CA1203539A - N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides - Google Patents
N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicidesInfo
- Publication number
- CA1203539A CA1203539A CA000359647A CA359647A CA1203539A CA 1203539 A CA1203539 A CA 1203539A CA 000359647 A CA000359647 A CA 000359647A CA 359647 A CA359647 A CA 359647A CA 1203539 A CA1203539 A CA 1203539A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- phenyl
- amino
- acetyl
- oxazolidin
- 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.)
- Expired
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
- C07D263/08—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to a method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of the formula (I) (I) wherein B is a group of the formula (IIa) (IIa) or a group of the formula (IIb) (IIb) R' is H;
R, R1 and R2, equal to or different from each other are: H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
A is -CH2- or n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5 alkyl substituted with halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN; SCN; phenyl; phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms:
acetyl;; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl;
phenyl; -SO2-alkyl or acetyl]
and R7 is selected rom the class consisting of phenyl-acetyl, acetoxyacetyl, hydroxyacetyl, methoxy-acetyl, acetyl, phenoxyacetyl, provided that when -(A)n-R4 is -CH3, or R7 is acetyl, at least one of R, R1, R2-and R3 is different from hydrogen.
The present invention relates to a method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of the formula (I) (I) wherein B is a group of the formula (IIa) (IIa) or a group of the formula (IIb) (IIb) R' is H;
R, R1 and R2, equal to or different from each other are: H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
A is -CH2- or n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5 alkyl substituted with halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN; SCN; phenyl; phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms:
acetyl;; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl;
phenyl; -SO2-alkyl or acetyl]
and R7 is selected rom the class consisting of phenyl-acetyl, acetoxyacetyl, hydroxyacetyl, methoxy-acetyl, acetyl, phenoxyacetyl, provided that when -(A)n-R4 is -CH3, or R7 is acetyl, at least one of R, R1, R2-and R3 is different from hydrogen.
Description
~ `~ lZW539 The present invention relates to new fungicidal compounds and more especially to new fun~icidal N-aryl-N-acyl-3-amino-oxazolidin-2-ones.
Fungicidal compounds of the class of N-phenyl-1,3-oxazolidin-2,4-diones are described in, for instance, Dutch Patent Application No. 68/17249 (Sumitomo), in French Patent No.
Fungicidal compounds of the class of N-phenyl-1,3-oxazolidin-2,4-diones are described in, for instance, Dutch Patent Application No. 68/17249 (Sumitomo), in French Patent No.
2,172,295 (BASF), and in selgium Patent No. 874,406 to Montedison, S.p.A.
Recently, there has also been described the bacteri-cidal and fungicidal activity of some derivatives of aniline and glycine which carry on the nitrogen atom a variously substituted phenyl group and an acylic group of varying nature.
More particularly, this acylic group may consist of an a- or ~-haloalkanoyl (German Patent Application DOS 2,513,789 -Ciba Geigy = U.S.P. 4,025,848),or of an acetyl group substituted in c~-position with a sulphur or oxygen atom in its turn bound to groups of varying nature (French Patent Application No. 7,510,722 - Ciba~eigy = British patent 1,500,581) or again of a 2-furoyl, 2-thienoyl or pyridyl-2-carbonyl group (German Patent Applications DOS 2,513,732 and 3,513,788 - Ciba-Geigy = U.S.P. 4,046,911). ~ethylalaninates are kno~,n which possess microbi-cidal activity; these methylalaninates carry on the nitrogen atom a 2,6-dialkyl-phenyl and one of the following groups:
cyclopropanoyl , acryloyl, crotonoyl Other derivatives of fungicidal acyl-anilines have recently been described in Belgian Patent No. 863.615 (Ciba-Geigy) and in German Patent ~pplication DOS 2 ,745, 633 (Chevron).
The interest in the search for new derivatives from acylanilines having fungicidal action originates from the exigency of finding acylaniline derivatives that will have a high fungicidal activity combined with a lack of phytotoxicity.
In fact, some of the already known products, although 12~3539 developing an excellent fungicidal activity, prove, however, to be also toxic for the plants that one wishes to protect against infec-tions by fungi.
The damages caused by the phytotoxicity to the plants to be protected can hardly be avoided by using a dose of a fungicidal compound that may be the best compromise between the fungicidal activity of the compound and its phytotoxicity.
In fact, in the practical application in agricultural cultivations, the quantity of product that actually remains on the plant varies considerably depending on various factors such as, for instance, the weather conditions, (particularly the frequency of rainfalls?, and the correctness and frequency of the applications carried out by the farmer.
It would be advant~geous to have oxazolidin-2-ones which are highly active fungicides and safe for use in fighting fungi infestations of useful plants without damage to the plants, even when used in large quantities.
A divisional application of the present application relates to compounds of the general formula ~I) \ / \
CH
C = O
C ~ / (I) R l 4 \ C / n R2 ~ O l ll '~Rl O
wherein R and Rl equal to or different from each other, are halogen, Cl-C4 alkyl or Cl-C4 alkoxy;
R is H, halogen or Cl-C4 alkyl, A is -CH2- or -CH-n is 0 or 1, R is -OR or -SR (R is Cl-C5 alkyl or a heterocyclic group of 5 or 6 atoms containing from 1 to 3 hetero-atoms) when n is 1 or R is a heterocyclic group of 5 to 6 atoms containing from 1 to 3 hetero-atoms or Cl-C5 alkyl substituted with one or more halogen atoms, when n is 1 or 0 and R is H or CH3 and which are endowed with very effective fungicide activity while having a very low phytotoxicity.
The present invention on the other hand provides com-pounds of the general formula (I) /
CH C =~o .. H2 - N\ B
wherein B is a group of the formula (IIa) R' Rl~ \f (~, ~4 ~IIa~
or a group of the formula (IIb) Rl ~ N \ R7 (IIb) R' is H;
R, R and R2, equal to or different from each other are: H, halogen, Cl-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
Recently, there has also been described the bacteri-cidal and fungicidal activity of some derivatives of aniline and glycine which carry on the nitrogen atom a variously substituted phenyl group and an acylic group of varying nature.
More particularly, this acylic group may consist of an a- or ~-haloalkanoyl (German Patent Application DOS 2,513,789 -Ciba Geigy = U.S.P. 4,025,848),or of an acetyl group substituted in c~-position with a sulphur or oxygen atom in its turn bound to groups of varying nature (French Patent Application No. 7,510,722 - Ciba~eigy = British patent 1,500,581) or again of a 2-furoyl, 2-thienoyl or pyridyl-2-carbonyl group (German Patent Applications DOS 2,513,732 and 3,513,788 - Ciba-Geigy = U.S.P. 4,046,911). ~ethylalaninates are kno~,n which possess microbi-cidal activity; these methylalaninates carry on the nitrogen atom a 2,6-dialkyl-phenyl and one of the following groups:
cyclopropanoyl , acryloyl, crotonoyl Other derivatives of fungicidal acyl-anilines have recently been described in Belgian Patent No. 863.615 (Ciba-Geigy) and in German Patent ~pplication DOS 2 ,745, 633 (Chevron).
The interest in the search for new derivatives from acylanilines having fungicidal action originates from the exigency of finding acylaniline derivatives that will have a high fungicidal activity combined with a lack of phytotoxicity.
In fact, some of the already known products, although 12~3539 developing an excellent fungicidal activity, prove, however, to be also toxic for the plants that one wishes to protect against infec-tions by fungi.
The damages caused by the phytotoxicity to the plants to be protected can hardly be avoided by using a dose of a fungicidal compound that may be the best compromise between the fungicidal activity of the compound and its phytotoxicity.
In fact, in the practical application in agricultural cultivations, the quantity of product that actually remains on the plant varies considerably depending on various factors such as, for instance, the weather conditions, (particularly the frequency of rainfalls?, and the correctness and frequency of the applications carried out by the farmer.
It would be advant~geous to have oxazolidin-2-ones which are highly active fungicides and safe for use in fighting fungi infestations of useful plants without damage to the plants, even when used in large quantities.
A divisional application of the present application relates to compounds of the general formula ~I) \ / \
CH
C = O
C ~ / (I) R l 4 \ C / n R2 ~ O l ll '~Rl O
wherein R and Rl equal to or different from each other, are halogen, Cl-C4 alkyl or Cl-C4 alkoxy;
R is H, halogen or Cl-C4 alkyl, A is -CH2- or -CH-n is 0 or 1, R is -OR or -SR (R is Cl-C5 alkyl or a heterocyclic group of 5 or 6 atoms containing from 1 to 3 hetero-atoms) when n is 1 or R is a heterocyclic group of 5 to 6 atoms containing from 1 to 3 hetero-atoms or Cl-C5 alkyl substituted with one or more halogen atoms, when n is 1 or 0 and R is H or CH3 and which are endowed with very effective fungicide activity while having a very low phytotoxicity.
The present invention on the other hand provides com-pounds of the general formula (I) /
CH C =~o .. H2 - N\ B
wherein B is a group of the formula (IIa) R' Rl~ \f (~, ~4 ~IIa~
or a group of the formula (IIb) Rl ~ N \ R7 (IIb) R' is H;
R, R and R2, equal to or different from each other are: H, halogen, Cl-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
- 3 -A is -CH2- or -CH-n is 0 ox 1~
R is H, Cl-C5 alkyl, Cl-C5 aLkyl substituted with one or m~re halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n=l); CN;SCN: phenyl;phenyl substituted with one or more members of the class consisting of Cl-C5 alkyl and halogen atoms; acetyl;
-C-O-(alkyl); -oR5; -SR ; -NR R ~with R and R
(equal to or different from each other) being H;
Cl-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl; phenyl;
-S02-alkyl or acetyl~T
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl,acetyl, and phenoxyacetyl, provided that when -(A~n-R is -CH3, or R is acetyl, at least one of R, Rl, R2 and R3 is different from hydrogen:
and which are endowed with very effective fungicide activity while having a very low phytotoxicity.
The heterocyclic groups may for example be : furyl, tetrahydrofuryl, thienyl, pyrimidyl, pyridyl, imidazolyl, pyrazolyl or triazolyl.
N-phenyl-N-acetyl-3-amino-oxazolidin-2-one of formula (II) : O
N
~ N-C-CH3 (II) has been described in the Journal of Organis Chemistry, 31, p. 968 (1966) but has not ~ re~nized , however, as possessing fungicidal activity.
1;~3~39 In accordance with another:aspect of the present inven-tion, there is provided a method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of the formula (I) \ / \ (I) CH2 N \ B
wherein s is a group of the formula (IIa) ~ ~' C ~ (A~n ~ R ~IIa~
or a group of the formula (IIb) Rl ~ N \ R7 (IIb) R' is H;
R, R and R2, equal to or different from each other are: H, halogen, Cl-C4 alkyl or Cl-C4 alkoxy;
R is H or CH3;
A is -CH2- or -CH-n is 0 or 1;
R is H; Cl-C5 alkyl; Cl-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n = l); CN; SCN; phenyl;
phenyl substituted with one or more members of the
R is H, Cl-C5 alkyl, Cl-C5 aLkyl substituted with one or m~re halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n=l); CN;SCN: phenyl;phenyl substituted with one or more members of the class consisting of Cl-C5 alkyl and halogen atoms; acetyl;
-C-O-(alkyl); -oR5; -SR ; -NR R ~with R and R
(equal to or different from each other) being H;
Cl-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl; phenyl;
-S02-alkyl or acetyl~T
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl,acetyl, and phenoxyacetyl, provided that when -(A~n-R is -CH3, or R is acetyl, at least one of R, Rl, R2 and R3 is different from hydrogen:
and which are endowed with very effective fungicide activity while having a very low phytotoxicity.
The heterocyclic groups may for example be : furyl, tetrahydrofuryl, thienyl, pyrimidyl, pyridyl, imidazolyl, pyrazolyl or triazolyl.
N-phenyl-N-acetyl-3-amino-oxazolidin-2-one of formula (II) : O
N
~ N-C-CH3 (II) has been described in the Journal of Organis Chemistry, 31, p. 968 (1966) but has not ~ re~nized , however, as possessing fungicidal activity.
1;~3~39 In accordance with another:aspect of the present inven-tion, there is provided a method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of the formula (I) \ / \ (I) CH2 N \ B
wherein s is a group of the formula (IIa) ~ ~' C ~ (A~n ~ R ~IIa~
or a group of the formula (IIb) Rl ~ N \ R7 (IIb) R' is H;
R, R and R2, equal to or different from each other are: H, halogen, Cl-C4 alkyl or Cl-C4 alkoxy;
R is H or CH3;
A is -CH2- or -CH-n is 0 or 1;
R is H; Cl-C5 alkyl; Cl-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n = l); CN; SCN; phenyl;
phenyl substituted with one or more members of the
- 4 a -class consisting of Cl-C5 alkyl and halogen atoms, acetyl; ~-O-(àlkyl); -oR5; -SR5; -NR5R6 L~with R5 and R6 (equal to or different from each other) being H; Cl-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl;
phenyl; -SO2-alkyl or acetyi7 and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R is -CH3, or R is acetyl, at least one of R, Rl, R2 and R3 is different from hydrogen.
The preparation of the compounds of general formula (I) is carried out by means of processes known in the normal practice of organic chemistry.
For instance, an arylhydrazine (3) may be prepared by reacting the corresponding aniline (1) with sodium nitrite (NaNO2) in hydrochloric acid, and by then reducing the diazonium salt (2) thus obtained (scheme 1, equation 1 below), as described for instance in Journal of American Chemical Society, 81 , p.4673 (1959) The aryl-hydrazine is then caused to react with 2-halo-ethyl or l-methyl-2-haloethyl-chloroformate (4) (in its turn prepared by the action of phosgene on a halohydrin) in the presence of a base, and the intermediate (5) thus obtained is then cyclized in the presence of bases, thereby obtaining intermediate (6) (scheme 1, equation 2). This process has been described in the jour. of Am. Chem. Soc. 48. 1951 (1926).
Intermediate (6) is then condensed by means of the proper acylic halide (7?, according to known techniques (scheme l,-equation 3). The condensation reaction between intermediate (6) - 4 b -1~03539 and acylic halide (7) may be substituted or replaced by analogous reactions known in the literature, which allow the introduction of particular acylic groups. For instance, the compounds of general formula (I), in which the acylic part R4 = -oR5 , -SR5 or -N \ R6 may be prepared by reacting intermediate (6) with phosgene or with haloacetyl or halopropion~l hal1des (such as, for i~stance, C1 C_CK 1 ~c ,/
,/
, /
/
/' /
i _ 4 c ~
` ` 12~3S39 Cl-C-CH-CH3 respectively) and by then substituting the halogen O Cl atom according to known techniques.
The compounds of formula (I), in which the acylic part is _Il_R , and where R4 is NHR5, may be prepared by reacting intermediate (6) with an isocyanate of the formula: R5-N -. C = O.
The compounds of formula (I), in which the acylic part is -Cl-CH2-lCI-CH3 (A = CH2; R4 = acetyl), may be prepared by O O
reacting the intermediate (6) with diketene.
Scheme 1: B being the group of formula (IIa) ffl e N1~2 N=N Cl NH`-NH2 1) ~ NaN02 ~ R ~ Reducer ~ R
(1) (2) (3) R3 .-IR3 ~-NH-C-O-CH-CH2X
2)(3) + Cl-~-O-CH-CH2X ~R ~
O R R2 r (4) (5) r ~/0 IN
NH
R' I .
-HX ~ (6) t R~R<2 .~
3) ~) + X C-(A)n-R P (I) - /X=halogen; R,R ,R ,R , R , A and n have the same meanings as in general fon~a(I)_/ . Reaction 3 is carried out in an inert solvent, in the presence of a halogenhydric acid-accepting base, at reflux t~ærature.
The above scheme may be used for the case wherein B is the group of fon~a (IIb).
The compounds of general formula (I) are endowed with an excellent fungicide activity against phytopathogenous fungi and their action has both a lD preventive character(i.e.,they hinder the inception of the disease,as well as a - curative character (when,that is, the infection is already in progress).
The most important class of phytopathogenous fungi which can be fought by using the compounds of the invention, is that of Phycomicetes which comprises Plasmopara ~E~ ~
Phytophtora spp., Peronospora æ, Pseudoperonospora spp. and Phvthium sPP .
- The fungicidal compounds of the invention are effective for fighting-fungi infections of useful plants such as vine, I
tomato, tobacco, potato and other cultivations.
They possess good systemic characteristics(i.e., they are carried into the various parts of the plant) wherefore it is ~ossible to apply these products both on the leaves as well as on the soil.
Moreover, the compounds of general formula (I) proved to be compatible with the plants that are to be protected ?
against fungi attacks.
The majority of the compounds of general formula (I) do not show any sign of phytotoxicity at the amounts tried out, while the remainder showed only a low phytotoxicity,lo~er, at any rate, than that of the previously known fungicides.
In practical agricultural applications, the compounds of formula (I) can be used as such or in form of suitable com-Gl positions, consistmg of the compounds of formula (I) as active principle, agri-culturalIy acceptable carriers (e.g.solid or liquid inert carriers)and,optionally, surfactants and other additives. If desired, active compounds, such as other fungicides, insecticides, plant-growth regulators and so on, may be present in the compositions.
The compounds may be formulated according to the normal agricultural practice, as dusts, powders, wettable powders, emulsifiable liquids, granular formulates and so on.
The amounts of compounds of formula (I) to be dis-tributed for fighting infections by fungi depends on various factors, such as the active compound used, the type of com-position or formulation, the kind of infection and its degree, the kind of agricultural cultivation to be protected from fungi attack, the climatic and weather conditions, and so on.
Generally, amounts of compounds of formula (I) com-prised between 10 and 500 g/ha are sufficient, the preferred amount being from 100 to 250 g/ha. The following examples are given to illustrate the invention in more detail, and are not intended to be limiting.
Preparation of N-~methoxYacetYl)-N-(2,6-dimethvl-phenyl)-3-amino-oxazolidin-2-one.
(A) PreParation of 2,6-dimethYlphenylhydrazine :
107 g of 2,6-xylidine were dripped into a solution of 220 ml of concentrated HCl in 150 ml of water. After cooling down to -5C, this mixture was thereupon additioned with a solution of 66 ml of NaNO2 in 150 ml of H2O, over a period of time of about 1 hour and under vigorous stirring.
To the yellow-orange colored suspension thus obtained were added, at 0C and in about 4 hours, 450 g of SnC12.2H2O in 600 ml of a 5N aqueous solution of HCl.
The mixture was then maintained under stirring for 24 ~`
1203~39 hours, allowing the temperature to rise up to +20C. The solid thus formed was filtered, dissolved in 700 ml of H20 and then treated with a solution of 230 g of NaOH in 300 ml of H2O, at a temperature of between 10 and 15 & , after which the product was extrac-ted with diethylether (3 x 250 ml).
The etheric extract, after washing with H2O and anhy-drification on Na2SO4, was brought up to a volume of 1500 ml with diethylether and then was treated with anhydrous gaseous HCl, until attaining the complete precipitation of the chloro-hydrate of 2,6-dimethylhydrazine.
The salt was then filtered and dried, thereby obtaining 40 g of a white solid having a melting point (m.p.) equal to 205-207 & with decomposition.
By treatment with NaOH, from the chlorohydrate was obtained 2,6-dimethyl-phenylhydrazine.
(B) PreParation of 3-(2,6-dimethylaniline) oxazolidin-2-one:
To 41.4 g of 2-bromoethyl-chloroformate, prepared from phosgene and ethylenic bromohydrine, in 200 ml of benzene, there were additioned, at 10 & , the following reactants: 36.5 g of 2,6-dimethyl-phenylhydrazine (see point A), and 18 g of pyridine in 100 ml of benzene. This addition once completed, the temperature was allowed to rise up to 20& under constant vigorous stirring.
The pyridine chlorohydrate was removed by washing with water. The benzenic solution was further washed with HCl and with water to a neutral pH, and was then dried on Na2SO4 and evaporated to yield 61 g of an oily product which, crystallized from ligroin, gave 43 g of a light colored solid having a m.p.
of 58C-63C, and which consisted of 1-(2,6-dimethylphenyl-2-(~-bromoethyl)-oxycarbonyl hydrazine. ~The IR spectroscopy gave:
v(C=O) = 1710 cm ; v~NH-CO) = 3180 cm ; v(NH-Ar) = 3340 cm 1~7 40 g ofi this intermediate were dissolved in 500 ml of 1~203539 toluene and the solution was treated with 1~ g of tetramethyl-guanidine. This mixture was reflux-heated for 3 hours under stirring. After cooling down, the mixture was washed with 200 ml of H2O and then with 100 ml of diluted HCl and finally again with 200 ml o H2O.
The aqueous phases, reunited, were extracted with CH2C12 (2 x 200 ml)-The combined organic phases were anhydrified on Na2SO4and then the solvent was evaporated, thereby obtaining a solid residue which was crystallized from ligroin-ethylacetate (2:1).
There were thus obtained 22.5 g of 3-(2,6-dimethyl-aniline)-oxazolidin-2-one having a m.p. of 107-110C. ~The IR
spectrum showed: v(C=O) = 1770 cm ; v(NH) = 3340 cm .~
The cyclization reaction was repeated, dissolving the intermediate with m.p. of 58-62C in ethanol containing sodium ethylate, and by then reflux-heating the solution. After an analogous treatment of the reaction mixture, the same inter-- mediate was isolated; it had a m.p. of 107-110C.
(C) To 2 g of the intermediate, prepared as described in (B), in 70 ml of toluene and 0.2 ml of dimethylformamide, there were added 1.1 g of methoxyacetyl chloride. The reaction mixture was then reflux-heated for 8 hours. After cooling down, the reaction mixture was subjected to complete evaporation of the solvents. The residue, consisting of 2,9 g of a thick oily product, was purified on a silica gel column, using as eluent a mixture of benzene/ethylacetate, in a 1/1 ratio.
Thereby were obtained, after removal of the solvents, 1.1 g of a syrupy product which crystallized spontaneously and which, after re-crystallization from ligroin/ethylacetate (1:1) mixture, yields 1 g of the desired compound whose characteristics have been recorded in Table 1 (compound No. 6).
C The IR spectrum gave : v(N-CO-CH2) = 1680 cm ; v(N-CO-O) =
EXAMP~E 2 Operating analogously to Example 1, and in accordance with the reactions at pages 5 and 6, there were prepared, in addition to Compound N 6, the other compounds reported in the following Table I:
- TABLE I(a) Table Ia - B being a group of the formula (IIa) Compound R Rl R2 R3 4 m.p.( ) IR(c) 10 N ` (C) -1 1 H H H H 1 CH2 Cl 71-4 1690-1760 3 H H H H 1 CH2 i.C3H7 oil 1680-1770 Table Ib - B being a group of the formula (IIb) Compound R Rl R2 R3 R7 m.p.(b) IR(c) N (0C) (cm_l) .
C 3 3 H H CH2C6H5 oil 1670-1770 8 2 C 3 3 H H CH O CO CH oil 1690-1770 9 2 3 3 H H CH2H 135-8 1690-1770( ) ~otes to Table I:
(a) The ele~ental analysis of all the compounds is consistent ~ith the assigned structure.
(b) Melting points have not been corrected.
(c) Only the bands corresponding to vC=O are reported.
( ~ vOH = 3300 `/
/
/
/
/
~ 10 a -EXAMP~E 3 Curative activitY on vine~PeronosPora~ (PlasmoPara vitivola ~B et C) Berl et de Toni) Vine leaves of Cv. Dolcetto, grown in pots in a con-ditioned environment stabilized at 25C and 60~ of relative humidity, were sprinkled on the lower faces thereof with an aqueous suspension of PlasmoPara viticola conidia (200,000 conidia/cc). After 24 hours of dwelling in a humidity (moisture) saturated environment, stabilized at 21C, the plants were treated by sprinkling both faces of the leaves with the products under examination in a hydroacetone solution at 20~ of acetone (vol./vol.).
At the end of the incubation period (7 days), the degree of infection was assessed by sight on the basis of a value scale with indexes going from :
0 : no control, infection equal to that of witness - plant (infected but non-treated plants) 1 : 1-20% reduction of the infection ;
2 : 20-60~ reduction of the infection ;
3 : 60~90~ reduction of the infection ;
4 : reduction of the infection greater than 90%.
The results obtained are-recorded in the following Table 2:
Curative activity against vine Peronospora by foliar application at the dose of 0.5~.
Compound No. ActivityCompound No. Activity 2 . 3 8 4 Curative activitY on PeronosPora of Tobacco (Peronospora tabacina Adam).
The leaves of tobacco plants Cv. Burley, grown in pots in a conditioned environment, were sprinkled, on the lower ~aces of the leaves, with a Peronospora tabacina conidia-suspension ~200,000 conidia/cc). After 6 hours of dwelling in a humidity saturated environment, the plants were transferred to a con-ditioned environment stabilized at 20C and 70~ of relative 10- humidity, for the incubation of the fungus. 24 hours after the infection, treatment was carried out by sprinkling both leaf faces with the product under examination, in a hydroacetone solution of 20% in acetone (vol./vol.).
At the end of the incubation period (6 days) the extent of the infection was assessed by sight according to a value scale with an index range equal to that of Example 3.
- The results of the test are recorded in the following Table 3:
Curative activity by foliar application at doses of 0.5% on plants infected with Peronospora of Tobacco.
Compound No. Activity Determination of the phvtotoxicity deqree Leaves of Cv. Dolcetto vine plants, grown in pots in a conditioned environment stabilized at 25C and 60% relative humidity, were treated by sprinkling both leaf faces with a lZ03S39 hydroacetone solution at 204 of acetone (vol./vol.) of the products under examination.
After 7 days, the extent or degree of phytotoxic symptoms were evaluated by sight according to a value scale with indexes ranging from 100 (for fully damaged plant) to 0 (for a healthy plant).
The corresponding data are recorded in Table 4, in comparison with the phytotoxicity indexes of the two compounds known to be shortly marketed, i.e.: "Furalaxyl" (British 10` Patent No. 1,448.810 - Ciba-Geigy) and "Ridomil" (French Patent Application No. 2,267,042 - Ciba-Geiqy).
Phytotoxity index for doses at 0.6%.
Compound No.Phytotoxicity index 6 ~ 0 "Furalaxyl" (1) 100 "Ridomil" (2)60 (1) "Furalaxyl" = N-(2,6-dimethylphenyl)-N-(l'-carbomethoxy-ethyl)-2-furoyl-amide :
H3CO-C-lH 1~3 H3C ~ ~CH3 '~
(2) "Ridomil" = N-(2,6-dimethylphenyl)-N -(l'-carbomethoxy-ethyl)-methoxyacetamide :
H3C-O-CI-CH ~C-CH20CH3 o 3C~CH3
phenyl; -SO2-alkyl or acetyi7 and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R is -CH3, or R is acetyl, at least one of R, Rl, R2 and R3 is different from hydrogen.
The preparation of the compounds of general formula (I) is carried out by means of processes known in the normal practice of organic chemistry.
For instance, an arylhydrazine (3) may be prepared by reacting the corresponding aniline (1) with sodium nitrite (NaNO2) in hydrochloric acid, and by then reducing the diazonium salt (2) thus obtained (scheme 1, equation 1 below), as described for instance in Journal of American Chemical Society, 81 , p.4673 (1959) The aryl-hydrazine is then caused to react with 2-halo-ethyl or l-methyl-2-haloethyl-chloroformate (4) (in its turn prepared by the action of phosgene on a halohydrin) in the presence of a base, and the intermediate (5) thus obtained is then cyclized in the presence of bases, thereby obtaining intermediate (6) (scheme 1, equation 2). This process has been described in the jour. of Am. Chem. Soc. 48. 1951 (1926).
Intermediate (6) is then condensed by means of the proper acylic halide (7?, according to known techniques (scheme l,-equation 3). The condensation reaction between intermediate (6) - 4 b -1~03539 and acylic halide (7) may be substituted or replaced by analogous reactions known in the literature, which allow the introduction of particular acylic groups. For instance, the compounds of general formula (I), in which the acylic part R4 = -oR5 , -SR5 or -N \ R6 may be prepared by reacting intermediate (6) with phosgene or with haloacetyl or halopropion~l hal1des (such as, for i~stance, C1 C_CK 1 ~c ,/
,/
, /
/
/' /
i _ 4 c ~
` ` 12~3S39 Cl-C-CH-CH3 respectively) and by then substituting the halogen O Cl atom according to known techniques.
The compounds of formula (I), in which the acylic part is _Il_R , and where R4 is NHR5, may be prepared by reacting intermediate (6) with an isocyanate of the formula: R5-N -. C = O.
The compounds of formula (I), in which the acylic part is -Cl-CH2-lCI-CH3 (A = CH2; R4 = acetyl), may be prepared by O O
reacting the intermediate (6) with diketene.
Scheme 1: B being the group of formula (IIa) ffl e N1~2 N=N Cl NH`-NH2 1) ~ NaN02 ~ R ~ Reducer ~ R
(1) (2) (3) R3 .-IR3 ~-NH-C-O-CH-CH2X
2)(3) + Cl-~-O-CH-CH2X ~R ~
O R R2 r (4) (5) r ~/0 IN
NH
R' I .
-HX ~ (6) t R~R<2 .~
3) ~) + X C-(A)n-R P (I) - /X=halogen; R,R ,R ,R , R , A and n have the same meanings as in general fon~a(I)_/ . Reaction 3 is carried out in an inert solvent, in the presence of a halogenhydric acid-accepting base, at reflux t~ærature.
The above scheme may be used for the case wherein B is the group of fon~a (IIb).
The compounds of general formula (I) are endowed with an excellent fungicide activity against phytopathogenous fungi and their action has both a lD preventive character(i.e.,they hinder the inception of the disease,as well as a - curative character (when,that is, the infection is already in progress).
The most important class of phytopathogenous fungi which can be fought by using the compounds of the invention, is that of Phycomicetes which comprises Plasmopara ~E~ ~
Phytophtora spp., Peronospora æ, Pseudoperonospora spp. and Phvthium sPP .
- The fungicidal compounds of the invention are effective for fighting-fungi infections of useful plants such as vine, I
tomato, tobacco, potato and other cultivations.
They possess good systemic characteristics(i.e., they are carried into the various parts of the plant) wherefore it is ~ossible to apply these products both on the leaves as well as on the soil.
Moreover, the compounds of general formula (I) proved to be compatible with the plants that are to be protected ?
against fungi attacks.
The majority of the compounds of general formula (I) do not show any sign of phytotoxicity at the amounts tried out, while the remainder showed only a low phytotoxicity,lo~er, at any rate, than that of the previously known fungicides.
In practical agricultural applications, the compounds of formula (I) can be used as such or in form of suitable com-Gl positions, consistmg of the compounds of formula (I) as active principle, agri-culturalIy acceptable carriers (e.g.solid or liquid inert carriers)and,optionally, surfactants and other additives. If desired, active compounds, such as other fungicides, insecticides, plant-growth regulators and so on, may be present in the compositions.
The compounds may be formulated according to the normal agricultural practice, as dusts, powders, wettable powders, emulsifiable liquids, granular formulates and so on.
The amounts of compounds of formula (I) to be dis-tributed for fighting infections by fungi depends on various factors, such as the active compound used, the type of com-position or formulation, the kind of infection and its degree, the kind of agricultural cultivation to be protected from fungi attack, the climatic and weather conditions, and so on.
Generally, amounts of compounds of formula (I) com-prised between 10 and 500 g/ha are sufficient, the preferred amount being from 100 to 250 g/ha. The following examples are given to illustrate the invention in more detail, and are not intended to be limiting.
Preparation of N-~methoxYacetYl)-N-(2,6-dimethvl-phenyl)-3-amino-oxazolidin-2-one.
(A) PreParation of 2,6-dimethYlphenylhydrazine :
107 g of 2,6-xylidine were dripped into a solution of 220 ml of concentrated HCl in 150 ml of water. After cooling down to -5C, this mixture was thereupon additioned with a solution of 66 ml of NaNO2 in 150 ml of H2O, over a period of time of about 1 hour and under vigorous stirring.
To the yellow-orange colored suspension thus obtained were added, at 0C and in about 4 hours, 450 g of SnC12.2H2O in 600 ml of a 5N aqueous solution of HCl.
The mixture was then maintained under stirring for 24 ~`
1203~39 hours, allowing the temperature to rise up to +20C. The solid thus formed was filtered, dissolved in 700 ml of H20 and then treated with a solution of 230 g of NaOH in 300 ml of H2O, at a temperature of between 10 and 15 & , after which the product was extrac-ted with diethylether (3 x 250 ml).
The etheric extract, after washing with H2O and anhy-drification on Na2SO4, was brought up to a volume of 1500 ml with diethylether and then was treated with anhydrous gaseous HCl, until attaining the complete precipitation of the chloro-hydrate of 2,6-dimethylhydrazine.
The salt was then filtered and dried, thereby obtaining 40 g of a white solid having a melting point (m.p.) equal to 205-207 & with decomposition.
By treatment with NaOH, from the chlorohydrate was obtained 2,6-dimethyl-phenylhydrazine.
(B) PreParation of 3-(2,6-dimethylaniline) oxazolidin-2-one:
To 41.4 g of 2-bromoethyl-chloroformate, prepared from phosgene and ethylenic bromohydrine, in 200 ml of benzene, there were additioned, at 10 & , the following reactants: 36.5 g of 2,6-dimethyl-phenylhydrazine (see point A), and 18 g of pyridine in 100 ml of benzene. This addition once completed, the temperature was allowed to rise up to 20& under constant vigorous stirring.
The pyridine chlorohydrate was removed by washing with water. The benzenic solution was further washed with HCl and with water to a neutral pH, and was then dried on Na2SO4 and evaporated to yield 61 g of an oily product which, crystallized from ligroin, gave 43 g of a light colored solid having a m.p.
of 58C-63C, and which consisted of 1-(2,6-dimethylphenyl-2-(~-bromoethyl)-oxycarbonyl hydrazine. ~The IR spectroscopy gave:
v(C=O) = 1710 cm ; v~NH-CO) = 3180 cm ; v(NH-Ar) = 3340 cm 1~7 40 g ofi this intermediate were dissolved in 500 ml of 1~203539 toluene and the solution was treated with 1~ g of tetramethyl-guanidine. This mixture was reflux-heated for 3 hours under stirring. After cooling down, the mixture was washed with 200 ml of H2O and then with 100 ml of diluted HCl and finally again with 200 ml o H2O.
The aqueous phases, reunited, were extracted with CH2C12 (2 x 200 ml)-The combined organic phases were anhydrified on Na2SO4and then the solvent was evaporated, thereby obtaining a solid residue which was crystallized from ligroin-ethylacetate (2:1).
There were thus obtained 22.5 g of 3-(2,6-dimethyl-aniline)-oxazolidin-2-one having a m.p. of 107-110C. ~The IR
spectrum showed: v(C=O) = 1770 cm ; v(NH) = 3340 cm .~
The cyclization reaction was repeated, dissolving the intermediate with m.p. of 58-62C in ethanol containing sodium ethylate, and by then reflux-heating the solution. After an analogous treatment of the reaction mixture, the same inter-- mediate was isolated; it had a m.p. of 107-110C.
(C) To 2 g of the intermediate, prepared as described in (B), in 70 ml of toluene and 0.2 ml of dimethylformamide, there were added 1.1 g of methoxyacetyl chloride. The reaction mixture was then reflux-heated for 8 hours. After cooling down, the reaction mixture was subjected to complete evaporation of the solvents. The residue, consisting of 2,9 g of a thick oily product, was purified on a silica gel column, using as eluent a mixture of benzene/ethylacetate, in a 1/1 ratio.
Thereby were obtained, after removal of the solvents, 1.1 g of a syrupy product which crystallized spontaneously and which, after re-crystallization from ligroin/ethylacetate (1:1) mixture, yields 1 g of the desired compound whose characteristics have been recorded in Table 1 (compound No. 6).
C The IR spectrum gave : v(N-CO-CH2) = 1680 cm ; v(N-CO-O) =
EXAMP~E 2 Operating analogously to Example 1, and in accordance with the reactions at pages 5 and 6, there were prepared, in addition to Compound N 6, the other compounds reported in the following Table I:
- TABLE I(a) Table Ia - B being a group of the formula (IIa) Compound R Rl R2 R3 4 m.p.( ) IR(c) 10 N ` (C) -1 1 H H H H 1 CH2 Cl 71-4 1690-1760 3 H H H H 1 CH2 i.C3H7 oil 1680-1770 Table Ib - B being a group of the formula (IIb) Compound R Rl R2 R3 R7 m.p.(b) IR(c) N (0C) (cm_l) .
C 3 3 H H CH2C6H5 oil 1670-1770 8 2 C 3 3 H H CH O CO CH oil 1690-1770 9 2 3 3 H H CH2H 135-8 1690-1770( ) ~otes to Table I:
(a) The ele~ental analysis of all the compounds is consistent ~ith the assigned structure.
(b) Melting points have not been corrected.
(c) Only the bands corresponding to vC=O are reported.
( ~ vOH = 3300 `/
/
/
/
/
~ 10 a -EXAMP~E 3 Curative activitY on vine~PeronosPora~ (PlasmoPara vitivola ~B et C) Berl et de Toni) Vine leaves of Cv. Dolcetto, grown in pots in a con-ditioned environment stabilized at 25C and 60~ of relative humidity, were sprinkled on the lower faces thereof with an aqueous suspension of PlasmoPara viticola conidia (200,000 conidia/cc). After 24 hours of dwelling in a humidity (moisture) saturated environment, stabilized at 21C, the plants were treated by sprinkling both faces of the leaves with the products under examination in a hydroacetone solution at 20~ of acetone (vol./vol.).
At the end of the incubation period (7 days), the degree of infection was assessed by sight on the basis of a value scale with indexes going from :
0 : no control, infection equal to that of witness - plant (infected but non-treated plants) 1 : 1-20% reduction of the infection ;
2 : 20-60~ reduction of the infection ;
3 : 60~90~ reduction of the infection ;
4 : reduction of the infection greater than 90%.
The results obtained are-recorded in the following Table 2:
Curative activity against vine Peronospora by foliar application at the dose of 0.5~.
Compound No. ActivityCompound No. Activity 2 . 3 8 4 Curative activitY on PeronosPora of Tobacco (Peronospora tabacina Adam).
The leaves of tobacco plants Cv. Burley, grown in pots in a conditioned environment, were sprinkled, on the lower ~aces of the leaves, with a Peronospora tabacina conidia-suspension ~200,000 conidia/cc). After 6 hours of dwelling in a humidity saturated environment, the plants were transferred to a con-ditioned environment stabilized at 20C and 70~ of relative 10- humidity, for the incubation of the fungus. 24 hours after the infection, treatment was carried out by sprinkling both leaf faces with the product under examination, in a hydroacetone solution of 20% in acetone (vol./vol.).
At the end of the incubation period (6 days) the extent of the infection was assessed by sight according to a value scale with an index range equal to that of Example 3.
- The results of the test are recorded in the following Table 3:
Curative activity by foliar application at doses of 0.5% on plants infected with Peronospora of Tobacco.
Compound No. Activity Determination of the phvtotoxicity deqree Leaves of Cv. Dolcetto vine plants, grown in pots in a conditioned environment stabilized at 25C and 60% relative humidity, were treated by sprinkling both leaf faces with a lZ03S39 hydroacetone solution at 204 of acetone (vol./vol.) of the products under examination.
After 7 days, the extent or degree of phytotoxic symptoms were evaluated by sight according to a value scale with indexes ranging from 100 (for fully damaged plant) to 0 (for a healthy plant).
The corresponding data are recorded in Table 4, in comparison with the phytotoxicity indexes of the two compounds known to be shortly marketed, i.e.: "Furalaxyl" (British 10` Patent No. 1,448.810 - Ciba-Geigy) and "Ridomil" (French Patent Application No. 2,267,042 - Ciba-Geiqy).
Phytotoxity index for doses at 0.6%.
Compound No.Phytotoxicity index 6 ~ 0 "Furalaxyl" (1) 100 "Ridomil" (2)60 (1) "Furalaxyl" = N-(2,6-dimethylphenyl)-N-(l'-carbomethoxy-ethyl)-2-furoyl-amide :
H3CO-C-lH 1~3 H3C ~ ~CH3 '~
(2) "Ridomil" = N-(2,6-dimethylphenyl)-N -(l'-carbomethoxy-ethyl)-methoxyacetamide :
H3C-O-CI-CH ~C-CH20CH3 o 3C~CH3
Claims (16)
1. Compounds of general formula (I) :
(I) in which R' is H;
R, R1 and R2, equal to or different from each other, are H, halogen, C1-C4 alkyl or C1-C4 alkoxyl;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n is 1); CN; SCN; phenyl;
phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms;
acetyl; ; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl; phenyl;
-SO2-alkyl or acetyl] provided that, when -(A)n-R4 is CH3, at least one of R, R1, R2 or R3 is -l5-different from hydrogen.
(I) in which R' is H;
R, R1 and R2, equal to or different from each other, are H, halogen, C1-C4 alkyl or C1-C4 alkoxyl;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n is 1); CN; SCN; phenyl;
phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms;
acetyl; ; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl; phenyl;
-SO2-alkyl or acetyl] provided that, when -(A)n-R4 is CH3, at least one of R, R1, R2 or R3 is -l5-different from hydrogen.
2. N-phenyl-N-chloroacetyl-3-amino-oxazolidin-2-one.
3. N-phenyl-N-phenylacetyl-3-amino-oxazolidin-2-one.
4. N-phenyl-N-(.beta.-methyl-propionyl)-3-amino-oxa-zolidin-2-one.
5. N-phenyl-N-methoxyacetyl-3-amino-oxazolidin-2-one.
6. Method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of formula (I) (I) wherein R' is H;
R, R1 and R2, equal to or different from each other, are H, halogen, C1-C4 alkyl or C1-C4 alkoxyl;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5-alkyl substituted with halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n = l)i CN;scN; phenyl;
phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms;
acetyl; ; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl;
phenyl; -SO2-alkyl or acetyl] provided that, when -(A)n-R4 is CH3, at least one of R, R1, R2 or R3 is different from hydrogen.
R, R1 and R2, equal to or different from each other, are H, halogen, C1-C4 alkyl or C1-C4 alkoxyl;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl; C1-C5-alkyl substituted with halogen atoms; C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl; halogen (when n = l)i CN;scN; phenyl;
phenyl substituted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms;
acetyl; ; -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl; C2-C5 alkenyl; C2-C5 alkynyl;
phenyl; -SO2-alkyl or acetyl] provided that, when -(A)n-R4 is CH3, at least one of R, R1, R2 or R3 is different from hydrogen.
7. Method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live an effective amount of at least one compound selected from the class consisting of N-phenyl-N-chloro-acetyl-3-amino-oxazolidin-2-one,N-phenyl-N-phenylacetyl-3-amino-oxazolidin-2-one, N-phenyl-N-(.beta.-methyl-propionyl)-3-amino-oxazolidin-2-one and N-phenyl-N-methoxyacetyl-3-amino-oxazolidin-2-one.
8. Compounds of the general formula (I) (I) wherein B is a group of the formula (IIa) (IIa) or a group of the formula (IIb) (IIb) R' is H;
R, R1 and R2, equal to or different from each other are: H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl;C1-C5 alkyl substituted with one or more halogen atoms, C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN ; SCN ; phenyl phenyl substi-tuted with one or more members of the classOconsisting of C1-C5 alkyl and halogen atoms; acetyl; (alkyl); -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl;
C2-C5 alkenyl; C2-C5 alkynyl; phenyl; -SO2-alkyl or acetyl]
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R4 is-CH3, or R7 is acetyl, at least one of R, R1, R2 and R3 is different from hydrogen.
R, R1 and R2, equal to or different from each other are: H, halogen, C1-C4 alkyl or C1-C4 alkoxy;
R3 is H or CH3;
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl;C1-C5 alkyl substituted with one or more halogen atoms, C3-C6 cycloalkyl; C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN ; SCN ; phenyl phenyl substi-tuted with one or more members of the classOconsisting of C1-C5 alkyl and halogen atoms; acetyl; (alkyl); -OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl;
C2-C5 alkenyl; C2-C5 alkynyl; phenyl; -SO2-alkyl or acetyl]
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R4 is-CH3, or R7 is acetyl, at least one of R, R1, R2 and R3 is different from hydrogen.
9. N-(2,6-dimethylphenyl)-N-phenylacetyl-3-amino-oxazoli-din-2-one.
10. N-(2,6-dimethylphenyl)-N-acetoxyacetyl-3-amino-oxazolidin-2-one.
11. N-(2,6-dimethylphenyl)-N-hydroxyacetyl-3-amino-oxazolidin-2-one.
12. N-(2,6-dimethylphenyl)-N-methoxyoxalyl-3-amino-oxazolidin-2-one.
13. N-(2,6-dimethylphenyl)-N-acetyl-3-amino-oxazolidin-2-one.
14. N-(2,6-dimethylphenyl)-N-phenoxyacetyl-3-amino-oxazolidin-2-one.
15. Method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live, an effective amount of at least one of the compounds of the formula (I) (I) wherein s is a group of the formula (IIa) (IIa) or a group of the formula (IIb) (IIb) R' is H;
R, R1 and R2, equal to or different.from each other are: H, halogen, C1-C4 alkyi or C1-C4 alkoxy, R3 is H or CH3 L
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl;C1-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl, C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN; SCN; phenyl; phenyl substitu-ted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms; acetyl; ;
-OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl;
C2-C5 alkenyl; C2-C5 alkynyl; phenyl; -SO2-alkyl or acetyl]
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R is -CH3, or R7 is acetyl, at least one of R, R1, R2 and R3 is different from hydrogen.
R, R1 and R2, equal to or different.from each other are: H, halogen, C1-C4 alkyi or C1-C4 alkoxy, R3 is H or CH3 L
A is -CH2 or ;
n is 0 or 1;
R4 is H; C1-C5 alkyl;C1-C5 alkyl substituted with one or more halogen atoms; C3-C6 cycloalkyl, C2-C5 alkenyl or ethinyl;
halogen (when n = 1); CN; SCN; phenyl; phenyl substitu-ted with one or more members of the class consisting of C1-C5 alkyl and halogen atoms; acetyl; ;
-OR5; -SR5; -NR5R6 [with R5 and R6 (equal to or different from each other) being H; C1-C5 alkyl;
C2-C5 alkenyl; C2-C5 alkynyl; phenyl; -SO2-alkyl or acetyl]
and R7 is selected from the class consisting of phenylacetyl, acetoxyacetyl, hydroxyacetyl, methoxyoxalyl, acetyl,and phenoxyacetyl, provided that when -(A)n-R is -CH3, or R7 is acetyl, at least one of R, R1, R2 and R3 is different from hydrogen.
16. Method for fighting fungi infections of plants consisting in distributing on the plants or on the soil in which the plants live an effective amount of at least one compound selected from the class consisting of N-(2,6-dimethylphenyl)-N-phenylacetyl-3-amino-oxazolidin-2-one, N-(2,6-dimethylphenyl)-N-acetoxyacetyl-3-amino-oxazolidin-2-one, N-(2,6-dimethylphenyl)-N-hydroxyacetyl-3-amino-oxazolidin-2-one, N-(2,6-dimethylphenyl)-N-methoxyalkyl-3-amino-oxazolidin-2-one, N-(2,6-dimethylphenyl)-N-acetyl-3-amino-oxazolidin-2-one and N-(2,6-dimethylphenyl)-N-phenoxyacetyl-3-amino-oxazolidin-2-one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000432137A CA1296340C (en) | 1979-09-07 | 1983-07-08 | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25538/79A IT1123564B (en) | 1979-09-07 | 1979-09-07 | N-ARIL-N-ACIL-3-AMINO-OSSAZOLIDIN-2-ONI FUNGICIDES |
| IT25538A/79 | 1979-09-07 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000432137A Division CA1296340C (en) | 1979-09-07 | 1983-07-08 | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1203539A true CA1203539A (en) | 1986-04-22 |
Family
ID=11217010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000359647A Expired CA1203539A (en) | 1979-09-07 | 1980-09-05 | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS5655381A (en) |
| AR (1) | AR228138A1 (en) |
| AU (1) | AU545683B2 (en) |
| BE (1) | BE885117A (en) |
| BR (1) | BR8005645A (en) |
| CA (1) | CA1203539A (en) |
| CH (1) | CH645513A5 (en) |
| CY (1) | CY1235A (en) |
| DE (1) | DE3033161A1 (en) |
| ES (1) | ES494856A0 (en) |
| FR (1) | FR2464649A1 (en) |
| GB (1) | GB2058071B (en) |
| GR (1) | GR69955B (en) |
| IL (1) | IL60950A (en) |
| IT (1) | IT1123564B (en) |
| KE (1) | KE3383A (en) |
| NL (1) | NL8004962A (en) |
| OA (1) | OA06743A (en) |
| ZA (1) | ZA805450B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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. |
| WO1982002713A1 (en) * | 1981-02-05 | 1982-08-19 | Sandmeier Rudolf | Fungicides |
| WO1982002714A1 (en) * | 1981-02-09 | 1982-08-19 | Sandmeier Rudolf | Fungicides |
| CH653676A5 (en) * | 1981-08-04 | 1986-01-15 | Montedison Spa | FUNGICIDE COMPOUND. |
| IT1168031B (en) * | 1981-10-01 | 1987-05-20 | Montedison Spa | FUNGICIDAL COMPOUNDS |
| CH654979A5 (en) * | 1982-01-26 | 1986-03-27 | Sandoz Ag | FUNGICIDES AND THEIR USE. |
| IT1152196B (en) * | 1982-05-27 | 1986-12-31 | Montedison Spa | FUNGICIDE COMPOUND |
| GB8504181D0 (en) * | 1985-02-19 | 1985-03-20 | Sandoz Ltd | Fungicides |
| US4771063A (en) * | 1985-06-06 | 1988-09-13 | Montedison S.P.A | Fungicidally active N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolidin-2-one |
| EP0284555A1 (en) * | 1987-03-12 | 1988-09-28 | Ciba-Geigy Ag | Process for the preparation of N-acyl-N-(oxazoliden-2-on-3-yl)-2,6-dialkyl-3-chloroanilines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097262A (en) * | 1977-04-22 | 1978-06-27 | E. I. Du Pont De Nemours And Company | Herbicidal acetamides |
| BE884661A (en) * | 1979-08-16 | 1981-02-09 | Sandoz Sa | NOVEL 3-AMINO-OXAZOLIDINE-2-ONES, THEIR PREPARATION AND THEIR USE AS FUNGICIDAL AGENTS |
| CH646158A5 (en) * | 1979-08-16 | 1984-11-15 | Sandoz Ag | 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. |
-
1979
- 1979-09-07 IT IT25538/79A patent/IT1123564B/en active
-
1980
- 1980-09-01 NL NL8004962A patent/NL8004962A/en not_active Application Discontinuation
- 1980-09-02 CH CH660380A patent/CH645513A5/en not_active IP Right Cessation
- 1980-09-02 FR FR8018915A patent/FR2464649A1/en active Granted
- 1980-09-02 IL IL60950A patent/IL60950A/en unknown
- 1980-09-02 AU AU61949/80A patent/AU545683B2/en not_active Ceased
- 1980-09-03 JP JP12124080A patent/JPS5655381A/en active Granted
- 1980-09-03 DE DE19803033161 patent/DE3033161A1/en not_active Ceased
- 1980-09-03 ZA ZA00805450A patent/ZA805450B/en unknown
- 1980-09-04 BR BR8005645A patent/BR8005645A/en not_active IP Right Cessation
- 1980-09-05 GR GR62813A patent/GR69955B/el unknown
- 1980-09-05 CA CA000359647A patent/CA1203539A/en not_active Expired
- 1980-09-05 BE BE0/202012A patent/BE885117A/en not_active IP Right Cessation
- 1980-09-06 ES ES494856A patent/ES494856A0/en active Granted
- 1980-09-08 GB GB8028922A patent/GB2058071B/en not_active Expired
- 1980-09-08 CY CY1235A patent/CY1235A/en unknown
- 1980-09-08 AR AR282439A patent/AR228138A1/en active
-
1981
- 1981-02-13 OA OA57326A patent/OA06743A/en unknown
-
1984
- 1984-03-01 KE KE3383A patent/KE3383A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8005645A (en) | 1981-03-17 |
| IL60950A0 (en) | 1980-11-30 |
| IL60950A (en) | 1985-05-31 |
| ES8106713A1 (en) | 1981-09-01 |
| GB2058071B (en) | 1983-11-09 |
| GR69955B (en) | 1982-07-22 |
| BE885117A (en) | 1981-03-05 |
| ES494856A0 (en) | 1981-09-01 |
| NL8004962A (en) | 1981-03-10 |
| AU545683B2 (en) | 1985-07-25 |
| DE3033161A1 (en) | 1981-04-02 |
| AU6194980A (en) | 1981-03-12 |
| GB2058071A (en) | 1981-04-08 |
| JPH0240664B2 (en) | 1990-09-12 |
| IT7925538A0 (en) | 1979-09-07 |
| KE3383A (en) | 1984-03-23 |
| CH645513A5 (en) | 1984-10-15 |
| CY1235A (en) | 1984-06-29 |
| OA06743A (en) | 1982-06-30 |
| FR2464649A1 (en) | 1981-03-20 |
| FR2464649B1 (en) | 1983-07-08 |
| JPS5655381A (en) | 1981-05-15 |
| ZA805450B (en) | 1981-08-26 |
| IT1123564B (en) | 1986-04-30 |
| AR228138A1 (en) | 1983-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2793956B2 (en) | Triazine derivative and herbicide containing the same as active ingredient | |
| US4229465A (en) | Cyanopyrrole derivatives | |
| DE69410894T2 (en) | 2-aminothiazolecarboxamide derivatives, process for their preparation and their use for controlling phytopathogenic organisms | |
| CS196415B2 (en) | Fungicide and process for preparing effective compounds | |
| CA1064952A (en) | Microbicidal compositions | |
| CA1203539A (en) | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides | |
| JPS626548B2 (en) | ||
| CS201517B2 (en) | Fungicide means | |
| CS241520B2 (en) | Fungicide and/or nematocide and method of active substance preparation | |
| US4152460A (en) | 3-Chloro-2,6-dinitro-N-(substituted phenyl)-4-(trifluoromethyl)benzenamines | |
| CA1296340C (en) | N-aryl-n-acyl-3-amino-oxazolidin-2-ones fungicides | |
| US4771063A (en) | Fungicidally active N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolidin-2-one | |
| US4303667A (en) | Phenylprrole derivatives | |
| US4187096A (en) | Biocidally-active 1,3-benzodithiole-2-thione compounds | |
| US4038403A (en) | Benzotriazole ovicides and larvicides | |
| JPH05125057A (en) | 1-phenyl-4-trifluoromethyluracil derivative and herbicide containing the same as active ingredient | |
| US4049820A (en) | Substituted urazole and thiourazole compounds as agricultural fungicidal agents | |
| JPH027949B2 (en) | ||
| US4331669A (en) | Fungicidal pyridyl arylureas, compositions containing them and method of controlling fungi and bacteria | |
| US4240821A (en) | Biocidally-active 1,3-benzodithiole-2-thione compounds | |
| EP0121344A2 (en) | N,N-substituted azolecarboxamide derivatives useful as fungicides and nematicides | |
| US5721192A (en) | Aminosulfonyl ureas | |
| US4357346A (en) | N-Haloalkyl thiobenzanilides and their use as fungicides | |
| US4472583A (en) | 4-Isothiocyanato-2,6-bis-(trifluoromethyl)pyridine | |
| US4920142A (en) | Fungicidal imidazole derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |