol) in toluene (200ml). After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After this time, 26.6 ml, 0.08 mole of a 3.0 M solution of phenylmagnesium bromide in diethyl ether was added via a syringe over 5 minutes. After the addition is complete, the mixture is stirred for 1 hour and 90 ml of 6N aqueous hydrochloric acid solution are added dropwise.

After the addition is complete, the reaction mixture is stirred for 1 hour and then filtered. The filtrate was diluted with 200 mL of diethyl 20-ether and then filtered. The filtrate was washed with saturated aqueous sodium chloride solution. The organic layer is dried over magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure to give a residue which is chromatographed on silica gel, eluting first with heptane and then with heptane / methylene chloride 2: 1. The appropriate fractions were combined and evaporated under reduced pressure to give 2-methylthio-6-phenylbenzaldehyde.

Step D: Synthesis of 2-mercapto-6-phenylbenzaldehyde as an Intermediate Under a nitrogen atmosphere, a solution of 1.5 g> 0.0064 mol of 2-methylthio-6-phenylbenzaldehyde in 10 ml of 2,4,5-trimethylpyridine is stirred at the same time. 1.7 g, 0.128 lithium molujodide is added. After the addition was complete, the reaction mixture was heated to 100 ° C and stirred at this temperature for 3 hours. The cooled mixture was then acidified to pH 2 by addition of concentrated hydrochloric acid and then extracted with 2 x 150 ml of methylene chloride. The extracts were combined, dried (MgSO4), filtered and the filtrate evaporated under reduced pressure to give 2-methyl-6-phenylbenzaldehyde.

Step E: Synthesis of 2- (4,6-dimethoxypyrimidin-2-ylthi) -6-phenylbenzaldehyde as an intermediate Under a nitrogen atmosphere, a solution of 0.57 t of 0.0029 mol of 2-mercapto-6-phenylbenzaldehyde was heated with stirring. in steps A-D, 0.62 g, 0.0029 moles of 4,6-dimethoxy-2-methylsulfonylpyrimidine, prepared in steps E-G of Example 1 and 0.36 g, 0.0029 moles of carbonate potassium in DMF (15 ml) at 85 ° C for 4 hours. After this time, the reaction mixture was poured into 100 mL of water and then extracted with 50 mL. ethyl acetate. The organic layer was dried over magnesium sulfate and then filtered. Filtrate 21

was evaporated under reduced pressure to give 2- (4,6-di-methoxypyrimidin-2-ylthio) -6-phenylbenzaldehyde

Step F Synthesis of 2- (4,6-dimethoxypyrimidin-2-ylthio) -6-phenylbenzoic acid To a stirred solution of 0.56 g, 0.0016 mol 2- (4,6-di-methoxypyrimidin-2-ylthio) Of 6-phenylbenzaldehyde in 15 ml of acetone is added a solution of 0.26 g, 0.0016 mol of permanganate and 0.22 g, 0.16 mol of sodium phosphate in the form of heptahydrate in 10 ml of water. After the addition was complete, the reaction mixture was stirred for 6 hours, then 1 ml of an aqueous solution saturated with sodium thiosulphate was added and the mixture was filtered through a pad of diatomaceous earth. The filtrate was filtered once more and then evaporated under reduced pressure to remove the acetone. The concentrate was diluted with 50 mL of water and then extracted with 2 x 50 mL of ethyl acetate. The aqueous layer was acidified to pH 3 with 10% aqueous hydrochloric acid and then extracted again with 3 x 75 mL of ethyl acetate. The extracts were combined and evaporated under reduced pressure to give 2- (4,6-dimethoxypyrimidin-2-ylthio) -6-phenylbenzoic acid. Example 4

Synthesis of 6-phenyl-2- (4,6-diraethoxypyrimidin-2-yloxy) benzoic acid

Step A: Synthesis of 2-ethoxycarbonyl-3 "phenylcyclohex-5-enone as intermediate In a nitrogen atmosphere, 0.1 g, 0.004 mol of sodium metal is reacted with 40 ml of ethanol. The solution is stirred and 13.0 g (0.100 mol) of ethyl acetoacetate are added. The reaction mixture is cooled in an ice bath and a solution of 13.2 g, 0.100 mol of trans-cinnamic aldehyde in 10 ml of ethanol is added dropwise over 10 minutes. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 18 hours.

The mixture was then saturated with hydrogen chloride gas and allowed to stand for 65 hours. The mixture was evaporated under reduced pressure to give 2-ethoxycarbonyl-3-phenyl-cyclohex-5-enone (24.4 g, 100%).

The reaction is repeated, replacing sodium metal with the sodium salt of ethyl acetoacetate. Thus, 12.6 g (0.097 mol) of ethyl acetoacetate, 0.5 g, 0.003 mol of sodium acetoacetate and 13.2 g, 0.100 mol of trans-cinnamic aldehyde are reacted in 50 ml of ethanol. 2-Ethoxycarbonyl-3-phenylcyclohex-5-enone (24.4 g) is recovered in 100% yield.

Step B: Synthesis of ethyl 6-phenylsalicylate intermediate Under a nitrogen atmosphere, a solution of 24.4 g, 0.100 mole of crude 2-ethoxycarbonyl-3-phenylcyclohex-5-enone in 50 mL of carbon tetrachloride in an ice bath was cooled and then stirred for 1 hour. A solution of 16.1 g, 0.100 mol of bromine in 50 ml of acetic acid is added dropwise. After the addition is complete, the reaction mixture is stirred in an ice bath for 30 minutes and then refluxed for 21 hours. The reaction mixture was cooled and stirred with 80 mL of methylene chloride and 80 mL of water. The layers were separated and the organic layer was washed with two portions of water and one portion of saturated aqueous sodium bicarbonate solution. The organic layer was dried over sodium sulfate and magnesium sulfate and then filtered. The filtrate was evaporated under reduced pressure to give a residue which was chromatographed on a silica gel column. A 2: 1 mixture of heptane and methylene chloride was used as eluent. Appropriate fractions were collected and evaporated under reduced pressure to give 7.1 g of ethyl 6-phenylsalicylate. The NMR spectrum was consistent with the proposed structure. - 23 -

Step C: Synthesis of 6-Phenylsalicylic Acid to the Intermediate To a stirred solution of 3.3 g (0.014 mol) of ethyl 6-phenylsilyllate in 30 mL of ethanol was added a catalytic amount of 1,4,7,10,13,16-hexaoxacyclooctadecane. A solution of 2.0 g, 0.030 mole of 85% potassium hydroxide in water was then added. After the addition was complete, the reaction mixture was heated to reflux and stirred for 4 hours. The reaction mixture was allowed to cool to room temperature and allowed to stand for 18 hours. The mixture was heated to reflux again and stirred for 4 hours. Thin layer chromatography can then be shown to terminate the lignite reaction. Potassium hydroxide (0.3 g, 85%) was added to the reaction mixture and then refluxed for 3 hours. The reaction mixture was cooled and the volatiles removed under reduced pressure. The aqueous concentrate was washed with two portions of diethyl ether, the diethyl ether extracts washed again, water used for washing and the aqueous concentrate was combined and acidified to pH 1 with concentrated hydrochloric acid. The mixture was extracted with three portions of ethyl acetate. The ethyl acetate extracts were combined, dried over magnesium sulfate, and filtered. The filtrate is evaporated under reduced pressure to a residue which is dissolved in hot ethanol and the solution decolourised with charcoal. The mixture was filtered through diatomaceous earth and the filtrate was evaporated under reduced pressure to give a residue. This residue was recrystallized from diethyl ether and hexane to give the .alpha.-phenylsalicylic acid, m.p. 143-146 ° C. After crystallization, the filtrate was evaporated under reduced pressure to give a solid which was combined with the previously obtained 6-phenylsalicylic acid to give a total of 2.8 g of this acid, m.p. 143-146 ° C. 24 -

Step D: Synthesis of 6-phenyl-2- (4,6-dimethoxy-pyrimidin-2-yloxy) -benzoic acid Under a nitrogen atmosphere, a mixture of 0.25 g, 0.0052 mol 50 to 6056 sodium hydride is cooled with stirring. in mineral oil in 60 ml of tetrahydrofuran in an ice bath, while 0.54 g, 0.0025 mol of 6-phenylsalicylic acid is added. The reaction mixture was stirred for 5 minutes and then 0.55 g (0.0025 mol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine was added. After the addition was complete, the ice bath was removed and the reaction mixture stirred for 50 minutes. Thin layer chromatography at this time showed that the reaction was more than 90%.

Then the reaction mixture is mixed with another reaction mixture containing the reaction product after reaction of 1.73 g, 0.0079 mol of 6-phenylsalicylic acid, 1.70 g, 0.0079 mol of 4.6-dimethoxy-2-methylsulfonylpyrimidine and 0.78 g 0.016 mol 50-60% sodium hydride in mineral oil in 120 ml tetrahydrofuran. The mixture was dissolved in water and the solution was washed with diethyl ether. The aqueous layer was acidified to pH 2 with 1N aqueous hydrochloric acid. The mixture was extracted with ethyl acetate, the extracts were combined, dried over magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give a foamy residue which was dissolved in diethyl ether and extracted with two portions of saturated aqueous sodium bicarbonate solution. The extracts were combined, acidified to pH 2 with a 6N aqueous hydrochloric acid solution and extracted with three portions of ethyl acetate. The extracts are combined, dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue which was recrystallized from methylene chloride / hexane to give 1.74 g of 6-phenyl-2- (4,6-dimethoxypyrimidin-2-yloxy) benzoic acid. The NMR spectrum of this material was consistent with the proposed structure. Example 5

Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (4-nitrophenyl) benzoic acid (Compound 27)

Step Synthesis of 2-ethoxycarbonyl-3- (4-nitrophenyl) -cyclo-5-enane (II) The stirred solution of 6.8 g, 0.052 mol of ethyl acetoacetate and 0.24 g, 0.002 mol of sodium ethyl acetoacetate in a small amount of ethanol is cooled in an ice bath. and over 20 minutes, a suspension of 9.5 g (0.054 mol) of 4-nitrosoic acid aldehyde in 100 ml of ethanol. After the addition was complete, the reaction mixture was allowed to warm to room temperature and then stirred at this temperature for 18 hours in a nitrogen atmosphere. The reaction mixture was then cooled with stirring on an ice bath and saturated with hydrogen chloride gas. The mixture was allowed to warm to room temperature and left to stand for 60 hours at this temperature. Then the mixture was evaporated under reduced pressure to give 15.5 g of 2-ethoxycarbonyl-3- (4-nitrophenyl) cyclohex-5-enone. The product is used without further purification.

Step B: Synthesis of Ethyl 6- (4-Nitrophenyl) Salicylate as a Intermediate A stirred solution of 15.5 g, 0.054 little 2-ethoxycarbonyl-3- (4-nitrophenyl) cyclohex-5-enone in 40 mL carbon tetrachloride is cooled in an ice bath. A solution of 2.8 mL of 0.054 mol of bromine in 40 mL of acetic acid was added in one portion. After the addition is complete, the reaction mixture is cooled for a further 40 minutes and then refluxed for 18 hours. After this time, the reaction mixture was cooled to room temperature, 45 ml of water, 45 ml of carbon tetrachloride and 45 ml of methylene chloride were added. The organic layer was separated, washed with two portions of water and one portion of saturated aqueous sodium bicarbonate solution. The mixture was filtered and the filtrate was evaporated under reduced pressure to give 16.4 g of ethyl 6- (4-nitro-phenyl) salicylate.

Note: Steps A and B of this example were performed according to Heuser and Pogany.

Step C: Synthesis of 6- (4-nitrophenyl) salicylic acid as an intermediate To a warm, stirred solution of 6.9 g (0.029 mol) of ethyl 6- (4-nitrophenyl) salicylate in 100 mL of ethanol was added a solution of 4.8 g, 0.072 mol of 85¾ potassium hydroxide in 50 ml. After the addition is complete, the reaction mixture is heated to reflux for about 16 hours. After this time, the ethanol was removed under reduced pressure. The aqueous concentrate was washed with diethyl ether and then acidified to pH 1 by addition of a 6N aqueous hydrochloric acid solution. The mixture is extracted with one portion of ethyl acetate. Separation of the aqueous and organic layers was incomplete. The mixture was passed through a layer of diatomaceous earth to separate the two layers. The organic layer was discarded and the aqueous layer was extracted with two portions of ethyl acetate. The extracts were combined, dried with magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to a solid residue which was recrystallized from diethyl ether / pentane to give 4.2 g of 6- (4-nitrophenyl) salicylic acid, m.p. The NMR spectrum was consistent with the expected structure.

Step P: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (4-nitrophenyl) benzoic acid (Compound 27)

Under a nitrogen atmosphere, a suspension of 1.4 g (0.028 mol) of 60% sodium hydride in mineral oil is stirred in 200 ml of THF (27 ml), while 3.7 g (0.014 mol) of 6- (4-nitrophenyl) salicylic acid are added. in THF. After the addition was complete, the reaction mixture was stirred for 5 minutes, then cooled in a water bath and crushed ice and a solution of 3.2 g, 0.015 mol of 4,6-dimethoxy-2-methylsulfonylpyrimidine prepared according to Example 1, steps E to G in 5 ml of tetrahydrofuran.

After the addition was complete, the reaction mixture was allowed to slowly warm to room temperature and then stirred for 18 hours. Thin layer chromatography showed a small amount of salicylic acid as an intermediate. 4.6-dimethoxy-2-methylsulfonylpyrimidine (0.25 g, 0.001 mol) was added, followed by tetrahylamine (15 ml). oiurs. Then it rea '. The mixture was heated to 35 ° C and stirred at this temperature for 2 hours. After this time, thin layer chromatography still shows the presence of salicylic acid as an intermediate. A catalytic amount of 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) was added and the mixture was heated at 35 ° C for 3 hours. After this time, the reaction mixture was evaporated under reduced pressure, the residue was dissolved in water and the solution was washed with two portions of ethyl acetate.

The aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and extracted with two portions of ethyl acetate. The extracts were combined, dried over magnesium sulfate, and filtered. The filtrate is evaporated under reduced pressure to a solid evaporator which is triturated with ethanol and washed with pentane.

The still impure solid was then recrystallized from ethanol to give 1.5 g of 2- (4,6-dimethoxy-pyrimidin-2-yloxy) -6- (4-nitrophenyl) -benzoic acid at room temperature. mp 150.5 ° C. The NMR spectrum of this material was consistent with the proposed structure. 28 Example 6

Synthesis of 2- (4,6-Dimethoxypyrimidin-2-yloxy) - O - (2,4,6-trimethylphenyl) benzoic acid (Compound 49)

Step A: Synthesis of 2- (2,6-difluorophenyl) -4,5-dihydro-4,4-dimethyloxazole as an Intermediate Mixed solution of 25.2 g, 0.283 mol 2-amino-2-methyl-1-propane in 83 ml of anhydrous methylene chloride was cooled with a water bath and crushed ice, and then a solution of 5.0 g, 0.142 mol of 2,6-difluorobenzyl chloride in 83 ml of anhydrous methylene chloride was added dropwise so that the temperature of the reaction mixture did not exceed 15 ° C. After the addition was complete, the reaction mixture was allowed to warm to room temperature for about 30 minutes and stirred at this temperature for 18 hours. After this time, the reaction mixture was washed with water and then with saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and then filtered. The filtrates were evaporated under reduced pressure to give 31.2 g of a white solid. Thionyl chloride (55.6 g, 0.467 mol) was added dropwise to this solid with stirring. The mixture was heated until a homogeneous mixture was obtained, which was stirred for 45 minutes and then poured into 150 ml of vigorously stirred diethyl ether. The diethyl ether is then decanted from the resulting solid which is then dissolved in water and the solution is neutralized with a 10% aqueous sodium hydroxide solution. The mixture was extracted with diethyl ether, the ether extracts were washed with saturated aqueous sodium chloride solution and then dried over magnesium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure to give a total of 25.3 g of 2- (2,6-difluorophenyl) -4,5-dihydro-4,4-dimethyloxazole. - 29 -

Step B: Synthesis of 2- [2-fluoro-6- (2,4,6-trimethyl-phenyl) -phenyl] -4,5-dihydro-4,4-dimethyloxazole as a Substitute. 10 mole of 2-mesitylmagnesium bromide (1.0 M tetrahydrofuran solution) in 200 mL of tetrahydrofuran and a solution of 17-6 g, 0.08 mole of 2- (2,6-difluorophenyl) -4 was added dropwise over 15 minutes. Of 6-dihydro-4,4-dimethyloxazole in 200 ml of tetrahydrofuran. After the addition is complete, the reaction mixture is heated to room temperature overnight; with a reflux condenser. After this time, the mixture is poured into water. The mixture was mixed. it is digested with diethyl ether and the extract is washed with saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 26.0 g of 2- [2-fluoro-6- (2,4,6-trimethylphenyl) phenyl] -4,5-dihydro-4,4-dimethyloxazole. The NMR spectrum is consistent with the proposed structure.

Step C: Synthesis of 2- [2-fluoro-6- (2,4,6-trimethylphenyl) phenyl] -4,5-dihydro-3,4,4-trimethyloxazolium iodide as an intermediate Mixed solution 10.0 g, 0.032 mol 2- [2-fluoro-6- (2,4,6-trimethylphenyl) phenyl] -4,5-dihydro-4,4-dimethyl-oxazole and 36.5 g, 0.257 mol of methyl iodide in 65 ml of nitro-methane is refluxed for 26 hours under reflux. After this time, the reaction mixture was concentrated to about 15 ml under reduced pressure and poured into 200 ml of cold diethyl ether with stirring. The resulting solid was filtered, washed with diethyl ether and dried to give 12.6 g of 2- (2-fluoro-6- (2,4,6-trimethylphenyl) phenyl) -4,5-dihydro-3,4,4 -trimethyloxazolium iodide. The NMR spectrum is consistent with the proposed structure. - 30 -

Step D: Synthesis of 2-fluoro-6- (2,4,6-trimethylphenyl) -benzaldehyde as an intermediate 9.0 g, 0.02 mol 2- [2-fluoro-6- (2,4,6-trimethylphenyl) phenyl] -4,5-dihydro-3,4,4-trimethyloxazolium iodide was completely dissolved in 52 ml of ethanol, and 1.1 g (0.03 mol) of sodium borohydride was carefully added with stirring over 10 minutes.

After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours. After this time, 166 mL of 3N aqueous hydrochloric acid solution was added slowly. After the addition was complete, the reaction mixture was heated to 110 ° C and stirred at this temperature for 2 hours. Then the mixture was cooled, diluted with water. and extracted with diethyl ether. The extract was washed with water and then saturated aqueous sodium chloride solution. The extract was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give 3.7 g of 2-fluoro-6- (2,4,6-trimethylphenyl) benzaldehyde. The NMR spectrum was consistent with the proposed structure.

Step E: Synthesis of 6, (2,4,6-trimethylphenyl) salicylaldehyde as an intermediate 3.0 g, 0.012 mol of 2-fluoro-6- (2,4,6-trimethylphenyl) -benzaldehyde is completely dissolved in 30 ml of tetrahydrofuran and then with stirring, 0.4 g of tetrabutylammonium bromide is added as a catalyst. The reaction mixture was then cooled in a bath with ice and ice (1.0 g, 0.025 mol) was added. After the addition was complete, the reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into water, acidified with concentrated hydrochloric acid and then extracted with diethyl ether. The ether extract is washed with water and then with a saturated aqueous sodium chloride solution. The extract was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue. This residue was subjected to silica gel column chromatography. The eluent was 5: 95 ethyl acetate / hexane. . The appropriate fractions were combined and evaporated to dryness under reduced pressure to give 0.4 g of 4- (2,4,6-trimethylphenyl) salicylaldehyde. The N-R spectrum was consistent with the proposed structure. The reaction was repeated once more in order to obtain a sufficient amount of the resulting reaction product.

Step F: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (2,4,6-trimethylphenyl) benzaldehyde as a product

This s'xou‘-3nina can be obtained. in a similar manner to Example 1, step H using 1.3 g, 0.005 mol of 6- (2,4,6-trimethylphenyl) salicylaldehyde, 1.2 g, 0.005 mol of 4,6-dimethoxy-2-methylsulfonylpyrimidine prepared according to Example 1 , steps E to G and 0.8 g, 0.006 moles of potassium carbonate in 8.5 ml of dimethylformamide. The crude product is triturated with diethyl ether and then chromatographed on a silica gel column. A 1: 2 mixture of ethyl acetate and hexane was used as eluent. The product fractions were combined and evaporated under reduced pressure to give 1.4 g of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (2,4,6-trimethylphenyl) benzaldehyde, m.p. 146-147 ° C. The NMR spectrum is consistent with the proposed structure.

Step G: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (2,4,6-trimethylphenyl) benzoic acid (Compound 49)

This material can be prepared analogously to Example 1, Step I using 1.3 g, 0.003 mol of 2- (4,6-dimethyl-pyrimidin-2-yloxy) -6- (2,4,6-trimethyl-phenyl) -benzaldehyde Sodium phosphate, 0.8 g, 0.005 mole of sodium phosphate heptohydrate in 22.5 ml of water and 39 ml of acetone. The reaction mixture is filtered through diatomaceous earth. The filtrate is acidified with concentrated hydrochloric acid. 32-2 when extracted with methylene chloride. The extract was washed with an aqueous solution, saturated sodium chloride, and then dried over sodium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure. The residue obtained is chromatographed on a silica gel column. Ethyl acetate / hexane (1: 3a) and then methanol / methylene chloride (2: 9) were used as eluents. The product fractions were combined and evaporated under reduced pressure to give 0.3 g of acid 2- (4.6). dimethoxypyrimidin-2-yloxy) -6- (2,4,6-trimethylphenyl) benzoic acid; The NMR spectrum is consistent with the proposed structure. Example 7

Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (pyridin-4-yl) benzoic acid (Compound Yo)

Step A: Synthesis of 3- (pyridin-4-yl) propenone as an intermediate. A solution of 20.0 g, 0.187 mol of 4-pyridinecarboxaldehyde and 56.8 g, 0.187 mol of formyl methylentrifenylphosphorane in 350 ml of toluene was heated under a nitrogen atmosphere for one hour at room temperature. under reflux. After this time, the reaction mixture was cooled and evaporated under reduced pressure. The concentrate is dissolved in diethyl ether and the solution is stored in a freezer. After cooling, the solution is filtered and the filtrate is concentrated under reduced pressure. The concentrate was evaporated under high vacuum to give 28.7 g of material, the theoretical yield was 24.9 g. The concentrate was stored in the freezer for 18 hours and then redissolved in diethyl ether. Pentane was added to the solution until an oily material precipitated out of the solution. The mixture was stirred while cooling in an acetone / dry ice bath. The resulting solid was filtered to give 3- (pyridin-4-yl) propenal (22.3 g), m.p. The NMR spectrum is consistent with the proposed structure. - 33 -

Step B: Synthesis of 2-ethoxycarbonyl-3- (pyridin-4-yl) -cyclohex-5-enone as an intermediate

The product can be obtained in a manner similar to Example 5, Step A using 21.8 g, 0.163 mol of 3- (pyridin-4-yl) propenal, 20.6 g, 0.158 mol of ethyl acetoacetate and 0.8 g, 0.005. mole of the sodium salt of ethyl acetate in 60 ml of ethanol. Chloride gas was bubbled through the mixture and then the reaction mixture was stirred at room temperature for 18 hours. 2-Ethoxycarbonyl-3- (pyridin-4-yl) cyclohex-5-enone (38.6 g) is obtained. The product is free of further purification.

Step C: Synthesis of ethyl 6- (pyridin-4-yl) salicylate as the intermediate

This material can be obtained in a similar manner to Example 5, Step B, using 38.6 g, 0.158 mol of 2-ethoxycarbonyl-3- (pyridin-4-yl) cyclohex-5-enone, 8.5 ml, 0.160 mol of bromine, 110 ml of acetic acid and 110 ml of tetrachloromethane. The residue is chromatographed on silica gel. The eluent was first methylene chloride and then 5% methanol in methylene chloride. The product fractions were combined and evaporated under reduced pressure. The residue was triturated with hot methanol and the resulting solid was filtered to give 4.8 g of ethyl 6- (pyridin-4-yl) salicylate with a melting point of 169.5-172 ° C. structure.

Step D: Synthesis of phenylmethyl-6- (pyridin-4-yl) salicylate as an intermediate A mixture of 1.4 g, 0.006 mol of ethyl 6- (pyridin-4-yl) salicylate, 6.2 g, was heated under stirring under stirring. 0.057 moles of phenylmethanol, 0.2 g, 0.001 moles of isopropoxiditanate and 10 g of molecular sieve 4A (beads) in 100 ml of tetrahydrofuran are refluxed for 30 hours. After this time, the reaction mixture was filtered through a 34 layer diatomaceous earth. The filter cake was washed with tetrahydrofuran, the filtrate and washings were combined and evaporated under reduced pressure to an oil.

This liquid was combined with a similar product from the previous reaction in which 0.002 mol of salicylate was used and the product was chromatographed on a silica gel column. The eluent used was a mixture of ethyl acetate and hexane at a concentration of 20 to 100% ethyl acetate. The product fractions were combined and evaporated under reduced pressure to yield 1.5 g of phenylmethyl 6- (pyridin-4-yl) salicylate by step mp 170-172.5 ° C. The NMR spectrum was consistent with the proposed structure.

Step E: Synthesis of phenylmethyl 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (pyridin-4-yl) benzoate as intermediate product (Compound 106) 0.10 g is stirred under nitrogen. 0.002mol 60 & sodium hydride in mineral oil in 8 ml of dimethylformamide, and a solution of 0.65 g, 0.002 mol of phenylmethyl-6- (pyridin-4-yl) salicylate in 4 ml of dimethylformamide is added. The reaction mixture was stirred for 5 minutes while adding a solution of 0.49 g (0.002 mol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine prepared in Example 1, step E to G in 3 ml of dimethylformamide. After this time, the reaction mixture was heated to 80 ° C and stirred at this temperature for 1.5 hours. The mixture was cooled, water was added and the resulting mixture was extracted with three portions of ethyl acetate. The combined extracts were washed with water and then with saturated aqueous sodium chloride solution, and the organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to an oily residue which was crystallized from a diethyl ether. The resulting solid was filtered off and washed with hexane. The solid was dried to give 0.69 g of phenylmethyl 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (pyridin-4-yl) benzoate, m.p. 115-117 ° C. the spectrum is consistent with the proposed structure. 35 -

Step F: Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (pyridin-4-yl) benzoic Acid (Compound 36) Under a nitrogen atmosphere, 0.04 g of 10% palladium carbonate is stirred as the catalyst in 30 ml of methanol and 0.42 g (0.001 mol) of phenylmethyl 2- (4,6-dimethoxy-pyrimidin-2-yloxy) -6- (pyridin-4-yl) -benzoate are added. The reaction vessel was evacuated and re-filled with nitrogen. Finally, a nitrogen-filled flask is attached to the syringe and the syringe is passed through a septum overlapping the neck of the reaction vessel. The reaction mixture is stirred in this hydrogen atmosphere. The sample of the reaction mixture is analyzed by thin layer chromatography to demonstrate that the reaction is complete. The reaction vessel is again pumped and washed several times with nitrogen. The reaction mixture was filtered through a pad of diatomaceous earth and the filtrate was evaporated under reduced pressure to an oil. This product is crystallized from carbon tetrachloride. The solid obtained is triturated with a mixture of carbon tetrachloride and hexane. The solid was filtered and dried to give 0.11 g of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- (pyridin-4-yl) benzoic acid. The NMR spectrum is consistent with the proposed structure. Example 8

Synthesis of 2- (4,6-dimethoxy-1,3,5-triazin-2-yloxy) -6- (4-chloro-phenyl) -benzoic acid (Compound 113)

Step A: Synthesis of 4-chlorocinnamic aldehyde as an intermediate. A stirred solution of 4-chlorobenzaldehyde (20.0 g, 0.142 mol) and 52.0 g (0.171 mol) of formylmethylene triphenylphosphane in 215 mL of acetonitrile was heated at 60 ° C for 18 h. Then the reaction mixture was cooled and 50 g of silica gel was added. The acetonitrile was evaporated under reduced pressure - 36 -

The silica gel reaction mixture was applied to a top silica gel column, eluting with ethyl acetate / hexane (1: 2). The product fractions were combined and evaporated under reduced pressure to an oil, which was crystallized from ethyl acetate and hexane. hexane in a ratio of 1: 6 to give 11.8 g of 4-chlorocinic aldehyde with a melting point of 51 to 56 ° C. The NMR spectrum was consistent with the proposed structure.

Step B: Synthesis of 2-ethoxycarbonyl-3- (4-chlorophenyl) -cyclobox-5-ene as intermediate

This compound was prepared in analogy to Example 5, Step A, using 11.3 g, 0.071 mol of 4-chlorocinnamaldehyde, 9.0 g, 0.069 mol of ethyl acetoacetate and 0.3 g, 0.002 mol of sodium ethyl acetoacetate in 26 ml of ethanol. The crude reaction mixture was evaporated under reduced pressure, the residue dissolved in diethyl ether, washed with water and then with saturated aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give 20.6 g of material containing 50% pure 2-ethoxycarbonyl 3- (4-chlorophenyl) cyclohex-5-enone.

Step C: Synthesis of ethyl 6- (4-chlorophenyl) salicylate as the intermediate To a stirred solution of 20.0 g, 0.036 mol 50% 2-ethoxycarbonyl-3- (4-chlorophenyl) cyclohex-5-enone in 100 mL toluene was added 8 1 g, 0.36 mole of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. After the addition is complete, the reaction mixture is warmed to 0 ° C to 85 ° C and stirred at this temperature for 18 hours. The mixture was cooled and diethyl ether (200 mL) was added. The solution was washed with water (3 x 200 mL) and then with a saturated aqueous sodium chloride solution. - 37 -

The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue which was chromatographed on a silica gel column. Wash the column with a 1: 4 mixture of ethyl acetate and hexane. The product fractions were combined and evaporated under reduced pressure to a residue. The NMR spectrum of the residue showed that the product had a purity of 80%. The residue is therefore subjected to a second chromatography on a silica gel column. Ethyl acetate / hexane (7.5: 92.5) was used as eluent. The product fractions were combined and evaporated under reduced pressure to give 0.8 g of ethyl 6- (4-chlorophenyl) salicylate with temperature. t: '' 1 to 54 ° r

Step D: Synthesis of 6- (4-chlorophenyl) salicylic acid as an intermediate

This compound can be obtained analogously to Example 5, Step C using 0.80 g, 0.003 mol of ethyl 6- (4-chlorophenyl) salicylate and 0.57 g, 0.009 mol of 85% potassium hydroxide in 6.6. ml of ethanol and 12.1 ml of water. 0.73 g of 6- (4-chlorophenyl) salicylic acid is obtained.

Step E: Synthesis of phenylmethyl 6- (4-chlorophenyl) salicylate as an intermediate 7 under nitrogen with a solution of 0.68 g, 0.003 mol of 6- (4-chlorophenyl) salicylic acid in 17 ml of dimethylformamide while adding 0.11 g, 0.003 mole of 60% sodium hydride in mineral oil. After the addition was complete, the reaction mixture was stirred for 30 minutes and then 0.35 g (0.003 mol) of phenylmethyl chloride was added followed by 0.41 g (0.003 mol) of sodium iodide. After the addition is complete, the reaction mixture is stirred for a further 4 hours and then poured into a 1N aqueous hydrochloric acid solution. The mixture was extracted with diethyl ether. The extract was washed with water and then with a saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to an oil which was subjected to silica gel chromatography. A 5: 95 mixture of ethyl acetate in hexane was used as eluent. The product fractions were combined and evaporated under reduced pressure to give 0.56 g of phenylmethyl 6- (4-chlorophenyl) salicylate The NMR spectrum is consistent with the proposed structure.

Step F: Synthesis of 2-chloro-4,6-diethoxyethoxy-1,3,5 "triazine as an intermediate To a stirred solution of 45.0 g of methanol and 5.0 µg of water with 16.8 g, 0.20 mol of sodium bicarbonate. and 18.5 g, 0.1 moles of cyanogen chloride, while the temperature of the reaction mixture was raised to 35 DEG C. and the carbon dioxide was released, and after slowing the gas evolution, the reaction mixture was heated to reflux for 30 minutes. The mixture was cooled and the solid was filtered off, washed several times with water and then dried to give 13.0 g of 2-chloro-4,6-dimethoxy-1,3,5-triazine, m.p. C. After recrystallization of the solid of heptane, the melting point is 75-76 ° C.

Step C: Synthesis of phenylmethyl 2- (4,6-dimethoxy-1,3,5-triazin-2-yloxy) -6- (4-chlorophenyl) benzoate as intermediate

This compound can be obtained analogously to Example 7, step E using 0.55 g, 0.002 mol of phenylmethyl-6- (4-chlorophenyl) salicylate, 0.28 g, 0.002 mol of 2-chloro-4,6-dimethoxy-1, 3,5-triazine and 0.06 g, 0.002 mol of 60 µl sodium hydride in mineral oil in 5.1 ml dimethylformamide. After the addition was complete, the reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with a 1N aqueous hydrochloric acid solution, water and a saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to an oil. The product fractions were combined and evaporated under reduced pressure to give 0.63 g of phenylmethyl-2- (4-methyl-hexane). 6-dimethoxy-1,3,5-triazin-2-yloxy) -6- (4-chlorophenyl-benzoate. NMR spectrum is consistent with the proposed structure).

Step H: Synthesis of 2- (4,6-dimethoxy-1,3,5-triazin-2-yloxy) -6- (4-chlorophenyl) -benzoic acid (Compound 113)

A solution of 0.63 g, 0.001 mol of phenylmethyl 2- (4,6-dimethoxy-1,3,5-iriazin-2-yloxy) -6- (4-chlorophenyl) benzoate in 14 ml of acetic acid and 48 ml of ethanol is placed in Parr's 250 ml hydrogenation apparatus along with 0.02 g of 10% palladium on charcoal. The mixture was hydrogenated in a Parr apparatus. After the theoretical amount of hydrogen was fed, the reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was washed with methylene chloride, and the ethanol-acetic acid layer was evaporated under reduced pressure to remove the ethanol. The concentrate was then shaken with a mixture of water and ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The mixture was filtered and the filtrate was evaporated under reduced pressure to give 0.43 g of 2- (4,6-dimethoxy-1,3,5-triazin-2-yloxy) -6- (4-chlorophenyl) benzoic acid. The NKR spectrum was in line with the proposed structure. 40 - Example 9

Synthesis of isopropylideneamino-2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoate (Compound 90)

Step A: Synthesis of 4-nitrophenyl-2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoate intermediate A stirred solution of 1.0 g, 0.003 mol of 2- (4,6-dimethoxypyrimidine) under nitrogen was stirred. -2-yloxy) -6-phenyl-benzoic acid, prepared according to Example 1, in 30 ml of methylene chloride, cooled to 0 ° C, and 0.3 g, 0.003 mol of 4-nitrophenol is added simultaneously. After dissolving the phenol, 0.6 g of 0.003 mol of dicyclohexylcarbodiimide (DCC) are added. After the addition was complete, the reaction mixture was stirred at 0 ° C for 1 hour and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was filtered and the filtrate was washed with fresh methylene chloride. The filtrate and washings were combined and evaporated under reduced pressure. The residue was dissolved in diethyl ether and the solution was filtered. The filtrate was evaporated under reduced pressure to give 1,4 g of 4-nitrophenyl-2- (4,6-dimethoxypyrimidin-2-yloxy). ) -6-phenyl-benzoate. The NMR spectrum is consistent with the intended structure.

Step B: Synthesis of isopropylideneamino-2- (4,6-dimethoxy-pyrimidin-2-yloxy) -6-phenyl-benzoate (Compound 90) Under a nitrogen atmosphere, a stirred solution of 1.4 g, 0.003 mol of 4-nitrophenyl-2- (4 , 6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoate, 0.3 g, 0.004 mol acetonoxime and 0.8 g, 0.006 mol potassium carbonate in 55 ml acetonitrile are refluxed for 1.5 hours under reflux cooler. After this time, the mixture was cooled to room temperature and filtered through a short pad of silica gel. The filter cake was washed with ethyl acetate. The filtrate and washings were combined and evaporated under reduced pressure. The residue is chromatographed on a silica gel column. A 1: 1 mixture of ethyl acetate and heptane was used as eluent. The product fractions were combined and evaporated under reduced pressure, the residue was dissolved in ethyl acetate and the solution was washed with 5% aqueous potassium hydroxide solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.3 g of isopropylideneamino-2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoate. The NMR spectrum is consistent with the expected one, dr. Example 10

Synthesis of Propin-2-yl-2- (4,6-dimethoxypyrimidin-2-yloxy) -o-phenylbenzoate (Compound 78) A solution of 0.38 g, 0.001 mol of 2- (4,6 dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid (Compound 1, prepared according to Example 5) and 0.22 g, 0.002 mol of potassium bicarbonate in 15 ml of dimethylformamide at 85 ° C and stirred for 1 hour. At this time, a catalytic amount of potassium iodide and 0.19 g, 0.002 mole of a solution of 30% propin-2-yl bromide in toluene were added. After the addition is complete, the reaction mixture is stirred at 85 DEG C. for 1 hour, cooled and diluted aqueous hydrochloric acid is added with vigorous stirring.

The mixture was extracted with ethyl acetate, the extract was washed with a saturated aqueous sodium chloride solution, the organic layer was dried over magnesium sulfate and filtered through a short pad of silica gel. The column is washed with ethyl acetate. Washing material and extract were combined and evaporated under reduced pressure to give 0.32 g of propin-2-yl-2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoate. The NMR spectrum is consistent with the proposed structure. 42 - Example 11

Synthesis of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid ammonium salt (Compound 106)

Solution. 0.57 g, 0.002 mol of 2- (4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid, 0.2 g of ammonium hydroxide, 5 ml of ethanol and 5 ml of tetrahydrofuran are stirred in a sealed container for 16 hours. The solid was filtered off and washed with a small amount of acetone to give 0.18 gamma salt of 2- (4} 6-dimethoxypyrimidin-2-yl, 1H) -6-phenylbenzoic acid, m.p. ° C. NMR-sprinter is consistent with the proposed structure. A few drops of ammonium hydroxide are added to the filtrate and the mixture is evaporated under reduced pressure to a solid residue which is recrystallized from acetone / heptane to give 1.10 g of 2- (4,6-dimethoxypyrimidine-2-ammonium salt). yloxy) -6-phenylbenzoate, m.p. 147-151 ° C. The NMR spectrum is consistent with the intended product. Both fractions were pooled. Example 12

Synthesis of 2- (5-chloro-4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid (Compound 62)

Step A: Synthesis of 5-chloro-4,6-dimethoxy-2-methylsulfonyl-pyrimidine intermediate Under a nitrogen atmosphere, a solution of 9.7 g, 0.045 moles of 4,6-dimethoxy-2-methylsulfonylpyrimidine and 6 N-chlorosuccinimide, 0 g, 0.045 mole in 25 ml of glacial acetic acid at 95-100 ° C for 3 hours. The mixture was allowed to cool to room temperature and stirred for 18 hours. Neat layer chromatography showed that the reaction was not complete - 43 -

The reaction mixture was then heated at 80 ° C for 1.5 hours, then at 90 to 95 ° C for 1 hour and then at 115 ° C for 1.3 hours. After this time, the reaction mixture was poured into a mixture of water and ice-water. The resulting solid was filtered off and washed with water. The resulting dried solid was chromatographed on silica gel column. The eluent was 3: 1 ethyl acetate / heptane. The product fractions were combined and evaporated under reduced pressure to yield 3.8 g of 5-chloro-4,6-dimethoxy-2-methylsulfonylpyrimidine, m.p. to 185 ° C. The NMR spectrum is consistent with the proposed structure.

Step B: Synthesis of 2- (5-chloro-4,6-dimethoxy-pyrimidin-2-yloxy) -6-phenyl-benzoic acid (Compound 62)

This compound can be prepared analogously to Example 5, Step D using 0.50 g, 0.002 mole of 6-phenylsalicylic acid prepared as described in Example 4, steps A to C, 0.89 g, 0.004 mole of 5-chloro- -4,6-dimethoxy-2-methylsulphonylpyrimidine and 0.18 g, 0.006 mol of 80% sodium hydride in 60 ml of tetrahydrofuran. After the addition was complete, the reaction mixture was evaporated under reduced pressure and the residue was dissolved in 70 mL of water and washed with ethyl acetate (3 x 50 mL). The aqueous layer was acidified with 20 mL of 1N aqueous hydrochloric acid. The mixture was extracted with ethyl acetate (3 x 50 mL). The extracts were combined, dried over magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure and the residue was washed with pentane to give 0.84 g of 2- (5-chloro-4,6-dimethoxypyrimidin-2-yloxy) -6-phenylbenzoic acid. The NMP-spectrum is consistent with the proposed structure. 44 -

Herbicidal efficacy

The herbicidal activity of the compounds of general formula (Ib) is examined on the following plants:

Abutilcn theophrastiAlopecurus myosuroidesIpomea lasunosaSetaria viridisSorghum halopenseStellaria mediaXa nthi ': pensy 1 vanicum Preparation of experimental areas cloudfish foxtail foxtail foxtail bark beetle chickweed bunch In the case of pre-emergence, two flat disposable bowls with δ x 15 x 25 cm depth 6 are filled 5 cm light sandy soil, steam sterilized. The soil is leveled, compressed, and there are 6 equally spaced 13 cm and 0.5 cm deep glands. The five troughs in the first bowl are seeded with semacucum, wheat, soy, sorghum, and birch, the sixth groove is seneosad, the second bowl holds the seeds of batat, cloud, rape, clover and chick. Then the soil is again pressed and overgrown with the same amount of the same soil to a depth of about 0.5 cm.

The plates are then poured and the solution of the test compound described below is applied. Then the dishes are placed in a greenhouse and are regularly watered for 21 days, after which phytotoxicity is established.

Flat plates are also prepared to determine post-emergence toxicity, deposited in a glazing and watered for 8-10 days, after which time the plants are sprayed with the test compound. After spraying, the leaves are kept dry for 24 hours, then regularly incubated for 21 days, after which phytotoxicity is read. 45 -

Application of herbicide

For both pre-emergence and post-emergence applications, the herbicides are applied in solution in a mixture of water and acetone in an amount of up to 0.1 kg / h and then in portions of this dose, i.e. 4.0 kg / h, 2.0. kg / ha similarly. Fred then uses 100 µl of the test substance solution in the respective concentration on each of the flat dishes. After emergence, the substances are used as a foliar spray using 5 ml of the test solution on each flat dish. Solution Preparation

For the plates of the above dimensions, the use of 8.0 kg / h of 0.025 g of substance per well is used. A stock solution of 0.2 g of the test substance was prepared in 40 ml of acetone containing 0.5% by volume of sorbitan monolaurate as emulsifier and / or non-dissolution aid. For a 6.0 kg / h dose, 10 ml of the stock solution is diluted with water to 200 ml and the solution is applied to the soil at 100 ml per dish. For the 8.0 kg / h post-emergence dose, 10 ml of the stock solution without dilution is used in a 5 ml solution on a single well. The remaining 20 ml of the stock solution was diluted with an equal volume of acetone with an emulsifier to give a 40 bn stock solution containing 0.1 g of the substance to be examined, and the above procedure was soaked, i.e. 20 ml of the solution was used at a dose of 4 kg / ha the other 20 ml for the preparation of the lower dose test solutions. p-ytotoxicity is expressed as a percentage of the extermination of the pleo. The values are determined as described in the 0 s ICO assay in Research et al., Weed Science, 2nd ed., B. Truelove, Sd., Southern Weed Science Society, Auburn University, Auburn, Alabama, 1977. . rating system: - 46 -

Herbicidal Effect Rating System - Main Description Damage Description of the Condition in% Appraisal Weed Control 0 No Effect No Damage to the Plant No Poisoning 10 Slight Slight Change Very Slight Color Effect or Suppression Slight Delayed Weed Growth 20 Color Change or Weak the growth of weed suppression 10 change, however, not permanently weak to inadequate suppression 40 moderate moderate damage, inadequate plant usually habitat suppression of damage lasts less well-recovered up to middle-doubt effect 60 permanent impairment moderate recovery · effect - 47 - evaluation in% versus control major evaluation description of damage crop description weed status 70 severe damage severe damage and loss of habitat weaker than sufficient suppression 80 plants almost destroyed, several survive only good suppression 90 only randomly surviving plants very good suppression 100 perfect effect complete destruction of plants complete post-weed control

For use as herbicides, the active compounds are formulated into herbicidal compositions by admixing the herhicidally effective amount with excipients and carriers commonly used in the art to facilitate application to the crop, taking into account that The choice of formulation and method of application may affect the efficacy of the individual substances sold. For agricultural use, the herbicidal compounds can be processed into relatively large-sized granules, which may be water-soluble or water-dispersible granules, wettable dusts and powders, emulsifiable concentrates, solutions or any other formulations. other types of devices depending on their intended use.

Said herbicidal compositions may be used either as sprays after dilution with water, as dusts or in granular form on areas where vegetation suppression is desired. 48 -

It is possible to use a small amount of active substance, for example 0.1.0.2 or 0.5%, but also 95% or more of the active ingredient.

Dusts are free-flowing mixtures of the active ingredient with a finely divided solid carrier such as talc, natural clays, diatomaceous earth, various types of flours, such as flour or cottonseed flour, and other organic and inorganic solids which are dispersing agents and carriers for a toxic substance. These solids have an average particle diameter of less than 50 µm. Typical dusts contain 1.0 parts or even herbicides & 99.0 parts of talc.

Wettable powders are also a suitable pre-emergence and post-emergent use. These are finely divided particles which can be easily dispersed in water or other vehicle. These wettable powders are applied to the soil in the dry state or as an emulsion in water or other liquid. Typical carriers for use herein are Fuller Clay, kaolin, silica, and other highly absorbent, readily wetting organic diluents. The wettable powders usually contain 5 to 80% of the active ingredient depending on the absorbency of the inorganic carrier and usually also contain small amounts of wetting agent, dispersing agent or emulsifier to facilitate dispersion. For example, the composition contains 80.8 parts of herbicide, 17.9 parts of Palmetto clay, 1.0 parts of sodium sodium sulfonate and 0.3 parts of sulfonated aliphatic polyester as wetting agent. For example, the following compositions may be used:

Ingredient% by weight active ingredient sodium 40,0lignosulfonate 20,0attapulgite 40,0 total 100,0 49 - component% by weight active ingredient 90,0 dioctylsulfosuccinate sodium 0,10 synthetic fine silica 9,9 total 100,0 component by weight active ingredient 20 Sodium sodium naphthalene sulfonate 4.0 sodium lignosulfonate 4.0 methylcellulose with low viscosity 3.0 attapulgite 69.0 total 100.0 component% by weight active ingredient base: 96% hydrated magnesium aluminum silicate 2% sodium lignosulfonate powder 2% sodium anionic naphthalene sulfonate sodium sodium salt 25% , 00 75.00 total 100.00

Typically, a surfactant and / or oil is added to the post-emergence application composition to facilitate dispersion through the leaves or to facilitate absorption of the active ingredient into the grid. 50 -

Another suitable formulation is an emulsifiable concentrate (EC), a homogeneous liquid or paste dispersible in water, or other dispersing agent, which can only be a herbicidal compound and a liquid. or a solid emulsifier, or may they also contain a liquid carrier such as xylene, heavy oil-containing aromatic fractions? isophorone or other non-volatile organic solvent. These concentrates are dispersed in water or other liquid carrier prior to use and are usually used in the form of a spray. The content of the active substance can be varied according to the way of use, usually 0.5 to 95% by weight. virtuous active ingredients.

For example, the following compositions may be used: component: active ingredient mixture of alkylnaphthalene-sulfonate ethers and polyoxyethyleneepoxidized soybean oilxylene total electrolyte active ingredient mixture of alkylnaphthalenesulphonate ethers polyoxyethylene oxylene total emulsifiable concentrates% w / w 53,01 6,00 1,00 39,99 100.00% 10.00 4.00 86.00 100.00

Other liquid compositions are similar to emulsifiable concentrates except that they are a suspension in a liquid carrier, usually water. These compositions may also contain a small amount of precipitate and contain from about 0.5% to about 95%, preferably from about 10% to about 50%, by weight of the active ingredient. These compositions may be diluted with water or other liquid and are typically used as a spray.

Specific examples of these compositions can be formulated as follows: component% by weight active ingredient 46.00 colloidal silicate-aluminum silicate 0.40 sodium alkylnaphthalenesulfonate 2.00 paraformaldehyde 0.10 water 40.70 propylene glycol 7.50 acetylene alcohols 2.50 xanthan rubber 0.80 total 100.00 component% by weight active ingredient 45.00water 48.50cleaned clay smectit 2.00xanthan gum 0.50 alkylnaphthalene sulfonate sodium 1.00 acetylene alcohols 3.00 total 100.00

Typical surfactants, dispersants or emulsifiers for agricultural use are, for example, alkyl sulfonates, alkylarylsulfonates and the corresponding sulfates and their sodium salts, alkylaryl polyether alcohols, sulfated higher alcohols, polyethylene oxides, sulfonated animal 52 - and vegetable oils, sulfonated petroleum oils, esters of aliphatic acids with polyhydric alcohols and addition products of these esters with ethylene oxide and addition products of higher mercaptans with ethylene oxide. A number of other types of usable surfactants are commonly available. Wetting agents are usually used in amounts of 1 to 15% by weight.

Other suitable formulations are solutions or suspensions of the active ingredient in relatively non-volatile solvents such as water, corn oil, kerosene, propylene glycol, other suitable solvents. A suitable example is the following suspensions: suspension in oil; % active ingredient 5,00 polyoxyethylene sorbitol hexaoleate 5,00 higher aliphatic hydrocarbon oils 70,00 total 100,00 aqueous suspension: active ingredient polyacrylic acid thickener dodecylphenolpolyethylene glycol etherhydrogen sodium phosphate dibasic sodium phosphate% w / w 40,00 0,30 0,50 1,00 0,50 1 , 00 56,70 total 100,00

Other suitable compositions are simple solutions of the active ingredient in a solvent in which the active ingredient is substantially soluble in the desired concentration. These include, for example, acetone, alkylated naphthalenes, xylene or other organic solvents. Such granulates, in which the herbicidal substance is contained in the form of relatively coarse particles, can be applied to soil application. Pressure sprays, typically aerosols, in which the active ingredient is dispersed in finely divided form due to the spraying of low-boiling carriers, such as fluorocarbons, are also suitable. Water-dispersible or soluble granular materials may also be used. These are bulk materials that can be readily dissolved in water or suspended in water. Similar compositions are described, for example, in U.S. Patent No. 3,920,442. In the case of granules, emulsifiable concentrates, concentrated concentrates, solutions and the like can be diluted with water to a concentration in the range of 0.1 or 0.2 to 1. , 5 or 2% by weight. The active compounds according to the invention can also be formulated and / or applied together with insecticides, herhicides, fungicides, nematicides, plant growth regulators, fertilizers or other chemicals for agricultural use or can be used to sterilize the soil or as selective herbicides. . It is always necessary to use an effective concentration of the substance. It may be a low amount, for example 1 to 250, preferably 4 to 30 g / ha. When used in the field where herbicides are lost, a higher amount, for example four times the abovementioned amount, can be used.

With regard to mixing the compounds of the invention with other herbicides, they may be known herbicides, for example typuchloroacetanilide, such as alachlor, metolachlor, diethatyl-ethyl, bentazone, triazine herbicides such asatrazine and cyanazine, dinitroaniline herbicides such as tri- fluralin, arylureas such as diuron and fluometuron or o2 - [(2-chlorophenyl) methyl] -4,4-dimethyl-3-isoxazolidinone.

By the process according to the invention it is also possible to obtain the substances listed in the following tables:

Table 1

Compound X No. Y P R 1 R 4 R 4 K 1 H H H 3 O 3 H 3 H 2 O-C 3 H 3 OCH 3 OCH 3 H 3 4-C 1 H 3 OCH 3 OCH 3 H 3 3 -H 2 H 2 OCH 3 OCH. HH 4 O-CH 3 HH 3 O-CH 3 HH OCH 3 OCH 3 HH 7 3-CH 3 HH OCH 3 OCH, HH 8 4-CH 3 HH OCH 3 OCK-, HH 9, 2-Cl HH OCH 2 OCH 3 HH 10 3 OCH3 HH ° ch3 ° ch3 HH12 4-SO2CH3 HH och3 OCH3 HH13 4-CH (CH3) 2 HH and OCH3 JHH 14 4-C73 HH OCH3 OCH3 HH 15 3 4 ~ OCH.-O- H OCH.CH HH 3 j 16 3-OCH3 4- och3 H och3 OCH3 HH - 55 - v''1 '' ';

nina 2. X Y P R R1 R4 M

17 4-0CH 2 F H H OCH, OCH 3 H 18 4-OCH (CH 3) 2 H H CCH, OCH 3 H 19 4-CCH 2 C = CH H H OCH 3 OCH 3 H 2 O 3 -Cl 4 Cl to OCH. OCK3 H H 21 3-C1 5- Cl K OCH. 0 CCH3 HH 22 4-¾ HH OCH3 HH 24 3-0CF2CHCiF HH och3 OCH3 HH 25 4-CN HH OCH3 HH 27 4- N02 HK och3 och3 Π H 28 3-NH2 HH och3 OCH3 HH 29 4-NH2 HH och3 OCH3 HH 30 3-NHC (O) CH (CH3 ^ 2 HH OCH, OCH, HH3 31 3-NHC (O) NH2 HH) OCH3 OCH3 HH 32 3-NHS (O) 2CH3 KH OCH3 OCH3 HH 33 4-OC (O) CH, HH OCH3 OCH3 HH 35 3-OS (O) 2CH3 HH OCH, J och3 KH 36 3-0 KH och3 och3 HH 37 3-CF3 HH OCH3 OCH3 H * T n 38 3-00,4-F) HH cch3 OCH3 HH 39 3-CSO) '0' HH OCH, OCH, HH 3 3 40 2-C1 4-C1 H OCH, CCH, HH 56

nina δ. X Y P R R 1 R 4 M 41 2-C 5 -C 1 H CCH 3 and H 3 H 4 3 -F 4 -CH 3 H OCH. J och3 HH 43 3-CH3 4-FH OCH3 OCH3 HH 44 3-NO2 4-C1 H OCH3 OCH3 HH 45 2-CH3 6-CH3 H OCH3 OCH3 HH 46 3-CH-, j J * -T 'i <γτττvv X - - 3 och3 ty 47 3-CH 3 5-CH 3 H och 3 OCR. H 1 H 45 2-CH-, 4-CH 3 5-CH 3 OCH 3 OCH 3 H 49 2-CH. .5 4-CH. 6-CH 3 OCH 3 OCH 3 H 3 O 3 -CH 3 4-CH 3 5-CH 3 OCH 3 OCH 3 H 51 K H 1 Cl 2 H 3 O 52 H 2 H 3 CH 3 CH 3. J H H 53 H H Cl OCH 3 H H 54 H K H OCH 3 \ t OCH 3 H 55 H K H OCH (CH 3) 2 OCH 3 H 56 H 2 H 2 OC. 2 5 oc ^ 5 HR 57 KHH GCH (CHJ> £ OCH (CH-). H 3 H 58 HHH ochf 2 OCH 2 HH 59 HHH Cl OCH 3 60 3 K 60 HHK Cl ooh 3 no 2 H 61 HHH Cl OCH3 0 H 62 HHH OCH3 OCH3 Cl H 63 HHH OCH3 OCH3 Br H 64 HHH och3 OCH3 CH- J ri 65 HHH OCH OCR CN H i '', ·· - · · '- 57 - Compound no. XYPR R1 R4 66 - HKH 0CH3 OCH3 NO 2 H 67 HHH OCH3 OCH3 NO 2 H 68 KKH OCR3 OCH3 co2 CH3 h 69 HHH 0CH3 OCH3 0 H 70 HKH 0CH3 och3 H c2h5 71 τ r '4 H TT (XH. J HHH 0CH3 OCH3 H CK, CF, t 3 73 HHH OCH3 HCHH3CH3 OCH3 H ch2cn 75 4-C1 HH OCK, J OCK, H ch2cn 76 HHH OCH3 OCH3 H CH (CH3) CN 78 HHH °° η3 cch3 H ce2c ch 79 4-C1 H f OCK3 OCH, j H ch2c ch 60 4-CN HH OCH3 OCH3 H CH20 81 3-N02 EH OCH3 OCH3 H GH20 83 3-NHCH20 HH OCK3 OCH3 H CH, O 64 3-nhs (o) 2cr3 HH OCH3 OCE, H CH20 65 3-NHS ( O) 20 HE cch3 OCH3 H CE20 86 3-N [s (O), 0k 2 c HH CCH 3 OCH 3 H CH 2 O 37 HHH OCH 3 OCH3 N CH2CH2N (CH3) 2 88 H u M COH-J OCH, 3 E + - I CH, CH, N (CH3), 89 HHH OCH, J OCH3 H ce2s (o) 2ch3 90 HHH OCH3 OCH3 HN = C (CH-) 2-58-

«Ι '^ A <r» vzw «.wuK

nina δ. X Y P R R1 R4 Ai 91 ττ Π K H OCE. OCK3 H h = c (ck3) sch3 92 HHH CCH3 OCH3 H 0.4-NO2 93 4-C1 HH OCH3 OCH3 JH 0.4-NO / 94 HHH och3 OCH3 Hck2co2h 95 KHH OCH ~ J och3 H CH (CH3 97 HHH OCH3 OCH3 H CH2CO2C2H5 98 4-C1 HH OCH3 OCH3 H CH2CO2C2H5 99 KHH OCH3 HCH (GO ') C ^ H -) ^ .5 3 2 100 HHH och3 och3 H ch2co2o (ch3) 3 101 HHH och3 OCK3 H CHCH3) CO2C (CK3) ~

102 HHH OCH3 OCH, H CHOC (O) N (CH3) 2 3 103 HHH OGE-OCH3 H ch2c (o) n (c2h5) 104 HHH ock3 OCH3 H Na + 105 4-01 HH OCH3 OCH3 H Na + 106 HHH OCH3 COH 3 H NHf 107 KKH CCH 3 OCH-1 H + NH, CH (CK 3 3 <108 4-Cl HH OCH 3 OCH 3 H + nh 3ch (cr 3) 2 109 4-01 HH OCH 3 ”3 H + NH (CH 2 CH 2 OH), 110 4-NHC (0; C.H_j 7 kcaplex Η H £ ethanol 0CH7 och3 HH 111 HHH NHC "h

Compound S. X Y P R R1 R4 M 112 H H H och3 cch3 - H 113 4-C1 H Ooh3 OCH3 - H 114 4-F H H ooh3 OCH-? - H 115 4-CH3 HK OCB3 OCK3 TH 116 HHH OCH3 Cl - H 117 KHH OCK3 0K3 - H 118 KHH OCHK3 - CH20 119 4-FHH OCH3 - CH 0 120 HHH 0CH3 Cl - CR20 121 HHH OCH Cn3 - CH20 - 60 -

Table 1A

OCHJ merges

nina no? in WX "Y 'BR' la C CH CH CH with CR 4 H 2a C CH 3 of CR 3a C CH CH CK 0 CR 4 H 4a c CH CH O CH CR 4 H 5a c CH CH CH N CR 4 H 6a c CH CH N CH CR4 K7a c CH CH NN CR4 K 8a c CH CH N 0 CR4 H 9a rt CH CK N with CR4 H 10a c CH N CH N CR4 H 11a G CH ΓΙ CH 0 CR4 H 12a G CH N CH with CR4 H 13a CN CH CH N CR 4 H 14a c CH CHN CR 4 H 17a c CH NNG CR 4 H • 18a c CK NNS CR 4 H 19a c N CH NK CR4 H -61 - compound PVWX "Y * BR '20a CM CH N 0 CR4 H 21a c N CH N with CR4 H 22a c KNNN CR4 H 23a N CH CH NN CR4 H 24a CH CH CH N CR 4 H 26a N CH CH N CH C H 4 H 27 a C CH CH CCH-J S CR 4 H 28a C CH CH CCH 5 with N - 62

Table 1B

merge-

nina δ. CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 N CK NH 8b NN CH CH NH 9b CK K CH 1 NNH 10b CH 2 CH 2 CH 2 CH 3

Table 2

Identification properties Compound No. melting point (° C) empirical formula 1 75-78 C19H16N2G5 2 125-129 ClgH15ClN2O5 3 - * i - - 49 '' 19nl5 L1 ^ 2 θ5 4 134.5-148 CiSHi5fn2o5 5 134-138 C13H15 ™ 2 ° 5 6 79-80 C20H18K2 ° 5 7 oil C2OH18N2 ° 5 8 148-149 ConH, zN, Oc 20 lo 2 5 9 136-140 C19H15G1N2 ° 5 10 162-163 C2OH18N2 ° 6 11 128.5-129 5 C2OH18N2 ° 6 12 137-141 C20I18N2O7S 13 59-65 C22H22N2 ° 5 14 143-145 C2OH15F3N2O5 15 70 (decomposition) C20H18N2 ° 7 16 147-149 -64- empirical formula

Table Compound No. melting point (° C) 1a 139-140 2a pa 4a

C17H16O5S17H11A6O17H1O6

Table 3 Herbicidal efficacy before use Compound 1 3 4 5 Lot No (g / ha) 125 125 125 125 Percentage evaluation compared to control ------------------- -----------------— ------------------------- · · - • - .. ...-.......- —.....- - - cloud 95 95 95 95 95 95 95 100 soya 95 95 95 90 batat 95 95 95 95 black 95 90 '95 90 sorghum 95 95 95 95 chickweed 100 95 95 95 wheat 100 85 100 100 beet 85 95 90 95 maize 100 100 100 100 - 65 - 6 125 7 8 9 125 125 125 compound no. 70 95 95 95 95 soybean 95 95 95 85 batat 95 85 95 85 black 95 95 95 85 sorghum 95 90 95 90 chickweed 90 95 95 95 wheat 9? ος ICO yo beet 85 85 90 60 maize 90 95 100 95 compound No. 9 10 11 12 dose (g / ha) 125 62.5 62.5 62.5 percent rating compared to cloud control 80 90 85 15 fag 100 95 95 95 Soya 95 95 95 40 Batat 95 80 85 20 Beef 95 90 90 85 Sorghum 95 95 95 50 Chickweed 95 95 95 95 Wheat 95 90 95 30 Beet 80 80 90 10 Maize 95 95 95 40 - 66 Compound no. g / ha) rating 13 62.5 percent 14 62.5 in 15 15.5.5n with 16 62.5 control cloud 30 70 85 90 scratch 95 100 100 95 soy 95 95 95 95 batat 90 90 90 90 90 90 95 100 sorghum 95 95 95 95 chickweed 100 100 100 wheat 40 95 95 100 beetroot 80 85 80 85 maize 95 100 100 100 compound No. 18 20 21 22 dose (g / ha) 62.5 62.5 62.5 300 percent rating compared to control tnračňák 60 15 70 90 scratch 95 90 80 95 soybean 70 50 85 95 batát 80 20 70 95 black 90 0 0 85 sorgh 80 70 70 95 chick 95 95 85 95 wheat 15 10 20 100 beet 85 50 60 90 corn 85 15 90 100 - 67 - compound δ.dose (g / ha) rating 23 31.3 percent 23 31.3 in scrape 24 62.5 ropes with 25 300 control cloudiness 5 0 30 50 fox 5 0 80 95 soy 0 0 0 85 batat 10 0 15 70 bar 5 0 0 yo sorghum 15 0 50 95 chickweed 0 5 80 95 wheat 0 5 0 100 beetroot 20 0 30 15 maize 5 5 15 100 compound no 26 27 28 29 dose (g / ha) 250 62,5 250 62 5 percent rating compared to cloud control 95 80 50 10 scratch 95 95 85 50 soybean 85 95 15 5 batat 90 85 60 5 whips 95 90 85 50 sorghum 95 90 70 20 chickweed 95 100 85 90 wheat 100 95 5 0 beet 80 70 10 15 Maize 95 100 15 15 68 - Compound No. 30 31 32 33 Dose (g / ha) 62.5 62.5 1000 100 Percent Rating Compared to Cloud Control 5 5 55 50 Para 85 0 95 90 Soya 0 0 80 80 batat 10 0 55 60 bar 0 20 95 60 sorghum 20 10 95 70 poultry? 6 'qz 9 5 95 Wheat 0 0 85 0 May 20 20 70 50 Maize 15 0 85 50 Compound No. 34 35 36 37 Dose (g / ha) 125 125 31.3 31.3 Percent Rating Compared to Cloudfly 60 80 10 80 psara 40 95 70 70 soya 60 60 0 85 batat 40 90 40 95 bac 15 95 0 70 sorghum 20 90 0 85 chickweed 60 100 90 95 wheat 5 100 0 $ 0 beet 30 90 5 70 maize 20 100 10 90 - 69 - Compound No. 38 39 40 41 Dose (g / ha) 31.3 2§0 300 300 Percent Rating Compared to Cloud Control 60 10 60 5 Tartar 70 60 95 70 Soya 50 15 40 10 Batat 60 50 90 10 Ber 90 70 30 30 sorghum 40 70 80 50 chickweed 85 40 100 95 wheat 10 5 10 io beet 30 10 60 5 maize 30 15 60 30 compound no 42 43 44 45 dose (g / ha) 62,5 62,5 300 500 rating percent as compared to cloud control 80 70 0 30 fag 95 90 70 0 soybean 95 95 30 10 sweet pot 85 90 60 50 black 90 70 85 0 sorghum 95 95 95 5 chick 95 95 80 0 wheat 70 100 20 0 beet 80 70 30 0 corn 95 95 95 10 - 70 - sl oučenina No. 47 48 51 52 Dose (g / ha) 125 500 300 500 Percentage evaluation compared to a cloud-blower control 70 80 15 40 Foxtail 95 95 5 90 Soya 90 80 0 40 Batat 90 90 0 70 Ber 30 70 5 90 Sorghum 90 90 0 90 chickweed. 9? 100 0 cO Wheat 80 60 § 90 rape. 60 90 0 0 maize 90 70 10 90 Compound No. 53 54 54 55 Dose g / ha) 250 300 100 250 Percent Rating Compared to Cloud Control 70 90 90 0 Sag 100 95 95 15 Soya 80 95 95 0 Batat 90 95 95 0 bers 90 90 40 20 sorghum 95 95 95 20 chickweed 100 100 95 15 wheat 95 100 100 5 blades 40 85 90 0 maize 100 95 95 30 - 71 - compound lot (g / ha) rating 56 250% in 57 250 comparison 58 250 s kontroloi 58 25Θ cloud 20 30 50 80 scratch 90 20 95 90 soybean 0 0 0 0 ba t 15 30 30 60 bar 10 0 20 30 sorghum 20 0 60 90 chickweed 85 50 95 80 wheat 40 0 30 60 beet 15 20 30 40 maize 5 30 90 85 compound lot (g / ha) rating 59 250% in 60 1000 comparison with 6o 1000 control 62 250 l cloud 15 0 0 60 letter 40 5 10 95 soy 30 5 0 90 packet 15 0 0 90 steer 50 0 5 70 sorghum 50 15 5 85 chickweed 90 80 80 95 wheat 5 5 5 35 beet 10 5 0 60 maize 15 10 10 80 - 72 - compound lot (g / ha; rating 63 1000% in 64 1000 comparison with 65 1000 control 66 1000 t cloud 40 80 30 5 scratch 30 90 0 5 soybean 90 95 35 90 batat 70 90 0 80 bar 0 70 0 20 sorghum 60 95 20 5 chickweed C "not done 50 95 wheat 5 70 0 5 beet 60 80 15 10 Maize 60 70 50 10 Compound No. 67 68 69 70 Dose (g / ha) 1000 1000 1000 500 Rating% Compared to Cloudfly 30 5 5 60 Tartar 90 5 10 80 Soybean 5 5 5 80 Batat 40 0 0 70 boron 5 5 10 50 sorghum 50 40 10 85 chickweed 95 40 95 95 wheat 5 10 ID 70 beet 20 20 0 50 maize 40 50 10 50 73 - compound δ. 71 72 73 74 Dose (g / ha) 1000 300 125 300 Rating% compared to control Cloud 80 80 90 90 95 100 90 95 100 Soy 95 85 95 90 Batat 95 90 85 90 Beef 90 90 95 100 Sorghum 100 9) 95 00 chickweed 100 95 95 J.OO wheat 95 90 95 90 beet 80 60 80 60 maize 95 80 90 70 compound no 75 76 77 78 dose (g / ha) 1000 1000 1000 250 rating% compared to control cloud 80 90 90 90 95 95 95 95 soya 90 95 90 90 batat 90 95 95 90 leg 40 90 30 90 sorghum 95 95 90 95 chickweed 100 95 95 100 wheat 15 95 10 95 beet 80 85 90 90 corn 95 100 95 95 - 74 - compound No. 79 80 87 88 Dose (g / ha) 1000 1000 125 125 Rating% Compared to Cloud Control 85 60 0 0 Scroll 100 90 10 20 Spja 90 0 20 5 Batat 95 0 5 0 Black 95 10 50 30 Sorghum 95 50 30 5 chickweed 100 100 80 1> wheat 60 60 0 0 beet 85 0 0 0 maize 90 5 15 5 compound No. 89 90 90 91 dose (g / ha) 125 250 31,3 1000 rating% compared to control cloud 15 95 80 95 psara 10 95 95 95 soya 10 95 90 95 sweet pot 10 90 80 95 black 60 95 90 100 sorghum 20 90 90 100 bird 80 100 100 100 wheat 5 85 80 100 beet 5 85 70 90 maize 15 90 90 100 - 75 - compound δ. 92 94 95 96 dose (g / ha) 250 1000 300 1000 rating% compared to cloud control 50 90 20 90 leaflet 95 90 60 100 soybean 30 95 10 90 batat 95 50 20 85 bark 70 0 0 80 sorghum 85 5 60 chickweed 95 100 80 • i-kz Ό wheat 20 75 0 100 beet 20 70 0 70 maize 40 70 20 100 compound No. 97 98 99 100 dose (g / ha) 300 1000 300 1000 rating% compared to control cloud 40 85 40 95 wildflowers 85 95 90 95 soybeans 90 90 50 90 batat 60 90 50 100 whips 70 90 10 95 sorghum 90 95 40 100 chickweed 95 100 100 100 wheat 15 30 0 100 beet 20 90 10 80 maize 40 95 30 100 - 76 - compound δ. 101 102 104 105 dose (g / ha) 1000 1000 31.3 30 rating% compared to cloud control 40 100 90 90 bark 95 95 95 100 soybean 80 90 95 90 ba melt 40 90 90 95 bru 80 50 85 90 sorghum 95 95 95 95 chickweed 10 ·; ICO Wheat 80 95 100 70 Beet 70 40 80 90 Corn 80 95 95 100 Compound No. 106 107 108 109 Dose (g / ha) 31.3 31.3 30 30 Rating% Compared to Cloud Control 85 80 85 80 Passage 95 95 100 95 soya 95 95 95 90 batat 90 80 95 85 beef 85 70 95 85 sorghum 95 95 95 95 chickweed 100 100 100 100 wheat 100 95 80 70 beet 85 70 85 80 maize 95 90 100 95 77 compound δ. 110 111 112 112 dose (g / ha) 62.5 250 1000 100 rating% compared to cloud control 20 0 95 95 fare 60 0 95 95 soy 15 0 95 95 batate 40 0 95 95 bare 70 0 100 90 sorghum 10 0 1.00 / -K / Chickweed 60 0 100 95 Wheat 15 0 100 100 Beet 10 10 90 70 Maize 15 10 100 100 Compound No. 113 114 115 116 Dose (£ / ha) 300 300 300 1000 Rating% compared to control Cloud 95 95 95 30 100 100 95 95 85 Soy 95 95 95 70 Batat 90 90 95 60 100 100 100 5 100 100 100 50 100 100 100 95 Wheat 100 100 100 60 95 80 70 15 100 100 100 30 - 78 - compound δ.dose (g / ha) evaluation 117 1000% compared to control cloud fly 90 leaf 95 soybean 95 batat 95 bark 1o sorghum 95 chickweed 100 wheat 100 beet 90 corn Z.

* Z - 79 -

Table 3a

Herbicidal efficacy when used before the emergence of Compound No. 1a 2a 3a dose (g / ha) 125 125 62.5 evaluation% compared to control cloud 55 70 90 fag 95 95 95 soybean 95 85 95 batat g =, 85 80 bar 9o 55 90 sorghum 90 90 95 chickweed 100 95 95 wheat 95 90 90 beet 85 60 80 maize 95 95 95 compound No. 4a 27 and 28a 62.5 300 300% compared to control dose (g / ha) rating cloud 85 95 90 95 95 95 soya 95 90 90 batat 85 90 90 90 90 95 95 95 95 95 95 95 95 95 95 95 90 80 20 95 95 100 80

Table 3b

Herbicidal efficacy at Compound No. Dose (g / ha) Evaluation Cloudworm Soybean Batat Berry Sorghum Chickweed Wheat Beet used before emergence 2b Jb 10b 100 300 300% compared to control 85 95 30 100 80 95 95 0 95 95 15 20 100 60 os 3 00 15 luo 100 95 100 100 5 40 90 0 95 100 10 ψ tt ^? S *** ^ »

Table 4

Post-emergence herbicidal efficacy Compound No. 1 3 4 5 Dose (g / Tia) 125 125 125 125 Evaluation% Compared to Cloud 100 100 100 S 100 100 95 100 Soy 95 100 95 100 Batat 9> 100 100 90 boring 95 100 60 95 sorghum 100 100 100 100 bird 100 100 100 100 wheat 100 70 100 95 beet 95 100 95 95 maize 100 90 100 100 compound lot (g / ha) evaluation 6 125% in 7 125 comparisons with 8 125 control 9 125 cloud 60 10 50 40 fox 100 ICO 100 95 soybean 100 90 100 85 sweet pot 80 40 85 80 black 60 20 100 10 sorghum 100 100 100 70 chick 80 90 100 80 wheat 50 40 100 85 beet 30 85 90 70 corn 40 25 100 85 - 82 - Compound δ.dose (g / ha) Rating 10 62.5% in 11 62.5 Compared with 12 62.5 Control 13 62.5 Clouds 85 50 50 40 Tabs 35 90 100 100 Soya 90 90 35 95 batát 90 80 80 85 bér 15 70 95 100 sorghum * 7 Π 90 95 100 chickweed 95 95 95 95 wheat 50 60 100 100 rape 95 95 30 95 maize 80 90 95 100 compound No. 14 15 16 18 Dose (g / ha) 62.5 62.5 62.5 62.5 Rating% compared to control Cloud 50 50 80 80 10 100 100 100 95 Soya 95 95 95 95 Batat 90 85 90 80 bér 90 95 100 95 sorghum 100 100 95 95 chickweed 95 100 100 95 wheat 100 100 100 95 beet 95 95 95 90 maize 100 95 100 100 - 83 - compound 20 20 22 22 dose (g / ha) 62,5 62 , 5,300 31.3 ratings% compared to cloud control 30 20 95 0 scribe 95 40 100 0 soybean 90 90 100 20 batat 80 80 95 0 bar 0 10 95 5 sorghum 70 70 100 15 chickweed 95; 0 i. 00 0 wheat 40 70 100 5 beet 60 20 100 0 corn 85 100 100 10 compound lot (g / ha) rating 23 31.3% in 24 62.5 leveling with 25 300 control 26 250 cloud 0 30 50 70 5 5 95 95 Soy 5 80 95 95 20 70 90 90 5 5 30 100 10 30 95 100 Chickweed 10 95 100 100 Wheat 0 70 100 100 Beet 0 50 85 90 Maize 5 85 100 100 - 84 - Compound No. 27 28 29 30 Dose (g / ha) 62.5 250 62.5 62.5 Rating% compared to control Cloud 30 60 30 30 10 Tabacco ICO 100 85 85 Soya 95 90 85 60 Batat 85 70 60 20 bar 70 70 60 15 sorghum 85 95 70 50 chickweed ICO 95 qr. 20 Wheat 90 100 80 85 Beet 80 70 15 20 Maize 100 85 90 95 Compound No. 31 32 33 34 Dose (g / ha) 62.5 1000 100 125 Rating% compared to control Tartanak 0 80 20 85 Tabarine 10 95 100 70 soybean 20 90 85 90 sweet pot 20 85 15 80 black 5 95 70 95 sorghum 5 100 80 100 chickweed 15 95 100 70 wheat 30 100 50 95 beet 5 70 85 60 corn 5 95 30 80 - 85 - compound lot (g / ha) rating 35 125% in 36 31,3 comparisons with 39 31,3 control 38 31,3 cloud 70 10 50 40 bark 100 80 60 95 soybean 90 85 90 90 batat 60 80 85 80 bark 30 30 70 80 sorghum 80 60 95 95 chickweed 100 20 70 90 wheat 100 50 100 95 beet 80 15 70 60 corn 80 15 70 60 compound lot (g / ha) rating 39 250% in 40 300 comparison with 41 300 control 42 62,5 cloud 10 $ 0 40 50 Para 80 90 30 95 Soya 85 95 90 95 Batat 50 70 50 80 Beef 85 95 30 60 Sorghum 60 100 50 95 Chickweed 30 70 10 95 Wheat 70 95 15 100 Beet 50 40 60 70 Maize 40 95 20 100 - 86 - compound δ .batch (g / ha) Rating 43 62.5% in 44 300 Comparison with 45 500 Control 47 125 Cloud 70 80 20 50 Fox 95 100 70 95 Soy 100 70 15 90 Batat 855 85 50 70 Ber 95 50 5 40 Sorghum Q5 Wheat 100 100 0 40 Beet 85 85 10 60 Maize 100 100 15 90 Compound No. 48 51 52 53 Dose (g / ha) 500 300 500 250 Rating% in comparison with the control of the cloud-blower 90 20 30 80 bark 100 40 95 100 soybean 80 15 70 80 batat 50 20 70 80 bark 40 15 90 100 sorghum 60 15 80 100 chickweed 95 5 95 100 wheat 30 80 95 100 beet 80 0 40 40 corn 70 30 40 100 - 87 - compound δ. 54 54 55 56 Dose (g / ha) 300 100 250 250 Rating% compared to control Tartan 90 90 20 10 Tartar 100 95 50 95 Soy 55 95 15 60 Batat 90 90 15 60 Ber 60 15 90 40 Sorghum 95 90 50 80 Chickweed 5>> 20 Wheat 100 100 10 100 Beet 90 95 20 0 Maize 100 100 15 50 Compound No. 57 58 58 59 Dose (g / ha) 250 250 250 250 Rating% compared to control Cloud 0 0 20 30 30 40 70 60 Soya 10 10 0 60 Batat 0 0 30 70 Beef 0 50 70 80 Sorghum 30 80 50 40 Chickweed 0 0 50 40 Wheat 0 50 90 40 Beet 0 0 20 40 Maize 20 60 80 50 88 - Compound δ.dose (g / ha) Rating 60 1000% in 61 1000 Comparison with 62 250 Control 63 1000 Cloud 0 0 20 40 Tab 5 0 95 30 Soy 20 30 95 100 Batat 0 0 60 90 Ber 50 15 80 90 Sorghum 30 10 90 95 Chickweed 0 5 95 Wheat 5 15 90 40 Rape 10 0 70 40 Maize 40 5 50 30 Compound No. 64 6? 66 67 dose (g / ha) 1000 1000 1000 1000 rating% compared to cloud control 40 20 0 15 scratch 95 30 15 90 soybean 100 90 100 95 cotton 80 20 90 60 whey 90 85 15 50 sorghum 100 80 40 80 chickweed 100 50 30 80 wheat 100 40 20 95 beet 70 30 30 15 maize 100 30 30 95 89 - compound δ, dose (g / ha) evaluation 68 1000% in; 69 1000 comparison with 70 500 control 71 1000 cloud engine 15 60 5 20 bar code 60 15 100 80 soybean 85 85 95 90 batat 10 80 85 5 bar SO 10 90 70 sorghum 60 15 70 95 chickweed 40 '95 i wheat 90 15 100 100 beet 0 20 0 15 maize 70 40 50 90 compound lot (g / ha) rating 72 300% in 73 125 comparison 74 300 with control 75 1000 cloudfish 20 30 50 100 fag 90 95 95 95 soybean 95 95 90 90 batat 30 90 70 100 bark 70 20 40 40 sorghum 95 100 85 80 chickweed 90 100 100 90 wheat 100 95 40 40 beet 15 40 30 90 maize 95 100 40 85 90 - compound no dose (g / ha) rating 76 1000% in 77 1000 comparison with 78 250 control 7 $ 1000 cloud engine 30 70 70 70 bar code 100 95 100 100 soybean 95 95 90 90 batat 60 85 40 80 bar 50 60 90 70 sorghum 100 95 100 95 chick 95 100 '100 100 wheat 100 30 100 80 beet 70 90 60 90 maize 100 95 'nn compound no dose (g / ha) rating 80 1000% in 87 125 comparison 88 125 with control 89 125 cloud 0 5 0 0 ps árka 80 95 5 0 soybean 50 95 15 90 sweet pot 5 70 10 20 black 10 80 20 20 sorghum 30 85 15 60 chickweed 90 95 0 0 wheat 70 - 80 10 60 beet 20 10 0 0 maize 30 60 5 40 91 - compound no 90 90 91 92 dose (g / ha) 250 31,3 1000 250 rating% compared to cloud control 90 30 100 30 fox 100 100 100 70 soybean 100 95 100 90 batat 85 80 100 80 wheer 85 70 100 70 sorghum 95 90 100 80 chickweed 100 100 100 90 wheat 100 95 100 95 beet 90 60 100 70 maize 100 85 100 50 compound lot (g / ha) rating 94 1000% in 95 300 comparisons 96 1000 with control 96 1000 clouds 0 10 85 30 psara 95 40 100 80 soya 80 40 90 95 sweet pot 10 10 50 10 sweet 10 40 50 70 sorghum 100 95 100 100 chick 80 30 100 50 wheat 10 60 30 100 beet 50 10 85 80 corn 100 50 100 100 92 - compound δ .batch (g / ha) evaluation ák ratchet sowbean soybean batat bark sorghum chickweed corn beet 97300% ve 20 90 90 15 15 85 40 80 20 98 99 100 1000 300 1000 comparison with control 90 70 100 100 95 100 90 95 95 90 40 100 85 70 100 95 100 100 100 90 1OU 80 100 100 90 20 100 95 100 100 Compound No. 101 102 104 105 Dose (g / ha) 1000 1000 31.3 30 evaluation% compared to control ač račňák 20 100 80 30 foxtail 40 100 100 100 soybean 70 100 95 90 sweet potato 30 95 95 80 black 30 95 40 70 sorghum 90 100 90 95 chickweed 90 95 95 100 wheat 60 100 100 70 beet 20 90 85 85 Maize 60 100 100 40 93 - Compound δ.dose (g / ha) Rating 106 31.3% in 107 31.3 Compared with 108 30 Control 109 30 Cloud 80 70 30 40 Fox 100 95 100 100 Soy 95 95 90 85 batat 90 90 80 80 whet 90 50 70 60 sorghum 95 100 95 95 chick 95 i XJ 100 95 wheat 100 100 80 70 beet 70 70 95 70 maize 100 100 80 50 compound or 110 111 112 112 dose (g / ha) 62.5 250 1000 100 ratings% compared to cloud control 0 0 100 95 bold 95 0 100 100 soybean 85 10 95 95 batat 10 0 100 90 bark 60 90 100 100 sorghum 60 50 100 100 chickweed 60 0 100 100 wheat e 50 0 100 100 beet 0 0 100 90 maize 80 20 100 100 94 - compound lot (g / ha) rating «rs. - 113 300% in 114 300 comparison with 115 300 control 116 1000 cloud engine 90 95 90 40 fox 100 100 100 100 soybean 95 100 95 85 batat 65 100 60 60 whip 95 100 100 70 sorghum 100 100 100 80 chickweed 11 »100 100 100 wheat 100 100 100 95 beet 95 100 80 15 maize 100 100 100 30 compound δ.dose (g / ha) rating 117 1000% compared to control cloud fly 90 95 95 soybean 95 batter 90 bar 95 sorghum 100 chickweed 100 wheat 100 corn 90 100 95 -

Table 4a

Herbicidal efficacy after emergence Compound No. la 27a 28a dose (g / h; a) 125 300 300 rating% compared to control cloud 95 95 85 fag 95 100 100 soy 90,? 100 batát 90 90 50 bar 70 100 90 sorghum 95 100 100 chick 95 100 95 wheat 90 100 95 beet 95 95 20 maize 90 100 100 96 -

Table 4b

Herbicidal efficacy in post-emergence use Compound No. 2b 3b 10b dose (g / ha) 100 300 300 rated ^% compared to cloud-control 85 100 60 fox 95 100 30 soybean S5 100 r? , t '· batát 90 100 60 bér 15 100 40 sorghum 95 100 30 chickweed 95 100 60 wheat 100 100 20 beet 80 95 0 maize 100 100 40

Claims (5)

</ - - 97 - PATENT REQUIREMENTS 1. 6-aryl-2-substituted benzoic acid derivatives of formula I co2m wherein 2 A is oxygen, sulfur or -NR, p wherein R is hydrogen, alkyl, -C (O) -NH 2 or -C (O) alkyl, B is -CH-, -CR 1 - or -N- R and R &lt; 1 &gt; are each independently alkyl, alkoxy, halo-alkoxy, halo or alkylamino, and R &lt; 1 &gt; is hydrogen, alkyl, phenyl, nitro, cyano, amino, alkoxycarbonyl or halogen, M is hydrogen, alkyl, alkenyl , alkynyl, phenylalkyl, haloalkyl, cyanalkyl, alkylthioalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkoxycarbonylalkyl, carboxyalkyl, di (alkoxycarbonyl) alkyl, dialkylaminocarbonylalkyl, dialkylideneamino, alkylthioalkylideneamino, ammonium, optionally substituted alkyl or hydroxyalkyl, cat ion the phenyl radical optionally substituted by a nitro group, a halogen atom, a 98-alkyl radical, a haloalkyl radical or an alkyloxy radical, and Q denotes a radical of the general radical of formula II wherein X, Y, and P are each independently hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower alkylthio, lower alkylsulfonyl, alkylsulfonylamino, alkylsulfonyloxy, arylsulfonyloxy, di (arylsulfonyl) amino, benzyl-amino , alkylcarbonylamino, anisocarbonylamino, alkoxycarbonyl, alkylcarbonyloxy, alkylsulfonylamino, phenylsulfonylamino, salts of said amino acid groups, lower alkenyl, lower alkynyl, lower alkenyloxy, lower alkynyloxy, cyano, nitro or amino, or form X ε Y alkylenedioxyheterocycle or an aromatic heterocyclic ring of thiophene, furan, pyrrole, pyrrazole, isoxazole, isothiazole, imidazole, oxazole, thiazole, oxadiazole, thiadiazole, triazole, tetrazole, pyridine, pyrimidine, pyrazine, pyridazine and triazine. 2. 6-.alpha.-yl-2-substituted benzoic acid derivatives according to claim 1, characterized in that 14 represents a hydrogen atom, A represents an oxygen atom, B represents a -CH-, and R1 represents a methoxy group. 3. 6-aryl-2-substituted benzoic acid derivatives according to claim 2, characterized in that 99 - Q represents a group X where X, v and? are independently hydrogen or hydrogen. 8, halo, alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfonyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, nitro or amino, or X and Y together form an alkylenedioxyheterocyclic ring of 1 to 3 carbon atoms. 4. A 6-aryl-2-substituted benzoic acid derivative according to claim 2, wherein Q is a thiophene ring. 5. 6-aryl-2-substituted benzoic acid derivatives according to claim 3, characterized in that P and Y are hydrogen. 6. 6-aryl-2-substituted benzoic acid derivatives of the formula (5), characterized in that X represents a halogen atom, a lower alkyl group or a lower alkoxy group. 7. 6-aryl-2-substituted benzoic acid derivatives according to claim 6, characterized in that X represents a chlorine or fluorine atom. 8. An o-aryl-2-substituted benzoic acid derivative according to claim 1, wherein X is methyl. 9. 6-aryl-2-substituted benzoic acid derivatives according to claim 6, characterized in that X is attached to the carbon atom at the 3 or 4 position of the phenyl ring. 10. A herbicidal composition comprising, as active ingredient, a compound of formula (I) according to claim 1 in admixture with a suitable carrier. benzoic acid of formula (I) according to claim 1, characterized in that the compound of general formula (a), when T is formyl, is oxidized, or (b) when T is cyano, alkoxycarbonyl or aryloxycarbonyl, the compound is hydrolyzed or c. ) when T is di (alkoxy) methyl, the compound is hydrolysed with subsequent oxidation, or d) when T is methylcarbonyl, the compound is oxidized using hypohalite, or e) if T is halogen, reacting compound 101 with an alkyl lithium derivative followed by treatment with carbon dioxide and an acid. 12. A method for producing a compound of formula wherein A, B, Q, R and are as defined in formula I and T is formyl, cyano, methylcarbonyl, dialkoxymethyl, -C (OH) OH, alkyloxycarbonyl or aryloxycarbonyl or a halogen atom characterized by reacting a compound of formula T wherein A, Q and ΐ are as defined above, in the presence of a base with a compound of formula G Wherein 33 is as defined in formula I and G is methylsulfonyl or chloro. 13. A method for producing a compound of formula (CCuM) A N R 1 wherein the individual substituents are as defined in claim 1, characterized in that the compound of the general formula T Q Wherein R a) when T is a carboxyl group, the compound is esterified or b) when T is -C (O) Cl, the compound is reacted with an alcohol or phenol. 14. A method for controlling undesired plants, characterized in that an effective amount of a compound according to claim 1 is applied to their growth site.