Note: Descriptions are shown in the official language in which they were submitted.
105~11B
This lnvention relates to novel herbicidal compositions
comprised of a diphenyl ether her~icide and a paraquat or
diquat salt, and to methods of controlling weeds with these -~
compositions
A wide variety of diphenyl ether herbicides can be
used in the composi~ions of this invention. Among the preferred
classes of diphenyl ether herbicides ara those containing a
2~-dichlorophenyl ring or a 2-chloro-~~trifluoromethylphenyl
ring and those containing a ~-nitrophenyl or a 3-subs~uled
lO ~-nitrophenyl ring. The most preferred diphenyl ethers are ;~
: those of the formula~
CF3 ~ -
.;~ , . .
~'.'' I ``
'''~' ~Z ~ ' . ,
' ~ ` N 2 ' ! , ~ ~ ~
~. ., .:
wherein X is a hydrogen atom~ a halogen atom~ a trihalomethyl
group, an alkyl group, or a cyano group~
Y is a hydrogen atom~ a halogen atom~ or a tirhalomethyl
- group~ and
Z is a hydrogen atom~ a hydroxy groUp~ an alkoxy group,
-` ; an alkyl group~ a halogen atom~ an amino group~ an
`~l alkylthio groupS a cyano group~ a carboxy group~ a -
;; 20 carbalkoxy group, a carboxyalkyl group, a carbalkoxy~
alkyl group~ an alkanoyloxy group~ an alkanoyloxy
group7 or a carbamoyloxy group. ~-~
, , .
'' , , - ' " ~ ' ' ~ :,' ',
-2-
.,
~ Among the compounds embraced by Formula I the more
: preferred are 2-chloro-4-trifluoromethylphenyl 3-substituted ~:
~-nitrophenyl ethers. All Or the compounds of Formula I are
disclosed in co-pending Canadian application number 165,96
of ~o~t o. sayer et al. filed March 13, 1973.
. ~pecific diphenyl ethers which can be used include
2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ~
ether, 2-chloro-~-trifluoromethylphenyl 3-carbomethoxy-4- ;
nitrophenyl ether, 2-chloro-4-trifluoromethyl 3-(1-carbethoxy) ~ :
ethoxy-~-nitrophenyl ether~ 2-chloro-4-trifluoromethylphenyl~
4-nitro-3-methoxycarbonylphenyl ether~ and the like. .
.. ..
The preferred compositions of the present in~ention :~
contain 2-chloro-~-trifluoromethylphen~l 3-ethoxy-~-nitrophenyl ;
.....
ether in admixture with a paraquat salt of the formula: : .
. `~
CN3 ~ _CH3.2A ~ -
wherein A is an anion~ preferably chloride. ~ ~
In general~ the compositions o~ the present invention . .
,, . . ~.
will contain the active ingredients in a weight ratio of ether
to paraquat or diquat salt of from about 1:10 to about 10:1
20more usually about 6:1 to about 1:6, e.g. about 1:1.
The herbicidal compositions Or this invention :.
exhibit synargistic activity in the control Or a broad spectrum :
~' ' ` ' . . ~ . .
., . ~.' ','.
', '`. .~:
:: 3
: -
of monoco~yledonou~ and dicotyledonous weeds, and are thus
particularly useful as chemical sur~nerfallowing agents. They
_ are especially effective against weeds of the Compositae
family~ such as Lactuca nulchella ~blue letiuce~ and Cirsium :-~
arvense (Canada thistle). However, they may also ~e used to
control weeds of the Ai~oa~e~e~ ~n~ranthaceae~ Carvo~hvllaceae~ l
; Cheno~odi~ceae~ Convolvul~e~e, Cruciferae, Cv~eraceae, ~ -
Gramine~e, Leeuminosae, Ma~vace~e, Polv~onaceae, Rubiaceae, ~ ;
Scrophul~riaceae, Solanace~e and Umbelliferae families.
In general~ the compositions are applied post~emergence, ;
that is~ after the weeds have emerged from the growth medium,
in a herbicidally effective amount. The compositions will
generally be used so as to give an application rate of the
ether of from about 0.15 to about 8 lbs./acre~ more usually
about 0.25 to about 2 lbs./acre and an application rate of
~ paraquat or diquat salt of about 0~25 to about 2 lbs./acre. ~
., ~ . . .-
~` In chemical summer~allow trials 9 treatments of
Lactuca ~ulchella and Cirsium arvense with a tank mix combi-
nation of 2-chloro-~-trifluoromethylphenyl 3-ethoxy~ nitro-
phenyl ether and a paraquat or diquat salt7 produced a
synergistic effect in controlling these weed species.
Applications to blue lettuce were made to established
plants 0.1 - 0.25 m~ in height and to plants clipped back to a
uniform height of 0.1 m. A one-half square meter area was
. .
chosen at random in each replication for each treatment. The ~
plants were cut at ground le~el and their fresh weights and ~;
heights were taken~ Tharea~ter~ plants were air-drled and `~
their dry weights were taken.
:
~ .
' : .
;'~ ~":''
~5~8
Applications to Canada thistle were made at the 2-10
leaf stage. The infestation was natural from stolons already
present in the soil. The ten largest Canada thistle plants ;~
were harvested for each treatment and their fresh weights and
heights were recorded.
, Table I sets forth the average weights and heights of
treated and untreated blue lettuce plants and the average
, percent control achieved by the test compounds. The results
were the same for the clipped and unclipped plants.
Table II shows a comparison of the actual percent of ,~
- weed control (taken from Table I) with the expected percent ~,
control~ as calculated using Colby's method of determini,ng
synergism. This method involves the use of the following '
' --- formula: ,
~'~ 15 ' ( 100 ' '~
,,, ' ! wherein A equalsthe percent control by herbicide A at x , -
` ~ kg/~a. ' ~;
,, B equals the percent control by herbicide B at y ';
kg/Ha.
'' 20 E equals the expected control by A + B at x + y
' -, ' kg/Ha.
- . .-
~able III sets for the percènt control calculated '~
,for weed counts x heights for each treatment of Lacbuca ~
pulchella referred to in Table I. The following formula was " '
, , 25 used to determine the data in Table III. '',~
`'`i ' ' ' '', ';.
'~ , 100 - (weed count per plot x weed height per Plot x 100)'
~weed count in control plot x weed height control plot) ,'~
: . -5- :
, . . .. .
.~ ' ',
'; , ~
~' ' , ' . ' ' ' ~` ' '~'
-
1~5i~1~8 ~
The data in Table III was then subjected to Colby's test
for determining synergism as shown in Table IV.
Table V shows the average fresh weights and heights of
treated and untreated Canada thistle and the average percent ~;
control achieved by the test compounds. The data in Table V
was then subjected to Colby's test for synergism as shown in
~able VI.
In Tables I to VI, Compo~ld I and Compound II are
respectively 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-
phenyl ether and 2-chloro-4-trifluoromethylphenyl 4-nitrophenyl
eth~r. The data in these tables demonstrates the unexpected
synergistic activity of herbicidal compositions comprising a ;
paraquat or diquat salt and a diphenyl ether herbicide~ when
compared to the individual activity of the components of the
15 composition. ` ;
'" ' ` ' ' . ~;'
"
.
. ~ ,:
:
; `, ' ' '
~
: b' ~
~ ~
-6- ~
,
,
- ;
'f
~ , ,
lOS~L8
.~ o o ~ CO ~ ~ ~ ~ o ~ o
. ~ C~ CO ~i J ~ ~ o~ co ~ O ~ \O r i o U~
O'~ ~) ~ C' .~ 1~ ~ ~ CO a~ o~ o
~ ~ ~ : .'
. . ~ ';
., ~1 _
C~ ~ O\ ~ CO ~ O ~ O ~ ~ ~ CO
,, ~ ) ~ ~ \J ~ CO O r~ CO ~ ~i ~~ a:) .. -'
~.'' ~; CO ~ ~ ~ ~
.. ' ~-: '
:', , `'"~"' ~.
U:l ,_1 ~ ~ ~ $ t o ~' ~o o o c~
. ~ ,~ , ~ ~.
~,, ~ c~ ~ ~ ~ ~ ~ c~ o ~ ~ o co ~ ~ ~ r~
!: ' ' :: ' ~ ~3 ~ 3 1 ~ ~ O ~ ) O C~ ~ O O ~ ~ O r~
~! .. ~ ~ ~I co ~ ~ ~o co cs~ ~ h
, cq t:~l c4
~ P . ~ . ,~
H ~ H F ~ C\~ C~ co co ~o ls~ O ~ (~ ~ co O C~ q ` ;.
~: ~ ~ ~ C) ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ O . ''
'.''; * ~: p ~ ~C CO ~ ~ ~ ~ C~ I r I ~ ~ CO ~ CO
H ~; m ~ h
~ h ~ F'l c~ _ O O ~ ~ O O C\l ~ O \0 ~n CO .
,~ . . . ~ `0 b~ ~ co r-i C~ ~) N ~i ~ CS~ O cO (Y~ O \D ~, CS~ ~ ~ rt ~ r-l N rl N r-l fr) ~ ~I CO C~
. ~ ..
H CO ~ cO CO ~ co co
~ ~ N ~ N N ~I N N .:`~.
,~,. ~ O O O O O O O '' :~
,_ + t + + + + + ~ : :
a)~I ~1) N CO ~t CO ~D ~0 ~ N CO :i~ N co N N ` ~
p; ,~ O ~1 ~I N O O O O rl~I N r-l 0 ~1 ~1 ` ~ .
` ,: ~,
` ~ ~ "',; :,'
H ~ H
~¦ H H H ~ o~ H a h O
.. `~ ~3 h~ h~ + ~ .-t t ~ + .~ So~ o
E I V ~ P~ H H H H H H Iq V V H
~ ~ ~ N ~r) ~ ~ ~ C` co C~ O r-i t~
: j - :' ~ ~: ~ .
." `' ' '~'
~ , -7- :
- lOS;~
'.; ,
_~ G~ C` CO CO f~)
0 X C' ~O CO ~O CO ~
~ .bO h ~:1
'
0
:~ ~h ~ ~ Ol O C~l O ~ ~) `
_ ~ CO ~O O ~O ~)
CO ~ ~ O ~ ~ ,~,'
l . '.
1 O CU ~ Oi ~I co co ,' "
.5;' 0 Q ~ (~
rl ~1
, ~ O
a~ ~ l o ~) ~o ~
h ~ ~ coC' O C` ~i :~
4 c~ ~, co co ~ ~ ' '.~'
"~, _ , ~ ` ~ ` ~
,:. ~ . : :
o ~ cs~ o ~ a~ ~
1 ~ D ,~ D ~ D
:;: H U~ 0--~ ¦ O ~(~1 0 ~ C~ . -
H f~, coo~ ~ O,~ ~ ,
E l ~ co ~ co co
~ O O O O O O'
.~ _. ~ ~ + , i~
a~ ~o ~o ~JcoC~ ,.
.'"~ 'O ~ ~ ~ ~ 1
, v ~;
h h h h r~
i:'. ' '`
,:~ ~ 1~ 4 ~ +
H H H H I~
~ ' E I . O O O o o o '~
', O , O O O O o
~,~ ~ V V V V V
.: . , ,::
'
r :
l~S;~
` h
~
. ' ~'' .,
~, o . ~ 1 o o ct
.~ ~
~ . ~D C~l ~ ~)O~ O~ ~)~ (~ O a~ r~) :
m ~ ~D ~ c- ~ ~ ~ ~ o~ o co ~
. ~ ,
R . ,,
'.
_
'
' ~ .
H . ~ O 0~1 ~ ~ O O O O O
~1 1 l
. O C-- OO CO ~ C~.l O O O O O
~- F~l co O O.~ o O O O O O
~r; ~ ,
.' ~ . : ~.
. H ~ ~ ;`
~:)H ,- il C~ ~ CO 01 O ~O ~ O O O 0~ ~5) ` `
,~ $ . ~ O ~ O O O 1~ CO ' ,' `'
H ~ .~, a l ~ ~ ~ 1~ C~ 1~ ~) O O O co co
. . ~ ~ O ' ~ - :
H C~ æ
g H ~ CO OO ~ ~ C~O 0~ O C' ~ 1
~3*. . C~ ~1 CO O O \~ S) O O~
p m + ~ 0 ~ cs~
" .
" ~: :
~ CO ~O CO CO ~ CO
.. ~ . bJ ~ C~l co ~ co ~o O O O O O O ,'' .'~
~D 01 ~ ~ ~ ; -
, _ . .. . . . . + ~ + I + + -~ ~ -
o ~ ~ ~ O O ~ ;.
:, ' 'td ~ ~O ,~
.;, ~ o o
:, ~
:
H H ~I H ~
o iy ~ h
O O O o ~ ~ ~
O ~ h ~ + + + + + +
O O O o ~ ~ ::
l V V V V 1~ ~, H H H H H H :~
': ' -
::
- , ~ C~l ~ ~ ~ ~D ~ co ~ O
!
:'
:, ~
-- .
_9_ .
~,, .
~ 5~L8
o
~. ~¦ ~ ~ ,
. ~ . O , ::
~, ~
..
.`,: ~ ~ co ~o o ~ , ~ .
H ~ ~0 '~ c ,~ ; ~
.,, t~ -',~,` ``
., ~ ~ o ~
H ~ I r~ CS~ O~ O
o ~1 ~ o ~ ~ ~ 3
.` H~ 1 -~ CO ~ i . !~ :
H ~ ~;
:. ~I H
~ ~ ~t ~ co ~co co co co
r,, 1-1 . r~ ~ r;Q ~ 0 0 0 0 0 0 ,'.,~ :
m ~, C~ ~ ~ ~ ~D ~ cO ~
P; o ~ ~ ~ ~o r~
C~ ~ o O r~
~ ~_ . ". ~:
` ' ~ ' ' CO ~ O
O.'~ ' ~ P h
+ ~::, .
H ~ ~ H H H H H ~ - ~ ``' ;
F~ rlO ' O r~
`: . E-l ~ c~ ~ H ;~
' ' ' :` ' -
, - :
. --10--
. ~ . ` , . : , ,
:: - . . : . , , ` : -
. . 1, :
3~05~
,
.
O ~ co ~D co ~ ~ ~ C~,~ O O
h ~ C~ :
~ . ' '
. '''. ~.'
~ ~_ ~ 0~ ~) . t 01 ) C~l ~ ~ 1--1
.
i, _ O O C~ CO~I O ~ 0'~
`" ~'
., ~
. '
h ~ o, ~ ¦
I
Pl ~ O
~ o ~ ~ a
~q ~ ,~ ~ 0 ; "'' ~.'.
P~ ~ . `,'~
H . s~ ,`':~.
. ~ ' C ~COCO~CO C` ~ `.
CO ~ Cc~ CO C~ '~
~ O r~ i O O O O ~! ~ .i ri O ~; r i ~ ~ ~
cs a ~ ~ fa ~a ~ a
o~ o ~o3 ~,hd ~,~ + + + ~ + + ~ s~ ~ . .~
E~ P. ~ H H H ~ H H ,'~ - ~ ?
'`', ' , ' ~''`~ '
, :
~OS;~8
~;
_~ ~ r~ ~ C~ ~I CO ~D
'c ~ ~ ~ ~ ~ ~ C~l
~, ~
. C~ ~ '
~;5! ' ' ~
'~ ~ 'l 00 ~ O r-i ~
i~OC~
f, :
I` ' O J~ J CS~ ~
S ~ ~> ~ O ~o ~ ~ O
o'
." , ~* . ~,
~ O ~
o r~
~ ~ol Q~ o~o~o~ o ~
r~J co ~
; _ O O r; ~ ~_i ~ - ::
-~
~:',' O
f~ ~ ~ f~
H H H H H 1--1
I ~ ~ ~ 'U ~ ~ : ' '
~` ~3; r~
V C~ V
~: '' ` `.
f'` ' `'
'''' ' " , . " ' ~." ~
~05~1~B
The compositions of the invention are generally
applied to the growth medium or to plants to be treated in a
herbicidal formulation which also comprises an agronomically
acceptable carrier. By agronomically acceptable carrler i5
meant any substanca which can be used to dissolve, disperse, or
diffuse a herbicidal compound in the composition without impair-
ing the effectiveness of the herbicidal compound and which by
itself has no detrimental effect on the soil, equipment, crops,
or agronomic environment. The herbicidal compositions of the
invention can be either solid or liquid formulations or solutions.
For example, the compositions can be formulated as we~table ~,o C'
powders, emulsifiable concentrates, dusts, granular formulations, '''
aerosols, or flowable emulsion concentrates. In such formula- `'
. .
''; tions, the compounds are extended with a liquid or solid carrier
and, when desired, suitable surfactants are incorporated. The
two components of the compositions can be combined together in '~
a single solution or for~lulation or they can be added as separate
'solutions or formulations to a spray tank prior to application of
the mixture. While it is preferred that the two active ingred-
ients be applied in admixtura, it is within the scope of the
invention that they be applied sequentially to the area where
.; , , .
weeds are to be controlled.
Adjuvants, such as wetting agents, spreading agents,
dispersing agents, stickers, adhesives, and the like, can also
,
be advantageously employed in accordance with agricultural ~
' practices. Examples of adjuvants which are commonly used in the ~ ~'
.. , .:., ,
'; art can be found in the John W. McCutcheon, Inc. publication
'~ "Detergents and Emulsifiers Annual." ' -'
:' ~.: :
-13~
,, - .~', '.
~OS;~
,
The components of the heIbicidal fcompositions
of the in~ention can be clissolved in any appropriate sol-
vent. Examples of solvents which are use~ul in the practice
of this invention include alcohols, ketones, aromatic
hydrocarbons, halogenated hydrocarbons~ dimethylformamide~
dioxane', ~imethyl sul~o~ide~ and the like. Mixtures of
these solvents can also be used~ The concentration of f
!:
the solution can vary from about 2% to about 98~ with a
preferred range being about 25% to about 75%0
~10 - For the preparation of emulsifiable concentrates~
the components of the compositions can be dissolved in
organic solvents~ such as benzene~ toluene~ xylene~ methyl-
ated naphthalene, corn oil~ pine oil~ o-dichlorobenzene,
isophorone, cyclohexanone~ methyl oleate~ and the like~ ;
or'in mixtures'of these solvents~ together with an emul- i~
sifying agent which permits dispersion in water. Suitable
. . . .- ' emulsifiers include, for example~ the` ethylene oxide deriv-
atives of alkylphenols or long~chain alcohols~ mercaptans~
' carboxylic acids~ and reactive amines and partially ester-
ified polyhydric alcohols~ Solvent-soluble sulfates or
sulfonates~ such as the alkaline earth salts or ~nine salts
of alkylbenzenesulfonates and the fatty alcohol sodium
sulfates~ having surface-active properties can be used as
i
' emulsifiers either alone or in conjunction with an ethylene ~
oxide reaction pro'duct. Flowable emulsion concentrates . ~' ;
are formulated similarly to the emulsifiable c'oncentrates
~ 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 acidO ' ;~
3 The concentration o~ the active ingredient in emulsifiable `~
'` -:;
-- ::
, I
~ ~(35~3LJ.8
concentrates is ~sually about lO~o to 60% and in flowable
emulsion concentrates~ this can be as high as about 75%0
Wettable powders suitable for spraying, can be
prepared by admixing the components of the compositions `~
with a ~inely divided solid, such as clays, inorganic
silicates and carbonates~ and silicas and incorporating
wetting agents, sticking agents~ and/or dispersing agents
in such mixtures. The concentration of active ingredients
in such ~ormulations is usually in the range of about 20
to 98%, preferably about 40% to 75%. A dispersing agent
~an constitute about 0.5% to about 3% of the composition,
and a wetting aOent can constitute from about 0.1% to about
5% of the composition.
Dusts can be prepared by mixing the active com-
ponents with finel~ divided inert solids which may be
organic or inorganic in nature. Materials useful for this
purpose include, for example7 botanical flours, silicas,
., , ~
silicates, carbonates and clays. One convenient method i -
o~ preparing a dust is to dilute a wettable powder with a ~;
Xinely divided carrier. Dust concentrates containing about
20% to 80% of the acti~e ingredient are commonly made and
are subsequently diluted to about 1% to 10% use concen~
tration.
Granular formulations can be prepared by impreg- `~
`~ 25 nating a solid such as granular fuller's earth~ ~ermiculit;e~ ~ `
~ ground corn cobs, seed hulls, including bran or other grain `~
: ... , , . . ~,
hulls~ or similar material. A solution of one or both ~;
active components in a volatile organic solvent can be
sprayed or mixed with the granular solid and the solvent ~ -
can be sprayed or mixed with the granular solid and the
~15
:1 ~)S~l~&~
solvent then removed by evaporation. The granular material
can have any suita~le size, with a ~referable size rangs
of 16 to 60 meshO The active ingredient will usually
comprise about 2 to 15% of the granular of the granular
formulation.
The herbicidal compositions of the invention can
also be mixed with fertilizers or fertilizing materials be-
fore their applicationO In one type of solid fertilizing
composition in which the composition can be used, particles
`10 of a fertilizer or fertilizing ingredients~ such as a~onium
sulfate, ammonium nitrate, or ammonium phosphate~ can be
~oated with one or more of the ethers. The compositions
and solid fertilizing material can also be admixed in
: mixing or blending equipment, or they can be incorporated -~
1~ with fertilizers in gra~ular formulations. Any relative ; -
proportion of the active ingredients and fertilizer can be
used which is su1table for the crops and weeds to be trèated. ;~
~ The total active ingredients will commonly be from about
; 5~ to about 25% of the fertilizing composition. These com~
positions provide fertilizing materials which promote the
rapid growth of desired plants, and at the same time con- l~
trol the growth of undesired plants.
The herbicidal compositions of the invention can
be applied as herbicidal sprays by methods commonly employed, `~
such as conventional high-gallonage hydraulic sprays, low- ;
gallonage sprays~ airblast spray~ aerial sprays and dusts. j-
For low volume applications a solution of the active com~
ponents is usually usedO The dilution and rate of
;. -
: .
.
-76- ~ ~
(35~
application will usually depend upon such factors as the t~pe
of equipment employed, the method of applicatlon, the area
to be treated and the type and stage of development of the
weeds.
~he ether and paraquat or diquat salt herbicides of this
invention may be used in conjuction with other compatible
herbicides such as one or more of -those listed in the
Canadian application referred to above and the various
individual herbicides listed in the latest editions of (A)
Pesticide Manual, British Crop Protection Council, (B) index
des produits phytosanitaires, AC~A-FNGPC, (C) Pesticide
Handbook - Entoma and (D) Pesticide Index, D.E.H. Frear.
It is to be understood that changes and variations
may be made without departing from the spirit and scope of
the invention defined by the appended claims.
' ' ' ~ ' ' .' ~:
.... . ...... .
'`'''' ' ' ~
:: : - .
': ;' , - " ' ~;,-;:'
: ' ' ' , ., ' ~ '
~ -17- ~
.- ,~ : :
. . ~:'' . ,
'
