Classifications

• • 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
  • C07D403/12—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 linked by a chain containing hetero atoms as chain links
• • 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
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • 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, or other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes a series of novel herbicidal 1-aryl ⁇ 2 -1 ,2,4-triazolin-5-ones and 5-thiones, herbicidal 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, as a number of the novel aryltriazolinones described herein show a selectivity favorable to soybean, corn, cotton, wheat, rice, sunflower, or other crops at application levels which inhibit the growth of or destroy a variety of weeds.
• Various herbicidal 1-aryl- ⁇ 2 -1,2,4-triazolin-5ones are known in the art.
• U.S. Patent No. 4,318,731 and corresponding British Patent No. 2,056,971 disclose herbicidal aryltriazolinones of the formula
• R 1 is alkyl
• R 2 is hydrogen, alkyl, or alkenyl
• X is hydroxy, alkyl, alkoxy, alkoxyalkoxy, alkenyl oxy, or alkyl oxycarbonylalkyloxy.
• British Patent No . 2 , 090 , 250 a continuation-inpart of the above British patent , adds to the above genus compounds wherein R 2 is alkynyl, halomethyl, or haloethyl, and X is alkoxy, alkenyloxy, alkynyloxy, alkoxyalkoxy, hydroxy, halomethyloxy, or haloethyloxy.
• European Patent Application Publication No. 55,105 discloses a series of herbicidal aryltriazolinones of the formula
• R is alkyl, alkenyl, or cycloalkyl
• X is chlorine or bromine
• Y is hydrogen or alkoxy
• Japanese Kokai 81-32,468 discloses herbicidal aryltriazolinones of the formula
• R is hydrogen, alkyl , or 2-propenyl , and R 1 is methyl or alkoxy.
• R n is hydrogen or represents 1 to 4 same or different radicals selected from halogen, nitro, cyano, optionally halosubstituted alkyl, alkoxy, or alkylthio, and optionally substituted phenyl or phenoxy
• R 1 is alkyl, alkoxyalkyl, dialkoxyethyl, dialkylaminoethyl, or cycloalkyl.
• U.S. Patent No. 4,315,767 discloses herbicidal bicyclic compounds of the following formula
• V is hydrogen, halogen, methyl, or alkoxy
• X is hydrogen, halogen, cyano, methyl, methoxy, or nitro
• Y is hydrogen, halogen, or methyl
• m and n are 0 to 4 (m plus n is 2 to 4)
• Q is oxygen or sulfur
• Z is oxygen, S(O) p , or NR 1 wherein p is 0-2 and R 1 is alkyl, provided that when m plus n is 2 or 4 then Y and X are other than hydrogen, and when Z is S(O) p then n is 1 to 4.
• V is hydrogen, halogen, hydroxy, alkyl, or -OR 1 ;
• R 1 is optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, optionally substituted alkenyl, alkynyl, optionally substituted benzyl, alkylaminocarbonyl, (alkyl) (methyl or methoxy)aminocarbonyl, acyl, alkoxy carbonyl, or -CHR 7 R 8 wherein R 7 is hydrogen or alkyl and R 8 is cyano, acetyl, hydroxycarbonyl, alkoxycarbonyl, hydroxymethyl, alkoxymethyl, alkylcarbonyloxymethyl, hydroxycarbonylethenyl, alkoxycarbonylethenyl, or a group -CO-NR 11 R 12 wherein R 11 is hydrogen, alkyl, alkenyl, or alkoxy, and R 12 is hydrogen or alkyl;
• X is halogen, cyano,
• a class of ⁇ 2 -1,2,4-triazolin-5-ones is disclosed as fungicides in U.S. 4,098,896.
• the disclosed genus has the formula
• R is alkyl, alkenyl, alkynyl, cycloalkyl, or optionally substituted phenyl or arylalkyl
• R 1 is haloalkyl or haloalkenyl
• R 2 is optionally substituted alkyl, alkenyl, or alkynyl, or optionally substituted aryl, arylalkyl, or alkylaryl.
• the present application describes a novel class of herbicidal 1-ary.1- ⁇ 2 -1,2,4-triazolin-5-ones and 5thiones characterized primarily in that the 1-aryl moiety is a 2 ,4,5-trisubstituted-phenyl group in which the C-5 substituent is a group -OR wherein R is an oxygen-, sulfur- or nitrogen-containing heterocycle or an alkyl group substituted therewith.
• Any alkyl, alkenyl, or alkynyl group herein or the alkyl, alkenyl, or alkynyl portion of any group may be a straight chain or branched chain radical.
• 1-methylethyl, methylcyclopropyl, 2-methyl-2-propenyl, and 1-methyl-2-propynyl are branched chain examples of alkyl, cyclic alkyl, alkenyl, and alkynyl radicals respectively.
• Any halogen may be fluorine, chlorine, or bromine.
• Haloalkyl, haloalkenyl, and haloalkynyl radicals may have one or more same or different halogen atoms.
• Any aryl group or the aryl portion of any group may be a hydrocarbyl group such as phenyl or it may contain one or more heteroatoms such as in thienyl or furyl. Any aryl may be substituted, for example, with halogen or alkyl of 1 to 4 carbon atoms.
• X 1 and X 2 are independently selected from halogen, haloalkyl, and alkyl; w is oxygen or sulfur;
• R is a three- to eight-membered ring heterocyclic group of one or two, same or different, ring heteroatoms selected from oxygen, sulfur, and nitrogen, or an alkyl radical substituted with said heterocyclic group;
• R 1 is alkyl, haloalkyl, cyanoalkyl, alkenyl, alkynyl, or a group of the formula -alkyl-Y-R 3 ;
• R 2 is halogen, alkyl, cyanoalkyl, haloalkyl, arylalkyl, or a group of the formula -alkyl-Y-R 3 ;
• R is alkyl, alkenyl, or alkynyl; and Y is oxygen or S(O) r in which r is 0 to 2.
• the R substituent heterocyclic group may be saturated, unsaturated, or aromatic. It may be substituted with halogen, alkyl, or haloalkyl, or it may be adjoined to a benzene ring at two adjacent ring carbon atoms to form a benzoheterocycle bicyclic group, the two adjacent ring carbon atoms being, common to both the heterocyclic ring and the benzene ring.
• sulfur-containing heterocycles the sulfur may be present in divalent form or as the S-oxide or S-dioxide.
• R is an optionally substituted and optionally benzene-adjoined nitrogen-containing heterocycle or an alkyl radical of 1 to 5 carbon atoms substituted with said heterocycle.
• the R substituent for this group of compounds is a non-aromatic heterocycle, preferably containing only one nitrogen atom and no other heteroatoms, the nitrogen atom preferably being substituted with an alkyl group of 1 to 5 carbon atoms, particularly a methyl group.
• This aspect of the invention is exemplified herein by compounds 29 and 31 below wherein R is 1 -methyl-3-pyrrolidinyl.
• a second aspect of the present invention comprises the compounds of formula I above wherein R is an aromatic, optionally substituted and optionally benzeneadjoined, oxygen- or sulfur-containing heterocycle or an alkyl group of 1 to 5 carbon atoms substituted therewith.
• R is an optionally substituted furanyl, furanylalkyl, thienyl, or thienylalkyl radical.
• R is furfuryl and 2-thienylmethyl respectively.
• a further aspect of the present invention comprisesthe compounds of formula I above wherein R is a non-aro matic, optionally substituted and optionally benzeneadjoined, oxygen- or sulfur-containing heterocycle or an alkyl group of 1 to 5 carbon atoms substituted therewith.
• R is a non-aro matic, optionally substituted and optionally benzeneadjoined, oxygen- or sulfur-containing heterocycle or an alkyl group of 1 to 5 carbon atoms substituted therewith.
• This group of compounds represents a preferred embodiment of the present invention.
• the R substituent heterocycle is preferably saturated, but may be unsaturated, and is preferably unsubstituted or substituted with alkyl of 1 to 5 carbon atoms, particularly methyl, or it may be substituted with halogen such as fluorine, chlorine, or bromine or haloalkyl of 1 to 5 carbon atoms, for example, chlorodifluoromethyl.
• R heterocycle contains two ring heteroatoms, they may be the same or different, oxygen or sulfur, preferably the same, and are separated from each other in the ring by at least one carbon atom.
• sulfur-containing heterocycles the sulfur may be present in divalent form or as the S-oxide or S-dioxide.
• the R substituent heterocycle for. these compounds of the invention will be recognized as being a cyclic ether or thioether or an S-oxide or S-dioxide derivative of a cyclic thioether.
• R groups for this subgenus are 3-tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyran-2-ylmethyl, 1,3-dioxolan-2-ylmethyl, 2-(1,3-dioxolan-2-yl)ethyl, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl, 3-(2-methyl-1,3-dioxolan-2-yl)propyl, 1 ,3-dioxan-4-ylmethyl, 1 ,4-benzodioxan2-ylmethyl, tetrahydro-4H-pyran-4-yl, 5,6-dihydro-2Hpyran-3-ylmethyl, 2 ,2-dimethyl-1,3-dithiolan-4-ylmethyl, tetrahydro-4H-thiopyran-4-yl, tetrahydrothien3-yl, 1-oxotetrahydrothien
• Additional examples include 1,4-dithiacycloheptan-6-yl, 1 ,4-dithiacyclohe ⁇ t-5-ene-6-yl, tetrahydro-4H-pyran-3yl, glycidyl, 2,3-epithiopropyl, and 2,2-bis(chlorodifluoromethyl)-1,3-dioxolan-4-ylmethyl.
• X 1 and X 2 are independently selected from halogen, haloalkyl of 1 to 3 carbon atoms, and alkyl of 1 to 5 carbon atoms;
• W is sulfur or, preferably, oxygen;
• R is 1-methyl-3-pyrrolidinyl, furfuryl or 2-thienylmethyl, or preferably 3-tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyran-2-ylmethyl, 1 ,3-dioxolan-2-ylmethyl, 2-(1,3-dioxolan-2-yl)ethyl, 2,2-dimethyl-l,3-dioxolan-4-ylmethyl, 3-(2-methyl-1 ,3-dioxolan-2-yl)propyl, 1,3-dioxan-4-ylmethyl, 1,4-benzodioxan-2-ylmethyl, tetrahy ⁇ ro-4H-pyran-4-yl, 5,6-dihydro-2H-pyran-3-ylmethyl, 2,2-dimethyl-1,3-dithiolan-4-ylmethyl, tetrahydro-4H
• R 2 is halogen, alkyl, haloalkyl, cyanoalkyl, or arylalkyl wherein each alkyl is of 1 to 5 carbon atoms, or a group (CH 2 ) n -Y-R 3 wherein n is 1 to 5;
• R 3 is alkyl of 1 to 5 carbon atoms or alkenyl or alkynyl of 2 to 5 carbon atoms;
• Y is oxygen or S(O) in which r is 0 to 2.
• the substituents X 1 and X 2 may be the same, and in such instances each will usually be a fluorine. chlorine, or bromine atom (preferably chlorine); less frequently, a methyl group.
• X 1 and X 2 are different, X 1 will advantageously be fluorine or chlorine, preferably fluorine, and X will frequently be selected from among chlorine, bromine, haloalkyl such as difluoromethyl, and alkyl such as methyl.
• X 2 is preferably chlorine.
• the R 1 substituent is preferably a haloalkyl radical of 1 to 3 carbon atoms and having one or more independently selected halogen atoms, preferably selected from fluorine and chlorine; more preferably, a fluoroalkyl radical such as 3-fluoropropyl or, especially, difluoromethyl.
• R1 substituents of particular interest include alkyl of 1 to 5 (preferably 1 to 3) carbon atoms such as n-propyl, cyanoalkyl of 1 to 3 alkyl carbon atoms such as cyanomethyl, alkenyl of 2 to 5 (preferably 3 to 5) carbon atoms especially 2-propenyl, alkynyl of 2 to 5 (preferably 3 to 5) carbon atoms such as 2- ⁇ ropynyl, or a group -(CH 2 ) 2 -Y-R 3 in which Y is oxygen or sulfur and R 3 is alkyl of 1 to
• R 1 will be selected from n-propyl difluoromethyl, 3-fluoropropyl, cyanomethyl, and 2-propenyl.
• R 2 is preferably alkyl of 1 to 5 (more preferably 1 to 3) carbon atoms, especially methyl; haloalkyl of 1 to 3 carbon atoms, particularly a fluoroalkyl such as fluoromethyl or difluoromethyl; cyanoalkyl of 1 to 3 alkyl carbon atoms, for example, cyanomethyl; benzyl; or a group -(CH 2 ) n -Y 3 -R 3 in which n is 1 or 2, Y is oxygen or sulfur, and R 3 is alkyl of 1 to 5 carbon atoms such as methyl or ethyl.
• R 2 will frequently and advantageously be fluoromethyl, difluoromethyl, or, especially, unsubstituted methyl.
• R substituent is 3-tetrahydrofuranyl, tetrahydrofurfuryl, or 1,1-dioxotetrahydrothien-3-yl, particularly 3-tetrahydrofuranyl, generally show very high herbicidal activity, especially where preferred groups are selected for the other substituents.
• R preferred radicals for R include: tetrahydropyran-2-ylmethyl, 1,3-dioxolan-2-ylmethyl, 2-(1,3dioxolan-2-yl)ethyl, 2,2-dimethyl-1,3-dioxolan-4-yl methyl, 1,3-dioxan-4-ylmethyl, tetrahydro-4H-pyran-4-yl, tetrahydrothien-3-yl, and 1-oxotetrahydrothien-3-yl.
• R is 3-(2-methyl-1,3-dioxolan-2-yl)propyl, 5,6-dihydro-2Hpyran-3-ylmethyl, 2,2-dimethyl-1 ,3-dithiolan-4-ylmethyl, or tetrahydro-4H-thiopyran-4-yl.
• the present compounds may generally be prepared by reaction of an appropriately substituted 5-hydroxyphenyltriazolinone (01a) or the thione analog (01b) with R-X, wherein X is a good leaving group, in the presence of a base as illustrated in the following equation.
• the present compounds containing a sulfinyl or a sulfonyl group in R, R 1 , or R 2 may be prepared by oxidation of the corresponding thio compound, generally with hydrogen peroxide, as described in detail in Examples 25, 26, 27, and 34 below for certain R groups.
• the aryltriazolin-5-thiones (W is sulfur) may be prepared by methods within the skill of the art, for example, by treating an appropriately substituted aryltriazolin-5-one with phosphorous pentasulfide in toluene under reflux conditions.
• the intermediates R-X and 01a are either known in the art and, therefore, are available by known methods, or may be prepared by methods analogous or similar to known methods or by methods within the skill of the art.
• U.S. Patent No. 4,318,731 and British Patent No. 2,090,250 disclose preparation of a number of the present hydroxyphenyl intermediates 01a wherein X and X 2 are chlorine atoms by dealkylation of the corresponding alkyloxyphenyl or alkenyloxyphenyl compound.
• Many of the hydroxyphenyl intermediates 01a for the present exemplary compounds were prepared by dealkylation of the corresponding isopropoxy or methoxy compound in the presence of concentrated sulfuric acid, a mixture of hydrobromic and acetic acids, or boron tribromide.
• Further methods for preparing intermediate compounds are illustrated in the following chemical equations in which steps A and B are analogous to the method of U.S. Patent 3,290,327, issued December 6, 1966.
• Phenylhydrazines (03) useful in step B above may be prepared by the method shown in the following chemical equations in which step F itself represents a
• X 1 and X 2 are halogen such as chlorine
• substituents may be added to the molecule later in the reaction sequence, 3-methoxyphenylhydrazine being used in step B.
• An alternative method for producing the aryltriazolinone 04 from the phenylhydrazine 03 is shown in the following chemical equations.
• Example 1 1 - [2,4-DICHLORO-5-(3-TETRAHYDROFURANYLOXY)PHENYL]3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 -1,2,4-TRIAZOLIN-5-ONE
• Step 1 3-Tetrahydrofuranyl 4-methylphenylsulfonate
• Step 2 1- [2 ,4-Dichloro-5-(3-tetrahydrofuranyloxy)phenyl]-3-methyl-4-difluoromethyl- - ⁇ 2 -1,2,4-triazol ⁇ n-5one
• the reaction mixture was cooled and concentrated to dryness to give an oily black residue which was partitioned between diethyl ether and water.
• the ether layer was washed sequentially with 10% hydrochloric acid, water, 10% aqueous solution of sodium hydroxide, water, and brine.
• the ether layer was dried over magnesium sulfate, filtered, and the filtrate concentrated to give 0.82 g of a viscous yellow oil.
• 1,3-dioxolan-2-ylmethyl bromide was added to a previously heated (110oC) then cooled (25oC) mixture of 0.75 g
• Example 7 1 - ⁇ 2,4-DICHLORO-5-[2-(1,3-DIOXOLAN-2-YL)ETHOXY]PHENYL ⁇ -3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 -1,2,4-TRI ⁇
• Example 8 1-[2,4-DICHLORO-5-(2,2-DIMETHYL-1,3-DIOXOLAN-4YLMETHOXY) PHENYL]-3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 -1,2,4-TRIAZOLIN-5-ONE
• 0.687 g (0.0024 mole) of 2,2-dimethyl-1,3-dioxolan-4-ylmethyl 4-methylphenylsulfonate was added to a mixture of 0.75 g (0.0024 mole) of
• Furfuryl bromide was prepared by the method of Example 21 of U.S. Patent No. 4,282,219 as follows. A stirred solution of 2.0 g (0.02 mole) of furfuryl alcohol in 20 mL of diethyl ether was cooled to 5°C, and a solution of 2.0 g (0.007 mole) of phosphorus tribromide in 6 mL of diethyl ether was added dropwise over 30 minutes. Upon complete addition, the reaction mixture was stirred an additional 15 minutes at 5oC. The clear diethyl ether solution was then decanted from a dark residue. The clear solution was stirred at 5-6oC with 0.5 g of anhydrous potassium carbonate for 10 minutes. The solution was decanted away from the potassium carbonate and kept cold. The unstable product, furfuryl bromide, was used as such without delay in the following reaction.
• the reaction mixture was filtered, and the filtrate washed sequentially with water, 10% hydrochloric acid, water, twice with a 10% aqueous solution of sodium hydroxide, and twice with water.
• the organic layer was dried over magnesium sulfate, filtered, and the filtrate concentrated to give 1.6 g of a dark oily-solid residue.
• the residue crystallized upon treatment with petroleum ether, wgt. 0.91 g, mp 134-135oC.
• a sample for analysis was prepared by recrystallization from ethanol, m.p. 135-137oC.
• Example 4 0.615 g (0.0024 mole) of tetrahydro-4H-pyran-4-yl 4-methylphenylsulfonate was added to a previously heated (60oC) then cooled (25°C) mixture of 0.75 g (0.0024 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazo lin-5-one and 0.065 g (0.0027 mole) of sodium hydride in 8 mL of dimethylformamide, and the mixture was heated at about 90°C for 16 hours to give 0.42 g of product, mp 149-151oC. The nmr spectrum was consistent with the proposed structure.
• This compound was prepared by the reduction of 14 g (0.125 mole) of 5,6-dihydro-2H-pyran-3-carbaldehyde with 2.88 g (0.074 mole) of sodium borohydride in a 1:1 mixture of dioxane and water; wgt. 15 g.
• Step 2 5,6-Dihydro-3-chloromethyl-2H-pyr an Reaction of 5 g (0.0438 mole) of 5,6-dihydro-3-hydroxymethyl-2H-pyran with 11.51 g (0.0448 mole) of triphenyl phosphine in the presence of 20 mL of carbon tetrachloride at room temperature for about 40 hours produced this intermediate as a solid material.
• Step 3 1-[2,4-Dichloro-5-(5,6-dihydro-2H-pyran-3ylmethoxy)phenyl]-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4triazolin-5-one in the manner of Example 4, 0.3 g (0.0023 mole) of
• Example 17 1 - [2,4-DICHLORO-5-(3-TETRAHYDROFURANYLOXY)PHENYL]3-METHYL-4-(2-PROPENYL)- ⁇ 2 -1,2,4-TRIAZOLIN-5-ONE
• 0.61 g (0.0025 mole) of 3-tetrahydrofuranyl 4-methylphenylsulfonate was added to a mixture of 0.75 g (0.0025 mole) of 1-(2,4-dichloro-5hydroxyphenyl)-3-methyl-4-(2-propenyl)- ⁇ 2 -1,2,4-triazolin-5-one and 0.06 g (0.0025 mole) of sodium hydride in 30 mL of dimethylformamide, and the mixture was heated at reflux temperatures for 3 hours then stirred at room temperature for about 64 hours to give 0.7 g of a solid product.
• 3-tetrahydrofuranyl 4-methylphenylsulfonate was added to a mixture of 1.0 g (0.0033 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-3-methyl-4-n-propyl- ⁇ 2 -1,2,4-triazolin-5one and 0.08 g (0.0033 mole) of sodium hydride in dimethylformamide, and the mixture was heated at 80-90oC for 2 hours, at reflux temperature for 6.5 hours, then stirred at room temperature for 16 hours and finally heated at reflux temperature for an additional 5 hours to give 1.0 g of product as an oil which solidified upon standing, mp 107-112°C. A sample of the product was recrystallized from ethyl acetate-hexane for analytical purposes, m.p. 116-117oC.
• Example 19 1 - ( 2,4-DICHLORO-5-TETRAHYDROFURFURYLOXYPHENYL)3-METHYL-4-n-PROPYL- ⁇ 2 -1 ,2,4-TRIAZOLIN-5-ONE in the manner of Example 4, 0.49 g (0.003 mole) of tetrahydrofurfuryl bromide was added to a mixture of 0.90 g (0.003 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-3methyl-4-r ⁇ -pro ⁇ yl- ⁇ 2 -1,2,4-triazolin-5-one and 0.075 g (0.0031 mole) of sodium hydride in dimethylformamide, and the mixture was heated at 80oC for 45 minutes, then stirred at room temperature for 16 hours, and again heated (90-100oC) for 1 hour. Analysis (TLC) of the reaction mixture showed the reaction to be incomplete.
• Powdered potassium carbonate (0.21 g, 0.0015 mole) and an additional 0.49 g (0.003 mole) of tetrahydrofurfuryl bromide were added, and the reaction mixture was heated at 90-100oC for 2.5 hours, stirred at room temperature for 16 hours, heated at reflux temperature for 6.5 hours, stirred at room temperature for 16 hours, and, finally, heated at reflux for 5 hours to give 0.97 g of product as a viscous oil.
• Example 20 1 - [2,4-DICHLORO-5-(2,2-DIMETHYL-1,3-DITHIOLAN-4-YLMETHOXY)PHENYL] -3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 -1,2,4 ⁇
• Step 2 4-Chloromethyl-2,2-dimethyl-1,3-dithiolan
• a solution of 3.46 g (0.021 mole) of 2,2-dimethyl-4-hydroxymethyl-1,3-dithiolan in 15 mL of toluene was added dropwise 2.35 g (0.020 mole) of thionyl chloride, and the mixture was heated gradually to 80-85oC, maintained at that temperature for 0.75 hour, then stirred at room temperature for 16 hours.
• the mixture was filtered, and the filtrate concentrated to dryness at 60°C/100 mm Hg to give a residual oil. Distillation of the oil gave 1.81 g of product, bp 75-78oC/1.25-1.35 mm
• Step 3 1- [2 ,4-Dichloro-5- ( 2 ,2-dimethyl-1 ,3-dithiolan-4-ylmethoxy) phenyl ] -3-methyl-4-difluoromethyl- ⁇ 2 ⁇
• Step 2 Pyruvic acid, 3-methoxyphenyl hydrazone.
• a stirred solution of 45 g (0.33 mole) of 3methoxyphenyl hydrazine in 400 mL aqueous 1N hydrochloric acid and 400 mL of ethanol was added dropwise a solution of 31.5 g (0.36 mole) of pyruvic acid in 30 mL of water.
• reaction mixture was stirred at ambient temperature for 3 hours, and 200 mL of water was added. The mixture was filtered to give 56 g of product; mp 113-114oC.
• Step 3 1-(3-Methoxyphenyl)-3-methyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 4 1-(3-Methoxyphenyl)-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 5 1-( 2,4-Dibromo-5-methoxyphenyl)-3-methyl-4difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 6 1-( 2,4-Dibromo-5-hydroxyphenyl)-3-methyl-4difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 7 1 - [2 ,4-Dibromo-5-( 3-tetrahydrofuranyloxy) phenyl] -3-methyl-4-difluoromethyl- ⁇ 2 -1 ,2 ,4-trizaolin-5one
• Example 22 step 6
• 0.06 g (0.0025 mole) of sodium hydride, and 0.41 g (0.0025 mole) of tetrahydrofurfuryl bromide in dimethylformamide gave 0.8 g of product as an oil.
• Step 1 3-Tetrahydrothienyl 4-methylphenylsurfonate
• a chilled solution of 1.12 g (0.0098 mole) of tetrahydrothiophene-3-ol in 15 mL of pyridine was added 1.91 g (0.01 mole) of 4-methylphenylsulfonyl chloride, and the reaction mixture was stirred in the cold, about 16oC, for 1 hour then placed in a cold refrigerator for 16 hours. The reaction mixture was allowed to warm to room temperature and was stirred for 1 hour. An additional 0.3 g (0.0016 mole) of 4-methyl ⁇ henylsulfonyl chloride was added, and the reaction mixture was stirred at room temperature for 64 hours. The reaction mixture was poured into water, and the whole was extracted with methylene chloride. The methylene chloride solution was dried and concentrated to give 1.28 g of product as an oil.
• Step 2 1-[2,4-Dichloro-5-(3-tetrahydrothienyloxy)phenyl]-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5one
• Example 27 1 - [ 2 , 4-D ICHLORO- 5 - ( 2 , 2-D IMETHYL- 1,1,3,3-TETRAOXO ⁇
• Step 1 4-Methyl-3-methoxyphenyl hydrazine.
• the compound was prepared by a method analogous to that of Example 22, Step 1.
• the reaction of 100 g (0.73 mole) of 4-methyl-3-methoxyaniline and 50.5 g (0.73 mole) of sodium nitrite in the presence of 330 g (1.46 moles) of stannous chloride dihydrate, 1160 mL of concentrated hydrochloric acid and 250 mL of water gave 58.0 g of product as an oil.
• the nmr spectrum was consistent with the proposed structure.
• Step 2 Pyruvic acid, 4-methyl-3-methoxyphenyl hydrazone.
• This compound was prepared by a method analogous to that of Example 22, Step 2.
• the nmr spectrum was consistent with the proposed structure.
• Step 3 1 - (4-Methyl-3-methoxyphenyl)-3-methyl ⁇ 2 -1,2,4-triazol ⁇ n-5-one.
• Step 4 1-(4-Methyl-3-methoxyphenyl)-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one.
• This compound was prepared by a method analogous to that of Example 22, Step 4. The reaction of 60.0 g
• Step 5 1-(2-Chloro-4-methyl-5-methoxyphenyl)-3methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one.
• Step 6 1-(2-Chloro-4-methyl-5-hydroxyphenyl)-3methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one.
• Step 7 1 - [2-Chloro-4-methyl-5-(tetrahydro-4Hthiopyran-4-yloxy)phenyl]-3-methy1-4-difluoromethyl ⁇
• Step 2 1-[2,4-Dibromo-5-(1-methyl-3-pyrrolidinyloxy)phenyl]-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 2 1-( 2-Bromo-4-methyl-5-hydroxyphenyl)-3methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 3 1- [2-Bromo-4-methyl-5-(3-tetrahydrofuranyloxy )phenyl]-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Example 33 1-(2-CHLORO-4-METHYL-5-TETRAHYDROFURFURYLOXYPHENYL)3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 -1,2,4-TRIAZOLIN-5-ONE in the manner of Example 4, the reaction of 0.8 g (0.0028 mole) of 1-(2-chloro-4-methyl-5-hydroxyphenyl)-3methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one (which may be prepared as described in Example 28, steps 1-6), 0.07 g (0.0029 mole) of sodium hydride, and 0.46 g (0.0028 mole) of tetrahydrofurfuryl bromide in dimethylformamide gave 0.47 g of product as an oil.
• Example 21 10 mL (0.116 mole) of a 30% aqueous solution of hydrogen peroxide, and 25 mL of glacial acetic acid was heated at reflux temperature for 3 hours. The reaction mixture was concentrated to a residue. The residue was dissolved in methylene chloride and washed with a 10% aqueous solution of sodium hydroxide. The methylene chloride layer was dried and concentrated to give 0.25 g of product as an oil.
• Example 35 1-[2,4-DICHLORG-5-(3-TETRAHYDROFURANYLOXY)PHENYL] -3-CHLORO-4-(2-PROPENYL)- ⁇ 2 -1 , 2, 4TRIAZOLIN-5-ONE in the manner of Example 4, the reaction of 1.8 g
• This compound was prepared by a method similar to that of Example 1.
• the intermediate 1-(2,4-dichloro-5-hydroxyphenyl)3-ethyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one may be prepared by a method similar to that of Example 38
• step 1 steps 1 -6 below starting with 2 ,4-dichlorophenol and proceeding via the intermediates 2,4-dichloro-5-(1methylethoxy)aniline (step 1), 2,4-dichloro-5-( 1-methylethoxy)phenylhydrazine (step 2), 2-ketobutyric acid
• step 4 1,2,4-triazolin-5-one (step 4), and 1-[2,4-dichloro-5(1-methylethoxy) phenyl]-3-ethyl-4-difluoromethyl ⁇ 2 -1,2,4-triazolin-5-one.
• 3-Methoxyphenylhydrazine prepared from 10.0 g (0.0573 mole) of the hydrochloride salt by treatment with potassium carbonate in the presence of water and xylene, was reacted with 10.4 g (0.06 mole) of ethyl pivaloylcarbamate in the presence of 1.5 g of phosphorus pentoxide in xylene to give 3.84 g of product.
• Step 2 1 -( 3-Methoxyphenyl)-3-(1,1-dimethylethyl)-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 3 1 -( 2,4-Dichloro-5-methoxyphenyl)-3( 1,1-dimethylethyl)-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 5 1-[2,4-Dichloro-5-(3-tetrahydrofuranyloxy)phenyl]-3-(1,1-dimethylethyl)-4-difluoromethyl- ⁇ 2 ⁇
• This compound was prepared by a method similar to that of Example 1.
• Step 1 4-Chloro-2-fluoro-5-methoxyaniline
• the intermediate 4-chloro-2-fluoro-5-methoxyaniline was prepared from commercially available 2-chloro-4fluorophenol as detailed by E. Nagano, et al. in European Patent Application 69,855.
• Step 4 1-(4-Chloro-2-fluoro-5-methoxyphenyl)3-methyl- ⁇ 2 -1,2,4-triazolin-5-one
• the reaction mixture was cooled to ambient temperature and extracted with an aqueous 10% sodium hydroxide solution.
• the extract was neutralized with gaseous carbon dioxide, and a solid was collected by filtration.
• Step 5 1 - ( 4-Chloro-2-fluoro-5-methoxyphenyl3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Chlorodifluoromethane 10.0 g (0.12 mole) was bubbled into the reaction mixture. After complete addition, the reaction mixture was warmed to reflux and stirred for one hour. The hot solution was decanted from a pot residue and cooled to ambient temperature. Methylene chloride was added to the cooled mixture to dissolve a solid precipitate. The mixture was washed with 10% hydrochloric acid, then with an aqueous 10% sodium hydroxide solution. The organic layer was dried with anhydrous magnesium sulfate and filtered.
• Step 6 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)3-methyl-4-dif luoromethyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step 7 1-[4-Chloro-2-fluoro-5-(3-tetrahydrofuranyloxy) phenyl]-3-methyl-4-d ⁇ fluoromethyl- ⁇ 2 -1,2,4triazolin-5-one
• This compound was prepared by the method similar to that of Example 1.
• the nmr spectrum was consistent with the proposed structure.
• This compound was prepared by the reaction of 0.7 g (0.00238 mole) of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4-triazolin-5-one with 0.4 g (0.00242 mole) of tetrahydrofurfuryl bromide in the presence of 0.06 g (0.00247 mole) of sodium hydride and 30 mL of dimethylformamide; yield, 0.25 g as an oil .
• 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), rice (Oryza sativa var. Labelle), wheat (Triticum aestivium var.
• Two disposable fiber flats (8 cm x 15 cm x 25 cm) for each rate of application for each candidate herbicide for preemergence testing were filled to an approximate depth of 6.5 cm with steam sterilized sandy loam soil.
• the soil was leveled and impressed with a template to provide six evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds or tubers of cotton, soybean, corn, rice, wheat, and yellow nutsedge were planted in the furrows of the first flat, and seeds of bindweed, morningglory, velvetleaf, barnyardgrass, green foxtail, and johnsongrass were planted in the furrows of the second flat.
• the six-row template was again employed to firmly press the seeds or tubers into place.
• 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.
• Flats for postemergence testing were prepared in the same manner.
• the flats for the preemergence test were first watered, then drenched with a solution of test compound as described below.
• the flats were placed in a green house 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 foliage of the emerged test plants was sprayed with a solution of the test compound. After spraying, the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
• the candidate herbicides were applied as aqueous-acetone solutions at rates equivalent to 8.0 kilograms/hectare (kg/ha) and submultiples thereof, i.e., 4.0 kg/ha, 2.0 kg/ha, and so on.
• Preemergence applications were made as soil drenches using 100 mL of test solution of appropriate concentration for each of the two flats/compound.
• Postemergence applications were made as foliage sprays using 5 mL of test solution for each of the two flats.
• an application rate of 8.0 kg/ha of test compound is equivalent to 0.025 g/flat.
• a stock solution of 0.2 g of test compound in 40 mL of acetone containing 0.5% v/v of sorbitan monolaurate emulsifier/solubilizer was prepared.
• 10 mL of the stock solution was diluted with water to give 200 mL of test solution for application as a soil drench to both flats for the compound, 100 mL/flat.
• 10 mL of the stock solution was used undiluted as a spray, 5 mL/flat.
• the remaining 20 mL of stock solution was diluted with an equal volume of acetone-emulsifier to give 40 mL of a second stock solution, containing 0.1 g of test compound, and the process above repeated, i.e., 20 mL of the solution being used for the 4.0 kg/ha application rate, and 20 mL for the preparation of lower rate test solutions by the same process.
• 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 below by numbers which correspond to those in Table 1 above.
• these active herbicidal compounds may be formulated as granules of relatively large particle size, as 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 in the area 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 act 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 which are homogeneous liquid or paste compositions which are 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, and other non-volatile organic solvents.
• 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 from 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 are useful herein with the present herbicidal compounds.
• the active herbicidal compounds of this inventiqn may be formulated and/or applied with insecticides, fungicides, nematocides, plant growth regulators, fertilizers, and other agricultural chemicals and may be used as effective soil sterilants as well as herbicidally. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the compound is of course employed.

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