DK172104B1 - Substituted triazolinones, methods and intermediates for their preparation as well as their use - Google Patents

Description

DK 172104 B1

The invention relates to novel substituted triazolinones, methods and intermediates for their preparation as well as their use as herbicides.

It is known that certain nitrogen heterocyclic compounds, e.g. 4-Amino-3-methyl-6-phenyl-1,2,4-triazin-5-one or N-isobutyl-2-oxymimidazolidine-1-carboxamide has herbicidal properties, cf. eg. German Publication No. 2,364,474 and R. Wegler "Chemie der Pfanzenschutz- und Schådlingsbekåmpfungsmiddel", volume 5, page 219 (1977).

10 However, the herbicidal effect of these already known compounds against problem weeds, as well as their compatibility with important crop plants, is not entirely satisfactory in all applications.

JP-A-52/125 168 describes 4-amino-3-alk (en / yn) yl-1,2,4-triazolin-5-one derivatives, their synthesis and their use as herbicides.

Furthermore, certain substituted triazolinones, f. items 1- (N, N-dimethylcarbamoyl) -3-phenyl-4-amino-1,2,4--triazolin-5-one, cf. J. Heterocycl. Chem. 17, 1691-1696 (1980) and Org. Mass. Spectrom. 14, 369-378 (1979).

So far, there is no known effect of these already known triazolinones as herbicides.

The novel substituted triazolinones of the invention are characterized in that they have the general formula 25 I

R 1, - N 1 NH 2 1 (I) 2 B1 haloalkenyl or haloalkynyl with each 2 to 8 carbon atoms and 1 to 15, respectively 13 or different halogen atoms, cyanoalkyl of 1-8 carbon atoms, hydroxyalkyl of 1-8 carbon atoms and 1-6 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl with each up to 6 carbon atoms in the individual alkyl and alkenyl moieties, alkylaminoalkyl or dialkylaminoalkyl with each 1-6 carbon atoms in the individual alkyl moieties, cycloalkyl having 3-11 carbon atoms or each especially optionally one or 10 several times, the same or differently substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl each having 3-8 carbon atoms in the cycloalkyl or cycloalkenyl moiety and, if necessary, 1-6 carbon atoms in the straight or branched alkyl moiety, the substituents 15 are selected from the following: halogen, cyano and each straight or branched chain alkyl or haloalkyl each having 1-4 carbon atoms and, if necessary, 1-9 the same or different halogen atoms or straight or branched halogen alkenyl having up to 4 carbon atoms and 1-5 identical or 20 different halogen atoms or each twice to linked alkanediyl or alkenediyl with 1-4 carbon atoms respectively, or R2 means heterocyclylalkyl having 1-6 carbon atoms in the straight chain or branched alkyl moiety wherein the heterocyclyl group has the formula O, O, path, Ό, #, S3, c.

) o or —t / \ 1H

Wherein Z means oxygen or sulfur; or R2 each represents straight or branched chain alkoxy of 1-8 carbon atoms, alkenyloxy of 2-8 carbon atoms or alkyloxy of 2-8 carbon atoms and finally each of which optionally means one or more times, the same or different substituted aralkyl , aryl or aryloxy each having 6-10 carbon atoms in the aryl moiety and, if so, 1-8 carbon atoms in the alkyl moiety, the alkyl substituents being selected from halogen and cyano, and the aryl substituents being selected from 10 halogen, alkyl and alkoxy, or R2 being benzyl with condensed -O-CH 2 -O group in the phenyl moiety, X means oxygen or sulfur and Y means oxygen or sulfur.

The compounds of formula I may optionally exist as geometric and / or optical isomers or isomer mixtures of different composition depending on the nature of the substituents R1 and R2. Both the pure isomeric and isomeric mixtures are encompassed by the invention.

It has been found according to the invention that the novel substituted triazolinones of the general formula I according to the invention can be prepared by a process which is characterized in that:

a) hydrazones of formula II

1 '* 3

R1 = N - N = C

T ~ T (II, II) nh-r2 wherein R 1, R 2, X and Y have the above meanings and R 3 and R 4 independently represent hydrogen, straight chain or branched alkyl of 1-4 carbon atoms, phenyl or benzyl, is reacted with an acid, optionally in the presence of a diluent,

b) 1H-triazolinones of formula III

4 DK 172104 B1 R1 ^ -N ^ NH, 1T 2 (III) 5 I ^

H

in which

R 1 and X have the above meanings, reacted with iso (thio) cyanates of formula IV

R 2 -N = C = Y (IV) wherein R 2 and Y have the above meanings, optionally in the presence of a diluent and optionally in the presence of a reaction aid, or

c) triazolinones of formula V

R 1 - N "NH 2 Ti (V) T 0-R 5 wherein R 1, X and Y have the above meanings, and

R5 is alkyl, aryl or arylalkyl, reacted with amines of formula VI

R2-NH2 (VI) wherein R2 is as defined above, optionally in the presence of a diluent and optionally in the presence of a reaction aid.

Furthermore, it has been found in accordance with the invention that the novel substituted triazolinones of general formula I have herbicidal properties.

Surprisingly, the substituted triazolinones of the general formula I according to the invention exhibit a significantly stronger herbicidal activity against problem weeds than the nitrogen heterocyclic compounds known in the art, e.g. 4-amino-3-methyl-6-phenyl-1,2,4-tri-azin-5-one, which are chemically and effectively related.

The invention thus also relates to: - herbicidal agents which are characterized by a content of at least one substituted triazolinone according to the invention, - a method for controlling weeds which is characterized in that substituted triazolinones according to the invention are caused to affect the weeds and / or its habitat, - the use of substituted triazolinones according to the invention for the control of weeds, and - a method for the preparation of herbicidal agents which are characterized by mixing substituted triazolinones 20 according to the invention with extenders and / or surfactants.

The substituted triazolinones of the invention are generally defined by Formula I.

Preferred are compounds of formula I in which R 1 is hydrogen, methyl, ethyl, n- or i-propyl, hydrogen, each optionally 1-3 times optionally with fluorine and / or chlorine substituted methyl, ethyl, n- or i. - propyl, n-, i-, s- or tert-butyl, allyl, propargyl, each straight or branched pentyl, hexyl, heptyl, octyl, butenyl, pentenyl, hexenyl, butynyl, pentynyl or hexynyl; and in addition each optionally means 1-3 times, the same or different, with fluorine, chlorine, methyl, ethyl and / or cyano substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl, cyclohexylethyl or DK 172104 B1 and 6 are cycloheptyl and furthermore, benzyl, phenylethyl or phenyl, X means oxygen or sulfur, and Y means oxygen or sulfur.

In detail, in addition to the compounds mentioned in the Preparative Examples, the following substituted triazolinones of general formula I are mentioned: 10 »1 I ^ (I) ^^ HH-R2

R1 r2 X Y

7CH3 20 / - (CH3 H y 0 0 ch3 \ 0 o

F

25 _ CH3 ° 0 ch3 ch3 -C (CH3) 3 o s 30 35

R1 R2 X Y

0 7 DK 172104 B1

CH3 -ccch3> 3 S S

5

ch3 - <T) S S

ch3 'I hJ ° ° 10 c2h5 -C (CH3) 3 oo C2H5 -C (CH3) 3 os c2h5 -C (CH3) 3 so 15 c2H5 - / 7) os c2H5 - ^ T) S o 20 C2H5 “KZ) ° 0

C2H5)> O S

C2HS)> S O

CH3

c2h5? cr-Q O O

S-Configurat ion

H -C (CH 3) 30 O

30 H -ZiT) O O

35

R1 R2 X Y

0 8 DK 172104 B1 5 H) 0 0

H -C (CH 3) 30 S

H -C (CH * a) q S O

H O S

η - <ε> * °? »3 15 ch3 -c-ch2-och3 oo ch3 / CH3 ch3 -ch-ch ^ oo I CH3 CH * a 20 CHq I ^ ch3 ch3 -c-ch2-n ^ oo I ch3 ch3 25 <[H3 ch3 -c-ch2 O o «ch3 ch3 -ch — CH-C2H5 oo 30 ch3 ch3 35 0 R1 R2 xy 9 DK 172104 B1 OCHg

5 CH3 -CH-ζ ^ -OCH3 O O

ch3 ch3 ch3 -ch — ζ ^ -ch3 o o

10 I

ch3 ch3 -ch - ^> - C2H5 o o ch3

CH3 -CH-Br O O

CH3

Cl

20 ch3 -CH - <() ~ C1 O O

I ^ 7 ch3

Cl ^ l ch3 ch2 X o o CHg

25 J

CH-, I ch3 ch3 -c-ch <o o I CH3 ch3 30 CH3 CH3 -C o o ch3 35

R1 R2 X Y

10 DK 172104 B1 o CHo 5 ch3 -c-CH-C2H5 oo ch3 ch3 CHo I ch3 ch3 -c-ch2-ch <oo ”J„ 3 CH * ch3 ch3 I 3 I 3 ch3 -cc-ch3 oo II 3 ch3 ch3 15 CH3 ch3 -c-ch2 — oo ch3 20 ch3 -ch-cooc2h5 oo ch3 ch3 -CH-CH2-CH2-CH- (CH2) 2-CH3 oo ch3 ch3 25 (CHo) o “CHra ch3 -ch <oo (CH2) 2-CH3 C2h5 ch3 -c-ch3 oo

30 Γ H

C2H5 35

F1 R2 X Y

11 DK 172104 B1 o

5 CH3 - / 7) O O

Cl CFg ch3 -ch2-ch2 <5 O o 10

CH3 -CH2-CH2— ^) “Br O O

and 3 ch 3 -ch 2 -ch 2 - ζ and 3 o o AND -a ch 3 -CH-CH 2 - <"% CH 3 o

20 J

ch3 o o ch3? CH3 Cl o o 25 CH / ^ C1 H3C ^ CH3

CH3 H3C C1 O O

Cl H3CwCH3 ch3 ^ ZS ^ Cl o o

30 XI

35 0 12 DK 172104 B1

R1 R2 X Y

5 CH3 0 0

Cl CH3 ch3 -ch2-c> <^ H: h3 o o CH3 CH3

CH3 O O

CH3 CH3 CH3 -C ~ (I O o ch3 20 CH3 -fKH 0 0 ch3 ch3 -CH- (CH2) 3-CH3 o C2H5

CH3 -CH- (CH2) 2-CH3 O O

c2h5 ch3 ch3 - (CH2) 3-CH <o o ch3 30 35

R1 R2 X Y

13 DK 172104 B1 CHo in 3 ch-ch3 ch3 -ch <oo CH-CH ~ i 3 ch3 ch3 -CH-CH2 ~ * / I oo ch3 and3 ch3 -ch2-ch <oo and3 15 <f «3 ch3 - ch-c-ch3 oo II 3 CN CH3 ch3 20 ch3 -ch-ch2-c- <3 oo ch3 ch3 ch3 -ch2 — oo 25 ch3 ch3 -C-CH3 os ch3 30 ch3 os CH3 R-Configuration 35 0 R1 R2 X y 14 DK 172104 B1

5 CH 3 -CH- {y 0 S

CHg S-Configuration ch3 CHq -ch-ch <os In ch3 ch, 10 d ch3 -ch-ch2-och3 os ch3 CH3 - (CH2) 2 "CH3 os 15 CH3 ch3 -ch <os ch3 ch3 ch3 -ch2-ch <os ch3

20 CH3 -CH-C2H5 O S

ch3 ch3 XX o s 25 CH3 - (I 0 s ch3 -cch2) 2-ch3 s o ch3 - (ch2) 3 ~ ch3 s o 30 CH3 ch3 -ch2-ch <s o ch3 ch3 -ch-c2h5 s o ch3 35 DK 172104 B1

Used e.g. 1- (N-Isobutylcarbamoyl) -4-isopropyl-idenimino-3-methyl-1,2,4-triazolin-5-one as a starting compound, the course of the reaction can be carried out. process a) according to the invention is illustrated by the following reaction scheme: 5

HaC> -N ^ N = C ^ e II I ch3 h2o / h I ^ - (CH3) 2CO0 NH-CH2-CH (CH3) 2

HAC> N ^ NH2

Ti NH-CH2 “CHCCH3) 2

Used e.g. 4-Amino-3-methyl-1,2,4- (1H) -triazolin-5-one and tert-butyl isocyanate as starting compounds, the reaction process of process b) of the invention can be illustrated by the following reaction scheme: 4 (CH3) 3C-N »C * 0 N ^ N ^ o

H

CH3 ^ jj - * ^ 2 30 -> 0 = C-HH-C (CH3) 3

Used e.g. 1-Ethoxycarbonyl-4-amino-3-methyl-1, 2,4-triazolin-5-one and N, N-diethyl-propane-1,3-diamine as starting compounds can proceed the process by process 16 c) according to the invention is illustrated by the following reaction scheme: 5 * H 2 N-CH 2 -CH 2 -C 2 -N <2 "5 rr-N 2 o C 2 H 5 o = c-oc 2 H 5 CH 3" mV 2 H 2 - CoHc-OH v II 1 I c2h5 o = c-nh-ch2-ch2-ch2 “N <c2h5

The hydrazones required as starting compounds for carrying out process a) according to the invention are generally defined by formula II. In this formula II, R1 and R2 preferably represent the groups already mentioned as preferred for these substituents in the discussion of the compounds of formula I according to the invention.

The hydrazones of formula II with the exception of compounds 1- (N-4-bromophenylthiocarbamoyl) -4-phenylideneamino-1,2,4-triazoline-5-thione 1- (N-4-bromophenylthiocarbamoyl) - 4- (4) -hydroxyphenylideneamino) - 1,2,4-triazoline-5-thione, 1- (N-4-bromophenylthiocarbamoyl) -4- (2-nitrophenylideneamino) - 1,2,4-triazoline-5-thione, 1- (N- 4-Bromophenylthiocarbamoyl) -4- (3-nitrophenylideneamino) - 1,2,4-triazoline-5-thione are not yet known and are also the subject of the present invention. However, they are obtained by analogy with known methods (cf., e.g., Acta Pol. Pharm. 38., 153-162 (1981),

35 respectively. C.A. £ 5 .; J), e.g. in that 1-unsubstituted 4-amino triazolinones of formula III

17 DK 172104 B1 R1 · ^ .- N- ^ NHo TI - Ν ^ Ν ^ χ (III)

5 H

in which

R 1 and X have the meanings given above, reacted with aldehydes or ketones of formula VII

Wherein R3 and R4 have the above meanings, at temperatures between 40 and 120 ° C, optionally in the presence of 20 of a diluent, e.g. methylene chloride or toluene, and optionally in the presence of a catalyst, e.g. p-toluene sulfonic acid, and the thus-prepared 1-unsubstituted triazolinone hydrazones of formula VIII R * \ - N- ^ N = Cv.

Μ In R4 (VIII>

H

Wherein R 1, R 3, R 4 and X have the above meanings, either in a subsequent second step iso (thio) cyanates are reacted

of formula IV

R 2 -N = C = Y (IV) wherein R 2 and Y have the meanings given above, at temperatures between 50 and 150 ° C, optionally in the presence of a diluent, e.g. methylene chloride or dioxane, and optionally in the presence of a reaction aid, e.g. triethylamine,

5 or alternatively in a subsequent second step, react with (thio) chloroformic acid esters of formula IX

Y

s I

Wherein R5 and Y have the above meanings, at temperatures between -20 and 40 ° C, optionally in the presence of a diluent, e.g. tetrahydrofuran, and optionally in the presence of a reaction aid, e.g. sodium hydride or potassium tert.butanolate,

and the triazolinones of formula X thus produced

20 ^ r3

Rlv -, - N'N = Cv ^ II I F4 ΝΝ | ί- ^ χ (X) Y = C-O-R5 wherein R1, R3, R4, R5, X and Y have the meanings given above,

in a subsequent third step is reacted with amines of formula VI

Wherein R2 is as defined above, at temperatures between 20 and 50 ° C, optionally in the presence of a diluent such as tetrahydrofuran, and optionally in the presence of a base, e.g. sodium hydroxide or potassium hydroxide.

DK 172104 B1 19

Thereby, it is also possible and advantageous to carry out the reaction of the 1-unsubstituted triazolinone hydrazones of formula VIII with (thio) chloroformic acid esters of formula IX and the subsequent reaction of the thus-prepared triazolinones X with amines of formula VI reaction step in a so-called single-container method, cf. Example 3.

The 1-unsubstituted 4-amino triazolinones of formula III are known or can be prepared analogously to known methods, cf. eg. J. Heterocycl. Chem. Ιέ, 403 (1979), J. Heterocycl. Chem. 17, 1691 (1980), Europ. J. Med. Chem.

18. 215 (1983), Chem. Ber. 98, 3025 (1965) or Liebigs

Ann. Chem. 637. 135 (1960).

The aldehydes and ketones of formula VII are commonly known compounds in organic chemistry.

The 1-unsubstituted triazolinone hydrazones of formula VIII are largely known, cf. eg. J. Heterocycl. Chem. 20, 77-80 (1983), J. Heterocycl. Chem. 16, 403-407 (1979), Chim. Acta. Overture. 7, 269-290 (1979), J. chem. Soc., 20 Perkin Trans. II, 1973. 9-11 and J. org. Chem. 36, 2190-2192 (1971).

The (thio) chloroformic acid esters of formula IX are commonly known compounds in organic chemistry.

The triazolinones of formula X mentioned as intermediates are partly known, cf. eg. Acta. Pole. Pharm. , 38 / 153-162 (1981), respectively. C.A. 95: 203841j.

The novel and also objects of the present invention are triazolinones of the formula Xa 30 (Xa) (j TR <1,5 Y = C-O-R5 35 20 wherein R1-1 means straight or branched alkyl of 1-4, especially 1-3 carbon atoms, especially methyl, R 3, R 4, R 5, X and Y are as defined above.

R 5 represents straight or branched alkyl of 1-4 carbon atoms or means phenyl or benzyl, and X and Y each independently represent oxygen or sulfur, preferably oxygen.

The starting compounds for carrying out process b) according to the invention are generally defined by formula III. In this formula III, R 1 and X preferably represent the groups already mentioned as preferred for these substituents in the discussion of the compounds of formula I according to the invention.

The 1H-Triazolinones of Formula III are known or can be obtained by analogy with known methods, cf. eg. J. Heterocycl. Chem. 16, 403 (1979), J. Heterocycl. Chem. 17/1691 (1980), Europ. J. Med. Chem. 18, 215 (1983), Chem.

Ber. : 98, 3025 (1965) and Liebigs Ann. Chem. 637. 135 (1960).

The further iso (thio) cyanates required as starting compounds for carrying out process b) of the invention are generally defined by formula IV. In this formula IV, R 2 and Y preferably represent the groups already mentioned as preferred for these substituents in the discussion of the compounds of formula I according to the invention.

The iso (thio) cyanates of formula IV are mostly known compounds in organic chemistry. The compounds 2,2,2-trifluoroisopropyl cyanate and 2,2,2-trifluoro-1,1-dimethylethyl cyanate are not yet known, but can be prepared by known methods. Thus, the iso (thio) cyanates are obtained e.g. by reacting the corresponding amines with phosgene, optionally in the presence of a base, e.g. triethylamine, cf. eg. German Patent Nos. 2,804,082 and 2,512,514, U.S. Patent Nos. 3,584,028, and 3,331,654, Japanese Patent No. 50/29599, Synthesis 1985, page 682, or J. Am. Chem. Soc. 77, 1901-1902 (1955).

21 DK 172104 B1

The starting compounds necessary for carrying out process c) according to the invention are generally defined by formula V. In this formula V, R 1, X and Y preferably represent the groups already mentioned 5 as preferred for these substituents in the discussion of the compounds of formula In accordance with the invention.

The triazolinones of formula V are partly known, cf. eg. J. Heterocycl. Chem. 17, 1691-1696 (1980).

The novel and also objects of the present invention are the triazolinones of formula Va

Rl'Sj — V ™ * JL4. Y = C-O-R 5 wherein R 1 represents straight or branched alkyl of 1-4, especially 1-3 carbon atoms, especially preferred methyl, and r5 means straight or branched alkyl of 1-4 carbon atoms or means phenyl or benzyl and X and Y have the above meanings.

They are obtained by analogy with the preparation of the known compounds of formula V in that 1H-triazolinones of formula 11a 25 "" • "[j-pw2 (IIla) I

H

30 wherein

R 1 and X have the meanings given above, reacted with (thio) chloroformic acid esters of formula IX

R5-0-C-Cl (IX)

II

Y

Wherein R5 and Y have the above meanings, at temperatures between -20 and 40 ° C, optionally in the presence of a diluent, e.g. tetrahydrofuran, and optionally in the presence of a reaction aid, e.g. potassium tert.butanolate or sodium hydride (cf. also the preparation examples).

The 1H-Triazolinones of formula IIla are known or can be obtained by analogy with known methods, cf. eg. J.

Heterocycl. Chem. 16, 403 (1979), J. Heterocycl. Chem. 17th

1691 (1980), Europ. J. Med. Chem. 18, 215 (1983), Chem.

Ber. 98, 3025 (1965) and Liebigs Ann. Chem. 637, 135 (1960).

As acids for carrying out process a) according to the invention, all inorganic and organic acids useful for hydrazone cleavage 15 can usually be used. Preferably, inorganic mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid are used.

As diluents for carrying out process a) according to the invention, all the usual inorganic or organic solvents can be used. Preferably, polar, water-miscible organic solvents, especially alcohols such as methanol, ethanol, propanol or butanol, mixtures thereof with water or pure water are used as diluents.

The reaction temperatures in carrying out process a) of the invention can be varied within a larger range. Usually, temperatures are between 20 and 150 ° C, preferably at temperatures between 50 and 120 ° C.

Process a) according to the invention is usually carried out at normal pressure or under reduced pressure. If operated under reduced pressure, pressure ranges between 20 and 400 mbar may be used, preferably between 100 and 200 mbar.

For carrying out process a) according to the invention, usually 1-50 moles, preferably 1-20 moles of acid 35 per mole are used. moles of hydrazone of formula II. Thereby, the hydrazone of formula II is dissolved in an appropriate amount of diluent, the required amount of acid is added and the mixture is slowly evaporated over several hours under reduced pressure.

In a particular embodiment, it is also possible to carry out process a) according to the invention and preparation 5 of the necessary starting compounds of formula II in one reaction step in a so-called single container method.

Thereby, it is possible, as starting compounds, to select the triazolinones of formula X and to react in a single container method one after the other with amines of formula VI 10 and then with acid according to process a) according to the invention (cf. also the preparation examples) or alternatively as starting compounds to choose triazoline. -hydrazones of formula VIII and reacting them in a single-container method one after another with (thio) chloroformic acid esters of formula 15, then with amines of formula VI and finally with acid according to process a) according to the invention.

As diluents for carrying out process b) according to the invention, inert organic solvents can be used. Particularly included are aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, e.g. gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform or carbon tetrachloride, ethers, e.g. diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or 25-diethyl ether, nitriles, e.g. acetonitrile or propionitrile, amides, e.g. dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, or esters, e.g. ethyl acetate.

Process b) according to the invention is optionally carried out in the presence of a suitable reaction aid. As such, all common inorganic or organic bases can be used. These include, for example. tertiary amines, e.g. triethylamine, N, N-dimethylaniline, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine or dibutyltin dilaurate, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonone (DBN) ).

24 DK 172104 B1

The reaction temperatures in carrying out process b) according to the invention can be varied within a larger range. Usually, temperatures are between 0 and 150 ° C, preferably at temperatures between 20 and 100 ° C.

For carrying out process b) according to the invention, 1.2-2.0 moles, preferably 1.0-1.5 moles of iso (thio) cyanate of formula IV and optionally 0.001-2.0 moles, preferably 0.001-1, are usually used. , 0 moles of reaction aid per mole of 1H - triazolinone of formula III. The reaction, the work-up and the isolation of the reaction products are carried out by conventional methods.

As diluents for carrying out process c) according to the invention, inert organic solvents can be used.

In particular, these include aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, e.g. gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform and carbon tetrachloride, ethers, e.g. diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles, e.g. acetonitrile or propionitrile, amides, e.g. dimethylformamide, dimethylacetamide, N-methylform anilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide, esters, e.g. ethyl acetate, or sulfoxides, e.g.

Dimethyl sulfoxide.

Process c) of the invention may optionally be carried out in the presence of a suitable reaction aid. As such, all common inorganic or organic bases can be used. These include, for example, alkali metal hydroxides, e.g. sodium hydroxide or potassium hydroxide, alkali metal carbonates, e.g. sodium carbonate, potassium carbonate or sodium hydrogen carbonate, as well as tertiary amines, e.g. triethylamine, Ν, Ν-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonone (DBN) or diazabicycloundecene (DBU).

DK 172104 B1

The reaction temperatures in carrying out process c) of the invention may be varied within a larger range. Usually, temperatures are between 0 and 120 ° C, preferably at temperatures between 20 and 50 ° C.

For the purpose of carrying out process c) according to the invention, 1.0 to 5.0 moles, preferably 1.0 to 2.5 moles of amine of formula VI, and optionally 1.0 to 2.0 moles, preferably 1.0 to 1, are usually used. , 2 moles of reaction aid per moles of triazolinone of formula V. The reaction, work-up and isolation of the reaction products are carried out by conventional methods.

In a particular embodiment, it is also possible to carry out process c) according to the invention and the preparation of the necessary starting compounds of formula V in one reaction step by a so-called single container method.

Thereby, starting from 1H-triazolinones of formula V, they are reacted successively by the single-container method first with (thio) chloromyric esters of formula IX and then with amines of formula VI according to method c) of the invention.

Another method for the preparation of compounds of formula I according to the invention is that oxadiazolinones of formula XI

25 1

R

N 1 -N 2 O (XI) r NH-R 2 wherein R 1, R 2 and Y have the above meanings are reacted with hydrazine hydrate at temperatures between 20 and 100 ° C in the presence of a suitable diluent, e.g. methanol or ethanol,

35 and the thus-prepared carboxylic acid derivatives of formula XII

26 DK 172104 B1 0 0

. II II

R1-C-NH-N-C-NH-NHo (XII) I Y = C-NH-R2 wherein

R 1, R 2 and Y have the above meanings, are thermally cyclized at temperatures between 80 and 200 ° C in the presence of a suitable diluent, e.g. toluene, chlorobenzene or dichlorobenzene.

The oxadiazolinones of formula XI are known (cf., for example, French Patent No. 1,415,605, CA 64.:P5105g and Dutch Publication No. 6,510,645, CA 65: P2274d-f, respectively) or may be obtained by ordinary known methods, e.g. by reacting the corresponding 4H-oxadiazolinones with iso (thio) cyanates of formula IV analogous to the practice of process b) of the invention or with the synthesis of the starting compounds of formula II.

The purification of the final products of formula I is carried out by conventional methods, e.g. column chromatographic or by recrystallization. The characterization is done by the melting point or for non-crystallizing compounds by the proton nuclear resonance spectrum.

The active compounds of the invention can be used as defoliants, desiccants, plant control agents and especially as herbicides. Weeds in the broadest sense are understood to mean all plants that grow in places where they are undesirable. Whether the compounds of the invention act as total or selective herbicides depends in particular on the amount used.

The active compounds of the invention may e.g. used in the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, 35 Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Cheno podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Ambrosia, Ambrosia Solanum, Rorippa, Rotala, Lindernia, La- 172104 Bl 27 mium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.

Dicotyledonous plants of the genera: Gossypium, Glycine,

Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, 5 Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledonous weeds of the butchers: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachi-aria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, 10 Cynodon, Monochoria, Fimbristylis, Sagittaria, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledonous plants of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus and Allium.

However, the use of the active compounds of the invention is by no means limited to these genera, but extends in the same way to other plants as well.

Depending on the concentration, the compounds are suitable for total weed control, e.g. in industrial and track areas, and on roads and squares with and without woodland. Also, the compounds can be used for weed control in enduring cultures, e.g. forestry, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, rubber, 25 oil palm, cocoa, berry and hop plants and for selective weed control in annual crops.

The compounds of formula I according to the invention are particularly suitable for the selective control of mono- and dicotyledonous plants, especially in dicotylous cultures such as e.g. sack-30 beets.

Also worth mentioning is the excellent effect against the difficult-to-control problem weed (Mercurialis).

The active compounds can be transferred into the usual forms of preparations, such as solutions, emulsions, spray powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension emulsion concentrates, with natural and synthetic substances impregnated with active substance and microcapsules in polymeric substances.

These compositions are prepared in a known manner, e.g.

5 by mixing the active substances with extenders, i. liquid solvents and / or solid carriers, optionally using surfactants, ie. emulsifiers, dispersants and / or foaming agents.

When water is used as an excipient, e.g.

also organic solvents are used as auxiliary solvents. As liquid solvents, in particular: aromatic hydrocarbons, e.g. xylene, toluene or alkyl naphthalenes, chlorinated aromatic and aliphatic hydrocarbons, e.g. chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, e.g. cyclohexane, paraffins, e.g. mineral oil fractions, mineral and vegetable oils, alcohols, e.g. butanol or glycol and their ethers and esters, ketones, e.g. acetone, methyl-ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents, e.g. dimethylformamide and dimethyl sulfoxide as well as water.

As solid carriers, e.g. ammonium salts and natural stone flour species, such as kaolines, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone flour species such as high dispersion silica, alumina and silicates are used. As solid carriers for granules, e.g. Crushed and fractionated natural minerals such as calcite, marble, pumice, 30 sepiolith and dolomite, synthetic granules of inorganic and organic flour, as well as granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks are used. As emulsifying and / or foaming agents, e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfonates, B1 alkylsulfates, arylsulfonates and protein hydrolysates. As dispersants, e.g. lignin sulfite waste liquor and methyl cellulose are used.

Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latexic polymers, e.g. gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Additional additives may be mineral and 10 vegetable oils.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide and berlin blue, and organic dyes, e.g. alizarin, azo and metalphtha locyanin dyes, as well as trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The compositions usually contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds of the invention can themselves, in or in their compositions, also be used for weed control in admixture with known herbicides, with ready-made preparations or tank mixtures being possible.

Known herbicides, e.g. 1-amino-6-ethyl thio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or N- (2-benzothiazolyl) -N, N -25-Dimethylurea for weed control in cereals, 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1 (1-Dimethylethyl) -3-methylthio-1,2,4-triazine-5 (4H) -one for weed control in soybeans. Also mixtures with 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid; chloroacetic acid N- (methoxymethyl) -2,6-diethylanilide; methyl 6,6-dimethyl-2,4-dioxo-3 - [1- (2-propenyloxyamino) -butylidene] -cyclohexanecarboxylic acid; methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate; 5-amino-4 - chloro-2-phenyl-2,3-dihydro-3-oxy-pyridazine; ethyl 2- {[(4-35-chloro-6-methoxy-2-pyrimidinyl) -aminocarbonyl] -aminosulfonyl} -benzoate; exo-1-methyl-4- (1-methylethyl) -2- (2-methyl-phenylmethoxy) - 7 -oxabicyclo (2,2,1) heptane, - ethyl-2 - {[( 4 - chloro-6-methoxy-2-pyridinyl) -arainocarbonyl] -aminosulfonyl} -benzoate; 3,6-dichloro-2-pyridinecarboxylic acid; N, S-diethyl-N - cyclohexyl-thiolcarbamate; 3- (methoxycarbonylaminophenyl) -5-N-phenylcarbamate; 2- [4- (2,4-Dichlorophenoxy) -phenoxy] -propionic acid and its methyl or ethyl ester, 4-amino-6-tert-butyl-3-ethylthio-1,2,4-triazine-5 ( 4H) -one; 2- {4 - [(6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid and its methyl or ethyl ester, 2- [4- (3,5-dichloropyrid-2-yloxy) -phenoxy] -propionic acid (trimethylsilyl methyl ester), 5- (2-chloro-4-trifluoro-methylphenoxy) -N-methylsulfonyl-2-nitrobenzamide; 2- (4-t (3-chloro-5- (trifluoromethyl) -2-pyridinyl) -oxy] -phenoxy} -propanoic acid or -propanoic acid ethyl ester; 2- [4- (2,4-dichlorophenoxy) -phenoxy] propionic acid methyl ester, 2- [5-methyl-5- (1-methyl-ethyl) -4-oxo-2-imidazolin-2-yl] -3-quinolinecarboxylic acid; 1- isobutylaminocarbonyl-2-imidazolidinone; -cyclohexyl-5,6-trimethylene-uracil; N-methyl-2- (1,3-benzothiazol-2-yloxy) -acetanilide; 2-chloro-N- (2,6-dimethylphenyl) -Nt (1H ) -pyrazol-1-yl-methyl] -acetamide; 2-ethyl-6-methyl-N- (1-methyl-2-methoxyxy) -chloroacetanilide; 3- (ethoxycarbonylaminophenyl) -N - (3 (methylphenyl) carbamate, 2- [1- (ethoxamino) butylidene] - 5- (2-ethylthiopropyl) -1,3-cyclohexanedione; N, N-diisopropyl - S- (2,3,3- trichloroallyl) thiol carbamate or 2,6-dinitro-4-trifluoromethyl-N, N-dipropylaniline are possible, some mixtures also exhibit synergistic effect.

Also, mixing with other known active compounds such as fungicides, insecticides, acaricides, nematodicides, bird bites, plant nutrients and soil structure enhancers is possible.

The active substances can be used per se, in the form of their preparations or the uses thereof prepared by further dilution such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in a conventional manner, e.g. by irrigation, spraying, spraying or spraying.

31 DK 172104 B1

The active compounds of the invention can be applied both before and after germination of the plants.

They can also be incorporated into the soil before sowing.

The amount of active substance used may vary within a larger range. It depends in particular on the nature of the desired effect. Usually, the amount applied is between 0.01 and 10 kg of active substance per day. ha of land area, preferably between 0.05 and 5 kg per hectare. ha.

The preparation and use of the active substances 10 according to the invention will be apparent from the following examples.

Preparation Examples

Example 1 H3C \ -Ν'ΉΗρ li 1 2 Νηΐ ^ ο ° NH-CH2-CH (CH3) 2 20 (Process a)

To 11.1 g (0.04 mol) of 1- (N-butylcarbamoyl) -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one in 100 ml of ethanol is added 20 ml of concentrated hydrochloric acid, and the solution is evaporated over 5 hours on a rotary evaporator at 60 ° C and ca.

200 mbar. The residue is crystallized by rinsing with ethanol / diethyl ether (1: 1) and dried in the air.

4.3 g (50% of theory) of 4-amino-1- (N-isobutylcarbamoyl) -3-methyl-triazolin-5-one are obtained, m.p. 183 ° C.

32 DK 172104 B1

Example 2 3 Ti 1 2 5 I / CH3 O = C - NH-C-CHO "CH33 (Method b)

To 3.42 g (0.03 mol) of 4-amino-3-methyl-1,2,4 - (1H) -10-triazolin-5-one in 80 ml of absolute acetonitrile are added 3.6 g (0.036 mol) tert.Butyl isocyanate and 0.05 to 0.1 g of diazabic cycloundecene (DBU) and stir for 2 hours at 20 ° C and evaporate in vacuo, the residue is taken up in methylene chloride, washed with water, dried with sodium sulfate and evaporated for 15 minutes. in vacuo, and the residue is crystallized by tearing off with ethyl ether.

5.0 g (78.3% of theory) of 4-amino-1- (N-tert. Butylcarbamoyl) -3-methyl-1,2,4-triazolin-5-one are obtained, m.p. 132 ° C.

20

Example 3 CH3X, - 3 π in 2 25 I Cl ^ l

O = C-NH-CH 2. XX

(Method a - single container variant)

To 8.2 g (0.03 mol) of 4-isopropylidenimino-3-methyl-30-1-phenoxycarbonyl-1,2,4-triazolidin-5-one in 50 ml of absolute tetrahydrofuran is added 4.2 g (0.03 mole) 2,2-dichlorocyclopropylmethylamine, then stirred for 12 hours at 20 ° C, evaporated in vacuo, the residue taken up in 100 ml of ethanol and 3 ml of concentrated hydrochloric acid added and stirred for 3-4 hours at 60 ° C. and 200 mbar. For working up, evaporate in vacuo and the residue is taken up in methylene chloride, washed three times with saturated aqueous sodium hydrogen carbonate solution, dried with sodium sulfate and evaporated in vacuo. The residue is crystallized by tearing off with diethyl ether.

4.4 g (52% of theory) of 4-amino-1- [N-5- (2,2-dichlorocyclopropylmethyl) carbamoyl] -3-methyl-1,2,4- triazoline-5 on with m.p. 149 ° C.

Example 4 10 to 2 Νηι- ^ο ch 30 = C-NH-C- (CH 2) 2-CH 3 ch 3 (Process c)

To 3.2 g (0.0137 mol) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one in a mixture of 25 ml of tetrahydrofuran and 10 ml of dioxane are added. 8.9 g (0.088 mole) of 1,1-dimethylbutylamine, which is heated for 24 hours at reflux temperature and evaporated in vacuo, the residue is taken up in methylene chloride, washed with 2% sodium hydroxide and water, dried over sodium sulfate, the solvent is removed in vacuo and the residue is crystallized by tearing off with diethyl ether.

1.9 g (61% of theory) of 4-amino-1- [N-25 - (1,1-dimethylbutyl) carbamoyl] -3-methyl-1,2,4-triazolin-5-one are obtained. with m.p. 110 ° C.

Similarly, and in accordance with the general preparation, the following substituted triazolinones of the general formula I are obtained: 34 N-NH 2

Table I

Ex. Physical No. R1 R2 XY Data 15 9h3 i *) 5 CH3 -CH-J 0 0 1.5 (d) R-Configurat ion CHg I i- \ 1H-NMR *) 6 CH3 -CH-C 2 0 0 1, 5 Cd) * '-' S-Configurat ion

7 C 2 H 5 - H 2> 0 0 Mp. 139 ° C

Ex. - Physical No. R1 R2 X Y data 5 --------

Table I (continued) 35 DK 172104 B1

8 H ~ ^ ~ H ^ 0 0 Mp. 161 ° C

9 CH3 -CH (CH3) 2 O 0 Mp. 63 ° C

10 ch3 - (CH2) 5-CH2Cl1 oo 1h-nmr * :) 1 »45 (m, 4H) 11 -CH2- <3> OO Mp. I33 ° C

13 CH 3 -CH (C 2 H 5) 2 O O Mp. 103 ° C

14 CH3 -CH-CH (CH3) 20 O mp. 103 ° C

CH3

CH3 - H H O O Mp. 105 ° C

CH3

18 CH 3 -CH 2 -CH 3 · Mp 135 ° C

CH-,

17 CH3 -CH2-C-CH3 O O Mp. 106 ° C

øH (decomposition) w

Ex. Physical No. R1 R2 -X Y data 5 -—-

Table I (continued) 36 DK 172104 B1 18 CHg -CH- (CH2),> 0 O nR ° 1.5496 ch3

19 ch3 y s O Mp. 128 ° C

CH

20 CHg -C-CHg S O Mp. 100 ° C

CH

21 H - (CHg) g-CHgCl O O Mp. 131 ° C

c ^ h5

22 ch3 - ^ H ^> - CHg O O Mp. 153 ° C

C2H5 CHo I 3

23 CH 2 -C-CH 2 Cl 1 mp. 118 ° C

CH

24 CHg -CH2 -CH = CH2 O O Mp. 92 ° C

ISLAND

II

CHg -CHg-C-OCgHg O O Mp. 127 ° C

EJcs. Physical No. R1 R2 —X Y data 5 -

Table X (continued) 37 DK 172104 B1 CHpCl in 26 ch3 “C-CHg 0 0 nfi2 1.5055 ch2ci CH, i 27 CH3 -C-CHC12 o o Mp. 176 ° C ch3 CHO in 28 C2H5 -CH2-C-CH3 O O: I 4.4; 7.95 ch3 ch2f

29 CH3 -C-CH3 O O Mp. 133 ° C

ch2f ch2f i

Mp 30 DEG-40 DEG C.

ch2f ch3 31 CH3 -C- / y 0 0 1H-HMR *): I - 4.36; ch3 8.23

Table I (continued) 38 DK 172104 B1

Ex. Physical No. R1 R2 -X Y data 5 - CHo in 32 CH3 -C-C2H5 0 O Mp. 990 q ch 3 33 CH 3 -CH- (CH 2) 3-CH (CH 3) 20 H-NMR +: I 4.40; CH3 7.61

34 CH 3 - H 2 - CF 3 O mp. 162 ° C

CH 3 -CH 2 198 ° C

36 CH3 - (CH2) 3-CH3 O O m.p. 108-

109 ° C

37 CH3 CH3 O O m.p. in £ 8-

170 ° C

38 CH3 - (CH2) 2 ~ CH3 O O m.p. 134 ~

136 ° C

CH-, 1 3

39 ch3 -CH - C-CH3 O O m.p. 149 ° C

ch3 ch3

Table T (continued) 39 DK 172104 B1

Ex. Physical No. R1 R2 X Y data 5 -—- CHg in 3 40 CH3 -C-CF3 0 0 Mp. 149-

At 151 ° C

ch3 41 CH3 I 0 0 Mp. 93-

N-1 94 0 C

42 CH3 -CH2-CH2-CN O 0 Mp. 175-

178 ° C

43 CH3 -CH2-CH- (CH2) 3-CH3 O mp. 91-

At 92 ° C

c2h5 ch3 in 44 C2H5 -C-C2H5 0 0 m.p. 102-

At 103 ° C

ch3 ch3 I 3

45 CH3 -C-CH2-F o o Mp. 178 ° C

CH3

46 CH3 - <7> CH3 0 o Mp. 113 ° C

47 ch3 -CH2> 0 0 Mp. 109 ° C

C2H5

Ex. Physical No. R1 R2 - X Y data 5 -

Table I (continued) 40 DK 172104 B1

48 CH 3 H 2 O Mp. 148 ° C

49 CH 3 -CH XX 0 O 1 H-HMR *) i I 0.35-0.6; CH3 0.93

50 ch3 ~ CH2 ~~ ^ 0 0 Mp. 175 ° C

CH3

51 CH3 -C-CH2-N 0 0 0 Mp. 211 ° C

I N- '(Hydro- CH3 chloride) ch3

52 CH3 -CH2-C2 O O Mp. 152 ° C

CH3

53 CH3 _c2H5 0 0 m.p. 185 ° C

CH-, I ch3

54 CH3 -CH2 “C-CH2 ~ NV 0 O Mp. 198 ° C

I CH3 (Hydro-CH3 chloride) CH-, I Cl

55 CH 3 -C-CH = C <0 O m.p. 135 ° C

In Cl ch3

Ex. Physical No. R1 R2 - X Y data 5 -

Table I (continued) 41 CH 172104 B1 /, r-ia v 56 CH3 - C C (CH3) 30 O mp. 200-

-20 ° C

CH3 i

57 CH3 -C-CsCH0 0 Mp. H9 ° C

ch3 58 CH3 · -CH-CH2-C10 O Mp. 135 <> c ch3 CHo CH3 I 3!

59 CH3 -C-CH2-C-CH3 O 0 Mp. 122 ° C

ch3 ch3

60 CH3 -CH-CF3 0 0 m.p. 141 ° C

ch3 ch3 in 61 CH3 -C-CN O O Mp. £ 17, Island ch3

62 CH3 -CH- (CH2) 4-CH3 O Mp. 67 ° C

CH3

63 CH3 -CH-CH2-0CH3 O O Mp. 120 ° C

CH3

Table I (continued) 42 DK 172104 B1

Ex. Physical No. R1 R2 -X Y data 5 -

64 CH3 - (CH2) 2-0CH3 O O m.p. 114 ° C

C2H5

65 CH3 -CH-CH2-N <O O Mp. 84 ° C

In C2Hg (Hydro-CH3 chloride)

66 CH3 - (CH2) 3-CH3 O S Mp. 147 ° C

67 CH3 -CH2- ^ O S Mp. 195 ° C

68 CH3 -C2H5 0 S Mp. 205 ° C

69 CH3 -CH3 O S Mp. 212 ° C

70 CH-, -CH— / S O O Mp. 139 ° C

",ISLAND

71 CH3 -CH-CH-C1 O 0 Mp. 114 »c 3 I I ch3 ch3

Cl 72 CH3 -CH-CH = C <0 0 ng ° 1.5328 I Cl ch3 ch2ci

73 CH3 -CH <0 0 Mp. 120 ° C

CH = CH2

Ex. Physical No. R1 r2 - X Y data 5 ---

Table I (continued) 43 DK 172104 B1

CPU

I 3 Cl 74 CH3 -C-CH-CH = C <0 0 nfc ° 1.3840 I I Cl CH3 ch3 ch2ci

75 CH 3 -CH 2 and 0 0 m.p. 158 ° C

CH2C1 -ch2-ch-ch2ci

Cl (3: 1)

76 CH3 -CH-CH2Cl1 0 m.p. 147 ° C

C2H5 77 CH3 -CH-CH;> ~ N / \) 0 O nR2 1.4995 IN ^ (Hydro- CH3 chloride) CH-, i 3 78 CH3 -C- (CH2) 3-CH3 0 0 n | 2 1.4891 ch3 79 -CH3 -CH- (CH2) 5-CH3 OO ng ° 1.4920 ch3 CH ·,

80 CH3 -CH-CH2-C-CH3 O O Mp. 140 ° C

ch3 ch3

Table I (continued) 44 DK 172104 B1

Ex. Physical No. R1 R2 -X Y data 5 -

C H

81 CH3 -CH2-CH (+ 0) Mp 115 C

C2H5

82 CH3 O Mp. 134 ° C

CH3

83 ch3 yL) 0 0 Mp. 164 ° C

ch3 84 CH3 - <^ H) 0 O Mp. 144 o £ CH3 (cis) 85 CH3 Γη] ^ CH3 O O Mp. 121 ° c h3c ^ s ^ s: h3

CgHg 86 CH3 - / O O O 1H-NHR *): 2.33 C2H5

87 CH3 -CH2-CF3 O O Mp. 152 ° C

88 CH3 - <D O S Mp. 178 ° C

Ex. Physical No. R1 R2 y Data 5 —---- ---

Table I (continued) 45 DK 172104 B1

Cl

89 CH3 -CH o o Mp. 156 ° C

90 CH 3 0 Mp * 167 ° C

91 CH3 -CH2—0 0 SmP * 113 0 C

92 CH3 -0Η- <Π 0 0 M.p. 133 ° C

ch3 CH2-CH (CH3) 2

93 CH 3 -CH <0 0 m.p. 98 ° C

(CH2> 2 - <^ _}

94 CH3 - <CH2) 2 - ^ _} 0 0 Mp. 15 6 0 C

CH 3 O

95 CH 3 - (CH 2) 2 - v OCH 3 O 210 ° C

? IN

96 CH-, (l) 0 mp 175 ° C

3 -CH2 ^ v ^

Ex. Physical No. R1 R2 - X Y data 5 -------

Table I (continued) 46 DK 172104 B1

97 CH3 -CH2-CH-C2H5 0 0 m.p. 106 ° C

CH3

98 CH3 - (CH2) 2-CH (CH3) O 104 ° C

99 CH3 -CH-p O O m.p. 120 ° C

Cp3 (decomposition) dwGl

100 CH3 -CH2 CH3 o o Mp. 108 ° C

CH3 Cl

101 ch3 -0H2-C-ClO 0 Mp. 151 ° C

CH3

102 CH3 '(CH2) ° Mp. 151 ° C

CH-, I ch3 103 CH3 -C-CH (O O Mp 134 »c I ch3 ch3 104 CH3 -CH- (CH2) 2-CH3 O 0 ng ° 1.4972 ch3 DK 172104 Bl

Ex. Physical No. R1 R2 -X Y data 5 -

Table I (continued) 47 c2h5

105 CH 3 -C-C 2 H 5 O Mp. 128 ° C

C2H5

106 CH3 - O 101 ° C

CH3

107 CH3 -CH- (CH2) 2-CH <0 O m.p. 73 ° C

In CH3 CH3 C2H5 108 CH3 - (CH2) 3-N <0 O ng ° 1.5815 C2H5 (Hydrochloride) ch3

109 CH3 - (CH2) 3-N <0 O m.p. 210 ° C

CH3 (Hydrochloride)

110 CH3 -CH-CH2-CN O O m.p. 145 ° C

C2H5 111 CH3 -CH-CH2-CH-C2H5 0 O ng ° 1.4890 c2h5 ch3 ch3 112 CHg -CH-CH2-CH <O o ng ° 1.4858 I ch3 ch3

Ex. Physical No. R1 R2 - X Y data 5 ---

Table I (continued) 48 DK 172104 B1

113 CH3 -CH-CH2-W / \ 0 0 Mp. 108 ° C

In V / (Hydro-CH3 chloride)

114 CH3 - (CH2) 4-CH3 O O m.p. 81 ° C

C2Hc 115 CH3 -CH- (CH?) O-N <0 o nS ° 1.5100 I C2H5 (Hydro-CH3 chloride) ch3 116 CH3 -CH-CH2-N <O O ng ° 1.5150 I CH3 (Hydro-CH3 chloride)

117 CH3 [hJ 0 0 m.p. 157 ° C

vxxC2H5

118 CH3 ThJ O O Mp. 116 ° C

119 CH3 L_J 0 0 m.p. 145 ° C

'X ^: 2H5

120 CH3 [_ O 0 Mp. 118 ° C

DK 172104 B1

Ex. Physical No. R1 R2 -X Y data 5 - 49

Table I (continued)

121 CH3 -CH2-CH2-0C2H5 O Mp. J23 ° C

122 CH3 0 0 m.p. 2X3 0 C

h3c ^ ch3 ch3

123 CH3 CH = C (o Mp 93 ° C

CH3

124 CH3 _CH3 O O Mp. 93 ° C

1 H NMR *): H35xfH3 1.58 (dd>; 125 CH3 CH = C <O 0.77 (t)

Cl 2.76 <t) / CH 2 s

126 CH 3 -CH <CH 2) 9 0 O m.p. 142 ° C

CH2 ^ 127 CH3 "CH2 ~~ ^ / ^) O O Mp 123 ° c (Endo-Form) ~ ch2 ^^; h3

128 CH3 C ~ \ l 0 0 Mp * 131 0 C

(Exo-Form)

129 CH3 -CH-CH2HC> 0 0 Mp 133 133 C

CH3

130 CH3 -CH2-fj \ O O m.p. 125 ° C

EJcs. Physical No. R1 R2 X Y data 5 -

Table I (continued) 50 DK 172104 B1

131 CH3 -CH- <V) 0 O Mp. 117 ° C

1 CH-NMR 1): 132 ch3 -c-ch2-ch2-C O 0.45 (e); I '-' 7.04-7.43 CH3 (m)

133 CH3 -CH2-CH2— ^ F 0 0 Mp. 168 ° C

134 CH3 -CH- / h \ O O m.p. 118 ° C

25 C H

c2h5 CHo

135 CH-i -CH-C-CHo O O m.p. 157 ° C

30 J I I J

c2h5 ch3 CHg

136 CH3 -CH2-C2> C10 O Mp. 180 ° C

CH3

CH13 -CH2 -CH2-ClO O m.p. 188 ° C

45 138 CH3 -CH— ^ ~ c2H5 0 0 Mp. 95 ° C

The ch3 50 H NMR spectra are recorded in deuterochloroform (CDCl3) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as 5-value in ppm.

51 DK 172104 B1

Preparation of the Udanase Compounds Examples II-1 ✓ CH 3 H CH 3 NH-CH 2 -CH (CH 3) 2 To 6 g (0.04 mol) of 4-isopropylidenimino-3-methyl-1H-triazolin-5-one and 4 g (0.04 mol) of triethylamine in 20 ml of dioxane is dropped at 20 ° C with stirring 12 g (0.12 mol) of isobutyl isocyanate and stirred after completion of addition for 3 hours at 100 ° C. For the work up, the reaction mixture is evaporated in vacuo and the residue is taken up in 100 ml of methylene chloride, washed several times with 100 ml of water, dried with sodium sulfate and freed from solvent in vacuo.

11.2 g (100% of theory) of 1- (N-iso-butylcarbamoyl) -4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one are obtained as oil.

1 H-NMR (CDCl 3): S = 0.85 (d, 6H) ppm.

Similarly, and in accordance with the general preparations, the following starting compounds of the general formula II are obtained: 52 DK 172104 B1

R1 ^, - N-N * C

li I ^ R4 5 NNjK * ^ (II) Y NH-RZ Table 2 10 R3 1 o /

Ex. R-1- Rz = C X Y Physical No. \ data 15 R4

11-2 CH3 - (H SC C CH3) 2 0 0 Mp * 125 0 C

11 -3 ch 3 - (h) = CH-CH (CH 3) 2 o 1h-nmr *):

11-4 CH3 -CH-C2H5 = C (CH3) 20 O mp. 87 ° C

CH3

11-5 CH3 -CH (CH3) 2 = C (CH3> 2 o 0 mp. 107 0 C

II-6 CH3 -CH (C2H5) 2 = C (CH3) 20 O Mp. 68 ° C

II-7 CH3 -CH-CH (CH3)? = C (CH 3) 20 O 1 H-NMR * 1: 3 0.54 (d, CH 3)

Table 2 (continued) 53 DK 172104 B1 R3.

i - / 5 Ex. R1 R2 = C X Y Physical No. \ data r4

11-8 CH3 -CH2) C (CH3) mp. 115 ° C

CH?

II-9 CH 3 -C-CH 2 Cl = C (CH 3) 20 mp. 88 ° C

CH3

11-10 CH 3 - / H 2> C (CH 3) 2 O O m.p. 139 ° C

ch3 11-11 CH3 - // ~~ CH3 = C (CH3) 2 0 o Oil c2h5

11-12 CH3 -CH2-C00C2Hs = C (CH3) O mp. 108 ° C

11-13 CH3 -CH2 -CH = CH2 = C (CH3) mp. 86 ° C

CF3

11-14 CH3 - ^ = C (CH3) 20 Mp. 158 ° C

CHF OCF3 = C (CH3) 20 O Mp. 218 ° C

CF3

11-16 CH3 - ^ Cl = C (CH3) 2 o o Mp. 185 ° C

Table 2 (continued) 54 DK 172104 B1 R3 - 5 Ex. R1 r2 -q X y Physical No. \ data ___V_ 10 ^ H3

11-17 CH3 -CH2-C-CH3 »C (CH3) mp. 121-122 ° C

ch3 15

Rlcsmwpel III-l 20 yCH3 H ^ C \ -N ^ N = C>, 3 NI ch3 N ^ N ^ o

H

31 (49) (0.1 mole) of 4-amino-3-methyl-1,2,4- (1H) triazolin-5-one (cf. Europ. J. Med. Chem .; Chim. Ther. LtJ, 215-220 [1983]) and 0.1 g of p-toluenesulfonic acid in 100 ml (79.06 g, 1.36 mol) of acetone are stirred for 40 hours at 70 ° C and then evaporated in vacuo.

15.4 g (100% of theory) of 4-isopropyl-idenimino-3-methyl-1,2,4- (1H) -triazolin-5-one are obtained, m.p. 140--144eC.

55 DK 172104 B1

Example V-1 CH3 \ -Ν-ΉΗ?

To 2

5 o-c-o-O

To 2.3 g (0.02 mol) of 4-amino-3-methyl-1,2,4- (1H) -triazolin-5-one in 25 ml of absolute tetrahydrofuran are added 2.7 g (0.024 mol) potassium tert.butanolate stirred for 1 hour at 20 ° C and then dropwise stirred with 3.1 g (0.02 mol) of chloroformic acid phenyl ester, stirred for 12 hours at room temperature, the pH is adjusted with glacial acetic acid to 5, which is evaporated to dryness. in vacuo, and the residue is taken up in chloroform, washed with water, dried with sodium sulfate, evaporated in vacuo and crystallized by rinsing with ether.

1.1 g (23.5% of theory) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one is obtained, m.p.

175 ° C.

20

Example X-1 ch 3 CH 2 -N- "N = C <3 Ti ch 3

25 N ^ N ^ O

0 * C-0-

To 15.4 g (0.1 mole) of 4-isopropylidenimino-3-methyl-1,2,4- (1H) -triazolin-5-one in 100 ml of absolute tetrahydrofuran is added at room temperature first 13.4 g ( 0.12 mole) of potassium tert-butanolate and stir for 1 hour at room temperature; then 15.5 g (0.1 mole) of chloromyric acid phenyl ester are added and stirred for an additional 12 hours at 20 ° C. For working up, acidify with glacial acetic acid and evaporate in vacuo, 35 and the residue is taken up in chloroform, washed with water, dried with sodium sulfate, evaporated in vacuo and recrystallized from acetone.

10 g (36.5% of theory) of 4-isopropylidimino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one are obtained by snip. 162 * C.

Example X-2 CH3 CH3V-N ^ N = C <io 3 Li · ch3 O = C-O-C2H5

To 7.7 g (0.05 mole) of 4-isopropylidenimino-3-methyl-1, 1,2,4- (1H) -triazolin-5-one in 50 ml of absolute tetrahydrofuran is added at 20 ° C 1.5 g (0.05 mole) of sodium hydride and stirred for 1 hour at room temperature, then stirred with stirring, 5.4 g (0.05 mole) of chloroformic acid ethyl ester and, after completion of addition, stirred an additional 12 hours at 20 ° C.

For processing, glacial acid is acidified, evaporated in vacuo and the residue taken up in methylene chloride, washed with water, dried with sodium sulfate, evaporated in vacuo and recrystallized from isopropanol.

5.0 g (44% of theory) of 1-ethoxycarbonyl-4-isopropylidenimino-3-methyl-1,2,4-triazolin-5-one are obtained, m.p. 91'C.

57 DK 172104 B1

Application Examples In the following application examples, the compounds listed below are used as comparative compounds: = tH5vJU ^ 1H2 (A) n ^ n ^ x: h3 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5-one 10 (known from German Patent Specification No. 2,364,474, Examples 1-22) p I 0 I 1 I HN 1 'NC-NH-CH (CH 3) 2 (B) o N-isobutyl-2-oxymidazolidine-1-carboxamide (known from R. Wegler "Chemie der Pflanzenschutz- und Schådlingingsbekåmpfungsmittel", Volume 5, page 219 (1977).

20

Example A

Pre-Margin Experiment Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable composition of active substance, 1 part by weight of active substance is mixed with the specified amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of experimental plants are sown in normal soil and poured after 24 hours with the active ingredient preparation. Thus, the amount of water per appropriately constant area unit. The concentration of active substance in the preparation does not play any role, decisive is only the amount of active substance applied per day. unit area. After 3 weeks, the degree of damage of the plants is assessed in percentage damage in comparison with the development of the untreated controls. By this means: 5 0% = no effect (as untreated controls) 100% = total extinction.

In this experiment, e.g. the compounds of Preparative Examples 2, 14, 23, 32, 41, 45, 48 and 57 show a significantly better herbicidal effect against problem weeds and, in addition, a distinctly better selectivity towards plant crops, e.g. sugar beet, than Comparative Compound B.

Example B

Postmergens experiments

Solvent: 5 parts by weight acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether 20 To prepare a suitable composition of active substance, one part by weight of active substance is mixed with the specified amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

25 With the active ingredient preparation, test plants having a height of 5-15 cm are sprayed, so that in each case the required amounts of active substance per area unit is applied. The concentration in the spray liquid is chosen so that in each case the desired amounts of active substance are applied in 30 2000 liters of water per day. ha. After 3 weeks, the degree of damage of the plants is evaluated in percentage damage compared to the development of the untreated controls. By this means: 0% = no effect (like untreated controls) 100% = total extinction.

35 In this experiment, e.g. the compounds of Examples 1 and 48 as well as 1, 2, 3, 14, 23, 32, 41, 45, 48, 59 DK 172104 B1 57 and 78 show a significantly better herbicide effect in controlling mono- and dicotyledonous weeds than Comparative Compound A or B .

Claims (21)

60 DK 172104 B1 Patent claims. 1. Substituted triazolinones, characterized in that they have the general formula I Wherein R1 represents hydrogen, straight or branched alkyl of 1-8 carbon atoms or cycloalkyl of 3-7 carbon atoms, R2 means hydrogen, each straight or branched alkyl of 1-18 carbon atoms, alkenyl of 2-8 carbon atoms, alkynyl of 2-8 carbon atoms, haloalkyl of 1-8 carbon atoms and 1-17 of the same or different halogen atoms, haloalkenyl or haloalkynyl of 2-8 carbon atoms and 1- 15, 13, respectively, or different halogen atoms, cyanoalkyl of 1-8 carbon atoms, hydroxyalkyl of 1-8 carbon atoms and 1-6 hydroxy groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl each having up to 6 carbon atoms in the individual alkyl and alkenyl moieties , alkylaminoalkyl or dialkylaminoalkyl having each 1-6 carbon atoms in the individual alkyl moieties, cycloalkyl having 3-11 carbon atoms or each optionally one or more times, the same or differently substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cyclone oalkenyl alkyl having each 3-8 carbon atoms in the cycloalkyl, or cycloalkenyl moiety, respectively and, if necessary, 1-6 carbon atoms in the straight or branched alkyl moiety, the substituents being selected from the following: halogen, cyano and each straight or branched alkyl or haloalkyl with each 1-4 carbon atoms and, if necessary, 1-9 identical or different halogen atoms or straight or branched halogen alkenyl with up to 4 carbon atoms and 1-5 same or different halogen atoms or each twice twice linked to alkanediyl or alkendiyl, respectively with each 1-4 carbon atoms, or R2 means heterocyclylalkyl having 1-6 carbon atoms in the straight or branched alkyl portion, wherein the heterocyclyl group has the formula O-, O, #, Ό. tf. tf.o.o, -O, o or -f / 15 wherein Z means oxygen or sulfur; or R2 each represents straight or branched chain alkoxy of 1-8 carbon atoms, alkenyloxy of 2-8 carbon atoms or alkyloxy of 2-8 carbon atoms, and finally each 20 optionally means one or more times, the same or different substituted aralkyl, aryl or aryloxy with each 6-10 carbon atoms in the aryl moiety and, if applicable, 1-8 carbon atoms in the alkyl moiety, the alkyl substituents being selected from halogen and cyano, and the aryl substituents being selected from halogen, alkyl and alkoxy, or R2 being benzyl having condensed -O -CH 2 -O group in the phenyl moiety, X means oxygen or sulfur, and Y means oxygen or sulfur. Substituted triazolinones of formula I according to claim 1, characterized in that R 1 is hydrogen, methyl, ethyl, n- or i-propyl, R 2 represents hydrogen, each optionally 1-3 times with fluoro and / or chloro substituted methyl , ethyl, n- or i-propyl, n-, i-, s- or tert-butyl, allyl, propargyl, each straight or branched pentyl, hexyl, heptyl, octyl, butenyl, pentenyl, hexenyl, butynyl, pentynyl or hexynyl; and in addition, each optionally means 1-3 times, the same or different, with fluoro, chloro, methyl, ethyl and / or cyano substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl, cyclohexylethyl or cycloheptyl and further means benzyl, phenylethyl or phenyl. A process for the preparation of substituted triazolinones of formula I according to claim 1, characterized in that a) hydrazones of formula II 1 are R 3 N 1 R 4 (II) 2 Y NH-R2 wherein R1, R2, X and Y has the meanings given in claim 1, 20 and R 3 and R 4 independently of one another means hydrogen, alkyl, aralkyl or aryl, reacted with an acid, optionally in the presence of a diluent, b) 1 H-triazolinones of formula III R 1 , -N ^ H2 Ila * {iin H in which R 1 and X have the above meanings are reacted with iso (thio) cyanates of formula IV R2-N = C = Y (IV) 63 in which R2 and Y have the above meanings, optionally in the presence of a diluent and optionally in the presence of a reaction aid, 5 or c) triazolinones of formula V ΰ-κΛχ (V) 10 Jc wherein R 1, X and Y have the above meanings and R 5 is alkyl, aryl or arylalkyl, is reacted with amines of formula VI R2-NH2 (VI) wherein R2 is as defined above, optionally in the presence of a diluent and optionally in the presence of a reaction aid. Herbicidal agents, characterized by a content of at least one substituted triazolinone of formula I according to claims 1 and 2. Method for controlling weeds, characterized in that substituted triazolinones of formula I according to claims 1 and 2 are caused to affect the weed and / or its habitat. Use of substituted triazolinones of formula I according to claims 1 and 2 for the control of weeds. 35 64 DK 172104 B1 Process for the preparation of herbicidal agents, characterized in that substituted triazolinones of formula I according to claims 1 and 2 are mixed with extenders and / or surfactants. 5 Hydrazones, characterized in that they have the general formula II ^ r3 R1 ^ -N ^ N * cC 10 || In r4 (II) 2 T NH-R2 wherein R 1, R 2, X and Y are as defined in claim 1, and R 3 and R 4 are independently hydrogen, straight or branched alkyl of 1-4 carbon atoms, phenyl or benzyl, with the exception of compounds 20 1- (N- 4-bromophenylthiocarbamoyl) -4-phenylideneamino-1,2,4-triazolin-5-thione 1- (N-4-bromophenylthiocarbamoyl) -4- (4-hydroxyphenylideneamino) -1,2,4-triazoline-5-thione, 1- (N-4-bromophenylthiocarbamoyl) -4- (2-nitrophenylideneamino)-1,2,4-triazoline-5-thione, 1- (N-4-bromophenylthiocarbamoyl) -4- (3-nitrophenylideneamino) - 1.2 .4- Triazolin-5-thione. 9. Triazolinones, characterized by the formula 3. Va R1_1v_-Ν-ΉΗ2 (Va) Y = C-O-R5 35 wherein 65 DK 172104 B1 R1-1 means straight-chain or branched alkyl of 1-4 carbon atoms, R5 means straight-chain or branched alkyl of 1-4 carbon atoms or means phenyl or benzyl, and 5 X and Y independently means oxygen or sulfur. 10. Triazolinones, characterized by the formula Xa R1'1 - ^ - N'H * C ^ R ΙΰΑ * (Xa> 1 5 Y * C-O-R5 wherein R 1 "1 means straight or branched alkyl of 1-4 carbon atoms and R 4 independently of each other means hydrogen, straight or branched alkyl of 1-4 carbon atoms, phenyl or benzyl, R5 means straight or branched alkyl of 1-4 carbon atoms or means phenyl or benzyl, and X and Y independently represent oxygen or sulfur.