CA1303046C - N-amino-2-oxo-3-oxazolidine derivatives - Google Patents

Abstract

Case 130-3882 Abstract of the Disclosure The lnvention provides novel N-amino-2-oxo-3-oxazo-lidine derivatives of formula I
I

whereln R1 is

Description

13~3~6 case 130-~82 The present invention provides compounds useful in the combatlng oE phytopathogenic fungi.
More specif~cally the present invention provides compounds of formula I, N N ~

R3 \ ~5 R

S wherein Rl ls wherein R7 und R8, independently, are Cl 4alkyl, halogen or Cl 4alkoxy, and R~ is hydrogen, Cl 4alkyl or halogen, R2 is CO-~t 10wherein Rlo is Cl 4alkoxy-Cl_4alkyl, Cl_4alkyl-thio-Cl ~alkyl, 2-uryl, 2-tetrahydro-furyl, halogenated 2-furyl, halo-genated 2-tetrahydrofuryl, l-lmlda zolyl~ethyl, l-pyrrazolyl~ethyl, .52-tetrahydrofuryloxymethyl, 2-tetra-hydropyranyloxymethyl, or Cl_4halogen-alkyl, and lt3, ~4, R5 and R6 are lndependently hydrogen or Cl ~alkyl.

.' ,1_ ., , ~

13~3C~6 - 2 - 130-3~82 When any of R3, R4, R5~ R6~ R7~ R8 9 includes an alkvl group (e.g. alkoxy), this is preferably Cl 3alkyl, i.e. methyl, ethyl, n-propyl or i-propyl.

When either of R7 or R8 is halogen, this is F, Cl, Br or I, preferably F, Cl or Br, more preferably Cl or Br, particularly Cl.
~ en any of Rg or Rlo is or includes halogen this is F, Cl, Br or I, preferably ~, Cl or Br, particularly Cl or Br.
Preferred halogenated 2-furyl significances of Rlo are monohalogenated 2-furyl, e.g. 5-chloro-2-furyl and 5-bromo-2-furyl.
Preferred Cl 4halogenalkyl significances of Rlo are Cl 4chloroalkyl, or Cl 4bromoalkyl, e.g. chlororethyl, 15 bromomethyl and C2H5CHBr-.
Preferred halogenated 2-tetrahydrofuryl significances of RlG are monohalogenated 2-tetrahydrofuryl, particularly monochlorinated or ~.onobrominated 2-tetrahydrofuryl e.g.
5-chloro-2-tetrahydrofuryl.
Preferred Cl 4alkoxy-C1 4alkyl significances of Rlo are Cl 3alkoxymethyl, particularly CH30CH2- and C2H50CH2-.
Preferred Cl 4alkylthio-C1 4alkyl si~nificances of Rlo are Cl 3alkylthiomethyl, e.g. CH3SCH2-.
Rlo is preferabably Cl_4alkoxy-Cl_4alkyl, 2-furyl ; 25 or 5-halo-2-furyl.
~ When one of R3 and R4 is Cl 4alkyl, the other is 13~3Q~6 - 3 - 130-38~2 preferably hydrogen.
When one of R5 and R6 is Cl 4alkyl, the other is preferably hydrogen.
Thus, a preferred group of compounds are the compounds of formula Ia, ~ 7. ~
Rg~ R2' ~ Ia wherein R2' is -COCH20CH3, -COCH20C2H5, -C0-(2-furvl) or -C0-(5-halo-2-furyl), R7/ and R8' indeper.dently are CH3, Cl or Br and Rg' is H, Cl, Br or methyl whereby R7' and R8' are preferably identical.
According to a further aspect of the present inven-tion, the compounds of formllla I are produced by intra-molecular condensation of a compound of formula II

H " R5~ ~R6 R~R4 R - N
C - R

1' 3~ R4, R5, R6 and Rlo are as defined above and Y is halogen.
Y is preferably chlorine or bromine, particularly chlorine.
The above intramolecular condensation can be carried " 13~?3Q~6 out in a conventional manner. The reaction is exothermic.
It can e.g. be carried out in a water free medium using as solvent an ether such as dimethoxyethane, an hydro-carbon such as toluene or an other solvent which is inert under the reaction conditions. The reaction temperature is not critical and can lie between about 0~ and 100C.
Since the reaction is exothermic one starts the reaction conveniently at room temperature and allows the reaction temperature to rise gradually.
The reaction is conveniently carried out in the presence of an acid binding agent such as sodium hydride, sodium amide or a sodium alcoholate e.g.
sodium ethylate.
The intramolecular condensation can also be carried 15 out in an aqueous/organic two-phase system in the presence of an anorganic base e.g. sodium hydroxide and optionally a catalytic amount of a phase transfer catalyst.
The organic phase may comprise any appropriate inert water immiscible solvent such as hydrocarbons or halogenated 20 carbons, e.g. xylene, toluene, o-dichloro benzene or di-chloromethane. Appropriate phase transfer catalysts are quaternary ammonium compounds such as benzyltrimethyl ammonium bromide, quaternary phosphonium compounds such as benzyltriphenyl phosphonium chloride and crown ethers 25 such as 18-crown-6.
The compounds of formu~a II are novel. They may be 13~3(~6 obtained by acylation of compounds of formula III
O R5~ /R6 R3~ ~ 4 Rl - NH - NH - C - O C C - Y III
wherein Rl, R3~ R4~ R5, R6 and Y are as deined above, with a compound of formula IV, R - C - Z IV
wherein Rlo is as defined above, and Z is halogen, particularly Cl,or 0-CORlor wherein Rlo is as defined above.
Suitable solvents for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbcns such as chlorobenzene. The reaction is conveniently 10 effected at a temperature of from about 50 to about 120C, e.g. 80C.
The compounds of formula III may be obtained by conversion of compounds of formula V, Rl - NH - NH2 V
wherein Rl is as defined above, with a compound of formula VI

.

o R5~ /R6 R3~ ~ R4 X - C - O - C C Y VI
wherein R3, R4, R5, R6 and Y are as defined above, and X is halogen, particularly C1.
This conve~sion may be effected at a tem~erature of from about 0 to about 10C in water or in an organic 13~`3Q~6 solvent which is inert under the reaction conditions, conveniently in the presence of a base e.g. an organic amine or sodium hydrogen carbonate.
The starting materials and reagents employed in the processes described above are either known or, insofar as they are not known, they may be pxoduced in analogous manner to the processes described herein or to kno~7n processes.
The compounds of formula I have useful fungicidal activity, particularly against phytopathogenic fungi, especially against fungi of the class Oomycetes as indicated by a significant effect in the following tests.
Test A : Fun~icidal effect aaainst PhytophLhora infestans __ _ _ __ _ _ _ Young potted potato plants (3-5 leaf stage) are sprayed with an aqueous spray suspension containing 0.003% (weight/volume) of a compound of lormula I, e.g.
2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation 2~ Example I). ~to hours later, the treated plants are inoculated with a spore suspension of Phytophthora infestans and the plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperature of 16C and a day length of 16 hours.
Disease control is evaluated 4-5 days later by comparing the treated plants with untreated, similarly inoculated ` 13~?3C~

~ 7 - 130-3882 plants. With the above test compound, substantial control of the fungal infestation is observed without any sign of phytotoxivity on the host plants.

Test B : Fun~icidal effect a~ainst Plasmo~ara S viticola _ _ _ _ _ _ _ _ Young potted plants of grape vine (3-6 leaf stage) are sprayed with an aqueous spray suspension containing 0.0008% (weight/volume) of a compound of ormula I, e.g.
2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example I). Two hours later, the treated plants are inoculated with a spore suspension of Plasmopara ~iticola and the plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient tempera-ture of 15 - 22C (fluctuating over a 24hr-period) and a day length of 16 hours. Disease control is evaluated 6 days after inoculation by comparing the treated plants with untreated, similarly inoculated plants. With the . test compound, substantial control of the fungal infection is observed without any sign of phytotoxicity on the host plants.
Test C : Curative fun~icidal effect a~ainst __ _________ _______________ _____ Plasmo~ara viticola ______ ____________ Young potted plants of grape vine (3-6 leaf stage) are inoculated in the same way as determined in Test B, but the application of the compound, e.g. 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide ~3~3~

~formulated in accGrdance with Formulation Example I), follows only after 3 days after inoculation; the incubation conditions are the same as described in Test B.
Disease control is evaluated as stated in Test B. With the test compound, substantial control of the fungal infection is observed.
Test D : Eradicative fun~icidal eflect a~ainst PlasmoPara viticola The procedure to evaluate this kind of activity is lO evaluated as described in Test C, with the exception that the treatment is carried out only 6 days af.er inoculation, when sporulation on the lower leaf surface is already evident. Disease control evaluated 7 days after application of,e.g.,0.012~ of the compound 2-methoxy-lS N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example I), reveals a stopping effect on already sporulating zones, ln that sporulation ceases completely.
Test E : Translocation in treated leaves of qra~e_v_nes Fxcised leaves of grape vine are treated with an aqueous spray suspension containing 0.012~ of a compound of formula I, e.g. 2-methoxy-N-(2~6-dimethylphenyl)-~1-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with 25 Formulation Example I),in that only the lower half of such leaves is treated. ~Yo hours after treatment, the whole ~3{~3(~6 leaf is inoculated with a spore suspension of Pl-asmo?ara Viticola after which the leaves are incubated in a tent providing 100~ atmospheric humidity at conditions as described in Test B. Although only the lower half of the leaves was treated as stated above, with the test compound substantial disease control on the entire leaf inoculated was observed. The same effect was also observed, when only the upper half of the leaves was treated. This Test thus shows, that the 2-me~hoxy-N-(2~6-dimethylphenyl)-N-(-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example I), is distributed within a leaf both acropetally and basipetally.
Test F : Soil Treatment In vivo, employing Pythium aphanidermatum. The funyus is cultivated in a sterile mixture of sand and corn meal (97:3 v/v) to which water is added in a ratio OL about 1:4 (v/v); cultivation lasts for 4 days at 25C. The fungus is then mixed into a semi-sterile mixture of peat and sand which then is treated with a suspension containing the formulated active ingredient to give concentration of 10 to 160 ppm (e.g. 10, 40 and 160 ppm) calculzted per volume substrate). The substrate is transferred to pots of 5 cm di2meter which are seeded with cucumber seeds. The planted pots are incubated at 24C and 60 - 70~ relative humidity in an incubation chamber for 7 days, after which disease attack is determined by comparing the number of healthy 13~J 31~
- 10 - 130-3~82 emerged plants with that in untreated, similarly inoculated check pots. The compound of Example 1, hereinafter, used in the wettable powder formulation given above provides full disease control.
Tests analogous to Test F give similar results with peas and sugar beets.

Each of the compounds listed below in the following Examples is found to possess fungicidal properties indicating their usefulness as fungicides.
lG Particularly effective fungicidal activity is found in the above tests with the co~pounds of for~ula Ia wherein R ' is COCH20C2H5, R7 and R8 3 9 wherein R2' is C0-(2-furyl), R7' and R8' are CH3 and Rg' is H, 5 wherein R2' is C0-(5-bromo-2-furyl), R7' and R8' are CH3 and Rg' is H, wherein R2' is COCH20CH3, R7' and R8' are Cl and Rg' is H, wherein R2' is COCH20CH3, R7' and R8' are CH3 and Rg' is 3-Br 0 and especially ~lith the compound of for~ula Ia, - wherein R2' is COCH20CH3, R7' and R8' are CH3 and Rg' is H.

i3~3~
~ 11 ~ 130-3882 The invention therefore also provides a method of combating phytopathogenic fungi, especially of the class Oomycetes, in plants, seeds or soil, which process comprises treating the plants, seeds or soil with a fungicidally effective amount of a compound of formula I.
Fungi of the class Oomycetes, against which the method of the invention is particularly effective, are those of the genus Phytophthora in plants such as potatoes, tomatoes, tobacco, citrus, cacao, rubber, apples, strawberries, vegetables and ornamentals, e.g.
Phytophthora infestans in potatoes and tomatoes; of the genus PlasmoPara viticola in grape vines; of the genus Peronos~ora in plants such as tobacco, e.g. Peronospora tabacina in tobacco; of the genus Pseudoperonos~ora in plants such as hops and cucumber, e.g. PseudoperonosDora humuli in hops; of the genus Bremia in plants such as lettuce, e.g. Bremia lactucae in lettuce; of the genus Pythium causing damping-off and root rots in a great number of plants, such as vegetables, sugar beets, ornamentals and conifers, e.g. Pythium aphanidermatum in sugar beets; of the genus Sclerospora in plants such as sorghum and corn, e.g. Sclerospora sorqhis in sorghum.
For use in the method of the invention, the amount of the preparation to be employed will vary depending on such factors as the species of fungi to be combated, `- ~3t~30~;
~ 12 ~ 130-3882 the time and nature of application and the amount and nature of the compound of formula I employed in the preparation.
However, in general, satisfactory results are obtained when applied to a locus, e.g. on crops or to soil with a dosage rate in the range of from 0.05 to 5 kg, preferably from 0.1 to 3 kg of a compound of formula I/ha treated locus, the application being repeated as required. When employed as a seed dressing, satisfactory results are obtained when applied at a rate of from about 0.05 to 0.5, preferably about 0.1 to 0.3 g compound of formula I/kg seed.

According tG a preferred method of the invention , the compounds of formula I are used in association ~ith other fungicides which are effective against phytopathogenic fungi, such combinations having an enhanced or broadened fungicldal activity.

A particularly preferred ~.ethod of the invention comprises applying to the locus to be treated fungici-~ally effective amounts ofa component a) comprising a compound of formula I and of a component b) selected from a compcnent bl) a copper fungicide or a component b2) captan or olpet or 13~3CI~

~ 13 ~ 130-3882 a component b3) mancozeb or maneb.
Examples of copper fungicides suitable for use as component bl) are copper (II) carbonate, copper (II) calcium sulphate, copper (II) calcium oxychloride, tetracupric oxychloride, ~ordeaux mixture, Burgundy mixture, cuprous oxide, cupric hydroxide, copper (II) oxychloride or also copper complexes sucn as copper tri-ethanolamine hydroxide of the formula [Cu N(CH2CH20H)3 ]-(OH)2, commercially available under the Trademark K-Lox, or bis(ethylenediamine)-copper (II) sulphate of the formula [Cu(H2NCH2CH2NH2)2]S04, commercially available under the Trademark Komeen, and mlxtures thereof, parti-cularly cuprous oxide, copper (II) oxychloride, cupric hydroxide and a mixture of copper (II) calciur.~ sulphate and copper (II) oYychloride.
Captan, Folpet, Mancozeb and Maneb are the common names for protective fungicides effective against foliage diseases (Pesticide Manual, 5th Ed., by H. Martin and C.R. Worthing, page 76, 281, 328 and 329 resp.).
The method of this invention wherein component a) and component b) are used, is effective against a wide range of ~hytopathogenic fungi.
Preferably component a) is applied at a rate of 100-400 g/ha and component b) at a rate of 200-2000 g/ha.
Preferably the weight ratio of component a) :
component b) is in the range of 1:1 to 1:]0, more 13~?30~6 preferably of 1:2 to 1:10, particularly of 1:2 to 1:7.
The method of the invention wherein co~ponent a) and component b) are used is particularly effective against phytopathogenic fungi in plants such as potato, tomato, and other Solanaceae tobacco, citrus, cacao, rubber, apple, strawberry, vegetables and ornamentals, e.g.
against fungi of the genus Plasmopara, e.g. PlasmoPara viticola in grape vine, of the genus Gui~nardia, e.g.
Gu~naridia bidwelli in grape vine of the genus Phoma 10 in grape vine, of the genus Pseudopeziza, e.g. Pseudo-peziza tracheiphila in grape vine, of the genus Gloeosporium, e.g. Gloeosporium ampelo~hagum in grape vine of the genus Botrytis in grape vine and lettuce, e.g.
Botrytis cinerea in gra,pe vine, of the genus PhytoPhthora, 15 Phytophthora infestans in potato, tomato or other Solanaceae, PhYtophthora ~arasitica in tomato or other Solanaceae, Phyto~hthora cryptogaea in tomato and other Solanaceae, PhYtophthora mexicana in tomato and other -Solanaceae~Phyt~E~ nicotianae in tobacco and Phytoph-20 thora palmivora in rubber or cacao, of the genus Perono-spora, e.g. PeronosPora tabacina in tobacco, of the genus Pseudoperonospora~ e.g. PseudoperonosPora humuli in hop, of the genus Bremia in plants such as lettuce, e.g. Bremia lactucae, of the genus Pythium, e.g. Pythium aphanidermatum 25 in sugar beet, of the genus Alternaria, e.g. Alternaria -solani in potato, tomato and other Solanaceae, Alternaria ~3~3(~

tenuis in tobacco, of the genus Spondy~ocladium, e.g.
Spondvlocladium atrovirens in potato, of the genus Rhizoctonia, e.g. Rhizoctonia solani in potato, tomato and other Solanaceae, of the genus Cladosporium, e.g.
Cladosporium fulvum in tomato or other Solanaceae, of the genus Colletotrichum in plants such as cacao or tomato, e.g. Colletotrlchum atramentarium in tomato or other Solanaceae,of the genus Glome-rella, e.g.
Glomerella lYcopersici in tomato and other Solanaceae, 10 of Corticium spp in tomato and other Solan_ eae, of the genus Botryodiplodia, e.g. Botryodiplodia theobromae in cacao. This method of the invention allo~Js the control of a si~nificantly wider range of fungal diseases -than by treatment with only one of the components.

In general, a greater than additive effect of the components is observed, especially after treatment with concentrations of component a) and component b) allowing a practically complete, more specifically more than 80%, control of the fungi, particularly when copoer 20 ~II) oxychloride, cuprous oxide, captan, mancozeb or maneb is used as component b), and especially when used against phytopathogenic fungi of the class Oomycetes, -``` 13~3~6 -16_ 130-3882 especiaily against Oomycetes of the genus Phytophthora, e.g. PhYtophthora infestans, of the genus Plasmopora, e.g. Plasmo~ora viticola, of the genus Peronospora, e.~. Peronospora tabaccina, of the genus Pseudoperono-spora, e.g. Pseudoperonospora humuli, of the genus Bremia, e.g. Bremia lactucae, and of the genus Pythium, -e.g. P~thium aphanidermatum.
The method of the invention wherein the components a) and b) are used, is especially indicated for co~batinq or preventing fungi in grape vines, tomato and other Solanaceae and in cacao when a component bl) is used, in grape vines when a component b2) is used and in grape vines, potato, tomato and other Solanaceae, tobacco and hop when a component b3) is used.
The components a) and b) may be employed in formulation form and applied e.g. as a tank mix or separately. They are, however, preferably applied in admixture in the form of an aqueous spray or oil based concentrate.
The useful fungicidal activity obtained after treatment with a component a) and a component b) is illustrated by the following tests.
Test G : Fun~icidal effect a~ainst Phyto~hthora ___ ___________ ___ _____ infestans The test is carried out as described in Test A, whereby the plants are treated with a tank mix of an ~3~3~ 6 ~ 17 - 130-3882 aqueous spray suspension containing component a) and component b) in concentrations indicated in Tables Al to A6 below. The disease control is evaluated 4-5 days later by comparing the results with the effect that would be obtained if only an additive effect would arise. A
more than additive effect is indicated,as illustrated in the following Tables Al to A6.

Table Al Table A2 Component a) of Component a) of ~~~
Example 1 hereinafter Example 1 hereinafter . (in PP: n) _ _ (ir _~m) ~- 0 2 8 32 ~ 0 1 2 1 8 32 0 . 0- 30 - 70 90 X 0 0- -40- ~0 100 . 0 40 80 100 ~ ~ 050 100 100 o 2 . __ (30) (80) (loo) ~ Q 2 (40) (80) (100) ~ ~, 8 20 60 90 100 ~ ~ 3080 1100 100 o ~ _ . _ (45) (90) (90) ~o - 8 (60) (85) (100) .~ 32 60 80 100 100 Q,_ 32 l75 gO 100 100 ~ ~ (70) (90) (95) ~ _ _(85) (95) (100) ( ) calculated additive effect (1) in commercially available Copper-Sandoz form (2) in commercially available Kocide 101 form :., . .~ ' '`

~3~3C~

Table A3 Ta~le A
Component a) of Component a) of Example l hereinafter Exa~ple l hereir.after (i I P~ ~) ' _ _~i ~ ~m) 0- _ _2_ 88 l32 ~ _ 0 _ -80 - l30 20 50 lO0 lO0 ~ 3070 90 lO0 2(45) (85) (lO0) _ 2 (40) (80) (1003 _ 40 80-- lO0---- lO0 ~ 8 20 90 100 lO~
~ 8 _ (60) (90) (lO0) G ( 50) (85) (lC0) o 70 90 loo lO0 g 32 80lO0 103 lO0 ~ 32 _ (80) (95) (lO0) _ _ _ (90) (95) (lO0) ( ) calculated additive effect.

Table A5 Table A6 Component a)~~of Component a) of Ex~ample l hereinafter Example l hereinafter _ (i l P ~m) (i l ppm) 0 G 20 80 95 ~ 0 030 70 95 ~ 2 1 20 80 lO0 lO0 ~ 3070 90 lO0 Q l (35) (85) (95) ~ 2 (50) (80) (lO0) N - 40 90 lO0 lO0 _ 4085 100 lO0 g 8 _ (50) (90) (100) R 8 _ (60) (80) (lO0) 32 75 95 lO0 lO0 ~ 85 lO0 lO0 lO0 ~ __ __ 80) (95) (lO0) _ 32 (90) (95) (lO0) ( ) calculated additive effect.

:13~?3046 Test H : Fungicidal effect aqainst Plasmo~ara viticola _ _ _ _ _ _ _ _ The Test is carried out as described in Test B, whereby the plants are treated with a tank mix of an aqueous spray suspension containin~ component a) and component b) in concentrationsindicated in Tables Bl to B6 below. The observed effect is given by the following Tables Bl to B6.
Table Bl Table B2 Component a) of Com_onent a) of Example 1 hereinafte l Example 1 hereinafter (i ~ Pi ,m) (i ~ p~ 'm) _ 0 2 8 32 0 2 8 32 0 1O 30 70 100 ~c _ 0- 40 70 lOo 'x _ llO 30 70 100 ~ ~ ~0 40 70 100 o 2 (35) (75) (100) ~ ~ 2 _ (45) (75) (100) , 50 60 100 1001 ~ ~ 8 40 60 100 100 o 8 65) (85) (100) ~ _ (60) 80) (100) ~.~ 80 85 100 100 ~ _ 70 80 100 100 v- 32(85) (95) (100) ~ ~ 32 l (80) (90) (100) ( ) calculated additive effect (1) in commercially available Copper-Sandoz form (2) in commercially available Kocide 101 form , .

~ . -, ~3~3~4~i Table B3 Table B4 Component a) of Co~ponent a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in p~m) _ _ _ 2 8 32 ~ _ 2 8 32 0 ~ 40 80 100 ~ 0 0 40 70 100 2 l40 60 100 100 t ~ 2 0 40 80 100 - L (~5) (90) (100) ~ _ (40) (70) (100) 8 70 80 100 100 z 8 7095 100 100 _ (80) (95) (100) ~ (80) (90) (100) 00 100 100 100 ~ 32 100 100 100 100 ~ 32 (100) (100) (100) ~ (100) (100) (10~) ( ) calculated additive effect.

Table B5 Table B6 Co~.~onent a) of Com~poner.t a) of Example 1 hereinafter Exa~ple 1 hereinafter (in l~e n) (i n pPm) 0 0- 40 80 100 ~ 0 1 0- 35 ~ 80 100 ~2 20 60 100-- 100- ~ _ 2050 90 100 Q _ (50) (85) (100) ~ 2(50) (85) (i00) N 8 1 70 95 100 100 _ 8 6090 100 100 o(80) (95) (100~ ~ (75) (90) (100) 90 100 100 100 ~ 32 95100 100 100 __ __ (95) (100) (100' ~ _ (100) (100) (100) (- ) Calculated additive effect.

The compounds of formula I are conveniently employed as fungicidal compositions in association with agricul-turally acceptable caxriers or diluents. Such composi-tions also form part of the present invention. They may contain aside from a compound of formula I as active agent, other active agents, such as fungicides, parti-~ .

:13~3~f~6 cularly a fungicide selected from the group comprised by component b) as defined hereinbefore. They may be employed in either solid or liquid application forms e.g.
in the form of a wettable powder, an emulsion concentrate, a water dispersible suspension concentrate ("flowable"), a dusting powder, a granulate, a delayed release form, incorporating conventional carriers, diluents and/or adjuvants. Such compositions may be produced in conventional manner.
The compositions of the invention co~prising both components a) and b) may for example be obtained by mixing said components a? and b), optionally with a carrier and other formulating ingredients.
Particularly formulations to be applied in spraying 15 forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylaryl-; sulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenol and an ethoxylated fattyalcohol.
In general, the formulations include from 0.01 to 90~ by weight of active agent, said active agent consisting either of at ]east one compound of formula I
or mixtures thereof with other active age~ts, such as fungicides e.g. a component b) as defined hereinbefore.

~3~3(~6 Concentrate forms of composition generally contain between about 2 and 80%, preferably between about 5 and 70~ by weight of active agent. Liquid application forms of formulation may contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
The invention is illustrated by the following Examples wherein parts and percentages are by weight and temperatures are in C.

13~?3~6 Formulation Exam~le I : Wettable ~owder _________._____ 50 Parts of 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide are arouna with 2 parts of lauryl sulphate, 3 parts sodium lignin sulphonate and 45 parts of finely divided kaolinite until the mean particle size is below 5 ~icrons. The resulting wettable powder so obtained is diluted with water before use to a concentration of between 0.01% to 5~ active agent. The resulting spray liquor may be applied by foliar spray 10 as well as by root drench application.
Formulation Example 2 : Granulate Onto 94.5 parts by weight of ~uartz sand in a tumbler mixer is sprayed 0.5 parts by weight of a binder (non-ionic tenside) and the whoie thoroughly mixed. 5 Parts by weight of powdered 2-methoxy-N-(2,6-dimethylphenyl)-15 N-(2-oxo-3-oxazolidinyl)-acetamide are then added ; and thoroughly mixing continued to obtain a granulate formulation with a particle size in the range of from 0.3 to 0.7 mm. The granulate may be applied by incorpor-ation into the soil adjacent the plants to be treated.

13~3Q~6 Formulation Examples 3 to 6 (wettable powders) % by weight _ Example 3 4 5 6 Component a)(l) 12.65 6.25 12.5 6.25 copper (II) oxychloride (~-56% Cu) 47 47 cuprous oxide (~- 88% Cu) 29 29 Na laurylsulphate 1 1 1 1 ligninsulphonate 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-3-oxazolidinyl)-acetamide All the components of the formulation are mixed, milled and mixed again in conventional manner.

13V3C~6 Formulation Exam~les 7 to 9 (wettable powders) -l % by weight Example 7 8 _ _ _ Component a)(l) 25 12.5 6.25 Component b2(2) 50 50 50 Na oleoylmethyltauride 2 2 2 Condensation product of Na alkyl naphthalene-sulphonate and formal-dehyde 5 5 5 silica gel 5 5 5 Xaolin 13 25.5 31.75 (1) e.g. 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide ~2) e.g. Folpet All the components of the formulation are mixed, milled and mixed again in conventional manner.

13~3C~6 - 2~ - 130-3882 Formulation Examples 10 to 12 (wettable powders) % by weight Example 10 11 12 Component a)(l) 25 12.5 6.25 Component b3)(2) 50 50 50 Na laurylsulphate 1 1 1 ligninsulphonate 4 4 4 Silica gel 5 5 5 Kaolin 15 27.5 33.75 (1) e.g. 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (2) e.g. mancozeb The formulation is obtained by mixing the components, subsequently milling the mixture and repeated mixing in conventional manner.

13~3~6 Example 1 : 2-Methoxy-N-(216-dimethyl~henyl)-N-(2-oxo-3-oxazolldinyl)-acetamide 11.8 g (0.0375 mol) 2-Chloroethyl 2-(methoxy-acetyl)-2-(2,6-dimethylphenyl)-hydrazinecarboxylate are added portion-wise to a suspension of 2.0 g sodium hydride (in form of about 55% by weight in mineral oil) in 100 ml absolute toluene at room temperature under a blanket of nitrogen. The reaction temperature rises gradually during this addition up to 40. After the addition is complete the mixture is stirred during 30 minutes without cooling and afterwards cooled to 10.
The vnreacted sodium hydride is then destroyed with ethanol, the obtained solution washed with water dried with MgS04 and the solvent removed in vacuo to give the end title compound which is recrystallised from ethanol to yield the title compound as colourless crystals.
m.p. 103-104.
Example la : 2-Chloroethyl 2-(m_thox~vacetyl)_2- (_L_-dimethyl~henyl)-hydrazinecarboxylate The starting material used in Example 1 is obtained as follows:
A mixture of 14.7 g (0.06 mol) 2-chloroethyl 2-(2,6-dimethylphenyl)-hydrazinecarboxylate and 16.2 g (0.1 mol) methoxy acetic acid anhydride [(CH30C~2C0)20]
are stirred in 100 ml dry toluene during 1 hour at 80.
After cooling, the solution is washed with water, then 13~3~46 -28 ~ 130-3882 with a 5~ NaHC03 aqueous solution and then again with water.
The solution is dried with MgS04 and the solvent removed in vacuo to give the title compound of Example la.

Example lb : 2-Chloroethyl 2-(2L6-dlmethyl~henyl)-hydrazinecarboxyl.ate To a mixture of 127 g ( 0.935 mol) 2,6-dimethyl.
phenylhydrazine, 102.5 g ~1.3 mol) pyridine and 400 ml water is added, at 0-5, 133.5 g ( 0.935 mol) chloro-10 formic acid ~-chloroethyl ester. After the addition is complete, the mixture is stirred for 2 hours at room temperature, the formed precipitate filtered off, washed with water and dried. The so obtained title compound is recrystallised from toluene to yield 15 colourless crystals, m.p. 74-75.
According to a preferred alternative procedure of Example 1, la and lb, one proceeds as follows:
Example 2 : 2-Methoxy-N-(2,6-dimethyl~henyl)-N-(2-oxo-________ ______________ _ ___ ____________ 3-oxazolidinyl)-acetamide 236.1 g (0;75 mol) 2-Chloroethyl 2-(methoxyacetyl)-2-(2,6-dimethylphenyl)-hydrazinecarboxylate, 375 ml xylene and 187 ml water are stirred with external cooling, while 82.5 ml (0.82 mol) of an aqueous solution of sodium hydroxide (containin~ ~ 0.4 g NaOH per ml) are added at 25 a rate to maintain the internal temperature at approx. 20.

13~3( 1~6 - 2g - 130-3882 The mixture is stirred after completion of the addition for 1 hour at 20, and for 2 hours at 0. The solid is filtered off, washed with 150 ml water and dried to yield the title compound as a slightly coloured solid, m.p. 102-103.
Example 2a : 2-Chloroethyl 2-(methoxyacetyl)-2-(_,6-dimethyl~henyl)-hydrazinecarboxylate 200 g (0.825 mol) 2-Chloroethyl 2-(2,6-dimethyl-phenyl)-hydrazinecarboxylate in 500 ml xylene are warmed 10 to 80, and added to a warm (80) solution of 2-methoxy-acetylchloride in 250 ml xylene, prepared in situ by treating 73.5 g (0.826 mol) 2-methoxyacetic acid in 250 ml xylene with 107.1 g (0.9 mol) ~hionyl chloride at 80 for 2 hours. The mixture is heated for 30 minutes at 80, 15 then worked up as described in Example la.
Example 2b : 2-Chloroethyl 2-(2L6-dimethyl~henxl)-hydrazinecarboxylate A mixture of 17.7 g (0.1 mol) 2,6-dimethylphenyl-hydrazine hydrochloride, 21.2 g (0.2 mol) sodium 20 carbonate in 50 ml water and 50 ml xylene are stirred for 30 minutes at room temperature, then cooled to 5. 14.3 g (0.1 mol) chloroformic acid 2~chloroethylester is then added over a period of 1 hour, the temperature being maintained at 5. The mixture is stirred at 5 for 25 another hour, at the end of which 100 ml water are added, the precipitate thus formed filtered off, washed with water and dried. Further work-up as in Example lb.

13~3Q46 In analogous manner to that described in the preceding Examples 1 and 2 the following compounds of formula I are produced Ex. R3 R4 R5 R6 R7 R8 Rg Rlo M p.

3 H H H H CH3 CH3 H CH20C2H$ 62-4 4 H H H H CH3 Cl H CH20CH3 99-100 H H H H CH3 CH3 H ~ 190-1 6 H H H H CH3 CH3 4-Cl CH20CH3 107-9 9 H H H H CH3 CEI3 H CH2Cl 134-6 10 H H H H CH3 C1 H CH2Cl 135-6 11 H H H H CH3 CH3 H CH20CHtCH3)2 12 H H EI H CH3 Cl H CH20CH(CH3)2 13 H H H H CH3 Cl H ~ 166-7 14 H H H H CH3 CH3 H CH2SC4H9(n) oil H H H H C~3 Cl H CH2SC4Hg(n) oil 16 H H H H CH3 CH3 H C,H-C2H5 123-4 Br Cl 18 H H H H -H3 CH3 EJ CH2Br 143-4 19 H H H H ~H3 CH3 H ~ 119-20 20 H H H H Cl Cl H CH20CH3 107-3 21 H H H H Cl C1 H CH2Cl 142-4 :13(~3~6 Ex R3 R4 R5 R 6 R 7 R N R 9 1 o M p .
_ _ _ .. _ .
22 H H H H Cl Cl H ~ 173-4 23 H H H H CH3 CH3 H CH2N ~ 139-41 24 H H H H CH3 CH3 4-CH3 CH20CH3 oil 25 H H H H CH3 C2H5 H CH2C1 oil 27 H H H H CH3 CH3 3-Br CH20CH3 96-7 28 H H H H CH3 CH3 3-Br CH2Cl 182-3 29 H H H H CH3 CH3 3-Br ~ 145-8 30 H H H H CH3 Br 4-CH3 CH20CH3 125-6 31 H H H H CH3 Br 4-CH3 CH2Cl 124-6 32 H H H H CH3 Br 4-CH3 ~ 193-4 34 H H H H CH3 CH3 H . ~ 149-52 35 H H H H CH3 CH3 4-Cl CH2Cl ~um 36 H H H H CH3 CH3 4-Cl ~ 164-5 38 H H H H CH3 CH3 H C~20C3H7(n)oil 13~3~

_ _ __ __ .
~x. 3 R4 R5 R6 R7 R8 Rg 10 . M p.

39 H Ei H H CH3 CE~3 H CH20C4H9(n~

41 H H H H CH3 CH3 H CH~CH2CH=CH2 98-100 43 H H H H CH3 CH3 H CH2 ~ 107-8 44 H H CH3 H CH3 CH3 H CH20(H379-80 H H H H CH3 CH3 H CH2N ~1462_4 46 H H H H C2H5 C2H5 H ~

47 H H H H C2H5 C2H5 H CH2Cl 88-9 48 H H H H Br Br H CH20CH3150-2 9 H H H H Cl Cl 4-Cl CH20CH3128-9 H H H H C2H5 C2H5 4-Cl CH20CH3114-6 1 H H H H Br Cl 4-CH3 CH20CH3 131-4 2 H H H H ~H3 C2H5 H CH20CH3 96-8 3 H H H H CH3 CH3 4-Br CH20CH3137-8

Claims (14)

1. A method of combatting phytopathogenic fungi in plants, seeds or soil which comprises applying thereto a fungicidally effective amount of a compound of formula I

I

wherein R1 is wherein R7 and R8, independently, are C1-4alkyl, halogen or C1-4 alkoxy, and R9 is hydrogen, C1-4alkyl or halogen, R2 is CO-R10, wherein R10 is C1-4alkoxy-C1-4alkyl, C1-4alkyl-thio-C1-4alkyl,

2-furyl, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1-imidazolylmethyl, 1-pyrrazolylmethyl, 2-tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl, or C1-4halogenalkyl, and R3, R4, R5 and R6 are independently hydrogen or C1-4 alkyl.

Case 130-3882 2. The method according to Claim 1 wherein R2 is -COCH2OCH3, -COCH2OC2H5, -CO-(2-furyl) or -CO-(5-halo-2-furyl), R3, R4, R5,R6, R7 and R8 are independently CH3, Cl or Br and R9 is H, Cl, Br or CH3.

3. The method according to Claim 2 wherein R7 and R8 are identical.

4. The method of Claim 3, wherein R7, R8, R9 and R10 are a) CH3, CH3, H and CH2OCH3 respectively, b) CH3, CH3, 3-Cl and CH2OCH3 respectively, or c) CH3, CH3, 3-Br and CH2OCH3 respectively.

5. A method for fighting phytopathogenic fungi infections of plants, seed or soil in which plants live which comprises applying thereto a fungicidally effective amount of a component a) comprising a compound of formula I as defined in Claim 1, and of a component b) selected from a component b1) a copper fungicide or a component b2) captan or folpet or a component b3) mancozeb or maneb.

6. The method of Claim 5, wherein - in formula I - R2 is -COCH2OCH3, -COCH2OC2H5, -CO-(2-furyl) or -C0-(5-halo-2-furyl), R3, R4, R5,R6, R7 and R8 are independently CH3, Cl or Br and R9 is H, Cl, Br or CH3.

7. The method of Claim 6, wherein R7 and R8 are identical.

8. The method of Claim 7, wherein R7, R8, R9 and R10 are a) CH3, CH3, H and CH2OCH3 respectively b) CH3, CH3, 3-Cl and CH2OCH3 respectively or c) CH3, CH3, 3-Br and CH2OCH3 respectively.

Case 130-3882

9. A method of Claim 8 wherein the compound of formula I is N-methoxyacetyl-N-(2,6-dimethyl-phenyl)-3-aminooxazolidone and component b) is selected from captan, folpet, mancozeb or maneb.

10. A method of Claim 9, wherein component b) is mancozeb.

11. A fungicidal composition comprising a compound of formula I
stated in Claim 1 in association with a fungicidal component b) selected from a copper fungicide, captan, folpet, mancozeb or maneb.

12. A fungicidal composition of Claim 11 wherein the weight ratio of the compound of formula I: component b) is in the range of 1:1 to 1:10.

13. A fungicidal composition of Claim 12, wherein the compound of formula I is N-methoxyacetyl-N-(2,6-dimethylphenyl)-3-amino-oxa-zolidone and component b) is captan, folpet, mancozeb or maneb.

14. A process for the production of a compound of formula I stated in Claim 1 characterised by intromolecular condensation of a compound of formula II
II
wherein R1, R3, R4, R5, R6 and R10 are as defined in Claim 1 and Y is halogen.