Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Anilides and herbicides containing them
to present invention relates to anilides,
herbicides containing these compounds as active ingredi-
ens, and a method of controlling undesirable plant
growth using these compounds.
British Patent guy has disclosed the use ox
3,4-dichloropropionic acid aniline as a herbicide, in
particular as a herbicide for rice. However its
toleration by soybean and Indian corn is inadequate.
A pertain improvement in the selectivity of herbicidal
anilides in these crops has been achieved with Cyril-
anilides 7 ego
Of S COOK (British Patent 1,344,735)
Of
and with 0-aryla~ilidesg ego
Al 0 NHCCC2~5 (US. Patent 3,976,470).
Of
We have found that anilides of the general for
mute I
X 0 issuer (I)
Yin Z
where X is hydrogen, fluorine bromide, iodine, alkyd,
alkoxy, haloalkyl, haloalkoxy, alkylthio, alkylsulfinyl
or alkylsulfonyl of l to 6 carbon atoms, cycloalkyl of
3 to 6 carbon atoms, phenol, bouncily or benzyloxy and y
~~',
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is hydrogen, halogen, alkyd, alkoxy, halsalXyl, halo-
alkoxy, alkylthio, alkylsulfiny~l or alkylsulfonyl of 1
to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms,
phenol, bouncily or benzyloxy, or X and Y together are a
saturated or unsaturated 3-membered or 4-membered
alkaline radical, n is 1 or 2, Z is halogen and R is
alkyd ox 1 to 4 carbon atoms or alkoxyalkyl of 2 to 5
carbon atoms, and is trifluoromethyl if X is haloalkoxy,
are very useful for controlling undesirable plants in crops
such as rice, cereals, groundnuts and the like. m e
unexpectedly good toleration of specific compounds by
soybean and Indian corn, whilst extremely important
bridled weed species are destroyed, is surprising
X and Y are, for example hydrogen, phenol,
benzyloxy~, fluorine, bromide, iodine, straight-chain or
branched alkali alkoxy~ haloalkyl, haloalkoxy, alkylthio,
alkylsul~inyl or alkylsulfon~l of 1 to 6 carbon atoms,
preferably of 1 to 4 carbon atoms, cycloalkyl of 3 to
6 carbon atoms, ego methyl, eighth, isopropyl, n-propyl,
isobutyl, tert.-butyl, n-pentyl, n-hexyl, methoxy, elk-
isopropox~s~, sec.~-butoxy~, trifluoromethyl, Delaware-
methoxy, trifluoromethoxy, 2-chloro-2,1,1-trifluoro-
methoxy, methylthio, me-thylsulfonyl, isopropylthio and
cy~lohexyl, and Y can also be chlorine. If n is 1, X
and Y together can also be a 3-membered or 4-membered
alkaline or alkenylene radical which is unsubstituted or
`:
substituted by methyl, ego a trim ethylene, tetramethylene
1,1,3,,3-tetr~methyltrimethy~lene or buta-1,3-dienylene.
radical,
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I,
Z is, for example fluorine , chlorine or Bryan.
Z can also be trifluoromethyl if X is haloalkoxy .
R is, for example, alkyd of 1 to 4 C atoms and
alkoxyalkyl of 2 to 5 C atoms, ego methyl, ethyl,
I: npropyl, i-propyll n bottle, methoxymethyl or l-me~hoxy-
ethyl
I . . Preferred compounds of the formula I are those
' where X is alkyd, alko~y-or haloalkoxy, each of 1 to 4
J carbon atoms
.10 The anilides of the formula I are obtained, for
example, by reacting an amine of the formula II.
X~0~2
1. . Yin Z (II)
3 where X, Y, Z and n have the above meanings, with an
acid chloride of the formula III
Clocker (III)
or an acid android of the formula R-CO-O-CO-R9
where R has the above meanings, in the presence ox an
acid acceptor and a solvent
` Examples ox suitable solvents are water, Alcoa
hots, in particular aliphatic alcohols ego methanol,
ethanol and isopropanol, aliphatic chlorohydrocarbons9
I ego chloroform, ethylene chloride and dichloroethane~
and kittens, ego acetone, deathly eighteen and methyl.
ethyl kitten.: .
Suitable cold acceptors include the conventional
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I bases such as alkali metal hydroxides, bicarbonates and
s carbonates, alkaline earth metal oxides, hydroxides,
bicarbonates and carbonates and tertiary organic bases,
especially sodium hydroxide sodium carbonate sodium
f bicarbonate, calcium oxide, triethylamine9 pardon,
N,N~dimeth~laniline~ N9N-dimethyl cyclohexyl~mine,
f quinoline and tri-n-butylamine.
e starting substances ox the formulae II and
including the acid hydrides are used in approxi-
10 Mattel stoichiometric amounts, Leo not more than 10
mole % more or less of starting substance of the formula
II is used in comparison with starting substance of the
formula III. The reaction is carried out at prom --
-20 to ~150C, preferably from +20 to *60C.
Some of the amine of the formula II are known
they can be prepared by the methods described in
; Hobnail, Methadone don organ. Chemise, volume XI/l,
page 341 et seq., George Thieme-Verlag, Stuttgart, 1957.
The acid chlorides ox the formula III and the acid
20 androids are known.
EXAMPLE 1
2~.8 parts by weight ox 4 (4'-ethylphenoxy)-
3-chloroaniline were dissolved in 200 parts by weight of
acetone, and 12.6 parts by weight of sodium bicarbonate
dissolved in 150 parts by weight of water were added.
` 11.6 parts by weight ox propionyl chloride were then
added drops at 20C. The mixture was subsequently
stirred at room temperature for some hours, poured into
ice-water and filtered with suction. 28.9 parts by
,
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; weight of N-4-(4'-ethylphenoxy) 3-chlorophenyl-
' propionamide of melting point 83 - 85C were obtained.
The-following compounds, for example, were pro
pared Al cor=e~cn~ ruckuses.
.
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L 3 Z 8
6 - 0 .. Z . 0050/35205
i
,' X~O~NH-C0-R
i. Y
n
No X Y Z R rip
n
it 1 2 5 H Of ~2H5 83 - 85 C
, 2 6 5 H Of C2H5 131 - 133 C
3 OOZE H Of OH 100 102 C
4 OCHF2 En H C2H5.108 - 110 C
5 OCHF2 H Of C2~5 71 - 73 C
6 OOZE H Of clue 97 - 100C
Of C2~5 97~ SKYE
H 'rip Of C2H51 lo - 112 C
5 n-C3H7 H Of C2H5 67 - 69C
I 10 icky H Of C2H5 92 - 93 C
I t-C4Hg H Of. C2H5 118 - 121 C
n~4H9 H Of C2H5 78 80C
13 Clue H Of C2H5 130 - 132 C
14 icky H Of C2H5 I l
lSOC3H7 (n) H Of C2H5 72 - 75 C
17OCF Shekel H Of C2H5 79 81C
13OCF2CHFCl H H C2 5 123 - 125-C
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Nub X Y Z R
lo 19 OUCH H Of CH20CH3 68 70C
SHEA H Of C2~5 98 or 100 C
1 22 (C~2)3 Of c22H~ 93 95 C
j 23 -(GO YO-YO in Of C2H5 113 - 114 C
24 (OH) 4J 5-positioncl Cc22H5 113 - 115 C
27 H OKAY Go C2H5 oil
28 H clue Of C2H5 101 _ 103 C
29 SCHICK H Cal Cc22H55 83 - 85 C
31 -C(C~ )2C~2C(C~3)2 C2H5 107 - 110 C
Ye in 3-position C2H5 80 - 83 C
33 C2H5 H Of CH(CH3)0C~ 51 - 53 C
34 OCHF2 H Of PSYCHIC oil
OCHF2 H H CH(CH3)0C~3 98 - 100 C
C2~5 Of SWISH 108 - 110C
41 OH Of n-C4Hg oil
Ll5 OUCH H Of CH(CH,)CCH3 oil
C6H_ H H OH 202 - 204 C
I OUCH_ H Of CH(C~3)0CH3 a- link
I SHOWOFF H CF3 SHEA oil
The following compounds may be prepared analogously:
of
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I .
No, X n R
1 5 3 7 H C1 C2H5
i, 26 By H Of C2H5
36 CF3 H Of C2H5
37 H H H 3 7
38 C2H5 H . Clunk
' 39 CH(CH3)2 H Con C3H7
Jo 42 C2H5 H By C2H5
43 n-C3H7 H Of ( 3) 3
44 SCHICK H C1 ( 3 3
,, 10 47 OUCH H Of 3 7
The influence of representatives of the novel herbicidal
anilides on the growth of unwanted and crop plants is demonstrated
in greenhouse experiments.
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List of plants used in the experiments
Botanical name Abbreviation in table
_ _ _ _ .
Amaranths sup.
Amaranths retro~lexus
Arachys hypogaea Arachys hype
Couch lore
Chenopodium album Chenopod. alp.
, Euphoria nucleate EuphorbO genie.
'I Gallium apron
Gleason Max
Hordeum vulgar
Lamium purpureum Lamium purr.
Lamium sup.
Ours saliva Ours satin.
Sesbania exaltata Sesbania exalt.
Side puns Ida spin
Synapse alga
~riticum aestivum Critic. cost.
Zeta may
The vessels employed were plastic flowerpots having a volume
of 300 cm , and which were filled with a sandy loam containing
about lo humus. The seed of the test plants were sown shallow,
and separately, according to species. In the case of soybean,
i peat was added to ensure better growth. The rice plants were also
grown in a peat enriched substrate An impairment of the results
on leaf treatment post emergence treatment) is not to be feared,
particularly as the prior art comparative compounds are used under
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the same conditions. For this pos~emergence treatment, plants were
used which had been sown direct in the experiment vessels and had
grown there, or which had been grown separately as seedlings and
transplanted into the experiment vessels a few days before treat-
mint. The test plants were then from 3 to 15 cm Howe depending on
growth form The active ingredients were applied by suspending or
- emulsifying spray powders or emulsion conceIltrates of the active
ingredient in water, and spraying the mixture through finely
distributing nozzles. The prior art agents used for comparison
purposes were
A Of 0 NHCOC2H5
C1 So 3,976,470)
B Of S NHCOC2H5 (British 344, 735)
I
and
C Of NHCOC2H5 (British 903,766)~
Of
In the post emergence treatment, the application rates varied
from active ingredient to active ingredient, and were either 0.25,
0.5 or 1.0 kg/ha.
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;¦ In the reemergence treatment, the active ingredients were
Jo applied (here too in water as vehicle) immediately after the test
plants had been planter. Shortly before or after plotting the
soil was sprinkler irrigated to initiate swelling and germination
of the seeds Transparent plastic covers were then placed on the
vessels to ensure uniform germination, insofar as this was not
impaired by the chemicals.
The pots were set up in the greenhouse - species from warmer
areas at from 20 to SUE and species from moderate climates at
10 to 25C. The experiments were run or from 2 to 4 weeks.
I, During this period, the plant were tended and their reactions to
the various treatments assessed. The scale used for assessment was
0 to 100, 0 denoting no damage or normal emergence, and 100
' denoting non emergence or complete destruction of at least the
J. visible plant parts.
Jo on investigations in the greenhouse into selective herbicidal
action on post emergence application, compound no 27, at
Al 0.5 kg/ha, was tolerated by soybeans much better than prior art
I: comparative agent An and also combated important broad leaved
I weeds.
Jo The greenhouse experiments also revealed that compound
I no. I on post emergence application at 1.0 kg/ha~ had an
Jo excellent herh~cidal action and damaged neither soybean nor Indian
corn plants. Comparative compound C caused considerable damage
Prior art comparative compounds A and B, which are chemically
closer, also caused heavy damage to these crops, although not as
much as agent C.
The greenhouse experiments further showed that the novel
Jo an.ilides, such as compounds nos. 5 and 1 at 0.5 kg~ha applied
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post emergence, had a very good action on various broad leaved weed
species, without damaging groundnut plants.
In post emergence application tests in the greenhouse active
ingredients nosy 2, 3, Al 10, 13, 14, 17, 21, 23, 28, 29 and 30,
at 1~0 kg/ha, had a more or less strong action on broad leaved
unwanted plants and were well tolerated by rice and wheat plants.
These greenhouse experiments further revealed that compound
no. 9, applied post emergence at 0.25 kg/ha, and compound no. 16 7
applied post emergence at 0~5 kg/ha, had a good action on broad-
leaved unwanted plants and were selective in crop plants such as
rice, wheat, groundnuts and soybeans. Compound no. 28, appliedpostemergence at 0.5 kg/ha, exhibited a good herbicidal action on
broad leaved weeds without damaging the cereal specie barley
Compound nos. 14, 11 and 17 r applied reemergence at
3.0 kg/ha, had a herbicidal action on Synapse alga as broad leaved
test plant.
The agents may be applied during emergence of the unwanted
plants, but are preferably applied post emergence (leaf treatment.
If certain crop plants tolerate the active ingredients less well,
I application techniques may be used in which the herbicidal agents
are sprayed from suitable equipment in such a manner that the
leaves of sensitize crop plants are if possible not touched, and
the agents reach the soil or the unwanted plants growing beneath
the crop plants (post-directed, lay-by treatment
The amount of active ingredient applied depends on the growth
stage of the plant and the Sicily of the year, and varies from
0.1 to 10 kg and moxie of active ingredient per Hector.
To increase the spectrum of action and to achieve synergistic
effect, the novel anilides may be mixed and applied together with
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numerous representatives of other herbicidal or growth-regulating
active ingredient groups. Examples of suitable mixture components
are Dennis, 4H-3,1benzoxazine derivatives, benæothiadiazinones,
such as 3-isopropyl-2,1,3-benzothiadiazin-4-one-2 t 2-dioxide and
its sodium salt, 2,6-dinitroanilines, N-phenylcarb~mates, trio].-
garb mates, halocarboxylic acids treasons, asides, ureas,
diphenyl ethers, triazinones, uracils, benzofuran derivatives,
cyclohexane-1,3--dione derivatives, etc.
It may also be useful to apply the novel compounds, either on
their own or combined with other herbicides, in admixture with
other crop protection agents, ego agents for combating pests or
phytopathogenic fungi or bacteria The compounds may also be mixed
with solutions of mineral salts used to remedy nutritional ox
trace element deficiencies Non-phytotcxic oils and oil concern-
trades may also be added
Application may be effected for instance in the form of
directly spray able solutions, powders suspensions, dispersions,
emulsions, oil dispersions, pastes, dusts broadcasting agents, or
granules by spraying, atomizing, dusting, broadcasting or
watering. the ohms of application depend entirely on the purpose
for which the agents are being used, but they must ensure as fine
a distribution ox the active ingredients as possible
For the preparation of solutions, emulsions, pastes and oil
dispersions to be sprayed direct, mineral oil fractions of medium
to high boiling point, such as kerosene or diesel oil 9 further
; coal-tar oils and oils of vegetable or animal origin, aliphatic~
I` cyclic and aromatic hydrocarbons such as Bunsen Tulane zillion,
paraffin, tetrahydronaphthalene, alkylated naphthalenes and their
derivatives such as methanol, ethanol propanol, buttonhole, sheller
:`
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I 0050/35205
form, carbon tetrachloxide, cyclohexanol~ cyclohexanone, sheller-
Bunsen, isophorone, etc., and strongly polar solvents such as
dimethylformamide, dim ethyl sulfoxide, N-methylpyrrolidone, water,
etc. are suitable
Aqueous formulations may be prepared from emulsion concern-
trades, pastes, oils dispersions or wettable powders by adding
water. To prepare emulsions pastes and oil dispersions the in-
gradients as such or dissolved in an oil or solvent may by home-
jounced in water by means of wetting or dispersing agents, ad-
hornets or emulsifiers. Concentrates which are suitable for
dilution with water may be prepared from active ingredient,
wetting agent, adherent, emulsifying or dispersing agent and
possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth
metal and ammonium salts of ligninsulfonic acid, naphthalenesul
ionic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyd
sulfates and alkyd sealants, alkali metal and alkaline earth
metal salts of dibutylnaphthalenesulfonic acid, laurel ether
sulfate, fatty alcohol sulfites, alkali metal and alkaline earth
metal sells ox fatty acids, salts ox sulfated hexadecanols, Hyatt-
decanol~, and octadecanols, sells of sulfated fatty alcohol glycol
ethers, condensation products of sulfonated naphthalene and
naphthalene derivatives with formaldehyde, condensation products
of naphthalene or naphthalenesulfonic acids with phenol and
formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated
isooctylphenol, ethoxylated octylphenol and ethoxylated nonyl
phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol
ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty
alcohol ethylene oxide condensates, ethoxylated castor oil, polyp
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oxyethylene alkyd ethers ethoxylated polyoxypropylene~ laurel
alcohol polyglycol ether acutely, sorbitol ester, Logan, sulfite
waste liquors and methyl cellulose.
Powders, dusts end broadcasting agents may be prepared by
mixing or grinding the active ingredients with a solid carrier.
Granules ego coated, impregnated or homogeneous granules,
may be prepared by bonding the active ingredients to solid
carriers. Examples of solid carriers are mineral earths such as
silicic acid, silica gels, silicates, talc, kaolin, Attaclay,
lo limestone, lime, chalk, bole, loss, clay, dolomite diatomaceous
earth, calcium sulfate magnesium sulfate magnesium oxide, ground
plastics, fertilizers such as ammonium sulfate, ammonium
phosphate, ammonium nitrate and ureas, and vegetable products
such as grain flours bark meal wood meal, and nutshell meal,
cellulosic powders, etch
The formulations contain from 0.1 to 90, and preferably 1 to
60, by weight of active ingredient.
Examples of such formulations are given below.
EXAMPLE
90 parts by weight ox compound l is mixed with lo parts by
weigh of N-methyl-alpha-pyrrolidone. A mixture is obtained which
is suitable for application in the Norm of very fine drops.
E.YA~IPLE II
lo parts by weight of compound 27 is dissolved in a mixture
consisting of 90 parts by weight of zillion 6 parts by weight of
the adduce of 8 to lo moles of ethylene oxide and l mole of oleic
acid-N-monoethanolamide, 2 parts by weight of the calcium salt of
dodecylbenzenesulfonic acid and 2 parts by weight of the adduce
of 40 moles of ethylene oxide and l mole of castor oil.
I
ooze. ooze
EXAMPLE III
20 parts by weight of compound 20 is dissolved in a mixture
consisting of 60 parts by weight of cyclohexanone, 30 parts by
weight of isobutanol, S parts by weight of the adduce of 7 moles
of ethylene oxide and 1 mole of isooctylphenol, and 5 parts by
weight of the adduce of 40 moles of ethylene oxide and 1 mole of
castor oil
EAGLE IV
20 parts by weight of compound 1 is dissolved in a mixture
consisting of 25 parts by weight of cyclohexanone, 65 parts by
weight of a mineral oil fraction having a boiling point between
210C and 280C, and 10 parts by weight of the adduce of 40 moles
of ethylene oxide and 1 mole of castor oil.
EXAMPLE
80 parts by weight of compound 5 is well mixed with 3 parts
by weight of the sodium salt of diisobutylnaphthalene-alpha-
~ulfonic acid, 10 parts by weight of the sodium salt of a Logan-
-sulfonic acid obtained from a sulfite waste liquor, and 7 parts
by weight of powdered silica golf and triturated in a hammer mill.
EXAMPLE VI
5 parts by weight of compound 2 is intimately mixed with
95 parts by weight of particulate kaolin. A dust is obtained
containing I by weight of the active ingredient.
EXAMPLE VII
30 parts by weight of compound 3 it intimately mixed with a
mixture consisting of 92 parts by weight of powdered silica gel
and 8 parts by weight of paraffin oil which has been sprayed onto
the surface of this silica gel. A formulation of the active
ingredient is obtained having good adherence.
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17 OOZE 0050/35205
EXAMPLE VIII
40 parts by weigh of compound 6 is intimately mixed with
10 parts of the sodium salt of a phenolsulfonic acid urea-form-
alluded condensate; 2 parts of silica gel and 48 parts of water
to give a stable aqueous dispersion.
EXAMPLE IX
20 parts of compound 1 is intimately mixed with 12 parts or
the calcium salt of dodecylbenzenesulfonir acid, 8 parts of a
fatty alcohol polyglycol ether, 2 parts ox the sodium salt ox a
I phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a
paraffinic mineral oil. A stable oily dispersion is obtained.
I
