JPS5826876A - Bactericidal compound - 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 relates to fungicidal compounds, in particular N-(λ6-dimethylphenyl)-N-methoxyaceter-6-amino-13-oxazolin-2-one, its use as a fungicide and It relates to its manufacturing method.

Italian patent applications No. 25.558 A/79 (Montegisson) and No. 24168 A/8 G (Sandoz) describe fungicidal compounds belonging to the group of N-aryl-N-acyl-3-aminoxazolidin-2-ones. was written.

In the above compounds, the aryl group consists of a phenyl group which may be substituted with groups of various nature such as alkyl, alkoxy and halogen. Fragmented acyl groups are derived from various carboxylic acids, such as various substituted saturated or unsaturated fatty acids, aromatic acids, heteroaromatic acids, and the like.

Furthermore, an alkyl group may be present at the 4th or 5th position of the 1 oxazolidine ring.

Here, the present inventor discovered a N-(2,6-dimethylphenyl)-N-methoxyacetyl-3-amino-13-oxazolin-2-one compound having the following formula: %. The compound I tt is endowed with fungicidal activity and is also useful as a fungicide, especially in the agricultural and horticultural fields.

The preparation of Compound I can be conveniently carried out by a three-step process as described below.

Note that the following symbols are used to explain the method that is the object of the present invention.

R= -〇HtOCHs The illegal first step is to condense 22-dialkoxyethyl chloroformate (chloroformate ester of glycolaldehyde dialkyl acecool) and arylhydrazine to form 6-arylcarbazic acid 2.2 -dialkoxyethyl ■.

(I[) 0II)----
>Ar-NH-NH-C-0-CL-CH(OR'
)t CN) (wherein R1 represents C8-C4 alkyl) Reaction 1 is carried out in an inert solvent in the presence of a hydrohalic acid-accepting base. Generally, an operating temperature of about 0°C is preferred.

Chloroformate esters of formula (1) are known compounds or can be easily prepared by reaction of phosgene with glycolaldehyde acetal.

The main third step consists of acylating the carbazic acid ester IV' obtained in the first step with a suitable acyl halide.

(V) R Again, the reaction is carried out in an inert solvent in the presence of a hydrohalic acid-accepting base.

This reaction does not require specific reaction conditions, but for convenience it is preferably carried out at room temperature.

The compound of formula V (methoxyacetyl halide) is a known compound.

The third stage of the main state is the 3-(2,6
This is the cyclization of λ2-dialkoxyethyl -dimethylphenyl)-3-(methoxyacetyl)carbazate.

This cyclization was performed using concentrated sulfuric acid and concentrated HeS
In one step if Oa (96-concentration) is used,
Or 5 o% H! When S04 is used, the intermediate N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-3-amino-4-hydroxy-13-oxazolidin-2-one Release,
This can be progressed by processing with high frequency 804.

VIF Reaction 3, whether performed with concentrated sulfuric acid or with more dilute acid, involves adding the carbazic acid ester directly to the sulfuric acid and then completely dissolving the mixture. This is done by stirring and keeping at room temperature for a few minutes until the temperature reaches room temperature. The compounds of formula (1) are new and are the object of the present invention as such.

This third step can be carried out in a similar manner using other concentrated strong acids in place of the sulfuric acid.

Compound ① is obtained by hydrogenating the double bond of the t6-oxazoline ring to form N-(2,6-simethylphenyl)-
It is useful herein as an intermediate for the preparation of N-methoxyacetyl-3-amino-15-oxazolidin-2-one (described in the aforementioned Italian patent application).

The hydrogenation reaction is carried out using hydrogen in the presence of a suitable catalyst.

As mentioned above, Compound I is endowed with fungicidal activity against plant pathogens.

Its action has a prophylactic character (i.e. prevents the development of disease)
and curative properties (if the infection is already advanced).

Furthermore, it has good systemic properties (ie, is transported to all parts of the plant).

In practical applications in the field of agriculture and horticulture, the fungicide of formula (2) can be used as it is or in the form of a suitable composition.

Such compositions contain as active ingredients a fungicide of the formula ■;
It consists of a solid or liquid carrier and optionally a surfactant and other additives.

The fungicidal compounds object of the present invention can be formulated by known techniques in the form of emulsifiable liquids, dry powders, wettable powders, etc.

If desired, it is possible to add other active ingredients to the composition or formulation, such as insecticides, other fungicides, plant growth inhibitors, etc.

The amount of the compound of formula (1) required to provide good and satisfactory protection of agricultural and horticultural crops against fungal attack depends on various factors, such as the type of composition or formulation, the fungi to be controlled, the degree of infection, etc. , depends on the type of crop to be protected, climate and environmental factors.

Examples are provided below to further illustrate the invention.

Example 1 A solution prepared by dissolving 2.45 liters of phosgene (COCI) in 40 mm of toluene was kept at 5°C.
Glycolaldehyde diethylacetal FHO-C
Ht-CH (OC* mountain) was added dropwise to a 20% toluene solution containing 3 g of triethylamine.

The reaction mixture was then allowed to stand for 12 hours, after which the formed precipitate (triethylamine hydrochloride) was taken from house to house.

The volatile components of the reaction mixture were then removed by evaporation under reduced pressure and a colorless liquid residue (4,5,
9) was obtained.

This residue was then distilled under reduced pressure to give 17II31HI
Both fractions were obtained as a colorless liquid, boiling at 80 DEG-82 DEG C. under a pressure of i and consisting of the desired product.

IR=1780cIIl (νC=O) Example 2 A solution prepared by dissolving 18 g of dimethylphenylhydrazine and t621 triethylamine in 100-methylene chloride was kept at 5°C with stirring, and was prepared by the method described in Example 1. 2.81 chloroformic acid ester was added.

The reaction mixture was allowed to stand for 12 hours, after which time the solvent was removed by evaporation under reduced pressure.

The residue was then diluted with 50% diethyl ether and the insoluble material (triethylamine hydrochloride) was separated.

The solvent was again removed by evaporation under reduced pressure, which gave a pale yellow oil of &I11 containing the fragmented product.

IR=3340cR (NH-CO) 1720cPIL (νC=0) Example 3 Preparation C X-〇-C Mountain/5-(2,6-dimethylphenyl)calcuccinic acid prepared as described in Example 2 2.2 -jethoxyethyl and 1
A solution of 11 g of triethylamine dissolved in 60 toluene [,12,9 of methoxyacetyl chloride was dissolved in 10
A solution prepared by dissolving - in toluene was added dropwise at room temperature. The reaction mixture was kept stirring at room temperature for 4 hours, then
Remove the solvent by evaporating under reduced pressure.

The semisolid residue was then diluted with 50% diethyl ether and the insoluble material was filtered off.

The solvent was removed from the solution by evaporation under reduced pressure, thus giving the desired product &8JF, which was then chromatographed on a silica gel column (eluent:
1 This was purified by ethyl acetate/toluene.

IR=326oaR-'(νNK) 1750m-'(j'C=0) 1700(1@'(νc=o) Example 4 2,4N carbazic acid ester obtained by K as described in Example 3, 20 m of concentrated H kept stirring at room temperature K,
804 (96% concentration) K dissolved.

At 11 min 15 min the reaction mixture was poured onto 40p ice and then neutralized with 50% NLOH solution. The resulting mixture was then extracted with ethyl acetate (2X 50m) followed by methylene chloride (2X50d).

The combined organic phase was dried over anhydrous N&*804 and the solvent was removed by evaporation under reduced pressure. In this way, t2. consisting of the desired product. f was obtained as a red oil, which was then subjected to thin layer chromatography (eluent: 35
:65 ratio of ethyl acetate to toluene) and then purified by papermaking to obtain the product of Kyosha 11.

IR=3140cIL (νCH=CH)1780α
(νC=O) 1700α (νC=0) Example 5 Intermediate N-(2,6-dimethylphenyl)-N-methoxyacetyl-3-amino-4-hydroxy-13-oxazolidin-2-one Performed by complete isolation , Two-Step Preparation of the Same Compound as Example 4 The synthesis of Example 4 was carried out in a similar manner, except that 50 sulfuric acid was used in place of concentrated sulfuric acid.

The reaction mixture was processed by the same procedure as described in Example 4 and fcfP1 preparation to give the intermediate 3-amino-4-hydroxyoxazolidinone as a white crystalline solid (mp=130-132
℃).

IR=32601 (v0H) 1790 cPIL (vC=0) 1690 cm (vC=0) Treatment of this intermediate with concentrated sulfuric acid gave the same compound as described in Example 4. It showed the same characteristics.

Example 6 Pass Plasmopara vicipora (plasmoparav)
curative fungicidal activity against 1) olcett) grown in pots in a controlled environment.

Plasmopara vitivora (B, etc.,) on the lower surface of leaves of seed vines Berl et da 7
Aqueous suspension of conidia of C. oni (1-920aO00
1i conidia) and 9.

After 48 hours in a humid saturated environment at 21°C, the plants were divided into two groups.

One of the groups was treated by spraying both sides of the leaves with an aqueous acetone suspension fi (20 volumes of acetone) of the test compound.

The entire plant was then transferred into an environment of controlled temperature of 25° C. and relative humidity of 60° C.

After the end of the fungal incubation period (7 days), the degree of fungal infection of the treated plants was evaluated in comparison to the degree of infection of infected untreated plants.

At a dosage of 100 ppm, the compounds of the present invention
showed a reduction in infection rate.

b) Peronospora tapasina (peronospora)
tabaeina) An aqueous suspension of conidia of Veronospora tapasina Adam (20Q, 000 conidia per 1 -) on the lower surface of the leaves of tobacco plants of the BsIrley species grown with traces of curative fungicidal activity against K. was scattered. After 6 hours in a humidity-saturated environment, the plants were divided into two groups and transferred to a constant temperature of 20° C. and relative humidity of 70° C. for incubation of the fungi.

48 hours after infection, one group of plants was treated with an aqueous acetone suspension of the test compound on both sides of its leaves.
! It was treated by sparging with L (20 vol. of acetone).

At 8 to 9 days of the incubation period (6 days), the degree of fungal infection of the treated plants was evaluated in comparison to the degree of infection of untreated plants.

At a dosage of 10 ppm, the compounds of the invention
showed the reduction rate of bacterial infection.

Agent's name: Motohiro Kurauchi Same as Akira Kurahashi

Claims (7)

[Claims] (1) N-(2,6-dimethylphenyl)-N-methoxyacetyl-3-amino-1,3-oxazolin-2-one compound of the following formula (%). (2) 2.2-dialkoxyethyl chloroxylate of the following formula % formula % () (where % R' is C8-C4° alkyl) and 2.6- of the following formula
Dimethylphenylhydrazine is condensed in an inert solvent in the presence of a hydrohalide-accepting base to give a λ2-dialkoxyethyl arylcarbazate of the formula (where R1 is C7-C4 alkyl). A methoxyacetyl halide of the following formula (where 2 is CI or Br) is reacted in an inert solvent in the presence of a hydrohalic acid-accepting base to obtain the compound IVK of the formula CHt 0CRs 1 0= 3-(2
, 6-dimethylphenyl)-3-methoxyacetylcar/< ,) is obtained, and this compound (i) is cyclized by treating it with a strong acid. Method for producing the compound described in Section 1. (3) The method according to claim 2, characterized in that the cyclization of intermediate compound (1) is carried out in concentrated sulfuric acid. (4) The method according to claim 2, characterized in that the cyclization of intermediate compound (1) is carried out using sob sulfuric acid to obtain an intermediate of the following formula, and then this intermediate is treated with concentrated sulfuric acid. . (5) The following formula (6) A method for controlling fungal infections of useful plants, which comprises spraying an effective amount of the microorganism according to claim 1 on crops as it is or in the form of an appropriate composition. (7) A fungicidal composition containing the compound according to claim 1 as an active ingredient, an inert carrier, and other additives as optional ingredients.