AU732154B2 - Benzothiophene derivates as herbicides - Google Patents
Benzothiophene derivates as herbicides Download PDFInfo
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- AU732154B2 AU732154B2 AU93441/98A AU9344198A AU732154B2 AU 732154 B2 AU732154 B2 AU 732154B2 AU 93441/98 A AU93441/98 A AU 93441/98A AU 9344198 A AU9344198 A AU 9344198A AU 732154 B2 AU732154 B2 AU 732154B2
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- alkyl
- haloalkyl
- formula
- alkyi
- substituted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/80—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 1,2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
- C07D413/06—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 linked by a carbon chain containing only aliphatic carbon atoms
Description
WO 99/09023 PCTI/ PQ O1/ A'7 -1- BENZOTHIOPHENE DERIVATES AS HERBICIDES The present invention relates to novel herbicidally active substituted bicyclic benzoyl derivatives, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth.
Isoxazolyl- and pyrazolyl-benzoyl and bicyclic benzoyl derivatives having herbicidal activity are known and are described, for example, in WO 96/26192, WO 96/26206 and WO 97/08164.
New substituted bicyclic benzoyl derivatives having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I
R,
R
2 -S(O)o o
R
3 Q R4
I
R
wherein R, is Ci-C 4 alkyl, C 1
-C
4 haloalkyl, C 1
-C
4 alkoxy-Cl-C 4 alkyl, C 1
-C
4 alkoxycarbonyl, cyano, cyano- Cl-C 4 alkyl, hydroxy-C 1
-C
4 alkyl, amino-C 1
-C
4 alkyl, CHO, C 1
-C
4 alkyl-ON=CH, C 2
-C
6 alkenyl,
C
1
-C
4 alkoxycarbonyl-C 2
-C
6 alkenyl or a group -CH(OR 2 0
)OR
21
R
20 and R 2 1 are each independently of the other Cl-C 4 alkyl; or R 20 and R 21 together are
-(CH
2 n, is 2, 3 or 4;
R
2 is hydrogen or Ci-C 4 alkyl;
R
3 and R 4 are each independently of the other hydrogen, C1-C 4 alkyl or halogen; n is 0, 1 or 2;
I
WO 99/09023 PrT/VDnv inn A'?
R
5 is Cl-C 4 alkyl, C 1
-C
4 haloalkyl, 0 2
-C
6 alkenYl, C 2
-C
6 alkynyl, Cl-C 4 alkoxy, Cl-C 4 haloalkoxy,
C
1
-C
4 alkyl-S(O),1 2 (0 1
-C
4 alkyl) 2
NS(O)
2
C
1
-C
4 alkyl-S(O) 2 O, halogen, nitro or cyano; nl 2 isO0, 1 or 2; Q is OH, halogen or a group
R
8 t7 (Q1(, 2 N (Qs) or OH N 0
R
8 NH-9
AQ),
R
13
R
1 4 0
R
6 and R 7 are each independently of the other hydrogen, OH, CI-C 4 alkyI, C 2
-C
6 alkenyl, 0 2
-C
6 alkynyl, C 1
-C
4 alkoxycarbonyl, Cl-C~alkyl-S(O)Q 2 Cl-C 4 alkyl-NHS(O) 2 phenyl or phenyl substituted by CI-C 4 alkyI, C 1
-C
4 haloalkyl, Cl-C 4 alkoxy, C 1
-C
4 haloalkoxy, Cl-C 4 alkylcarbonyl, Cl-C 4 alkoxycarbonyl, amino, Cl-C 4 alkylamino, di-Cl-C 4 alkylamino, Cl-C 4 alkyl-S(O)n 2
C
1
-C
4 alkyl-S(O) 2 0, Cl-C 4 haloalkyI-S(O)n 2 Cl-C 4 haloalkyl-S(O) 2 0, Cl-C 4 alkyl-S(O) 2
NH,
C
1
-C
4 alkyl-S(O) 2
N(C
1
-C
4 alkyI), halogen, nitro, COOH or cyano; or R 6 and R 7 are each independently of the other Cl-C 4 haloalkyl, -NH-Cl-C 4 alkyl, -N(Cl-C 4 alkyl) 2
C
1
-C
6 alkoxy, cyano, nitro or halogen; or adjacent R 6 and R 7 together are -(CH 2 3 n 3 is 2, 3,4, 5or 6; W is oxygen, sulfur, -C(Rl 8 2 or -N(R 22 n 6 is 0 or 1, or when W is -C(Rl 8 2 n 6 may additionally be 2 or 3; each R 1 8 independently of the other is hydrogen, Cl-C 4 alkyl, C 1
-C
4 haloalkyl or Cl-C 4 alkoxycarbonyl; or WO 99/09023 WO 9909023PCT/EP98/05247 -3- RIB together with one of the adjacent substituents R 7 forms a single bond when n 6 is 1, and the remaining gemninal R 6 and R 7 are other than hydrogen;
R
22 is hydrogen, C 1
-C
4 alkyl or Cl-C 4 alkoxycarbonyl;
R
8 is OH, Cl -C 4 alkoxy, C 1
-C
4 alkylcarbonyloxy, Cl -C 4 al koxycarbonyloxy, R 23
R
24
N-C(O)O,
phenylthio, C 1
-C
4 alkylthio, Cl-C 4 alkyl-S(O) 2 0, (C 1
-C
4 alkoxy) 2 P(O)O, C 1
-C
4 alkyl(C 1
-C
4 alkoxy)P(O)O, H(Cl-C 4 alkoxy)P(O)O or benzoyloxy;
R
23 and R 24 are each independently of the other hydrogen or Cl-C 4 alkyl; Y is oxygen, sulfur or -(CH 2 )r, 5 -1 n 5 is 0, 1, 2, 3or 4;
R
9 is hydrogen, Cl-C 6 alkyl, Cl-C 4 alkylcarbonyl, C 1
-C
4 alkoxycarbonyl, (Cl-C 4 alkyl)NHCO or (Cl-C 4 alkyl) 2
NCO;
RIO, R 1 1 and R 12 are each independently of the others hydrogen, Cl-C 4 alkyl, C 1
-C
4 alkoxycarbonyl, phenyl or phenyl substituted by C 1
-C
4 alkyI, CI-C 4 haloalkyl, Cl-C 4 alkoxy, C 1
-C
4 haloalkoxy, C 1
-C
4 alkylcarbonyl, C 1
-C
4 alkoxycarbonyl, amino, Cl-C 4 alkylamino, di-C 1
-C
4 alkylamino, Cl-C~alkyl-S(O),1 2
C
1
-C
4 alkyl-S(O) 2 0, CI-C 4 haloalkyl-S(O), 2 Cl -C 4 haloalkyl-S(O) 2 0,
C
1
-C
4 alkyl-S(O) 2 NH, C 1
-C
4 alkyl-S(O) 2
N(C
1
-C
4 alky), halogen, nitro, GOGH or cyano;
R
13 is hydrogen; halogen; Cl-C 4 alkyI; C 1
-C
4 alkyl substituted by unsubstituted or R 17 substituted phenyl; C 1
-C
4 haloalkyl; C 2
-C
6 alkenyl; C 2
-C
6 alkenyl substituted by unsubstituted or R 17 -Substituted phenyl; C 2
-C
6 alkynyl; C 2
-C
6 alkynyl substituted by unsubstituted or R 17 substituted phenyl; C: 3
-C
6 haloalke nyl; C 3
-C
6 haloalkynyl; C 3
-C
6 CYCloalkyl; C 3
-C
6 cycloalkyl substituted by halogen, R 15 or C00R 16 C00R 16 C0R 15 cyano; nitro; CONH- 2 (Cl-C 4 alkyl)NHCO; (C 1
-C
4 alkyI) 2 NCO; (Cl-C 4 haioalkyl)NHCO; (C 1
-C
4 haloalkyl) 2 NCO; CI-C 4 alkyl-
S(O),
2
C
1
-C
4 alkyl-S(O)n 2 substituted by unsubstituted or R 17 -substituted phenyl; C 1
-C
4 alkoxy-C 2
-C
6 alkyl-S(O)n 2
C
2
-C
6 alkenyl-S(O)n 2
C
2
-C
6 alIkeny-S(O)" 2 substituted by unsubstituted or R 17 -substituted phenyl; C 2
-C
6 alkynyl-S(O), 2 or C 2
-C
6 alkynyl-S(O)" 2 substituted by unsubstituted or R 17 -substituted phenyl;
R
15 is C 1
-C
4 alkyl, Cl-C 4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, C 3
-C
6 haloalkynyl, phenyl or R 17 -substituted phenyl;
R
1 6 is hydrogen, C 1
-C
4 alkyl or Cl-C 4 haloalkyl;
R
17 is halogen, Cl-C 4 alkyl, CI-C 4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, WO 99/09023 PCTJEP0 5OIf~147 -4-
C
3
-C
6 haloalkynyl, C 1
-C
4 alkoxy-C 1
-C
4 alkyl, C 1
-C
4 alkoXY-C 3
-C
6 alkenyl, C1 -C 4 alkoXY-C 3
-C
6 alkynyl, cyano, nitro, COOH, Cl-C 4 alkoxycarbonyl, Cl-C 4 haloalkoxycarbonyl, Cl-C 4 alkyl-
S(O)Q
2 Cl-C 4 haloalkyl-S(O)n 2 phenyl-S(O), 2 phenyl-S(O),, 2 substituted on the phenyl ring by halogen, Cl-C 4 alkyl, C 1
-C
4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 alkynyl, cyano, nitro, COOH, 01-04alkoxycarbonyl, C 1
-C
4 alkyI-S(O), 2
C
1
-C
4 haIoaIky-S(O), 2 01 -C 4 alkylcarbonyl, di-0 1
-C
4 alkylamino, Cl-C 4 alkoxy, Cl-C 4 haloalkoxy, C 1
-C
4 alkyI-S(O) 2 0 or C 1
-C
4 haloalkyl-S(O) 2 0; 01-04alkylcarbonyl, di-C 1
-C
4 alkylamino, Cl-C 4 alkyl-S(O) 2 NH, C 1
-C
4 alkyl-S(O) 2
N(C
1
-C
4 alkyl), Cl-C 4 haloalkyl-S(O) 2 NH, C 1
-C
4 haloalkyl-S(O) 2
N(C
1
-C
4 alkyt), NH 2
S(O)
2 (Cl-C 4 alkyl)NHS(O) 2 (Cl-C 4 alkyI) 2
NS(O)
2
CONH
2
(C
1
-C
4 alkyI)NHCO, (C 1
-C
4 alkyI) 2 NCO, NH 2
CS,
(Cl-C 4 alkyl)NHCS, (0 1
-C
4 alkyl) 2 NCS, C 1
-C
4 alkoxy, Cl-C 4 haloalkoxy, C 3
-C
6 alkenyloxy,
C
3
-C
6 alkynyloxy, C 1
-C
4 alkyl-S(O) 2 0, Cl -C 4 haloalkyl-S(O) 2 0, phenyl-S(O) 2 0 or phenyl-
S(O)
2 0 substituted on the phenyl ring by halogen, C 1
-C
4 alkyl, Cl-C 4 haloalkyl, C 3
-C
6 alkenyl,
C
3
-C
6 alkynyl, cyano, nitro, COCH, Cl-C 4 alkoxycarbonyl, C 1
-C
4 alkyl-S(O)n 2 Cl-C 4 haloalkyl-
S(O),
2
C
1
-C
4 alkylcarbonyl, di-Cl-C 4 alkylamino, CI-C~alkoxy, C 1
-C
4 hatoalkoxy, Cl -C 4 alkyl-
S(O)
2 0 or Cl-C 4 haloalkyl-S(O) 2 0; and
R
14 is C 1
-C
4 alkyl, Ci -C 4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, C 3
-C
6 haloalkynyl, C 3
-C
6 cycloalkyl or 0 3
-C
6 cycloalkyl substituted by halogen, Cl-C 4 alkyl, C 1
-C
4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, C 3
-C
6 haloalkynyl, phenyl or phenyl substituted by halogen, Cl-C 4 alkyl, C 1
-C
4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 alkynyl, cyano, nitro, COOH, 01 -C 4 alkoxycarbonyl, 01 -C 4 alkyI-S(O)1 2
C
1
-C
4 haloalkyI-S(O), 2
C
1
-C
4 alkyicarbonyl, di-Cl-C 4 alkylamino, Cl-C 4 alkoxy, 01 -C 4 haloalkoxy, C 1
-C
4 alkyl-S(O) 2 0 or C 1
-C
4 haloalkyl-
S(O)
2 0, and the agrochemically acceptable salts and stereoisomers of those compounds of formula 1.
In the above definitions, halogen is to be understood as meaning iodine or, preferably, fluorine, chlorine or bromine.
The alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, cyanoalkyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylaminocarbonyl, dialkylaminocarbonyl, (alkyl) 2
NS(O)
2 alkyl(alkoxy)P(O)O, alkyl substituted by unsubstituted or R 1 7 substituted phenyl, alkenyl substituted by unsubstituted or R 17 -substituted phenyl, alkoxycarbonylalkenyl, alkyiS(O) 2 N(alkyl), (alkyl) 2 NCO, (alkyl) 2 NCS ,alkenyl-S(O), 2 substituted by WO 99/09023 PT/EP98/05247' unsubstituted or R 17 -substituted phenyl, alkoxyalkenyl, alkenyloxy and alkynyloxy.
Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
Examples of alkenyl radicals that may be mentioned are vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
Examples of alkynyl radicals that may be mentioned are ethynyl, propargyl, 1-methylpropargyl, 3-butynyl, but-2-yn-1 -yl, 2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1 -pentynyl, pent-4yn-1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
Suitable haloalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Of the alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4trifluoro-but-2-yn- 1 -yl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- WO 99/09023 PCTtPPQ2/fiC')A-I sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chloromethylsulfonyl, trichioromethylsulfonyl, 2-f luoroethylsulfonyl, 2,2,2-tnifluoroethylsulfonyl or 2,2,2-trichioroethylsulfonyl.
Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl, but-2-en-1 -ylsulfonyl, pentenylsulfonyl or 2-hexenylsulfonyl.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
Alkylamino is, for example, methylamino, ethylamino or an isomer of propyl- or butyl-amino.
Dialkylamino is, for example, dimethylamino, diethylamino or an isomer of dipropyl- or dibutyl-amino.
Alkylcarbonyl is especially acetyl or propionyl.
Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secbutoxy or tert-butoxy.
Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy.
Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymnethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-f luoroethoxy, 2-chloroethoxy, 2,2,2-trichioroethoxy or pentafluoroethoxy.
The cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or per- WO 99/09023 WO 9909023PCT/EP98/0527 -7halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl, 2fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2dichloro-3,3-difluorocyclobutyl, fluorocyclopentyl, difluorocyclopentyl, chlorocyclopentyl, perfluorocyclopentyl, chlorocyclohexyl and pentachlorocyclohexyl.
Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
Phenyl per se, or as part of a substituent, such as, for example, phenylthio or benzoyloxy, may be unsubstituted or substituted, in which case the substituents may be in the ortho-, meta- or para-position. Unless specifically indicated, substituents are, for example, C1-C4alkyl, C 1
-C
4 alkoxy, halogen or Cl-C 4 haloalkyl.
Corresponding meanings may also be given to the substituents in combined definitions, such as, for example, alkyl-S(O)-, alkyl-ON=CH-, (alkyl) 2 NCO-, alkenyl-SO-, alkynyl-S(O).
2 alkylcarbonyloxy-, haloalkoxycarbonyl-, haloalkyl-S(O) 2 haloalkyl-SO-, (alkyl) 2
NS(O)
2 alkyl-S(O) 2 alkyl substituted by unsubstituted or R 17 -substituted phenyl, alkenyl substituted by unsubstituted or R 17 -substituted phenyl, alkyl-S(O) 2 NH-, haloalkyl-S(O) 2
NH-,
alkylNHS(O) 2 alkylNHCO-, haloalkylNHCO-, (alkyl) 2 NCS-, H(alkoxy)P(O)O-, alkyl(alkoxy)P(O)O-, (alkoxy) 2 alkoxycarbonyl-alkenyl, alkyl-S(O)1 2 substituted by unsubstituted or R 1 7 -substituted phenyl, alkoxy-alkyl-S(O)1 2 and alkynyl-S(O),' 2 In the definitions of cyanoalkyl, alkylcarbonyl, alkoxycarbonylalkenyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy and haloalkoxycarbonyl, the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
The compounds of formula I wherein Q is a group Q, to Q 4 and RB is OH can be in the form of mixtures of the following isomeric forms 1, to 14 and Ic: WE:) 99/09023 -8- R2 3 S(O) 0 0R2 R S(O) OH 0 R3 ni R 3 nI
R
5 0 (CH 2 )n4 R 5 0 I-(H)n 11 12 R2 0
OH
3 4 C R44 2 0 Z 3 R4 K 0 (CH 2 n R 5 R 2 R (0 0 0
C
R 5 HO Zi-(CH 2 n 14 In the above isomeric compounds of formulae 11 to 14 and Ic: when Z, C(R 6
)R
7
Z
2 (W)n 6
Z
3
C(R
6
)R
7 and n 4 0, the right-hand portion of the isomeric compounds represents the group 01; when Z, CH, Z 2 0, S or -(CH 2 )n 5
Z
3 =COH and n 4 2, the right-hand portion of the isomeric compounds represents the group Q 2 when Z, OH 2
Z
2
CHNHR
9
Z
3
OH
2 and n 4 0, the right-hand portion of the isomeric compounds represents the group 03; or when Z, NR 10
Z
2 0, Z 3
C(R
6
)R
7 and n 4 0, the right-hand portion of the isomeric compounds represents the group Q4.
The compounds of formula I wherein 0 is a group Q 5 may also be in the form of mixtures of the following isomeric forms 16, 17 and le: WO 99/09023 PCTIEP98/05247 -9- R, R, R R1 R R 3 S) R 3 S(O) OH R C CR RII N R N N N R, OH R, O R,2 R12 16 17
R
2 R S(O)
R
3 R SO)n O R4 O N
R
R
I
R R12 le The invention includes all those isomeric forms I1 to 14, Ic, 16, 17 and le and their mixtures I1 to 14 and Ic, and 16, 17 and le.
The invention likewise includes the salts that the compounds of formula I having azide
R
R
2 S(O) 0
OH
I V n n hydrogen, for example the compounds of formulae 13 and 16 r 3)
R
s 0 (CH,)n4
R
R~ (on o OH and R4 C N-.R and the derivatives having carboxylic acid and Rs
R
1 sulfonamide groups carboxy-substituted phenyl, alkyl-S(0) 2 NH and haloalkyl-S(O) 2
NH
groups) are able to form with bases. Those salts are, for example, alkali metal salts, e.g.
sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, attention is WO 99/09023 PrTCn/980524 WO 99/09023 DTf'AJrA7 -10drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium. Suitable salt formers are described, for example, in WO 97/41112.
Among the alkali metal and alkaline earth metal hydrides attention is drawn, for example, to sodium hydride and calcium hydride, and among the carbonates attention is drawn to the carbonates of sodium, potassium, caesium, calcium, barium, magnesium and lithium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C 1
-C
18 alkylamines, C 1
-C
4 hydroxyalkylamines and C 2
-C
4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-npropylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The salts of compounds of formula I having basic groups, especially having basic amino groups, for example alkylamino and dialkylamino groups, in the definition of R 6
R
7 or R 17 are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, WO q/n0n2 P'T/FDo/0AI 11 oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
The possibility of the presence of at least one asymmetrical carbon atom in the compounds of formula I, for example in the substituent R1, where R, is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group, or where R 1 and R 2 and/or R 3 and R 4 and R 6 and R 7 are different from one another, means that the compounds may occur in the form of optically active single isomers or in the form of racemic mixtures.
Because rotation between the benzoyl and the Q 1 to Q 6 ring systems is hindered, the compounds of formula I may also be in the form of rotational isomers (atropisomers).
In the present invention, "compounds of formula I" is to be understood as including both the pure optical antipodes and the racemates or diastereoisomers and atropisomers.
When an aliphatic C=C or C=N-O double bond (syn/anti) is present, geometric isomerism may occur. The present invention relates to those isomers also.
Preference is given to compounds of formula I wherein R 1 is Ci-C 4 alkyl, C 1
-C
4 haloalkyl, C1-C 4 alkoxy-C 1
-C
4 alkyl, C 1
-C
4 alkoxycarbonyl, cyano, cyano-C 1
-C
4 alkyl, CHO, C 1
-C
4 alkyl- ON=CH, C 2
-C
6 alkenyl, C 1
-C
4 alkoxycarbonyl-C 2
-C
6 alkenyl or a group -CH(OR 20 W is oxygen, sulfur, -C(Re) 2 or -N(R 22 each R 1 8 independently of the other is hydrogen,
C
1
-C
4 alkyl or C 1
-C
4 alkoxycarbonyl; and R 22 is hydrogen, Ci-C 4 alkyl or C 1
-C
4 alkoxycarbonyl.
Ra Also preferred are compounds of formula I wherein Q is a group O' (Q2),
SR
7 N (Q 5 or N (Q 6
R
6 and R 7 are each O N OH N O Rio 12 independently of the other C 1
-C
4 alkyl or C 1
-C
4 alkyl-S(O) 2 n 2 is 0; Re is OH, C 1
-C
4 alkoxy,
C
1
-C
4 alkylcarbonyloxy, phenylthio or Cl-C 4 alkylthio; Rio, R 11 and R 1 2 are each independently WO 99/09023 WO 9909023PCT/P0a/n05'7 -12of the others hydrogen, C 1
-C
4 alkyl or Cl-C 4 alkoxycarbonyl; R 1 3 is halogen, Cl-C 4 alkyl, C 3
-C
6 cycloalkyl, C00R 16 C0R 1 5 or cyano; R 14 is C 1
-C
4 alkyl, C 3
-C
6 alkynyl, C 3 -C6cycloalkyl or
C
3
-C
6 CYCloalkyl substituted by halogen, C 1
-C
4 alkyl, C 1
-C
4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, C 3
-C
6 haloalkynyl or phenyl; R 15 is Cl-C 4 alkyl, Cl-C 4 haloalkyl, C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 alkynyl, C 3
-C
6 haloalkynyl or phenyl; and R 16 and Y are as defined for formula 1.
Also preferred are compounds of formula I wherein 0 is a group (0 1 or
R
6
R
7 0
R
8 NH
R
6 and R 7 are each independently of the other Cj-C 4 alkyl or Cl-C 4 alkyI-S(O)1 2 n 2 is 0; R 8 is OH, Cl-C 4 alkoxy, Cl-C 4 alkylcarbonyloxy, phenylthio or Cl-C 4 alkylthio; W is oxygen or -C(RIB) 2
R
1 8 is hydrogen; n 6 is 1; and R 9 is (Cl-C 4 alkyI)- NHCO or (C 1
-C
4 alkyI) 2
NCO.
Preference is given also to compounds of formula I wherein n is 1 or 2.
The process according to the invention for the preparation of compounds of formula I 0 11 wherein R, to R 5 and n are as defined for formula 1; 0 is a group
R
6
R
7 WO 99/09023 Pr"TI/P DO Q/n A 7 -13- R8 0 8
R
6 S(02), (Q3) or R 7 Re is OH; and R 6 R, O'f N O R 8 NH I Rio
R
7
R
9 Rio, W, n 6 and Y are as defined for formula I is carried out analogously to known procedures and comprises either a) reacting a compound of formula III R1 Ri R2 S(O) 0 7V c..
x 011), RC3 R 4
R
wherein R 1 to Rs and n are as defined and X is a leaving group, e.g. halogen, in an inert organic solvent in the presence of a base with a compound of formula IV 0 I z (IV), HO Zi (CH2) (CH2) n4 wherein Z, is C(R 6
)R
7
Z
2 is (W)n 6
Z
3 is C(R 6
)R
7 and n 4 is 0 group Q 1 Z, is CH, Z 2 is oxygen, sulfur or -(CH 2 )ns- Z 3 is CH and n 4 is 2 group Q2);
Z
1 is CH 2
Z
2 is CHNHR 9
Z
3 is CH 2 and n 4 is 0 group Q3); or Zi is NRio, Z 2 is oxygen, Z 3 is C(R 6
)R
7 and n 4 is 0 group Q4), and R 6
R
7 Rg, Rio, W, n 6 and n 5 are as defined for formula I, to form a compound of formula Ic R (c) "A WO 99/09023 PCT/FEP98/O5247 -14and then isomerising that compound, for example in the presence of a base and a catalytic amount of a cyanide source; or b) reacting a compound of formula Id R1
R
2 s(o)n.
O
R
C
-OH (Id), Rs wherein R, to Rs and n are as defined, with a compound of formula IV 0 Z3 (IV), HO Z;X HO Z' (CH2 n4 wherein Z 1
Z
2
Z
3 and n 4 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula Ic R, 0 RR O)S(O) o(I
R
4 CH 2 n4 and then isomerising that compound, for example as described under Route a).
The process according to the invention for the preparation of compounds of formula I R1
R
2 0 R3. C.Q
(I)
WO 99/09023 wherein R, to Rs and n are as defined for formula I; Q is a group PCTIEP98/05247 R1 I N OH N
I
and
R
11 and R 1 2 are as defined for formula I is carried out analogously to known procedures and comprises either: a) reacting a compound of formula III (Ill), wherein R 1 to Rs and n are as defined and X is a leaving group, e.g. halogen, with a compound of formula IVa
R
12
N
HO
(IVa), wherein R 11 and R 12 are as defined, in an inert organic solvent in the presence of a base to form a compound of formula le
R,
2 R3" R4
R
12 I N
\NN
(le), and then isomerising that compound, for example in the presence of a base and a catalytic amount of a cyanide source; or b) reacting a compound of formula Id WO 99/09023 WO 9909023PCT/EP98/05247 -16- 0 11
OH
(ld), wherein R, to R 5 and n are as defined, with a compound of formula IVa R12 HO
I
(lVa), wherein Ri, and R 12 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula le
R
3 7
R
4 0 N,.
ii N (le), and then isomerising that compound as described under Route a).
The process according to the invention for the preparation of compounds of formula I
R
4 wherein R, to R 5 and n are as defined for formula 1; 0 is a group R13
(Q
6
R
13 is hydrogen, Cl-C 4 alkyl, C 1
-C
4 alkyl substituted by unsubstituted or R 1 7 -substituted phenyl, Cl -C 4 haloalkyt, C2-C 6 alkenyl, C 2
-C
6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl, C 2
-C
6 alkynyl, C 2
-C
6 alkynyl substituted by unsubstituted or R 17 -Substituted phenyl, WO 99/09023 WO 99/09023PCT/E7P98/f52d'7 -17-
C
3
-C
6 haloalkenyl, C 3
-C
6 haloalkynyl, C 3
-C
6 cycloalkyl, 0 3
-C
6 cycloalkyl substituted by halogen,
R,
5 or COOR1 6
C
1
-C
4 alkYl-S(O), 2 Cl-C 4 alkyl-S(O)1 2 substituted by unsubstituted or R 17 substituted phenyl, C 1
-C
4 aIkoxy-C 2
-C
6 aIkyl-S(O)11 2
C
2
-C
6 alkenyl-S(O)1 2
C
2
-C
6 alkenyl-S(O)11 2 substituted by unsubstituted or R 17 -substituted phenyl, C 2
-C
6 alkynyI-S(O),1 2 or C 2
-C
6 alkynyl-
S(O).
2 substituted by unsubstituted or R 1 7 -substituted phenyl; and R 14 to R 1 7 and n 2 are as defined for formula 1, is carried out analogously to known procedures and comprises either: a) converting a compound of formula V R2 S(O)n 0 R4 C-.CH2-c -11RM
R
wherein R, to R 5
R
14 and n are as defined, in the presence of a base, carbon disulfide and an alkylating reagent of formula VI
R
25 -Xl (VI), wherein R 25 is C 1
-C
4 alkyl, Cl-C 4 alkyI substituted by unsubstituted or R 1 7 -substituted phenyl, C1 -C 4 alkoxy-C 2
-C
6 alkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkenyl substituted by u nsubstituted or R17r substituted phenyl, C 2
-C
6 alkynyl or C 2
-C
6 alkynyl substituted by unsubstituted or R 17 substituted phenyl; R 1 7 is as defined for formula 1, and X, is a leaving group, e.g. halogen or sulfonate, into a compound of formula VII R4CI -CR
(VII),
SR
25
R
2 wherein R, to R 5
R
1 4
R
25 and n are as defined, then cyclising that compound with hydroxylamine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If WO 99/09023 WO 9909023PCTIEP98/05247 -18-
R
2 S(O) n
R
1 3
FR
3 11 C
NI)
wherein R, to R 5
R
1 4 and n are as defined, R 13 is R 25 S and R 25 is C 1
-C
4 alkyI, Cl-C 4 alkyl substituted by unsubstituted or R 17 -substituted phenyl, C 1
-C
4 alkoXY-C 2
-C
6 alkyI, C 2
-C
6 alkenyl,
C
2
-C
6 alkenyl substituted by unsubstituted or R 1 7 -substituted phenyl, C 2
-C
6 alkynyl or C 2
-C
6 alkynyl substituted by unsubstituted or R 17 -substituted phenyl, and then oxidising that compound, for example with meta-chloroperbenzoic acid (m-CPBA); or b) converting a compound of formula V R 3 11 11 R wherein R, to R 5
R
1 4 and n are as defined, with an orthoacid amnide of formula ViII R260 C N(R)2 Vl)
R
26 0
R
13 wherein R 13 is hydrogen, Cl-C 4 alkyl, Cl-C 4 alkyl substituted by unsubstituted or R 17 substituted phenyl, C 1
-C
4 haloalkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkenyl substituted by unsubstituted or R 1 7 -Substituted phenyl, C 2
-C
6 alkynyl, C 2
-C
6 alkynyl substituted by unsubstituted or R 17 substituted phenyl, C 3
-C
6 haloalkenyl, C 3
-C
6 haloalkynyl, C 3
-C
6 cycloalkyl or 0 3
-C
6 cycloalkyl substituted by halogen, R 15 or C00R 16
R
15 to R 1 7 are as defined for formula I; and R 26 and
R
27 are each independently of the other Cl-C 4 alkyl, into a compound of formula IX
R
2 S(O)n a 0
R
3 11 11
R
5
R
13 2 0) 2 WO 99/09023 PCT/EP98/0f5247 -19wherein R 1 to Rs, R 1 3
R
14 n and R 27 are as defined, and then cyclising that compound in the presence of hydroxylamine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If
R,
R1 R2 S(0) n O R13
R,
5 R C f R14 he process according to the invention for the preparation of compounds of formula Id R O OH (Id)
RS
wherein Ri, R3 to Rs and n are as defined for formula I and R2 is C-C is carried out analogously to known procedures and comprises either: a) etherifying a compound of formula XX OH O C'OR28 (XX),
R,
wherein Rs is as defined for formula I and R28 is Cl-C4alkyl, with a compound of formula XXV
R
3 Ri C=C-OH---Hal
(XXV),
wherein R 1
R
3 and R 4 are as defined for formula I and Hal is halogen, to form a compound of formula XXI WO 99/09023 PCT/EP98/05247
SCH
2 O 0 RI 11 C, OR 28
(XXI),
R
wherein R 1
R
3 to R 5 and R 28 are as defined, subjecting that compound to a Claisen rearrangement and then acylating the resulting compound of formula XXII H 2
C
OH 0 R3C OR 28
(XXII)
with a compound of formula XXVI
S
Hal-C-N(C -C 4 akyl) 2
(XV)
wherein Hal is chlorine, bromine or iodine, to yield a compound of formula XXIII N(C 1 -C 4 alky 1) 2 H 2 C RI
S
O 0 11 C OR 28 (XXIII), R which is subjected to a rearrangement and yields a compound of formula XXIV N(C 1 -C 4 alky 1) 2 H 2 C
R
1 S 0
R
3 (XXIV),
R
4 OR 28 then hydrolysing and cyclising that compound to form a compound of formula Id WO 99/09023 PCT/EP98/05247 -21 (Id), wherein R 1 and R 3 to Rs are as defined, R 2 is CH 3 and n is 0, and then oxidising that compound (n is 1 or or b) first brominating a compound of formula XX
(XX),
wherein R 5 and R 28 are as defined, to yield a compound of formula XXb
OR
28 (XXb), subjecting that compound to a coupling reaction in the presence of a catalyst and an organometal reagent of formula XXVb Ri R
CH
2 =C-C-Sn(R 29 3
I
R4 (XXVb), wherein R 1
R
3 and R 4 are as defined and R 2 9 is C 1
-C
4 alkyl, to yield a compound of formula XXII
'OR
2
(XXII),
wherein RI, R 3 to R 5 and R 28 are as defined, and reacting that compound further analogously to the method described under Route a) to form a compound of formula Id.
WO 99/09023 PCT/EP98/05247 -22- The process according to the invention for the preparation of compounds of formula Id
RI
R2 S(O) 0 aR C OH (Id) wherein R 1
R
3 to Rs and n are as defined for formula I and R 2 is CH 3 is carried out analogously to known procedures and comprises reacting a compound of formula XXa
OR
28 (XXa), wherein Rs is as defined and R 28 is CI-C 4 alkyl, with a compound of formula XXVa R3 R1 C=C--CH-SH (XXVa), R4 wherein R 1
R
3 and R 4 are as defined, to yield a compound of formula XXIa
R
3 R4-. CH 2 SS O R I I R OR 28 (XXIa), Rs subjecting that compound to a Claisen rearrangment to yield a compound of formula XXIIa
H
2 C, ,R,
OR
28 (XXIIa), which is then hydrolysed and cyclised to form a compound of formula Id WO 99/09023 PCT/EP98/05247 -23- (Id), wherein R 1 and R 3 to Rs are as defined, R 2 is CH 3 and n is 0, and then oxidising that compound (n is 1 or 2).
The process according to the invention for the preparation of compounds of formula I Q (I)
R
wherein R 1 to Rs and n are as defined for formula I and Q is halogen is carried out analogously to known procedures and comprises treating a compound of formula Id
COH
(Id), wherein R 1 to Rs and n are as defined, with a halogenating agent.
The preparation of the compounds of formula I is illustrated in more detail in the following Reaction Schemes 1 to 6.
WO 99/09023 WO 9909023PCT/EP98/05247 24 Reaction Scheme 1 Route a): 0 x 0 z HO Zi-..(CH2)n base e.g. (C 2
H,)
3
N,
solvent e.g. CH 3
CN,
0-110 0
OC
0 Z3 isomerisation: I base e.g. (C 2
H
5 3
N,
O Z 1
(H
2 KCN cat.
(H)n 4
IC
2 S(O)n0 0
R
3 n 1
C
R5 R'i( 2 )n4 I (R 8
OH)
Route b): 0
OH
0 HO Zi (C H 2 )n base e.g. (C 2
H,)
3 N, coupling reagent e.g. -z solvent e.g. CH 3
CN,
0-1 10 0
C
0 Z isomerisation: .3 base e.g. (C 2
H
5 3
N,
ZA\ ~KCNct -i
(CH
2 cat I-
(OH
2 n I (R 8
OH)
WO 99/09023 WO 9909023PCT/EP98/fl5247 In Reaction Scheme 1 when Z, C(R 6
)R
7
Z
2 (W)1 6
Z
3
C(R
6
)R
7 and n 4 0, the right-hand portion of the compounds of formula I represents the group Q 1 when Z, CH, Z 2 0, S or -(CH 2 )n 5
Z
3 OH and n 4 2, the right-hand portion of the compounds of formula I represents the group Q 2 when Z, CH 2
Z
2
CHNHR
9
Z
3
OH
2 and n 4 0, the right-hand portion of the compounds of formula I represents the group 0 3 or when Z, NRjo, Z 2 0, Z 3
C(R
6
)R
7 and n 4 the right-hand portion of the compounds of formula I represents the group Q 4 Reaction Scheme 2 Route a): R
R
1 2, S(0) 0
R
12
R
3 n 1
R
4 X H N base e.g. (C H )N, solvent e.g. CH 3
R
5 R1 -11 OOC Ill IVa
RR
R R R 12 2 1() 2 0 NNisomerisation:
R
3 ni 1 n 1NNbaseeg(C H N, 4 C R Kcat N R 11 cat.HO_ HO I (Q=Q 5 WO 99/09023 WO 9909023PCTIEP98/05247 26- Route b): 0 11
COH
R
12 HO N,~ base e.g. (C 2 Hi 5 3 N, coupling reagent e.g.
IJ+ Cl
CH
3 solvent, e.g. CH 3
CN,
0-11lOeC
RV
R4 isomerisation: base e.g. (C 2
H
5 3
N,
KCN cat.
R37 0O1 11
-C
N
N
HO
R
12 I(00=5) WO 99/09023 WO 9909023PCT/EP98/35247 27- Reaction Scheme 3 Route a): 0 11
OH
2
R
14
K
2 00 3
/CS
2
R
25
*X
1
VI
solvent e.g. DMF, or
KF/AI/CS
2
R
2 V1 solvent e.g. CH3CN, or NaH/CS 2
R
2 V1 solvent e.g. DMSO
R
2 S(o) n 0
R,
3
R
3
II
R, N R5 101 0% R5 R 2 SS SR 2
VII
N
2 0H -H CI, base e.g.
N aQAc/C 2 5HSO e.g. m-CPBA It (R 1 3
=R
25
S-)
R
2 0
R
5
R
14 If 3 R 2 SO- or R 25 S02-) Route b): 0 11
-C'
OH 2
R
14
R
26 0
R
26 0k
R
1 3 Vill o 0 c R 1 4 11
'C
R 1 3 N(R 27 2 NH 2 OH.- HO!, base e.g.
NaOAc/C 2
HOH
R2 S(O) 0
R
1
R
5 R1 WO 99/09023 PCT/EP98/05247 -28- For the preparation of compounds of formula I wherein Q is a group Q1 to Q4 and Re is OH, according to Reaction Scheme 1, Route the starting materials used are carboxylic acid derivatives of formula III wherein X is a leaving group, e.g. halogen, for example iodine, bromine or especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino or part of an activated ester, e.g. N=C-NH-' (formed from dicyclohexylcarbodiimide o- (DCC) and the corresponding carboxylic acid) or C -NH(CH 2 3 N(CH) (formed from o- N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid). Those starting materials are reacted in an inert organic solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, and in the presence of a base, for example an alkylamine, e.g.
triethylamine, an aromatic amine, e.g. pyridine or 4-dimethylaminopyridine (DMAP), with a dione derivative of formula IV to form isomeric enol ethers of formula Ic. The esterification takes place at temperatures of from 0°C to 110°C.
The isomerisation of the ester derivatives of formula Ic to form the dione derivatives of formula I (Re OH) can be carried out, for example, analogously to EP-A-0 369 803 in the presence of a base, for example an alkylamine, e.g. triethylamine, or a carbonate, e.g.
potassium carbonate, and a catalytic amount of a cyanide source, for example acetone cyanohydrin or potassium cyanide.
According to Reaction Scheme 1, Route the desired diones of formula I (R 8 OH) can be obtained, for example, analogously to Chem. Lett. 1975, 1045 by esterification of the carboxylic acids of formula Id with the dione derivatives of formula IV in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, in the presence of a base, for example an alkylamine, e.g. triethylamine, and a coupling agent, for example 2-chloro-l-methyl-pyridinium iodide.
The esterification is carried out, depending upon the solvent used, at temperatures of from 0°C to 110°C and yields first, as described under Route the isomeric ester of formula Ic, which can be isomerised as described under Route for example in the presence of a base and a catalytic amount of a cyanide source, to form the desired dione derivative of formula I (R 8
OH).
WO 99/09023 PTT/EP90 ICA7 29- According to Reaction Scheme 2, the compounds of formula I wherein Q is a group Qs can be obtained in a manner analogous to that described, for example, in Reaction Scheme 1 or Tetrahedron 36, 2409 (1976), either a) by esterification of a carboxylic acid derivative of formula III with the hydroxypyrazole derivative of formula IVa in an inert organic solvent and in the presence of a base, or b) by esterification of the carboxylic acid of formula Id with the hydroxypyrazole derivative of formula IVa in an inert solvent in the presence of a base and a coupling agent, and subsequent isomerisation of the intermediately formed ester of formula le, for example with the aid of a base and a catalytic amount of cyanide source.
The preparation of the compounds of formula I wherein Q is the group Q 6 can be carried out in accordance with Reaction Scheme 3 advantageously either via Route a) by reacting the P-diketone derivative of formula V, e.g. analogously to Synthesis 1991, 301; ibid. 1988, 793; or Tetrahedron 32, 3055 (1976), with carbon disulfide in the presence of a base, for example a carbonate, e.g. potassium carbonate, a metal hydride, e.g. sodium hydride, or potassium fluoride on aluminium, and an alkylating reagent of formula VI wherein X, is a leaving group, e.g. halogen, for example iodine, bromine or especially chlorine, R 2 5 sOS 2 CH3SO 2 0- or CH 3
/SO
2 O- The reaction is advantageously carried out in a solvent, for example an amide, e.g. N,N-dimethylformamide (DMF), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), or a nitrile, e.g. acetonitrile. The resulting ketene thioacetal of formula VII is cyclised with the aid of hydroxylamine hydrochloride in the presence of a base, for example sodium acetate, in a solvent, for example an alcohol, e.g. ethanol, or an ether, for example tetrahydrofuran, to form a compound of formula If wherein R 1 3 is R 25 The cyclisation reaction is advantageously carried out at temperatures of from 0°C to 100°C. If desired, the compound of formula If can be oxidised analogously to known standard procedures, e.g. with peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to form the corresponding sulfone or sulfoxide of formula If (R 13
R
25 SO- or R 25
SO
2 or can be carried out via Route by converting the p-diketone derivative of formula V analogously to J. Het.
Chem. 20, 645 (1983) with an orthoacid amide of formula VIII, for example WO 99/09023 PCT/FPO/f0l M7 dimethylformamide dimethyl acetal, into the enamine derivative of formula IX and then cyclising that derivative with the aid of hydroxylamine hydrochloride, in the presence of a base, e.g. sodium acetate, in a solvent, for example an alcohol, e.g. ethanol, to form a compound of formula If.
The preparation of the 4-benzoylisoxazole derivatives of formula I (Q=Qs) wherein R 13 is COORe, CORs, cyano, nitro or CONH 2 can also be carried out, for example, analogously to WO 96/21357 and references cited therein.
The carboxylic acids of formula Id can be prepared analogously to known procedures, e.g.
in accordance with the methods given in Reaction Schemes 4 and 5 below.
WO 99/09023 WO 9909023PCTIEP98/05247 31 Reaction Scheme 4 Route a) OH 0 11 OR 28 R 5 alkenylation: R
R
cL=c-H 2 -HaI R4 xxv claisen rearrangement
T
H
2 C R OH 0 11
R
3 R4COR2
OR
2 acylation e.g.
S
Hal-c
N(C
1
-C
4 alkyl) 2 Xxv' 1) hydrolysis 2) cyclisation
N(C
1 -c 4 alkyl), RI =S O 0 R 3 R 4 C O R 28
R
xxiII rearrangement T, solvent
N(C
1 -c 4 alkyl) 2 H cS 0 3 R4 OR 28 R
XXIV
0
~OH
Id (R 2 =CH 3 n= 0) e.g.
M-CPBA
solvent, 0-1100C
IOH
Id (R,=0H 3 n= 1 or 2) WO 99/09023 WO 9909023PCTIEP98/05247 32- Route b): bromination: Br 2 Lewis acid, solvent, 0-1 00 0
C
OR
28 XXb coupling 1 1 CH 2 C-Sn(R 29 3
R
4 XXVb solvent, 0-200 0
C
Pd[(C 6 H 5 3 p]l
XXII
Reaction Scheme Br 0 11 aromat. nucleophilic OR 28 substitution e.g.
Rj R
R
1 1 X~a R .=C-CH 2 SH, solvent, X~a R4 XXVa base, 0-200 0
C
IOR 2
B
XXIa
H
2
C,
Claisen rearrangement
T
0
OH
1) hydrolysis 2) cyclisation 1 XXIla Id (R 2 =CH 3 n=0) e.g.
rn-C PBA
OH
Id (R 2
=CH
3 n= I or2 WO 99/09023 PCT/FpOI/0l52 d7 -33- The alkenylation of the salicylic acid derivative of formula XX wherein R 28 is C 1
-C
4 alkyl in accordance with Route a) in Reaction Scheme 4 is carried out, for example, analogously to standard etherification methods by means of reaction with an allyl halide of formula XXV wherein Hal is halogen, especially chlorine, bromine or iodine, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g. acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride. The reaction temperatures are generally in the range of from 0°C to 110°C.
The subsequent Claisen rearrangement of the allyl ether of formula XXI in Reaction Scheme 4 can be carried out, for example, thermally at temperatures of from 1000C to 3000C, optionally in an inert solvent, for example an aromatic hydrocarbon, e.g. xylene.
Alternatively the thermal Claisen rearrangement can be carried out, for example, also without a solvent in a microwave oven. Such Claisen rearrangements are described, for example, in C. Ferri, "Reaktionen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff..
In accordance with Reaction Scheme 4, the resulting phenol derivative of formula XXII is then acylated, for example with a thiocarbamoyl halide of formula XXVI, e.g. N,N-dimethylthioformyl chloride, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g, acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride.
The acylation is advantageously carried out at temperatures of from 0°C to 110°C.
The rearrangement of the thiocarbamate of formula XXIII in Reaction Scheme 4 is effected, for example, thermally in an inert solvent, for example an ether, e.g. diphenyl ether, at temperatures of from 100°C to 3000C and yields the thiolcarbamate of formula XXIV. That compound is then hydrolysed and cyclised using base or acid catalysis to form a compound of formula Id wherein R 2
CH
3 and n 0. This is effected advantageously either with a metal hydroxide, e.g. sodium hydroxide, or with a mineral acid, e.g. hydrochloric acid or sulfuric acid, at temperatures of from 0°C to 110°C. Suitable solvents are, for example, water, ethers, e.g. tetrahydrofuran, halogenated hydrocarbons, e.g. dichloromethane, and aromatic hydrocarbons, e.g. toluene.
WO 99/09023 PCT/EP98/05247 -34- The resulting benzothiophene derivative of formula Id wherein R 2 is methyl and n is 0 can then be oxidised in accordance with various standard methods. Advantageously the oxidation is carried out, for example, with hydrogen peroxide in an acidic solvent, for example an organic acid, e.g. acetic acid, or with an organic peracid, for example metachloroperbenzoic acid (m-CPBA), in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene. The reaction temperatures for the oxidation are generally in the range of from 0°C to 110 C. The degree of oxidation at the sulfur atom (n 1 or 2) can be controlled by the amount of oxidising agent.
The above reaction sequence via acylation of the phenol derivative of formula XXII to form a thiocarbamate of formula XXIII, rearrangement of the latter compound to form a thiolcarbamate of formula XXIV and hydrolysis and cyclisation to form a compound of formula Id (n 0) is carried out, for example, analogously to Org. Synth. 51, 139 (1971), and the oxidation to form a compound of formula Id (n 1 or 2) is carried out, for example, as described in H. O. House, "Modern Synthetic Reactions" W. A. Benjamin, Inc., Menlo Park, California, 1972, pages 334-335 and 353-354.
The electrophilic bromination according to Route b) in Reaction Scheme 4 is carried out, for example, analogously to Chem. Communic. 1972, 214. The bromination of the salicylic acid derivative of formula XX can be effected, for example, in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, and in the presence of a Lewis acid, for example titanium halide, e.g. titanium tetrachloride, at temperatures of from 0°C to 100°C.
The subsequent coupling of the resulting bromosalicylic acid derivative of formula XXb to a trialkyltin-olefin of formula XXVb wherein R 29 is C 1
-C
4 alkyl is carried out analogously to Angew. Chem. 98, 504 (1986) in an organic solvent, for example an ether, e.g. tetrahydrofuran, an aromatic hydrocarbon, e.g. toluene, and in the presence a palladium catalyst, for example tetrakis(triphenylphosphine)palladium. The reaction temperature is advantageously from 0°C to 200°C. The coupling product of formula XXII obtained by Route b) can then, for example in a manner analogous to that described under Route be acylated, rearranged, hydrolysed and cyclised, and optionally oxidised to form a compound of formula Id.
The aromatic nucleophilic substitution of the ortho-bromobenzoic acid ester of formula XXa wherein R 28 is C 1
-C
4 alkyl in Reaction Scheme 5 can be carried out analogously to known procedures, as described, for example, in J. March, "Advanced Organic Chemistry", 4th WO 99/09023 PCT/EP98/05247 Edition, John Wiley Sons, New York, 1992, pages 641-676. Accordingly, the benzoic acid ester of formula XXa is reacted with an alkenyl sulfide of formula XXVa in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g. acetone, or a nitrile, e.g. acetonitrile, in the presence of a base, for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride, at temperatures of from 0 C to 200"C.
The subsequent Claisen rearrangement of the resulting thioallyl ether of formula XXIa in Reaction Scheme 5 can advantageously be carried out in a manner analogous to that described in J. Org. Chem. USSR 13, 2437 (1977) and under Reaction Scheme 4 for the allyl ether of formula XXI, at temperatures of from 1 00C to 300°C. The subsequent hydrolysis and cyclisation of the thiophenol of formula XXlla and the optional oxidation of the resulting dihydrobenzo[b]thiophene derivative of formula Id are advantageously likewise carried out as already described under Reaction Scheme 4.
The activated carboxylic acid derivatives of formulae III and I in Reaction Schemes 1 and 2 (Route wherein X is a leaving group, for example halogen, e.g. bromine, iodine or especially chlorine, can be prepared according to known standard procedures as described, for example, by C. Ferri in "Reaktionen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff., such as, for example, in accordance with Reaction Scheme 6 below.
Reaction Scheme 6 R1 III or I In accordance with Reaction Scheme 6, the preparation of the compounds of formula III (X leaving group) and I (X halogen) is carried out, for example, advantageously by the use of a halogenating agent, for example a thionyl halide, e.g. thionyl chloride or bromide; a phosphorus halide or phosphorus oxyhalide, e.g. phosphorus pentachloride or phosphorus phosphorus haide or phosphorus oxyhalide, e.g. phosphorus pentachloride or phosphorus WO 99/09023 PCTIEP98/05247 -36.
oxychloride, or phosphorus pentabromide or phosphoryl bromide; or an oxalyl halide, e.g.
oxalyl chloride, or by the use of a reagent for forming activated esters, for example N,N'dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X. Where the compound of formula X is a halogenating agent, the group X is, for example, a leaving group, for example halogen, e.g. fluorine, bromine or iodine or especially chlorine, and W 1 is, for example, PC12, SOCI, SOBr or CICOCO.
The operation is optionally carried out in an inert organic solvent, for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the reaction mixture, preferably at from 40 to 150°C, and in the presence of a catalytic amount of N,N-dimethylformamide. Such reactions are known and various variations thereof in respect of the leaving group X are described in the literature.
The compounds of formulae V, VII and IX (Reaction Scheme 3) are novel. They are important intermediates for the synthesis of the compounds of formula If. The invention therefore relates also to those compounds.
The compounds of formula IV (Reaction Scheme 1) wherein Z 1
C(R
6
)R
7
Z
2 (W)n6, Z 3
C(R
6
)R
7 and n 4 0 are known and can be prepared in a manner analogous to that described, for example, in US-A-5 006 150, WO 97/08164, DE-OS-3 818 958 and DE-OS-3 902 818.
The compounds of formula IV (Reaction Scheme 1) wherein Z 1 CH, Z 2 O, S or -(CH 2 Z3 CH and n 4 2 are known and can be prepared in a manner analogous to that described, for example, in EP-A-0 338 992.
The compounds of formula IV (Reaction Scheme 1) wherein Z, CH 2
Z
2
CHNHR
9
Z
3
CH
2 and n 4 0 are known and can be prepared in a manner analogous to that described, for example, in EP-A-0 278 907.
The compounds of formula IV (Reaction Scheme 1) wherein Z, NRio, Z 2 0, Z 3
C(R
6
)R
7 and n 4 0 are known and can be prepared in a manner analogous to that described, for example, in WO 96/26192 and US-A-5 336 662.
WO 99/09023 PCT/EPO9/01247 -37- The compounds of formula IVa (Reaction Scheme 2) wherein R 11 and R 1 2 are as defined for formula I are known and can be prepared in a manner analogous to that described, for example, in WO 96/26206 and WO 97/08164.
The compounds of formula V in Reaction Scheme 3 can be obtained in accordance with standard procedures, for example from the corresponding esters of formula XXVII R COR 2
(XXVII),
R
wherein R 1 to Rs and n are as defined for formula I and R 28 is C 1
-C
4 alkyl, for example via Claisen condensation, or from the compounds of formula III by reaction with a ketocarboxylic acid salt of formula XXVIII COO' M
CH
2
(XXVIII),
COR
1 4 wherein R 14 is as defined for formula I and M+ is an alkali metal ion (see, for example, WO 96/26192, EP-A-0 496 631).
The salicylic acid derivatives of formula XX (Reaction Scheme 4) are either known (some of them being commercially available, for example when Rs is amino (4-aminosalicylic acid)) or can readily be prepared by standard procedures, for example starting from 4-aminosalicylic acid via diazotisation, Sandmeyer reaction and aromatic, nucleophilic substitution (see e.g.
J. March, "Advanced Organic Chemistry", 4th Edition, John Wiley Sons, New York, 1992, pages 641-676) or Heck reaction of the resulting halide.
The benzoic acid derivatives of formula XXa (Reaction Scheme 5) are either known or can readily be obtained by bromination of the corresponding benzoic acid derivatives (see Reaction Scheme 4, Route The reagents of formulae VI, VIII, X, XXV, XXVa, XXVb and XXVI used in Reaction Schemes 3 to 6 are either known or can be prepared analogously to disclosed procedures.
WO 99/09023 PCT/EP98/05247 -38- For the preparation of all other compounds of formula I functionalised in accordance with the definitions of R 1 and R 2 (2-position of the dihydrobenzo[b]thiophene ring), a large number of known standard procedures are available, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. EP-A-0 796 856).
For the preparation of all other compounds of formula I functionalised in accordance with the definition of R 8 wherein Q is a group Q1 to Q 4 a large number of known standard procedures are available, for example alkylation, acylation and treatment with a sulfur reagent P 2
S
5 or Lawesson), the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. WO 97/08164 and DE-OS-3 902 818).
All other compounds within the scope of formula I can readily be prepared, taking into account the chemical properties of the dihydrobenzo[b]thiophene or Q moiety in relation to the structure of the dihydrobenzo[b]thiophene or Q rings, in a manner analogous to that described in Preparation Examples P1 to P11 or, for example, to that described in the patent specifications indicated.
The end products of formula I can in conventional manner be isolated by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluant. The sequence in which it is advantageous to carry out certain reactions in order to avoid possible secondary reactions will also be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers. The isomers can be separated according to methods known per se.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to WO 99/09023 PrT/1VDQ /n A 39 mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending on the nature of the compound of formula I to be formulated, suitable surfaceactive compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
In addition, the surfactants conventionally employed in formulation technology, which are described in, inter alia, "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, "Tensid-Taschenbuch", Carl Hanser Verlag, MunichNVienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 by weight, especially from 0.1 to 95 by weight, of herbicide, from 1 to 99.9 by weight, especially from 5 to 99.8 WO 99/09023 PCT/EP98/05247 by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 by weight, especially from 0.1 to 25 by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I can be used successfully either in the form of a mixture of the isomeric forms 11 to 14 and Ic (Q is a group Q 1 to Q 4 and R 8 is OH) or 16, 17 and le (Q is a group Qs) or in the form of pure isomeric forms I1 to 14 or Ic, or e1, 17 or le, generally on plants or the locus thereof, at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate but do not limit the invention.
WO 99/09023 -41 Preparation Examples: Example P1: 2-Allvloxy-4-chlorobenzoic acid methyl ester PCT/EP98/05247 g (0.36 mol) of potassium carbonate are added, with stirring, to 56 g (0.3 mol) of 4chlorosalicylic acid methyl ester in 200 ml of dimethyl sulfoxide. When the slightly exothermic reaction has subsided, 40 g (0.33 mol) of allyl bromide are added dropwise at 250C. The reaction mixture is stirred at 220C for 16 hours, poured into water and extracted by shaking with diethyl ether. The combined ether phases are washed with water, dried with sodium sulfate and concentrated by evaporation. The residue is recrystallised from a small amount of hexane. 62 g (91.2 of theory) of the desired product having a melting point of 61-620C are obtained.
Example P2: 2-Hydroxy-3-(3-propenvl)-4-chlorobenzoic acid methyl ester 97.9 g (0.432 mol) of 2-allyloxy-4-chlorobenzoic acid methyl ester (Example P1) are melted in a round-bottomed flask and irradiated in a microwave oven at 500 watts for 5 minutes. An exothermic reaction takes place. The reaction mixture is allowed to cool and yields 97.1 g (99.1 of theory) of the desired product having a melting point of 32-35'C.
WO 99/09023 PCT/PP9/n5d7 42 Example P3: 2-Oxy-(N.N-dimethvl-thiocarbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester
CH
3
'N-CH
S j- 0 s= 0 0 I I C"OCH3
CI
97 g (0.428 mol) of 2-hydroxy-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P2) and 69 g (0.5 mol) of potassium carbonate are stirred in 400 ml of dimethylformamide for 1/2 hour. A solution of 55.6 g (0.45 mol) of N,N-dimethyl-thiocarbamoyl chloride in 200 ml of dimethylformamide is then added dropwise thereto. The reaction mixture is stirred at 220C for 22 hours. To complete the reaction, 11 g (0.09 mol) of N,Ndimethyl-thiocarbamoyl chloride and 15 g (0.11 mol) of potassium carbonate are added.
After a further 24 hours at 22°C, the reaction mixture is poured into an ice-water mixture and extracted by shaking with ethyl acetate. The ethyl acetate phase is washed with water, then with brine, dried over sodium sulfate and concentrated by evaporation. The residue is chromatographed on silica gel (eluant: ethyl acetate/hexane yielding 114.5 g (85 of theory) of the desired product in the form of an oil.
Example P4: 2-Mercapto-(N,N-dimethyl-carbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester
CH
3 N-CH3 S o ^C-OCH3 Cl 114.5 g (0.365 mol) of 2-oxy-(N,N-dimethyl-thiocarbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P3) dissolved in 150 ml of diphenyl ether are added dropwise, in the course of 5 hours, to 100 ml of diphenyl ether at 205-210'C. The temperature is maintained at 2050C for a further 1 1/2 hours. After cooling, the diphenyl ether is distilled WO 99/09023 PCT/EPQ/na547 -43off at a pressure of 0.04 mbar. The residue is chromatographed on silica gel (eluant: ethyl acetate/hexane yielding 90.2 g (78.8 of theory) of the desired product in the form of an oil.
Example P5: 4-Chloro-2-methvl-2.3-dihydro-benzo[b]thiophene-7-carboxylic acid
CH
3
S
COOH (Comp. No. 1.001)
CI
90.2 g (0.287 mol) of 2-mercapto-(N,N-dimethylcarbamoyl)-3-(3-propenyl)-4-chlorobenzoic acid methyl ester (Example P4) is heated under reflux for 20 hours in 150 ml of acetic acid and 200 ml of concentrated hydrochloric acid. The reaction mixture is concentrated in a rotary evaporator and the residue is stirred with water and cooled. The solid substance is filtered off and drying is carried out in vacuo at 60'C, yielding 66 g (100 of theory) of the expected product having a melting point of 215-218'C.
Example P6: 4-Chloro-2-methvl-1,1-dioxo-2,3-dihvdro-benzo[b]thiophene-7-carboxylic acid
CH
3 0
/I
S=0 COOH (Comp. No. 1.027) Cl g (0.0875 mol) of 4-chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P5) are suspended in 150 ml of acetic acid and heated to 70°C. 24 ml of approx.
hydrogen peroxide are then added dropwise thereto. The reaction is exothermic. At 0 C, the heating bath is removed and the dropwise addition is continued in such a manner that the temperature remains at 80'C. The reaction mixture is then maintained at 70-75 0
C
for 1 hour. The reaction mixture is then concentrated using a rotary evaporator until crystals are deposited. Water is then added; the mixture is cooled and the precipitated crystals are filtered off. After drying in vacuo at 60'C, 17 g (74 of theory) of the desired product having a melting point of 223-225'C are obtained.
WO 99/09023 PCT/EP98/05247 -44- Example P7: 4-Chloro-2-methyl-1,1-dioxo-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid chloride
CH
3 0 Cl 16.7 g (0.06 mol) of 4-chloro-2-methyl-1,1-dioxo-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P6) are heated to 90 0 C in 100 ml of toluene. 3 drops of dimethylformamide are added and then 9.5 g (0.08 mol) of thionyl chloride are added dropwise thereto in the course of 20 minutes, a clear solution being obtained. The reaction mixture is heated at 100°C for 3 hours and then concentrated by evaporation using a rotary evaporator, yielding 17 g of the desired product in the form of a solid substance.
Example P8: (2.3-Dihvdro-4-chloro-2-methylbenzofb1thiophen-7-yl)(2-hydrox-6-oxo-1 cyclohexen-1 -l)methanone S.S-dioxide O
CH
3 O O0 (Comp. No. 2.027) OH CI g (0.094 mol) of triethylamine are added at 50C to 3.6 g (0.0314 mol) of 1,3cyclohexanedione in 80 ml of methylene chloride. At 5'C, 8.8 g (0.0314 mol) of 4-chloro-2methyl-1,1-dioxo-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid chloride (Example P7) in ml of methylene chloride are added dropwise. After 1 hour at 220C, 0.5 ml of acetone cyanohydrin are added. After 5 1/2 hours, the reaction mixture is extracted by shaking with 2N hydrochloric acid. The methylene chloride phase is separated off, dried with sodium sulfate and concentrated by evaporation, and the residue is dissolved in a small amount of warm acetone. On being left to stand the product crystallises out. After filtration, 5.5 g of theory) of the expected product having a melting point of 170-1720C are obtained.
WO 99/09023 PCT/EP98/05247 Example P9: 4-Chloro-2-methyl-2,3-dihydro-benzo[blthiophene-7-carboxylic acid chloride
CH
3
S
COCI
CI
45.7 g (0.2 mol) of 4-chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid (Example P5), 23.8 g (0.22 mol) of thionyl chloride and a few drops of dimethylformamide are heated in 300 ml of toluene at 100°C for 18 hours. Concentration by evaporation yields the desired product, which can be used further without purification.
Example P10: (2,3-Dihvdro-4-chloro-2-methvlbenzo[blthiophen-7-yl)(1,3-dimethyl-5hydroxy-1 H-pyrazol-4-vl)methanone N CH 3 CH3
N
O O OH (Comp. No. 10.001)
CH,
CI
2.3 g (0.02 mol) of 1,3-dimethylpyrazolone-5 and 2.2 g (0.022 mol) of triethylamine are suspended in 80 ml of ethyl acetate and cooled to 50C, and then 5.0 g (0.02 mol) of 4chloro-2-methyl-2,3-dihydro-benzo[b]thiophene-7-carboxylic acid chloride (Example P9) in ml of ethyl acetate are added. The reaction mixture is stirred at 22 0 C for 18 hours, the salts are filtered off and concentration by evaporation is carried out using a rotary evaporator. The residue is dissolved in 70 ml of dimethylformamide, and 2.2 g (0.022 mol) of triethylamine and 0.2 g of potassium cyanide are added. The reaction mixture is left to stand at 220C for 18 hours and the dimethylformamide is evaporated off. Ethyl acetate and ml of glacial acetic acid are added to the residue and the resulting solution is extracted by shaking with water. The organic phase is separated off, dried with sodium sulfate and concentrated by evaporation. Trituration with diethyl ether yields the desired product having a melting point of 191-193oC.
WO 99/09023 PCT/EP98/05247 -46- Example P11: (2,3-Dihvdro-4-chloro-2-methylbenzorb1thiophen-7-yl)(1,3-dimethyl-5hydroxy-1 H-pyrazol-4-vl)methanone S,S-dioxide N CH CH i-N
O
OH O (Comp. No. 10.027)
CH
3
CI
g (0.0115 mol) of 3-chloroperbenzoic acid dissolved in 30 ml of methylene chloride are added to 1.7 g (0.0052 mol) of (2,3-dihydro-4-chloro-2-methylbenzo[b]thiophen-7-yl)(1,3dimethyl-5-hydroxy-1 H-pyrazol-4-yl)methanone (Example P10) in 40 ml of methylene chloride. The reaction mixture is left to stand at 22°C for 2 days and is extracted by shaking with saturated, aqueous sodium hydrogen carbonate solution. The hydrogen carbonate phase is acidified with concentrated hydrochloric acid and the resulting precipitate is filtered off. The solid substance so obtained is triturated with diethyl ether and isolated by filtration, yielding 1.6 g of the desired product having a melting point of 230-233'C.
In analogous manner, and in accordance with methods such as those described in the general Reaction Schemes 1 to 5 and the references indicated therein, it is also possible to prepare the preferred compounds listed in the following Tables.
Table 1: A preferred group of compounds of formula I corresponds to general formula Id R1
R
2
O
R wherein the meanings of the corresponding substituents R 4
OH
Rs
R
1 to Rs and n are given in Table A, so that 819 specific compounds of formula Id are disclosed.
WO 99/09023 PCTIEP98/05247 -47- Table 2: A further preferred group of compounds of formula I corresponds to general R1 2 S(O) 0 0 formula Ig R- wherein the meanings of the corresponding R4
R
5
OH
substituents R 1 to Rs and n are given in Table A, so that 819 specific compounds of formula Ig are disclosed.
Table 3: A further preferred group of compounds of formula I corresponds to general formula Ih wherein the meanings of the corresponding substituents R 1 to R 5 and n are given in Table A, so that 819 specific compounds of formula Ih are disclosed.
Table 4: A further preferred group of compounds of formula I corresponds to general formula li wherein the meanings of the corresponding substituents R 1 to Rs and n are given in Table A, so that 819 specific compounds of formula li are disclosed.
Table 5: A further preferred group of compounds of formula I corresponds to general R2 -S(0)nO O formula Ij R 3 R4 Rs OH NH H, wherein the meanings of the corresponding substituents R 1 to Rs and n are given in Table A, so that 819 specific compounds of formula Ij are disclosed.
WO 99/09023 PCT/EP98/05247 -48 Table 6: A further preferred group of compounds of formula I corresponds to general formula lk 0C3
OH
3 wherein the meanings of the corresponding substituents R, to R 5 and n are given in Table A, so that 819 specific compounds of formula 1k are disclosed.
Table A Compd. R 2 No.
.001 H .002 H .003 H .004 H .005 H .006 H .007 H .008 H .009 H .010 H .011 H .012 H .013 H .014 H .015 H .016 H .017 H .018 H .019 H .020 H
R
3
R
4
R
5 n
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3 01
F
Br
SO
2 Me SMe
SO
2 NMe 2
OF
3
OH
3 OH(0H 3 2 N0 2 00H 3
OCF
2
CF
3
ON
01
F
Br
SO
2 Me SMe
SO
2 NMe 2
OF
3 WO 99/09023 WO 9909023PCT/EP98/05247 49
R
3
R
4 R5 n Compd. R 2 .022 .023 .024 .025 .026 .027 .028 .029 .030 .031 .032 .033 .034 .035 .036 .037 .038 .039 .040 .041 .042 .043 .044 .045 .046 .047 .048 .049 .050 .051 -I OH3 -i CH 3 -I OH 3 -I OH3 -I OH 3 -I OH 3 -I OH 3 -I OH 3 -I OH 3 -I OH 3 -I OH 3 H OH 3 H OH 3 H OH 3 H OH 3 H OH 3 H OH 3 H OH 3 H OH 3 H OH 3
CH
2 H OH 3
OH
2 H CH 3
CH
2 H 0H 3 0H 2 H 0H 3 0H 2 H CH 3 0H 2 H 0H 3 0H 2 H 0H 3 0H 2 H CH 3 0H 2 H 0H 3 0H 2 H 0H 3 0H 2 H CH 3
CH
2 H OH 3 1 H OH(0H 3 2 1 H NO 2 1 H 00H 3 1 H 00F 2 0F 3 1 H ON 1 H 01 2 H F 2 H Br 2 H SO 2 Me 2 H SMe 2 H SO 2 N Me 2 2 H OF 3 2 H OH 3 2 H OH(CH 3 2 2 H NO 2 2 H 00H 3 2 H 00F 2 0F 3 2 H ON 2 H 01 0 H F 0 H Br 0 H SO 2 Me 0 H SMe 0 H SO 2 NMe 2 0 H OF 3 0 H OH 3 0 H OH(0H 3 2 0 H NO 2 0 H OCH 3 0 H 00F 2
CF
3 0 WO 99/09023 WO 9909023PCT/EP98/05247 Compd. R 2 No.
.052 H .053 H .054 H .055 H .056 H .057 H .058 H .059 H .060 H .061 H .062 H .063 H .064 H .065 H .066 H .067 H .068 H .069 H .070 H .071 H .072 H .073 H .074 H .075 H .076 H .077 H .078 H .079 CH 3 .080 CH 3 .081 CH 3 .082 CH 3
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
R
3
R
4
R
5 n H H CN 0 H H CI H H F 1 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H CF 3 1 H H CH 3 1 H H CH(CH 3 2 1 H H NO 2 1 H H OCH 3 1 H H OCF 2
CF
3 1 H H CN 1 H H CI 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H CF 3 2 H H CH 3 2 H H CH(CH 3 2 2 H H NO 2 2 H H OCH 3 2 H H OCF 2
CF
3 2 H H CN 2 H H CI 0 H H F 0 H H Br 0 H H SO 2 Me 0 WO 99/09023 WO 9909023PCT/EP98/05247 -51 Compd. R 2 No.
.083 CH 3 .084 OH 3 .085 OH 3 .086 OH 3 .087 CH 3 .088 OH 3 .089 CH 3 .090 OH 3 .091 OH 3 .092 OH 3 .093 OH 3 .094 OH 3 .095 OH 3 .096 OH 3 .097 OH 3 .098 OH 3 .099 OH 3 .100 OH 3 .101 OH 3 .102 OH 3 .103 OH 3 .104 OH 3 .105 OH 3 .106 OH 3 .107 OH 3 .108 OH 3 .109 OH 3 .110 OH 3 .111 OH 3 .112 OH 3 .113 OH 3
R,
0H 3 0H 2 0H 3
CH
2 0H 3 0H 2 0H 3
CH
2
OH
3
CH
2
CH
3
CH
2 0H 3 0H 2 0H 3 0H 2 0H 3
CH
2
CH
3
CH
2 0H 3 0H 2
CH
3
CH
2 0H 3 0H 2 0H 3
CH
2
CH
3
CH
2
CH
3 0H 2 0H 3
CH
2
CH
3 0H 2
CH
3
CH
2 0H 3 0H 2
CH
3 0H 2 0H 3
CH
2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2 0H 3
CH
2
CH
3
OH
2 0H 3 0H 2
CH
3
CH
2
R
3
R
4
R
5 n H H SMe 0 H H SO 2 NMe 2 0 H H CF 3 0 H H OH 3 0 H H OH(CH 3 2 0 H H NO 2 0 H H OCH 3 0 H H 00F 2 0F 3 0 H H CN 0 H H Ci 1 H H F 1 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H CF 3 1 H H CH 3 1 H H CH(CH 3 2 1 H H NO 2 1 H H OCH 3 1 H H 00F 2 0F 3 1 H H CN 1 H H CI 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H CF 3 2 H H CH 3 2 H H OH(CH 3 2 2 WO 99/09023 PCT/EP98/05247 -52- Compd. R 2 No.
.114 CH 3 .115 CH 3 .116 CH 3 .117 CH 3 .118 H .119 H .120 H .121 H .122 H .123 H .124 H .125 H .126 H .127 H .128 H .129 H .130 H .131 H .132 H .133 H .134 H .135 H .136 H .137 H .138 H .139 H .140 H .141 H .142 H .143 H .144 H
R
3
R
4 Rs n
CH
3
CH
2 CHaCH 2 CHaCH 2
CH
3
CH
2
CH
3
CH
3
CH
3
CH
3
CH
3 CHa
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3 H H NO 2 2 H H OCH 3 2 H H OCF 2
CF
3 2 H H CN 2 H CH 3 Cl 0 H CH 3 F 0 H CH 3 Br 0 H CH 3
SO
2 Me 0 H CH 3 SMe 0 H CH 3
SO
2 NMe 2 0 H CH 3
CF
3 0 H CH 3
CH
3 0 H CH 3
CH(CH
3 2 0 H CH 3
NO
2 0 H CH 3
OCH
3 0 H CH 3
OCF
2
CF
3 0 H CH 3 CN 0 H CH 3 Cl 1 H CH 3 F 1 H CH 3 Br 1 H CH 3
SO
2 Me 1 H CH 3 SMe 1 H CH 3
SO
2 NMe 2 1 H CH 3
CF
3 1 H CH 3
CH
3 1 H CH 3
CH(CH
3 2 1 H CH 3
NO
2 1 H CH 3
OCH
3 1 H CH 3
OCF
2
CF
3 1 H CH 3 CN 1 H CH 3 Cl 2 WO 99/09023-- Oompd. R 2
RR
3
R
4
R
5 n No.
.145 H CH 3 H CH- 3 F 2 .146 H OH 3 H CH 3 Br 2 .147 H OH 3 H OH 3
SO
2 Me 2 .148 H OH 3 H OH 3 SMe 2 .149 H OH 3 H OH 3
SO
2 NMe 2 2 .150 H OH 3 H OH 3
OF
3 2 .151 H OH 3 H 0H3 OH 3 2 .152 H CH 3 H OH 3
OH(CH
3 2 2 .153 H OH 3 H OH 3
NO
2 2 .154 H OH 3 H OH 3 00H 3 2 .155 H OH 3 H OH 3 00F 2 0F 3 2 .156 H CH 3
CH
2 H OH 3 ON 2 .157 H CH 3
CH
2 H OH 3 01 0 .158 H CH 3
CH
2 H OH 3 F 0 .159 H CH 3
CH
2 H OH 3 Br 0 .160 H CH 3
CH
2 H OH 3
SO
2 Me 0 .161 H CH 3
CH
2 H OH 3 SMe 0 .162 H 0H 3
CH
2 H OH 3
SO
2 NMe 2 0 .163 H CH 3 0H 2 H OH 3
OF
3 0 .164 H CH 3
CH
2 H OH 3
OH
3 0 .165 H CH 3
CH
2 H OH 3
CH(CH
3 2 0 .166 H CH 3
CH
2 H OH 3
NO
2 0 .167 H CH 3
CH
2 H OH 3 00H 3 0 .168 H CH 3
CH
2 H OH 3 00F 2 0F 3 0 .169 H 0H 3
CH
2 H OH 3 ON 0 .170 H CH 3
CH
2 H OH 3 cI 1 .171 H 0H 3 0H 2 H OH 3 F 1 .172 H CH 3
CH
2 H OH 3 Br 1 .173 H CH 3
CH
2 H OH 3
SO
2 Me 1 .174 H 0H 3 0H 2 H OH 3 SMe 1 .175 H 0H 3 0H 2 H OH 3
SO
2 NMe 2 1 PCT/EP98/05247 WO 99/09023-- Compd. R 2 R, R 3
R
4 Rs No.
.176 H 0H 3
CH
2 H OH 3
OF
3 1 .177 H CH 3
CH
2 H CH 3
OH
3 1 .178 H CH 3
OH
2 H OH 3 CH(0H 3 2 1 .179 H CH 3
CH
2 H OH 3
NO
2 1 .180 H CH 3
CH
2 H CH 3
OOH
3 1 .181 H CH 3
CH
2 H CH 3
OCF
2
OF
3 1 .182 H CH 3
OH
2 H OH 3 CN 1 .183 H CH 3
CH
2 H OH 3 CI 2 .184 H CH 3
CH
2 H OH 3 F 2 .185 H CH 3
CH
2 H OH 3 Br 2 .186 H CH 3
OH
2 H OH 3
SO
2 Me 2 .187 H CH 3
OH
2 H OH 3 SMe 2 .188 H CH 3 0H 2 H OH 3
SO
2 NMe 2 2 .189 H CH 3
CH
2 H OH 3
OF
3 2 .190 H OH 3
OH
2 H OH 3
OH
3 2 .191 H CH 3
OH
2 H OH 3 OH(0H 3 2 2 .192 H CH 3 0H 2 H OH 3
NO
2 2 .193 H 0H 3
CH
2 H OH 3 00H 3 2 .194 H 0H 3 0H 2 H OH 3 00F 2 0F 3 2 .195 H CH 3
OH
2 H OH 3 ON 2 .196 OH 3
CH
3
OH
2 H OH 3 01 0 .197 OH 3
CH
3 0H 2 H OH 3 F 0 .198 OH 3 0H 3 0H 2 H OH 3 Br 0 .199 OH 3
CH
3 0H 2 H OH 3
SO
2 Me 0 .200 OH 3 0H 3 0H 2 H OH 3 SMe 0 .201 OH 3
CH
3 0H 2 H OH 3
SO
2 NMe 2 0 .202 OH 3
CH
3 0H 2 H OH 3
OF
3 0 .203 OH 3 0H 3 0H 2 H OH 3
OH
3 0 .204 OH 3 0H 3 0H 2 H OH 3 OH(0H 3 2 0 .205 OH 3
CH
3
CH
2 H OH 3
NO
2 0 .206 OH 3
CH
3 0H 2 H OH 3
OCH
3 0 PCT/EP98/05247 WO 99/09023 WO 9909023PCT/EP98/05247 55 Compd. R 2 No.
.207 OH 3 .208 OH 3 .209 OH 3 .210 OH 3 .211 OH 3 .212 OH 3 .213 OH 3 .214 OH 3 .215 OH 3 .216 OH 3 .217 OH 3 .218 OH 3 .219 OH 3 .220 OH 3 .221 OH 3 .222 OH 3 .223 OH 3 .224 OH 3 .225 OH 3 .226 OH 3 .227 OH 3 .228 OH 3 .229 OH 3 .230 OH 3 .231 OH 3 .232 OH 3 .233 OH 3 .234 OH 3 .235 OH 3 .236 OH 3 .237 OH 3
R
3
R
4 A5 n 0H 3
CH
2 0H 3 0H 2
CH
3 0H 2 0H 3 0H 2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2 0H 3 0H 2
CH
3
CH
2
CH
3
CH
2 0H 3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
OH
3
CH
2 0H 3 0H 2 0H 3 0H 2
CH
3
CH
2 0H 3 0H 2 0H 3
CH
2
CH
3 0H 2
CH
3 0H 2
CH
3 0H 2 0H 3
CH
2
CH
3
CH
2
OH
3
CH
2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2 H OH 3 00F 2 0F 3 0 H OH 3 ON 0 H OH 3 01 1 H OH 3 F 1 H OH 3 Br 1 H OH 3
SO
2 Me 1 H OH 3 SMe 1 H OH 3
SO
2 NMe 2 1 H OH 3
OF
3 1 H OH 3
OH
3 1 H OH 3
OH(CH
3 2 1 H OH 3
NO
2 1 H OH 3 00H 3 1 H OH 3 00F 2 0F 3 1 H OH 3 ON 1 H OH 3 cI 2 H OH 3 F 2 H OH 3 Br 2 H OH 3
SO
2 Me 2 H OH 3 SMe 2 H OH 3
SO
2 NMe 2 2 H OH 3
CF
3 2 H OH 3
OH
3 2 H OH 3
OH(OH
3 2 2 H OH 3
NO
2 2 H OH 3
OOH
3 2 H OH 3 00F 2 0F 3 2 H OH 3 ON 2
OH
3
OH
3 CI 0 0H 3 0CH 3 F 0
OH
3
OH
3 Br 0 WO 99/09023 WO 9909023PCT/EP98/05247 56 Oompd. R 2 No.
.238 CH: .239 OH .240 CH.
.241 OH .242 CH: .243 CH .244 CH .245 CH: .246 OH: .247 OH: .248 OH
R
3
R
4 Rs n 3 3 3 3 3 3 3 3 3 3 .249 .250 .251 .252 .253 .254 .255 .256 .257 .258 .259 .260 .261 .262 .263 .264 .265 .266 .267 .268
H
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
2
OH
3
OH
2
CH
3 0H 2
OH
3
CH
2
OH
3
CH
2
CH
3
OH
2
CH
3
OH
2
OH
3
CH
2
OH
3
OH
2 0H 3 0H 2
CH
3
CH
2
OH
3
CH
2
CH
3
OH
2
OH
3
CH
2
OH
3
CH
2
OH
3
CH
2
OH
3
CH
2
OH
3
CH
2
OH
3
OH
2
CH
3
CH
2
OH
3
OH
2 0H 3
CH
2
OH
3
CH
2
OH
3
CH
2
CH
3 0H 2
OH
3
CH
2 0H 3
CH
2
OH
3
CH
2 0H 3 0H 2
OH
3
CH
2
CH
3
CH
2
OH
3
OH
3
SO
2 Me 0
OH
3
OH
3 SMe 0
OH
3
OH
3
SO
2 NMe 2 0
OH
3
OH
3
OF
3 0
OH
3
OH
3
OH
3 0
OH
3
OH
3 OH(0H 3 2 0
OH
3
OH
3
NO
2 0
OH
3
OH
3
OOH
3 0
OH
3
OH
3
OOF
2
OF
3 0
OH
3
OH
3 ON 0
OH
3
OH
3 01 1 0H 3 0CH 3 F 1
OH
3
OH
3 Br 1
OH
3
OH
3
SO
2 Me 1
OH
3
OH
3 SMe 1
OH
3
OH
3
SO
2 NMe 2 1
OH
3
OH
3
OF
3 1
OH
3
OH
3
CH
3 1
OH
3
OH
3 OH(0H 3 2 1
OH
3
OH
3
NO
2 1
OH
3
OH
3
OCH
3 1
OH
3
OH
3 00F 2 0F 3 1
OH
3
OH
3 ON 1
OH
3
OH
3 01 2 0H 3 0CH 3 F 2
OH
3
OH
3 Br 2
OH
3
OH
3
SO
2 Me 2
OH
3
OH
3 SMe 2
OH
3
OH
3
SO
2 NMe 2 2
OH
3
OH
3
OF
3 2
OH
3
OH
3
OH
3 2 WO 99/09023 WO 9909023PCT/EP98/05247 .57 Compd. R 2 No.
.269 OH 3 .270 OH 3 .271 OH 3 .272 OH 3 .273 OH 3 .274 H .275 H .276 H .277 H .278 H .279 H .280 H .281 H .282 H .283 H .284 H .285 H .286 H .287 H .288 H .289 H .290 H .291 H .292 H .293 H .294 H .295 H .296 H .297 H .298 H .299 H
R
3
R
4
R
5 n
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2
OH
3
CH
2
CH
3
OH
2
OH
3
OH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH(CH
3 2 2
OH
3
CH
3 N0 2 2
OH
3
OH
3
OCH
3 2
OH
3
OH
3
OCF
2
OF
3 2
CH
3
OH
3 CN 2 H 01 cI 0 H 01 F 0 H CI Br 0 H CI SO 2 Me 0 H 01 SMe 0 H 01 SO 2 NMe 2 0 H 01 OF 3 0 H 01 OH 3 0 H 01 OH(0H 3 2 0 H CI NO 2 0 H 01 OOH 3 0 H 01 OOF 2
OF
3 0 H 01 ON 0 H 01 01 1 H CI F 1 H 01 Br 1 H CI SO 2 Me 1 H 01 SMe 1 H 01 SO 2 NMe 2 1 H CI OF 3 1 H CI OH 3 1 H CI OH(0H 3 2 1 H Cl NO 2 1 H Ol OCH 3 1 H CI 00F 2 0F 3 1 H Cl ON 1 WO 99/09023 WO 9909023PCTIEP98/05247 -58 Oompd. R 2 No.
.300 H .301 H .302 H .303 H .304 H .305 H .306 H .307 H .308 H .309 H .310 H .311 H .312 H .313 H .314 H .315 H .316 H .317 H .318 H .319 H .320 H .321 H .322 H .323 H .324 H .325 H .326 H .327 H .328 H .329 H .330 H
R
3
R
4 R5 n
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3 0H 3
CH
2
OH
3
CH
2 0H 3 0H 2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2 0H 3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2 H 0! Cl 2 H 01 F 2 H 01 Br 2 H 01 SO 2 Me 2 H CI SMe 2 H 01 SO 2 NMe 2 2 H 0! OF 3 2 H 01 OH 3 2 H 01 OH(0H 3 2 2 H 01 NO 2 2 H CI 00H 3 2 H 01 OCF 2
CF
3 2 H 01 ON 2 H 01 01 0 H 01 F 0 H 01 Br 0 H 01 SO 2 Me 0 H 01 SMe 0 H 01 SO 2 N Me 2 0 H 01 OF 3 0 H 01 OH 3 0 H 01 OH(CH 3 2 0 H 01 NO 2 0 H 0! 00H 3 0 H CI OOF 2
CF
3 0 H 01 ON 0 H CI cI 1 H 01 F 1 H CI Br 1 H CI SO 2 Me 1 H 01 SMe 1 WO 99/09023- Oompd. R 2
RR
3
R
4
R
5 n No.
.331 H 0H 3 0H 2 H CI SO 2 NMe 2 1 .332 H CH 3
CH
2 H CI CF 3 1 .333 H CH 3
CH
2 H CI CH 3 1 .334 H CH 3
OH
2 H CI CH(CH 3 2 1 .335 H CH 3 0H 2 H CI NO 2 1 .336 H CH 3
CH
2 H CI OCH 3 1 .337 H CH 3
CH
2 H CI OOF 2
CF
3 1 .338 H CH 3
CH
2 H CI ON 1 .339 H CH 3
CH
2 H CI CI 2 .340 H 0H 3 0H 2 H CI F 2 .341 H CH 3
CH
2 H CI Br 2 .342 H CH 3
CH
2 H CI SO 2 Me 2 .343 H CH 3
CH
2 H CI SMe 2 .344 H CH 3
OH
2 H CI SO 2 NlMe 2 2 .345 H CH 3
CH
2 H CI OF 3 2 .346 H CH 3
CH
2 H CI CH 3 2 .347 H CH 3
CH
2 H CI CH(CH 3 2 2 .348 H CH 3
CH
2 H CI NO 2 2 .349 H CH 3
CH
2 H CI 00H 3 2 .350 H CH 3
CH
2 H CI OCF 2
CF
3 2 .351 H CH 3
CH
2 H CI CN 2 .352 CH 3
OH
3
CH
2 H CI CI 0 .353 OH 3
CH
3
CH
2 H Cl F 0 .354 OH 3 0H 3 0H 2 H CI Br 0 .355 OH 3
CH
3
CH
2 H CI SO 2 Me 0 .356 OH 3
OH
3
OH
2 H Cl SMe 0 .357 OH 3
OH
3
OH
2 H CI SO 2 NMe 2 0 .358 OH 3 0H 3 0H 2 H CI CF 3 0 .359 OH 3 0H 3 0H 2 H Cl OH 3 0 .360 OH 3
CH
3 0H 2 H CI CH(CH 3 2 0 .361 OH 3
CH
3
CH
2 H CI NO 2 0 PCT[EP98/05247 WO 99/09023 WO 9909023PCT/EP98/05247 60 Oompd. R 2 No.
.362 CH 3 .363 OH 3 .364 OH 3 .365 OH 3 .366 OH 3 .367 OH 3 .368 OH 3 .369 OH 3 .370 OH 3 .371 OH 3 .372 OH 3 .373 OH 3 .374 OH 3 .375 OH 3 .376 OH 3 .377 OH 3 .378 OH 3 .379 OH 3 .380 OH 3 .381 OH 3 .382 OH 3 .383 OH 3 .384 OH 3 .385 OH 3 .386 OH 3 .387 OH 3 .388 OH 3 .389 OH 3 .390 OH 3 .391 H .392 H
R
3
R
4
CH
3 0H 2 0H 3 0H 2
CH
3
CH
2 0H 3 0H 2 0H 3 0H 2 0H 3
CH
2 0H 3 0H 2
CH
3 0H 2
CH
3
CH
2
CH
3 0H 2
CH
3
CH
2 0H 3 0H 2
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2 0H 3
CH
2 0H 3
CH
2
CH
3 0H 2
CH
3
OH
2
CH
3 0H 2
CH
3 0H 2
CH
3 0H 2
CH
3
CH
2 0H 3 0H 2 0H 3
CH
2
CH
3 0H 2
CH
3
CH
2
CH
3 0H 2
CH
3 0H 2
OH
3
OH
3 H 01 00H 3 0 H 0! 00F 2 0F 3 0 H 01 ON 0 H 01 01 1 H 01 F 1 H 01 Br 1 H 01 SO 2 Me 1 H 01 SMe 1 H 01 SO 2 NMe 2 1 H 01 CF 3 1 H Cl OH 3 1 H CI OH(0H 3 2 1 H CI NO 2 1 H 01 00H 3 1 H 01 00F 2 0F 3 1 H 01 ON 1 H 01 01 2 H 01 F 2 H CI Br 2 H 01 SO 2 Me 2 H CI SMe 2 H CI SO 2 NMe 2 2 H CI OF 3 2 H 01 OH 3 2 H CI OH(CH 3 2 2 H CI NO 2 2 H 01 00H 3 2 H Cl 00F 2 0F 3 2 H CI ON 2 H H CI 0 H H F 0 WO 99/09023 WO 9909023PCTIEP98/05247 61 Compd. R 2 No.
.393 H .394 H .395 H .396 H .397 H .398 H .399 H .400 H .401 H .402 H .403 H .404 H .405 H .406 H .407 H .408 H .409 H .410 H .411 H .412 H .413 H .414 H .415 H .416 H .417 H .418 H .419 H .420 H .421 H .422 H .423 H
R
3
R
4
R
5 n
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3 H H Br 0 H H SO 2 Me 0 H H SMe 0 H H SO 2 NMe 2 0 H H OF 3 0 H H OH 3 0 H H CH(O H 3 2 0 H H NO 2 0 H H 00H 3 0 H H OCF 2
OF
3 0 H H ON 0 H H 01 1 H H F 1 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H OF 3 1 H H OH 3 1 H H OH(0H 3 2 1 H H NO 2 1 H H 00H 3 1 H H OCF 2
OF
3 1 H H ON 1 H H 01 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H OF 3 2 WO 99/09023 -6 Compd. R 2
RR
3
R
4 Rs n No.
.424 H OH 3 H H OH 3 2 .425 H OH 3 H H OH(0H 3 2 2 .426 H OH 3 H H NO 2 2 .427 H OH 3 H H 00H 3 2 .428 H OH 3 H H OCF 2
CF
3 2 .429 H OH 3 H H CN 2 .430 H CH 2 0H H H CI 0 .431 H CH 2 0H H H F 0 .432 H CH 2 0H H H Br 0 .433 H CH 2 0H H H SO 2 Me 0 .434 H CH 2 0H H H SMe 0 .435 H CH 2 0H H H SO 2 NMe 2 0 .436 H CH 2 0H H H OF 3 0 .437 H CH 2 0H H H OH 3 0 .438 H CH 2 0H H H CH(CH 3 2 0 .439 H CH 2 0H H H NO 2 0 .440 H CH 2 0H H H OCH 3 0 .441 H CH 2 0H H H OOF 2
CF
3 0 .442 H CH 2 0H H H CN 0 .443 H CH 2 0H H H 01 1 .444 H CH 2 0H H H F 1 .445 H CH 2 0H H H Br 1 .446 H CH 2 0H H H SO 2 Me 1 .447 H CH 2 0H H H SMe 1 .448 H CH 2 0H H H SO 2 NMe 2 1 .449 H CH 2 0H H H CF 3 1 .450 H CH 2 0H H H OH 3 1 .451 H CH 2 0H H H OH(0H 3 2 1 .452 H CH 2 0H H H NO 2 1 .453 H CH 2 0H H H 00H 3 1 PCTIEP98/05247 .454 H CH 2 0H H H 0F0F 1 H H OCF2CF3 1 WO 99/09023 -6 Compd. R 2
RR
3
R
4
R
5 n No.
.455 H CH 2 0H H H ON 1 .456 H CH 2 0H H H CI 2 .457 H CH 2 0H H H F 2 .458 H CH 2 0H H H Br 2 .459 H CH 2 0H H H SO 2 Me 2 .460 H CH 2 0H H H SMe 2 .461 H CH 2 0H H H SO 2 NMe 2 2 .462 H CH 2 0H H H CF 3 2 .463 H CH 2 0H H H OH 3 2 .464 H CH 2 0H H H CH(CH 3 2 2 .465 H CH 2 0H H H NO 2 2 .466 H CH 2 0H H H 00H 3 2 .467 H CH 2 0H H H OCF 2
CF
3 2 .468 H CH 2 0H H H CN 2 .469 H CO 2
CH
3 H H CI 0 .470 H CO 2
CH
3 H H F 0 .471 H CO 2
CH
3 H H Br 0 .472 H C0 2 0H 3 H H SO 2 Me 0 .473 H CO 2
CH
3 H H SMe 0 .474 H C0 2 0H 3 H H SO 2 NMe 2 0 .475 H CO 2
CH
3 H H CF 3 0 .476 H CO 2
CH
3 H H OH 3 0 .477 H CO 2
CH
3 H H CH(CH 3 2 0 .478 H CO 2
CH
3 H H NO 2 0 479 H CO 2
CH
3 H H OCH 3 0 .480 H CO 2
CH
3 H H OCF 2
CF
3 0 .481 H CO 2
CH
3 H H ON 0 .482 H CO 2
CH
3 H H CI 1 .483 H CO 2
CH
3 H H F 1 .484 H CO 2
CH
3 H H Br 1 .485 H CO 2
CH
3 H H SO 2 Me 1 PCT/EP98/05247 WO 99/09023 -6 Compd. R 2
RR
3
R
4
R
5 n No.
.486 H CO 2
CH
3 H H SMe 1 .487 H CO 2
CH
3 H H SO 2 NMe 2 1 .488 H CO 2
CH
3 H H CF 3 1 .489 H CO 2
CH
3 H H CH 3 1 .490 H CO 2
CH
3 H H CH(CH 3 2 1 .491 H C0 2
CH
3 H H NO 2 1 .492 H CO 2
CH
3 H H OCH 3 1 .493 H CO 2
CH
3 H H OCF 2
CF
3 1 .494 H CO 2
CH
3 H H CN 1 .495 H CO 2
CH
3 H H CI 2 .496 H C0 2
CH
3 H H F 2 .497 H 00 2
CH
3 H H Br 2 .498 H CO 2
CH
3 H H SO 2 Me 2 .499 H CO 2
CH
3 H H SMe 2 .500 H CO 2
CH
3 H H SO 2 NMe 2 .2 .501 H CO 2
CH
3 H H CF 3 2 .502 H C0 2
CH
3 H H CH 3 2 .503 H C0 2
CH
3 H H CH(CH 3 2 2 .504 H CO 2
CH
3 H H NO 2 2 .505 H CO 2
CH
3 H H OCH 3 2 .506 H CO 2
CH
3 H H OCF 2
CF
3 2 .507 H CO 2
CH
3 H H CN 2 .508 H CH=O H H cI 0 .509 H CH=O H H F 0 .510 H CH=O H H Br 0 .511 H CH=O H H SO 2 Me 0 .512 H CH=O H H SMe 0 .513 H CH=O H H SO 2 NlMe 2 0 .514 H CH=O H H CF 3 0 .515 H CH=O H H CH 3 0 .516 H CH=O H H CH(CH 3 2 0 PCTIEP98/05247 WO 99/09023 -6 Oompd. R 2
RR
3
R
4 Rs n No.
.517 H OH=O H H NO 2 0 .518 H OH=O H H 00H 3 0 .519 H OH=O H H OOF 2
CF
3 0 .520 H CH=O H H CN 0 .521 H CH=O H H cI 1 .522 H CH=O H H F 1 .523 H OH=O H H Br 1 .524 H OH=O H H SO 2 Me 1 .525 H OH=O H H SMe 1 .526 H CH=O H H SO 2 NMe 2 1 .527 H CH=O H H OF 3 1 .528 H CH=O H H OH 3 1 .529 H OH=O H H CH(CH 3 2 1 .530 H OH=O H H NO 2 1 .531 H OH=O H H 00H 3 1 .532 H OH=O H H OOF 2
CF
3 1 .533 H CH=O H H ON 1 .534 H OH=O H H CI 2 .535 H OH=O H H F 2 .536 H OH=O H H Br 2 .537 H OH=O H H SO 2 Me 2 .538 H OH=O H H SMe 2 .539 H OH=O H H SO 2 N Me 2 2 .540 H OH=O H H OF 3 2 .541 H OH=O H H OH 3 2 .542 H OH=O H H CH(0H 3 2 2 .543 H OH=O H H NO 2 2 .544 H OH=O H H 00H 3 2 .545 H OH=O H H OOF 2
CF
3 2 .546 H OH=O H H ON 2 PCTIEP98/05247 .547 H CH=NOOH 3 H H C H H cl 0 WO 99/09023 WO 9909023PCT/EP98/05247 -66 Compd. R 2 No.
.548 H .549 H .550 H .551 H .552 H .553 H .554 H
R
3
R
4 Rs n .555 .556 .557 .558 .559 .560 .561 .562 .563 .564 .565 .566 .567 .568 .569 .570 .571 .572 .573 .574 .575 .576 .577 .578
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3
CH=NOCH
3 H H F 0 H H Br 0 H H SO 2 Me 0 H H SMe 0 H H SO 2 NMe 2 0 H H CF 3 0 H H CH 3 0 H H CH(CH 3 2 0 H H N0 2 0 H H OCH 3 0 H H OCF 2
CF
3 0 H H CN 0 H H cI 1 H H F 1 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H CF 3 1 H H OH 3 1 H H CH(CH 3 2 1 H H N0 2 1 H H OCH 3 1 H H OCF 2
CF
3 1 H H ON 1 H H CI 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 WO 99/09023 WO 9909023PCT/EP98/05247 -67 Compd.
No.
.579 .580 .581 .582 .583 .584 .585 .586 .587 .588 .589 .590 .591 .592 .593 .594 .595 .596 .597 .598 .599 .600 .601 .602 .603 .604 .605 .606 .607 .608 .609
R
3
R
4
OH=NOCH
3
CH=NOCH
3
OH=NOCH
3
OH=NOCH
3
OH=NOOH
3
OH=NOCH
3
CH=NOCH
3
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2
OH
2
NH
2
OH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2 H H CF 3 2 H H OH 3 2 H H CH(CH 3 2 2 H H N0 2 2 H H OCH 3 2 H H OOF 2
CF
3 2 H H ON 2 H H CI 0 H H F 0 H H Br 0 H H SO 2 Me 0 H H SMe 0 H H SO 2 NMe 2 0 H H OF 3 0 H H OH 3 0 H H OH(CH 3 2 0 H H N0 2 0 H H 00H 3 0 H H 00F 2 0F 3 0 H H ON 0 H H cI 1 H H F 1 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H CF 3 1 H H OH 3 1 H H OH(CH 3 2 1 H H NO 2 1 H H OCH 3 1 WO 99/09023 WO 9909023PCT/EP98/05247 -68 Compd. R 2 No.
.610 H .611 H .612 H .613 H .614 H .615 H .616 H .617 H .618 H .619 H .620 H .621 H .622 H .623 H .624 H .625 H .626 H .627 H .628 H .629 H .630 H .631 H .632 H .633 H
R
3
R
4 R5 n
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
OH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
CH
2
NH
2
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
H H 00F 2 0F 3 1 H H ON 1 H H 01 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H CF 3 2 H H OH 3 2 H H OH(0H 3 2 2 H H NO 2 2 H H OCH 3 2 H H 00F 2 0F 3 2 H H ON 2 H H 01 0 H H F 0 H H Br 0 H H SO 2 Me 0 H H SMe 0 H H SO 2 NMe 2 0 H H OF 3 0 H H OH 3 0 H H OH(CH 3 2 0 H H NO 2 0 H H OCH 3 0 H H 00F 2 0F 3 0 H H ON 0 H H 01 1 H H F 1 H H Br 1 .634 .635 .636 .637 .638 .639 .640 WO 99/09023 WO 9909023PCTIEP98/05247 69 Compd. R 2 No.
.641 H .642 H .643 H .644 H .645 H .646 H .647 H .648 H .649 H .650 H .651 H .652 H .653 H .654 H .655 H .656 H .657 H .658 H .659 H .660 H .661 H .662 H .663 H .664 H .665 H .666 H .667 H .668 H .669 H .670 H .671 H
R
3
R
4
R
5 n
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
ON
OH(OH)0H 3 OH(OH)0H 3 CH(OH)0H 3 CH(OH)0H 3
CH(OH)CH
3 CH(OH)0H 3 CH(OH)0H 3 OH(OH)0H 3 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H OF 3 1 H H OH 3 1 H H OH(0H 3 2 1 H H N0 2 1 H H 00H 3 1 H H 00F 2 0F 3 1 H H ON 1 H H 01 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H OF 3 2 H H OH 3 2 H H OH(0H 3 2 2 H H NO 2 2 H H 00H 3 2 H H 00F 2 0F 3 2 H H ON 2 H H 01 0 H H F 0 H H Br 0 H H SO 2 Me 0 H H SMe 0 H H SO 2 NMe 2 0 H H OF 3 0 H H OH 3 0 WO 99/09023 Oompd. R 2
RR
3
R
4
R
5 n No.
.672 H OH(OH)CH 3 H H OH(CH 3 2 0 .673 H OH(OH)0H 3 H H NO 2 0 .674 H OH(OH)0H 3 H H 00H 3 0 .675 H CH(OH)CH 3 H H OCF 2
OF
3 0 .676 H CH(OH)0H 3 H H CN 0 .677 H OH(OH)0H 3 H H cI 1 .678 H CH(QH)CH 3 H H F 1 .679 H OH(OH)0H 3 H H Br 1 .680 H CH(QH)CH 3 H H SO 2 Me 1 .681 H OH(OH)0H 3 H H SMe 1 .682 H OH(OH)CH 3 H H SO 2 NMe 2 1 .683 H CH(OH)0H 3 H H OF 3 1 .684 H OH(OH)CH 3 H H OH 3 1 .685 H OH(OH)0H 3 H H CH(0H 3 2 1 .686 H CH(OH)CH 3 H H NO 2 1 .687 H OH(OH)0H 3 H H 00H 3 1 .688 H CH(OH)0H 3 H H 00F 2
CF
3 1 .689 H CH(OH)0H 3 H H ON 1 .690 H CH(OH)CH 3 H H CI 2 .691 H OH(OH)0H 3 H H F 2 .692 H OH(OH)0H 3 H H Br 2 .693 H OH(OH)0H 3 H H SO 2 Me 2 .694 H OH(OH)0H 3 H H SMe 2 .695 H OH(OH)0H 3 H H SO 2 NMe 2 2 .696 H OH(OH)0H 3 H H OF 3 2 .697 H OH(OH)0H 3 H H OH 3 2 .698 H OH(OH)0H 3 H H OH(CH 3 2 2 .699 H OH(OH)0H 3 H H NO 2 2 .700 H OH(OH)0H 3 H H 00H 3 2 .701 H OH(OH)0H 3 H H OCF 2
OF
3 2 .702 H OH(OH)CH 3 H H ON 2 PCTIEP98/05247 WO 99/09023 -7 Oompd. R 2 R, R 3
R
4
R
5 n No.
.703 H CH=CHCH 3 H H cI 0 .704 H CH=CHCH 3 H H F 0 .705 H CH=CHOH 3 H H Br 0 .706 H CH=OHCH 3 H H SO 2 Me 0 .707 H OH=OHCH 3 H H SMe 0 .708 H CH=CHOH 3 H H SO 2 NMe 2 0 .709 H CH=OHCH 3 H H CF 3 0 .710 H CH=CHCH 3 H H CH 3 0 .711 H OH=CHCH 3 H H CH(CH 3 2 0 .712 H CH=CHCH 3 H H NO 2 0 .713 H CH=CHOH 3 H H 00H 3 0 .714 H CH=CHCH 3 H H OOF 2
CF
3 0 .715 H OH=CHCH 3 H H ON 0 .716 H CH=CHCH 3 H H CI 1 .717 H CH=CHCH 3 H H F 1 .718 H CH=CHOH 3 H H Br 1 .719 H OH=OHOH 3 H H SO 2 Me 1 .720 H CH=CHCH 3 H H SMe 1 .721 H CH=CHCH 3 H H SO 2 NMe 2 1 .722 H CH=CHOH 3 H H CF 3 1 .723 H CH=CHCH 3 H H OH 3 1 .724 H CH=CHCH 3 H H CH(CH 3 2 1 .725 H CH=CHCH 3 H H NO 2 1 .726 H CH=CHCH 3 H H OCH 3 1 .727 H CH=CHCH 3 H H OCF 2
CF
3 1 .728 H CH=CHCH 3 H H CN 1 .729 H CH=CHCH 3 H H CI 2 .730 H OH=OHOH 3 H H F 2 .731 H CH=OHCH 3 H H Br 2 .732 H OH=OHOH 3 H H SO 2 Me 2 .733 H CH=CHCH 3 H H SMe 2 PCT/EP98/05247 WO 99/09023 72 Oompd. R 2
RR
3
R
4
R
5 n No.
.734 H CH=CHCH 3 H H SO 2 NMe 2 2 .735 H CH=CHCH 3 H H CF 3 2 .736 H CH=CHCH 3 H H OH 3 2 .737 H CH=CHCH 3 H H CH(0H 3 2 2 .738 H CH=CHCH 3 H H NO 2 2 .739 H CH=OHOH 3 H H OCH 3 2 .740 H CH=CHOH 3 H H OOF 2
CF
3 2 .741 H CH=CHCH 3 H H CN 2 .742 H CH=CHOO 2
CH
3 H H CI 0 .743 H OH=CHCO 2
OH
3 H H F 0 .744 H OH=CHCO 2
CH
3 H H Br 0 .745 H OH=OHCO 2
CH
3 H H SO 2 Me 0 .746 H CH=CHCO 2
CH
3 H H SMe 0 .747 H CH=CHCO 2
CH
3 H H SO 2 NMe 2 0 .748 H CH=OHCO 2
CH
3 H H CF 3 0 .749 H CH=CHOO 2
OH
3 H H OH 3 0 .750 H CH=OHOO 2
CH
3 H H CH(CH 3 2 0 .751 H CH=OHCO 2
CH
3 H H NO 2 0 .752 H CH=CHCO 2
OH
3 H H OCH 3 0 .753 H CH=OHCO 2
CH
3 H H OCF 2
OF
3 0 .754 H OH=CHCO 2
CH
3 H H ON 0 .755 H CH=CHOO 2
OH
3 H H 01 1 .756 H OH=0H00 2 0H 3 H H F 1 .757 H OH=0H00 2 0H 3 H H Br 1 .758 H OH=0H00 2 0H 3 H H SO 2 Me 1 .759 H CH=OHCO 2
OH
3 H H SMe 1 .760 H CH=CHCO 2
OH
3 H H SO 2 NMe 2 1 .761 H OH=0HC0 2 0H 3 H H CF 3 1 .762 H OH=CHCO 2
OH
3 H H OH 3 1 .763 H OH=0H00 2 0H 3 H H OH(CH 3 2 1 .764 H CH=CHCO 2
OH
3 H H NO 2 1 PCT/EP98/05247 WO 99/09023 WO 9909023PCT/EP98/05247 -73 Compd. R 2 No.
.765 H .766 H .767 H .768 H .769 H .770 H .771 H .772 H .773 H .774 H .775 H .776 H .777 H .778 H .779 H .780 H .781 OH 3 .782 OH 3 .783 CH 3 .784 OH 3 .785 CH 3 .786 CH 3 .787 OH 3 .788 OH 3 .789 OH 3 .790 OH 3 .791 OH 3 .792 OH 3 .793 OH 3 .794 OH 3 .795 OH 3
R,
OH=CHC0 2 0H 3
OH=CHCO
2
CH
3
CH=CHCO
2
CH
3
OH=CHCO
2
OH
3
OH=CHCO
2
OH
3 CH=CHC0 2 0H 3 CH=CHC0 2
CH
3
CH=CHCO
2
CH
3
OH=CHOO
2
CH
3
CH=CHCO
2
CH
3 CH=CHC0 2 0H 3 CH=CHC0 2 0H 3
CH=CHCO
2
CH
3 CH=CHC0 2
OH
3
CH=CHCO
2
CH
3 CH=0HC0 2 0H 3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
R
3
R
4
R
5 n 00H 3 00F 2 0 F 3
ON
0I
F
Br
SO
2 Me SMe S0 2 NMe 2
CF
3
CH
3
OH(CH
3 2 N0 2
OCH
3 00F 2
CF
3
ON
0I
F
Br
SO
2 Me SMe
SO
2 N Me 2
CF
3
OH
3
OH(CH
3 2
NO
2
OOH
3
OCF
2
CF
3
CN
CI
F
WO 99/09023 PCT/EP98/05247 -74- Compd. R 2 No.
.796 CH 3 .797 CH 3 .798 CH 3 .799 CH 3 .800 CH 3 .801 CH 3 .802 CH 3 .803 CH 3 .804 CH 3 .805 CH 3 .806 CH 3 .807 CH 3 .808 CH 3 .809 CH 3 .810 CH 3 .811 CH 3 .812 CH 3 .813 CH 3 .814 CH 3 .815 CH 3 .816 CH 3 .817 CH 3 .818 CH 3 .819 CH 3
R
3
R
4
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3 H H Br 1 H H SO 2 Me 1 H H SMe 1 H H SO 2 NMe 2 1 H H CF 3 1 H H CH 3 1 H H CH(CH 3 2 1 H H NO 2 1 H H OCH 3 1 H H OCF 2
CF
3 1 H H CN 1 H H Cl 2 H H F 2 H H Br 2 H H SO 2 Me 2 H H SMe 2 H H SO 2 NMe 2 2 H H CF 3 2 H H CH 3 2 H H CH(CH 3 2 2 H H NO 2 2 H H OCH 3 2 H H OCF 2
CF
3 2 H H CN 2 WO 99/09023-- Table 7: Compounds Of formula 11 Ri
CH
3
R
2 S(O) n0
S(O),
R
3
N
R4I N 0
R
Compd. R 2 R, R 3
R
4 R5 n n 2 Phys. data No.
7.001 H CH 3 H H CI 0 0 7.002 H CH 3 H H F 0 0 7.003 H OH 3 H H Br 0 0 7.004 H CH 3 H H SO 2 Me 0 0 7.005 H CH 3 H H SMe 0 0 7.006 H CH 3 H H SO 2 NMe 2 0 0 7.007 H OH 3 H H CF 3 0 0 7.008 H OH 3 H H OH 3 0 0 7.009 H OH 3 H H OH(0H 3 2 0 0 7.010 H CH 3 HH NO 2 0 0 7.011 H CH 3 H H 00H 3 0 0 7.012 H OH 3 H H 00F 2
CF
3 0 0 7.013 H OH 3 H H ON 0 0 7.014 H OH 3 H H CI 1 0 7.015 H OH 3 HH F 1 0 7.016 H OH 3 H H Br 1 0 7.017 H OH 3 H H SO 2 Me 1 0 7.018 H OH 3 H H SMe 1 0 7.019 H OH 3 H H SO 2 NMe 2 1 0 7.020 H OH 3 H H OF 3 1 0 7.021 H OH 3 H H OH 3 1 0 7.022 H OH 3 H H CH(0H 3 2 1 0 7.023 H OH 3 H H NO 2 1 0 7.024 H OH 3 H H OOH 3 1 0 7.025 H OH 3 H H OCF 2
CF
3 1 0 PCT/EP98/05247 WO 99/09023 -7 Compd. R 2 R, R 3
R
4
R
5 nl n 2 Phys. data No.
7.026 H CH 3 H H ON 1 0 7.027 H OH 3 H H cl 2 0 129-1300C 7.028 H CH 3 HH F 2 0 7.029 H OH 3 H H Br 2 0 7.030 H OH 3 H H SO 2 Me 2 0 7.031 H OH 3 HH SMe 2 0 7.032 H OH 3 H H SO 2 NMe 2 2 0 7.033 H OH 3 HH OF 3 2 0 7.034 H OH 3 H H OH 3 2 0 7.035 H OH 3 H H OH(0H 3 2 2 0 7.036 H OH 3 H H NO 2 2 0 7.037 H OH 3 H H 00H 3 2 0 7.038 H OH 3 H H OCF 2
OF
3 2 0 7.039 H OH 3 HH ON 2 0 7.040 H OH 3 HH 01 0 0 7.041 H OH 3 H H F 0 0 7.042 H OH 3 H H Br 0 0 7.043 H OH 3 H H SO 2 Me 0 0 7.044 H OH 3 H H SMe 0 0 7.045 H OH 3 H H SO 2 NMe 2 0 0 7.046 H OH 3 H H OF 3 0 0 7.047 H OH 3 H H OH 3 0 0 7.048 H OH 3 H H OH(0H 3 2 0 0 7.049 H OH 3 H H NO 2 0 0 7.050 H OH 3 H H 00H 3 0 0 7.051 H OH 3 H H OOF 2
OF
3 0 0 7.052. H OH 3 H H ON 0 0 7.053 H OH 3 H H Cl 1 0 7.054 H OH 3 H H F 1 0 7.055 H OH 3 H H Br 1 0 7.056 H OH 3 H H SO 2 Me 1 0 7.057 H OH 3 H H SMe 1 0 PCT/EP98/05247 WO 99/09023 -77- Compd. R 2 R, R 3
R
4 Rs n n 2 Phys. data No.
7.058 H CH 3 H H SO 2 NMe 2 1 0 7.059 H CH 3 H H CF 3 1 0 7.060 H CH3 H H CH 3 1 0 7.061 H CH 3 H H CH(CH 3 2 1 0 7.062 H CH 3 H H NO 2 1 0 7.063 H CH 3 H H OCH 3 1 0 7.064 H CH 3 H H OCF 2
CF
3 1 0 7.065 H CH3 H H CN 1 0 7.066 H CH 3 H H Cl 2 0 7.067 H CH 3 H H F 2 0 7.068 H CH 3 H H Br 2 0 7.069 H CH 3 H H SO 2 Me 2 0 7.070 H CH 3 H H SMe 2 0 7.071 H CH 3 H H SO 2 NMe 2 2 0 7.072 H CH 3 H H CF 3 2 0 7.073 H CH 3 H H CH 3 2 0 7.074 H CH 3 H H CH(CH 3 2 2 0 7.075 H CH 3 H H NO 2 2 0 7.076 H CH3 H H OCH 3 2 0 7.077 H CH 3 H H OCF 2
CF
3 2 0 7.078 H CH 3 H H CN 2 0 7.079 H CH 3 H H Cl 0 1 7.080 H CH 3 H H F 0 1 7.081 H CH 3 H H Br 0 1 7.082 H CH 3 H H SO 2 Me 0 1 7.083 H CH 3 H H SMe 0 1 7.084 H CH 3 H H SO 2 NMe 2 0 1 7.085 H CH 3 H H CF 3 0 1 7.086 H CH 3 H H CH 3 0 1 7.087 H CH 3 H H CH(CH 3 2 0 1 7.088 H CH 3 H H NO 2 0 1 7.089 H CH 3 H H OCH 3 0 1 PCT/EP98/05247 WO 99/09023 -78- Compd. R 2
R
1 Ra R 4 Rs n n 2 Phys. data No.
7.090 H CH 3 H H OCF 2
CF
3 0 1 7.091 H CH 3 H H CN 0 1 7.092 H CH 3 H H CI 1 1 7.093 H CH 3 H H F 1 1 7.094 H CH 3 H H Br 1 1 7.095 H CH 3 H H SO 2 Me 1 1 7.096 H CH 3 H H SMe 1 1 7.097 H CH 3 H H SO 2 NMe 2 1 1 7.098 H CH 3 H H CF 3 1 1 7.099 H CH 3 H H CH 3 1 1 7.100 H CH 3 H H CH(CH 3 2 1 1 7.101 H CH 3 H H NO 2 1 1 7.102 H CH 3 H H OCH 3 1 1 7.103 H CH 3 H H OCF 2 CFa 1 1 7.104 H CHa H H CN 1 1 7.105 H CH 3 H H CI 2 1 7.106 H CH 3 H H F 2 1 7.107 H CHa H H Br 2 1 7.108 H CH 3 H H SO 2 Me 2 1 7.109 H CH 3 H H SMe 2 1 7.110 H CH 3 H H SO 2 NMe 2 2 1 7.111 H CH 3 H H CF 3 2 1 7.112 H CH 3 H H CH 3 2 1 7.113 H CH 3 H H CH(CHa) 2 2 1 7.114 H CH 3 H H NO 2 2 1 7.115 H CH 3 H H OCH 3 2 1 7.116 H CH 3 H H OCF 2
CF
3 2 1 7.117 H CH 3 H H CN 2 1 7.118 H CH 3 H H CI 0 2 7.119 H CH 3 H H F 0 2 7.120 H CH 3 H H Br 0 2 7.121 H CH 3 H H SO 2 Me 0 2 PCT/EP98/05247 WO 99/09023 WO 9909023PCT/EP98/05247 79.
Compd.
No.
7.122 7.123 7.124 7.125 7.126 7.127 7.128 7.129 7.130 7.131 7.132 7.133 7.134 7.135 7.136 7.137 7.138 7.139 7.140 7.141 7.142 7.143 7.144 7.145 7.146 7.147 7.148 .7.149 7.150 7.151 7.152
R
2 R 1
R
3
R
4 Rs n n 2 Phys. data
CH
3
OH
3
OH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3 SMe
SO
2 NMe 2
OF
3
OH
3 CH(0H 3 2 N0 2 00H 3 00F 2 0F 3
ON
0I
F
Br
SO
2 Me SMe
SO
2 NMe 2
OF
3
OH
3 OH(0H 3 2
NO
2 O0H 3 00 F 2 0F 3
ON
0I
F
Br S0 2 Me SMe
SO
2 NMe 2
OF
3
OH
3
CH(CH
3 2 1 2 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 7.153 H OH 3 H H NO 2 2 2 WO 99/09023 WO 9909023PCTIEP98/05247 Oompd.
No.
7.154 7.155 7.156 7.157 7.158 7.159 7.160 7.161 7.162 7.163 7.164 7.165 7.166 7.167 7.168 7.169 7.170 7.171 7.172 7.173 7.174 7.175 7.176 7.177 7.178 7.179 7.180 7.181 7.182 7.183 7.184
R
2 R, R3 R 4
R
5 n n 2 Phys. data
H
H
H
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3 00H 3 O0F 2
CF
3
ON
0I
F
Br S0 2 Me SMe
SO
2 NMe 2
OF
3
OH
3 OH(0H 3 2 N0 2 00H 3 00F 2
CF
3
ON
0I
F
Br S0 2 Me SMe
SO
2 NMe 2
OF
3
OH
3 OH(0H 3 2
NO
2 00H 3
OOF
2
OF
3
ON
0I
F
7.185 OH 3
OH
3 H H Br 2 0 WO 99/09023 PCT/EP98/05247 -81 Compd.
No.
7.186 7.187 7.188 7.189 7.190 7.191 7.192 7.193 7.194 7.195
R
2
R
1
R
3
R
4 Rs n n 2 Phys. data
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
SO
2 Me SMe
SO
2 NMe 2
CF
3
CH
3
CH(CH
3 2
NO
2
OCH
3 OCF2CF 3
CN
Table 8: A further group of compounds of formula I corresponds to general formula Im CH3 R1
O
1 O 0 0 R 3
N
R 4 wherein the meanings of the corresponding substituents R 1 to Rs and n are given in Table B, so that 78 specific compounds of formula Im are disclosed.
Table 9: A further group of compounds of formula I corresponds to general formula In R1
R
2 S(O)n
O
Ra 3 N wherein the meanings of the corresponding substituents R4
R
R
1 to Rs and n are given in Table B, so that 78 specific compounds of formula In are disclosed.
WO 99/09023 PCT/EP98/05247 -82- Table 10: A further group of compounds of formula I corresponds to general formula lo wherein the meanings of the corresponding
CH
3 substituents R 1 to Rs and n are given in Table B, so that 78 specific compounds of formula lo are disclosed.
Table 11: A further group of compounds of formula I corresponds to general formula Ip
R
2 S(O) 0 RR N N n
N
Rs OH
\C
2
H
wherein the meanings of the corresponding substituents R 1 to Rs and n are given in Table B, so that 78 specific compounds of formula Ip are disclosed.
Table B Compd.
No.
.001 .002 .003 .004 .005 .006 .007 .008 .009 .010 .011 .012
R
2
R
1
R
3
R
4
R
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3 Cl
F
Br
SO
2 Me SMe
SO
2 NMe 2
CF
3
CH
3
CH(CH
3 2
NO
2
OCH
3
OCF
2
CF
3 WO 99/09023 WO 9909023PCT/EP98/05247 -83 Oompd.
No.
.013 .014 .015 .016 .017 .018 .019 .020 .021 .022 .023 .024 .025 .026 .027 .028 .029 .030 .031 .032 .033 .034 .035 .036 .037 .038 .039 .040 .041 .042 .043 .044
R
2 R, R 3
R
4
R
5 n
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
CH
3
H
OH
3
H
CH
3
H
OH
3
H
CH
3
H
CH
3
H
OH
3
H
CH
3
H
OH
3
H
OH
3
H
OH
3
H
OH
3
H
OH
3
H
OH
3
H
CH
3
H
CH
3
H
OH
3
H
CH
3
H
OH
3
H
OH
3
H
CH
3
H
OH
3
H
OH
3
H
OH
3
H
OH
3
H
CH
3
H
OH
3
H
OH
3
H
ON
0I
F
Br
SO
2 Me SMe S0 2 NMe 2
OF
3
OH
3 OH(0H 3 2 N0 2 00H 3 00F 2
CF
3
ON
0I
F
Br S0 2 Me SMe
SO
2 NMe 2
OF
3
OH
3
OH(CH
3 2 N0 2 00H 3 00F 2
CF
3
ON
0I
F
Br S0 2 Me SMe
OH
3
OH
3
H
OH
3
OH
3
H
OH
3
OH
3
H
OH
3
OH
3
H
WO 99/09023 WO 9909023PCT/EP98/05247 -84 Compd.
No.
.045 .046 .047 .048 .049 .050 .051 .052 .053
R
2 R, R 3
R
4
R
5 n .054 .055 .056 .057 .058 .059 .060 .061 .062 .063 .064 .065 .066 .067 .068 .069 .070 .071 .072 .073 .074 .075 .076
CH
3
OH
3 H H SO 2 NMe 2 0
OH
3
CH
3 H H CF 3 0
OH
3
OH
3 H H CH 3 0
CH
3
OH
3 H H CH(CH 3 2 0
OH
3
CH
3 H H N0 2 0
OH
3
CH
3 H H 00H 3 0
OH
3
OH
3 H H OCF 2
CF
3 0
CH
3
CH
3 H H CN 0
OH
3
OH
3 H H cI 1
CH
3
CH
3 H H F 1
CH
3
CH
3 H H Br 1
OH
3
OH
3 H H SO 2 Me 1
OH
3
OH
3 H H SMe 1
OH
3
OH
3 H H SO 2 NMe 2 1
CH
3
OH
3 H H OF 3 1
CH
3
OH
3 H H OH 3 1
OH
3
OH
3 H H OH(CH 3 2 1
OH
3
OH
3 H H NO 2 1
OH
3
OH
3 H H OCH 3 1
OH
3
OH
3 H H 00F 2 0F 3 1
CH
3
OCH
3 H H ON 1
OH
3
OH
3 H H 01 2
CH
3
OCH
3 H H F 2
OH
3
OCH
3 H H Br 2
OH
3
OH
3 H H S0 2 Me 2 0H 3 0CH 3 H H SMe 2
OH
3
OH
3 H H SO 2 NMe 2 2
OH
3
OH
3 H H OF 3 2
OH
3
OH
3 H H OH 3 2
OH
3
OH
3 H H CH(0H 3 2 2
CH
3
CH
3 H H NO 2 2
OH
3
OH
3 H H 00H 3 2 WO 99/09023 WO 9909023PCTAEP98105247 Oompd.
No.
.077 .078
R
2 R, R 3
R
4
R
5 n
OH
3
OH
3
H
OH
3
CH
3
H
00F 2 0F 3
ON
Table 12: Compounds of formula lq Compd. R 6 (03) R 7
R
6 (05) n Phys. data No.
12.001 12.002 12.003 12.004 12.005 12.006 12.007 12.008 12.009 12.01 12.011 12.012 12.013 12.014 12.015 12.016 12.017 12.018
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
OH
3 OH=0H 2 Br SMe
H
OH
3
CH=CH
2 Br SMe
H
OH
3
OH=CH
2 Br SMe
OH
3
OH=CH
2 Br
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3 159-1 61 00 157-1590C WO 99/09023 WO 9909023PCT/EP98/05247 -86- Oompd. R 6
(C
3 R7 R 6 (CO) n Phys. data No.
12.019 12.02 12.021 12.022 12.023 12.024 12.025 12.026 12.027 12.028 12.029
CH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3
CH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3 CH-3
OH
3
OH
3
OH
3 SMe
H
OH
3 CH=0H 2 Br SMe
H
OH
3 OH=0H 2 Br SMe
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
'R
6 in Table 12 above means that the substituent R 6 is bonded to carbon atom 3 in the compound of formula 1q; and accordingly 'R 6 means that the substituent R 6 is bonded to carbon atom 5 in the compound of formula 1q.
Table 13: Compounds of formula Ir R7 CI HO* R18 Compd.
No.
13.001 13.002 13.003 13.004 13.005 13.006
R
6
R
6
R
H H H H H H H H H H H H H H H H H H Ris
OH
3
OF
3 00 2
CH
2
CH
3
OH
3 OF7 3 C0 2
CH
2
CH
3 Phys. data viscous oil viscous oil wo 99/09023 WO 9909023PCT/EP98/05247 -87 Compd.
No.
13.007 13.008 13.009 13.010 13.011 13.012 13.013 13.014 13.015 13.016 13.017 13.018 13.019 13.020 13.021 13.022 13.023 13.024 13.025 13.026 13.027 13.028 13.029 13.030 13.031 13.032 13.033 13.034 13.035 13.036 13.037 13.038
R
6
R
6 R7s dt
H
H
H
OH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OF
3 C0 2
CH
2
CH
3
H
OH
3
OF
3 O0 2
CH
2
CH
3
H
OH
3
OF
3 C0 2 0H 2 0H 3
H
OH
3
OF
3 00 2
CH
2 0H 3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
OH
3
OF
3 00 2
CH
2
CH
3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
129-1320C viscous oil 139-1400C 179-1800C viscous oil amorphous WO 99/09023 PCT/EP98/05247 -88- Compd. R 6 R6 R7 R7 Ra n Phys. data No.
13.039 CH 3
CH
3
CH
3 H CH 3 1 13.040 CH 3
CH
3
CH
3 H CF 3 1 13.041 CH 3
CH
3
CH
3 H C0 2
H
2 CH 3 1 13.042 CH 3
CH
3
CH
3 H H 2 resin 13.043 CH 3
CH
3
CH
3 H CH 3 2 13.044 CH 3
CH
3 CHa H CF 3 2 13.045 CH 3
CH
3
CH
3 H CO 2
CH
2
CH
3 2 13.046 CH 3
CH
3
CH
3
CH
3 H 0 13.047 CH 3
CH
3
CH
3
CH
3
CH
3 0 13.048 CH 3
CH
3
CH
3
CH
3
CF
3 0 13.049 CH 3
CH
3
CH
3
CH
3 C0 2
CH
2
CH
3 0 13.050 CH 3
CH
3
CH
3
CH
3 H 1 13.051 CH 3
CH
3 CHa CHa CH 3 1 13.052 CH 3
CH
3
CH
3
CH
3
CF
3 1 13.053 CH 3
CH
3
CH
3
CH
3 C0 2
CH
2
CH
3 1 13.054 CH 3
CH
3
CH
3
CH
3 H 2 13.055 CH 3
CH
3
CH
3
CH
3
CH
3 2 13.056 CH 3
CH
3
CH
3
CH
3
CF
3 2 13.057 CH 3
CH
3
CH
3
CH
3 C0 2
CH
2
CH
3 2 13.058 SCH 3 H CH 3 H H 0 125-128°C 13.059 S0 2
CH
3 H CH 3 H H 0 viscous oil 13.060 SCH 3 H CH 3 H CH 3 0 13.061 SCH 3 H CH 3 H CF 3 0 13.062 SCH 3 H CH 3 H CO 2
CH
2
H
3 0 13.063 SCH 3 H CH 3 H H 1 13.064 SCH 3 H CH 3 H CH 3 1 13.065 SCH 3 H CH 3 H CF 3 1 13.066 SCH 3 H CH 3 H CO 2
CH
2
CH
3 1 13.067 SCH 3 H CH 3 H H 2 13.068 SCH 3 H CH 3 H CH 3 2 13.069 SCH 3 H CH 3 H CF 3 2 13.070 SCH 3 H CH 3 H CO 2
CH
2
CH
3 2 WO 99/09023 WO 9909023PCT/EP98/05247 89 Compd.
No.
R
6 R6 R Phys. data 111-1130C 13.071 SCH 3 13.072 SOH 3 13.073 SCH 3 13.074 SCH 3 13.075 SCH 3 13.076 SCH 3 13.077 SOH 3 13.078 SCH 3 13.079 SOH 3 13.080 S0 2
CH
3 13.081 SOH 3 13.082 SCH 3 13.083 SCH 3 13.084 SOH 3 13.085 SCH 3 13.086 SCH 3 13.087 SCH 3 13.088 SCH 3 13.089 SOH 3 13.090 SCH 3 13.091 SCH 3 13.092 SCH 3 13.093 SCH 3 13.094 SCH 3 13.095 SOH 3 13.096 SOH 3 13.097 SCH 3 13.098 SOH 3 13.099 SCH 3 13.100 SCH 3 13.101 SCH 3 13.102 SCH 3
OH
3
OH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
CH
3
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
OH
3
OF
3 C0 2 0H 2
CH
3
H
OH
3
OF
3 C0 2
CH
2
CH
3
H
H
OH
3
OF
3
OF
3 00 2
CH
2
CH
3
H
OH
3
OF
3 C0 2
CH
2
CH
3
H
OH
3
CF
3 C0 2 0H 2
CH
3
H
OH
3
OF
3 C0 2 0H 2
CH
3
H
OH
3
OF
3 C0 2 0H 2 0H 3
H
OH
3 resin 244-2460C viscous oil (E isomer) viscous oil (Z isomer) WO 99/09023 WO 9909023PCT/EP98/05247 90 Oompd. R 6 No.
13.103 SCH 3 13.104 SCH 3 13.105 SCH 3 13.106 SOH 3 13.107 SCH 3 13.108 SCH 3 13.109 SCH 3 13.110 SCH 3 13.111 SOH 3 13.112 SCH 3 13.113 SOH 3 13.114 SCH 3 13.115 SOH 3 13.116 SOH 3 13.117 SCH 3 13.118 SCH 3 13.119 SCH 3 13.120 SCH 3 13.121 SOH 3 13.122 SCH 3 13.123 SOH 3 13.124 SCH 3 13.125 SCH 3 13.126 SCH 3 13.127 SOH 3 13.128 SOH 3 13.129 SOH 3 13.130 SOH 3 13.131 SCH 3 13.132 SOH 3 13.133 SCH 3 13.134 00H 3 Phys. data
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
SOH
3
SCH
3
SCH
3
SCH
3
SCH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SCH
3
SOH
3
SCH
3
SCH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SOH
3
SCH
3
SOH
3
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
OF
3 C0 2
CH
2
CH
3
H
OH
3
OF
3 C0 2
CH
2 0H 3
H
OH
3
OF
3 C0 2 0H 2
CH
3
H
OH
3
OF
3 C0 2
CH
2
CH
3
H
OH
3
OF
3 C0 2 0H 2
CH
3
H
OH
3
CF
3 C0 2
CH
2
CH
3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
H
OH
3
OF
3 C0 2
CH
2 0H 3
H
2 2 2 2 0 0 0 0 1 2 2 2 2 0 0 0 0 WO 99/09023 PCT/EP98/05247 91 Compd. R 6 R6 R 7Rs n Phys. data No.
13.135 00H 3 H H H OH 3 0 13.136 00H 3 H H H CF 3 0 13.137 00H 3 H H H CO 2
CH
2
CH
3 0 13.138 00H 3 H H H H 1 13.139 00H 3 H H H CH 3 1 13.140 OCH 3 H H H CF 3 1 13.141 00H 3 H H H CO 2
CH
2
CH
3 1 13.142 OCH 3 H H H H 2 13.143 00H 3 H H H OH 3 2 13.144 00H 3 H H H CF 3 2 13.145 OCH 3 H H H CO 2
CH
2
CH
3 2 13.146 OCH 3 H OH 3 H H 0 1 3.147 OCH 3 H OH 3 H OH 3 0 13.148 OCH 3 H OH 3 H OF 3 0 13.149 OCH 3 H OH 3 H C0 2 0H 2
CH
3 0 13.150 00H 3 H OH 3 H H 1 13.151 OCH 3 H OH 3 H OH 3 1 13.152 00H 3 H OH 3 H CF 3 1 13.153 00H 3 H OH 3 H CO 2
CH
2
CH
3 1 13.154 00H 3 H OH 3 H H 2 13.155 00H 3 H OH 3 H OH 3 2 13.156 00H 3 H OH 3 H CF 3 2 13.1 57 00H 3 H OH 3 H 00 2
OH
2 0H 3 2 13.158 00H 3
OH
3
OH
3 H H 0 resin (E isomer) 13.159 OCH 3
OH
3
OH
3 H H 0 104-1 0500 (Z isomer) 13.1 60 00H 3
OH
3
OH
3 H OH 3 0 13.161 00H 3
OH
3
OH
3 H OF 3 0 13.162 00H 3
OH
3
OH
3 H 00 2 0H 2 0H 3 0 13.163 00H 3
OH
3
OH
3 H H 1 13.164 00H 3
OH
3
OH
3 H OH 3 1 13.165 O0H 3
OH
3
OH
3 H OF 3 1 13.166 00H 3
OH
3
OH
3 H C0 2
CH
2
CH
3 1 WO 99/09023 PCT/lElD08 CIA-7 -92- Oompd. R 6
R
6
R
7 R7RIB n Phys. data No.
13.167 OCH 3
CH
3
OH
3 H H 2 resin (Z isomer) 13.168 00H 3
CH
3
OH
3 H H 2 resin (E isomer) 13.169 OCH 3
OH
3
OH
3 H CH 3 2 13.170 OCH 3
OH
3
OH
3 H OF 3 2 13.171 00H 3
OH
3
OH
3 H 00 2
CH
2 0H 3 2 13.172 OCH 3
CH
3
OH
3
OH
3 H 0 13.173 OOH 3
CH
3
CH
3
OH
3
CH
3 0 13.174 00H 3
OH
3
OH
3
OH
3
OF
3 0 13.175 00H 3
OH
3
CH
3
OH
3 C0 2
CH
2 0H 3 0 13.176 00H 3
CH
3
CH
3
OH
3 H 1 13.177 00H 3
OH
3
OH
3
OH
3
OH
3 1 13.178 OCH 3
OH
3
OH
3
OH
3
OF
3 1 13.179 00H 3
OH
3
OH
3
OH
3 C0 2
OH
2 0H 3 1 13.180 00H 3
OH
3
OH
3
OH
3 H 2 13.181 00H 3
OH
3
OH
3
OH
3
OH
3 2 13.182 00H 3
OH
3
OH
3
OH
3
OF
3 2 13.183 00H 3
OH
3
OH
3
OH
3 00 2 0H 2 0H 3 2 13.184 00H 3 H 00H 3 H H 0 13.185 00H 3 H 001-3 H OH 3 0 13.186 00H 3 H O0H 3 H CF 3 0 13.1 87 00H 3 H 00H 3 H 00 2 0H 2 0H 3 0 13.188 00H 3 H 00H 3 H H 1 13.189 00H 3 H 00H 3 H OH 3 1 13.190 00H 3 H O0H 3 H CF 3 1 13.191 00H 3 H 00H 3 H 00 2
CH
2 0H 3 1 13.192 O0H 3 H 00H 3 H H 2 13.193 O0H 3 H O0H 3 H OH 3 2 13.194 00H 3 H 00H 3 H OF 3 2 13.195 00H 3 H 00H 3 H 00 2 0H 2 0H 3 2 13.196 00H 3
OH
3 00H 3
OH
3 H 0 13.197 00H 3
OH
3 00H 3
OH
3
OH
3 0 13.198 00H 3
OH
3 00H 3
OH
3
OF
3 0 WO 99/09023 WO 9909023PCTEP9/0527 93 Oompd. R 6 R6 Rf7l1 Phys. data No.
13.199 00H 3
OH
3
OCH
3
OH
3
OO
2
CH
2
CH
3 0 13.200 00H 3
OH
3
OCH
3
OH
3 H 1 13.201 00H 3
OH
3 00H 3
OH
3
OH
3 1 13.202 00H 3
OH
3
OCH
3
OH
3
CF
3 1 13.203 00H 3
OH
3 00H 3
CH
3 C0 2
CH
2
CH
3 1 13.204 00H 3
OH
3
OCH
3
CH
3 H 2 13.205 00H 3
OH
3 00H 3
OH
3
OH
3 2 13.206 00H 3
OH
3 00H 3
OH
3
CF
3 2 13.207 00H 3
OH
3 00H 3
OH
3 C0 2 0H 2
CH
3 2 13.208 SOH 3
OH
3 00H 3 H H 0 amorphous 13.209 SOH 3
OH
3 00H 3 H OH 3 0 13.210 SOH 3
OH
3 00H 3 H OF 3 0 13.211 SOH 3
OH
3 00H 3 H C0 2 0H 2 0H 3 0 13.212 SOH 3
OH
3 00H 3 H H 1 13.213 SOH 3
OH
3 00H 3 H OH 3 1 13.214 SOH 3
OH
3 00H 3 H OF 3 1 13.215 SCH 3
OH
3 00H 3 H 00 2 0H 2 0H 3 1 13.216 SOH 3
OH
3 00H 3 H H 2 166-1680C 13.217 SOH 3
OH
3 00H 3 H OH 3 2 13.218 SOH 3
OH
3 00H 3 H OF 3 2 13.219 SOH 3
OH
3 00H 3 H 00 2 0H 2 0H 3 2 13.220 SCH 3
OH
3 00H 3
OH
3 H 0 13.221 SOH 3
OH
3
OCH
3
OH
3
OH
3 0 13.222 SOH 3
OH
3 00H 3
OH
3
CF
3 0 13.223 SOH 3
OH
3
OOH
3
OH
3 C0 2 0H 2
OH
3 0 13.224 SOH 3
OH
3 00H 3
OH
3 H 1 13.225 SOH 3
OH
3 00H 3
OH
3
OH
3 1 13.226 SOH 3
OH
3 00H 3
OH
3
OF
3 1 13.227 SOH 3
OH
3 00H 3
OH
3 00 2 0H 2 0H 3 1 13.228 SOH 3
OH
3 00H 3
OH
3 H 2 13.229 SOH 3
OH
3 00H 3
OH
3
OH
3 2 13.230 SOH 3
OH
3 00H 3
OH
3
OF
3 2 WO 99/09023 WO 9909023PCT/EP98/05247 -94- Compd.
No.
13.231 13.232 13.233 13.234 13.235 13.236 13.237 13.238 13.239 13.240 13.241 13.242 13.243 13.244 13.245 13.246 13.247 13.248 13.249 13.250 13.251 13.252 13.253 13.254 13.255 13.256 13.257 13.258 R6R 6
R
7 Phys. data
SCH
3
OH
3
CH
3
CH
3
OH
3
OH
3
CH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OH
3
OH
3
OH
3 00H 3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
CH
2
CH=CH
2
CH
2
OH=CH
2
OH
2
OH=CH
2
OH
2 CH=0H 2
OH
2
OH=CH
2
OH
2 CH=0H 2
CH
2
OH=CH
2
OH
2
CH=CH
2
OH
2 OH=OH2
CH
2 OH=0H 2
CH
2 CH=0H 2
CH
2 C0H
CH
2
CCH
CH
2
CCH
CH
2 00H
OH
2 00H
OH
2 00H
CH
2 00H
CH
2 00H
OH
2 C0H
OH
2 00H
CH
2 00H
OH
2 00H
CH
2 C0H
OH
2 CH=0H 2
OH
2 OH=0H 2
OH
2
CH=CH
2
CO
2
CH
2
CH
3
H
OH
3
CF
3 00 2 0H 2
CH
3
H
OH
3
CF
3 00 2 0H 2
CH
3
H
OH
3
CF
3 00 2
CH
2
CH
3
H
OH
3
OF
3 O0 2 0H 2 0H 3
H
OH
3
OF
3 00 2
CH
2
CH
3
H
OH
3
OF
3 C0 2
CH
2
CH
3
H
OH
3
OF
3 viscous oil viscous oil 13.259 OH 3
OH
3
OH
3
OH
2 OH=0H 2 C0 2
CH
2
CH
3 WO 99/09023 WO 9909023PCT/EP98/05247 95 Oompd.
No.
13.260 13.261 13.262 13.263 13.264 13.265 13.266 13.267 13.268 13.269 13.270 13.271 13.272 13.273 13.274 13.275 13.276 13.277 13.278 13.279
R
6
R
6 R Phys. data
CH
3
CH
3
OH
3
OH
3
OH
3
OH
3
CH
3
OH
3
CH
3
OH
3
OH
3
OH
3
CH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
3
OH
2
OH=CH
2
CH
2 OH=0H 2
OH
2 OH=0H 2
OH
2
OH=CH
2
OH
2
OH=CH
2
OH
2 CH=0H 2
OH
2 OH=0H 2
OH
2
CCH
CH
2 00H
CH
2 00H
OH
2 00H
OH
2 00H
OH
2 00H
OH
2
CCH
OH
2 00H
CH
2 00H
CH
2 00H
OH
2 C0H
OH
2 00H
CH
2
CCH
H
OH
3
OF
3 00 2 0H 2
CH
3
H
OH
3
OF
3 C0 2
CH
2 0H 3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
OH
3
OF
3 00 2 0H 2
CH
3
H
OH
3
OF
3 C0 2
CH
2
CH
3 Table 0: Physico-chemical data for prepared compounds in the above-mentioned Tables 1 6 and A, and also 8-1 1 and B. The figure before the point indicates the number of the Table, e.g. 1.027 indicates in Table 1 compound No. 027 of Table A, and 11.027 indicates in Table 11 compound No. 027 of Table 0.
Compd.
No.I 1.001 1.002 1.003 Physico-chemical data m.p. 21 5-21 800 m.p. 18000 m.p. 204-2060C WO 99/09023 -9 Compd. Physico-chemical data No.
1.005 m.p. 225-2260C 1.008 m.p. 213-21600 1.016 m.p. 194-1960C 1.027 m.p. 223-2250C 1.029 m.p. 220-2300C 1.030 m.p. 222 0
C
1.031 m.p. 263-2640C 1.033 m.p. 187-1 890C 1.034 m.p. 220-221001 2.001 m.p. 123-1260C 2.002 m.p. 127-129*C 2.003 m.p. 112-1140C 2.005 m.p. 133-134 0
C
2.008 m.p. 173-17400 2.027 m.p. 170-172 0
C
2.028 m.p. 168-17100C 2.029 m.p. 173-174 0
C
2.030 m.p. 252 0
C
2.033 m.p. 132-1 3500 2.034 m.p. 206 0
C
2.807 m.p. 134-1350C 3.027 m.p. 183-1840C 3.029 m.p. 185-186 0
C
3.033 m.p. 141-144 0
C
5.027 resin 6.005 resin 6.027 m.p. 194-19500 6.029 m.p. 189-190 0
C
9.001 m.p. 129-13000 9.027 m.p. 178-180 0
C
10.001 m.p. 191.19300 10.003 m.p. 192.19300 PCT/EP98/05247 WO 99/09023 PCT/IFPq98/n47 -97- Compd. Physico-chemical data No.
10.016 m.p. 199-200°C 10.027 m.p. 230-233°C 10.029 m.p. 191-192 C 10.033 m.p. 222-224°C 11.001 m.p. 185-188 0
C
11.027 m.p. 216-218 0
C
11.040 m.p. 117-120°C 11.066 m.p. 213-215 0
C
Examples of specific formulations for compounds of formula I, such as emulsifiable concentrates, solutions, wettable powders, coated granules, extruder granules, dusts and suspension concentrates, are described on pages 9 to 13 of WO 97/34485.
Biological Examples Example B1: Herbicidal action prior to emergence of the plants (pre-emergence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots.
Immediately after sowing, the test compounds, in the form of an aqueous suspension or emulsion prepared from a 25 wettable powder (Example F3, as described, for example, in WO 97/34485, or in the form of an emulsion (prepared from a 25 emulsifiable concentrate (Example Fl, as described, for example, in WO 97/34485), are applied by spraying in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown in a greenhouse under optimum conditions.
After a test duration of 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 total damage, 9 no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Cyperus, Sinapis, Solanum The compounds according to the invention exhibit good herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B1.
WO 99/09023 PCT/EP98/05247 -98- Table B1: Pre-emergence action: Test plant: Cyperus Sinapis Solanum Conc.
[g a.i./ha] Compound No.
2.001 6 2 2 2000 2.003 1 1 1 2000 2.027 3 2 2 2000 2.029 1 1 1 2000 2.034 3 5 3 2000 2.807 2 2 5 2000 3.027 3 1 1 2000 6.029 3 2 2 2000 9.001 3 2 1 2000 10.001 4 5 3 2000 10.027 3 3 2 2000 11.027 4 4 1 2000 12.012 3 7 3 2000 13.007 2 2 2 2000 13.022 3 2 2 2000 13.030 4 4 2 2000 13.038 3 2 2 2000 The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 to F8, as described, for example, in WO 97/34485.
Example B2: Post-emergence herbicidal action In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastics pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension or emulsion of the test compounds of formula I, prepared from a 25 wettable powder (Example F3, as described, for example, in WO 97/34485, or in the form of an emulsion (prepared from a 25 emulsifiable concentrate (Example Fl, as described, for example, in WO 97/34485), in a concentration corresponding to 2000 g of active ingredient/ha (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a WO 99/09023 PCT/EP98/05247 -99scale of nine ratings (1 total damage, 9 no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Sinapis, Solanum, Stellaria In this test too, the compounds of formula I exhibit strong herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B2.
Table B2: Post-emergence action: Test plant: Setaria Sinapis Solanum Stellaria Conc.
[g a.i./ha] Compd. No.
2.001 3 1 2 4 2000 2.002 6 2 1 4 2000 2.003 4 2 2 3 2000 2.005 4 2 2 3 2000 2.008 5 2 2 2 2000 2.027 3 1 2 3 2000 2.028 3 2 2 3 2000 2.029 5 2 2 2 2000 2.030 5 2 2 2 2000 2.034 3 2 2 3 2000 2.807 3 2 1 2 2000 3.027 4 1 1 4 2000 3.029 5 2 2 2 2000 5.027 3 2 1 2 2000 6.005 2 2 2 2 2000 6.027 5 1 4 3 2000 6.029 7 1 1 2 2000 7.027 8 2 2 4 2000 9.001 4 1 1 3 2000 9.027 3 2 2 4 2000 10.001 3 1 1 3 2000 WO 99/09023 PCT/EPO9/0247 -100- 10.003 3 1 2 3 2000 10.016 3 2 3 3 2000 10.027 3 1 2 4 2000 10.029 3 3 2 3 2000 11.001 2 1 2 3 2000 11.027 2 2 2 2 2000 11.040 1 2 2 2 2000 11.066 2 1 2 2 2000 12.012 3 1 1 3 2000 13.001 4 1 1 3 2000 13.007 3 1 2 2 2000 13.022 5 1 1 2 2000 13.030 5 1 1 2 2000 13.034 3 1 1 3 2000 13.038 3 1 1 2 2000 13.042 4 1 1 2 2000 13.058 6 2 2 3 2000 13.059 7 3 2 4 2000 13.071 7 2 1 2 2000 13.079 4 1 1 3 2000 13.080 6 1 1 2 2000 13.158 2 1 1 2 2000 13.159 3 3 3 3 2000 13.167 2 1 1 2 2000 13.168 2 2 2 2 2000 13.216 6 2 4 2 2000 13.240 3 1 2 3 2000 13.252 3 3 2 3 2000 The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 to F8, as described, for example, in WO 97/34485.
P.\OPERA\Ml\9344 1-98 sp, dOcl-(/Ol/O)l 100A- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.
*o o oo* *o *oo *ooo ooo *o o* oo
Claims (2)
101- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: A compound of formula I R2 S(O) 0 wherein R, is C 1 -C 4 alkyI, Cl-C 4 haloalkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, Cl-C 4 alkoxycarbonyl, cyano, cyano- Cl -C 4 alkyI, hydroxy-Cl-C 4 alkyl, amino-Cl-C 4 alkyl, CHO, Cl-C 4 alkyI-ON=CH, C 2 -C 6 alkenyl, Cl -C4alkoxycarbonyl-C 2 -C 6 alkenyl or a group CH(0R 20 )0R 21 R 20 and R 21 are each independently of the other C 1 -C 4 alkyl; or R 20 and R 21 together are nj is 2, 3 or 4; R 2 is hydrogen or C 1 -C 4 alkyI; R 3 and R 4 are each independently of the other hydrogen, C 1 -C 4 alkyI or halogen; n isO0, 1 or 2; R 5 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 6 alkeny[, C 2 -C 6 alkynyl, CI-C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkyI-S(O), 2 (Cl-C 4 alkyl) 2 NS(O) 2 Cl-C 4 alkyl-S(O) 2 0, halogen, nitro or cyano; n 2 isO0, 1 or 2; S .5*S S. Q is OH, halogen or a group R 8 4) ,N (Q 5 or NH- WO 99/09023 PCT/EP98/05247 102 R 13 (Q 6 R): 4 0 R 6 and R 7 are each independently of the other hydrogen, OH, Cl-C 4 alkyI, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cl-C 4 alkoxycarbonyl, C 1 -C 4 alkyl-S(O)1 2 Cl-C 4 alkyl-NHS(O) 2 phenyl or phenyl substituted by Cl-C 4 alkyl, Cl-C 4 haloalkyl, Cl-C 4 alkoxy, C 1 -C 4 haloalkoxy, Cl-C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, amino, Cl-C 4 alkylamino, di-Cl-C 4 alkylamino, Cl-C 4 alkyI-S(O)1 2 Cl -C 4 alkyl-S(O) 2 0, C 1 -C 4 haloalkyl-S(O),1 2 C 1 -C 4 haloalkyl-S(O) 2 0, Cl-C~alkyl-S(O) 2 NH, C 1 -C 4 alkyl-S(O) 2 N(C 1 -C 4 alkyI), halogen, nitro, COCH or cyano; or R 6 and R 7 are each independently of the other Cl-C 4 haloalkyl, -NH-Cl-C 4 alkyl, -N(Cl-C 4 alkyl) 2 Cl-C 6 alkoxy, cyano, nitro or halogen; or adjacent R 6 and R 7 together are -(CH 2 ),1 3 n 3 is 2,3, 4, 5or6; W is oxygen, sulfur, -C(Rl 8 2 or -N(R 22 nr, is 0 or 1, or when W is -C(R 18 2 n 6 may additionally be 2 or 3; each R 18 independently of the other is hydrogen, C 1 -C 4 alkyl, CI-C 4 haloalkyl or Cl-C 4 alkoxy- carbonyl; or R 18 together with one of the adjacent substituents R 7 forms a single bond when n 6 is 1, and the remaining gemninal R 6 and R 7 are other than hydrogen; R 22 is hydrogen, C 1 -C 4 alkyl or Cl-C 4 alkoxycarbonyl; R 8 is OH, CI -C 4 alkoxy, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyloxy, R 23 R 24 N-C(O)O, phenylthio, C 1 -C 4 alkylthio, Cl-C 4 alkyl-S(O) 2 0, (C 1 -C 4 alkoxy) 2 P(O)O, Cl-C 4 alkyl(C 1 -C 4 alkoxy)P(O)O, H(Cl-C 4 alkoxy)P(O)O or benzoyloxy; R 23 and R 24 are each independently of the other hydrogen or Cl-C 4 alkyl; Y is oxygen, sulfur or -(CH 2 )n 5 n 5 is 0,1, 2, 3or 4; R 9 is hydrogen, Cl-Cralkyl, Cl-C 4 alkylcarbonyl, Cl-C 4 alkoxycarbonyl, (Cl-C 4 alkyl)NHCO or (Cl-C 4 alkyl) 2 NCO; WO 99/09023 PCT/VPQR/flr,')A-7 -103- Rio, Ril and R 12 are each independently of the others hydrogen, Cl-C 4 alkyl, Cl-C 4 alkoxy- carbonyl, phenyl or phenyl substituted by CI-C 4 alkyl, Cl-C 4 haloalkyl, C 1 -C 4 alkoxy, CI-C 4 haloalkoxy, C 1 -C 4 alkylcarbonyl, Cl-C 4 alkoxycarbonyl, amino, Cl-C 4 alkylamino, di-C 1 -C 4 alkyI- amino, Cl-C~AlkyI-S(O)n 2 C 1 -C 4 alkyI-S(O) 2 0, Cl C 4 haloalky-S(O)n 2 C 1 -C 4 haloalkyl-S(O) 2 0, C 1 -C 4 alkyI-S(O) 2 NH, C 1 -C 4 alkyl-S(O) 2 N(C 1 -C 4 alkyl), halogen, nitro, COOH or cyano; R 13 is hydrogen; halogen; Cl-C 4 alkyl; C 1 -C 4 alkyl substituted by unsubstituted or R 17 substituted phenyl; Cl-C 4 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl; C 2 -C~alkynyl; C 2 -C 6 alkynyl substituted by unsubstituted or R 17 substituted phenyl; C 3 -C 6 haloalkenyl; C 3 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 3 -C 6 CYCloalkyl substituted by halogen, R 1 5 or C00R 16 C00R 16 COR 1 5 cyano; nitro; CONH- 2 (Cl-C 4 alkyl)NHCO; (C 1 -C 4 alkyl) 2 NCO; (Cl-C 4 haloalkyl)NHCO; (C 1 -C 4 haloalkyl) 2 NCO; CI-C 4 alkyl- S(O)n 2 Cl-C 4 alkyl-S(O), 2 substituted by unsubstituted or R 17 -substituted phenyl; C 1 -C 4 alkoxy-C 2 -C 6 alkyl-S(O), 2 C 2 -C 6 alkenyI-S(O),, 2 C 2 -C 6 alkenyl-S(O),, 2 substituted by unsubstituted or R 1 7 -substituted phenyl; C 2 -C 6 alkynyl-S(O)n 2 or C 2 -C 6 alkynyl-S(O),, 2 substituted by unsubstituted or R 17 -substituted phenyl; R 15 is Cl-C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 halo- alkynyl, phenyl or R 17 -substituted phenyl; R 1 6 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R 17 is halogen, C 1 -C 4 alkyl, Cl-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, CI -C 4 alkoxy-C, -C 4 alkyl, C 1 -C 4 alkoXY-C 3 -C 6 alkenyl, C 1 -C 4 alkoxy-C 3 -C 6 alkynyl, cyano, nitro, COOH, C 1 -C 4 alkoxycarbonyl, Cl-C 4 haloalkoxycarbonyl, C 1 -C 4 alkyl- S(O)n 2 Cl-C 4 haloalkyl-S(O), 2 phenyi-S(O), 2 phenyl-S(O), 2 Substituted on the phenyl ring by halogen, CI-C 4 alkyl, Cl-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COOH, C 1 -C 4 alkoxycarbonyl, CI-C 4 alkyl-S(O), 2 CI-C 4 haloalky-S(O)n 2 Cl-C 4 alkylcarbonyl, di-C 1 -C 4 alkyl- amino, Cl-C 4 alkoxy, Cl-C 4 haloalkoxy, C 1 -C 4 alkyl-S(O) 2 0 or C 1 -C 4 haloalkyl-S(O) 2 0; 01-04- alkylcarbonyl, di-C 1 -C 4 alkylamino, Cl-C 4 alkyl-S(O) 2 NH, C 1 -C 4 alkyI-S(O) 2 N(C 1 -C 4 alkyl), CI-C 4 haloalkyl-S(O) 2 NH, C 1 -C 4 haloalkyl-S(O) 2 N(Cl-C 4 alkyl), NH 2 S(O) 2 (Cl-C 4 alkyl)NHS(O) 2 (C 1 -C 4 alkyl) 2 NS(O) 2 CONH- 2 (C 1 -C 4 alkyl)NHCO, (C 1 -C 4 alkyI) 2 NCO, NH 2 CS, (Cl-C 4 alkyl)NHCS, (C 1 -C 4 alkyl) 2 NCS, C 1 -C 4 alkoxy, Cl-C 4 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Cl-C 4 alkyl-S(O) 2 0, Cl-C 4 haloalkyl-S(O) 2 0, phenyl-S(O) 2 0 or phenyl- S(O) 2 0 substituted on the phenyl ring by halogen, C 1 -C 4 alkyl, CI-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COOH, Cl-C 4 alkoxycarbonyl, Cl-C 4 alkyI-S(O),, 2 CI-C 4 haloalkyl- WO 99/09023 WO 9909023PCT/EP98/05247 -104 S(O),1 2 Cl-C 4 alkylcarbonyl, di-Cl-C 4 alkylamino, C 1 -C 4 alkoxy, Cl-C 4 haloalkoxy, Cl-C 4 alkyl- S(O) 2 0 or Cl-C 4 haloalkyl-S(O) 2 0; and R 14 is Cl -C 4 alkyl, Cl-C 4 haloalkyl, 0 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 halo- alkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by halogen, CI-C 4 alkyl, C 1 -C 4 halo- alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl or phenyl substituted by halogen, 0 1 -C 4 alkyl, Cl-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COCH, C 1 -C 4 alkoxycarbonyl, Cl-C 4 alkyI-S(O)n 2 Cl-C 4 haloalky-S(O)n 2 C 1 -C 4 alkylcarbonyl, di-Cj-C 4 alkylamino, C 1 -C 4 alkoxy, Cl-C 4 haloalkoxy, Cl-C 4 alkyI-S(O) 2 0 or Cl-C 4 haloalkyl- S(O) 2 0, or an agrochemically acceptable salt or a stereoisomner of such a compound of formula 1. 2. A compound according to claim 1, wherein R, is C 1 -C 4 alkyl, Cl-C 4 haloalkyl, 0 1 -C 4 alkoxy- Cl-C 4 alkyl, Cl-C 4 alkoxycarbonyl, cyano, cyano-0 1 -C 4 alkyI, CHO, C 1 -C 4 alkyl-ON=CH, C 2 -C 6 al kenyl,C01-C 4 alkoxycarbonyl-C 2 -C 6 alkenyl or agroup CH(0R 20 )0R 2 1 W is oxygen, sulfur, -0(RlB) 2 or -N(R 22 each RIB independently of the other is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxycarbonyl; and R 22 is hydrogen, 0 1 -C 4 alkyl or 0 1 -C 4 alkoxycarbonyl. 3. A process for the preparation of a compound of formula I RII R3 C WO 99/09023-10- wherein R, to R 5 and n are as defined in claim 1; 0 is a group PCT/EP98/05247 R 7 AQ), ~n 6 R 6 R 7 R 8 0Y) 0 8 N (03) or (Q 4 R 8 is OH; and R 6 R 7 R 9 Rio, W, n 6 and Y are as defined in claim 1, which comprises either a) reacting a compound of formula III 0 *CX (111), wherein R, to R 5 and n are as defined and X is a leaving group, in an inert organic solvent in the presence of a base with a compound of formula IV (IV), wherein Z, is C(R 6 )R 7 Z 2 is (W)n 6 Z 3 is C(R 6 )R 7 and n 4 is 0 group Qi); Z, is CH, Z 2 is oxygen, sulfur or -(CH 2 5 Z 3 is OH and n 4 is 2 group Q 2 Z, is CH 2 Z 2 is CHNHR 9 Z 3 is OH 2 and n 4 is 0 group Q3); or Z, is NR 10 Z 2 is oxygen, Z 3 is C(R 6 )R 7 and n 4 is 0 group 04), and R 6 R 7 R 9 Rio, W, n 6 and n 5 are as defined in claim 1, to form a compound of formula Ic WO 99/09023 PCT/EP98/05247 -106- R3 R4 R (Ic), (CH 2 4 and then isomerising that compound; or b) reacting a compound of formula Id O 0 SII 'C=OH (Id), wherein R 1 to R 5 and n are as defined, with a compound of formula IV 0 Z3 H o zI (CH 2 (IV), wherein Z 1 Z 2 Z 3 and n 4 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula Ic R S(n O R J (ic), and then isomerising that compound. WO 99/09023 WO 9909023PCT/EP98/05247 107 4. A compound of formula V 3I I II R wherein R, to R 5 R 14 and n are as defined in claim 1. A compound of formula VII R 2 0 0 R 3 I I I I SR 25 S 2 wherein R, to Rs, R 1 4 and n are as defined in claim 1; R 25 is Cl-C 4 alkyl, C 1 -C 4 alkyl substituted by unsubstituted or R 17 -substituted phenyl, C 1 -C 4 alkoxy-C 2 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R 1 7 -substituted phenyl, C 2 -C 6 alkynyl or C2-C6- alkynyl substituted by unsubstituted or R 17 -substituted phenyl; R 1 7 is halogen, C 1 -C 4 alkyI, Cl -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, Cl -C 4 alkoxy- C 1 -C 4 alkyI, CI -C 4 alkoXY-C 3 -C 6 alkenyl, Cj-C 4 alkoXY-C 3 -C 6 alkynyl, cyano, nitro, COOH, C 1 C 4 alkoxycarbonyl, C 1 -C 4 haloalkoxycarbonyl, C 1 -C 4 alkyl-S(O)1, 2 Cl-C 4 haloalkyl-S(O)1 2 phenyl-S(O),, 2 phenyl-S(O)r, 2 substituted on the phenyl ring by halogen, Cl-C 4 alkyI, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COCH, Cl-C 4 alkoxycarbonyl, C 1 -C 4 alkyl- S(O)1 2 C 1 -C 4 haloalkyI-S(O), 2 C 1 -C 4 alkylcarbonyl, di-C 1 -C 4 alkylamino, Cl-C 4 alkoxy, CI-C 4 haloalkoxy, Cl-C 4 alkyl-S(O) 2 0 or Cl-C 4 haloalkyl-S(O) 2 0; C 1 -C 4 alkylcarbonyl, di-Cl-C 4 alkyI- amino, C 1 -C 4 alkyl-S(O) 2 NH, C 1 -C 4 alkyI-S(O) 2 N(C 1 -C 4 alkyI), Cl-C 4 haloalkyl-S(O) 2 NH, C 1 -C 4 haloalkyl-S(O) 2 N(Cl-C 4 -alkyl), NH 2 S(O) 2 (Cl-C 4 alkyI)NHS(O) 2 (Cl-C 4 alkyl) 2 NS(O) 2 CONH- 2 (Cl-C 4 alkyl)NHCO, (C 1 -C 4 alkyI) 2 NCO, NH 2 CS, (C 1 -C 4 alkyl)NHCS, (C 1 -C 4 aikyI) 2 NCS, C 1 -C 4 alkoxy, Cl -C 4 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 4 alkyl-S(O) 2 0, C 1 -C 4 halo- alkyl-S(O) 2 0, phenyl-S(O) 2 0 or phenyl-S(O) 2 0 substituted on the phenyl ring by halogen, C 1 -C 4 alkyl, Cl-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COOH, Cl-C 4 alkoxy- carbonyl, Cl-C 4 alkyl-S(O),1 2 Cl-C 4 haloalkyl-S(O)n 2 C 1 -C 4 alkylcarboryl, di-C 1 -C 4 alkylamino, WO 99/09023 WO 9909023PCT[EP98/(15247
108- C 1 -C 4 alkoxy, Cl-C 4 haloalkoxy, C 1 -C 4 alkyl-S(O) 2 0 or C 1 -C 4 haloalkyl-S(O) 2 0; and n 2 is 0, 1 or 2. 6. A compound of formula IX R3II II I I I R 13 N(R'2) 2 wherein R, to R 5 R 14 and n are as defined in claim 1; R 1 3 is hydrogen, Cl-C 4 alkyl, C 1 -C 4 alkyI substituted by unsubstituted or R 17 -Substituted phenyl, C 1 -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or Rir-substituted phenyl, C 2 -C 6 alkynyl, C 2 -C 6 alkynyl substituted by unsubstituted or R 17 -Substituted phenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyI substituted by halogen, Ris or C00R 16 R 1 7 is halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -Crhaloalkynyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyI, C 1 -C 4 alkoXY-C 3 -C 6 alkenyl, C 1 -C 4 alkoXY-C 3 -C 6 alkynyl, cyano, nitro, COON, C 1 -C 4 alkoxycarbonyl, Cl-C 4 haloalkoxycarbonyl, C 1 -C 4 alkyl-S(O),, 2 C 1 -C 4 haloalkyl- S(O), 2 phenyl-S(O), 2 pheny-S(O)n 2 substituted on the phenyl ring by halogen, Cl-C 4 alkyI, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COON, C 1 -C 4 alkoxycarbonyl, C 1 -C~Alkyl-S(O)n 2 CI-C 4 haloalkyl-S(O)n 2 C 1 -C 4 alkylcarbonyl, di-Cl-C 4 alkylamino, Cl-C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkyl-S(O) 2 O or C 1 -C 4 haloalkyl-S(O) 2 0; CI-C 4 alkyI- carbonyl, di-Cl-C 4 alkylamino, Cl-C~alkyl-S(O) 2 NH, C 1 -C 4 alkyl-S(O) 2 N(C 1 -C 4 alkyI), C 1 -C 4 haloalkyl-S(O) 2 NH, C 1 -C 4 haloalkyl-S(O) 2 N(Cl-C 4 a~kyl), NH 2 S(O) 2 (C 1 -C 4 alkyl)NHS(O) 2 (C 1 -C 4 alkyI) 2 NS(O) 2 CONH- 2 (Cl-C 4 alkyl)NHCO, (C 1 -C 4 alkyl) 2 NCO, NH 2 CS, (C 1 -C 4 alkyI)- NHCS, (C 1 -C 4 alkyI) 2 NCS, C 1 -C 4 alkoxy, CI-C 4 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Cl-C 4 alkyl-S(O) 2 0, C 1 -C 4 haloalkyl-S(O) 2 0, phenyl-S(O) 2 0 or phenyl-S(O) 2 0 substituted on the phenyl ring by halogen, CI-C 4 aIkyl, Cl-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COON, C 1 -C 4 alkoxycarbonyl, Cl-C 4 alkyI-S(O), 2 Cl-C 4 haloalkyl-S(O)n 2 CI-C 4 alkyl- carbonyl, di-Cl-C 4 alkylamino, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, Cl-C 4 alkyI-S(O) 2 0 or CI-C 4 halo- alkyl-S(O) 2 0; n 2 is 0, 1 or 2; R 1 5 is Cl-C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl or R 17 -substituted phenyl; R 16 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and R 27 is Cl-C 4 alkyl. P:\OPER\Mal\93441 -fl spc doc-(4)602/l -109- 7. A herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective content of a compound of formula I, and an inert carrier. 8. A method of controlling undesired plant growth, wherein a compound of formula I, or a composition comprising such a compound, is applied in a herbicidally effective amount to the crops of useful plants or to the locus thereof. 9. The use of a composition according to claim 7 in controlling undesired plant growth. A compound of formula I according to claim 1 or a compound of formula V according to claim 4 or a compound of formula VII according to claim 5 or a compound of formula IX according to claim 6, substantially as hereinbefore described with reference to the Examples. DATED this 6th day of February, 2001 Novartis AG By DAVIES COLLISON CAVE Patent Attorneys for the Applicants
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH195097 | 1997-08-20 | ||
| CH1950/97 | 1997-08-20 | ||
| PCT/EP1998/005247 WO1999009023A1 (en) | 1997-08-20 | 1998-08-18 | Benzothiophene derivates as herbicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU9344198A AU9344198A (en) | 1999-03-08 |
| AU732154B2 true AU732154B2 (en) | 2001-04-12 |
Family
ID=4222392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU93441/98A Ceased AU732154B2 (en) | 1997-08-20 | 1998-08-18 | Benzothiophene derivates as herbicides |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1005467A1 (en) |
| CN (1) | CN1261884A (en) |
| AU (1) | AU732154B2 (en) |
| BR (1) | BR9811314A (en) |
| CA (1) | CA2291101A1 (en) |
| WO (1) | WO1999009023A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9916177A (en) | 1998-10-06 | 2001-08-14 | Idemitsu Kosan Co | Trichetone derivatives and herbicides |
| DE19935218A1 (en) * | 1999-07-27 | 2001-02-01 | Aventis Cropscience Gmbh | Isoxazolyl-substituted benzoylcyclohexanediones, process for their preparation and their use as herbicides and plant growth regulators |
| MXPA02002450A (en) * | 1999-09-08 | 2004-09-10 | Aventis Cropscience Uk Ltd | New herbicidal compositions. |
| AU2001242451A1 (en) * | 2000-03-09 | 2001-09-17 | Syngenta Participations Ag | Acylated phenyl or pyridine herbicides |
| AU2001284480A1 (en) * | 2000-12-21 | 2002-07-01 | Idemitsu Kosan Co. Ltd. | Benzothiophene derivatives and herbicidal compositions containing the same |
| BR112016000059B1 (en) | 2013-07-02 | 2020-12-29 | Syngenta Participations Ag | bi or tricyclic heterocycles compounds, composition comprising said compounds, method for combating and controlling pests, method for protecting plant propagation material from attack by pests and plant propagation material coated with said composition |
| CN112430228B (en) * | 2020-11-25 | 2021-09-07 | 四川大学 | Chiral 2, 3-dihydrobenzo [ b ] thiophene 1, 1-dioxide, derivative and preparation method |
| WO2023094304A1 (en) | 2021-11-25 | 2023-06-01 | Syngenta Crop Protection Ag | Microbiocidal heterobiaryl amide derivatives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997008164A1 (en) * | 1995-08-25 | 1997-03-06 | E.I. Du Pont De Nemours And Company | Bicyclic herbicides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5946272A (en) * | 1982-09-09 | 1984-03-15 | Nissan Chem Ind Ltd | Pyrazole derivative, its preparation and selective herbicide containing said derivative |
| DE3862944D1 (en) * | 1987-02-09 | 1991-07-04 | Ciba Geigy Ag | NEW CYCLOHEXANDIONE. |
| US5006150A (en) * | 1987-06-05 | 1991-04-09 | Sandoz Ltd. | Substituted heterocyclohexane-3,5-diones |
| HU206242B (en) * | 1988-04-18 | 1992-10-28 | Sandoz Ag | Herbicidal compositions comprising substituted benzoyl bicyclodione derivatives as active ingredient |
| UA48120C2 (en) * | 1994-08-01 | 2002-08-15 | Рон-Пуленк Егрікалче Лімітед | Method of weed control, herbicidal composition, product, which contains synergetic herbicidal composition |
| US5627131A (en) * | 1995-01-09 | 1997-05-06 | Zeneca Limited | Herbicidal compositions of 4-benzoylisoxazole and antidotes therefor |
| AU4875296A (en) * | 1995-02-24 | 1996-09-11 | Basf Aktiengesellschaft | Isoxazolyl-benzoyl derivatives |
| AU710172B2 (en) * | 1995-02-24 | 1999-09-16 | Basf Aktiengesellschaft | Pyrazolylbenzoyl derivatives |
-
1998
- 1998-08-18 AU AU93441/98A patent/AU732154B2/en not_active Ceased
- 1998-08-18 EP EP98946374A patent/EP1005467A1/en not_active Withdrawn
- 1998-08-18 CA CA002291101A patent/CA2291101A1/en not_active Abandoned
- 1998-08-18 WO PCT/EP1998/005247 patent/WO1999009023A1/en not_active Application Discontinuation
- 1998-08-18 CN CN 98806742 patent/CN1261884A/en active Pending
- 1998-08-18 BR BR9811314-3A patent/BR9811314A/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997008164A1 (en) * | 1995-08-25 | 1997-03-06 | E.I. Du Pont De Nemours And Company | Bicyclic herbicides |
Also Published As
| Publication number | Publication date |
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| CN1261884A (en) | 2000-08-02 |
| WO1999009023A1 (en) | 1999-02-25 |
| EP1005467A1 (en) | 2000-06-07 |
| CA2291101A1 (en) | 1999-02-25 |
| BR9811314A (en) | 2000-08-29 |
| AU9344198A (en) | 1999-03-08 |
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