EP1144392A1

EP1144392A1 - Novel tetrazolinone derivatives

Info

Publication number: EP1144392A1
Application number: EP00900007A
Authority: EP
Inventors: Toshio Goto; Seishi Ito; Yukiyoshi Watanabe
Original assignee: Nihon Bayer Agrochem KK
Current assignee: Bayer CropScience KK
Priority date: 1999-01-08
Filing date: 2000-01-04
Publication date: 2001-10-17
Also published as: AU1676900A; JP2000256331A; CN1335840A; WO2000040568A1; HK1044150A1; CA2357867A1

Abstract

Novel tetrazolinone derivatives of formula (I) wherein R represents a group (a), R?3 and R4¿ each independently represents a hydrogen atom, alkyl, haloalkyl, cycloalkyl, aralkyl or phenyl, R5 represents phenyl, aralkyl, phenoxyalkyl or phenylthioalkyl, R?1 and R2¿ each independently represents alkyl, haloalkyl, cycloalkyl, alkenyl, alkinyl, aralkyl or phenyl, or R?1 and R2¿ may form, together with the nitrogen atom to which they are bonded, a heterocyclic group, a process and intermediates for their preparation and their use as selective herbicides.

Description

Novel Tetrazolinone derivatives

The present invention relates to novel tetrazolinone derivatives, to a process for their preparation and to their use as herbicides.

In Japanese Laid-Open Patent Publications No. 82258/1995, No. 97372/1995 and No. 118246/1995 the preparation of certain tetrazolinone derivatives and 1-substi- tuted-5(4H)-tetrazolinones, the intermediates thereof is disclosed. Moreover, in EP- A-146 279 it is shown that some tetrazolinone derivatives have herbicidal activities. However, the herbicidal activity of these compounds is not satisfying in every respect.

There have now been found novel tetrazolinone derivatives of the formula (I)

in which

R represents a group

R^J

— C— FT

R⁴ and

R³ and R⁴ each independently represent a hydrogen atom, C,.₆ alkyl, C,.₆ haloalkyl,

C_3.8 cycloalkyl, C₇.₉ aralkyl or optionally substituted phenyl (substituents to the phenyl being 1 to 5 groups selected from the group consisting of halogen,

C,„₆ alkyl, C,_.6 haloalkyl, C,.₆ alkoxy, C^ haloalkoxy, C,.₆ alkylthio, C,.₆ halo- alkylthio, phenyl, phenoxy and nitro),

R⁵ represents optionally substituted phenyl, optionally substituted C_7.12 aralkyl, optionally substituted phenoxy-C alkyl or optionally substituted phenylthio- C|.₄ alkyl (substituents to these groups being 1 to 5 groups selected from the group consisting of halogen, C,.₅ alkyl, C,.₆ haloalkyl, C,.₆ alkoxy, C,.₆ halo- alkoxy, C,.₆ alkylthio, C,.₆ alkylsulfinyl, C,.₆ alkylsulphonyl, C,_.6 halo- alkylthio, phenyl, phenoxy, C alkoxy carbonyl, nitro and cyano),

R¹ and R² each independently represent C,._I0 alkyl, C,.₆ haloalkyl, C₃.₈ cycloalkyl,

C₂.₁₀ alkenyl, C₂_₆ alkinyl, optionally substituted C₇.₉ aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,.₆ haloalkyl, C,_.6 alkoxy, C,_.6 haloalkoxy, C,.₆ alkylthio, C,.₆ haloalkylthio, phenyl, phenoxy and nitro), or

R¹ and R², together with the nitrogen atom to which they are bonded, form a 5- or 6- membered heterocyclic group, which may be optionally condensed with cyclohexane or benzene or may be optionally substituted by C alkyl or halogen,

provided that in case R represents non-substituted C₇.₉ aralkyl or substituted benzyl

(substituents to the benzyl being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,.₆ haloalkyl, C,.₆ alkoxy, C,.₆ haloalkoxy,

C,.₆ alkylthio, C,.₅ alkylsulfinyl, C,.₆ alkylsulphonyl, C,.₆ haloalkylthio, phenyl, phenoxy, C_M alkoxycarbonyl, nitro and cyano),

R¹ represents C,.₆ alkyl, C,.₆ haloalkyl, C₃.₈ cycloalkyl, C₂.₆ alkenyl, C₂.₆ alkinyl, optionally substituted C₇.₉ aralkyl or optionally substituted phenyl (substituents to these groups being 1-5 groups selected from the group consisting of halogen, C,_.6 alkyl, C,.₆ haloalkyl, C,.₆ alkoxy, C,.₆ haloalkoxy, C,.₆ alkylthio,

C,_₆ haloalkylthio, phenyl, phenoxy, methoxycarbonyl, ethoxy, carboxy, cyano and nitro) and

R² represents C₇.₁₀ alkyl, C,.₆ haloalkyl, C₃ or C₇.₈ cycloalkyl, C_7.10 alkenyl or C_2.6 alkinyl,

or

R¹ and R², together with the nitrogen atom to which they are bonded, form a 5- or 6- membered heterocyclic group, which are condensed with cyclohexane or ben- zene and may be optionally substituted by C_M alkyl or halogen.

The compounds of the formula (I), according to the invention, can be obtained by a process in which

a) compounds of the formula (II)

in which R is defined as mentioned above,

are reacted with compounds of the formula (III)

in which R¹ and R² are defined as mentioned above, and M represents a commonly known leaving group such as halogen (e.g. chloro, bromo or iodo), sulfonate (e.g. triflate, mesylate, toluenesulfonate) or alkoxy etc., with chloro, bromo being particularly preferred, in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.

The compounds of the formula (I), according to the present invention have strong herbicidal activities and especially exhibit an excellent herbicidal action combined with a good compatibility with the crops. In this regard they constitute an improvement with regard to the known compounds described in the aforementioned EP-A- 146 279 which are similar to the compounds of the formula (I). Therefore, the compounds of the present invention posses a significant value as selective herbicides.

In the formulae:

Halogen in "halogen", "haloalkyl", "haloalkoxy" and "haloalkylthio" represents fluoro, chloro, bromo or iodo, and preferably is fluoro, chloro or bromo.

"Alkyl" may be straight chain or branched chain and there may be mentioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or iso-pentyl, tert-amyl, pentan-3-yl, neopentyl, n-hexyl.

"Alkoxy" may be straight chain or branched chain and there may be mentioned, for example, methoxy, ethoxy, propoxy, iso-propoxy, n-, iso-, sec- or tert-butoxy, n- pentyloxy, n-hexyloxy.

"Alkylthio" may be straight chain or branched chain and there may be mentioned, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio.

"Alkylsulfinyl" may be straight chain or branched chain and there may be mentioned, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butyl- sulfmyl. "Alkylsulfonyl" may be straight chain or branched chain and there may be mentioned, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfo- nyl, n-butylsulfonyl.

"Cycloalkyl" includes, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclo- heptyl and cyclooctyl.

As "alkenyl" there may be mentioned, for example, allyl, 1-methyl-allyl, 1,1-dimeth- ylallyl.

As "alkinyl" there may be mentioned, for example, propargyl, 1-methyl-propargyl, 1 , 1 -dimethylpropargyl.

As "aralkyl" there may be mentioned, for example, benzyl, phenethyl, 1-phenylethyl,

3-phenylpropyl, 1 -methyl-2-phenylethyl, 2-methyl-2-phenylethyl, α,α-dimethyl- benzyl, l-methyl-3-phenylpropyl, α-propylbenzyl, -isopropylbenzyl, l-ethyl-2- phenylethyl, ,-butylbenzyl, l-ethyl-3-phenylpropyl.

"Haloalkyl" may be straight chain or branched chain and there may be mentioned, for example, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromo- ethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 3-chloropropyl, 1 ,3-difluoropropan-2-yl, 1,1,1 -trifluoro- propan-2-yl, 2,2,3,3,4,4,4-heptafluorobutyl, 3-bromopropyl.

Haloalkyl part in "haloalkoxy" and "haloalkylthio" may be as defined in the above- mentioned "haloalkyl".

As " alkoxy carbonyl" there may be mentioned, for example, methoxycarbonyl, eth- oxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl. "5- or 6-membered heterocyclic group" may be optionally condensed with cyclohexane or benzene and there may be mentioned, for example, pyrrol- 1-yl, pyrrolidin- 1-yl, piperidin-1-yl, indol-1-yl, indolin-1-yl, octahydroindol-1-yl, 1,2-dihydro- quinolin-1-yl, 1, 2,3, 4-tetrahydroquinolin- 1-yl, decahydroquinolin-1-yl. Moreover, these heterocyclic groups may be optionally substituted by C alkyl such as methyl, ethyl, propyl, isopropyl, n-, sec-, iso- or tert-butyl etc., or halogen such as fluoro, chloro etc. and in case that a plurality of substituents exist, they may be identical or different each other.

As a preferable group of compounds of the present invention there can be mentioned the compounds of the formula (I)

in which

R represents a group

in which

R³ and R⁴ each independently represent a hydrogen atom, C,„₅ alkyl, C,.₅ haloalkyl,

C_3.7 cycloalkyl, C₇.₈ aralkyl or optionally substituted phenyl (substituents to the phenyl being 1 to 3 groups selected from the group consisting of halogen, C_M alkyl, C haloalkyl, C_M alkoxy, C,.₄ haloalkoxy, C_M alkylthio, C haloalkylthio, phenyl, phenoxy and nitro),

R⁵ represents optionally substituted phenyl, optionally substituted C₇.₁₀ aralkyl, optionally substituted phenoxy-C,.₃ alkyl or optionally substituted phenylthio- C,_.3 alkyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C,.₃ haloalkyl, C,.₅ alkoxy, C,.₅ haloalkoxy, C,.₅ alkylthio, C,.₅ alkylsulfinyl, C,.₅ alkylsulphonyl, C,_.5 haloalkylthio, phenyl, phenoxy, C,.₃ alkoxycarbonyl, nitro and cyano),

R¹ and R² each independently represent C,.₅ alkyl, C,_₅ haloalkyl, C_3.7 cycloalkyl, C_2.5 alkenyl, C₂.₅ alkinyl, optionally substituted C_7.9 aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C,.₅ haloalkyl, C,.₅ alkoxy, C,_.5 haloalkoxy, C,„₅ alkylthio, C,_₅ haloalkylthio, phenyl, phenoxy and nitro), or

R¹ and R², together with the nitrogen atom to which they are bonded, form a 5- or 6- membered heterocyclic group, which may be optionally condensed with cyclohexane or benzene or may be optionally substituted by methyl, ethyl, n- propyl, isopropyl, fluoro, chloro or bromo

provided that in case R represents non-substituted C₇.₉ aralkyl or optionally substituted benzyl (substituents to the benzyl being 1 to 4 groups selected from the group consisting of halogen, C,_₅ alkyl, C,_₅ haloalkyl, C,_₅ alkoxy,

C,_.5 haloalkoxy, C,_₅ alkylthio, C,.₅ alkylsulfinyl, C,_₅ alkylsulphonyl, C,_.5 haloalkylthio, phenyl, phenoxy, C,.₃ alkoxycarbonyl, nitro and cyano),

R¹ represents C,_₅ alkyl, C,.₅haloalkyl, C₃.₇ cycloalkyl, C₂.₅ alkenyl, C₂.₅ alkinyl, optionally substituted C₇.₉ aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C,_.5 haloalkyl, C,.₅ alkoxy, C,.₅ haloalkoxy, C,_₅ alkylthio,

C,_.5 haloalkylthio, phenyl, phenoxy, methoxy carbonyl, ethoxy carbonyl, cyano and nitro) and

R² represents C,.₅ haloalkyl, C₃ or C₇ cycloalkyl or C₂.₅ alkinyl, or R¹ and R², together with the nitrogen atom to which they are bonded, may form a 5- or 6- membered heterocyclic group, which are condensed with cyclohexane or ben- zene and may be optionally substituted by methyl, ethyl, n-propyl, isopropyl, fluoro, chloro or bromo.

Furthermore, as a more preferable series of compounds there can be mentioned the compounds of the aforementioned formula (I)

in which

R represents a group

in which

R³ and R⁴ each independently represent a hydrogen atom, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, chloromethyl, trifluoromethyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, benzyl or optionally substituted phenyl (substituents to the phenyl being 1 to 2 groups selected from the group consisting of fluoro, chloro, methyl, trifluoromethyl, methoxy, tri- fluoromethoxy, difluoromethoxy, methylthio, trifluoromethylthio and nitro),

R³ represents phenyl, benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 1- methyl-2-phenylethyl, 2-methyl-2-phenylethyl, ,α-dimethylbenzyl, phenoxy- methyl, 1 -phenoxy ethyl, 2-phenoxyethyl, phenylthiomethyl, 1-phenyl- thioethyl or 2-phenylthioethyl (where these groups may be substituted by 1 to 3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso- propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ehtylthio, iso-propylthio, methylsulfinyl, methylsulfonyl, trifluorometh- R and R each independently represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-chloroethyl, cyclopropyl, cyclo- pentyl, cyclohexyl, cycloheptyl, allyl, propargyl, l-methyl-3-propinyl or 1,1- dimethyl-3-propinyl, or

1 9

R and R each independently represent benzyl, phenethyl, 1-phenylethyl, 3-phenyl- propyl, l-methyl-2-phenylethyl, 2-methyl-2-phenylethyl, ,α-dimethylbenzyl or phenyl (where these groups may be optionally substituted by 1 to 3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n- propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifiuoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, eth- ylthio, iso-propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano), or

1

R and R , together with the nitrogen atom to which they are bonded, may form pyr- roli din- 1-yl, 2-methylpyrrolidin-l-yl, 2,5 -dimethylpyrrolidin- 1-yl, piperidin- 1-yl, 2-methylpiperidin-l-yl, 2,6-dimethylpiperi din- 1-yl, octahydroindol-1-yl, 2-methyloctahydroindol-l-yl, indolin-1-yl, 2-methylindolin-l-yl, 5-fluoro-2- methylindolin-1-yl, 2,3-dimethylindolin-l-yl, decahydroquinolin-1-yl, 2- methyldecahydroquinolin- 1-yl, 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 2-methyl- 1 ,2,3,4-tetrahydroquinolin- 1 -yl, 6-fluoro-2-methyl- 1 ,2,3,4-tetrahydroquino- lin-l-yl, 6-chloro-2-methyl-l ,2,3,4-tetrahydroquinolin-l -yl, 2,6-dimethyl- 1 ,2,3,4-tetrahydroquinolin- 1 -yl, 2,2-dimethyl- 1 ,2,3,4-tetrahydroquinolin- 1 -yl,

6-fluoro-2,2-dimethyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 2,2,4-trimethyl-

1, 2,3, 4-tetrahydroquinolin- 1-yl, 6-chloro-2,2,4-trimethyl-l,2,3,4-tetrahydro- quinolin- 1 -yl, 2,2-dimethyl- 1 ,2-dihydroquinolin- 1 -yl, 6-fluoro-2,2-dimethyl- 1,2-dihydroquinolin-l-yl, 2,2,4-trimethyl-l,2-dihydroquinolin-l-yl or 2,2,4,6- tetramethyl- 1 ,2-dihydroquinolin- 1 -yl, provided that in case R represents benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, l-methyl-2-phenyl ethyl, 2-methyl-2-phenylethyl, α,α-dimethylbenzyl or substituted benzyl (substituents to the benzyl are 1 to 3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso- propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ehtylthio, methylsulfinyl, methylsulfonyl, iso-propylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano),

R¹ represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 1-chloroethyl, cyclopropyl, cyclopentyl, cyclohexyl, cy- cloheptyl, allyl, propargyl, l-methyl-3-propinyl or l,l-dimethyl-3-propinyl, benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, l-methyl-2-phenylethyl, 2- methyl-2-phenylethyl, α,α-dimethylbenzyl or phenyl (where these groups may be optionally substituted by 1 to 3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert- butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, iso-propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano), and

R represents 1-chloroethyl, cyclopropyl, cycloheptyl or propargyl, or

R and R , together with the nitrogen atom to which they are bonded, may form octa- hydroindol-1-yl, 2-methyloctahydroindol-l-yl, indolin-1-yl, 2-methylindolin- 1-yl, 5-fluoro-2-methylindolin-l-yl, 2,3-dimethylindolin-l-yl, decahydro- quinolin- 1 -yl, 2-methyldecahydroquinolin- 1 -yl, 1 ,2,3 ,4-tetrahydroquinolin- 1 - yl, 2-methyl-l,2,3,4-tetrahydroquinolin-l-yl, 6-fluoro-2-methyl-l,2,3,4-tetra- hydroquinolin-1-yl, 6-chloro-2 -methyl- 1, 2,3, 4-tetrahydroquinolin- 1-yl, 2,6- dimethyl-l,2,3,4-tetrahydroquinolin-l-yl, 2,2-dimethyl- 1,2, 3, 4-tetrahydro- quinolin- 1 -yl, 6-fluoro-2,2-dimethyl- 1 ,2,3 ,4-tetrahydroquinolin- 1-yl, 2,2,4- trimethyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 6-chloro-2,2,4-trimethyl- 1 ,2,3 ,4- tetrahydroquinolin- 1 -yl, 2,2-dimethyl- 1 ,2-dihydroquinolin- 1 -yl, 6-fluoro-2,2- dimethyl- 1 ,2-dihydroquinolin- 1 -yl, 2,2,4-trimethyl- 1 ,2-dihydroquinolin- 1 -yl or 2,2,4, 6-tetramethyl- 1 ,2-dihydroquinolin- 1 -yl.

The radical definitions listed above, whether general or listed in ranges of preference can be combined as desired with one another, thus including combinations between the preferred ranges cited.

The compounds of the above formula (I) contain an asymmetric carbon atom, as shown by the following formula

In which, the carbon atom represented as C* is asymmetric carbon atom. The compounds of the formula (I) which are meant according to the invention are the pure, optically active enantiomers as well as mixtures in appropriate ratio of optically active enantiomers (including the racemate).

Therefore, the compounds of the above formula (I), according to the invention are optically active enantiomers or mixtures thereof.

Furthermore, as specific examples of the compounds of the formula (I), according to the invention, there may be shown the following compounds in Table 1. Table 1

Table 1 (continued)

Using, for example, l-(l-methyl-3-phenylpropyl)-5(4H)-tetrazolinone and N-ethyl-

N-cyclohexylcarbamoyl chloride as starting materials in the preparation process a) of the compounds of the aforementioned formula (I), said preparation process can be illustrated by the following reaction formula:

The starting materials (compounds of the formula (II)) in the above-mentioned preparation process a) are, except in case in which R represents non-substituted C₇.₉ aralkyl or substituted benzyl (substituents to the benzyl being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,.₆ haloalkyl, C,.₆ alkoxy, C,.₆ haloalkoxy, C,.₆ alkylthio, C,.₆ alkylsulfinyl, C,.₆ alkylsulphonyl, C,.₆ haloalkylthio, phenyl, phenoxy, C alkoxycarbonyl, nitro and cyano), novel compounds which were not described in the literature.

In the especially preferred compounds of formula (II) the substituent R has the same meaning as described for the preferred or more preferred definition of R of compounds according to formula (I).

The compounds of the formula (II) can be in general prepared, for example, by the following preparation processes b) or c). Preparation process b):

Compounds of the formula (IV)

R-N=C=O (IV)

in which R is as defined above,

are reacted with trimethylsilyl azide in the presence of a catalytic quantity of boron trifluoride-ether-complex.

Preparation process c):

Compounds of the above-mentioned formula (IV) are reacted with sodium azide in a polar solvent in the presence of a catalytic quantity of aluminium chloride.

The compounds of the formula (IV) which are used as starting materials in the above-mentioned preparation processes b) and c) include isocyanates known in the area of organic chemistry and can be easily obtained, for example, by reacting amines represented by the formula (V)

R-NH₂ (V)

in which R is as defined above,

with, for example, phosgene according to the method described in "SHIN JIKKEN KAGAKU KOUZA" (New experimental chemistry lecture) Vol. 14, III, pp.1490- 1496 (published by Maruzen Ltd. on February 20, 1978).

Compounds of the above-mentioned formula (V) can be synthesized, for example, similarly to the methods described in "SHIN JIKKEN KAGAKU KOUZA" (New experimental chemistry lecture) Vol. 14, III, pp.1332-1398 (published by Maruzen Ltd. on February 20, 1978) or Organic Reactions, Vol. 5, 1949, 301-330 (John Wiley & Sons, Inc.).

As typical examples of the compounds of the formula (II) the following compounds can be mentioned:

(l-(2-methylphenyl)ethyl)-5(4H)-tetrazolinone,

(l-(3-methylphenyl)ethyl)-5(4H)-tetrazolinone,

(l-(4-methylphenyl)ethyl)-5(4H)-tetrazolinone,

(l-(3-fluorophenyl)ethyl)-5(4H)-tetrazolinone,

(l-(4-chlorophenyl)ethyl)-5(4H)-tetrazolinone,

(l-(3-trifluoromethylphenyl)ethyl)-5(4H)-tetrazolinone,

•( 1 -(3 ,4-dimethylphenyl)ethyl)-5 (4H)-tetrazolinone,

■( 1 -(2,4-dichlorophenyl)ethyl)-5(4H)-tetrazolinone,

(l-(2,3,4-trichlorophenyl)ethyl)-5(4H)-tetrazolinone,

(l-(4-fluorophenyl)propyl)-5(4H)-tetrazolinone,

■( 1 -(3 -methoxypheny l)propyl)-5 (4H)-tetrazolinone,

•(l-(3-fluorophenyl)butyl)-5(4H)-tetrazolinone,

-(2-methyl-l-phenylpropyl)-5(4H)-tetrazolinone,

■(.-cyclohexylbenzyl)-5(4H)-tetrazolinone,

■(diphenylmethyl)-5(4H)-tetrazolinone,

-benzyl-2-methylpropyl)-5(4H)-tetrazolinone,

-(l-methyl-3-phenylpropyl)-5(4H)-tetrazolinone,

-(., -dimethyl-4-fluorobenzyl)-5(4H)-tetrazolinone,

-( 1 -methy l-2-phenoxyethyl)-5 (4H)-tetrazolinone,

-(l-methyl-phenylthioethyl)-5(4H)-tetrazolinone

-(l-(R)-(2-methylphenyl)ethyl)-5(4H)-tetrazolinone,

-(l-(S)-(3-methylphenyl)ethyl)-5(4H)-tetrazolinone,

-(l-(R)-(3-fluorophenyl)ethyl)-5(4H)-tetrazolinone, l-(l-(S)-(3-fluorophenyl)ethyl)-5(4H)-tetrazolinone, 1 -(1 -(R)-(2,4-difluorophenyl)ethyl)-5(4H)-tetrazolinone, 1 -( 1 -(R)-(4-fluorophenyl)propyl)-5 (4H)-tetrazolinone, 1 -(1 -(S)-(4-fluorophenyl)propyl)-5(4H)-tetrazolinone, 1 -(2-methyl- 1 -(R)-phenylpropyl)-5(4H)-tetrazolinone,

1 -(1 -(R)-methyl-3-phenylpropyl)-5(4H)-tetrazolinone, 1 -( 1 -(R)-methy l-2-phenoxyethyl)-5 (4H)-tetrazolinone and the like.

As typical examples of the compounds of the formula (III) to be reacted with the compounds of the above-mentioned formula (II) are carbamoyl chlorides which are well known in the area of organic chemistry the following compounds can be mentioned:

N,N-diethylcarbamoyl chloride, N-cyclohexyl-N-ethylcarbamoyl chloride,

N,N-di-n-propylcarbamoyl chloride,

N-cyclopropyl-N-n-propylcarbamoyl chloride,

N-cyclopentyl-N-isopropylcarbamoyl chloride,

N,N-diallylcarbamoyl chloride, N,N-dipropargylcarbamoyl chloride,

N-isopropyl-N-phenylcarbamoyl chloride,

N-2-chlorophenyl-N-isopropylcarbamoyl chloride,

N-3-bromophenyl-N-isopropylcarbamoyl chloride,

N-4-fluorophenyl-N-isopropylcarbamoyl chloride, N-(4-methylphenyl)-N-isopropylcarbamoyl chloride,

N-benzyl-N-ethylcarbamoyl chloride,

1 -indolinylcarbonyl chloride,

1,2,3,4-tetrahydroquinolin-l-ylcarbonyl chloride,

2-methyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -ylcarbonyl chloride, 2,2-dimethy 1-1 ,2,3, 4-tetrahydroquinolin-l -ylcarbonyl chloride,

N- 1 , 1 -dimethylpropargyl-N-phenylcarbamoyl chloride, N-methyl-N-phenylcarbamoyl chloride, N-ethyl-N-phenylcarbamoyl chloride, N-n-propyl-N-phenylcarbamoyl chloride, N-cyclohexyl-N-isopropylcarbamoyl chloride, 2-methyl- 1 ,2-dihydroquinolin- 1 -ylcarbonyl chloride,

2,2-dimethyl- 1 ,2-dihydroquinolin- 1 -ylcarbonyl chloride and the like.

The reaction of the preparation process a) are conducted usually in an inert organic solvent. As examples of such inert organic solvents in said reaction there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetetrachloride, 1,2- dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane

(DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); nitriles, for example, acetonitrile, propionitrile; acid amides, for example, dimethylformamide

(DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazol- idinone, hexamethylphosphoric triamide (HMPA) etc.

The preparation process a) may be conducted in the presence of an acid binding agent. As a preferable example of the usable base 4-dimethylaminopyridine (DMAP) can be mentioned.

In case of using DMAP as an acid binding agent, the reaction of the preparation process a) may be conducted usually at about -10 to about 200°C, preferably about 25 to about 140°C under normal pressure. Optionally it is possible to conduct it under elevated pressure or under reduced pressure.

Moreover, it is possible to conduct the reaction of the preparation process a) using other acid binding agents than DMAP. As such acid binding agents there can be mentioned inorganic salts (for example, sodium carbonate, potassium carbonate etc.), alkyl alcoholates (for example, sodium methoxide, sodium ethoxide, potassium tert- butoxide), sodium hydroxide, potassium hydroxide, lithium hydroxide, organic bases (for example, triethylamine, 1 , 1 ,4,4-tetramethylethylenediamine, N,N-dimethylani- line, pyridine etc.).

In case of conducting said reaction using these acid binding agents, the compounds of the formula (I) can be selectively obtained by using DMAP as a catalyst.

Reaction temperature in this case may be in a range of usually about 0 to about

150°C, preferably about 25 to about 100°C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

The compounds of the formula (I), according to the present invention can be prepared, for example, by reacting 1 mole of the compound of the formula (II) with about 1 mole to about 1.5 moles of the compound of the formula (III) in the presence of about 1 mole to about 1.5 moles of DMAP as a base and in an above described inert solvent.

The compounds of the formula (I) can also be prepared by reacting 1 mole of the compound of the formula (II) with about 1 mole to about 1.5 moles of the compound of the formula (III) in the presence of about 0.01 mole to about 0.3 moles of DMAP as a catalyst and, for example, about 1 mole to about 1.5 moles of potassium carbon- ate as a base and in such an inert solvent as described above.

The compounds of the formula (I), according to the present invention, thus obtained can be isolated and purified, for example, by means of crystallization, chromato- graphy etc.

The reaction of the aforementioned preparation process b) may be conducted using a boron trifiuoride-ether-complex as a catalyst. The reaction temperature may be usually about 0 to about 200°C, preferably about 50 to about 150°C. The reaction is conducted preferably under normal pressure.

Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

The preparation process b) may be conducted by reacting 1 mole of the compound of the formula (IV) with about 1 mole to about 2 moles of trimethylsilyl azide in the presence of about 0.005 moles to about 0.01 mole of boron trifluoride-ether-complex as a catalyst.

The reaction of the preparation process c) may be conducted usually in a polar solvent. As usable polar solvents there can be mentioned, for example, acid amides such as dimethylformamide, dimethylacetamide etc. and sufoxides such as dimethyl- sulfoxide, sulfolane etc. The reaction temperature may be generally about 0 to about 200°C, preferably about 20 to about 150°C. The reaction is conducted preferably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

The preparation process c) may be conducted by reacting usually 1 mole of the compound of the formula (IV) with about 1 mole to about 1.5 moles of sodium azide in the presence of about 0.05 moles to about 1 mole of aluminium chloride as a catalyst and in a polar solvent, for example, dimethylformamide.

The active compounds of the formula (I), according to the present invention, have, as shown in the test examples, which are described later, excellent herbicidal activities and can be used as herbicidal agents for controlling weeds. In this regard "Weeds" mean, in the broadest sense, all plants which grow in locations where they are unde- sired. The compounds, according to the present invention, act as total or selective herbicides depending upon the applied concentration. The active compounds of the present invention can be used, for example, as selective herbicides between the following weeds and cultures.

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipo- moea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindemia etc.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras- sica, Lactuca, Cucumis, Cucurbita etc.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro- pyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischae- mum, Agrostis, Alopecurus, Cynodon etc.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Se- cale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.

The use of the active compounds of the formula (I), according to the present inven- tion, is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner.

According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional breeding and opti- mizing processes or by biotechnological and genetic engineering methos or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plant parts also includes harvested corps and propagation material, e.g. cuttings, tubers, bulbs, rhiozomes, shoots and seeds.

According to the invention the plants and plant parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting, fogging, spreading and in the case of propagation material also by coating using one or multiple layers.

The active compounds of the present invention can, depending upon the applied concentration, non-selectively control weeds and may be used, for example, on industrial terrain, rail tracks, paths, places with or without tree plantings.

Moreover, the active compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, for example, afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hopfields etc. and can be applied for the selective controlling of weeds in annual cultures.

The active compounds of the formula (I), according to the present invention, can be made into the customary formulations, when they are applied. As such formulations there can be mentioned, for example, solutions, emulsions, wettable powders, sus- pensions, powders, soluble powders, granules, tablets, suspension-emulsion concentrates, microcapsules, in polymeric substances, jumbo formulations etc. These formulations can be prepared according to per se known methods, for example, by mixing the active compound with extenders, namely liquid diluents and/or solid diluents or carriers, optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents. When water is used as extender, for example, organic solvents can be used as auxiliary solvents.

As liquid diluents or carriers there can be mentioned generally aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols and their ethers and esters etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for ex- ample, dimethylformamide, dimethylsulphoxide etc.) and water.

As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc.

As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.), synthetic granules of inorganic and organic meals, granules of organic material (for ex- ample, sawdust, coconut shells, maize cobs and tobacco stalks etc.) etc.

As emulsifier and/or foam-forming agents there can be mentioned nonionic and ani- onic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates etc.)], albumin hydrolysis products etc. As dispersants include, for example, ligninsulphite waste liquor and methyl cellulose.

Tackifiers may also be used in formulations (powders, granules, emulsions). As usable tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc.).

Colorants may also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc.), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc.

Said formulations can contain in a range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight of the compounds of the aforementioned formula (I).

The active compounds of the present invention can be used as such or in their formulation forms for controlling weeds. They can be used also as a mixed agent with known herbicides. Such mixed agent can be previously prepared as a final formula- tion form or can be prepared by tank-mixing on occasion of application.

The active compounds of the formula (I) of the present invention can be used also with a safener and their application as a selective herbicide may be broadened by such a mixing. As an example of the safener l-(α,α-dimethylbenzyl)-3-p-tolylurea can be mentioned.

As possible combinations as the above-mentioned mixed agents there can be mentioned, for example, the following known herbicides:

4-amino-6-(l ,l-dimethylethyl)-3-ethylthio-l,2,4-triazin-5(4H)-one, l-amino-6-ethyl- thio-3-(2,2-dimethylpropyl)-l,3,5-triazin-2,4(lH,3H)-dione, or N-(2-benzothiazolyl)- N,N'-dimethylurea etc. for controlling weeds in cereals culture;

4-amino-3-methyl-6-phenyl-l,2,4-triazin-5(4H)-one etc. for controlling weeds in sugar cane culture;

4-amino-6-(l,l-dimethylethyl)-3-methylthio-l,2,4-triazin-5(4H)-one etc. for controlling weeds in soybean culture;

Surprisingly, mixed agents of some of the compounds of the formula (I) of the pres- ent invention show synergistic effects.

In case of using the active compounds of the formula (I) of the present invention they can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsions, suspensions, powders, granules or used in the use forms prepared by further dilution.

The active compounds of the formula (I) of the present invention can be applied by watering, spraying, atomizing, dusting or granule application etc.

The active compounds of the formula (I) of the present invention can be applied at any stages before and after germination of plants. They may also be mixed into the soil before sowing.

The application amount of the active compounds may be varied in a substantial range and are fundamentally different according to the nature of the desired effect. If used as herbicides, as the application amount there can be mentioned, for example, ranges of about 0.01 to about 5 kg, preferably about 0.1 to about 3 kg of active compounds per hectare.

Then the preparations and applications of the compounds of the present invention will be described more specifically by the following examples. However, the present invention should not be restricted to them in any way. "Parts" mean "parts by weight" unless specified.

Preparation examples of the compounds

Synthesis Example 1

l-(l-Methyl-3-phenylpropyl)-5(4H)-tetrazolinone (1.0 g), dimethylaminopyridine (0.67 g) and N-cyclohexyl-N-ethylcarbamoyl chloride (1.04 g) are dissolved in toluene (20 ml) and stirred at 80°C for 8 hours on heating. After naturally cooling the reaction mixture is washed with water (2 times x 10 ml), dried with anhydrous sodium sulfate and then the solvent is distilled off under reduced pressure. The residue is treated by silica gel column chromatography (eluant: hexane: ethyl acetate = 3:1) to obtain l-(l-methyl-3-phenylpropyl)-4-(N-cyclohexyl-N-ethylcarbamoyl)-5(4H)- tetrazolinone (1.65 g). n_D ²⁰ 1.5215

The compounds obtained in the same manner as the above-mentioned Synthesis Example 1 are shown in the following Table 2 together with the compound obtained in Synthesis Example 1. Table 2

Tabelle 2 (continued)

Synthesis Example 2 (Intermediate)

l-Methyl-3-phenylpropyl isocyanate (7.68 g), trimethylsilyl azide (7.58 g) and a catalytic amount of boron trifluoride-ether-complex are mixed and refluxed for 16 hours on heating. Excess amount of trimethylsilyl azide is distilled off under reduced pressure and the residue is treated by silica gel column chromatography (eluant: hexane : ethyl acetate = 1 :1) to obtain l-(l-methyl-3-phenylpropyl)-5(4H)-tetrazoli- none (8.70 g). n ^2ϋ 1.5372

Synthesis Example 3 (Intermediate)

Sodium azide (1.95 g) is suspended in anhydrous dimethylformamide (18 ml) and anhydrous aluminium chloride (0.2 g) is added in argon stream under ice cooling and stirred for 15 minutes. Then l-methyl-3-phenylpropyl isocyanate (5.25 g) is added drop by drop and the reaction mixture is stirred for 3 hours in argon stream on heating at 70-75 °C. After natural cooling, the reaction mixture is added to a mixture of sodium sulfite (0.5 g), water (100 ml) and ice (50 g) on stirring, acidified with 10% hydrochloric acid and extracted ethyl acetate. After drying the organic layer with anhydrous sodium sulfate, the solvent is distilled off under reduced pressure and the residue is treated by silica gel column chromatography (eluant: hexane : ethyl acetate 1 :1) to obtain l-(l-methyl-3-phenylpropyl)-5(4H)-tetrazolinone (4.82 g). n_D ^2U 1.5372 Specific examples of the compounds obtainable in the same manner as the above- mentioned Synthesis Examples 2 or 3 are shown in the following Table 3 together with the compounds obtained in Synthesis Examples 2 and 3.

Table 3

Tabelle 3 (continued)

Biological test examples

Test Example 1: Test for herbicidal effect against paddy field weeds

Preparation of formulation of the active substances:

Carrier: Acetone 5 parts by weight

Emulsifier: Benzyloxypolyglycolether 1 part by weight

A formulation of the active substances is obtained as emulsion by mixing 1 part by weight of an active substance with the above-mentioned amount of carrier and emulsifier. A prescribed amount of said formulation is diluted with water to prepare a formulation for testing.

Test method

In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5 leafstage (15 cm tall) were transplanted in a 500 cm² pot filled with paddy field soil. Then seeds of barnyard grass, cow hairs, smallflower, bulrush, monochoria and broad-leaved weeds (common false pimpernel, Indian toothcup, long stemmed water wort, Am- mannia multiflora Roxb., Dopatrium junceum Hammilt etc.) were sown and water was poured on the soil to a depth of about 2-3 cm.

5 days after the rice transplantation a formulation of each active compound prepared according to the above-mentioned preparation method was applied to the surface of the water. The herbicidal effect was examined on the day after 3 weeks from the treatment during which period the water depth of 3 cm was maintained. The herbicidal effect was rated as 100% in the case of complete death and as 0% in the case of no herbicidal effect.

As a result, the compounds of the present invention Nos. 6, 8, 18, 26, 27, 38, 46 and

48 showed at the chemical amount of 0.5 kg/ha sufficient herbicidal effect against paddy field weeds and showed safety to the transplanted paddy rice. Formulation Example 1 (granule)

To a mixture of 10 parts by weight of the compound 6, 30 parts by weight of bento- nite (montmorilonite), 58 parts by weight of talc and 2 parts by weight of ligninsul- phonate salt, 25 parts by weight of water are added, well kneaded, made in granules of 10-40 mesh by extrusion granulation and dried at 40-50°C to obtain granules.

Formulation Example 2 (granule)

95 parts by weight of clay mineral particles having a particle size distribution of 0,2-

2 mm are put in a rotary mixer. While rotating it, 5 parts by weight of compound 18 are sprayed together with a liquid diluent in the mixer, wetted uniformly and dried at 40-50°C to obtain granules.

Formulation Example 3 (Emulsifiable concentrate)

30 parts by weight of the compound 26, 5 parts by weight of xylene, 8 parts by weight of polyoxyethylenealkyl phenyl ether and 7 parts by weight of calcium alkyl- benzenesulphonate are mixed and stirred to obtain an emulsion.

Formulation Example 4 (Wettable powder)

15 parts by weight of the compound 38, 80 parts by weight of a mixture of white carbon (fine particles of hydrous amorphous silicon oxide) and powder clay (1 :5), 2 parts by weight of sodium alkylbenzenesulphonate and 3 parts by weight of sodium alkylnaphthalenesulphonate-formalin-polymer are mixed in powder form to obtain a wettable powder. Formulation Example 5 (Water dispersible granule)

20 parts by weight of the compound 46, 30 parts by weight of sodium ligninsulpho- nate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatoma- ceous earth powder are well mixed, added with water, well kneaded and then extruded with a 0.3 mm screen and dried to obtain a water dispersible granule.

Claims

1. Compounds of the general formula (I)

in which

R represents a group

and

in which

R³ and R⁴ each independently represent a hydrogen atom, C,_₆ alkyl, C,_₆ haloalkyl, C₃.₈ cycloalkyl, C₇.₉ aralkyl or optionally substituted phenyl (substituents to the phenyl being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,.₆ haloalkyl, C,.-₆ alkoxy, C,_₆ haloalkoxy, C,.₆ alkylthio, C,.₆ haloalkylthio, phenyl, phenoxy and nitro),

R⁵ represents optionally substituted phenyl, optionally substituted C₇.₁₂ aral- kyl, optionally substituted phenoxy-C _M alkyl or optionally substituted phenylthio-C,.₄ alkyl (substituents to these groups being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,_.6 haloalkyl, C,.₆ alkoxy, C,.₆ haloalkoxy, C,.₆ alkylthio, C,.₆ alkylsulfinyl, C,.₆ alkylsulphonyl, C,.₆ haloalkylthio, phenyl, phenoxy, C_M alkoxycarbonyl, nitro and cyano),

R¹ and R² each independently represent C,._I0 alkyl, C,.₆ haloalkyl, C_3.8 cycloalkyl, C₂_,₀ alkenyl, C₂.₆ alkinyl, optionally substituted C_7.9aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,_.6 haloalkyl, C,.₆ alkoxy, C,.₆ haloalkoxy, C,_₆ alkylthio, C,_.6 haloalkylthio, phenyl, phenoxy, cyano and nitro), or

R¹ and R², together with the nitrogen atom to which they are bonded, form a 5- or 6-membered heterocyclic group, which may be optionally con- densed with cyclohexane or benzene,and may be optionally substituted by C ι.₄ alkyl or halogen,

provided that in case R represents non-substituted C₇.₉ aralkyl or substituted benzyl (substituents to the benzyl being 1 to 5 groups selected from the group consisting of halogen, C,.₆ alkyl, C,_₆ haloalkyl, C,.₆ alkoxy,

C,.₆ haloalkoxy, C,.₆ alkylthio, C,.₅ alkylsulfinyl, C,.₆ alkylsulphonyl, C,_₆ haloalkylthio, phenyl, phenoxy, C,.₄ alkoxycarbonyl, nitro and cyano),

R¹ represents C,.₆ alkyl, C,.₆ haloalkyl, C₃.₈ cycloalkyl, C₂.₆ alkenyl, C₂.₆ alkinyl, optionally substituted C₇.₉ aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 5 groups selected from the group consisting of halogen, C,_₆ alkyl, C,.₆ haloalkyl, C,.₆ alkoxy, C,_.6 haloalkoxy, C,.₆ alkylthio, C,.₆ haloalkylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, cyano and nitro) and R² represents C₇.,₀ alkyl, C,.₆ haloalkyl, C₃ or C_7.8 cycloalkyl, C_7.10 alkenyl or C₂.₆ alkinyl, or R¹ and R², together with the nitrogen atom to which they are bonded, can form a 5- or 6-membered heterocyclic group, which are condensed with cyclohexane or benzene and may be optionally substituted by C_M alkyl or halogen.

The compounds of the formula (I) according to claim 1

in which

R represents a group

in which

R³ and R⁴ each independently represent a hydrogen atom, C,.₅ alkyl, C,_₅ haloalkyl, C₃.₇ cycloalkyl, C₇.₈ aralkyl or optionally substituted phenyl (substituents to the phenyl being 1 to 3 groups selected from the group consisting of halogen, C alkyl, C haloalkyl, C,.₄ alkoxy, C_M halo- alkoxy, C,.₄ alkylthio, C,.₄ haloalkylthio, phenyl, phenoxy and nitro),

R⁵ represents optionally substituted phenyl, optionally substituted C₇.₁₀ aralkyl, optionally substituted phenoxy-C,.₃ alkyl or optionally substituted phenylthio-C,_.3 alkyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C haloalkyl, C,_₅ alkoxy, C,.₅ haloalkoxy, C,.₅ alkylthio, C,.₅ alkylsulfinyl, C,_₅ alkylsulphonyl, C,.₅ haloalkylthio, phenyl, phenoxy, C,_₃ alkoxycarbonyl, nitro and cyano), R¹ and R² each independently represent C^ alkyl, C,.₅ haloalkyl, C_3.7 cycloalkyl, C₂.₅ alkenyl, C₂.₅ alkinyl, optionally substituted C_7.9 aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,_.5 alkyl, C,_₅ haloalkyl, C,.₅ alkoxy, C,.₅ haloalkoxy, C,.₅ alkylthio, C,_.5 haloalkylthio, phenyl, phenoxy and nitro), or

R¹ and R², together with the nitrogen atom to which they are bonded, form a 5- or 6-membered heterocyclic group, which may be optionally condensed with cyclohexane or benzene or may be optionally substituted by methyl, ethyl, n-propyl, iso-propyl, fluoro, chloro or bromo,

provided that in case R represents C₇.₉ aralkyl or optionally substituted benzyl (substituents to the benzyl being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C,_₅ haloalkyl, C,.₅ alkoxy, C,_.5 haloalkoxy, C,.₅ alkylthio, C,_₅ alkylsulfinyl, C,.₅ alkylsulphonyl, C,.₅ haloalkylthio, phenyl, phenoxy, C,.₃ alkoxycarbonyl, nitro and cyano),

R¹ represents C,_₅ alkyl, C,.₅ haloalkyl, C₃.₇ cycloalkyl, C₂.₅ alkenyl, C₂.₅ alkinyl, optionally substituted C₇.₉ aralkyl or optionally substituted phenyl (substituents to these groups being 1 to 4 groups selected from the group consisting of halogen, C,.₅ alkyl, C,.₅ haloalkyl, C alkoxy, C_|.₅ haloalkoxy, C,.₅ alkylthio, C,.₅ haloalkylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, cyano and nitro) and

R² represents C,.₅ haloalkyl, C₃ or C₇ cycloalkyl or C₂.₅ alkinyl, or R¹ and R², together with the nitrogen atom to which they are bonded, can form a

5- or 6-membered heterocyclic group, which are condensed with cyclohexane or benzene and may be optionally substituted by methyl, ethyl, n-propyl, iso-propyl, fluoro, chloro or bromo. The compounds of the formula (I) according to claim 1

in which

R represents a group

in which

R³ and R⁴ each independently represent a hydrogen atom, methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, chloromethyl, trifluoromethyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, benzyl or optionally substituted phenyl (substituents to the phenyl being 1 to 2 groups selected from the group consisting of fluoro, chloro, methyl, trifluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy, methylthio, trifluoromethylthio and nitro),

R⁵ represents phenyl, benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 1 -methyl-2-phenylethyl, 2-methyl-2-phenylethyl, α,α-dimethylbenzyl, phenoxymethyl, 1 -phenoxy ethyl, 2-phenoxy ethyl, phenylthiomethyl, l-phenylthioethyl or 2-phenylthioethyl (where these groups may be substituted by 1-3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ehtylthio, iso-propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano),

R¹ and R² each independently represent methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-chloroethyl, cyclo- propyl, cyclopentyl, cyclohexyl, cycloheptyl, allyl, propargyl, 1- methyl-3-propinyl or l,l-dimethyl-3-propinyl, or

R' and R² each independently represent benzyl, phenethyl, 1-phenylethyl, 3- phenylpropyl, l-methyl-2-phenylethyl, 2-methyl-2-phenylethyl, α,α- dimethylbenzyl or phenyl (where these groups may be optionally substituted by 1-3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ehtylthio, iso- propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, 2,2,2- trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxy- . carbonyl, nitro and cyano), or

R¹ and R², together with the nitrogen atom to which they are bonded, may form pyrrolidin-1-yl, 2-methylpyrrolidin-l-yl, 2,5-dimethylpyrrolidin-

1-yl, piperidin-1-yl, 2-methy lpiperidin- 1-yl, 2,6-dimethylpiperidin-l- yl, octahydroindol-1-yl, 2-methyloctahydroindol-l-yl, indolin-1-yl, 2- methylindolin-1-yl, 5-fluoro-2-methylindolin-l-yl, 2,3-dimethyl- indolin- 1 -yl, decahydroquinolin- 1 -yl, 2-methyldecahydroquinolin- 1 - yl, 1, 2,3, 4-tetrahydroquinolin- 1-yl, 2-methyl- 1,2,3, 4-tetrahydro- quinolin-1-yl, 6-fluoro-2-methyl- 1,2, 3, 4-tetrahydroquinolin- 1-yl, 6- chloro-2-methyl- 1,2,3, 4-tetrahydroquinolin- 1-yl, 2,6-dimethyl- 1,2,3 ,4- tetrahydroquinolin- 1-yl, 2,2-dimethyl- 1,2,3, 4-tetrahydroquinolin- 1-yl, 6-fluoro-2,2-dimethyl-l,2,3,4-tetrahydroquinolin-l-yl, 2,2,4-trimeth- yl- 1,2,3, 4-tetrahydroquinolin- 1-yl, 6-chloro-2,2,4-trimethyl-l,2,3,4- tetrahydroquinolin- 1 -yl, 2,2-dimethyl- 1 ,2-dihydroquinolin- 1 -yl, 6- fluoro-2,2-dimethyl-l,2-dihydroquinolin-l-yl, 2,2,4-trimethyl- 1,2- dihydroquinolin- 1 -yl or 2,2,4,6-tetramethyl- 1 ,2-dihydroquinolin- 1 -yl,

provided that in case R represents benzyl, phenethyl, 1-phenylethyl, 3-phenyl- propyl, l-methyl-2-phenylethyl, 2-methyl-2-phenylethyl, α,α-dimeth- ylbenzyl or substituted benzyl (substituents to the benzyl being 1-3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ehtylthio, methylsulfinyl, methylsulfonyl, iso-propylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano),

R¹ represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 1-chloroethyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, allyl, propargyl, l-methyl-3-propinyl, 1,1-di- methyl-3-propinyl, benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 1 -methyl-2-phenylethyl, 2-methyl-2-phenylethyl, .α-dimethylbenzyl or phenyl (where these groups may be optionally substituted by 1-3 groups selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, iso-propoxy, trifluoromethoxy, difluoromethoxy, 2,2,2- trifluoroethoxy, methylthio, ethylthio, iso-propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro and cyano), and

R² represents 1 -chloroethyl, cyclopropyl, cycloheptyl or propargyl, or

R¹ and R², together with the nitrogen atom to which they are bonded, may form octahydroindol-1-yl, 2-methyloctahydroindol-l-yl, indolin-1-yl,

2-methylindolin-l-yl, 5-fluoro-2-methylindolin-l-yl, 2,3-dimethyl- indolin- 1 -yl, decahydroquinolin- 1 -yl, 2-methy ldecahydroquinolin- 1 - yl, 1 ,2,3,4-tetrahydroquinolin- 1 -yl, 2-methyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 6-fluoro-2-methyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 6- chloro-2-methyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl, 2,6-dimethyl- 1 ,2,3,4- tetrahydroquinolin- 1 -yl, 2,2-dimethyl- 1 ,2,3 ,4-tetrahydroquinolin- 1 -yl,

6-fluoro-2,2-dimethyl- 1,2,3, 4-tetrahydroquinolin- 1-yl, 2,2,4-trimethyl- 1,2,3, 4-tetrahydroquinolin- 1-yl, 6-chloro-2,2,4-trimethyl-

1 ,2,

3,4-tetrahydroquinolin- 1 -yl, 2,2-dimethyl- 1 ,2-dihydroquinolin- 1 - yl, 6-fluoro-2,2-dimethyl-l,2-dihydroquinolin-l-yl, 2,2,4-trimethyl- 1,2-dihydroquinolin-l-yl or 2,2,4, 6-tetramethyl-l,2-dihydroquinolin-

1-yl.

4. A process for the preparation of the compounds of the formula (I)

in which

R is defined as mentioned in claim 1.

a) compounds of the formula (II)

in which R is difined as in one of the claims 1 , are reacted with compounds of the formula (III)

in which R and R are as defined in claim 1, and

M represents a leaving group,

in the presence of an inert solvent, and if appropriate, in the presence of an acid binding agent.

5. Herbicidal composition, characterized in that they contain at least one tetrazolinone derivative of the formula (I) according to claim 1.

6. Process for combating weeds, characterized in that a tetrazolinone derivative of the formula (I) according to claim 1 is allowed to act on weeds and/or their habitat.

7. Use of a tetrazolinone derivative of the formula (I) according to claim 1 for combating weeds.

8. Process for the preparation of herbicidal compositions, characterized in that a tetrazolinone derivative of the formula (I) according to claim 1 is mixed with extenders and/or surface active agents.

9. Tetrazolinone derivatives represented by the formula

in which

R is as defined in Claim 1 ,

provided that R never represents non-substituted C₇.₉ aralkyl or substituted benzyl.