BR112018076886B1 - 3-AMINO-1,2,4-TRIAZINE DERIVATIVES, PROCESS FOR PREPARING SAID DERIVATIVES, HERBICIDAL COMPOSITION OR PLANT GROWTH REGULATION COMPOSITION, METHOD FOR CONTROLLING HARMFUL PLANTS OR PLANT GROWTH REGULATION AND USE OF SAID DERIVATIVES - Google Patents

Abstract

3-AMINO-1,2,4-TRIAZINE DERIVATIVES AND THEIR USE TO CONTROL UNWANTED PLANT GROWTH. The invention relates to compounds of general formula (I), their agrochemically compatible salts, a method for their production and their use in the field of plant protection.

Description

[001] The invention relates to the technical field of crop protection compositions, particularly that of herbicides for the selective control of broad-leaved weeds and grasses in plantations of useful plants and in the ornamental garden sector and for the general control of broadleaf weeds and weedy grasses in areas of the environment where plant growth is harmful.

[002] More particularly, the invention relates to 3-amino-1,2,4-triazine derivatives, processes for their preparation and their use to control harmful plants.

[003] The compounds of formula (I) according to the invention have, in position 3 of 1,2,4-triazine, a partially hydrogenated bicyclic substituent linked through an amine to the aromatic system in the alpha position, where the triazine can can also be substituted in position 5 and position 6 and the amino substituent R1 together with the substituent in the adjacent position (R2) can form a ring.

[004] The prior art does not describe the herbicidal action of these 1,2,4-triazines.

[005] The use of known selective herbicides for controlling harmful plants or as plant growth regulators in various plantations of useful plants often confers an application rate that incurs high costs or results in undesirable damage to useful plants. Furthermore, in many cases the use of active compounds is not economical due to comparatively high production costs.

[006] Therefore, it is desirable to provide alternative chemical active compounds that can be used as herbicides or plant growth regulators and that are associated with certain advantages when compared to systems known in the prior art.

[007] It is an object of the present invention to provide alternative active compounds that can be used as herbicides or plant growth regulators, having satisfactory herbicidal action and a broad spectrum of activity against harmful plants and/or having high selectivity in plantations of useful plants. .

[008] The objective is achieved by means of 3-amino-1,2,4-triazine derivatives of formula (I) as claimed in claim 1, which can be used advantageously as herbicides and also as plant growth regulators. plant.

[009] Therefore, the present invention provides the compounds of formula (I) and the agrochemically acceptable salts in which

[010] R1 represents hydrogen, amino, hydrazino, hydroxyamino, ((C1-C6)-alkyl)-amino, ((C3-C6)-cycloalkyl)-amino, di-((C1-C6)-alkyl)-amino , (C1-C6)-alkylcarbonylamino and bis-((C1-C6)-alkyl)-carbonylamino;

[011] R2 is selected from the group consisting of hydrogen, halogen, hydroxy, nitro, amino, cyano, C(O)OH, C(O)NH2; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkylcarbonyloxy, (C1-C6)-haloalkylcarbonyloxy, (C1 -C6)-alkylcarbonyl-(C1-C4)-alkyl; (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, (C1 -C6)-haloalkoxycarbonyl- (C1-C6)-alkyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkoxycarbonyl- (C1-C6)-haloalkyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkenylcarbonyl, (C2-C6)-haloalkenylcarbonyl, (C2-C6)-alkenyloxy, (C2-C6)-haloalkenyloxy, (C2 -C6)-alkenyloxycarbonyl, (C2-C6)-haloalkenyloxycarbonyl; (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C2-C6)-alkynylcarbonyl, (C2-C6)-haloalkynylcarbonyl, (C2-C6)-alkynyloxy, (C2-C6)-haloalkynyloxy, (C2 -C6)-alkynyloxycarbonyl, (C2-C6)-haloalkynyloxycarbonyl; tri-(C1-C6)-alkylsilyl-(C2-C6)-alkynyl, di-(C1-C6)-alkylsilyl-(C2-C6)-alkynyl, (C1-C6)-alkylsilyl-(C2-C6)- alkynyl; phenylsilyl-(C2-C6)-alkynyl; (C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-arylcarbonyl and (C6-C14)-aryloxycarbonyl, each of which can be substituted on the aryl part by halogen, (C1-C6 )-alkyl and/or (C1-C6)-haloalkyl; (C6-C14)-aryl-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkoxy, (C6-C14)-aryl-(C1-C6)-alkylcarbonyl, (C6 -C14)-aryl-(C1-C6)-alkylcarbonyloxy, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyl, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyloxy; aminocarbonyl-(C1-C6)-alkyl, di-(C1-C6)-alkylaminocarbonyl-(C1-C6)-alkyl; N-((C1-C6)-haloalkanoyl)aminocarbonyl, ((C6-C14)-aryl)aminocarbonyl, di-((C6-C14)-aryl)aminocarbonyl, ((C1-C6)-alkyl)aminocarbonyl, di- ((C1-C6)-alkyl)aminocarbonyl, N-((C1-C6)-alkylsulfonyl)aminocarbonyl, N-((C1-C6)-haloalkylsulfonyl)aminocarbonyl, N-((C6-C14)-arylsulfonyl)aminocarbonyl; (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkoxy; (C3-C8)-cycloalkyl which may optionally be substituted on the cycloalkyl radical by (C1-C6)-alkyl and/or halogen; (C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(C1-C6)-alkyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkyl, (C3-C8)-cycloalkyl-(C1 -C6)-alkoxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6 )-alkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6)- haloalkoxycarbonyl, (C3-C8)-cycloalkylcarbonyloxy, (C3-C8)-cycloalkoxycarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyloxy , (C3-C8)-cycloalkyl-(C1-C6)-alkoxy carbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxy carbonyloxy; (C3-C8)-cycloalkenyl, (C3-C8)-cycloalkenyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkyl, (C3 -C8)-cycloalkenyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkenylcarbonyl, (C3-C8)-cycloalkenyloxycarbonyl, (C3-C8 )-cycloalkenyl-(C1-C6)-alkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxycarbonyl, (C3-C8)- cycloalkenyl-(C1-C6)-haloalkoxycarbonyl, (C3-C8)-cycloalkenylcarbonyloxy, (C3-C8)-cycloalkenyloxy carbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkenyl -(C1-C6)-haloalkylcarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxy carbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxy carbonyloxy; hydroxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkoxy, cyano-(C1-C6)-alkoxy, cyano-(C1-C6)-alkyl; and (C1-C6)-alkylsulfonyl, (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-haloalkylsulfonyl, (C1-C6)-haloalkylthio, (C1-C6)-haloalkylsulfinyl, ( C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-alkyl, (C1- C6)-haloalkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-haloalkylthio-(C1-C6)-alkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-alkyl, (C1-C6) -alkylsulfonyl-(C1-C6)-haloalkyl, (C1-C6)-alkylthio-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfonyl -(C1-C6)-haloalkyl, (C1-C6)-haloalkylthio-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfonyloxy, ( C1-C6)-haloalkylsulfonyloxy, (C1-C6)-alkylthiocarbonyl, (C1-C6)-haloalkylthiocarbonyl, (C1-C6)-alkylthiocarbonyloxy, (C1-C6)-haloalkylthiocarbonyloxy, (C1-C6)-alkylthio-(C1- C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkoxy, (C1-C6)-alkylthio-(C1-C6)-alkylcarbonyl, (C1-C6)-alkylthio-(C1-C6) -alkylcarbonyloxy; (C4-C14)-arylsulfonyl, (C6-C14)-arylthio, (C6-C14)-arylsulfinyl, (C3-C8)-cycloalkylthio, (C3-C8)-alkenylthio, (C3-C8)-cycloalkenylthio and (C3 -C6)- alkynylthio; or

[012] R1 can be attached to R2 through a bond, resulting in a 5- to 7-membered partially hydrogenated carbocycle or heterocycle having at least one heteroatom selected from the group consisting of N, O, S and P, which carbocycle or heterocycle is optionally substituted by one or more substituents selected from the group consisting of hydroxy, =O, =N-O-H, =N-O-(C1-C6)-alkyl, =N-O-benzyl, =N-O-phenyl, phenyl, phenyl substituted by a or more identical or different halogen atoms, (C1-C6)-alkyl, (C3-C6)-cycloalkyl and (C1-C6)-haloalkyl;

[013] R3 is selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy, (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6) -alkoxycarbonyl and aminocarbonyl;

[014] R4 and R5 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, hydroxy, (C1-C6)-alkoxy and (C1- C6)-haloalkoxy; or

[015] R4 and R5 together with the carbon atom to which they are attached form a saturated three- to seven-membered ring that may contain one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen;

[016] R6 and R7 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy, (C1-C6) -haloalkoxy, (C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-arylcarbonyl and (C6-C14)-aryloxycarbonyl; or the radicals R6 and R7 together form a (C1-C7)-alkylene group that may contain one or more oxygen and/or sulfur atoms, in which the (C1-C7)-alkylene group may be mono- or polysubstituted by halogen and the respective halogen substituents may be identical or different;

[017] n is the current number 0, 1 or 2;

[018] R8, R9, R10 and R11 are each independently selected from the group consisting of hydrogen, halogen, cyano, C(O)OH, C(O)NH2, (C1-C6)-alkyl, ( C1-C6)-alkylcarbonyl, (C1-C6)-alkyloxycarbonyl, (C1-C6)-alkylaminocarbonyl, (C1-C6)-dialkylaminocarbonyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy, (C1- C6)-haloalkoxy, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C2-C6)-alkynylcarbonyl, (C2-C6)-haloalkynylcarbonyl, (C2-C6) -alkynyloxy, (C2-C6)-haloalkynyloxy, (C2-C6)-alkynyloxycarbonyl, (C2-C6)-haloalkynyloxycarbonyl and nitro, in which the radicals R9 and R10 can be attached to each other via the -O-CH2-O- group forming a ring;

[019] partially hydrogenated portion of the amine;

[020] R12 and R13 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C1-C6)-haloalkyl; It is

[021] R14 is selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C1-C6)-haloalkyl.

[022] The amino group in position 3 of 1,2,4-triazine in bis(amino)triazines of formula (I) according to the invention has a partially hydrogenated bicyclic substituent, said partially hydrogenated bicyclic substituent being attached to amine in the alpha position to the aromatic system.

[023] With an excellent efficacy profile and excellent plant compatibility, the compounds of formula (I) are notable for their cheap preparation, as the substances of the invention can be prepared from cheap and readily available precursors by inexpensive processes. . Therefore, it is possible to do without the use of intermediaries that are expensive and difficult to obtain.

[024] The following is a description of preferred, particularly preferred and very particularly preferred definitions of each of the individual substituents. The other substituents of the general formula (I) that are not specified in this document have the definition presented above. The same also applies to the current number n, that is, the current number n in the following representations is 0, 1 or 2.

[025] A first representation of the present invention covers the compounds of general formula (I) in which

[026] R1 is preferably selected from the group consisting of hydrogen, amino, ((C1-C6)-alkyl)amino, ((C3-C6)-cycloalkyl)amino and di-((C1-C6)-alkyl)amino ;

[027] R1 is particularly preferably selected from the group consisting of hydrogen, amino, ((C1-C3)-alkyl)amino, ((C3-C6)-cycloalkyl)amino and di-((C1-C3)-alkyl) amino;

[028] R1 is very particularly preferred, selected from the group consisting of hydrogen, amino, NH(CH3), N(H)-cyclopropyl and N(CH3)2; and, in which

[029] R1 more preferably represents hydrogen and amino and very particularly preferably amino.

[030] A second representation of the present invention covers the compounds of general formula (I) in which

[031] R2 is preferably selected from the group consisting of hydrogen, halogen, hydroxy, nitro, amino, cyano, C(O)OH, C(O)NH2; (C1-C6)-alkyl, (C1-C6)-haloalkyl; (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C2-C6)-alkynyl, (C2-C6)-haloalkynyl; (C6-C14)-aryl which can be substituted on the aryl part by halogen, (C1-C6)-alkyl and/or (C1-C6)-haloalkyl; (C1-C6)-alkoxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl; ((C1-C6)-alkyl)aminocarbonyl, di-((C1-C6)-alkyl)aminocarbonyl, N-((C1-C6)-alkylsulfonyl)aminocarbonyl, N-((C1-C6)-haloalkylsulfonyl)aminocarbonyl, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl; (C1-C6)-alkylsulfonyl, (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-haloalkylsulfonyl, (C1-C6)-haloalkylsulfinyl, (C4-C14)-arylsulfonyl and (C6 -C14)-arylsulfinyl; (C1-C6)-alkoxy-(C1-C6)-alkyl,

[032] R2 is most preferably selected from the group consisting of halogen, cyano, C(O)OH, (C1-C6)-alkyl, C1-C6-haloalkyl; (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C2-C6)-alkynyl, (C2-C6)-haloalkynyl; phenyl that can be substituted on the aryl part by halogen, (C1-C6)-alkyl and/or (C1-C6)-haloalkyl; ((C1-C3)-alkoxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl; ((C1-C3)-alkyl)aminocarbonyl, di-((C1-C3)-alkyl)aminocarbonyl ; , (C1-C3)-alkylsulfinyl, (C1-C3)-haloalkylsulfonyl, (C1-C6)-haloalkylsulfinyl, (C4-C14)-arylsulfonyl and (C6-C14)-arylsulfinyl;

[033] R2 is particularly preferably selected from the group consisting of Cl, Br, cyano, C(O)OH, C(O)NH2; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl; (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C2-C6)-alkynyl, (C2-C6)-haloalkynyl; phenyl which can be substituted by F, Cl, Br, methyl and/or trifluoromethyl; (C1-C3)-alkoxy-(C1-C3)-alkyl, hydroxy-(C1-C3)-alkyl; ((C1-C2)-alkyl)aminocarbonyl, di-((C1-C2)-alkyl)aminocarbonyl, N-((C1-C2)-alkylsulfonyl)aminocarbonyl, N-((C1-C2)-haloalkylsulfonyl)aminocarbonyl; (C3-C6)-cycloalkylcarbonyl, (C3-C6)-cycloalkoxycarbonyl; (C1-C3)-alkylsulfonyl, (C1-C3)-alkylsulfinyl, (C1-C3)-haloalkylsulfonyl, (C1-C6)-haloalkylsulfinyl, (C4-C14)-arylsulfonyl, (C6-C14)-arylsulfinyl;

[034] R2 is more particularly preferably selected from the group consisting of Cl, cyano, C(O)NH2; (C1-C3)-haloalkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-haloalkylcarbonyl; (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; methoxy-(C1-C3)-alkyl, hydroxy-(C1-C3)-alkyl; ((C1-C2)-alkyl)aminocarbonyl, di-((C1-C2)-alkyl)aminocarbonyl, (C1-C3)-alkylsulfonyl, (C1-C3)-alkylsulfinyl; and in what

[035] R2 more preferably represents Cl, cyano, C(O)NH2, trifluoromethyl, acetyl (C(O)CH3), trifluoroacetyl (C(O)CF3), methoxy-(C2-C3)-alkyl, hydroxy-( C2-C3)-alkyl, (C1-C2)-alkoxycarbonyl, (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, methylaminocarbonyl, dimethylaminocarbonyl, methylsulfonyl and methylsulfinyl.

[036] A third representation of the present invention covers the compounds of general formula (I) in which

[037] R3 preferably represents hydrogen.

[038] A fourth representation of the present invention covers the compounds of general formula (I) in which

[039] R4 and R5 are each preferably and independently selected from the group consisting of hydrogen, hydroxy, (C1-C6)-alkyl, (C1-C6)-alkylphenyl and (C1-C6)-alkoxy;

[040] R4 and R5 are each particularly preferably independently selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C1-C6)-alkoxy;

[041] R4 and R5 are each very particularly preferably independently selected from the group consisting of hydrogen, (C1-C3)-alkyl (C1-C6)-alkoxy; and in what

[042] R4 and R5 more preferably each independently of each other represents hydrogen or methyl.

[043] In this fourth representation, it is especially preferred for at least one of the radicals R4 and R5 to represent hydrogen. In other words, when in each case at least one of the radicals R4 and R5 is hydrogen and the other radical R4 and R5 is not hydrogen, especially (C1-C6)-alkyl, preferably methyl (CH3).

[044] A fifth representation of the present invention covers the compounds of general formula (I) in which

[045] R4 and R5 together with the carbon atom to which they are attached form a saturated three- to six-membered ring that may contain a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;

[046] R4 and R5 together with the carbon atom to which they are attached preferably form a saturated three- to six-membered ring that may contain an oxygen atom;

[047] R4 and R5 together with the carbon atom to which they are attached, preferably form a saturated three- to six-membered ring that may contain an oxygen atom; and in what

[048] R4 and R5 together with the carbon atom to which they are attached form, most preferably, a saturated three-membered ring that may contain an oxygen atom or form a 4-pyran ring.

[049] A sixth representation of the present invention covers the compounds of general formula (I) in which

[050] R6 and R7 are preferably independently selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C6-C14)-aryl;

[051] R6 and R7 are particularly preferably independently selected from the group consisting of hydrogen, methyl and phenyl;

[052] R6 and R7 very particularly preferably each independently of the other represents hydrogen or methyl; and in what

[053] R6 and R7 most preferably represent hydrogen. A seventh representation of the present invention encompasses the compounds of general formula (I) in which

[054] R8 is preferably selected from the group consisting of hydrogen, halogen, (C1-C6)-alkyl, (C1-C6)-alkoxy and (C6-C14)-aryl;

[055] R8 is particularly preferably selected from the group consisting of hydrogen, halogen, (C1-C3)-alkyl and (C6-C8)-aryl;

[056] R8 is more particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine, CH3 and phenyl and in which

[057] R8 most preferably represents hydrogen or CH3.

[058] An eighth representation of the present invention covers the compounds of general formula (I) in which

[059] R9 is preferably selected from the group consisting of hydrogen, halogen, (C1-C6)-alkyl and (C1-C6)-alkoxy;

[060] R9 is particularly preferably selected from the group consisting of hydrogen, chlorine, fluorine and (C1-C3)-alkoxy;

[061] R9 is more particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine and methoxy; and in what

[062] R9 most preferably represents hydrogen.

[063] A ninth representation of the present invention covers the compounds of general formula (I) in which

[064] R10 is preferably selected from the group consisting of hydrogen, halogen, cyano, aminocarbonyl, hydroxycarbonyl, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy, (C2-C6 )-alkenyl, (C2-C6)-alkynyl, (C1-C6)-alkyl-(C2-C6)-alkynyl, hydroxy-(C1-C6)-alkyl-(C2-C6)-alkynyl, (C1-C6 )-alkoxy-(C2-C6)-alkynyl and aryl-(C2-C6)-alkynyl;

[065] R10 is particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methoxy (OCH3), (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3 )-alkoxy, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C3)-alkyl-(C2-C4)-alkynyl, hydroxy-(C1-C3)-alkyl-(C2-C4 )-alkynyl, (C1-C3)-alkoxy-(C2-C4)-alkynyl and phenyl-(C2-C4)-alkynyl;

[066] R10 is more particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, C=CH and C=CCH3; and in what

[067] R10 most preferably represents hydrogen or CH3.

[068] A tenth representation of the present invention covers compounds of general formula (I) in which

[069] R11 is preferably selected from the group consisting of hydrogen and (C1-C6)-alkyl;

[070] R11 is particularly preferably selected from the group consisting of hydrogen and (C1-C4)-alkyl;

[071] R11 most particularly preferably represents hydrogen or methyl; and in what

[072] R11 most preferably represents hydrogen.

[073] An eleventh representation of the present invention covers the compounds of general formula (I) in which

[074] two last groups mentioned the carbon atom is linked to the aromatic portion and the O or S heteroatom is linked to the partially hydrogenated portion of the amine;

[075] or S is linked to the partially hydrogenated portion of the amine; and in which

[076] X more preferably represents a chemical bond or CH2.

[077] A twelfth representation of the present invention covers the compounds of general formula (I) in which

[078] n is preferably 0 or 1.

[079] In the context of the present invention, it is possible to combine the individual preferred, particularly preferred, very particularly preferred and most preferred meanings of the substituents R1 to R11 and 2, preferably 0 or 1.

[080] This means that the present invention covers compounds of general formula (I), in which, for example, the substituent R1 has a preferred meaning and the substituents R2 to R14 have the general meaning or the substituent R2 has a preferred meaning , the substituent R3 has a particularly preferred or very particularly preferred meaning, and the remaining substituents have a general meaning.

[081] Four of these combinations of the definitions presented above for the substituents R1 to R11 and X are illustrated by way of example below and each is described as additional representations:

[082] Combination of the definitions given above for the substituents R1 to R11 and X in each case as being particularly preferred (twelfth representation), combination of the definitions given above for the substituents R1 to R11 and X in each case as being very particularly preferred (thirteenth representation), and combining the definition presented above for the substituent R1 as being very particularly preferred with the definitions presented above for the substituents R1 to R11 and X in each case as being particularly preferred (fourteenth representation).

[083] The representations cited above that are based on combinations of substituents are explicitly disclosed below for clarification:

[084] A thirteenth representation of the present invention covers the compounds of general formula (I) in which

[085] R1 is selected from the group consisting of hydrogen, amino, ((C1-C3)-alkyl)amino, ((C3-C6)-cycloalkyl)amino, di-((C1-C3)-alkyl)amino;

[086] R2 is selected from the group consisting of Cl, Br, cyano, C(O)OH, C(O)NH2; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl; (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C2-C6)-alkynyl, (C2-C6)-haloalkynyl; phenyl which can be substituted by F, Cl, Br, methyl and/or trifluoromethyl; (C1-C6)-alkoxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl; ((C1-C2)-alkyl)aminocarbonyl, di-((C1-C2)-alkyl)aminocarbonyl, N-((C1-C2)-alkylsulfonyl)aminocarbonyl, N-((C1-C2)-haloalkylsulfonyl)aminocarbonyl; (C3-C6)-cycloalkylcarbonyl, (C3-C6)-cycloalkoxycarbonyl; (C1-C3)-alkylsulfonyl, (C1-C3)-alkylsulfinyl, (C1-C3)-haloalkylsulfonyl, (C1-C6)-haloalkylsulfinyl, (C4-C14)-arylsulfonyl, (C6-C14)-arylsulfinyl;

[087] R3 represents hydrogen;

[088] R4 and R5 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C1-C6)-alkoxy;

[089] R6 and R7 are independently selected from the group consisting of hydrogen, methyl and phenyl;

[090] R8 is selected from the group consisting of hydrogen, halogen, (C1-C3)-alkyl and (C6-C8)-aryl;

[091] R9 is selected from the group consisting of hydrogen, chlorine, fluorine and (C1-C3)-alkoxy;

[092] R10 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methoxy (OCH3), (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)- alkoxy, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C3)-alkyl-(C2-C4)-alkynyl, hydroxy-(C1-C3)-alkyl-(C2-C4)- alkynyl, (C1-C3)-alkoxy-(C2-C4)-alkynyl and phenyl-(C2-C4)-alkynyl;

[093] R11 is selected from the group consisting of hydrogen and (C1-C4)-alkyl; It is

[094] is linked to the partially hydrogenated portion of the amine.

[095] A fourteenth representation of the present invention covers the compounds of general formula (I) in which

[096] R1 is selected from the group consisting of hydrogen, amino, NH(CH3), N(H)-cyclopropyl and N(CH3)2;

[097] R2 is selected from the group consisting of Cl, cyano, C(O)NH2; (C1-C3)-haloalkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-haloalkylcarbonyl; (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; (C1-C3)-alkoxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl; ((C1-C2)-alkyl)aminocarbonyl, di-((C1-C2)-alkyl)aminocarbonyl; (C1-C3)-alkylsulfonyl, (C1-C3)-alkylsulfinyl;

[098] R3 represents hydrogen;

[099] R4 and R5 are each independently selected from the group consisting of hydrogen, (C1-C3)-alkyl, (C1-C6)-alkoxy;

[100] R6 and R7 each independently represent hydrogen or methyl;

[101] R8 is selected from the group consisting of hydrogen, fluorine, chlorine, CH3 and phenyl;

[102] R9 is selected from the group consisting of hydrogen, fluorine, chlorine and methoxy;

[103] R10 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, C=CH and C=CCH3;

[104] R11 represents hydrogen or methyl; It is

[105] is linked to the partially hydrogenated portion of the amine.

[106] A fifteenth representation of the present invention encompasses compounds of general formula (I) in which

[107] R1 represents hydrogen and amino;

[108] R2 is selected from the group consisting of Cl, cyano, C(O)NH2, trifluoromethyl, acetyl (C(O)CH3), trifluoroacetyl (C(O)CF3), (C1-C2)-alkoxycarbonyl, ( C1- C2)-haloalkoxycarbonyl, (C2-C3)-alkenyl, (C2-C3)-haloalkenyl, (C1-C3)-alkoxy-(C1-C3)-alkyl, hydroxy-(C1-C3)-alkyl, methylaminocarbonyl , dimethylaminocarbonyl, methylsulfonyl and methylsulfinyl;

[109] R3 represents hydrogen;

[110] R4 and R5 each independently represent hydrogen or methyl;

[111] R6 and R7 represent hydrogen;

[112] R8 represents hydrogen or CH3;

[113] R9 represents hydrogen;

[114] R10 represents hydrogen or CH3;

[115] R11 represents hydrogen; It is

[116] X represents a chemical bond or CH2.

[117] A sixteenth representation of the present invention encompasses compounds of general formula (I) in which

[118] R1 is selected from the group consisting of hydrogen, amino, NH(CH3), N(H)-cyclopropyl and N(CH3)2;

[119] R2 is selected from the group consisting of Cl, cyano, C(O)NH2; (C1-C3)-haloalkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-haloalkylcarbonyl; (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl; (C2-C6)-alkenyl, (C2-C6)-haloalkenyl; methoxy-(C2-C3)-alkyl, hydroxy-(C2-C3)-alkyl; ((C1-C2)-alkyl)aminocarbonyl, di-((C1-C2)-alkyl)aminocarbonyl; (C1-C3)-alkylsulfonyl, (C1-C3)-alkylsulfinyl;

[120] R3 represents hydrogen;

[121] R4 and R5 together with the carbon atom to which they are attached form a saturated three- to six-membered ring that can contain an oxygen atom;

[122] R6 and R7 each independently represent hydrogen or methyl;

[123] R8 is selected from the group consisting of hydrogen, fluorine, chlorine, CH3 and phenyl;

[124] R9 is selected from the group consisting of hydrogen, fluorine, chlorine and methoxy;

[125] R10 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, C=CH and C=CCH3;

[126] R11 represents hydrogen or methyl; It is

[127] X represents a chemical bond or CH2.

[128] In the context of the present invention, the compound of general formula (I) also includes compounds quaternized on a nitrogen atom by a) protonation, b) alkylation or c) oxidation. In this regard, mention should be made of the corresponding N-oxides.

[129] The compounds of formula (I) are capable of forming salts. Salts can be formed by the action of a base on compounds of formula (I) that carry an acidic hydrogen atom. Examples of suitable bases are organic amines such as trialkylamines, morpholine, piperidine or pyridine, as well as ammonium hydroxides, carbonates and bicarbonates, alkali metals or alkaline earth metals, especially sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate , sodium bicarbonate and potassium bicarbonate. These salts are compounds in which the acidic hydrogen is replaced by a suitable agricultural cation, for example, metal salts, especially alkali metal salts or alkaline earth metal salts, especially sodium and potassium salts or ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NRR'R"R'"]+, in which R to R''' each, independently of one another, represent an organic radical, in particular alkyl , aryl, aralkyl or alkylaryl. Also suitable are alkylsulfonium and alkylsulfoxonium salts, such as (C1-C4)-trialkylsulfonium and (C1-C4)-trialkylsulfoxonium salts.

[130] The components of formula (I) can form salts by addition of a suitable inorganic or organic acid, for example, mineral acids, for example, HCl, HBr, H2SO4, H3PO4 or HNO3 or organic acids, for example, carboxylic acids , such as formic acid, acetic acid, oxalic acid, lactic acid, salicylic acid or sulfonic acid, for example p-toluenesulfonic acid, dialkylamino, piperidino, morpholino or pyridino. In this case, these salts will comprise the conjugate base of the acid as the anion.

[131] Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups that for their part can be protonated, such as amino groups.

[132] The components of formula (I) and their salts are also referred to below in abbreviated form as "compounds (I)" according to the invention or used according to the invention.

[133] In general formula (I) and in all other formulas of the present invention, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio radicals and the corresponding unsaturated and/or substituted radicals may, in each case, be straight or branched chain in the carbon skeleton. Unless specifically stated, preference is given to radicals with lower carbon skeletons, for example those with 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms or in the case of unsaturated groups, with 2 to 6 carbon atoms. carbon, in particular 2 to 4 carbon atoms. Alkyl radicals, either alone or in compositional definitions, such as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, tert-butyl or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptis, such as n-heptyl, 1-methyl hexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the definition of possible unsaturated radicals corresponding to alkyl radicals; in which at least one double or triple bond is present, preferably a double or triple bond, respectively. Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en- 1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.

[134] Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cycloalkyl groups may be present in bi- or tricyclic form.

[135] If the haloalkyl groups and haloalkyl radicals of haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl etc. are determined, the lower carbon skeletons of these radicals having, for example, 1 to 6 carbon atoms or 2 to 6 carbon atoms, especially 1 to 4 carbon atoms or preferably 2 to 4 carbon atoms, and the unsaturated radicals and /or corresponding substitutes will be in each case straight or branched chair in the carbon skeleton. Examples are difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl.

[136] The alkylene groups in these radicals are the lower carbon skeletons, for example, those having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms or preferably 2 to 4 carbon atoms, and also the unsaturated radicals and/or or corresponding substitutes on the carbon skeleton which may, in each case, be straight or branched chain. Examples are methylene, ethylene, n- and isopropylene and n-, s-, iso-, t-butylene.

[137] The hydroxyalkyl groups in these radicals are the lower carbon skeletons, for example, those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, and also the corresponding unsaturated and/or substituted radicals on the carbon skeleton that it can, in each case, be straight or branched chain. Examples of these are 1,2-dihydroxyethyl and 3-hydroxypropyl.

[138] The halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl and alkynyl partially or fully substituted by halogen, preferably by fluorine, chlorine or bromine, especially by fluorine and/or chlorine, for example monohaloalkyl, perhaloalkyl, CF3, CF2Cl, CHF2, CH2F , CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy e.g. OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; the same applies correspondingly to haloalkenyl and other halogen-substituted radicals.

[139] Aryl is a monocyclic, bicyclic or polycyclic aromatic system, for example, phenyl or naphthyl, preferably phenyl.

[140] Mainly for reasons of higher herbicidal activity, better selectivity and/or better preparation capacity, the compounds of general formula (I) according to the invention or the agrochemical salts or their quaternary N derivatives that are of particular interest are those in which the individual radicals have one of the preferred definitions already specified or specified below or especially those in which one or more preferred definitions already specified or specified below occur in combination.

[141] The preferred or general radical definitions cited above apply to the final products of general formula (I) and, correspondingly, to the starting materials and intermediates necessary in each case for the preparation. These radical definitions can be exchanged among themselves, that is, including the established preferential ranges among them.

[142] The present compounds of general formula (I) have, in the binding site with amino-1,2,4-triazine, a chiral carbon atom which, in the structure shown below, is indicated by the marker (*):

[143] According to the rules of Cahn, Ingold and Prelog (CIP rules) this carbon atom can have a configuration (R) or a configuration (S).

[144] The present invention covers compounds of general formula (I) with configurations (S) and (R), that is, the present invention covers compounds of general formula (I) in which the carbon atom in question has (1) a configuration (R); or (2) a configuration (S). Furthermore, the scope of the present invention also covers (3) any mixtures of compounds of general formula (I) having an (R) configuration (compounds of general formula (I-R)) with compounds of general formula (I) having a configuration ( S) (compounds of general formula (I-(S)), the present invention also encompassing a racemic mixture of compounds of general formula (I) having the (R) and (S) configuration.

[145] However, in the context of the present invention, preference is given to the use of compounds particularly of general formula (I) having configuration (R) with a selectivity of 60 to 100%, preferably 80 to 100%, especially 90 to 100 %, most particularly 95 to 100% wherein the particular compound (R) is present with an enantioselectivity in each case of more than 50% ee, preferably 60 to 100% ee, especially 80 to 100% ee, most particularly 90 to 100% ee, more preferably 95 to 100% ee, based on the total content of the compound (R) in question.

[146] Thus, the present invention relates especially to compounds of general formula (I*) in which the stereochemical configuration of the carbon atom marked by (*) is present with a stereochemical purity of 60 to 100% (R), preferably 80 to 100% (R), especially 90 to 100% (R), most particularly 95 to 100% (R).

[147] Taking into account the rule of Cahn, Ingold and Prelog, on the carbon atom marked (*) there may also be a situation in which, due to the priority of the substituents in question, the configuration (S) is preferred on the carbon atom marked by (*). This is the case, for example, when the radicals R4 and/or R5 correspond to a C1-C6-alkoxy radical.

[148] Therefore, in the context of the present invention, preference is given especially to compounds of general formula (I) whose spatial organization corresponds to that of compounds of general formula (I) in which R4 and R5 = hydrogen having the configuration (R) with a selectivity of 60 to 100%, preferably 80 to 100%, especially 90 to 100%, much more particularly 95 to 100% wherein the respective analogous compound (R) is present with an enantioselectivity in each case of more than 50% ee, preferably 60 to 100% ee, especially 80 to 100% ee, most particularly 90 to 100% ee, more preferably 95 to 100% ee, based on the total content of the analogous compound (R) in question. Thus, the present invention relates especially to compounds of general formula (I) in which the stereochemical configuration of the carbon atom marked by (*) is present with a stereochemical purity of 60 to 100% (R or analogue of R), preferably 80 to 100% (R or R analogue), especially 90 to 100% (R or R analogue), most particularly 95 to 100% (R or R analogue).

[149] In particular, the compounds of general formula (I), according to the invention, may have other centers of chirality at the carbon atoms marked in the present invention, any stereochemical configuration is possible at the carbon atoms marked by (*) , (**) It is (***):

[150] In the context of the present invention, any stereochemical configuration is possible on the carbon atoms marked by (*), (**) and (***):

[151] Furthermore, depending on the respective radicals chosen, other stereoelements may be present in the compounds of general formula (I) according to the invention.

[152] If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) may occur.

[153] If, for example, one or more asymmetric carbon atoms are present, enantiomers may occur.

[154] The corresponding stereoisomers can be obtained from the mixtures obtained in the preparation by usual separation methods, for example, by chromatographic separation processes. Likewise, it is possible to selectively prepare stereoisomers using stereoselective reactions using optically active starting materials and/or auxiliaries. Thus, the invention also relates to all stereoisomers included in the general formula (I), but not shown in their specific stereomeric form and mixtures thereof.

[155] Particular preference is given to compounds of general formula (I) wherein the chiral carbon atom marked by (*) has an (R) configuration and the chiral carbon atom marked by (**) has an (S) configuration.

[156] The possible combinations of the various substituents of general formula (I) must be understood so that the general principles of the construction of chemical compounds need to be observed, that is, formula (I) does not cover any compounds known to the person skilled in the art as chemically impossible.

[157] Examples of the compounds of general formula (I) are shown below in table form.

[158] Table 1 below specifies the substituents defined in general terms in formula (I). In this table: - "StNR3” is the stereochemical system on the carbon atom to which NH and R3 are attached, "StR4R5" and "StR6R7” are analogously the carbon atoms to which the respective substituents are attached, - the bonding of the substituents is on the left in each case, - if two bonding sites are presented for n = 0, the table does not contain an entry in the corresponding field for R6 and R7. Table 1: Examples of compounds of general formula (I)

[159] The present invention also provides processes for preparing the corresponding compounds of general formula (I) and/or their salts and/or their agrochemically acceptable quaternized nitrogen derivatives: wherein the radicals R1 to R11 and X and n have the above meanings and where, according to a first process a) a compound of general formula (II) wherein R1, R2 has the meaning given above and Z1 represents an exchangeable radical or a leaving group, reacts with an amine of general formula (III) or an acid addition salt of the amine of general formula (III) wherein R3 to R11 and radicals X have the above meaning.

[160] The exchangeable radical Z1 or the leaving group Z1 represents fluorine, chlorine, bromine, iodine, a (C1-C4)-alkylsulfanyl or a (C1-C4)-alkylsulfinyl or a (C1-C4)-alkylsulfonyl, a unsubstituted phenyl-(C1-C4)-alkylsulfonyl or a phenyl-(C1-C4)-alkylsulfonyl that is mono- or polysubstituted by fluorine, chlorine, bromine or (C1-C4)-alkyl or (C1-C4)-alkoxy or represents a (C1-C4)-alkylphenylsulfonyl.

[161] If necessary, a Z1 radical can be converted into another group with better exchangeability. For example, in the context of a two-stage one-pot method, a (C1-C4)-alkylsulfanyl can be converted to an oxidizing agent such as m-chloroperbenzoic acid or Oxone® into a (C1-C4)-alkylsulfinyl or a (C1-C4)-alkylsulfonyl or mixtures thereof and then reacted with an amine of general formula (III) or an acid addition salt using an auxiliary base, for example, triethylamine or potassium carbonate.

[162] The reaction can optionally also be catalyzed by various auxiliaries, for example, by the reactants potassium phosphate, copper(I) iodide and N,N-diethyl-2-hydroxybenzamide or in the form of a Buchwald-Hartwig coupling by the special transition metal catalyst systems.

[163] The compounds of general formula (II) are commercially available or can be prepared by known methods. The substituted 1,2,4-triazines of general formula (II) are a class of compounds that are very familiar to those skilled in the art. There are a large number of different synthetic methods of general applicability (for a review, see, e.g., Houben-Weyl Methods of Organic Chemistry, 4th Edition (1997), Vol. E 9c, Hetarenes IV, pages 582-666 and literature cited).

[164] The amines of general formula (III) or their acid addition salt are commercially available or their synthesis is described in WO 2004/069814 A1. b.) Compounds of general formula (I) can also be prepared initially by preparing a compound of general formula (II-a), wherein Z2 represents a radical from the group consisting of halogen, cyano, (C1-C6)-alkoxycarbonyl, (C1-C6)-alkylcarbonyl and (C1-C6)-alkylthio that can be modified or exchanged, by the process described in a ).

[165] Thus, for example, in the case where Z2 represents cyano, the cyano group can be hydrolyzed with bases such as aqueous sodium hydroxide or potassium hydroxide to produce carboxamides.

[166] In the case where Z2 represents a halogen atom, preferably chlorine, it can react, for example, with alcohols, optionally using additional bases, such as sodium, sodium hydride or the alkoxide of the alcohol in question, to produce alkoxy derivatives in the position R2.

[167] In the case where Z2 represents halogen, preferably bromine or iodine, it can react, for example, under palladium catalysis with aromatic, heteroaromatic or aliphatic boronic acids (Suzuki reaction) or with alkenes or alkynes to produce the target structures corresponding to formula (I).

[168] In the case where Z2 represents (C1-C6)-alkylthio, this group can be converted with an oxidizing agent such as m-chloroperbenzoic acid or Oxone® into (C1-C6)-alkylsulfinyl or (C1-C6)- alkylsulfonyl.

[169] In the case where Z2 represents alkoxycarbonyl (C1-C6), these esters can be hydrolyzed, for example, with bases, such as aqueous sodium hydroxide or potassium hydroxide solution, to produce the corresponding carboxylic acids [formula 1, R2 = C(O)OH]. In turn, the resulting carboxylic acids can in turn react, for example, with amines using auxiliary reagents such as propanephosphonic anhydride (T3P) to produce substituted carboxamides in the R2 position. The resulting carboxylic acids can also be converted, for example, to carbonyl chlorides and then reacted with amines to produce R2-substituted carboxamides.

[170] In the case where Z2 represents (C1-C6)-alkoxycarbonyl, these esters can react, for example, with Grignard reagents (RAMgHal) to produce the corresponding alcohols [formula 1, R2 = C(RA)2OH].

[171] In the case where Z2 represents (C1-C6)-alkylcarbonyl, these ketones can react, for example, with Grignard reagents (RAMgHal) to produce the corresponding alcohols [formula 1, R2 = C[(C1-C6) -alkyl](RA)OH].

[172] If necessary, a Z2 radical can also be converted to another Z2 radical first. Thus, for example, by means of the processes described above, it is possible to first prepare an intermediate of type (II-a) in which the radical Z2 represents halogen, preferably chlorine, which can be converted with nucleophiles, for example, cyanide. sodium, in nitrile (Z2 = cyano) or, for example, with mercaptans, optionally using additional bases, such as sodium, sodium hydride or the thiolate of the thiol in question, in compounds where Z2 = (C1-C6)-alkylthio. c.) Compounds of general formula (I), in which R1 represents amino, can also be prepared by condensation of type (IV) guanidines or their acid addition salts. with acylcyanides of formula (V) (see, for example, Houben-Weyl Methods of Organic Chemistry, 4th Edition (1997), Vol. E 9c, Hetarenes IV, page 597; Chem. Ber. 1960, 93, 2209). d.) Compounds of general formula (II) in which the radical Z1 represents (C1-C4)-alkylthio and the radical R1 represents amino can be prepared in a manner analogous to the process described in c.) with the alternative use of (IV) S-(C1-C4)-alkyl isothiosemicarbazides or their acid addition salts of general formula (IVa) (see, for example, Houben-Weyl Methods of Organic Chemistry, 4th Edition (1997), Vol. E 9c, Hetarenes IV, page 597; Bull. Chem. Soc. Jpn. 1978, 51, 1846).

[173] The sets of compounds of formula (I) and/or their salts that can be synthesized by the reactions mentioned above can also be prepared in a parallel manner, in which this can be carried out manually, automated or fully automated. It is possible, for example, to automate the reaction procedure, preparation or purification of products and/or intermediates. Generally speaking, this means a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (editor: Günther Jung), Wiley, 1999, on pages 1 to 34.

[174] For the parallelized reaction and preparation procedure, it is possible to use several commercially available instruments, for example, reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB11 3AZ, England or MultiPROBE Automated Workstations from PerkinElmer, Waltham, Massachusetts 02451, USA. For parallel purification of compounds of general formula (I) and their salts or of intermediates occurring in the course of preparation, available apparatus include chromatography apparatus, for example, from Teledyne ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504 , USA.

[175] Detailed apparatus leads to a modular procedure in which individual processing steps are automated, but manual operations need to be performed between processing steps. This can be avoided by partially or completely using integrated automation systems in which the respective automation modules are operated, for example, by robots.

[176] The implementation of single or multiple synthesis steps can be supported by the use of polymer-supported reagents/scavenger resins. The specialist literature describes a number of experimental protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

[177] With the exception of the methods described here, compounds of general formula (I) and their salts can be prepared completely or partially by solid phase supported methods. For this purpose, individual intermediates or all intermediates in the synthesis or adapted by the synthesis for the corresponding procedure are bound to a synthesis resin. Solid phase supported synthesis methods are adequately described in the technical literature, for example, Barry A. Bunin in “The Combinatorial Index”, Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (editor: Günther Jung) , Wiley, 1999. The use of solid phase-supported synthesis methods allows several protocols, which are known in the literature and which in turn can be performed manually or in an automated manner.

[178] In both solid and liquid phases, the implementation of individual or multiple synthesis steps can be supported by the use of microwave technology. Specialized literature describes a number of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (editor: C. O. Kappe and A. Stadler), Wiley, 2005.

[179] The preparation of the processes described in this document produces the compounds of formula (I) and their salts in the form of sets of substances that are called libraries. The present invention also provides libraries comprising at least two compounds of formula (I) and their salts.

[180] Due to the herbicidal property of the compounds of general formula (I), the invention also provides for the use of the compounds of general formula (I) according to the invention as herbicides for controlling harmful plants.

[181] Herbicides are used on agricultural crops used during various stages of cultivation. Therefore, the application of some products occurs before or during sowing. Others are applied before the cultivated plant emerges, that is, before the seedling breaks through the surface of the earth (pre-emergence herbicides). Lastly, post-emergence herbicides will be used if they already have seed leaves or foliage has been formed by the crop plant.

[182] The compounds of the invention can be used pre-emergence or post-emergence, with preference being given to the use of the compounds of the invention in pre-emergence.

[183] Pre-emergence treatment includes treating the area under cultivation before sowing (ppi = pre-plant incorporation) and treating sown crop areas that do not yet support any growth.

[184] The compounds of formula (I) according to the invention and their salts, also equally and collectively referred to as compounds of formula (I) have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous plants. The active compounds also have great control over perennial weeds that are difficult to control and produce branches from rhizomes, root branches or other perennial organs. It does not matter here whether the substances are applied by the pre-seeding method, pre-emergence method or post-emergence method.

[185] Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of general formula (I) according to the invention are cited, without any intention that the enumeration is to impose a restriction on species in particular.

[186] On the side of monocotyledonous weed species, e.g., Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, Ischaemum, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria, Sphenoclea and also Cyperus species predominantly from the annual group and on the sides of perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species are well controlled.

[187] In the case of dicotyledonous weed species, the spectrum of activity extends, for example, to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual and Convolvulus, Cirsium, Rumex and Artemisia in the case of perennial weeds. Furthermore, herbicidal action is observed in case of dicotyledonous weeds such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Emex, Galeopsis, Galinsoga, Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa , Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium.

[188] If the compounds of general formula (I) according to the invention are applied to the soil surface before germination, the emergence of weed seedlings will be prevented completely or the weeds will grow until they reach the cotyledonous stage, but then they stop growing and finally die completely after three or four weeks.

[189] If the active compounds of general formula (I) are applied after emergence to the green parts of plants, growth will also stop very quickly after treatment, and the weeds will remain in the growth stage at the time of application or die. completely after a certain period, so that the competition between weeds, which is harmful to crop plants, is eliminated very early and lastingly.

[190] Although the compounds of general formula (I) according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, plants cultivating economically important crops, for example, wheat, barley, rye, rice, corn, sugar beet, cotton, rapeseed and soybeans are only insignificantly damaged. It is for this reason that the present compounds are highly suitable for the selective control of unwanted plant growth in agriculturally useful plants.

[191] Furthermore, the substances of general formula (I) according to the invention have excellent growth-regulating properties in crop plants. They enter the plant's metabolism in a regulatory manner and, therefore, can be used to objectively influence plant constituents and facilitate harvesting, such as, for example, triggering desiccation and delayed growth. Furthermore, they are also suitable for general control and inhibition of unwanted plant growth without killing the plants in the process. Plant growth inhibition plays an important role in mono- and dicot crops; This can reduce or completely prevent plant toppling.

[192] Due to the herbicidal and plant growth regulatory properties, active compounds can also be used to control harmful plants in the harvest of genetically modified plants that are known or still in development. In general, transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or plant disease pathogens such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties are related, for example, to the cultivated material with respect to quantity, quality, storage capacity, composition and specific constituents. For example, there are known transgenic plants with an increased starch content or altered starch quality or those with a different fatty acid composition in the cultivated material. Other properties in particular may be tolerance or resistance to abiotic stressors, for example, heat, low temperatures, drought, salinity and ultraviolet radiation.

[193] It is preferable to employ the compounds of general formula (I) according to the invention or their salts in economically important transgenic crops of useful plants and ornamental plants, for example, cereals, such as wheat, barley, rye, oats, sorghum and millet, rice, cassava and corn or other sugar beet crops, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.

[194] It is preferable to employ the compounds of general formula (I) as herbicides in plantations of useful plants that are resistant, or that have become resistant, through recombinant means, to the phytotoxic effects of herbicides.

[195] Conventional means of producing new plants that have modified properties compared to existing plants consist, for example, of traditional methods of cultivation and generation of mutants. Alternatively, new plants with altered properties can be generated with the help of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, there have been descriptions in several cases of: - genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/011376, WO 92/014827, WO 91/019806), - transgenic plants of crops that are resistant to certain herbicides of the glufosinate type (cf., for example, EP 0242236, EP 0242246) or the glyphosate type (WO 92/000377) or the sulfonylurea type (EP 0257993, US 5013659), - plants transgenic crop plants, for example cotton, capable of producing Bacillus thuringiensis toxins (Bt toxins), which make plants resistant to certain pests (EP 0142924, EP 0193259), - transgenic crop plants that have a modified fatty acid composition (WO 91/013972) production and increased stress tolerance (EP 0305398), - transgenic crop plants that produce important pharmaceutical or diagnostic proteins), - transgenic crop plants that show higher yields or better quality, - transgenic crop plants that show a combination, for example, the new properties mentioned above ("gene stacking").

[196] Several molecular biology techniques that can be used to produce novel transgenic plants with modified properties are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, "Trends in Plant Science" 1 (1996) 423-431) .

[197] For these recombinant manipulations, nucleic acid molecules that allow mutagenesis or sequence change by recombination of DNA sequences can be introduced into plasmids. With the help of standard methods it is possible, for example, to combine base changes, remove parts of sequences or add natural or synthetic sequences. To join DNA fragments to each other, adapters or linkers can be placed on the fragments; see, for example, Xambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone" [Genes and clones], VCH Weinheim 2nd edition, 1996.

[198] For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect, or expression of at least one a suitably created ribozyme that specifically cleaves transcripts of the above gene product.

[199] To this end, firstly it is possible to use DNA molecules that include the entire coding sequence of a gene product inclusive of any flanking sequences that may be present and also DNA molecules that only include parts of the coding sequence, in which case it is necessary for these portions to be long enough to have an antisense effect on the cells. It is also possible to use DNA sequences that have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them.

[200] By expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired compartment of the plant cell. However, to obtain localization in a specific compartment, it is possible, for example, to join the coding region to DNA sequences, which ensures localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Nucleic acid molecules can also be expressed in plant cell organelles.

[201] Transgenic plant cells can be regenerated by known techniques to provide whole plant growth. In principle, transgenic plants can be plants of any desired plant species, i.e. not only monocots but also dicotyledonous plants.

[202] In this way, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=external) genes or gene sequences.

[203] It is preferable to use the compounds of general formula (I) according to the invention in transgenic crops that are resistant to growth regulators, for example, dicamba or to herbicides that inhibit essential plant enzymes, for example, acetolacto synthase ( ALS), EPSP synthases, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD) or against herbicides from the sulfonylurea group, glyphosate, glufosinate or benzolisoxazoles and similar active compounds.

[204] When the active compounds of the general formula (I) according to the invention are used in transgenic crops, not only do the effects on the harmful plants observed in other crops occur, but also often the effects that are specific to the application in the transgenic crop in particular, for example, an altered or specifically comprehensive weed spectrum that can be controlled, altered application rates that can be used for application, preferably good combination with the herbicides to which the transgenic crop is resistant, and influence of growth and production of transgenic crop plants.

[205] Therefore, the invention also relates to the use of compounds of general formula (I) according to the invention, as herbicides to control harmful plants in transgenic crop plants.

[206] The compounds of general formula (I) can be formulated in various ways, according to the necessary biological and/or physicochemical parameters. Possible formulations include, for example, wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, solutions sprayables, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), powdered products (DP), dressings, granules for distribution and soil application, granules (GR) in form of microgranules, spray granules, absorption and adsorption granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes.

[207] These types of individual formulations are known in principle and are described, for example, in: Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973, K. Martens, "Spray Drying" Handbook, 3a. Ed. 1979, G. Goodwin Ltd. London.

[208] Required formulation assistants such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; H.v. Olphen, “Introduction to Clay Colloid Chemistry,” 2a. ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2a. ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents," Chem. Pub. Co. Inc., N.Y. 1964, Schonfeldt, "Grenzflachenaktive Ãthylenoxidaddukte [Interface active ethylene oxide adducts]”, Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, "Chemische Technologie [Chemical Technology]", Volume 7, C Hanser Verlag Munich, 4th Ed. 1986.

[209] Based on these formulations, it is also possible to produce combinations with other active pesticide compounds, for example, insecticides, acaricides, herbicides, fungicides and also with protectants, fertilizers and/or growth regulators, for example, in the form of a ready-made formulation or tank mix.

[210] Wettable powders are preparations that can be uniformly dispersed in water and, as well as the active compound, without considering a diluent or inert substance, also comprise surfactants of the ionic and/or non-ionic type (wetting agents, dispersing agents), for example example, polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, polyglycol ether fatty alcohol sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To produce wettable powders, active herbicidal compounds are finely ground in conventional apparatus such as hammer mills, blower mills and air jet mills, and mixed simultaneously or subsequently with formulation auxiliaries.

[211] Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or relatively high-boiling aromatics or hydrocarbons or mixtures of organic solvents, with addition of one or more surfactants of the ionic and/or non-ionic type (emulsifiers). Examples of emulsifiers that can be used are: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty acids, polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, e.g., sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, e.g., polyoxyethylene sorbitan fatty acid esters.

[212] Powders are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite or diatomaceous earth.

[213] Suspension concentrates can be water or oil based. They can be produced, for example, by wet grinding using standard commercial ball mills and optionally the addition of surfactants, as already listed above, for example, for the other types of formulation.

[214] Emulsions, e.g. Oil-in-water (EW) emulsions can be prepared, for example, by means of agitators, colloidal mills and/or static mixers using aqueous organic solvents and if appropriate, surfactants, as have, for example, been listed above in connection with o other types of formulation.

[215] Granules can be produced by spraying the compound ingredient onto adsorptive granular inert material or by applying active compound concentrates to the surface of carriers, such as sand, kaolinites or granular inert material, by means of adhesives, for example, polyvinyl alcohol , sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the usual way for the production of fertilizer granules - if desired as a mixture with fertilizers.

[216] Water dispersible granules are generally produced by the usual processes such as spray drying, fluidized bed granulation, container granulation, mixing with high speed mixers and extrusion without solid inert material.

[217] For the production of container, fluidized bed, extruder and spray granules, see e.g. the processes in "Spray - Drying Handbook" 3a. Ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook", 5a. Ed., McGraw-Hill, New York 1973, pp. 8-57.

[218] For further details regarding the formulation of crop protection agents, see, for example, G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook," 5a. ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[219] Agrochemical formulations generally contain 0.1% to 99% by weight, especially 0.1 to 95% by weight of the active compound of formula (I).

[220] In wettable powders, the concentration of the active compound is, for example, approximately 10% to 90% by weight; the remainder 100% by weight consists of the components of the usual formulation. In emulsifiable concentrates, the concentration of the active compound can be approximately 1% to 90% and preferably 5 to 80% by weight. Formulations in the form of powders comprise 1 to 30% by weight of active compound, preferably normally 5 to 20% by weight of active compound; sprayable solutions contain from approximately 0.05% to 80% by weight, preferably from 2% to 50% by weight of active compound. In the case of water-dispersible granules, the content of the active compound depends partly on whether the active compound is present in liquid or solid form and in which auxiliaries, fillers, etc. are used. of granulation. In water-dispersible granules, the content of the active compound is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.

[221] Furthermore, the aforementioned active compound formulations optionally comprise respective wetting, dispersing, emulsifying, penetrating, preservative, antifreeze and solvent adhesive agents, fillers, carriers and dyes, foam deformers, evaporation inhibitors and customary agents that influence pH and viscosity.

[222] The compounds of general formula (I) or their salts can be used as such or in the form of preparations (formulations) in a combination with other pesticide-active substances, for example, insecticides, acaricides, nematicides, herbicides, fungicides, protectants, fertilizers and/or growth regulators, for example, in the form of a finished formulation or a tank mix.

[223] For application, formulations in commercial form are diluted, if appropriate, in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Powder-type preparations, granules for soil application or spreading granules and sprayable solutions are normally not diluted with other inert substances before application.

[224] The required application rate of compounds of formula (I) varies according to external conditions, such as, inter alia, temperature, humidity and the type of herbicide used. It can vary within broad limits, for example between 0.001 to 10.0 kg/ha or more of the active substance but is preferably between 0.005 and 5 kg/ha.

[225] The present invention is illustrated in detail by the following examples, but these examples do not restrict the invention in any way.

A. Synthesis examples 6-Chloro-N3-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1,2,4-triazine-3,5-diamine ( Ex. 1,3)

[226] In a microwave oven, 1.100 g (6.667 mmol) of 3,6-dichloro-1,2,4-triazine-5-amine, 1.290 g (8.001 mmol) of (1R,2S)-2 ,6-dimethylindan-1-amine and 5.210 g (26.669 mmol) of dicyclohexylmethylamine in 10.0 ml of 1-methylpyrrolidin-2-one were heated at 160°C for 1 h. The mixture was poured into water and extracted three times with ethyl acetate. The combined organic phases were washed successively four times with water and once with saturated aqueous sodium chloride solution and dried over sodium sulfate, the solvent was removed by distillation under reduced pressure, and the residue was purified by chromatography (start: acetate from ethyl/n-heptane (5:95), in 30 min to ethyl acetate/n-heptane (60:40).Crystallization of the crude product from a mixture of ethyl acetate and n-heptane (4:1) yielded 1,210 g (44%) of 6-chloro-N3-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1,2,4- triazine-3,5-diamine.

6-(4-Chlorophenyl)-N3-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1,2,4-triazine-3, 5-diamine (Ex. 1.79)

[227] To a solution of 0.150 g (0.518 mmol) of 6-Chloro-N3-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]- 1,2,4-triazine-3,5-diamine (see above, Ex. 1,3) in 4.0 ml of 1,2-dimethoxyethane, 0.185 g (0.776 mmol) of 2-(4-chlorophenyl)- 4,4,5,5- tetramethyl-1,3,2-dioxaborolane, 0.018 g (0.026 mmol) of palladium(II) bis(triphenylphosphine) chloride and 0.414 ml (1.035 mmol) of an aqueous cesium carbonate solution of 2.5 molar were added in succession under argon. In a microwave oven, the mixture was heated at 80°C for 3 h. Water and ethyl acetate were added, and the aqueous phase was washed twice with ethyl acetate. The combined organic phases were dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by chromatography [start: ethyl acetate/n-heptane (5:95), in 25 min for ethyl acetate/ n-heptane (50:50)]. This yielded 0.153 g (81%) of 6-(4-Chlorophenyl)-N3-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1 ,2,4-triazine-3,5-diamine.

Ethyl 5-amino-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4-triazine-6-carboxylate (Ex. 1.32)

[228] 0.759 g (3.081 mmol) of meta-chloroperbenzoic acid dissolved in 20 ml of trichloromethane was added dropwise to a solution of 0.300 g (1.400 mmol) of ethyl 5-amino-3-(methylsulfanyl)-1,2, 4-triazine-6-carboxylate in 20 ml of trichloromethane. The mixture was stirred at 0°C for 1 h, and 0.543 g (4.201 mmol) of N,N-diisopropylethylamine and 0.309 g (2.100 mmol) of (1R)-1,2,3,4-tetrahydronaphthalene-1 -amine dissolved in 2 ml of trichloromethane were added in succession. The mixture was stirred at 50°C for 2 h, water and dichloromethane were added, and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were dried over sodium sulfate, the solvent was removed under reduced pressure, and the residue was taken up in acetonitrile. The insoluble residue (3-chlorobenzoic acid) was filtered, and the solvent was removed under reduced pressure, yielding, after purification of the residue by chromatography [start: ethyl acetate/n-heptane (5:95), in 60 min for acetate of ethyl/n-heptane (45:55)], 0.338 g (73%) of ethyl 5-amino-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1 ,2,4-triazine-6-carboxylate.

5-Amino-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4-triazine-6-carboxylic acid (Ex. 1.28)

[229] 0.245 g (0.782 mmol) ethyl 5-amino-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4-triazine-6-carboxylate (see, above, Ex. 1.32) were mixed in 6 ml of methanol and added to a solution of 0.263 g (4.691 mmol) of potassium hydroxide in 6 ml of water. The mixture was heated under reflux for 2 hours. After removing the alcohols under reduced pressure, the remaining aqueous solution was adjusted to pH 2 using concentrated hydrochloric acid. Filtration and drying of the precipitate formed yielded 0.169 g (72%) of 5-amino-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4- triazine-6-carboxylic acid as a colorless solid.

5-Amino-N-methyl-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4-triazine-6-carboxamide (Ex. 1.34)

[230] At 0°C, 0.377 g (0.592 mmol) of propanephosphonic anhydride (T3P, 50% conc. solution in tetrahydrofuran) was added to a solution of 0.130 g (0.456 mmol) of 5-amino-3 -[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4-triazine-6-carboxylic acid (see above, Ex. 1.28), 0.017 g (0.547 mmol) of methanamine (2 molar solution in tetrahydrofuran) and 0.138 g (1.367 mmol) of triethylamine in 5 ml of dichloromethane, and the mixture was stirred at 25°C for 12 h. Water was added to the mixture, and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by chromatography [start: ethyl acetate/n-heptane (5:95), over 40 min for ethyl acetate at 100%], yielding 0.015 (11%) of 5-amino-N-methyl-3-[(1R)-1,2,3,4-tetrahydronaphthalen-1-ylamino]-1,2,4- triazine-6-carboxamide. 1-{5-Amino-3-[(1R)-2,3-dihydro-1H-inden-1-ylamino]-1,2,4-triazin-6-yl}ethanone (Ex. 1.29 ) 1. 0.785 g (18.692 mmol) of lithium hydroxide was added to a solution of 1.000 g (4.673 mmol) of ethyl 5-amino-3-(methylsulfanyl)-1,2,4-triazine-6-carboxylate in 20 ml of tetrahydrofuran, and the mixture was stirred at 25°C for 4 hours. The solvent was removed under reduced pressure, 20 ml of water was added to the residue, and the pH was adjusted to 4 using 4N hydrochloric acid. Filtration and drying of the precipitate formed yielded 0.800 g (90%) of 5-amino-3-(methylsulfanyl)-1,2,4-triazine-6-carboxylic acid as a colorless solid. 2. Successively, 1.79 ml of triethylamine, 0.781 g (5.106 mmol) of 1-hydroxybenzotriazole (HOBt), 0.975 g (5.106 mmol) of N'-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDCxHCl) and 0.500 g (5.106 mmol) of N-methoxymethanamine were added to a solution of 0.800 g (4.255 mmol) of 5-amino-3-(methylsulfanyl)-1,2,4-triazine-6-carboxylic acid in 10 ml of dimethylformamide, and the mixture was stirred at 25°C for 16 h. 20 ml of water was added to the mixture and the aqueous phase was extracted three times with ethyl acetate. After drying the combined organic phases in sodium sulfate, the solvent was distilled under reduced pressure yielding 0.870 g (88%) of 5-amino-N-methoxy-N-methyl-3-(methylsulfanyl)-1,2,4 -triazine-6-carboxamide as a yellow oil. 3. At 0°C, 6.67 ml (12.987 mmol) of methylmagnesium bromide (1molar solution in THF) was added to a solution of 0.600 g (2.597 mmol) of 5-amino-N-methoxy-N-methyl -3-(methylsulfanyl)-1,2,4-triazine-6-carboxamide in 10 ml of tetrahydrofuran, and the mixture was stirred at 25°C for 5 hours. Saturated aqueous ammonium chloride solution was added dropwise to the mixture, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by chromatography [ethyl acetate/n-hexane (20:80)], yielding 0.200 g (41%) of 1 -[5-amino-3-(methylsulfanyl)-1,2,4-triazin-6-yl]ethanone. 1H-NMR (400 MHz in CDCI3): δ = 2.54 (3H, s), 2.62 (3H, s), 8.20 (1H, bs), 8.52 (1H, bs). 4. At 0°C, 0.442 g (1.791 mmol) of meta-chloroperbenzoic acid dissolved in 20 ml of trichloromethane was added dropwise to a solution of 0.150 g (0.814 mmol) of 1-[5-amino-3-(methylsulfanyl )-1,2,4-triazin-6-yl]ethanone in 40 ml of trichloromethane. The mixture was stirred at 20°C for 1 h, and 0.316 g (2.443 mmol) of N,N-diisopropylethylamine and 0.163 g (1.221 mmol) of (1R)-indan-1-amine dissolved in 2 ml of trichloromethane were added. in succession. The mixture was stirred at 50°C for 2 h, water and dichloromethane were added, and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were dried over sodium sulfate, the solvent was removed under reduced pressure, and the residue was taken up in acetonitrile. The insoluble residue (3-chlorobenzoic acid) was filtered, and the solvent was removed under reduced pressure, yielding, after purification of the residue by chromatography [start: ethyl acetate/n-heptane (5:95), in 60 min for acetate of ethyl/n-heptane (45:55)], 0.108 g (49%) of 1-{5-amino-3-[(1R)-2,3-dihydro-1H-inden-1-ylamino] -1,2,4-triazin-6-yl}ethanone (Ex. 1.29). N3-(3,4-Dihydro-2H-chromen-4-yl)-6-(trifluoromethyl)-1,2,4-triazine-3,5-diamine (Ex. 1.47) 1. 25 ml of a saturated aqueous solution of ammonium hydroxide were added to a solution of 18.00 g (42.92 mmol) of 5-chloro-3-(methylsulfanyl)-6-(trifluoromethyl)-1,2,4-triazine in 33 ml of 1,4-dioxane, and the mixture was stirred at 25°C for 10 min. 150 ml of water was added. Filtration and washing the formed solid with water and n-hexane yielded 14.6 g (88%) of 3-(methylsulfanyl)-6-(trifluoromethyl)-1,2,4-triazine-5-amine as a brown solid . 1H-NMR (400 MHz in CDCl3): δ = 2.61 (3H, s), 5.51 (2H, bs). 2. 0.250 g (1.130 mmol) of 3-(methylsulfanyl)-6-(trifluoromethyl)-1,2,4-triazine-5-amine and 0.337 g (2.260 mmol) of chroman-4-amine in 2.0 ml of 1-methylpyrrolidin-2-one are heated at 180°C for 30 h. The solvent was removed under high vacuum, the residue was mixed in ethyl acetate and water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed successively once with water and once with saturated aqueous sodium chloride solution and dried over sodium sulfate, the solvent was removed by distillation under reduced pressure, and the residue was purified by chromatography (acetonitrile/water ). Under reduced pressure, acetonitrile was removed from the product fraction, the aqueous solution that remained was adjusted to pH 9 using saturated aqueous sodium carbonate solution, and the mixture was extracted three times with dichloromethane. After drying the combined organic phases over sodium sulfate, the solvent was distilled under reduced pressure yielding 0.035 g (10%) of N3-(3,4-dihydro-2H-chromen-4-yl)-6-( trifluoromethyl)-1,2,4-triazine-3,5-diamine (Ex. 1.47).

NMR data from selected examples List of NMR peaks

[231] 1H-NMR data from selected examples are presented in the form of 1H-NMR peak lists. For each signal peak, first the δ value in ppm, and then the signal intensity in parentheses. Pairs of δ signal-value intensity numbers for different signal peaks are listed separated by semicolons.

[232] Therefore, the peak list for an example has the following format: δi (intensityi); δ2 (intensity2); ……..; δi (intensityi); ……..; δn (intensityn)

[233] The intensity of the sharp signals is related to the height of the signals in a printed example of an NMR spectrum in cm and shows the actual relationships of the signal intensities. In the case of broad signals, several peaks or the center of the signal and their relative intensity can be shown in comparison to the most intense signal in the spectrum.

[234] To calibrate the chemical shift of the iH NMR spectrum, we use tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak can, but need not, occur in the NMR peak lists.

[235] iH NMR peak lists are similar to conventional iH NMR printouts and, as such, generally contain all peaks listed in a conventional NMR interpretation.

[236] Furthermore, like conventional iH NMR prints, they can show solvent signals, stereoisomer signals of the target compounds, which also constitute the object of the invention, and/or impurity peaks.

[237] When reporting compound signals in the delta range of solvents and/or water, our iH NMR peak lists show the general solvent peaks, for example, DMSO peaks in DMSO-D6 and the water peak, which generally has a high intensity on average.

[238] Stereoisomer peaks of target compounds and/or impurity peaks generally have a lower intensity on average than peaks of target compounds (e.g., with a purity > 90%).

[239] These stereoisomers and/or impurities may be common to the particular preparation process. Its peaks can thus help in identifying the reproduction of our preparation process with reference to "by-product fingerprints".

[240] An expert, who calculates the peaks of the target compounds using known methods (MestreC, ACD simulation, but also with expected values evaluated empirically), can, if necessary, isolate the peaks of the target compounds, using filters as an option. additional intensity. This isolation would be similar to relevant peak selection in conventional 1H NMR interpretation.

[241] Further details of the 1H NMR peak lists can be found in Research Dissemination Database #564025. B. Formulation Examples a) A powder product is obtained by mixing 10 parts by weight of a compound of formula (I) and/or its salts and 90 parts by weight of talc as an inert substance and spraying the mixture into a hammer mill. b) A water-dispersible wettable powder is readily obtained by mixing 25 parts by weight of a compound of formula (I) and/or its salts, 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent and grinding the mixture in a fixed disc mill. c) A water-dispersible dispersion concentrate is readily obtained by mixing 20 parts by weight of a compound of formula (I) and/or its salts with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, e.g., from approximately 255 to over 277°C) and grinding the mixture in a friction ball mill at a thickness less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I) and/or its salts, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier. e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of formula (I) and/or its salts, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, grinding the mixture in a fixed disc mill and granulating the powder in a fluidized bed by spray application of water as a granulating liquid. f) Water-dispersible granules are also obtained by homogenization and pre-pulverization in a colloidal mill, 25 parts by weight of a compound of formula (I) and/or its salts, 5 parts by weight of sodium 2,2'- dinaphthylmethane-6,6'-disulfonate 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, then grinding the mixture in a grinding mill beads and atomization and drying of the resulting suspension in a spray tower through a single-stage nozzle.

C. Biological examples Test description 1. Herbicidal effect on crop plant pre-emergence and compatibility

[242] Seeds of monocotyledonous and dicotyledonous weeds and crop plants are arranged in sandy clay soil and wood fiber containers and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as an aqueous suspension or emulsion at a water application rate equal to 600 to 800 L /ha with the addition of 0.2% wetting agent.

[243] After treatment, the containers are placed in a greenhouse and maintained under ideal growing conditions for the test plants. Damage to test plants is assessed visually after a 3-week test period by comparison with untreated controls (herbicidal activity in percentage (%): 100% activity = plants died, 0% activity = as control plants ). In the tables below, the following abbreviations are used: Unwanted plants/weeds Table 2: Pre-emergence effectiveness Table 3: Pre-emergence effectiveness Table 4: Pre-emergence effectiveness Table 5: Pre-emergence effectiveness Table 6: Pre-emergence effectiveness

[244] As shown by the results, the compounds of the invention have excellent pre-emergence herbicidal activity against a broad spectrum of grass and broadleaf weeds. For example, the compounds in Tables 2 to 6 have very good herbicidal activity against noxious plants such as Veronica persicam, Stellaria media and Matricaria inodora in the pre-emergence method at an application rate of 320 g/ha and less active substance per hectare . Therefore, the compounds of the invention are suitable for controlling unwanted plant growth by the pre-emergence method.

2. Herbicidal effect on post-emergence and crop plant compatibility

[245] Monocotyledonous and dicotyledonous weed seeds and crop plants are placed in sandy clay soil in wood fiber containers, covered with soil, and grown in a greenhouse under ideal growing conditions. 2 to 3 weeks after sowing, test plants are treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are sprayed onto the true parts of the plant as an aqueous suspension or emulsion at a water application rate equal to 600 to 800 L/ ha with the addition of 0.2% wetting agent. After the test plants have been left to rest in the greenhouse under ideal growth conditions for approximately 3 weeks, the action of the preparations is assessed visually in comparison to untreated controls (herbicidal action in percentage (%): 100% activity = as plants died, 0% activity = as control plants). Table 7: Post-emergency activity Table 8: Post-emergency activity Table 9: Post-emergency activity Table 10: Post-emergency activity

[246] As the results show, the compounds according to the invention have excellent post-emergence efficacy against a broad spectrum of weeds and broad-leaved weeds. For example, the compounds in Tables 7 to 10 have very good herbicidal activity against noxious plants such as Veronica persicam and Stellaria media in the post-emergence method at an application rate of 320 g/ha and less active substance per hectare. Therefore, the compounds of the invention are suitable for controlling unwanted plant growth by the post-emergence method.

Claims (15)

1. Compounds CHARACTERIZED by the fact that they are of the general formula (I) and their agrochemically acceptable salts, wherein R1 represents amino, ((C1-C6)-alkyl)-amino, ((C3-C6)-cycloalkyl)-amino; R2 is selected from the group consisting of halogen, cyano, C(O)OH; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-alkylcarbonyloxy; (C1-C6)-alkoxy; (C2-C6)-haloalkenyl; (C2-C6)-alkynyl; tri-(C1-C6)-alkylsilyl-(C2-C6)-alkynyl; (C6-C14)-aryl, which can be replaced in the aryl part by halogen; aminocarbonyl-(C1-C6)-alkyl; N-((C1-C6)-alkylsulfonyl)aminocarbonyl, N-((C6-C14)-arylsulfonyl)aminocarbonyl; and (C1-C6)-alkylsulfonyl and (C1-C6)-alkylsulfinyl; R3 is hydrogen; R4 and R5 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl, hydroxy and (C1-C6)-alkoxy; R6 and R7 are hydrogen; n is 0, 1 or 2; R8, R9, R10 and R11 are each independently selected from the group consisting of hydrogen, halogen and (C1-C6)-alkyl; and X represents O or S. 2. Compounds of general formula (I), according to claim 1, CHARACTERIZED by the fact that R2 is selected from the group consisting of halogen, cyano, C(O)OH; (C1-C6)-alkyl, C1-C6-haloalkyl; (C1-C6)-alkylcarbonyl; (C2-C6)-haloalkenyl; (C2-C6)-alkynyl; (C6-C14)-aryl which can be replaced in the aryl part by halogen; ((C1-C6)-alkyl)aminocarbonyl, N-((C1-C6)-alkylsulfonyl)aminocarbonyl; (C1-C6)-alkylsulfonyl and (C1-C6)-alkylsulfinyl. 3. Compounds of general formula (I), according to claim 1 or 2, CHARACTERIZED by the fact that R11 is selected from the group consisting of hydrogen and (C1-C6)-alkyl. 4. Compounds of general formula (I), according to any one of claims 1 to 3, CHARACTERIZED by the fact that the current number n is 0 or 1. 5. Compounds of formula (I), according to any one of claims 1 to 4, CHARACTERIZED by the fact that R1 is selected from the group consisting of amino, ((C1-C3)-alkyl)amino and ((C3- C6)-cycloalkyl)amino; R2 is selected from the group consisting of Cl, Br, cyano, C(O)OH; (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl; (C2-C6)-haloalkenyl; (C2-C6)-alkynyl; ((C1-C2)-alkyl)aminocarbonyl, N-((C1-C2)-alkylsulfonyl)aminocarbonyl; (C1-C3)-alkylsulfonyl and (C1-C3)-alkylsulfinyl; R3 is hydrogen; R4 and R5 are each independently selected from the group consisting of hydrogen, (C1-C6)-alkyl and (C1-C6)-alkoxy; R6 and R7 are hydrogen; R8 is selected from the group consisting of hydrogen, halogen and (C1-C3)-alkyl; R9 is selected from the group consisting of hydrogen, chlorine and fluorine; R10 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine and (C1-C3)-alkyl; R11 is selected from the group consisting of hydrogen and (C1-C4)-alkyl; X is selected from the group consisting of O and S; and n is 0 or 1. 6. Compounds of general formula (I) According to any one of claims 1 to 5, CHARACTERIZED by the fact that the chiral carbon atom marked by (*) has a configuration (R). 7. Compounds of general formula (I) According to any one of claims 1 to 5, CHARACTERIZED by the fact that the chiral carbon atom marked by (*) has a configuration (R) and the chiral carbon atom marked by (**) has a configuration (S) . 8. Process for preparing compounds of general formula (I) or their agrochemically acceptable salts: wherein the radicals R1 to R11 and X and n are as defined in any one of claims 1 to 7, and the process is CHARACTERIZED by the fact that - a compound of general formula (II) wherein R1, R2 are as defined in any one of claims 1 to 7 and Z1 represents an exchangeable radical or a leaving group selected from the group consisting of fluorine, chlorine, bromine, iodine, (C1-C4)-alkylsulfanyl, ( C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, phenyl-(C1-C4)-unsubstituted alkylsulfonyl or phenyl-(C1-C4)-alkylsulfonyl which is mono- or polysubstituted by fluorine, chlorine, bromine or (C1 - C4)-alkyl or (C1-C4)-alkoxy and represents (C1-C4)-alkylphenylsulfonyl; - is reacted with an amine of general formula (III) or an acid addition salt of the amine of general formula (III) wherein the radicals R3 to R11 and X and n are as defined in any one of claims 1 to 7. 9. Process for preparing compounds of general formula (I): wherein the radicals R1 to R11 and X and en are as defined in any one of claims 1 to 7, and the process is CHARACTERIZED by the fact that - a compound of general formula (II-a) wherein Z2 is selected from the group consisting of halogen, cyano, (C1-C6)-alkoxycarbonyl, (C1-C6)-alkylcarbonyl and (C1-C6)-alkylthio is prepared by the process as defined in claim 8 and subsequently - the radical Z2 is converted by known processes into a radical R2, wherein R2 is as defined in any one of claims 1 to 7. 10. Process for preparing compounds of general formula (I) or their agrochemically acceptable salts: wherein R1 represents amino and the radicals R2 to R11 and acid addition salt - is condensed with acylcyanides of formula (V) wherein the radical R2 is as defined in any one of claims 1 to 7. 11. Herbicidal composition or plant growth regulating composition CHARACTERIZED by the fact that it comprises one or more compounds of general formula (I) or its salts as defined in any one of claims 1 to 7. 12. Method of controlling harmful plants or regulating plant growth CHARACTERIZED by the fact that an effective amount of one or more compounds of general formula (I) or their salts as defined in any one of claims 1 to 7 is(are) applied to plants, parts of the plant, seeds of the plant or an area under cultivation. 13. Use of the compounds of general formula (I) or their salts, as defined in any one of claims 1 to 7, CHARACTERIZED by the fact that it is as herbicides or as plant growth regulators. 14. Use, according to claim 13, CHARACTERIZED by the fact that the compounds of general formula (I) or their salts are used to control harmful plants or regulate the growth of plants in plantations of useful or ornamental plants. 15. Use, according to claim 13 or 14, CHARACTERIZED by the fact that the crop plants are transgenic crop plants.