GB2104068A - N-(2,6-dimethylphenyl)-N- methoxyacetyl-3-amino-1,3- oxazolin-2-one, and use as a fungicide - Google Patents
N-(2,6-dimethylphenyl)-N- methoxyacetyl-3-amino-1,3- oxazolin-2-one, and use as a fungicide Download PDFInfo
- Publication number
- GB2104068A GB2104068A GB08222469A GB8222469A GB2104068A GB 2104068 A GB2104068 A GB 2104068A GB 08222469 A GB08222469 A GB 08222469A GB 8222469 A GB8222469 A GB 8222469A GB 2104068 A GB2104068 A GB 2104068A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- formula
- methoxyacetyl
- yield
- dimethylphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/38—One oxygen atom attached in position 2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/26—Oxygen atoms attached in position 2 with hetero atoms or acyl radicals directly attached to the ring nitrogen atom
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
N-(2,6-dimethylphenyl)-N- methoxyacetyl-3-amino-1,3-oxazolin- 2-one of formula: <IMAGE> possesses curative and preventative fungicidal activity and may be obtained by cyclization of 2,2- dialkoxy-ethyl 3-(2,6-dimethylphenyl)- 3-(methoxyacetyl)-carbazate with a strong acid.
Description
SPECIFICATION N-(2,6-dimethylphenyl)-N-methoxyacetyl-3-amino-1,3-oxazolin-2-one, its preparation and use as a fungicide
This invention relates to a fungicidal compound in particular to the compound N-(2,6dimethylphenyl)-N-methoxyacetyl-3-amino-1 ,3-oxazolin-2-one, to its preparation and to its use as a fungicide.
Italian Patent Application No. 25,538 A/79 (Montedison S.p.A.) and No. 24,168 A/80 (Sandoz
AG) disclose fungicidal compounds belonging to the class of N-aryl-N-acyl-3-amino-oxyazolydin-2ones. In these compounds the aryl groups consist of a phenyl group which may be substituted with groups of different characters, e.g. alkyl, alkoxy and halogen. The acyl group is derived from a range of carboxylic acids e.g. saturated or unsaturated aliphatic acids which may be substituted, aromatic acids and heteroaromatic acids. Alkyl groups may be present in either the 4- or 5-position on the oxazolydine ring of the compounds.
The present invention provides a new fungicidal compound N-(2,6-dimethylphenyl)-N methoxyacetyl-3-a mino- 1 ino-l ,3-oxazolin-2-one of formula:
Compound I is endowed with fungicidal activity and finds utility as fungicide, particularly in agricultural applications.
The compound (I) can be conveniently prepared by a three-stage process.
In the description of the process the following symbols are used:
R represents -CH2OCH3 Ar represents
The first stage of the process comprises condensing a 2,2-dialkoxy-ethyl chloroformiate (a chloroformiate of glycolic aldehyde dialkylacetal) (11) with the arylhydrazine (III), to yield a 2,2-dialkoxyethyl-3-arylcarbazate (IV):
in which R1 represents an alkyl group having 1 to 4 carbon atoms.
Reaction (1) is conducted in an inert solvent and in the presence of a halogenhydric acidaccepting base. It is generally preferred to operate at a temperature of about OOC.
The chloroformiates of formula (II) are known compounds and are readily prepared by reaction of phosgene (COCI2) with an acetal of glycolic aldehyde.
The second stage of the process comprises the acylation of the carbazate (IV) obtained for the first stage by a suitable acyl-halide (V):
The reaction is also conducted in an inert solvent and in the presence of a halogenhydric acidaccepting base.
The temperature for this reaction is not critical and for convenience is preferred to operate at room temperature.
The acyl halide of formula (V) (methoxyacetyl-halide) is a known compound.
The third stage of the process comprises the cyclisation of the 2,2-dialkoxy-ethyl 3-(2,6dimethylphenyl)-3-(methoxyacetyl)-carbazate (VI) obtained from the second stage.
The cyclization is carried out by using a strong acid e.g. sulphuric acid, and may be conducted in a single stage if concentrated H2SO4 (96% concentration) is used, or in two stages when using 50%
H2S04, by isolating intermediate N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-3-amino-4-hydroxy- 1 3- oxazolidin-2-one (VII) and by treating this intermediate compound with concentrated H2SO4:
Reaction (3) both when a single stage and two stage reaction is conducted by adding the carbazate (Vl) directly to the sulphuric acid and by then maintaining the mixture under stirring for a few minutes at room temperature until achieving complete dissolution. The third stage of the process may be carried out in an analogous way replacing the sulphuric acid with other concentrated strong acids.
The compound of formula (VII) is novel and forms a further aspect of the invention.
Compound (I) is also useful as intermediate for the preparation of compound N-(2,6 dimethylphenyl)-N-methoxyacetyl-3-amino- ,3-oxazolidin-2-one, which is in the previously cited
Italian Patent Applications, by hydrogenation of the double bond in the 1 3-oxazoline ring. The hydrogenation reaction may be conducted using hydrogen in the presence of a suitable catalyst.
Compound (I) is endowed with fungicidal activity against phytopathogenous fungi. Its action possesses a preventive character i.e. it hinders the onset of the disease as well as a curative character i.e. it combats an established infection.
Moreover, the compound possesses good systematical characteristics i.e. it is carried to all the parts of the plant.
For practical applications in agriculture, the fungicidal compound (I) may be used either as such or in the form of suitable compositions. Such compositions comprise the compound (I) as an active ingredient together with a solid or liquid carrier and optionally surfactants and other additives. The fungicidal compound (I) may be formulated, according to conventional techniques into emulsifiable liquid, dry powder, wettable powder, etc. If desired, it is possible to add to the compositions or formulations other active ingredients e.g. insecticides, other fungicides and phyto-growth regulators.
The quantity of compound of formula (I) necessary for obtaining a good and satisfactory protection of the agricultural cultivations from the attacks by fungi, depends on various factors, e.g. the type of composition or formulation, the type of fungus to be combatted, the degree of infection, the type of cultivation to be protected, as well as the climatical and environmental factors.
The invention will now be illustrated by the following Examples.
Example 1
Preparation of the 2,2-diethoxyethyl chloroformiate
20 ml of toluene containing 3.5 g of diethylacetal of glycolic aldehyde (HO-CH2-CH(0C2H5)2) and 3 g of triethylamine were added dropwise to a solution of 2.45 g of phosgene (COCI2) in 40 ml of toluene, maintained at 50C. The reaction mixture was allowed to stand for twelve hours, whereupon it was filtered to separate the precipitate that had formed (triethylamine chlorohydrate).
The volatile components of the reaction mixture were then removed by evaporation at reduced pressure to yield 4.5 g of a colourless liquid residue. This residue was distilled under vacuum and the fraction boiling at 80 to 820C at a pressure of 1 7 mmHg was gathered which consisted of the desired product in the form of a colourless liquid (2.8 g).
lR=l 780 cm- (P C=O).
Example 2
Preparation of 2,2-diethoxyethyl 3-(2,6-dimethylphenyl)-carbazate
2.8 g of the chloroformiate prepared in Example 1 were added to a solution of 1.8 g of dimethylphenylhydrazine and 1.62 g of triethylamine in 100 ml of methylene chloride, maintained under stirring at 50C. The reaction mixture was allowed to stand for 12 hours, whereafter the solvent was eliminated by evaporation at reduced pressure. The residue was then diluted with 50 ml of diethylether and the insoluble substance (triethylamine chlorohydrate) was separated by filtering.
The solvent was removed by evaporation at reduced pressure, to yield 3.1 g of a pale yellow oil consisting of the desired product.
IR 3340 cm-l (v NH-CO), 1720 cam~' (P C=O).
Example 3
Preparation of 2,2-diethoxyethyl 3-(2,6-dimethylphenyl)-3-methoxyacetyl-carbazate
A solution of 1.2 g of methoxyacetyl chloride dissolved in 10 ml of toluene was added dropwise to a solution of the 2,2-diethoxyethyl 3-(2,6-dimethylphenyl)-carbazate prepared in Example 2, and 1.11 g of triethylamine and 60 ml of toluene at room temperature. The reaction mixture was maintained under stirring for 4 hours at room temperature after which the solvent was removed by evaporation under reduced pressure.
The semisolid residue was then diluted with 50 ml of diethylether and the insoluble substances was removed by filtering.
The solvent was removed from the filtrate by evaporation at reduced pressure to yield 3.8 g of the desired product which was then purified by chromatography on a silica gel column (eluent: ethylacetate-toluene in a 1:1 ratio).
IR: 3260 cm~1 (v NH), 1 750 cm-l (v C=O), 1700 cm-' (v C=O).
Example 4
Preparation of N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-3-amino-1 ,3-oxazolin-2-one
2.4 g of the carbazate obtained in Example 3, were dissolved in 20 ml of concentrated H2SO4 (at 96% concentration) maintained under stirring at room temperature. After 1 5 minutes, the reaction mixture was poured on 40 g of ice and then neutralized with a 30% NaOH solution. The resulting mixture was extracted with ethylacetate (2x50 ml) and with methylene chloride (2x50 ml).
The combined organic phases were dried on anhydrous Na2SO4 and the solvents were then eliminated by evaporation at reduced pressure. 1.2 g of a reddish oil were obtained which was then purified by thin-layer chromatography (eluent: ethylacetate-toluene in a 35:65 ratio), to yield 1 g of the desired product.
IR: 3140 cm-l, (v CH=CH), 1780 cam~' (v C=O), 1700 cm-l (v C=O).
Example 5
Preparation of the same product as in Example 4, in two stages, with the isolation of intermediate N-(2,6-dimethylphenyl)-N-methoxyacetyl-3-amino-4-hydroxy-1,3-oxazolidin-2-one
The procedure of Example 4 was adopted with the exception that 50% sulphuric acid was used in
place of the concentrated sulphuric acid. The intermediate 3-amino-4-hydroxy-oxazolidinone was
isolated in the form of a white crystalline solid (melting point=130 to 1 320C).
IR: 3260 cm (V Or), 1790 cm-' (P C=O), 1 690 cm-' (P C=O).
The intermediate was treated with concentrated sulphuric acid, to yield the desired product as obtained in Example 4, which compound exhibited the same characteristics.
Example 6
Determination of the fungicide activity of compound: N-(2,6-dimethylphenyl)-N-methoxyacetyl 3-amino-i ,3-oxazolin-2-one a) Curative fungicide activity against Plasmopara vitivola.
A number of vine plants cv Dolcetto, grown in pots in a conditioned environment, were sprayed with an aqueous suspension of conidia of P. viticola (B. et C.) Berl et de Toni (200,000 conidia/ml) on the lower leaf face. After a 48 hour residence in a humidity saturated environment at 21 OC, the plants were subdivided into two groups.
One group of plants were treated by spraying a water-acetone suspension (20% in volume of acetone) of the product on both faces of the leaves.
The two groups of plants were then transferred into an environment at a conditioned temperature of 250C and at 60% of relative humidity.
At the end of the incubation period of the fungus (7 days) the degree of fungal infection of the treated plants in comparison with that of the untreated plants was evaluated.
At a dosage rate of 100 ppm the compound showed a 100% reduction of the infection.
b) Curative fungicide activity against Peronospora tabacina.
A number of tobacco plants cv Burley, grown in pots, were sprayed with an aqueous suspension of conidia of P. tabacina Adam (200.000 conidia per ml) on the lower leaf face. After 6 hours residence in a humidity saturated environment, the plants were divided into two groups and transferred into an environment with the temperature stabilized on 200C and with a relative humidity of 70%, for the incubation of the fungus.
After 48 hours from the infection, one group of plants was treated on both leaf faces, by spraying with a water-acetone suspension (20% volume of acetone) of the product.
At the end of the incubation period (6 days) the degree of fungal infection of the treated plants in comparison with that of the untreated plants was evaluated.
At the dosage rate of 1 00 ppm, the compound showed a 100% reduction of the fungal infection.
Claims (11)
1. N-(2,6-dimethyl phenyl )-N-methoxyacetyl-3-a mino-l ,3-oxazolin-2-one of formula:
2. A process for the preparation of the compound claimed in Claim 1 in which a 2,2-dialkoxyethyl chloroformiate of formula:
in which R1 is an alkyl group containing from 1 to 4 carbon atoms, is condensed with 2,6-dimethyl phenylhydrazine of formula:
in an inert solvent and in the presence of a halogenhydric acid-accepting base to yield 2,2dialkoxyethyl arylcarbazate of formula:
in which R1 is as defined above, compound (IV) is reacted with methoxyacetyl-halide of formula::
in which Z represents CI or Br in an inert solvent and in the presence of a halogenhydric acid-accepting base to yield 2,2-dialkoxy-ethyl 3-(2,6-dimethylphenyl)-3-methoxyacetyl-carbazate of formula:
in which R' is as defined above, and compound (VI) is cyclized by treatment with a strong acid to yield the desired product.
3. A process as claimed in Claim 2, in which the cyclization of a compound (VI) is carried out in concentrated sulphuric acid.
4. A process as claimed in Claim 2, in which the cyclization of compound (VI) is conducted in a 50% sulphuric acid, to yield a compound of the formula:
which is then treated with concentrated sulphuric acid to yield the desired product.
5. A process as claimed in Claim 2 substantially as herein described with reference to Example 4 or Example 5.
6. A compound of formula:
7. A method for combatting fungal infections in useful plants consisting in spreading over the plants an effective amount of the compound as claimed in Claim 1, either as such or in the form of a composition.
8. A method as claimed in Claim 7 in which the compound is applied at a dosage rate of about 100 ppm.
9. A method as claimed in Claim 7 substantially as herein described with reference to Example 6.
10. A fungicidal composition containing, as an active ingredient, a compound as claimed in Claim 1, together with an inert carrier.
11. A composition as claimed in Claim 10 substantially as herein described with reference to
Example 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23362/81A IT1138137B (en) | 1981-08-04 | 1981-08-04 | DERIVATIVES OF N-ARYL-N-ACYL-3-AMINO-1,3-OSSAZOLIDIN-2-ONI USEFUL AS FUNGICIDES AND AS INTERMEDIATES |
| IT25442/81A IT1140315B (en) | 1981-12-04 | 1981-12-04 | N-methoxy:acetyl 3-amino-1,3-oxalin-2-one deriv. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2104068A true GB2104068A (en) | 1983-03-02 |
| GB2104068B GB2104068B (en) | 1985-07-24 |
Family
ID=26328376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08222469A Expired GB2104068B (en) | 1981-08-04 | 1982-08-04 | N-(2,6-dimethyphenyl)-n-methoxyacetyl-3-amino-1,3 -oxazolin-2-one, and use as a fungicide |
Country Status (5)
| Country | Link |
|---|---|
| CH (1) | CH653676A5 (en) |
| DE (1) | DE3229000A1 (en) |
| FR (1) | FR2511000B1 (en) |
| GB (1) | GB2104068B (en) |
| NL (1) | NL8203049A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1123564B (en) * | 1979-09-07 | 1986-04-30 | Montedison Spa | N-ARIL-N-ACIL-3-AMINO-OSSAZOLIDIN-2-ONI FUNGICIDES |
| EP0030923A1 (en) * | 1979-12-18 | 1981-06-24 | Ciba-Geigy Ag | 3-(N-acyl-phenylamino)-2-oxazolidinones, process for their preparation and their use as microbicides or in microbicidal agents |
| DE3030026A1 (en) * | 1980-08-08 | 1981-03-26 | Sandoz-Patent-GmbH, 79539 Lörrach | Fungicidal 3-acylamino-oxazolidinone derivs. - prepd. by cyclisation of 2-haloethyl 2-acyl-2-phenyl-hydrazine carboxylate cpds. |
-
1982
- 1982-07-30 CH CH461682A patent/CH653676A5/en not_active IP Right Cessation
- 1982-07-30 FR FR8213333A patent/FR2511000B1/en not_active Expired
- 1982-07-30 NL NL8203049A patent/NL8203049A/en not_active Application Discontinuation
- 1982-08-03 DE DE19823229000 patent/DE3229000A1/en not_active Ceased
- 1982-08-04 GB GB08222469A patent/GB2104068B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2511000A1 (en) | 1983-02-11 |
| FR2511000B1 (en) | 1987-07-31 |
| DE3229000A1 (en) | 1983-02-24 |
| GB2104068B (en) | 1985-07-24 |
| NL8203049A (en) | 1983-03-01 |
| CH653676A5 (en) | 1986-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0577788A1 (en) | Insect control with substituted oxadiazole and thiadiazole compounds | |
| USRE27347E (en) | Vii. chs | |
| CA1203539A (en) | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides | |
| EP0027111A1 (en) | Lepidoptericidal isothiourea compounds | |
| CA1194485A (en) | Derivatives of n,n-substituted azolecarboxamide and agricultural and horticultural fungicidal or nematicidal composition containing same as active ingredient | |
| SU919580A3 (en) | Fungicidal composition | |
| US4477461A (en) | N-Aryl-N-acyl-3-amino-1,3-oxazolidine-2-thiones having fungicidal activity | |
| CS201517B2 (en) | Fungicide means | |
| GB2104068A (en) | N-(2,6-dimethylphenyl)-N- methoxyacetyl-3-amino-1,3- oxazolin-2-one, and use as a fungicide | |
| US4401675A (en) | Fungicidal carbazates | |
| EP0494227B1 (en) | Fungicidal 3-imino-1,4-oxathiins | |
| US4097512A (en) | N-tetrachlorofluoroethylthio-halo-benzoyl anilides and their use as fungicides | |
| US4303667A (en) | Phenylprrole derivatives | |
| CA1149393A (en) | 5-substituted oxazolidine herbicide antidotes | |
| EP0412681B1 (en) | Azolidine derivatives, process for preparing the same and agricultural and horticultural fungicide | |
| US3956303A (en) | Certain dithiazolylidene ureas | |
| JPH08183781A (en) | Triazine derivative and herbicide containing it as an active ingredient | |
| US3355352A (en) | Fungicidal composition | |
| JPS59225167A (en) | Bactericidal unsaturated 1,4-diketone | |
| EP0056314B1 (en) | N-haloalkyl thiobenzanilides, production thereof, compositions containing them and their use as fungicides | |
| JP3054977B2 (en) | Fungicidal furanone derivative | |
| US3881018A (en) | Substituted amidophenylguanidine fungicides | |
| US4357346A (en) | N-Haloalkyl thiobenzanilides and their use as fungicides | |
| EP0121344A2 (en) | N,N-substituted azolecarboxamide derivatives useful as fungicides and nematicides | |
| US4771063A (en) | Fungicidally active N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolidin-2-one |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930804 |