Note: Descriptions are shown in the official language in which they were submitted.
8~6
:
.
CIBA-ÇEIGY AG 5-1163~/+
',
Herbicidally active substituted diphenyl ether derivatives, processes
;
for their manufacture and herbicidal compositions containing them,
and their use or selective weed control
The present invention relates to novel herbicidally active
substituted diphenyl ether derivatives, processes for their manufac-
ture, herbicidal compositions which contain these novel compounds as :~
active ingredients, and a method of selectively controlling weeds in
crops o cultivated plants which comprises the use of the novel deri-
vatives and the compositions containing them. ; ; ~ ~ :
In addition to m ~erous variously substituted (phenoxy)-a~
phenoxy-alkanecarboxylic acid derivatives, substituted 3- and 4-
~phenogy)-phenoxy alkanols, their corresponding phenylthio analogues,
mercaptans, esters, amines and further derivatives have also become
known from the literature ~German Offenlegungsschrift 2,611,695 and
2,533,172, US pa~ent 4,046,798).
: It has been found that certain 3-(phenoxy)-phenoxy alkanolsand their derivatives ha~e:in many respects a superior herbicidal
action to these prior art compounds.
~ I ~ :
:
:
:. :
:: , :: : : :
: ~ :
The active compounds of khe present invention have the formula
R
( lR6)m ~_ ~I-C~-12~~
X - ~ - R (I)
R5 ( 3)m
wherein
Rl is c~ cl~ alkyl or the -CH20H group,
R2 is hydrogen, halogen, the nitro or cyano group,
R3 is hydrogen, halogen, Cl-C4 alkyl or the nitro group,
R4 and R5 each independently of the other represent hydrogen, CF3, CN or N02,
R6 is hydrogen or halogen,
m is an integer from O to 3,
X and ~ each independently of the other are oxygen or sulfur,
Z is halogen or a ~OHg -SH, -OR7 or -S-R
()n
wherein R7 is alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl or
benzyl, which radicals can also be substituted by halogen, CF3,:NO2, CN,
alkyl, alkylthio, alkoxy~ -OH, NH2, alkylamino, dialkylamino, and/or alkoxy-
carbonyl, and R7 can also be a -CONH-alkyl, -CO-NH-aryl, -CO-N~dialkyl), ` :
-CO-aryl or -CO-alkyl group, the alkyl and aryl moieties of which can addition-
ally be substituted by halogen, and R7 can finally also be a radical
CH
-CO-CH-O ~ ~ ~ ~ ~ (R10)1-3 .
Q
: 2 _
k~ ~ ~
'
`
366 ~ -
in which ~he recurring or non-recurring substituent Rlo can be the same or
different and is halogen, NO2, CN, C~3 or alkyl~ Q is =CH- or -N- and n is O,
l or 2.
e active cornpounds of the formula I can be obtained from phenoxy-
phenols or phenylthio-(thio)phenols of the formula II
. ~
: y_~
R ~ ~ R (Il)
R4
or from corresponding phenolates by a variety of rr.ethods known to the skilled
person, for example by reaction with compounds of the formula ~
; 11 .
B - C ~ CH ~ Z
^ H
lC wherein B is halogen or a sulfonic acid ester group, for example 2-bromo-
propanol, in the presence or absence of an acid acceptor, and subsequent
esteriflcation of the resulting propanols.
~ Alcohols ~Z = OH) are also obtained by saponification of the
; corresponding haloalkyl compounds (Z = halogen), which have been obtained
from alcohols and halogenating agents, such as thionyl chloride. Alcohols
are furthermore obtained by rcduction of corresponding carboxylates, for
; exarnple with LiAlH4 or lithium borohydride.
` Mercaptans (Z = SH) are obtained for exarnple from the corresponding
halogen compounds (Z - halogen) by reaction with metal hydrogen sulfides or ~
:: --
~'
'~ ~ ',
" ~ ,.' , ~'
i6
metal hydrogen xanthates or by reactio~ with thiourea and subsequent a~aline
cleavage o~ the resulting thiuronium sa:Lts.
Ethers and thioethers (Z = OR7 and SR7) are obtained by reacting
the corl~esponding halogen compounds (Z - halogen) wlth alcohols or mercaptans
or by reacting the corresponding alcohols or mercaptans (Z = OH or SH) with
halides.
Esters and thioesters are obtained in a mc~nner known per se by react-
ing corresponding alcohols or mercaptans (Z = OH or SH) with acid halides,
acid anhydrides or carbamoyl halides5 in the presence of acid acceptors.
Sulfoxides and sulfones are obtained by oxidation of the correspond-
ing thioethers, for example with H2O2 or permanganate.
Some of the starting materials of the formula II are known, Start-
ing materials of the formula II which have not yet been described can be ob-
tained by methods which are known per se, for example those described in
German Offenlegungsschrift 2,643,438 and 2,639,796. If a substituent R2 is
; halogen or the cyano group, it can be introduced in known manner from the
corresponding nitro compound by reducing the nitro group to the amino group,
diazotising this latter, and replacing the diazo group by halogen or -CN.
The above reactions are preferably carried out in a solvent or di-
luent which is inert to the reactants. Suitable solvents or diluents arethose of the most widely different classes, such as aliphatic and aromatic,
unsubstituted or halogenated hydrocarbons, and also polar inert organic sol-
vents, such as ethers, ketones, amides etc. Specific
~;:
.~
~ - 4 - _
~ ' ~
~;
`' ,' . ~ . , .
examples are diethyl ether, butanone, methylene chloride, ~e~hyl ethyl
ketone, dimethoxy ethane, dimethyl formamide and tetrahydrofurane.
Suitable basic acid acceptors for the reaction with halogen
compounds can be aqueous alkali metal hydroxides, such as KO~ a~d ~aOH,
and alkali metal carbonates (K2CO3, NaECO3), alcoholates (NaOCH3), and
also in particular organic bases, such as triethylamine, pyridine atc.
: Preferred compounds of ~he formula I are those in which X isoxygen, namely phenoxyphenyl derivatives; and Y is also preferably
oxygen.
Within ~he group of preferred compounds of the formula I in which
X and Y are oxygen, par~icularly interesting compounds are those where- ;
in Rl is the methyl group and R3 is hydrogen or halogen, and R2 re-
presents either hydrogen, halogen or the cyano group.
: Among the less important nitro compounds (R2 = N02~ are those
of the following formula: :
CE3
(R6)m O-CH-CH -Z
O ~ NO
R5 (R3)~
wherein R3 is hydrogen or halogen and the other symbols are as defined
for formula I.
The compounds of the formula I have a good broad activity
spectrum against weeds (monocots), but are well tolerated by dicotyle-
. donous cultivated plants and by different types of cereals, and a~etherefore useful both as pree~ergence and postemergence herbicides for
.~
~he selective control of grass-like weeds in crops of cul~ivated plants.
.~
~ '' .
The follo~ing Examples illustrate the manufacture o~ a number o~
active compounds (active substances) of the formula I. Further active
compound~ obtained in corresponding manner are listed in the subsequent
table.
:' ~
~ ,:
:
, :
. ,:
,;, - :
- ~ ' :,'',
.. . .
"- '
-
. ' . ~, ~
86~
- 7 -
Example 1: 1.5 g (0.39 mole) of lithiu~l al~inium hydride are
charged into 100 ml of absolute et~er. With efficient stirring, a solu-
tion of 21.5 g (0.052 mole) of methyl-3-(2'-chloro-4l-trifluoromethyl-
phenoxy)-a-(6-chlorophenoxy)-propionate in 25 ml of ether is added
dropwise, such that the reaction mixture is ke!pt at the boil. When the
addition is complete, the reaction mixture is subsequently stirred or
1 hour at boiling temperature. After addition of 50 ml of water and
50 ml of 10% sulfuric acid, the ethereal phase is separated and the
a~ueous phase is extracted twice with 100 ml of ether. The combined
ethereal extracts are ~ashed once with water cmd dried over sodium
sulfate. The solvent is distilled off and the residue is chromatographed
on Alox I, affording 17.8 g of a bro~n oil, which is the propanol of
the formula
1 3
Cl O~ I O~I
( ~l 2
C~3~0 ~CL
Analysis: C calculated 50.37% H calculated 3.4%
C found 50.3 % H found 3 5%
: 29 g (0.1 mole) of 2,4-dichloro-37-hydroxy-4'-chloro-
diphenyl ether are dissolved in 100 ml of 2-butanone. With efficient I ;
stirring9 37.2 g of 3-bromo-1,2-propanedîol, 38.7 g of potassium
carbonate and a trace of potassi7m7 iodide are added to the above
solution. The reaction mixture is stirred for 6 hours at 100C bath
temperature and then filtere~. The filtrate is concentrated and the
resulting crystal slurry is recrystallised from benzine, affording
28.8 e of the compound
~,
'~ ;_!
' ' ' ~'
,
,
: ' : :
-- 8
Cl
C~o~l
OCH~
C~2
with a melting point of 105~110C.
: , .
Example 3: 0.8 g of lithium borohydride i8 charged into 100 ml of
absolute ether. With good stirring, a solution of 15 g of methyl 3-(2'-
chloro-4'-trifluoromethylphenoxy)-~-(6-cyanophenoxy)-propionate in
25 ml of ether is added dropwise, such that the reaction mixture is kept
at the boil. When the addition i9 complete, the reaction mi~ture is
stirred or 1 hour at boiling temperature. Af~er addition of 8 ml of
ethyl acetate, followed by the addition of 4 ml of 10~ ammonium chloride
solution, the mixture i9 filtered and the ethereal phase is separated.
The solvent is distilled off by rotary evaporation and the residual
oil is distilled in a bulb tube, affording 7 g of oily end product of ;~ ;
the formula -
Cl
F3C ~ o ~ ~
OC~C~ OH
CH
; with a boiling point of 180~C/O.OOl torr.
; All derivatives which contain CN or N02 as functional group can
be reduced in the same manner.
Ex__ple 4: 3 g of a sodium hydride dispersion in oil (approx. 55%)
are charged into lOO ml of tetrahydrofura~e and, wi~h efficient stirring,
- " , : :
.-.: : : . :
. . ~ . : : : . , : ~
`
_ 9 _
a solution of 19.6 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-
(6-chlorophenoxy)-propanol in 50 ml of tetrahydrofurane is added drop-
wise under nitrogen. The reaction mixture is stirred for 1 hour at
about 35C and then, after the dropwise addition of 7 g of dimethyl
carbamoyl chloride, stirred for a further hour. A~ter addition of water,
the organic phase is separated and concentrated. ~he residual oil is
distilled in a high vacuum: b.p~ 177-180C/0.03 torr.
Yield: 17 g of the compound of the formula
F3~ ~ O ~ O C~3
Cl OCHCH2OCN
CH3 3
~ .
,
Example 5: 4.~ g (0.031 mole) of potassium carbonate are suspended
in a solution of 10 g (0.03 mole~ of 4-(2'-chloro-4'-trifluorome~hyl-
3 phenoxy)-phenol and 3.75 g (0.03 mole) of 2-chloro-n-propylmethy~
sulfide in 30 ml of acetonitrile and the reaction mixture is refl~xed
- for 3 hours and then co~centrated. The residue is stirred in 200 ml of
ether and the ethereal solu~ion is washed with three 200 ml portîons
of 20% sodium carbonate solution, dried and concentrated, afording
11 g of final product with a refractive index of ~ 3 = 1.5642 and
having the formula
CH3
- Cl OCHCH~SCH3
~ ~ N2
~'
: ~
-
~ ,.,
:, ..
:, : . :::
::
. .: ~ .
36~
- 10 -
The follo~ing table lists the compounds of the formula I
described in the foregoing Examples as well as further such compounds
: of ~he invention. In the table~ the basic compounds of the formula I
and the radicals Z belonging to them are listed separately. :~
,
A.) Basic compounds
I H3
Cl OC~ 12oZ
L~ ~3C~ 0~ CL
CH3
Cl OC~C~2-Z
2. F3C ~
CX3
Cl OC~lCa2 Z ;~
3. ~3C_~_ o ~ C~
:
CH3
~1 OC~ ~ 2 Z
4. ~1 ~ O ~ Cl
`: : :
- :
.
., , :
.
66
,
.
~ .
- ~3
Cl OC~C~2-~
5. CL~ Br
. , :
C~3 ~:
, Cl C~H2-z
6. Cl ~- O ~ 2
', '
~3
i ~:1 O~I~a2 z
7 . B~ O ~ Cl
:~ :
M
Br OalF~2 Z
8. C~ ~ N~2
:. .
- :
' _
, : .
:
. :
- -, . - .
,. . . .
.::
: :
.
-- 12 --
~ H3
,Br oc~c~2-æ
9. Br ~0 ~C~
CR3 :
oC~C
10., F3C~ O~Cl
Ca3 ~
1!~0~ OCHC~l2-Z '.:
11. F3r~ 0 ~- cl ;
Ca3
OC~lCa2-Z
- 12- F3C:~ O ~ 2
.
,. . .
:. .
:. ~
; .
:
~' ~"
, . .
`~ . . , ~ . . ~ :
.: - . . ...
C~3
"
3~ ~)
, 3
, ~Cl ~OC~C~2~:
14. ~lC~)~ Cl
.,
. 3
~ ,~Ca~2-~
15. C~O ~N02
::
C~3
~0
16. Cl~O~Cl
~: .
., `
, . ,
- , .` ~ ` ,
r ~
- 14 -- .
C~3
~0~ I~12-Z
L7. Br~0 ~Cl
.
~' ' .
~3
~1 OC~2 Z ~:~
18. 2~ ~ Cl
~ 3
c~ ocac~ z
~; 19 . F3r~ ~Cl
C~
, 3
Z
20. F3C_~ ~ ~2 ~ :
, ~
~;
'`'
_.
'
,: ~ , . :
., ~ :. . .. . ::
-- 15 --
i B. ) Radicals Z
~' .
a) -t)H
b)
O
C) -O
d~ ~C-C~ ~ CF3
''
Cl
e) ` -OC-CH-O~O ~_ Cl
~1
f) -OC-CII-O~ ~ CF3
.
.:
.
- ~ ~
-- 16 --
g) ~
O
h) -OCNEl~H
,' o :'
,_~ CF3
O :
~' ~
~.
Cl
O-C-CH-O~ O~-- Cl
C~3
k) ~ C2~s
, ~
. ~
. `
1) ~S2~3
, \-- :
~..
:
., , ~
;~ ' ''
6~ii
-- 17 ~
~3 -S~R R - ~al, N02, CN, CF3,
\~/ alkyl, alkoxy
) -SCH2~'
P) -S~Z~2
q) ~C~2c~2
~' ` .
r) -0~2C~
.
:
8) -OCH3
~ R R = Hal, N02 ~ CN, CF 3,
t) ~~W alkyl, alkoxy
,:
:
.
- 18 - ~
:
~2~3
V) -O-C-N/ R z H / alkyl, alkoxy
'' \R - .
i w~ SC2~5 '
O ;':
x) -O-C~ O~CL R= ~I~ C~3
s Cl
,
3 ~
.1 C~3 C:H3
'
3~ .
Z) So~C~2~3
:"
-.,, ' : '''
.,
- . .: . :, '' ~ . . :
- lg
Selected individual compounds of the formula I, including those
described in the Examples, are listed in the following table. They fall
under the narrower form~la:
R
~2) ,1
R~ CR~-C}12-Z
R5 R3
,~ .
, ,.
.
:~ "
: ~ '
:: ' ' . : . : ': , :
: :
,
:. , : ~ : . : , . , :
-- 20 --
_ ~
. '.
.~q ~
~ ~ ~ ~ ~,, o
~d ~ ~
o ~ . U) ~ ~ ~ U~ ~ ~ o o o
' o o o o
c~ ~ n ~ u
~, \ 4~ O O O
CJ ~ ~ ~ e~ r o
~ o cf~ a c~
.
..~
:
. ~,
. ~ æ ~ ~ T ~ ~ ,,, ~ e ~ o
~ ~ I I I ~ I I ,
Y T
. ~.
_. ~ C~ Y C~ y y y , , y U
~ _ . _ ~
~;~ 5: :~; S Z ~ s
~:~ ~ _ 3
3: -'
~s;
~_ :
Ct: C.~ U C~ Y Y ~ ~ Y C:
_ ~ __ , ~ _ __ _ _ _
~ ~ S D ~ a ~
_ ~
ll ~
.' ~ ~ ,~ O
S
''r~ ~ _ _ ___ _ _ _ .
~. .
': ,, :
'' .
~,
-- 21 --
.
.
,
i~' Z ,~q o o
~ ~ o I o o o ,,\
ZZ~ O U~ 0 Y~ ~ ZZ~ r~
~ ~ ~ O _l
ra P~
:', ~ .Q
__, .
Z' ,1
i.~ . ~ O~
i, , ~ C Z ~ Z ~
,~ ~ Z C~
8 8 8
. . o cll o j T
_ ~
~ ZY`O
~ ,
.. Z _ ~ ~Z
,., _~o ~'Z ~ y, ~ y
.~, C2S ~ ZZ ~ ~ ~ ~
.. ,, ,,_ __ . __
~' ~U~ ~ X X
: ` ~
~ ~ ~-7 ~ ~ ~ ~ ~ ~ ~ ~
~;~ ~ 1Z X ~ ~
:: ~ ~
~ ~: : ~ oz ~ o
: - ~
~` l~; c~ v ~ v c~ ~ `
~ -- ~
: ~ . - ~
:~ ~ o ~ u~ ` ~
:
-- 22 -- .
,~ __ _ -~
o O O
o o o\ ~ \ :'
,~ ~ o o ,, I o ~ ~ o o
,~ ~ , o _, o ~ '
to .
;; ~ ~ . ~
., . , , _ _ _
,1 .
C~
.1 C~ ~ '
l ~ ~
., ~
~~ol ~ o ~ o ~ ~ = ~
,, ~ ~ = s S ~
..
~: ~ = ~ o~ Zo~ o`~ ZZ Z `
, . _ . _ __ _ _
'. , X~ ;~
., ~ ' ~ ~ ~ ~ ~ ~ ~ ~
_ _ , _ _ _, _, . _ . _ _ _
',,
c~ ~ a: 5 ~ S 3:~ =
: . ~
.` CC~ Z C~ 0~
-.,. CIC ~
_ __ ~
~, O ~ u~ ~ ~ ~ ~ ~ '5 ~
~' ' C' _~ '
'' "~ r -- . -
~i
: ~
~ ~ :
~ ~ o
~ o oo o o
o ~ Q
.
~.a
~1 A~ ~ .
~ o I e (~
o o o ~ o ~ ~1 ~ O
. .. .. ,, ,
_
~0 ~ 5
. _ _ _ _ _ _,
,
~D
. ~ ~ '.
1~ ~ 5 3~
_
.,
1~4 ~4 ~ ~ ~ ~ ~ '
~ d' ~
r S 5: :c 3 5
__ . .
0~ ~ S
_ __ ~ .
~ 2
c~ : ~ ~ ~ ~ ~ ~ ~ ~ ~r
'.,~' _~_
;'
,
~'', ' .
,.,',', ~, ' :
- 24 -
C~l :
)~ Ul
~ ~ ,~
o o
'o `o 'o 'o '~ 'o `o 'o ~''o 'o 'o
~' ~.a , `~
' . :' , '
'
., ~''.
., ~ ~ : ,,
', . ~
. T , T = , , ~ T
.
.. .
.
~ ~ ~ ~ ~ ~ c~
~;~ ~ ul c~
. 1~ ~ ~ S U~
~ ' . . ~
:~ r ~ 0~ 0~ 0~ " " 0~ 5 0~
_ . , . . _ , .
U~
_ :: S 2 2: 8 = 2
,,, ~ ~
'.: O O `D 1~ ~ ~ O _I ~ ~ ~ u~ ~ r~
.. ,; 0~ ~ ~ ~ ~ 11'1 UO U'~ U'l Ul In u~ Ir~
~,)
` .," _ ,, , -- :
. ~
,
-- 25 --
__ _ ~
~ ~1 ~
~ C~
,i C 7
,u, 'o '~ ~ 'o 'o
,~ C
.
3,~
~ ., ~:
~ I ~
~, e~l~O ~ oc~
'. , . _ ~
~ v _ C~ y 1~ ~u
~ ~ X`~
__. _. . o
~ ~ ~ ~ ~ ~ C~ ~
~5 Y Y, Y Y ~ .
~ r ~_J
_ ,_ .. ~
_ - . :,
~ ~ ,
~ ~ Z ~ V ~
_ .. ~
n: ~ ~ o
c~ v v ~ v æ
: ___
~ ~ ~ :
~'
.,
.
- :.
,
- 26 -
The invention also relates to herbicidal compositions which
contain a novel active compound (active substance) o~ the fonmula I,
and to a preemergence and postemergence method of controlling weeds, ;~
in particular monocotyledonous grass-like weeds.
The compositions of the present invention c~n be in the conven-
tional formulations.
'; '
The compositions of the present invention are obtained in known
manner by intimately mixing and grinding active substances of the
formula I with suitable carriers and/or adjuvants, with or without the ~ --
addition of antifoamsl wetting agents, dispersants or solvents which
, .
are inert to the active substances. The active substances can be ~ ;~
processed to the following formulations:
solid formulations: dusts, tracking powd2rs, granules (coated
grantlles, impregnated grallules and homogeneous granules);
active substance concentrates which are dispersible in wa~er:
wettable powders, pastes, e~ulsions, emulsifiable concentrates;
liquid formulations: solutions.
:
The above described compositions contain between l and 80~ of
active substance and can also be diluted before application to low ~ ~;
concen~rations, for example to about 0.05 to 1%. The rates of applica-
tion are ordinarily from 0.1 to lO kg of active substance~ha, prefer~
ably from 0.25 to 4 kg/ha. The active suhstances can be formulated for
example as follows ~parts are by weight):
Granules
The following substances are used to formulate 5% granules:
par~s of active substance,
:
0.25 parts of epichlorohydrin,
0.25 parts of cetylpolyethylene glycol ether with 8 moles of
ethylene oxide,
3.50 parts of polyethylene glycol,
-, 91 parts of kaolin (particle size 0.3-0.8 mm).
~ ~.
. :
'': ' ` ` ~ ~ '
; . ,
- 27 -
The active substance is mixed with epichlorohydrin and the
mixture i9 disso`l~ed in 6 parts of acetone; the polyethylene glycol
and cetylpolyethylene glycol ether are then added. The resul~ing solu-
tion is sprayed on kaolin, and the acetone is subsequently evaporated
in vacuo.
.. .
We~table powders
The ollowing constituents are used to formulate a) a 50%, b3 a 25%
; and c) a 10~ wettable powder:
a) 50 parts of the active substance of Example 1,
5 parts of sodium dibutylnaphthylsulfonate,
3 parts of naphthalenesulfonic acid/phenolsulfonic acid/
formaldehyde concentrate ~3:2:1),
~'. 20 parts of kaolin,
22 parts of Champagne chalk;
, . .
b) 25 parts of the above active substance,
, 5 parts o sodium oleylmethyltauride,
`¦ 2.5 parts o naphthalenesulfonic acid/formaldehyde condensate
. 0.5 part of carboxymethyl cellulose,
:,
:~ 5 parts of neutral potassiu~ aluminium silicate,
:
62 parts of kaolin;
:
c) 10 parts of the above active substance,
3 parts of a mixture of the sodiu~ salts o~ saturated fatty
alcohol sulfates,
S parts of naphthalenesulonic acid/formaldehyde condensate,
, 82 parts o kaolin.
The indicated active substance is applied to the corresponding
carriers (kaolin and chalk3 and then these are mixed and ground, afford-
ing wettable powders of excellent wettability and suspension powerO
By diluting these wettable powders with water it is possible to obtain
' ~
' ._
:
,
,
:, , ,
6 ~:
- 28 -
suspensions of the desired concentration o active substance. Such
suspensions are used for controlling grass-like weeds in crops o
cultivated plants.
Paste
The following substances are used to formulate a 45% paste:
45 parts of active substance,
5 parts of sodium aluminium silicate,
14 parts of cetylpolyethylene glycol ether with 8 moles of
ethylene oxide,
1 part of oleylpolyethylene glycol ether with 5 moles of
ethylene oxide,
2 parts of spindle oil,
10 parts of polyethylene glycol,
23 parts of water. -
The active substance is homogeneously mixed with the adjuvants
in appropriate devices and ground, yielding a paste fro~ which, by ;
dilution with water, it is possible to obtain suspensions of the desired
concentration of active substance.
~ .
Emulsifiable Concentrate
The following ingredients are mixed to formulate a 25% emulsifiable
concentrate: .
25 parts of the active substance of Example 2,
10 parts of a mixture of nonylphenolpolyoxyethylene and
calcium dodecylbenzenesulfonate,
55 parts of xylene,
10 parts of cyclohexanone.
This concentrate can be diluted with water to produce emulsions
of suitable concentrations.
:
.
..
ri
~ , .
.
'
'
'
~ 6~i
- 29 -
Instead of the active substance indicated respectively in the
above formulation examples, i~ i5 also possible ~o use another of the
compounds embracPd by the formula I.
Compositions of the invention which contain, as active component,
at least one active substance of the formula I, are particularly suit-
able for the selective preemergence and, in particular, postemergence,
control of monocotyledonous weeds in crops of dicotyledonous cultivated
plants~ for example soya bean, cotton, sugar beet, leguminosae, clover,
alfalfa, melons, cucumbers, ~obacco etc.
The following test methods were employed to establish the use~
fulness of the compounds of the formula I as preemergence and post-
emergence herbicides~
.
Preemergence herbicidal action ~inhibition of germination)
In a greenhouse, immediately a~ter sowing the test plants in
seed dishes, the surface of the soil i9 treated with an aqueous dis-
persion of the active substances, obtained from a 25% wettable powder
or emulsifiable concentrate. Four different concentration series were
used, corresponding to 4, 2, l and 0.5 kg o~ ac~ive su~stance per
hectare respectively. The seed dishes are kept in the greenhouse at
22-25C and 50-70% relative humidity. The test is evaluated 3 weeks
later according to the following rating:
1 - plants have not germinated or are totally withered
2-3 - very strong action
4-6 = medium action
7-8 = slight action
9 = no action (as untreated control)
. ~
.
-- :
`.:
:
'' : ' . , . :'
.
~l~lB66
- 30 ~
~'": ' .'
The following test plants were used:
hordeum (barley) setaria italica
triticu~i (wheat) echinochloa crus galli
zea (maize) beta vulgaris
sorghum hybr~ sida spinosa
oryza (rice) sesbania exaltata
glycine (soya) amaranthus retroflexus
gossypium ~cotton) sinapsis alba
avefia fatua ipomoea purpurea
lolium perenne galium aparine
alopecurus myosuroides pastinaca sa~iva
bromus tectorum rumex sp.
cyperus esculentus chrysanthemum leucu~.
rottboellia exaltata abutilon sp. -~
digitaria sanguinalis solanum nigrum
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Postemergence herbicidal action (Contact herbicide)
A large number (at least 7) of weeds and cultivated plants,
`~ both monocots and dicots, were sprayed after emergence (in ~he 4- to
6-leaf stage) with an aqueous active substance dispersion at rates~of
0.25, 0.5, 1, 2 and 4 kg of active substance per hectare and kept ae
24-26C and 45-60% reIative humidity. The test was evaluated~, as in
,: i
the preemergence test, 15 days after treatment in accordance with the
same rating.
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In a comparison test, 4 compounds of the inven-tion (No.'s 10,
12, 13, 16) were tested with two similarly substituted 4-phenoxy-
phenoxy-diphenyl ether derivatives of German Offenlegungsschrift
2,611,695 for their postemergence action against monocotyledonous and
dicotyledonous weeds.
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The test method and evaluation correspond to the above described
contact herbicide test at a rate ~f application of 4 kg o~ active sub-
stance per hectare.
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i The comparison compounds of German Offenlegungsschrift 2,611,695 were: :
ResuLts
Weeds Compo~mds of the invention Prior art
(German Offenlegungs-
schrift 2,611,695)
No.'s lO 12 13 16 A B
Avena fatua 1 1 1 1 7 7 ~:
. Setaria 1 1 2 1 8 4
; Lolium 2 1 1 2 7
Sola~um 1 1 1 1 8 9
Sinapsis 1 1 1 1 8 8
. Stellaria 1 l 1 1 3 7
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