Note: Descriptions are shown in the official language in which they were submitted.
~4~;3
The Disclosure
This invention relates to novel compounds which
show activity as herbicides, to novel herbicidal compositions
which contain these compounds, and to new methods of con-
trolling weeds with these herbicidal compositionsO
Certain diphenyl ethers have been shown to be effec-
tive weed control agents. However, the herbicidal effec-
tiveness of a given diphenyl ether cannot be predicted
from an examination of the substituent groups attached to
the phenyl rings in the ether, and often quite closely re-
lated compounds will have quite dif~erent weed control
abilities~ Various diphenyl ethers may have overlapping or
complementary areas of activity or selectivity, and can thus
be useful 1n combination to control a variety of weeds u~on
a~ ca~ion of a sin~le com~osition. Furthermore~ the
di~hen~l ethers heretofore dlsclosed as herbicides are not
completely e~fective. An ideal herbicide should give selec-
tive weed control, over the full growing season, with a
single administration at low rates of application. It should
be able to control all common weeds by killing them as the
seed, the germinating seed, the seedling, and the growing
plant. At the same time, the herbicide should not be phyto-
toxic to the crops to which it is applied and should decom-
pose or otherwise be dissipated so as not to poison the soil
permanently. The known diphenyl ether herbicides fall short
of these ideals, and it would thus Pe desirable to have new
herbicides which show even more selective control of unde-
sirable plants among desirable crop plants or which complement
known herbicides in activity.
In accordance with the present invention, there is
-2- ~ ~
~.'
~ , , ,
SG3
provided a new class of novel diphenyl ethers having the
formula
1~
.
y O X (I)
' ~ .
~/\
: ~ COZ
N02
:~ wherein X is a hydrogen atom, a halogen atom, preferably a
fluorine atom or a chlorine atom, a trihalomethyl
group, preferably a trifluoromethyl group, a
(Cl-C4)alkyl group, preferably a methyl group,
or a cyano group,
~ Y is a hydrogen atom, a halogen atom~ preferably a
: ~ lO fluorine atom or a chlorine atom, or a trihalo-
. ~ -
methyl group, preferably a trifluoromethyl group,
and
Z is a ~roup of the formula -OZ' or -~RZ', wherein Z'
is an alkenyl group, preferably having 2 to 6
carbon atoms, a haloalkenyl group, preferably having
: 3 to 6 carbon atoms, a haloalkynyl group, preferably
having 3 to 6 carbon atoms, an aralkenyl group,
~; preferably having 8 to 12 carbon atom~, mostprefer-
ably a phenyl or halo-, methyl-, or nitro-substituted
-3-
.
'.,~.`
.' ,~ . .
l~V~3
phenyl(C2-C4)alkenyl group~ a cycloalkenyl group,
preferably monocyclic and having 4 to 7 carbon
atoms, or an ~oxyalkyl ~roup, preferably havin~
3 to 6 carbon atoms, and
R is a ~ydrogen atom or an alkyl group, preferably
having 1 to 11 carbon atoms.
The Z' and R substituents can have either a straight- or
branched-chain configuration. When Z' is d halo~substituted
unsaturated hydrocarbyl group, there are preferably 1 or 2
substituents
These novel compounds have been found to show
unexpected activity as weed control agents. In a preferred
embodiment of the invention, X is a halogen atom, most
preferably a chlorine atom, Y is a hydrogen atom or a halo-
gen atom~ preferably a chlorine atom and Z is a group ofthe formula -OZ'~ In another preferred embodiment, Z is
an alkenyloxy group, most preferably an allyloxy gro~p.
Examples of the compounds of the invention
embraced by Formula I include:
Allyl 2-nitro-5-(2-chloro-~,a,~-trifluoro-p-tolyloxy)benzoate
Propynyl 2-nitro-5-(2-cyano-a,a,a-trifluoro-p-tolyloxy)-
benzoate
Glycidyl 2-nitro-5-(2-cyano-6,a,a,a-tetrafluoro-p-tolyloxy)-
benzoate
~2-Cyclohexenyl 2-nitro-5-(a,a~a,a~a~ -hexafluoro-2~LI-
xylyloxy)benzoate
Vinyl 2-nitro-5-(2,6-dichloro-a,a,N-trifluoro-~-tolyloxy)-
benzoate
~3-Butenyl 2-nitro-5-(2-chloro-a,a,a-trifluoro-~-tolyloxy)-
berlzoate
~-Methylallyl 2-nitro-5-~2-chIoro-a,a,a-trifluoro-~-tolyloxy)-
benzoate
a,a-Dimethylallyl 2-nitro-5-(6-chloro-2-methyl-a,a,~-tri-
fluoro-p-tolyloxy)benzoate
:
~ .L~_
, ~
!j, ~
63
~3-Cyclopentenyl 2-nitro-5-(2-bromo-a~a~u-trifluor
tolyloxy)benzoate
-Butenyl 2-nitro-5-(a~ trifluoro-~-tolyloxy)benzoate
Allyl 2-nitro 5-(2-cyano-~,a~a-trifluoro-p-tolyloxy)benzoate
~-Styryl 2-nitr~-5-(2-cyano-6-chloro~,a,a-trifluoro-~-
~olYioxy)be~zoate
-Methyl-a2-cyclobutenyl 2-nitro-5-(2-chloro-a,a,a trifluoro-
~-tolyloxy)benzoate
~ ,~ -Dimethylallyl 2-nitro-5-(2,6-dichloro-~,a,a-trifluoro-
p-tolyloxy)benzoate
2-Chloroallyl 2-nitro-5-(2-chloro-N,a,a-trifluoro-p-tolyloxy)-
benzoate
3-Chloropropynyl 2-nitro-5-(2,6-dichloro-a,a~a-trifluoro-p-
tolyloxy)benzoate
2,3-Dichloroallyl 2-nitro~5-(2-chloro~a,a,a-trifluoro-p~
tolyloxy)benzoate
2,3,3-Trichloroallyl 2-nitro-5 (2-cyano-a,a,~-trifluoro-p-
tolyloxy)benzoate
N-Allyl-2-nitro-5-(2-chloro-,a,a-trifluoro-p-tolyloxy)-
benzam~de
N-Propynyl-2-nitro-5~2-cyano-a~a,a-trifluoro-~-tolyloxy)-
benzamide
N-Glycidyl-N-methyl-2-nitro-5-(2-cyano-6,a,a,a-tetrafluoro-
~-tolyloxy)benzamide
N-~2-Cyclohexenyl-2-nitro-5-(a,a,a,a',a',a'-hexa luoro-234-
xylyloxy)benzamide
N-Vinyl-2-nitro-5-(2,6-dichloro-a,a,a-trifluoro-p-tolyloxy)-
benzamide
N-~3-Butenyl-N-ethyl-2-nitro-5-(2-chloro-a,a,a-trifluoro-p-
tolyloxy)benzamide
N-~-Methylallyl-2-nitro-5-(2-bromo-a,a,a-trifluoro-p-tolyloxy)-
benzamide
N-a,a-Dimethylallyl-2-nitro-5-(6-chloro-2-rr.ethyl-a,,,C~-tri-
fluoro-~-tolyloxy)benzamide
N-~3-Cyclopentenyl-N-butyl-2~nitro-5-(2-bromo-a,a,a-trifluoro-
_-tolyloxy)benæamide
N-~2-Butenyl-2-nitro-5-(a,~,a-trifluoro-~-tolyloYy)benzamide
; N~ ~yl-N-methyl 2-nitro-5-(2-cyano-a,a,a-~r1fluoro-~-tolylo.Yy)-
benzamide
,; , .
--5--
13563
N-~-StynyL-2~nitro-5-(2-cyano-6-chloro~ -trifluoro p-
tolylo~y)ben~amide
N~ Methyl-~2-cyclobutenyl-2-nitro-5-(2-chloro-a,a,u-tri-
fluoro-~-tolyloxy)benzamide
N-~ ,~ -Dimethylallyl-2-nitro-5-(2,6-dichloro-a,a,~-tri-
fluoro-p~tolyloxy)benzamide
N-2-Chloroallyl-2-nitro-5-(2-chloro-~,a,~-trifluoro-_-
tolyloxy)benzamide
N-3-Chloropropynyl-N-ethyl-2-nitro-5-~2,6-dichloro-a,a,a~
trifluoro-p-tolyloxy)benzamide
N-2,3-Dichloroallyl-2-nitro-5-(2-chloro-a,~,a-trifluoro-p-
tolyloxy)benzamide
N-2,3,3-Trichloroallyl-2-nitro-5-(2-cyano-~,a,a-trifluoro-
p-tolyloxy)benzamide
and the like.
The novel diphenyl ethers of the invention are
useful both as preemergence and as postemergence herbicides.
Preemergence herbicides are ordinarily used to treat the soil
in which ~he desired crop is to be planted by application
either be~ore seeding, during seeding, or, as in most appli-
cations, after seeding and before the crop emerges. Post-
emergence herbicides are those which are applied after the
plants have emerged and during their growth period. Com-
pounds of the invention are particularly active against
broadleaf weeds.
Among the crops on which the diphenyl ethers of the
invention can be advantageously employed are, for example,
soybeans, corn, wheat, barley, rice and other cereal crops
and the like.
When used in transplanted rice crops, the ethers
can be applied either preemergence or postemergence to the
; weeds -- that is, they can be applied to the growth medium
of the transplanted plants either before the weed plants have
i
:
-6-
...
:
: L14~5~3
emerged or while they are in their early stages of growth.
The et~ers can be applied to the growth medium either
before or after the rice has been transplanted to that
medium.
~he diphenyl ethers of the invention can be applied
in any amount which will give the desired degree of weed
control. A pre~erred rate o~ application of the herbicides
of the invention is from about 0.1 to about 12, and most
preferably about 0.25 to 4, pounds of the diphenyl ether
per acre.
Under some conditions, the diphenyl ethers o~ the
invention may be advantageously incorporated into the soil
or other growth medium prior to planting a crop. This
incorporation can be carried out by any convenient means,
including by simple mixing with the soil, by applying the
diphenyl ether to the surface of the soil and then disking
or dragging into the soil to the desired depth, or by
- employing a li~uid carried to accomplish the necessary
penetration and impregnation.
A diphenyl ether of the invention can be applied
to the growth rnedium or to plants to be treated either by
itself or, as is generally done, as a component ln a herbi-
cidal composltion or formulation which also comprises an
agronomically acceptable carrier. By agronomically-
acceptable carrier is meant any substance which can be used
to d~ssolve, disperse, or diffuse a herbicidal compound in
the composition without impairing the effectiveness of the
herbicidal compound and which by itself has no detrimental
effect on the soil, equipment, crops, or agronomic environment.
Mixtures of the diphenyl ethers of the invention may be used
5~;3
in any of these herbicidal formulations. The herbicidal
compositions of the invention can be either solid or liquid
formulations or solutions. For example, the diphenyl ethers
can be formulated as wettable powders, emulsifiable concen-
trates, dusts~ granular formulations, aerosols, or flowableemulsion concentrates. In such formulations, the compounds
are extended with a liquid or solid carrier and, when
desired, suitable surfactants are incorporated.
It is usually deslrable, particularly in postemer-
gence applications, to include adjuvants, such as wetting
agents, spreading agents, dispersing agents, stickers, adhes-
ives, and the like, in accordance with agricultural prac-
tices~ Examples of ad~uvants which are commonly used in
the art can be found in the John W. McCutcheon, Inc. publi-
cation "Detergents and Emulsifiers Annual."
The diphenyl ether compounds of this invention
; can be dissolved in any appropriate solvent. Examples of
solvents which are useful in the practice of this invention
include alcohols, ketones, aromatic hydrocarbons, halogenated
hydrocarbons, dimethylformamide, dioxane, dimethyl sulfoxide,and the ]ike. Mixtures of these solvents can also be used.
The concentration of the solution can vary from about 2% to
about 98% with a preferred range being about 25% to about 75%.
For the preparation of emulsifiable concentrates,
the diphenyl ether can be dissolved in organic solvents,
such as benzene, toluene, xylene, methylated naphthalene~
corn oil, pine oil, o-dichlorobenzene, isophorone, cyclo-
hexanone, methyl oleate, and the like, or in mixtures of
these solvents, together with an emulsifying agent which
permits dispersion in water. Suitable emulsifiers include,
.
,., ~
,.
for example, the ethylene oxide derivatives of alkylphenols
or long~chain alcohols, mercaptans, carboxylic acids, and
reactive amines and partially esterified polyhydric alco-
hols. Solvent-soluble sulfates or sulfonates, such as the
alkaline earth salts or amine salts of alkylbenzenesulfonates
and the fatty alcohol sodium sulfates, having surface-active
properties can be used as emulsifiers either alone or in
conjunction with an ethylene oxide reaction product. Flow-
able emulsion concentrates are formulated similarly to the
emulsifiable concentrates and include, in addition to the
above components, water and a stabilizing agent such as a
water-soluble cellulose derivative or a water-soluble salt
of a polyacrylic acid. The concentration of the active
ingredient in emulsi~iable concentrates is usually about 10
to 60~ and in ~lowable emulsion concentrates, this can be
as high as about 75%.
Wettable powders suitable for spraying, can be
prepared by admixing the compound with a finely divided solid,
such as clays, inorganic silicates and carbonates, and
silicas and incorporati~g wetting agents, sticking agents,
and/or dispersing agents in such mixtures. The concen-
tration of active ingredients in such formulations is usually
in the range of about 20% to 98%, preferably about 40% to
75%. A dispersing agent can constitute about 0.5% to about
; 25 3% of the composition, and a wetting agent can constitute
~rom about 0.1% to about 5% of the composition.
Dusts can be prepared by mixing the compounds of the
invention with finely divided inert solids which may be
organic or inorganic in nature. Materials useful for this
3 purpose include, for example, botanical flours, silicas,
~, _ g_
;';
5~3
carbonates and clays. One convenient method of preparing
a dust is to dilute a wettable powder with a finely divided
carrier. Dust concentrates containing about 20% to 80%
of the active ingredient are commonly made and are subse-
quently diluted to about 1% to 10% use concentration.
C~ranular formulations can be prepared by impregnating a solid such as a granular fuller's earth, vermicu-
lite~ ground corn cobs, seed hulls, including bran or other
grainhulls, or similar material. A solution of one or more
of-the diphenyl ethers in a volatile organic solventiS then
removed by evaporation. The granular material can have
any suitable size, with a pref'erable size range of 16 to
60 mesh. The diphenyl ether will u~ually comprise about
2 to 15% of the granular formulation.
The diphenyl ethers of the invention can also be
mixed with fertilizers or fertilizing materials before
their application. In one type of solid fertilizing compo-
sition in which the diphenyl ethers can be used~ particles
of a fertilizer or fertilizing ingredients, such as ammonium
sulfate, ammonium nitrate, or ammonium phosphate, can be
coated with one or more of the ethers. The solid diphenyl
ethers and solid fertilizing material can a]so be admixed
in mixing or blending equipment, or they can be incorporated
with fertilizers in granular formulations. Any relative
proportion of diphenyl ether and fertilizer can be used which
is suitable for the crops and weeds to be treated. The
diphenyl ether will commonly be from about 5% to about 25%
o~ the fertilizing composition. These compositions provide
fertilizing materials which promote the rapid growth of
desired plants, and at the same time control the growth of
.
--10--
.. . _ . . . . . . . .. . . .
~l~US6~3
undesired plan~s.
The diphenyl el;hers of the invent~on can be appliecl
as herbicidal sprays by methods commonly emp3oyed~ such as
' conventional high-gallonage hydraulic sprays, low gallona~e
sprays, airblast spray, aerial sprays and dusts. For low
volume applications a solution of the compound is usually
used. The dilution and rate of application will usually
depend upon such factors as the type of equipment employed,
the methods o~ application, the area to be treatecl and the
type and stage of development o~ the weeds.
For some applications 9 it may be desirable to add
one or more other herbicides along with diphenyl ethers of
the invention. Examples of other herbicides which can be
incorporated to provide additional advantages and e.~ective-
ness include:
''C'arb'o'xy'l'i'c Ac'ids' _nd Deri~atives
2,3,6-trichlorobenzoic acid and its salts
2,3~5,6-tetrachlorobenzoic acid and its salts
: 2-methoxy-3,5,6-trichlorobenzoic acid and its salts
2-methoxy-3,6-dichlorobenzoic acid and its salts
2,3-dichloro-6-methylbenzoic acid and its salts
2,4-dichlorophenoxyacetic acid and its salts and esters
2,4,5-trichlorophenoxyacetic acid and its salts and esters
2-methyl-4-chlorophenoxyacetic acid and its salts and esters
2-(2,4,5-trichlorophenoxy)propionic acid and its salts and
esters
4-(2,4-dichlorophenoxy)butyric acid and its salts and esters
4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and
esters
2,3,6-trichlorophenylacetic acid and its salts
3,6-endoxohexahydrophthalic acid
i 6 3
dlmethyl 2,3,5,6-tetrachloroterephthalate
trichloroacetic acid and its salts
2,2-dichloroproplonic acid and its salts
2,3-dichloroisobutyric acid and its sa:lts
''Carba:mic''Aci'd'~erivatives
ethyl N,N-di'(n-propyl)thiolcarbamate
propyl N,N-di'(n-propyl)thiolcarbamate
ethyl N-ethyl-N-(_~butyl)thiolcarbamate
.; propyl N-ethyl-N-(n-butyl)thiolcarbamate
2-chloroallyl N,N-diethyldithiocarbamate
- N-methyldithiocarbamic acid salts
ethyl l-hexamethyleneiminecarbo-t~iolate
' isopropyl N-phenylcarbamate
. isopropyl N-(_-chlorophenyl)carbamate
4~chloro-2-butynyl N-'(m-chlorophenyl)carbamate
methyl N-(3,4-dichlorophenyl)carbamate
.
,:
I ''Phenols
~ dinitro-o-(s'ec-butyl)phenol and its salts
~ O
'- pentachlorophenol and its salts
, 20 ' ''S stituted Ureas
? 3- ( 3 ~ 4-dichlorophenyl)-1,1-dimethylurea
;: 3-phenyl-1,1-dimethylurea
,' 3-(3,4-dichlorophenyl)-3-methoxy-1,1-dimethylurea
'. 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea
:~ 25 3- ( 3,4-dichlorophenyl)-1 n-butyl-l-methylurea
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea
, 3- ( 4-chlorophenyl)-1-methoxy-1-methylurea
r. 3- ( 3,4-dichlorophenyl)-1,1,3-trimethylurea
;,
--1 2--
i$~
., .
'.63
3-(3,4-dichlcrophenyl)~ diethylurea
dichloral urea
''Subs'ti'tut'ed ~ri.azines
2-chloro-4,6-bis(ethylamino)-s-triazine
2-chloro-4-ethylami.no-6-isopropylamino)'-s-triazine
2-chloro-4,6-bis(methoxypropylamino)'--s-triazine
2-methoxy-4,6-bis(isopropylamino)'-s-triazine
2-chloro-4-ethylamino-6-(3-methoxypropylamino)'-s-triazine
2-methylmercapto-4,6-bis(isopropylamino)'-s-triazine
2-methylmercapto-4,6-bis(ethylamino)'-_-triazine
2--methylmercapto-4-ethylamino-6-isopropylamino-s-triazine
2-chloro-4,6-bis(isopropylamino)'-s-triazine
2-methoxy-4,6 bis~ethylamino)'-s-triazine
2-methoxy-4-ethylamino-6-isopropylamino'-s-triazine
2-methylmercapto-4-(2-methoxyethylamino)-6-i.sopropyoamino-s
triazine
''Dip'h'e'ny'l' Eth'e'r Derivati'ves
2,4-dichloro-4'-nitrodiphenyl ether
2,4,6-trichloro-4'-nitrodiphenyl ether
2,4-dichloro-6-~luoro-4'-nitrodiphenyl ether
3-methyl-4 ! -nitrodiphenyl ether
3,5-dimethyl-4'-nitrodiphenyl ether
2,4'-dinitro-4-trifluoromethyldiphenyl ether
2,4-dichloro 3'-methoxy-4'-nitrodiphenyl ether
2 chloro-4-trifluoromethyl-3'-ethoxy-4'-nitrodiphenyl ether
2-chloro-4~-trifluoromethyl-4'-nitrodiphenyl ether
2-chloro-4-trifluoromethyl-3'-carbethoxy-4'-nitrodiphenyl
ether
2,4-dichloro-3'-carbomethoxy-4'-nitrodiphenyl ether
''Ani'li~des
N-(3,4-dichlorophenyl)propionamide
-I3-
'
6~
N-t3~4-dichlorophenyl)methacrylamide
N-(3~chloro-4-methylphenyl)-2-methylpentanamide
N-(3,4-dichlorophenyl)trimethylacetamide
N-(3,4-dic,hlorophenyl)-a~a-dimeth~lvaleramide
N-isopro~yl-N-phenylchloroacetamide
N-n-butoxymethyl-N-(2,6~di.ethylphenyl)chloroacetamide
N-n-me~hoxymethyl-N-(2,6-diethylphenyl)chloroacetamide
' Urac'ils
5-bromo 3-s-butyl-6-methyluracil
5-bromo-3-cyclohexyl-1,6-dimethyluracil
. 3-cyclohexyl-5,6-trimethyleneuracil
5-bromo-3-isopropyl-6-methyluraci'1
3-t'_ --butyl-5-chloro-6-methyluracil
''Nit'ri'les
2,6-dichlorobenzonitrile
diphenylacetonitrile
3,5-dibromo-4-hydroxybenzonitrile
3,5-diiodo-4-hydroxybenzonitrile
''Othe'r 'Organic' Herbic'ides
2-chloro-N,N-diallylacetamide
N-(l,l-dimethyl-2-propynyl) 3,5-dichlorobenzamide
maleic hydrazide
3-amino~1,2,4-triazole
monosodium methanearsonate
' disodium methanearsonate
N,N-dimethyl-a,a-diphenylacetamide
N,N-di(n propyl)-2,6-dinitro-4-trifluoromethylaniline
N,N-di'(n-propyl)-2,6-dinitro-4-methyl~niline
NgN~di(n-propyl)-2,6-dinitro-4-methylsulfonylaniline
0-(2,4-dichlorophenyl)-0-methyl-isopropylphosphoramido-
thioate
.
~ -14-
. . .. ... . . .. ....
,
35~3
4-amino-3,5,6-trichloropicollnic acid
2,3-diehloro-1,4-naphthoquinone
di(metho~ythiocarbonyl)disulfide
3-isopropyl-lH-2,1,3-benzothiazidin- (4)3H-one-2,2-dioxide
6,7-dihydrodipyrido[1,2-a:2',1'-c]pyrazidinium salts
1,1'-dimethyl-4,4'bipyridinium salt 5
3,4,5~6-tetrahydro~3,5-dimethyl-2-thio 2H-1~3,5-thiadiazine,
When mixtures of herbicides are employed, the relati~e
proportions which are used will depend upon the crop to be
treated and the degree of selectivity in weed control
~hich is desired.
~he ethers of the invention can be prepared by
esterification or amidi~ication of a diphenyl ether of the
formula
CF3
`: 1
~01
;': ' 1~\ '
y X (II)
~0
y
NO2 COOH
wherein X and Y are as defined above, or of the corresponding
acid chloride, ~ith an alcohol of the formula
Z'-OH (IIIa)
or with an amine of the formula
20 Z'-NHR (IIIb)
wherein Z' and R are as defined above.
: -15-
O ~
. - . ...
63
The esterification is generally carried out at a temperature
of about Q to a~out 120~C, and preferably at room tempera-
ture, optionally in tne presence of an inert organic sol-
vent, such as a hydrocarbon or chlorinated hydrocarbon.
In the esterification reaction~ one equivalen-t of the
alcohol is generally employed, although excess alcohol
can be used as a solvent in the reaction. When the acid
chloride is used as the reagent, an acid sca~enger is
generally used. In the esterification reaction, typical
acid scavengers include inorganic bases, such as potassium
hydroxide, and amines, such as 2,6-lutidine, while in the
amidification reaction, an excess of one equivalent of tne
amine starting reagent can function as the acid scavenger.
Other conventional esterification and amidification techniques,
such as transesterification, transamination, the Schotten-
Baumann reaction, and the like, can also be used.
A modification of the above preparative method
for preparing the esters of the inven~ion in~olves the
reaction of a metal salt~ such as the sodium salt~ of an
acid of ~rmula II with a halide of the formula Z'-Hal,
where Hal is a halogen,preferably chlorine or bromine, atom.
This reaction is generally carried out at a temperature of
about 0 to about 120C, preferably room temperature, and
in an inert organic solvent, such as benzene.
Another route to the compounds of the invention
involves the nitration of a diphenyl ether of the formula:
-16-
;
'~:
- .. ... v
563
~3
~,
Y X (IV)
~0~
COZ
wherein X, Y, and Z are as defined above,
using typical nitrating agents such as potassium nitrate
in sulfuric acid, acetyl nitrate, mixed sulfuric acid/nitric
acid, nitrosonium tetrafluoroborate, and the like. The
nitration reaction is generally carried out at about -20
to about 100C, preferably about 0 to about 5C, optionally
in the presence of an inert organic solvent, such as
methylene chloride or other chlorinated hydrocarbon.
Ethers of the invention can also be prepared
by condensi.ng a phenol of the formula
V)
X ` .-
OH
~ wherein X and Y are as defined above with a substituted halo-
: benzene of the formula
:
:,. .
.:'
- ' rr-
~` ~
-~4V563
` (VI)
COZ
NO.2
wherein Xl is a halogen a~om, preferably a ~luorine atom,
and Z is as defined above. This reaction is generally
carried out at a temperature of about 0 to about 250 C,
preferably about 75 to about 200C, optionally in the presence
o~ an appropriate solvent, such as sulfolane, dimethylsulfo~ide
dimethylformamide, hexamethylphosphorous'riamide~ or other
inert polar organic solvent.
The~diphenyl ether precursors can be prepared by
reacting a suitably substituted phenol~ or the potassium or
sodium salt o~ the phenol, with a suitably substituted halo-
benzene~ such as a chloro- or fluorobenzene in the presence
of an alkaline agen~. Such precursors and their preparation
-- . . . .
æe~descr~x~ ln U.S. Pa~ent 3,928,416, of Bayer et al., granted
}5 December 23, 1975,
The following examples will further illustrate
this inventlon but are not intended to limit it in any way.
In Table I, typlcal diphenyl ethers of the invention are
listed with their elemental analyses. Specific, illustrati~e
preparations of the compounds of Examples 1, 7, and 12 are set
forth after Table I. A11 temperatures are in degrees Centi-
grade and parts and percentages are by ~reight unless otherwise
indicated.
-18-
~.--
563 `~
--61--
,~
_ ~
~ =S 3 ~`J r', N r l ~) r~~ ~ rl t~J r-l
U~ ~ ~
~_1 ~10 ~ =~ 3
.~ ~ 3 Ir\ ~ D ~ 3
~1 ~ ~ ~
~ .
¢
' ' ~ ~1
,~ O ~ ~ ~ ~ ~ ~ U~
~ æ ~ c~ .N ~ O
O~ :I~ .
\~\ ~ .
¢ r, ~ ~
E~ I ~ ) . u~
C ~/ r~ O r l ~1 ~ 3
~ ~ ~ O ~U~
V
u~
~v ~ ~v
H P-~ S~ V ~ V
~3 l ~1 O tli O t~ O ~) O ~ O ~ O ~
1 l ~ V ~I v ~ c~ ~ v ~ C) ~ C) 4~ v
:~1 V~ \ . ¢)
¢ p:;
' ~ ~ E~ ~~
~ ~ o
~. ~ 1 ~1 , .
P~ ~n ~7
. H 1~ .~I
.~)
m c~ v c~
~I ~ 11 _
. C~ U V~ O
_ . ~ rO ~OC X_ ~ m
~; o
~1 C~,
. E~
`~9
. .
S~3
, " ~ ,_ , -
00 r~ O N
r~ O ~ r~ . r~ -
. ~ N r~,r) r-l~ r~r-l rl~r) r~l ~J rl
~ r~ `~r-( `~~1 ~'r~ `~r~ `~ r-l ~'
U~ . ~ IS~ =~ N ~r~ O
rl =~ .~D . L~ . N ~ ~ . N -
'~n ~; . ~. ~. ~ . ~ . ~ . t--
r~ ~ ~1~
~)
~
r-l Lr~ IY) ~ ~r) 1~ O
. (~ (X7 O ~ O -
~ N N N N t~)
S~ ~ ~ ~C~l--' ~ `' ~ ~ ~ ~`'
~ . ~ ,
r-l
~J r-l ~1 a~ O ~ O
'D If ~ N OO O~
(~) ~ r~ N ~D . C~ r-l -
V IS\ 1~\r~ ~ trl ~ ~C) ~ O~ O lS~
0 ~ V S~ r~ c ) U~
C)~ r~ r-i~5 r~ rl::~ ~I r-l
_,O ~ O ~ O ~ O ~ O ~ O ~
C~ 4 C) ~~ O
a~
' ~ ~ * I
E I~ r~
' ~ O
rl
C'J N
,,
, ~ V C~ Q~
V / ¦ ~N r1
'. N }~ ~ ~vN \ ¦ V
:~, lll ll rl ~
V V C~--V V N ~h
V N I ~ N N ~ O
V ~ ~_~ ~ ~ V
o o o o o æ
I I I I I I
. . o
. ~ '
~. a): o
rl C)
.'
.~ X O r~ N h
~1 ~--O;~ r l rl r-l *
.,
~,. .
,,,
.,.
,~ .
:~ .
U563
Example 1
Preparation of Al]yl 2-nitro 5-(2-chloro-a~a2a-trifluoro-
p-'t'olyloxy-~benzoate-
Oxalyl chloride (51 g. 0.4 mole) is added drop-
wise to a solution of 2-nitro-5-(2-chloro~ ,a,a-trifluoro-
' p-tolyloxy)benzoic acid (109 g. 0.3 mole) in benzene
(200 ml.) and the solution heated under reflux for 18
hours. Solvent and excess reagent are stripped off and
fresh benzene (250 ml.) and allyl alcohol (18 g 0.31 mole)
are added, followed by 2,6-lutidine (35 g. 0.32 mole) in
benzene (50 ml.)~ added dropwise at room temperature. The
mixture is diluted with ether~ washed with water, dried,
and filtered through a little silica gel. The solvents
are removed, and, after standing, the residue solidifies
and is slurried ln hexane to give 114 g. of allyl-2-nitro-5-
(2-chloro-a,a,a-trifluoro-~-tolyloxy)benzoate as a waxy
solid.
Preparatio'n of ,a-Dimethylallyl 2-nitro-5-(2-chloro-~,a,a-
trifluoro-p-tolyloxy)benzoate
; To a solution of 8.7 g (0.10 mol) of 2-methyl-
3-buten-2-ol in 100 ml of tetrahydrofuran at 25 is added
portionwise 4.2g of a 57% oll dispersion of sodium hydride
(0.10 mol). The solution ls stirred magnetically until
gas evolution ceases. A solution of 38.og (0.10 mol) of
2-nitro-5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)benzoyl
chloride in 50 ml of benzene is added dropwise with stirring.
After 3 hours the solution is evaporated to dryness under
vacuum, diluted with 200 ml of ether, extracted with 100
3o ml of dilute aqueous sodium bicarbonate soluion, extracted
with 100 ml of water and dried.
F
4~5~3
The solution is vacuum filtered through a short
column.of silica gel, and then evaporated under vacuum
to give 22.55 g of N3~-dimethylallyl 2-nitro-5-(2-chloro-
a~,a-trifluoro-p-tolyloxy)benzoate as a light yellow
oil.
xample 12
__~tion ~of'N-'Al'lyl'-2'-ni'tro-5-('2-c'hloro~ -trifIuoro-
' p-tol'yloxy)ben'z'amide
A solution of 2-nitro-5~(2-chloro-a~ -tri-
fluoro-~-tolyloxy)benzoyl chloride (o.o875 mole in 82.5
ml of benzene, prepared as in Example 1) is added drop-
wise at room te~perature to a solution of allylamine
(10 g, 0.175 mole in 100 ml of benzene). Heat is evolved
and allylamine hydrochloride precipitates. After stirring
overni~ht, the solution is diluted with ether (150 ml)
and extracted with dilute hydrochloric acid (150 ml) and
water (150 ml). An unldentified solld (8g) is filtered
off and discarded. The solvent is then removed to give
33.93 g. of N-allyl-2-nitro-5-(2-chloro-~,a,~-trifluoro-
~-tolyloxy)benzamide as a yellow oil, which solidifies
on standing. Recrystallization from isopropanol and 5~
methanol gives 28.74 g. of the product amide with a melting
point of 64-~8C.
The following examples show the herbicidal
properties of diphenyl ethers of the invention.
Example '13
This example shows the herbicidal activity of
diphenyl ethers of the invention towards a number-of common
weeds. Using the procedure described below, diphenyl
ethers were evaluated for control of some or all of the
-22~
.''' .
following weeds:
Dicots (D)
cocklebur`(Xan`thium pensy _ anic'um)
marigold (_aget'es spp.)
morningglory ('I'p'omoea _urpurea~
tomato (Lycopersicon esculentum)
velvetleaf ('Abuti'lon the'op'hrasti)
Mono'c'ots (M)
. .
barnyardgrass ('Echi'nochIoa'c'rus'~al'li)
downy brome'('Bromus''t'e'ct _ um)
~oxtail ('S'e'taria'fab'erii)
nutsedge'('Cype'rus''es'cul'ent'us)
wild oats ('A've'na 'f ua)
The following test procedure is employed. Seeds
of selected crops and weeds are planted in soil in flats.
~or preemergence tests, the flats are treated with the
test compound immediately after the planting. For post-
emergence tests, the seeds are allowed to germinate, and
after two weeks the flats are treated with the test
compound immediately after the planting. The compound
to be evaluated is dissolved in acetone, diluted with
water, and sprayed over the flats using a carrier volume
equivalent to 50 gallons per acre at the rate of appli-
cation of two and four pounds per acre. About two weeks
?5 after the application of the test compound, the state of
growth of the plants is observed and the phytotoxic,effect
of the compound is evaluated. The results of typical
, tests are summari~ed in Table II, which gives the average
'~ percent control achieved by the test compounds in terms
' 30 of the percent of the plants which are killed by the compounds.
,,
, -23-
f
.,. ,
,.
:.
ABLE II
HE.RBICIDAL A~TIVITY
. ~
Compound of Rate Preemergence Postemergence
Example No. (lbiA) M D M D
1, 4 76 51 75 98
~ 2 51* 46~ 85~ 100
2 L~ 87 98 68 99
2 82 98 36 86
3 4 94 93 49 91
2 76 85 45 85
4 4 gLl 96 74 100
2 81 97 73 98
4 92 95 69 100
: 2 79 90 6ll 99
6 4 87 90 22 96
. 2 78 80 lL~ 70
7 Ll 9l~ 99 61 ~6
2 8l~ 98 51 92
8 4 98 99 66 93
2 95 9' 71 96
9 4 92 99 69 98
2 96 94 54 9ll
4 96 99 68 100
2 95 86 65 100
11 4 95 93 52 96
2 9l~ 90 34 99
93 18 71
2 86 70 0 80
~average of two tests
3 Similar tests also showed tolerance of the com-
pound of Example 1 to the following crops: corn1 soybeans~
wheat and rice.
Example 14
The compounds of Example 1 to 12 were also eval-
uated in conventional field tests. In one typical field
test, the compound of Example 1 [allyl 2-nitro-5-(2-chIoro-
-24-
~l~V~3
a,a,~-trifluorb-p-tolyloxy)benzoate] was tested for control
of a number o~ annual- grasses and broadleaf weeds and for
tolerance to a number of common crops. Table II summarizes
these tests results.
. .
TABLE'III
-
FI~LD TEST ACTIVI'TY
-
Preemer~ence
Rate TEIa % Weed Control
''Annual' Grassesb ''BrbadIeaf WeedsC'~d
.
lQ 0.25 14 35 83
0 90
1.0 14 98 100
98 95
RateTEIa% Weed Control
~ _ An'_uaI Grassesb~roadIeaf WeedsC~d
'' `0.25 6 97 100
'' 25 80 97
1.0 6 100 100
98 100
a) treatment to evaluation interval (days)
b) including crabgrass, foxtail, fall panicum
~ c) preemergence including lambsquarters, ragweed,
'~ pigweed
d) postemergence including ragweed, pigweed,
' purslane, smartweed, galinsoga
Among the crops which showed tolerance to this compound in
field tests were corn, soybeans, cotton, barley and rice
in preemergence application and corn, soybeans, barley and
` 30 rice in postemergence applications.
In another field test, the compounds of Examples 1
to 12 were evaluated for weed control and for crop tolerance
to soybeans and corn. Among the weeds which occurred
naturally in or were seeded into the field test plots were
,, ~ .
' ~ 35 velvetleaf, morningglory, sicklepod`(Cas's'ia'ob't'usifola),
, -25-
:. J
....
.,, ~
lal~lbsquarters (Chenopod:Lum album), pigweed (Amaranthus
retroflexus), pur~].ane (PortuIaca oleracea), chickweed
(Stellaria media), a.nd barnyardgrass.
. _ ,
Table III summarizes typical results from these
tests.
TABLE III
FIELD TEST ~CTI~ITY
o
a~ ~ O td ~ O
Compound of Rate TEI ~ O .
Example No. (Ib/A) (days) ~ Q '~
1 0.5 ~ 30 ~ 3o o 10 ~ 100
2 30 100 994372 100 100 100 92
2 0.5 30 37 23 0 17 77 100 100 43
2 30 98 8520 70 98 100 100 85
3 0.5 30 78 37 0 30 87 100 100 52
2 30 100 1002775 100 100 100 97
4 . 0.5 30 85 40 07 85 100 10063
2 30 100 953758 100 100 10097
0.5 30 27 27 013 90 95 10010
2 30. 98 621073 100 100 10072
6 .5 30 23 27 0 0 78 95 100 45
2 30 87 5310 70 99 100 100 68
7 0.5 30 23 30 0 20 83 85 100 0
2 30 63 40 0 65 98 100 100 80
8 0.5 30 78 37 0 20 82 100 100 3
2 30 100 ~99288 100 100 100 97
9 0.5 30 97 57 0 37 72 100 100 50
2 30 100 997085 100 100 100 100
0.5 30 30 30 030 77 98 10062
2 30 100 883070 100 100 10083
11 0.5 30 27 27 0 13 1~377 ~ao o
2 30 98 6310 47 97 100 100 73
12 0.5 30 37 27 0 10 1~787 100 33
2 30 98 40 0 78 98 100 100 77
-26-
.
, :
. ,
563
~ 11 of the compounds showed tolerance to soy-
beans and corn at the rates tested.
It is to be understood that changes and variations
can be made without departin~ ~rom the spirit and scope
of this invention as defined by the appended claims.
-27-~
.
