PH27146A - Heterocyclic substituted azoles and azines and their use as herbicides - Google Patents

Heterocyclic substituted azoles and azines and their use as herbicides Download PDF

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Publication number
PH27146A
PH27146A PH37651A PH37651A PH27146A PH 27146 A PH27146 A PH 27146A PH 37651 A PH37651 A PH 37651A PH 37651 A PH37651 A PH 37651A PH 27146 A PH27146 A PH 27146A
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Philippines
Prior art keywords
alkyl
hydrogen
propynyl
general formula
sulphur
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PH37651A
Inventor
Michael Ganzer
Wilfried Franke
Gabriele Dorfmeister
Richard Rees
Gerhard Johann
Friedrich Arndt
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Schering Ag
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Publication of PH27146A publication Critical patent/PH27146A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • 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
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic 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
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • 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
    • 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
    • A01N43/82—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 three ring hetero 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
    • A01N43/72—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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

TT TT—
HETEROCYCLIC SUBSTITUTED AZOLES AND AZINES
AND THEIR USE AS HERBICIDES
Description
This invention relates to new substituted asoles and ezines, processes for their preparation and their use as herbicides.
It is §nown that certain triawmolopyridiazine and bensothiasolylazolidines possess herbicidal amotivity (BP applications O 176 101 and 0 230 874). However the herbicidal activity of these known compounds is not al- ways sufficient or selectivity problems can occur in im- portant orops.
The object of the present invention is to make nev compounds that do not show these disadvantages and have improved biological properties over the known com- pounds,
It has now been found that heterocyclic substituted asoles and asines of general formulas I
R
0 N % ~ - y x | | (1),
Iw in which
. TY
Ry is hydrogen, €,-Cg-alkyl, Cy-Cg-alkenyl, Cy-Cs- alkynyl, halo-C,~C, -alkyl, halo ~C5=Cg-alke~ «l_-C_ = «C= C_~ nyl, halo 3~Cs alkynyl, Oy Cy cycloalkyl, 3 -C,-oycloalkyl-0, C,-alkyl, halo-C,-C,-oyclo- alkyl, halo-Cy-C,-oycloalkyl-C,~C,~ alkyl, C,y-
C,-alkoxy-C,-C,-alkyl, C,~C,-alkoxy-C,-C,-al- koxy=-C, C= elkyl, cyano-C,~C,-alkyl, carboxy-C, -
Cy-alkyl, C,-Cg-alkoxycarbonyl-C,-C,-alkyl, halo y C,-C4-alkoxy carbonyl-C,-C,-alkyl, C=C, ~ulkoxy-
C,-C,-alkoxycarbonyl=~ C,~C5-alkyl, C,-Cq4-alkoxy- carbonyl-C,-C- alkoxycarbonyl Cy -Cy- alkyl, C,-
Cg5-alkylaginosarbonyl-C,~0,- alkyl or di-C,-Cy- al- kylaminocarbonyl-0, -C,- alkyl. 1 is hydrogen, fluorine or chlorine,
X is the group (CR,R,)=W or (CRy)eV, in which V and W , are bonded directly to the phenyl nucleus. n is 0 or 1.
W is the group CR,Rg or NR, or oxygen or sulphur, with the proviso that when £ = 4, snd n=l, Wis not oxygen and vhen 2 = z, or z), and nn =» O,W in : not sulphur,
Vv is the group CR, or nitrogen,
EE 7 loge : R., R., (and R_ are the same or different and are 2" 5h 5 . each hydrogen, halogen, Cy-Cy-alkyl or halo-
C,-C5-alkyl,
Re is hydrogen, methyl or halomethyl, }
Z is a heterocyclic group of formula 0 : NY | CH L
Lo 1) . / . -
CH J ~y , a, 2, i
OL R
Ny a IT 8 9 o °e
U
: = N 0 ~y <Q 7 2 5
Ze
By Ris R
R 27 13
N
N (CH)
Lo " pL Pp / i
N ~8 - 0 2, Pg
L is halogen, C Cy -alkyl, halo-C,-Cg-alkyl, cyano
Loy o-
eo HF or ¢,~Cy- alkoxy, optionally substituted by up to 9 halogen atone,
Q is the group CH or nitrogen, with the proviso that when Qu N and n = 1, W is not oxygen and when Q = CH or N and n = O, W is not sulphur.
Uy is oxygen or sulphurg . vu, in oxygen or sulphur,
Ryo Rg and Rg are each straight-chained, branched or cyolic C,~C,-alkyl, optionally substituted by ha- > 10 logen, or
R, and Rg together with the adjnGent nitrogen and car- bon atoms form a 5 to 7 membered heterocyelio ring, that is saturated or unsaturated, and op- tionally conteins other hetero atoms, such as 0, 8 or N, and is optionally substituted by one to three methyl groups or one to six halogen atoms,
T is the group D-E.
D is a group (OR) gRy dys
E is oxygen or sulphur or a group BO, 80, NR, g or or CRyoR20, mn i» 0 or 1, p is 1 or 2, oo
Ripe Rise RBpue Rigs Rice Rigs Rigs Rig and Ry, are hydro-
: L946 gen, hydroxy, C,-C, alkyl, halo-C,-Cy-alkyl, C,-Cy- alkoxy, c,-Y5- alkylthio, C,~C,~alkylearbonyloxy or
Gy ~0,- alkoxycarbonyl, and
Ran is hydrogen, 0;-C5- dkyl, halo-C,-Cg- alkyl,
C5=Cq alkenyl or Cy=Oc- alkynyl, surprisingly show an outstanding selectivity to orops whilst at the same time have interesting herbicidal activity.
The expression "halogen'! means fluorine, ohlo- rine, bromine and iodine. The term "haloalkyl" means that one or more hydrogen atoms of the alkyl are re- placed by halogen.
Examples of heterocyclic rings are pyrrole, oxa- sole, thiazole, imidazole, pyridine, oxazine, thiazine, pyrimidine, pyrasine, trissine, oxadiarine and thiadie- sines well as their di- , tetra- or preferably hexahydro ’ ’ derivatives.
The compounds of the invention of general formula
I can be prepred by a process in which
A) when Z is a 3,4-dimethyl-3-pyrroline-2,5-dion-l-yl ; group, a compound of general formula II
IN : : . od
J r = 6 «
Co ly "1 o. N_ . NH, a.
I
] Y (11 in which Ris X and Y have the meanings given under general formula I, is treated with 2,2'-dimethyl- maleic anhydride.
B) When 2 is a 4,5.6.7-tetrahydro=-2H-1,2,3~ tria- solo /3,4-a/ pyridin-8-ium-3-olat-2-yl group, a com- pound of general formula II
Ry 1] 1
On, NN NH
AE. r (11) in which Ry» X and Y have the meanings given under general formula I, is diamotised with nitrous acid, treated with piperidine-2-carboxylic escid, and oyo- lised using » dehydrating agent.
C) when Z ie a 2,3,5,647,8-hexahydro-1H-imidase/1,5- &/- pyridine-1,3,dion-2,y1 or a 2,3,5,6,7,8-pxahydro ' 1H-1,3,4-triasolo/T, 2-87 pyridine-1,3-dion-2-yl group, a compound of general formula II
: : Fe . Ma
Q N — STN NR,
J I | (11) in which Riv X and Y have the meanings given under general formula I, is treated with a compound of i generdl formula V or VI u,
U
0 q (v) 0 ’ | (VI) ! . 1 Cc —
Sn o, in whidh Q, uv, and vu, have the meanings given under gerioral formula I and Roy is C,~Cj-alkyl,
D) when 2 im a 2,3,5,6, 7+8-hexahydro-1H-imidaso/1,5- o/- pyridine-l,3-dion-2-yl or a 2,3,5,6,7,8-hexahydro- 18-1,3,b-trianolo/T,2-a/ pyridine-1,3-dion-2-yl group, &_¢ompound of general formula III
J
; Ry : | N ol HeCalU 0 . : \ ) ~~ 1 (111) x 'q li - 8 /
A i
Ss 77 [¢e in which Ryo Ups X and Y have the meanings given under general formula I, is reacted with a oom- pound of general formula VII
H- ST a
R,.0 Q 22 c (VII)
Us in which @ end vu, have the meanings given under general formula I and Ry, is C,=Cy~ alkyl,
E) when Z is a group of general formula
R
1h : R
Ris 15
Ris \
Ng in which Ro Ryqgr Ryo Rig and T have the meanings given under general formula I, a compound of genersl formula Illa ! Ry 1 0 _ - oT N=C = Ss } i SE (111)
X _ ~ Y
J
J in which Ry» X and Y have the meanings given under general formula I, is treated with a compound of general formula VIII . fas . 12
EEN (VIIY)
NE, in whigh R os Ry 50 Ry po Ry and T have the meanings given under general formula I, and then cyclised to a thiadiaaole ring in the presence of an oxidising agent. /
T) when X ie a 44,5,6,7-tetrahydroindazol-2-y1 group apd L in Cy-C,-alkyl or helo-C,~C,-alkyl, a compound of |general formula IV fo f
N
Co o TN NH NE,
X | |, (xv) i ' i in| which Ryo X and Y have the meanings given under general formula I, is reacted with a compound of gene- ral ‘formula IX
A h oC Lo
29) 9 } 0 ce ol ~ (1x) ¥ 0 . i hi h R C= QC, «0; = n whie 23 is Ca Cy alkyl or hale Cc, Cy alkyl,
G) when 2 ie a 4,5,6,7-tetrahydroindacol-2-yl and L is Cy=Cy- alkoxy, a compound of general formula X
R © oo * Co t } i
Ox. N n pa Te N ! (x) '
X--- . oo EEN H
Y ; 3 in which Ro X end Y have the memnings given under general férbula I, except R, is not hydrogen, is treated with a dimlkyl sulphate or alkyl tosylate,
H) when 2 is a 4,3,6,7-tetrahydroindazol~2-y1 group and
L 1a halogen or cyano, a eompound of general formula X . 0. . . 7 Ss os i ° N.S NT . a. , “A Xx) a X | ) H ( , 1 SL N / } Y : co h su gy
J
SPY in which Rs X and ¥ have the meanings ghven under general formula I, except Ry is not hydrogen, is converted to the corresponding compound in which L is halogen, using a phosphorus halide, a phosplorus oxyhalide, phosgene, thionyl chloride or oxalyl chlo- ride, and if niscessary convertédg this with sodium oyanide to ths corresponding compound in which L is eyano. !
I) when 2 is & 2H-1,2,4-trisgolin-3-on-2-yl group, a compound of general formula IV
CA
{ Tn oy" rl " ~ NH-NH,
X by " (Iv) in which Ryo X and Y have the meanings given under general formula I, is reacted with a compound of
Co general formula XI vo 0 i ' Le R, . R,,0 1 (x1) - 0 Rg in vhich; R, and Ry have the meanings given under gene-
CL cc . ral Farmila I and Rah is 1 4 alkyl, ’ J) when Z2 is a 3H-1,3,4~0xadisgol-2-0n=3-y1 group; a : 0 h : : - 12 - J
JF sompound of general formula XII 0
Ry
Co .C. . "R oO ~~ N . - NH~NH © co | (X11)
X
1 in, which Ry» Ros X and Y have the meanings given / under general formula I, is reacted with phospgene, = rj functionally reactive derivative. / ; : \ ; X) when Z is a 5,6,7,8-tetrahydroquinaroline-2,4(1H, [oo ae 3H)~ dion-3-yl group or a 1,2,445,67~~hexahydro«2,4- dioxo-3H-cyclopentapyrimidin-3-yl group, a compound of general formula XXIX
Noo fv R " ; H / f jl ;
BLM
° (cn) / | ti J CR (XXII) . | CA ee X OR 5°00 -
A oo in which Ry» X, ¥ and p have the meanings given under
Cd ; / general forkula I, and R,g is C,-C alkyl, is cyolised fl fo : /; under bssid conditions and optionally treated with a @ompound of general formula XXIII 3 ; Ryn p (XXIII) / ; | ; { i , ;
Fro - 1B -
oo 27/10 in which Ron has the meaning given under general formula I, except hydrogen, and B is halogen or p-toluenesulphonite, optionally using an acid bind- dng reagent, s The reaction to process variant A) is suit- ably carried out at 20°C to 200%¢, optionally in the presence of a solvent, whereby 2.2'-dimethylmaleio anhydride is reacted in a molar amount of 1 to 3 equivalent of he amine of formula II. The reaction time is between 1 to 24 hours. Uenerally, the react- fon is carried out in the presence of en acid, such as for exemple acetic, where the acetic acid for ex- ample can also act as solvent, It is however also pos- sible to react both reactahts using an inert solvent, such as for example dichloromethane or dimethyl sulpho- xide, and to cyclise the resulting intermediate addition product with an acid anhydride, such as for example ace- tic anhydride.
The reaction according to process variant B) is 20 . generally carried out in three stages without interme- diate purification of the products, according to the following renction scheme:
e Ns HR RE 2 WIR i 0 TRE I RS SR RE i TRE Te . - . & ’ 27) Yu ; - 12 - 1 0 N NH x AN 2 3 (11)
X yd y ’
I ® _o
NY N N, 6 \ (XIV) pd Y | i ~ c yd .
HO
. 0 ! nw
NS N N= No {XV) 3
X
7 Y o® . ®
A ’ (1 a) ~N" “ N 3 NT x v -" 15 - -
Tre ry R rarer Fo Roget Prop mae enh Tatas Creme ere wm a em pe 3 gegen © 4 ema) nn typ 7
HATE TE pee VIEL TT Ca BE Tn RT
CRI ree Re DE Hn Sade Le TT
CL eegRRRe pian hm Sn a bee a Te Re ba ne Ee Ta : ' Lo
The aniline of general formula II, in which
Ris X and Y have the meanings given under general formula I, can be diazotised in conventional manner m agusous acid muspension, at a temperature of -20°% to +10%, with sodium nitrite, with a resction time of 0.5 to 3 hours.
Tha compounds of peneral formula XIV, in which @ is halogen, especially chlorine, or other inorganic groups, such as hydrogen sulphate, or orgenie groupe, such as acetate, ares then treated, at « tempsrature of -20°C to +20°, with pipsridine-2-carboxylic acid and an acid-bénding agent, such as for example a trialkyl- amine,
The sompounds of general formula XV can by cyclised with an soid anhydride, such as for example acetic anhy- ‘ dride, using a base, such as for example pyridine, in an inert solvent, such as for example ether, to give the com- pound of formula I.
The reaction according to process varimnt C) is suitably carried out at a temperature above 20%, for example at 100°C or at the reflux temperature of the reaction mixture. When the reactant is an anhydride of general formula V, the reaction is suitably carried out in the presence of an acid, such as acetic meid, in which the mcetic acid for example also acts as solvent. It ia - 1B = a however also possible that both reactants are re- acted with or without an inert solvent, auch as for example dichloromethane or dimethyl sulphoxide, and the intermediate resulting addition product is cye- ised with an scid anhydride, such as for example acetic anhydride.
The reaction according to process variant D) is carried out in an inert solvent mt a temperature between 20°C and 150%¢, suitably at the boiling point of the solvent. Suitable solvents are {or example alipha- tic end aromstic, optionally chlorinated, hydrocarbons, guoh as petroleum ether, bensens, toluene, xylene, di- chlorome thene, chloroform, tetrnchloremethane, 1,2-di- ¢hloroethane and chlorobenzene, no well as ethers, such - 15 as diethyl snd di-n-butyl ether, methyl tert, butyl ether, tetrahydrofuran, dioxan, and ketones, such as for example acatone, methyl athyd-ketond;limethyl iso- propyl ketonas, ns well as nitriles, such as moetonitrile and propionitrile, sulphoxides such ms dimethyl sulpho- ide, or sulphonate.
The isocyanates or imothiooyanstes of general for- mula III uand ns starting material, can ansily be prepared from tie aniline of general formula II, in which Ry» X aad ¥ have the meanings given in general formula I, by known processes using phosgene or thiophosgene or their reactive
“T40
J
EAS derivatives. , The reaction according to process variant EB) oan be carried out in an inert nolvent, such as for ¥ example ether, methylene chloride, chloroform or ethyl 5 acetate, at a temperature of -50% to +50%, by react- ing a compound of general formula Illa, in whieh Ro / A and Y have the meanings given under general formula
I, with a compound of general formula VIII in which Ry oe
Rye Ryo Rig snd T have the meanings given in general formula XI. The reaction time is between 0.5 to 10 hours.
The resulting compound of general formula XVI
R 1h Rig 1
R, H R 3. T el] h o NH
X . s ~ Sy (XVI) is thermally unstable and therefore is preferably re- acted in the next reaction without isolation.
The formation of the ring can be carried eut using an oxidising agent in an organic solvent. Example of or- ganic molvents are inert solvents, such ns methylene chlo- ride, chloroform, N,N-dimethylformamide and ethyl acetate. ‘The condensation renction for the ring formation oan be : carried out in the prasence of active acid acceptors gene-
eo PIN ; : rally used with oxidising agents. Suitable acid acceptors are organic bases, such as triethylamine, pyridine and dimethylaniline, and inorganic bases “such as sodium hydroxide and scdium carbonate. As oxidising agents there can be used bromine, chlorine, * sodium hypochlorite andothers., When a substituent R represents at least a hydroxy group, the oxidising
A agent can be iodine. » | The reaction according to process variant F) is © 10 suitably carried out using a catalyst in a suitable solvent. The reaction temperature lies between rocm temperature and 150°¢, preferably at the reflux tem- perature of the reaction mixture. Suitable solvents ’ are for example dimethyl sulphoxide, halogenated hydro- carbons, such as for example methylene chloride and chloroform, aromatic hydrocarbons, such as for example benzene, toluene, xylene, chlorobenzene and dichloro- benzene, as well as other solvents which are inert to the reactants, such as for example diethyl ether, tetra- hydrofuran or dimethylformamide.
As catalysts there can be used acids, such as acetic or sulphuric acid, as well as ion exchange re- . agents.
The nydrazines of general foruula TV used as start- ing materials, in which Ryo X and Y have the meanings v 19 = - ORIGINAL MN
L --
J
: “HL given in general formula I, are obtained by treat- ing compounds of genaral formula II in acidic aqueous suspension at a tomperature of «20% to +10% with sodium nitrite and then by reaction with a reducing agent, such as for example tin chloride.
The reaction according to process variants @) and H) oan optionally be carried out with or without a solvent. The reaction temperatures lie between room temperature and 180°C, preferably at the reflux tempe- rature of the reaction mixture. Suitmble solvents in- olude methylene chloride, chloroform, benzene, toluene, chlorobenzene, dichlorobenzene and xylene, as well as } vther solvents inert to the reactants.
The starting materials used for processes G) and
H) of general formula X, in which R,, X and Y have the I meanings given in general formula I, e:cept Ry is not hydrogen, can be obtained according to the following reaction scheme in which, in the compound of general forays XVII, Rs is a ¢,-Cy, alkyl group. 1
ON NH-NH,
TU wo (iv) 0 1 Ras 0 hl ] : 5 | (XVII) _
BAD ORIGINAL EB
27g h 0 Tr i il ) oe MA I (x) ge N nN “
L | ) ,
TTS
The reaction is suitebly carried out in a so0l- vent at a temperature runge of 80% to 200°C. over 05 to 20 hourr. Possible solvents include toluene, xylene and acetic acid.
Compounds of general formula X can exist in three tautomeric forms, but for simplicity those are not shown "in the formula X above.
The reaction according to process variant 1) is carried out using a catalyst in e suitable solvent. The reaction temperature lie between room temperature and 150°C, preferably at the reflux temperature ¢f the re- action mixture. BSuiteble sclventse are for example di- methyl sulphoxide, halogenated hydrocarbon8, such as for sxample methylene chloride end chloroform, aromatic hydrosarbona such a» for exsmple benzene, toluene, xy- lene, ohlorobgnsene anes dichlorobenzens, as well as other solvents which ere inert to the reactents, such as for example diathyl ether, tetrahydrofuran or dimethylforaa- mide. ~ - A = BAD ORIGINAL ky 5
F146
Catalysts which can be used are acids, such as acetic acid or sulphuric acid, as well ns don excahange reagents.
The reaction according tov process variant J) oan be oarried out with or without the une of an inert solvent. Suitable solvents are for example dimethyl sul- phoxide, halogensted hydrocarbons, such ns for example ’ methylene chloride end chlorcform, aromatie hydrocarbone, . ouch az for example benrene, toluene, xylene, chlavBenrene and dichlorobensaney ns wel) as other solvents which are inert to the reactants, such ae for exsmrle diethyl ether, tetrahydrofuran or dimethylformamide,
The starting compound of genersl formula XII, in ‘which Bo Xe¥Y and Ry have the meenirge piven under gene- ral formula I, are obtained by rescting the hydrazine of generel feryuls IV, in which Ris X sand Y heve the mean .inge given under gsnerml formula I, with en ecid deriva- tive of formula XVINI, in which Ro is C=C, slkoxy or halo, according to the following renction acheme: pl oF 7) NR-NEH, (iv)
Lo
CL rx x : 0 . / | j ¢ (XVIII) oo | 6 F — TT on - i%2 - ‘ap ORIGINAL a
0 )
Ry c 0 o_ NN. al NR-NH Ry
Xo Et
Fy (x11)
The reaction according the process variant K) is generally carried out in a suitable solvent with the addition of a base, such as for example an alkali hydroxide or slcoholate, sodium hydride or triethyl- amine, optionally in a two phase system with the addi- tion of a phase transfer catalyst and at temperature between of the phase transfer catalyst and at tempera- - tures between 0°C and 150°C, preferably at the reflux temperature of the solvent. i
The starting materials of formula XXII can be ob- tained according to the following remction scheme?
Fa . 0 eg " > - NaC=0 ll
NUN (IIIB)
ENG
’ . Cc
R 00C (XxvI)
Ry u 2%
PP
MN. rd rd 7 .
Q. ON ZT (Sn.)
I | hs | 2p (XXII)
Y—- ” ~. aN one” ~~ ~~ I Ry - 23a dHY
The reaction of compounds of formula IXXIbp in which Riv X and Y have the meanings given under general formula I, with the enamido esters of formulas XXVI, in which p 1s 1 or 2 and Rog 18 0,-C,~ alkyl, is suitably oarried out in inert solvent, such as for example dio- xane. The reaction temperatures lie betwsen room tem- peraturs and 200%, preferably at the boiling point of the solvent.
Generally the starting materials are used in sto- chiometric amounts. An excess of one or the other can sometimes be advantageous,
The compounds of the invention prepared by the above-mentioned processes can be isolated from the re- action mixture by conventional means , for example by distillation of the solvent at normal or reduced pres- sure or by extraction. CL
An inoreased purity can as a rule be obtained by column chromatography as well as by fractional dis- tillation. -
The compounds of the invention are generally crystalline or viscous substances, that are usually high- ly soluble in halogenated hydrocarbons, such as ahloro- form, sulphoxides, auch as dimethyl sulphoxide, or es- ters, such as ethyl acetate. Co " The starting materials of general formula III and - 24 a
23) qe
IV are mainly new, but oan be prepared by in an ana- logous manner to known Frocesses.
The g¢tive substances of the invention show a good herbicidal activity mgainst broad leaved weeds and grasens. A selective use of the oompounds of the invention in various crops is possible for example in rape. bet, soya beans, cotton, rice, barley, wheat and other cereals. Individual active substances are particularly suitable as selective herbicides in beet, cotton, soya and cereals. However the compounds oan be used tor control of weeds ih permanent crops, such 4g for example forestry, ornamental trees, fruit, vine, dhtrus, nut, banana, coffees, tea, rubber, oil palm, cocoa, barry fruit and hop platations and for the selective con- ‘trol of weeds in annual orops. 1
Sh | The compounds of the invention can used for example
Bh | against the following plant species: ; Dicotyledonous weeds of the species Sinapis, Lepi- : : dium, Calium, Stetlaris, Matricaria, Anthemis, Galinsoga,
Chenopodium, Bressioa, Urtios, Senecio, Amaranthus, Por- tulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesba- ; : nia, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Ropi- ; Ppa, Lamium, Veronioa, Abutilon, Datura, Viola, Galeopsis,
Papaver, Centaurea and Crysanthemum.
Monocotyldonous weeds of the species Avena, Alopecurus, ~ 2s
Echinochdoa, Setaria, Panicum, Digitaria, Poa, Eleusine,
Brechisria, Lolium, Bromus, Cyperus, Agropyron, Sagitta- ria, Monocharia, Fimbristylis, Eleoceris, Tachavirun and
Apera.
The rates of use vary depending on the manner of pre~ snd postemergent use between 0.05 and 5 kg/hs.
The compounds of the invention can be used either alone or in admixture with one another or with other mc- tive agents. Optionally, other plant-protective esgents or pesticides oan be added, depending on the purpose for the treatment. When it is desired to brosdem the spectrum of activity , other herbicides can also be added. Herbioci- delly sotive mixing partners suitable in this connection inelude for example, the active agents listed in Weed Aba- tracts, vol. 34, No. 5 (19865 under the hesding "Lists of common names and abbrevistions employed for currently used . herbicides end plant growth regulators in Weed Abstracts".
An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable ad- juvants, such as organic solvents, wetting agents and oiln.
Such additives may allow a desrense in the dose.
Suitable mixture partners may include phospholipids, " e.g. phosphatidyloholine, hydrogenated phosphatiiiyloholines phosphatidylethanolamines, N-aoyl-phoasphatidylethanclamines, phosphatidylinositol, phosphatidylserine, lysolecithin or - % =
271 7¢ phosphatidylglycerol.
The designated active ingredients or their mixtures oan suitable be used, for example, as pov- ders, dusts, granules, solutions, emulsions or sus- pensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wett- ing, emulsifying and/or dispersing adjuvants. : Suitable liquid carriers are, for example alipha- tic and aromatic hydrocarbons, such as bensene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil fractions and plants oils.
Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, taloum, kaolin, attapulgite, limestone, silicic acid and plant -products, e.g. flours.
As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkyl- phenyl ethers, naphthalenosulphonic acids and their salts, 7 Phenolsulphonic acids and their salts, formsldehyde conden- sates, fatty alcohol sulphates, as well as substituted bens senessulphonic acide and their salts.
The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions cen contain about 10 to 90 per- 2% cent by weight active ingredients, and about 20 to go pr-
I1Ye cent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight or sur- factant.
The agents can be applied in customary fashion, for example with Vater as the carrier in spray mix- ture volumes of approximately 100 to 1,000 1/ha. The agents can be applied using low-volume of ultra-low- volume techniques or in the form of so-called micro- granules. . 5, . J
The preparation of these formulations can be car- ried out {0 knbun mannsr, for example by milling or mix- ing processes. Optionally, individual components can be : mixed just before ues for example by the so-called com- monly used tank-mixing method.
Formulations can be prepared, for example, from the following ingredients.
A) Wattable Powder 2 percent by weight active ingredient percent by weight bentonite 20 35 percent by weight colloidal silicic acid 8 percent by weight cwlecium 1ignosulphonate -~ 2 percent by weight sodium salt of N-methyl-N- oleyl-taurine )
i . 234 b
B) Paste 45 percent by weight active ingredient percent by weight sodium aluminium sili- cate 5 15 percdnt by weight cetyl polygycol ether with 8 mol pf ethylene oxide 2 percent by weight spindle oil percent by weight polyethylene glycol 23 percent by weight water 10 C) Bmulsifiable Consentrat 20 percent by weight active ingredient 75 percent by weight &sophorone 8 percent by weight of a mixture of caloium dodecylbenzenesulphonate and nonylphenol- polyoxyethylene }
The following examples illustrate the preparation compounds according to the invention.
Example 1.01 ( process E) 6-(6,6-Dinethyl-3,5,6,7-tetrahydropyrrolo/Z,1-a7 [L.2.4/- thiadianol-3-ylidenimino)-4-(2-propynyl)-2H-1,k-benzoxa- sin-3¢4H)~one 2.6 g 2-Amino-h,k-dimethylpyrroline hydrochloride was ? suspended in 20 ml methylene dichloride. A solution of 0.75 g sodium hydroxide in 5 ml water was added drop- 29 wise with stirring at 0°C and the mixture stirred for 30
: Aly minutes until the reaction mixture became olear. A solution of 6-isothiecynato-4-(2-propynyl)-2H-1,4- bensoxazin-3(4H)~one in 100 ml methylene dichloride vas added dropwise at such a rate that the temperature did not rise above 5%. The mixture was then stirred for 3 hours, whereby the temperature rose to 20%. With cooling to .20%, a solution of 2.3 g bromine in 10 ml methylens chloride was slowly added dropwise and the mix- ture stirred for 1 hour, whereby the temperature rose to 10°C. Then the solution was washed in turn with 30 ml water, 30 ml 5% aqueous sodium hydroxide and 30 ml water.
The methylene dichloride phase wes dried over anhyirous magnesium sulphate, filtered and concentrated. The resi- due wes purified by silica gel column chromatography.
Yield: 1.5 g = 25% of theory :
Mp1 65°C
Preparation of the Starting Material for Bxample 1.01 6=-1sothiocyanato=b-(2~propynyl)-2H-1.4 benzoxasin-3 (48)-one 4 g 6-Amino-h-(2-propynyl)-2H-1.h bYenzoxazin-3{4H)-one was dissolved in 100 ml methylene chloride and treated at 5% with a suspension of 2.60 g calcium carbonete in 20 ml water, 2.9 g Thiophosgene was then added dropwise . at such a rate that the temperature did not rise above « 30 w
TY ¢ 5%. After 10 hours at room temperatures, the phases vers separated. The organic phase was washed with 50 ml water, dried over Meso, and the solvent removed un- der reduced pressure.
Yield: 4.1 g = 84% of theory | 7
Mp: 120-122°C.
In a similnr manner the following compounds were pre~ pared according to process E.
Example , Physical
No Nang ; constant 1.02 6~(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo- np:133°C [21-07 [Ar2:47 thisdiasol-3-ylidenimine)- ly-mo thyl-2H-1, k-bensoxazin-3( 4H) ~ohe 1.03 6-(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo- mp: 62% 13 [221-67 [342,47 thisdiexmol-3-ylidenimino)- ¢-fluoro-i-(2-propynyl)-2H-1,4k=benzoxasin-3(4H) -one 1.04 L4-(2,3-Dibrome-2-propynyl)-6-(6,6-dimethyl- np165°C 3,5,6,7-tetrahydropyrrole~/2,1-¢/ [3.2.87 _ thiadiazol-3-ylidenimino)-7-fluoro-2H-1,k- benzoxasin-2(4H)-one 1.08 5-(6,6-Dimethyl-5,6-dihydro-3H-thiasolo~ mp:195°C
S71 Yc
Exsuple Physical
No Name ] Constant [243-97 [1,2,4]thindiagol-3-ylideninino) - 6-f1luoro-3-(2-propynyl)-2(3H)-benzothiago- lone 1.06 5-(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo- mp:190°C /2,1-07 /1,2,4/tniadiasol -3-ylideniiino)- 6-2luoro-3-(2-propynyl)-2(38)-bensothiasoe- lone 3 1.07 6-(6,6-Dimethyl-5,6-dihydro-3li-thiadiasolo- mp:124-26°0 [23-0124] thiadiazol-3-ylideniminoe)- 4~(2-propynyl)=2H=1,-bensoxazin-3(sf)=- one 1.08 6-(6,6-Diiethyl-3,5,6,7-tetrahydropyrrolo= mp:110°C 1% [2o1-67/1,2,44/thiadierol-3-ylidenimino)- h-(2-propenyl)-2H=1,h-benroxagin-3( kHO-one 1.09 6-(6,6-Dimethyl-5,6-dihydro-3H-thiazolo- mp: 93°C [2e3-07/1,2,1/thisd1asol-3-ylideninino)- 4-(2-propynyl)=-28-1,4-benzoxazin-3(4B)- one 1.10 6-(6,6-Dimethyl=5,6-dihydro~3H-thiadiazolo~ mp1 53°0 /[2,3-0] [1,2,4/thindlasol-3-ylideninino)- 4-propyl-2H-1,4=-bensoxazin-3(4H)-one
>F {bs
Example Physical
NO Name Constant © l.11 6-66,6-Dimethyl=3,5,6,7-tetrahydropyrrole- apt 11.6068 [Z1-¢] [1.2.47 thiadinzol-3-ylideninino )-
Ypropyl-2E-1,lb-benzoxazin-3(4H)~-one l.12 7-(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo- mp:168°C [Aa-¢] [3.2.4 thiadiazol-J-ylideninino)- 1-(2-propynyl)=-2(1H)-quinokalinone 1.13 7a(6 ,6=Dime thyl=5,6-dihydro-3R-thisgolo~ up1174°0
LBy3-e7 [La thiadiezrol-3-ylidenimino)=- 1-(2-propynyl)-2-(1H) -quinexalindne 1.1% 6-(6,6-Dimathyl=3,5,6,7-tatranydropyrrolo- np165°C [21-87 [T2847 thindiagol-3-ylidenimino)- l(2-propynyl)-2l-1,4-benzthiazin-3(4H)-one 1.15 6~(6,6-bimethyl-5,6-dihydro-3H~thiazole- mp1135-140°0 [2o3-¢] A247 thiadiazol-3-ylidenimine)- 7-f1luoro-l-(2-propynyl)-20-1,4-benroxazin- 3(4H)=-one 1.16 6-(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo- mp1161°0C [2-71.24 thiadiazol-3-ylidenimino)~ : 7-flunro-h-propyl-28-1,h-benroxasin=3(hi)-one i 1.17 6-(6,6-Dimethyl-5,6-dihydro-3H-thisgolo- mp! 156°C - 33 a
5714e
Example Physical
Neo Name Constant [243-97 [112,47 thiadiasol-3-ylidenimine)- mpi156°C 7=-fluoro=l-propyl-2H=1,4-benroxssin-3« (4H) ~one 1.18 4-Oyanonethyl-G-(6,6-dimethyl~3,5,6,7- mpt170-171°C tetrahydropyrrolo/2,1-¢/ /I,2,4/thindiancl~ 3-ylidenimino)-2H-1,4-benzoxazin-3(4H)-one 1.16 G-(6-Methyl-3,%,6,7-tetrahydropyrrolo- mpt171-172°%C
L21-g/ [1,2,47thirdiezol-3-ylidenimino)-
Ye(2-propynyld-2H=~1 b-benzoxazin-3(hH)-one 1.20 ?=Fluoro-6-(S-methyl=3,5,6,7=-tetrahydro- mp1161-162°C pyrrolo/Z,1-¢/ /1,2,47thisdiazol=3-ylideninino)-
Le{2-propynyl}-2H-1,4-benzoxazin-2( 4H) -one 1.21 5-(6,6-Dimethyl-3,5,6,7~tetrshydropyrrolo~ mp:113°¢ [241-¢//1,2,4] thindiagolo-3-ylidenimine)-
Z-propyf-2( 3H) -beneoxanolone 1.22 Y5-(6,6-Pimethyl-5,6-dihydro-3H-thiazolo- mp1113°¢
L[2e3edr [12,47 thiadinsol-3-ylidenimino)e 7. 3epropyl-2(3H)~banzoxarolons 1.23 5-(6,6-Dimethyl-3,5,6,7-tetrahydropyrrolo~ mp:124-127° /[21-¢//1,2,/thindiuzol-3-ylideninino)-
Co } 2 Je
Example Physical
No Name Constant / / 6=fluoro-3-propyl-2(3H)-bensoxasolone 1.24 8a(6,6~Dimsthyl-5,6-dihydro~3-thingole- mp:1l41-242°C | [23-67 [T,2,4] thisdiszol-3-ylideninine)- i 6-fluerc~3«propyl-2(3H)=benroxagzolone { .
I , 1425 5-(G6,6-Dimethyl=3,5,6,7-tetrahydropyrrole- mp:258% i 1231-07 [1,2,47 thiedirzol-3-ylidenimino)- 3=(2-propynyl)=2( 3H) -benzoxuzrolone 11,28 5-(6,6-Dimothyl=53,6-dihydro-3Hd-thinsolo- mp1137°C [Bo3-0] [1.2,4] thiadinrol~3-ylidenimine)- 3-(2-propynyl)-2(3H)-benzoxanolone ) 1027 5-(6,6-Dimethyl-3,5,6,7~tetrahydropysrolo~ upt169-173°0 [2.1~¢7 [1,2,li/thizdiasol-3-y1lideninine)- 6-flucro-3-(2-propynyl)-2(3H)=-benzoxazolone 1,28 5-(6,6-Direthyl-9,6~dihydro~3li-thiarolo- mp:138-142% . [2,3-¢7/1,2,47 tniadiagol-3-ylideninino)- ; 8-f1luoro-3-f2~propynyl)-2( 3d) -bensoxazolone
So 1.29 6-(6,6-Dimathyl=-3,5,6,7=telrahydropyrrole. /
A
"0, 20 [21-7 [1,2 i/thisdinrol-3-y1idenining)- i 3-nethyl-l-prepyl~1,3-dihydro-2(@8)-indolone “- 35 a oo Sg e 1.30 6-(6,6-Dimethyl-5,6~dihydro=-3H-thiazolo= [243-97 [A,2,47th1adlas01-3-y11deninino)~ 3-methyl-lepropyle-l,3-dihydro-2(2H)-indolone i 1.31 7-(6,6~-Pimethyl-3,5,6,7~tetrahydropyrrolo- 21-0] (1,2, thiadissol-3-ylidenimino)- 1-(2-propynyl)=2(1H)-quinoxalihone
Example 2.01 (Process A) 1-/6-Fluero-2-oxo-3-(2-propynyl)-2,3-dihydrobensoxasol- 5-y1/- 3,4-dimethyl-3-pyrroline+2,5(1H)-dione oo } 2.8 g 2,3-dimethylmaleic anhydride was added to b g \ .
S5-emino-6-fluoro=-3-(2-propynyl)-2(3H)~bensoxasolone ; in 50 ml acetic mcid. The mixture wes stirred for 8 hours at 80°C. The cooled reagtion mixture was poured into 500 ml fce/water and the precipitated crystals se- parated and washed with water. The product was dried in vacuo at 50°C.
Yield: 2.3g = 38% of theory
Mp: 165°
In a similar manner the following compounds were pre- pared according to process A.
: 211yu
Exanple Physical
Ne Fame 0 Constant 2.02 1-/8-Fluoro-2-oxo-3-(2-propynyl)-2,3- mpt 229% dihydrobensthiasol-5-y)7-3,4-dinethyl-3-
S pyrroline~-2,5(1H)-dione 2.03 1-/3-oxo0-b=(2-propynyl )3,4-dihydre-2B-1,4- mp:279°C bensthiasin-6-yl/-3,4-dimethyl-3-pyrroline- 2,5-(18)~dione 2.04 1-/2-ox0-2,3-dihydro-1H-bensimidazol-5-y}/- mp:280°C 3,4=dimethyl-3-pyrroline-2,5(1H)-dione 2,05 1-/2-0x0-1-(2-propynyl)-1H-quinoxalin-7- mp1265°C yd/ 3.4-dimethyl-3-pyrroline-2,%5(1H)-dione 2.06 1-/3-0xp-1-(2-propynyl)-3,b=dihydro~1f- quinoxalin-7-yl/-3,4-dinethyl-3-pyrroline- 18 2,5(18)~dione . ) : 2.07 1-/2-0x0+3-(2-propynyl)-2,3-dihydrobenzoxesol- 5-y1/-3,44dinethyl-3-pyrroline-2,5(14)-dione 2.08 1-(2-Oxe-3+propyl-2,3-dihydrebensoxasol- mp1110°C ” 5-y1/-344-dime thyl-3-pyrroline-2,5(1H) dione 2.09 1-(3-Methyl-2-oxo0-1-propyl-l,3-dihydro=- mp1180°C 2H-indol-6iyl/~ 3,4-dimethyl-3-pyrroline-
BN - 37 -
: : SF Ya 2,5(1R)-dione 2,10 1-/3-Methyl-2-ox0-1-(1~methylethyl)- mp:1h2-144° 1,3-dihydro-2H-indol-6-y1/=3,b-dime- thyl-3-pyrroline-2,5(1H)-dione
Example 3.01 (process D) 2-/7-Fluoro~3-oxo-h- (2-propynyl)-3,4-dihydro-2H-1,4- benaoxasin-6-y1/ perhydroimidase/T,5-o/ pyridine-1,3- dione 4.1 ml Ethyl piperidine-2-carboxylate was added to = solution of 6.4 g 7-fluoro-b-(2-propynyl)-1,4-bensoxa~ sin-3(4H)-on-6-y1 isocyanate in 50 wl tetrahydrofuran.
The mixture was heated under reflux for 10 hours. After cooling, the solvent was removed under reduced pressure and the residue purified on a silice column with ethyl aoetate/hexane.
Yield: 4.8 g « 52% of theory
Mpt 202-204°%
In a similar manner the following compounds were pre- pared acoording to process D. - 38 a
SE SH (L
Exemple Physical
No Name ~ Constant 3.02 2-/3-0x0-4-( 2-propynyl)=3,4-dihydro~ mp: 180-185% oY -2B-1,4=benzoxasin-6-y1/ perhydroimi- daso/1, 5-a/ ~-pyridine-1,3-dione 3.03 2-/3-0x0-l=( 2-propenyl)-3,ki-dihydro- mp: 157-158 ~2K-1,4=bensoxasin- 6-y1/ perhydroimi- dago/1 ’ S-a/-pyridine 1,3-dione 3.0k 2-/7-Fluoro-3-oxo-4- (2-propynyl)-3,4-dihydro mp: 151% : 2H-1,4-bensoxasin-6-y1/-3-thioxoperhydre- imidaso/1,5-8/pyridin-1-one - 3.08 2-/B-Fluoro-2-oxo-3-(2-propynyl)-2, 3. mpt189-195°0 dihydrobensoxagol-3-yl/-3-thioxoperky- droimidaso/l . 5-¢/pyridin-1- one 1% 3,06 2-(7-Fluoro-3-oxo-k-propyl-3,4-dihydro- : 2H-1,4~be soxantaeb-yLiperhydrotnidase’ /1.5-p/pyridine-1,3-dione 3 i ! /) : 3,07 2-/2-0x0-1-( 2-propynyl)-18-quinoxalin-7-y1/- apt 199-2000 perhydroinidaso/T,5-a/pyridine-1,3-dione \ 3.08 2-/2-Oxo-1-(2-propynyl)-3, 4idihydro-1He quinoxalin-7-yl/perhydroinidesc/I * 5-a7-
SE IF « pyridine~1,3-dione 3,09 2-/2-0x0-3~ (2-propynyl)=2,3-dihydrobennoxa- 201-5-y1/ perhydroimideso /1,%-s/ pyridine- 1,3-dione 3 3.10 2-/6-Fluoro .p.oxo-3-(2-propynyl)-2,3-dihydro- benzoxazin-5-y17 perhydroinideso/1,%-a/pyridine-~ 1l,3~dione 3.1) 2-(3~Methyl-2-oxo-1-propyl-1,3-dihydre-2i=indol- -6~y1/ perhydroimidazo/1,5-8/pyridine-1,3-dione
Jo 312 2-(3-Methyl-2-oxo-1-propyl-1,3-dihydro-2Heindol- -6-y1/perhydro-1H-1,2,4-triazolo [.2-87pyridine- 1,3-dione
Lt it 3.13 2-/B-Fltoro-2-ox0-3-(2-propynyl)-2,3-dihydrodenso- xas01-5-y1/psrhydro-1E-1,2,4~triazole [J2-a/prri- dine-1,3-dione 3,14 2-(2-Oxo-1-propyl-lH-quinoxalin-7-yl)- perhydro-1K- 1,2,4-triasolo/T,2-a/pyridine-1,3¢dione )
Example ba01 (Process K) 3-(3-Oxo-4-propyl-3,4-dihydro-28-1 k-benzoxasin-6-yl)~ 5,6,7,8-tetrahydroquinoxaline-2,4(1H,30)-dione (i
A solution of 4.4 g ethyl 2+/3-(3<ox0~l=propyl=3,k- « 4o =
. ] SY U i ah dro-21-1, b-bensoxanin-6-y1) ureidg/-1-cyelohexaub- carboxylate in 50 ml ethanol vas added to a solution of 2.0 g sodium in 100 ml ethaiol and the reaction mix- pure heated at boiling point for 1 hour. After the re- action had finished, the solption was concentrated and the residue taken up in 300 m1 water. The precipitate was filtered off and the filtrate acidified with hydro- shloric acid. The resultingprecipitate was separated, washed with water and reorystalligzed from ethyl acetate/ diisopropyl ether. : Yield: 3.56 g = 56% of theory
Mp1 > 250°C /
Example 4.02 (process K) 1-Nethyl-3-(lh-propyl-3,b-dinydro-28-1,b-bensexasin-6- 1% 71)=5,647,B-tetrahydroquinoxaline-2,4(1R,3H)-dione 0.17 g 80% sodium hydride suspension was added ‘to a solution of 2.0 g 3-(h-propyl-1, b-bennoxasin-3( bE)-on-
S=y1)=5,6,7,8-tetrahydroquinoxaline-2,4 (1H,38)-dione in 20 ml dimethyl formamide and the mixture stirred at 60°C for 1 hour. It Wms allowed to cool to room tempe- srature and 0.77 g iodomethane added. It was then heated at 60°C for 2 hour. After eooling the crystalline precipi- : tate wan separated and recrystallised from ethyl acetate/ diisopropyl ether.
Yield: 1.3 g = 65% of Gheors (o - b1 =
: SFC
Mp: 218%
Example 5.01 (process I) 2-/B-Fluoro-2-ox0=3-(2-propynyl)-2,3-dihydrobensthia- 201=5-717~2,3,5,6,7,8-hexahydro=1,2,k-triazolo/F,3-a/ pyridin-3-one 2.8 g 1-Ethoxycarbonyl-2~piperidbne and 1 g phosphorus : pentoxide were added to a solution of 3.6 g S-hydrazino- 6-fiuoro-3-{2-propynyl )bensthiazolone in 40 ml xylene and the rixture heated for 2 houre at reflux. After cool- ing, it was added to 100 ml water and the organic phase : " geparated. The organic phase was washed with 40 ml aqueous potasaium hydrogen ¢arbonate, dried over magnesium sulphate and concentrated. The residue was ohromatograpked on sili- oa gel using a mixture of ethyl acetate and hexane as elunt, 13 Yield: 380 mg = 6.7% of theory
Mp: 184-160°C
Preparhtion of the Starting Material for Example 5.01 5-Hydbapino-6-luoro-3-(2-propypyl)-2( He-bansthiasolons hb g iAntno-6- f1uoro-3-(2-propynyl)-2( 3H) -bensthiasolons vas disnolved ih 50 ml concentrated hydrochlorio ameid and 3 — stirred for about 30 minutes at room tempera- vurk. 1t was coolsd to ~5 to +5 °C and a solution of 1.3 8 sodium nitrite in 5.6 ml water added dropwise. The mix- - ture vas then gtirres for 30 minutes and cooled to -30°C. tf : oo - h2 -
CL 2416
A solution of 6.8 g tin (II) ohloride in 15 ml hydro- ohloric acid was slowly added dropwise. The mixture was then stirred for 2 hours, with the temperature held at between -10 and 0°C. Solid material was filtefed off and the filtrate neutralused and extracted three : times with 50 ml ethyl mcetats. The extracts were dried over magnesium sulphate snd the solvent removed under re- duced pressure.
Yields 2.6 g » 61% of theory
In a similar manner the following sompounds were prepared according to process I.
Example Physical
NO Name Vonatant 5.02 2-/2-Oxo-3-(2-propynyl)-2,3-dihydro- mp! 190°C benzoxatol-5-317/2,3,5.,6,7,8-hexahy~ I dro 1,2,4-triazolo/%,3-a/pyridin-3- one : 3.03 2-/7-Fluoro-3-oxo=h-(2-propynyl)-3,4-di- ap1194°0-196°C hydro-2H«),4-bensoxasin-6-y1/2,3,5,6,7,8~ hexahydro-1,2,4-triazolo/l,3-a/pyridin -3~one 3.04 2./5-Fluoro-2-oxo-1-(2-propynyl)-3,h-di- 2 hydro-1H-quinoxalin-§-y1/-2,3,5,6,7,8-hexa- | hydro-1,2,h-triazolo/B,3-a/ pyridin-3-one
: oFlL
Example Physical
No Name gonstant 5.08 2-/8-Fluoro-2-oxo-1(2-propynyl)-1H- pmt190-192°C qunoxalin-7-yl7-2,3,5,6,7,8-hexahydro- 1,2,4-triazolo/R,3-a/pyridin-3-one 4 5.06 2-/8-Fluoro-2-oxo-3,4-dihydro-1H- pn1190-192°C quinoxalin=7-y17~2,3,5,6,7,8-hgxahydro- 1,2 mtr iagolo/l,3-s pyr tdin-3-one
Example 6.01 . | (process B) 28/7-F1uoro-3-oko~(2-propynyl)-3gh-dihydro-2H-1,b-bens- oxanin-6-y17-i,5,6,7-totrahydro-2h-1,2,3-trianolo/3, b-a/ ~pyridin-8-ium-3-ocleate 5,0 g 6 -Amino-7-luoro-h-(2-propynyl)-2i-1,4-bensoxe- sin-3(4H)-one was suspended in a mixture of 12.2 ml con- centrated hydrachlorie acid and 52 ml water and the mix- ture cooled to -10° to +3°C. A solution of 1.74 g so- dium nitrite in 6 a water vas added dropwise at such a rate that the temperature did not rise sbove-5°C. After the addition, the mixture was stirred for 1 hour at -s°c and excess nitrous acid destroyed with urea until a test with lodine-storch paper was negative. The resulting solution vas warned to 0°C and added dropwise to an ice~ cooled molution of 2.9 g pipecolinc acid and 10.3 al trie ethylemine in 38 mlwwater. After the addition, the mix- ture was stirred for 1 hour at 0°C snd the mixture extected = kh -
Co 29) several times with methylene chloride. The combined orgenic phases were dried over magnesium sulphate and the solvent evaporated. The residue was taken up in "60 ml ether and treated with 5.2 ml acetic amhydride and 2.6 ml pyridine. The mixture was stirred overnight at room temperature and poured into 130 ml ice/water.
It was extracted with ethyl acetate and the extract died over magnesium sulphate and the:eolvent evapor- ated. The residue was chromatographed on silica gel using ethyl acetate/methanol (95:5) as eluent.
Yield: 1.0 g &« 13% of theory
Mp: 202-203°C
In a aimilar manner the following compounds were prepared according to process B. 1% Example Physical
Mo 0 Heme = Constant 6302 2-/B-F1jhoro-2-oxo~(2-propynyl)-2,3-dihydro- mp:203°0 bensoxesol-5-y3/ 4,5,6,7-tetrahydro-2H-1, . 2,3,~trianolo/3,4-a/pyrédén-8-iun-3-olute 6.03 2-/6-Fluoro-2-oxo0-3-(2-propynyl)=2,3-di- mp 210°C hydro-bensthiazol-5-y1/-h,5,6,7-tetrahy~ dro-26-1,2,3-triazolo/3,k-a/ pyridin-8-ium-3- : oleate:
Exsmple 7.01 (process J) 3-(3-Me thyl-2-oxo-1-propyl-1,3-aihydro-2-H-indol-6- 717-5-(1,1-dinethylethyl)-1,3,b-oxsdiazel-2(3H)-one 1 ) . 2.6 g 3.Methyl-6-/F*-(2,2-dimethylpropanoyl) hydra- $ sing/-1-propyl-1H-indol-2(3R)-one was dissolved in 15 ml of a 20% solution of phosgene in toluene and the mixture heated for 4 hours at reflux. It was stirred overnight at room temperature, 20 ml methanol carefully added snd the solvent distilled under re- duced pressure. The residue was chromatographed on silica gel ueing hexane/ethyl acetate (7:3) as eluent. 14eld: 1.7 g = 61% of theory
Ne : 1.5366
Preparation of the starting Material for Example 7.01 3-Hothyl-6-/N'(2,2-dinethylpropanoyl dhydrasing/-1- pro- pyl-1H-indol-2(3H)~-one 2.% g Triethylanine was added to a solution of 35.9 8 ’ 6-hydrazino-3-nethyl-1-propyl-1i-indol-2(3H)-one in a mixture of SO ml toluene end 20 ml soetonitrile. 3.1 Eg
Pivaloyl chloride wes added dropwise whereby the tenm- : perature rose to sbout 40°C. The mixture was then stie- red for 1.5 hours, agitated with 100 =l each of water and aqueous potmssitim hydrogen carbonate, dried over magnesium sulphate and the solvent removed. The rosi-
CC. 46 =
Fo 93 YL due was chromatographed on siliom gel using hexane/ ethyl acetate as eleuent.
Yield: 2.7 g = 33% of theory
In a similar manner the following compounds 8 vere prepared according to process J.
Example Physical
No Name Constant 7.02 3-/2-Ox0-3-(2-propynyl)~2,3-dihydro- Mpt127-130°C bengoxazol-8-yl/-5-(1,1-dimethylethyl)~ 1,3, k-oxadiazol-2(3H)-one 7.03 3-/7-Fluoro-3-oxo-4-(2-propynyl)-3,4- mpt1L3-14k4%g dihydro-1,k-benzoxasin-6-yl/-5-(1,1- dimethylethyl)-1,3,A-oxndisxol-2(3H)~ one : 15 7.04 3-f8-Fluore -3-oxo-1-(2-propynyl)-3,b- np:66-68°0 dihydro-1H-quinoxalin-7-yl/-5-(1,1-di~ nethylethyl)-1,3,k-oxadiazol-2(3H)~one 7.03 3-/B-Fluoro-2-oxo-1-(2-propynyl)-1H- ap1152-153° quinoxalin-7-y1/-5-(1,1-dimethylethyl)=~ 1,3,4-0xadiazol-2(3H)-one 7.06 3-/7-F1uoro-3-oxo-3,4-dihydro-28-1,4- np? 171-172% benzoxagin-6-y1/-5-(1,1-dimethylethyl)-
Lo 2714u 1,3,4-0xadiazol-2(3H)~one 7.07 3-/B6-Fluoro-2-oxo-3,4-dihydro-1H- mpe 248°0 quinoxalin-7-yl/-8-(1,1-dimethylethyl)- 1,3, b-0xadiazol-2(3H)~one :
S Example 8.01 (process RH) 3-Chloro-2=-/2-0x0-3~(2~propynyl)-2,3-dihydrobenzoxazol- i $-y1/-44,546,7-te trahydro-2A-1indarole
A mixture of 4.5 g 2~/2-0x0-3-(2-propynyl)-2,3-dihydro- banzexeRol=5-y1/=1,3,4,5,6,7~ hexahydre-2H-indagol-3- one and 20 ml oxalyl chloride was heated for 4 hours at reflux, After cooling, the mixture was poured into 100 nl ice/water and extrmoted with methylene chloride. The oombined organic phases were agitated with saturated aqueous potassium hydrogen carbonate and water and dried over magnesium sulphate. The aolvent removed under re- duced pressure. The residue was chromatographed on sili- ea gel using a mixture of hexane and ethyl acetate as eluent.
Yield: 3.9 g = 82% of theory
Mp: 143-146
Preparation of the Starting Material for Example 8.01 2-/2-0x0-3-(2-propynyl)-2,3-dihydrobensoxasol-3-y1/- l, 3 ° b . 5 ’ 6 . 7~hexahydro-20~indasol-3-one
CC —————————————————————————— A Serr = -— Tm em a —— ae : 24ly
A mixture of 4.9 g ethyl 2-cyoclohexanecarboxylate and a solution of 5.8 g 5_hydrasine-3-(2-propynyl)-2(3H)- benzoxasolone in 24 ml acetic acid was heated for 1 hour under reflux. Excese acetic acid was removed un- 3 duced pressure. The residue was recrystallised from isopropyl ether.
Tield : 5.8 g = 65% of theory
Mp: 177-180°C
In a minilar manner the following compounds were prepared according to process He.
Exemple Physical
No Name Constant 8.02 3-Chloro-2-/7-Fluoro-3-oxe ol=(2-propynyld)= ap:150°0 3,4-dihydro-2H-1,-bensoxasin-6-y1/-k45¢6.7- tetrahydro~2H-indazole . 8.03 3-Chloro-2-/6-fluoro ~3-0x0~1~(2-propynyl)- ppt 195°C 3, b-dihydro-1A-quinoxalin-7-y1/=4,5:6,7= tetrahydro-2H-indazole
The following example illustrate the possibilities for use of the compounds of the invention.
Example A
In a greenhouse, the noted plant species were treated post-emergently with the noted compcunds of the invention,
at a rate of O.1 kg active ingredient/ha. The com- pounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 litres water/ha. Three weeks after the treatment, the oom- pounds of the invention showed a high crop selective- ly with excellent activity against the weeds.
In the following table: 0 =» no damage 4 = total destruction
TREAX = Triticum aostivun
BRSSS = Brassica spe.
BOLSS = Solanum spe
HELAN « Helianthus annuus
ABUTH = Abutilon theophrasti
MATCH = Matricaria chamomilla
VIOSS = Violas sp
IPOSS = Ipomeea purpurea
VERPE = Veronice persica
GALAP « Galium aparine 0 TBS HAMNVIV
R R 0 EB AI PE A ££ 8 LL UT OOR RIL
Compounds of ABB ATO SB 8 PA
Invention X 8 8 N H H 8 8 BP oOFIve
Example 1.01 O 4 bh 4 4 4 4 4 4 4
Example 1.02 0 3 bh 4h & 4 4 4 4 4
Example 1.03 O 4 Lk 4 4 4 4 4 4 4
Example 1.04 0 4 4 4 4 2 2 & 4 4
Example 1.05 1 1 4 3 4 4 4 4 4 3
Example 1.06 01 4 3 L 4 3 4 3 2
Example 1.08 Cc 2 - 3 kh 32 4 & o
Example 1.09 0 3 ~ 4 4 4 4 4 4 3
Example 1.10 1 1 - 3 4 4 3 4 4 3
Example 1.11 0 3 - 3 4 4 - 4 &
Example 1.12 0 3 4 « 4h & - & & 2
Example 1.15 1 3 b- 4 4 4 4 3 3
Example 1.16 1 4 4 - 4h 3 3 3 3 2
Example 1.17 0 2 4 « 4 33 3 22 © Example 1.18 1 3 3 . 4 3 2 3 4 1
Exemple 1.19 1 3 4 - b3 3 3 4 2
Example 1.20 1 4 bh 4h 3 hy
Example 1.23 0 3 4 - 4 3 2 3 3 3
Example 1.27 0 2 &k - 4 3 3 4 3 3
Example 1.28 0 1 4 ~ 4 3 3 4 2 2
Untreated 0 0 00000 0 00
Example B
In a greenhouse, the compounds of the invention shown in the table were applied at the rates given. For this the compounds were applied in vessels containing 1500 ml
SE atl water . As test plants there vere used Echinochloa erus-galli (SCHCG) in the 2 to 5 leaved stage, There wesks after the treatpent, the compounds of the in- vention showed strong sctivity againet Echinochloa
Ss orus-galii.
In the following Table! 0 = no damage : 1. = slight damage 2 = medium danage 3 - " damage h - tote destruction
LY E
LY c
Ht ! RB : 15 Compound of Water application. Cc the invintion =n a : i!
Example 1.01 3 3
Example 1.02 3 4
Untreated 0 : { : !
Example. Cc
Thla greenhouse, the noted plant species were treated
A
- post-emergently with the noted compounds of the invent- 16m) at a rate of 0.01 kg active ingredient/ha. The o apounds of the imvention were sprayed evenly over the v lants as emulsions or suspensions in 500 litres water/ha.
No 2 ; - 52 =
Three weeks after the treatment, the sompounds of the } invention showed a high crop selectivity with excellent activity against the weeds. The comparison saterial did not show the high efficacy. | E
In the following table: o - No damage ; bh = total damage
HRZAX = Triticum aestivum
ZEANX = Zea mays
VI088 = Viola ep
VERPE = Veronica persica
B0LSS = Solanum sp,
SEBEX = Sesbania exaltata
IP0S8 = Epomoea purpurea
ABUTE = Abutilon theophrasti .
T 2 VV 8 8 I A
REIEGOTET PSB
Z A ORL BB OUVY
Compounds of A XM 8 Pp 85 ¢£ 8 T
Invention X X 8 £8 X 8 K
Exauple 1.01 0 0 3 3 § 4 4 ‘5
Example 2.01 0 0 3 4 4 2 4 A
Example 2.02 1 0 3 3 he ok
Example 3.01 - 1 2 4 & bh bh
Bxample 3.02 0 0 « 3 - ~- 3 & - 53% a oo SA) 4L ; /
Example 6.01 2 0 3 4 & Wb & & . \ ateented | ' 900000000" - Gompariscs : | :
Oxadiazoh Oo 000 0 pp 1 § 2
A
In a grgantionas, the noted plant species were treated pre-emergently with the noted compounds of the invent ion, at 'a rate of 0.1 kg active ingredients/ha. The compounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 litres water/ ha. Three weeks after the treatment, the compounds of the invention showed a high orop selectivity in sugar- beet, wheat and maize, with excellent activity against the weeds. The comparison material did not show the same 1% nigh selectivity .
In the following table? 0 = no damage 1: = 1 = 24% damage 2 mn 25 ~ 74% damage 3 = 75 - 89% damage bh = 90 = 100% damage BEAVX = Bete vulgaris sltissima )
TREAX = Triticum aestivum
ZEAMX = Zea mays ; GALAP = Gallium aparine - sh -
EE EEE = 29 14v
MATCH = Matricaris chamomilla : : BT 2 G M . ERE AA ~ AZ ALT
Compounds of V AM AC invention XxX X X PH
Example 3.0h 0 - - ~- &
Example 4.01 | - 00 4
Untréated 0 0 0 0 0
Comparison )
Oxadiskon 1 110 &
Exanple E "In a greenhouse, the noted plant species were treated post-smeggently with the noted cempounds of the invent- 10h, at a rate of 0.1 kg active ingredient/ha. The com- oo ponds of the invention were sprayed evenly over the plants as emulsion or suspension im 500 litres water/ha.
Tub weeks after the treatment, the compounds of the in- ; vention shoved a high crop selectivity in maize with ex- cellent activity against the weeds. The comparison ma- tertal did not show the same high selectivity.
A In the following table: : 0 ‘ no damage / ; 1 g e 1 - 20% damage 2 | x 25 ~ 74% damage a
Lo
Po - 55 = i .
Co i 29(u 's 3 = 25 ~ 89% damage b = 90 ~ 100% damage
ZEAMK = Zea mays "
ABUTH = Abutilon theophrasti
MATCH = Matriceria chamémilla - POL8S = Polyganum Sp.
S0L8A = Bolsnum sp.
VERPE = Veronica persica oo Z AMP SV 1) E B A O OE : A u T L L R
Compounds of ! Me cs 8 P ' invention XxX H BR 8 8 E ; Example 3.04 0 - 3 3 bh 3 / Example 3,05 0 4 - 4 3 4 / Untreated oO 00 0 OO / Comparison / Oxadiason 1 0&4 3 & 4
In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invent- / 1én, at a rate of 1.0 kg active ingredient/ha. The com- pounds of the invention were sprayed evenly over the ; nts as emulsions or suspensions in 500 1itres water/ | a. One week after the treatment, the compounds of the favent on shoved excellent activity against the weeds.
A RE cL. ot qe
In the following table: 0 = no damage l = 1 ~ 24% damage 2 = 25 ~ 74% damage 3 a 75 -89% damage h e 90 - 100% damage
ALOMY = Aopecurus myosuroides
AVEFA = Avena fatua
BETVI = Sataris viridis cYPES = Cyperus esculentus
ABUTH = Abutilon theophrasti 1P0SS =Ipomes purpurea
HATCH e Matricaria chamomilla
AAS CATIH
IL VEY BP A oO E Y PU OT
Compounds of HF VETS C invention Y Al 8s BB 8B B / Example 6.01 O bh ub bb bh bh
Example 6.02 Hb & bh 3 4 hb hb
Example 6.03 hb 4 hk 4 bh bb
Untreated 0 00O0OT OO
Example G "In a greenhouse, the noted plant species vere treated
I
Co. TYG post-emergently with the noted compounds Bf the in- vention, at a rate of 0.1 kg active ingredient/ha.
The compounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 litres water/ha. One week after the treatment, the compounds of the invention showed a high crop selcti- vity in wheat with excellent activity against the weeds.
In the following table: o = no damage 1 = 1 « 24% damage 2 uw 28 « 74% dam ge 3 = 75 - 89% damage 4 w= 90 = 100% damage
PRIAX = Tritious aestivum
ABUTH = Abutilom theophrasti
GALAP = Oalium aparine
IPOSS = Ipomea purporea
MATCH = Matricarie chamomilla - T AG I HM oo R B AP A oo | 2 UL 07
Compounds of AT A 8 OC invention X M P 8 M
Example 6.01 1 0h 3 4 4
Example 6.02 1 4 3 3 3
. . HY
Untreated 0O 0 0 0 0
Example H
In a greanhouse, the noted plant species were treated post-emergently with the noted compounds nf the invent-~ ion at a rate pf 0/3 kg active ingradient/hs. The con- pounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 litres water/ ha. Two weeks after the treatment, the compounds of the invention showed a high crop selectivity in wheat and maize with excellent activity against the weeds,
In the fnllowing table: 0 = no damnnge 1 = 1 - 2h dervage 2 = 2% - 744 dnnage 3 = 75 = 80% damnpa ’ 4 x 90 ~ 100% damage
TRZAX = Triticum aestivum
LEAMX = Zep mays
ABUTH = Abutilon theophrasti 1P0SG =Ipomen purpurea
MATCH = latricaria chamomilla
S50L85 = Solanum spe.
ViOsSs = Viele =p,
T & A I HH 8 V
RoE oBEoA oT 2)
BAD ORIGINAL &50 —
"or 2F Yl 2 AU Oo T L 0
Compounds of AHP 83 ¢ 8 8 dovention _ ___X X MW 3 H 8 8
Exemple 1.13 oO 0 3 % 3 4h 2
Example 1.1h4 0 0 4 4 2 4 1
Example 1.21 oO 0 4 3 3 4 2
Example 1.22 Oo 0 4 3 8 4 3
Example 1.2h 0 0 k 4 3 4 3 : Example 1.25 0 0 uh 4 3 4h 3
Exemple 1.26 oOo 03 3 8 4 3
Example 2.05 2 1 4 4 3 y 1
Untreated gg 0 ¢ cc 0 0 0 — a0 ORIGINAL >

Claims (2)

~ - SFL © 97146 CLAIMS
1. Hetrocyclic susbtituted azoles and azines of general formula I R 1 \ 0 LE . 1 (1), _ 1 in which CoC v «CO - -C - Ry is hydrogen, “ Ce alkyl, 3 Cg alkenyl, Cy 5 alkynyl, halo-C,=C -elkenyl or cyano=G,=C,= alkyl, Y is hydrogen or fluorine, ~ pa . 5 X is the group (CR RSD 4 or (CR, I=V, in which v © and W are bonded directly to the phenyl nucleus. n ie 0 or 1,
sl . W. is the group CH, Rg or NR¢ or oxygen or sulphur, # : with the proviso that when 24 = sy and n= 1, WV is not oxygen and when 3 = 4, or Ly and n = 0, W is not sulphur, . LA is nitrogen, Rye Ry Ry, and Ry are the came or different and are emch hydrogen or © -Csm alkyl, BAD ORIGINAL Re
Lo .
IE ye
Re. is hydrogen, Z ie a hetevocyclie group of formula i O~ ,-CH ~~ Ty 1 N P \ ANN 0 Lo 2, i z, "i ol “a A 1 0. 0 ] ~~ Favs “ Le MN Lo ~ . Z 3 %y,
Q . ON oom ~~ Uy - ~~ OF Y ey Ze : Rie” Fis R
R . {27 13 EB . R,, . "r ~ N § (Oy J ~N SUNT : 8 0 / N on Zz Co 7 8 A. ORIGINAL A Lo dA
© A - 27146 L is halogen, Q is the group Cll or nitrogen, with the proviso that when §{ = N and n = 1, W ie not oxygen and when ¢ = CH or N and n =0Q W is not sulphur, uy is oxygen or sulphur, u, is oxygen, Ry and Ro together with the adjacent nitrbpen and : carbon atoms form, a 5 to 7 membered he trocyclic . ring, that is saturated, Rg is a brenched Cy=C,mnlkyl, BE ia sulphur or a gorup CR gh, P is 2, : 1 J C=, = Ryo iy 59 Hypo STL Rig and Ry area hydrogen or 1~5y alkyl, and Ryn is hydrogen or Cy s alkyl,
2. A herbicidal composition which comprises a compound according to claim 1, in admixture with carriers and - diluents, 3, A method of combating wecda which comprises applying to the weeds or their locus a herbicidally effective artount of a compound according to cleim 1. ) =) /
Br. MICHALL GANZER CF
Dr. WILFRIED FRANKE C=
Dr. GABRIELE DORFHUISTER | &F
Dr. RICHARD REES | &
Dre. GLRUARD QORARN CA pr. FRIEDRICH ARNDT J < - 63 - Inventors — a
PH37651A 1987-10-09 1988-10-07 Heterocyclic substituted azoles and azines and their use as herbicides PH27146A (en)

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DE19873734745 DE3734745A1 (en) 1987-10-09 1987-10-09 TETRAHYDROPYRROLO (2,1-C) (1,2,4) -THIADIAZOL-3-YLIDENIMINOBENZOXAZINONE AND OTHER HETEROCYCLICALLY SUBSTITUTED AZOLES AND AZINES, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDES

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Families Citing this family (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH075591B2 (en) * 1986-08-25 1995-01-25 住友化学工業株式会社 Benzothiazolone derivative and herbicide containing the same as active ingredient
AU605304B2 (en) * 1987-06-22 1991-01-10 Nihon Tokushu Nayaku Seizo K.K. Benzo-fused cyclic compounds
JP2584641B2 (en) * 1987-11-27 1997-02-26 日本曹達株式会社 Heterocyclic compounds and herbicides thereof
US5322835A (en) * 1988-04-20 1994-06-21 Sumitomo Chemical Company, Limited N-phenylimides, and their production and use
JPH02131482A (en) * 1988-07-21 1990-05-21 Nippon Tokushu Noyaku Seizo Kk Herbicidal benzothiazolones
JPH04501567A (en) * 1989-06-09 1992-03-19 チバ―ガイギー　アクチェンゲゼルシャフト heterocyclic compound
DE3922847A1 (en) * 1989-07-07 1991-01-17 Schering Ag SUBSTITUTED BENZOXAZOLINONE AND BENZOXAZINONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDAL ACTION
AU627906B2 (en) * 1989-07-14 1992-09-03 Nissan Chemical Industries Ltd. Uracil derivatives and herbicides containing the same as active ingredient
US5084084A (en) * 1989-07-14 1992-01-28 Nissan Chemical Industries Ltd. Uracil derivatives and herbicides containing the same as active ingredient
BR9004801A (en) * 1989-09-26 1991-09-10 Sumitomo Chemical Co COMPOUND AND PROCESS FOR ITS PREPARATION, HERBICIDE COMPOSITION, PROCESS FOR EXTERMINATING HARMFUL WEEDS AND USE OF THAT COMPOUND
US5314864A (en) * 1989-09-26 1994-05-24 Sumitomo Chemical Company, Limited N-aminouracil derivatives, and their production and use
JP3064374B2 (en) * 1989-10-02 2000-07-12 住友化学工業株式会社 Uracil derivative, method for producing the same, and herbicide containing the same as an active ingredient
CA2026960A1 (en) * 1989-10-12 1991-04-13 Masayuki Enomoto Benzoxazinyl-pyrazoles, and their production and use
CA2028755A1 (en) * 1989-11-09 1991-05-10 Adam C. Hsu Benzoxazolone compounds and the use thereof as microbicides
DE4006555A1 (en) * 1990-02-27 1991-08-29 Schering Ag METHOD AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF SUBSTITUTED 1-BENZTHIAZOLYL-3,4-DIMETHYL-3-PYRROLIN-2,5 (1H) -DIONES
EP0448188A3 (en) * 1990-03-15 1992-02-26 Schering Aktiengesellschaft Process and intermediates for the preparation of substituted 6-(3,5,6,7-tetrahydropyrrolo-(2,1-c)(1,2,4)-thiadiazol-3-ylidenimino)-7-fluoro-2h-1,4-benzoxazin-3(4h)-ones
DE4008691A1 (en) * 1990-03-15 1991-09-19 Schering Ag Prodn. of pyrrolo:thiadiazol:ylidene:imino-benzoxazinone herbicides - from 2-amino-5-fluoro-phenol via new chloro:acetanilide cpds. under mild reaction conditions
DE4012512A1 (en) * 1990-04-12 1991-10-17 Schering Ag Selective synergistic herbicide mixt.
US5238906A (en) * 1990-11-27 1993-08-24 Sumitomo Chemical Company, Limited Pyridone derivatives and use
HUT62296A (en) * 1990-12-18 1993-04-28 Sandoz Ag Herbicidal composition comprising hydantoin derivative as active ingredient and process for producing the active ingredient
DE4117508A1 (en) * 1991-05-24 1992-11-26 Schering Ag SUBSTITUTED BENZTHIAZOLE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN AGENT WITH HERBICIDAL EFFECT
HU9303465D0 (en) * 1991-06-06 1994-04-28 Ciba Geigy Ag New herbicides
DE4125246C1 (en) * 1991-07-26 1993-02-04 Schering Ag Berlin Und Bergkamen, 1000 Berlin, De
DE4132089A1 (en) * 1991-09-23 1993-03-25 Schering Ag HERBICIDES WITH SYNERGISTIC EFFECT
DE4136740A1 (en) * 1991-11-05 1993-05-06 Schering Ag Berlin Und Bergkamen, 1000 Berlin, De HERBICIDES WITH SYNERGISTIC EFFECT
US5252536A (en) * 1991-12-31 1993-10-12 American Cyanamid Company Substituted indolinones useful as herbicidal agents
DE4208778C1 (en) * 1992-03-17 1993-09-23 Schering Ag Berlin Und Bergkamen, 13353 Berlin, De
DE4217952A1 (en) * 1992-05-30 1993-12-02 Basf Ag Quinoxaline-2,3 (1H, 4H) diones
ES2072804B1 (en) * 1992-10-08 1996-02-16 Schering Ag DERIVATIVES OF SUBSTITUTED BENZOTIAZOLES, PROCEDURE FOR PRODUCING THEM AND HERBICIDE COMPOSITIONS THAT CONTAIN THEM.
WO1994018836A1 (en) * 1993-02-17 1994-09-01 Schering Aktiengesellschaft Synergistic herbicidal composition on the basis of thidiazimin
DE4305542C1 (en) * 1993-02-20 1994-07-21 Schering Ag Herbicidal agents with synergistic effects
WO1994022860A1 (en) * 1993-03-26 1994-10-13 E.I. Du Pont De Nemours And Company Herbicidal triazolinones
US6380178B1 (en) 1999-05-04 2002-04-30 American Home Products Corporation Cyclic regimens using cyclocarbamate and cyclic amide derivatives
US6462032B1 (en) 1999-05-04 2002-10-08 Wyeth Cyclic regimens utilizing indoline derivatives
US6498154B1 (en) 1999-05-04 2002-12-24 Wyeth Cyclic regimens using quinazolinone and benzoxazine derivatives
US6417214B1 (en) 1999-05-04 2002-07-09 Wyeth 3,3-substituted indoline derivatives
US6391907B1 (en) 1999-05-04 2002-05-21 American Home Products Corporation Indoline derivatives
US6358947B1 (en) 1999-05-04 2002-03-19 American Home Products Corporation Tetracyclic progesterone receptor modulator compounds and methods
US6369056B1 (en) 1999-05-04 2002-04-09 American Home Products Corporation Cyclic urea and cyclic amide derivatives
US6358948B1 (en) 1999-05-04 2002-03-19 American Home Products Corporation Quinazolinone and benzoxazine derivatives as progesterone receptor modulators
US6509334B1 (en) 1999-05-04 2003-01-21 American Home Products Corporation Cyclocarbamate derivatives as progesterone receptor modulators
US6399593B1 (en) 1999-05-04 2002-06-04 Wyeth Cyclic regimens using cyclic urea and cyclic amide derivatives
US6319912B1 (en) 1999-05-04 2001-11-20 American Home Products Corporation Cyclic regimens using 2,1-benzisothiazoline 2,2-dioxides
US6329416B1 (en) 1999-05-04 2001-12-11 American Home Products Corporation Combination regimens using 3,3-substituted indoline derivatives
US6380235B1 (en) 1999-05-04 2002-04-30 American Home Products Corporation Benzimidazolones and analogues
US6306851B1 (en) 1999-05-04 2001-10-23 American Home Products Corporation Cyclocarbamate and cyclic amide derivatives
US6355648B1 (en) 1999-05-04 2002-03-12 American Home Products Corporation Thio-oxindole derivatives
US6339098B1 (en) 1999-05-04 2002-01-15 American Home Products Corporation 2,1-benzisothiazoline 2,2-dioxides
US6407101B1 (en) 1999-05-04 2002-06-18 American Home Products Corporation Cyanopyrroles
US6423699B1 (en) 1999-05-04 2002-07-23 American Home Products Corporation Combination therapies using benzimidazolones
US6444668B1 (en) 1999-05-04 2002-09-03 Wyeth Combination regimens using progesterone receptor modulators
UA73119C2 (en) 2000-04-19 2005-06-15 American Home Products Corpoir Derivatives of cyclic thiocarbamates, pharmaceutical composition including noted derivatives of cyclic thiocarbamates and active ingredients of medicines as modulators of progesterone receptors
AU6594401A (en) * 2000-05-24 2001-12-03 Bayer Aktiengesellschaft 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxalines
JP2002205992A (en) * 2000-11-08 2002-07-23 Takeda Chem Ind Ltd Bicyclic triazolone derivative and herbicide comprising the same
CN101152932B (en) * 2006-09-27 2011-12-14 华东理工大学 Feed device of carbonaceous solid powder with a plurality of discharge doors and feed method thereof
CN103221409B (en) 2010-10-01 2016-03-09 巴斯夫欧洲公司 The benzo * zionoes of weeding
EP3278667A1 (en) 2016-08-05 2018-02-07 Basf Se Method for controlling ppo-inhibitor resistant weeds
CN111356693A (en) 2017-11-23 2020-06-30 巴斯夫欧洲公司 Herbicidal phenyl ethers
WO2019101513A1 (en) 2017-11-23 2019-05-31 Basf Se Herbicidal pyridylethers
CN110156767B (en) * 2019-04-12 2020-12-11 南开大学 Cycloalkane pyrimidine diketone compound, preparation method and application thereof, and pesticide herbicide
EP4091450A1 (en) * 2021-05-19 2022-11-23 Syngenta Crop Protection AG 3,3-difluoro-2-oxoindoline derivatives useful in weed control

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1644218A1 (en) * 1967-06-19 1970-12-17 Bayer Ag Monoazo dyes
US4619687A (en) * 1984-09-27 1986-10-28 Sumitomo Chemical Company, Limited Triazolopyridazines and their use as herbicides
JPH06777B2 (en) * 1984-10-03 1994-01-05 住友化学工業株式会社 Tetrahydrophthalimide derivative and herbicide containing the same as an active ingredient
US4720297A (en) * 1985-09-27 1988-01-19 Sumitomo Chemical Company, Limited Benzothiazolones, and their production and use as herbicides
JPH0670060B2 (en) * 1986-03-17 1994-09-07 住友化学工業株式会社 Benzothiazolone derivative and herbicide containing the same as active ingredient
JPH0670055B2 (en) * 1986-01-06 1994-09-07 住友化学工業株式会社 Imidazopyridine derivative and herbicide containing the same as active ingredient
ES2037668T3 (en) * 1986-01-06 1993-07-01 Sumitomo Chemical Company, Limited A PROCEDURE FOR THE PRODUCTION OF BENZOTIAZOLYLAZOLIDINE COMPOUNDS.
EP0235567B1 (en) * 1986-01-29 1994-01-12 Sumitomo Chemical Company, Limited Indazole compounds, their production, use and intermediates
JPS62223181A (en) * 1986-03-25 1987-10-01 Sumitomo Chem Co Ltd Production of tetrahydrophthalimide derivative
JPS6314782A (en) * 1986-07-07 1988-01-21 Nippon Tokushu Noyaku Seizo Kk Novel dialkylmaleinimide compound and herbicide
JPH075591B2 (en) * 1986-08-25 1995-01-25 住友化学工業株式会社 Benzothiazolone derivative and herbicide containing the same as active ingredient
US4755217A (en) * 1987-01-15 1988-07-05 Fmc Corporation Triazinedione herbicides
AU605304B2 (en) * 1987-06-22 1991-01-10 Nihon Tokushu Nayaku Seizo K.K. Benzo-fused cyclic compounds
US4877444A (en) * 1987-08-27 1989-10-31 Sumitomo Chemical Company, Limited Tetrahydroindazolyl-benzoxazines and use

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EP0311135B1 (en) 1993-06-02
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HUT49356A (en) 1989-09-28
JP2765873B2 (en) 1998-06-18
DE3734745A1 (en) 1989-04-20
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BR8805182A (en) 1989-05-23
AR244235A1 (en) 1993-10-29
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