Note: Descriptions are shown in the official language in which they were submitted.
~ 3~ AG-1161
NOVEL ORTHO-ALKOXY-SUBSTITUTED 2-HALOACETANILIDES,
HEIR M~ OF_~EPARATION AND THEIR USE AS HERBICIDES
Background of the Invention
The invention herein pertains to the field of 2-
haloacetanilides, their preparation, herbicidal composi-
tions containing same as active ingredient and method of usethereof~ In more particular, the herbicidal compositions
herein have particular application in the control of un-
desired plants associated with monocotyledons such as wheat,
sorghum and rice and dicotyledons such as sugarbeets and
soybeans.
Description of the Prior Art
.
It is known in the prior art to prepare 2-haloacet-
anilides having a variety of substituents on the-phenyl ring
and on the anilide nitrogen atom.
As more or less relevant to the compounds of this
invention the prior art discloses various 2-haloacetanilides
which may be substituted with alkyl, alkoxy and/or alkoxyalkyl
radicals or other substituents on the phenyl ring and on the
nitrogen atom. See, for example, German Patent Application
Numbers 2,402,983 and 2,405,183 and U. S. Patent Numbers
3,966,811 and 3,976,471.
Said '983 German patent application discloses herbi-
cidal compounds which may be substituted with alkyl and/or
alkoxyalkyl radicals in the 2' and 6' positions and with an
alkoxyalkyl radical on the nitrogen atom. EIowever, the
alkoxyalkyl radical on the nitrogen atom in said '983 patent
must have no less than two carbon atoms separating the nitro-
gen and oxygen atoms as distinguished from alkoxymethyl-sub-
stituted 2-haloacetanilides. Moreover, said '983 German
patent application does not disclose any examples whatever of
any 2-haloacetanilides having alkoxyalkyl radicals on the
anilide ring or, further, any process for preparing such com-
pounds.
The '183 German application and the '811 and '471
`. ~
2- AG-1161
1~3~
U. S. patents disclose 2-haloacetanilide compounds which may
be substituted with alkoxyalkyl radicals on the phenyl ring,
but not in either of the ortho (2' and 6') positions as
required in the present invention. Moreover, the nitrogen
substituents in the '811 and '471 patents are distinct from
those herein; that in '811 patent being a 2,2-dialkoxyethyl
radical and that in the '471 patent being an alkylideneamino-
oxymethyl radical.
Other less relevant prior art compounds include 2-
haloacetanilides which may be substituted with alkoxyalkyl or
dialkoxyalkyl radicals on the nitrogen atom, but not on the
phenyl ring which may have other substituents thereon; typical
of such compounds are those described in U. S. Patent Numbers
3,442,945, 3,547,620, 3,983,174, 3,952,056, 3,937,730,
4,019,894, 4,021,224, 4,025,554 and 4,086,080.
As relevant to processes for producing analogous
compounds as those described and claimed herein, the closest
prior art appears to be the processes described in the above-
mentioned patents. Illustrative prior art processes involve
the haloacetylation of the appropriately-substituted aniline,
e.g., secondary aromatic amines wherein the phenyl ring and
nitrogen have their substituents affixed-prior to haloacetyla-
tion. Another process involves the reaction of the appropri-
ately-substituted aniline with haloalkanols, e.g., 2-halo-
propanol to introduce the hydroxyalkyl chain on the nitrogenatom, followed by chloroacetylation and, finally, by etheri-
fication of the hydroxyalkyl group with an alcohol to obtain
the corresponding N-alkoxyalkyl compound.
An earlier process involves the haloacetylation of
the appropriately-substituted-phenylazomethine to obtain the
N-halom~thyl adduct thereof which is then reacted with an
alcohol to obtain the corresponding N-alkoxyalkyl compound.
Alternatively, the N-halomethyl adduct is reacted with an
appropriately-substituted salt of an o~ime to obtain the
corresponding product (3,976,471 above).
-3- ~ AG-1161
As relevant to one embodiment of this invention
described below, i.e., wherein silver or other heavy metal
tetrafluoroborate is used as catalyst, J~ C. Sheehan et al (JOI~E1
~merican Ch~m. SO~r 89.;2, pages 362 et se~., esp. 364 and 368,
January 18, 1967), describe a neopentyl rearrangement of 2-
bromo-3,3-dimethyl-N-_-butylbutyramide by use of silver tetra-
fluoroborate. However, that process is described as a dehydro-
bromination resulting in the removal of the 2-halogen atom.
~ccordingly, the process described by Sheehan et al teaches
the labiliky o the 2-halogen atom in the presence of silver
tetrafluoroborate.
The prior art is devoid of disclosure of a process
for producing 2-haloacetanilides by reacting an alcohol with
ortho-benzylic halide lntermediates to produce the corresponding
ether derivative.
Summary of the Invention
The present invention xelates to a new ~lass of
herbicidal 2-haloacetanilide compounds, process for preparing
these compounds, herbicidal compositions containing said com-
pounds as active ingredient and herbicidal method of use,
particularly- to control noxious weeds in soybeans, sugarbeets,
wheat, rice and sorghum.
In more particular, the compounds of this invention
are those having the formula
o
R C-CH2X
N
1 ) ~30R4
wherein
X is halogen,
R and Rl are independently hydrogen, Cl_10 alkyl,
alkoxymethyl or alkoxymethyl substituted with Cl 4 alkyl groups,
R2 and R3 are independently hydrogen, Cl 4 alkyl or
alkoxy groups,
R4 is hydrogen, Cl 10 alkyl or alkenyl, phenyl or
phenyl substituted with Cl 5 alkyl or alkoxy, halogen or nitro
-4- AG-1161
groups and
n i5 an integer from 0-4 inclusive.
The novel process herein involves the preparation
of compounds within the scope of Formula I which comprises
reacting a compound having the formula
R C-CH X
N 2
II l R2 1
~ ~C-X
(Rl)n ~ R3
with a compound of the formula
III R40H
wherein the R-R4 groups are de~ined above and Xl is a chloro,
bromo or iodo atom, preerably in the presence of heavy metal
cations, e.g., silver, lead, mercury, etc., or other Lewis
Acids, e.g., AlCl3, SnC14, ZnC12, etc. The cations are de-
rived from compounds such as acetates, oxides, nitrates, tetra-
fluoroborates and the like. Alternatively, when Xl is bromo
or iodo, alkali metal and alkaline earth Cl 10 alkoxides, e.g.,
the methoxides, ethoxides, propoxides, butoxides, etc., of
sodium, potassium, rubidium, magnesium, zinc, cadmium and
mercury, may be used in lieu of the compound of Formula III.
The discovery of the above process is unexpected
because of the known lability of the 2-halogen on the N-acetyl
radical. Thus, with compounds having halogen sites with essen-
tially the same or relatively similar reactivities, a problem
was created with respect ko differentially replacing the halogen
on haloalkyl-substituted aryl moieties, e~g., benzylic or
xylylic halogens, while preserving the halogen at the 2-acetyl
position to produce desired deri~atives. For example, prior
attempts by the inventor to react either I- or OCH3- anions with
one or both of the benzylic haloalkyl moieties on the compound
2',6~-bis (chloromethyl)-N-(methoxymethyl)-2-chloroacetanilide
resulted in the partial displacement of chlorine at all three
halogen sites. Thus, the simple replacement of chlorine by
nucleophiles in such systems was clearly inadequate.
5 ~3~6~1 AG~
It was discovered by this inventor that the halogen
on halomethyl-substituted aryl molecules, e.g., benzylic halo-
gens, xylylic halogens, etc., could be selectively activated
without activating the otherwise equally labile 2-acetyl halo-
gen by use of silver tetrafluoroborate (AgBF4). Moreover, asnoted above, in alternative embodiments,in some cases, e.g.,
when the o-positions are iodoal~yl or bromoalkyl radicals,
-
these radicals can be etherified in excess alcohol with an equiva-
lent of alkali metal or alkaline earth alkoxide,e.g., sodium
alkoxide.
The process conditions are not critical although
best conducted at temperatures within the range of from about
-80 to 180C, preferably from 0 125C and still more preferably
from 25-100C, although higher and lower temperatures may also
be used for sufficient reaction times and pressures (which may
be subatmospheric or superatmosphere) as to assure complete re-
action. In like manner, concentrations o reactants are not
critical, but it will be understood by those skilled in the
art that the ratios of reactants will be appropriately selected
following the detailed description and working embodiments
herein.
As used herein, the term "alkyl" and combined forms
thereof as in "alkoxymethyl" is understood to include primary,
secondary and tertiary alkyl radicals.
The preferred compounds herein for use in herbicidal
compositions are those in which (having reference to Formula I)
X is chlorine, bromine or iodine and, especially chlorine; R
and R4 are lower alkyl groups, particularly methyl; R is an
Cl 10 alkyl or alkoxymethyl radical, particularly Cl 5 alkyl or
alkoxymethyl radical and R2 and ~3 are hydrogen atoms.
Representative compounds of the present invention in-
clude those in which the R-R4 groups of the above formula in-
- clude methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl,
secondary isobutyl and tertiary butyl radicals and the R, R
and R4 radicals further include n-amyl, branch chain amyls,
the normal and branched hexyls, heptyls, octyls, nonyls, and
decyls and corresponding R4 C2 10 alkenyl groups, preferably
C2 4 alkenyl groups, particularly the allyl radical.
In one aspect of this invention, preferred compounds
3~ AG-ll61
- are N, 2'-bis or N, 2',6'-tris ~alkox~methyl)-2-haloacetanilides
wherein the alkoxymethyl radicals have the same alkyl radical
in the alkoxy moiety. These compounds are prepared by using
silver tetrafluoroborate catalyst dissolved in an alcohol sol-
vent of Formula III wherein R4 is the same alkyl radical as thatin ~he alkoxy moiety of R in Formula II. In such case, etheri-
fication occurs selectively at the 2' and/or 6'-haloalkyl posi-
tion(s), as exemplified in Example 18 below. On the other hand,
~hen the R4 alkyl radical o~ Formula III is different from that
in the alko~y moiety in the alkoxymethyl radical R of Formula II,
transetherification can occur between the R4 and R groups result-
ing in N,2'-bis or N,2',6'-tris (alkoxymethyl) compounds having
the same R4 alkyl radical in the alkoxymethyl positions.
Another aspect of this invention concerns 2-haloacet-
15 anilid~ compounds having different alkoxymethyl radicals on theN atom and in the 2' and/or 6' positions (i.e., the ortho posi-
tions relative to the anilide nitrogen atom). Compounds of this
type are prepared by reacting N,2'-bis or N,2',6'-tris (alkoxy-
methyl)-2-haloacetanilides of Formula I with an alcohol of Formula
III wherein R4 is dif~erent from and usually larger than the
alkyl moiety in the N and 2' and/or 6' positions in the presence
of an organic sulfonic acid such as methyl sulfonic acid. In
such case, transetherification occurs selectively between the R4
and alkoxymethyl radical on the nitrogen atom; the preparation
of compounds of this type is exemplified in Example 22 below.
The transetheri~ic~tion process discussed in this paragraph is
the subject of a separate invention by a dif~erent inventorship
entity in the assignee's laboratories.
Alternatively, the foregoing compounds having the same
or different alkoxyme~hyl radicals in N and 2' and/or 6' positions
may be prepared by the N-alkylation o the anion o~ a secondary
2-haloacetamide having one or more o-alkoxymethyl su~stituents
with an alkylating agent such as a haloalkyl alkyl ether, e.g.,
chloromethyl methyl ether;
Example 23 below exemplifies this N-alkylation pro-
cess to prepare N~2'~-bis(alkoxymethyl)-2-haloacetanilides~ Com-
pounds of the type discussed in this and the preceding paragraph
may also be prepared ~y reaction of metal salts of the alcohols
of Formula III, e.g., R40M wnere M is an alkali~ne earth) metal,
7- ~t316~1 AG-1161
with compounds of Formula II wherein R is alkox~methyl, X i5
chlorine and Xl is bromo or iodo.
The herbicidal compositions herein are useful as
selective herbicides by applying them to the locus of undesir-
able plants to be controlled and desirable plants to be protected.
The invention will be more clearly understood byreference to the following detailed description.
Detailed Description of the Invention
The compounds of this invention are derived from
intermediate compounds characterized in relevant part by having
halomethyl substituents in one or both ortho-positions of the
anilide ring. These intermediate compounds are themselves
novel and the subject of another invention by the inventor
herein who has discovered a plurality of methods for the
production of the intermediates. Among these methods may
be mentioned the frae radical halogenation, preferably in the
presence of ultraviolet light, of 2-haloacetanilides. Chlori-
nation readily occurs to give mono-chlorination at the N-
methyl and/or o-alkyl position, but no reaction at the alpha
or nuclear centers. Bromination, with elemental bromine, but
more particularly with N-bromosuccinimide, is selective,
giving only o-alkyl mono-bromination, even in the presence of
an N-methyl moiety. Exemplary processes for preparing the
intermediates used in this will be described in examples which
follow; all temperature readings are degrees Centigrade.
Example 1
This example describes alternative methods for the
preparation of the intermediate starting material, N-(methoxy~
methyl)-2',6'-bis(chloromethyl)-2-chloroacetanilide used to
prepare an invention compound.
l(a). 2-Chloro-N,2',6'-trimethylacetanilide (21.1 g, 0.1
mol) was placed in 200 ml CCl~ and an internal 0.2 amp UV
source illuminated within the 500 ml flask. Chlorine (0.1
mol, 7 g) was introduced subsurface with stirring, The reac-
tion was mildly exothermic, with temperature climbing from20 to 40. After all chlorine had been added, an essentially
colorless soLution was obtained, while nmr showed an obvious
mixture with both the -CH3 group on both the ring and the N
8- ~3~ AG~1161
atom undergoing substitution. Neither ClCH2C(O) norring H
moieties were affected. The mixture was cooled to ca 5 and
another 0.1 mol chlorine added with nmr still indicating a
mixture of mono-chlorinated N-CH3 and ring -CH3. Finally, a
third molar equivalent of chlorine was added, with a good
deal of spectral simplification. The material was permitted
to stand over the weekend, then solvent removed to give vis-
cous oil. Portions of this were recrystallized from pentane-
ether to give crystals, mp 70~75. Carbon dissulfide also
was a good solvent for recrystallization. This material, on
the basis of nmr (and its further reactions) was assigned the
structure, 2-chloro-N, 2'~6'-tris(chloromethyl) acetanilide.
The b~lk of the viscous oil (7 g) was heated in 250
ml methanol on a steam bath for 10 minut~s, let cool gradually,
then stripped of all but ca 50 ml methanol. White crystals
developed, and 5 g of these were filtered off, mp 111-114.
Recrystallization from carbon tetrachloride, mp 117-118.
Analysis: Calc'd for C12H14C13NO2(%): C, ~6.40; H, 4.54, N, 4.51;
Cl, 34.24
Found: C, 44.48; H, 4.33; ~, 4.64;
Cl, 34.96.
The product was identified as the above-mentioned intermediate.
l(b). It was also demonstrated that said intermediate
could be prapared from the preformed N-chloromethyl compound
(derived from chloroacetyl chloride and azomethi~e of 2,6-
xylidine). 2-Chloro-N-(chloromethyl)-2',6'-acetoxylidide
(10 g, 0.04 mol) in 200 ml CC14 was reacted with 0.081 mol
(5.8 g) chlorine at 40-45. Additional 1.4 g C12 was added
to make up losses from chlorine volatility. Solvent was
removed and the residue boiled with ca 300 ml methanol for
lt2 hour, then two-thirds of this volume was removed, the
contents scratched, filtered to give 6.4 g.
-9- AG-1161
Example 2
Two grams (0.0065 mol) of the compound of Example 1,
i.e., N-(methoxymethyl)-2',6'-bis(chloromethyl)-2-chloroacet-
anilide was placed in 25 ml methanol, warmed to dissolve, and
0.0135 mol (2.7 g) silver tetrafluoroborate (AgBF4) dissolved
in 10 ml methanol was added. Material stirred with heating
at 35-40. Only 0.8 g Ag Cl collected on filtering. Small-
scale investigation revealed that little more precipitate
could be collected from this filtrate on heating, but more
precipitate resulted on heating if more AyBF4 was added.
Therefore 2.5 g additional AgBF4 was added and the material
actually heated at reflux three minutes, and kept above 55
for 10 minutes more. The filtrate was boiled once again in
the filtering flask on a hot plate, then filtered to give 0.1
g (total AgCl precipitate 1.6 g). The filtered solution was
placed in the refrigerator overnite. Then 2.0 g more AgBF4
was added and material boiled ca 5 minutes, to give 0.1 g
more AgCl (total 7.2 g AgBF4). The methanol solution was
reduced to 1/5 its volume, then added to 5~ NaHC03 solution.
There was an immediate precipitate Ag2O (3.1 g). This was
filtered off and salt (NaCl) added with CH2Cl2. The aqueous
salt solution was extracted several times with CH2C12. After
drying, organic solution was vacuum treated to give 1.2 g
light yellow oil.
Analysis: Calc'd for C H2 ClNO4(%): C, 55.72; H, 6.68;
14 0
N, 4.64; Cl, 11.75
Found: C, 55.71; H, 6.69;
N, 4.65; Cl, 11.78
Upon repeating the procedure a second time using
3.1 g of said intermediate 2.1 g yield of final product was
obtained.
The product was identified as N,2',6'-tris(methoxy-
methyl)-2-chloroacetanilide by NMR.
Example 3
N-(methoxymethyl~-2',6'-bis(chloromethyl)-2-chloro-
acetanilide (2.5 g, 0.0081) was placed in 100 ml isopropanol
-1 o- 1~31~1 AG-1161
with 8.6 g AgBF4, then refluxed l hour, cooled. AgCl (2.3 y~
was recovered. The material was treated with 5~ NaHCO3 solu-
tion, then extracted with CH2Cl2 with salt being added to in-
sure complete Ag~ removal and ether-amide recovery. The
S mixture was ~iltered, organic solution separated and material
vacuum treated to remove solvent to give 2.3 g oil which by
nmr showed no CH30; and three-isopropoxy groupings. The
crude (1.7 g) was distilled at 200-210 (0.05 mm) in a Kugel-
rohr to give 1.3 g amber oil distilled; nmr unchanged.
Anal. Calc~d for C20H3~ClNO4(%): C, 62.24; H, 8.36; Cl, 9.19
N, 3.63
Found: C, 62.10; H, 7.84; Cl, 8.25
N, 4.16
The product was identified as N,2',6~tris(isopropoxymethyl)-
2-chloroacetanilide.
Example 4
2',6'-bis(l-chloroethyl)-N-me~hyl-2-bromoacetani-
lide (0.01 mol) was placed in ca. 75 ml methanol which con-
tains 2.4 g (0.012 mol) AgBF4. After standing overnite in
the dark, the mixture is filtered to recover AgCl, stripped of
solvent, taken up in pure methylene chloride washed with
aqueous solution of NaCl and Na2CO3, and dried over Mg504.
After filtering and drying, material vacuum treated to remove
solvent, and residue recrystallized and/or vacuum sublimed.
Anal- Calc'd ~or C15H22BrN3(~) C, 52-33; Br~ 23-21; N~ 4.07
Found: C, 49.75; Br, 25.57; N, 3.98
The product, m.p. 86-95C obtained in 19% yield was identified
as 2',6'-(bis-1-methoxyethyl)-N-methyl-2-bromoacetanilide.
Example 5
. .
2'-(Bromomethyl)-6'-t-butyl-N-methyl-2-bromoacetanilide
(3.7 g, 0.01 mol) was placed in 150 ml methanol, and 2.4 g
AG-1161
AgBF4 in 50 ml methanol was added. Material was permitted to
stand three hours, 1.6 g AgBr filtered off; further standing
overnite gave 0.1 g more AgBr (theory 1.9 g). The material
was vacuum treated to remove solvent, and the residue treated
with the usual mixture of CH2C12/NaCl/10% Na2CO3. After
filtering (canvas filter), the filtrate stripped to give oil
which crystallized on standing. Recrystallization from
hexane, mp 55-60, 2.1 y. Second recrystallizatian from
heptane gave a white solid, mp 72-74.
Anal. Calc'd for C15H22BrNO2(%): C, 54.88; H, 6.76; Br, 24.34;
N, 4.27
Found: C, 54.87; H, 6.77; Br, 24.26
N, 4.29
The product was identified as 2'-(methoxymethyl)-6'-t-butyl-N-
methyl-2-bromoacetanilide.
Example 6
2'-Bromomethyl-6'-t-butyl-N-methyl-2-chloroacetanilide
(5 g, 0.015 mol) was dissolved in 250 ml ethanol and 3.3 g of
a clear solution of 3.3 g AgBF4 in 50 ml ethanol added at room
temperature thereto. There was an instantaneous precipitate
of yellow AgBr. Material permitted to stand in the dark over-
night, then AgBr filtered off and ethanol removed under vacuum.
The residue taken up in methylene chloride, washed with 150
ml 10% Na2CO3 (to which some NaCl had been added). After
filtering the two liquid phases, the organic layer was sepa-
rated, washed once more with water, then solvent removed in
vacuo. The residue was recrystallized from heptane,
and a second recrystallization from ethanol to give 3.0 g
yield, m.p. 77-78C.
Anal. Calc'd for C16H24ClNO2(%): C, 64.52; H, 8.12; N, 4.70
Found: C, 63.50; H, 7.81; N, 4.82
The product ~as identified as 2l~ethoxymethyl)-6'-t-butyl-N-
methyl-2-chloroacetanilide.
-12- ~131~ AG-1161
~xample 7
2'-(Bromomethyl)-6'-t-butyl-N-methyl-2-chloroacet-
anilide ~1.7 g, 0.005 mol) was placed in ethylene dichloride
and added to a solution consisting of 0.7 g p-cresol and 1.0
g AgBF4 in ethylenedichloride. There was an instant, theory
precipitate of AgBr. After standing no more than 1/2 hour,
solution treated with NaCl solution and filtered to remove
last vestiges o~ silver ion. The ethylene dichloride solution
was then washed with 5% NaOH to remove phenol. After these
washed, CH2C12 added and organic solution given a final water
wash. After drying over MgS04, filtering and vacuum treat-
ment to remove solvent the residue was recrystallized from
isopropanol, then once again to give 0.3 g white solid
product, m.p. 148-152C.
Anal. Calc'd for C H ClNO (%): C, 70.08; H, 7.28; N, 3.89
- 21 26 2
. Found: C, 69.93; H, 7.29; N, 3.84
The product was identified as 2'~ tolyloxymethyl)-6'-_-
butyl-N-methyl-2-chloroacetanilide.
Example 8
2'-(Bromomethyl)~6'-t-butyl-N-methyl-2-chloroacetani-
lide (1.6 g, 0.005 mol) was placed in methanol and a methanol
solution of 0.95 g sodium p-nitrophenate was added. The
material was refluxed 2 hours, cooled, scxatched, 0.8 g solid
precipitate, mp 185-186. Portion recrystallized from aceto-
nitrile, to obtain whitç crystals, mp 186-187C.
Anal. Calc'd for C20H23ClN2O4(~): C, 61-46; H, 5.93; Cl, 9.07i
N, 7.17
Found: C~ 61.37; H, 6.01; Cl, 9.12;
N, 7.09
The product was identified as 2'~ nitrophenoxymethyl)-6'-
t-butyl-N-methyl-2-chloroacetanilide.
-13- 1131~ AÇ-1161
Example 9
2'-fchloromethyl)-6'-t-butyl-N-methyl-2-chloroacetani-
lide (0.01 mol) was placed in about 75 ml t-butanol containing
2.4 g (0.012 mol) ~gBF4. After standing overnight in the
dark, the mixture was filtered to recover AgCl, stripped of
solvent, taken up in pure CH2C12, washed with aqueous solution
of NaCl and Na2CO3 and dried over MgSO4. After filtering
and drying, the material was vacuum treated to remove solvent
and the residue recrystallized and/or vacuum distilled.
Anal. Calc'd for C18 H28ClNO2(~): C, 66.34; H, 8.66; N, 4.30
Found: C, 65.21; H, 8.49; N, 4.41
The product, mp 65-67C, obtained in 46~ yield was identified
as 2'~ butoxymethyl)-6'-t-butyl-N-methyl-2-chloroacetanilide.
Example 10
The same procedure in Example 9 was followed, but
suhstituting n-propanol for t butanol. The product, a white
solid, mp 53-54C, was obtained in 64% yield and had the
following elemental analysis:
Calc'd for C17H26ClNO2(%): C, 65.47; H, 8-40; N~ 4-49
C, 64.42; H, 8.15; N, 4.63
The product wasidentified as 2'-(n-propoxymethyl)-6'-t-butyl-N-
methyl-2-chloroacetanilide.
Example 11
Following the identical procedure in Example 6, but
substituting methanol for ethanol, a white solid recrystallized
from methanol having mp 74-75C was obtained in 70~ yield.
Anal. Calc d for C15H22ClNO2(%): C, 63-48; H~ 7-81; N~ 4.94
Found: C, 63.47; H, 7.83; N, 4.97
The product was identified as 2'-(methoxymethyl)-N-methyl-2-
chloroacetanilide~
-14~ 6~ AG-1161
Example 12
2'-(Bromomethyl)-6'-_-butyl-2-chloroacetanilide
(1.6 g, 0.005 mol) was placed in 25 ml methanol, and 1 g (ca
0.005 mol) AgBF4 added in 20 ml methanol. There was an
instant precipitate of theory AgBr. Without further delay,
the filtered methanol solution was vacuum treated to remove
solvent and 10% Na2CO3 solution added to the residue, along
with methylene chloride solution and NaC1. After filtering
through a sintered glass funnel with minimum suction, the
methylene chloride layer was separated, then vacuum treated
to remove solvent. The solid residue, mp 70-90, 0.8 g re-
crystallized from variety of solvents the best being cold,
aqueous methanol. For analytical sample, the material, a
white solid, was vacuum sublimed, oil bath 100-110 (0.05
mm), mp 101-102~
Anal- Calc d for Cl4H20clNo2(%) C, 62.33; H, 7.47; Cl, 13.1~;
N, 5.19
Found: C, 61.45; E, 7.40; Cl, 12.82;
N, 5.01
The product was identified as 2'-~methoxymethyl)-6'-t-butyl-
2-chloroacetanilide.
The above product could alternatively be prepared by
reacting 3.2 g of the above 2'-bromomethyl starting material
in methanol with 0.01 mol sodium methoxide (7.0 ml, 1.48M
NaOCH3 in CH30HI. Reaction heated at 50-60, cooled, let
stand, stripped, water/CH2C12 added. CH2C12 solution stripped
off and solid recrystallized methylcyclohexane to give product
identical with that described above.
Example 13
Following the same procedure in Example 12 but using
ethanol as the alcohol, a white ~olid recrystalliæed from hep-
tane, was obtained in 55% yield, mp 110-112C.
Anal. Calc'd ~or C15H22ClN2(%) C, 61-87; H, 8-16; N~ 5-L5
Found: C, 61.02; E, 7.55; N, 5.07
-15- ~131~ AG-1161
The product was identified as 2l-(ethoxymethyl)-6~-t-butyl-2
chloroacetanilide.
Example 14
Following -the same procedure in Example 13, but
substituting isopropanol as the alcohol, a greyish solid, mp
98-100C, was obtained in 50% yield.
Anal. Calc'd for C16H2~ClNO2(%): C, 64.53; H, 8.12; N, 4.70
Found: C, 64.35; H, 8.09; N, 4.72
The product was identified as 2'-(isopropoxymethyl)-6'-t-
10 ~utyl-2-chloroacf~tanilide.
Following the same procedure as in Example 13, but
substituting n-butanol as the alcohol, 2'-(n-butoxymethyl)-
6'-t-butyl-2-chloroacetanilide, mp 75-77C, was obtained in
lS 45% yield.
Anal. Calc'd for C H26ClNO2(~): C, 65.47; H, 8.40; N, 4.49
17
Found: C, 65.53; H, 8.41; N, 4.54
Example 16
In similar manner as described in Example 4, but
using n-propanol as the alcohol, 2'-(n-propoxymethyl~-6'-t-
butyl-2-chloroacetanilide, mp 40C, was obtained in 40~ yield.
Anal. Calc'd for C16H24ClNO2(~): C, 64.52; H, 8.12; N, 4.70
Foundo C, 63.33; H, 7.89; N, 4.73
Example 17
2'-(Bromomethyl)-6'-t-butyl-2-chloroacetanilide (3.2
g, 0.01 mol) was dissolved in 75 ml of allyl alcohol, then
2.4 g (0~012 mol) of silver tetrafluoroborate dissolved in 75
ml allyl alcohol was added. The mixture was allowed to stand
~31~ AG-1161
overnight in the dark. Filtered and stripped of solvent.
The resultant oil was dissolved in CH2C12 and washed once with
NaCl solution, then twice with water. The organic layer was
dried over MgSO4 and stripped to leave an oil which was
crystallized from pentane. Yield 1.7 g, mp 65-67C.
Anal- Calc'd for C16H22ClN2(~ C, ~4-96; H~ 7.50; N~ 4-74
Found: C, 63.85; H, 7.21; N, 4.~8
The product was identified as 2'-(allyloxymethyl)-6'-t-butyl-
2-chloroacetanilide.
Example 18
2'-(Bromomethyl)-6'- t-butyl-N-(methoxymethyl)-2-
chloroacetanilide (4.2 g, 0.0113'mol) was placed in 250 ml
methanol and 50 ml of solution of 3.3 g AgBF4 in 50 ml metha-
nol was added. There was an instant precipitate of AgBr, but
the mixture was allowed to stand overnite in the dark, then
filtered rom 89% theory AgBr. After methanol had been re-
moved, the residue was treated in methylene chloride to a
mixture of sodium chloride and 10% sodium hydroxide. The
liquid phases were filtered and the organic phase separated
from the filtrate. After solvent removal, 3.0 g of oil remain-
ed which gave consistent nmr structure. The material was dis-
tilled in kugelrohr at 200~206 (0.1 mm) to give 2.0 g nearly
colorless oil in 59% yield.
in Calc'd ~or Cl6H24ClNO3(%): C, 61i24, H, 7.71; N, 4.46;
_ _ _ __ Found. C, 60.95; Hz 7,.77; N, ,4.~5
Cl, 11~44
------------~m~e- p-roaucF-was identi~ied as 2'-(mëthoxymethyl)-6l-t-butyl-N-
_ ~methoxymethyl~- -chl,,o,r,o,ace~ta~ilide.
Example 19
Following the procedure in the preceding examples,
but using as starting materials 2'-(bromomethyl)-6'-t-butyl-
W-(ethoxymethyl)-2-chloroacetanilide and ethanol, a white
-17- ~131~6~ AG-1161
solid, mp 114-116 was obtained.
Anal. Calc d for C18H28ClNO3(%): C, 63.24; H, 8.26; N, 4.10
Found: C, 62.64; H, 7.90; N, 4.87
The product was identified as 2'-(ethoxymethyl)-6'-t-~utyl-
N-(ethoxymethyl)-2-chloroacetanilide~
Example 20
Two grams of 2'-formyl-6'-t-butyl-2-chloroacetani-
lide was dissolved in 10 ml methanol and 10 g (CH30)3CH, few
drops of SOC12 added to form catalytic amount of HCl.
Material was refluxed on the steam bath 45 minutes, after
having stood overnite at room temperature (not necessary).
A few drops o~ 50~ caustic was added to neutralize acid, and
cooled solution vacuum stripped to give semi-solid residue
(pH ca. 8-9). pH adiusted to 12-14, by adding caustic and water.
The resulting solid filtered, washed on filter cake with water,
dried in oven at 60 for 2-3 hours to give 2.1 g. (87% yield) o~
white solid, mp 127-132C. Anal. sample from isopropanol.
Calc'd for C15H22ClNO3(%): C, 60.10; H, 7.40; N, 4~67
Found: C, 58.92; H, 7.12; N, 4.77
The product was identified as 2'-(dimethox~methyl)-6'-t-butyl-
2-chloroacetanilide.
Example 21
Five grams (0.012 mol) of 2~,3~-bis-(bromomethyl)-6~-
t-butyl-2-chloroa~etanilide was placed in 175 ml methanol,
then mixed~ with 7.0 AgBF4 dissolved in the same solvent.
Material let stand overnite in the dark, with AgBr iltered
off. Methanol evaporated, CH2C12 added, treated with NaCl/
N~2CO3, filtered through clay, washed once again with water.
After stripping solvent after drying, solid recrystalIized
from ether. Anal. sample vacuum sublimed, mp 115-117.
Calc'd for C16H24ClNO3(%~: C, 61.24; H, 7.71; Cl, 11.30; N, 4.46
Found: C, 58.05; H, 7.42; Cl, 10.64; N, 4.24
The product, a greyish solid obtained in 50% yield, was identi-
fied as 2',3'- bis-(methoxymethyl)-6'-_-butyl-2-chloroacetanilide.
-18~ 16~1 AG-1151
The acetanilide starting material of this example
was prepared as follows:
In a 1 liter flask lS g (0.059 mol) of 2',3'-dimethyl-
6'-t-butyl-2'-chloroacetanilide was dissolved in 600 ml CC14.
Reaction provided with two white flood lites. The reaction
mixtuxe was heated to reflux, then sparged with nitrogen.
Bromine (9.44 g, 0.059 mol) in 50 ml CC14 was added dropwise.
During bromine addition, nmr monitoring revealed that reaction
did not proceed stepwise, but rather both arylmethyl groups
10 were brominated at nearly the same rate. Total of two molar
equivalents of molecular bromine was added, and nmr o reaction
mixture at this stage showed clean reaction in good yield.
After standing over weekend, reaction mixture filtered, mp 180-
182, recrystallized gave 187-189. Vacuum sublimation for
lS elemental analysis gave mp 195-197. Yield 50%.
Anal. Calc'd for C14H18Br2ClNO(~): C, 40.85; H, 4.41; N, 3.40
~ound: C, 40.~0; ~, 4.37; N, 3.40
This product was identified as in the lead sentence of this
example.
Example 22
This example illustrates the preparation of compounds
having different alkyl radicals in the alkoxy moiety of the
alkoxymethyl radicals attached to the N- and o-positions.
Three (3) grams of 6'-methyl-N,2'-bis(methoxymethyl)-
25 2-chloroacetanilide were mixed with 75 ml of n-butanol and 5
microdrops of methyl sulfonic acid; the mixture was refluxed
over soxhlet filled with 3 A mol sieve. The reaction, by GLC,
was completed in about one hour. The material was stripped,
leaving some butanol, taken up in benzene, washed once with
30 NaHCO3, evaporated to 75C (0.4 mm) to give 3.0 g (87% yield) by
GLC of an oil.
Anal- Calcld for C16H24ClNO3 (%): C, 61.12; H, 7.71; N, 4.46
Eound: C, 62.12; H, 8.01; N, 4.29
The product was identified as 2'-(methoxymethyl)-6l-methyl-N-
35 (n-butoxymethyl)-2-chloroacetanilide by Nmr.
Example 23
Twenty-six (26) grams of 2'-methyl-6'-(methoxymetnyl)-2-~hloro-
acetanilide dissolved in about 200 ml of an 80:20 diethyl ether:
-19- ~3~ AG-1161
tetrahydrofuran mixture was treated with well-rinsed KH; theory
H2 evolved. Excess chloromethyl methyl ether was added. After
reaction and aqueous washes, crude material showed GLC assay
nearly equivalent to a distilled heart cut,26 g yield (84%).
The material chromatographed through Florisil to give 19 g oil,
b.p. 180C (0.05 mm).
~nal- Calc'd or C13H18ClN3 (%): C, 57.46; H~ 6-68; N~ 5-15
Found: C, 57.32; H, 6.72; N, 5.13
The product was identified as 2'-methyl-N,6'-bis(methoxymethyl)-
10 2-chloroacetanilide.
The process used in this example may be modified by
use of a starting acetanilide having a different alkoxymethyl
radical in the o-positions from that placed on the N atom by
the halomethyl alkyl ether.
Examples 24-28
In similar manner as described in the above examples,
other compounds corresponding to Formula I above wer-e prepared;
these compounds are identified in Table I together with certain
physical properties.
-20~ AG-1161
i6~
O et~ D Q t`
U~
Ul
a~
~1 ~ t` O ~ ~ O n ~r ~ o ~1 ~o ~D O O 1~
,~ ~ r o ~ ~I CO O a~ ~ ~D Lr) ~ ~ ~D
C~
~ ~ $ æ c~ x z c~ ~: z c~ æ c~ ~ z
~1
w
c~ ^ r co
I ~
. o ~ l ~1 ~ ~1_
~ ~ ~3 ~ l ~1 1 ~D .
H. ' E3 ~1 a~ ~1 0 ~ O
~~ m--~ ~ o ~ ~_
ZO Z Z o Z
O ~1 ~D ~r o ~ ~
s~ e m :~ m ::c m
rl s~ ~ ~I ~ O U~
e ~ c~
~,
I
~1 rl I
I ~ ~_
_,, .,,I ,_, I a~
I ~ d w ~ ~~ :~
--~dI ~I ~ a) II x ~
,~ O ~:5
a)~ u
C~ 1 ~~ o
X
~~ o~ s~~ o
o~ o
oo ~X OX--o X ~~--
o~5)oIoI~ oa)oI~
~Z o ~ ~~Z o
I~ I ~
I I ~~1 0 O OO ~1 0
--o~ ~ ~
a)
O
~C Z t~
~3~
AG-1161
-21-
.
Examples 29-62
Yet other compounds corresponding to Formula I
herein and contemplated as within the scope of this invention
. are shown in Table II. In the examples, the individual
compounds are those whose members are identified by Formula
S ~.
. .
, .
. . .
.
.
. .
. .
. .
...... .
. . .
:-.
.,,
. .
... .
'~ ~
AG-116 1
-- 22 --
x I ~ m m c~ o m H c~ m c) c~ ~ c) c) m c~ m c~ ~ H O m m
~1
r~ ~ X ~ r ~ o r. ~ x
~ N
~1
x r~ c x ~ x x ~: r~
a~
~~1
F!:; x 5: ~ x ~ : x ~ x m ~
H
H ~: ¦ O ~1 ~ I ~1 ~ ~ ~1 ~ ~1 ~1 0 ~1 ~ ~1 ~) ~r ~1 0 ~1 ')
Q u) ~ 0
r~r~ r
~r~: X ~ X ~ m ~ x
_` U~ Lf y
u~ ~
o
o
~ ~ .
,~ ~ ~ ~ ~Y7 ~ ~ ~ ~1
,~, tc ~ r~ r~ ~ ~ r~ ~ h ~ Q ~ R~ ~ r~ r~
0
o o ,1l 1 1
mm
o ~
ll
:: ~: X ~ : X ~ r ~ $r~ $~
s~
a) Q~Q ~ Q O O O
U~ I I I
X ~ ~ o ~ ~ ~ ~ ~ ~ o ~ ~ ~ u~ ~ 1` 0~ ~ O
.....
.
~3~
-23- AG-1161
X I t) c) C~ C.) U C~
~ ~1 ~ ~ ~ ~ ~1
~1 $ ~ ~ ~ 0~ m ~ .~
o ~ a~ ~ a
o
I
i ~1 1 a
~r ~
x ~ $ m m ~ m
--
oP~
s: ~ ~ m ~ P: m ::: m o o m
~ I ,~ ~ ,1 ~1 ~1 ,1 ,1 ~1 ~1 0 0
H
: _
~ C~
O O
~ $ x m P::q m m ~ m
~_ ~ C~
~a
o ~
.,,
U~
~ ~,
u~
~1 ~ ~ ~ m
- ~ ~ ~c m ~ x
Q~ U :q Q R C )
_ Q ~ ~ Y Z-l ~1 ~ m
I ~ U C~ C~ V
~ I J ' ' ' _,
~ ~ o
~ m p ~ ' I
~; o ~ o ~ o o o o o ~ ~I o o
o ~ o x ~ m ~:
I ~ I I I I I ~ ~ I I
a) I
I ~ ~ ~ ~ ~n ~ 1~ ~0 cn o ,~ ~
~3~6~ AG-1161
-24-
As noted above, compounds according to this inven-
tion have been found to be effective as herbicides in the
partial or total inhibition of undesirable vegetation. Tables
IIIA and IVA summarize results of tests conducted to determine
the pre-emergent herbicidal activity and Tables IIIB and IVB
the post-emergent herbicidal activity of representative com-
pounds.
The pre-emergent test was conducted as follows:
A good grade of top soil was 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 was
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 was
weighed into a pan. A known amount of the active ingredient
applied in a solvent or as a wettable powder and the soil
were thoroughly mixed, and used as a cover layer for prepared
pans. After treatment, the pans were moved into a greenhouse
bench where they were watered from below as needed to give
adequate moisture for germinatîon and growth.
Unless noted otherwise, approximately 2 weeks after
seeding and treating, the plants were observed and the results
recorded. Tables IIIA and IVA 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 o
25-49
50-74 2
75-100 3
The post-emergent tests were conducted as follows:
The active ingredients are applied in spray form to
two or three week old specimens of various plant species. The
-25~ t~ AG-1161
spray, a solution or wettable powder suspension containing
the appropriate rate of active ingredient to give the desired
test rate and a surfactant, is applied to the plants. The
treated plants are placed in a greenhouse and unless other-
wise noted approximately two weeks later the effects ranging
from no response to total inhibition are observed and recorded.
The results are shown in Tables IIIB and IVB in which the
post-emergent herbicidal activity index is as follows:
~ Control Rat g
0-24 0
Z5-49
50-74 2
75-99 3
lO0 4
The plant species utilized in these tests 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 Nutsedge K Barnyardgrass
20 D MorninggloryH Quackgrass
66~L
~~5~ AG-1161
Table IIIA
Plant Species
Compound of
E~ample No. Lb/A (Rg/Ha) ~ B C D E F G H I J K
2 5.0(5.6) 0 0 1 0 0 1 2 1 0 3 3
3 5.0(5.6) 0 0 0 0 1 0 0 0 3 1 3
4 10.0(11~2) 0 0 0 1 0 0 1 0 0 0 0
5.0(S.6) 0 0 0 1 0 0 0 0 0 1 1
5.0(5.6) 0 0 1 1 3 3 0 0 0 3 3
6 5.0(5.6) 1 1 1 1 3 2 3 3 1 2 3
7 10.0(11.2) 3 0 1 0 3 2 1 1 0 3 3
8 10.0 (11.. 2) 1 0 0 1 0 0 0 0 0 3 3
5.0(5.6) 1 0 0 1 0 0 1 0 0 1 1
9 5.0(5.6) o 0 0 0 2 0 3 2 0 2 3
5.0(5.6) 0 0 0 0 3 1 2 1 0 3 3
11 5.0(5.6) 0 0 0 1 3 1 2 0 0 1 3
12 5.0 (5-6) 0 0 1 2 3 1 2 1 0 2 3
13 5.0(5.6) 0 0 1 0 2 1 2 1 0 2 3
14 5.0(5.6) 0 0 1 1 3 0 3 1 1 3 3
5.0(5.6) 1 0 1 0 2 2 3 3 0 3 3
16 10.0(11.2) 0 0 1 0 3 1 3 3 1 2 3
5.0(5.6) 0 0 1 0 1 0 2 2 1 2 3
17 10.0(11.2) 0 1 1 1 2 1 1 2 0 2 3
5.0(5.6) 0 0 1 0 3 0 1 1 0 0 3
1~ 5.0(506) 0 0 1 1 3 1 1 2 1 3 3
1~ 10.0(11.2) 0 0 1 1 2 0 2 2 1 3 3
5.0~5.6) 0 0 1 0 2 0 1 2 1 1 2
lOoO(11.2) 1 0 1 1 3 1 1 1 0 1 3
5.0(5.6) 0 0 0 0 2 0 1 0 0 0 2
22 10.0(11.2) 1 1 1 1 1 1 2 3 1 3 3
5.0(5.6) 1 1 1 1 1 0 1 3 1 2 3
23 5.0(5.6) 0 0 0 0 2 0 0 0 0 0 1
24 5.0(5.6) 1 1 2 2 3 3 2 0 0 3 3
5.0(5.6) 3 0 0 Q 1 2 0 1 0 1 3
26 10.0(11~2) 3 2 2 2 3 3 3 2 0 3 3
5.0(5.6) 3 1 1 2 3 3 2 1 0 3 3
27 lQ.Q(11.2) 0 0 Q 0 0 0 0 0 0 0 3
5.0(5.6) 0 0 0 0 0 0 0 0 0 0 3
':
~L~3~;6~
-27- AG-1161
Table IIIA (Cont'd)
Pre-Em~ent
Plant Species
Compound of
Example No. Lb/A (K~/Ha) A B C D E F G H I J K
.
28 10.0(11.2) 3 2 1 3 3 3 3 2 0 3 3
5.0(5.6) 2 2 1 2 3 1 3 2 0 3 3
Table IIIB
Post-Emergent
Plant Species
Compound of
Example No. Lb/A (K~/Ha) A B C D E F G H I J K
2 5.0(5.6) 0 1 0 1 0 0 0 0 - 0
4 10.0(11.2) 0 1 0 1 4 1 0 l 0 0 0
10.0(11.2) 0 1 1 2 1 0 0 0 0 0 0
6 10.0(11.2) 1 1 l 1 2 1 0 1 0 0 2
7 10.0(11.2) 0 l 0 0 1 1 0 0 0 0
8 lO.0(11.2) 1 l 0 0 0 0 0 0 0 0 0
9 10.0(11.2) l 1 0 1 4 4 0 0 0 1 2
10.0(11.2) 1 1 l 1 1 1 1 1 1 0 2
11 10.0(11.2) 0 1 0 l l 0 0 0 0
12 10.0(11.2) 0 l 0 l 0 0 0 0 0 0 0
13 10.0(11.2) 1 1 0 l 1 1 0 0 0 0
14 lO.0(11.2) 0 0 0 1 l 0 0 0 0 0
10.0(11.2) 1 1 0 1 l 1 0 0 0 0
16 10.0(11.2) 1 1 1 1 2 1 1 1 0 0 2
17 10.0(11.2) Q 1 0 1 1 0 1 0 0 0 2
18 10.0(11.2) 1 1 0 1 1 1 0 0 :- 0 2
10.0(11.2) 0 0 1 1 0 0 l 1 0 0 0
23 lO.0(11.2~ 0 0 1 0 0 0 0 0 0 0 0
- 24 10.0(11.2) 0 1 0 1 0 2 0 0 0 0 2
10.0(11.2) 0 l 0 1 0 0 0 0 0 0 2
26 10.0(11.2) 0 1 0 l - 1 1 0 0 0 2
28 10.0(11.~) 0 1 1 l 0 0 1 l 0
` -28- ~3~6~ 1161
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 Bromus tectorum (Downy brome)
B Cocklebur S Panicum Spp.
Q Wild Buck-. K Barnyardgrass
wheat
D Morning- T Crabgrass
glory
The results axe summarized in Tables IVA and IVB.
13~6~
-29- AG-1161
Table IVA
Pre-Emergent
Plant S~ecies
Compound of
Example No. Lb/A (I;~/Ha) L M N O P ~ Q D R E F C J S K T
2 5.0 (5.6) 0 l 1 0 l 0 0 1 1 2 1 0 0 3 3 3
1.0 (1.12) 0 1 0 1 2 0 0 0 1 0 1 0 2 3 3 3
0.?5 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 3
0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
3 1.0 (1.12) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1
0.05 (0.061 0 0 - 0 0 0 0 0 0 0 0 0 0
l.0 (1.12) 1 0 0 2 3 0 1 0 1 1 1 0 0 2 3 3
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3
0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1
6 5.0 (5.6) 1 2 2 3 3 0 1 0 1 1 l 0 2 3 3 3
l.0 (1.12) 0 l l l 2 0 0 0 0 1 0 0 l 2 3 3
0.25 (0.28) 0 0 0 0 2 0 0 0 0 1 0 0 l 2 2 2
0.05 (0.06) ~0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
7 5.0 (5.6) 0 1 0 1 0 0 0 0 1 0 1 0 0 2 3 3
1.0 (1.12) 0 0 0 1 0 0 0 0 0 0 1 0 0 l 3 3
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 Z
8 5.0 (5.6) 1 2 0 0 0 0 0 0 l 0 0 0 0 0 3 2
1.0 (1.12) 0 l 0 0 0 0 0 0 0 0 0 0 0 0 l l
9 1.0 (1.12) 3 1 1 1 2 3 l 0 1 2 l l 1 2 3 3
0.25 (0.2~) 3 1 0 1 1 3 0 0 1 l 0~1 0 1 2 2
0.05 (0.06) 3 0 0 0 0 3 0 0 0 o 0 0 0 0 0 0
. .
5.0 (5.6) 1 3 2 3 3 0 0 1 2 3 3 l 3 3 3 3
l.0 (1.12) 1 2 2 2 3 0 0 0 0 1 1 0 2 3 3 3
0.25 (0.28) 1 l l 1 2 0 0 0 0 0 1 0 2 2 3 3
0.05 (0.06) 0 0 0 1 0 0 0 0 0 0 1 0 0 1 l 2
11 5,0 (5-6) 2 3 l 2 3 0 0 0 1 2 2 l 2 3 3 3
1.0 (1.12) 1 2 0 0 1 0 0 0 1 2 1 0 l 3 3 3
0.25 (0.~8) 1 1 0 0 1 0 0 0 0 2 0 0 0 2 3 2
0.05 (0.06) 1 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1
~- ~13~
~30- AG-1161
Table I~IA
Pre-E~er~ent
Plant Species
Compound of
Example No. L~/A (K~/Ha) L M N O P B Q D R E F C J S K T
12 1.0 (1.12) 2133300111003333
0. '5 (0.28) 1 0 0 1 1 0 0 0 1 0 0 0 2 2 2 3
0.05 (0.06) 0 0 0 0 0 Q 0 0 0 0 0 0 0 0 0 1
13 5.0 (5.6) 3333332333313333
1.0 (1.12) 21223302 2 2 0 1 2 333
0.25 (0.28) 1 1 0 1 1 0 0 310001333
0~05 (0.06) 0 0 0 1 1 0 0 0 1 0 0 0 0 0 1 1
0.01 (0.011) 0000030000000000
14 5.0 (5.6) 2 2 333102 2 3 2 33333
1.0 (1.12) 2 1 2 33 0 0 1 2 2 1 1 3 333
0.25 (0.28) 1 0 0 0 1 0 0 0 0 0 0 0 0 1 3 3
0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
0.01 (0.11) 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0
5.0 (5.6) 2 3 3 3 3 1 0 1 3 3213333
1.0 (1.12) 1 2 2 3 2 0 0 0 2 1 1 0 2 2 3 3
0.25 (0.28) 010100000000112 2
16 5.0 (5.6) 1 2 1 3310123 2 1 333 3
1.0 (1.12) 0101100011102 3 3 3
0.25 (0.28) 0001000011001223
0.05 (0.06~ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2
17 5.0 (5.6) 2 2 3 2302111103 3 3 3
1.0 (1.12) 1010100000001133
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2
18 5.0 (5.6) 2 222302223 2 1 3333
1.0 (1.12) 1 1 1 1 2 0 1 2 2 2 1 0 2 333
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2
0.05 (0.06) 0 0 0 1 0 0 0 1 0 0 0 0 0 0 1 2
19 5.0 (5.6) 1 2 3 3 3 0 0 2 1 2 2 0 3333
1.0 (1.12~ 1 1 0 1 300111103333
0.25 (0.28) 0 1 0 0 1 0 0 0 1 1 0 0 2 2 2 2
5.0 (5.6) 2 1 2 2 301111113333
1.0 (1.0) 0 0 0 0 0 0 0 0 1 0 0 0 1 1 2 2
:' ' : ,
.: . ,
66~
-31~ AG-1161
Table IVA (Cont '~)
Plant Species
Compound of
Example No. L_ (Kg/Ha) L M N O P B Q D R E F C J S K T
22 5.0 (5.6) 0 0 1 1 2 0 0 1 1 1 0 1 3 33 3
1.0 (1.12) 0 0 0 1 1 0 0 0 0 1 0 0 2 2 33
0.25 (0.28) 0 1 0 0 0 0 0 0 0 1 0 0 0 0 1 2
0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
24 5.0 (5.6) 0 2 0 1 3 2 3 2 2 3 3 2 1 3 3 3
1.0 (1.12) 0 1 0 0 2 0 0 1 1 1 1 0 0 3 33
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 1 0 0 3 33
0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2
5.0 (5.6) 0 1 1 0 31 3 1 1 2 3 0 1 3 3 3
1.0 (1.12) 0 - 0 0 1 0 2 0 0 3 2 0 2 3 3 3
0.25 (0.~8) 0 1 2 0 0 0 0 0 0 0 ~ 0 1 3 3 3
0.05 (0.06) 0001000000000032
0.01 (0.11) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
26 5.0 (5.6) 1 2 2 33 3 2 3 3 - 313333
1.0 (1.1;~) 0 3 1 331313 - 3 03333
0.25 (0.28) 0 2 1 2 3 0 0 0 2 - 2 0 1 3 33
0.05 (0.06) 0 0 0 0 0 0 0 0 0 - 1 0 0 1 3 3
0.01 (0.11) 000001000 - 20003 2
27 5.0 (5.6) 0 0 0 0 0 0 1 0 1 3300033
1.0 (1.12) 00000000 - 31000 2 3
0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
28 5.0 (5.6) 0 323323333303333
1.0 (1.12) 0 2 0 2 3 1 3223303333
0.25 (0.28) 0 1 0 0 1 0 0 0 0 3 300333
0.05 (0.-06) 0000001003200022
,~ . .
6~;~
-32- AG-1161
Table IVB
Post-Emergent
Plant S ecie~
Compound of P
Example No. Lb/A (Kg/Ha) L M N O P B Q D R E F C J S K T
9 5.0 (5~6) 2 1 0 1 1 1 1 2 1 2 1 1 0 1 3 3
1.0 (1.12) 1 0 0 0 0 0 1 1 1 1 0 1 0 0 2 2
0.25 (0.28) 1 0 0 0 0 0 1 1 1 0 0 0 0 0 1 1
0.05 (0.06) 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
~33- ~ ~ 3~ 6~ ~ AG-1161
The herbicidal compositions of this invention in-
cluding concentrates which require dilution prior to appli-
cation contain at least one active ingredient and an adju-
vant in li~uid 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 particu-
late solids, ~ranules, 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 emulsi-
fying agent or any suitable combination of these.
The compositions of this invention, particularly
liquids and wettable powders, preferably contain as a con-
ditioning 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 acetyleni~ 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 dis-
persants are methyl cellulose, polyvinyl alcohol, sodium
lignin sulfonates, polymeric alkyl, naphthalene sulfonates,
sodium naphthalene sulfonate, and the polymethylene bisnaphtha-
lene sulfonate.
Wettable powders are water-dispersible compositions
containing one or more active ingredients, an inert solid
6~L
-34~ ~G-1161
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 re-
quired, from about 0.1 to 2~0 paxts of the solid inert extender
can be replaced by a corrosion inhibitor of anti-foaming `agent
or both.
Aqueous suspensions may be prepared by mixing to-
gether and grinding an aqueous slurry o water-insoluble active
ingredient in the presence of dispersing agents to obtain a
concentrated slurry of very inely-divided particles. The
resulting concentrated aqueous suspension is characterized
by its extremely small particle size, so that when diluted
and sprayed, coverage is very uni~orm.
Emulsifiable oils are usually solutions o active
ingredient in water-immiscible or partially water-immiscible
solvents together with a surface active agent. Suitable
solvents for the active ingredient o this invention include
hydrocarbons and water-immiscible ethers, esters or ketones.
The aqueous suspensions and emulsifiable oil compo-
sitions ge~erally contain from about 5 to 95 parts (preferably
5-50 parts) active ingredient, about 0.25 to 50 parts (preer-
ably 1-25 parts) surace active agent and where required
about 4 to 94 parts solventj alI parts being by weight based
on the total weight of emulsifiable oil.
Granules are physically stable particulate composi-
tions comprising active ingredient adhering to or distributed
through a basic matrix of an inert, finely-divided particulate
~3~
~35~ AG-1161
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 vermicuiite are
examples o~ operable classes o~ particulate mineral extenders.
The pre~erred extenders are the porous, absorptive, preformed
particles such as preformed and screened particulate atta-
pulgite or heat expanded, particulate vermiculi~e, and the
finely-divided clays such as kaolin clays, hydrated attapul-
gite or bentonitic clays. These extenders are sprayed orblended with the active ingredient to form the herbicidal
granules.
The granular compositions of this invention general-
ly contain ~rom about 5 parts to about 30 parts by weight of
active ingredient per 100 parts by weight of clay and O to
about 5 parts by weight of surface active agent per
lOO parts by weight of particulate clay. The preferred granu-
lar compositions contain from about 10 parts to about 25 parts
by weight o~ active ingredient per 100 parts by weight of
~ 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
o~ this invention include, ~or example, triazines, ureas,
carbamates, acetamides, acetanilides, uracils, acetic acid or
phenol derivatives, thiolcarbamates, triazoles, benzoic acids,
nitriles, biphenyl ethers and the like such as:
3-amino-2,5-dichlorobenzoic acid
3-amino-1,2,4-triazole
5-amino-4-chloro-2-phenyl-3(2H~-pyridaæinone
2-chloro-4-ethylamino-6-isopropylamino-s-triazine
2-chloro-N,N-diallylacetamide
2-chloroallyl diethyldithiocarbamate
N'-(4-chlorophenoxy) phenyl-N,N-dimethylurea
131~
-36- AG-1161
N,N-dimethyl-N~(3-chloro-4-methylphenyl) urea
S-(.4-chlorobenzyl).N~N-diethylthiolc~rbamate
isopropyl N-(3-chlorophenyl) carbamate
2,2-dichloropropionic acid
S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate
2-methoxy-3,6-dichlorobenzoic acid
2,6-dichlorobenzonitrile
N,N-dimethyl-2,2-diphenylacetamide
6,7-dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt
3-(3,4-dichlorophenyl)-1,1-dimethylurea
4,6-dinitro-o-sec-butylphenol
1,3-dimethyl-3-t2-benzothiazolyl) urea
ethyl N,N-dipropylthiolcarbamate
2,3,6-trichlorophenylacetic acid
5-bromo-3-isopropyl-6-methyluracil
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea
2-methyl-4-chlorophenoxyacetic acid
3-(~-chlorophenyl)-1,1-dimethylurea
l-butyl 3-(3,4-dichlorophenyl)-1-methylurea
N-l-naphthylphthalamic acid
1,1'-dimethyl-4,4'-bipyridinium salt
2-chloro-4,6-bis~isopropylamino)-s-triazine
2-chloro-4,6-bis(ethylamino)-s-triazine
2,4-dichlorophenyl-4-nitrophenyl ether
alpha, alpha, alpha~trifluorc-2,6-dinitro-N,N-
dipropyl-p-toluidine
S-propyl dipropylthiolcarbamate
2,4-dichlorophenoxyacetic acid
: N-isopropyl-2-chloroacetanilide
2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide
2'-methyl-6'-ethyl-N-(2~methoxyprop-2-yl)-2-
chloroacetanilide
: : monosodium acid:methanearsonate
disodium methanearsonate
N-(l,l-dimethylpropynyl)-3,5-dichlorobenzamide
2-chloro-~,~,a-trifluoro-p-tolyl-3-ethoxy-4-nitro-
dinhenyl ethe~
Sodium 5-f2-chloro-4-ttrifluoromethyl)phenoxy]-2
nitrobenzoate
Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate
-37- AG-1161
4-amino-6-t-butyl-3-methylthio-1,2,4-triazin-5-one
N-~2,4-dimethyl-5-~[(tri~luoromethyl)sulfonyl]amino~
phenyl~ acetamide
3-isopropyl~lH-2,1,3-benzothiadiazin-4-(3H)-one 2,2-
dioxide
3-methyl-4-amino-6~phenyl-1,2,4-triazine-5-one
N-(phosphonomethyl) glycine and its Cl 6 monoalkyl
amine and alkali metal salts and combinations thereof in ratios
of 1-4 lb/acre (1.12-4.48 kg/ha) to 1-10 lb/acre of compounds
of this inverltion-
Fertilizers useful in combination with the active in-
gredients 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.
When operating in accordance with the present invention,
effective amounts of the acetanilides of this invention are ap-
plied 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 thereo~, the type and condition of soil, the amount
of rainfall and the speci~ic 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 acetani-
lide is usually employed. Lower or highex rates may be required
in some instances. One skilled in the art can readily determine
from this specification, including the above example, the opti-
~3~- AG-1161
mum rate to be applied in any particular case.
The term "soil" is employed in its ~roadest sense
to be inclusive of all conventional "soils" as defined in
Webster's New International Dictionary, Second Edition, Una-
bridged (1961). Thus the term refers to any substance ormedia 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 con-
strued as limitations except to the extent indicated in the
following claims.
