UA73488C2 - 1,3,5-triazine derivatives, herbicide composition based thereon and intermediary compounds - Google Patents

Abstract

The invention relates to novel substituted 1,3,5-tnazines of general formula (I), in which A represents CHR3R4 or represents C1-halogenoalkyl-substituted C3-C6-cycloalkyl, C3-C6-alkinyl or C1-C4-cyanoalkyl, where R1, R2, R3 and R4 are each as represented in the description, and to processes for their preparation, to novel intermediates, including their preparation, and to the use of the compounds of general formula (I) as herbicides. , (I)

Description

Description of the invention

The present invention relates to new substituted 1,3,5-triazines, methods and new intermediate compounds for their preparation and to their use as herbicides.

Some substituted 1,3,5-triazines, which have herbicidal activity, have already been described, see Japanese patent application UR-A 19400/1961, US patent 05-A 3816419, US patent IO5-A 3932167, Japanese patent application UR-A 192873/1983, international application MO-A 90/093781. Also compounds (K)-6-chloro-M-(1-cyclohexylethyl)-M'-ethyl-1,3,5-triazine-2,4-diamine, 70 (5)-6-khpor-M-(1 -cyclohexylethyl)-M'-ethyl-1,3,5-triazine-2 4-diamine and (K,5)-6-chloro-M-(1-cyclohexylethyl)-M'-ethyl-1,3,5 -triazine-2,4-diamine are already described in the literature as herbicidally active compounds | see 2. Maishpogesy, S; Viovzs. (1987), 42, 663-669 - in Spet. ABbvigasiv 107:91770|. However, until now these compounds were not of particular importance.

This invention, therefore, represents new substituted cyclohexylalkylamino-1,3,5-triazines of the general formula (I) in: kn F

And residential complex

A-Y M E in which

A represents SNE ZB" or represents C 1-haloalkyl-substituted cycloalkyl with 3-6 carbon atoms, alkynyl with 3-6 carbon atoms or (C.-C.)-cyanoalkyl, c where o

BZ and 27 simultaneously or independently of each other represent optionally cyano-, halogen- or apoxy with 1-4 carbon atoms - substituted alkyl with 1-6 carbon atoms, represent haloalkyl with 1-4 carbon atoms or represent cycloalkyl with 3- 7 carbon atoms, which is optionally substituted by nitro, cyano, hydroxyl, halogen, in turn, in each case, optionally cyano-, halogen- or alkoxy with 1-4 carbon atoms - substituted by alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl having, in each case, from 1 to 6 carbon atoms, or in turn optionally cyano-, halogen- or alkyl with 1-4 carbon atoms -substituted cycloalkyl having from 3 to 6 carbon atoms, and where the total number of carbon atoms of BZ and B" is more than 3. so

Ge represents amino, formylamino, represents dialkylaminoalkylideneamino, which has up to 6 M carbon atoms, or represents in each case optionally cyano-, halogen-, or alkoxy with 1-4 carbon atoms -substituted alkylcarbonylamino, alkoxycarbonylamino, or alkylaminocarbonylamino, which have in in each case, from 1 to b carbon atoms in the alkyl group, and 2 represents in each case an optional hydroxyl-, cyano-, or halogen alkoxy with 1-4 carbon atoms - substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulfinyl or -c alkylsulfonyl, which in each case have from 1 to 6 carbon atoms, or represents optionally cyano-, halogen- or alkyl with 1-4 carbon atoms - substituted cycloalkyl, which has from 3 to b carbon atoms. Preferred substituents or choices of radicals present in the formulas listed above are described below.

And preferably represents SNE ZE", preferably represents C .-haloalkyl -substituted cycloalkyl with 5-6 carbon atoms, preferably represents 1,1-dimethyl-2-propynyl or preferably represents -I 1-cyano-1-methylethyl, where o vZiv7 preferably simultaneously or independently represent optionally cyano-, fluoro-, chlorine-, methoxy-,

ЧК» ethoxy-, n- or iso-propoxy-substituted alkyl with 1-5 carbon atoms, represent haloalkyl with 1-3 carbon atoms, or represent cycloalkyl with 3-6 carbon atoms, which is optionally substituted by nitro, cyano, hydroxyl, fluorine, chlorine, bromine, in turn in each case optionally cyano-, fluorine-, chlorine-,

IR f) bromo-, methoxy-, ethoxy-, n- or iso-propoxy -substituted with methyl, ethyl, n- or iso-propyl, n-, i-, sec- or tert-butyl, methoxy, ethoxy, n- or iso-propoxy, n-, iso-- sec or tert-butoxy, methylthio, ethylthio, n- or iso-propylthio, n-, iso-, sec or tert-butylthio, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, or alternatively in each case optionally cyano-, fluoro-, chloro-, bromo-, methyl-, ethyl-, n- or iso-propyl, n-, iso -, sec- or tert-butyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and where the total number of carbon atoms ЕЗ and БЕ" is greater than 3,

He preferably represents amino, formylamino, dimethylaminomethyleneamino or diethylaminomethyleneamino, 60 or represents in each case optionally cyano-, fluoro-, chloro-, methoxy, ethoxy, n- or iso-propoxy-substituted acetylamino, propionylamino, n- or iso- butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or iso-propoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or iso-propylaminocarbonylamino,

IN? preferably represents in each case optionally hydroxyl-, cyano-, fluoro-, chloro-, bromo-, or methoxy-, ethoxy, n- or iso-propoxy-substituted methyl, ethyl, n- or iso-propyl, n- , iso-. sec- or tert-butyl,

methoxy, ethoxy, n- or iso-propoxy, n-, iso-l sec or tert-butoxy, acetyl, propionyl, n- or iso-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, methylthio, oethylthio, n - or iso-propylthio, n-, iso-l-second or tert-butylthio, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, or represents in each case optionally cyano- , fluoro-, chloro-, methyl or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

And especially preferably represents SNE ZV", represents trifluoromethyl-substituted cyclohexyl, represents 1,1-dimethyl-2-propynyl or represents 1-cyano-1-methylethyl, where

VZ Her K7 especially preferably simultaneously or independently represent in each case optionally cyano-, fluoro-, chloro-, methoxy-, ethoxy-, n- or iso-propoxy-substituted methyl, ethyl, n- or iso-propyl, n -, iso-, sec- or tert-butyl, represent 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3-chloropropyl or represent cyclopentyl or cyclohexyl, where the cycloalkyl radicals are optionally substituted by hydroxyl, fluorine, chlorine, in turn, in each case optionally fluoro-, chloro-, methoxy-, ethoxy-, n- 75 or iso-propoxy-substituted methyl, ethyl, n- or iso-propyl, methoxy, ethoxy, n- or iso- propoxy, methylthio, ethylthio, n- or iso-propylthio, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, or in turn optionally fluoro-, chloro-, methyl- , ethyl-, n- or iso-propyl-substituted cyclohexyl, and where is the total number of carbon atoms of BZ and B? greater than 3,

B" especially preferably represents amino, formylamino, dimethylaminomethyleneamino, acetylamino or propionylamino.

IN? especially preferably represents in each case optionally fluoro-, chloro-, methoxy-, ethoxy-substituted methyl, ethyl, n- or iso-propyl.

And most preferably represents SNE ZBE", represents trifluoromethyl-substituted cyclohexyl, ch 29 represents 1,1-dimethyl-2-propynyl or represents 1-cyano-1-methylethyl, Ge) where

BZ and 7 most preferably simultaneously or independently of each other represent methyl, ethyl, n- or iso-propyl, represent 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3-chloropropyl, or represent cyclopentyl or cyclohexyl , and where the total number of carbon atoms of KZ and B" is greater than 3,

B" most preferably represents amino, formylamino, ethylcarbonylamino or methylcarbonylamino.

IN? most preferably represents in each case 1-fluoroethyl, difluorochloromethyl, dichloromethyl or "I 1-fluoro-1-methylethyl.

The general or preferred definitions of radicals presented above apply both to the final products of the formula (I) and, accordingly, to the starting materials or intermediate compounds necessary in each case to obtain them. These definitions of radicals can be combined with each other if desired, that is, include compounds in the specified preferred framework.

According to this invention, preference is given to those compounds of formula (I) which contain a combination of the values listed above as preferred.

According to the present invention, particular preference is given to those compounds of formula (I) which contain a combination of the values listed above as particularly preferred. and According to this invention, the greatest preference is given to those compounds of formula (I) which contain "" a combination of the values listed above as the most preferred.

Halogen includes fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Saturated or unsaturated hydrocarbon radicals, such as alkyl, also in combination with heteroatoms, such as - and alkoxy, are in each case straight or branched as far as possible. Alkyl with 1-6 carbon atoms is, for example, methyl, ethyl, n- or iso-propyl, n-, iso--. sec- or tert-butyl, n-, iso-, tert- or neo-pentyl, n-, iso-, sec-, tert- or neo-hexyl.

Alkynyl radicals can in each case have a straight or branched chain. Alkynyl with 2-6 to 50 carbon atoms is, for example, ethynyl, 1-propynyl, 2-propynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl.

IR e) The following radicals can be cited as examples of optionally substituted cycloalkyl radicals: cyclopropyl, 2-methylcyclopropyl, 2-chlorocyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2-fluorocyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2-fluorocyclohexyl, cycloheptyl and so on.

Haloalkyl radicals that may be mentioned as examples include: fluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromomethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 3-fluoropropyl, 3-chloropropyl and so on . o Cyano-substituted alkyl radicals that may be mentioned as examples include: cyanomethyl, i.e.) 1-cyanoethyl, 2-cyanoethyl, 3-cyanopropyl, 1-cyanopropyl, 1-cyano-1-methylethyl, 4-cyanobutyl and so on .

Alkyl carbonyl radicals that may be mentioned as examples include: methyl carbonyl, ethyl carbonyl, 60 n-propyl carbonyl, iso-propyl carbonyl, n-butyl carbonyl, and so on.

Optionally substituted radicals can be mono- or polysubstituted, and, in the case of polysubstitution, the substituents can be the same or different.

The compounds of the general formula (I) according to this invention contain at least one asymmetrically substituted carbon atom, and therefore they can be present in different enantiomeric (K- and Z-configurations) or 65 diastereomeric forms. The present invention relates both to various possible individual enantiomeric or stereoisomeric forms of the general formula (I) and to mixtures of the indicated isomeric compounds.

New substituted 1,3,5-triazines of general formula (I) have interesting biological properties. In particular, they have a strong herbicidal effect.

Examples of compounds of general formula (I) are listed in Table 1 below.

Table t"

Table 1

A che 70 vom F var

A-M M V n

A: "SNAV"

Mom KOMI KO ON KO snchnsno oral sch (snah (sne so with

MnSno (SNSE (snuyensnenesv o

MNSOSnh (Sn (SnzsnenbsneSN" - them and sno g" (bno -I (95) sh" at 50

IR e)

F) name) 60 b5

She

So n

A SN yu SHE 00001 (sne (sno knsno (nos sno chnsno (sno sia 7 (sno o (sne)

Footnote t chnsto (introduced so "sn so (snie ch sne ih nnsno Sas " (sno and knsno (bno nos « o, s z -I o i o 50 i42) 52 iF) ime) 60 b5

IN

AH km F y k-k v n d:-SNAV" yu AKA i

And with 7 o her so

Table 1!" (continued)

Table 1 (continued) «

E so m AH, and -

F kov,

KE "

VN UM PN No Z i

И» » з о з со и з» о ю c) b5

New substituted 1,3,5-triazines of general formula (I) are obtained when:

(a) biguanides of general formula (II)

NN... NN.

OK mo w in M cm

ЕИ 1 1 n n in which virgin! such as defined above - Mabo acid adducts of compounds of the general formula (II) - interact with alkoxycarbonyl compounds of the general formula (II) t2-co-ovB5 (PI) in which

B2 is as defined above, and B0 is alkyl, if appropriate, in the presence of an excipient and, if appropriate, in the presence of a diluent. and, if appropriate, the obtained compounds of the general formula (I) are subjected to further transformation, within the limits of the definition of substituents, by conventional methods, or (B) 1,3,5-triazines of the formula (Ia), in which VE is amino,

VE:

Her village

MM (in) (8)

LA

А--МхМ М МН, n where A and B2 are as defined above, d) interact with carbonyl halides of the general formula (IM) со вбх2 (М) « g : ' : (ze) where K" represents formyl or represents neoob" necessarily cyano-, halo- or alkoxy with 1-4 carbon atoms - substituted alkylcarbonyl, which has, in each case, from 1 to 6 carbon atoms in the alkyl group, and X2 /i- represents chlorine or bromine, in the presence of a diluent and, if acceptable, in the presence of a base, or (c) "compounds of the general formula (Ia), in which B is amino, react with carboxylic anhydrides of the general formula (M) C c bod (U) ;" where KZ is as defined above, in the presence of a diluent and, if appropriate, in the presence of a base, -i or (a) the compounds of the general formula (Ia) in which K is amino, react with carboxylic acid esters of the general formula (MI) Щ» bo (MI o bo (MI) 42) where B? and 25 are as defined above in the presence of a diluent and, if appropriate, in the presence of a base, or (e) a compound of the general formula (Ia) in which B is amino ,

F! interact with carboxylic acids of the general formula (MII) o vbon (MI) 60 where KE is as defined above in the presence of a diluent and, if appropriate, in the presence of a condensing agent.

When using, for example, 1-(1-cyclohexylethyl)-biguanide and methyl trifluoroacetate as starting materials, the reaction proceeds according to method (a) according to this invention, which can be illustrated by the following scheme: b5

MN, o Osn, Well you are, I

Тчн ХК -- - м'отмо Я 5000

When using the hydrogen chloride adduct of 1-(1-ethylpropyl)-biguanide and methyl 1-fluoro-1-methylacetate as starting materials, the reaction proceeds according to method (a) according to this invention, which can be illustrated by the following scheme: no

And min, n. n t o OSN, ns MM base I . XX pd in M

M Mo MNOens 3

Co t sun, P 1 2 r snn nn E M MN»

CH,

When using, for example, M-(1-ethylpropt)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and acetyl chloride as starting materials, the reaction proceeds according to the method ( b) according to this invention, which can be illustrated by the following scheme: c ne ns o

Y min, sn; nm about NM

D Aa t, "M c) so

IOM t ns no

I5 o) 3 I 3 | schi kn (ee)

IOM, E os

E dream "

SN, Z co

When using, for example, M-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and acetic 3o anhydride as starting materials, the reaction proceeds as by method (c) according to this invention, which in can be illustrated by the following diagram:

And Ke n.s with « hv, SYA, : nm o o NM t s X thing AH ; MM nyu o sen ne MM o zhiva va MA y

Mn MN: And MO education,

E dream

CH, 3 -I 2) When using, for example, M-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and ethyl acetate as starting materials materials, the reaction takes place according to method (4) according to this invention, which can be illustrated by the following diagram: со не т т, , сн сн з | basis I

Н Zm ny ne tov, --- n.s MM 8) ovo Ж че в ko E 2 E Нн m сн, СН, 60 When using, for example, M-(1-ethylpropt)-6-(1-fluoro- 1-methylethyl)-1,3,5-triazine-2,4-diamine and acetic acid as starting materials, the reaction proceeds according to method (e) according to this invention, which can be illustrated by the following scheme: b5 n.s ns 2 CH in: nm Go) condensing

And the agent "Ah, oh no, I'm not dead -- 8 --" mustache! J. H ana hv Mo sen

E 2 E sn NN Z sy, z

Formula (II) gives a general idea about the biguanides used as starting materials in the method according to this invention for obtaining compounds of the general formula (I). In the general formula (I), A preferably or most preferably has those values that were already indicated above in relation to the description of the compounds of the general formula (I) according to this invention as the preferred or most preferred values of A. t Suitable acid adducts of the compounds of the formula (II ) are addition products with protonic acids, such as, for example, with hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

Starting materials of the general formula (II) have not yet been described in the literature; being novel compounds, they also form part of the subject matter of this invention.

Among the intermediate compounds of the general formula (II), special attention should be paid to the subgroup in which A represents SNAZV", where BZ represents optionally cyano-, halogen- or alkoxy with 1-4 carbon atoms, substituted alkyl with 1-6 carbon atoms and B? represents cyclohexyl, which is optionally substituted by nitro, cyano, hydroxyl, Ha halogen, in turn, in each case, optionally cyano-, halogen-, or alkoxy with 1-4 atoms substituted by alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, which in each case have from i9) 1 to b carbon atoms, or, in turn, optionally cyano-, halogen or alkyl with 1-4 carbon atoms substituted cycloalkyl, which has from 3 to 6 carbon atoms, and where WZ is preferably in each case optionally cyano-, fluoro-, chloro-, methoxy-, ethoxy, n- (ee) or iso-propoxy-substituted methyl, ethyl, n- or iso-propyl, n-, repeat, iso- or tert-butyl, represents co 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 33-fluoropropyl or 3-chloropropyl and KE " preferably represents cyclohexyl, which is optionally substituted by hydroxyl, fluorine, chlorine, in turn, in each case, optionally by " fluoro-, chloro-, methoxy-, ethoxy-, n-, or iso-propoxy-substituted methyl, ethyl, n- or iso-propyl, methoxy, c ethoxy, n- or iso-propoxy, methylthio, ethylthio, n- or iso-propylthio, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, methylsulfonyl, ethylsulfinyl, n- or iso-propylsulfonyl, or in turn, y- in each case, optionally fluoro-, chloro-, methyl-, ethyl-, n- or iso-propyl-substituted cyclohexyl. 25 in all formulas of compounds according to this invention preferably represents formyl or alkylcarbonyl with 1-3 carbon atoms, and especially preferably, represents formyl, methylcarbonyl or ethylcarbonyl. "

New biguanides of the general formula (II) are obtained when substituted amines of the general formula (MI!) - А-МНо (MI) . is" in which

And such as defined above - Mabo acid adducts of compounds of the general formula (MI), such as, for example, hydrochlorides - interact with - and cyanoguanidine ("dicyanodiamide") of the formula (IX) in c; e nu M ah) bo o nn so if appropriate in the presence of an auxiliary compound, such as, for example, hydrogen chloride, and, if appropriate, in the presence of a diluent, such as, for example, n-decane or 1,2-dichlorobenzene, at temperatures from 100920 to 2002 (see examples of obtaining)

After obtaining the biguanides of the general formula (II), they can be used directly, without intermediate isolation, to obtain compounds of the general formula (I) by the methods according to the present invention. i) Examples of hydrochlorides of compounds of general formula (II) according to this invention include: 1-methylbutylbiguanide hydrochloride, 1,2-dimethylpropylbiguanide hydrochloride, 1,3-dimethylbutylbiguanide hydrochloride, 1-ethylpropylbiguanide hydrochloride, 1-ethylbutylbiguanide hydrochloride, 1-ethyl- 2-methylpropylbiguanide 60 hydrochloride, 1-ethylpentylbiguanide hydrochloride, 1-ethyl-2-methylbutylbiguanide hydrochloride, 1-ethyl-3-methylbutylbiguanide hydrochloride, 1-ethyl-2,2-dimethylpropylbiguanide hydrochloride, 1-cyclopropylpropylbiguanide hydrochloride, 1-cyclopentylpropylbiguanide hydrochloride, 1-cyclohexylpropyl-biguanide hydrochloride, 1-propylbutylbiguanide hydrochloride, 1-isopropyl-butylbiguanide hydrochloride, 1-propylpentylbiguanide hydrochloride, 1-isopropyl-2-methylpropylbiguanide hydrochloride, 65 1-isopropylpentylbiguanide hydrochloride, 1-butylpentylbiguanide hydrochloride, 1-isobutylpentylbiguanide hydrochloride, 1 ,5-dimethylhexylbiguanide hydrochloride, 1-pentylhexylbiguanide hydrochloride,

1-ethyl-3-fluoropropylbiguanide hydrochloride, 3-chloro-1-ethylpropylbiguanide hydrochloride, 1-ethyl-2-fluoropropylbiguanide hydrochloride, 1-ethyl-4-fluorobutylbiguanide hydrochloride, 4-chloro-1-ethylbutylbiguanide hydrochloride, 2-trifluoromethylcyclohexylbiguanide hydrochloride, 3-trifluoromethylcyclohexylbiguanide hydrochloride, 4-trifluoromethylcyclohexylbiguanide hydrochloride, 1,1-dimethyl-2-propynylbiguanide hydrochloride, 1-cyano-1-methylethylbiguanide hydrochloride and so on.

Substituted amines of the general formula (MI) required as precursors are known and/or can be obtained by methods known from the literature, see You Zos. Sleep ERhapse 1952, 276-279; ogr. reference 1953, 974-981;

howl Spent Zos. Darap 57 (1984), 1570-1575; 9). At. Spent boss. 76 (1954), 4564-4570; vol. reference 80 7/0 (1958), 5270-5272, LIKKEM KASBAKO KOO7A (and esiigez oi ekhregitepia! spetivigu), published by Spetis! Zosiegu oh

Huarap, vol.14, p.1339 (1978), published by Magigep; in). At. Spent boss, 75, 3212 (1953); U. At. Spent 5os., 78, 860 (1956); U. At. Spent Zos, 66, 1517 (1944); Apdem Spent Yippee Ea., 7, 919 (1968); U. Spet. Zos., 2348 (1926); Bupipevziz, 717 (1980); Ogd. Keacy, Z, 267 (1946); 9). Spent Bos., 267 (1941); Ogd. Keacy, Z, 307 (1946); Ogd. Keasi., 3, 337 (1946); U. Ogu. Spent OB, 16,1031 (1980); Ragtasso Ea. Zsi., 22, 1037 (1967); 9.

Vioi Spet., 120, 772 (1937); international application MUO 92/12121; European patent application EP-A176327;

C5-8233428; German patent application OE-A 2843480 and so on.

Examples of hydrochlorides of compounds of the general formula (MIII) according to this invention are: 1-methylbutylamine hydrochloride, 1,2-dimethylpropylamine hydrochloride, 1,3-dimethylbutylamine hydrochloride, 1-ethylpropylamine hydrochloride, 1-ethylbutylamine hydrochloride, 1-ethyl-2-methylpropylamine hydrochloride, 1-ethylpentylamine hydrochloride, 1-ethyl-2-methylbutylamine hydrochloride, 1-ethyl-3-methylbutylamine hydrochloride, 1-ethyl-1,1-dimethylpropylamine hydrochloride, 1-cyclopropylpropylamine hydrochloride, 1-cyclopentylpropylamine hydrochloride, 1-cyclohexylpropylamine hydrochloride , 1-propylbutylamine hydrochloride, 1-isopropylbutylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-isopropylpentylamine hydrochloride, 1-butylpentylamine hydrochloride, 1-isobutylpentylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-pentylhexylamine hydrochloride, 1-ethyl-3-fluoropropylamine hydrochloride, 3-chloro-1-ethylpropylamine hydrochloride e, i) 1-ethyl-2-fluoropropylamine hydrochloride, 1-ethyl-4-fluorobutylamine hydrochloride, 4-chloro-1-ethylbutylamine hydrochloride, 2-trifluoromethylcyclohexylamine hydrochloride, 3-trifluoromethylcyclohexylamine hydrochloride, 4-trifluoromethylcyclohexylamine hydrochloride, 1,1- dimethyl-2-propynylamine hydrochloride, 1-cyano-y. methylethylamine o zo Hydrochloride, and so on.

The compounds of formula (IX) are synthetic compounds known in organic chemistry. co

Formula (II) gives a general definition of alkoxycarbonyl compounds used further as starting compounds in the method according to this invention for obtaining compounds of the general formula (I). In the general formula (II), K? preferably or especially preferably has the meaning already indicated above in the description of compounds of the general formula (I) according to this invention as the best or especially best for y-2, y5 is preferably an alkyl having from 1 to 4 carbon atoms, in particular, methyl or ethyl.

The starting materials of the general formula (II) are known chemical compounds for synthesis | see, for example, German patent application OE-A 4131242, European patent applications EP-A 850911, EP-A 468681, Japanese patent application R-A 301844/1993, 3. Ogd. Spet., 33, 4279 (1968) and so on). Examples of similar compounds are: methyl 1-fluoropropionate, ethyl 1-fluoropropionate, propyl 1-fluoropropionate, butyl 1-fluoropropionate, methyl ts 1-fluoro-1-methylpropionate, ethyl 1-fluoro-1-methylpropionate, propyl 1-fluoro- 1-methylpropionate, butyl h 1-fluoro-1-methylpropionate and so on. » The compounds of general formula (Ia), which are used as starting compounds in methods (b), (c), (a) and (e), are new and can be obtained, for example, as a subgroup of compounds of formula (I) by the method (and).

Examples of these compounds are: M-(1-methylbutyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, - M-(1,2-dimethylpropyl)- 6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine, o IM-(1,3-dimethylbutyl)-6-(1-fluoro-1-methylethyl)-1,3,5 -triazine-2,4-diamine,

IM-(1,5-dimethylhexyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, i- M-(1-ethylpropyl)-6-(1 -fluoroethyl)-1,3,5-triazine-2,4-diamine, about 20 M-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2, 4-diamine,

M-(1-ethylbutyl)-6-(1-fluoroethyl)-1,3,5-triazine-2 4-diamine, co M-(1-ethylbutyl)-6-(1-fluoro-1-methylethyl)- 1,3,5-triazine-2,4-diamine,

M-(1-ethyl-2-methylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine,

M-(1-ethylpentyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and so on. 22 Compounds of formulas (IM), (M), (MI) and (MII) are well-known synthetic compounds of organic chemistry. In the specified

HF) in KZ compounds is preferably formyl, is in each case optionally cyano-, fluoro-, chloro-, methoxy-, ethoxy, n- or iso-propoxy-substituted acetyl, propionyl, n- or iso-butyroyl, methoxycarbonyl, where ethoxycarbonyl, n- or |iso-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or iso-propylaminocarbonyl, and especially preferably is formyl, methylcarbonyl, ethylcarbonyl, acetyl or 60 propionyl. KZ is most preferably formyl, ethyl carbonyl, methyl carbonyl.

Examples of compounds of the general formula (IM) are: acetyl chloride, acetyl bromide, propionyl chloride.

Examples of compounds of general formula (M) are: acetic anhydride and propionic anhydride.

Examples of compounds of general formula (MI) are: methyl formate, ethyl formate, n-propyl formate, n-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate and bo n-butyl propionate.

Examples of compounds of general formula (MI) are: formic acid, acetic acid, and propionic acid.

The method of obtaining compounds of the general formula (I) by method (a) according to this invention is preferably carried out using a diluent. Suitable diluents for carrying out the method according to this invention include, in addition to water, preferably organic solvents. They include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated, hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxymethane (DMM), tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol 70 diethyl ether; ketones such as acetone, methyl ethyl ketone (MEK), butanone, methyl isopropyl ketone or methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile or butyronitrile; amides such as

M,M-dimethylformamide, M,M-dimethylacetamide, M-methylformanilide, M-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide; alcohols such as methanol, ethanol, n- or iso-propanol, butanol, ethylene glycol, monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or distilled water.

Suitable auxiliary compounds for the reactions according to the method according to this invention are, in general, conventional inorganic or organic bases or acid acceptors. They preferably include acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides of alkali or alkaline earth metals, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate , potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, methoxide, ethoxide, n- or iso-propoxide , n-, iso-, second or third sodium butoxide, or methoxide, ethoxide, n- or iso-propoxide, n-, iso-l. secondary or tertiary potassium butoxide; In addition, also basic organic nitrogen compounds such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, M,M-dimethylcyclohexylamine, dicyclohexylamine, (8) ethyl-dicyclohexylamine, M,M-dimethylaniline, M ,M-diethylaniline, M,M-dimethylbenzylamine, pyridine, 2-methyl-,

3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 33,4-dimethyl- and 33,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 1,1,4 ,4-tetramethylmethylenediamine (TMEDA), 4-dimethylaminopyridine, M-methylpiperidine, so 1,4-diazabicyclo|2.2.2)octane (DABKO), 1,5-diazabicyclo|4.3.0|non-5-ene (DBN) or 1,8-diazabicyclo|5.4.O)undec-7-ene (DBU), as well as organolithium compounds, such as, for example, methyl plythium, so n-butyllithium, t-butyllithium, tert-butyllithium, phenyllithium, lithium isopropylamide, n -butyllithium " DABKO, "E n-butyllithium " DBN, n-butyllithium " TMEDA and so on.

When carrying out the process according to this invention, the reaction temperature can vary in a relatively wide range. In general, the process is carried out at a temperature from 02С to 1502С, preferably from 102С to 12096.

The process according to this invention is usually carried out at atmospheric pressure. However, it is also possible to carry out the process according to this invention at elevated or reduced pressure - usually from 0.1 bar to 10 bar.

To carry out the process according to the present invention, the starting compounds are usually used in 0 equimolar quantities, 1 mol of the compound of the general formula (I) can interact with, for example, 1-2 mol of the compound of the general formula (I) in the presence of a base, for example, 1 -2 moles of sodium ethoxide, in diluent and ethanol. However, it is also possible to use a relatively large excess of one of the components. The reaction "" is usually carried out in a suitable diluent in the presence of an auxiliary compound, and the reaction mixture is usually stirred at the required temperature for several hours. Processing is carried out by conventional methods (see production examples). -i The process according to this invention according to methods (a), (b), (c), (4) and (e) of obtaining compounds of the general formula (I) is preferably carried out using a diluent. Suitable diluents for carrying out the process according to this invention include, in addition to water, preferably inert organic solvents. These solvents include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated,

Hydrocarbons, such as, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, tetrachloromethane; ethers such as diethyl ether, methyl ethyl ether, diisopropyl co ether, dibutyl ether, dioxane, dimethoxymethane (DMM), tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones such as acetone, methyl ethyl ketone (MEK), butanone, methyl isopropyl ketone or methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile or butyronitrile; amides such as

M.M-dimethylformamide, M,M-dimethylacetamide, M-methylformanilide, M-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide; alcohols, (F, such as methanol, ethanol, n- or iso-propanol, butanol, ethylene glycol, ethylene glycol monomethyl ether, co ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or distilled water. in Suitable auxiliary compounds for the methods of this invention according to methods (a), (b), (c) or (4) are generally common inorganic or organic bases or acid acceptors. They preferably include acetates, amides, carbonates, bicarbonates, hydrides , hydroxides or alkoxides of alkali or alkaline earth metals, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, 65 potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, methoxide, ethoxide, n- or iso-propoxide, n-, iso-. sodium sec- or tert-butoxide, or potassium methoxide, ethoxide, n- or iso-propoxide, n-, iso-l sec or tert-butoxide; in addition, also basic organic nitrogen compounds such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, M,M-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, M,M-dimethylaniline, M,M-diethylaniline, M,M, M-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,b-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl- pyridine, 5-ethyl-2-methylpyridine, 1,1,4,4-tetramethylmethylenediamine (TMEDA), 4-dimethylaminopyridine, M-methylpiperidine, 1,4-diazabicyclo|2.2.2)octane (DABKO), 1,5- diazabicyclo|4.3.0|non-5-ene (DBN) or 1,8-diazabicyclo(|5.4.O)undec-7-ene (DBU). 70 The process according to the present invention according to method (e) is preferably carried out in the presence of a condensing agent. Examples of such condensing agents include: dicyclohexylcarbodiimide, acetic anhydride, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, aluminum oxide, silicon tetrachloride, titanium tetrachloride, and so on.

When carrying out the process according to this invention according to methods (B), (c), (4) or (e), the temperature /5 of the reaction can vary within relatively wide limits. In general, the process is carried out at a temperature from 0 C to 1502 C, preferably from 02 C to 12090 C.

The process according to this invention is usually carried out at atmospheric pressure. However, it is also possible to carry out the process according to this invention at elevated or reduced pressure - usually from 0.1 bar to 10 bar.

To carry out the process according to the present invention according to method (B), the starting compounds are usually used in equimolar quantities, 1 mol of the compound of the general formula (Ia) can interact with, for example, 0.8-2.0 mol of the compound of the general formula (IM) in the presence base, for example, 1-3 moles of triethylamine. However, it is also possible to use a relatively large excess of one of the components.

To carry out the process in accordance with this invention according to method (c), the starting compounds are usually Ha p;' used in equimolar quantities, 1 mol of a compound of the general formula (Ia) can interact with, for example, 0.8-2.0 mol of a compound of the general formula (M) in the presence of a base, for example, 1-3 mol of i) triethylamine. However, it is also possible to use a relatively large excess of one of the components.

To carry out the process according to the present invention according to method (4), the starting compounds are usually used in equimolar quantities, 1 mol of the compound of the general formula (Ia) can interact with, for example, 0.8-2.0 mol of the compound of the general formula (MI) in the presence of a base, for example, 1-3 moles of sodium methoxide. However, it is also possible to use a relatively large excess of one of the components. co

To carry out the process according to the present invention according to method (e), the starting compounds are usually used in equimolar quantities, 1 mol of the compound of the general formula (Ia) can interact with, for example, 0.8-2.0 mol of the compound of the general formula (IM) in the presence of an agent that condenses, for example, dicyclohexylcarbodiimide. However, it is also possible to use a relatively large excess of one of the components.

The active compounds according to this invention are particularly suitable for use as defoliants, desiccants, top killers and, especially, herbicides. Weeds, in the broadest sense, "mean all plants that grow in an area in which they are undesirable. Whether the compounds of this invention act as general or selective herbicides depends mainly on the amount used. Active - c compounds according to this invention can be used, for example, for the following plants: Dicotyledonous weeds of the genus: Bipari5, IIeridiit, Sait, ZieYMagia, Maiygisaga, Apipetiv, Saiipzoda, "» Speporodisht, Opisa, Bepesio, Atagapiyiv, Rogishasa, Hapipiisht , Sopmoimshiiv5, Irotoea, Roiudopyt, Zezbapia,

Atrgosia, Sigvits, Sagatsivus, Zopspiv, Zoiapitus, Cogirra, Koiiaia, Iipdegpia, Atisht, Megopis, Archiope, Etech,

Vaishga, Mioia, SaIeorziz, Rarameg, Sepiatsgea, Toiisht, Kapipsciov, Tagahasit. -I Dicot agricultural crops of the genus: Sovzvzurisht, Siusipe, Weba, Yuatsysiv, RIazeoiv5, Rivit, zZoYapit, I ipit, Irotoea, Misia, Miso(apa, I usoregzisop, Agaspiv, Vgazvisa, I asiisa, Sisytiv and Sisygria. o Monocot burs' Genus: Espippospioa, Zegagia, Rapisit, Oidiagia, Riiiieot, Roa, Reviisa, Epieizipe, Vgaspiagia, o. Izspaetit, Zrpeposiea, Oasiuosiepisht, Adgoviiz, APIoresygiv, so Arega, Aediior, RNaiagiv. (Che Monocot agricultural crops of the genus: Ogula, 7ea, Tiyistt, Nogdetst, Amepa, besaie, Zogoyit,

Rapisit, Zasspagyt, Apapaz, Azragadiz, AiIit.

However, the use of the active compounds according to the present invention is in no way limited to the specified genera, but also extends in the same way to other plants.

When used in the forms presented here, the active compounds according to this invention can also be used in transgenic plants. In this case, a synergistic effect is obtained. The active compounds according to the present invention are suitable, depending on the concentration, for the complete control of weed growth, for example on industrial sites or railway tracks, and on paths or areas with or without planting trees. Equally, the active compounds according to the present invention can be used to control the growth of weeds in perennial crops, for example, forest plantations, ornamental tree plantings, orchards, vineyards, citrus plantations, nut groves, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, coconut palm plantations, succulent fruit plantations and hop plantations, on lawns, turf and pastures, and for selective 65 Weed control in annual crops.

The compounds of formula (I) according to this invention have a strong herbicidal effect and a wide spectrum of activity when used on the ground and on the aerial parts of plants. Up to a certain limit, they are also suitable for selective control of monocotyledonous and dicotyledonous weeds, in particular, monocotyledonous crops, both before and after germination.

Active compounds can be converted into conventional pharmaceutical forms such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, concentrates of suspensions and emulsions, natural and synthetic materials impregnated with the active compound, and microcapsules. in polymeric substances.

These preparations are obtained by known methods, for example, by mixing active compounds with fillers, i.e., liquid solvents and/or solid carriers, optionally using 7/0 surface-active substances, i.e., emulsifiers and/or dispersants and/or foaming agents.

In the case of using water as a filler, as auxiliary solvents can also be used, for example, organic solvents. Suitable liquid solvents are mainly: aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, /5 for example mineral or vegetable fractions oil, alcohols such as butanol or glycol as well as ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsulfoxide and water.

Suitable solid carriers are, for example, ammonium salts and natural ground minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic ground minerals such as fine silica, alumina and silicates; suitable solid carriers for the granules are, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic stone flour, and granules of organic materials such as sawdust, coconut shells, corn kernels and tobacco stalks; suitable emulsifiers and/or foaming agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and protein hydrolysates; i) suitable dispersants are, for example, lignin-sulfite liquid waste and methyl cellulose.

Thickeners such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or matrices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalins so zo | leticins, and synthetic phospholipids, can be used in preparative forms. Other additives can be mineral and vegetable oils. co

It is possible to use dyes, such as inorganic pigments, for example, iron oxide, titanium oxide, and Berlin azure, and organic dyes, such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and trace elements, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. me)

Preparative forms usually contain from 0.1 to 9595 wt. of the active compound, preferably from 0.5 to 9095. M

To control the growth of weeds, the active compound according to this invention, as such or in the form of a preparative form, can also be used in a mixture with known herbicides, ready-made mixtures or tank mixtures are possible.

Examples of known herbicides suitable for mixtures include: acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium) ametryn, amidochlor, pt)c amidosulfuron, anilophos, asulam, atrazine, azafenidin, azimsulfuron, benazoline( -ethyl), benfuresate, bensulfuron(-mitiv), bentazone, benzobicyclone, benzofenap, benzoylprop(-ethyl), bialafos, bifenox, ;" bispyribac(-sodium), bromobutide, bromophenoxime, bromoxynil, butachlor, butroxidim, butylate, cafenstrol, caloxidim, carbetamide, cafentrazone(-ethyl), chlomethoxifene, chloramben, chloridazon, chlorimuron(-ethyl),

Chlornitrophen, chlorsulfuron, chlorotoluron, cinidone(-ethyl), cinmethylin, cinosulfuron, clefoxidim, -I klethodim, clodinafop(-propargyl), clomazon, clomeprop, clopyralid, clopyrasulfuron(-methyl), chloransulam(-methyl), cumiluron, cyanazine, cybutrin, cycloate, cyclosulfamuron, cyclooxydim, and cigalofop(-butyl), 2,4-0, 2,4-0O8, 2,4-OR, desmedifam, diallate, dicamba, diclofop(-methyl), diclosulam, their diethyl( -ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, 5p dimethamethrin, dimethenamid, dimexiflam, dinitramine, difenamide, diquat, dithiopyr, diuron, dimron, epropodan, co ERTS, esprocarb, etalfluralin, ethametsulfuron(-mitiv), etofumesate, ethoxyphene, ethoxysulfuron, c ethobenzanide, fenoxaprop(-P-ethyl), fentrazamide, flamprop(-isopropyl), flamprop(-isopropyl-y), flamprop(-methyl), flazasulfuron, florasulam, fluazifop(-P-butyl) , fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropine, flumetsulam, fluometuron, dv Ffluorochlo ridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-methyl), flurprimidol, flurtamone, fluthiacet(-methyl), flutiamide,

F) fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(ethoxyethyl), ka haloxyfop(-P-methyl), hexazinone, imazametabenz(-methyl), imazametapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapir, imazasulfuron, iodosulfuron(-methyl, -sodium), ioxynil, isopropalin, isoproturon, bo isouron, isoxaben, isoxachlortol, isoxaflutol, isoxapyrifop, lacgofen, lenacil, linuron, MCRA, MORW, mefenacet, mesotrione, metamitron, metazachlor, metabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxacyclomefon, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, b5 pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), promethrin, propachlor, propanil, propahizafop, propisochlor, propizamide, prosulfocarb, prosulfuron, pyra flufeni(-ethyl), pyrazolate,

pyrazosulfuron(-ethyl), pyrazoxifene, pyribenzoxime, pyributycarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), hinclorac, hinmerac, quinoclamine, hyzalofop(-P-ethyl), hyzalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, symetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), bulphosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxidim, terbuthylazine, terbutrin, tenilchlor, thiafluamide, thiazopyr, thidiazimin, triphensulfuron(-methyl), thiobencarb, thiocarbazyl, tralkoxidim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphan, trifluralin and triflusulfuron.

It is also possible to mix with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners. 70 To improve compatibility with agricultural crops, it is also possible to mix the compounds of general formula (I) with one or more protective agents, an example of an agent that protects is 1-(b,o-dimethylbenzyl)-3-p-tolylurea.

Active compounds can be applied as such, in the form of preparative forms or in the form of forms prepared from them by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are applied in the usual ways, for example, watering, spraying, spraying, scattering.

The active compounds according to the present invention can be applied either before or after emergence. They can also be applied to the soil before planting.

The amount of active compound that is applied can vary widely. It mainly depends on the nature of the desired effect. Of course, the consumption rate is from 1g to 10kg of active compound per hectare of soil surface, preferably from 5g to 5kg per hectare.

The preparation and use of active compounds according to this invention is described with the help of the following examples.

Examples of obtaining Ga

Preparation Monday at 2 "A SN. for so zo MM

Sun with Sun,

At room temperature (approximately 2022), a solution of 4.7 g (d85 mmol) of sodium methoxide in 100 ml of methanol C is added with stirring to a mixture of 20 g (8 mmol) of (K,5)-1-cyclohexyl-ethyl-biguanide hydrochloride, 10 g and (vVO mmol) methyl of 2-fluoropropanoate and 100 ml of methanol, and the reaction mixture was stirred at room temperature for 15 hours. After concentration in a vacuum created by a water pump, the residue is shaken with methylene chloride and water and the organic phase is dried over sodium sulfate and filtered. The solvent is carefully removed from the filtrate under reduced pressure.

9.2 g (4390 from theoretical) of "(K,5)-ME"1-cyclohexyl-ethyl)-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine are obtained in the form amorphous residue. -o s IsdR-1,832)

And Example 2 about sleep;

H

-I niya 0; with "Anoosn,

M M

(ee) ' sn, n

IR e)

A mixture of 3.5 g (1 mmol) of (MK,5)-M'-(1-cyclohexyl-ethyl)-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine (from example 1) and 25 ml of propionic anhydride are stirred at a temperature of 13093 for 60 minutes. Volatile components are then carefully driven off under reduced pressure. (F) Z,vg (9090 from theoretical) is obtained from (K,5)-M-(4-(1-cyclohexyl-ethylamino)-6-(1-fluoroethyl)-1,3,5-triazine-2- il|- propionamide in the form of an amorphous residue. in IsdR-3,149)

Example Z b5 n nm" zo 95 "Am sn,

AND

E teo sn, n

A mixture of 3.5 g (1 mmol) of (MK,5)-M'-(1-cyclohexyl-ethyl)-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine (from example 1) , 2.5 g (21 mmol) of M,M-dimethylformamide of dimethyl acetal and 5 Oml of 1,4 dioxane are stirred at room temperature (approximately 2022) for 15 hours. After adding 8Oml of water and 3ml of concentrated hydrochloric acid, the mixture is stirred at room temperature for another 60 minutes. The crystalline product is then isolated by suction filtration. 12 1.8 g (4790 from theoretical) of (K,5)-M-I4-(1-cyclohexyl-ethylamino)-6-(1-fluoroethyl)-1,3,5-triazin-2-yl|-formamide are obtained with a melting point of 12726.

IodR-Z3,049)

Example 4 n.s 2 sv, nm

HC school

M M

Dissolve 4.94 g of ethylpropylamine hydrochloride in 5 Oml of 1,2-dichlorobenzene. 3.3 g of cyanoguanidine are added and the mixture is then stirred at a temperature from 1509C to 1709C for 3 hours. The crystalline product is then isolated by filtration with suction and washed three times with simple ether (1 Oml). Fractions of the volatile solvent are then carefully distilled off under reduced pressure to obtain ethylpropylbiguanide, which is used for subsequent reactions without further purification. co

Next, 1.10 g of metallic sodium is mixed with 150 g of methanol. After the sodium reacts completely, to the mixture

Add 5.29 g of ethylpropyl biguanide and stir the mixture at room temperature for 48 hours. Volatile methanol is then driven off under reduced pressure. The solid residue was mixed with 8 ml of water and the mixture was extracted with ethyl acetate (120 ml). The organic phase is dried over anhydrous sodium sulfate and the solvent is distilled off under reduced pressure. "

Purification by silica gel column chromatography (mobile phase: ether/n-hexane - 1:1) gives the desired product. From c 3.20 g are obtained (3395 from the theoretical). M-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine "" with a melting point of 104-10620. " Example 5

N zo -i sn, nm iy X i» M M (o)

IS

- :;e n with so sn, 1 year. M-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and 5.63 g of triethylamine are suspended in

ZOml of tetrahydrofuran. At a temperature of 590, add 3.39 g of acetyl chloride and heat the mixture with the reverse

Refrigerate for 2 hours. The reaction mixture is mixed with bOml of saturated sodium bicarbonate solution and extracted with 8Oml of ethyl acetate. The organic phase is dried over anhydrous magnesium sulfate to give

F, the crude product, which, after purification by chromatography on a column with silica gel (mobile phase: ether/n-hexane - 1:1), gives the desired product.

With an almost quantitative yield, 1.17 g of M-acetyl-M'-1-ethylprotyl-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine with a melting point of 109-11126.

Similarly to the methods of examples 1-5 and in accordance with the general description of the production process according to this invention, it is also possible to obtain, for example, the compounds of the general formula (I) presented in Table 1 below. b5

A: "Ah, they are 0

A-M A. it is in

NN

Table 1: Examples of compounds of formula (I)

Physical and

And the stereochemical data

SN, MN; SES Iva Re 3.51" to (racemat) 7 sn, Mne SE(SNz)yu | yud Re 1.93 3 to (racemat)

I, sia; |Sesi isa re 423 no (racemat) sch o sn, st; about | sSv(SNaryu od R 3,302 to o (racemat) (ee)

I: 10th of SNESN | od Re 3.04 G» c) n. then Y o (racemat) "YI (ze) 11 SN, n ST(SN")" | oo Re 3.44" - nm A (racemate)

Nz SNESN:i so Re 1,835

I - c (EK enantiomer) ;» 13 sn, МН СЕ(СНа» Z va Re 1.93 3 to (B enantiomer) -I o 14 sn, Mn; sna ad P- 321 t» to (B enantiomer) oo 50 so (F) ko bo b5

15 SN, sat SNESNI | udeRe 311 to t h (KE enantiomer) 16 sy, sia; СЕ(СН3) а Р: 3.25 в то недо (К enantiomer) 17 се, st сНс бо Р- 293 то ко (В enantiomer) и8 сн, Mn; SNESNU | ode 1.82

And that (5 enantiomer) uh sn, Mne SEN)" od Ra 1.922 o (8 enantiomer) sn, MN" sne Ivo Re 3.20 s 29 to (5 enantiomer) Ho) 51 sn, st 1SNESNU od

AH co

She Ge) (5 enantiomer) and (se) "I sn; sia; |SR(SNI" SubRe call

ON | Pho mo (5 enantiomer) | i- 23 sy, se sne isdR-2,3 2 neo (5 enantiomer) « | s 24 sya, MN SNESNI od R-2,057 . and that (B enantiomer) -I (95)

Sg» o 50 42) (F) ko bo b5

25 s, MH ST(CHnI» | o P: 2137 o (B enantiomer) s, MH» SNESNZ | jud Re 2.057 to (8 enantiomer) 27 sn, Mne CE(СНо» od Ra 2127 to (8 enantiomer) snisnIsНЈsn( СН») Mne (СНа)еСЕ | t. pl. 108-141 S

I (racemate) 29 (СснзСнеСнНЬsН(СН»з) Мне СНУСНЕ | p" 1.51590 (racemate) (СснзЬСснСнСН(СН») Мне (СНУШЕ | t. pl. 123425 (racemate) (Ссна»ононНенНнЬсн) Mne (СНУШСЕ t. pl. 107-1 ts s (СН3) (racemate) at 32 (СнNoСН(СНН») МН; SNISNE (| t. pl. 89-00 (racemate) so

З3 (SeNESN(SeNev) МН (СНзЖСеЕ | t. pl. 104-10676 со (racemate) З 4 (СоНЕСН(СёН») МНСОСсН. (СснНЗЖСЕ t. pl. 109-111 о (racemate)) - 35 Es Mne ( SnzeSE Gb 1.4780

Fi (racemate) "shi c Values of sad P, given in table 1, are determined according to EEC Oigesiime 79/831 Appeh M.A8 using HPLC:z" (high-performance liquid chromatography) on a column with a reverse phase (C 18). Temperature: 4326. (a) Mobile phase for determination in the acid interval: 0.196 aqueous phosphoric acid, acetoniryl; linear gradient from 10965 acetonitrile to 9095 acetonitrile - corresponding data in Table 1 are marked 2), -I (B) Mobile phase for determination in the neutral interval: 0.01 molar aqueous solution of phosphate buffer, acetonitrile; linear gradient from 1095 acetonitrile to 9095 acetonitrile - the relevant data in Table 1 are marked 9), i» Calibration is carried out using unbranched alkan-2-ones (which have from 6 to 16 carbon atoms) 5or With known values of IdR (IdR values are determined using retention time, through linear interpolation between two successive alkanones). co The value of lambda tah is determined using the UV spectrum from 200 nm to 40 Ohm in the maximum of the chromatographic signals.

Starting materials of formula (II):

Example (1-1)

N. nn. yu gor chvi n. km m M M x NSI n Nn Nn 60

A mixture of 28.4 g (004 mol) (K,5)-1-cyclohexyl-ethylamine, 350 ml of toluene, 150 ml of decane and 48 g of 3095 strong aqueous hydrochloric acid is subjected to azeotropic distillation. The liquid is driven off until an internal temperature of 135 9C is reached. At this temperature, 33.bg (0.4 mol) of cyanoguanidine is added to the remaining mixture and the reaction mixture is stirred at a temperature of 13523 for 2 hours. The mixture is cooled to about room temperature, about 100 ml of acetone is added, and the crystalline product is isolated by filtration with suction.

67.9 g (6995 from theoretical) of (K,5)-1-cyclohexyl-ethyl-biguanide hydrochloride are obtained as a solid product.

Analogous to the method of example II-1, it is also possible to obtain, for example, compounds of the general formula (I) presented in Table 2 below.

N. M NN. M 11) (

UNTIL

VE M. M

1 ' from

Nn n I

Table 2: Examples of compounds of formula (I).

In each case, these compounds are hydrochlorides.

Physical and stereochemical

And the data

What i-Z sn, Mne (5 enantiomer) with shchi to 6) i-4 E.N, (K enantiomer) so i bo Ф « pc-5 sn, Mne (5 enantiomer) with zv to h

Examples of use «

Example A-1 statement -

Testing before germination with Solvent: 5 parts by weight. of acetone: with» Emulsifier: 1 part by mass. alkylaryl polyglycol ether

To obtain a suitable preparative form of the active compound, 1 part by mass. of the active compound is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The seeds of the tested plants are sown in ordinary soil. After about 24 hours, the preparative form of the active compound is sprayed onto the soil (95) in such a way that the determined desired amount of the active compound falls 1" per unit area. The concentration of the liquid for spraying is such that the specified desired amount of active compound in 1000 liters of water is applied per hectare. (ee) After three weeks, the degree of damage to the plants is estimated to be 95 damage compared to the growth of untreated donkeys. co r

The numbers mean:

O9o - no effect (as on untreated control plants) 10095 - complete destruction

In this test, for example, the compound of preparative example 1 shows a strong effect against weeds, and in

GF) at the same time is well tolerated by agricultural crops, such as, for example, corn. 7 Example A-2

Testing before germination in Solvent: 5 parts by mass. acetone

Emulsifier: 1 part by mass. benzyloxypolyglycol ether

To obtain a suitable preparative form of the active compound, 1 part by mass. of the active compound is mixed with the specified amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration. in Seeds of the tested plants (Espiposioa sgiz daii, Zeyaga migidis, Atagapiys imidis and Roiudopyt bBishthei

ME!I5ZM) are sown in ordinary soil. The preparative form of the active compound is sprayed on the ground in such a way that the determined desired amount of the active compound falls on a unit of area.

After four weeks, the degree of damage to the plants is estimated to be 90 damage compared to the growth of untreated plants.

The numbers mean:

O9o - no effect (as on untreated control plants) 10095 - complete destruction

In this test, for example, the compounds of preparative examples 32, 33, 34 and 35 demonstrate a strong effect against the above-mentioned weeds. 70 Example B-1

Testing after germination

Solvent: 5 parts by mass. acetone

Emulsifier: 1 part by mass. alkylaryl polyglycol ether

To obtain a suitable preparative form of the active compound, 1 part by mass. of the active compound is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

Tested plants with a height of 5-15 cm are sprayed with the preparative form of the active compound in such a way that the specified desired amount of the active compound falls on a unit of area. The concentration of the liquid for spraying is such that the determined desired amount of the active compound is applied in 1000 liters of water/ha.

After three weeks, the degree of plant damage is estimated to be 95 damage compared to the growth of untreated plants.

The numbers mean:

O9o - no effect (as on untreated control plants) 10095 - complete destruction of

In a successful test, for example, the compounds of preparative examples 1, 2, C, 4, 5, 6, 7, 8 and 9 show a strong effect against weeds, and at the same time are well tolerated by agricultural crops, such as, i) for example, corn.

Example 8-2

Testing after seed germination Solvent: 5 parts by mass. acetone

Emulsifier: 1 part by mass. of benzyloxypolyglycol ether so

To obtain a suitable preparative form of the active compound, 1 part by mass. of the active compound is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration. me)

Tested plants (Espiposioa sgiv daiyi, Zeyagia migidiv, Atagapiyivs Imidiz and Roiudopyt Bishtei MEM), which are, on average, at the 2nd leaf stage, are sprayed with the preparative form of the active compound in such a way that the determined desired amount of the active compound falls on a unit of area.

After three weeks, the degree of plant damage is estimated to be 95 damage compared to the growth of untreated plants. "

The numbers mean: with О9o - no effect (as on untreated control plants) 10095 - complete destruction;" In this test, for example, the compounds of preparative examples 28, 29, 31 and 35 demonstrate a strong effect against the above-mentioned weeds.

Table A-1: Testing before germination/greenhouse -I (95)

Active compound, example Norma Corn | ABryshop Atagapipyv

Cheka" receipt of Mo expenses slogan

IR e)

SN, MN, se x-4 5B M-i M

N a

F) sleep, ko E m VOLO pes SN NNYA B b5

Table B-1-1: Post-emergence testing/greenhouse 2 Active compound example Standard | Corn | Zeiapa | Atagap- receiving Me spending tive slogan about sleep; N m-

M. m

N. M

Art

E sn,

BOM ii Fields of BLAME con is

Table 8-1-2; Post germination/greenhouse testing

Active compound, example Norma | bBegaia | Arishop | Atagap" from the receipt of Me expenses tob (8) slogans

SN, MN;

Ms. So

M-/- m and co

Heh h

E sv, co

SD saliva Bo Bo BANYA BI SAN I (8) sleep, Well k-

M

-- m h

N ke - s SN, y E a columns Bil Bon Bl VN BIJ -I (95) g» o 50 s

F) name) 60 b5

Table B-1-3: Post-emergence/greenhouse testing

Active compound, example Norm Atagap- Hapirisht obtaining Me consumption tive slogan 70 sv, MN; -

M-- m

Nn M-

And a

BOM Beh PENA PANI Po Po

SN, MN. k-( - M u. sn,

E n) 100 100 cm bod i, o

Table B-1-4: Testing after germination/greenhouse p

Active compound, example of Norm Zeiag | Atagap- haptmpit Ge) receipt of Mo expenses tive "I ha.s/ha so

Ge) sn, m chn k- sn) i m o h

E SI shsh s. i "Ya rya i yar p sn ny

Z M n- ZH x - -i m i o. o sn, iz E (ee)

Bl BNO Po BY Ba B

IR e)

F) name) because b5

Table B-1-5; Post germination/greenhouse testing

An active compound, an example of Norma beyaip | Atagap- | Steamed | Hapipit receipt of Mo expenses tn slogans about sleep, from Mon-Sn.

M-th Ohm

NN M sn,

E sn, com o PI pos po pin no, sn, MSH--i k- i

Sh-/ m and shcha

E s s (8)

BAL Bon Bon BI BI NN s zo Examples of preparative forms

An example of preparative Form 1 (granules) with 25 parts by weight. 10 parts by weight of water are added to the mixture. compounds of preparative example 28, 30 parts by weight. "g of bentonite (montmorillonite), 58 parts by mass. talc and 2 parts by mass. lignin-sulfonate salt. The components are thoroughly mixed with each other and used to obtain, in an extrusion granulator, granules (particle size 10-4Omish), which are dried at a temperature of 40-5026. uh-

Example of preparative Form 2 (emulsifiable concentrate)

30 parts by mass. compounds of preparative example 32, 55 parts by weight. xylene, 8 parts by mass. polyoxyethylene alkylphenyl ether and 7 parts by mass. of calcium alkylbenzenesulfonate are mixed and, with stirring, processed to obtain an emulsifiable concentrate.

An example of preparative Form C (wettable powder) shsh with 15 parts by weight. compounds of preparative example 33, 80 parts by weight. a mixture (5:1) of "white soot" and (finely crushed particles of hydrogenated amorphous silicon dioxide) and sprayed loam and from part of the mass. "" of sodium naphthalenesulfonate/formalin condensate are combined and mixed to form a wettable powder.

An example of preparative Form 4 (wettable granules) - and 20 parts by weight. compounds of preparative example 35, 30 parts by weight. sodium ligninsulfonate, 15 parts by mass. bentonite and 35 parts by mass. calcined powdered diatomaceous earth is intensively mixed with water. The resulting product is granulated by extrusion through a 0.3 mm sieve. Drying produces capsules that are wettable.

Cheka" be o

Claims (7)

The formula of the invention IR e) 1. Derivatives of 1,3,5-triazine of the general formula (1): 2 ЧО) Ee 7 ry Ф) M muyu to 1 А-М ИЧ и бо Н in which A stands for SNEZVU, where 65 VZ and 7 simultaneously or independently one from one means alkyl with 1-6 carbon atoms or means cycloalkyl with 3-6 carbon atoms and where the total number of carbon atoms KZ and 27 is more than 3, B" means amino, formylamino, alkylcarbonylamino with 1-6 carbon atoms in the alkyl group and B" means haloalkyl with 1-4 carbon atoms in the alkyl group. 2. Derivatives of 1,3,5-triazine according to claim 1, in which A means SNEZEU, where BZ and B" independently mean isopropyl, sec-butyl and cyclohexyl, VE! means amino, formylamino, acetylamino, propionylamino, 70 B? means fluoro-, chloro-substituted methyl, ethyl or isopropyl. C. Derivatives of 1,3,5-triazine according to claim 1, in which A means SNEZVU, where BZ 27 independently means ethyl, isopropyl or cyclohexyl, B" means amino, formylamino, acetylamino or propionylamino, B? means fluoro-, chloro-substituted methyl, ethyl or isopropyl. 4. Derivatives of 1,3,5-triazine according to claim 1, in which A means SNEZVU, where BZ Her 87 independently means methyl, ethyl or cyclohexyl, B" means amino, formylamino, ethylcarbonylamino or methylcarbonylamino, B? means 1-fluoroethyl , difluorochloromethyl, dichloromethyl or 1-fluoro-1-methylethyl. 5. Compounds of the general formula (I): сч жно НО (1) (ee) Н Н со in which "A means SNEZE, where BZ means alkyl with 1-4 carbon atoms and KE" means cycloalkyl with 3-6 carbon atoms , o B" means amino, formylamino, alkylcarbonylamino with 1-6 carbon atoms in the alkyl group, and their acid addition salts. 6. Compounds according to claim 5, in which A means SNEZVU, "where KZ means alkyl with 1-4 carbon atoms and VE" means cyclohexyl. - 7. Herbicidal composition, which is characterized in that it contains a compound according to any of claims 1-4 and with conventional fillers and/or surfactants. ;" и Official " ; " " ; ; t official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2005, M 8, 15.08.2005. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. -i (95) sh» (ee) IR e) ime) 60 b5