Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
I 19 36-1499
This invention relates to novel N-chloroacet~1-2-methyl
6-acylaniline compounds and derivatives whereof, methods of their
use as herbicides and herbicidal compositions thereof.
United States Patent 4,141,989 discloses 3-(N-chloro-
acetyl-(-N-2,6-dialkylphenylamino)-gamma-butyrolacatones) as
fungicides
United States Patent 4,055V410 discloses substituted
broom and chloroacetamides ho herbicides.
It has now been wound that the placement of certain
substituents on the 6-position of N~chloroacetyl~2-methyl
analines results in compounds having herbicidal activity. The
compounds of the invention are particularly effective for pro-
emergent treatment of grassy weeds.
The compounds of the invention are included in a
broader class of compounds of general formula:
Al
N-- C SHUCKS (I)
R2 R
wherein Al is alkyd of 1 to 4 carbon atoms; or alkoxy of ] to
4 carbon atoms;
R is alkenyl having 2 to 13 carbon atoms, substituted alkyd of
1 to 13 or substituted alkenyl of 1 to 13 carbon atoms substitute
Ed with 1 or 2 hydroxy groups or 1 or 2 alkoxy groups of 1 to 4
carbon atoms or 1 or 2 alkenyloxy groups of 2 to 4 carbon atoms;
azalea of 2 to 4 carbon atoms; a group of the formula
\ / \ 5
-C \ (CUR on
wherein n-2, 3 or 4; R4 it alkyd of 1 to 3 carton atoms and R5
USSR 287,617 - 1 -
is hydrogen or alkyd of 1 to 3 carbon atoms; or a group of the
formula R4
-C--NOR6
wherein R4 is defined above and R6 is hydrogen or alkyd of 1 to
3 carbon atoms;
R3 is hydrogen or alkyd of 1 to 4 carbon atoms; X is halogen; and
Y is oxygen or sulfur.
However the present invention is restricted to a come
pound of the formula I'
SUE
- No ITCH Of to')
/ \
R" R'
wherein R' and R" are independently methyl or ethyl and R3 is
hydrogen or methyl.
Thus it has now been found that, although the come
pounds of Formula I hereinabove have good reemergence activity
against grasses, that within this genus the compounds of the
sub-genus indicated by Formula (I') above (compounds of the
present invention have surprisingly superior reemergence
activity against grasses.
The compounds of Formula I' are effective at very low
dosages and exhibit safety with respect to soybean, cotton, and
peanut crops. The compounds of Formula (I') wherein R is
methyl, are slightly less active than the compounds wherein R3
is hydrogen but also have a slightly higher safety factor with
respect to the aforementioned crops. In terms of reemergence
activity against gasses per unit cost best results are obtained
.~,
I
using the compound of Formula I' wherein R3 is hydrogen or
methyl and R' and R" are each methyl.
The compounds of formula I generally can be made
according to the following schemes, and it will be seen that the
compounds of the present invention (I') are included within these
schemes by selection of suitable values of appropriate sub-
stituent groups
. I
I
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hydrochloride, and a base, erg., an inorganic alkali metal carbonate such
as potassium carbonate or a trialkylamine such as trieth~lamine. also,
although or convenience, chloroacet~l chloride has been shown as the
assaulting agent, because it is preferred, other haloacetyl halides ego.
~oromoacetyl bromide) could also be used.
Typically, the acylation is conducted at temperatures in the
range of about from 2C to 15QC, preferably 10 to 5~C, for about from
lo minutes to 72 hours, pref~ra~l~ I to 24 hours using about prom 0.5
to I moles, preferably 1 to 3 moles of the assaulting agent per mole
of aniline reactant. Typically, the ablation is conducted in a suitable
inert organic solvent such as, for example, alkyd ethers, ego. ethyl
ethers, aromatics ego, Bunsen, Tulane), halogenated alikeness ethylene
chloride); alkali esters ego., ethyl acetate), liquid alikeness (e.g.,
hexane), and the like.
Also, although for simpliclt~ the aniline reactant has been
shown as unsubstituted at the N position in the reaction equations, the
N R substituted compounds can be prepared in the same manner by using
the~a~propriate R3 substituted starting material.
Generally, the above reactions are conducted as liquid phase
I reactions and hence pressure is generally not material except so far as
it affects the temperature of reactions conducted at reflex. For example,
the reactions can be conducted at pressures on the range of from 20Q to
5~0Q mm Hug and conveniently are conducted at atmospheric or ambient pressure.
The compounds of the present invention are, in general
her~icidal in both pro- and post-emergent applications but are particularly
effective in reemergent applications For pro emergent control of undesir-
axle vegetation, the herbicidal compounds will be applied in herbicidally
e~ec~ive amounts to the locus or growth medium of the vegetation, ego,
sill infested with seeds and/or seedlings of such vegetation. Such applique-
ion will inhibit the grittily of or kill the seeds germinating seeds end
-aye-
seedlings. For post-emergent applications, the herbicidal compounds
Wylie be applied directly to the collage and other plant parts. Generally,
the her~icidal compounds of the invention are effective against weed
grasses as, well as broad leaved weeds,. Some ma be selective with respect
to the type of application and/or type of weed. The compounds of the
invention are particularly effective as pre~eme~gent herbicides against
weed grasses.
The compounds, when applied Jo growling plants above the ground
in such an amount that the compounds will not kill beneficial plants,
also show efficient plant growth regulating or retarding effects and may be
advantageously employed, for example, to prevent or retard the
I
01 I
growth of lateral buds in plants and to promote the
thinning out of superfluous fruits in various fruit trees.
The compounds can be applied in any of a variety
of compositions In general, the compounds can be
extended with a carrier material of the kind used and
commonly referred to in the art such as inert solids,
water and organic liquids.
The compounds will be included in such compost
lions in sufficient amount so thaw they can exert an
herbicidal or growth regulating effect. Usually from
about 0.5 to 95~ by weight of the compounds are included
in such formulations.
Solid compositions can be made with inert pow-
dons. The compositions thus can be homogeneous powders
that can be used as such, diluted with inert solids to
form dusts, or suspended in a suitable liquid medium for
spray application. The powders usually comprise the
active ingredient admixed with minor amounts of condition
in agent. Natural clays, either absorptive, such as
attapulgite, or relatively non absorptive, such as china
clays, diatomaceous earth, synthetic fine silica, calcium
silicate and other inert solid carriers of the kind con-
ventiollal1y employed in powdered herbicidal compositions
can be used. The active ingredient usually makes up from
0.5-90~ of these powder compositions. The solids oared-
warily should be very finely divided. For conversion of
O the powders to dusts talc, pyrophyllite, and the like,
are customarily used.
squid compositions including the active come
pounds described above can be prepared by admixing the
compound with a suitable liquid delineate medium. Typical
of the liquid media commonly employed are methanol, bent
zone, Tulane, and the like The active ingredient us
ally makes up from about 0.5 to 50~ of these liquid combo-
sessions. Some of these compositions are designated to be
used as such, and others to be extended with large quanta-
ties of water.
I
01
--10--
Compositions in the form of wettable powders or
liquids can also include one or more surface active
agents, such as wetting, dispersing or emulsifying agents.
the surface active agents cause the compositions of
wettable powders or liquids to disperse or emulsify easily
in water to give aqueous sprays.
The surface active agents employed can be of the
anionic, cat ionic or non ionic type. whey include, or
example, sodium long-chain carboxylates, alkyd aureole Swahili-
notes, sodium laurel sulfate, polyethylene oxides, lignin
sulfonates and other surface active agents.
When used as a reemergent treatment, it is
desirable to include a fertilizer, an insecticide, a
lung it ire or another herbicide.
The amount of compound or composition ad minis-
toned will vary with the particular plant part or plant
growth medium which is to be contacted, the general toga-
lion of application -- i.e., sheltered areas such as
greenhouses, as compared to exposed areas such as fields
-- as well as the desired type of control Generally for
both pro- and post-emergent herbicidal control, the come
pounds of the invention are applied at rates of 0.2 to 60
kg/ha, and the preferred rate is in the range 0.5 to 40
kg/ha. For plant growth regulating or retarding activity,
it is essential to apply the oxide compounds at a concern-
traction not so high as to kill the plants. Therefore, the
application rates for plant growth regulating or retarding
activity will generally be lower than the rates used for
p` killing the plants. Generally, such rates vary from 0.1
to 5 kg/ha~ and preferably from 0.1 to 3 kg/ha.
Herbicidal tests on representative compounds of
the invention were made using the following methods
I` Reemergent ~erbicidal Test
An acetone solution of the test compound was
prepared by mixing 375 my of the compound, 118 my of a
non ionic surfa~tant and 18 ml of acetone. 10 ml of this
solution was added to 40 ml of water to give the test
solution.
-11~
Seeds of the test vegetation voyeur planted in a pot of soil rid
the test solution was sprayed unto onto the soil surface at a dose
of 270$ micrograms/cm2. The pot was Atwood and placed in a greenhouse.
The pot was watered intermittently and observed for seedling emergence,
wealth of emerging seedlings, etch for a 3-week period. At the end of
this period, the her~icidal effectiveness of the compound was rated based
on the physiological observations A 0 to 100 scale was used, 0 wrier-
setting no phytotoxicity, 100 representing complete kill the results
of these tests appear in Tables I and IA.
Post-Emergent Her~icidal Test
The test compound was formulated in the same manner as described
above for the reemergent test. This formulation was uniformly sprayed
on 2 similar pots of 24-day-old plants (approximately 15 to 25 plants per
jot) at a dose of 27~5 microgram/cm20 After the plants had dried they
were placed in a greenhouse and then watered intermittently at their bases,
as needed. The plants wore observed periodically for phytotoxic effects
and physiological and morphological responses to the treatment After
3 weeks the herbicidal effectiveness of the compound was rated based on
these obserYationsO A 0-to-100 scale was used 0 representing no phytotox-
icily and lo representing complete kilo The results of these tests appear
in Table I.
Example 1 - Preparation of
A. Nastily 2-~ethyl-6-acet~laniline ~76.1 g) in water ~300 my
ethanol ~300 ml), concentrated hydrochloric acid ~300 ml) and concentrated
sulfuric acid ~15 ml3 were reflexed for I hours. The solution was cooled
and concentrated ammonillm hydroxide was added to pal 10. The solution was
extracted with dichloromethane. The extract were dried McCoy) and
s~rippedO 2-methyl_6-acetylaniline ~49.3 go was obtained as a tan solid.
I By 2-~ethyl_6-acetylaniline C2S g) and pardon
~2605 g) in 1 liter ethylene chloride were cooled in an
~2i~3~
01 12-
ice acetone bath. A solution of chloroacetyl chloride
(37.g g) in 100 ml ethylene chloride was dripped in slow-
05 lye The solution was stirred at room temperature for 2
hours, washed with 10% Hal, 10% Naomi dried McCoy) and stripped. Yield: the title product as a white solid, MY
88-89C.
Example 2 - Preparation of 2,4,5-Trimethyl-
2-(3-methyl-2-chloroacetam dophenyl) dioxolane
The product from Example 1 (1006 9) 213-
dihydroxy butane (8.5 g) and pylon sulfonic acid (1.5
g) in 200 ml Bunsen were reflexed to 2 hours, removing
water with a Dean stark trap. The solution wash washed
with 10% Noah, dried ~gSO4) and stripped. The product
was chromatographed on a silica gel column, eluding with
3Q~ ethyl ether:hexane. Yield: 3.8 9 of the title prod-
vat, my 55-57C.
Example 3 - Preparation of (methyl-
2'-chloroacetamido) acetophenone O-methyloxime
I -- -
2-Methyl~6-acetylaniline (from Example lay was
reflexed with methoxyamine hydrochloride in ethanol to
yield (3'-methyl-2'-amino) acetophenone Methyl oxide
(I).
- US Compound I (1.72 g) and 1 g triethy]amine in 35
ml ethylene chloride were cooled in an ice bath and long
chloroacetyl chloride was added slowly.
The solution was stirred at room temperature
overnight r washed with 10% clue, 10% Nikko, water and
dried (McCoy). The solvent was stripped to yield 1.2 g of
the title product, mop 119-120C.
Example 4
` Preparation of 2-methyl-6-chlorocarbony~nitrobenzene
In this example or 14 moles of 3-methyl-2-nitro-
benzoic acid were reflexed with 6.43 moles (468 ml) of
thinly chloride for three hours and then allowed to stand
overnight. The mixture was then again reflexed until the
mixture turned a dark brown color. Excess thinly
chloride was removed by evaporation affording 434.4 g of
the title product.
I
~2~3~
01 -13-
Example 5
Preparation of 2-methyl-6-methoxycarbonyl-nitroben2ene
05 In this example a solution containing 1.002 mole
of 2-methyl-6-chlorocarbonyl-nitroben2ene in 200 ml of
ethyl ether and a small amount of ethylene chloride was
added to mixture containing 1.5 mole (60.8 ml) of methanol
10002 mole (139.7 ml) of triethylamine and 200 ml of ethyl
ether at about 0C. The resulting mixture was stirred for
one hour and then allowed to stand overnight. The mixture
was then filtered and the filtrate washed with dilute
aqueous acid and then washed with an aqueous sodium vicar-
borate solution. The washed filtrate was dried and
evaporated affording 183.3g of the title product.
Similarly, by using the appropriate alkanol in
place of methanol, the corresponding homology of the title
compounds used as starting materials for the corresponding
products indicated in Tables A and B can be prepared.
Example 6
Preparation of 2'-methyl-6l-methoxycarbonylaniline
In this example 0.02 mole of 2-methyl-6-methoxy-
carbonyl-nitroben~ene in 25 ml of acetic acid was added
drops to a slurry containing 6.59 of zinc dust sup-
I penned in 25 ml of water at 30-35C. The resulting ego-
thermic reaction is controlled by maintaining the mixture
at about room temperature about 20-25C) through external
cooling. The reaction product mixture was filtered to
remove the zinc dust and the filtrate, then washed sequent
tidally with ethylene chloride and water, and then
extracted with ethylene chloride. The extract was washed
with an aqueous ammonium hydroxide, then with water and
filtered through diatomaceous earth The filtrate was
then dried and evaporated affording 2.7 g of the title
I product as an Gil-
Example 7
Preparation of
methyl hydroxy~ methylethyI)-aniline
In this example a solution containing 381.46 9
of methyl iodide in 500 ml ox ethyl ether was added drop
wise to 65.3 g of magnesium submerged in ethyl ether at
-
- "
I
0 1
room temperature and under neutron the mixture was then
cooled and then a solution containing 0.67 moles of 2'-
methyl-6'-methoxycarbonylaniline in 500 ml of ethyl ether
was drops added thereto. The mixture was then reflexed
for 2-1/2 hours, then cooled and 750 ml of saturated
aqueous ammonium chloride solution carefully added drop-
wise. Additional ammonia chloride solution was then
added and the resulting mixture filtered through autumn-
Swiss earth. The water layer in the filtrate was decanted
from the ether layer and washed with ether. The ether
washings were combined will the ether layers washed with
water, dried and evaporated to dryness affording the title
product.
Similarly, by following the same procedure but
using the appropriate alkyd or alkenyl iodide and subset-
tuned aniline starting materials, corresponding alkyd or
alkenyl homology of the title compounds needed as starting
materials for the corresponding products listed in Table B
hereinbelow were prepared.
Example 8
Preparation of
2'-methyl-6'-(l-ethoxy-1-methylethyl)-aniline
In this example 0.03 moles of boron trifluoride
ethyl ether ate was added drops to a mixture containing
0~03 moles of 2l-methyl-6'-(l-hydroxy-l-methylethyl)
aniline in 50 ml of ethanol and 50 ml Mullen chloride.
The mixture was reflexed for two hours and then allowed to
stand for two days. The mixture was then poured into
about 700 ml of saturated aqueous sodium bicarbonate soul-
lion stirred and extracted with methyl chloride. The
extract was filtered through diatomaceous earth, dried and
evaporated affording 5.4 g of the title product as an oil.
similarly, by following the same procedure using
the appropriate alkanol or alkenol starting material and
boron trifluoride ether ate, the corresponding interim-
dilates for the products listed in Table B hereinbelow were
prepared.
I
~L2~3~
Al -15-
Example 9
Preparation ox 2' methyl ethoxy-1-methyl-
05 ethyl)-N-chloroacetylaniline
In this example 1~45 g (1.03 my of chloroacetyl
chloride was added drops to a solution containing 1.44
g (2 ml) of triethylamine and 0.0129 mole of methyl'-
(l-ethoxy-l--methylethyl)aniline in ethylene chloride at
about but below 20C. The mixture was then reflexed and
then allowed to stand Overnight at room temperature.
Another 0.51 ml of chloroacetyl chloride and 1 ml of in-
ethyl amine was then added drops. The mixture was then
again reflexed and allowed to stand overnight at room
lo temperature The mixture was then washed with saturated
aqueous sodium bicarbonate, dried and evaporated affording
the title compound as a brown oil.
Example 10
Preparation of
methyl' methylprop-l-enyl)-N-chloroacetylanlllne
In this example a mixture of 0.0089 mole of 2'-
methyl-6'-(1-hydroxy-1-methylpropyl)-aniline was saturated
with gaseous hydrogen chloride and then reflexed for one
hour the mixture was then poured into aqueous 10~ (wt.)
sodium hydroxide. The organic phase was separated washed
with aqueous 10% (White sodium hydroxide and extracted with
ethylene chloride. The extract was then dried and
evaporated affording a mixture of the Claus and trays
isomers of 2'-methyl-6'-(1-methylprop-1-enyl)-aniline as
an oil.
0.007 mole of chloroacetyl chloride was added
drops to a mixture of 0~007 moles of methyl-
methylprop-l-enyl~-aniline and 0.008 moles (1.15 ml) of
~triethylamine in ethylene chloride at about but below
20C. The mixture was then reflexed and then allowed to
stand overnight at room temperature. The mixture was then
again reflexed and allowed to stand for two days (over the
weekend) at zoom temperature Thin layer chromatographic
(plate) analysis showed the presence of a small amount of
starting material. An additional 0.55 ml of triethylamine
and 0.3 ml of chloroacetyl shrouds added and the
.
.
.
Lo
01 -16-
mixture again reflexed and allowed to stand overnight at
room temperature. The mixture was then washed with
aqueous sodium bicarbonate, dried and evaporated affording
1.7 g of the title compound as a slightly crystallized oil
(mop. 71-74C).
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TABLE I
05 HERBICIDAL ACTIVITY
Pre/Post % Control
No. L M P C W O
165/60 60/6~ 75/20 97/6Q 100/60 93/15
2 55/0 55/0 60/0 1~0/2~ 100/45 98/20
3 I 0/0 0/0 90/0 90/0 55/0
0/0 0/0 0/0 90/0 90/0 50/0
5 10/0 0/0 0/0 9S/0 100/0 70/0
6 50/0 78/0 95/0 -100/65 100/85 98i~
7 0/0 30/0 0/0 92/0 g5/30 90/10
8 45/0 8~/0 85/0 100/55 100/85 95/20
g I 0/0 I 100/0 90/0 15/0
10 40j0 30/0 60~0 95/0 100/60 15/~
11 0/0 0/0 0/0 90/0 95/o 0/0
12 0/30 0/20 0/25 sluice 97/15 30/0
L = Labs quarter condom album)
M - Mustard brusque arvensis)_
P = Pugged ran thus retro~lex~ls~
C = Crabgrass
W = War grass
O = Wild Oats
.
.
I
01 -22-
TABLE_ IA
o REEMERGENCE HERBICIDAL ACTIVITY
Reemergence % Control
No. L M P C W O S R
13100 60 60 100 100 I 60 60
14100 85100 100 100 100 80 go
15 70 60 I 1~0 100 99 63 1~0
16 75 65 70 100 100 I 15 100
17 85 65 75 lo lG0 98 50 lo
18 65 60 a loo loo 93 40 lo)
19100 98100 100 100 93 85 100
20 95 72 88 100 100 95 80 100
Al 99 73 85 lo lo 93 83 lo
L = Lambs quarter (Chenopodium album)
M = Mustard (Brusque arvensis)
P = Pugged (Amaranths retroflexus)
C = Crabgrass Digit aria sanguinalis)
W = Watrgrass (Echinochola crusgalli)
O = Wild Oats vow
S = Soy Bean
R = Rigors
As can be seen from the above table, the come
pounds listed in this table have excellent reemergence
herbicidal activity and especially so the compounds ides-
tidied as 14 (i.e. 2`-methyl-6'-(1-methyl-1-methoxyethyl)-
I N-c~loroacetylanilinP3 and 19 (i.e. 2'-methyl-6~-(1-ethyl-
l-methoxypropyl)-N-chloroacetylaniline).
I` Obviously, many modifications and variations of
the invention described hereinabove and below in the
claims, can be made without departing from the essence and
scope thereof.
.
.
