CA2092797A1 - Optically active pyrimidinyl- or triazinyl-oxy (or -thio) carboxylic acid derivatives, processes for their preparation, and use as herbicides or plant growth regulators - Google Patents

Abstract

Abstract of the Disclosure Optically active pyrimidinyl- or triazinyl-oxy (or -thio) carboxylic acid derivatives, processes for their prepar-ation, and use as herbicidss or plant growth regulators.

The invention relates to optically active pyrimidinyl-or triazinyl-oxy (or -thio) carboxylic acid derivatives of the formula (I) (I) in which X, Y, R1, R2, R3 and R4 are as defined in claim 1, in an an enantiomeric purity of the L form of greater than zero.

The compounds of the formula (I) according to the inven-tion have an outstanding herbicidal activity against a broad range of harmful plants.

Description

2~92~97 HOECHST AKTIENGESELLSCHAFT HQE 92/FO75 Dr.WE/wo Description Optically active pyrimidinyl- or triazinyl-oxy (or -thio) carboxylic acid derivatives, processe~ for their prepar-ation, and use as herbicides or plant growth regulator6.

It is known that a large number of natural substances which have a biological activity are optically active, i.e. rotate the plane of the polarized light to the right (~) or the left (-) due to the presence of one or more asymmetric carbon atoms. These compounds ver~ frequently have a higher biological activity than corresponding compounds which have been obtained synthetically and which are optically inactive. Similarly, this applies to some synthetically produced active substances such as pharmaceuticals or crop protection agents which have asymmetric carbon atoms and which are usually obtained during synthesis in the form of opticall~ inactive racemates, i.e. mixtures of identical amounts of the dextrorotatory and laevorotatary enantiomers. Here too, the separation of isomers result~ not infrequently in the discovery that the activity of one of the two enantiomers exceeds the activity of the racemate. ~owever, as a rule it cannot be predicted whether the laevorotatory or dextrorotatory form i8 the active form in the particular case and whether there i8 a connection at all between effectiveness and optical activity.

In recent years, compounds have been disclosed from the class of the pyrimidinyloxycarboxylic acid derivatives which are interesting due to their herbicidal and plant-growth-regulating properties; see, for example, EP-A-0,347,811, EP-A-0,409,369, EP-~-0,409,368, EP-A-0,400,741. The~e compounds have an asymmetric carbon ~tom in the adjacent position ("~-po~ition~ or 2-position) relative to the carboxylic acid derivative ' -" 2~9~7~7 group, so that there exist two enantiomeric, opticallyactive forms which are generally termed as the D and L
form according to the nomenclature based on the Fischer projection, and as enantiomers with (R) or (S) configur-ation, more exactly (2R) and (2S) configuration,respectively, based on the Cahn-Ingold-Prelog nomen-clature (see Angew. Chem. 78 (1966) 413 et 3eq.).

It has now been found that the L enantiomers of some of these compounds are distinguished by a considerably more powerful herbicidal activity compared with the racemates.

The invention therefore relates to optically active pyrimidinyl- or triazinyl-oxy (or -thio) carboxylic acid derivatives of the formula (I) ~N R3 y ~ X ~ / (I) 2~N ~r R4 in which 15 X is 0 or S, Y is N or CH, R1 and R2 independently of one another are hydrogen, alkyl, alkoxy, alkylthio, halogen, haloalkoxy, amino, alkylamino or dialkylamino, R3 is an aliphatic or araliphatic radical of the formula ` 2~92797 ~7 Rl~f R9 t R 6 R ~

Rs and R6 independently of one another are hydrogen or alkyl or R5 and R~ together with the carbon atom linkinq them are a 3- to 6-membered ring which may contain one oxygen atom and which may be substituted by one or more alkyl groups, R7 is hydrogen, halogen, alkyl which is unsubsti-tuted or ~ubstituted by one or more radicals selected from the group comprising halogen, hydroxyl, alkoxy and alkylthio, or is cyclo-alkyl, hydroxyl, cyano, aryl or arylalkyl, the last-mentioned two radicals being unsubstituted or substituted in the aryl moiety, R3 is alkyl, phenyl or substituted phenyl or RB
together with R10 and the ethenylene group linking them are a cyclopentene or cyclohexene ring which is unsubstituted or substituted by one or more alkyl groups, R9 is hydrogen or alkyl, R10 radicals independently of one another are hydrogen or alkyl or R10 together with R8 and the ethenylene group linking them are a cyclopentene ring or cyclohexene ring which is unsubstituted or substituted by one or more alkyl groups, Rll is hydrogen, halogen, nitro, alkyl, haloalkyl, alkoxy, alkylsulfonyl, alkylsulfinyl or alkylthio, ' , ' ~

2~92~7 R4 is hydroxyl, -O~Cat+, an aliphatic saturated or mono- or polyunsaturated hydrocarbonOxY radical, preferably having one to 24 carbon atoms, in particular a radical selected from the group compri~ing alkoxy, alkenyloxy and alkynyloxy, the radi~al being unsubstituted or substituted by one or more radic~ls 6elected from the group comprising halogen, al~oxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, phenyl, phen-oxy, phenylthio, the three last-mentioned radicals being un~ubstituted or substituted, aminocarbonyl, alkylaminocarbonyl anddialkyl-~minocarbonyl, oris phenoxy, substituted phenoxy, alkylidenaminoxy, cycloalkyloxy or halogen or R4 is the radical of a 5- or 6-membered cyclic lactone, preferably of a lactone radical which is bonded in the ~-position relative to the CO
group, or R4 is a radical of the formula -D1-CR12R13-D2-L or -0-5i-RIs - Rl6 Cat+ i8 the equivalent of a mono-, di- or poly-valent cation, R12 and Rl3 independently of one another are hydrogen, alkyl, alkenyl, alkynyl, aryl, substituted aryl, benzyl, alkoxy, alkenyl, alkynyloxy, aryloxy or substituted aryloxy, R14, R15 and R1s independently of one another are alkyl, alkenyl or alkynyl, phenyl or sub-~tituted phenyl, D1 is 0, S or NR17, R17 is hydrogen or alkyl, 20g2~7 D2 is a direct bond or a saturated or un~aturated hydrocarbon group, L is an acid derivative radical of the formula -C0-0-R18 or -C0-S-R1B and 5 Rls is hydrogen, alkyl, alkenyl or alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals sel-ected from the halogen group, or is cycloalkyl, cycloalkenyl, benzyl, phenyl or substituted phenyl, in an enantiomeric purity of the L form of greater than zero.

Decisive for the classification of the compounds of the formula (I) as L form or L enantiomer is, in analogy to the conventional classification of D- and L-glycer-aldehyde or D- and L-amino acids, the orientation of the pyrimidinyl- or triazinyl-oxy (or -thio) ~adical as reference ligand in the horizontal plane of the Fischer projection formula, the acid derivative group being arranged above the horizontal plane mentioned and the group of the formula R3 being arranged below the horiz-ontal plane mentioned, in each ca~e in the vertical plane. The L form of the compounds of the formula (I~
corxesponds to the (~S) configuration in accordance with the Cahn-Ingold-Prelog nomenclature.

The abovementioned term "enantiomeric purity" in percent [% ee], which is also termed "enantiomeric exces~", is to be understood as meaning the following quotient (see, for example, B. Testa "Grundl~gen der Stereochemie"
[Fundamental Principles of Stereochemistry], Verlag Chemie GmbH, Weinheim 1983, pages 144-145):

% ee = [IL-D)/(L+D)] x 100.

20927~

In the above mathematical formula, ~L~ and "D" are the concentrations of the L or the D form in the particular enantiomer mixture. The compounds of the formula (I) preferably exist in an L-enantiomeric purity of 40 to 100 percent, better 60 to 100 percent, in particular 80 to 100 percent. Thi~ corresponds to an amount of preferably 70 to 100 percent of L form, better 80 to 100 percent of L form, in particular 90 to 100 percent of L form, relative to the mixture of the D and L enantiomers.

In formula (I) and hereinafter, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio as well as the corresponding unsaturated and/or sub-stituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless specifically indicated otherwise, preferred carbon skeletons in these radicals are those having 1 to 4 carbon atoms, or, in the case of unsaturated groups, those having 2 to 4 carbon atoms. Alkyl radicals, also in the composite meanings such as alkoxy and haloalkyl etc., are methyl, ethyl, n-or i-propyl, n-, i-, t- or Z-butyl; alkenyl and alkynyl radicals have the meanings of the unsaturated radicals which are pos~ible and which correspond to the alkyl radicals, such as 2-propenyl, 2- or 3-butenyl, 2-propynyl and 2- or 3-butinyl. Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl is alkyl which is aub-stituted by one or more identical or different atoms selected from the halogen group; haloalkyl is, for example, CF3, CHF2, CH2CF3, CCl3, CClF2, CFCl2, CF2CF2. The same applies to haloalkenyl, haloalkoxy and other radical~ which are sub6tituted by halogen. Aryl is, for example, phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; aryloxy preferably has the meaning of the oxy radical~ which correspond to the abovementioned aryl radicals, in particular phenoxy. Heteroaryl, or hetero-aryl in heteroaryloxy, is, for example, pyridyl, pyrimidyl, pyridazyl, thienyl, furyl, pyrrolyl, pyrazolyl 20927~7 and imidazolyl, preferably pyridyl and thienyl, but also bicyclic or polycyclic aromatic or araliphatic compound~.
Optionally substituted aryl or aryloxy, heteroaryl, heteroaryloxy, phenyl, phenoxy, benzyl, benzyloxy, or optionally substituted bicyclic radicals which have aromatic moieties are preferably in each case the corres-ponding unsubstituted radical or are a sub~tituted radical derived therefrom, the substituents being, for example, one or more, preferably 1, 2 or 3, radicals selected from the group comprising halogen, alkyl, haloalkyl alkoxy, haloalkoxy, nitro, cyano, alkoxy-carbonyl, alkylcarbonyl, alkanoyl, carbamoyl, mono- and dialkylaminocarbonyl, mono- and dialkylamino, alkyl-sulfinyl and alkylsulfonyl, and, in the case of radicals having carbon atoms, thoæe having 1 to 4, in particular 1 or 2, carbon atoms, being preferred. As a rule, pre-ferred substitutents are those selected from the halogen group, for example fluorine and chlorine, C1-C4-alkyl, preferably methyl or ethyl, C1-C4-haloalkyl, preferably trifluoromethyl, C1-C4-alkoxy, preferably methoxy or ethoxy, C1-C4-haloalkoxy, nitro and cyano. Particularly preferred are the substituents methyl, methoxy and chlorine.

Example~ of silicon-containing radicals R4 are trialkyl-silylalkoxy, aryldialkylsilylalkoxy, diarylalkylsily-alkoxy, trialkylsililylalkenyloxy, aryldialkylsilyl-alkenyloxy, diarylalkylsilylalkenyloxy, trialkylsilyl-alkynyloxy,aryldialkylsilylalkynyloxy,diarylalkylsilyl-akindyloxy, trialkylsilyloxy, aryldialkylsilyloxy, diarylalkylailyloxy.

Particularly interesting are compounds o~ the formula (I) according to the invention, in which R1 and R2 independently of one another are C1-C4-alkyl, C1-C4-alkoxy, halogen, C1-C4-haloalkoxy, C~-C4-alkylamino or di(Cl-C4-alkyl)amino, preferably methyl, methoxy, chlorine or methylamino, in -`` 20927~
- B -particular one of the two radicals i5 methoxy and the other radical is methyl, methoxy, chlorine or methylamino~

Other particularly interesting compounds of the formula (I) according to the invention are those in which R5 and R5 independently of one another are hydroqen or C1-C4-alkyl or R5 and R6 together with the carbon atom linking them are a 3- to 6-membered ring which can contain one oxygen atom and which can be substituted by one or more C1-C4-alkyl radicals, R7 is hydrogen, halogen, C1-C4-alkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkylthio, or is C3-C~-cycloalkyl, hydroxyl, cyano, thienyl, naphthyl or dihydronaphthyl, the last-mentioned three radicals being unsubstituted or subRtituted, or is a radical of the formula R
- ( C H 2 ) p ~/

p is 0, 1, 2 or 3, R8 i~ C1-C4-alkyl, phenyl or sub~tituted phenyl or R8 together with R10 and the ethenylene group linking them are a cyclopentene or cyclohexene ring which is un~ub~tituted or ~ubstituted by one or more C1-C4-alkyl radicals, R9 is hydrogen or C1-C4-alkyl, R10 radicals independently of one another are hydrogen or C1~C4-alkyl or R10 together with RB
and the ethenylene group linking them are a cyclopentene or cyclohexene ring which iB

2~9~7 unsubstituted or sub6tituted by one or more C1-C4-alkyl, radical~
Rl1 is hydrogen, halogen, nitro, C~-C~2-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-alkyl-sulfonyl, C~-C4-alkylsulfinyl or C1-C4-alkyl-thio.

Other particularly interesting compounds of the formula (I) according to the invention are those in which R3 is an aliphatic, araliphatic or aromatic radical of the formula _C~,5R6R7 R5 and R5 independently of one another are hydrogen or C1-C4-alkyl or R5 and R6 together with the carbon atom linking them are a 5- or 6-membered ring and R7 is hydrogen, halogen, C1-C4-alkyl, phenyl or benzyl, preferably hydrogen or methyl.

R3 is preferably isopropyl, 2,2-dimethylethyl or cyclo-pentyl.

Other particularly interesting compounds of the formula (I) according to the invention are those in which R4 i8 hydroxyl, -O Cat', C1-C1B-alkoxy, C2-C18-alkenyloxy, C2-C1~-alkynyloxy, the last-mentioned three radical~ being unsub~tituted or ~ubstituted by one or more radicals selected from the group compri~ing halogen, C1-C4-alkoxy, C1-C4-alkylthio, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, phenyl, phenoxy, phenylthio, the three last-mentioned radicals being unsubstituted or substituted, aminocarbonyl, (C1-C4-alkyl)amino-carbonyl and di(C1-C4-alkyl)aminocarbonyl, or is 7 ~ ~

phenoxy, ~ubstituted phenoxy, (C1-C6-alkylidene)aminoxy, c3-cB-cycloalkyloxy or halogen, or R4 is the radical of a ~-butyrolactone or ~-valerolactone which is bonded in the ~-position relative to the CO group and which is unsubstituted or substituted by halogen, C1-C4-alkyl or (Cl-C4-alkoxy~carbonyl, or R4 is a radical of the formula -D1-CRl2Rl3-D2-L or -O-Si-R
I

Rl6 Cat+ is the equivalent of an alkali metal or alkaline earth metal or an ammonium salt of a primary, secondary, tertiary or quaternary amine or diamine or polyamine, R12 and R13 independently of one another are hydrogen, Cl-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, subetituted phenyl, benzyl, C~-C4-alkoxy, Cz-C4-alkenyl, Cz-C4-alkynyloxy, phenoxy or substituted phenoxy, R~ R1s and R16 independently of one another are C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl, phenyl or substituted phenyl, D1 is O, S or NR17, R17 is hydrogen or C1-C4-alkyl, 25 D2 is a direct bond or a group of the formula CH2 or CH2CHz, L is an acid derivative radical of the formula--CO-O-R1~ or -CO-S-R;8, preferably -CO-O-R1~, and 30 R1~ is hydrogen, Cl-C18-alkyl, Cz-C~-alkenyl or Cz-C~-alkynyl, the last-mentioned three radi-cals being un~ubstituted or substituted by 2~27~7 one or more radicals ~elected from the halogen group, or is C3-C8-cycloalkyl, C3-C8-cyclo-alkenyl, benzyl, phenyl or substituted phenyl.

Other particularly interesting compounds of the formula (I) according to the invention are those in which R4 is hydroxyl, -O~Cat*, C1-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C3-C6-cycloalkyl-oxy, phenyloxy, (C1-C4-alkyloxy)-C1-C4-alkoxy, (C~-C4-alkyl)carbonyl-Cl-C4-alkoxy~ Cl-C4-lD haloalkyloxy, C1~C4-alkylidenaminoxy, (C1-C4-alkylthio)-C1-C4-alkoxy, phenyl-C1-C4-alkoxy, ~ubstituted phenyl-Cl-C4-alkoxy, phenoxy-Cl-C4-alkoxy, substituted phenoxv-C1-C4-alkoxy, phenylthio-Cl-C4-alkoxy, ~ubstituted phenyl-thio-C1-C4-alkoxy, such as nitrophenylthio-Cl-C4-alkoxy, or a benzyloxy radical which i6 substituted by (C1-C4)alkyl or (C1-C4)alkoxy, benzoxy or benzoxy which is substituted by C1-C4-alkyl, C1-C4-alkoxy, halogen or nitro, or R4 i~ a radical of the formula Dl-cRl2Rl3-D2-L, Cat+ iB the equivalent of an alkali metal, ~uch as sodium or potassium, or of an ammonium ~alt of a primary, secondary, tertiary or quaternary amine, D1 is 0, S, NH, methylamino or ethylamino, D2 i8 a direct bond, R12 and Rl3 independently of one another are hydrogen, Cl-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl or benzyl, preferably hydrogen or methyl, L iB an acid derivative radical of the formula -co-o-Rl8 or -Co-S-R19 Rl8 is hydrogen, C1-C4-alkyl, C2-C8-alkenyl or C2-C4-alkynyl, cyclohexyl, cyclopentyl, cyclo-hexenyl, cyclopentenyl, benzyl, phenyl or substituted phenyl.

20~2~7 Preferred compounds of the formula (I) according to the invention are those in which R4 is hydroxyl, -O~Catl or C1-C4-alk~xy.

Other preferred compounds of the formula tI) according to the invention are those in which the individual radicals or groups contain two or more radical~ or groups which have been designated as being preferred.

The present invention furthermore relates to the process for the preparation of compounds of the formula tI), which comprises (a) reacting a compound of the formula (II) H CoR4 R3 - C - XH (Il), in which R3, R4 and X have the meanings mentioned in formula (I), with a compound of the formula (III) N U C 1 ~(~ (111), N~

in which NUC1 is a leaving group, for example from the group comprising halogen, alkylsulfonyl, benzylsulfonyl and eubstituted benzylsulfonyl, and R1, R2 and Y have the meaning mentioned in formula (I), in the presence of an organic or inorganic base, or 2 ~ 7 (b) reacting a compound of the formula (IV) ~ 4 (l~
H COR

in which NUC2 is a leaving group, for example from the group compriæing halogen, tolylsulfonyloxy and methylsulfonyloxy, and R3 and R4 are as defined in formula (I), with a compound of the formula (V) H X ~
N~ 2 R

in which R1, R2, X and Y have the meanings mentioned in formula (I), in the presence of an inorganic or organic base, or 0 (c) in the event that, in formula tI), R4 is OH or -O~Catt, reacting a compound of the formula (I), in which R4 is not hydroxyl or -O~Catt, but preferably an alkoxy radical, with the aid of bases in water or water/alcohol mixtures to give the free acid of the formula (I) in which R4 is hydroxyl, or (d) in the event that, in formula (I), R4 is other than OH or -O~Catt, reacting a compound of the formula (I), in which R4 is hydroxyl, with thionyl chloride, oxalyl chloride, chlorocarbonate, carbonyldiimidazole or dicyclohexylcarbodiimide/4-(N,N-dimethylamino)pyridine in a manner known per se to give an activated carboxylic acid derivative and reacting the latter with a compound of the formula (VI) R4-H (VI) in which R4 i6 as defined in formula (I), with the exception of the meanings hydroxyl and -O~Cat~, in the presence of an inorganic or organic base to give compounds of the formula (I) in which R4 is as defined in formula (VI), or (e) employing a mixture of the L form o~ the formula (I) with the corresponding D form, in particular a racemic mixture, and then carrying out a racemate resolution process, or (f) in the event that, in formula (I), R4 is other than OH or -O~Cat', reacting a compound of the formula (I) in which R4 i5 hydroxyl with a halogen compound of the ~ormula (VII) R-~al (VII) in which R i8 defined in such a way that R-O- has the meaning of Rb as in formula (I), in the presence of an inorganic or organic base.

Suitable bases for the reactions (a), (b), (d) and (f) are, for example, inorganic base~ from the group of the alkali metal carbonates such as Na2CO3, K2CO3, NaHCO3 or KHCO3, alkali metal hydrides such as NaH and XH, and alkali metal fluorides, such as RF, or organic bases, for example tertiary amines such as triethylamine or DBU
(1,8-diazabicyclo[5.4~0]undec-7-ene).

2~92~97 Bases which are suitable for the reaction as in (C) are, for example, inorganic water-~oluble bases such as alkali metal hydroxides and alkaline earth metal hydroxides, preferably alkali metal hydroxides such as NaOH or XOH.

As a rule, it is advantageous or expedient to carry out these reactions in the pre~ence of a non-aqueous, aprotic solvent. Solvents which can be employed in these reac-tions are hydrocarbons such as n-heptane, benzene, toluene or xylene, halogenated hydrocarbons such as CH2Cl2, CHCl3 and CCl4, ethers such as diethyl ether, diglyme, monoglyme, dioxane and tetrahydrofuran (T~F), aprotic polar solvents, ~uch as dimethyl formamide (DMF), N,N-dimethylacetamide, dimethyl 8ul foxide (DMSO) and acetonitrile.

It can also be advantageous to carry out the reactions in the presence of catalysts, for example crown ethers or N,N,N',N'-tetramethylenediamine.

The starting substances of the formulae II-VI are known or can be synthe~ized analogously to known processes; cf.
EP-A-347,811, EP-A-400,369, EP-A-409,368, EP-A-400,741 and publications cited therein; in particular, optically active compounds of the formula (II) are to be prepared by the processes described or cited in J. Org. Chem.
1991, 56, 2499; Tetrahedron 35, 1601-1605 (1979), Tetra-hedron 32, 1101-1106 (1976), Tetrahedron Lett. 1975, 2187-2190, Bull. Chem. Soc. Jpn. 1968, ~1, 2178;
optically active compounds of the formula (IV) can be pxepared, inter alia, from the optically active compounds of the formula (II) in which X i~ an oxygen atom under customary conditions by converting the 2-hydroxyl group into a leaving grcup, for example by means of exchange or esterification reactions. The optically active compounds of the formulae (II) and (IV) are also accessible from the optically inactive enantiomer mixtures by racemate resolution.

2Q927~7 The optically active compounds of the formula (I) are also accessible from the optically inactive enantiomer mixtures by racemate resolution. A possible method of racemate resolution i8, for example, at the level of the racemic compounds in which R4 is hydroxyl, by salt form-ation with optically active amines such as brucine and strychnine followed by separation of the diastereomeric salts which have been formed. Alternatively, the enan-tiomers can be eparated by chromatography over ~pecific separating materials which have been modified with optically active compounds. For racemate resolution processes see, for example, ~ouben-Weyl "Methoden der organischen Chemie~ [Methods of Organic Chemi~try], Volume 11/2, p. 316 et ~eq.
~he compounds of the formula (I) according to the inven-tion have an excellent herbicidal activity against a broad range of economically important monocotyledon and dicotyledon harmful plants. The active substances also act efficiently on perennial weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control. In this context, it does not matter whether the substances are applied by the pre-plant, pre-emergence or post-emergence method.

Specifically, examples may be mentioned of ~ome represen-tatives of the monocotyledon and dicotyledon weed florawhich can be controlled by the compounds according to the invention, without the enumeration being intended as a restriction to certain species.

Examples of weed species on which the active sub~tances act efficiently are, from amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and also Cyperus species from the annual sector and from amongst the perennial species Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus specie~.

2~2~7 In the case of the dicotyledon weed 6pecies, the range of action extends to species such as, for ~xample, Galium, ~iola, Veronica, Lamium, Stellaria, Amaranthu~, Sinapis, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds.

The active substances according to the inventi~n equally effect outstanding control of weeds which occur under the specific conditions of rice growing such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.

If the compounds according to the invention are applied to the soil surface before germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledon stage but then their growth stops and, eventually, after three to four weeks have elapsed, they die completely.

If the active substances are applied post-emergence on the green parts of the plant~, growth equally Rtops drastically a very shoxt time after the treatment, and the weed plants remain at the growth ~tage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated at a very early point in time and in a sustained manner.

Even though the compounds according to the invention have an excellent herbicidal activity against monocotyledon and dicotyledon weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soya are damaged not at all, or only to a negligible extent. For these reas-ons, the present compounds are highly suitable for selectively controlling undesired plant growth in plant-ings for agricultural use.

- 20~7~7 In addition, the substances according to the invention have excellent growth-regulating properties in crop plants. They engage in the plant metabolism in a regulating manner and can thus be employed for the targetted influencing of plant constituents and for facilitating harvesting such as, fsr zxample, by provok-ing desiccation and stunted growth. Furthermore, they are also suitable for generally regulating and inhibiting undesired vegetative growth, without simultaneously destroying the plants. Inhibition of vegetative growth plays an important role in many monocotyledon and dicotyledon crops because lodging can be reduced hereby, or prevented completely.

The compounds according to the invention can be employed in the conventional preparations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. The in~ention therefore also relates to herbi-cidal and plant-growth-regulating compositions which comprise compounds of the formula ~I).

The compounds of the formula (I) can be formulated in various ways, depending on the prevailing biological and/or chemico-physical parameters. Examples of possible formulations which are suitable are: wettable powder6 (WP), water-soluble powders (SP), water-soluble con-centrates, emulsifiable concentrates (EC), emulsion6(EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspen~ion concentrates (SC), dispersions on an oil or water basis, solutions which are miscible with oils, capsule su6pensions (CS), dusts (DP~, seed-dressing agents, granules for broadcasting and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxe~.

20927~P~) These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie~ [Chemical Technology], Vol. 7, C.
Hauser Verlag Munich, 4th Ed. 1986; Wade van Valkenbury, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K.
Martens, "Spray Drying~ ~andbook, 3rd Ed. 1979, G.
Goodwin Ltd., ~ondon.

The necessary formulation auxiliaries ~uch as inert materials, surfactants, ~olvents and other additives are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluent and Carriers", 2nd Ed., Darland Books; Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J.
Wiley & Sons, N.Y.; C. Marsden, "Solventæ Guide", 2nd Ed., Interscience, N.Y., 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y., 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-Active Ethylene Oxide Adduct~], Wi~s. Verlagsgesell., Stuttgart 1976; Winnacker-KUchler, "Chemi6che Technologie"
[Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed., 1986.

Based on these formulations, it i~ also possible to prepare combinations with other pesticidally active substances such as, for example, insecticides, acari-cides, herbicides, fungicides, safeners, fertilizer~
and/or growth regulators, for example in the form of a ready mix or a tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain ionic and/or nonionic surfactants (wetting agent~, dispersants), for example polyoxy-ethylated alkylphenol~, polyoxyethylated fatty alcohol6, polyoxyethylated fatty amines, fatty alcohol polyglycol --` 2~92~

ether sulfates, alkanesulfonateæ, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2~-dinaphthylmethane-6,6~-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurinate, in addition to a diluent or inert substance. To prepare the wettable powders, the herbicidal active substances are ground finely, for example in conventional apparatuses such as hammer mills, blowing mills and air-jet mills and are mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons, or mixtures of the organic solvents with the addition of one or more ionic and/or nonionic surfactants (emulsifiers). Emul-sifiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium dodecyl-benzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ether~, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as, for example, sorbitan fatty acid esters or polyoxyethylene sorbitan estexs such as, for example, polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays, such as kaolin, bentonite and pyro-phyllite, or diatomaceous earths.

Suspension concentrates can be water- or oil-based. ~hey can be prepared, for example, by wet grinding by means of commercially available bead mill~, and if appropriate with an addition of surfactants as they have already been mentioned for example above in the case of the other formulation types.

,, --`` 2~27~7 Emulsions, for example oil-in-water emulsions (2W~, can be prepared for example by means of stirrers, colloid mills and/or static mixers using aqueous organic ~olvents and, if appropriate, surfactants as they have already been mentioned for example above in the case of the other formulation types.

Granules can be prepared either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers, such as ~and, kaolinite~ or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the preparation of fertilizer granules, if desired in a mixture with fertilizers.

Water-disper~ible granules are generally prepared by the conventional processes such as spray drying, fluidized-bed granulation, disk granulation, mixing by means of high-speed mixers and extrusion without solid inert material. For the preparation of disk, fluidized-bed, extruder and spray granules, see, for example, processe~
in "Spray-Drying Handbook" 3rd Ed. 1979, G. Goodwin Ltd., London; J.E. Brown~ng, "Agglomeration~, Chemical and Engineering 1967, pages 147 et seq. and "Perry' B Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further detail~ on the formulation of crop protection products see, for example, G.C. Klingman, ~Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, ~Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

20~2~7 The agrochemical preparations comprise, as a rule, ~.1 to 99 % by weight, in particular 0.1 to 95 ~ by weight, of active substance of the formula (I).

The active substance concentration in wettable powders is, for example, about 10 to 90 ~ by weight, the remain-der to 100 % is composed of conventional formulation components. In the case of emul6ifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80, % by weight. Formulations in the form of dusts comprise 1 to 30, preferably in mo~t cases 5 to 20, % by weight of active substance. Sprayable solutions comprise approximately 0.05 to 80, preferably 2 to 50, %
by weight of active substance. In the case of water-dispersible granules, the active sub~tance content depends partly on whether the active compound is in liquid or solid form and on which granulation auxili-aries, fillers and the like are used. The water-dispersible granules contain for example between 1 and 95 % by weight, preferably between 10 and 80 % by weight, of active substance.

In addition, the active sub6tance formulations mentioned comprise, if appropriate, the adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, preser-vatives, antifreeze agents and solvents, fillers, car-riers and colorants, antifoams, evaporation inhibitorsand pH and viscosity regulators which are conventional in each case.

Components which can be used in combinations with the active substances according to the invention in mixed formulations or in a tank mix are, for example, known active substances as they are described, for example, in Weed Research 26, 441-445 (1986), or "The Pe~ticide Manual", 9th Ed., ~he British Crop Protection Council, 1990/91, Bracknell, England, and the literature cited therein. Examples of herbicides which are known from the - ~0~2'~7 literature and which can be combined with the compounds of the formula (I) are the following active substance~
(Note: either the common name in accordance with the International Organization for Standardization (ISO) or the chemical name, if appropriate together with a conven-tional code number, are used to ~enote the compounds):
acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2~nitrophenyl]-2-methoxyethylidene]amino]oxy]acetic acid and methyl [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-phenyl]-2-methoxyethylidene]amino]oxy]acetate; alachlor;
alloxydim; ametryn; amidosulfuron; amitrol; AMS, i.e.
ammonium sulfamate; anilofos; asulam; atrazin; azi-protryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; ben-furesate; bensulfuron-methyl; bensulide; bentazone;
benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron;
bialaphos; bifenox; bromacil; bromobutide; bromofenoxim;
bromoxynil; bromuron; buminafos; busoxinone; butachlor;
butamifos; butenachlor; buthidazole; butralin; butylate;
carbetamide; CDAA, i.e. 2-chloro-N,N-di-2-propenylacet-amide; CDEC, i.e. 2-chloroallyl diethyldithiocarbamate;
CGA 184927, i.e. 2-[4-[(5-chloro-3-fluoro-2-pyridinyl)-oxy]phenoxy]propanoic acid and 2-propynyl 2-[4-[(5-chloro-3-fluoro-2-pyridinyl)oxy]phenoxy]propanoate;
chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorbufam; chlorfenac;
chlorflurecol-methyl; chloridazon; chlorimuron-ethyl;
chlornitrofen; chlorotoluron; chloroxuron; chlorpropham;
chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cin-methylin; cinosulfuron; clethodim; clomazone; clomeprop;
cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim;
cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB;
dalapon; desmedipham; desmetryn; di-allate; dicamba;
dichlobenil; dichlorprop; diclofop-methyl; diethatyl;
difenoxuron; difenzoquat; diflufenican; dimefuron;
dimethachlor; dimethametryn; dimethazone; chlomazon;
dimethipin; dimetrasulfuron; cinosulfuron; dinitramine;

20~27~7 dinoseb; dinoterb; diphenamid; dipropetryn; diquat;
dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, i.e.
5-cyano~ 1,1-dimethylethyl)-N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin; etho-fumesate; ~5231, i.e. N-E2-chloro-4-fluoro-5-~4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1~-tetrazol-1-yl]phenyl]-ethanesulfonamide; F6285, i.e. 1-t5-(N-methylsul~onyl)-amino-2,4-dichlorophenyl]-3-methyl-4-difluoromethyl-1,2,4-triazol-5-one; fenoprop; fenoxan, ~. clomazon;
fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasul-furon; fluazifop and its ester derivatives; fluchloralin;
flumetsulam; N-[2,6-difluorophenyl]-5-methyl-(1,2,4)-triazolo[1,5a]pyrimidine-2-~ulfonamide; flumeturon;
flumipropyn; fluorodifen; fluoroglycofen-ethyl;
fluridone; flurochloridone; fluroxypyr; flurtamone;
fomesafen; fosamine; furyloxyfen; glufosinate;
glyphosate; halosaten; haloxyfop and its ester deri-vatives; hexazinone; Hw 52, i.e. N-(2,3-dichlorophenyl)-4-(ethoxymethoxy)benzamide; imazamethabenz-methyl;
imazapyr; imazaquin; imazethamethapyr; imazethapyr;
imazosulfuron; ioxynil; isocarbamid; isopropalin; i~opro-turon; isouron; isoxaben; i~oxapyrifop; karbutilate;
lactofen; lenacil; linuron; MCPA; MCPB; mecoprop;
mefenacet; mefluidid; metamitrol; ~etazachlor; metha-benzthiazuron; metham; methazole; methoxyphenone; methyl-dymron; metobromuron; metolachlor; metoxuron; metribuzin;
met~ulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-~3-chloro-4-(1-methyl-ethyl)phenyl]-2-methylpentanamide; naproanilide; naprop-amide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazol; neburon; nico~ulfuron;
nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflu-razon; orbencarb; oryzalin; oxadiazon; oxyfluorfen;
paraquat; pebulate; pendimethalin, perfluidone;
pheni~opham; phenmedipham; picloram; piperopho~;

2~9~7 piributicarb; pirifenop-butyl; pretilachlor; primisul-furon-methyl; procyazine; prodiamine; profluralin;
proglinazine-ethyl; prometon; prometryn; propachlor;
propanil; propaquizafop and its ester derivatives;
propazine; propham; propyzamide; prosulfalin; pro-sulfocarb; prynachlor; pyrazolinate; pyrazon; pyrazo-sulfuron-ethyl; pyrazoxyfen; pyridate; quinclorac; quin-merac; quinofop and its ester derivatives; quizalofop and its ester derivatives; quizalofop-ethyl; ~uizalofop-p-tefuryl; renriduron; dymron; S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5/6,7-tetrahydro-2H-indazole; S 482, i.e. 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]-4,5,6,7-tetrahydro-lH-isoindole-1,3(2H)-dione; secbumeton; sethoxydim; siduron;
simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy~propanoic acid and methyl 2-[[7-~2-chloro-4-(trifluoromethyl)-phenoxy]-2-naphthalenyl]oxy]propanoate; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthi-uron; terbacil; terbucarb; terbuchlor; terbumeton;
terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[~2-ethyl-6-methylphenyl)Pulfonyl~-lH-1,2,4-triazole-1-carboxamide; thiazafluron; thifensulfuron-methyl; thio-bencarb; tiocarbazil; tralkoxydim; tri-allate; tria-sulfuron; triazofenamide; tribenuron-methyl; triclopyr;
tridiphane; trietazine; trifluralin; trimeturon; verno-late; WL 1105~7, i.e. 5-phenoxy-1-[3-(trifluoromethyl)-phenyl]-lH-tetrazole.

If appropriate, formulations which are in commercially available form are diluted for use in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, soil granules or granules for broadcasting as well as sprayable solutions are conventionally not diluted with further inert substances before use.

~` 20927~7 The application rate of the compounds of the formula (I) required varies with the external conditions ~uch as, inter alia, temperature, humidity and nature of the herbicide used. It can vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active ingredient, but it is preferably between 0.005 and 5 kg/ha.

A. Chemical Examples I) Methyl L-2-(4,6-dimethoxypyrimidin-2-yloxy)-3-methylbutanoate (Example 2 of Table 1) A mixture of 4.4 g (0.015 mol) of 2-benzylsulfonyl-4,6-dimethoxypyrimidine, 2.0 g (0.015 mol) of L-~-hydroxyisovaleric acid and 2.10 g (0.015 mol) of potassium carbonate is ~tirred for 4 hours in 40 ml of dimethyl sulfoxide at 100C. For working up, the reaction ~olution is poured into ice-water and, after filtration with suction, 2.5 g (61 ~ of theory) of methyl L-2-(4,5-dimethoxypyrimidin-2-yloxy)-3-methylbutanoate is obtained in the form of colorless crystals of m.p. 30-32C. The angle of rotation of the polarized light is ~]DZ~ = -31.49~.

II) L-2-(4,6-Dimethoxypyrimidin-2-yloxy)-3-methyl-butanoic acid (Example 1 of Table 1) In a steam bath, 1.3 g (0.005 mol) of methyl L-2-(4,6-dimethoxypyrimidin-2-yloxy)-3-methylbutanoate and 10 ml of concentrated sodium hydroxide solution are heated in a mixture of 50 ml of water and 30 ml of methanol, and the mixture is subsequently stirred for 1 hour. After an addition of water and acidification of the mixture, the latter is sub-jected to filtration with suction, and 0.7 g (58 %

2~92797 of theory) of L-2-(4,6-dimethoxypyrimidin-2-yloxy)-3-methylbutanoic acid i8 obtained in the form of colorless crystals of m.p. 126-128C. ~he angle of rotation of the compound is ~]D20 = -18.23.

The other compounds of Table 1 are obtained analogously to the process examples I) and II) or the processes as they are described further above.

In Table l, Ph is phenyl.

2~79~

Table l: Compounds of the formula (Ia) R ' y ~ X ~
~N C

. . -- _ ., Ex . Rl R2 R3 R4 X Y m . p . $C) No. _ _ or 1 OCH3 OCH3i-propyl OH O CH .[1~288D,-213 8 _ 2 " " ~ OCH3 ~ ,l [3a]D322 =
_ -31,49 3 " " " C2H5 " R [405~3D,7 5=o _ _ 4 " " " OC3H, ~n) u _ " OC,~H~ (i)_ _ 6 ll " " OC H (n) ll R
_ 4 9 _ 7 " " ,l OCH2scH3 ,l ,l 1,5109 _ _ -82,67 8 ll llll OCH CO CH H ll ~ 2 3 9 ., " ll OCH Ph R
2 _ 10 ll ll ll O N=c(cH3)2 ll " ~
_ _ 11 ll " " OCH2CH = CH2 ll ll 3 ~303 _ _ .
12 ~ " ll OCH2C J CH ll ll [o~2~ _ 13 OH ~ N
j 14 l OCH3 --,l u ~2~

_ . , , ,~ -.
Ex. Rl R2R3 R4 X Y or lnD~20]

t)C2H~ .. ..
16 ll ll " OC H (n) " "

17 __ u OC3H, (i) .. ..
18 u OC4HQ (n) " "
19 . .. OCH~,SCH~ ., ..
u OCH2C02C~3 u ..
21 ll ll ll OCH Ph ,. ,.
2_ _ 22 O-N = C~C:H3)2 _ u 23 OCH~,CH = CH~, u u 24 OCH2C ~ CH ., ,.
25 OCH3 OCH3 Cyclo- OH u CH
pentyl _ _ 26 OCH3 _ u 27 C2H5 .. _ __ 28 OC3H, (n) __ 29 OC3H, (i) _ _ OC4Hg (n) u u 31 OCH2SCH3 _ 32 OCH2CO2CH3 u _ 33 OCH2Ph u u 34 u .. O-N = C(CH3)~ ., u _ _ O-CH2CH = CH~ ,. ~
OCH2C CH ,l ..
37 ll .. ., OH O N
_ 38 " ,. ll OCH3 u u 39 u C2H5 _ OC3H, (n) u u 41 u OC3H, (i) u u 42 u OC4Hg (n) " "

- 2~927~7 R1 R2 R3 R4 X _ m P ~ ~0C) No. or [n l D
43 1~ ~ R OCH SCH n u I :~ ~ _ 44 .. .. .. OCH CO CH .. ., .
.. .. .. OCH Ph ,. ..
I 2 _ 46 .. .. .- O-N = C(CH ) R
I 3 2 ~ _ 1~ ~ ~ ~ OCH2CH -- CH, ~ ., .. u OCH2C ~ CH ~
49 .. .. t-Butyl OH O CH 145-147 [O]D =
¦ _ _ -17,99 .. .. .. OCH3 ., " 120-122 [o]20 =
-33.76 I _ _ 51 .. .. " OC2H5 " " 1[a323D15-4O

I _ ¦~ ~ ~ OC3H, (n) " u 53 ., .. .. OC H (i) .. ..
l 3 7 .. OC4Hg (n) " "
.. .. " OCH2SCH3 " " 92~29o4 [O]D =
_ -66,59 1~ u OCH2C02CH3 u _ L~ u .. OCH2Ph u u 58 ,. .. ll O-N=C(CH ) ,. u L~ r OCH2CH ~ CH2 _ ~ 11 L~ .. ., OCH2C ~ CH .. ll 61 ,. ll ll OH O N
I .
~ . OCH3 ..
L~ .. _ u OC~Hs n ~
L~ " OC3H, (n) ', "

L~ _ OC3H, (i) u u 2ash~7 .. ~ __ ~ - ., ENX R1 R2 R3 R4 X y or [n $, ' __ _ D I
66 OC4Hq(n) ~ R .
67 oCH2SCH3 R
68 . _ OCH ~CO2CH3 ,. R l 69 ,l ,l ~ OCH Ph ~ ~ l 2_ _ . I
R R O-N=CtCH~)~
71 ., ,l R OCH CH=CH ~ R
r . ~ 2 2 72 _ . OCH~C ~ CH ~ ~

73 ,l " hCYxyl~ OH O CH [17]1D1073 _ . . ~ _ -16.58 74 ,l ,l ,l OCH3 ~ N 98-10C

_ .
75 ll ll ll OC2H5 R ll 76 OC3H,(n) _ ,, 77 _ OC3H~(i) _ _ 78 _ OC4Hg(n) _ _ 79 OCH2SCH3 ~ _ .
., _ OCH2cO2cH3 _ _ OCH~Ph ~ _ a O-N=c(cH~)2 N
1~ u OCH2CH = CH2 u 84 ~ N N OCH C CH
I 2 _ ~ u u R OH O N _ ~ OCH~ _ _ ~
L~ o~2H5 n u 88 ll r I R OC3H~(n) ~ ~
89 R l OC3H,(i) R R
OC4Hg(n) N R
91 R OCH~SCH~ R R

'''~

', 2~9~797 Ex ~ R1 R2 R3 - R~ X Y m . p . ~C) No. or lnD ]
_ _ 92 OCH3 OCH3 hCey~l - OcH2co2cH3 O N
_ 93 ~l n u OCH Ph ., "

_ n O-N = C(CH3)2 ~
., .. OCH2CH = CH~ ,. ..
96 .. .. OCH2C CH .. ,.
97 n ~ sec- OH O CH 114-116 ~utyl _ [a1~'3D,2 0=

. 98 .. .. .. OCH3 ~ ~ oi10 . _ 30,9 99 .. ., .. C2H5 ~ ., 1o]l2 -__ _ -30,4 100 OC3H7 (n) " "
101 OC3H, (i) n l~
102 ll ll " _ ~L~ " "
103 ll llll OC~2~ ~ ~
104OCH2cO2cH3 " "
105 ll ll " OCH Ph .. "
~ _ ~_ ~ nO-N =C(CH3)2 ., u 107 n I~ u ~ ~ u E~ = = OCH2C CH ., OH O N
~_ " OCH3 ,. ,.

L~ " OC2H5 ,.
E~ ~1 ~ a OC3H, (n) R ~

" OC3H, (i) " "
OnC4Hg (n) _ y 1~ . . . OCH2SCH3 ,. "

20~2797 Ex. Rl - R2 ~ -P~3 114 X Y m. p . $C) No. _ _ _ or [nD ]
1 16 ., .. u OCH2CO~,CH, 117 .. .. u OCH2Ph _ 118 .. .. u O-N=C(CH ) 3~
119 .. .. OCH2CH = CH
120 OCH ,C ~ CH .. ll 121 ll ll u O-K+ ., CH 200 [~],D15=
_ _ .
122 _ _ _ O Li+ " ll [a+]oD,42-o 123 .. .. ,. O-[HN (C2Hs)3] ,l ,l [a3,D80O =
_ 124 .. .. iso- O~Na+ ll N 242-244 C3H7 -1,22 125 .. O-K+ _ ~ 220!-222 . -0,76 126 .. ., ll O~U+ ll N 224i226 -1,43 127 _ O-NH4+ _ _ 128 OCH3 OCH3 soc O~Na+ O CH

129 ll N C3H, O-[HN(C2H~)3] " ~ 1[o]4D8o58=
_ -5,37 130 ,, ,, tert- O-Li+ ,, u [O] io _ C4Hg + 1,83 131 ------ o Na+ _ _ [2O2]62-228 _ +1,34 2~92797 Ex R1 ~ R3 R4 X _ _ 132 __ C3H7 o CH2CO2c2Hs __ B. Formulation examples a) A dust is obtained by mixing 10 parts by weight of a compound of the formula II) and 90 parts by weight of talc as inert substance and comminuting the mixture 5in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of ~odium oleoylmethyltaurasate wetting and dispersing agent and grinding the mixture in a pinned-disk mill.

c) A dispersion concentrate which is readily dispersible in water i8 obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (~Triton X 207), 3 parts by weight of isotridecanolpolygycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, approx. 255 to above 277C), and grinding the mixture in a ball mill to a fineness of below 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.
e) Water-dispersible granules are obtained by mixing 2~79 ~

75 parts by weight of a compound of the formula (I), lO ~ " - of calcium ligninsulfonate, 5 " " " of ~odium lauryl sulfate, 3 ' " of polyvinyl alcohol and 7 " " " of kaolin, grinding the mixture in a pinned-disk mill and granulating the powder in a fluidized bed by spraying on water as granulation li~uid.

f) Water-dispersible granules are also obtained by homogenizing, in a colloid mill, 25 part(s) by weight of a compound of the formula (I), " " " of sodium 2,2'-dinaphthyl-methane-6,6'-disulfonate, 2 " " " of sodium oleoylmethyltaurate, 1 " " " of polyvinyl alcohol, 17 " " " of calcium carbonate and ~ " " of water, and precomminuting the mixture, followed by grinding in a bead mill and by atomizing and drying the resulting suspension in a spray tower by means of a single-sub-stance nozzle.

C. Biological exampleæ

1. Herbicidal action pre-emergence Seeds or rhizome pieces of monocotyledon and dicotyledon weed plant~ are placed in sandy loam soil in plastic pots and covered with fioil. The compounds according to the invention (L forms) as well as the corresponding D forms and racemates, formulated in the form of wettable powders or emulsion concentrates, are then applied to the surface of the soil cover in the form of aqueous ~uspensions or emulsions at an application rate of 600 tn 800 l of water/ha (converted), in various dosages.

,. ' :

2~92797 After the treatment, the pots are placed in the green-house and kept under good growth conditions for the weeds. After the test plants have emerged, the damage to the plants or the negative effect on the emergence is scored visually after a test period of three to four weeks by comparison with untreated controls. As shown by the test results, the compounds according to the in~en-tion have a good herbicidal activity pre-emergence against a broad range of grass weeds and dicotyledon weeds. For example, the compounds of Examples 1, 2, 3, 7, 10, 11, 12, 49, 50, 51, 55, 97, 98, 99, 121, 122, 123, 124, 125, 126, 128, 129, 130, 131 and 132 of Table 1 have a very good herbicidal action against harmful plants such as Alopecurus myosuroides, Amaranthus retroflexus, Avena sativa, Poa annua, Setaria pumila, Sinapis alba, Stellaria media, Echinochloa crus-galli and Lolium multiflorum when applied pre-emergence at an application rate of 0.3 kg to 0.005 kg of active ingredient per hectare. In contrast, the trials with the D form and with the racemic mixtures of the D and L forms of the com-pounds mentioned result in considerably less pronounced pre-emergence actions in the test plants mentioned, while the application rates were the same.

2. Herbicidal action post-emergence Seeds or rhizome pieces of monocotyledon and dicotyledon weeds are placed in sandy loam soil in plastic po~s, covered with soil and grown in a greenhou~e under good growth conditions. Three weeks after sowing the test plants are treated in the three-leaf stage.
The compounds according to the invention (L forms) and, in comparison experiments, the corresponding D forms and racemates, all of which are formulated as wettable powders or a~ emulsion concentrates, are sprayed in various dosages onto the green parts of the plants at an application rate of 600 to 800 1 of watertha (converted) and, after the test plants have remained in the -- 20927~7 greenhouse for about 3 to 4 weeks under optimum qrowth conditions, the effect of the preparations are scored visually by comparing them with untreated controls. The compositions according to the invention also have a good herbicidal activity against a broad range of economically important grass weeds and dicotyledon weeds when applied post-emergence. For example, the compound~ of Examples 1, 2, 3, 7, 10, 11, 12, 49, 50, 51, 55, 97, 98, 99, 121, 122, 123, 124, 125, 126, 128, 129, 130, 131 and 132 of Table 1 have a very good herbicidal action against harmful plants such as Alopecurus myosuroides, Amaranthus retroflexus, Avena sativa, Poa annua, setaria pumila, Sinapis alba, Stellaria media, Echinochloa cru~-galli and Lolium multiflorum when applied post-emergence at an application rate of 0.3 kg to 0.005 kg of active ingredient per hectare. In contrast, the trials with the D form and with the racemic mixtures of the D and L forms of the compounds mentioned result in considerably less pronounced post-emergence actions in the test plants mentioned, while the application rates were the same.

.

Claims (10)

1. A compound of the formula (I) (I) in which X is O or S, Y is N or CH, R1 and R2 independently of one another are hydrogen, alkyl, alkoxy, alkylthio, halogen, haloalkoxy, amino, alkylamino or dialkylamino, R3 is an aliphatic or araliphatic radical of the formula or R5 and R6 independently of one another are hydrogen or alkyl or R5 and R3 together with the carbon atom linking them are a 3- to 6-membered ring which may contain one oxygen atom and which may be substituted by one or more alkyl groups, R7 is hydrogen, halogen, alkyl which is unsubsti-tuted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, alkoxy and alkylthio, or is cyclo-alkyl, hydroxyl, cyano, aryl or arylalkyl, the last-mentioned two radicals being unsubstituted or substituted in the aryl moiety, R8 is alkyl, phenyl or substituted phenyl or R8 together with R10 and the ethenylene group linking them are a cyclopentene or cyclohexene ring which is unsubstituted or substituted by one or more alkyl groups, R9 is hydrogen or alkyl, R10 radicals independently of one another are hydrogen or alkyl or R10 together with R8 and the ethenylene group linking them are a cyclopentene ring or cyclohexene ring which is unsubstituted or substituted by one or more alkyl groups, R11 is hydrogen, halogen, nitro, alkyl, haloalkyl, alkoxy, alkylsulfonyl, alkylsulfinyl or alkylthio, R4 is hydroxyl, -O-Cat+, an aliphatic saturated or mono- or polyunsaturated hydrocarbonoxy radical, the radical being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, phenyl, phen-oxy, phenylthio, the three last-mentioned radicals being unsubstituted or substituted, aminocarbonyl, alkylaminocarbonyl and dialkyl-aminocarbonyl, or is phenoxy, substituted phenoxy, alkylidenaminoxy, cycloalkyloxy or halogen or R4 is the radical of a 5- or 6-membered cyclic lactone, or R4 is a radical of the formula -D1-CR12R13-D2-L or Cat+ is the equivalent of a mono-, di- or poly-valent cation, R12 and R13 independently of one another are hydrogen, alkyl, alkenyl, alkynyl, aryl, substituted aryl, benzyl, alkoxy, alkenyl, alkynyloxy, aryloxy or substituted aryloxy, R14, R15 and R16 independently of one another are alkyl, alkenyl or alkynyl, phenyl or sub-stituted phenyl, D1 is 0, S or NR17, R17 is hydrogen or alkyl, D2 is a direct bond or a saturated or unsaturated hydrocarbon group, L is an acid derivative radical of the formula -CO-O-R18 or -CO-S-R18 and R18 is hydrogen, alkyl, alkenyl or alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals sel-ected from the halogen group, or is cycloalkyl, cycloalkenyl, benzyl, phenyl or substituted phenyl, in an enantiomeric purity of the L form of greater than zero.

2. A compound as claimed in claim 1, wherein R1 and R2 independently of one another are C1-C4-alkyl, C1-C4-alkoxy, halogen, C1-C4-haloalkoxy, C1-C4-alkylamino or di(Cl-C4-alkyl)amino.

3. A compound as claimed in claim 1 or 2, wherein R5 and R5 independently of one another are hydrogen or C1-C4-alkyl or R5 and R6 together with the carbon atom linking them are a 3- to 6-membered ring which may contain one oxygen atom and which may be substituted by one or more C1-C4-alkyl radicals, R7 is hydrogen, halogen, C1-C4-alkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkylthio, or is C3-C8-cycloalkyl, hydroxyl, cyano, thienyl, naphthyl or dihydronaphthyl, the last-mentioned three radicals being unsubstituted or substituted, or is a radical of the formula p is 0, 1, 2 or 3, R8 is C1-C4-alkyl, phenyl or substituted phenyl or R8 together with R10 and the ethenylene group linking them are a cyclopentene or cyclohexene ring which is unsubstituted or substituted by one or more C1-C4-alkyl radicals, R9 is hydrogen or C1-C4-alkyl, R10 radicals independently of one another are hydrogen or C1-C4-alkyl or R10 together with R8 and the ethenylene group linking them are a cyclopentene or cyclohexene ring which is unsubstituted or substituted by one or more C1-C4-alkyl radicals, R11 is hydrogen, halogen, nitro, C1-C12-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkyl-sulfonyl, C1-C4-alkylsulfinyl or C1-C4-alkyl-thio.

4. A compound as claimed in one of claims 1 to 3, wherein R3 is an aliphatic, araliphatic or aromatic radical of the formula R5 and R6 independently of one another are hydrogen or C1-C4-alkyl or R5 and R6 together with the carbon atom linking them are a 5- or 6-membered ring and R7 is hydrogen, halogen, C1-C4-alkyl, phenyl or benzyl.

5. A compound as claimed in one of claims 1 to 4, wherein R4 is hydroxyl, -O-Cat+, C1-C18-alkoXy, C2-C18-alkenyloxy, C2-C18-alkynloxy the last-mentioned three radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy, C1-C4-alkylthio, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, phenyl, phenoxy, phenylthio, the three last-mentioned radicals being unsubstituted or is substituted, aminocarbonyl, (C1-C4-alkyl)amino-carbonyl and di(C1-C4-alkyl)aminocarbonyl, or phenoxy, substituted phenoxy, (C1-C6-alkylidene)aminoxy, C3-C8-cycloalkyloxy or halogen, or R4 is the radical of a .gamma.-butyrolactone or .delta.-valerolactone which is bonded in the .alpha.-osition relative to the CO group and which is unsubstituted or substituted by halogen, C1-C4-alkyl or (C1-C4-alkoxy)carbonyl, or R4 is a radical of the formula -D1-CR12R13-D2-L or Cat+ is the equivalent of an alkali metal or alkaline earth metal or an ammonium salt of a primary, secondary, tertiary or quaternary amine or diamine or polyamine, R12 and R13 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl, substituted phenyl, benzyl, C1-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyloxy, phenoxy or substituted phenoxy, R14, R15 and R16 independently of one another are C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl, phenyl or substituted phenyl, D1 is O, S or NR17, R17 is hydrogen or C1-C4-alkyl, D2 is a direct bond or a group of the formula CH2 or CH2CH2, L is an acid derivative radical of the formula -CO-O-R13 or -CO-S-R18, and R18 is hydrogen, C1-C18-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, the last-mentioned three radi-cals being unsubstituted or substituted by one or more radicals selected from the halogen group, or is C3-C8-cycloalkyl, C3-C8-cycloalkenyl, benzyl, phenyl or substituted phenyl.

6. A compound as claimed in one of claims 1 to 5, wherein R4 is hydroxyl, -O-Cat+, C1-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C3-C6-cycloalkyl-oxy, phenyloxy, (C1-C4-alkyloxy)-C1-C4-alkoxy, (C1-C4-alkyl)carbonyl-C1-C4-alkoxy, C1-C4-haloalkyloxy, C1-C4-alkylidenaminoxy, C1-C4-alkylthio)-C1-C4-alkoxy, phenyl-C1-C4-alkoxy, substituted phenyl-C1-C4-alkoxy, phenoxy-C1-C4-alkoxy, substituted phenoxy-C1-C4-alkoxy, phenyl-thio-C1-C4-alkoxy, substituted phenylthio-C1-C4-alkoxy, or a benzyloxy radical which is substituted by (C1-C4)alkyl or (C1-C4)alkoxy, benzoxy or benzoxy which is substituted by C1-C4-alkyl, C1-C4-alkoxy, halogen or nitro, or R4 is a radical of the formula D1-CR12R13-D2-L, Cat+ is the equivalent of an alkali metal, or of an ammonium salt of a primary, secondary, tertiary or quaternary amine, D1 is O, S, NH, methylamino or ethylamino, D2 is a direct bond, R12 and R13 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl or benzyl, L is an acid derivative radical of the formula -CO-O-R13 or -CO-S-R18, R18 is hydrogen, C1-C4-alkyl, C2-C8-alkenyl or C2-C4-alkynyl, cyclohexyl, cyclopentyl, cyclo-hexenyl, cyclopentenyl, benzyl, phenyl or substituted phenyl.

7. A process for the preparation of compounds of the formula (I) as claimed in claim 1, which comprises (a) reacting a compound of the formula (II) (II), in which R3, R4 and X have the meanings mentioned in formula (I), with a compound of the formula (III) (III), in which NUC1 is a leaving group, and R1, R2 and Y
have the meaning mentioned in formula (I), in the presence of an organic or inorganic base, or (b) reacting a compound of the formula (IV) (IV) in which NUC2 is a leaving group, and R3 and R4 are as defined in formula (I), with a compound of the formula (V) (V), in which R1, R2, X and Y have the meanings mentioned in formula (I), in the presence of an inorganic or organic base, or (c) in the event that, in formula (I), R4 is OH or -O-Cat+, reacting a compound of the formula (I), in which R4 is not hydroxyl or -O-Cat+, with the aid of bases in water or water/alcohol mixtures to give the free acid of the formula (I) in which R4 is hydroxyl, or (d) in the event that, in formula (I), R4 is other than OH or -O-Cat+, reacting a compound of the formula (I), in which R4 is hydroxyl, with thionyl chloride, oxalyl chloride, chlorocarbonate, carbonyldiimidazole or dicyclohexylcarbodiimide/4-(N,N-dimethylamino)-pyridine in a manner known per se to give an activated carboxylic acid derivative and reacting the latter with a compound of the formula (VI) R4-H (VI) in which R4 is as defined in formula (I), with the exception of the meanings hydroxyl and -O-Cat+, in the presence of an inorganic or organic base to give compounds of the formula (I) in which R4 is as defined in formula (VI), or (e) employing a mixture of the L form of the formula (I) with the corresponding D form, and then carrying out a racemate resolution process, or (f) in the event that, in formula (I), R4 is other than OH or -O-Cat+, reacting a compound of the formula (I) in which R4 is hydroxyl with a halogen compound of the formula (VII) R0-Hal (VII) in which R0 is defined in such a way that R0-O- has the meaning of R4 as in formula (I), in the presence of an inorganic or organic base.

8. A herbicidal and plant-growth-regulating agent, which comprises a compound of the formula (I) as claimed in one of claims 1 to 6 as well as customary formulation auxiliaries.

9. The use of the compounds of the formula (I) as claimed in one of claims 1 to 6 as herbicides or plant growth regulators.

10. A method for controlling harmful plants or for regulating the growth of plants, which comprises applying one or more compounds of the formula (I) as claimed in one of claims 1 to 6 to the plants, parts of the plants, seeds of the plants or the area on which the plants grow.