The disclosure herein pertains to 2-haloacetamides characterized by substitution on the nitrogen atom of certain heterocyclymethyl radicals and by substituted or unsubstituted cycloalkenyl or phenyl radicals and to a process for the preparation thereof. These compounds are useful as herbicides.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The invention herein pertains to the field of herbicides. More 
particularly, the field of this invention pertains to the use of 
2-haloacetamides as herbicides. 
2. Description of the Prior Art 
It is known in the prior art to use various 2-haloacetamides as herbicides, 
either individually or in combination with other herbicides. 
Among herbicidal compounds of the prior art are those acetamides having in 
varying arrangements substitutions of alkyl, cycloalkyl, alkenyl, 
cycloalkenyl, alkoxy, halogen, aryl, etc. groups, all of which may be 
further substituted with other radicals. 
Illustrative of the 2-haloacetamides of the prior art and of those most 
closely related to the 2-haloacetamides disclosed and claimed herein are 
the 2-haloacetamides disclosed in U.S. Pat. Nos. 3,495,967, 3,574,746, 
3,586,496, 3,901,917, 3,819,661, 3,946,045, 4,012,222, 4,097,262, 
4,055,410 and 4,155,744. In the '967 patent the 2-chloroacetamides are 
characterized by substitutions on the nitrogen atom including a 
benzothiophene radical which may have other substituents. The '746 and 
'496 patents are directed generally to the same 2-haloacetamides which are 
characterized by a C.sub.5-7 cycloalken-1-yl group and other substituents 
on the amide nitrogen. The '917 patent relates to 2-haloacetanilides 
characterized in having a thienylmethylene group which may be substituted 
with a lower alkyl group substituted on the nitrogen atom and the '661 
patent relates to 2-haloacetanilides which are substituted on the nitrogen 
atom with a furfuryl or tetrahydrofurfuryl. The '045 and '222 patents 
disclose 2-haloacetanilides characterized by a dioxolanyl-lower alkyl 
group on the anilide nitrogen atom. The '410 patent relates to 
2-haloacetanilides substituted on the nitrogen atom with 
2,4-dioxothiazolidinylmethyl or 2,4-dioxoimidazolidinylmethyl radicals and 
the '744 patent relates to 2-haloacetamides characterized by substitutions 
on the nitrogen atom of cycloalkenyl and heterocyclic radicals. The '262 
patent relates to 
N-(O-substituted-phenyl)-N-[(2-oxooxazolidin-3-yl)-methyl)-2-haloacetamide 
s. 
Prior art processes for producing various 2-haloacetamides involve the 
haloacetylation of the appropriate aniline or cyclohexylideneimine to get 
the corresponding product. 
As will be apparent, the most relevant 2-haloacetamides of the prior art 
have a heterocyclic and cycloalkenyl or phenyl (which may be substituted) 
group attached to acetamide or acetanilide nitrogen atom. However, this 
above prior art fails to disclose the novel 2-haloacetamides and process 
of the present invention as will be apparent from the discussion below. 
SUMMARY OF THE INVENTION 
The present invention relates to herbicidally active compounds, a novel 
process for preparing same, herbicidal compositions containing these 
compounds and herbidical method of use of said compositions in 
agricultural crops, particularly rice. 
The herbicidal compounds of this invention are characterized by the formula 
##STR1## 
wherein X is chlorine, bromine or iodine; 
R is a C.sub.5-7 cycloalkenyl or phenyl radical or such R radical 
substituted with C.sub.1-6 alkyl, thioalkyl, alkoxy, alkoxyalkyl, 
polyalkoxy, C.sub.2-6 alkenyl or alkynyl, C.sub.5-10 aryl, halogen, 
NO.sub.2, CF.sub.3 or a C.sub.5-6 heterocyclic ring containing O or S 
hetero atoms; 
Y is O, S or NR.sub.4 ; R.sub.4 is hydrogen or C.sub.1-4 alkyl; 
R.sub.1 is hydrogen or said radicals as may be substituted on R; and 
n is an integer from 0-4 inclusive. 
Compounds of particular interest include those where in the above Formula 
I, R is a lower alkyl- and/or alkoxy-substituted phenyl or lower 
alkyl-substituted cycloalken-1-yl group and Y is sulfur. 
A preferred species of this invention is 
N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-[(2-oxo-3-(2H)-benzothiazolyl)methyl] 
-2-chloroacetanilide. Other species will be described below. 
The novel process of this invention involves preparing the compounds of 
Formula I by reacting a compound of the formula 
##STR2## 
with a compound of the formula 
##STR3## 
wherein X.sup.1 is a halogen, X, Y, R, R.sub.1 and n are as defined above, 
in the presence of a base and preferably in the presence of a phase 
transfer catalyst. The reaction is carried out at temperatures within the 
range 0.degree.-120.degree. C., preferably between 10.degree.-60.degree. 
C. 
The preferred bases for use in this process are alkali metal hydroxides, 
although other bases such as elemental metals, metal fluorides, hydrides, 
oxides, carbonates or alkoxides may also be used. 
Preferred phase transfer catalysts are the quaternary ammonium halide 
salts, e.g., aryl or aralkyl trialkyl ammonium halide salts such as benzyl 
triethyl ammonium bromide or chloride. Other phase transfer catalysts 
include the acyclic and cyclic polyethers, e.g., "18-crown-6" cyclic 
ethers in combination with alkali metal hydroxide as base. 
The compounds of this invention are useful as herbicides.

DETAILED DESCRIPTION OF THE INVENTION 
The compounds according to this invention may be prepared by alternative 
processes. Example 1 describes the preparation of an invention compound by 
using an N-alkylation process previously developed by the inventor herein. 
This process involves converting a sec-2-haloacetamide to an anion thereof 
under basic conditions, then reacting the anion with an alkylating agent, 
preferably in the presence of a phase transfer catalyst. The said 
N-alkylation process and variations thereof contributed by another 
employee in the laboratories of the assignee herein is the subject of 
copending U.S. Ser. No. 63,005 filed Aug. 2, 1979 as a 
continuation-in-part of U.S. Ser. No. 896,879 filed Apr. 17, 1978, now 
abandoned. 
EXAMPLE 1 
2-chloro-N-(2,6-dimethyl-1-cyclohexen-1-yl)-acetamide (4 g, 0.02 mol), 
3-chloromethyl-2-benzothiazolinone (5.5 g, 0.0275 mol), benzyltriethyl 
ammonium bromide (2 g) and 75 ml of methylene chloride were charged to a 
500 mL round bottom flask. With stirring, sodium hydroxide (15 g of 50% 
aqueous) was added all at once. Stirred one hour. 150 ml water added. 
Methylene chloride layer separated, dried over MgSO.sub.4, filtered and 
solvent removed in vacuo leaving an amber foam. This foam was taken up in 
hot isopropanol. When cool, filtered 4.4 g of white crystals, mp 
133.degree.-136.degree. C., plus small amount of higher melting material. 
Further recrystallization did not remove higher melting material. Solid 
was chromatographed through silica gel with chloroform as eluant. 
Fractions 10 and 11 held product. Evaporation of solvent gave 2.6 g of 
white crystals, mp 141.degree.-143.degree. C. 
Anal. calc'd for C.sub.18 H.sub.21 ClN.sub.2 O.sub.2 S(%): Calc'd: C, 
59.25; H, 5.80; N, 7.68; Found: C, 59.11; H, 5.82; N, 7.69. 
The product was identified as 
N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-[(2-oxo-3(2H)-benzothiazolyl)methyl]- 
2-chloroacetamide. 
The starting materials used in the processes of this invention are well 
know. Thus, the sec-amide starting materials of the type used in Example 1 
are disclosed in U.S. Pat. No. 3,574,746. The benzothiazolinone derivative 
is disclosed in U.S. Pat. No. 3,050,526. 
EXAMPLE 2 
This example illustrates an alternative and novel process for preparing 
compounds according to this invention. 
N-(chloromethyl)-2'-methoxy-6'-methyl-2-chloroacetanilide, 3.6 g (0.0137 
mol), in 100 ml of CH.sub.2 Cl.sub.2 were mixed with benzothiazolin-2-one, 
2.2 g (0.0145 mol) and 1.0 g benzyl triethyl ammonium bromide. To this 
mixture with stirring was added 30 ml of 50% caustic; the mixture was 
allowed to react for about three hours. On work up 5.8 g crude product was 
isolated, then recrystallized from isopropanol to a light buff-colored 
solid, m.p. 120.degree.-121.degree. C. 
Anal. calc'd for C.sub.18 H.sub.17 ClN.sub.2 O.sub.3 S(%): Calc'd: C, 
57.37; H, 4.55; N, 7.43; Found: C, 56.89; H, 4.51; N, 7.34. 
The product was identified as 
N-(2'-methoxy-6'-methyl)-N-[(2-oxo-3(2H)-benzothiazolyl)methyl]-2-chloroac 
etanilide. 
The benzothiazolin-2-one is a commercially-available product and the 
N-(chloromethyl)-2-chloroacetanilide derivative may be prepared by the 
conventional process of chloroacetylating the corresponding substituted 
phenylazomethine as described, e.g., in U.S. Pat. Nos. 3,637,847 and 
3,547,620. 
EXAMPLES 3-11 
Following the same general procedures described in Examples 1 and 2, but 
subtituting the appropriate starting materials and reaction conditions, 
other 2-haloacetamides according to Formula I above are prepared. The same 
or equivalent solvents, bases and catalysts, together with appropriate 
temperatures and times are readily used in these process embodiments. 
Typical other compounds prepared in accordance with the above procedures 
are shown in Table I together with certain of their physical properties. 
TABLE I 
__________________________________________________________________________ 
Example Empirical Analysis 
No. Compound Formula M.P. .degree.C. 
Element 
Calc'd. 
Found 
__________________________________________________________________________ 
3 N--[(2-oxo-3(2H)--benzothia- 
C.sub.18 C.sub.17 ClN.sub.2 O.sub.2 S 
152-153 
C 51.91 
51.95 
zolyl)methyl]-2'-6'-diethyl- H 4.75 
4.77 
2-chloroacetanilide N 7.76 
7.77 
4 N--[(2-oxo-3(2H)--benzothia- 
C.sub.19 H.sub.23 ClN.sub.2 O.sub.2 S 
135-160 
C 60.23 
60.29 
zolyl)methyl]-N--(2-ethyl-6- H 6.12 
6.15 
methyl-1-cyclohexen-1-yl)-2- N 7.39 
7.37 
chloro-acetamide, mixed with 
its -N--[(2-oxo-3(2H)--benzo- 
thiazolyl)methyl]-N--(2-methyl- 
6-ethyl-1-cyclohexen-1-yl)- 
2-chloroacetamide 
5 N--[(2-oxo-3(2H)--benzothia- 
C.sub.20 H.sub.25 ClN.sub.2 O.sub.2 S 
147-148 
C 61.13 
60.87 
zolyl)methyl]-N--(2,6-diethyl- H 6.41 
6.40 
1-cyclohexen-1-yl)-2-chloro- N 7.13 
7.05 
acetamide 
6 N--[(5-chloro-2-oxo-3(2H)--benzo- 
C.sub.18 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2 S 
183-187 
C 54.12 
53.98 
thiazolyl)methyl]-N--(2,6- H 5.05 
5.11 
dimethyl-1-cyclohexen-1-yl)- N 7.02 
6.98 
2-chloroacetamide 
7 N--[(6-bromo-2-oxo-3(2H)-- 
C.sub.18 H.sub.20 BrCN.sub.2 O.sub.2 S 
125-127 
C 48.72 
48.83 
benzothiazolyl)methyl]-N--(2, H 4.54 
4.58 
6-dimethyl-1-cyclohexen- N 6.31 
6.29 
1-yl)-2-chloroacetamide 
8 N--[(6-ethoxy-2-oxo-3(2H)-- 
C.sub.20 H.sub.25 ClN.sub.2 O.sub.2 S 
135-137 
C 58.74 
58.82 
benzothiazolyl)methyl]-N--(2, H 6.16 
6.19 
3-dimethyl-1-cyclohexen-1-yl)- N 6.85 
6.82 
2-chloroacetamide 
9 N--[(2-oxo-3(2H)--benzothia- 
C.sub.18 H.sub.25 ClN.sub.2 O.sub.2 S 
95-99 
C 58.60 
58.65 
zolyl)methyl]-N--(2,6-dimethyl- 
H 6.83 
6.83 
1-cyclohexen-1-yl)-2-chloro- N 7.59 
7.58 
amide 
10 N--[(2-oxo-3(2H)--benzothia- 
C.sub.17 H.sub.19 ClN.sub.2 O.sub.2 S 
134-139 
C 58.19 
58.15 
zolyl)methyl]-N--(2-methyl-1- H 5.46 
5.50 
cyclohexen-1-yl)-2-chloro- N 7.98 
7.96 
amide 
11 N--[(2-oxo-3(2H)--benzoxazolyl) 
C.sub.18 H.sub.21 ClN.sub.2 O.sub.3 
140-142 
C 61.98 
61.99 
methyl]-N--(2,6-dimethyl-1- H 6.07 
6.10 
cyclohexen-1-yl)-2-chloro- N 8.03 
8.03 
amide 
__________________________________________________________________________ 
As noted above, the compounds of this invention have been found to be 
effective as herbicides, particularly as preemergence herbicides, although 
post-emergence activity has also been shown. Tables II and III summarize 
results of tests conducted to determine the pre-emergent herbicidal 
activity of the compounds of this invention. 
The pre-emergence tests are conducted as follows: 
A good grade of top soil is placed in aluminum pans and compacted to a 
depth of three-eighths to one-half inch from the top of the pan. On the 
top of the soil 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. 
A known amount of the active ingredient applied in a solvent or as a 
wettable powder suspension and the soil are thoroughly mixed, and used as 
a cover layer for prepared pans. After treatment, the pans are moved into 
a greenhouse bench where they are watered from below as needed to give 
adequate moisture for germination and growth. 
Approximately 2-3 weeks after seeding and treating, the plants are observed 
and the results recorded. Table II below summarizes such results. The 
herbicidal rating is obtained by means of 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 
______________________________________ 
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 legend: 
______________________________________ 
A Canada Thistle 
E Lambsquarters 
I Johnsongrass 
B Cocklebur F Smartweed J Downy Brome 
C Velvetleaf 
G Yellow Nutsedge 
K Barnyardgrass 
D Morningglory 
H Quackgrass 
______________________________________ 
TABLE II 
______________________________________ 
Pre-Emergent 
Com- 
pound of 
Example Plant Species 
No. Kg/ha A B C D E F G H I J 
K 
______________________________________ 
1 11.0 0 0 0 2 0 3 2 2 3 2 
3 
5.6 0 1 0 2 1 1 0 2 0 2 3 
2 11.2 0 0 0 0 1 0 3 1 0 2 3 
5.6 0 0 0 0 1 0 3 2 0 1 3 
3 11.2 0 0 0 0 0 0 1 1 0 1 3 
5.6 0 0 0 0 0 0 1 0 0 1 3 
4 11.2 2 0 0 0 3 0 0 0 3 1 3 
5.6 1 0 0 0 1 0 0 0 0 1 3 
5 11.2 0 0 0 0 1 0 0 0 0 0 1 
5.6 0 0 0 0 1 0 0 0 0 0 1 
6 11.2 1 0 0 0 3 0 0 1 0 0 3 
5.6 0 0 0 0 0 0 0 0 0 0 1 
7 11.2 0 0 0 0 1 0 0 0 0 0 1 
5.6 0 0 0 0 0 0 0 0 0 0 1 
8 11.2 0 -- 0 0 0 0 0 0 0 0 0 
5.6 0 0 0 0 0 0 0 0 0 0 1 
9 11.2 0 0 0 0 1 3 0 1 0 2 3 
5.6 0 0 0 0 1 0 0 0 0 0 3 
10 11.2 0 0 0 1 0 0 1 0 0 3 3 
5.6 0 0 0 3 0 0 1 3 0 3 3 
11 11.2 0 0 0 0 1 0 1 3 0 3 3 
5.6 0 0 0 0 2 0 3 1 0 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 
Q Wild Buckwheat K Barnyardgrass 
D Morningglory T Crabgrass 
______________________________________ 
The results are summarized in Table III. 
TABLE III 
__________________________________________________________________________ 
Pre-Emergent 
Compound of Plant Species 
Example No. 
kg/ha 
L M N O P B Q D R E F C J S K T 
__________________________________________________________________________ 
1 5.6 1 1 0 2 1 -- 
0 0 -- 
1 0 0 0 2 3 3 
1.12 0 1 1 2 3 -- 
0 0 -- 
2 0 0 3 3 3 3 
0.28 0 1 0 2 0 -- 
0 0 -- 
2 1 0 0 3 3 3 
0.056 
1 1 0 0 0 0 0 1 0 1 1 0 0 3 3 3 
0.0112 
0 0 0 1 1 0 0 3 1 1 1 0 1 3 3 2 
0.0056 
0 0 0 1 0 -- 
0 3 -- 
1 1 0 0 3 3 3 
2 5.6 0 0 2 3 1 0 0 0 2 1 2 0 3 3 3 3 
1.12 0 0 0 3 1 0 0 0 0 3 2 0 3 3 3 3 
0.28 0 0 0 1 0 0 0 0 0 2 1 0 1 1 3 1 
0.056 
0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 0 
0.0112 
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 
3 5.6 0 0 0 0 0 0 0 0 0 0 0 0 2 3 3 3 
1.12 0 0 0 0 0 0 0 0 0 0 1 0 1 1 3 2 
0.28 0 0 0 1 0 0 0 0 0 0 0 0 0 0 3 1 
4 5.6 0 1 0 1 0 3 0 1 3 3 3 0 0 2 3 3 
1.12 0 0 0 0 0 0 0 0 0 2 3 0 0 0 3 3 
0.28 0 1 0 0 0 -- 
0 1 0 0 0 0 0 0 0 2 
6 5.6 0 1 0 0 0 0 0 0 3 1 1 0 0 0 1 3 
1.12 0 1 0 1 0 0 0 0 3 3 2 0 0 0 0 2 
9 5.6 0 1 2 2 2 -- 
0 0 0 1 1 0 2 3 3 3 
1.12 0 0 0 2 0 0 0 0 0 0 0 0 0 0 3 2 
0.26 0 0 0 0 0 0 0 -- 
-- 
0 0 0 0 0 2 1 
10 5.6 0 0 1 3 0 0 0 0 0 3 2 0 2 2 3 3 
1.12 0 0 0 0 0 0 0 0 0 1 1 0 0 0 2 3 
0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 3 
0.056 
0 0 0 0 0 0 0 0 0 1 0 0 0 0 3 3 
__________________________________________________________________________ 
EXAMPLES 12-45 
The compounds in the following examples may also be prepared by substantial 
repetition of the general procedures described in Examples 1 and 2, 
modified as to starting materials, reaction temperatures, times, solvents, 
catalysts, bases, etc., to account for the nature of the particular 
reactants, as will be apparent to those skilled in the art. In Tables IV 
and V, the individual compounds are those whose members are identified by 
the generic formulae. In Table IV, Formula IA relates to compounds wherein 
R is characterized by substituted or unsubstituted 1-cycloalken-1-yl 
radicals; in Table V, Formula IB relates to compounds wherein R is 
characterized by substituted or unsubstituted phenyl radicals. 
TABLE IV 
______________________________________ 
##STR4## IA 
Cpd. of 
Ex. No. 
X Y n R.sub.1 
R 
______________________________________ 
12 C1 O 0 -- 2-methyl-6- 
methoxy-1- 
cyclopenten-1-yl 
13 Br S 1 4-CH.sub.3 
2-ethyl-1- 
cyclohexen-1-yl 
14 Cl NCH.sub.3 
0 -- 2-methoxy- 
methyl-6- 
methyl-1-cyclo- 
hexen-1-yl 
15 Cl NH 1 5-OCH.sub.3 
1-cyclohepten-1-yl 
16 Br S 3 4,5,6- 2,6-dimethyl- 
trimethyl 
1-cyclohexen-1-yl 
17 Cl S 1 4-SCH.sub.3 
2,6-diethyl-1- 
cyclopenten-1-yl 
18 Cl S 0 -- 2-allyl-1- 
cyclohepten-1-yl 
19 Br S 0 -- 2-propargyl-6- 
methyl-1- 
cyclohexen-1-yl 
20 Cl O 0 -- 2-CF.sub.36-methyl- 
1-cyclohexen-1-yl 
21 Br S 3 4,5,6- 2-chloro-6- 
trimethyl 
methyl-1-cyclo- 
penten-1-yl 
22 Cl NC.sub.3 H.sub.7 
0 -- 2-NO.sub.26-methyl- 
1-cyclohepten-1-yl 
23 Cl S 1 4-furfuryl 
2,6-dimethyl-1- 
cyclohexen-1-yl 
24 Cl S 0 -- 2-furfuryl-6- 
ethyl-1-cyclo- 
hexen-1-yl 
25 Cl S 1 5-allyl 
3-tetrahydro- 
furfuryl-6-n- 
propyl-1-cyclo- 
hexen-1-yl 
26 Cl S 0 -- 2,5-dimethyl-1- 
cyclopenten-1-yl 
27 Cl S 0 -- 2-methyl-1- 
cyclopenten-1-yl 
______________________________________ 
TABLE V 
______________________________________ 
##STR5## IB 
Cpd. of 
Ex. No. 
X Y n R.sub.1 
R 
______________________________________ 
28 Cl S 0 -- 2,6-dimethyl- 
phenyl 
29 Br S 1 6-Cl 2-methyl-6- 
ethylphenyl 
30 Br S 2 5,6-diCl 
2-t-butyl-6- 
chlorophenyl 
31 Cl O 0 -- 2-methylthio-6- 
methylphenyl 
32 Cl O 1 4-phenyl 
2-nitrophenyl 
33 Br NH 0 -- 2-benzyl-6- 
methylphenyl 
34 Cl NCH.sub.3 1 5-furfuryl 
phenyl 
35 Cl Nn-C.sub.4 H.sub.9 
0 -- 2-CF.sub.36-ethyl- 
phenyl 
36 Cl S 3 4,5,6- 2,3-dimethyl- 
trimethyl 
phenyl 
37 Cl S 0 -- 2-propargyl-6- 
ethylphenyl 
38 Cl O 1 4-NO.sub. 2 
2-methoxy- 
methyl-6- 
methylphenyl 
39 Cl S 0 -- 2-(2-methoxy- 
ethoxy)-6- 
methylphenyl 
40 Cl S 1 4-Br 2-allyl-6- 
methoxyphenyl 
41 Cl S 0 -- 2-t-butyl-6- 
chlorophenyl 
42 Cl S 1 4-ethoxy 
2-tetrahydro- 
furfuryl-6- 
ethylphenyl 
43 Cl S 0 -- 2-furfuryl-6-n- 
propylphenyl 
44 Cl S 0 -- 2-methyl-6- 
isobutoxyphenyl 
45 Cl S 0 -- 2-(trifluoro- 
methyl)-6- 
methylphenyl 
______________________________________ 
The compound of Example 1 has been found to be particularly efficacious as 
a rice herbicide. In Table VI, data is presented showing the effect of 
said compound on the major Asian rice weeds Echinochloa crusgalli (EC), 
Monochoria vaginalis (MV), Cyperus serotinus (CS), Eleocharis kuroguwai 
(EK) and Sagittaria trifolia (ST) in transplanted rice at rates within the 
range of 0.25-2.0 lb/A (0.28-2.24 kg/ha); observations were made 18 days 
after treatment. 
TABLE VI 
______________________________________ 
Compound of 
Rate Percent Inhibition 
Example No. 
(Kg/Ha) Rice EC MV CS EK ST 
______________________________________ 
1 2.24 10 100 100 100 100 5 
1.12 0 100 100 100 100 5 
0.56 0 100 100 90 100 5 
0.28 0 100 100 80 100 0 
______________________________________ 
It is thus seen that the compound of Example 1 selectively controlled all 
weeds in the test, except Sagittaria trifolia at rates as low as 0.28 
kg/ha, the minimum test rate, while maintaining rice safety (i.e., 15% or 
less injury) at 2.24 kg/ha or more. 
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 napthalene 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 deriviatives 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, 
napthalene 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 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 or 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 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 the 
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 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 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 amd 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 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. 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: 
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 
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-diphenylacetamide 
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 
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 1.0 
Free acid of complex organic 
5.59 
phosphate of aromatic or aliphatic hydro- 
phobe base (e.g., GAFAC RE-610, register- 
ed trademark of GAF Corp) 
Polyoxyethylene/polyoxypropylene 
1.11 
block copolymer with butanol (e.g., Tergitol 
XH, registered trademark of Union Carbide 
Corp.) 
Phenol 5.34 
Monochlorobenzene 77.16 
100.00 
B. Compound of Example No. 4 25.00 
Free acid of complex organic 
5.00 
phosphate of aromatic or aliphatic hydro- 
phobe base (e.g., GAFAC RE-610) 
Polyoxyethylene/polyoxypropylene 
1.60 
block copolymer with butanol (e.g., Tergitol 
XH) 
Phenol 4.75 
Monochlorobenzene 63.65 
100.00 
II Flowables 
A. Compound of Example No. 1 25.00 
Methyl cellulose 0.3 
Silica aerogel 1.5 
Sodium lignosulfonate 3.5 
Sodium N--methyl-N--oleyl-taurate 
2.0 
Water 66.7 
100.00 
B. Compound of Example 4 45.0 
Methyl cellulose .3 
Silica aerogel 1.5 
Sodium lignosulfonate 3.5 
Sodium N--methyl-N--oleyl taurate 
2.0 
Water 47.3 
100.00 
III. Wettable Powders 
A. Compound of Example No. 2 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. 3 80.0 
Sodium dioctyl sulfosuccinate 
1.25 
Calcium lignosulfonate 2.75 
Amorphous silica (synthetic) 
16.00 
100.00 
C. Compound of Example No. 6 10.0 
Sodium lignosulfonate 3.0 
Sodium N--methyl-N--oleyl-taurate 
1.0 
Kaolinite clay 86.0 
100.00 
IV. Water-Soluble Powders 
A. Compound of Example 1 10.0 
Sodium dioctyl sulfosuccinate 
2.0 
Silica aerogel 5.0 
Methyl violet 0.1 
Sodium bicarbonate 82.9 
100.00 
B. Compound of Example 4 90.0 
Ammonium phosphate 10.0 
100.00 
V. Dusts 
A. Compound of Example No. 2 2.0 
Attapulgite 98.0 
100.00 
B. Compound of Example No. 3 60.0 
Montmorillonite 40.0 
100.0 
C. Compound of Example No. 6 30.0 
Ethylene glycol 1.0 
Bentonite 69.0 
100.00 
D. Compound of Example No. 10 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. 4 30.0 
Diatomaceous earth (20/40) 70.0 
100.00 
C. Compound of Example No. 6 1.0 
Ethylene glycol 5.0 
Methylene blue 0.1 
Pyrophyllite 93.9 
100.00 
D. Compound of Example No. 10 5.0 
Pyrophyllite (20/40) 95.0 
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. One skilled in 
the art can readily determine from this specification, including the above 
examples, 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.