SI8012040A8 - Process for preparing new 3-amino-2-oxo-oxazalidine derivates - Google Patents

Description

A process for the preparation of novel 3-amino-2-oxoxazolidine derivatives

Technical field of the invention

C 07D 263/13; C C7D 413/00

C 07D 407/00; A 01N 9/22.

The present invention relates to the field of organic synthesis, i.e. to a process for the preparation of novel 2-amino-2-oxo-oxazolidine derivatives useful for the suppression of phytopathogenic fungi.

A technical problem

There was a need to find a new, technologically advanced process for the preparation of novel 3-aroino-2-oxo-oxazolidine derivatives useful for the control of phytopathogenic fungi, in good yields and with satisfactory purity.

The state of the art

The compounds of formula (I) mentioned below are novel, and the process for their preparation has not yet been described.

Description of solution to a technical problem with implementation examples

Specifically, the present invention is refers to procedure for preparation of compounds with formula ^R \ < ^N 0 A 'VZ I rA ^{1 R} 4 * 6 where it is ^R 1 v 4 )

- 3 where are R? R and _Q, independently, C ^^ alkyl, halogen, or C ^^ alkoxy, and

Rg hydrogen, C ^ _{? |} alkyl or halogen, ®2 is CO-R _1O, wherein R q is C ^^ alkoxy-C ^^ alkyl, C ^ alkylcarbonylC ^^ alkyl, 2-f belongs, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2 -tetrahydrofuryl, 1-imidazolylmethyl, 1-pyrazolylmethyl, 2-tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl, or _?) halogenalkyl, and are

R ^, R ^, R ^ and Rg are independently hydrogen or C1-6 alkyl.

If any of R ^, R ^, R ^, Εθ, R ?, Rg or R ^ represents or includes an alkyl group (e.g. alkoxyl), this is preferably C1-6 alkyl, e.g. methyl, ethyl, n-propyl or i-propyl.

if any of R? or Rg is halogen, is F,

Cl, Br or I, preferably F, Cl or Br, more preferably Cl or Br, especially Cl.

v

If any of R ^ or R> jq is or includes halogen, it is F, Cl, Br or I, preferably F, Cl or Br, in particular Cl or Br.

Preferred halogenated 2-furyl means for R ^ q are monohalogenated 2-furyl, e.g. 5-chloro-2-furyl and 5-bromo-2furyl.

Preferred C 1-4 haloalkyl means for C 1-4 chloroalkyl, or C 1-6 bromoalkyl, e.g. chloromethyl, bromomethyl and C ^^ CHBr-.

Preferred halogenated 2-tetrahydrofuryl means for Ηηθ are monohalogenated 2-tetrahydrofuryl, in particular monochlorinated or monobrominated 2-tetrahydrofuryl, e.g. 5-chloro-2tetrahydrofuryl.

Preferred C ^ _ _{7 |} alkoxy-C ^ _{Z |} alkyl means C 1-4 alkoxymethyl, in particular CH 2 OCH 2 - and C 2 H 5 OCH 2 -.

Preferred C 1-6 alkylthio-C ^ _{? |} alkyl means for R>, q are C> alkylthiomethyl, e.g. CH ^ SCHg-.

βηθ is preferably C1-6alkoxy-C1-6alkyl, 2-furyl or 5-halo-2-furyl.

if one of R1 and R4 is alkyl, the other is preferably hydrogen.

if one of R ^ and Rg is C ^ _{7 |} alkyl, the second is preferably hydrogen.

Thus, the preferred group of compounds is that of formula Ia

wherein R £ --COCl ^ OCH ^ -C0CH ₂ 0C ₂ ^H 5 '^"co" (2-furyl) or -CO- (5-halo-2-furyl)

R? and R 8 is independently CH 2, Cl or Br and R 4 is H, Cl, Br or methyl, with bases, e.g. sodium hydroxide and optionally a catalytic amount of phase transfer catalyst. The organic phase may contain any water-immiscible inert solvent such as hydrocarbons or halogenated hydrocarbons, e.g. xylene, toluene, o-dichlorobenzene or dichloromethane. Suitable catalysts for phase transfer are quaternary ammonium compounds such as benzyltrimethylammonium bromide, quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride and crown ethers such as 18-crown-6 (18-crown-6 compound).

The compounds of formula I are novel. They can be obtained by acylating compounds of formula ^{0 R} c ^R c ^R -x "" / θ 3 \ / 4 ^R 1 - NH - NH - C - O -CC-Υ III where R ^, R ^, R ^, R ^, Εθ and Y the above meaning, with a compound of the formula

II

R ₁₀ - C - Z IV where it has the above meaning and is

By halogen, in particular chlorine, or Ο-ΟΟΕ ^ θ, where Ε ^ θ has the above meaning.

Suitable solvents for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chloro-6 benzene. The reaction is advantageously carried out at a temperature of about 5θ to about 120 ° C, e.g. 80 ° C.

A compound of formula III can be obtained by converting compounds of formula V

- NH - NH ₂ V Where R4 has the above meaning, with a compound of the formula? ^R 3 \ X ^R 4 VI

X - C - O-C-C-Y wherein R 2, R 4, R 4, R 8 and Y have the above meaning and X is halogen, in particular chlorine.

This conversion can be carried out at a temperature of about 0 to about 10 ° C in water or in an organic solvent which is inert under the reaction conditions, preferably in the presence of a base, e.g. organic amine, or sodium hydrogen carbonate.

The starting materials and reagents used in the methods described herein are either known or, if unknown, can be prepared in an analogous manner, as in the methods described or known procedures.

The compounds of formula I have useful fungicidal efficacy, especially against phytopathogenic fungi, in particular against fungi of the genus Oomycetes, indicating a significant effect in the following tests.

- 7 Test A: fungicidal effect against Pythophthora _- infestation

Young potato plants (in stages 3 to 5 leaves) in pots are sprayed with an aqueous spray suspension containing 0.003% (w / v) of a compound of formula I, e.g. 2-methoxy-N (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (formulated according to the preparation of Example I). Two hours later, the treated plants were inoculated with a suspension of Phytophthora infestans spores and then transferred to the tent, which produced 100% relative atmospheric humidity at an ambient temperature of 16 ° C and a duration of 16 hours. Disease control is assessed 4 to 5 days later by comparing treated plants with untreated, similarly inoculated plants.

In the above test compound, significant control of fungal infestation was found, without any sign of phytotoxicity on the host plants.

Test B: i £ 5Ei £ i © 5i_ £ Sinek_to_Plasmopara_yiticola

The young vines (in stages 3 to 6 leaves) in the pots are sprayed with an aqueous spray suspension containing 0.0008% (w / v) of a compound of formula I, e.g. 2-methoxy-N (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (formulated according to the preparation of Example I). Two hours later, inoculate the treated plants with a suspension of Plasmopara viticol spores and then transfer the plants to a tent in which 100% relative atmospheric humidity is generated at temperature

- 8 surroundings of 15 to 22 ° C (fluctuation over a 24-hour period) and a duration of 16 hours. Disease control was evaluated 6 days after inoculation by comparing treated plants with untreated, similarly inoculated plants. A significant control of the fungal infection is observed with the test compound without any sign of phytotoxicity on the host plants.

Test C: curative fungi cid effect against Plasmopara.wind cola

Young vine plants (in stages 3 to 6 leaves) are inoculated in pots in the same manner as determined in test B, except that the application of the compound, e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (formulated according to the preparation of Example I), only 3 days after inoculation; the incubation conditions are the same as those described in test B. The disease control is assessed as indicated in test B.

A known control of fungal infection is observed with the test compound.

Test D: eradikatiyen_fungiciden_effect_to_Plasmopara viticola

The process of evaluating this type of efficacy is as described in Test C, with the exception of processing only 6 days after inoculation, when sporulation of the lower leaf surface is already apparent. Disease control is evaluated 7 days after application e.g. 0.012% of compound 2-methoxy-N- (2,6-dimethylphenyl) - 9 -: ·

N- (2-oxo-3-oxesolidinyl) -acetamide (formulated in accordance with the preparation of Example I) exhibits an inhibitory effect on zones that already sporulate to such an extent that sporulation ceases completely.

Test E; translocation_of_processed_truck_trucks

The cut leaves of the vine are treated with an aqueous spray suspension containing 0.012% of a compound of formula I, e.g. 2methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (formulated according to the preparation of Example I), treating only the lower half of these leaves. Two hours after treatment, the entire leaf is inoculated with a suspension of Plasmopara viticol spores and then incubated in a tent that produces 100% atmospheric moisture under the conditions described in Test B. Although only the lower half of the leaves is treated as indicated above, with the test compound, significant control of the disease over the entire leaf inoculated, although only the top half of the leaves was treated. This test therefore shows that 2-methoxy-N- (2,6-dimethylphenyl) -N - (- oxo-3-oxazolidinyl) -acetamide (formulated according to the preparation of the example

I), acropetally as well as basipetally distributed in the leaf.

Test F; processing_ soil

This treatment takes place in vivo using Pythium aphanidermatum. The fungus is grown in a sterile mixture of sand and corn flour (97: 3 vol / vol) which is added with water in a ratio of about 1: 4

- 10 (vol / vol); cultivation lasts 4 days at 25 ° C. The fungus is then mixed into a semi-sterile mixture of peat and sand, in which it is then treated with a suspension containing the formulated effective ingredient to obtain a concentration of 10 to 160 ppm (e.g. 10, 40 and 160 ppm) calculated on the volume of the substrate. Transfer the substrate to 5 cm diameter pots in which the cucumber seeds are sown. The seedlings were incubated at 24 ° C and 60 to 70% relative humidity in the incubation chamber for 7 days, then determined by disease onset by comparing the number of healthy emerged plants and those in untreated, similarly inoculated control pots. The compound of Example I below, used in the above-mentioned wettable powder preparation, gives complete control of the disease.

Tests analogous to Test F give similar results with peas and beets.

For each of the compounds listed in the following examples, they were found to have fungicidal properties, indicating their usefulness as fungicides.

A particularly effective fungicidal activity was found in the above tests for compounds of formula Ia wherein R1 is COCHgOCl2, R3? and Rg is CH ^ and R ^ is H, where G is 0- (2-furyl), R? and Rg is CH2 and R4 is H, where R8 is C0- (5-bromo-2-furyl), R? and Rg, are CH ^ and R ^, is H, where RA, C0CH ₂ 0CH ^, R? and Rg is Cl and R ^ is H, where RA> COC ^ OCH ^, R? and R are CH ^ and R ^ is 3-Br and in particular in compounds of the formula Ia, where R, COC ^ OCH ^ £ R and R are CH, and R ₅ is H.

The invention therefore proposes a method for the control of phytopathogens from fungi, in particular of the order Oomjcetes, on plants, seeds or soil, 'comprising the process of treating plants, seeds or soil>

t r

with a fungicidally effective amount of a compound of formula I. ^?

Fungi of the order Oomycetes against which the procedure is in _; of the invention are particularly effective, those of the genus Phytophthora I on plants such as potatoes, tomatoes, tobacco, citrus fruits, j cocoa, gum, apple, strawberries, vegetables and ornamental plants, e.g. Phytophthora infestans on potatoes and tomatoes; I f

the genus Plasmopara viticola on the vine; the genus Peronospora on plants like tobacco, e.g. Tobacco peronospora tobacco; genus Pseudoperonospora on plants such as hops and cucumbers, e.g. Pseudoperonospora humuli on hops; the genus Bremia on plants, such as salads, e.g. Bremia lactucae on lettuce; the genus Pythium, which causes wilting and root rot in a large number of plants, such as vegetables, sugar beets, ornamental plants and conifers, e.g. Pythium aphanidermatum on sugar beet; the genus Sclerospora on plants such as sorghum and maize, e.g. Sclerospora | sorghis in sorghum. |

When using the process of the invention, the amount of preparation used will vary depending on factors such as the genus of suppressed fungi, the time and nature of application, and the amount and nature of the compound of formula I used in the preparation. 'F

However, generally satisfactory results are obtained when applied to a site, e.g. to crops or to the soil, j f

i

- 12 in a dosage range of 0.05 to 5 kg, preferably 0.1 to 3 kg, of the compound of formula I / hectare of treated site, with repeated application if used as seed treatment to obtain satisfactory application results and an amount of from about 0.05 to 0.5, preferably about 0.1 to 0.3 g, of the compound of formula I / per kg of seed.

According to a preferred method of the invention, compounds of formula I are used together with fungicides that are effective against phytopathogenic fungi, against which compounds of formula I are not or not sufficiently effective, this method allowing treatment of a wider range of phytopathogenic fungi than with the compounds of formula I above.

A particularly preferred embodiment of the invention is the application to the treated site of a fungicidally effective amount of component a) comprising a compound of formula I and component b) selected from component b1) of copper fungicide or component b2) captana or folpet or component b3) mancozeb or maneb.

Examples of copper fungicides suitable for use as component b1) are copper (II) carbonate, copper (II) calcium sulfate, copper (II) calcium oxychloride, tetra-cupric oxychloride, burgundy broth, burgundy broth, cuproxide, cupri -hydroxide, copper (II) oxychloride, or also copper complexes, such as copper triethanolamine hydroxide of the formula [Cu ΝζΟΙ ^ ΟΗ ^ ΟΗ) ^] - 13 (0H) ₂ , commercially available under the trademark K-Lox, or bis (ethylenediamine) - Cu (II) sulphate of the formula [CuCHgNCHgCHgNIL) ^} · SO ^, commercially available under the trademark Komeen, and mixtures thereof, in particular copper oxide, copper (II) oxychloride, cuprihydroxide or mixtures of copper (II) calcium sulphate and copper ( II) oxychloride.

Captan, folpet, mancozeb and maneb are common names for protective fungicides effective against leaf diseases (Pesticide Manual, 5 · ed., H. Martin and C.R. Vorthing, p.

76, 281, 328 and 329).

The method of the invention, where component a) and component b) are used, is effective against a wide range of phytopathogenic fungi.

Preferably, apply component a) in an amount of 100 to 400 g / ha and component b) in an amount of 200 to 2000 g / ha.

Preferably, the weight ratio of component a) to component b) is in the range 1: 1 to 1:10, more preferably 1: 2 to 1:10, in particular 1: 2 to 1: 7.

The process of the invention, where component a) and component b) are used, is particularly effective against phytopathogenic fungi in plants such as potatoes, tomatoes and other solanaceae, such as tobacco, citrus, cocoa, gum, apple, strawberry, vegetable and ornamental plants, e.g. . against fungi of the genus Plasmopara, e.g. Plasmopara viticola on vines of the genus Guignardia, e.g. Guignaridia bidwelli on a vine of the genus Phoma

- 14 on the vine, genus Pseudopeziza, e.g. Pseudopesis of tracheiphil on the vine, genus Gloeosporium, e.g. Gloeosporium ampelophagum on vines, genus Botrytia on vines and vegetables, e.g. Botrytis cinerea on the vine of the genus Phytophthora, Phytophthora infestana of potato, tomato or other Solanaceah, Phytophthora paraaitica on tomatoes and other Solanaceah, Phytophthora cryptogaea on tomatoes and other Solanaceah, Phytophthora mexicana on tomatoes and other Solanaceah, Phytophthora nicotianae on tomato and Phytophthora palmivora on gumijevcu or to cacao, but to the genus Peronospora, e.g. Tobacco peronospora tabacina, but of the genus Pseudoperonospora, e.g. Pseudoperonospora humuli on hops, of the genus Bremia on plants, such as salads, e.g. Bremia lactucae, of the genus Pythium, e.g. Pythium aphanidermatum on beet, genus Alternaria, e.g. Alternaria schooled on potatoes, tomatoes and other Solanaceae, Alternaria tenuis on tobacco, genus Spondylocladium, e.g. Spondylocladium atrovirens on potato genus Rhizoctonia, e.g. Rhizoctonia cultivated on potatoes, tomatoes and other Solanaceae of the genus Cladosporium, e.g. Cladosporium fulvum on tomatoes or other Solanaceae, of the genus Colletotrichum on plants, such as cocoa or tomato, e.g. Colletotrichum atramentarium on tomatoes or other Solanaceah, of the genus Glomerella, e.g. Glomerella lycopersici on tomato and other Solanaceah ^ Corticium spp on tomato and other Solanaceah, genus Botryodiplodia, e.g. Botryodiplodia theobromae on cacao. Such a procedure in

According to the invention, control of a much wider range of fungal diseases is possible than by treatment with a single component.

In general, a greater than additive effect of the components is observed, especially after treatment with the concentrations of component a) and component b), which allows practically complete, more precisely above 80% fungal control, especially when copper (II) oxychloride, cuproxide is used , captan, mancozeb or maneb as component b), especially when used against phytopathogenic fungi of the order Oomycetes, in particular against Oomycetes of the genus Phytophthora, e.g. Phytophthora infestans, of the genus Plasmopora, e.g. Plasmopora viticola, genus Peronospora, e.g. Peronospore tabaccina, of the genus Pseudoperonospora, e.g. Pseudoperonospora humuli, of the genus Bremia, e.g. Bremia lactucae and the genus Pythium, e.g. Pytbium aphanidermatum.

The process of the invention, using components a) and b), is particularly suitable for suppressing or inhibiting fungi on vines, tomatoes and other Solanaceae and cocoa beans when using component b1), on vines when using component b) and on vines, tomatoes, potatoes and other Solanaceae, tobacco and hops when using component b3).

Components a) and b) can be used in the form of a preparation and applied e.g. as a mixture of the tank or separately. Preferably, however, they are generally used in a mixed form of an aqueous spray or oil-based concentrate.

- 76 The useful fungicidal efficacy achieved after treatment with component a) and component b) is illustrated by the following tests.

Test G: fungicidal _- effect_ £ roti_ ^ jtoghthora_infestans_

The test is carried out as described in test A, the plants being treated with a mixture of a tank, namely an aqueous spray suspension containing component a) and component b) at the concentrations listed in Tables A ^ to Αθ below. We evaluate disease control 4 to 5 days later by comparing the results with the effect that would be achieved if only an additive effect occurred. A greater than additive effect is demonstrated, as shown by the following tables A ^ to Αθ.

Table Αη Table A £

Component a) of Example 1 below (in ppm) v S- / you • rl ra Λ4 o r- \ t β O Pl P pi Pi P> Λ) '-' 0 2 8 32 0 0 30 70 90 2 0 40 (30) 80 (80) 100 (100) 8 20 60 (45) 90 (90) 100 (90) 32 60 80 (70) 100 (90) 100 (95)

Component a) Examples 1 below (in ppm) 0 2 8 32 tJ • H ra 0 0 40 80 100 P e ti P · 2 0 50 (40) 100 (80) 100 (100) id 8 30 80 (60) 100 (85) 100 (100) H strain 32 | 75 90 (85) 100 (95) 100 (100)

() calculated additive effect (1) in commercially available Copper-Sendoz form (2) in commercially available Kocide 101 form

- 17 Table Α ^

Component a) at measure 1 below (in ppm e CU cu H ω cu »J o in. 0 2 8 32 0 0 30 80 100 2 20 50 (45) 100 (85) 100 (100) 8 40 80 (60) 100 (90) 100 (100) 32 70 90 (80) 100 (95) 100 (100)

Table A ^

Component a) of Example 1 below (in ppm) e cu CU z < H cu < o 0 0 0 2 8 32 40 80 100 2 30 70 (40) 90 (80) 100 (100) 8 20 90 (50) 100 (85) 100 (ICO) 32 80 100 (90) 100 (95) 100 (100)

() calculated additive effect.

Table A ^

Component a) of Example 1 below (in ppnC Mancozeb (in ppm) 0 2 8 32 0 0 20 80 95 2 20 80 (35) 100 (85) 100 (95) 8 32 40 90 (50) 100 (90) 100 (100) 75 95 (80) 100 (95) 100 (100)

Table Αθ

Component a) of Example 1 below (in ppm) Z CU cu n o c rt s 0 2 8 32 0 0 30 70 95 2 30 70 (50) 90 (80) 100 (100) 8 40 85 (60) 100 (80) 100 (100) ^{32 85} 100 (90) 100 (95) 100 (100)

() calculated additive effect

- 18 Test H: fungicidal effect of £ roti_Plasmo £ ara viticol

The test is performed as described in Test B, wherein the plants are treated with a mixture of a tank, namely an aqueous spray suspension containing component a) and component b) at the concentrations listed in Tables B to B_ below.

Ί o

The observed effect is given in the following Tables B 'to B _c .

and o

Table Β _ή 'Table B ₂

Component a) of Example 1 below (in ppm ' v • H (0 1 S 'OP » ¹ PP * P» m t> 0 2 8 32 0 0 30 ' 70 100 2 10 30 (35) 70 (75) 100 (100) 8 50 60 (65) 100 (85) 100 (100) 32 80 85 (85) 100 (95) 100 (100)

Component a) of Example 1 below (in ppm) 0 2 8 32 Ldroxide ppm) 0 0 40 70 100 2 20 40 (45) 70 (75) 100 (100) and ► h 8 40 60 (60) 100 : 80) 100 (100) dcu 32 70 80 (80) 100 (90) 100 (100)

() calculated additive effect (1) in commercially available Copper-Sandoz form (2) in commercially available Kocide 101 form.

- 19 Table

Component a) Example 1 below (in ppm) FOLPET (ppm) 0 2 8 32 0 0 40 80 100 2 40 60 (65) 100 (90) 100 (100) 8 70 80 (80) 100 (95) 100 (100) 32 LOO 100 (100) 100 (100) 100 (100)

Table B ₄

Component a) Primoral hereinafter (in ppm) 0 2 8 32 e cu cu 0 0 40 70 100 }> 2 0 40 (40) 80 (70) 100 (100) CΑΡΤΑΝ 8 70 95 (80) 100 (90) 100 (ICO) ³² 100 100 (100) 100 (100) 100 (100)

() Calculated additive effect.

Table B ^

? ..........- - The component a) of Example 1 below (in p ^ m Mancozeb (in ppm) 0 2 8 32 0 0 40 80 100 2 20 60 (50) 100 (85) 100 (100) 8 70 95 (80) 100 (95) 100 (100) 32 90 100 (95) 100 (100) 100 (100)

Table Βθ

Component a) of Example 1 below (in ppm) E cu Cu ► n o c (V 0 2 8 32 0 0 35 80 100 2 20 50 (50) 90 (85) 100 (100) 8 60 90 (75) 100 (90) 100 (ICO) ^{32 95} 100 (100) 100 (100) 100 (100)

() calculated additive effect

- 20 The compounds of formula I are advantageously used as fungicidal compositions together with agriculturally acceptable carriers or diluents. Such compositions also form part of the present invention In addition to the apoy of formula I, other effective agents, such as fungicides, in particular a fungicide selected from the group comprising component b) as defined above, are used as an effective agent. They can be used in either solid or liquid usable forms, e.g. in the form of a wettable powder, an emulsion concentrate, a water-dispersible suspension concentrate (flovable ”), a spreading powder, a granulate, a delayed-release form, comprising conventional carriers, diluents and / or additives. Such compositions may be produced in the usual manner.

The compositions of the invention comprising both component a) and b) can be obtained e.g. by mixing said components a) and b), optionally with a carrier and other formulating ingredients.

Distributed preparations can be applied in spray forms such as water-dispersible concentrates or wettable powders, which may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalenesulfonate, alkylarylsulfonate, ligninsulfonate, fatty alkylsulfate, ethoxylated alkylphenol and ethoxylated fatty alcohol.

Generally, the compositions include 0.01 to 90 wt. % of the effective agent, the latter being either.

- 21 from at least one compound of formula I or mixtures thereof with other effective agents, such as fungicides, e.g. component b) as defined above.

The concentrate forms of the composition generally contain between 2 and 80%, preferably between about 5 and 70% by weight. % effective asset. Liquid formulations for the preparation of the preparation may contain 0.01 to 20% by weight, preferably 0.01 to 5% by ^{weight of} 3% effective agent.

The invention is illustrated by the following examples, wherein the parts and percentages are by weight and the temperature in ° C.

- 22 Formulation Example II The wettable powder of parts of 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3oxazolidinyl) -acetamide is ground with two parts of lauryl sulfate, parts of sodium ligninsulfonate and 45 parts of finely divided kaolinite, until the average particle size is below 5 ^ tm. The resulting wettable powder is diluted with water before use to a concentration between 0.01 and 5% of the effective agent. The resulting spray liquid can be applied by leaf spraying or root irrigation.

Formulation Example 2: Granulate

94.5 wt. Spray parts of quartz sand in a mixer with 0.5 1 parts by weight of binder (non-ionic surfactant) and mix thoroughly. Then 5 wt. portions of the powdered 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide and stirring thoroughly to obtain

The granulate can be applied to the soil in addition to the treated plants.

- 23 Formulate Examples 3 to 6: (wettable powders)

Mas. % Example 3 4 5 6 (1) Component a) ^K ' 12,65 6.25 12.5 6.25 Copper (III) oxychloride • (^ 56% Cu) 47 47 Copper oxide 88% Cu) 29 29 Na-laurylsulfate 1 1 1 1 Ligninsulfonate 10 10 10 10 Kaolin 29.5 35.75 39.5 45.75

(1) e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3oxazolidinyl) -acetamide

All components of the preparation are mixed, milled and mixed again in the usual manner.

- 24 Formulate Examples 7 to 9 (wettable powders)

Mas. % Example 7 8 9 (1) Component a) ' ¹ 25 12.5 6 _} 25 f?) Component b2 ^v ' 50 50 50 Na-oleoylmethyltavride 2 2 2 Condensation product of Na-alkyl-naphthalenesulfonate and formaldehyde 5 5 5 Silica gel 5 5 5 Kaolin 13 25 _; 5 31 _? 75

and (1) e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3oxazolidinyl) -acetamide (2) e.g. folpet

All components of the preparation are mixed, milled and mixed again in the usual manner.

- 25 Formulate Examples 10 to 12 (wettable powders)

Mas. % Example 10 11 12 Component a) Component Na-laurylsulfate Ligninsulfonate Silica gel Kaolin 25 50 1 4 5 15 12 j 5 50 1 4 5 27 _? 5 6.25 50 1 4 5 33 ^ 75

(1) e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3oxazolidinyl) -acetamide (2) e.g. mancozeb

The preparation is obtained by mixing the components, then grinding the mixture and mixing again in the usual manner.

- 26 EXAMPLE 1

2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide '

11.8 g (0.0575 mol) of 2-chloroethyl-2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazinecarboxylate was added portionwise to a suspension of 2.0 g of sodium hydride (in the form of about 55 parts by weight in mineral oil) in 100 ml of absolute toluene at room temperature under nitrogen. The reaction temperature gradually increases during this addition to 40 °. After the addition is complete, the mixture is stirred for 30 minutes without cooling and then cooled to 10 °. The crude sodium hydride was then decomposed with ethanol, the resulting solution was washed with water, dried with magnesium sulfate and the solvent removed in vacuo to give the final title compound, which was recrystallized from ethanol to give the title compound as colorless crystals from the ground.

103 to 104 °.

EXAMPLE 1a

2-chloroethyl-2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazincarboxylate

The starting material used in Example 1 is obtained as follows:

A mixture of 14.7 g (0.06 mol) of 2-chloroethyl-2- (2,6-dimethylphenyl) -hydrazinecarboxylateine 16.2 g (0.1 mol) of methoxy-acetic acid anhydride [(CH ^ OCI ^ CO ^ O ] is mixed in 100 ml of dry

-27 toluene for 1 hour at 80 °. After cooling, the solution is washed with water, then with 5% aqueous sodium bicarbonate solution and then again with water.

The solution was dried with magnesium sulfate and the solvent removed in vacuo to give the title compound of the example

18.

EXAMPLE 1b

2-chloroethyl-2- (2,6-dimethylphenyl) -hydrazincarboxylate

Mixtures of 127 g (0.935 mol) of 2,6-dimethylphenylhydrazine,

102.5 g (1.5 moles) of pyridine and 400 ml of water are added at 0 to 5 ° 133.5 6 (0.935 moles) of chloroformic acid β-chloroethyl ester. After complete addition, the mixture was stirred for 2 hours at room temperature, the precipitate formed was filtered off, washed with water and dried. The title compound thus obtained is recrystallized from toluene to give colorless crystals from the ground. 74 to 75 ° ·

Following the preferred alternative method of Examples 1, 1a and 1b, we proceed as follows:

EXAMPLE 2

2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide

236.1 g (0.75 mol) of 2-chloroethyl-2- (methoxyacetyl) 2- (2,6-dimethylphenyl) -hydrazincarboxylate, 375 ml of xylene and 187 ml of water are stirred under external cooling while adding

- 28 82.5 ml (0.82 mol) of aqueous sodium hydroxide solution (containing about 0.4 g sodium hydroxide per ml) at such a rate as to maintain the internal temperature at about 20 °.

The mixture was stirred after adding 1 hour at 20 ° and 2 hours at 0 °. The solid was filtered off, washed with 150 ml of water and dried to give the title compound as a light colored solid from the ground. 102 to 103 °.

EXAMPLE 2a

2-chloroethyl-2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazincarboxylate

200 g (0.825 mol) of 2-chloroethyl-2- (2,6-dimethylphenyl) hydrazincarboxylate in 500 ml of xylene are heated to 80 ° and a warm (80 °) solution of 2-methoxy-acetyl chloride in 250 ml of xylene prepared in situ with treatment 73.5 g (0.826 mol)

2-methoxy-acetic acid in 250 ml of xylene with 107.1 g (0.9 mol) thionyl chloride at 80 ° for 2 hours. The mixture was heated to 80 ° C for 30 minutes and then treated as described in Example 1a.

EXAMPLE 2b

2-chloroethyl-2- (2,6-dimethylphenyl) -hydrazincarboxylate

A mixture of 17.7 g (0.1 mol) of 2,6-dimethylphenyl hydrazine hydrochloride, 21.2 g (0.2 mol) of sodium carbonate in 50 ml

- 29 water and 50 ml of xylene are stirred for 50 minutes at room temperature and then cooled to 5 °. Then 14.5 6 (0.1 mol) of 2-chloroethyl ester of chloroformic acid are added over a period of 1 hour while maintaining the temperature at 5 °. The mixture was stirred at 5 ° for an additional hour, after which time 100 ml of water was added, the precipitate formed was filtered off, washed with water and dried. Further processing is carried out as in Example 1b.

In the analogous manner as described in the preceding Examples 1 and 2, the following compounds of formula 1 are prepared:

trt · mer no. ^R 3 ^R 4 ^R 5 ^R 6 ^R 7 ^R 8 ^R 9 ^R 10 Tel. (° C) 3 H H H H ^CH 3 CH ₃ H ch ₂ oc ₂ h ₅ 62-4 4 H H H H ^CH 3 Cl H CH ₂ OCH ₃ 99-100 5 H H H H ^CH 3 CH ₃ H 190-1 6 H H H H CH ₃ ^CH 3 4-CI CH ₂ OCH ₃ 107-9 7 H ^CH 3 ^CH 3 H CH ₃ C » ₃ H CH ₂ OCH ₃ 8 H H H H CH ₃ ^C «3 H CK ₂ SCH ₃ 113-5 9 H H H H ^CH 3 CH ₃ H CH ₂ C1 134-6 10 H H H H ^CH 3 Cl H CH ₂ C1 135-6 11 H H H H ^CH 3 ^CK 3 H CH ₂ OCH (CH ₃ ) ₂ 12 H H H H ^CH 3 Cl H CH ₂ 0CH (CH ₃ ) ₂ 13 H H H H ^CH 3 Cl H -ώ 166-7 14 H H H H ^C «3 ^CH 3 H CH ₂ SC ₄ H _g (n) oil 15 H H H H ch ₃ Cl H CH ₂ SC ₄ H _g (n) oil 16 H H H H ch ₃ ^CH 3 H ch- ^c 2h ₅ Br 123-4 17 H H H H CH ₃ ^CH 3 H CH-CH- 1 ci 147-8 18 H H H H ^{: H} 3 CH ₃ H CH ₂ Br 143-4 19 H H H H : h ₃ CH ₃ H ΐ £ ϊ ^ΒΓ 119-20 20 H H H H Cl Cl H CH ₂ OCH ₃ 107-9 21 H H H S Cl Cl H ch ₂ ci 142-4 '

T® mei no. ^R 3 ^R 4 ^R 5 ^R 6 ^R 7 ^R 8 ^R 9 ^R 10 Tal. (° C) 22 H H H H Cl Cl H Ό 173-4 23 H H H H CH ₃ ^CH 3 H Ν '! ^CH 2 ^N J 139-41 24 H H H H ^CH 3 ^CK 3 ⁴ -ch ₃ CH ₂ OCH ₃ oil 25 H H H H CH ₃ ^C 2 ^H 5 H CH ₂ C1 oil 26 H H H H ^CH 3 ch ₃ 3-CI CH ₂ OCH ₃ 90-2 27 H H H H ch ₃ CH ₃ 3-Nr CH ₂ OCH ₃ 96-7 28 H H H H ^CH 3 ^CH 3 3-Nr CH ₂ C1 182-3 29 H H H H ^CH 3 CH ₃ 3-Nr o 145-8 30 H H H H ^CH 3 Nr 4-CH ₃ CH ₂ OCH ₃ 125-6 31 H H H H ^CH 3 Nr 4-CH ₃ CH.C1 r \ 124-6 32 H H H H ^CH 3 Nr 4-CH ₃ £ j) 193-4 33 H H H H ^CH 3 ch ₃ H CHOCH- 1 ^CH 3 90-4 34 H H H H ^C »3 ^CH 3 H 12) 149-52 35 H H H H ^CH 3 ^CH 3 4-CI CH ₂ C1 tire 36 H H H H ^CH 3 CH ₃ 4-CI Ώ 164-5 37 H H H H ^C 2 ^H 5 ^C 2 ^H 5 H CH ₂ OCH ₃ 109-12 38 H H H H ^CH 3 ^CH 3 H CH ₂ OC ₃ H _? (n) oil

Si- mei $ t. * 3 ^R 4 ^R 5 ^R 6 ^R 7 ^R 8 ^R 9 ^R 10 Tal. (° C) 39 H H H H CH ₃ ^CH 3 H CH ₂ OC ₄ H _g (n) 40 H H H H ^CH 3 ch ₃ H CH-OCH-CH 1 ZJ ^CH 3 41 H H H H ^CH 3 ^CH 3 H CH £ CH ₂ CH = CH ₂ 98-100 42 H H H H CH ₃ ^CH 3 H CH ₂ OCH ₂ C £ CH 91-93 43 H H H H ^CH 3 ^CH 3 H CH ₂ 0> ^ 107-8 44 H H ^C »3 H ^CH 3 ^CK 3 H CH ₂ OCH ₃ 79-80 45 H H H H ^CH 3 ^CH 3 H ^CH 2 <3 56 46 H H H H ^C 2 ^H 5 ^C 2 ^H 5 H ΰ 142-4 47 H H H H C ₂ ^h 5 ^C 2 ^H 5 H CH ₂ C1 88-9 48 H H H H Nr Nr H CH ₂ OCH ₃ 150-2 49 H H H H 31 Cl 4-C1 CH ₂ OCH ₃ 128-9 50 H H H H 2 ₂ H ₅ ^C 2 ^H 5 4-C1 CH ₂ OCH ₃ 114-6 51 H H H- H 3r Cl 4-CH ₃ CH ₂ OCH ₃ 131-4 52 H H H H ^{: H} 3 ^C 2 ^H 5 H CH ₂ OCH ₃ 96-8 53 H H H H CH ₃ ^CH 3 4-Nr CH ₂ OCH ₃ 137-8

An indication of the best known applicant for the economic exploitation of the invention

2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-5-oxazolidinyl) acetamide '

11.8 g (0.0575 mol) of 2-chloroethyl-2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrezinecarboxylate were added portionwise to a suspension of 2.0 g of sodium hydride (in the form of about 55 parts by weight in mineral oil) in 100 ml of absolute toluene at room temperature under nitrogen. The reaction temperature gradually increases during this addition to 40 °. After the addition is complete, the mixture is stirred for 50 minutes without cooling and then cooled to 10 °. The crude sodium hydride was then decomposed with ethanol, the resulting solution was washed with water, dried with magnesium sulfate and the solvent removed in vacuo to give the final title compound, which was recrystallized from ethanol to give the title compound as colorless crystals from the ground.

105 to 104 °.

For

SANDOZ A.G. :

Claims (3)

PATENT APPLICATIONS 1. A process for the preparation of new 3-amino- 2 oxo-oxazolidine of formula I where they are meant R? methyl, Rg methyl, ethyl, chlorine, Rg hydrogen, chlorine in position 4, R ₁₀ -CH ₂ OCH ₃ , -CH ₂ OC ₂ H ₅ , -CH ' ₂ SCH ₃ , -CH ₂ C1, Rg hydrogen, R8 is hydrogen or methyl, wherein the compound of formula II II in which they have Rg, Rg, Ry, Rg, Rg and R _{1Q have} the above meaning and Y stands for halogen, intramolecularly cyclized at 0 ° to 50 ° C in anhydrous organic medium and in the presence of an acid binding agent. (Priority 16 August 1979). - 35 2. The process according to claim 1, characterized in that toluene or xylene is used as the organic medium. Process according to claim 1, characterized in that sodium hydride is used as the acid-binding agent. (The importance of R ^ = 3-chlorine or 3-bromine is therefore given priority on 13 August 1980). For SANDOZ AG .: 17198-VIII-86-MS SUMMARY We propose a process for the preparation of novel 3-amino-2-oxo-oxazolidine I derivatives by intramolecular cyclization of compound II having R ^, R ^, R? to R ^ g the meaning given in claim 1.