The invention relates to novel difluoromethoxy-, trifluoromethoxy-, 1,1,2,2-tetrafluoroethoxy-, alkenyloxy- and alkynyloxypyridine and quinoline compounds and a method for controlling undesirable plant species therewith.

SUMMARY OF THE INVENTION 
The invention is difluoromethoxy-, trifluoromethoxy-, 
1,1,2,2-tetrafluoroethoxy-, alkenyloxy- and alkynyloxypyridine and 
quinoline compounds having the structures: 
##STR1## 
wherein R.sub.1 is C.sub.1 -C.sub.4 alkyl; 
R.sub.2 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.6 cycloalkyl; and when 
R.sub.1 and R.sub.2 are taken together with the carbon to which they are 
attached they may represent C.sub.3 -C.sub.6 cycloalkyl optionally 
substituted with methyl; 
R is hydrogen; 
##STR2## 
C.sub.1 -C.sub.12 alkyl optionally substituted with one of the following 
groups: C.sub.1 -C.sub.3 alkoxy, halogen, hydroxy, C.sub.3 -C.sub.6 
cycloalkyl, benzyloxy, furyl, phenyl, halophenyl, loweralkylphenyl, 
loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano or 
triloweralkylammonium; 
C.sub.3 -C.sub.12 alkenyl optionally substituted with one of the following 
groups: C.sub.1 -C.sub.3 alkoxy, phenyl, halogen or loweralkoxycarbonyl or 
with two C.sub.1 -C.sub.3 alkoxy groups or two halogen groups; 
C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one or two C.sub.1 
-C.sub.3 alkyl groups; 
C.sub.3 -C.sub.10 alkynyl; or a cation; 
W is O or S; 
X is hydrogen, halogen or methyl; 
Y is hydrogen, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 
hydroxyloweralkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.4 alkylthio, 
phenoxy, C.sub.1 -C.sub.4 haloalkyl, nitro, cyano, C.sub.1 -C.sub.4 
alkylamino, di-C.sub.1 -C.sub.4 -loweralkylamino, C.sub.1 -C.sub.4 
alkylsulfonyl or phenyl optionally substituted with one C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy or halogen, difluoromethoxy, 
trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, C.sub.3 -C.sub.8 stright or 
branched alkenyloxy optionally substituted with one to three halogens, or 
C.sub.3 -C.sub.8 straight or branched alkynyloxy optionally substituted 
with one to three halogens; 
Z is hydrogen, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 
hydroxyloweralkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.4 alkylthio, 
phenoxy, C.sub.1 -C.sub.4 haloalkyl, nitro, cyano, C.sub.1 -C.sub.4 
alkylamino, di-C.sub.1 -C.sub.4 -loweralkylamino, C.sub.1 -C.sub.4 
alkylsulfonyl or phenyl optionally substituted with one C.sub.1 -C.sub.4 
alkyl or C.sub.1 -C.sub.4 alkoxy or halogen, C.sub.3 -C.sub.8 straight or 
branched alkenyloxy optionally substituted with one to three halogens, or 
C.sub.3 -C.sub.8 straight or branched alkynyloxy optionally substituted 
with one to three halogens; 
with the proviso that at least one of Y and Z is difluoromethoxy, 
trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy C.sub.3 -C.sub.8 straight or 
branched alkenyloxy optionally substituted with one to three halogens, or 
C.sub.3 -C.sub.8 straight or branched alkynyloxy optionally substituted 
with one to three halogens; 
L, M, Q and R.sub.7 each represent hydrogen, halogen, C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 
-C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 haloalkyl, difluoromethoxy, 
trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, NO.sub.2, CN, phenyl, 
phenoxy, amino, C.sub.1 -C.sub.4 alkylamino, diloweralkylamino, 
chlorophenyl, methylphenyl, phenoxy substituted with one Cl, CF.sub.3, 
NO.sub.2 or CH.sub.3 group, C.sub.3 -C.sub.8 straight or branched 
alkenyloxy optionally substituted with one to three halogens, or C.sub.3 
-C.sub.8 straight or branched alkynyloxy optionally substituted with one 
to three halogens; with the proviso that at least one of L, M, Q or 
R.sub.7, is difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 
C.sub.3 -C.sub.8 straight or branched alkenyloxy optionally substituted 
with one to three halogens, or C.sub.3 -C.sub.8 straight or branched 
alkynyloxy optionally substituted with one to three halogens; 
the N-oxides thereof when W is O provided that R cannot be unsaturated 
alkyl and Y or Z cannot be alkylamino, dialkylamino or alkylthio; 
the optical isomers thereof when R.sub.1 and R.sub.2 are not the same; 
the tautomers thereof; 
the acid addition salts thereof except when R is a salt-forming cation. 
In the above description of the compounds of the invention in this 
application, when R is a cation, it is preferably an alkali metal, 
alkaline earth metals, manganese, copper, iron, zinc, cobalt, lead, 
silver, nickel, ammonium or organic ammonium. 
The compounds of the present invention may be prepared by the procedures 
described in the pending application for U.S. Letters Patent of Marinus 
Los, Ser. No. 382,041, filed May 25, 1982, incorporated herein by 
reference thereto. 
The substituted quinolines are prepared by starting with the appropriately 
substituted aniline and using the reactions previously described and shown 
in Flow Diagram I below. 
##STR3## 
The substituted pyridines are prepared by one or both of two methods. In 
the first case the product can be derived by alkylation of the 
appropriately substituted 5-pyridinol described in the pending 
application. This is shown in Flow Diagram II below. 
##STR4## 
where R.sub.10 is CF.sub.2 H--, C.sub.3 -C.sub.8 straight or branched 
alkenyl or alkynyl optionally substituted with one to three halogens. 
Alternatively the alkenyloxy or alkynyloxy group is introduced into the 
molecule prior to carboxylation as illustrated in Flow Diagram III below. 
##STR5## 
where R.sub.10 =C.sub.3 -C.sub.8 straight or branched alkenyl or alkynyl. 
By yet another modification the trifluoromethoxy group can be introduced at 
an earlier stage of the synthetic sequence as shown in Flow Diagram IV 
below. 
##STR6## 
The starting material for the above sequence is described by E. J. Blanz, 
et al., J. Med. Chem., 13, 1124(1970). The method is described in the 
above identified pending application. 
The pyridine derivatives in which Z=alkenyl or alkynyl groups are most 
readily prepared by the displacement of the compounds in which Z=Cl by the 
anion of the appropriate alcohol. This is shown in Flow Diagram V below. 
##STR7## 
in which R.sub.10 is C.sub.3 -C.sub.8 straight or branched alkenyl or 
alkynyl optionally substituted with one to three halogens. Cyclization of 
the appropriate acid with dicyclohexylcarbodiimide gives the 3,5-dione as 
shown in Flow Diagram VI below. 
##STR8## 
When the cyclization is carried out in acetic anhydride, the other isomer, 
the 2,5-dione, is obtained as shown in the Flow Diagram VII below. 
##STR9## 
The preparation of the N-oxides can be accomplished as shown in Flow 
Diagram VIII below. 
##STR10## 
In order to prepare the compounds where Z=alkenyloxy or alkynyloxy, the 
chloro derivative is converted to its N-oxide as shown below and the 
chlorine then displaced by the appropriate alkenyl or alkynyl alkoxide 
followed by acid hydrolysis as illustrated in Flow Diagram IX below. 
##STR11## 
The difluoromethoxy-, trifluoromethoxy-, 1,1,2,2-tetrafluoroethoxy-, 
alkenyloxy-, and alkynyloxypyridine and quinoline compounds of the 
invention are exceedingly effective herbicidal agents useful for the 
control of an exceptionally wide variety of herbaceous and woody annual 
and perennial monocotyledonous and dicotyledonous plants. Moreover, these 
compounds are herbicidally effective for controlling weeds indigenous to 
both dry land and wet land and are unique in their effectiveness in 
controlling the above-said plants when applied to the foliage thereof or 
to soil or water containing seeds or other propagating organs of said 
plants such as tubers, rhizomes or stolons, at rates of from about 0.016 
to 4.0 kg/ha, and preferably at rates from about 0.032 to 2.0 kg/ha. 
Additionally, it has been found that some of the compounds of the invention 
are selective herbicides when applied to the foliage of plants or to soil 
containing seeds of said plants at relatively low rates of application, 
i.e., at from 0.016 to about 2.0 kg per hectare, depending on the compound 
used and crop treated, and that certain compounds are effective for 
increasing branching of leguminous crops and effecting early maturation of 
grains. 
It is, of course, obvious that rates of application above the 4.0 kg/ha 
level can also be used to effectively kill undesirable plant species; 
however, rates of application of toxicant above the level necessary to 
kill the undesirable plants should be avoided since application of 
excessive amounts of toxicant is costly and serves no useful function in 
the environment. 
Among the plants which may be controlled with the compounds of this 
invention are: Elatine triandra, Sagittaria pygmaea, Scirpus hotarui, 
Cyperus serotinus, Eclipta alba, Cyperus difformis, Rotala indica, 
Lindernia pyridoria, Echinochloa crus-galli, Digitaria sanguinalis, 
Setaria viridis, Cyperus rotundus, Convolvulus arvensis, Agropyron repens, 
Datura stramonium, Alopecurus myosuroides, Ipomoea spp., Sida sponosa, 
Ambrosia artemisiifolia, Eichhornia crassipes, Xanthium pensylvanicum, 
Sesbania exalta, Avena fatua, Abutilon theophrasti, Bromus tectorum, 
Sorghum halepense Lolium spp., Panicum dichotomiflorum, Matricaria spp., 
Amaranthus retroflexus, Cirsium arvense and Rumex japonicus. 
Since the difluoromethoxy-, trifluoromethoxy-, 
(1,1,2,2-tetrafluoroethoxy)-, alkenyloxy-, and alkynyloxypyridine and 
quinoline derivatives, wherein R.sub.3 is a salt-forming cation, are water 
soluble, these compounds can simply be dispersed in water and applied as a 
dilute aqueous spray to the foliage of plants or to soil containing 
propagating organs thereof. These salts also lend themselves to 
formulation as flowable concentrates. 
Wettable powders can be prepared by grinding together about 20 to 45% by 
weight of a finely divided carrier such as kaolin, bentonite, diatomaceous 
earth, attapulgite, or the like, 45 to 80% by weight of the active 
compound, 2 to 5% by weight of a dispersing agent such as sodium 
lignosulfonate, and 2 to 5% by weight of a nonionic surfactant, such as 
octylphenoxy polyethoxy ethanol, nonylphenoxy polyethoxy ethanol or the 
like. 
A typical flowable liquid can be prepared by admixing about 40% by weight 
of the active ingredient with about 2% by weight of a gelling agent such 
as bentonite, 3% by weight of a dispersing agent such as sodium 
lignosulfonate, 1% by weight of polyethylene glycol and 54% by weight of 
water. 
A typical emulsifiable concentrate can be prepared by dissolving about 5 to 
25% by weight of the active ingredient in about 65 to 90% by weight of 
N-methylpyrrolidone, isophorone, butyl cellosolve, methylacetate or the 
like and dispersing therein about 5 to 10% by weight of a nonionic 
surfactant such as an alkylphenoxy polyethoxy alcohol. This concentrate is 
dispersed in water for application as a liquid spray. 
When the compounds of the invention are to be used as herbicides where soil 
treatments are involved, the compounds may be prepared and applied as 
granular products. Preparation of the granular product can be achieved by 
dissolving the active compound in a solvent such as methylene chloride, 
N-methylpyrrolidone or the like and spraying the thus-prepared solution on 
a granular carrier such as corncob grits, sand, attapulgite, kaolin or the 
like. 
The granular product thus prepared generally comprises about 3 to 20% by 
weight of the active ingredient and about 97 to 80% by weight of the 
granular carrier.