Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~133502
HERBICIDAL ESTERS OF 4-TRIFLUOROMETHYL-3'-
CARBOXY-4'-NITRO` DIPHENYL ETHERS
.:
Compounds of the formula
/~ ,~' `; '
y X '
- 1 ~
' ~O~ `. .'
~ CO2~(CHR ) (CHR2) ,03 R3
5wherein X is a hydrogen atom, a halogen atom, a trihalomethyl
group, an alkyl group, or a cyano group,
Y is a hydrogen atom or a halogen atom, :
Rl is a hydrogen atom or an alkyl group,
R is a hydrogen atom or an alkyl group, -
lOR3 is a hydrogen atom or an alkyl group,
m is an integer of 1 to 50, and ~:~
n is an integer of 0 to 6,
n' is an integer of 0 to 6, provided that the sum of : : :
n and n' is an integer of 2 to 6, .~ . :
15and compositions containing these compounds exhibit herbici-
dal activity.
' ~
'',''
,
1~3350;~
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 compositions.
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 o~ten quite closely related
compounds will have quite different weed control abilities.
Various diphenyl ethers may have overlapping or complementary
areas of activity or selectivity, and can thus be useful in
combination to control a variety of weeds upon application `;
of a single composition. Furthermore, the diphenyl ethers - ~
hereto~ore disclosed as herbicides are not completely effec- ~`
tive. An ideal herbicide should give selective weed
control, over the full growing season, with a single admin~
istration 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 phytotoxic to
the crops to which it is applied and should decompose or
otherwise be dissipated so as not to poison the soil perman-
ently. The known diphenyl ether herbicides fall short of
these ideals, and it would thus be desirable to have new
herbicides which show even more selective control of. unde-
sirable plants among desirabIe crop plants or which complement ~;
known herbicides in activity.
In accordance with the present invention, there 1s
. . .
`::
~133SOZ
provided a new class of novel diphenyl ethers ha~ing the
formula
_ CF3
I \X ;~ ~
O (I)
NO CO2[(CHRl) (CHR2)n,o]mR3
wherein X is a hydrogen atom, a halogen atom, preferably a :
fluorine atom or a chlorine atom, a trihalomethyl
group, preferably a trifluoromethyl group, an
alkyl group, preferably havlng 1 to 4 carbon atoms, - ~.
most preferably a methyl group, or a cyano group,
Y is a hydrogen atom or a halogen atom, preferably a
fluorine atom or a chlorine atom,
R is a hydrogen atom or a (Cl-C4)alkyl group, prefer-
ably a methyl group~
R is a hydrogen atom or a (Cl-C4)alkyl group, prefer~
ably a methyl group,
R3 is a hydrogen atom or a (Cl-C4)alkyl group, pre~er-
ably a methyl group,
m is an integer of 1 to S0, and preferably is 1 to 2, -.
n is 0 or an integer o~ 1 to 6,
.
n' is 0 or an integer o~ 1 to 6, provided that the sum ;`
o~ n and n' is an integer of 2 to 6, preferably 2. -::~
~hen the X, R , R , or R substituent is an alkyl group, it
can have elther a straight- or branched-chain configuration.
-3-
..
1133502
These novel compounds have been ~ound to show unex-
pected activity as weed control agents. In a preferred embod-
iment of the invention, X is a halogen atom, most preferably
a chlorine atom, Y is a hydrogen atom or a halogen atom,
preferably a chlorine atom, and either Rl or R2 is a hydrogen
atom. Most preferably both Rl and R2 are hydrogen atoms.
Examples of the compounds of the invention embraced
by Formula I include:
2-Chloro-4-trifluoromethyl-3'-(2-methoxy)ethoxycarbonyl-4'-
nitrodiphenyl ether
2-Chloro-4-trifluoromethyl-3'-(2-hydroxy)ethoxycarbonyl-4'-
ni;trodiphenyl ether
4-Trifluoromethyl-3'-(~-methoxypentaethoxy)carbonyl-4'-
nitrodiphenyl ether
2-Bromo-4-trifluoromethyl-3'-(~-hydroxypentaethoxy)carbonyl-4'- `
nitrodiphenyl ether ~ ;
2,4-Bis-trifluoromethyl-3'-(~-hydroxydecaethoxy)carbony1-4'-
nitrodiphenyl ether
2,6-Dichloro-4-trifluoromethyl-3'-(~-hydroxydecaethoxy)carbon-
yl-4'-nitrodiphenyl ether
2-Fluoro-6-chloro-4-trifluoromethyl-3'-(~-propoxypentadeca-
ethoxy)carbonyl-4'-nitrodiphenyl ether ~`
2-~ethyl-4-trifluoromethyl-3'-(~-hydroxypentaedecaethoxy)-
carbonyl-4'-nitrodiphenyl ether ~`
25 2-Cyano-4-trifluoromethyl-3'-(~-isobutoxypentadecaethoxy)- ~ ~ -
carbonyl-4'-nitrodiphenyl ether ~ ;
2-Iodo-4-trifluoromethyl-3'-'w-t-butoxyeicosaethoxy)carbonyl-
4'-nitrodiphenyl ether
4-Trifluoromethyl-3'-t~_hydroxyeicosaethoxy)carbonyl-4'-
3o nitrodiphenyl ether
2-Chloro-4-trifluoromethyl-3'-tw-methoxypentaethoxypentato-
methyl)ethoxy)carbonyl-4t-nitrodiphenyl ether
2-Chloro-4-trifluoromethyl-3'-tw-hydroxyhexamethylene)oxy-
carbonyl-4'-nitrodiphenyl ether
5 4-Trifluoromethyl-3'-t2-methoxypropoxy)carbonyl-4'-nitro-
diphenyl ether
2-Fluoro-6-bromo-4-trifluoromethyl-3'-t3-ethyl-4-ethoxy-
butoxy)carbonyl-4'-nitrodiphenyl ether
_4_
- .
~335~)Z
The novel diphenyl ethers of the invention are use~ul both
as preemergence and as postemergence herbicides. Preemer- -
gence herbicides are ordinarily used to treat the soil in
WhiCh the desired crop is to be planted b~ applicatio
.' / :
~ ~'~'.
~.,.~ ~ ., ,
-4a-
~3350Z
either before 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-
5 pounds of the invention are particularly active againstbroadleaf 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.
I~hen 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
emerged or while they are in their early stages of growth.
The ethers can be applied to the growth medium either be`fore ;
or after the rice has been transplanted to that medium. -~
The diphenyl ethers of the invention can be applied
in any amount which will give the deslred degree of weed
control. A preferred rate of 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 of 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
-5-
` ~133S02
employing a liquid carrier to accomplish the necessary
penetration and impregnation.
A diphenyl ether of the invention can be applied
to the growth medium or to plants to be treated either by
5 itself or, as is generally done, as a component in a herbi-
cidal composition or formula~ion which also comprises an
agronomically acceptable carrier. By agronomically-acceptable ;
carrier is meant any substance which can be used to dissolve,
disperse, or diffuse a herbicidal compound in the composition
without impairing the effectiveness of the herbicidal com-
pound 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 in any
ol 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 concentrates,
dusts, granular formulations, aerosols, or flowable emulsion
concentrates. In such formulations, the compounds are exten-
ded with a liquid or solid carrier and, when desired, suitable
surfactants are incorporated. ~ `
It is usually desirable, 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 practices.Examples of ad;uvants which are commonly used in the art can
be found in the John W. McCutcheon, Inc. publication "Deter-
gents and Emulsifiers Annual." ~
The diphenyl ether compounds of this lnvention can ~ :
be formulated in any appropriate solve~it. Examples of
-6-
',: ~' '
3SOZ
solvents which are useful in ~he practice of this invention
include wa~er, alcohols, ketones, aromatic hydrocarbons,
halogenated hydrocarbons, dimethylformamide, dioxane, dimethyl
sulfoxide, and the like. Mixtures of these solvents can also
be used. The concentration of the solution can vary from
about 2~ to about 9800 with a preferred range being about 25~ `~
~o 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
~ermits 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 emulsifiable concentrates is usually about 10%
to 60~ and in flowable emulsion concentrates, this can be ~,;
3G as high as about 75%.
--7--
il3350Z
l.~ettable 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 incorporating T,~etting agents, sticking agents,
5 and~or dispersing agen~s 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
3% of the composition, and a wetting agent can constitute
from 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
purpose include, ~or example, botanical flours, silicas,
':
. .
-8- ~`
~3350Z
~`
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 subsequently diluted to
about 1% to 10~i use concentration.
Granular formulations can be prepared by impregnating
a solid such as a granular fuller's earth, vermiculite, ground
corn cobs, seed hulls, including bran or other grainhulls, or~ ~
similar material. A solution of one or more of the diphenyl ;
10 ethers in a volatile organic solvent is then removed by evapora~ -~
tion. The granular material can have any suitable size, with a
preferable size range of 16 to 60 mesh. The diphenyl ether will
usually 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 applica~
tion. In one type of solid fertilizing composition 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 also be admixed in mixing or blending equipment,
or they can be incorporated with fertilizers in granular formu- `~
lations. Any relative proportion of diphenyl ether and ferti-
lizer can be used which is suitable for the crops and weeds to
25 be treated. The diphenyl ether will commonly be from about 5% ~ i
to about 25% of the fertilizing composition. These composi-
tions provide fertilizing materials which promote the rapid
growth of desired plants, and at the same time control the ;
growth of ~ `
`~"
'`': :. '
_ 9 _
~ "'
~1335~
undesired plants.
The diphenyl ethers o~ the invention can be applied
2S herbicidal sprays by methods commonly employed, such as
conventional high-gallonage hydraulic sprays, low gallonage
sprays, airblast spray, aerial sprays and dusts. For low
volume applications a solution of the compound is usually
used. The dilution and rate o~ application will usually ~ -
depend upon such factors as the type of equipment employed,
the methods o~ application, the area to be treated and the
type and stage of development o~ the weeds.
For some applications, 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~fective-
ness include:
` ~arboxyl`i`c Acid`s and Derivat`ives -
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
30 2,3,6-trichIorophenylacetic acid and its salts ~
3,6-endoxohexahydrophthalic acid ~ `
,;
: ., ~
', ~
- . .
1133502
~ dimethyl 2,3,~,6-tetrachloroterephthalate
trichloroacetic acid and its salts . .
2,2-dichloropropionic acid ancl its salts
2,3-dichloroisob`utyric acid and its salts
Carbamic Acid Derivatives
ethyl N,N-di(n-propyl)thiolcarbamate
propyl N,N-di(n-propyl)thiolcarbamate . ;~
ethyl N-ethyl-N-(n-butyljthiolcar~amate
propyl N-ethyl-N-(n-butyl)thiolcarbamate
2-chloroallyl N,N-diethyldithiocarbamate :
N-methyldithiocarbamic acid salts ~.
ethyl l-hexamethyleneiminecarbothiolate : :
isopropyl N-phenylcarbamate
isopropyl N-(_-chlorophenyl)carbamate
4-chloro-2-butynyl N-(m-chlorophenyl)carbamate
methyl N-(3,4-dichlorophenyl)carbamate ` ~
: ~ '` ``,
Phenols
dinitro-o-(sec-butyl)phenol and its salts
pentachlorophenol and its salts
Substituted Ureas ;
3-t3,4-dichlorophenyl)-1,1-dimethylurea
3-phenyl~ dimethylurea
3-(3,4-dichlorophenyl)-3-methoxy-1,1-dimethylurea
- 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea
3-(3,4-dichlorophenyl)-1-n-butyl-1-methylurea
3-(3,4-dlchlorophenyl)-1-methoxy-1-methylurea .`
3-(4-chlorophenyl)-1-methoxy-1-methylurea
3-(3,4-dlchlorophenyl)-1,1,3-trimethylurea :
.~
--11-- '-' ,` ` '
~13350Z
3-(3,4-dichlorophenyl)-1,1-diethylurea
dichloral urea
Substitut'ed Triaz'i`nes
2-chloro-4,~-bis(ethylamino)'-s-triazine
2-chloro-4-ethylamino-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-metnoxypropylamino)'-s-triazine
2-methylmercapto-4,6-bis(isopropylamino)'-s-triazine
2-methylmercapto-4,6-bis(ethylamino)'-s-triazine
2-meihylmercapto-4-ethylamino-6-isopropylamino-s-triazine
2-chloro-4,3-bis(isopropylamino)'-s-triazine ;~
2-methoxy-4l6-bis(ethylamino)-s-triazine
2-methoxy-4-ethylamino-6-isopropylamino-s-triazine
2-methylmercapto-4-~2-methoxyethylamino)-6-isopropyoamino-s- ~'
triaæine .
D`iphenyl` Ether Derivat`ives
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-tri~luoromethyldiphenyl ether
2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether
2-chloro-4-tri~luoromethyl-3'-ethoxy-4'-nitrodiphenyl ether
2-chloro-4-tri~luoromethyl-4'-nitrodiphenyl ether :
2-chloro-4-trifluoromethyl-3'-carbethoxy-4'-nitrodiphenyl
ether :~
2,4-dichloro-3'-carbomethoxy-4'-nitrodiphenyl ether '
.. .. .. : :.
''Anilid'es '' : :'
N-(3,4-dichlorophenyl)propionamide
-12~
1~33502
N-(3,4-dichlorophenyl)methacrylamide ~ :
N-(3-chloro-4-methylphenyl)-2--methylpentanamide
N-(3,4-dichlorophenyl)trlmethylacetamide
N-(3,4-dichlorophenyl)-a~-dimeth.vlvaleramide
N-isopropyl-N-phenylchloroacetamide :;
N-n-butoxymethyl-N-(2,6-diethylphenyl)chloroacetamide :~
N-n-methoxymethyl-N-(2,6-diethylphenyl)chloroacetamide
' Uracïls
5-bromo-3-s-butyl-6-methyluracil -~
5-bromo-3-c~ lchexyl-1,6-dimethyluracil
3-cycl'ohexyl-5,6-trimethyleneuracil :: .
5-bromo-3-isopropyl-6-methyluracil ~;
3-tert-butyl-5-chloro-6-methyluracil
' Nitriles
2,o-dichlorobenzonitrile ~.
diphenylacetonitrile ~ ;
3,5-dibromo-4-hydroxybenzonitrile ~ :
- 3,5-diiodo-4-hydroxybenzonitrile '~'~
Other OrGanic Herbicldes
O
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-tri~luoromethylaniline ~ "
N,N-di'(n-propyl)-2,6-dinitro-4-methyl~niline
N,N-di'(n-propyl)-2,6-dinitro-4-methylsulfonylaniline :
0-(2,4-dichlorophenyl)-0-methyl-isopropylphosphoramido-
thioate :~
-13- ~': `''
il33502
4-amino-3,5,5-trichloropicolinic acid
2,3-dichloro-1,4-naphthoquinone
di(methoxythiocarbonyl)disullide
3-isopropyl-lH-2,1,3-benzothiadiazin- (4)3H-one-2,2-dioxide ~. .
6,7-dihydrodipyrido[1,2-a:2~,1'-c~pyrazidinium salts
1,1'-dimethyl-4,4'-bipyridinium salts
3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine. :
4-~mino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5-
(4H)-one
3-Amino-2,5-dichlorobenzoic acid
N3, ~3-Diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylene- :.
diamine
N-(2-chloroethyl)-2,6-dinitro-M-propyl-4-trifluoromethyl-
aniline ~ .
5 N-Cyclopropylmethyl-a,~,~trifluoro-2,6-dinitro-N-propyl-_-
toluidine
N-(l-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine ~ ~ -
S-(0,0-diisopropyl)phosphorodithioate ester of N-(2-mercapto- :
ethyl)benzenesulfonamide `~
20 2-(-Naphthoxy)-r~,N-diethylpropionamide ~ .
2-Chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl- ~:
ethyl)acetamide
Methylsulfanilylcarbamate
3-(p-(p-Chlorophenoxy)phenyl)-l,l-dimethylurea .
.
Phosphonomethylglycine
Methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate -
Methyl 2-(4-(4-tri~luoromethylphenoxy)phenoxy)propionate
When mixtures of herbicides are employed, the relative propor- `~
tions which are used will depend upon the crop to be treated
30 and the degree of selectivity in weed control which is .
desired.
:-
The ethers of the invention can be prepared by ester- . ~
ification or transesterification of a diphenyl ether of the ~ :
-14- - :
,
~33~0Z
formula
IF3
y I X ` ':.
o (II)
~ ~'` ~"
¦ COOR
N2
wherein X and Y are as defined above, and R is a hydrogen ~ -
atom or an alkyl group, or of the corresponding acid chloride, ; ;~
with an alcohol of the formula
Ho-[(cHRl)n(cHR2)n~o]mR3 (III)
wherein Rl, R2, R3, m, n and n' are as defined above. One ~
method which is commonly used for preparing the carbinols of
Formula III is the polymerization or copolymerization of the
~ . ,~. .
corresponding alkyleneoxides by conventional techniques.
The esterification is generally carried out at a temperature
of about 0 to about 200C, and preferably at about 100 to about ~`; ;
:;-;:: . ~ .
150C, optionally in the presence of an inert organic solvent, `
15 such as a hydrocarbon or chlorinated hydrocarbon. In the ~ `~
., .~
esterification reaction, one equivalent of the alchohol 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 scavenger may be used. Typical acid
scavengers include inorganic bases, such as potassium hydrox-
ide, and amines, such as 2,6-lutidine, and the like.
:''"'`
- 15 -
' ;, .,-. .
.~ ,
~L133502
The free acid can also be esterified using a tri-
alkylorthoformate, without any additional acid catalyst.
Other conventional esterification techniques, such as trans~
esterification in the presence of an acid catalyst and the
like, can also be used.
A modification of the above preparative method for
preparing the esters of the invention involves the reaction
. .
of a metal salt, such as the sodium salt, of an acid of
Formula II with a halide of the formula ;~
Hal[(CHRl)n(CHR2)n,O]mR3 (IV)
where Rl-, R2, m, n, and n' are as defined above and Hal is
a halogen, preferably chlorine or bromine, atom. This reac-
tion is generally carried out at a temperature of about 0
to about 200C, preferably about lO0 to about 150C, and in
15 an inert organic solvent, such as benzene or toluene. ~ `
The diphenyl ether precursors can be prepared by
reacting a suitably substituted phenol, or the potassium or
sodium salt of the phenol, with a suitably substituted halo- ` ;
benzene, such as a chloro- or fluorobenzene in the presence
of an alkaline agent. Such precursors and their preparation
are described in U.S. 3,928,416, of Bayer et al., granted
December 23, 1975,
Another route to the compounds of the invention
involves the nitration of a diphenyl ether of the fo ~ ;
~ '~"' ,,''' .
~" ` :~'. '
;~,'
-16-
.
.
1~33502
- lF3 ;~
~O~ ' ' `~''
1~\ ,~
Y X (V) .-
J~ ",.
C02[(CHRl)n(CHR2) ,o~mR3
wherein X, Y, and Rl, R2, R3, m, n and n' 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 nitra~
tion reaction is generally carrled out at about -20 to about
100C, preferably about O 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
condensing a phenol of the formula
CH3
~ (VI)
Y OH X ~
wherein X and Y are as defined above with a substituted halo- ; `
benzene of the formula ~;~
. ,
-17_ `
~```, `
, ~:
. . .
~133502
xl
_ I o I (VII) i- ~
~- "
¦ \Co2[(CHRl)n(CHR2)n,o~mR3
2 ~ ;
wherein Xl is a halogen atom, preferably a fluorine atom, `;
and Rl, R , R3, m, n and n' are as defined above. This reac- -
tion is generally carried out at a temperature of about 0 to ;
about 250C, preferably about 75 to about 200C, optionally in
the presence of an appropriate solvent, such as sulfolane,
dimethylsulfoxide, dimethylformamide, hexamethylphosphoroustri-
amide, or other inert polar organic solvent. ;~
The following examples will further illustrate
this invention but are not intended to limit it in any way. `-~
In Table I, tYpical diphenyl ethers of the invention are
listed with their elemental analyses. A specific illustra~
tive preparation of the compounds of Examples 2 and 4 are set
forth before Table I. All temperatures are in degrees
Celsius and parts and percentages are by weight unless other-
wise indicated. -~
Example 2
Preparation of 2-Chloro-4-trifluoromethyl-3'-t2-methoxy)-
ethoxYcarbonYI-4~-nitrodiphenyl ether
a. Preparation of 2-methoxyethyl-m-fluorobenzoate
A solution m-fluorobenzoyl chloride (15.8 g. 0.1
mole) and 2-methoxyethanol (8.4 g. 0.11 mole) is heated in `~
glyme (100 ml.) for 8 hours at 60C. The solvent is removed
under reduced pressure and the residue distilled to give 9.3
g. f 2-methoxyethyl-_-fluorobenzoate, b.p. 70-75C/0.2 mm.
-18-
,f'. ~ ~
~133502
` b. Preparation of 2-methoxyethyl-5-fluoro-2-
; nitrobenzoate
2-MethoxyethyI-_-fluorobenzoate (9.3 g. 0.047
mole) is added dropwise at 5C to concentrated sulfuric
acid (100 ml). A solution of potassium nitrate (4.7 g. ;~
0.047 mole) in concentrated sulfuric acid (25 ml) is then
~ ;
added, the mixture is stirred at room temperature for two
hours, and then poured onto ice. Extraction with carbon
tetrachloride followed by drying and stripping of the solution
yields 2-methoxyethyl-5-fluoro-2-nitrobenzoate, which on
recrystallization from ligroin/benzene has a melting point
of 49.~-50.5C.
c. Preparation o~ 2-chloro-4-trifluoromethyl-3'-
(2-methoxy)ethoxycarbonyl-4'-nitrodiphenyl ether
A mixture of 2-chloro-4-trifluoromethylphenol ;~
(3.92 g, 0.02 mole) and potassium carbonate (2.89 g. 0.02
mole) is stirred overnight in dimethyl sulfoxide (50 ml.) at ;~
room temperature. 2-Methoxyethyl-5-fluoro-2-nitrobenzoate ;
(4.86 g., 0.02 mole) is added and the mixture stirred over-
night, poured onto ice, and extracted with carbon tetra- ~ `
chloride. The extract is stripped ~o give 2-chloro-4-
trifluoromethyl-3'-(2-methoxy)ethoxycarbonyl-4'-nltrodiphenyl
ether (7.5 g.) which solidifies on standing, and has a 1;
melting point of 60-62C. ~
. .
Example 4
a. Preparation of 2-chloro-4-trifluoromethyl-3'- ~
(~_methoxy hexadecaethoxy)carbonyl-4'- ~ `
nitrodiphenyl ether
A solution of 2-chloro-4-trirluoromethyl-3'-chloro-
carbonyl-4'-nitrodiphenyl ether (9.5 g, 0.025 mole) in -
toluene (300 ml) is heated under reflux for 4 hours in the
presence of ethylene glycol monomethyl ether, of average
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molecular weight 750 Ag., 0.025 mole). The toluene is then
removed under reduced pressure to give 26 g of 2-chloro-4-
trifluoromethyl-3'-(~-methoxy hexadecaethoxy) carbonyl-4'-
nitrodiphenyl ether `~
b. Preparation of 2-chloro-4-trifluoromethyl-3'-
(~-methoxy dotetracontaethoxy) carbonyl-4'-
nitrodiphenyl ether
A solution of 2-chloro-4-trifluoromethyl-3'-chloro-
carbonyl-4'-nitrodiphenyl ether (0.48 g, 0.0013 moles) in
toluene (300 ml) is heated under reflux for 4 hours in thè
presence of ethylene glycol monomethyl ether, of average
molecular weight 1900 (2.5g., 0.0013 moles). The toluene ;
is then removed under reduced pressure to give 2.4 g of 2-
chloro-4-trifluoromethyl-3'-(~-methoxy dotetracontaethoxy)-
15 carbonyl-4'-nitrodiphenyl ether. ;~
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The following examples show the herbicidal proper-
ties of diphenyl ethers of the invention. - ~;
Example 5
This example shows the herbicidal activity of ~ ~
diphenyl ethers of the invention towards a number of common ~-
.reeds. Using the procedure described below, diphenyl ethers
are evaluated for control of various plant species.
The following test procedure is employed. Seeds of ~
selected crops and weeds are planted in soil in flats. For `
preemergence tests, the flats are treated with the test com-
pound immediately after the planting. For postemergence ~ -
tests, the seeds are allowed to germinate, and after two
weeks the flats are treated with the test compound immed-
iately 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 application of two pounds
per acre. About two weeks 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 summarized in Table II, which `~
gives the average percent control achieved by the test
compounds with 0 representing no weed control and 100 com- `
plete kill of the plant. ``~
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1133S02
TABLE II
HERBIC'IDAL ACTIVITY
Compound #2 Com~ound #l
Common Scientific Pre- Post Pre- ' Post :
5 Name ` Name emer- emer- emer- emer-
Monocots ~~~' gence gence gence gence ''~
barnyardgrass ~chin'ochloa
` cru`sgal'li'' 100 100 99 100
downybrome Bromus tectorum100 90 90 40
green foxtail ' Setaria viridis100 100 100 100
Johnsongrass S'orghum ~ .
(seedling) `-halepense 100 100 _ _ ,
yellow nutsedge ' Cyperus
esculentus 50 100 90 70
quackgrass Agropyron repens 0 40 0 40 ~ ';
wild oats Avena fatua 70 99 90 99 ~'~
'oermudagrass Cynodon dactylon - 60 - 0
yellow millet Panicum ' :
' miIiaceaum - - 100 100 :.. , ~'
Dicot's
Bindweed Convolvulus ' ~
arvensis'~~~ 0 100 50 100 " ~::',,`
Cocklebur Xanthium ' :
pensylvanicum 0 100 50 0 ~:
Coffeeweed Sesbania spp. 100 100 30 loo
Morningglory Ipomoea spp. 0 100 0 100 ~'
Black nightshade Solanum nigrum 100 100 100 100
velvetleaf 'Abutilon
'theophras't'i 40 100 100 100 ~ ,'
30 safflower Carthamus . '
'tincto'ri'us 0 99 30 100 ~ ,:
Example 6 ,~
, .
The compounds of Examples l to 3 were also evaluated .
in conventional field tests. In one typical field test, the ,`.
compound of Example 2 was tested for control of a number of ,':',.
-23- '
~133S02
.
annual grasses and broadlea~ weeds and for tolerance to a
number of common crops. Table III summarizes these tests
results, using the same scale o~ control as in Table II.
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It is to be understood that changes and variations
can be made without departing from the spirit and scope of -
this invention as defined by the appended claims. ;
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