Arylphosphonodiamide compounds and herbicidal compositions thereof

FIELD OF THE INVENTION 
This invention relates to the use of certain arylphosphonodiamides as 
herbicides. 
Some phosphonodiamide derivatives of herbicidal diphenyl ethers are 
described in U.S. Pat. No. 4,39,624 of Maier et al. Some herbicidal alkyl 
phosphonodiamides are disclosed in British Patent 1,350,286 of Nissan 
Chemical Industries, Ltd. and in Bakumenko et al., Khim. Sel'sk. Khoz., 
vol. 4, p. 691 (1966). 
DESCRIPTION OF THE INVENTION 
In one aspect this invention relates to the use as herbicides of certain 
arylphosphonodiamides which have the formula: 
##STR2## 
in which 
R is hydrogen, mono- or poly-halo, mono- or di-(C.sub.1 -C.sub.4 alkyl), 
C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, phenoxy or nitro; 
R.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sub.3 is C.sub.1 -C.sub.6 alkyl; 
R.sub.2 is C.sub.2 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, 
optionally substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
haloalkyl, C.sub.1 -C.sub.4 haloalkoxy, one or more halogens, or two 
C.sub.1 -C.sub.4 alkoxy groups, or one C.sub.1 -C.sub.4 alkyl and one 
C.sub.1 -C.sub.4 alkoxy group, phenyl-(C.sub.1 -C.sub.2) alkyl or pyridyl; 
or 
R.sub.1 and R.sub.2, and/or R.sub.3 and respectively, taken together with 
the nitrogen atom, form a 4-8 member ring, optionally including an oxygen 
heteroatom; 
and R is C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, 
optionally substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
haloalkyl, C.sub.1 -C.sub.4 haloalkoxy, one or more halogens, or two 
C.sub.1 -C.sub.4 alkoxy groups, or one C.sub.1 -C.sub.4 alkyl and one 
C.sub.1 -C.sub.4 alkoxy group, phenyl-(C.sub.1 -C.sub.2 alkyl) or pyridyl; 
provided that if R.sub.1 is hydrogen, R.sub.2 is alkyl or cycloalkyl. 
Many of the compounds within the formula above are novel, but some 
compounds falling within this genus have been disclosed in articles 
relating to investigations in chemical synthesis or spectroscopy. These 
include Hoffmann et al, Chem. Ber., vol. 93, p. 861 (1960) and Nielsen et 
al, J. Chem. Eng. Data, vol. 9, p. 167 (1964). 
The novel compounds which form another aspect of this invention have the 
general formula: 
##STR3## 
in which 
R is hydrogen mono- or poly-halo, mono- or di-(C.sub.1 -C.sub.4 alkyl), 
C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, phenoxy or nitro; 
R.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sub.3 is C.sub.1 -C.sub.6 alkyl; 
R.sub.2 is C.sub.2 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, 
optionally substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
haloalkyl, C.sub.1 -C.sub.4 haloalkoxy, one or more halogens, or two 
C.sub.1 -C.sub.4 alkoxy groups, or one C.sub.1 -C.sub.4 alkyl and one 
C.sub.1 -C.sub.4 alkoxy group, phenyl-(C.sub.1 -C.sub.2)alkyl or pyridyl; 
or 
R.sub.1 and R.sub.2, and/or R.sub.3 and respectively, taken together with 
the nitrogen atom, form a 4-8 member ring, optionally including an oxygen 
heteroatom; 
and is R.sub.4 C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl, 
optionally substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
haloalkyl, C.sub.1 -C.sub.4 haloalkoxy, one or more halogens, or two 
C.sub.1 -C.sub.4 alkoxy groups, or one C.sub.1 -C.sub.4 alkyl and one 
C.sub.1 -C.sub.4 alkoxy group, phenyl-(C.sub.1 -C.sub.2 alkyl) or pyridyl; 
provided that if R.sub.1 is hydrogen, R.sub.2 is alkyl or cycloalkyl; 
excluding compounds in which 
a) R.sub.1 -R.sub.4 are all ethyl or 
b) R.sub.2 and R.sub.4 are both phenyl. 
The term "alkyl" includes straight and branched chained saturated acyclic 
hydrocarbyl moieties having the indicated number of carbon atoms. 
Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, 
n-butyl, sec.-butyl, t-butyl, isobutyl, n-amyl and n-hexyl. The term 
"cycloalkyl" includes saturated cyclical hydrocarbyl moieties, such as 
cyclopentyl and cyclohexyl. The terms "halogen" or "halo" include chloro, 
bromo, fluoro and iodo. Substituted phenyl groups for R.sub.2 and R.sub.4 
may contain one or more of the indicated substituents. Preferred 
substituents are chloro, fluoro, nitro, methyl, ethyl, i-propyl, t-butyl, 
methoxy, ethoxy and trifluoromethyl. 
Preferred compounds of this series include those in which R.sub.1 -R.sub.4 
are all alkyl groups, particularly alkyl groups having from 3 to 4 carbon 
atoms, particularly straight chain groups, such as n-propyl and n-butyl. 
Most preferred are compounds in which R.sub.1 -R.sub.4, or R.sub.3 and 
R.sub.4, are n-butyl. 
As used herein, the term "herbicide" means a compound or composition which 
adversely controls or modifies the growth of plants. By the term 
"herbicidally effective amount" is meant any amount of such compound or 
composition which causes an adverse modifying effect upon the growth of 
plants. By "plants", it is meant germinant seeds, emerging seedlings and 
established vegetation, including roots and above-ground portions. Such 
controlling or modifying effects include all deviations from natural 
development, such as killing, retardation, defoliation, desiccation, 
regulation, stunting, tillering, leaf burn, dwarfing, and the like. 
The compounds of this invention have been found to be active herbicides, 
particularly post-emergent herbicides; i.e. they may be applied to control 
or kill existing vegetation which has already emerged from the soil. Some 
of the compounds of this invention have demonstrated such postemergence 
herbicidal activity in a relatively short time, and against some weeds, 
with a very strong effect. Herbicides having such rapid and extensive 
post-emergence activity are sometimes referred to as "contact and burn" or 
"burn-down" herbicides and are used, among other applications, for 
clearing vegetation from land such as building lots, highway median 
strips, railroad track beds, and crop land prior to planting or in minimum 
till or no-till farming. Some of the compounds of this invention also 
demonstrate pre-emergence activity, that is, control or killing of 
vegetation by application prior to the emergence of vegetation from the 
soil. Pre-emergence herbicides may be applied by techniques such as 
incorporation into, or spraying or spreading onto, the surface of the 
soil. 
Compounds showing "contact-and-burn" effect, but little or no pre-emergence 
activity, may be useful in clearing land prior to planting since planting 
of a crop can be done relatively soon after the herbicide is applied. 
The compounds of this invention may be prepared from starting 
phosphonodichlorides and appropriate amines, in one or two steps, by the 
general reaction 
##STR4## 
Preferably the two amines are reacted stepwise with the arylphosphonyl 
dichloride. 
Processes of this type in general are carried out at temperatures of from 
about 0.degree. to about 1 20.degree. C., preferably from about 20.degree. 
to about 60.degree. C., preferably in the presence of an inert solvent, 
such as an aromatic hydrocarbon (preferably toluene), dichloromethane or 
ether. The hydrogen chloride produced during the reaction is generally 
removed by using a stoichiometric excess of the reactant amine or a 
stoichiometric amount of a tertiary amine such as triethylamine. 
For compounds in which R.sub.1 is not hydrogen, it is preferable to form an 
intermediate chloroamide by first reacting the phosphonodichloride with an 
excess of an amine R.sub.1 R.sub.2 NH, and then introducing a second amine 
R.sub.3 R.sub.4 NH in the form of the salt R.sub.3 R.sub.4 N.sup.-M.sup.+ 
obtained, for instance, from the amine and an n-alkyllithium.

The following represent examples of preparation of compounds of this 
invention. 
EXAMPLE 1 
Preparation of N,N-Dipropyl-N'-(s-butyl) phenylphosohonodiamide 
(Compound No. 2) 
Phenyl phosphonic dichloride (2.75 g, 14.1 mmol) and di-n-propylamine (1.43 
g, 14.1 mmol) were added sequentially to a solution of triethylamine (3.14 
g, 30 mmol) in 25 ml of toluene with stirring and cooling in an ice bath, 
under nitrogen. After 10 minutes, the reaction mixture was stirred at room 
temperature for 1 hour, filtered, and again cooled. Then, sec.-butylamine 
(1.03 g., 14.1 mmol) was added and stirring was continued overnight. 
The reaction mixture was mixed with water, phase-separated, washed with 
saturated brine and dried. The solvent was removed, resultant oil was 
combined with 20 ml hexanes, filtered and again rotary evaporated to yield 
3.1 g of an oil. The structure was confirmed by spectroscopic analyses. 
EXAMPLE 2 
Preparation of N,N,N',N'-tetra-n-butyl-4-methoxyohenylphosohonodiamide 
(Compound No. 5) 
4-Methoxyphenyl phosphonic dichloride (1.5 g, 6.7 mmol) in a small amount 
of methylene dichloride was added to di-n-butylamine (3.6 g, 28 mmol) in 
50 ml methylene dichloride with stirring at room temperature under 
nitrogen. Following an additional 30 minutes, the crude product mixture 
was washed with 5% HCl (until the extracts were acidic) and water. Drying 
and rotary evaporation gave 2.1 g of a crude yellow oil which was 
chromatographed. The compound eluting with an R.sub.F of 0.53 (25% ethyl 
acetate, silica gel 60) was collected and evaporated to yield 0.55 g of 
intermediate N,N-di-n-butyl-4-methoxyphenylphosphonoamide chloride. This 
material gave satisfactory spectroscopic analyses. 
The intermediate chloroamide was heated with lithium dibutylamide, prepared 
from dibutylamine (0.32 g, 1.45 eq.) amd n-butyllithium (1.5 ml, 1.6M in 
hexane), in 5 ml of dry ether with stirring under nitrogen at 0.degree.. 
After 30 minutes, the crude product mixture was water washed and dried. 
Rotary evaporation yielded 0.52 g of a yellow oil which was 
chromatographed over silica gel using 1:1 ethyl acetate-hexanes as the 
eluent. There was collected 0.30 g of a colorless oil following rotary 
evaporation. Spectroscopic analysis confirmed the structure as the desired 
product. 
Table I depicts representative compounds of this invention, prepared by one 
of the processes described above. Most or all these compounds were 
obtained as oils. Structures were compared by spectroscopic analyses. 
TABLE I 
______________________________________ 
##STR5## 
Cmpd. 
No. R R.sub.1 R.sub.2 R.sub.3 
R.sub.4 
______________________________________ 
1. H n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
2. H H sec-C.sub.4 H.sub.9 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
3. H CH.sub.3 
C.sub.6 H.sub.5 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
4. H CH.sub.3 
C.sub.6 H.sub.5 
CH.sub.3 
C.sub.6 H.sub.5 
5. 4-OCH.sub.3 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
6. H n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
7. H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
8. 3-OCH.sub.3 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
9. H H C.sub.6 H.sub.5 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
10. H i-C.sub.4 H.sub.9 
i-C.sub.4 H.sub.9 
i-C.sub.4 H.sub.9 
i-C.sub.4 H.sub.9 
11. H C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
12. H 
##STR6## C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
13. H (CH.sub.2).sub.6 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
14. H CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
15. H n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 CH.sub.2 
n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 CH.sub.2 
16. H CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
17. H n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 CH.sub.2 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
18. H C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
19. 2,5-CH.sub.3 
n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 CH.sub.2 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
20. 2,5-CH.sub.3 
CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
21. 2,5-CH.sub.3 
CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
CH.sub.3 
C.sub.6 H.sub.5 CH.sub.2 
22. 4-OCH.sub.3 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
23. H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
n-C.sub.6 H.sub.13 
n-C.sub.6 H.sub.13 
24. H C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
25. H n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
26. H CH.sub.3 
2-CH.sub.3 C.sub.6 H.sub.4 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
27. H CH.sub.3 
3-CH.sub.3 C.sub.6 H.sub.4 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
28. H CH.sub.3 
4-CH.sub.3 C.sub.6 H.sub.4 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
29. H (CH.sub.2).sub.3 
n-C.sub.4 H.sub.9 
C.sub.6 H.sub.5 
30. H (CH.sub.2).sub.3 
C.sub.2 H.sub.5 
C.sub.6 H.sub.5 
31. H CH.sub.3 
C.sub.6 H.sub.5 
n-C.sub.4 H.sub.9 
n-C.sub.4 H.sub.9 
32. H CH.sub.3 
3-CF.sub.3 C.sub.6 H.sub.4 
n-C.sub.3 H.sub.7 
n-C.sub.3 H.sub.7 
______________________________________ 
Herbicidal Activity Tests 
Compounds in Table I were tested for herbicidal activity as follows: 
The herbicidal effect was observed by comparing the extent of weed control 
in test flats treated with the compounds against that occurring in similar 
non-treated control flats. All were applied at 3.57 lb/A (4 kg/ha) to 
pre-emergence and post-emergence screening flats. An 80 gal/A (748.3 l/ha) 
spray volume was utilized. Post-emergence flats were seeded 12 days prior 
to treatment. Pre-emergence flats were seeded one day prior to treatment. 
Overhead watering of pre-emergence flats and soil surface watering of 
post-emergence flats, so as to avoid wetting the foliage, were carried out 
for the duration of the test. 
Weed seeds were planted in a flat at a seed depth of 0.5 inch (1.3 cm). 
Soil for flats was prepared using loam soil fortified with 17-17-17 
fertilizer (N-P.sub.2 O.sub.5 -K.sub.2 O on a weight basis) and Captan 80W 
fungicide. The test weeds were as follows: 
______________________________________ 
COMMON NAME SCIENTIFIC NAME 
______________________________________ 
green foxtail Setaria viridis 
watergrass Echinochloa crusgalli 
wild oat Avena fatua 
annual morning glory 
Ipomoea purpurea 
velvetleaf Abutilon theophrasti 
wild mustard Brassica kaber 
curly dock Rumex crispus 
(some compounds) 
yellow nutsedge Cyperus esculentus 
______________________________________ 
The spray solutions were prepared by dissolving 240 mg of test compound in 
20 ml of acetone containing 1% polyoxyethylene sorbitan monolaurate 
emulsifier, then adding 20 ml of water to the resulting solution. The 
stock solutions were applied using a linear spray table. Pre-emergence 
flats are raised to the level of the post-emergence foliage canopy by 
setting the flats on a wooden block. 
The degree of weed control was visually assessed and recorded as percentage 
control compared to the growth of the same species in an untreated check 
flat of the same age. The rating scale ranges from 0 to 100%, where 0 
equals no effect with plant growth equal to the untreated control, and 100 
equals complete kill. 
Ratings were taken in pre-emergence tests approximately 12-18 days after 
treatment (DAT). In post-emergence tests, ratings were taken at two 
intervals. On the sixth day after treatment, overall control was rated, as 
an indication of total vegetative control, or "contact and burn" activity. 
Approximately 12-18 days after treatment, the tests were rated for overall 
post-emergence activity. 
Results are listed in Table II below, expressed as average control of the 
three grassy (GR) (wild oat, watergrass, foxtail) and three broadleaf 
weeds (BL) (morning glory, mustard, velvetleaf), and of nutsedge (NS). 
TABLE II 
__________________________________________________________________________ 
% Control, 3.57 kg/ha 
Pre-emergence Post-emergence 
Compound 
12-18 DAT 6 DAT 12-18 DAT 
No. GR avg. 
BL avg. 
NS GR avg. 
BL avg. 
NS GR avg. 
BL avg. 
NS 
__________________________________________________________________________ 
1. 0 0 0 10 30 0 33 50 0 
2. 0 0 0 30 90 0 67 100 0 
3. 0 0 0 30 50 10 33 53 0 
4. 0 0 0 10 30 0 0 73 0 
5.*** 0 0 0 -- -- -- 18 44 15 
6. 0 0 0 -- -- -- 67 100 0 
7. 0 0 0 20 80 0 43 100 0 
8. 0 0 0 20 90 5 62 98 10 
9. 0 0 0 25 60 0 0 83 0 
10. 0 0 0 -- -- -- 0 26 0 
11. 0 0 0 -- -- -- 52 63 0 
12. 0 0 0 -- -- -- 13 23 0 
13. 0 0 0 -- -- -- 30 50 0 
14. 0 0 0 -- -- -- 18 56 0 
15. 0 0 0 -- -- -- 0 28 0 
16. 0 0 0 -- -- -- 7 19 0 
17. 0 0 0 -- -- -- 33 38 0 
18. 0 0 0 -- -- -- 0 29 0 
19. 0 0 0 -- -- -- 47 5 0 
20. 0 0 0 -- -- -- 62 50 0 
21. 0 0 0 -- -- -- 49 44 0 
22.* 8 28 0 60 100 25 6 100 5 
23.* 0 38 0 60 95 15 10 100 5 
24.* 0 30 0 65 98 15 13 100 5 
25.* 0 36 0 40 90 10 6 86 0 
26.* 0 10 0 30 85 5 41 76 5 
27.* 0 13 0 30 85 0 26 80 0 
28.** 0 13 0 30 85 5 26 76 0 
29.* 0 0 0 30 85 10 5 83 5 
30.* 0 41 0 30 90 5 21 80 5 
31.* 0 25 0 30 85 5 15 83 0 
32.* 0 15 0 20 75 5 28 83 5 
__________________________________________________________________________ 
*Application rate: 4 kg/ha 
**Application rate: 2 kg/ha 
***Application rate: 1.5 kg/ha 
Selected compounds were further tested against the same weeds at a lower 
application rate of 1.5 kg/ha. In general, control of grassy weeds was 
lower, but for the most part, control of broadleaf weeds remained at 80% 
or above. 
In practice, a pure compound can be used as a herbicide. However, in 
general, the compounds are first formulated with one or more inert 
carriers or diluents suitable for herbicidal use, before being applied. 
The compositions or formulations, including a compound as described herein, 
may exist in any one of a number of solid or liquid forms. Examples of 
liquid forms are emulsifiable concentrates, flowables and pastes. Such 
compositions may contain, in addition to the active compound or compounds, 
various carriers or diluents; surface active agents (wetting agents, 
dispersing agents and/or emulsifying agents); solvents (water, or organic 
solvents such as aromatic solvents or chlorinated aliphatic solvents); 
adhesives; thickeners; binders; antifoaming agents; and other substances 
as mentioned herein. Solid carriers or diluents included in such 
compositions or formulations may include, for example, ground natural 
minerals such as kaolins, alumina, calcium carbonate, silica, kieselguhr, 
clay, etc.; ground synthetic minerals such as various silicates and 
aluminosilicates and ground vegetable products such as bark, cornmeal, 
sawdust, cellulose powder and the like. 
To manufacture solid compositions, the active substances are mixed with 
solid carriers or diluents such as those mentioned above and the mixture 
is ground to the appropriate size. Granules can be manufactured by 
dissolving an active compound in an organic solvent and applying the 
mixture, for example, by atomization, onto an absorptive granulated inert 
material, such as silica. Adhesives may be utilized to assist in the 
incorporation of the compound onto the solid particles. Pellets or 
granules can be manufactured by extrusion with appropriate carriers and 
binders. 
Wettable powders, flowables, and pastes are obtained by mixing and grinding 
an active compound with one or more dispersing agents and/or solid 
carriers or diluents. Also included may be wetting agents and/or 
dispersing agents, for example, lignins, methyl cellulose, 
naphthalenesulfonic acid derivatives, fatty alcohol sulfates and various 
types of alkali and alkaline earth metal salts of fatty acids. 
Emulsifiable concentrates are generally obtained by dissolving the active 
compound in an organic solvent, for example, butanol, cyclohexanone, 
xylenes, or higher boiling aromatic hydrocarbons. To obtain suspensions or 
emulsions in water wetting agents are generally also added. 
The compositions may also be used in the form of microcapsules. 
Microcapsules consist of fully enclosed or encapsulated droplets or 
granules containing the active compound, enclosed within an inert porous 
membrane, so as to permit escape of the encapsulated material into the 
surrounding medium or environment at a controlled rate. 
Useful encapsulating materials include natural and synthetic rubbers or 
latexes, cellulosic materials, styrenebutadiene copolymers, 
polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes 
and starch xanthates. 
It is possible to use highly concentrated liquid compositions containing up 
to about 95% by weight of the active compound, or even the active compound 
alone for those compounds which are liquids, when applying the compound in 
the form of a finely divided liquid by use of various atomizing equipment, 
for example by airplane crop-spraying techniques. For other purposes, 
however, the various types of compositions which can be utilized for these 
compounds will contain varying amounts of the compound according to the 
type of composition and the intended use. 
In general, compositions may contain from 0.1 to 95% of the active 
compound, more preferably from 0.5 to 90%. Some typical compositions will 
contain an active compound as follows: Wettable powders, flowables and 
pastes--20 to 90% active compound; oil suspensions, emulsions, solutions 
and emulsifiable concentrates--5 to 90% active compound; aqueous 
suspensions--10 to 50% active compound; dusts and powders--1 to 25% active 
compound; granules and pellets--1 to 20% active compound. 
The rate of application of the active compound to a locus to be controlled 
will depend on the activity of the compound and/or composition and the 
nature of the seeds and plants to be controlled and will vary from about 
0.05 to about 50 pounds per acre (about 0.06 to about 56 kg/ha). 
Compositions containing one or more of the active compounds described, in a 
herbicidally effective amount, may be applied to the plant or locus to be 
controlled in any conventional manner. Thus, powders and various liquid 
compositions containing the active compound can be applied by the use of 
power dusters, boom and hand sprayers and spray spray dusters, or applied 
from airplanes as mists or sprays. When applied in the latter method, they 
may be effective in very low dosages. To modify or control growth of 
germinating seeds or emerging seedlings, liquid compositions may be 
applied to the soil with conventional methods and may be distributed in 
the soil to a depth of one-half inch below the soil surface. The 
compositions need not be admixed with the soil particles, but can be 
applied merely by sprinkling on the surface of the soil. 
Compositions including active compounds may also be applied by addition to 
irrigation waters supplied to the field to be treated. This method of 
application permits penetration of the compounds into the soil as the 
water is absorbed therein. 
______________________________________ 
EXAMPLES OF TYPICAL COMPOSITIONS 
______________________________________ 
Ingredient Weight % 
______________________________________ 
Oil 
Active Compound 1 
Oil solvent-heavy aromatic naphtha 
99 
Total 100 
Emulsifiable Concentrate 
Active Compound 50 
Kerosene 45 
Emulsifying agent (mixture of long 
5 
chain ethoxylated polyethers with 
long chain sulfonate) 
Total 100 
Emulsifiable Concentrate 
Active Compound 90 
Kerosene 5 
Emulsifying agent (mixture of long 
5 
chain ethoxylated polyethers with 
long chain sulfonate) 
Total 100 
Dusts and/or Powders 
Ingredient Wt. % Wt. % Wt. % 
______________________________________ 
Active Compound 0.5 50.0 90.0 
Attapulgite Clay Powder 
93.5 44.0 4.0 
Sodium lignin sulfonate 
5.0 5.0 5.0 
Sodium dioctyl sulfosuccinate 
1.0 1.0 1.0 
TOTAL 100.0 100.0 100.0 
______________________________________ 
The compositions of the invention may comprise, in addition to one or more 
compounds of the invention, one or more compounds not of the invention but 
which possess biological activity. Compounds not of this invention may be 
other pesticidal agents, such as herbicides, fungicides, insecticides, 
acaricides, nematocides, bactericides, and plant growth regulators. Such 
compositions may also contain soil disinfectants or fumigants and may 
further contain fertilizers, thus making it possible to provide 
multi-purpose compositions containing one or more of the compounds 
described herein as well as, optionally, other pesticides and also 
fertilizers, all intended and formulated for use at the same locus. 
Accordingly, in yet a still further embodiment, the invention provides an 
herbicidal composition comprising a mixture of at least one herbicidal 
compound of formula (I) as hereinbefore defined with at least one other 
herbicide. 
The other herbicide may be any herbicide not having the formula (I). It 
will generally be an herbicide having a complementary action in the 
particular application. 
Examples of useful complementary herbicides include: 
A. Benzo-2,1,3-thiodiazin-4-one-2,2-dioxides such as 
3-isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (bentazone); 
B. hormone herbicides, particularly the phenoxy alkanoic acids such as 
4-chloro-2-methylphenoxyacetic acid (MCPA), S-ethyl 4-chloro-O-tolyloxy 
thioacetate (MCPA-thioethyl), 2-(2,4-dichlorophenoxy) propionic acid 
(dichlorprop), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 
4-(4-chloro-2-methylphenoxy)butyric acid (MCPB), 2,4-dichlorophenoxyacetic 
acid (2,4-D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), 
2-(4-chloro-2-methylphenoxy) propionic acid (mecoprop), 
3,5,6-trichloro-2-pyridyloxyacetic acid (trichlopyr), 
4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid (fluroxypyr), 
3,6-dichloropyridine-2-carboxylic acid (clopyralid), and their derivatives 
(e.g. salts, esters and amides); 
C. 1,3-dimethylpyrazole derivatives such as 2-[4-(2,4-dichlorobenzoyl) 
1,3-dimethylpyrazol-5-yloxy] acetophenone (pyrazoxyfen), 
4-(2,4-dichlorobenzoyl)1,3-dimethylpyrazol-5-yltoluene sulfonate 
(pyrazolate) and 
2-[4-(2,4-dichloro-m-toluolyl)-1,3-dimethylpyrazol-5-yloxy]-4,-methylaceto 
phenone (benzofenap); 
D. Dinitrophenols and their derivatives (e.g. acetates such as 
2-methyl-4,6-dinitrophenol (DNOC), 2-t-butyl-4,6-dinitrophenol (dinoterb), 
2-sec.-butyl-4,6-dinitrophenol (dinoseb) and its ester, dinoseb acetate; 
E. dinitroaniline herbicides such as 
N',N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamin 
(dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline 
(trifluralin), 
N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline 
(ethalfluralin), N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine 
(pendimethalin); and 3,5-dinitro-N.sup.4, N.sup.4 -dipropylsulphanilamide 
(oryzalin); 
F. arylurea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea 
(diuron), N,N-dimethyl-N'-[3-(trifluoromethyl) phenyl]urea (flumeturon), 
3-(3-chloro-4-methoxyphenyl)1,1-dimethylurea (metoxuron), 
1-butyl-3-(3,4-dichlorophenyl)-1-methylurea (neburon), 
3-(4-isopropylphenyl)-1,1-dimethylurea (isoproturon), 
3-(3-chloro-p-tolyl)-1,1-dimethylurea (chlorotoluron), 
3-[4-(4-chlorophenoxy) phenyl]-1,1-dimethylurea (chloroxuron), 
3-(3,4-dichlorophenyl)-1-methylurea (linuron), 
3-(4-chlorophenyl)-1-methoxy-1-methylurea (monolinuron), 
3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (chlorobromuron), 
i-(1-methyl-1-phenylethyl)-3-p-tolylurea (daimuron), and 
1-benzothiazol-2-yl-1,3-dimethylurea (methabenzthiazuron); 
G. phenylcarbamoyloxyphenylcarbamates such as 
3-[methoxycarbonylamino]phenyl (3-methylphenyl)carbamate (phenmedipham) 
and 3-[ethoxycarbonylamino]-phenyl phenylcarbamate (desmedipham); 
H. 2-phenylpyridazin-3-ones such as 
5-amino-4-chloro-2-phenylpyridazin-3-one (chloridazon), and 
4-chloro-5-methylamino-2-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl) 
pyridazin-3(2H)-one (norflurazon); 
I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (lenacil), 
5-bromo-3-sec.-butyl-6-methyluracil (bromacil) and 
3-t-butyl-5-chloro-6-methyl-uracil (terbacil); 
J. triazine herbicides such as 2-chloro-4-ethyl 
amino-6-(i-propylamino)-1,3,5-triazine (atrazine), 
2-chloro-4,6-di(ethylamino)-1,3,5-triazine (simazine), 2-azido- 
4-(i-propylamino)-6-methylthio-1,3,5-triazine (aziprotryne), 
2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2- methylpropionitrile 
(cyanazine), N.sup.2, N.sup.4 
-di-isopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (prometryn), N.sup.2 
-(1,2-dimethylpropyl)-N.sup.4 
-ethyl-6-methylthio-1,3,5-triazine-2,4-diamine (dimethametryn), 
N.sup.2,N.sup.4 -diethyl-6-methylthio-1,3,5-triazine-2,4-diamine 
(simetryne), and N.sup.2 -tert.-butyl-N.sup.4 
-ethyl-6-methylthio-1,3,5-triazine-2,4-diamine (terbutryn); 
K. phosphorothioate herbicides such as S-2-methyl-piperidinocarbonyl-methyl 
O,O-dipropyl phosphorodithioate (piperophos), S-2-benzenesulphonamidoethyl 
O,O-diisopropyl phosphonodithioate (bensulide), and O-ethyl 
O-6-nitro-m-tolyl sec.-butylphosphoramidothioate (butamifos); 
L. thiolcarbamate herbicides such as S-ethyl N-cyclohexyl-N-ethyl 
thiocarbamate (cycloate), S-propyl dipropyl-thiocarbamate (vernolate), 
S-ethyl-azepine-1-carbothioate (molinate), S-4-chlorobenzyl 
diethylthiocarbamate (thiobencarb), S-ethyl di-isobutyl-thiocarbamate 
(butylate)*, S-ethyl di-isopropylthiocarbamate (EPTC)*, 
S-2,3,3-trichloroallyl diisopropyl thiocarbamate (triallate), 
S-2,3-dichloroallyl diisopropyl thiocarbamate (diallate), S-benzyl 
1,2-dimethylpropyl (ethyl) thiocarbamate (esprocarb), S-benzyl 
di(sec.-butyl) thiocarbamate (tiocarbazil), 
6-chloro-3-phenylpyridazin-4-yl S-octyl thiocarbamate (pyridate), and 
S-1-methyl-1-phenylethylpiperidine-1-carbothioate (dimepiperate); 
FNT *These compounds are preferably employed in combination with a safener such 
as 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid). 
M. 1,2,4-triazin-5-one herbicides such as 
4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (metamitron) 
and 4-amino-6-butyl-4,5-dihydro-3-methylthio-1, 3,4-triazin-5-one 
(metribuzin); 
N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 
3,6-dichloro-2-methoxybenzoic acid (dicamba) and 
3-amino-2,5-dichlorobenzoic acid (chloramben); 
O. anilide herbicides such as 
2-chloro-2',6'-diethyl-N-(2-propoxyethyl)acetanilide (pretilachlor), 
N-butoxymethyl-2-chloro-2',6,-diethylacetanilide (butachlor), the 
corresponding N-methoxy compound (alachlor), the corresponding N-i-propyl 
compound (propachlor), 3',4'- dichloropropionanilide (propanil), 
2-chloro-N-[pyrazol-1-ylmethyl]acet-2,-6,xylidide(metazachlor), 
2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl) acetotoluidide 
(metolachlor), 2-chloro-N-ethoxymethyl-6'-ethylacetotoluidide 
(acetochlor), and 2-chloro-N-(2-methoxyethyl)acet-2',6'-xylidide 
(dimethachlor); 
P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile 
(dichlobenil), 3,5-dibromo-4-hydroxy-benzonitrile (bromoxynil) and 
3,5-diiodo-4-hydroxy-benzonitrile (ioxynil); 
Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (dalapon), 
trichloroacetic acid (TCA) and salts thereof; 
R. diphenylether herbicides such as ethyl 
2-[5-(2-chloro-trifluoro-p-tolyloxy)-2-nitrobenzoyl]oxy propionate 
(lactofen), 
D-[5-(2-chloro-.alpha.,.alpha.,.alpha.-trifuoro-p-tolyl)-2-nitrobenzoyl] 
gycolic acid (fluroglycofen) or salts or esters thereof, 
2,4-dichlorophenyl-4-nitrophenyl ether (nitrofen), 
methyl-(2,4-dichlorophenoxy)-2-nitrobenzoate (bifenox), 
2-nitro-5-(2-chloro-4-trifluoromethyl-phenoxy) benzoic acid (acifluorfen) 
and salts and esters thereof, 2-chloro-4-trifluoromethylphenyl 
3-ethoxy-4-nitrophenyl ether (oxyfluorfen) and 
5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamid 
e (fomesafen); 2,4,6-trichlorophenyl 4-nitrophenyl ether (chlornitrofen) 
and 5-(2,4-dichlorophenoxy)-2-nitroanisole (chlomethoxyfen); 
S. phenoxyphenoxypropionate herbicides such as 
(RS)-2-[4-(2,4-dichlorophenoxy) phenoxy]propionic acid (diclofop) and 
esters thereof such as the methyl ester, 
2-[4-(5-trifluoromethyl)-2-(pyridinyl)oxy]phenoxypropanoic acid 
(fluazifop) and esters thereof, 
2-[4-(3-chloro-5-trifluoromethyl)-2-pyridinyl)oxy] phenoxypropanoic acid 
(haloxyfop) and esters thereof, 2-[4-(6-chloro-2-quinoxalinyl)oxy] 
phenoxypropanoic acid (quizalofop) and esters thereof and 
(.+-.)-2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy] propionic acid 
(fenoxaprop) and esters thereof such as the ethyl ester; 
T. cyclohexanedione herbicides such as 
2,2-dimethyl-4,6-dioxo-5-[1-(2-propenyloxyimino)butyl] cyclohexane 
carboxylic acid (alloxydim) and salts thereof, 2-(1-ethoxyimino) 
butyl-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexan-1-one (sethoxydim), 
2-(1-ethoxyimino)butyl-3-hydroxy-5-thian-3 -ylcyclohex-2-enone 
(cycloxydim), 2-[1(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone 
(tralkoxydim), and (.+-.)-2-(E)-1-[(E)-3-chloroallyloximino] 
propyl-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone (clethodim); 
U. sulfonyl urea herbicides such as 2-chloro-N (4-methoxy-6-methyl-1, 
3,5-triazin-2-yl)-aminocarbonyl) benzenesulphonamide (chlorosulfuron), 
methyl 
2-[([(4,6-dimethyl2-pyrimidinyl)amino]-carbonyl)amino]-sulphonylbenzoic 
acid (sulfometuron), 
2-([(3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbonyl]amino)-sulphonyl)be 
nzoic acid (metsulfuron) and esters thereof; 
-(4,6-dimethoxypyrimidin-2-ylcarbamoylsuphamoly)-O-toluic acid 
(benzsulfuron) and esters thereof such as the ester thereof methyl, 
3-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureido- 
sulphonyl]thiophene-2-carboxylate (DPX-M6313), 2-(4-chloro-6-methoxy 
pyrimidin-2-yl carbamoylsulphamoyl benzoic acid (chlorimuron) and esters 
such as the ethyl ester thereof, 
2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulphamoyl)-N,N-dimethyl-nicotinami 
de, 2-[4,6-bis(difluoromethoxy)pyrimidin-2-ylcarbamoylsulphamoyl] benzoic 
acid (pirimisulfuron) and esters such as the methyl ester thereof, 
2-[3-(4-methoxy-6-methyl-1,3,5-triazin-zyl)-3-methylureidosulphonyl] 
benzoic acid esters such as the methyl ester thereof (DPX-LS300) and 
5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulphamoyl)-1-methylpyrazole-4-carb 
oxylic acid (pyrazosulfuron); 
V. imidazolidinone herbicides such as 
2-(4,5-dihydro-4-isopropyl-4-methyl-5-oxoimidazol-2-yl) 
quinoline-3-carboxylic acid (imazaquin), methyl 
6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate and p-toluate 
isomer (imazamethabenz), 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) 
nicotinic acid (imazapyr) and isopropylammonium salts thereof, 
(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic 
acid (imazethapyr); 
W. arylanilide herbicides such as 
benzoyl-N-(3-chloro-4-fluorophenyl)-L-alanine (flamprop) and esters 
thereof, ethyl N-benzoyl-N-(3,4-dichlorophenyl)-DL-alaninate 
(benzoylprop-ethyl), 
N-(2,4-difluorophenyl)-2-(3-trifluoromethyl)phenoxy-3-pyridinecarboxamide 
(diflufenican); 
X amino acid herbicides such as N-(phosphonomethyl)-glycine (glyphosate) 
and DL-homoalanin-4-yl (methyl) phosphinic acid (gluyfosinate) and their 
salts and esters, trimethylsulfonium N-(phosphonomethyl)-glycine 
(sulphosate), and bilanafos; 
Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA); 
Z. herbicidal amide derivative such as 
(RS)-N,N-diethyl-2-(1-naphthyloxypropionamide) (napropamide), 
3,5-dichloro-N-(1,1-dimethylpropynyl)benzamide (propyzamide), 
(R)-1-(ethylcarbamoyl)ethyl carbanilate (carbetamide), 
N-benzyl-N-isopropylpivalamide (tebutam), 
(RS)-2-bromo-N-(.alpha.,.alpha.-dimethylbenzyl)-3,3-dimethylbutyramide 
(bromobutide), N-[3-(1-ethyl-1-methylpropyl)-isoxazol-5-yl] 
2,6-dimethoxybenzamide, (isoxaben), N-phenyl-2-(2-naphthyloxy) 
propionamide (naproanilide), N,N-dimethyl-diphenylacetamide (diphenamid), 
and N-(1-naphthyl)phthalamic acid (naptalam); 
AA. miscellaneous herbicides including 
2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran methanesulfonate 
(ethofumesate), 7-oxabicyclo 
(2.2.1)heptane,1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-exo 
(cinmethylin), 1,2-dimethyl-3,5-diphenylpyrazolium ion (difenzoquat) and 
salts thereof such as the methyl sulfate salt, 
2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazoldin-3-one (clomazone), 
5-tert.-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2(3H)-on 
e (oxadiazon), 3,5-dibromo-4-hydroxy benzaldehyde 2,4-dinitrophenyloxime 
(bromofenoxim), 4-chlorobut-2-ynyl-3-chlorocarbanilate (barban), 
(RS)-2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane (tridiphane), 
(3RS,4RS;3RS,4SR)-3-chloro-4-chloromethyl-1-.alpha.,.alpha.-.alpha.-triflu 
ro-m-tolyl-2-pyrrolidone (in the ratio 3:1) (flurochloridone), 
dichloroquinoline 8-carboxylic acid (quinchlorac) and 
2-(1,3-benzothiazol-2-yl-oxy)-N-methylacetanilide (mefanacet); 
BB. examples of useful contact herbicides include bipyridylium herbicides 
such as those in which the active entity is the 
1,1'-dimethyl-4,4'-dipyridylium ion (paraquat) and those in which the 
active entity is the 1,1-ethylene-2,2,-dipyridylium ion (diquat).