CA1246571A - Propionic acid esters - Google Patents
Propionic acid estersInfo
- Publication number
- CA1246571A CA1246571A CA000447244A CA447244A CA1246571A CA 1246571 A CA1246571 A CA 1246571A CA 000447244 A CA000447244 A CA 000447244A CA 447244 A CA447244 A CA 447244A CA 1246571 A CA1246571 A CA 1246571A
- Authority
- CA
- Canada
- Prior art keywords
- signifies
- alkyl
- diethyl
- propionyloxy
- phenoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6539—Five-membered rings
- C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
- C07F9/650994—Six-membered rings having the nitrogen atoms in the positions 1 and 4 condensed with carbocyclic rings or carbocyclic ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
- C07F9/65324—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
Abstract
-a-Abstract The invention is concerned with propionic acid esters of the formula I
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally mono-substituted or multiply substituted phenyl, the optionally present sub-stituents being halogen atoms, C1-4--b-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, a process for their manufacture, weed control compositions which contain these compounds as the active substance as well as the use of such com-pounds or compositions for the control of weeds.
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally mono-substituted or multiply substituted phenyl, the optionally present sub-stituents being halogen atoms, C1-4--b-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, a process for their manufacture, weed control compositions which contain these compounds as the active substance as well as the use of such com-pounds or compositions for the control of weeds.
Description
57~
RaN 6102/40 The invention is concerned with propionic acid esters of the seneral formula Rl 0 3 ~ /OR
A-O--/ O ,o-o-cH-coo-(cH2~ )n (C~2)P \oR4 ~; wherein A signifies one of the following groups (a) or (b) ~ i/ \~ (R) (a) (b) R signlfies hydrogen, halogen, Cl_4-alkyl, trifluoromethyl, Cl 4~alkoxy or Cl_4-alkylthio, X signi~ies oxygen, sulphur or -NR -, Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom, Rl s gnifies hydrogen or Cl 4 alkyl and R signifies hydrogen, Cl_4-alkyl, Cl_4-haloalkyl or optionally mono-substituted or multiply substltuted phenyl, the optionally present sub-stit~en~ being halogen atoms, Cl 4-Pa/30.1.84 ~J~ ~7 al~yl sroups, Cl_4-alkoxy groups and nitro groups, cr Rl and R2 together wlth ~he carbon atom to which ~hey are at~ached signify an o~tionally substituted C5_8-cycloalkane ring, the optionally present substituents being one to three Cl_4-alkyl groups, R and R each independently signify Cl 6-alkyl or phenyl, R signifies hydrogen or Cl 4~alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2.
The compounds of ormula I possess herbicidal prop-exties and are ~uita~l~ as actlve substances of weed con-trol compositions. Accordingly, the invention also in-cludes weed control compositions which contain compounds of formula I as the active substance, a process for the manufacture of these compounds as well as the use of such compounds or compositions for the control of weeds.
In formula I above the term "halogen" embraces fluorine, chlorine, bromine and iodine and the term "Cl_4-haloalkyl" embraces Cl 4-alkyl substituted with one or more halogen atoms. The term "Cl 4-alkyl'l or "Cl 6-alkyl" means not only straight-chain but also branched-chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobut~l, tert.butyl, n-pentyl, isoamyl, neo-pentyl and n-hexyl. This also applies to the alkyl portion of the alkoxy, alkylthio and haloalkyl groups. In the case of multiple substitution the substituents can be the same or different. Where q signifies 2, the symbols R can likewise be the same or different.
The pre~ence of at leas. one asymmetric carbon atom 57~
in the com2ounds of formula I means that ~he compounds can occur in isomeric forms which stand in enantiomeric or diastereomeric relationship ~o one ano~her. The same applies ~o the compounds of formula I in which~ in addition, R3 and R4 have different significances. The separated isomeric forms have optical activity. Accordingly, formula I is intended to embrace the racemates as well as all of the possible isomeric forms.
In the compounds of formula I a ha:Logen atom which may be present is preferably chlorine. Cyclohexane is the preferred C5 ~-cycloalkane group (CRlR2)O
Independently of one another R preferably signifies hydrogen or halogen, especially chlorine; Rl and R2 each preferably slgnify hydrogen, methyl or ethyl; R3 and R4 each preferably signify Cl_4-alkyl; and q pre~erably signi-fies 1.
Furthermore, the D-forms of the compounds o~ formula I
are preferred.
Especially preferred compounds of formula I are:
Diethyl / D-2-[p-(6-chloro-2-quinoxalyloXy)phenoxy]-propionyloxy /methylphosphonate and diethyl r D-~-~p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy 7methylphosphonate.
The process in accordance with the invention for the manufacture of the compounds of formula I comprises a) reacting an acid of the general formula ~2~&57~
A-O--\ O /--O-C~-COOH II
C'~3 wherein A has the significance given above, or a reactive derivative thereof, with an alcohol of the .10 general formula Rl O / OR
lSgl-~CH2)m~~l2n 2 P \oR4 III
h in Rl R2 R3, R4, m, n and p have the significances given above 20and zl signifies hydroxy or a leavlng group, b) reacting a phenol of the general formula A-O- / O ~.-OH IV
30wherein A has the significance given above, or preferably an alkali metaL salt thereof, with a compound of the general formula R / OR
z2_cH-COO-(CH2)m~(l)n (C~2)P \ 4 V
.: 3 57~
wherein R-, ~2, R3, R4, m, n and p have the significances given above and z2 signifies a leaving group (e.g~
chlorine, bromine, iodi.ne, mesylo~y or tosyloxy), or c~ reactlng a halide of he general formula A-Hal VI
wherein A has the significance given above and Hal signifies halogen, especially chlorine, with a phenol of the general formula Rl 0 3 .~ OR
HO--\ O /~-O-CH-COO~(CH2)m~(C)n (C~2)P \ 4 VII
h in Rl R2 R3 R4~ m, n and p have the significances given above, or preferably an alkali metal salt thereof.
Process variant a) is an esterification which can be carried out according to methods known per se; for example, in accordance with the following variants alj, a2) and a3):
Educt ~2~
, al) Free acid of ~ormula II Compound of formula III
35or a sal~ thereof in which Z signifies a leaving group such as chlorine, bromine, iodine, mesyloxy or tosyloxy ~2~ 7~
.
a2) Halide, imldazolide or an~ Compound of formula hydride of an acid of III i~ which zl signifies formula II hydroxy a3) Free acid of formula II Compour.d of formula III
in which 2 signifies hydrox~.
In process variant al) the term "salt" signlfies, for example, an alkali metal salt (e.g. the sodium, potassium or lithium salt), an alkaline ~axth metal salt (e.g. the maynesium, calcium or barium salt), a salt of an organic base (e.g. a mono , di- or trialkylammonium salt or a pyridinium salt) or the ammonium salt. The term 'lleav:Lng group" used in connection ~ith æl preferably stands for chlorine, bromine or iodine.
The esterification of an acid of formula II or, pre~erably, a salt thereof with a compound of formula III
ls pref2rably carried out in an inert diluent and at a temperatuxe of about -10C to 100C. ~ temperature range between 20C and 70C is especially preferred. Inert organic solvents are preferably used as the diluent. Pre-ferred solvents are aliphatic ketones (e.g. ace~one andethyl methyl ketone) and dipolar aprotic solvents (e.g.
dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidone, sulpholane and hexamethylphosphoric acid triamide).
When the free acid of formula II is used, the reaction is conveniently carried out in the presence of a base or an acid acceptor. For this purpose there can be used all customarily usable inorganic and organic acid-binding agents, preferably alkali metal and alkaline earth metal carbonates and bicarbonates and tertiary amines (e.g.
triethylamine, dimethylaniline and pyridine).
The reaction according to process variant a2) is conveniently carried out in an inert diluent such as an ether (e.g. diethyl ether), a hydrocar~on ~e.g. n-hexane, henzene or tolue~e) or a chlorinatPd hydxocarbon ~e.g.
dichloromethane, chloro~orm or carbon te~:rachlorlde) and at room temperature or an eleva~ed temperature (e.g. up to the reflux temperature of the reaction mixtuxe~.
When an acid halide o the acid of formuLa II is used, the reaction is conveniently carried out in the presence of an acid-binding a~ent at about -10C to 30C. 5uitab1e acid-binding agentC are inorganic bases (e.g. alkali m tal and al~aline earth metal carbonates and bicarbonates), but especially organic bases (e.g. tertiary amines, especially triethylamine or pyridine)~ The acid halide is preferably the acid chloride. When t~e anhydride of thQ acid of formula II is used, the reaction i5 conveniently carried out in the presence of an acid-binding agent, especially an organic base such as a tertlary amine (e.g. triethylamine, dimethyi-aniline or pyridine) at a temperature between 0C and 40C, especially at room temperature, or in the absence of an acid-binding agent at an elevated temperature.
In process variant a3), the reaction is conveniently carried out in an inert organic diluent such as an ali-phatic or cyclic ether (e.g. diethyl ether, diisopropylether, 1,2-dimethoxyethane, tetrahydrofuran or dioxan), a chlorinated hydrocarbon (e.g. dichloromethane, chloroform, car~on tetrachloride or trichloroethane) or an aromatic hydrocarbon (e.g. benzene, toluene or a xylene) and at a temperature between 0C and the reflux temperature of the reaction mixture. The reaction is conveniently carried out in the presence of an acid catalyst or a condensing agent such as sulphuric acid, hydrochloric acid, p-toluene-sulphonic acid, dicyclohexylcarbodiimide or carbonyldi-imidazole. Carbonyldiimida201e is preferably used 25the condensing agent a~d in this case the reaction is preferably carried out in the presence of an ether as the diluent. Thus, for example, the acid of for~ula II is 5~
dissolved or suspended in an iner~ organic diluent, especially an alicyclic or cyclic ether, and the solution or suspension is added to a solution or suspension of c~rbonyldiimidazole in the same diluent. After the resulting evolution o~ carbon dioxide has finished ~he mlxture is treated with a solution of ~he alcohol o formula III which has previously been treated wi~h a catalytic amou~t of ~odium or sodium hydride until the hydrogen evolution has finished. The reaction is preferably carried out in a temperature range between room temperature and about 50C and is normally completed within about 2 hours4 The reaction according to process variant b~ is con-veniently carried out in an inert organic qolvent, espec-ially a dipolar aprotic solvent such as dimethylormamide, dimethyl sulphoxide, N-me~hylpyrrolidone, qulpholane or hexamethylphosphoric a~id trlamide. The reaction temp-erature is not critlcal; it preferably lies between 20C
and lS0C, especially between 40C and 80C. The phenol of formula IV is preferably reacted in the form of an alkali metal salt, especially the sodium salt. This can be carried out by reacting the phenoL with the compound of formula V in the presencs of a base such as sodium or potassium hydroxide or ~odium or potassium carbonate. In a further embodiment or this process variant the phenol is reac~ed with the compound of formula V in the presence of an acid-binding agent such as calcium hydroxide, triethyl~
amine or pyridine in a manner known per se.
Process variant c) can be carried out conveniently by convarting the phe~ol of formula VII into an alkali metal salt, ~or example using sodium hydride or potassium hydro-xide with azeotropic removal of water, and subsequently re-acting thesaltwith the halide of formula VI. The last-mentioned reaction step is conveniently carried out in a dipolar aprotic solvent (e.g. dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidone, sulpholane or hexamethyl-phosphoric acid triamide) or in pyridine at a temperature ~2~57~
be~ween 50C and 200C, pre~erably between 80C and 150C.
In a further embodiment o~ this process varian~ the halide is reacted with the phenol itselC in ~he presence of an 5 organic acid-binding agent such as triethylamir.e ox pyri-dine in a manner known per se.
In each case the product obtained can ~e isolated and purified according to methods known per se.
Insofar as no planned synthesis for the isolation of pure isomers is carried out, the product normally results as a mixture o two or more isomers. The isomers can be separated according to methods known per se. If desired, they can also be manufactured by synthesis from correspond-ing optically active starting materials.
The startlng materials of ormulae II, III, IV and VI
as well as reactive derivatives o~ the acids of 0rmul3 II
and the alkali metal salts of the phenols of formula IV are either known or can be produced in a ~anner known per se.
The compounds of formula V used as starting materials in process variant b) are novel; they can be produced, for example, in accordance with ~he following Reaction Scheme:
57~L
Z~-C~ COOH
S
C~3 VIII
so~l2 R _ oR3 Z2_lH. COCl + ~o-(CX2)m (C)n ( 2 P \ oR4 IX (Acid-binding agent) III' R O / OR
Z~-C -COO-(I ~2)m (l)~ 2 P \oR4 In the above Reaction Scheme Rl, R2, R3, R4, m, n~ p and Z have the signlficances given above. The reaction conditions are familiar to the person skilled Ln the art.
The phenols of formula VII and their alkali metal salts used as starting materials in process variant c) are also novel; they can be produced, fox example, as illu-strated in the following Reaction Scheme:
~.2~57~
o ~ o o o~v ~
=~ o '0~ 0. ~ ' ~
~, ~/
O O ~ er o, o=~
. ,_~
. ,,~
~-1 _ ' U .
Q ~ O
u~ O Q ~ ~
\ / ~o --O ~ ~ 0=~
~ Q~ Y
_ _I _ O O
C~ ~ .~ / . ,. _ ~ U E~ ~ , o ~ O
V _ O ~
a ,~ ~ , u o~ + ~
Ci ~ O ~0 ~ ~ I I / T ~ ~ y--:~ ~ O = ~ I f-`) I , ~ ~ O
U~ / x _ C) I / \
S ~0 o ~ 0 . O I T ~ ~ ) H
\./ g ,., ~ 3r) 0 i ?.~57~
In Ihe above Reaction Scheme Rl, R2, R , R4, m, n, p and z2 have the significances given above and R6 signi~ies methyl or benzyl. The reaction conditions are familiar to the person skilled in the art; for the final step ~J
(R6 = CH3) _ VII (ether cleavage) reference is made especially to J. Org. Chem. 44, 1247-1251 (1979).
The compounds of formula I possess herbicidal prop-ertles and are especially suitable for the control ofweeds, especially of slender fox~ail (Alopecurus myosuroides) and types of millet such as, for example, coc~ls foot (Echinochloa crus-galli), great oxtail millet (Setaria faberii) and hair-like millet (Panicum capillare) in cereals, especially barley, oats and wheat plantations, as well as ln rice, cotton, soya, sugar beet and vegetable plantations. The compounds in accordance with the ln-vention are particularly suitable for the control of weeds in cotton, soya and sugar beet plantations.
In general t a concentration of 10-100 g o~ active substance of formula I/ha, preferably 20-50 g of active substance of formula I/ha, is sufficient to produce the desired her~icidal effect.
The compounds of formula I are not only pre-emergence herbicides but also post-emergence herbicides.
The weed controL composition in accordance with the invention contains an efective amount of at least one compound of formula I, as defined above, as well as form-ulation adjuvants. The composition conveniently contains at least one of the fGllowing formulation adjuvants:
solid carrier substances; solvents or dispersion medla;
tensides (wetting and emulsifying agents); dispersing agents (without tenside action); and stabilizers. With the use of these and other adjuvants the compounds of formula I, namely the herbicidal active substances, can be converted 57~L
into the usual formulations such as dusts, pcwders, gran-ulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and ~he li~e.
The compounds of formula I are generally insoluble in water and can be formulated according to ~.he methods which are usual for water-insoluble compounds using the respective formulation adjuvants. The manufacture of the composltions can be carried out in a manner known per se;
for example, by mixing the xespective active substance with solid carrier substances, by dissolution or suspension in quitable solvents or dispersion media, lf necessary using tensides as wetting or emulsifying agents and/or dispersing agents, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.
As solid carrier substances there essentially come into consideration: natural mlneral substances such as chalk, dolomite, limestone, aluminas and silicic acid and salts thereof (e.g. siliceous earth, kaolin, bentonite, talc, attapulgite and montmorillonite); synthetic mi~eral substances such as highly dispersible silicic acid, alumin-ium oxide and silicates; organic substances such as cel-lulose, starch, urea and synthetic resins; and fertilizerssuch as phosphates and nitrates, whereby such carrier sub-stances can be present, for example, as powders or as gran-ulates.
As solvents or di~persion media there essentially come into consideration: aromatics such as benze~e, toluene, xylenes and alkylnaphthalenes~ chloxinated aro-matics and ch1Orinated aliphatic hydrocarbons such as chloro-benzenesl chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. pet-roleum fractions); alcohols such as butanol and glycol, as well as their ethers and esters; ketones such as ace-tone, methyl e~hyl ketone, methyl isobutyl ketone and cyclo-~J~ 57 hexanone; and strongly polar solvents or d~ spersion medla such a~ dimethylformamide, N-methylpyrrolidone and dimethyl sulphoxide, such solvents preferably having flash points of s at least 30C and boiling points o~ at least 50C, and water. Among the solvents or dispersion media there also come into consideration so-called liquifiad gaseous extend-ers or carrier substances, these being products w~ich are gaseous at room temperature and under normal pressure.
Examples of such products are especially aerosol propellan.s such as halogenated hydrocarbons (e.g. dichlorodifluoro-methane). If the weed control com~osition in accordance with the invention is present in the form of a pressurized pack, then a solvent is conveniently used in addition to the propellant.
The tensides (wetting and emulsifying agents) can be non-ionic compounds such as condensation products o~ fatty ac~ds, fatty alcohols or fatty~substituted phenols with ethylene oxide; fatty acid esters and ethers o~ sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamlne oxides.
The tensides can also be anionic compounds such as soaps; fatty sulphate esters (e.g. dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate);
alkyl sulphonates, aryl sulphonates and fatty-aromatic sulphonates such as alXylbenzene sulphonates (e.g. calcium dodecylbenzene sulphonate) and butylnaphthalene sulphonates;
and more ccmplex fatty sulphonates, for example the amide condensation Products of oleic acid and N~methyltaurine and the sadium sulphonate of dioctyl succinate.
Finally, the tensides can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethyl-ammonium chlorides, alXyltrimethylammonium chlorides and ethoxylated ~uaternary ammoniu~ chlorides.
~.?,'Y,~57~
As dispersing agents (wi~hout tenside action) thers essentially come into consi deration: lignin, sodium and ammonium salts of lignin sulphonic acids, sodium salts o maleic anhydride-diisobutylene copolymers, sodium and ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphite lyes.
As dispersing agents, which are especially suitable as thickening or anti-settling agents, there can be used, for example, methylcellulose, carboxyme~ylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.
lS Ex~nples of suitable stabilizers are acid-binding agents (e.g. epichlorohydrin, phenyl glycidyl ether and soya epoxides); antioxidants (e.g. gallic acid esters and butylhydroxytoluene); UV-absorbers (e.g. substituted benzo-phenones, diphenylacrylonitrile acid esters and cinnamlc acid esters); and deactivators ~e.g. salts of ethylenedi-aminotetraacetic acid and polyglycols).
The weed control compositions in accordance with the in~ention can contain, in addition ~o the compounds or formula I, synergists and other active substances ~e.g. in-secticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for intensifying the activity or for broadening the spectrum of activity.
The weed control compositions in accordance with the invention generally contain between 0.001 and 95 weight percent, pre~erably between 5 and 75 weight percent, of one or more compounds of formula I as the active substance(s).
They can be present, for example, in a form which is suitable .or storage and transport. In such formulations (e.g.
emulsifiable concentrates) the active substance concen-tration is normally in the higher range, preferably between lO and 75 weight percent, especially between 25 and 50 7~
weight percent. These formulations can then be diluted, for example with the same or dif~erent inert substances, to give activ~ substance concentrations which are suitable for practical use, i.e. preferably about 0.1 to 10 weight per-cent, especially about 1 to 5 weight percent~ The active substance concentrations can~ however, also be smaller or greater.
As mentioned above, the manufacture of the weed con-trol compositions in accordance with th~ in~ention can be carried out in a manner known ~er se.
For the manufacture of pulverous preparations the active substance, i.e. at least one compound of formula I, can be mixed with solid carrier substance ~e.g. by grlnd-ing together) or the solid carrier substance can be im-pregnated with a solution or suspensio~ o~ the active sub-stance and then the solvent or dispersion medium can be removed by evaporation, heating or sucking-off under reduced pressure. By adding tensides or dispersing agents such pulverous preparations can be made readily wettable with water, so that they can be converted into aqueous suspen-sions which are suitable, or example, as spray compositions.
The compound of formula I can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is d~spersible in water or it can be mixed with a so~id pre-granulated carrier substance to form a product in the form of a granulate.
When desired, the compound of formula I can be dis-solved in a water-immiscible solvent ~uch as, for example, a high-boiling hydrocarbon, which conveniently contains dissolved emulsifying agent, so that the solution becomes self-emulsifying upon addition to water. Alternatively, the active subs~ance can be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concen~ration. Moreover, the active substance can - 17 ~
be dissolved in a solvent and thereafter the solution can be mixed with an em~lsifying agent~ Such a mixture can like~ise be diluted wi~h water to the desired concentration~
In this manner there are obtained emulsiiab1e concentrates or ready-for-use emulsions.
The use of the weed con~rol compositions in accordance with the invention can be carried out according ~o usual application methods such as sprinkling, spra~ing, dusting, watering or scattering. The method in accordance with tha invention for the control of weeds comprises treating the locus to be protected against weeds and/or the weeds with a compound in accordance with the invention or a weed control composition in accordance with the invention.
~2~ 57~
The following Exa~ples illustrate the invention in more detail:
I Manufacture of the active substances of ~ormula I:
Exam~le 1 A solution of 2.37 g ~ pyridine in 10 ml of dichloro-methane is added dropwise while stirring to a solutior., cooled to 0C, of 10.53 g Qf D-2-[p-(6-chloro 2-quinoxalyl-oxy)phenoxy]-propionyl chloride and 4.88 g of dieth~l hydrox~methylphosphonate in 50 ml o~ dichloromethane. The mixture is stirred at room temperature for l hour and sub-sequently evaporated to dryness under reduced pressure.
Therea~ter ~he residue ls dlssolved in ethyl acetate and ~he solution i9 extracted with water and dilute sodium bicarbonate solution, dried over a drying agent and evaporated to dryness.
The residue is purified by chromatography on silica gel with dichloromethane/diethyl ether (7:1). There is obtained diethyl ~ D-2-~p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy 7methylphosphonate; [a]D ~ 34.67 (c = 0.93%
i~ CXC13).
In an analogous mannar, from D-2-~p-(6-fluoro-2 quinoxalyloxy)phenoxy]-propionyl chloride and diethyl hydroxymethylphosphonate there is obtained diethyl / D-2-[p~(6-fluoro-2-quinoxalyloxy)phenoxy]-propionyloxy 7methylphosphonate, ~a]20 + 28.08 (c = 1.14%
i~ C~C13);
from D-2-[p-(6~7-dichloro-2-quinoxalyloxy)phenoxy~-propionyl chloride and diethyl 2-hydroxyethylphosphonate there is obtained diethyl 2-r D-2-[p-(6,7 dichloro-2-; quinoxalyloxy)phenoxy]-propionyloxy 7-ethylphosphonate, E~] ~ ~ 32.08 (c = 0.95% in CHC13);
5~
from D-2-[p-(6,7-dichloro-2-quinoxalyloxy)phenoxyj-pro-pionyl chloride and diethyl hydroxyme~hylphosphonate there is obtained diethyl / D-2- [p- ~6, 7~dichloro-2-qulnoxalyloxy) -phenoxy]-propionylo~xy_7methylphosphonate, ~]20 ~ 35.67 (c - 1.00~ in CHC13);
rom D-2-[p-(i,6-dichloro-2-quinoxalyloxy)phenoxy]-propion-yl chloride and diethyl 2~hydroxyethylphosphona~e th~re is obtained diethyl 2-/ D-2-Lp-(5,6-dlchloro--2-quincxalyloxy)-phenoxy]-propionyloxy /-e~hylphosphonate, [a]20 + 27.69 ( c = 1 ~ 07% in CHC13 );
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy~-propionyl chloride and diethyl DL-l-hydroxy~thylphosphonats there is obtained diethyl DL-l-~ D-2-[p-(6-chloro-2-quinoxalylcxy)-phenoxy]-propionyloxy 7-ethylphosphonate, [a]20 + 26.80 (c = 1.10% in CHC13);
from D-2-[p-t6-chloro-2-~uinoxalyloxy)phenoxy]-propionyl chloride and diethyl 2-hydroxyethylphosphonate there is obtained diethyl 2- r D-2-[p-(6-chloro-2-quinoxalyloxy)-phenoxy]-propionyloxy 7-ethylphosphonate, []D0 +27.92 (c = 1.04~ in CHC13);
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyl chloride and dibutyl hydroxymethylphosphonate there is obtained dibutyl / D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy /methylphosphonate, [a]20 + 33.11 (c = 1.06 in CHC13~i ,;""s~
-.L~)57 from D 2-[p~(6-chloro~2-quinolyloxy)phenoxy]-prooionyl chloride and diethyl hydroxymetnylphosphonate there is obtained diethyl / D-2-[p-( 6-chloro-2-qu:inolylo~y) phenoxy3 -propionyloxy 7methylphosphonate, [~]20 ~34.24 ~c = 1.03~ in C~C13);
from D-2-~p-(6-chloro-2-quinolyloxy)phenoxy]-propionyl chloride and diethyl DL-l-hydroxyethylphosphonate there is 10 obtained diethyl DL-l-/ D-2- [p- (6-chloro 2-quinolyloxy)-phenoxy]-propionyloxy 7-ethylphosphonate, ~a]20 ~30,550 (c = 1.02% in CHC13); and from D-2~[p-(6-chloro-2-quinolyloxy~phenoxy]-propionyl chloride and diethyl 2-hydro~yethylphosphonate there is obtain~ldiethyl 2-/ D-2-~p-(6-chloro-2-qulnolyloxy)-phenoxy]-pro~lonyloxy 7-ethylphosphonate, ~a~20 ~ 27.39 (c = 1.02% ln C~Cl3).
Example 2_ A solution of 10.29 g of D-2-[p-(6-chloro-2-quinolyl-oxy)phenoxy]-propionic acid in 50 ml of absolute dimethyl-formamide is added dropwise at room temperature to a sus-pension of 1.37 g of a 55~ sodium hydride dispersion in150 ml of absolute dimethylformamide and the mixture is stirred at 50C for 30 minutes. A solution of 8.16 g of diethyl 3-bromopropylphosphonate in 10 ml of absolute di-methylformamide is subsequently added thereto and the mixture is stirred at room temperature for 3 hours. The mixture is then adjusted to pH 5-6 with 2N hydrochloxic acid. The sol~ent is then distilled of at 50C under reduced pressure a~d the residue is treated with 200 ml of ethyl acetate and extracted three times with 100 ml of water each time. The organic phase is dried over anhydrous sodium sulphate and evaporated to dry~ess under reduced pressureO The residue is purified by chromatography on silica gel with dichloromethane/ethyl acetate (3:1).
- 21 ~ 5~
There is obtained diethyl 3~/ D-2-[p-~6~chlors~2-quinolyl oxy)phenoxy]-propionyloxy 7-propylphosphonate, [~120 1 29.08 tc = 0.83% in C~C13).
s Example 3 a) 24.42 g of L~2-~p toluenesulphonyloxy)-propionic acid are heated to boiling for 4 hours with 59.5 g of thio~yl chloride and the mixture is subsequently evaporated to dryness under reduced pressure. The residue is dissolved in 150 ml of dichloromethane and treated at room temperature with 16.82 g of die~hyl hydroxymethylphosphonate. The mixture is then cooled to 0-5C while s~irring and treated dropwise during 15 minutes with a solution of 8.70 g o~
pyridine in 25 ml o~ dichloromethane. The mixture is subsequently stirred at room temperature for 3 hours and the solvent is distilled of~ under rPduced pressure. The residue is dissolved in ethyl acetate, the solution is washed wlth water and the organic phase is dried o~er anhydrous sodium sulphate and evaporated. The resulting residue is purified by chromatography on silica gel with diethyl ether and subsequently distilled in a bulb-tube.
Th~re is ob~ained diethyl ~L-2-~p-toluenesulphonyloxy)-propionyloxy]methylphosphonate, b.p. abou~ 210C/0.05 mm~g,[a~20 -30.32 (c = l.lO~ in C~C13).
b) 2.72 g of p-~6-chloro-2-quinoxalyloxy)-phenol are added to a suspension of 0.43 g of a 55~ sodium hydride dispersion in 25 ml of dimethylformamide and the mixture is stirred at room temperature for 2 hours. A solution of 3,94 g of diethyl [~-2-(p-toluenesulphonyloxy) propionyloxy~
methylphosphonate in 15 ml of dimethylformamide is added dropwise during lO minutes and the mixture is stirred at room temperature for 3 hours and subsequently evaporated under reduced pressure. The residue is then dissolved in ethy} acetate, the solution is washed with water and the organic phase is dried over anhydrous sodium sulphate and evaporated under reduced pressure. The resulting residue is purified by chromatography on silica gel with die~hyl ether, There is obtained diethyl / D-2-[p-~6-chloro-2-quin-oxalyloxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20 ~33.21 (c = 1.06~ in CHC13).
a) 46 g of D-2 (p-benzyloxyphenoxy)-propionic acid are stirred at 90C for 2 hours with 110 ml Qf thionyl chloride~
The mixture is subsequently evaporated to dryness under reduced pressure, the residue is dissolved in 190 ml of di~hloromethane and the solution is treated at room temp-erature with 29.4 g of diethyl hydroxymethylphosphonate~
The mlxture is cooled to 5-10C while stirring and treated dropwise during 20 minutes with a.soLution of 14.22 g o~
pyridine in 20 ml of dichloromethane. The mlxture is then stirred at room temperature ~or a further 30 minutes, washed in sequence with 2N hydrochloric acid, 2N sodium hydroxide solution and water, dried over anhydrous sodium sulphate and evaporated to dryness. The residue is purified by chromatography on silica gel with ethyl acetate/
n-hexane (3:1).
There is obtained diethyl ~D-2-(p~benzyloxyphenoxy)-propionyloxy]methylphosphonate, [a]20 1 36.04 (c = 1.07 in CHC13), ~ = 1.5304.
b) 10 g of diethyl [D-2-(p-benzyloxyphenoxy) propionyl-oxy]methylphosphonate are dissolved in 150 ml of methanol and 1 g of pall~dium/active carbon (10% Pd) is added to the solution. The mixture is hydrogenated at normal pressure and room temperature for 20 hours, the catalyst is subsequently filtered off and the filtrate is evaporated to dryness under reduce pressure. The residue is purified . by chromatography on silica gel with ethyl acetate/~-hexane (2~
57~L
There is obtained diethyl ~D~2 (p-hydroxypheno~y)-propionyloxy]methylphosphonate, [a]20 ~39.40o (c = 1.00%
in CXCl3), nD = 1.5033.
c~ A solution of 2 g of diethyl [D-2-(p-hydroxyphenoxy)-propionyloxy~methylphosphonate in 25 ml of dimethyl sul-phoxide is treated wi~h 0.14 g of sodium hydride and the mixture is stirred at room temperature ror 30 minutes.
A solution of l.Ol g o 2-chlorobenzthiaæole in lO ml of dimethyl sulphoxide is subsequently added dropwise thereto during 5 minutes and the mixture is stirred at 95C for 12 hours. The mixture ~s then poured on to lO0 ml of ice-water and extracted with ethyl acetate. The organic phase is washed with water~ dried over anhydrous sodium sulphate and evaporated under reduced pressure. The residue is puriied by chromatography on silica gel with ethyl acetate~
n-hexane (2:l).
There is obtained diethyl r D-2-[p-(2-benzthiazolyl-oxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20 +9~06 (c = 0.89~ in CHCl3).
In an analogous manner, from diethyl ~D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-phosphonate and 2,5-dichlorobenzthiazole there is obtained diethyl / D-2-[p-~5-chloro-2-benzthiazolyloxy)phenoxy]-propio~yloxy_7methylphosphonate, [a]D ~18.00 (c = l.06 in CHCl3); and from diethyl [D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-phosphonate and 2,4,6-trichlorobenzthiazole there is ob-tained diethyl / D-2 ~p-(4~6-dichloro-2-benzthiazolylo~y)-phenoxy]-propionyloxy /methylphosphonate, [a]D 119.47 (c - 0.76~ in CHCl3).
~?71~7
RaN 6102/40 The invention is concerned with propionic acid esters of the seneral formula Rl 0 3 ~ /OR
A-O--/ O ,o-o-cH-coo-(cH2~ )n (C~2)P \oR4 ~; wherein A signifies one of the following groups (a) or (b) ~ i/ \~ (R) (a) (b) R signlfies hydrogen, halogen, Cl_4-alkyl, trifluoromethyl, Cl 4~alkoxy or Cl_4-alkylthio, X signi~ies oxygen, sulphur or -NR -, Y signifies the methine group, i.e.
the group -CH=, or a nitrogen atom, Rl s gnifies hydrogen or Cl 4 alkyl and R signifies hydrogen, Cl_4-alkyl, Cl_4-haloalkyl or optionally mono-substituted or multiply substltuted phenyl, the optionally present sub-stit~en~ being halogen atoms, Cl 4-Pa/30.1.84 ~J~ ~7 al~yl sroups, Cl_4-alkoxy groups and nitro groups, cr Rl and R2 together wlth ~he carbon atom to which ~hey are at~ached signify an o~tionally substituted C5_8-cycloalkane ring, the optionally present substituents being one to three Cl_4-alkyl groups, R and R each independently signify Cl 6-alkyl or phenyl, R signifies hydrogen or Cl 4~alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2.
The compounds of ormula I possess herbicidal prop-exties and are ~uita~l~ as actlve substances of weed con-trol compositions. Accordingly, the invention also in-cludes weed control compositions which contain compounds of formula I as the active substance, a process for the manufacture of these compounds as well as the use of such compounds or compositions for the control of weeds.
In formula I above the term "halogen" embraces fluorine, chlorine, bromine and iodine and the term "Cl_4-haloalkyl" embraces Cl 4-alkyl substituted with one or more halogen atoms. The term "Cl 4-alkyl'l or "Cl 6-alkyl" means not only straight-chain but also branched-chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobut~l, tert.butyl, n-pentyl, isoamyl, neo-pentyl and n-hexyl. This also applies to the alkyl portion of the alkoxy, alkylthio and haloalkyl groups. In the case of multiple substitution the substituents can be the same or different. Where q signifies 2, the symbols R can likewise be the same or different.
The pre~ence of at leas. one asymmetric carbon atom 57~
in the com2ounds of formula I means that ~he compounds can occur in isomeric forms which stand in enantiomeric or diastereomeric relationship ~o one ano~her. The same applies ~o the compounds of formula I in which~ in addition, R3 and R4 have different significances. The separated isomeric forms have optical activity. Accordingly, formula I is intended to embrace the racemates as well as all of the possible isomeric forms.
In the compounds of formula I a ha:Logen atom which may be present is preferably chlorine. Cyclohexane is the preferred C5 ~-cycloalkane group (CRlR2)O
Independently of one another R preferably signifies hydrogen or halogen, especially chlorine; Rl and R2 each preferably slgnify hydrogen, methyl or ethyl; R3 and R4 each preferably signify Cl_4-alkyl; and q pre~erably signi-fies 1.
Furthermore, the D-forms of the compounds o~ formula I
are preferred.
Especially preferred compounds of formula I are:
Diethyl / D-2-[p-(6-chloro-2-quinoxalyloXy)phenoxy]-propionyloxy /methylphosphonate and diethyl r D-~-~p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy 7methylphosphonate.
The process in accordance with the invention for the manufacture of the compounds of formula I comprises a) reacting an acid of the general formula ~2~&57~
A-O--\ O /--O-C~-COOH II
C'~3 wherein A has the significance given above, or a reactive derivative thereof, with an alcohol of the .10 general formula Rl O / OR
lSgl-~CH2)m~~l2n 2 P \oR4 III
h in Rl R2 R3, R4, m, n and p have the significances given above 20and zl signifies hydroxy or a leavlng group, b) reacting a phenol of the general formula A-O- / O ~.-OH IV
30wherein A has the significance given above, or preferably an alkali metaL salt thereof, with a compound of the general formula R / OR
z2_cH-COO-(CH2)m~(l)n (C~2)P \ 4 V
.: 3 57~
wherein R-, ~2, R3, R4, m, n and p have the significances given above and z2 signifies a leaving group (e.g~
chlorine, bromine, iodi.ne, mesylo~y or tosyloxy), or c~ reactlng a halide of he general formula A-Hal VI
wherein A has the significance given above and Hal signifies halogen, especially chlorine, with a phenol of the general formula Rl 0 3 .~ OR
HO--\ O /~-O-CH-COO~(CH2)m~(C)n (C~2)P \ 4 VII
h in Rl R2 R3 R4~ m, n and p have the significances given above, or preferably an alkali metal salt thereof.
Process variant a) is an esterification which can be carried out according to methods known per se; for example, in accordance with the following variants alj, a2) and a3):
Educt ~2~
, al) Free acid of ~ormula II Compound of formula III
35or a sal~ thereof in which Z signifies a leaving group such as chlorine, bromine, iodine, mesyloxy or tosyloxy ~2~ 7~
.
a2) Halide, imldazolide or an~ Compound of formula hydride of an acid of III i~ which zl signifies formula II hydroxy a3) Free acid of formula II Compour.d of formula III
in which 2 signifies hydrox~.
In process variant al) the term "salt" signlfies, for example, an alkali metal salt (e.g. the sodium, potassium or lithium salt), an alkaline ~axth metal salt (e.g. the maynesium, calcium or barium salt), a salt of an organic base (e.g. a mono , di- or trialkylammonium salt or a pyridinium salt) or the ammonium salt. The term 'lleav:Lng group" used in connection ~ith æl preferably stands for chlorine, bromine or iodine.
The esterification of an acid of formula II or, pre~erably, a salt thereof with a compound of formula III
ls pref2rably carried out in an inert diluent and at a temperatuxe of about -10C to 100C. ~ temperature range between 20C and 70C is especially preferred. Inert organic solvents are preferably used as the diluent. Pre-ferred solvents are aliphatic ketones (e.g. ace~one andethyl methyl ketone) and dipolar aprotic solvents (e.g.
dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidone, sulpholane and hexamethylphosphoric acid triamide).
When the free acid of formula II is used, the reaction is conveniently carried out in the presence of a base or an acid acceptor. For this purpose there can be used all customarily usable inorganic and organic acid-binding agents, preferably alkali metal and alkaline earth metal carbonates and bicarbonates and tertiary amines (e.g.
triethylamine, dimethylaniline and pyridine).
The reaction according to process variant a2) is conveniently carried out in an inert diluent such as an ether (e.g. diethyl ether), a hydrocar~on ~e.g. n-hexane, henzene or tolue~e) or a chlorinatPd hydxocarbon ~e.g.
dichloromethane, chloro~orm or carbon te~:rachlorlde) and at room temperature or an eleva~ed temperature (e.g. up to the reflux temperature of the reaction mixtuxe~.
When an acid halide o the acid of formuLa II is used, the reaction is conveniently carried out in the presence of an acid-binding a~ent at about -10C to 30C. 5uitab1e acid-binding agentC are inorganic bases (e.g. alkali m tal and al~aline earth metal carbonates and bicarbonates), but especially organic bases (e.g. tertiary amines, especially triethylamine or pyridine)~ The acid halide is preferably the acid chloride. When t~e anhydride of thQ acid of formula II is used, the reaction i5 conveniently carried out in the presence of an acid-binding agent, especially an organic base such as a tertlary amine (e.g. triethylamine, dimethyi-aniline or pyridine) at a temperature between 0C and 40C, especially at room temperature, or in the absence of an acid-binding agent at an elevated temperature.
In process variant a3), the reaction is conveniently carried out in an inert organic diluent such as an ali-phatic or cyclic ether (e.g. diethyl ether, diisopropylether, 1,2-dimethoxyethane, tetrahydrofuran or dioxan), a chlorinated hydrocarbon (e.g. dichloromethane, chloroform, car~on tetrachloride or trichloroethane) or an aromatic hydrocarbon (e.g. benzene, toluene or a xylene) and at a temperature between 0C and the reflux temperature of the reaction mixture. The reaction is conveniently carried out in the presence of an acid catalyst or a condensing agent such as sulphuric acid, hydrochloric acid, p-toluene-sulphonic acid, dicyclohexylcarbodiimide or carbonyldi-imidazole. Carbonyldiimida201e is preferably used 25the condensing agent a~d in this case the reaction is preferably carried out in the presence of an ether as the diluent. Thus, for example, the acid of for~ula II is 5~
dissolved or suspended in an iner~ organic diluent, especially an alicyclic or cyclic ether, and the solution or suspension is added to a solution or suspension of c~rbonyldiimidazole in the same diluent. After the resulting evolution o~ carbon dioxide has finished ~he mlxture is treated with a solution of ~he alcohol o formula III which has previously been treated wi~h a catalytic amou~t of ~odium or sodium hydride until the hydrogen evolution has finished. The reaction is preferably carried out in a temperature range between room temperature and about 50C and is normally completed within about 2 hours4 The reaction according to process variant b~ is con-veniently carried out in an inert organic qolvent, espec-ially a dipolar aprotic solvent such as dimethylormamide, dimethyl sulphoxide, N-me~hylpyrrolidone, qulpholane or hexamethylphosphoric a~id trlamide. The reaction temp-erature is not critlcal; it preferably lies between 20C
and lS0C, especially between 40C and 80C. The phenol of formula IV is preferably reacted in the form of an alkali metal salt, especially the sodium salt. This can be carried out by reacting the phenoL with the compound of formula V in the presencs of a base such as sodium or potassium hydroxide or ~odium or potassium carbonate. In a further embodiment or this process variant the phenol is reac~ed with the compound of formula V in the presence of an acid-binding agent such as calcium hydroxide, triethyl~
amine or pyridine in a manner known per se.
Process variant c) can be carried out conveniently by convarting the phe~ol of formula VII into an alkali metal salt, ~or example using sodium hydride or potassium hydro-xide with azeotropic removal of water, and subsequently re-acting thesaltwith the halide of formula VI. The last-mentioned reaction step is conveniently carried out in a dipolar aprotic solvent (e.g. dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidone, sulpholane or hexamethyl-phosphoric acid triamide) or in pyridine at a temperature ~2~57~
be~ween 50C and 200C, pre~erably between 80C and 150C.
In a further embodiment o~ this process varian~ the halide is reacted with the phenol itselC in ~he presence of an 5 organic acid-binding agent such as triethylamir.e ox pyri-dine in a manner known per se.
In each case the product obtained can ~e isolated and purified according to methods known per se.
Insofar as no planned synthesis for the isolation of pure isomers is carried out, the product normally results as a mixture o two or more isomers. The isomers can be separated according to methods known per se. If desired, they can also be manufactured by synthesis from correspond-ing optically active starting materials.
The startlng materials of ormulae II, III, IV and VI
as well as reactive derivatives o~ the acids of 0rmul3 II
and the alkali metal salts of the phenols of formula IV are either known or can be produced in a ~anner known per se.
The compounds of formula V used as starting materials in process variant b) are novel; they can be produced, for example, in accordance with ~he following Reaction Scheme:
57~L
Z~-C~ COOH
S
C~3 VIII
so~l2 R _ oR3 Z2_lH. COCl + ~o-(CX2)m (C)n ( 2 P \ oR4 IX (Acid-binding agent) III' R O / OR
Z~-C -COO-(I ~2)m (l)~ 2 P \oR4 In the above Reaction Scheme Rl, R2, R3, R4, m, n~ p and Z have the signlficances given above. The reaction conditions are familiar to the person skilled Ln the art.
The phenols of formula VII and their alkali metal salts used as starting materials in process variant c) are also novel; they can be produced, fox example, as illu-strated in the following Reaction Scheme:
~.2~57~
o ~ o o o~v ~
=~ o '0~ 0. ~ ' ~
~, ~/
O O ~ er o, o=~
. ,_~
. ,,~
~-1 _ ' U .
Q ~ O
u~ O Q ~ ~
\ / ~o --O ~ ~ 0=~
~ Q~ Y
_ _I _ O O
C~ ~ .~ / . ,. _ ~ U E~ ~ , o ~ O
V _ O ~
a ,~ ~ , u o~ + ~
Ci ~ O ~0 ~ ~ I I / T ~ ~ y--:~ ~ O = ~ I f-`) I , ~ ~ O
U~ / x _ C) I / \
S ~0 o ~ 0 . O I T ~ ~ ) H
\./ g ,., ~ 3r) 0 i ?.~57~
In Ihe above Reaction Scheme Rl, R2, R , R4, m, n, p and z2 have the significances given above and R6 signi~ies methyl or benzyl. The reaction conditions are familiar to the person skilled in the art; for the final step ~J
(R6 = CH3) _ VII (ether cleavage) reference is made especially to J. Org. Chem. 44, 1247-1251 (1979).
The compounds of formula I possess herbicidal prop-ertles and are especially suitable for the control ofweeds, especially of slender fox~ail (Alopecurus myosuroides) and types of millet such as, for example, coc~ls foot (Echinochloa crus-galli), great oxtail millet (Setaria faberii) and hair-like millet (Panicum capillare) in cereals, especially barley, oats and wheat plantations, as well as ln rice, cotton, soya, sugar beet and vegetable plantations. The compounds in accordance with the ln-vention are particularly suitable for the control of weeds in cotton, soya and sugar beet plantations.
In general t a concentration of 10-100 g o~ active substance of formula I/ha, preferably 20-50 g of active substance of formula I/ha, is sufficient to produce the desired her~icidal effect.
The compounds of formula I are not only pre-emergence herbicides but also post-emergence herbicides.
The weed controL composition in accordance with the invention contains an efective amount of at least one compound of formula I, as defined above, as well as form-ulation adjuvants. The composition conveniently contains at least one of the fGllowing formulation adjuvants:
solid carrier substances; solvents or dispersion medla;
tensides (wetting and emulsifying agents); dispersing agents (without tenside action); and stabilizers. With the use of these and other adjuvants the compounds of formula I, namely the herbicidal active substances, can be converted 57~L
into the usual formulations such as dusts, pcwders, gran-ulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and ~he li~e.
The compounds of formula I are generally insoluble in water and can be formulated according to ~.he methods which are usual for water-insoluble compounds using the respective formulation adjuvants. The manufacture of the composltions can be carried out in a manner known per se;
for example, by mixing the xespective active substance with solid carrier substances, by dissolution or suspension in quitable solvents or dispersion media, lf necessary using tensides as wetting or emulsifying agents and/or dispersing agents, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.
As solid carrier substances there essentially come into consideration: natural mlneral substances such as chalk, dolomite, limestone, aluminas and silicic acid and salts thereof (e.g. siliceous earth, kaolin, bentonite, talc, attapulgite and montmorillonite); synthetic mi~eral substances such as highly dispersible silicic acid, alumin-ium oxide and silicates; organic substances such as cel-lulose, starch, urea and synthetic resins; and fertilizerssuch as phosphates and nitrates, whereby such carrier sub-stances can be present, for example, as powders or as gran-ulates.
As solvents or di~persion media there essentially come into consideration: aromatics such as benze~e, toluene, xylenes and alkylnaphthalenes~ chloxinated aro-matics and ch1Orinated aliphatic hydrocarbons such as chloro-benzenesl chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. pet-roleum fractions); alcohols such as butanol and glycol, as well as their ethers and esters; ketones such as ace-tone, methyl e~hyl ketone, methyl isobutyl ketone and cyclo-~J~ 57 hexanone; and strongly polar solvents or d~ spersion medla such a~ dimethylformamide, N-methylpyrrolidone and dimethyl sulphoxide, such solvents preferably having flash points of s at least 30C and boiling points o~ at least 50C, and water. Among the solvents or dispersion media there also come into consideration so-called liquifiad gaseous extend-ers or carrier substances, these being products w~ich are gaseous at room temperature and under normal pressure.
Examples of such products are especially aerosol propellan.s such as halogenated hydrocarbons (e.g. dichlorodifluoro-methane). If the weed control com~osition in accordance with the invention is present in the form of a pressurized pack, then a solvent is conveniently used in addition to the propellant.
The tensides (wetting and emulsifying agents) can be non-ionic compounds such as condensation products o~ fatty ac~ds, fatty alcohols or fatty~substituted phenols with ethylene oxide; fatty acid esters and ethers o~ sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamlne oxides.
The tensides can also be anionic compounds such as soaps; fatty sulphate esters (e.g. dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate);
alkyl sulphonates, aryl sulphonates and fatty-aromatic sulphonates such as alXylbenzene sulphonates (e.g. calcium dodecylbenzene sulphonate) and butylnaphthalene sulphonates;
and more ccmplex fatty sulphonates, for example the amide condensation Products of oleic acid and N~methyltaurine and the sadium sulphonate of dioctyl succinate.
Finally, the tensides can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethyl-ammonium chlorides, alXyltrimethylammonium chlorides and ethoxylated ~uaternary ammoniu~ chlorides.
~.?,'Y,~57~
As dispersing agents (wi~hout tenside action) thers essentially come into consi deration: lignin, sodium and ammonium salts of lignin sulphonic acids, sodium salts o maleic anhydride-diisobutylene copolymers, sodium and ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphite lyes.
As dispersing agents, which are especially suitable as thickening or anti-settling agents, there can be used, for example, methylcellulose, carboxyme~ylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.
lS Ex~nples of suitable stabilizers are acid-binding agents (e.g. epichlorohydrin, phenyl glycidyl ether and soya epoxides); antioxidants (e.g. gallic acid esters and butylhydroxytoluene); UV-absorbers (e.g. substituted benzo-phenones, diphenylacrylonitrile acid esters and cinnamlc acid esters); and deactivators ~e.g. salts of ethylenedi-aminotetraacetic acid and polyglycols).
The weed control compositions in accordance with the in~ention can contain, in addition ~o the compounds or formula I, synergists and other active substances ~e.g. in-secticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for intensifying the activity or for broadening the spectrum of activity.
The weed control compositions in accordance with the invention generally contain between 0.001 and 95 weight percent, pre~erably between 5 and 75 weight percent, of one or more compounds of formula I as the active substance(s).
They can be present, for example, in a form which is suitable .or storage and transport. In such formulations (e.g.
emulsifiable concentrates) the active substance concen-tration is normally in the higher range, preferably between lO and 75 weight percent, especially between 25 and 50 7~
weight percent. These formulations can then be diluted, for example with the same or dif~erent inert substances, to give activ~ substance concentrations which are suitable for practical use, i.e. preferably about 0.1 to 10 weight per-cent, especially about 1 to 5 weight percent~ The active substance concentrations can~ however, also be smaller or greater.
As mentioned above, the manufacture of the weed con-trol compositions in accordance with th~ in~ention can be carried out in a manner known ~er se.
For the manufacture of pulverous preparations the active substance, i.e. at least one compound of formula I, can be mixed with solid carrier substance ~e.g. by grlnd-ing together) or the solid carrier substance can be im-pregnated with a solution or suspensio~ o~ the active sub-stance and then the solvent or dispersion medium can be removed by evaporation, heating or sucking-off under reduced pressure. By adding tensides or dispersing agents such pulverous preparations can be made readily wettable with water, so that they can be converted into aqueous suspen-sions which are suitable, or example, as spray compositions.
The compound of formula I can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is d~spersible in water or it can be mixed with a so~id pre-granulated carrier substance to form a product in the form of a granulate.
When desired, the compound of formula I can be dis-solved in a water-immiscible solvent ~uch as, for example, a high-boiling hydrocarbon, which conveniently contains dissolved emulsifying agent, so that the solution becomes self-emulsifying upon addition to water. Alternatively, the active subs~ance can be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concen~ration. Moreover, the active substance can - 17 ~
be dissolved in a solvent and thereafter the solution can be mixed with an em~lsifying agent~ Such a mixture can like~ise be diluted wi~h water to the desired concentration~
In this manner there are obtained emulsiiab1e concentrates or ready-for-use emulsions.
The use of the weed con~rol compositions in accordance with the invention can be carried out according ~o usual application methods such as sprinkling, spra~ing, dusting, watering or scattering. The method in accordance with tha invention for the control of weeds comprises treating the locus to be protected against weeds and/or the weeds with a compound in accordance with the invention or a weed control composition in accordance with the invention.
~2~ 57~
The following Exa~ples illustrate the invention in more detail:
I Manufacture of the active substances of ~ormula I:
Exam~le 1 A solution of 2.37 g ~ pyridine in 10 ml of dichloro-methane is added dropwise while stirring to a solutior., cooled to 0C, of 10.53 g Qf D-2-[p-(6-chloro 2-quinoxalyl-oxy)phenoxy]-propionyl chloride and 4.88 g of dieth~l hydrox~methylphosphonate in 50 ml o~ dichloromethane. The mixture is stirred at room temperature for l hour and sub-sequently evaporated to dryness under reduced pressure.
Therea~ter ~he residue ls dlssolved in ethyl acetate and ~he solution i9 extracted with water and dilute sodium bicarbonate solution, dried over a drying agent and evaporated to dryness.
The residue is purified by chromatography on silica gel with dichloromethane/diethyl ether (7:1). There is obtained diethyl ~ D-2-~p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy 7methylphosphonate; [a]D ~ 34.67 (c = 0.93%
i~ CXC13).
In an analogous mannar, from D-2-~p-(6-fluoro-2 quinoxalyloxy)phenoxy]-propionyl chloride and diethyl hydroxymethylphosphonate there is obtained diethyl / D-2-[p~(6-fluoro-2-quinoxalyloxy)phenoxy]-propionyloxy 7methylphosphonate, ~a]20 + 28.08 (c = 1.14%
i~ C~C13);
from D-2-[p-(6~7-dichloro-2-quinoxalyloxy)phenoxy~-propionyl chloride and diethyl 2-hydroxyethylphosphonate there is obtained diethyl 2-r D-2-[p-(6,7 dichloro-2-; quinoxalyloxy)phenoxy]-propionyloxy 7-ethylphosphonate, E~] ~ ~ 32.08 (c = 0.95% in CHC13);
5~
from D-2-[p-(6,7-dichloro-2-quinoxalyloxy)phenoxyj-pro-pionyl chloride and diethyl hydroxyme~hylphosphonate there is obtained diethyl / D-2- [p- ~6, 7~dichloro-2-qulnoxalyloxy) -phenoxy]-propionylo~xy_7methylphosphonate, ~]20 ~ 35.67 (c - 1.00~ in CHC13);
rom D-2-[p-(i,6-dichloro-2-quinoxalyloxy)phenoxy]-propion-yl chloride and diethyl 2~hydroxyethylphosphona~e th~re is obtained diethyl 2-/ D-2-Lp-(5,6-dlchloro--2-quincxalyloxy)-phenoxy]-propionyloxy /-e~hylphosphonate, [a]20 + 27.69 ( c = 1 ~ 07% in CHC13 );
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy~-propionyl chloride and diethyl DL-l-hydroxy~thylphosphonats there is obtained diethyl DL-l-~ D-2-[p-(6-chloro-2-quinoxalylcxy)-phenoxy]-propionyloxy 7-ethylphosphonate, [a]20 + 26.80 (c = 1.10% in CHC13);
from D-2-[p-t6-chloro-2-~uinoxalyloxy)phenoxy]-propionyl chloride and diethyl 2-hydroxyethylphosphonate there is obtained diethyl 2- r D-2-[p-(6-chloro-2-quinoxalyloxy)-phenoxy]-propionyloxy 7-ethylphosphonate, []D0 +27.92 (c = 1.04~ in CHC13);
from D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyl chloride and dibutyl hydroxymethylphosphonate there is obtained dibutyl / D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy /methylphosphonate, [a]20 + 33.11 (c = 1.06 in CHC13~i ,;""s~
-.L~)57 from D 2-[p~(6-chloro~2-quinolyloxy)phenoxy]-prooionyl chloride and diethyl hydroxymetnylphosphonate there is obtained diethyl / D-2-[p-( 6-chloro-2-qu:inolylo~y) phenoxy3 -propionyloxy 7methylphosphonate, [~]20 ~34.24 ~c = 1.03~ in C~C13);
from D-2-~p-(6-chloro-2-quinolyloxy)phenoxy]-propionyl chloride and diethyl DL-l-hydroxyethylphosphonate there is 10 obtained diethyl DL-l-/ D-2- [p- (6-chloro 2-quinolyloxy)-phenoxy]-propionyloxy 7-ethylphosphonate, ~a]20 ~30,550 (c = 1.02% in CHC13); and from D-2~[p-(6-chloro-2-quinolyloxy~phenoxy]-propionyl chloride and diethyl 2-hydro~yethylphosphonate there is obtain~ldiethyl 2-/ D-2-~p-(6-chloro-2-qulnolyloxy)-phenoxy]-pro~lonyloxy 7-ethylphosphonate, ~a~20 ~ 27.39 (c = 1.02% ln C~Cl3).
Example 2_ A solution of 10.29 g of D-2-[p-(6-chloro-2-quinolyl-oxy)phenoxy]-propionic acid in 50 ml of absolute dimethyl-formamide is added dropwise at room temperature to a sus-pension of 1.37 g of a 55~ sodium hydride dispersion in150 ml of absolute dimethylformamide and the mixture is stirred at 50C for 30 minutes. A solution of 8.16 g of diethyl 3-bromopropylphosphonate in 10 ml of absolute di-methylformamide is subsequently added thereto and the mixture is stirred at room temperature for 3 hours. The mixture is then adjusted to pH 5-6 with 2N hydrochloxic acid. The sol~ent is then distilled of at 50C under reduced pressure a~d the residue is treated with 200 ml of ethyl acetate and extracted three times with 100 ml of water each time. The organic phase is dried over anhydrous sodium sulphate and evaporated to dry~ess under reduced pressureO The residue is purified by chromatography on silica gel with dichloromethane/ethyl acetate (3:1).
- 21 ~ 5~
There is obtained diethyl 3~/ D-2-[p-~6~chlors~2-quinolyl oxy)phenoxy]-propionyloxy 7-propylphosphonate, [~120 1 29.08 tc = 0.83% in C~C13).
s Example 3 a) 24.42 g of L~2-~p toluenesulphonyloxy)-propionic acid are heated to boiling for 4 hours with 59.5 g of thio~yl chloride and the mixture is subsequently evaporated to dryness under reduced pressure. The residue is dissolved in 150 ml of dichloromethane and treated at room temperature with 16.82 g of die~hyl hydroxymethylphosphonate. The mixture is then cooled to 0-5C while s~irring and treated dropwise during 15 minutes with a solution of 8.70 g o~
pyridine in 25 ml o~ dichloromethane. The mixture is subsequently stirred at room temperature for 3 hours and the solvent is distilled of~ under rPduced pressure. The residue is dissolved in ethyl acetate, the solution is washed wlth water and the organic phase is dried o~er anhydrous sodium sulphate and evaporated. The resulting residue is purified by chromatography on silica gel with diethyl ether and subsequently distilled in a bulb-tube.
Th~re is ob~ained diethyl ~L-2-~p-toluenesulphonyloxy)-propionyloxy]methylphosphonate, b.p. abou~ 210C/0.05 mm~g,[a~20 -30.32 (c = l.lO~ in C~C13).
b) 2.72 g of p-~6-chloro-2-quinoxalyloxy)-phenol are added to a suspension of 0.43 g of a 55~ sodium hydride dispersion in 25 ml of dimethylformamide and the mixture is stirred at room temperature for 2 hours. A solution of 3,94 g of diethyl [~-2-(p-toluenesulphonyloxy) propionyloxy~
methylphosphonate in 15 ml of dimethylformamide is added dropwise during lO minutes and the mixture is stirred at room temperature for 3 hours and subsequently evaporated under reduced pressure. The residue is then dissolved in ethy} acetate, the solution is washed with water and the organic phase is dried over anhydrous sodium sulphate and evaporated under reduced pressure. The resulting residue is purified by chromatography on silica gel with die~hyl ether, There is obtained diethyl / D-2-[p-~6-chloro-2-quin-oxalyloxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20 ~33.21 (c = 1.06~ in CHC13).
a) 46 g of D-2 (p-benzyloxyphenoxy)-propionic acid are stirred at 90C for 2 hours with 110 ml Qf thionyl chloride~
The mixture is subsequently evaporated to dryness under reduced pressure, the residue is dissolved in 190 ml of di~hloromethane and the solution is treated at room temp-erature with 29.4 g of diethyl hydroxymethylphosphonate~
The mlxture is cooled to 5-10C while stirring and treated dropwise during 20 minutes with a.soLution of 14.22 g o~
pyridine in 20 ml of dichloromethane. The mlxture is then stirred at room temperature ~or a further 30 minutes, washed in sequence with 2N hydrochloric acid, 2N sodium hydroxide solution and water, dried over anhydrous sodium sulphate and evaporated to dryness. The residue is purified by chromatography on silica gel with ethyl acetate/
n-hexane (3:1).
There is obtained diethyl ~D-2-(p~benzyloxyphenoxy)-propionyloxy]methylphosphonate, [a]20 1 36.04 (c = 1.07 in CHC13), ~ = 1.5304.
b) 10 g of diethyl [D-2-(p-benzyloxyphenoxy) propionyl-oxy]methylphosphonate are dissolved in 150 ml of methanol and 1 g of pall~dium/active carbon (10% Pd) is added to the solution. The mixture is hydrogenated at normal pressure and room temperature for 20 hours, the catalyst is subsequently filtered off and the filtrate is evaporated to dryness under reduce pressure. The residue is purified . by chromatography on silica gel with ethyl acetate/~-hexane (2~
57~L
There is obtained diethyl ~D~2 (p-hydroxypheno~y)-propionyloxy]methylphosphonate, [a]20 ~39.40o (c = 1.00%
in CXCl3), nD = 1.5033.
c~ A solution of 2 g of diethyl [D-2-(p-hydroxyphenoxy)-propionyloxy~methylphosphonate in 25 ml of dimethyl sul-phoxide is treated wi~h 0.14 g of sodium hydride and the mixture is stirred at room temperature ror 30 minutes.
A solution of l.Ol g o 2-chlorobenzthiaæole in lO ml of dimethyl sulphoxide is subsequently added dropwise thereto during 5 minutes and the mixture is stirred at 95C for 12 hours. The mixture ~s then poured on to lO0 ml of ice-water and extracted with ethyl acetate. The organic phase is washed with water~ dried over anhydrous sodium sulphate and evaporated under reduced pressure. The residue is puriied by chromatography on silica gel with ethyl acetate~
n-hexane (2:l).
There is obtained diethyl r D-2-[p-(2-benzthiazolyl-oxy)phenoxy]-propionyloxy 7methylphosphonate, [a]20 +9~06 (c = 0.89~ in CHCl3).
In an analogous manner, from diethyl ~D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-phosphonate and 2,5-dichlorobenzthiazole there is obtained diethyl / D-2-[p-~5-chloro-2-benzthiazolyloxy)phenoxy]-propio~yloxy_7methylphosphonate, [a]D ~18.00 (c = l.06 in CHCl3); and from diethyl [D-2-(p-hydroxyphenoxy)-propionyloxy]methyl-phosphonate and 2,4,6-trichlorobenzthiazole there is ob-tained diethyl / D-2 ~p-(4~6-dichloro-2-benzthiazolylo~y)-phenoxy]-propionyloxy /methylphosphonate, [a]D 119.47 (c - 0.76~ in CHCl3).
~?71~7
- 2~ -II. Formulation Exam~les:
Exam~le 5 For the manufacture of an emulsifia~le concentrate the ingredients listed hereinafter are mixed with one another:
10 Compound of formula I 250 g/l N~Methyl-2-pyrrolidone 300 g/l Emulsifier A 100 g/l Emulsifier B 25 g/l Solvent mixture of alkylbenzenes ad1000 ml Emulsifier consisting of 60 parts of an ethylene oxide-propylene oxide block polymerizate, 20 parts of calcium dodecylbenzene sulphonate and 20 parts of a mixture of isobutanol and C10-alkylbenzenes.
Emulsifier consisting of 70 parts of calcium dodecyl-benzenesulphona~e and 30 parts of a mixture of isobutanol and C10-alkylbenzenes.
The thus obtained concentrate emulsifies spontan-eously in water. The resulting emulsion is suitable 25 a ready-for-use spray liquor.
Exam~e 6 For the manufacture of a suspension concentrate the ingredients listed hereinafter are mixed with one another and rinely ground in a bead mill:
Welght E~ent Compound of formula I 25 Ethylene glycol 8.0 : Formaldehyde (30%) 1.0 5~
Silicic acid, highly dispersible C.5 Silicon anti-foam agent 0.5 Nonylphenol-(10)-etho.Yylate 2.0 5 Sodium polyphsnol~ormaldehyde sulphonate 4.0 Xanthan gum 0.3 Distilled water ad 100.0 The thus-obtained suspension concentrate disperses spontaneously in watex and gives a ready-for-use spray liquor.
1~
Exam~le 5 For the manufacture of an emulsifia~le concentrate the ingredients listed hereinafter are mixed with one another:
10 Compound of formula I 250 g/l N~Methyl-2-pyrrolidone 300 g/l Emulsifier A 100 g/l Emulsifier B 25 g/l Solvent mixture of alkylbenzenes ad1000 ml Emulsifier consisting of 60 parts of an ethylene oxide-propylene oxide block polymerizate, 20 parts of calcium dodecylbenzene sulphonate and 20 parts of a mixture of isobutanol and C10-alkylbenzenes.
Emulsifier consisting of 70 parts of calcium dodecyl-benzenesulphona~e and 30 parts of a mixture of isobutanol and C10-alkylbenzenes.
The thus obtained concentrate emulsifies spontan-eously in water. The resulting emulsion is suitable 25 a ready-for-use spray liquor.
Exam~e 6 For the manufacture of a suspension concentrate the ingredients listed hereinafter are mixed with one another and rinely ground in a bead mill:
Welght E~ent Compound of formula I 25 Ethylene glycol 8.0 : Formaldehyde (30%) 1.0 5~
Silicic acid, highly dispersible C.5 Silicon anti-foam agent 0.5 Nonylphenol-(10)-etho.Yylate 2.0 5 Sodium polyphsnol~ormaldehyde sulphonate 4.0 Xanthan gum 0.3 Distilled water ad 100.0 The thus-obtained suspension concentrate disperses spontaneously in watex and gives a ready-for-use spray liquor.
1~
Claims (23)
1 Compounds of the general formula I
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitro-gen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally monosubstituted or multiply substituted phenyl, the optionally present substituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cyclo -alkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2.
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitro-gen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally monosubstituted or multiply substituted phenyl, the optionally present substituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cyclo -alkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2.
2. Compounds according to claim 1, wherein R sig-nifies chlorine.
3. Compounds according to claim 1 wherein R1 signifies hydrogen, methyl or ethyl.
4. Compounds according to any one of claims 1 to 3, wherein R2 signifies hydrogen, methyl or ethyl.
5. Compounds according to any one of claims 1 to 3, wherein R3 and R4 each independently signify C1-6-alkyl.
6. Compounds according to any one of clalms 1 to 3 wherein q signifies 1.
7. Compounds according to any one of claims 1 to 3 in the D-form.
8. Diethyl [D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy]methylphosphonate.
9. Diethyl [D-2-[p-(6-chloro-2-quinolyloxy)pheroxy]-propionyloxy]methylphosphonate.
10. A compound according to claim 1, selected from:
Diethyl [D-2-[p-(6-fluoro-2-quinoxalyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl 2-[D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl [D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]methylphosphonate, diethyl 2-[D-2 [p-(5,6-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl DL-1-[D-2-[p-(6-chloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl 2-[D-2-[p-(p-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy]-ethylphosphonate, dibutyl[D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl DL-1-[D-2-[p-(6-chloro-2-quinolyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl 2-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy]-ethylphosphonate, diethyl 3-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy]-propylphosphonate, diethyl[D-2-[p-(2-benzthiazolyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl[D-2-[p-(5-chloro-2-benzthiazolyloxy)-phenoxy]-propionyloxy]methylphosphonate and diethyl[D-2-[p-(4,6-dichloro-2-benzthiazolyloxy)-phenoxy]-propionyloxy]methylphosphonate.
Diethyl [D-2-[p-(6-fluoro-2-quinoxalyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl 2-[D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl [D-2-[p-(6,7-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]methylphosphonate, diethyl 2-[D-2 [p-(5,6-dichloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl DL-1-[D-2-[p-(6-chloro-2-quinoxalyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl 2-[D-2-[p-(p-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy]-ethylphosphonate, dibutyl[D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl DL-1-[D-2-[p-(6-chloro-2-quinolyloxy)-phenoxy]-propionyloxy]-ethylphosphonate, diethyl 2-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy]-ethylphosphonate, diethyl 3-[D-2-[p-(6-chloro-2-quinolyloxy)phenoxy]-propionyloxy]-propylphosphonate, diethyl[D-2-[p-(2-benzthiazolyloxy)phenoxy]-propionyloxy]methylphosphonate, diethyl[D-2-[p-(5-chloro-2-benzthiazolyloxy)-phenoxy]-propionyloxy]methylphosphonate and diethyl[D-2-[p-(4,6-dichloro-2-benzthiazolyloxy)-phenoxy]-propionyloxy]methylphosphonate.
11. A compound according to claim 1 as a weed control agent.
12. A weed control composition which contains an effective amount of at least one compound of the general formula I
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally mono-substituted or multiply substituted phenyl, the optionally present sub-stituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently sig-nify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, as well as formulation adjuvants.
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally mono-substituted or multiply substituted phenyl, the optionally present sub-stituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently sig-nify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, as well as formulation adjuvants.
13. A weed control composition according to claim 12 which contains an effective amount of diethyl [D-2-[p-(6-chloro-2-quinoxalyloxy)phenoxy]-propionyloxy] methyl-phosphonate or diethyl [D-2-[p-(6-chloro-2-quinolyloxy)-phenoxy]-propionyloxy] methylphosphonate as well as form-ulation adjuvants.
14. A process for the manufacture of compounds of the general formula I
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally monosubstituted or multiply substituted phenyl, the optionally present substituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, which process comprises a) reacting an acid of the general formula II
wherein A has the significance given above, or a reactive derivative thereof, with an alcohol of the general formula III
wherein R1, R2, R3, R4, m, n and p have the significances given above and Z' signifies hydroxy or a leaving group, b) reacting a phenol of the general formula IV
wherein A has the significance given above, or an alkali metal salt thereof, with a compound of the general formula V
wherein R1, R2, R3, R4, m, n and p have the significances given above and Z2 signifies a leaving group, or c) reacting a halide of the general formula A-Hal VI
wherein A has the significance given above and Hal signifies halogen, with a phenol of the general formula VII
wherein R1, R2, R3, R4, m, n and p have the significances given above, or an alkali metal salt thereof.
wherein A signifies one of the following groups (a) or (b) (a) (b) R signifies hydrogen, halogen, C1-4-alkyl, trifluoromethyl, C1-4-alkoxy or C1-4-alkylthio, X signifies oxygen, sulphur or -NR5-, Y signifies the methine group or a nitrogen atom, R1 signifies hydrogen or C1-4-alkyl and R2 signifies hydrogen, C1-4-alkyl, C1-4-haloalkyl or optionally monosubstituted or multiply substituted phenyl, the optionally present substituents being halogen atoms, C1-4-alkyl groups, C1-4-alkoxy groups and nitro groups, or R1 and R2 together with the carbon atom to which they are attached signify an optionally substituted C5-8-cycloalkane ring, the optionally present substituents being one to three C1-4-alkyl groups, R3 and R4 each independently signify C1-6-alkyl or phenyl, R5 signifies hydrogen or C1-4-alkyl, m, n and p each independently signify the number 0 or 1, the sum thereof being at least 1, and q signifies the number 1 or 2, which process comprises a) reacting an acid of the general formula II
wherein A has the significance given above, or a reactive derivative thereof, with an alcohol of the general formula III
wherein R1, R2, R3, R4, m, n and p have the significances given above and Z' signifies hydroxy or a leaving group, b) reacting a phenol of the general formula IV
wherein A has the significance given above, or an alkali metal salt thereof, with a compound of the general formula V
wherein R1, R2, R3, R4, m, n and p have the significances given above and Z2 signifies a leaving group, or c) reacting a halide of the general formula A-Hal VI
wherein A has the significance given above and Hal signifies halogen, with a phenol of the general formula VII
wherein R1, R2, R3, R4, m, n and p have the significances given above, or an alkali metal salt thereof.
15. A method for the control of weeds, which method com-prises treating the locus to be protected against weeds and/
or the weeds with an effective amount of one of the com-pounds set forth in claims 1 to 3.
or the weeds with an effective amount of one of the com-pounds set forth in claims 1 to 3.
16. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of one of a composition as set forth in claim 12 or 13.
17. Compounds according to claim 1 wherein R signifies chlorine and R1 signifies hydrogen, methyl or ethyl.
18. Compounds according to claim 17 wherein R2 signifies hydrogen, methyl or ethyl.
19. Compounds according to claim 18 wherein R3 and R4 each independently signify C1-6-alkyl.
20. Compounds according to any one of claims 17, 18 or 19 wherein q signifies 1.
21. Compounds according to any one of claims 17, 18 or 19 in the D-form.
22. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of one of the compounds set forth in claims 17, 18 or 19.
23. The compositions according to claims 12 or 13 wherein the formulation adjuvants are selected from solid carrier substances; solvents or dispersion media;
tensides including wetting and emulsifying agents;
dispersing agents and stabilizers.
tensides including wetting and emulsifying agents;
dispersing agents and stabilizers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH184383 | 1983-04-06 | ||
| CH1843/83 | 1983-04-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246571A true CA1246571A (en) | 1988-12-13 |
Family
ID=4219905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000447244A Expired CA1246571A (en) | 1983-04-06 | 1984-02-13 | Propionic acid esters |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0121871B1 (en) |
| JP (1) | JPS59196898A (en) |
| AT (1) | ATE32079T1 (en) |
| AU (1) | AU565524B2 (en) |
| CA (1) | CA1246571A (en) |
| DE (1) | DE3468881D1 (en) |
| DK (1) | DK149484A (en) |
| ES (1) | ES8602351A1 (en) |
| GR (1) | GR79920B (en) |
| IE (1) | IE57199B1 (en) |
| IL (1) | IL71415A (en) |
| NO (1) | NO841354L (en) |
| NZ (1) | NZ207703A (en) |
| ZA (1) | ZA842432B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3402982A1 (en) * | 1984-01-28 | 1985-08-01 | Bayer Ag, 5090 Leverkusen | PHENOXYPROPIONYLOXYALKANPHOSPHONIC ACID ESTER |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0054715A3 (en) * | 1980-12-18 | 1982-09-22 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Esters of propanoic acid, preparation of these compounds, weed killers containing these compounds as active ingredients, use of such compounds and compositions for the control of weeds |
| US4462994A (en) * | 1981-05-19 | 1984-07-31 | Nissan Chemical Industries, Inc. | N-Containing heterocyclic ring-substituted O-arylphosphate derivatives, preparation thereof, and insecticides, acaricides and nematocides containing said derivatives |
| JPS5832890A (en) * | 1981-08-21 | 1983-02-25 | Sumitomo Chem Co Ltd | Phosphonic ester derivative, its preparation, hebicide containing the same as active ingredient |
-
1984
- 1984-02-13 CA CA000447244A patent/CA1246571A/en not_active Expired
- 1984-02-29 DK DK149484A patent/DK149484A/en not_active IP Right Cessation
- 1984-03-29 EP EP84103484A patent/EP0121871B1/en not_active Expired
- 1984-03-29 DE DE8484103484T patent/DE3468881D1/en not_active Expired
- 1984-03-29 AT AT84103484T patent/ATE32079T1/en active
- 1984-03-30 NZ NZ207703A patent/NZ207703A/en unknown
- 1984-03-30 ZA ZA842432A patent/ZA842432B/en unknown
- 1984-03-31 IL IL71415A patent/IL71415A/en not_active IP Right Cessation
- 1984-04-05 GR GR74315A patent/GR79920B/el unknown
- 1984-04-05 IE IE842/84A patent/IE57199B1/en unknown
- 1984-04-05 ES ES531320A patent/ES8602351A1/en not_active Expired
- 1984-04-05 JP JP59068367A patent/JPS59196898A/en active Pending
- 1984-04-05 NO NO841354A patent/NO841354L/en unknown
- 1984-04-06 AU AU26615/84A patent/AU565524B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0121871B1 (en) | 1988-01-20 |
| IL71415A (en) | 1987-08-31 |
| IE57199B1 (en) | 1992-06-03 |
| GR79920B (en) | 1984-10-31 |
| DE3468881D1 (en) | 1988-02-25 |
| AU565524B2 (en) | 1987-09-17 |
| ES531320A0 (en) | 1985-12-01 |
| IL71415A0 (en) | 1984-06-29 |
| AU2661584A (en) | 1984-10-11 |
| NO841354L (en) | 1984-10-08 |
| DK149484A (en) | 1984-10-07 |
| ES8602351A1 (en) | 1985-12-01 |
| IE840842L (en) | 1984-10-06 |
| ZA842432B (en) | 1984-11-28 |
| EP0121871A1 (en) | 1984-10-17 |
| DK149484D0 (en) | 1984-02-29 |
| JPS59196898A (en) | 1984-11-08 |
| ATE32079T1 (en) | 1988-02-15 |
| NZ207703A (en) | 1987-06-30 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |