DE3033161A1 - N-ARYL-N-ACYL-3-AMINO-OXAZOLIDIN-2-ONE AND FUNGICIDES CONTAINING THEM - Google Patents

Description

PATENTA N WALT E

dr. V. SCHMIED-KOWARZIK. · Dr. P. WEINHOLD · Munich D1PL.-ING. G. DANNENBERG · dr. D. GUDEL dipl-ing. S. SCHUBERT- Frankfurt

SIEGFRIEDSTRASSE 8 8OOO MÖNCHEN 4O

TELEPHONE: (089) 335024 f 335025 TELEX: 5215679

SK / SK K.2774

Montedison SpA
Forο Buonaparte 31
Milan / Italy

N-Aryl-N-acyl-3-amino-oxazolidin-2-ones and fungicides containing them

1300U / 1089

The present invention relates to new fungicidal agents, in particular to those of the class of 3-aminooxazolidin-2-ones, which show a high fimgicidal activity with good tolerance in useful plants which should be protected against fungus infestation. The present invention also relates to the use of the new connections.

Fungicidal compounds of the class of the N-phenyl-1,3-oxazolidine-2,4-diones are e.g. in the HoIl. Patent application 68/17249, in FR-PS 2 172 295 and in the IT patent application 20579 A / 78.

Recently, the bactericidal and fungicidal activity of certain derivatives of aniline and glycine which contain a phenyl group substituted by various substituents and varying acyl groups on the nitrogen atom has also been described.

This acyl group can in particular be selected from a ος or ß-haloalkanoyl group (DE-OS 2 513 789) or an acetyl group which is in the ^ -position with a sulfur or oxygen atom is substituted, which in turn is bound to different groups (FR patent application 7 510 722) or a 2-furoyl, 2-thienoyl or pyridyl-2-carboxyl group (DE-OS 2 513 732 and 2 513 788) exist. Furthermore, the microbiocidal activity of methylalaninates described which on the nitrogen atom a 2,6-dialkylphonyl group and one of the following groups contain: Cyclopropanoyl, Acryloyl, Crotonoyl (Switzerland. Patent applications Λ 980/74 and 2 906/75).

Other derivatives of fungicidal acyl anilines have recently been introduced in BE 'PS 863 C-15 and in DE-OS 2,745,533.

1-30014 / 1089 ORIGINAL. INSPECTED

302 6Ί

The research into new derivatives of acylanilines with fungicidal action results from the desire to find acylaniline derivatives with high fungicidal activity and lacking phytotoxicity. Although the already known compounds often have an excellent fungicidal activity, However, compared to the plants to be protected and toxic * When used in such a dose that provides the best compromise between their fungicidal activity and their phytotoxicity, so can their phytotoxicity in The damage caused to plants to be protected can hardly be avoided.

In practical use in agricultural crops, the actual amount of product remaining on the plant varies depending on various factors, v / io weather conditions (in particular the frequency of rainfalls), the accuracy and frequency of those carried out by the farmer. Applications, considerably. Therefore, a fungicidal preparation with good fungicidal activity and a simultaneous, high safety factor must be available, so that even high amounts of product do not cause any damage to the treated plants.

It has now been found that compounds with the general j formula

(D

in which

130014/1089 ORIGINAL BATHROOM

1 2

it and. R ', which are equal or different - :.' jh.u; dejt, for H,

Halogen, C ₁ -C ₇₁ alkyl or Ll ' ¹ for H or CTI-. stf-ht,

Alkoxy-tshon;

Λ for -Clip- or

CH ₇ .

-CH-

; eht,

η has a fourth of 0 or 1 and
rl for H, a C ^ j-Cc alkyl group, a C ^ -C- cycloalkyl group, a Cp-C, -alkenyl group, ethynyl, halogen (v / enn η = 1), CN, SCN, one optionally substituted with C ^ -C ₁ , - alkyl groups or halogen atoms o phenyl group, a heterocyclic group with 5 or υ atoms, which contains 1 to 3 heteroatoms (especially furyl, tetrahydrofuryl, thienyl, pyrimidyl, pyridyl, imidazolyl, pyrazolyl, triazolyl), acetyl, COO-alkyl, -OR " ⁵ ,

5 5 r ~ 5 6 -31t, -NR stands /. Where R and R ", which are the same or different

. R ⁶

can be different, for H, C ^ -C ^ alkyl, Cp-C ₁ - alkenyl, Cp-C ₁ - alkynyl, phenyl, a heterocyclic group with 5 or t atoms, which contains 1 to 3 heteroatoms,

Alkyl or acetyl 7

(jine fungicidal activity at the same time, very little Have piiytotoxicity.

Thus the oil of the present invention is the use the connections of. Formula (i) in combating

Fungus infections in crops. !

! TTuι * c'.no dor fall under the above general formula (i) - j \ · μ ! "·, 'Verb'ndungen is known from the literature, namely |

SO ₂ -

ii-Phenyl-N-acetyl-ZJ-cmino-oxazolidin-S-one of the formula (II):

C = O

N -C-CH ₇
ti J

(II)

(v ;; l

J3 0 0 14/1089 BATH ORIGINAL

3 O 3 3161

However, Compound (II) has no fungicidal activity known.

Another object of the present invention is to provide of compounds of the general formula (i) in which

12 ~ *>

at least one of the radicals R, R, R and R has a different meaning as hydrogen when - (A) -R '= CH-. is.

The compounds of the general formula (I) are prepared by customary organic chemistry processes. For example, an arylhydrazine (3) can be prepared by reacting the corresponding aniline (1) with sodium nitrite (NaNOp) in hydrochloric acid and then reducing the diazonium salt (.2) obtained in this way (cf. scheme 1, equation 1;

• e.g. J.Am.Chem.Soc., 81., page 4675 (1959). Then that will Arylhydrazine with 2-haloethyl or 1-methyl-2-haloethyl chloroformate (4) (which in turn is produced by the action of phosgene on a halohydrin) in the presence of a base, and the intermediate (5) thus obtained becomes the intermediate in the presence of a base (6) cyclized (Scheme 1, Equation 2). This method is described, for example, in J. Am. Chem. Soc, 48, 1951 (1926).

The intermediate (6) is then condensed in a corresponding manner with the appropriate acyl halide (7) (scheme 1, equation 3). The condensation between the intermediate (6) and the acyl halide (7) can be replaced by analogous "known reactions" which allow the introduction of special acyl groups R ¹ -OR, -SR

or -N

/ R-

is,

e.g. by implementing the intermediate '

Product (6) with phosgene or with haloacetyl or halopropionyl halides (e.g. Cl-C-CH ₀ Cl or

it ^ 0

13 0014/1089
BATH ORIGINAL

Cl-C - CH-CH-) and subsequent substitution of the halogen

Il f

0 cl

citoins produced in a known manner.

Compounds of the formula (I) in which the acyl part -C-R

is, where R ^μ stands for NHR, can be prepared by reacting the intermediate (6) with an isocyanate of the formula RN = C = O.

The compounds of the formula (i) in which the acyl part is -C-CH ₀ -C-CIl (A = CH ₀ ; R ^{/ | -} = acetyl) can be converted

Il ^ Il 5 * -

15 0 0

setting of the intermediate product (6) made with diketene

will.

Scheme 1

NH-NH,

aNO, / HCl>

H-NH-CO-CH-CH X η 2

(5) (4) X (5) 35 R— -HX, R ^r (6) / \ \ N ^
NH -οΊ

.1300U / 10
BATH ORIGINAL

(6)

+ X-C-

-HX

■ j) \ oj -ι- Λ-υ - (, Α; _η -κ '^ (I)

(X stands for halogen; R, R ¹ , R ² , R ^D , R ^[ , A and η have the meanings given for formula (I)). Reaction 3) is carried out in an inert solvent in the presence of a hydrohalic acid accepting base at reflux temperature.

The compounds of the general formula (i) have a drawing fungicidal activity against phytopathogeno fungi, whereby their effect is preventive (i.e. the development of an iV-.rar · - prevention) and is also curative (i.e. when ready; an infection has taken place).

The main classes of phytopathogenic fungi associated with the Compounds according to the invention which can be combated are Phycomicetes, the Plasmopara spp., Phytophtora spp., Perono spora spp. and Pseudo? eronospora spp. and Phythium spp. include.

The fungicidal compounds according to the invention are suitable for use Control of fungus infections in crops such as vines! Tomatoes, tobacco, potatoes and other crops. You own ii good systemic properties (i.e. they are divided into the different Parts of plants transported), which is why they can be used both on the leaves and on the ground The compounds of the general formula (I) have proven to be much more common with the plants to be protected against fungus infestation than proven to be tolerable. Most of the twists according to the invention "the Formula (I) show no signs of phytotoxicity at the levels tested, while the rest show only a low phytotoxicity, which is in any case below that of known fungicides.

In agricultural practice, the fungicidal compounds can den- Fo: ^i; v.cl (i) per se or in the form of suitable preparations, the one compound of the formula

13 0 0U / 1089 BAD ORIGINAL

"40 -

(I) as an active ingredient as well as solid or:. · Liquid inert Carriers and optionally surfactants and other additives. If necessary, in the Pres provide other active compounds such as other fungicides, insecticides, plant growth regulators, etc., present Rome.

In normal agricultural practice, the compounds can be air, dust, powder, wettable powder, emulsifiable Liquids, granular formulations, etc. formulated will.

The amount to be applied to combat fungus infections of the compounds of formula (i) depends on various factors, such as the active compound used, the type of preparation or formulation, the type of infection and its extent, the type of before fungus infestation . "protective agricultural culture, the climatic and conditions, etc.

Πον / öhnlloh suffice with a fungicidal compound of the Formula (I) between 10 and 500 g / ha, amounts between 100 and 250 g / ha being preferred.

The following examples illustrate the present invention.

Ώ ei ν, ρ ie 1 1

Preparation of N- (methoxyacetyl) -N- (2,6-dimethylphenyl) -ü-amino-oxazolidin-2-one

A) Production of Z, 6-dimethylphenyl hydrazine.

1 3 0 0 * 1 4/1 0 8 9 BAD ORIGINAL

107 g of 2,6-xylidine were concentrated in a solution of 220 ml. HCl added dropwise to 150 ml of water. After cooling to -5 ° C., a solution of 66 ml of NaNO ₂ in 150 ml of water was added to the mixture over the course of about 1 hour and with vigorous stirring. _{450 g of SnOl 2} -2HpO in 600 ml of a 5N aqueous HCl solution were added to the yellow-orange suspension obtained in this way at ⁰ ° C. and in about 4 hours. The mixture was then stirred for 24 hours, the temperature being allowed to rise to 20 ^° C. The contaminant thus formed was filtered off, dissolved in 700 ml of H ₂ O and then treated with a solution of 230 g of NaOH in 300 ml of H ₂ O at a temperature between 10 and 15 ° C., whereupon the product was treated 3 times with 250 ml of diethyl ether each time was extracted.

The essential extracts were washed with water and dried on Na ₂ SO. brought to a volume of 1500 ml with diethyl ether and then treated with anhydrous gaseous HCl until the chlorohydrate of 2,6-dimethylhydrazine has precipitated out completely. The salt was filtered off and dried and yielded 40 g of a white pesticide with a P. of 205 to 207 ⁰ C (u dec.). Treatment with NaOH gave 2,6-dimethylphenylhydrazine from the chlorohydrate.

B) Preparation of 3- (2,6-dimethylaniline) oxazolidin-2-one To 41.4 g of phosgene and a Äthylenbromhydrin prepared 2-Bromathylchlorformiates in 200 ml of benzene, the following reactants were added at 10 ⁰ C: 36.5 g of 2,6-dimethylphenylhydrazine (see paragraph A) and 18 g of pyridine in 100 ml of benzene. After the addition had ended, the temperature was allowed to rise to 20 ^° C., with constant vigorous stirring. The pyridine chlorohydrate was removed by washing with water. Then the benzene solution was washed further with HCl and with water until a neutral pH value _{, dried over Na 2} SO, and evaporated to 61 g of an oily product, which after recrystallization from ligroin 43 g of a light-colored pest with a P. of 58 to 63 ⁰ C

1 30014/1089

delivered, which from 1- (2,6-dimethylphenyl) -2- (ß-bromoethyl) -

V (NH-Ar) =

oxycarbonylhydrazine.
IR = V (O = O) = 1710 cm "¹; V (NH-CO) = 3180 cm 3340 cm" ¹ .

" ¹

40 g of this intermediate product were dissolved in 500 ml of toluene and then treated with 16 g of tetramethylguanidine. This mixture was then heated to reflux for 3 hours with stirring. After cooling, the mixture was _{washed with 200 ml of H 2} O, then with 100 ml of dilute hydrochloric acid and again with 200 ml of water. The combined aqueous phase was extracted twice with 200 ml of CH ₂ Cl _{2 each time.} The combined organic phases were on Na ₂ SO. dried, then the solvent was evaporated to give a solid residue which was recrystallized from 2: 1 ligroin: ethyl acetate. Thus there was obtained 22.5 g of 3- (2,6-dimethylaniline) oxazolidin-2-one having a melting point 107-110 ⁰ C.
IR = Ί (C = O) = 1770 cm " ¹ } V (NH) = 3340 cm" ¹ .

The cyclization was repeated using a 3P. 58-62 ⁰ C in ethanol containing sodium ethylate, dissolved and then heated the solution to reflux again. After a similar treatment of the reaction mixture, the same intermediate product was obtained with an i ¹ . from 107 to 110 ⁰ C isolated.

C) To 2 g of the intermediate, prepared as in paragraph B) in 70 ml of toluene and 0.2 ml of dimethylformamide was 1.1 g Methoxyacetyl chloride added. The reaction mixture was refluxed for 8 hours, cooled, and then full constant evaporation freed from the solvents. The residue consisting of 2.9 g of a thick oily product became Purified on a silica gel column, using as eluant a 1: 1 mixture of benzene: ethyl acetate was used. Removal of the solvent gave so 1.1 g of a syrupy product which crystallized spontaneously and after recrystallization from a 1: 1 mixture

13 0014/1089

from ligroin: ethyl acetate 1 g
those mentioned in Table 1
ferte.
5 IR =>) (IT-CO-CH ₂ ) = 1680 cm
Example 2 the desired connection with
Properties (compound 6)
~ ¹ ; 5 (N-CO-O) = 1780 cm = ¹ . Table 1 R. H R " 3
It 11 Λ R ⁴ ( ^Ü C) (cm) Following the procedure of Example 1, the in
connections listed:
Table 1 ₁₀ (The elemental analysis of all compounds corresponded to
the assumed structure) H H H H. 1 CH ₂ Cl ■ 71-4 1690-1760 Verb.
Kr. H H H II I. ^CH 2 ^C 6 ^H 5 112-4 1.680-1760 15 1 H 6-CH ₃ II H 1 CH ₂ ^UC 3 ^H 7 oil L680-1770 2 2-CH ₃ 6-CH ₃ II H 1 CH ₂ Cl 88-92 L635-1770 3 2-CH ₃ 6-CII H H 1 ^CH 2 ^C 6 ^H 5 oil 1670-1770 1 20 ⁴ 2-CH H H H 1 CH ₂ OCH ₃ 103-6 1680-1780 5 H r.-cn Π II 1. ^CH 2 OCH ₃ 86-91 1690-1760 6th 2-Cn.
2-CH ₃ 6-CH ₃ Il
II H
H 1
1 CH ₂ 0-CO-CH,
OH oil
135-8 1690-1770
1690-1770 ⁽⁴⁾ 7th 2-CH ₃ 6-CH ₃ II II O - CO-OCH,
• 3 116-9 1680-1730-
-1790 8th
9 2-CH, 6-CII. H H 1 CH ₂ H 132-5 J670-1770 10
30th ₂ -c " ₃ H II 1 CII
2 OC H
6 5 109-12 1690-1780 11 ₃₅ (2) = melting points not corrected
(3) = only the bands corresponding to C = O are indicated
(4) = ϊ> OH = 3300 cm " ¹ 12th

1300U / 1089

Example 3 '"* -

Curative activity in Peronospora vines (Plasmopara viti-Gola (B. et C) Berl.et de Toni)

Vine leaves from Cv. Dolcetto grown in pots in a conditioned environment of 25 ° C and 60 ° / o relative humidity were sprayed on the underside of the leaf with an aqueous conidia suspension of Plasmopara viticola (200,000 conidifin / ml). After 24-hour stay in a stabilized at 21 ⁰ C, feuohtigkeitsgesättigten environment, the plants were fractionated by spraying both leaf faces with a 20- ^ aqueous-acetone solution of the test products (vol./vol.) Treated. After an incubation period of 7 days, the extent of infection was determined visually based on the following rating:

0 = no control, infection as with control plants,

that are infected but untreated

1 = 1 to 20% reduction in infection

2 = 20 to 60 percent reduction in infection

3 = 60 to 90% reduction in infection

4 = more than 90% reduction in infection. The following table 2 shows the values achieved.

Table 2

Curative activity against vine downy mildew by application to the foliage in a dose of

0.5 ^ o

link activity link activity 1 3 7th 4th 2 3 8th 4th 3 4th 9 4th 4th 4th 10 4th 5 4th 11 4th 6th 4th 12th 4th

example

Curative activity against downy mildew in tobacco (Peronospora tabacine Adam)

The leaves of tobacco plants grown in pots in a conditioned environment, Cv. Burley, were on the underside of the sheet with a conidia suspension of Peronospora taba-l

130014/1089

cine (200,000 conidia / ml). After 6-hour stay in a humidity saturated environment, the plants were transferred to a relative to 20 ⁰ C and 70 ⁰ Jo moisture stabilized environment for the purpose of incubation of the fungus. 24 hours after infection, the treatment was carried out by spraying both sides of the leaf with the. Test product in a 20% aqueous-acetylene solution (vol. Vol.). After an incubation period of 6 days, the extent of the infection was determined visually according to the. Evaluation of example 3 determined. Table 3 gives the test results.

Table 3

Curative activity in downy mildew infections in tobacco plants; Application to the foliage. in doses of 0.5 ^ ₀

15 connection

activity

4 4

6 4

Example 5

Determination of phytotoxicity

The leaves of vine plants grown in pots in a conditioned environment of 25 ° C and 60% relative humidity, Cv. Dolcetto, were made by spraying both sides of the leaf treated with a 20% aqueous-acetone solution (vol / vol) of the test products. After 7 days, the extent was the phytotoxicity symptoms visually according to a rating from 100 - = completely damaged plant to 0 = healthy Plant rated. The corresponding data are in Table 4 compared to the phototoxicity indices of two more recent commercial products on the market, namely

so "Furalaxyl" according to GB PS 1 448 810 and "Ridomil" according to the FR-PS 2 267 042 listed.

"Furalaxyl" is N- (2,6-dimethylphenyl) -N- (i'-carbomethoxyethyl) -2-furoylamide according to the following formula:

UCO-C-CH

C)

H C

1300U / 1089 ORIGINAL INSPECTED

"Ridomil" is N- (2,6-dimethylphenyl) -N- (i'-carbomethoxyethyl) -methoxyacetamide with the following formula:

H CO - C - CII

C - ClI OClI

Table 4
Phytotoxicity index at doses of 0.6

15 connection

Phytotoxicity index

"Furalaxyl"
"Ridomil"

10

100 60

In the abovementioned radicals: halogen stands for F, Cl, Br or I and

C ₁ -C ^ alkyl for methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buk; yl and tert-butyl.

In C ₁ -C ^ alkoxy, the alkyl radicals have the above meaning. In C ₁ -C ₅ alkyl, pentyl and isopentyl, for example, are added to the abovementioned radicals.

C ₂ -C ₅ alkenyl is, for example, vinyl, propenyl, allyl, the butenyl and pentenyl radicals and

C ₂ -C ₅ alkynyl is, for example, acetylenyl, propynyl ,. the butynyl and pentynyl radicals.

C ₃ -C ₆ cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

In COO alkyl, alkyl is preferably an alkyl radical having 1 to 8, in particular one having 1 to 6 carbon atoms (See definition above, including hexyl and isohexyl to be mentioned).

1300U / 1089

An alkyl group substituted with halogen atoms can e.g. contain 1, 2 or 3 halogen atoms.

5 A substituted phenyl group can, for example, be 1 or 2 of the contain specified substituents.

1300 rev / 10

Claims (1)

303 P a t e η t a η s ρ r ü ch e 1.- fungicide,
formula containing a compound of general , 3 f.:=Ö (D in which 1 2
R, R and. R, which are identical or different, represent H, halogen, C ₁ -C ^ alkyl or C ₁ -C ^ alkoxy '; B? represents H or CH ₃ , stands, ₃
A for -CH ₂ - or -CH- η has a "fourth of 0 or 1 and R for H, a C ₁ -C ₁ alkyl group optionally substituted by halogen atoms, a C ₃ -C ^ cycloalkyl group, a C ₂ -C ₅ alkenyl group, ethynyl, halogen (when η == 1), CN, SCN, a phenyl group optionally substituted with C ₁ -Cc- alkyl groups or halogen atoms, a heterocyclic group with 5 or 6 atoms which contains 1 to 3 heteroatoms (in particular furyl, tetrahydrofuran, thienyl, pyrimidyl, pyridyl, imidazolyl, pyrazolyl, triazolyl), ^ acetyl, COO-alkyl, -OR ⁵ -SR ⁵ , ■ R ⁶ stands / where R ⁵ and R, which are identical or different can be different, for H, C ₁ -C ₅ alkyl, C ₂ -C ₅ alkenyl, Cp-Cc alkynyl, phenyl, a heterocyclic group with 5 or 6 atoms which contains 1 to 3 heteroatoms, SO ₂ -alkyl or acetyl stand/
as well as usual carriers and auxiliaries. 130014/1089 ORIGINAL 2. Fungicide according to claim 1, characterized in that it is used against Plasmopara viticola in vines and against Peronospora tabacina in tobacco plants. 3. N-aryl-N-acyl-3-amino-oxazolidin-2 ~ ones of the general formula (i) according to claim 1, with the proviso that - if the radical (A) _n -R ^{4 is} CH ^ , - one of the residues RR ¹ , R ² and F? must be different from hydrogen. 4.- Compounds according to claim 3, characterized in that R = R ¹ = R ² = R ³ = H, η = 1, sovrie - (A) _n -R ⁴ * CH ₃ are. 5.- compounds according to claim 3, namely N-phenyl-N-chloroacetyl ^ -amino-oxazolidin ^ -one, N-phenyl-N-phenylacetyl-3-amino-oxazolidin ~ 2-one, N-phenyl-IT- (ß-methylpr opi onyl) ^ -aniino-oxazolidin - ^ - one, IT-Phenyl-1 ^ -methoxyacetyl-S-amJno-oxazolidin ^ -one. 6.- Compounds according to claim 3, characterized in that R = R ¹ = CH ,, R ² = R ³ = H. 7. Compounds according to claim 3 and 6, namely Ii- (2,6-dimethylphenyl) -li-chloroacetyl-3-amino-oxazolidin-2-one, H- (2,6-Dimethylphenyl) -N-phenylacetyl-3-amino-oxazolidin-2-one, N- (2,6-Diraethylphenyl) -W-methoxyacetyl-3-amino-oxazolidin-2-one, N- (2,6-Dimethylphenyl) -If-acet oxyacetyl-3-amino-oxazolidin-2-one, IT- (2,6-dimethylphenyl) -li-hydroxyacetyl-3-amino-oxazolidin-2-one, li- (2,6-dimethylphenyl) -N-carbomethoxycarbonyl- (or -N-meth- oxyoxalyl- ^ 3-amino-oxazolidin-2-one, W- (2,6-Dimethylphenyl) -lf-acetyl-3-amino-oxazolidin-2-one and N- (2,6-Dimethylphenyl) -N-pheiioxyacetyl-3-amino-oxazolidin-2-one. 1300U / 1089