N-(BENZENESULFONYL) CARBAMATES-HERBICIDAL ANTIDOTES

N-(BENZENESULFONYL) CARBAMATES - ANTIDOTES D'HERBICIDES

English Abstract

Abstract of the Disclosure
N-(substituted benzenesulfonyl) carba-
mates as new compositions of matter useful as
active herbicidal antidotes to protect against
and decrease crop injury when used with a thio-
carbamate herbicide when applied in various
methods; improved hervicidal compositions and
utility of said compositions to protect against
and decrease phytotoxic crop injury when employ-
ing thiocarbamate herbicides and a two-part
herbicide system comprising a first-part of
one or more thiocarbamate herbicide and a second
part of an effective antidote therefor compound
said antidote compounds of the class N-benzene
sulfonyl carbamates having the formula
<IMG>
wherein X is hydrogen, bromo, chloro, methoxy,
trifluoromethyl, and methyl; n is an integer from
1 to 3 inclusive, provided that when X is bromo,
trifluoromethyl, or methoxy, n is 1; and R is
selected from alkyl, haloalkyl wherein halo is chloro
or fluoro, alkenyl, haloalkenyl and wherein halo is
chloro, alkynyl, trifluoroacetamidomethyl, dialkylamino

cyanoalkylthioalkyl, phosphonomethyl, lower alkyl
substituted phenyl, 4-chlorophenylthiomethyl,
alkoxyalkyl, alkythioalkyl, cyanoalkyl, alkoxy-
carbonylalkyl, formamidoalkyl, alkoxycarbonylalkenyl,
alkylcarbonylalkyl, 1,3-dioxacyclohexane-5,5-methy-
lene, phenyl, chlorophenyl, benzyl, 4-chlorobenzyl,
4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl,
3-phenylpropyn-2-yl, methylthioacetimino, acetone
imino and benzaldimino

Claims

FOR FOREIGN FILING
PR-4391/4781
WHAT IS CLAIMED IS:
1. Compounds according to the formula
<IMG>
in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl,
and methyl;
n is an integer from 1 to 3 inclusive, pro-
vided that when X is bromo, trifluoromethyl,
or methoxy, n is 1;
and R is selected from haloalkyl having 2 to
6 carbon atoms, inclusive, wherein halo is
chloro or fluoro from 1 to 6, inclusive, halo-
alkenyl having 3 to 6 carbon atoms, inclusive,
and wherein halo is chloro from 1 to 4 inclu-
sive, dialkylamino having a total of 2 to 8
carbon atoms, inclusive, cyanoalkylthioalkyl
having a total of 3 to 6 carbon atoms, inclu-
sive, phosphonomethyl, trifluoroacetamidomethyl,
lower alkyl substituted phenyl said lower alkyl
each having 1 to 4 caxbon atoms, inclusive,
4-chlorophenylthiomethyl, alkoxyalkyl having
2 to 6 carbon atoms, inclusive, alkylthioalkyl
having 2 to 6 carbon atoms, inclusive, cyanoalkyl
havang 2 to 6 carbon atoms, inclusive, alkoxy-
carbonylalkyl having 3 to 7 carbon atoms, inclu-
sive, formamidoalkyl having 2 to 6 carbon atoms,
inclusive, alkoxycarbonylalkenyl having 4 to 7
56

carbon atoms, inclusive, alkylcarbonylalkyl
having 3 to 6 carbon atoms, inclusive,
1,3-dioxacyclohexane-5,5-methyl methylene,
chlorophenyl, 4-chlorobenzyl, 4-methoxybenzyl,
3-pyridylmethyl, phenoxyethyl, 3-phenyl-
propyn-2-yl, methylthioacetimino, acetone
imino and benzaldimino;
also provided that when X is trifluoromethyl
and n is 1, then R can be alkyl having 1 to
4 carbon atoms, inclusive, alkenyl having 3
to 6 carbon atoms, inclusive, and alkynyl having
3 to 6 carbon atoms, inclusive.
2. The compound according to Claim 1, in which X is
hydrogen and R is haloalkyl.
3. The compound according to Claim 2 in which R is
2,2,2-trifluoroethyl.
4. The compound according to Claim 2 in which R is
is 2-chloroethyl.
5. The compound according to Claim 2 in which R
is 2,2-dichloroethyl.
6. The method of decreasing injury to crops, said
injury due to a thiocarbamate herbicide, comprising applying
into the seed furrow to the seed and adjacent soil in the
open furrow prior to covering to achieve a planted state, a
non-phytotoxic antidotally effective amount of a compound
corresponding to the formula
<IMG>
in which X is hydrogen, bromo, chloro, methoxy, trifluoro-
methyl, and methyl; n is an integer from 1 to 3 inclusive,
provided that when X is bromo, trifluoromethyl, or methoxy,
n is 1; and R is selected from haloalkyl having 2 to 6 carbon
57

atoms, inclusive, wherein halo is chloro or fluoro from 1 to 6,
inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive
and wherein halo is chloro from 1 to 4, inclusive, dialkylamino
having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthio
alkyl having a total of 3 to 6 carbon atoms, inclusive, phos-
phonomethyl, trifluoroacetamidomethyl, lower alkyl substituted
phenyl said lower alkyl each having 1 to 4 carbon atoms,
inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having 2 to 6
carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon
atoms, inclusive, cyanoalkyl having 2 to 6 carbon atoms, in-
clusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, in-
clusive, formamidoalkyl having 2 to 6 carbon atoms, inclusive,
alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive,
alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-
dioxacyclohexane-5,5-methyl methylene, chlorophenyl, 4-chloro-
benzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-
phenylpropyn-2-yl, methylthioacetimino, acetone imino and
benzaldimino, also provided that when X is trifluoromethyl and
n is 1, then R can be alkyl having 1 to 4 carbon atoms,
inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and
alkynyl having 3 to 6 carbon atoms, inclusive.
7. The method according to Claim 6 in which X is 3-
trifluoromethyl and R is haloalkyl.
8. The method according to Claim 6 in which X is
3-chloro and R is haloalkyl.
9. A two-part composition comprising (1) an active
thiocarbamate herbicide and (2) a compound having the formula
<IMG>
in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl,
and methyl; n is an integer from 1 to 3 inclusive, provided
that when X is bromo, trifluoromethyl, or methoxy, n is 1; and
58

R is selected from haloalkyl having 2 to 6 carbon atoms,
inclusive, wherein halo is chloro or fluoro from 1 to 6,
inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive
and wherein halo is chloro from 1 to 4, inclusive, dialkyl-
amino having a total of 2 to 8 carbon atoms, inclusive
cyanoalkylthioalkyl having a total of 3 to 6 carbon atoms,
inclusive, phosphonomethyl, trifluoroacetamidomethyl, lower
alkyl substituted phenyl said lower alkyl each having 1 to 4
carbon atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl
having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2
to 6 carbon atoms, inclusive, cyanoalkyl having 2 to 6 carbon
atoms, inclusive, alkoxycarbonylalkyl having 3 to 7 carbon
atoms, inclusive, formamidoalkyl having 2 to 6 carbon atoms,
inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms,
inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms,
inclusive, 1,3-dioxacyclohexane-5,5-methyl methylene, chloro-
phenyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl,
phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetone
imino and benzaldimino also provided that when X is trifluoro-
methyl and n is 1, then R can be alkyl having 1 to 4 carbon
atoms, inclusive, alkenyl having 3 to 6 carbon atoms, inclusive,
and alkynyl having 3 to 6 carbon atoms, inclusive.
10. A two-part herbicide system comprising a first
part of one or more thiocarbamate herbicides and a second part
of a compound being antidotally active with said carbamate
herbicide said compound of the second part having the formula:
<IMG>
in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl,
and methyl; n is an integer from 1 to 3 inclusive, provided
that when X is bromo, trifluoromethyl, or methoxy, n is 1; and
59

is selected from haloalkyl having 2 to 6 carbon atoms,
inclusive, wherein halo is chloro or fluoro from 1 to 6,
inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive and
wherein halo is chloro from l to 4, inclusive, dialkylamino
having a total of 2 to 8 carbon atoms, inclusive, cyanoalkyl-
thioalkyl having a total of 3 to 6 carbon atoms, inclusive,
phosphonomethyl, trifluoroacetamidomethyl, lower alkyl
substituted phenyl said lower alkyl each having 1 to 4 carbon
atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having
2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 to 6
carbon atoms, inclusive, cyanoalkyl having 2 to 6 carbon
atoms, inclusive, alkoxycarbonylalkyl having 3 to 7 carbon
atoms, inclusive, formamidoalkyl having 2 to 6 carbon atoms,
inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms,
inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms,
inclusive, 1,3-dioxacyclohexane-5,5-mekhyl methylene, chloro-
phenyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl,
phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino,
acetone imino and benzaldimino also pxovided that when X is
trifluoromethyl and n is 1, then R can be alkyl having 1 to 4
caxbon atoms, inclusive, alkenyl having 3 to 6 carbon atoms,
inclusive, and alkynyl having 3 to 6 carbon atoms,
inclusive.

Description

~7~
Background of the Invention
While many herbicides are immediately toxic to a large
number of weed pests, it is known that the effect of many
herbicides upon important plant cultivations is either non-
selective or no-t adequately selective. Thus, many herbicides
damage not only the weeds to be controlled but, to a greater or
lesser extent, the desirable cultivated plants as well. This
holds true for man~ her~icidal compounds which have been
commercially successful and are commercially available. These
herbicides include types such as triazines, urea derivatives,
halogenated acetanilides, carbamates, thiocarbamates and the
like. Some examples of these compounds are described in U.S.
Patents No. 2,913,327, 3,037,853, 3,175,897, 3,185,720,
3,198,786 and 3,582,314.
The side effect of injury to a cultivated crop by
various herbicides is particularly inconvenient and unfortunate.
When used in the recommended amounts in the soil to control
broadleaf weeds and grasses, serious malformation or stunting
of the crop plants sometimes result. This abnormal growth in
2Q the crop plants sometimes result. This abnormal growth in
the crop plants results in loss of crop yield. The search
; continues for good selective herbicides.
Previous attempts are described to overcome this
problem. The treatment of t~e crop seed with certain "hormonal"
antagonistic agents prior to planting is described; see U.S.
Patents 3,13],509 and 3,564,768. The protective agents, as well
as the herbicide, in these prior processes are largely specific
~'f~
~7

~7,~ ~?r~
to certain cultivated plant species or in the nature of the
antagoni.stic agents. The prior antagonistic agents have not
been notably successful. The aforementioned patents specifically
exemplify and describe the treatment oE seeds employing compounds
of a different chemi.cal class, not suggestive of the present
invention.
U.S. Patents 3,7~9,760 and 3r933~894~ and East German
Patent DL 74982 disclose certain N-benzenesulonyl carbamate
. compounds, disclosed herein. Also, in Berichte, Vol. 37 at
10 Page 699, certain compounds are specifically disclosed. None
of these references anticipate or make obvious the utility of
the compounds as herbicidal antidotes for thiocarbamate herbi-
cides, in particular for S-n-propyl N,N-di-n-propylthiocarbamate.
None of the references anticipate or make obvious the improved
r, herbicidal compositi.ons for use employing N-benzenesulfonyl
carbamates and an active thiocarbamate herbicide, particularly
S-n-propyl N,N-di-n-propylthiocarbamate.
. Descripti.on of the Invention
~ It has been di.scovered that cul~ivated crop plants, can
:: ~ 20 be protected against injury ~y thiocar~amate-type herbicides,
,r~ and said injury can be decreased when the thiocarbamate-type
. herbici.des r each alone or in mixtures or combination with other
Y - compounds, are applied in a variety of ways. Further r as an
,~ ~ alternative effect, the tolerance of the plants, to these herbi
cides, can be suhstantially- increased by adding to the soil an
: antidote compound of the type N ~substituted benz~nesulfonyl)
r~ . carbamates:, th.exe~ore~ the present inYention also includes a
t~o-part h.erbi~cide system comp~ising a first part of one or more
"
:~ -3~
:,
,

thiocarbamate herbicide and a second part of an effective anti-
dote compound therefore, said anti`~dote compounds corresponding
to the following formula
~f ~ ~ C OR
in which ~ is hydrogen, bromo, chloro, methoxy, trifluoromethyl,
and methyl; n is an integer from 1 to 3 inclusive, provided that
when X is bromo, trifluoromethyl, or methoxy, n is l; and R
is selected from alkyl having 1 to 4 carbon atoms, inclusive,
haloalkenyl having 3 to 6 carbon atoms, inclusive and wherein
halo is chloro from 1 to 4, inclusive, alkynyl having 3 to 6
carbon atoms, inclusive, trifluoracetamidomethyl, dialkylamino
having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthio-
alkyl having a total of 3 to 6 carbon atoms, inclusive, phos-
phonomethyl, lower alkyl ~ubstituted phenyl said lower alkyl
each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthio-
methyl, alkoxyalkyl having ~ ~o ~ carbon atoms, inclusive,
alkylthioalkyl having 2 to 6 carbon atoms, inclusive cyanoalkyl
having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkyl
having 3 to 7 carbon atoms, inclusive, formamidoalkyl having 2
to 6 carbon atoms, inclùsive, alkoxycarbonylalkenyl havin~ 4
to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6
carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methy-
lene, phenyl, chlorophenyl, benzyl, 4-chlorobenzyl, 4-methoxy-
: benzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn~2-yl,
` methylthioacetimino, acetone amino and ~enzaldimino.
~ . Cer~ain compounds disclosed herein are considered new
~ composltions of matte.r and correspond to the following formula
O ~ O
P~ C - OR
--4--

~7~
in which X is hydrogen, b.romo, chloro~ methoxy, trifluoromethyl,
and methyl; n is an integer from 1 to 3 inclusive, provided that
when X is bromo, tri.fluoromethyl, or methoxy, n is l; and R is
selected from haloalkyl having 2 to 6 carbon atoms, inclusive,
wherein halo is ch.loro or fluoro from 1 to 6, inclusive, halo-
alkenyl having 3 to 6 carbon atoms, inclusive and wherein halo
i.s chloro from 1 to 4, inclusive, dialkylamino having a total of
2 to 8 carbon atoms, inclusive, cyanoalkylthioalkyl having a
total of 3 to 6 carbon atoms, inclusive, phosphonomethyl, tri-
fluoroacetamidomethyl, lower alkyl substituted phenyl said lower
alkyl each having 1 to 4 carbon atoms, inclusive, 4-chloro-
phenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclu-
sive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive
cyanoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonyl-
alkyl having 3 to 7 carbon atoms~ ï.nclusive, formamidoalkyl
having 2 to ~ carbon atoms/ inclusive, alkoxycarbonylalkenyl
ha~ing 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having
3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl
methylene, chlorophenyl, 4-chlorobenzyl, 4-methoxyhenzyl,
3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthio-
acetimino, acetone imino and benzaldimino.
~lso provided that when X is trifluoromethyl and n is 1,
, then R can be alkyl having 1 to 4 carbon atoms inclusive, alkenyl
having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to
6 carbon atoms, inclusi~e.
In the a~ove descriptions, the followïng embodiments are
intended ~or the various substi.tuent groups: For R, haloalkyl
preferahly includes those members which. contain from 1 to 6 car-
~ bon atoms, i.nclusi.ve~ i.n ~oth straight chain and branched chain
:.: 30 configurations and th.e term "halo" includes chloro, bromo and
s;
-5-
`.' ~3

fluoro, as mono, _, tri, tetra7 or hexa substitutions that is
from 1 to 6 halo substituents. As exemplary of the alkyl portion
within the preferred embodiment are the following: Methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and
tert.-but~l. For R, alkynyl preferably includes those members
which contain from 3 to 6 carbon atoms and at least one acety-
lenic or triple bond such as in propargyl (propynyl), 2-butynyl,
3-butynyl, 1,1-dimethyl-3-butynyl, and the like. Chloroalkenyl
preferably includes those members which contain from 3 to 6
carbon atoms, inclusive, and at least one olefinic double bond.
~ther substituent groups are as indïcated in carbon content in
the above description.
As an alternative mode of action, the compounds of this
invention may interfere with the normal herbicidal action of
the thiocarbamate-type and other herbicides to render them
selective in their action. The o~servation noted with the pres-
ence of the herein described antidote i5 a decrease in phyto-
toxuity with respect to various crops, otherwise observed when
various thiocarbamate herbicides are used for weed control.
Whichever mode of action is present, the corresponding beneficial
and desirable effect is the continued herhicidal effect of the
thiocarbamate with the accompanying decreased herbicidal effect
on desired crop species. This advantage and utility will become
more apparent hereinafter.
Therefore, the terms, "herbicide antidote" or "antidotal
amount", is meant to describe that effect which tends to counter-
act the normal injurious herbicidal response that the herbicide
might otherwise prod~ce. ~hether it is to be termed a remedy,
,;lnterferant, protectan~, antagonist or the like, will depend
!:~
~, -6-
~ .
~'' .

7~
upon the exact mode of actlon. The mode of action is varied,
but the effect, which is desirable, is the result of the method
of treating the seed, soil or furrow in which a crop is planted.
Hitherto, there have been no systems which have been
satisfactory Eor this purpose.
The compounds of this invention represented by the avove
formulas can be prepared by several different procedures
depending upon the starting materials.
One general method for preparing N-benzenesulfonyl alkynyl
la carbamates is the reaction of an appropriate alkynol with ben-
zenesulfonyl isocyanate. More particularly, the reaction is
performed in the presence of a solvent such as benzene or chloro-
form with catalytic amounts of triethylamine and dibutyl tin
dilaurate. In some instances, a catalyst is not required. After
the reaction is complete, the product is recovered by filtration
or evaporation of the solvent. I~necessary, the product can be
recrystallized from a suitable solvent.
A general method for preparing N-benzenesulfonyl alkyl
carbamates is ~he reaction of an appropriate benzenesulfonamide
with an alky~ chloroformate in th~ presence of a catalyst, such
as potassium carbonate. A solvent is normally employed to
facilitate the reaction and aid in the work-up of the product.
After filtration, extraction and dryin~, the product can be
; purified further by trituration with hexane or recrystallization
from a suitable solvent. In mos-t instances, the structure was
confirmed by infrared, nuclear magnetic resonance or mass
spectroscopy.
The compounds of the presen~ invention and their prepar-
ation are more particularly illustrated by the following examples.
7-

~ ~r 7~
Following the examples of preparation is a table of compounds
which are prepared according to the procedures described herein.
Compound numbers have been assigned to them and are used for
identification throughout the balance of the specification.
EXAMPI.E I
Preparation of 2-butyn-1-yl p~toluenesulfonyl carbamate.
To a solution o~ 2-butyn-1-ol, 1.75 g. (0.025 mole) in 25
ml~ chloroform was added slowly 4.9 gO ~0.025 mole) p-toluene-
sulfonyl isocyanate. An exothermic reaction resulted. The
product was removed by evaporating the solvent~ There was
obtained a yield of 6.4 g. of the title compound, m.p. 85-90C.
EXAMPLE II
Preparation of 2-bromopropyl p-toluenesulfonyl carbamate.
In a similar procedure as described in Example 1, 2-bromo-
1-propanol, 3.4 g~ (0.0~5 mole~ in 25 ml. chloroform and 4.9 g.
(0.025 mole) p-toluenesulfonylisocyanate were reacted. After a
similar work-up to remove the solvent, there was obtained a
yield of 8.4 g. of the title compound, n30 1.5375.
,.
EXAMPLE III
Prepara-tion of hexafluoroisopropyl p-toluenesulfonyl carbamate.
In a simllar procedure as described in Example 1, sym-
hexafluoroisopropanol, 4.2 g. in 25 ml. chloroform and 4.9 g.
(0.025 mole) p toluenesulfonylisocyanate were reacted with 2
drops of triethylamine as catalyst. After a similar wor~ up to
remove the solvent, there was obtained a yield of 8.9 g. of the
title compound, m.pO 69-75C.
... .
; -8
.: ~
,,
,~ , . . .

~7~
EXAMPLE IV
Preparation of N-(p-chlorobenzenesul~onyl~-propargyl carbamate.
To a solution of 1.7 g. (0.03 mole) of propargyl alcohol
in 20 ml. of benzene containing one drop of triethylamine and
one drop o* dibutyl tin dilaurate was added a solution of 6.5
g. (0.03 mole) p chlorobenzenesulfonyl isocyanate in 25 ml.
benzene. The reaction was exothermic and the temperature was
allowed to rise to 30C. The mixture was stirred several hours
at room temperature and the precipitated solid was filtered and
washed with a small amount of hexane and dried. There was
obtained a yield of 8.0 g. ~98% of theory~ of the title compound,
` m.p. 106-108C. A pure sample melted at 120.5-121C. The
; structure was confirmed by infrared, nuclear magnetic resonance,
and mass spectroscopy.
EXAMPLE V
Preparation of N-(p-chloro~enzenesulfonyl~-ethyl carbamateO
p-Chlorobenzenesulfonamide ~6.1 g., 0.032 mole), potas-
sium carbonate (10.8 g., 0.078 molel, and ethyl chloroformate
(3.7 g., 0.034 mole) in 40 ml. of acetone were stirred and re-
fluxed for two hours. During the heating period the mixture~ecame thick and was diluted with another 30 ml. of acetone.
The cooled mixture was poured into 150 ml. of water and filtered
through Celite. Th~ filtrate was acidi~ied with hydrochloric
acid with cooling ~pH about 2~ and the product extracted with
benzene. The extract was washed with water and dried over anhy-
drous magnesium sulfate. Removal of the solvent left the title
compound as a solid. There was obtained a yield of 5.5 g.
C65~ of theorv) of the title compound, m.p. 85-90C. Th~ struc-
ture was confirmed by IR.
_ g_
,
,( ,,
,,
,; .

EXAMPLE VI
Preparation of N-(p-methoxybenzenesulfonyl)-ethyl carbamate.
p-Methoxybenzenesulfonamide (5.0 g., 0.032 mole~
potassium carbonate (10.8 g., 0.078 mole), and ethyl chloroformate
(3.7 g., 0.034 mole) in 40 ml. of acetone were refluxed for
2.5 hours. The product was worked up in a similar manner as in
Example V. There was obtained a yield of 3.9 g. ~47% of theory)
of the title compound, m.p. 110-116C.
The following is a table of the compounds which are pre-
pared according to the aforementioned procedures. Compoundnumbers have been assigned to them and are used for identification
throughout the balance of the specification.
TABLE I
X~ r--~ H
N C OR
m.p.C
COMPOUND or n
NUMBER _ R D
1 4-CH3 CH(CH3~2 sticky*
2 4-OCH3 C2H5 110-116
3 4-Cl C2H5 85-90
4 4-CH3 CH(CF3)2 69-75
4-CH2 CH2CH2Br 1.5460
6 4-CH3 CH2CH2C1 1.5348
7 4-CH2 CH2CHBrCH3 1.5375
8 4-CH3 CH2CF3 120-125
9 4-CH3 CH2cH(cl~cH2cl semi-solid*
4-CH3 CH2C(CH3)ClCH2C1 1.5640
--10--

TABLE I ~continued)
m.p.C.
COMPOUND or n3
NUMBER X R D
11 4-Cl CH2CHC12 114-115
12 4-Cl CH2CF3 142-145
13 4-Cl CH~CF3~2 83-87
14 4-Br CH2CH2Cl semi-solid*
4-Cl CH2CH~Cl~CH2Cl semi-solid*
16 4-Cl CH2CH2B~ 92-98
10 17 4-CH3 CH C - CCH 85-90
18 4-Cl CH2C = CH 106-108
~ 19 4-Cl OEI2CH2C _ CH 102-104
,~ ~ 20 4-Cl C(CH3~2CH2C - CH 108-110
, . 21 4-Cl CH C - CCH 141~142
22 4~CH3 CH2CH2C = CH glass*
23 H CH2C - CH 78 80
24 H CH C CHCH 114-116
~ - - 3
H CH2CH~C - CH semi-solid*
26 H CH2CCl-CH2 semi-solid*
2Q 27 4-Br CH~C - CH 124-125
28 4-Br CH C - CCH 134-135
: 29 H CH2~F3
H CH2CH2Cl semi-solid*
..
3I E CH2CHC12 semi-solid*
. : 32 E CH3. 127~130
:
"~
,.,
'., ~
,,
,,

~o~
TABLE I ( con tin ue d )
m.p. C.
COMPOUND o r n
NUMBER_ X R D_
33 H C2~I5 1.5003
34 H n C3H7 1.4942
H c C3 7 1.4952
36 H CH2CC13 121-122
37 H CH2CF2CF2H 94-97
38 H CH2CH=CH2 1O5175
39 4-CH3 CH2CC12CH2C1 1.5300
4-CH3 CH2CH=CH2 1.5375
41 4-CH3 CH2C(CH3) CH2 1.5300
42 4-CEI3 CH2C~Cl~=CEI2 1.5340
43 4-CH3 CH2~-~CH 1.5384
44 4-CH3 C(CH3)3C - CH glass*
4-CH3 C(CH3)2C - CCH3 glass*
46 4-CH3 CH(i-C3H7~ CH glass*
47 4-CH3 N(C2Hs)2 semi-solid*
48 4-CH3 CH2NHCCF3 sticky
49 4-CH3 CH2P(~)(o~I)2 semi-solid
4-CH3 C 2S ~ 1 65-70
51 4-Cl CH3 127-130
52 4-Cl n C3 7 1.5111
~3 4-Cl C2 4 semi-solid
-12-
';

TABLE I ( continued )
m. p . C .
COl~IPOUND aE, n30
NUMBER_ X R D
54 4-Cl CH2CH=CH2 1.5262
4-Cl CH2C (Cl) =CH289--92
56 ~ 4--Cl CH2C (O) OC2H51.4783
57 4 -Cl phenyl 101- 104
58 4-Cl CH2~> 174-176
59 4-Cl CH2C C~ 109-111
3-CF3 C2H5 59--63
61 3-CH3 CH2CF8 91-96
62 3-CF3 CH2CH-CX2 66-70
63 3-CF3 CH C--CH 76-77
64 3,4-diCl C2H5 100-102
2-CF3 C2X5 129 131
- 66 3-Cl C2H5 1.5155
67 : 3--Cl CH2CF3 108--110
68 3-Cl CH2CH=CH2 58-61
69 3--Cl CH2C----CH 73-76
3--C l CH2 C_CCH 3 95 - 97
; 71 2,4 ~ 6-CH3 C2H5 159~160
72 2,4,6-C~3 C-C3~7 112-114
2,4,6-C~3 CH2CF3 159-162
74 2,4,6-CH3 CH2CC13 139-141
--13--
,.
.:
, ~ .
:,

TABLE I (continued~
m.p.C.
COMPOUND 30
NUMBER X R or nD
2,4,6-CH3 CH C CH 150-151
76 2,4,6-CH3 4-Cl-phenyl 131-132
77 2,4,6-CH3 -N=CH ~ 120-122 dec.
78 4-CH3 C2H4F 1.5022
79 4-CH3 C2H4SC2H4CN 1.5482
4-CH3 3,4-di-CH3-phenyl 80-82
81 4-CH3 -N=C(CH3)sCH3 145-147
82 4-CH3 t C4H9 119-122
83 4-Cl C2H4F 1.5192
~ 84 4-Cl CH2CF2CF2H 82.85
!' 85 4-C1 C~CH3)(C2H5)C - CH 122-124
86 4-Cl C2H4OC2H5 semi-solid*
87 4-Cl C2H4SC2H5 1.5360
88 4~Cl C~CH3~2CN 68-71
89 4-Cl C2H4C(o~cH3 94-98
4-Cl CH2 ~ ~ viscous semi-
/ ~ o solid*
CH3
; 91 4-?Cl CH~CH3)C(O)OC2H5 1.4950
92 4-Cl C2H4NHC (O)H 154-157 dec.
`~ 23 4-Cl C(CH3)=CHC(O)OC2H5 1.5100
94 4-C1 4-Cl-phenyl 159-160
4-C1 2-Cl-phenyl 77-80
.;
:~,
! ~, - 14-
.i.'
,; '~
"~;

7~
TABLE I (continued~
m.p.C.
COMPOUND n
NUMBER X R D
96 4-C1 3,4-diCH3-phenyl 100-103
97 4-C1 3,4,5-tri-CH3-phenyl 1.5473
98 4-C1 2-i-C3H7-Phen~l 1.5471
99 4-C1 3,5-di-1-C3H7-phenyl 1.5415
100 4-C1 3-t-C4Hg-phenyl oil*
101 4-Cl benzyl 98-101
102 4-C1 4-C1-benzyl 138-139
103 4 Cl 4-CH30-benzyl 119-122
104 4-Cl phenoxy-CH2CH2 98-99
105 4-Cl -N-C(CH3~2 161-162
106 4-Cl -N=c(cH3lscH3 125-128
107 4-Cl -N=CH-phenyl 120-124 dec.
*Structure confirmed ~y either infrared or nuclear magnetic
resonance spectroscopy.
-15-
~.~s

~7~ ~
The herbicides indicated in the tables and elsewhere
are used at rates which produce effective control of undesir-
able vegetation. The range of rates employed herein produce
representative results within the recommended amounts set forth
by the supplier. Therefore, the weed control in each instance
is commercially acceptable within the desired or recommended
amount .
It is clear that the class of herbicidal agent described
and illustrated herein is characterized as effective
herbicide exhibiting such activity. The degree of this
herbicidal activity varies among specific compounds and among
combinations of specific compounds within the class. Similarly,
the degree of activity to some extent varies among the species
of plants to which a specific herbicidal compound or combination
may be applied. Thus, selection of a specific herbicidal
compound or combination to control undesirable plant species
re~dily may be made. Within the present invention, the prevention
of injury to a desired crop species in the presence of a specific
compound or combination may be achieved. The beneficial plant
species which can be protected by thïs method is not intended to
be limited by the specific crops employed in the examples.
The herbicidal compound employed in the utility of
this invention is an active thiocarbamat~ herbicide of a general
type. That is, it is a mem~er o~ the class of herbicidally
active compounds effective agains-t a wide range of plant species
with no discrimination bet~een desira~le and undesirable species.
The method of controlling vegetation comprises applying an
herhicidally effective amount of the herein described her~icidal
compound to the area or plant locus where control is desired.
'30 The compositions as set forth in this invention include those
; -16-
:
; ,' :,'
. , ~
.

wherei.n the antidote i.s as described above and the preferred
active herbicial compound is selected from the class of thio-
carbamate herbicides and includes the following as representative
members, S-ethyl dipropyl thiocarbamate, S-ethyl dilsobutyl
thiocarbamate, S-propyl di-n-propyl thiocarbamate, S-ethyl
cyclohexyl ethyl thiocarbamate, S-ethyl hexahydro-lH-azeplne-l
carbothioate, ~,3,3-trichloroallyl N,N-diisopropyl thiocarbamate,
S-isopropyl l-(5-ethyl-2-methylpiperidine~ carbothioate; alone
and with various combinations thereof and with such other classes
of herbicidal compounds, as triazines, for example, 2-chloro-4-
ethylamino-6-isopropylamino-s-triaz.ine, 2-chloro-~,6-bis(ethyl-
amino)-3-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl
amino~-2-methylpropionitrlle, 2-chloro-4-cyclopropylamino-6-
; isopropylamino-s-triazine.
As an embodiment within the scope of the present
invention is a two part or package herbicide sys-tem comprising
a first part of one or more thiocarbamate herbicide and a second
part of an antldote compound therefore it is understood that
the antidote compound is used in an effectlve amount to render
the two-part herbicide system selecti.ve i.n decreasing phytotoxic
effects to desi.red or bene~icial crops and yet phytotoxic to
the undesirable or un~anted vegetation. Thus the soil treated
by such a system becomes extremely useful and desirable, allow-
ing previously injured crops to be planted ln said treated soil,
otherwise injured by the herbi.cï.de when used alone. Hence, soil
treated ~ith herbicide and antidote ;.s described herein ;s
~enefi.cial, desirable and useful.
An herbicide as used h.erein means a compound ~hich
controls or modifies the growth of vegeta~ion or plants. Such
-17-
.,

7~
controlling or modifying effects include all deviations from
natural de~elopment; for example, killing, retardation, defolia-
tion, desiccation, regulation, stunting, tillering, stimulation,
dwarfing and the like. By "plants", it is meant germinant seeds,
emerging seedlings and established vegetation including the
roots and above-ground portions.
Evaluation Procedures
Flats to be used for growing the crops and weed
species were filled with loamy sand soil. Stock solutions
of the herbicide and each candidate antidote were prepared as
follows:
A. Her~icide - S-n-propyl N,N-di-n-propyl
thiocarbamate - BERNAM ~ 6E - 1560 mg. of
VERNAM 6E was diluted in 250 ml. of water
so that 5 ml. applied to a flat is equiva-
lent to 6 lb/A per flat ~based on the
surface area of a flat~
B. Antidote - of each candidate, 78 mg. was
dissolved in 20 ml. of acetone with l~
Tween 20 ~ (polyoxyethylene sorbitan mono-
laurate~ so that 5 ml. when applied by pre-
plant incorporation technique (PPI) is equal
to 5 lb/A per flat.
The herbicide and antidotes were applied to the soil
together as a tank mix employing pre-plant incorporation tech-
nique. To prepare the com~ined tank mix, 5 ml. of the VERNAM
were admixed, followed by incorporation into the soil from the
flats during incorpora-tion in a rotary mixer.
-18-
:

One row each of the following weeds and crop was
seeded into the treated soil in the flats: Watergrass
(Echinochloa crusgalli), foxtail (Setaria viridis), and
soybeans (Glycine max).
The flats were placed on greenhouse benches where
temperature were maintained between 70-90F. The soil was
watered by sprinkling to assure good plant growth. Injury
ratings were taken 2 and 4 weeks after the applications were
made. Individual flats treated with the herbicide alone were
included to provide a basis for determining the amount of injury
reduction provided by the herbicide antidotes.
The following table includes results as per cent
protection for the crop according to the procedure discussed
above. The per cent protection is determined by a comparison
with flats not treated with the candidate antidotes of this
invention.
TABLE II
Application Method : Pre-plant Incorporation - PPI (Tank
Mix2
20 Crop Species : Soybeans (Glycine max)
' Weed Species : Foxtail (Setaria vlridis~
Watergrass (Echinochloa crusgalli)
* = ~ injury
*~ = % protection
, ~
, .
~ f,~, ~
;

-
PPI (6 lb/A) (Tank Mix~
COMPOUND
NUMBERSoybeans Watergrass Foxtail
VERNAM 6 lb/A40* 100* 100*
1** 75 0 0
2 75 0 0
3 10Q 0 5
4 37.5 0 0
~5 0 0
6 25 Q o
7 25 0 0
8 75 Q 0
Q 0
0 0
11 75 0 0
12 100 0 0
13 50 0 0
14 25 0 0
0 0
16 5Q a o
17 100 0 5
18 100 Q 5
19 lQ0 0 5
0 0
21 1~0 0 5
22 75 0 0
23a lQ0 Q
24a 75 0 0
, 1 a Q o o
i 30
j -20-
, ~
:~.

7~
TABLE II (continued)
PPI (~6 lb/A~ (Tank Mix)
COMPOUND
NUMBER o~beans Watergrass Foxtail
26a 75 0 0
27a 100 0 0
28a 100 0 0
29a 75 0 0
30a 67.5 0 0
= Pre-plant incorporation of VE~NAM ~ and antidote applied
separately prior to ;ncorporation.
Seed Treatment Test
Small flats were filled with Felton loamy sand soil.
Soil incorporated herbicides were applied at this time. The
soil from each flat was placed into a five-gallon cement mixer
where the soil was mixed as the herbicides were applied using a
pre-determined amount of a stock solution containing 780 mg. of
approximately 75% active ingredient to 125 ml. of water. Five
ml. of stock solution was applied to the soil in a volumetric
pipet. Five ml. of stock solution contained an equivalence of
herbicide which equals six (6) pounds per acre when applied to
the soil in the flats. After the her~icide incorporation, the
soil was placed back into the flats.
Flats of the herbicide-treated and untreated soil were
then ready to be planted. A pint sample of soil was removed
from each flat and placed next to each flat for later use in
covering up the seeds. The soil ~as leveled and rows one-half
inch deep were made for planting seeds. Alternating rows of
- treated and untreated crop seeds were sown. In each tes~,
, -

~76~
soybean (Glycine maxl seeds were planted in each row. Rows
~ere approximately 1-1/2 inches apart in the flat. Seeds were
treated by preparïng a stock solution by dissolving 250 mg. of
the antidote compound in 2.5 ml. of acetone, then using 0.5
ml. of the stock solution to treat 10 g. of soybean seed
equivalent to 0.5~ w/w. Antldote compounds can also be applied
as liquid slurries and powders or dusts. In some cases,
acetone is used to dissolve powdered or solid compounds so
they could be more effectively applied to the seeds.
~fter the flats were seeded, they were covered with
the one pint of soil which had been removed just prior to
planting. Flats were placed on greenhouse benches where
temp~ratures ranging from 70-79~F. Flats were watered by sprinkling as
needed to assure good plant growth. Per cent control ratings
were taken four weeks after the treatments were applied.
In each test, the`herbicide was applied alone, in
combination with the seed protectant, and the seed protectant
was applied alone to check for phytoxicity. The untreated
adjacent row was employed to observe any beneficial lateral
movement of the antidote compound through the soil. The degree
of the effect was noted by comparison with the control.
In this seed treatment test with the herbicide S-n-
propyl N,N-di-n-propyl thiocarbamate, Compound No. 17 exhibited
; 5a% protection to the treated soybean seeds. That is, the
injury was reduced by at least 50% to the emerging soybean plants
grown from seed treated with Compound No. 17, compared to
~; untreated seed grown in soil containing the thiocarbamate
;' herbicide.
,; -22-
,,,
1,.
,.,
...
., ~ .

Evaluation Procedure and Method
Flats to be used for growing the crops and weed
species were filled with loamy sand soil. Various methods
of application were employed, such as pre-plant incorporation
of 1~ the herbicide and antidote separately, and 2~ as a tank
mix with the herbicide and antidote together. The application
was by incorporation, whereinafter the seeds were planted in
soil treated with an effective herbicidal composition of
thiocarbamate herbicide and antidote; application by an in-furrow
treatment of the seeds and surrounding soil in ~hich the
herbicide had been applied previously to the ~oil; and
treatment of the crop seeds with an antidote candidate prior
to planting in herbicïde treated soil.
Stock solutions of other representative thiocarbamate
herbicides and antidote candidates were prepared as follows:
Herbicides
C. S-ethyl di-n-propyl thiocarbamate - EPTC
EPTAM ~ 6E - 260 mgO dissolved in 200 ml.
~ater such that 4 ml. applied to the soil
from a planting fl~t is equivalent to 1 l~/A
applïed in 80 gal. of ~ater per acre and 3
ml. is équivalent to 0.75 l~/A.
D. S-isopropyl 1-(5-ethyl-2-methyl-piperidine~
carhothioate ~R-12001i, 390 mg. dissolved
in 200 ml. of a etone with 1% Tween 20 ~ ,
or 975 mg. in 250 ml. of acetone, such that
5 ml. of solution applied to a planting flat
is equivalent of 2 l~/A pre-plane incorporated
and 6 ml. is equivalent to 6 lb/A respectively.
3Q E. 5-eth~l di~ïso~utyl thiocarbamate - SUTAN ~
6E or 5-ethyl cyclohexy-l ethyl thiocarbamate -
RONEET ~ 6E - 52~ ~g. dlssolved in 20Q ml.
~ater such that 4 ml. applied to the soil from
a plantïng flat is equïvalent to 2 lb/A, applied
ïn 80 gal. of water per acre. For 6 lb/A or
.~

12 lh/A, 13Q0 m~. or 26 m~. ~as dissolved
in 25a ml. water, such that 6 ml. was
equivalent to the desired amount,
respectively.
F. 2,3,3-trïchloroallyl N~N-diisopropyl thio-
carbc~mate - AVADE~ BW ~ 4E - 1219 mg.
dissolved in 3Q0 ml. dïstilled water, such
that 6 ml. is equivalent to 3 lb/A when
applied to the soil from a planting flat
pre-plant incorporated.
G. S-ethyl~hexahydro-l~-azepine-l-carbothioate -
ORDRAM 8E - 857 mg. dissolved in 250 ml.
water such that 5 ml. is equivalent to 4 lb/A
and 2.5 ml. is equivalent to 2 lb/A when
applied to the soil from a planting flat
pre-plant incorporated.
Antidotes
H. For each candidate compound employed, 250 mg.
active ingredient was diss~lved in 2.5 ml.
acetone, with 1% Tween 20 ~ (polyoxy-
ethylene ~orbitan monolaurate) such that 0.5
ml. of solution per 10 gm. of seeds is egual
to 1/2% w/w. For seed treatment of 1/4%, 0.25
ml. was diluted with 0O25 ml. o~ acetone, such
that 0.5 ml. of solution for 10 gm. of seeds is
equal to 1/4% w/w. This solution was used for
the seed treatment procedure in varying amounts
and dilutions for example for 0.10~, 0.1 ml. is
diluted with 0.4 ml. of acetone.
r. For each candidate compound employed in the
'lin-furrow" method of application, 95 mg. of
active ingredient was dissolved in 15 ml. of
acetone with 1% Tween 20 ~ such ~hat 1.5 ml.
applied to the seed and~soil in the furrow, in
one-half of the flat was equivalent to 5 lb/A.
- When 1.0 lb/A is desired 0.3 ml. is diluted
with 1.2 ml~ of acetone.
.,
.,
`; J. For each candidate compound employed in the
tank mi~ pre-plant incorporation test, 39
. 4Q m~ o.~ actl~e in~redient ~as dissolved in 10
s ~ ~1. of acetone ~ith 1% Tween 2Q ~ , such
that 5~ml. when applied to t~e soil of a
;~ flat was- eguivalent to 5 l~/A.
~!
. .
~ 24-
.
!
~;
J

~7~
In-furrow application of the antidote employed the
ahove stock solutions. As a preparatory step, a one pint
sample of soil was removed from eac~ flat to be retained and
used later to cover the seeds after treatment with the stock
solutions. The soil was leveled before planting. The
herbicide stock solution was applied respectively to separate
flats and pre-plant incorporated in the soil from the planting
flat at the equivalent rate of 1 lb/A active ingredient or the
indicated rate.
- 10 Rows 1/4-inch deep were made lengthwise in each
treated flat, preparatory to seeding. After seeding, the flats
were sectioned into t~o equal portions using a wooden barrier
and 1-1/2 ml. of additive stock solution I was atomized directly
onto the exposed seed and soil in the open furrow in one-half
of the flat~ The untreated section of the flat served as an
herbicide check and also made it possible to o~serve any lateral
movement o the antidote through the soil. The seeds were
covered with the one pint sample of untreated soil which had
been removed earlier.
For tank mixes to be applied as a pre-plant
incorporated application, the following solutions and procedure
were employed. Five milliliters ~5 ml.) of herbicide stock
solukions A or C were each mixed wi~h five millilit~rs (5 ml.) of
~ antidote candidate stock solution J such that the equivalent of
; 1 lb/A and 5 lbs/A of her~icide and antidote, respectivelyr were
applied and incorporated into the soil of each flat. For pre-
plant incorporation, the mixed stock solutions weEe injected into
the soïl during incorporatiGn in a 5-gallon rotary mixer.
~ Other stoc~ solutions ere employed at indicated rates in the
1 30 tank mix procedure.
,, -25-
.. ..
,,.
,~.

~7~
For seed treatment, lQ grams of seed in a suitable
container was shaken with a. 5 ml. of antidote stock solution H,
or other stock solution as indicated, such that the seed
treatment was equivalent to 0.5% w/w, 0.25% w/w, 0.125% w/w or
0.1% w/w. 5haking was continued until the seeds were uniformly
covered. The antidote compounds may be applied as liquid
slurries and powder or dust treatments. The treated seeds were
planted in soil in which herbicide stock solution had been
pre-plant incorporated into the soil at a rate equivalent to
l lb/A active ingredient.
All fla-ts were placed on greenhouse benches where
temperatures were maintained between 70-90F. The soil was
watered by sprinkling to assure good plant growth. Injury
ratings were taken 2 and 4 weeks after the applications were
made. Individual control flats treated with the herbicide alone
~ere included to provide a basis for determining the amount of
injury reduction provided by the herbicide antidotes. The
results of these tests are tabulated in Table III.
TABLE III
ANTIDOTE ACTIV_TY
Application Method: Seed Treatment - ST
In-Furrow - IF
Pre-Plant Incorporation - PPI (Tank
Mix)
Crop Species: Barley - ~A ~Hordeum vulgare (L.~]
; Corn -~ CN ~Zea maize~
Cotton - CT I~ y~ hirsutum]
-26-

TABLE III (con~inued~
Crop Species: Grain Sorghum - GS ~So~hum ~ ]
Rice - R ~)ry:a S`t.;.~.]
Soybeans - SB [Glycine max]
Wheat - WT [ Tri ticum ae s tivum ]
Weed Species: Watergra5~ - WG [Echinochloa crusgalli]
Green :Fox~ail ~ FT ~Setaria viridLs]
Wild Oats - WO [Avena fatua (L- ? ]
Shattercane ~- SC [ ~ bicolor]
Result - Percent injury with antidote presen~/percent injury
of herbicidF alone.
COMPOUNDMET~IOD OF
NUMBERHERBICIDE APPLICATION 'RATE CROP RESULT
1 ORDR~M PPI . 6~5 CN 60/90
RONEET PPI 6~5 CN 85/95
RONEET: PPI 2~5 ~.S 40/50 .
ORD~AM PPI 4~5 SB 70/80
RONEETPPI ' 2~5 SB 60/70
VERNAM PPI 6-~5 SB 10/40
~ IF 6~5 SB 20~40
: 3 ORDRAM ST 4~125 BA 10/30
;
; RONEET ST 2~.10 BA 50/80
R-12001 PPI 2~1 7BA 30/60
~ ~ ST 2~.25 BA 30190
" VERNAM ST 1~.10 BA 40/60
OR'~RAM PPI 6+5 CN 50l90
. '~ONEET PPI 6~5 CN 30/95
: PPI 6tO.5 CN 30/50
i~
,s,
-27-
.
,.; ~

~ ~ 7
TABLE III (continued)
COMæOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
3 cont. VERNAM PPI 6~5 CN 60¦75
EPTAM PPI 0.75~5 GS 60/100
ORDRAM PPI 2+5 GS 45/82
ST 2f.l25 GS 55/75
RONEET PPI 3~5 GS 40/75
ST 3-~.125 GS 50/70
R-12001 ~PI 2-~5 GS 58/92
ST 2~.125 GS 45/85
SUTAN PPI 2~5 GS 50/95
ST 2+.125 GS 70/95
VERNAM ST . 1~.125 GS 65/95
EPTAM PPI 51-1 SB 30/65
- ORDRAM PPI 4+1 SB 40~80
RONEET PPI 2~ SB 10/70
SUTAN PPI 5+1 SB 45/65
VERNAM IF 6~1 SB ~ 0/40
ST 6~.062 SB 10/45
ORDR~M ST 4~.125 WT 10¦20
RONEET IF 2+1 WT 75/90
R-12001 PPI 2~1 WT 60l95
R-12001 ST 2~.062 WT 40/70
VERN~M IF 1~5 WT 60/90
4 ORDRAM PPI 6~5 CN 80/90
RONEET PPI 6~5 CN 75/95
RONEET PPI 2~5 SB 60/70
VERNAM PPI 6+5 25/40
~ '
- -28-
.

~ ~ 7
TABLE III (continued)
COMPOUND MEI~IOD OF
NUMBERHERBICIDEAPPLICATION RATECROP RESULT
ORDRAM PPI 6~5 CN 80/90
RONEET PPI 6~5 CN 80/95
RONEET PPI 2+5 GS 40/50
6 0RDRAM PPI 6~5 CN 80/90
RONEET PPI 6+5 CN 80/95
RONEET PPI 2+5 GS 40/50
ORDRAM PPI 4~5 SB 50/80
7 ORDRAM PPI 6+5 CN 70/90
RONEET PPI 6~5 70/95
ORDRAM PPI 4+5 SB 70/80
8 ORDRAM PPI 6~5 CN 80/90
RONEET PPI 6~5 CN 80/95
VERN~M IF 5~5 CT 30/60
RONEET PPI 3~5 GS 50/75
VERNAM IF 6+5 SB 20/40
9 ORDRAM PPI 6~5 CN 70f90
RONEET PPI 6~5 CN 70/95
VERN~M IF 5+5 CN 50/75
VERNAM IF 1~5 R 40/60
VERNAM IF 1~5 ~T 60/87
ORDRAM PPI 6~5 CN 80/90
RONEET PPI 6~5 CN 75~95
VERNAM IF 5-~5 CT 70/80
ORDRA~ PPI 2+5 GS 50/85
RONEET PPI 2~5 GS 40/50
~29

TABLE III ~continued)
__
COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
. ., _ . ~ . ~ .
11 ORDRAM PPI 6 +5 CN 70/90
RONEET PPI 6+5 CN 75/95
VERNAM IF 6+5 CN 0/70
ORDRAM PP~ 2~5 GS 75/85
ROMEET PPI 2+5 SB 50/70
; VF.RNAM IF 6+1 SB 20/40
:
. 12 ORDRAM PPI 6~ CN 70/90
RONEET PPI 6+5 CN 75/95
i ORDRAM PPI 2 ~5 GS 62 / 82
RONEET PPI 3+5 GS 50/75
. R-12001 PPI 2+5 GS 50/90
VERNAM IF 1+5 GS 50/100
ORDRAM PPI 4+5 SB 20/80
RONEET PPI 2~5 SB 40/70
VERNAM IF 6-~ SB 10/40
;
,~ 13 RONEET PPI" 6+5 CN 75/95
VERNAM IF 5~5 CT 60/80
ORDRAM PPX 4~5 SB 70/80
RONEET PPI 2~5 SB ~0/70
- 14 VERNAM IF 5~5 BA 50/82
,
', ~ VERNAMIF 5+5 CN 50/70
~: VERNAM IF 1~5 WT 60/75
; 15ORDRAMPPI 6+5 CN 75/90
VERNAM IF 5~5 CN 40/50
:: ORDRAM PPI 2+5 GS 70/85
,"
-30-
,

~a76
TABLE III (continued)
COMl?OUND ~El~lOD OF
NU~ER HERBICIDE APPLICATION RATE CP~OP RESULT
15 cont. VERN~MIF 1+5 GS60/100
EPTAMPPI 5+5 SB 35/65
ORDRAMPPI 4-.'5 SB 50/80
RONEETPPI 2~5 SB50 /7 0
SUTANPPI 5~5 SB 30/65
VERNAMIF 6~1 SB 20/50
16 ORDRAMPPI 6+5 CN 80/90
ORDR~MPPI 2~5 GS 60/85
RONEETPPI 2~5 GS 40/50
VERNAMIF 1~5 GS60/100
ORDRAMppT 4~5 SB 60/80
17 ORDRAMST . 4 tO "5 BA 10/30
RONEETST 2 t0.25 13A10/80
R-12001PPI 2~5 BA 40/60
R-12001ST 3~0.25 BA 25/90
SUTAN ST 2~0 . 25 BA 0/75
VERNAMIF 1~5 BA30/100
ORDRAMPPï 2~5 GS 10/82
ORD~AMST 2~0.25 GS 40175 ~-
RONEETPPI 3~5 GS 50/75
RO~EETST 2~.2$ GS 10/70
R-12001PPI 2~5 GS 68/92
R-12001ST 2~0.25 GS 25/85
SUTAN ST 2-0 . 25 GS 10/95
VERNAMIF 1~5 GS40/100
VERN~MST 1~0.25 GS 30/-95
-31-

7 ~
TABIE III (continued)
CO~IPOUND METHOD OF
NUMBER HERBICIDEAPPLICATION RATE CROPRESULT
17 cont. EPTAM PPI 5+5 SB 40/57
EPTAM ST 5+0.5 SB 0/50
SUTAN PPI 5~5 SB 30/65
VERNAM IF 6+5 SB 10/50
ORDRAM ST 6~0.125 WT 10/30
R~12001 PPI 2+5 WT 80/95
18 ORDRAM ST 4~0.125 BA 10/30
RONEET ST 2-~ .10 BA 20/80
R-12001 PPI 2~5 ~A 10/60
R-12001 ST 3~Q.10 BA 30/90
SUTAN ST 2-0.10 BA 0/75
VERNAM IF 1~5 BA 30/95
PPI 1~5 BA ~0/95
ST 1~0.10 BA10 /60
ORDRAM PPI 6~5 CW 30/90
RONEET PP~ 6+~ C~ 70/95
R-12001 PPI 6tO.5 CN 20/50
VERNAM PPI 6~5 CN 50/75
VERNAM IF 5~5 CN 40/90
EPTAM PPI .75+5 GS50/100
ORDRAM PPI 2+5 GS 30/82
ORD~AM ST 2~0.125 GS 50/75
RONEET PPI 2~5 GS 20/75
RONEET ST ~+0.125 GS 2Q/70
R 12001 ST 2~0.1?5GS 50/85
SUTAN PPI 2+5 GS 75/95
-32 -

7~
TABLE III (continued)
COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
18 cont, SUTAN ST 2~0.125 GS 60/95
VERNAMPPI 1-~5 GS60/100
IF 1-~5 GS40/100
ST l~O.125 GS 60/95
R-12001PPI 2~5 R 60/70
VERNAMIF 1~5 R 80/100
EPTAMPPI 5~5 SB 20/65
ORDRA~PPI 4~5 SB 40/80
RONEETPPI 2~5 SB 30/70
SUTANPPI 5~5 SB 20/65
VERN~MIF 6~1 SB 13/50
ST 6~0.125 SB 15/25
. ORDRAMST 4~0.125 WT 5/30
RONEETST 1~n.25 WT 70/95
R-12001PPI 2~5 WT 75/95
ST 2f~o63 WT 40/70
VERNAMIF 1~5 WT70/100
. 19 R-12aOlPPI 2~5 BA 30160
`. VERNl~PPI 1~5 BA 40/95
VERN~ IF 1~5 BA 20/96
ORDRAMPPI 6 ~5 CN6 0 / 90
, RONEETPPI 6~5 CN 50/95
VERNAM IF 5~5 CN 50/90
. EPTAMPPI 0.75.~5 GS60/100
ORDRAMPPI 2~5 GS S2/82
, RONEETPPI ~5 GS 20/75
R ï2001PPI 2~5 GS 62/92
" .
33-
s'

TAB~ III (c ontinued)
COMPOUND METHOD OF
NU~ER ~ERBICIDEAPPLICATIONRATE CROP RESULT
19 cont. SUTAN PPI 2~5 GS 70/95
VERNAM PPI 1-~5 GS 6 0/100
VERNAM IF 1+5 GS 50/100
R-12001 PPI. 2~5 R 50/70
VERNAM IF 1-~5 R 80/100
RONEET PPI 2 ~5 SB 40 / 70
VERNAM IF 6+1 SB 10/40
~-12001 PPI 2~1 WT 50/95
VERNAM IF 1~5 W~T 80/100
VERNAM IF 1~5 BA 50/95
ORDRAM PPI 6~5 CN 70/90
RONEET PPI 6+5 CN 70/95
VERNAM IF 5~5 CN 70/90
VERNAM IF 5~5 CT 60/8()
VERNAM IF 1~5 R 85 / ~ 00
VERNAM IF 6~1 SB 20 /40
21 R lZOOl PPI 2~5 BA 30/60
VE~N~M PPI 1-~5 BA 60/95
VERNAM IP 1~5 BA 30/95
OR~RAM PPX 6~5 CN 60/90
RONEET PPI 6-~5 CN 70/95
VERNAM IF 5~5 CN 60/90
EPTAM PPI 0.75~5 GS 40/lOO
O~DRAM PPI 2~5 GS 25~82
RONEET PPI 2~5 GS 40/75
R-12001 PPI 2~5 GS 45/92
-34 -

:~3
TABIE III (continued)
COMPOUND ~ETHOD OF
NU~El~ HER13XCIDEAPPLICATION RATE CROP RESULT
21 cont, SUTAN PPI 2-~5 BA 30/95
VERN~M PPI 1+5 GS 60 /100
VERNAM IF ~ 5 GS 40/100
R-12001 PPI 2~5 GS 40/70
RONEET PPI 2+5 SB 50/70
VER~AM IF 6+1 SB 25/50
R~12001 PPI 2~5 WT 50/95
VERNAM IF 1~5 WT 80/100
. 22 ORDRAM PPI 6+5 CN 60/90
RONEET PPI 6+5 C~ 85/95
. O~DRAM PPI 4~5 SB 70/80
RO~EET PPI 2+5 SB 60/70
VERNAM IF 6~1 SB 30/40
23 VERNAM IF 1+5 BA 20/90
~:RNAM IF 5+5 - CN 20/90
EPTAM PPI 0.75~5 GS 70/100
ORD3~ PPI 2~ GS 60/80
. RONE:ETPPI: 3~5 GS 50/75
RONEET IF 3-~5 GS 30/75
~: R-12001 PPI 2~5 GS 50/90
24 VERNAM IF 1~5 BA 10/90
,.:
VER~;M IF 5~5 CN 50/90
EPTAM PPI 0 . 75~5 GS 40/100
ORI3RA~ PPI 2+5 GS 40/80 .
~.,.
~j; RONEET PPI 3~5 GS 20/75
,~j
: -35-
,;'''

~Q76`~
TABLE III (continued)
CO~OUND METHOD OF
NI~ER HERBICIDE APPLICATION RATE CROP RE~ULT
24 con~. RONEET IF 2+5 GS 30/65
R-12001 PPI 2~5 GS 30/90
SUTAN PPI 2~5 GS 40/95
VERNAM IF l~S GS 20/96
VE~NAM IF 1-~5 ~A 20/70
VERNAM IF 5~5 CN 20/90
RONEET IF 2t~ GS 30/65
VERNAM IF 1~5 GS 30/96
VERNAM IF 1-~5 R 50/100
26 VERNAM ` IF 5-~5 CN 60/90
VERNAM IF 1+5 GS 60/96
27 ORDRAM . ST 4~0.125 BA 0/30
RONEET ST 2~0.25 BA 10/80
R-12001 PPI 2~5 BA 10/60
R-12001 ST 3~0.125 BA 0/70
SUTAN ST 2~0c25 BA 0/75
VER~AM IF 1~5 BA 10/70
. VERMAM ST 1~0 ~ 10 BA 20/60
. VERN~M IF 5t~ CN 40/90
: EPTA~ PPI 0.75~5 CT50/100
ORDRAM PPI 2~5 CT 50/80
ORDRAM ST 2~00125 CT 40/75
RONEET PPI 3~5 CT 30/75
RONEET IF 3~ CT 40/65
.
-36 -
.

~7
TAB I (continued)
COMPOUND METHOD OF
NUMBER ~ERBICIDEAPPLICATION TE CROP RESULT
27 cont . RQNEET ST 3-~0.125CT 20/70
R-12001 PPI 2-.'5 CT 50/92
R-12001 ST 2tO .125 CT 30/85
SUTAN ST. 2-~0.125CT 30/95
EPT~M PPI 0.75+5 GS 50/100
ORDRA~ PPI 2~5 , GS 50/80
ORDRAM ST 2~0.125GS 40/75
RONEET PPI 3~5 GS 30t75
IF 3~1 ~S 40/65
ST 3~0.125GS 20/70
R~12001 ST 2~0.125GS 30/85
SUTAN ST 2~0.125GS 30/95
VERNAM IF 1~5 GS 30/96
ORDRAM ST 6t0.125WT 10/30
R~12001 ST 2~0.062WT 40/70
28 VERNAM IF 1~5 BA 20/70
VERNAM IF 5~5 CN 50/90
ORDRAM ST 2~0.125GS 45/75
RONEET IF 2~5 GS 40/65
RONEET ST 3t0.125GS 30/70
R-12001 PPI 2+5 GS 50/95
; . R-12G01 ST 2~0.125GS 30/85
SUTAN ST 2~0.125GS 40/95
VERNAM IF 1~5 &S 20/96
VERNAM ST 1~0.125GS 40/95
ORDRAM ST 6~0L 125 WT 0/40
-37 -
/
.,

~ 9
TABLE III (c ontinued ~
COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
28 cont. R-12001 PPI 2+5 WT 50/95
R-12001 ST 2+.125WT 30/70
29 ORDRAM ST 4~0.125 BA 10/30
R-12001 PPI 2+1 BA 40/60
VERNAM ST 1-~0.50BA 50t95
EPTAM PPI 5~5 CN 20/85
R-12001 PPI 5+0.5 CN 20/50
~PTAM PPI 0.75~5 GS 40/100
ORDRAM PPI 2~5 GS 30/80
ORDRAM ST 2~0.125 GS 40/75
RONEET PPI 3~5 &S 30/75
RONEET IF 3+2 GS 40/65
RONEET ST 3*0.125 &S 20/70
- SUTAN PPI 2~5 GS 30/95
VERNAM IF 1+5 GS 40/100
VERNAM PPI' 6+5 SB 15/40
31 EPTAM PPI 5+5 CN 30/85
VERN~M IF 5+5 S8 10/40
32 VER~AM IF 1~5 ~A 60/70
; VERNAM IF 1~5 CT 40 /60
: VERNAM IF 1+5 GS 70/100
VERN~M IF 1~5 SB 0/42
, 33 VERNAM IF 1~5 BA 60/70
f. VERNAM IF 1~5 GS 50/100
VERNAM IF 1~5 R 70/95
:,
-38 -
. .

COMPQUND ME lHOD OF
NU~ER HERBICIDEAPPI.ICATI ON RATE CROP ~ESULT
33 cont. VERNAM IF 1~5 SB 30/60
34 VERNAM IF 1~5 BA 50/70
VERNAM IF 1~5 CN 70/90
VERNAM IF 1+5 GS 60/100
VERNAM IF 6~1 SB 10/42
VERNAM IF 1~5 BA 60/70
VERNAM IF 1~5 CT 40/60
VERNAM . IF 1~5 GS 50/100
VERNAM IF 6~5 SB 20/42
36 VERNA~ IF 1~5 BA 30/60
VERNAM IF 1+5 CN 50/95
VERN~M IF 1~5 GS 50/100
37 VERNAM IF lf5 BA 20/60
VERNAM IF 6~5 CN 60/95
VERN~M IF 1+5 CT 20/5û
VERNAM IF 1~5 GS 40/100
VERNAM I~. 1t5 WT 6û/90
38 VERNAM IF 1~5 BA 20/60
VERNAM IF . 6~ CN 10/95
VERNAM l~ ^ 6+5 SB 20/50
- 39 RONEET PPI 6~5 C~ 75/95
VERNA~ IF 1~5 BA 60/100
ORDRAM PPI 6~5 CN 70/90
VERNAM IF 1-~5 GS 60/100
VERNAM PPI 6+5 SB 10/40
41 VERNAM IF 1~5 BA 40/50
ORDRAM PPI 2~5 GS 60/80
-39-
,

COMPOUND ~ETHOD OF
NUMBERHERBICIDE APPLICATION RATE CROP RESULT
42 VERNAM IF 1-~5 BA 30/50
RONEET PPI 2 +5 GS 40 / 75
VERNAM PPI SB 40/60
43 ORDRAM PPI 6~5 CN 70/90
RONEET PPI 2+5 &S 40/50
ORDRAM PPI 4~5 SB 50/80
VERNAM IF 1~5 ~T 60/90
44 VERNAM -IF 6~5 GN 50/70
yERNAM IF 1~5 CT 40/70
RONEET PPI 3~5 ~S 60/75
VERNAM IF 1-~5 R 40/95
VERNAM PPI 4~5 SB 40/50
46 VERNAM IF 1~5 BA 30/50
RONEET PPI 3~5 GS 50/75
VERNAM IF 1~5 R 30195
47 VERNAM PPI 6+1 SB 10/40
~ERN~M IF 6~5 SB 60/80
VERNAM IF 1~5 WT 50/75
48 ORDRAM :PPL 2~5 GS 60/85
VER~M PPI 6~5 SB 30/40
49 VERNAM IF 5~5 CN 40/70
. RONEET PPI 2-~5 SB 50/70
VER~AM PPI 6+5 SB 30/40
VERNAM IF 1~5 BA 60/90
VERNAM IF 1~5 R 50/90
ORDRAM PPI 4+5 SB 50/80
-40-

~
TAB (continued)
COMPOUN~ METHOD OF
NUMBER . HERBICIDE APPLIC~TION RATE CROP RESULT
.
50 cont. VERNAM IF 6+1 SB 30/40
51 VERNAM IF 1~5 BA 30/83
EPTAM PPI O.75~5 GS 50/100
ORDRAM ST 2~00125 GS 50/75
: RONEET ST 3~0.125 &S 30/70
VERNAM IF 1~5 GS 60/100
VERN~M IF 6~0~5 SB 10/40
52 EPTAM PPI 0.75+5 GS 50/100
RONEET PPI 3~5 GS 20/75
` . RONEET IF 3~1 GS 40/75
,. SUTAN PPI 2~5 GS 40/95
VERNAM IF 1~5 GS 40/100
VERNAM PPI 6~5 SB 10/50
. IF 6~5 SB 10~30
53 ORD~AM PPI 6~5 CN 50/90
. "
ORDRAM PPI 2~5 GS 60/85
,: VER~AMi IF lt~ R 50/95
54 ~ERNAM IF 1~5 BA 10/60
. VERNAM IF 6~5 CN 40/70
. EPTAM PPI 0~75~5 GS 30/100
ORDRAMi PPI 2~5 GS 40/80
' RONEET PPI 3+5 GS 20/75
.'. RONEET IF 3-~5 GS 10/75
. ~-12001 PPI 2~5 GS 20/90
'. SUTAN PPI 2~5 GS 30/95
.,
-41-
,
,;

TABLE III (continued)
, .
COMPOUND METHOD OF
NUMBERHERBICIDE APPT.TCATION RATE CROP RESULT
54 cont. VERNAM IF 1+5 GS 30/100
VERNAM PPI 6~5 SB 0/50
VERNAM IF 1+5 WT 60/90
55 ORDRAM PPI. 6+5 CN 70/90
VERNAM IF 6~5 C~ 70/90
VERNAM IF 1+5 GS 75/100
VERNAM PPI 6+5 SB 10/40
~ERNAM IF 6~1 SB 20/40
56 ORDRAM PPI 6~5 CN 70/90
RONEET PPI 2~5 GS 40/50
VERNAM PPI 6~5 SB 10/40
VERNAM IF 6~1 SB 20/40
57 VERNAM P~I 6~Q.5 SB 20/40
VERNA~ IF 6~5 SB 40/60
58 VERNAM PPI 6~1 SB 10/40
VERNAM IF 1~5 WT 50/78
59 VERMAM IF 1~5 GS 70/100
VERN~M PPI 6~5 SB 30/50
VERNAM IF 6~5 SB 10/30
VERNAM IF 1~5 BA 30155
VEP~NAM IF 1+S GS 60/85
61 VERNAM IF 6~5 CN 80/90
VE~NAM IF 1+5 CT 40/50
62 VERNAM IF 1+5 BA 30/55
VERN~M IF 6~5 CN 70/90
-42-

7~
TABLE III (continued)
-
COMPOUND METHOD OF
ERHERBICIDE APPLICATION RATE CROP RESULT
63 VERNAM IF 1+5 BA 20/55
VERNAM IF 6~5 CN 50/90
VF,RNAM IF 6~5 SB 30/55
64 VERNAM IF 1+5 CT 40/60
VERNAM IF 1~5 GS 40/100
VERNAM -IF 1+5 BA 40/60
yERN~M IF 1+5 CN 30/95
. VERNAM IF 1~5 GS 40/95
VERNAM IF 6+5 SB 0/60
, 66 VERN~M IF 1~5 BA 30t55
VERNAM IF 6~5 CN 30/90
VERNAM IF 1~5 GS 40/85
67 VERNAM IF 1~5 BA 40/55
, VERNAM IF 6+5 CN 70/9O
VERNAM IF 1~5 GS 60/85
VERNAM IF 1~5 WT 60/70
68 VERN~M IF 1~5 BA 30l55
, VERNAM IF 6~5 C~ 30/90
VERNA~ IF 1~5 GS 40/85
VERNAM IF 6~5 SB 30/55
~. VERNAM IF 1~5 WT 50/70
.~ 69 VERMAM IF 1~5 BA 20/55
~: VERNAM IF 6~5 CN 30/90
.~; VERNAM IF 1+5 GS 40/85
~,.
-43-
,,;

~Q~ ~9
TABLE III (c on~inued)
CGMæOUND ~THOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
VERM~M IF 1-~5 BA 30/55
VERNAM IF 6~-5 CN 40/90
VERNAM IF 1~5 GS 30/85
VERNAM IF 6+5 SB 30/55
71 VERN~M IF 1~5 BA 40/50
VERN~M IF 5~5 SB 10/40
72 VERNAM IF 1~5 WT 40/75
73 VERN~M IF 6+5 SB 30/60
74 VERNAM IF 1~5 WT 50/75
; 75 VERNAM IF 1~5 BA 30/50
VERNAM IF 1~5 WT 40/75
76 VERNAM IF 1~5 CT 55/70
~ERNAM IF . 1~5 ~T 50/75
77 VERMA~ IF 1+5 BA 30/60
VERNAM IF 6~1 SB 10/40
78 R~12001 IF 6~5 CT 50/65
VERNAM XF 1+5 CT 10/50
VERNAM IF 6~5 SB 40/60
79 VERNAM IF 6~5 SB 30/60
VERN~M IF 1~5 BA 40/70
VERNAM IF 1~5 GT 40/60
VERNAM IF 1~5 R 60/95
VERNAM IF 6~5 SB 40/60
. -44 -

76
TABLE III (continued)
COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
.
81 VERNAM IF 1~5 CT 40/50
82 VERNAM IF 1~5 GS60/100
VERNAM PPI 6tO.5 SB 20/40
83 VE~NAM IF 6+5 CN 50/95
VERNAM IF 1+5 CT 30/50
VERNAM -IF 1+5 GS80/100
yERNAM IF 6+1 SB 10/50
84 VERNAM IF l+S GS 70/95
VERNAM IF 6~1 SB 0/40
RONEET IF 3+5 GS 30/75
VERNAM IF 1~5 GS50/100
VERNAM PPI 6+5 SB 10/SO
86 VERNAM IF 1~ RA 70/83
VERN~M IF 6+5 CN 60/90
- VERNAM IF 1~5 GS70/100
VERNAM PPI 6+1 SB 20/40
87 ~RN~ IF 6-~5 CN 80/90
~ERNAM IF 1~5 GS60/100
VERNAM IF 6~5 SB 40/60
88 VERNAM IF 6+5 CN 80/00
VERNAM IF 1~5 GS80/100
VERNAM IF 6+1 SB 10/42
89 VERN~M IF 1~5 CT lO/50
VERN~ IF 6~5 SB 30/60
-45-
:
~ " : - ~

7~
TABLE III (c ontinued)
COMPOUND METHOD OF
NU~ER HERBICIDE APPLICATION RATE CROP RESULT
VERNAM IF 1+5 BA 30/55
VERNAM IF 6~1 SB 0/50
VERNAM IF 1+5 WT 60/85
91 VERNAM IF- 1+5 CT 20/50
VERNAM IF 6~5 SB 30/55
92 VERNAM IF 1+5 BA 20/55
VERN~M IF 1~5 CT 30/50
VER~AM IF 6~5 SB 20/50
93 V~RNAM IF 1~5 GS 60/95
VERNAM IF 6~5 SB 40/60
94 VERNAM IF 1~5 GS 80/100
VERNAM IF 6~5 SB 30/50
VERNAM IF ~1~5 WT 70/~5
: 95 VE~N~M IF 6+5 CN 80/90
VERNAM IF 1~5 R 20/70
6 VERNAM IF 1~5 BA 40/70
VER~AM IF lt~ CT 40 /60
VERN~M IF 1~5 R 60/95
. V~RN~ IF 6~5 SB 30/60
- 97 ~ERN~M IF 1+5 BA 40/55
98 VERNAM IF 6~5 SB 30/55
99 VERNhM IF 1~5 BA 30/55
. VERNAM IF 1~5 R 20/70
;::
; 100 VE~NAM IF 1~5 BA 30/55
. VERMAM IF 1~5 R 60/70
;,:,
1, .
. ~46 -
,,:

~7
TAl~J~. III (continued~
C 02IPOUND METEIOD OF
NIJMBERHE:R ICIDEAPPLICA ON RATE CROPRESULT
101 VERNAM IF 1~5 BA40/55
VERNAM IF 6~5 SB20/50
VERNAM IF 1t~5 WT6 0/85
102 VERNAM IF' 1~5 BA30/55
VERNAM IF 1+5 CT40/50
VERNAM IF 6+5 SB 0/50
103 R-12001 IF 6~5 CT50/65
VERNAM IF 1~5 CT30/50
VERNAM ` IF 6~5 SB 0/60
VER~AM IF 1~5 WT60/85
104 VERNAM IF 1~5 BA40/55
VERN~M IF 6~5 SB30/60
VERN~I IF 1~5 WT60/70
105 VERNAM IF 1~5. BA40l55
VERMAM IF,. 6~5 SB 0/60
VERNaM IF 1~5 WT60/85
106 YERNAM IF 1t-5 BA30~60
VERN~M IF 6t-5 CN70/95
VERNAM IF 6+5 S1330¦60
107 VE~RN~M IF 6~5 SB 0/60
VERNAM IF 1~5 WT60/85
'
-47- ,

~ ~ 7 ~ ~
In side~by-side tests with various weed species and
crops, it was ~ound that weed control was maintained while at
the same ~ime the crop species were protec~ed or iniury de-
creased, when compared to a check or control flat. The control
~lat contained no antidote compound candida~e. The following
table further exemplifies those results.
TABLE IV .
~`~
HERBICIDE RATE GS SC WG
RONEET ~ 3 lb/A- 50 50 lO0
(PPI)
COMPOUND
NDMBER RATE (IF~ GS SC WG
2 l lb/A 40 lO0 lO0
33 l lb/A 30 lO0 lO0
l lb/a 30 lO0 lO0
36 l lblk lO 100 lO0
37 l lb/A 25 lO0 lO0
38 l lb/A 1. 30 lO0 lO0
lO0 lO0
l lb/A 15 lO0 lO0
68 l lb/A 40 lO0 lO0
69 l lb/A 40 lO0 lO0
l lb/A 15 lO0 lO0
93 1 lb/A 40 lO0 lO0
g3 5 :Lb/A 30 lO0 lO0
106 l lb/A 40 lO0 lO0
,,
. -48~

~7
~9
Perc ent Inj ury
HERBICIDE RATE RC w'r WG WO
ORDRAM~) 8 lb/A 25 30 100 100
(PPI )
_
COMPOUND
NLTMBER ~ RC WT WG WO
3 1 lb/A 50 20 100 100
5 lb/A O 60 0 O
17 1 lb/A 50 10 100 100
5 lb/A 20 0 100 100
18 5 lb/A 20 10 100 100
19 1 lb/A 60 20 100 100
S lb/A O 60 100 100
1 lb/A 40 10 100 100
5 lb/A 10 10 10(~ lOû
27 1 lb/A 60 10 100 100
5 lb/A 10 50 lQO lOQ
29 5 lb/A 20 LO lQO 100
47 5 lb/A 20 2Q 100 100
51 5 lb/A 40 20 100 100
94 5 :Lb/A 40 10 100 100
96 5 lb/A 60 lO 100 100
/
': -4g-
s
, .

TABLE IV (continued~
ORDRAM ~ 8 lb/A PPI
COMPOUND
NUMBER RATE ~F) R WT WG WO
32 1 lb/A 40 20 100 100
5 lb/A O 10 80 100
35. 1 lb/A 10 10 100 100
37 l lb/A 40 10 100 100
- 38 5 lb/A 30 10 100 100
e ~
HERBICI~E KATE C. WG FT
SUTAN ~ 12 lb/A 50 100100
COMPOUND RATE ~PPI
NUMBER . TANK MIX C WG FT
; 3 5 lb/A 20 100 100
1~ 5 1~/~ " 4~ 100 100
19 5 lbiA 40 100 100
21 5 lb/A ~0 100 100
: 23 5 lb/A 40 100 100
24 5 lb/A : 30 100 130
29 5 lb/A 20 100 100
51 5 lb/A ?~ 100 100
The compounds and compositions of this invention
were employed in efective herbicidal compositions comprising
the antidote and a thiocarbamate herbicide as described herein-
above-. The herbicidal compositions were tested in the above
-5~-
,

~ ~ 7
manner.
A preferred herbicidal composition comprises a thio-
carbamate herbicide and an antidotally effective amount of an
antidote compound therefor corresponding to the formula in
~ N- ~ OR
. which ~ is hydrogen, methyl, methox~, chloro or bromo; and R is
alkyl having 1 to 4 carbon a~oms~ inclusive, haloalkyl having
2 to 6 carbon atoms~ inclusive, wherein halo is chloro, bromo
or fluoro from 1 to 6, inclusi~e; alkenyl having 3 to 6 carbon
atoms, inclusive, chloroalkenyl having 3 to 6 carbon atoms, in
clusive, or alkynyl having 3 to 6 carbon atoms, incluslve, di-
alkylamino, having 2 to 6 carbon atoms, inclusive~ trifluor-
acetamidomethyl, 4-chlorophenylthiomethyl, phenyl, 3-phenyl~
propyn-2~yl, 3-pyridylmethyl and phosphonomethyl.
The compositions of the present în~rention for the pro-
tectio~ of cul~ivated crop plants ~-omprise the active herbicidal
compound and an antidote therefor selected from the above-de-
scribed compounds. The compositions of herbicide and antidote
, can be prepared by conven~ional me~hods through ~he thorough
.~ mixing and grinding of the ac ~ive herbicide agents and the anti-
dote with suitable carriers and/or other distributiol media,
possibly with the addition of dispe~sion agents or solvents.
,;
The antidote compounds and composi~ions of the present
inventio~ can be used in any co~venient form. A solvent or
inert carrier is not necessary in view of low volume spray tech-
nology which permits ~he use of nea~ ~echnical grade materials
. as sprays Thus, the antidote compounds and composition wi~h
.. the thiocarbamate herbicide can be formulated into emulsifiable
-
-51-
. .
, . , :,, , , , "

~ ~ 7 ~ ~9
liquids, emulsifiable concentrates, liquid, wettable powder,
powders, granular or any other convenient form. In its
preferred form, a non-phytotoxic quantity of an herbicidal
antidote compound is admixed with a selected herbicide and
incorporated into the soil prior to or after planting the seed.
It is to be understood, however, that the herbicide can be
incorporated into the soil and thereafter ~he antidote compound
can be incorporated into the soil. Moreover, the crop seed
itself can be treated wlth a non-phytotoxic quantity of the
compound and planted into the soil which has been treated with
.
herbicide, or un~reated with the herbicide and subsequently
treated with the herbicide. The addition of the antidote com-
pound does not aff~ct the herbicidal activity of the herbicide.
The alternative methods o~ application have been exemplified in
the above examples.
The amount of antidote compound present ~an range
be~ween about 0.001 to about 30 parts by weight of antidote
compound described herein per eaoh part by weight of herbicide.
The exact amount o antidote compound will usually be determined
on econ~mic ratios or the most éfective amou~ usable~ It is
understood that a non~phytotoxic, bu~ effective quantity of
a~tidote compound will be employed in the herbicidal composi~ions
and methods described herein.
Ater treatment with the antidote and herbicide there
~s obtain as a resultant thereo~ soil which is novel in compo-
sition. Said 50il iS improved in its capabi~ity to grow crops
and to ofer weed con~rol. Fur~her said soil trea~ed with herbi- -
cide and an~idote has the particular utility for allowing seed
',
.,
~ -52~
"
... .

of crops oth~rwise injured by the herbicide to be planted and
grown. The herbicide has its utility in controlling undesir-
able vegetation; the antidote compound decrease the injury from
the herbicide upon the crop species, and the soil ~reated with
herbicide and antidote compound provides an improved media to
grow the crop in the presence of an othe~ise injurious herbicide.
In the utility of the present antidote compounds
and impro~ed herbicide system the thiocarbamate can be applied
to the soil. Application of the herbicide to the soil can take
place by preplant incorporation. In conjunction with the prior
application of the herbicide employing the present invention
crop seeds aré planted. Seed planting is followed by applica-
tion of the antidote as a preemergence surface application. This
sequen~e of application of herbicide, seed plan~ing and anti-
dote is unusual and fully e~fective in decreaslng injury to
the plant crop, otherwise injured by the thiocarbama~e.
~e~
Variou~ antidote compounds described herein have been
~: fouad capable of decreasing in~ury ~o the class of cxops known
as legumes~ By legumes is meant those plants that have a sym-
biotic relationship with nitrogen fixing organisms. For example,
so~beans, varieties of Phaeseolus vulgaris (L. ~, peanuts, alfalfa,
c lover and ~he like .
The following test was performed to determine the
efficac~ as decreased injury of the 1~ ume crops by a representa-
tive thiocarbamate herbicide, EPTAM ~ (EPTC), S-ethyl
di~n-propyl thiocarbamate with compounds described hereinabove.
'
-53-

~ ~ r ~
Various edible bean and pea varieties were tested. The anti-
dotes were applied at 1 and 2 lb/A preplant incorporated, tank
mixed with EPTC at 6 lb/A preplant incorporated.
Stock Solutions:
.. . . . .
Antidote: For each candidate compound employed
.
39 mg. dissolved in 25 ml. aceton~; 2.5 ~1. equivalent to
1 lb/A preplant lncorporated.
Herb : EPTAM ~ 6E: 1560 mg. dis301ved in 250
ml. watex; 5 ml. equivalent ~o 6 lb/A preplant incorporated.
- The crops tested were Navy bean - NB, Kidney bean - KB,
Pinto bean - ~B (various varieties of Phaeseolus vulgaris L.)
and peas (Pisum sati~um L~) The weed species included in the
tests were wa~ergras~ - wg and foxtail ~.
TABLE V
Perce~t InlurY
~71 ~I--a~--~e~lr7rla¦~
NB PB WG FT
EPTC 6 lb/A65 , 50 100 100
C~MPOUND
NUMBER RATE~ NB PB~ WG FT
3 1 lb/A30 20 100 100
2 lb/A20 20 100 100
17 1 1~l~30 50 100 100
2 lb/A50 40
18 1 lbA25 30 100
2 lb/A50 40
': .
",
' -54-
:

TABLE V (continued~
COMPOUND
NUMBER R~TE NB PB WG Fl~
28 1 lb/A 50 40
2 lb/A 50 30 100 100
29 1 lb/A 0 40 100 lO0
2 lb/A 30 20 100 100
33 1 lb/A 40 40 100 100
2 lb/A 50 40 100 100
51 l lb/A 40 20 100 100
2 lb/A 50 30 100 100
54 1 lb/A 30 40 100 100
2 lb/A 50 0 100 100
57 l lb/A 50 30 100 100
2 lb/A 50 40 lO0 ïO0
1 lb/A 50 40 100 100
2 l~/A 50 10 100 100
A~ two pounds :~or a~re compound number 3 also exhibi-
ted comple~e protection (100%) of kidney leave~. Compound
number 28 exhib~-ke~ S0 percent protection of kidney b ans at
two po~mds per acre. I~1ury to pea~ was decrea~d 37.5 percent
with compound number 28 at two pounds per acre.
-55-