CA1281724C - Haloalkyl triazolinones - Google Patents

Abstract

ABSTRACT
Herbicidal 1-aryl-1,2,4-triazolin-5(1H)-ones of the formula:
in which X1 is F or C1;
Z is nitro or a group of the formula -OR, -CO-R6, -CH2CO-R6, or -CH(CH3)CO-R6;
R1 is alkyl of 1 to 4 carbon atoms or haloalkyl of 1 to 3 carbon atoms; and R2 is fluoroalkyl of 1 to 4 carbon atoms.

Description

HALOALKYL TRIAZOLINONES
This invention relates to herbicidal l-aryl-4,5-dihydro-1,2,4-triazol-5(lH)-ones having a halo-alkyl group on the carbon at the 3-position of the triazolinone ring.
The herbicidal activity of certain l-aryl-4,5-dihydro-1,2,4-triazol-5(1H)-ones (also known as l-aryl-~ -1,2,4-triazolin-5-ones) having an alkyl group attached to the carbon at the 3-position of the heterocyclic ring has been described in the patent literature, as discussed below.
British published patent application 2,090,250 discloses herbicidal compounds of the formula Cl - ~ ~ N_R2 N~L Rl wherein R is an alkyl group, R is an alkynyl group, a halomethyl group, or a haloethyl group and X
is an alkoxy group, an alkenyloxy group, an alkoxy-alkoxy group, an alkynyloxy group, a hydroxy group, a halomethyloxy group, or a haloethyloxy group.
Japanese Kokai 107975 discloses herbicidal com-pounds of the formula Y ~ ~ R '-.'f '7~4 (Rl is 1-4C alkyl; R2 is H, 1-4C alkyl, halo-methyl or 3-4C alkynyl; X is Cl or F, Y is Cl, Br, OH
or OR3; R3 is 1-4C alkyl or benzyl; z is H, car-boxy, cyanomethoxy, COOR4, COSR5 or CON(R6)(R7);
R4 is 1-4C alkyl or 3-4C alkoxyalkyl; R5 is 1-4C
alkyl, and R6 and R7 are H, 1-4C alkyl or alkoxy).
U.S. patent 4,318,731 discloses herbicidal com-pounds of the formula Cl O

Cl ~ 1 wherein Rl is Cl-C4 alkyl; R is hydrogen, Cl-C6 alkyl or C1-C4 alkenyl; and X is hydroxy, Cl-C4 alkyl, C1-C6 alkyloxy, an alkyloxyalkyloxy of which two alkyls may be the same or different and each alkyl is Cl-C4, a C2-C4 alkenyloxy, or an alkyloxycar-bonylalkyloxy of which two alkyls may be the same or different and each alkyl is C1-C4.
Also, U.S. patent 4,404,019 discloses herbicidal compounds of the formula Y ~ F ~
-R

wherein R is a Cl-C4 =lkyl group, a C3-C4 :

.

1~17~4 alkenyl group or a C3-C4 cycloalkyl group, X is a chlorine or bromine atom and Y is a hydrogen atom ~r a Cl-C4 alkoxy group.
The compounds of this invention are herbicidal aryl-4,5-dihydro-1,2,4-triazol-5( lH) -ones (such as those in the prior art, e.g. described above) in which, however, the carbon atom at the 3-position of the triazole ring carries a Cl-C4 haloalkyl group whose halogens are selected from F, Cl and Br, par-ticularly a fluoroalkyl (e.g. difluoromethyl) group.
The compounds of the invention are those which have the following formula:

Ar- N~- R

where R is said haloalkyl group and R may be hydrogen, but preferably is alkyl (e.g. of 1 to 6, preferably 1 to 4, carbon atoms); haloalkyl (e.g. of 1 to 5, preferably 1 to 3, carbon atoms particularly fluoroalkyl); cyanoalkyl (e.g. of 2 to 5 carbon atoms, for example, cyanomethyl); alkenyl (e.g. of 2 to 5 carbon atoms such as 2-propenyl): alkynyl (e.g. of 2 to 5 carbon atoms such as 2-propynyl); alkoxyalkyl (e.g. of 2 to 8 carbon atoms, for example, 2-methoxy-ethyl), amino; alkylamino (e.g. of 1 to 6 carbon atoms) alkoxy (e.g. of 1 to 6, preferably 1 to 4, carbon atoms); haloalkenyl or haloalkynyl; or alkyl-thioalkyl (e.g. of 2 to 8 carbon atoms, for example 2-methylthioethyl) or the corresponding alkylsulfinyl-~'' ' . :
- ~ -alkyl or aikylsulfonylalkyl groups (having, respec-tively 1 or 2 oxygen atoms on the S atom); and Ar is an aryl radical. Ar is further defined by the limita-tion that the 3-Methyl-4-Difluoromethyl Analogs of the compounds of this invention are herbicides, said Analogs being compounds which are otherwise identical to compounds of this invention except that said Analogs have, at the 3- and 4-positions of the 4,5-di-hydrotriazol-(lH)-ring, a CH3 and a CHF2 substi-tuent, respectively. The aryl radical thus represents a group useful in the l-aryl-4,5-dihydro-1,2,4-tria-zol-5(1H)-one art to give herbicidal compounds when attached at the l-position of an appropriate known 4,5-dihdyro-1,2,4-triazol-5(lH)-one. For instance any of the aryl radicals of the aforementioned patents may be used.
The Ar radical is preferably such that said 3-Methyl-4-Difluoromethyl Analog has marked herbicidal properties. For instance, the 3-Methyl-4-Difluoro-methyl Analogs of the preferred compounds show at least 50% kill of at least one of the following species of plants when applied under at least one of the following modes at the rate of 0.5 kg/ha, and more preferably show such kill of at least 50% when applied at the rate of O.l kg/ha: Species: velvetleaf (Abutilon theophrasti), green foxtail (Setaria viridis): Modes: pre-emergent, post-emergent. Testing for such herbicidal activity may be carried out in the manner described below (under the heading "Herbicidal Activity").
Ar is preferably a ring-substituted aryl radi-cal. For instance it may have a benzene ring such as the radical indicated by the following formula ~' >~
Z H

wherein X may be for instance hydrogen or halogen, preferably fluorine or chlorine, the halogen atom advantageously being positioned at the C-2 carbon atom of the phenyl ring;
x2 may be hydrogen, halogen such as fluorine, chlorine, or bromine, alkyl of 1 to 6 (preferably l to 4) carbon atoms, particularly methyl, haloalkyl of l to 5 carbon atoms, for example, trifluoromethyl, alkoxy of l to 6 (preferably l to 4) carbon atoms:
Z may, for instance, be hydrogen: halogen such as fluorine, chlorine, or bromine: alkyl of l to 6 tpre-ferably l to 4) carbon atoms: cyanoalkyl: haloalkyl of l to 5 carbon atoms: nitro; a group -OR; or a group -CO-R6 or CH2CO-R6 or CH(CH3)CO-R6; or a group -OSO2R9;
R may be hydrogen, alkyl of l to 6 (preferably l to 4) carbon atoms which may be substituted with cycloalkyl of 3 to 7 carbon atoms (for example, methyl or l-methylethyl, or cyclohexylmethyl), cycloalkyl of 3 to 7 carbon atoms which may be sub5tituted with alkyl of l to 6 carbon atoms (for example, cyclopentyl or methylcyclopropyl), alkoxyalkyl of 2 to 8 carbon atoms (for example, ethoxymethyl), cyanoalkyl of 2 to 7 carbon atoms such as cyanomethyl or 2-cyanoethyl, alkenyl of 2 to 5 carbon atoms such as 2-propenyl, alkynyl of 2 to 5 carbon atoms such as 2-propynyl, haloalkyl of l to 5 (preferably l to 3) carbon atoms 17~4 especially a fluoroalkyl, haloalkenyl of 2 to 5 carbon atoms, haloalkynyl of 2 to 5 carbon atoms such as 3-bromo-2-propynyl, alkylsulfonyl of 1 to 6 (prefer-ably 1 to 4) carbon atoms (wherein the alkyl moiety may be substituted with halogen, especially fluorine or chlorine, cyano, alkoxy or alkylthio of 1 to 4 carbon atoms such as methoxy or methylthio, or alkyl-amino or dialkylamino in which each alkyl is of 1 to 4 carbon atoms), alkylaminosulfonyl or dialkylaminosul-fonyl wherein each alkyl is of 1 to 4 carbon atoms, arylsulfonyl such as phenylsulfonyl, alkylcarbonyl of 2 to 7 carbon atoms such as acetyl, or a 5- or 6-mem-bered ring heterocyclic group of 1 or 2 same or dif-ferent heteroatoms selected from O, S (including the S-oxide and S-dioxide), and N or an alkyl radical of 1 to 5 (preferably 1 to 3) carbon atoms substituted with said heterocyclic group. R may also be a group -CR3R4(CH2)n-Co-Ql-R5 in which n is 0 to 2 (preferably 0); R and R4 may be independently hydrogen or alkyl or alkoxy of 1 to 4 carbon atoms, Ql is O, S
or NR7 wherein R7 may be H or alkyl of 1 to 6 (preferably 1 to 4) carbon atoms and R may be hydrogen, alkyl of 1 to 6 (preferably 1 to 4) carbon atomc, alkoxyalkyl or alkylthioalky~ of 2 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms (especially fluoroalkyl or chloroalkyl), alkenyl of 2 to 5 carbon atoms such as 2-propenyl, cycloalkenyl of 5 to 7 carbon atoms which may be substituted with alkyl of 1 to 4 carbon atoms (for example, 2-cyclohexenyl), cyclohexenylalkyl of 6 to lO carbon atoms (for example, 3-cyclohexenylmethyl), phenyl or benzyl : (which may be ring-substituted with fluorine, chlo-rine, bromine, or alkyl, alkoxy, or alkylthio of 1 to 4 carbon atoms), cyanoalkyl of 2 to 7 carbon atoms such as cyanomethyl, alkynyl of 2 to 5 carbon atoms such as 2-propynyl, alkylideneamino of l to 6 (prefer-ably l to 4) carbon atoms which may be substituted with cycloalkyl of 3 to 7 carbon atoms, cycloalkylideneamino of 5 to 7 carbon atoms which may be substituted with alkyl of l to 4 carbon atoms. When Ql is NR7, R5 may additionally be alkoxy, alkylthio, or alkylsulfo~yl, each of l to 6 carbon atoms, phenylsulfonyl, or phenyl-alkylsulfonyl of l to 3 alkyl carbon atoms.
As a preferred feature of the invention there is provided an herbicidal compound of the formula:

xl o ~ 1 Cl ~ O ~ N N -R
~ N ~
Z~ R

in which xl is F or Cl;
Z is nitro or a group of the formula -OR, -CO-R6, -CH2CO-R6, or -CH(CH3)CO-R6;
R is alkyl of 1 to 6 carbon atoms which is un-substltuted or is substituted with cycloalkyl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms which is unsubstituted or is sub-stituted with alkyl of 1 to 6 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoalkyl of 2 to 7 carbon atoms, alkenyl of 2 to 5 car-bon atoms, alkynyl of 2 to 5 carbon atoms, haloalkyl of 1 to 5 carbon atoms, haloalkenyl of 2 to 5 carbon atoms, haloalkynyl of 2 to 5 carbon atoms, alkylsulfonyl of l to 6 carbon atoms (wherein the alkyl moiety is unsubsti-B~

7~4 - 7a -tuted or is substituted with F, Cl, CW, alkoxy or alkylthio of 1 to 4 carbon atoms, or alkyl-amino or dialkylamino in which each alkyl is of 1 to 4 carbon atoms), alkylaminosulfonyl or dialkylaminosulfonyl in which each alkyl is of 1 to 4 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms, or a group of the formula -C(R3)(R4)(CH2)n-Co-Q1R5 or -C(R3)(R4)(CH2)n-Co-N(R7)(R8) in which n is 0 to 2;
R3 and R4 are independently H, alkyl of 1 to 4 carbon atoms, or alkoxy or 1 to 4 carbon atoms;
Ql is O or Si R5 is H, alkyl of 1 to 6 carbon atoms, alkoxyal-kyl or alkylthioalkyl of 2 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, cycloalkenyl of 5 to 7 car-bon atoms which is unsubstituted or is substi-tuted with alkyl of 1 to 5 carbon atoms, cyc-lohexenylalkyl of 6 to 10 carbon atoms, phenyl or benzyl (which may be ring-substituted with fluorine, chlorine, bromine, or alkyl, alkoxy, or alkylthio of 1 to 4 carbon atoms), cyanoal-kyl of 2 to 7 carbon atoms, alkynyl of 2 to 5 carbon atoms, alkylideneamino of 1 to 6 carbon atoms which is unsubstituted or is substituted with cycloalkyl of 3 to 7 carbon atoms, or cycloalkylideneamino of 5 to 7 carbon atoms, which is unsubstituted or is substituted with alkyl of 1 to 4 carbon atoms;
R6 is hydroxy, alkoxy or alkylthio of 1 to 6 car-bon atoms, alkoxyalkoxy of 2 to 6 carbon atoms, amino, or alkylamino or dialkylamino wherein each alkyl is of 1 to 6 carbon atoms and is unsubstituted or is substituted with alkoxy of 1 to 4 carbon atoms;

7~4 - 7b -R7 is H or alkyl of 1 to 6 carbon atoms;
R8 is R5 or alkoxy of 1 to 6 carbon atoms, alkyl-thio of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, phenylsulfonyl, or phe-nylalkylsulfonyl of 1 to 3 alkyl carbon atoms;
Rl is alkyl of 1 to 4 carbon atoms or haloalkyl of 1 to 3 carbon atoms; and R2 is fluoroalkyl of 1 to 4 carbon atoms.
As indicated above, R of the -OR substituent may be a heterocyclic group or an alkyl radical substituted with a heterocyclic group. The R group of this type may be any of those disclosed in my copending Canadian Ap-plication No. 465,372, filed October 12, 1984, which discloses aryltriazolinones whose aryl groups have such -OR substituents. The "Ar" radical of this invention may be any of the aryl radicals disclosed in those ap-plications. Among the R groups, on those aryl radicals, which may be employed are l-methyl-3-pyrrolidinyl, fur-furyl or 2-thienylmethyl, or preferably 3-tetrahydrofur-anyl, 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-benzodioxan-2-ylmethyl, tetrahydro-4H-pyran-4-yl, 5,6-dihydro-2H-pyran-3-ylmethyl, 2,2-dimethyl-1,3-dithiolan-4-ylmethyl, tetrahydro-4H-thiopyran-4-yl, tetrahydro-thien-3-yl, 1-oxotetrahydrothien-3-yl, l,l-dioxotetra-hydrothien-3-yl, 2,2-dimethyl-1,1,3,3-tetraoxo-1,3-dithiolan-4-ylmethyl, 1,4-dithiacycloheptan-6-yl, 1,4-dithiacyclohept-5-17~4 ene-6-yl, tetrahydro-4H-pyran-3-yl, glycidyl, 2,3-epi-thiopropyl, 2,2-bis(chlorodifluoromethyl)-1,3-dioxo-lan-4-ylmethyl, or 1,1-dioxotetrahydro-4H-thiopyran-4-yl .
As indieated above, Z may be a group -CO-R6, -CH2CO-R6 or -CH(CH3)CO-R6 where R6 is hydroxy, alkoxy or alkylthio of 1 to 6 carbon atoms sueh as methoxy or methylthio, alkoxyalkoxy of 2 to 6 earbon atoms (for example, 2-methoxyethoxy), amino, or alkylamino or dialkylamino wherein each alkyl is of 1 to 6 (pre-ferably 1 to 4) carbon atoms and may be substituted with alkoxy of 1 to 4 carbon atoms (for example, methylamino, dimethylamino, or (methyl)(2-methoxy-ethyl)amino).
As indieated above, R of the -OR substituent may be a group -CR3R4(CH2)nCoQl-R5. Aryl triazolinones whose aryl radieals have such -OR substituents of this type are diselosed in my copending Canadian Applica-tion No. 493,598, filed October 22, 1985. The "Ar"
radieal of this invention may be any of the aryl radieals diselosed in that copending application.
As indieated above, Z may also be a group -OSO2R9 where R9 is alkyl, haloalkyl, cyanoalkyl, arylalkyl, cyclie alkyl, alkenyl, haloalkenyl, arylalkenyl, alkynyl, haloalkynyl, arylalkynyl, aryl, or a group of the formula - tCH2 )mNR3 R4 or -alkyl-Y-R5 wherein m is 0 to 5; R3 is hydrogen or alkyl; R4 is alkyl or a group of the formula -alkyl-Y3 -R8 ; R8 is alkyl, alkoxycarbonylalkyl, alkenyl, or alkynyl; and Y3 is oxygen or S()r in which r is 0 to 2. MY U.S. Patent No. 4,705,557, issued November 10, 1987, ) .

, .

.
' 7 ~: ~
g discloses aryl triazolinones whose aryl groups have a 5-substituent designated in said applications as "-OSO2R". The "Ar" radical of this invention may be any of the aryl radicals disclosed in those applica-tions. Among the -OSO2R9 groups, on those aryl rad-icals, which may be used are those in which R9 is methyl, ethyl, propyl, l-methylethyl, butyl, 2-methylpropyl, l-methylpropyl, 3-methylbutyl, chloro-methyl, dichloromethyl, 3-chloropropyl, bromomethyl, difluoromethyl, trifluoromethyl, cyanomethyl, benzyl, cyclopropyl, 2-propenyl, 2,3,3-trichloro-2-propenyl, 2-propynyl, 3-bromo-2-propynyl, dimethylamino, di-methylaminoethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-(2-propenoxy)ethyl, 2-(2-propenthio)ethyl, 2-(2-propyn-oxy)ethyl, 2-(methoxycarbonylmethoxy)ethyl, and 2-(methoxycarbonylmethylthio)ethyl.
Frequently, the aryl radical will be a dihalo-phenyl radical, preferably a 2,4-dihalophenyl radical, for example, a 5-(alkoxy or alkynyloxy of up to 6 carbon atoms) -2,4-dihalophenyl radical such as a 4-chloro-2-fluoro-5-(1-methylethoxy)phenyl or 4-chloro-2-fluoro-5-(2-propynyloxy)phenyl radical.
It will be understood that any alkyl alkenyl or alkynyl groups of the compound may be straight chain or branched chain radicals. Thus, l-methylethyl, 2-methyl-2-propenyl, and 1-methyl-2-propynyl are branched chain examples of alkyl, alkenyl, and alkynyl radicals respectively. The halogen may be fluorine, chlorine, bromine or iodine. The haloalkyl radical may have one or more same or different halogen atoms.
Included in the genus above are compounds in which Z is hydroxy, which, while generally herbicidal 1 o at high application rates, are more useful as inter-mediates than as herbicides. As useful intermediates in the preparation of the more herbicidally active members of the genus, such compounds form a preferred embodiment of the invention.
With respect to herbicidal properties, in the embodiments presently of most interest, the substi-tuents Xl and x2 are preferably both halogen, with xl being fluorine or chlorine and x2 being chlo-10 rine or bromine. The X halogen will usually be positioned at the C-2 carbon atom of the phenyl ring.
The compounds wherein Xl is fluorine are particu-larly preferred.
The present compounds may be prepared by methods 15 described in the literature or by methods analogous and similar thereto and within the skill of the art.
To make the compounds of the present invention in which R2 is CHF2, it is particularly convenient to start with CHF2COOH, by converting the latter into 20 an ester of difluoroacetylcarbamic acid (e.g. an ester of the formula CHF2-CO-NHCO-O-lower alkyl), as by first converting the starting material into its acid chloride (e.g. by reaction with SOC12) and then reacting the latter with a lower alkyl urethane of the 25 formùla NH2CO-O-lower alkyl as illustr~ted in Step A
of Example 1, below.
The ester of difluoroacetylcarbamic acid may then be converted into a l-aryl-4,5-dihydro-3-difluoro-methyl-1,2,4-triazol-5(1H)-one by reacting it with an 30 aryl hydrazine, as illustrated in Step B of Example 1. The aryl group of that hydrazine may carry all the substituents desired in the final compound (as is the case in the process for making compound lO described at the end of Step B of Example 1) or those substi-35 tuents, and any R substituent, may be added in . "

. : ' :

~317~4 subsequent reactions, as illustrated in Steps C, D, E, F and G of Example 1. One or both of the (halogen) substituents at the 2- and/or 4-position of the phenyl group may be introduced subsequently, e.g. by halo-genating (as with SO2C12) a 1-aryl-4,5-dihydro-3-difluoromethyl-4-methyl-1,2,4-triazol-5(lH)-one having hydrogen at one of those 2- and/or 4-positions and having any appropriate group at the 5-position of the phenyl group.
Instead of the alkyl difluoroacetylcarbamate one may use a haloacetonitrile (such as F2HC-CN or F3C-C~ or F2ClC-CN) for reaction with the aryl hydrazine (as illustrated in Step A of Example 2, below) to form the polyhaloacetamidine, which may then be reacted with phosgene to form a 1-aryl~4,5-dihydro-3-polyhalomethyl-4,5-dihydro-1,2,4-triazol-5(lH)-one (as illustrated in Step B of Example 2). Subsequent reactions may add an R substituent at the 4-posi-tion of the 4,5-dihydro-1,2,4-triazol ring (as in Step C of Example 2) and/or vary the substituents on the aryl radical.
In these synthesis methods (e.g. the particular routes described above and in the Examples) there are formed useful intermediates which are l-aryl-4,5-di-hydro-1,2,4-triazol-5(1H)-ones having H on the nitro-gen at the 4-position of the 4,5-dihydrotriazol ring and h~aloalkyl of 1 to 4 carbon atoms (e.g. CHF2, CF3 or CClF2) on the carbon at the 3-position of that ring. (It will be understood that these com-pounds may also exist in their tantomeric forms as l-aryl-1,2-dihydro-1,2,4-triazol-5(lH)-ones having hydrogen on the nitrogen at the 2-position. The l-aryl group of such an intermediate may be a substi-tuted phenyl radical identical with that present in the final compound or it may be a substituted phenyl . . .

.

i7~4 radical containing an easily replaceable substituent (e.g., a methoxy group at the 5-position of the phenyl radical, as in a 5-methoxy-4-chloro(or bromo)-2-fluoro-phenyl radical) which phenyl radical can then be con-verted, by replacing that substituent, to the final substituted phenyl radical, preferably after first converting it to the corresponding phenolic radical te.g. a 5-hydroxyphenyl radical). When the aryl group i5 to have a 2-F substituent it is preferred that the F substituent be present before formation of the heterocyclic ring, e.g. by using a fluorophenyl hydrazine as the reactant.
Some representative compounds of this invention are identified in the following table.

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The following Examples illustrate the preparation of the compounds of this invention.
Example 1 N-(2-CHLOROPHENYLSULFONYL) l-t2-CHLORO-4-FLUORO-5-(3-DIFLUOROMETHYL-4,5-DIHYDRO-4-METHYL-5-OXO-lH-1,2,4-TRIAZOL-l-YL)PHENOXY]PROPIONAMIDE

Step A Ethyl difluoroacetylcarbamate During a thirty minute period 65.4 g (0.55 mole) of thionyl chloride was added dropwise to 50.0 g (0.52 mole) of difluoroacetic acid with stirring, while maintaining a reaction temperature of 20-25C. After complete addition the mixture was stirred at room temperature for 1.5 hours and 46.4 g (0.52 mole/ of urethane was added. The resultant mixture was heated at reflux for approximately three hours then allowed to cool to room temperature and stir-for approximately 18 hours. The reaction mixture was again heated at 77C for two hours. Unreacted materials were removed from the reaction mixture by evaporation under reduced pressure leaving 81.1 g of ethyl difluoroacetylcarba-mate as a semi-solid residue.
The nmr spectrum was consistent with the proposed structure.

Step B 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(lH)-one To a stirred mixture of 8.0 g (0.042 mole) of 4-chloro-2-fluoro-5-methoxyphenylhydrazine and 8.4 g (0.05 mole) of ethyl difluoroacetylcarbamate in 120 mL
of xylene was added 2.1 g of phosphorus pentoxide.
After complete addition the mixture was heated at reflux for one hour. While still hot, the reaction .

7'~4 mixture was decanted from a dark residue into a clean flask. This residue was washed with xylene and the wash was combined with the decanted reaction mixture.
The resultant mixture was stirred at room temperature for one hour. A precipitate formed and was removed by filtration and saved for later purification. The filtrate was extracted with three lS0 mL portions of an aqueous 10% sodium hydroxide solution. The basic washes were combined and extracted with xylene. Dur-ing the extraction an oil formed a third phase in the bottom of the separatory funnel and was removed from the other two phases. The basic aqueous phase was separated from the organic phase and filtered through a celite pad. The filtrate was washed with two por-tions of diethyl ether and acidified with concentrated hydrochloric acid. The acidified aqueous mixture was stirred at room temperature forming a brown precipi-tate. Collection of the precipitate by filtration yielded l.S g of 1-(4-chloro-2-fluoro-5-methoxy-phenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one. The precipitate which was previously saved for purification was stirred in 70 mL of an a~ueous 10% sodium hydroxide solution. The basic mixture was filtered through a celite pad to remove insoluble materials. The filtrate was acidified with concen-trated hydrochloric acid producing a white solid.
This solid was collected by filtration to yield an additional 0.7 g of product (mp 188-190C).
The nmr spectrum was consistent with the proposed structure.
Compound 10, 1-[2,4-dichloro-5-(1-methylethoxy)-phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(lE~)-one, and 1-(3-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(lE~)-one were prepared by ; 35 the method of Example 1, Step B, from 2,4-dichloro-~a~7~4 5-(1-methylethoxy)phenylhydrazine or 3-methoxyphenyl-hydrazine, respectively.

Step C 1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one A stirred mixture of 2.0 g t0.0067 mole) of 1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-difluoro-methyl-4,5-dihydro-1,2,4-triazol-5(lH)-one and 2.1 g (0.015 mole) of potassium carbonate in 50 mL of acetone was heated at reflux for 30 minutes forming a thick slurry. Iodomethane (4.3 g, 0.03 mole) was added in one portion to the refluxing reaction mix-ture. After complete addition the mixture was stirred at reflux for 45 minutes. The mixture was cooled to room temperature and the solvent evaporated under reduced pressure leaving a solid residue. This residue was partitioned between water and methylene chloride. The two phase mixture was filtered through a celite pad. The organic phase was removed and was washed in succession with four portions of an aqueous 10% sodium hydroxide solution, and one portion each of an aqueous 10% hydrochloric acid solution, a saturated aqueous sodium carbonate solution, and water. After washing, the organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 1.6 g of 1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-difluoro-methyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one.
A portion of this material was recrystallized from ; 30 ethanol and water to provide the product as a light tan solid (mp 127-129C), Compound 22.
The nmr spectrum was consistent with the proposed structure.

::
"

1~17~4 Analysis calcd for CllHgClF3N3O2: C 42.94: H 2.95: N 13.66, Found: C 42.74: H 3.15: N 13.35.
The following compounds were also prepared by the process of Example 1, Step C, from 1-(4-chloro-2-fluoro-5-methoxy-phenyl-3-difluoromethyl-4,5-di-hydro-1,2,4-triazol-5(1H)-one: 1-(2,4-dichloro-5-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(lH)-one, or 1-(3-methoxyphenyl)-3-difluoro-methyl-4,5-dihydro-1,2,4-triazol-5(1H)-one and one of the following:

Compound Reagent 4 iodo.nethane 6 iodomethane 11 iodomethane 12 allyl bromide 27 iodoethane 33 chloromethyl methyl ether Compounds which contain a 4-difluoromethyl group (i.e. Compounds 3 and 5) may be prepared by a process analogous to Example 1, Step C, by reacting 1-(3-meth-oxyphenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-tria-zol-5(lH)-one or 1-(2,4-dichloro-5-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one first with sodium hydroxide and tetrabutylammonium bromide in cyclohexane and tetrahydrofuran followed by chlorodifluoromethane.

Step D 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one To a stirred ice cold solution of 1.5 g (0.0048 17~4 mole) of l-(4-chloro-2-fluoro-5-methoxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one in 80 mL of methylene chloride was added dropwise 14.2 mL of a 1 M solution of boron tribromide in methylene chloride. After complete addition the mixture was allowed to warm to room temperature and stir for approximately 18 hours. The mixture was poured into ice water and the resultant mixture stirred until the ice had melted. The organic phase was separated from the mixture and was washed with two portions of water. After washing, the organic phase was dried over anhydrous magnesium sulfate and fil-tered. Evaporation of the filtrate under reduced pressure yielded 1.2 g of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydrG-4-methyl-1,2,4-triazol-S(lH)-one (mp 153-155~C), Compound 23.
The nmr spectrum was consistent with the proposed structure.
Compounds 1, 2, 28 and 38 were prepared by the process disclosed in Example 1, Step D, from the corresponding l-(2-halo-4-chloro-5-alkoxyphenyl)-1,2,4-triazol-5(lH)-one.

Step E tert-Butyl 2-~2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionate A mixture of 0.7 g (0.0023 mole) of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one, 0.9 g (0.0067 mole) of potassium carbonate, and 0.6 g (0.0027 mole) of tert-butyl 2-bromopropionate in 40 mL of acetone was stirred at room temperature for approximately 72 hours. The reaction mixture was partitioned between water and methylene chloride and the organic phase was 7'~4 washed with water. After drying over anhydrous magne-sium sulfate the organic phase was filtered.
Evaporation of the filtrate under reduced pressure yielded 0.9 g of tert-butyl 2-~2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionate as an oil, Compound 40.
The nmr spectrum was consistent with the proposed structure.
The following compounds were also prepared by the process of Example 1, Step E, from 1-(2,4-dichloro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one, Compound 2; 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one, Compound 23; 1-(2,4-dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one; 1-(2,4-di-chloro-5-hydroxyphenyl)-3-trifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one, Compound 38;
1-(2,4-dichloro-5-hydroxyphenyl)-4-ethyl-3-difluoro-methyl-4,5-dihydro-1,2,4-triazol-5(lH)-one, Compound 28; 1-(2,4-dichloro-5-hydroxyphenyl)-3-difluoro-methyl-4,5-dihydro-4-(2-propenyl)-1,2,4-triazol-5(lH)-one; or l-(2,4-dichloro-5-hydroxyphenyl)-4-cyano-methyl-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one and one of the following:

-- . .

' ' - :. ' ` :. ' `

i.7'~4 Compound Reagent 7 propargyl bromide 8 propargyl bromide 13 propargyl bromide 16 methyl bromoacetate 17 bromo acetonitrile 18 iodoacetamide propargyl bromide 21 ethyl 2-bromopropionate propargyl bromide 29 propargyl bromide 32 chloromethyl methyl ether 34 propargyl bromide 37 propargyl bromide In addition, the following compounds were pre-pared in a manner analogous to Example 1, Step E, replacing potassium-carbonate and acetone with sodium.
hydride and N,N-dimethylformamide, from one of the 1,2,4-triazol-5(1H)-one intermediates listed above and one of the following:
-Compound Reagent 9 3-tetrahydrofuryl 4-methyl-benzenesulfonate 14 ethyl 2-bromopropionate ethyl 2-bromopropionate 19 3-tetrahydrofuryl 4-methyl-benzenesulfonate 26 ethyl 2-bromopropionate .
Step F 2-~2-Chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionic acid :~, : ~
, - -::
,, :

-.

A mixture of 0.8 g (0.002 mole) of tert-butyl 2-[2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihy-dro-4-methyl-5-oxo-1~-1,2,4-triazol-1-yl)phenoxy]pro-pionate and 59.2 g (0.52 mole) of trifluoroacetic acid was stirred at room temperature for two hours. Most of the trifluoroacetic acid was removed from the mix-ture by distillation under reduced pressure leaving a residue. This residue was partitioned between methyl-ene chloride and water. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.5 g of 2-[2-chloro-4-fluoro-5-(3-difluoro-methyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionic acid as an oil.
The nmr was consistent with the proposed structure.

Step G N-(2-Chlorophenylsulfonyl) 2-E2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionamide]

A stirred mixture of 0.4 g (0.0011 mole) of 2-[2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid, 0.2 g (0.0011 mole) of 2-chlorophenylsulfonyl isocyanate and a catalytic amount (0.03 g) of 4-di-methylaminopyridine in 40 mL of toluene was heated at reflux for approximately 18 hours. The mixture was cooled and evaporated under reduced pressure to yield 0.5 g of N-(2-chlorophenylsulfonyl) 2-~2-chloro-4-fluoro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-ly)phenoxy]propionamide as a solid (mp 162-166C), Compound 39.
The nmr spectrum was consistent with the proposed structure.

1~17'~4 Example 2 1-[2,4-DICHLORO-5-(1-METHYLETHOXY)PHENYL~-3-TRIFLUOROMETHYL-4,5-DIHYDRO-4-METHYL-1,2,4-TRIAZOL-5(1H)-ONE

Step A N-[2,4-Dichloro-5-(l-methylethoxy)anilino]-trifluoroacetamidine Under a dry nitrogen atmosphere a stirred solu-tion of 2.4 g (0.01 mole) of 2,4-dichloro-5-(1-me,hyl-ethoxy)phenylhydrazine in 140 mL of methanol was cooled to -60C in a dry ice-isopropanol bath.
Trifluoroacetonitrile (23.2 g, 0.24 mole) was bubbled into the cold solution durîng a two minute period.
After complete addition the cold solution was stirred for 30 minutes, then allowed to warm slowly to room temperature during the next three hours. A stream of nitrogen gas was bubbled into the room temperature solution to aid in the vaporization and removal of trifluoroacetonitrile, leaving a liquid xesidue. This residue was evaporated further under reduced pressure to leave a resinous material. This material was stirred in cold pentane to produce a solid. The pentane was decanted and the solid triturated in fresh cold pentane. The pentane was decanted and the solid dried under reduced pressure to yield 2.9 g of N-[2,4-dichloro-5-(1-methylethoxy)anilino]trifluoro-acetamidine (mp 80.5-81C).
The nmr spectrum was consistent with the proposed structure.
In addition to the above intermediate, N-[2,4-di-chloro-5-(1-methylethoxy)anilino]chlorodifluoroacetami-dine and N-(4-chloro-2-fluoro-5-methoxyanilino)chloro-difluoroacetamidine were prepared by the process described in Example 2, Step A, from the correspond-:

~317~4 ingly substituted phenylhydrazine and chlorodifluoro-acetonitrile.

Step B 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl~-3-trifluoromethyl-4,5-dihydro~1,2,4-triazol-5(lH)-one Under a dry nitrogen atmosphere a stirred solu-tion of 2.1 g (0.0062 mole) of ~-[2,4-dichloro-5-(1-methylethoxy)anilino]trifluoroacetamidine in 130 mL of toluene was cooled in an ice bath. To this was added 5.2 mL (0.037 mole) of triethylamine followed by the dropwise addition of 45.6 mL of a 2.9% (0.013 mole) phosgene in toluene solution. After complete addition the mixture was heated quickly to 65C and stirred at that temperature for 45 minutes. The mixture was allowed to cool to room temperature and stir for approximately 18 hours. The mixture was diluted with 25 mL of water and stirred vigorously for a brief period. Sufficient concentrated hydrochloric acid was added to make the aqueous phase acidic (pH
2). The acidic aqueous phase and the organic phase were shaken briskly after which the organic phase was separated from the mixture and saved for further purification. The aqueous phase was extracted with methylene chloride and the extract evaporated to leave a yellow solid. This solid was dissolved in toluene and the resultant solution added to the saved organic phase from above. The combined organic phase was stirred at room temperature with decolorizing carbon and filtered through a celite pad. The filtrate was extracted with a 1 ~ sodium hydroxide solution. This extract was washed with toluene and acidified with concentrated hydrochloric acid to pH 2. Sodium chlo-ride was added to the acidic solution to the point of .

saturation. A precipitate formed upon cooling this solution and was collected by filtration. The filter cake was rinsed with several portions of ice cold water and dried under reduced pressure to yield 1.8 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-tri-fluoromethyl-4,5-dihydro-1,2,4-triazol-5(lH)-one (mp 160-161C), Compound 36.
The nmr was consistent with the proposed structure.
Analysis calc'd for C12HloC12F3~302: C 40.47: H 2.83: N 11.80:
Found: C 39.01: H 2.96: N 11.38.
Also prepared by the process of Example 2, Step B, were 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4~5-dihydro-l~2~4-triazol-5(lH) one and l-(4-chloro-2-fluoro-5-methoxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one (Compound 30) from the correspondingly substituted chlorodifluoroacetamidine.

Step C 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-trifluoromethyl-4,5-dihydro-4-methyl~1,2,4-triazol-5(lH)-one Under a dry nitrogen atmosphere 0.1 g (0.0038 mole) of dry sodium hydride was added to a stirred solution of 1.3 g (0.0035 mole) of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-trifluoromethyl-4,5-di-hydro-1,2,4-triazol-5(1H)-one in 30 mL of N,N-di-methylformamide. The mixture was stirred at room ; temperature for 20 minutes and 0.6 g (0.0038 mole) of iodomethane was added. After complete addition the mixture was warmed to 65C and stirred at that tem-perature for one hour. The mixture was allowed to cool to room temperature and stir for approximately 18 .

.

.

L7 ~ L~

hours. Most of the solvent was removed by distilla-tion under reduced pressure to leave a liquid resi-due. This residue was partitioned between water and diethyl ether. The organic phase was washed first with a 2 N sodium hydroxide solution followed by water. The organic solution was dried over an anhy-drous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 1.2 g of l-~2,4-dichloro-5-(1-methylethoxy)phenyl]-3-tri-fluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one as a solid (mp 96-98C), Compound 35.
The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C13H12C12F3N3O2: C 42.18; H 3.27; N 11.35;
Found: C 41.52; H 3 18; N 11.14.
Compound 31 was prepared by the manner of Example 1, Step C from Compound 30. Compound 24 was prepared in an analogous manner from 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-di-hydro-1,2,4-triazol-5(lH)-one using potassium carbonate and acetone in place of sodium hydride and N,N-dimethylformamide.
Characterizing properties of some of the compounds of the invention are given in the following Table.

-Cmpd. Melting Elemental Analysis ~o. P~int (C) Empirical Formula C H N
1 Solid CloHscl2F4N3o2 2 190-192 CloH7cl2F2N3o2 C 38.73 2.27 13.55 F 38.74 2.26 13.31 3 86-88 CllHgF4N3O2 4 113-115 CllHllF2N3O2 131-138 C1lH7cl2F4N3O2 6 156-159 CllHgC12F2N302 7 121-124 C13HgC12F2N3O2 8 Solid C13H7C12F4N3O2 9 Oil C14HllC12F4N3O3 Solid C12HllC12F2N302 11 95-97 C13Hl3cl2F2N3O2 12 81-83 ClsHl5cl2F2N3O2 13 69-74 ClsHllcl2F2N3O2 14 Oil ClsHl5cl2F2N3O4 Oil C17Hl7cl2F2N3O4 16 Solid C13Hllcl2F2N3O4 17 132-135 C12HgC12F2N402 18 190-193.5 Cl2Hlocl2F2N4o2 19 Oil C14Hl3cl2F2N3O3 106-107 C13H9clF3N302 C 47.08 2.73 12.67 F 46.98 2.80 12.61 21 Oil C1sHl5clF3N3O4 TABLE 2 (aontinued) Cmpd. Melting Elemental ~nalysis o. Point (C) Empirical Formula C H N
22 127-129 CllHgclF3N3o2 C 42 94 3 15 13 35 23 153-155 CloH7clF3N3o2 146-147.5 C13H8C13F2N32 F 40 48 2 04 10 61 26 Oil ClsHl4cl3F2N3O4 27 oi 1 C14Hlscl2F2N3O2 28 120-124 CllHgcl2F2N3O2 29 104-107 Cl4Hllcl2F2N3o2 F 46 85 3 lG 11 54 200-205 CloH6cl2F3N3o2 F 37 33 2 16 12 63 31 78-88 CloH8cl2F3N3o2 32 114-116 C12HllclF3N3O3 33 Solid C12HllClF3N303 34 oi 1 cl4H8ClF3N42 96-98 q 3Hl2cl2F3N3o2 F 41 52 3 18 11 14 36 160-161.5 C12H10C12F3N32 F 39 01 2 96 11 38 37 132.5-134.5 C13H8Cl2F3N3O2 F 42 83 2 54 10 70 38 174-175 CloH6cl2F3N3o2 C 36 61 2 14 12 10 39 162-166 Cl9H15C12F3N45S
Oil C17H19ClF3N304 0936W30093W~.d ~ ~1724 HERBICIDAL ACTIVITY
The plant tests species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hlrsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticum aestivium var.
Prodax), field bindweed (Convolvulus arvensis), morningglory (Ipomea lacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), johnsongrass (Sorghum halepense), yellow nutsedge (Cyperus esculentus), and rice (Oryza sativa).
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 solu-tion of the test compound in a mixture of acetone and water containing a small amount (up to 0.5~ v/v) of sorbitan monolaurate emulsifier/solubilizer. The concentration 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 foliage of the emerged test plants was sprayed with a solution of the test compound in acetone-water con-taining up to 0.5% sorbitan monolaurate. After spray-ing the foliage was kept dry for 24 hours, then .

1~317'~4 watered regularly for 21 days, and phytotoxicity data recorded.
Phytotoxicity data were taken as percent con-trol. Percent control was determined by a method similar to the O to 100 rating system disclosed in "Research Methods in Weed Science," 2nd ed., B. True-love, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977. The present rating system is as follows:

317'~4 Herbicide Rating System Rating Description Percent of Main Crop Weed Control Categories Description Description O No effect No crop No weed reduction or control injury Slight discolora- Very poor tion or stunting weed control Slight Some discolora- Poor weed effect tion, stunting control or stand loss Crop injury more Poor to pronounced but not deficient not lasting weed control Moderate injury, Deficient crop usually weed control recovers Moderate Crop injury more Deficient to effect lasting, recovery moderate weed control Lasting crop Moderate injury no recovery weed control Heavy injury and Control stand loss somewhat less than satisfactory Severe Crop nearly des- Satisfac-troyed a few tory to good survivors weed control Only occasional Very good to live plants left excellent control 100 Complete Complete crop Complete effect destruction weed destruction , ~

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 used above.
In the Tables of herbicidal data below "kg/ha" is kilograms per hectare.

'` ' ~ ' ' ' 7'~4 Table 3 Pre-emergence Herbicidal Activity % Control Compound No. 1 2 3 4 Rate (Kg/ha) 8.0 8.0 8.0 8.0 Species RICE - - ~ ~

GREEN FOXTAIL 100 100 ~ 0 100 YELLOW NUTSEDGE

Compound No. 5 6 7 8 Rate (Kg/ha) 2.0 2.0 2.0 2.0 Species Table 3 (Continued) Compound No. 9 10 11 12 Rate (Kgtha) 2.0 2.0 1.0 1.0 Species Compound No. 13 14 15 16 Rate (Kg/ha) 2.0 2.0 2.0 1.0 Species ~Z817'~4 Table 3 (Continued) Co~pound No. 17 18 19 20 Rate (Kg/ha) 1.0 1.0 1.0 0.125 Species Compound No. 21 22 23 24 Rate (Kg/ha) 1.0 1.0 8.0 1.0 Species ~: JOHNSONGRASS 70 100 100 100 :~ - YELLOW NUTSEDGE 100 100 - 0 ., - ~ . , ' ' Table 3 (Continued) Compound No. 25 26 27 28 Rate (Kg/ha) 0.5 2.0 1.0 2.0 Species .

Compound No. 29 30 31 32 Rate (Kg/ha) 0.5 8.0 0.5 0.5 Species JOHNSONGRASS lO0 0 60 100 Table 3 (Continued) Compound No. 33 34 35 36 Rate (Kg/ha) I.0 0.5 I.0 8.0 Species .

Compound No. 37 39 40 Rate (Kg/ha) 1.0 1.0 2.0 Species RICE 95 go 95 ~;~817~4 Table 4 Post-emergence Herbicidal Activity % Control Compound No. 1 2 3 4 Rate (Kg/ha) 8.0 8.0 8.0 8.0 Species RICE - - ~ ~

YELLOW NUTSEDGE

Compound No. 5 6 7 8 Rate (Kg/ha) 2.0 2.0 2.0 2.0 Species ~8~7~4 Table 4 (Continued) Compound No. 9 10 11 12 Rate (Kg/ha) 2.0 8.0 1.0 1.0 Species Compound No. 13 14 15 16 Rate (Kg/ha) 2.0 2.0 2.0 1.0 Species ., ~ , . ' ' 12817~4 Table 4 (Continued) Compound No. 17 18 19 20 Rate (Kg/ha) 1.0 1.0 I.O O.I25 Species Compound No. 21 22 23 24 Rate (Kg/ha) 1.0 1.0 8.0 1.0 Species , ~8~7~4 Table 4 (Continued) Compound No. 25 26 27 28 Rate (Kg/ha) 0.5 2.0 1.0 0.5 Species Compound No. 29 30 31 32 Rate (Kg/ha) 0.5 8.0 0.5 0.5 Species ~Z8~24 Table 4 (Continued) Compound No. 33 34 35 36*
Rate (Kg/ha)1.0 0.5 1.0 8.0 Species JOHNSO~GRASS80 50 80 20 Compound No.37 39 40 Rate (Kg/ha)1.0 1.0 2.0 Species SOYBEAN 95 go 95 ~Data given are data for % Kill 7~4 For herbicidal application, the active compounds as above defined are formulated into herbicidal com-positions 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. Thus, for agri-cultural use 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.
For preemergence application these herbicidal compositions are usually applied either as sprays, dusts, or granules in the areas in which suppression of vegetation is desired. For postemergence control of established plant growth, 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 cotton seed flours, and other organic and inor-ganic solid~ 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 con-taining 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 orm 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. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.g 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 postempergence application to facili-tate dispersion on the foliage and absorption by the plant.
Other useful formu-lations for herbicidal applica-tions are emulsifiable concentrates. Emulsifiable concentrates are homogeneous liquid or paste composi-tions 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. For herbicidal application these concen-trates 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 .

~. .

8~ 4 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 sul-fates 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.
Other useful formulations for herbicidal applica-tions include simple solutions of the active ingre-dient in a dispersant in which it is completely solu-ble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic sol-vents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of parti-cular utility for aerial distributioh or for penetra-tion of cover crop canopy. Pressurized sprays, typi-cally aerosols wherein the active ingredient is dis-persed in finely divided form as a result of vaporiza-tion of a low boiling dispersant solvent carrier, such as the Freons, may also be used. Water-soluble or water-dispersible granules are also useful formula-tions for herbicidal application of the present com-pounds. Such granular formulations ars free-flowing, non-dusty, and readily water-soluble or water-misci-ble. 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 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 selec-.

8~7~4 tive herbiciaes in agriculture. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of S course employed.
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 herbi-cides such as 2-chloro-N-(2,6-diethylphenyl)-N-(meth-oxymethyl)acetamide (Alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-(1-methylethyl)acetamide (Metolachlor), and N-chloroacetyl-N-(2,6-diethyl-phenyl)glycine (Diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(lH)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (Bentazon):
triazine herbicides such as 6-chloro-N-ethyl-N-(l-methylethyl)-1,3,5-triazine-2,4-diam'ine (Atrazine), and 2- [4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-amino -2-methylpropanenitrile (Cyanazine); dinitrol-aniline herbicides such as 2,6-dinitro-N,N-dipropyl-~ 4-(trifluoromethyl)benzeneamine (Trifluralin): and ;~ aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N~,N-dimethylurea (Diuron) and N,N-dimethyl-N'-[3-~tri-fluoromethyl)phenyl]-urea (Fluometuron).
It is apparent that various modifications may be made in the formulation and application of the com-pounds of this invention, without departing from the inventive concepts herein, as defined in the following ,~ :, '; 30 claims.
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Claims (5)

The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:

1. An herbicidal compound of the formula:
in which X1 is F or C1;
Z is nitro or a group of the formula -OR, -CO-R6, -CH2CO-R6, or -CH(CH3)CO-R6;
R is alkyl of 1 to 6 carbon atoms which is un-substituted or is substituted with cycloalk-yl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms which is unsubstituted or is substituted with alkyl of 1 to 6 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, cyanoalkyl of 2 to 7 carbon atoms, alkenyl of 2 to 5 carbon atoms, alkynyl of 2 to 5 carbon atoms, haloalkyl of 1 to 5 carbon atoms, haloalkenyl of 2 to 8 carbon atoms, haloalkynyl of 2 to 5 carbon atoms, alkyl-sulfonyl of 1 to 6 carbon atoms (wherein the alkyl moiety is unsubstituted or is substi-tuted with F, C1, CN, alkoxy or alkylthio of 1 to 4 carbon atoms, or alkylamino or dial-kylamino in which each alkyl is of 1 to 4 carbon atoms), alkylaminosulfonyl or dial-kylaminosulfonyl in which each alkyl is of 1 to 4 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms, or a group of the formula -C(R3)(R4)(CH2)n-CO-Q1R5 or -C(R3)(R4)(CH2)n-CO-N(R7)(R8) in which n is 0 to 2;
R3 and R4 are independently H, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms;
Q1 is O or S;
R5 is H, alkyl of 1 to 6 carbon atoms, alkoxy-alkyl or alkylthioalkyl of 2 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms, al-kenyl of 2 to 5 carbon atoms, cycloalkenyl of 5 to 7 carbon atoms which is unsubstitu-ted or is substituted with alkyl of 1 to 4 carbon atoms, cyclohexenylalkyl of 6 to 10 carbon atoms, phenyl or benzyl (which may be ring-substituted with fluorine, chlorine, bromine, or alkyl, alkoxy, or alkylthio of 1 to 4 carbon atoms), cyanoalkyl of 2 to 7 carbon atoms, alkynyl of 2 to 5 carbon atoms, alkylideneamino of 1 to 6 carbon atoms which is unsubstituted or is substi-tuted with cycloalkyl of 3 to 7 carbon atoms, or cycloalkylideneamino of 5 to 7 carbon atoms, which is unsubstituted or is substituted with alkyl of 1 to 4 carbon atoms;
R6 is hydroxy, alkoxy or alkylthio of 1 to 6 carbon atoms, alkoxyalkoxy of 2 to 6 carbon atoms, amino, or alkylamino or dialkylamino wherein each alkyl is of 1 to 6 carbon atoms and is unsubstituted or is substituted with alkoxy of 1 to 4 carbon atoms;
R7 is H or alkyl of 1 to 6 carbon atoms;
R8 is R5 or alkoxy of 1 to 6 carbon atoms, al-kylthio of 1 to 6 carbon atoms, alkylsulfo-nyl of 1 to 6 carbon atoms, phenylsulfonyl, or phenylalkylsulfonyl of 1 to 3 alkyl car-bon atoms;
R1 is alkyl of 1 to 4 carbon atoms or haloalkyl of 1 to 3 carbon atoms; and R2 is fluoroalkyl of 1 to 4 carbon atoms.

2. The compound of claim 1 wherein R1 is CH3 or CHF2 and R2 is CHF2.

3. The compound of claim 2 wherein Z is -OR or -CH(CH3)CO-R6.

4. An herbicidal composition comprising an herbicidally effective amount of a compound of claim 1 in admixture with a suitable carrier.

5. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of the composition of claim 4.