HALOALKYL TRIAZOLINONES

This invention relates to herbicidal 1-aryl- 4, 5-dihydro-l, 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(lH)-ones (also known as

2 -aryl-Δ -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

wherein R 1 is an alkyl group, R2 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

(R., is 1-4C alkyl; R_ is H, 1-4C alkyl, halo¬ methyl or 3-4C alkynyl; X is Cl or F; Y is Cl, Br, OH or OR_; R_ is 1-4C alkyl or benzyl; Z is H, car- boxy, cyano ethoxy, COOR., COSR _ς or CON(R 6) (R7);

R. is 1-4C alkyl or 3-4C alkoxyalkyl; R _g is 1-4C alkyl; and R _g and R_ are H, 1-4C alkyl or alkoxy).

U.S. patent 4,318,731 discloses herbicidal com¬ pounds of the formula

wherein R 1 is C.-C ^* : alkyl; R2. is hydrogen, C. -C, alkyl or C.-C. alkenyl; and X is hydroxy, C. -C. alkyl,

C. -C _β alkyloxy, an alkyloxyalkyloxy of which two alkyls may be the same or different and each alkyl is

C.-C., a C--C. alkenyloxy, or an alkyloxycar- bonylalkyloxy of which two alkyls may be the same or different and each alkyl is C.-C..

Also, U.S. patent 4,404,019 discloses herbicidal compounds of the formula

wherein R is a C ₁ ~C ₄ alkyl group, a C ₃ ~C ₄

alkenyl group or a C ₃ ~C ₄ cycloalkyl group, X is a chlorine or bromine atom and Y is a hydrogen atom or a C, -C. alkoxy group.

The compounds of this invention are herbicidal aryl-4, 5-dihydro-l, 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 C. -C. 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:

2 1 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 alkylsulfonylalkyl 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 CH ₃ and a CHF ₂ substi- tuent, respectively. The aryl radical thus represents a group useful in the l-aryl-4,5-dihydro-l,2,4-tria- zol-5(1H)-one art to give herbicidal compounds when attached at the 1-position of an appropriate known 4,5-dihdyro-l,2,4-triazol-5(1H)-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 0.1 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

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;

2

X may be hydrogen, halogen such as fluorine, chlorine, or bromine, alkyl of 1 to 6 (preferably 1 to 4) carbon atoms, particularly methyl, haloalkyl of 1 to 5 carbon atoms, for example, trifluoromethyl, alkoxy of 1 to 6 (preferably 1 to 4) carbon atoms;

Z may, for instance, be hydrogen; halogen such as fluorine, 'chlorine, or bromine; alkyl of 1 to 6 (pre¬ ferably 1 to 4) carbon atoms; cyanoalkyl; haloalkyl of 1 to 5 carbon atoms; nitro; a group -OR; or a group -CO-R ⁶ or CH ₂ CO-R ⁶ or CH(CH ₃ )CO-R ⁶ ; or a group -OSO-R ⁹ ;

R may be hydrogen, alkyl of 1 to 6 (preferably 1 to 4) carbon atoms which may be substituted with cycloalkyl of 3 to 7 carbon atoms (for example, methyl or 1-methylethyl, or cyclohexylmethyl) , cycloalkyl of 3 to 7 carbon atoms which may be substituted with alkyl of 1 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 1 to 5 (preferably 1 to 3) carbon atoms

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 ace yl, 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 al-so be a group

-CR ³ R ⁴ (CH ) -CO-Q ¹ -R ⁵ in which n is 0 to 2 (preferably 0); R 3 and R4 may be independently hydrogen or alkyl or alkoxy of 1 to 4 carbon atoms, Q is 0, S or NR 7 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 atoms, alkoxyalkyl or alkylthioalkyl 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 10 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 1 to 6 (prefer¬ ably 1 to 4) carbon atoms which may be substituted with cycloalkyl 3 to 7 carbon atoms, cycloalkylidene- amino of 5 to 7 carbon atoms which may be substituted with alkyl of 1 to 4 carbon atoms. When Q is NR 7, R5 may additionally be alkoxy, alkylthio, or alkylsulfonyl, each of 1 to 6 carbon atoms, phenylsul- fonyl, or phenylalkylsulfonyl of 1 to 3 alkyl carbon atom.

As indicated above, R of the -OR substituent may be a heterocyclic group or an alkyl radical substi¬ tuted with a heterocyclic group. The R group of this type may be any of those disclosed in my copending application Serial No. 655,960, filed September 28, 1984, and its parent application Serial No. 541,596, filed October 13, 1983-; which disclose aryltriazolin- ones whose aryl groups have such -OR substituents (the present application is a continuatioή-in-part of both those applications and incorporates, by reference, their entire disclosures.) The "Ar" radical of this invention may be any of the aryl radicals disclosed in those applications. Among the R groups, on those aryl radicals, which may be employed are l-methyl-3-pyr- rolidinyl, furfuryl or 2-thienylmethyl, or preferably 3-tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydro- pyran-2-ylmethyl, 1, 3-dioxolan-2-ylmethyl, 2-(l,3-di- oxolan-2- 1)ethyl, 2, 2-dimethyl-l, 3-dioxolan-4-yl- methyl, 3-(2-methyl-l, 3-dioxolan-2-yl)propyl, 1,3-di- oxan-4-ylmethyl, 1,4-benzodioxan-2-ylmethyl, tetrahy- dro-4H-pyran-4-yl, 5, 6-dihydro-2H-pyran-3-ylmethyl, 2, 2-dimethyl-l, 3-dithiolan-4-ylmethyl, tetrahydro-4H- thiopyran-4-yl, tetrahydrothien-3-yl, 1-oxotetrahydro- thien-3-yl, 1, l-dioxotetrahydrothien-3-yl, 2, 2-di¬ methyl-l,1,3, 3-tetraoxo-l, 3-dithiolan-4-ylmethyl, 1, 4-dithiacycloheptan-6-yl, 1, 4-dithiacyclohept-5-

ene-6-yl, tetrahydro-4H-pyran-3-yl, glycidyl, 2,3-epi- thiopropyl, 2, 2-bis(chlorodifluoromethyl)-l, 3-dioxo- lan-4-ylmethyl, or 1, l-dioxotetrahydro-4H-thio- pyran-4-yl.

_ As indicated above, Z may be a group -CO-R ,-

-CH-CO-R or -CH(CH ₃ )CO-R where R is hydroxy, alkoxy or alkylthio of 1 to 6 carbon atoms such as methoxy or methylthio, alkoxyalkoxy of 2 to 6 carbon atoms (for example, 2-methoxyethoxy) , amino, or alkyl- amino or dialkylamino wherein each alkyl is of 1 to 6 (preferably 1 to 4) carbon atoms and may be substi¬ tuted with alkoxy of 1 to 4 carbon atoms (for example, methylamino, dimethylamino, or (methyl) (2-methoxy- ethyl)amino) .

As indicated above R of the -OR substituent may

3 4, , 1 5 be a group -CR R (CH ₂ ) COQ -R . Aryl triazolmones whose aryl radicals have such -OR substituents of this type are disclosed in my copending application Serial No. 666,933 filed October 31, 1984. (The present application is a continuation-in-part of that applica¬ tion, whose entire disclosure is incorporated herein by reference.) The "Ar" radical of this invention may be any of the aryl radicals disclosed in that copend¬ ing application.

9 As indicated above Z may also be a group -OSO-R

9 where R is alkyl, haloalkyl, cyanoalkyl, arylalkyl, cyclic alkyl, alkenyl, haloalkenyl, arylalkenyl, alkynyl, haloalkynyl, arylalkynyl, aryl, or a group of

3 ' 4' 5 ' the formula -(CH ) NR R or -alkyl-Y-R wherein m

3' 4' is 0 to 5; R is hydrogen or alkyl; R is alkyl

3 ' 8' 8' or a group of the formula -alkyl-Y -R ; R is alkyl, alkoxycarbonylalkyl, alkenyl, or alkynyl; and Y 3 ' is oxygen or S(O) in which r is 0 to 2. My copending application Serial No. 650,755 filed September 13,

1984 and its parent application Serial No. 533,013

filed September 15, 1983 (of both of which this appli¬ cation is a continuation-in-part, the entire disclo¬ sure of said copending applications being incorporated herein by reference) disclose aryl triazolinones whose aryl groups have a 5-substituent designated in said applications as "-OSO^R". The "Ar" radical of this invention may be any of the aryl radicals disclosed in

9 those applications. Among the -OSO^R groups, on those aryl radicals, which may be used are those in

9 which R is methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1-methylpropyl, 3-methylbutyl, chloromethyl, dichloro ethyl, 3-chloropropyl, bromo- methyl, difluoro ethyl, trifluoro ethyl, cyanomethyl, benzyl, cyclopropyl, 2-propenyl, 2, 3, 3-trichloro-2- propenyl, 2-propynyl, 3-bromo-2-propynyl, dimethyl- amino, dimethylaminoethyl, 2-methoxyethyl, 2-ethoxy- ethyl, 2-(2-propenoxy)ethyl, 2-(2-propenthio)ethyl,

2-(2-propynoxy)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, 1-methylethyl, 2-methyl-2-propenyl, and l-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

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 X 1 and X2 are preferably both halogen, with

X 1 being fluorine or chlori.ne and X2 being chlo¬ rine or bromine. The X halogen will usually be positioned at the C-2 carbon atom of the phenyl ring. The compounds wherein X is fluorine are particu¬ larly preferred.

The present compounds may be prepared by methods 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 R 2 is CHF ₂ , it is particularly convenient to start with CHF ₂ COOH, by converting the latter into an ester of difluoroacetylcarbamic acid (e.g. an ester of the formula CHF ₂ -CO-NHCO-0-lower alkyl), as by first converting the starting material into its acid chloride (e.g. by reaction with S0C1 ₂ ) and then reacting the latter with a lower alkyl urethane of the formula NH ₂ CO-0-lower alkyl as illustrated 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(lH)-one by reacting it with an 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 10 described at the end of Step B of Example 1) or those substi¬ tuents, and any R substituent, may be added in

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 S0 ₂ C1 ₂ ) a l-aryl-4, 5-dihydro-3- difluoromethyl-4-methyl-l, 2, 4-triazol-5(IH)-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 F-HC-CN or F C-CN or F C1C-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 l-aryl-4, 5-dihydro- 3-polyhalomethyl-4, 5-dihydro-l, 2,4- ^* triazol-5 (IH)-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-l, 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(lH)-ones having H on the nitro¬ gen at the 4-position of the 4, 5-dihydrotriazol ring and haloalkyl of 1 to 4 carbon atoms (e.g. CHF„, CF, or CC1F-) 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 1-aryl-l, 2-dihydro-l, 2, 4-triazol-5(IH)-ones having hydrogen on the nitrogen at the 2-position. The 1-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

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 (e.g. a 5-hydroxyphenyl radical). When the aryl group is 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.

tN CN a a u u

II II

CN CN CN CN a a

< i. m ^** _ ^• • ^* • ^■ > fc. cι co en υN u fe en I B a a B B B B a a a a a* I u u cj cj u cj cj c u a J cj u

CN C-i a cj

s a, - ε o H ( n <* Λ Λ CO <Tι O .-I CN CO

CJ s IH i— ! H H

ω ω to to to to to to to to to to t-* H H 2! o

H O tf tD Nl Ol Ul ili U W H O D 03 -J σ> ui •^

• o 13 a _*

»-_ ^* - ^■ _ o Ω Ω Ω Ω o ^* -_ ^■* _ >53 *. Ω I-* I-* o Ω Ω Ω Ω ix

H t-* H I- ¹ H

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω

H I-* t-* t-* I-* ιx 'tO

Ω B Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω |» co a to X toX toX co acoacoacoacoacacoa co a ω a ω a ω a to a ω a t-

UI Ul I ^* Ω a

II Ω to a

s-τ -

I81 0/98 OΛλ

Table 1 (Continued)

Cmpd No. X X R IT

32 F Cl OCH ₂ OCH ₃ CHF. *t CH ₃

33 F Cl OCH„ CHF- CH-,OCH ₃

34 F Cl 0CH-,C__CH CHF, CH ₂ C

35 Cl Cl OCH(CH ₃ ) ₂ CH ₃

^CF 3

36 Cl Cl OCH(CH ₃ ) ₂ CF ₃ H

37 Cl Cl 0CH ₂ C=CH CF ₃ CH ₃

38 Cl Cl OH CF-. CH -,

Cl t~*

39 Cl θCH(CH ₃ )CONHS0 ₂ - θ CHF, CH, n

40 F Cl OCH(CH_)C0 C(CH_) CF ₂

3'3 CH, 41 F Cl OCH(CH ₃ ) ₂ CHF,

_* i CH, 42 F Cl OCH ₂ SCH ₃ CHF, CH, 43 F Cl 0CH ₂ C CHF, CH, 44 F Cl OCHF CHF,

_ CH, 45 F Cl OCH(CH ₃ )C≡CH CHF, CH,

n c oo c m c o fo co oo 00 oo oo oo 00

•"""l UZ <><> >>>> l-M 33 -- EC 33 Ω a B E E B E

BJI J CJ CJ CJ CJ CJ CJ CJ CJ J CJ J CJ J CJ

oo oo

H r-l fa fa J CJ CJ CJ CN CN CN CN CN CN CN

CN OO CN OO CN OO CN fa fa oo fa fa fa fa fa

CN fa fa fa fa fa fa fa S E fa E E E E E 05I J CJ CJ CJ U CJ CJ CJ CJ CJ J CJ CJ J CJ

Ό <_•

3 a

CJ CJ α J

Xl fa fa fa fa fa U fa fa U fa fa fa fa fa

^* t3 σ. o -— l N o '-φ in o ^. αo σ. o r-l CN oo e o ^• >* ιn ιn ιn ιn ιn ιn ιn ιn in m o o Vθ O cj a

Table 1 ( Continued)

Cmpd , •« _"

No. X ¹ X ² z R R

64 F Cl OCH ₂ C(CI)=CC: CHF, CH,

_

65 F Cl OS0 ₂ CF ₃ CHF, CH,

66 F Cl OS0 ₂ CH(CH ₃ ) ₂ CHF,

._ CH ,

67 F Cl OCH CsCH CHF, CH ₂ OCH ₃

_

68 F Cl OCH C=CH CHF, CH ₂ CH=CH ₂

71 Cl Cl OCH(CH ₃ )CH ₂ OCH ₃ CHF, CH,

.0

72 Cl OCH

2 NO ? ⁾ CHF, CHF,

74 Cl OS0 ₂ CH ₂ CH ₂ OCH ₃ CHF ₂ CH ₃

75 F Cl OS0 ₂ (CH ₃ ) ₂

^CF 3 CH ₂ CH ₃ 76 F Cl OCH ₂ CH=CH ₂ CHF, CH ₂ SCH ₃

Table 1 (Continued)

Cmpd No. X X R

77 F Cl OCH ₂ OCH ₃ CHF .,__ CH ₂ S0 ₂ CH ₃

78 F Cl OCH ₂ C=CH CHF, *t NH ₂

79 F Cl 0CH ₂ C≡.CH CHF, 0CH ₃

80 F Cl 0CH ₂ C=CH CHF, NHCH ₃

81 Cl CF ₃ 0CH ₂ C=CH CHF, CH ₃

82 F OCH, OCH(CH ₃ ) ₂ ^CF 3 CH ₃

83 F Cl OCH ₂ C0 ₂ C ₂ H ₅ CHF •,t CH ₃

84 F Cl OCH(CH ₃ )C0 ₂ C ₂ H ₅ CF, ^CH 3

85 F Cl OCH(CH ₃ )C0 ₂ C ₂ H ₅ CF ₂ C1 CH ₃ oo

86 F Cl OCH(CH ₃ )C0 ₂ CH ₂ SCH ₃ CHF, CH, I

87 Cl 0CH(CH ₃ )C0 ₂ o CHF, CH,

88 F Cl 0CH(CH ₃ )C0 ₂ -CH ₂ rO CHF, CH,

89 F Cl 0CH(CH ₃ )C0 ₂ -C(CH ₃ ) ₂ C=CH CH ₂ CH,

90 F Cl 0CH(CH ₃ )Cp ₂ -C(CH ₃ ) ₂ CN CHF ₂ CH,

91 F Cl 0CH(CH ₃ )C0 ₂ CH(CH ₃ ) ₂ CHF ₂ CH,

92 F Cl OCH(CH ₃ )C0 ₂ CH ₂ CN CHF, CH,

oo a a CJ u o

00 CN CN OO 00 Γ C^ ΓO Γ ΓO Γ ΓO ΓO Γ ΓO a B B S B J CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ

CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN fa fa fa' fa fa fa fa fa fa fa fa fa fa fa fa fa fa

CN E E E B E E E E E E E a B B E E E

CJ U CJ CJ CJ CJ CJ CJ J CJ CJ CJ CJ CJ CJ CJ CJ

oo

CN --I H H i-I H r-I H E H iH H r-l rH rH H r-l r-l

XI CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ J CJ CJ CJ CJ U CJ

XI fa b fa fa fa fa fa fa a fa fa fa fa fa fa fa fa

-σ • oo ^* -f in o r^ co σi O i-i oo ^ in ^ i^. αD σi ε o σ. σ. σ. <n σ. σi σi o o o o o o o o o o

CJ a ^' H H f-l rH r-l r-. H H H i-'

Table 1 (Continued)

Cmpd

No. X ^J X" R" K-

110 F Cl OCH(CH ₃ CONHCH ₂ CH ₂ OCH ₃ CHF ₂ CH ₃

111 F Cl OCH(CH ₃ CONHC(CH ₃ ) ₂ CN CHF ₂ ^CH 3

112 F Cl 0CH(CH ₃ CON(CH ₃ )(OCH ₃ ) CHF ₂ CH ₃

113 F Cl OCH(CH ₃ CONHCH ₂ CH=CH ₂ CHF ₂ CH ₃

114 F CH, OCH(CH ₃ CON(CH ₃ ) ₂ CHF ₂ CH ₃

115 F CH, OCH(CH ₃ CONHCH CHF ₂ CH ₂ C

116 F Cl OCH(CH ₃ CONH ₂ CHF ₂ CH ₂ OCH ₃

117 F Cl OCH(CH ₃ CO HCH ₂ C0 ₂ CH ₃ CHF, CH, t

118 F Cl 0CH(CH ₃ CONHCH ₂ CONH ₂ CHF, CH, o

119 F Cl OCH(CH ₃ CON(CH ₂ CN) ₂ CHF, _ CH,

120 F Cl OCH(CH ₃ CONHS0 ₂ CH ₃ CHF *,i CH,

121 F Cl OCH(CH., CON(Na)S0 ₂ CH ₃ CHF, CH,

co co oo co ro ro co co co co co c^o oo oo co co tZ UZ ^Z UZ £ Ά *∑* Q * ^ IZ E *** -C re

CJ U CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ U CJ u

CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN fa fa fa fa fa fa fa fa fa fa fa fa fa fa fa fa

CN __ ₁ I ₄ __j __{ J^ __J S_) X h_ ^* ~Z~ _{I f} cC ^* _ ₄ *_! ^* fi B B

«l CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ J CJ J J

CN H H H H iH r-I H i-H rH H rH rH H H

XI CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ CJ

XI 03 fa fa fa fa fa fa fa fa fa fa fa fa fa fa

vO r» co σι θ H c oo <-j ^, ι vo r^ co σι o H e o CM N CN CN OO OO OO OO OO OO OO OO OO OO <ψ <* cj a H H H iH iH rH H H iH H H H rH H H H

Table 1 (Continued)

Cmpd No. X ¹ χ ² Z R ² R ¹

142 F Cl CONHS0 ₂ N(C ₂ H ₅ ) ₂ CHF ₂ CH ₃

143 Cl Cl C0 ₂ CH ₃ CHF ₂ CH ₃ 144 F CH ₃ C0NHCH ₃ CHF ₂ CH ₃

145 F Cl ^C0 2 ^C 2 ^H 5 CHF ₂ CH ₂ CN

146 F Cl C0 ₂ C ₂ H ₅ CF Cl CH ₂ OCH ₃

147 F Cl CONHCH C≡CH CHF ₂ CH ₃

148 F Cl C0NHS0 ₂ — (θ CHF ₂ CH ₃ ro t Cl

149 F Cl CH ₂ C0 ₂ CH ₃ CHF ₂ CH ₃

150 F Cl CH(CH ₃ )C0 ₂ C ₂ H ₅ CHF ₂ CH ₃

151 F Cl CH(CH ₃ )C0 ₂ H CHF ₂ CH ₃

152 F Cl CH ₂ C0 ₂ a CHF ₂ CH ₃

153 F Cl CH(CH ₃ )C0NH- ₂ CHF ₂ CH ₃

154 F Cl CH(CH ₃ )COSC H _j - CHF ₂ CH ₃

155 F Cl CH ₂ C0 ₂ CH ₂ CH ₂ 0CH ₃ CF ₃ CH ₃

156 F Cl CH(CH ₃ )CONHC ₂ H ₅ CHF ₂ CHF ₂

157 F Cl CH(CH ₃ )CONHS0 ₂ CF ₃ CHF ₂ CH ₃

Table 1 (Continued)

Cmpd No. z R ² R ¹

158 Cl CH(CH ₃ CHF ₂ CH ₂ CH=CH ₂

159 F Cl CH ₂ CONHS0 ₂ N(.CH ₃ ) ₂ CHF ₂ CH ₃

Other representative compounds are those which are identical with compounds 1-160 ' respectively, except that X is F and X is Br. Still other representative t compounds are those which are identical with compounds 1-100 respectively, except that '

X 1 is F and X2 is CF . Other representative compounds are those which are identical with compounds 1-126, 128-160 re ^' spectively except that X1 is Br.

0 ^Q 32W30093Wmd

The following Examples illustrate the preparation of the compounds of this invention.

Example 1

N-(2-CHL0R0PHENY SU F0NYL) l-[2-CHL0R0-4-FLU0R0-

5-(3-DIFLU0R0METHYL-4, 5-DIHYDRO-4-METHYL-5-OXO-

1H-1,2,4-TRIAZ0L-1-YL.)PHEN0XY]PR0PI0NAMIDE

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 20-25°C. 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 allo.wed to cool to room temperature and stir for approximately 18 hours. The reaction mixture was again heated at 77°C 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 l-(4-Chloro-2-fluoro-5-methoxyphenyl)-3- difluoromethyl-4, 5-dihydro-l, 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 niL 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

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 150 πiL 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 b ^* ro ^* wh precipi¬ tate. Collection of the precipitate by filtration yielded 1.5 g of l-(4-chloro-2-fluoro-5-methoxy- phenyl)-3-difluoromethyl-4, 5-dihydro-l, 2,4-triazol- 5(lH)-one. The precipitate which was previously saved for purification was stirred in 70 m of an aqueous 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 188-190°C).

The nmr spectrum was consistent with the proposed structure.

Compound 10, l-[2,4-dichloro-5-(1-methylethoxy)- phenyl]-3-difluoromethyl-4, 5-dihydro-l, 2,4-triazol- 5(lH)-one, and l-(3-methoxyphenyl)-3-difluoromethyl- 4, 5-dihydro-l, 2,4-triazol-5(lH)-one were prepared by the method of Example 1, Step B, from 2,4-dichloro-

5-(l-methylethoxy)phenylhydrazine or 3-methoxyphenyl- hydrazine, respectively.

Step C l-(4-chloro-2-fluoro-5-methoxyphenyl)- 3-difluoromethyl-4, 5-dihydro-4-methyl- 1,2, 4-triazol-5(IH)-one

A stirred mixture of 2.0 g (0.0067 mole) of l-(4-chloro-2-fluoro-5-methoxyphenyl)-3-difluoro- methyl-4, 5-dihydro-l, 2,4-triazol-5(IH)-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 l-(4-chloro-2-fluoro-5-methoxypheny1)-3-difluoro- methyl-4, 5-dihydro-4-methyl-l, 2,4-triazol-5(lH)-one. A portion of this material was recrystallized from ethanol and water to provide the product as a light tan solid (mp 127-129°C) , Compound 22.

The nmr spectrum was consistent with the proposed structure.

Analysis calcd for

C _ι;L H _g ClF _{3 3} 0 ₂ : 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 l-(4-chloro-2- fluoro-5-methoxy-phenyl-3-difluoromethyl-4, 5-di- hydro-1, 2,4-triazol-5(lH)-one; l-(2,4-dichloro-5- methoxyphenyl)-3-difluoromethyl-4, 5-dihydro-l,2,4- triazol-5(lH)-one; or l-(3-methoxyphenyl)-3-difluoro- methyl-4, 5-dihydro-l, 2,4-triazol-5(lH)-one and one of the following:

Compound Reagent

4 iodomethane

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 l-(3-meth- oxyphenyl)-3-difluoromethyl-4, 5-dihydro-l, 2, 4-tria- zol-5(IH)-one or l-(2,4-dichloro-5-methoxyphenyl)- 3-difluoromethyl-4, 5-dihydro-l, 2,4-triazol-5(lH)-one first with sodium hydroxide and tetrabutylammonium bromide in cyclohexane and tetrahydrofuran followed by chlorodifluoromethane.

Step D l-(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

mole) of l-(4-chloro-2-fluoro-5-methoxyphenyl)- 3-difluoromethyl-4, 5-dihydro-4-methyl-l, 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 l-(4-chloro-2-fluoro-5- hydroxyphenyl)-3-difluoromethy1-4, 5-dihydro-4-methyl- 1, 2,4-triazol-5(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- difluoromethy1-4, 5-dihydro-4-methyl-5-oxo- 1H-1, 2, 4-triazol-l-yl)phenoxy]propionate

A mixture of 0.7 g (0.0023 mole) of l-(4-chloro- 2-fluoro-5-hydroxyphenyl)-3-difluoromethyl-4, 5-dihydro- 4-methyl-l,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

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-difluoromethy1-4, 5-dihydro-4-methyl-5-oxo-lH- 1, 2,4-triazol-l-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 l-(2,4-dichloro-5- hydroxyphenyl)-3-difluoromethy1-4, 5-dihydro-4-methyl- 1, 2,4-triazol-5(lH)-one, Compound 2; l-(4-chloro-2- fluoro-5-hydroxyphenyl)-3-di luoromethyl-4, 5-dihydro- 4-methyl-l,2,4-triazol-5(lH)-one, Compound 23; l-(2,4- dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4, 5- dihydro-4-methyl-l, 2,4-triazol-5(IH)-one; 1-(2,4-di- chloro-5-hydroxyρhenyl)-3- ^' trifluoromethy1-4, 5-dihydro- 4-methyl-l, 2,4-triazol-5(lH)-one, Compound 38; l-(2, 4-dichloro-5-hydroxyphenyl)-4-ethy1-3-difluoro¬ methy1-4, 5-dihydro-l, 2,4-triazol-5( IH)-one, Compound 28; l-(2,4-dichloro-5-hydroxyphenyl)-3-difluoro¬ methy1-4, 5-dihydro-4-(2-propenyl )-l, 2,4-triazol-5( 1H)- one; or l-(2,4-dichloro-5-hydroxyphenyl)-4-cyano- methyl-3-difluoromethy1-4, 5-dihydro-l, 2, 4-triazol- 5(lH)-one and one of the following:

Compound Reagent

7 propargyl bromide

8 propargyl bromide 13 propargyl bromide 16 methyl bromoacetate 17 bromo acetonitrile 18 iodoacetamide 20 propargyl bromide 21 ethyl 2-bromopropionate 25 propargyl bromide 29 propargyl bromide 32 chloromethyl methyl ether 34 propargyl bromide 37 propargyl bromide

In addition, the following compounds were pre- pare ^' d -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(lH)-one intermediates listed above and one of the following:

Compound Reagent 9 3-tetrahydrofuryl 4-methyl- benzenesulfonate

14 ethyl 2-bromopropionate 15 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-l, 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-lH-l, 2,4-triazol-l-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-l,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-[2-chloro-

4-fluoro-5-(3-difluoromethyl-4, 5-dihydro- 4-methyl-5-oxo-lH-l, 2, 4-triazol-l-yl)- phenoxyjpropionamide]

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-l, 2, 4-triazol-l-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-l, 2, 4-triazol-l-ly)phenoxy]propionamide as a solid (mp 162-166°C), Compound 39.

The nmr spectrum was consistent with the proposed structure.

Example 2 1-C2,4-DICHL0R0-5-(l-METHYLETHOXY)PHENYL]- 3-TRIFLU0R0METHYL-4, 5-DIHYDR0-4-METHYL- 1,2,4-TRIAZ0L-5(IH)-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-methyl- ethoxy)phenylhydrazine in 140 mL of ethanol was cooled to -60 ^β C in a dry ice-isopropanol bath. Trifluoroacetonitrile (23.2 g, 0.24 mole) was bubbled into the cold solution during 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 residue. 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-(l-methylethoxy)anilino]trifluoro¬ acetamidine (mp 80.5-81°C).

The nmr spectrum was consistent with the proposed structure.

In addition to the above intermediate, N-[2,4-di- chloro-5-(l-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-

ingly substituted phenylhydrazine and chlorodifluoro¬ acetonitrile.

Step B l-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-

3-trifluoromethyl-4, 5-dihydro-l,2,4-triazol- 5(lH)-one

Under a dry nitrogen atmosphere a stirred solu¬ tion of 2.1 g (0.0062 mole) of N-[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 65°C 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 N 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 l-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-tri- fluoromethyl-4, 5-dihydro-l, 2,4-triazol-5(IH)-one (mp 160-161 ^o C), Compound 36.

The nmr was consistent with the proposed structure. Analysis σalc'd for

^C 12 ^H 10 ^C1 2 ^F 3 ^N 3°2 ^: ° ^{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 l-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3- chlorodifluoromethyl-4, 5-dihydro-l,2,4-triazol-5(IH)- one and l-(4-chloro-2-fluoro-5-methoxyphenyl)-3- chlorodifluoromethyl-4, 5-dihydro-l, 2,4-triazol-5(IH)- one (Compound 30) from the correspondingly substituted chlorodifluoroacetamidine.

Step C l-[2, 4-Dichloro-5-( 1-methylethoxy)phenyl]-

3-trifluoromethyl-4, 5-dihydro-4-methyl-l,2,4- triazol-5(IH)-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 l-[2,4-dichloro- 5-(1-methylethoxy)phenyl]-3-trifluoromethyl-4, 5-di- hydro-1, 2, 4-triazol-5(lH)-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 65°C and stirred at that tem¬ perature for one hour. The mixture was allowed to cool to room temperature and stir for approximately 18

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-(l-methylethoxy)phenyl]-3-tri- fluoromethy1-4, 5-dihydro-4-methyl-l, 2,4-triazol-5(1H)- one as a solid (mp 96-98°C), Compound 35.

The nmr spectrum was consistent with the proposed structure. Analysis calc'd for

^C 13 ^H 12 ^C1 2 ^F 3 ^N 3°2 ^{: 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 l-[2, 4-dichloro-5-( 1- methylethoxy)phenyl]-3-chlorodifluoromethyl-4, 5-di- hydro-1, 2,4-triazol-5(IH)-one using potassium carbonate and acetone in place of sodium hydride and N, -dimethyIformamide.

Characterizing properties of some of the compounds of the invention are given in the following Table.

TABLE 2

Cmpd. Melting Elemental Analysis No. Point (°C) Empirical Formula C H ____

1 Solid C10H5CI2F4N3O2

2 190-192 C ₁₀ H7Cl2F ₂ 3θ2 C 38.73 2.27 13.55

F 38.74 2.26 13.31

3 86-88 CUH9F4N3O2

4 113-115 ^c llHllF ₂ N ₃ 0 ₂

5 131-138 C11H7CI2F43O2

6 156-159 C _ι;L H9Cl2F2N3θ2

7 121-124 C-.3H9CI2F2N3O2

8 Solid C-.3H7CI2F4N3O2

9 Oil C14H11CI2F4N3O3

10 Solid _< CI2HUCI2F2N3O2 .

11 95-97 C13H13CI2F2N3O2

12 81-83 C15H15CI22N3O2

13 69-74 C15H11CI2 2N3O2

14 Oil C15H15 I2 2N3O4

15 Oil C17H17CI2F2N3O4

16 Solid C13H11CI2F2N3O4

17 132-135 C ₁₂ H ₈ Cl2F ₂ 4θ2

18 190-193.5 ^c 12HlθCl2F2 ^N 4θ2

19 Oil C14H13CI2F2N3O3

20 106-107 C ₁ 3H ₉ ClF ₃ 3θ2 C 47.08 2.73 12.67 F 46.98 2.80 12.61

21 Oil C15-H15CIF3N3O4

TABLE 2 (Continued)

Cmpd. Melting Elemental Analysis No. Point (°C) Empirical Formula C H N

22 127-129 C-.-H9CIF3N3O2 C 42.94 2.95 13.66

F 42.74 3.15 13.35

23 153-155 C-.0H7CIF3N3O2

24 69-72 ^c 13 ^H 12 ^cl 3 ^F 2N3θ2 C 40.39 3.13 10.87

F 40.92 3.28 10.96

25 146-147.5 C ₁₃ H ₈ Cl3F ₂ 3θ2 C 40.81 2.11 10.98

F 40.48 2.04 10.61

26 Oil C15H14CI32N3O4

27 Oil C ₁ 4H ₁ 5Cl2F2N ₃ θ2

28 120-124 C11H9CI2F2 3O2

29 104-107 ^C 14 ^H 11 ^C1 2 ^F 2 ^N 3°2 C 46.43 3.06 11.60

F 46.85 3.10 11.54

30 200-205 C ₁₀ H ₆ Cl2F3N ₃ θ2 ^{* *} _* C 36.61 1.84 12.81

F 37.33 2.16 12.63

31 78-88 C _L oH ₈ Cl ₂ F ₃ N3θ2

32 114-116 C ₁₂ HnClF3N3θ3

33 Solid C12HH IF3N3O3

34 Oil C ₁₄ H ₈ ClF3N4θ2

35 96-98 ^C 13 ^H 12 ^C1 2 ^F 3 ^N 3°2 C 42.18 3.27 11.35

F 41.52 3.18 11.14

36 160-161.5 C-.2H10CI2F3N3O2 C 40.47 2.83 11.80

F 39.01 2.96 11.38

37 132.5-134.5 C ₁₃ H ₈ Cl2F3 ₃ 0 ₂ C 42.63 2.20 11.48

F 42.83 2.54 10.70

38 174-175 C ₁₀ H ₆ Cl2F3 ₃ θ2 C 36.61 1.84 12.81

F 38.24 2.14 12.10

39 162-166 C ₁ 9H ₁ 5Cl ₂ F ₃ 4θ5S

40 Oil C17H19C1F3N304

0936W30093Wπri

HERBICIDAL ACTIVITY

The plant tests species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville) , soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticu 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

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 0 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:

Herbicide Rating System

Rating Description Percent of Main Crop Weed Control Categories Description Description

No effect No crop No weed reduction or control injury

10 Slight discolora¬ Very poor tion or stunting weed control

20 Slight Some discolora¬ Poor weed effect tion, stunting control or stand loss

30 Crop injury more Poor to pronounced but not deficient not lasting weed control

40 Moderate injury, Deficient crop usually weed control recovers

50 Moderate Crop injury more Deficient to effect lasting, recovery moderate weed control

60 Lasting crop Moderate injury no recovery weed control

70 Heavy injury and Control stand loss somewhat less than satisfactory

80 Severe Crop nearly des¬ Satisfac¬ troyed a few tory to good survivors weed control

90 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.

Table 3

Pre-erne .rgence Herbiciidal Activity

% Control

Compound No. 1 2 3 4 Rate (Kg/ha) 8.0 8.0 8.0 8.0 Species

COTTON 100 100 0 10

SOYBEAN 100 60 0 20

FIELD CORN 90 90 0 0

RICE - - - -

WHEAT 90 90 0 0

FIELD BINDWEED 100 100 0 20

MORNINGGLORY 100 90 0 70

VELVETLEAF 100 100 0 90

BARNYARDGRASS 100 90 . 0 70

GREEN FOXTAIL 100 100 0 100

JOHNSONGRASS 100 ^" 90 .° 70

YELLOW NUTSEDGE — — - —

Compound No. 5 6 7 8 Rate (Kg/ha) 2.0 2.0 2.0 2.0 Species

COTTON 50 100 100 100

SOYBEAN 70 90 100 100

FIELD CORN 100 100 100 100

RICE 90 100 100 100

WHEAT 100 100 100 100

FIELD BINDWEED 70 80 100 100

MORNINGGLORY 80 100 100 100

VELVETLEAF 100 100 100 100

BARNYARDGRASS 100 100 100 100

GREEN FOXTAIL 100 100 100 100

JOHNSONTAIL 100 100 100 100

YELLOW NUTSEDGE 90 100 90 90

Table 3

(Continued)

Compound No. 9 10 11 12 Rate (Kg/ha) 2.0 2.0 1.0 1.0 Species

COTTON 90 10 60 40

SOYBEAN 100 0 100 60

FIELD CORN 100 70 90 80

RICE 100 - 80 30

WHEAT 100 0 90 40

FIELD BINDWEED 90 30 90 50

MORNINGGLORY 100 50 90 80

VELVETLEAF 100 70 100 100

BARNYARDGRASS 100 60 100 100

GREEN FOXTAIL 100 40 100 100

JOHNSONGRASS 100 80 100 90

YELLOW NUTSEDGE 90 — 80 20

Compound No. 13 14 15 16 Rate (Kg/ha) 2.0 2.0 2.0 1.0

Species

COTTON 100 100 90 60

SOYBEAN 100 30 0 0

FIELD CORN 90 40 70 0

RICE 90 80 40 10

WHEAT 90 80 80 0

FIELD BINDWEED 100 100 100 60

MORNINGGLORY 100 80 100 70

VELVETLEAF 100 100 100 10

BARNYARDGRASS 100 100 100 60

GREEN FOXTAIL 100 100 100 10

JOHNSONGRASS 100 100 90 40

YELLOW NUTSEDGE 80 100 80 20

Table 3

- (Continued)

Compound No. 17 18 19 20 Rate (Kg/ha) 1.0 1.0 1.0 0.125 Species

COTTON 100 40 100 100

SOYBEAN 60 10 90 100

FIELD CORN 100 80 100 100

RICE 100 30 100 100

WHEAT 100 0 100 100

FIELD BINDWEED 90 90 70 100

MORNINGGLORY 100 100 100 100

VELVETLEAF 100 90 ^' 100 100

BARNYARDGRASS 100 80 100 100

GREEN FOXTAIL 100 100 100 100

JOHNSONGRASS 100 70 100 100

YELLOW NUTSEDGE 90 30 100 . 90

Compound No. 21 22 23 24 Rate (Kg/ha) 1.0 1.0 8.0 1.0 Species

COTTON 80 80 100 0

SOYBEAN 10 100 100 60

FIELD CORN 40 100 100 90

RICE 70 100 - 60

WHEAT 80 100 100 70

FIELD BINDWEED 80 100 100 60

MORNINGGLORY 80 100 100 10

VELVETLEAF 100 100 100 60

BARNYARDGRASS 100 100 100 100

GREEN FOXTAIL 100 100 100 100

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

COTTON 20 50 20 10

SOYBEAN 70 50 20 10

FIELD CORN 100 30 90 90

RICE 60 80 70 30

WHEAT 40 20 80 30

FIELD BINDWEED 100 100 50 10

MORNINGGLORY 50 90 80 20

VELVETLEAF 100 100 100 20

BARNYARDGRASS 100 100 100 70

GREEN FOXTAIL 100 90 100 100

JOHNSONGRASS 90 40 100 90

YELLOW NUTSEDGE 60 50 60 10

Compound No. 29 30 31 32

Rate (Kg/ha) 0.5 8.0 0.5 0.5

Species

COTTON 40 0 30 90

SOYBEAN 100 0 60 100

FIELD CORN 100 0 90 100

RICE 80 - 70 100

WHEAT 100 0 90 100

FIELD BINDWEED 100 0 20 100

MORNINGGLORY 60 0 20 100

VELVETLEAF 100 0 100 100

BARNYARDGRASS 100 0 100 100

GREEN FOXTAIL 100 0 100 100

JOHNSONGRASS 100 0 60 100

YELLOW NUTSEDGE 70 - 80 100

Table 3

(Continued)

Compound No. 33 34 35 36 Rate (Kg/ha) 1.0 0.5 1.0 8.0 Species

COTTON 90 80 20 0

SOYBEAN 80 90 30 0

FIELD CORN 100 90 90 0

RICE 90 80 60 -

WHEAT 100 90 50 0

FIELD BINDWEED 100 90 80 0

MORNINGGLORY 90 90 80 0

VELVETLEAF 100 100 100 0

BARNYARDGRASS 100 100 100 0

GREEN FOXTAIL 100 100 100 0

JOHNSONGRASS 100 90 100 - 0

*

YELLOW NUTSEDGE ^* 90 70 20 —

Compound No. 37 39 40 Rate (Kg/ha) 1.0 ^* 1.0 2.0 Species

COTTON 80 100 100

SOYBEAN 100 70 70

FIELD CORN 100 70 100

RICE 95 90 95

WHEAT 100 70 100

FIELD BINDWEED 100 100 100

MORNINGGLORY 100 100 95

VELVETLEAF 100 100 100

BARNYARDGRASS 100 100 100

GREEN FOXTAIL 100 100 100

JOHNSONGRASS 100 95 100

YELLOW NUTSEDGE 60 100 100

Table 4

Post-emergence Herbici< 3al Activity

% Control

Compound No. 1 2 3 4 Rate (Kg/ha) 8.0 8.0 8.0 8.0 Species

COTTON 100 100 40 10

SOYBEAN 90 90 0 20

FIELD CORN 100 90 0 0

RICE - - - -

WHEAT 100 100 0 0

FIELD BINDWEED 100 100 0 10

MORNINGGLORY 100 100 0 0

VELVETLEAF 100 100 0 0

BARNYARDGRASS 100 100 0 10

GREEN FOXTAIL 100 100 80 0

JOHNSONGRASS 100 100 30 20

YELLOW NUTSEDGE — — — —

Compound No. 5 6 7 8 Rate (Kg/ha) 2.0 2.0 2.0 2.0 Species

COTTON 100 80 100 100

SOYBEAN 100 90 100 100

FIELD CORN 100 100 100 100

RICE 100 100 100 100

WHEAT 100 100 100 100

FIELD BINDWEED 90 100 100 100

MORNINGGLORY 80 100 100 100

VELVETLEAF 100 100 100 100

BARNYARDGRASS 100 100 100 100

GREEN FOXTAIL 100 100 100 100

JOHNSONGRASS 100 100 100 100

YELLOW NUTSEDGE 100 100 90 80

Table 4 (Continued)

Compound No. 9 10 11 12 Rate (Kg/ha) 2.0 8.0 1.0 1.0 Species

COTTON 100 40 100 100

SOYBEAN 100 20 90 70

FIELD CORN 100 40 100 80

RICE 100 - 90 30

WHEAT 100 0 100 90

FIELD BINDWEED 100 100 100 90

MORNINGGLORY 100 0 100 100

VELVETLEAF 100 80 100 100

BARNYARDGRASS 100 0 100 100

GREEN FOXTAIL 100 40 100 100

JOHNSONGRASS 100 0 100 90

YELLOW ^" NUTSEDGE 80 — 60 0

Compound No. 13 14 15 16 Rate (Kg/ha) 2.0 2.0 2.0 1.0 Species

COTTON 100 100 100 60

SOYBEAN 100 50 60 40

FIELD CORN 100 70 100 . 40

RICE 90 80 100 10

WHEAT 100 80 100 0

FIELD BINDWEED 100 100 100 100

MORNINGGLORY 100 80 80 80

VELVETLEAF 100 100 100 100

BARNYARDGRASS 100 100 80 100

GREEN FOXTAIL 100 100 100 100

JOHNSONGRASS 100 100 80 40

YELLOW NUTSEDGE 70 70 50 0

Table 4

(Continued)

Compound No. 17 18 19 20 Rate (Kg/ha) 1.0 1.0 1.0 0.125 Species

COTTON 100 50 90 100

SOYBEAN 60 20 80 80

FIELD CORN 90 20 90 100

RICE 30 10 100 100

WHEAT 100 10 100 100

FIELD BINDWEED 100 100 100 100

MORNINGGLORY 100 90 100 100

VELVETLEAF 100 100 100 100

BARNYARDGRASS 100 80 100 100

GREEN FOXTAIL 100 100 100 100

JOHNSONGRASS 100 60 100 100

YELLOW NUTSEDGE . 90 0 90 80

Compound No. 21 22 23 24 Rate (Kg/ha) 1.0 1.0 8.0 1.0 Species

COTTON 100 100 100 100

SOYBEAN 50 100 90 40

FIELD CORN 70 100 100 30

RICE 90 100 - 10

WHEAT 100 100 100 10

FIELD BINDWEED 100 100 100 90

MORNINGGLORY 100 100 100 60

VELVETLEAF 100 100 100 100

BARNYARDGRASS 90 100 100 90

GREEN FOXTAIL 100 100 100 90

JOHNSONGRASS 90 90 100 50

YELLOW NUTSEDGE 90 100 — 0

Table 4

(Continued)

Compound No. 25 26 27 28 Rate (Kg/ha) 0.5 2.0 1.0 0T5

Species

COTTON 100 100 90 90

SOYBEAN 80 50 70 30

FIELD CORN 70 20 80 30

RICE 40 70 90 40

WHEAT 30 30 80 20

FIELD BINDWEED 100 100 80 30

MORNINGGLORY 100 90 70 20

VELVETLEAF 100 90 100 70

BARNYARDGRASS 30 60 80 10

GREEN FOXTAIL 90 80 100 100

JOHNSONGRASS 30 20 90 70

YELLOW NUTSEDGE 20 ^■ 40-- ^• 10 10

Compound No. 29 30 31 32 Rate (Kg/ha) 0.5 8.0 0.5 0.5

Species

COTTON 90 30 90 100

SOYBEAN 50 10 70 100

FIELD CORN 90 10 60 100

RICE 40 - 40 100

WHEAT 60 10 60 100

FIELD BINDWEED 90 30 90 100

MORNINGGLORY 90 30 70 100

VELVETLEAF 100 10 100 100

BARNYARDGRASS 70 10 ND 100

GREEN FOXTAIL 90 20 90 100

JOHNSONGRASS 80 10 20 100

YELLOW NUTSEDGE 50 — 70 100

Table 4

(Continued)

Compound No. 33 34 35 36* Rate (Kg/ha) 1.0 0.5 1.0 8.0 Species

COTTON 80 90 80 0

SOYBEAN 70 80 70 30

FIELD CORN 80 100 60 20

RICE 50 90 30 -

WHEAT 80 50 60 20

FIELD BINDWEED 70 90 80 0

MORNINGGLORY 100 70 80 20

VELVETLEAF 100 100 100 0

BARNYARDGRASS 90 30 90 20

GREEN FOXTAIL 100 80 90 0

JOHNSONGRASS 80 50 80 20

YELLOW NUTSEDGE 40 _β * 40 20 _

Compound No. 37 39 40 Rate (Kg/ha) 1.0 1.0 2.0 Species

COTTON 100 100 100

SOYBEAN 95 90 95

FIELD CORN 100 100 100

RICE 95 50 90

WHEAT 95 95 100

FIELD BINDWEED 100 100 100

MORNINGGLORY 100 100 100

VELVETLEAF 100 100 100

BARNYARDGRASS 100 100 100

GREEN FOXTAIL 100 100 100

JOHNSONGRASS 100 100 100

YELLOW NUTSEDGE 70 95 100

*Data given are data for % Kill

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 herb ^' icidal 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 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 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 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. For example, 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 postempergence application to facili¬ tate dispersion on the foliage and absorption by the plant.

Other useful formulations 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

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 distribution 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 are 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-

tive herbicides 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 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- oxymethyDacetamide (Alachlor), 2-chloro-N-(2-ethyl- 6-methylphenyl)-N-(2-methoxy-(1-methylethyl)acetamide (Metolachlor) , and N-chloroacetyl-N-(2, 6-diethyl- phenyDglycine (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- (1-methylethyl)-1,3, 5-triazine-2,4-diamine (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 claims.