The invention described in this application per- tains to weed control in agriculture, horticulture, and other fields where there is a desire to control unwanted plant growth. More specifically, the pre¬ sent application describes herbicidal 2-aryl-l,2,4- triazine-3,5(2H,4H)-diones, sulfur analogs thereof, compositions of them, methods of preparing them, and methods for preventing or destroying undesired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The present compounds may be used to effectively control a variety of both grassy and broadleaf plant species. The present invention is particularly useful in agriculture, as a number of the compounds described herein show a selectivity favorable to soybean, corn, cotton, wheat, rice, or other crops at application levels which prevent the growth of or destroy a variety of weeds. l,2,4-Triazine-3,5(2H,4H)-diones as a class are generally associated with the pharmaceutical or animal health arts and are commonly referred to therein as 6-azauracils. Such compounds, however, are relatively unknown in the herbicide art. In particular, there does not appear to be any disclo¬ sure of 2-aryltriazinediones in the art. Herbicidal activity is disclosed in German Of enlegungsschrift No. 3,016,304 for optionally substituted triazine- diones having the formula

where R is hydrogen, hydroxymethyl or an ester derivative thereof such as a benzoic acid ester, optionally substituted aminomethyl, optionally halo- substituted 2-tetrahydrofuranyl, 2-(2H,5H)dihydro-

2 furanyl, or 2-tetrahydropyranyl, and R is hydro¬ gen, an optionally substituted aminomethyl, optional¬ ly halo-substituted 2-tetrahydrofuranyl, or 2-tetra- hydropyranyl, with certain provisos.

It has now been discovered that 2-aryl-l,2,4-tri- azine-3,5-(2H,4H)-diones and the corresponding sulfur analogs have herbicidal properties and may be used effectively either preemergently or postemergently for herbicidal purposes.

The herbicidal compounds of this invention have the formula

where A is an aryl radical, preferably a ring-sub- stituted aryl radical. 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, or phenoxy or phenylmethoxy which may be ring substi¬ tuted with halogen or alkyl or alkoxy of 1 to 4 carbon atoms;

Z may be hydrogen or, preferably, a substituent or group selected from fluorine, chlorine, bromine, iodine, cyano, nitro, amino, alkoxycarbonylamino of 1 to 6 (preferably 1 to 4) alkyl carbon atoms, di-... (alkylcarbonyl)amino in which each alkyl is of 1 to 6 (preϊerably 1 to 4) carbon atoms, hydroxysulfonyl, alkyl of 1 to 6 (preferably 1 to 4) carbon atoms, haloalkyl of 1 to 5 carbon atoms, -QR, -CO-R , -S(0) _m R ⁸ , -Q ² R ⁹ , -0S0,R ¹⁰ , -NHN-CR ¹¹ * ¹² , and

Q-CR ^J R ⁴ -(CH ₂ ) _n -C0-Q ⁱ -R ^:3 .

For Z = -QR, Q may be 0, S, or NR ; R may be hydrogen or alkyl of 1 to 6 (preferably 1 to 4) carbon atoms; and R may be alkyl of 1 to 6 (preferably 1 to 4) carbon atoms ^' which may be substituted with cyclo- alkyl of 3 to 7 carbon atoms (for example, methyl, 1-methylethyl, or cyclohexylraethyl) , cycloalkyl of 3 to 7 (preferably 5 or 6) carbon atoms which may be substituted with alkyl of 1 to 6 carbon atoms (for example, cyclopentyl or methylcyclopropyl) , alkoxy- alkyl of 2 to 8 (preferably 2 to 4) carbon- atoms (for example, ethoxymethyl) , alkoxyalkoxyalkyl of 3 to 8 (preferably 3 to 5) carbon atoms (for example, 2-meth- oxyethoxymethyl), alkylthioalkyl of 2 to 8 (preferably 2 to 4) carbon atoms or the sulfinyl or sulfonyl derivative thereof, tri(alkyl of 1 to 4 carbon atoms)-

silyl(alkyl of.1 to 4 carbon atoms) such as trimethyl- silylmethyl, cyanoalkyl of 1 to 5 (preferably 1 to 3) alkyl carbon atoms such as cyanomethyl or 2-cyano- ethyl, alkenyl of 2 to 5 (preferably 3 to 5) carbon atoms such as 2-propenyl, alkynyl of 2 to 5 (pre¬ ferably 3 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 (preferably 3 to 5) carbon atoms, haloalkynyl of 2 to 5 (preferably 3 to 5) carbon atoms such as 3-bromo-2- propynyl, alkylcarbonyl of 1 to 6 (preferably 1 to 4) alkyl carbon atoms such as acetyl, or dialkylamino- carbonyl or dialkylaminothiocarbonyl in which each alkyl is of 1 to 6 (preferably 1 to 4) carbon atoms. The compounds in which Z = -QR, especially where

X 1 is 2-F and X2 is Cl or Br, form a preferred embodiment of the invention; particularly where Q is sulfur, more particularly where Q is oxygen. Fre¬ quently, R will be selected from among alkyl, cyano- alkyl, alkynyl, haloalkynyl, and alkoxyalkyl. Typi¬ cal such R groups include, for example, -1-methylethyl, cyanomethyl, 2-propynyl, 3-bromo-2-propynyl, and methoxymethyl. Preferably R will be 1-methylethyl or, especially, 2-propynyl or methoxymethyl. For Z = -CO-R , R may be hydroxy, alkoxy or alkylthio of 1 to 6 (preferably 1 to 4) carbon atoms such as methoxy or methylthio, alkoxyalkoxy of 2 to 6 (preferably 2 to 4) carbon atoms (for example, 2-meth- oxyethoxy) , amino, or alkylamino or dialkylamino wherein each alkyl is of 1 to 6 (preferably 1 to 4) carbon atoms and may be substituted with alkoxy of 1 to 4 carbon atoms (for example, methylamino, dimethyl- amino, or methylC2-methoxyethyl)amino). For example, Z, defined as -CO-R , may be C0 ₂ H, C0 ₂ alkyl, CO-S-alkyl, C0 ₂ alkyl-0-alkyl, C0NH _2> or CONH-alkyl or C0N(alkyl) ₇ in which any alkyl may be substituted with alkoxy. Compounds in which Z is -CO-R ,

especially where X1 is 2-F and X2 is Cl or Br, form

be a oms or alkenyl or alkynyl of 2 to 5 (preferably 3 to 5) carbon atoms. For example, Z may be -SO-CH,,

-S0 ₂ CH(CH ₃ ) ₂ , -S0 ₂ CH CH=CH ₂ , or -SO-CH ₂ C=CH.

For Z = -Q R , Q may be sulfur or, prefer- q ably, oxygen, and R may be a 5- or 6-membered ring heterocyclic group of 1 or 2 same or different (pre¬ ferably the same) heteroatoms selected from 0,S (including the S-oxide and S-dioxide), and N or an alkyl radical of 1 to 5 (preferably 1 to 3) carbon

9 atoms substituted with said heterocyclic group. R will frequently be

(a) an optionally substituted and optionally benzene-adjoined nitrogen-containing heterocycle or an alkyl radical of 1 to 5 carbon atoms substituted with said heterocycle; (b) an aromatic, optionally substituted and optionally benzene-adjoined, oxygen- or sulfur- containing heterocycle or an alkyl group of 1 to 5 carbon atoms substituted therewith; or, advanta¬ geously, (c) a non-aromatic, optionally substituted and optionally benzene-adjoined, oxygen- or sulfur- containing heterocycle or an alkyl group of 1 to 5 carbon atoms substituted therewith.

9 Examples of R groups include l-raethyl-3- pyrrolidinyl, furfuryl, 2-thienylmethyl, 3-tetrahy- drofuranyl, tetrahydrofurfuryl, tetrahydropyran-2-yl- methyl, l,3-dioxolan-2-ylmethyl, 2-(l,3-dioxolan-2- yl)ethyl, 2, 2-dimethy1-1 ,3-dioxolan-4-ylmethyl, 3-(2-methyl-l,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-di- methyl-l,3-dithiolan-4-ylmeth.yl, tetrahydro-4H-

thiopyran-4-yl, tetrahydrothien-3-yl, 1-oxotetra- hydrothien-3-yl, 1,l-dioxotetrahydrothien-3-yl, 2,2-dimethyl-1,1,3,3-tetraoxo-1,3-dithiolan-4-y1- methyl, 1, l-dioxotetrahydro-4H-thiopyran-4-yl, and l,3-oxothiolan-2-ylmethyl.

For Z = -OS0 ₂ R ¹⁰ , R ¹⁰ may be alkyl of 1 to.6 (preferably 1 to 4) carbon atoms (which may be substi¬ tuted with halogen, cyano, alkoxy or alkylthio of 1 to 4 carbon atoms, or alkylamino or dialkylamino in which alkyl is of 1 to 4 carbon atoms), phenyl, or alkyl¬ amino or dialkylamino in which alkyl is of 1 to 4 carbon atoms. Examples of such Z substituents include phenylsulfonyloxy, methylsulfonyloxy, ethylsulfonyl¬ oxy, propylsulfonyloxy, butylsulfonyloxy, 1-methyl- ethylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methyl- propylsulfonyloxy, 3-methylbutylsulfonyloxy, chloro- methylsulfonyloxy, 3-chloropropylsulfonyloxy, tri- fluoromethylsulfonyloxy, methylaminosulfonyloxy, di¬ methylaminosulfonyloxy, dimethylaminoethylsul onyloxy, 2-methoxyethylsulfonyloxy, 2-ethoxyethylsulfonyloxy, and cyanomethylsulfonyloxy.

For Z = -NHN=C(R ¹¹ )(R ¹² ), one of R ¹¹ and R ¹² may be hydrogen or alkyl of 1 to 4 carbon atoms and the other may be alkyl of 1 to 4 carbon atoms, or C(R ¹¹ )(R ¹ ) taken as a unit may be cycloalkyl of 3 to 7 (preferably 5 to 7) carbon atoms. For example, Z may be NHN=C(CH ₃ ) ₂ , NHN=CHCH ₂ CH ₃ , NHN=C(CH ₃ )(C ₂ H ₅ ), NHN=C(CH ₂ ) ₃ CH, or NHN=C(CH ₂ ) ₄ CH.

R3 ' » ' '

For Z = -Q-Ci-(CHώ ₇ ) _n n-C0-Q ¹ -R ⁵ , n may be 0 to 2,

R ⁴ preferably 0; R may be hydrogen or alkyl of 1 to 4 carbon atoms; R may be hydrogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms; Q and

1 7 7 Q may be independently 0, S, or NR in which R is hydrogen 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 which may be substi¬ tuted with cycloalkyl of 3 to 7 carbon atoms (for example, methyl, cyclopropylmethyl, cyclopentylmethyl, or cyclohexylmethyl) , cycloalkyl of 3 to 7 carbon atoms which may be substituted with alkyl of 1 to 4 carbon atoms (for example, methylcyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, or cycloheptyl) , alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms (especially fluoro- alkyl 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) , cycloalkenylalkyl of 6 to 10 carbon atoms (for example, 3-cyclohexenyl- methyl), phenyl or phenylmethyl (each of which may be ring-substituted with fluorine, chlorine, bromine, or alkyl, alkoxy, or alkylthio of 1 to 4 carbon atoms), cyanoalkyl of 1 to 5 alkyl carbon atoms such as cyano¬ methyl, alkynyl of 2 to 5 carbon atoms such as 2-pro- pynyl, alkylimino of 1 to 6 (preferably 1 to 4) carbon atoms which may be substituted with- cycloalkyl of 3 to 7 carbon atoms, or cycloalkylimino of 5 to 7 carbon atoms which may be substituted with alkyl of 1 to 4 carbon atoms; or Q and R may together represent a phenylsulfonylamino group in which the phenyl is unsub- stituted or substituted with halogen such as fluorine, chlorine, or bromine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkoxycarbonyl of 1 to 4 alkyl carbon atoms. This subgenus, especially where X is 2-F and 2 X is Cl or Br, forms a preferred embodiment of the invention; particularly where n is 0 and one of R

4 and R is H and the other is H, CH ₃ , C ₂ H ₅ , 0CH ₃ , or

0C ₂ H _s . Where Q or Q ¹ is NR ⁷ , R ⁷ is preferably H. Examples of Z substituents where Q is NR include those of the formulas -NHCH ₂ C0 ₂ R ⁵ and -NHCH(CH.,)C0 ₂ R ⁵

where R is methyl, ethyl, propyl, butyl, 2-methoxy- ethyl, 2-propoxyethyl, 2-cyanoethyl, 2,3-dichloropro- pyl, 2, 2-dichloroethyl, cyclopentylmethyl, cyclopentyl, 1-methylethyl, 1-ethylpropyl, or 1-methylpropyl.

Thus, Z may be H or a substituent or group such as ,

The aryl moiety of the present aryltriazinediones may be a heteroaromatic radical such as a furyl, thienyl, pyridyl, pyrimidyl, oxazolyl, pyrrolyl, isoxazolyl, thiazolyl, or isothiazolyl radical which may carry one or more substituents, for example, halogen and/or alkyl or alkoxy of 1 to 6 (preferably 1 to 4) carbon atoms. Preferably, however, the aryl moiety will be a phenyl radical, particularly a halophenyl radical, more particularly a dihalophenyl radical.

In a preferred embodiment for herbicidal activity, the present compounds will have the formula:

in which X 1 and X2 are both halogen atoms and Z is as defined above. X is preferably chlorine or, especially, fluorine. X 2 is preferably chlorine or bromine. With respect to the triazinedione portion of the molecule, R may be alkyl of 1 to 6 (preferably 1 to

4) carbon atoms; haloalkyl of 1 to 5 (preferably 1 to

3) carbon atoms; cyanoalkyl of 1 to 5 (preferably 1 to 3) alkyl carbon atoms; alkenyl or alkynyl of 2 to 5 (preferably 3 to 5) carbon atoms; alkoxyalkyl, alkyl¬ thioalkyl, alkylsulfinylalkyl, or alkylsulfonylalkyl of 2 to 5 (preferably 2 to 4) carbon atoms; or amino. R will frequently and conveniently be a lower alkyl group such as methyl or ethyl, especially methyl. When R is haloalkyl, the alkyl radical may be substituted with one or more same or different halogen atoms, pre- ferably the same and preferably fluorine. Typical fluoroalkyl groups include luoromethyl, difluoro- methyl, 2-fluoroethyl, and 3- luoropropyl. Examples of other R ¹ substituents include cyanomethyl, amino, 2-propenyl, 2-propynyl, 2-methoxyethyl, methylthio- methyl, methylsulfinylmethyl, and methylsulfonyl- ethyl. In a preferred embodiment, R is methyl or a fluoromethyl having 1 or 2 fluorine atoms, especially methyl. 2 R may be hydrogen; halogen, especially fluorine, chlorine, or bromine; alkyl of 1 to 4 carbon atoms, especially methyl; haloalkyl of 1 to 4 carbon atoms, particularly a fluoroalkyl such as trifluoromethyl; cyanoalkyl of 1 to 4 alkyl carbon atoms such as cyano¬ methyl; alkenyl of 2 to 4 carbon atoms such as 2-pro- penyl; alkynyl of 2 to 4 carbon atoms such as 2-pro- pynyl; alkoxyalkyl of 2 to 4 carbon atoms, for example,

2-methoxyethyl; amino; hydroxycarbonyl; or alkoxycar- bonyl of ϊ to 4 alkyl carbon atoms. Compounds in which

2 R is hydroxycarbonyl, while in themselves or as salts are generally herbicidal at high application rates, are more useful as intermediates (for the

2 corresponding compounds in which R is hydrogen) than

2 as herbicides. In a preferred embodiment, R is hydrogen or methyl, especially hydrogen.

1 2 The groups W and W are independently selected from oxygen and sulfur. Thus, W 1 and W2 may both be oxygen or sulfur, W 1 may be oxygen and W2 may be

sulfur, or W1 may be sulfur and W2 may be oxygen. In a preferred embodiment W 1 and W2 are both oxygen.

A preferred subgenus for high herbicidal activity comprises the compounds of the formula

2 in which X is bromine or chlorine and Z is as defined above. Compounds in which the fluorine atom at C-2 of the phenyl ring is replaced by a chlorine atom and Z is other than hydrogen are also of particular interest. It will be understood that any alkyl, alkenyl or alkynyl group herein may be straight chain or branched chain radicals. Thus, 1-methylethyl, 2-methyl-2-pro- penyl, and l-methyl-2-propynyl are branched chain examples of alkyl, alkenyl, and alkynyl radicals respectively. Halogen may be fluorine, chlorine, bromine, or iodine. Haloalkyl radicals may have one or more same or different halogen atoms.

Any herbicidal compound of the present invention in 2 which R is C0 ₂ H or in which Z is or contains

S0,H or C0 ₂ H may, of course, be converted into a salt such as a sodium, potassium, calcium, ammonium, magnesium, or mono-, di-, or tri(C. to C. alkyl)- a moniura salt which may also be used as an herbicide. Such salts are within the scope of the present inven¬ tion.

A number of the compounds of the invention may more readily exist in hydrated form rather than as non- hydrated materials. It will be understood that the presence or absence of water of hydration in the compounds is of no concern in determining the metes and bounds of the present invention.

The present compounds may be prepared by methods described in the literature or by methods analogous or similar thereto and within the skill of the art.

Many of the present compounds may be prepared as illustrated in the following chemical equations: Method A: R ² = H or C0 ₂ H

(CONHCO2C2H 5) 2

II II I

Id

e

An appropriately substituted aniline, II, is treated first with aqueous hydrochloric acid, sodium acetate, and sodium nitrite, then with malonyldiure- thane and sodium acetate to produce intermediate III. Compound III is cyclized by treatment first with ethanolic potassium hydroxide in tetrahydrofuran, then with aqueous hydrochloric acid to give the triazine- dionecarboxylic acid Ic which is decarboxylated in the presence of mercaptoacetic acid and xylene to give the intermediate Compound Id. Treatment of Id with R Y, in which Y is a suitable leaving group, in the presence of a base gives the N-substituted triazinedione Ie.

Method B: R = H, alkyl

II IV

V

VI

An appropriately substituted aniline is reacted with sodium nitrite and tin (II) chloride in aqueous hydrochloric acid to produce the corresponding hydra- zine, Compound IV, which is converted to hydrazone V by treatment with acetone in sulfuric acid and tetrahydro- furan. Treatment of V with potassium cyanate in aqueous acetic acid gives triazolidinone VI which upon

2 reaction with R C0C0 ₇ H and sulfuric acid in dioxane produces triazinedione Ih. Reaction of Ih with R 1Y wherein Y is a leaving group gives product li. The methods illustrated above for producing Ie and li are generally applicable where the starting material Compound II is readily available, either commercially or by preparation, and the substituent Z is stable under the conditions of the process. In some instances the desired Z substituent may be unstable under the conditions used in preparing the starting material II or in converting II into product Ie or li. In such cases or where it is otherwise not desirable or con¬ venient to have the desired Z substituent in place at the outset, in Compound II, it may be advantageous to incorporate the desired Z group into the molecule further on in the process, for example, subsequent to the addition of the R group.

For example, the products in which Z is -OR , -OS0 ⁾ 2 ₇ ⁱ R ¹⁰ , ^' -OCR ³ R ⁴ CO-Q ¹ R ⁵ , or -OR (R is other than

lower alkyl) may advantageously be prepared from Compound Ie (or li) in which Z is lower alkoxy or benzyloxy as illustrated in the following chemical equations :

dealkylate

I

Ig

In the equations above R represents the appropriate radical -R ⁹ , -S0 ₂ R ¹⁰ , -CR ³ R ⁴ -CO-Q ¹ R ⁵ , or -R and Y represents a leaving group. The phenolic intermediate If is readily prepared from the corre¬ sponding compound Ie in which Z is lower alkoxy or benzyloxy by -treatment with an acidic reagent such as concentrated sulfuric acid, concentrated hydrobromic acid, or a mixture of hydrobromic and acetic acids to effect dealkylation, or, where Z is benzyloxy, by hydro- genolysis over. palladium on charcoal (H ₂ /Pd/C/C ₂ H-OH) . Reaction of the 5-hydroxyphenyl intermediate If with the appropriate R ⁹ -Y, R ¹⁰ -S0 ₇ Y, Y-CR ³ R ⁴ -CO-Q ¹ R ⁵ , or R-Y, i.e., R 13-Y in the equation above, in the presence of a base gives product Ig.

Similarly, products corresponding to Ie or li in which Z is -SR , where R has the meaning given above, may be prepared by treatment of the corresponding 5-mercaptophenyl compound with R -Y. The 5-mercaptophenyl compound may be prepared from the corresponding compound in which Z is hydrogen (Ie or

li, Z = H) by the sequence of steps illustrated below:

HN0 ₃ /H ₂ S0 ₄ H ₂ /PT

Ie 5-NO„ 0 ₂

5- H _r

C ₂ H ₅ OH (Z-H) Ik

Ik α>NaN0 ₂ /HCl ^ Sn/HCl ₅ -SH (2) S0 ₂ /CuCl

II Im

Compound Ie in which Z is hydrogen may be nitrated to give the corresponding 5-nitro compound Ij, which may be reduced to give the corresponding 5-amino compound Ik. Compound Ik may be treated first with NaN0 ₂ /HCl, then with S0 ₂ /CuCl to give the 5-chlorosulfonyl com¬ pound II which may be reduced with Sn/HCl to give the corresponding 5-mercapto compound Im.

As with the 5-OH and 5-SH intermediates, the 5-NH ₂ compound, Ik, -is an important intermediate which may be alkylated or acylated to introduce other Z substituents into the molecule. Compounds in which Z is alkoxycarbonylamino, di(alkylcarbonyl)amino, -NR ⁷ R, or -NR ⁷ -CR ³ R ⁴ -CO-Q ¹ R ⁵ may be prepared in this manner from the corresponding 5-NH ₂ compound.

An alternative method for introducing certain -NHR or -NH-CR ³ R ⁴ -CO-Q ¹ R ⁵ Z groups is illustrated in the equa¬ tion below:

5-NH + CH COCH- BHg-THF 5- HCH(CH,).

•J _THF i t

Ik

For example, Compounds 89 (Z = -NHCH(CH ₃ ) ₂ ) , 206 (Z = -NH-cyclohexyl), and 232 (Z = -NH-CH(CH ₃ )-C0 ₂ C ₂ H ₅ ) shown in Table 1 below were prepared by condensing the corresponding 5-NH- compound with the appropriate ketone in the presence of borane in tetrahydrofuran. The compound of formula Ie or li in which Z is

- l o ¬

-NHN=CRllR12 may also be produced from the corre¬ sponding compound in which Z is -NH ₂ by reacting the 5-NH- compound with NaN0 ₂ and SnCl ₂ in aqueous HC1 to give the corresponding hydrazine (Ie, Z = -NHNH.) , followed by condensation with R ¹¹ COR ¹ .

The amino compounds (Ie or li, Z = -NH ₂ ) may also be converted into the corresponding compounds in which Z is a halogen atom by treatment with nitrous acid under conditions which give a diazonium salt followed by treatment of the salt with the appropriate halogen reagent, for example, CuCl, CuBr, I, or HBF..

1 2 The compounds of formula I in which W or W or both are sulfur may be prepared as follows. Compound

Ie or li may be treated with one equivalent of P^S _ς in pyridine to give the corresponding compound of formula I in which W is sulfur; or Ie or li may be treated with at least two equivalents of 2S5 to produce the dithione derivative (I, W = W = S).

Compound I in.which W 1 is sulfur and W2 is oxygen may be prepared by substituting KSCN for KOCN in Method B above to produce the triazolidinethione corresponding to the triazolidinone VI which may then be carried through the Method B process to give the 1,2,4-tria- zine-3-thione-5-one product. The novel intermediates for the present herbicidal compounds are also part of the present invention, particularly compounds VII, VIII, IX, and X.

In each of the compounds above, X1, X2, W1,

2 1 and W are as defined above. Preferably X and

2 X are both halogen, especially fluorine, chlorine, or bromine. In a particularly preferred embodiment,

1 2 X is chlorine or, especially, fluorine and X is chlorine or bromine. W 1 and W2 are preferably both oxygen.

For compound VII, R is an alkyl group, prefer¬ ably of 1 to 4 carbon atoms, which may be substituted or unsubstituted, and:

Z is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, alkoxycarbonylamino of 1 to 6 alkyl carbon atoms, di(alkylcarbonyl)amino in which each alkyl is of 1 to 6 carbon atoms, hydroxysulfonyl, halo- sulfonyl, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms, -QR, -CO-R ⁶ , -S(0) R ⁸ , -Q ² R ⁹ ,

-0S0 ₇ R ¹⁰ , NHN=CR ^U R ¹² , or -Q-CR ³ R ⁴ -C0-Q ¹ -R ⁵ ;

Q and Q 1 are independently 0, S, or NR7 in

7 which R is hydrogen or alkyl of 1 to 6 carbon atoms; Q ² is 0 or S;

R is hydrogen, alkyl of 1 to 6 carbon atoms (which is unsubstituted or substituted with cycloalkyl of 3 to 7 carbon atoms), cycloalkyl of 3 to 7 carbon atoms (which is unsubstituted or substituted with alkyl of 1 to 6 carbon atoms), benzyl, alkoxyalkyl of 2 to 8 carbon atoms, alkoxyalkoxyalkyl of 3 to 8 carbon atoms, alkylthioalkyl, alkylsulfinylalkyl, or alkylsulfonyl- alkyl of 2 to 8 carbon atoms, tri(alkyl of 1 to 4 car¬ bon atoms)silyl(alkyl of 1 to 4 carbon atoms), cyano- alkyl of 1 to 5 alkyl carbon atoms, alkenyl or halo- alkenyl of 2 to 5 carbon atoms, alkynyl or haloalkynyl of 2 to 5 carbon atoms, haloalkyl of 1 to 5 carbon atoms, alkylcarbonyl of 1 to 6 alkyl carbon atoms, or dialkylaminocarbonyl or dialkylaminothiocarbonyl in which each alkyl is of 1 to 6 carbon atoms;

R is hydrogen or alkyl of 1 to 4 carbon atoms, 4 and R is hydrogen, alkyl of 1 to 4 carbon atoms, or

alkoxy of 1 to 4 carbon atoms;

R is hydrogen, alkyl of 1 to 6 carbon atoms (which is unsubstituted or substituted with cycloalkyl of 3 to 7 carbon atoms) , cycloalkyl of 3 to 7 carbon atoms (which is unsubstituted or substituted with alkyl of 1 to 4 carbon atoms), alkoxyalkyl 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 carbon atoms (which is unsubstituted or substi- tuted with alkyl of 1 to 4 carbon atoms), cycloalkenyl- alkyl of 6 to 10 carbon atoms, phenyl or phenylmethyl (each of which is unsubstituted or ring-substituted with fluorine, chlorine, bromine, or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms) , cyanoalkyl of 1 to 5 alkyl carbon atoms, alkynyl of 2 to 5 carbon atoms, alkylimino of 1 to 6 carbon atoms (which is unsubsti¬ tuted or substituted with cycloalkyl of 3 to 7 carbon atoms) , or cycloalkylimino of 5 to 7 carbon atoms (which is unsubstituted or substituted with alkyl of 1 to 4 carbon atoms); or Q and R together represent a phenylsulfonylamino group in which the ^" phenyl is unsubstituted or substituted with fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkoxycarbonyl of 1 to 4 alkyl carbon atoms;

R 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 sub- stituted with alkoxy of 1 to 4 carbon atoms; g R is alkyl of 1 to 6 carbon atoms or alkenyl or alkynyl of 2 to 5 carbon atoms and m is 1 or 2; 9 R is a 5- or 6-membered ring heterocyclic group of 1 or 2 same or different heteroatoms selected from 0,S, and N or an alkyl radical of 1 to 5 carbon atoms substituted with said heterocyclic group;

R is alkyl of 1 to 6 carbon atoms (which is

unsubstituted or substituted with halogen, cyano, alkoxy or alkylthio of 1 to 4 carbon atoms, or alkyl¬ amino or dialkylamino in which alkyl is of 1 to 4 carbon atoms), phenyl, or alkylamino or dialkylamino in which alkyl is of 1 to 4, carbon atoms; and

R is hydrogen or alkyl of 1 to 4 carbon atoms and R 12 is alkyl of 1 to 4 carbon atoms, or

C(R )(R ¹² ) taken as a unit is cycloalkyl of 3 to 7 carbon atoms.

Preferably Z is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxysulfonyl, chloro- sulfonyl, or a group -OR in which R is alkyl of 1 to 6 carbon atoms, benzyl, alkoxyalkyl of 2 to 4 carbon atoms, or alkenyl or alkynyl of 2 to 5 carbon atoms. In a particularly preferred embodiment Z is -OR in which R is alkyl of 1 to 4 carbon atoms or benzyl.

For compound VIII (R = H) , Z is as defined above

2 for compound VII and R is hydrogen, hydroxycarbonyl,

2 or alkyl of 1 to 4 carbon atoms such as methyl. R is preferably hydrogen or hydroxycarbonyl.

2 For compound IX (R - C0 ₇ H), Z is as defined above for compound VII and R is alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms, cyano¬ alkyl of 1 to 5 alkyl carbon atoms, alkenyl or alkynyl of 2 to 5 carbon atoms, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, or alkylsul onylalkyl of 2 to 5 carbon atoms. R is preferably alkyl of 1 to 4 carbon atoms, cyanoalkyl of 1 to 3 alkyl carbon atoms, fluoroalkyl of 1 to 3 carbon atoms, alkenyl or alkynyl of 3 to 5 carbon atoms, alkoxyalkyl of 2 to 4 carbon atoms, alkylthioalkyl of 2 to 4 carbon atoms, alkyl¬ sulfinylalkyl of 2 to 4 carbon atoms, or alkylsul- fonylalkyl of 2 to 4 carbon atoms. For example, R may be methyl, ethyl, cyanomethyl, 2-propenyl, 2-pro- pynyl, fluoromethyl having 1 or 2 fluorine atoms,

2-fluoroethyl, 3-fluoropropyl, methoxymethyl, methyl- thiomethyl, methylsulfinylmethyl, or methylsulfonyl-

methyl, especially methyl.

For compound X (Z = OH, SH, or NH ₇ ), R is as defined above for compound IX and R 2 is hydrogen or

2 alkyl of 1 to 4 carbon atoms such as methyl, R is preferably hydrogen.

Representative compounds of the invention are shown in Table 1. Characterizing data for many of the com¬ pounds are given in Table 2.

The preparation and herbicidal activity of repre- sentative compounds of this invention are illustrated further in the examples below. All temperatures are in degrees Celsius, and all pressures are in mm Hg.

EXAMPLE I 2-( 2, 4-DICHL0R0PHENYL)-4, 6-DIMETHYL-1, 2, 4-TRIAZINE- 3,5-(2H,4H)-DIONE

Step A 2-( 2, 4-Dichlorophenyl)-6-methyl- l,2,4-triazine-3,5(2H,4H)-dione

To a stirred solution of 4.32 g (0.020 mole) of 2,4-di- chlorophenylhydrazine hydrochloride in 100 L of water and 50 mL of ethanol was added dropwise 2.14 g (0.024 mole) of pyruvic acid in 50 mL of water. Upon complete addition, a precipitate formed and was collected by filtration and dried under reduced pressure at ambient temperature. The solid hydrazone product was dissolved in 100 mL of toluene to which 4.8 g (0.041 mole) of thionyl chloride was added. The resultant mixture was stirred and heated at reflux for 0.5 hour. Distilla¬ tion of the solvent under reduced pressure left a solid residue, which was dissolved in 100 mL of toluene. Urethane (2.2 g, 0.024 mole) was added, and the resul¬ tant solution heated at reflux with stirring for two hours. The solvent was removed from the mixture by distillation under reduced pressure to leave a resi¬ due. This residue was subjected to column chromato-

graphy on silica gel, eluting with ethyl acetate:hep- tane (1:1). Appropriate fractions were combined, and the solvent removed by evaporation to leave a gummy residue. The residue was dissolved in 75 mL of ethanol and 75 mL of IN sodium hydroxide. The resultant solu¬ tion was heated to 60°C, then poured into a mixture of 3N hydrochloric acid and ice. A solid formed which was collected by filtration and dried under reduced pres¬ sure. Recrystallization from tetrahydro uran:heptane provided 2.0 g of 2-( 2,4-dichlorophenyl)-6-methyl- l,2,4-triazine-3,5(2H,4H)-dione (mp 197°C dec), Compound 4 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Step B 2-(2,4-Dichlorophenyl)-4,6-dimethyl- l,2,4-triazine-3,5(2H,4H)-dione

A solution of 1.1 g (0.0040 mole) of 2-( 2,4-dichloro- phenyl)-6-methyl-l , 2,4-triazine-3,5(2H,4H)-dione in 5 mL of N,N-dimethylformamide was added to a stirred mixture of 0.11 g (0.0045 mole) of sodium hydride in 10 mL of N,N-diraethylformamide. After 0.5 hour, 0.63 g (0.0045 mole) of iodomethane in 5 mL of N,N-dimethyl- formamide was added, and the resultant mixture was stirred for approximately 18 hours. The mixture was poured into water and the resulting precipitate was collected and dissolved in ethyl acetate. The organic solution was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to leave a solid. The solid was purified by recrystallization from hep¬ tane to yield 0.52 g of 2-(2,4-dichlorophenyl)-4,6-di- methyl-l,2,4-triazine-3,5(2H,4H)-dione (mp 109-110°C), Compound 5 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE I I 2 - [ 4-CHLORO- 2-FLUORO- 5- ( l-METHYLETHOXY)PHENYL ] - 1 , ^' 2 , 4-TRIAZINE- 3 , 5 ( ^' 2H , 4H) -DI0NE

Step A Methyl (2-chloro-4-fluorophenyl) carbonate

To a stirred solution of 20.0 g (0.14 mole) of 2-chloro-4-fluorophenol and 6.64 g (0.17 mole) of sodium hydroxide in 100 mL of water at 15°C was added 17.7 g (0.19 mole) of methyl chloroformate. After complete addition, the mixture was stirred for 15 minutes then extracted with ethyl acetate. The organic phase was washed with a IN sodium hydroxide solution, then dried over anhydrous magnesium sulfate. The dried extract was filtered, and the filtrate evaporated under reduced pressure to provide methyl (2-chloro-4-fluoro¬ phenyl) carbonate as a solid.

Step B 2-Chloro-4-fluoro-5-nitrophenol

To a stirred mixture of methyl (2-chloro-4- luoro¬ phenol) carbonate prepared in Step _. A in 21.7 L of concentrated sulfuric acid was added dropwise 11.1 mL of concentrated nitric acid. The reaction mixture was kept at a temperature below 30°C throughout the addi¬ tion. After complete addition, the mixture was stirred at room temperature for one hour, then poured into 500 mL of ice water. The aqueous mixture was extracted with ethyl acetate. The extract was washed in succes¬ sion with water, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride. The washed extract was dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure to leave a solid residue, methyl (2-chloro-4- fluoro-5-nitrophenyl) carbonate. This residue was dissolved in 100 mL of ethanol to which was added 150

mL o£ a IN sodium hydroxide solution. The mixture was heated on a steam bath for 30 minutes, cooled, and poured into a mixture of ice and hydrochloric acid. The resultant acidic mixture was extracted with ethyl acetate. The extract was dried over anhydrous magne¬ sium sulfate and was filtered. The filtrate was evaporated under reduced pressure to give an oil which crystallized slowly. Recrystallization from heptane gave 15.8 g of 2-chloro-4-fluoro-5-nitrophenol. The nmr spectrum was consistent with the assigned structure.

Step C 4-Chloro-2-fluoro-5-(1-methylethoxy)- nitrobenzene

To a stirred solution of 15.8 g (0.083 mole) of 2-chloro-4-fluoro-5-nitrophenol in 90 mL of acetone was added 17.1 g (0.12 mole) of potassium carbonate follow¬ ed by a solution of 21.0 g (0.12 mole) of 2-iodopropane in 10 mL of acetone. After complete addition, the reaction mixture was heated at 60°C for approximately 18 hours. The mixture was cooled and poured into a mixture of ice and concentrated hydrochloric acid. The resultant mixture was extracted with ethyl acetate, and the extract was washed with a IN sodium hydroxide solu¬ tion. The washed extract was dried over anhydrous magnesium sulfate and was filtered. The solvent was evaporated under reduced pressure to leave 17.7 g of 4-chloro-2-fluoro-5-(l-methylethoxy)nitrobenzene as a solid.

Step D 2-[4-Chloro-2-fluoro-5-(l-methylethoxy)- phenyl]-l, 2,4-triazine-3, 5(2H,4H)-dione

Hydrogenation of 2.8 g (0.012 mole) of 4-chloro-2- fluoro-5-(l-methylethoxy)nitrobenzene in the presence of 30 mL of acetic acid and 0.2 g of platinum oxide

produced 4-chloro-2- luoro-5-(1-methylethoxy)aniline, which was not isolated from the reaction mixture. The platinum catalyst was removed by filtration, and the filtrate was diluted with 100 mL of water and 10 mL of concentrated hydrochloric acid. The acid solution was cooled to 0°C, and a solution of 0.84 g (0.012 mole) of sodium nitrite in 10 mL of water was added. The solu¬ tion was stirred at 0°C for 30 minutes, then a solution of 5.0 g (0.061 mole) of sodium acetate in 10 mL of water was added. After stirring for a short period of time, the solution was added to a mixture of 3.0 g (0.12 mole) of malonyldiurethane [prepared by the method of Backes, et al. , J. Chem. Soc. , 359, (1921)] and 25.0 g (0.29 mole) of anhydrous sodium acetate in 300 mL of water at 10°C. After complete addition, the mixture was stirred at 10°C for 30 minutes. The mix¬ ture was extracted with ethyl acetate, and the extract washed with a saturated aqueous sodium chloride solu¬ tion. The washed extract was dried over anhydrous magnesium sulfate, filtered, and the filtrate evapo¬ rated under reduced pressure to give 6.0 ^~ g of a solid.

The solid was dissolved in a mixture of 80 mL of ethanol and 80 mL of tetrahydrofuran. To this was added 40 mL of a 10% aqueous potassium hydroxide solu- tion. The resultant mixture was stirred for 15 minutes and washed with ethyl acetate. The aqueous phase was made acidic with dilute hydrochloric acid, and the acidic solution extracted with ethyl acetate. The extract was treated with decolorizing charcoal and dried over anhydrous magnesium sulfate. The extract was filtered, and the filtrate was concentrated under reduced pressure to leave 3.2 g of a residue. The residue was heated at 150°C in 6.0 mL of mercaptoacetic acid for three hours. The mixture was cooled to room temperature, diluted with ethyl acetate, and extracted with a saturated aqueous sodium bicarbonate solution. The organic phase was dried over anhydrous magnesium

sulfate and filtered. The solvent was evaporated from the filtrate under reduced pressure to yield 2.0 g of 2- [4-chloro-2- luoro-5-(l-methylethoxy)phenyl]-l, 2,4- triazine-3, 5(2H,4H)-dione as an oil, Compound 17 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE III 2-[2,4-DICHLORO-5-(2-PROPYNYLOXY)PHENYL]-

4-METHYL-l,2,4-TRIAZINE-3,5(2H,4H)-DIONE

Step A 3-Hydroxyacetanilide

To a stirred solution of 66.0 g (0.60 mole) of 3-amino- phenol in 180 mL of water was added dropwise 77.9 g (0.76 mole) of acetic anhydride. After complete addi¬ tion, the reaction mixture was heated on a steam bath for 10 minutes, then cooled to 0°C. A precipitate formed and was collected by filtration. The filter cake was washed with cold water and dried- in a desiccator for two hours to yield 81.0 g of 3-hydroxyacetanilide (mp 144-146°C).

Step B 2,4-Dichloro-5-hydroxyacetanilide

Chlorination of 53.0 g (0.35 mole) of 3-hydroxyaceta- nilide with chlorine gas in 400 mL of glacial acetic acid at 15-20°C for one hour produced 23.5 g of 2, 4-dichloro-5-hydroxyacetanilide (mp 226-228°C).

Step C 2,4-Dichloro-5-(l-methylethoxy)acetanilide

A stirred mixture of 22.0 g (0.1 mole) of 2,4-di- chloro-5-hydroxyacetanilide, 25.5 g (0.15 mole) of 2-iodopropane, and 20.7 g (0.15 mole) of potassium

carbonate in 150 mL of acetone was heated at reflux temperature for approximately 18 hours. The mixture was cooled, filtered, and the filtrate evaporated under reduced pressure to leave a solid. The solid was recrystallized from ethanol to yield 22.3 g of 2,4-di- chloro-5-(l-methylethoxy)acetanilide (mp 129-130°C).

Step D 2, 4-Dichloro-5-(l-methylethoxy)aniline

A stirred mixture of 22.3 g of 2,4-dichloro-5-(l- methylethoxy) acetanilide, 60 mL of concentrated hydro¬ chloric acid, and 60 mL of water was heated at reflux for 0.5 hour. The mixture was cooled in a refrigera¬ tor, and the resulting precipitate was collected by filtration. The solid was suspended in water, and the mixture was treated with sodium carbonate until it was slightly basic. The resultant mixture was extracted with diethyl ether. The extract was washed with water, and the ether removed by distillation under reduced pressure to leave an oil. Distillation of the oil under reduced pressure produced 14.0 g of 2,4-di- chloro-5-(l-methylethoxy)aniline (bp 102°C at 0.1 mm Hg).

Step E 2-[2,4-Dichloro-5-(l-methylethoxy)- phenyl]-l, 2,4-triazine-3,5(2H,4H)- dione-6-carboxylic acid

To a stirred mixture of 10.0 g (0.045 mole) of 2,4-di- chloro-5-(l-methylethoxy)aniline in 200 mL of water was added 30 mL of concentrated hydrochloric acid. The resultant mixture was cooled to 0°C, and a solution of 3.13 g (0.45 mole) of sodium nitrite in 30 mL of water was added during 15 minutes. After complete addition, 30.0 g (0.35 mole) sodium acetate in 60 mL of water was added, and the resulting mixture was _. stirred at 0°C for one hour. The cold reaction mixture was added por-

tionwise to a stirred solution of 11.7 g (0.0477 mole) of malonyldiurethane [prepared by the method of Backes, et al., J. Chem. Soc. , 350, (1921)] and 50.0 g (0.59 mole) of anhydrous sodium acetate in 1500 mL of water at 0°C. After complete addition the mixture was stirred at 0°C for one hour, and the resulting precipi¬ tate was collected by filtration and washed with water. The filter cake was dissolved in a mixture of 250 mL of tetrahydrofuran and 250 mL of ethanol. To this solution was added 150 mL of a 10% aqueous potas¬ sium hydroxide solution. The resultant mixture was stirred for 0.5 hour and made acidic with 60 mL of con¬ centrated hydrochloric acid. Most of the tetrahydro¬ furan was removed from the mixture by evaporation under reduced pressure to leave an aqueous residue. The residue was extracted with ethyl acetate, and the extract treated with decolorizing charcoal. The extract wa.s dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave 17.9 g of 1-[2,4-dichloro-5-(1- methylethoxy)phenyl]-l, 2,4-triazine-3, 5(2H,4H)-dione- 6-carboxylic acid, Compound 11 in the tables.

The preparation of Compound 11 was repeated. The product was found to have a melting point of 195-197°C (dec.) and its nmr and ir spectra were consistent with the assigned structure.

Step F 2- [2,4-Dichloro-5-(l-methylethoxy)phenyl] l,2,4-triazine-3,5(2H, 4H)-dione

A stirred mixture of 10.0 g (0.028 mole) of 2-[2,4-di- chloro-5-(l-methylethoxy)phenyl]-l, 2,4-triazine-3,5- (2H,4H)-dione-6-carboxylic acid in 10 mL of mercapto¬ acetic acid was heated at 140°C for two hours. The reaction mixture was cooled to room temperature and partitioned between ethyl acetate and saturated aqueous sodium bicarbonate. The organic phase was washed with

two portions of saturated aqueous sodium bicarbonate, and then with saturated aqueous sodium chloride. The washed organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 7.5 g of 2-[2,4-di- chloro-5-(l-methylethoxy)phenyl]-l,2,4-triazine- 3, 5(2H, 4H)-dione, Compound 51 in the tables.

Compound 6 in the tables was prepared in a similar manner (Step E and F) from the appropriately substi- tuted aniline.

Step G 2- [2,4-Dichloro-5-(l-methylethoxy)phenyl]- 4-methy1-1, 2,4-triazine-3, 5(2H,4H)-dione

To a stirred mixture of 0.6 g (0.025 mole) of sodium hydride in 15 mL of N,N-dimethylformamide was added a solution of 7.5 g (0.024 mole) of 2- [2,4-dichloro-5- (l-methylethoxy)phenyl]-l, 2,4-triazine-3,5(2H, 4H)-dione in 30 mL of N,N-dimethylformamide with external cooling to maintain the reaction temperature below 40°C. After complete addition, the mixture was allowed to come to room temperature and was stirred for one hour. A solu¬ tion of 3.5 g (0.025 mole) of iodomethane in 10 mL of N,N-dimethylformamide was added to the reaction mix- ture, and stirring was continued for an additional hour at room temperature. The reaction mixture was poured into ice water, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to produce 2-[2,4-di- chloro-5-(l-methylethoxy)phenyl]-4-methyl-l, 2,4-triazine- 3, 5(2H, 4H)-dione as an oil, Compound 12 in the tables. The preparation of Compound 12 was repeated. The product was found to have a melting point of 111-112°C after chromatographic purification on a silica gel column. The nmr and ir spectra of this sample were

consistent with the assigned structure. Compounds 2, 7, 8, and 18 were also prepared in this manner from the appropriately substituted anilines (prepared by the methods of Example III, Steps E and F) and iodo- methane. Compounds 3, 15 and 19 were prepared from 3-brorao-l-propene and the appropriately substituted triazinedione. Similarly, reaction of the appropri¬ ately substituted triazinedione with propargyl bromide, bromoethane, and l-chloro-2-fluoroethane gave Compounds 25, 29, and 41 respectively.

Step H 2-( 2,4-Dichloro-5-hydroxyphenyl)-4-methyl- l,2,4-triazine-3,5(2H, 4H)-dione

The oil prepared in Step G (Compound 12) was stirred with 10 mL of concentrated sulfuric acid at 0°C for 10 minutes, and the mixture was poured into ice water. The aqueous mixture was extracted with ethyl acetate, and the solvent was removed from the extract by evapor- ation under reduced pressure to give a residue. The residue was purified by column chromatography on silica gel, eluting with ethyl acetate :heptane (1:1). Evapor¬ ation of the appropriate fractions gave 4.4 g of 2-(2, 4-dichloro-5-hydroxyphenyl)-4-methyl-l, 2, 4-tri- azine-3,5-(2H,4H)-dione (mp 199-201°C), Compound 9 in the tables.

The nmr spectrum was consistent with the assigned structure.

Step I 2- [2,4-Dichloro-5-( 2-propynyloxy)phenyl]-

4-methyl-l, 2,4-triazine-3,5(2H, 4H)-dione

Under a dry nitrogen atmosphere a solution of 1.0 g (0.003 mole) of 2-( 2, 4-dichloro-5-hydroxyphenyl)-4- methyl-1, 2, 4-triazine-3, 5( 2H, 4H)-dione in 15 mL of N,N-dimethylformamide was added slowly to a stirred mixture of 0.09 g (0.0037 mole) of sodium hydride in 15

mL of N,N-dimethylformamide. After complete addition, the mixture was stirred at 28°C until hydrogen evolu-

,. tion" ceased, then at 45°C for 30 minutes. The reaction mixture was cooled to room temperature, and a solution of 0.57 g (0.0038 mole) of 3-brorao-l-propyne in 5 mL of N,N-dimethylformamide was added. The mixture was stirred at room temperature for approximately 18 hours, poured into water, and extracted with ethyl acetate. The extract was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed from the filtrate by evaporation under reduced pressure to leave an oil. The oil was purified by preparative chromatography on silica gel, eluting with ethyl acetate :heptane (1:1), to yield 0.8 g of 2-[2,4-di- chloro-5-(2-propynyloxy)phenyl]-4-methyl-l ,2,4-triazine- 3,5(2H,4H)-dione (mp 119-120°C), Compound 20 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Compound 21, 2- [4-chloro-2-fluoro-5-( 2-propynyl- oxy)phenyl]-4-methyl-l, 2,4-triazine-3, 5(2H,4H)-dione, was also prepared by the method of Example III, Steps H and I, from the appropriately substituted triazinedione.

EXAMPLE IV 2-[2,4-DICHLORO-5-(l-METHYL£THOXY)PHENYL]- 4, 6-DIMETHYL-1, 2, 4-TRIAZINE-3, 5( 2H, 4H)-DIONE

Step A 2, 4-Dichloro-5-( l-raethylethoxy)phenyl- hydrazine

A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of water was added to a stirred solution of 50.0 g (0.23 mole) of 2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentrated hydrochloric acid at 0°C over 30 minutes. After complete addition, the mixture was

stirred at 0°C for 30 minutes. A solution of 114.0 g (0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentrated hydrochloric acid was added dropwise to the reaction mixture. After complete addition, the mixture was stirred for one hour. The resultant white slurry was filtered. The filter cake was added to a 20% aqueous sodium hydroxide solution and stirred for 30 minutes. The basic mixture was filtered, and *the filter cake recrystallized from methanol and water to yield 37.0 g of 2,4-dichloro-5-(l-methylethoxy)phenyl- hydrazine.

Step B 1- [2,4-Dichloro-5-( l-methylethoxy)phenyl] ^• 3,3-dimethyl-l, 2,4-triazolidin-5-one

To a stirred solution of 12.7 g (0.054'mole) of 2,4-di- chloro-5-(l-methylethoxy)phenylhydrazine in a mixture of 100 mL of tetrahydro uran and 30 mL of acetone was added 0.5 mL of a 2N sulfuric acid solution. The reac- tion mixture was stirred at room temperature for 30 minutes after which the solvent was removed by evapora¬ tion under reduced pressure. The residue was dissolved in ethyl acetate, and the organic solution was washed with water. The washed organic solution was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure leaving 14.6 g of an oil. The oil was dissolved in 50 mL of glacial acetic acid and 2 mL of water. To this solution was added portionwise 4.5 g (0.56 mole) of potassium cyanate. After complete addition, the mixture was stirred at room temperature for approximately 18 hours. An addi¬ tional 0.5 g of potassium cyanate was added, and the reaction mixture was stirred for five hours. The mix¬ ture was then diluted with water and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, filtered, and the filtrate evapo¬ rated under reduced pressure leaving an oil. The oil

was dissolved in 20 mL of ethyl acetate and, upon the addition of 10 mL of heptane, formed a precipitate. The precipitate was collected by filtration and recrystallized from ethyl acetate and heptane to give 4.5 g of 1- [2,4-dichloro-5-(l-methylethoxy)phenyl]- 3,3-dimethyl-l,2,4-triazolidin-5-one (mp 162-163°C). The nmr and ir spectra were consistent with the assigned structure.

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

6-methyl-l, 2,4-triazine-3,5(2H,4H)-dione

To a stirred mixture of 1.0 g (0.0031 mole) of l-[2,4- dichloro-5-(l-methylethoxy)phenyl]-3,3-dimethyl-l, 2,4- triazolidin-5-one in 10 mL of p-dioxane was added

0.29 g (0.0031 mole) of pyruvic acid and one drop of concentrated sulfuric acid. The mixture was stirred at room temperature for one hour, then an additional 0.25 g (0.0029 mole) of pyruvic acid was added. The mixture was heated at 90°C for three hours, then poured into water. The mixture was extracted with ethyl acetate, and the solvent was evaporated from the extract under reduced pressure to give an oil. The oil was purified by thin-layer preparative chromatography on silica gel, eluting with ethyl acetate:heptane (1:1). Extraction of the appropriate bands gave 0.6 g of 2- [2,4-dichloro- 5-(1-methylethoxy)phenyl]-6-methyl-l,2,4- riazine- 3,5(2H,4H)-dione as a solid (mp 163-164°C), Compound 10 in the tables. The nmr and ir spectra were consistent with the assigned structure.

Step D 2- [2,4-Dichloro-5 _. -(l-methylethoxy)phenyl] ^■ 4,6-dimeth l-l,2,4-triazine-3,5(2H,4H)- dione

In a manner similar to Example III, Step G, the reac-

tion of 0.28 g (0.00085 mole) of 2- [2,4-dichloro-5-(1- methylethoxy)phenyl ]-6-methyl-l, 2,4-triazine-3,5(2H,4H)- dione with 0.037 g (0.00093 mole) of sodium hydride (60% in oil) and 0.13 g (0.00093 mole) of iodomethane in 10 mL of N,N-dimethyl ormamide produced 0.19 g of 2- [2,4-dichloro-5-(l-methylethoxy)phenyl]-4,6-dimethyl- 1, 2, 4-triazine-3,5( 2H, 4H)-dione as a low melting solid, Compound 13 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Compound 16, 2- [2,4-dichloro-5-( 1-methylethoxy)- phenyl]-6-methyl-4-(2-propenyl)-l, 2,4-triazine-3,5- (2H, 4H)-dione, was also prepared by the method of Example IV using 3-bromo-l-propene rather than iodo- methane in Step D. Similarly, Compound 50, 2-[4- chloro-2-fluoro-5-( 1-me hylethoxy)phenyl ]-4-(3-fluoro- propyl)-l,2, 4-triazine-3, 5( 2H,4H)-dione, was prepared by treating Compound 17 (Example II D) with 1-chlbro- 3-fluoropropane.

EXAMPLE V 2- [2,4-DICHLORO-5-(1-METHYLETHOXY)PHENYL]-4-METHYL- l,2,4-TRIAZINE-3,5(2H,4H)-DIONE-6-CARBOXYLIC ACID

In a manner similar to Example III, Step G, the reac¬ tion of 6.6 g (0.018 mole) of 2- [2,4-dichloro-5-( 1- methylethoxy)phenyl]-l, 2,4-triazine-3,5(2H, 4H)-dione- 6-carboxylic acid (Compound 11, Example III E) with 1.5 g (0.037 mole) of sodium hydride (60% in oil) and 2.6 g (0.018 mole) of iodomethane in 35 mL of N,N-dimethyl- formamide produced 2.1 g of 2- [2, 4-dichloro-5-(1- methylethoxy)phenyl]-4-methyl-l, 2,4-triazine-3,5-(2H, 4H)' dione-6-carbαxylic acid as a solid (mp 230°C d), Com¬ pound 14 in the tables. The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE VI

ETHYL 2, 4-DICHLORO-5- [4-METHYL-l, 2, 4-TRIAZINE- 3,5(2H,4H)-DI0NE-2-YL]PHEN0XYACETATE

In a manner similar to Example II, Step C, the reaction ^" of 0.86 g (0.0030 mole) of 2-( 2, -dichloro-5-hydroxy- phenyl)-4-methyl-l,2,4-triazine-3, 5(2H,4H)-dione (Compound 9, Example III H) with 0.62 g (0.0045 mole) of potassium carbonate and 0.75 g (0.0045 mole) of ethyl bromoacetate in 10 mL of acetone produced an oil. The oil crystallized upon treatment with heptane to yield 0.85 g of ethyl 2,4-dichloro-5- [4-methyl- 1, 2,4-triazine-3,5(2H,4H)-dione-2-yl]phenoxyacetate (mp 115-117°C), Compound 22 in the tables. The nmr and ir spectra were consistent with the assigned structure.

Compounds 27 and 28 were prepared in a similar manner by treatment of Compound 9 with ethyl 2-bromo- propionate and chloroacetonitrile respectively. The nmr and ir spectra were consistent with the assigned structures.

EXAMPLE VII

2-(2,4-DICHLORO-5-METHYLSULFONYLOXYPHENYL)- 4-METHYL-l,2,4-TRIAZINE-3,5(2H,4H)-DI0NE

A solution of 0.35 g (0.0031 mole) of methanesul onyl chloride in 5 mL of tetrahydrofuran was added to a stirred solution of 0.8 g (0.0028 mole) of 2-(2,4-di- chloro-5-hydroxyphenyl)-4-methyl-l, 2,4-triazine-3,5- (2H,4H)-dione (Compound 9, Example III H) and 0.30 g (0.0031 mole) of triethylamine in 10 mL of tetrahydro¬ furan. The reaction mixture was stirred at room temperature for approximately 18 hours, then diluted with water. The resultant mixture was extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate. The dried extract was filtered, and

the filtrate was evaporated under reduced pressure to give 0.81 g of 2-( 2 ,4-dichloro-5-methylsulfonyloxy- phenyl)-4-methyl-l, 2 ,4-triazine-3, 5(2H,4H)-dione as a solid, Compound 23 in the tables. The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE VIII 2-[2,4-DICHL0R0-S-(l-METHYLETH0XY)PHENYL]-4- (2-FLU0R0ETHYL)-1,2,4-TRIAZINE-3, 5(2H,4H)-DIONE

To a stirred mixture of 0.084 g (0.0035 mole) of sodium hydride in 20 mL of tetrahydrofuran was added a solution of 1.0 g (0.003 mole) of 2- [2 ,4-dichloro-5- (l-methylethoxy)phenyl]-l, 2,4-triazine-3, 5(2H,4H)-dione (Compound 51, Example III, Step F) in 5 mL of tetra¬ hydrofuran. The resulting mixture was stirred at room temperature for one hour. Tetrabutylammonium bromide (0.5 g, 0.002 mole) and potassium hydroxide (0.5 g, 0.009 mole) were added, and the mixture was heated at 60-70°C for approximately 1.5 hours. While maintaining the temperature at 60°C, a solution of 0.5 g (0.004 mole) of l-bromo-2-fluoroethane in 5 mL of tetrahydro¬ furan was added. After complete addition, the mixture was allowed to cool to room temperature and was stirred for approximately 18 hours. The mixture was parti¬ tioned between dilute aqueous hydrochloric acid and ethyl acetate. The organic phase was dried over anhy¬ drous magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure produced an oil. The oil was subjected to column chromatography on silica gel, eluting with ethyl acetate:n-heptane (1:1). Evaporation of the appropriate fractions provided a solid which was recrystallized from ethyl acetate:n-heptane to give 0.4 g of 2- [2,4-dichloro- 5-(1-methylethoxy) henyl]-4-(2-fluoroethyl)-1, 2,4- triazine-3,5(2H, 4H)-dione, Compound 26 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE IX 2-[4-CHLORO-2-FLUORO-5-(3-BROMO-2-PROPYNYLOXY)- PHENYL]-4-METHYL-l,2,4-TRIAZINE-3,5(2H,4H)-DIONE

To a stirred mixture of 0.05 g (0.002 mole) of sodium hydride in 5 mL of tetrahydrofuran was added a solution of 0.55 g (0.0018 mole) of 2- [4-chloro-2-fluoro-5- (2-propynyloxy)phenyl]-4-methyl-l, 2,4-triazine- 3, 5( 2H,4H)-dione (Compound 21, see Example III, Step J) in 5 mL of tetrahydrofuran. To this mixture was added a solution of 0.28 g (0.0018 mole) of bromine in 5 mL of tetrahydrofuran. After complete addition, the reaction mixture was ^• stirred at room temperature for one hour. Water, 5 mL, ^' was added to the mixture, and the total stirred at room temperature for two days. The mixture was partitioned between water and ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.45 g of 2-[4-chloro-2-fluoro-5-(3-bromo-2-propynyloxy)phenyl]- 4-methyl-l, 2,4-triazine-3, 5( 2H, 4H)-dione as a solid (mp 127-129°C), Compound 48 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE X METHYL 2-[2-CHLORO-4-FLUORO-5-(2,3,4,5-TETRAHYDRO- 4-METHYL-3,5-DIOXO-l,2,4-TRIAZIN-2-YL)PHENOXY]- PROPIONATE

Step A 2-(4-Chloro-2- luoro-5-hydroxyphenyl)- 4-methyl-l,2,4-triazine-3,5(2H,4H)-dione

Treatment of 2- [4-chloro-2- luoro-5-(l-methylethoxy)-

phenyl]-4-methyl-l,2,4-triazine-3,5(2H,4H)-dione (Compound 18, see Example III G) with sulfuric acid in the manner of Example III H produced the phenolic compound 2-(4-chloro-2- luoro-5-hydroxyphenyl)-4- methyl-l,2,4-triazine-3,5(2H,4H)-dione, Compound 30 in the tables.

The nrm spectrum was consistent with the assigned structure.

Step B Methyl 2- [2-chloro-4-fluoro-5-( 2 ,3,4, 5- tetrahydro-4-methyl-3, 5-dioxo-l,2,4- triazi -2-yl)phenoxy]proprionate

Treatment of Compound 30 with methyl 2-chloropropionate in the presence of potassium carbonate in the manner of Example VI gave methyl 2- [2-chloro-4- luoro-5-( 2,3, 4,5- tetrahydro-4-methy1-3,5-dioxo-1,2,4-triazin-2-yl)phen- oxy]propionate, Compound 42 in the tables.

The nmr spectrum was consistent with the assigned structure.

Compounds 43, 44 and 49 were prepared in a similar manner by treatment of 2-(4-chloro-2- luoro-5-hydroxy- phenyl)-4-methyl-l ,2,4-triazine-3,5(2H,4H)-dione with ethyl chloroacetate, propargyl bromide, and iodoacet- amide respectively.

The nmr and ir spectra were consistent with the assigned structures.

Other compounds of the invention may be prepared by the methods exemplified above or by methods within the skill of the art.

HERBICIDAL ACTIVITY The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S) , wheat (Triticum aestivium var. Prodax) , field bindweed (Convolvulus arvensis), morn-

ingglory (Ipomea lacunosa or Ipomea hederacea) , velvet- leaf (Abutilon theophrasti) , barnyardgrass (Echinochloa crus galli) , green foxtail (Setaria viridis) , and johnsongrass (Sorghum halepense). 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 approxi- mately 0.5 cm.

The flats for the preemergence test were watered, then drenched with the appropriate amount of a solution of the test compound in a mixture of acetone and water containing a small amount (up to 0.5% v/v) of sorbitan monolaurate 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 oliage of the emerged test plants was sprayed with a solution of the test compound in acetone-water contain¬ ing up to 0.5% sorbitan monolaurate. After spraying the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded. Phytotoxicity data were taken either as percent kill or percent control. Percent control was deter¬ mined by a method similar to the 0 to 100 rating system disclosed in "Research Methods In Weed Science," 2nd ed. , B. Truelove, Ed. ; Southern Weed Science Society; Auburn Unversity, Auburn, Alabama, 1977. The present rating system is as follows:

Herbicide Rating System

Rating Description

Percent of Main Crop Weed

Control Categories Description Description

0 No effect No crop reduction No weed control or injury

10 Slight discoloration Very poor weed or stunting control

20 Slight Some discoloration, Poor weed control effect stunting or stand loss

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

40 Moderate injury, Deficient weed crop usually control recovers

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

60 Lasting crop Moderate weed injury no recovery control

70 Heavy injury and Control somewhat stand loss less than satis¬ factory

80 Severe Crop nearly des¬ Satisfactory to effect troyed a few good weed control survivors

90 Only occasional Very good to live plants left excellent control

100 Complete Complete crop Complete weed effect destruction destruction

Herbicidal data at selected application rates are given for various compounds of the invention in Table 3 and Table 4 below. The test compounds are identified therein by numbers which correspond to those in Table 1. In Tables 3 and 4 below:

"kg/ha" is kilograms per hectare, "% K" is percent kill, and "% C" is percent control.

It is clear from the data that the generic class of aryltriazinediones and sulfur analogs thereof described and illustrated herein is characterized by herbicidal activity, and that the degree of this activity varies among specific compounds within this class and to some extent among the species of plant to which these com- pounds may be applied. Thus, selection of a specific herbicidal compound for control of a specific plant may readily be made.

For herbicidal application, the active compounds as above defined are formulated into herbicidal composi- tions, by admixture, in herbiςidally effective amounts, with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingre¬ dients 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 agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, as water- soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concen¬ trates, 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 cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc. Wettable powders, also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate disper¬ sion. For example, a useful wettable powder formula¬ tion contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.

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 concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingre¬ dient 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 herbi¬ cidal composition. Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts, polyhydric alcohols, and other types of surface active agents, many of which are available in commerce. The surface active agent, when used, normally comprises 1% to 15% by weight of the herbicidal composition.

Other useful formulations for herbicidal applica¬ tions include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used. Water-soluble or water-dis- persible granules are also useful formulations for herbicidal application of the present compounds. Such

granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful herein with the present herbicidal compounds.

The active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture. 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- 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-(l-methylethyl)-(lH)-2, 1, 3-benzo- thiadiazin-4-(3H)-one-2, 2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)- 1, 3, 5-triazine-2, -diamine (atrazine), and 2- [4- chlor0-6-(ethylamino)-1, 3,5-triazin-2-yl]amino -2- methylpropanenitrile (cyanazine); dinitrolaniline herbicides such as 2, 6-dinitro-N,N-dipropyl-4-(tri- fluoromethyDbenzeneamine (trifluralin) ; and aryl urea herbicides such as N" -( 3,4-dichlorophenyl)-N,N-di- methylurea (diuron) and N,N-dimethyl-N' - [3-(tri luoro- methyl)phenyl ]urea (flupmeturon) .

It is apparent that various modi ications 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 claims.

(Except where indicated otherwise, l = W ² = oxygen).

Compound Number _χi_ ¹ - z - ¹ — ² -

1 H H H CH ₃ H

2 F H H CH ₃ H

3 H Cl H CH ₂ CH=CH ₂ H

4 Cl Cl H H CH ₃

5 Cl Cl H CH ₃ CH ₃

6 ^" F Cl H H H ^■

7 F Cl H CH ₃ H

8 ⁴ Cl Cl H CH ₃ H

9 Cl Cl OH CH ₃ H

10 Cl Cl 0CH(CH ₃ ) ₂ H CH ₃

11 Cl Cl OCH(CH _{3 2} H C0 ₂ H

12 Cl Cl 0CH(CH ₃ ) ₂ CH ₃ • H

13 Cl Cl 0CH(CH ₃ ) ₂ CH ₃ CH ₃

14 Cl Cl 0CH(CH ₃ ) ₂ CH ₃ C0 ₂ H

16 Cl Cl 0CH(CH ₃ ) ₂ CH ₂ CH=CH ₂ CH ₃

17 F Cl 0CH(CH ₃ ) ₂ H H

18 F Cl 0CH(CH ₃ ) ₂ CH ₃ H

19 F Cl 0CH(CH ₃ ) ₂ CH ₂ CH=CH ₂ H

20 Cl Cl OCH C=CH CH ₃ H

21 F Cl 0CH ₂ C2CH CH ₃ H

22 Cl Cl 0CH ₂ C0 ₂ C ₂ H ₅ CH ₃ H

23 Cl Cl 0S0 ₂ CH ₃ CH ₃ H

24 ¹ F Cl 0CH ₂ CsCH CH ₃ H

Table 1 Representative Compounds

Compound Number ¹ - ² Z _* ² _

25 Cl Cl 0CH(CH ₃ ) ₂ CH ₂ C=CH H

26 Cl Cl 0CH(CH ₃ ) ₂ CH ₂ CH ₂ F H

27 Cl Cl 0CH(CH ₃ C0 ₂ C ₂ H ₅ CH ₃ H

28 Cl Cl 0CH ₂ CN CH ₃ H

29 Cl Cl 0CH(CH ₃ ) ₂ C ₂ H ₅ H

30 F Cl OH CH ₃ H

31 H Cl H H C0 ₂ H

32 H Cl 0CH ₃ H C0 ₂ H

33 H Cl H H H

34 H CH ₃ H H H

35 H CH ₃ H CH ₃ H

36 . H Cl H CH ₃ H

37 H Cl 0CH ₃ H H

38 H 0CH ₃ H H H

39 H Cl 0CH ₃ CH ₃ H

40 H 0CH ₃ H CH ₃ H

41 F Cl 0CH(CH ₃ ) ₂ CH ₂ F H

42 F Cl 0CH(CH ₃ )C0 ₂ CH ₃ CH ₃ H

43 F Cl 0CH ₂ C0 ₂ C ₂ H ₅ CH ₃ H

44 F Cl 0CH ₂ C≡CH CH ₂ F H

45 F Cl 0CH(CH ₃ ) ₂ CH ₂ CN H .

46 F Cl N0 ₂ CH ₃ H

47 F Cl NH ₂ CH ₃ H

49 F Cl 0CH ₂ C0NH ₂ CH ₃ H

50 F Cl 0CH(CH ₃ ) ₂ CH ₂ CH _{2 2} F H

51 Cl Cl 0CH(CH ₃ ) ₂ H H

52 F Cl 0CH ₂ C=CI CH ₃ H

53 F Br 0CH(CH ₃ ) ₂ CH ₃ H

54 F H 0CH(CH ₃ ) ₂ CH ₃ H

55 F CH ₃ 0CH CH ₃ ) ₂ CH ₃ H

Table 1

Representative Compounds

Compound Number _X2 z _R±_ R2

56 F CF ₃ 0CH ₂ C≡CH CH ₃ H

57 F 0CH ₂ C≡CH CH ₃ H

^0C 6 ^H 5

58 F 0CH ₂ C ₆ H ₅ 0CH(CH ₃ ) ₂ CH ₃ H

59 F Cl NHCH ₃ CH ₃ H

60 F Cl N CH _{3 2} CH ₃ H

61 ¹ F Cl OS0 ₂ CH ₃ CH ₃ H

62 F Cl C0 ₂ H CH ₃ H

63 F Cl C0 ₂ CH ₃ CH ₃ H

64 F Cl C0 ₂ C ₂ H ₅ CH ₃ H

65 F Cl C0-SCH ₃ CH ₃ H

66 F Cl C0 ₂ CH ₂ CH ₂ 0CH ₃ CH ₃ H

67 F Cl C0NH ₂ CH ₃ H

68 F Cl C0NHCH ₃ CH ₃ H

69 F Cl C0N(CH ₃ ) ₂ CH ₃ H

70 F Cl C0NHCH ₂ CH ₂ OCH ₃ ^' CH ₃ H

71 F Cl C0N(CH ₃ )CH ₂ CH ₂ 0CH ₃ CH ₃ H

72 F Cl 0CH(CH ₃ ) ₂ CH ₂ C=CH H

73 F Cl 0CH(CH ₃ ) ₂ NH ₂ H

74 F Cl _. 0CH ₂ C=CH CH ₂ CN H

75 F Cl NHCHCONHCHCH- CH ₃ H ! 1 ³ CH _{3 .} C ₂ H ₅

76 F Cl OCHCONHCHCH. CH ₃ I 1 ³ CH ₃ C ₂ H ₅

77 F Cl CH- CH-

78 Cl >Ό CH. H

79 F Cl CF, CH. H

80 F Cl SH CH, H

81 F Cl SO^H CH, H

82 F Cl SCH, CH. H

Table 1

Representative Compounds

Compound Number ¹ - ² z Rl R2

83 F Cl S0CH ₃ CH, H

84 F Cl S0 ₂ CH ₃ CH H

85 F Cl SCH CH _{3 2} CH ₃ H

86 F Cl SCH ₂ C=CH CH ₃ H

87 F Br NHCH(CH ₃ C0 ₂ C ₂ H ₅ CH ₃ H

88 F Cl NHCH(CH ₃ )CONHCH ₃ CH ₃ H

89 F Cl NHCH(CH ₃ ) ₂ CH ₃ H

90 F Cl NHCH ₂ C=CH CH, H

91 Cl NH -α CH.

92 F Cl NHC0CH ₃ CH, H 93 F Cl NHC0 ₂ CH ₃ CH. H

94 Cl ° _> CH.

95 F Cl 0C ₂ H CH, H 96 F Cl 0CH ₂ 0CH ₃ CH. H

97 Cl K3 CH, H

99 Cl OCH CH.

100 Cl OCH CH.

101 Cl 0 CH. H

103 Cl o- CH.

Table 1 Representative Compounds

Compound Number χi _^ _Z Rl R2

105 Cl CH. 3-CH-

106 F Cl CH ₃ H so ₂

107 F Cl 0SO ₂ N(CH ₃ ) ₂ CH ₃ H

108 F Cl 0S0 ₂ C ₆ H ₅ CH ₃ H

109 F Cl OCH CsCH CH ₂ (CH ₂ ) ₂ F H

110 F Cl OCH CBCH CH ₂ S0 ₂ CH ₃ H

111 F Cl OCH ≡CH CH ₂ CH ₂ 0CH ₃ H

112 F Cl 0CH ₂ C≡CH CH ₃ C ₂ H ₅

113 F Cl OH H H

114 ¹ - F Cl 0CH(CH ₃ ) ₂ CH ₃ H

115 ² F Cl OCH ₂ CsCH CH ₃ H

116 ² F Cl 0CH(CH ₃ ) ₂ CH ₃ H

117 ³ F Cl 0CH ₂ C≡CH CH ₃ H

118 ³ F Cl 0CH(CH ₃ ) ₂ CH ₃ H

119 F Cl 0CH(CH ₃ ) ₂ CH ₂ 0CH ₃ H

120 F Cl 0CH(CH ₃ ) ₂ CH ₃ H

121 F 0CH ₃ OCH ^' (CH ₃ ) ₂ CH ₃ H

123 F Cl ° Γ CH ₃ H

124 F Cl 0CH ₂ SCH CH ₃ H

125 F Cl 0CH ₂ CH=CH ₂ CH ₃ H

126 F Cl 0CH ₂ C(C1)=CH ₂ CH ₃ H

127 F Cl 0-C0-CH ₃ CH ₃ H

128 F Cl 0CH ₂ C0 ₂ H CH ₃ H

Table 1

Representative Compounds

Compound Number ¹ - X ² Z -A ¹ — Λ ² .

129 F Cl 0CH ₂ C0 ₂ CH ₃ CH ₃ H

130 F Cl 0CH ₂ C0 ₂ CH ₂ ] CH ₃ H

131 F Cl 0CH ₂ C0 ₂ CH ₂ -< CH ₃ H

133 F Cl 0CH ₂ C0 ₂ ^]- CH ₃ H

135 F Cl 0CH ₂ C0 ₂ -(^ CH ₃ H

136 F Cl 0CH ₂ C0 ₂ -c^ CH ₃ H

137 F Cl 0CH-C0 -CH(CH ) _1- CH 2 2 | 2 5, 2 CH ₃ ■ H

138 F Cl 0CH ₂ C0-NH-CH ₂ 0CH ₃ CH ₃ H

139 F Cl 0CH ₂ C0-NH-CH ₂ SCH ₃ CH ₃ H

140 F Cl 0CH ₂ C0 ₂ CH ₂ CF ₃ CH ₃ H

141 F Cl 0CH(CH ₃ )C0 ₂ CH ₂ - CH ₃ H CHC1 ₂

142 F Cl 0C(CH ₃ ) ₂ C0 ₂ CH ₂ - CH ₃ H CH ^a 'CH ₂

143 F Cl OCH ₂ C0 ₂ - CH ₃ H

144 F Cl 0CH ₂ C0 ₂ CH ₂ -( CH ₃ H

Table 1

Representative Compounds

Compound Number ¹ - ² Z -Λ ¹ — _* ² .

145 F Cl 0CH ₂ C0 ₂ C ₆ H ₅ CH ₃ H

146 F Cl OCH ₂ C0 ₂ CH ₂ C ₆ H ₅ CH ₃ H

147 F Cl 0CH(CH ₃ )C0 ₂ CH ₂ CN CH ₃ H

148 F Cl OCH ₂ C0 ₂ CH C3CH CH ₃ H

149 F Cl 0CH ₂ C0 ₂ N ^» C(CH _{3 2} CH ₃ H

150 Cl 0CH ₂ CO ₂ N=CH ^: -o CH.

152 F Cl 0CH ₂ C0 ₂ N= H H

153 ^A F Cl 0CH(CH ₃ ) ₂ H H 154 ² F Cl 0CH(CH ₃ ) ₂ H H 155 ³ F Cl 0CH(CH ₃ ) ₂ H H 156 ¹ F Cl 0CH ₂ C=CH H H

F Cl 0CH ₂ C=CH H H

158 ³ F Cl 0CH ₂ O=CH H H

159 ¹ F Cl OH H H

2 160 F Cl OH H H

161 ^" F Cl OH H H

162 ¹ F Cl OH CH ₃ H 163^ F Cl OH CH ₃ H 164" F Cl OH CH ₃ H 165 ¹ F Cl 0CH(CH ₃ ) ₂ H C0 ₂ H 166 2 F Cl OCH(CH ₃ ) ₂ H C0 ₂ H 167~ F Cl 0CH(CH ₃ ) ₂ H C0 ₂ H 168 ¹ F Cl OCH ₂ CsCH H C0 ₂ H 169 ² F Cl OCH ₂ CsCH H C0 ₂ H 170" F Cl OCH ₂ C≡CH H C0 ₂ H

Table 1 Representative Compounds

Compound Number _ i_ ² z Rl R2

190 F Cl Cl CH ₃ H

191 ^• F Cl 0CSN CH ₂ CH ₃ ) ₂ CH ₃ H

192 F Cl SC0N(CH ₂ CH ₃ ) ₂ CH ₃ H

193 F Cl 0CH CH ₃ C0 ₂ C(CH _{3 3} CH ₃ H

194 F Cl NHN=C(CH _{3 2} CH ₃ H

195 F Cl 0CH ₂ 0CH ₂ CH ₂ 0CH ₃ CH ₃ H

196 F Cl 0CH(CH ₃ ) ₂ CH ₂ SCH ₃ H

197 F Cl 0CH(CH ₃ ) ₂ CH ₂ S0CH ₃ H

198 F Cl 0CH(CH ₃ C0 ₂ H CH ₃ H 199 ¹ F Br 0CH(CH ₃ ) ₂ CH ₃ H

200 F Cl 0 CH _{2 2} CH ₃ CH ₃ H

Table 1

Representative Compounds

Compound Number ² Z A ¹ . A ² .

201 F Cl 0(CH ₂ ) ₂ CH=CH ₂ CH, H

202 F Cl 0CH ₂ CN CH, H

203 ¹ F Br 0CH ₂ C=CH CH, H

204 ² F Br 0CH ₂ C=CH CH H

205 ³ F Br 0CH ₂ CsCH CH, H

206 F Cl NHCH(CH ),CH CH. H r ² I

207 F Cl 0CH(CH ₃ )C0 ₂ CH(CH CH, H

3^2

208 F Cl 0CH(CH ₃ )C0-SC ₂ H ₅ CH. H

0

209 Cl 0CHCNHS0 ₂ ^" @ ^_cl CH. H CH ₃

0 Cl

210 F . Cl 0CHCNHS0 ₂ - θ) CH ₃ H CH ₃

211 F Cl 0CH ₃ CH ₃ H

212 F Cl OCH ₂ SOCH ₃ CH ₃ H

213 F Cl 0CH ₂ S0 ₂ CH ₃ CH ₃ H

214 F Cl F H H

215 F Cl F CH ₃ H

2 216 F Br OCH(CH ₃ ) ₂ CH ₃ H

3 217 F Br 0CH(CH ₃ ) ₂ CH ₃ H

218 F Cl so ₂ cι CH ₃ H

0

219 F Cl 0CH(U-S-θ)-Cl CH ₃ H CH ₃ ^•

220 F Cl 0CH(0C ₂ H ₅ C0 ₂ C ₂ H ₅ CH ₃ H

221 F Cl OCH(OCH ₃ C0 ₂ CH ₃ CH ₃ H 0

222 F Cl SCHCNHS0 ₂ -<@>-Cl CH ₃ H

CH.

Table 1 Representative Compounds

Compound Number _ i_ ² Z Rl R ²

223 F Cl SCH(CH ₃ )C0 ₂ CH(CH ₃ ) ₂ CH, H

224 F Cl SCH(CH-)-CH CH, H 1 ^{2 3} I

225 F Cl SCH ₂ OCH ₃ CH, H

226 F Cl SCH ₂ CN CH, H

227 F Br 0CH ₂ C≡CH CH- H

228 Cl OCHCNHSO -®-OCH ₃ CH.

CH ₃

229 F Cl 0CH ₂ Si(CH _{3 3} CH, H

230 F Cl 0C ₂ H ₅ CH. H

232 F Cl NHCH CH ₃ C0 ₂ C ₂ H ₅ CH ₃ H 233 F Br 0CH(CH ₃ )C0 ₂ CH(CH 3 ^y 2 CH, H

234 . F Br 0CH ₂ 0CH ₃ CH, H

0

235 F Br OCHCNHS0 ₂ -^^-Cl CH. H

CH ₃

236 F Cl 0(CH ₂ ) ₂ F CH, H

237 F Cl 0CH ₂ CF ₃ CH. H

238 F Cl CH.

Table 1

Representative Compounds

Compound Number ¹ - Λ ² Z Rl R ²

239 F Cl 0CH ₂ C≡CH CHF, H

240 F Br H CH ₃ ^" H

241 ¹ F Br H CH ₃ H

2 242 F Cl H CH ₃ H

243 F Cl 0C(CH ₃ ) ₂ C0 ₂ C ₂ H ₅ CH, H

0-1

244 F Cl ^0CH 2-< _S ] CH,

245 F Cl CN CH H

246 F Cl CH ₃ CH H

247 F Cl CF ₃ CH H

248 F Cl C0 ₂ Na CH, H

249 F Cl S0 ₃ Na CH H

250 F Br 0CH(CH ₃ )C0 ₂ Na CH, H

1. w ¹ = o, w ² = s

2. W ¹ = S, W ² = 0

3. ¹ = W ² - S

4. X = 3-C1

TABLE 2 Characterizing Data

Compound [ Elemental Analysis

Number M.P.(°C) E mpirical Form ula C H N

1 79-81 C10H9N3O2

2 oil C ₁₀ H ₈ FN ₃ O ₂ / C 53.22 3.80 18.62 0.25 H ₂ 0 F 53.55 3.48 18.09

3 99-100 C12H10CIN3O2 C 54.66 3.82 15.94

F 54.63 3.57 16.15

4 197(d) C ₁₀ H ₇ Cl ₂ N 3θ2

5 109-110 C11H9CI2N3O2

6 202-203 C9H5CIFN 3O2

7 114-116 C10H7CIFN3O2

8 167-168 C 10H7CI2N3O2 C 44.14 2.59 Ϊ5.44 F 43;85 2.40 15.22

9 199-201 C 10H7CI2N3O3

10 163-164 C13H13CI2N3O3 C 47.29 3.97 12.73 F 47.47 3.82 12.33

11 195-197(d) C13H11 CI2N3O5/ C 42.30 3.28 11.38 0.5 H ₂ 0 F 42.38 3.31 11.75

12 111-112 C13H13CI2N3O3 C 47.29 3.97 12.73

F 47.18 4.03 12.43

13 oily solid C14H15 CI2N 3O3

14 230(d) C14H13CI2N3O3

15 103-104 C15H15CI2N3O3 C 50.58 4.24 11.80

F 50.30 4.25 11.52

16 74-75 C16H17CI2N3O3

17 on C12H11 CIFN3O3

18 82-84 Ci3H ₁₃ ClFN ₃ θ3

19 84-86 C15H15CIFN3O3

TABLE 2 (Continued)

Compound Ele m ental Analysis

Number .P.(°C) E mpirical Formula C H N

20 119-120 Ci3H ₉ Cl ₂ N3θ ₃

21 122-123 C 13H9CIFN 3O3

22 115-117 C14H1 CI2N3O5

23 oil C11H9CI2N 3O5S C 36.08 2.48 11.48 F 36.99 2.70 10.85

24 134-135 C 13H9CIFN 3O3S

25 142-144 C15H13CI2N3O2 C 50.87 3.70 11.86

F 50.37 3.95 11.66

26 cάl C13H14CI2FN 3O3 C 46.43 3.90 11.60 F 46.45 3.66 11.48

27 108-110 C15H15CI2N3O5 C 46.41 3.89 10.82 F 46.14 3.70 • 10.65

28 169-170 C ₁₂ H ₈ Cl2N ₄ θ3 C 43.46 2.58 16.95 F 43.27 2.36 16.69

29 82-83 C14H15 I2N 3O3 C 48.86 4.39 12.21 F 49.25 4.22 12.15

30 183(d) C ₁₀ H ₇ ClFN3θ ₃

31 155(d) C ₁₀ H ₆ ClN ₃ O ₄

32 157(d) C _n H ₈ ClN3θ ₅ C 48.34 2.70 18.79

F 48.32 2.81 18.51

33 229-230 C9H6CIN3O2 C 57.82 4.61 20.23 F 58.11 4.50 19.73

34 200-202 C 10H9N3O 2/ C 60.82 5.10 19.34 0.25 H ₂ 0 F 61.35 5.40 19.85

35 136-137 C11H11N3O2 C 50.54 3.39 17.68 F 50.70 3.66 17.92

36 152-154 C ₁₀ H ₈ ClN 3θ ₂ C 43.48 3.83 15.22 F 43.61 3.28 13.10

TABLE 2 (Continued)

Compound Ele m ental Analysis

Number ^' M.P.(°C) E mpirical Formula C H N

37 170-173 C ₁₀ H ₈ C1N ₃ 03/ C 50.63 4.67 17.71 1.25 H2O F 50.12 3.85 16.14

38 192(d) C10H9N3O3/H2O C 48.54 3.89 15.44

F 48.47 3.71 14.10

39 108-110 C11H10CIN3O3/ C 56.65 4.75 18.01 0.25 H2O F 56.26 4.55 17.66

40 114-116 C11H11N3O3 C 47.07 3.65 12.67 F 47.20 3.77 12.22

41 111-113 C13H12CIF2N3O3 C 47.01 3.66 11.75 F 46.51 3.69 11.31

42 100-102 C ₁₄ H ₁₃ C1FN ₃ 05

43 oil C ₁₄ H ₁₃ ClFN 3θ ₅

44 ^' oil C ₁₃ H ₈ ClF ₂ N3θ3 C 47.65 2.46 12.82 F 48.10 2.58 12.03

45 oil C ₁₄ H ₁₂ C1FN ₄ 03 C 49.64 3.57 16.54

F 49.44 3.90 14.65

46 132-134 C ₁₀ H ₆ C1FN ₄ 0 ₄ C 39.95 2.01 18.64

F 40.22 1.98 18.51

47 150-152 C ₁₀ H ₈ C1FN ₄ 0 ₂ C 44.38 2.98 20.70

F 44.30 3.29 20.40

48 127-129 Cι ₃ H ₈ BrClFN ₃ θ3

49 208(d) Cι ₂ H ₁₀ ClFN ₄ 0 ₄

50 70-71 Cι ₅ H ₁₆ ClF ₂ N3θ ₃ C 50.08 4.48 11.68 F 50.26 4.45 12.00

53 89-92 C ₁₃ Hi3BrFN ₃ 03 C 43.59 3.66 11.73 F 43.47 3.40 11.72

55 oil C ₁₄ H ₁₆ FN ₃ 0 ₃

74 oil C ₁₄ H ₈ C1FN ₄ 0 ₃

TABLE 2 (Continued)

Compound [ Elemental Analysis

Number M.P.(°C) Empirical Formula C H N

75 194-197 C ₁₇ H2iClFN ₅ θ3

76 155-156 C ₁₇ H ₂₀ C1FN ₄ 0 ₄ C 51.20 5.05 14.05 F 51.20 5.19 14.22

77 138-139 CπHgClFNsOz C 40.99 3.36 15.58 F 40.88 2.90 13.65

78 122-123 C ₁₅ H ₁₅ ClFN3θ3

82 128-131 C11H9CIFN3O2S

85 95-97 C ₁ 3H ₁ 3C1FN ₃ 0 ₂ S

86 foam C ₁₃ H9C1FN ₃ 0 ₂ S

89 solid C ₁₃ H ₁₄ C1FN ₄ 0 ₂ C 49.93 4.51 17.92 F 50.55 4.55 17.31

96 109-111 C ₁₂ H _n ClFN ₃ 0 ₄ C 45.66 3.51 13.31 F 45.45 3.35 12.92

113 >225 C ₉ H ₅ C1FN ₃ 0 ₃ C 41.96 1.96 16.31 F 43.20 2.54 14.69

114 80-81 C ₁₃ H ₁₂ C1FN ₃ 0 ₂ S C 47.35 3.97 12.74

F 47.71 4.05 12.69

119 100-102 C ₁₄ H ₁₅ C1FN ₃ 0 ₄ C 48.92 4.40 12.22

F 49.09 4.32 11.95

124 oil C ₁₂ H _n ClFN3θ ₃ S C 43.46 3.34 12.67 F 43.89 3.46 12.12

125 oil CX3HHC1FN303 C 50.09 3.56 13.48 F 50.16 3.73 13.00

182 134-135 C ₁₃ H9C1FN ₃ 02S

183 61-63 C ₁₅ H ₁₇ C1FN ₃ 03 C 52.72 5.01 12.29 F 52.55 4.95 11.53

184 oil C ₁₄ H ₁₄ C1F ₂ N ₃ 0 ₃ C 48.64 4.08 12.15 F 47.88 3.81 11.68

TABLE 2 (Continued)

Compound Elemental Analysis

Number M.P.(°C) E mpirical Formula C H N

185 73-74 CI6H19CIFN3O3 C 54.01 5.38 11.81 F 54.55 5.59 11.40

186 168-171 C ₁₀ H ₈ Cl ₂ N ₄ θ2

187 foam Cι ₄ Hι ₂ Cl ₂ N ₄ 0 ₄ / C 44.23 3.45 14.73 0.5 H2O F 44.15 3.15 14.44

188 172-173 C ₁₀ H ₆ Cl3N3θ ₂ C 39.18 1.97 13.71 F 39.83 2.35 13.55

189 182-185 C ₁₀ H ₆ C1FIN ₃ 0 ₂ C 31.48 1.59 11.01 F 33.48 1.83 11.59

190 140-142 C ₁₀ H ₆ C1 ₂ FN ₃ 0 ₂ C 41.41 2.08 14.49 F 41.65 2.13 14.05

191 120-121 C ₁₅ H ₁₆ CLFN ₄ 0 ₃ S C 46.57 4.17 14.48 F 46.47 4.02 14.29

192 156-157 C ₁₅ H ₁₆ C1FN ₄ 0 ₃ S C 46.57 4.17 14.48

F 46.66 4.14 14.37

193 86-88 C ₁₇ Hι ClFN ₃ 0 ₄ C 50.94 5.03 10.48

F 51.13 4.75 10.35

194 146-147 Ci3Hι ₃ ClFN ₅ 0 ₂ C 47.94 4.02 21.50 F 48.20 3.77 21.46

195 on Cι ₄ Hι ₅ ClFN ₃ 0 ₅ / C 45.60 4.37 11.39 0.5 H ₂ 0 F 45.67 4.07 11.20

196 95-97 Cι ₄ Hι ₅ ClFN ₃ 0 ₃ S C 46.73 4.20 11.68 F .46.76 4.24 11.39

197 138-140 Ci ₄ H ₁₅ ClFN ₃ 0 ₄ S C 44.74 4.02 11.18 F 44.15 3.78 10.99

198 123-125 C13HU CIFN 3O 5 C 45.43 3.23 12.23 F 45.14 3.23 11.95

200 88-89 Ci3H ₁₃ ClFN ₃ θ3 C 49.77 4.18 13.39 F 49.74 4.07 13.34

201 oil C14H13CIFN3O3 C 51.62 4.02 12.90 F 51.32 4.04 12.50

TABLE 2 (Continued) o mpound Elemental Analysis

Number M.P.(°C) E mpirical Formula C H N ^'

202 153-155 C ₁₂ H ₈ C1FN ₄ 0 ₃ C 46.39 2.60 18.03 F 46.08 2.49 17.81

206 gum Cι ₆ H ₁₈ ClFN ₄ 0 ₂ C 54.47 5.14 15.83

F 55.83 4.80 15.36

207 oil Cι ₆ H ₁₇ ClFN ₃ 0 ₅ C 49.82 4.44 10.89

F 47.82 4.31 10.22

208 oil C ₁₅ H ₁₅ ClFN 3θ ₄ S C 44.75 4.02 11.18

F 44.72 3.71 10.06

209 97(d) C ₁₉ Hi ₅ Cl ₂ FN ₄ 0 ₆ S/ C 42.63 3.20 10.46 H ₂ 0 F 42.61 4.06 9.44

210 solid C ₁ 9H ₁₅ Cl ₂ FN ₄ θ6S/ C 42.63 3.20 10.46 H ₂ 0 F 42.73 4.27 - 9.33

211 145-146 C _n H ₉ ClFN ₃ 03 C 46.25 3.18 14.71 F 45.90 2.80 14.46

212 164-166 C ₁₂ H _n ClFN ₃ 0 ₄ S C 41.45 3.19 12.08

F 41.45 3.07 11.67

213 154-156 C ₁₂ H _n ClFN ₃ 0 ₅ S C 39.62 3.05 11.55 F 39.30 3.15 11.13

214 233-234 C ₉ H ₄ C1F ₂ N ₃ 0 ₂ C 41.64 1.55 16.19

F 41.50 1.78 15.76

215 110-111 C ₁₀ H ₆ C1F ₂ N ₃ 02 C 43.90 2.21 15.36 F 43.64 2.13 15.21

218 123-125 Cι ₀ H ₆ Cl ₂ FN ₃ O ₄ S C 33.92 1.71 11.87

F 34.11 1.79 11.78

219 solid C ₁₉ H ₁₄ C1 ₂ FN ₃ 0 ₄ S

220 oil C ₁₆ H ₁₇ C1FN ₃ 0 ₆ C 47.83 4.27 10.46 F 47.93 4.13 10.18

221 oil C ₁₄ H ₁₃ C1FN ₃ 0 ₆

222 110(d) C ₁₉ H ₁₅ C1 ₂ FN ₄ 0 ₅ S ₂

TABLE 2 (Continued)

Compound Ele ental Analysis

Number M.P.(°C) Empirical Formula C H N

223 oil C16H17CIFN3O4S C 47.82 4.26 10.46 F 46.14 4.10 10.04

224 51-53 C ₁₅ H ₁₅ C1FN ₃ 0 ₂ S

225 95-98 C ₁₂ H _n ClFN ₃ 0 ₂ S

226 123-125 C ₁₂ H ₈ C1FN ₄ 0 ₂ S

227 123-124 Cι ₃ H ₉ BrFN3θ ₃ C 44.09 2.56 11.87 F 44.40 2.35 11.42

228 195-196 C20H18CIFN4O7S C 46.83 3.53 10.92 F 46.94 3.80 10.39

229 125-126 C14H17CIFN3O3S1 C 46.99 4.79 11.74 F 47.26 4.62 11.65

230 solid C ₁₂ H _n ClFN ₃ θ3 •

231 solid C ₂ ιHι ₈ ClFN ₄ 0 ₈ S C 46.72 3.17 10.38 F 44.35 3.72 7.43

232 oil C ₁₅ H ₁₆ C1FN ₄ 0 ₄ / C 45.29 4.81 14.08 1.5 H ₂ 0 F 45.40 4.63 13.65

233 gum Ci6Hι ₇ BrFN ₃ θ3 C 44.67 3.98 9.77

F 44.35 3.93 9.44

234 79-81 ^c 12 ^H ll ^BrFN 3°4 C 40.02 3.08 11.68 F 39.86 2.91 11.29

235 120(d) C ₁ 9H ₁₅ BrClFN ₄ 0 ₆ S/ C 39.36 2.96 9.66 H ₂ 0 F 39.62 2.78 8.49

236 134-136 C ₁₂ H ₁₀ C1F2N ₃ 03 C 45.37 3.17 13.23 F 44.88 2.86 12.87

237 gum C ₁₂ H ₈ ClF ₄ N3θ3 C 40.75 2.28 11.88 F 40.51 2.26 11.16

Table 3 Preemergence Herbicidal Activity

Compound No. " 1 2 3 4

Rate (kg/ha) 8.0 8.0 8.0 8.0

%K %c %c

Species

Cotton 0 90 90 0

Soybean 0 90 90 0

Field Corn 0 70 100 0

Wheat 0 80 100 0

Field Bindweed 0 90 100 0

Morningglory 30 90 90 0

Velvetleaf - 90 - 0

Barnyardgrass 0 90 100 0

Green Foxtail 0 100 - 0

Johnsongrass 30 80 100 0

Compound No. 5 6 7 8

Rate (kg/ha) 8.0 8.0 8.0 8.0

%c %c %C

Species

Cotton 0 10 100 ^' 0

Soybean 0 50 100 0

Field Corn 0 50 100 0

Wheat 0 50 100 10

Field Bindweed 0 50 100 20

Morningglory 0 30 100 50

Velvetleaf 0 100 100 -

Barnyardgrass 0 20 100 80

Green Foxtail 0 90 100 -

Johnsongrass 0 80 100 90

Compound No. 9 10 11 12

Rate (kg/ha) 8.0 8.0 8.0 8.0

%K %K %κ %K

Species

Cotton 20 0 0 10

Soybean 0 0 0 100

Field Corn 0 0 0 70

Wheat 10 0 0 100

Field Bindweed 0 0 0 100

Morningglory 10 0 0 100

Velvetleaf 0 100 0 100

Barnyardgrass 10 0 0 100

Green Foxtail - 100 0 100

Johnsongrass 10 0 0 100

Preemergence Herbicidal ActiviIX

Compound No. 13 15 16 17

Rate (kg/ha) 4.0 8.0 8.0 8.0

IK IK %κ ικ

Species

Cotton 0 0 0 0

Soybean 40 10 0 10

Field Corn 60 0 0 33

Wheat 40 20 0 0

Field Bindweed 50 0 100 0

Morningglory 0 0 80 ^• 0

Velvetleaf 100 100 0 -

Barnyardgrass 100 30 0 0

Green Foxtail - 100 95 -

Johnsongrass 100 30 0 0

Compound No. 18 19 20 21

Rate (kg/ha) 8.0 8.0 8.0 2.0

IC C ic IC

Species

Cotton 100 80 100 100

Soybean 100 90 100 100

Field Corn 100 100 100 100

Wheat 100 100 100 100

Field Bindweed 100 100 100 100

Morningglory 100 100 100 100

Velvetleaf 100 - 100 100

Barnyardgrass 100 100 100 100

Green Foxtail - - 100 100

Johnsongrass 100 100 100 100

Compound No. 22 23 24 25

Rate (kg/ha) 8.0 8.0 0.5 8.0 ic ic IC %C

Species

Cotton 100 90 100 0

Soybean 100 90 100 0

Field Corn 90 100 100 0

Wheat 0 100 100 20

Field Bindweed 100 80 100 0

Morningglory 70 90 90 20

Velvetleaf 90 100 100 0

Barnyardgrass 90 100 100 80

Green Foxtail 90 100 100 90

Johnsongrass 80 100 100 80

Table 3

Preemergence Herbicidal Activity

Compound No. 26 27 28 29

Rate (kg/ha) 8.0 4.0 4.0 8.0

IC C IC IC

Species

Cotton 20 90 50 60

Soybean 40 30 50 90

Field Corn 90 80 100 90

Wheat 90 30 70 60

Field Bindweed 70 100 10 90

Morningglory 50 40 50 70

Velvetleaf 100 100 100 100

Barnyardgrass 80 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 90 100 80 100

Compound No. 30 31 32 33

Rate (kg/ha) 8.0 8.0 8.0 8.0 C C C C

Species

Cotton. 100 0 0 40

Soybean 100 0 0 40

Field Corn 100 0 0 30

Wheat 100 0 0 0

Field Bindweed 100 0 0 0

Morningglory 100 0 0 0

Velvetleaf 100 0 0 0

Barnyardgrass 100 0 0 ^• 0

Green Foxtail 100 0 0 0

Johnsongrass 100 0 0 0

Compound No. 34 35 36 37

Rate (kg/ha) 8.0 8.0 4.0 8.0 C IC IC IC

Species

Cotton 0 90 90 0

Soybean 0 80 90 70

Field Corn 0 80 100 20

Wheat 0 70 100 0

Field Bindweed 0 40 100 0

Morningglory 0 80 100 0

Velvetleaf 0 100 100 0

Barnyardgrass 0 90 100 0

Green Foxtail 0 90 100 0

Johnsongrass 0 80 100 0

Table 3

Preemergence Herbicidal Activity

Compound No. 38 39 40 41 Rate (kg/ha) 8.0 8.0 8.0 0.5

IC C IC IC

Species

Cotton 0 20 90 50

Soybean 0 50 90 90

Field Corn 0 60 100 90

Wheat 0 10 90 100

Field Bindweed 0 0 90 80

Morningglory 0 90 80 90

Velvetleaf 0 90 100 100

Barnyardgrass 0 50 100 100

Green Foxtail 0 80 100 100

Johnsongrass 0 20 100 100

Compound No. 42 43 44 45 Rate (kg/ha) 1.0 1.0 0.5 4.0 C IC IC IC

Species

Cotton 100 40 100 100

Soybean 100 70 100 100

Field Corn 30 60 100 100

Wheat 60 0 100 100

Field Bindweed 100 100 100 100

Morningglory 100 100 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 100 90 100 100

Compound No. 46 47 48 49 Rate (kg/ha) 4.0 4.0 0.25 2.0

IC C IC

Species

Cotton 10 10 0 100

Soybean 90 100 0 100

Field Corn 10 30 50 100

Wheat 10 30 0 20

Field Bindweed 0 20 0 100

Morningglory 10 40 0 100

Velvetleaf 100 100 100 100

Barnyardgrass 0 70 80 100

Green Foxtail 90 60 90 100

Johnsongrass 10 70 60 100

Table 3

Preemergence Herbicidal Activity

Compound No. 50 53 55 73

Rate (kg/ha) 2.0 0.25 0.5 4.0

IC C IC IC

Species

Cotton 80 0 30 40

Soybean 50 10 20 50

Field Corn 90 95 90 40

Wheat 100 100 0 90

Field Bindweed 40 80 30 100

Morningglory 100 100 20 100

Velvetleaf 100 95 100 100

Barnyardgrass 100 100 30 100

Green Foxtail 100 100 40 100

Johnsongrass 100 95 20 90

Compound No. 75 76 77 78

Rate (kg/ha) 1.0 1.0 1.0 1.0

IC IC IC C

Species

Cotton 100 90 100 30

Soybean 100 80 100 100

Field Corn 100 100 100 80

Wheat 100 90 90 70

Field Bindweed 100 90 100 40

Morningglory 100 90 100 50

Velvetleaf 100 100 100 100

Barnyardgrass 100 90 100 100

Green Foxtail 100 100 100 100

Johnsongrass 100 100 100 100

Compound No. 82 85 86 89

Rate (kg/ha) 2.0 0.5 0.125 0.5

IC C • C C

Species

Cotton 100 30 20 70

Soybean 100 30 20 80

Field Corn 100 90 90 95

Wheat 95 30 40 95

Field Bindweed 95 20 20 80

Morningglory 100 20 30 40

Velvetleaf 100 100 100 100

Barnyardgrass 100 80 95 95

Green Foxtail 100 95 90 100

Johnsongrass 100 40 60 100

Table 3

Preemergence Herbicidal Activity

Compound No. 96 113 114 119

Rate (kg/ha) 0.5 8.0 1.0 0.5

IC C IC C

Species

Cotton 70 0 40 10

Soybean 70 50 80 50

Field Corn 100 20 100 80

Wheat 100 10 100 20

Field Bindweed 100 10 70 20

Morningglory 100 10 90 30

Velvetleaf 100 20 100 100

Barnyardgrass 100 60 100 40

Green Foxtail 100 20 100 70

Johnsongrass 90 30 100 70

Compound No. 124 125 182 183

Rate (kg/ha) 0.5 1.0 0.5 0.5

IC IC C IC

Species

Cotton 100 90 100 0

Soybean 100 100 100 0

Field Corn 100 100 100 20

Wheat 100 100 100 30

Field Bindweed 100 100 100 30

Morningglory 100 100 90 0

Velvetleaf 100 100 100 80

Barnyardgrass 100 100 100 80

Green Foxtail 100 100 100 90

Johnsongrass 100 100 100 90

Compound No. 184 185 186 187

Rate (kg/ha) 0.5 0.5 4.0 4.0

IC IC C IC

Species

Cotton 10 10 10 30

Soybean 30 0 10 20

Field Corn 100 10 10 20

Wheat 60 0 0 20

Field Bindweed 30 0 0 0

Morningglory 30 10 0 20

Velvetleaf 90 10 80 40

Barnyardgrass 90 20 20 10

Green Foxtail 100 20 0 10

Johnsongrass 90 0 0 10

Table 3

Preemergence Herbicidal Activity

Compound No. 188 189 190 191

Rate (kg/ha) 2.0 1.0 1.0 8.0

IC IC C IC

Species

Cotton 20 30 40 60

Soybean 10 30 30 60

Field Corn 20 40 90 70

Wheat 0 30 40 40

Field Bindweed 10 30 20 80

Morningglory 20 20 30 60

Velvetleaf 80 100 100 100

Barnyardgrass 0 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 30 90 100 100

Compound No. 192 193 194 195

Rate (kg/ha) 8.0 8.0 4.0 0.5

IC C C IC

Species

Cotton 90 100 100 80

Soybean 60 100 100 70

Field Corn 100 100 100 100

Wheat 60 100 100 70

Field Bindweed 100 100 100 80

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 90

Compound No. 196 197 198 200

Rate (kg/ha) 2.0 4.0 1.0 1.0

IC IC IC IC

Species

Cotton 20 50 100 60

Soybean 20 50 95 50

Field Corn 90 100 50 100

Wheat 30 80 80 90

Field Bindweed 10 60 90 70

Morningglory 20 40 100 100

Velvetleaf 80 100 100 100

Barnyardgrass 100 50 100 100

Green Foxtail 100 90 100 100

Johnsongrass 90 90 95 100

Table 3

Preemergence Herbicidal Activity

Compound No. 201 202 206 207

Rate (kg/ha) 1.0 1.0 4.0 1.0

IC %c C C

Species

Cotton 50 90 30 100

Soybean 50 90 70 100

Field Corn 100 90 95 70

Wheat 80 50 80 90

Field Bindweed 80 100 100 100

Morningglory 50 100 80 80

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 80 100

Green Foxtail 100 100 100 100

Johnsongrass 90 90 100 100

Compound No. 208 209 210 211

Rate (kg/ha) 1.0 1.0 1.0 2.0

IC IC IC IC

Species

Cotton 100 95 100 100

Soybean 100 80 70 95

Field Corn 80 10 20 100

Wheat 80 30 60 100

Field Bindweed 100 100 100 100

Morningglory 100 100 95 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 70 100

Green Foxtail 100 95 80 100

Johnsongrass 95 90 70 100

Compound No. 212 213 214 215

Rate (kg/ha) 2.0 4.0 8.0 4.0 C IC IC C

Species

Cotton 100 100 10 100

Soybean 100 100 50 100

Field Corn 100 100 50 100

Wheat 100 100 30 100

Field Bindweed 100 100 90 100

Morningglory 100 100 70 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 20 100

Green Foxtail 100 100 100 100

Johnsongrass 100 100 60 100

Table 3

Preemergence Herbicidal Activity

Compound No. 218 219 220 221

Rate (kg/ha) 8.0 1.0 2.0 2.0 C IC C IC

Species

Cotton 20 20 30 70

Soybean 0 30 90 95

Field Corn 20 30 70 70

Wheat 10 20 0 30

Field Bindweed 50 30 30 100

Morningglory 20 50 95 100

Velvetleaf 100 100 80 80

Barnyardgrass 30 90 90 95

Green Foxtail 100 100 90 100

Johnsongrass 90 60 70 95

Compound No. 222 223 224 225

Rate (kg/ha) 1.0 1.0 1.0 0.25

IC C IC IC

Species

Cotton 70 100 30 10

Soybean 40 100 70 20

Field Corn 30 95 80 95

Wheat 10 70 20 90

Field Bindweed 90 90 20 80

Morningglory 100 100 90 100

Velvetleaf 100 100 100 100

Barnyardgrass 0 95 100 100

Green Foxtail 0 100 100 90

Johnsongrass 0 95 80 40

Compound No. 226 227 228 229

Rate (kg/ha) 2.0 0.125 0.5 4.0 C C C IC

Species

Cotton 100 50 90 20

Soybean 100 30 95 30

Field Corn 100 100 0 80

Wheat 100 100 30 50

Field Bindweed 90 95 100 80

Morningglory 100 70 100 95

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 70 90

Green Foxtail 100 100 95 100

Johnsongrass 100 100 100 95

Table 3

P:reemergence Herbicidal Activity

Compound No. 230 231 232 233 234

Rate (kg/ha) 2.0 0.5 2.0 0.5 0.125 C C IC IC IC

Species

Cotton 90 80 100 70 80

Soybean 95 70 100 95 10

Field Corn 100 10 40 40 95

Wheat 100 20 90 60 100

Field Bindweed 100 100 100 100 100

Morningglory 95 90 60 95 100

Velvetleaf 100 100 100 100 100

Barnyardgrass 100 20 70 100 100

Green Foxtail 100 30 100 100 100

Johnsongrass 100 70 30 80 100

Table 4

Postemergence Herbicidal Activity

Compound No. 1 2 3 4

Rate (kg/ha) 8.0 8.0 8.0 8.0

IK IC IK IC

Species

Cotton 0 30 100 0

Soybean 0 40 0 20

Field Corn 0 30 30 0

Wheat 0 30 50 10

Field Bindweed 0 40 100 0

Morningglory 0 40 100 0

Velvetleaf 0 60 100 0

Barnyardgrass 0 0 30 30

Green Foxtail 0 20 100 0

Johnsongrass 0 0 100 0

Compound No. 5 6 7 8

Rate (kg/ha) 8.0 8.0 8.0 8.0 C IC C IK

Species

Cotton 20 60 100 0

Soybean 20 60 100 0

Field Corn 0 70 100 0

Wheat 20 20 100 0.

Field Bindweed 0 30 100 0

Morningglory 0 30 100 0

Velvetleaf 0 60 100 0

Barnyardgrass 0 20 100 100

Green Foxtail 0 100 100 -

Johnsongrass 0 40 100 100

Compound No. 9 10 11 12

Rate (kg/ha) 8.0 8.0 8.0 8.0 K IK K K

Species

Cotton 0 20 0 100

Soybean 0 0 0 100

Field Corn 0 0 0 100

Wheat 0 0 0 100

Field Bindweed 0 0 10 100

Morningglory 0 20 0 100

Velvetleaf 0 100 0 100

Barnyardgrass 0 0 0 100

Green Foxtail 0 0 0 100

Johnsongrass 0 0 10 100

Table 4

Postemergence Herbicidal Activity

Compound No. 13 15 16 17

Rate (kg/ha) 4.0 8.0 8.0 8.0 K K IK K

Species

Cotton 70 95 20 0

Soybean 0 0 0 0

Field Corn 30 0 30 30

Wheat 0 0 0 0

Field Bindweed 70 0 70 70

Morningglory 20 60 10 10

Velvetleaf 100 100 100 100

Barnyardgrass 0 20 20 20

Green Foxtail - 100 100 100

Johnsongrass 90 60 100 100

Compound No. 18 19 20 21

Rate (kg/ha) 8.0 8.0 8.0 0.25

I IK K IC

Species

Cotton 100 - 100 100 100

Soybean 100 100 100 70

Field Corn 100 100 100 100

Wheat 100 100 100 100

Field Bindweed 100 100 100 100

Morningglory 100 100 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 100 100 100 100

Compound No. 22 23 24 25

Rate (kg/ha) 8.0 8.0 0.5 8.0

IC IC IC IC

Species

Cotton 100 80 100 30

Soybean 90 100 80 40

Field Corn 70 100 90 0

Wheat 20 90 80 40

Field Bindweed 90 50 100 0

Morningglory 90 70 100 10

Velvetleaf 100 100 100 50

Barnyardgrass 100 100 100 30

Green Foxtail 100 100 100 100

Johnsongrass 30 100 100 30

Table 4

Postemergence Herbicidal Activi 11

Compound No. 26 ^• 27 28 29

Rate (kg/ha) 8.0 8.0 8.0 8.0 C IC IC C

Species

Cotton 90 100 80 100

Soybean 60 90 90 70

Field Corn 90 70 100 100

Wheat 100 100 40 100

Field Bindweed 60 100 50 100

Morningglory 50 80 80 100

Velvetleaf 100 100 90 100

Barnyardgrass 90 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 90 100 70 100

Compound No. 30 31 32 33

Rate (kg/ha) 8.0 8.0 8.0 8.0 C C IC IC

Species

Cotton 100 10 10 10

Soybean 90 20 10 30

Field Corn 100 20 20 20

Wheat 80 20 10 20

Field Bindweed 100 0 10 20

Morningglory 100 10 10 30

Velvetleaf 100 0 10 20

Barnyardgrass 100 30 20 20

Green Foxtail 100 20 10 20

Johnsongrass 100 30 20 20

Compound No. 34 35 36 37

Rate (kg/ha) 8.0 8.0 8.0 8.0

IC C IC C

Species

Cotton 20 90 90 0

Soybean 10 80 90 0

Field Corn 20 10 90 0

Wheat 20 30 30 0

Field Bindweed 10 30 100 0

Morningglory 20 10 100 10

Velvetleaf 20 100 100 0

Barnyardgrass 30 30 80 0

Green Foxtail 10 80 100 50

Johnsongrass 20 30 80 0

Table 4

Postemergence : Herbicidal Activity

Compound No. 38 39 40 41

Rate (kg/ha) 8.0 8.0 8.0 0.5

IC C C IC

Species

Cotton 10 30 60 100

Soybean 10 40 60 70

Field Corn 20 30 30 80

Wheat 10 30 30 70

Field Bindweed 10 30 40 100

Morningglory 10 20 60 100

Velvetleaf 0 60 80 100

Barnyardgrass 10 40 30 80

Green Foxtail 30 70 90 100

Johnsongrass 0 50 50 90

Compound No. 42 43 44 45

Rate (kg/ha) 1.0 1.0 0.5 4.0

IC IC IC IC

Species

Cotton 100 100 100 100

Soybean 100 90 100 90

Field Corn 70 80 100 100

Wheat 100 20 100 100

Field Bindweed 100 100 100 100

Morningglory 100 90 100 100.

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 100 100

Green Foxtail 100 100 100 100

Johnsongrass 100 60 100 100

Compound No. 46 47 48 49

Rate (kg/ha) 4.0 4.0 0.25 2.0

IC IC IC IC

Species

Cotton 10 90 50 100

Soybean 10 90 30 100

Field Corn 0 10 0 100

Wheat 0 10 0 10

Field Bindweed 10 50 10 90

Morningglory 40 30 10 90

Velvetleaf 0 90 90 100

Barnyardgrass 10 0 0 100

Green Foxtail 50 90 20 100

Johnsongrass 20 0 0 50

Table 4

Postemergence Herbicidal Activity

Compound No. 50 53 55 73

Rate (kg/ha) 2.0 0.25 0.5 4.0

IC C IC C

Species

Cotton 80 90 40 80

Soybean 50 80 30 50

Field Corn 100 90 10 40

Wheat 70 40 20 80

Field Bindweed 80 80 20 80

Morningglory 20 80 40 80

Velvetleaf 100 100 80 100

Barnyardgrass 90 90 10 20

Green Foxtail 100 100 30 90

Johnsongrass 90 60 0 80

Compound No. 75 76 77 78

Rate (kg/ha) 1.0 1.0 4.0 1.0 C C C IC

Species

Cotton ^' 100 90 100 100

Soybean 100 90 90 60

Field Corn 80 40 80 20

Wheat 70 30 50 40

Field Bindweed 100 100 100 80

Morningglory 100 90 100 80

Velvetleaf 100 100 100 100

Barnyardgrass 80 30 100 50

Green Foxtail 100 80 100 50

Johnsongrass 80 50 80 40

Compound No. 82 85 86 89

Rate (kg/ha) 2.0 0.5 0.125 0.5

IC C IC IC

Species

Cotton 95 95 95 - 80

Soybean 95 90 70 90

Field Corn 100 80 90 95

Wheat 90 50 70 80

Field Bindweed 100 95 95 70

Morningglory 90 80 100 60

Velvetleaf 100 100 100 100

Barnyardgrass 100 70 90 90

Green Foxtail 100 100 100 90

Johnsongrass 80 60 30 90

Table 4

Postemergence Herbicidal Activity

Compound No. 96 113 114 119

Rate (kg/ha) 0.5 8.0 1.0 0.5

IC IC C IC

Species

Cotton 100 0 100 70

Soybean 90 20 90 30

Field Corn 100 20 100 20

Wheat 90 10 50 10

Field Bindweed 100 10 100 70

Morningglory 100 10 100 40

Velvetleaf 100 20 100 100

Barnyardgrass 100 20 100 30

Green Foxtail 100 10 100 40

Johnsongrass 90 10 70 30

Compound No. 124 125 182 183

Rate (kg/ha) 4.0 1.0 0.5 0.5

IC IC IC C

Species

Cotton 100 100 100 80

Soybean 100 80 80 60

Field Corn 100 100 90 100

Wheat 100 90. 80 30

Field Bindweed 100 100 100 30

Morningglory 100 100 100 40

Velvetleaf 100 100 100 90

Barnyardgrass 100 100 100 10

Green Foxtail 100 100 100 90

Johnsongrass 100 80 100 30

Compound No. 184 185 186 187

Rate (kg/ha) 0.5 0.5 4.0 4.0 C IC C IC

Species

Cotton 90 30 30 30 ^•

Soybean 60 10 20 10

Field Corn 100 30 10 20

Wheat 70 10 10 20

Field Bindweed 80 10 20 0

Morningglory 70 30 0 0

Velvetleaf 100 50 30 10

Barnyardgrass 50 10 20 0

Green Foxtail 100 30 0 0

Johnsongrass 80 0 0 0

Table 4

Postemergence Herbicidal Activity

Compound No. 188 189 190 191

Rate (kg/ha) 2.0 1.0 1.0 8.0

IC IC IC C

Species

Cotton 30 80 80 80

Soybean 10 60 80 60

Field Corn 10 20 40 90

Wheat 20 20 20 50

Field Bindweed 30 30 50 30

Morningglory 10 70 90 70

Velvetleaf 100 100 100 100

Barnyardgrass 10 20 80 90

Green Foxtail 20 40 90 90

Johnsongrass 0 20 30 80

Compound No. 192 193 194 195

Rate (kg/ha) 8.0 8.0 4.0 0.5

IC IC C C

Species

Cotton 90 100 100 70

Soybean 50 100 80 30

Field Corn 90 100 100 30

Wheat 50 100 40 30

Field Bindweed 30 100 90 50

Morningglory 100 100 100 80

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 90 90

Green Foxtail 100 100 80 100

Johnsongrass 100 100 30 80

Compound No. 196 197 198 200

Rate (kg/ha) 2.0 4.0 1.0 1.0

IC IC C IC

Species

Cotton- 90 90 100 100

Soybean 70 30 100 80

Field Corn 20 0 95 95

Wheat 0 0 100 90

Field Bindweed 60 0 100 100

Morningglory 30 0 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 90 30 100 100

Green Foxtail 100 70 100 100

Johnsongrass 0 80 100 95

Table 4

Postemergence Herbicidal Activity

Compound No. 201 202 206 207

Rate (kg/ha) 1.0 1.0 4.0 1.0

IC IC IC C

Species

Cotton 95 100 90 100

Soybean 70 90 80 100

Field Corn 100 100 100 50

Wheat 70 40 40 90

Field Bindweed 100 100 95 100

Morningglory 100 100 90 90

Velvetleaf 100 100 100 100

Barnyardgrass 95 100 95 100

Green Foxtail 100 100 100 100

Johnsongrass 40 80 100 80

Compound No. 208 209 210 211

Rate (kg/ha) 1.0 1.0 1.0 2.0 C IC IC IC

Species

Cotton 100 100 50 100

Soybean 100 90 20 95

Field Corn 20 20 10 100

Wheat 90 30 20 100

Field Bindweed 100 100 100 100.

Morningglory 100 100 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 95 100

Green Foxtail 100 100 95 100

Johnsongrass 70 70 60 100

Compound No. 212 213 214 215

Rate (kg/ha) 2.0 4.0 8.0 4.0

IC IC IC IC

Species

Cotton 100 100 30 100

Soybean 100 100 50 100

Field Corn 100 100 80 100

Wheat 100 100 30 100

Field Bindweed 100 100 90 100

Morningglory 100 100 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 60 100

Green Foxtail 100 100 95 100

Johnsongrass 100 100 80 100

Table 4

Postemergence Herbicidal A< :tivity

Compound No. 218 219 220 221

Rate (kg/ha) 8.0 1.0 2.0 2.0 C IC C C

Species

Cotton 70 95 80 95

Soybean 60 60 100 95

Field Corn 30 70 90 95

Wheat 10 50 40 50

Field Bindweed 90 80 90 100

Morningglory 40 90 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 0 70 100 100

Green Foxtail 90 95 100 100

Johnsongrass 0 30 50 100

Compound No. 222 223 224 225

Rate (kg/ha) 1.0 1.0 1.0 0.25 C IC IC IC

Species

Cotton 95 100 100 100 ^•

Soybean 80 100 80 80

Field Corn 40 40 40 60

Wheat 30 95 40 60

Field Bindweed 100 100 60 95

Morningglory 95 100 50 90

Velvetleaf 100 100 100 100

Barnyardgrass 0 100 10 60

Green Foxtail 60 100 40 90

Johnsongrass 0 100 10 40

Compound No. 226 227 228 229

Rate (kg/ha) 2.0 0.125 0.5 4.0

IC IC IC IC

Species

Cotton 100 90 100 90

Soybean 95 60 100 60

Field Corn 100 90 30 30

Wheat 100 90 80 50

Field Bindweed 100 100 100 80

Morningglory 100 95 100 100

Velvetleaf 100 100 100 100

Barnyardgrass 100 100 100 90

Green Foxtail 100 100 95 95

Johnsongrass 100 95 95 70

Table 4

Postemerg'ence Herbicidal Activity

Compound No. 230 231 232 233 234

Rate (kg/ha) 2.0 0.5 2.0 0.5 0.125

IC C IC C C

Species

Cotton 100 40 100 95 70

Soybean 100 80 100 95 60

Field Corn 100 0 100 40 80

Wheat 100 50 100 80 70

Field Bindweed 100 100 100 100 70

Morningglory 100 100 100 80 80

Velvetleaf 100 100 100 95 100

Barnyardgrass 100 20 100 100 80

Green Foxtail 100 40 . 100 100 95

Johnsongrass 95 10 100 30 40