Note: Descriptions are shown in the official language in which they were submitted.
6~
This invention is in the chemical arts. More
particularly, it relates to those arts pertainln~ to aromatic
amines and herbicides.
In summary, this invention comprises a group of N-
phenyl amines represented by the formula:
~c~ N--~4~
in which Rl and R2 are independently lower alkyl, R' is selected
from the group consisting of mono-, di- and trihaloacetyls, R~ is
lower alkylene and R5 is hydrogen lower alkyl or a salt-forming
cation. Compounds of the ~eneral formula in ~ ich R' represents
hydrogen are intermediates for the production of the novel
compounds of the invention.
In the definitions, lower alkyl encompasses C1-C7 alkyl
and includ0s both straight and branched chain alkyls, examples of
which include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
t-butyl, pentyl and the like. Halo comprises fluoro, chloro,
bromo and iodo. Lower alkylene encompasses Cl-C7 alkylene and
includes both straight and branched chain alkylenes having 1-7
carbon atoms, examples o~ which include ethylene, propylene, 1-
methylethylene, 2-methylethylene, butylene, 1-methylpropylene, 2-
methylpropylene, 3-methylpropylene, 1,1-dimethylethylene, 1,2-
dimethylethylene, 2,2-dimethylethylene and the like. Examples of
salts include ammonium salt, alkali metal salts (sodium,
potassium and the like, alkali sarth metal salts (calcium,
magnesium and the like) and amine salts (methylamine,
diethylamine, tripropylamine, diphen~lamine and -the like).
Examples of Cl-C7 alkanol esters include the methyl ester, ethyl
ester, the propyl ester, the isopropyl ester and the like. Aryl
includes phenyl, tolyl, naphthyl and the like.
fi~
-- 2
Examples of compounds covered by the generic formula,
including some intermediates in which R' = H, are:
1. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
2. N-dichloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
3. N-trichloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
4. N-(2,6-dichlorophenyl)-glycine ethyl es-ter
5. N-chloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl es-ter
6. N-dichloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl ester
7. N-trichloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl ester
8. 4-(N-trichloroacetyl-2',6'-dichloroanilino)-butyric acid
sodium salt
9. N-chloroacetyl-N-(2,6-diethylphenyl)-alanine ethyl ester
10. N-carbethoxyethyl-N-chloroacetyl-2,6-diethylaniline
11. N-chloroacetyl-N-(2-methyl-6-e-thylphenyl)-alanine ethyl
ester
12. N-carbethoxyethyl-N-chloroacetyl-2-me-thyl-6-ethylaniline
13. N-chloroace-tyl-N-(2,6-dimethylphenyl)-glycine
14. N-chloroacetyl-N-(2,6-dimethylphenyl)-glycine sodium salt
15. N-chloroacetyl-N-(2,6-dimethylphenyl)-glycine ammonium salt
16. N-chloroace-tyl-N-(2,6-dimethylphenyl)-glycine ethyl es-ter
17. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine
~8. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine sodium salt
19. N-chloroacetyl-N-(2,6-die-thylphenyl)-ylycine ammonium salt
20. N-chloroacetyl-N-(2-methyl-6-ethylphenyl)-glycine
21. N-chloroacetyl-N-(2-methyl-6-ethylphenyl)-ylycine sodium
salt
22. N-chloroace-tyl-N-(2-methyl-6-ethylphenyl)-glycine ammonium
salt
23. N-chloroasetyl-N-(2-methyl-6-ethylphenyl)-glycine ethyl
ester
24. N-bromoacetyl-N-(2,6-die-thylphenyl)-glyCine
25. N-bromoacetyl-N-(2,6-diethylphenyl)-glycine sodium salt
26. N-bromoacetyl-N-(2,6-diethylphenyl)-glycine ammonium sal-t
27. N-bromoace-tyl-N-(2,6-diethylphenyl)-glycine ethyl aster
-- 3
The compounds representad by the formula range in color
from brown to yellow and in state at 20-25~C. from liquid to
solid. In general, the esters of this invention are insoluble in
water, but in solvents such as acetone and the like, and such as
benzene and the like, they are soluble to the extent suitable for
herbicidal uses. On the other hand, in general, the inventive
acids, salts, amides and hydrazides are soluble in water at least
to the extent suitable for herbicidal uses. The compounds of
this invention are characterized by both pre- and post-emergence
toxicity -to a number of weeds. On the other hand, at
concentrations at which the toxiaities o~ the compounds of this
invention are not tolerated by such weeds, a number of desirable
plants are relatively unaffected by these compounds. Hence, the
compounds of this invention are useful as selective herbicides.
The compounds of this invention are made by reacting in
a liquid reactlon medium containing a base such as potassium
hydroxide or the liko corresponding phenyl amine:
R~
R
with a haloalkanola acid or ester of the formula:
X - R4- C~
in which X is halo, to form the compounds of the class in whîch
R' is hydrogen. The compounds are reacted with mono-, di- and
tri-haloacetylhalide~ of the formula:
o
X ~ C~ i n )~
~.
-- 4 --
in which n is 0-~, to form the compounds of this invention,
however, is not limitad to these ways of making the compounds of
this invention.
For herbicidal uses the compounds o this invention
preferably are incorporated into a dispersible composition. This
composition comprises an effective ~uantity of phytotoxic
material, and application aid material.
The phytotoxic material consists essentially of at
least one compound of this invention. In some embodiments of this
composition the phytotoxic material comprises only one compound
of this invention. In other embodiments the phytotoxic material
comprises -two or more compounds of this invention. In still
other embodiments, it comprises other substances having
phytotoxic activity.
Specific embodiments of the composition of this
invention range from concentra-tes of the phytotoxic ~aterial to
the ultimate use composition that is applied in the field.
Accordingly, an effective concentration of the phytotoxic
material in the composition of this invention is in a broad
range, generally being from about 0.1 to about 90~ by weight of
the composition. Higher and lower concentrations, however, are
within the broader concspts of this invention. In concentrate
embodiments, the concentration of the phytotoxic material
generally is in a range from about 10 to about 90~ by weight of
the composition and preferably in a range from about 10 to about
50~ by weight of the composition. In -the ultimate use
embodiments, the concentra-tion generally is in a range from about
0.1 to about 20-~ by weight of the composition and preferably in a
range from about 0.5 to about 10-~ by weight of the composition.
Ap~ 2t.0r aid mat~r-~?l. .iS generalLv inert material
that facilita-tes ~istribution or dispersion of the phytotoxic
N
~5~3~3
-- 5
material when it is applied to soil or to foliage of undesirable
plants. It encompasses diluents, carriers, extenders,
surfactan-ts, spreading agents, sticking agents, wind drift
control agents, and -the like.
In those embodiments of the composition of this
invention, which are normally solid, the application aid material
generally comprises an inert solid in a divided condition.
Some embodiments of the solid composition are granular,
while others are dispersible powders or dusts.
The granular compositions are of the coa-ted type, the
impregnated type or the incorporated type.
The coated type of granular composition is made by
dusting a wettable powder or ground powder comprising the
phytotoxic material onto inert granular carrier material which
either before or after the dusting has been admixed with an inert
adhesive or a sticker. Water, oils, alcohols, glycols, aqueous
gums, waxes and the like including mixtures thereof, are used as
stickers. Examples of inert granular carrier ma-terial include
attaclay, corn cobs, vermiculite, walnut hulls and almost any
granular mineral or organic material screened to the desired
particle size (generally 15-60 mesh, preferably about 30 mesh,
U.S. screen size). Generally the phytotoxic material is abou-t 2-
20% by weight of -the composition, and the granular carrier
material is generally about 60-93~ by weight of -the composi-tion.
In the case of the impregnated type of granular
composition, the phytotoxic ma-terial as such when liquid or after
melting, or dissolved in a solvent, is sprayed on or poured into
the inert granular carrier material. The solvent can be removed
by evaporation, or permitted to remain. In either case, -the
phytotoxic material impregnates the particles of -the granular
carrier material. Examples of the iner-t granular carrier
. ~
6- ~576~
material include those just mentioned wi-th respect to the coated
type of granular composition. The phytotoxic material is
generally about 2-20~ by weight of the composition, while the
granular carrier material is generally about 80~98~ by weight of
the composition.
The incorporated type of granular composition is made
by admixing the phytotoxic material with an inert finely divided
solid such as, ~or example, clay, carbon, plaster of paris and
the like, and made into a mud with water or other inert
evaporable liquid. The mud is then dried to a solid sheet or
cake, broken up or comminuted, and screened to the desired
particle size (generally 15-60 mesh, preferably 30 mesh, U.S.
screen size). In other embodiments, the mud is put into a
granulating pan and granules are formed therein with subsequent
removal of the water or solvent. In still another procedure, -the
mud is extruded through a die into rods which are cut into small
pieces. In the incorporated type of granular composition, the
phytotoxic material generally is about 2-50~ by weight of the
composition, and the solid carrier material is about 50-98% by
weight of the composition.
In all granular embodiments of the composition of this
invention, various additives in minor concentrations relative to
the carrier material also can be present.
In other embodiments of -the solid composition of this
invention, the carrier is usually a dispersible inert solid. A
typical dispersible solid of this type is clay. Other suitable
solids ldispersible solid) include talc, attapulgite, pyropylite,
diatomaceous earth, kaolin, aluminum magnesium silicate,
montmorillonite, fullers earth, sawdust and -the lika. The solid
dispersible composition can be air dispersible, in which case it
is usually referred to as a dust. Generally, when it is in-tended
'-~nat- the compc3ltion be wa'er d:~spersible, the compos1tion
preferably contains emulsifying material ~one or more
~j 7~0~3
-- 7
surfactants) at a concentration sufficient to enable a suspension
of the desired degree of stability to be formed when the
composition is admixed with a suitable quantity of water. The
composition in such case is usually referred to as a wettable
powder. A typical dispersible solid composition of this
invention generally comprises about 10-80~ by weight of the
phytotoxic material, about 20-90~ by weight of solid carrier
material and, when emulsifying material is present, about 1-10%
by weight of emulsifying material.
Other specific embodiments of the herbicidal
composition of this inven-tion comprise homogeneous liquid
solutions of phytotoxic material in inert, preferably volatile
solvents for the phytotoxic material. Examples of suitable
solvents when the phytotoxic material is wa-ter-insoluble include
isophorone, cyclohexanone, methyl isobutyl ketone, xylene and the
like. When the phytotoxic ma-terial is water-soluble, water is a
suitable solvent. Such a solution, which can be regarded as a
concentrate, typically comprises about 10-50% by weight of
phyto-toxic material and about 50-90% by weight of solvent. The
solution can be applied as is, or diluted with more solvent and
applied or, when water immiscible, dispersed in water, or water
dispersed in it, and applied. Preferably, when i-t is intended
that the solution be dispersed in water or wa-ter dispersed in it,
the mixture of solution and water also comprises emulsifying
material at a concentration sufficient to enable a dispersion of
the desired degree of s-tability to be formed when the solution or
concentrate is mixed with water. A typical emulsifying material
concentration is about 1-10% by weight of the concentrate. The
water concentration generally is such that -the phytotoxic
material concentra-tion preferably is about 0.5-10% by weight of
the total composi-tion.
Examples of the surfactants employed in bo-th the liquid
and solid compositions of this inven-tion comprise the well known
surface active agents of the anionic, cationic and non-ionic
~.f`~-
~576~)~
types and include alkali mstal (sodium or potassium) oleates and
similar soaps, amine salts of long chain fa-tty acids (oleates),
sulfonates, animal and vegetable oils (fish oils and castor oil),
sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic
acids, alkylnaphthalene sodium sulfonates, sodium lauryl
sulfonate, disodium monolauryl phosphate, sorbitol laurate,
pentaerythritol monostearate, glyceryl monosterate,
poly(oxyethylene), ethylene oxide condensates of stearic acid,
stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl
amina and the like, lauryl amine salts, dehydroabietyl amine
salts, lauryl pyridinium bromide, stearyl trime-thylammonium
bromide, and cetyl dimethylbenzylammonium chloride. Still other
examples are listed in "Detergents and Emulsifiers - 1968 Annual"
by John W. McCutcheon.
In addition to the phyto-toxic material and application
aid material, some specific embodiments of the herbicidal
composition of -this invention comprise one or more other
components, examples of which include plant growth regulators,
insecticides~ fungicides, plant nutrients and the like.
The herbicidal composition of this invention is used by
applying it by conventional ways and means to soil and to foliage
of weeds.
The rate of application of the composition of this
invention is such as to provide an effective concentration of the
phytoto~ic material in the soil, on the weed oliage, or both in
the soil and on the foliage, depending on the me-thod of
application and what is desired.
The bes-t mode now contemplated of carrying out -this
invention is illustrated by the following working examples of
various aspects of this invention, including specific
emb(3~-3im~n-}c~ T~s ~vent;~ lS not llmited to these specific
embodiments. In -these examples all percentages are by weight
~d
9 ~5~V~
unless otherwise indicated all parts by weight are indicated by
"w", all parts of volume are indicated by "v", and each part by
weight (w) bears the same relationship to each part by volume (v)
as the kilogram does to the liter.
E~ample 28
This example illustrates a specific embodiment of a
process for making N-chloroacetyl-N-(2,6-diethylphenyl)-glycine
ethyl ester, the E~ample 1 compound.
Ethyl bromoacetat0 (4~0 w) is added dropwise to a
stirred mixture of 2,6-diethylaniline (429 w), potassium
hydroxide (161 w) and dimethylformamide (1500 v). During the
addition of ethyl bromoac~tate, the temperature of the reaction
mixture typically rises slightly. After addition is complete,
the mixture is stirred at 90-llO~C. for one hour. During this
period of time ths potassium hydroxide dissolves and a white
precipitate slowly forms. The reaction mixture is cooled to 20-
25C., poured into water (2000 v) and extracted with diethyl
ether (700 v) three times. The ether extracts are combined,
washed in water, an aqueous solution of hydrochloric acid (10~),
an aqueous solution of sodium bicarbonate ~5%), and water, and
then dried. The diethyl ether is r0moved by evapora-tion under
reduced pressure. The residue (~26.8) is typically a red oil.
It consists essentially of N-(2,6-diethylphenyl)-glycine ethyl
ester.
In similar fashion -the other intermediate compounds in
which R' is H are made from the corresponding anilines and
haloalkanoic acids or esters.
To a stirred solu-tion of the 2,6-di0thylphenylglycine
ethyl ester (531.5 w) in benæene (2.5 v) is added dropwise
chloroacetyl ch]o~ide (306 w) followed by pyridine (196 w).
During the additions the temp0rature of the reaction mixture
N
~5~
- 10 -
typically rises from 20-25C. to about 40C. After the additions
are complete, the resulting reaction mixture is stirred at 40-
50C. for 3 hours, cooled to 20-25C., and filtered. The
filtrate is washed with the water, an aqueous solu-tion of
hydrochloric acid (10%), an aqueous solution of sodium
bicarbonate (5~), and water, and then dried. The benzene is
removed by evaporation under reduced pressure. The residue
~711.0 w), the desired product, is typically a red oil which
crystallizes on standing. A typical analysis of the product is:
N = 4.4%, C1 = 11.9%; (calculated: N = 4.4%, Cl - 11.3%). The
product consists essentially of N-chloroacetyl-(2,6-
diethylphenyl)-glycine ethyl ester.
In similar fashion tha other compounds of this
invention in which R ' iS mono-, di- and trihaloacetyl are made
from the corresponding compounds in which R' is H, and -the
I corresponding mono-, di- and -trihaloacetyl halides.
Example 29
This example illustrates a specific embodiment of the
herbicidal composition of -this invention.
The general formulation o-f the composition is:
Components Concentration
Phy-to-toxic material 1 w
Poly(oxyethylene)sorbitan
monolaurate in which the
average oxyethylene content
is 20 mole % 1 v
Toluene 1 v
The phytotoxic material in this example consists of the
product of Example 28.
The composition of the foregoing formulation is made by
admixing the components at 20-25 C. It ~s a water emulsi~iable
concentrate.
This emulsifiable concentrate is used by admixing it
with water to give an emulsion containing N-chloroacetyl-N-(2-6-
diethylphenyl)-glycine e-thyl ester at the desired concentration.
This general formulation is applicable to the other
compounds of this invention, whether alone or in mixture.
The herbicidal utilities of the compounds of this
invention are illustrated by the test data set forth in the
following Table. These test data were obtained in actual routir-e
greenhouse testing of products consisting essentially of the
compounds of this invention. In each case a water emulsi~iable
t concentrate was made by dissolving a sample (15 w) of the product
in acetone (400 v) and then admixing a commercially available
emulsifier [a blend of polyoxyethylene (20) sorbitan monooleate
in which -the average oxygethylene content is about 20 mole %,
mono- and diglycerides of fat forming fatty acids, and an
antioxidant mixture consisting essentially of butylated
hydroxyanisole, butylated hydroxytoluene, citric acid and
propylene glycol] (20 v). The liquid concentrate was then
dispersed in water and the resulting emulsion applied by spraying
at standard test ra-tes.
In the post emergence (foliage spray) -test, the
emulsion was sprayed at rates of 1 and 10 pounds of test product
per acre on growing plants a-t the first true leaf stage. The
plants were millet, corn, mustard, cotton, tomato and marigold.
After a prescribed interval of time during which the sprayed
plants as well as unsprayed plants of the same age were subjected
to favourable growing conditions in a greenhouse, the sprayed
plal~ts v,ere insL,3cted for injur-~ and li]l, compa:red with the
unsprayed plants, and the extent of injury or kill rated on a
N
)8
- 12 -
scale of 0-10 with 0 being no injury or kill and 10 being 100
injury or kill.
In the pre-emergence (soil germination) test the
emulsion was sprayed a-t rates of 2 and 20 pounds of test product
per acre on soil freshly seeded with the seeds of soybean,
millat, corn, mustard and cotton. After subjecting the sprayed
seeded soil as well as unsprayed soil freshly seeded with thess
seeds to controlled favourable growing conditions in a greenhouse
for a time sufficient for germination and plant growth, the
containers of the soil were inspected for plant growth and
injury, and compared to the containers of unsprayed seeded soil.
The extent of injur~ or kill was rated on a scale of 0-10 with 0
being no injury or kill and 1~ being 100~ injury or kill.
Although they do not form part of the invention, the
intermediates of the general formula in which R' represents
hydrogen possess herbicidal activity and the test results for the
intermediates are included in the Table for reference purposes~
N
- 13 _ ~ r~
¦ O C~ O ~ O ~; O O O O O O O N O O O _l O ~ 'd 11~
'a~ O ~ O O O O O O O O O (~ ~ o o v~ O ~ O c~ o
E-~ ~
C C:
C O t'1 ~ O ~ ~ N O O O O N ~ O ~ ~ O 0~ O O O O O CO O
_~ ~
O O O O O O ~ O O O O O `O Ir- O O O O O 0~ O O O o o
O l
O O t` ~ ) 0--I O O O ~ O ~') O ~ ~O O N t~ O O O ~ O cr~
N(`~NON N NO ~ CNN O N O N O
Il~
~ N 117 0 t`~O ~ O ~ N`O ~ N ~ O ~ O O O ~` N ~D
I
l
N O O ~N OO Cl~ O ~! ~ ~O O ~ ~ (') `D O O ~ l 0)
¦ N a~ O U~ O ~' O ~') O ~D O N --I O ~1 O~ O ~ O t~) O ~ O ~
~ ~1 ~
~1 ~ o ~ ,~ V) o N O N O ~ O O 0~ N O O ~` .1 0 '1 O
a ::
2 ~¦ ~ N ~ N ~ N O ~ O ~1 0 (O O N O N ~ N O ~ O N O
ol ~ ~ O u~ O ~ O ~ O u~ O O ~ r) o u~ o
O ~10 -~ O ~ O ~ O ~- O .-10 ~ O ~10 -~ O ~10 _1 ~0
o ol
O'
O X _I N ~ ~Ul 'D N a~ O ~-
N
7~
Thus, it can be observed that the compounds of this
invention are herbicidal. They also exhibit selective herbicidal
activity. For example, in field testing of a 2 pound per gallon
emulsifiable concentrate in which the phytotoxic material
consisted essentially of N-chloroacetyl-N-~2,6-die-thylphenyl)-
glycine eth~1 ester, the Example 1 compound, the activity of this
compound was found to be primarily against grass weeds, but it
also performed very well in controlling pig weed and smart weed.
Crops which were found to be tolerant to relatively high rates of
this compound are sugar beets, corn, wheat, peas, cotton, peanuts
and soybeans. Although greenhouse data showed low tolerance by
sorghum and rice in this compound, these crops tolerated this
compound under field conditions at rates that gave excellent
grass control. Also, this compound was found to give effective
wild oat control without injury to wheat or to barley.
Thus, this invention provides new and useful compounds
and new and useful herbicidal compositions containing them.
Other features, advantages and specific embodiments of
this invention will become readily apparent to those exercising
ordinary skill in the art after reading the foregoing
disclosures. Such specific embodiments are within the scope of
the claimed subject matter unless expressly indicated to the
contrary by claim language. Moreover, while specific embodiments
of this invention have been described in considerable detail,
variations and modifications of them can be eff~cted without
depar-ting from the spirit and scope of the inven-tion as disclosed
and claimed.
The term "consisking essentially of" as used in this
specification excludes any unrecited substance at a concentration
sufficient to substantially adversely affect the essen-tial
properties and charac-teristics of the composition of matter being
deL.ned, whi'P pa~:;mtting 'h~ p'L'e'S~.Ce of one or more l1nr~.ited
~ ~ ~3
- 15 -
substances at concentrations insufficient to substantially
adversely affect said essential properties and characteristics.
N
