Triester derivatives of N-phosphonomethylthionoglycine as herbicides

This invention relates to triester derivatives of N-phosphonomethylthionoglycine which represent a new class of organic chemical compounds. This invention further relates to herbicidal compositions and methods employing such compounds.

This invention relates to triester derivatives of 
N-phosphonomethylthionoglycine which represent a new class of organic 
chemical compounds. This invention further relates to herbicidal 
compositions containing such derivatives and to herbicidal methods 
employing such compounds and compositions. 
BACKGROUND OF THE INVENTION 
U.S. Pat. No. 3,799,758 issued to John E. Franz on Mar. 26, 1974 describes 
the preparation and herbicidal utility of N-phosphonomethylglycine and its 
esters, amides, and salts. 
U.S. Pat. No. 4,120,689 issued to Gerard A. Dutra on Oct. 17, 1978 
describes alkyl[di-(benzyl) or di-(aryl)] esters of 
N-phosphonomethylglycine which are produced by the reaction of a dibenzyl 
or diaryl phosphite with an N-methylene alkyl glycinate trimer. These 
esters and the hydrolysis products thereof containing at least one 
benzyloxy or aryloxy group bonded to phosphorous are compounds disclosed 
as having the formula 
##STR1## 
wherein 
R is a member of the group consisting of phenyl, benzyl, naphthyl, 
biphenyl, and phenyl, benzyl or naphthyl groups substituted with from 1 to 
3 groups selected from the class consisting of hydroxyl, lower alkyl, 
lower alkoxy, lower alkylthio, trifluoromethyl, carbo (lower alkoxy), 
nitro or halo; 
R.sub.1 is hydrogen or an R group; and 
R.sub.2 is a lower alkyl group or hydrogen, and the strong acid salts of 
the compounds wherein neither R.sub.1 or R.sub.2 is H. These compounds are 
useful as postemergent herbicides. 
Several N-protected thionoglycinate esters are described in the chemical 
literature. Specifically, the sulfonamide-protected derivative represented 
by the formula 
##STR2## 
has been demonstrated by W. Reid and W. Von der Emden [Liebigs Ann. Chem., 
642, 128-33 (1960)]. Carboxamide protecting groups have also been 
frequently employed to produce derivatives represented by the formula 
##STR3## 
Specific examples include those wherein R is phenyl and R.sub.1 is methyl 
[G. Lowe and A. Williams, Biochem. J., 96, 189-93 (1965); wherein R is 
benzyloxy and R.sub.1 is ethyl [W. Reid and W. Emden, ibid]; and wherein R 
is benzyl or phenethyl and R.sub.1 is methyl [P. R. Carey et al, 
Biochemistry, 21, 3102-8 (1982)]. 
However, there are no examples in the chemical literature of fully 
deprotected thionoglycinate esters or simple N-alkyl derivatives thereof 
which are stable at room temperature and are represented by the formula 
##STR4## 
wherein R.sub.1 is hydrogen or an alkyl group, and R.sub.2 is lower alkyl. 
It will be apparent from a study of the above patents and publications that 
none of them disclose or suggest thionoglycinate esters containing an 
N-[(diaryloxyphosphinyl)methyl]group. In fact, one would anticipate that 
such compounds could not be prepared in light of the known facile reaction 
between thiono ester groups and primary or secondary amines [R. Rapp, 
Canad. J. Chem., 46, 2255-61 (1968); M. K. Kaloustian et al, J. Org. 
Chem., 44, 666-8 (1979); M. K. Kaloustian and R. B. Nader, J. Org. Chem., 
46, 5052-54, (1981)], as well as amino acids, [P. Campbell and B. A. 
Lapinskas, J. Am. Chem. Soc., 99, 5378-82 (1977)] at room temperature. 
BRIEF SUMMARY OF THE INVENTION 
In accordance with the present invention, there is provided novel triester 
derivative of N-phosphonomethylthionoglycine which exhibit unique chemical 
stability and are represented by the formula 
##STR5## 
wherein Y is an alkyl group containing 2-6 carbon atoms as well as the 
strong acid salts of these compounds. The above described compounds are 
herbicidally active. 
DETAILED DESCRIPTION OF THE INVENTION 
The compounds of this invention are prepared by reacting an appropriate 
acetamidic ester described in U.S. Pat. No. 4,104,050 to Dutra of the 
formula 
##STR6## 
wherein Y is as aforedefined with hydrogen sulfide in the presence of a 
hydrogen chloride acceptor to form a compound of Formula I. 
The reaction temperature for the aforerecited reaction is in the range from 
about -50.degree. C. to about +100.degree. C., and is preferably from 
about -30.degree. C. to about +30.degree. C., although greater or lower 
temperatures may be employed if desired. 
The hydrogen chloride acceptor is typically an amine, preferably a tertiary 
amine, which will not react with the reactants employed or products 
formed. Examples of suitable tertiary amine hydrogen chloride acceptors 
include trimethylamine, triethylamine, tributylamine, trihexylamine, 
1,5-diazabicyclo-[5.4.0]-undec-5-ene, pyridine, quinoline, mixtures 
thereof, and the like. 
The compounds of Formula I represent the first known recoverable examples 
of simple N-alkylthionoglycinate derivatives. As such, they represent a 
unique class of organic compounds which incorporate a reactive thiono 
ester moiety in the same molecule as a reactive secondary amine group. 
The chemical behavior of the amine function in compounds of Formula I was 
characterized as typical of a secondary amine by salt formation and amide 
derivatization. The compounds of Formula I can be treated with a strong 
acid to form strong acid salts of the formula 
##STR7## 
wherein Y is as aforedefined, and HX is a strong acid. These salts are 
also herbicidally active. 
The strong acid salts of compounds of Formula III are produced by 
dissolving compounds of Formula I in a suitable inert solvent, such as 
ethyl acetate or chloroform, and then adding a strong acid. The salt 
precipitates or a nonsolvent for the salt is added, such as diethyl ether, 
and the salt forms an insoluble oil or a solid. 
The strong acids which can be employed to produce compounds of Formula III 
are those which have a pKa of 2.2 or less as measured in aqueous solution. 
Examples of suitable acids include hydrochloric, hydrobromic, hydriodic, 
methane sulfonic, benzene sulfonic, p-nitrobenzene sulfonic, 
trifluoroacetic, and the like. 
The compounds of Formula I also react with trifluoroacetic anhydride in an 
inert aprotic solvent and in the presence of a suitable acid scavenger to 
produce compounds of the formula 
##STR8## 
wherein Y is as aforedefined. These trifluoroacetamide derivatives also 
have limited herbicidal properties. 
The chemical reactivity of the thiono ester group in the compounds of 
Formula I was characterized as typical of other known thiono esters by 
reaction with piperidine to produce a thioamide of the formula 
##STR9## 
The term "alkyl" is employed throughout the claims and description to mean 
a monovalent radical in a straight, cyclic, or branched chain, usually of 
the formula C.sub.n H.sub.2.sbsb.n+.sub.1, wherein n is an integer from 2 
to 6. 
Typical groups representative of the term "alkyl" include, for example, 
ethyl, propyl, isopropyl, butyl, neo-pentyl, cyclohexyl, and the like.

The following illustrative, nonlimiting examples will serve to further 
demonstrate to those skilled in the art the process of this invention 
wherein specific compounds within the scope of this invention can be 
prepared. 
EXAMPLE I 
Ethanethioic Acid, 2-[[(Diphenoxyphosphinyl)Methyl]Amino]-O-Ethyl Ester 
.alpha.-[[(diphenoxyphosphinyl)methyl]amino]acetamidic acid, ethyl ester 
dihydrochloride was prepared as a white solid from 
diphenyl-N-phosphonomethylglycinonitrile (9.1 g, 0.03 mole) and absolute 
ethanol (2.8 g, 0.06 mole). This solid was dissolved in 150 ml of dry, 
distilled pyridine at -10.degree. C. Then H.sub.2 S was bubbled in for 2 
hours. The resulting heterogeneous mixture was stirred overnight at 
0.degree. C., filtered, and concentrated in vacuo to give a yellow oil. 
This oil was partitioned between diethyl ether and water. The ether layer 
was separated, dried over MgSO.sub.4, filtered, and concentrated to give a 
yellow oil (7.2 g, 66%). This oil slowly crystallized on standing at room 
temperature to give ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-ethyl ester as a yellow solid, 
m.p. 52.degree.-54.degree. C., corresponding to a compound of Formula I 
wherein Y is ethyl. NMR(.sup.1 H, .sup.31 P, .sup.13 C), IR, and TLC 
results were all consistent with pure product. 
Anal. Calc'd. for C.sub.17 H.sub.20 NO.sub.4 PS: C, 55,88; H, 5.52; N, 
3.83; S, 8.78. Found: C, 55.62; H, 5.60; N, 3.80; S, 8.67. 
EXAMPLE 2 
Ethanethioic Acid, 
2-[[Diphenoxyphosphinyl)Methyl]Amino]-O-(2,2-Dimethylpropyl) Ester 
.alpha.-[[(diphenoxyphosphinyl)methyl]amino]acetamidic acid, 
(2,2-dimethylpropyl) ester dihydrochloride was prepared as a white solid 
from diphenyl-N-phosphonomethylglycinonitrile (24.2 g, 0.08 mole) and 
neo-pentyl alcohol (14.1 g, 0.16 mole). This solid was dissolved in 300 ml 
of dry, distilled pyridine at -10.degree. C. Then H.sub.2 S was bubbled in 
for 3 hours. The resulting heterogeneous mixture was maintained overnight 
at 0.degree. C., filtered, and concentrated in vacuo to give a yellow oil. 
This oil was partitioned between ether and water. The ether layer was 
washed with cold 10% aqueous NaOH, separated, dried over MgSO.sub.4, 
filtered, and concentrated to give 8.0 g of an orange oil. This oil was 
further purified by flash chromatography on silica gel eluting with 40% 
cyclohexane/60% ethyl acetate to give ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-(2,2-dimethylpropyl) ester as a 
yellow oil (4.6 g) with a refractive index n.sub.D.sup.27.5 =1.6650 
corresponding to a compound of Formula I wherein Y is neo-pentyl. NMR 
(.sup. 1 H, .sup.31 P, .sup.13 C), IR, and TLC results were all consistent 
with pure product. 
Anal. Calc'd. for C.sub.20 H.sub.26 NO.sub.4 PS: C, 58.95; H, 6.43; N, 
3.44; S, 7.87. Found: C, 58.90; H, 6.44; N, 3.44; S, 7.77. 
EXAMPLE 3 
Ethanethioic Acid, 2-[[(Dipenoxyphosphinyl)Methyl]Amino]-O-(1-Methylethyl) 
Ester 
.alpha.-[[(diphenoxyphosphinyl)methyl]amino]acetamidic acid, 
(1-methylethyl) ester dihydrochloride was prepared as a white solid from 
diphenyl-N-phosphonomethylglycinonitirile (24.2 g, 0.08 mole) and 
isopropanol (6.2 ml, 0.08 mole). This solid was dissolved at -10.degree. 
C. in 300 ml of dry, distilled pyridine. Then H.sub.2 S was bubbled in for 
2 hours. The resulting heterogeneous mixture was stirred at 0.degree. C. 
for 1 hour, filtered, and concentrated in vacuo to give a yellow oil. This 
oil was partitioned between diethyl ether and water. The ether layer was 
separated, dried over MgSO.sub.4, filtered, and concentrated to give a 
yellow oil (16 g, yield 53%). This oil slowly crystallized on standing in 
a freezer to give ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-(1-methylethyl) ester as a light 
brown solid, m.p. 40.degree.-43.degree. C., corresponding to a compound of 
Formula I wherein Y is isopropyl. NMR (.sup.1 H, .sup.31 P, .sup.13 C), 
IR, and TLC results were all consistent with pure product. 
Anal. Calc'd. for C.sub.18 H.sub.22 NO.sub.4 PS: C, 56.98; H, 5.84; N, 
3.69; S, 8.45. Found: C, 56.83; H, 5.88; N, 3.66; S, 8.44. 
EXAMPLE 4 
Ethanethioic Acid, 2-[[(Diphenoxyphosphinyl)Methyl]Amino]-O-Ethyl Ester, 
p-Nitrobenzene Sulfonic Acid Salt 
2.0 g (0.0055 mole) of ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-ethyl ester was dissolved in 100 
ml of acetonitrile. Then p-nitrobenzene sulfonic acid (1.1 g, 0.0055 mole) 
was added. When no crystallization occurred, the resulting solution was 
concentrated in vacuo to give a yellow oil. This oil could be successfully 
crystallized by dissolving it in a minimum amount of ethyl acetate and 
then adding diethyl ether to the cloud point. This produced ethanethioic 
acid, 2-[[(diphenoxyphosphinyl)methyl]amino]-O-ethyl ester, p-nitrobenzene 
sulfonic acid salt as white needles (2.1 g, yield 67%), m.p. 
64.degree.-66.degree. C. 
Anal. Calc'd. for C.sub.23 H.sub.25 N.sub.2 O.sub.9 PS.sub.2 : C, 48.59; H, 
4.43; N, 4.93; S, 11.28. Found: C, 48.58; H, 4.45; N, 4.90; S, 11.25. 
EXAMPLE 5 
Ethanethioic Acid, 
2-[[(Diphenoxyphosphinyl)Methyl]Amino]-O-(2,2-Dimethylpropyl) Ester, 
Methane Sulfonic Acid Salt 
1.00 g (0.0024 mole) of ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-(2,2-dimethylpropyl) ester was 
dissolved in 5 ml of deuterochloroform. Then 1 equivalent of 
methanesulfonic acid (0.24 g, 0.0024 mole) was added. When no 
crystallization occurred, the resulting solution was concentrated in vacuo 
to give a yellow oil. This oil crystallized upon standing under vacuum at 
room temperature. This produced ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-(2,2-dimethylpropyl) ester, 
methane sulfonic acid salt as a light yellow solid, (1.0 g, yield 80%), 
m.p. 93.degree.-95.degree. C. 
Anal. Calc'd. for C.sub.21 H.sub.30 NO.sub.7 PS.sub.2 : C, 50.09; H, 6.00; 
N, 2.78; S, 12.73. Found: C, 49.81; H, 5.90; N, 2.92; S, 12.86. 
EXAMPLE 6 
Ethanethioic Acid, 
2-[[(Diphenoxyphosphinyl)Methyl](Trifluoroacetyl)Amino]-O-(2,2-Dimethylpro 
pyl) Ester 
Ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl]amino]-O-(2,2-dimethylpropyl) ester (5.0 
g, 0.012 mole) was dissolved in 200 ml of toluene containing triethylamine 
(2.5 g, 0.024 mole). Then trifluoroacetic anhydride (5.1 g, 0.024 mole) 
was carefully added dropwise. A vigorous reaction occurred. The resulting 
heterogeneous mixture was maintained at room temperature for 3 days, then 
cold 5% aqueous NaOH was added. The toluene layer was separated and 
concentrated to give 3.0 g (50%) of an orange oil. This oil was further 
purified by flash chromatography on silica gel eluting with 60% 
cyclohexane/40% ethyl acetate to give ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl(trifluoroacetyl)amino]-O-(2,2-dimethylprop 
yl) ester as a waxy yellow solid, m.p. 41.degree.-44.degree. C., 
corresponding to a compound of Formula IV wherein Y is neo-pentyl. NMR 
(.sup.1 H, .sup.31 P), IR, and TLC results were all consistent with pure 
product. 
Anal. Calc'd. for C.sub.22 H.sub.25 F.sub.3 NO.sub.5 PS: C, 52.48; H, 5.01; 
S, 6.37. Found: C, 52.47; H, 5.04; S, 6.36. 
EXAMPLE 7 
Ethanethioic Acid, 
2-[[(Diphenoxyphosphinyl)Methyl](Trifluoroacetyl)Amino]-O-(1-Methylethyl) 
Ester 
Ethanethioic acid, 2-[[(diphenoxyphosphinyl)methyl]amino]-O-(1-methylethyl) 
ester (5.0 g, 0.013 mole) was dissolved in 200 ml of toluene containing 
triethylamine (2.7 g, 0.026 mole). Then trifluoroacetic anhydride (5.50 g, 
0.026 mole) was carefully added dropwise. A vigorous reaction occurred. 
The resulting heterogeneous reaction was maintained at room temperature 
for 3 days, then cold 5% aqueous NaOH was added. The toluene layer was 
washed with an equal volume of water, separated, dried over MgSO.sub.4, 
filtered, and concentrated to give an orange oil (4.2 g, yield 67%), 
corresponding to a compound of Formula IV wherein Y is isopropyl. NMR 
(.sup.1 H, .sup.31 P), IR, and TLC results were all consistent with pure 
product. 
Anal. Calc'd. for C.sub.20 H.sub.21 F.sub.3 NO.sub.5 PS: C, 50.53; H, 4.45; 
N, 2.95; S, 6.74. Found: C, 50.37; H, 4.51; N, 3.13; S, 7.20. 
EXAMPLE 8 
Ethanethioic Acid, 
2-[[(Diphenoxyphophinyl)Methyl](Trifluoroacetyl)Amino]-O-Ethyl Ester 
Ethanethioic acid, 2-[[(diphenoxyphosphinyl)methyl]amino]-O-ethyl ester 
(7.3 g, 0.02 mole) was dissolved in 250 ml of toluene containing 
triethylamine (4.05 g, 0.04 mole). Then trifluoroacetic anhydride (8.4 g, 
0.04 mole) was carefully added dropwise. A vigorous reaction occurred. The 
resulting heterogeneous mixture was maintained at room temperature for 3 
days, then 200 ml of cold water was added. The toluene layer was washed 
with an equal volume of cold 5% aqueous NaOH and then water, separated, 
dried over MgSO.sub.4, filtered, and concentrated to give 6.0 g of an 
orange oil which solidified upon storage in a freezer. Tritration with 
petroleum ether gave ethanethioic acid, 
2-[[(diphenoxyphosphinyl)methyl](trifluoroacetyl)amino]-O-ethyl ester as a 
light yellow solid (2.80 g, yield 30%). m.p. 71.degree.-72.degree. C., 
corresponding to a compound of Formula IV wherein Y is ethyl. NMR (.sup.1 
H, .sup.31 P), IR, and TLC results were all consistent with pure product. 
Anal. Calc'd. for C.sub.19 H.sub.19 F.sub.3 NO.sub.5 PS: C, 49.46; H, 4.16; 
N, 3.04; S, 6.95. Found: C, 49.61; H, 4.21; N, 3.19; S, 7.37. 
EXAMPLE 9 
Phosphonic Acid, [[[2-(1-Piperidinyl)-2-Thioxoethyl]Amino]Methyl]-, 
Diphenyl Ester 
Ethanethioic acid, 2-[[(diphenoxyphosphinyl)methyl]amino]-O-ethyl ester 
(8.8 g, 0.024 mole) was dissolved under nitrogen in 200 ml of diethyl 
ether. Piperidine (2.05 g, 0.024 mole) was then added, and the resulting 
solution was stirred overnight at room temperature. The ether layer was 
decanted away from a dark insoluble oil. The ether layer was absorbed on 
to 20 g of silica gel and purified by column chromatography eluting with 
20% cyclohexane/80% ethyl acetate to give phosphonic acid, 
[[[2-(1-piperidinyl)-2-thioxoethyl]amino]methyl]-, diphenyl ester as a 
yellow oil (1.7 g, yield 20%), n.sub.D.sup.26.5 =1.5870. NMR (.sup.1 H, 
.sup.31 P) and TLC results were all consistent with pure product. 
Anal. Calc'd. for C.sub.20 H.sub.25 N.sub.2 O.sub.3 PS: C, 59.39; H, 6.23; 
N, 6.93; S, 7.93. Found: C, 59.32; H, 6.29; N, 6.77; S, 7.76. 
EXAMPLE 10 
The post-emergence herbicidal activity of some of the compounds of this 
invention was demonstrated by greenhouse testing in the following manner. 
A good grade of top soil is placed in aluminum pans having holes in the 
bottom and compacted to a depth of 0.95 to 1.27 cm. from the top of the 
pan. A predetermined number of seeds of each of several dicotyledonous and 
monocotyledonous annual plant species and/or vegetative propagules for 
ther perennial plant species are placed on the soil and pressed into the 
soil surface. The seeds and/or vegetative propagules are covered with soil 
and leveled. The pans are then placed on a sand bench in the greenhouse 
and watered from below as needed. After the plants reach the desired age 
(two to three weeks) each pan, except for the control pans, is removed 
individually to a spraying chamber and sprayed by means of an atomizer 
operating at a positive air pressure of approximately 1.46 kg/cm.sup.2 
absolute. The atomizer contains 6 ml of a solution or suspension of the 
chemical. In that 6 ml is an amount of a cyclohexanone emulsifying agent 
mixture to give a spray solution or suspension which contains about 0.4% 
by weight of the emulsifier. The spray solution or suspension contains a 
sufficient amount of the candidate chemical in order to give application 
rates corresponding to those set forth in the tables. The sprays solution 
is prepared by taking an aliquot of a 1.0% by weight stock solution or 
suspension of the candidate chemical in an organic solvent, such as 
acetone or tetrahydrofuran or in water. The emulsifying agent employed is 
a mixture comprising 35 weight percent butylamine dodecylbenzene sulfonate 
and 65 weight percent of a tall oil ethylene oxide condensate having about 
11 moles of ethylene oxide per mole of tall oil. The pans are returned to 
the greenhouse and watered as before and the injury to the plants as 
compared to the control is observed at approximately two and four weeks as 
indicated in the tables under WAT and the results recorded. In some 
instances, the two-week observations are omitted. 
The post-emergence herbicidal activity index used in Tables I and II is as 
follows: 
______________________________________ 
Plant Response Index 
______________________________________ 
less than 25% 0 
inhibition 
25 to less than 50% 
1 
inhibition 
50 to less than 75% 
2 
inhibition 
75 to 99% inhibition 
3 
100% inhibition 4 
(complete kill) 
______________________________________ 
The plant species utilized in these tests are identified by letter in 
accordance with the following legend: 
______________________________________ 
A - Canada Thistle* K - Barnyardgrass 
B - Cocklebur L - Soybean 
C - Velvetleaf M - Sugar Beet 
D - Morning Glory N - Wheat 
E - Lambsquarters, Common 
O - Rice 
F - Smartweed, Pennsylvania 
P - Sorghum 
G - Yellow Nutsedge* 
Q - Wild Buckwheat 
H - Quackgrass* R - Hemp Sesbania 
I - Johnsongrass* S - Panicum Spp 
J - Downy Brome T - Crabgrass, Large 
______________________________________ 
*Established from vegetative propagules. 
The letter "N" in the tables indicates that the particular species was 
absent in the test. 
TABLE I 
__________________________________________________________________________ 
Compound of 
Plant Species 
Example No. 
WAT kg/h 
A B C D E F G H I J K 
__________________________________________________________________________ 
I 2 11.2 
2 3 3 2 3 4 2 3 3 1 3 
4 4 4 4 4 4 4 3 3 4 3 4 
2 5.6 
4 2 3 2 2 4 1 3 4 1 3 
4 4 4 4 4 3 4 2 3 4 3 4 
II 2 11.2 
2 1 1 1 2 4 2 1 2 0 3 
4 1 2 3 2 2 4 2 2 3 2 3 
2 5.6 
0 1 1 1 0 1 0 0 2 1 1 
4 0 1 1 2 2 2 2 1 3 2 2 
III 2 11.2 
1 1 1 2 1 4 2 1 3 1 2 
4 2 2 1 2 3 4 2 1 4 1 3 
2 5.6 
1 1 1 1 1 1 1 2 0 0 2 
4 1 1 1 2 2 4 2 3 2 1 3 
IV 2 11.2 
2 2 3 3 3 3 2 2 3 2 3 
4 4 3 4 4 4 4 3 4 3 3 4 
2 5.6 
2 2 2 2 1 3 1 0 1 0 3 
4 4 3 3 3 3 4 2 2 3 3 4 
V 2 11.2 
1 2 1 1 3 4 1 0 1 1 1 
4 1 4 2 2 3 4 2 1 3 2 3 
2 5.6 
2 1 2 2 3 2 1 1 3 2 2 
4 2 1 1 2 3 2 2 1 3 2 3 
__________________________________________________________________________ 
TABLE II 
__________________________________________________________________________ 
Compound of Plant Species 
Example No. 
WAT kg/h 
L M N O P B Q D R E F C J S K T 
__________________________________________________________________________ 
I 2 5.6 4 4 3 3 4 3 4 4 1 N 4 3 2 4 4 4 
4 4 4 4 4 4 4 4 4 2 N 4 4 3 4 4 4 
2 1.12 
3 4 2 2 3 2 2 N 4 N 3 2 1 3 3 4 
4 3 4 3 2 4 2 2 N 4 N 4 4 1 4 4 4 
2 .28 1 0 2 0 1 1 2 1 0 1 2 1 1 2 2 2 
4 1 1 1 0 2 2 1 2 0 2 2 1 1 2 3 3 
II 2 5.6 2 3 3 2 3 N 3 3 N 3 4 3 3 4 3 4 
4 3 3 3 3 4 N 4 4 N 4 4 4 3 4 4 4 
2 1.12 
1 0 2 1 1 0 2 2 1 2 1 2 1 3 2 3 
4 1 1 1 1 2 0 2 2 1 3 1 1 1 3 3 3 
2 .28 0 1 1 0 1 N 2 1 0 3 3 1 0 3 1 3 
0 1 1 0 1 N 2 2 2 3 3 1 0 3 1 3 
III 2 5.6 3 3 2 1 3 1 2 2 1 2 3 2 1 4 3 4 
4 3 4 3 2 3 1 3 2 2 3 4 2 2 4 3 4 
2 1.12 
1 2 2 1 2 1 1 2 1 2 2 2 2 4 3 2 
4 1 3 2 3 3 1 1 2 1 3 4 2 2 4 3 3 
2 .28 1 4 1 2 1 1 1 2 1 N 2 1 1 3 1 2 
4 1 4 1 2 2 0 1 2 4 N 1 1 1 3 2 2 
IV 2 5.6 3 4 4 3 3 3 3 4 3 3 4 3 3 4 4 4 
4 3 4 4 3 4 4 3 4 4 4 4 4 3 4 4 4 
2 1.12 
2 3 3 3 3 2 2 3 1 4 4 2 3 4 3 4 
4 2 3 3 3 4 3 3 4 1 4 4 3 3 4 4 4 
2 .28 1 1 1 0 1 2 1 2 1 2 2 2 1 3 3 3 
4 1 1 2 0 3 2 1 2 1 1 1 1 1 4 3 3 
2 .056 
0 0 0 0 1 0 1 2 0 0 1 0 1 2 2 2 
4 0 1 0 0 1 0 1 1 0 0 1 0 0 3 2 1 
V 2 5.6 2 2 2 1 2 2 2 2 2 4 3 2 1 3 2 3 
4 2 2 2 1 2 2 3 2 2 4 3 3 2 3 3 3 
2 1.12 
1 1 2 0 1 2 2 2 2 2 2 2 1 1 2 3 
4 1 2 2 0 2 1 1 1 2 2 2 1 1 1 2 3 
2 5.6 1 1 2 1 2 3 2 2 1 4 4 2 2 3 3 N 
4 1 3 2 3 4 3 2 2 1 4 4 3 3 3 3 N 
2 1.12 
1 1 1 0 1 0 1 1 1 1 1 0 2 3 2 3 
4 1 1 2 0 3 0 1 1 0 2 0 0 3 3 2 3 
2 .28 1 0 0 0 1 0 1 0 0 1 0 0 0 1 1 1 
4 1 0 1 0 1 0 0 0 0 1 0 0 0 1 0 1 
__________________________________________________________________________ 
From the test results presented in Tables I and II, it can be seen that the 
post-emergent herbicidal activity of the compounds of this invention is, 
for the most part, general in nature. In this regard it should be 
recognized that each individual species selected for the above tests is a 
representative member of a recognized family of plant species. 
Typically, herbicidal compounds of this invention are provided in the form 
of concentrates which require dilution prior to application to plants. The 
usual means for diluting the herbicide is the preparation of herbicidal 
compositions wherein the compound possessing herbicidal activity is mixed 
with other materials. Such other materials may be in either liquid or 
solid form and comprise adjuvants, inert materials, etc. 
The herbicidal composition containing herbicidal compounds of this 
invention are prepared in the usual manner by combining them with other 
materials which are well known in the herbicide art. The following is a 
description of herbicidal compositions employing the herbicidal compounds 
of this invention together with known materials and formulations typically 
utilized in the herbicide art. 
The herbicidal compositions, including concentrates which require dilution 
prior to application to the plants, of this invention contain from 5 to 95 
parts by weight of at least 1 compound of this invention and from 5 to 95 
parts by weight of an adjuvant in liquid or solid form, for example, from 
about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 
parts by weight of a dispersant, and, from 4.5 to about 94.5 parts by 
weight of inert liquid extender, e.g., water, acetone, tetrahydrofuran, 
all parts being by weight of the total composition. Preferably, the 
compositions of this invention contain from 5 to 75 parts by weight of at 
least 1 compound of this invention, together with the adjuvants. Where 
required, from about 0.1 to 2.0 parts by weight of the inert liquid 
extender can be replaced by a corrosion inhibitor, such as ethanol 
mercaptan, sodium thiosulfate, dodecylmono or dimercaptan, or antifoaming 
agent, such as a dimethylpolysiloxane or both. The compositions 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, pellets, 
solutions, dispersions, or emulsions. Thus, the active ingredient can be 
used with an adjuvant, such as a finely-divided solid, a liquid of organic 
origin, water, a wetting agent, a dispersing agent, an emulsifying agent, 
or any suitable combination of these. 
The herbicidal compositions of this invention, particularly liquids and 
soluble powders, preferably 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. The incorporation of a 
surface-active agent into the compositions greatly enhances their 
efficacy. By the term "surface-active agent" it is understood that wetting 
agents, dispersing agents, suspending agents, and emulsifying agents are 
included therein. Anionic, cationic, and nonionic agents can be used with 
equal facility. 
Preferred wetting agents are alkyl benzene and alkyl naphthalene 
sulfonates, sulfated fatty alcohols, amines or acid amides, long chain 
acid ester of sodium isothionate, esters of sodium sulfosuccinate, 
sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated 
vegetable oils, polyoxyethylene derivatives of phenols and alkylphenols 
(particularly isooctylphenol and nonylphenol), and polyoxyethylene 
derivatives of the mono-higher fatty acid esters of hexitol anhydrides 
(e.g., sorbitan). Preferred dispersants are methyl celluose, polyvinyl 
alcohol, sodium lignosulfonates, polymeric alkyl naphthalene sulfonates, 
sodium naphthalene sulfonate, polymethylene bisnaphthalene-sulfonate, and 
sodium N-methyl-N-(long chain acid)-laurates. 
When operating in accordance with the present invention, effective amounts 
of the compounds or compositions of this invention are applied to the 
plants or are incorporated into aquatic media in any convenient fashion. 
The application of liquid and particulate solid compositions to plants or 
soil can be carried out by conventional methods, e.g., power dusters, boom 
and hand sprayers, and spray dusters. The compositions can also be applied 
from airplanes as a dust or a spray because of their effectiveness at low 
dosages. The application of herbicidal compositions to aquatic plants is 
usually carried out by adding the compositions to the aquatic media in the 
area where control of the aquatic plants is desired. 
The application of an effective amount of the compounds or compositions of 
this invention to the plant is essential and critical for the practice of 
the present invention. The exact amount of active ingredient to be 
employed is dependent upon the response desired in the plant as well as 
such other factors, as the plant species and stage of development thereof, 
and the amount of rainfall as well as the specific compound employed. In 
foliar treatment for the control of vegetative growth, the active 
ingredients are applied in amounts from about 0.112 to about 56.0 or more 
kilograms per hectare. It is believed that one skilled in the art can 
readily determine from the teachings of this specification, including 
examples, the approximate application rate. 
There are several possible methods for applying liquid compositions of this 
invention to emerged plants. Such methods include the use of wiper systems 
whereby the plant to be treated is contacted with an absorbent material 
containing the particular liquid composition, a portion of which is 
thereby released onto the plant upon contact therewith. Such wiper systems 
typically comprise a reservoir of the liquid composition into which a 
portion of the absorbent material is placed and is fed therethrough. 
Generally, substances employable as absorbent material include substances 
of any shape or form capable of absorbing the liquid composition and 
releasing a portion of the same upon contact with the plant. Typical 
absorbent materials include felt, foam rubber, cellulose, nylon, sponges, 
hemp, cotton, burlap, polyester over acrylic, combinations thereof and the 
like. Forms of absorbent material include rope, twine, string, cloths, 
carpets, combinations thereof, and the like. These forms may be assembled 
in any manner desired including a pipe rope wick, a wedge rope wick, a 
multi-rope wick, and the like. 
In another possible application method, liquid compositions may be 
selectively applied to weeds by the use of recirculating sprayer systems 
wherein the recirculating spray unit is mounted on a tractor or high 
clearance mobile equipment, and the spray is directed horizontally onto 
the weeds growing over a crop. Spray not intercepted by the weeds is 
collected in a recovery chamber before contacting the crop and is reused. 
Roller applications may also be employed to apply liquid compositions to 
weeds growing over a crop. 
In yet another possible application method, shielded applicators may be 
employed to direct the liquid composition in the form of a spray onto the 
weeds while effectively shielding the crops from the spray. 
These and other possible application methods for selectively applying 
liquid compositions to weeds are discussed in detail in "Innovative 
Methods of Post-Emergence Weed Control", McWhorter, C. G., Southern Weed 
Science Society, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; Auburn 
University Printing Service, Auburn, Ala., U.S.A., the teachings of which 
are incorporated herein by reference in their entirety. 
Another possible method of applying liquid compositions of this invention 
to plants includes controlled droplet application which is also known as 
the ultra low-volume chemical application. Controlled droplet application 
involves the production of uniform or nearly uniform spray drops of a 
predetermined size and the conveyance of these drops with negligible 
evaporation to a spray target. In particular, this method comprises 
feeding spray solutions to a rotary atomizer comprising a small disk with 
serrated edges that disperses liquid into droplets as the disk spins. 
Different droplet sizes are produced by changing solution flow rates to 
the spinning disk or changing the speed of rotation of the disk. 
Those of skill in the art will recognize that the physical and chemical 
characteristics of the compound or composition employed will determine to 
a large extent the particular application method selected therewith. 
The aforementioned and other methods for applying liquid compositions to 
plants are discussed in detail in "Rope Wick Applicator--Tool With A 
Future", Dale, James E., pp. 3-4; "The Recirculating Sprayer and 
Roundup.RTM. Herbicide", Derting, Claude W., pp. 5-7; and "C.D.A. 
Herbicide Application", McGarvey, Frank X., Weeds Today, Volume 11, Number 
2, pp. 8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Ill., U.S.A., 
the teachings of which are incorporated herein by reference in their 
entirety. 
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.