Note: Descriptions are shown in the official language in which they were submitted.
~2~6~5
-1 -
HERBICIDAL 2-HALOACETANILIDES
Background of the Invention
Field of the Invention
~his invention pertains to the field of 2-
haloacetanilides and their use in the agronomic arts,
e.g., as herbicides.
Description of the Prior Art
The prior art relevant to this invention
includes numerous disclosures of 2-haloacetanilides
which may be unsubstituted or substituted with a wide
variety of substituents on the anilide nitrogen atom and
on the anilide ring including alkyl, alkoxy,
alkoxyalkyl, halogen, etc., radicals.
As relevant to the invention compounds, which
are characterized by havin~ a methyl or ethyl radical on
the anilide nitrogen, an alkoxy ~radical in one ortho
position and a methyl radical in the other ortho
position, the closest prior art known to the inventor
are U. S. Patent Numbers 3,268,584, 3,4~2,945, 3,7i3,492
and 4,152,137. The '492 and '137 patents disclose
generic formulae for herbicidal compounds which broadly
encompass the invention compounds. However, the only N-
alkyl-substituted 2-haloacetanilide compound
specifically disclosed by either of the '492 or '137
patents is propachlor, i.e., N-isopropyl-2-
chloroacetanilide, a well-known commercial herbicide;
neither patent discloses any herbicidal data relative to
25 propachlor. U.S. Patent Number 2,863,752 (Re 26,961)
discloses compounds of a class encompassing propachlor
(not specifically named) and homologs and analogs
thereof. Of the compounds within the scope of the '752
patent, propachlor was found to be the most herbicidally
efficacious, hence, was developed as a commercial
herbicide. Said '752 patent discloses that the
compounds therein may be used at rates as low as 1.0
lb/A (1.12 kg/ha); however, as shown in Example IV the
experimental data presented therein is limited to
application rates of 5 lb/A (5.6 kg/ha) and 25 lb/A (28
-2- ~%~ 5
kg/ha). Additionally, N-ethyl-2-chloroacetanilide is a
named species in said '752 patent; yet, U.S. Patent No.
4~137,070 discloses that that compound (Example 406 in
the '070 patent) is an antidote for the herbicide EPTC.
In contrast to the foregoing '752 compounds, the
compounds of this invention are highly effective
selective herbicides against exceedingly hard-to-control
weed species at application rates well below 1.~ lb/A,
e.g., ranging to below one-sixteenth tl/16) lb/A (0.07
kg/ha)
More structurally relevant to the invention
compounds than propachlor or related compounds, perhaps,
are compounds disclosed in said '584 and '945 patents.
In particular, Example 13 of said '584 patent aiscloses
the compound N-tert-butyl-2'-methoxy-2-
chloroacetanilide and Example 6~ of said '945 patent
discloses the compound 2'-methoxy-6'-tert-butyl-2-
chloroacetanilide. Thus, propachlor differs from the
invention compounds in the type of substituent radicals
in two positions, i.e., both ortho positions o~ the
molecule, as well as the particular alkyl radical
attached to the nitrogen atom. Said Example 13 in said
'584 patent differs in the type of substituent in one
ortho position, the particular alkoxy radical in the
other ortho position and the particular alkyl radical
attached to the nitrogen atom and said Example 67 in
said '945 patent differs ~rom the invention compounds in
the type of substituent attached to the nitrogen atom
and the particular alkyl and alkoxy radicals,
respectively, attached to the ortho positions of the
anilide molecule.
U.S. Patent No. 4,146~387 discloses
2-haloacetanilide compounds which may be substituted
with alkyl radicals on the nitrogen atom and in both
ortho positions. The compounds of the '387 patent are
described as known herbicides of the type disclosed,
e.g.~ in the above-mentioned '945 and '752 patents,
including propachlor.
~.
_3~ 65
The above '584 patent contains some herbicidal
data relative to the above-mentioned compound having a
chemical configuration most closely related to the
invention compounds, and some data are presented for
other homologous and analogous compounds less-closely
related in chemical structure. More particularly, these
most relevant references, while disclosing herbicidal
activity on a variety of weeds, do not disclose any data
for any compounds which are shown to additionally and/or
simultaneously control the hard-to-kill annual weeds
such as Texas panicum, itchgrass (raoulgrass), wild
proso millet, alexandergrass, red rice, shattercane and
seedling johnsongrass, while also controlling or
suppressing a broad spectrum of other noxious perennial
and annual weeds, e.g., yellow nutsedge, smartweed,
lambsquarter, pigweed, foxtails, large crabgrass and
barnyardgrass.
A highly useful and desirable property of
herbicides is the ability to maintain weed control over
an ex~ended period of time, the longer the better during
each crop season. With many prior art herbicides, weed
control is adequate only for 2 or 3 weeks, or, in some
superior cases~ perhaps up to 4-6 weeks, before the
chemical loses its effective phytotoxic properties.
Accordingly, one aisadvantage of most prior art
herbicides is their relatively short soil longevity.
Another disadvantage of some prior art
herbicides, somewhat related to soil longevity under
normal weather conditions, is their susceptibility to
leaching into the soil, hence, the lack of weed control
persistence under heavy rainfall which inactivates many
herbicides.
A further disadvantage of many prior art
herbicides is limitation of their use in specified types
of soil, i.e., while some herbicides are effective in
soils having small amounts of organic matter, they are
ineffective in other soils high in
~f~
,,
organic matter or vice-versa. It is, therefore,
advantageous that a herbicide be useful in all types o~
soil ranging from light organic to heavy clay and muck.
Yet another disadvantage of many prior art
herbicides is the limitation to a particular effective
mode of application, i.e., as a preemergence surface
application or as a preplant soil incorporation mode of
application. It is highly desirable to be able to apply
a herbicide in any mode of application, whether by
surface application or preplant incorporated.
And, finally, a disadvantage in some
herbicides is the necessity to adopt and maintain
special handling procedures due to the toxic nature
thereof. Hence, a further desideratum is that a
herbicide be safe to handle.
It is, therefore, an o~ject of this invention
to provide a group of herbicidal compounds which
overcome the above-mentioned disadvantages of the prior
art and provide a multiplicity of advantages in a single
group of herbicides.
It is an object of this invention to provide
herbicides which selectively control hard-to-kill annual
weeds such as Texas panicum, raoulgrass, wild proso
millet, alexandergrass, red rice, shattercane and
seedling johnsongrass, while also controlling or
suppressing a broad spectrum of less-resistant perennial
and annual weeds such as mentioned above, while
maintaining crop safety in a plurality of crops
including soybeans, cotton, peanuts, rape, bush beans,
alfalfa and/or vegetable crops.
It is a further object of this invention to
provide herbicidal effectiveness in the soil for
extended periods ranging up to at least 12 weeks.
Yet another object of this invention is to
provide herbicides which resist leaching and dilution
due to high moisture conditions, e.g., as heavy
; rainfall.
~''
,. . .
.~ .
-5~ 6~6~
Still another object of this invention is the
provision of herbicides which are effective over a wide
range of soils, e.g., ranging from light-medium organic
to heavy clay and muck.
Another advantage of the herbicides of this
invention is the flexibility available in the mode of
application, i.e., by preemergence surface application
and by preplant soil incorporation.
Finally, it is an advantage of the herbicides
of this invention that they are safe and require no
special handling procedures.
The above and other objects of the invention
will become more apparent from the detailed description
below.
1~ Summary of the Invention
The present invention~relates to herbicidally
active compounds, herbicidal compositions containing
these compounds as active ingredients and herbicidal
method of use of said compositions in various crops.
It has now been found that a selective group
of 2-haloacetanilides characterized by specific
combinations of alkyl radicals on the anilide nitrogen
atom and in one ortho position and specific alkoxy
radicals in the other ortho position possess
unexpectedly superior and outstanding herbicidal
properties vis-a-vis prior art herbicides, including the
most-closely-related compounds of the most relevant
prior art.
A primary feature of the herbicidal
compositions of this invention is their ability to
control a wide spectrum of weeds, including weeds
controllable by current herbicides and, additionally, a
plurality of weeds which, individually and/or
collectively, have heretofore escaped control by a
single class of known herbicides, while maintaining crop
safety with respect to a plurality of crops including,
particularly, soybeans, cotton, peanuts, rape, bush
beans (snap beans), alfalfa and others as
'
-6~ 6~
well. While prior art herbicides are useful for
controlling a variety of weeds, including on occasion
certain resistant weeds, the unique herbicides of this
invention have been found to be capable of controlling
or greatly suppressing a plurality of resistant weeds,
most notably annual weeds, such as Texas panicum,
itchgrass, wild proso millet (Panicum miliaceum),
alexandergrass, red rice, shattercane and seedling
johnsongrass, while controlling and/or suppressing other
less-reslstant perennial and annual weeds.
The compounds of this invention are
characterized by the formula
C C 2 \ /
N
R2 ~1~ ORl
~
R3
wherein R is methyl or ethyl;
~ Rl is a Cl_6 alkyl radical, preferably C3 5
- 25 alkyls;
R2 is methyl, ethyl or t-butyl, preferably
methyl, and
R3 is hydrogen or methyl in a meta position
preferably hydrogen;
provided that:
When R is ethyl, Rl is n-butyl, R2 is methyl
and R3 is hydrogen;
When R3 is methyl, R and R2 are also methyl
and Rl is isopropyl or n-butyl;
When R3 is hydrogen and R and R2 are both
methyl, Rl is ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, n-pentyl/ isopentyl, 2-methylbutyl,
l-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl;
';i~
-7_ ~Z~6~5
When R2 is ethyl, R is methyl and R1 is
isopropyl and
When R2 is t-butyl, R and R1 are both methyl.
Preferred species of this invention are as follows:
N-methyl-2'-isopentyloxy-6'-methyl-2-chloro-
acetanilide.
N-methyl-2'-n-propoxy-6'-methyl-2-chloro-
acetanilide.
N-methyl-2'-n-butoxy-6'-methyl-2-chloroacet-
anilide.
N-methyl-2'-sec-butoxy-6'-methyl-2-chloro-
acetanilide.
N-ethyl-2'-n-butoxy-6l-methyl-2-chloroacet-
anllide.
N-methyl-2'-isopropoxy-6'-methyl-2-chloro-
acetanilide.
N-methyl-2'-isobutoxy-6'-methyl-2-chloroacet
anilide.
N-methyl-2'-isopropoxy-6'-ethyl-2-chloroacet-
anilide.
The utility of the compounds of this invention
as the active ingredient in herbicidal compositions
formulated therewith and the method of use thereof will
be described below.
Detailed Description of the invention
The compounds of this invention may be made in
a variety of ways. For example, these compounds may be
prepared by a process involving the N-alkylation of the
anion of the appropriate secondary 2-haloacetanilide
with an alkylating agent under basic conditions. The N-
alkylation process is described in Examples l and 2
herein.
~61~i~
--8--
Example 1
This example describes the preparation of one
preferred species, N-methyl-2 7 -n-butoxy-6'-methyl-2-
chloroacetanilide. In this example dimethyl sulfate is
used as the alkylating agent to prepare the N-alkyl-2-
chloroacetanilide from the corresponding sec-amide
anion.
2'-n-butoxy-6'-methyl-2~chloroacetanilide, 4.9
gms (0.02 mol), dimethyl sulfate 2.6 gms (0.02 mol) and
2.0 gms of triethyl benzyl ammonium, bromide were mixed
in 250 ml of CH2C12 under cooling. Fifty (50) ml of 50%
NaOH were then added all at once at 15C and the mixture
stirred for two hours. Water (100 ml) was added and the
resultant layers separated. The organic layer was
washed with water~ dried over MgS04 and evaporated by
Kugelrohr. ~ clear liquid, b.p; 135C at 0.07 mm Hg was
obtained in 78% yield (4.2 gms) and recrystallized upon
standing to a colorless solid7 m.p. 41-42. 5Co
Anal. Calc'd for C14H20CINO2 (%3: C, 62.33; H, 7,47;
Cl, 13.14
Found: C, 62.34; H, 7.49;
Cl, 13.16
The product was identified as N-methyl-2'-n-butoxy-6'-
methyl-2-ch]oroacetanilide.
Example 2
To a chilled (15C) mixture of 2'-n-butoxy-6'-
methyl-2-chloroacetanilide, 5.6 g (0.022 mol), diethyl
sulfate, 4.0 g (0.024 mol), and 2.2 g of triethyl benzyl
ammonium bromide in 250 ml of methylene chloride, was
added all at once 50 ml of 50~ NaOH and the mixture was
stirred for 5.0 minutes. Water (150 ml) was added, and
the resulting layers separated; the organic layer was
washed wi~h water, dried with MgSO4, then evaporated by
Kugelrohr to give 4.1 g (66~yield~ of a clear liquid,
b.p. 114C at 0.05 mm ~g.
.
. ,
-9- ~2~ S
Anal, Calc'd for C15H22CINO2 (%): C, 63.48; H, 7.81;
Cl, 12.49.
Found: C, 63.50; H, 7.~5;
Cl, 12.48.
The product was identified as N-ethyl-2'-n-butoxy-6'-
methyl-2~chloroacetanilide.
Examples 3-19
Following substantially the same procedures,
quantities of reactants and general conditions described
in Examples 1 and 2, but substituting the appropriate
sec-anilide to obtain the corresponding N-alkylated end
product, other N-methyl-2-haloacetanilides according to
the above formula were prepared; these compounds are
identified in Table 1.
-10- 12~ 5 AG-1223
oo o ~r co ~ o ~ o o -~ ~ ~ o ~ ~ ~ ~ ~ u~ ~ ~r ~ ,1 ~`
co ~ oo ~ t~ ~ 1 O O C~ o ~ ~r ~ ~ -n ,l ~ r` ~D
~ ... .... ... ... ... ... ... ...
O ~ r` ~ o t--~ ~ ~--~ ~ I` ~ ~ r~ ~ ~ ~ ~ ~ t--~ ~ D ~r
h ~ ~1 ~9 ~1 ~ _I ~ ~1 ~D ,1 ~D ~1 ~D .-1 n _i
U~ ~
~,~
,1 ~ o co ~ er ,~ o o co ~7 ~ ~ ~ ~ _I ~ ~r ~1 ~D
,1
~ C~ C) U ~ U ~ C~ U :r: C) u m
_l
o ~ ~ ~ o .
~C o u~ o u~ r~ ~ ~ ,I Ln ~ ~1
~0 ~, ~0 00 _~O I I -
~ ~ O 0 ~ 0 ~ 0 ~ 0 ~ ~
H~ _
0~ 0~ 0~ 0~ 0 0~ 0~ 0
z z æ æ z; z æ z;
U ~ C~ ~) ~ U C~
5~ ~ ~ ~0 0 CO o C~ O
O ~ C $ ~ $
e~
U ~ C~ V
o t) ~ C~ o o o c) o a) x o I ~ c~
~ ~ 9 ~ ~ t) o ~ o I a~
~ ~ O ~ ~ O X S~ ~0
~:3 ~ I O ~ I Ll SAI O ~ O O X ~1
~0 ~ O I 0 ~0 ~ ~ O ~-1 0 0
O r~ ~1 0 r-l O O O ~1 ~ ~
O - ~a - ~ . ~ . ~ .. I .. ~ _ I _ ~
S~ ~ O S a) ~ ~ ~ ~ Q
æ~s ~ æ~ ~ æ~D ~ z~ ~ æ~D ~ z~ Z.9 ~
Q.
O ~ ~ ~ o
X Z
-
3L~ 6i5 AG-12 2 3
~:1 ~ In a~ O ~ ~ U~ r o o~
~ ... ... ,..... ... ...
h ~D ~ ~ ~ ~ ~9 ~ ~D ~i ~D ~1 ~o ~ ~o ~1
U~ ~
u~ ~ ~ ~ O o~ ,1 ~ ~ r o~ ~ 1--~ co ,~ o~ a~ ,1 ~ ~ ~ o c~ ~ ~
... ... ... ... ... ... ... ...
w u~u ~ u m z um u c~ m o ~ m u u mu v~cc
-
~J
U-- o o
_m o co u~ 0 ~ O ~D
. ~ o ~ ~ I O ~ O O O I Q, ~ O ~ O
P~ ~ ~ ~ o ~
O ~-; o , o ~ o o o ~ Ei
~~q ~ ~
H
O O O O O O O O
d ~1:1 Z Z Z 'Z Z Z Z Z
~n~ ~ ~ ~1 ~ ,~
~ ~ U C~ U U C~ ~ U V
E~~ I E; ~r ~`I o o ~ t'`l
o :c ~ :r m m ~ m
o ~ U ~ C~
, x I
~1~`3 X O ~C U O o ~ o o ~ ~ I
.C I O ~ O (~ Ql ,I X ~ ~ ~1 ~ I
J' ~ ~ ~ s o .s ~,~ ~ _l ~ I
O ~ h c~ ~ o X U
OJ O ~1 0 Q~ J I o J ~3,~ r
Q '~ U ~ ~I Q ~
O - ~ ~ S ~:
N ~9 ~ N I N I ~ ~ ~ ~ N
s x o ,S ~ ~ .c ~ ~ s ~1 ~ ~ ; ~ 5 x o s ~ o
o s~ ~ I-rl ~ O ~ ' ~ X ~ -
o ~ ~ a) ~ o ~ o o
~ z ~ ~ z ~o ~ rz 1~ ~ Z ~ Z U~ 1~ Z ~ U Z Q V --
a~
Q~
O 'I ~ ~ ~r Lr) ~D r~ co
Z ~1 ~1 ~ ~ ~ ~
- L 2 ~ L~5 AG-l ~ 23
;r ~
~ . . .
o ~ CO ,~
~4
U~
.,, ~
U~ ~ ~ o
~ ~1 I
_
~ C) ~r co
~1 ,,
~v
,_
o l:i _~
U~
. ~ ,
~o P~ ~ ~ o
v m--
H
O
Z;
~ ~ ~ ~1
El ~1 ~ N
O ~
E4 ~D
C~
-I O
~ O
~ l l
_~
O
P' --IJ
~ I Ei~
~) ~ I
I . .,
r~
I ~rl
~ ~1 ~
~X
0
ZQ ~
o
Z ,
X
~3
The secondary anilides u~ ~a~s ~ ~rting
materials in the above N-alkylation process are prepared
by known methods, e.g., haloacetylation of the
corresponding aniline. For example, the starting sec-
anilide used in Example 1 was prepared as follows:
2-n-butoxy-6-methylaniline, 27.4 g tO.0153
mol), in 250 ml of methylene chloride was stirred
vigorously with a 10% sodium hydroxide solution (0.25
mol) while a solution of chloroacetyl chloride, 17.4 gm
(0.0154 mol), in methylene chloride was added over 30
minutes keeping the tempera-ture between 15-25C with
external cooling. The reaction mixture was stirred for
a further 60 minutes~ After the addition was complete,
the layers separated and the methylene chloride layer
washed with wa~er, dried and evaporated in vacuo to
obtain 28.3 g of a white solid, ~.p. 127-128C.
Anal. Calc d for C13H18CINO2 (%): C, 61.05; H, 7.09;
Cl, 13.86.
Found: Cl 61.04; H, 7.08;
Cl, 13.86.
The product was identified as 2'-n-butoxy-6'-methyl-2-
chloroacetanilide.
The secondary anilides used as starting
materials in Examples 3-19 were prepared in a similar
manner.
The primary amines used to prepare the above-
mentioned secondary anilides may be prepared by known
means, e.g., by catalytic reduction of the corresponding
2-alkoxy-6-alkyl-nitrobenæene in ethanol using platinum
oxide catalyst.
As noted above, the compounds of this
invention have been found to be e~fective as herbicides,
particularly as pre-emergence herbicides, although post-
emergence activity has also been shown. The pre-
emergence tests referred to herein include both
greenhouse and field tests. In the greenhouse tests,
the herbicide is applied either as a surface application
after planting the seeds or vegetative
-:~
~ / .
-14
propagules or by incorporation into a quantity of soil
to be applied as a cover layer over the test seeds in
pre-seeded test containers. In the Eield tests, the
herbicide is pre-plant incorporated ("P.P.I.") into the
soil, i.e., the herbicide is applied to the surface of
the soil, then incorporated therein by mixing means
followed by planting of the crop seeds.
The surface application test method used in
the greenhouse is performed as follows:
Containers, e.g., aluminum pans typically 9.5"
x 5.25" x 2.75" (24.13 cm x 13.34 cm x 6.99 cm) or
plastic pots 3.75" x 3.75" x 3" (9.53 cm x 9.53 cm x
7.62 cm3 having drain holes in the bottom, are level-
filled with Ray silt loam soil then compacted to a level
15 0.5 inch (1.27 cm~ from the top of the pots. The pots
are then seeded with plant species to be tested, then
covered with a 0.5 inch layer of the test soil. The
herbicide is then applied to the surface of the soil
with a belt sprayer at 20 gal/A, 30 psi (187 1/ha, 2.11
20 kg/cm2). Each pot receives 0.25 inch (0.64 cm) water as
overhead irrigation and the pots are ~hen placed on
greenhouse benches for subsequent sub-irrigation as
needed. As an alternative procedure, the overhead
irrigati-on may be omitted. Observations o~ herbicidal
effects are made about three weeks after treatment.
The herbicide treatment by soil incorporation
used in greenhouse tests are as follows:
A good grade of top soil is placed in aluminum
pans and compacted to a depth of three-eights to one-
half inch from the top of the pan~ On the top of thesoil is placed a predetermined number of seeds or
vegetative propagules of various plant species. The
soil required to level fill the pans after seeding or
adding vegetative propagules is weighed into a pan. The
soil and a known amount of the active ingredient applied
in a solvent or as a wettable powder suspension are
thoroughly mixed, and used to cover the prepared
O, ~
-15- ~2~
pans. After treatment, the pans are given an initial
overhead irrigation of water, equivalent to one-fourtn
inch (0.64 cm) rainfall, then watered by subirrigation
as needed to give adequate moisture for germination and
growth. As an alternative procedure, the overhead
irrigation may be omitted. Observations are made about
2-3 weeks after seeding and treating.
Tables II and III summarize results of tests
conducted to determine the pre-emergence herbicidal
activity of the compounds of this invention; in these
tests, the herbicides were applied by soil incorporation
and sub-irrigation watering only; a dash (-) means that
the indicated plant was not tested. The herbicidal
rating was obtained by means of a fixed scale based on
the percent injury of each plant species. The ratings
are defined as follows:
% Control Rating
_ _
0-24 o
25-49
50 -74 2
75-100 3
The plant species utilized in one set of
tests, the data for which are shown in Table II, are
identified by letter in accordance with the following
25 legend: -
A Canada Thistle E Lambsquarters I Johnsongrass
B Cockelbur F Smartweed J Downy Brome
C Velvetleaf G Yellow Nutsedge K Barnyardgrass
D Morningglory H Quackgrass
~ i
.~ `,
-16~ S
Table II
Pre-Emergent
Plant Species
Co~pound of
Example No. kg/h A B C D E F G H I J K
1 112 33333333333
56 32 2 33333333
211.2 3 1 1 2 3 3 - 3333
5.6 30113 3 - 3 1 33
311.2 3 2 33 3 3 33333
5.6 313 2 3333233
4 11.2 32333333333
5.6 21323333333
11.2 3 2 333333333
5.6 32333333333
6 11.2 32 2 3 3333333
5.6 322033333233
7 11.2 333333 3 333 3
5.6 3123333 3 3 33
8 11.2 3 23333331 3 3
5.6 32223333333
9 11.2 30333333333
5.6 30 2 33333333
1.12202331 2 3 1 3 3
11 . 2 2 2 33333 3 333
- 5.6 31323223233
11 112 32 2 33333333
56 22 2 2 3233333
12 11 2 3 2 2 3 3333 3 3 3
56 31133233233
13 11.2 - 2 2 2 3 333 ~ 33
5.6 ~ 11133 2 3 - 33
14 11.2 31333233333
5.6 00233233133
11. ~ 11233333333
5.6 2012213203 3
16 11. 2 3 1 1 2 3 3 3 3 3 3 3
5.6 2000323 3 333
-17- ~2~6~6~
Table II (Cont'd)
Pre-Emergent
Plant Species
Compound of
xample No. kg/ha A B C D E F G H I ~ K
17 11.2 31102333333
5.6 30223233333
18 11.2 32333333333
5.6 32233333333
19 11.2 31223333233
5.6 30223333133
The compounds were further tested by utilizing
the above procedure on the following plant species:
L Soybean R Hemp Sesbania
M Sugarbeet E Lam~squarters
N Wheat F Smartweed
O Rice C Velvetleaf
P Sorghum J Downy Brome
B Cocklebur S Panicum Spp.
Q Wild Buckwheat K Barnyardgrass
D Morningglory T Crabgrass
The results are summarized in Table III.
-18~ ?~
Table III
Pre-Emergent
Plant Species
Compound of
Example No. k~/ha L M N O P B Q D R E F C J S X T
1 5.6 3333333333333333
1.12 2323312233313333
0.28 0213312123303333
0.06 0111312012203333
0.01 0000001011100133
0.006 00000 - 0011000232
2 5.6 123331123331333 -
1.12 023330103330333 -
0.28 012220003110333 -
0.06 000200003000113 -
0.01 000100001000001 -
3 5.6 2333323333333333
1.12 1333322023323333
0.28 1223~3010 ~ 3303333
0.06 0111000003100333
0.01 0000301000002333
0.006 0000000001100011
4 506 2333333333323333
1.12 0223313233223333
0.2~ 02333 - 1333113333
0.06 01113 - 0010003333
0.01 0000000 - 00000123
5.6 3333323333333333
1.12 2333313333323333
0.~8 0222311133323333
0~05 0112200033312333
0.01 0000000011100133
0.006 0100000021100012
6 5.6 333332323333333 -
1.12 233331222332333 -
0.28 02133 ~ 112322333 -
0.06 010000001310333 -
.01 000100101100203 -
7 5.6 1333313333333333
1.12 0333303333323333
: 0.28 0232202223213333
: 0.06 0211110322111333
0.01 1101000110001023
~: ~ 0.006 0000000120001022
~' i'~i' - .
Table III (Cont'd)
Pre-Emergent
Plant Species
Compound of
Example No. kg/ha L M N O P B Q D R E F C J S K T
8 5.6 2 33331 2 333333333
1.112 0 2 2 3302 2 2 3 2 1 3333
0.28 0 2 2 33010 2 3 2 0 3333
0.06 0 1 0 2301001001 2 33
0.01 0100000013 2 0 0 1 3 3
9 5.6 33333 2 33333333 3 3
1.12 1 2 3331 2 2 2 3113333
0.28 0 1 2 2 2 0 1 3 2 3 2 1 2 2 33
0.06 0 1 2 1 1 0 0 0 2 0 2 0 0 2 33
0.01 0 1 2 0 0 0 0 0 2 1 1 0 0 0 2 3
5.6 2 2 33303333 2 33333
1.12 0 2 2 3311233 2 2 3333
0.28 0 2 1 3302 2 2 30 2 3333
0.06 0 1 0 1 2 0 0 0 3 2 0 2 3333
0.01 0100000010010003
11 5.6 1 333313333313333
1.12 0 1 2 33022 2 3303333
0.28 0 1 2 33-0113303333
0.06 - 00121000 2 3202233
0.01 0000000000000013
12 5.6 2 2 33313133313333
1.12- 0 2 33313 2 33313333
0.28 0 2333000132033 3 3
0.06 0 0 2 3302001203333
0.01 0000000020001033
13 5.6 1 23 2 32333332333 -
1.12 0223312 2 3331333 -
0.28 0 2230011 2 3 2 0 2 33 -
0.06 0 1 1 1 0 0 0 0 1 210033 -
0.01 000000000010101 -
14 5.6 33333133333 2 3333
1.12 23 2 33023333 2 3333
0.2~ 22 2 2 3023 2 2 2 1 3333
0.06 0 2 1 2 1 0 1 2 1 2 2 0 2233
0.01 0 1 1 1 0 0 1 1 1 1 0 0 0 0 2 3
0.006 0 1 0 1 0 0 1 1 1 1 0 0 0 0 1 3
5.6 23333133333 2 333 3
1.12 0 2 3331 2 1 1 3203333
0.28 0 :L 1 1 1 0 1 0 0 1 1 0 3333
0.06 0 1 0 0 0 0 0 0 0 1 0 0 0 2 3 3
0.01 0 0 0 0 0 0 0 0 0 1 1 0 0 0 2 2
, ~ .
-20~
Table III (Cont'd)
Pre-~mergent
Plant Species
Compound of
Example No. kg/ha L M N O P B Q D R E F C J S K T
16 5.6 133331223331333 -
1.12 022330212230333 -
0.28 021330001330233 -
0.06 010100003100323 -
0.01 000000000000111 -
17 5.6 033330113331333 -
1.12 022330102220333 -
0.28 021320001010333 -
0.06 000100001100113 -
0.01 0 0 0 0 0 - O O O O O O O O 1 -
18 5.6 3333333333323333
1.12 0333200333223333
0.28 0223302023213338
0.06 0200202002303333
0~01 0200000000 - 00033
-21- ~Z~ 5
The herbicides of this invention have 'Deen
found to possess unexpectedly superior properties as
pre-emergence herbicides, most particularly in the
selective control of the hard-to-kill annual weeds,
Texas panicum, seedling johnsongrass, shattercane,
alexanderyrass, wild proso millet, red rice and
itchgrass, while also controlling or suppressing many
other less-resistant perennial and annual weeds.
Selective control and increased suppression of
the above-mentioned weeds with the invention herbicides
have been found in a variety of crops including
soybeans, cotton, peanuts, rape and snap beans (bush
beans). Selectivity has been shown in some tests at
varying rates of application in sugarbeets and garden
peas; however, some crops, particularly grass crops, are
usually less tolerant to the invention herbicides than
are the foregoing cropsn
In order to illustrate the unexpectedly
superior properties of the compounds of this invention
both on an absolute basis and on a relative basis,
comparative tests were conducted in the greenhouse with
compounds of the prior art most closely related in
chemical structure to the invention compounds~ The
prior art compounds are identified as follows-
A. N-tert-butyl-2-methoxy-2-chloroacetanilide.
(E~ample 13, U.S. Patent No 3,268,584)
B. 2'-t-butyl-6'-methoxy-2-chloroacetanilide.
(Example 67, U.S. Patent No. 3~442,945)
C. N-isopropyl-2-chloroacetanilide (common name
"propachlor'l~. U.S. Patent NoO 2,863l752
(Re Patent No. 26,961);
Propachlor is referenced in the above-
me~tioned U.S. Patent Nos. 3,773,492 and
4,152,137 and is the activ~ ingredient in
the commercial hexbicide "Ramrod~", a
registered trademark of Monsanto Company.
In the discussion of data below, reference is
-22- ~ 6~
made to herbicide application rates symbolized as "GR15"
and "GR85", these rates are given in kilograms per
hectare Skg/ha) which are convertible into pounds per
acre (lbs/A) by dividing the kg/ha rate by 1.12. GR15
defines the maximum rate of herbicide required to
produce 15% or less crop injury, and GR85 defines the
minimum rate required to achieve 85% inhibition of
weeds. The GR15 and GR85 rates are used as a measure of
potential commercial performance, it being understood,
of course, that suitable commercial herbicides may
exhibit greater or lesser plant injuries within
reasonable limits.
A further guide to the effectiveness of a
chemical as a selective herbicide is the "selectivity
lS factor" ("SF") for a herbicide in given crops and weedsO
The selectivity factor is a measure of the relative
degree of crop safety and weed injury and is expressed
in terms of the GR15/GR85 ratio, i.e., the GR15 rate for
the crop divided by the GR85 rate for the weed, both
rates in kg/ha (lb/A). In the tables below, selectivity
factors are shown in parenthesis following the GR85 rate
for each weed; the symbol "NS" indicates "non-
selective." Marginal or questionable selectivity is
indicated by a dash (-); a blank space means that the
indicated plant was not in the test or that the plant
failed to germinate.
Since crop tolerance and weed control are
inter-related, a brief discussion of this relationship
in terms of selectivity factors is meaningful. In
-30 general, it is desirable that crop safety factors, i.e.,
herbicide tolerance values, be high, since higher
concentrations of herbicide are frequently desired for
one reason or anothex. Conversely, it is desirable that
weed contxol rates be small, i.e., the herbicide
possesses high unit activity, for economical and
possibly ecological reasons. ~owever, small rates of
application of a herbicide may not be adequate to
control certain weeds and a larger rate may be
-23-
required. Hence the best herbicides are those which
control the greatest number of weeds with the least
amount of herbicide and provide the greatest degree of
crop safety, i.e., crop tolerance. Accordingly, use is
made of "selectivity factors" (defined above) to
quantify the relationship between crop safety and weed
control. With reference to the selectivity factors
listed in the tables, the higher the numerical value,
the greater selec-tivity of the herbicide for weed
control in a given crop.
In a first comparative test, greenhouse pre-
emergence herbicidal activity data are presented in
Table IV comparing the relative efficacy of the compound
of Example 1, representative compounds of this
invention, with relevant compounds of the prior art,
vi~., Compounds A, B and C, as selective herbicides
against particular weeds commonly associated with
soybeans. The test data in Table IV for all compounds
was obtained under identical test conditions, i.e., soil
incorporation with an initial overhead irrigation; the
data represent the averages of two replicate runs for
each compound; two different samples o~ the compound of
Example 1 were used and the data in the table represent
- the average from both test samples. The weeds used in
-25 the tests herein have the following abbreviations in the
tables: Texas panicum (TP), seedling johnsongrass
(SJG), shattercane (~C), alexandergrass (A&), wild proso
millet (WPM), fall panicum (FP), red rice (RR) and
itchgrass (IG).
-~4- AC; 1223
~ô
V I I I ~
H _ _ _ _
~ ~ ~ O
J~
P~ I I I
~_ _ _ _
~ ~ ~ Co
. A A ~
~ ~
o
~ _ a~ ~
~ I I A A
c~
,~ ~ ~ o
r-i ~1 0 D
~ J~ V
~1
~^ ~ I I I U~
1~ ~ r~
K -- ~ ~ A
~ ~ ~ o
~ . ,V¢
~ ~ ~ o
.
~) ~
o
A A `~
_
~ I I I A
tn ~ ~ c~
o
~ ~ ~ o
/~ ~\ A V
U~
~ ~,, ~D .
,~ ,1
.~ i o
/~ A A
u~ ~ Q
~ ~ X ~ /~
~ ~ m c~
-25- ~2~6~
Reference to the data in Table IV will sho~7
that with respect to weed control, none of the prior art
compounds exhibited positive selective weed control
against any weed in soybeans at the maximum rate of
application, i.e., 1.12 kg/ha, but for the sole
exception of Compound C against fall panicum, and even
there, the selectivity factor was one-fold less than
that for the compound of Example 1. In marked contrast,
the compound of Example 1 selectively controlled every
weed in the test at extremely low rates of application~
while maintaining soybean safety up to 0.71 kg/ha. Of
particular note is the fact that the compound of
Example 1 controlled seedling johnsongrass, shattercane,
alexandergrass, fall panicum and itchgrass; at 0.07
kg/ha (the minimum rate used) or less and also
controlled the remaining weeds, i.e., Texas panicum,
wild proso mille~ and red rice a~ rates of only 0.10,
0.14 and 0.18 kg/ha, respectively.
Additional tests were conducted in the
greenhouse in order to compare the relative herbicidal
efficacy of prior art compounds A-C with the compounds
of Examples 1, 3-5 and 8-17, representative of the
invention compounds. The tests were conducted by soil
incorporation of the herbicide at application rates
within the range of from 0.07 to 1.12 kg/ha (0.0625-1.0
lb/A) and an initial overhead irrigation followed by
subsequent subirrigation watering as needed.
Observations were made 19 days after treatment. The
data from the additional tests are shown in Table V; the
names of the weeds are abbreviated as in Table I~ and
selectivity factors are shown in parentheses after the
GR85 rates for each weed.
~3~
- 2 6 - A~1223
o o ~n ~ o o i o ~ _ O o
_ _ ,i ~ ~ co co ,iu~ J
A ~ Z ~ A i
i O ~ a:~ o 1`
i ~i ~ ~ ~i ~ ner In O ~
,i O O O o ,i~1 0 0 o O O o
_ ~ ô o o ô ~ _ o o o o o
o o ~ o
~ O ~ O ~O
oa~ r 5~
o o o o o o o o o o o o
~i~iooooooooooooo
V V V Y V V V V V V V V
O O o o O , o O
ri
I i I ~ ~ A A A,i A f~ r ,i A
i~ _ _ _ _ _ _ _ __ _ ~_ _ _ _
~i ~~-i O O O O O~i 0 00 0 ~ O
A/~ V
_ ~ ô o ô ô _ o ô
o o ~ Oo~ ~ o c~ ~
A
o
,i o,i o o o o ,i i Oo ,
~ ~:~ ~ i ~ V
~_ _ ~ ~ _
~ ~ o _ o ~ w ~ _ ô
C~ ~ O O
~ ^ ~ r-lCO r--i ~ir i ~ ~ ~r1~ ~ ~i
C) I I I A A ~ ~ J~ A A ~ ~ A
t~ ~i ~ 1~ ~ o )ct:~ oo~
r-i r--i~i O ~i O O O In
~i r-i~i O C) O O O O O O O O O r i
A A ~ V V
_ _ _
OOO~ OOO
~D ~ O ~9 ~ ~ O O
i;~ '` Ai XX ~ ~; co ;; X 5;; oo co A
~ r5~
r-lr--i ~i OO O O O r iO O ~i O ~i
~I~i~i OO O~ C) OO OO O O O
VV VV V V
_ ~
_ o o a o ~ __ _ _
r~ ,, ,, o ~ OO O _ ~ O
' ~ ~ ~ ,O ~ O O
_ --~r i ~i~i ~ir-l C0 ~ t~i
J\ A
r~ir~i~i O O O O ~i ~i U') ~i~~1 r~
~~i~i~i O O O O C~ O OC:~ O O O O
a~ A A V
lf ) ~ ~ ~i r i r~i ~i t- i ~i ~i r-l r~i ~i ~i r~i ~i L0 r-i
t--i '~ ~ ~i r-i ~i r-i r~i ~i ~i --i --i --i ~Di ~1 .~i O ~i
A/~ A A ~~ , A
O
~ ~i~ ~Il ~ ~n ~I r~ 1~i r i ~i
6~
- 2 7 - AG-1223
O In
oo n
~ r~
o o
_
o o
r-- t~
o o
V V
o
~r
r)
o o
_ _
o ~
ô
o o
~ o
~ r--I A
O ~
V
,~ O
Q~ ~ ~
_ _
CO ~D
U~
O O
~ ~; ~
-28~ 6~
Referring to the data in Table V, it will be
noted that within the limits of the herbicide test
rates, Compound A did not selectively control any of
test weeds in soybeans CGmpound B only marginally
selectively controlled fall panicum (not a particularly-
resistant weed) and Compound C selectively controlled
only fall panicum and, marginally, Texas panicum,
alexandergrass and red rice. But for the sole
exceptions of Compound C against fall panicum (GR~5 of
0.28 kg/ha) and Compound B against alexandergrass and
fall panicum (GR85 of 1 00 kg/ha), none of the prior art
compounds controlled any of the weeds in the test at
less than 1.12 kg/ha (1.0 lb/A).
In sharp contrast, but for isolated instances
against certain weeds, all of the invention compounds
exhibited outstanding positive selective control of
every weed in soybeans. In only a few instances was the
selective control marginal, e.g~, that of the compounds
of Examples 8 and 17 against red rice; Example 9 against
wild proso millet and red rice; Example 14 against wild
proso millet and Example 15 against shattercane.
Moreover, in contrast with the prior art compounds and
again with the noted exceptions, all of the invention
compounds controlled all-of the weeds at extremely low
rates of application, ranging from no greater than 0.56
kg/ha t0.5 lb/A) downwardly to less than ~.07 kg/ha
(0.0~25 lb/A) a remarkable performance in absolute terms
in view of the highly-resistant nature of the weeds
tested (excepting fall panicum) and particularly
relative to the inability of the most relevant compounds
of the prior art to control any of the test weeds,
except as noted above.
Preferred compounds o~ this invention were
further tested in the field to determine their selective
preemergence herbicidal activity and soil longevity
against the annual weeds Texas panicum, bristly starbur
and Florida pusley in peanuts tFlorunner). Observations
-29- ~2~ S
were made at 4, 8 and 12 weeks after treatment (WAT) by
surface application of the herbicides; soil type was a
Dothan sandy loam with 1.3~ organic matter; the results
are shown in Table VI.
:~%~ 5
P~12~3
~ , $U~ o, U~$
.~ ~ u~ ~ c~ c~ ~ u~ r oo LO co oo co
'~ o l~ I ~ ,,,,
ou~ o I I Ln Ln
~ I
~ j o ~ ~o o ~o~
.~ ~1
er
~ ~ 1~ o ~o
~1 ~ ~ I ~
P o ~ o
u~ ~ ~ o ~ o In c~ O
er 00 ~
~ ooo,1 oo~u~ ooo~ ~
~I ~
~1 o~ 0~0~ oO~
~!
o ~ ~ o o ~ s) o u~
er
~ O ~ '
The data in Table VI show ~ha~ ~ eS compound of
Example 2 selectively controlled all three weeds in
peanuts-at rates within the range of 2.24 to 4.48 kg/ha
for up t.o 12 WAT. Selective control of one or more of
the test weeds was also exhibited by the compounds of
Examples 1 and 3 at lesser rates for up to 12 WAT,
indicating that of the three test compounds, the
compound of Example 2 had the highest safety factor in
peanuts under conditions of this test.
Yet other tests were conducted in the field to
determine the relative efficacy of the compounds of
Examples 1, 3 and 4 against wild proso millet in
soybeans for a period up to 12 weeks after treatment
when applied either as surface applications (SA) or pre-
plant incorporated (PPI). The soil was a sandy loam
with 1.7% organic matter; a 2.5 inch (6.35 cm) rainfall
occurred 2 days after treatment, the results of this
test are shown in Table VII.
s
-32- AG~1223
~1 oo o o o o ~ ~ ~ o 1` ~ co
E~ ~
~1 ~1 ~ '` ~ ~ ~ ~ u~ ~ ~ co ~ ~n
U~l ~ r~ co 1~ ~ ~` co co ~D In C
H I ~ CO O CO ~ ~ O O Lr) 1~ O CO
.~ CO
~ O CO O U~ O CO C~ 00 Cl~ O ~ O
ul U~ ~ ~ ~ co ~ ~o c~ ~o ~9 CO CO ~
O
,~, H¦ t'`l CO Lt~ t~l ~ 11~ 1~ 00 Lt~ ~r) O O
a~ ~: ~ Gl ~ I` co ~n 1` 1` c~ co oo c~ co ~
3 ~
~1
Q
H ~ :
H~ H
~ ~ O O O ~ O ~ O Co O O O O
2 ~ ~ ~ ,~ ~
~ ~1 Q ~
U~
j.~ ~ ~ ~ o co u~ ~ l`
R co ~ 1 ~ o 0 0 1` ~ a~ 1~ o L~1
:~ V~
u~ a~
O 1` 1` 0 0 L~ ~ I
, E~ ~
~ .,~
~I Ln~ oLn~o ~u~
u~
a~
~r ~D 0 ~ er ~ CO
. . . . . . . . . . . . .,~
O
O ~1 ~ ~
.. ' O S~ X X
C~ 1~
-33- ~ Z~
The data in Table VII show that a 3.36 kg/ha
rate of each compound selectively controlled wild proso
millet in soybeans for 3, 8 and 12 WAT in the surface
applications. Thus, certain treatments of the crop with
the invention compounds provided season long control of
wild proso millet, since germination and emergence of
this species increases progressively with the growing
season. The greater degree of injury to soybeans in the
PPI treatments was deemed to be due to excessively deep
and uneven incorporation by the disc harrow and the
rainfall occurring 2 days after treatment. In this
test, the surface application treatments provided
superior weed control and crop safety.
In yet another field test, the compounds of
Examples 1, 3 and 4 were tested for their herbicidal
activity on the very resistant annual weed seedling
johnsongrass with both surface application and pre-plant
incorporation herbicide treatments. This field test was
conducted in a clay soil (58% clay and 3.1~ organic
matter). Observations were made at 4 and 8 weeks aEter
treatment; the results are shown in Table VIII.
- 34- ~ C6~ i AG 1223
¢1 o o o co ~ ~ co ooco co oo u~ 0
C'~l ~ co co 1~ c~ ~D r--~o 1~ co co ~
0 ~ h
~f ~0
o H ~ ~ o u~ C~') ~ r~ oo
o co 0
O rl
~L
~I ~ r~
a~ ~ o
u~ ~ ~1 1` u~ oo o r~ 1~ o co r~ V ~ u~ bO
~ P~
.,_
~ C~
.
.
~1 l ~ o r~
~ L) E~ U~
¢ au H ~ 00 ~ 00 ~') ~) C~l ~ CO CO O 00
E~ P~ ~ P~
o ¢1 ~ C~ ~ ~ ~ CO ~ o ~ c~
E~ ~ I ~ ~ ~ ~ ~ ~ ,
~ ,
H ul C') ~) OO C~l CO C~l O ~') ' ) c~
I:~j
t~l OC .... .... ....
'O
O X X X
E3
C~
,~
~L2~
-35-
The compound of Example 4 selectively
controlled seedling johnsongrass in soybeans at the 2.24
kg/ha for as long as ~ weeks after treatment under PPI
conditions and at the 3.36 and 4.48 kg/ha rates under
surface application conditions. The compound of Example 1
selectively controlled seedling johnsongrass at the 3.36
kg/ha rate for at least 4 weeks after treatment under
surface application conditions.
As indicated by data in the above tables,
compounds according to this invention are suitable used
under either surface application or soil incorporation
treatments, the preferred treatment depending upon
various factors such as soil, climate, etc.- Generally
however, surface application of the herbicides are
preferred over soil incorporation.
In laboratory tests to determine the
resistance of the herbicide to leaching into the soil
and resulting herbicidal efficacy, the compound of
Example 1 was formulated in acetone and then sprayed at
different concentra~ions onto a weighed amount of Ray
silt loam contained in pots having filter paper covering
drainage holes in the pot bottoms. The pots containing
the treated soil were subjected to leaching by placing
on~a turntable which rotated under two nozzle tips of a
water container calibrated to deliver one inch (2.5 cm)
of water per hour simulating rainfall. ~eaching rates
were adjusted by varying the amount of time on the
turntable. Water was delivered to the soil in the pots
and allowed to percolate through the filter paper and
drainage holes. The pots were then allowed to sit for
three days at ambient room temperature. The treated
soil in the pots was then removed, crumbled and placed
as a surface layer on top of other pots containing Ray
silt loam soil seeded with barnyardgrass seeds. The
pots were then placed on greenhouse benches, sub-
irrigated and allowed to grow for 2-3 weeks. Visual
ratings of percent growth inhibition compared to control
(untreated) pots and fresh weights for barnyardgrass
were made 18 days after treatment and recorded; the data
-36- ~2~6~
from three replications of these tests are shown in
Table IX.
Table IX
- Barnyardgrass
Percent Fresh Percent
Compound Rate Rain Inhibition Weight of
of Ex. 1 (Kg/Ha) (Cm) (Avg. of 3 replications) Controls
2.24 0 100 0 0
0.64 100 0 0
1.27 100 0 0
2.54 100 0 0
5.08 100 0 0
10.16 95 0 0
0.56 0 100 0 0
0.64 100 0 0
1.27 100 0 0
2.54 100 0 0
5.08 95 0 0
10.1695 ~ 0 0
0~14 0 100 0 0
0.64 100 0 0
1.27 100 0 0
2.54 95 0 0
5.0~ 95 0.20 3.3
10.16 ~0 0.83 14.1
The data in Table IX indicate that the
compound of Example 1, representative of the invention~
compounds, was quite resistant to leaching into the soil
under conditions of heavy rainfall and exhibited-no less
than 90~ control of barnyardgrass at application rates
as low as 0.14 kg/ha (0.125 lb/a) under 10.16 cm of
rainfall.
A distinct advantage of a herbicide is its
ability to function in a wide variety of soil types.
Accordingly, data is presented in Table X showing the
herbicidal effect of the compounds of Examples 1 and 3
on alexandergrass (AG) and barnyardgrass (BYG) in
soybeans in a wide variety of soil types and organic
matter content. The herbicide treatments were applied
by surface application with overhead irrigation as
;~. ',
,i,, .:~,
described above; selectivity factors for the weeds are
shown in parentheses after the GR85 rates for the weeds.
-38- AG--1223
~2~6~5
_ C ~ .,. .. , o o o o o
O
~A N U~ 1 Z--I Z;
Co ~
__ _ _ __ ____ __
~D ~ ~r co ~ ~r q~ e~ er ~
.. . .. . .. . - ~3
:` o o o o o o ~ t`l ~J ~`I o O
00 ~ ,a ~, v
U~
; C
-- O
~!1 ~ ~ O 1` o o o oo o c:~ o ~1
.. , ,, .. . -
~ CO CO O
~p 00 ~1 ~ ~r ~ ~~ ~ er ~r Q
~1 ~1 r~ ~ ,~ ,1 ~ ~~ ~ ~ ~1 0
.. .. .. .. ..
V V ~ O o o o ,~ o
~ "
,~~ ~ ~ ~
~a~ ~: ~ .,,
r~~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~r ~ ~ ~ ,
E~ ~ ~ _I ,1 ~ ~ ~ ~ r-l ~ ~ ~~1 ~1
In ~ ~ .. . .. .. .. .. Q~
_ o~ ~ y
C~ U~
4~
I O
o 0 C7 tO
~I 0~ . I O .
a~ ~ I O ~ a~
s~ ~
S~
~ ~1 o r7 0 a~
O ,I t~l ~D u~ ~ t' a~ ~
5~ 0
Q~
aJ U~
: o
O
C
~ O ~ ~ C)
0 1:
O ~ 0:
ul X X :~ X X F: X X ~1 X X ~I X X ~1 O X
.,, ~) ~ ~ ~ ~ o o ~ ~ ~
O ~ O
u~r~ u~ a v
-39- ~6~
The data in Table X show that the invention compounds
were largely insensitive to soil type. In more
particular, the compound of Example 1 exhibited positive
selective control of alexandergrass and barnyardgrass in
soybeans in all soil in the test containing organic
matter ranging from 1.0~ O.M. content in ~ay silt loam
to 22.1% O.M. in Florida muck soil. Similarly, the
compound of Example 3 exhibited positive selective
control of the weeds in test in soybeans in all soil
types, except against barnyardgrass in Florida sand
(6.8% O.M.) and Florida muck. Since the compound of
Example 3 did selectively control both alexandergrass
and barnyardgrass in Drummer silty clay loam soil having
approximately the same organic matter content as Florida
sand, but a much higher clay content (37.0~) and in
soils having higher O.M. and clay content as in
Brazilian sandy clay loam, it is believed that the low
clay content (1.8%) in the Florida sand contributed to
non-selective control of barnyardgrass in that soil.
The compounds of this invention have their
most important application in soybeans and peanuts.
However, selective weed control has been established in
a variety of other crops as indicated in Table III
above. In yet other tests, the compound of Example 1
was also shown to be useful in snap beans and garden
peas at rates up to 1.0 lb/a, in cotton, rape, carrot
and red beet up to 0.5 lb/a or more and in alfalfa, flax
and cabbage on the order of 0.25-0.5 lb/a.
Toxicology studies on the compounds of
Examples 1, 3 and 4 have indicated the following
properties:
-40~ 5
Compound o~
Toxicoloyy Example No.
1 3 4
,
OLD50, Mg/Kg 3370 2300 2400
DLD, Mg/Kg. >2000>1000<1260 >3100<5010
~ye irritation slightsevere moderate
Skin irritation nonecorrosive corrosive
The corrosive nature of the compound of Example 3 may be
due to a contaminant, dimethyl sulfate, found in the
preparation of the sample on which toxicology studies
~ere conducted. It is apparent that the above compounds
may be safely used with the normal degree of care
re~uired for compounds having the indicated
toxicological properties. The indicated relative degree
of safe handling characteristics for the compounds of
the respective examples appears to be:
Example 1 > Example 4 > Example 3.
Therefore, it will be appreciated from the
foregoing detailed description that compounds according
to this invention have demonstrated unexpected and
outstandingly superior herbicidal properties both
absolutely and relative to the most structurally-
relevant compounds of the prior art, one of which(Compound C) is a commercial herbicide. More
particularly, the compounds of this invention have
proven to be outstanding selective herbicides,
particularly in the control of hard-to kill annual
grasses in soybeans, peanuts and other crops. In more
particularr compounds according to this invention
exhibit outstanding control of the annual grasses Texas
panicum, itchgrass, wild proso millet, alexandergrass,
seedling johnsongrass, shattercane and red rice, while
controlling and/or suppressing other less-resistant
annual grasses and perennials, including those mentioned
in Tables II and III above and others such as bristly
starbur, Florida Pusley, etc,
~Z~6~6~;
-41-
The herbicidal compositions of this invention
including concentrates which requi,re dilution prior to
application contain at least one active ingredient and
an adjuvant in liquid or solid form. The compositions
are prepared by admixing the active ingredi.ent with an
adjuvant including diluents, extenders, carriers and
conditioning agents to provide cornpositions in the form
of Einely-divided particulate solids, yranules, 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 compositions of this invention,
particularly liquids and wettable 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,
-42- ~206~S
cationic and non-ionic 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 esters of sodium
isothionate, esters of sodium sulfosuccinate, sulfated
or sulfonated fatty acid esters, petroleum sulfonates,
sulfonated vegetable oils, ditertiary acetylenic
glycols, polyoxyethylene derivatives of 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 cellulose, polyvinyl
alcohol, sodium lignin sulfonates, polymeric alkyl,
naphthalene sulfonates, sodium naphthalene sulfonate,
and the polymethylene bisnaphthalene sulfonate.
Wettable powders are water-dispersible
compositions containing one or more active ingredients,
an inert solid extender and one or more wetting and
dispersing agents. The inert solid extenders are
usually of mineral origin such as the natural clays,
diatomaceous earth and synthetic minerals derived from
silica and the like. Examples of such extenders include
kaolinites, attapulgite clay and synthetic magnesium
silicate. The wettable powders compositions of this
invention usually contain from about 0.5 to 60 parts
(preferably from 5-20 parts) of active ingredient, from
about 0.25 to 25 parts (preferably 1-15 parts) of
wetting agent, from about 0.25 to 25 parts (preferably
30 1.0~15- parts) of dispersant and from 5 to about 95 parts
(preferably 5-50 parts) of inert solid extender, all
parts being by weight of the total composition. Where
required, from about 0.1 to 2.0 parts of the solid inert
extender can be replaced by a corrosion inhibitor of
anti-foaming agent or both.
; Other formulations include dust concentrates
~2~
-43-
comprising from 0.1 to 60% by weight of the active
ingredient on a suitable extender; these dusts may be
diluted for application at concentrations within the
range of from about 0.1-10% by weight.
Aqueous suspensions or emulsions may be
prepared by stirring an aqueous mixture of a water-
insoluble active ingredient and an emulsification agent
until uniform and then homogenized to give stable
emulsion of very finely-divided particles. The
resulting concentrated aqueous suspension is
characterized by its extremely small particle size, so
that when diluted and sprayed, coverage is very uniform.
Suitable concentrations of these formulations contain
from about 0.1-60% preferably 5-50% by weight of active
ingredient, the upper limit being determined by the
solubility limit of active ingre~ient in the solvent.
In another form of aqueous suspensions, a
water-immiscible herbicide is encapsulated to form
microencapsulated phase dispersed in an aqueous phase.
In one embodiment, minute capsules are formed by
bringing together an aqueous phase con-taining a lignin
sulfonate emulsifier and a water-immiscible chemical and
polymethylene polyphenylisocyanate, dispersing the
water-immiscible phase in the aqueous phase followed by
addition of a polyfunctional amine. The isocyanate and
amine compounds react to form a solid urea shell wall
around particles of the water-immiscible chemical, thus
forming microcapsules thereof. Generally, the
concentration of the microencapsulated material will
30 range from about 480 to 700 g/1 of total composition,
preferably 480 to 600 q/l.
Concentrates are usually solutions of active
ingredient in water-immiscible or partially water-
immiscible solvents together with a surface active
agent. Suitable solvents for the active ingredient of
'',, .
_44~ 5
this invention include dimethylformide,
dimethylsulfo~ide, N-methylpyrrolidone, hydrocarbons and
water-immiscible ethers, esters or ketones. However,
other high strength liquid concentrates may be
formulated by dissolving the active ingredient in a
solvent then diluting, e.g., with kerosene, to spray
concentration.
The concentrate compositions herein generally
contain from about 0.1 to 95 parts (preferably 5-60
parts) active ingredient, about 0.25 to 50 parts
(preferably 1-25 parts) surface active agent and where
required about 4 to 94 parts solvent, all parts being by
weight based on the total weight of emulsifiable oil.
Granules are physically stable particulate
compositions comprising active ingredient adhering to or
distributed through a basic matr~x of an inert, finely-
divided particulate extender. In order to aid leaching
of the active ingredient from the particulate, a surface
active agent such as those listed hereinbefore can be
present in the composition. Natural clays,
pyrophyllites/ illite and vermiculite are examples of
operable classes of particulate mineral extenders. The
preferred extenders are the porous, absorptive,
preformed particles such as preformed and screened
particulate attapulgite or heat expanded, particulate
vermiculite and the finely-divided clays such as ~aolin
clays, hydrated attapulgite or bentonitic clays. These
extenders are sprayed or blended with the active
ingredient to form the herbicidal granules.
The granular compositions of this invention
may contain from about 0.1 to about 30 parts preferably
from about 3 to 20 parts by weight of active ingredient
per 100 parts by weight of cla~ and 0 to about 5 parts
-45-
by weight of surface active agent per 100 parts by
weight of particulate clay.
The compositions of this invention can also
contain other additaments, for example, fertilizers,
other herbicides, other pesticides, safeners and the
like used as adjuvants or in combination with any of the
above-described adjuvants. Chemicals useful in
combination with the active ingredients of this
invention include, for example, triazines, ureas,
carbamates, acetamides, acetanilides, uracils, acetic
acid or phenol derivatives, thiolcarbamates, triazoles,
benzoic acids, nitriles, biphenyl ethers and the like
such as:
Heteroc clic Nitro en/Sulfur Derivatives
Y g
2-Chloro-4-ethylamino-6-isopropylamino-s-triazine
2-Chloro-4,6-bis(isopropylamino)-s-triazine
2-Chloro-4,6-bis(ethylamino)-s-triazine
3-Isopropyl-lH-2,1,3-benzothiadiazin-4-(3H)-one
2,2 dioxide
3-Amino-1,2,4-triazole
6,7-Dihydrodipyrido(1,2-a:2'rl'-c)-pyrazidiinium
salt
5-Bromo-3-isopropyl-6-methyluracil
1,1'-~imethyl-4,4'-bipyridinium
Ureas
N'-(4-chlorophenoxy) phenyl-N,N-dimethylurea
N,N-dimethyl-N'-(3-chloro-4-methylphenyl) urea
3-(3,4-dichlorophenyl)-1,1-dimethylurea
1~3-Dimethyl-3-(2-benzothiazolyl) urea
3-(p-Chlorophenyl)-l,l-dimethylurea
l-Butyl-3-(3,4-dichlorophenyl)-1-methylurea
~Z~16S
-46-
Carbamates/Thiolcarbamates
2-Chloroallyl diethyldikhiocarbamate
S-(-4-chlorobenzyl)N,N-diethylthiolcarbamate
Isopropyl N-t3-chlorophenyl) carbamate
S-2,3-dichloroallyl N,N-diisopropylthio~carbamate
Ethyl N,N-dipropylthiolcarbamate
S-propyl dipropylthiolcarbamate
Acetamides/Acetanilides/Anil-nes/Amides
2-Chloro-N,N-diallylacetamide
N,N-dimethyl-2,2-diphenylacetamide
N (2,4-dimethyl-5- [[(trifluoromethyl)sulfonyl]
amino]phenyl)acetamide
N-Isopropyl 2-chloroacetan~lide
2'~6'-Diethyl-N-methoxymethyl-2-chloroacetanilide
2'-Methyl-~' ethyl-N-(2-methoxyprop-2-yl)-2-
chloroacetanilidea,~,a -Trifluoro-2,6-dinitro-N,N-
dipropyl-~-toluidine
N-(l,l--dimethylpropynyl)-3,5-dichlorobenzamide
Acids/Esters/Alcohols
2,2-Dichloropropionic acid
2-Methyl 4-chlorophenoxyacetic acid
2,4-Dichlorophenoxyacetic acid
Methyl-2-e4-(2,4-dichlorophenoxy)phenoxy]
propionat~
3-Amino-2,5-dichlorobenzoic acid
2-Methoxy-3,6-dichlorobenzoic acid
2s3,6-T.richlorophenylacetic acid
Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-
nitrobenzoate
.~
~2~3~
-47- AG-1223
~,6-~initro-o-sec-bu~yipnenol
N-(phosphonomethyl) g1~cine and its C
monoalkyl amil~ and alk1ine m~ta1 sa~.~ and
combinations thereof
:5 Ethers
2,4-Dichlorophenyl-4-nitrophenyl ether
2-Chloro~ , a -trif1uoro-p-tolyl-~-ethoxy- .
4-nitrodiphenyl ether
Miscellaneous
2,6-Dichlorobenzonitrile
Monosodium a~id methanearsonate
Disodium me~hanearsonate
Fertilizers useful in combination with tAe active
ingredients include, for example, ammonium nitrate,
urea, potash ana superphosphale. Other useful
aaditaments include materials in which plant org~nisms
take root and grow such as compost, manure, humus, s~nd
and the like~
Herbicio~l formulations of the types described
above are exemplified in several illustrative
em~od~ments below.
I. Emulsifl~le Concentrates _ EC's~
Wei~ht Percent
A. Compound of Example No. l 35O6
C~lcium dodecylbenzene 5ul-
fonate/polyoxyethylene ethers blend
(e.g., Atlox~ 3437F) 5.0
Mono~hlorobenzene 29.7
C~ aromatic hyarocar~on 29.7
10(~. 0
,~
-48- 12~6~65 AG~
B. Compound of Example ho. 3 ~5.U
Calcium dodecyl sulfonate/al-
kylaryl polyether alcohol blend ~.U
Cg aromatic hydrocarbons solvent li.0
1~0.
C. Compound of Example No. 4 5.0
Calcium dodecylbenzene sulfonate~
polyoxyethylene ethers blend (e.g., Atlox
3437F) 1.0
Xylene 94.0
10~. ()O
II. _i~uid Concentrates
Weight Percent
A~ Compound of Example No. 5 10.0
Xylene gO.0
100.00
B. Compound of Example No. 6 ~5.0
Dimethy1 suifoxi~e 15.0
11~O . O()
~:20~ C. Compound of Example No. 18 50.0
N-methylpyrrolidone 50.0
130.
D. Compound of Example No~ 19 5.0
: Ethoxylated castor oii 2000
Rhodamine B .5
Dimetnyl formami~e 74.5
, ~ : i00.00
-49- 3~Z~S ~G~
IIl. Er.lulsions
~eignt Per~ent
A. Compound of Exdmple No. 7~0.0
Polyoxyethylene/polyoxy-
propylene block copolymer with butanol
(e.g., Tergitol~ XH) ~.0
Water 56.0
100. 00
B. Compound of Example No~ 8 5.0
Polyoxyethylene~polyoxy~
propylene block copolymer with butanol 3~5
Water 91.5
100. OU
IV. Wettable Powders
Weight pe~-cent
A. Compound of Example No. 925.0
Soaium lignosulfonate 3~0
: Sodium N-methyl-N-oleyl-taurate 1.0
Amorphous siiica (synthetic) 71.0
lOOoO0
B. Compound of Example No. 10 80.0
Sodium dloctyl sulfosuccinate 1.25
:~ Calcium lignosulfonate 2.75
~norphous si~ica (synthetic) 1~.0~
~25 100.00
C. Compound of Example No. 11 10.0
Soàiulll lignosul~onate 3.0
Sodium ~-methyl-N-oleyl-taurate l.0
: Kaolinit~ clay 86.0
100.~0
~50~ ~ 2~.
V. Dusts
weiyh~ Per~ent
A. Compound of Example No. 12 2.0
Attapulg ite 9~3 . 0
iO0. 00
B. Compound of Example No. 1360.0
Montmorillonite 40.0
100. 00
C. Compound of Example No. l~30.G
lQ ~entonite 70.0
lQ0.0
D. Compound of Example No. 15 l.0
Diatomaceous earth 99.0
100. 00
}5 VI. Granules
Weiyht Per~ent
~ ~ A. Compound of Example No. 1615~0
: Granular attapulgi~e (20/40 mesh) 85.0
100. 00
B. ompound of Example No. 17 30.0
Diatomaceous earth (20/40) 70.0
1 0 0 . O ()
C. Compound o Example NoO 18 0.5
Bentoni~ (20/40) 99.S
10~.00
D. Compound ol ExampLe No. 1~5.0
~: : Pyrophylllte ~;20/40) ~5.()
lOU. OC
'
~Z(36~i5
A~ J
VLI. ~1crocapsuies
A. Compound of Example No. 1
encapsulated in polyurea snell wall 4~.
Sodium lignosulfonate (e.g.
~~eax ~a~ )
Water ~9 9
lUOo OO
B. Compound of Example No. 3
encapsulated in polyurea shell wall 10.0
10Potassium lignosulfonate (e.g.,
Re~as C-21~ ) .5
Wa~er 89.5
10~. 0
C. Compound of Example No. 4 en-
15capsu~ated in polyurea shell wail ~0.0
: Magnesium salt of lignosulfate
(Treax ~ ~ 2.0
: Water 1~.0
1()0. 0~
20 ~ When operating in accordance with the present
: invention, effective amounts of the acetaniiides of
this invention are applied to the soiL containing the
: : plants, or are incorporated into aquatic rlledia in any
: convenient fashion. The application of liquid and
particulate solid compositions to the soil can be
carried out by conventional methods, e.g., power
d~s~ers, boom and hand sprâyers and spray dusters. The
compositions can also be applied f~om airplanes as a
dust o a spray because of t}~eir e~fectiveness at ïow
30: ~osages. The application of herbicidal compositions
: ~ to aquatic pl~nts is usually carried out by a~ding t~le
co~positions to the aquatic media in the area where
~ control of t~e a~uatic plants is desired.
: ~,
- 5 2 - ~2~6~5
Tne application of an efEective amoun~ of the
compounds of this invention to the locus of unàesired
weed~ is essential and cri~ical ~or the practice o~ th~
present invention. The exact amount o~ active
ingredient to be employe~ is dependent upon various
factors, including the plant species and stage of
developn~ent thereof, the type and condition of 50il,
the amount of rainfall and the specific acetanilide
employed. In selectlve preemergence application to the
plants or to the soil a dosage of rom 0.~2 to about
11.2 ~g/ha, preferably from about 0.04 to about 5.6
kg/ha, or suitably from 1.1~ to 5.6 kg/ha of
acetaniLide is usually employed. Lower or higher rates
may be required in some instarlces. One skilled in the
arf can readiiy determi~ne from this specification,
including the above example, the optimum rate to be
applied in any particuiar case.
The term l'soil" is employed in its broadest sense
to be inclusive o~ all conventional "soils" as defined
in Webster's New International Dictionary, Second
Edition, Unabrldged (1961). 'rhus the term refers to
any substance or media in which vegetation may take
root and grow, and includes not only ear~h but also
compost, manure, muckj humus, sand and the like,
adapted to support plant growth.
Although the inv~ntion is described with respect
to speci~ic modifications, the details t~lereof are not
to be construed as limitations except to the extent
_ndi-a~ea in ~le foilovlrg clairs.
:
