Note: Descriptions are shown in the official language in which they were submitted.
58~
- 1 - 21489-6644F
This application is a divisional *rom application No.
469,230, filed December 4th, 1984.
Application 469l230 relates to novel herbicidal 2-phenoxy-
propionic acid cyanamides, to the preparation thereof, to herbi-
cidal compositions containing them as active ingredients, and to
methods of usin~ the novel compounds and compositions containing
them for selectively controlling weeds in crops of cultivated
plants.
The 2-phenoxypropionic acid cyanamides of application
469,230 are of the formula I
T-O ~ O~CH-CO-N-R (I),
wherein CH3 CN
R is hydrogen, Cl-C4alkyl, C3-C4alkenyl, C3-C4alkynyl or
C2-C4alkoxyalkyl, and
T is a rad.ical
~ ~ ~1 N
wherein
A is oxygen or sulfur,
X is fluorine, chlorine, bromine, iodine or trifluoro-
methyl,
is hydrogen, fluorine, chlorine, bromine or trifluoro-
methyl, and
Z is nitrogen or the methine bridge.
Herbicidal 2-phenoxypropionamide5 containing further
5-14680/1-~2/=/DIV I
~ ,v
~2465~
- 2 - 21489-6644F
substituents in the para-position of the phenyl nucleus are known
from the literature, e.g. DE-OS 2 433 067, 2 531 643, 2 639 796, 2
640 730 or 3 004 770.
Surprisingly, it has been found that the novel compounds
of application 469,230 are superior to the compounds of this class
described in the literature for selectively con~rolling weeds in
crops of useful plants.
~ Jithin the scope of application 469,230, the symbols R
and T in the definition of formula I are for example the following
substituents: R is generally hydrogen, methyl, ethyl, isopropyl,
n-propyl, the four butyl isomers, or is allyl, methallyl,
2-butenyl, 3-butenyl, propargyl, 2-butynyl, 3-butynyl, methoxy-
methyl, methoxyethyl, ethoxymethyl or ethoxyethyl; and T is gener-
ally a radical selected from the group consisting of phenyl,
2-pyridinyl, 2-quinolinyl, 2-quinoxalinyl, 2-benzoxazolyl or 2
benzothiazolyl, which radical is substituted by at least the
radical X. Preferably R is hydrogen or a saturated radical; e.g.
C1-C4alkyl or C2-C4 alkoxyalkyl and T is a radical such as
2-benzoxazolyl or 2-quinoxalinyl.
On account of their good selective ~lerbicidal activity,
particularly interesting compounds of formula I are those wherein
either
a) R is hydrogen or C1-C4alkyl, or
b) T is the rad~cal ~ , or
~65~
X ~ N
\//\ /~
o a
c) T is the radical I 11 ~ , or
~' D-- ~
~ N
Cl ~ O
\ // \ / \ '
~ \
d) T is the radical
~ / \ //
N
Among the eompounds of subgroup a), those compounds are preferred
wherein R is Cl-C4alkyl; among the eompounds of subgroup b), those
compounds are preferred wherein either X is trifluoromethyl, Y is
hydrogen and Z is the methine bridge; Gr X is trifluoromethyl, Y i9
hydrogen and Z is nitrogen; or X and Y are ehlorine and Z is
nitrogen; or X is chlorine, Y is fluorine and Z is nitrogen; i.e. T
is a radical seleeted from the group eonsisting of 4-trifluoro-
methylphenyl, 5-trifluoromethylpyridin-2-yl, 3,5-diehloropyridin-
2-yl and 5-chloro-3-fluoropyridin-2-yl.
Among the eompounds of subgroup e), those eompounds are preferred
wherein X is fluorine or chlorine.
Very particularly preferred subgroups of compounds of formula I are
those wherein R is Cl-C~alkyl and T is either 4-trifluoromethyl-
phenyl or 5-trifluoromethylpyridin-2-yl or 3,5-dichloropyridin-2-yl
or 5-chloro-3-fluoropyridin-2-yl, which last type is most particul-
arly preferred; or wherein R is Cl-C4alkyl and T is 6-fluoroquinoxa-
lin-2-yl or 6-chloroquinoxalin-2-yl; or wherein R is Cl-C4alkyl and
T is 6-chlorobenzoxazol-2-yl.
~ . '
65~3~
- 4 - 21489-6644F
The compounds of formula I of application 469,230 can be
prepared by several routes. These include:
; (a~ reacting a 2-phenoxypropionyl halide of formula II
; T-O~ O-CH-C0-Hal ~II),
~ CH3
- wherein
T is as defined for formula I and Hal is chlorine or
bromlne, with a cyanamine of formula III
H - N - R
CN (III),
wherein R is as defined for formula I, in the presence of an aci.d
acceptor.
If R has a meaning other than hydrogen, the compounds
of subformula Ia
T-O~O-CH-CO-N-R ( Ia),
wherein
~ T is as defined for formula I and R is Cl-C4alkyl,
C3-C4alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, can be obtained by
reacting a corresponding cyanamino compound of subformula Ib
T-o~30-CH-Co-N-H
C 3 (Ib),
`~
:
~: '
~l24~;S~3~
- 5 - 21489~6644F
wherein
T is as definea for formula I, with a halogen compound of
formula IV
Hal - Rl (IV),
wherein
Rl is as defined for formula Ia a:nd Hal is chlorine,
bromine or iodine, in the presence of an acid acceptor.
(b) reacting a phenoxypropionic acid derivative of formula
V
CH3 O
1 0 H-O ~ O - CH - C - N -R (V),
CN
wherein
R is as defined for formula I, with a halide of formula
VI
T - Hal (VI),
wherein
T is as defined for formula I and Hal is fluorine, chlo-
rine, hromine or iodine, in the presence of an acid acceptor.
(cj reacting a propionic acid derivative of formula VII
CH o
1 3 11
Hal - CH - C - 7 R (VII),
CN
wherein
R is as defined for formula I and Hal is chlorine~ bro-
mine, tosyl or mesyl, with a hydroquinone derivative of formula
VIlI
658~
- 6 - 21489-6644
T - O - ~ OH (VIII),
wherein
T is as defined for formula I t in the presence of an acid
acceptor.
The different reactions to obtain compounds of formula I
or of formula Ia ~-ia formula Ib are conveniently carried QUt in
aprotic, inert organic solvents. Examples of such solvents are:
hydrocarbons such as benzene, toluene, xylene or cyclohexane;
chlorinated hydrocarbons such as methylene chloride, chloroform,
lo carbon tetrachloride, or chlorobenzene; ethers such as diethyl
ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl
ether, tetrahydrofuran or dioxan; nitriles such as acetonitrile or
propionitrile; amides such as dimethylformamide, diethylformamide
or N-methylpyrrolidinone. The reaction temperatures are preferably
in the range from -20 to +120C. Preferred bases are tertiary
amines such as trimethylamine, triethylamine, quinuclidine, 1,4-
diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]-non-5-ene or
1,8-diazabicyclo[5.4.0]undec-7-ene. However, the bases employed
may also be inorganic bases, e.g. hydrides such as sodium hydride
and calcium hydride, hydroxides such as sodium hydroxide and potas-
sium hydroxide, carbonates such as sodium and potassium carbonate,
or bicarbonates such as potassiurn and sodium bicarbonate.
Most of the intermediate of formulae II, III, IV, VI and
VIII are known or can be prepared by methods analogous to known
ones.
The intermediates of formulae V and VII are novel and have
:.
65~3~
- 7 - 21489-6644F
been specially developed and prepared for the synthesis of com~
pounds of formula I.
The propionic acid derivative of formula VII
CH3 0
1 11
: Hal - CH - C - N - R (VII)
CN
is obtained by reactlng a propionyl halide of formula IX
CH~ O
11
Hal - CH - C - Hal (IX),
wherein Hal is as deined or formula VII and Hal1 is chlorine or
bromine, with a cyanamine of formula X
H - N - R
(X~,
CN
wherein R is as defined for ormula VII, in the presence of an
I acid acceptor.
.
In accordance with a variant of the above process, the
compounds of subormula VIIa ~
Cl H 3 0
Hal - CH - - NH - CN ~VIIa)
'
: can also be prepared by first reacting the propionyl halide of
.:
formula IX with a cyanamlne of formula XI
H2N - CN (XI),
" ~
.
: ~
581
- 8 - 21489-6644
in the presence of an acid acceptor, and, if desired, reacting
these compounds of formula VIIa wi-th an alkylating agent which in-
troduces the radical Rl as defined for formula IV.
The intermediates of formulaV canbe prepared from com-
pounds of formula VII by reacting the compound of formula VII
CH o
1~3 ll
Hal - CH - C - N - R (VII)
CN
with 4-benzyloxyphenol, in the presence of a base, and treating the
resultant product of formula XII
CII3 O
I ~ CH2- ~ ~ - O-CEI - C - N - R (XII),
CN
wherein R is as defined for formula I, with hydrogen, in the pre-
sence of a hydrogenation catalys-t, e.g. palladium on carbon.
The starting materials of formula IX, X or XI are known
or can be prepared by known methods. The novel intermediates of
formula XII have been specially developed and prepared for the syn-
thesis of compounds of formula I.
The preparatlon of the novel intermediates of formulae
V and VII is carried out according to methods known per se. The
reaction conditions are in each case chosen in accordance with the
requirements of the reagents employed.
::
6S831
_ 9 _ 21489-6644F
Compounds of subformula Ic
X ~ O~O-CE~-CO-N-R (IC)
whereln R and X are as defined for formula I, can be prepared by
the novel process of this invention which comprises either
a) reacting a 3-nitropyridine of formula XIII
X ~N02
~N~
Hal2
wherein X is as defined for formula I and Hal2 is fluorine, chlo-
rine or bromine, with hydroquinone, ln the presence of a base,
to give a compound of formula XIV
X\~/N02
~ ~ - O- ~ OH (XIV),
reducing this intermediate, in the presence of a metal catalyst,
to give an amino compound of formula XV
X ~H2
O- ~ -OH ~XV),
.
~2~65~
.
10 -
dia~otising this amino compound and converting it ~ith a fluorinat-
ing agent into a compound of formula XVI
X F
\ // \ /
O ._~,
I 11 // ~
o-O-- ~-OH (XVI),
~/ \ /
N ~=o
-
and reacting this fluorinated intermediate with a propionic acid
derivative of formula VII, in the presence of a base, or by
b) reacting the nitropyridine of formula XIII with a propionic acid
ester of formula XVII
o-~ Cll
~ 3
HO~ O-CH-COO-alkyl (XVII)~
=0
wherein alkyl is Cl-C4alkyl, in the presence`of a base, reducing the
resultant intermediate of formula XVIII
X ~ N2
\~\ /
. O_. CH
-O-- o-O-CH-COO-alkyl (XVIII),
'~/ \ /
N -O
in the presence of a metal catalyst, to give the amino compound of
formula XIX
- X ~- NH
._O CH
~-O~ O-CH-COO-alkyl (XIX),
~: \\/\ /
N ~=.
-` 124G581
-- 11 --
dia~otising this intermediate and converting it with a fluorinating
agent into a compound of formula XX
X F
\//\ /
. . ~-. CH
11 R ~ 1 3
~-0-- o-O-CH-COO-alkyl (XX),
~/ \ /
N o=~
saponifying this ester and converting it with a halogenating agent
into a 2-phenoxypropionyl halide of subformula IIa
F
Cll
~ 3
X-- o-O-~ -O-CH-CO-Hal (IIa),
\ / \ /
=N o=~
wherein Hal and X are as defined for formula II, and reacting said
2-phenoxypropionyl halide with a cyanamine of formula III, in the
presence of a base.
.
In accordance with a variant of the above process, the intennediates
of formula XVIII can also be obtained by reacting~the compounds of
formula XIV wlth a propionic acid es~ter of formula XXI
ICil3
Hal-CH-COO-alkyl (XXI),
.,
wherein llal is chlorine or bromine and allcyl is Cl-C4alkyl, in the
presence of a base.
The reaction conditions for these per se known reaction steps, e.g.
catalysts, solvents and reaction temperatures, are known from the
literature.
The starting materials of formulae XIII and XVII are known.
~ "
. _.
658~L
- 12 - 21489-6644F
The in~ermediates of formulae XIV, XV and XVIII are novel
and have been specially developed for the synthesis of com-
pounds of formula Ic. These intermediates and the novel pro-
cess together with variants a and b likewise constitute the
present invention. The compounds of formula IIa, wherein X is
halogen, are also novel.
Thus this invention provides a compound of the formula
X ~ D
~ N~-O- ~ -O-E
wherein X is fluorine, chlorine, bromine, iodine or trifluoro-
methyl, D is amino or nitro and E is hydrogen or -CH(CH3)-COO
alkyl, wherein alkyl is Cl-C4-alkyl, provided that E is hydro-
gen when D is amino~
The compounds of formula I are obtained as racemates. Both
enantiomers of the compounds of formula I and mixtures thereof
constitute an object of the invention. Unless a particular iso-
mer is expressly mentioned, what is said in the description
always refers to the racemates.
The compounds of formula I are stable compounds and no
protective measures are required for handling them.
When used at low rates of application, the compounds of
formula I have good selective herbicidal properties, in par-
ticular against monocot weeds, which make them most suitable
for use in crops of useful dicot plants, in particular cotton,
soybeans, rape, sugar beet, fodder heet and sunflowers. Some
of the compounds of formula I of the invention can also be
used as selective-herbicides in crops of monocot plants such
as cereals, e.g. wheat and barley.
S~
- 13 - 21~9-6644F
In some cases damage is also caused to weeds w~ich have only been
controlled up to now with total herbicides.
When used higher rates of application, the compounds of
formula I act as total herbicides.
The selective herbicidal activity of the compounds of
the invention is observed both in pre- and postemergence applica-
tion. Accordingly, these compounds can be used with equally good
success for selectively controlling weeds, in particular grass
weeds, pre- and postemergence.
Application 469,203 also relates to herbicidal composi-
tions containing a novel compound of formula I and to methods of
controlling monocot weeds, in particular grasses, pre- and post-
emergence.
The compounds of the formula I are used in unmodified
form or, preferably, together with the adjuvants conventionally
employed in the art of formulation, and are therefore formulated
in known manner to emulsifiable concentrates, directly sprayable
or dilutable solutions, dilute emulsions, wettable powders, soluble
powders, dusts, granulates, and also encapsulations in e.g. poly-
mer substances. As with the nature of the compositions r the methods
of applications, such as spraying, atomising, dusting, scattering
or pouring, are chosen in accordance with the intended objectives
and the prevailing circumstances.
The formulations, i.e. the compositions containing the
compound (active ingredient) of the formula I and~ where approp-
riate, a solid or li~uid adjuvant, are prepared in known manner,
:IL2~58~
- 13a - 21489-6644E
e.g. by homogeneously mixing and/or grinding the active ingredients
with extenders, e.g. solvents, solid carriers and, where approp-
riate, surface-active compounds (surfactants)O
Suitable solvents are: aromatic hydrocarbons~ preferably
the fractions containing 8 to 12 carbon atoms r e.g. xylene mix-
tures or substituted naphthalenes, phthalates such as dibutyl
phthalate or dioctyl phthalate, aliphatic hydrocarbons such as
cyclohexane or paraffins, alcohols and glycols and their ethers
and esters, such as ethanol, ethylene glycol, ethylene glycol mono-
methyl or monoethyl ether, ketones such as cyclohexanone, strongly
polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide
or dimethylformamide, as well as vegetable oils, epoxidised veget-
able oils such as epoxidised coconut oil or soybean oil, or water.
~2~658~ ~
. . .
- 14 -
The solid carriers used e.g. for dusts and dispersible powders are
normally natural mineral fillers such as calcite, talcum, kaolin,
montmorillonite or attapulgite. In order to improve the physical
properties it is also possible to add highly dispersed silicic acid
or highly dispersed absorbent polymers. Suitable granulated adsorp-
tive carriers are porous types, for example pumice, broken brick,
sepiolite or bentonite; and suitable nonsorbent carriers are
materials such as calcite or sand. In addition, a great number of
pregranulated materials of inorganic or organic nature can be used,
e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to be
formulated, suitable surface-active compounds are nonionic, cationic
and/or anionic surfactants having good emulsifying, dispersing and
wetting properties. The term "surfactants" will also be understood
as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and
water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal
salts or unsubstituted or substituted ammonium salts or higher fatty
acids (ClO-C22), e.g. the sodium or potassium salts of oleic or
stearic acid, or of natural fatty acid mixtures which can be
obtained e.g. from coconut oil or tallow oil. ~ention may also be
made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used,
especially fatty sulfonates, fatty sulfates, sulfonated ben~imid-
azole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali
metal salts, alkaline earth metal salts or unsubstitued or substi-
tuced ammonium salts and contain a C8-C22alkyl radical which also
includes the alkyl moiety of acyl radicals, e.g. the sodium or
calcium salt of lignosulfonic acid, of dodecylsulfate or oE a
~IL246~ii81
- 15 -
mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and
sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-
ted benzimidazole derivatives preferably contain 2 sulfonic acid
groups and one fatty acid radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-
ethanolamine salts of dodecylbenzene sulfonic acid, dibutylnaph-
thalenesulfonic acid, or of a naphthalenesulfonic acid~formalde-
hyde condensation product. Also suitable are corresponding phospha-
tes, e.g. salts of the phosphoric acid ester of an adduct of
p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholi-
pids.
Non-ionic surfactants are preferably polyglycol ether derivatives of
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated
fatty acids and alkylphenols, said der;vatives containing 3 to 10
glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)
hydrocarbon moiety and 6 to 18 carbon atoms in the allcyl moiety of
the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts
of polyethylene oxide with polypropylene glycol, ethylenediamine
propylene glycol and alkylpolypropylene glycol concaining 1 to 10
carbon atoms in the alkyl chain, which adducts contain 20 to 250
ethylene glycol ether groups and 10 to 100 propylene glycol ether
groups. These compounds usually contain 1 to 5 ethylene glycol units
per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-
polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid
esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan
trioleate are also suitable non-ionic surfactants.
~246S8~L
- 16 -
Cationic surfactants are preferably quaternary ammonium salts which
contain, as N-substituent, at least one C8-C22alkyl radical and, as
further substituents, unsubstituted or halogenated lower alkyl,
benzyl or hydroxy-lower alkyl radicals. The salts are preferably in
the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-
trimethylammonium chloride or ber.zyldi(2-chloroethyl)ethylammonium
bromide.
The surfactants customarily employed in the art of formulation are
described e.g. in the following publications:
"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing
Corp., Ridgewood, New Jersey, 1981; ~1. Stache, "Tensid-Taschenbuch",
2nd Edition, C. ~lanser Verlag~ Munich & Vienna, 1981; M. and J. Ash,
"Encyclopedia of Surfac~ants", Vol. I-III, Chemical Publishing Co.,
New York, 1980-81.
The herbicidal compositions usually contain 0.1 to 95 %, preferably
0.1 to 80 %, of a compound of the formula I,
1 to 99.9 ~, of a solid or liquid adjuvant, and 0 to 25 ~, pre-
ferably 0.1 to 25 %, of a surfactant.
Preferred formulations are composed in particular of the following
constituents t~ = percentage by weight):
Emulsifiable concentrates
active ingredient: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %, preferably 70 to 85 %
Dusts
active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 99 %
6~i81
Suspension concentrates
act;ve ingredient:5 to 75 %, preferably 10 to 50 %
water:94 to 25 %, preferably 90 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %
Wettable powders
active ingredlent: 0.5 to 90 ~, preferably 1 to 80 ~
surfactant: 0.5 to 20 ~, preferably 1 to 15 %
solid carrier:5 to 95 %, preferably 15 to 90
Granulates
active ingredient: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %.
Whereas eommercial products will be preferably formulated as
eoncentrates, the end user will normally employ dilute for~ulations.
The formulations ean be diluted to a concentration as low as 0.001 %
The rates of application are normally from 0.01 to 10 kg a.i./ha,
preferably from 0.025 to 5 kg a.i./ha.
The compositions may also contain further ingredients such as
stabilisers, antifoams, viscosity regulators, binders, tackifiers,
as well as fertilisers and other compounds for obtaining special
effects.
Preparatory Examples:
Example Pl: 2-[4-(4-Trifluoromethylphenoxy)phenoxy~propionic acid
N-cyanamide ~compound 1.4)
._ ~ o----
// ~
F3C-- o-0-- -0-CH-C0-NH-CN
\ / \ / I
~ =o CH3
~Z~658~
- 18 -
10.4 g (0.1575 mole) of 85 % potassium hydroxide are dissolved in
75 ml of water. 3.5 g (0.0825 mole) of cyanamide are added at 20C
and the clear, colourless solution is cooled to 10C. Then a
solution of 25.8 g (0.075 mole) of 2-[4-(4-trifluoromethylphenoxy)-
phenoxy]propionyl chloride in 15 ml of acetone is added dropwise
such that the temperature does not exceed 15C. After the reaction
mixture has been stirred for 45 minutes at this temperature, 9 g
(0,09 mole) of 37 % aqueous hydrochloric acid are added dropwise at
5 C. The product precipitates as an oil which crystallises on
standing over 30 minutes. The colourless crystals are isolated by
filtration, washed with water, dried over phosphorous pentoxide,
affording 24.9 g (95.0 % of theory) of 2-[4-(4-trifluoromethyl-
phenoxy)phenoxy]propionic acid N-cyanamide with a meleing point of
125-127C.
Example P2: 2-[4-(4-TriEluoromethylphenoxy)phenoxy]propionic acid
N-cyano-N-methylamide (compound 1.3)
17.5 g (0.05 mole) of 2-[4-(4-trifluoromethylphenoxy)phenoxy~-
propionic acid N-cyanamide are dissolved in 60 ml of methylethyl
ketone and with 7.6 g (0.055 mole) of potassium carbonate heated for
30 minutes to reflux. Then 3.6 ml (0.057 mole) of methyl iodide are
added at 30C to the colourless suspension and the mixture is
stirred for two hours at the same temperature. The reation mixture
is then filtered and the filtrate is concentrated by evaporation.
The oily residue is chromatographed through silica gel eluted with
petroleum ether/ethyl acetate (3:1) and the main fraction is
concentrated by evaporation, affording 10.9 g (59.9 ~ of theory) of
2-~4-(4-trifluoromethylphenoxy)phenoxy]propionic acid N-cyano-N-
methylamide as a clear, colourless oil with a refractive index of
n23 = 1.5228.
r
'
~Z~6S81
.
-- 19 --
Example P3: 2-[4-(6-Chlorobenzoxazol-2-yloxy)phenoxy]propionic acid
N-cyano-N-butylamide (compound 2.4)
Cl
11 -- .-o-cH-co-N-cH2-cH2cH2cH3
~./ \~// =- C~3 CN
a) 2-Bromopropionic acid N-cyano-N-methylamide
10.5 g (0.25 mole) of cyanamide are dissolved in 250 ml of 2N
potassium hydroxide solution and the solution so obtained is cooled
to +10C. At this temperature 26.5 ml (0.25 mole) of 2-bromo-
propionyl bromide are added dropwise and the reaction mixture i8
stirred for one hour at the same temperature. Then 16.8 g (0.2 mole)
of sodium bicarbonate are added. 63 g (0.5 mole) of dimethylsulEate
are subsequnetly added dropwise at 20C and the reaction mixture is
stirred for 4 hours and extracted with methylene chloride. The
combined orgnaic phases are dried over sodium sulfate and con~
centrated by evaporation, affording as residue 27.5 g of crude
product. Vacuum distillation of this crude products yields 13.6 g
(28.5 % of theory) of 2-bromopropionic acid N-cyano-N-methylamide
with a boiling point of 45-47C at 0.008 mbar.
b) 2-(4-Benzyloxyphenoxy)propionic acid N-cyano-N-methylamide
~ith efficient stirring, 19.1 g (0.1 mole) of 2-bromopropionic acid
N-cyano-N-methylamide are added dropwise to a solution of 20.0 g
(0.1 mole) of hydroquinone monobenzyl ether and 16.5 g (0.12 mole)
of potassium carbonate in 200 ml of dimethylformamide. After the
slightly exothermic reaction has subsided, the reaction mixture is
heated for 3 hours to 40C. The precipitated salts are then removed
by filtration and the filtrate is concentrated by evaporation. The
residue is dissolved in ether and the ether solution is extracted
with dilute sodium hydroxide solution. The organic phase is dried
.
~2465~1 ~
- 20 -
over sodium sulfate, the solvent is evaporated o~f and the residue
is distilled in vacuo, affording 19.5 g (63 % of theory) of
2-(4-benzyloxyphenoxy)propionic acid N-cyano-N-methylamide with a
melting point of 56-58C.
c) 2-(4-Hydroxyphenoxy)propionic acid N-cyano-N-butylamide
16.5 g (0.047 mole) of 2-(4-benzyloxyphenoxy)propionic acid N-cyano-
N-butylamide, prepared according to Example b), are hydrogenated
with hydrogen in 170 ml of dioxan, in the presence of 1.7 g of 5 %
palladium on carbon catalyst. The catalyst is then removed by
filtration and the filtrate is concentrated by evaporation. The
residue is chromatographed through silica gel eluted with ethyl
acetate/hexane (1:3), affording 7.5 g (61 % of theory) of
2-(4-hydroxyphenoxy)propionic acid N-cyano-N-butylamide as a
colourless oil. nDS: 1.5132.
d) 4.4 g (0.017 mole) of 2-(hydroxyphenoxy)propionic acid N-cyano-N-
butylamide, 3.8 g (0.02 mole) of 2,6-dichlorobenzoxazole and 3.5 g
(0.025 mole) of potassium carbonate are stirred in 50 ml of aceto-
nitrile for 10 I-ours at room temperature. The salts are theo
removed by filtration and the filtrate is concentrated by evapora-
tion. The residue is chromatographed through silica gel eluted with
ethyl acetate/hexane (1:3), affording 2-[4-(6-chlorobenzoxazol-2-
yloxy)phenoxy~propionic acid N-cyano-N-butylamide with a melting
point of 91-92C.
Example P4: 2-Bromopropionic acid N-cyano-N-butylamide
29.5 g (0.137 mole) of 2-bromopropionyl bromide are added dropwise
at 15C to 13.4 g (0.137 mole) of butyl cyanamide and 13.8 g
(0.137 mole) of triethylamine in lS0 ml of ether. The mixture is
stirred for 3 hours at 20 to 25C, then filtered to remove the
precipitated salt. The filtrate is extracted with dilute hydro-
chloric acid and the extract is dried over sodium sulfate and
concentrated by evaporation. The oily residue is distilled under
~246S81
- 21 -
high vacuum, affording 22.6 g (70.8 % of theory) of 2-bromopropionic
acid N-cyano-N-butylamide with a boiling point of 53-54C at
0.0052 mbar.
Example P5: 2-~4-(5-Chloro-3-fluoropyridin-2-yloxy)phenoxy~propionic
acid N-cyano-N-methylamide (compound 1.26)
F
._~ .-o CH
~ 3
Cl-- -0-~ -0-CH-C0-N-CH
.=N = C~
a) 4-(S-Chloro-3-n;tropyridin-2-yloxy)phenol
A mixture of 85.9 g to.78 mole) of hydroquinone, 1200 ml of aceto-
nitrile and 53.9 g (0.39 mole) of potassium carbonate is heated to
60C, then a solution of 115.8 g (0.60 mole) of 2,5-dichloro-3-
nitropyridine in 500 ml of acetonitrile is added dropwise over
6 hours and the mixture is stirred for 36 hours. The solvent is
removed by distillation and the residue is poured into a mixture of
ice-water and hydrochloric acid. After extraction with methylene
chloride, the combined organic phases are dried over magnesium
sulfate, treated with activated carbon, filtered and concentrated.
The residue is purified by crystallisation in a mixture of hexane
and ethyl acetate, affording 99 g (62 ~ of theory) of 4-(5-chloro-
3-nitropyridin-2-yloxy)phenol with a melting point of 125-126C.
b) 4-(3-Amino-S-chloropyridin-2-yloxy)phenol
110.7 g (0.415 mole) of 4-(5-chloro-3-nitropyridin-2-yloxy)phenol
are dissolved in 1200 ml of dioxan and, after addition of 22.0 g of
Raney nickel catalyst, hydrogenated with hydrogen at 20-25 C. The
catalyst is then removed by filtration, the solution is concentrated
'`
65~3~
- 22 -
and the residue is stirred in hexane and the product is filtered and
dried, aEfording 96.0 g (98 % of theory) of 4-(3-amino-5-chloro-
pyridin-2-yloxy)phenol with a melting point of 174C.
c) 4-(5-Chloro-3-fluoropyridin-2-yloxy)phenol
122.5 g (0.518 mole) of 4-t3-amino-5-chloropyridin-2-yloxy)phenol
are introduced at -8 to 0C into a vessel charged with 400 g
(20 moles) of hydrogen fluoride. Then 37.3 g (0.540 mole) of sodium
nitrite are added in portions over one hour. The mixture is stirred
for 2 hours at 0C and slowly heated to 55C in an autoclave. Excess
hydrogen fluoride is removed by distillation and the residue is
taken up in 200 ml of methylene chloride and the solution is
neutralised with ice-water and ammonia, the organic phase is dried
and concentrated by evaporation, affording 112 g of 4-(5-chloro-3-
fluoropyridin-2-yloxy)phenol with a melting point of 97-98C.
d) 48.0 g (0.20 mole) oE 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol
and 38.2 g (0.20 mole) of 2-bromopropionic acid N-cyano-N-methyl-
amide are dissolved in 400 ml of acetonitrile. 35.9 g (0.26 mole) of
potassium carbonate and 0.33 g (0.002 mole) of potassium iodide are
added to the solution and the reaction mixture is heated for
13 hours to 80 C. The precipitate is removed by filtration, the
filtrate is concentrated by evaporation and the residue is taken up
in 500 ml of methlyene chloride. The solution is purified by
treatment with activated carbon and filtration through silica gel.
The filtrate is concentrated by evaporation and the residue is
crystallised from a mixture of hexane and ethyl acetate, affording
61 g of 2-~4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic
acid N-cyano-N-methylamide.
~2~L65~
- 23 -
Example P6: 2-[4-(5-Chloro-3-fluoropyridin-2-yloxy)phenoxy3propionic
acid N-n-butyl-N-cyanamide (compound 1.28)
a) Methyl 2-L4-(5-chloro-3-nitropyridin-2-yloxy)phenoxy3propionate
38.6 g (0.20 mole) of 2.5-dichloro-3-nitropyrid;ne, 41.2 g
(0.21 mole) of methyl 2-(4-hydroxyphenoxy)propionate, 400 ml of
acetonitrile, 35.9 g (0.26 mole) of potassium carbonate and 0.33 g
(0.002 mole) of potassium iodide are heated for 13 hours to 80C.
The reaction mixture is filtered and the filter cake is washed with
acetonitrile. The filtrate is concentrated by evaporation and the
residue is taken up in 500 ml of methlyene chloride. After treating
the solution with 15 g of activated carbon, it is filtered through a
layer of silica gel and the filtrate is concentrated by evaporation.
The residue is crystallised from a mixture of hexane and ethyl
acetate, aEfording 65.7 g (93.1 ~ of theory) of methyl 2-~4-(5-
chloro-3-nitropyridin-2-yloxy)phenoxy~propionate with a melting
point of 91-92C.
b) Methyl 2-[4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]propionate
190.8 g (0.541 mole) of methyl 2-[4-(S-chloro-3-nitropyridin-2-yl-
oxy)phenoxy]propionate are dissolved in 1.9 1 of dioxan. 40 g of
Raney nickel catalyst are added and hydrogenation is effected with
hydrogen at 20-25C. The catalyst is then removed by filtration, the
solvent is distilled off and the still warm oily residue is crystal-
lised by stirring it in hexane. The crystalline precipitate is
isolated by filtration and dried, affording 167.4 g (96 % of theory)
of methyl 2-C4-(3-amino-5-chloropyridin-2-yloxy)phenoxy]propionate
with a melting point of 92-94G.
c) Methyl 2-~4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy~propionate
A vessel is charged with 400 g (20 moles~ of hydrogen fluoride and
167.4 g (0.518 mole) of methyl 2-C4-(3-amino-5-chloropyridin-2-yl-
oxy)phenoxy]propionate are added in portions at a temperature from
` ~ ~Z~6Sl3~ -
- 24 -
-8 to 0 C. 37.3 g (0.540 mole) of sodium nitrate are added over one
hour and the mixture is stirred for two hours before it is slowly
heated in an autoclave to 55C. Excess hydrogen fluoride is removed
by distillation and the residue is taken up in a mixture of 200 ml
of methylene chloride and ice-water and the solution is neutralised
with concentrated ammonia. The neutralised solution is extracted
three times with methylene chloride ^nd the organic extracts are
washed with water, dried and concentrated by evaporation, affording
81.0 g (48 % of theory) of methyl 2-~4-(5-chloro-3-fluoropyridin-2-
yloxy)phenoxy]propionate with a melting point of 63-64.
d) 2-[4-(5-Chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic acid
A mixture of 67.0 g (0.206 mole) of methyl 2-[4-(5-chloro-3-fluoro-
pyridin-2-yloxy)phenoxy]propionate, 350 ml of dioxan and 250 ml of
lN sodium hydroxide solution is stirred for 2 hours at 40C. The
reaction mixture is poured into a mixture of ice and 150 ml of 2N
hydrochloric acid and extracted twice with ethyl acetate. The
extracts are washed with a saturated solution of sodium chloride,
dried over magnesium sulfate, filtered and concentrated by evapora-
tion, affording 63.6 g (99 % of theory) of 2-~4-(5-chloro-3-fluoro-
pyridin-2-yloxy)phenoxy~propionic acid with a melting point of
95-97C.
~'
e) 2-[4-(5-Chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride
63.6 g of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionic
acid are dissolved in 700 ml of toluene, then 200 ml of toluene are
removed from this solution by distillation. AÇter cooling to 90C,
25 ml (0.34 mole) of thionyl chloride are added dropwise and the
solution is stirred for 14 hours at this temperature. The reaction
mixture is then concentrated to a volume of 200 ml and the resultant
solution of 2-t4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxylpropion
chloride in toluene is used direct for the following reaction step.
, .
~24658~L ~
f) While cooling with ice, a solution of 9.9 g ~0.030 mole) of
2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propionyl chloride in
30 ml of toluene is added dropwise to a solution of 3.5 g
(0.035 mole) of triethylamine and 3.2 g (0.033 mole) of n-butyl-
cyanamine in 40 m of toluene. After 5 hours, the precipitate is
removed by filtration and the filtrate is purified by chromatography
through silica gel. The eluate is concentrated by evaporation,
affording 2-~4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy~propionic
acid N-n-butyl-N-cyanamide as a yellowish oil. n25: 1.5482.
Example _7: 2R-[4-(5-Chloro-3-fluoropyridin-2-yloxy)phenoxy~-
propionic acid N-ethyl-N-cyanamide
While cooling with ice, a solution of 4.43 g (0.030 mole) of
1,8-diazabicyclo[5.4.0~undec-7-ene (97 %) in 10 ml of acetonitrile
is added dropwise to a solution of 2.1 g (0.030 mole) of ethyl-
cyanamine and 9.9 g (0.030 mole) of 2R-~4-(5-chloro-3-Eluoropyridin-
2-yloxy)phenoxy3propionyl chloride (m.p. 47-48C) in 30 ml of
acetonitrile~ After 4 hours, the reaction mixture is concentrated.
The desired 2R-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]propio-
nic acid N-ethyl-N-cyanamide is obtained by chromatographing the
residue through silica gel and concentrating the eluate (solvent
mixture: ethyl acetate/hexane 1:1) by evaporation.
~xample P8 2-~4-(6-Fluoroquinoxalin-2-yloxy)phenoxy3propionic acid
N-cyan-N-ethylamide (compound 3.18)
10 g (0.039 mole) of 4-(6-fluoroquinoxalin-2-yloxy)phenol, 9.6 g
(0.047 mole) of 2-bromopropionic acid N-cyano-N-ethylamide and 8.1 g
(0.058 mole) of potassium carbonate are stirred for 14 hours at room
temperature in 100 ml of acetonitrile. The precipitated salts are
removed by filtration and the filtrate is concentrated by evapora-
tion. The residue is chromatographed through silcia gel eluted with
ethyl acetate/hexane (1:3), affording 7.1 g (48 % of theory) of
2-[4-(6-fluoroquinoxalin-2-yloxy)phenoxy]propionic acid N-cyano-N-
ethylamide with a melting point of 108-111 C.
~2~65~ `
- 26 -
The intermediates and compounds of formula I listed in the following
tables are obtained in analogous manne~.
Table 1:
/
//
X-- -0-~ -0-CH-C0-N-R
\ / \ / I I
~=z ~=~ CH3 CN
Compoun ~ X ~ Y ~ Z ¦ R ~ Phy.i~l d~
1.1 3 N ¦ CH3 ¦ nD : 1.5210
1.2 ¦ CF3 ¦ H N H m p.: 137-138C
1.3 I CF3 I H CH CH3 nD : 1.5228
1.4 CF3 H CH H m.p.: 125-127C
1.5 Cl Cl N CH3 m.p.: 89-90C
1.6 Cl Cl N H nD : 1.5574
1.7 C1 Cl N C2H5
1.8 Cl Cl N C4H9~n
1.9 Cl Cl N -CH2-CH=CH2
1.10 Cl Cl N -(CH2)2-OCH3
1.11 CF3 H N C2H5 m.p. 50-55 C
1.12 CF3 H N 4 9
1.13 CF3 H N ¦ -CH2CH=CH2
1.14 CF3 H N ~ -(CH2)2-OCH3 ¦ nD : 1.5122
l.l5 CF3 H CH l C2H5
~2~6581
- 27 -
Table 1: (continued)
Compound ~ X ~ Y ~ Z ~ R ~ Physical data
1.16 CF3 I H ¦ CH I C4H9
1.17 I CF3 I H I CH ¦ -CH2-CH=CH2 I m.p. 79-80 C
1.18 ¦ CF I H ¦ N I -~CH ) -OCH
1.19 ¦ CF3 ¦ Cl ¦ N ¦ a I m.p. 93-94 C
1.20 CF3 Cl N CH3 m.p. 94-95 C
1.21 CF3 Cl N C2H5
1.22 CF3 Cl N C4H9~n nD : 1.5180
1.23 CF3 Cl N -CH2-CH=CH2
1.24 CF3 Cl N -(CH2)2-OC3 nD : 1.5162
1.25 Cl F N H
1.26 Cl F N c~3
1.27 Cl F N C2H5 nD : 1.5545
1.28 Cl F N 4 9 nD : 1.5482
1.29 Cl F N -CH2-CH=CH2
¦ 1.30 ¦ Cl F 1 2)2 3 ¦
~Z46581 . J~
- 28 -
Table 2: X ^ A
\R\ / \ . .
-O-o -OCH-CO-N-R
// \ / I I
~ / \ // =. CH3 CN
: N
¦ Compound ¦ A ¦ X ¦ R Physical data
No. l l l
~ ~ .
2.1 ¦ O I Cl H
2.2 O Cl CH3
2.3 O Cl C2H5
2.4 O Cl C4H9~n m.p. 91-92~C
2.5 O Cl -CH -CH=CH
2.6 O Cl -(CH2)2-OCH3
2.7 O Cl -CH2-C _ CH
2.8 S Cl H
2.9 S Cl CH3
2.10 S Cl C2H5
2.11 S Cl C4Hg-n .
2.12 S Cl -CH2-CH=CH2
2.13 S Cl -(CH2)2-OCH3
2.14 O F H
2.15 O F CH3
2.16 ¦ S ¦ F H
2.l7 ¦ S ¦ F ~ CH3
2.18 ¦ O 1 3
2.19 ¦ O 1 3 1 3
l _
:
~?~465~
- 29 -
Table 3:
X Z
\R\ /~
. O ~ ~-o CH
I 11 I D ~ 1 3
o-O-- -OCHCON-R
~/\// \ / I
N ~=o CN
_ I
No. A Z R ¦ Physical data
. _ .
3.1 Cl N H m.p. 152-154C
3.2 Cl N CH3 m.p. 106-108 C
3.3 Cl N C2H5 m.p. 106-111C
3.4 Cl N C4H9-n m.p. 62-65C
3.5 Cl N -CH2-CH-CH2
3.6 Cl N -(CH2)2-OCH3 n40: I.5794
3.1 Cl CH H
3.8 Cl CH CH3
3.9 Cl CH C2H5
3.10 Cl CH C4H9~n
3.11 Cl CH -CH2-CH=CH2
3.12 Cl CH -(CH2)2-OCH3
3.13 F N H m.p, 167-169~C
3.14 F N CH3 m.p. 141-143C
3.15 F CH H
3.16 F CH ~ CH3
3.17 F ¦ N C4Hg-n m.p. 94-95C
3.18 F ~ N ¦ C2H5 m.p. 108-111C
_ 30 - ~2~658~
Table 4: ICH3
Hal-CII-C01N-R
CN
. . _
Compound llal R Physical data
. .
4.1 Br H
4.2 Br CH3 b.p. 45-47C/0.008 mbar
4.3 Cl H
4.4 Cl CH3
4.5 Cl C4H9-n
4.6 Br C4Hg-n b.p. 53-54C/0.0052 ~bar
4.7 Br C2H5 b.p. 40-45C/0.0075 mbar
Br -(Cll2)2-cH3 b.p. 85C/0.02 mbar
Table 5~ CH
~ 3
E-O-o -O-CH-CO-N-R
\ / I
,=. CN
No . _ __ R Physical data
.. _ . __ .
5.1 benzyl H
5.2 benzyl CH3 m.p. 56-58C
5.3 benzyl C2H5 m.p. 57-63C
5.4 benzyl C~Hg-n m.p. 103-109C
5.5 H H
5.6 H CH3 oil
5.7 H C2H5
5.8 ¦ H C4Hg-n n25: 1.5132
~24~8~ '
- 31 -
Table 6s X ~ No2
\//\ /
~ CH3
1 11 // ~ I
~ -0-~ -O-CH-COO-alkyl
~/ \ /
N ~=.
No. l Alkyl ¦ Physical data
_ _
6.1 Cl CH3 m.p. 91-92C
6.2 Br CH3
6.3 F CH3
6.4 C1 C2H5
6.5 Cl C4H9~n
6.6 CF3 CH3
6.7 CF3 C4H9~n
Table 7: X . NH2
\~\/
-o CH
11 D ~ 1 3
-0-- -O-CH-COO-alkyl
~/ \ /
N =o
No. X Alkyl ¦ Physical data
. _ . I _ .
7 1 Cl CH3 m.p. 92-94 C
7.3 F CH3
7.4 Cl C2H5
7.5 Cl C4H9~n oil
7.6 CF3 ¦ CH3
I
5~ .
-- 32 --
Table 8~
X ~ F
\ // \ /
~ o-- CH
o --O--- ~--O--Cl~--CO-Q
~/ \ /
N =-
_ X Q ~ Physical data
8.1 Cl OH m.p. 95-97C
8 .2 Cl ONa
8 .3 Cl OH
8 .4 Br OH
8.5 F OH ¦
8 . 6 CF3 OH
8.7 Cl Cl I oil
8 8 Cl Br ¦
8.10 Br Cl ¦
8111 C~3 C
- /
~4658~;;
- 33 -
Table 9:
X ~ NO
\//\ / 2
O 0--~
I 11 // ~
o ~-0-- ~-OH
~/ \ /
N =~
Compound ¦ X ¦ Physical data
. No. .
~ _
Table 10:
X NH
\//\/
I 11 //
-O- -OH
/ \ /
N -~
Compound X Physical data
10.1 Cl m.p. 174C
:
~IL24G58~
- 34 -
Table 11:
X F
\ // \ /
9~ c--o
I 11 // ~
tt-O-- -OH
~/ \ /
N =.
1~ 1
Compound ¦ X ¦ Physical data
ll.l ~ Cl ~ m.p. 97-98
11.3 F
11.4 CF3
Formulation Examples
Example F1:
Formulation Examples for liquid active ingrediellts of formula I
-- _
(throughout, percentages are by weight)
a) Emulsifiab e concentrates a) b) c)
a compound of formula I20 % 40 % 50 %
calcium dodecylbenzenesulfonate 5 % 8 % 5.8
castor oil polyethylene glycol ether
(36 moles of ethylene oxide) 5 % - -
tributylphenol polyethylene glycol ether
(30 moles of ethylene oxide) - 12 % 4.2 %
cyclohexanone - 15 % 20 %
xylene mixture 70 % 25 % 20 ~
Emulsions of any required concentration can be produced from such
concentrates by dilution with water.
~ ~v~
!
465E~
- 35 -
b) Solutions a) b) c) d)
a compound of formula I 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether 20 % - - -
polyethylene glycol (MG 400) - 70 %
N-methyl-2-pyrrolidone - 20 ~ - ~
epoxidised coconut oil - - 1 % 5 %
petroleum distillate (boiling range
160 1~0) - _ 94 %
These solutions are suitable for application in the form of micro-
drops.
c) Granulates a) b)
-
a compound of formula I 5 % 10
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %
The active ingredient is dissolved in methylene chloride, the
solution is sprayed onto the carrier, and the solvent is subsequent-
ly evaporated off in vacuo.
d) Dusts a) b)
a compound of formula I 2 % 5 %
highly dispersed silicic acid 1 % 5 %
talcum 97 X
kaolin - 90 %
Ready-for-use dusts are obtained by intimately mixing the carriers
with the active ingredient.
658~
- 36 -
Example F2:
Formulation examples for solid compound of the formula I
(throughout, percentages are by weight)
a) Wettable powders a) b) c)
a compound of formula I 20 % 60 ~ 0.5 %
sodium lignosulfonate 5 % 5 % 5 %
sodium lauryl sulfate 3 % - -
sodium diisobutylnaphthalenesulfonate - 6 ~ 6 %
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid 5 % 2.7% 27 %
kaolin 67 %
sodium chloride - - 59.5 %
The active ingredient i8 thoroughly mixed with the adjuvants and the
mixture i9 thoroughly ground in a suitable mill, affording wettable
powders which can be diluted with water to give suspensions of the
desired concentration.
b) Emulsifiable concentratea) b)
a compound of formula I 10 % 1 %
octylphenol polyethlnee glycol ether
(4-5 moles of ethylene oxide) 3 ~ 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether
(36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mixture 50 % 79 %
Emulsions of any required concentration can be obtained from this
concentrate by dilution with water.
~2~65!3~L
- 37 -
c) Dusts a) b) c)
a compound of formula I5 % 8 % 0.1 %
talcum 95 ~ ~ 99 9 %
kaolin - 92 %
Ready-for-use dusts are obtained by mixing the active ingredient
with the carriers, and grinding the mixture in a suitable mill.
d) Extruder granulate a) b)
a compound of formula IlO % l %
sodium lignosulfonate 2 % 2 %
carboxymethylcellulose l % l %
kaolin 87 % 96 %
The active ingredient is mixed and ground with the adjuv~nts, and
the mixture is subsequently moistened with water. The mixture is
extruded and then dried in a stream of air.
e) Coated granulate
a compound of formula I 3 %
polyethylene glycol (MG 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a
mixer, to the kaolin moistened with polyethlene glycol. Non-dusty
coated granulates are obtained in this manner.
f) Suspension concentrate a) b)
a compound of formula I40 % 5 %
ethylene glycol lO % lO %
nonylphenol polyethylene glycol
(15 moles of ethylene oxide) 6 ~ 1
sodium lignosulfonate lO %
carboxymethylcellulose 1 % l
~2 f~;i58~ ~
- 38 -
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8
water 32 ~ 77 %
The finely ground active ingredient is intimately mixed with the
adjuvants, giving a suspension concentrate from which suspensions of
any desired concentration can be obtained by dilution with water.
Biological Examples:
-
For purposes of comparison the test results obtained with compound A
Cl ~ N
\//\/~
o o ~ CH
~ 3
o-o-o -0-CH-C0-N(CH ) (A),
~/\R \ / 3 2
N .-.
known from DE-OS 3 004 770, page 12, no. 58, are appended to the
results of Biological Examples Bl and B2.
Example Bl: Preemergence herbicidal action
In a greenhouse, immediately after sowing the test plants in seed
dishes, the surface of the soil is treated with an aqueous disper-
sion of the test compounds, obtained from a 25 % emulsifiable
concentrate or from a 25 % wettable powder with test compounds,
which, on account of their insufficient solubility, cannot be
formulated to emulsifiable concentrates. Two different concentration
series were used, corresponding to 1 and 0.5 kg of test compound per
hectare respectively. The seed dishes are kept in the greenhouse at
22 -25 C and 50-70~ relative humidity. The test is evaluated 3 weeks
later in accordance with the following rating:
65~
- 39 -
1 = plants have not germinated or are totally withered
2-3 = very strong action
4-5 = average action
7-8 = slight action
9 = no action
In this test, the tested compounds of formula I were most effective
against monocot grass weeds, whereas no or only insignificant damage
was caused to cultivated plants such as wheat, barley, sugar beet,
soybeans and cotton at the given rates of application. The compari-
son compound A is virtually ineffective.
Results:
\ Compound ~
\ No. 1.1 1.2 1.3 1.4
T \ kg/ha kg/ha kg/ha kg/ha
pla t I ~ O 5 1 ~ 0.5 1 ~0.5
. _ _ .
: Lolium 1 1 1 2 1 2 1 2
Alopecurus 1 1 1 1 1 2 2 2
Digitaria 1 1 1 1 1 1 1
Echinochloa 1 1 1 2 1 1 1
Sorghum 1 1 1 1 1 1 1 2
Rottboellia 1 1 1 1 1 1 1
soybeans 9 9 7 7 9 9 9 9
cotton 9 9 9 9 9 9 9 9
sugar beet 9 9 9 9 9 _ _ 9 9
-- ~.Z465~
- 40 ~
\
\ Compound
\ No.
Test \ 1.5 1.6
plant \
. ` \\ ~ ~ ~V~' ~ .
LoIium 1 1 1 3
Alopecurus 1 2 2 4
Digitaria 1 1 2
Echinochloa 1 1 1 3
Sorghum 1 1 1 2
Rottboellia . 1 1 2 2
barley 7 9 7 8
wheat 6 8 8 9
\ _
\ Compound
\ 3.3 . 3.4 3.17 3.18 A
Test\
plant \ kg/ha kg/ha kg/ha kg/ha kg/ha
~ . \ 1 0.5 10.5 10.5 10.5 10.5 .
: Lolium 7 9 5 8 3 3 2 4 9 9
Alopecurus ~ 4 3 4 1 2 1 2 8 9
i Digitaria 2 4 1 1 1 1 1 1 4 6
Echinochloa 2 2 2 6 1 1 1 1 9 9
Sorghum 1 3 2 7 1 3 1 2 9 9
; Rottboellia 2 6 3 7 4 4 1 2 8 9
barley 9 9 8 9 8 9 8 9 9 9
wheat 8 9 7 9 4 4 3 5 9 9
65i~3~
- 41 -
Example ~2: Postemergence herbicidal action (Contact herbiside):
A large number of weeds and cultivated plants, both mono- and
dicotyledonous, are sprayed postemergence in the 4- to 6-leaf stage
with an aqueous active ingredient dispersion in rates of 0.25, 0.5
and 1 kg of test compound per hectare and kept at 24-26C and
45-60 % relative humidity. The test was evaluated at least 15 days
after treatment in accordance with the same rating as employed in
the preemergence test.
In this test, the compounds of formula I were also most effective
against monocot grass weeds. The cultivated plants such as wheat,
barley, sugar beet, cotton and soybeans were either not damaged or
only damaged at higher rates of application of compound. The
comparison compound A is virtually ineffective.
Results:
\ I
\ Compound
\ 1.1 1.2 1.3 1.4
Test\ kg/ha kg/ha kg/ha kg/ha
~\\ l ~
Lolium 1 2 2 3 2 2 3 3
Alopecurus 1 2 2 3 1 2 2 6
Digitaria 1 1 1 1 1 1 1 1
Echinochloa 1 1 1 1 1 1 1
Sorghum 1 1 1 1 1 1 1 2
Rottboellia 1 1 1 2 1 1 1 2
soybeans 9 9 9 9 6 9 9 9
cotton 7 9 9 9 8 8 9 9
sugar beet ¦ 8 ¦ 9 8 9 8 B 8
;
~2~6S8~
- 4~ -
l \ '
¦ \ Compound
\ No.
Test \ 1.5 1.6
plant \
\ ~ D ~ ~ ~ .
Avena 1 2 2 5
Lolium 2 2 4 5
Alopecurus 1 2 4 8
Digitaria 1 1 1 2
Echinochloa 1 1 1
Sorghum 1 1 1 3
Rottboellia 1 1 1 3
barley 3 7 9 9
wheat 8 9 9 _ 9
\ -
Compound .
\ 3.3 3.4 3.17 3.18 A
Test \
plant \ kg/ha kg/ha kg/ha kg/ha kg/ha
\ l l I
. \ I 1 0.5 10.5 10.5 10.5 10.5
Lolium 1 2 3 3 1 1 1 2 7 9
Alopecurus 2 2 1 1 1 1 1 2 9 9
Digitaria 1 1 1 1 1 1 1 1 5 8
Echinochloa 1 1 1 1 1 1 1 1 8 9
Sorghum 1 1 1 1 1 1 1 1 8 9
Rottboellia 1 1 1 1 1 1 1 1 6 9
soybeans 9 9 7 8 8 8 8 9 7 9
cotton 8 9 8 9 7 9 8 8 7 9
sugar beet 8 9 8 9 ¦ 7 8 ~ 8 9
