EP0199794A4 - Aryl-triazolinones herbicides. - Google Patents

Aryl-triazolinones herbicides.

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Publication number
EP0199794A4
EP0199794A4 EP19850905564 EP85905564A EP0199794A4 EP 0199794 A4 EP0199794 A4 EP 0199794A4 EP 19850905564 EP19850905564 EP 19850905564 EP 85905564 A EP85905564 A EP 85905564A EP 0199794 A4 EP0199794 A4 EP 0199794A4
Authority
EP
European Patent Office
Prior art keywords
alkyl
compound
haloalkyl
formula
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19850905564
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German (de)
English (en)
Other versions
EP0199794A1 (fr
Inventor
Lester Lawrence Maravetz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FMC Corp
Original Assignee
FMC Corp
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Publication date
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Publication of EP0199794A1 publication Critical patent/EP0199794A1/fr
Publication of EP0199794A4 publication Critical patent/EP0199794A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • 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
    • C07D405/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention described in this application pertains to weed control in agriculture, horticulture, and other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes certain herbicidal ary1 triazolinones, compositions of them, methods of preparing them, and methods for preventing or destroying undesired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired.
  • the present compounds may be used to effectively control a variety of both grassy and broadleaf plant species.
  • the present invention is particularly useful in agriculture; a number of the compounds described herein show a selectivity favorable to certain crops at application levels which inhibit the growth of or destroy a variety of weeds.
  • One aspect of this invention relates to herbicidal compounds of the general formula
  • X is bromine, chlorine, or fluorine or haloalkyl
  • R 1 may be halogen (e.g. chlorine), alkyl (e.g. of 1 to 5 carbon atoms), haloalkyl (e.g. of 1 to 5 carbon atoms such as difluoromethyl), alkoxyalkyl (e.g. of 2 to 6 carbon atoms such as methoxymethyl), cyanoalkyl (e.g. of 2 to 6 carbon atoms such as cyano methyl), arylalkyl such as benzyl, alkylthio (e.g.
  • alkylthioalkyl e.g., of 1 to 3 carbon atoms independently with respect to each alkyl, such as methylthiomethyl
  • alkylsulfinylalkyl or alkylsulfonylalkyl e.g., 1,3-butanediol
  • alkylthioalkyl e.g., of 1 to 3 carbon atoms independently with respect to each alkyl, such as methylthiomethyl
  • R 8 may also be phenyl (or phenyl substituted with e.g., hal
  • R 3 is an alkylene radical (e.g. a lower alkylene such as -CH 2 - or -CH(CH 3 )-) or a haloalkylene radical (e.g. -CHF-) and R 4 is an alkyl radical (e.g. CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 ).
  • R 1 be methyl and R 2 be CHF 2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
  • R 2 of that patent is hydrogen, an alkyl group, or an alkenyl group. It has been found now that the replacement of an alkyl group by a CHF 2 or CH 2 F group yields compounds of much greater herbicidal activity. This is shown, for instance, in
  • the herbicidal esters of the aspect of the invention described above may be hydrolyzed to produce the corresponding acids, i.e., to compounds of the foregoing formula in which the substituent para to "X" is -OR 3 COOH (i.e. carboxyalkoxy). I have found that these acids are also effective herbicides, somewhat less potent than the corresponding esters.
  • the acids are also useful as intermediates for the preparation (as by esterif ication or amide formation) of other herbicidal compounds.
  • the acids may be converted to their salts, such as their sodium, potassium, ammonium, calcium, magnesium, or mono, di or trialkylammonium salts, which may be used as herbicides.
  • R 4 is a substituted alkyl group, an alkenyl group (e.g. allyl or methallyl) or an alkynyl group (e.g., propargyl) or a monovalent cyclic group having a ring of 5 or 6 atoms (e.g. an aromatic or hetero cyclic or alicyclic ring) whose valence is on a carbon atom of said ring, and Z is O oo S.
  • Corresponding compounds in;which Z is sulfur and R 4 is unsubstituted alkyl (e.g. of 1-4 carbon atoms) have also been found to be effective herbicides.
  • suitable substituents on the alkyl group are: nitro; halo (Cl,F,Br); furyl or tetrahydrofuryl; acetyl (CH 3 CO);
  • -CO-N(R II )(R III ) where -N(R II ) (R III ) is the residue (minus hydrogen) of ammonia or of a primary or secondary amine (e.g. methylamine, dimethylamine or other lower alkylamine); cyano;
  • R IV is the residue of an alcohol (such as the residue of a lower alkanol, e.g. a methyl or ethyl radical); phenyl or substituted phenyl; alkylamino, dialkylamino or a trialkylammonium salt (such as that shown in compound no. B20 below); alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl
  • radicals the alkyl is preferaby methyl or other lower alkyl
  • phenoxy in which radicals the alkyl is preferaby methyl or other lower alkyl
  • phenoxy in which radicals the alkyl is preferaby methyl or other lower alkyl
  • phenoxy in which radicals the alkyl is preferaby methyl or other lower alkyl
  • phenoxy in which radicals the alkyl is preferaby methyl or other lower alkyl
  • phenoxy phenylthio, phenylsulfinyl, or phenylsulfonyl (in which radicals the phenyl moiety may be substituted or unsubstituted).
  • R 4 is alkenyl or alkynyl it may be substituted with one of the foregoing substituents.
  • the substituents may be, for instance, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogen, cyano, nitro, hydroxy, amino or alkyl or dialkylamino or carboxyl. It is preferred that X, Y, R 1 and R 2 be as defined above for Formula I, and particularly that X be chlorine or (more preferably) fluorine, Y be chlorine, R 1 be methyl and R 2 be CHF 2 . However, within the broader scope of this aspect of the invention R 2 substituents may be alkyl (e.g.
  • haloalkyl e.g. of 1 to 5 carbon atoms, such as CHF 2
  • alkenyl of 2 to 5 carbon atoms e.g. allyl
  • alkynyl of 3 to 5 carbon atoms e.g. propargyl
  • cyanoalkyl e.g. CH 2 CN or CH 2 CH 2 CN
  • thiocyanoalkyl e.g. CH-SCN
  • a group of the formula -alkylene-Y 1 -R 5 in which said alkylene group e.g.
  • -CH 2 -) has 1 to 5 carbon atoms, Y being oxygen or S(O) r in which r is 0 to 2, and R 5 being alkyl
  • alkenyl of 2 to 5 carbon atoms e.g. allyl
  • R 3 is an alkylene radical (e.g. -CH 2 - or -CH(CH 3 )-) or a haloalkylene radical (e.g. -CHF-), and - is -NH 2 or the residue of a primary or secondary am.irie or of a sulfonamide.
  • alkylene radical e.g. -CH 2 - or -CH(CH 3 )-
  • a haloalkylene radical e.g. -CHF-
  • R 6 and R 7 may be, each, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, alkylsulfonyl, haloalkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl (including heteroarylsulfonyl such as thienylsulfonyl), aralkylsulfonyl, aminosulfonyl, dialkylaminosulfonyl, alkylaminosulfonyl, alkenylsulfonyl, phenylalkenylsulfonyl.
  • R 6 may be bicyclic or polycyclic such as benzofuranyl, dihydrobenzofuranyl benzofuransulfonyl, dihydrobenzofuransulfonyl, naphthalenesulfonyl, benz ⁇ dioxosulfonyl, anthraquinonesulfonyl.
  • R 6 , R 7 may carry one or more substituents such as halogen, nitro, amino, alkoxy, alkyl, haloalkgxy, alkenyloxy, haloalkenyloxy, alkoxyalkoxy, alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy or dialkylaminocarbonyloxy, acylamino, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or hydroxycarbonyl (but when one of R 6 , R 7 is connected to the nitrogen of formula III by an oxygen or sulfur atom, then the other of R 6 , R 7 is H or a group connected to that nitrogen by a carbon-nitrogen linkage or a salt-forming group, such as indicated below).
  • R 6 and R 7 may together comprise a divalent group, such as an alkylene or haloalkylene or alkyloxyalkylene group or thio
  • N R 6 R 7 together comprise a pyrrolidino, piperidino, morpholino, or thiazolidino ring
  • any of which may also carry a carboxylic ester or amide substituent.
  • the salt-forming group e.g. when
  • R is alkylsulfonyl, cycloalkylsulfonyl or arylsulfonyl) may be a metal (e.g. Na, K or Ca) or ammo nium (e.g. NH 4 or lower alkyl-substituted ammonium).
  • R 6 and R 7 may comprise a divalent group such that NR 6 R 7 together constitute, for instance,
  • a saccharin ring structure e.g. which is an active herbicide (such as compound C62 below) and which upon hydrolysis, can lead to other active herbicides such as compounds C58 and C59.
  • an active herbicide such as compound C62 below
  • Y and R 1 may be as defined above for Formula I, and R 2 may be as defined above for Formula II. It is preferred that R 1 be methyl and R 2 be CHF 2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
  • Still another aspect of this invention relates to herbicidal compounds of the formula
  • X, Y, R 1 and R 2 have the meanings given in connection with Formula I (for X, Y and R 1 ) and
  • X is chlorine or
  • 5-position of the benzene ring is -OR 3 COCl) with the corresponding oxime in the presence of an acceptor for
  • HCl such as triethylamine or sodium carbonate or sodium hydroxide.
  • any alkyl, alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms
  • the compounds of this invention may be prepared by methods generally described in the literature or by methods analogous or similar thereto and within the skill of the art.
  • One type of method starts with an intermediate in which the substituent para to "X" is hydroxyl.
  • one may use the intermediate described in "Synthetic Process Example 6" of UK patent application GB 2 090 250 published 7 July 1982, in which X and Y are Cl, R 1 is CH, and R 2 is CHF 2 (the corresponding compound in which R 2 is
  • CH 2 F is made by substituting chlorofluoromethane for the chlorodifluoromethane used in "Synthetic Process Example 1" of that published patent application).
  • the OH group of the intermediate may then be converted to the desired substituent, as by a conventional etherification reaction, e.g., by reacting it with the appropriate bromide in the presence of a known acceptor of HBr such as NaH or a mixture of K 2 CO 3 and Nal.
  • the synthesis may employ a substituted phenylhydrazine, whose hydrazine portion is then modified to form a triazolinone ring.
  • modification (which in Examples 2 and 3 is effected by reaction with pyruvic acid and then with a phosphoryl azide) may also be effected by other techniques, such as by treating the substituted phenylhydrazine with any of the following four types of reagents:
  • R 1 is as defined above, e.g. methyl
  • a haloalkylnitrile e.g. a fluoroalkyl, fluorochloroalkyl or fluorobromoalkyl nitrile such as CICF 2 CN, followed by reaction with a source of phosgene, so that the reaction may proceed along the following lines, for instance (and as also illustrated in Example 16 below), to form the aryl 3-haloalkyl triazoline, thus:
  • the "Ar" portion of the aryl hydrazine (whose hydrazine portion is then modified to form the triazoline ring) has halo substituents at its 2 and 4 positions and an alkoxy group at its 5 position.
  • the Ar group may be a phenyl radical or a fluorophenyl (e.g. 2-fluorophenyl) or a nitrophenyl (e.g. 3-nitrophenyl) alkoxyphenyl (e.g.
  • halonitrophenyl particularly a fluoronitrophenyl (such as 2-fluoro-5- nitrophenyl) or haloalkoxyphenyl (such as 2-fluoro-5- alkoxyphenyl) and the aryl triazoline may then be treated to (a) alkylate the nitrogen at the 4-position of the triazoline ring (in known manner, e.g. with an alkyl or fluoroalkyl halide, such as with ClCHF 2 to add the preferred - CHF 2 substituent) and (b) to introduce additional substituents onto the aromatic ring, as by halogenation with chlorine or bromine (e.g.
  • the alkylation of the nitrogen at the 4-position may be effected first, after which the nitro group (if present) may be reduced to an amino group in conventional manner, the amino group may be converted to a hydroxyl group (as by conventional diazotization) and then, preferably after etherifying the OH to form an alkoxy (e.g. methoxy) group, the compound may be halogenated as above to place the halogen substituent or substituents on its benzene ring. The resulting compound may then be modified at the 5-position of the benzene ring to form the herbicidal compounds of this invention.
  • the starting material may be 2-fluoro-5-nitrophenylhydrazine, .which may be treated as described above to produce successively a series of novel compounds such as 1-(2-fluoro-5-nitrophenyl)-4, 5-dihydro-3-methyl-1, 2, 4- triazol-5(1H)-one, then 1-(2-fluoro-5-nitropheny1-4, 5- dihydro-4-difluoromethyl-3-methyl-1, 2, 4-triazol-5(1H)- one.
  • this alkylation step may be delayed until after the abovedescribed halogenation of the benzene ring or even until after the conversion of the alkoxy (or other) group at the 5-position of the benzene ring to one of the groups described at that position in Formulas I, II, III and IV (and Tables 2, 3, 4, and 5) above.
  • the series of new compounds will include, successively, (from 2-fluoro-5-nitrophenyl hydrazine) such compounds as 1-(2-fluoro-5-nitro- phenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5- (1H)-one, then 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro- 4-methyl (or difluoromethyl)-3-difluoromethyl-1,2,4- triazol-5(1H)-one.
  • 2-fluoro-5-nitrophenyl hydrazine such compounds as 1-(2-fluoro-5-nitro- phenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5- (1H)-one, then 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro- 4-methyl (or difluoromethyl)-3-difluoromethyl-1,2,4- triazol-5(1H)-
  • the series of novel compounds will include, successively, such compounds as 1-(3-nitrophenyl)-4,5-dihydro-3-difluoromethyl1,2,4-triazol-5(1H)-one, then 1-(3-nitrophenyl)-4,5- dihydro-4-methyl (or difluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one.
  • Example 11 illustrates a process for making a compound of this invention having a sulfonamide group at the 5-position of the benzene ring by reacting (a) a compound having an oxypropionic acid substituent at that 5-position with (b) an aryl sulfonylisocyanate.
  • Another method for introducing the sulfonamide group is by reacting (a) a compound having a phenolic OH group at that 5-position with (b) an N-aryl (or alkyl etc.) sulfonylalkanoic acid amide having a reactive leaving substituent (e.g. Br, Cl, mesylate or tosylate) on the alkane portion of the molecule, e.g.
  • a reactive leaving substituent e.g. Br, Cl, mesylate or tosylate
  • Such a reaction can be carried out in the presence of a base (e.g. in acetone in the presence of sodium or potassium carb-onate). This method is illustrated in Example 14 below.
  • a base e.g. in acetone in the presence of sodium or potassium carb-onate.
  • Step A 4-Chloro-2-fluoro-5-methoxyaniline from 2 -chl oro - 4-f luorophenol
  • Step D 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5- dihydro-3-methyl-1,2,4-triazol-5(1H)-one
  • Step E 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4, 5- dihydro-4-difluoromethyl-3-methyl-1,2, 4- triazol-5(1H)-one
  • Step F 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4- difluoromethyl-4,5-dihydro-3-methyl-1,2,4- triazol-5(1H)-one
  • Compound Al was also prepared by the method of Example 2, Step H, from Compound 2.
  • a stirred mixture of 100.0 g (0.73 mole) of 4-methyl- 3-methoxyaniline in 800 mL of concentrated hydrochloric acid was cooled to -5°C.
  • a solution of 501.5 g (0.73 mole) of sodium nitrite in 250 mL of water was added slowly while maintaining the temperature of the reaction mixture below 0°C.
  • the resultant mixture was stirred at; -5°C for 30 minutes.
  • a cold solution of 330.0 g (1.46 mole) of tin (II) chloride dihydrate in 360 mL of concentrated hydrochloric acid was added over one hour. After complete addition the resultant mixture was allowed to warm to room temperature. A solid precipitate formed and was collected by filtration and stirred in 200 mL of water.
  • the supernatant liquid was decanted and washed with aqueous 10% hydrochloric acid followed by an aqueous 10% sodium hydroxide solution.
  • the organic layer was dried with magnesium sulfate and filtered.
  • the filtrate was evaporated under reduced pressure to leave a solid. This solid was triturated with petroleum ether and filtered.
  • the filter cake was air dried to yield 18.5 g of 4-difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5-(1H)-one.
  • Step E 1-(2-Chloro-4-methyl-5-methoxyphenyl)- 4-difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-one
  • Step F 1-(2-Chloro-4-methyl-5-hydroxyphenyl)- 4-difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-one
  • To a stirred solution of 16.0 g (0.053 mole) of 1-(2-chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-raethyl-1,2,4-triazol-5(1H)-one in 100 mL of methylene chloride at 10°C was added dropwise 39.6 g (0.16 mole) of boron tribromide. The resultant mixture was stirred at room temperature for two days. This mixture was washed with 100 mL of water.
  • Step H 2-[4-Chloro-5-(4-difluoromethyl-4,5- dihydro-3-methyl-5-oxo-1H-1,2,4-triazol- -1-yl)-2-methylphenoxy]propionic acid
  • Compound 11 was also prepared by the method of Example 4 from Compound A1 and n-butanol.
  • Step B N-Methylsulfony1-2-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-1H- 1,2,4-triazol-1-yl)phenoxy]propionamide
  • a mixture of 0.56 g of the oil from Step A and 0.56 g (0.0059 mole) of methanesulfonamide was heated at 80°C for 3.5 hours. The mixture was cooled and diluted with water, forming a gummy precipitate. The water was decanted, and. the residue was partitioned between water and methylene chloride.
  • the organic phase was washed with three 100 ml portions of water, dried over anhydrous magnesium sulfate, and filtered.
  • the filtrate was evaporated under reduced pressure to leave a tan solid which was dissolved in 30 mL of IN sodium hydroxide and 50 mL of water.
  • the basic mixture was filtered, and the filtrate was made acidic with concentrated hydrochloric acid. A precipitate formed and was collected by filtration.
  • Compounds C4, C5 and C6 were prepared by the process described in Example 6 using trifluoromethanesul- fonamide, ammonia and methylamine respectively in Step B.
  • Compounds C2 and C18 were prepared by the method of Example 6 from Compound A2, using methylamine and methanesulfonamide respectively in Step B.
  • Step B 1-(2,4-Dibromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol- 5(1H)-one
  • the reaction mixture was stirred at room temperature for 20 minutes, then heated at 70°C for 1-1/2 hours. The mixture was allowed to cool and was stirred at room temperature for approximately 18 hours. The solvent was removed by evaporation under reduced pressure, leaving a residue which was partitioned between deithyl ether and water.
  • the organic phase was washed in succession with water, an aqueous 10% sodium hydroxide solution, water, aqueous 10% hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and water. The organic phase was dried" over anhydrous magnesium sulfate, then filtered.
  • Compound B4 was also prepared by the method of Example 8 from the acid chloride of Compound A2 and 2-propyn-1-ol.
  • Step B 1-(2,4-Dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol- 5(1H)-one
  • Step C Ethyl 2-[2,4-dichloro-5-(4-fluoromethyl- 4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenoxy]propionate
  • Compound C25 was prepared by the method of Example 11 using 2-chlorobenzenesulfonyl isocyanate. Examp le 12
  • Step B 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]- 3-difluoromethyl-4,5-dihydro-1,2,4-triazol- 5(1H)-one
  • This aqueous phase was decanted from the oily residue and fresh water added to wash the residue.
  • This residue was dissolved in 160 mL of methylene chloride and filtered through a celite pad. The filtrate was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave a semi-solid residue.
  • the residue was triturated with approximately 125 mL of petroleum ether to provide 8.2 g of 1-[2,4-dichloro- 5-(1-raethylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro- 1,2,4-triazol-5(1H)-one.
  • Step C 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]- 3-difluororaethyl-4,5-dihydro-4-methyl-1,2,4- triazol-5(1H)-one.
  • Step D 1-(2,4-Dichloro-5-hydroxyphenyl)-3-difluoro- methyl-4,5-dihydro-4-methyl-1,2,4-triazol- 5(1H)-one
  • Compound B25 was prepared by the method of Lonord et al., J. Org. Chem. 27, 282-284 (1962) from Compound B23.
  • Compound A5 was prepared by the hydrolysis of Compound 22 using the procedure described by Kurtev et al., Synthesis (1975), 106-108.
  • the resultant cloudy solution was filtered through a pad of celite and the filtrate was extracted with methylene chloride.
  • the clarified aqueous solution was basified with approximately 8 mL of an aqueous 10% sodium hydroxide solution.
  • the filter cake was washed with water to yield 1.31 g of N'-(4-chloro-2- fluoro-5-methoxyphenyl)acetamidrazone (mp 106-107°C).
  • Step B 1-(4-Chloro-2-fluoro-5-methoxyphenyl)- 4, 5-dihydro-3-methyl-1,2,4-triazol- 5(1H)-one
  • the resultant solution was filtered and the filtrate was extracted with three 25 mL portions of an aqueous 10% sodium hydroxide solution followed by three 25 mL portions of IN sodium hydroxide. Each set of three similar extracts were combined and washed with methylene chloride. Both of the washed extracts were acidified with concentrated hydrochloric acid producing a precipitate from each.
  • Step B 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]- 3-chlorodifluoromethyl-4,5-dihydro-1,2,4- triazol-5(1H)-one
  • Step B the reaction of 13.86 of the oily residue from Step A plus 2.7 g of similar material prepared in a separate experiment and 19.87 g (0.1 mole) of trichloromethyl chloroformate in 600 mL of toluene produced 5.4 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one (mp 115-119°C).
  • Step C 1-[2, 4-Dichloro-5-(1-methylethoxy)phenyl]- 3-chlorodifluoromethyl-4,5-dihydro-4-methyl- 1,2,4-triazol-5(1H)-one
  • Step D 1-(2,4-Dichloro-5-hydroxyphenyl)-3- chlorodifluoromethyl-4,5-dihydro-4- methyl-1,2,4-triazol-5(1H)-one
  • the plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticum aestivium var.
  • Prodax rice (Oryza sativa), field bindweed (Convolvulus arvensis), morningglory ( Ipomea lacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), and johnsongrass (Sorghum halepense), yellow nutsedge (Cyperus esculentus).
  • Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats.
  • a topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.
  • the flats for the preemergence test were watered, then drenched with the appropriate amount of a solution of the test compound in a mixture of acetone and water containing a small amount (up to 0.5% v/v) of sorbitan monolaurate emulsif ier/solubilizer.
  • the conccntration of the test compound in solution was varied to give a range of application rates, generally 8.0 kg/ha and submultiples thereof.
  • the flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded..
  • the flats for the postemergence test were placed in a greenhouse and watered for 8-10 days, then the foilage of the emerged test plants was sprayed with a solution of the test compound in acetone-water containing up to 0.5% sorbitan monolaurate. After spraying, the foilage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
  • Phytotoxicity data were taken either as percent kill or percent control. Percent control was determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science,” 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977. The present rating system is as follows:
  • Herbicidal data at selected application rates are given for various compounds of the invention in the tables below.
  • the test compounds are identified in the tables of herbicidal data below by numbers which correspond to those used above.
  • the active compounds as above defined are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
  • the present herbicidal compounds may be formulated as granules of relatively large particle size, water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions or as any of several other known types of formulations, depending on the desired mode of application.
  • these herbicidal compositions are usually applied either as sprays, dusts, or granules to the areas in which suppression of vegetation is desired.
  • sprays or dusts are most commonly used.
  • These formulations may contain as little as 0.5% to as much as 95% or more by weight of active ingredient.
  • Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which att as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc.
  • Wettable powders also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant.
  • the wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid.
  • Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion.
  • a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
  • Emulsifiable concentrates are homogeneous liquid or paste compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent.
  • a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent.
  • these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
  • the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
  • Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alcohols; and other types of surface active agents, many of which are available in commerce.
  • the surface active agent when used, normally comprises 1% to 15% by weight of the herbicidal composition.
  • compositions for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents.
  • Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
  • Pressurized sprays, typically aerosols wherein.the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons may also be used.
  • Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds.
  • Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible.
  • the soluble or dispersible granular formulations described in U.S. patent No. 3,920,442, incorporated herein by reference, are useful herein with the present herbicidal compounds.
  • the active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture.
  • an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, 7 g/ha or lower.
  • the active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide (alachlor), 2-chloro-N-(2- ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)- acetamide (metolachlor), and N-chloroacety1-N-(2,6- diethylphenyl)glycine (diethaty1-ethyl); benzothiadiazinone herbicides such as 3-( 1-methylethyl)-(1H)2,l,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Aryl-triazolinones herbicides comprenant des composés de formule (I), où X est de préférence un halogène tel que du fluor, Y est de préférence un halogène tel que du chlore, R1 est de préférence méthyle, R2 est de préférence CH2, R3 est de préférence CH(CH3), Z est oxygène ou soufre, R4 peut être alkyle, alkyle substitué, alkényle, alkynyle, monovalent cyclique possédant un anneau de 5 ou 6 atomes ou ZR4 peut être un reste d'une amine, d'un sulfonamide ou d'un oxime.
EP19850905564 1984-10-31 1985-10-21 Aryl-triazolinones herbicides. Withdrawn EP0199794A4 (fr)

Applications Claiming Priority (2)

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US66693384A 1984-10-31 1984-10-31
US666933 1984-10-31

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EP0199794A4 true EP0199794A4 (fr) 1987-09-28

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EP (1) EP0199794A4 (fr)
JP (1) JPS61501991A (fr)
KR (1) KR880001297B1 (fr)
CN (1) CN85108193A (fr)
AU (2) AU573930B2 (fr)
BR (1) BR8507017A (fr)
CA (1) CA1266667A (fr)
HU (1) HUT41611A (fr)
IL (1) IL76857A0 (fr)
RO (1) RO96607A (fr)
WO (1) WO1986002642A1 (fr)

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US4743291A (en) * 1984-10-31 1988-05-10 Fmc Corporation Herbicidal aryl triazolinones
JPS6299368A (ja) * 1985-10-26 1987-05-08 Nippon Nohyaku Co Ltd Δ↑２−１，２，４−トリアゾリン−５−オン誘導体及びその製法並びにその用途
AU572739B2 (en) * 1985-10-26 1988-05-12 Nihon Nohyaku Co., Ltd. 1,2,4-triazolin-5-one derivatives
US4846875A (en) * 1987-07-21 1989-07-11 Fmc Corporation Herbicidal triazolinones
EP0354622A1 (fr) * 1988-08-11 1990-02-14 Shell Internationale Researchmaatschappij B.V. Herbicides à base d'oxadiazolone
CA1331463C (fr) * 1988-08-31 1994-08-16 Kathleen Megan Poss Triazolinones herbicides
UA26918C2 (uk) 1988-08-31 1999-12-29 Фмк Корпорейшн Похідhі триазоліhоhу, що проявляють гербіцидhу активhість, гербіцидhа композиція, спосіб придушеhhя росту бур'яhів
US4985065A (en) * 1989-05-10 1991-01-15 Fmc Corporation Tetrazolinone herbicides
JPH05208975A (ja) * 1991-12-02 1993-08-20 Mitsubishi Kasei Corp テトラヒドロフラン誘導体およびこれを有効成分とする除草剤
DE19802697A1 (de) 1998-01-24 1999-07-29 Bayer Ag Selektive Herbizide auf Basis von N-Aryl-triazolin(thi)onen und N-Arylsulfonylamino(thio)carbonyltriazolin(thi)onen
US6492527B1 (en) 1999-10-13 2002-12-10 Fmc Corporation Process to prepare aryltriazolinones and novel intermediates thereto
WO2003029226A1 (fr) * 2001-09-26 2003-04-10 Basf Aktiengesellschaft Phenoxyalkyl-, phenylthioalkyl-, phenylaminoalkyl- et phenylalkyl-sulfamoylcarboxamides a substitution heterocyclyle
EP1663204B1 (fr) 2003-08-29 2014-05-07 Exelixis, Inc. Modulateurs c-kit et leurs procedes d'utilisation
KR101256139B1 (ko) * 2009-01-05 2013-04-23 동부대우전자 주식회사 전자동 세탁기의 세제투입장치
KR101256138B1 (ko) * 2009-01-05 2013-04-23 동부대우전자 주식회사 전자동 세탁기의 세제투입장치
CN103493822B (zh) * 2013-09-05 2015-12-02 江苏东宝农化股份有限公司 具有广谱除草作用的除草剂
CN103493821B (zh) * 2013-09-05 2015-12-02 江苏东宝农化股份有限公司 一种具有广谱增效除草作用的除草剂

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FR2565228A1 (fr) * 1984-05-31 1985-12-06 Nihon Nohyaku Co Ltd Derives de la 2-1,2,4-triazoline-5-one et compositions herbicides en contenant

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US404019A (en) * 1889-05-28 Pessary
US3922162A (en) * 1974-03-28 1975-11-25 Velsicol Chemical Corp 2-Alkyl-4-aryl-1,2,4-triazolidin-3-ones
US4318731A (en) * 1979-08-25 1982-03-09 Nihon Nohyaku Co., Ltd. Δ2 -1,2,4-triazolin-5-one derivatives and herbicidal usage thereof
JPS5653662A (en) * 1979-10-08 1981-05-13 Nippon Nohyaku Co Ltd Preparation of delta2-1,2,4-triazolin-5-ones
CH651029A5 (de) * 1980-12-25 1985-08-30 Nihon Nohyaku Co Ltd Triazolin-derivate, verfahren zu ihrer herstellung und sie enthaltende herbizide mittel.
AU3507784A (en) * 1983-10-13 1985-05-07 Fmc Corporation Herbicidal
AU566839B2 (en) * 1984-03-29 1987-10-29 Fmc Corporation Herbicidal 1-aryl-2-1, 2, 4-triazolin-5-ones

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CA1266667C (fr) 1990-03-13
HUT41611A (en) 1987-05-28
AU5066385A (en) 1986-05-15
IL76857A0 (en) 1986-02-28
CN85108193A (zh) 1986-12-17
AU1333988A (en) 1988-06-23
CA1266667A (fr) 1990-03-13
BR8507017A (pt) 1987-01-06
RO96607A (fr) 1989-03-30
KR870700612A (ko) 1987-12-30
WO1986002642A1 (fr) 1986-05-09
KR880001297B1 (ko) 1988-07-22
AU573930B2 (en) 1988-06-23
EP0199794A1 (fr) 1986-11-05
JPS61501991A (ja) 1986-09-11

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