This application is a 371 of PCT/US94/10342 filed Sep. 12, 1994. 
This invention relates to certain heteroaryl substituted anilides which are 
useful as herbicides and their agriculturally suitable compositions as 
well as methods for their use as general or selective preemergent or 
postemergent herbicides or as plant growth regulants. 
New compounds effective for controlling the growth of undesired vegetation 
are in constant demand. In the most common situation, such compounds are 
sought to selectively control the growth of weeds in useful crops such as 
cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed 
growth in such crops can cause significant losses, reducing profit to the 
farmer and increasing costs to the consumer. In other situations, 
herbicides are desired which will control all plant growth. Examples of 
areas in which complete control of all vegetation is desired are areas 
around railroad tracks, storage tanks and industrial storage areas. Them 
are many products commercially available for these purposes, but the 
search continues for products which are more effective, less costly and 
environmentally safe. 
WO93/11097 discloses herbicidal anilide derivatives wherein an optionally 
substituted phenyl group occupies the ortho-position. In contrast, the 
compounds of the present invention bear a heteroaromatic group at that 
location and are therefore not disclosed therein. 
SUMMARY OF THE INVENTION 
The invention comprises compounds of Formula I: 
##STR2## 
X is a single bond; O; S; or NR.sup.4 ; Y is O; S; or NCH.sub.3 ; 
Z is CH or N; 
W is CH or N; 
R.sup.1 is C.sub.1 -C.sub.5 alkyl optionally substituted with C.sub.1 
-C.sub.2 alkoxy, OH, 1-3 halogens, or C.sub.1 -C.sub.2 alkylthio; 
CH2(C.sub.3 -C.sub.4 cycloalkyl); C.sub.3 -C.sub.4 cycloalkyl optionally 
substituted with 1-3 methyl groups; C.sub.2 -C.sub.4 alkenyl; C.sub.2 
-C.sub.4 haloalkenyl; or optionally substituted phenyl; 
R.sup.2 is H; chlorine; bromine; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 
alkoxy; C.sub.1 -C.sub.2 alkylthio; C.sub.2 -C.sub.3 alkoxyalkyl; C.sub.2 
-C.sub.3 alkylthioalkyl; cyano; nitro; NH(C.sub.1 -C.sub.2 alkyl); or 
N(C.sub.1 -C.sub.2 alkyl).sub.2 ; 
R.sup.3 is C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 haloalkoxy; C.sub.1 
-C.sub.4 haloalkylthio; halogen; cyano; nitro; or methylthio; 
R.sup.4 is H; CH.sub.3 or OCH.sub.3 ; and agriculturally suitable salts 
thereof. 
Preferred compounds of Formula I for reasons of greatest herbicidal 
activity and/or ease of synthesis are: 
1. Compounds of Formula I wherein: 
R.sup.1 is C.sub.1 -C.sub.4 alkyl optionally substituted with methoxy or 
1-3 halogens; C.sub.2 -C.sub.4 alkenyl; or C.sub.2 -C.sub.4 haloalkenyl; 
R.sup.2 is chlorine; bromine; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 
alkoxy; cyano; nitro; NH(C.sub.1 -C.sub.2 alkyl); or N(C.sub.1 -C.sub.2 
alkyl).sub.2. 
2. Compounds of Preferred 1 wherein: 
X is a single bond; 
R.sup.3 is C.sub.1 -C.sub.2 haloalkyl; C.sub.1 -C.sub.2 haloalkoxy; C.sub.1 
-C.sub.2 haloalkylthio; chlorine or bromine. 
3. Compounds of Preferred 2 wherein: 
Q is Q-1 or Q-2. 
Specifically preferred for greatest herbicidal activity and/or ease of 
synthesis are: 
2-methyl-N-[4-methyl-2-[6-(trifluoromethyl)-2-pyridinyl]phenyl]-propanamid 
e; and 
2-methyl-N-[4-methyl-2-[2-(trifluoromethylthio)-4-pyrimidinyl]-phenyl]-prop 
anamide. 
Further embodiments of the invention include: 
A composition for controlling growth of undesired vegetation comprising a 
herbicidally effective mount of a compound of Formula I as defined herein 
and at least one of a surfactant, solid or liquid diluent. 
A method of controlling the growth of undesired vegetation comprising 
applying to the locus to be protected a herbicidally effective amount of 
the composition described above. 
DETAILED DESCRIPTION OF THE INVENTION 
Compounds of General Formula I can be readily prepared by one skilled in 
the art by using the reactions and techniques described in Schemes 1-7 of 
this section as well as by following the specific procedures given in 
Examples 1-13. The definitions of Q, X, Y, Z and R.sup.1 -R.sup.4 are as 
described in the Summary of the Invention. 
Scheme 1 illustrates the preparation of compounds of Formula I whereby 
substituted phenyl compounds of Formula IIa wherein X.sup.2 is triakyltin 
(e.g., Me.sub.3 Sn), triakylsilyl (e.g., Me.sub.3 Si), or a boronic acid 
derivative (e.g., B(OH).sub.2) are coupled with heterocycles of Formula 
Ilia wherein X.sup.1 is chlorine, bromine, iodine or 
trifluoromethylsulfonyloxy (OTf). The coupling is carried out by methods 
known in the art: for example, see Tsuji, J., Organic Synthesis with 
Palladium Compounds, Springer-Verlag, Berlin (1980); Negishi, E., Acc. 
Chem. Res. (1982), 15, 340; Stille, J. K., Angew. Chem. (1986), 98, 504; 
Yamamoto, A. and Yamagi, A., Chem. Pharm. Bull. (1982), 30, 1731 and 2003; 
Dondoni et at., Synthesis (1987), 185; Dondoni et al., Synthesis (1987), 
693; Hoshino et al., Bull. Chem. Soc. Jpn. (1988), 61, 3008; Sato, M. et 
al., Chem. Left. (1989), 1405; Miyaura et al., Synthetic Commun. (1981), 
11,513; Siddiqui and Sniekus, Tetrahedron Lat. (1988), 29, 5463; Sharp at 
al., Tetrahedron Lett. (1987), 28, 5093; Hatanaka et at., Chem. Lett., 
(1989), 1711; Bailey, T. R., Tetrahedron Lett. (1986), 27, 4407, 
Echavarren, A. M. and Stille, J. K., J. Am. Chem. Soc. (1987), 109, 5478, 
and Ali et al., Tetrahedron Lat. (1992), 48, 8117. The coupling of IIa and 
IIIa is carried out by heating the mixture in the presence of a transition 
metal catalyst such as tetrakis(triphenylphosphine) palladium(O) or 
bis(triphenylphosphine)-palladium (11) dichloride in a solvent such as 
toluene, acetonitrile, glyme, or tetrahydrofuran optionally in the 
presence of an aqueous inorganic base such as sodium hydrogen carbonate or 
an organic base such as triethylamine. One skilled in the art will 
recognize that when IIIa contains more than one reactive substituent, then 
the stoichlometric ratios of reagents will need to be adjusted to minimize 
his-coupling. 
##STR3## 
Conversely, the anilides of Formula I can be prepared by reversing the 
reactivity of the two substrates. Substituted phenyl compounds of Formula 
lib wherein X.sup.2 is chlorine, bromine, iodine or 
trifluoromethylsulfonyloxy (OTf) can be coupled with heteroaromatic 
compounds of Formula IIIb wherein X.sup.1 is trialkyltin (e.g., Me.sub.3 
Sn), trialkylsilyl (e.g., Me.sub.3 Si), or a boronic acid derivative 
(e.g., B(OH).sub.2). The procedure for conducting the coupling is the same 
as those described and referenced above. 
By methods also reported in the above cited literature, compounds of 
Formula IIa and IIIb are prepared by treating the corresponding halide 
(i.e., wherein X.sup.1 and X.sup.2 is bromine or iodine) with a metalating 
agent such as n-butyllithium followed by quenching with a trialkyltin 
halide, trialkylsilyl halide, boron trichloride, or trialkyl borate. 
Some compounds of Formula IIa can also be prepared from the corresponding 
ortho-unsubstituted compound (i.e., wherein X.sup.2 is hydrogen) by 
treatment with a base such as n-butyllithium followed by quenching with a 
trialkyltin halide, trialkylsilyl halide, or trialkyl borate as reported 
in the same literature references. This preparation requires that 
--NHC(.dbd.O)XR.sup.1 is an ortho-metalation directing group known in the 
an (e.g., trimethylacetylamido): see for example, Fuhrer, W., J. Org. 
Chem., (1979), 44, 1133. 
Anilides and heteroaromatics of Formula II and III wherein X.sup.1 and 
X.sup.2 are chlorine, bromine, iodine, OTf, and hydrogen are either known 
or readily prepared by procedures and techniques well known in the art, 
for example: Houben-Weil, Methoden der Organische Chemie, IV edition, 
Eugen Muller, Ed., Georg Thieme Verlag; Turchi, I. J., The Chemistry of 
Heterocyclic Compounds, Vol. 45, pp. 36-43, J. Wiley & Sons, New York 
(1986); L. S. Wittenbrook, G. L. Smith, R. J. Timmons, J Org. Chem. 
(1973), 38, 465-471; and P. Reynaud, et al., Bull. Soc. Chim. Fr. (1962), 
1735-1738. 
Compounds of Formula I can also be prepared by one skilled in the art from 
anilines of Formula IV by treatment with an appropriate acyl chloride or 
acid anhydride (X.dbd.direct bond), chloroformate (X.dbd.O), 
chlorothiolformates (X.dbd.S), carbamoyl chloride (X.dbd.NCH.sub.3), or 
isocyanate (X.dbd.NH) under conditions well known in the literature, for 
example: Sandler, R. S. and Karo, W., Organic Functional Group 
Preparations, 2nd Edition, Vol. I, p 274 and Vol. H, pp 152, 260, Academic 
Press (Scheme 2). 
##STR4## 
Alternatively, anilines of Formula IV can be convened into the 
corresponding isocyanate by treatment with phosgene or known phosgene 
equivalents (e.g., C1C(.dbd.O)OCCl.sub.3), and then condensed with an 
appropriate alcohol or amine of Formula V to afford anilides of Formula I 
(Scheme 3). These techniques are well known in the literature. For 
example, see Sandlet, R. S. and Karo, W., Organic Functional Group 
Preparations, 2nd Edition, Vol. II, 152, 260, Academic Press; Lehman, G. 
and Teichman, H. in Preparative Organic Chemistry, 472, Hilgetag, G. and 
Martini, A., Eds., John Wiley & Sons, New York, (1972); Eckert, H. and 
Forster, B., Angew. Chem., Int. Ed., (1987), 26, 894; Babad, H. and 
Zeiler, A. G., Chem. Rev., (1973), 73, 75. 
##STR5## 
Anilines of Formula IV are readily prepared by palladium catalyzed coupling 
of an ortho-substituted nitrophenyl compound of Formula VIa, wherein 
X.sup.2 is as defined above, with a heteroaromatic compound of Formula 
III, wherein X.sup.1 is as defined above, followed by catalytic or 
chemical reduction of the nitro group (Scheme 4). As described for Scheme 
1, the reactivity of the substrates can be reversed, i.e. the coupling is 
carded out using an ortho-substituted nitrophenyl compound of Formula VIb 
and a heteroaromatic compound of Formula IIIb. 
Reduction of nitro groups to amino groups is well documented in the 
chemical literature. See for example, Ohme, R. and Zubek, A. R. and Zubek, 
A. in Preparative Organic Chemistry, 557, Hilgetag, G. and Martini, A., 
Eds., John Wiley & Sons, New York: (1972). 
##STR6## 
In some cases, it is desirable to perform the palladium coupling reaction 
on an N-protected form of the aniline, for example the 
2,2-dimethylpropanamide. Upon completion of the coupling reaction, the 
N-protecting group can be removed, for example by treatment of the 
2,2-dimethylpropanamide with acid, to liberate the amino group. 
In other cases, it is advantageous to prepare compounds of Formula IV, not 
by the cross-coupling methods described above, but rather by elaboration 
of a substituted ortho-nitrobenzoic acid, or a derivative thereof (Formula 
VII), under any of a number of ring closure methodologies (Scheme 5). 
Subsequent reduction of the nitro compounds of Formula VIII provides 
compounds of Formula IV. One skilled in the art will recognize that these 
same ring closure methodologies can be used to elaborate a substituted 
ortho-aminobenzoic acid, or a derivative thereof, into compounds of 
Formula IV. 
##STR7## 
wherein X.sup.3 can be any of a number of heterocycle building blocks, 
including, but not limited to those shown below: 
X.sup.3 .dbd.CO2H, COCl, CO.sub.2 -alkyl, CONH.sub.2, C(.dbd.S)NH.sub.2, 
CHO, CN, C(.dbd.NOH)NH.sub.2, COCH.sub.2 NH.sub.2, and COCH.sub.2 
-halogen. 
Compounds of Formula VII are well known in the art or may be made by simple 
functional group interconversions on ortho-substituted nitrobenzenes. 
Numerous methods for conversion of these X.sup.3 substituents into 
5-membered heterocycles are well known in the literature and can be 
applied by those skilled in the art for the preparation compounds of 
Formula VIII wherein Q is Q-3, Q-4, Q-5 or Q-6. For example, see A. R. 
Katritzky and C. W. Rees, Comprehensive Heterocyclic Chemistry, Vol. 6, 
pp. 216-222; 293-306; 386-391; 492-508, Pergamon Press, London (1984); R. 
Elderfield, Heterocyclic Compounds, Vol. 5, pp. 302-319; 495-505, J. Wiley 
& Sons, New York (1957); ibid., Vol. 7., pp. 508-518; 558-569, J. Wiley & 
Sons, New York (1961); I. J. Turehi, M. J. S. Dewar, Chem. Rev. (1975), 
75(4), 389-436; A. M. Van Leusen, B. E. Hoogenboom, H. Siderius, 
Tetrahedron Lett. (1972), 2369-2372; F. Yokokawa, Y. Hamada, T. Shioiri, 
Synlett (1992), 153-155. This strategy is illustrated in Example 13. 
In some instances, it may be necessary, or more convenient, to introduce 
the desired substituents after the coupling reaction was performed. This 
can be accomplished by electrophilic substitution (Scheme 6), or 
nucleophilic substitution and functional group modifications (Scheme 7) 
using procedures well documented in the literature. These strategies are 
illustrated in Examples 3-13. 
##STR8## 
Variation of the substituent R.sup.3 on the heterocycle Q of compounds of 
Formula I may be achieved by one of two ways. First, one skilled in the 
art may simply select the appropriate heteroaromatic compound of Formula 
III a, b for the palladium coupling in Schemes 1 and 4 to give examples 
with a variety of values for R.sup.3. Alternatively, it may at times be 
convenient to vary R.sup.3 by performing various functional group 
transformations on the previously assembled aryl-substituted heterocycle 
of Formula I as shown in Scheme 7. Methods to perform these 
transformations are well known in the literature. Some examples include 
conversion of chloro to bromo (L. J. Street, et al., J. Med. Chem. (1992), 
35, 295-304), bromo to trifluoromethyl (J. Wrobel, et al., J. Med. Chem. 
(1989), 32(II), 2493-2500), cyano (G. P. Ellis, T. M. Romney-Alexander, 
Chem. Rev. (1987), 87, 779-794), alkoxy and alkylthio, aldehyde to 
difluoromethyl (W. J. Middleton, J. Org. Chem. (1975), 40, 574-578), thiol 
to trifluoromethylthio (V. I. Popov, V. N. Boiko, L. M. Yagupolskii, J. 
Fluor. Chem. (1982), 21, 365-369) and amino to a variety of substituents 
via the diazonium salts. Electrophilic aromatic substitution or 
metallation chemistry are also useful methods for incorporating certain 
substitutents. 
##STR9## 
One skilled in the art will recognize that the above methods may require 
the use of protecting groups or subsequent functional group 
interconversions to avoid undesired side reactions with substituents which 
may be sensitive to the reaction conditions. One skilled in the an will 
also recognize that compounds of Formula I and the intermediates described 
above can be subjected to various electrophilic, nucleophilic, radical, 
organometallic, oxidation, and reduction reactions to add substituents or 
modify existing substituents. 
Without further elaboration, it is believed that one skilled in the art 
using the preceding description can utilize the present invention to its 
fullest extent. The following examples are, therefore, to be construed as 
merely illustrative, and not limiting of the disclosure in any way 
whatsoever.