The disclosure herein relates to a group of N-alkyl-2-haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly transplant rice. The herbicides herein are particularly effective against annual and perennial weeds commonly associated with rice.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention pertains to the field of 2-haloacetanilides and their use in 
the agronomic arts, e.g., as herbicides, particularly for use in 
transplant rice. 
2. Description of the Prior Art 
The invention compounds are characterized as 2-chloroacetanilides having an 
n-butoxy radical in one ortho position, an ethyl radical in the other 
position, and as a substituent on the anilide nitrogen ring a C.sub.1-5 
alkyl radical, perferably methyl or ethyl. 
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/or on the anilide 
ring including alkyl, alkenyl, alkynyl, alkoxy, polyalkoxy, alkoxyalkyl, 
heterocyclyl, halogen, etc., radicals. The most relevant compounds of the 
prior art in this area appear to be those disclosed in the following 
references: U.S. Pat. Nos. 3,268,584, 3,442,945, 3,773,492 and 4,152,137. 
However, none of those prior art references disclose any data for 
compounds of the type disclosed herein as being useful transplant rice 
herbicides, nor do they disclose or suggest the particular species of this 
invention. 
The 2-haloacetanilides of the prior art which are known to have utility as 
transplant rice herbicides differ significantly in structure from those 
disclosed herein. Specifically, said prior art herbicides all contain 
lower alkyl radicals in both ortho positions to the anilide nitrogen atom 
and an alkoxyalkyl radical on said nitrogen atom. Accordingly, those prior 
art rice herbicides are non-related and non-suggestive of those disclosed 
herein. However, in order to provide a basis for comparison, the relative 
herbicidal efficacy of preferred compound of this invention is compared 
with that of relevant prior art herbicides; data are presented in tables 
herein. 
The above-mentioned 2-haloacetanilides of the prior art are MACHETE.RTM. 
(registered trademark of Monsanto Company), the active ingredient of which 
is 2',6'-diethyl-N-(n-butoxymethyl)-2-chloroacetanilide (common name 
"butachlor"); 2',6'-diethyl-N-(n-butoxyethyl)-2-chloroacetanilide ("ethyl 
butachlor" herein); 
2-tert-butyl-6-methyl-N-(n-butoxymethyl)-2-chloroacetanilide (common name 
"terbuchlor"), and 2',6'-diethyl-N-(2-propoxyethyl)-2-chloroacetanilide 
(common name "pretalachlor"). Butachlor and ethyl butachlor are disclosed 
as rice herbicides in U.S. Pat. No. 3,663,200; terbuchlor is disclosed as 
a transplant rice herbicide in U.S. Pat. No. 3,955,959 and pretalachlor is 
disclosed as a rice herbicide in U.S. Pat. No. 4,168,965. Of the foregoing 
herbicides, only MACHETE herbicide has achieved commercial status. 
While the above rice herbicides have been found useful, there is a 
continuing need for improved rice herbicides which control resistant weeds 
of economical significance at lower rates of application, maintain control 
or suppression of such weeds for longer periods of time, while maintaining 
safety to the rice crop and improved toxicity with respect to fish and 
mammals. 
The above prior art herbicides have been found to share one or more 
undesirable properties as transplant rice herbicides. Among certain 
disadvantages of those prior art herbicides are: (1) their generally weak 
performance in the control and/or suppression of the 
economically-significant resistant perennial weeds Eleocharis kuroguwai 
and Sagittaria trifolia and (2) diminishing efficacy in the control or 
suppression of the perennial weed Cyperus serotinus and the annual weeds 
Echinochloa crus-galli and, to a lesser extent, Monochoria vaginalis, 
within a period from 2-6 weeks. 
These performance weaknesses are particularly apparent at lower rates of 
application, i.e. down to 0.17 lb/A (0.19 kg/ha) and lower. In fact, field 
tests have shown that in some treatments some of the prior art herbicides 
failed to selectively control Eleocharis kuroguwai at rates below 2.67 
lb/A (3 kg/ha) or even up to 5.36 lb/A (6 kg/ha), or higher, for periods 
as short as 2 or 3 weeks. Similarly, in field tests, it was also found 
that some of the above prior art rice herbicides failed to provide any 
meaningful suppression of Sagittaria trifolia after four or five weeks. 
It is, therefore, an object of this invention to provide a class of 
herbicides which are particularly useful in transplant rice. 
A further object of this invention is the provision of selected herbicides 
which: (1) are safe (i.e., produce no more than about 15% injury) on 
transplant rice at rates up to at least 5.0 lb/A (5.60 kg/ha); (2) 
selectively control Echinochloa crus-galli, Monochoria vaginalis and 
Cyperus serotinus at rates below 0.35 kg/ha (0.34 lb/A) for up to at least 
seven weeks; (3) selectively control Eleocharis kuroguwai at rates as low 
as 3.0 kg/ha (2.67 lb/A) for as long as five weeks and (4) provide 
increased suppression of Sagittari trifolia for up to seven weeks. 
It is a further object of this invention to provide a transplant rice 
herbicide having improved fish toxicity relative to the above prior art 
herbicides. 
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. 
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, 
particularly transplant rice. 
It has now been found that a selective group of 2-haloacetanilides 
characterized by specific combinations of radicals on the anilide nitrogen 
atom, a specific alkoxy radical in one ortho position and an ethyl radical 
in the other ortho position possess unexpectedly superior and outstanding 
selective herbicidal properties as transplant rice herbicides vis-a-vis 
prior art herbicides of related structure of the most relevant prior art, 
including a commercial rice herbicide. 
A primary feature of the herbicidal compositions of this invention is their 
ability to control and/or suppress annual and perennial weeds in 
transplant rice, particularly the prevalent and economically-significant 
annuals such as Echinochloa crus-galli, Monochoria vaginalis and resistant 
perennial species such as Cyperus serotinus, Eleocharis kuroguwai and 
Sagittaria trifolia and other noxious weeds. 
The compounds of this invention are characterized by the formula 
##STR1## 
wherein R is a C.sub.1-5 alkyl radical, including the n-, sec- and 
iso-propyls, butyls and pentyls, but preferably methyl or ethyl. 
The preferred species of compounds of this invention are: 
N-methyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide and 
N-ethyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide 
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 the invention of others and is described in more detail in co-pending 
U.S. Ser. No. 63,005 filed Aug. 2, 1979, assigned to the same assignee 
herein and in Examples 1 and 2 herein.

EXAMPLE 1 
This example describes the preparation of one preferred species, 
N-methyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. In this example 
dimethyl sulfate is used as the alkylating agent to prepare the 
N-methyl-2-chloroacetanilide from the corresponding sec-amide anion. 
To a chilled (15.degree. C.) mixture of 
2'-n-butoxy-6'-ethyl-2-chloroacetanilide, 6.2 g (0.023 mol), dimethyl 
sulfate, 3.0 g (0.024 mol), and 2.3 g of triethyl benzyl ammonium chloride 
in 250 ml of methylene chloride, was added all at once 55 ml of 50% NaOH 
and the mixture was stirred for 15.0 minutes. Water (100 ml) was added, 
and the resulting layers separated; the organic layer was washed with 
water, dried with MgSO.sub.4, then evaporated by Kugelrohr to give 5.8 g 
(89% yield) of a clear liquid, b.p. 115.degree. C. at 0.05 mm Hg. 
Anal. Calc'd for C.sub.15 H.sub.22 ClNO.sub.2 (%): C, 63.48; H. 7.81; Cl, 
12.49 Found: C, 63.52; H, 7.83; Cl, 12.52 
The product was identified as 
N-methyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 
EXAMPLE 2 
2'-n-butoxy-6'-ethyl-2-chloroacetanilide, 5.4 gms (0.02 mol), diethyl 
sulfate, 3.4 gms (0.22 mol) and 2.0 gms of triethyl benzyl ammonium 
chloride were mixed in 150 ml of CH.sub.2 Cl.sub.2 under cooling. 
Forty-five (45) ml of 50% NaOH were then added all at once at 18.degree. 
C. and the mixture stirred for ten minutes. Water (150 ml) was added and 
the resultant layers separated. The organic layer was washed with water, 
dried over MgSO.sub.4 and evaporated by Kugelrohr. A clear liquid 
(yellows), b.p. 113.degree. C. at 0.05 mm Hg was obtained in 22% yield 
(1.3 gms). 
Anal. Calc'd for C.sub.16 H.sub.24 ClNO.sub.2 (%): C, 64.53; H, 8.12; Cl, 
11,90. Found: C, 64.26; H, 8.16; Cl, 11.79 
The product was identified as 
N-ethyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 
The secondary anilides used as starting 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 
Examples 1 and 2 was prepared by mixing 2-n-butoxy-6-ethylaniline in 
methylene chloride and stirring vigorously with a 10% sodium hydroxide 
solution while a solution of chloroacetyl chloride in methylene chloride 
was added over a period of about one-half hour, keeping the temperature 
between 15.degree.-25.degree. C. with external cooling. The reaction 
mixture was stirred for about a further 60 minutes. After the addition was 
complete, the layers separated and the methylene chloride layer washed 
with water, dried and evaporated in vacuo to obtain a white solid, m.p. 
132.degree. C. 
Anal. Calc'd for C.sub.14 H.sub.20 ClNO.sub.2 (%): C, 62.33; H, 7.47; Cl, 
13.14. Found: C, 62.33; H, 7.49; Cl, 13.16 
The product was identified as 2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 
The primary amine used to prepare the above-mentioned secondary anilide may 
be prepared by known means, e.g., by catalytic reduction of the 
corresponding 2-alkoxy-6-alkyl-nitrobenzene in ethanol using platinum 
oxide catalyst. 
As noted above, the compounds of this invention have been found to be 
effective against major Asian weeds as transplant rice herbicides. 
However, pre-emergence and post-emergence herbicidal activity against 
other weeds in other crops has also been shown. Tables I and II summarize 
results of tests conducted to determine the pre-emergent herbicidal 
activity of the compounds of this invention. 
The pre-emergent tests were conducted 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 the soil is placed a 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 weighted 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 pans. After treatment, the pans are moved into a greenhouse bench 
where they are watered by subirrigation as needed to give adequate 
moisture for germination and growth. 
Approximately 2 weeks after seeding and treating, the plants were observed 
and the results recorded. Tables I and II below summarize such results. 
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 0 
25-49 1 
50-74 2 
75-100 3 
Undetermined 5 
______________________________________ 
The plant species utilized in one set of tests, the data for which are 
shown in Table I, are identified by letter in accordance with the 
following legend: 
______________________________________ 
A Canada Thistle 
E Lambsquarters 
I Johnsongrass 
B Cocklebur F Smartweed J Downey Brome 
C Velvetleaf G Yellow K Barnyardgrass 
D Morningglory Nutsedge 
H Quackgrass 
______________________________________ 
TABLE I 
______________________________________ 
Pre-Emergent 
Compound 
of Example Plant Species 
No. kg/h A B C D E F G H I J 
K 
______________________________________ 
1 11.2 3 5 2 1 3 3 3 3 3 3 
3 
5.6 3 5 2 2 3 2 3 3 3 3 3 
2 11.2 5 0 1 2 3 3 3 3 3 3 3 
5.6 5 0 0 0 3 3 3 3 2 3 3 
______________________________________ 
The compounds were further tested by utilizing the above procedure on the 
following plant species: 
______________________________________ 
L Soybean R Hemp Sesbania 
M Sugarbeet E Lambsquarters 
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 II. 
TABLE II 
__________________________________________________________________________ 
Pre-Emergent 
Compound of 
Plant Species 
Example No. 
kg/h 
L M N O P B Q D R E F C J S K T 
__________________________________________________________________________ 
1 5.6 
1 3 3 3 3 0 3 3 3 3 3 1 3 3 3 3 
1.12 
0 2 2 3 3 5 2 2 3 3 3 1 3 3 3 3 
0.28 
0 1 2 3 3 5 1 0 3 2 2 0 3 3 3 3 
0.06 
0 0 1 1 2 0 1 0 3 0 0 0 3 3 3 3 
0.01 
0 0 0 1 0 5 1 5 2 0 0 0 1 1 2 3 
0.006 
0 0 0 1 0 5 0 0 2 0 0 0 0 0 1 1 
2 5.6 
1 2 3 3 3 1 2 1 2 3 3 1 3 3 3 5 
1.12 
0 2 2 3 3 0 1 0 2 2 2 0 3 3 3 5 
0.28 
0 1 1 1 1 0 0 0 0 0 0 0 3 3 3 5 
0.06 
0 0 0 0 0 0 0 0 0 0 0 0 1 1 3 5 
0.01 
0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 5 
__________________________________________________________________________ 
The herbicides of this invention have been found to possess unexpectedly 
superior properties as transplant rice herbicides, most particularly in 
the effective control and/or suppression of the economically significant 
annual weeds, Echinochloa crus-galli and Monochoria vaginalis and the 
resistant perennials Cyperus serotinus, Eleocharis Kuroguwai and 
Sagittaria trifolia, while also controlling or suppressing many other 
less-resistant perennial and annual weeds. 
In order to illustrate the unexpectedly superior properties of compounds 
according to this invention both on an absolute basis and on a relative 
basis, comparative tests were conducted in the greenhouse and in the 
field. In some of these tests, known transplant rice herbicides (including 
MACHETE herbicide, the only current commercial 2-haloacetanilide rice 
herbicide) were tested for comparative purposes. The prior art 
2-haloacetanilide herbicides are identified as follows: 
A. 2',6'-diethyl-N-(n-butoxymethyl)-2-chloroacetanilide (U.S. Pat. No. 
3,663,200). 
B. 2',6'-diethyl-N-(n-butoxyethyl)-2-chloroacetanilide (U.S. Pat. No. 
3,663,200). 
C. 2'-methyl-6'-tert-butyl-N-(n-butoxymethyl)-2-chloroacetanilide (U.S. 
Pat. No. 3,955,959). 
D. 2',6'-diethyl-N-(n-propoxyethyl)-2-chloroacetanilide (U.S. Pat. No. 
4,168,965). 
In the discussion of data below, occasional reference is made to herbicide 
application rates symbolized as "GR.sub.15 " and "GR.sub.85 "; these rates 
are given in kilograms per hectare (kg/ha) which are convertible into 
pounds per acre (lbs/A) by dividing the kg/ha rate by 1.12. GR.sub.15 
defines the maximum rate of herbicide required to produce 15% or less crop 
injury, and GR.sub.85 defines the minimum rate required to achieve 85% 
inhibition of weeds. The GR.sub.15 and GR.sub.85 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 factor" ("SF") for a herbicide in given crops and 
weeds. The selectivity factor is a measure of the relative degree of crop 
safety and weed injury and is expressed in terms of the GR.sub.15 
/GR.sub.85 ratio, i.e., the GR.sub.15 rate for the crop divided by the 
GR.sub.85 rate for the weed, both rates in kg/ha (lb/A.) 
Since crop tolerance and weed control are inter-related, a brief discussion 
of this relationship in terms of selectivity factors is meaningful. In 
general, it is desirable that crop safety factors, i.e., herbicide 
tolerance vlaues, be high, since higher concentrations of herbicide are 
frequently desired for one reason or another. Conversely, it is desirable 
that weed control rates be small, i.e., the herbicide possesses high unit 
activity, for economical and possibly ecological reasons. However, small 
rates of application of herbicide may not be adequate to control certain 
weeds and a larger rate may be 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; the 
higher the numerical value, the greater selectivity of the herbicide for 
weed control in a given crop. 
In one comparative test in the greenhouse, herbicidal activity data were 
obtained and are presented in Table III comparing the relative efficacy of 
the compounds of Examples 1 and 2, representative compounds of this 
invention, with compound A (a commercial rice herbicide), as selective 
herbicides against economically-significant Asian weeds commonly 
associated with transplant rice. 
The test procedure used in this greenhouse test is as follows: Ray silt 
loam top soil containing about 0.05% by weight of krillium and sifted 
through a 0.5 in. (0.6 cm) screen is fumigated about 5-10 days prior to 
use. Pots are then filled with said Ray silt loam soil to a level to allow 
for a 1 in. (2.54 cm) flooding depth. Rice plants (Bluebelle) of 2 to 3 
weeks age are transplanted to the pots and bulbs or seeds of the test 
weeds also planted in the pots. The pots are then flooded and the test 
chemical applied to the surface of the flood water. The flood water is 
reduced to allow for germination of the Echinochloa crus-galli 
(barnyardgrass) seed and subsequently reflooded and maintained in that 
condition. Observations of percent inhibition using a scale of 0-100% are 
made about 3 weeks after transplant (WAT). 
The test data in Table III for all compounds was obtained under identical 
test conditions. The weeds used in the tests herein have the following 
abbreviations in the tables: Echinochloa crus-galli (EC), Monochloria 
vaginalis (MV), Cyperus Serotinus (CS), Eleocharis Kuroguwai (EK) and 
Sagittaria trifolia (ST). 
TABLE III 
______________________________________ 
Com- Rate Percent Inhibition 
pound (Kg/Ha) Rice EC MV CS EK ST 
______________________________________ 
A 2.24 15 100 100 100 100 15 
1.12 10 100 100 90 100 30 
0.56 10 100 100 85 100 45 
0.28 5 96 98 100 50 15 
Ex. 1 2.24 20 100 100 100 100 90 
1.12 15 100 100 100 100 85 
0.56 0 100 100 100 100 85 
0.28 5 100 100 85 100 75 
Ex. 2 2.24 25 100 100 100 100 55 
1.12 15 100 100 100 100 70 
0.56 10 100 100 100 100 25 
0.28 0 100 100 100 100 30 
______________________________________ 
Reference to the data in Table III will show that in this sheet, both 
invention compounds exhibited higher unit activity (i.e. phytotoxicity per 
unit of herbicide applied) against every weed in the test than did 
Compound A. In more particular, at 0.28 kg/ha (0.25 lb/A) the compound of 
Example 2 gave 100% control of every weed, except ST; the compound of 
Example 1 gave 100% control of three of five weeds, i.e., EC, MV and EK, 
at 0.28 kg/ha, and all weeds, except ST, at 0.56 kg/ha (0.5 lb/A). But for 
the slightly anomalous value in CS, Compound A did not give 100% control 
of any weed in the test, at 0.28 kg/ha although control of EC, MV and EK 
were complete at 0.56 kg/ha. A most significant fact of the test data in 
Table III is the relative control of the perennial weeds, EK, at 0.28 
kg/ha, and ST, at all test rates, of the invention compounds vis-a-vis 
Compound A. But for the slightly anomalous value of 45% control of ST at 
0.56 kg/ha, the invention compounds exhibited substantially greater 
control of ST than Compound A, by a factor of at least two. The 
outstanding superior control of ST by the compound of Example 1 vs. that 
of Compound A at all rates of application is particularly striking. It 
will also be noted that in this test, the compound of Example 1 exhibited 
positive selective control of ST in rice at 0.56 kg/ha, whereas greatly 
improved suppression of that weed was realized by the compound of Example 
2 vs. Compound A. The data in Table III also indicate that rice was 
slightly more tolerant of Compound A than the invention compounds at 2.24 
kg/ha, though not greatly so. 
In further comparative tests, a preferred compound of this invention 
(Example 1) was tested in the field with prior art Compounds A-D. These 
tests were conducted under conditions reflecting herbicide application 
times generally favorable to all herbicides in the test. The timing of 
application of herbicides to transplant rice is very important, whether, 
as in some instances, prior to transplanting the rice; in other instances, 
at the time of transplanting or else after transplanting. Application 
times are conventionally referred to as "days before transplant" (DBT) or 
"days after transplant" ("DAT"). The field test data in Table IV was 
obtained from a test in which the herbicides were applied at the time of 
transplant, i.e., "0 DAT", with observations being made weekly up to six 
weeks after transplant ("WAT") beginning at two weeks after transplant; 
for illustrative and representative purposes, only the early, middle and 
late period observations, i.e., 2 WAT, 4 WAT and 6 WAT, are shown in Table 
IV. The data in Table IV is for rates of application common to all 
herbicides in the test, i.e., from 3.0 kg/ha (2.67 lb/A) down to 0.375 
kg/ha (0.34 lb/A). All herbicides were applied at their actual or expected 
use rates, i.e., as granules containing 2.5% by weight herbicide for the 
compound of Example 1, Compounds B, C and D and 5.0% by weight for 
Compound A. 
TABLE IV 
__________________________________________________________________________ 
Percent Inhibition 
(Herbicide Applied 0 DAT) 
Rice EC MV CS EK ST 
Rate WAT WAT WAT WAT WAT WAT 
Compound 
(Kg/Ha) 
2 4 6 2 4 6 2 4 6 2 4 6 2 4 6 2 4 6 
__________________________________________________________________________ 
Ex. 1 3.0 25 22 23 98 100 
100 
100 
100 
100 
95 99 100 
97 92 
65 47 22 
18 
1.5 5 0 2 100 
100 
100 
100 
100 
100 
92 83 73 87 83 
37 30 8 5 
0.75 3 0 2 98 100 
98 
100 
99 
97 
62 53 25 82 75 
50 43 12 8 
0.375 
10 7 5 97 100 
100 
98 
100 
93 
77 73 50 73 40 
3 42 8 5 
A 3.0 10 2 3 98 100 
100 
100 
100 
100 
73 68 50 90 88 
68 42 33 12 
1.5 8 23 5 95 100 
97 
100 
100 
100 
90 82 77 83 78 
28 60 33 20 
0.75 2 0 0 90 100 
100 
100 
98 
100 
95 93 93 45 22 
0 52 20 15 
0.375 
8 10 7 60 72 
60 
98 
87 
82 
67 67 63 65 33 
10 37 22 7 
B 3.0 7 2 3 97 100 
100 
100 
100 
97 
72 62 37 100 
94 
72 32 30 13 
1.5 10 3 0 90 98 
98 
98 
100 
100 
82 83 45 73 65 
17 62 12 7 
0.75 3 2 3 87 93 
88 
95 
98 
100 
70 53 12 63 42 
0 27 15 7 
0.375 
7 3 7 55 68 
37 
97 
90 
80 
62 55 3 48 37 
7 27 10 5 
C 3.0 22 27 30 98 100 
100 
100 
100 
100 
95 100 
100 
82 90 
80 53 35 18 
1.5 12 18 18 100 
100 
100 
100 
100 
100 
93 99 100 
85 93 
67 38 30 17 
0.75 2 2 2 100 
100 
100 
100 
100 
100 
70 82 77 68 58 
18 33 18 8 
0.375 
3 0 0 98 100 
98 
100 
100 
97 
93 92 72 63 52 
18 30 5 0 
D 3.0 8 7 5 99 100 
100 
100 
98 
98 
67 65 60 85 75 
22 22 28 18 
1.5 10 8 7 97 98 
93 
98 
100 
100 
92 93 93 70 67 
47 23 27 22 
0.75 2 2 0 90 100 
100 
100 
99 
100 
73 77 70 63 40 
10 28 10 7 
0.375 
0 3 2 73 88 
83 
90 
95 
83 
82 65 33 62 20 
0 20 2 0 
__________________________________________________________________________ 
Reference to the data in Table IV will show that when the herbicides were 
applied on the day the rice was transplanted, i.e., 0 DAT, the rice was 
more sensitive to the compound of Example 1 ("Example 1" hereafter for 
brevity) and Compound C at 3 kg/ha than the other herbicides; similarly, 
Example 1 and Compound C exhibited higher unit activities at 0.375 kg/ha 
(0.34 lb/A) against the annual grasses, EC and MV; Compound C had the 
highest unit activity against the perennial CS, followed by Example 1 at 
the 4 WAT and 6 WAT observations; Example 1 exhibited the best control of 
both perennials, EK and ST at 2 WAT, but at 4 WAT and 6 WAT Compound C 
maintained the highest unit activity against EK followed by Example 1 and 
Compound B; at 4 WAT and 6 WAT Compounds A and C had the highest unit 
activity against ST. 
It is to be noted that although Example 1 and Compound C generally 
exhibited the overall highest unit activities against the weeds in the 
test, the narrow margin of safety of Compound C in rice (i.e., injury rate 
slightly greater than 15% at 1.5 kg/ha (1.34 lb/A after 4 WAT) renders it 
a less suitable transplant rice herbicide than Example 1 which was safe in 
rice at rates above 1.5 kg/ha and slightly less than 3.0 kg/ha, under 
conditions of this test. Moreover, as will be shown by the data in Table V 
from another field test, the timing of application of the herbicide of 
Example 1 is much more effective when applied subsequent to the day of 
transplant; hence, the data shown in Table IV for the performance of 
Example 1 does not reflect its optimum performance. 
In Table V are presented field data showing the relative performance of the 
compound of Example 1 and Compounds A-D applied 9 DAT, with observations 
being made weekly from 3 WAT to 7 WAT; again, for illustrative and 
representative purposes, only the early, middle and late period 
observations are reported in Table V, the herbicide rates and 
concentrations of active ingredients the same as is shown in Table IV. 
TABLE V 
__________________________________________________________________________ 
Percent Inhibition 
(Herbicide Applied 9 DAT) 
Rice EC MV CS EK ST 
Rate WAT WAT WAT WAT WAT WAT 
Cpd. 
(Kg/Ha) 
3 5 7 3 5 7 3 5 7 3 5 7 3 5 7 3 5 7 
__________________________________________________________________________ 
Ex. 1 
3.0 15 
15 10 100 
100 
100 
100 
100 
100 
100 
100 
100 
93 
93 
67 72 
43 
38 
1.5 10 
7 5 100 
98 100 
100 
100 
100 
82 100 
67 82 
65 
0 40 
13 7 
0.75 7 
2 0 100 
100 
100 
100 
100 
100 
93 93 95 83 
68 
13 43 
33 13 
0.375 
13 
7 7 90 88 78 100 
100 
100 
100 
98 97 80 
52 
15 50 
23 18 
A 3.0 12 
7 5 93 93 90 100 
100 
100 
88 100 
100 
68 
40 
0 52 
23 13 
1.5 12 
7 5 88 90 85 100 
100 
100 
100 
100 
100 
55 
25 
0 35 
5 3 
0.75 13 
3 7 80 75 70 92 
87 
60 
70 50 38 37 
12 
3 26 
10 8 
0.375 
10 
8 8 23 20 17 90 
98 
80 
80 33 67 40 
22 
3 37 
12 7 
B 3.0 12 
5 2 95 95 92 100 
100 
97 
75 72 65 55 
43 
18 42 
25 12 
1.5 10 
2 5 90 80 85 98 
100 
100 
87 85 67 42 
32 
0 40 
25 13 
0.75 12 
5 3 68 53 50 97 
98 
88 
78 67 67 28 
5 
0 38 
12 10 
0.375 
12 
0 5 57 55 47 100 
95 
77 
93 100 
77 27 
3 
0 5 
2 5 
C 3.0 10 
5 8 98 100 
100 
100 
100 
100 
95 100 
100 
83 
93 
74 30 
13 3 
1.5 18 
15 13 98 100 
100 
100 
100 
100 
62 87 83 70 
77 
38 48 
17 7 
0.75 10 
7 8 92 95 97 100 
100 
100 
93 93 82 75 
68 
32 32 
8 0 
0.375 
17 
8 10 82 78 82 97 
98 
60 
58 60 43 52 
23 
15 47 
10 2 
D 3.0 15 
5 8 100 
100 
100 
100 
100 
100 
90 100 
100 
84 
78 
45 73 
60 52 
1.5 10 
5 7 78 75 78 100 
100 
100 
77 77 100 
52 
30 
0 43 
25 22 
0.75 10 
5 2 88 92 88 100 
87 
100 
77 67 33 45 
20 
0 42 
25 18 
0.375 
8 
7 7 62 48 57 95 
98 
95 
92 87 67 50 
23 
0 45 
12 7 
__________________________________________________________________________ 
Referring to the data in Table V, it is immediately apparent that Example 1 
had the highest unit activity of all herbicides in the test against every 
weed in the test, except for Compound D against ST, while simultaneously 
maintaining safety in the rice at 3.0 kg/ha (2.67 lb/A), the maximum test 
rate. Similarly noteworthy is the observation that at most rates of 
application, particularly the lowest ones, Example 1 maintained the 
highest degree of selective control of EC, MV and CS for the longest 
period of time, i.e., 7 WAT; comparable suppression of EK as Compound C at 
the lowest and highest rates of application and second after Compound D in 
the suppression of ST at 7 WAT. It will be noted that in those instances 
where Compounds C and D exhibited somewhat higher unit activity than 
Example 1, i.e., against EK and ST, respectively at 7 WAT, both of those 
compounds lacked the overall degree of control and suppression of the 
remaining weeds in the test. 
The superiority of Example 1 over the prior art herbicides is further 
evidenced by reference to the selectivity factors (GR.sub.15 /GR.sub.85 
ratios) of the respective compounds against the several weeds in the test. 
Thus, based on the data in Table V, Example 1 exhibited selectivity 
factors of 16 against EC, MV and CS in transplant rice for 3-7 WAT, 
whereas the selectivity factors for the prior art herbicides against the 
same weeds were as follows (at various periods between 3 WAT and 7 WAT): 
Compound A: 2, 8 and 2, respectively; Compound B: 2, 8 and 1, 
respectively; Compound C: 4, 8 and 4, respectively and Compound D: 1, 8 
and 1, respectively. Against EK, Example 1 had a selectivity factor of 
about 2 up to 5 WAT; Compound C had a selectivity factor of greater than 1 
at 5 WAT and Compound D had a selectivity factor of about 1 for 3 WAT and 
Compounds A and B were non-selective even at 3 WAT. 
It is clear from the foregoing that the Compound of Example 1 exhibited 
overall superiority vis-a-vis the prior art compounds as a selective 
herbicide for transplant rice. 
It is an additional advantage of the herbicides of this invention that the 
optimum time for application thereof to the rice is approximately nine 
days after transplant. Thus, the farmer can transplant his rice and let it 
grow for nine days while he attends to other chores needing immediate 
attention, or other pursuits, then return to the rice fields for 
application of the herbicide. In contrast, the current practice with 
Machete, the commercial herbicide, is to apply the herbicide within the 
period of three days before to four days after transplant (one practice is 
to apply the herbicide on the day of transplant); in this practice, the 
farmer is obliged to concern himself not only with transplanting the rice, 
but also treating with the herbicide, or vice-versa, all within a matter 
of hours or a few days. 
In another comparative test in the greenhouse, the compound of Example 2 
and Compound B were tested in Upland seeded rice. It was found that the 
compound of Example 2 selectively controlled Echinochloa crus-galli at 
0.064 kg/ha (0.0573 lb/A) while maintaining rice safety at the maximum 
test rate of 1.12 kg/ha (1.0 lb/A), resulting in a selectivity factor of 
at least 17.5. In contrast, Compound A, (a commercial rice herbicide), 
required 0.14 kg/ha (0.125 lb/A) to selectively control the same weed with 
rice safety also maintained at 1.12 kg/ha resulting in a selectivity 
factor of at least 8, i.e., less than one-half that of the compound of 
Example 2. 
In further tests in the greenhouse, the compound of Example 2 was tested 
for its activity against annual weeds in sugarbeets at test rates within 
the range of 0.07 to 1.12 kg/ha (0.0625 to 1.0 lb/A). The GR.sub.15 and 
GR.sub.85 rates for sugarbeets and the various weeds are shown in Table 
VI; the selectivity factors for the herbicide against the weeds in 
sugarbeets are shown in parentheses below the weeds; "NS" means 
non-selective within the test limits. The following abbreviations are used 
in the table: barnyardgrass (BYG), wild oats (WO), downy brome (DB); 
redroot pigweed (RRP), blackgrass (BG), large crabgrass (LCG) and yellow 
foxtail (YFT). 
TABLE VI 
______________________________________ 
GR.sub.15 Rate 
GR.sub.85 Rate 
(Kg/Ha) (Kg/Ha) 
Sugarbeets 
BYG WO DB RRP BG LCG YFT 
______________________________________ 
0.56 &lt;0.07 0.28 0.14 &gt;1.12 0.21 0.07 &lt;0.07 
(&gt;8.0) (2.0) (4.0) 
(NS) (2.7) 
(8.0) 
(&gt;8.0) 
______________________________________ 
The data in Table VI show that the compound of Example 2 selectively 
controlled every weed in the test, except redroot pigweed at rates well 
below 0.56 kg/ha (0.5 lb/A), thus proving the versatility of that compound 
as an effective herbicide in important crops. 
In view of the importance of fish toxicity considerations, tests were 
conducted with the compound of Example 1 on carp (7 cm) according to 
Japanese protocol; test data are shown in Table VII. Since U.S. Pat. No. 
3,955,959 mentioned above discloses carp toxicity data for butachlor 
(Compound A) and terbuchlor (Compound C), also obtained according to 
Japanese protocol, the toxicity data in said U.S. Pat. No. 3,955,959 for 
these compounds is also presented in Table VII for comparative purposes. 
TABLE VII 
______________________________________ 
Fish Toxicity 
(Carp) 
TLM* (PPM) 
Compound 48 hours 96 Hours 
______________________________________ 
Ex. 1 3.2 2.4 
A 1.0 0.76 
C 1.8 1.4 
______________________________________ 
*Median Tolerance Limit (LC.sub.50) 
The data in Table VII indicate that the compound of Example 1 was less than 
one-third as toxic to carp as Compound A, the commercial rice herbicide, 
and almost one-half as toxic as Compound C. Since the expected use rate of 
the compound of Example 1 is about one-half that of Compound A, the data 
in Table VII would indicate that the expected fish kill of the compound of 
Example 1 would be only one-sixth that of Compound A. TLM values will vary 
plus or minus a few tenths of a part per million from test to test within 
the same test protocol and from one test protocol to another, but such 
differences are within reproducibility limits are of no significance. 
It is apparent that the above compounds may be safely used with the normal 
degree of care required for compounds having the indicated toxicological 
properties. 
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 structurally-relevant compounds of the prior art, one of which 
(Compound A) is a commercial herbicide. More particularly, the compounds 
of this invention have proven to be outstanding selective herbicides, 
particularly in the control of economically-significant Asian annual and 
perennial weeds in transplant rice. In more particular, compounds 
according to this invention exhibit outstanding control of the annual 
grasses Echinochloa crus-galli and Monochoria vaginalis and perennials 
such as Cyperus serotinus, Eleocharis kuroguwai and Sagittaria trifolia, 
while controlling other less-resistant annual grasses and perennials, 
including those mentioned in Tables I, II and VI above, and others. 
The herbicidal compositions of this invention, including concentrates which 
require 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 ingredient with an adjuvant including 
diluents, extenders, carriers and conditioning agents to provide 
compositions in the form of finely-divided particulate solids, granules, 
pellets, solutions, dispersions or emulsions. Thus the active ingredient 
can be used with an adjuvant such as a finely-divided 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, 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 sulfonates. 
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 95 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 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 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 a 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 ingredient in the solvent. 
In another form of aqueous suspension, 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 containing 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 range from about 
480 to 700 g/l of total composition preferably 480 to 600 g/l. The 
microencapsulation process referred to here is described in more detail in 
the assignee's copending U.S. Ser. No. 23,566 filed Mar. 26, 1979. 
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 this invention 
include dimethylformide, dimethylsulfoxide, 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 matrix of an inert, 
finely-divided particulate extender. In order to aid leaching of the 
active ingredient from the particulate, a surface active agent such as 
those listed hereinbefore can be present in the composition. Natural 
clays, pyrophyllites, illite and vermiculite are examples of operable 
classes of particulate mineral extenders. The preferred extenders are the 
porous, absorptive, preformed particles, such as preformed and screened 
particulate attapulgite, or heat expanded, particulate vermiculite and the 
finely-divided clays such as kaolin clays, hydrated attapulgite or 
bentonitic clays. These extenders are sprayed or blended with the active 
ingredient to form the herbicidal 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 clay and 0 to about 5 parts 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. Other herbicidal compounds useful in combination with the 
active ingredients of this invention, particularly for use in transplant 
rice, include, for example, methyl-5(2,4-dichlorophenoxy)-2-nitrobenzoate 
(common name "bifenox", active ingredient in Modown.RTM. herbicide), 
1-3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl paratoluene sulfonate 
(code designation "SW-751"), .alpha.-(.beta.-naphthoxy) propionanilide 
(coded MT-101"), 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether (coded 
"X-52"), 3,4-dichloropropionanilide (common name "propanil"), etc. For use 
in other non-rice crops, other herbicidal compounds may also be combined 
with compounds according to this invention. For example, such other 
compounds include triazines, ureas, carbamates, acetamides, acetanilides, 
uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, 
benzoic acids, nitriles, biphenyl ethers and the like such as: 
Heterocyclic Nitrogen/Sulfur Derivatives 
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-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2 dioxide 
3-Amino-1,2,4-triazole 
6,7-Dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt 
5-Bromo-3-isopropyl-6-methyluracil 
1,1'-Dimethyl-4,4'-bipyridinium 
5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)1,3,4-oxadiazol-2-one 
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)-1,1-dimethylurea 
1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea 
Carbamates/Thiolcarbamates 
2-Chloroallyl diethyldithiocarbamate 
S-(4-chlorobenzyl)N,N-diethylthiolcarbamate 
Isopropyl N-(3-chlorophenyl) carbamate 
S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate 
Ethyl N,N-dipropylthiolcarbamate 
S-propyl dipropylthiolcarbamate 
Acetamides/Acetanilides/Anilines/Amides 
2-Chloro-N,N-diallylacetamide 
N,N-dimethyl-2,2-diphenylaetamide 
N-(2,4-dimethyl-5-[[(trifluoromethyl)sulfonyl]amino]phenyl)acetamide 
N-Isopropyl-2-chloroacetanilide 
2',6'-Diethyl-N-methoxymethyl-2-chloroacetanilide 
2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide 
.alpha.,.alpha.,.alpha.-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine 
N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide 
Acids/Esters/Alcohols 
2,2-Dichloropropionic acid 
2-Methyl-4-chlorophenoxyacetic acid 
2,4-Dichlorophenoxyacetic acid 
Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate 
3-Amino-2,5-dichlorobenzoic acid 
2-Methoxy-3,6-dichlorobenzoic acid 
2,3,6-Trichlorophenylacetic acid N-1-naphthylphthalamic acid 
Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 
4,6-Dinitro-o-sec-butylphenol 
N-(phosphonomethyl) glycine and its C.sub.1-6 monoalkyl amine and alkaline 
metal salts and combinations thereof 
Ethers 
2,4-Dichlorophenyl-4-nitrophenyl ether 
2-Chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl 
ether 
Miscellaneous 
2,6-Dichlorobenzonitrile 
Monosodium acid methanearsonate 
Disodium methanearsonate 
The herbicides of this invention may be used singly, as mixtures with other 
herbicides and may be used in sequential use with other herbicides. For 
example, treatments of a transplant rice crop with the herbicides of this 
invention may be followed with treatments of other herbicides or mixtures 
such as S-4-chlorobenzyl diethylthiocarbamate (common name "benthiocarb") 
plus 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common name "simazine") 
or 3-isopropyl-(1H)-benzo-2,1,3-thiadiazine-4-one-2,2-dioxide (common name 
"bentazone") or 4-(4-chloro-2-methylphenoxy)butyric acid (common name 
"MCPB"). Field tests have indicated that the compound of Example 1 is 
less-efficacious in direct-seeded rice, because this rice culture is less 
tolerant than transplant rice. However, because of the high unit activity 
of compounds according to this invention against annual and perennial 
weeds associated with rice, it is within the purview of this invention to 
combine these herbicides with safeners or antidotes, to enhance the 
tolerance of both transplanted and direct-seeded rice thereto. Exemplary 
safeners contemplated as useful with the herbicides of this invention 
include the phenylglyoxylonitrile-2-oxime cyanomethyl ether described in 
U.S. Pat. No. 4,152,137, 2,4-disubstituted-5-thiazolecarboxylic acids and 
derivatives thereof as disclosed in the assignee's copending U.S. Ser. No. 
906,183 and other known safeners for 2-haloacetanilides in rice. 
Fertilizers useful in combination with the active ingredients include, for 
example, ammonium nitrate, urea, potash and superphosphate. Other useful 
additaments include materials in which plant organisms take root and grow 
such as compost, manure, humus, sand and the like. 
Herbicidal formulations of the types described above are exemplified in 
several illustrative embodiments below. 
______________________________________ 
Weight Percent 
______________________________________ 
I. Emulsifiable Concentrates 
A. Compound of Example No. 1 
50.0 
Phosphate ester of ethoxylated 
alcohols (e.g., GAFAC.RTM. RE-610) 
4.125 
Ethoxylated tertiary amines de- 
rived from fatty oils such as palm oil 
(e.g., Ethomeen.RTM. C/12) 
0.875 
Monochlorobenzene 13.5 
C.sub.9 aromatic solvent (T-400) 
31.5 
100.00 
B. Compound of Example No. 2 
46.45 
GAFAC RE-610 4.125 
Ethomeen.RTM. C/12 0.875 
MCB 48.55 
100.00 
C. Compound of Example No. 1 
5.0 
Calcium dodecylbenzene sulfonate/ 
polyoxyethylene ethers blend (e.g., Atlox 
3437F) 1.0 
Xylene 94.0 
100.00 
II. Liquid Concentrates 
A. Compound of Example No.1 10.0 
Xylene 90.0 
100.00 
B. Compound of Example No. 2 
85.0 
Dimethyl sulfoxide 15.0 
100.00 
C. Compound of Example No. 1 
50.0 
N-methylpyrrolidone 50.0 
100.00 
D. Compound of Example No. 2 
5.0 
Ethoxylated castor oil 20.0 
Rhodamine B .5 
Dimethyl formamide 74.5 
100.00 
III. Emulsions 
A. Compound of Example No. 1 
40.0 
Polyoxyethylene/polyoxy- 
propylene block copolymer with butanol 
(e.g., Tergitol.RTM. XH) 4.0 
Water 56.0 
100.00 
B. Compound of Example No. 2 
5.0 
Polyoxyethylene/polyoxy- 
propylene block copolymer with butanol 
3.5 
Water 91.5 
100.00 
IV. Wettable Powders 
A. Compound of Example No. 1 
25.0 
Sodium lignosulfonate 3.0 
Sodium N-methyl-N-oleyl-taurate 
1.0 
Amorphous silica (synthetic) 
71.0 
100.00 
B. Compound of Example No. 2 
80.0 
Sodium dioctyl sulfosuccinate 
1.25 
Calcium lignosulfonate 2.75 
Amorphous silica (synthetic) 
16.00 
100.00 
C. Compound of Example No. 1 
10.0 
Sodium lignosulfonate 3.0 
Sodium N-methyl-N-oleyl-taurate 
1.0 
Kaolinite clay 86.0 
100.00 
V. Dusts 
A. Compound of Example No. 1 
2.0 
Attapulgite 98.0 
100.00 
B. Compound of Example No. 2 
60.0 
Montmorillonite 40.0 
100.00 
C. Compound of Example No. 1 
30.0 
Bentonite 70.0 
100.00 
D. Compound of Example No. 2 
1.0 
Diatomaceous earth 99.0 
100.00 
VI. Granules 
A. Compound of Example No. 1 
15.0 
Granular attapulgite (20/40 mesh) 
85.0 
100.00 
B. Compound of Example No. 2 
30.0 
Diatomaceous earth (20/40) 
70.0 
100.00 
C. Compound of Example No. 1 
0.5 
Bentonite (20/40) 70.0 
100.00 
D. Compound of Example No. 2 
5.0 
Pyrophyllite (20/40) 95.0 
100.00 
VII. Microcapsules 
A. Compound of Example No. 1 
encapsulated in polyurea shell wall 
49.2 
Sodium lignosulfonate (e.g. 
Reax 88.RTM. B) 0.9 
Water 49.9 
100.00 
B. Compound of Example No. 2 
encapsulated in polyurea shell wall 
10.0 
Potassium lignosulfonate (e.g., 
Reax.RTM. C-21) .5 
Water 89.5 
100.00 
C. Compound of Example No. 1 en- 
capsulated in polyurea shell wall 
80.0 
Magnesium salt of lignosulfate 
(Treax.RTM. LTM) 2.0 
Water 18.0 
100.00 
______________________________________ 
When operating in accordance with the present invention, effective amounts 
of the acetanilides of this invention are applied to the soil containing 
the plants, or are incorporated into aquatic media 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 dusters, 
boom and hand sprayers and spray dusters. The compositions can also be 
applied from airplanes as a dust or a spray because of their effectiveness 
at low dosages. The application of herbicidal compositions to aquatic 
plants is usually carried out by adding the compositions to the aquatic 
media in the area where control of the aquatic plants is desired. 
The application of an effective amount of the compounds of this invention 
to the locus of undesired weeds is essential and critical for the practice 
of the present invention. The exact amount of active ingredient to be 
employed is dependent upon various factors, including the plant species 
and stage of development thereof, the type and condition of soil, the 
amount of rainfall and the specific acetanilide employed. In selective 
preemergence application to the plants or to the soil a dosage of from 
0.02 to about 11.2 kg/ha, preferably from about 0.04 to about 5.60 kg/ha, 
or suitably from 1.12 to 5.6 kg/ha of acetanilide is usually employed. 
Lower or higher rates may be required in some instances. For example, in 
some upland-seeded rice tests, compounds according to this invention have 
shown a measurable amount of injury to barnyardgrass at extremely low 
rates. Thus, in one test, the compound or Example 2 exhibited 20% control 
of barnyardgrass at 0.0087 kg/ha (0.0078 lb/A). One skilled in the art can 
readily determine from this specification, including the above example, 
the optimum rate to be applied in any particular case. 
The term "soil" is employed in its broadest sense to be inclusive of all 
conventional "soils" as defined in Webster's New International Dictionary, 
Second Edition, Unabridged (1961). Thus the term refers to any substance 
or media in which vegetation may take root and grow, and includes not only 
earth but also compost, manure, muck, humus, sand and the like, adapted to 
support plant growth. 
Although the invention is described with respect to specific modifications, 
the details thereof are not to be construed as limitations except to the 
extent indicated in the following claims.