Note: Descriptions are shown in the official language in which they were submitted.
2~3~L
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This invention relates to novel phenoxy-phenoxy-pro-
pionic acid amides of the formula I
~- O ~NO 2
-CH-C~N
(R~ ) n CH3 O 3
in which
R1 is halogen, ~ and/or CF3;
n is 1 or 2,
R2 is hydrogen or (C1-CI~)alkyl;
R3 is (C3-C6)alkenyl, (C3-C6)alkinyl, hydroxy-(C1-C4)-
alkyl9 (Cl-C4)alkoxy-(C1-C4)alkyl, di-~C1-C4)alkylamino-
(C1-C4)alkyl, cyano-(C1-C4)alkyl, (C1-C4)alkylthio-(C1-
C4)alkyl, (C5-C6)cycloalkyl, methyl-cyclohexyl, phenyl-
(C1-C4~alkyl, pyridyl or pyrimidyl;
or
R2 and R3 together form a 4 to 7-membered ring in which
up to 2 carbon atoms can be replaced by N and/or O.
The compounds of the formula I according to the in-
vention can be prepared by reacting phenoxy-phenoxy-pro-
pionic acid halides of the formula II (method A~ or
phenoxy-phenoxy-propionic acid~esters of the formula III
~method B) with corresponding amines of the formula IV
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(R1 ) ~ ~ 2 ~-o-~-NO
O-CH-C-Hal n
Cl 3 o O-CIH-~IC-OR
(II) CH3 o
(III)
. R = (C~-C8)-ALt~yl
.' ~ ~ .
~ H-N ~IV)
.~
(I)
or by reacting substituted 3-hydroxy-4-nitro-diphenyl
ethers with halopropionic acid amides (method C):
O ~ -N02 (V) + Hal-CH-CON \
n OH CH3 3
Method A) The reaction of the acid halides (II) with
amines is preferably carried out in an inert organic such
as, for example, methyl ethyl ketone, dimethoxyethane,
benzene, toluene, or xylene. The reaction i.s carried out
in the presence of a tertiary organic base such as, for
example, triethyl amine, or in the presence of an alkaline
compound such as, for example, MgO or K2C03 in order to
bind the hydrogen halide set free by salt formation. The
reaction temperature is generally in the range of from 25
to 80C
,
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When the reaction is terminated, the salt formed is fil-
tered off or washed out with water and the amide I is iso-
lated, optionally after removal of the organic solvent.
Method B) The phenoxy-phenoxy-propionic acid esters (III)
are converted into the corresponding amides (I) by reaction
with an excess amount of the respective amine IV, preferably
in aquoeus solution at temperatures from 40 to 80C.
Method C) The direct reaction of V with VI is usual-
ly carried out in one of the solvents specified sub A) and
10 in the presence of bases such as, for example, K2C03 or
triethyl amine, to bind the hydrogen halide set free. Al-
ternatively, phenolates obtained e.g. by reacting V with
alkali can be used as starting materiaL. In this case, the
reaction temperature is in the range of from 40C to the
15 boiling point of the solvent.
The starting compounds of the formulae II, III and V
are prepared by methods known from literature, for example
as described in DE-OS 2,632,581.
The compounds I obtained as described above can be purified
20 by conventional methods, for example by recrystallization.
As compared with known compounds of similar structure
(cf. DE-OS 2,632,581, US-PS 3,652,645), the compounds of
the invention are iistinguished by a better herbicidal ac-
tivity and selectivi'cy in crops. Particularly in the pre-
25 emergence process they exhibit a good herbicidal effectagainst a number of mono- and dicotyledonous weeds which
raise importar.t ecor.omical problems in various agricultu-
ral regions. They control for example goose grass (Galium),
29 an important weed in European and American agricul tural
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- 5 - HOE 7~/F 258
areas, besides other types of weeds.
The compounds in accordance with the invention (I)
are well tolerated by a great number of crop plants, for
example cereals, rice, maize, soy bean, cotton, and rape.
In cultures of the said plants no or minor damages only
are observed even with concentrations of 2.4 kg/hectare.
The novel compounds can therefore be used for the
manufacture of herbicidal compositions containing from 2
to 95 % of the compounds as active substance. The composi-
tions can be formulated as emulsifiable concentrates,wettable powders, sprayable solutions, dusts and granules,
together with the usual additives.
~ ettable powders are formulations which are uniform-
ly dispersible in water and which, in addition to the ac-
tive compound and a diluent or inert material, also containwetting agents, for example, polyoxethylated alkylphenols,
polyoxethylated fatty alcohols, alkylsulfonates or alkyl-
phenylsulfonates and dispersing agents, for example sodium
ligninsulfonate, sodium-2,2l-dinapthylmethane-6,6'-disul-
fonate, sodium-dibutylnaphthalenesulfonate, or the sodium
salt of oleoylmethyl taurine.
Emulsifiable concentrates are obtained by dissolving
the active compound in an organic solvent, for example,
butanol, cyclohexanone, dimethyl formamide, xylene or even
higher boiling aromatics or hydrocarbons, and adding one
or severa] emulsifiers, for example, calcium alkylarylsul-
fonates such as calcium dodecylbenzene-sulfonate, or non
ionic emulsifiers such as fatty acid polyglycol esters,
29 alkylaryl polyglycol ethers, fatty alcohol polyglycol
,-
,
,
~ 2~
- 6 - H~E 78/F 258
ethers, propylene oxide/ethylene oxide/ethylene oxide con-
densation products, fatty alcohol/propylene oxide/ethyle-
ne oxide condensation products, alkyl polyglycol ethers,
sorbitan fatty acid esters, poyoxyethylene sorbitar. fatty
acid esters or polyoxethylene sorbitol esters.
Dusts are obtained by grinding the active compound
together with finely divided solid substances, for example
talc, natural clays such as kaolin, bentonite, pyrophillite
or diatomaceous earth.
Sprayable solutions, frequently commercialized as aero-
sols, contain the active substance dissolved in an organic
solvent and a suitable inert propellant.
Granules can be manufactured e:ther by spraying the
active compound onto absorbent, granular inert material or
by applying active compound concentrates by means of adhe-
sives, for example polyvinyl alcohol, sodium polyacrylate
or even mineral oils, onto the surfaces of carriers, such
as sand, kaolinites or granular inert material. Suitable
formulations can a]so be manufactured by 'che customary me-
thods of manufacture of fertilizer granules, if desired inadmixture with fertilizers.
In the herbicidal compositions the conentrations of
the active compounds in the commercial formulations may
vary. In wettable powders, the active compound concentra-
- 25 tion varies, for example, between about 10 and 80 %, the
remainder consisting of the abovementioned formulation ad-
ditives. in the case of emulsifiable concentrates, the ac-
tive compound concentration is about 10 % to 80 %. Dust
29 formulations usually contain 5 - 20 % of active compound,
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- 7 - ~OE 78/F 258
and sprayable solutions about 2 - 20 %. In the case of
granules, the active compound content in par~ depends on
whether the active compound is in a liquid or solid form
and what granulation auxiliaries, fillers and the like are
used.
The commerci.al concentrates are diluted prior to appli-
cation in the usual manner, for example by means of water
in the case of wettable powders and emulsifiable concentra-
tes. Dusts, granules and sprayable solutions need not be
diluted with further inert material prior to use. The
amount of active ingredients necessary for obtaining the
desired result depends on external conditions such as tem-
perature, humidity and the like. It may vary within wide
limits, for example between 0.1 and 10.0 kg Or active sub-
stance per hectare, preferably however, between 0.3 and5 kg/hectare.
The active compounds according to the invention can be
combined with other herbicides and soil insecticides.
According to another possible mode of application the
active compounds according to the invention are mixed with
fertilizers whereby compositions having a fertilizing and
a herbicidal effect are obtained.
The following examples illustrate the invention.
EXAMPLES OF PREPARATION:
.
Method A~
0.1 mol of triethyl amine is added to 0.1 ~ol of an
acid chloride (II) dissolved in 50 ml of toluene and 0.1
mol of an a~ine (IV) is added dropwise at 25 to 40C.
29 The toluene phase is separated, washed with water and
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- 8 - HOE 78/F 258
dried over sodium sulfate. After distillation of the to-
luene, the end product is isolated and purified by recry-
stalliæation.
Method B)
:
0.1 mol of phenoxy-phenoxy-propionic acid ester (III)
is added at 40C to 0.2 mol of a 50 % aqueous amine solu-
ti.on (IV). The mixture is stirred for 2 hours at 50C, fil~
tered off with suction, the precipitate is washed with wa-
ter and the crystalline residue is dried.
The co~pounds prepared by the aforesaid rnethods are
listed in the following table.
'~ ,~O~NO2 o
(R1 )n O-CH-C-N~
CH3
Ex. (Rl)n R2 R3 ¦ m.p. L C_7 ¦ method
(or nD)
2, 4-Cl H -(CH2)2 -OCH3 133-135 3
2 4-Br H -CH2 ~CH-CH2 . A
3 2, C1, 4-Br H -CH2 -CH-CHz . B
4 2 9 4-Br H -(CH2)2-C~;3 - A
2 5 4~Cl H -C ( C~3 )2 CN 160~161 A
6 2, 4~Cl H -CH2 -CH=CH2 125 127 A
~- 7 2,4-Cl H -(C~2 )2 ~OH oil A
8 2, 4-Cl H ~C (CH3 )2 -CH~ OH 105-108 3
9 2, 4-Cl H ~CH2 ~ 157-159 A
2, 4--Cl H -C (CH3 )2 ~) 113-116 A
.,
3~
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EX IR1) n R2 R3 ~-~-/ oc7 ¦ ~,ethod
_~ ~
11 2-Cl, 4-~F3 H -CH2 -CH=CH2 123-126 A
12 2~-Cl,4-CF3 H -(CH2 )~-OCH3 102-105 B
13 2,4-Cl H _(CH2 )2-Sc~3 109~1'1 B
14 2,4-Cl H _(CH2 )3-SCH3 82 B
2, 4-C1 H - ( CH~ )3 -~ ( CH3 )~ 74- 77 B
16 2, 4-Cl CH3 -CH-C-CH 98-101 A
~ CH5 .
17 2,4-Cl CH3 -(CH2)2-CN oil A
18 2,4-Cl H -(CH2)3-OcH(cH3)2 84- 86 A J
19 2,4-Cl H CH ~ 167-170 A
2,4-Cl H ~ 165-16 8 A
21 2,4-Cl H ~
22 2,4-Cl -CH CH -O~CH CH -91 - 93 B
23 2,4-Cl -C~`~2CH2CH2CH2CH2 96 - 99 B
24 2,4-Cl -CH2CH2C~HCH2CH2113 -115 A
CH3
2,4-Cl 2 2 2 2 63 - 65 A
26 2-Cl,4-CF3 H ( 2)2 3 95 - 98 A
27 2-Cl~4-CF3 H -(CH2)3-N(CH3)281 - 83 A
28 2-Cl,4-CF3 H ~CH2)2 OH 98 -101 A
29 4-CF3 H -(CH2)2-OCH3 88 - 91 A
4-CF3 H -CH2-CH=CH2 128 -130 A
31 4-CF3 H ( ~)2 3 83 - 85 A
32 4-CF3 H -(CH2)3-N(C~13)2 63 - 65 A
33 4-CF3 H -~CH2)2-H 95 - 98 A
.
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- 10 - HOE 78/F 258
EXAMPLES OF FORMULATION
.
E X A M P L E A:
A wettable powder which is easily dispersible in wa-
ter ls obtained by mixing
25 parts by weight of 2-/3-(2',4'-dichlorophenoxy)-6-nitro-
phenoxy7~propionic acld methoxyethyl amide as ac-
tive substance,
64 parts by weight of kaolin containing quartz as inert
material,
10 parts by weight of potassium lignosulfonate and
1 part by weight of sodium oleoyl-methyl tauride as wet-
ting and dispersing agent, and grinding the
mixture in a pin mill.
E X A M P L E B:
A dust composition suitable for use as a herbicide is
obtained by mixing
10 parts by weight of 2-/3-(2',4'-dichlorophenoxy)-6-nitro-
phenoxy7-propionic acid methoxyethyl amide as ac-
tive substance and
90 parts by weight of talc as inert material
and grinding the mixture in a hammer mill.
E X A M P L E C:
.
An emulsifiable concentrate is obtained from
15 parts by weight of 2-/~-(2',4'-dichlorophenoxy)-6-nitro-
phenoxy7-propionic acid methoxyethyl amide
75 parts by weig~t of cyclohexanone as solvent and
10 parts by weight of oxethylated nonyl phenol (10 EO) as
emulsifier.
.
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3~ ~
~ HOE 78/F 258
E ~ A M P L E D:
A granular formulation consists, for exa~ple, of about
2 to 15 parts by weight of 2-~3-(2',4'-dichlorophenoxy)-6-
nitrophenoxy7-propionic acid methoxyethyl
amide and i.nert granular carrier material
such as attapulgite, granular pumice and
quartz sand.
BIOLOGICAL E AMPLES:
(Pre-emergence application)
After sowing weeds in pots the compounds of the inven-
tion were sprayed on the soil in the form of aqueous dis-
persions of wettable powder concentrates. The plants were
controlled as regards the herbicidal effect and the result
was visually evaluated and expressed as percent of damage.
The results in Table I show that the substances ex-
hi.bited very good herbicidal properties and kept well
under control a great number of weeds.
Post-emergence application
Various weeds were sown in pots and allowed to grow
for about 3 weeks in a greenhouse to a height of 15 to 25
cm. The plants were then treated with the compounds ac-
cording to the invention. The visual evaluation approxi- : -
mately 4 weeks after application showed that the compounds
according to the invention satisfactorily combated the
weeds and that they were superior to the comparative com-
pound Bifenox 5-(2,4-dichlorophenoxy)-2-n'~trobenzoic acid '.
methyl ester (cf. Table I).
Crop tolerance
29 Crop plants were sown in pots and treated prior to
,
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- 1~ _ HOE 78/F 258
emergence with the compounds according to the invention.
The pots were kept under greenhouse conditions. The re-
sults were evaluated 4 weeks after application Or the com-
pounds and are listed in Table II. Even a high dosage of
2.4 kg of active substance (AS)/hectare did no or only
little damage to the crop plants. The invention compounds
are therefore useful for the selective control of weeds in
crop cultures.
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- 13 - HOE 78/F 258
Table
Herbicidal activity against various weeds in percent
______________ .______________________________________________
pre-emergence application ~ Pa~lemceragtieonne
~Ex. Ikg AS/
No. ha S~I ¦ ~G A~iR i~T CRS MAT A~R CRS
---- _. ,............... _ .
6 2,4 100 65 100 90 75 _ _
0,6 90 _ 100 _ _ _ _
1 2,4 100 100 100 96 95 _ _
0~6 100 95 100 95 85 _ _ _
7 2,4 95 75 100 100 100 65 _
OD 6 85 _ 100 98 100 65 _
11 2S4 100 95 100 100 100 90 _
12 2,4 100 100 100 100 100 100 _
0,6 100 100 100 100 100 100 _
22 2,4 100 100 100 80 ._ _ _
0,6 90 60 100 80 _ _ _
8 204 75 75 100 90 75 _100
9 2,4 65 75 100 75 65 _ ~5
13 2~4 65 _ 100 98 85 90 95 80
0~6 35 _ 100 95 35 85 70 40
14 2,4 65 _ 100 _ 65 _ 8Q
2D4 ~ _ 100 75 _ _ 95
16 2~4 _ _ _ _ _ 100100 98
0~6 _ _ _ _ _ 95100 80
18 2,4 100 85100 100100 98100 100
OG 6 95 65100 85 35 90100 98
2,4 _ _ _ _ .~ 95100 98
006 _ _ _ _ _ 90100 80
23 2~4 _ _100 _ _ 100100 100
0,6 _ _ 95 _ _ 8598 60
,4 294 _ _100 _ _ 95100 98
0~6 _ _ _ _ _ 80100 80
204 98 ~100 90 85 95100 100
0~6 65 _100 35 35 90100 80
26 2,4 100 98100 100100 100100 100
0~6 100 60100 100100 100100 100
27 2~4 100 90100 100100 100100 100
0 ~6 98 20100 100100 100100 100
28 2,4 100 100100 100100 100100 100
0a6 100 100¦ 100 100100 100100 100
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~ 14 - HOE 78/F 258
Ex kg ha/ SAL ECG A~IR l.~T CRS ~T A~l~ CRS
. _ _ .. _ . .
29 2~4100 100 100 100 80 _ _
006100 100 100 100 60 _ _
2~4100 95 100 _ _90100 95
0~6100 50 100 _ _7C 98 70
31 2~4100 80 100 100 90 _ _
32 2 4695 30 100 80 40 _ _
0~6 ~ _ 100 _ _ _ _
33 2~4100 100 100 100 98 _ _
0,6100 98 100 100 98 _ _
Compara-tlve
agent
(Bifenox)
20485 90 100 100 6035 70 20
0,665 50 95 100 35 0 _
SAL = Setaria
ECG = Echinochloa
AMR = Amaranthus
MAT = Matricaria
CRS = Chrysanthemum
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-- 15 -- HOE 78/F 258
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