LT3949B - Herbicidal triazolinones, method for preparing thereof, herbicidal compositions and method for control of undesirable plants - Google Patents

Abstract

The herbicide compound, which is Q - changed 1-phenyl-4,5-dihydro-1,2,4-triazole-5(1H)-one, where Q is a substitute, connected to the atom of the carbon in the fifth position of the phenyl group, whereQ - -CH(R<2>)C(R<3>)(R<4>)Q<1> or -CH=C(R<4>)Q<1>; R<2> and R<3> each, one independently from another, mean the hydrogen or halogen;R<4> - hydrogen or lower alkyl;Q<1>-COOH, COOZ, COOR<5>, CON(R<6>)(R<7>), CN, CHO or C(O)R<5>;Z - a group, that is composed of salt;R<5> - alkyl, alkoxycarbonylalkyl, cykloalkyl or aralkyl;R<6> and R<7> each, one independently from another, mean residues, alkyl, cykloalkyl, alkenyl, alkoxy, phenyl, benzyl, SO2R<6> or are changed in one of the mentioned residues by the halogen, alkyl or cyan; the analogues of the 5-metoxy and 5- propargyloxy are the herbicides.

Description

The present invention relates to herbicidal l-aryl-4,5-dihydro-1,2,4-triazol-5 H / -one.

Some of the 1aryl-4,5-dihydro-1,2,4-triazol-5 / 1H / -ones (also known as l-aryl-Δ -1,2,4-triazol-5-ones) have been described in the patent literature. ) herbicidal activity.

Published British Patent Application No. No. 2090250 discloses herbicidal compounds of the following formula:

• wherein R is alkyl; R 'is an alkynyl, halomethyl or haloethyl group and X is an alkoxy, alkenyloxy, alkoxyalkoxy, alkynyloxy, hydroxyl, halomethyloxy or haloethyloxy group.

Japanese Kokai 58-225070 discloses herbicidal compounds of the following formula:

1-4C alkyl or 3-4C alkoxy in which R ¹ is 1-4C alkyl; R 'is H, 1-AC alkyl, halomethyl or 3-4C alkynyl, X is C ₂ or Z; Y is Cl, Br, OH or OR ³ , R ³ is 1-4C alkyl or benzyl;

Z - H, carboxyl or cyanomethoxy group, or COOR ⁴ ,

COSR ⁵ , CON (R ⁶ ) (R ⁷ ); R ⁴ LT 3949 B sialkyl; R ⁵ is 1-4C alkyl; R ⁶ and R ² are H, 1-4C alkyl or alkoxy.

c;

U.S. Pat. No. 4318731 discloses herbicidal compounds of the following formula:

X 2 wherein C ₁ -C ₄ alkyl; R is hydrogen, C 1 -C 4 alkyl or CR-C 4 alkenyl; X is hydroxy, C 1 -C ₆ alkyl, C ₁ -C ₆ alkyloxy or alkyloxyalkyloxy, wherein the two alkyls may be the same or different (each alkyl is C ₁ -C ₄ , C ₂ -C ₄ alkenyloxy or alkyloxycarbonylalkyloxy wherein two the alkyls may be the same or different (each alkyl is CR-C ₄ ).

U.S. Pat. 4404019 discloses herbicidal compounds:

such formulas

wherein R is a C ₄ -C ₄ alkyl group, a C ₃ -C ₄ alkenyl group or a C ₃ -C ₄ cycloalkyl group; X is a chlorine or bromine atom; Y is a hydrogen atom or a C 1 -C 6 alkoxy group.

U.S. Pat. No. 4213773 discloses 1,2,4-triazolin5-ones with a fused ring of the formula:

wherein V is alkyl; X is F, Cl, Br, CN, CH ₃ , CH ₃ O or NO ₂ ; Y is H, F, Cl, Br or CH ₃ ; Z is H, F, Cl or Br; n = 3.5; m = 0-2; Q = 0 or S.

International Applications (WO 85/01637, published April 25, 1985; WO 85/04307, published October 10, 1986; WO 86/02642, published May 9, 1986, and WO 87/00730); published Feb. 12, 1987) discloses other various substituted aryl-1,2,4-triazolin-5-ones in which the aryl group at the 5-position of the benzene ring is substituted, for example, by alkoxy, alkynyloxy, alkenyloxy, tetrahydrofuranyloxy or similar heterocycloxy, a group oR ³ COOR ⁴ (wherein R ³ - alkylene or haloalkylene and R ⁴ may be substituted with alkyl, alkenyl, etc.), alkyl, cyanoalkyl, COR ^6, CH2COR ⁶ or CH (CH 3) COR ⁶ (where R ^6, for example, alkoxy or alkyl substituted with an amine).

The compounds of the present invention are the herbicidal 1-aryl 4,5-dihydro-1,2,4-triazol-5 (1H) -ones, as known (references above), but substituted with a carbon atom at position 5 of the benzene ring as follows:

Q is a fragment of a formula

-CH (R ² ) CCR ³ C (R ⁴ ) O ¹ or -CH = C (R ⁴ ) Q ¹ wherein Q ⁴ is a carboxyl group (i.e. COOH) or a salt, ester amide or nitrile thereof.

In this way, O ¹ may be CO ₂ H, CO ₂ Z, CO ₂ R ⁵ , CON (R ⁶ ) (R ⁷ ) or CN.

In another aspect of the present invention, O ¹ may be an aldehyde or ketone group such as -CHO or COR ⁵ . Z may be a salt-forming group which forms a basic salt with a carboxylic acid, such as sodium, potassium, calcium, ammonium, magnesium ions, or mono-, di-, or tri (Οχ-Ο ₄ ) ammonium ions, or sulfonium or sulfoxonium ions .

R ³ can be alkyl, alkoxycarbonylalkyl, cycloalkyl (e.g. having 3 to 6 carbon atoms such as cyclopropyl or cyclopentyl), aralkyl (benzyl or substituted benzyl such as chlorobenzyl, acylbenzyl or haloalkylbenzyl such as 4-chlorobenzyl or aryl).

4-trifluoromethylbenzyl).

7th

R and R independently of one another may be H, OH, alkyl, cycloalkyl, alkynyl (e.g., propynyl), alkoxy, phenyl, benzyl or SO ₂ R ⁶ (wherein R ^{6 is} any other than H), or any of the aforesaid having an additional substituent; such additional substituents may be halogens: haloalkyl (e.g. chloroethyl), halophenyl (chlorophenyl), halobenzyl (chlorobenzyl), or alkyl or cyano.

3

In the above formula, Q, R and R may each independently be hydrogen or halogen (such as chlorine, bromine or fluorine), while R ⁴ may be H or lower alkyl.

Other substituents in the herbicidal 1-aryl-4,5-dihydro-1,2,4-triazol-5/1 H / -one of the present invention may be any of the known herbicidal aryltriazolinones mentioned above. For example, these other substituents are selected such that the 5-methoxy- and 5-propargyloxy analogs of the present invention are herbicides; the 5-methoxy analog of the compound of the present invention has the formula in all respects identical to the formula of the compound of the present invention except that the carbon atom at the 5-position of the benzene ring is substituted with methoxy instead of the aforementioned substituent Q.

The 5-propargyloxy analogue except that the carbon atom at the 5-position of the benzene ring is substituted with propargyloxy instead of the aforementioned substituent Q. Thus, the 5-methoxy analogue of compound no. 3 is 1- (2,4, -dichloro-5-methoxyphenyl) -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5H / -one, and 5 is - propargyloxy analogue for compound no. 3 is 1- (2,4-dichloro-5-propargyloxyphenyl) -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5 (H) -one.

In the compounds of the present invention, the 5-methoxy and 5-propargyloxy analogs have pronounced herbicidal properties. For example, said analogues kill 50% of at least one of the following plant species using 0.5 kg / ha at one of the following regimes and preferably at least 50% at 0.1 kg / ha:

Species:

fibrous galenium (Abutelon theophzasti), green fescue (Seratia viridis);

Modes:

before the emergence of sprouts, the emergence of sprouts. Tests for such herbicidal activity may be performed as described in the section Herbicidal activity.

The compounds of the present invention are shown in Table 1 below.

Many of the present invention suffer from formulas:

can be described in se-

O

R

Formula I Formula II wherein Q, R, R and R have the meanings given above, and the substituents R and R ^{1 on the} triazolinone ring may be any one of those known in the literature. For example, both R and R ¹ independently of one another may be lower alkyl (preferably methyl) or halide lower alkyl such as fluorinated lower alkyl (e.g. CF 2 CHF 2 or CHF 2). R may also be a halogen atom (e.g., chlorine). Preferably R is methyl and R ^x is CHF 2 · X may be hydrogen, halogen such as chlorine, bromine, or fluorine (preferably fluorine); alkyl, such as lower alkyl (e.g., methyl); haloalkyl such as halogenated lower alkyl (e.g. CF ₃ , CH ₂ F or CHF ₂ ); alkoxy such as lower alkoxy (e.g. methoxy); nitro. The substituent Y may be: hydrogen; halogen such as chlorine, bromine or fluorine (preferably chlorine or bromine); alkyl, such as lower alkyl (e.g., methyl; alkoxy, such as lower alkoxy (e.g., methoxy); haloalkyl, such as halogenated lower alkyl (e.g., fluoroalkyl); halogenated lower alkylsulfinyl (e.g., SOF ₃ ); halogenated lower alkoxy (e.g., -OCHF ₂ ) The preferred substituents for Z, Y in this case are: 2-F, 4-C 1, 2-F, 2,4-dichloro, 2-Br, 4-C 1, 2-F ,

4-CF ₃ .

In each aspect of the invention, it is often desirable that any side of an alkyl, alkenyl, alkynyl, or alkylene (such as the hydrocarbon side of an alkoxy or haloalkoxy group) has less than 6 carbon atoms, such as 1-3 or 1-4 carbon atoms, and that any side of the cycloalkyl would have a ring of 3-7 (preferably 3-6) carbon atoms.

Any acidic compound of the present invention, including sulfonamides, wherein NR ⁶ R ⁷ -NHSO ₂ R ^C can be converted to the corresponding base salt, such as the salt containing the cation Z (Z as previously mentioned).

These compounds are in volume or analogous to oechnology.

may be obtained by the methods described in the following literal examples or similar to them, as appropriate

In step A of Examples 1 and 3, the amino acids of formula

Formula III (same as the compound disclosed in Example 1 of International Patent Application WO / 87/03782, published July 2, 1987) is reacted (by Meerwein's arylation reaction or modification thereof) with an olefinic acid.

Compound 4, CHR = CR Q, affords the compound of formula 1, wherein Q is -CH (R ² ) C (R ³ ) (R ⁴ ) q 10 R ³ - halogen.

In this type of reaction, the amino compound is converted to the diazonium salt, which then reacts by a radial mechanism with the olefinic compound. Meerwein's arylation reaction is discussed in Doyle et al., J. Org. Chem., 42, 2431 (1977), which also describes a modification of this reaction using alkyl nitrite with copper halide in Step A of Examples 1 and 3 as described by Doyle et al. modification. Instead, it is possible to use an unmodified reaction which initially produces the developmental thiazonium halide in an acidic aqueous halogen solution and then, after the addition of an appropriate solvent (e.g. acetone), mixes with the olefinic compound, followed by the addition of a copper salt such as copper chloride.

4 1

Examples of olefinic compounds of the formula CHR = CR Q include methyl acrylate, ethyl acrylate, methyl methacrylate, methyl crotonate, methyl 3-chloroacrylate, methacrolein, vinyl methyl ketone, methacrylic nitrile and acrylamide.

The product obtained by the reactions described above (i.e.

a compound of Formula I wherein Q:

-CH (R ² ) C (R ^J ) (R ⁴ ) Q ¹ , and R ³ - halogen may be further reacted to provide other compounds of the present invention.

Removal of the hydrogen halide (e.g., sodium hydride) from this compound (if R is hydrogen) will yield the compound of formula II above wherein Q: -CH = C (R ⁴ ) Q ¹ (as in

In Example B). This compound can be halogenated or hydrogenated to give a compound wherein Q: -CH (R ² ) C (R ³ ) (R ⁴ ) Q ⁴ , and R ³ 2 is hydrogen (hydnnant as in Example 1C) or R and R ³ halogen (by halogenation as in Example 2). When Q ^T : -CO ₂ H (as in Example 3 A), the acidic compound of formula 1 can be converted (as in Examples 4 and 5) into the corresponding amide by first treating with thionyl chloride (yielding an acid halide where Q ⁴ , e.g. COC1) followed by ammonia or amine. Variants of amide formation, including the carbolimide combination, are exemplified in Examples 3B, 6 and 7, Examples 3B and 6 are derived from a carboxylic acid (e.g., Formula 1) and an amine in the presence of dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and a base such as such as N, N-diisopropylethylamine or triethylamine in a triplexer such as tetrahydrofuran. In Example 7, the amide is obtained from carboxylic acid and sulfonamide in the presence of 1,1-carboxyldiimidazole and a strong base, such as 1,8-diazabicyclo / 5.4.0 / undec-7-ene, soluble in kiy.

Instead of the parent amino compound (e.g., Formula III), one can start with another compound having a CH ₂ group instead of the NH ₂ group and react with a Wittig or Wadsworth-Emmons reagent to provide a compound of Formula II. Thus, the reagent may be a phosphorane alkylidene having an alkylidene group of formula C (R ⁴ ) C 0 such as (C 6 H 5) 3 P = CHCO ² R ⁵ (or a phosphonate ylide having a phosphonate diethyl ether attached directly to the P atom). the formula -CH (10 (such as (C ₂ H ₅ O) ₂ P (O) CH ₂ CO ₂ R ⁵ )) is used in combination with NaH according to the known reaction. R ⁵ is preferably lower alkyl such as methyl or ethyl. The compound of formula II may be hydrogenated to give a compound of formula I wherein R and R are hydrogen, or may be halogenated to give a compound of formula I wherein R and R are both halogen. loss of hydrogen halide to a compound of formula 2 wherein R ⁴ is halogen, followed by hydrogenation to a compound of formula 1 wherein R is halogen and R and R are hydrogen.

Preparation of a compound of formula III with a CHO group instead of NH ₂ is given in Example 8 below.

Instead of the starting compound containing the triazoline ring and

The coupling of the Q substituent may begin with a compound of the following formula

Formula IV and then form a triazoline ring. Compounds of formula IV are disclosed, for example, in European Patent Application Nos. 300387 and no. 300398. The NH ₂ group can be converted to the triazolinone ring in a known manner. For example, it can be converted to the NHNH ₂ (which is hydrazine) group by conventional diazotization and subsequently reduced to sodium sulfite and the hydrazine group to the triazolinone ring. Examples of such methods are described in U.S. Pat. 4818275 Paragraph 3, line 49, paragraph 5, line 8. Another method for converting a hydrazine group into a triazolinone ring is described in Japanese Patent Application Nos. 60-136572 and no. 60-136573, published May 1985; July 20 If X and Y are substitutes other than H, it can be connected at various stages of the process. In Examples 1-8 below, such substituents are coupled to form a Q-substituted compound. Any one or both of these substituents may be added later than the substituent Q; for example, the chloro substituent may be attached to the benzene ring at one of the halogenation steps modifying the Q substituent as described above.

The invention is further illustrated by the following examples. In this application the compositions are expressed in parts by weight and the temperature (unless otherwise stated) is ° C.

example

3- [2,4-Dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) -phenyl] -methyl-propionate

Stage A

2-Chloro-3- [2,4 [dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] methyl propionate

To a cold (0 ° C) stirred mixture of 28.7 g (0.333 M) methyl acrylate, 2.51 g (0.0244 M) tert-butyl nitrite and 2.6 g (0.019 M) copper (II) chloride in A solution of 1- (5-amino-2,4-dichlorophenyl) -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4- acetonitrile (15 g) in 15 ml of acetonitrile was added dropwise. triazol-5 (1H) -one solution. After mixing both solutions, the reaction mixture was warmed to room temperature and stirred for about 18 hours. It was then diluted with 15 mL of 2 N hydrochloric acid. The mixture was extracted four times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under anhydrous atmosphere to give an oil. The oil was purified by silica gel column chromatography eluting with n-heptane; ethyl acetate (4: 1) to give 5.0 g of 2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2), 4-triazol-1-yl) phenyl] methyl propionate. Compound 3 of Table 1.

Stage C

3- [2,4-Dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) -phenyl] -methyl-propionate

0.59 g (0.0016 M) of methyl 3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-) hydrogenation of triazol-1-yl) phenyl] -2-propenoate (Compound 39) gave about 0.2 g (0.0009 M) platinum (IV) oxide in about 15 mL of ethyl acetate to give 0.59 g of methyl 3- [2, 4-Dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propionate in the form of a clear oil which crystallized on crystallization. The crystals were triturated with petroleum ether and filtered, m.p. t. 70-73 ° C. Compound 1 of Table I.

example

2,3-dibromo-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] methyl propionate.

In the same manner as Abbot, 0.24 g (0.00063 M) of methyl 3- [2,4-dichloro-5- (4-difluoromethyl-4) -althoresen (Org. Syn. Coli. Vol. , 5-Dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] -2-propenoate (Compound 39) was treated with 6 drops of bromine in 15 mL of carbon tetrachloride to give 0.40 g 2,3-dibromo-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] methyl propionate as a solid. Compound 10 of Table 1.

The NMR spectrum agrees with the proposed structure.

example

N-Cyclopropyl-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propionamide

Stage A

2-Chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propanoic acid .

To a stirred mixture of 26.3 g (0.366 M) acrylic acid, 2.83 g (0.275 M) tert-butyl nitrite and 2.94 g (0.022 M) copper (II) chloride are added slowly in 75 ml of acetonitrile. , 65 g (0.0183 M) of 1- (5-amino-2,4-dichlorophenyl) 4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5 (1H) -one. The reaction mixture was stirred at room temperature for 3 hours. It is then taken up in 2N hydrochloric acid and extracted with diethyl ether. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under anhydrous atmosphere to isolate a yellow solid. The solid was pulverized, mixed with water and filtered. After drying the precipitate, 5.9 g of 2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydromethyl-5-oxo-1H-1,2,4-triazole-2-) are obtained. ii) phenyl] propionic acid. Table 1 Compound 2.

The spectrum agrees with the proposed structure. The melting point of compound 2 thus synthesized is 138-141 ° C.

Stage B

N-cyclopropyl-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propionamide.

0.50 g (0.0013 M) of 2-chloro-3- [2,4 [dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,2] 4-Triazol-1-yl) phenyl] propanoic acid (Compound 2), 0.071 g (0.0013 M) cyclopropylamine, 0.17 g (0.0013 M) 1-hydroxy 3949 B-hydroxybenzotriazole hydrate and 0.18 g The (0.0014 M) N, Ndiisopropylethylamine mixture is cooled to about 15 ° C in about 15 mL of tetrahydrofuran. To this cooled mixture was added 0.26 g (0.0013 M) of 1,3-dicyclohexycarbodiimide. After the addition is complete, the reaction mixture is allowed to warm to room temperature and stirred for about 18 hours. The reaction mixture is then filtered. The filtrate is diluted with carbon tetrachloride and washed successively with 1 N hydrochloric acid solution, aqueous sodium hydroxide solution, water, saturated aqueous sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under an evaporated atmosphere gave 0.43 g of the solid compound N-cyclopropyl-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo). 1H-1,2,4-triazoll-yl) phenyl] propionamide, m.p. 139-143 ° C. Compound 17 of Table 1.

NMR and IR spectra are consistent with the proposed structure.

example

N-methyl-N-methoxy-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro _v -3-methyl-5-oxo-lH-l, 2,4 -triazol-lil) phenyl] propoinamide.

0.50 g (0.0013 M) of 2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1 H -1,2,2 4-Triazol-1-yl) phenyl] propanoic acid (Compound 2) with 5 mL of thionyl chloride was heated under reflux for 3 hours. The mixture is cooled and excess thionyl chloride is removed by distillation under a reduced atmosphere leaving a solid residue. The residue is mixed with a cold solution of 0.13 g (0.0014 M) N, O-dimethylhydroxylamine hydrochloride and 0.11 g (0.0014 M) pyridine in 20 ml of tetrahydrofuran. The resulting mixture was stirred at room temperature for about 18 hours. The reaction mixture was diluted with diethyl ether and washed successively with 1 M hydrochloric acid, water, and saturated sodium chloride solution. The washed organic phase is dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under anhydrous atmosphere gave 0.37 g of an oil consistency of N-methyl-N-methoxy-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-). oxo (1H-1,2,4-triazol-1-yl) phenyl] propionamide. Compound 22 of Table I.

NMR and IR spectra are consistent with the proposed structure.

example

N-Methylsulfonyl-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propionamide

In the same manner as in Example 4, 0.50 g (0.0013 M) of 2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo) Reaction of 1H-1,2,4-triazol-1-yl) phenyl] propanoic acid (Compound 2) with 5 ml of thionyl chloride gives the product. To this product was added 0.50 g (0.0052 M) of methanesulfonamide. The mixture was heated and stirred at 120 ° C for 2 hours. The mixture is then cooled, diluted with methylene chloride and the resulting precipitate is removed by filtration. The filtrate is washed with water. The organic phase is dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under an evaporated atmosphere gave 0.21 g of N-methylsulfonyl-2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2). , 4-Triazol-1-yl) phenyl] propionamide in the form of foam. Compound 25 of Table 1.

NMR and IR spectra are consistent with the proposed structure.

example

2-Chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] -N - (4-Chlorophenyl) propionamide

0.50 g (0.0013 M) of 2-chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1 H-1,2 4-triazol-1-yl) phenyl] propanoic acid (Compound 2), 0.16 g (0.0013 M) 4-chloroaniline, 0.17 g (0.0013 M) 1-hydroxybenzotriazole hydrate and 0.18 g (0). , 0014 M) A solution of N, N-diisopropylethylamine in about 15 mL of tetrahydrofuran is cooled to 0 ° C. To this cooled reaction mixture was added 0.26 g (0.0013 M) of 1,3-dicyclohexylcarboyimide. After the addition is complete, the reaction mixture is warmed to room temperature and stirred for about 18 hours, then filtered. The filtrate is diluted with carbon tetrachloride and washed successively with 1 N hydrochloric acid, 10% aqueous sodium hydroxide solution, water and saturated aqueous sodium chloride solution. The organic phase is dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate in an evaporated atmosphere gave 0.28 g of an oil of 2chloro-3- [2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-) oil consistency. triazol-1-yl) phenyl] -N- (4-chlorophenyl) propionamide. Compound 23 of Table 1.

NMR and IR spectra are consistent with the proposed structure.

example

2-Chloro-3- [2-chloro-4-fluoro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-l-yl) phenyl] -N- (4-methylphenylsulfonyl) propionamide.

To a stirred solution of 0.19 g (0.0012 M) of 1,1'-carbonyldiimidazole in 3 ml of tetrahydrofuran was added 0.45 g (0.0012 M) of 2-chloro-3- [2-chloro-4-fluoro -5- (4-Difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] propanoic acid (prepared according to the method of Example 3, Step A from l) - (5-Amino-4-chloro-2-fluorophenyl) -4-difluoromethyl-1,4,5-dihydro-3-methyl-1,2,4-triazol-5 (1H) -one)) in 5 ml of tetrahydrofuran.

The reaction mixture was diluted with 5 mL of tetrahydrofuran and stirred for 30 minutes at room temperature and then heated under reflux for 30 minutes. The reaction mixture was cooled to room temperature and 0.20 g (0.0012 M) paratoluene sulfonamide was added. After stirring for about 10 minutes, 0.17 g (0.0012 M) of 1,8-diazobicyclo [5.4.0] undec-7-ene was added. The resulting mixture was stirred at room temperature for about 18 hours and then partitioned between diethyl ether and IN hydrochloric acid. The organic phase was washed with water, then with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under an evaporated atmosphere and the residue was purified on a silica gel column, eluting with n-heptane: ethanol: chloroform (1: 1: 1).

0.23 g of solid 2-chloro-3- [2-chloro-4-fluoro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole) are obtained. -yl) phenyl] -N- (4-methylphenylsulfonyl) propionamide. Melting point 267-269 ° C. Compound 38 of Table 1.

The NMR spectrum agrees with the proposed structure.

example

3- [2, -Chloro-4-fluoro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] ethyl propenoate

Stage A

2- (2-Chloro-4-fluoro-5-nitrophenyl) -1,3-dithiane

To a solution of 2-chloro-4-fluoro-5-nitrobenzaldehyde (53.2 g, 0.261 M) in 800 mL of methylene chloride was added 42.2 g (0.390 M) of 1,3-propanethiol, followed by 6.4 mL (0, 052 M) Boron Trifluoride Etherate. The resulting mixture was stirred at room temperature under a dry nitrogen atmosphere for about 48 hours. Boron trifluoride etherate and 1,3-propandithiol were additionally added as analysis of the reaction mixture indicated the presence of unreacted 2-chloro-4-fluoro-5-nitrobenzaldehyde. The resulting mixture was further stirred for 5 hours. The reaction mixture was then diluted with 300 mL of 5% aqueous sodium hydroxide solution. The organic phase was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under anhydrous atmosphere left a solid residue which was dissolved in a mixture of methylene chloride and n-heptane and crystallized. The product was further purified by filtration of its solution and evaporation of the filtrate under a reduced atmosphere. 56.9 g of a solid were obtained, which analysis by NMR showed 90% of 2- (2-chloro-4-fluoro-5-nitrophenyl) -1,3-dithiane and 10% of 1,3-propanediol.

Stage B

2- (5-amino-2-chloro-4-fluorophenyl) -1,3-dithiane

To a stirred mixture of 20.0 g (0.0681 M) of 2- (2-chloro-4-fluoro-5-nitrophenyl) -1,3-dithiane and 150 ml of acetic acid was added 75 ml of tetrahydrofuran, followed by portions of 15.8 g ( 0.269 M) iron powder. The reaction mixture is then warmed to 50 ° C for 30 minutes, cooled in an ice bath and diluted with diethyl ether. The resulting mixture was filtered through a celite filter. after addition of water to the filtrate, the organic phase was separated and stirred vigorously with sodium bicarbonate solution until the mixture became slightly alkaline. The aqueous phase was separated from the organic phase and extracted with diethyl ether. The extraction was combined with the organic phase and the mixture was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate in an evaporated atmosphere gave 13.5 g of solid 2- (5-amino-2-chloro-4-fluorophenyl) -1,3-dithian. Melting point 112-115 ° C.

The NMR spectrum is consistent with the proposed structure.

Stage C

4-Chloro-2-fluoro-5- (1,3-dithian-2-yl) acetaldehyde phenylhydrazone 10.0 g (0.0379 M) of 2- (5-amino of chloro-4-fluorophenyl) -1,3-dithiane and 100 ml of concentrated hydrochloric acid was added dropwise to a solution of 2.55 g (0.0379 M) of sodium nitrite in 20 ml of water. The mixture was stirred at -5 ° C for approximately 45 minutes. Thereafter, 17.1 g (0.0758 M) of SnCl ₂ · 2H ₂ O in 30 ml of concentrated hydrochloric acid was added dropwise. The resulting mixture was stirred for 1 hour then slowly added 5.16 g (0.007 M) acetaldehyde in 200 mL of water and stirred again for 1 hour, whereupon the precipitate formed. Filtration, washing with water and drying gave 4-chloro-2-fluoro-5- (1,3-dithian-2-yl) acetaldehyde phenylhydrazone.

Step D - [4-Chloro-2-fluoro-5- (1,3-dithian-2-yl) phenyl] -4,5-dihydro-3-methyl-1,2,4-triazole-5 (1H) -on

To a stirred mixture of 5.00 g (0.0145 M) of 4-chloro-2-fluoro-5- (1,3-dithian-2-yl) acetaldehyde phenylhydrosone in 50 ml of acetic acid was added 1.38 g (0.017 M) of potassium. cyanate solution in 5 ml water. The mixture was stirred at 15 ° C for about 1.5 hours. If the thin layer of the reaction mixture shows chromatographic analysis in the presence of 4-chloro-2-fluoro-5- (1,3-dithian-2-yl) acetaldehyde phenylhydrazone, additional aqueous potassium cyanate solution may be added. Subsequently, at a temperature of 15 ° C, 30 ml of a 5% aqueous sodium hypochlorite solution are added and the mixture is stirred at 15 ° C for approximately 1 hour. Distillation of the solvents in an inert atmosphere gives a precipitate which is dissolved in ethyl acetate and washed successively with a saturated aqueous sodium bicarbonate solution, water and a saturated aqueous sodium chloride solution. The washed organic solution was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate in an evaporated atmosphere gave 1- [4-chloro-2-fluoro-5- (1,3-dithian-2-yl) phenyl] -4,5-dihydro-3-methyl-1,2,4-triazole. -5 (1H) -one.

2.5 g (0.0072 M) of 1- [4-chloro-2-fluoro-5- (1,3-dithian-2-yl-phenyl) -4,5-dihydro-3-methyl-1,2- A mixture of 4-triazol-5 (1 H) -one and 3.0 g (0.022 M) of anhydrous potassium carbonate in 30 ml of anhydrous dimethylformamide is heated at 90 ° C under a stream of dry hydrogen until chloroform difluoromethane is bubbled through until the phlegm begins to form in the reaction flask. After about 1 hour, the reaction mixture is cooled and poured into approximately 300 ml of cold water. The resulting precipitate is collected by filtration, washed with water and dried to give l- [4-chloro-2-fluoro-5 (1). , 3-dithian-2-yl) phenyl / -4-difluoromethyl-4,5-dihydro-3-methyl 1-1,2,4-triazol-5 (1H) -one.

Stage F

1- (4-Chloro-2-fluoro-5-formylphenyl) -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5 (1H) -one.

To a solution of 5.5 g (0.031 M) bromosuccinimide in 80 ml of acetonitrile and 20 ml of water, which is well mixed and cooled, is slowly added 2.0 g (0.0051 M) of 1- [4-chloro-2-fluoro-5- ( 1,3-Dithian-2-yl) phenyl] -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-trazol-5 (1H) -one, 25 ml acetone and 25 ml acetonitrile . The reaction mixture was stirred at 0 ° C for 1 hour, then about 15 mL of a saturated sodium hydrosulfite solution and 25 mL of a mixture of methylene chloride and 25 mL of n-heptane were added. The reaction mixture is shaken in a separatory funnel, the organic phase is separated off and washed successively with a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride. The washed organic phase is dried over anhydrous magnesium sulfate and filtered. After evaporation of the filtrate in an evaporated atmosphere, the resulting residue was purified on a silica gel column. 1- (4-Chloro-2-fluoro-5-formyl-phenyl) -4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5 (1H) -one is obtained.

G s tadi j a

3- [2-Chloro-4-fluoro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl] ethyl propenoate

To a stirred solution of 1.0 g (0.0034 M) of 1- (4-chloro-2-fluoro-5-formylphenyl (4-difluorophenyl-4,5-dihydro-3-methyl-1,2,4-triazole-5 (1 H)) - and 15 ml of toluene were added 1.2 g (0.0034 M) of carbethoxymethylenetriphenylphosphorane, and the reaction mixture was stirred at room temperature for about 3 hours, then refluxed for about 1 hour, then cooled and diluted with diethyl ether. washed with: water, 1 N hydrochloric acid, aqueous sodium bicarbonate solution, aqueous saturated sodium chloride solution, the washed organic phase was dried over anhydrous magnesium sulfate and filtered, and the filtrate was evaporated under an inert atmosphere and purified by silica gel column chromatography to give 3- [2-chlorine. -4-Fluoro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-2-yl] phenyl ethyl propenoate.

Herbicidal activity

The test plant species used to demonstrate the herbicidal activity of the compounds of the present invention are: cottonwood (Gossypium hirsutum), soybean (Glycine max. Var. Williams), corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivium var. Wheaton), Rice (Oryza sativa var. Labelle), Spinach (Ipomea lacumosa or Ipomesa Helderacea), Grass mustard (Brassica kaber), Abutilon theophrasti, Echinochloa crus-galli, Seratia (Seratia) Sorghum halepense).

Bag preparation

Before the emergence of sprouts:

For the study of the effect of each dose of each herbicide, two disposable bags (8 cm x 15 cm x 26 cm) are filled with a 6.5 cm layer of steam-sterilized sandy soil. The soil is leveled and 6 symmetrically arranged grooves 13 cm long and 0.5 cm deep are made in the template (both baskets). Seeds of wool, soybean, corn, rice and wheat (sixth empty) are sown in the five grooves of the first basket, while seeds of mustard, spinach, fiberglass, papLT 3949 B, green shoots and sorghum are sown in the second basket. With template seeds. stamped into the ground. Each bag is filled with a 0.5 cm layer of soil (consisting of equal parts of sand and loam). The bags are first watered with water followed by the test compound solution according to the procedure described below.

When sprouts appear:

For this regimen, 2 bags of each herbicide are also prepared for each dosing. They are prepared in the same way as the previous ones. The prepared baskets are watered for 8-11 days and the resulting vegetation is sprayed with the test compound solution as described below.

Application of herbicides

For both test regimens, herbicides are prepared in water-acetone solutions, usually at twice the decreasing dose: 8 kg / ha, 4 kg / ha, 2 kg / ha, and so on.

Four bags (two before sprouting and two after emergence) are placed side by side and sprayed with 30 ml of the test solution, i. approximately 7.5 ml per bag. Before the emergence of the sprouts, the soil is sprayed and the plants are sprayed. Two bags of seeds (prior to sprouting) are watered regularly for two weeks after treatment, while the toxicity parameters are recorded. In the germination test, the leaves are dry for 24 hours after spraying and then watered for 2 weeks and recorded for toxicity.

Preparation of test solutions

For bags of the specified size, a dosage of 8.0 kg / ha is equivalent

0.06 g / basket or 0.24 g for 4 bags. A total solution of 0.48 g of the test herbicide in 60 ml of a water-acetone (1: 1) mixture containing 0.5% (v / v) emulsifier sorbitan monolaurate is divided into 30 ml (0.24 g herbicide each). . At 8% (8.0 kg / ha), one of the 30 ml parts is sprayed onto 4 bags undiluted (7.5 ml / bag). The other 30 ml is diluted with another 30 ml of water-acetone mixture to obtain 60 ml of a solution containing 0.24 g herbicide. This solution is again divided into 30 ml portions containing 0.12 g herbicide each. One part is used without further dilution for four baskets (4 kg / ha) and the other 30 ml is diluted again to give 60 ml of a solution containing 0.12 g herbicide. Half-life gives 2 x 30 ml of a solution containing 0.06 g herbicide. One part is used (30 ml, 0.06 g) at a dose of 2.0 kg / ha and the other is doubled and so on.

Phytotoxicity was controlled by percentage, in a similar manner (0: 100 ratio) as described in Research Methods in Weed Science 2nd ed. In B. Truelove, Ed. , Southern Weed Science Society. Auburn University, Auburn, Alabama, 1977.

Herbicide Dosing System

Dosing percentage control Description of the main categories Description of the culture Weed description 0 There is no effect Negative effects for growth or damage Weeds Non- controlled 10th Minor fading or a pause in growth Very slight control

Dosing percentage control Basic categories description Description of the culture Weed description 20th Insignificant effect Certain fading, stunting or shoots death Slight control 30th Significant cultural violations but not lasting Slight or not enough control 40 A minor violation, the culture usually persists Not enough control 50 Gentle Long term damage, survival questionable Insufficient ar moderate control 60 Long-term cultural damage, she no longer remains Moderate weed control 70 Severe lesion, loss of shoots Not enough control 80 Strong The culture is almost dead, the single plants remain Satisfactory or good control 90 Live single plants remain Very good control 100 Full Culture in full bloom Complete evil effect vo destruction of grasses

The herbicidal parameters of the various compounds of the present invention, selected from dosage regimens, are shown in Tables 3 and 4. The numbering of the test compounds is as given in Table 1 3949 B

Upon entering. The reduction in kg / ha in Tables 3 and 4 refers to kilograms per hectare.

When using herbicides, the active compounds are formulated into herbicidal compositions by mixing them with stimulants and carriers commonly used in the art to facilitate dispersion of active ingredients and the fact that the composition and mode of application of the toxic agent can affect the activity of the agent under certain conditions. Thus, when used in agriculture, these herbicidal compounds may be formulated in the form of relatively large granules, water-soluble or water-dispersible, finely ground powders, wettable powders, emulsifiable concentrates, solutions or other formulations, depending on the desired mode of use.

In areas where growth inhibition is required, these herbicidal compounds may be used in the form of water-soluble aerosols, dusts or granules. These compositions may contain from 0.1%, 0.2%, 0.5% to 95% (w / w) of the active ingredient.

Rusts are selected from free-flowing mixtures of the active ingredient with very finely divided solids such as talc, natural clays, kieselguhr, powders, for example, of cotton seed and walnut shell or other organic and inorganic materials which are poisonous dispersants and carriers. The particles of these shredded materials have average dimensions less than 50 microns. A dust formulation containing 1.0 parts or less of the herbicidal compound and 99.0 parts of talc is typical. Moisturizing powder is also convenient for herbicides used both before and after emergence. They are composed of finely divided particles capable of easily dispersing in vanLT 3949 B deck or other dispersed media. Moisturizing powders are used in the soil in the form of either dry dust or emulsion water or other liquid. Typical carriers for such powders include Fuerer's earth, kaolin clays, silica and other highly absorbent, readily wettable inorganic solvents. The wettable powder will typically contain from 5% to 80% of the active ingredient and a small amount of wetting, dispersing or emulsifying agent to facilitate dispersion, depending on the carrier. For example, the wettable powder contains 80.8 parts herbicidal compound, 17.9 parts Palmet clay, 1.0 part sodium lignosulfonate, and 0.3 part sulfonated aliphatic polyester (wetting agents).

Other wettable powder formulations

The component % by weight Active substance 40.00 Sodium lignosulfonate 20, 00 Atapulgite clay 40.00 Total: 100.00 The component % by weight Active substance 90.00 Sodium dioctylsulfosuccinate 0.10 Fine synthetic silica 9, 90 Total: 100.00 The component % by weight Active substance 20.00 Sodium alkylnaphthalenesulfonate 4.00 Sodium lignosulfonate 4.00 Low viscosity methylcellulose 3.00 Atapulgite clay 69.00 Total: 100.00

The component

Active substance

Basis:

% hydrated aluminum-magnesium silicate 2% sodium 1ignosulfonate powder% anionic sodium alkylnaphthalenesulfonate powder% by weight

25, 00 75, 00

Total:

100.00

An additional moisturizing agent and / or oil is added to facilitate foliar application and plant uptake into the post-emergence mixture.

Other formulations for herbicidal use are emulsifiable concentrates (EC). These are homogeneous liquids or pastes which can be dispersed in water or other dispersed media, which may consist entirely of the herbicidal compound and the liquid or solid emulsifying agent, or may contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorane or other volatile organic solvent. For herbicidal use, these concentrates are dispersed in water or other carrier and are usually used for watering. Depending on the application of the composition, the amount of the main active ingredient may vary, but will usually be 0.5-95% by weight of the total herbicidal composition.

The following are examples of emulsifiable concentrates:

The component

Active substance

Mixture of alkylnaphthalenesulphonate and polyoxyethylene ethers Epoxidised soybean oil Xylene%

53, 01

6, 00 1.00 39, 99

100.00

Total :

Component of weight ΐ

Active substance - 10.00

Mixture of alkylnaphthalenesulphonate and polyoxyethylene 4,00 ethers

Xylene 86.00

Total: 100.00

Such formulations resemble EC except that the active substance is suspended in a liquid carrier (usually water). Like EC, they may contain small amounts of surfactants. The active ingredient is present in an amount of 0.5-95% (often 10-50%) by weight of the composition. For application, they are dissolved in water or a liquid carrier and are generally used in aerosol form.

The following are examples of such formulas:

Component% by weight

Active substance 46.00

Colloidal magnesium-aluminum silicate 0.40

Sodium alkylnaphthalenesulfonate 2.00

Paraldehyde 0.10

Water 40.70

Propylene Glycol 7.50

Acetylene Alcohols

Xanthogen Resin 0.80

Total: 100.00

Component% by weight

Active substance 45.00

Water 48.50

Purified White Clay 2.00

Xanthogenic resin 0.50

Sodium alkylnaphthalenesulfonate 1.00

Acetylene Alcohols

100.00

Total:

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, alkyl and alkylaryl sulfonates, and their sodium salts; alkylaryl polyether alcohols; sulfonated higher alcohols; polyethylene oxides; sulphonated animal oils; sulphonated petroleum oils; esters of fatty acids and polyhydric alcohols and the ethylene oxide products thereof; and additional long-chain mercaptans and ethylene oxide products. There are many other useful surfactants available for sale. The surfactant generally comprises 1-15% of the total weight of the composition.

Other useful formulations include simple solutions or suspensions of the active ingredient in a relatively solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents. Examples of suspensions are:

Oily suspension by weight

Active substance 25.00

Polyoxyethylene-sorbitol-hexoleate 5.00

Oil 70.00

Total: 100.00

Aqueous suspension by weight

Active substance 40.00

Polyacrylic acid thickener 0,30

Dodecylphenol-polyethylene glycol ester 0.50

Sodium hydrogen phosphate 1.00

Sodium dihydrogen phosphate 0.50

Polyvinyl alcohol 1.00

Water 56.70

100.00

Total

Other useful herbicidal formulations include simple solutions of the active ingredient in a solvent in which it is completely dissolved to the required concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents. Granule recipes that contain relatively coarse-grained particulate matter are particularly useful when airborne or permeable to culture. It is also possible to use aerosols in which the active ingredient is comminuted by evaporation in a low-boiling dispersion carrier such as freon, fluorinated hydrocarbons.

Water-soluble or water-dispersible granules are also convenient for the herbicidal application of these compounds. Such granule formations are loose, dust-free and easily miscible and soluble in water. Soluble or dispersible granules described in U.S. Pat. No. 3920442, also suitable for the aforementioned herbicidal compounds. For the farmer using granules, emulsifiable concentrates, flowable concentrates, solutions and the like in the field. they can be diluted with water to give an active ingredient concentration of 0.2% to 2.0%.

The active herbicidal compounds of the present invention may be formulated and / or used in combination with insecticides, fungicides, nematocides, growth regulators, fertilizers and other agricultural chemicals, as well as effective soil sterilizers and selective herbicides. The active ingredients of the present invention, alone or in combination with other chemicals, are selected in effective amounts and concentrations; For example, with compound 5 (Table 1) applied at seedling emergence, broadleaf weeds (e.g., galen, rot, thistle, porcupine) can be used at doses of 7 g / ha or less, eg 7-125 g / ha. ) for control with minimal or no damage to basic structure, such as maize, in fields with high herbicide losses and high doses (eg 4 times higher).

The active herbicidal compounds of the present invention may be used in combination with other herbicides, e.g., they may be mixed with the same or greater amounts of known herbicides, such as chloroacetanyl herbicides: 2-chloro-N- (2,6-diethylphenyl) -N-methoxy -methyl (acetamide) (alachlor); 2-Chloro-N- (2-ethyl-6-methylphenyl-N- (2-methoxy-1-methylethyl (acetamide) (metolachlor)); N-chloroacetyl-N- (2,6-diethylphenyl) glycine [(diethyl- benzothiodiazine herbicides such as 3- (1-methylethyl) - (1H) -2,1,3-benzothiothiazine-4- (3 H) 15 -one-2,2-dioxide (bentazone); triazine herbicides such as ethylene; 6-chloro-N-ethyl-N- (1-methylethyl) -1,3,5-triazine-2,4-diamine (atrazine) and 2- [4-chloro-6- (etalamin) -1,3,5- triazin-2-yl] amino-2-methylpropanenitrile (cyanazine); dinitroaniline herbicides such as 2,6-dinitro-N, N-dipropyl-4- (trifluoromethyl-benzenamine) (trifluoralin); aryl urea herbicides such as N (3,4-dichlorophenyl) -N, N-dimethyl-urea (diuron) and N, N-dimethyl-N '- [3- (trifluoromethyl) -phenyl] urea (fluorometuron); and 2- [(2- chloro (phenyl) methyl] -4,4-dimethyl-3-isoxazolidinone.

table

The compound No. X Y 0 R ¹ 1 Cl Cl CH, CH ₂ CO ₂ CH ₃ CHF ₂ 2 Cl Cl CH ₂ CH (cdco ₂ h chf ₂ 3 Cl Cl CH ₂ CH (Cl) co ₂ ch ₃ chf ₂ 4 Cl Cl CH ₂ CH (C 1) CO ₂ C ₂ H ₅ chf ₂ 5 F Cl CH ₂ CH (Cl) co ₂ c ₂ h ₅ chf ₂ 6th Cl Cl CH ₂ CH (Br) CO, C ₂ H ₅ chf ₂ 7th Cl Cl CH ₂ CH (Cl) CO ₂ CH (CH ₃ ) ₂ chf ₂ 8th Cl Cl CH ₂ CH (Cl) co ₂ ch (CH ₃ ) ch ₂ ch ₃ chf ₂ 9th Cl Cl CH ₂ CH (Cl) co ₂ ch ₂ c ₆ h ₅ chf ₂ 10th Cl Cl CH (Br) CH (Br) CO ₂ CH ₃ chf ₂ 11th Cl Cl CH (Br) CH (Br) CO ₂ C ₂ H ₅ chf ₂ 12th Cl Cl CH (CH ₃ ) CH (Cl) CO ₂ C ₂ H ₅ chf ₂ 13th F Cl CH ₂ C (Cl) (CH ₃ ) co ₂ ch ₃ chf ₂ 14th Cl Cl CH ₂ CH (C 1) C (O) NH ₂ chf ₂ 15th Cl Cl CH ₂ CH (Cl) C (O) nhch ₃ chf ₂ 16th Cl Cl CH ₂ CH (Cl) C (O) n (CH ₃ ) 2 chf ₂ 17th Cl Cl CH ₂ CH (Cl) C (O) NH-cyclopropyl chf ₂ 18th Cl Cl CH ₂ CH (Cl) C (0) nhch ₂ ch-ch ₂ chf ₂ 19th Cl Cl CH ₂ CH (Cl) C (O) nhch ₂ cn chf ₂ 20th Cl Cl CH ₂ CH (Cl) C (0) ΝΗ0Η chf ₂

table (continued)

The compound No. X Y 0 r ¹ 21st Cl Cl CH ₂ CH (Cl) C (O) NHOCH ₃ chf ₂ 22nd Cl Cl CH ₂ CH (Cl) C (O) N (CH ₃ ) OCH ₃ chf ₂ 23rd Cl Cl CH ₂ CH (Cl) c (O) NHC ₆ H ₄ -4-Cl chf ₂ 24th Cl Cl CH ₂ CH (Cl) C (O) NHCH ₂ C ₆ H ₄ -4-Cl chf ₂ 25th Cl Cl CH ₂ CH (Cl) C (O) NHSO ₂ CH ₃ chf ₂ 26th Cl Cl CH ₂ CH (C1) (O) NHSO ₂ C ₆ H ₄ -4-Cl chf ₂ 27th Cl Cl CH ₂ CH (Cl) C (O) NHSO ₂ C ₆ H ₄ -4 -CH ₃ chf ₂ 28th F Cl ch ₂ ch (CH ₃ ) co ₂ ch ₃ chf ₂ 29th F Cl CH ₂ CH (Cl) c (O) NH-cyclopropyl chf ₂ 30th F Cl CH ₂ CH (Cl) C (O) nhch ₂ cn chf ₂ 31st F Cl CH ₂ CH (Cl) C (O) N (CH ₃ ) OCH ₃ chf ₂ 32 F Cl CH ₂ CH (C 1) C (O) NHSO ₂ CH ₃ chf ₂ 33 F Cl CH ₂ CH (C 1) C (O) NHSO ₂ CF ₃ chf ₂ 34 F Cl CH ₂ CH (Cl) C (O) NHSO ₂ C ₆ H ₄ -2-Cl chf ₂ 35 F Cl CH ₂ CH (Cl) C (O) n H 50 ₂ c ₆ h ₄ -3-ci chf ₂ 36 F Cl CH ₂ CH (Cl) C (O) NHSO ₂ C ₆ H ₄ -4-Cl chf ₂ 37 F Cl CH ₂ CH (Cl) C (O) NHSO ₂ CH (CH ₃ ) ₂ chf ₂ 38 F Cl CH ₂ CH (Cl) C (O) NHSO ₂ C ₆ H ₄ -4 -CH ₃ chf ₂ 39 Cl Cl CH-CHCO ₂ CH ₃ (trans) chf ₂ 40 Cl Cl CH-CHCO ₂ C ₂ H ₅ (trans) chf ₂ 41 F Cl CH-CHCO ₂ C ₂ H ₅ (trans) chf ₂ 42 Cl Cl CH-CHCO ₂ CH ₂ C ₆ H ₅ (trans) chf ₂ 43 F Cl CH-C (CH ₃ ) CO ₂ CH ₃ (trans) chf ₂ 44 Cl Cl CH ₂ CH (Cl) CH chf ₂

table (continued)

The compound No. X Y 0 R ¹ 45 F Cl CH ₂ CH (Cl) co ₂ ch ₃ CHF ₂ 46th F Cl CH ₂ CH (Cl) COOH chf ₂ 47 Cl Cl CH ₂ CH (Cl) COCH ₃ chf ₂ 48 Cl Cl CH ₂ CH (Cl) conhch ₂ ch ₂ ch ₅ chf ₂ 49 Cl Cl CH ₂ CH (Cl) ch ₂ ch (Cl) conhch ₂ ch ₂ ch ₃ chf ₂ 50 Cl Cl CH ₂ CH (Cl) CONHCH (CH ₃ ) CH ₂ CH ₃ chf ₂ 51 Cl Cl CH ₂ CH (Cl) CONH-cyclopentyl chf ₂ 52 Cl Cl CH-CHCONH-cyclopentyl (trans) chf ₂ 53 Cl Cl CH-CHCONHCH ₂ CH ₂ CH ₂ CH ₃ (trans) chf ₂ 54 Cl Cl CH-CHCONHCH (CH ₃ ) CH ₂ CH ₃ (trans) chf ₂ 55 F Cl CH-CHCO ₂ CH ₃ (cis / 'trans mix) chf ₂ 56 F Cl CH ₂ CH (Cl) CO ₂ CH (CH ₃ ) ₂ chf ₂ 57 Cl Cl CH ₂ CH (Cl) CONHCH (CH ₃ ) ₂ chf ₂ 58 Cl Cl CH-CHCONHCH (CH ₃ ) 2 (trans) chf ₂ 59 Cl Cl CH ₂ CH (Cl) conhc ₂ h ₅ chf ₂ 60 Cl Cl CH-CHCONHC ₂ H ₅ (trans) chf ₂ 61 F Cl CH ₂ CH (Cl) CHO chf ₂ 62 F Cl CH ₂ CH (Cl) CO ₂ Ca 1/2 * chf ₂ 63 F Cl CH ₂ CH (Cl) CO ₂ K chf ₂ 64 F Cl CH ₂ CH (Cl) CO ₂ NH (C ₂ H ₅ ) ₃ chf ₂ 65 Cl Cl CH ₂ CH (Cl) co ₂ ch ₃ cf ₂ chf ₂ 66 F Cl CH ₂ CH (Cl) co ₂ ch ₃ cf ₂ chf ₂

canes * Calcium salt containing 2 equivalents of acidic table36 (cont.)

The compound No. X Y 0 R ¹ 67 F Cl CH ₂ CH (Cl) co ₂ c ₂ h ₅ cf ₂ chf ₂ 68 F Cl CH ₂ C (Cl) CH ₂ C (Cl) (CH ₃ ) CO ₂ CH ₃ cf ₂ chf ₂ 69 Cl Cl CH ₂ CH (Cl) CO ₂ CH ₂ CO ₂ CH ₃ chf ₂ 70 Cl CL CH ₂ CH (Br) CO ₂ CH ₃ chf ₂ 71 F Cl CH ₂ CH (Cl) CO ₂ Well chf ₂ 72 Cl Cl CH ₂ CH (Cl) C (O) NHSO ₂ CH ₂ C ₆ H ₅ chf ₂ 73 Cl Cl CH-CHCO ₂ H (trans) chf ₂ 74 Cl Cl CH-CHC (O) NH ₂ (trans) chf ₂

table

MELTING TEMPERATURES DETERMINED

Compound No. t. melt ( ^J C) Compound No. t. melt (° C) 1 70-73 30th 158-160 2 138-141 31st 125-127 3 oil 34 foam 4 oil 35 oil 5 oil 36 foam 6th oil 37 foam 7th oil 38 267-269 8th oil 39 148-151 9th oil 40 140-141 10th cool 41 119-122 11th 58-60 42 101-105 12th oil 43 96-98 13th oil 44 oil 14th 164-167 45 oil 15th foam 46th > 280 16th oil 47 oil 17th 139-143 48 oil 18th oil 49 oil 19th 155-157 50 oil 20th foam 51 153.3-155 21st foam 52 162-164 22nd oil 53 74-76 23rd oil 54 85-88

table

Compound No. t.lyd. (° C) Compound No. t. melt (° C) 24th oil 55 cool 25th foam 57 foam 26th foam 58 188-191 27th foam 59 141-142 28th oil 60 81-83 29th foam 62 > 280 63 195 (splits) 69 oil 64 oil 70 oil 65 oil 71 173-174 66 oil 72 oil 67 oil 73 210-212 68 oil 74 180-184

Foam-labeled compounds were isolated in the form of 5 amorphous solid products with no defined melting point.

table

HERBICIDAL ACTIVITY BEFORE EMERGENCY (% CONTROL)

Compound No. 1 2 3 Application rate (kg / ha) Species 0.5 0.5 0.5 Woolen 0 90 50 Soya 0 0 5 Corn 30th 10th 10th Rice 60 10th 5 Wheat 5 0 5 Shit 50 100 95 Soil mustard 70 90 100 Fiberglass galenical 95 100 100 Common rolling stock 30th 5 70 Green doggie 50 10th 85 Sorg 50 30th 50 Compound No. 4 5 6th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 70 90 30th So ya 5 0 5 Corn 10th 5 10th Rice 15th 10th 5 Wheat 10th 20th 0 Shit 100 100 50 Soil mustard 100 100 60 Fiberglass galenical 100 100 100 Common rolling stock 40 20th 0 Green doggie 5 5 0 Sorg 70 40 5

Table 3 (continued) Compound No. 7th 8th 9th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 90 80 80 Soya 0 0 0 Corn 15th 10th 10th Rice 15th 5 30th Wheat 0 0 5 Shit 90 40 100 Soil mustard 100 90 95 Fiberglass galenical 95 100 100 Common rolling stock 50 5 70 Green doggie 50 10th 30th Sorg 20th 60 85 Compound No. 10 11th 12th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 5 10th 50 Soya 10th 0 0 Corn 0 20th 40 Rice 15th 40 30th Wheat 0 5 60 Shit 30th 50 100 Soil mustard 100 100 95 Fiberglass galenical 100 100 100 Common rolling stock 85 100 95 Green doggie 100 95 100 Sorg 50 90 85

Table 3 (continued) Compound No. Application rate (kg / ha) Species 13th 0.5 14th 0.5 15th 0.5 Woolen 30th 90 80 So ya 0 95 95 Corn 10th 95 95 Rice 5 95 95 Wheat 20th 95 95 Shit 100 100 95 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 60 100 95 Green doggie 5 100 100 Sorg 30th 100 100 Compound No. 16th 17th 18th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 80 60 70 Soya 90 100 90 Corn 95 95 90 Rice 95 90 90 Wheat 95 100 95 Shit 70 100 95 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 95 100 90 Green doggie 100 100 100 Sorg 95 100 95

table (continued)

Compound No. 19th 22nd 23rd Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 20th 40 15th So ya 50 5 5 Corn 80 85 0 Rice 60 30th 5 Wheat 95 90 0 Shit 100 95 15th Soil mustard 100 100 95 Fiberglass galenical 100 100 100 Common rolling stock 95 100 5 Green doggie 95 100 95 Sorg 100 95 20th Compound No. 24th 25th 26th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 30th 80 85 Soya 10th 5 5 Corn 5 80 50 Rice 5 40 40 Wheat 5 85 50 Shit 50 100 80 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 70 70 15th Green doggie 100 95 60 Sorg 50 80 50

table (continued)

Compound No. 27th 28th 29th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 10th 0 100 So ya 5 0 100 Corn 70 5 100 Rice 40 5 100 Wheat 70 15th 100 Shit 85 20th 100 Soil mustard 100 50 100 Fiberglass galenical 100 100 100 Common rolling stock 80 40 100 Green doggie 95 0 100 Sorg 70 20th 100 Compound No. 30th 31st 33 Application rate (kg / ha) 0.25 0.5 0.25 Species Woolen 80 70 10th So ya 80 100 0 Corn 85 95 15th Rice 95 85 0 Wheat 95 95 5 Shit 100 100 85 Soil mustard 100 100 90 Fiberglass galenical 100 100 95 Common rolling stock 80 100 5 Green doggie 100 100 5 Sorg 85 95 15th

table (continued)

Compound No. Application rate (kg / ha) Species 34 0.25 36 0.25 37 0.25 Woolen 95 30th 70 So ya 0 0 5 Corn 5 15th 30th Rice 5 5 40 Wheat 5 10th 15th Shit 100 100 100 Soil mustard 95 100 100 Fiberglass galenical 100 100 100 Common rolling stock 5 90 30th Green doggie 0 85 0 Sorg 10th 10th 30th Compound No. 39 40 41 Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 30th 10th 20th Soya 10th 15th 0 Corn 30th 30th 10th Rice 60 40 10th Wheat 10th 5 30th Shit 5 20th 95 Soil mustard 95 100 100 Fiberglass galenical 95 100 100 Common rolling stock 80 90 10th Green doggie 100 100 70 Sorg 95 30th 20th

table (continued)

Compound No. 42 43 48 Application rate (kg / ha) 0.5 0.5 0.25 Species Woolen 90 5 20th Soya 5 5 70 Corn 5 10th 80 Rice 15th 10th 40 Wheat 5 10th 80 Shit 20th 80 50 Soil mustard 80 100 100 Fiberglass galenical 10th 100 100 Common rolling stock 20th 50 95 Green doggie 50 100 100 Sorg 20th 40 95 Compound No. 49 50 51 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 15th 10th 20th So ya 20th 50 30th Corn 40 70 80 Rice 15th 10th 15th Wheat 20th 50 40 Shit 20th 70 60 Soil mustard 50 100 80 Fiberglass galenical 100 100 100 Common rolling stock 85 95 95 Green doggie 100 100 100 Sorg 70 80 95

Table 3 (continued) Compound No. Application rate (kg / ha) Species 52 0.25 53 0.25 54 0.25 Woolen 20th 40 15th Soya 10th 10th 40 Corn 30th 30th 20th Rice 0 0 5 Wheat 5 10th 20th Shit 30th 30th 60 Soil mustard 100 95 100 Fiberglass galenical 100 100 100 Common rolling stock 5 15th 20th Green doggie 80 95 95 Sorg 15th 60 70 Compound No. 57 58 59 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 80 15th 70 Soya 90 80 90 Corn 95 50 90 Rice 70 60 90 Wheat 95 70 90 Shit 80 70 85 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 95 40 100 Green doggie 100 100 100 Sorg 95 70 100

Table 3 (continued) Compound No. 60 62 63 Application rate (kg / ha) 0.25 0.125 0.125 Species Woolen 5 80 50 Soya 15th 0 30th Corn 30th 0 0 Rice 50 30th 50 Wheat 30th 5 5 Shit 50 100 90 Soil mustard 60 100 100 Fiberglass galenical 100 100 100 Common rolling stock 80 70 50 Green doggie 100 40 80 Sorg 95 30th 30th Compound No. 64 65 66 Application rate (kg / ha) 0.125 0.125 0.0625 Species Woolen -70 15th 0 So ya 0 10th 0 Corn 0 5 5 Rice 30th 20th 5 Wheat 5 0 0 Shit 100 80 100 Soil mustard 100 70 0 Fiberglass galenical 100 100 95 Common rolling stock 60 10th 10th Green doggie 70 50 0 Sorg 60 40 5

table (continued)

Compound No. 67 68 69 Application rate (kg / ha) 0.0625 0.0625 0.25 Species Woolen 10th 0 20th So ya 0 0 15th Corn 0 0 15th Rice 10th 0 5 Wheat 5 0 5 Shit 50 5 95 Soil mustard 50 10th 30th Fiberglass galenical 50 0 100 Common rolling stock 5 0 15th Green doggie 0 5 0 Sorg 0 0 15th Compound No. 70 72 73 74 Application rate (kg / ha) 0.25 0 .25 0 .25 0.5 Species Woolen 5 5 0 5 So ya 0 5 0 10th Corn 100 10th 0 50 Rice 0 10th 0 70 Wheat 0 5 0 40 Shit 20th 40 5 20th Soil mustard 0 95 0 100 Fiberglass galenical 90: L00 0 95 Common rolling stock 0 30th 5 70 Green doggie 0 60 0 95 Sorg 0 30th 0 95

table

HERBICIDAL ACTIVITY IN THE EVENING OF PLANTS (% CONTROL)

Compound No. Application rate (kg / ha) Species 1 0.5 2 0.5 3 0.5 Woolen 95 100 100 So ya 50 40 60 Corn 50 30th 60 Rice 20th 30th 40 Wheat 30th 40 20th Shit 90 95 100 Soil mustard 80 95 100 Fiberglass galenical 30th 100 100 Common rolling stock 50 30th 70 Green doggie 50 15th 95 Sorg 30th ND 80 Compound No. 4 5 6th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 90 100 100 Soy a 80 80 40 Corn 50 50 40 Rice 50 60 15th Wheat 50 80 30th Shit 100 100 90 Soil mustard 100 100 95 Fiberglass galenical 100 100 100 Common rolling stock 85 90 20th Green doggie 50 100 15th Sorg ND 70 10th

table (continued)

Compound No. 7th 8th 9th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 100 100 100 Soy a 80 50 95 Corn 40 40 50 Rice 40 20th 20th Wheat 40 40 20th Shit 100 100 100 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 60 40 20th Green doggie 30th 40 15th Sorg 40 30th 40 Compound No. 10th 11th 12th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 100 95 100 So ya 60 40 ' 60 Corn 50 50 70 Rice 20th 15th 50 Wheat 40 30th 95 Shit 90 90 100 Soil mustard 95 70 95 Fiberglass galenical 100 100 100 Common rolling stock 70 90 95 Green doggie 40 50 85 Sorg ND ND 95

table (continued)

Compound No. 13th 14th 15th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 100 100 100 Soya 70 85 95 Corn 50 70 90 Rice 50 30th 90 Wheat 90 90 90 Shit 100 100 100 Soil mustard 100 100 95 Fiberglass galenical 100 100 100 Common rolling stock 95 95 100 Green doggie 100 95 100 Sorg 70 ND 90 Compound No. 16th 17th 18th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 95 100 100 So ya 80 100 80 Corn 80 100 70 Rice 70 95 80 Wheat 80 100 90 Shit 100 100 95 Soil mustard 85 100 85 Fiberglass galenical 100 100 100 Common rolling stock 100 95 70 Green doggie 95 100 100 Sorg 85 95 80

table (continued)

Compound No. 19th 22nd 23rd Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 100 100 70 So ya 90 50 40 Corn 95 85 60 Rice 80 40 25th Wheat 100 80 30th Shit 100 100 90 Soil mustard 80 80 80 Fiberglass galenical 100 100 90 Common rolling stock 60 85 20th Green doggie 90 90 40 Sorg 95 95 40 Compound No. 24th 25th 26th Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 100 100 100 Soya 80 70 90 Corn 60 85 60 Rice 10th 60 40 Wheat 20th 60 40 Shit 100 100 100 Soil mustard 80 100 95 Fiberglass galenical 100 100 100 Common rolling stock 40 30th 70 Green doggie 80 70 95 Sorg 60 100 60

Table 4 (cont'd) Compound No. Application rate (kg / ha) Species 27th 0.5 28th 0.25 29th 0.5 Woolen 100 80 100 Soya 80 60 95 Corn 85 80 100 Rice 60 50 95 Wheat 80 60 100 Shit 100 85 100 Soil mustard 100 90 100 Fiberglass galenical 100 100 100 Common rolling stock 30th 30th 100 Green doggie 60 95 100 Sorg 80 60 100 Compound No. 30th 31st 33 Application rate (kg / ha) 0.5 0.5 0.25 Species Woolen 100 100 100 Soya 85 85 80 Corn 80 70 50 Rice 70 60 15th Wheat 100 100 20th Shit 100 100 100 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 50 95 30th Green doggie 100 95 15th Sorg 95 95 20th

table (continued)

Compound No. 34 36 37 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 100 100 100 Soya 60 40 70 Corn 30th 60 70 Rice 20th 10th 40 Wheat 50 20th 20th Shit 100 100 100 Soil mustard 100 100 100 Fiberglass galenical 100 100 100 Common rolling stock 60 90 50 Green doggie 70 100 5 Sorg 50 30th 30th Compound No. 39 40 41 Application rate (kg / ha) 0.5 0.5 0.5 Species Woolen 70 90 100 Soya 40 40 95 Corn 70 50 70 Rice 40 15th 70 Wheat 30th 40 70 Shit 70 90 100 Soil mustard 100 80 100 Fiberglass galenical 100 95 100 Common rolling stock 70 80 95 Green doggie 80 40 100 Sorg 85 ND 80

table (continued)

Compound No. 42 43 48 Application rate (kg / ha) 0.5 0.5 0.25 Species Woolen 100 100 100 So ya 40 100 80 Corn 70 100 80 Rice 15th 60 40 Wheat 15th 95 40 Shit 100 100 100 Soil mustard 90 100 90 Fiberglass galenical 100 100 100 Common rolling stock 5 95 95 Green doggie 10th 100 100 Sorg 60 70 90 Compound No. 49 50 51 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 100 100 100 Soya 70 80 95 Corn 30th 80 40 Rice 20th 40 15th Wheat 15th 20th 15th Shit 95 100 70 Soil mustard 70 80 70 Fiberglass galenical 100 100 100 Common rolling stock 50 70 15th Green doggie 85 100 60 Sorg 80 85 20th

table (continued)

Compound No. 52 53 54 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 95 100 95 Soya 50 50 70 Corn 60 40 50 Rice 15th 30th 30th Wheat 10th 15th 30th Shit 50 50 70 Soil mustard 95 80 100 Fiberglass galenical 100 100 100 Common rolling stock 15th 10th 15th Green doggie 100 50 95 Sorg 5 10th 50 Compound No. 57 58 59 Application rate (kg / ha) 0.25 0.25 0.25 Species Woolen 90 90 100 Soya 90 90 90 Corn 90 50 100 Rice 80 40 95 Wheat 95 60 95 Shit 100 90 100 Soil mustard 95 100 100 Fiberglass galenical 100 100 100 Common rolling stock 95 60 100 Green doggie 100 90 100 Sorg 95 95 100

table (continued)

Compound No. 60 62 63 Application rate (kg / ha) 0.25 0.0313 0.0313 Species Woolen 90 90 95 Soya 95 70 50 Corn 50 70 60 Rice 60 5 10th Wheat 40 10th 10th Shit 90 100 100 Soil mustard 100 80 70 Fiberglass galenical 100 100 100 Common rolling stock 20th 50 40 Green doggie 40 20th 0 Sorg 100 20th 40 Compound No. 64 65 66 Application rate (kg / ha) 0.0313 0.125 0.0625 Species Woolen 80 95 90 So ya 50 90 40 Corn 90 40 70 Rice 10th 30th 30th Wheat 10th 40 20th Shit 100 100 100 Soil mustard 85 60 70 Fiberglass galenical 100 100 100 Common rolling stock 60 70 30th Green doggie 15th 20th 15th Sorg 20th 60 10th

Table 4 (cont'd) Compound No. 67 68 69 Application rate (kg / ha) 0.0625 0.0625 0.25

Species

Woolen 95 40 90 Soya 40 50 80 Corn 70 60 70 Rice 50 5 20th Wheat 40 10th 15th Shit 100 70 100 Soil mustard 100 10th 20th Fiberglass galenical 100 95 100 Common rolling stock 70 15th 30th Green doggie 70 15th 50 Sorg 40 10th 30th Compound No. 79 72 73 74 Application rate (kg / ha) 0.25 0.25 0.25 0.5 Species Woolen 80 100 60 85 Soya 50 80 30th 50 Corn 20th 70 60 60 Rice 5 15th 10th 30th Wheat 10th 30th 10th 50 Shit 90 100 30th 80 Soil mustard 50 90 40 95 Fiberglass galenical 100 100 100 100 Common rolling stock 30th 10th 30th 90 Green doggie 30th 70 70 80 Sorg 20th 20th 15th

Claims (19)

DEFINITION OF INVENTION A compound having Q-substituted 1-phenyl-4,5-dihydro-1,2,4-triazol-5 (1H) -one, wherein Q is substituted with a carbon atom at the 5-position of the phenyl group and wherein: Q is -CH (R ² ) C (R ³ ) (R ⁴ ) O ¹ or -CH = C (R ⁴ ) Q ¹ ; R ² is H or halogen and R ³ is halogen; R ⁴ is H or lower alkyl; in addition, this compound is: (a) a carboxylic acid with Q - COOH or b) a salt, ester, amide or nitrile of this carboxylic acid; in addition, a 5-methoxy analogue and a 5-propargyloxy analogue of this compound having herbicidal activity. 2. The herbicidal compound according to claim 1, wherein the Q substituent is 1-phenyl-4,5-dihydro-1,2,4-triazol-5 (1H) -one, wherein the Q substituent is linked to the phenyl ring 5. carbon atom in position 2A and wherein: Q is -CH (R ² ) C (R ³ ) (R ⁴ ) O ¹ or -CH = C (R ⁴ ) Q ¹ ; R is H or halogen and R is halogen; R ⁴ is H or lower alkyl; O ¹ - COOH, COOZ, COOR ⁵ , CON (R ⁶ ) (R ⁷ ), CN, CHO or C (O) R ⁵ Z is a salt-forming group; R ⁵ is alkyl, alkoxycarbonylalkyl, cycloalkyl or aralkyl; R ⁶ and R 'are each independently alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, phenyl, benzyl, SO ₂ R ⁶ or one of the foregoing radicals substituted with halogen, alkyl or cyano; in addition, the 5-methoxy analog and the 5-propargyloxy analog of this compound. 3. The herbicidal compound according to claim 2, which has the formula: wherein R is halogen, haloalkyl; lower alkyl or lower R ¹ lower alkyl or haloalkyl; X is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, halogenated lower alkylsulfinyl or halogenated lower alkoxy. 4. A compound according to claim 3 wherein R is CH ₃ , R ¹ is CHF ₂ , X is F or Cl, and Y is Cl or Br. 5. A compound according to claim 4, wherein Q is CH ₂ CH (Cl) COOR ⁵ and R ^J is lower alkyl. 6. A compound according to claim 3 wherein R ⁵ is ethyl, X is F and Y is Cl. 7. A compound according to claim 4 wherein Q is -CH = CHQ ^; group. 8. A compound according to claim 3, wherein Q is a -CH ₂ CH (Cl) 0 ¹ group. 9. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 1 in admixture with a suitable carrier. 10. A method of inhibiting undesirable growth of vegetation comprising the use of a herbicidally effective amount of a composition according to claim 9 in a focal area requiring such control. 11. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 3 in admixture with a suitable carrier. 12. A method of inhibiting undesirable growth of vegetation comprising the use of a herbicidally effective amount of a composition according to claim 11 in a focal area requiring such control. 13. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 5 in admixture with a suitable carrier. 14. A method of inhibiting the growth of vegetation undesirable growth, which comprises using a herbicidally effective amount of a composition according to claim 13 in a focal area requiring such control. 15. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 7 in admixture with a suitable carrier. 16. A method of inhibiting undesirable growth of vegetation comprising the use of a herbicidally effective amount of a composition according to claim 15 in a focal area requiring such control. 17. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 8 in admixture with a suitable carrier. 18. A method of inhibiting undesirable growth of vegetation comprising the use of a herbicidally effective amount of a composition according to claim 17 in a focal area requiring such control. A compound of the formula O II ^ N-R ¹ M R or wherein R is halogen, lower alkyl or haloalkyl; R ¹ or lower alkyl or haloalkyl; X is hydrogen, haloalkyl, alkyl, haloalkyl, alkoxy or nitro; Y is hydrogen, halogen, alkyl, haloalkyl, alkoxy, halogenated lower alkylsulfinyl or halogenated lower alkoxy; R ² is H or halogen; R ³ is halogen; R ⁴ is H or lower alkyl; Q ^: - COOH, COOZ, COOR ⁵ , CON (R ⁶ ) (R ⁷ ), CN, CHO or C (O) R ⁵ ; Z is a salt-forming group; R ⁵ is alkyl, alkoxycarbonylalkyl, cycloalkyl or aralkyl; R ⁶ and R ⁷ - are each, independently of one another, are a radical alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, phenyl, benzyl, SO ₂ R ⁶ or one of the following radicals substituted by halogen, alkyl or cyano; method of obtaining, characterized by performing: (a) a compound of the formula Interaction of NH according to Meerwein's arylation reaction with a compound of formula CH (R ² ) = C (R ⁴ ) (Q ⁴ ); b) a compound of the formula O R interaction according to a Wittig reaction with alkilidenfosforanu which alkilideninė formula = C (R ⁴⁾ Q ¹ or fosfonatilidu containing P atom directly connected -CHfR'bc) ¹ Group 15; c) reacting a compound of formula wherein Q is -CH (R ² ) C (R ³ ) (R ⁴ ) O ¹ or -CH = C (R ⁴ ) (Q ⁴ ) at elevated temperature in the presence of a base of a compound of formula R ¹ ^ ¹ wherein X ¹ is Cl, Br, I or arylsulfonyloxy.