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AU2047399A - Substituted aryloxy alkyl amino triazines - Google Patents

Substituted aryloxy alkyl amino triazines Download PDF

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Publication number
AU2047399A
AU2047399A AU20473/99A AU2047399A AU2047399A AU 2047399 A AU2047399 A AU 2047399A AU 20473/99 A AU20473/99 A AU 20473/99A AU 2047399 A AU2047399 A AU 2047399A AU 2047399 A AU2047399 A AU 2047399A
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AU
Australia
Prior art keywords
substituted
cyano
ethyl
fluorine
enantiomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
AU20473/99A
Inventor
Markus Dollinger
Mark Wilhelm Drewes
Rolf Kirsten
Stefan Lehr
Andreas Lender
Randy Allen Myers
Hans-Jochem Riebel
Uwe Stelzer
Katharina Voigt
Yukiyoshi Watanabe
Ingo Wetcholowsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Bayer CropScience KK
Original Assignee
Bayer AG
Nihon Bayer Agrochem KK
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Filing date
Publication date
Application filed by Bayer AG, Nihon Bayer Agrochem KK filed Critical Bayer AG
Publication of AU2047399A publication Critical patent/AU2047399A/en
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

- 1 Substituted aryloxyalkylaminotriazines The invention relates to novel substituted aryloxyalkylaminotriazines, to processes for their preparation and to their use as herbicides. 5 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. 10 This invention, accordingly, provides the novel substituted aryloxyalkylamino triazines of the general formula (I) R N R2 N N R () Z 11 N N O 0 I 4 Ar H R 15 in which
R
1 represents hydrogen or represents optionally hydroxyl-, cyano-, halogen- or C I-C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms, 20 R 2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C 1
-C
4 -alkoxy-substituted alkyl, alkylcarbonyl or alkoxy carbonyl having in each case 1 to 6 carbon atoms in the alkyl groups,
R
3 represents optionally hydroxyl-, cyano-, halogen- or Cl-C 4 -alkoxy-sub 25 stituted alkyl having 2 to 6 carbon atoms or represents optionally cyano-, halogen- or C I-C 4 -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, -2
R
4 represents hydrogen or alkyl having I to 4 carbon atoms, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, 5 where the possible heterocyclyl groupings are preferably selected from the following group: furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, 10 benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group: 15 hydroxyl, cyano, carbamoyl, thiocarbanoyl, 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-, C 1
-C
4 alkyl-, C 1
-C
4 -halogenoalkyl-, C 1
-C
4 -alkoxy- or C 1
-C
4 -halogenoalkoxy-sub 25 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-, 30 halogen-, C 1
-C
4 -alkoxy-, C 1
-C
4 -alkyl-carbonyl-, C 1
-C
4 -alkoxy-carbonyl-,
C
1
-C
4 -alkylthio-, C I-C 4 -alkylsulphinyl- or C 1
-C
4 -alkylsulphonyl-substituted -3 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
-C
4 -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms. 5 The novel substituted aryloxyalkylaminotriazines of the general formula (I) are obtained when (a) aryloxyalkylbiguanides of the general formula (II) 10 H N H , N R 3 N N N Ar I I I R H H in which 15 RI, R 2 , R 3 , R 4 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) 20 Z-CO-OR' (III) in which 25 Z is as defined above and R' represents alkyl, -4 if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, when 5 (b) substituted halogenotriazines of the general formula (IV) x N N R3 Z N N Ar H 10 in which
R
3 , R 4 , Ar and Z are as defined above and X represents halogen, 15 are reacted with nitrogen compounds of the general formula (V) R , R2 N (V) H 20 in which,
R
1 and R 2 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence 25 of a diluent, -5 or when (c) substituted aminotriazines of the general formula (VI) 1 2 R N-R N N (VI) 5 Z N Y in which RI, R 2 and Z are as defined above and 10 Y1 represents halogen or alkoxy, are reacted with aryloxyalkylamines of the general formula (VII)
R
3
H
2 N O Ar 15 R4 in which Ar, R 3 and R 4 are as defined above, 20 if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or when 25 -6 (d) to prepare compounds of the formula (I) in which R 2 is different from hydrogen, aryloxyalkylaminotriazines of the general formula (Ia) 5 R NH N N R 3 Z N NO Ar (Ia) H R 4 in which 10 RI, R 3 , R 4 , Ar and Z are as defined above, are reacted with alkylating or acylating agents of the general formula (VIII) Y2-R2 (VIII) 15 in which
R
2 is as defined above, except for hydrogen, and 20 Y 2 represents halogen, -O-R 2 or -O-CO-R 2 , if appropriate in the presence of reaction auxiliary and if appropriate in the presence of a diluent, 25 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).
-7 The novel substituted aryoxyalkylaminotriazines of the general formula (I) have strong and selective herbicidal activity. 5 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 10 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. 15 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 R 2 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 R 3 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 -8 represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
R
4 represents hydrogen or methyl, 5 Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, where the possible heterocyclyl groupings are preferably selected from the 10 following group: furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, 15 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, 25 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-, 30 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- -9 butoxy, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- or chlorine-substituted methylenedioxy or ethylenedioxy, 5 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-, 10 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 15 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 20 ("preferable"), particular emphasis is given to the following groups: (A) the compounds of the formula (1) in which R 1 , R 2 , R 3 , R 4 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; 25 (B) the compounds of the formula (I) in which R 1 , R 2 , R 3 , R 4 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. 30 The invention relates in particular to compounds of the formula (I) in which - 10 R 1 represents hydrogen or represents in each case optionally cyano-, fluorine-, methoxy- or ethoxy-substituted methyl or ethyl,
R
2 represents hydrogen, or represents in each case optionally cyano-, fluorine-, 5 chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl or propionyl,
R
3 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy substituted ethyl, n- or i-propyl, 10 R 4 represents hydrogen, Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are in each case preferably selected from the 15 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-, 25 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, 30 and -11 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 5 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. 10 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 R 1 , R 2 , R 3 , R 4 and Z are as defined above and Ar represents in each case optionally substituted phenyl or naphthyl, 15 where the possible substituents are as defined above, with the proviso that the substituents of the carbon atom to which R 3 is attached are arranged in the R configuration; (B') the compounds of the formula (I), in which R 1 , R 2 , R 3 , R 4 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 R 3 is attached are arranged in the S configuration. 25 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. 30 - 12 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. 5 Group 1
NH
2 N' N
C
2
H
5 Z <N N OI 1 H (a: racemates, b: R enantiomers, c: S enantiomeres) 10 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 15 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 20 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, 25 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- -13 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 5 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 10 NH2 N' N C 2 H F Z<N <N 0 / (1-2) H (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 3 NH2 NJ N C 2 H CI Z N O (1-3) H 20 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
- 14 Group 4 NH2 N N C 2 H Br H (1-4) (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 5
NH
2 N <N C 2 H
NO
2 Z N (1-5) H 10 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 6 NH2 N N C 2 H
CH
3 Z<N<N O (1-6)
H
- 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 7
NH
2 N N C 2 H
CF
3 I i (1-7) H (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 8 NH2 N: N C 2 H OCH 3 (1-8) H 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -16 Group 9 NH 2 NJ N C 2 H OCHF 2 I (1-9) H 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 10 10 NH 2 NJ N C 2 H OCF 3 (1-10) H (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 11 N: N C 2 H OC 2
H
5 ZN'N O
H
- 17 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 12 NH 2 N-: N C 2 H SCH Z<N<N O (1-12) H (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 13 NH2 N - N C 2
H
5
N(CH
3
)
2 Z N N (1-13) H 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 - 18 Group 14
NH
2 N-k N C 2 H N(C2H) Z~N~<N 0(1-14) H 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 15 10
NH
2 N N C2
H
3 C NeS0 2
CH
3 Z NO (1-15) H (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 16 NH2 N N
C
2
H
5 <NKN 0 F (1-16) H ! -19 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Groupe 17
NH
2 N) N
C
2
H
5 Z N N(1-17) H 10 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 18 15 NH 2 N) N
C
2
H
5 Z N) N 0 Br H (a: racemates, b: R enantiomers, c: S enantiomers) 20 Z has here, for example, the meanings given above in group 1.
- 20 Group 19
NH
2 N N
C
2
H
5 Z N> N 0 NO 2 (1-19) H 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 20 10
NH
2 N N
C
2
H
5 NOCH0) H (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 21
NH
2 N) N
C
2
H
5 Z<N<N 0 CF 3 (1-21) H "" -21 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 22 NH 2 N) N
C
2
H
5 Z N)NN O OCH 3 (1-22) H 10 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 23 15 NH2 N) N C 2
H
5 Z N N (1-23) H (a: racemates, b: R enantiomers, c: S enantiomers) 20 Z has here, for example, the meanings given above in group 1.
- 22 Group 24
NH
2 N N C 2
H
5 Z N N
-
(1-24) Z N CI 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 25 10 NH 2 N- N
C
2 H 1N (I-25) H N B (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 26 NH2 NA N
C
2 H Z N (1-26)
NO
2 - 23 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 27
NH
2 N: N
C
2
H
5 Z N> C 0 (1-27) H ON' 'CH 3 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 28 NH2 N N
C
2
H
5 ZC (1-28) H O N .C 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -24 Group 29
NH
2 N: N C 2 H z<0(1-29) H
OCH
3 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 30 10 NH2 N) N
C
2 H z (1-30) H
OCHF
2 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 31 NH2 N) N
C
2 H I I N! N) (1-31) H O
OCF
3 - 25 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 32 NH2 N : N
C
2
H
5 Z<N 0(1-32)
OC
2
H
5 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 33 NH 2 N~ N C 2
H
5 W~N OA (1-33) H N.IC 15
OCH(CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 - 26 Group 34 NH2 N N
C
2
H
5 z N0(1-34)
SCH
3 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 35 10
NH
2 NJ N
C
2 H z N N(1-35)
SOCH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 36 NH2 N N
C
2 H Z N N(1-36)
SO
2
CH
3 - 27 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 37 N': N CAH Z~N> N 0CI (1-37) H N O CI (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 38 NH2 NJ N
C
2 H ZI N <N 0 CI H (1-38) 15 CI (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -28 Group 39 NH 2 N' N C 2
H
5 CI Z N<O C (1-39) H b"'CI (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 40 N H2 N: N C 2 H CI Z <N N O H (1-40) 10 CI (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 41 NH2 N: N
C
2 H Z Br H (1-41) Br -29 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 42
NH
2 N) N C 2 H Z <N N O0 F - I H (1-42) CI (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 43
NH
2 N) N
C
2 H Z<N KN 0 7 Br H (1-43) 15 F (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
-30 Group 44
NH
2 N. N
C
2 H Z <N N 0 F I I H (1-44)
CH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 45 NH2 N: N
C
2 H 0 F H .(1-45) 10
C
2
H
5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 46 NH2 N N
C
2
H
5 0 F I | H (1-46)
F
-31 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 47 NH2 N) N
C
2 H H (1-47)
CH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 48 NH2 N N
C
2 H Z N 'N O C 2
H
5 H (1-48)
C
2 H 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
- 32 Group 49 NH2 NJ N
C
2
H
5 Z <N<N 0
CH
3 H (1-49) OMe (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 50 NH2 N N
C
2
H
5 ZNAN O
CH
3 H (1-50) 10
C
2
H
5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 51 NH2 N: N
C
2 H Z0N N O
CF
3 H (1-51)
CF
3 - 33 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 52 NH 2 N) N
C
2
H
5 Z <N N O CI I | H (1-52) OMe (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 53 NH2 Nj N
C
2 H Z 7 OMe I I H (1-53) OMe 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
- 34 Group 54
NH
2 N. N C 2 H Z N<N 0
OC
2
H
5 H (1-54)
OC
2
H
5 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 55 10 NH2 N : N C 2
H
5 Z N)NN 0 I (1-55) H (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 56
NH
2 N N
C
2 H Z N )N 0 H (1-56)
C
2
H
-35 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 57 NH2 N) N
C
2
H
5 H (1-57)
OC
2
H
5 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 58 NH2 N) N
C
2 H H (1-58) 15
OCH(CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
- 36 Group 59
NH
2 NJ N
C
2
H
5 ZI N N O H (1-59)
CH(CH
3
)
2 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 60 10 NH 2 NJ N
C
2 H Z <NAN O H (1-60)
CH(CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1.
-37 Group 61
NH
2 N- N
C
2 H ZANAN O H
OCHF
2 (1-61) (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 62
NH
2 NJ N C 2 H Z <N N O H (1-62) 10 OCF 3 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 63 NH2 N5 N
C
2 H ZANAN O I I H (1-63)
SO
2
CH
3 -38 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 64
NH
2 N) N C 2 H 50 H (1-64)
N(CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 65 NH2 N N
C
2 H ZI N N O H (1-65) 15
N(C
2
H
5
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1.
-39 Group 66 NH2 N: N
C
2 H H (1-66)
NHSO
2
CH
3 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 67 10 NH2 NJ N
C
2
H
5 Z N<N 0 H (1-67)
NHCOCH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1.
-40 Group 68 NH2 N) N
C
2 H Z <N<N O H (1-68) H3C
NSO
2
CH
3 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 69 10 NH2 N) N C2H Z <N'KN 0 H (1-69)
H
3 C NsCOCH 3 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1.
-41 Group 70 NH2 N : N C 2
H
5 ZANAN O H (1-70)
N(SO
2
CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 71 NH2 N) N
C
2 H Z N N 0 (1-71) 10 C 2
H
5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 72 NH2 NJ N
C
2 H Z NN 0(1-72) HC(3
CH(CH
3
)
2 -42 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 73 NH2 N: N
C
2
H
5 Z<NCKN 0(1-73) H N CAH (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 74 NH2 N: N
C
2 H z(1-74) H N"O 15
OCH
5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -43 Group 75
NH
2 N : N C 2
H
5 (1-75)
N(CH
3
)
2 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 76 10 NJ. N C 2
H
5 (1-76) H
N(C
2
H
5
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) 15 Z has here, for example, the meanings given above in group 1. Group 77 NH2 N-: N C 2 H Z(1-77) H
N(C
2
HS)
2 -44 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 78 NH2 N) N
C
2
H
5 Z)NNKN 01-78) H 7g
NHSO
2
CH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 79 NH2 N: N
C
2 H H 79 15
N(SO
2
CH
3
)
2 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -45 Group 80
NH
2 N: N C 2 H Z<N <N O H
NCH
3 (1-80) N
SO
2
CH
3 5 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 81 10 NH2 N N
C
2
H
5 ZN N 0 z% (1-81) H
COOC
2 H (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 82 NH2 N) N
C
2 H z N N(1-82) HC C H CO0CH(CH 3
)
2 -46 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 83 NH2 N: N
C
2 H Z <N 0(1-83)
C(CH
3
)
3 (a: racemates, b: R enantiomers, c: S enantiomers) 10 Z has here, for example, the meanings given above in group 1. Group 84 HN CH3 N N C 2 H Z<N KN O (1-84) H N 15 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 20 -47 Group 85 HN C2
H
5 N' N
C
2
H
5 (1-85) H (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 86
CH
3 N ,CH 3 N: N
C
2 H (1-86) H 10 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 87 CH3 O- N N N
C
2 H (1-87)
H
-48 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 Group 88
NH
2 N N CH(CH 3
)
2 Z N' N 0 (1-88) H 10 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. Group 89 15
C
2 H 0~ N
C
2
H
5 Z~N~N 0(1-89) H HONN (a: racemates, b: R enantiomers, c: S enantiomers) 20 Z has here, for example, the meanings given above in group 1.
-49 Group 90 NH2 N: N C 2
H
5 CH 3 Z <N<N O H (1-90)
CH
3 (a: racemates, b: R enantiomers, c: S enantiomers) 5 Z has here, for example, the meanings given above in group 1. Group 91
NH
2 N) N
C
2
H
5 Z> N<N O
CH
3 H (1-91) 10 CH 3 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 15 Group 92 N) N
C
2 H H F (1-92)
F
- 50 (a: racemates, b: R enantiomers, c: S enantiomers) Z has here, for example, the meanings given above in group 1. 5 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: HH, NH 2 0 OCH H N N C 2
H
5
C
2 + H, 0-- N N C2
CF
3 N N N H H HI
F
3 C" N N 10 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 15 scheme: CI NHC2 H S CHH2NC2 H N N C 2
H
5 2 NE N C 2
H
5 F3C N ON-HCI F3C<NANO HH Using, for example, 2-amino-4-methoxy-6-trifluoromethyl-1,3,5-triazine and 20 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: -51 NH 2 CA NH 2 NA N + O N N C H
F
3 N OC H 2 N K -HOCH 3 F3CNN<NO Using, for example, 2-amino-4-(1-phenoxymethyl-propylanino)-6-trifluoromethyl 1,3,5-triazine and acetyl chloride as starting materials, the course of the reaction in 5 the process (d) according to the invention can be illustrated by the following formula scheme: CH HQ HH NH 2 O N ' 0 CIO~ N N C2s N F ''ZNj C FaC N O - HCI F3C N 10 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', R 2 , R 3 , R 4 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 15 invention, as being preferred or as being particularly preferred for RI, R 2 , R 3 , R 4 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, 20 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, -52 sulphuric acid, methanesulphonic acid, benzenesulphonic acid and p-toluene sulphonic acid. The aryloxyalkylbiguanides of the general formula (H) are obtained when substituted 5 aryloxyalkylamines of the general formula (VII)
R
3
H
2 N O'Ar in which 10
R
3 , R 4 and Ar are as defined above, - and/or acid adducts of compounds of the general formula (VH), such as, for example, the hydrochlorides 15 are reacted with cyanoguanidine ("dicyanodiamide") of the formula (IX) H , N HN N (IX) H H 20 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). 25 The aryloxyalkylamines of the general formula (VH) required as precursors for this purpose are known and/or can be prepared by processes known per se (cf. Acta Pol.
- 53 Pharm. 53 (1996), 47-52 - quoted in Chem. Abstracts 126:46897; Angew. Chem. 106 (1994), 1041-1043; Bull. Soc. Chim. Beig. 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 5 355351; EP 601486; ZA6903772; Preparation Examples). The formula (II) 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 10 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. 15 The starting materials of the formula (III) are known chemicals for synthesis. The formula (IV) 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), R 3 , R 4 , Ar and Z 20 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
3 , R 4 , Ar and Z; X preferably represents fluorine or chlorine, in particular chlorine. 25 The starting materials of the general formula (IV) 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). 30 The substituted halogenotriazines of the general formula (IV) are obtained when corresponding dihalogenotriazines of the general formula (X) - 54 N N (X) Z N ' 1 'X in which 5 X and Z are as defined above and XI represents halogen, 10 are reacted with substituted aryloxyalkylamines of the general formula (VII)
R
3
H
2 N O'Ar in which 15
R
3 , R 4 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 20 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 25 compounds of the formula (I). In the formula (VI), R 1 , R 2 and Z preferably or in particular have those meanings which have already been mentioned above, in - 55 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 1 , R 2 and Z; YI preferably represents fluorine, chlorine, methoxy or ethoxy, in particular chlorine or methoxy. 5 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 aryloxyalkylamines 10 further to be used as starting materials in the process (c) according to the invention. In the formula (VII), R 3 , R 4 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 3 , R 4 and Ar. 15 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). 20 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), RI, R 3 , R 4 Ar and Z preferably or in particular have those meanings which have already been mentioned above, in 25 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 1 , R 3 , R 4 Ar and Z. As novel substances, the starting materials or the general formula (Ia) form part of 30 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.
-56 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 (VIII) provides a general definition of the alkylating or acylating agents 5 further to be used as starting materials in the process (d) according to the invention. In the formula (VIII), R 2 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 R 2 , except for hydrogen; Y 2 preferably represents fluorine, chlorine, 10 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. 15 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 20 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 25 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 30 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- -57 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). 5 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; 10 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; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; 15 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. 20 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. 25 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. 30 In carrying out the processes according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also - 58 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 5 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 10 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: 15 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. 25 Monocotyledonous weeds of the genera: 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, Alopecurus 30 and Apera.
- 59 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 5 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 10 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. 15 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. 20 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. 25 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, 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 30 solvents as auxiliary solvents. Suitable liquid solvents are essentially the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and -60 chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, 5 methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water. Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous 10 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 15 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. 20 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 25 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, 30 copper, cobalt, molybdenum and zinc.
-61 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 5 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 10 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, 15 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, 20 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, 25 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 30 acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), -62 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, 5 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, 10 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, 15 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. 20 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 25 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 30 emergence of the plants. They can also be incorporated into the soil before sowing.
-63 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. 5 The preparation and use of the active compounds according to the invention can be seen from the following examples.
- 64 Preparation Examples: Example 1
NH
2 N N C 2
H
5 O CH3
F
3 C N N 0 H
CH
3 (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), 1.3 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 10 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. 15 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; logP: 3.77 b). Analogously to Example 1, and in accordance with the general description of the 20 preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below. R11 R2 N N N R () 0, Z N N Ar
H
- 65 Table 1: Examples of the compounds of the formula (I) Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 2 H H C 2
H
5 H CH 3 (amorphous) (racemate)
CF
3 3 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate) logP: 3.03 b)
CF
3 4 H H C 2
H
5 H N CH 3
CH
3 (amorphous) (racemate)
CH
3 logP: 1.74 a) 5 H H C 2
H
5 H s CH 3
C
2
H
5 (amorphous) (racemate) CH, logP: 3.05 b) 6 H H C 2
H
5 H C 3
H
7 -i (amorphous) (racemate) logP: 3.51 b)
CF
3 7 H H C 2
H
5 H N CH 3
C
3
H
7 -i (amorphous) (racemate)
CH
3 8 H H C 2
H
5 H CH 3 (amorphous) (racemate)
C
2
HS
- 66 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 9 H H C 2
H
5 H HO CH 3 (amorphous) (racemate)
C
2
H
5 10 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate)
C
2
H
5 11 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate)
C
2
H
5 12 H H C 2
H
5 H Br Y C2H5 (amorphous) (racemate)
C
2
H
5 13 H H C 2
H
5 H Br CH 3 (amorphous) (racemate)
C
2
H
5 14 H H C 2
H
5 H CF 3 (amorphous) (racemate) CI 15 H H C 2
H
5 H CI CH 3 (amorphous) (racemate)
CI
- 67 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 16 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate) CI 17 H H C 2
H
5 H H H 3
CHFCH
3 (amorphous) (racemate) cH 3 logP: 3.16 b) 18 H H C 2
H
5 H CH c CF(CH 3
)
2 (amorphous) (racemate)
CH
3 logP: 3.53 b) 19 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate) logP: 3.01 b)
CF
3 20 H H C 2
H
5 H CF(CH 3
)
2 (amorphous) (racemate) logP: 3.34 b)
CF
3 21 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate) logP: 2.70 b)
CH
3 22 H H C 2
H
5 H CF(CH 3
)
2 (amorphous) (racemate) logP: 3.04 b)
CH
3 - 68 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 23 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate) logP: 2
.
6 4 b)
CH
3 24 H H C 2
H
5 H CH 3 (amorphous) (racemate) logP: 2.25 b)
CH
3 25 H H C 2
H
5 H CF 3 (amorphous) (racemate) logP: 3.36 b)
CH
3 26 H H C 2
H
5 H CF(CH 3
)
2 (amorphous) (racemate) logP: 2.87 b) F 27 H H C 2
H
5 H CF 3 (amorphous) (racemate) logP: 3.18 b) F 28 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate) logP: 2
.
5 6 b) F 29 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate) logP: 2.52 b)
F
- 69 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 30 H H C 2
H
5 H c yCH (amorphous) (racemate) logP: 2.98 b) F 31 H H C 2
H
5 H (amorphous) (racemate) logP: 2.80 b) F 32 H H C 2
H
5 H OMe C 2
H
5 m.p.: 75*C (racemate) OMe 33 H H C 2
H
5 H OMe Br C 2 H (amorphous) (racemate) OMe logP: 3.24 b) 34 H H C 2
H
5 H OMe CHFCH 3 m.p.: 82*C (racemate) OMe logP: 2.45 b) 35 H H C 2
H
5 H OMe CF(CH 3
)
2 (amorphous) (racemate) OMe logP: 2.74 b) 36 H H C 2
H
5 H OMe CF 3 m.p.: 92*C (racemate) OMe logP: 3.08 b) 37 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate) 38 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate) - 70 Ex. R 1
R
2
R
3
R
4 Ar Z Physical data No. and stereo chemical specifications 39 H COCH 3
C
2
H
5 H CHFCH 3 m.p.: 126*C (racemate) 40 H H C 2
H
5 H CF 3 m.p.: 100*C (racemate) 41 H H C 2
H
5 H CF 3 (amorphous) (racemate) CI 42 H H C 2
H
5 H CF 3 (amorphous) (S enantiomer) CI 43 H H C 2
H
5 H CF 3 (amorphous) (R enantiomer) 44 H H C 2
H
5 H CF 3 (amorphous) (S enantiomer) 45 H H C 2
H
5 H CF 3 (amorphous) \ (R enantiomer) CI 46 H COCH 3
C
2
H
5 H CF 3 m.p.: 99*C (R enantiomer) - 71 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 47 H COCH 3
C
2
H
5 H CF 3 m.p.: 102*C (S enantiomer) 48 H COCH 3
C
2
H
5 H CF 3 m.p.: 99*C (R enantiomer) C1 49 H COCH 3
C
2
H
5 H CF 3 m.p.: 106*C (S enantiomer) CI 50 H H C 2
H
5 H HO (amorphous)
H
3 C (racemate) CH 3
CF
3 51 H H C 2
H
5 H CH 3 HO CH 3 (amorphous) (racemate)
CH
3 52 H H C 2
H
5 H CH 3 i-C 3
H
7 (amorphous) (racemate) logP: 3.61 b)
CH
3 53 H H C 2
H
5 H CH 3 CI CH 2 CI (amorphous) (racemate) logP: 3.40 b)
CH
3 - 72 Ex. R 1
R
2 R3 R 4 Ar Z Physical data No. and stereo chemical specifications 54 H H C 2
H
5 H CH 3
C
2
H
5 (amorphous) (racemate) logP: 3.08 b)
CH
3 55 H H C 2
H
5 H CH 3
CF(CH
3
)
2 (amorphous) racematee) - logP: 3.48 b)
CH
3 56 H H C 2
H
5 H CH 3
CF
3 (amorphous) (racemate) logP: 3.79 b)
CH
3 57 H H C 2
H
5 H C C 2
H
5 logP: 1.79 a) (racemate) -73 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 58 H H C 2
H
5 H CH 3 CkyCH 3 logP: 2.69 a) (racemate) 59 H H C 2
H
5 H CH 3 logP: 1.84 a) (racemate) 60 H H C 2
H
5 H CH 3 Br CH 3 logP: 2.78 a) (racemate) 61 H H C 2
H
5 H CH 3 HO Y CH 3 logP: 1.58 a) (racemate) 62 H H C 2
H
5 H ., CH 3
CH
2 0CH 3 logP: 1.65 a) (racemate) 63 H H C 2
H
5 H CH 3
CH
2 OH logP: 1.44 a) (racemate) 64 H H C 2
H
5 H CF(CH 3
)
2 logP: 1.90 a) (S enantiomer) 65 H COCH 3
C
2
H
5 H CF(CH 3
)
2 logP: 3.06 a) (S enantiomer) 66 H COC 2
H
5
C
2
H
5 H CF(CH 3
)
2 (amorphous) (S enantiomer) 67 H COC 2
H
5
C
2
H
5 H CF 3 (amorphous) (S enantiomer) - 74 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 68 H H C 2
H
5 H CI CF 3 logP: 4.12 b) (racemate) CI 69 H H C 2
H
5 H C1 CF(CH 3
)
2 logP: 3.83 b) (racemate) C 70 H H C 2
H
5 H C1 logP: 3 .80 b) 1A (racemate) CI 71 H H C 2
H
5 H C1 CI 02Hs logP: 4.31 b) (racemate) C 72 H H C 2
H
5 H C1 Br Y C 2
H
5 (amorphous) (racemate) C1 73 H H C 2
H
5 H C1 Br CH3 (amorphous) (racemate) CI 74 H H C 2
H
5 H CH 3 CI CH3 logP: 3.21 b) (racemate) - 75 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 75 H H C 2
H
5 H CH 3
C
2
H
5 logP: 2.71 b) (racemate) 76 H H C 2
H
5 H CH 3
CF
3 logP: 3.44 b) (racemate) 77 H H C 2
H
5 H CH 3 Br O CH 3 logP: 3.34 b) (racemate) 78 H H C 2
H
5 H CH 3 HO Y CH3 logP: 2.27 b) I (racemate) 79 H H C 2
H
5 H C1 C 2
H
5 m.p.: 79*C (racemate) C1 80 H H C 2
H
5 H CI CF 3 m.p.: 118*C (racemate) C1 81 H H C 2
H
5 H CI CHFCH 3 m.p.: 101*C (racemate) 82 H H C 2
H
5 H C1 CI CH 3 (amorphous) (racemate) C1 83 H H C 2
H
5 H C1 CI C 2 H (amorphous) (racemate) - 76 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 84 H H C 2
H
5 H C1 Br CH 3 (amorphous) I (racemate) 85 H H C 2
H
5 H C1 C 2
H
5 (amorphous) (racemate) 86 H H C 2
H
5 H Cl CH(CH 3
)
2 (amorphous) (racemate) 87 H H C 2
H
5 H Cl CI cH 3 (amorphous) (racemate) 88 H H C 2
H
5 H Cl CF 3 (amorphous) (racemate) 89 H H C 2
H
5 H CI CF(CH 3
)
2 logP: 3.04 b) (racemate) 90 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate)
OCH
3 91 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.74 b) (racemate)
OCH
3 - 77 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 92 H H C 2
H
5 H CF 3 m.p.: 110*C (racemate)
OCH
3 93 H H C 2
H
5 H -.. , Br C 2 H (amorphous) (racemate)
OCH
3 94 H H C 2
H
5 H (amorphous) (racemate)
OCH
3 95 H H C 2
H
5 H Br..>< CH 3 (amorphous) (racemate)
OCH
3 96 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate)
CH(CH
3
)
2 97 H H C 2
H
5 H CI CH 2 CI (amorphous) (racemate)
CH(CH
3
)
2 98 H H C 2
H
5 H CH(CH 3
)
2 (amorphous) (racemate)
CH(CH
3
)
2 - 78 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 99 H H C 2
H
5 H ci CH 3 (amorphous) (racemate)
CH(CH
3
)
2 100 H H C 2
H
5 H CH 2 0CH 3 (amorphous) (racemate)
CH(CH
3
)
2 101 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate)
CH(CH
3
)
2 102 H H C 2
H
5 H C 2
H
5 (amorphous) (racemate)
CH
3 103 H H C 2
H
5 H CIyCH 3 (amorphous) (racemate)
CH
3 104 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.13 a) (racemate)
CH
3 105 H H C 2
H
5 H CHFCH 3 (amorphous) (racemate)
CH
3 106 H H C 2
H
5 H CH 2
OCH
3 (amorphous) (racemate)
CH
3 107 H H C 2
H
5 H F CH 3 (amorphous) (racemate) - 79 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 108 H H C 2
H
5 H F CH 2 0CH 3 (amorphous) (racemate) 109 H COC 2
H
5
C
2
H
5 H F CF(CH 3
)
2 m.p.: 94*C (racemate) 110 H COC 2
H
5
C
2
H
5 H F CH 3 m.p.: 114*C (racemate) 111 H COC 2
H
5
C
2
H
5 H F CHFCH 3 (amorphous) (racemate) 112 H H C 2
H
5 H CH 3
CF(CH
3
)
2 logP: 3
.
12 b) (racemate) 113 H H C 2
H
5 H CH 3 Cl CH 3 (amorphous) (racemate)
CH
3 114 H H C 2
H
5 H CH 3 HOyCH 3 (amorphous) (racemate)
CH
3 115 H H C 2
H
5 H CF(CH 3
)
2 logP: 2
.
7 7 b) (racemate) - 80 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 116 H COCH 3
C
2
H
5 H CF(CH 3
)
2 (amorphous) (racemate) 117 H COC 2
H
5
C
2
H
5 H CF(CH 3
)
2 (amorphous) (racemate) 118 H COC 2
H
5
C
2
H
5 H CHFCH 3 (amorphous) (racemate) 119 H H C 2
H
5 H CI CH 3 logP: 2.85 b) (racemate) 120 H COC 2
H
5
C
2
H
5 H CF 3 logP: 3.08 b) (racemate) 121 H COCH 3
C
2
H
5 H CINCH 3 logP: 2.86 b) (racemate) 122 H COC 2
H
5
C
2
H
5 H CIy CH: logP: 2.86 b) (racemate) 123 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.76 b) (R enantiomer) 124 H H C 2
H
5 H CHFCH 3 logP: 2.43 b) (R enantiomer) 125 H COCH 3
C
2
H
5 H CF(CH 3
)
2 (amorphous) (R enantiomer) - 81 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 126 H COC 2
H
5
C
2
H
5 H CF(CH 3
)
2 (amorphous) (R enantiomer) 127 H COC 2
H
5
C
2
H
5 H CHFCH 3 (amorphous) (R enantiomer) 128 H H C2H5 H F C 2
H
5 logP: 2.43 b) 0. C/ (racemate)
H
2 129 H H C 2
H
5 H F H 3 C logP: 3.34 b)
C
2
H
5 (racemate) 130 H H C 2
H
5 H F CHF 2 logP: 2.67 b) (racemate) 131 H COCH 3
C
2
H
5 H F CF(CH 3
)
2 logP: 3.20 b) (racemate) 132 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.76 b) racematee)
CH
5 133 H H C 2
H
5 H CHFCH 3 logP: 3.41 b) racematee)
CH
5 134 H H C 2
H
5 H C 2
H
5 logP: 3.38 b) racematee)
CH
5 - 82 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 135 H H C 2
H
5 H C1 ECH3 logP: 3.85 b) (racemate)
CH
5 136 H H C 2
H
5 H CHFCH 3 logP: 2.26 a) (racemate) 137 H H C 2
H
5 H C 2
H
5 logP: 1.79 a) (racemate) 138 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.24 a) (racemate) 139 H COCH 3
C
2
H
5 H C1 CHFCH 3 (amorphous) (racemate) 140 H H C 2
H
5 H F CF(CH 3
)
2 (amorphous) F (racemate) 141 H H C 2
H
5 H F CH 2 0CH 3 (amorphous) F (racemate) 142 H H C 2
H
5 H -I F CF 3 (amorphous) F (racemate) 143 H H C 2
H
5 H .. aF CH(CH 3
)
2 (amorphous) F (racemate) - 83 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 144 H H C 2
H
5 H F ClrCH3 (amorphous) (racemate) 145 H H C 2
H
5 H F CHFCH 3 (amorphous) (racemate) 146 H H C 2
H
5 H CH 3
CF(CH
3
)
2 (amorphous) (racemate) F 147 H H C 2
H
5 H CH 3 C25 (amorphous) (racemate) F 148 H H C 2
H
5 H CH 3 CF3 (amorphous) (racemate) 149 H H C 2
H
5 H CH CHFCH 3 (amorphous) (racemate) F 150 H H C 2
H
5 H .- F CF(CH 3 )2 logP: 3.12 b) (racemate) F 151 H H C2H5 H F CH2OCH3 logP: 2.37 b) (racemate)
F
- 84 Ex. R 1
R
2 R3 R4 Ar Z Physical data and stereo No. chemical specifications 152 H H C 2
H
5 H ,,qF Cl CH 3 logP: 3.21 b) racematee) F 153 H H C 2
H
5 H F CHFCH 3 logP: 2.78 b) racematee) F 154 H H C 2
H
5 H CH 3
C
2
H
5 logP: 2.88 b) CH3 O C/ racematee) 3
H
2 155 H H C 2
H
5 H ,,a CH 3
CH
2 0CH 3 logP: 2.60 b) (racemate) CH 3 156 H H C 2
H
5 H CH 3
CHFCH
3 logP: 3.07 b) racematee)
CH
3 157 H H C 2
H
5 H CH 3
CF(CH
3
)
2 logP: 3.43 b) racematee)
CH
3 158 H H C 2
H
5 H CH 3
C(CH
3
)
3 logP: 4.35 b) racematee)
CH
3 - 85 Ex. RI R 2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 159 H H C 2
H
5 H OCH 3
CF(CH
3
)
2 logP: 2.57 b) racematee) 160 H H C 2
H
5 H OCH 3
CF
3 logP: 2.86 b) racematee) 161 H H C 2
H
5 H OCH 3
CHFCH
3 logP: 2.24 b) (racemate) 162 H H C 2
H
5 H OCH 3
C
2
H
5 logP: 2.22 b) (racemate) 163 H H C 2
H
5 H OCH 3 Cl yrCH3 logP: 2.65 b) racematee) 164 H H C 2
H
5 H OCH 3
C
2
H
5 logP: 2.13 b) 0-.. C racematee) 165 H H C 2
H
5 H CI CF(CH 3
)
2 m.p.: 88*C racematee) 166 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.47 b) racematee)
C
2
H
5 - 86 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 167 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.78 b) racematee)
CH(CH
3
)
2 168 H H C 2
H
5 H -, Cl CF(CH 3
)
2 logP: 3.63 b) racematee) C1 169 H COCH 3
C
2
H
5 H CF(CH 3
)
2 logP: 4.08 b) racematee)
CH(CH
3
)
2 170 H COCH 3
C
2
H
5 H N CI CF(CH 3
)
2 logP: 3.90 b) racematee) CI 171 H COCH 3
C
2
H
5 H CI CF(CH 3
)
2 logP: 3.52 b) racematee) 172 H COCH 3
C
2
H
5 H CF(CH 3
)
2 logP: 2.85 a) racematee)
OCH
3 173 H COC 2
H
5
C
2
H
5 H CF(CH 3
)
2 logP: 3.10 a) racematee)
OCH
3 174 H O C 3 Hy-i C 2
H
5 H CF(CH 3
)
2 logP: 3.28 a) racematee)
OCH
3 -87 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 175 H H C 2
H
5 H CH 3
CF
3 (amorphous) (racemate)
CH
3 176 H H C 2
H
5 H CH 3
CF(CH
3
)
2 logP: 2.41 a) (racemate)
CH
3 177 H H C 2
H
5 H CH 3
CHFCH
3 logP: 2.44 a) (racemate)
CH
3 178 H H C 2
H
5 H CH 3
C
2
H
5 logP: 1.92 a) (racemate)
CH
3 179 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.91 b) (racemate) 180 H H C 2
H
5 H CHFCH 3 logP: 3
.
5 2 b) (racemate) - 88 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 181 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.42 b) racematee) 182 H H C 2
H
5 H CHFCH 3 logP: 3.06 b) racematee) 183 H H C 2
H
5 H CF 3 logP: 3.70 b) racematee) 184 H H C 2
H
5 H CH 2
OCH
3 logP: 2.61 b) (racemate) 185 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.41 b) racematee) 186 H H C 2
H
5 H CHFCH 3 logP: 2.44 a) racematee) - 89 Ex. RI R 2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 187 H H C 2
H
5 H CF 3 logP: 3.74 a) (racemate) 188 H H C 2
H
5 H CH 2
OCH
3 logP: 1.90 a) racematee) 189 H H C 2
H
5 H F CF(CH 3
)
2 logP: 2.75 b) racematee) 190 H H C 2
H
5 H F CF 3 logP: 3.03 b) racematee) 191 H H C 2
H
5 H F C 2
H
5 logP: 2.44 b) racematee) 192 H H C 2
H
5 H F CHFCH 3 logP: 2.46 b) racematee) 193 H H C 2
H
5 H F C1 CHa logP: 2.87 b) I- racematee) - 90 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 194 H H C 2
H
5 H C1 CF(CH 3
)
2 logP: 3.05 b) racematee) OCH 195 H H C 2
H
5 H C1 CF 3 logP: 3.32 b) racematee) OCH: 196 H H C 2
H
5 H C1 C 2
H
5 logP: 2.69 b) racematee) OCH: 197 H H C 2
H
5 H OCH 3
CF(CH
3
)
2 logP: 2.70 b) F racematee) 198 H H C 2
H
5 H OCH 3
CF
3 logP: 3
.
0 0 b) 199 H H C2H15 H OCH 3 CF(CH3)2 logP: 2.90 b) racematee)
CH
3 200 H H C 2
H
5 H OCH 3
CF
3 logP: 3.21 b) *--C 3(racemate)
CH
3 -91 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 201 H H C 2
H
5 H OCH 3
C
2
H
5 logP: 2.54 b) (racemate)
CH
3 202 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.13 b) (racemate)
OC
2
H
5 203 H H C 2
H
5 H CH 2 0CH 3 logP: 2.38 b) (racemate)
OC
2
H
5 204 H H C 2
H
5 H CF 3 logP: 3.42 b) (racemate)
OC
2
H
5 205 H H C 2
H
5 H -. CHFCH 3 logP: 2.78 b) (racemate)
OC
2
H
5 206 H H C 2
H
5 H CH 3
CF(CH
3
)
2 logP: 3.43 b)
CH
3 racematee) 207 H H C 2
H
5 H CH 3
CF
3 logP: 3.73 b)
CH
3 (racemate) - 92 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 208 H H C 2
H
5 H CH 3
C
2
H
5 logP: 3.03 b)
CH
3 (racemate) 209 H H C 2
H
5 H CH 3
CHFCH
3 logP: 3.05 b)
CH
3 (racemate) 210 H H C 2
H
5 H CH 3 CI CH 3 logP: 3.53 b)
CH
3 racematee) 211 H H C 2
H
5 H C1 X CH 2 CI logP: 3
.
3 0 b) F (racemate) F 212 H H C 2
H
5 H OCH 3
CF(CH
3
)
2 logP: 1
.
80 b) OCH: (racemate) 213 H H C 2
H
5 H OCH 3
CF
3 logP: 2.77 b) OCHI (racemate) 214 H H C 2
H
5 H F CF(CH 3
)
2 logP: 2.85 b) F (racemate) - 93 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 215 H H C 2
H
5 H F CF 3 logP: 3
.
14 b) F racematee) 216 H H C 2
H
5 H F C 2
H
5 logP: 2.50 b) F racematee) 217 H H C 2
H
5 H F CHFCH 3 logP: 2.55 b) F racematee) 218 H H C 2
H
5 H F C yCH 3 logP: 2.95 b) F racematee) 219 H H C 2
H
5 H OCH 3
CF(CH
3
)
2 logP: 2.61 b) F- racematee) 220 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.80 b) F racematee) 221 H H C 2
H
5 H CF 3 logP: 3.12 b) F racematee) 222 H H C 2
H
5 H C 2
H
5 logP: 2.43 b) F racematee) -94 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 223 H H C 2
H
5 H CHFCH 3 logP: 2.48 b) F racematee) 224 H H C 2
H
5 H ClrCH3 logP: 2.90 b) F racematee) 225 H H C 2
H
5 H CN CF(CH 3
)
2 logP: 2.47 b) racematee) F 226 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.50 b) NC racematee) F 227 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.59 b) CN racematee) F 228 H H C 2
H
5 H CF(CH 3
)
2 logP: 2.62 b) racematee)
CH
3 229 H H C 2
H
5 H CF 3 logP: 2.93 b) racematee)
CH
3 - 95 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 230 H H C 2
H
5 H C 2
H
5 logP: 2.25 b) racematee)
CH
3 231 H H C 2
H
5 H CHFCH 3 logP: 2
.
3 0 b) racematee)
CH
3 232 H H C 2
H
5 H CHClCH 3 logP: 2.71 b) racematee)
CH
3 233 H H C 2
H
5 H F CF(CH 3
)
2 logP: 3.31 b) racematee)
CF
3 234 H H C 2
H
5 H CF(CH 3
)
2 logP: 3.52 b) racematee)
OCF
3 235 H H C 2
H
5 H CF 3 logP: 3.79 b) racematee)
OCF
3 - 96 Ex. R 1
R
2 R3 R 4 Ar Z Physical data and stereo No. chemical specifications 236 H COC 2
H
5
C
2
H
5 H CH 3
CF(CH
3
)
2 logP: 3.77 b) (racemate) 237 H COC 2
H
5
C
2
H
5 H F CF(CH 3
)
2 logP: 3.65 b) (racemate) F 238 H COC 2
H
5
C
2
H
5 H F CF(CH 3
)
2 logP: 3.32 b) (racemate) The logP 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. 5 (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. 10 (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 carried out using unbranched alkan-2-ones (having 3 to 16 carbon 15 atoms) with known logP values (determination of the logP 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.
- 97 Starting materials of the formula (I): Example (II-1) H. H.. N N
C
2 H H<N N 'IN O CH 3 xHCI I I I H H H
CH
3 5 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 10 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-[I1-(3,5-dimethyl-phenoxymethyl)-propyl] 15 biguanide hydrochloride (racemate) as a solid product. Analogously to Example (1-1), 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 3 2 N N N Ar 20 R H H -98 Table 2: Examples of the compounds of the formula (II) - (hydrochlorides) Ex. No. RI R2 R3 R4 Ar Physical data and stereochemical specifications 11-2 H H C 2
H
5 H (amorphous) (racemate) 11-3 H H C 2
H
5 H CI 1-4 H H C 2
H
5 H C1 11-5 H H C 2
H
5 H CI 11-6 H H C 2
H
5 H CH 11-7 H H C 2
H
5 H CH 3 11-8 H H C 2
H
5 H
CH
3 11-9 H H C 2
H
5 H (amorphous) (racemate)
CF
3 - 99 Ex. No. R 1 R2 R3 R4 Ar Physical data and stereochemical specifications 11-10 H H C 2
H
5 H
C
2
H
5 11-11 H H C 2
H
5 H
CH(CH
3
)
2 II-12 H H C 2
H
5 H OMe 11-13 H H C 2
H
5 H F 1-14 H H C 2
H
5 H
N(CH
3
)
2 11-15 H H C 2
H
5 H CH 3
CH
3 11-16 H H C 2
H
5 H C1 Cl 11-17 H H C 2
H
5 H C1
CI
-100 Ex. No. RI R2 R3 R4 Ar Physical data and stereochemical specifications 1-18 H H C 2
H
5 H F F 11-19 H H C 2
H
5 H OMe OMe II-20 H H C 2
H
5 H CI
CH
3 11-21 H H n-C 3
H
7 H 11-22 H H n-C 3
H
7 H
CH
3 11-23 H H i-C 3
H
7 H 11-24 H H i-C 3
H
7 H
CH
3 II-25 H H i-C 3
H
7 H
CF
3 - 101 Starting materials of formula (VII): Example (VII-1)
C
2
H
5
H
2 N xHCI
CH
3 5 Step 1
C
2 H HO
CH
3 A mixture of 21.6 g (0.20 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 10 mixture is then taken up in approximately double the amount of toluene, washed with IN 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. 15 This gives 28 g (78% of theory) of 1-(3-methyl-phenoxymethyl)-propanol of boiling point 84*C (at 0.4 mbar). Step 2
CH
3 C 2 H 20
CH
3 -102 177 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 5 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. 10 This gives 227 g (90% of theory) of 1-(3-methyl-phenoxymethyl)-propyl methanesulphonate as an oily residue. 1 H-NMR (CDCl 3 , 8): 3.08 ppm (s, SO 2
CH
3 ). 15 Step 3
C
2
H
5
H
2 NO
CH
3 210 g (0.81 mol) of 1-(3-methyl-phenoxymethyl)-propy methanesulphonate are 20 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 25 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).
-103 This gives 102 g (72% of theory) of 1-(3-methyl-phenoxymethyl)-propylamine (boiling point: 80*C-82 0 C at 0.7 mbar). Step 4
C
2
H
5
H
2 N x HCI 5
H
3 101 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 10 product is isolated by filtration with suction. This gives 83 g (67% of theory) of 1-(3-methyl-phenoxymethyl)-propylamine hydrochloride. 15 Resolution of the enantiomers of the compounds of the formula (VII):
C
2 H
H
2 N 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 20 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 25 dichloromethane ("extract solution A").
-104 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, 5 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-l-phenoxymethyl-propylamine is taken up in 300 ml of water and 10 60 ml of conc. 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)-1-phenoxymethyl-propylamine (79.5% of theory, 93.2% ee). 15 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.
R
3
H
2 N O Ar (VIl) 20 Table 3: Examples of the compounds of the formula (VH) Ex. No. R 3 R4 Ar Product description VII-2 C 2
H
5 H racemate: b.p.: 75 0 C/1 mbar R enantiomer: [a]D = -24.0' S enantiomer: [a]2 = +23.9* VII-3 C 2
H
5 H racemate: amorphous R enantiomer: [a]2 = -20.9* - 105 Ex. No. R 3 R4 Ar Product description S enantiomer: [a]20 = +17.14 VII-4 C 2
H
5 H
CH
3 VII-5 C 2
H
5 H C1 VII-6 C 2
H
5 H racemate: b.p.: 88*C/0.3 mbar hydrochloride: m.p.: 130*C CI VII-7 C 2
H
5 H CH 3 VII-8 C 2
H
5 H racemate: b.p.: 88*C/1.1 mbar
CF
3 VII-9 C 2
H
5 H racemate: b.p.: 88*C/0.16 mbar hydrochloride: m.p.: 85*C
C
2
H
5 V1-l10 C 2
H
5 H
CH(CH
3
)
2 -106 Ex. No. R 3 R4 Ar Product description VII-1I C 2
H
5 H
OCH
3 VII-12 C2H5 H racemate: b.p.: 81*C/0.8 mbar hydrochloride: m.p.: 140*C F VII-13 C 2
H
5 H
N(CH
3
)
2 VII-14 C 2
H
5 H CH 3 racemate: b.p.: 88*C-90*C/ 0.9 mbar
CH
3 VII-15 C2H5 H CH 3
CH
3 VII-16 C 2
H
5 H C1 CI VII-17 C 2
H
5 H CI
CI
- 107 Ex. No. R 3 R4 Ar Product description VII-18 C 2
H
5 H F F VII-19 C 2
H
5 H q OCH 3
OCH
3 - 108 Amendment to Table 1: Examples 26a and 26 f The two optical isomers (enantiomers) contained in the racemate described under 5 Example 26 in Table 1 above have also been prepared individually as such: a) R enantiomer - logP: 2.86 (at pH 7.5); b) S enantiomer - logP: 2.86 (at pH 7.5). 10 Use examples: In the use examples described below, the known compound of the formula (A) was used as comparative substance:
NH
2 N N
CH
3
H
3 C N N CH (A)
CH
3 H 15 H 3 N-[2-(3,5-Dimethyl-phenoxy)-1 -methyl-ethyl]-6-(1 -fluoro-1-methyl-ethyl)-1,3,5 triazine-2,4-diamine - known from EP 411153.
-109 Example A Pre-emergence test 5 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 10 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 15 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 1 of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in 20 comparison to the development of the untreated controls. The figures denote: 0 % = no effect (like untreated control) 25 100 % = 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). 30 "ai." = active ingredient 00 l 00 o: 0 C-4 1:0 000 000 0 4_ 0 0 0 C 00 0 0 0 U-ZZ 0 0 u 0.0 z >0 Il 03 cn0 0 0 C1C2 0 Cg0 0 cl 0 0 C 0 z 0 u .0 /> C, C.) c0 0 0 C0 00 00 W.) 0 0 0 00 00 to0 Ic~ 0 zz 0 .0 z Zd Z i 0 U0 0 0 0 c0 0 0 00 zz U c'J z Um z
LJ
- 115 Example B Post-emergence test 5 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 10 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 15 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. 20 The figures denote: 0 %= no effect (like untreated control) 100 %= total destruction 25 In this test, for example, the compounds of Preparation Example 1, 2, 3, 4, 5, 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).
o> 0 0 I 0 00 -) 0 IC., C). 00 0 z\ 0 E z-I: CS C N IN,~m 0d 0 00C 0 r000 N0 0) 0 0 r.. 0 00 .0. 00 Z-I z I/ Z" 0 - /zz E. z / C -, 000 In M 00 0 Z) 0 0 00 uC C.) c- 0 0 C0 * 0 0C' 0) CC> tn 0 0 C2 00 = - 0D 00 0 0 0 - -0 0 0l LL I:I= - L > 0.0 zz ,~ zz 0 0) 00 00 UC, 000 00 0 0 0 0 C 00 Il zc 0 cl 0 CU 0 0 0 rn0 0 0 0) Cd 0 C4-4 00 00 0 0=6 E C)) 0a 0
>
_ I SC 0' 0 o C> 00 0-0 ,6 z 00 0l) E 00 u0 * - 0 Cu 0 z iZ 0 .0 IdI

Claims (8)

1. Substituted aryloxyalkylaminotriazines of the general formula (I) R N "IR2 N N R3 (1) z N N O I 4 Ar 5 H R in which R 1 represents hydrogen or represents optionally hydroxyl-, cyano-, 10 halogen- or C 1 -C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms, R 2 represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen- or C 1 -C 4 -alkoxy-substituted alkyl, alkyl 15 carbonyl or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl groups, R 3 represents optionally hydroxyl-, cyano-, halogen- or CI-C4 alkoxy-substituted alkyl having 2 to 6 carbon atoms or represents 20 optionally cyano-, halogen- or C 1 -C 4 -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms, 25 Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, - 125 where the possible heterocyclyl groupings are preferably selected from the following group: furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, 5 oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, and where the possible substituents are in each case preferably selected from the following group: 10 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, alkyl 15 thio, 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-, C 1 20 C 4 -alkyl-, C I-C4-halogenoalkyl-, C 1 -C 4 -alkoxy- or C I-C 4 -halogeno alkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy, and 25 Z represents halogen, represents in each case optionally hydroxyl-, cyano-, halogen-, C 1 -C 4 -alkoxy-, C 1 -C 4 -alkyl-carbonyl-, C 1 -C 4 alkoxy-carbonyl-, C 1 -C 4 -alkylthio-, C 1 -C 4 -alkylsulphinyl- or CI-C4 alkylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxy 30 carbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents optionally -126 cyano-, halogen- or C I-C 4 -alkyl substituted cycloalkyl having 3 to 6 carbon atoms.
2. Compounds of the formula (I) according to Claim 1, characterized in that 5 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, 10 R 2 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, 15 R 3 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, 20 R 4 represents hydrogen or methyl, Ar represents in each case optionally substituted phenyl, naphthyl, tetralinyl or heterocyclyl, 25 where the possible heterocyclyl groupings are preferably selected from the following group: furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, 30 oxazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, pyrrolyl, pyridinyl and pyrimidinyl, -127 and where the possible substituents are in each case preferably selected from the following group: 5 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 10 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 15 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 20 fluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- or chlorine-substituted methylenedioxy or ethylenedioxy, and 25 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 30 sulphinyl-, 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- - 128 or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propyl sulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or 5 cyclohexyl.
3. Compounds of the formula (I) according to Claim 1, characterized in that R 1 represents hydrogen or represents in each case optionally cyano-, 10 fluorine-, methoxy- or ethoxy-substituted methyl or ethyl, R 2 represents hydrogen, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl or propionyl, 15 R 3 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted ethyl, n- or i-propyl, R 4 represents hydrogen, 20 Ar represents in each case optionally substituted phenyl or naphthyl, where the possible substituents are in each case preferably selected from the following group: 25 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 30 chlorine-substituted acetyl, propionyl, n- or i-butyroyl, methoxy carbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethyl thio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propyl- -129 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 5 fluoromethoxy- or trifluoromethoxy- substituted phenyl or phenoxy, and in each case optionally fluorine-or chlorine-substituted methylene dioxy or ethylenedioxy, and 10 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 15 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, 20 characterized in that (a) aryloxyalkylbiguanides of the general formula (II) H N H ' N R 3 N N N Ar (H) R H H R 25 in which RI, R 2 , R 3 , R 4 and Ar are as defined in Claim 1, -130 - and/or acid adducts of compounds of the general formula (II) are reacted with alkoxycarbonyl compounds of the general formula (III) 5 Z-CO-OR' (III) in which Z is as defined in Claim 1 and 10 R' represents alkyl, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, 15 or that (b) substituted halogenotriazines of the general formula (IV) X N N R 3 Z N N ' Ar 20 H R 4 in which R 3 , R 4 , Ar and Z are as defined above and 25 X represents halogen, are reactced with nitrogen compounds of the general formula (V) - 131 R , R 2 N MV H in which, 5 R 1 and R 2 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, 10 or that (c) substituted aminotriazines of the general formula (VI) 1 2 N N N (VI) 15 Z N Y in which R 1 , R 2 and Z are as defined above and 20 YI represents halogen or alkoxy, are reacted with aryloxyalkylamines of general formula (VII) - 132 R 3 H 2 N O Ar in which 5 Ar, R 3 and R 4 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, 10 or that (d) to prepare compounds of the formula (I) in which R 2 is different from hydrogen, 15 aryloxyalkylaminotriazines of the general formula (Ia) R N, N N R3 Z N N Ar (la) H R 4 in which 20 RI, R 3 , R 4 , Ar and Z are as defined above, are reacted with alkylating or acylating agents of the general formula (VIII) 25 Y2-R2 (VIII) - 133 in which R 2 is as defined above, except for hydrogen, and 5 Y 2 represents halogen, -O-R 2 or -O-CO-R 2 , if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, 10 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). 15
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 20 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. 25
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.
AU20473/99A 1997-10-24 1998-10-14 Substituted aryloxy alkyl amino triazines Abandoned AU2047399A (en)

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