CA2039770A1 - 2-aryl-6-hetarylpyridine derivatives - Google Patents

2-aryl-6-hetarylpyridine derivatives

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Publication number
CA2039770A1
CA2039770A1 CA 2039770 CA2039770A CA2039770A1 CA 2039770 A1 CA2039770 A1 CA 2039770A1 CA 2039770 CA2039770 CA 2039770 CA 2039770 A CA2039770 A CA 2039770A CA 2039770 A1 CA2039770 A1 CA 2039770A1
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Prior art keywords
phenyl
alkyl
methyl
carbon atoms
formula
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CA 2039770
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French (fr)
Inventor
Akihiko Yanagi
Ulrich Heinemann
Peter Babczinski
Klaus Lurssen
Hans-Joachim Santel
Robert R. Schmidt
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

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

Abstract

ABSTRACT OF THE DISCLOSURE
Herbicidal 2-aryl-6-hetarylpyridines of the formula (I) in which R1 represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 independently of one another represent hydrogen or alkyl, Het represents in each case unsubstituted or substituted pyridyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, thienyl, furyl, thiazolyl, isothiazolyl, oxazolyl or isoxazolyl, and Z represents hydrogen, halogen or the groups -Xn-R5-1 or , where Le A 27 559-US

X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent in each case optionally substituted alkyl, alkenyl or alkynyl, R6 represents hydrogen or alkyl, or R5-2 and R6 together with the nitrogen atom to which they are bonded form a 5- to 7-membered satura-ted or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups, and n represents 0 or 1, with certain exceptions.
Le A 27 559

Description

- 2 ~ 3 ~ ~ 7 ~

~Ae invention relates to new 2-aryl-6-hetaryl-pyridine derivatives, to new intermediates and a plural-ity of processes for their preparation, and to their u6e as herbicides.
It has already been disclosed that ~ertain 4 sub~tituted 2,6-dlphenylpyridine deri~atives hav~ herbi-cidal properties (cf. ~P-A 263,958).
The following compounds are al80 known: 5-methyl-3-trifluoromethyl-1-(6-phenyl-4-trifluoromethyl-2-pyrid-yl)-pyrazole (cf. J. Heterocycl. Chem., 6 (2), 223 (1969)); 2-(4-dimethyl2mino-phenyl)-~-(2,5-dimethyl-pyrrol-1-yl)-pyridine (cf. J. Amer. Chem. Soc. k8, 326 (1946)); 6-phenyl-(2,2'-bipyridyl) (cf. Chem. Ber. 109, 3864 (1976)); 4-methylthio-6-phenyl-2,2'-bipyridine ~cf.
US Patent 4,451,659); 4-methyl-2-phenyl-6-(2-thienyl)-pyridine (cf J. Org. Chem. 50 (7), 1125-6 (1985)); 6-~4-(bromomethyl)phenyl]-2,2'-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine (cf. Inorg. Chem. 22 (20), 2818-24 (1983)); 4-(methylthio)-2-phenyl-6-~2-~hienyl)-pyridine ~0 (cf. J. Org. Chem. 47 (16), 3027~38 (198~ However, nothing i8 known about ~he pos~ibility of using the abovementionad compound~ as a herbicide.
New 2-Aryl-6-hetarylpyridine derivati~es of the general formula (I) Z
R4~R3 ` .
1?~ SI~
~61t ~ ,.
~2 ~e A 27 5$9 ~ 1 7 '~ ~

in which Rl represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogeno~lkyl, R3 and R~ independ~ntly of one another repre~ent hydrogen or alkyl, Het repre~ents in ~ach case unsubstituted or substituted pyridyl, pyrazinyl, pyrrolyl, pyrazolyl~ imidazolyl, thienyl, furyl, thi~201yl~ i~othiazolyl, oxazolyl or isoxazolyl, and Z represent~ hydrogen~ halogen or the group~

~R5~ or -N , where R

X reprQsent3 oxygen or sulphur, R5~1 and R5-2 independently of one another represent in each ca~e optionally substituted alkyl, alkenyl or alkinyl, R5 repre~ent~ hydrogen or alkyl, or R5-Z and Rff together with the nitrogen atom to which they are bonded form a S- to 7-membered satura-ted or unsaturated ring which optionally contains a further hetero atom and which i8 optionally ~ub6tituted by 1 or 2 alkyl group~, ~nd ~ repre~ents 0 or 1, with the e~ception o~ the compound~ 5-~ethyl-3-trifluoro-methyl-1-(6-phenyl-4-trifluorometh~1~2-pyri~yl)-pyrazole (cf. J. Heterocycl. Chem.l 6 ~2~, 223 (1969)); 2-~4-dimethylam~no-phenyl)-6-(2ls-dimethylpyrrQ~ yl~ pyri-Le A 2? ~59 2 -2~3~J~

dine (cf. J. Amer. Chem. 50c. 68, 326 (1946)); 6-phenyl-(2,2~-bipyridyl) (cf. Chem. Ber. 109, 3~S4 (1976)); 4-methylthio-6-phenyl-2,2~-bipyridins ~cf. ~S Patent 4,451,659);4-methyl-2-phenyl-6-(2-thienyl)-pyridine(cf.
J. Org. Chem. 50 (7), 1125-6 tl985)); 6-[4-(bromomethyl~-phenyl]-2l2r-bipyridine; 6 (4-methylphenyl)-2,2'-bipyri-dine (cf. Inorg. Chem. 22 (20), 2818-24 (19B3)) ~nd 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine ~cf. J. Org.
Ch~m. 47 (16), 3027-38 (1982))~
have been found.
~urthermore, i~ has been found ~hat the new 2-aryl 6-hetarylpyridine derlvatives of the formula (I~ -in which 5 Rl represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 ~ndependently of one another represen~ hydrogen or alkyl, 0 Het represents in each case unsubs~ituted or substituted pyridyl, pyrazinyl, pyrrolyl, pyrazslyl, imidazolyl, thienyl, furyl, thiazolyl, isothiazolyl, oxa~olyl or i30xazolyl, and 8 repr~ent~ hydrogen, halogen or the groups ~e A 27 559 - 3 7 ~

-X~-R5-l or -N I where X represents oxygen or ~ulphur~
R5~l and R5-2 independently of one another repre~en~
~n each case optionally substitu~ed alkyl, alkenyl or alkinyl, R6 ropre~ents hydrogen or alkyl, ~r R5-2 and RB together with the nitroqen atom to which they are bonded form a 5- to 7-membered ~atura-tad or unsaturated ring which optionally contains a further hetero at~m and ~hich i8 optionally Eubstituted by 1 or 2 alkyl groups and n represent~ 0 or 1, with the exception of the compounds already mentioned above, are obtained by one of the proce~ses describ2d belows a) The 2-ary1-6-hetarylpyridine derivative~ according ~0 to the invantion of the fcrmula (~a~

R4 ~ 3 (Ia) ~~
R

in which Rl~ k2, R3, R4~ R5l and Het have the abov~ment~oned ~saning are obta~ned when l,S-disxo compounds of the formula ~.
.

e A 27 559 - 4 -, 2 ~ 3 ~

(II) or isomers thereof of ha formula (IIa) R4 ~ 3 (~I) ~ o 0 ~ ~t R

R4 ~ 3 (II~) ~o ~ .
~ ','.
in which R
Rl, R2, R3, R', R5-~ and Het have the abovementioned meaning are ~eacted with ammonia or an ammonium aalt, if appropriate in the presence of a diluent~
b) The 2-ary1-6-hetarylpyridine derivatives according 1~ to the in~ention of the formula (Ib) R4~;R3 (I~ 3 k~ .
~2 in which Zl repre~ents -OR5~l or -Nf Hnd ~R6 ~e A 27 $59 - 5 -- , .

2~3~

R , R , R , R , R , R , R and Het have the above~
mentioned meaning, are obtained when 4-~ulphonylalky1-2-ary1-6~hetary1-p~ridine derivati~es of the formula (III~
~7 R4 ~ 3 tIII) ~ ~t in which R2 2, R3, R~ ~nd ~et have the abovementioned ~saning and R7 represent6 alkyl are reacted either ~) with compounds of the formula (IV) R5-l_OM (IV) in which R5~l ha~ the abovementioned meaning and ~ repre~ents an alkali metal ca~ion, if appropriate in the presence of a diluent, or ~) with ~mines of the formula (V) ,~5-2 (V~
~6 in which Rs-2 and R6 have the above~nt~oned m~aning, if ~ppropriate in he pre~ence of a dlluent and Le A 27 ~59 - 6 -'' -2~3397r~l3 if appropriate under increased pres~ure.
c) The 2-ary1-6-hetarylpyridine derivatives according to the inv~ntion of the formula (Ic) z2 Rq ~ 3 (Ic) ~ I-t R~
in which Rl, R2, R3, R4 and Het have the abovementioned meaning and Z2 represents halogen, are obtained when 4-hydroxy-2-aryl-6-hetarylpyridine deriva~iv~s of the formula (VI) OH
R4 ~ 3 (VI) ~ot in which R~, R2, R3, R4 and Het have the abo~ementioned mean-ing, ~re reacted with a h~logenating rea~entl if approp-riate in the presence of a diluent.
d) The 2-ary1-6-het~rylpyridine deri~atives according to the invention of the formula (Id) e ~ 27 5~9 _ 7 2~3~
-R4 ~ 3 (Id ~t R

in wh~ch Rl, R2, R3, R~ and Het have the abovemention~d meaning and Z3 repre~ents hydrogen, in each ca~e optio~ally sub~tituted alXyl, alkenyl or alk~nyl, are obtainad when the 2-aryl-6-hetarylpyridine d6rivatives according to the invention of the formula (Ic) z2 R4 ~ 3 (Ic) ~ ~t :
R
in which Rl, R2, R3, R~ and Het have the abovementioned ~eaning ::
and Z2 repre~ent~ halogen ~) are either dehalogena~ed in the presence of a cataly6t, under hydrogen pr~sure, if ~pprop-ria~e in ~he pre~ence of a diluent ~nd if Appropriate in the presence of a ba~e, or ~) ~re reaeted with di~ter deriv~tiv~s of ~he ~0 fo~mul~ (VII) Le A 27 5S~ - 8 -.. . .

- ~ ~ ,6~ ~ r~

R5-3-c~ 8 (VII~
COOR
in which R5-3 rapre3enka hydrogen or in each case optionally substituted alkyl, alkenyl or alkinyl and R~ reprasent~ methyl or ethyl, if appropriate in the presence of a diluent and if appropriate in the pre~ence o~ a base, snd the result~ng compounds are hydroly~ed, if appropriate in the pr2sence of a diluent and in the presence of a ba~e, ~nd the pxoduc~ are 3ub~equently decarboxylated in the presence of an acid.
Pin~lly, it h~s been found that the new 2-a~yl-6-hetarylpyridine derivative~ of the formula (I) have a very good herbicidal activity.
In the intQnmediates and precursors and for all ran~es covered by the definition~, ~he xadicals (Rl, R~, ~2t etc~ defined in ~he ac~ive compounds o the formula (I) lik~w~e have the meanin~s indica~ed in the ca~e of the compounds o~ the formula (I). This i~ al80 true correspondingly ~or the radicals which ~re mentioned several time~ in precursors and inter~ediates.
The term alkyl ~n the de~initions o~ Rl, R3, R~, R5 nd R~ repre~ents tr~i~h~ chain or branched alkyl Aaving preferably 1 to 6, particularly prefer~bly 1 to 4~
and, in particuIar, 1 or 2, carbon at~3. 8x~ple~ which e ~ 27 ~9 ~ 9 :
:

- .
.

; -~

;

- ~`3~7~
may be men~ioned are methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl and t-pentyl.
The term alkoxy in the definition of R1 represents straight-chain or branched alkoxy having preferably 1 to 6, particularly preferably 1 to 4, carbon atoms per alkyl radical; ~he followin~ may be mentioned by way of example and as bein~ preferred: methoxy, ethoxy, n- and i-propoxy, n~ - and t-butoxy, n-hexoxy and i~h~xoxy.
The term halogenoalkyl in ~he definitions of Rl and R2 represents straight-chain or branched alkyl having pr~ferably 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atom~, ~nd 1 to 13, preferably 1 to 6, identical or different halogen atom~, the following bQing mentioned by way of example: fluoromethyl, chloro methyl, bromomethyl, ~luoroethyl, chloroethyl, bromo-ethyl, fluoro-n-propyl, chloro-n-prop~l, difluoromethyl, trifluorvmethyl, dichloromethyl, trichloromethyl, di-fluoroethyl, trifluoroethyl, trichloroethyl, chloro-difluoromethyl, trifluorochloroethyl, chlorobutyl,fluorobutyl.
The term halogen in the definitions of Rl, R2 and z generally repre~ent~ ~luorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, and particularly preferably fluorine and chlorine.
The term8 alkenyl and alkinyl in the definition~
of RS~l ~nd R5-2 generally represent straight-chain or branched ~lkenyl or alkinyl having preferably 2 ~o 6, particularly preferably 2 to 4, and especi~lly preferably 2 or 3, carbon ato~s. The following may be mentioned by Le A ?7 559 - lo -:-7 ~ ~

way of example: vinyl, allyl, propenyl-(2)-, l-butenyl, 2-butenyl, 3-butenyl, ethinyl, l-propinyl, 2-propinyl, 1-butinyl, 2-butinyl, 3-butinyl.
In the case that, in the definition of Z, the two radicals R5-2 ~nd RB together with the nitrogen at~m to which they are bonded form a ring, the latter contains 5 to 7, prçferably 5 or 6, xing member~. The ring can contain 1 to 3 double bonds, ~ut it is preferably satura-ted. The ring C~n contain a furthar hetero ~tomj prefer-ably o~y~en, sulphur or nitrogen, and it can be 0ubsti-tuted by 1 or 2 alkyl groups, preferably by ~ne alkyl group. The following may be men~ioned by way of example:
pyrrolidino, piperidino, morpholino, N-methylpip4razino, thiomorpholino and 2,6-dimethylmorpholino.
~he ~ubstituents of the heterocyclQs enumerated in the case of Het or in terms such a~ o~tionally ~ubsti-tuted alkyl, optionally substituted alkenyl or optionally sub~tituted alkinyl in the definition of ~ have the meanings given below.
Haloaen a~ a sub~tituent generally repre~ent~
fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, particularly preferably ~luorine and chlorine.
Alkyl ~s a substituent generally represents straight-~hain or branched alkyl, preferably having 1 to 6, p~rticularly pre~erably 1 to 4, carbon atom6, methyl and ethyl being e~pecially preferred.
Alkoxy as a ~ubstituent g~nerally represents ~traight-~h~in or br~nched alkoxy h~vlng 1 to ~, parti-cularly preferably 1 to 4, carbon atom~ in the re~pec~ive Le A 27 $S9 - 11 -r~ 7 ~
alXyl radi~al; the following may be mentioned by way of example: methoxy, ethoxy, n- and i-propoxy, n~ , s-and t-butoxy, n-hexoxy and i-hexoxy.
Halo~enoal~yl and halogenoalko~y as ~ub6tituents generally repre~ent ~traight-chain or branched halogeno-alkyl or halogenoalkoxy in each case having 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and in ea~h ca~e 1 to 13, preferably 1 to 9, ident~cal or different halogen ~tom~ ~8 defined under halo~en; the ~ollowing may be ment~oned by way of ~xamples ~luoro-methyl, chloromethyl, bromomethyl, fluorosthyl, chloro-ethyl, bromoethyl, fluoro-n-propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl, dichloromethyl, tri-chloromethyl, difluoroe~hyl, trifluoroethyl, trichloro-ethyl, chlorodifluoro-methyl, trifluorochloroethyl, chlorobutyl, fluorobutyl, fluoroethoxy, chloroethoxy, bromomethoxy, fluoropro~oxy, chloropropoxy, bromopropoxy, fluorobutoxy, chlorobutoxy, fluoro-i-propoxy, chloro-i propoxy, difluoromethoxy, tr~fluoromethoxy, dichloro methoxy, trichloromethoxyj difluoroethoxy, tri~luoro-ethoxy, tetrafluoroethoxy, trichloroethoxy, ~hloxodi-fluoromethoxy and trifluorochloroethoxy.
Alkylthio as a sub~tituent in khe radicals generally r2presents straight-chain or branched al~ylthio ha~ing preferably 1 to 6 carbon atoms, for example it is understood a~ meaning the ~ollowing ~roups: ~ethylthio-, ethylthio-, propylthio-, bu~ylthio-, pentylthio as well as their i~omers ~uch as, for example, ~-propyl~hio, i-, ~- and t-butylthio~ l methyl~butylthio, 2-~athyl-bu~yl-thio- and 3-methyl-butylthio. Preferred ~lkylthio Le A 27 ~59 - 12 -.
.. , ,: . :
. ..

.

2 ~
radicals contain 1 ~o 4 carbon atoms. Particularly preerred are methylthio, e~hylthio, n~ , s-propylthio and n-, i-, - and t-butylthio.
Alko~ycarbonylalkyl a~ a substitu~n~ generally repre~ent~ straight-chain or branched alkoxycarbonylalkyl ha~ing 1 to 6, preferably 1 to 4, ~arbon atom~ in ~he alkoxy radical and 1 to 4, preferably 1 to 2, carbon atom~ in the al~yl radical; the following may be men-tioned by way of exampl~s me~hoxyc~rbonylmethyl, ethoxy-carbonylmethyl, n-propoxycarbonylmethyl, i-propoxy-carbonylmethyl, n~ , 8- and ~-butoxycarbonylmethyl.
Halo~enoalkylthio as a substituent in the radi-¢als generally represents straight-chain or branched haloganoalkylthio having preferably 1 to 6 carbon atom~, particularly preferably 1 to 4 carbon atoms, and in each case 1 to 13, pref~rably 1 to 9, identical or different halogen atoms as defined under halogen; the following may be mentioned by way of ~x~mples fluoroethylthio, chloro-ethylthio, bromoethylthio, fluoropropylthio, chloro-propylthio, bromopropylthio, fluorobutylthio, chloxo-butylthio, bromobutylthio, fluoro-i-propylthio, chloro-i-propylthio, difluorom~thylthio, trifluor~methylthio, dichloromethylthio, trichloromethyl~hio, difluoroethyl-thio, trifluoroethylthio, te~rafluoroethylthio, tri-chloroe~hylthio, chlorodifluoromethylthio and ~rifluoro-chloroethylthioO
~ ilalkylamino as a sub~ti~uent in the radicals gener~lly repre~ent~ ~n amino group hav~ng 1 or 2 alkyl groups which can in each c~sa bB ~traight~chain or branched and i~entical or diff~ren~ and preferably Le A 27 ~5~ - 13 ~3~77~

co~tains in each case 1 to 6, in particular 1 to 4, carbon atoms, with methyl, e~hyl, n- and i-propyl being ~entioned. The following may be li~ted a~ e~amples:
methylamino, ethylamino, n-propylamino, i-propylamino, dimethylamino~ di~thylamino, di-n-propylamino and di-i-propylamino~
Preferred compounds of the formula (I~ are tho~a in which R~ r~presents hydrogen, halogen, in each case ~traight-chain or branched alkyl or alkoxy having in each ca~e 1 to 6 ~arbon atoms, or represents straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R2 represents hydrogen, halogen, ~traight-chain or branched halogenoalkyl having 1 to 6 carbon atoms snd 1 to 13 identical or different halogen atoms, R3 and R4 independently of one another in each ca~e repre~ent hydrogen or ~traight-Ghain or branched 2~ alkyl having 1 to 6 carbon atoms, Het repre~nts pyridyl, pyrazinyl, pyrrolyl, pyTazolyl, lmidazolyl, thienyl, furyl f thiazolyl, isothia~olyl, oxazolyl or i~o~azolyl, ~ach of which is unsubsti-tuted or mono~ubstituted or polysubstltuted by identical or different ~ubstituents ~ the Pollowing ~eing 3alected as fiubstituen~s:
halogen, cyano, nitro, ~traight-chain or br2nched alkyl havlng 1 to 6 carbon a~om~, ~trai~ht-chain or br~nched halogeno~lkyl ha~ing 1 ~o 6 car~on atom~
and 1 to 13 identical or different halog~n atoms, in I~L~iLL~ 4 ~

... . ~ .
.. . .-.

~ 3 each case straight-chain or branched alkoxy or al~ylthio in each case having 1 to 6 carbon atoms, in each ca~e straight-chain or branched halogeno-al~ylthio or halogenoalkoxy in each case having 1 to 5 6 carbon atoms and in each case 1 ~o 13 identical or different halogen atoms, phenylEmino, (di)alkylamino having 1 to 6 carbon atoms in the xespective straight-chain or bran hed alkyl moi~ies, ~here~ in the ca~e of dialkyl2mino, the two radicals together with the nitrogen atom to which they are bonded optionally form a 5- to 6-membered saturated or unsaturated ring which optionally contain~ an oxygen, sulphur or nitrogen atom 2nd which i~
optionally substituted by 1 or 2 alkyl ~xoup~ having l or 2 carbon atom~, Z represents hydrogen, halogen or the groups -Xn-R5-l or - ~ , where ~R6 , X represents oxygen or ~ulphur, R5-l and R5-2 independently of one another represent ~l~yl having 1 to 8 carbon atom~, ~lkenyl having 2 to 6 carbon atoms or alki~yl having 2 to 6 carbon atoms, each of which i8 ~traight-chain or branched and optionally mons~ubstitu-ted or polysubstituted by identicAl or differ-ent ~ubstituent~, the ~ubstituent~ ~elected in each ca~e being: halogen~ cyano, straight-~hain or branched alko~y ha~lng 1 to 6 car~on atom~, ~nd ~traight-chain or br~nched alko~ycarbonyl-Le A 27 559 - 15 -r~

alkyl ha~ing 1 to 6 carbon atoms in the alkoxy moie~y and 1 to 4 carbon atoms in the alkyl moiety, R~ represent~ hydrogen, ~traight-chain or branched al~yl having 1 to 6 carbon atom~, or R5-2 and R6 toge~her with the nitrogen atom to which they are bonded form a 5- or 6-membered ~atura-ted ring which op~ionally contains an oxygen, sulphur or nitrogen atom and which i~ option-ally mono~ub~tituted or di~ubstituted by methyl and/or ethyl, and n rep~e~ent6 0 or 1, with the exception of the compounds S-methyl-3-trifluoro-methyl-l-(6-phenyl-4-trifluoromethyl-2-pyTidyl)-pyra~ole, 2-(4-dLmethylamino-phenyl)-6-(2,5-dim~thyl-pyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine, 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-~4-(bro~methyl)phenyl~-2,2'-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine.
Particularly preferred compounds of th~ foxmula (I) are those in which R1 repre6ents hydrogen, ~luorine, chlorine, bromine~
methyl, ethyl, npropyl, i-propyl, n-butyl, i butyl, s-~utyl~ t~butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s~butoxy or t-butoxy, or repr~sent~ straightchain or branch~d h~logeno--alkyl having 1 to 4 carbon atoms and 1 ~o 9 fluorine andfor chlorine atoms, 30 R2 repre~ents hydxogen, fluorin~, chlorine, br~mine, :.
, 7 ~

~traight-chain or branc~ed halogenoalkyl having 1 to 4 carbon atom~ and 1 to 9 fluorine and/or chlorine atoms, R3 and R4 independ~ntly of one another in each ca~e repre~ent hydrogen, me~hyl, ethyl, n-propyl, i~
propyl, n-butyl, i-butyl, ~-butyl or t-butyl, Het repre3ents pyridyl, pyrazinyl, p~rrolyl, pyrazolyl, imidazolyl, thienyl, ~uryl, thiazolyl r isothiazolyl, oxazolyl or ~soxazolyl, each of which iB UnBUb8t~ -tuted or monosub~tituted to tri~ubstituted ~y identical or different substituents, the 8ubetitu-ents sQl~cted in each ca~e being: fluorine, chlorine, bro~ine, iodine, cyano, nitro, methy}, ethyl, n- or i-propyl, n-, i-, 8- or t-butyl, in each case straight-chain or bxanched halogenoalkyl, halogenoalkoxy or halogenoalkylthio each of which has 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, phenylamino or tdi)al~ylamino having 1 to 4 carbon atoms in the re6pective straight-chain or branched alkyl moietie~, where, in the ca~e of dial~ylAmino, two alkyl moietie~ ~oge~her with the nitrogen atom to which they are bonded can form a 5-or 6-membered saturated ring which optionally contain~ an oxy~en, sulphur or nitrogen atom and which i~ optionally ~bstitu~ed by 1 or 2 me~hyl g~oups, Z represents hydrogen, fluorine, ~hlorine, bro~ine or the group~

Le ~ 27 559 ~ 17 -.

~3~'~7~

-Xn-R5-l or -N , where RB

X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent alkyl having 1 to 6 carbon at~ms, ~traight-chain or branched alkenyl having 2 to 4 carbon atoms or straight-chain or br2nched alkinyl ha~ing 2 to 4 ~arbon ~tom~, each of which i8 - 10 optionally monosubst~tuted or di~ub~tituted by identical or different ~ubstituents, the substituents chosen in each case being.
fluorine, ahlorine, ~romine, cyano, straight-chain or branched alkoxycarbonylalkyl having 1 to 4 carbon atom6 in the alkoxy moie~.y ~nd 1 or 2 carbon atom~ in ~he alkyl moiety, R6 repre~ents hydrogen, methyl, ethyl, n- or ~-propyl, n-, i , s- or t butyl, or Rs-2 and R6 together with the nitrogen atom ~o which they are bonded form a 5- or 6 membered satura-ted ring which optionally contains an oxygen, sulphur or nitrogen atom and which i~ option-ally sub~tituted by 1 or 2 ~thyl groups such as, in particular, pyrrolidino, piperidino, morpholino,thiomorpholino,N-methyl-piperazino or 2,6-dimethylmorpholino, and n repressnts 0 or 1, with the exception of the compound~ 5-methyl-3-trifluoro-methyl-1-(6-phenyl~4-trifluoromethyl-2-pyridyl)-pyTazole, 2-(4-dimethylamino-phenyl~-6-(2,5-dimethyl-pyrrol-1-yl)-e A 2? ~59 - lB

- ' ' pyridine~ 6-phenyl-(2,2~-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine, 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-t4-(bromomethyl)phenyl~-2,2~-bipyridine, 6-~4-methylphenyl)-2,2' bipyridine and 4-(methylthio)-2~
phenyl-6-(2-thienyl)-pyridine.
Esp6cially preferred compounds o~ the formula ~I) are tho~e in whi~h R1 represents hydro~en, fluorine, chlorine, br~mine, methyl, ethyl, n-propyl, i-propyl, metho~y, ethoxy, trifluoromet~yl, difluoromethyl or trichlorome~hyl, R2 represen~s hydrogen, fluorine, chlorine, bromine, ~rifluoromethyl, difluoromethyl or trichlaromethyl, R9 and R~ independently of one another represant ~ydrogen, methyl or ~thyl, He~ represent~ pyridyl, pyrrolyl, thienyl, furyl or thiazolyl, each of which is unsub~tituted or mono-substituted or disubstituted by identical or differ~
ent substitu2nts, the substituent~ chosen being:
fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethylt methoxy and methyl~hio, represent~ hydrogen, fluorine, chlorine, bromine or the groups -Xn-R5-l or -N\ , where X represent~ oxygen or sulphur, R5~1 and R5-2 indep~ndently of one another repre~ent~
~athyl, ethyl, n-propyl, i-propyl, n-butyl, ~-butyl, iobu~yl, t-~utyl, ~ethox~methyl, etho~ymathyl, methoxycarbonylmethyl, Le A 27 559 - 19 -~ ~ 3 ~ 7 ~ ~
ethoxycarbonylmethyl, allyl or propargyl, R6 represents hydrog2n, methyl, ethyl, n propyl or i-propyl, or R5-2 and R6 ~ogether wi~h the ni~rogen atom to ~-hich they are bonded represQnt pyrrolidino, piperi-dino, ~orpholino, thiomo~pholino, N-methyl-piperazino or 2,6-di~ethylmorpholinG, and n repre~ents 0 or 1, with the a~ception of the compounds ~lready mentioned above.
The following 2 aryl-6-hetarylpyxidine deriva-tives of ~he general formula (1) may be mentioned indivi-dually to the compounds ~ant~oned in the preparation example~:
Z
R~ (I) ~ R

Lo A 27 559 - 20 -.
-able 1 Rl R2 R3 R4 z Het.
, .~_ . ., _ 3 - CF'3 H H H- OC~3 ~N

3-CF3 H H H-OC2H5 {~N

3-CF3 H H H-O~ H2~C~C~2 {~N

3-CF3 H H H-O~:H2-C~cH

3-CF3 H f-l H-SCH3 ~3 3~CF3 H H HC2H5 ~

3~CF3 H CH3 H-OCH3 ~N

2-C:F3 H H H-SCH3 ~1 2-CF3 H H H-OCH3 {31 2-CF'3 H H H-OC2H5 ~3 :

Le ~ 27 5$9 ~ 21 - ~
' :

, - .

. : . :

2~3~7'7~
Table 1 ( Continuation ~ -Rl R2 R3 R4 z H~

2-CF3 H H H OC2H5 ~3 2-CF3 H H H-OCH2-C~CH ~3 4-CF3 H H H -SCH3 {~

.
4-CF3 H H H -5~2~5 {~

4-CF3 H H H -OC2H5 ~N
r~

3-CF3 5-CF3 H H OC2H5 ~_~

3-CF'35-t:F3 H H -Ot:2Hs ~l!~

~N
3 - CF3 5 - CF3 H }l ~J

, .
7 '~ ~

Table 1 (Continuation) Rl R2R3 R4 z H~

3-Cl H H H -SC2H5 {~N

3-Cl H H H -OCH3 ~01 3-Cl H H H -OC~H7-n ~

3-Cl H H CH3 -OCH3 ~;;;3 3-Cl H H H -DC2H5 ~
C1~3 5 CH3 3-Cl H H H -OCH2-C~CH2 --~ 3H7 n 3-Cl H CH3 H -N~
C3H7 n 3 - C 1 H H H --N~

3-CI H H 11 -CH3 ,J;~3 3 - C I H H CH3 OC1i3 ~N

d~ - 2 3 - . :

P~l ~

able 1 ( Continuation Rl R2R3 R4 z H-~
__. _ . . . . . . .

3-Cl H H H -C2~5 --~1 ~3 3-C 1 H CH3 H -OCH2-C~CH ~3 Z-C 1 H H H C2~15 ~;3 2-Cl H H H -C2H5 ~N

2-Cl H H H OC2H5 ~[~3~C~3 2-Cl H H H -SC2H5 ~N

2-Cl H }~ c~3 - OCM3 ~3 2 C 1 H H H -OCH3 ~3 2 - C 1 H H H o C~l3 ~3 Le 27 ~;~ ~ 24 -2~7~

Table 1 ( Continuation ) Rl R2 R3 R4 z H~
.. _ _ . ...... . . ~

4-Cl ll H H -OCH3 ~1 4 - C 1 H H H 002H5 ~3 4 - C 1 H H H - OCH2 - C~CH2 --~\N

4-Cl HC2H5 H -OC31~7-n {~

~1-Cl H H H -N(~2HS)2 ~>

4-Cl H H CH3 -N~C~13 2-C1 4-Cl H H -SCH3 ~3 ~5 2-C1 4-Cl H H -SCH3 2~Cl 4-Cl H H ~C2~J5 ~ ~ ~;
S
2-C1 4-Cl H H -OC~3 ~N

:

I~ - 2~

,, ;: ' ' ::

~3~77~

~ble 1 ( Continuation ) Rl R2 R3 ~?4 z Het . _ 2-C1 4-Cl M H -OCH3 ~

2-C1 4-CI H H OC2H5 _Q

3-C1 5-Cl H H -C2H5 ~3 3-C1 5-Cl H H-OCH2-C~CH2 ~N

3-C1 5-Cl H H-OCH2-C~CH {~N

3-C1 5-CI H H -C~f3 ~3 3-C1 5-CI CH3 }i--N N-CH3 ~_~N

2-C1 3-Cl H H -SCH3 ~N

3-C1 4-Cl ~ S~3 ~

3-C1 4-Cl H CH3-OCH3 --Q

- 2~ -7 ~ ~
Table 1 ( Continuation ) R~ ~2 R3 R4 Z ~t . .

2 - C 1 5 - C 1 H H - OC 21{5 ~[~31 3-F H H H -OCH3 {~N

3-F H ` H H -OCH3 ~3 3-F H H H -OC2H5 {~N

3-F H CH3 M ~C2~5 ~N

3-F H C2H5 ff C2H5 3-F H H H -O~H2-~ 5~J

3-F H H H -oc~-c~cH2 ,.

3 - F }I H H - N O ~3 27 ~9 - ~7 Table 1 ~ Continuation ) RlR2 R3 R4 Z H~

3-F H H H M~C4H9-r~ ~3 C4H9-n 0 3-F'4-CH3 H H -N~ --CN

3-F 4 -CH3 H H -CH ~

2-F H H H -0~2H5 {~N

2 - F H H H OC 2H5 ~3 S

2-F H H CH3 ~C2H5 ~3 4-F H H H -SCH3 ~

4-F H H H SCH3 ~} Cl 4-F H H H -SC2H5 ~3 --N

I-e A 27 SS9 - 28 -~3~J~

~able 1 ( Continuation) Rl R2 R3 R't Z H~

~-F H CH3 H -OCH ~ ~N

4-F H ~1 ~ -OCH3 ~

4-F H H H OC2H5 ~3 4-F H H H -OC2H5 {~) 2-F 4-F H H -SCH3 {~N

2-F 4-F H H -OCH3 ~N

2-F 4-F H H -5C2H5 {~N

2-F 4-F H H OC2H5 {~N

2-F 4-F CH3 H-OCH2-C}~eH2 --O

2-F 4-F H H_OCH2_C~EGH

. ..
.:

2~3~
Table 1 ( Continuation ) Rl R2 R3 R4 Z H~t 2-F 4-F H H Sc2H5 ~

3-F 4-F H H -OCH~ ~N

3-F 4-F H H -OC2Hs ~3 3-F 4-~ H H C2ff5 ~1 3-CH3 H H H -SCH3 ~1 3-CH3 H ff H -SCH3 ~3 3-CH3 H H ll -OCH3 {~N

3-Cff3 H -~ 2H5 }I ~OCH3 Le A._2 7 ~,5 9 ~ 3 ~ _ . . . ~ .

able 1 (Continuation) 2~39~ 1~

~1 R~ R3 R4 z H~ ~
~ .
3-CH3 H H H 0~ 2H5 {~N

3 - CH3 H H H OC2H5 ~3 2-CH3 H H H O~ 2H5 ~N

2-CH3 H CH3 H -Ol:H3 ~

4-CH3 H H H -OCH3 ~Q~:l .

4-CH3 H H CH3 -OCH3 -~>

3-C~H5 ~ H 11 -t 2H5 ~3 3-C2Hs H ~ H -5C2HS {;~N

e 27 ~59 - 31 -, .; . , , : : , .. . . . .

~3~
able 1 (Continuation~

Rl R2R3 R4 z H~

3-C2H5 H H H ^OCH2-C~CH2 ~3 3 C2H5 H H H -C~2-~CH2 ~I~CH3 3~C2H5 H H H -N~ --0~

3-C2~5 H H H -CH3 ~,[~1 -4-C2Hs H H H -OC2H5 ~3 3-OCH3 H H ~ oc2H5 \_ 3-OCH3 H H H -~2~5 ~, 3 - OCH3 H CH3 1~ oc2H5 ~

3-OCH3 ~ ~3 H -8C~H5 Oi e A 27 55~ - 32 -, .

. .

3 ~ P' rl ~
Table 1 ( Continuation ) R 1 R2R3 R4 Z H~ t ~ :3~7 - n _~

C3H~-n N~

2-OC~3 H H H -SCH3 {~

2 - OCH3 H H H OC2H5 {~

,:
2-OCH3 H H H -CH~ ~3 H H H CH3 -C2H5 {~Cl H H H CH3 oC~Hs ~3 ~, H H H -C2~5 C 2~5 ~~

:

I.e A 27 . 5~g - 33 -~ - - ' . - ~ - . .

If, for example, 3-methyl*hio-1-(4-pyridyl)-5-(3-trifluorophenyl)-2-pentene-l~5-dione and ammonium aceta~e nre u~ed a3 starting substances, the course of the reaction of process (a) according to the invantion ~y b~
represented by the following equations ICH~

f ~1 ~ N~4g~C}13COOe F3C ~ ~ ~

_ > F3C ~ N
If, for ex~mple, 2-(3-chlorophenyl)-4-methyl-~ulphonyl-6-(4-pyTidyl)-pyridine and pota~sium ethylate 10 ~re uued a starting 6ubstances, the cour~e of the r~action of proces~ (b-~) according to ~he invention may be represented by the.iollowing equation:

~ ~ C2HSOK
Cl~ ~ ~

~e A 27 ~9 - 34 -2 ~ 7 ~

l C2H5 .~, ~
Cl~ ~

If, for example, 2-(3-chlorophenyl)-4-methyl-sulphon~l-6-(4-pyridyl)-p~ridine and die~hylamine are u~ed as 0tarting ~b~nces, process (b-~ accordin~ to the invention may bs represented by the following ~qua-tion~

~ N
Cl~ 1 2H5 N(C2H5~2 C~
If, for e~ample, 2~(4 chlorophenyl) 4-hydroxy~6-(3-pyridyl)-pyridine and phosphoryl chloride are u~ed as starting ~bstance~, ~rocess ~c) according to ~he inven-tion ~y ~e represented by ~he fsllowing equation:

: Le A 27 559 _ 35 _ :

:

~ ~3 OH

Cl ~ ~ ~OC13 >

If, for example/ 2-(4-chlorophe~yl)-4-chloro-6-(3-pyridyl)-p~ridine i8 u~ed as starting ~ub~t~nce and S hydrogen and palladium/charcoal a~ catalyst, process (d-~) according ~o the invention may be represent2d by the following equation:
Cl ~ H2, Pd/charcoal C1 ~ ~ N ba~e ~1 ~ N

If, for ~xample, 2 (4 chlorophenyl3-4-chloro~6 ~9L~ L~ 36 -- : , . . .
:

(2-~hienyl)-pyridine and diethyl malonate are u~ad a~
starting ~ub~tances, process (d-~ accordin~ to the invention ~ay be repre~Qnted by the follo~ing equation:

Cl ~ ~ H2C~ - >

'C 02C2H5 ~ ~C02C2H5 ~ 3 Cl ~ ~ 2) acid~ ~

Some of the compounds o$ the formula (II~ ~nd (IIa) are known. They can be prepared analo~ou~ly to known proce~ses, fox e~ample by reacting ketones of the formula (VIII) o ll (VIII ) ~ot -C -CH3 in whi~h Het has the abovementioned meaning, with ~ryl-substi~uted ~-oxoketene dithio~etal deriva-tives of the formula (I~) Le A~27_~9 r 37 _ .

2 ~

Rl o 5-l (IX) ~ `SRS-in which Rl, R2 and R5~l have the abovcmentioned meaning, or by reacting ketones of the formula (X) Rl o ~ -C~3 l~) in which R1 and R2 ha~e the abovementioned meaning, with hetaryl-substituted u-oxoketene dithioacetal deriva-tives of the formula (XI) ,SR5-1 (XI) H~t-C-CH'C
~SR5-1 in which R5~1 and Het have the abovementioned meaning, if appropriate in the presence of a diluent ~uch a~
diethyl ether, dioxane, diethylene glycol dLmethyl ather or tetrahydrofuran, and if appropriate in ~he presence of a ba~e ~uch a6, for example, sodi~m ~ydride or potas~i~m tert-butylate, at temperatures between 0C and ~SODC (cf.
EP 0,263,958).
Likewi~e, some of the aryl-~ub~tituted he A 27_559 - 38 -' '~

2 ~ 3 ~

~-oxo-ketene dithioacetal derivatives of the fonmula (IX) and hetaryl-substituted ~-o~oketene dithioacetal derivat-ives o~ the formula (XI~ are known and/or can be prepar d by known processes, for ex~mple by reacting acetyl compound~ o~ the formula (XII) O (XII) Il in which R
has the meaning of Het or where Het, Rl and R2 have the abovementioned meaning, with carbon disulphide, if appropriate in the presence of a diluent such as N,N-dimethylformamide or dioxane, in the presence of a base such as, for example, potassium tert-butylate or sodium hydride, and sub~equently with an al~ylation reagent of the formula I~III) R5~ (XIII) in which R5~1 has the abovementioned msaning and y1 represents chlorine, bromine or iodine, at temperatures be~ween ~C and +50C (cf. J. Ch~m. Soc., Perkin Trsn~ 6), 549-553 (197B)3.
A~etophenone derivative~ of the for~ula (X~, ke~ones of the fonmula (VIII), acetyl compounds of the ~L~ 39 -c~
formula (XII~ and alkylation reagents of the formula (XIII) are g~nerally ~nown compounds of organic chemi~-try.
In formula ~III), R7 preferably represent6 straight-chain or branched al~yl ha~ing 1 to 4 carbon atoms, in particular m~thyl or ethyl~
The 4-~ulphonylalkyl-2-aryl-6-hetarylp~ridine derivative~ of the formula tIIIJ are new. However, they can be prep~red analogously to known procesee~ tcf. EP
0,263,958J, by reacting 2-aryl-5-hetarylpyridine deriva-tives o~ the formula (Ia) SR5-i R4 ~ R3 (Ia~
~o~
R
in which Rl, R~, R3, R~, R5~1 and Het have the ~bovementioned mean-ing, with an oxidant 6uch as, for example, metachloroper-benzoic or hydrogen peroxide/formic acid, if appropriate in the precence of a catalyst ~uch as, for example, ammonium molybdate, if appropriate in the presence of a diluent ~uch as, for example, hexane, heptane, petroleum ether, benzene, toluene, chlorobenzene, diethyl ether, dioxane, tatrahydrofuran, ac~tone, meth.nol, ethanol, wa~er or mixtures o~ these diluentsl a~ temperakures be~ween 0C and +130C.
In formula (IV), N repres~nts an alkali metal e A 27 552 ~ 40 ~

:: :

2 ~ 3 ~1~ 7 I ~

cation, preferably a sodium or pota~sium cation.
Th~ compounds of the formula ~IV~ and ~he amines of the ~ormula (V) are generally known compounds of organic chemi~try.
The 4-hydroxy-2-a~yl-6-he~arylpyridine deriva-tives of the formula (VI) ~re new. However, they can be prepared analogou~ly to known processes (cf. ~P-A
0t263,958), ~y reacting 4-sulphonylalkyl-2_aryl_6_het-arylpyTidine derivative~ of th~ ormulQ (III) R4 ~ 3 ~(III) ~Ho~
in which R2 Rl, R2, R3, R4, R7 and Het have the abovementioned meaning, with alkali mstal hydroxide ~uch as, for example, ~odium hydroxide ox pota88ium h~droxide, if appropriate in the presence of a diluent such a~, for examplef methanol, ethanol, water, dimethylformamide, acetonitrile, tetra-hydrofuran or dioxane, a~ ~empe.ratures between 9C ~nd +160C.
In ~ormula (VII~, ~Q R5-3 preferably repre6ents hydrog~n, straight chain or branched alkyl having 1 to 8 carbon atoms, straight-chsin or bran~hed alkenyl having 2 to 6 carbon atoms or ~tr~ight-chain or branrhed alkinyl having 2 to 6 carbon atom~, in each ~a~e optionally monos~b~t~tu-ted or polysub~tituted by identical or diffexent e A 27 ~ 41 7 ~ ~

substituents, suitable substituents in each case being: halogen, cyano, ~traight-chain or branched ~lko~y having 1 to 6 carbon atom6 and straight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms in th~ alkoxy moiety; particularly preferably represents hydrogen, alkyl having 1 to 6 carbon a$oms, straight-chain or branched alkenyl having 2 to 4 carbon atoms or straight-chain or branched alkinyl having 2 to 4 carbon ato~s, $n each case ~0 optionally monosub~tituted or di~ub~tituted by identical or di~ferent substituents, suitable sub6tituent~ in each ca~e being: fluorine, chlorin~, bromin~, cyano, s~raight-chain or branched alkoxy having 1 to 4 carbon atom~, and ~raight-chain or branched alkoxycarbonyl having 1 to 4 c~rbon atoms in the alkoxy moiety;
R5-3 in particular represants hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, 8-butyl, i-butyl, t-butyl, ~ethoxyme~hyl, ~tho~ymethyl, methoxycarbonylmethyl, ethoxycarbonylme~hyl, allyl or propargyl.
In formula ~VII), R8 preferably represents methyl or ethyl.
Diester derivatives of the formula (VII) are ~5 ~enerally known compound~ of organic chemistryO
Procesx (a) according to the invention is pxefer-ably carried out u~ing diluentq. Suitable diluents for thi~ purpo8e are virtually all inert organic solv~n~.
~he~e include ethers such ~ diethyl ether, di~opropyl e~her, dio~ane, tetrahydrofuran and diethylene ylycol L~ ~ 27 5~ 42 -- . - . . : ~ , -- . : .

.~ . .

3 ~

dLmethyl ether; carboxylic acids such ~8 formic acid and acetic acid; alcohols such as methanol, ethanol, isoprop-anol, tert-butanol, octanol, cyclohexanol, diethylene glycol nnd glycerol; amides such as formamide, N,N-dimethyl sulphoxide and sulpholane, and also mixture~ of the abovementioned diluents. Tetrahydrofuran or N,N-dLmethylformamide are preferably used.
When carrying out process (a) according to the invention, th~ reaction temperature~ can be ~ari~d within a ~ub~tan~ial range. In general, the proce~ ~s carried out at temperatures between 0C and +100C, preferably at temperatures between 0C and ~50C.
For carrying out proce~& (a) according to the invention, 1 to 20 mole6, pref~rably 5 to 10 moles, of ammonium salt (for example ammonium acetate or ammonium chloride) or ammoniates are generally employed per ~ole of 1,5 dioxo compound of the ~ormula (II).
In this context it i8 also possible ~o prepare the 1,5-dioxo compounds of the fo~nula (II), which are 2~ rsquired a6 star~ing compounds for carrying out proce~s (a) according to the inv~ntion, in a prec~diny reaction directly in the reaction vessel and to further react the product directly from the reac~ion mixture, without isolation ('~one-pot process").
In all processe6, the reaction is carrisd out and the reaction products are isolated by generally customary methods.
Process ~b-~) according to the invention i5 praferably carried out u~ing diluents. Suitable diluent~
for this purpo6e are ~irtually all inert organic ~1Lj~Z~ 3 -.. .

- : ~
, ~, ' ~ ' ' , :

~3~ Jl~

solvents~ These preferably include aliphatic and aro-matic, optionally ~halogenated hydrocarbon~ such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, ethers such as dieth~l ether and diisopropyl ether, glycol dimethyl e~her and diglycol dimethyl ether, tetrahydrofuran and dioxane, nitriles such as, for example, acetonitrile and is~butyronitril~;
alcohol~ such a6 methanol, ethanol, isopropanol and tert-butanol; tertiary a~ines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine and ~-methylmorpholine;
amides such as form2mide, N,N-dimethylformamide and acetamide; additionally dimethyl sulphoxide and ~ulpho-lane, and also mixkures of the abovementioned diluents.
When carrying out process (b~) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the proces~ i8 carried out at temperatures between 0C and ~150C, preferably at temperatures between 0C and ~120C.
For carrying out process (b-~) according to the invention, 1 to 15 moles, preferably 1 to 10 moles, o~
compound of the formula (IV) are generally employed per mole of 4-sulphonylalXyl-2-aryl-6-hetarylpyridine deriva-tive of the formula (III).
Process (b-~) according to the invention i~
pre~erably carried out u~ing diluents. Suitable diluents for this purpose are virtually all inert organic ~ol-vents. ~hese preferably include aliphatic and ~romatic, optionally haloge~ated hydrocarbon~ such a~ pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, Le A ~7 559 _ 44 _ ~3 ,-~77 ~

ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon te~rachloride, chlorobenzene and o-dichlorobenzene, ethers ~uch ~5 diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones ~uch as acetone, me~hyl ethyl ketone, methyl i30propyl ke~one ~nd methyl isobutyl ket~ne, e8ter8 such as methyl acetate and ethyl acetate, nitriles such ~B, for example, ncetonitrile ~nd propionitri}e; ~mld~s ~uch a~, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, alcohols, ~u~h as, for exampl~, methanol, ~thsnol, isopropanol, tert-butanol, carboxylic ac~d~ ~uch as, for example, formic acid and acetic acid, water, and ~lso dimethyl sulphoxide, tetram~thylene s~lphone and hex~methylphosphoric tri2~ide, or mixtures of the abovementioned diluent~.
When carrying out process (b-~) according to ~he in~en~ion, the reaction temperatures can be ~aried within a ~ubst~ntial ran~e. In general, ~he proc~ i8 carried out at t~mperature~ bstween 0C and ~180C, preferably ~t temperatures between +20C and ~120C.
For carrying out process (b-~3 according to the in~ention, 1 to 100 moles, preferably 1 ~o 10 molefi, of amin2 of the formula (V) are senerally employed per mole of 4-sulphonylalkyl-2-aryl-6-hetarylpyridine deriva~ive of the formula ~III).
Process (b-~) according to the invention i~
prefer~bly c~rr~ed out under ~tmo~pheric pre~Gure, but it i8 al~o possible for the proce~s ~o be carried out und~r 30 incre~ed pre~ure.

Le A 27 5S~ - 45 -Rroce~s (c) according to the invention i~ prefer-ably carried out u~ing diluent~. ~uitable diluent6 for this purp~e nre virtually all inert organic 801~ent8.
These preferably include aliphatic and aromatic, option-ally halogenated hydrocarbon~ 3u~h as ~entane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, ~oluene, ~ylene, methylene chloride, e~hylene chloride, chloroform, carbon tetrachlorider chlorobenzene and o dichloroben~ene, e~her~ such as die~hyl e~her and dibutyl e~her, glycol dimethyl ether and diglycol di-methyl ether, tetrahydrofuran and dioxane, ketones such as ac~tone, me~hyl ethyl ketone, methyl isopropyl ke~one and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, aceto nitrile and propionitrile, amide~ such as, ~ox example, dimethyl~ormamide, dimethylacetamide and N-methyl-pyrro-lidone, and al~o dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.
Proces~ (c) according to ~he invention i6 carried ~0 out using halogenation reagents. Thionyl chloride, phosgene, phosphoryl chloride, phosphorus pentachloxide, phosphoryl bromide or phosphorus tribromida are prefer-ably used.
When carrying out proces~ (c3 according ~o the invention, the reaction temperature~ can be varied within a substantial range. In general, the process i8 carried out at temperatures be~ween 0C and ~200C, preferably at t~mperatures between +50-C and +150DC.
For c~rryinq out proce~ ~c) according to the in~ention, 1 to 50 ~ole~, preferably 1 ~c 10 mole~, of Le A 27 559 ~ 46 -'~

halogenation reagent are generally employed p2r mole of 4-hydroxy-~-ary1-6-hetarylpyridine derivativ~ of the formula (VI).
Process (d-~) according to the inven~ion i~
S preferably carr~ed out using diluents. Suitable diluen~s for this purpose are virtually all inert oxganic ~ol-vents. These include ben~ene, toluene, xylene, tetra-hydrofuran and dioxane, ester6 such as methyl aceta~e and ethyl ~catate, alcohols such as ~ethanol, ~thanol and i~opropanol, and also water. ~ater, methanol, ethanol, ethyl acetate and toluene, or mixture~ of the~e dil~ent~, ~re preferably u~ed.
~ hen carrying out proce~s (d~ ccording to the invention, the reaction temperatures can be var~d within lS a substantial range. In ganeral, the proce~s i~ carried QUt at temperatures between 0C and +100C, preferably at temperatures between ~20~C and +50C.
Process (d-~) according ~o the invention i8 preferably carried out using catalyst6. Suitable as catalyst~ ~re cu~tomary halogenation ca~alysts ~uch a~, for example, Raney nickel, or el~mental pla~inum or palladium, palladium~active charcoal being preferably used.
Proce6s (d-~) according ~o the invention i~
carried out in the pre~ence of bases. Suitable a~ base~
are, for example, alkali metal hydroxides ~uch s, ~or example, 30dium hydroxide and pota~ium hydroxide, ~lkaline earth ~etal hydroxides such a8, for example, cal~ium hydroxide, alkali metal carbonates, ~lkali m~tal 3Q acet~tes and alkali metal alcoholates su~h as sodium ~eLlLi~ 5~ - 47 -57 ~1 carbonate~ potassium carbonate, sodium methylate, potas-8ium methyla~e, sodium ethylate or potas~ium ~thylate, ammonia, amine~ ~uch as diethyl~mine, or ba~ic ion exchangers.
Process (d-~) according to the invention i~
generally effe~ted at a hydrogen pressure of 1 to 5 atmo~pheres, preferably a~ 1 to 3 atmo~phere~. For working up, the ca~alys~ i8 filtered off, the reaction solution i8 treated with water, and the ~xture i~
e~tracte~ with organic 301~ent~. Further w~rki~g-up i~
carried out by custo~ary method~.
For carrying out proce3s (d-~) according to tha invention, 1 to 10 ~oles, preferably 1 to 5 ~oles, of hydrogen and 0.01 to 1 mole, preferably 0.01 to 0.1 mole, of catalyst, are generally ~mployed per mole of compound of the formula (Ic).
Proces~ (d-~) according to the invention is preferably carried out using diluent~. Suitable diluent~
for this pUrpO82 are virtu~lly all inert organic ~ol-vents. The~e preferably include aliphatic and aromatic, optionally halogenated hydrocarbon~ such a~ b~nzene, toluene, xylene, methylene chloride, e~hylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ether~ ~uch as diethyl ether and dibutyl ether, tetrahydxofuran and dioxane, ketone~ ~uch a8 acetone~ methyl ethyl ke~one, methyl isopropyl ketone and methyl i~obutyl ketcne, ~ters such as methyl acetate and ethyl acet~te, ni~riles ~uch as, for example, aceto-ni~rile and propionitrile, di~e~hyl ~ulpho~ide and `~
~ulpholane, and al80 ~ixture~ of the~e diluents.

_A_27 S59 - 48 -, ~9~ ~

When carrying out khe fir~t reaction ~ep of process (d-~) according to the invention, the reac~ion temperature~ can be varied within a s~bstantial range. In general, the first reaction step i8 carried out at temperatures between -10C and +180C, pre~erably at temperatures between 0C and +150~C.
The first reaction step of proce~s (d-~) accord-ing to the in~ention ~ B carried out in the presence of bases. Alkali me~al h~dride~ such a~, for a~ample, sodium hydride~ alkyllithium such as n-butyllithium, lithium diHlkylamides such as, for e~ample, lithium diisopropyl-amide ~LDA), alkali metal alcoholates ~uch as, for example, sodium methanolate and sodium ethanolate, and metal hydroxides such as, ~or ~xample, ~odium hydroxide, lS are preferably u~ed.
For caxrying out the first reaction ~tep of proces~ (d-~ according to the in~ention, 0.5 to 2 moles, preferably } to 1.5 moles, of diestex derivative of the formula (VII~ and 1 to 3 mole~, pre~erably 1 to 2 moles, of ba~e are generally employed per mole of c~mpound of the formula (Ic).
When carrying ou~ the ~econd reaction step of proce~ (d-~) according to the inYention, the reaction temperatures can be varied within a ~ubstantial range. In general, the second reaction step i~ carried out at temperatures between O~C and +150C, preferably at temperatures between ~10C and +100C.
The ec~ond reaction ~tep of process (d-~ accord-~ng to the invention i8 ~arried out in the pre~enc~ of bases. Alkali ~etal ~ydrsxides such a~, for e~Emple, k5-lL~L~ 49 -2 ~

sodium hydroxide, and alkali metal carbonate~ such a~, for example, sodium carbonate, are preferably used.
For carrying out the ~econd reaction ~tep of process td-~) according to the invention, 1 to 6 mole6, preferably 2.1 to 5 mole~, of ba~e are ~ener~lly employed per mole of c~mpound of ~he formula (Ic) used.
In the decarboxyla$ion reaction of pr~cess (d-~) according to the in~ention, the reaction temperature~ can be varied within a ~ubstantial range. In gen~ral, the decarboxylation reaction ~ carried out at t~mperatures between O~C nd t200DC, preferably at temperAture~
between +20C and +150C.
The decarboxylat~on reaction of proce~s (d-~) according to the invention i~ carried out in the pr~sence of acid~. Inorganic acids 8uch as, for exampl~, sulphuric acid or hydrochloric acid, and organic acids ~uch a~, for example, ~cetic acid, are pre~erably used.
For car~ying out the decarboxylation xeaction of process (d-a) according to the invsn~ion, 1 to 10 moles, preferably 2.5 to 6 moles~ of acid are gener~lly employed per mole of compound of the formula (Ic) used.
Process ~d-~) accoxding to the invention iB
carried out by cu~omary methods. For working up, the reaction mi~ture i~ rendered neutral, concentrated and extracted. ~he product i~ purified by chromatography or recrys~allization.
The active ~ompound~ according to the ~nvantion can be used A8 defoliants/ de~iccant3, a~ents for des-troying bro~d-leaved plant~ and, e~pecially~ as w~ed-ki~ler~. By weeds, in the broadest ~ense, ~here ~xe ~o be ?

, 2 ~ 7 ~

understood all plant~ which grow in locations where they are undesired. Whether the ~ub~tances according to the invention act as total or selective herbicides depend~
essentially on the amount u~ed.
The active compound~ according ~o the invention can be u~ed, for exEmple, in connection with the ~ollow-ing plant~s Dicotyledon æeeds of the qenera: Sinapis, ~epidium, Galium, Stellaria, ~atri~aria, Anthe~
~alin~oga, Chenopodium, ~rtica, Sanecio, ~m~ran~hu~, Por~ula~a, Xanthiumr Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cir~ium, Carduus, Sonchu~, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veroni~a, Abutilon, kmex, Datura, Viola, Galeopsis, Papaver and CQntaurea.
Dicotyledon culture~ of the genera: Go88ypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum~ Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-sica, Lactuca, Cucumi8 and Cucurbita.
Monocotyledon weeds of the aenera: ~chinochlo~, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, ~vena, Cyperus, Sorghum, Agropyron, Cynodon, ~onochoria, Fimbri~tylis, Sagittaria, Eleochari~, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, AgroQtis, Alopecurus and Apera.
Nonoco~yledon cultures of the genera: Ory~a, Zea, Triticum, ~ordeum, ~vena, Secale, Sorghum; Panicum, S~ccharum, Ananas, ~sparayu~ and Allium.
However~ the u~e ~f the ~ctive compound~ ac~ord-ing to the invention i8 in no way restricted ~o thsRe Le A 27,559 - 51 w . ' ' ~ : ,'. ' ` ` 2~3~

genera, but also ex~ends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weed~, for example on indu~trial terrain and rail track~, and on path~ ~nd squares with or wi~hou~ tree plantings.
~qually, ths compounds can be 2mployed for combating weeds in p~rennial cultur~s, for example affore~tation~, decorative tree plantings, orchards, vineyard~, citru~
groves, nnt orchard~, banana plantations, coffee planta-tion~, tea plantation~, rubb r planta~ion~, oil palm plantations, cocoa plantation~, ~oft fruit plant~ngs and hopfield~, and for the selective combating of weed~ in annual cultures.
In this context, the active compound~ of the formula (I) according to the invention are particularly suitable for sele~tively combating monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon cultures, b~th pre- and post-emergence.
In addition, some of the active compound of the formula (I) according to the invention have a fungicidal nctivity, for example ~gainst Pyricularia oryzae on rice.
The active compound~ can be converted into the cu~t~mary formulations, ~uch ~ solution~, emul~ions, wettable powders, su~pensions, powder~, dusting agents, pastes, soluble powders, granules, suspension-æmulsion concentratefi, na~ural and ~ynthetic ~ater~als impregna~ed with active compound, and very fine cap~ule~ in polymeric ~ubstances.
These formulations are produced in a known I~L~L~ 52 -'.` ' ' :. ' , ~ ~' ''',. ~. .
. .

.
.
,' ~ ' .

2~3~

manner, for example by mixing ~he cti~e ~ompounds with extender~, that 1B li~uid solvents and/or solid carriers, optionally wi~h the use of fiurfa~e-active agents, that i~
emul~ifying agents and/or dispersing agents and/or foam-S formLng agents.
In the casa of the use of water as an extender, organic 801vent8 can, for example, also be used a~
auxiliary solvents. As liquid solvents, there are suit-able $n ~he main: ~romatics, such a~ ~ylene, toluene, or alkyl~aphthalenes, chlor~nated axomat~cs ~nd chlorinated ~liphatic hydrocarbon~, ~uCh as chlorobenzenes, chloro-ethylenes or ~ethylene chloride, ~liphatic hydrocarbon~, ~uch as eyclohexane or paraffina, for example petroleum fraction8, mineral and vogetable oilæ, alcohols, ~uch as butanol or glycol a8 well as their ethers and e~ters, ketones, such as acetone, ~ethyl ethyl ketone, me~hyl i~obutyl ketone or cyclohexanone, ~trongly polar 801-~ent~, 8uch as dLmethylformamide and dimethyl ~ulphoxide, as well as water.
As ~olid carriers there ~re suitables for example ammonium salts and ground natural minerals, ~uch as kaolins, clay3, talc, chalk, quartz, attapulgite, mont-morillonite or diatomaceou6 earth, and ground 0ynthetic minerals, such as highly disper~e ~ilica, alumi~a ~nd 6il~cates, a~ solid carriers for granules there are ~uitable: for example cru~hed and fractionated natural rocka such as calcite, marble, pumice, sepiolite and dolomite, ~ well as synthetic granules of inorganic ~nd organic ~eals, and granules of organic ma~erial such a~
sawdu~t, coconut ~hells, maize cob~ and tohacco ~talks,o Le A 27 559 - 53 -- ' ' ''.' . :

~ ~ ~ $ ~ t¦ .~

as emul~ifying and/or ~o~m-forming Agents there are suitable: ~or example non-ionic and anionic emulsifier~, such as polyoxyethylene fatty acid e~ters, polyoxy-ethylene ~atty alcohol ethers, for ~mple alkylaryl 5 polyglycol ether~, alkylsulphonate~, alkyl sulpha~e~, a~ylsulphonate6 as well aB albumen hydrolysis product~;
as di~persing agents there are ~uitables for example lignin-~ulphite waste liquors and methylcellulose.
8dhe~ives ~uch as carbo~ymethylcQllulose and natural and synthet~c polymers in the f~rm o~ p~wder~, granules or latexes, such ~ gum arabic, polyvi~yl alcohol and polyvinyl acetate, a~ well a~ natur~l phos-pholipids, such as cephalins and lecithin6, and s~nth~tic phospholipid~, can be used in the formulations. Further additives can be mineral and vegetable Qils.
It i~ possible to U82 colorants such as inorganic pigment~, for example iron oxide, titanium oxide and Prus3ian Blue, and organic dyestuffs, ~uch a~ alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and ~race nutrients such as salt~ o~ iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weed~, the active compound~ accord-ing to the invention, as ~uch or in the form of their for~ulations, can also be used a~ mixture3 wi~h known herbicide~, finished formulations or ~ank mixes being po~ible.
~uitable herbicides for the mi~ture~ are Xnown Le A 27 559 _ 54 ~

.
. , , . ' , : ~ . :

: ~ .
' ~ .- ~ ' .

2 ~

h~rbicides, such a~, for example, l amino-6-ethylthio 3-(2,2-dimethylpropy~ 3,s-triazine-2,4(1H~3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N~N'-dimethylurea (M~TABENZTHIA2URON) for comba~ing weeds in cereal~; 4-amino-3-methyl-6-pheny~ 2~4-triazin-5(4H)-~ne (MET~-NITRON) for c~mbating weeds in ~ugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5t4H~one (METRIBUZIN~ for combating weed~ in 80ya beans. 2~4-Dichlorophenoxyacet~c ~cid (2,4-~); 4-(2,4-dichlorophen-oxy)-butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 5~(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoi~ acid (ACIFLUOREEN); N-~methoxym~thyl)-2,6-diethyl-chloroace~anilide (ALACH~OR); 2-chloro-4-e~hyl-smino-6-isopropylamino-1,3,5-triazine (ATRAZINE); methyl 2-[[tt[(4,6-dim8thoxypyrimidin-2-yl)-amino]-carbonyl]
~mino]-sulphonyl]-methyl]-benzoate (B~NSULFURON); 3-i~opropyl-2,1,3-benzothiadiazin-4-one 2g2-dioxide (BENTAZONE); methyl 5-(2,~-dichlorophenoxy)-2-nitro-benzoate (BIFENOX); 3,5-dibroms-4-hydroxy-~enzonitrile (BRO~OXYNIL); ~-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl-acetamide (BUTACHLOR); ethyl 2-{t(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}benzene~ulphonamide (CHLORSULFURON~; ~,N-dimethyl-N'-t3-chloro-4-methyl-phenyl)-ure~ ~ OELORTOLURON~; exo-l-methyl-4-(1-methyl-ethyl)-2-(2-methylphenyl-methoxy~-7-oxabicyclo-(2,2,1~-heptane (CINNETHYLIN); 3,6-dichloro-2-pyridinecar~oxylic ~cid (CLOPYRALID); 2-chloro-4-ethylamino-6-(3-cyanopro-pylamino) 1,3,5-trlazin~ (CY~AZIN); 2-~4-(2,4-dichloro-Le A 27 ~ 55 -phenoxy)-phenoxy]-propionic acid, its methyl estex or it~
ethyl ester (DICLOFOP~ETHYh); 2-[(2-chlorophenyl)-~ethyl~-4,4-dimethylisoxazolidin-3-one (DI~ETHAZONE); ~-ethyl N,N-di-n-propyl-~hiocarbamate (EPTANE); 4-amino-6-t-butyl-3-e~hylthio-~,2,4-tri~zin-5(4H)-one (ETHIOZI~);
2-{4-[(6-chloro-2-ben~oxazolyl)-oxy]-phenoxy}-prop~noic acid, its methyl ester or it~ e~hyl ester (F~NO~APROP~;
2-[4-(5-trifluoromethyl-2-pyrldyloxy)-pheno~y]-propanoic acid or it~ butyl e3ter (FLUAZIFOPBUTYL); N,N-dime~hyl-N'-(3-trifluorome~hylphenyl)-urea ~FLUO~TURON); 1-methyl-3-phenyl-5-53-tr~fluorom~thylphenyl)-4-pyridone (FLURIDONE); [(4-amino-3,5-dichloro-6-fluoro-2-pyridin-yl)-oxy]-ac~tic acid or it~ l methylheptyl e~t~r (FLUR-OXYPYR); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methyl-sulphonyl-2-nitrobenzamide (FONESAFEN); 2-{4-~(3-chloro-5-(trifluor~methyl)-2-pyridinyl~-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP~; 3-cyclohexyl-6 dimethylamino-l-methyl-1,3,5-triazinQ-2,4-dione (HEXAZIN-ONE); methyl-2-[4,5-dihydro-4-methyl-4-~1-methylethyl)-5 oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate (INAZAMETHA-BENZ); 2-(4,5-dihydro-4-methyl-4-isopropyl-5-o~o~
lmidazol-2-yl~-pyridine-3-carboxylic acid (IMAZAP7R); ~-t5-methyl-5-(1-methylethyl)-4 oxo-2-imidazolin-2-yl]-3-[quinolinecarboxylic acid (INAZAQUIN); 2-14,5-dihydro-4-methyl-4-isopropyl-5-oxo-(lH)-imidazol-2-yl]-5-ethyl-pyridine-3-c~rbo~ylic ~cid (INAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNI~); N,N-dimethyl-~'-(4~i~o-propylphenyl)-urea ~ISOPRO~URON); 2-ethoxy-1-methyl-2~
oxo-ethyl 5-~2-chloro-4-(trifluoromethyl)-pheno~y]-2-nitrobenzoate (LACTOF~); (2-msth~1-4-chlorophenoxy)-Le ~ ?7 55~

. . . . . .

. ~ , . : . :

.

~C~7~

aceti~ acid (MCP~); (4-chloro-2-me~hylphenoxy~propionic acid (~CPP); N-methyl-2-(1,3-benzo~hiazol-2-yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethylphenyl)-N-[(lH)-pyrazol-1-yl-me~hyl]-acetamide (METAZACHLOR); 2-ethyl-6-methyl-N-(l-methyl-2-me~hoxye~hyl~-chloroacet-anilide (METOLACHLOR); 2-{[~((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amLno )-carbonyl~amino]-sulphonyl}-banzoic acid or it~ ~ethyl e~ter (METSULFURON); S-ethyl ~,N-hexamethylens-thiolcarbamate (~OLINATE~; 4-(di-n-propyl-amino)-3~5-dinitrobenzenesulphonamide ~ORYZALIN); (2-chloro-4-trifluoromethylphenyl)-~3-ethoxy-4-nitxo-phenyl ether (O~YFLUOREEN); N~ ethylpropyl~-3,4-dim~thyl-2,6-dinitroaniline(P~ND~ETHALIN);2-chloro-N-~sopropylacet-anilide (PROPAC.HLOR); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE); 2-Cl-(~thoxamino~-butylidena~-S-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 2-chloro-4,6-bis-(ethylamino)-1,3,5-tri-azine (SIMAZINE); 2,4-bis-[N-Qthylamino]-6-methylthio-1,3,5-triazine (SIMæTRyNE); 4-e~hylamino-2-t-butylamino-6-methylkhio-s-triazine (TERBUTRYNE); ~ethyl 3-[tll~4-methoxy-6-methyl-1,3,5-tria~in-2 yl)-amino]-carbonyl3-amino]-sulphonyl~-thiophQne-2-carboxylate (THIANETURON);
S-2,3,3-trichloroallyl ~,N-diisopropyl-thiolcarbamate (TRIALLATE); 2,6-dinitro-4-trifluoromethyl-~,N-dipropyl-aniline (TRIFLUR~LIN) and ethyl 2-~4 (6-chloro-2-quinoxa-linyloxy)-pheno~y]-propionate (QUIZALOFOPE~HYL~ are also pos~ible. Surprisin~ly, some mixture~ al~o show a syner-gi~tic action.
Mixtures with other kno~n acti~e compounds, ~uch a~ fungicide6, insecticides, acari~ides, nematicides, he_A 27~59 - 57 -. ~. ~ ....

.

~3~ 77~

bird repellants, plant nutrient~ and agents which Lmprove ~oil structure, are also possible.
The active compounds can be used a8 such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such a6 ready-to-u6e ~olutions, ~uspension~, em~ ions~ powder~, pa~tes and granules. They are u~ed in the cus~omary manner, for e~ample by watering, ~praying, atomizing or ~cattering.
The active compounds according to the invention can be applied either before or after ~mergence of the plants.
They can al80 be incorporated into the 80il before sowing.
~he amount of active compound u8ed can vary within a ~ubstantial xange. It depends essentially on the nature of the desired effect. In general, the amounts used are between OoO1 and 15 kg of active co~pound per hectare of 80il surface, preferably between 0.05 and 10 kg per ha.
The preparation and u8e of the active compounds according to the invention can be seen fxom the followiny example~.

~rL~L~Z~ 8 -2 ~

Preparation Examples xample 1 Proce~s (a) (nOne-pot ~ariant~) 3.8 g (0.02 ~ol) of 3-trifluoromethylacetopheno~e and 5.2 g (0.046 ~ol) of potassium tert-butylate ~n 100 ml of tetrahydrofuran are stirred for 30 minute~ at room tempera~ure. Tha reaction mixture i~ 3ubse~usntly treated with 4.5 g ~0.02 mol) of 3,3-bis-(methyl~hio)-1-(4-pyridyl)-2-propen-1-one, and this mixture iB stirred for one hour at room temperature. 100 ml of concentrsted acetic acid and 15 g of ammonium acetate are then added, and the mixture i8 refluxed for 4 hours, during which process the tetrahydroIursn is distilled off by means of a water separator. After cooling, the reaction mixture is rendered neutral u6ing sodium hydroxide solution, extracted by shaking with ethyl acetate ~ and dried over sodium sulphats. The r~sulting ~olution i~ freeà îrom solven~ under reduced pres~ure.
0.9 g (13% of theory) of 4-methylthio-6-(4-pyridyl)-2-(3-$rifluoromethylphenyl)-pyridln0 of malting point 145C (de~omposi~ion) are obtained.

Le_A 27 ~9 _ 59 _ , ;

7~ P.~ 7 ~

~xample 2 oc2ff5 Cl~

Process (b-~) 1.7 g (0.005 mol) of 2-(3-chlorophenyl)-4-methyl-sulphonyl-6-(4-pyTidyl)-pyridine are tre~ted with 1.3 g (0.015 mol) of potassium ethyl~te in 30 ml of dry ethan-ol, and the mixture i8 refluxed for 16 hours. It i8 ~ubsequently concentrated under reduced pressure and the residue i~ tsken up in methylene chlor~de. The ~olution i~ wa~hed twice with ~ater, dried over sodiu~ sulphate, and the solvent i8 removed under reduced pressure. The residue i8 stirred wi~h diethyl ether, and the reEulting crystalline product i8 filtered off with suction and dried. 0.7 g (45% of theory) of 2-(3-chlorophenyl)-4- :
Qthoxy-6-(4-pyridyl)-pyridine of melting point 123C i8 ~ .
ob~ained. ~ :
The compound~ of th~ g~neral formula (I3 ~R1 ~ (I) ~ ~.

whi~h are li~ted in Table 2 ar~ obtained ~nalogously to Preparation ~xamples 1 and 2 and following the generaI

: `:

Le A~27~ 60 -.. ,,, :
~.

, . , :
: :

~ .

instructions for processes (a), (b), (c~ and (d) accord-ing to the invention.

I,~ A ?7 ~$~

, . . . - -2~3~

Table 2 No R R2 R3 R4 ~ llelting .

32-CH3 H H H -~CH3 ~3 oil 4 4-Cl H H H -SCH3 ~ ~13~ C

5 4-Cl H H H -SCH3 ~ 105 C

6 4-Cl H H H -SCH3 ~3 120 C

7 4-Cl H H H -SCH3 --G 141 C
8 3-Cl H H H -SCH3 ~3 oil 9 3-Cl H H ~ -SCH3 f~3 oil 103-CF`3 H H H -SCH3 ~3 84C

113-C~3 H H H -SCH3 ~3 oil ~N
124-Cl H H 11 -~2~5 ~7 147 C

~ - 62 -''~ , ,, ' ~ '' ' ' ' 2~r TablQ 2 ( t:~ontinua tion ) Ex. ~lelting ~ ~ Rl E~2 R3 R4 z llot point ~ ~ ,. . .

134 _r 1 H H H C2H5 ~31 oil 14 4-Cl 11 H H OC2H5 ~[~3 108 C

15 3-CF3 H 11 H -SCH3 ~ oil 16 3-C~3 H H H -5CH3 ~ oil CH3 S ~H3 17 3-CF3 H H H -SCH3 ~[~;3 75o C

18 3-CF3 H H ff -S~H3 ~ 78 C
~H3 19 3-CF'3 H H H -SCH3 ~[~ 66 C

CH~
20 3-CF3 H H }I -SCS~

-:

Le ~ ?7 559 - 63 -. : . - ~ .
..

- :- ~ .. ..
- - - . . -, ..

2 ~
, ~

Table 2 (Cont~nuation) E:x. Nelting No . Rl R2 R3 R4 Z H~t. po$nt 21 3-CF3 H H M OC2H5 ~1~¦ oll 22 3-CF3 H H H -OC2~15 ~3 69 C
c~3 233-CF3 H 11 MC2H5 ~¦ .oil S

243-CF3 H H H-C2HS ~3 78 C
S

253-C~3 H H HOC2H5 ,1~3~ oil 26 3-CF3 H H H ~~ 2H5 ~,N~

27 H H H H-SCH3 ~ 74 C

2~3-CF3 H H H-OCH3 ~3 75o S:

29 H H H H-SC~3 ~3~ 921:

Le A 27 ~59 - 64 -.. ~ .. . .

, J~

Table 2 ( Continuation) l~x. ~Qltin~
2ilo . Rl R2 R3R4 z H~t pO~ nt ~N
H H H H-SCH3 ~) 97o C

31 H H H He2H5 ,1~1 74o C

32 ~ H H H-OC2H5 ~ 77 C

34 H H H H-OC~H5 ~[~l~c1050 C

3-Cl H H H-SCH3 ~ 92 C

36 3-Cl H H H-OC2H5 ~[~3 dO C

37 3-CI H H H-OC2H5 ~ 141 C

38 3-Cl H H HOC2H5 ~¢3~ B~ C

Le A 27 ~5~ -6~ -Table 2 ( Continuation ) Ex. Xelting No. ~1 R2 R3 R4 z Hot.point , . . . .

39 3-Cl H H H -SCH3 ~1115 C

3-Cl H H H -OCH3 ~ oil 41 3-Cl H H H-OC(CH3~3 ~3 oil 42 3-Cl H H H-OC 3H7-n ~374o C

43 3-C1 5-Cl H H -SCH ~ ~31334 C

~4 3-Cl H H CH3-SCH3 ~3 60 C

2-F 4-F H H -SCH3 ~ 7B C

46 3-CF3 5-CF3 H H -SCH3 ~31314 C

47 4-Cl H H c~3-SCH3 ~ 103 C

~8 3-Cl H H H -C~ 2 ~3 724 C

Le P~ 27 ~59 - 66 -- ~ ` 2~3~ ~7~

Table 2 ( Continuation ) Bx. Nelting No ~ Rl Ea2 R3 R4 z H~t. point 49 4-Cl H H CH3 -C2H5 ~ oil 2-F 4-F H H C2H5 ~ 61C

51 3-Cl 5-Cl H H C2H5 ~ 123~

52 H H H CH3 -SCH3 ~ oil 53 3-CI H H CH3 -C2H5 ~ oil ~:

54 H H H -C2H5 ~SCH3 ~ oil H H R CH3 -C2H5 ~ oil 56 4-Cl H H H -SCH3 ~ 127C

57 2-Cl H H H -SCH3 ~ 134C

58 2-CH3 H H H -SCH3 ~ oil 59 4-CI H H H -SCH3 ~ 113-S ~ ,5C

~LaL~ 7 -`

2 ~ 7 ~

Table ~ (Continuation) ~x Nelting No R1 R2 R3 R4 Z H point . .

4-Cl H H H -SCH3 ~ 133C

61 4-Cl H H H -SCH3 ~ ~3-0 94,5~C

62 4-Cl H H H -SCH3 ~ 100-63 4-Cl H H H -SCH3 ~ 125-S 126,5C
_CH
64 4-Cl H H H -SCH3 ~ 143~C

4-Cl H 8 H -SCH3 ~ 142-~H3 66 4-Cl H H H -SCH3 ~ 88-90C
c~3 S7 4-Cl H H H -SCH3 ~ 123-~ C~3125c e A 27 559 68 -.

' , ' ' ' ' , ~3~7~

Tabler2 ~Continuation) ~x. ~elti~g ~- Rl R2 R3 R4 z Hs~ poi~t .. . . . . ~

68 4~Cl H H H -SCH2COOC2H5 ~ o.~l 69 4-Cl H H H -SCH3 ~ 25~ C
C~3 S CH3 ~H3 N
4-Cl H H H -SCH3 I ~1 126-~ S~CH31;27 C

71 2-CH3 H H H -SCH3 { ~ l oll ~N
72 2-CH3 H H H -SCH3 ~ oil 73 2-CH3 H H H -SCH3 ~ oil Cy~N
74 4-Cl H H H -SCH3 ~ 123 C

h--N
Z-~H3 H H H -SCH3 ~SCH3 oil 77. 4-~ H H H -SCH3 Le A 27 559 - 69 -.. . . :, :

- .

Table 2 (Continuation) lelt~ng ~ Rl E~2 R3 R4 z H-t point . .

7~3 3-CF3 H H H -SCH

79 4-F' H H H -SCH3 ~N

3-Cl H H H -SCH3 ~ 81 C

81 3-Cl H H H -SCH3 ~ 88 C

82 4-Cl H H H -SCH3 ~3 1198 C

83 4-Cl H H H -SCH3 ~ 3 C

84 4-Cl H H H -SCH3 ~ 1 l080 C

4-Cl H H H -SCH3 ~ 139,5-86 4-Cl H H H -OC2H5 ~1 125 C

87 3-E3r H H H -SCH3 --01 130 C

- : , , ' ' - : ' Table 2 ( Continuation ) ~x. ~elting -88 3-Cl H H H -OCH ~ OJ 118 C

89 2-Cl H H H -SCH3 ~3 118 C

3-CF3 H H H -SCH3 ~ 131 c 91 3-CF3 H H H -SCH3 ~ 106 C

92 2-Cl H H H -SCH3 ~ 144 C

93 3-Cl H H H -SC2H5 --CN 115C

3-Cl H H H -SCH3 ~\ 98 C

3-Cl H H H -OC2}~5 ~ 105 C

96 3-Cl H H H OC2H5 ~3 oil 97 3-Cl H H H -SC2}~5 ~ 112 C

98 3-Cl H H H -OCH3 ~3 63 C

7 5~ - 71 able 2 (Continuation) ~blting No R~ ~2 R3 R4 z H-~ point 99 3-Br H H H -OCH3 ~N 130 C

100 3-Cl H -CH3 H -SCH3 --GN 140 C

101 3-Cl H H H -OCH2-CH=CH2 ~N 128 C

102 2-Cl H H H OC2H5 ~N 121 C

103 2-Cl H H H -OCzHs ~ 73 C

104 Z-CF3 H H H -SCH3 ~ N oil 105 3-F H H H -SCH3 ~N 104 C

106 2-CF3 H H H -C2Hs ~N 128 C

107 3-F H H H -C2H5 ~N 100 C

108 4-Cl H H H -N~ ~1 19;~ C

109 3-Cl H H H -NHC3~7n {~ 142 C

3~ ~ 7~ :

Preparation of the ~tartin~ csmpounds E~ample (III-l~

Cl~

2.5 g (0.008 ~ol) of 4-methylthio 2-(3-~hloro-phenyl)-6-(4-pyridyl)-pyridine in 30 ml of dry methylene chloride ar~ treated with 0.7 ~ tO.016 mol) of formic acid and 0.1 g of ammonium molybdate. 2.3 g (O.024 mol) of 35~ strength hydrogen peroxide solution are added dropwise at room temperature to the vi~orou~ly stirred mixture. The mixture i~ stirred for 16 hours a~ room temperature, ~nd the organic phase i8 Beparated of f and washed with sodium hydrogen sulphi~e ~olution. ~hs resulting ~olution i8 dried over ~odium sulphate and concentrated. The residue i8 stirred with diethyl ether, and the reaulting cryBtalline product i~ filtered off with ~uction and dried. 2.1 g (76% of theory) of 2-(3-chlorophenyl)-4-methyl6ulphonyl-6-(4-pyridyl)-pyridine of melting point 217C are obtained.
~he compound~ of the ~eneral formula (III) Le A 27 ~59 _ 73 _ . .,:
;: , 7 ~

R4~3 ( I I I ) E~2 which are listed in Tab1Q 3 ~re obtainerl analogou~ly ~o Preparation l~xample ( III-1) and ~ollowing the general preparation in3truct ~ ons .
5Table 3 Ex. Ileltin~
No . R 1R2 R3 R4 R7 H~ t point _ _ III-2 4-C1 H H H CH3 ~3 1?9 C

3 4-C1 H H H CH3 ~ 130 C
(deCOmP. 3 I I I -4 4-C1 H H ~ CH3 ~3 175 C
s I I I -5 3-CF3 H H H CH3 ~3 1 36 C
o I I I - 6 3 - ~F3 H H H ~H3 J~l 1 4 20 C
0~~~ ~3 ~deC~mP. t 7 3-CF3 H H ~ C~3 ~Q 140 C
I
C3~3 :
Le A 27 559 : - 74 -~ :

; ~
, .

- 2~3~ 77~3 Table 3 ( Continuation ) 2x Nelting No R~ R2 R3 R4R7 H-~ point III-8 3-CF3 H H HCH3 ~3 151 C

III-9 3-CF3 }I H H CH3 ~¦ 1570C

I I I -103-CF3 H 3 ~S--`C}I

III-11 H H H HCH3 ~3 186C

III-12 H H H HCH3 ~j~ 177C

I i I - 1 3 H H ~O~--CH 3 III-14 H H H HCH3 ~ 196 C

III-15 3-C1 H H HCH3 ~3 129 C

I I I-16 3-C1 H H HCH3 ~ 142 C

Le ~ 27 559 - 75 _ 7 ~ ~

able 3 (Continuation) Ex. Nelting No. Rl R2 R3 R4 R7 H~ point .

I I I - 1 7 3 - C 1 H H H --~o,--CH3 III-18 3-Cl S-Cl H H CH3 ~3203~ C

III-19 4-C1 H H ~3 CH3 ~3176 C

I I I -2C3-CF3 S-CF3 H H CH3 ~3222 C

III-21 2-F 4-F H H CH3 ~ 151C

III-22 3-C1 H H CH3 CH3 ~3 134C

III-23 H H H CH3 ~3 ~3164 C

III-24 H H H-C2~s C~33 ~¦ 1400 C

III-25 4-C1 H H H CH3 ~N240~ C

111-26 2-C1 H 11 H Cli3 ~N 74~ C

Le A 27 55~ ~ 7~ -- :;, ~. .

, - . 2 ~ P~ ~

Table 3 (Continuation) Ex. ~elting No. Ra R2 R3 R4 R7 Ho~ po~nt III-27 3~Cl H H H CH3 ~ ~8~C

~Il-28 3-C1 H H H CH3 ~ 173C

III-29 3-Br H H H CH3 ~ 220C

III-30 3-CF3 H H H CH3 ~ 227C

III-31 3-CF3 H H H CH3 ~ 229C

Le A 27 559 - 77 _ .

2~3~

Example (IX-1~
¦¦ ,SCH3 N ~ -C~-C~
~8,~ SCH3 20.1 g (0.265 mol) of carbon disulphide are added to 30.3 g (0.25 mol) of 4-acetylpyridine in 300 ml of dry dimethylformamide, and 16.5 g ~0.55 mol) of sodium hydride (~n the form ~f an 80~ susp~nSion i~ oil3 are then ~dded ~n portions. During this proceæ~, the t~mpera-ture rises t~ about 40DC. The mixture is ~tirred ~or 30 minutes at room t~mperature, and 88.8 g (0.623 mol) of methyl iodide are then added dropwi8e over a period of 30 minutes. The reaction mixture i6 3tirred for 3 hour6 at room temperature and i~ then treated with 600 ml of ice-water. The resulting precipitate i~ filtered o~f with ~uction, washed with water and recry~tallized from isopropanol. l9.B ~ (35~ of theory) of 3,3-bi~-(methyl-thio)-1-(4~pyridyl)-2-propen-1-one of melting point 252~C
(decomposition) are obtained.
Example (IX-2j 3,3-Bi~(methylthio)-1-(3-thienyl)-2-propen-1-one of ~elting point 102C ars obtained analogously to Preparation Example (IX-l).

Le A 27 ~9 - 78 . . .

.

7 i~ ~
Use Example~
~xample A

Post-emergence test (greenhouse) Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of a~ti~e compound, 1 part by weight of active c~mpound iB mixed with the sta~ed amount of ~olvent, the stated amount of emulsifier iB added and the concentrate iB diluted with water to the desired concentration.
Test plant~ which have a height of 5 - 15 cm are sprsyed with the preparation of the active compound in such a way as to apply t~e particular amounts of active compound de~ired per unit area. The concentration of the ~pray liquor is so chosen that th~ par~icular ~mnunts of a~tive c~mpound de~ired are applied in 1,000 1 of water/ha. After ~hree weeks, the degree of damage to the plants is rated in % damage in comparison to the develop-ment of the un~reated control. The igures denote:
0% = no action (like untreated control) 100% = total destruc~ion In this test, a very good act~vi~y and selec-tivity towards crop plants iB shown, for example, by the compound6 of the following Preparation Ex2mples: 2, 87 23 and 3~.

Le A 27 5~$9 - 79 . .: . . . .

. . . . .

'~3~77~ ~

Example B
Pre-emergence ~est (greenhouse) SolYent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether ~o produce a suitable preparation of active compound, 1 part by weight of active compound ia mixed with the stated amoun~ of solvent, the stated amount of emul~ifier i8 added and the conc~ntrate is dilu~d with water to the desired concentration.
Seeds of the test plants are ~own in normal 80il and, after 24 hours, watered with the preparation of ~he active compound. It is expedient to keep con~tant ~he amount of water per unit area. ~he concentration of the active compound in ~he preparation is of no importance~
only the amount of acti~e compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. ~he figures denote:
0% = no action (like untreated control) 1004 = total destruction In thiR test, a clearly BuperiOr activity and selectivity towards crop plants compared with the prior art is shown, for example, by the compounds of the following Preparation Examples: 27, 39 and 2.

Le A 27 559 - B0 -- : . - .
: .

Claims (23)

1. A 2-aryl-6-hetarylpyridine of the formula (I) in which R1 represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 independently of one another represent hydrogen or alkyl, Het represents in each case unsubstituted or substituted pyridyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, thienyl, furyl, thiazolyl, isothiazolyl, oxazolyl or isoxazolyl, and Z represents hydrogen, halogen or the groups -Xn-R5-1 or , where X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent in each case optionally substituted alkyl, alkenyl or alkynyl, and R6 represents hydrogen or alkyl, or R5-2 and R6 together with the nitrogen atom to which they are bonded form a 5- to 7-membered Le A 27 559 - 81 -saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups, and n represents 0 or 1, with the exception of the compounds 5-methyl-3-trifluoro-methyl-1-(6-phenyl-4-trifluoromethyl-2-pyridyl)-pyrazole,
2-(4-dimethylamino-phenyl)-6-(2,5-dimethylpyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine; 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-[4-(bromomethyl)phenyl]-2,2'-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine.
2. A 2-aryl-6-hetarylpyridine according to claim 1, in which R1 represents hydrogen, halogen, in each case straight-chain or branched alkyl or alkoxy having in each case 1 to 6 carbon atoms, or represents straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R2 represents hydrogen, halogen, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R3 and R4 independently of one another in each case represent hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, Het represents pyridyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, thienyl, furyl, thiazolyl, isothiazolyl, Le A 27 559 - 82 -oxazolyl or isoxazolyl, each of which is unsubsti-tuted or monosubstituted or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkoxy or alkylthio in each case having 1 to 6 carbon atoms, in each case straight-chain or branched halogeno-alkylthio or halogenoalkoxy in each case having 1 to 6 carbon atoms and in each case 1 to 13 identical or different halogen atoms, phenylamino and (di)alkylamino having 1 to 6 carbon atoms in the respective straight-chain or branched alkyl moities, where, in the case of dialkylamino, the two radicals together with the nitrogen atom to which they are bonded optionally form a 5- to 6-membered saturated or unsaturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 alkyl groups having -1 or 2 carbon atoms, Z represents hydrogen, halogen or the groups -Xn-R5-1 or , where X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent alkyl haYing 1 to 8 carbon atoms, alkenyl Le A 27 559 - 83 -having 2 to 6 carbon atoms or alkynyl having 2 to 6 carbon atoms, each of which is straight-chain or branched and optionally monosubstitu-ted or polysubstituted by identical or differ-ent substituents selected from the group consisting of halogen, cyano, straight-chain or branched alkoxy having 1 to 6 carbon atoms, and straight-chain or branched alkoxycarbonyl-alkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, and R6 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or R5-2 and R6 together with the nitrogen atom to which they are bonded form a 5- or 6-membered satura-ted ring which optionally contains an oxygen, sulphur or nitrogen atom and which is option-ally monosubstituted or disubstituted by a member selected from the group consisting of methyl and ethyl, and n represents 0 or 1, with the exception of the compounds 5-methyl-3-trifluoro-methyl-1-(6-phenyl-4-trifluoromethyl-2-pyridyl)-pyrazole, 2-(4-dimethylamino-phenyl)-6-(2,5-dimethyl-pyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine, 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-[4-(bromomethyl)phenyl]-2,2]-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine.
3. A 2-aryl-6-hetarylpyridine according to claim 1, Le A 27 559 - 84 -in which R1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, or represents straight-chain or branched halogeno-alkyl having 1 to 4 carbon atoms and 1 to 9 fluorine or chlorine atoms, R2 represents hydrogen, fluorine, chlorine, bromine, straight chain or branched halogenoalkyl having 1 to
4 carbon atoms and 1 to 9 fluorine or chlorine atoms, R3 and R4 independently of one another in each case represent hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl, Het represents pyridyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, thienyl, furyl, thiazolyl, isothiazolyl, oxazolyl or isoxazolyl, each of which is unsubsti-tuted or monosubstituted to trisubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, in each case straight-chain or branched halogenoalkyl, halogenoalkoxy or halogenoalkylthio each of which has 1 to 4 carbon atoms and 1 to 9 fluorine or chlorine atoms, phenylamino and (di)alkylamino having 1 to 4 carbon atoms in the respective straight-chain or branched alkyl moieties, where, in the case of dialkylamino, two alkyl moieties together with the Le A 27 559 - 85 -nitrogen atom to which they are bonded can form a 5-or 6-membered saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2- methyl groups, Z represents hydrogen, fluorine, chlorine, bromine or the groups -Xn-R5-1 or , where X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms or straight-chain or branched alkynyl having 2 to 4 carbon atoms, each of which is optionally monosubstituted or disubstituted by identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano and straight-chain or branched alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and l or 2 carbon atoms in the alkyl moiety, and R6 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or R5-2 and R5 together with the nitrogen atom to which they are bonded form a 5- or 60membered satura-ted ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by 1 or 2 methyl groups, Le A 27 559 - 86 -and n represents 0 or 1, with the exception of the compounds 5-methyl-3-trifluoro-methyl-1-(6-phenyl-4-trifluoromethyl-2-pyridyl)-pyrazole, 2-(4-dimethylamino-phenyl)-6-(2,5-dimethyl-pyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine, 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-[4-(bromomethyl)phenyl]-2,2'-bipyridine, 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine.

4. A 2-aryl-6-hetarylpyridine according to claim 1, in which R1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl or trichloromethyl, R2 represents hydrogen, fluorine, chlorine, bromine, trifluoromethyl, difluoromethyl or trichloromethyl, R3 and R4 independently of one another represent hydrogen, methyl or ethyl, Het represents pyridyl, pyrrolyl, thienyl, furyl or thiazolyl, each of which is unsubstituted or mono-substituted or disubstituted by identical or differ-ent substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethyl, methoxy and methylthio, Z represents hydrogen, fluorine, chlorine, bromine or the groups Xn-R5-1 or , where Le A 27 559 X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represents methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, methoxymethyl, ethoxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, allyl or propargyl, and R6 represents hydrogen, methyl, ethyl, n-propyl or i-propyl, or R-2 and R6 together with the nitrogen atom to which they are bonded represent pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino or 2,6-dimethylmorpholino, and n represents 0 or 1, with the exception of the compounds 5-methyl-3-trifluoromethyl-1-(6-phenyl-4-trifluoromethyl-2-pyridyl)-pyrazole, 2-(4-dimethyl-amino-phenyl)-6-(2,5-dimethylpyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine; 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-[4-(bromomethyl)phenyl]-2,2'-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine.
5. 2-(3-Chlorophenyl)-4-ethoxy-6-(4-pyridyl)-pyridine of the formula .
6. 2-(3-Chlorophenyl)-4-methylthio-6-(3-thienyl)-pyridine of the formula .
7. 2-(3-Trifluoromethylphenyl)-4-ethoxy-6-(3-thienyl) pyridine of the formula .
8. 2-Phenyl-4-methylthio-6-(3-thienyl)-pyridine of the formula .
9. 2-(3-chlorophenyl)-4-methylthio-6-(4-pyridyl)-pyridine of the formula
10. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.
11. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 9 in admixture with a solid diluent or carrier, a liquefied normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9.
13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.
14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.
15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90 % by weight of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.
16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied as a pre-emergence herbicide.
17. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied as a post-emergence herbicide.
18. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 15 kg/ha.
19. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied to an area of cultivation at a rate of between 0.05 and 10 kg/ha.
20. A process for preparing a 2-aryl-6-hetarylpyridine derivative of the formula (I) (I) in which R1 represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 independently of one another represent hydro-gen or alkyl, Het represents an unsubstituted or substituted hetero-cycle and Z represents hydrogen, halogen or the groups -Xn-R5-1 or , where X represents oxygen or sulphur, R5-1 and R5-2 independently of one another represent in each case optionally substituted alkyl, alkenyl or alkinyl, R6 represents hydrogen or alkyl, or R5-2 and R6 together with the nitrogen atom to which they are bonded form a 5- to 7-membered saturated or unsaturated ring which optionally contains a further hetero atom and which is optionally substituted by 1 or 2 alkyl groups, and n represents o or 1, with the exception of the compounds 5-methyl-3-trifluoromethyl-1-(6-phenyl-4-trifluoromethyl-2-pyridyl)-pyrazole, 2-(4-dimethyl-amino-phenyl)-6-(2,5-dimethyl-pyrrol-1-yl)-pyridine, 6-phenyl-(2,2'-bipyridyl), 4-methylthio-6-phenyl-2,2'-bipyridine; 4-methyl-2-phenyl-6-(2-thienyl)-pyridine, 6-[4-(bromomethyl)phenyl]-2,2'-bipyridine; 6-(4-methylphenyl)-2,2'-bipyridine and 4-(methylthio)-2-phenyl-6-(2-thienyl)-pyridine, which process comprises:
a) for a 2-aryl-6-hetarylpyridine derivative of the formula (Ia) (Ia) in which R1, R2, R3, R4, R5-1 and Het have the abovementioned meaning reacting a 1,5-dioxo compound of the formula (II) or isomer thereof of the formula (IIa) (II) (IIa) in which R1, R2, R3, R4, R5-1 and Het have the abovementioned meaning with ammonia or an ammonium salt, or b) for a 2-aryl-6-hetarylpyridine derivative of the formula (Ib) (Ib) in which Z1 represents OR5-1 or and R1, R2, R3, R4, R5-1, R5-2, R6 and Het have the above-mentioned meaning, reacting a 4-sulphonylalkyl-2-aryl-6-hetarylpyridine derivative of the formula (III) (III) in which R1, R2, R3, R4 and Het have the abovementioned meaning and R7 represents alkyl either .alpha.) with a compound of the formula (IV) R5-1-OM (IV) in which R5-1 has the abovementioned meaning and M represents an alkali metal cation, or .beta.) with an amine of the formula (V) (V) in which R5 2 and R have the abovementioned meaning, or c) for a 2-aryl-6-hetarylpyridine derivative of the formula (Ic) in which R1, R2, R3, R4 and Het have the abovementioned meaning and Z2 represents halogen, reacting a 4-hydroxy-2-aryl-6-hetarylpyridine derivative of the formula (VI) (VI) in which R1, R2, R3, R4 and Het have the abovementioned meaning, with a halogenating reagent, or d) for a 2-aryl-6-hetarylpyridine derivative of the formula (Id) (Id) in which R1, R2, R3, R4 and Het have the abovementioned meaning and Z3 represents hydrogen, in each case optionally sub-stituted alkyl, alkenyl or alkinyl, starting with a 2-aryl-5-hetarylpyridine derivatlve of the formula (Ic) (Ic) in which R1, R2, R3, R4 and Het have the abovementioned meaning and Z2 represents halogen, either .alpha.) dehalogenating the compound of formula Ic) in the presence of a catalyst, under hydrogen pressure, or .beta.) reacting the compound of the formula Ic) with a diester derivative of the formula (VII) (VII) in which R5-3 represents hydrogen or in each case optionally substituted alkyl, alkenyl or alkinyl and R8 represents methyl or ethyl, and hydrolyzing the compound so obtained in the presence of a base, and subsequently decarboxylating the product in the presence of an acid.
21. A process for preparing a herbicidal composition comprising admixing a compound according to any one of claims 1 to 9 with a suitable dlluent or carrier and/or surface active agent.
22. A 4-alkylsulphonyl-2-aryl-6-hetarylpyridine of the formula (III) in which R1 represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 independently of one another represent hydro-gen or alkyl, Het represents an unsubstituted or substituted hetero-cyclic radical and R7 represents alkyl.
23. A 4-hydroxy-2-aryl-6-hetarylpyridine of the formula (VI) in which R1 represents hydrogen, halogen, alkyl, alkoxy or halogenoalkyl, R2 represents hydrogen, halogen or halogenoalkyl, R3 and R4 independently of one another represent hydrogen or alkyl, and Het represents an unsubstituted or substituted hetero-cyclic radical.
CA 2039770 1990-04-07 1991-04-04 2-aryl-6-hetarylpyridine derivatives Abandoned CA2039770A1 (en)

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DE19904011361 DE4011361A1 (en) 1990-04-07 1990-04-07 2-Aryl-6-hetero:aryl-pyridine cpds. - useful as defoliants, desiccants, weedkillers and fungicides
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US8455638B2 (en) 2007-09-06 2013-06-04 Merck Sharp & Dohme Corp. Soluble guanylate cyclase activators
US8507512B2 (en) 2009-02-26 2013-08-13 Merck Sharp & Dohme Corp. Soluble guanylate cyclase activators

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US5747423A (en) * 1996-07-15 1998-05-05 American Cyanamid Company Herbicidal 6-thienyl and 4-thienyl pyrimidines
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US7820654B2 (en) 2004-09-23 2010-10-26 Dr. Reddy's Laboratories Ltd. Pyrimidine compounds, process for their preparation and compositions containing them
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US5783522A (en) * 1993-07-16 1998-07-21 Basf Aktiengesellschaft Substituted 2-phenylpyridines
US6165941A (en) * 1993-07-16 2000-12-26 Basf Aktiengesellschaft Substituted 2-phenylpyridines
US8455638B2 (en) 2007-09-06 2013-06-04 Merck Sharp & Dohme Corp. Soluble guanylate cyclase activators
US8507512B2 (en) 2009-02-26 2013-08-13 Merck Sharp & Dohme Corp. Soluble guanylate cyclase activators

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