JPS63166874A - Steribizing composition containing optically active tetrahydro-2-fran derivative - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides optically active (as, l'R) -3-
[N-(methoxyacetyl)-N-(3-chloro-2,
6-dimethylphenyl)] aminotetrahydrofuran-
The present invention relates to a method for producing 2-one, a composition for controlling microorganisms containing the compound as an active ingredient, and a method for using the composition as a microbial controlling agent in plant protection.

3-[N-(methoxyacetyl)-N-(3-chloro-
2,6-dimethylphenyl)]aminotetrahydrofuran-2-o is disclosed in German Patent Publication No. 28042
Publication No. 99 or equivalent British citizenship MB, ilF No. 1
No. 577,702, it is disclosed as a compound effective for controlling microorganisms. According to the publication, the compound represented by the following formula I: has as a structural feature an asymmetric center at the asterisked position. In racemic form,
This compound can be divided by conventional methods into optical antipodes, ie, different steric structures with different strengths of microbial control action.

The publications on the above do not indicate how large the difference in activity is, and also that of the two enantiomers,
There is no mention of which one actually has the greater microbial control effect.

Furthermore, the above-mentioned publications discuss other possibilities of the existence of isomers due to the furanone ring within a wide chemical scope.
How many books have you read yet?

However, the compounds of formula 1, which are conventionally obtainable as racemates, are not exclusively available as a set of enantiomeric forms due to asymmetric substitution at the carbon atom (−〇) position indicated by an asterisk. rather, it exists as a mixture of four isomers, ie, two diastereomeric pairs of enantiomers.

The reason is that the molecule has rotamerism (atrobisomerism) caused by symmetrical chlorine substitution containing the asymmetric center mentioned above. 3-[N-(methoxyacetyl)
The racemic form of -N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o, namely compound 30 in DE 2804299, melts at 140°C and 115°C, respectively. and two enantiomers that can be separated from each other
It is a 1:1 mixture of pairs of diastereomers.

A suitable separation method is adsorption chromatography. Both sets of enantiomers, as racemates, can be separated into their optical antipodes by conventional methods. 3-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o(as,
I's) and (aR.

The l'R) enantiomer melts at 140 °C and is obtained as a by-product (as, I's) (aR,
'l'R) enantiomer set, 5-[N-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aaminotetrahydrofur-2-oni/ (n (aR,I's) and (
aS.

The enantiomer of 1'l (,) melts at 115°C (
aR,1'8) (as, l'R) from the desired set of enantiomers can be isolated, for example, by chromatography on an optically active phase.

The approximately 1:1 composition of diastereomers of the enantiomeric set obtained according to DE 2804299 varies from 45 to 55 times.

In the present invention, 5-[N-(methoxyacetyl)-N
The (aS,l'R) enantiomer of -(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o has a significantly enhanced microbial control action compared to the mixture of isomers of formula I. It was found to have unexpected long-term effects.

The invention therefore also relates to compounds of the formula (I) in which the proportion of the (as, i'l) enantiomer is greater than 25% by weight as theoretically expected to be a racemic mixture of diastereomers of the two pairs of enantiomers. . In a narrower sense,
The present invention provides (aS.

I) a weight pot in which the ratio of enantiomers is at least 28;
Preferably it relates to compounds of formula I which are at least 40% by weight, most preferably at least 50% by weight. Most preferred for practical purposes as a plant fungicide, the ratio of (as) enantiomers is at least 7.
0 to 4, especially a compound of at least 90% weight. The present invention further provides 3-[N-(methquinacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o
S, l'R) enantiomer.

Racemic (aR, I's) (as, l'R) -
3-[N-(methoxyacetyl)-N-(5-chloro-
2,6-dimethylphenyl)] aminotetrahydrofuran-2-o also has a substantially increased microbial control activity and a longer duration of action compared to the isomer mixture of formula
The amount of increase is smaller than that of the (aS,l'R) enantiomer.

(aR,I'5)(aS,11(,
) The enantiomeric set is particularly suitable for use as a plant fungicide.

Therefore, the present invention provides (aR, I's) and (aS, l'R
) Also relates to racemic mixtures of isomers.

3-[N-(methoxyacetyl)-N-(3-chloro-
The preparation of the (as, l'R) enantiomer of aminotetrahydrofuran-2-o (2,6-dimethylphenyl)] is carried out using the isomer mixture of formula I and the 115 obtained therefrom.
Melts at °C (aR.

山)(as,l箕)-3-[:N-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]
It is carried out by a two-step chromatographic separation of aminotetrahydrofuran-2-o.

The first step in the separation of racemic mixtures of diastereomeric sets of two pairs of enantiomers is carried out on a fixed solid phase using a liquid phase (eluent), (aR,I's) (
as, l'R) The desired set of enantiomers can be obtained. For this separation step, all adsorption materials known to the engineer can be used, such as silica gel, A/201, or organic polymers W! (polyamide, polyacrylamide, etc.), as well as agarose, sepharose, and human-modified cellulose 1kii1! can be used. Acetylated or benzoylated cellulose is particularly suitable. The set of (aR,I's) (as, 1B) s-nanthiomers can be used in the form as obtained, in formulated form as a plant fungicide, or can be further separated.

The second separation step is performed on an optically active bath (aR,l
'S)- and (a8.l'R)-5-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o racemic mixture solution is separated into its individual enantiomers and extracted from the solution (aS.

l′R,)-3-[N-(methoxyacetyl)-N-(
5-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-o.

Acetylated cellulose, such as acetylated or benzoylated cellulose, can be used, for example, as the optically active phase. By way of example, triacetylcellulose and triacetyl(3-methylbenzoyl)cellulose are mentioned.

In a preferred variant of the separation method described above, all four enantiomers of the isomer mixture obtained according to the Federal Republic of Germany@2804299 can be separated in one step instead of in two steps. In this variant, a dilute solution of the mixture to be separated in a 1:1 mixture of hexanoglobanol is adsorbed onto modified cellulose as the optically active phase and treated with a suitable mobile phase (eluent). It is continuously eluted. The solution is preferably adsorbed onto affurated cellulose (e.g. affurated or benzoylated cellulose), preferably tris(3-methylbenzoyl)cellulose, as fixing phase, followed by a 1=1 to 9:1 mixture of hexane/isopropanol. eluted at The solution of eluted isomers is fractionated and collected, and the isomers are
Obtained as a residue after distilling off the solvent mixture.

In another preferred variant of the production method, 140
The set of (as, I'5) (aR, l'R) enantiomers obtained as a by-product after melting at °C and separating the mixture of isomers can be racemized once more to the starting mixture. can. Such racemization or isomerization is for example (as, I'S) (aft.

l'R) by heating the set of enantiomers in the melt to 140 DEG -180 DEG C., preferably in the presence of a tetraalkylammonium salt, for example tetrabutylammonium bromide, until equilibrium is achieved. The product obtained again consists of a diastereomeric set of two pairs of enantiomers and can be recycled into the separation process. The invention also relates to this additional racemization method.

(aR, l'8) -5-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]
Racemization of aminotetrahydrofuran-2-o can also be carried out by opening the lactone fR with alkali and subsequent cyclization under appropriate conditions. The racemate obtained by this method can also be reused in this separation method.

The absolute conformations of the enantiomers have been determined by X-ray structural analysis and can be shown as follows.

The present invention further relates to German Patent Application No. 2
(al'L, i'R)-(a
s, 1m)-3-[N-(methoxyacetyl)-N-(
The present invention also relates to a method for producing aminotetrahydrofuran-2-(5-chloro-2,6-dimethylphenyl)]. 1
:1 or about 1=1 (45:55 to 55:45)
A set of diastereomers in a ratio of is a particularly suitable plant fungicide and likewise constitutes another object of the invention.

In the production method of the present invention, the combination of a) a method for total separation of the two isomers of the intermediate, and b) a subsequent chlorination method is used according to the following formula:
−1
Goto
(aR, l'R) and (as, l'FI-
') The mixture of enantiomers can be used as a fungicide in the form obtained, or it can be subsequently separated by chromatography to obtain the (as, I) enantiomer by the method of the first step a). You can also do it.

Racemic 5-[N-(methoxyacetyl)-N-(2,6-dimethylphenyl)] used as starting material
Aminotetrahydrofuran-2-o is also described in German Patent Publication No. 2804299 or British Patent Specification No. 1.
No. 577702.

In the chromatographic axiom step a) above, all adsorbent materials known to the person skilled in the art, such as soligel, A
603, or organic polymer resins (polyamide, polyacrylamide, etc.), as well as acarose, sepharose,
and in particular modified cellulose can be used. Acetylated or benzoylated cellulose is particularly suitable.

(l'R)-3-methoxyacetyl)-N-(2,6-
dimethylphenyl)] aminotetrahydrofuran-2-
The chlorination of O is conveniently carried out in an inert solvent. Suitable solvents are chlorinated aromatic and aliphatic hydrocarbons such as chlorobenzene, methylene chloride, chloroform, carbon tetrachloride and the like. It is preferred to use lower alkane carboxylic acids such as formic acid, acetic acid and propionic acid. A preferred solvent is formic acid.

Chlorination is preferably carried out at 0°C to 50°C, for example at room temperature.

It is also advantageous to carry out the chlorination in the presence of Lewis acids, such as aluminum chloride, zinc chloride, iron(1) chloride or tin(rv) chloride. A preferred Lewis acid is iron(1) chloride. Lewis acids are used at 1-8% of the (li) isomer to be chlorinated. Chlorination can also be carried out without a Lewis acid. Chlorination is carried out at normal pressure or at slightly elevated pressure. Although sulfuryl chloride is used for chlorination, chlorine is the preferred chlorinating agent.

a) Method for separating racemic 3-[N-(methoxyacetyl)-N-(2,6-cyphthylphenyl)]aminotetrahydrofuran-2-onecara l'R) enantiomer on solid phase (adsorption chromatography) and b) chlorination produces (aR, l'R) (as, l'R) isomers (atropisomers
)) How to obtain a mixture of highly active (
aS, l'R) -3-[N-(methoxyacetyl)-
An active ingredient exhibiting a bactericidal effect to the same extent as N-(2,6-cyphthylphenyl)]aminotetrahydrofuran-2-o is produced in a high yield.

In particular, (as, I'R) -3-[N-())xy7cetyl)-N-(2,6-cyphthylphenyl)]aminotetrahydrofuran-2-one and also racemic I
> (akL, f's) (as, l'H,) -
5-[N-(methoxyacetyl)-N-(2,6-cyphthylphenyl)]aminotetrahydrofuran-2-one and I/c3-[N-(methoxyacetyl)-N-(2
, 6-cyphthylphenyl)]-aminotetrahydrofuran-2-o, the mixture of (aR, l'R) and (aS, l'R) isomers is the four isomers described in DE 2804299 It was found that it has a much stronger microbial control action than the racemic form, which exists as a compound.

The mixture of these two isomers and the (aS,l'R) enantiomer, when used in practice, has a microbicidal spectrum that is very useful for protecting cultivated plants without causing any undesirable side effects on the plants. have Examples of cultivated plants within the scope of the invention typically include grains, corn, rice, vegetables, beets, soybeans, peanuts,
Mention may be made of fruit trees, ornamental plants, and especially plants of the Solanaceae family, such as grapes, hops, cucurbits (cucumbers, marrows, melons), potatoes, tobacco and tomatoes, as well as bananas, cocoa and natural rubber plants.

The above mixture of the (aS, l'R) enantiomer or its isomers is used in the cultivation of the above or related plants.
Fungi infesting plants or their parts (fruits, flowers, leaves, stems, tubers, roots) can be suppressed or eradicated, and at the same time, later growing plant parts can be protected from attack by such fungi. .

This mixture may be effective against phytopathogenic fungi belonging to the following classes: Comycetes [e.g. Erysif-77- (Er.
ysiphaceae)): Basidiomycetes, such as especially Aspergillus; Deuteromycota [e.g.
Phytophthora (formerly known as Phytophthora);
), Peronospora , Pseudoperonospora
a), Pythi-um and Plasmopara. The isomers also exhibit osmotic effects. They can also be used as a dusting agent to protect seeds (fruits, tubers, grains) and continuous trees from fungal infections and phytopathogenic fungal substances occurring in the soil. The mixture of the present invention comprises: 1. II species, and they are ecologically harmless.

Without being limited in any way, the crops to be protected within the scope of the present invention include, for example, the following plant species: Class 8i9 (wheat, corn, rye, oats, rice, sugar corn and related crops): beets; Carrots, sugar beets and fodder beets); carcasses, miliforms and soft fruits (apples, pears, plums,
peaches, almonds, cherries, strawberries, raspberries, and blackberries); legumes (fava beans, lentils, peas, soybeans); oil products (oil, mustard,
Poppy, olive, sunflower, coconut, castor rt
h [things, cocoa beans, peanuts); Cucurbitaceae plants (cucumbers, marrows, melons); fiber plants (
Cotton, azalea, hemp, jute); Species plants (orange, lemon, grapefruit, mantaline); Wild ivy (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, horsetail, paprika): Lauraceae (
or corn, tobacco, nuts, coffee, sucrose, tea, vines, chestnuts, hops, bananas, pineapple, grass (e.g. on golf courses) and dried grass.

The compounds of the invention are usually applied in the form of compositions and may be applied simultaneously or sequentially to the planting pond or to the plants or material to be treated, if desired with further other compounds.

These compounds may be fertilizers, nutrient supplements or other substances that affect the growth of other plants. It can also be used as a selective herbicide, insecticide, fungicide, bactericide, nematicide, molluscicide, optionally with other carriers, surfactants or application promoting adjuvants customary in formulation technology. agent or a mixture of several of these substances.

Suitable carriers and auxiliaries can be solid or liquid and are substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersants, wetting agents, adhesives, adhesives, binders or fertilizers. obtain. Particularly useful adjuvants are phospholipids.

A preferred method of application of a compound of the invention or an agrochemical composition containing at least one of the compounds is foliar spraying. The number of applications and the amount of application are based on the corresponding pathogenic bacteria (fungi).
depending on the risk of spread. However, the compounds can also be impregnated into the plant cultivation area using liquid formulations or
Alternatively, by applying it to the soil in solid form, for example granular form (soil application), it can penetrate the plant via the soil and through the roots (osmotic action).

The compounds can also be applied to the seeds (coating) by impregnating the seeds with a liquid formulation containing one of the compounds of the invention or by coating the seeds with a solid formulation. In special cases other types of application are also possible, for example selective treatment of plant stems or buds.

The compounds of the invention can be used in their neat form or, preferably with auxiliaries customary in the pharmaceutical industry, and can be prepared by the official method as emulsion stock solutions, coatable pastes, etc.
aste), directly sprayable or dilutable solutions,
It is formulated into dilute emulsions, wettable powders, aqueous solutions, powders, granules, and encapsulates, for example with polymeric substances. The nature of the composition, as well as the method of application, such as spraying, atomizing, dusting, scattering, painting or injecting, will vary based on the intended audience and environment of use. Advantageous application rates are usually 50 y to 5
Kl active ingredient (a,i, )/ha, preferably from 100g to 2 @a,i,/ha, R also preferably from 200y to 600g a,i,/ha.

Preparations, i.e. compositions, formulations or mixtures containing a compound according to the invention (active principle) and, where appropriate, solid or liquid auxiliaries, can be prepared, for example, by combining the active principle with a solvent, solid carrier and suitable admixture. are prepared by homogeneously mixing and/or milling with fillers such as surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably moieties having 8 to 12 carbon atoms, such as kinerene mixtures or substituted naphthalenes; phthalates such as diotylphthalate or dioctyl phthalate; 7-chlorohexane. or aliphatic hydrocarbons such as paraffins; alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether;
A ketone of cyclohexanone: a strong polar solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide: and a vegetable oil such as evoquinated coconut oil or soybean oil: or water.

Solid carriers which can be used, for example in dusts and fractional powders, are usually natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve the physical properties. Suitable granulated absorbent carriers are of the porous type, e.g. pumice, crushed brick,
Sepiolite is bentonite; and suitable non-absorbent carriers are materials such as calcite or sand. Furthermore, a large number of pre-granulated mineral and organic materials can be used, especially dolomite or pulverized plant residues.

Depending on the nature of the compound of formula 1 to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties.

The term "surfactant" is to be understood to also include mixtures of surface-active agents.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are alkali metal salts, alkaline earth metal salts, as yet unsubstituted or substituted ammonium salts of higher fatty acids (Cto-Cu), such as oleic acid or stearic acid, or for example coconut oil or sacrificial oil. It is a sodium salt or potassium salt of a natural fatty acid mixture obtained from. Fatty acid methyltaurate salts may also be used.

However, so-called synthetic surfactants, especially aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates, are also frequently used. The fatty sulfonates or sulfates are usually alkali metal salts, alkaline earth metal salts. They are in the form of salts or unsubstituted or substituted ammonium salts and contain C8-C22 alkyl groups, including the alkyl part of the afur group, such as lignosulfonic acid, which is obtained from natural fatty acids. It is a sodium or calcium salt of a mixture of fatty alcohol sulfates.

These compounds include salts of sulfuric esters and mixtures of fatty alcohol sulfates such as sodium or calfram.

These compounds also include salts of sulfuric acid esters and salts of sulfonic acids of aliphatic alcohol/ethylene oxide adducts. The sulfonated benzimidazo-Am conductor preferably contains two sulfonic acid groups, one aliphatic group containing from 8 to 221 carbon atoms, and gold. Examples of alkylarylsulfonates are the sodium, calcilam or triethanolamine salts of dodenlebenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid/formaldehyde synthesis products. Corresponding phosphates, such as phosphoric acid esters of p-nonylphenolic compounds containing 4 to 14 moles of ethylene oxide, are also suitable.

The nonionic surfactants are preferably aliphatic or cycloaliphatic alcohols or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkylphenols, which derivatives contain from 5 to 30 glycol ether groups, (aliphatic) 8 to 20 carbon atoms in the hydrocarbon portion and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Other suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide and polypropylene glycol, ethylene diamine polyglobylene glycol and alkyl polypropylene glycols containing from 1 to 10 carbon atoms in the alkyl chain; The adduct contains 20 to 250 ethylene glycol ether groups and 10 to 100 10 pyrene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

A typical example of a nonionic surfactant is nonylphenol.
Polyethoxyethanol, castor 7 oil polyglycol ether, polypropylene/polyethylene oxide 7 adduct,
They are tributylphenoquine 7-bolyethoxyethanol, polyethylene glycol and octylphenoquine ethoxyethanol. Fatty acid esters of polyoxy7ethylene norbitane and polyoxyethylene rubitan triolate are also suitable nonionic surfactants.

Cationic surfactants preferably contain at least one C8-C22 alkyl group as one substituent and lower unsubstituted or halogenated alkyl groups, penzyl groups or lower hydroxyalkyl groups as other substituents. A quaternary ammonium salt containing a group. The salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, for example stearyltrimethylammonium chloride or benzyldi, (2-chloroethyl)ethylammonium bromide.

Surfactants customary in the pharmaceutical industry are described, for example, in the following publication: "McCutchan's Detergens and Emulsifiers 7 = z 7 /l/
(Mc Cutcheon's Detergent
sand Emulsifier8 Annual)
'MC Publishers, Ridgewood, New Chassis, 1979; Dr. Helmut '/z Tuff, 'Tensid-Handbuch.
) (Surfactant Handbook) 2° Carl Han-ser Verla
g), Mienchen and Vienna.

1981.

In the storage field, preferred additives are those that are safe for human and animal nutrition.

The fungicidal compositions of the present invention usually contain from α1 to 95% by weight of (aS,l′R) among the four isomers of the compound of formula (II) in a proportion higher than the amount corresponding to the theoretical amount of 25% by weight. Contains 99.9 to 5% of the z-nantiomer with 2% by weight solid and/or liquid carrier.

Preferred compositions contain at least 28% by weight of the active ingredient (aS
, l'R) enantiomer and, in addition, an equal or smaller amount of the (aR,I'S) enantiomer.

A more preferred composition is one in which the active ingredient contains 40% by weight or more of the (aS,l'R) enantiomer;
11 and an equal or smaller amount of (aR).

The l'R) enantiomer, or the like, is one that contains a lesser amount of the (aL4.1'8) enantiomer.

Particularly preferred compositions contain 50% by weight of the active ingredient (
aS, l'R) enantiomer, and in addition, the active ingredient contains (aR, l'R) enantiomer or (aR, I'S ) enantiomer with a total of 1
It is characterized in that it is contained in an amount of 0.00% by weight or an amount smaller than that.

More preferred compositions are those in which the active ingredient contains the tn (as, l'R) enantiomer at 70 wt.
It contains the (aS, l'R) enantiomer of

Therefore, the features listed above are (a, 8, t'a
) enantiomers are preferably the predominant constituent, (aR,l'R) or (al(,,I's)
The ratio of enantiomers follows, with each of the remaining enantiomers being present in lesser amounts, 3-CN-
Concerning the amounts of the four isomers of (methoxyacetyl)-N-(3-chloro2,6-cyphthylphenyl)]aminotetrahito. The amounts indicated relate exclusively to compounds of formula 1 and include minor amounts of other compounds that may be present in the compositions of the invention.

Although commercially available products are preferably formulated as concentrates, the end user typically employs dilute formulations.

The compositions may also contain other auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders, adhesives as well as fertilizers, or other active ingredients for obtaining special effects. .

Such agrochemical compositions also constitute the present invention.

The following examples illustrate the invention, but the invention is not limited to what is described therein. Part and amount are based on weight.

Production Example tl 5-[N-(methoxyacetyl)-to-(5-
rioo-2,6-') methyl phenyl)] aminotetrahydrofuran-2-o (aB.

1'S) (as, I'R) xsu7 f o?
-(i') group, and 3-[N-(methoxyacetyl)-
N-(3-chloro-2,6-cyphthylphenyl)]aminotetrahydro7ran-2-one (as, I'5)(
aR.

1m) Preparation of sets of enantiomers.

3-[N-(methoxyacetyl)-N-(3-chloro-
70 g of the isomer mixture of 2,6-dimethylphenyl)]]aminotetrahydrofuran-2one were separated into individual Separate into isomers.

Result: (as,4'S)(aR,l'R)-3-CN-(
methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one 35 By melting point 140°C, (as, f'5) (14) (aS, i'R)- 5-[N
-(methoxyacetyl) -N-(5-chloro-2,6
-dimethylphenyl)] aminotetrahydrofuran-2
-one 526y, melting point 115°C.

t 2 (14) (aS, 4'S)-3-CN -(
methoxyacetyl) -N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one and (aR,i'R)-5-CN-(methoxyacetyl)-N-(5-chloro- 2,6-dimethylphenyl)]
Preparation of aminotetrahydrofuran-2-one enantiomer (asf'5)(aR,4'R)-3-CN-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]]]aminotetrahydro 7 runs - 2 on 1
was mixed with ethanol (95%
The individual enantiomers are separated using an eluent consisting of a mixture of (% by volume) and water (5% by volume).

Result: (aR,'f'R) -5-CN -(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)
] Aminotetrahydrofuran-2-one α215F Melting point 117-120°C, [α]: (in cH'cls) Knee 4
4±1° (ee>98%), (as, t's) -5-CN -(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]
Aminotetrahydrofuran-2-one L232p.

Melting point 115-117℃, [αml”: (CH (in Js)
Knee 64±1° (ee>99%).

1-3 (aR,t'5)-3-CN-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one (14)
(aS,i'R)-3-CN-(methoxyacetyl)
-N-(5-chloro-2,6-dimethylphenyl)]Aminotetrahydrofuran-2-one enantiomer production (&gj'S)(&S,i'R) -5-[N-(methoxyacetyl)-N ethanol (95% by volume) and The individual enantiomers are separated using an eluent consisting of a mixture of 5 volumes and 1 volume of water.

Result: (as,4'5)-5-CN-(methoxyacetyl)
-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one α154F.

Melting point 98-. 100℃, [α:] sweet (CHCJ, medium) knee 9t2 ± 1° (ee>95%), highly active (14)
(aS, i′R)-5-[N-(methoxyacetyl)-
N-(5-chloro-246-dimethylphenyl)]aminotetrahydrofuran-2-one α152y Melting point 94~
96℃l CC1J: CCHCl, medium): +96°±1
°(ee>99%).

1.4 3-[N-(methoxyacetyl)-N-(3-
chloro-2,6-dimethylphenyl)] aminotetrahydrofuran-2-o (ms, 1's).

Preparation of the individual isomers of (aR, rs) and (as, I'R) by a single separation step from the mixture 1% solution of the isomer mixture in a 1=1 mixture of hexane/2-propatur An HPLC column packed with 20 μm of tris(!I-methylbenzoyl) cellulose (
46 x 25 txm) K Kakeru. Chromatography is carried out using an eluent consisting of a hexane/2-propatol (60:49) mixture at a flow rate of Fi1 sl/min. Four isomers were separated under these conditions. The retention times for the individual isomers are shown below: Isomer Retention time) (aR,1'S) zt7(as,i'
s) s t.

(as, t'R) 42.5(aR, f
'R) 67.7 isomer was isolated in pure form after evaporation of the solvent mixture and drying of the residue (physical data correspond to the values given in the previous examples). Cykutris(3-methylbenzoyl)cellulose used for the stationary phase was produced as follows.

Heptatool 50y is added to tris(3-methylbenzyl)cellulose 10F in 500-methylene chloride. The resulting solution was then treated with a solution of sodium lauryl sulfate (240 m) in a, yc4, K, 400 ypm.
Add dropwise while stirring. Thereafter, methylene chloride is distilled off at 40 to 42°C (bath temperature) while stirring at the same rotational speed. The residue is isolated by filtration and washed with water and ethanol. The powdered product was dried at 80°C in a vacuum dryer.
Dry for 20 hours. Yield: 9.6y (theoretical amount of 96
%). If desired, spherical particles with a diameter of 10-20 μm are fractionated by sieving or sedimentation. Other physical properties of the product are shown below.

Specific surface area: 5zBrn2/y Heat of fusion ΔH (by BET): 12-7J/1! (t'R)-3-CN-(methoxyacetyl)-N-
(3-chloro-2,6-dimethylphenyl)]3-[N-(
Selective preparation of (aR4'R) and (as, t'R) mixtures of (methoxyacetyl)-N-C5-chloro-2,6-cymelphenyl)]aminotetrahydrofuran-2-o can be easily carried out by and with high yield (Example 2
．． 1). Upon formulation, this mixture can be used as a highly effective plant microbial control agent. However, if desired the (aS , i'R) enantiomer can also be separated from them (Example 2.2)
.

(t'R) used as starting material for chlorination
-5-CN-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aminotetrahydro 7
Ran-2-one can be separated from the corresponding racemate according to the method of Example 2.0.

Preparation Examples Enantiomeric intermediate (t's) -3-CN-(methoxyacetyl)-N-(5-chloro-muro-dimethylphenyl)] aminotetrahydrofuran-2-one and (i
'R)-5-CN-(methoxyacetyl)-N-(3
Separation of 3-CN-(methoxyacetyl)-N-(3-chloro-
2,6-dimethylphenyl)] aminotetrahydrofuran-2-one 2 was dissolved in ethanol (95% by volume) and water (5% by volume) under a pressure of 2 bar in a medium pressure chromatography column packed with triacetylcellulose. The mixture is separated into individual enantiomers using an eluent.

Result: (l'R)-3-[N-(methoxyacetyl)-N-
(5-Rio2,6-dimethylphenyl)]aminotetrahydrofuran-2-one 1808. .

Melting point 65-65°C, Ca): (in cacls):
-ats±1°(e>99chi), (1'5)-3-[N-(methoxyacetyl)-N-(
3-Chloro-2,6-dimethylphenyl)] aminotetrahydrofuran-2-one α978y Melting point 62-64℃
, [α] sweet (in CHCl s) knee 8α3±1° (e
e>95chi) Z 1 (aR, t'R) - and (as, 4'R)
-3-CN-(methoxyacetyl)-N-(5-chloro-2,6-dimethylphenyl)]aminotetrahytone Formula I
(t'R)-3-CN-(methoxyacetyl)-N
-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one L222F, formic acid 30
Dissolve in ml. The salt gcto6p is bubbled into the solution at room temperature in the presence of traces of iron(1) chloride. The solution is stirred for about 1 hour and the solvent is evaporated under reduced pressure. Dissolve the residue in ethyl acetate and extract the solution with water. The extract is dried over sodium sulfate and filtered, after which the filtrate is concentrated by evaporation. The dried mixture melts at 79-82°C and consists of about 50% of each of the two isomers (ie the ratio of isomers varies from 45:55 to 55:45).

2.2 Preparation of pure (as,t'R)-3-CN-methoxyacetyl)-N-(3-chloro-z6-dimethylphenyl)]aminotetrahydrofuran-2-o by chlorination in Example 2. The resulting residue is dissolved in ethyl acetate. The solution is extracted with water, the aqueous extract is dried over sodium sulfate, filtered and the filtrate is concentrated by evaporation. The crude mixture is separated on a flash column packed with silica gel and eluted with a 1=3 mixture of ethyl acetate/hexane.

Result: (aR,'i'R) -5-CN -(methoxyacetyl) -N -(3-10rho-2,6-dimethylphenyl)]]]] aminotetrahydro7ran-2-one 1070
f.

[α] Enemy (CH (J3): +658°±2°.

(ms, 4'R)-3-CN-(methoxyacetyl)-N-(s-chloro-2,6-dimethylphenyl)]
Aminotetrahydrofuran-2-one 11075F [α
:l” (CH (J, middle): +88±3°.

Formulas containing isomers and mixtures thereof that can be prepared according to Examples 1.1 to 1.4 and zl and 2.2. It is possible to produce emulsions with a concentration of .

2 Solution a) b) c) d
) Polyethylene glycol 400-70% --H-methyl-2-pyrrolidone --204 --Epoxidized coconut oil --1 5% These solutions are suitable for application in the form of microdroplets.

(5) Granules a) b) Kaolin
94% - Highly dispersed silicic acid
1chi - attapulgite -90
% active ingredient is dissolved in methylene chloride, this solution is sprayed onto the carrier and the solvent is subsequently removed under reduced pressure.

4 Powder a) b
) Highly dispersed silicic acid 1% talc
97% - Kaolin
- A ready-to-use powder is obtained by uniformly mixing 90% active ingredient and carrier and milling in a suitable mill.

i Hydrating agent a) b) e)
Sodium lignosulfonate 5 5
% - Sodium lauryl sulfate 3%
-5% Sodium diisobutylnaphthalene sulfonate 6%
10% Highly Dispersible Silicic Acid 54 10% 10% Kaolin 62% 27
- After thoroughly mixing the active ingredient with the auxiliary agent, the mixture is thoroughly ground in a suitable mill to obtain an irrigation agent that can be diluted with water to obtain a suspension of the desired concentration. It will be done.

& Emulsion stock solution calcium dodecylbenzenesulfonate 5%
Cyclohexanone 30 Thyxylene mixture 50% By diluting this emulsion stock solution with water, an emulsion of the desired concentration can be obtained.

2 Powder a)
b) Talc 95% - Kaolin - 92% The active ingredient is mixed with the carrier and the mixture is crushed in a suitable mill to obtain a ready-to-use powder.

& Extruded Granules Sodium Lignosulfonate 2% Carboxymethyl Cellulose 1% Kaolin 87% The active ingredients are mixed and milled with auxiliaries and the mixture is subsequently moistened with water. The mixture is extruded and dried in a stream of air.

Coated granules polyethylene glycol 200 3% kaolin
94 grams of the finely ground active ingredient are applied uniformly to the polyethylene glycol-moistened kaolin in a mixer. This method provides dust-free coated granules.

11 Suspension stock solution Ethylene glycol 10% Sodium lignosulfonate 10% Carboxymethylcellulose 1% 57% Formaldehyde aqueous solution 12% 75cs aqueous emulsion Silicone oil 18% Water
By homogeneously mixing the 32 finely ground active ingredient with auxiliaries and diluting with water, a suspendable concentrate is obtained, from which a suspension of the desired concentration can be obtained.

5 Biological Example 51 Sugar beet (Beta vulgaris) C. sugar beet*ev, ri') Kleinvanzleben Monogeum
rm)) on Viteum ultimum (R7thium
ultimuz) and Zea mays
() corn * eve sweet corn (Swea
Pythium ultimum (Pythi
Test method for Pythium ultimum: Mix the mycelium of Pythium ultimum with soil at 1 o 1 soil and 500 m of mycelial suspension.
, a 250 d plastic dish is filled with the fungus/soil mixture. After 4 days of incubation at 10° C., each mold is sown with 10 seeds of the test plants (corn or sugar beet). The next day, 50 ml of a spray solution of each test compound prepared from 25% hydrating powder and water was added to 2 q of λα4α and [
Pour into each mold at a concentration of LO2 ppm. After a cultivation period of 7 days at 22° C., the effect of the test compounds was evaluated by counting the number of germinated plants according to the following criteria.

Microbial control effect (%) Standard>95 1 80-95 550-80
60-50 9(
(No effect) The results are shown in Table 1.

First Table: Formula I according to German Patent Publication No. 20804299
(aR, 1's) (as, t'R) diastereomer pair 45% and (14) (aS, 'I'5) of the compound of
(aR,'t'R) A mixture consisting of 55% of the diastereomeric pair.

◆Evaluation as the average of three equivalent tests The 2-semiconductor 3) of the present invention showed bactericidal activity even at concentrations reduced to a6~(L 2 ppm).

&2 Phytophthora 1nfestans on tomato plants
a) Residual-protective effect After a cultivation period of 5 weeks, tomato plants were sprayed with a spray mixture prepared from the watering agent of the test compound (α02% a, i
-). After 24 hours, the tomato plants are infected with a fungal spore suspension. The fungal attack is evaluated after the plants have been grown for 5 days at 20°C with a relative humidity of 90-100°C.

b) Systemic action The tomato plants are sprayed after a cultivation period of 3 weeks with a spray mixture prepared from an irrigation agent of the test compound (0002% a, 1.0002% a, based on the volume of the soil). The spray mixture is ±
1. Be careful not to touch the upper part of the plant.

After 48 hours, the treated plants are infected with a suspension of fungal sporangia. Fungal attack is evaluated after the infected plants have been grown for 5 days at 20° C. with a relative humidity of 90-100°C.

The results were evaluated according to the criteria described in Example 51, and the concentrations necessary to achieve criteria 1-2 were determined in each case.
The concentration factors (f) obtained by this method are listed in Table 2 based on the concentration of the most effective (as, I'R) enantiomer.

53 (Grape Seedling Acv, Gutedel)
Plastic bitekola (Plasmopa) on grapes
raViticola) [grape seedlings,
eV, Gutedal (C
Hasselas), in 5 bodies, 1 plant per each test compound) a) Foliar application for residual abdominal action Five week old grape seedlings were sprayed with a spray mixture prepared from the formulation of the test compound and after 1 day , a suspension of sporangia of Plasmoparavitecola (200,000 spores/, j)
Infect with. Infected seedlings are grown in a greenhouse at 20°C. Following a 14 hour cultivation period at 100 degrees relative humidity,
Cultivation was carried out for 4 days at 75 to 85 cm, and finally 100
Further overnight cultivation at % humidity will cause sporulation. Evaluation of fungal attack is carried out after this 6-day cultivation period (according to the same criteria as in Example 51).

b) Osmosis Five week old grape seedlings are sprayed with a spray mixture prepared from the formulation of the test compound. After 5 days, the plants are infected with a sporangial suspension of Plasmopara bitecola (200,000 sporangia/ml). The test is carried out as described in a).

The concentration factors calculated according to Example 52 are shown in Table 3.

54 Pythium debary on Beta vulgaris
anum) was cultured in Carrot Chip nutrient solution and added to the soil and sand mixture. Flowerpots were filled with the infected top weir and then sugar beet seeds were sown into them. Immediately after sowing, an aqueous suspension of the test compound formulated as an irrigation agent is poured into ±i1 (20 ppm of active ingredient based on the volume of the bed). The pots are then left in a greenhouse at 20°C for 3 weeks. During this period, the soil is kept at a uniformly moist DK by gradual spraying with water.

The test is evaluated by counting the number of sprouted sugar beet plants and healthy and diseased plants.

The concentration factors calculated according to Example 52 are shown in Table 2.

&5 Pythium on Zea mats
Pythium dabaryanum
) is cultured in carrot chip nutrient solution and added to the soil and sand mixture. A flowerpot is filled with the clay wall dyed in this manner, and corn seeds are sown into the pot. Immediately after sowing, an aqueous suspension of the test compound formulated as an irrigation agent is poured into the soil fill (±20 ppm of active ingredient based on the volume of the bed). The pots are then left in a greenhouse at 20°C for 5 weeks. During this period, the soil break is kept evenly moist by gradually spraying with water.

The test is evaluated by counting the number of sprouted sugar beet plants as well as healthy and diseased plants.

The concentration factors calculated according to Example 52 are shown in Table 2.

Table 2 Table 2 shows that the (as,t'R) enantiomer of the invention has an average of 3- It can be seen that the effect is 30 times better.

56 Inhibition of bacterial growth in vitro (agar introduction test) A solution of each test compound α75 (Lld) in acetone is diluted with 15 d of water under sterile conditions. A solution of each bacterial species im
1 or a sterile dilution prepared by adding water to the nutrient medium 19-K in a 9 ann diameter veterinary dish.
, introduced at 50°C. The concentration of each test compound was 5 cLa (LO5 and Ilo05 ppm) for each type. After 2 hours, these dishes and control dishes without test compound were plated on agar disks (diameter CL b Phytophthora capsie (overgrown side facing down)
i) Inoculate. The inoculated medium was kept at a relative humidity of 60-70%.
, 18° C. and kept in the dark until evaluation. 4-6
After 215 days of bacterial growth in control vetri dishes, the modulus of the test compound on radial growth (T vs. control test) was evaluated by plotting logarithmically on graph paper. To compare individual test compounds, the concentration of each test compound (EL s) at which growth is 50% of the control test.

value). The ELSa values are shown in FIG.

In Figure 3 Test 1 Pfi 56, an approximately 1:1 mixture of the highly active (as, 4'R) enantiomer and the (14) (aS, t'R) enantiomer provides a similarly pronounced effect. It is shown that gender is achieved.

57 Example for examining long-term activity as a fungicide Each test compound formulated as an irrigation agent was stirred in 10 ml of water and mixed with ±20 ml of water. Concentrations of test compounds are based on dry conditions.

Tobacco plants (Hoc) grown in disinfected soil
ks) seeds] in soil containing a fungicide (5A
'planted in the body). Two days later, Phytophthoraa nicotheanii (Phytophthoraa
The infection was artificially infected by inoculating with 2×20 d of spore suspension (10000 sporangia/MI) of M. n1cotianae).

The rating is based on the degree of damage to the leaves, dead stems, and damage.
It is conducted regularly according to the standard ■ of ~100 schools. Let R=O when the protection is complete.

Until the first typical signs of damage appear, the plant
considered protected. Trials are continued for 100 days while the tobacco plants ripen.

The long-term activity of individual test compounds is compared using a factor. This determines the period (in days) during which protection ■ exhibits an effect equivalent to that of isomer mixture 0 (as defined in Table 1) after 50 days at a concentration of α25 p pyH, for each test compound used at different concentrations. It is done by investigating. The comparison factor (f) is calculated according to the following formula.

Concentration (ppm) s.

The factors so calculated for the individual test compounds are summarized in Table 4. This allows for the (aS, l'R) enantiomer, as well as (&S, i'S) and (14) (
It can be seen that the pair of enantiomers aS, l'R) exhibits a distinctly longer duration of action than the other S enantiomers and mixtures of the two.

Table 4 a) Residual protective effect b) Osmosis The test method corresponds to that described in Example 52.

a) Residual protective effect b) Osmosis The test method corresponds to that described in Example 5.5.

(aR,'i's) (as,4'R) enantiomeric pair and (aR* 'i'R) (aS e'R) diastereomer are both tested in parallel and their The activity is the most active tested in parallel (as,
't'R) enantiomer. Table 5, similar to Table 2, shows how high the concentration of each diastereomer can be used to achieve the same full activity (95%, criterion 1) as the (ms, 4'R) enantiomer. Shows what to do.

What are the results of Table 5 showing that the (aS + 4′R) enantiomer is a significantly superior active ingredient compared to the Pond enantiomer and the racemic compound (mixture of isomers) of the prior art? In contrast, Table 5 shows that the activities of the enantiomeric pairs are surprisingly similar even though the active (as,4'R) enantiomer is only one of the two constituents of each pair. This indicates that it exhibits a certain degree of activity.

This result shows a clear interfering effect of the enantiomers that can increase biological activity.

Claims (48)

[Claims] (1) As an active ingredient, 3-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]amino in which the proportion of the active (aS,l'R) enantiomer is greater than 25% A disinfectant composition containing from 0.1 to 95% by weight of four possible isomers of different coordination of tetrahydrofuran-2-one, together with a suitable carrier. (2) The composition according to claim 1, wherein the proportion of the (aS, l'R) enantiomer is 28% by weight or more. (3) The composition according to claim 1, wherein the proportion of the (aS, l'R) enantiomer is 40% by weight or more. (4) The composition according to claim 1, wherein the proportion of the (aS, l'R) enantiomer is 50% by weight or more. (5) The composition according to claim 1, wherein the ratio of the (aS, l'R) enantiomer is 70% by weight or more. (6) 3-[N-(methoxy-acetyl)-N-(3-
Claim 1 characterized in that the aminotetrahydrofuran-2-one (chloro-2,6-dimethylphenyl) consists overwhelmingly (at least 90% by weight) of the (aS,l'R) enantiomer. Compositions as described. (7) The active (aS,l′R) enantiomer constitutes the highest proportion, followed by (aR,l′R) or (aR
, l'S) enantiomers are in the same high or lower proportion. (8) The composition according to claim 7, wherein the active ingredient consists essentially of a mixture of (aS, l'R) and (aR, l'R) enantiomers. (9) The composition according to claim 7, wherein the active ingredient consists essentially of a mixture of (aS, l'R) and (R, l'S) enantiomers. (10) The ratio of (aS, l'R) enantiomers is 25
% higher than 3-[N-(methoxyacetyl)-N-(3
-chloro-2,6-dimethylphenyl)]amino-tetrahydrofuran-2-one. (11) A compound according to claim 10, characterized in that the proportion of the (aS,l'R) enantiomer is at least 28% by weight. (12) A compound according to claim 10, characterized in that the proportion of the (aS, l'R) enantiomer is at least 40% by weight. (13) A compound according to claim 10, characterized in that the proportion of the (aS, l'R) enantiomer is at least 50% by weight. (14) A compound according to claim 10, characterized in that the proportion of the (aS, l'R) enantiomer is at least 70% by weight. (15) A compound according to claim 10, characterized in that the proportion of the (aS, l'R) enantiomer is at least 90% by weight. (16) 3-[N-(methoxyacetyl)-N-(3-
(aS,l'R) enantiomer of aminotetrahydrofuran-2-one (chloro-2,6-dimethylphenyl)]. (17) (aR, l'S)- and (aS, l'R)-3
-[N-(methoxyacetyl)-N-(3-chloro-2
, 6-dimethylphenyl)] racemic form of aminotetrahydrofuran-2-one. (18) 3-[N-(methoxyacetyl)-N-(3-
(aS, l'R) and (aR,
l'R) Mixture of diastereomers. (19) From the set of (aS, l'S) (aR, l'R) enantiomers, the corresponding racemates consisting of the enantiomers of the two pairs of diastereomers are obtained by adsorption onto the immobilized solid phase and elution with the liquid phase. 3-[
N-(methoxyacetyl)-N-(3-chloro-2,6
-dimethylphenyl)] aminotetrahydrofuran-2
A method for producing a set of (aR, l'S) and (aS, l'R) enantiomers of -one. (20) Claim 1, characterized in that the solid phase is an adsorption material based on agarose, Sepharose, cellulose, polyamide or polyacrylamide.
The method described in Section 9. (21) The method according to claim 20, wherein the adsorbent material is benzoylated or acetylated cellulose. (22) The method according to claim 21, wherein the adsorbent material is triacetyl cellulose. (23) The method according to claim 19, characterized in that the solid phase is an adsorption material based on silica gel or aluminum oxide. (24) (aR, l'S)- and (aS, l'R)-3
-[N-(methoxyacetyl)-N-(3-chloro-2
, 6-dimethylphenyl)] aminotetrahydrofuran-2-one is separated into the individual enantiomers by chromatography on an optically active solid phase, and then from the solution (aS, l'R ) of 3-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one (
aS, l'R) method for producing enantiomer. (25) The method according to claim 24, characterized in that triacetylcellulose is used as the optically active solid phase. (26) The method according to claim 24, characterized in that tris(3-methylbenzoyl)-cellulose is used as the optically active solid phase. (27)(l'R)-3-[N-(methoxyacetyl)
-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one in a suitable solvent,
(aR, l'R) (aS, l'R) consisting of chlorination in the presence or absence of a Lewis acid at 0-50 °C
-3-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one production method. (28) a) adsorbed onto a solid phase, and b) obtained (l′
The racemic 3-[N-(methoxyacetyl)-N-(
(aR, l'R) (aS, l
'R)-3-[N-(methoxyacetyl)-N-(3-
A method for producing aminotetrahydrofuran-2-one (chloro-2,6-dimethylphenyl). (29) Silica gel or Al_2O_3 as the solid phase
29. A method according to claim 28, characterized in that the method uses: (30) The method according to claim 28, characterized in that a solid phase based on cellulose is used. (31) The method according to claim 30, characterized in that acylated cellulose is used as the solid phase. (32) The method according to claim 31, characterized in that acetylated cellulose is used as the solid phase. (33) The method according to claim 32, characterized in that triacetyl cellulose is used as the solid phase. (34) The method according to claim 31, characterized in that benzoylated cellulose is used as the solid phase. (35) Tris(3-methylbenzyl)-
32. A method according to claim 31, characterized in that cellulose is used. (36) The method according to claim 27 or 28, wherein the solvent for the chlorination step is a halogenated hydrocarbon. (37) The method according to claim 27 or 28, wherein the solvent for the chlorination step is an alkane carboxylic acid. (38) The method according to claim 37, wherein the alkanecarboxylic acid is formic acid. (39) The method according to claim 37, wherein the alkanecarboxylic acid is acetic acid. (40) The method according to claim 27 or 28, wherein the chlorination is carried out at room temperature. (41) The method according to claim 27 or 28, characterized in that chlorine is used as the chlorinating agent. (42) The method according to claim 27 or 28, characterized in that sulfuryl chloride is used as the chlorinating agent. (43) The method according to claim 27 or 28, wherein the chlorination is carried out in the absence of a Lewis acid. (44) The method according to claim 27 or 28, wherein the Lewis acid is aluminum chloride, zinc chloride or tin(IV) chloride. (45) The method according to claim 27 or 28, wherein the Lewis acid is iron (III) chloride. (46)(l'R)-3-[N-(methoxyacetyl)
-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one solution is chlorinated,
The resulting (aR, l'R) enantiomer was subjected to adsorption chromatography to extract 3-
[N-(methoxyacetyl)-N-(3-chloro-2,
6-dimethylphenyl)] aminotetrahydrofuran-
Optically active 3-[N-(methoxyacetyl)-
A method for producing the (aS, l'R) isomer of N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one. (47) A substantial amount of 3-[N-
(aS,l'R) isomer or substantial 3-[N-
A mixture of (aR, l'S) and (aS, l'R) isomers of (methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one was added to plants or A method for controlling plant-damaging microorganisms, comprising application to their habitat. (48) 3-[N-(methoxyacetyl)-N-(3-chloro-2,6-dimethylphenyl)]aminotetrahydrofuran-2-one (a) in an amount effective for controlling microorganisms.
A method for controlling plant-damaging microorganisms, comprising applying R, l'R) and (aS, l'R) isomers to plants or their habitats.