Herbicidal substituted-phenyl-1,2,4-triazol-5(1H)-thiones and -ones

The invention described in this application pertains to weed control in agriculture, horticulture, or other fields where there is a desired to control unwanted plant growth. More specifically, the present application describes novel herbicidal substituted-phenyl-1,2,4-triazol-5(1H)-thiones and -ones, herbicidal compositions containing the new compounds, methods of preparing these compounds, and methods for controlling undesired plant growth by preemergence and/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.
A number of 1,2,4-triazol-thiones and -ones are known in the art. French Patent Application 2,546,887, published Dec. 7, 1984, for example, discloses (as reported in Derwent Abstracts, accession no. 85-020678/04) pesticidal triazol-3-thiones of the Formula ##STR3##
wherein R.sup.1 is alkyl or aryl, and R.sup.2 is aryl, benzyl, 2-hydroxyethyl, anilino or aroylamino.
Belgium Patent Application 802,530, published Jan. 21, 1974, discloses (as reported in Derwent Abstracts, accession no. 07240V/05) insecticidal and acaricidal compounds of the Formula ##STR4## where R.sup.6 is R.sup.4 or --CH.sub.2 --X--P(Y)R.sup.1 R.sup.2, R.sup.8 is R.sup.5 or --CH.sub.2 --X--P(Y)R.sup.1 R.sup.2, only one of R.sup.6 and R.sup.8 is --CH.sub.2 --X--P(Y)R.sup.1 R.sup.2, R.sup.7 is R.sup.3 and is F.sub.2 CCl or 1-6C-fluoroalkyl when R.sup.8 is R.sup.5, X, Y and Z are O or S and Z is O when R.sup.8 is R.sup.5, R.sup.1 is 1-4C-alkyl, (1-4C-alkyl)amino or 1-4C-alkoxy, R.sup.2 is 1-4C-alkyl, (1-4C-alkyl)amino, 1-4C-alkoxy or Ph, R.sup.3 and R.sup.4 are each 1-6C-alkyl or 3-8C-cycloalkyl and are 3-4C-alkenyl when R.sup.6 is R.sup.4, R.sup.5 is 1-6C-alkyl, 3-8C-cycloalkyl or phenyl optionally substituted by halogen or methyl.
U.S. Pat. No. 3,922,162, issued Nov. 25, 1975, discloses herbicidal compounds of the Formula ##STR5##
wherein R is alkyl, X is selected from the group consisting of alkyl, alkoxy, alkylthio, halogen, haloalkyl, and nitro, and n is an integer from 1 to 3.
Belgium Patent Application 876,557, published Nov. 26, 1979, discloses (as reported in Derwent Abstracts, accession no. 85976B/48) fungicidal compounds of the Formula ##STR6## wherein R.sup.1 is H or R.sup.2, R.sup.2 is cycloalkyl or 1-6C alkyl, or R.sup.1 and R.sup.2, together with the triazoline ring, form a spiran optionally substituted by methyl in the 1 and 3 positions, R.sup.3 is 1-6C-alkyl, phenyl, phenyl substituted by 1-3 alkyl groups or NO.sub.2, and X is O or S, provided that when X=O, then R.sup.4 =H, phenyl or phenyl substituted by 1-3 halogens, and when X=S, then R.sup.4 =1-6C-alkyl, phenyl or phenyl substituted by 1-3 halogens.
Grashey et al., Chem-Ztg., Vol. 100(11), p. 496 (1976) discloses (as reported in Chemical Abstracts, on-line registry no. 13136-33-9) 2,4-dihydro-5-methyl-2,4-diphenyl-3H-1,2,4-triazol-3-thione, a compound of the Formula ##STR7## and 2,4-dihydro-4,5-diphenyl-2-(phenylmethyl)-3H-1,2,4-triazole-3-thione, a compound of the Formula ##STR8## These compounds appear (based on Chemical Abstracts, accession no. CA86(19):139948j) to be intermediates in disclosed synthesis processes.
Lanquist, J. Chem. Soc. C, (2), pp. 323-4 (1970) discloses (see also Chemical Abstracts, on-line registry no. 25976-83-4) as an intermediate 1,3-dimethyl-4-phenyl-.DELTA..sup.2 -1,2,4-triazolin-5-thione, a compound of the Formula ##STR9##
Abdel-Fattah et al., Egypt. J. Chem., Vol. 27(3) pp. 321-8 (1985) discloses (as reported in Chemical Abstracts on-line registry no. 54559-49-8) 4,5-dihydro-3,4-diphenyl-5-thioxo-1H-1,2,4-triazol-1-propanenitrile, a compound of the Formula ##STR10## This compound appears (based on Chemical Abstracts, accession no. CA:105(25):226455a) to be the product of a reaction involving 1,2,4-triazol-5-thiones.
Khripak et al., Khim. Geterosikl. Soedin., (7), pp. 1000-2 (1975) discloses (as reported in Chemical Abstracts on-line registry no. 56807-56-8) 2,4-dihydro-2-(hydroxymethyl)-4,5-diphenyl-3H-1,2,4-triazol-3-thione, a compound of the Formula ##STR11## This compound appears (based on Chemical Abstracts, accession no. CA83(17):147418q) to be the product of a reaction involving 1,2,4-triazol-5-thiones.
Giudicelli et al., Bull. Soc. Chim. Fr., (3), pp. 870-4 (1969) discloses (as reported in Chemical Abstracts on-line registry no. 960-57-6) 1-methyl-3,4-diphenyl-.DELTA..sup.2 -1,2,4-triazoline-5-thione, a compound of the Formula ##STR12##
German Patentschrift 160,447, published Aug. 3, 1983 discloses herbicidal 1,2,4-triazolin-5-ones of the Formula ##STR13##
wherein R.sup.1 and R.sup.2 are each H or optionally substituted alkyl, aryl, aralkyl, or cycloalkyl, where typical substitutions are one or more of halo, hydroxy, amino (optionally substituted by alkyl and/or aryl), alkoxy, aryloxy, alkylthio or arylthio.
The herbicidal compounds of the present invention are compounds of Formula I ##STR14## wherein:
Ar is selected from ##STR15##
R is selected from haloalkyl;
R.sup.1 is selected from alkyl;
R.sup.2 is selected from hydrogen, halogen, alkyl, haloalkoxy, haloalkyl, alkoxy, alkynyl, alkylthio, nitro, amino and cyano;
R.sup.3 is selected from hydrogen, halogen, alkyl, alkoxy, alkynyl, nitro, amino, mono- or disubstituted amino, cyano and hydroxy;
R.sup.4 is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, trimethylsilylalkynyl, cyano, nitro, amino, haloalkyl, mono- or disubstituted amino, tetralkylammonium halide, hydroxy, alkoxy, phenoxy, benzyl, benzyloxy, alkylthio, alkylsulfonyl, alkylcarbonyl, phenylcarbonyl, pyrrolidinyl, piperidinyl, morpholinyl, alkylthioalkoxy, vinyloxy, alkylvinyloxy, halovinyloxy, allyloxy, cycloalkylalkoxy, cycloalkoxy, and haloalkoxy;
R.sup.5 is selected from hydrogen, halogen, alkyl, alkoxy, haloalkoxy and haloalkyl; or
R.sup.3 and R.sup.4 or R.sup.4 and R.sup.5 may be joined to form --OCH.sub.2 O--, --CH.sub.2 C(CH.sub.3).sub.2 O--, --OC(CH.sub.3)(CH.sub.2 CH.sub.3)O--, --N(CH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.2 CH.sub.3)--, --OCH.sub.2 CH.sub.2 N[CH(CH.sub.3).sub.2 ]--, --OCH.sub.2 CH.sub.2 O--, --OC(CH.sub.3).sub.2 O--, --C(O)C(CH.sub.3).sub.2 O-- or --CH.sub.2 CH.sub.2 CH.sub.2 O--,
R.sup.6 is selected from hydrogen, halogen, alkyl and alkylthio;
R.sup.7 and R.sup.8 are alkyl, not necessarily the same; and
W is selected from S and O.
As used herein, the term halogen, employed alone or in combination with other terms, denotes a species selected from the group consisting of chlorine, fluorine and bromine.
It is often preferable that any alkyl group or alkyl portion of any group herein have 1-6 carbon atoms, and that any alkenyl or alkynyl group or alkenyl or alkynyl portion of any group herein have 3-6 carbon atoms.
A preferred subgenus of this invention comprises the compounds of Formula I in which:
R is fluoroalkyl, most preferably CF.sub.3 ;
R.sup.1 is CH.sub.3 ;
W is S; and
Ar is ##STR16## wherein:
R.sup.2 is halogen, alkyl, haloalkyl or haloalkoxy, more preferably haloalkoxy, most preferably OCHF.sub.2 ;
R.sup.3 is hydrogen, halogen or alkyl, more preferably halogen, most preferably F or Cl;
R.sup.4 is alkoxy, vinyloxy, cycloalkoxy or mono- or disubstituted amino, more preferably cycloalkoxy or alkoxy, most preferably cyclobutoxy or isopropoxy; or
R.sup.3 and R.sup.4 are joined to form --CH.sub.2 C(CH.sub.3).sub.2 O--, --OC(CH.sub.3)(CH.sub.2 CH.sub.3)O-- or --C(O)C(CH.sub.3).sub.2 O--;
R.sup.5 is halogen, alkyl or haloalkoxy, most preferably difluoromethoxy; and
R.sup.6 is preferably hydrogen or halogen, more preferably halogen, most preferably F, Cl.
Specific embodiments exhibiting particularly effective weed control at low preemergence and/or postermergence application rates and/or showing a selectivity particularly favorable to certain crop plants include compounds of the Formula ##STR17## wherein: R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is ##STR18## R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is NH(CH.sub.2 CH.sub.3);
R is CF.sub.3, R.sup.2 is SCH.sub.3, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.5 is Cl;
R is CF.sub.3, R.sup.2 is Cl, R.sup.3, R.sup.5 and R.sup.6 are H, and R.sup.4 is N(CH.sub.2 CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.3, R.sup.5 and R.sup.6 are H, and R.sup.4 is N(CH.sub.2 CH.sub.3)(CH.sub.2 CF.sub.3);
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH.sub.2 CH.sub.2 Br;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is ##STR19## R is CF.sub.3, R.sup.2 is OCHF.sub.2, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.5 is Cl;
R is CF.sub.3, R.sup.2, R.sup.3, R.sup.5, and R.sup.6 are F, and R.sup.4 is N(CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.2, and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH.dbd.CF.sub.2 ;
R is CF.sub.3, R.sup.2 is F, R.sup.3 and R.sup.6 are H, R.sup.4 is N(CH.sub.2 CH.sub.3).sub.2, and R.sup.5 is Cl;
R is CF.sub.3, R.sup.2, R.sup.3, R.sup.5, and R.sup.6 are F, and R.sup.4 is N(CH.sub.2 CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OC(CH.sub.3).sub.3 ;
R is CF.sub.3, R.sup.2 is Cl, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.5 is CH.sub.3 ;
R is CF.sub.3, R.sup.2 is F, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH.sub.3, and R.sup.5 is Cl;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH.sub.2 CH.dbd.CH.sub.2 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is N(CH.sub.2 CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 is NH.sub.2, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.6 is H;
R is CF.sub.3, R.sup.2 is F, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.5 is Cl;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 are R.sup.6 are H, and R.sup.4 is OCH.sub.2 CH.sub.2 CH.sub.3 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Br, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH(CH.sub.3).sub.2 ;
R is CHF.sub.2, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH(CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH.sub.2 CH.sub.3 ;
R is CF.sub.3, R.sup.2 is Cl, R.sup.3 and R.sup.4 are joined to form --C(O)C(CH.sub.3).sub.2 O--, R.sup.5 is OCHF.sub.2, and R.sup.6 is H;
R is CF.sub.3, R.sup.2 is Cl, R.sup.3 and R.sup.6 are H, R.sup.4 is OCH(CH.sub.3).sub.2, and R.sup.5 is OCHF.sub.2 ;
R is CF.sub.3, R.sup.2 is Cl, R.sup.3 and R.sup.4 are joined to form --CH.sub.2 C(CH.sub.3)O--, R.sup.5 is OCHF.sub.2, and R.sup.6 is H;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH(CH.sub.3).sub.2 ;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.4 are joined to form --CH.sub.2 C(CH.sub.3).sub.2 O--, and R.sup.6 is H;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.4 are joined to form --C(O)C(CH.sub.3).sub.2 O--, and R.sup.6 is H;
R is CF.sub.3, R.sup.2 and R.sup.5 are Cl, R.sup.3 and R.sup.6 are H, and R.sup.4 is OCH.dbd.CH.sub.2.
The compounds of this invention may be prepared by following the procedures described below, or by methods analogous or similar thereto and within the skill of the art. These procedures are not intended to limit the scope of the appended Claims. ##STR20##
Following Method A, an appropriately substituted aniline (I) may be treated with thiophosgene (W=S) in chloroform in the presence of potassium carbonate and water to produce the substituted phenyl isothiocyanate, (II). Alternatively, aniline (I) may be treated with phosgene (W=O) in chloroform to produce the phenyl isocyanate, (II). The reaction of (II) with the appropriate hydrazine, e.g., methylhydrazine, in ethanol (for W=S) or toluene (W=O) produces the 4-(substituted-phenyl)-2-methyl-3-thiosemicarbazide, or -semicarbazide, (III). The treatment of (III) with the appropriate anhydride, e.g., trifluoroacetic anhydride, in toluene yields the corresponding 3-substituted-4,5-dihydro-1-methyl-4-(substituted-phenyl)-1,2,4-triazol-5(1H)-thione or -one, (IV). ##STR21##
Following Method B, an appropriately substituted 4,5-dihydro-4-(nitrophenyl)-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--NO.sub.2) may be reduced with iron powder in dilute hydrochloric acid and ethanol to produce the corresponding 4-aminophenyl-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--NH.sub.2). Subsequent reaction of (IV, R.sup.4 =--NH.sub.2) with an alkyl halide, e.g., ethyl iodide, and sodium bicarbonate in acetonitrile produces appropriately substituted 4-(mono- and dialkyl aminophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--NH(alkyl) or R.sup.4 =--N(alkyl).sub.2). ##STR22##
Following Method C, the reaction of appropriately substituted 4,5-dihydro-4-(3-methylcarbonylphenyl)-1,2,4-triazol-5(1H)-thione, (IV, R.sup.3 =--C(O)CH.sub.3), with methyltriphenylphosphonium bromide and n-butyllithium in tetrahydrofuran produces the corresponding 4,5-dihydro-4-[3-(1-methylethenyl)phenyl]-1,2,4-triazol-5(1H)-thione, (IV, R.sup.3 =--C(CH.sub.3).dbd.CH.sub.2). ##STR23##
Following Method D, the treatment of an appropriately substituted 4-(ethoxyphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--OCH.sub.2 CH.sub.3), with pyridine hydrochloride and heat produces the corresponding 4-(hydroxyphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--OH). The reaction of 4-(hydroxyphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--OH), with an alkyl halide, e.g., iodopropane, and potassium carbonate in N,N-dimethylformamide yields the corresponding 4,5-dihydro-4-(alkoxyphenyl)-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--OC.sub.3 H.sub.7). ##STR24##
Following Method E, heating a mixture of an appropriately substituted compound, (IV, W=S, R.sup.4 =F), with a cyclic amino compound such as pyrrolidine, yields the corresponding 4,5-dihydro-4-(pyrrolidin-1-yl)-phenyl-1,2,4-thiazol-5(1H)-thione, (IV, R.sup.4 = ##STR25##
Following Method F, the reaction of an appropriately substituted 4-(aminophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--NH.sub.2), prepared as described in Method B) with sodium nitrite and potassium iodide in dilute sulfuric acid produces the corresponding 4-(iodophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione (IV, R.sup.4 =I). Subsequent reaction of 4-(iodophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =I), with copper (I) phenylacetylide in pyridine yields the substituted 4-(phenylethynylphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--C.tbd.C--C.sub.6 H.sub.5). The process described in this latter step is described in Stevens et al., J. Org. Chem., Vol. 28, pp. 3313-3315 (1963). ##STR26##
Following Method G, the reaction of a substituted 4-(iodophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =I, prepared as described in Method F), with (trimethylsilyl) acetylene and a catalytic amount of bis-(triphenylphosphine) palladium (II) chloride and copper (I) iodide in a mixture of triethylamine and acetonitrile produces the substituted 4-(trimethylsilylethynylphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione (IV, R.sup.4 =--C.tbd.CSi(CH.sub.3).sub.3). Treatment of the resultant compound, (IV, R.sup.4 =--C.tbd.CSi(CH.sub.3).sub.3), with tetrabutylammonium fluoride in tetrahydrofuran yields the substituted 4-(ethynylphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione, (IV, R.sup.4 =--C.tbd.CH).
A variety of substituted aniline compounds (I) are commercially available. However, in those cases where an aniline starting material (I) having the desired substitutions is not available through commercial sources, one of the following processes may be employed. ##STR27##
Following Intermediate Method 1, a substituted aniline, for example 2,5-difluoroaniline, may be reacted with 4-methylphenylsulfonyl chloride in pyridine to form N-(4-methylphenylsulfonyl)-2,5-difluoroaniline, (V). Nitration of (V) with sodium nitrite in nitric acid, acetic acid and water produces N-(4-methylphenylsulfonyl)-2,5-difluoro-4-nitroaniline, (VI). The reaction of (VI) with aqueous sulfuric acid yields 2,5-difluoro-4-nitroaniline, (VII). Subsequent reaction of (VII) with acetic anhydride and a small amount of dimethylaminopyridine (DMAP) in methylene chloride produces N-(2,5-difluoro-4-nitrophenyl)-acetamide (VIII). Treatment of (VIII) with a borane/dimethyl sulfide complex in tetrahydrofuran yields N-ethyl-2,5-difluoro-4-nitroaniline, (IX). Repeating the previous two steps, the reaction of (IX) first with acetic anhydride (to produce N-(2,5-difluoro-4-nitrophenyl)-acetamide, (X)) followed by treatment with a borane/dimethyl sulfide complex yields N,N-diethyl-2,5-difluoro-4-nitroaniline, (XI). Hydrogenation of (XI) with platinum oxide in ethanol produces the desired 2,5-difluoro-4-diethylaminoaniline, (XII). ##STR28##
Following Intermediate Method 2, the reaction of 2,5-dichloro-4-nitroaniline with acetic acid, sulfuric acid and hydrogen peroxide produces 2,6-dichloro-1,4-dinitrobenzene, (XIII). Heating the resultant compound (XIII) in diethylamine produces 2,6-dichloro-4-nitrophenyl-N,N-diethylaniline, (XIV). Subsequent hydrogenation of (XIV) with platinum oxide in ethanol provides 3,5-dichloro-4-diethylaminoaniline, (XV). ##STR29##
Following Intermediate Method 3, the reaction of catechol with 2-butanone and phosphorus pentoxide in methylene chloride produces 2-ethyl-2-methyl-1,3-benzodioxole, (XVI). Nitration of (XVI) with nitric and sulfuric acid in methylene chloride yields 2-ethyl-2-methyl-5-nitro-1,3-benzodioxole, (XVII). Subsequent hydrogenation of the compound (XVII) with platinum oxide in ethanol produces 5-amino-2-ethyl-2-methyl-1,3-benzodioxole, (XVIII). ##STR30##
Following Intermediate Method 4, the reaction of 2-hydroxy-4-nitroaniline with sodium hydride and 1,2-dibromoethane in N,N-dimethylformamide produces 2,3-dihydro-7-nitro-1,4-benzoxazine, (XIX). The reaction of (XIX) with sodium hydride and 2-iodopropane in N,N-dimethylformamide yields 2,3-dihydro-4-(1-methylethyl)-7-nitro-1,4-benzoxazine, (XX). Hydrogenation of (XX) with platinum oxide yielded (XXI). ##STR31##
Following Intermediate Method 5, the reaction of 2-chloro-5-nitropyridine, (XXII) with diethylamine produces 2-diethylamino-5-nitropyridine, (XXII). The reduction of this compound (XXII) with iron powder in aqueous hydrochloric acid and ethanol yields 5-amino-2-diethylaminopyridine, (XXIII).
Preparation of compounds of the invention is further illustrated by the following Examples. These Examples are not intended to limit the scope of the appended Claims.

EXAMPLE 1
4-(4-Diethylaminophenyl)-3-trifluoromethyl-1-(2-hydroxyethyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione
Step A
4-(4-Diethylaminophenyl)-2-(2-hydroxyethyl)-3-thiosemicarbazide
To a stirred solution of 5.0 g (0.024 mole) of 4-diethylaminophenyl isothiocyanate in 200 ml of ethanol was added 2.45 g (0.0290 mole) of 2-hydroxyethylhydrazine. The reaction mixture was stirred at room temperature for approximately 24 hours. The mixture was evaporated to dryness under reduced pressure to yield 7.3 g of a solid containing 4-(4-diethylaminophenyl)-2-(2-hydroxyethyl)-3-thiosemicarbazide. The nmr spectrum was consistent with the proposed structure contaminated with a small amount of 2-hydroxyethylhydrazine.
Step B
4-(4-Diethylaminophenyl)-3-trifluoromethyl-1-(2-hydroxyethyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione
A solution of 3.0 g (0.010 mole) of 4-(4-diethylaminophenyl)-2-(2-hydroxyethyl)-3-thiosemicarbazide and 2.52 g (0.0120 mole) of trifluoroacetic anhydride in 250 ml of toluene was stirred at room temperature for approximately 24 hours. The reaction mixture was neutralized with an aqueous sodium bicarbonate solution. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined. The combined organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography to yield 0.5 g of 4-(4-diethylaminophenyl)-3-trifluoromethyl-1-(2-hydroxyethyl)-4,5-dihydro-1,2,4-triazol-5(1H)-thione as an oil, Compound 171 of Table 1. The nmr and mass spectra were consistent with the proposed structure.
EXAMPLE 2
4-(2-Chloro-4-diethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione and 4-(2-chloro-4-ethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Step A
4-(2-chloro-4-nitrophenyl)-2-methyl-3-thiosemicarbazide
To a stirred solution of 60.0 g (0.280 mole) of 2-chloro-4-nitrophenyl isothiocyanate in 500 ml of ethanol was added 12.9 g (0.280 mole) of methylhydrazine. This mixture was heated and was stirred at 65.degree. C. for approximately 18 hours. The mixture was then heated to reflux and was cooled. A solid had formed and was collected by filtration. The filter cake was rinsed with aqueous ethanol and was dried under reduced pressure to yield 59.0 g of 4-(2-chloro-4-nitrophenyl)-2-methyl-3-thiosemicarbazide, mp 164.degree.-167.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
4-(2-chloro-4-nitrophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
To a stirred mixture of 58.6 g (0.225 mole) of 4-(2-chloro-4-nitrophenyl)-2-methyl-3-thiosemicarbazide in 250 ml of toluene was added 56.7 g (0.270 mole) of trifluoroacetic anhydride. The resulting slurry became exothermic to the point of reflux and was allowed to cool slowly to room temperature. This mixture was stirred at room temperature for approximately 18 hours during which time a solution formed. This organic solution was neutralized by washing with an aqueous 10% sodium hydroxide solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was extracted with ethyl acetate, leaving 65.8 g of a solid. This solid was stirred in 900 ml of ethanol. The mixture was heated at reflux and then was filtered hot to remove insoluble material. The filtrate was allowed to cool slowly, and a small amount of water was added to the ethanol to initiate crystallization. The crystalline material was collected by filtration to yield 25.6 g of 4-(2-chloro-4-nitrophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione, mp 152.degree.-155.degree. C., Compound 93 of Table 1. The nmr spectrum was consistent with the proposed structure. An additional 6.0 g of product was obtained by purification of the mother liquor by column chromatography.
Step C
4-(4-Amino-2-chlorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
To a stirred mixture of 18.8 g (0.0337 mole) of iron powder in 400 ml of concentrated hydrochloric acid, 20 ml of water, and 300 ml of ethanol was added slowly 28.5 g of 4-(2-chloro-4-nitrophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione. This mixture was heated at reflux for eight hours and then was cooled to room temperature and stirred for approximately 18 hours. The mixture was heated to reflux and was filtered hot. The filter cake was washed with methylene chloride. The wash and the filtrate were combined, and the solvents were removed by evaporation under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with diethyl ether to yield 23.4 g of 4-(4-amino-2-chlorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 145.degree.-147.degree. C., Compound 94 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step D
4-(2-chloro-4-diethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione and 4-(2-chloro-4-ethylaminophenyl-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
To a stirred solution of 3.5 g (0.011 mole) of 4-(4-amino-2-chlorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione in a 100 ml of acetonitrile were added in succession 2.9 g (0.034 mole) of sodium bicarbonate and 3.7 g (0.024 mole) of iodoethane. The reaction mixture was heated at reflux for approximately 18 hours. An additional 1.8 g (0.011 mole) of iodoethane was added, and the reaction was stirred at room temperature for two days. The mixture was cooled, and the solvent was evaporated under reduced pressure, leaving a residue. Water was added to the residue, and the mixture was extracted with methylene chloride. The organic extract was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography to produce two fractions. The first fraction yielded 0.5 g of 4-(2-chloro-4-diethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 108.degree.-110.degree. C., Compound 98 of Table 1. The second fraction yielded 1.5 g of 4-(2-chloro-4-ethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 87.degree.-90.degree. C., Compound 96 of Table 1.
EXAMPLE 3
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-[3-(1-methylethenyl)phenyl]-1,2,4-triazol-5(1H)-thione
Step A
2-Methyl-4-(3-methylcarbonylphenyl)-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 20.0 g (0.113 mole) of 3-methylcarbonylphenyl isothiocyanate and 5.21 g (0.113 mole) of methylhydrazine in 150 ml of ethanol yielded 19.9 g of 2-methyl-4-(3-methylcarbonylphenyl)-3-thiosemicarbazide as a solid, mp 125.degree.-127.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(3-methylcarbonylphenyl)-1,2,4-triazol-5(1H)-thione
A mixture of 19.4 g (0.0871 mole) of 2-methyl-4-(3-methylcarbonylphenyl)-3-thiosemicarbazide and 36.6 g (0.174 mole) of trifluoroacetic anhydride in 150 ml of toluene was stirred at room temperature for approximately 18 hours. The reaction mixture was neutralized with an aqueous, 10% sodium hydroxide solution. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 20.3 g of 3-trifluoromethyl-4,5-dihydro- 1-methyl-4-(3-methylcarbonylphenyl)-1,2,4-triazol-5(1H)-thione as a thick oil. The nmr spectrum of the oil indicated that it contained about 65% of the desired product, the balance being reaction by-products.
Step C
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-[3-(1-methylethenyl)phenyl]-1,2,4-triazol-5(1H)-thione
Under a dry nitrogen atmosphere 23.8 ml of a 1.55M solution of n-butyllithium in hexane was added dropwise to a stirred solution of 15.8 g (0.0443 mole) of methyltriphenylphosphonium bromide in 300 ml of dry tetrahydrofuran. This mixture was stirred at room temperature for 2.5 hours, and a solution of 11.1 g of the oil from Step B in 50 ml of tetrahydrofuran was added dropwise. After complete addition, the reaction mixture was heated at reflux for 2.5 hours. The mixture was cooled to room temperature and was poured into 300 ml of an aqueous, 2N sodium hydroxide solution. This mixture was extracted with 300 ml of diethyl ether. The organic extract was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel eluting with ethyl acetate: n-heptane (25:75) to yield 3.7 g of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-[3-(1-methylethenyl)phenyl]-1,2,4-triazol-5(1H)-thione as a solid, mp 64.degree.-66.degree. C., Compound 27 of Table 1.
EXAMPLE 4
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(4-n-propoxyphenyl)-1,2,4-triazol-5(1H)-thione
Step A
4-(4-Ethoxyphenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 2.5 g (0.0698 mole) of 4-ethoxyphenyl isothiocyanate and 3.22 g (0.0698 mole) of methylhydrazine in 100 ml of ethanol yielded 12.5 g of 4-(4-ethoxyphenyl)-2-methyl-3-thiosemicarbazide as a solid. The nmr spectrum was consistent with the proposed structure.
Step B
4-(4-Ethoxyphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 12.5 g (0.0530 mole) of 4-(4-ethoxyphenyl)-2-methyl-3-thiosemicarbazide with 11.2 g (0.0530 mole) of trifluoroacetic anhydride in 100 ml of toluene yielded 14.6 g of 4-(4-ethoxyphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 93.degree.-95.degree. C., Compound 60 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step C
3-Trifluoromethyl-4,5-dihydro-4-(4-hydroxyphenyl)-1-methyl-1,2,4-triazol-5(1H)-thione
A mixture of 12.6 g (0.109 mole) of pyridine hydrochloride and 11.0 g (0.0363 mole) of 4-(4-ethoxyphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione was heated at 215.degree. C. and stirred for one hour. The mixture was cooled and dissolved in water. The aqueous solution was extracted with a mixture of tetrahydrofuran:diethyl ether (50:50). The organic phase was extracted with an aqueous, 10% sodium hydroxide solution. The basic extract was acidified, forming a precipitate. This solid was collected by filtration and dried to yield 7.1 g of 3-trifluoromethyl-4,5-dihydro-4-(4-hydroxyphenyl)-1-methyl-1,2,4-triazol-5(1H)-thione, mp 150.degree.-152.degree. C. The nmr spectrum was consistent with the proposed structure.
Step D
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(4-n-propoxyphenyl)-1,2,4-triazol-5(1H)-thione
A stirred mixture of 1.5 g (0.0058 mole) of 3-trifluoromethyl-4,5-dihydro-4-(4-hydroxyphenyl)-1-methyl-1,2,4-triazol-5(1H)-one and 1.0 g (0.0069 mole) of potassium carbonate in 15 ml of N,N-dimethylformamide was heated at 80.degree. C. While maintaining that temperature, 0.98 g (0.0058 mole) of 1-iodopropane was added. The reaction mixture was stirred at 80.degree. C. for approximately 18 hours. The mixture was cooled and diluted with water. This mixture was extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. The residue was purified by column chromatography on silica gel, eluting with methylene chloride, to yield 1.4 g of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-(4-n-propoxyphenyl)-1,2,4-triazol-5(1H)-thione as a solid, mp 68.degree.-70.degree. C., Compound 61 of Table 1. The nmr spectrum was consistent with the proposed structure.
EXAMPLE 5
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(pyrrolidin-1-yl)phenyl-1,2,4-triazol-5(1H)-thione
Step A
4-(4-Fluorophenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 10.0 g (0.0653 mole) of 4-fluorophenyl isothiocyanate with 3.01 g (0.0654 mole) of methylhydrazine in 100 ml of ethanol yielded 10 g of 4-(4-fluorophenyl)-2-methyl-3-thiosemicarbazide as a solid, mp 148.degree.-150.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
4-(4-Fluorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 9.59 g (0.0480 mole) of 4-(4-fluorophenyl)-2-methyl-3-thiosemicarbazide with 10.1 g (0.0480 mole) of trifluoroacetic anhydride in 100 ml of toluene yielded 12.3 g of 4-(4-fluorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 94.degree.-96.degree. C., Compound 8 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step C
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(pyrrolidin-1-yl)-1,2,4-triazol-5(1H)-thione
A stirred mixture of 1.37 g (0.00490 mole) of 4-(4-fluorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione in 25 ml of pyrrolidine was heated at reflux for approximately 18 hours. The mixture was cooled, and most of the pyrrolidine was removed by distillation under reduced pressure, leaving a residue. This residue was partitioned between water and methylene chloride. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 0.9 g of 3 trifluoromethyl-4,5-dihydro-1-methyl-4-(pyrrolidin-1-yl)phenyl-1,2,4-triazol-5(1H)-thione as a solid, mp 150.degree.-153.degree. C., Compound 75 of Table 1.
EXAMPLE 6
3-Trifluoromethyl-4-[4-(3-trifluoromethyl-1-methyl-1,2,4-triazol-5-yl)phenyl]-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione and 4-(4-cyanophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Step A
4-(4-Cyanophenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 7.8 g (0.049 mole) of 4-cyanophenyl isothiocyanate with 2.24 g (0.0490 mole) of methylhydrazine in 50 ml of ethanol yielded 10.0 g of 4-(4-cyanophenyl)-2-methyl-3-thiosemicarbazide as a solid, mp 178.degree.-179.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
3-Trifluoromethyl-4-[4-(3-trifluoromethyl-1-methyl-1,2,4-triazol-5-yl)phenyl]-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione and 4-(4-cyanophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
A mixture of 5.2 g (0.025 mole) of 4-(4-cyanophenyl)-2-methyl-3-thiosemicarbazide and 5.3 g (0.025 mole) of trifluoroacetic anhydride in 100 ml of toluene was stirred at room temperature for approximately 18 hours. The reaction mixture was neutralized by washing with an aqueous sodium carbonate solution. The aqueous wash was extracted with toluene, and the organic phases were combined. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with petroleum ether:ethyl acetate (9:1). Two products were obtained by column chromatography: the first was 0.25 g of 4-(4-cyanophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione, mp 60.degree.-61.degree. C., Compound 29 of Table 1; the second was 0.36 g of 3-trifluoromethyl-4-[4-(3-trifluoromethyl-1-methyl-1,2,4-triazol-5-yl)phenyl]-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione, mp 65.degree.-66.degree. C., Compound 79 of Table 1. The nmr spectra were consistent with the proposed structure.
EXAMPLE 7
4-(2-Chloro-4-phenylethynylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Step A
4-(2-chloro-4-iodophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
To a stirred, warm (40.degree. C.) solution of 10.8 g (0.0648 mole) of potassium iodide in 80 ml of water was added dropwise a solution of 10.0 g (0.0324 mole) of 4-(4-amino-2-chlorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione (Compound 94 of Table 1, prepared in Step C of Example 2), 2.70 g (0.389 mole) of sodium nitrite, and 20.0 g (0.204 mole) of concentrated sulfuric acid in 125 g of ice-cold water. The resultant mixture was stirred at 40.degree. C. for three hours. The mixture was cooled and was extracted with methylene chloride. The extract was washed with an aqueous sodium metabisulfite solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with petroleum ether:diethyl ether (75:25) to yield 5.0 g of 4-(2-chloro-4-iodophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 117.degree.-119.degree. C., Compound 91 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step B
4-(2-chloro-4-phenylethynylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Using the process described by Stevens, et al., (J. Org. Chem., Vol. 28, pp. 3313-3315 (1963), the reaction of 4.6 g (0.011 mole) of 4-(2-chloro-4-iodophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione with 1.8 g (0.011 mole) of copper (I) phenylacetylide in 100 ml of dry pyridine under a dry nitrogen atmosphere produced 3.1 g of 4-(2-chloro-4-phenylethynylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 50.degree.-53.degree. C., Compound 92 of Table 1. The nmr and ir spectra were consistent with the proposed structure.
EXAMPLE 8
4-(4-Ethynyl-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Step A
4-Iodo-2-methylphenyl isothiocyanate
To a stirred mixture of 9.9 g (0.086 mole) of thiophosgene, 5.0 g (0.036 mole) of potassium carbonate in 55 ml of water and 100 ml of chloroform was added a solution of 20.0 g (0.0862 mole) of 4-iodo-2-methylaniline in 50 ml of chloroform. Additional potassium carbonate was added to make the reaction mixture basic. An additional 9.9 g of thiophosgene was added, and the reaction mixture was stirred at room temperature for approximately 18 hours. The mixture was partitioned between water (100 ml) and chloroform (100 ml). The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with methylene chloride to yield 22.6 g of 4-iodo-2-methylphenyl isothiocyanate as a solid, mp 51.degree.-53.degree. C.
The ir spectrum was consistent with the proposed structure.
Step B
4-(4-Iodo-2-methylphenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 22.3 g (0.0810 mole) of 4-iodo-2-methylphenyl isothiocyanate with 3.74 g (0.0811 mole) of methylhydrazine in 175 ml of ethanol yielded 16.7 g of 4-(4-iodo-2-methylphenyl)-2-methyl-3-thiosemicarbazide as a solid, mp 160.degree.-161.degree. C. The nmr spectrum was consistent with the proposed structure.
Step C
3-Trifluoromethyl-4,5-dihydro-4-(4-iodo-2-methylphenyl)-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 16.4 g (0.0511 mole) of 4-(4-iodo-2-methylphenyl)-2-methyl-3-thiosemicarbazide with 11.8 g (0.0562 mole) of trifluoroacetic anhydride in 150 ml of toluene yielded 17.4 g of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-(4-iodo-2-methylphenyl)-1,2,4-triazol-5(1H)-thione as a solid, mp 104.degree.-107.degree. C., Compound 106 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step D
3-Trifluoromethyl-4,5-dihydro-1-methyl-4-(2-methyl-4-trimethylsilylethynylphenyl)-1,2,4-triazol-5(1H)-thione
To a stirred mixture of 5.00 g (0.0125 mole) of 3-trifluoromethyl-4,5-dihydro-4-(4-iodo-2-methylphenyl)-1-methyl-1,2,4-triazol-5(1H)-thione and 2.46 g (0.0250 mole) of trimethylsilylacetylene in 20 ml of acetonitrile and 100 ml of triethylamine was added 0.0880 g (0.000125 mole) of bis(triphenylphosphine)palladium (II) chloride and 0.048 g (0.00025 mole) of copper (I) iodide. The reaction mixture was heated at reflux for approximately 18 hours. The solvents were removed from the reaction mixture by evaporation under reduced pressure, leaving a residue. This residue was dissolved in chloroform, and the organic solution was washed in succession with an aqueous, saturated sodium chloride solution and an aqueous, 20% ammonium chloride solution. The washed organic phase was evaporated under reduced pressure, leaving a dark oil. This oil was purified by column chromatography on silica gel, eluting with chloroform, to yield 4.7 g of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-(2-methyl-4-trimethylsilylethynylphenyl)-1,2,4-triazol-5(1H)-thione as a solid, mp 90.degree.-93.degree. C., Compound 113 of Table 1. The nmr spectrum was consistent with the proposed structure.
Step E
4-(4-ethynyl-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
To a stirred mixture of 4.40 g (0.0119 mole) of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-(2-methyl-4-trimethylsilylethynylphenyl)-1,2,4-triazol-5-(1H)-thione in 75 ml of tetrahydrofuran was added 10.8 g (0.0414 mole) of tetrabutylammonium fluoride. This mixture was stirred for about 20 minutes, and the reaction was partitioned between 75 ml of diethyl ether and 150 ml of an aqueous sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with diethyl ether, to yield 2.5 g of 4-(4-ethynyl-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as an oil, Compound 111 of Table 1. The nmr spectrum was consistent with the proposed structure.
EXAMPLE 9
4-(4-DIETHYLAMINO-2,5-DIFLUOROPHENYL)-3-TRIFLUOROMETHYL-4,5-DIHYDRO-1-METHYL-1,2,4-TRIAZOL-5(1H)-THIONE
Step A
N-(4-Methylphenylsulfonyl)-2,5-difluoroaniline
A stirred mixture of 15.0 g (0.116 mole) of 2,5-difluoroaniline and 24.4 g (0.128 mole) of 4-methylphenylsulfonyl chloride in 50 ml of pyridine was heated at reflux for approximately 18 hours. The reaction mixture was cooled and poured into 500 ml of 6N hydrochloric acid. This acidic mixture was allowed to stand at room temperature for two days. A precipitate formed and was collected by filtration. The filter cake was washed with dilute hydrochloric acid and was dried under reduced pressure to yield 25.0 g of N-(4-methylphenylsulfonyl)-2,5-difluoroaniline. The nmr spectrum was consistent with the proposed structure.
Step B
N-(4-Methylphenylsulfonyl)-2,5-difluoro-4-nitroaniline
The nitration of 12.0 g (0.042 mole) of N-(4-methylphenylsulfonyl)-2,5-difluoroaniline with 0.2 g (0.0035 mole) of sodium nitrite and 17.4 g (0.276 mole) of fuming nitric acid in 86 ml of glacial acetic acid and 86 ml of water yielded 12.2 g of N-(4-methylphenylsulfonyl)-2,5-difluoro-4-nitroaniline as a solid. The nmr spectrum was consistent with the proposed structure.
Step C
2,5-Difluoro-4-nitroaniline
To a stirred mixture of 12.2 g (0.0370 mole) of N-(4-methylphenylsulfonyl)-2,5-difluoro-4-nitroaniline in 20 ml of water was added 70 ml of concentrated sulfuric acid. This mixture was heated at 90.degree. C. for 15 minutes and then was allowed to cool and stir at room temperature for five days. The reaction mixture was poured into ice-water, and the aqueous mixture was neutralized with concentrated ammonium hydroxide. The resulting solid was collected by filtration. The filter cake was washed with water and was dried under reduced pressure to yield 6.15 g of 2,5-difluoro-4-nitroaniline. The nmr spectrum was consistent with the proposed structure.
Step D
N-(2,5-Difluoro-4-nitrophenyl)acetamide
A mixture of 6.0 g (0.034 mole) of 2,5-difluoro-4-nitroaniline, 6.5 g (0.064 mole) of acetic anhydride, and approximately 0.1 g (0.0008 mole) of dimethylaminopyridine in 300 ml of methylene chloride was stirred and heated at reflux for two hours. The reaction mixture was allowed to cool and stir at room temperature for approximately 18 hours. The solvent was removed from the mixture by distillation under reduced pressure, leaving a residue. To this residue was added 32.5 g (0.318 mole) of acetic anhydride and several drops of concentrated sulfuric acid. This mixture was stirred at room temperature for approximately 18 hours. Approximately 300 ml of water was added to the mixture causing a vigorous exotherm and a solid to form. This solid was collected by filtration. The filter cake was washed with water and was dried under reduced pressure to yield 6.5 g of N-(2,5-difluoro-4-nitrophenyl)acetamide. The nmr spectrum was consistent with the proposed structure.
Step E
N-Ethyl-2,5-difluoro-4-nitroaniline
To a cold (0.degree. C.), stirred solution of 6.3 g (0.029 mole) of N-(2,5-difluoro-4-nitrophenyl)acetamide in 100 ml of dry tetrahydrofuran was added dropwise 8.8 ml of a 10M boranedimethyl sulfide complex in tetrahydrofuran. The reaction mixture was heated until a gentle reflux was maintained with no external heating. When this reflux subsided, the mixture was reheated at reflux for three hours. The reaction mixture was cooled to 0.degree. C., and methanol was added dropwise until no gas evolution was seen upon subsequent addition. This mixture was allowed to stand at room temperature for two days. The solvent was removed from the mixture by distillation under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with methylene chloride to yield 5.6 g of N-ethyl-2,5-difluoro-4-nitroaniline as a solid. The nmr spectrum was consistent with the proposed structure.
Step F
N-Ethyl-N-(2,5-difluoro-4-nitrophenyl)acetamide
To a stirred mixture of 5.4 g (0.027 mole) of N-ethyl-2,5-difluoro-4-nitroaniline in 100 ml of acetic anhydride was added three drops of concentrated sulfuric acid. This mixture was stirred at room temperature for 30 minutes, and was poured into 200 ml of ice and water. The aqueous mixture was extracted with three portions of ethyl acetate. The extracts were combined and washed in succession with an aqueous, saturated sodium chloride solution and water. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 6.1 g of N-ethyl-N-(2,5-difluoro-4-nitrophenyl)acetamide as a solid. The nmr spectrum was consistent with the proposed structure.
Step G
N,N-Diethyl-2,5-difluoro-4-nitroaniline
Following procedures similar to those employed in Step E of this Example, the reaction of 4.2 g (0.017 mole) of N-ethyl-N-(2,5-difluoro-4-nitrophenyl)acetamide with 5.1 ml of a 10M borane dimethyl sulfide complex in tetrahydrofuran in 100 ml of dry tetrahydrofuran yielded 3.6 g of N,N-diethyl-2,5-difluoro-4-nitroaniline. The nmr spectrum was consistent with the proposed structure.
Step H
4-Diethylamino-2,5-difluoroaniline
Hydrogenation of 3.4 g (0.015 mole) of N,N-diethyl-2,5-difluoro-4-nitroaniline with approximately 0.1 g (0.0004 mole of platinum in 250 ml of ethanol yielded 3.0 g of 4-diethylamino-2,5-difluoroaniline. The nmr spectrum was consistent with the proposed structure.
Step I
4-Diethylamino-2,5-difluorophenyl isothiocyanate
In a manner similar to Step A of Example 8, the reaction of 3.0 g (0.026 mole) of thiophosgene with 2.6 g (0.013 mole) of 4-diethylamino-2,5-difluoroaniline and 7.2 g (0.052 mole) of potassium carbonate in 100 ml of chloroform and 100 ml of water yielded 3.2 g of 4-diethylamino-2,5-difluorophenyl isothiocyanate. The nmr and ir spectra were consistent with the proposed structure.
Step J
4-(4-Diethylamino-2,5-difluorophenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 2.9 g (0.012 mole) of 4-diethylamino-2,5-difluorophenyl isothiocyanate with 0.55 g (0.012 mole) of methylhydrazine in 75 ml of ethanol yielded 3.4 g of 4-(4-diethylamino-2,5-difluorophenyl)-2-methyl-3-thiosemicarbazide. The nmr spectrum was consistent with the proposed structure.
Step K
4-(4-Diethylamino-2,5-difluorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 3.1 g (0.011 mole) of 4-(4-diethylamino-2,5-difluorophenyl)-2-methyl-3-thiosemicarbazide with 2.3 g (0.011 mole) of trifluoroacetic anhydride in 50 ml of toluene yielded 2.3 g of 4-(4-diethylamino-2,5-difluorophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione, Compound 138 of Table 1. The nmr spectrum was consistent with the proposed structure.
EXAMPLE 10
4-(3,5-DICHLORO-4-ETHYLAMINOPHENYL)-3-TRIFLUOROMETHYL-4,5-DIHYDRO-1-METHYL-1,2,4-TRIAZOL-5(1H)-THIONE
Step A
2,6-Dichloro-1,4-dinitrobenzene
A stirred mixture of 15.0 g (0.0725 mole) of 2,6-dichloro-4-nitroaniline in 300 ml of glacial acetic acid, 90 ml of hydrogen peroxide (30% aqueous solution), and 6 ml of concentrated sulfuric acid was heated at 100.degree. C. for 3.5 hours, and then an additional 90 ml of hydrogen peroxide (30%) was added. The reaction mixture was cooled and was diluted with 600 ml of water. A solid formed and was collected by filtration. The filter cake was washed in succession with concentrated sulfuric acid and concentrated hydrochloric acid. The washed solid was dissolved in diethyl ether, and the organic solution was neutralized by washing with an aqueous, 10% sodium hydroxide solution. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with ethyl acetate:petroleum ether (25:75) to yield 9.1 g of 2,6-dichloro-1,4-dinitrobenzene, mp 109.degree.-112.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
2,6-Dichloro-N,N-diethyl-4-nitroaniline
A stirred mixture of 4.5 g (0.019 mole) of 2,6-dichloro-1,4-dinitrobenzene in 75 ml of diethylamine was heated at reflux for two days. The reaction mixture was cooled, and the solvent was removed by distillation under reduced pressure, leaving a residue. The residue was partitioned between water and diethyl ether. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. This residue was purified by column chromatography on silica gel, eluting with methylene chloride, to yield 3.7 g of 2,6-dichloro-N,N-diethyl-4-nitroaniline. The nmr spectrum was consistent with the proposed structure.
Step C
3,5-Dichloro-4-diethylaminoaniline
The hydrogenation of 3.7 g (0.014 mole) of 2,6-dichloro-N,N-diethyl-4-nitroaniline with approximately 0.1 g (0.0004 mole) of platinum oxide in 250 ml of ethanol yielded 1.9 g of 3,5-dichloro-4-diethylaminoaniline as an oil. The nmr spectrum was consistent with the proposed structure.
Step D
3,5-Dichloro-4-diethylaminophenyl isothiocyanate
Following procedures similar to those employed in Step A of Example 8, the reaction of 1.9 g (0.0082 mole) of 3,5-dichloro-4-diethylaminoaniline with 1.88 g (0.0163 mole) of thiophosgene and 5.0 g (0.036 mole) of potassium carbonate in 20 ml of water and 100 ml of chloroform yielded 2.2 g of 3,5-dichloro-4-diethylaminophenyl isothiocyanate as an oil. The ir spectrum was consistent with the proposed structure.
Step E
4-(3,5-Dichloro-4-diethylaminophenyl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 2.2 g (0.0080 mole) of 3,5-dichloro-4-diethylaminophenyl isothiocyanate with 0.37 g (0.0080 mole) of methylhydrazine in 75 ml of ethanol produced a quantitative yield of 4-(3,5-dichloro-4-diethylaminophenyl)-2-methyl-3-thiosemicarbazide. The nmr spectrum was consistent with the proposed structure.
Step F
4-(3,5-Dichloro-4-diethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 2.6 g (0.0080 mole) of 4-(3,5-dichloro-4-diethylaminophenyl)-2-methyl-3-thiosemicarbazide with 2.0 g (0.0096 mole) of trifluoroacetic anhydride in 75 ml of toluene yielded 1.0 g of 4-(3,5-dichloro-4-diethylaminophenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a solid, mp 128.degree.-130.degree. C., Compound 151 of Table 1. The nmr and mass spectra were consistent with the proposed structure.
EXAMPLE 11
4-(2-ETHYL-2-METHYL-1,3-BENZODIOXOL-5-YL)-3-TRIFLUOROMETHYL-4,5-DIHYDRO-1-METHYL-1,2,4-TRIAZOL-5(1H)-THIONE
Step A
2-Ethyl-2-methyl-1,3-benzodioxole
To a stirred solution of 20.0 g (0.180 mole) of catechol and 0.8 g (0.40 mole) of 2-butanone in 200 ml of methylene chloride was added 128.0 g (0.902 mole) of phosphorus pentoxide. The reaction mixture was stirred at room temperature for two days. The stirring was stopped, and the reaction solids were allowed to settle. The reaction mixture was decanted into a separatory funnel. The solid material was washed with methylene chloride, and the wash was decanted into the above separatory funnel. The combined organic phase was washed with aqueous, saturated sodium bicarbonate solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 17.3 g of 2-ethyl-2-methyl-1,3-benzodioxole.
Step B
2-Ethyl-2-methyl-5-nitro-1,3-benzodioxole
The nitration of 16.5 g (0.100 mole) of 2-ethyl-2-methyl-1,3-benzodioxole with 7.7 ml of nitric acid (70% solution in water) and 10 ml of concentrated sulfuric acid in 100 ml of methylene chloride yielded 2.6 g of 2-ethyl-2-methyl-5-nitro-1,3-benzodioxole. The nmr spectrum was consistent with the proposed structure.
Step C
5-Amino-2-ethyl-2-methyl-1,3-benzodioxole
The hydrogenation of 2.55 g (0.0120 mole) of 2-ethyl-2-methyl-5-nitro-1,3-benzodioxole with 0.3 g (0.0013 mole) of platinum oxide in 100 ml of ethanol yielded 2.0 g of 5-amino-2-ethyl-2-methyl-1,3-benzodioxole as an oil. The nmr spectrum was consistent with the proposed structure.
Step D
(2-Ethyl-2-methyl-1,3-benzodioxol-5-yl) isothiocyanate
Using procedures similar to those employed in Step A of Example 8, the reaction of 1.9 g (0.011 mole) of 5-amino-2-ethyl-2-methyl-1,3-benzodioxole with 2.4 g (0.021 mole) of thiophosgene and 6.2 g (0.045 mole) of potassium carbonate in 10 ml of water and 70 ml of chloroform yielded 2.3 g of (2-ethyl-2-methyl-1,3-benzodioxol-5-yl) isothiocyanate as an oil. The nmr spectrum was consistent with the proposed structure.
Step E
4-(2-Ethyl-2-methyl-1,3-benzodioxol-5-yl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 2.1 g (0.0095 mole) of (2-ethyl-2-methyl-1,3-benzodioxol-5-yl) isothiocyanate with 0.44 g (0.0095 mole) of methylhydrazine in 50 ml of ethanol yielded 1.7 g of 4-(2-ethyl-2-methyl-1,3-benzodioxol-5-yl)-2-methyl-3-thiosemicarbazide as a solid. The nmr spectrum was consistent with the proposed structure.
Step F
4-(2-Ethyl-2-methyl-1,3-benzodioxol-5-yl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 1.5 g (0.0056 mole) of 4-(2-ethyl-2-methyl-1,3-benzodioxol-5-yl)-2-methyl-3-thiosemicarbazide with 1.3 g (0.0062 mole) of trifluoroacetic anhydride in 75 ml of toluene yielded 1.3 g of 4-(2-ethyl-2-methyl-1,3-benzodioxol-5-yl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as a gummy solid, Compound 162 of Table 1. The nmr and mass spectra were consistent with the proposed structure.
EXAMPLE 12
4-[2,3-DIHYDRO-4-(1-METHYLETHYL)-1,4-BENZOXAZIN-7-YL]-3-TRIFLUOROMETHYL-4,5-DIHYDRO-1-METHYL-1,2,4-TRIAZOL-5(1H)-THIONE
Step A
2,3-Dihydro-7-nitro-1,4-benzoxazine
Under a dry nitrogen atmosphere a solution of 41.0 g (0.270 mole) of 2-amino-5-nitrophenol in 250 ml of N,N-dimethylformamide was added dropwise to a stirred mixture of 6.48 g (0.270 mole) of sodium hydride in 250 ml of N,N-dimethylformamide. When the evolution of gas ceased, 50.0 g (0.270 mole) of 1,2-dibromothane was added dropwise, and the resulting mixture was stirred at room temperature for approximately 18 hours. The reaction mixture was diluted with water, and this mixture was extracted several times with methylene chloride. The organic extracts were combined and washed with several portions of an aqueous, 10% sodium hydroxide solution. The washed organic phase was filtered through a pad of silica gel. The filtrate was evaporated under reduced pressure to yield 3.8 g of 2,3-dihydro-7-nitro-1,4-benzoxazine. The nmr spectrum indicated a small amount of N,N-dimethylformamide was present in the product.
Step B
2,3-Dihydro-4-(1-methylethyl)-7-nitro-1,4-benzoxazine
Under a dry nitrogen atmosphere, a solution of 3.7 g (0.020 mole) of 2,3-dihydro-7-nitro-1,4-benzoxazine in 50 ml of N,N-dimethylformamide was added to a stirred solution of 0.60 g (0.025 mole) of sodium hydride in 100 ml of N,N-dimethylformamide. Upon cessation of hydrogen evolution, 3.4 g (0.020 mole) of 2-iodopropane was added. The reaction mixture was stirred at room temperature for approximately 18 hours, then was heated at 65.degree. C. for 24 hours, and finally was heated at 80.degree. C. for 24 hours. The reaction mixture was cooled and diluted with water. The aqueous mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a residue. Analysis of this residue by nmr spectroscopy indicated it was a mixture of 2,3-dihydro-4-(1-methylethyl)-7-nitro-1,4-benzoxazine and 2,3-dihydro-7-nitro-1,4-benzoxazine.
Step C
7-Amino-2,3-dihydro-4-(1-methylethyl)-1,4-benzoxazine
The hydrogenation of 1.2 g of the mixture from Step B with approximately 0.1 g (0.0004 mole) of platinum oxide in 250 ml of ethanol produced an oil. Analysis of this oil by nmr spectroscopy indicated that it contained a mixture of 7-amino-2,3-dihydro-4-(1-methylethyl)-1,4-benzoxazine and 7-amino-2,3-dihydro-1,4-benzoxazine.
Step D
2,3-Dihydro-4-(1-methylethyl)-1,4-benzoxazin-7-yl isothiocyanate
Following procedures similar to those employed in Step A of Example 8, the reaction of 1.0 g of the mixture from Step C with 1.2 g (0.010 mole) of thiophosgene and 2.9 g (0.029 mole) of potassium carbonate in 100 ml of water and 100 ml of chloroform yielded 1.3 g of a residue. Analysis of this residue by nmr spectroscopy indicated that it contained a mixture of 2,3-dihydro-4-(1-methylethyl)-1,4-benzoxazin-7-yl isothiocyanate and 2,3-dihydro-1,4-benzoxazin-7-yl isothiocyanate.
Step E
4-[2,3-Dihydro-4-(1-methylethyl)-1,4-benzoxazin-7-yl]-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 1.3 g of the mixture from Step D with 0.25 g (0.0056 mole) of methylhydrazine in 250 ml of ethanol yielded 1.7 g of a solid. Analysis of this solid by nmr spectroscopy indicated that it contained a mixture of 4-[2,3-dihydro-4-(1-methylethyl)-1,4-benzoxazin-7-yl]-2-methyl-3-thiosemicarbazide and 4-(2,3-dihydro-1,4-benzoxazin-7-yl)-2-methyl-3-thiosemicarbazide.
Step F
4-[2,3-Dihydro-4-(1-methylethyl)-1,4-benzoxazin-7-yl]-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 1.7 g of the mixture from Step E with 1.27 g (0.00606 mole of trifluoroacetic anhydride in 500 ml of toluene produce a reside. Purification of this residue by column chromatography yielded 0.3 g of 4-[2,3-dihydro-4-(1-methylethyl)-1,4-benzoxazine-7-yl]-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione as an oil, Compound 164 of Table 1. The nmr spectrum was consistent with the proposed structure.
EXAMPLE 13
4-(2-DIETHYLAMINOPYRIDIN-5-YL)-3-TRIFLUOROMETHYL-4,5-DIHYDRO-1-METHYL-1,2,4-TRIAZOL-5(1H)-THIONE
Step A
2-Diethylamino-5-nitropyridine
A stirred mixture of 27.6 g (0.174 mole) of 2-chloro-5-nitropyridine in 500 ml of diethylamine was heated at reflux for two days. The excess diethylamine was removed by distillation under reduced pressure, leaving a residue. This residue was dissolved in methylene chloride, and the organic solution was washed with an aqueous, 10% sodium hydroxide solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield 33.2 g of 2-diethylamino-5-nitropyridine as a solid. The nmr spectrum was consistent with the proposed structure.
Step B
5-Amino-2-diethylaminopyridine
Following procedures similar to those disclosed in Artland, et al., J. Heterocyclic Chem., Vol. 14, 129-134 (1977), the reaction of 10.0 g (0.0512 mole) of 2-diethylamino-5-nitropyridine with 147.0 g (0.659 mole) of tin (II) chloride dihydrate in diethyl ether and concentrated hydrochloric acid produced a residue. This reaction was repeated, and the residues were combined, giving a total of 20 g. The combined residue was purified by column chromatography on silica gel, eluting with acetone to yield 16.2 g of 5-amino-2-diethylaminopyridine as an oil. The nmr spectrum was consistent with the proposed structure.
Step C
(2-Diethylaminopyridin-5-yl) isothiocyanate
Using procedures similar to those employed in Step A of Example 8, the reaction of 15.9 g (0.096 mole of 5-amino-2-diethylaminopyridine with 22.2 g (0.193 mole) of thiophosgene and 5.0 g (0.036 mole) of potassium carbonate in 50 ml of water and 150 ml of chloroform yielded 3.8 g of (2-diethylaminopyridin-5-yl) isothiocyanate as a solid. The nmr spectrum was consistent with the proposed structure.
Step D
4-(2-Diethylaminopyridin-5-yl)-2-methyl-3-thiosemicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 3.5 g (0.017 mole) of (2-diethylaminopyridin-5-yl) isothiocyanate with 0.86 (0.019 mole) of methylhydrazine in 150 ml of ethanol yielded 2.5 g of 4-(2-diethylaminopyridin-5-yl)-2-methyl-3-thiosemicarbazide as a solid, mp 147.degree.-149.degree. C. The nmr spectrum was consistent with the proposed structure.
Step E
4-(2-Diethylaminopyridin-5-yl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-thione
Following procedures similar to those employed in Step B of Example 3, the reaction of 2.25 g (0.00890 mole) of 4-(2-diethylaminopyridin-5-yl)-2-methyl-3-thiosemicarbazide with 1.9 g (0.0089 mole) of trifluoroacetic anhydride in 200 ml of toluene yielded 1.3 g of 4-(2-diethylaminopyridin-5-yl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5-(1H)-thione as a solid, mp 96.degree.-98.degree. C., Compound 182 of Table 1. The nmr and mass spectra were consistent with the proposed structure.
EXAMPLE 14
4-(4-Bromo-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-one
Step A
4-(4-Bromo-2-methylphenyl)-2-methyl-3-semicarbazide
Following procedures similar to those employed in Step A of Example 2, the reaction of 10.0 g (0.0472 mole) of 4-bromo-2-methylphenyl isocyanate with 2.17 g (0.0472 mole) of methylhydrazine in 150 ml of tetrahydrofuran yielded 7.36 g of 4-(4-bromo-2-methylphenyl)-2-methyl-3-semicarbazide as a solid, m.p. 127.degree.-128.degree. C. The nmr spectrum was consistent with the proposed structure.
Step B
4-(4-Bromo-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-one
Following procedures similar to those employed in Step B of Example 3, the reaction of 0.06 g (0.274 mole) of 4-(4-bromo-2-methylphenyl)-2-methyl-3-semicarbazide with 5.75 g (0.0274 mole) of trifluoroacetic anhydride in 100 ml of toluene yielded 4.6 g of 4-(4-bromo-2-methylphenyl)-3-trifluoromethyl-4,5-dihydro-1-methyl-1,2,4-triazol-5(1H)-one as a solid, mp 80.degree.-83.degree. C., Compound 198 of Table 1. The nmr spectrum was consistent with the proposed structure.
Representing compounds of the invention are set forth in Table 1. Identifying properties for these compounds are found in Table 2. The compounds are identified in Table 2 by numbers which correspond to the Compound Numbers assigned in Table 1.
The substituted-phenyl-1,2,4-triazol-5(1H)-thiones and -ones disclosed herein are useful for controlling undesired plant growth. To demonstrate this activity, representative compounds underwent pre- and postemergence evaluations using a variety of broadleaf and grasseous crops and weeds. The results of these evaluations are shown in Tables 3 and 4. The compounds are identified in Tables 3 and 4 by numbers which correspond to the Compound Numbers assigned in Table 1. The plant test species used in demonstrating the herbicidal activity of this invention included cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), lima bean (Phaseolus lunatus L.), field corn (Zea mays var. Agway 425 x or PN3732), rice (Oryza sativa var. Labelle), wheat (Triticum aestivium var. Wheaton), field bindweed (Convolvulus arvensis), morningglory (Ipomoea lacunosa or Ipomoea hederacea) (reported as "Gloryspp" in Tables 3 and 4), velvetleaf (Abutilon theophrasti) (reported as "Velvetlf" in Tables 3 and 4), wild oat (Avena fatua), barnyardgrass (Echinochloa crus-galli) (reported as "Barnydgr" in Tables 3 and 4), green foxtail (Setaria viridis) (reported as "Foxgreen" in Tables 3 and 4), johnsongrass (Sorghum halepense) (reported as "Johngr" in Tables 3 and 4), tomato (Lycopersicon esculentum), and wild mustard (Brassica kaber) (reported as "Mustwild" in Tables 3 and 4).
To prepare a stock solution for testing, 0.48 gram of a compound of the invention was weighed into a flask and then dissolved in 60 ml of an aqueous acetone solution (water:acetone, 50:50) containing 0.5% (v/v) of sorbitan monolaurate emulsifier/solubilizer. Upon dissolution, the 60 ml solution was divided into two 30 ml portions, each portion being equivalent to 8.0 kg/ha when sprayed onto four 15 cm.times.25 cm test flats. One 30 ml portion was set aside for future use. The second portion was diluted with an additional 30 ml of the aqueous acetone/emulsifier solution to provide 60 ml of a 4.0 kg/ha solution. A 30 ml portion of this solution was diluted in the same manner as described above to provide 60 ml of a 2.0 kg/ha solution. Successive serial dilutions were made to provide test solutions for the remaining application rates. The test flats consisted of disposable fiber flats, 8 cm.times.15 cm.times.25 cm, which were filled to a depth of approximately 6.5 cm with steam sterilized sandy loam soil. The soil was leveled and impressed with a template to provide evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of the crops or weeds were planted in the furrows, one species per furrow, and the template was again employed to firmly press the seeds into place. A topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.
For postemergence testing, the flats were planted with the test species 8 to 11 days prior to treatment. The various dilutions of the compounds of the invention were then sprayed directly onto the soil surface of the two preemergence test flats, on the foliage of the two postemergence test flats. The treated flats were maintained in a greenhouse for two weeks prior to evaluation for herbicidal activity.
Herbicidal data at application rates equivalent to 8.0 kilograms/hectare (kg/ha) and/or submultiples thereof, i.e., 4.0 kg/ha and 2.0 kg/ha, are given for various compounds of the invention in Table 3 (preemergence activity) and Table 4 (postemergence activity). In some instances in Tables 3 and 4, the data is reported as percent kill (% K), and in other instances, the data is reported in the Tables as percent control (% C).
Percent kill, as reported in Tables 3 and 4, denotes the percentage of plants killed following application of the compounds of the invention.
Percent control, as also reported in Tables 3 and 4, is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science", 2nd ed., B. Truelove, ed., Southern Weed Science Society, Auburn University, Auburn, Ala., 1977. The rating system is as follows:
______________________________________Herbicide Rating SystemRating DescriptionPercent of Main Crop WeedControl Categories Description Description______________________________________ 0 No effect No crop No weed reduction control or injury10 Slight dis- Very poor weed coloration control or stunting20 Slight Some dis- Poor weed effect coloration, control stunting or stand loss30 Crop injury Poor to defi- more pronounced cient weed but not lasting control40 Moderate injury, Deficient weed crop usually control recovers50 Moderate Crop injury Deficient to effect more lasting, moderate weed recovery doubt- control ful60 Lasting crop Moderate weed injury, no control recovery70 Heavy injury and Control some- stand loss what less than satisfactory80 Severe Crop nearly des- Satisfactory troyed, a few to good weed survivors control90 Only occasional Very good to live plants left excellent control100 Complete Complete crop Complete weed effect destruction destruction______________________________________
In Tables 3 and 4, no entry means that the compounds were not tested against the particular plant species.
Compounds 25, 120, 121, 202, and 203 were not tested in pre- or postemergence evaluations (Tables 3 and 4) due to insufficient quantities of test compound.
For use in herbicidal applications, the active compounds may be, if desired, formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. 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 concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
These herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired. These formulations may contain as little as 0.1% to 0.2% or 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 or less of the herbicidal compound and 99.0 parts of talc.
Wettable powders, also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Other possible wettable powder formulations are:
______________________________________ % by Wt.______________________________________Component:Active ingredient 40.00Sodium lignosulfonate 20.00Attapulgite clay 40.00Total 100.00Active ingredient 90.00Dioctyl sodium sulfosuccinate 0.10Synthetic fine silica 9.90Total 100.00Active ingredient 20.00Sodium alkylnaphthalenesulfonate 4.00Sodium lignosulfonate 4.00Low viscosity methyl cellulose 3.00Attapulgite clay 69.00Total 100.00Active ingredient 25.00Base:96% hydrated aluminum magnesium silicate 75.002% powdered sodium lignosulfonate2% powdered anionic sodium alkyl-naphthalenesulfonateTotal 100.00______________________________________
Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and adsorption by the plant.
Other useful formulations for herbicidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid or paste compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. 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 ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
The following are examples of emulsifiable contrate formulations which may be used in herbicidal applications:
______________________________________Component: % by Wt.______________________________________Active ingredient 53.01Blend of alkylnaphthalenesulfonate 6.00and polyoxyethylene ethersEpoxidized soybean oil 1.00Xylene 39.99Total 100.00Active ingredient 10.00Blend of alkylnaphthalenesulfonate 4.00and polyoxyethylene ethersXylene 86.00Total 100.00______________________________________
Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
The following are examples of flowable formulations which may be used in herbicidal applications:
______________________________________Component: % by Wt.______________________________________Active ingredient 46.00Colloidal magnesium aluminum silicate 0.40Sodium alkylnaphthalenesulfonate 2.00Paraformaldehyde 0.10Water 40.70Propylene glycol 7.50Acetylenic alcohols 2.50Xanthan gum 0.80Total 100.00Active ingredient 45.00Water 48.50Purified smectite clay 2.00Xanthan gum 0.50Sodium alkylnaphthalenesulfonate 1.00Acetylenic alcohols 3.00Total 100.00______________________________________
Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the composition.
Other useful formulations include simple solutions or suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents. The following illustrate specific suspensions which may be useful in herbicidal applications.
______________________________________ % by Wt.______________________________________Oil Suspension:Active ingredient 25.00Polyoxyethylene sorbitol hexaoleate 5.00Highly aliphatic hydrocarbon oil 70.00Total 100.00Aqueous Suspension:Active ingredient 40.00Polyacrylic acid thickener 0.30Dodecylphenol polyethylene glycol ether 0.50Disodium phosphate 1.00Monosodium phosphate 0.50Polyvinyl alcohol 1.00Water 56.70Total 100.00______________________________________
Other useful formulations for herbicidal applications 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 Freon.TM. fluorinated hydrocarbons, may also be used. Water-soluble or water dispersible granules are also useful formulations for herbicidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. Pat No. 3,920,442 are useful herein with the present herbicidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
In addition, 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 amount may be as low as, e.g., about 1 to about 50 g/ha, preferably about 4 to 30 g/ha. For field use, where there are losses of herbicide, higher application rates (e.g., four times the rates mentioned above) may be employed.
The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g., they may be mixed with, for example, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2ethyl-6-methylphenyl-N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine (diethatyl-ethyl) benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzsothiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine (atrazine), and 2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl-]amino-2-methylpropanenitrile (cyanazine); dinitroaniline herbicides such as 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl) benzeneamine (trifluralin); aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenylurea (fluo-meturon); and 2-[(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone.
As will be apparent to those skilled in the art, various modifications may be made in the formulations and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.
Tables 1 through 4 follow. These Tables set forth representative compounds of the invention and identify various properties thereof, including the herbicidal utility of these compounds.
TABLE 1__________________________________________________________________________NOVEL 4-(SUBSTITUTED ARYL)-4,5-DIHYDRO-1,2,4-TRIAZOL-5(1H)-THIONES__________________________________________________________________________ ##STR32##Cmpd.No. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6__________________________________________________________________________1 H CH.sub.3 H H Cl H H2 CH.sub.3 CH.sub.3 H H Cl H H3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 H H Cl H H4 CCl.sub.3 CH.sub.3 H H Cl H H5 CF.sub.3 CH.sub.3 H H H H H6 CF.sub.3 CH.sub.3 F H H H H7 CF.sub.3 CH.sub.3 H F H H H8 CF.sub. 3 CH.sub.3 H H F H H9 CF.sub.3 CH.sub.3 Cl H H H H10 CF.sub.3 CH.sub.3 H Cl H H H11 CF.sub.3 CH.sub.3 H H Cl H H12 CF.sub.3 CH.sub.3 Br H H H H13 CF.sub.3 CH.sub.3 H Br H H H14 CF.sub.3 CH.sub.3 H H Br H H15 CF.sub.3 CH.sub.3 H I H H H16 CF.sub.3 CH.sub.3 CH.sub.3 H H H H17 CF.sub.3 CH.sub.3 H CH.sub.3 H H H18 CF.sub.3 CH.sub.3 H H CH.sub.3 H H19 CF.sub.3 CH.sub.3 H H CH.sub.2 CH.sub.3 H H20 CF.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H H21 CF.sub.3 CH.sub.3 CF.sub.3 H H H H22 CF.sub.3 CH.sub.3 H CF.sub.3 H H H23 CF.sub.3 CH.sub.3 H H CF.sub.3 H H24 CF.sub.3 CH.sub.3 CCH H H H H25 CF.sub.3 CH.sub.3 H C CH H H H26 CF.sub.3 CH.sub.3 CCSi(CH.sub.3).sub.3 H H H H27 CF.sub.3 CH.sub.3 H C(CH.sub.3)CH.sub.2 H H H28 CF.sub.3 CH.sub.3 H CN H H H29 CF.sub.3 CH.sub.3 H H CN H H30 CF.sub.3 CH.sub.3 NO.sub.2 H H H H31 CF.sub.3 CH.sub.3 H NO.sub.2 H H H32 CF.sub.3 CH.sub.3 H H NO.sub.2 H H33 CF.sub.3 CH.sub.3 NH.sub.2 H H H H34 CF.sub.3 CH.sub.3 H NH.sub.2 H H H35 CF.sub.3 CH.sub.3 H H NH.sub.2 H H36 CF.sub.3 CH.sub.3 H NH(CH.sub.3) H H H37 CF.sub.3 CH.sub.3 H H NH(CH.sub.2 CH.sub.3) H H38 CF.sub.3 CH.sub.3 H H NH(C.sub.6 H.sub.5) H H39 CF.sub.3 CH.sub.3 H H NH(COCH.sub.3) H H40 CF.sub.3 CH.sub.3 H N(CH.sub.3).sub.2 H H H41 CF.sub. 3 CH.sub.3 H H N(CH.sub.3).sub.2 H H42 CF.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H43 CF.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 HCl H H44 CF.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3)(CH.sub.2 CH.sub.2 F) H H45 CF.sub.2 CF.sub.2 CF.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H46 CON(CH.sub.3).sub.2 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H47 CF.sub.3 CH.sub.3 H H N(n-C.sub.3 H.sub.7).sub.2 H H48 CF.sub.3 CH.sub.3 H H N(CH.sub.3)(n-C.sub.3 H.sub.7) H H49 CF.sub.3 CH.sub.3 H H N(CH.sub.3)[CH(CH.sub.3).sub.2 ] H H50 CF.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3)(CH.sub.2 CF.sub.3) H H51 CF.sub.3 CH.sub.3 H H N(CH.sub.3)(C.sub.6 H.sub.4, H-F) H52 CF.sub.3 CH.sub.3 H N.sup.+ (CH.sub.3).sub.4 I.sup.- H H53 CF.sub. 3 CH.sub.3 H OH H H H54 CF.sub.3 CH.sub.3 H H OH H H55 CF.sub.3 CH.sub.3 OCH.sub.3 H H H H56 CF.sub.3 CH.sub.3 H OCH.sub.3 H H H57 CF.sub.3 CH.sub.3 H H OCH.sub.3 H H58 CF.sub.3 CH.sub.3 H OCH(CH.sub.3).sub.2 H H H59 CF.sub.3 CH.sub.3 H H OCH(CH.sub.3).sub.2 H H60 CF.sub.3 CH.sub.3 H H OCH.sub.2 CH.sub.3 H H61 CF.sub.3 CH.sub.3 H H O(CH.sub.2).sub.2 CH.sub.3 H H62 CF.sub.3 CH.sub.3 H H O(CH.sub.2).sub.3 CH.sub.3 H H63 CF.sub.3 CH.sub.3 H O(CH.sub.2).sub.4 CH.sub.3 H H H64 CF.sub.3 CH.sub.3 H H O(CH.sub.2).sub.4 CH.sub.3 H H65 CF.sub.3 CH.sub.3 H H OC.sub.6 H.sub.5 H H66 CF.sub.3 CH.sub.3 H H OC.sub.6 H.sub.4, 4-F H H67 CF.sub.3 CH.sub.3 H H OCH.sub.2 C.sub.6 H.sub.5 H H68 CF.sub.3 CH.sub.3 H H SCH.sub.3 H H69 CF.sub.3 CH.sub.3 H H SO.sub.2 CH.sub.3 H H70 CF.sub.3 CH.sub.3 H H CH.sub.2 C.sub.6 H.sub.5 H H71 CF.sub.3 CH.sub.3 H C(O)CH.sub.3 H H H72 CF.sub.3 CH.sub.3 H H C(O)CH.sub.3 H H73 CF.sub.3 CH.sub.3 H C(O)C.sub.6 H.sub.5 H H H74 CF.sub.3 CH.sub.3 H H C(O)C.sub.6 H.sub.5 H H75 CF.sub.3 CH.sub.3 H H ##STR33## H H76 CF.sub.3 CH.sub.3 H H ##STR34## H H77 CF.sub.3 CH.sub.3 H H ##STR35## H H78 CF.sub.3 CH.sub.3 ##STR36## H H H H79 CF.sub.3 CH.sub.3 H H ##STR37## H H80 CF.sub.3 CH.sub.3 Cl Cl H H H81 CF.sub.3 CH.sub.3 Cl H Cl H H82 CF.sub.3 CH.sub.3 F H Cl H H83 CF.sub.3 CH.sub.3 F H F H H84 CF.sub.3 CH.sub.3 Cl H H Cl H85 CF.sub.3 CH.sub.3 F H H F H86 CF.sub.3 CH.sub.3 Cl H H H Cl87 CF.sub.3 CH.sub.3 F H H H F88 CF.sub.3 CH.sub.3 H Cl Cl H H89 CF.sub.3 CH.sub.3 H Cl H Cl H90 CF.sub.3 CH.sub.3 Cl H Br H H91 CF.sub.3 CH.sub.3 Cl H I H H92 CF.sub.3 CH.sub.3 Cl H CCC.sub.6 H.sub.5 H H93 CF.sub.3 CH.sub.3 Cl H NO.sub.2 H H94 CF.sub.3 CH.sub.3 Cl H NH.sub.2 H H95 CF.sub.3 CH.sub.3 Cl H NH(CH.sub.3) H H96 CF.sub.3 CH.sub.3 Cl H NH(CH.sub.2 CH.sub.3) H H97 CF.sub.3 CH.sub.3 Cl H N(CH.sub.3).sub.2 H H98 CF.sub.3 CH.sub.3 Cl H N(CH.sub.2 CH.sub.3).sub.2 H H99 CF.sub.3 CH.sub.3 H Cl CH.sub.3 H H100 CF.sub.3 CH.sub.3 CH.sub.3 Cl H H H101 CF.sub.3 CH.sub.3 CH.sub.3 H Cl H H102 CF.sub.3 CH.sub.3 CH.sub.3 H H Cl H103 CF.sub.3 CH.sub.3 CH.sub.3 H H H Cl104 CF.sub.3 CH.sub.3 CH.sub.3 H F H H105 CF.sub.3 CH.sub.3 CH.sub.3 H Br H H106 CF.sub.3 CH.sub.3 CH.sub.3 H I H H107 CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H H108 CF.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H H109 CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H110 CF.sub.3 CH.sub.3 CH.sub.3 H H H CH.sub.3111 CF.sub.3 CH.sub.3 CH.sub.3 H CCH H H112 CF.sub.3 CH.sub. 3 CH.sub.3 H CCC.sub.6 H.sub.5 H H113 CF.sub.3 CH.sub.3 CH.sub.3 H CCSi(CH.sub.3).sub.3 H H114 CF.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 H H115 CF.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3 H116 CF.sub.3 CH.sub.3 CF.sub.3 H NH[C(O)C.sub.6 H.sub.5 ] H H117 CF.sub.3 CH.sub.3 NO.sub.2 H F H H118 CF.sub.3 CH.sub.3 NO.sub.2 H Cl H H119 CF.sub.3 CH.sub.3 NO.sub.2 H Br H H120 CF.sub.3 CH.sub.3 NO.sub.2 H CF.sub.3 H H121 CF.sub.3 CH.sub.3 NO.sub.2 H NH[C(O)CH.sub.3 ] H H122 CF.sub.3 CH.sub.3 NH.sub.2 H F H H123 CF.sub.3 CH.sub.3 NH.sub.2 H Cl H H124 CF.sub.3 CH.sub.3 NH[C(O)CH.sub.3 ] H Cl H H125 CF.sub.3 CH.sub.3 NH[C(O)C.sub.6 H.sub.5 ] H F H H126 CF.sub.3 CH.sub.3 OH H NO.sub.2 H H127 CF.sub.3 CH.sub.3 OH H OH H H128 CF.sub.3 CH.sub.3 OH H OCH.sub.2 CH.sub.3 H H129 CF.sub.3 CH.sub.3 OCH.sub.3 H NO.sub.2 H H130 CF.sub.3 CH.sub.3 OC(S)N(CH.sub.3).sub.2 H NO.sub.2 H H131 CF.sub.3 CH.sub.3 OCH.sub.3 H OCH.sub.3 H H132 CF.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 H OCH.sub.2 CH.sub.3 H H133 CF.sub.3 CH.sub.3 SCH.sub.3 H NO.sub.2 H H134 CF.sub.3 CH.sub.3 SC(O)N(CH.sub.3).sub.2 H NO.sub.2 H H135 CF.sub.3 CH.sub.3 Cl Cl Cl H H136 CF.sub.3 CH.sub.3 Cl H Cl Cl H137 CF.sub.3 CH.sub.3 F H Cl F H138 CF.sub.3 CH.sub.3 F H N(CH.sub.2 CH.sub.3).sub.2 F H139 CF.sub.3 CH.sub.3 F H N(CH.sub.2 CH.sub.3)[C(O)CH.sub.3 F H140 CF.sub.3 CH.sub.3 Cl H N(CH.sub.2 CH.sub.3).sub.2 Cl H141 CF.sub.3 CH.sub.3 F H OCH.sub.3 Cl H142 CF.sub.3 CH.sub.3 Cl H OCH.sub.3 Cl H143 CF.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H144 CF.sub.3 CH.sub.3 Cl H Cl H Cl145 CF.sub.3 CH.sub.3 F H N(CH.sub.2 CH.sub.3).sub.2 H F146 CF.sub.3 CH.sub.3 H Cl Cl Cl H147 CF.sub.3 CH.sub.3 H F Cl F H148 CF.sub.3 CH.sub.3 H Cl OCH(CH.sub.3).sub.2 Cl H149 CF.sub.3 CH.sub.3 H Cl NH[(CH.sub.2).sub.3 CH.sub.3 ] Cl H150 CF.sub.3 CH.sub.3 H Cl N(CH.sub.3).sub.2 Cl H151 CF.sub.3 CH.sub.3 H Cl N(CH.sub.2 CH.sub.3).sub.2 Cl H152 CF.sub.3 CH.sub.3 H F OCH(CH.sub.3).sub.2 F H153 CF.sub.3 CH.sub.3 H F N(CH.sub.3)(CH.sub.2 CH.sub.3) F H154 CF.sub.3 CH.sub.3 H Cl N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2 Cl H155 CF.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 H156 CF.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3157 CF.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H158 CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 OCH.sub.3 H159 CF.sub.3 CH.sub.3 NO.sub.2 H F (CH.sub.2).sub.3 CH.sub.3 H160 CF.sub.3 CH.sub.3 H OCH.sub.2 O H H161 CF.sub.3 CH.sub.3 H CH.sub.2 C(CH.sub.3).sub.2 O H H162 CF.sub.3 CH.sub.3 H OC(CH.sub.3)(CH.sub.2 CH.sub.3)O H H163 CF.sub.3 CH.sub.3 H N(CH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.2 CH.sub.3) H H164 CF.sub.3 CH.sub.3 H OCH.sub.2 CH.sub.2 N[CH(CH.sub.3).sub.2 H H165 CF.sub.3 CH.sub.3 H OCH.sub.2 CH.sub.2 O H H166 CF.sub.3 CH.sub.2 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H167 CF.sub.3 CH(CH.sub.3).sub.2 H H N(CH.sub.2 CH.sub.3).sub.2 H H168 CF.sub.3 CH.sub.2 CH.sub.2 OH H H H H H169 CF.sub.3 CH.sub.2 CH.sub.2 OH H H Cl H H170 CF.sub.3 CH.sub.2 CH.sub.2 OH H H Br H H171 CF.sub.3 CH.sub.2 CH.sub.2 OH H H N(CH.sub.2 CH.sub.3).sub.2 H H172 CF.sub.3 CH.sub.2 CH.sub.2 CN H H Br H H173 CF.sub.3 CH.sub.2 C.sub.6 H.sub.5 H H H H H174 CF.sub.3 CH.sub.2 C.sub.6 H.sub.5 H H Cl H H175 CF.sub.3 CH.sub.2 C.sub.6 H.sub.5 H H Br H H176 C.sub.6 H.sub.5 CH.sub.3 H H Cl H H177 C(O)CH.sub.2 CH.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H178 CO.sub.2 CH.sub.3 CH.sub.3 H H N(CH.sub.2 CH.sub.3).sub.2 H H__________________________________________________________________________ ##STR38##Cmpd.No. R R.sup.1 R.sup.4__________________________________________________________________________179 CF.sub.3 CH.sub.3 H180 CF.sub.3 CH.sub.3 N(CH.sub.3).sub.2181 CF.sub.3 CH.sub.3 N(CH.sub.2 CH.sub.3).sub.2182 ##STR39##__________________________________________________________________________ ##STR40##Cmpd.No. R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6__________________________________________________________________________183 H H H H H184 Cl H H H H185 F H H H H186 NO.sub.2 H H H H187 H Cl H H H188 H F H H H189 H H Cl H H190 H H F H H191 H H CH(CH.sub.3).sub.2 H H192 H H OH H H193 H H OCH.sub.3 H H194 H H OCH(CH.sub.3).sub.2 H H195 H H O(CH.sub.2).sub.4 CH.sub.3 H H196 H H SO.sub.2 CH.sub.3 H H197 CH.sub.3 H Cl H H198 CH.sub.3 H Br H H199 CF.sub.3 H NO.sub.2 H H200 NO.sub.2 H Br H H201 NO.sub.2 H CF.sub.3 H H202 NO.sub.2 H NH[C(O)CH.sub.3 ] H H203 H Cl OCH(CH.sub.3).sub.2 Cl H204 OC(CH.sub.2).sub.2 CH.sub.2 H H H__________________________________________________________________________ ##STR41##Cmpd.No. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6__________________________________________________________________________205 CF.sub.3 CH.sub.3 OCHF.sub.2 H OCH(CH.sub.3).sub.2 Cl H206 CF.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 OCH.sub.3 H207 CF.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 CH.sub. 3 H208 CF.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 OCHF.sub.2 H209 CF.sub.2 CH.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H210 CF.sub.3 CH.sub.3 Cl H ##STR42## Cl H211 CF.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H212 CF.sub.3 CH.sub.3 Cl H OC(CH.sub.3).sub.2 O H213 CF.sub.3 CH.sub.3 Cl NO.sub.2 OCH(CH.sub.3).sub.2 Cl H214 CF.sub.3 CH.sub.3 Cl NHSO.sub.2 CH.sub.3 OCH(CH.sub.3).sub.2 Cl H215 CF.sub.3 CH.sub.3 Cl H N(C.sub.2 H.sub.5)(COCH.sub.3) Cl H216 CF.sub.3 CH.sub.3 Cl NH.sub.2 OCH(CH.sub.3).sub.2 Cl H217 H CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H218 CF.sub.3 CH.sub.3 Cl H NH(C.sub.2 H.sub.5) Cl H219 CF.sub.3 CH.sub.3 Cl H OCHCH.sub.2 Cl H220 CF.sub.3 CH.sub.3 Cl COC(CH.sub.3).sub.2 O Cl H221 CF.sub.3 CH.sub.3 Cl H O(C.sub.3 H.sub.7) Cl H222 Cl CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H223 CF.sub.3 n-C.sub.4 H.sub.9 Cl H OCH(CH.sub.3).sub.2 Cl H224 CF.sub.3 ##STR43## Cl H OCH(CH.sub.3).sub.2 Cl H225 N(CH.sub.3).sub.2 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H226 CN CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H227 CF.sub.3 CH.sub.3 Cl H OCH.sub.2 CHCH.sub.2 Cl H228 CF.sub.3 CH.sub.3 Cl CH.sub.2 CH.sub.2 CH.sub.2 O Cl H229 CF.sub.3 CH.sub.3 Cl H OC(CH.sub.3)CH.sub.2 Cl H230 OCH.sub.3 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H231 CF.sub.3 CH.sub.2 CH.sub.2 OH H H N(C.sub.2 H.sub.5).sub.2 H H232 CF.sub.3 CH.sub.3 F H OCH(CH.sub.3).sub.2 Cl H233 CF.sub.3 CH.sub.3 Cl H NHCOCH.sub.3 H H234 CF.sub.3 CH.sub.3 Cl H OCH.sub.2 SCH.sub.3 H H235 CF.sub.3 CH.sub.3 F H N(C.sub.2 H.sub.5).sub.2 Cl H236 CF.sub.3 CH.sub.3 Cl H OCH.sub.2 O H237 CF.sub.3 CH.sub.3 Cl H N(C.sub.2 H.sub.5)(COCF.sub.3) H H238 CF.sub.3 CH.sub.3 Cl H CH.sub.3 Cl H239 CF.sub.3 CH.sub.3 Cl H OC(CH.sub.3).sub.3 Cl H240 CF.sub.3 CH.sub.3 CF.sub.3 H OCH(CH.sub.3).sub.2 H H241 CF.sub.3 CH.sub.3 F H OCH.sub.3 Cl SCH.sub.3242 CF.sub.3 CH.sub.3 SCH.sub.3 H OCH(CH.sub.3).sub.2 Cl H243 CF.sub.3 CH.sub.3 Cl H ##STR44## Cl H244 CF.sub.3 CH.sub.3 Cl H ##STR45## Cl H245 CF.sub.3 CH.sub.3 Cl H ##STR46## Cl H246 CF.sub.3 CH.sub.3 Cl CH.sub.2 C(CH.sub.3).sub.2 O Cl H247 CF.sub.2 Cl CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H248 C.sub.2 F.sub.5 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H249 CHF.sub.2 CH.sub.3 Cl H OCH(CH.sub.3).sub.2 Cl H250 CF.sub.3 CH.sub.3 Cl COC(CH.sub.3).sub.2 O OCHF.sub.2 H251 CF.sub.3 CH.sub.3 Cl H OC(CH.sub.3)(C.sub.2 H.sub.5)O H252 CF.sub.3 CH.sub.3 Cl CH.sub.2 C(CH.sub.3).sub.2 O OCHF.sub.2 H253 CF.sub.3 CH.sub.3 CF.sub.3 H N(CH.sub.3).sub.2 H H254 CF.sub.3 CH.sub.3 CF.sub.3 H OCH(CH.sub.3).sub.2 Cl H255 n-C.sub.4 H.sub.9 CH.sub.3 H H OCH.sub.3 H H256 CF.sub.3 CH.sub.3 Cl H N(CH.sub.3).sub.2 Cl H257 CF.sub.3 CH.sub.3 Br H OCH(CH.sub.3).sub.2 Br H258 CF.sub.3 CH.sub.3 Br H OCH(CH.sub.3).sub.2 H H259 CF.sub.3 CH.sub.3 Cl H OCH.sub.2 CF.sub.3 Cl H260 CF.sub.3 CH.sub.3 Cl H OCHCF.sub.2 Cl H261 CF.sub.3 CH.sub.3 Cl H OCH.sub.2 CH.sub.2 Br Cl H__________________________________________________________________________
TABLE 2______________________________________Identifying PropertiesCmpd. MP Empirical Elemental AnalysisNo. (.degree.C.) Formula C H N______________________________________ 1 290-292 C.sub.9 H.sub.8 ClN.sub.3 S C 47.87 3.57 18.62 F 47.27 3.36 18.81 2 137-140 C.sub.10 H.sub.10 ClN.sub.3 S C 50.10 4.20 17.53 F 50.14 4.21 17.59 3 227-231 C.sub.16 H.sub.14 ClN.sub.3 S C 60.85 4.47 13.30 F 60.62 4.48 13.41 4 182-183 C.sub.10 H.sub.7 Cl.sub.4 N.sub.3 S C 35.01 2.06 12.25 F 35.16 2.09 12.31 5 oil C.sub.10 H.sub.8 F.sub.3 N.sub.3 S 6 59-61 C.sub.10 H.sub.7 F.sub.4 N.sub.3 S 7 89-90 C.sub.10 H.sub.7 F.sub.4 N.sub.3 S C 43.32 2.55 15.16 F 42.42 2.62 14.90 8 94-96 C.sub.10 H.sub.7 F.sub.4 N.sub.3 S 9 119-121 C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 S C 40.90 2.40 14.31 F 40.66 2.26 14.28 10 81-83 C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 S C 40.90 2.40 14.31 F 40.97 2.27 14.36 11 73-74 C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 S C 40.90 2.40 14.31 F 40.94 2.45 14.43 12 116-117 C.sub.10 H.sub.7 BrF.sub.3 N.sub.3 S 13 108-110 C.sub.10 H.sub.7 BrF.sub.3 N.sub.3 S 14 73-75 C.sub.10 H.sub.7 F.sub.3 IN.sub.3 S C 35.52 2.09 12.43 F 35.56 2.16 12.45 15 140-141 C.sub.10 H.sub.7 F.sub.3 IN.sub.3 S 16 89-91 C.sub.11 H.sub.10 F.sub.3 N.sub.3 S C 48.35 3.69 15.38 F 48.07 3.63 15.50 17 oil C.sub.11 H.sub.10 F.sub.3 N.sub.3 S C 48.35 3.69 15.38 F 48.45 3.55 15.27 18 102-104 C.sub.11 H.sub.10 F.sub.3 N.sub.3 S C 48.35 3.69 15.38 F 48.24 3.72 15.58 19 oil C.sub.12 H.sub.12 F.sub.3 N.sub.3 S C 50.17 4.21 14.63 F 48.26 4.19 13.61 20 oil C.sub.13 H.sub.14 F.sub.3 N.sub.3 S 21 145-147 C.sub.11 H.sub.7 F.sub.6 N.sub.3 S 22 56-59 C.sub.11 H.sub.7 F.sub.6 N.sub.3 S 23 107-108 C.sub.11 H.sub.7 F.sub.6 N.sub.3 S C 40.37 2.16 12.84 F 40.13 2.15 12.87 24 90-91 C.sub.12 H.sub.8 F.sub.3 N.sub.3 C 50.88 2.83 14.84 F 51.28 2.81 14.12 25 -- C.sub.12 H.sub.8 F.sub.3 N.sub.3 S 26 79-81 C.sub.15 H.sub.16 F.sub.3 N.sub.3 SSi 27 64-66 C.sub.13 H.sub.12 F.sub.3 N.sub.3 S C 52.17 4.01 14.05 F 52.03 3.88 13.92 28 165-166 C.sub.11 H.sub.7 F.sub.3 N.sub.4 S C 46.48 2.48 19.71 F 46.39 2.68 19.96 29 60-61 C.sub.11 H.sub.7 F.sub.3 N.sub.4 S 30 190-193 C.sub.10 H.sub.7 F.sub.3 N.sub.4 O.sub.2 S 31 oil C.sub.10 H.sub.7 F.sub.3 N.sub.4 O.sub.2 S 32 108-109 C.sub.10 H.sub.7 F.sub.3 N.sub.4 O.sub.2 S C 39.48 2.32 18.41 F 40.63 2.66 17.95 33 173-175 C.sub.10 H.sub.9 F.sub.3 N.sub.4 S 34 gum C.sub.10 H.sub.9 F.sub.3 N.sub.4 S 35 104-107 C.sub.10 H.sub.9 F.sub.3 N.sub.4 S 36 gum C.sub.11 H.sub.11 F.sub.3 N.sub.4 S 37 139-142 C.sub.12 H.sub.13 F.sub.3 N.sub.4 S C 47.68 4.30 18.54 F 47.76 4.43 18.42 38 177-179 C.sub.16 H.sub.13 F.sub.3 N.sub.4 S 39 244-246 C.sub.12 H.sub.11 F.sub.3 N.sub.4 OS 40 oil C.sub.12 H.sub.13 F.sub.3 N.sub.4 S 41 151-152 C.sub.12 H.sub.13 F.sub.3 N.sub.4 S C 47.68 4.30 18.54 F 47.41 4.16 18.38 42 110-113 C.sub.14 H.sub.17 F.sub.3 N.sub.4 S C 50.91 5.15 16.97 F 51.71 5.10 16.74 43 210-211 C.sub.14 H.sub.18 ClF.sub.3 N.sub.4 S 44 99-102 C.sub.14 H.sub.16 F.sub.4 N.sub.4 S 45 109-110 C.sub. 16 H.sub.17 F.sub.7 N.sub.4 S 46 154-157 C.sub.16 H.sub.23 N.sub.5 OS 47 gum C.sub.16 H.sub.21 F.sub.3 N.sub.4 S 48 59-60 C.sub.14 H.sub.17 F.sub.3 N.sub.4 S 49 85-86 C.sub.14 H.sub.17 F.sub.3 N.sub.4 S 50 110-113 C.sub.14 H.sub.14 F.sub.6 N.sub.4 S 51 99-102 C.sub.17 H.sub.14 F.sub.4 N.sub.4 S 52 >220 C.sub.13 H.sub.16 F.sub.3 IN.sub.4 S 53 131-134 C.sub.10 H.sub.8 F.sub.3 N.sub.3 OS 54 72-75 C.sub.10 H.sub.8 F.sub.3 N.sub.3 OS 55 138-140 C.sub.11 H.sub.10 F.sub.3 N.sub.4 OS C 45.67 3.46 14.53 F 45.62 3.18 14.37 56 oil C.sub.11 H.sub.10 F.sub.3 N.sub.3 OS 57 oil C.sub.11 H.sub.10 F.sub.3 N.sub.3 OS 58 oil C.sub.13 H.sub.14 F.sub.3 N.sub.3 OS C 49.21 4.42 13.25 F 49.50 4.71 13.09 59 89-91 C.sub.13 H.sub.14 F.sub.3 N.sub.3 OS C 49.21 4.42 13.25 F 49.02 4.28 13.13 60 93-95 C.sub.12 H.sub.12 F.sub.3 N.sub.3 OS 61 68-70 C.sub.13 H.sub.14 F.sub.3 N.sub.3 OS C 49.21 4.42 13.25 F 49.35 4.35 13.05 62 69-70 C.sub.14 H.sub.16 F.sub.3 N.sub.3 OS 63 oil C.sub.15 H.sub.18 F.sub.3 N.sub.3 OS 64 52-53 C.sub.15 H.sub.18 F.sub.3 N.sub.3 OS 65 84-86 C.sub.16 H.sub.12 F.sub.3 N.sub.3 OS C 54.70 3.44 11.96 F 54.63 3.35 12.01 66 116-117 C.sub.16 H.sub.11 F.sub.4 N.sub.3 OS 67 -- C.sub.17 H.sub.14 F.sub.3 N.sub.3 OS 68 71-75 C.sub.11 H.sub.10 F.sub.3 N.sub.3 S.sub.2 69 207-209 C.sub.11 H.sub.10 F.sub.3 N.sub.3 O.sub.2 S.sub.2 70 103-104 C.sub.17 H.sub.14 F.sub.3 N.sub.3 S C 58.45 4.01 12.03 F 58.35 4.12 11.87 71 gum C.sub.12 H.sub.10 F.sub.3 N.sub.3 OS 72 151-153 C.sub.12 H.sub.10 F.sub.3 N.sub.3 OS C 47.84 3.32 13.95 F 48.82 3.41 13.79 73 122-124 C.sub.17 H.sub.12 F.sub.3 N.sub.3 OS C 56.20 3.31 11.57 F 55.97 3.48 11.30 74 141-142 C.sub.17 H.sub.12 F.sub.3 N.sub.3 OS C 56.20 3.31 11.57 F 56.32 3.30 11.29 75 150-153 C.sub.14 H.sub.15 F.sub.3 N.sub.4 S 76 133-135 C.sub.15 H.sub.17 F.sub.3 N.sub.4 S 77 65-66 C.sub.14 H.sub.15 F.sub.3 N.sub.4 OS 78 115-117 C.sub.14 H.sub.1 OF.sub.6 N.sub.6 S 79 65-66 C.sub.14 H.sub.10 F.sub.6 N.sub.6 S 80 118-120 C.sub.10 H.sub.6 C.sub.12 F.sub.3 N.sub.3 S C 36.59 1.83 12.80 F 36.82 2.02 12.55 81 oil C.sub.10 H.sub.6 C.sub.12 F.sub.3 N.sub.3 S 82 74-75 C.sub.10 H.sub.6 F.sub.5 N.sub.3 S 83 80-85 C.sub.10 H.sub.6 BrF.sub.4 N.sub.3 S 84 149-151 C.sub.10 H.sub.6 Cl.sub.2 F.sub.3 N.sub.3 S C 36.59 1.83 12.80 F 36.51 1.95 12.59 85 52-55 C.sub.10 H.sub.6 F.sub.5 N.sub.3 S 86 117-119 C.sub.10 H.sub.6 Cl.sub.2 F.sub.3 N.sub.3 S 87 80-83 C.sub.10 H.sub.6 F.sub.5 N.sub.3 S 88 96-97 C.sub.10 H.sub.6 Cl.sub.2 F.sub.3 N.sub.3 S C 36.59 1.83 12.80 F 36.47 1.74 12.83 89 130-131 C.sub.10 H.sub.6 Cl.sub.2 F.sub.3 N.sub.3 S 90 90-93 C.sub.10 H.sub.6 BrClF.sub.3 N.sub.3 S C 32.22 1.61 11.28 F 32.70 1.75 10.82 91 117-119 C.sub.10 H.sub.6 ClF.sub.3 IN.sub.3 S 92 50-53 C.sub.18 H.sub.11 ClF.sub.3 N.sub.3 S C 54.89 2.80 10.67 F 54.78 2.69 10.70 93 152-155 C.sub.10 H.sub.6 ClF.sub.3 N.sub.4 O.sub.2 S 94 145-147 C.sub.10 H.sub.8 ClF.sub.3 N.sub.4 S 95 127-130 C.sub.11 H.sub.10 ClF.sub.3 N.sub.4 S 96 87-90 C.sub.12 H.sub.12 ClF.sub.3 N.sub.4 S 97 122-125 C.sub.12 H.sub.12 ClF.sub.3 N.sub.4 S C 42.79 3.57 16.64 F 42.83 3.42 16.70 98 108-110 C.sub.14 H.sub.16 ClF.sub.3 N.sub.4 S 99 oil C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 S100 75-76 C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 S C 42.94 2.95 13.65 F 42.94 2.95 13.79101 oil C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 S102 104-105 C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 S C 42.94 2.95 13.65 F 42.73 2.73 12.68103 99-101 C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 S C 42.94 2.95 13.65 F 42.47 3.01 13.74104 75-76 C.sub.11 H.sub.9 F.sub.4 N.sub.3 S105 80-84 C.sub.11 H.sub.9 BrF.sub.3 N.sub.3 S C 37.52 2.58 11.93 F 37.31 2.45 11.83106 104-107 C.sub.11 H.sub.9 F.sub.3 IN.sub.3 S C 33.09 2.26 10.53 F 33.17 2.27 10.33107 97-99 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S108 71-72 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S109 100-101 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S110 74-76 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S C 50.17 4.18 F 49.94 3.89111 oil C.sub.13 H.sub.10 F.sub.3 N.sub.3 S C 52.53 3.37 14.14 F 52.29 3.09 13.87112 111-113 C.sub.19 H.sub.14 F.sub.3 N.sub.3 S C 61.13 3.75 11.26 F 60.87 3.62 11.20113 90-93 C.sub.16 H.sub.18 F.sub.3 N.sub.3 SSi114 84-85 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S C 50.17 4.18 14.63 F 49.51 14.45 14.56115 84-85 C.sub.12 H.sub.12 F.sub.3 N.sub.3 S C 50.17 4.18 F 49.98 4.06116 220-222 C.sub.18 H.sub.12 F.sub.6 N.sub.4 OS117 94-96 C.sub.10 H.sub.6 F.sub.4 N.sub.4 O.sub.2 S118 131-134 C.sub.10 H.sub.6 ClF.sub.3 N.sub.4 O.sub.2 S119 114-116 C.sub.10 H.sub.6 BrF.sub.3 N.sub.4 O.sub.2 S120 -- C.sub.11 H.sub.6 F.sub.6 N.sub.4 O.sub.2 S121 gum C.sub.12 H.sub.10 F.sub.3 N.sub.5 O.sub.3 S122 166-168 C.sub.10 H.sub.8 F.sub.4 N.sub.4 S123 144-146 C.sub.10 H.sub.8 ClF.sub.3 N.sub.4 S124 207-210 C.sub.12 H.sub.10 ClF.sub.3 N.sub.4 OS C 41.08 2.85 15.98 F 40.81 2.62 15.76125 135-137 C.sub.17 H.sub.12 F.sub.4 N.sub.4 OS126 193-195 C.sub.10 H.sub.7 F.sub.3 N.sub.4 O.sub.3 S127 171-174 C.sub.10 H.sub.8 F.sub.3 N.sub.3 O.sub.2 S128 oil C.sub.12 H.sub.12 F.sub.3 N.sub.3 O.sub.2 S129 138-140 C.sub.11 H.sub.9 F.sub.3 N.sub.4 O.sub.3 S130 166-169 C.sub.13 H.sub.12 F.sub.3 N.sub.5 O.sub.3 S.sub.2131 88-90 C.sub.12 H.sub.12 F.sub.3 N.sub.3 O.sub.2 S132 oil C.sub.14 H.sub.16 F.sub.3 N.sub.3 O.sub.2 S133 134-137 C.sub.11 H.sub.9 F.sub.3 N.sub.4 O.sub.2 S134 217-220 C.sub.13 H.sub.12 F.sub.3 N.sub.5 O.sub.3 S.sub.2135 125-127 C.sub.10 H.sub.5 Cl.sub.3 F.sub.3 N.sub.3 S136 123-125 C.sub.10 H.sub.5 Cl.sub.3 F.sub.3 N.sub.3 S137 oil C.sub.10 H.sub.5 ClF.sub.5 N.sub.3 S138 88-89 C.sub.14 H.sub.15 F.sub.5 N.sub.4 S139 129-133 C.sub.14 H.sub.13 F.sub.5 N.sub.4 OS140 oil C.sub.14 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 S141 123-124 C.sub.11 H.sub.8 Cl.sub.2 F.sub.3 N.sub.3 OS142 141-143 C.sub.11 H.sub.8 Cl.sub.2 F.sub.3 N.sub.3 OS143 97-99 C.sub.13 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS144 80-84 C.sub.10 H.sub.5 Cl.sub.3 F.sub.3 N.sub.3 S145 106-108 C.sub.14 H.sub.15 F.sub.5 N.sub.4 S146 118-121 C.sub.10 H.sub.5 Cl.sub.3 F.sub.3 N.sub.3 S C 33.10 1.38 11.59 F 32.60 1.43 11.46147 115-117 C.sub.10 H.sub.5 ClF.sub.5 N.sub.3 S148 -- C.sub.13 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS149 73-75 C.sub.14 H.sub.15 Cl.sub.2 F.sub. 3 N.sub.4 S C 42.11 3.76 14.04 F 42.15 3.74 14.11150 gum C.sub.12 H.sub.11 Cl.sub.2 F.sub.3 N.sub.4 S C 38.81 2.96 15.09 F 38.55 3.14 14.84151 128-130 C.sub.14 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 S152 77-78 C.sub.13 H.sub.12 F.sub.5 N.sub.3 OS153 83-85 C.sub.13 H.sub.13 F.sub.5 N.sub.4 S154 118-121 C.sub.16 H.sub.19 Cl.sub.2 F.sub.3 N.sub.4 S155 63-66 C.sub.13 H.sub.14 F.sub.3 N.sub.3 S156 100-103 C.sub.13 H.sub.14 F.sub.3 N.sub.3 S C 51.83 4.65 F 51.62 4.36157 100-102 C.sub.13 H.sub.14 F.sub.3 N.sub.3 S158 161-163 C.sub.13 H.sub.14 F.sub.3 N.sub.3 O.sub.3 S C 44.70 4.01 12.03 F 44.53 4.03 12.03159 oil C.sub.14 H.sub.14 F.sub.4 N.sub.4 O.sub.2 S160 148-151 C.sub.11 H.sub.8 F.sub.3 N.sub.3 O.sub.2 S C 43.57 2.66 13.86 F 43.21 2.53 13.51161 97-99 C.sub.14 H.sub.14 F.sub.3 N.sub.3 OS162 gum C.sub.14 H.sub.14 F.sub.3 N.sub.3 O.sub.2 S C 48.70 4.06 12.17 F 49.49 4.29 16.77163 104-106 C.sub.16 H.sub.20 F.sub.3 N.sub.5 S164 oil C.sub.15 H.sub.17 F.sub.3 N.sub.4 OS165 154-157 C.sub.12 H.sub.10 F.sub.3 N.sub.3 O.sub.2 S166 88-90 C.sub.15 H.sub.19 F.sub.3 N.sub.4 S167 109-111 C.sub.16 H.sub.21 F.sub.3 N.sub.4 S168 oil C.sub.11 H.sub.10 F.sub.3 N.sub.3 OS169 130-132 C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 OS C 40.81 2.80 12.98 F 40.94 2.81 13.03170 137-139 C.sub.11 H.sub.9 BrF.sub.3 N.sub.3 OS C 35.89 2.46 11.41 F 36.02 2.50 11.36171 oil C.sub.15 H.sub.19 F.sub.3 N.sub.4 OS172 136-137 C.sub.12 H.sub.8 BrF.sub.3 N.sub.4 S C 38.21 2.14 14.85 F 38.35 2.35 15.05173 148-150 C.sub.16 H.sub.12 F.sub.3 N.sub.3 S C 57.31 3.61 12.53 F 57.41 3.62 12.66174 88-91 C.sub.16 H.sub.11 ClF.sub.3 N.sub.3 S C 51.97 3.00 11.36 F 51.98 3.14 11.33175 oil C.sub.16 H.sub.11 BrF.sub.3 N.sub.3 S176 208-210 C.sub.15 H.sub.12 ClN.sub.3 S C 59.70 4.01 13.92 F 59.06 3.78 14.06177 148-149 C.sub.16 H.sub.22 N.sub.4 OS178 168-169 C.sub.15 H.sub.20 N.sub.4 O.sub.2 S179 oil C.sub.10 H.sub.4 F.sub.7 N.sub.3 S180 73-76 C.sub.12 H.sub.9 F.sub.7 N.sub.4 S181 37-40 C.sub.14 H.sub.13 F.sub.7 N.sub.4 S182 96-98 C.sub.13 H.sub.16 F.sub.3 N.sub.5 S C 47.13 4.83 21.15 F 47.07 5.13 20.92183 79-82 C.sub.10 H.sub.8 F.sub.3 N.sub.3 O184 84-87 C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 O185 oil C.sub.10 H.sub.7 F.sub.4 N.sub.3 O186 oil C.sub.10 H.sub.7 F.sub.3 N.sub.4 O.sub.3187 102-104 C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 O C 43.24 2.52 15.14 F 43.03 2.37 14.98188 45-46 C.sub.10 H.sub.7 F.sub.4 N.sub.3 O189 oil C.sub.10 H.sub.7 ClF.sub.3 N.sub.3 O C 43.24 2.52 15.14 F 43.28 2.46 15.03190 98-100 C.sub.10 H.sub.7 F.sub.4 N.sub.3 O191 56-57 C.sub.13 H.sub.14 F.sub.3 N.sub.3 O C 54.74 4.91 14.74 F 55.02 5.05 14.44192 205-206 C.sub.10 H.sub.8 F.sub.3 N.sub.3 O.sub.2193 76-78 C.sub.11 H.sub.10 F.sub.3 N.sub.3 O.sub.2 C 48.35 3.66 15.38 F 48.21 3.45 15.17194 83-85 C.sub.13 H.sub.14 F.sub.3 N.sub.3 O.sub.2195 oil C.sub.15 H.sub.18 F.sub.3 N.sub.3 O.sub.2196 147-148 C.sub.11 H.sub.10 F.sub.3 N.sub.3 O.sub.3 S C 41.12 3.14 13.10 F 42.06 3.14 12.94197 65-67 C.sub.11 H.sub.9 ClF.sub.3 N.sub.3 O198 80-83 C.sub.11 H.sub.9 BrF.sub.3 N.sub.3 O C 39.30 2.68 12.50 F 39.26 2.40 12.34199 155-156 C.sub.11 H.sub.6 F.sub.6 N.sub.4 O.sub.3200 120-122 C.sub.10 H.sub.6 BrF.sub.3 N.sub.4 O.sub.3201 138-140 C.sub.11 H.sub. 6 F.sub.6 N.sub.4 O.sub.3202 gum C.sub.12 H.sub.10 F.sub.3 N.sub.5 O.sub.4203 -- C.sub.13 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 O.sub.2204 99-101 C.sub.14 H.sub.14 F.sub.3 N.sub.3 O.sub.2205 105 C.sub.14 H.sub.13 ClF.sub.5 N.sub.3 O.sub.2 S206 gum C.sub.14 H.sub.15 ClF.sub.3 N.sub.3 O.sub.2 S207 84 C.sub.14 H.sub.15 ClF.sub.3 N.sub.3 OS208 oil C.sub.14 H.sub.13 ClF.sub.5 N.sub.3 O.sub.2 S209 99-102 C.sub.14 H.sub.15 Cl.sub.2 F.sub.2 N.sub.3 OS210 167-170 C.sub.14 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS211 118-121 C.sub.12 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 OS212 48-51 C.sub.13 H.sub.11 ClF.sub.3 N.sub.3 O.sub.2 S213 151-153 C.sub.13 H.sub.11 Cl.sub.2 F.sub.3 N.sub.4 O.sub.3 S214 62-66 C.sub.14 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.3 S.sub.2215 58-61 C.sub.14 H.sub.13 Cl.sub.2 F.sub.3 N.sub.4 OS216 48-50 C.sub.13 H.sub.13 Cl.sub.2 F.sub.3 N.sub.4 OS217 101-103 C.sub.12 H.sub.13 Cl.sub.2 N.sub.3 OS218 gum C.sub.12 H.sub.11 Cl.sub.2 F.sub.3 N.sub.4 S219 111-114 C.sub.12 H.sub.8 Cl.sub.2 F.sub.3 N.sub.3 OS220 165-168 C.sub.14 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 O.sub.2 S221 140-143 C.sub.13 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS222 69-72 C.sub.12 H.sub.12 Cl.sub.3 N.sub.3 OS223 liquid C.sub.16 H.sub.18 Cl.sub.2 F.sub.3 N.sub.3 OS224 111-112 C.sub.19 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 OS225 131-134 C.sub.14 H.sub.18 Cl.sub.2 N.sub.4 OS226 103-105 C.sub.13 H.sub.12 Cl.sub.2 N.sub.4 OS227 125-128 C.sub.13 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 OS228 64-67 C.sub.13 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 OS229 oil C.sub.13 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 OS230 oil C.sub.13 H.sub.15 Cl.sub.2 N.sub.3 O.sub.2 S231 oil C.sub.15 H.sub.19 F.sub.3 N.sub.4 OS232 viscous C.sub.13 H.sub.12 ClF.sub.4 N.sub.3 OS oil233 211-214 C.sub.12 H.sub.10 ClF.sub.3 N.sub.4 OS234 148-151 C.sub.12 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 OS235 oil C.sub.14 H.sub.15 ClF.sub.4 N.sub.4 S236 110-113 C.sub.11 H.sub.7 ClF.sub.3 N.sub.3 O.sub.2 S237 109-111 C.sub.14 H.sub.11 ClF.sub.6 N.sub.4 OS238 123-126 C.sub.11 H.sub.8 C.sub.12 F.sub.3 N.sub.3 S239 87-88 C.sub.14 C.sub.12 F.sub.3 N.sub.3 OS240 78-80 C.sub.14 H.sub.13 F.sub.6 N.sub.3 OS241 gum C.sub.12 H.sub.10 ClF.sub.4 N.sub.3 OS.sub.2242 120-121 C.sub.14 H.sub.15 ClF.sub.3 N.sub.3 OS.sub.2243 133-136 C.sub.15 H.sub.14 Cl.sub.2 F.sub.3 N.sub.3 OS244 56-60 C.sub.16 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 OS245 104-108 C.sub.14 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS246 56-60 C.sub.14 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 OS247 liquid C.sub.13 H.sub.12 Cl.sub.3 F.sub.2 N.sub.3 OS248 87-90 C.sub.14 H.sub.12 Cl.sub.2 F.sub.5 N.sub.3 OS249 110-113 C.sub.13 H.sub.13 Cl.sub.2 F.sub.2 N.sub.3 OS250 150-152 C.sub.15 H.sub.11 ClF.sub.5 N.sub.3 O.sub.3 S251 oil C.sub.14 H.sub.13 ClF.sub.3 N.sub.3 O.sub.2 S252 viscous C.sub.15 H.sub.13 ClF.sub.5 N.sub.3 O.sub.2 S oil253 114-116 C.sub.13 H.sub.12 F.sub.6 N.sub.4 S254 70-72 C.sub.14 H.sub.12 ClF.sub.6 N.sub.3 OS255 oil C.sub.14 H.sub.19 N.sub.3 OS256 106 C.sub.12 H.sub.11 Cl.sub.2 F.sub.3 N.sub.4 S257 48-52 C.sub.13 H.sub.12 Br.sub.2 F.sub.3 N.sub.3 OS258 gum C.sub.13 H.sub.13 BrF.sub.3 N.sub.3 OS259 167-169 C.sub.12 H.sub.7 Cl.sub.2 F.sub.6 N.sub.3 OS260 122-126 C.sub.12 H.sub.6 Cl.sub.2 F.sub.5 N.sub.3 OS261 140-143 C.sub.12 H.sub.9 BrCl.sub.2 F.sub.3 N.sub.3 OS______________________________________
TABLE 3__________________________________________________________________________Preemergence Herbicidal Activity (% Control)__________________________________________________________________________ Compound No. 1* 2* 3* 4* 5 6 7* 8 9* 10* 11 12 13 14* 15 16* 17 18 19 20 21 22 23 24 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 0 10 30 0 0 0 0 10 0 40 5 0 0 5 5 20 10 0 0 10LIMABEAN 100 0 0 0 0 0 0 0 0CORN 0 0 0 80 30 0 0 30 95 0 10 10 30 30 0 10 90 0 0 0WHEAT 0 0 10 0 0 0 0 0 30 0 0 0 70 0 5 5 60 0 0 0 0TOMATO 60 0 0 0 0 0 0 0 50VELVETLF 0 0 0 0 10 60 0 0 0 0 90 0 20 30 10 0 20 50 30 80 10 0 0 0BINDWEED 0 0 0 0 0 0 0 20 70 0WILDOAT 80 0 0 0 60 0 0 60 90BARNYDGR 0 0 0 0 20 60 90 0 50 80 100 50 80 100 80 95 60 95 95 95 80 70 0 0FOXGREEN 20 20 0 0 0 30 0 0 10 0 80 40 90 70 40 95 90 30 90 100 50 70 0 10GLORYSPP 10 60 0 70 30 60 20 20 80 70 70 10 0 0 0COTTON 10 5 0 20 20JOHNGR 90 80 95 95 95RICE 95 10 50 95 95MUSTWILD 0 0 0 20__________________________________________________________________________ Compound No. 26 27 28* 29 30 31 32* 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 Rate (kg/ha)Species 8 4 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 2 2 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 10 0 0 0 30 0 0 0 0 0 40 0 20 0 50 5 20 0 0 0 10 0 70LIMABEAN 0 0CORN 0 5 0 0 0 10 0 0 0 0 50 50 0 0 40 20 60 5 5 0 0 40 10 70WHEAT 0 0 0 0 0 10 0 0 0 0 0 10 0 20 30 0 30 0 10 0 0 60 0 30TOMATO 0VELVETLF 0 20 90 10 0 50 0 0 0 0 70 100 0 0 100 50 70 30 30 0 0 80 80 95BINDWEED 0 0 60WILDOAT 0BARNYDGR 0 90 40 90 0 70 0 0 0 0 70 90 0 20 100 95 95 80 95 0 0 90 95 95FOXGREEN 0 30 80 90 0 95 0 0 0 0 80 95 0 0 95 90 95 95 90 0 0 95 95 100GLORYSPP 0 20 0 10 0 40 10 0 10 50 70 0 70 70 70 70 10 80 0 0 70 80 70COTTON 0 10 0 0 0 10 0 0 50JOHNGR 20 70 95 50 70 80 95 95 95 100RICE 80 50 70 95 20 0 10 10 90MUSTWILD 0 40 60 0 5 0 70 70__________________________________________________________________________ Compound No. 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65* 66 67* 68 69 70 71 72 73 Rate (kg/ha)Species 8 2 8 8 8 8 8 8 8 8 8 8 8 4 8 8 8 8 8 8 2 8 8 8__________________________________________________________________________SOYBEAN 90 0 0 10 50 0 0 5 0 60 80 20 5 0 0 0 10 0 30 0 0 10 0 0LIMABEAN 0 0CORN 60 5 0 0 90 0 10 50 70 30 95 95 5 20 0 0 0 0 60 0 5 10 0 0WHEAT 60 0 0 0 0 0 40 10 5 50 50 70 5 10 10 0 0 0 50 0 0 30 0 0TOMATO 0 0VELVETLF 90 5 0 10 50 0 30 40 90 95 80 20 0 0 0 0 0 40 0 50 60 0 0BINDWEED 0 0WILDOAT 0 0BARNYDGR 100 80 0 80 90 0 95 95 100 95 95 100 95 10 70 0 0 0 30 0 80 50 0 80FOXGREEN 100 90 0 30 90 90 90 95 95 100 100 100 95 0 90 90 0 0 80 50 95 90 0 90GLORYSPP 80 10 0 70 70 0 90 95 80 90 95 80 10 5 10 0 80 0 10 50 0 10COTTON 0 0 0 20 30 10 0 0 0JOHNGR 50 95 95 95 95 95 70 0 60RICE 5 50 90 90 100 95 0 5 5MUSTWILD 0 0 0 50 0 95 5 0 10__________________________________________________________________________ Compound No. 74 75 76 77 78 79 80 81* 82 83 84 85 86 87 88* 89 90 91 92 93 94 95 96 97 Rate (kg/ha)Species 8 8 8 8 8 4 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 30 0 0 0 5 20 0 0 0 0 0 0 0 0 5 30 20 0 0 0 40 30 70LIMABEAN 0 0CORN 0 30 0 0 0 20 20 0 0 0 10 20 0 0 0 5 90 60 0 0 0 50 20 90WHEAT 0 30 0 95 0 5 0 0 0 0 10 20 0 0 0 5 60 40 0 0 0 30 50 50TOMATO 0 0VELVETLF 0 50 0 20 0 40 10 0 0 0 20 0 0 20 10 80 80 0 0 0 90 90 100BINDWEED 70 90WILDOAT 20 0BARNYDGR 0 80 0 80 0 40 70 95 0 70 90 80 70 40 90 90 90 95 0 0 90 90 100 95FOXGREEN 0 90 0 0 0 30 90 100 0 70 90 60 90 50 90 50 95 100 0 0 0 95 95 100GLORYSPP 0 30 0 30 0 0 60 0 20 20 30 0 30 40 80 95 0 0 0 95 95 95COTTON 0 0 50 0JOHNGR 70 95 90RICE 20 40 70 30MUSTWILD 0 0 80 100__________________________________________________________________________ Compound No. 98 99* 100* 101* 102* 103* 104 105 106 107 108 109 110 111 112 113 114* 115 Rate (kg/ha)Species 4 8 8 8 8 8 8 8 4 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 0 0 0 0 0 0 80 10 0 5 0 0 70 20 30 0 0LIMABEAN 0 0 0 0 0 0CORN 20 30 0 0 0 0 20 90 95 100 100 100 20 95 0 0 60 90WHEAT 5 40 100 60 50 20 20 10 90 80 95 30 40 0 0 100 70TOMATO 50 80 50 0 100 40VELVETLF 60 0 40 0 0 20 0 90 80 90 80 90 0 80 0 0 90 80BINDWEED 60 40 0 0 0 80 80WILDOAT 30 80 0 90 0 95BARNYDGR 95 90 100 80 90 0 90 100 100 100 100 100 50 100 40 70 100 100FOXGREEN 100 100 100 100 100 100 30 100 100 95 100 100 70 100 20 50 100 90GLORYSPP 70 60 90 90 80 70 80 0 80 40 0 70COTTON 0 70 0 0 20 40 10 0JOHNGR 100 100 100 100 100 100 95 100RICE 0 50 100 100 100 95 95MUSTWILD 50 60 0 70 30 20 0__________________________________________________________________________ Compound No. 116 117 118 119 122 123 124 125 126 127 128 129 130 131 132 133 134 135 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 4__________________________________________________________________________SOYBEAN 0 0 0 10 10 0 10 10 0 0 0 0 0 0 30 0 0 10LIMABEANCORN 0 40 0 90 10 0 5 10 0 0 10 0 0 20 50 0 20 10WHEAT 100 40 0 50 10 30 50 30 0 0 0 0 0 20 40 0 0 5TOMATOVELVETLF 0 40 90 60 0 80 50 0 0 0 30 0 0 60 80 0 0 60BINDWEEDWILDOATBARNYDGR 0 90 70 95 10 60 10 0 30 0 90 40 0 50 90 0 0 95FOXGREEN 50 95 95 90 10 90 10 10 60 0 80 0 0 90 90 0 10 100GLORYSPP 0 40 30 70 10 60 50 10 0 0 60 0 0 10 90 0 0 80COTTON 40 30JOHNGR 10 100RICE 20 60MUSTWILD 80 0__________________________________________________________________________ Compound No. 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 Rate (kg/ha)Species 8 2 2 8 2 8 8 8 8 8 8 8 2 8 4 8 2 4__________________________________________________________________________SOYBEAN 0 0 80 40 60 80 50 80 30 0 40 0 10 10 80 0 10 70LIMABEANCORN 10 5 80 0 50 90 0 70 70 20 60 10 50 50 90 20 80 90WHEAT 0 0 40 0 50 80 50 70 30 20 70 10 30 0 60 10 30 20TOMATOVELVETLF 10 10 70 10 80 80 60 60 60 70 60 0 70 40 90 60 70 90BINDWEEDWILDOATBARNYDGR 95 90 100 80 95 100 95 100 90 100 90 80 95 100 95 100 95 100FOXGREEN 90 70 100 90 95 100 100 100 90 95 100 100 95 95 100 100 100 100GLORYSPP 60 10 70 40 85 80 90 60 50 70 80 10 80 80 90 30 70 95COTTON 0 5 20 50 0 5 10 70 0 5 0JOHNGR 60 90 100 100 50 100 95 100 95 90 95RICE 20 20 70 40 5 70 20 70 20 95 95MUSTWILD 10 10 80 70 0 70 60 80 50 5 10__________________________________________________________________________ Compound No. 154 155 156 157 158 159 160* 161 162 163 164 165 166 167 168* 169* 170* 172* Rate (kg/ha)Species 8 8 8 8 4 8 8 4 4 8 2 2 2 8 8 8 8 8__________________________________________________________________________SOYBEAN 20 40 40 40 5 0 0 5 5 0 20 5 5 0 0LIMABEAN 0 0 0 0 0CORN 0 90 90 60 90 0 30 70 30 0 5 10 5 0 0WHEAT 10 80 90 10 50 90 90 10 10 0 5 5 0 30 0TOMATO 0 0 0 0 0VELVETLF 20 90 90 70 70 0 0 40 5 0 70 20 30 20 0 0 0 0BINDWEED 0 0 0 0 0WILDOAT 40 0 0 0 0BARNYDGR 90 100 100 90 95 50 100 95 95 0 95 80 60 10 0 0 0 0FOXGREEN 95 100 100 70 95 90 100 95 95 0 100 85 90 10 0 0 0 0GLORYSPP 50 95 90 40 90 0 95 60 0 70 80 5 90COTTON 20 20 0 20 5 5 5 10 0JOHNGR 100 100 40 95 80 95 70 30 50RICE 100 100 80 95 70 30 20 50 5MUSTWILD 0 50 60 20 5 0 15 20 0__________________________________________________________________________ Compound No. 173* 174* 175* 176* 177 178 179 180 181 182 183 184 185 186 187 188 189 190 Rate (kg/ha)Species 8 8 8 8 8 8 8 2 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 0 0 70 90 95 0 0 0 10 0 0 0 0LIMABEAN 0 0 0 0CORN 0 0 50 50 60 95 0 10 0 70 10 0 10 0WHEAT 0 0 30 5 50 90 0 20 0 10 30 0 20 0TOMATO 0 0 0 0VELVETLF 0 0 0 0 0 0 30 60 90 100 0 0 0 60 0 0 50 0BINDWEED 0 0 0 0WILDOAT 0 0 0 40BARNYDGR 0 0 0 0 0 0 80 100 100 100 0 10 0 80 10 0 0 0FOXGREEN 0 0 0 0 0 0 60 100 100 100 0 10 0 100 50 20 0 0GLORYSPP 0 0 60 95 90 100 0 0 0 40 0 0 0 0COTTON 0 80JOHNGR 100 100RICE 95 80MUSTWILD 10__________________________________________________________________________ Compound No. 191 192 193 194 195 196 197 198 199 200 201 204 205 206 207 208 209 210 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 1 1 1 0.5 2 8__________________________________________________________________________SOYBEAN 0 0 20 10 0 0 0 10 0 0 0 20 5 10 5 10 0 0LIMABEANCORN 20 0 30 40 10 0 10 40 0 0 0 20 5 10 5 50 0 0WHEAT 0 20 40 10 10 0 0 40 0 0 20 20 10 10 0 40 0 0TOMATOVELVETLF 10 0 10 40 10 0 70 90 0 0 0 10 70 5 70 70 0 0BINDWEEDWILDOATBARNYDGR 70 10 20 90 10 0 95 95 0 30 0 30 100 100 95 100 50 20FOXGREEN 60 10 20 100 10 0 95 100 0 0 0 10 100 100 100 100 90 90GLORYSPP 30 0 20 80 10 0 80 95 0 0 0 10 15 50 20 70 0 0COTTON 0 30 0 10 0 5JOHNGR 30 80 90 95 95 100RICE 40 95 5 90 5 15MUSTWILD 0 0 30 0 10 60__________________________________________________________________________ Compound No. 211 212 213 214 215 216 217 219 220 221 222 223 224 225 226 227 228 Rate (kg/ha)Species 1 8 1 1 8 1 8 2 0.5 1 8 8 8 8 8 1 1__________________________________________________________________________SOYBEAN 40 0 0 10 60 15 30 5 5 0 0 10 0 0 90 10 10LIMABEANCORN 90 0 5 20 60 5 30 70 70 5 0 0 0 0 0 5 5WHEAT 15 20 0 10 40 0 0 0 40 0 0 20 0 0 0 15 5TOMATOVELVETLF 80 90 40 10 90 70 0 85 70 20 40 30 0 0 0 40 70BINDWEEDWILDOATBARNYDGR 100 90 90 40 95 95 70 100 90 95 0 50 0 0 0 90 90FOXGREEN 100 100 95 60 95 100 95 95 100 90 0 90 0 0 95 100 100GLORYSPP 85 90 15 20 90 5 20 80 90 30 0 30 0 0 0 50 20COTTON 5 0 5 0 0 60 0 0 5JOHNGR 100 70 30 95 95 95 95 85 95RICE 90 10 10 40 90 80 20 70 70MUSTWILD 40 15 10 60 0 20 0 60 30__________________________________________________________________________ Compound No. 229 230 232 234 235 236 237 238 239 240 241 242 243 244 245 246 Rate (kg/ha)Species 2 8 2 1 1 2 8 2 1 1 1 1 8 8 2 1__________________________________________________________________________SOYBEAN 0 0 20 0 0 0 30 0 10 0 10 0 0 20 15 10LIMABEANCORN 15 0 95 10 50 5 30 0 60 5 5 10 0 0 20 30WHEAT 0 0 90 0 20 5 10 0 10 5 5 10 10 20 40 70TOMATOVELVETLF 90 0 80 20 100 5 90 5 40 5 0 0 0 80 90 95BINDWEEDWILDOATBARNYDGR 100 0 100 100 95 90 100 100 95 90 30 40 70 20 100 100FOXGREEN 100 0 100 95 100 95 95 100 100 95 80 95 80 95 100 100GLORYSPP 90 0 70 70 70 60 95 0 50 0 0 15 30 70 90 95COTTON 10 10 0 0 0 0 0 0 0 0 50 0JOHNGR 95 95 90 80 95 95 85 50 40 5 95 95RICE 70 90 5 60 15 70 40 5 0 0 30 70MUSTWILD 80 70 80 30 15 0 0 5 0 0 95 90__________________________________________________________________________ Compound No. 247 248 249 250 251 252 254 259 260 261 Rate (kg/ha) Species 2 1 1 1 8 1 1 2 1 1__________________________________________________________________________ SOYBEAN 10 0 0 30 0 90 5 10 5 5 LIMABEAN CORN 70 0 10 50 20 80 10 50 50 5 WHEAT 10 0 5 30 20 70 5 15 0 0 TOMATO VELVETLF 50 15 70 70 0 90 70 85 90 30 BINDWEED WILDOAT BARNYDGR 95 90 95 100 50 100 90 95 100 80 FOXGREEN 100 95 95 100 95 100 100 100 100 95 GLORYSPP 70 15 40 70 20 90 80 90 95 10 COTTON 5 5 5 10 50 5 0 0 0 JOHNGR 95 90 95 100 95 95 95 100 60 RICE 5 30 60 50 85 5 50 5 15 MUSTWILD 95 40 40 5 90 5 85 0 20__________________________________________________________________________ *Data represents % Kill (% K) rather than % Control (% C)
TABLE 4__________________________________________________________________________Postemergence Herbicidal Activity (% Control)__________________________________________________________________________ Compound No. 1* 2* 3* 4* 5 6 7* 8 9* 10* 11 12 13 14* 15 16 17 18* 19* 20 21 22 23 24 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 0 30 10 0 10 0 0 60 20 30 50 0 50 0 60 10 20 10 30LIMABEAN 0 0 0 0 0 0 0 0 0 0 0CORN 0 0 20 10 0 10 0 0 50 0 10 20 0 20 0 60 10 20 40 30WHEAT 0 0 20 0 0 0 0 0 20 0 10 10 0 0 0 40 10 30 10TOMATO 0 0 0 0 0 0 0 0 0 0 0VELVETLF 0 0 0 0 0 0 0 10 0 0 60 0 30 0 30 0 0 0 0 40 10 20 10BINDWEED 0 0 0 0 0 0 0 0 0 0 0WILDOAT 0 0 0 0 0 0 0 0 0 0 0BARNYDGR 0 0 0 0 30 20 0 10 0 0 20 10 10 0 40 0 40 0 0 40 20 40 30 30FOXGREEN 0 0 0 0 10 0 0 20 0 0 20 0 20 0 30 0 20 0 0 30 10 30 40 10GLORYSPP 20 0 10 50 20 40 40 10 40 30 30 10COTTONJOHNGRRICEMUSTWILD__________________________________________________________________________ Compound No. 26 27 28* 29 30 31 32* 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 2 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 20 40 0 30 10 50 0 10 40 30 20 50 10 0 50 40 40 50 50 10 40 50 40 50LIMABEAN 0 0CORN 40 20 0 30 10 50 0 10 20 30 0 70 10 0 70 50 60 70 30 0 10 40 50 70 50WHEAT 10 20 0 10 10 30 0 10 50 10 0 30 0 0 10 20 50 50 10 0 20 10 30 40 20TOMATO 0VELVETLF 10 50 0 40 0 50 0 10 60 10 0 60 10 0 20 20 70 60 20 0 60 60 60 50BINDWEED 0 0WILDOAT 0BARNYDGR 20 50 0 40 20 60 0 20 30 30 0 70 10 0 30 40 70 70 15 10 20 70 70 80 60FOXGREEN 10 50 40 70 10 70 0 60 50 10 10 70 20 0 20 30 70 60 10 60 10 30 70 70 80GLORYSPP 10 50 0 40 0 40 10 10 10 20 40 10 0 40 40 60 60 10 0 30 50 90 40COTTON 5JOHNGR 0RICE 10MUSTWILD 10__________________________________________________________________________ Compound No. 51 52 53 54 55 56 57* 58 59 60 61 62 63 64 65* 66 67* 68 69 70 71 72 73 74 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 2 8 8 8 8__________________________________________________________________________SOYBEAN 50 30 40 30 10 60 50 50 40 50 60 40 20 0 10 0 50 40 30 30 0 20 20LIMABEAN 0 0 0CORN 50 0 20 40 10 60 60 80 60 60 20 30 0 0 10 0 70 20 70 20 0 0 0WHEAT 0 10 20 20 20 40 5 30 30 40 20 20 0 0 0 0 50 20 15 20 0 0 0TOMATO 0 0 0VELVETLF 60 20 0 40 0 50 0 50 70 80 50 50 30 50 0 0 0 50 10 60 30 0 0 0BINDWEED 0 0 0WILDOAT 0 0 0BARNYDGR 70 10 20 40 10 60 0 40 80 50 70 60 50 10 0 0 0 70 20 90 30 0 0 0FOXGREEN 50 50 20 50 10 50 0 20 80 70 70 60 20 50 0 0 0 60 40 10 10 0 50 0GLORYSPP 60 20 20 40 10 60 50 60 60 70 50 70 50 10 50 10 70 20 0 0 0COTTON 80JOHNGR 10RICE 30MUSTWILD 40__________________________________________________________________________ Compound No. 75 76 77 78 79 80 81* 82 83 84 85 86 87 88* 89 90 91 92 93 94 95 96 97 98 99* Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 40 10 30 10 30 20 0 0 10 30 0 50 10 0 50 60 50 10 20 30 50 50 50 50 0LIMABEAN 0 0 0CORN 30 0 60 20 40 0 0 10 20 20 60 20 40 0 30 70 50 10 10 10 60 70 70 80 0WHEAT 50 0 20 20 40 0 0 10 10 20 10 40 0 0 30 20 40 10 10 20 50 50 50 40 0TOMATO 0 20 0VELVETLF 60 20 30 10 60 0 0 10 20 40 30 30 70 0 40 30 80 0 30 30 60 80 70 60 0BINDWEED 0 0 0WILDOAT 0 0 0BARNYDGR 60 30 80 10 60 0 0 20 20 30 70 50 30 0 40 70 60 10 90 20 70 90 70 70 0FOXGREEN 80 0 40 10 40 10 0 30 50 80 50 40 40 0 50 20 60 20 70 20 50 60 70 50 0GLORYSPP 50 20 30 10 30 30 10 10 50 10 20 80 30 60 50 0 10 10 50 60 50 40COTTONJOHNGRRICEMUSTWILD__________________________________________________________________________ Compound No. 100* 101* 102* 103* 104 105 106 107 108 109 110 111 112 113 114* 115 116 117 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 0 0 0 0 30 60 40 40 50 40 30 60 30 20 0 50 0 40LIMABEAN 0 0 0 0 0CORN 0 0 0 0 40 70 60 70 70 70 20 80 20 10 0 50 0 60WHEAT 0 0 0 0 20 10 0 40 50 50 0 60 0 0 0 20 0 20TOMATO 0 0 0 0 0VELVETLF 0 0 0 0 30 50 40 20 50 20 20 80 20 10 0 30 0 80BINDWEED 0 0 0 0 30 0WILDOAT 0 0 0 0 0BARNYDGR 0 0 0 0 40 60 60 70 80 70 30 90 0 20 0 50 0 90FOXGREEN 0 0 0 0 90 100 40 40 70 20 30 60 20 10 0 60 0 60GLORYSPP 30 60 60 50 50 50 20 70 10 10 40 0 60COTTON 50JOHNGR 100RICEMUSTWILD__________________________________________________________________________ Compound No. 118 119 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 4 8__________________________________________________________________________SOYBEAN 30 10 5 40 30 10 60 0 50 10 0 40 40 10 0 30 20 60LIMABEANCORN 30 80 20 50 20 10 50 10 40 10 0 30 50 0 0 20 20 70WHEAT 10 20 30 40 30 10 20 0 0 0 0 10 40 0 0 10 10 50TOMATOVELVETLF 30 20 0 30 30 10 20 0 30 10 0 40 20 0 0 20 30 60BINDWEEDWILDOATBARNYDGR 60 95 10 70 30 10 50 10 40 40 0 60 70 0 0 50 30 50FOXGREEN 70 20 10 70 30 10 20 10 60 10 0 40 30 0 0 50 20 60GLORYSPP 50 10 0 60 30 10 60 0 30 10 0 60 30 0 0 10 40 60COTTON 10JOHNGR 30RICE 20MUSTWILD 30__________________________________________________________________________ Compound No. 138 139 140 141 142 143 144 146 147 148 149 150 151 152 153 154 155 156 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 2 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 80 30 50 60 50 50 50 50 10 40 30 40 60 60 50 20 70 40LIMABEANCORN 70 0 50 60 70 80 30 40 100 70 40 60 40 70 80 40 70 60WHEAT 20 0 40 40 50 20 10 10 20 10 10 40 40 60 60 10 30 20TOMATOVELVETLF 50 60 70 30 20 40 70 50 90 30 70 60 80 50 80 30 40 60BINDWEEDWILDOATBARNYDGR 80 20 70 80 60 50 70 50 20 60 80 70 80 80 80 20 70 70FOXGREEN 70 50 70 10 0 10 70 40 70 30 60 40 60 90 90 0 40 30GLORYSPP 60 60 60 20 30 40 60 50 40 30 60 60 70 50 80 10 70 70COTTON 60 20 50JOHNGR 30 80 90RICE 20 10 50MUSTWILD 20 80 30__________________________________________________________________________ Compound No. 157 158 159 160* 161 162 163 164 165 166 167 168* 169* 170* 172* 173* 174* 175* Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 30 40 5 0 20 40 10 60 30 50 20 0LIMABEAN 0 0 0 0 0 0 0 0CORN 70 70 10 0 50 40 20 70 50 60 10 0WHEAT 40 20 10 0 40 10 20 50 30 40 10 0TOMATO 0 0 0 0 0 0 0 0VELVETLF 80 50 20 0 80 40 0 50 40 60 0 0 0 0 0 0 0 0BINDWEED 0 0 0 0 0 0 0 0WILDOAT 0 0 0 0 0 0 0 0BARNYDGR 70 60 20 0 90 60 0 70 40 80 10 0 0 0 0 0 0 0FOXGREEN 70 90 10 0 80 60 0 80 50 90 10 0 0 0 0 0 0 0GLORYSPP 60 30 20 80 30 20 50 40 60 20COTTONJOHNGRRICEMUSTWILD__________________________________________________________________________ Compound No. 176* 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193__________________________________________________________________________ Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 10 0 0 50 50 30 50 40 40 60 40 20 40 20 60 10 50LIMABEAN 0CORN 10 0 0 70 70 30 20 20 20 30 20 10 30 10 30 10 20WHEAT 0 0 0 10 20 20 20 20 10 40 20 0 10 10 30 10 30TOMATO 0VELVETLF 0 0 0 0 60 50 30 10 10 0 70 0 10 30 10 70 0 20BINDWEED 0WILDOAT 0BARNYDGR 0 0 0 0 80 50 90 30 10 20 90 40 10 20 30 50 10 30FOXGREEN 0 0 0 60 60 50 20 60 10 50 100 30 20 30 10 50 10 40GLORYSPP 0 0 0 50 40 20 10 10 0 80 0 10 20 10 70 0 60COTTONJOHNGRRICEMUSTWILD__________________________________________________________________________ Compound No. 194 195 196 197 198 199 200 201 204 205 206 208 209 210 211 212 213 215 Rate (kg/ha)Species 8 8 8 8 8 8 8 8 8 1 8 0.5 8 8 8 8 8 8__________________________________________________________________________SOYBEAN 40 30 0 50 50 10 20 10 20 50 60 60 50 0 60 40 40 70LIMABEANCORN 50 30 0 40 50 0 0 0 10 80 70 20 0 0 60 40 20 0WHEAT 20 30 0 30 20 0 0 0 10 10 70 5 30 0 60 20 20 30TOMATOVELVETLF 40 30 0 30 50 0 20 0 20 40 80 85 60 50 95 70 70 50BINDWEEDWILDOATBARNYDGR 50 60 0 60 40 0 30 0 10 15 70 70 50 0 50 50 40 50FOXGREEN 70 80 0 20 50 0 0 0 20 70 80 95 90 0 50 90 80 40GLORYSPP 70 30 0 60 60 0 20 0 20 40 70 70 50 40 50 70 50 70COTTON 20 30JOHNGR 10 80RICE 10 5MUSTWILD 50 70__________________________________________________________________________ Compound No. 216 220 221 223 224 225 232 234 235 236 237 238 239 240 241 242 243 244 Rate (kg/ha)Species 8 0.5 8 8 8 8 8 8 1 2 8 8 1 8 8 8 8 8__________________________________________________________________________SOYBEAN 60 70 30 50 10 10 60 40 35 30 50 50 30 40 50 40 20 40LIMABEANCORN 80 60 0 50 50 0 70 10 60 30 70 60 20 70 70 20 10 40WHEAT 20 10 10 10 10 0 50 20 40 15 50 30 10 30 60 20 0 20TOMATOVELVETLF 60 80 60 30 20 0 20 0 80 50 50 60 50 50 60 40 40 20BINDWEEDWILDOATBARNYDGR 70 70 40 40 30 0 70 40 60 20 70 80 40 90 80 30 0 10FOXGREEN 80 85 60 20 20 0 10 10 70 20 70 70 50 50 90 30 0 30GLORYSPP 40 70 60 40 20 0 20 30 60 70 60 60 50 60 50 40 30 20COTTON 30 30 30 5JOHNGR 90 60 15 40RICE 5 50 15 10MUSTWILD 15 95 10 40__________________________________________________________________________ Compound No. 245 246 247 248 249 250 251 252 261__________________________________________________________________________ Rate (kg/ha) Species 8 8 8 8 8 1 8 1 8__________________________________________________________________________ SOYBEAN 50 50 50 40 60 60 50 70 60 LIMABEAN CORN 60 80 60 20 80 70 30 90 30 WHEAT 40 60 30 0 60 10 30 30 20 TOMATO VELVETLF 50 30 30 40 70 60 60 70 60 BINDWEED WILDOAT BARNYDGR 50 40 40 40 60 70 20 70 20 FOXGREEN 80 80 30 70 70 90 70 70 70 GLORYSPP 50 30 20 40 50 60 60 50 20 COTTON 30 40 JOHNGR 80 70 RICE 50 40 MUSTWILD 60 80__________________________________________________________________________ *Data represents % Kill (% K) rather than % Control (% C)

Number	Name	Date
3922162	Krenzer	Nov 1975
4702763	Maravetz	Oct 1987
4761174	Chang et al.	Aug 1988

Herbicidal substituted-phenyl-1,2,4-triazol-5(1H)-thiones and -ones

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