NZ206662A - Phenoxypropionic acid derivatives and herbicidal compositions - Google Patents
Phenoxypropionic acid derivatives and herbicidal compositionsInfo
- Publication number
- NZ206662A NZ206662A NZ206662A NZ20666283A NZ206662A NZ 206662 A NZ206662 A NZ 206662A NZ 206662 A NZ206662 A NZ 206662A NZ 20666283 A NZ20666283 A NZ 20666283A NZ 206662 A NZ206662 A NZ 206662A
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- NZ
- New Zealand
- Prior art keywords
- formula
- halogen
- acid derivatives
- carbon atoms
- alkoxy
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
- C07C43/1782—Unsaturated ethers containing hydroxy or O-metal groups containing six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Description
New Zealand Paient Spedficaiion for Paient Number £06662
2
HO ORAWMSS
'■r f ^ \S ^
* \ev^
Priority
_ , . Ot- IVl-S* Date(s): fir-'• • • ■
. . QI-I2-&
Complete Specification Filed:
CO -7PQ. 13 ' C& I. £p. ??.'$
Xo
Class:
ep.?S:Ji?. j.
.76.
Publication Date: P.O. Journal, No
N.Z.No.
NEW ZEALAND Patents Act 1953
COMPLETE SPECIFICATION
"PHENQXYPROPIONIC ACID DERIVATIVES."
<5,
I ,
We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany,
do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : -
- 1 - (Followed by 1A.)
- 1/*-
206662
The invention relates to new phenoxypropionic acid derivatives, several processes for their preparation and their use as herbicides. The invention also relates to new intermediates and a process for their preparation.
ionic acid derivatives have herbicidal properties (compare (U.K. specification) 1, 5'82 , 271> arid" ' "
U.S. Patent Specification 4,046,553). Thus, for example, benzyl 2-C4-(3,5-dichloro-pyrid-2-yloxy)-phenoxyD-10 propionate and (2-phenoxy)-ethyl 2-C4-(4-trifluoromethyl-phenoxy)-phenoxy3-propionate, can be used for combating weeds. However, the action of these substances is not always satisfactory.
It is already known that numerous phenoxyprop-
The new phenoxypropionic acid derivatives of the
formula r
2
3
(I)
in whi ch represents a radical of the formula
wherein
represents hydrogen or halogen, X2 represents halogen or trifluoromethyl, X3 represents halogen or trifluoromethyl, X^ represents hydrogen or halogen and X5 represents hydrogen or halogen, Y represents oxygen or the radical S0m,
2066 62
wherein m represents 0, 1 or 2,
and
R2 and R3 independently of one another represent 5 hydrogen, halogen, alkyl with 1 to 4 carbon atoms,
alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, nitro, cyano or alkoxy-carbonyl with 1 to 4 carbon atoms in the alkoxy group,
have now been found.
The phenoxypropionic acid derivatives of the formula (I) contain an asymmetric carbon atom in the propionic acid part and can therefore exist in two enantiomeric forms. The invention relates both to the pa r-15 ticular racemates and to the R- and S-enantiomers.
It has furthermore been found that the new phenoxypropionic acid derivatives of the formula CI) are obtained by a process in which a) phenoxypropionyI chlorides of the formula
CH3 <II>
r1-o-fl y-o-ch-co-cl in which
R^ has the abovementioned meaning,
are reacted with hydroxy- compounds of the formula
HO-CH2-"cH2-Y-CH2-f^ <I">
in which
R2, R3 and Y have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, the product is then oxidised, or
b) phenol derivatives of the formula
<»>
-OH
in which has the abovementioned meaning,
are reacted with propionic acid derivatives of the formu la
A
?H3 ? CH3
z-ch—c-o-ch2-c-ch2-y-ch (v)
CHj i n w h i c h 2 3
~7 R , R and Y have the abovementioned meaning
and
Z represents halogen, tosylate or mesylate, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, the product is then oxidised. 15 Finally, it has been found that the new phenoxy-
propionic acid derivatives of the formula (I) are distinguished by an outstanding herbicidal activity.
Surprisingly, the phenoxypropionic acid derivatives of the formula (I) according to the invention have 20 substantially better herbicidal properties than the compounds benzyl 2-C4-(3,5-di-chloropyrid-2-yloxy)-phenoxyD-propionate and (2-phenoxy)-ethyI 2-C4-C4-trifluoromethyl-phenoxy)-phenoxy3-propionate, which are known from the prior art and are structurally similar 25 compounds of analogous type of action.
Formula (I) provides a general definition of the ^ substances according to the invention. In this formula,
— R^ represents a radical of the formula
JUa»»
2.066 £2
in which, preferably,
*
X' represents hydrogen or chlorine,
X2 represents chlorine or trifluoromethyl, 5 X3 represents chlorine or trifluoromethyl,
X^ represents hydrogen or chlorine and X5 represents hydrogen or chlorine.
Y represents oxygen or the radical S0m, m representing 0, 1 or 2, and the radicals R2 and R3 independently of 10 one another preferably represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, nitro, cyano or a IkoxycarbonyI with 1 or 2 carbon atoms in the alkoxy group.
Particularly preferred phenoxypropionic acid derivatives of the formula (I) are those in which r1 represents a radical of the formula
CI CI
CF3
-Q- .
.-f or Cl-^
and
2 T
Y and R and RJ have the abovementioned meanings. The R-enantiomers of these particularly preferred phenoxypropionic acid derivatives, that is to say those
compounds of the formula BE BUI3
w
R2
y v CH^° CH3 /-/\
L1 -0-Q-O-CV^O-ch2-C-CH2-Y-CH2^^3
(I)
which have the R-configuration on the asymmetrically substituted carbon atom, are also particularly preferred.
In the above formula, the asymmetrically substi-5 tuted carbon atom is labelled by (*).
If 2-£4-(5-t rifluoromethyl-pyrid-2-yloxy)-phenoxy3-propionyl chloride and 2,2-dimethyl-propane-1,3-dio I monobenzyl ether are used as starting substances, the course of process Ca) according to the invention can be 10 represented by the following equation:
Qj \ CH3 CH^
"° \ /"°"ch-c°-c1 + ho-ch2-c-ch2-o-ch2
■o
/ ^ / S. CH"* 0 CH7
"hc1 > cf3"\^"q"\/"q"^h—c-o-ch2-c-ch2-o-ch2
o
If 4-<2-chloro-4-t rifluoromethyl-phenoxy)-phenol and (2,2-dimethyl-3-benzy loxy)-propy I 2-bromo-2-propion-15 ate are used as starting substances, the course of process (b) according to the invention can be represented by the following equation:
ZQ666Z
(c1 ch3 o ch3
"hbr > cf3-/^y-o-^y-o-ch—c-o-ch2-c-ch2-o-ch2-/ y
~~ _ CH3
Formula (II) provides a general definition of the phenoxypropionyl chlorides required as starting sub-5 stances in process (a) according to the invention. In this formula, preferably represents those radicals which have already been mentioned as preferred for the substituent R^ in connection with the description of the substances of the formula (I) according to the inven-10 t ion.
The phenoxypropionyl chlorides of the formula (II) are known, or they can be prepared in a.simple manner by known methods (compare (U.K. specifications 1,579,201, 2, 042, 503 and 1, 599 ,121 _ and Hew Z-ealand. 15 latent Specification No.187756.
Thus, the substances of the formula (II) can be obtained, for example, by reacting the acids on which they are based with thionyl chloride.
For synthesis of the R-enantiomers of the phenoxy-20 propionic acid derivatives of the formula (I), the R-enantiomers of the phenoxypropionyl chlorides of the formula (II) are required as starting substances in carrying out process (a) according to the invention.
These substances are also known, or they can be prepared 25 in a simple manner by known methods (compare U.K. specification ) 2,042,503).
Formula (III) provides a general definition of the hydroxy compounds also required as starting substances Au * DD Oil
in process (a) according to the invention. In this formula, R2, R3 and Y preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the sub-5 stances of the formula (I) according to the invention.
The hydroxy compounds of the formula (III) are not yet known. They can be prepared by a process in which compounds of the formula ch3 (vi)
ho-ch2-c-ch,-y1-h ifl3
in which
Y^ represents oxygen or sulphur,
are reacted with benzyl halides of the formula r2 (vii)
Hal~CH2-0[
in which ^
R2 and R3 have the abovementioned meaning and
Hal represents chlorine, bromine or iodine,
in the presence of an acid acceptor and, if appropriate,
in the presence of a diluent, and, if appropriate, if
Y^ represents sulphur, the substances thereby formed,
of the formula
?H3 (Ilia)
ho-ch2-c-ch2-s-ch2 •
ch3
i n w h i c h
O 7
R and R have the abovementioned meaning,
are oxidised with hydrogen peroxide in the presence of a 25 diluent.
All those acid acceptors and diluents which are
206162
mentioned as preferred in connection with the description of process (a) according to the invention (see below) can preferably be used in carrying out the first stage of this preparation of hydroxy compounds of the formula (III) 5 The oxidation in the second stage of the process for the preparation of the compounds of the formula (III) can be carried out in any of the inert solvents which can usually be used for such reactions. Methylene chloride can preferably be used.
The reaction temperatures can be varied within a substantial range in the process for the preparation of the hydroxy compounds of the formula (III). In general, the first stage is carried out at temperatures between -20°C and +160°C, preferably between 0°C and +140°C. 15 The second stage is generally carried out at temperatures between -20°C and +50°C, preferably between 0°C and 40°C.
The reactants are employed in approximately equi-molar amounts in the preparation of the hydroxy compounds 20 of the formula (III) by the above process. However, it is also possible to use one of the two components in a larger excess. If oxidation of the substance of the formula (Ilia) initially formed is desired, the oxidising agent 1s used In the particular calculated amount. Work-25 ing up 1s 1n each case carried out by customary methods.
Formula (IV) provides a definition of the phenol derivatives required as starting substances in process (b) according to the invention. In this formula, preferably has those meanings which have already been ment-30 ioned as preferred for this substituent in connection with the description of the substances of the formula (I) according to the Invention.
The phenol derivatives of the formula (IV) are known, or they can be prepared in a simple manner by 35 known methods (compare (U.K. specification 2^042,5,03,
U.K. specification 1,599,121, New Zealand Patent Specification No.187756 and U.K. specification 2,002,368).
14JUN/985 ]
^ e i m
206662
Formula (V) provides a general definition of the propionic acid derivatives also required as starting sub-5 stances in process (b) according to the invention. In this formula, R2, R3 and Y preferably have those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
Z preferably represents chlorine, bromine, tosylate (-OSOj-^^-CH^) or mesylate (-OSOg'CHj).
The propionic acid derivatives of the formula (V) are not yet known. However, they can be prepared by a process in which hydroxy compounds of the formula
. ch_
,3 /; v (hi)
ho-ch2-c-ch2-y-ch2
ch3
in which
R2, R3 and Y have the abovementioned meaning, are reacted with lactic acid derivatives of the formula
Tn3 (VIII)
Z-CH-CO-Cl
in which
Z has the abovementioned meaning,
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.
The hydroxy compounds of the formula (III) 25 required as starting substances in the preparation of the propionic acid derivatives of the formula (V) and preparation thereof have already been treated in connection with the description of process (a) according to the invention. The lactic acid derivatives of the formula 30 (VIII) also required as reactants for the reaction for
Z066 6%
the synthesis of the propionic acid derivatives of the formula (V) are known, or they can be prepared in a simple manner by known methods.
It is necessary to use the S-enantiomers of the propionic acid derivatives of the formula (V) for synthesis of the R-enantiomers of the phenoxypropionic acid derivatives of the formula (I) by process <b), since Ualden inversion takes place on the asymmetric carbon atom of the propionic acid derivatives of the formula
CH, o CH-
(V)
Z-ch^k><H2--C-CH2-Y-CH2-^^3
in the course of the reaction. In the above formula (V), the asymmetric carbon atom is labelled by (*). The S-enantiomers of lactic acid derivatives of the formula (VIII) required as starting substances for the prepara-15 tion of the S-enantiomers of the propionic acid derivatives of the formula (V) are known, or they can be prepared in a simple manner by known methods.
Processes (a) and (b) according to the invention and the process for the preparation of the substances of 20 the formula (V) are preferably carried out using diluents. Suitable diluents are virtually all the inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyctohexane, petroleum ether, 25 benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ch lorobenzene and o-dich lorobenzene, ethers,
such as diethyl ether and dibutyl either, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and 30 dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,
esters, such as methyl acetate and ethyl acetate, nitriles,
such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethyIformamide, dimethyl-acetamide and N-methyl-pyrrolidone, and dimethyIsu Iphox-ide, tetramethylene sulphone and hexamethyIphosphoric 5 acid triamide.
Acid acceptors which can be used both in processes (a) and (b) according to the invention and in the process for the preparation of the compounds of the formula (V) are all the acid-binding agents which can usually be 10 employed for such reactions. Preferred acid acceptors are alkali metal hydroxides and alkaline earth metal hydroxides and oxides, such as, for example, sodium and potassium hydroxide, calcium hydroxide and calcium oxide, alkali metal carbonates and alcoholates, such as sodium 15 and potassium carbonate and sodium and potassium methylate and ethylate, and furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, tri-methylamine, dimethyIani I ine, dimethyIbenzyI amine, 1,5-diazabieyeloC4,3,0Dnon-5-ene (DBN), 1,8-diazabicyc lo-20 C5,4,0Dundec-7-ene (DBU) and pyridine.
The reaction temperatures can be varied within a substantial range both in processes (a) and (b) according to the invention and in the process for the preparation of the compounds of the formula (V). In 25 general, the reaction is in each case carried out at temperatures between -20°C and +160°C, preferably between 0°C and +140°C.
Processes (a) and (b) according to the invention and also the process for the preparation of the compounds 30 of the formula (V) are in general carried out under normal pressure. However, they can also be carried out under increased or reduced pressure.
For carrying out processes (a) and (b> according to the invention and the process for the preparation of 35 the compounds of the formula (V), the starting substances required in each case are generally employed in approxi-
2 06 6 6Z
mately equimolar amounts. However, it is also possible to use one of the two particular components employed in a larger excess. The reactions are in general carried out in a suitable diluent in the presence of an acid 5 acceptor, and the reaction mixture is stirred for several hours at the particular temperature required. Working up is in each case carried out by customary processes. In general, a procedure is followed in which water is added to the reaction mixture, the mixture is extracted 10 several times with an organic solvent of low water-miscibility and the combined organic phases are dried and concentrated by stripping off the solvent.
Some of the new compounds are obtained in the form of oils, some of which cannot be distilled without 15 decomposition, but can be freed from the last volatile constituents by so-called "incipient distillation", that is to say by prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this manner.
To prepare those compounds of the formula (I) in which Y represents S0m and m represents 1 or 2, those substances of the formula (I) in which Y represents sulphur can be oxidised by customary methods with the particular required amount, or with an excess, of oxidis-25 ing agent, if appropriate in the presence of a catalyst and in the presence of a diluent.
All the customary oxygen-donating oxidising agents can be used as the oxidising agents. Hydrogen peroxide, peracetic acid and m-chloroperbenzoic acid are 30 preferably used.
Possible diluents for carrying out this oxidation are all the organic solvents which can usually be employed for such oxidation reactions. Glacial acetic acid and methylene chloride can preferably be used. 35 Catalysts which can be used for this oxidation are all the reaction accelerators which can customarily
be employed for such oxidation reactions. Formic acid and sulphuric acid can preferably be used.
The temperatures for the oxidation can be varied within a certain range. In general, the oxidation is 5 carried out between -20°C and +50°C, preferably between 0°C and +40°C.
In carrying out the oxidation, the starting compound of the formula (I) is generally reacted with the particular calculated amount or with a slight excess of 10 oxidising agent. Working up is in each case carried out by customary methods.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-15 killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used. 20 The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthem is, Galinsoga, 25 Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abuti Ion, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea. 30 Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, L a c -tuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, 35 Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Bra-chiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro-
2 06 6 62
pyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera. Monocotyledon cultures of the genera: Oryza, Zea, Triti-5 cum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, flnanss, Asnaraaus and Allium.
However, the use of the active comnounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other 10 plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the 15 compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, 20 cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wett-25 able powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in known manner,
for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surfaca-active agents, that is, emulsifying agents and/or dispersing agents, and/or 35 foam-forming agents.
In the case of the use of water as an extender,
2 066 62
organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated ali-5 phatic hydrocarbons, such as chlorobenzenes, chloroethyl-enes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions and mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, 10 ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or eyelohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
As solid carriers there are suitable: for 15 example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmoriIlonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for granules 20 there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco 25 stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsi-fiers, such as polyoxyethylene-fatty acid esters, poly-oxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, a Iky Isu Iphonates, alky Isulphates, 30 arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcel lulose and natural and synthetic polymers in the form of powders, 35 granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
•2 06 6 62
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-5 stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90X.
The active compounds according to the invention,
as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixing being possible.
Suitable herbicides for the mixtures are the known herbicides such as, for example, 1-amino-6-ethyl-th i o-3-(2,2-di methyIp ropyl)-1,3,5-triazine-2,4dH,3H)-dione or N-(2-benzthiazo lyl)-N,N'-dimethyl-urea for combating weeds in cereals; 4-amino-3-methyl-6-pheny1-1,2,4-20 triazin-5C4H)-one for combating weeds in sugar beet and 4-ami no-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one for combating weeds in soya bean. Surprisingly, some mixtures also show a synergistic action.
Mixtures with other known active compounds, such 25* as fungicides, insecticides, acaricides, nematicides,
bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared 30 therefrom by further dilution, such as ready-to-use solutions, suspensions, emu Is ions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomising or scattering.
The active compounds according to the invention 35 can be applied either before or after emergence of the plants. They can also be incorporated into the soil
2 066 62
- 17 -before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts 5 used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following 10 examples.
Preparation Examples Example 1
CI
/ , ^ ch7 o ch_ 7
C1-0~°"0-°-'H—C-°-CH2-C.CH2-0-CH2-{3
I) (Process b)
A mixture of 2.6 g (0.01 mol) of 4-(3,5-dich loro-
pyrid-2-yloxy)-pheno I, 3.3 g (0.0097 mol) of (2,2-di-methyl-3-benzyloxy)-propyI 2-bromo-propionate and 1.4 g (0.01 mol) of potassium carbonate in 100 ml of aceto-nitrile was heated under reflux for 5 hours. The reac-20 tion mixture was then cooled to room temperature and poured into 200 ml of water. The mixture was extracted with two 100 ml portions of ether. The combined organic phases were dried over sodium sulphate and concentrated by stripping off the solvent under reduced pressure. The 25 residue which remained was freed from traces of volatile constituents by warming it slightly under a high vacuum. 4.5 g (89.3% of theory) of (2,2-dimethyl-3-benzyloxy)-propyl 2-C4-(3,5-dichloro-pyrid-2-yloxy)-phenoxy]-pro-pi onate were obtained in this manner in the form of a 30 liquid of refractive index n2®=1.5542.
Preparation of the starting substances
20666Z
ch, o ch, .
. 3 „ ,3 /) ^ (V-1)
Br-CH—C-0-CH2-C-CH2-0-CH2
ch3
o
A solution of 17.2 g (0.1 mol) of 2-bromo-propionyl chloride in 100 ml of toluene was added to a 5 mixture of 194 g (0.1 mo I) of 2,2-dimethyl-3-hydroxy-propyl benzyl ether and 11 g (0.11 mol) of triethylamine in 200 ml of toluene at room temperature. The mixture was stirred at room temperature for a further 14 hours and then worked up by a procedure in which water was 10 first added, the reaction mixture was then extracted several times with toluene and the combined toluene phases were dried and concentrated by stripping off the solvent under reduced pressure. 19 g (58% of theory) of (2,2-dimethyl-3-benzyloxy)-propy I 2-bromo-propionate were 15 obtained in this manner.
CHo
3 (III-1)
ho-ch2 -c-ch2 -o-ch2
ch \=j
CH3
A solution of 126.5 g (1 mol) of benzyl chloride in 200 ml of toluene was added dropwise to a mixture of 208 g (2 mols)of 2,2-dimethyl-propane-1,3-dio I, 56 g 20 (1 mol) of potassium hydroxide and 50 ml of water in
200 ml of toluene at 60°C, while stirring. The mixture was stirred at 80°C for a further 14 hours and then worked up by a procedure in which the reaction mixture was poured into water and then extracted several times 25 with toluene and the combined organic phases were dried and concentrated by stripping off the solvent under reduced pressure. The residue which remained was distilled. 100 g (51.5% of theory) of 2,2-dimethy1-3-hydroxy-propyI benzyl ether were obtained in this manner. 30 Boiling point: 113°C/6 mbar
II) Preparation of the compound of the formula :i ch3
-o-ch2 -c—ch2 -o-ch2 ch3
-o by process variant (a):
First 1.9 g (0.01 mol) of 2,2-dimethyl-3-hydroxy-5 propyl benzyl ether and then 1 g (0.01 mol) of triethyl-amine were added dropwise to 3.45 g (0.01 mol) of 2-C4-(3,5-dichloropyrid-2-yloxy)-phenoxyD-propionyl chloride in 50 ml of toluene at 20°C.
The reaction mixture was subsequently stirred at 10 20°C for 14 hours and then worked up as in process variant (b).
4.5 g (89.3X of theory) of (2,2-dimethy l-3-benzy I-oxy)-propyl 2-C4-(3,5-dichloro-pyrid-2-yloxy)-phenoxyD-propionate were obtained in the form of a liquid of 15 refractive index n^=1 .5530.
The compounds listed in Examples 2 and 3 which follow were also prepared by the method described in Example 1 under (II), using the R-enantiomer of the particular propionyl chloride as the starting substance. 20 Example 2
ch, o ch,
I W tl I -J
— N
Example 3
•O
(R) kl24= + 3,7°
o-ch—c-0-ch2-c ch2-0-ch2
™3r .1 24
/. i t \ ch. o • ch, cf3-v^_vo-^y-0-ch c-0-ch2-c ch2-0-ch2
■o ch3
<R' M " . - 3.5°
2066 62
Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active com pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, 15 only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in X damage in comparison to the development of the untreated control. The figures denote:
0% = no action (like untreated control)
100X = total destruction
In this test, active compound (1) according to the invention exhibits a very good activity.
Claims (9)
1) Phenoxypropionic acid derivatives of the formula ,*2 CH,0 CH, J R1 -°.^°H:H-5-0-CH2-C-CH2-Y-CH2Hf\ ^ (1 } CH^ in which r1 represents a radical of the formula o r wherei n represents hydrogen or halogen, 2 X represents halogen or trifluoromethyl, X3 represents halogen or trifluoromethyl, X^ represents hydrogen or halogen and X5 represents hydrogen or halogen, Y represents oxygen or the radical S0m, wherein m represents 0, 1 or 2, and R2 and R3 independently of one another represent hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, nitro, cyano or alkoxy-carbonyl with 1 to 4 carbon atoms in the alkoxy group. 2) Process for the preparation of phenoxypropionic acid derivatives of the formula /r2 y v CH,0 CH- / r1 -Q.°-CH^ch24.CH2.Y.CH2^3 J - 23 - i n whi ch R^ represents a radical of the formula X1 '-6- 2 „ „ or wherein whe rei n represents hydrogen or halogen, p X& represents halogen or trifluoromethyl, X3 represents halogen or trifluoromethyl, X^ represents hydrogen or halogen and represents hydrogen or halogen, Y represents oxygen or the radical S0m/ m represents 0, 1 or 2, and 2 X R and R^ independently of one another represent hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, nitro, cyano or alkoxy-carbonyl with 1 to 4 carbon atoms in the alkoxy group, characterised in that a) phenoxypropionyl chlorides of the formula (II) K1 O A "3 K °~V y-O—CH-CO-C1 i n whi ch R^ has the abovementioned meaning, are reacted with hydroxy compounds of the formula CH R2 HO-CH2-pH2-*-CH2^^3 (III> <2 0 6 6 6 2. - 24 - in which R2, R3 and Y have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, the product is then oxidised, or b) phenol derivatives of the formula r1 -0-q-oh in which R^ has the abovementioned meaning, are reacted with propionic acid derivatives formula ch3 o ch3 z-ch—c-0-ch2-c-ch2-y-ch2-/^s ch3 in which
2 T R , RJ and Y have the abovementioned meaning and Z represents halogen, tosylate or mesylate, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, the product is then oxidised.
3) Herbicidal agents, characterised in that they contain at least one phenoxypropionic acid derivative of the formula (I).
4) Method of combating weeds, characterised in that phenoxypropionic acid derivatives of the formula (I) are applied to the weeds and/or their environment.
5) Use of phenoxypropionic acid derivatives of the formula (I) for combating weeds.
6) Process for the preparation of herbicidal agents, characterised in that phenoxypropionic acid derivatives of the formula (I) are mixed with extenders and/or (IV) of the - 25 - surface-active substances.
7. R-enantiomer8 of Phenoxypropionic acid derivatives of the formula CH O CH I*2 R,-°-^^o-CH^c-o-cH2-c-CH2-y-eH?-/^ CH« k (*.) 3 in which R1 represents a radical of the formula wherein X^ represents hydrogen or halogen, X2 represents halogen or trlfluoroaethyl, * X represents halogen or trifluoromethyl, X* represents hydrogen or halogen and X5 represents hydrogen or halogen, Y represents oxygen or the radical S0m, whereln » represents 0, 1 or 2, and ft2 and Independently of one another represent hydrogen, halogen, alkyl with 1 to 4 carbon atoas, alkoxy with 1 to 4 carbon atoas, alkylthlo with 1 to 4 carbon atoas, nltro, cyano or alkoxy-carbonyl with 1 to 4 carbon atoas 1n the alkoxy group* 2-0 & (> 6 - 26 -
8. A derivative according to claim 1 or claim 7 substantially as herein described or exemplified.
9. A process according to claim 2 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823247929 DE3247929A1 (en) | 1982-12-24 | 1982-12-24 | PHENOXYPROPIONIC ACID DERIVATIVES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NZ206662A true NZ206662A (en) | 1985-09-13 |
Family
ID=6181692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ206662A NZ206662A (en) | 1982-12-24 | 1983-12-21 | Phenoxypropionic acid derivatives and herbicidal compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0112532A3 (en) |
| JP (1) | JPS59130236A (en) |
| AU (1) | AU2247183A (en) |
| BR (1) | BR8307114A (en) |
| CA (1) | CA1188696A (en) |
| DE (1) | DE3247929A1 (en) |
| DK (1) | DK596683A (en) |
| ES (1) | ES528375A0 (en) |
| GR (1) | GR79442B (en) |
| IL (1) | IL70507A0 (en) |
| NZ (1) | NZ206662A (en) |
| ZA (1) | ZA839551B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PH18417A (en) * | 1981-06-25 | 1985-06-24 | Nihon Tokushu Noyaku Seizo Kk | Substituted phenoxypropionates and herbicidal compositions |
| JPS58183666A (en) * | 1982-04-20 | 1983-10-26 | Nippon Tokushu Noyaku Seizo Kk | Substituted phenoxypropionic ester, intermediate for preparing the same, preparation of said ester and intermediate and herbicide |
-
1982
- 1982-12-24 DE DE19823247929 patent/DE3247929A1/en not_active Withdrawn
-
1983
- 1983-12-12 EP EP83112469A patent/EP0112532A3/en not_active Withdrawn
- 1983-12-16 AU AU22471/83A patent/AU2247183A/en not_active Abandoned
- 1983-12-21 NZ NZ206662A patent/NZ206662A/en unknown
- 1983-12-21 IL IL70507A patent/IL70507A0/en unknown
- 1983-12-22 CA CA000444138A patent/CA1188696A/en not_active Expired
- 1983-12-22 ZA ZA839551A patent/ZA839551B/en unknown
- 1983-12-22 GR GR73347A patent/GR79442B/el unknown
- 1983-12-23 DK DK596683A patent/DK596683A/en not_active Application Discontinuation
- 1983-12-23 ES ES528375A patent/ES528375A0/en active Granted
- 1983-12-23 JP JP58242354A patent/JPS59130236A/en active Pending
- 1983-12-23 BR BR8307114A patent/BR8307114A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0112532A3 (en) | 1985-06-12 |
| DE3247929A1 (en) | 1984-07-12 |
| IL70507A0 (en) | 1984-03-30 |
| EP0112532A2 (en) | 1984-07-04 |
| CA1188696A (en) | 1985-06-11 |
| DK596683D0 (en) | 1983-12-23 |
| ES8502090A1 (en) | 1984-12-16 |
| BR8307114A (en) | 1984-08-07 |
| DK596683A (en) | 1984-06-25 |
| AU2247183A (en) | 1984-06-28 |
| ZA839551B (en) | 1984-08-29 |
| JPS59130236A (en) | 1984-07-26 |
| GR79442B (en) | 1984-10-30 |
| ES528375A0 (en) | 1984-12-16 |
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