CA1234139A - Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds - Google Patents
Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weedsInfo
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- CA1234139A CA1234139A CA000471811A CA471811A CA1234139A CA 1234139 A CA1234139 A CA 1234139A CA 000471811 A CA000471811 A CA 000471811A CA 471811 A CA471811 A CA 471811A CA 1234139 A CA1234139 A CA 1234139A
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Abstract
ABSTRACT
Compounds, and processes to prepare them, of the formula II
(II) wherein R3 is C1-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, C1-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independ-ently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, -S(O)n-C1-C4-alkyl, -S(O)n-C1-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or C1-C4-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl or C1-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is C1-C4-alkoxy, and two of the substituents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl are described. These compounds find use in the preparation of related dihydropyrones of the formula I
Compounds, and processes to prepare them, of the formula II
(II) wherein R3 is C1-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, C1-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independ-ently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, -S(O)n-C1-C4-alkyl, -S(O)n-C1-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or C1-C4-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl or C1-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is C1-C4-alkoxy, and two of the substituents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl are described. These compounds find use in the preparation of related dihydropyrones of the formula I
Description
~4~3~
This application is a Divisional Application from Application 404,230, filed June lst, 1982.
Application 404,230 relates to novel dihydropyrones having herbicidal activity, to processes for producing them, to novel starting products used therein, to compositions containing the novel dihydropyrones as active ingredients/ and to the use thereof for combatiny weeds.
I'hese dihydropyrones, includiny the acid addition salts thereof, coorespond to the formula I
Rl~ /-\ /C-R
j j (I) R2 , ~H--~
wherein Rl and R2 independently of one another are each a C1-C4-alkyl yroup, or one of the two substituents is also hydroyen, or Rl and R2 jointly form a C2-C6-alkylene bridge, R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy, C3-C5-alkoxyalkoxy or hydroxyl, and X, Y
and Z independently of one another are each hydrogen, halogen, cl-c4-alkyl, cl~C4-alkXYI Cl-C4-halalkYl' Cl-C4-~;23~
haloalkoxy, -S(O)n-Cl~C4~alkYl~ ~S()n Cl C4 where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are each N02, CN
or NR5R6, where R5 and R6 independently of one another are each hydrogen, Cl-C4-alkyl, Cl-C4-alkylcarbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl.
Cl-C~-Alkyl as substituent or as part of a substituent is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl and in particular methyl and ethyl.
C2-C6-Alkenyl and C2-C4-alkynyl can be straight-chain or branched chain. Preferred groups are allyl and propargyl.
An alkylene bridge ~ormed by Rl and R2 can be a straight-chain or branched-chain group, particularly a -(CH2)3- or -(CH2)4- group.
By halogen as substituent or as part of a substituent are meant ~luorine, chlorine, bromine and iodine atoms.
Haloalkyl groups can be mono- or polysubstituted by the aforementioned halogen atoms, for example CH2J, CC13, CHC12, CH2~r and especially CF3, CHF2, CH2CH2Cl, CF2CHF2, CH2CF3 and CH2CC13.
Suitable salts are in particular metal salts, and salts with quaternary ammonium bases or organic nitrogen bases.
Metals suitable for salt formation are for example:
alkaline-earth metals, such as magnesium or calcium, especially however the alkali metals, such as lithium, potassium or sodium. Also applicable as salt formers are transition metals, such as iron, nickel, cobalt, copper, ~inc, chromium or manganese.
Examples of quaternary ammonium bases are the ammonium cation, tetraalkylammonium cations in which the alkyl groups independently of one another are straight-chain or branched-chain cl-C6-alkyl groups, such as the tetramethyl-ammonium cation, the tetraethylammonium cation or the ~;~34~3~
trimethylethylammonium cation, and also the trimethyl-benzylammonium cation, the triethylbenzylammonium cation, the trimethyl-2-hydroxyethylammonium cation and the trimethyl-2-chloroethylammonium cation.
Example of organic nitrogen bases suitable for forming salts are: primary, secondary and tertiary, a~iphatic and aromatic amines which can be hydroxylated on the hydrocarbon radical, such as: methylamine, ethylamine, propylamine, isopropylamine, the four isomeric butylamines, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethyl-amine, triethylamine, tri-n-propylamine, quinuclidine, pyridine, quinoline, isoquinoline as well as methanolamine, ethanolamine, propanolamine, dimethanolamine, diethanolamine or triethanolamine.
Compounds of the formula I in which Rl and R2 are alkyl groups can be in the form of two diastereoisomers, of which the one exhibits a cis configuration, the other a trans configuration. It is possible to separate the isomers from isomeric mixtures of compounds of the formula I in a manner known per se, for example by column chromatography. The present invention embraces cis isomers, trans isomers and isomeric mixtures of compounds of the formula I.
Preferred compou~ds of the formula I are those in which the phenoxy group is in the p- or m-position, especially in the p-position, and in which Rl is Cl-C4-alkyl, and R2 is methyl or ethyl, or one of the substituents Rl and R2 is also hydrogen, or Rl and R2 together form a -(C~12)3- or -(CH2)4- group, R3 is Cl-C4-alkoxy, which can be straight-chain or branched-chain, or allyloxy, propargyloxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, methoxymethoxy or 2-(methoxy)-ethoxy, and one of the sub-stituents X, Y and Z is hydrogen, and the two other 3~
substituents independently of one another are hydrogen, chlorine, bromine, iodine, fluorine, me-thyl, ethyl, methoxy, trifuoromethyl, trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methylthio, methylsulfinyl, methylsulfonyl, trifluorome-thylthio, difluoromethylthio, trifluoromethylsulfinyl, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, amino, methylamino or dimethylamino.
In Application 404,230 it is disclosed that the compounds of formula I are produced using a process analogous to that described in Bull. Soc. Chim. de France (1968), 288-298, by a) reacting a compound of the formula II
o fH2 o ~0~o~ ~ (II) ~
wherein R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independently of one another are each hydrogen, h logen C -C -alkyl, Cl-C4-alkoxy, Cl C4 cl_c4_halOalkoxy/ -s(o)n-cl-c4-alkylr ~S(0)n~Cl~C4~halalkYl' where n is 0, 1 or 2, or -they are each C(0)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are each NO2, CN or
This application is a Divisional Application from Application 404,230, filed June lst, 1982.
Application 404,230 relates to novel dihydropyrones having herbicidal activity, to processes for producing them, to novel starting products used therein, to compositions containing the novel dihydropyrones as active ingredients/ and to the use thereof for combatiny weeds.
I'hese dihydropyrones, includiny the acid addition salts thereof, coorespond to the formula I
Rl~ /-\ /C-R
j j (I) R2 , ~H--~
wherein Rl and R2 independently of one another are each a C1-C4-alkyl yroup, or one of the two substituents is also hydroyen, or Rl and R2 jointly form a C2-C6-alkylene bridge, R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy, C3-C5-alkoxyalkoxy or hydroxyl, and X, Y
and Z independently of one another are each hydrogen, halogen, cl-c4-alkyl, cl~C4-alkXYI Cl-C4-halalkYl' Cl-C4-~;23~
haloalkoxy, -S(O)n-Cl~C4~alkYl~ ~S()n Cl C4 where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are each N02, CN
or NR5R6, where R5 and R6 independently of one another are each hydrogen, Cl-C4-alkyl, Cl-C4-alkylcarbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl.
Cl-C~-Alkyl as substituent or as part of a substituent is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl and in particular methyl and ethyl.
C2-C6-Alkenyl and C2-C4-alkynyl can be straight-chain or branched chain. Preferred groups are allyl and propargyl.
An alkylene bridge ~ormed by Rl and R2 can be a straight-chain or branched-chain group, particularly a -(CH2)3- or -(CH2)4- group.
By halogen as substituent or as part of a substituent are meant ~luorine, chlorine, bromine and iodine atoms.
Haloalkyl groups can be mono- or polysubstituted by the aforementioned halogen atoms, for example CH2J, CC13, CHC12, CH2~r and especially CF3, CHF2, CH2CH2Cl, CF2CHF2, CH2CF3 and CH2CC13.
Suitable salts are in particular metal salts, and salts with quaternary ammonium bases or organic nitrogen bases.
Metals suitable for salt formation are for example:
alkaline-earth metals, such as magnesium or calcium, especially however the alkali metals, such as lithium, potassium or sodium. Also applicable as salt formers are transition metals, such as iron, nickel, cobalt, copper, ~inc, chromium or manganese.
Examples of quaternary ammonium bases are the ammonium cation, tetraalkylammonium cations in which the alkyl groups independently of one another are straight-chain or branched-chain cl-C6-alkyl groups, such as the tetramethyl-ammonium cation, the tetraethylammonium cation or the ~;~34~3~
trimethylethylammonium cation, and also the trimethyl-benzylammonium cation, the triethylbenzylammonium cation, the trimethyl-2-hydroxyethylammonium cation and the trimethyl-2-chloroethylammonium cation.
Example of organic nitrogen bases suitable for forming salts are: primary, secondary and tertiary, a~iphatic and aromatic amines which can be hydroxylated on the hydrocarbon radical, such as: methylamine, ethylamine, propylamine, isopropylamine, the four isomeric butylamines, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethyl-amine, triethylamine, tri-n-propylamine, quinuclidine, pyridine, quinoline, isoquinoline as well as methanolamine, ethanolamine, propanolamine, dimethanolamine, diethanolamine or triethanolamine.
Compounds of the formula I in which Rl and R2 are alkyl groups can be in the form of two diastereoisomers, of which the one exhibits a cis configuration, the other a trans configuration. It is possible to separate the isomers from isomeric mixtures of compounds of the formula I in a manner known per se, for example by column chromatography. The present invention embraces cis isomers, trans isomers and isomeric mixtures of compounds of the formula I.
Preferred compou~ds of the formula I are those in which the phenoxy group is in the p- or m-position, especially in the p-position, and in which Rl is Cl-C4-alkyl, and R2 is methyl or ethyl, or one of the substituents Rl and R2 is also hydrogen, or Rl and R2 together form a -(C~12)3- or -(CH2)4- group, R3 is Cl-C4-alkoxy, which can be straight-chain or branched-chain, or allyloxy, propargyloxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, methoxymethoxy or 2-(methoxy)-ethoxy, and one of the sub-stituents X, Y and Z is hydrogen, and the two other 3~
substituents independently of one another are hydrogen, chlorine, bromine, iodine, fluorine, me-thyl, ethyl, methoxy, trifuoromethyl, trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methylthio, methylsulfinyl, methylsulfonyl, trifluorome-thylthio, difluoromethylthio, trifluoromethylsulfinyl, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, amino, methylamino or dimethylamino.
In Application 404,230 it is disclosed that the compounds of formula I are produced using a process analogous to that described in Bull. Soc. Chim. de France (1968), 288-298, by a) reacting a compound of the formula II
o fH2 o ~0~o~ ~ (II) ~
wherein R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independently of one another are each hydrogen, h logen C -C -alkyl, Cl-C4-alkoxy, Cl C4 cl_c4_halOalkoxy/ -s(o)n-cl-c4-alkylr ~S(0)n~Cl~C4~halalkYl' where n is 0, 1 or 2, or -they are each C(0)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are each NO2, CN or
2~ NR5R6, where R5 and R6 independently of one another are each ; hydrogen, Cl-C4-alkyl, C1-C4-alkylcarbonyl, Cl-C4-haloalkyl-~23~3~
carbonyl or Cl-C4-haloalkylsulfonyl, in an inert solvent, with a compound of the formula III
Mg(OR )2 (III) wherein R' is a straight-chain or branched-chain Cl-C4-alkyl group;
b) reacting the resulting reaction product, in an inert solvent, with a compound of the formula V
Rl O
R2-C~I = C - C - Cl (V) wherein Rl and R2 independently of one another are each a Cl-C4-alkyl group, or one of the two substituents is also hydrogen, or Rl and R2 jointly form a C2 C6-alkylene bridge; and c) cyclising the resulting product with an alcoholic solution of a strong acid, and, when R3 in the formula I is hydroxyl, saponifying the ester obtained, or optionally converting in the resulting ester of the formula I the group R3, by transesterification, into another group R3 defined under the formula I.
The reactions described under a) and b) are in each case performed in an inert solvent. Suitable inert solvents are for example: benzene, toluene, xylene, ether, tetrahydrofuran or dioxane.
The reaction of a compound of the ~ormula II with a compound of the Eormula III is advantageously per;Eormed at a temperature within the range of O to 150C; and the reaction of the reaction product obtained under a) with a compound of the formula V at a temperature within the range of -10C to room temperature.
The magnesium alcoholate of the ~ormula III used in the reaction described under a) can be produced in situ by ~23~
reaction of magnesium with a corresponding alcohol in the presence of CC14.
The cyclisation described under c) can be performed with an alcoholic solution of a catalytic amount of a strong acid under reflux, for example with an alcoholic so]ution of hydrochloric acid, which is also obtainable in situ by reaction of acetyl chloride with alcohol.
The conversion of a yroup R3 into another group R3 defined under the formula I by transesterification can be carried out, in a manner known per se, by adding to a compound of the formula I a correspon~ing alcohol in the presence of a strong acid.
This invention is concerned with these intermediates of the formula II.
Thus in its broadest aspect this invention provides a compound of the formula II j~
Cl-R3 0.~C~ X (II) -~ O--~ ~
wherein R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z
independently of one another are each hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, ~S(0)n~
Cl-C4-alkyl, -S(0)n-Cl-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(0)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are _ 7 _ ~ ~3~3~
each N02, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, Cl-C4-alkyl, Cl-C4-alkylcarbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is Cl-C4-alkoxy, and two of the substi-tuents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
In Application 404,230 -the starting products of the formula II
are divided into Group A, and Group B, and can be produced by processes known per se or in an analogous manner.
Group A consists of compounds of the formula II in which the phenoxy group is in the p-position, R3 is Cl-C4-alkoxy, and two of the substituents X, Y and Z are hydroyen, and the third substituent is hydrogen, fluorine, chlorine, bromine or trifluoromethyl. These are known compounds.
This application is coneerned with Group B which consists of eompounds of the formula II in which R3 is Cl-C4-alkoxy, C2-C6-alkenylox-y, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and ~, Y and Z independently of one another are each hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, -S(~)n-Cl-C4-alkyl, -S(0)n-Cl-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(0)OR4, where R4 is hydrogen or Cl-C~-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are eaeh hydrogen, Cl-C4-alkyl, Cl-C4-alkylearbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-posi-tion, R3 is Cl-C4-allcoxy, and two of the substituents X, Y and Z are hydrogen, -the third ~2~3~
g substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
The compounds of the formula II, Group B, which have been specially developed for the production of the compounds of the formula I according to the invention, are still novel and likewise form subject matter of the present invention.
A process for producing 4-(4'-chlorophenoxy)-benzoyl-acetic acid ethyl ester by reaction of 4-(4'-chlorophenoxy)-benzoic acid with thionyl chloride and sodium-acetyl-acetic acid ethyl ester and subsequent deacetylation is described in Arzneimittelforschung (Pharmacological Research) 30 (1), No. 3 (1980), 454-459.
In the German O~fenlegungsschrift No. 2,436,012 are described 4-phenoxy-benzoylacetic acid and alkyl esters thereof in which the phenoxy group is unsubstituted or substituted by a fluorine, chlorine or bro~ine atom or by a trifluoro-methyl group. The alkyl esters are obtainable by Friedel-Crafts acylation of the corresponding diphenyl ethers with malonic ester chlorides, and the corresponding acids by subsequent saponification.
In addition to being obtainable by the processes already mentioned in the foregoing, compounds of the formula II
can also be produced, using a process analogous to that described in J. Amer. Chem. Soc. 70 (1948), 3356-3360, by reaction of phenoxyphenyl derivatives with malonic acid methyl ester chloride.
Furthermore, compounds of the formula II in which R3 is cl-C4-alkoxy can be produced, using a process analogous to that described in Tetrahedron 20 (1964), 1625-1632, according to the following reaction scheme:
-. .
~:3~L~39 - c~3 i ~~ y1) NaH (2 equiv.) ~ dioxane z 11 R OCOR
(VI~I) 7 7 2 ) IlO~c O~
~. ~ >~
(II) In the above formulae, X, Y and Z have the meanings given for formula II, and R7 is Cl-C4-alkyl.
The compounds of the formula VIII ~re known and can be produced by me-thods anaLogous to known methods (cf. for example US Patent Specification No. 4,125,729; and Belgian Patent Specification No. 639,727 [Ref. in Chem. Abst. ~2 (1965), 14581h]).
The production of compounds of the formula II by a process analogous to the last-mentioned process is further illustrated in the following Example.
Example 9: 4-(3l-Trifluoromethyl-phenoxy)-benzoylacetic acid methy] ester.
To a mixture of 29 g of NaH (2 equiv.; 55% oil disper-sion, washed three times with toluene) and 54 g of dimethyl-carbonate in 400 ml of dioxane are added dropwise, at 85~C, 84.2 g of 4-(3'-trifluoromethylpllenoxy)-acetophenone , -~239L~
dissolved in 160 ml of dioxane, whereupon an evolution of hydrogen immediately occurs. After the reaction has subsided, the reaction mixture is stirred at 85C for a further 2 hours, and 100 ml of acetic acid are then added dropwise with ice cooling. To the paste obtained are added 400 ml of ether and about 200 g of neutral Alox I (aluminium oxide (alumina) Woelm, activity stage I), and the mixture is filtered. The filtrate is concentrated by evaporation, dissolved in acetone, washed successively with water, a ln saturated NaHC03 solution and a saturated NaCl solution, dried, and concentrated by evaporation. The viscous product obtained can be used directly for the production of compounds of the form-1la I, or it is distilled at 10 2 Torr and 160C, or recrystallised from hexane (m.p. 50-55C).
The yield of pure product is about 65 g (65% of theory).
The following compounds of the formula II can be produced in an analogous manner: -C~12 Ij_o~
~0/ l ~. Y
~ O~ z ' Table I: Group B Compounds ~ .
No. R3 X Y Z in.p.~C
(Constitution~
.. ~
B-l C2H5 2-C1 4-Cl 11 (viscous) B-2 OCH3 2-Cl 4-CF3 H (viscous) B-3 3 3 ( ~3 H S-CF3 9G
B-4 OCH3 3-Cl 11 5-C1 61-63 B-5 OC~; 2-C1 4-CF3 H (viscous) 1,-6 OC~i~C~.~Cl 3-CF3 H H
, . ~
~23~39 Table 1 (continuation): Group B Cornpo~ndS
_ _ No. R3 ~ y _ . _ (Constitution`
B-7 0cll2cH=cH2 3-CF3 H H
B-8 0cll2c-cH 3-CF3 H H _ B-ll OC~I2CC13 3-Cl H H ~
B-12 OCH2cH=cH23-Br H H
B-13 OC2H5 3-J H H (viscous) B-l4 OC2H5 3-OCF3 H H (viscous) B-15 OCH2cH2cl3 OCF3 H _ B-16 C2H5 3-OCEIF2 H H (viScous)
carbonyl or Cl-C4-haloalkylsulfonyl, in an inert solvent, with a compound of the formula III
Mg(OR )2 (III) wherein R' is a straight-chain or branched-chain Cl-C4-alkyl group;
b) reacting the resulting reaction product, in an inert solvent, with a compound of the formula V
Rl O
R2-C~I = C - C - Cl (V) wherein Rl and R2 independently of one another are each a Cl-C4-alkyl group, or one of the two substituents is also hydrogen, or Rl and R2 jointly form a C2 C6-alkylene bridge; and c) cyclising the resulting product with an alcoholic solution of a strong acid, and, when R3 in the formula I is hydroxyl, saponifying the ester obtained, or optionally converting in the resulting ester of the formula I the group R3, by transesterification, into another group R3 defined under the formula I.
The reactions described under a) and b) are in each case performed in an inert solvent. Suitable inert solvents are for example: benzene, toluene, xylene, ether, tetrahydrofuran or dioxane.
The reaction of a compound of the ~ormula II with a compound of the Eormula III is advantageously per;Eormed at a temperature within the range of O to 150C; and the reaction of the reaction product obtained under a) with a compound of the formula V at a temperature within the range of -10C to room temperature.
The magnesium alcoholate of the ~ormula III used in the reaction described under a) can be produced in situ by ~23~
reaction of magnesium with a corresponding alcohol in the presence of CC14.
The cyclisation described under c) can be performed with an alcoholic solution of a catalytic amount of a strong acid under reflux, for example with an alcoholic so]ution of hydrochloric acid, which is also obtainable in situ by reaction of acetyl chloride with alcohol.
The conversion of a yroup R3 into another group R3 defined under the formula I by transesterification can be carried out, in a manner known per se, by adding to a compound of the formula I a correspon~ing alcohol in the presence of a strong acid.
This invention is concerned with these intermediates of the formula II.
Thus in its broadest aspect this invention provides a compound of the formula II j~
Cl-R3 0.~C~ X (II) -~ O--~ ~
wherein R3 is Cl-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z
independently of one another are each hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, ~S(0)n~
Cl-C4-alkyl, -S(0)n-Cl-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(0)OR4, where R4 is hydrogen or Cl-C4-alkyl, or they are _ 7 _ ~ ~3~3~
each N02, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, Cl-C4-alkyl, Cl-C4-alkylcarbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is Cl-C4-alkoxy, and two of the substi-tuents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
In Application 404,230 -the starting products of the formula II
are divided into Group A, and Group B, and can be produced by processes known per se or in an analogous manner.
Group A consists of compounds of the formula II in which the phenoxy group is in the p-position, R3 is Cl-C4-alkoxy, and two of the substituents X, Y and Z are hydroyen, and the third substituent is hydrogen, fluorine, chlorine, bromine or trifluoromethyl. These are known compounds.
This application is coneerned with Group B which consists of eompounds of the formula II in which R3 is Cl-C4-alkoxy, C2-C6-alkenylox-y, C2-C4-alkynyloxy, Cl-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and ~, Y and Z independently of one another are each hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, -S(~)n-Cl-C4-alkyl, -S(0)n-Cl-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(0)OR4, where R4 is hydrogen or Cl-C~-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are eaeh hydrogen, Cl-C4-alkyl, Cl-C4-alkylearbonyl, Cl-C4-haloalkylcarbonyl or Cl-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-posi-tion, R3 is Cl-C4-allcoxy, and two of the substituents X, Y and Z are hydrogen, -the third ~2~3~
g substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
The compounds of the formula II, Group B, which have been specially developed for the production of the compounds of the formula I according to the invention, are still novel and likewise form subject matter of the present invention.
A process for producing 4-(4'-chlorophenoxy)-benzoyl-acetic acid ethyl ester by reaction of 4-(4'-chlorophenoxy)-benzoic acid with thionyl chloride and sodium-acetyl-acetic acid ethyl ester and subsequent deacetylation is described in Arzneimittelforschung (Pharmacological Research) 30 (1), No. 3 (1980), 454-459.
In the German O~fenlegungsschrift No. 2,436,012 are described 4-phenoxy-benzoylacetic acid and alkyl esters thereof in which the phenoxy group is unsubstituted or substituted by a fluorine, chlorine or bro~ine atom or by a trifluoro-methyl group. The alkyl esters are obtainable by Friedel-Crafts acylation of the corresponding diphenyl ethers with malonic ester chlorides, and the corresponding acids by subsequent saponification.
In addition to being obtainable by the processes already mentioned in the foregoing, compounds of the formula II
can also be produced, using a process analogous to that described in J. Amer. Chem. Soc. 70 (1948), 3356-3360, by reaction of phenoxyphenyl derivatives with malonic acid methyl ester chloride.
Furthermore, compounds of the formula II in which R3 is cl-C4-alkoxy can be produced, using a process analogous to that described in Tetrahedron 20 (1964), 1625-1632, according to the following reaction scheme:
-. .
~:3~L~39 - c~3 i ~~ y1) NaH (2 equiv.) ~ dioxane z 11 R OCOR
(VI~I) 7 7 2 ) IlO~c O~
~. ~ >~
(II) In the above formulae, X, Y and Z have the meanings given for formula II, and R7 is Cl-C4-alkyl.
The compounds of the formula VIII ~re known and can be produced by me-thods anaLogous to known methods (cf. for example US Patent Specification No. 4,125,729; and Belgian Patent Specification No. 639,727 [Ref. in Chem. Abst. ~2 (1965), 14581h]).
The production of compounds of the formula II by a process analogous to the last-mentioned process is further illustrated in the following Example.
Example 9: 4-(3l-Trifluoromethyl-phenoxy)-benzoylacetic acid methy] ester.
To a mixture of 29 g of NaH (2 equiv.; 55% oil disper-sion, washed three times with toluene) and 54 g of dimethyl-carbonate in 400 ml of dioxane are added dropwise, at 85~C, 84.2 g of 4-(3'-trifluoromethylpllenoxy)-acetophenone , -~239L~
dissolved in 160 ml of dioxane, whereupon an evolution of hydrogen immediately occurs. After the reaction has subsided, the reaction mixture is stirred at 85C for a further 2 hours, and 100 ml of acetic acid are then added dropwise with ice cooling. To the paste obtained are added 400 ml of ether and about 200 g of neutral Alox I (aluminium oxide (alumina) Woelm, activity stage I), and the mixture is filtered. The filtrate is concentrated by evaporation, dissolved in acetone, washed successively with water, a ln saturated NaHC03 solution and a saturated NaCl solution, dried, and concentrated by evaporation. The viscous product obtained can be used directly for the production of compounds of the form-1la I, or it is distilled at 10 2 Torr and 160C, or recrystallised from hexane (m.p. 50-55C).
The yield of pure product is about 65 g (65% of theory).
The following compounds of the formula II can be produced in an analogous manner: -C~12 Ij_o~
~0/ l ~. Y
~ O~ z ' Table I: Group B Compounds ~ .
No. R3 X Y Z in.p.~C
(Constitution~
.. ~
B-l C2H5 2-C1 4-Cl 11 (viscous) B-2 OCH3 2-Cl 4-CF3 H (viscous) B-3 3 3 ( ~3 H S-CF3 9G
B-4 OCH3 3-Cl 11 5-C1 61-63 B-5 OC~; 2-C1 4-CF3 H (viscous) 1,-6 OC~i~C~.~Cl 3-CF3 H H
, . ~
~23~39 Table 1 (continuation): Group B Cornpo~ndS
_ _ No. R3 ~ y _ . _ (Constitution`
B-7 0cll2cH=cH2 3-CF3 H H
B-8 0cll2c-cH 3-CF3 H H _ B-ll OC~I2CC13 3-Cl H H ~
B-12 OCH2cH=cH23-Br H H
B-13 OC2H5 3-J H H (viscous) B-l4 OC2H5 3-OCF3 H H (viscous) B-15 OCH2cH2cl3 OCF3 H _ B-16 C2H5 3-OCEIF2 H H (viScous)
3 7 3-0CIIF H H -B-20 C2H5 3-SCH3 H H (viscous) B-21 OC3H7n 3-SCH3 .I H ~
B-22 OC2~15 3-SOCil3 H H
B-23 C2H5 3-SO~>C~I3 il H (viscous) B-24 C2ll5 3-OC[ CIIF ll H (viscous) B-25C~12C~12cl .3~CF2cll~2 H ~ .
E-26C2ll5 3-SCIlF2 H 1l (viscous) r-~7 _ _ _ _ _ _ .
_ ~ 23~39 1'1 Table 1 (con inuation): Group B Compounds _ .
No . ~3 ~ y z m .p . C
(Cons ti tU tion) .
B-28C2H5 3-OCI-13 H 11 (viscous) B-30OC~133-(:(O)OC113 H 1-1 (viscous) B-31OC2~53-C(O):)C21-15 H H
B-34C2H53-N(CH3)2 H H (viscous) B-35C2H5 3-CN H 11 (viscous) B-360cH2cH2cl 3-CN H H -B-3SC2ll5 H 4-SCF3 H
B-40C2H5 H 4-OCHF2 H _ B-41OC2H5 H 4-OCF3 H _ B-43OC2H5 2-C1 3-Cl H
B~44 C2ll5 3-C1 4-Cl H
~~45 OC2H5 2-Cl 1I G-Cl B-47C2ll5 2-Br 3-Br H
B-48C2ll52-OC113 H H
- ~
.
~ . ~
",, ~ . .
3~3~
_ 15-Table 1 (~ontinuation): ~roup B Compounds ~0. R ~ Y z m.p.C
3 (Constitution~
B-!,9~C2}T5 H 4-OCH3 H
B-54OCH3 3-CN H H 62-66 .
o~c\ ~ ~ o ~ $
3 ~
z Table 2: Group B
.
No. R3 ~ y Z Constitution B-55 OCH3 3-Cl 11 H viscous _ ~23~3~
In the following two examples are given typical preparation procedures for two dihydropyrones of the formula I.
Example 2: 2-(4'-[3"-Chlorophenoxy~-phenyl)-3-methoxy-carbonyl-5-ethyl-5,6-dihydro-4-pyrone.
a) 10 ml of abs. methanol and 1 ml of CC14 are dissolved in 50 ml of abs. ether, and to the solution are added 1.1 g of magnesium chips. As evolution of ll2 commences, 13.7 g of 4-(3'-chlorophenoxy)-benzoylacetic acid methyl ester, dissolved in a small amount of ether, are added dropwise.
The reaction to 2-[4'-3"-chlorophenoxy)-benzoyl] -2-(methoxy-magnesium)-acetic acid methyl ester occurs immediately with a considerable heat of reaction. To the golden-yellow solution obtained are added 100 ml of abs. toluene, and the ether as well as unreacted methanol are subsequently distilled off.
b) The solution o 2-L4'-(3"-chlorophenoxy)-benzoyl]-2-(methoxymagnesium)-acetic acid methyl ester in toluene, obtained according to a), is coo]ed to 5C, and 5.5 g of 2-ethylacrylic acid chloride are subsequently added dropwise.
The mixture is allowed to react fully for two hours at room 3 ,y~
123~3~
temperature, and 50 ml of abs. acetonitrile are then added.
The homogeneous solution obtained is poured into ice/
conc. H2S04 and stirred for 15 minutes. The product is extracted with ether, washed successively with 2 N
H2S04, a saturated NaHC03 solution and a saturated NaCl solution, dried, and concentrated by evaporation to leave a viscous reddish-brown oil.
c) The viscous oil obtained according to b) is dissolved in 200 ml of methanol; there is then added 1 ml of acetyl chloride, and the solution is refluxed overnight. It is subsequently concentrated by evaporation; and the residue is taken up in ether, and treated with active charcoal.
Concentration by evaporation is again performed, and the viscous oil obtained is caused to crystallise in a petroleum ether/ether mixture. The yield is 7.4 g (42.5% of theory) of 2 (4'-[3"-chlorophenoxy]-phenyl)-3-methoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone, m.p. 99-101C.
Example3 : 2-(4'-[4"-Chlorophenoxy]-phenyl)-3-ethoxy-carbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone.
a) In a manner analogous to that described in Example 1, there is prepared, from 14 g of 4-(4'-chlorophenoxy)-benzoylacetic acid ethyl ester, 1.2 g of magnesium chips and 10 ml of ethanol, a solution of 2-[4'-(4"-chloro-phenoxy)-benzoyl]-2-(ethoxymagnesium)-acetic acid ethyl ester in toluene.
b) To the solution oE 2-[4'-(4"-chlorophenoxy)-benzoyl]-2-(ethoxymagnesium)-acetic acid ethyl ester in toluene obtained according to ~) are added dropwise, with coolîng of the solution to -5C, 5.7 g of 2,3-dimethylacrylic acid chloride. The mixture is allowed to fully react for 2 hours at room temperature, and 50 ml of abs. acetonitrile are added. The homogeneous solution obtained is poured into ice/conc. H2SC4 dnd stirred for 15 minutes. The ., ~34~3~
- 18 ~
reaction product is extracted with ether, and successively washed with 2 N H2S04, with a saturated NaHC03 solution and with a saturated NaCl solution; it is subsequently dried, and concentrated by evaporation to leave a viscous oil.
c) The viscous oil o'btained according to b) is cyclised under reflux overnight in 200 m'l of ethanol and 1 ml of acetyl chloride. The solution is concentrated by evaporation and chromatographed on 1100 g of silica gel in ether/
hexane 1:1. There are isolated 4.8 g of trans-2-(4'-[4"-chlorophenoxy]-phenyl) 3-ethoxycarbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone (m.p. 94-96C, Rf (ether/hexane 1:1) about 0.3), and also 1.2 g of cis-2-(4'-L4"-chlorophenoxy]-phenyl)-3-ethoxycarbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone (m.p. 88-90C, Rf (ether/hexane l:l) about 0.2). The structure was defined on the basis of the different coupling CH(S)-CH(6) P
[JCH(5) CH(6)(Cis): 3 Hz; JCH(5)-CH(6)( ): 12 Hz].
;~
3~
The compounds of the formula I have excellent herbicidal properties. The compounds are suitable for combating both monocotyledonous and dicotyledonous plants, and they can be applied using either the pre-emergence method or the post-emergence method. The compounds of the formula I or compositions containing them can be used particularly advantageously for selectively combating weeds in cultivated crops of cereals.
Compounds of the formula I which are particularly ~0 worthy of mention by virtue of their advantageous properties are: 2-(4'-~3"-trifluoromethyl-phenoxy]-phenyl)-3-methoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone and 2-~4'-[3"-trifluoromethyl-phenoxy]-phenyl)-3-ethoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone.
In the case of stereoisomeric compounds (for example compounds 5 and 6), the activity o~ the cis compound is greater than that of the trans compound.
. ..
B-22 OC2~15 3-SOCil3 H H
B-23 C2H5 3-SO~>C~I3 il H (viscous) B-24 C2ll5 3-OC[ CIIF ll H (viscous) B-25C~12C~12cl .3~CF2cll~2 H ~ .
E-26C2ll5 3-SCIlF2 H 1l (viscous) r-~7 _ _ _ _ _ _ .
_ ~ 23~39 1'1 Table 1 (con inuation): Group B Compounds _ .
No . ~3 ~ y z m .p . C
(Cons ti tU tion) .
B-28C2H5 3-OCI-13 H 11 (viscous) B-30OC~133-(:(O)OC113 H 1-1 (viscous) B-31OC2~53-C(O):)C21-15 H H
B-34C2H53-N(CH3)2 H H (viscous) B-35C2H5 3-CN H 11 (viscous) B-360cH2cH2cl 3-CN H H -B-3SC2ll5 H 4-SCF3 H
B-40C2H5 H 4-OCHF2 H _ B-41OC2H5 H 4-OCF3 H _ B-43OC2H5 2-C1 3-Cl H
B~44 C2ll5 3-C1 4-Cl H
~~45 OC2H5 2-Cl 1I G-Cl B-47C2ll5 2-Br 3-Br H
B-48C2ll52-OC113 H H
- ~
.
~ . ~
",, ~ . .
3~3~
_ 15-Table 1 (~ontinuation): ~roup B Compounds ~0. R ~ Y z m.p.C
3 (Constitution~
B-!,9~C2}T5 H 4-OCH3 H
B-54OCH3 3-CN H H 62-66 .
o~c\ ~ ~ o ~ $
3 ~
z Table 2: Group B
.
No. R3 ~ y Z Constitution B-55 OCH3 3-Cl 11 H viscous _ ~23~3~
In the following two examples are given typical preparation procedures for two dihydropyrones of the formula I.
Example 2: 2-(4'-[3"-Chlorophenoxy~-phenyl)-3-methoxy-carbonyl-5-ethyl-5,6-dihydro-4-pyrone.
a) 10 ml of abs. methanol and 1 ml of CC14 are dissolved in 50 ml of abs. ether, and to the solution are added 1.1 g of magnesium chips. As evolution of ll2 commences, 13.7 g of 4-(3'-chlorophenoxy)-benzoylacetic acid methyl ester, dissolved in a small amount of ether, are added dropwise.
The reaction to 2-[4'-3"-chlorophenoxy)-benzoyl] -2-(methoxy-magnesium)-acetic acid methyl ester occurs immediately with a considerable heat of reaction. To the golden-yellow solution obtained are added 100 ml of abs. toluene, and the ether as well as unreacted methanol are subsequently distilled off.
b) The solution o 2-L4'-(3"-chlorophenoxy)-benzoyl]-2-(methoxymagnesium)-acetic acid methyl ester in toluene, obtained according to a), is coo]ed to 5C, and 5.5 g of 2-ethylacrylic acid chloride are subsequently added dropwise.
The mixture is allowed to react fully for two hours at room 3 ,y~
123~3~
temperature, and 50 ml of abs. acetonitrile are then added.
The homogeneous solution obtained is poured into ice/
conc. H2S04 and stirred for 15 minutes. The product is extracted with ether, washed successively with 2 N
H2S04, a saturated NaHC03 solution and a saturated NaCl solution, dried, and concentrated by evaporation to leave a viscous reddish-brown oil.
c) The viscous oil obtained according to b) is dissolved in 200 ml of methanol; there is then added 1 ml of acetyl chloride, and the solution is refluxed overnight. It is subsequently concentrated by evaporation; and the residue is taken up in ether, and treated with active charcoal.
Concentration by evaporation is again performed, and the viscous oil obtained is caused to crystallise in a petroleum ether/ether mixture. The yield is 7.4 g (42.5% of theory) of 2 (4'-[3"-chlorophenoxy]-phenyl)-3-methoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone, m.p. 99-101C.
Example3 : 2-(4'-[4"-Chlorophenoxy]-phenyl)-3-ethoxy-carbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone.
a) In a manner analogous to that described in Example 1, there is prepared, from 14 g of 4-(4'-chlorophenoxy)-benzoylacetic acid ethyl ester, 1.2 g of magnesium chips and 10 ml of ethanol, a solution of 2-[4'-(4"-chloro-phenoxy)-benzoyl]-2-(ethoxymagnesium)-acetic acid ethyl ester in toluene.
b) To the solution oE 2-[4'-(4"-chlorophenoxy)-benzoyl]-2-(ethoxymagnesium)-acetic acid ethyl ester in toluene obtained according to ~) are added dropwise, with coolîng of the solution to -5C, 5.7 g of 2,3-dimethylacrylic acid chloride. The mixture is allowed to fully react for 2 hours at room temperature, and 50 ml of abs. acetonitrile are added. The homogeneous solution obtained is poured into ice/conc. H2SC4 dnd stirred for 15 minutes. The ., ~34~3~
- 18 ~
reaction product is extracted with ether, and successively washed with 2 N H2S04, with a saturated NaHC03 solution and with a saturated NaCl solution; it is subsequently dried, and concentrated by evaporation to leave a viscous oil.
c) The viscous oil o'btained according to b) is cyclised under reflux overnight in 200 m'l of ethanol and 1 ml of acetyl chloride. The solution is concentrated by evaporation and chromatographed on 1100 g of silica gel in ether/
hexane 1:1. There are isolated 4.8 g of trans-2-(4'-[4"-chlorophenoxy]-phenyl) 3-ethoxycarbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone (m.p. 94-96C, Rf (ether/hexane 1:1) about 0.3), and also 1.2 g of cis-2-(4'-L4"-chlorophenoxy]-phenyl)-3-ethoxycarbonyl-5,6-dimethyl-5,6-dihydro-4-pyrone (m.p. 88-90C, Rf (ether/hexane l:l) about 0.2). The structure was defined on the basis of the different coupling CH(S)-CH(6) P
[JCH(5) CH(6)(Cis): 3 Hz; JCH(5)-CH(6)( ): 12 Hz].
;~
3~
The compounds of the formula I have excellent herbicidal properties. The compounds are suitable for combating both monocotyledonous and dicotyledonous plants, and they can be applied using either the pre-emergence method or the post-emergence method. The compounds of the formula I or compositions containing them can be used particularly advantageously for selectively combating weeds in cultivated crops of cereals.
Compounds of the formula I which are particularly ~0 worthy of mention by virtue of their advantageous properties are: 2-(4'-~3"-trifluoromethyl-phenoxy]-phenyl)-3-methoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone and 2-~4'-[3"-trifluoromethyl-phenoxy]-phenyl)-3-ethoxycarbonyl-5-ethyl-5,6-dihydro-4-pyrone.
In the case of stereoisomeric compounds (for example compounds 5 and 6), the activity o~ the cis compound is greater than that of the trans compound.
. ..
Claims (7)
1. A compound of the formula II
(II) wherein R3 is C1-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, C1-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4 haloalkyl, Cl-C4-haloalkoxy, -S(O)n-C1-C4-alkyl, -S(O)n-C1-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or C1-C4-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-haloalkyl-carbonyl or C1-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is C1-C4-alkoxy, and two of the substituents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
(II) wherein R3 is C1-C4-alkoxy, C2-C6-alkenyloxy, C2-C4-alkynyloxy, C1-C4-haloalkoxy or C3-C5-alkoxyalkoxy, and X, Y and Z independently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4 haloalkyl, Cl-C4-haloalkoxy, -S(O)n-C1-C4-alkyl, -S(O)n-C1-C4-haloalkyl, where n is 0, 1 or 2, or they are each C(O)OR4, where R4 is hydrogen or C1-C4-alkyl, or they are each NO2, CN or NR5R6, where R5 and R6 independently of one another are each hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-haloalkyl-carbonyl or C1-C4-haloalkylsulfonyl, with the proviso that, when the phenoxy group is in the p-position, R3 is C1-C4-alkoxy, and two of the substituents X, Y and Z are hydrogen, the third substituent is not hydrogen, fluorine, chlorine, bromine or trifluoromethyl.
2. A compound of the formula II according to claim 1, wherein R3 is C1-C4 alkoxy which can be straight-chain or branched-chain, or allyloxy, propargyloxy, 2,2,2-trichloro-ethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, methoxymethoxy or 2-(methoxy)-ethoxy, and one of the substituents X, Y and Z is hydrogen, and the two other substituents independently of one another are hydrogen, chlorine, bromine, iodine, fluorine, methyl, ethyl, methoxy, trifluoromethyl, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methylthio, methylsulfinyl, methyl-sulfonyl, trifluoromethylthio, difluoromethylithio, trifluoro-methylsulfinyl, methoxycarbonyl, ethoxycarbonyl, nitro, cyano, amino, methylamino or dimethylamino.
3. A compound of the formula II according to claim 2, wherein the phenoxy group is in the p-position.
4. A compound of the formula II according to claim 3, wherein R3 is a methoxy or ethoxy group, and one of the substi-tuents X, Y and Z is hydrogen, and the two other substituent independently of one another are hydrogen, chlorine, methyl, trifluoromethyl, trifluoromethoxy, difluoromethylthio or cyano.
5. A compound of the formula II according to claim 4, wherein one of the substituents X, Y and Z is hydrogen, and the two other substituents independently of one another are hydrogen, chlorine, trifluoromethyl or trifluoromethoxy.
6. A compound of the formula II according to claim 5, wherein x is trifluoromethoxy, and Y and Z are hydrogen.
7. The compound accoding to claim 6, which is 4-(3'-trifluoromethoxyphenoxy)-benzoylacetic acid ethyl ester. --.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000471811A CA1234139A (en) | 1981-06-03 | 1985-01-09 | Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH363081 | 1981-06-03 | ||
| CH3630/81-5 | 1981-06-03 | ||
| CA000404230A CA1195334A (en) | 1981-06-03 | 1982-06-01 | Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds |
| CA000471811A CA1234139A (en) | 1981-06-03 | 1985-01-09 | Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1234139A true CA1234139A (en) | 1988-03-15 |
Family
ID=25669704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000471811A Expired CA1234139A (en) | 1981-06-03 | 1985-01-09 | Dihydropyrones, processes for producing them, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1234139A (en) |
-
1985
- 1985-01-09 CA CA000471811A patent/CA1234139A/en not_active Expired
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