This invention relates to novel pyrazole carboxylates having the formula ##STR1## and their use as herbicides.

This invention relates to novel pyrazolecarboxylates having the formula 
##STR2## 
wherein R is selected from the group consisting of hydrogen, 
agriculturally acceptable cations, alkyl having from 1 to 8 carbon atoms, 
phenoxy lower alkyl, chlorinated allyl lower alkylthio lower alkyl and 
tetrafluorocyclobutyl methyl; R.sub.1 is selected from the group 
consisting of hydrogen and lower alkyl; and X and Y are independently 
selected from the group consisting of hydrogen, trifluoromethyl, halo, 
lower alkyl and lower alkoxy; provided that X, Y and R may not 
simultaneously be hydrogen. 
As used herein the term "lower alkyl" or "lower alkoxy" is meant to include 
those alkyl or alkoxy radicals having from 1 to 3 carbon atoms, inclusive. 
The term agriculturally acceptable cations is understood to mean those 
cations which are commonly used in herbicidal compositions to form the 
salt of the free acid, including but not limited to the alkali metal, 
substituted amine and ammonium cations. 
A novel aspect of the present invention includes the preparation of the 
novel pyrazolecarboxylates of the above formula in accordance with the 
following reaction 
##STR3## 
In the above reaction E may be hydrogen or carboethoxy, e.g., 
##STR4## 
R, R.sub.1, X and Y are as previously defined. The specific solvent 
utilized is within the skill of the art, however, ethyl ether or acetic 
acid are preferred. 
In preparing pyrazolecarboxylates of the invention in which R.sub.1 is 
ethyl or propyl, E in Equation I above should be carboethoxy and 
preferably the reaction should proceed in acetic acid. More specifically, 
said pyrazolecarboxylates of the invention may be prepared by preparing a 
solution containing equimolar quantities of the appropriate propenoic acid 
ester and the appropriate alkyl carbazate in acetic acid. The solution is 
then heated at reflux for a time sufficient to complete the reaction, 
usually 1 to 2 hours. After removing the solvent by evaporation under 
reduced pressure, the residue is dissolved in ether and washed free of 
acetic acid with aqueous NaHCO.sub.3. After the ether solution is dried, 
filtered and concentrated, the more volatile impurities are removed by 
Kugelrohr distillation.

The following examples are presented to more particularly illustrate the 
preparation of the novel pyrazolecarboxylates of the invention and are not 
intended as a restriction of the scope of the invention. Temperatures are 
understood to be in degrees Centigrade (.degree. C.). 
EXAMPLE 1 
To a stirred solution of 6.30 g. (0.02 mol) of ethyl 
2-(.alpha.,.alpha.,.alpha.-trifluoro-m-toluoyl)-3-dimethylaminopropenoate 
in 50 ml. of ethyl ether cooled to -10.degree. was added 3.3 g. of ethyl 
3-ethylcarbazate (0.02 mol) assuming 80% purity. The ether was distilled 
off and replaced with 30 ml. of ethanol. The ethanol solution was heated 
at reflux for 4 hours. Glacial acetic acid (10 ml) was added and the 
solution heated at reflux. After 2 hours all starting material had been 
consumed. The solvent was removed under reduced pressure. The residual oil 
was dissolved in 100 ml. of ether and the solution washed with water, and 
5% NaHCO.sub.3 until free of acetic acid, again with water, then dried 
(MgSO.sub.4), filtered and concentrated to 5.79 g. viscous oil which 
resisted crystallization from ethyl ether, hexane, pentane, and Et.sub.2 
O-hexane, Et.sub.2 O-pentane mixtures. 
The product was determined by NMR to be 
##STR5## 
Anal. Calc'd. C, 57.69; H, 4.84; F, 18.25; N, 8.97. Found C, 57.63; H, 
4.76; F, 18.27; N, 8.82. 
EXAMPLE 2 
To 4.94 g. (0.02 mol) ethyl 2-benzoyl-3-dimethylaminopropenoate dissolved 
in 50 ml. of ethanol was added 3.0 g of ethyl isopropylcarbazate with 1.5 
ml. of acetic acid. An additional 25.0 ml. of acetic acid was added and 
the solution heated to reflux for about 18 hours. The solvent was removed 
by evaporating and the resulting oil taken up in 100 ml. of ether and 
washed with water, HCl (5%), water, saturated NaHCO.sub.3, water and then 
dried over MgSO.sub.4, filtered and concentrated. Dry column 
chromatography on 270 g. Silica gel-G of 4.15 g of the oil gave two 
components developed with a 1:4 ethyl ether:pentane solution. Evaporative 
distillation gave 1.30 g. of a compound having the following formula 
##STR6## 
Anal. Calc'd: C, 69.74; H, 7.02; N, 10.84 Found: C, 69.83; H, 7.05; N, 
10.74. 
EXAMPLE 3 
A mixture of 0.025 mol of ethyl 
2-(m-chlorobenzoyl)-3-dimethylaminopropenoate and 0.025 mol of ethyl 
3-isopropylcarbazate in 25 ml. of acetic acid was heated to reflux for 1.5 
hours and allowed to settle overnight at room temperature. After removing 
the solvent by distillation, the residue was dissolved in 200 ml. of ether 
and the ether solution washed with water, then with a saturated solution 
of NaHCO.sub.3 until free of acetic acid. After drying, filtering and 
concentrating, 7.27 g of an orange liquid remained. Upon evaporative 
distillation, 4.0 g. was obtained of a compound having the formula 
##STR7## 
Anal. Calc'd. C, 61.54; H, 5.85; Cl, 12.11; N, 9.57. Found C, 61.60; H, 
5.81; Cl, 11.92; N, 9.50. 
Preparation of pyrazolecarboxylates in which R.sub.1 is hydrogen or methyl 
may be accomplished as follows: 
##STR8## 
More specifically, a solution of 0.005 to 0.020 moles of the appropriate 
propenoic acid ester in 30-50 ml. of a solvent, preferably ethyl ether, is 
cooled in an ice-methanol bath with magnetic stirring to 0.degree. to 
-20.degree. C. An equimolar amount of the appropriate hydrazine in 10-20 
ml. of ether is added dropwise in 10-15 minutes. The reaction is complete 
within 5-60 minutes. The ether is washed with 5% HCl, dried, filtered and 
evaporated to an oil which shows two products on glc. Isomer P.sub.1 is 
about 90% of the product. The two isomers are separated either by 
fractional crystallization or column chromatography. Note that in Equation 
II above E is hydrogen. 
The following examples are presented to further illustrate the preparation 
of the novel pyrazolecarboxylates of the invention and are not intended as 
a restriction of the scope of the invention. As in the above examples, 
temperatures are understood to be in degrees Centigrade (.degree. C.). 
EXAMPLE 4 
A solution of 1.92 g (0.005 mol) of ethyl 2-(3', 
5'-bis-trifluoromethylbenzoyl)-3-dimethylaminopropenoate in 30 ml. of 
ether was cooled to -20.degree.. After heating to reflux, a solution of 
0.5 g of methyl hydrazine in 10 ml. of ether was added dropwise in 30 
minutes with rapid stirring. To this solution was added a reaction mixture 
formed by adding dropwise a solution of 0.5 g of methyl hydrazine in ether 
to a solution of 1.92 g of the propenoate in 30 ml. of ether at 
-20.degree.. Upon washing the combined solutions with water and 5% HCl, 
drying, filtering and concentrating, 4.0 g of a colorless oil was 
obtained. This oil was then dissolved in pentane. Overnight crystals 
formed having a structure as follows: 
##STR9## 
Anal. Calc'd. C, 59.99; H, 5.63; F, 16.75; N, 8.23. Found C, 59.84; H, 
5.68; F, 16.64; N, 8.40. 
EXAMPLE 5 
A solution of 5.63 g of ethyl 2-(m-chlorobenzoyl)-3-dimethylaminopropenoate 
(0.02 mol) in 50 ml. ethyl ether was cooled to -10.degree.. A solution of 
2.4 ml. of 98% methyl hydrazine in 15 ml. of ether was added dropwise in 
10 minutes. The mixture was stirred at room temperature for 30 minutes and 
washed with 5% HCl, dried (MgSO.sub.4) and filtered and concentrated to a 
slightly yellow oil. The oil was crystallized twice from hexane to give 
2.50 g of slightly yellow needles having the formula 
##STR10## 
Anal. Calc'd. C, 58.99; H, 4.95; Cl, 13.39; N, 10.58. Found C, 58.94; H, 
5.00; Cl, 13.44; N, 10.51. 
Alternatively the pyrazolecarboxylates of the invention may be prepared in 
accordance with the following examples. 
EXAMPLE 6 
A mixture of 3.05 g of ethyl 
3-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-4-pyrazolecarboxylate 
(0.0125 mol), 10 ml. of methyl iodide and 3.4 g of anhydrous potassium 
carbonate in 60 ml. of anhydrous acetone was heated at 40.degree. for 30 
hours. After cooling, the solid was separated and the solution 
concentrated to a yellow oil. The nmr of the crude oil indicated the 
presence of two isomers. Upon separation by chromatography 2.2 g of a 
product was obtained having the formula 
##STR11## 
Anal. Calc'd. C, 56.38; H, 4.39; F, 19.11; N, 9.39. Found C, 56.33; H, 
4.31; F, 18.96; N, 9.14. 
EXAMPLE 7 
A solution of 1-methyl-3-phenyl-4-pyrazolecarbonyl chloride and excess of 
2,2,3,3-tetrafluorocyclobutylmethyl alcohol was heated on a steam bath for 
one hour. The reaction mixture was crystallized from ether-hexane to give 
1.75 grams of a white solid. By NMR analysis the product was determined to 
be 
##STR12## 
Anal. Calc'd. C, 56.14; H, 4.12; N, 8.18. Found C, 55.99; H, 4.16; N, 7.93. 
EXAMPLE 8 
A solution of 18.0 grams of 
1-methyl-3-(.alpha.,.alpha.,.alpha.-m-tolyl)-4-pyrazolecarboxylic acid 
ethyl ester and 24 grams of sodium hydroxide in 150 ml. of a 50% ethanol 
solution was heated at reflux for 2 hours. The reaction mixture was 
concentrated under vacuum and acidified with HCl to give 14.6 grams of a 
white solid. The solid was recrystallized from ether-methanol to give a 
white solid having the structure 
##STR13## 
Anal. Calc'd. C, 53.34; H, 3.36; N, 10.37. Found C, 53.24; H, 3.31; N, 
10.37. 
EXAMPLE 9 
A solution of 2.0 g (0.01 mol) of 1-methyl-3-phenyl-4-pyrazolecarboxylic 
acid and 100 ml. of a 0.1000 N potassium hydroxide solution (Fisher 
certified) was stirred at room temperature for 64 hours. The reaction 
mixture was concentrated under vacuum at 50.degree. to give 2.2 g (92%) of 
a white solid having the structure 
##STR14## 
Anal. Calc'd. C, 54.98; H, 3.78; N, 11.66. Found C, 54.72; H, 3.76; N, 
11.68. 
In accordance with the procedures described above the following compounds 
have been prepared. 
Table I 
__________________________________________________________________________ 
##STR15## 
Compound Analysis 
Example 
R R.sub.1 
X Y C H F N Cl 
__________________________________________________________________________ 
10 C.sub.2 H.sub.5 
Isopropyl 
3-CF.sub.3 
H Calc'd 
58.89 
5.25 
17.47 
8.58 
Found 
59.11 
5.12 
17.31 
8.62 
11 C.sub.2 H.sub.5 
CH.sub.3 
4-Cl H Calc'd 
58.99 
4.95 10.58 
13.39 
Found 
59.12 
4.90 10.55 
13.30 
12 C.sub.2 H.sub.5 
CH.sub.3 
4-CF.sub.3 
H Calc'd 
56.38 
4.39 
19.11 
9.39 
Found 
56.46 
4.50 
19.29 
9.31 
13 
##STR16## 
CH.sub.3 
3-CF.sub.3 
H Calc'd Found 
49.76 49.72 
3.19 3.20 
6.83 6.82 
14 
##STR17## 
CH.sub.3 
3-CF.sub.3 
H Calc'd Found 
52.26 52.53 
3.51 3.50 
8.13 7.97 
15 sec-butyl CH.sub.3 
3-CF.sub.3 
H Calc'd 
58.89 
5.25 8.58 
Found 
58.75 
5.21 8.46 
16 n-hexyl CH.sub.3 
3-CF.sub.3 
H Calc'd 
61.01 
5.97 7.91 
Found 
60.84 
6.08 7.89 
17 CH.sub.2 CH.sub.2OC.sub.6 H.sub.5 
CH.sub.3 
3-CF.sub.3 
H Calc'd 
61.54 
4.39 7.18 
Found 
61.45 
4.39 7.10 
18 CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 
CH.sub.3 
3-CF.sub.3 
H Calc'd 
53.62 
4.78 7.82 
Found 
53.70 
4.78 8.05 
19 Na.sup.+ CH.sub.3 
H H Calc'd 
58.93 
4.04 12.49 
Found 
59.09 
3.79 12.60 
20 Li.sup.+ CH.sub.3 
H H Calc'd 
59.36 
4.81 12.58 
Found 
59.35 
4.78 12.28 
21 Li.sup.+ CH.sub.3 
3-CF.sub.3 
H Calc'd 
49.30 
3.75 9.60 
Found 
49.59 
3.25 9.51 
22 Na.sup.+ CH.sub.3 
3-CF.sub.3 
H Calc'd 
47.01 
3.13 9.15 
Found 
46.92 
2.72 8.84 
23 C.sub.2 H.sub.5 
H 3-OCH.sub.3 
5-OCH.sub.3 
Calc'd 
60.86 
5.84 10.14 
Found 
61.09 
5.71 10.01 
24 C.sub.2 H.sub.5 
CH.sub.3 
3-CH.sub.3 
H Calc'd 
68.61 
6.72 11.35 
Found 
68.83 
6.60 11.47 
25 (CH.sub.2).sub.3 CH.sub.3 
CH.sub.3 
3-CF.sub.3 
H Calc'd 
58.89 
5.25 8.58 
Found 
58.62 
4.97 8.57 
26 C.sub.2 H.sub.5 
CH.sub.3 
4-OCH.sub.3 
H Calc'd 
64.60 
6.20 10.76 
Found 
64.52 
6.23 10.74 
27 C.sub.2 H.sub.5 
CH.sub.3 
3-OCH.sub.3 
5-OCH.sub.3 
Calc'd 
62.06 
6.25 9.65 
Found 
62.29 
6.42 9.68 
__________________________________________________________________________ 
In accordance with the present invention, the pyrazolecarboxylates of the 
foregoing formula A possess herbicidal properties. Table II summarizes 
results of tests conducted to determine the pre-emergent as well as the 
post-emergent herbicidal activity of the compounds. The pre-emergent test 
was conducted as follows: 
A good grade of top soil was placed in aluminum pans and compacted to a 
depth of 3/8 to 1/2 inch from the top of the pan. On the top of the soil 
was placed a predetermined number of seeds or vegetative propagules of 
various plant species. The soil required to level fill the pans after 
seeding or adding vegetative propagules was weighed into a pan. A known 
amount of the active ingredient applied in a solvent or as a wettable 
powder and the soil were thoroughly mixed, and used as a cover layer for 
prepared pans. After treatment the pans were moved into a greenhouse bench 
where they were watered from below as needed to give adequate moisture for 
germination and growth. 
Unless noted otherwise, approximately 28 days after seeding and treating, 
the plants were observed to determine all deviations from the normal 
growth habit and the results recorded. A herbicidal rating code was used 
to signify the extent of phytotoxicity of each species. The ratings are 
defined as follows: 
______________________________________ 
% Control Rating 
______________________________________ 
0-24 0 
25-49 1 
50-74 2 
75-100 3 
______________________________________ 
The post-emergent tests were conducted as follows. The active ingredients 
are applied in spray form to 2 or 3-week old specimens of various plant 
species. The spray, a solution or wettable powder suspension containing 
the appropriate rate of active ingredient to give the desired test rate 
and a surfactant, is applied to the plants. The treated plants are placed 
in a greenhouse and unless otherwise noted approximately 4 weeks later the 
effects are observed and recorded. The results are shown in Table II in 
which the post-emergent herbicidal rating code is as follows: 
______________________________________ 
% Control Rating 
______________________________________ 
0-24 0 
25-49 1 
50-74 2 
75-99 3 
100 4 
______________________________________ 
The plant species utilized in these tests are identified by letter in 
accordance with the following legend: 
______________________________________ 
A Canada Thistle G Nutsedge 
B Cocklebur H Quackgrass 
C Velvetleaf I Johnsongrass 
D Morningglory J Bromus tectorum 
E Lambsquarter K Barnyard grass 
F Smartweed 
______________________________________ 
TABLE II 
__________________________________________________________________________ 
Rate Pre-Emergent Post-Emergent 
Compound 
Kg/Ha 
A B C D E F G H I J K A B C D E F G H I J K 
__________________________________________________________________________ 
1 *11.2 
1 1 3 2 3 3 0 1 0 2 3 1 1 1 1 1 1 1 1 1 1 1 
11.2 
1 0 3 0 3 1 0 0 0 1 3 1 1 1 1 1 0 0 
0 
0 
0 0 
4 *11.2 
1 0 1 1 3 1 0 0 0 1 3 2 2 1 2 1 1 0 
0 
0 
0 0 
11.2 
0 0 0 0 3 0 0 0 0 1 2 1 2 0 2 2 0 0 
0 
0 
0 1 
12 11.2 
0 0 0 0 3 2 1 0 0 1 2 1 0 0 0 0 0 0 
0 
0 
0 0 
6 *11.2 
2 0 3 3 3 3 0 0 0 2 3 1 1 1 3 2 0 0 
0 
0 
0 1 
11.2 
0 0 3 3 3 3 0 0 0 1 3 1 1 1 2 1 1 0 
0 
0 
0 0 
13 *11.2 
1 0 1 1 2 2 0 0 0 1 1 1 1 2 2 2 1 0 
1 
1 
1 1 
14 *11.2 
1 0 1 1 3 2 1 1 1 1 2 1 1 1 1 1 1 0 
0 
1 
0 1 
15 11.2 
0 0 0 0 3 1 0 0 0 0 3 1 1 1 0 2 0 0 
0 
1 
0 0 
16 *11.2 
0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 2 1 0 
0 
1 
0 1 
17 *11.2 
3 0 0 1 3 0 0 0 0 0 0 1 0 0 0 0 0 0 
0 
0 
0 0 
18 *11.2 
0 0 1 1 3 1 0 0 0 1 1 1 1 1 1 2 1 0 
1 
0 
0 1 
25 11.2 
2 0 1 0 3 3 0 0 0 2 3 0 1 1 1 3 0 0 
0 
1 
1 1 
26 *11.2 
0 0 0 0 0 0 0 0 0 0 0 
26 11.2 0 0 1 1 4 4 0 
0 
0 
0 1 
__________________________________________________________________________ 
.sup.* Plants observed approximately 14 days after treatment. 
In addition, each of the compounds herein have been found to be effective 
in controlling up to 50% of at least one or more of the plant species 
listed above. A preferred embodiment is those pyrazolecarboxylates in 
which X is CF.sub.3, especially in the meta position, R is alkyl and 
R.sub.1 is lower alkyl, especially methyl. Specifically preferred are the 
compounds of Examples 1 and 6. 
In addition, it should be noted that many of the novel pyrazolecarboxylates 
of the invention selectively inhibit the growth of undesirable weeds in 
the presence of crop plants, such as soybeans. 
For the sake of brevity and simplicity, the term "active ingredient" has 
been used herein and is used hereinafter to describe the 
pyrazolecarboxylate compounds of Formula A. 
In practicing the herbicidal methods of this invention, the active 
ingredients can be used alone or in combination with a material referred 
to in the art as an adjuvant in liquid or solid form. Herbicidal 
formulations are prepared by admixing the active ingredient with an 
adjuvant including diluents, extenders, carriers and conditioning agents 
to provide compositions in the form of finely-divided particulate solids, 
granules, pellets, solutions, dispersions or emulsions. Thus, the active 
ingredient can be used with an adjuvant such as a finely-divided 
particulate solid, a liquid of organic origin, water, a wetting agent, 
dispersing agent, an emulsifying agent or any suitable combination of 
these. The herbicidal formulations usually contain from about 0.01 to 
about 99 percent by weight of active ingredient. 
Typical finely-divided solid carriers and inert solid extenders which can 
be used with the active ingredients include, for example, the talcs, 
natural and synthetic clays (e.g. kaolinites and attapulgite), pumice, 
silica, synthetic calcium and magnesium silicates, diatomaceous earth, 
quartz, Fuller's earth, salt, sulfur, powdered cork, powdered wood, ground 
corn cobs, walnut flour, chalk, tobacco dust, charcoal, volcanic ash, 
cottonseed hulls, wheat flour, soybean flour, tripoli and the like. 
Typical liquid diluents include for example: petroleum fractions such as 
kerosene, hexane, xylene, benzene, Diesel oil, toluene, acetone, ethylene 
dichloride, Stoddard solvent, alcohols such as propanol, glycols and the 
like. 
Herbicidal formulations, particularly liquids and wettable particles, 
usually contain as a conditioning agent one or more surface-active agents 
in amounts sufficient to render a given composition readily dispersible in 
water or in oil. By the term "surface-active agent" it is understood that 
wetting agents, dispersing agents, suspending agents and emulsifying 
agents are included therein. 
Specific surface-active agents which can be used in the herbicidal 
formulations of this invention are set out, for example, in Searle U.S. 
Pat. Nos. 2,426,417; Todd 2,655,447; Jones 2,412,510 and Lenher 2,139,276. 
In general, less than 50 parts by weight of the surface-active agent is 
present per 100 parts by weight of phytotoxic formulation. 
Preferred wetting agents are alkyl benzene and alkyl naphthalene 
sulfonates, sulfated fatty alcohols, amines or acid amides, long chain 
acid esters of sodium isothionate, esters of sodium sulfosuccinate, 
sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated 
vegetable oils, polyoxyethylene derivatives of alkylphenols (particularly 
isooctylphenol and nonylphenyl) and polyoxyethylene derivatives of the 
mono-higher fatty esters of hexitol anhydrides (e.g. sorbitan). Preferred 
dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin 
sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene 
sulfonate, polymethylene bis-naphthalenesulfonate and sodium 
N-methyl-N-(long chain acid) laurates. 
Wettable powder formulations usually contain from about 5 to about 95 parts 
by weight of active ingredient, from about 0.25 to 25 parts by weight of 
wetting agent, from about 0.25 to 25 parts by weight of the dispersant and 
from 4.5 to about 94.5 parts by weight of inert solid extender, all parts 
being by weight of the total formulation. Where required, from about 0.1 
to 2.0 parts by weight of the solid inert extender can be replaced by a 
corrosion inhibitor or anti-foaming agent or both. 
Aqueous suspensions can be prepared by mixing together and grinding an 
aqueous slurry of water-insoluble active ingredient in the presence of 
dispersing agents to obtain a concentrated slurry of very finely divided 
particles. The resulting concentrated aqueous suspension is characterized 
by its extremely small particle size, so that when diluted and sprayed 
coverage is very uniform. 
Dusts are dense finely divided particulate formulations which are intended 
for application to the soil in dry form. Dusts are characterized by their 
free-flowing and rapid settling properties so that they are not readily 
windborne to areas where they are of no value. Dusts contain primarily an 
active ingredient and a dense, free-flowing finely divided particulate 
extender. However, their performance is sometimes aided by the inclusion 
of a wetting agent such as those listed hereinbefore under wettable powder 
compositions and convenient in manufacture frequently demands the 
inclusion of an inert, absorptive grinding aid. Suitable classes of 
grinding aids are natural clays, diatomaceous earth and synthetic minerals 
derived from silica and silicate. Preferred grinding aids include 
attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic 
calcium and magnesium silicates. 
The inert finely divided solid extender for the dusts can be either of 
vegetable or mineral origin. The solid extenders are characterized by 
possessing relatively low surface areas and are poor in liquid absorption. 
Suitable inert solid extenders for herbicidal dusts include micaceous 
talcs, pyrophyllite, dense kaolin clays, ground calcium phosphate rock and 
phyllite, and tobacco dust. The dusts usually contain from about 0.5 to 95 
parts active ingredient, 0 to 50 parts grinding aid, 0 to 50 parts wetting 
agent and 5 to 99.5 parts dense solid extender, all parts being by weight 
and based on the total weight of the dust. 
The wettable powders described above may also be used in the preparation of 
dusts. While such wettable powders could be used directly in dust form, it 
is more advantageous to dilute them by blending with the dense dust 
diluent. In this manner, dispersing agents, corrosion inhibitors, and 
anti-foam agents may also be found as components of a dust. 
Emulsifiable oil formulations are usually solutions of active ingredient in 
water-immiscible or partially water-immiscible solvents together with a 
surface-active agent. Suitable solvents for the active ingredient of this 
invention include hydrocarbons and water-immiscible ethers, esters or 
ketones. Suitable surface-active agents are anionic, cationic and 
non-ionic such as alkyl aryl polyethoxy alcohols, polyethylene sorbitol or 
sorbitan fatty acid esters, polyethylene glycol fatty esters, fatty 
alkyllol amide condensates, amine salts of fatty alcohol sulfates together 
with long chain alcohols and oil soluble petroleum sulfonates or mixtures 
thereof. The emulsifiable oil formulations generally contain from about 5 
to 95 parts active ingredient, about 1 to 50 parts surface active agent 
and about 4 to 94 parts solvent, all parts being by weight based on the 
total weight of the emulsifiable oil. 
Granules are physically stable particulate formulations comprising active 
ingredient adhering to or distributed through a basic matrix of an inert, 
finely divided particulate extender. In order to aid leaching of the 
active ingredient from the particulate, a surface active agent such as 
those listed hereinbefore under wettable powders can be present in the 
composition. Natural clays, pyrophyllites, illite and vermiculite are 
examples of operable classes of particulate mineral extenders. The 
preferred extenders are the porous, absorptive, preformed particles such 
as preformed and screened particulate attapulgite or heat expanded, 
particulate vermiculite, and the finely divided clays such as kaolin 
clays, hydrated attapulgite or bentonitic clays. These extenders are 
sprayed or blended with the active ingredient to form the herbicidal 
formulations. 
The mineral particles which are used in the herbicidal formulations usually 
have a size range of 10 to 100 mesh, but preferably such that a large 
majority of the particles have from 14 to 60 mesh with the optimum size 
being from 20 to 40 mesh. Clay having substantially all particles between 
14 and 80 mesh and at least about 80 percent between 20 and 40 mesh is 
particularly preferred for use in the herbicidal formulations. The term 
"mesh" as used herein means U.S. Sieve Series. 
The granular herbicidal formulations generally contain from about 5 parts 
to about 30 parts by weight of active ingredient per 100 parts by weight 
of clay and 0 to about 5 parts by weight of surface-active agent per 100 
parts by weight of particulate clay. The preferred granular formulations 
contain from about 10 parts to about 25 parts by weight of active 
ingredient per 100 parts by weight of clay. 
The herbicidal formulations can also contain other additaments, for 
example, fertilizers, plant growth regulants, pesticides and the like used 
as adjuvant or in combination with any of the above-described adjuvants. 
When operating in accordance with the present invention, effective amounts 
of the active ingredients are applied to the plant system. By application 
to the "plant system" is meant the application of the active ingredient in 
or on soil or plant growth media and/or applied to above ground portions 
of plants in any convenient fashion. Application to the soil or growth 
media can be carried out by simply mixing with the soil, by applying to 
the surface of the soil and thereafter dragging or discing into the soil 
to the desired depth, or by employing a liquid carrier to accomplish the 
penetration and impregnation. The application of liquid and particulate 
solid herbicidal formulations to the surface of soil or to above ground 
portions of plants can be carried out by conventional methods, e.g. powder 
dusters, boom and hand sprayers and spray dusters. The formulations can 
also be applied from airplanes as a dust or a spray because of their 
effectiveness at low dosages. In a further method, the distribution of the 
active ingredients in soil can be carried out by admixture with the water 
employed to irrigate the soil. In such procedures, the amount of water can 
be varied with the porosity and water holding capacity of the soil to 
obtain the desired depth of distribution of the active ingredients. 
The application of an effective amount of the active ingredients of this 
invention to the soil or growth media and/or plant is very important for 
the practice of one embodiment of the present invention. The exact amount 
of active ingredient to be employed is dependent upon such factors as the 
plant species and stage of development thereof, the specific soil and 
depth at which the active ingredients are distributed in the soil and the 
amount of rainfall as well as the specific active ingredient employed. In 
foliar treatment for the modification of vegetative growth, the active 
ingredients are applied in amounts greater than 1.12 kilograms and up to 
about 28 or more kilograms per hectare. In applications to soil for the 
modification of the germination or subsequent growth of seeds or 
vegetative propagules or growth of established vegetation, the active 
ingredients are applied in amounts from above 1.12 to about 56 or more 
kilograms per hectare. Generally, application amounts of 5.6 kilograms or 
more per hectare are preferred. It is believed that one skilled in the art 
can readily determine from the teachings of this specification the general 
procedure for any application. 
In summary, in general the active ingredients may be formulated with the 
active ingredient in minor or major proportions in accordance with the 
table below: 
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Concentration of 
Type of Formulation Active Ingredient 
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1. Granules of relatively 
5 to 50% 
large particle size 
2. Powdery dusts 2 to 90% 
3. Wettable powders 2 to 90% 
4. Emulsifiable concentrates 
5 to 95% 
5. Solutions .01 to 95% 
6. One of the less common types 
.01 to 95% 
of formulations depending on 
the desired mode of application 
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Although this invention has been described with respect to specific 
modifications, the details thereof are not to be construed as limitations, 
for it will be apparent that various equivalents, changes and 
modifications may be resorted to without departing from the spirit and 
scope thereof and it is understood that such equivalent embodiments are 
intended to be included herein.