CA2307093A1 - Substituted aryloxyalkylaminotriazines - Google Patents

Abstract

The invention relates to novel substituted aryloxy alkyl amino triazines of formula (I) wherein R1 stands, for example, for H or C1-C6 alkyl; R2 stands, for example, for H, C1-C6-alkyl or C1-C6 alkyl carbonyl; R3 stands, for example, for C2-C6 alkyl, R4 stands for example for H or C1-C4 alkyl; AR stands, for example, for substituted or unsubstituted phenyl and Z stands, for example, halogen, C1-C6 alkyl, C1-C6 hydroxy alkyl, C1-C6 halogen alkyl or C3C6 cyclo alkyl. The invention also relates to a method for the production and use thereof as herbicides.

Description

Le A 32 685-Foreign countries Bi/wa/ vos/W6/ V 31.07.1998 Substituted aryloxyalkylaminotriazines The invention relates to novel substituted aryloxyalkylaminotriazines, to processes for their preparation and to their use as herbicides.
A number of substituted aryloxyalkylaminotriazines is already known from the (patent-) literature (cf. EP 273328, EP 411153 / WO 90/09378). However, these compounds have hitherto not attained any particular importance.
..
This invention, accordingly, provides the novel substituted aryloxyalkylamino-triazines of the general formula (I) z R~~NiR
N ~ N R3 (I) I
Z~N~N~~~
R4 Ar in which R ~ represents hydrogen or represents optionally hydroxyl-, cyano-, halogen-or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C 1-C4-alkoxy-substituted alkyl, alkylcarbonyl or alkoxy-carbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, R' represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-sub-stituted alkyl having 2 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, Le A 32 685-Foreign countries R4 represents hydrogen or alkyl having 1 to 4 carbon atoms, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, where the possible heterocyclyl groupings are preferably selected from the following group:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, halogen, in each case optionionally hydroxyl, cyano or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, di-.".~ 20 alkylamino, alkylcarbonylamino, alkylsulphonylamino, bis-alkylcarbonyl-amino, bis-alkylsulphonyl-amino, N-alkyl-N-alkylcarbonyl-amino or N-alkyl-N-alkylsulphonyl-amino having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-sub-stituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, and Z represents halogen, represents in each case optionally hydroxyl-, cyano-, halogen-, C 1-C4-alkoxy-, C 1-C4-alkyl-carbonyl-, C 1-C4-alkoxy-carbonyl-, C 1-C4-alkylthio-, C 1-C4-alkylsulphinyl- or C 1-C4-alkylsulphonyl-substituted Le A 32 685-Foreign countries alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents optionally cyano-, halogen- or C 1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.
S
The novel substituted aryloxyalkylaminotriazines of the general formula (I) are obtained when (a) aryloxyalkylbiguanides of the general formula (II) ,~..
H, H, RvN~N~N D.A~ (II) R' H H R°
in which 1 S R ~ , R2, R', R4 and Ar are as defined above, - and/or acid adducts of compounds of the general formula (II) -....
are reacted with alkoxycarbonyl compounds of the general formula (III) Z-CO-OR' (III) in which Z is as defined above and R' represents alkyl, Le A 32 685-Foreign countries if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, when (b) substituted halogenotriazines of the general formula (IV) X
N~N R' (N) Z N N ~ ~Ar H R°
in which R', R4, Ar and Z are as defined above and X represents halogen, are reacted with nitrogen compounds of the general formula (V) -..
R'~ , RZ
N (V) H
in which, R~ and R2 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, Le A 32 685-Foreign countries A
- -or when (c) substituted aminotriazines of the general formula (VI) R\ ~Rz N
N ~ N (VI) Z~N~Y' ,~..
in which RI, R2 and Z are as defined above and Y1 represents halogen or alkoxy, are reacted with aryloxyalkylamines of the general formula (VII) R' HzN ~.A~ (VII) Ra in which Ar, R3 and R4 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when Le A 32 685-Forei~~n countries (d) to prepare compounds of the formula (I) in which R2 is different from hydrogen, aryloxyalkylaminotriazines of the general formula (Ia) R'~ ~ H
N
N~N R3 (Ia) Z N N Ar i H R' in which R~, R3, R4, Ar and Z are as defined above, are reacted with alkylating or acylating agents of the general formula (VIII) Y2-R2 (VIII) ,.,.. in which R2 is as defined above, except for hydrogen, and Y2 represents halogen, -O-R2 or -O-CO-R2, if appropriate in the presence of reaction auxiliary and if appropriate in the presence of a diluent, and further conversions within the scope of the above definition of substituents are carried out, if appropriate, by customary methods on the compounds of the general formula (I) obtained according to processes described under (a), (b), (c) or (d).

Le A 32 685-Forei,~n countries The novel substituted aryoxyalkylaminotriazines of the general formula (I) have strong and selective herbicidal activity.
The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in different enantiomeric (R- and S-configured forms) or diasteromeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms ....
of the compounds of the general formula (I) and to the mixtures of these isomeric compounds.
In the definitions, the hydrocarbon chains, such as alkyl- including in combination with heteroatoms, such as an alkoxy or alkylthio- are in each case straight-chain or branched.
l~
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which ... 20 R 1 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy- substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 25 R2 represents hydrogen, represents formyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy- substituted methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl or ethoxy-carbonyl, 30 R3 represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyi, n-, i-, s- or t-butyl or Le A 32 685-Foreign countries _g_ represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R4 represents hydrogen or methyl, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, ....
where the possible heterocyclyl groupings are preferably selected from the following group:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, '.., 20 in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- or chlorine-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxy-carbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, dimethylamino, diethylamino, acetyl-amino, propionylamino, methylsulphonylamino, ethylsulphonylamino, bis-acetyl-amino, bis-methylsulphonyl-amino, N-methyl-N-acetyl-amino or N-methyl-N-methylsulphonylamino, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, n-, i-, s-or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-Le A 32 685-Foreign countries butoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- or chlorine-substituted methylenedioxy or ethylenedioxy, S and Z represents fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy, n-, i-, s- or t-butoxy-, methylthio-, ethylthio, n- or i-propylthio-, ...
methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethyl-suphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Among the compounds of the formula (I) defined above as being preferred ("preferable"), particular emphasis is given to the following groups:
(A) the compounds of the formula (I) in which R1, R2, R3, R4 and Z are as defined above and Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are as defined above;
(B) the compounds of the formula (I) in which R1, R2, R3, R4 and Z are as defined above and Ar represents optionally substituted heterocyclyl, where the possible heterocyclyl groupings and the possible substituents are as defined above.
The invention relates in particular to compounds of the formula (I) in which Le A 32 685-Foreign countries R~ represents hydrogen or represents in each case optionally cyano-, fluorine-, methoxy- or ethoxy-substituted methyl or ethyl, R2 represents hydrogen, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl or propionyl, R3 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, ,....
R4 represents hydrogen, Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-.., 20 butoxy, in each case optionally fluorine- or chlorine-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, tri-fluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, di-fluoromethoxy- or trifluoromethoxy- substiuted phenyl or phenoxy, and in each case optionally fluorine-or chlorine-substituted methylenedioxy or ethylenedioxy, and Le A 32 685-Foreign countries Z represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propyl-thio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-, methyl-sulphonyl-, ethylsulphonyl-, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Among the compounds of the formula (I) defined above as being particularly preferred, particular emphasis is given to the following groups:
(A') the compounds of the formula (I) in which R1, R2, R3, R4 and Z are as defined above and Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are as defined above, with the proviso that the substituents of the carbon atom to which R' is attached are arranged in the R
configuration;
(B') the compounds of the formula (I), in which R~, R2, R3, R4 and Z are as defined ,,..~ 20 above and Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are as defined above, with the proviso that the substituents of the carbon atom to which R3 is attached are arranged in the S
configuration.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.

Le A 32 685-Forei~~n countries Examples of the compounds of the formula (I) according to the invention are listed in the groups below. The general formulae here in each case represent the R
enantiomers, the S enantiomers and the racemates.
Group 1 N ~ N CZHS
°'°"' Z~N~N~~ ~ (I-1) I
H
(a: racemates, b: R enantiomers, c: S enantiomeres) Z has here, for example, the meanings given in the list below:
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, fluoromethyl, difluoromethyl, tri-fluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromo-methyl, chlorodifluoromethyl, fluorodichloromethyl, bromodifluoromethyl, trichloro-methyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-bromo-ethyl, 1-chloro-1-fluoro-ethyl, 1-fluoro-propyl, 2-fluoro-propyl, 3-fluoro-propyl, 1-chloro -..
propyl, 2-chloro-propyl, 3-chloro-propyl, 1-bromo-propyl, 1-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl, 1-fluoro-1-methyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-1-ethyl-propyl, 1-fluoro-2-methyl-propyl, 1-chloro-2-methyl-propyl, 2-chloro-1-methyl-ethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 1,1-dichloro-ethyl, 2,2,2-trifluoro-ethyl, 1,2,2,2-tetrafluoro-ethyl, perfluoroethyl, 1,1-difluoro-propyl, 1,1-dichloro-propyl, perfluoropropyl, 1-fluoro-butyl, 1-chloro-butyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, 1-hydroxy-ethyl, 1-hydroxy-1-methyl-ethyl, 1-hydroxy-propyl, methoxymethyl, ethoxymethyl, dimethoxy-methyl, 1-methoxyethyl, 2-methoxy-ethyl, 1,1-dimethoxy-ethyl, 1-ethoxyethyl, 2-ethoxy-ethyl, 2,2-dimethoxy-ethyl, 2,2-diethoxy-ethyl, 2-methoxy-1-methyl-ethyl, 2-methoxy-1-ethyl-ethyl, 2-ethoxy-1-methyl-ethyl, 2-ethoxy-1-ethyl-ethyl, 2,2-bis-Le A 32 685-Forei.Qn countries methoxy-methyl, methylthiomethyl, ethylthiomethyl, 1-methylthio-ethyl, 2-methyl-thioethyl, 1-ethylthio-ethyl, 2-ethylthioethyl, methylsulphinylmethyl, ethylsulphinyl-methyl, methylsulphonylmethyl, ethylsulfonylmethyl, cyclopropyl, 1-cyano-cyclo-propyl, 1-fluoro-cyclopropyl, 1-chloro-cyclopropyl, 2-Cyano-cyclopropyl, 2-Fluoro-cyclopropyl, 2-chloro-cyclopropyl, 2,2-difluoro-cyclopropyl, 2,2-dichloro-cyclo-propyl, cyclobutyl, 2,2-difluoro-cyclobutyl, 2,2,3-trifluoro-cyclobutyl, 2,2-difluoro-3-chloro-cyclobutyl, cyclopentyl, cyclohexyl.
Group 2 ,e,.
~z N ~ N CzHs F
~O
Z N N ~ ~ (I-2) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 3 NHz N ~~N CZHS CI
ZI _N_ _N- v C ~ (I-3) I
H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 4 N ~~N CZHS Br Z"N- _N-I
H
(I-4) (a: racemates, b: R enantiomers, c: S enantiomers) ,.._ Z has here, for example, the meanings given above in group 1.
Group 5 N ~ N CZHS NOZ
Z- _N- _N- v 0 ~ (I-5) I
H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Gr, oup 6 N ~ N CZHS CH3 Z- _N- _N- v 0 ~ (I-C) I
H

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Gr_ oup 7 NHz N ~~N CZHS CF3 j~ ~O
..-. Z N N ~ ~ (I-7) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 8 ~z .,.-- N ~ N C2H5 OCH3 Z~N~N~O ~ (I-g) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 9 N ~~N C2H5 OCHFZ
Z N N I
(I-9) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 10 N ~~N CZHS OCF3 ZI _NI _N' v 0 ~ (I-10) ~I
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 11 N ~ N CZHS OCZHS
Z_ _N_ _N- v 0 ~ (I-11) I
H

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 12 N ~ N CZHS SCH3 -~~ Z~N~N~~ ~ (I-12) ~I
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.
Group 13 z ~... N ~ N CZHS N(CH3)z Z~N~N~~ ~ (I-13) I
H
IS
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 14 i N N CZHS N(CzHs)z Z~N~N~~ ~ (I-14) ~I
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 1 S
l0 ~z N ~ N C H H3C~N~SOzCH3 Z~N~N~~ ~ (I-15) I I
H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 16 NHz N ~~N CZHS
Z~N~N~~ ~ F (I-16) ~I

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Grouse 17 ,..~ N / N CzHs Z~N~N~~ ~ CI (I-17) H ~I
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 18 r-~.
N ~ N CZHS
Z~N~N~O ~ Br (I_18) ~I
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 19 NHz N ~~N CZHS
Z~N~N~O / NOz (I-19) I
H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 20 ~z N ~ N CZHS
ZI _N- _N- v 0 / CH3 (I-20) I
H
~..
(a: racemates, b: R enantiomers, c: S enantiomers) I 5 Z has here, for example, the meanings given above in group 1.
Group 21 ~z N ~ N CZHS
Z' _N_ _N- v 0 / CF3 (I-21) I
H

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 22 ,.." N ~~N CzHs ZI _N- _N- v 0 / OCH3 (I-22) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.
Group 23 IS
NHz N ~ N CZHs ZI _N- _N_ v 0 / I-23 ( ) I
H
F
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.

Le A 32 685-Foreign countries Group 24 NHz N ~ N CZHS
~O
Z N N ~ ~ (I-24) H
CI
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 25 z N ~ N CzHs Z' _N_ _N- v 0 ~ (I-25) H
Br s-~.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 26 NHz N ~~N C2H5 Z"N_ -N' (I-26) H
NOz Le A 32 685-Forei,~n countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 27 N ~ N CZHS
~C ~
.",- Z N N (I-27) H

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 28 NHZ
..~ N /\N CzHs ~O
Z N N I (I-28) H

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Forei;~n countries Group 29 z N ~ N CZHS
ZI _N- _N- v 0 ~ I-( 29) H

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 30 N ~ N C2H5 ~O
Z N N ~ (I-30) H
OCHFz ,....
(a: racemates, b: R enantiomers, c: S enantiomers) 1 S Z has here, for example, the meanings given above in group 1.
Groin 31 NHz N ~~N CZHS
Z' _N- _N_ v 0 ~ I-31 ( ) I
H

Le A 32 685-Forei;~n countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 32 N ~~N CZHS
,... ZI _N_ _N-(I-32) H
OCZHS
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 33 ..-- N ~ N C2H5 ZI _N_ _N-(I-33) I
H
OCH(CH3)2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 34 N ~~N CzHS
ZI _N- _N-I I (I-34) H

.r,.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 35 N ~ N CzHs Z_ _N_ _N- v 0 ~ I-I ~ ( 35) H

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 36 z N ~ N CZHS
Z_ _N- _N-I I (I-36) H

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 3 7 N ~ N CZHS
Z~N~N~~ / CI
,.~ ~ (I_37) H
CI
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 38 ~z ,,..~ N ~ N
Z"N- _N CI
I
H (I-38) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 39 ~z N ~ N CZHS CI
j~ /~O
Z N N I (I-39) H \
CI
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 40 z N ~ N CZHS CI
j~ ~O
Z N N
H \ ~ (I-40) CI
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Groin 41 NHz N ~~N CZHS
~O / Br Z N N
H \~ (I-41 ) Br Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 42 z N ~ N CZHS
.... ~ ~O / F
Z N ' vN
H \I
(I-42) CI
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 43 NHz N ~~N CZHS
~O / Br Z N N
H \ I (I-43) F
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreigy countries Group 44 z N~ N
Z- _N_ (I-44) J
(a: racemates, b: R enantiomers, c: S enantiomers) ,.-.
Z has here, for example, the meanings given above in group 1.
Group 45 r~.
~z N ~ N CzHs Z~N~N~~ / F
\I
(I-45) CzHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 46 ~z N ~ N CZHS
Z~N~N~~ / F
\ I (I-46) F

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
S Group 47 N ~ N C2H5 ~O / CI
Z N N I
H ~ (I-47) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 48 z s1 N ~ N CzHs ZI _N- _N- v C / CzHs ~I
(I-48) CzHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 49 ~z N ~ N CZHS
Z~N~N~O / CH3 H \ I (I-49) OMe (a: racemates, b: R enantiomers, c: S enantiomers) ,...
Z has here, for example, the meanings given above in group 1.
Group 50 ~z N ~ N CZHS
Z~N~N~O / CH3 H
(I-50) CzHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group S 1 ~z N ~ N CzHs Z~N~N~O / CF3 I
H \ (I-51 ) Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 52 NHz N ~~N CZHS
.,....
ZI _N_ _N- v 0 / CI
(I-52) OMe (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 53 .~,~. N ~~N CzHs ZI _N- _N_ v 0 / OMe (I-53) OMe (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Fore~n countries Group 54 z N ~~I N CZHs Z~N~N~O / OCzHs ~I
(I-54) OCZHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 55 NHz N ~~N CZHs Z' _N_ _N- v 0 ~ I (I-55) I I
H
r..,.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 56 z N ~ N C2Hs ZI _N- _N_ ( H ~ (I-56) CzHs Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 57 NHz N ~~N C2H5 Z' _N- _N- v 0 /
I
H \ (I-57) OCzHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 58 z N ~ N CZHS
ZI _N- _N- v 0 /
I
H \ (I_58) OCH(CH3)z (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 59 N ~~N CZHS
Z~N~N~~
~I
(I-59) CH(CH3)2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 60 N ~~N CZHS
Z~N~N~C
~I
(I-60) CH(CH3)2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Forei;~n countries Group 61 N ~ N C2H5 ZI _N- _N- v 0 ~I
OCHFZ (I-61 ) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 62 ....
z N ~ N CZHS
Z' _N- _N_ ~I
(I-62) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.
Group 63 N ~ N CzHs Z_ _N- _N-I I
H ~ (I-63 ) Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 64 z N ~ N CZHS
r~, Z~N~N~~
I
H ~ (I-64) N(CH3)z (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 65 NHz N ~ N CZHS
Z~N~N~~
H
(I-65 ) N(CzHs)z (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 66 z N ~ N CZHS
ZI _N- _N- v 0 I
H \ (I-66) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.
Group 67 ~z N ~ N CZHS
ZI 'N_ -N- v 0 /
I
H \ (I_67) (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.

Le A 32 685-Foreign countries Group 68 N ~~N CZHS
ZI _N_ _N-I
H
(I-68) N
H3C~ ~SOZCH3 s-.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 69 z N ~~I N CZHS
ZI _N- _N-I
H
"'' (I-69) N
H3C~ ~COCH3 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 70 z N ~ N CZHS
ZI _N- _N-(I-70) N(SOZCH3)z (a: racemates, b: R enantiomers, c: S enantiomers) ....
S
Z has here, for example, the meanings given above in group 1.
Group 71 z N ~ N CzHS
~O
Z N N I (I-71 ) H
CzHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Groun 72 z N ~ N CZHS
Z' _N- _N_ I I (I-72) H
CH(CH3)z Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 73 ~z N ~ N CZHs -.. Z~N~N~~ /
(I-73 ) H
CsHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Groin 74 NHz N~N CzHs ZI _N- _N- v C /
(I-74) H
1 S ~CsHs (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foregn countries Group 75 z N ~ N CZHS
~O
Z N N ( (I-75) H
N(CH3)z .-.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Groin 76 N ~ N CzHs (I-76) Z~N~N~~
~I
N(CZHS)z ....
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 77 z N ~ N CZHS
Z- _N- -N- v C
I (I-77) I
H
N(C2H5)z Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 78 N ~~N CZHS
,.... ZI _N- _N-I I (I_78) H

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 79 NHz o--~ N ~~N CZHS
ZI _N- _N_ I (I-79) i H
N(SOzCH3)z (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Foreign countries Group 80 NHz N i~N CzHS
ZI _NI _N_ H \ I N~CHs (I-80) I

(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 81 NHz N ~~N CZHS
ZI _N- _N-I I (I-81 ) H \
COOCzHs ,.
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 82 z N ~ N CZHS
ZI _N- _N-I I (I-82) H \
COOCH(CH3)z Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group I.
S Group 83 N ~~N CZHS
-.~ Z~N~N~~
(I-83 ) H
C(CH3)s (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 84 HN'CH3 ..... ~
N-/ _N CZHS
~O
Z N N ~ I (I-84) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 685-Forei;en countries Group 85 HN~C2Hs N i _N CzHs j~ ~O
Z N N ~ I (I-85) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 86 ....

O/~N~CH3 N-/ _N CZHS
~O
Z N N ~ ~ {I-86) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 87 H
O N~
N~N C2H5 ~O
Z N N ~ ~ (I-87) H

Le A 32 685-Foreisn countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 88 NHz N ~~N CH(CH3)z ~O
Z N N ~ ~ (I-88) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 89 ..-. ~ s H
O N~
N i _N CZHS
Z' _N_ _N_ v 0 ~ (I-89) H
(a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.

Le A 32 b85-Foreign countries Group 90 N ~~N
Z- _N- _N
I
H (I-90) (a: racemates, b: R enantiomers, c: S enantiomers) S
Z has here, for example, the meanings given above in group 1.
Group 91 ~z N ~ N C2H5 Z~N~N~~ / CH3 I
H \ (I-91 ) ~H' (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Group 92 ~z N ~ N CZHS
~/
Z N N
H \ ~ F (I-92) F

Le A 32 685-Foreign countries (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
Using, for example, 1-(1-phenoxymethyl-propyl)-biguanide and methyl trifluoro -acetate as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme:
H. H. ~z O ~ OCH3 N N CZHS
+ H . ~ j~ ~ O ---~ ~ ~ ~CzHs CF3 N N N ' H H H \ ~ F3C N N- v 0 \
H ~ /
Using, for example, 2-chloro-4-(1-phenoxymethyl-propylamino)-6-trifluoromethyl-1,3,5-triazine and ethylamine as starting materials, the course of the reaction and the process (b) according to the invention can be illustrated by the following formula scheme:
..,., NHCzHs N ~ 1 CzHs HzN~ N ~~N C H
z s ~O - HCI ~ ~O
F3C N N \ I F3C N H /
~I
Using, for example, 2-amino-4-methoxy-6-trifluoromethyl-1,3,5-triazine and 1-phenoxymethyl-propylamine as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme:

Le A 32 685-Foreign countries NHZ C H

N~N + H NI v 0 \ _ p N ~ N CZHS
~ ~ ~~~ 'O
F3C_ ' _ _OCH3 ~ / F3C_ _N_ _N_ v \
H
Using, for example, 2-amino-4-(1-phenoxymethyl-propylamino)-6-trifluoromethyl-1,3,5-triazine and acetyl chloride as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following formula scheme:
,CH3 H

N N CZHS ~ N ~ N CZHS
~O - HCI
F3C N N / ~ F3C N N /
H \ H \
The formula (II) provides a general definition of the aryloxyalkylbiguanides to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (II), R~, R2, R3, R4 and Ar preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the IS invention, as being preferred or as being particularly prefenred for R~, R2, R3, R4 and Ar.
The starting materials of the general formula (II) have hitherto not been disclosed in the literature; as novel substances, they form part of the subject-matter of an earlier, not prior-published patent application (cf. DE-A-19641691 dated 10.10.1996 -LeA31995).
Suitable acid adducts of compounds of the formula (II) are their addition products with protic acids, such as, for example, with hydrogen chloride, hydrogen bromide, Le A 32 685-Foreign countries sulphuric acid, methanesulphonic acid, benzenesulphonic acid and p-toluene-sulphonic acid.
The aryloxyalkylbiguanides of the general formula (II) are obtained when substituted aryloxyalkylamines of the general formula (VII) HZN ~ . p,~ (VII) R°
in which R', R4 and Ar are as defined above, - and/or acid adducts of compounds of the Seneral formula (VII), such as, for example, the hydrochlorides -are reacted with cyanoguanidine ("dicyanodiamide") of the formula (IX) H, N
II N
H.N~N~ 11X) i i H H
if appropriate in the presence of a reaction auxiliary, such as, for example, hydrogen chloride, and if appropriate in the presence of a diluent, such as, for example, n-decane or 1,2-dichloro-benzene, at temperatures between 100°C and 200°C (cf. EP
492615, Preparation Examples).
The aryloxyalkylamines of the general formula (VII) required as precursors for this purpose are known and/or can be prepared by processes known per se (cf. Acta Pol.

Le A 32 685-Foreign countries Pharm. 53 ( 1996), 47-52 - quoted in Chem. Abstracts 126:46897; Angew. Chem.

(1994), 1041-1043; Bull. Soc. Chim. Belg. 85 (1976), 421-425; loc. cit. 86 (1977), 1003-1007; J. Med. Chem. 10 (1967); 717-724; J. Am. Chem. Soc. 97 (1975), 6900-6901; Tetrahedron Lett. 35 (1994), 3745-3746; DE 3222152; DE 3221540; EP
355351; EP 601486; ZA6903772; Preparation Examples).
The formula (III) provides a general definition of the alkoxycarbonyl compounds further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (III), Z preferably or in ,_ particular has that meaning which has already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Z; R' preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the formula (III) are known chemicals for synthesis.
The formula (N) provides a general definition of the substituted halogenotriazines to be used as starting materials in the process (b) according to the invention for preparing compounds of the formula (I). In the formula (IV), R3, R4, Ar and Z
preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R3, R4, Ar and Z; X preferably represents fluorine or chlorine, in particular chlorine.
The starting materials of the general formula (N) have hitherto not been disclosed in the literature; as novel substances, they form part of the subject-matter of an earlier, not prior-published patent application (cf. DE-A-19641691 dated 10.10.1996 -LeA31995).
The substituted halogenotriazines of the general formula (IV) are obtained when corresponding dihalogenotriazines of the general formula (X) Le A 32 685-Foreign countries X
N ~ N (X) w Z~N~X' in which S
X and Z are as defined above and X ~ represents halogen, are reacted with substituted aryloxyalkylamines of the general formula (VII) HZN ~ ~ Ar (VII) Ra in which ~~ 15 R', R4 and Ar are as defined above, if appropriate in the presence of an acid acceptor, such as, for example, ethyldiisopropylamine, and if appropriate in the presence of a diluent, such as, for example, tetrahydrofuran or dioxane, at temperatures between -50°C and +50°C (cf.
the Preparation Examples).
The formula (VI) provides a general definition of the substituted aminotriazines to be used as starting materials in the process (c) according to the invention for preparing compounds of the formula (I). In the formula (VI), R~, R2 and Z preferably or in particular have those meanings which have already been mentioned above, in Le A 32 685-Foreign countries connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R~, R2 and Z; Y~
preferably represents fluorine, chlorine, methoxy or ethoxy, in particular chlorine or methoxy.
The starting materials of the general formula (VI) are known and/or can be prepared by processes known per se (cf. WO 95/11237).
The formula (VII) provides a general definition of the substituted aryioxyalkylamines further to be used as starting materials in the process (c) according to the invention.
In the formula (VII), R', R4 and Ar preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R', R4 and Ar.
The starting materials of the general formula (VII) are known and/or can be prepared by processes known per se (cf. DE 3426919; DE 4000610; DE 4332738, EP 320898;
EP 443606; Tetrahedron: Asymmetry 5 ( 1994), 817-820; Tetrahedron Lett. 29 (1988), 223-224; loc. cit. 36 (1995), 3917-3920; Preparation Examples).
The formula (Ia) provides a general definition of the aryloxyalkylaminotriazines to be used as starting materials in the process (d) according to the invention for preparing compounds of the formula (I). In the formula (Ia), R ~ , R3, R4 Ar and Z
preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R~, R', R4 Ar and Z.
As novel substances, the starting materials or the general formula (Ia) form part of the subject-matter of the present application, but some of them also form part of the subject-matter of an earlier, not prior-published patent application (cf.

Le A 32 685-Foreign countries DE-A-19641691 dated 10.10.1996 - LeA31995); they can be prepared by the processes (a), (b) or (c) according to the invention (cf. the Preparation Examples).
The formula (V1TI) provides a general definition of the alkylating or acylating agents further to be used as starting materials in the process (d) according to the invention.
In the formula (VIII), R2 has preferably or in particular that meaning, which has already been given above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R2, except for hydrogen; Y2 preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, acetyloxy or propionyloxy, in particular chlorine, methoxy or acetyloxy.
The starting materials of the general formula (VIII) are known chemicals for synthesis.
The processes according to the invention for preparing compounds of the formula (I) are, if appropriate, carried out using a reaction auxiliary. Suitable reaction auxiliaries for the processes (a), (b), (c) and (d) are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, 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, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclo-hexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-Le A 32 685-Foreien countries pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
T.....
Suitable diluents for carrying out the processes (a), (b), (c) and (d) according to the invention are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride;
ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as methyl isopropyl ketone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide;
1 S esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the processes (a), (b), (c) and (d) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between -20°C and +300°C, preferably between -10°C and +250°C.
The processes (a), (b), (c) and (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
In carrying out the processes according to the invention, the starting materials are generally employed in approximately equimo(ar amounts. However, it is also Le A 32 685-Foreien countries possible, in each case, to employ a relatively large excess of one of the components.
The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred for a number of hours at the temperature required. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are .-..
not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, ,,... 20 Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the eg nera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Aiopecurus and Apera.

Le A 32 685-Foreien countries Monocotyledonous cultures of the ;genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for the control -., of weeds in perennial crops, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual cultures.
1~
The compounds of the formula (I) according to the invention are suitable in particular for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as ,.-.
solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid earners, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially the following:
aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and - Le A 32 685-Foreign countries chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fi-actions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid Garners are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Le A 32 685-Foreign countries The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For the control of weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example ,.....
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlorotoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), ,,...
difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthi-acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate-(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), Le A 32 685-Foreign countries hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, S metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, -.
propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-{-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, 1 S sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.

Le A 32 685-Forei;~n countries The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
,d.-.

Le A 32 685-Foreign countries Preparation Examples:
Example 1 NHZ
N ~ N CZHS
~ ' 3 F3C~N~N~~ ~ CH
H

(process (a)) '" 5 A mixture, prepared at -10°C, of 3.2 g (10 mmol) of (R/S)-1-[1-ethyl-2-(3,5-dimethyl-phenoxy)-ethyl]-biguanide hydrochloride (racemic), I .3 g ( 10.6 mmol) of methyl trifluoroacetate, 1.0 g (20 mmol) of sodium methoxide, 2.75 g of zeolite molecular sieve and 20 ml of methanol is stirred at about 0°C for approximately 15 hours. The mixture is then filtered off with suction, the filtrate is diluted with water to about three times its volume and shaken with ethyl acetate and the organic phase is separated off, washed with water, dried with sodium sulphate and filtered.
The solvent is carefully distilled off from the filtrate under water pump vacuum.
..
This gives 2.0 g (92% pure according to HPLC, i.e. 52% of theory) of (R/S)-2-amino-4-trifluoromethyl-6-[ 1-(3,5-dimethyl-phenoxymethyl)-propylamino]-1,3,5-triazine (racemate) as an amorphous residue; loge: 3.77 b>.
Analogously to Example 1, and in accordance with the general description of the preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table I below.
R'~ , RZ
N
N ~ N R3 (I) Z~N~N ~~Ar i Le A 32 685-Foreign countries Table 1: Examples of the compounds of the formula (I) Ex. R~ R2 R3 R4 Ar Z Physical data No. and stereo-chemical specifications 2 H H C2H5 H ~ CH3 (amorphous) (racemate) 3 H H C2H5 H ~ C2H5 (amorphous) ( / (racemate) loge: 3.03 b~

4 H H C2H5 H ~ w c", CH3 (amorphous) (racemate) cH, logP: 1.74 a>

5 H H C2H5 H I ~ c", C2H5 (amorphous) (racemate) c"' logP: 3.05 b>

-..

6 H H C2H5 H ~ C3H~-i (amorphous) ( / (racemate) loge: 3.51 b~

7 H H C2H5 H I ~ c", C3H~_i (amorphous) (racemate) CHI

8 H H C~HS H ~ CH3 (amorphous) (racemate) C2Hs Le A 32 685-Foreign countries Ex. R~ RZ R3 R4 Ar Z Physical data No. and stereo-chemical specifications HO"CH3 (amorphous) (racemate) CZHs 10 H H C2H5 H ~ CHFCH3 (amorphous) -.. ~ / (racemate) CZHs 11 H H C2H5 H ~ CZHS (amorphous) (racemate) CzHs 12 H H C~HS H ~ B~~c2~5 (amorphous) (racemate) CzHs .~--- 13 H H C2H5 H ~ B~~cH3 (amorphous) (racemate) CzHs 14 H H C2H5 H ~ CF3 (amorphous) (racemate) CI

15 H H C2H5 H ~ cycH3 (amorphous) (racemate) CI

Le A 32 685-Forei,~n countries Ex. R~ R2 R3 R4 Ar Z Physical data No. and stereo-chemical specifications 16 H H C2H5 H ~ CHFCH3 (amorphous) (racemate) CI

17 H H C2H5 H I w c", CHFCH3 (amorphous) (racemate) c", logP: 3.16 b>

18 H H C2H5 H I ~ c", CF(CH;)2 (amorphous) (racemate) c", logP: 3.53 b>

19 H H C2H5 H ~ CHFCH~ (amorphous) (racemate) loge: 3.01 b>

20 H H C2H5 H ~ CF(CH3)2 (amorphous) (racemate) ..-, loge: 3.34 b~

21 H H C2H5 H ~ CHFCH; (amorphous) (racemate) loge: 2.70 b~

22 H H C2H5 H ~ CF(CH3)2 (amorphous) (racemate) loge: 3.04 b>

Le A 32 685-Foreign countries Ex. RI R2 R3 R4 Ar Z Physical data No. and stereo-chemical specifications 23 H H C2H5 H ~ C2H5 (amorphous) (racemate) loge: 2.64 b>

24 H H C2H5 H ~ CH3 (amorphous) -. ~ / (racemate) loge: 2.25 b>

25 H H C2H5 H ~ CF3 (amorphous) (racemate) loge: 3.36 b>

26 H H C2H5 H ~ CF(CH3)2 (amorphous) ( / (racemate) loge: 2.87 b) F

.., 27 H H C2H5 H ~ CF3 (amorphous) (racemate) loge: 3.18 b~

F

28 H H C2H5 H ~ CHFCH3 (amorphous) (racemate) loge: 2.56 b>

F

29 H H C2H5 H ~ C2H5 (amorphous) (racemate) loge: 2.52 b>

F

Le A 32 685-Foreign countries Ex. R R2 R3 R4 Ar Z Physical ~ data No. and stereo-chemical specifications ~ cycH, (amorphous) 30 H H C H H ~

(racemate) loge: 2.98 b1 F

31 H H C2H5 H ~ (amorphous) (racemate) loge: 2.80 b>

F

32 H H C2H5 H I ~ oMe C2H5 m.p.:75C

(racemate) OMe 33 H H C2H5 H I w ""e B~~cZHs (amorphous) (racemate) OMe to P: 3.24 b~

34 H H C2H5 H I w ""e CHFCH~ m.p.:82C

(racemate) OMe to P: 2.45 b~

''~ 35 H H C2H5 H I w ""e CF(CH3)2(amorphous) (racemate) OMe to P: 2.74 b) 36 H H C2H5 H I ~ OMe CF3 m.p.:92C

(racemate) OMe to P: 3.08 b~

37 H H C2H5 H ~ CHFCH3 (amorphous) (racemate) 38 H H C2H5 H ~ C2H5 (amorphous) (racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data No. and stereo-chemical specifications 39 H COCH3 C2H5 H ~ CHFCH3 m.p.:126C

(racemate) 40 H H C2H5 H ~ CF3 m.p.:100C

(racemate) s....

41 H H C2H5 H CFA (amorphous) (racemate) CI

42 H H C2Hg H CF3 (amorphous) (S enantiomer) CI

43 H H C2H5 H ~ CF3 (amorphous) (R enantiomer) ,tea 44 H H C2H5 H ~ CF3 (amorphous) (S enantiomer) 45 H H C2H5 H CF3 (amorphous) (R enantiomer) CI

46 H COCH3 C2H5 H ~ CF3 m.p.:99C

(R enantiomer) Le A 32 685-Foreign countries Ex. R R2 R3 R4 Ar Z Physical I data No. and stereo-chemical specifications 47 H COCH3 C2H5 H ~ CF3 m.p.:102C

(S enantiomer) 48 H COCH3 C2H5 H CF3 m.p.:99C

\ (R enantiomer) -"

CI

49 H COCH3 CZHS H CF3 m.p.:106C

\ (S enantiomer) CI

50 H H C2H5 H ~ Ho (amorphous) (racemate) 51 H H C2H5 H CH3 HO"CH3 (amorphous) '~~~ ~ \ (racemate) 52 H H C2H5 H CH3 i-C3H~ (amorphous) (racemate) IogP: 3.61 b>

53 H H C~HS H CH3 cycH2ci (amorphous) (racemate) loge: 3.40 b~

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data No. and stereo-chemical specifications 54 H H C2H5 H ~H3 C2H5 (amorphous) (racemate) loge: 3.08 b) 55 H H C2H5 H CH3 CF(CH3)2(amorphous) \ (racemate) loge: 3.48 b) 56 H H C2H5 H CH3 CF3 (amorphous) \ (racemate) loge: 3.79 b) 57 H H C2H5 H ~ C~ C2H5 loge: 1.79 a) ( i (racemate) .,.-,.

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 58 H H C2H5 H ~ cH3 cycH3 loge: 2.69 a~
(racemate) 59 H H C2H5 H ~ CH3 IogP: 1.84 a>
(racemate) ,,.-, 60 H H C2H5 H ~ CH3 Br\ 'CH3 loge: 2.78 a~
( , (racemate) 61 H H C2H5 H I ~ cH3 HO"CH3 loge: 1.58 a~
(racemate) 62 H H C2H5 H ~ CH3 CH-,OCH; loge: 1.65 a~
(racemate) 63 H H C2H5 H ~ CHa CH20H loge: 1.44 a~
(racemate) r-,, 64 H H C2H5 H ~ CF(CH3)2 loge: 1.90 a~
( S enantiomer) 65 H COCH3 C2H5 H ~ CF(CH3)2 loge: 3.06 a~
(S enantiomer) 66 H COC2H5 C2H5 H I ~ CF(CH3)2 (amorphous) (S enantiomer) 67 H COC2H5 C2H5 H ~ CF3 (amorphous) (S enantiomer) Le A 32 685-Foreign countries Ex. R I R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 68 H H C2H5 H ~ CI CF3 loge: 4.12 b) (racemate) CI
69 H H C2H5 H ~ CI CF(CH3)2 loge: 3.83 b) (racemate) ,.-.
CI
70 H H C2H5 H ~ CI loge: 3.80 b) (racemate) CI
71 H H C2H5 H ~ CI cyc2H5 loge: 4.31 b) (racemate) CI
72 H H C2H5 H ~ CI Br~cZHs (amorphous) (racemate) ,,-..
CI
73 H H C2H5 H ~ CI Br~cH3 (amorphous) (racemate) CI
74 H H C2H5 H cH3 cyc"3 loge: 3.21 b) (racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 75 H H C2H5 H ~H3 C2H5 loge: 2.71 b) (racemate) 76 H H C2H5 H ~H3 CF3 loge: 3.44 b) ( \ (racemate) .. /

77 H H C2H5 H Cola Br~cH3 loge: 3.34 b) (racemate) 78 H H C2H5 H CH3 HO"CH3 loge: 2.27 b) (racemate) 79 H H C2H5 H \ CI C2H5 m.p.:79C

(racemate) CI

-.

80 H H C2H5 H \ CI CF; m.p.:118C

(racemate) CI

81 H H C2H5 H \ CI CHFCH3 m.p.: 101 C

(racemate) CI

82 H H C2H5 H \ CI c~~cH3 (amorphous) (racemate) CI

83 H H C2H5 H ~ CI cycz"5 (amorphous) (racemate) CI

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications C~ B'~cH3 (amorphous) (racemate) 85 H H C2H5 H ~~ C2H5 (amorphous) (racemate) .,.-..

86 H H C2H5 H ~~ CH(CH3)~ (amorphous) (racemate) 87 H H C2H5 H c~ ci\ /cH3 (amorphous) (racemate) 88 H H C2H5 H ~~ CFA (amorphous) (racemate) ,,~..

89 H H C2H5 H ~~ CF(CH3)2 loge: 3.04 b>

(racemate) 90 H H C2H5 H \ CHFCH~ (amorphous) (racemate) 91 H H C2H5 H \ CF(CH3)2 loge: 2.74 b>

(racemate) Le A 32 685-Foreign countries _77_ Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 92 H H C2H5 H ~ CF3 m.p.:110°C
(racemate) 93 H H C2H5 H I ~ Br\ 'CzHs (amorphous) (racemate) ,,-..

94 H H C2H5 H ~ (amorphous) (racemate) 95 H H C2H5 H ~ B~~CH3 (amorphous) (racemate) 96 H H C2H5 H ~ C2H5 (amorphous) (racemate) CH(CH3)2 97 H H C2H5 H ~ ~ycH2c~ (amorphous) (racemate) CH(CH3)2 98 H H C2H5 H ~ CH(CH3)~ (amorphous) ( / (racemate) CH(CH3)2 Le A 32 685-Foreign countries _78_ Ex. R1 R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications ~ cycH3 (amorphous) I (racemate) CH(CH3)z 100 H H C2H5 H ~ CH20CH3 (amorphous) (racemate) ,.-..

CH(CH3)2 101 H H C2H5 H ~ CHFCH3 (amorphous) (racemate) CH(CH3)~

102 H H C2H5 H ~ C2H5 (amorphous) (racemate) 103 H H C2H5 H ~ c~~cH3 (amorphous) (racemate) A

104 H H C2H5 H ~ CF(CH3)2 loge: 2.13 a) (racemate) 105 H H C2H5 H ~ CHFCH3 (amorphous) (racemate) 106 H H C2H5 H ~ CH20CH~ (amorphous) (racemate) 107 H H C2H5 H ~ F CHg (amorphous) (racemate) Le A 32 685-Foreign countries Ex. R1 R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 108 H H C2H5 H \ F CH20CH; (amorphous) (racemate) 109 H COC2H5 C2H5 H \ F CF(CH3)2 m.p.:94C

( / (racemate) 110 H COC2H5 C2H5 H \ F CH3 m.p.:114C

(racemate) 111 H COC2H5 C2H5 H \ F CHFCH~ (amorphous) (racemate) 112 H H C2H5 H cH3 CF(CH3)2 loge: 3.12 b>

(racemate) 113 H H C2H5 H \ CH3 c~~cH3 (amorphous) (racemate) -, 114 H H C2H5 H \ CH3 HO~CH3 (amorphous) I (racemate) /

115 H H C2H5 H \ CF(CH3)2 loge: 2.77 b>

(racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 116 H COCH3 C2H5 H ~ CF(CH3)2 (amorphous) I (racemate) 117 H COC2H5 C2H5 H ~ CF(CH3)2 (amorphous) I (racemate) I H COC2H5 C2H5 H ~ CHFCH3 (amorphous) ( / (racemate) 119 H H C2H5 H ~ cyc"3 loge: 2.85 b>

I (racemate) 120 H COC2H5 C2H5 H ~ CFA loge: 3.08 b~

( / (racemate) 121 H COCH3 C2H5 H ~ cyc"3 loge: 2.86 b~

(racemate) 122 H COC~HS C2H5 H ~ cyc"3 loge: 2.86 b>

( / (racemate) 123 H H C2H5 H ~ CF(CH3)2 loge: 2.76 b>

(R enantiomer) 124 H H C2H5 H ~ CHFCH3 loge: 2.43 b>

(R enantiomer) 125 H COCH3 C2H5 H ~ CF(CH3)2 (amorphous) I (R enantiomer) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 126 H COC2Hg C2H5 H ~ CF(CH3)2 (amorphous) I (R enantiomer) 127 H COC2H5 C2H5 H ~ CHFCH3 (amorphous) (R enantiomer) 128 H H C2H5 H ~ F i zHs loge: 2.43 b>

WC/ (racemate) Hz 129 H H C2H5 H I ~ F H3C~ loge: 3.34 b~
CzHs (racemate) 130 H H C2H5 H ~ F CHF2 loge: 2.67 b>

(racemate) 131 H COCH3 C2H5 H ~ F CF(CH3)2 loge: 3.20 b~

(racemate) -.

132 H H C2H5 H ~ CF(CH3)2 IogP: 3.76 b~

(racemate) CsHs 133 H H C2H5 H ~ CHFCH3 loge: 3.41 b>

(racemate) CsHs 134 H H C2H5 H ~ C2H5 loge: 3.38 b>

(racemate) CsHs Le A 32 685-Foreign countries Ex. RI R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 135 H H C2H5 H ~ cyc"3 loge: 3.85 b~

I (racemate) CsHs 136 H H C2H5 H ~ CHFCH3 loge: 2.26 a~

(racemate) .--> cl 137 H H C2H5 H ~ C2H5 loge: 1.79 a~

(racemate) C~

138 H H C2H5 H ~ CF(CH;)2 loge: 2.24 a) (racemate) 139 H COCH~ C2H5 H ~ CI CHFCH3 (amorphous) (racemate) CI

140 H H C2H5 H ~ F CF(CH3)2 (amorphous) ,,_, ~ / (racemate) F

141 H H C2H5 H ~ F CH20CH3 (amorphous) (racemate) F

142 H H C2H5 H ~ F CF3 (amorphous) (racemate) F

143 H H C2H5 H ~ F CH(CH3)~ (amorphous) (racemate) F

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 144 H H C2H5 H ~ F ci\ /cH, (amorphous) (racemate) F

145 H H C2H5 H ~ F CHFCH3 (amorphous) (racemate) F

.....
146 H H C2H5 H ~ CH3 CF(CH3)2 (amorphous) (racemate) F

147 H H C2H5 H ~ CH3 C2H5 (amorphous) (racemate) F

148 H H C2H5 H ~ ~H3 CF3 (amorphous) (racemate) F

149 H H C2H5 H ~ CH3 CHFCH3 (amorphous) '' (racemate) F

150 H H C2H5 H ~ F CF(CH3)2 loge: 3.12 b~

(racemate) F

151 H H C2H5 H ~ F CH20CH3 loge: 2.37 b>

(racemate) F

Le A 32 685-Foreign countries Ex. R1 R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 152 H H C2H5 H ~ F ci\ /cH3loge: 3.21 b) (racemate) F

153 H H C2H5 H ~ F CHFCH3 loge: 2.78 b) (racemate) r.., F

154 H H C2H5 H ~ CH3 i ZHS loge: 2.88 b) OwC/ (racemate) 155 H H C2H5 H ~ CH3 CH20CH3 loge: 2.60 b) I (racemate) 156 H H C2H5 H ~ CH3 CHFCH~ loge: 3.07 b) . I / (racemate) " CH3 157 H H C2H5 H ~ CH3 CF(CH3)2loge: 3.43 b) (racemate) 158 H H C2H5 H ~ CH3 C(CH3)3 loge: 4.35 b) (racemate) Le A 32 685-Forei;en countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 159 H H C2H5 H oCH3 CF(CH3)2 loge: 2.57 b>

(racemate) 160 H H C2H5 H ocH3 CF3 IogP: 2.86 b~

~ (racemate) /

161 H H C2H5 H oCHs CHFCH3 loge: 2.24 b>

(racemate) 162 H H C2H5 H ocH3 C2H5 loge: 2.22 b>

(racemate) 163 H H C2H5 H ocH3 cycH3 loge: 2.65 b>

(racemate) ,-~ /

164 H H C2H5 H oCH3 i 2H5 loge: 2.13 b>

oy/ (racemate) 165 H H C2H5 H ~ ~~ CF(CH;)2 m.p.:88C

(racemate) 166 H H C2H5 H ~ CF(CH;)2 loge: 3.47 b>

(racemate) CzHs Le A 32 685-Foreihn countries Ex. R R2 R3 R4 Ar Z Physical ~ data and stereo-No. chemical specifications 167 H H C2H5 H ~ CF(CH3)2 loge: 3.78 b) (racemate) CH(CH3)z 168 H H C2H5 H ~ CI CF(CH3)2 loge: 3.63 b) .. ~ / (racemate) CI

169 H COCH3 C2H5 H ~ CF(CH3)2 loge: 4.08 b) (racemate) CH(CH3)z 170 H COCH; C2H5 H ~ CI CF(CH3)2 loge: 3.90 b) ( / (racemate) CI

171 H COCH3 C2H5 H ~ CI CF(CH3)2 loge: 3.52 b) (racemate) 172 H COCH3 C2H5 H ~ CF(CH3)2 loge: 2.85 a) (racemate) 173 H COC2H5 C2H5 H ~ CF(CH3)2 loge: 3.10 a) (racemate) 174 H o~c3H~' C2H5 H ~ CF(CH3)2 loge: 3.28 a) I (racemate) Le A 32 685-Foreign countries _87_ Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 175 H H C2H5 H ~H3 CF3 (amorphous) ( \ (racemate) 176 H H C2H5 H CHa CF(CH3)2loge: 2.41 a~

,....

(racemate) 177 H H C2H5 H CHs CHFCH3 loge: 2.44 ~ a~

(racemate) 178 H H C2H5 H CH3 C2H5 loge: 1.92 a~

(racemate) .-k 179 H H C2H5 H CF(CH3)2loge: 3.91 b~

(racemate) 180 H H C2H5 H CHFCH3 loge: 3.52 b~

(racemate) Le A 32 685-Foreign countries _88_ Ex. R R2 R3 R4 Ar Z Physical ~ data and stereo-No. chemical specifications 181 H H C2H5 H ~ CF(CH3)2loge: 3.42 b~

/ (racemate) /

182 H H C2H5 H ~ CHFCH; loge: 3.06 b~

/ (racemate) /

~ H H C2H5 H ~ CF; loge: 3.70 183 b>

/ (racemate) /

184 H H C2H5 H ~ CH~OCH; loge: 2.61 b~

/ (racemate) ,' 185 H H C2H5 H CF(CH3)2loge: 2.41 b~

(racemate) /

/

186 H H C2H5 H CHFCH3 loge: 2.44 a>

(racemate) /

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 187 H H C2H5 H CF3 loge: 3.74 a) (racemate) /

/

'~ 188 H H C2H5 H CH20CH3 loge: 1.90 a) (racemate) /

189 H H C2H5 H F CF(CH3)2 loge: 2.75 b) (racemate) 190 H H C2H5 H F CFA logP: 3.03 b) (racemate) -~ /

191 H H C2H5 H F C2H5 loge: 2.44 b) (racemate) 192 H H C2H5 H F CHFCH3 loge: 2.46 b) (racemate) 193 H H C2H5 H F cyc"3 loge: 2.87 b) (racemate) Le A 32 685-Foreien countries Ex. R1 R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 194 H H C2H5 H ~~ CF(CH3)2 loge: 3.05 b~

(racemate) OCH

195 H H C2H5 H ~~ CF3 loge: 3.32 b>

....
(racemate) OCH

196 H H C2H5 H ~~ C2H5 loge: 2.69 b~

(racemate) OCH

197 H H C2H5 H oCH3 CF(CH3)2 loge: 2.70 b>

(racemate) F

-.

198 H H C2H5 H oCH3 CF3 loge: 3.00 b~

(racemate) F

199 H H C2H5 H OCH3 CF(CH3)2 loge: 2.90 b>

(racemate) 200 H H C2H5 H ocH3 CF3 loge: 3.21 b>

\ (racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 201 H H C2H5 H ocH3 C2H5 loge: 2.54 b~

(racemate) 202 H H C2H5 H \ CF(CH3)2 loge: 3.13 b>

(racemate) OCzHs 203 H H C2H5 H \ CH20CH; loge: 2.38 b>

(racemate) OCZHS

204 H H C2H5 H \ - CFA loge: 3.42 b~

(racemate) OCZHS

205 H H C2H5 H \ CHFCH3 loge: 2.78 b~

(racemate) OCZHS

206 H H C2H5 H ~H3 CF(CH3)2 loge: 3.43 b>

CH3 (racemate) 207 H H C2H5 H ~H3 CF3 loge: 3.73 b~

\ CH3 (racemate) Le A 32 685-Foreign countries Ex. R R2 R3 R4 Ar Z Physical ~ data and stereo-No. chemical specifications 208 H H C2H5 H cH3 C2H5 loge: 3.03 b>

\ CH3 (racemate) 209 H H C2H5 H cH3 CHFCH3 loge: 3.05 b>

\ CH3 (racemate) -..

210 H H C2H5 H CH3 ci\ /cH3loge: 3.53 b~

\ CH3 (racemate) 211 H H C2H5 H \ cycH2ci loge: 3.30 b~

(racemate) F

212 H H C2H5 H ocH3 CF(CH;)2loge: 1.80 b>

OCH (racemate) /

213 H H C2H5 H ocH3 CF3 loge: 2.77 b~

OCH (racemate) 214 H H C2H5 H F CF(CH~)-,logP: 2.85 b>

(racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 215 H H C2H5 H F CF3 loge: 3.14 b~

\ F (racemate) 216 H H C2H5 H F C2H5 loge: 2.50 b~

\ F (racemate) 217 H H C2H5 H F CHFCH3 IogP: 2.55 b~

\ F (racemate) 218 H H C2H5 H F cycH3 loge: 2.95 b~

\ F (racemate) 219 H H C2H5 H ocH3 CF(CH3)2 loge: 2.61 I b>

(racemate) ,.... / F

220 H H C2H5 H \ CF(CH3)2 loge: 2.80 b~

(racemate) F

221 H H C2H5 H \ CFA logP: 3.12 b>

(racemate) F

222 H H C2H5 H \ C2H5 loge: 2.43 b>

(racemate) F

Le A 32 685-Forei;~n countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 223 H H C2H5 H ~ CHFCH3 loge: 2.48 b) / (racemate) F

224 H H C2H5 H ~ cyc"3 loge: 2.90 b) I (racemate) /

F

,, 225 H H C2H5 H CN CF(CH3)2 loge: 2.47 b) W (racemate) F

226 H H C2H5 H ~ CF(CH3)2 IogP: 2.50 b) (racemate) NC

F

227 H H C2H5 H ~ CF(CH3)-,logP: 2.59 b) / (racemate) ~CN

-~ F

228 H H C2H5 H ~ CF(CH3)2 loge: 2.62 b) / (racemate) O
I

229 H H C2H5 H ~ CF3 loge: 2.93 b) / (racemate) O
I

Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 230 H H C2H5 H ~ C2H5 loge: 2.25 b1 (racemate) O
I

231 H H C2H5 H ~ CHFCH3 loge: 2.30 b~

(racemate) O
I

232 H H C2H5 H ~ CHC1CH3 loge: 2.71 b~

(racemate) O
I

233 H H C2H5 H F CF(CH~)2loge: 3.31 b~

(racemate) -..

234 H H C2H5 H ~ CF(CH3)2loge: 3.52 b~

(racemate) 235 H H C2H5 H ~ CF3 loge: 3.79 b~

(racemate) Le A 32 685-Foreign countries Ex. R~ R2 R3 R4 Ar Z Physical data and stereo-No. chemical specifications 236 H COC2H5 C2H5 H ~H3 CF(CH3)2 loge: 3.77 b>

(racemate) 237 H COC2H5 C2H5 H \ F CF(CH3)2 loge: 3.65 b>

( / (racemate) ,,...

F

238 H COC2H5 C2H5 H F CF(CH3)2 loge: 3.32 - b>

(racemate) The loge values given in Table 1 were determined in accordance with EEC
Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) using a reversed-phase column (C 18). Temperature: 43°C.
(a) Mobile phases for the determination in the acidic range: 0.1% aqueous phosphoric .~~ acid, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - the corresponding test results are marked with a) in Table 1.
(b) Mobile phases for the determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90%
acetonitrile - the corresponding test results are marked with b) in Table 1.
Calibration was carned out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known loge values (determination of the loge values by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.

Le A 32 685-Forei~~n countries Starting materials of the formula (II):
Example (II-I) HMI HMI CzHs H~N~N~N~O / CH3 x HCI
H H H

.-.
A mixture, ground in a mortar, of 12 g (52 mmol) of (R,S)-1-ethyl-2-(3,5-dimethyl-phenoxy)-ethylamine hydrochloride (racemic) and 4.3 g (52 mmol) of cyano-guanidine (dicyanodiamide) is heated in a round-bottomed flask ("neat", i.e.
without addition of a diluent) to 160°C. The resulting melt is kept at this temperature for approximately 30 minutes, with magnetic stirring. After slight cooling, the melt, which is still warm, is dissolved in 70 ml of methanol, and the solvent is then carefully distilled off under water pump vacuum.
This gives 16.2 g (100% of theory) of 1-[1-(3,5-dimethyl-phenoxymethyl)-propyl]-biguanide hydrochloride (racemate) as a solid product.
-..
Analogously to Example (II-1), it is also possible to prepare, for example, the compounds of the formula (II) or their hydrochlorides listed in Table 2.
H~N H~N R' (II) R ~ j~ ~ O
N N N ~ ~Ar R' H H R°

Le A 32 685-Foreign countries Table 2: Examples of the compounds of the formula (II) - (hydrochlorides) Ex. No. RI R2 R3 R4 Ar Physical data and stereochemical specifications II-2 H H C2H5 H ~ (amorphous) / (racemate) JET
II-4 H H C~HS H
/
C~
i II-5 H H C2H5 ' H
/
C~
II-6 H H C2H5 H ~H3 II-8 H H C~HS H

II-9 H H C2H5 H ~ (amorphous) / (racemate) Le A 32 685-Foreien countries Ex. No. RI R2 R3 R4 Ar Physical data and stereochemical specifications CzHs II-11 H H C~HS H
y"""' CH(CH3)2 II-12 H H C~HS H
OMe F
Il-14 H H C2H5 H
/
-...
N(CH3)z II-15 H H C2H5 H ~H3 /
'CI
CI

/
CI

Le A 32 685-Forei;~n countries Ex. No. R 1 R2 R3 R4 Ar Physical data and stereochemical specifications 'F
F
II-19 H H C2H5 H ~ onne "..~ OMe II-20 H H C~HS H
/
C

II-21 H H n-C~H~ H ~
/
II-22 H H n-C;H~ H

..-..
II-23 H H i-C3H~ H
/
II-24 H H i-C3H~ H
/

II-25 H H i-C3H~ H
/

Le A 32 685-Foreign countries Starting materials of formula (VII):
Example (VII-1) CzHs ~ 'O / x HCI
HZN-Step 1 r~
CzHs ~ /O
HO

A mixture of 21.6 g (U.20 mol) of m-cresol, 20.0 g (0.26 mol) of 1,2-epoxy-butane and 0.5 g (0.02 mol) of lithium hydroxide is stirred at 180°C for 20 hours. The mixture is then taken up in approximately double the amount of toluene, washed with 1 N aqueous sodium hydroxide solution and then with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the ,,.... residue is distilled under relatively strongly reduced pressure at a bath temperature of at most about 160°C, the product crystallizing in the condenser.
This gives 28 g (78% of theory) of 1-(3-methyl-phenoxymethyl)-propanol of boiling point 84°C (at 0.4 mbar).
Step 2 CH3 CzHs OZS~ ~O
O

Le A 32 685-Foreign countries 177 g (0.98 mol) of 1-(3-methyl-phenoxymethyl)-propanol are initially charged in 980 ml of pyridine and, at room temperature, 112 g (0.98 mol) of methanesulphonyl chloride are slowly metered in with stirring. The reaction mixture is stirred at 20°C
for 15 hours and subsequently concentrated under water pump vacuum. The residue is taken up in water, acidified with conc. hydrochloric acid and shaken with methylene chloride, and the organic phase is washed with water, dried with sodium sulphate and filtered. 'From the filtrate, the solvent is carefully distilled off under water pump vacuum.
~....
This gives 227 g (90% of theory) of 1-(3-methyl-phenoxymethyl)-propyl methanesulphonate as an oily residue.
1H-NMR (CDCI;, 8): 3.08 ppm (s, S02CH3).
Step 3 CZHS
~ 'O
HZN_ -' CHs 210 g (0.81 mol) of 1-(3-methyl-phenoxymethyl)-propyl methanesulphonate are dissolved in 500 ml of methanol and, in an autoclave, ammonia is metered in at about 100°C and at most about 2 bar until the end of the ammonia uptake becomes evident by the internal pressure measured. The autoclave is opened and the content is then transferred into a round-bottomed flask and concentrated under water pump vacuum, and the residue is admixed with 400 ml of 2N aqueous sodium hydroxide solution and shaken with methylene chloride. The organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is distilled under relatively strongly reduced pressure (bath temperature at most about 150°C).

Le A 32 685-Foreign countries This gives 102 g (72% of theory) of 1-(3-methyl-phenoxymethyl)-propylamine (boiling point: 80°C-82°C at 0.7 mbar).
Step 4 sue.
C2Hs O / x HCI
H2N_ CHs 101 g (0.57 mol) of 1-(3-methyl-phenoxymethyl)-propylamine are initially charged in 1500 ml of tetrahydrofuran and, at from 0°C to 20°C, hydrogen chloride (gas) is introduced with stirring until the solution is saturated. The resulting crystalline product is isolated by filtration with suction.
This gives 83 g (67% of theory) of 1-(3-methyl-phenoxycnethyl)-propylamine hydrochloride.
,,-..
Resolution of the enantiomers of the compounds of the formula (VIII:
CZHs ~ 'O
HZN_ 74.2 g (0.45 mol) of 1-phenoxymethyl-propylamine and 51.5 g (0.50 mol) of methyl methoxyacetate are initially charged in 450 ml of methyl-t-butyl ether. At 40°C, 3.7 g of ~Novozym 435 (from Novo Nordisk) are added, and the mixture is stirred at this temperature for 150 minutes. The mixture is filtered off with suction and the filtrate is admixed with 250 ml of ice-water and 39 ml of conc. hydrochloric acid and stirred for 20 minutes. The organic solvent is then distilled off under water pump vacuum and the residue is, after addition of 200 ml of water, extracted three times with dichloromethane ("extract solution A") Le A 32 685-Foreign countries The aqueous phase is adjusted to pH=13 using 2N aqueous sodium hydroxide solution and extracted with dichloromethane. The extract is dried with sodium sulphate and filtered and the filtrate is concentrated under water pump vacuum, S giving 35.1 g of (S)-1-phenoxymethyl-propylamine (94.5% of theory, ee 88.3%).
The extract solution A is dried with sodium sulphate and filtered; the filtrate is concentrated under water pump vacuum. The resulting crude product (R)-N-methoxyacetyl-1-phenoxymethyl-propylamine is taken up in 300 ml of water and ,.-60 ml of cone hydrochloric acid and heated under reflux at the boil for 20 hours. The mixture is extracted with dichloromethane, the extract is dried with sodium sulphate and filtered and the filtrate is concentrated under water pump vacuum, giving 30.7 g of (R)-I-phenoxymethyl-propylamine (79.5% of theory, 93.2% ee).
As described in the specific examples above, it is analogously also possible to prepare, for example, the compounds of the formula (VII) listed in Table 3 below.

(VII) HZN ~Ar Ra Table 3: Examples of the compounds of the formula (VII) Ex. No. R3 R4 Ar Product description VII-2 C2H5 H ~ racemate: b.p.: 75C/1 mbar R enantiomer: [a] D
= -24.0 S enantiomer: [aJD
= +23.9 VII-3 C~HS H ~ racemate: amorphous R enantiomer: [a] p = -20.9 CI

Le A 32 685-Foreien countries Ex. No. R3 R4 Ar Product description S enantiomer: [a] D = +17.1 °
VII-4 C2H5 H \
/

\
/
VII-ti C2H5 H \ racemate: b.p.: 88°C/0.3 mbar / hydrochloride: m.p.: 130°C
CI
VII-7 C~HS H CH3 I\
VII-8 C2H5 H \ racemate: b.p.: 88°C/1.1 mbar /
.-.

VII-9 C2H5 H \ racemate: b.p.: 88°C/0.16 mbar / hydrochloride: m.p.: 85°C
CzHs /
CH(CH3)z Le A 32 685-Foreign countries Ex. No. R3 R4 Ar Product description VII-11 C2H5 H \
/

VII-12 C2H5 H \ racemate: b.p.: 81°C/0.8 mbar / hydrochloride: m.p.: 140°C
F
w,., VII-13 C2H5 H \
N(CH3)z VII-14 C2H5 H \ CH3 racemate: b.p.: 88°C-90°C/
/ 0.9 mbar VII-15 C2H~ H CH3 w~. ~ /

VII-16 C2H5 H \
/
CI
VII-17 C2H5 H \
/
CI
CI

Le A 32 685-Foreign countries Ex. No. R3 R4 Ar Product description -F
F
VII-19 C2H5 H ~ OCH3 ,.-,.
~..

Le A 32 685-Foreign countries Amendment to Table 1:
Examples 26a and 26 f The two optical isomers (enantiomers) contained in the racemate described under Example 26 in Table 1 above have also been prepared individually as such:
a) R enantiomer - IogP: 2.86 (at pH 7.5);
b) S enantiomer - IogP: 2.86 (at pH 7.5).
Use examples:
In the use examples described below, the known compound of the formula (A) was used as comparative substance:
NHZ
N ~ N CH3 w j~ ~ O CH3 HsC N N ~ \ (A) N-[2-(3,S-Dimethyl-phenoxy)-1-methyl-ethyl]-6-( 1-fluoro-1-methyl-ethyl)-1,3,5-triazine-2,4-diamine - known from EP 411153.

Le A 32 685-Foreign countries Example A
Pre-emergence test Solvent: S parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 I of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated controls.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Example 1, 2, 3, 4, 5, 6, 37 and 38 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize (cf. Table A).
"ai." = active ingredient o o°o a .-..
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v i~ ~
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s ~ O O
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O
n. do a. '-' a \ /

U
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v ~ 00 o ~ Z=
z z a' U Z Z= N Z
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Q
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U

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V
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n ,rte.. U
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a. do a ... = U
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z= =z cz. . ~ °Q., W Z~ Z Z
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Q ~' ~ a. I U
Z
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c~
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z=
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E-~ Q G, Le A 32 685-Forei~~ countries Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants of a height of 5 - 15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied 1 S per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
f-..
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Example 1, 2, 3, 4, S, 6, 37 and 38 show strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize and wheat (cf. Table B).

a\

cd c~

w a, s~ o ,n o, U

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U

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N
V

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a. b0 a. ~

Q

c~
Z
.... ~ U
c ~ ~ U
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U
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per. W Z ~~ Z Z~ Z
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o . o Z ~, Z
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b O ~ ~ ~ Z Z
a. ...r O 7G
00 O ~ C U
Z Z
N
M
Q ~ _~ ~ U
.U
-a I E~ Q a, C
c~ a, a3 a>
o 0 O
o a.
cG
~.
c~
~,.. C
c~
a~
~.
' N
O

N
U 4.
.- O
Q.
d .w\
M
U
c z M
~,.. a~ Z=
o n, .N _ ~O N ~Z
fso. ~ x Z~~ Z
' ~ O ~W
O O-O
N U
M ~ U yes., Q ~ O.
E-~ Q

cd ~, c~ a, U n°., ~s U

a~

N

O
W
r~
CV r~U- O

L
CC
_O v7 U tt, _ O
a. bD
a. "
Q
,tee U

z z=
_ b o N ~, N
.T. ~ CCS
Z Z
W
4~1 ~ Q. w Z-\p '--' O .
!V ~ U
c~
<y' O ~ ~ U
Q Gr

Claims (8)

claims

1. Substituted aryloxyalkylaminotriazines of the general formula (I) in which R1 represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, R2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkyl-carbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, R3 represents optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 2 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R4 represents hydrogen or alkyl having 1 to 4 carbon atoms, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, where the possible heterocyclyl groupings are preferably selected from the following group:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, vitro, halogen, in each case optionionally hydroxyl, cyano or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, dialkylamino, alkylcarbonyl-amino, alkylsulphonylamino, bis-alkylcarbonyl-amino, bis-alkyl-sulphonyl-amino, N-alkyl-N-alkylcarbonyl-amino or N-alkyl-N-alkyl-sulphonyl-amino having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogeno-alkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, and Z represents halogen, represents in each case optionally hydroxyl-, cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxy-carbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents optionally cyano-, halogen- or C1-C4-alkyl substituted cycloalkyl having 3 to 6 carbon atoms.

2. Compounds of the formula (I) according to Claim 1, characterized in that R1 represents hydrogen or represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy- substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, R2 represents hydrogen, represents formyl, or represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxy-carbonyl or ethoxycarbonyl, R3 represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclo-pentyl or cyclohexyl, R4 represents hydrogen or methyl, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, ' where the possible heterocyclyl groupings are preferably selected from the following group:
furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, carbamoyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- or chlorine-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, dimethylamino, diethylamino, acetylamino, propionylamino, methylsulphonylamino, ethylsulphonylamino, bis-acetyl-amino, bis-methylsulphonyl-amino, N-methyl-N-acetyl-amino or N-methyl-N-methylsulphonylamino, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy or tri-fluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- or chlorine-substituted methylenedioxy or ethylenedioxy, and Z represents fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy, n-, i-, s- or t-butoxy-, methylthio-, ethylthio, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propyl-sulphonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propyl-sulphonyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

3. Compounds of the formula (I) according to Claim 1, characterized in that R1 represents hydrogen or represents in each case optionally cyano-, fluorine-, methoxy- or ethoxy-substituted methyl or ethyl, R2 represents hydrogen, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl or propionyl, R3 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, R4 represents hydrogen, Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are in each case preferably selected from the following group:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, in each case optionally fluorine- or chlorine-substituted acetyl, propionyl, n- or i-butyroyl, carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethyl-thio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propyl-sulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoro-methyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, di-fluoromethoxy- or trifluoromethoxy- substituted phenyl or phenoxy, and in each case optionally fluorine-or chlorine-substituted methylene-dioxy or ethylenedioxy, and Z represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or i-propyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

4. Process for preparing compounds of the formula (I) according to Claim 1, characterized in that (a) aryloxyalkylbiguanides of the general formula (II) in which R1, R2, R3, R4 and Ar are as defined in Claim 1, - and/or acid adducts of compounds of the general formula (II) - are reacted with alkoxycarbonyl compounds of the general formula (III) Z-CO-OR' ~~(III) in which Z is as defined in Claim 1 and R' represents alkyl, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that (b) substituted halogenotriazines of the general formula (IV) in which R3, R4, Ar and Z are as defined above and X represents halogen, are reactced with nitrogen compounds of the general formula (V) in which, R1 and R2 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that (c) substituted aminotriazines of the general formula (VI) in which R1, R2 and Z are as defined above and Y1 represents halogen or alkoxy, are reacted with aryloxyalkylamines of general formula (VII) in which Ar, R3 and R4 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or that (d) to prepare compounds of the formula (I) in which R2 is different from hydrogen, aryloxyalkylaminotriazines of the general formula (Ia) in which R1, R3, R4, Ar and Z are as defined above, are reacted with alkylating or acylating agents of the general formula (VIII) Y2-R2~~~ (VIII) in which R2 is as defined above, except for hydrogen, and Y2 represents halogen, -O-R2 or -O-CO-R2, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and further conversions within the scope of the above definition of substituents are carried out, if appropriate, by customary methods on the compounds of the general formula (I) obtained according to processes described under (a), (b), (c) or (d).

5. Herbicidal compositions, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.

6. Use of compounds of the formula (I) according to Claim 1 for controlling undesirable vegetation.

7. Method for controlling weeds, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on the weeds or their habitats.

8. Process for preparing herbicidal compositions, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.