CA2381639A1 - Substituted benzoxazoles - Google Patents
Substituted benzoxazoles Download PDFInfo
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- CA2381639A1 CA2381639A1 CA002381639A CA2381639A CA2381639A1 CA 2381639 A1 CA2381639 A1 CA 2381639A1 CA 002381639 A CA002381639 A CA 002381639A CA 2381639 A CA2381639 A CA 2381639A CA 2381639 A1 CA2381639 A1 CA 2381639A1
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- alkyl
- carbonyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The present invention relates to substituted benzoxazoles of general formula (I) wherein R1, R2 and R3 have the meanings cited in claim 1, and Het stands for a 5- or 6-membered heterocycle bonded by nitrogen and having general formulae (II-1) to (II-18). The invention also relates to agents containing such compounds as well as to a method for combating undesired plant growth; the compounds of general formulae (III), (IV) and (V) are used as intermedia te products for the production of the formula (I) compoun ds.
Description
~~50/50571 CA 02381639 2002-02-11 Substituted benzoxazoles The present invention relates to substituted benzoxazoles of the 5 formula I
Het ~ ~ R2 (I) p /N
in which Z is a chemical bond, 0 or S, R1 is hydrogen or halogen, RZ is halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, and R3 is C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-Cq-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-Cg-cycloalkoxy-C1-C4-alkyl, is amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl;
Het ~ ~ R2 (I) p /N
in which Z is a chemical bond, 0 or S, R1 is hydrogen or halogen, RZ is halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, and R3 is C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-Cq-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-Cg-cycloalkoxy-C1-C4-alkyl, is amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl;
is phenyl, phenyl-C1-C4-alkyl, where the phenyl rings may carry one, two or three substituents selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is C3-C8-cycloalkyl, C3-Ce-cycloalkyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl, 3- to 7-membered heterocyclyl-C1-C4-alkyl, where heterocyclyl contains one, two or three heteroatoms selected from oxygen, sulfur and nitrogen atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl and heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C1-C9-hydroxyalkyl, C1-C4-aminoalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy, di(C1-C4-alkyl)amino, C3-C6-alkenyl, C3-C6-alkynyl, C3-C4-alkenyloxy, C3-C4-alkenylthio, C3-C4-alkynyloxy and C3-Cg-alkynylthio;
or, if Z is a chemical bond, R3 may also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-CQ-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered, N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CHZ)n-CH(OH)-CHZ-R9, -(CHz)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CHZ)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1;
Het is an unsaturated, five- or six-membered heterocyclic radical which is attached to the benzoxazole moiety via a nitrogen atom and which is selected from radicals of the formulae II-1 to II-18 ''' 0050/50571 CA 02381639 2002-02-11 ,.
is C3-C8-cycloalkyl, C3-Ce-cycloalkyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl, 3- to 7-membered heterocyclyl-C1-C4-alkyl, where heterocyclyl contains one, two or three heteroatoms selected from oxygen, sulfur and nitrogen atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl and heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C1-C9-hydroxyalkyl, C1-C4-aminoalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy, di(C1-C4-alkyl)amino, C3-C6-alkenyl, C3-C6-alkynyl, C3-C4-alkenyloxy, C3-C4-alkenylthio, C3-C4-alkynyloxy and C3-Cg-alkynylthio;
or, if Z is a chemical bond, R3 may also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-CQ-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered, N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CHZ)n-CH(OH)-CHZ-R9, -(CHz)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CHZ)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1;
Het is an unsaturated, five- or six-membered heterocyclic radical which is attached to the benzoxazole moiety via a nitrogen atom and which is selected from radicals of the formulae II-1 to II-18 ''' 0050/50571 CA 02381639 2002-02-11 ,.
X X
Q R5 \ N' \ X Y N-~N - ~ ~N -N-N
R4 N R4 N R5~ R5, (II-1) (II-2) (II-3) X X X
R5 ~ N ~ R4 Y' \
I N- I 'N- N-RS~iN~ R4, R6 X' X' ~ X' R
(II_4) (II_5) (II-6) i R4.
N R5 ~ N N, i Nw ~~ \ / \ ~N-Y N=N R4, N
(II_7) (II-8) (II_9) R5\ X R5\ X R4 X
N~ N
R4 -~~ N- X N- R4 N
N~ N ~N
X R4 R4"
(II-10) (II-11) (II-12) X Y N R5~ ~ i N%\
~ N N ~ N -R4, N
R4 R4 ~ R4 X .
(II-13) (II-14) (II-15) 5 ~ N~ N
R ~N N~- N\ N- R4' ~ N-~Nv R4,. X
X. R5. R4 X.
(II-16) (II-17) (II-ls) xpedit: ROBIC/BREVETS 4eme 514 845 8705; 05/01/02 12:10; JetFax #287;Page 2/2 ~~~~/50571 CA 02381639 2002-02-11 in which R4, R4' and R4" independently of one another axe hydrogen, amino, C1-C4-alkylamina, di-C1-C~-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamina, halogen, cyano, carboxyl, CL-C6-alkyl, C,_C6_haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-Cg-alkoxy, C1-C6-haloalkoxy, C1-C~-haloalkylthio, C1-Cg-alkoxycarbonyl, C3-C6-alkenyloxy, C3-Cb-alkynyloxy, C1-C6-alkylthio, C~-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C3-Ce-cycloalkyl or C3-C8-cyclaalkyl-Ci-CQ-alkyl;
RS and R5' independently of one another are hydrogen, amino, hydroxyl, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyi, C~-C6-alkynyl, Cl-C6-alkoxycarbonyl, t C3-C8-cyclaalkyl, C3-C$-cycloalkyl-C1-C4-alkyl, phenyl or phenyl-C1-C6-alkyl;
and/or two of the radicals R~, ~t4', R4", R5 and RS' together with the cycle to which they are attached form a 8-, 5-, 5- or 7-membered ring which may be saturated or unsaturated, which rnay contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three radicals selected from the group consisting of C1-C4-alkyl and halogen;
1t6 and R~ independently of one another are hydrogen, Cl-Cg-alkyl, C1-C6-haloalkyl or C3-C6-cyclaalkyl, or together with the carbon atom to which they are attached r,~,.~ form a 4-, 5-, 6- or 7-membered ring which may be W saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three substituents selected from the group consisting of C~,-Cy-alkyl and halogen;
Q in the formula II-1 is O or S, X and X' independently of one another are p or S, and Y is O, S or a group N-RB in which R$ is hydrogen, Cl-C6-alkyl, C1-C6-halaalkyl. ox C3-Cg-cycloalkyl;
and the agriculturally useful salts of the compounds of the formula I.
Moreover, the invention relates to - the use of the compounds I as herbicides, - compositions comprising the compounds I as herbicidally active substances, 5 - methods for controlling undesirable vegetation using the compounds of the formula I, and - compounds of the formulae III, IV, V and X as intermediates for preparing the compounds I.
He ~ ~ R2 ( I I I ) He ~ ~ R2 ( IV ) He ~ ~ R2 (V) He \ / Rz (g) WO 97/08170 describes 3-(benzoxazol-7-yl)- and 3-(benzothiazol-7-yl)-6-(trifluoromethyl)uracils as herbicides.
Further 3-(benzothiazol-7-yl)uracils and their use as herbicides and for the desiccation/defoliation of plants are disclosed in WO 97/08171. WO 97/12886 provides, inter alia, certain 3-benzisoxazol-7-yl-2,4-(1H,3H)pyrimidinediones which are said to have herbicidal and desiccant action. Furthermore, DE-A 197 55 926 discloses benzazol-4-ylpyrimidinediones and the earlier German patent application P 198 52 802.7 discloses derivatives of 3-(benzazol-7-yl)pyrimidinediones.
It is an object of the present invention to provide novel herbicidally active compounds which allow better targeted control of undesirable plants than the compounds of the prior art.
We have found that this object is achieved by the benzoxazole derivatives defined at the outset which have, in the 7-position, a 5- or 6-membered heterocycle, attached via a nitrogen atom.
Furthermore, we have found herbicidal compositions comprising the compounds I and having very good herbicidal action. Moreover, we have found processes for preparing these compositions and methods for controlling undesirable vegetation using the compounds I.
a m ' 005050571 CA 02381639 2002-02-11 Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures. The present invention provides both the pure enantiomers or diastereomers and their mixtures.
Suitable agriculturally useful salts are, especially, the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not adversely affect the herbicidal action of the compounds I. Thus, suitable cations are, in particular, the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion which, if desired, may carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic molecule moieties mentioned in the definition of the substituents R1 to R9 or as radicals on cycloalkyl, phenyl or heterocyclic rings are - like the term halogen - collective terms for individual enumerations of the individual group members. All hydrocarbon chains, i.e. all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenylalkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl moieties can be straight-chain or branched.
Halogenated substituents preferably carry one to five identical ' 050/50571 CA 02381639 2002-02-11 or different halogen atoms. The term halogen denotes in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
- C1-Cq-alkyl: CH3, C2H5, CHZ-C2H5, CH(CH3)2, n-butyl, CH(CH3)-C2H5, CHZ-CH(CH3)2 or C(CH3)3:
- C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, CHzF, CHF2, CF3, CHZC1, CH(C1)2, C(C1)3, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C2F5, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-CZFS, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
- C1-C6-alkyl: a C1-CQ-alkyl radical as mentioned above or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably CH3, CzHg, CH2-C2H5, CH(CH3)2, n-butyl, C(CH3)3.
n-pentyl or n-hexyl;
- C1-C6-haloalkyl: a C1-C6-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, one of the radicals mentioned under C1-C4-haloalkyl, or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, ' 0050/50571 CA 02381639 2002-02-11 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl;
- cyano-C1-C4-alkyl: CH2CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1-(CHZCN)eth-1-yl, 1-(CH2CN)-1-(CH3)-eth-1-yl or 1-(CH2CN)prop-1-yl;
- hydroxy-C1-C4-alkyl: CH20H, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 3-hydroxybut-2-yl, 4-hydroxybut-2-yl, 1-(CHZOH)eth-1-yl, 1-(CH20H)-1-(CH3)-eth-1-yl or 1-(CH20H)prop-1-yl;
- amino-C1-C4-alkyl: CHZNH2, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 1-amino-but-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1-(CHZNHa)eth-1-yl, 1-(CH2NH2)-1-(CH3)-eth-1-y1 or 1-(CH2NH2)prop-1-yl;
hYdroxycarbonyl-C1-C4-alkyl: CHzCOOH, 1-(COOH)ethyl, 2-(COOH)ethyl, 1-(COOH)prop-1-yl, 2-(COOH)prop-1-yl, 3-(COOH)prop-1-yl, 1-(COOH)but-1-yl, 2-(COOH)but-1-yl, 3-(COOH)but-1-yl, 4-(COOH)but-1-yl, 1-(COOH)but-2-yl, 2-(COOH)but-2-yl, 3-(COOH)but-2-yl, 4-(COOH)but-2-yl, 1-(CH2COOH)eth-1-yl, 1-(CH2COOH)-1-(CH3)-eth-1-yl or 1-(CH2COOH)prop-1-yl;
- aminocarbonyl-C1-C4-alkyl: CHZCONHz, 1-(CONHZ)ethyl, 2-(CONHZ)ethyl, 1-(CONH2)prop-1-yl, 2-(CONHZ)prop-1-yl, 3-(CONHZ)prop-1-yl, 1-(CONH2)but-1-yl, 2-(CONH2)but-1-yl, 3-(CONHZ)but-1-yl, 4-(CONH2)but-1-yl, 1-(CONHz)but-2-yl, 2-(CONHZ)but-2-yl, 3-(CONH2)but-2-yl, 4-(CONH2)but-2-yl, 1-(CH2CONH2)eth-1-yl, 1-(CHZCONHZ)-1-(CH3)-eth-1-yl or 1-(CH2CONH2)prop-1-yl;
_ phenyl-C1-C4-alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1-(benzyl)eth-1-yl, 1-(benzyl)-1-(methyl)eth-1-yl or 1-(benzyl)prop-1-yl, preferably benzyl or 2-phenylethyl;
- heterocyclyl-C1-C4-alkyl: heterocyclylmethyl, 1-heterocyclylethyl, 2-heterocyclylethyl, 1-heterocyclylprop-1-yl, 2-heterocyclylprop-1-yl, 3-heterocyclylprop-1-yl, 1-heterocyclylbut-1-yl, 2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl, 4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl, 2-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 4-heterocyclylbut-2-yl, 1-(heterocyclylmethyl)eth-1-yl, 1-(heterocyclylmethyl)-1-(methyl)eth-1-yl or 1-(heterocyclylmethyl)prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclylethyl;
- C1-C4-alkoxy: OCH3, OCzHS, OCHy-C2H5, OCH(CH3)2, n-butoxy, OCH(CH3)-CzH5, OCH2-CH(CH3)2 or C(CH3)3, preferably OCH3, OC2H5 or OCH(CH3)z;
- C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, OCHZF, OCHF2, OCF3, OCHzCl, OCH(C1)Z, OC(C1)3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OCzFS, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCHZ-CzF5, OCFZ-CZFS, 1-(CHZF)-2-fluoroethoxy, 1-(CHZC1)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF2, OCF3, dichlorofluoromethoxy, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
- C1-C6-alkoxy: a C1-C4-alkoxy radical as mentioned above or, for example, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy, preferably OCH3, OC2H5, OCH2-CZH5, OCH(CH3)2, n-butoxy, OC(CH3)3, n-pentoxy or n-hexoxy;
' 0050150571 CA 02381639 2002-02-11 - C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, one of the radicals mentioned under C1-C4-haloalkoxy, or 5-fluoro-1-pentoxy, 5 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
- C1-C4-alkylthio: SCH3, SC2H5, SCHz-C2H5, SCH(CH3)2, n-butylthio, SCH(CH3)-C2H5, SCHZ-CH(CH3)Z or SC(CH3)3, preferably SCH3 or SC2H5;
- C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, SCH2F, SCHF2, SCF3, SCH2C1, SCH(Cl)2, SC(C1)3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthia, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, SC2F5, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoro ro lthio, 2-chloro ro lthio 3-chloro ro lthio P PY P PY . P PY
2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCHz-CZF5, SCFz-CzFs, 1-(CHzF)-2-fluoroethylthio, 1-(CHZC1)-2-chloroethylthio, 1-(CHZBr)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or SCFz-CF2-C2F5, preferably SCHF2, SCF3, dichlorofluoromethylthio, chlorodifluoromethylthio or 2,2,2-trifluoroethylthio;
- C1-C6-alkylthio: a C1-C4-alkylthio radial as mentioned above or, for example, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio, preferably SCH3, SCzHS, SCH2-C2H5, SCH(CH3)2, n-butylthio, SC(CH3)3, n-pentylthio or n-hexylthio;
0U5~~50571 CA 02381639 2002-02-11 1l - C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy - as mentioned above -, i.e., for example, CH2-OCH3, CHZ-OC2H5, n-propoxymethyl, CH2-OGH(CH3)2.
n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CHZ-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(I,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl, preferably CH2-OCH3, CH2-OC2H5, 2-(pCH3)ethyl or 2-(OCZH5)ethyl;
- C1-C4-haloalkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkoxy as mentioned, above, i.e., for example, 2-(OCHFZ)ethyl, 2-(OCF3)ethyl or 2-(OC2F5)ethyl;
- C1-C4-alkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylthio - as mentioned above -, i.e., for example, CHZ-SCH3, CHZ-SC2H5, n-propylthiomethyl, CH2-SCH(CH3)z, n-butylthiomethyl, (1-methylpropylthio)methyl, (2-methylpropylthio)methyl, CH2-SC(CH3)3, 2-(methylthio)ethyl, 2-(ethylthio)ethyl, 2-(n-propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl, 2-(ethylthio)propyl, 2-(n-propylthio)propyl, 2-(1-methylethylthio)propyl, 2-(n-butylthio)propyl, 2-(1-methylpropylthio)propyl, 2-(2-methylpropylthio)propyl, 2-(1,1-dimethylethylthio)propyl, 3-(methylthio)propyl, 3-(ethylthio)propyl, 3-(n-propylthio)propyl, 3-(1-methylethylthio)propyl, 3-(n-butylthio)propyl, 3-(1-methylpropylthio)propyl, 3-(2-methylpropylthio)propyl, 3-(1,1-dimethylethylthio)propyl, 2-(methylthio)butyl, 2-(ethylthio)butyl, 2-(n-propylthio)butyl, 2-(1-methylethylthio)butyl, 2-(n-butylthio)butyl, 2-(1-methylpropylthio)butyl, 2-(2-methylpropylthio)butyl, 2-(1,1-dimethylethylthio)butyl, 3-(methylthio)butyl, 3-(ethylthio)butyl, 3-(n-propylthio)butyl, 3-(1-methylethylthio)butyl, 3-(n-butylthio)butyl, 3-(1-methylpropylthio)butyl, 3-(2-methylpropylthio)butyl, 3-(1,1-dimethylethylthio)butyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(n-propylthio)butyl, 4-(1-methylethylthio)butyl, 4-(n-butylthio)butyl, 4-(1-methylpropylthio)butyl, 4-(2-methylpropylthio)butyl or 4-(1,1-dimethylethylthio)butyl, preferably CHZ-SCH3, CHz-SC2H5, 2-(SCH3)ethyl or 2-(SC2H5)ethyl;
15. - C1-C4-haloalkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylthio as mentioned above, i.e., for example, 2-(SCHFZ)ethyl, 2-(SCF3)ethyl or 2-(SC2F5)ethyl;
- (C1-C4-alkyl)carbonyl: CO-CH3, CO-CZHS, CO-CHZ-C2H5, CO-CH(CH3)2.
n-butylcarbonyl, CO-CH(CH3)-CZHS, CO-CH2-CH(CH3)2 or CO-C(CH3)3, preferably CO-CH3 or CO-CZHS;
- (C1-C4-haloalkyl)carbonyl: a (C1-C4-alkyl)carbonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, CO-CHZF, CO-CHFz, CO-CF3, CO-CHZC1, CO-CH(C1)Z, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C2F5, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO--CH2-CZFS, CO-CF2-CZF5, 1-(CH2F)-2-fluoroethylcarbonyl, 1-(CHZC1)-2-chloroethylcarbonyl, 1-(CHzBr)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CHZCl or 2,2,2-trifluoroethylcarbonyl;
- (C1-C4-alkyl)carbonyloxy: 0-CO-CH3, 0-CO-C2H5, 0-CO-CH2-C2H5, O-CO-CH(CH3)2, 0-CO-CHZ-CH2-C2H5, 0-CO-CH(CH3)-CZHS, 0-CO-CHZ-CH(CH3)2 or 0-CO-C(CH3)3. preferably 0-CO-CH3 or O-CO-CzHS;
- (C1-C4-haloalkyl)carbonyloxy: a (C1-C4-alkyl)carbonyl radical -as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, O-CO-CHZF, O-CO-CHFZ, 0-CO-CF3, O-CO-CHZCl, O-CO~H(C1)2, ~O-C(C1)3, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2.2,2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2-trichloroethylcarbonyloxy, O-CO-C2F5, 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy, 2,2-difluoropropylcarbonyloxy, 2,3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-dichloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy, 3,3,3-trichloropropylcarbonyloxy, O-CO-CH2-CZFS, O-CO-CF2-CzF5, 1-(CHZF)-2-fluoroethylcarbonyloxy, 1-(CHZC1)-2-chloroethylcarbonyloxy, 1-(CHZBr)-2-bromoethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably 0-CO-CF3, O-CO-CHZC1 or 2~2,2-trifluoroethylcarbonyloxy;
- (C1-C4-alkoxy)carbonyl: CO-OCH3, CO-OCzHS, CO-OCHZ-C2H5.
CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CH3)-C2H5, CO-OCH2-CH(CH3)2 or CO-OC(CH3)3, preferably CO-OCH3 or CO-OC2H5;
- (C1-C6-alkoxy)carbonyl: one of the abovementioned (C1-C4-alkoxy)carbonyl radicals or, for example, n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy-C0, 2,2-dimethylpropoxy-C0, 1-ethylpropoxy-CO, n-hexoxy-CO, 1,1-dimethylpropoxy-C0, 1,2-dimethylpropoxy-C0, 1-methylpentoxy-CO, 2-methylpentoxy-C0, 3-methylpentoxy~0, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-CO, 1,2-dimethylbutoxy-CO, 1,3-dimethylbutoxy-CO, 2,2-dimethylbutoxy-C0, 2,3-dimethylbutoxy-CO, 3,3-dimethylbutoxy-CO, 1-ethylbutoxy-C0, 2-ethylbutoxy-CO, 1,1,2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-CO, 1-ethyl-1-methylpropoxy-CO or 1-ethyl-2-methylpropoxy-C0, preferably CO-OCH3, CO-OC2H5, CO-OCHz-CZH5, CO-OCH(CH3)2.
n-butoxy-CO, CO-OC(CH3)3, n-pentoxy-CO or n-hexoxy-CO;
- {C1-C4-alkoxy)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkoxy)carbonyl - as mentioned above -, i.e., for example, CH2-CO-OCH3, CH2-CO-OCzHS, CH2-CO-OCHZ-C2H5, CH2-CO-OCH(CH3)2, n-butoxycarbonylmethyl, CH2-CO-OCH(CH3)-C2H5, CHz-CO-OCHZ-CH(CH3)2, CH2-CO-OC(CH3)3, 1-(CO-OCH3)ethyl, 1-(CO-OCzHS)ethyl, 1-(CO-OCHZ-CzHS)ethyl, 1-[CH(CH3)2]ethyl, l-{n-butoxycarbonyl)ethyl, 1-[1 methylpropoxycarbonyl]ethyl, 1-[2 methylpropoxycarbonyl]ethyl, 2-(CO-OCH3)ethyl, 2-(CO-OC2H5)ethyl, 2-(CO-OCH2-CZHS)ethyl, 2-[CO-OCH(CH3)2]ethyl, 2-(n-butoxycarbonyl)ethyl, 2-[1-methylpropoxycarbonyl]ethyl, 2-[2-methylpropoxycarbonyl]ethyl, 2-[CO-OC(CH3)3]ethyl, 2-(CO-OCH3)propyl, 2-(CO-OC2H5)propyl, 2-(CO-OCHz-C2H5)propyl, 2-[CO--aCH(CH3)2]propyl, 2-(n-butoxycarbonyl}propyl, 2-[1-methylpropoxycarbonyl]propyl, 2-[2-methylpropoxycarbonyl]propyl, 2-[CO-OC(CH3)3]propyl, 3-(CO-OCH3)propyl, 3-(CO-OCZHS)propyl, 3-(CO-OCH2-C2H5)propyl, 3-[CO-OCH(CH3)2]propyl, 3-(n-butoxycarbonyl)propyl, 3-[1-methylpropoxycarbonyl]propyl, 3-[2-methylpropoxycarbonyl]propyl, 3-[CO-OC(CH3)3]propyl, 2-(CO-OCH3)butyl, 2-(CO-OC2H5)butyl, 2-(CO-OCHZ-C2H5)butyl, 2-[CO-OCH(CH3)2]butyl, 2-(n-butoxycarbonyl}butyl, 2-[1_methylpropoxycarbonyl]butyl, 2-[2-methylpropoxycarbonyl]butyl, 2-[CO-OC(CH3)3]butyl, 3-(CO-OCH3)butyl, 3-(CO-OC2H5)butyl, 3-(CO-OCHZ-C2H5)butyl, 3-[CO-OCH(CH3)2]butyl, 3-(n-butoxycarbonyl)butyl, 3-[1-methylpropoxycarbonyl]butyl, 3_[2-methylpropoxycarbonyl]butyl, 3-[CO-OC{CH3}3]butyl, 4-(CO-OCH3)butyl, 4-(CO-OCZHS)butyl, 4-(CO-OCH2-C2H5}butyl, 4-[CO-OCH(CH3)2]butyl, 4-(n-butoxycarbonyl)butyl, 4-[1-methylpropoxycarbonyl]butyl, 4-[2-methylpropoxycarbonyl]butyl or 4-[CO-OC(CH3)3]butyl, preferably CH2-CO-OCH3, CHZ-CO-OC2H5, 1-(CO-OCH3)ethyl or 1-(CO-OC2H5)ethyl;
- (C1-C4-alkylthio)carbonyl: CO-SCH3, CO-SCzHS, CO-SCH2-C2H5, CO-SCH(CH3)2, CO-SCH2CHp-CZHS, CO-SCH(CH3}-CZHS, CO-SCHZ-CH(CH3)2 or CO-SC(CH3)3, preferably CO-SCH3 or CO-SCzHS;
(C1-C4-alkylthio)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkylthio}carbonyl - as mentioned above -, i.e., for example, CHZ-CO-SCH3, CHZ-CO-SC2H5, CH2-CO-SCH2-CZHS, CHZ-CO-SCH(CH3)2, CH2-CO-SCHZCH2-C2H5, CH2-CO-SCH(CH3)-CZHS, CHZ-CO-SCHZ-CH(CH3)2, CH2-CO-SC(CH3)3.
1-(CO-SCH3)ethyl, 1-(CO-SCZHS)ethyl, 1-(CO-SCHZ-CzHS)ethyl, ' X050/50571 CA 02381639 2002-02-11 1-[CO-SCH(CH3)z]ethyl, 1-(CO-SCHZCHz-CZHS)ethyl, 1-[CO-SCH(CH3)-CzHS]ethyl, 1-[CO-SCHz-CH(CH3)z]ethyl, 1-[CO-SC(CH3)3]ethyl, 2-(CO-SCH3)ethyl, 2-(CO-SCzHS)ethyl, 2-(CO-SCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)z]ethyl, 5 2-(CO-SCHzCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)-CZHS]ethyl, 2-[CO-SCHz-CH(CH3)z]ethyl, 2-[CO-SC(CH3)g]ethyl, 2-(CO-SCH3)propyl, 2-(CO-SCZHS)propyl, 2-(CO-SCHZ-CzHS)propyl, 2-[CO-SCH(CH3)z]propyl, 2-(CO-SCH2CHZ-C2H5)propyl, 2-[CO-SCH(CH3)-CZHS]propyl, 2-[CO-SCHz-CH(CH3)z]propyl, 10 2-[CO-SC(CHg)3]propyl, 3-(CO-SCH3)propyl, 3-(CO-SCZHS)propyl, 3-(CO-SCHZ-C2H5)propyl, 3-[CO-SCH(CH3)z]propyl, 3-(CO-SCHZCHZ-CZHS)propyl, 3-[CO-SCH(CH3)-C2H5]propyl, 3-[CO-SCHZ-CH(CH3)z]propyl, 3-[CO-SC(CH3)3]propyl, 2-(CO-SCH3)butyl, 2-(CO-SCZHS)butyl, 2-(CO-SCHz-CZHS)butyl, 15 2-[CO-SCH(CH3)z]butyl, 2-(CO-SCHzCHZ-C2H5)butyl, 2-[CO-SCH(CHg)-C2H5]butyl, 2-[CO-SCHz-CH(CH3)z]butyl, 2-[CO-SC(CH3)3]butyl, 3-(CO-SCH3)butyl, 3-(CO-SCZHS)butyl, 3-(CO-SCHz-CyHS)butyl, 3-[CO-SCH(CH3)z]butyl, 3-(CO-SCHZCHZ-C2H5)butyl, 3-[CO-SCH(CH3)-CZHS]butyl, 3-[CO-SCHZ-CH(CH3)z]butyl, 3-[CO-SC(CH3)3]butyl, 4-(CO-SCH3)butyl, 4-(CO-SCZHS)butyl, 4-(CO-SCHz-CZHS)butyl, 4-[CO-SCH(CH3)z]butyl, 4-(CO-SCH2CHZ-CZHS)butyl, 4-[CO-SCH(CH3)-C2H5]butyl, 4-[CO-SCHz-CH(CH3)z]butyl or 4-[CO-SC(CH3)3]butyl, preferably CHz-CO-SCH3, CHz-CO-SC2H5, 1-(CO-SCH3)ethyl or 1-(CO-SC2H5)ethyl;
- C1-C6-alkylsulfinyl: a C1-C4-alkylsulfinyl radical such as SO-CH3, SO-C2H5, SO-CHz-CZHS, SO-CH(CH3)z, SO-(n-CqHg), SO-CH(CH3)-CZHS, SO-CHz-CH(CH3)z or SO-C(CH3)3, or, for example, SO-(n-C5H11), 1-methylbutyl-SO, 2-methylbutyl-SO, 3-methylbutyl-S0, 2,2-dimethylpropyl-SO, 1-ethylpropyl-S0, n-hexyl-SO, 1,1-dimethylpropyl-SO, 1,2-dimethylpropyl-SO, 1-methylpentyl-S0, 2-methylpentyl-S0, 3-methylpentyl-SO, 4-methylpentyl-S0, 1,1-dimethylbutyl-S0, 1,2-dimethylbutyl-SO, 1,3-dimethylbutyl-S0, 2,2-dimethylbutyl-SO, 2,3-dimethylbutyl-S0, 3,3-dimethylbutyl-SO, 1-ethylbutyl-SO, 2-ethylbutyl-S0, 1,1,2-trimethylpropyl-SO, 1,2,2-trimethylpropyl-S0, 1-ethyl-1-methylpropyl-SO or 1-ethyl-2-methylpropyl-SO, preferably SO--CH3, SO-CzHS, SO-CHZ-CZH5, SO-CH(CH3)2, SO-(ri-CqHg), SO-C(CH3)3, SO-(n-C5H11) or SO-(n-C6H13);
- C1-C4-alkylsulfonyl: SOZ-CH3, SOz-CZHS, SOz-CHZ-CyHS, SOz-CH(CH3)z, n-butylsulfonyl, SOz-CH(CH3)-CzHS, SOz-CHZ-CH(CH3)z or SOz-C(CH3)3, preferably SOz-CH3 or SOz-CzHS;
- C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, SOz-CH2F, SOz-CHFZ, SOz-CF3, SOz-CHzCl, SOz-CH(C1)z, SOz--C(C1)3, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, SOz-C2F5, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, SOz-CHZ-C2F5, SOz--CFZ-CzFS, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably SOz-CH2C1, SOz-CF3 or 2,2,2-trifluoroethylsulfonyl;
- C1-Cs-alkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above or, for example, SOZ-(n-C5H11), 1-methylbutyl-SOz, 2-methylbutyl-SOz, 3-methylbutyl-SOz, 2,2-dimethylpropyl-SOz, 1-ethylpropyl-SOz, n-hexyl-SOz, 1,1-dimethylpropyl-SOz, 1,2-dimethylpropyl-SOz, 1-methylpentyl-SOz, 2-methylpentyl-SOz, 3-meth 1 ent 1-SO , 4-meth 1 ent 1-SO 1 1-dimeth lbut 1-SO
Y P Y z Y P Y 2. ~ Y Y z.
1,2-dimethylbutyl-SOz, 1,3-dimethylbutyl-SOz, 2,2-dimethylbutyl-SOz, 2,3-dimethylbutyl-SOz, 3,3-dimethylbutyl-SOz, 1-ethylbutyl-SOz, 2-ethylbutyl-SOz, 1,1,2-trimethylpropyl-SOz, 1,2,2-trimethylpropyl-SOz, 1-ethyl-1-methylpropyl-SOz or 1-ethyl-2-methylpropyl-SOz, preferably SOz-CH3, SOz-C2H5, SOz-CHZ-CzHS, SOz-CH(CH3)2.
SOz-(n-CqH9)r S02-C(CH3)3, S02-(ri-C5H11) Or SOz-(n-C6H13)i - C1-C4-alkylamino: H3C-NH-, HSCz-NH-, n-propyl-NH-, 1-methylethyl-NH-, n-butyl-NH-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1,1-dimethylethyl-NH-, preferably H3C-NH- or H5Cz-NH-;
- C1-C4-alkylamino-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylamino as defined above, i.e., for example, CHZCHz-NH-CH3, CHzCHz-N(CH3)z, CH2CHz-NH-C2H5 or CH2CHz-N(C2H5)z;
' ~ ~~50/50571 CA 02381639 2002-02-11 - (C1-C4-alkylamino)carbonyl: CO-NH-CH3, CO-NH-C2H5, n-propylamino, CO-NH-CH(CH3)Z, CO-NH-CHzCH2-CZHS, CO-NH-CH(CH3)-C2H5, CO-NH-CHz-CH(CH3)2 or CO-NH-C(CH3)3.
preferably CO-NH-CH3 or CO-NH-CZHS;
- (C1-C4-alkylamino)carbonyl-C1-C4-alkyl: C1-CQ-alkyl which is substituted by (C1-C4-alkylamino)carbonyl as mentioned above, preferably by CO-NH-CH3 or CO-NH-CZHS, as e.g. CH2-CO-NH-CH3, CH2-CO-NH-CzHS, CH2-CO-NH-CH2-C2H5, CH2-CO-NH-CH(CH3)y, CHz-CO-NH-CH2CH2-C2H5, CHZ-CO-NH-CH(CH3)-CZHS, CH2-CO-NH-CHZ-CH(CH3)2, CH2-CO-NH-C(CH3)3, CH(CH3)-CO-NH-CH3, CH(CH3)-CO-NH-CZHS, 2-(CO-NH-CH3)ethyl, 2-(CO-NH-C2H5)ethyl, 2-(CO-NH-CH2-CZHS)ethyl, 2-[CHy-CO-NH-CH(CH3)2]ethyl, 2-(CO-NH-CH2CHz-C2H5)ethyl, 2-[CO-NH-CH(CH3)-C2H5]ethyl, 2-[CO-NH-CHz-CH(CH3)2]ethyl, 2-[CO-NH-C(CH3)3]ethyl, 2-(CO-NH-CH3)propyl, 2-(CO-NH-CzHS)propyl, 2-(CO-NH-CH2-C2H5)propyl, 2-[CH2-CO-NH-CH(CH3)2]propyl, 2-(CO-NH-CH2CH2-CZHg)propyl, 2-[CO-NH-CH(CH3)-C2H5]propyl, 2-[CO-NH-CH2-CH(CH3)2]propyl, 2-[CO-NH-C(CH3)3]propyl, 3-(CO-NH-CH3)propyl, 3-(CO-NH-CZHS)propyl, 3-(CO-NH-CHZ-CzHS)propyl, 3-[CHZ-CO-NH-CH(CH3)2]propyl, 3-(CO-NH-CHZCH2-CzHS)propyl, 3-[CO-NH-CH(CH3)-CzHS]propyl, 3-[CO-NH-CHZ-CH(CH3)2]propyl, 3-[CO-NH-C(CH3)3]propyl, 2-(CO-NH-CH3)butyl, 2-(CO-NH-C2H5)butyl, 2-(CO-NH-CH2-C2Hg)butyl, 2-[CHZ-CO-NH-CH(CH3)2]butyl, 2_(CO-NH-CHyCH2-C2H5)butyl, 2-[CO-NH-CH(CH3)-C2H5]butyl, 2-[CO-NH-CHZ-CH(CH3)y]butyl, 2-[CO-NH-C(CH3)3]butyl, 3-(CO-NH-CH3)butyl, 3-(CO-NH-C2H5)butyl, 3-(CO-NH-CHZ-CZHS)butyl, 3-[CH2-CO-NH-CH(CH3)2]butyl, 3-(CO-NH-CH2CHz-C2H5)butyl, 3-[CO-NH-CH(CH3)-CZHS]butyl, 3_[CO-NH-CHZ-CH(CH3)2]butyl, 3-[CO-NH-C(CH3)3]butyl, 4-(CO-NH-CH3)butyl, 4-(CO-NH-CZHg)butyl, 4-(CO-NH-CH2-C2H5)butyl, 4-[CHZ-CO-NH-CH(CH3)Z]butyl, 4-(CO-NH-CHZCHz-C2H5)butyl, 4-[CO-NH-CH(CH3)-C2H5]butyl, 4-[CO-NH-CHZ-CH(CH3)2]butyl or 4-[CO-NH-C(CH3)3]butyl, preferably CH2-CO-NH-CH3, CHZ-CO-NH-C2H5, CH(CH3)-CO-NH-CH3 or CH ( CH3 )--CO NH-C2H5;
- di(C1-C4-alkyl)amino: N(CH3)Z, N(CZH5)2, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, '. ~ ~ 0~5~~505')1 CA 02381639 2002-02-11 N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino, preferably N(CH3)z or N(CZHS)2:
- di(C1-C4-alkyl)amino-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)amino as mentioned above, i.e., for example, CHZN(CH3)2, CH2N(CyHS)2, N,N-dipropylaminomethyl, N,N-di[CH(CH3)Z]aminomethyl, N,N-dibutylaminomethyl, N,N-di-(1-methylpropyl)aminomethyl, N,N-di(2-methylpropyl)aminomethyl, N,N-di[C(CH3)3]aminomethyl, N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl, N-methyl-N-[CH(CH~)2]aminomethyl, N-butyl-N-methylaminomethyl, N-methyl-N-(1-methylpropyl)aminomethyl, N-methyl-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-methylaminomethyl, N-ethyl-N-propylaminomethyl, N-ethyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl)aminomethyl, N-ethyl-N-[C(CH3)3]aminomethyl, N-[CH(CH3)z]-N-propylaminomethyl, N-butyl-N-propylaminomethyl, N-(1-methylpropyl)-N-propylaminomethyl, N-(2-methylpropyl)-N-propylaminomethyl, N-[C(CH3)3]-N-propylaminomethyl, N-butyl-N-(1-methylethyl)-aminomethyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminomethyl, N-[CH(CH3)y]-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-[CH(CH3)2]aminomethyl, N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methylpropyl)aminomethyl, N-butyl-N-[C(CH3)3]-aminomethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(2-methylpropyl)aminomethyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,N-di(n-propyl)aminoethyl, N,N-di[CH(CH3)2]aminoethyl, N,N-dibutylaminoethyl, N,N-di(1-methylpropyl)aminoethyl, N,N-di(2-methylpropyl)aminoethyl, N,N-di[C(CH3)3]aminoethyl, N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N-[CH(CH3)z]aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N-(1-methylpropyl)aminoethyl, N-methyl-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N-[CH(CH3)z]aminoethyl, N-butyl-N-ethylaminoethyl, N-ethyl-N-(1-methylpropyl)aminoethyl, N-ethyl-N-(2-methylpropyl)aminoethyl, N-ethyl-N-[C(CH3)3]aminoethyl, N-[CH(CH3)z]-N-propylaminoethyl, N-butyl-N-propylaminoethyl, N-(1-methylpropyl)-N-propylaminoethyl, N-(2-methylpropyl)-N-propylaminoethyl, N-[C(CH3)31-N-Propylaminoethyl, N-butyl-N-[CH(CH3)z]aminoethyl, N-[CH(CH3)z]-N-(1-methylpropyl)aminoethyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-[CH(CH3)z]aminoethyl, N-butyl-N-(1-methylpropyl)aminoethyl, N-butyl-N-(2-methylpropyl)aminoethyl, N-butyl-N-[C(CH3)3]aminoethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminoethyl or N-[C(CH3)3]-N-(2-methylpropyl)aminoethyl, in particular N,N~limethylaminoethyl or N,N-diethylaminoethyl;
- di(C1-C4-alkyl)aminocarbonyl: CO-N(CH3)z, CO-N(CzHS), CO-N CH -C H CO-N CH CH
( z z 5)z. [ ( 3)2]2. N.N-dibutylaminocarbonyl, CO-N[CH(CH3)-CzHS]z, CO-N[CHZ-CH(CH3)z]z~ CO-N[C(CH3)3]2~
N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-[C(CH3)3]aminocarbonyl, N-[CH(CH3)z]-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N-(1-methylpropyl)-N-propylaminocarbonyl, N-(2-methylpropyl)-N-propylaminocarbonyl, N-[C(CH3)3]-N-propylaminocarbonyl, N-butyl-N-[CH(CH3)z]aminocarbonyl, N-[CH(CH3)z]-N-(1-methylpropyl)aminocarbonyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-[CH(CH3)2]aminocarbonyl, , 0050/50571 CA 02381639 2002-02-11 N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methylpropyl)aminocarbonyl, N-butyl-N-[C(CH3)3]aminocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, 5 N-[C(CH3)3]-N-(1-methylpropyl)aminocarbonyl or N-[C(CH3)3]-N-(2-methylpropyl)aminocarbonyl, preferably CO-N(CH3)2 or CO-N(CyHS)2:
di(C1-C6-alkyl)aminocarbonyl: one of the abovementioned 10 di(C1-C4-alkyl)aminocarbonyl radicals or, for example, N(CH3)-(n-C5H11)r N(~2H5)-(n-~5H11)~ N(~H2-~zHS)-(n-~5H11)~
N(n-C4Hs)-(n-C5Hli)~ N(n-CSHii)-(n-C5Hii)~ N(n-CsHi3)-(n-CSHii).
N(CH3)-(n-C6H13). N(C2H5)-(n-CsHl3). N(CHz-C2H5)-(n-CsHl3).
N(n-C4H9)-(n-C6H13)i N(n-C5H11)-(n-C6H13) or N(n-C6H13)2:
- di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)phosphonyl such as -PO(OCH3)2, -PO(OC2H5)2, N,N-dipropylphosphonyl, N,N-di(1-methylethyl)phosphonyl, N,N-dibutylphosphonyl, NON-di(1-methylpropyl)phosphonyl, N,N-di(2-methylpropyl)phosphonyl, N,N-di(1,1-dimethylethyl)phosphonyl, N-ethyl-N-methylphosphonyl, N-methyl-N-propylphosphonyl, N-methyl-N-(1-methylethyl)phosphonyl, N-butyl-N-methylphosphonyl, N-methyl-N-(1-methylpropyl)-hos hon 1, N-meth 1-N 2-meth 1 ro 1 hos hon l, P P Y Y -( Y P PY )P P Y
N-(1,1-dimethylethyl)-N-methylphosphonyl, N-ethyl-N-propylphosphonyl, N-ethyl-N-(1-methylethyl)phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl-N-(1-methylpropyl)phosphonyl, N-ethyl-N-(2-methylpropyl)phosphonyl, N-ethyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylethyl)-N-propylphosphonyl, N-butyl-N-propylphosphonyl, N-(1-methylpropyl)-N-propylphosphonyl, N-(2-methylpropyl)-N-propylphosphonyl, N-(1,1-dimethylethyl)-N-propylphosphonyl, N-butyl-N-(1-methylethyl)phosphonyl, N-(1-methylethyl)-N-(1-methylpropyl)phosphonyl, N-(1-methylethyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)phosphonyl, N-butyl-N-(1-methylpropyl)phosphonyl, N-butyl-N-(2-methylpropyl)phosphonyl, N-butyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylpropyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)phosphonyl or N-(l,l-dimethylethyl)-N-(2-methylpropyl)phosphonyl, preferably by -PO(OCH3)2 or -PO(OCZHS)2, i.e., for example, CHZ-PO(OCH3)2.
CHZ-PO(OCZHS)2, CH(CH3)-PO(OCH3)2 Or CH(CH3)-PO(OC2H5)2;
- C3-C6-alkenyl: prop-1-en-1-yl, allyl, 1-rnethylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2r3_dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-,2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, e.g. 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3-dibromoa11y1, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
00'S~/50571 CA 02381639 2002-02-11 - cyano-C3-C6-alkenyl: for example 2-cyanoallyl, 3-cyanoallyl, 4-cyanvbut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl;
- C3-C6-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, preferably prop-2-yn-1-yl;
- C3-C6-haloalkynyl: C3-C6-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, 1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, l,l-difluorobut-2-yn-1-yl, 5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;
- cyano-C3-C6-alkynyl: for example 3-cyanopropargyl, 4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl;
- C3-C4-alkenyloxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkenyloxy such as allyloxy, but-1-en-3-yloxy, but-1-en-4-yloxy, but-2-en-1-yloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, i.e., for example, allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl, in particular 2-allyloxyethyl;
_ C3-C4_alkynyloxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynyloxy such as propargyloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy, but-2-yn-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, i.e., for example, propargyloxymethyl or 2-propargyloxyethyl, in particular 2-propargyloxyethyl;
- C3-C6-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
_ C3-C6-cycloalkylamino: cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino;
- C3-Ce-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
- C3-C8-cycloalkyl-C1-C6-alkyl: for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2-(cyclopropyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl, 2-(cyclohexyl)ethyl, 2-(cycloheptyl)ethyl, 2-(cyclooctyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclobutyl)propyl, 3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 3-(cycloheptyl)propyl, 3-(cyclooctyl)propyl, 4-(cyclopropyl)butyl, 4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)butyl, 4-(cycloheptyl)butyl, 4-(cyclooctyl)butyl, 5-(cyclopropyl)pentyl, 5-(cyclobutyl)pentyl, 5-(cyclopentyl)pentyl, 5-(cyclohexyl)pentyl, 5-(cycloheptyl)pentyl, 5-(cyclooctyl)pentyl, 6-(cyclopropyl)hexyl, 6-(cyclobutyl)hexyl, 6-(cyclopentyl)hexyl, 6-(cyclohexyl)hexyl, 6-(cycloheptyl)hexyl or 6-(cyclooctyl)hexyl;
- C3-C8-cycloalkyloxy-C1-C4-alkyl: cyclopropyloxymethyl, 1-cyclopropyloxyethyl, 2-cyclopropyloxyethyl, 1-cyclopropyloxyprop-1-yl, 2-cyclopropyloxyprop-1-yl, 3-cyclopropyloxyprop-1-yl, 1-cyclopropyloxybut-1-yl, 2-cyclopropyloxybut-1-yl, 3-cyclopropyloxybut-1-yl, 4-cyclopropyloxybut-1-yl, 1-cyclopropyloxybut-2-yl, 2-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 4-cyclopropyloxybut-2-yl, 1-(cyclopropyloxymethyl)eth-1-yl, 1-(cyclopropyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopropylmethyloxy)prop-1-yl, cyclobutyloxymethyl, 1-cyclobutyloxyethyl, 2-cyclobutyloxyethyl, 1-cyclobutyloxyprop-1-yl, 2-cyclobutyloxyprop-1-yl, 3-cyclobutyloxyprop-1-yl, 1-cyclobutyloxybut-1-yl, 2-cyclobutyloxybut-1-yl, 3-cyclobutyloxybut-1-yl, 4-cyclobutyloxybut-1-yl, 1-cyclobutyloxybut-2-yl, 2-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 4-cyclobutyloxybut-2-yl, _ 1-(cyclobutyloxymethyl)eth-1-yl, 1-(cyclobutyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclobutyloxymethyl)prop-1-yl, cyclopentyloxymethyl, 1-cyclopentyloxyethyl, 2-cyclopentyloxyethyl, 1-cyclopentyloxyprop-1-yl, 2-cyclopentyloxyprop-1-yl, 3-cyclopentyloxyprop-1-yl, 1-cyclopentyloxybut-1-yl, 2-cyclopentyloxybut-1-yl, 3-cyclopentyloxybut-1-yl, 4-cyclopentyloxybut-1-yl, 1-cyclopentyloxybut-2-yl, 2-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 4-cyclopentyloxybut-2-yl, 1-(cyclopentyloxymethyl)eth-1-yl, 1-(cyclopentyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopentyloxymethyl)prop-1-yl, cyclohexyloxymethyl, 1-cyclohexyloxyethyl, 2-cyclohexyloxyethyl, 1-cyclohexyloxyprop-1-yl, 2-cyclohexyloxyprop-1-yl, 3-cyclohexyloxyprop-1-yl, 1-cyclohexyloxybut-1-yl, 2-cyclohexyloxybut-1-yl, 3-cyclohexyloxybut-1-yl, 4-cyclohexyloxybut-1-yl, 1-cyclohexyloxybut-2-yl, 2-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 4-cyclohexyloxybut-2-yl, 1-(cyclohexyloxymethyl)eth-1-yl, 1-(cyclohexyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclohexyloxymethyl)prop-1-yl, cycloheptyloxymethyl, 1-cycloheptyloxyethyl, 2-cycloheptyloxyethyl, 1-cycloheptyloxyprop-1-yl, 2-cycloheptyloxyprop-1-yl, 3-cycloheptyloxyprop-1-yl, 1-cycloheptyloxybut-1-yl, 2-cycloheptyloxybut-1-yl, 3-cycloheptyloxybut-1-yl, 4-cycloheptyloxybut-1-yl, 1-cycloheptyloxybut-2-yl, 2-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 4-cycloheptyloxybut-2-yl, 1-(cycloheptyloxymethyl)eth-1-yl, 1-(cycloheptyloxymethyl)-1-(CH3)eth-1-yl, 1-(cycloheptyloxymethyl)prop-1-yl, cyclooctyloxymethyl, 1-cyclooctyloxyethyl, 2-cyclooctyloxyethyl, 1-cyclooctyloxyprop-1-yl, 2-cyclooctyloxyprop-1-yl, 3-cyclooctyloxyprop-1-yl, 1-cyclooctyloxybut-1-yl, 2-cyclooctyloxybut-1-yl, 3-cyclooctyloxybut-1-yl, 4-cyclooctyloxybut-1-yl, 1-cyclooctyloxybut-2-yl, 2-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 4-cyclooctyloxybut-2-yl, 1-(cyclooctyloxymethyl)eth-1-yl, 1-(cyclooctyloxymethyl)-1-(CH3)eth-1-yl or 1-(cyclooctyloxymethyl)prop-1-yl, in particular C3-C6-cycloalkoxymethyl or 2-(C3-C6-cycloalkoxy)ethyl.
3- to 7-membered heterocyclyl is to be understood as meaning both saturated, partially or fully unsaturated and aromatic heterocycles having one to three heteroatoms selected from a group consisting of one to three nitrogen atoms, one to two oxygen atoms and one or two sulfur atoms. Preference is given to saturated heterocycles, and among these in particular to those having one or two heteroatoms selected from oxygen and sulfur.
The saturated heterocycles may contain a carbonyl or. thiocarbonyl ring member.
~~5~/50571 CA 02381639 2002-02-11 Examples of saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: ' oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2-yl, oxetan-3-yl, 5 thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 10 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, 15 tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, 20 piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, 25 hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and hexahydro-1,4-diazepin-2-yl.
Saturated 5-or 6-membered N-bonded heterocyclyl is, for example,:
pyrrolidin-1-yl, tetrahydropyrazol-1-yl, piperidin-1-yl, hexahydropyrimidin-1-yl, piperazin-1-yl and morpholin-1-yl.
With respect to the use of the compounds of the formula I
according to the invention as herbicides, the variables Z, R1, RZ
and R3 preferably have the following meanings, in each case on their own or in combination:
Z is 0, S, or a single bond, in particular a single bond;
R1 is hydrogen, fluorine or chlorine;
RZ is halogen, in particular fluorine or chlorine, or cyano;
R3 is C1-C4-alkyl, C1-C4-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-Cq-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-Cq-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl;
is phenyl which may carry a substituent selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is saturated C3-C~-cycloalkyl, 3- to 7-membered saturated heterocyclyl which contains one, two or three heteroatoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member;
or, if Z is a chemical bond, R3 can also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CHz)n-CH(OH)-CHZ-R9 , -(CH2)n-CH(halo)-CHz-R9, -(CHZ)n-CHZ-CH(halo)-R9, -(CHZ)n-CH=CH-R9 or -(CHZ)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1.
Examples of particularly preferred radicals R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, propen-3-yl, propargyl, 2-buten-1-yl, 3-buten-1-yl, methoxymethyl, methoxyethyl, cyanomethyl, 2-cyanoethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, 2-chloroethyl, 2-chloromethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, dimethylaminocarbonylmethyl, hydroxymethyl, aminomethyl, methylaminomethyl, dimethylaminomethyl, diethylaminomethyl, 2-(methylamino)ethyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, (methylthio)carbonylmethyl, (ethylthio)carbonylmethyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxiran-2-yl, oxetan-2-yl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, oxepan-2-yl, thiiran-2-yl, thiethan-2-yl, tetrahydrothiophen-2-yl, tetrahydrothiopyran-2-yl, thiepan-2-yl, oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-3-yl, oxepan-3-yl, thiethan-3-yl, tetrahydrothiophen-3-yl, tetrahydrothiopyran-3-yl, thiepan-3-yl, tetrahydropyran-4-yl, oxepan-4-yl, tetrahydrothiopyran-4-yl, thiepan-4-yl, 2-oxocyclopropyl, 2-oxocyclobutyl, 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxocycloheptyl, 2-thioxocyclopropyl, 2-thioxocyclobutyl, 2-thioxocyclopentyl, 2-thioxocyclohexyl, 2-thioxocycloheptyl, 2-oxooxetan-3-yl, 2-oxothiethan-2-yl, 2-oxotetrahydrothien-3-yl, 2-oxotetrahydrothiopyran-3-yl, 2-oxothiepan-3-yl, 2-oxotetrahydrofuran-3-yl, 2-oxotetrahydropyran-2-yl, 2-oxooxepan-2-yl, 2-thioxooxetan-3-yl, 2-thioxothiethan-2-yl, 2-thioxotetrahydrothien-3-yl, 2-thioxotetrahydrothiopyran-3-yl, 2-thioxothiepan-3-yl, 2-thioxotetrahydrofuran-3-yl, 2-thioxotetrahydropyran-2-yl, 2-thioxooxepan-2-yl, -CHZ-CH(C1)-COOH, -CH2-CH(C1)-COOCH3, -CH2-CH(C1)-COOCHZCH3, -CH2-CH(C1)-COOCH(CH3)z, -CHZ-CH(C1)-COOCH2CH(CH3)2, -CH2-CH(C1)-COOCH(CH3)CH2CH3, -CHz-CH(C1)-COOC(CH3)3, -CHZ-CH(C1)-C00-n-C3H~, -CH2-CH(C1)-COO-n-CqH9, -CHZ-CH(Br)-COOH, -CHZ-CH(Br)-COOCH3, -CH2-CH(Br)-COOCH2CH3, -CH2-CH(Br)-COOCH(CH3)2.
-CH2-CH(Br)-COOCHZCH(CH3)Z, -CH2-CH(Br)-COOCH(CH3)CHyCH3, -CH2-CH(Br)-COOC(CH3)3, -CH2-CH(Br)-COO-n-C3H~, -CH2-CH(Br)-COO-n-C4H9, -CH=CH-COOH, -CH=CH-COOCH3, -CH=CH-COOCHZCH3, -CH=CH-COOCH(CH3)2, -CH=CH-COOCHZCH(CH3)2, -CH=CH-COOCH(CH3)CH2CH3, -CH=CH-COOC(CH3)3, -CH=CH-COO-n-C3H~, -CH=CH-COD-n-C4H9, -CH=CH(C1)-COOH, -CH=CH(Cl)-COOCH3, -CH=CH(Cl)-COOCH2CH3, -CH=CH(C1)-COOCH(CH3)z, -CH=CH(Cl)-COOCH2CH(CH3)2, -CH=CH(C1)-COOCH{CH3)CHZCH3, -CH=CH(C1)-COOC(CH3)3, -CH=CH(C1)-C00-n-C3H~, -CH=CH(C1)-COO-n-C4H9, -CH=CH(Br)-COOH, -CH=CH(Br)-COOCH3, -CH=CH(Br)-COOCHyCH3, -CH=CH(Br)-COOCH(CH3)z.
-CH=CH(Br)-COOCH2CH(CH3)Z, -CH=CH(Br)-COOCH(CH3)CH2CH3, -CH=CH(Br)-COOC(CH3)3, -CH=CH(Br)-COO-n-C3H~, -CH=CH(Br)-COO-n-C4H9, -CHZ-CH(C1)-CONH2, -CH2-CH(C1)-CONHCH3, -CHy-CH(C1)-CON(CH3)2, -CHZ-CH(C1)-CONHCZH5, -CHZ-CH(C1)-CON(CHzCH3)z, -CHz-CH(C1)-CONH-n-C3H~, -CHy-CH(C1)-CON(n-C3H~)2, -CH2-CH(Cl)-CONH-n-C4H9, 2$
-CHz-CH(C1)-CON(n-C4Hg)z , -CHz-CH(Br)--CONHz, -CHz-CH(Br)-CONHCH3, -CHz-CH(Br)-CON(CH3)z, -CHZ-CH(Br)-CONH-CZHS, -CHz-CH(Br)-CON(CHZCH3)z, -CHz-CH(Br)-CONH-n-C3H~, -CHz-CH(Br)-CON(n-C3H~)z, -CHz-CH(Br)-CONH-n-CqHg, -CHz-CH(Br)-CON(n-C4Hg)z , -CH=CH-CONHz, -CH=CH-CONHCH3, -CH=CH-COON(CH3)z, -CH=CH-COONHC2H5, -CH=CH-CON(CH2CH3)z, -CH=CH-CONH-n-C3H~, -CH=CH-CON(n-C3H~)z, -CH=CH-CONH-n-C4Hg, -CH=CH-CON(n-C4Hg)z, -CH=CH(C1)-CONHz, -CH=CH(C1)-CONHCH3, -CH=CH(C1)-CON(CH3)z, -CH=CH(C1)-CONHCZHS, -CH=CH(C1)-CON(CH2CH3)z, -CH=CH(C1)-CONH-n-C3H~, -CH=CH(C1)-CON(n-C3H~)z, -CH=CH(Cl)-CONH-n-C4Hg, -CH=CH(C1)-CON(n-CqHg)z , -CH=CH(Br)-CONHz, -CH=CH(Br)-CONHCH3, -CH=CH(Br)-CON(CH3)z, -CH=CH(Br)-CONH-CzHS, -CH=CH(Br)-CON(CHZCH3)z, -CH=CH(Br)-CONH-n-C3H~, -CH=CH(Br)-CON(n-C3H~)z, -CH=CH(Br)-CONH-n-C4Hg, -CH=CH(Br)-CON(n-C4Hg)z .
Very particularly preferably, R3 is C1-C4-alkyl, C1-C4-haloalkyl or phenyl which may be unsubstituted or may carry a substituent selected from halogen, C1-C4-alkyl and C1-C4-haloalkyl, is saturated C3-C~-cycloalkyl, especially cycloalkyl, C3-C~-cycloalkyl-C1-C4-alkyl, especially cyclopropylmethyl, 3- to 7-memebered saturated heterocyclyl which contains one, two or three heteroatoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member.
In other preferred compounds of the formula I, Het is a cycle of the formula II-4, II-5, II-6, II-10, II-14 or II-17, particular II-5 or II-6, attached via an imide nitrogen.
In other particularly preferred compounds of the formula I, Het is a nitrogen heterocycle which has at least one carbonyl or thiocarbonyl function and at least one endocyclic hydrazone structure and which is selected from the radicals of the formulae II-1, II-2, II-11 and II-12.
With regards to the herbicidal and/or desiccating or defoliating effectivity Het is preferably a radical of the formula II-1, II-2, II-5, II-6 or II-12 and in particular for a radical of the formula II-2, II-5 and II-12.
In Het, X and X' are preferably oxygen. Y is likewise preferably oxygen. Q in the formula II-1 is likewise preferably oxygen.
In the radicals Het, the variables R4, R4', R4" independently of one another preferably have the following meanings: hydrogen, C1-C6-alkyl, halogen, amino, C1-C6-haloalkyl, C1-C6-haloalkoxy, C1-C6-haloalkylthio or C1-C6-alkylsulfonyl.
In the radicals Het, the variables R5 and RS' independently of one another preferably have the following meanings: hydrogen, C1-C6-alkyl, amino or C1-C6-haloalkyl.
Preferred compounds of the formula I may also have radicals Het in which two of the radicals R4, R4', R4", R5 and RS' together with the cycle to which they are attached form a 5-, 6- or 7-membered ring which may be mono- or diunsaturated or saturated and which may contain one or two heteroatoms selected from oxygen and sulfur as ring member.
Among the compounds of the formula I in which Het is a cycle of the formula II-1, preference is given to those compounds in which X is oxygen. In these compounds, Q is preferably likewise oxygen.
In these compounds, R4 is preferably C1-C4-alkyl and in particular tert-butyl.
Among the compounds of the formula I in which Het is a cycle of the formula II-2, preference is given to those compounds in which X is oxygen. In these compounds, R5 is preferably hydrogen or C1-C4-alkyl and in particular methyl. R5 is preferably C1-C4-haloalkyl and in particular trifluoromethyl.
Among the compounds of the formula I in which Het is a cycle of the formula II-5, preference is given to those compounds in which X and X' are oxygen. In these compounds, R4 and R4' are preferably hydrogen or C1-C4-alkyl or they form together with the carbon atoms to which they are bonded a 6-membered carbocycle and in particular a cyclohexene- or benzene-cycle.
Among the compounds of the formula I in which Het is a cycle of the formula II-6, preference is given to those compounds in which X and X' are oxygen. Y is preferably likewise oxygen. In these compounds, R6 and R~ are preferably C1-C4-alkyl, in particular methyl or they form together with the carbon atom to which they are bonded a 5- or 6-membered saturated carbocycle.
Among the compounds of the formula I in which Het is a cycle of the formula II-12, preference is given to those compounds in which X is oxygen. In these compounds, R9 is preferably hydrogen, amino, C1-C4-alkyl and in particular methyl. R4' is preferably C1-C4-haloalkyl and in particular trifluoromethyl, or C1-C4-alkylsulfonyl, in particular. methylsulfonyl. R~" is in particular hydrogen.
Preference is given, in particular, to compounds of the formula 5 I-A., in which RZ is chlorine, Z is a single bond and Het is a radical of the formula II-1 in which X and Q are 0 and R4 is tert-butyl, and R1 and R3 have the meanings given in Table 1 (compounds I-Aa.l to I-Aa.558).
O' ' -NN ~ / CI
\ (I-A) ao Table 1:
Nr . R1 R3 or R3 ._,_ 2 H Me 3 H Et 4 H n-Pr 5 H n-Bu 6 H i-Pr 7 H CHZ-CH(CH3)2 8 H CH(Me)-C2H5 9 H C(CH3)3 10 H CHZ-CH=CHZ
Q R5 \ N' \ X Y N-~N - ~ ~N -N-N
R4 N R4 N R5~ R5, (II-1) (II-2) (II-3) X X X
R5 ~ N ~ R4 Y' \
I N- I 'N- N-RS~iN~ R4, R6 X' X' ~ X' R
(II_4) (II_5) (II-6) i R4.
N R5 ~ N N, i Nw ~~ \ / \ ~N-Y N=N R4, N
(II_7) (II-8) (II_9) R5\ X R5\ X R4 X
N~ N
R4 -~~ N- X N- R4 N
N~ N ~N
X R4 R4"
(II-10) (II-11) (II-12) X Y N R5~ ~ i N%\
~ N N ~ N -R4, N
R4 R4 ~ R4 X .
(II-13) (II-14) (II-15) 5 ~ N~ N
R ~N N~- N\ N- R4' ~ N-~Nv R4,. X
X. R5. R4 X.
(II-16) (II-17) (II-ls) xpedit: ROBIC/BREVETS 4eme 514 845 8705; 05/01/02 12:10; JetFax #287;Page 2/2 ~~~~/50571 CA 02381639 2002-02-11 in which R4, R4' and R4" independently of one another axe hydrogen, amino, C1-C4-alkylamina, di-C1-C~-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamina, halogen, cyano, carboxyl, CL-C6-alkyl, C,_C6_haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-Cg-alkoxy, C1-C6-haloalkoxy, C1-C~-haloalkylthio, C1-Cg-alkoxycarbonyl, C3-C6-alkenyloxy, C3-Cb-alkynyloxy, C1-C6-alkylthio, C~-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C3-Ce-cycloalkyl or C3-C8-cyclaalkyl-Ci-CQ-alkyl;
RS and R5' independently of one another are hydrogen, amino, hydroxyl, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyi, C~-C6-alkynyl, Cl-C6-alkoxycarbonyl, t C3-C8-cyclaalkyl, C3-C$-cycloalkyl-C1-C4-alkyl, phenyl or phenyl-C1-C6-alkyl;
and/or two of the radicals R~, ~t4', R4", R5 and RS' together with the cycle to which they are attached form a 8-, 5-, 5- or 7-membered ring which may be saturated or unsaturated, which rnay contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three radicals selected from the group consisting of C1-C4-alkyl and halogen;
1t6 and R~ independently of one another are hydrogen, Cl-Cg-alkyl, C1-C6-haloalkyl or C3-C6-cyclaalkyl, or together with the carbon atom to which they are attached r,~,.~ form a 4-, 5-, 6- or 7-membered ring which may be W saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three substituents selected from the group consisting of C~,-Cy-alkyl and halogen;
Q in the formula II-1 is O or S, X and X' independently of one another are p or S, and Y is O, S or a group N-RB in which R$ is hydrogen, Cl-C6-alkyl, C1-C6-halaalkyl. ox C3-Cg-cycloalkyl;
and the agriculturally useful salts of the compounds of the formula I.
Moreover, the invention relates to - the use of the compounds I as herbicides, - compositions comprising the compounds I as herbicidally active substances, 5 - methods for controlling undesirable vegetation using the compounds of the formula I, and - compounds of the formulae III, IV, V and X as intermediates for preparing the compounds I.
He ~ ~ R2 ( I I I ) He ~ ~ R2 ( IV ) He ~ ~ R2 (V) He \ / Rz (g) WO 97/08170 describes 3-(benzoxazol-7-yl)- and 3-(benzothiazol-7-yl)-6-(trifluoromethyl)uracils as herbicides.
Further 3-(benzothiazol-7-yl)uracils and their use as herbicides and for the desiccation/defoliation of plants are disclosed in WO 97/08171. WO 97/12886 provides, inter alia, certain 3-benzisoxazol-7-yl-2,4-(1H,3H)pyrimidinediones which are said to have herbicidal and desiccant action. Furthermore, DE-A 197 55 926 discloses benzazol-4-ylpyrimidinediones and the earlier German patent application P 198 52 802.7 discloses derivatives of 3-(benzazol-7-yl)pyrimidinediones.
It is an object of the present invention to provide novel herbicidally active compounds which allow better targeted control of undesirable plants than the compounds of the prior art.
We have found that this object is achieved by the benzoxazole derivatives defined at the outset which have, in the 7-position, a 5- or 6-membered heterocycle, attached via a nitrogen atom.
Furthermore, we have found herbicidal compositions comprising the compounds I and having very good herbicidal action. Moreover, we have found processes for preparing these compositions and methods for controlling undesirable vegetation using the compounds I.
a m ' 005050571 CA 02381639 2002-02-11 Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures. The present invention provides both the pure enantiomers or diastereomers and their mixtures.
Suitable agriculturally useful salts are, especially, the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not adversely affect the herbicidal action of the compounds I. Thus, suitable cations are, in particular, the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion which, if desired, may carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic molecule moieties mentioned in the definition of the substituents R1 to R9 or as radicals on cycloalkyl, phenyl or heterocyclic rings are - like the term halogen - collective terms for individual enumerations of the individual group members. All hydrocarbon chains, i.e. all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenylalkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl moieties can be straight-chain or branched.
Halogenated substituents preferably carry one to five identical ' 050/50571 CA 02381639 2002-02-11 or different halogen atoms. The term halogen denotes in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
- C1-Cq-alkyl: CH3, C2H5, CHZ-C2H5, CH(CH3)2, n-butyl, CH(CH3)-C2H5, CHZ-CH(CH3)2 or C(CH3)3:
- C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, CHzF, CHF2, CF3, CHZC1, CH(C1)2, C(C1)3, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C2F5, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-CZFS, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
- C1-C6-alkyl: a C1-CQ-alkyl radical as mentioned above or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably CH3, CzHg, CH2-C2H5, CH(CH3)2, n-butyl, C(CH3)3.
n-pentyl or n-hexyl;
- C1-C6-haloalkyl: a C1-C6-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, one of the radicals mentioned under C1-C4-haloalkyl, or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, ' 0050/50571 CA 02381639 2002-02-11 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl;
- cyano-C1-C4-alkyl: CH2CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1-(CHZCN)eth-1-yl, 1-(CH2CN)-1-(CH3)-eth-1-yl or 1-(CH2CN)prop-1-yl;
- hydroxy-C1-C4-alkyl: CH20H, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 3-hydroxybut-2-yl, 4-hydroxybut-2-yl, 1-(CHZOH)eth-1-yl, 1-(CH20H)-1-(CH3)-eth-1-yl or 1-(CH20H)prop-1-yl;
- amino-C1-C4-alkyl: CHZNH2, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 1-amino-but-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1-(CHZNHa)eth-1-yl, 1-(CH2NH2)-1-(CH3)-eth-1-y1 or 1-(CH2NH2)prop-1-yl;
hYdroxycarbonyl-C1-C4-alkyl: CHzCOOH, 1-(COOH)ethyl, 2-(COOH)ethyl, 1-(COOH)prop-1-yl, 2-(COOH)prop-1-yl, 3-(COOH)prop-1-yl, 1-(COOH)but-1-yl, 2-(COOH)but-1-yl, 3-(COOH)but-1-yl, 4-(COOH)but-1-yl, 1-(COOH)but-2-yl, 2-(COOH)but-2-yl, 3-(COOH)but-2-yl, 4-(COOH)but-2-yl, 1-(CH2COOH)eth-1-yl, 1-(CH2COOH)-1-(CH3)-eth-1-yl or 1-(CH2COOH)prop-1-yl;
- aminocarbonyl-C1-C4-alkyl: CHZCONHz, 1-(CONHZ)ethyl, 2-(CONHZ)ethyl, 1-(CONH2)prop-1-yl, 2-(CONHZ)prop-1-yl, 3-(CONHZ)prop-1-yl, 1-(CONH2)but-1-yl, 2-(CONH2)but-1-yl, 3-(CONHZ)but-1-yl, 4-(CONH2)but-1-yl, 1-(CONHz)but-2-yl, 2-(CONHZ)but-2-yl, 3-(CONH2)but-2-yl, 4-(CONH2)but-2-yl, 1-(CH2CONH2)eth-1-yl, 1-(CHZCONHZ)-1-(CH3)-eth-1-yl or 1-(CH2CONH2)prop-1-yl;
_ phenyl-C1-C4-alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1-(benzyl)eth-1-yl, 1-(benzyl)-1-(methyl)eth-1-yl or 1-(benzyl)prop-1-yl, preferably benzyl or 2-phenylethyl;
- heterocyclyl-C1-C4-alkyl: heterocyclylmethyl, 1-heterocyclylethyl, 2-heterocyclylethyl, 1-heterocyclylprop-1-yl, 2-heterocyclylprop-1-yl, 3-heterocyclylprop-1-yl, 1-heterocyclylbut-1-yl, 2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl, 4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl, 2-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 4-heterocyclylbut-2-yl, 1-(heterocyclylmethyl)eth-1-yl, 1-(heterocyclylmethyl)-1-(methyl)eth-1-yl or 1-(heterocyclylmethyl)prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclylethyl;
- C1-C4-alkoxy: OCH3, OCzHS, OCHy-C2H5, OCH(CH3)2, n-butoxy, OCH(CH3)-CzH5, OCH2-CH(CH3)2 or C(CH3)3, preferably OCH3, OC2H5 or OCH(CH3)z;
- C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, OCHZF, OCHF2, OCF3, OCHzCl, OCH(C1)Z, OC(C1)3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OCzFS, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCHZ-CzF5, OCFZ-CZFS, 1-(CHZF)-2-fluoroethoxy, 1-(CHZC1)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF2, OCF3, dichlorofluoromethoxy, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
- C1-C6-alkoxy: a C1-C4-alkoxy radical as mentioned above or, for example, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy, preferably OCH3, OC2H5, OCH2-CZH5, OCH(CH3)2, n-butoxy, OC(CH3)3, n-pentoxy or n-hexoxy;
' 0050150571 CA 02381639 2002-02-11 - C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, one of the radicals mentioned under C1-C4-haloalkoxy, or 5-fluoro-1-pentoxy, 5 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
- C1-C4-alkylthio: SCH3, SC2H5, SCHz-C2H5, SCH(CH3)2, n-butylthio, SCH(CH3)-C2H5, SCHZ-CH(CH3)Z or SC(CH3)3, preferably SCH3 or SC2H5;
- C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, SCH2F, SCHF2, SCF3, SCH2C1, SCH(Cl)2, SC(C1)3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthia, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, SC2F5, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoro ro lthio, 2-chloro ro lthio 3-chloro ro lthio P PY P PY . P PY
2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCHz-CZF5, SCFz-CzFs, 1-(CHzF)-2-fluoroethylthio, 1-(CHZC1)-2-chloroethylthio, 1-(CHZBr)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or SCFz-CF2-C2F5, preferably SCHF2, SCF3, dichlorofluoromethylthio, chlorodifluoromethylthio or 2,2,2-trifluoroethylthio;
- C1-C6-alkylthio: a C1-C4-alkylthio radial as mentioned above or, for example, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio, preferably SCH3, SCzHS, SCH2-C2H5, SCH(CH3)2, n-butylthio, SC(CH3)3, n-pentylthio or n-hexylthio;
0U5~~50571 CA 02381639 2002-02-11 1l - C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy - as mentioned above -, i.e., for example, CH2-OCH3, CHZ-OC2H5, n-propoxymethyl, CH2-OGH(CH3)2.
n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CHZ-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(I,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl, preferably CH2-OCH3, CH2-OC2H5, 2-(pCH3)ethyl or 2-(OCZH5)ethyl;
- C1-C4-haloalkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkoxy as mentioned, above, i.e., for example, 2-(OCHFZ)ethyl, 2-(OCF3)ethyl or 2-(OC2F5)ethyl;
- C1-C4-alkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylthio - as mentioned above -, i.e., for example, CHZ-SCH3, CHZ-SC2H5, n-propylthiomethyl, CH2-SCH(CH3)z, n-butylthiomethyl, (1-methylpropylthio)methyl, (2-methylpropylthio)methyl, CH2-SC(CH3)3, 2-(methylthio)ethyl, 2-(ethylthio)ethyl, 2-(n-propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl, 2-(ethylthio)propyl, 2-(n-propylthio)propyl, 2-(1-methylethylthio)propyl, 2-(n-butylthio)propyl, 2-(1-methylpropylthio)propyl, 2-(2-methylpropylthio)propyl, 2-(1,1-dimethylethylthio)propyl, 3-(methylthio)propyl, 3-(ethylthio)propyl, 3-(n-propylthio)propyl, 3-(1-methylethylthio)propyl, 3-(n-butylthio)propyl, 3-(1-methylpropylthio)propyl, 3-(2-methylpropylthio)propyl, 3-(1,1-dimethylethylthio)propyl, 2-(methylthio)butyl, 2-(ethylthio)butyl, 2-(n-propylthio)butyl, 2-(1-methylethylthio)butyl, 2-(n-butylthio)butyl, 2-(1-methylpropylthio)butyl, 2-(2-methylpropylthio)butyl, 2-(1,1-dimethylethylthio)butyl, 3-(methylthio)butyl, 3-(ethylthio)butyl, 3-(n-propylthio)butyl, 3-(1-methylethylthio)butyl, 3-(n-butylthio)butyl, 3-(1-methylpropylthio)butyl, 3-(2-methylpropylthio)butyl, 3-(1,1-dimethylethylthio)butyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(n-propylthio)butyl, 4-(1-methylethylthio)butyl, 4-(n-butylthio)butyl, 4-(1-methylpropylthio)butyl, 4-(2-methylpropylthio)butyl or 4-(1,1-dimethylethylthio)butyl, preferably CHZ-SCH3, CHz-SC2H5, 2-(SCH3)ethyl or 2-(SC2H5)ethyl;
15. - C1-C4-haloalkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylthio as mentioned above, i.e., for example, 2-(SCHFZ)ethyl, 2-(SCF3)ethyl or 2-(SC2F5)ethyl;
- (C1-C4-alkyl)carbonyl: CO-CH3, CO-CZHS, CO-CHZ-C2H5, CO-CH(CH3)2.
n-butylcarbonyl, CO-CH(CH3)-CZHS, CO-CH2-CH(CH3)2 or CO-C(CH3)3, preferably CO-CH3 or CO-CZHS;
- (C1-C4-haloalkyl)carbonyl: a (C1-C4-alkyl)carbonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, CO-CHZF, CO-CHFz, CO-CF3, CO-CHZC1, CO-CH(C1)Z, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C2F5, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO--CH2-CZFS, CO-CF2-CZF5, 1-(CH2F)-2-fluoroethylcarbonyl, 1-(CHZC1)-2-chloroethylcarbonyl, 1-(CHzBr)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CHZCl or 2,2,2-trifluoroethylcarbonyl;
- (C1-C4-alkyl)carbonyloxy: 0-CO-CH3, 0-CO-C2H5, 0-CO-CH2-C2H5, O-CO-CH(CH3)2, 0-CO-CHZ-CH2-C2H5, 0-CO-CH(CH3)-CZHS, 0-CO-CHZ-CH(CH3)2 or 0-CO-C(CH3)3. preferably 0-CO-CH3 or O-CO-CzHS;
- (C1-C4-haloalkyl)carbonyloxy: a (C1-C4-alkyl)carbonyl radical -as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, O-CO-CHZF, O-CO-CHFZ, 0-CO-CF3, O-CO-CHZCl, O-CO~H(C1)2, ~O-C(C1)3, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2.2,2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2-trichloroethylcarbonyloxy, O-CO-C2F5, 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy, 2,2-difluoropropylcarbonyloxy, 2,3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-dichloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy, 3,3,3-trichloropropylcarbonyloxy, O-CO-CH2-CZFS, O-CO-CF2-CzF5, 1-(CHZF)-2-fluoroethylcarbonyloxy, 1-(CHZC1)-2-chloroethylcarbonyloxy, 1-(CHZBr)-2-bromoethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably 0-CO-CF3, O-CO-CHZC1 or 2~2,2-trifluoroethylcarbonyloxy;
- (C1-C4-alkoxy)carbonyl: CO-OCH3, CO-OCzHS, CO-OCHZ-C2H5.
CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CH3)-C2H5, CO-OCH2-CH(CH3)2 or CO-OC(CH3)3, preferably CO-OCH3 or CO-OC2H5;
- (C1-C6-alkoxy)carbonyl: one of the abovementioned (C1-C4-alkoxy)carbonyl radicals or, for example, n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy-C0, 2,2-dimethylpropoxy-C0, 1-ethylpropoxy-CO, n-hexoxy-CO, 1,1-dimethylpropoxy-C0, 1,2-dimethylpropoxy-C0, 1-methylpentoxy-CO, 2-methylpentoxy-C0, 3-methylpentoxy~0, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-CO, 1,2-dimethylbutoxy-CO, 1,3-dimethylbutoxy-CO, 2,2-dimethylbutoxy-C0, 2,3-dimethylbutoxy-CO, 3,3-dimethylbutoxy-CO, 1-ethylbutoxy-C0, 2-ethylbutoxy-CO, 1,1,2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-CO, 1-ethyl-1-methylpropoxy-CO or 1-ethyl-2-methylpropoxy-C0, preferably CO-OCH3, CO-OC2H5, CO-OCHz-CZH5, CO-OCH(CH3)2.
n-butoxy-CO, CO-OC(CH3)3, n-pentoxy-CO or n-hexoxy-CO;
- {C1-C4-alkoxy)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkoxy)carbonyl - as mentioned above -, i.e., for example, CH2-CO-OCH3, CH2-CO-OCzHS, CH2-CO-OCHZ-C2H5, CH2-CO-OCH(CH3)2, n-butoxycarbonylmethyl, CH2-CO-OCH(CH3)-C2H5, CHz-CO-OCHZ-CH(CH3)2, CH2-CO-OC(CH3)3, 1-(CO-OCH3)ethyl, 1-(CO-OCzHS)ethyl, 1-(CO-OCHZ-CzHS)ethyl, 1-[CH(CH3)2]ethyl, l-{n-butoxycarbonyl)ethyl, 1-[1 methylpropoxycarbonyl]ethyl, 1-[2 methylpropoxycarbonyl]ethyl, 2-(CO-OCH3)ethyl, 2-(CO-OC2H5)ethyl, 2-(CO-OCH2-CZHS)ethyl, 2-[CO-OCH(CH3)2]ethyl, 2-(n-butoxycarbonyl)ethyl, 2-[1-methylpropoxycarbonyl]ethyl, 2-[2-methylpropoxycarbonyl]ethyl, 2-[CO-OC(CH3)3]ethyl, 2-(CO-OCH3)propyl, 2-(CO-OC2H5)propyl, 2-(CO-OCHz-C2H5)propyl, 2-[CO--aCH(CH3)2]propyl, 2-(n-butoxycarbonyl}propyl, 2-[1-methylpropoxycarbonyl]propyl, 2-[2-methylpropoxycarbonyl]propyl, 2-[CO-OC(CH3)3]propyl, 3-(CO-OCH3)propyl, 3-(CO-OCZHS)propyl, 3-(CO-OCH2-C2H5)propyl, 3-[CO-OCH(CH3)2]propyl, 3-(n-butoxycarbonyl)propyl, 3-[1-methylpropoxycarbonyl]propyl, 3-[2-methylpropoxycarbonyl]propyl, 3-[CO-OC(CH3)3]propyl, 2-(CO-OCH3)butyl, 2-(CO-OC2H5)butyl, 2-(CO-OCHZ-C2H5)butyl, 2-[CO-OCH(CH3)2]butyl, 2-(n-butoxycarbonyl}butyl, 2-[1_methylpropoxycarbonyl]butyl, 2-[2-methylpropoxycarbonyl]butyl, 2-[CO-OC(CH3)3]butyl, 3-(CO-OCH3)butyl, 3-(CO-OC2H5)butyl, 3-(CO-OCHZ-C2H5)butyl, 3-[CO-OCH(CH3)2]butyl, 3-(n-butoxycarbonyl)butyl, 3-[1-methylpropoxycarbonyl]butyl, 3_[2-methylpropoxycarbonyl]butyl, 3-[CO-OC{CH3}3]butyl, 4-(CO-OCH3)butyl, 4-(CO-OCZHS)butyl, 4-(CO-OCH2-C2H5}butyl, 4-[CO-OCH(CH3)2]butyl, 4-(n-butoxycarbonyl)butyl, 4-[1-methylpropoxycarbonyl]butyl, 4-[2-methylpropoxycarbonyl]butyl or 4-[CO-OC(CH3)3]butyl, preferably CH2-CO-OCH3, CHZ-CO-OC2H5, 1-(CO-OCH3)ethyl or 1-(CO-OC2H5)ethyl;
- (C1-C4-alkylthio)carbonyl: CO-SCH3, CO-SCzHS, CO-SCH2-C2H5, CO-SCH(CH3)2, CO-SCH2CHp-CZHS, CO-SCH(CH3}-CZHS, CO-SCHZ-CH(CH3)2 or CO-SC(CH3)3, preferably CO-SCH3 or CO-SCzHS;
(C1-C4-alkylthio)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkylthio}carbonyl - as mentioned above -, i.e., for example, CHZ-CO-SCH3, CHZ-CO-SC2H5, CH2-CO-SCH2-CZHS, CHZ-CO-SCH(CH3)2, CH2-CO-SCHZCH2-C2H5, CH2-CO-SCH(CH3)-CZHS, CHZ-CO-SCHZ-CH(CH3)2, CH2-CO-SC(CH3)3.
1-(CO-SCH3)ethyl, 1-(CO-SCZHS)ethyl, 1-(CO-SCHZ-CzHS)ethyl, ' X050/50571 CA 02381639 2002-02-11 1-[CO-SCH(CH3)z]ethyl, 1-(CO-SCHZCHz-CZHS)ethyl, 1-[CO-SCH(CH3)-CzHS]ethyl, 1-[CO-SCHz-CH(CH3)z]ethyl, 1-[CO-SC(CH3)3]ethyl, 2-(CO-SCH3)ethyl, 2-(CO-SCzHS)ethyl, 2-(CO-SCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)z]ethyl, 5 2-(CO-SCHzCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)-CZHS]ethyl, 2-[CO-SCHz-CH(CH3)z]ethyl, 2-[CO-SC(CH3)g]ethyl, 2-(CO-SCH3)propyl, 2-(CO-SCZHS)propyl, 2-(CO-SCHZ-CzHS)propyl, 2-[CO-SCH(CH3)z]propyl, 2-(CO-SCH2CHZ-C2H5)propyl, 2-[CO-SCH(CH3)-CZHS]propyl, 2-[CO-SCHz-CH(CH3)z]propyl, 10 2-[CO-SC(CHg)3]propyl, 3-(CO-SCH3)propyl, 3-(CO-SCZHS)propyl, 3-(CO-SCHZ-C2H5)propyl, 3-[CO-SCH(CH3)z]propyl, 3-(CO-SCHZCHZ-CZHS)propyl, 3-[CO-SCH(CH3)-C2H5]propyl, 3-[CO-SCHZ-CH(CH3)z]propyl, 3-[CO-SC(CH3)3]propyl, 2-(CO-SCH3)butyl, 2-(CO-SCZHS)butyl, 2-(CO-SCHz-CZHS)butyl, 15 2-[CO-SCH(CH3)z]butyl, 2-(CO-SCHzCHZ-C2H5)butyl, 2-[CO-SCH(CHg)-C2H5]butyl, 2-[CO-SCHz-CH(CH3)z]butyl, 2-[CO-SC(CH3)3]butyl, 3-(CO-SCH3)butyl, 3-(CO-SCZHS)butyl, 3-(CO-SCHz-CyHS)butyl, 3-[CO-SCH(CH3)z]butyl, 3-(CO-SCHZCHZ-C2H5)butyl, 3-[CO-SCH(CH3)-CZHS]butyl, 3-[CO-SCHZ-CH(CH3)z]butyl, 3-[CO-SC(CH3)3]butyl, 4-(CO-SCH3)butyl, 4-(CO-SCZHS)butyl, 4-(CO-SCHz-CZHS)butyl, 4-[CO-SCH(CH3)z]butyl, 4-(CO-SCH2CHZ-CZHS)butyl, 4-[CO-SCH(CH3)-C2H5]butyl, 4-[CO-SCHz-CH(CH3)z]butyl or 4-[CO-SC(CH3)3]butyl, preferably CHz-CO-SCH3, CHz-CO-SC2H5, 1-(CO-SCH3)ethyl or 1-(CO-SC2H5)ethyl;
- C1-C6-alkylsulfinyl: a C1-C4-alkylsulfinyl radical such as SO-CH3, SO-C2H5, SO-CHz-CZHS, SO-CH(CH3)z, SO-(n-CqHg), SO-CH(CH3)-CZHS, SO-CHz-CH(CH3)z or SO-C(CH3)3, or, for example, SO-(n-C5H11), 1-methylbutyl-SO, 2-methylbutyl-SO, 3-methylbutyl-S0, 2,2-dimethylpropyl-SO, 1-ethylpropyl-S0, n-hexyl-SO, 1,1-dimethylpropyl-SO, 1,2-dimethylpropyl-SO, 1-methylpentyl-S0, 2-methylpentyl-S0, 3-methylpentyl-SO, 4-methylpentyl-S0, 1,1-dimethylbutyl-S0, 1,2-dimethylbutyl-SO, 1,3-dimethylbutyl-S0, 2,2-dimethylbutyl-SO, 2,3-dimethylbutyl-S0, 3,3-dimethylbutyl-SO, 1-ethylbutyl-SO, 2-ethylbutyl-S0, 1,1,2-trimethylpropyl-SO, 1,2,2-trimethylpropyl-S0, 1-ethyl-1-methylpropyl-SO or 1-ethyl-2-methylpropyl-SO, preferably SO--CH3, SO-CzHS, SO-CHZ-CZH5, SO-CH(CH3)2, SO-(ri-CqHg), SO-C(CH3)3, SO-(n-C5H11) or SO-(n-C6H13);
- C1-C4-alkylsulfonyl: SOZ-CH3, SOz-CZHS, SOz-CHZ-CyHS, SOz-CH(CH3)z, n-butylsulfonyl, SOz-CH(CH3)-CzHS, SOz-CHZ-CH(CH3)z or SOz-C(CH3)3, preferably SOz-CH3 or SOz-CzHS;
- C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, SOz-CH2F, SOz-CHFZ, SOz-CF3, SOz-CHzCl, SOz-CH(C1)z, SOz--C(C1)3, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, SOz-C2F5, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, SOz-CHZ-C2F5, SOz--CFZ-CzFS, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably SOz-CH2C1, SOz-CF3 or 2,2,2-trifluoroethylsulfonyl;
- C1-Cs-alkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above or, for example, SOZ-(n-C5H11), 1-methylbutyl-SOz, 2-methylbutyl-SOz, 3-methylbutyl-SOz, 2,2-dimethylpropyl-SOz, 1-ethylpropyl-SOz, n-hexyl-SOz, 1,1-dimethylpropyl-SOz, 1,2-dimethylpropyl-SOz, 1-methylpentyl-SOz, 2-methylpentyl-SOz, 3-meth 1 ent 1-SO , 4-meth 1 ent 1-SO 1 1-dimeth lbut 1-SO
Y P Y z Y P Y 2. ~ Y Y z.
1,2-dimethylbutyl-SOz, 1,3-dimethylbutyl-SOz, 2,2-dimethylbutyl-SOz, 2,3-dimethylbutyl-SOz, 3,3-dimethylbutyl-SOz, 1-ethylbutyl-SOz, 2-ethylbutyl-SOz, 1,1,2-trimethylpropyl-SOz, 1,2,2-trimethylpropyl-SOz, 1-ethyl-1-methylpropyl-SOz or 1-ethyl-2-methylpropyl-SOz, preferably SOz-CH3, SOz-C2H5, SOz-CHZ-CzHS, SOz-CH(CH3)2.
SOz-(n-CqH9)r S02-C(CH3)3, S02-(ri-C5H11) Or SOz-(n-C6H13)i - C1-C4-alkylamino: H3C-NH-, HSCz-NH-, n-propyl-NH-, 1-methylethyl-NH-, n-butyl-NH-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1,1-dimethylethyl-NH-, preferably H3C-NH- or H5Cz-NH-;
- C1-C4-alkylamino-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylamino as defined above, i.e., for example, CHZCHz-NH-CH3, CHzCHz-N(CH3)z, CH2CHz-NH-C2H5 or CH2CHz-N(C2H5)z;
' ~ ~~50/50571 CA 02381639 2002-02-11 - (C1-C4-alkylamino)carbonyl: CO-NH-CH3, CO-NH-C2H5, n-propylamino, CO-NH-CH(CH3)Z, CO-NH-CHzCH2-CZHS, CO-NH-CH(CH3)-C2H5, CO-NH-CHz-CH(CH3)2 or CO-NH-C(CH3)3.
preferably CO-NH-CH3 or CO-NH-CZHS;
- (C1-C4-alkylamino)carbonyl-C1-C4-alkyl: C1-CQ-alkyl which is substituted by (C1-C4-alkylamino)carbonyl as mentioned above, preferably by CO-NH-CH3 or CO-NH-CZHS, as e.g. CH2-CO-NH-CH3, CH2-CO-NH-CzHS, CH2-CO-NH-CH2-C2H5, CH2-CO-NH-CH(CH3)y, CHz-CO-NH-CH2CH2-C2H5, CHZ-CO-NH-CH(CH3)-CZHS, CH2-CO-NH-CHZ-CH(CH3)2, CH2-CO-NH-C(CH3)3, CH(CH3)-CO-NH-CH3, CH(CH3)-CO-NH-CZHS, 2-(CO-NH-CH3)ethyl, 2-(CO-NH-C2H5)ethyl, 2-(CO-NH-CH2-CZHS)ethyl, 2-[CHy-CO-NH-CH(CH3)2]ethyl, 2-(CO-NH-CH2CHz-C2H5)ethyl, 2-[CO-NH-CH(CH3)-C2H5]ethyl, 2-[CO-NH-CHz-CH(CH3)2]ethyl, 2-[CO-NH-C(CH3)3]ethyl, 2-(CO-NH-CH3)propyl, 2-(CO-NH-CzHS)propyl, 2-(CO-NH-CH2-C2H5)propyl, 2-[CH2-CO-NH-CH(CH3)2]propyl, 2-(CO-NH-CH2CH2-CZHg)propyl, 2-[CO-NH-CH(CH3)-C2H5]propyl, 2-[CO-NH-CH2-CH(CH3)2]propyl, 2-[CO-NH-C(CH3)3]propyl, 3-(CO-NH-CH3)propyl, 3-(CO-NH-CZHS)propyl, 3-(CO-NH-CHZ-CzHS)propyl, 3-[CHZ-CO-NH-CH(CH3)2]propyl, 3-(CO-NH-CHZCH2-CzHS)propyl, 3-[CO-NH-CH(CH3)-CzHS]propyl, 3-[CO-NH-CHZ-CH(CH3)2]propyl, 3-[CO-NH-C(CH3)3]propyl, 2-(CO-NH-CH3)butyl, 2-(CO-NH-C2H5)butyl, 2-(CO-NH-CH2-C2Hg)butyl, 2-[CHZ-CO-NH-CH(CH3)2]butyl, 2_(CO-NH-CHyCH2-C2H5)butyl, 2-[CO-NH-CH(CH3)-C2H5]butyl, 2-[CO-NH-CHZ-CH(CH3)y]butyl, 2-[CO-NH-C(CH3)3]butyl, 3-(CO-NH-CH3)butyl, 3-(CO-NH-C2H5)butyl, 3-(CO-NH-CHZ-CZHS)butyl, 3-[CH2-CO-NH-CH(CH3)2]butyl, 3-(CO-NH-CH2CHz-C2H5)butyl, 3-[CO-NH-CH(CH3)-CZHS]butyl, 3_[CO-NH-CHZ-CH(CH3)2]butyl, 3-[CO-NH-C(CH3)3]butyl, 4-(CO-NH-CH3)butyl, 4-(CO-NH-CZHg)butyl, 4-(CO-NH-CH2-C2H5)butyl, 4-[CHZ-CO-NH-CH(CH3)Z]butyl, 4-(CO-NH-CHZCHz-C2H5)butyl, 4-[CO-NH-CH(CH3)-C2H5]butyl, 4-[CO-NH-CHZ-CH(CH3)2]butyl or 4-[CO-NH-C(CH3)3]butyl, preferably CH2-CO-NH-CH3, CHZ-CO-NH-C2H5, CH(CH3)-CO-NH-CH3 or CH ( CH3 )--CO NH-C2H5;
- di(C1-C4-alkyl)amino: N(CH3)Z, N(CZH5)2, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, '. ~ ~ 0~5~~505')1 CA 02381639 2002-02-11 N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino, preferably N(CH3)z or N(CZHS)2:
- di(C1-C4-alkyl)amino-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)amino as mentioned above, i.e., for example, CHZN(CH3)2, CH2N(CyHS)2, N,N-dipropylaminomethyl, N,N-di[CH(CH3)Z]aminomethyl, N,N-dibutylaminomethyl, N,N-di-(1-methylpropyl)aminomethyl, N,N-di(2-methylpropyl)aminomethyl, N,N-di[C(CH3)3]aminomethyl, N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl, N-methyl-N-[CH(CH~)2]aminomethyl, N-butyl-N-methylaminomethyl, N-methyl-N-(1-methylpropyl)aminomethyl, N-methyl-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-methylaminomethyl, N-ethyl-N-propylaminomethyl, N-ethyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl)aminomethyl, N-ethyl-N-[C(CH3)3]aminomethyl, N-[CH(CH3)z]-N-propylaminomethyl, N-butyl-N-propylaminomethyl, N-(1-methylpropyl)-N-propylaminomethyl, N-(2-methylpropyl)-N-propylaminomethyl, N-[C(CH3)3]-N-propylaminomethyl, N-butyl-N-(1-methylethyl)-aminomethyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminomethyl, N-[CH(CH3)y]-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-[CH(CH3)2]aminomethyl, N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methylpropyl)aminomethyl, N-butyl-N-[C(CH3)3]-aminomethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(2-methylpropyl)aminomethyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,N-di(n-propyl)aminoethyl, N,N-di[CH(CH3)2]aminoethyl, N,N-dibutylaminoethyl, N,N-di(1-methylpropyl)aminoethyl, N,N-di(2-methylpropyl)aminoethyl, N,N-di[C(CH3)3]aminoethyl, N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N-[CH(CH3)z]aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N-(1-methylpropyl)aminoethyl, N-methyl-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N-[CH(CH3)z]aminoethyl, N-butyl-N-ethylaminoethyl, N-ethyl-N-(1-methylpropyl)aminoethyl, N-ethyl-N-(2-methylpropyl)aminoethyl, N-ethyl-N-[C(CH3)3]aminoethyl, N-[CH(CH3)z]-N-propylaminoethyl, N-butyl-N-propylaminoethyl, N-(1-methylpropyl)-N-propylaminoethyl, N-(2-methylpropyl)-N-propylaminoethyl, N-[C(CH3)31-N-Propylaminoethyl, N-butyl-N-[CH(CH3)z]aminoethyl, N-[CH(CH3)z]-N-(1-methylpropyl)aminoethyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-[CH(CH3)z]aminoethyl, N-butyl-N-(1-methylpropyl)aminoethyl, N-butyl-N-(2-methylpropyl)aminoethyl, N-butyl-N-[C(CH3)3]aminoethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminoethyl or N-[C(CH3)3]-N-(2-methylpropyl)aminoethyl, in particular N,N~limethylaminoethyl or N,N-diethylaminoethyl;
- di(C1-C4-alkyl)aminocarbonyl: CO-N(CH3)z, CO-N(CzHS), CO-N CH -C H CO-N CH CH
( z z 5)z. [ ( 3)2]2. N.N-dibutylaminocarbonyl, CO-N[CH(CH3)-CzHS]z, CO-N[CHZ-CH(CH3)z]z~ CO-N[C(CH3)3]2~
N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-[C(CH3)3]aminocarbonyl, N-[CH(CH3)z]-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N-(1-methylpropyl)-N-propylaminocarbonyl, N-(2-methylpropyl)-N-propylaminocarbonyl, N-[C(CH3)3]-N-propylaminocarbonyl, N-butyl-N-[CH(CH3)z]aminocarbonyl, N-[CH(CH3)z]-N-(1-methylpropyl)aminocarbonyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-[CH(CH3)2]aminocarbonyl, , 0050/50571 CA 02381639 2002-02-11 N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methylpropyl)aminocarbonyl, N-butyl-N-[C(CH3)3]aminocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, 5 N-[C(CH3)3]-N-(1-methylpropyl)aminocarbonyl or N-[C(CH3)3]-N-(2-methylpropyl)aminocarbonyl, preferably CO-N(CH3)2 or CO-N(CyHS)2:
di(C1-C6-alkyl)aminocarbonyl: one of the abovementioned 10 di(C1-C4-alkyl)aminocarbonyl radicals or, for example, N(CH3)-(n-C5H11)r N(~2H5)-(n-~5H11)~ N(~H2-~zHS)-(n-~5H11)~
N(n-C4Hs)-(n-C5Hli)~ N(n-CSHii)-(n-C5Hii)~ N(n-CsHi3)-(n-CSHii).
N(CH3)-(n-C6H13). N(C2H5)-(n-CsHl3). N(CHz-C2H5)-(n-CsHl3).
N(n-C4H9)-(n-C6H13)i N(n-C5H11)-(n-C6H13) or N(n-C6H13)2:
- di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)phosphonyl such as -PO(OCH3)2, -PO(OC2H5)2, N,N-dipropylphosphonyl, N,N-di(1-methylethyl)phosphonyl, N,N-dibutylphosphonyl, NON-di(1-methylpropyl)phosphonyl, N,N-di(2-methylpropyl)phosphonyl, N,N-di(1,1-dimethylethyl)phosphonyl, N-ethyl-N-methylphosphonyl, N-methyl-N-propylphosphonyl, N-methyl-N-(1-methylethyl)phosphonyl, N-butyl-N-methylphosphonyl, N-methyl-N-(1-methylpropyl)-hos hon 1, N-meth 1-N 2-meth 1 ro 1 hos hon l, P P Y Y -( Y P PY )P P Y
N-(1,1-dimethylethyl)-N-methylphosphonyl, N-ethyl-N-propylphosphonyl, N-ethyl-N-(1-methylethyl)phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl-N-(1-methylpropyl)phosphonyl, N-ethyl-N-(2-methylpropyl)phosphonyl, N-ethyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylethyl)-N-propylphosphonyl, N-butyl-N-propylphosphonyl, N-(1-methylpropyl)-N-propylphosphonyl, N-(2-methylpropyl)-N-propylphosphonyl, N-(1,1-dimethylethyl)-N-propylphosphonyl, N-butyl-N-(1-methylethyl)phosphonyl, N-(1-methylethyl)-N-(1-methylpropyl)phosphonyl, N-(1-methylethyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)phosphonyl, N-butyl-N-(1-methylpropyl)phosphonyl, N-butyl-N-(2-methylpropyl)phosphonyl, N-butyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylpropyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)phosphonyl or N-(l,l-dimethylethyl)-N-(2-methylpropyl)phosphonyl, preferably by -PO(OCH3)2 or -PO(OCZHS)2, i.e., for example, CHZ-PO(OCH3)2.
CHZ-PO(OCZHS)2, CH(CH3)-PO(OCH3)2 Or CH(CH3)-PO(OC2H5)2;
- C3-C6-alkenyl: prop-1-en-1-yl, allyl, 1-rnethylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2r3_dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-,2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, e.g. 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3-dibromoa11y1, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
00'S~/50571 CA 02381639 2002-02-11 - cyano-C3-C6-alkenyl: for example 2-cyanoallyl, 3-cyanoallyl, 4-cyanvbut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl;
- C3-C6-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, preferably prop-2-yn-1-yl;
- C3-C6-haloalkynyl: C3-C6-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, 1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, l,l-difluorobut-2-yn-1-yl, 5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;
- cyano-C3-C6-alkynyl: for example 3-cyanopropargyl, 4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl;
- C3-C4-alkenyloxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkenyloxy such as allyloxy, but-1-en-3-yloxy, but-1-en-4-yloxy, but-2-en-1-yloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, i.e., for example, allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl, in particular 2-allyloxyethyl;
_ C3-C4_alkynyloxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynyloxy such as propargyloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy, but-2-yn-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, i.e., for example, propargyloxymethyl or 2-propargyloxyethyl, in particular 2-propargyloxyethyl;
- C3-C6-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
_ C3-C6-cycloalkylamino: cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino;
- C3-Ce-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
- C3-C8-cycloalkyl-C1-C6-alkyl: for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2-(cyclopropyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl, 2-(cyclohexyl)ethyl, 2-(cycloheptyl)ethyl, 2-(cyclooctyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclobutyl)propyl, 3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 3-(cycloheptyl)propyl, 3-(cyclooctyl)propyl, 4-(cyclopropyl)butyl, 4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)butyl, 4-(cycloheptyl)butyl, 4-(cyclooctyl)butyl, 5-(cyclopropyl)pentyl, 5-(cyclobutyl)pentyl, 5-(cyclopentyl)pentyl, 5-(cyclohexyl)pentyl, 5-(cycloheptyl)pentyl, 5-(cyclooctyl)pentyl, 6-(cyclopropyl)hexyl, 6-(cyclobutyl)hexyl, 6-(cyclopentyl)hexyl, 6-(cyclohexyl)hexyl, 6-(cycloheptyl)hexyl or 6-(cyclooctyl)hexyl;
- C3-C8-cycloalkyloxy-C1-C4-alkyl: cyclopropyloxymethyl, 1-cyclopropyloxyethyl, 2-cyclopropyloxyethyl, 1-cyclopropyloxyprop-1-yl, 2-cyclopropyloxyprop-1-yl, 3-cyclopropyloxyprop-1-yl, 1-cyclopropyloxybut-1-yl, 2-cyclopropyloxybut-1-yl, 3-cyclopropyloxybut-1-yl, 4-cyclopropyloxybut-1-yl, 1-cyclopropyloxybut-2-yl, 2-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 4-cyclopropyloxybut-2-yl, 1-(cyclopropyloxymethyl)eth-1-yl, 1-(cyclopropyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopropylmethyloxy)prop-1-yl, cyclobutyloxymethyl, 1-cyclobutyloxyethyl, 2-cyclobutyloxyethyl, 1-cyclobutyloxyprop-1-yl, 2-cyclobutyloxyprop-1-yl, 3-cyclobutyloxyprop-1-yl, 1-cyclobutyloxybut-1-yl, 2-cyclobutyloxybut-1-yl, 3-cyclobutyloxybut-1-yl, 4-cyclobutyloxybut-1-yl, 1-cyclobutyloxybut-2-yl, 2-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 4-cyclobutyloxybut-2-yl, _ 1-(cyclobutyloxymethyl)eth-1-yl, 1-(cyclobutyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclobutyloxymethyl)prop-1-yl, cyclopentyloxymethyl, 1-cyclopentyloxyethyl, 2-cyclopentyloxyethyl, 1-cyclopentyloxyprop-1-yl, 2-cyclopentyloxyprop-1-yl, 3-cyclopentyloxyprop-1-yl, 1-cyclopentyloxybut-1-yl, 2-cyclopentyloxybut-1-yl, 3-cyclopentyloxybut-1-yl, 4-cyclopentyloxybut-1-yl, 1-cyclopentyloxybut-2-yl, 2-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 4-cyclopentyloxybut-2-yl, 1-(cyclopentyloxymethyl)eth-1-yl, 1-(cyclopentyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopentyloxymethyl)prop-1-yl, cyclohexyloxymethyl, 1-cyclohexyloxyethyl, 2-cyclohexyloxyethyl, 1-cyclohexyloxyprop-1-yl, 2-cyclohexyloxyprop-1-yl, 3-cyclohexyloxyprop-1-yl, 1-cyclohexyloxybut-1-yl, 2-cyclohexyloxybut-1-yl, 3-cyclohexyloxybut-1-yl, 4-cyclohexyloxybut-1-yl, 1-cyclohexyloxybut-2-yl, 2-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 4-cyclohexyloxybut-2-yl, 1-(cyclohexyloxymethyl)eth-1-yl, 1-(cyclohexyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclohexyloxymethyl)prop-1-yl, cycloheptyloxymethyl, 1-cycloheptyloxyethyl, 2-cycloheptyloxyethyl, 1-cycloheptyloxyprop-1-yl, 2-cycloheptyloxyprop-1-yl, 3-cycloheptyloxyprop-1-yl, 1-cycloheptyloxybut-1-yl, 2-cycloheptyloxybut-1-yl, 3-cycloheptyloxybut-1-yl, 4-cycloheptyloxybut-1-yl, 1-cycloheptyloxybut-2-yl, 2-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 4-cycloheptyloxybut-2-yl, 1-(cycloheptyloxymethyl)eth-1-yl, 1-(cycloheptyloxymethyl)-1-(CH3)eth-1-yl, 1-(cycloheptyloxymethyl)prop-1-yl, cyclooctyloxymethyl, 1-cyclooctyloxyethyl, 2-cyclooctyloxyethyl, 1-cyclooctyloxyprop-1-yl, 2-cyclooctyloxyprop-1-yl, 3-cyclooctyloxyprop-1-yl, 1-cyclooctyloxybut-1-yl, 2-cyclooctyloxybut-1-yl, 3-cyclooctyloxybut-1-yl, 4-cyclooctyloxybut-1-yl, 1-cyclooctyloxybut-2-yl, 2-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 4-cyclooctyloxybut-2-yl, 1-(cyclooctyloxymethyl)eth-1-yl, 1-(cyclooctyloxymethyl)-1-(CH3)eth-1-yl or 1-(cyclooctyloxymethyl)prop-1-yl, in particular C3-C6-cycloalkoxymethyl or 2-(C3-C6-cycloalkoxy)ethyl.
3- to 7-membered heterocyclyl is to be understood as meaning both saturated, partially or fully unsaturated and aromatic heterocycles having one to three heteroatoms selected from a group consisting of one to three nitrogen atoms, one to two oxygen atoms and one or two sulfur atoms. Preference is given to saturated heterocycles, and among these in particular to those having one or two heteroatoms selected from oxygen and sulfur.
The saturated heterocycles may contain a carbonyl or. thiocarbonyl ring member.
~~5~/50571 CA 02381639 2002-02-11 Examples of saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: ' oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2-yl, oxetan-3-yl, 5 thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 10 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, 15 tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, 20 piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, 25 hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and hexahydro-1,4-diazepin-2-yl.
Saturated 5-or 6-membered N-bonded heterocyclyl is, for example,:
pyrrolidin-1-yl, tetrahydropyrazol-1-yl, piperidin-1-yl, hexahydropyrimidin-1-yl, piperazin-1-yl and morpholin-1-yl.
With respect to the use of the compounds of the formula I
according to the invention as herbicides, the variables Z, R1, RZ
and R3 preferably have the following meanings, in each case on their own or in combination:
Z is 0, S, or a single bond, in particular a single bond;
R1 is hydrogen, fluorine or chlorine;
RZ is halogen, in particular fluorine or chlorine, or cyano;
R3 is C1-C4-alkyl, C1-C4-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-Cq-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-Cq-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl;
is phenyl which may carry a substituent selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is saturated C3-C~-cycloalkyl, 3- to 7-membered saturated heterocyclyl which contains one, two or three heteroatoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member;
or, if Z is a chemical bond, R3 can also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CHz)n-CH(OH)-CHZ-R9 , -(CH2)n-CH(halo)-CHz-R9, -(CHZ)n-CHZ-CH(halo)-R9, -(CHZ)n-CH=CH-R9 or -(CHZ)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1.
Examples of particularly preferred radicals R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, propen-3-yl, propargyl, 2-buten-1-yl, 3-buten-1-yl, methoxymethyl, methoxyethyl, cyanomethyl, 2-cyanoethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, 2-chloroethyl, 2-chloromethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, dimethylaminocarbonylmethyl, hydroxymethyl, aminomethyl, methylaminomethyl, dimethylaminomethyl, diethylaminomethyl, 2-(methylamino)ethyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, (methylthio)carbonylmethyl, (ethylthio)carbonylmethyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxiran-2-yl, oxetan-2-yl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, oxepan-2-yl, thiiran-2-yl, thiethan-2-yl, tetrahydrothiophen-2-yl, tetrahydrothiopyran-2-yl, thiepan-2-yl, oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-3-yl, oxepan-3-yl, thiethan-3-yl, tetrahydrothiophen-3-yl, tetrahydrothiopyran-3-yl, thiepan-3-yl, tetrahydropyran-4-yl, oxepan-4-yl, tetrahydrothiopyran-4-yl, thiepan-4-yl, 2-oxocyclopropyl, 2-oxocyclobutyl, 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxocycloheptyl, 2-thioxocyclopropyl, 2-thioxocyclobutyl, 2-thioxocyclopentyl, 2-thioxocyclohexyl, 2-thioxocycloheptyl, 2-oxooxetan-3-yl, 2-oxothiethan-2-yl, 2-oxotetrahydrothien-3-yl, 2-oxotetrahydrothiopyran-3-yl, 2-oxothiepan-3-yl, 2-oxotetrahydrofuran-3-yl, 2-oxotetrahydropyran-2-yl, 2-oxooxepan-2-yl, 2-thioxooxetan-3-yl, 2-thioxothiethan-2-yl, 2-thioxotetrahydrothien-3-yl, 2-thioxotetrahydrothiopyran-3-yl, 2-thioxothiepan-3-yl, 2-thioxotetrahydrofuran-3-yl, 2-thioxotetrahydropyran-2-yl, 2-thioxooxepan-2-yl, -CHZ-CH(C1)-COOH, -CH2-CH(C1)-COOCH3, -CH2-CH(C1)-COOCHZCH3, -CH2-CH(C1)-COOCH(CH3)z, -CHZ-CH(C1)-COOCH2CH(CH3)2, -CH2-CH(C1)-COOCH(CH3)CH2CH3, -CHz-CH(C1)-COOC(CH3)3, -CHZ-CH(C1)-C00-n-C3H~, -CH2-CH(C1)-COO-n-CqH9, -CHZ-CH(Br)-COOH, -CHZ-CH(Br)-COOCH3, -CH2-CH(Br)-COOCH2CH3, -CH2-CH(Br)-COOCH(CH3)2.
-CH2-CH(Br)-COOCHZCH(CH3)Z, -CH2-CH(Br)-COOCH(CH3)CHyCH3, -CH2-CH(Br)-COOC(CH3)3, -CH2-CH(Br)-COO-n-C3H~, -CH2-CH(Br)-COO-n-C4H9, -CH=CH-COOH, -CH=CH-COOCH3, -CH=CH-COOCHZCH3, -CH=CH-COOCH(CH3)2, -CH=CH-COOCHZCH(CH3)2, -CH=CH-COOCH(CH3)CH2CH3, -CH=CH-COOC(CH3)3, -CH=CH-COO-n-C3H~, -CH=CH-COD-n-C4H9, -CH=CH(C1)-COOH, -CH=CH(Cl)-COOCH3, -CH=CH(Cl)-COOCH2CH3, -CH=CH(C1)-COOCH(CH3)z, -CH=CH(Cl)-COOCH2CH(CH3)2, -CH=CH(C1)-COOCH{CH3)CHZCH3, -CH=CH(C1)-COOC(CH3)3, -CH=CH(C1)-C00-n-C3H~, -CH=CH(C1)-COO-n-C4H9, -CH=CH(Br)-COOH, -CH=CH(Br)-COOCH3, -CH=CH(Br)-COOCHyCH3, -CH=CH(Br)-COOCH(CH3)z.
-CH=CH(Br)-COOCH2CH(CH3)Z, -CH=CH(Br)-COOCH(CH3)CH2CH3, -CH=CH(Br)-COOC(CH3)3, -CH=CH(Br)-COO-n-C3H~, -CH=CH(Br)-COO-n-C4H9, -CHZ-CH(C1)-CONH2, -CH2-CH(C1)-CONHCH3, -CHy-CH(C1)-CON(CH3)2, -CHZ-CH(C1)-CONHCZH5, -CHZ-CH(C1)-CON(CHzCH3)z, -CHz-CH(C1)-CONH-n-C3H~, -CHy-CH(C1)-CON(n-C3H~)2, -CH2-CH(Cl)-CONH-n-C4H9, 2$
-CHz-CH(C1)-CON(n-C4Hg)z , -CHz-CH(Br)--CONHz, -CHz-CH(Br)-CONHCH3, -CHz-CH(Br)-CON(CH3)z, -CHZ-CH(Br)-CONH-CZHS, -CHz-CH(Br)-CON(CHZCH3)z, -CHz-CH(Br)-CONH-n-C3H~, -CHz-CH(Br)-CON(n-C3H~)z, -CHz-CH(Br)-CONH-n-CqHg, -CHz-CH(Br)-CON(n-C4Hg)z , -CH=CH-CONHz, -CH=CH-CONHCH3, -CH=CH-COON(CH3)z, -CH=CH-COONHC2H5, -CH=CH-CON(CH2CH3)z, -CH=CH-CONH-n-C3H~, -CH=CH-CON(n-C3H~)z, -CH=CH-CONH-n-C4Hg, -CH=CH-CON(n-C4Hg)z, -CH=CH(C1)-CONHz, -CH=CH(C1)-CONHCH3, -CH=CH(C1)-CON(CH3)z, -CH=CH(C1)-CONHCZHS, -CH=CH(C1)-CON(CH2CH3)z, -CH=CH(C1)-CONH-n-C3H~, -CH=CH(C1)-CON(n-C3H~)z, -CH=CH(Cl)-CONH-n-C4Hg, -CH=CH(C1)-CON(n-CqHg)z , -CH=CH(Br)-CONHz, -CH=CH(Br)-CONHCH3, -CH=CH(Br)-CON(CH3)z, -CH=CH(Br)-CONH-CzHS, -CH=CH(Br)-CON(CHZCH3)z, -CH=CH(Br)-CONH-n-C3H~, -CH=CH(Br)-CON(n-C3H~)z, -CH=CH(Br)-CONH-n-C4Hg, -CH=CH(Br)-CON(n-C4Hg)z .
Very particularly preferably, R3 is C1-C4-alkyl, C1-C4-haloalkyl or phenyl which may be unsubstituted or may carry a substituent selected from halogen, C1-C4-alkyl and C1-C4-haloalkyl, is saturated C3-C~-cycloalkyl, especially cycloalkyl, C3-C~-cycloalkyl-C1-C4-alkyl, especially cyclopropylmethyl, 3- to 7-memebered saturated heterocyclyl which contains one, two or three heteroatoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member.
In other preferred compounds of the formula I, Het is a cycle of the formula II-4, II-5, II-6, II-10, II-14 or II-17, particular II-5 or II-6, attached via an imide nitrogen.
In other particularly preferred compounds of the formula I, Het is a nitrogen heterocycle which has at least one carbonyl or thiocarbonyl function and at least one endocyclic hydrazone structure and which is selected from the radicals of the formulae II-1, II-2, II-11 and II-12.
With regards to the herbicidal and/or desiccating or defoliating effectivity Het is preferably a radical of the formula II-1, II-2, II-5, II-6 or II-12 and in particular for a radical of the formula II-2, II-5 and II-12.
In Het, X and X' are preferably oxygen. Y is likewise preferably oxygen. Q in the formula II-1 is likewise preferably oxygen.
In the radicals Het, the variables R4, R4', R4" independently of one another preferably have the following meanings: hydrogen, C1-C6-alkyl, halogen, amino, C1-C6-haloalkyl, C1-C6-haloalkoxy, C1-C6-haloalkylthio or C1-C6-alkylsulfonyl.
In the radicals Het, the variables R5 and RS' independently of one another preferably have the following meanings: hydrogen, C1-C6-alkyl, amino or C1-C6-haloalkyl.
Preferred compounds of the formula I may also have radicals Het in which two of the radicals R4, R4', R4", R5 and RS' together with the cycle to which they are attached form a 5-, 6- or 7-membered ring which may be mono- or diunsaturated or saturated and which may contain one or two heteroatoms selected from oxygen and sulfur as ring member.
Among the compounds of the formula I in which Het is a cycle of the formula II-1, preference is given to those compounds in which X is oxygen. In these compounds, Q is preferably likewise oxygen.
In these compounds, R4 is preferably C1-C4-alkyl and in particular tert-butyl.
Among the compounds of the formula I in which Het is a cycle of the formula II-2, preference is given to those compounds in which X is oxygen. In these compounds, R5 is preferably hydrogen or C1-C4-alkyl and in particular methyl. R5 is preferably C1-C4-haloalkyl and in particular trifluoromethyl.
Among the compounds of the formula I in which Het is a cycle of the formula II-5, preference is given to those compounds in which X and X' are oxygen. In these compounds, R4 and R4' are preferably hydrogen or C1-C4-alkyl or they form together with the carbon atoms to which they are bonded a 6-membered carbocycle and in particular a cyclohexene- or benzene-cycle.
Among the compounds of the formula I in which Het is a cycle of the formula II-6, preference is given to those compounds in which X and X' are oxygen. Y is preferably likewise oxygen. In these compounds, R6 and R~ are preferably C1-C4-alkyl, in particular methyl or they form together with the carbon atom to which they are bonded a 5- or 6-membered saturated carbocycle.
Among the compounds of the formula I in which Het is a cycle of the formula II-12, preference is given to those compounds in which X is oxygen. In these compounds, R9 is preferably hydrogen, amino, C1-C4-alkyl and in particular methyl. R4' is preferably C1-C4-haloalkyl and in particular trifluoromethyl, or C1-C4-alkylsulfonyl, in particular. methylsulfonyl. R~" is in particular hydrogen.
Preference is given, in particular, to compounds of the formula 5 I-A., in which RZ is chlorine, Z is a single bond and Het is a radical of the formula II-1 in which X and Q are 0 and R4 is tert-butyl, and R1 and R3 have the meanings given in Table 1 (compounds I-Aa.l to I-Aa.558).
O' ' -NN ~ / CI
\ (I-A) ao Table 1:
Nr . R1 R3 or R3 ._,_ 2 H Me 3 H Et 4 H n-Pr 5 H n-Bu 6 H i-Pr 7 H CHZ-CH(CH3)2 8 H CH(Me)-C2H5 9 H C(CH3)3 10 H CHZ-CH=CHZ
11 H CHz-CH=CH-CH3 12 H CHzCH2-CH=CHZ
13 H CH2-C=CH
14 H CHMe-C = CH
15 H CH20Me 16 H CHzCH20Me 17 H CHzOCHZCH3 18 H CHzCHyOCH2CH3 19 H CHyCN
26 H CH2COOMe 27 H CH2COOEt 28 H CHzC00 n-Pr 29 H CHZCONMe2 31 H CHzNH2 33 H CHZN(CH3)p 34 H CHzN(CZHS)2 35 H CHzCHZNHCH3 36 H CHZCHZN(CH3)2 Nr . R1 R3 or R3' 37 H CH2CHzN(CZHS)2 38 H CHIC ( 0 ) SMe 39 H CHZC(0)SCyHS
40 H phenyl 41 H 4-Me-phenyl 42 H 4-C1-phenyl 43 H 3-Me-phenyl 44 H 2-Gl-phenyl 45 H 2-Me-phenyl 46 H 2-C1-phenyl 47 H cyclopropyl 4g H cyclobutyl 49 H cyclopentyl 50 H cyclohexyl 51 H cycloheptyl 52 H oxiran-2-yl 53 H oxetan-2-yl 54 H tetrahydrofuran-2-yl 55 H tetrahydropyran-2-yl 56 H oxepan-2-yl 57 H thiiran-2-yl 58 H thietan-2-yl 59 H tetrahydrothiofuran-2-yl 60 H tetrahydrothiopyran-2-yl 61 H thiepan-2-yl 62 H oxetan-3-yl 63 H tetrahydrofuran-3-yl 64 H tetrahydropyran-3-yl 65 H oxepan-3-yl 66 H thietan-3-yl 67 H tetrahydrothiofuran-3-yl 68 H tetrahydrothiopyran-3-yl 69 H thiepan-3-yl-70 H tetrahydropyran-4-yl 71 H oxepan-4-yl 72 H tetrahydrothiopyran-4-yl 73 H thiepan-4-yl 74 H 2-oxocyclopropyl 75 H 2-oxocyclobutyl Nr . R1 R3 or R3' 76 H 2-oxocyclopentyl 77 H 2-oxocyclohexyl 78 H 2-oxocycloheptyl 79 H 2-thioxocyclopropyl 80 H 2-thioxocyclobutyl 81 H 2-oxooxetan-3-yl 82 H 2-oxotetrahydrofuran-3-yl 83 H 2-oxotetrahydropyran-3-yl 84 H 2-oxooxepan-3-yl 85 H 2-thioxothietan-3-yl 86 H 2-thioxotetrahydrothien-3-yl g7 H 2-thioxotetrahydrothiopyran-3-yl 88 H 2-thioxothiepan-3-yl 89 H 2-thioxooxetan-3-yl 90 H 2-thioxotetrahydrofuran-3-yl 9l H 2-thioxotetrahydropyran-3-yl 92 H 2-thioxooxepan-3-yl 93 H 2-oxothietan-3-yl 94 H 2-oxotetrahydrothien-3-yl 95 H 2-oxotetrahydrothiopyran-3-yl 96 H 2-oxothiepan-3-yl 97 H -CH2-CH(C1)-CO-OCH3 98 H -CH2-CH(Cl)-CO-OC2H5 99 H -CH2-CH(C1)-CO-0(n-CgH~) 100 H -CH2-CH(C1)-CO-O(n-C9H9) 101 H -CH2-CH(C1)-CO-OCH(CH3)2 102 H -CH2-CH(Cl)-CO-OCH2-CH(CH3)2 103 H -CH2-CH(C1)-CO-OCH(CH3)-C2H5 104 H -CH2-CH(C1)-CO-OC(CH3)3 105 H -CH2-CH(Br)-CO-OH
106 H -CH2-CH(Br)-CO-OCH3 107 H -CH2-CH(Br)-CO-OC2H5 108 H -CH2-CH(C1)-CO-OH
109 H -CH2-CH(Br)-CO-0(n-C3H~) 110 H -CH2-CH(Br)-CO-O(n-C4H9) 111 H -CH2-CH(Br)-CO-OCH(CH3)2 112 H -CH2-CH(Br)-CO-OCH2-CH(CH3)2 113 H -CH2-CH(Br)-CO-OCH(CH3)-C2H5 114 H -CH2-CH(Br)-CO-OC(CH3)3 Nr . R1 R3 or R3 115 H -CH=CH-CO-OH
116 H -CH=CH-CO-OCH3 117 H -CH=CH-CO-OCZHS
118 H -CH=CH-CO-O(n-C3H~) 119 H -CH=CH-CO-O(n-C4Hg) 120 H -CH=CH-CO-OCH(CH3)z 121 H -CH=CH-CO-OCHz-CH(CH3)z 122 H -CH=CH-CO-OCH(CH3)-CzHS
123 H -CH=CH-CO-OC(CH3)3 124 H -CH=C(C1)-CO-OH
125 H -CH=C(C1)-CO-OCH3 126 H -CH=C(C1)-CO-OC2H5 127 H -CH=C(C1)-CO-0(n-C3H~) 128 H .CH=C(C1)-CO-0(n-C4Hg) 129 H -CH=C(C1)-CO-OCH(CH3)z 130 H -CH=C(C1)-CO-OCHz-CH(CH3)z 131 H -CH=C(C1)-CO-OCH(CH3)-C2H5 132 H -CH=C(C1)-CO-OC(CH3)3 133 H -CH=C(Br)-CO-OH
134 H -CH=C(Br)-CO-OCH3 135 H -CH=C(Br)-CO-OCyHs 136 H -CH=C(Br)-CO-0(n-C3H~) 137 H -CH=C(Br)-CO-0(n-C4Hg) 138 H -CH=C(Br)-CO-OCH(CH3)z 139 H -CH=C(Br)-CO-OCHz-CH(CH3)z 140 H -CH=C(Br)-CO-OCH(CH3)-CyH5 141 H -CH=C(Br)-CO-OC(CH3)3 142 H -CHZ-CH(Cl)-CO-NHz 143 H -CHZ-CH(C1)-CO-NH-CH3 144 H -CHZ-CH(C1)-CO-N(CH3)z 145 H -CHZ-CH(Cl)-CO-NH-C2H5 146 H -CHz-CH(C1)-CO-N(CzH5)z 147 H -CHz-CH(C1)-CO-NH-(n-C3H~) 148 H -CHz-CH(C1)-CO-N(n-C3H~)z 149 H -CHZ-CH(C1)-CO-NH-(n-CqHg) 150 H -CHZ-CH(C1)-CO-N(n-C4Hg)z 151 H -CHz-CH(Br)-CO-NHz 152 H -CHz-CH(Br)-CO-NH-CH3 153 H -CHZ-CH(Br)-CO-N(CH3)z ~~5~~50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3 154 H -CHZ-CH(Br)-CO-NH-CZHS
155 H -CHZ-CH(Br)-CO-N(CZHS)z 5 156 H -CHz-CH(Br)-CO-NH-(n-C3H7) 157 H -CHz-CH(Br)-CO-N(n-C3H~)z 158 H -CHZ-CH(Br)-CO-NH-(n-C4Hy) 159 H -CHz-CH(Br)-CO-N(n-CqH9)z 160 H -CH=CH-CO-NHz 161 H -CH=CH-CO-NH-CH3 162 H -CH=CH-CO-N(CH3)z 163 H -CH=CH-CO-NH-C2H5 164 H -CH=CH-CO-N(CZHS)z 15 165 H -CH=CH-CO-NH-(n-C3H~) 166 H -CH=CH-CO-N(n-C3H~)z 167 H -CH=CH-CO-NH-(n-C4H9) 168 H -CH=CH-CO-N(n-C4H9)2 20 169 H -CH=C(C1)-CO-NHz 170 H -CH=C(C1)-CO-NH-CH3 171 H -CH=C(C1)-CO-N(CH3)z 172 H -CH=C(C1)-CO-NH-CzHS
25 173 H -CH=C(C1)-CO-N(C2H5)z 174 H -CH=C(C1)-CO-NH-(n-C3H~) 175 H -CH=C(Cl)-CO-N(n-C3H~)z 176 H -CH=C(C1)-CO-NH-(n-C4H9) 177 H -CH=C(C1)-CO-N(n-C4H9)z 30 178 H -CH=C(Br)-CO-NHz 179 H -CH=C(Br)-CO-NH-CH3 180 H -CH=C(Br)-CO-NH(CH3)z 181 H -CH=C(Br)-CO-NH-CZHg 35 182 H -CH=C(Br)-CO-N(C2H5)z 183 H -CH=C(Br)-CO-NH-(n-C3H~) 184 H -CH=C(Br)-CO-N(n-C3H~)z 185 H -CH=C(Br)-CO-NH-(n-C4Hg) 186 H -CH=C(Br)-CO-N(n-C4H9)2 188 C1 Me 189 C1 Et 190 C1 n-Pr 191 C1 n-Bu 192 C1 i-Pr Nr . R1 R3 or R3' ~
193 C1 CHZ-CH(CH3)z 194 C1 CH(Me)-C2H5 195 Cl C(CH3)3 196 C1 CHz-CH=CHz 197 C1 CHZ-CH=CH-CH3 198 C1 CH2CHz-CH=CHz 199 C1 CHz-C=CH
200 C1 CHMe-C = CH
201 Cl CHZOMe 202 Cl CH2CHZOMe 204 C1 CHyCHZOCH2CH3 208 C1 CHZCl 211 C1 CH2CHzF
212 Cl CHZCOOMe 213 C1 CHzC00Et 214 C1 CH2C00 n-Pr 215 C1 CH2CONMez 217 C1 CHZNHz 219 C1 CHZN(CH3)2 220 Cl CH2N(CzH5)z 222 Cl CHZCHZN(CH3)z 223 Cl CHzCH2N(CzCl5)z 224 C1 CH2C(0)SMe 225 C1 CH2C(0)SCZHS
226 C1 phenyl 227 C1 4-Me-phenyl 228 C1 4-Cl-phenyl 229 C1 3-Me-phenyl 230 Cl 2-C1-phenyl 231 C1 2-Me-phenyl Nr . R1 R3 or R3 232 C1 2-C1-phenyl 233 C1 cyclopropyl 234 C1 cyclobutyl 235 C1 cyclopentyl 236 Cl cyclohexyl 237 C1 cycloheptyl 238 C1 oxiran-2-yl 239 C1 oxetan-2-yl 240 C1 tetrahydrofuran-2-yl 241 C1 tetrahydropyran-2-yl 242 C1 oxepan-2-yl 243 C1 'thiiran-2-yl 244 C1 thietan-2-yl 245 C1 tetrahydrothiofuran-2-yl 246 C1 tetrahydrothiopyran-2-yl 247 C1 thiepan-2-yl 248 Cl oxetan-3-yl 249 C1 tetrahydrofuran-3-yl 250 C1 tetrahydropyran-3-yl 251 C1 oxepan-3-yl 252 C1 thietan-3-yl 253 C1 tetrahydrothiofuran-3-yl 254 C1 tetrahydrothiopyran-3-yl 255 C1 thiepan-3-yl-256 C1 tetrahydropyran-4-yl 257 C1 oxepan-4-yl 258 C1 tetrahydrothiopyran-4-yl 259 C1 thiepan-4-yl 260 Cl 2-oxocyclopropyl 261 Cl 2-oxocyclobutyl 262 C1 2-oxocyclopentyl 263 C1 2-oxocyclohexyl 264 C1 2-oxocycloheptyl 265 C1 2-thioxocyclopropyl 266 Cl 2-thioxocyclobutyl 267 C1 2-oxooxetan-3-yl 268 C1 2-oxotetrahydrofuran-3-yl 269 C1 2-oxotetrahydropyran-3-yl 270 C1 2-oxooxepan-3-yl Nr. R1 R3 or R3' ~
271 C1 2-thioxothietan-3-yl 272 C1 2-thioxotetrahydrothien-3-yl 273 C1 2-thioxotetrahydrothiopyran-3-yl 274 C1 2-thioxothiepan-3-yl 275 Cl 2-thioxooxetan-3-yl 276 C1 2-thioxotetrahydrofuran-3-yl 277 CZ 2-thioxotetrahydropyran-3-yl 278 C1 2-thioxooxepan-3-yl 279 C1 2-oxothietan-3-yl 280 C1 2-oxotetrahydrothien-3-yl 281 C1 2-oxotetrahydrothiopyran-3-yl 15282 C1 2-oxothiepan-3-yl 283 C1 -CHz-CH(Cl)-CO-OCH3 284 C1 -CHz-CH(C1)-C0-OCZH5 285 C1 -CHz-CH(Cl)-CO-0(n-C3H~) 20286 C1 -CHz-CH(C1)-CO-0(n-C4Hg) 287 C1 -CHz-CH(C1)-CO-OCH(CH3)z 288 C1 -CHZ-CH(C1)-CO-OCHz-CH(CH3)z 289 C1 -CHz-CH(C1)-CO-OCH(CH3)-CZHS
25290 C1 -CHZ-CH(Cl)-CO-OC(CH3)3 291 C1 -CHz-CH(Br)-CO-OH
292 C1 -CHz-CH(Br)-GO-OCH3 293 C1 -CHz-CH(Br)-CO-OC2H5 294 Cl -CHz-CH(C1)-CO-OH
302g5 C1 -CHz-CH(Br)-CO-0(n-C3H~) 296 C1 -CHz-CH(Br)-CO-0(n-CqHg) 297 C1 -CHz-CH(Br)-CO-OCH(CH3)z 298 C1 -CHZ-CH(Br)-CO-OCHz-CH(CH3)z 35299 C1 -CHz-CH(Br)-CO-OCH(CH3)-CZHS
300 C1 -CHZ-CH(Br)-CO-OC(CH3)3 301 C1 -CH=CH-CO-OH
302 C1 -CH=CH-CO-OCH3 40303 C1 -CH=CH-CO-OCZHS
304 C1 -CH=CH-CO-0(n-C3H~) 305 C1 -CH=CH-CO-O(n-C4Hg) 306 C1 -CH=CH-CO-OCH(CH3)z 307 Cl -CH=CH-CO-OCHZ-CH(CH3)z 308 C1 -CH=CH-CO-OCH(CH3)-C2H5 309 C1 -CH=CH-CO-OC(CH3)3 ~U50/50571 CA 02381639 2002-02-11 Nr. R1 R3 or R3' 310 C1 -CH=C(C1)-CO-OH
311 C1 -CH=C(C1)-CO-OCH3 312 C1 -CH=C(C1)-CO-OC2H5 313 C1 -CH=C(C1)-CO-0(n-C3H~) 314 C1 -CH=C(C1)-CO-O(n-CqHg) 315 C1 -CH=C(Cl)-CO-OCH(CH3)2 316 C1 -CH=C(Cl)-CO-OCHz-CH(CH3)2 317 C1 -CH=C(Cl)-CO-OCH(CH3)-CyHS
318 C1 -CH=C(C1)-CO-OC(CH3)3 319 C1 -CH=C(Br)-CO-OH
320 C1 -CH=C(Br)-CO-OCH3 321 C1 -CH=C(Br)-CO-OCyH5 322 Cl -CH=C(Br)-CO-O(n-C3H~) 323 C1 -CH=C(Br)-CO-0(n-CqHg) 324 C1 -CH=C(Br)-CO-OCH(CH3)2 325 C1 -CH=C(Br)-CO-OCHZ-CH(CH3)Z
326 Cl -CH=C(Br)-CO-OCH(CH3)-C2H5 327 C1 -CH=C(Br)-CO-OC(CH3)3 328 C1 -CHZ-CH(C1)-CO-NH2 329 C1 -CHZ-CH(C1)-CO-NH-CH3 330 C1 -CHZ-CH(C1)-CO-N(CH3)2 331 C1 -CHZ-CH(C1)-CO-NH-CZH5 332 C1 -CH2-CH(Cl)-CO-N(CZHS)2 333 C1 -CHz-CH(C1)-CO-NH-(n-C3H~) 334 C1 -CHz-CH(C1)-CO-N(n-C3H~)2 335 C1 -CH2-CH(C1)-CO-NH-(n-C4Hg) 336 C1 -CHZ-CH(C1)-CO-N(n-C4Hg)Z
337 Cl -CHZ-CH(Br)-CO-NHZ
338 C1 -CHZ-CH(Br)-CO-NH-CH3 339 C1 -CH2-CH(Br)-CO-N(CH3)2 340 C1 -CHZ-CH(Br)-CO-NH-CzHS
341 C1 -CH2-CH(Br)-CO-N(C2H5)2 342 C1 -CHZ-CH(Br)-CO-NH-(n-C3H~) 343 C1 -CHz-CH(Br)-CO-N(n-C3H~)z 344 C1 -CH2-CH(Br)-CO-NH-(n-C4Hg) 345 C1 -CHz-CH(Br)-CO-N(n-CqH9)2 346 C1 -CH=CH-CO-NH2 347 C1 -CH=CH-CO-NH-CHI
348 C1 -CH=CH-CO-N(CH3)z Nr . R1 R3 or R3' 349 C1 -CH=CH-CO-NH--CZHS
350 Cl -CH=CH-CO-N(CZHS)2 5 351 C1 -CH=CH-CO-NH-(n-C3H~) 352 C1 -CH=CH-CO-N(n-C3H~)2 353 C1 -CH=CH-CO-NH-(n-C4Hg) 354 C1 -CH=GH-CO-N(n-C4Hg)2 355 C1 -CH=C(C1)-CO-NH2 356 C1 -CH=C(Cl)-CO-NH-CHg 357 C1 -CH=C(C1)-CO-N(CH3)y 358 C1 -CH=C(C1)-CO-NH-C2H5 359 C1 -CH=C(C1)-CO-N(C2H5)2 15 360 C1 -CH=C(C1)-CO-NH-(n-C3H~) 361 Cl -CH=C(C1)-CO-N(n-C3H~)2 362 C1 -CH=C(C1)-CO-NH-(n-C4Hg) 363 C1 -CH=C(C1)-CO-N(n-C4Hg)2 20 364 C1 -CH=C(Br)-CO-NH2 365 C1 -CH=C(Br)-CO-NH-CH3 366 C1 -CH=C(Br)-CO-NH(CH3)2 367 C1 -CH=C(Br)-CO-NH-C2H5 25 368 C1 -CH=C(Br)-CO-N(C2H5)2 369 C1 -CH=C(Br)-CO-NH-(n-C3H~) 370 C1 -CH=C(Br)-CO-N(n-C3H~)2 371 C1 -CH=C(Br)-CO-NH-(n-C4Hg) 372 C1 -CH=C(Br)-CO-N(n-CqHg)y 374 F Me 375 F Et 376 F n-Pr 35 377 F n-Bu 378 F i-Pr 379 F CHZ-CH(CH3)2 380 F CH(Me)-C2H5 40 381 F C(CH3)3 382 F CH2-CH=CH2 383 F CHZ-CH=CH-CH3 384 F CH2CH2-CH=CHZ
385 F CH2-C=CH
3 8 6 F CHMe-C = CH
387 F CH20Me Nr . R1 R3 or R3 388 F CH2CHy0Me 396 F CHZCHZCl 397 F CHzCH2F
398 F CH2COOMe 15399 F CHZCOOEt 400 F CHzC00 n-Pr 401 F CHZCONMey 402 F CHzOH
405 F CH2N(CH3)2 406 F CH2N(CZHS)y 408 F CH2CHZN (CH3 ) 2 409 F CH2CH2N(C2H5)2 410 F CHzC(O)SMe 411 F CH2C(O)SC2H5 30412 F phenyl 413 F 4-Me-phenyl 414 F 4-C1-phenyl 415 F 3-Me-phenyl 35416 F 2-C1-phenyl 417 F 2-Me-phenyl 418 F 2-C1-phenyl 419 F cyclopropyl 40420 F cyclobutyl 421 F cyclopentyl 422 F cyclohexyl 423 F cycloheptyl 424 F oxiran-2-yl 425 F oxetan-2-yl 426 F tetrahydrofuran-2-yl ~05~/50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3' --427 F tetrahydropyran-2-yl 428 F oxepan-2-yl 429 F thiiran-2-yl 430 F thietan-2-yl 431 F tetrahydrothiofuran-2-yl 432 F tetrahydrothiopyran-2-yl 433 F thiepan-2-yl 434 F oxetan-3-yl 435 F tetrahydrofuran-3-yl 436 F tetrahydropyran-3-yl 437 F oxepan-3-yl 438 F thietan-3-yl 439 F tetrahydrothiofuran-3-yl 440 F tetrahydrothiopyran-3-yl 441 F thiepan-3-yl-442 F tetrahydropyran-4-yl 443 F oxepan-4-yl 444 F tetrahydrothiopyran-4-yl 445 F thiepan-4-yl 446 F 2-oxocyclopropyl 447 F 2-oxocyclobutyl 448 F 2-oxocyclopentyl 449 F 2-oxocyclohexyl 450 F 2-oxocycloheptyl 451 F 2-thioxocyclopropyl 452 F 2-thioxocyclobutyl 453 F 2-oxooxetan-3-yl 454 F 2-oxotetrahydrofuran-3-yl 455 F 2-oxotetrahydropyran-3-yl 456 F 2-oxooxepan-3-yl 457 F 2-thioxothietan-3-yl 458 F 2-thioxotetrahydrothien-3-yl 459 F 2-thioxotetrahydrothiopyran-3-yl 460 F 2-thioxothiepan-3-yl 461 F 2-thioxooxetan-3-yl 462 F 2-thioxotetrahydrofuran-3-yl 463 F 2-thioxotetrahydropyran-3-yl 464 F . 2-thioxooxepan-3-yl 465 F 2-oxothietan-3-yl Nr. R1 R3 or R3' 466 F 2-oxotetrahydrothien-3-yl 467 F 2-oxotetrahydrothiopyran-3-yl 468 F 2-oxothiepan-3-yl 469 F -CHZ-CH(C1)-CO-OCH3 470 F -CHZ-CH(Cl)-CO-OC2H5 471 F -CHz-CH(C1)-CO-O(n-C3H~) 472 F -CH2-CH(C1)-CO-0(n-CqH9) 473 F -CH2-CH(C1)-CO-OCH(CH3)2 474 F -CHZ-CH(C1)-CO-OCHZ-CH(CH3)2 475 F -CHZ-CH(C1)-CO-OCH(CH3)-CZHS
476 F -CH2-CH(C1)-CO-OC(CH3)3 477 F -CH2-CH(Br)-CO-OH
478 F -CHZ-CH(Br)-CO-OCH3 479 F -CHz-CH(Br)-CO-OCzHs 480 F -CHy-CH(C1)-CO-OH
481 F -CHZ-CH(Br)-CO-O(n-C3H~) 482 F -CHZ-CH(Br)-CO-0(n-C4H9) 483 F -CHZ-CH(Br)-CO-OCH(CH3)2 484 F -CHZ-CH(Br)-CO-OCHZ-CH(CH3)2 485 F -CHZ-CH(Br)-CO-OCH(CH3)-CZH5 486 F -CH2-CH(Br)-CO-OC(CH3)3 487 F -CH=CH-CO-OH
488 F -CH=CH-CO-OCH3 489 F -CH=CH-CO-OC2H5 4g0 F -CH=CH-CO-O(n-C3H~) 491 F -CH=CH-CO-0(n-C4H9) 492 F -CH=CH-CO-OCH(CH3)2 493 F -CH=CH-CO-OCH2-CH(CH3)2 494 F -CH=CH-CO-OCH(CH3)-C2H5 495 F -CH=CH-CO-OC(CH3)3 496 F -CH=C(C1)-CO-OH
497 F -CH=C(C1)-CO-OCH3 498 F -CH=C(C1)-CO-OC2H5 499 F -CH=C(C1)-CO-0(n-C3H~) 500 F -CH=C(C1)-CO-0(n-C4H9) 501 F -CH=C(C1)-CO-OCH(CH3)2 502 F -CH=C(C1)-CO-OCHz-CH(CH3)2 503 F -CH=C(C1)-CO-OCH(CH3)-CZH5 504 F -CH=C(Cl)-CO-OC(CH3)3 Nr. R1 R3 or R3' 505 F -GH=C(Br)-CO-OH
506 F -CH=C(Br)-CO-OCH3 507 F -CH=C(Br)-CO-OC2H5 508 F -CH=C(Br)-CO-0(n-C3H~) 509 F -CH=C(Br)-CO-0(n-C4Hg) 510 F -CH=C(Br)-CO-OCH(CH3)2 511 F -CH=C(Br)-CO-OCHz-CH(CH3)2 512 F -CH=C(Br)-CO-OCH(CH3)-CzH5 513 F -CH=C(Br)-CO-OC(CH3)3 514 F -CH2-CH(C1)-CO-NHZ
515 F -CHZ-CH(C1)-CO-NH-CH3 516 F -CHZ-CH(Cl)-CO-N(CH3)2 _ 517 F -CHz-CH(C1)-CO-NH-CzH5 518 F -CH2-CH(C1)-CO-N(C2H5)2 519 F -CH2-CH(C1)-CO-NH-(n-C3H~) 520 F -CHZ-CH(C1)-CO-N(n-C3H~)2 521 F -CH2-CH(Cl)-CO-NH-(n-C4Hg) 522 F -CH2-CH(C1)-CO-N(n-C4Hg)z 523 F -CHZ-CH(Br)-CO-NH2 524 F -CHZ-CH(Br)-CO-NH-CH3 525 F -CHZ-CH(Br)-CO-N(CH3)z 526 F -CH2-CH(Br)-CO-NH-CZH5 527 F -CH2-CH(Br)-CO-N(CzHS)2 528 F -CH2-CH(Br)-CO-NH-(n-C3H~) 529 F -CH2-CH{Br)-CO-N(n-C3H~)Z
530 F -CHZ-CH(Br)-CO-NH-(n-CqHg) 531 F -CHZ-CH(Br)-CO-N(n-C4Hg)Z
532 F -CH=CH-CO-NH2 533 F -CH=CH-CO-NH-CH3 534 F -CH=CH-CO-N(CH3)2 535 F -CH=CH-CO-NH-CZHS
536 F -CH=CH-CO-N(CZHS)2 537 F -CH=CH-CO-NH-(n-C3H~) 538 F -CH=CH-CO-N(n-C3H7)2 539 F -CH=CH-CO-NH-(n-C4Hg) 540 F -CH=CH-CO-N(n-C4Hg)2 541 F -CH=C(C1)-CO-NH2 542 F -CH=C(C1)-CO-NH-CH3 543 F -CH=C(C1)-CO-N(CH3)2 0U5~~50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3' 544 F -CH=C(C1)-CO-NH-CZHS
545 F -CH=C(C1)-CO-N(C2H5)2 5 546 F -CH=C(G1)-CO-NH-(n-C3H~) 547 F -CH=C(C1)-CO-N(n-C3H~)Z
548 F -CH=C(G1)-CO-NH-(n-CqHg) 549 F -CH=C(C1)-CO-N(n-C4Hg)2 550 F -CH=C(Br)-CO-NHz 551 F -CH=C(Br)-CO-NH-CH3 552 F -CH=C(Br)-CO-NH(CH3)2 553 F -CH=C(Br)-CO-NH-CZH5 554 F -CH=C(Br)-CO-N(CZHS)2 15 555 F -CH=C(Br)-CO-NH-(n-C3H~) 556 F -CH=C(Br)-CO-N(n-C3H~)2 557 F -CH=C(Br)-CO-NH-(n-C4Hg) 558 F -CH=C(Br)-CO-N(n-C4Hg)2 Preference is in particular also given to compounds of the formula I-A, in which Z is a single bond, R3 is a group CH2-R3., wherein R3' and R1 have the meanings given in Table 1 (compounds I-Ab.l to I-Ab.558).
Preference is in particular also given to compounds of the formula I-A, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ac.l to I-Ac.558).
Preference is in particular also given to compounds of the formula I-A, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ad.l to I-Ad.558).
preference is in particular also given to compounds of the formula I-B, in which Z is a single bond, Het is a radical of the formula II-2 with X = oxygen, R4 = trifluoromethyl and R5 = me-thyl, RZ is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ba.l to I-Ba.558).
H C-N
~1--' / N (I-B) CF3 O' /'N
Preference is in particular also given to compounds of the formula I-B, in which Z is a single bond, R3 is a group CHZ-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Bb.l to I-Bb.558).
Preference is in particular also given to compounds of the formula I-B, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Bc.l to I-Bc.558).
Preference is in particular also given to compounds of the formula I-B, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Bd.l to I-Bd.558).
Preference is in particular also given to compounds of the formula I-C, in which Z is a single bond, Het is a radical of the formula II-5 with X = X' - oxygen, wherein R4 and R4' together with the carbon atoms to which they are bonded form a cyclohexene ring, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ca.l to I-Ca.558).
N ~ / 1 \\ \ ( I-C ) 0 0 ~N
Preference is in particular also given to compounds of the formula I-C, in which Z is a single bond, R3 is a group CHZ-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Cb.l to I-Cb.558).
~
' 0050/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-C, in which Z is an oxygen atom and R1 and R' have the meanings given in Table 1 (compounds I-Cc.l to I-Cc.558).
Preference is in particular also given to compounds of the formula I-C, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Cd.l to I-Cd.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is a single bond, Het is a radical of the formula II-5 with X = X' - Schwefel, wherein R4 and R4' toge-ther with the carbon atoms to which they are bonded form a cyclo-hexene ring, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-C'a.l to I-C'a.558).
N ~ / 1 ~~ ~ ( I-c' ~
S O ~N
Preference is in particular also given to compounds of the formula I-C', in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-C'b.l to I-C'b.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-C'c.l to I-C'c.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-C'd.l to I-C'd.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is a single bond, Het is a radical of the formula II-6 with X = X' - Y = oxygen, R6 and R~ = methyl, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (com-pounds I-Da.l to I-Da.558).
106 H -CH2-CH(Br)-CO-OCH3 107 H -CH2-CH(Br)-CO-OC2H5 108 H -CH2-CH(C1)-CO-OH
109 H -CH2-CH(Br)-CO-0(n-C3H~) 110 H -CH2-CH(Br)-CO-O(n-C4H9) 111 H -CH2-CH(Br)-CO-OCH(CH3)2 112 H -CH2-CH(Br)-CO-OCH2-CH(CH3)2 113 H -CH2-CH(Br)-CO-OCH(CH3)-C2H5 114 H -CH2-CH(Br)-CO-OC(CH3)3 Nr . R1 R3 or R3 115 H -CH=CH-CO-OH
116 H -CH=CH-CO-OCH3 117 H -CH=CH-CO-OCZHS
118 H -CH=CH-CO-O(n-C3H~) 119 H -CH=CH-CO-O(n-C4Hg) 120 H -CH=CH-CO-OCH(CH3)z 121 H -CH=CH-CO-OCHz-CH(CH3)z 122 H -CH=CH-CO-OCH(CH3)-CzHS
123 H -CH=CH-CO-OC(CH3)3 124 H -CH=C(C1)-CO-OH
125 H -CH=C(C1)-CO-OCH3 126 H -CH=C(C1)-CO-OC2H5 127 H -CH=C(C1)-CO-0(n-C3H~) 128 H .CH=C(C1)-CO-0(n-C4Hg) 129 H -CH=C(C1)-CO-OCH(CH3)z 130 H -CH=C(C1)-CO-OCHz-CH(CH3)z 131 H -CH=C(C1)-CO-OCH(CH3)-C2H5 132 H -CH=C(C1)-CO-OC(CH3)3 133 H -CH=C(Br)-CO-OH
134 H -CH=C(Br)-CO-OCH3 135 H -CH=C(Br)-CO-OCyHs 136 H -CH=C(Br)-CO-0(n-C3H~) 137 H -CH=C(Br)-CO-0(n-C4Hg) 138 H -CH=C(Br)-CO-OCH(CH3)z 139 H -CH=C(Br)-CO-OCHz-CH(CH3)z 140 H -CH=C(Br)-CO-OCH(CH3)-CyH5 141 H -CH=C(Br)-CO-OC(CH3)3 142 H -CHZ-CH(Cl)-CO-NHz 143 H -CHZ-CH(C1)-CO-NH-CH3 144 H -CHZ-CH(C1)-CO-N(CH3)z 145 H -CHZ-CH(Cl)-CO-NH-C2H5 146 H -CHz-CH(C1)-CO-N(CzH5)z 147 H -CHz-CH(C1)-CO-NH-(n-C3H~) 148 H -CHz-CH(C1)-CO-N(n-C3H~)z 149 H -CHZ-CH(C1)-CO-NH-(n-CqHg) 150 H -CHZ-CH(C1)-CO-N(n-C4Hg)z 151 H -CHz-CH(Br)-CO-NHz 152 H -CHz-CH(Br)-CO-NH-CH3 153 H -CHZ-CH(Br)-CO-N(CH3)z ~~5~~50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3 154 H -CHZ-CH(Br)-CO-NH-CZHS
155 H -CHZ-CH(Br)-CO-N(CZHS)z 5 156 H -CHz-CH(Br)-CO-NH-(n-C3H7) 157 H -CHz-CH(Br)-CO-N(n-C3H~)z 158 H -CHZ-CH(Br)-CO-NH-(n-C4Hy) 159 H -CHz-CH(Br)-CO-N(n-CqH9)z 160 H -CH=CH-CO-NHz 161 H -CH=CH-CO-NH-CH3 162 H -CH=CH-CO-N(CH3)z 163 H -CH=CH-CO-NH-C2H5 164 H -CH=CH-CO-N(CZHS)z 15 165 H -CH=CH-CO-NH-(n-C3H~) 166 H -CH=CH-CO-N(n-C3H~)z 167 H -CH=CH-CO-NH-(n-C4H9) 168 H -CH=CH-CO-N(n-C4H9)2 20 169 H -CH=C(C1)-CO-NHz 170 H -CH=C(C1)-CO-NH-CH3 171 H -CH=C(C1)-CO-N(CH3)z 172 H -CH=C(C1)-CO-NH-CzHS
25 173 H -CH=C(C1)-CO-N(C2H5)z 174 H -CH=C(C1)-CO-NH-(n-C3H~) 175 H -CH=C(Cl)-CO-N(n-C3H~)z 176 H -CH=C(C1)-CO-NH-(n-C4H9) 177 H -CH=C(C1)-CO-N(n-C4H9)z 30 178 H -CH=C(Br)-CO-NHz 179 H -CH=C(Br)-CO-NH-CH3 180 H -CH=C(Br)-CO-NH(CH3)z 181 H -CH=C(Br)-CO-NH-CZHg 35 182 H -CH=C(Br)-CO-N(C2H5)z 183 H -CH=C(Br)-CO-NH-(n-C3H~) 184 H -CH=C(Br)-CO-N(n-C3H~)z 185 H -CH=C(Br)-CO-NH-(n-C4Hg) 186 H -CH=C(Br)-CO-N(n-C4H9)2 188 C1 Me 189 C1 Et 190 C1 n-Pr 191 C1 n-Bu 192 C1 i-Pr Nr . R1 R3 or R3' ~
193 C1 CHZ-CH(CH3)z 194 C1 CH(Me)-C2H5 195 Cl C(CH3)3 196 C1 CHz-CH=CHz 197 C1 CHZ-CH=CH-CH3 198 C1 CH2CHz-CH=CHz 199 C1 CHz-C=CH
200 C1 CHMe-C = CH
201 Cl CHZOMe 202 Cl CH2CHZOMe 204 C1 CHyCHZOCH2CH3 208 C1 CHZCl 211 C1 CH2CHzF
212 Cl CHZCOOMe 213 C1 CHzC00Et 214 C1 CH2C00 n-Pr 215 C1 CH2CONMez 217 C1 CHZNHz 219 C1 CHZN(CH3)2 220 Cl CH2N(CzH5)z 222 Cl CHZCHZN(CH3)z 223 Cl CHzCH2N(CzCl5)z 224 C1 CH2C(0)SMe 225 C1 CH2C(0)SCZHS
226 C1 phenyl 227 C1 4-Me-phenyl 228 C1 4-Cl-phenyl 229 C1 3-Me-phenyl 230 Cl 2-C1-phenyl 231 C1 2-Me-phenyl Nr . R1 R3 or R3 232 C1 2-C1-phenyl 233 C1 cyclopropyl 234 C1 cyclobutyl 235 C1 cyclopentyl 236 Cl cyclohexyl 237 C1 cycloheptyl 238 C1 oxiran-2-yl 239 C1 oxetan-2-yl 240 C1 tetrahydrofuran-2-yl 241 C1 tetrahydropyran-2-yl 242 C1 oxepan-2-yl 243 C1 'thiiran-2-yl 244 C1 thietan-2-yl 245 C1 tetrahydrothiofuran-2-yl 246 C1 tetrahydrothiopyran-2-yl 247 C1 thiepan-2-yl 248 Cl oxetan-3-yl 249 C1 tetrahydrofuran-3-yl 250 C1 tetrahydropyran-3-yl 251 C1 oxepan-3-yl 252 C1 thietan-3-yl 253 C1 tetrahydrothiofuran-3-yl 254 C1 tetrahydrothiopyran-3-yl 255 C1 thiepan-3-yl-256 C1 tetrahydropyran-4-yl 257 C1 oxepan-4-yl 258 C1 tetrahydrothiopyran-4-yl 259 C1 thiepan-4-yl 260 Cl 2-oxocyclopropyl 261 Cl 2-oxocyclobutyl 262 C1 2-oxocyclopentyl 263 C1 2-oxocyclohexyl 264 C1 2-oxocycloheptyl 265 C1 2-thioxocyclopropyl 266 Cl 2-thioxocyclobutyl 267 C1 2-oxooxetan-3-yl 268 C1 2-oxotetrahydrofuran-3-yl 269 C1 2-oxotetrahydropyran-3-yl 270 C1 2-oxooxepan-3-yl Nr. R1 R3 or R3' ~
271 C1 2-thioxothietan-3-yl 272 C1 2-thioxotetrahydrothien-3-yl 273 C1 2-thioxotetrahydrothiopyran-3-yl 274 C1 2-thioxothiepan-3-yl 275 Cl 2-thioxooxetan-3-yl 276 C1 2-thioxotetrahydrofuran-3-yl 277 CZ 2-thioxotetrahydropyran-3-yl 278 C1 2-thioxooxepan-3-yl 279 C1 2-oxothietan-3-yl 280 C1 2-oxotetrahydrothien-3-yl 281 C1 2-oxotetrahydrothiopyran-3-yl 15282 C1 2-oxothiepan-3-yl 283 C1 -CHz-CH(Cl)-CO-OCH3 284 C1 -CHz-CH(C1)-C0-OCZH5 285 C1 -CHz-CH(Cl)-CO-0(n-C3H~) 20286 C1 -CHz-CH(C1)-CO-0(n-C4Hg) 287 C1 -CHz-CH(C1)-CO-OCH(CH3)z 288 C1 -CHZ-CH(C1)-CO-OCHz-CH(CH3)z 289 C1 -CHz-CH(C1)-CO-OCH(CH3)-CZHS
25290 C1 -CHZ-CH(Cl)-CO-OC(CH3)3 291 C1 -CHz-CH(Br)-CO-OH
292 C1 -CHz-CH(Br)-GO-OCH3 293 C1 -CHz-CH(Br)-CO-OC2H5 294 Cl -CHz-CH(C1)-CO-OH
302g5 C1 -CHz-CH(Br)-CO-0(n-C3H~) 296 C1 -CHz-CH(Br)-CO-0(n-CqHg) 297 C1 -CHz-CH(Br)-CO-OCH(CH3)z 298 C1 -CHZ-CH(Br)-CO-OCHz-CH(CH3)z 35299 C1 -CHz-CH(Br)-CO-OCH(CH3)-CZHS
300 C1 -CHZ-CH(Br)-CO-OC(CH3)3 301 C1 -CH=CH-CO-OH
302 C1 -CH=CH-CO-OCH3 40303 C1 -CH=CH-CO-OCZHS
304 C1 -CH=CH-CO-0(n-C3H~) 305 C1 -CH=CH-CO-O(n-C4Hg) 306 C1 -CH=CH-CO-OCH(CH3)z 307 Cl -CH=CH-CO-OCHZ-CH(CH3)z 308 C1 -CH=CH-CO-OCH(CH3)-C2H5 309 C1 -CH=CH-CO-OC(CH3)3 ~U50/50571 CA 02381639 2002-02-11 Nr. R1 R3 or R3' 310 C1 -CH=C(C1)-CO-OH
311 C1 -CH=C(C1)-CO-OCH3 312 C1 -CH=C(C1)-CO-OC2H5 313 C1 -CH=C(C1)-CO-0(n-C3H~) 314 C1 -CH=C(C1)-CO-O(n-CqHg) 315 C1 -CH=C(Cl)-CO-OCH(CH3)2 316 C1 -CH=C(Cl)-CO-OCHz-CH(CH3)2 317 C1 -CH=C(Cl)-CO-OCH(CH3)-CyHS
318 C1 -CH=C(C1)-CO-OC(CH3)3 319 C1 -CH=C(Br)-CO-OH
320 C1 -CH=C(Br)-CO-OCH3 321 C1 -CH=C(Br)-CO-OCyH5 322 Cl -CH=C(Br)-CO-O(n-C3H~) 323 C1 -CH=C(Br)-CO-0(n-CqHg) 324 C1 -CH=C(Br)-CO-OCH(CH3)2 325 C1 -CH=C(Br)-CO-OCHZ-CH(CH3)Z
326 Cl -CH=C(Br)-CO-OCH(CH3)-C2H5 327 C1 -CH=C(Br)-CO-OC(CH3)3 328 C1 -CHZ-CH(C1)-CO-NH2 329 C1 -CHZ-CH(C1)-CO-NH-CH3 330 C1 -CHZ-CH(C1)-CO-N(CH3)2 331 C1 -CHZ-CH(C1)-CO-NH-CZH5 332 C1 -CH2-CH(Cl)-CO-N(CZHS)2 333 C1 -CHz-CH(C1)-CO-NH-(n-C3H~) 334 C1 -CHz-CH(C1)-CO-N(n-C3H~)2 335 C1 -CH2-CH(C1)-CO-NH-(n-C4Hg) 336 C1 -CHZ-CH(C1)-CO-N(n-C4Hg)Z
337 Cl -CHZ-CH(Br)-CO-NHZ
338 C1 -CHZ-CH(Br)-CO-NH-CH3 339 C1 -CH2-CH(Br)-CO-N(CH3)2 340 C1 -CHZ-CH(Br)-CO-NH-CzHS
341 C1 -CH2-CH(Br)-CO-N(C2H5)2 342 C1 -CHZ-CH(Br)-CO-NH-(n-C3H~) 343 C1 -CHz-CH(Br)-CO-N(n-C3H~)z 344 C1 -CH2-CH(Br)-CO-NH-(n-C4Hg) 345 C1 -CHz-CH(Br)-CO-N(n-CqH9)2 346 C1 -CH=CH-CO-NH2 347 C1 -CH=CH-CO-NH-CHI
348 C1 -CH=CH-CO-N(CH3)z Nr . R1 R3 or R3' 349 C1 -CH=CH-CO-NH--CZHS
350 Cl -CH=CH-CO-N(CZHS)2 5 351 C1 -CH=CH-CO-NH-(n-C3H~) 352 C1 -CH=CH-CO-N(n-C3H~)2 353 C1 -CH=CH-CO-NH-(n-C4Hg) 354 C1 -CH=GH-CO-N(n-C4Hg)2 355 C1 -CH=C(C1)-CO-NH2 356 C1 -CH=C(Cl)-CO-NH-CHg 357 C1 -CH=C(C1)-CO-N(CH3)y 358 C1 -CH=C(C1)-CO-NH-C2H5 359 C1 -CH=C(C1)-CO-N(C2H5)2 15 360 C1 -CH=C(C1)-CO-NH-(n-C3H~) 361 Cl -CH=C(C1)-CO-N(n-C3H~)2 362 C1 -CH=C(C1)-CO-NH-(n-C4Hg) 363 C1 -CH=C(C1)-CO-N(n-C4Hg)2 20 364 C1 -CH=C(Br)-CO-NH2 365 C1 -CH=C(Br)-CO-NH-CH3 366 C1 -CH=C(Br)-CO-NH(CH3)2 367 C1 -CH=C(Br)-CO-NH-C2H5 25 368 C1 -CH=C(Br)-CO-N(C2H5)2 369 C1 -CH=C(Br)-CO-NH-(n-C3H~) 370 C1 -CH=C(Br)-CO-N(n-C3H~)2 371 C1 -CH=C(Br)-CO-NH-(n-C4Hg) 372 C1 -CH=C(Br)-CO-N(n-CqHg)y 374 F Me 375 F Et 376 F n-Pr 35 377 F n-Bu 378 F i-Pr 379 F CHZ-CH(CH3)2 380 F CH(Me)-C2H5 40 381 F C(CH3)3 382 F CH2-CH=CH2 383 F CHZ-CH=CH-CH3 384 F CH2CH2-CH=CHZ
385 F CH2-C=CH
3 8 6 F CHMe-C = CH
387 F CH20Me Nr . R1 R3 or R3 388 F CH2CHy0Me 396 F CHZCHZCl 397 F CHzCH2F
398 F CH2COOMe 15399 F CHZCOOEt 400 F CHzC00 n-Pr 401 F CHZCONMey 402 F CHzOH
405 F CH2N(CH3)2 406 F CH2N(CZHS)y 408 F CH2CHZN (CH3 ) 2 409 F CH2CH2N(C2H5)2 410 F CHzC(O)SMe 411 F CH2C(O)SC2H5 30412 F phenyl 413 F 4-Me-phenyl 414 F 4-C1-phenyl 415 F 3-Me-phenyl 35416 F 2-C1-phenyl 417 F 2-Me-phenyl 418 F 2-C1-phenyl 419 F cyclopropyl 40420 F cyclobutyl 421 F cyclopentyl 422 F cyclohexyl 423 F cycloheptyl 424 F oxiran-2-yl 425 F oxetan-2-yl 426 F tetrahydrofuran-2-yl ~05~/50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3' --427 F tetrahydropyran-2-yl 428 F oxepan-2-yl 429 F thiiran-2-yl 430 F thietan-2-yl 431 F tetrahydrothiofuran-2-yl 432 F tetrahydrothiopyran-2-yl 433 F thiepan-2-yl 434 F oxetan-3-yl 435 F tetrahydrofuran-3-yl 436 F tetrahydropyran-3-yl 437 F oxepan-3-yl 438 F thietan-3-yl 439 F tetrahydrothiofuran-3-yl 440 F tetrahydrothiopyran-3-yl 441 F thiepan-3-yl-442 F tetrahydropyran-4-yl 443 F oxepan-4-yl 444 F tetrahydrothiopyran-4-yl 445 F thiepan-4-yl 446 F 2-oxocyclopropyl 447 F 2-oxocyclobutyl 448 F 2-oxocyclopentyl 449 F 2-oxocyclohexyl 450 F 2-oxocycloheptyl 451 F 2-thioxocyclopropyl 452 F 2-thioxocyclobutyl 453 F 2-oxooxetan-3-yl 454 F 2-oxotetrahydrofuran-3-yl 455 F 2-oxotetrahydropyran-3-yl 456 F 2-oxooxepan-3-yl 457 F 2-thioxothietan-3-yl 458 F 2-thioxotetrahydrothien-3-yl 459 F 2-thioxotetrahydrothiopyran-3-yl 460 F 2-thioxothiepan-3-yl 461 F 2-thioxooxetan-3-yl 462 F 2-thioxotetrahydrofuran-3-yl 463 F 2-thioxotetrahydropyran-3-yl 464 F . 2-thioxooxepan-3-yl 465 F 2-oxothietan-3-yl Nr. R1 R3 or R3' 466 F 2-oxotetrahydrothien-3-yl 467 F 2-oxotetrahydrothiopyran-3-yl 468 F 2-oxothiepan-3-yl 469 F -CHZ-CH(C1)-CO-OCH3 470 F -CHZ-CH(Cl)-CO-OC2H5 471 F -CHz-CH(C1)-CO-O(n-C3H~) 472 F -CH2-CH(C1)-CO-0(n-CqH9) 473 F -CH2-CH(C1)-CO-OCH(CH3)2 474 F -CHZ-CH(C1)-CO-OCHZ-CH(CH3)2 475 F -CHZ-CH(C1)-CO-OCH(CH3)-CZHS
476 F -CH2-CH(C1)-CO-OC(CH3)3 477 F -CH2-CH(Br)-CO-OH
478 F -CHZ-CH(Br)-CO-OCH3 479 F -CHz-CH(Br)-CO-OCzHs 480 F -CHy-CH(C1)-CO-OH
481 F -CHZ-CH(Br)-CO-O(n-C3H~) 482 F -CHZ-CH(Br)-CO-0(n-C4H9) 483 F -CHZ-CH(Br)-CO-OCH(CH3)2 484 F -CHZ-CH(Br)-CO-OCHZ-CH(CH3)2 485 F -CHZ-CH(Br)-CO-OCH(CH3)-CZH5 486 F -CH2-CH(Br)-CO-OC(CH3)3 487 F -CH=CH-CO-OH
488 F -CH=CH-CO-OCH3 489 F -CH=CH-CO-OC2H5 4g0 F -CH=CH-CO-O(n-C3H~) 491 F -CH=CH-CO-0(n-C4H9) 492 F -CH=CH-CO-OCH(CH3)2 493 F -CH=CH-CO-OCH2-CH(CH3)2 494 F -CH=CH-CO-OCH(CH3)-C2H5 495 F -CH=CH-CO-OC(CH3)3 496 F -CH=C(C1)-CO-OH
497 F -CH=C(C1)-CO-OCH3 498 F -CH=C(C1)-CO-OC2H5 499 F -CH=C(C1)-CO-0(n-C3H~) 500 F -CH=C(C1)-CO-0(n-C4H9) 501 F -CH=C(C1)-CO-OCH(CH3)2 502 F -CH=C(C1)-CO-OCHz-CH(CH3)2 503 F -CH=C(C1)-CO-OCH(CH3)-CZH5 504 F -CH=C(Cl)-CO-OC(CH3)3 Nr. R1 R3 or R3' 505 F -GH=C(Br)-CO-OH
506 F -CH=C(Br)-CO-OCH3 507 F -CH=C(Br)-CO-OC2H5 508 F -CH=C(Br)-CO-0(n-C3H~) 509 F -CH=C(Br)-CO-0(n-C4Hg) 510 F -CH=C(Br)-CO-OCH(CH3)2 511 F -CH=C(Br)-CO-OCHz-CH(CH3)2 512 F -CH=C(Br)-CO-OCH(CH3)-CzH5 513 F -CH=C(Br)-CO-OC(CH3)3 514 F -CH2-CH(C1)-CO-NHZ
515 F -CHZ-CH(C1)-CO-NH-CH3 516 F -CHZ-CH(Cl)-CO-N(CH3)2 _ 517 F -CHz-CH(C1)-CO-NH-CzH5 518 F -CH2-CH(C1)-CO-N(C2H5)2 519 F -CH2-CH(C1)-CO-NH-(n-C3H~) 520 F -CHZ-CH(C1)-CO-N(n-C3H~)2 521 F -CH2-CH(Cl)-CO-NH-(n-C4Hg) 522 F -CH2-CH(C1)-CO-N(n-C4Hg)z 523 F -CHZ-CH(Br)-CO-NH2 524 F -CHZ-CH(Br)-CO-NH-CH3 525 F -CHZ-CH(Br)-CO-N(CH3)z 526 F -CH2-CH(Br)-CO-NH-CZH5 527 F -CH2-CH(Br)-CO-N(CzHS)2 528 F -CH2-CH(Br)-CO-NH-(n-C3H~) 529 F -CH2-CH{Br)-CO-N(n-C3H~)Z
530 F -CHZ-CH(Br)-CO-NH-(n-CqHg) 531 F -CHZ-CH(Br)-CO-N(n-C4Hg)Z
532 F -CH=CH-CO-NH2 533 F -CH=CH-CO-NH-CH3 534 F -CH=CH-CO-N(CH3)2 535 F -CH=CH-CO-NH-CZHS
536 F -CH=CH-CO-N(CZHS)2 537 F -CH=CH-CO-NH-(n-C3H~) 538 F -CH=CH-CO-N(n-C3H7)2 539 F -CH=CH-CO-NH-(n-C4Hg) 540 F -CH=CH-CO-N(n-C4Hg)2 541 F -CH=C(C1)-CO-NH2 542 F -CH=C(C1)-CO-NH-CH3 543 F -CH=C(C1)-CO-N(CH3)2 0U5~~50571 CA 02381639 2002-02-11 Nr . R1 R3 or R3' 544 F -CH=C(C1)-CO-NH-CZHS
545 F -CH=C(C1)-CO-N(C2H5)2 5 546 F -CH=C(G1)-CO-NH-(n-C3H~) 547 F -CH=C(C1)-CO-N(n-C3H~)Z
548 F -CH=C(G1)-CO-NH-(n-CqHg) 549 F -CH=C(C1)-CO-N(n-C4Hg)2 550 F -CH=C(Br)-CO-NHz 551 F -CH=C(Br)-CO-NH-CH3 552 F -CH=C(Br)-CO-NH(CH3)2 553 F -CH=C(Br)-CO-NH-CZH5 554 F -CH=C(Br)-CO-N(CZHS)2 15 555 F -CH=C(Br)-CO-NH-(n-C3H~) 556 F -CH=C(Br)-CO-N(n-C3H~)2 557 F -CH=C(Br)-CO-NH-(n-C4Hg) 558 F -CH=C(Br)-CO-N(n-C4Hg)2 Preference is in particular also given to compounds of the formula I-A, in which Z is a single bond, R3 is a group CH2-R3., wherein R3' and R1 have the meanings given in Table 1 (compounds I-Ab.l to I-Ab.558).
Preference is in particular also given to compounds of the formula I-A, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ac.l to I-Ac.558).
Preference is in particular also given to compounds of the formula I-A, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ad.l to I-Ad.558).
preference is in particular also given to compounds of the formula I-B, in which Z is a single bond, Het is a radical of the formula II-2 with X = oxygen, R4 = trifluoromethyl and R5 = me-thyl, RZ is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ba.l to I-Ba.558).
H C-N
~1--' / N (I-B) CF3 O' /'N
Preference is in particular also given to compounds of the formula I-B, in which Z is a single bond, R3 is a group CHZ-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Bb.l to I-Bb.558).
Preference is in particular also given to compounds of the formula I-B, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Bc.l to I-Bc.558).
Preference is in particular also given to compounds of the formula I-B, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Bd.l to I-Bd.558).
Preference is in particular also given to compounds of the formula I-C, in which Z is a single bond, Het is a radical of the formula II-5 with X = X' - oxygen, wherein R4 and R4' together with the carbon atoms to which they are bonded form a cyclohexene ring, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ca.l to I-Ca.558).
N ~ / 1 \\ \ ( I-C ) 0 0 ~N
Preference is in particular also given to compounds of the formula I-C, in which Z is a single bond, R3 is a group CHZ-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Cb.l to I-Cb.558).
~
' 0050/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-C, in which Z is an oxygen atom and R1 and R' have the meanings given in Table 1 (compounds I-Cc.l to I-Cc.558).
Preference is in particular also given to compounds of the formula I-C, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Cd.l to I-Cd.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is a single bond, Het is a radical of the formula II-5 with X = X' - Schwefel, wherein R4 and R4' toge-ther with the carbon atoms to which they are bonded form a cyclo-hexene ring, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-C'a.l to I-C'a.558).
N ~ / 1 ~~ ~ ( I-c' ~
S O ~N
Preference is in particular also given to compounds of the formula I-C', in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-C'b.l to I-C'b.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-C'c.l to I-C'c.558).
Preference is in particular also given to compounds of the formula I-C', in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-C'd.l to I-C'd.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is a single bond, Het is a radical of the formula II-6 with X = X' - Y = oxygen, R6 and R~ = methyl, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (com-pounds I-Da.l to I-Da.558).
O-N ~ ~ c1 (I-D) CHg 0 O~N
'~Z -R3 Preference is in particular also given to compounds of the formula I-D, in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Db.l to I-Db.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Dc.l to I-Dc.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is a sulfur atom and Rl and R3 have the meanings given in Table 1 (compounds I-Dd.l to I-Dd.558).
Preference is in particular also given to compounds of the formula I-E, in which Z is a single bond, Het is a radical of the formula II-12 with X = oxygen, R4 = methyl, R4' - trifluoromethyl and R4" - hydrogen, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ea.l to I-Ea.558).
F3 ~ ~N ~ ~ C1 N
(I-E) O' //N
~Z-R3 Preference is in particular also given to compounds of the formula I-E, in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Eb.l to I-Eb.558).
Preference is in particular also given to compounds of the formula I-E, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ec.l to I-Ec.558).
- ~ 050/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-E, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ed.l to I-Ed.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is a single bond, Het is a radical of the formula II-12 with X = oxygen, R4 = amino, R4' - methylsulfo-nyl and R4" - hydrogen, Rz is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-E'a.l to I-E'a.558).
\ ~ 2 H3C S(0)2 N \ / R
N (I-E') 0' //N
Preference is in particular also given to compounds of the formula I-E', in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-E'b.l to I-E'b.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-E'c.l to I-E'c.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-E'd.l to I-E'd.558).
Preference is in particular also given to compounds of the formula I-E", which are compounds of formula I, in which Z is a single bond, Het is a radical of the formula II-12 with X = oxy-gen, R4 = hydrogen, R4' - trifluoromethyl and R4" - hydrogen, RZ
is chlorine and R1 and R3 have the meanings given in Table 1 (com-pounds I-E"a.l to I-E"a.558).
Preference is in particular also given to compounds of the formula I-E", in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-E"b.l to I-E"b.558).
0~5~/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-E", in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ec".1 to I-E"c.558).
5 Preference is in particular also given to compounds of the formula I-E", in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-E"d.l to I-E"d.558).
The benzoxazoles of the formula I according to the invention can be obtained by different routes, for example by condensing a substituted 2-aminophenol of the formula III with carbonic acid or carboxylic acid derivatives:
Carbonic R1 R1 acid or Het R2 carboxylic Het ~ ~ Rz \ ~ acid derivative O ~N
HO NH ~I(2 (III) (I) The condensations of bifunctional 2-aminophenols with carbonic acid or carboxylic acid derivatives can be carried out in a manner known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. EBc, 1st Edition 1994, pp. 247-284; Vol. EBb, 1st Edition 1994, pp.
881-901; Vol. EBa, 1st Edition 1993, pp. 1032-1078). Preferred carbonic acid or carboxylic acid derivatives are the corresponding esters, anhydrides, acid chlorides, ortho esters, diimides, nitriles, imido esters, trichloromethyl-substituted compounds, isocyanates and their thio analogs.
Suitable solvents/diluents are, in particular, organic solvents, for example aromatic hydrocarbons, such as benzene, toluene and o-, m- or p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and dichloroethane, lower alcohols, such as methanol and ethanol, aliphatic or cyclic ethers, such as dimethoxyethane, tetrahydrofuran and dioxane, carbonic acid esters, such as ethyl acetate, or aprotic polar solvents, such as dimethylformamide and dimethyl sulfoxide.
If desired, the reaction can be accelerated by addition of catalytic amounts of an acid. Suitable acids are, in particular, mineral acids, such as hydrochloric acids, or sulfonic acids, such as p-toluenesulfonic acid, or their salts with nitrogen bases, such as, for example, pyridine. The amount of acid is preferably from 0.01 to 5 mold, based on the amount of III.
The reaction temperatures are preferably from 20°C to the reflux temperature of the reaction mixture in question, in particular from 60°C to reflux temperature.
0~5U/50571 CA 02381639 2002-02-11 The carbonic acid or carboxylic acid derivative is either used in approximately stoichiometric amounts or in excess. In suitable cases, it may also be possible to use a relatively large excess or to work without solvent. Preference is given to approximately stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of III.
The substituted 2-aminophenols III are advantageously obtained by reducing the corresponding 2-nitrophenols IV (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. XI/1, 4th Edition 1957, p. 431 ff.):
Het RZ Het R2 Reduction (IV) (III) Suitable reducing agents are, in particular, - elemental metals, such as iron, tin and zinc, - hydrogen in the presence of suitable catalysts, such as palladium or platinum on carbon or Raney nickel, or - complex hydrides, such as LiAlH4 and NaBH4, if appropriate in the presence of catalysts.
Suitable solvents are usually - depending on the reducing agent -carboxylic acids, such as acetic acid and propionic acid, mineral acids, such as hydrochloric acid or sulfuric acid, alcohols, such as methanol and ethanol, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, aromatic compounds, such as benzene and toluene, and mixtures of such solvents.
The reactions can be carried out at temperatures of from (-100)~C
to the boiling point of the reaction mixture in question.
The starting materials are usually employed in approximately stoichiometric amounts; however, in individual cases a multiple excess of one or the other component may be advantageous.
The 2-nitrophenols of the formula IV can be released from protected precursors which have a cleavable radical R at the phenol oxygen. Suitable radicals R are groups which protect the phenol group as ether, ester or carbonic acid derivative, for example alkyl, O-heterocyclyl, benzyl, alkylcarbonyl, arylcarbonyl or alkoxycarbonyl groups. Suitable radicals R and methods for their cleavage are known to the person skilled in the art, for example from Greene/Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, 2nd Edition 1991, p. 145 ff. and p.
279 ff.
Het ~ ~ R2 Het ~ ~ R2 Cleaving R-O N02 reagent HO N02 (IVa) (IV) Suitable cleaving reagents are, in particular:
- in the case of unsubstituted or substituted alkylphenols:
trimethylsilyl iodide, boron tribromide, boron trichloride, aluminum trichloride, lithium chloride or hydrogen bromide;
- in the case of unsubstituted or substituted benzylphenols:
boron trifluoride, hydrofluoric acid or hydrogen/catalyst, preferably noble metal catalysts, such as palladium or platinum;
- in the case of unsubstituted or substituted aryl esters:
sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, hydrogen chloride, sulfuric acid, ammonia, hydrazine or zinc.
The chosen solvent/diluent should preferably be inert to the cleaving reagent in question. If the halides trimethylsilyl iodide, boron tribromide, boron trichloride or aluminum trichloride are used, particular preference is given to halogenated solvents, such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane. Hydrogen bromide is preferably used in aqueous solution, very particularly preferably as a 48~
by weight strength solution; lithium chloride is preferably used in polar solvents, such as lower alcohols, dimethyl sulfoxide and dimethylformamide; hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, if appropriate with addition of a hydrogen transfer agent, such as cyclohexene or cyclohexadiene. Mineral bases or mineral acids and nitrogen bases are preferably used in aqueous medium. Depending on the solubility of the reagents, an organic solvent, such as, for example, a lower alcohol, is added, if appropriate.
The temperature for the cleavage reaction is preferably from O~C
to the boiling point of the reaction mixture in question.
The cleaving reagent is preferably employed in approximately stoichiometric amounts or in excess. The excess is particularly preferably between 1 and 10 molar equivalents, based on the amount of IVa.
Both the compounds of the formula IV and the compounds of the formula IVa can be prepared by nucleophilic exchange of the fluorine atom in 2-nitrofluorobenzenes of the formula V for an oxygen nucleophile R'Oe. Here, R' is hydrogen or one of the cleavable radicals R defined above. Whether the route via a protected derivative IVa is chosen or the 2-nitrophenol can be prepared directly from the 2-nitrofluorobenzene by exchange of fluorine for hydroxide depends on the stability of the radicals R1, RZ and Het in the compounds V.
Het ~ ~ R2 R' Oe Het ~ ~ RZ
F NOz R'-0 N02 (V) (IVa/IV) The exchange reaction of aromatically bonded fluorine for oxygen nucleophiles R'Oe are carried out in a manner known per se (c. f., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, 1976, Vol. 6/1c pp. 146-202 and Volume IX, 4th Edition 1955, pp. 7-18).
For this reaction, the following reagents are preferred reactants:
- for the exchange of F for OR: potassium benzoate, sodium nitrite, sodium hydroxide, potassium hydroxide, potassium carbonate, benzaldoxime, sodium acetate, potassium acetate, sodium methoxide, potassium methoxide, sodium trimethylsilanoate, dimethyl maleate, N-hydroxysuccinimide.
~
~ 0050/50571 CA 02381639 2002-02-11 - for the exchange of F for OH: sodium hydroxide, potassium hydroxide, lithium hydroxide.
In certain cases, the reactions can be carried out in the absence 5 of solvent/diluent. If a solvent/diluent is employed, preference is given to those in which the oxygen-group-transferring reagent is readily soluble. Particular preference is given to alcohols, such as ethanol, propanol or tert-butanol, aprotic polar solvents, such as dimethylformamide or dimethylacetamide, cyclic 10 ethers, such as dioxane or tetrahydrofuran, or aliphatic ethers, such as dimethoxyethane.
The reaction temperatures are preferably from 20~C to the reflux temperature of the reaction mixture in question, in particular 15 from 60~C to reflux temperature.
The oxygen-transferring reagent is either employed in approximately stoichiometric amounts or in excess. In suitable cases, it may also be possible to use a very large excess.
20 Preference is given to approximately stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of V.
The novel 2-nitrofluorobenzenes from V can be obtained in a manner known per se by reacting fluorobenzenes VI with nitrating 25 agents, i.e. N02+ transfer reagents (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. 10/1, 1971, p. 479 ff.):
Het ~ ~ R2 "N02+" Het ~ ~ R2 F F NOZ
(VI) (V) Suitable nitrating agents are, in particular, nitric acid, in a mixture with sulfuric acid or acetic anhydride, or nitronium salts, specially nitronium tetrafluoroborate. The mixture of nitric acid and sulfuric acid may comprise the two mixing partners in any ratio; preference is given to those mixtures in which the sulfuric acid predominates significantly or serves as solvent. This applies analogously to the mixture of nitric acid and acetic anhydride. Nitronium tetrafluoroborate is preferably used in aprotic polar solvents, for example in acetonitrile or nitromethane.
The reaction temperature is generally from (-80) to 80~C, in particular from (-20)~C to 30~C.
In the case of nitrations with the reagent nitric acid, the reaction is carried out using an approximately equimolar amount or particularly preferably an excess of nitrating agent. The excess may exceed the amount of VI by a large amount. Nitronium tetrafluoroborate is preferably used in an amount which is equimolar to that of the substrate, or in a small excess of from 1.1 to 1.5 molar equivalents.
The substituted fluorobenzenes of the formula VI can be prepared by customary syntheses for heterocycles or carbocycles, starting with known 2-aminofluorobenzenes VII or 2-fluorophenylhydrazines of the formula VIIa (scheme 1).
Scheme 1:
_ NHz ~ ~ RZ Het ~ ~ R2 F F
(VI) (VII) The compounds of formulas VI and VII are partly disclosed in the state of the art, e.g. in JP 0 9227535, US 4,818,272, US
4,919,708 and J. Heterocycl. Chem. 1987, 24, S.1391, or they can be prepared according to the methods described therein. With re-gards to compounds of formula VI and their preparation, these do-cuments are incorporated by reference.
Of course, it is also possible to carry out the synthesis sequence VII - VI - V - IV - III shown above using the corresponding amino compounds IIIa, IVb, IVc and Va (Scheme 2).
Scheme 2: R1 R1 ( VI I ) --~,. NH2 ~ ~ R2 ~ NH2 ~ ~ R2 \ \
F N02 R'-0 NOZ
(Va) (IVb) R1 (V) R1 (IVa) NH2 ~ ~ RZ ~ NHZ ~ ~ R2 ~ (III) (IVc) (IIIa) (IV) If appropriate, the amino group has to be protected in one or more steps. In each of the steps of this synthesis sequence, the amino group can be transformed into one of the radicals of the formulae II-1 to II-18.
It is also possible to synthesize the radical Het in the compounds I from 7-aminobenzoxazoles of the formula VIII (Scheme 3). The compounds of formula VIII are disclosed e.g. in WO 97/08170.
Scheme 3 NHZ ~ ~ RZ Het ~ ~ R2 O /N ~ O /N
(VIII) (I) Another route to prepare compounds of the invention of formula I
is shown in scheme 4:
00''J~/50571 CA 02381639 2002-02-11 Scheme 4:
1.N0+ R3COOH
Het ~ ~ R2 ~. Het ~ ~ R2 ~ Het ~ ~ R2 2 . N3 O_ /'N
(IX) (X) R3 (I) Het, R1, R2 and R3 in scheme 4 have the meanings mentioned above.
X is here a single bond. According to scheme 4, the anilines of formula IX, which are disclosed in the art, e.g. in WO 97/07104, are converted into the phenylazides of formula X by successive nitrosation into the diazonium compounds and subsequent reaction with an azide, the phenylazides being afterwards converted into the oxazoles of formula I, in which X is a single bond, by reac-ting X with a carboxylic acid of the formula R3COOH. The synthesis shown in scheme 4 is in a similar manner as the conversion of an-ilines into benzoxazoles being described in Houben-Weyl, Methoden der Organischen Chemie, Band EBa, 1993, S. 1087 ff. The azides of formula I are new and also subject of the present invention.
The diazonium salt of IX is prepared in a known manner, by reac-ting the aniline IX with a nitrite, e.g. sodium nitrite, potas-sium nitrite, in an aqueous acid solution, e.g. hydrochloric acid, hydrobromic acid, or sulfuric acid or by reacting X with a nitrite, e.g. tert-butyl nitrite or isopentyl nitrite in anhy-drous conditions, e.g. in glacial acetic acid containing hydroch-loric acid, in absolute alcohol, in dioxane or tetrahydrofurane, in acetonitrile or acetone. Conversion of the diazonium compounds into the arylazides takes place by reacting the diazonium com-pounds with an alkali azide or alkaline earth azide, e.g. sodium azide, or by reaction with trimethylsilylazide (see also: Organic Synthesis, Bd. IV, S. 75 and Bd. V, S. 829).
The reaction of azide compounds of the formula X with carboxylic acid R3-COON takes place in an inert organic solvent, e.g. in hy-drocarbons such as toluene or hexane, in halogenated hydrocarbons such as dichloromethane or chloroform, in ethers such as diethy-lether, dimethoxyethane, methyl-tert-butylether, dioxane or te-trahydrofurane, in amides such as dimethyl formamide, dimethyla-cet amide or N-methyl pyrrolidon, in acetonitril, or preferably without solvent in an excess of carboxylic acid R19COOH. In the latter case, the addition of a mineralic acid, such as phosphoric ~ ~ ~~SU/50571 CA 02381639 2002-02-11 acid and/or of a silylating reagent, such as a mixture of phosp-horous pentoxide and hexamethyldisiloxane can be helpful. The reaction takes place preferably at elevated temperatures, such as the boiling point of the reaction mixture.
The examples to follow shall furter describe the invention without restricting it.
Example 1:
3-(4-chloro-6-fluorobenzoxazol-7-yl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one (Comp. I-Aa.373 from Table 1) 1.0 g of 3-(5-amino-4-chloro-2-fluoro-6-hydroxyphenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one (from intermediate 7;
comprises 30~ of the 3-aminophenyl isomers) was initially charged in 30 ml of absolute ethanol, and 1.1 g of trimethyl orthoformate were added. The mixture was refluxed for 5.5 hours. The volatile components were then removed using water pump vacuum, and the product was purified by silica gel chromatography (mobile phase cyclohexane/ethyl acetate 95/5). Yield: 0.3 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 8.20(s, 1H); 7.40(d, 1H);
1.40(s, 9H).
Intermediate 1: 4-chloro-2,6-difluoraniline 30.0 g of 2,6-difluoraniline were mixed with 200 ml of concentrated acetic acid and heated at 80°C. 36.0 g of sulfuryl chloride were mixed with about the same amount of concentrated acetic acid and added dropwise to the heated solution. The solution was then refluxed for 6 hours. After cooling, the solution was concentrated under reduced pressure and the residue was stirred with water and pentane. The solid residue was filtered off and washed with water. The resulting solid was admixed with 200 ml of concentrated hydrochloric acid and refluxed for 2 hours. After cooling, the solution was carefully made weakly alkaline using aqueous sodium hydroxide solution and extracted three times with 100 ml of ethyl acetate. The organic phase was dried with sodium sulfate and the solvent was removed.
Yield: 34.0 g.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.85(d, 2H); 3.9-3.6(brd, 2H).
Intermediate 2: 4-chloro-2,6-difluorophenylhydrazine 25.0 g of 4-chloro-2,6-difluoroaniline were mixed with 277 ml of concentrated hydrochloric acid. The mixture was heated briefly until a fine suspension had formed. 10.6 g of sodium nitrite were dissolved in 60 ml of water and, at O~C, added dropwise to the suspension. The mixture was stirred at O~C for 2 hours. In a second flask, 86.7 g of tin dichloride dihydrate were initially charged in 52 ml of concentrated hydrochloric acid. At O~C, the 5 diazonium salt solution was added, resulting in the formation of a thick slurry and foaming of the mixture. The reaction mixture was then stirred at 20~C for 2 hours, poured onto water, insoluble .components were filtered off and the solution was adjusted to pH
11 using concentrated aqueous sodium hydroxide solution. The 10 precipitated solid was filtered off with suction and washed repeatedly with water. Yield: 16.2 g.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.90(d; 2H); 5.2-5.0(brd, 1H);
4.0-3.8 (brd, 2H).
15 Intermediate 3:
1-(4-chloro-2,6-difluorophenyl)-2-(2,2-dimethylpropionyl)hydra-zine 8.0 g of 4-chloro-2,6-difluorophenylhydrazine were dissolved in 20 200 ml of toluene. 27 ml of 10$ strength aqueous sodium hydroxide solution were added. With cooling, 5.66 g of pivaloyl chloride were then added dropwise at O~C, and the solution was stirred at 20°C for 3 hours. The organic phase was separated off, washed repeatedly with water and dried, and the solvent was removed.
25 Yield: 11.4 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.75(brd, 1H); 6.90(d, 2H);
6.30(brd, 1H); 1.2(s, 9H).
Intermediate 4:
30 3-(4-chloro-2,6-difluorophenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxa-diazol-2(3H)-one 11.0 g of 1-(4-chloro-2,6-difluorophenyl)-2-(2,2-dimethyl-propionyl)hydrazine in 100 ml of absolute toluene were mixed with 35 4.6 g of diphosgene. The mixture was refluxed for 3 hours, and another 5.0 g of diphosgene were then added. After a further 5 hours at reflux, a further 4.0 g of diphosgene and a drop of DMF were added, and the mixture was refluxed for 3 hours. After cooling, the mixture was neutralized with sodium bicarbonate 40 solution and the organic phase was then washed with water. Drying and removal of the volatile components gave a yield of 11.7 g of the desired product.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.10(d, 2H); 1.35(s, 9H).
~
~ 0050/50571 CA 02381639 2002-02-11 Intermediate 5:
3-(4-chloro-2,6-difluoro-3-nitrophenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one 11.5 g of 3-(4-chloro-2,6-difluorophenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one were dissolved in 15 ml of concentrated sulfuric acid. At O~C, 9 ml of 65~ strength nitric acid were added, and the mixture was stirred for 10 minutes. The mixture was then stirred into ice-water and extracted with 100 ml of tert-butyl methyl ether. The organic phase was washed with water and dried, and the volatile components were removed. Yield:
10.5 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.35(d, 1H); 1.35(s, 9H).
Intermediate 6:
3-(4-chloro-2-fluoro-6-hydroxy-5-nitrophenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one 8.25 g of 3-(4-chloro-2,6-difluoro-3-nitrophenyl)-5-(1,1 dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one were dissolved in 250 ml of absolute dimethylformamide. 8.25 g of sodium acetate were added, and the mixture was heated at 120~C for 45 minutes.
After cooling, water was added and the solution was adjusted to a slightly acidic pH by addition of dilute hydrochloric acid and extracted with tert-butyl methyl ether. The organic phase was dried and volatile components were removed. Yield: 7.8 g, comprising 30~ of the 3-vitro isomer formed by exchange of the fluorine para to the vitro group.
1H-NMR (270 MHz, CDC13): 8[ppm] = 7.05(d, 1H); 1.40(s, 9H).
Intermediate 7:
3-(5-amino-4-chloro-2-fluoro-6-hydroxyphenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one 7.8 g of the isomer mixture from intermediate 6 were taken up in a mixture of 170 ml of water and 17 ml of concentrated hydrochloric acid. The mixture was heated to 65~C and 6.63 g of iron powder were added a little at a time. The mixture was refluxed for 6 hours. After cooling, the mixture was extracted with ethyl acetate (150 ml), and drying of the organic phase and removal of the volatile components gave the product of value, comprising 30$ of the reduction product of the 3-vitro isomer from intermediate 6. Yield: 5.5 g of isomer mixture.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.85(d, 1H); 1.40(s, 9H).
Examples 2 to 6 ~
' ~ 0050/50571 CA 02381639 2002-02-11 In addition to those described above, Table 2 below lists further benzoxazole derivatives of the formula I which were prepared in a similar manner:
Table 2: 0 F
. ~ ~ ~ 1 HaC N ( I -Aa H C 0' / N
Example R3 m.p. [~C] 1H-NMR (CDC13) No. 8 [ppm]
1 H 99 $,20 (s), 7,40 (d), 1,40 (s, 9H) 2 CH3 117 7,30 (d), 2,70 (s, 3:[-i), 1,40 (s, 9H) 3 C2H5 oil "7,30 (d), 3,0 (q, 2H), 1,45 (t, 3H), 1,40 (s, 9H) 4 n-C4H9 oil 7,30 (d), 3,0 (t, 2H), 1,9 (q, 2H), 1,45 (m, 2H), 1,4 (s, 9H), 1,0 (t, 3H) 5 CHzCl oil 7,35 (d), 4,80 (s, 2:H), 1,40 (s, 9H) 6 phenyl 14 7 8,25 (d, 2H), 7,65-',~,5 (m, 3H), 7,35 (d), 1,4 (s, 9H) Examples 7 to 14 In a similar manner the compounds of examples 7 to 14, listed in Table 3, were prepared from 1-(4-Chlor-2,6-difluorphenyl)-3-tri fluormethyl-4-methyltriazol-5-on. All compounds had an oily con sistence.
Table 3: ~ F
H3C N_ ~ ~ ~ 1 / N (I_Ba) Example R3 1H-NMR (CDC13) No. b [ppm]
7 H 8,15 (s), 7,4 (d), 3,55 (s, 3H) g cH3 7,30 (d), 3,55 (s, 3H), 2,70 (s, 3H) 9 c2H5 7,30 (d), 3,55 (s, 3H), 3,0 (q, 2H), 1,45 (t, 3H) Example R3 1H-NMR (CDC13) No. b [ppm]
1o cH2c1 7,4 (d), 4,80 (s, 2H), 3,55 (s, 3H) 11 n-C3H~ 7,30 (d), 3,50 (s, 3H), 2,95 (t, 2H), 1,90 {q, 2H), 1,05 (t, 3H) 12 n-C4H9 7,30 (d), 3,50 (s, 3H), 2,95 (t, 2H), 1,90 (q, 2H), 1,45 (m, 2H), 1,0 (t, 3H) 13 C-C3H5 7,25 (d), 3,55 (s, 3H), 2,25 (m), 1,4-1,2 (m, 4H) 14 CHZ- ( c-C3H57,30 (d), 3,55 (s, 3H), 2,85 (d, 2H), ~ 1,25 (m), 0,55 (m, 2H), 0,35 (m, 2H) Example 15:
N-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4,5,6,7-te-trahydrophthalimide (Compd. I-Ca.419 from Table 1) In a similar manner to example 1, the title compound was prepared from 1-(4-chloro-2,6-difluorophenyl)-3-trifluoromethyl-4-methyl-triazole-5-one. The compound had an oily consistence.
1H-NMR (CDC13) 8 [ppm] 7,2 (d), 2,50 (s, br), 2,2 (m), 1,85 (s, br), 1,35-1,2 (m).
Example 16:
N-(4-chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4,5,6,7-te-trahydrophthalic acid dithioimide (Compd. I-C'a.419 from Table 1) 0,5 g N-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4.5,6,7- tetrahydrophthalimide were dissolved in 55 ml toluene and 0,61 g phosphorous pentasulfide were added. The solution was heated to reflux and kept at this temperature for 46 h. The reac-tion mixture was dried in vacuum and purified chromatographically on silicagel with cyclohexane/ethyl acetate (100:1 to 10:1 v/v).
0~8 g of the title compound were yielded as solid with a melting point of 132-135~C.
1H-NMR (CDC13)b [ppm] 7,1 (d, 1H), 2,50 (m 4H), 2,2 (m, 1H), 1,9 (m, 4H), 1,3-1,1 (m, 4H).
Example 17:
2-(4-chloro-1-ethyl-6-fluorobenzoxazole-7-yl)-4-methyl-5-trifluo-romethylpyridazine-3-one (Compd. I-Ea.375 from Table 1) 8~9 g 2-(5-amino-2-fluoro-4-chlorophenyl)-4-methyl-5-trifluorome-thylpyridazine-3-one (from WO 97/07104) were dissolved in 90 ml trifluoro acetic acid. 3.0 g (0.029 mol) t-Butylnitrit were added ~
' ' ~~50/50571 CA 02381639 2002-02-11 dropwise at 5 to 10~C. Stirring was continued for 30 min at 5 to 10~C and 2.7 g (0.041 mol) sodium azide were added in portions.
After 1 h at 5 to 10~C stirring was continued for 3 h at RT, the reaction mixture was poured into 200 ml ice-water and extracted 3 times with methylene chloride. The organic phase was successi-vely washed with water, aqueous 10~ sodium hydroxide solution and again with water, dried over sodium sulfate and evaporated at room temperature. 9.2 g of the azide were yielded as fair solid, which was directly used in the next reaction step.
1H-NMR (CDC13) 8 [ppm] 8.0 (s, 1 H), 7.4 (d, 1H), 7.3 (d, 1 H), 2.4 (t, 3 H).
1.63 g (0.0115 mol) P401o were stirred for 30 min at 90~C in 6 ml hexamethyldisiloxane and then cooled to room temperature. A solu-tion of 1.6 g (0.0046 mol) of the azide from the previous reac-tion step in 20 ml propionic acid was added dropwise and the mix-ture was kept at 40~C for 3 h. The reaction mixture was poured into ice-water, alkalized with 10 ~ aqueous sodium hydroxide so-lution, and the aqueous phase was extracted 3 times with ethyl acetate. The combined organic phases were washed with water, eva-porated and purified by chromatography on silicagel with cyclohe-xane/ethyl acetate (6:1 v/v). 0.28 g of the title compound were yielded as a viscous oil.
The compounds of examples 18 bis 14, listed in Table 4, were pre-pared in a similar manner.
Table 4: R4 p F
~ \
F3 N ~ ~ C1 N
(I-E) p' /'N
~ 0050/50571 CA 02381639 2002-02-11 Example R R3 1H-NMR ~~[ppm]
(CDC13) No.
17 CH3 CH2CH3 8.05 (s, H),7.3 (d, 1 H), 3.0 (q, H),2.4 (s, H), 1.5 3 H).
8t 5 18 CH CH2CH2CH3 o5 H),7.3 (d, 1 H), 3 (s, 1 2.9 (t, H),2.4 (s, H), 1.9 (m, 2 H), 1.0(t, 3 H).
19 CH3 CH(CH3)Z 8.05 (s, H),7.3 (d, 1 H), 3.2 (sept.1 ), .4 , 3 H), H 2 (s 1.4 (d, H) 0 20 CH3 c-C3H5 8.05 (s, H),7.3 (d, 1 H), 2.4 (s, H),2.2 (m, H), 1.3 1.4 (m, 4 .
H) 21 CH3 CHZ-(c-C3H5) 8.05 (s, H),7.3 (d, 1 H), 2.8 (d, H),2.4 (s, H), 1.2 (m, 1 H, .6 m, H), 0.3 (m, 0 ( 2 15 2 H).
23 H CHyCHyCH3 24 H CH(CH3)2 25 H c-C3H5 20 26 H CH2-(c-C3H5) Example 27:
2-(4-chloro-6-fluorobenzoxazole-7-yl)-4-amino-5-methylsulfonylpy-25 ridazin-3-one (Compd. I-E'a.373 from Table 1) In a similar manner to the procedure described in example 17 the title compound was prepared from 2-(5-Amino-2-fluoro-4-chlorophe-nyl)-4-methyl-5-trifluoromethylpyridazin-3-one (known from 30 WO 9707104).
1H-NMR (DMSO) b [ppm] 9.0 (s, 1H), 8.3 (br. s, 1 H), 8.0 (s 1 H), 7.7 (br. s 1 H), 7.1 (d, 1 H).
Example 28:
3-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazol-7-yl)-4,5-dihy-dro-5-(2-propyliden)-4-oxooxazol-2-one (Compd. I-Da.419 from Table 1) In a similar manner to the procedure described in example 1 the title compound was prepared from 2-(2,6-Difluoro-4-chlorophe-nyl)-4,5-dihydro-5-(2-propyliden)-4-oxooxazol-2-one. The title compound had an oily consistence.
The compounds I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions ~
which comprise I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, Soya and cotton, they act against broad-leaved weeds and grass weeds without inflicting substantial damage to the crop plants. This effect is observed mainly at low rates of application.
Depending on the application method in question, the compounds I, or herbicidal compositions comprising them, can also be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus °fficinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
In addition, the compounds I can also be used in crops which, by means of breeding, including genetic engineering methods, have been made tolerant to the action of herbicides.
The active ingredients I, or the herbicidal compositions, may be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that they come in as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of ~ ~ 0050/50571 CA 02381639 2002-02-11 undesirable plants which grow underneath, or the bare soil surface (post-directed, lay-by).
The compounds I, or the herbicidal compositions comprising them, can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
The use forms depend on the intended purposes; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their,derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg.
amines such as N-methylpyrrolidone, and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substituted benzoxazoles, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acid, eg, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, ~ ~ 0~5~/50571 CA 02381639 2002-02-11 isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or binding the active substances together with a solid carrier. Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The concentration of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98~ by weight, preferably from 0.01 to 95~ by weight, of at least one active Ingredient. The active ingredients are employed in a purity of from 90~ to 100, preferably 95~ to 100 (in accordance with NMR
spectra).
The compounds I according to the invention can be formulated, for example, as follows:
I. 20 parts by weight of Active ingredient of example 1 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoetha-nolamide, 5 parts by weight of calcium dodecylbenzenesulfo-nate and 5 parts by weight of the adduct of 40 mol of eth-ylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distribut-ing it therein gives an aqueous dispersion which comprises 0.02 by weight of the active ingredient.
II. 20 parts by weight of Active ingredient of example 2 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02 by weight of the active ingredient.
III. 20 parts by weight of Active ingredient of example 3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02$ by weight of the active ingredient.
IV' 20 parts by weight of Active ingredient of example 4 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1~ by weight of the active ingredient.
V. 3 parts by weight of Active ingredient of example 1 are mixed with 97 parts by weight of finely divided kaolin.
This gives a dust which comprises 3~ by weight of the ac-tive ingredient.
VI. 20 parts by weight of Active ingredient of example 5 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII. 1 part by weight of Active ingredient of example 6 is dis-solved in a mixture composed of 70 parts by weight of cy-clohexanone, 20 parts by weight of ethoxylated isooctylphe-nol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
VIII. 1 part by weight of Active ingredient of example 1 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol~ EM 31 (_ nonionic emulsifier based on ethoxylated castor oil; BASF
AG). This gives a stable emulsion concentrate.
0~5U/50571 CA 02381639 2002-02-11 To widen the spectrum of action and to achieve synergistic effects, the substituted benzoxazoles I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and applied jointly.
5 Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)-aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 10 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, 15 dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic 20 acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Furthermore, it may be advantageous to apply the compounds I, alone or in combination with other herbicides, also as a mixture with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for remedying nutritional and trace-element deficiencies. Nonphytotoxic oils and oil concentrates may also be added. Depending on the control target, the season, the target plants and the growth stage, the rates of application of active ingredient are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.).
Use Examples The herbicidal activity of compounds of formula I according to the invention was demonstrated by the following greenhouse expe-riments:
Plastic pots were used as culture containers, containing loamy sand with approximately 3.0~ of humus as substrate. The seeds of the test plants were sown separately according to their species.
For the pre-emergence treatment, the active compounds were sus-pended or emulsified in water and were applied directly after so-wing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subse-quently covered with plastic hoods until the plants had rooted.
This cover causes uniform germination of the test plants, unless this was adversely affected by the active compound.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and then treated with the active compounds which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to the treatment. The application rate for the post-emergence treatment was 31.2, 15.6 or 7.81 g/ha of active substance.
Depending on the species, the plants were kept at 10-25~C or 20-35~C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.
The plants used in the greenhouse experiments were of the following species:
Bayer code German name English name AMARE Zuruckgekrummter redroot pigweed Fuchsschwanz POLPE Flohknoterich lady's thumb ABUTH lindenblattrige velvet leaf Schonmalve The following tests were performed in the post-emergence treat-ment.
The compound of example 27 (Compound I-E~a.373 of Table 1) had a very good herbicidal activity against ABUTH, AMARE and POLPE with application rates of 31.2 and 15.6 g/ha a.S.
The compound of example 15 (Compound I-Ca.419 of Table 1) had a very good herbicidal activity against ABUTH, AMARE and POLPE with application rates of 15.6 and 7.81 g/ha a.S.
The compound of example 17 (Compound Nr. I-Ea.375) had a very good herbicidal activity against ABUTH, AAMARE and POLPE with ap-plication rates of 15.6 and 7.81 g/ha a.S.
The compound of example 13 (Compound Nr. I-Ba.419 had a good to very good herbicidal activity against ABUTH, AAMARE and POLPE
with application rates of 31.2 and 15.6 g/ha a.S.
'~Z -R3 Preference is in particular also given to compounds of the formula I-D, in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Db.l to I-Db.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Dc.l to I-Dc.558).
Preference is in particular also given to compounds of the formula I-D, in which Z is a sulfur atom and Rl and R3 have the meanings given in Table 1 (compounds I-Dd.l to I-Dd.558).
Preference is in particular also given to compounds of the formula I-E, in which Z is a single bond, Het is a radical of the formula II-12 with X = oxygen, R4 = methyl, R4' - trifluoromethyl and R4" - hydrogen, R2 is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-Ea.l to I-Ea.558).
F3 ~ ~N ~ ~ C1 N
(I-E) O' //N
~Z-R3 Preference is in particular also given to compounds of the formula I-E, in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-Eb.l to I-Eb.558).
Preference is in particular also given to compounds of the formula I-E, in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ec.l to I-Ec.558).
- ~ 050/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-E, in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ed.l to I-Ed.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is a single bond, Het is a radical of the formula II-12 with X = oxygen, R4 = amino, R4' - methylsulfo-nyl and R4" - hydrogen, Rz is chlorine and R1 and R3 have the meanings given in Table 1 (compounds I-E'a.l to I-E'a.558).
\ ~ 2 H3C S(0)2 N \ / R
N (I-E') 0' //N
Preference is in particular also given to compounds of the formula I-E', in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-E'b.l to I-E'b.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-E'c.l to I-E'c.558).
Preference is in particular also given to compounds of the formula I-E', in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-E'd.l to I-E'd.558).
Preference is in particular also given to compounds of the formula I-E", which are compounds of formula I, in which Z is a single bond, Het is a radical of the formula II-12 with X = oxy-gen, R4 = hydrogen, R4' - trifluoromethyl and R4" - hydrogen, RZ
is chlorine and R1 and R3 have the meanings given in Table 1 (com-pounds I-E"a.l to I-E"a.558).
Preference is in particular also given to compounds of the formula I-E", in which Z is a single bond, R3 is a group CH2-R3', wherein R3' and R1 have the meanings given in Table 1 (compounds I-E"b.l to I-E"b.558).
0~5~/50571 CA 02381639 2002-02-11 Preference is in particular also given to compounds of the formula I-E", in which Z is an oxygen atom and R1 and R3 have the meanings given in Table 1 (compounds I-Ec".1 to I-E"c.558).
5 Preference is in particular also given to compounds of the formula I-E", in which Z is a sulfur atom and R1 and R3 have the meanings given in Table 1 (compounds I-E"d.l to I-E"d.558).
The benzoxazoles of the formula I according to the invention can be obtained by different routes, for example by condensing a substituted 2-aminophenol of the formula III with carbonic acid or carboxylic acid derivatives:
Carbonic R1 R1 acid or Het R2 carboxylic Het ~ ~ Rz \ ~ acid derivative O ~N
HO NH ~I(2 (III) (I) The condensations of bifunctional 2-aminophenols with carbonic acid or carboxylic acid derivatives can be carried out in a manner known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. EBc, 1st Edition 1994, pp. 247-284; Vol. EBb, 1st Edition 1994, pp.
881-901; Vol. EBa, 1st Edition 1993, pp. 1032-1078). Preferred carbonic acid or carboxylic acid derivatives are the corresponding esters, anhydrides, acid chlorides, ortho esters, diimides, nitriles, imido esters, trichloromethyl-substituted compounds, isocyanates and their thio analogs.
Suitable solvents/diluents are, in particular, organic solvents, for example aromatic hydrocarbons, such as benzene, toluene and o-, m- or p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and dichloroethane, lower alcohols, such as methanol and ethanol, aliphatic or cyclic ethers, such as dimethoxyethane, tetrahydrofuran and dioxane, carbonic acid esters, such as ethyl acetate, or aprotic polar solvents, such as dimethylformamide and dimethyl sulfoxide.
If desired, the reaction can be accelerated by addition of catalytic amounts of an acid. Suitable acids are, in particular, mineral acids, such as hydrochloric acids, or sulfonic acids, such as p-toluenesulfonic acid, or their salts with nitrogen bases, such as, for example, pyridine. The amount of acid is preferably from 0.01 to 5 mold, based on the amount of III.
The reaction temperatures are preferably from 20°C to the reflux temperature of the reaction mixture in question, in particular from 60°C to reflux temperature.
0~5U/50571 CA 02381639 2002-02-11 The carbonic acid or carboxylic acid derivative is either used in approximately stoichiometric amounts or in excess. In suitable cases, it may also be possible to use a relatively large excess or to work without solvent. Preference is given to approximately stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of III.
The substituted 2-aminophenols III are advantageously obtained by reducing the corresponding 2-nitrophenols IV (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. XI/1, 4th Edition 1957, p. 431 ff.):
Het RZ Het R2 Reduction (IV) (III) Suitable reducing agents are, in particular, - elemental metals, such as iron, tin and zinc, - hydrogen in the presence of suitable catalysts, such as palladium or platinum on carbon or Raney nickel, or - complex hydrides, such as LiAlH4 and NaBH4, if appropriate in the presence of catalysts.
Suitable solvents are usually - depending on the reducing agent -carboxylic acids, such as acetic acid and propionic acid, mineral acids, such as hydrochloric acid or sulfuric acid, alcohols, such as methanol and ethanol, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, aromatic compounds, such as benzene and toluene, and mixtures of such solvents.
The reactions can be carried out at temperatures of from (-100)~C
to the boiling point of the reaction mixture in question.
The starting materials are usually employed in approximately stoichiometric amounts; however, in individual cases a multiple excess of one or the other component may be advantageous.
The 2-nitrophenols of the formula IV can be released from protected precursors which have a cleavable radical R at the phenol oxygen. Suitable radicals R are groups which protect the phenol group as ether, ester or carbonic acid derivative, for example alkyl, O-heterocyclyl, benzyl, alkylcarbonyl, arylcarbonyl or alkoxycarbonyl groups. Suitable radicals R and methods for their cleavage are known to the person skilled in the art, for example from Greene/Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, 2nd Edition 1991, p. 145 ff. and p.
279 ff.
Het ~ ~ R2 Het ~ ~ R2 Cleaving R-O N02 reagent HO N02 (IVa) (IV) Suitable cleaving reagents are, in particular:
- in the case of unsubstituted or substituted alkylphenols:
trimethylsilyl iodide, boron tribromide, boron trichloride, aluminum trichloride, lithium chloride or hydrogen bromide;
- in the case of unsubstituted or substituted benzylphenols:
boron trifluoride, hydrofluoric acid or hydrogen/catalyst, preferably noble metal catalysts, such as palladium or platinum;
- in the case of unsubstituted or substituted aryl esters:
sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, hydrogen chloride, sulfuric acid, ammonia, hydrazine or zinc.
The chosen solvent/diluent should preferably be inert to the cleaving reagent in question. If the halides trimethylsilyl iodide, boron tribromide, boron trichloride or aluminum trichloride are used, particular preference is given to halogenated solvents, such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane. Hydrogen bromide is preferably used in aqueous solution, very particularly preferably as a 48~
by weight strength solution; lithium chloride is preferably used in polar solvents, such as lower alcohols, dimethyl sulfoxide and dimethylformamide; hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, if appropriate with addition of a hydrogen transfer agent, such as cyclohexene or cyclohexadiene. Mineral bases or mineral acids and nitrogen bases are preferably used in aqueous medium. Depending on the solubility of the reagents, an organic solvent, such as, for example, a lower alcohol, is added, if appropriate.
The temperature for the cleavage reaction is preferably from O~C
to the boiling point of the reaction mixture in question.
The cleaving reagent is preferably employed in approximately stoichiometric amounts or in excess. The excess is particularly preferably between 1 and 10 molar equivalents, based on the amount of IVa.
Both the compounds of the formula IV and the compounds of the formula IVa can be prepared by nucleophilic exchange of the fluorine atom in 2-nitrofluorobenzenes of the formula V for an oxygen nucleophile R'Oe. Here, R' is hydrogen or one of the cleavable radicals R defined above. Whether the route via a protected derivative IVa is chosen or the 2-nitrophenol can be prepared directly from the 2-nitrofluorobenzene by exchange of fluorine for hydroxide depends on the stability of the radicals R1, RZ and Het in the compounds V.
Het ~ ~ R2 R' Oe Het ~ ~ RZ
F NOz R'-0 N02 (V) (IVa/IV) The exchange reaction of aromatically bonded fluorine for oxygen nucleophiles R'Oe are carried out in a manner known per se (c. f., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, 1976, Vol. 6/1c pp. 146-202 and Volume IX, 4th Edition 1955, pp. 7-18).
For this reaction, the following reagents are preferred reactants:
- for the exchange of F for OR: potassium benzoate, sodium nitrite, sodium hydroxide, potassium hydroxide, potassium carbonate, benzaldoxime, sodium acetate, potassium acetate, sodium methoxide, potassium methoxide, sodium trimethylsilanoate, dimethyl maleate, N-hydroxysuccinimide.
~
~ 0050/50571 CA 02381639 2002-02-11 - for the exchange of F for OH: sodium hydroxide, potassium hydroxide, lithium hydroxide.
In certain cases, the reactions can be carried out in the absence 5 of solvent/diluent. If a solvent/diluent is employed, preference is given to those in which the oxygen-group-transferring reagent is readily soluble. Particular preference is given to alcohols, such as ethanol, propanol or tert-butanol, aprotic polar solvents, such as dimethylformamide or dimethylacetamide, cyclic 10 ethers, such as dioxane or tetrahydrofuran, or aliphatic ethers, such as dimethoxyethane.
The reaction temperatures are preferably from 20~C to the reflux temperature of the reaction mixture in question, in particular 15 from 60~C to reflux temperature.
The oxygen-transferring reagent is either employed in approximately stoichiometric amounts or in excess. In suitable cases, it may also be possible to use a very large excess.
20 Preference is given to approximately stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of V.
The novel 2-nitrofluorobenzenes from V can be obtained in a manner known per se by reacting fluorobenzenes VI with nitrating 25 agents, i.e. N02+ transfer reagents (cf., for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. 10/1, 1971, p. 479 ff.):
Het ~ ~ R2 "N02+" Het ~ ~ R2 F F NOZ
(VI) (V) Suitable nitrating agents are, in particular, nitric acid, in a mixture with sulfuric acid or acetic anhydride, or nitronium salts, specially nitronium tetrafluoroborate. The mixture of nitric acid and sulfuric acid may comprise the two mixing partners in any ratio; preference is given to those mixtures in which the sulfuric acid predominates significantly or serves as solvent. This applies analogously to the mixture of nitric acid and acetic anhydride. Nitronium tetrafluoroborate is preferably used in aprotic polar solvents, for example in acetonitrile or nitromethane.
The reaction temperature is generally from (-80) to 80~C, in particular from (-20)~C to 30~C.
In the case of nitrations with the reagent nitric acid, the reaction is carried out using an approximately equimolar amount or particularly preferably an excess of nitrating agent. The excess may exceed the amount of VI by a large amount. Nitronium tetrafluoroborate is preferably used in an amount which is equimolar to that of the substrate, or in a small excess of from 1.1 to 1.5 molar equivalents.
The substituted fluorobenzenes of the formula VI can be prepared by customary syntheses for heterocycles or carbocycles, starting with known 2-aminofluorobenzenes VII or 2-fluorophenylhydrazines of the formula VIIa (scheme 1).
Scheme 1:
_ NHz ~ ~ RZ Het ~ ~ R2 F F
(VI) (VII) The compounds of formulas VI and VII are partly disclosed in the state of the art, e.g. in JP 0 9227535, US 4,818,272, US
4,919,708 and J. Heterocycl. Chem. 1987, 24, S.1391, or they can be prepared according to the methods described therein. With re-gards to compounds of formula VI and their preparation, these do-cuments are incorporated by reference.
Of course, it is also possible to carry out the synthesis sequence VII - VI - V - IV - III shown above using the corresponding amino compounds IIIa, IVb, IVc and Va (Scheme 2).
Scheme 2: R1 R1 ( VI I ) --~,. NH2 ~ ~ R2 ~ NH2 ~ ~ R2 \ \
F N02 R'-0 NOZ
(Va) (IVb) R1 (V) R1 (IVa) NH2 ~ ~ RZ ~ NHZ ~ ~ R2 ~ (III) (IVc) (IIIa) (IV) If appropriate, the amino group has to be protected in one or more steps. In each of the steps of this synthesis sequence, the amino group can be transformed into one of the radicals of the formulae II-1 to II-18.
It is also possible to synthesize the radical Het in the compounds I from 7-aminobenzoxazoles of the formula VIII (Scheme 3). The compounds of formula VIII are disclosed e.g. in WO 97/08170.
Scheme 3 NHZ ~ ~ RZ Het ~ ~ R2 O /N ~ O /N
(VIII) (I) Another route to prepare compounds of the invention of formula I
is shown in scheme 4:
00''J~/50571 CA 02381639 2002-02-11 Scheme 4:
1.N0+ R3COOH
Het ~ ~ R2 ~. Het ~ ~ R2 ~ Het ~ ~ R2 2 . N3 O_ /'N
(IX) (X) R3 (I) Het, R1, R2 and R3 in scheme 4 have the meanings mentioned above.
X is here a single bond. According to scheme 4, the anilines of formula IX, which are disclosed in the art, e.g. in WO 97/07104, are converted into the phenylazides of formula X by successive nitrosation into the diazonium compounds and subsequent reaction with an azide, the phenylazides being afterwards converted into the oxazoles of formula I, in which X is a single bond, by reac-ting X with a carboxylic acid of the formula R3COOH. The synthesis shown in scheme 4 is in a similar manner as the conversion of an-ilines into benzoxazoles being described in Houben-Weyl, Methoden der Organischen Chemie, Band EBa, 1993, S. 1087 ff. The azides of formula I are new and also subject of the present invention.
The diazonium salt of IX is prepared in a known manner, by reac-ting the aniline IX with a nitrite, e.g. sodium nitrite, potas-sium nitrite, in an aqueous acid solution, e.g. hydrochloric acid, hydrobromic acid, or sulfuric acid or by reacting X with a nitrite, e.g. tert-butyl nitrite or isopentyl nitrite in anhy-drous conditions, e.g. in glacial acetic acid containing hydroch-loric acid, in absolute alcohol, in dioxane or tetrahydrofurane, in acetonitrile or acetone. Conversion of the diazonium compounds into the arylazides takes place by reacting the diazonium com-pounds with an alkali azide or alkaline earth azide, e.g. sodium azide, or by reaction with trimethylsilylazide (see also: Organic Synthesis, Bd. IV, S. 75 and Bd. V, S. 829).
The reaction of azide compounds of the formula X with carboxylic acid R3-COON takes place in an inert organic solvent, e.g. in hy-drocarbons such as toluene or hexane, in halogenated hydrocarbons such as dichloromethane or chloroform, in ethers such as diethy-lether, dimethoxyethane, methyl-tert-butylether, dioxane or te-trahydrofurane, in amides such as dimethyl formamide, dimethyla-cet amide or N-methyl pyrrolidon, in acetonitril, or preferably without solvent in an excess of carboxylic acid R19COOH. In the latter case, the addition of a mineralic acid, such as phosphoric ~ ~ ~~SU/50571 CA 02381639 2002-02-11 acid and/or of a silylating reagent, such as a mixture of phosp-horous pentoxide and hexamethyldisiloxane can be helpful. The reaction takes place preferably at elevated temperatures, such as the boiling point of the reaction mixture.
The examples to follow shall furter describe the invention without restricting it.
Example 1:
3-(4-chloro-6-fluorobenzoxazol-7-yl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one (Comp. I-Aa.373 from Table 1) 1.0 g of 3-(5-amino-4-chloro-2-fluoro-6-hydroxyphenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one (from intermediate 7;
comprises 30~ of the 3-aminophenyl isomers) was initially charged in 30 ml of absolute ethanol, and 1.1 g of trimethyl orthoformate were added. The mixture was refluxed for 5.5 hours. The volatile components were then removed using water pump vacuum, and the product was purified by silica gel chromatography (mobile phase cyclohexane/ethyl acetate 95/5). Yield: 0.3 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 8.20(s, 1H); 7.40(d, 1H);
1.40(s, 9H).
Intermediate 1: 4-chloro-2,6-difluoraniline 30.0 g of 2,6-difluoraniline were mixed with 200 ml of concentrated acetic acid and heated at 80°C. 36.0 g of sulfuryl chloride were mixed with about the same amount of concentrated acetic acid and added dropwise to the heated solution. The solution was then refluxed for 6 hours. After cooling, the solution was concentrated under reduced pressure and the residue was stirred with water and pentane. The solid residue was filtered off and washed with water. The resulting solid was admixed with 200 ml of concentrated hydrochloric acid and refluxed for 2 hours. After cooling, the solution was carefully made weakly alkaline using aqueous sodium hydroxide solution and extracted three times with 100 ml of ethyl acetate. The organic phase was dried with sodium sulfate and the solvent was removed.
Yield: 34.0 g.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.85(d, 2H); 3.9-3.6(brd, 2H).
Intermediate 2: 4-chloro-2,6-difluorophenylhydrazine 25.0 g of 4-chloro-2,6-difluoroaniline were mixed with 277 ml of concentrated hydrochloric acid. The mixture was heated briefly until a fine suspension had formed. 10.6 g of sodium nitrite were dissolved in 60 ml of water and, at O~C, added dropwise to the suspension. The mixture was stirred at O~C for 2 hours. In a second flask, 86.7 g of tin dichloride dihydrate were initially charged in 52 ml of concentrated hydrochloric acid. At O~C, the 5 diazonium salt solution was added, resulting in the formation of a thick slurry and foaming of the mixture. The reaction mixture was then stirred at 20~C for 2 hours, poured onto water, insoluble .components were filtered off and the solution was adjusted to pH
11 using concentrated aqueous sodium hydroxide solution. The 10 precipitated solid was filtered off with suction and washed repeatedly with water. Yield: 16.2 g.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.90(d; 2H); 5.2-5.0(brd, 1H);
4.0-3.8 (brd, 2H).
15 Intermediate 3:
1-(4-chloro-2,6-difluorophenyl)-2-(2,2-dimethylpropionyl)hydra-zine 8.0 g of 4-chloro-2,6-difluorophenylhydrazine were dissolved in 20 200 ml of toluene. 27 ml of 10$ strength aqueous sodium hydroxide solution were added. With cooling, 5.66 g of pivaloyl chloride were then added dropwise at O~C, and the solution was stirred at 20°C for 3 hours. The organic phase was separated off, washed repeatedly with water and dried, and the solvent was removed.
25 Yield: 11.4 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.75(brd, 1H); 6.90(d, 2H);
6.30(brd, 1H); 1.2(s, 9H).
Intermediate 4:
30 3-(4-chloro-2,6-difluorophenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxa-diazol-2(3H)-one 11.0 g of 1-(4-chloro-2,6-difluorophenyl)-2-(2,2-dimethyl-propionyl)hydrazine in 100 ml of absolute toluene were mixed with 35 4.6 g of diphosgene. The mixture was refluxed for 3 hours, and another 5.0 g of diphosgene were then added. After a further 5 hours at reflux, a further 4.0 g of diphosgene and a drop of DMF were added, and the mixture was refluxed for 3 hours. After cooling, the mixture was neutralized with sodium bicarbonate 40 solution and the organic phase was then washed with water. Drying and removal of the volatile components gave a yield of 11.7 g of the desired product.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.10(d, 2H); 1.35(s, 9H).
~
~ 0050/50571 CA 02381639 2002-02-11 Intermediate 5:
3-(4-chloro-2,6-difluoro-3-nitrophenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one 11.5 g of 3-(4-chloro-2,6-difluorophenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one were dissolved in 15 ml of concentrated sulfuric acid. At O~C, 9 ml of 65~ strength nitric acid were added, and the mixture was stirred for 10 minutes. The mixture was then stirred into ice-water and extracted with 100 ml of tert-butyl methyl ether. The organic phase was washed with water and dried, and the volatile components were removed. Yield:
10.5 g.
1H-NMR (270 MHz, CDC13): b[ppm] = 7.35(d, 1H); 1.35(s, 9H).
Intermediate 6:
3-(4-chloro-2-fluoro-6-hydroxy-5-nitrophenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one 8.25 g of 3-(4-chloro-2,6-difluoro-3-nitrophenyl)-5-(1,1 dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one were dissolved in 250 ml of absolute dimethylformamide. 8.25 g of sodium acetate were added, and the mixture was heated at 120~C for 45 minutes.
After cooling, water was added and the solution was adjusted to a slightly acidic pH by addition of dilute hydrochloric acid and extracted with tert-butyl methyl ether. The organic phase was dried and volatile components were removed. Yield: 7.8 g, comprising 30~ of the 3-vitro isomer formed by exchange of the fluorine para to the vitro group.
1H-NMR (270 MHz, CDC13): 8[ppm] = 7.05(d, 1H); 1.40(s, 9H).
Intermediate 7:
3-(5-amino-4-chloro-2-fluoro-6-hydroxyphenyl)-5-(1,1-dimethyl-ethyl)-1,3,4-oxadiazol-2(3H)-one 7.8 g of the isomer mixture from intermediate 6 were taken up in a mixture of 170 ml of water and 17 ml of concentrated hydrochloric acid. The mixture was heated to 65~C and 6.63 g of iron powder were added a little at a time. The mixture was refluxed for 6 hours. After cooling, the mixture was extracted with ethyl acetate (150 ml), and drying of the organic phase and removal of the volatile components gave the product of value, comprising 30$ of the reduction product of the 3-vitro isomer from intermediate 6. Yield: 5.5 g of isomer mixture.
1H-NMR (270 MHz, CDC13): 8[ppm] = 6.85(d, 1H); 1.40(s, 9H).
Examples 2 to 6 ~
' ~ 0050/50571 CA 02381639 2002-02-11 In addition to those described above, Table 2 below lists further benzoxazole derivatives of the formula I which were prepared in a similar manner:
Table 2: 0 F
. ~ ~ ~ 1 HaC N ( I -Aa H C 0' / N
Example R3 m.p. [~C] 1H-NMR (CDC13) No. 8 [ppm]
1 H 99 $,20 (s), 7,40 (d), 1,40 (s, 9H) 2 CH3 117 7,30 (d), 2,70 (s, 3:[-i), 1,40 (s, 9H) 3 C2H5 oil "7,30 (d), 3,0 (q, 2H), 1,45 (t, 3H), 1,40 (s, 9H) 4 n-C4H9 oil 7,30 (d), 3,0 (t, 2H), 1,9 (q, 2H), 1,45 (m, 2H), 1,4 (s, 9H), 1,0 (t, 3H) 5 CHzCl oil 7,35 (d), 4,80 (s, 2:H), 1,40 (s, 9H) 6 phenyl 14 7 8,25 (d, 2H), 7,65-',~,5 (m, 3H), 7,35 (d), 1,4 (s, 9H) Examples 7 to 14 In a similar manner the compounds of examples 7 to 14, listed in Table 3, were prepared from 1-(4-Chlor-2,6-difluorphenyl)-3-tri fluormethyl-4-methyltriazol-5-on. All compounds had an oily con sistence.
Table 3: ~ F
H3C N_ ~ ~ ~ 1 / N (I_Ba) Example R3 1H-NMR (CDC13) No. b [ppm]
7 H 8,15 (s), 7,4 (d), 3,55 (s, 3H) g cH3 7,30 (d), 3,55 (s, 3H), 2,70 (s, 3H) 9 c2H5 7,30 (d), 3,55 (s, 3H), 3,0 (q, 2H), 1,45 (t, 3H) Example R3 1H-NMR (CDC13) No. b [ppm]
1o cH2c1 7,4 (d), 4,80 (s, 2H), 3,55 (s, 3H) 11 n-C3H~ 7,30 (d), 3,50 (s, 3H), 2,95 (t, 2H), 1,90 {q, 2H), 1,05 (t, 3H) 12 n-C4H9 7,30 (d), 3,50 (s, 3H), 2,95 (t, 2H), 1,90 (q, 2H), 1,45 (m, 2H), 1,0 (t, 3H) 13 C-C3H5 7,25 (d), 3,55 (s, 3H), 2,25 (m), 1,4-1,2 (m, 4H) 14 CHZ- ( c-C3H57,30 (d), 3,55 (s, 3H), 2,85 (d, 2H), ~ 1,25 (m), 0,55 (m, 2H), 0,35 (m, 2H) Example 15:
N-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4,5,6,7-te-trahydrophthalimide (Compd. I-Ca.419 from Table 1) In a similar manner to example 1, the title compound was prepared from 1-(4-chloro-2,6-difluorophenyl)-3-trifluoromethyl-4-methyl-triazole-5-one. The compound had an oily consistence.
1H-NMR (CDC13) 8 [ppm] 7,2 (d), 2,50 (s, br), 2,2 (m), 1,85 (s, br), 1,35-1,2 (m).
Example 16:
N-(4-chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4,5,6,7-te-trahydrophthalic acid dithioimide (Compd. I-C'a.419 from Table 1) 0,5 g N-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazole-7-yl)-4.5,6,7- tetrahydrophthalimide were dissolved in 55 ml toluene and 0,61 g phosphorous pentasulfide were added. The solution was heated to reflux and kept at this temperature for 46 h. The reac-tion mixture was dried in vacuum and purified chromatographically on silicagel with cyclohexane/ethyl acetate (100:1 to 10:1 v/v).
0~8 g of the title compound were yielded as solid with a melting point of 132-135~C.
1H-NMR (CDC13)b [ppm] 7,1 (d, 1H), 2,50 (m 4H), 2,2 (m, 1H), 1,9 (m, 4H), 1,3-1,1 (m, 4H).
Example 17:
2-(4-chloro-1-ethyl-6-fluorobenzoxazole-7-yl)-4-methyl-5-trifluo-romethylpyridazine-3-one (Compd. I-Ea.375 from Table 1) 8~9 g 2-(5-amino-2-fluoro-4-chlorophenyl)-4-methyl-5-trifluorome-thylpyridazine-3-one (from WO 97/07104) were dissolved in 90 ml trifluoro acetic acid. 3.0 g (0.029 mol) t-Butylnitrit were added ~
' ' ~~50/50571 CA 02381639 2002-02-11 dropwise at 5 to 10~C. Stirring was continued for 30 min at 5 to 10~C and 2.7 g (0.041 mol) sodium azide were added in portions.
After 1 h at 5 to 10~C stirring was continued for 3 h at RT, the reaction mixture was poured into 200 ml ice-water and extracted 3 times with methylene chloride. The organic phase was successi-vely washed with water, aqueous 10~ sodium hydroxide solution and again with water, dried over sodium sulfate and evaporated at room temperature. 9.2 g of the azide were yielded as fair solid, which was directly used in the next reaction step.
1H-NMR (CDC13) 8 [ppm] 8.0 (s, 1 H), 7.4 (d, 1H), 7.3 (d, 1 H), 2.4 (t, 3 H).
1.63 g (0.0115 mol) P401o were stirred for 30 min at 90~C in 6 ml hexamethyldisiloxane and then cooled to room temperature. A solu-tion of 1.6 g (0.0046 mol) of the azide from the previous reac-tion step in 20 ml propionic acid was added dropwise and the mix-ture was kept at 40~C for 3 h. The reaction mixture was poured into ice-water, alkalized with 10 ~ aqueous sodium hydroxide so-lution, and the aqueous phase was extracted 3 times with ethyl acetate. The combined organic phases were washed with water, eva-porated and purified by chromatography on silicagel with cyclohe-xane/ethyl acetate (6:1 v/v). 0.28 g of the title compound were yielded as a viscous oil.
The compounds of examples 18 bis 14, listed in Table 4, were pre-pared in a similar manner.
Table 4: R4 p F
~ \
F3 N ~ ~ C1 N
(I-E) p' /'N
~ 0050/50571 CA 02381639 2002-02-11 Example R R3 1H-NMR ~~[ppm]
(CDC13) No.
17 CH3 CH2CH3 8.05 (s, H),7.3 (d, 1 H), 3.0 (q, H),2.4 (s, H), 1.5 3 H).
8t 5 18 CH CH2CH2CH3 o5 H),7.3 (d, 1 H), 3 (s, 1 2.9 (t, H),2.4 (s, H), 1.9 (m, 2 H), 1.0(t, 3 H).
19 CH3 CH(CH3)Z 8.05 (s, H),7.3 (d, 1 H), 3.2 (sept.1 ), .4 , 3 H), H 2 (s 1.4 (d, H) 0 20 CH3 c-C3H5 8.05 (s, H),7.3 (d, 1 H), 2.4 (s, H),2.2 (m, H), 1.3 1.4 (m, 4 .
H) 21 CH3 CHZ-(c-C3H5) 8.05 (s, H),7.3 (d, 1 H), 2.8 (d, H),2.4 (s, H), 1.2 (m, 1 H, .6 m, H), 0.3 (m, 0 ( 2 15 2 H).
23 H CHyCHyCH3 24 H CH(CH3)2 25 H c-C3H5 20 26 H CH2-(c-C3H5) Example 27:
2-(4-chloro-6-fluorobenzoxazole-7-yl)-4-amino-5-methylsulfonylpy-25 ridazin-3-one (Compd. I-E'a.373 from Table 1) In a similar manner to the procedure described in example 17 the title compound was prepared from 2-(5-Amino-2-fluoro-4-chlorophe-nyl)-4-methyl-5-trifluoromethylpyridazin-3-one (known from 30 WO 9707104).
1H-NMR (DMSO) b [ppm] 9.0 (s, 1H), 8.3 (br. s, 1 H), 8.0 (s 1 H), 7.7 (br. s 1 H), 7.1 (d, 1 H).
Example 28:
3-(4-Chloro-1-cyclopropyl-6-fluorobenzoxazol-7-yl)-4,5-dihy-dro-5-(2-propyliden)-4-oxooxazol-2-one (Compd. I-Da.419 from Table 1) In a similar manner to the procedure described in example 1 the title compound was prepared from 2-(2,6-Difluoro-4-chlorophe-nyl)-4,5-dihydro-5-(2-propyliden)-4-oxooxazol-2-one. The title compound had an oily consistence.
The compounds I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions ~
which comprise I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, Soya and cotton, they act against broad-leaved weeds and grass weeds without inflicting substantial damage to the crop plants. This effect is observed mainly at low rates of application.
Depending on the application method in question, the compounds I, or herbicidal compositions comprising them, can also be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus °fficinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
In addition, the compounds I can also be used in crops which, by means of breeding, including genetic engineering methods, have been made tolerant to the action of herbicides.
The active ingredients I, or the herbicidal compositions, may be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that they come in as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of ~ ~ 0050/50571 CA 02381639 2002-02-11 undesirable plants which grow underneath, or the bare soil surface (post-directed, lay-by).
The compounds I, or the herbicidal compositions comprising them, can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
The use forms depend on the intended purposes; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their,derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg.
amines such as N-methylpyrrolidone, and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substituted benzoxazoles, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acid, eg, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, ~ ~ 0~5~/50571 CA 02381639 2002-02-11 isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or binding the active substances together with a solid carrier. Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The concentration of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98~ by weight, preferably from 0.01 to 95~ by weight, of at least one active Ingredient. The active ingredients are employed in a purity of from 90~ to 100, preferably 95~ to 100 (in accordance with NMR
spectra).
The compounds I according to the invention can be formulated, for example, as follows:
I. 20 parts by weight of Active ingredient of example 1 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoetha-nolamide, 5 parts by weight of calcium dodecylbenzenesulfo-nate and 5 parts by weight of the adduct of 40 mol of eth-ylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distribut-ing it therein gives an aqueous dispersion which comprises 0.02 by weight of the active ingredient.
II. 20 parts by weight of Active ingredient of example 2 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02 by weight of the active ingredient.
III. 20 parts by weight of Active ingredient of example 3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02$ by weight of the active ingredient.
IV' 20 parts by weight of Active ingredient of example 4 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1~ by weight of the active ingredient.
V. 3 parts by weight of Active ingredient of example 1 are mixed with 97 parts by weight of finely divided kaolin.
This gives a dust which comprises 3~ by weight of the ac-tive ingredient.
VI. 20 parts by weight of Active ingredient of example 5 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII. 1 part by weight of Active ingredient of example 6 is dis-solved in a mixture composed of 70 parts by weight of cy-clohexanone, 20 parts by weight of ethoxylated isooctylphe-nol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
VIII. 1 part by weight of Active ingredient of example 1 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol~ EM 31 (_ nonionic emulsifier based on ethoxylated castor oil; BASF
AG). This gives a stable emulsion concentrate.
0~5U/50571 CA 02381639 2002-02-11 To widen the spectrum of action and to achieve synergistic effects, the substituted benzoxazoles I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and applied jointly.
5 Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)-aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 10 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, 15 dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic 20 acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Furthermore, it may be advantageous to apply the compounds I, alone or in combination with other herbicides, also as a mixture with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for remedying nutritional and trace-element deficiencies. Nonphytotoxic oils and oil concentrates may also be added. Depending on the control target, the season, the target plants and the growth stage, the rates of application of active ingredient are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.).
Use Examples The herbicidal activity of compounds of formula I according to the invention was demonstrated by the following greenhouse expe-riments:
Plastic pots were used as culture containers, containing loamy sand with approximately 3.0~ of humus as substrate. The seeds of the test plants were sown separately according to their species.
For the pre-emergence treatment, the active compounds were sus-pended or emulsified in water and were applied directly after so-wing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subse-quently covered with plastic hoods until the plants had rooted.
This cover causes uniform germination of the test plants, unless this was adversely affected by the active compound.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and then treated with the active compounds which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to the treatment. The application rate for the post-emergence treatment was 31.2, 15.6 or 7.81 g/ha of active substance.
Depending on the species, the plants were kept at 10-25~C or 20-35~C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.
The plants used in the greenhouse experiments were of the following species:
Bayer code German name English name AMARE Zuruckgekrummter redroot pigweed Fuchsschwanz POLPE Flohknoterich lady's thumb ABUTH lindenblattrige velvet leaf Schonmalve The following tests were performed in the post-emergence treat-ment.
The compound of example 27 (Compound I-E~a.373 of Table 1) had a very good herbicidal activity against ABUTH, AMARE and POLPE with application rates of 31.2 and 15.6 g/ha a.S.
The compound of example 15 (Compound I-Ca.419 of Table 1) had a very good herbicidal activity against ABUTH, AMARE and POLPE with application rates of 15.6 and 7.81 g/ha a.S.
The compound of example 17 (Compound Nr. I-Ea.375) had a very good herbicidal activity against ABUTH, AAMARE and POLPE with ap-plication rates of 15.6 and 7.81 g/ha a.S.
The compound of example 13 (Compound Nr. I-Ba.419 had a good to very good herbicidal activity against ABUTH, AAMARE and POLPE
with application rates of 31.2 and 15.6 g/ha a.S.
Claims (14)
1. A substituted benzoxazole of the formula I
in which Z is a chemical bond, O or S, R1 is hydrogen or halogen, R2 is halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, and R3 is C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-C8-cycloalkoxy-C1-C4-alkyl, is amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl;
is phenyl, phenyl-C1-C4-alkyl, where the phenyl rings may carry one, two or three substituents selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl, 3- to 7-membered heterocyclyl-C1-C4-alkyl, where heterocyclyl contains one, two or three hetero atoms selected from oxygen, sulfur and nitrogen atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl and heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C1-C4-hydroxyalkyl, C1-C4-aminoalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy, di(C1-C4-alkyl)amino, C3-C6-alkenyl, C3-C6-alkynyl, C3-C4-alkenyloxy, C3-C4-alkenylthio, C3-C4-alkynyloxy and C3-C4-alkynylthio;
or, if Z is a chemical bond, R3 may also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered, N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CH2)n-CH(OH)-CH2-R9, -(CH2)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CH2)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1;
Het is an unsaturated, five- or six-membered heterocyclic radical which is attached to the benzoxazole moiety via a nitrogen atom and which is selected from radicals of the formulae II-1 to II-18 in which R4, R4' and R4" independently of one another are hydrogen, halogen, cyano, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, carboxyl, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-haloalkylthio, C1-C6-alkoxycarbonyl, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C3-C$-cycloalkyl or C3-C8-cycloalkyl-C1-C4-alkyl;
R5 and R5' independently of one another are hydrogen, amino, hydroxyl, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxycarbonyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl or phenyl-C1-C6-alkyl;
and/or two of the radicals R4, R4', R4", R5 and R5' together with the cycle to which they are attached form a 4-, 5-, 6- or 7-membered ring which may be saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three radicals selected from the group consisting of C1-C4-alkyl and halogen;
R6 and R7 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C3-C6-cycloalkyl, or together with the carbon atom to which they are attached form a 4-, 5-, 6- or 7-membered ring which may be saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three substituents selected from the group consisting of C1-C4-alkyl and halogen;
Q in the formula II-1 is O or S, X and X' independently of one another are O or S, and Y is O, S or a group N-R8 in which R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C3-C8-cycloalkyl;
and the agriculturally useful salts of the compound of the formula I.
in which Z is a chemical bond, O or S, R1 is hydrogen or halogen, R2 is halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, and R3 is C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-C8-cycloalkoxy-C1-C4-alkyl, is amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl;
is phenyl, phenyl-C1-C4-alkyl, where the phenyl rings may carry one, two or three substituents selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl, 3- to 7-membered heterocyclyl-C1-C4-alkyl, where heterocyclyl contains one, two or three hetero atoms selected from oxygen, sulfur and nitrogen atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl and heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C1-C4-hydroxyalkyl, C1-C4-aminoalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy, di(C1-C4-alkyl)amino, C3-C6-alkenyl, C3-C6-alkynyl, C3-C4-alkenyloxy, C3-C4-alkenylthio, C3-C4-alkynyloxy and C3-C4-alkynylthio;
or, if Z is a chemical bond, R3 may also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered, N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CH2)n-CH(OH)-CH2-R9, -(CH2)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CH2)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1;
Het is an unsaturated, five- or six-membered heterocyclic radical which is attached to the benzoxazole moiety via a nitrogen atom and which is selected from radicals of the formulae II-1 to II-18 in which R4, R4' and R4" independently of one another are hydrogen, halogen, cyano, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, carboxyl, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-haloalkylthio, C1-C6-alkoxycarbonyl, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C3-C$-cycloalkyl or C3-C8-cycloalkyl-C1-C4-alkyl;
R5 and R5' independently of one another are hydrogen, amino, hydroxyl, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxycarbonyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl or phenyl-C1-C6-alkyl;
and/or two of the radicals R4, R4', R4", R5 and R5' together with the cycle to which they are attached form a 4-, 5-, 6- or 7-membered ring which may be saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three radicals selected from the group consisting of C1-C4-alkyl and halogen;
R6 and R7 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C3-C6-cycloalkyl, or together with the carbon atom to which they are attached form a 4-, 5-, 6- or 7-membered ring which may be saturated or unsaturated, which may contain one or two oxygen and/or sulfur atoms as ring members and/or which may be substituted by one, two or three substituents selected from the group consisting of C1-C4-alkyl and halogen;
Q in the formula II-1 is O or S, X and X' independently of one another are O or S, and Y is O, S or a group N-R8 in which R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C3-C8-cycloalkyl;
and the agriculturally useful salts of the compound of the formula I.
2. A substituted benzoxazole as claimed in claim 1 in which Het is a nitrogen heterocycle which has at least one carbonyl or thiocarbonyl function and which is selected from the radicals of the formulae II-1, II-2, II-5, II-6 and II-12.
3. A substituted benzoxazole as claimed in claim 2 in which Het is a radical of the formula II-1 in which X and Q are oxygen and R4 is C1-C6-alkyl.
4. A substituted benzoxazole as claimed in claim 2 in which Het is a radical of the formula II-2 in which X is oxygen, R5 is hydrogen or C1-C4-alkyl, and R4 is C1-C4-haloalkyl.
5. A substituted benzoxazole as claimed in claim 2 in which Het is a radical of the formula II-5 in which X and X' are oxygen, R4 and R4' independently are hydrogen or C1-C4-alkyl, or form a 6-membered carbocyclic ring, together with the carbon atoms to which they are bonded.
6. A substituted benzoxazole as claimed in claim 2 in which Het is a radical of the formula II-6 in which X, X', and Y are oxygen, R6 and R7 are C1-C4-alkyl, or form a 5- or 6-membered saturated carbocyclic ring, together with the carbon atom to which they are bonded.
7. A substituted benzoxazole as claimed in claim 2 in which Het is a radical of the formula II-12 in which X is oxygen, R4 is selected from hydrogen, amino, and C1-C4-alkyl, R4' is C1-C4-haloalkyl or C1-C4-alkylsulfonyl and R4" is hydrogen.
8. A substituted benzoxazole as claimed in any of the preceding claims in which R1 is hydrogen, fluorine or chlorine and R2 is halogen or cyano.
9. A substituted benzoxazole according to any of the preceding claims in which R3 is C1-C4-alkyl, C1-C4-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl;
is phenyl which may carry a substituent selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is saturated C3-C7-cycloalkyl, 3- to 7-membered saturated heterocyclyl which contains one, two or three hetero atoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member;
or, if Z is a chemical bond, R3 can also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CH2)n-CH(OH)-CH2-R9 , -(CH2)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CH2)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1.
is phenyl which may carry a substituent selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
is saturated C3-C7-cycloalkyl, 3- to 7-membered saturated heterocyclyl which contains one, two or three hetero atoms selected from oxygen and sulfur atoms, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member;
or, if Z is a chemical bond, R3 can also, if desired, be hydrogen, hydroxyl, cyano, mercapto, amino, C1-C4-alkylamino, di-C1-C4-alkylamino, saturated, 5- or 6-membered N-bonded nitrogen heterocyclyl, C3-C6-cycloalkylamino, halogen, -(CH2)n-CH(OH)-CH2-R9 , -(CH2)n-CH(halo)-CH2-R9, -(CH2)n-CH2-CH(halo)-R9, -(CH2)n-CH=CH-R9 or -(CH2)n-CH=C(halo)-R9, in which R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl and n is 0 or 1.
10. A compound of the formula III, IV or V
in which R1, R2 and Het are as defined in claim 1.
in which R1, R2 and Het are as defined in claim 1.
11. A composition comprising at least one substituted benzoxazole of the formula I or an agriculturally useful salt of I as claimed in any of claims 1 to 9, and customary auxiliaries.
12. A method for controlling undesirable vegetation, which comprises allowing a herbicidally effective amount of at least one substituted benzoxazole of the formula I or an agriculturally useful salt of I as claimed in any of claims 1 to 9 to act on plants, their habitat and/or on seeds.
13. The use of substituted benzoxazoles of the formula I or their agriculturally useful salts as claimed in any of claims 1 to 9 as herbicides.
14. A compound of the formula x wherein R1, R2 and Het are as defined in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19938073 | 1999-08-12 | ||
| DE19938073.2 | 1999-08-12 | ||
| PCT/EP2000/007803 WO2001012625A2 (en) | 1999-08-12 | 2000-08-10 | Substituted benzoxazoles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2381639A1 true CA2381639A1 (en) | 2001-02-22 |
Family
ID=7918062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002381639A Abandoned CA2381639A1 (en) | 1999-08-12 | 2000-08-10 | Substituted benzoxazoles |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1200428B1 (en) |
| JP (1) | JP2003507377A (en) |
| AU (1) | AU6994600A (en) |
| CA (1) | CA2381639A1 (en) |
| DE (1) | DE50001813D1 (en) |
| WO (1) | WO2001012625A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR081331A1 (en) | 2010-04-23 | 2012-08-08 | Cytokinetics Inc | AMINO- PYRIMIDINES COMPOSITIONS OF THE SAME AND METHODS FOR THE USE OF THE SAME |
| US9133123B2 (en) | 2010-04-23 | 2015-09-15 | Cytokinetics, Inc. | Certain amino-pyridines and amino-triazines, compositions thereof, and methods for their use |
| AR081626A1 (en) | 2010-04-23 | 2012-10-10 | Cytokinetics Inc | AMINO-PYRIDAZINIC COMPOUNDS, PHARMACEUTICAL COMPOSITIONS THAT CONTAIN THEM AND USE OF THE SAME TO TREAT CARDIAC AND SKELETIC MUSCULAR DISORDERS |
| US8759380B2 (en) | 2011-04-22 | 2014-06-24 | Cytokinetics, Inc. | Certain heterocycles, compositions thereof, and methods for their use |
| CN112209894B (en) * | 2020-10-23 | 2023-06-06 | 贵州医科大学 | 5-aryl substituted 2-aminobenzoxazole derivative, preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753595A (en) * | 1995-08-31 | 1998-05-19 | Fmc Corporation | Herbicidal 3-(substituted benzoxazol-7-yl) and 3-(Substituted benzothiazol-7-yl)-1-substituted-6-trifluoromethyl-2 4-(1h 3h)pyrimidinediones |
| DE19532048A1 (en) * | 1995-08-31 | 1997-03-06 | Basf Ag | Substituted benzthiazoles as plant protection products |
| EP0853620A1 (en) * | 1995-10-04 | 1998-07-22 | Fmc Corporation | Herbicidal heterocyclic benzisoxazoles and benzisoxazolidinones |
| JPH09301973A (en) * | 1996-05-09 | 1997-11-25 | Kumiai Chem Ind Co Ltd | Chromene derivative and herbicide containing the same as active ingredient |
| US6077812A (en) * | 1997-02-26 | 2000-06-20 | Fmc Corporation | Cycloimido-substituted benzofused heterocyclic herbicides |
| DE19755926A1 (en) * | 1997-12-17 | 1999-06-24 | Basf Ag | Herbicidal 3- (benzazol-4-yl) pyrimidinedione derivatives |
| EA200100523A1 (en) * | 1998-11-16 | 2001-10-22 | Басф Акциенгезельшафт | 3- [BENZ (OX / TI) AZOL-7-IL] -1H-PYRIMIDIN-2,4-DIONS |
-
2000
- 2000-08-10 JP JP2001517523A patent/JP2003507377A/en not_active Withdrawn
- 2000-08-10 WO PCT/EP2000/007803 patent/WO2001012625A2/en active IP Right Grant
- 2000-08-10 EP EP00958421A patent/EP1200428B1/en not_active Expired - Lifetime
- 2000-08-10 AU AU69946/00A patent/AU6994600A/en not_active Abandoned
- 2000-08-10 CA CA002381639A patent/CA2381639A1/en not_active Abandoned
- 2000-08-10 DE DE50001813T patent/DE50001813D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003507377A (en) | 2003-02-25 |
| AU6994600A (en) | 2001-03-13 |
| WO2001012625A3 (en) | 2001-08-23 |
| DE50001813D1 (en) | 2003-05-22 |
| EP1200428B1 (en) | 2003-04-16 |
| WO2001012625A2 (en) | 2001-02-22 |
| EP1200428A1 (en) | 2002-05-02 |
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