AU615887B2

AU615887B2 - Fungicide azolyl-derivatives

Info

Publication number: AU615887B2
Application number: AU82975/87A
Authority: AU
Inventors: Giovanni Camaggi; Roberto Colle; Carlo Garavaglia; Franco Gozzo; Luigi Mirenna; Giuseppina Ratti
Original assignee: AGRIMONT Srl
Current assignee: AGRIMONT Srl
Priority date: 1986-12-23
Filing date: 1987-12-23
Publication date: 1991-10-17
Anticipated expiration: 2007-12-23
Also published as: AU8297587A

Description

.ili_ i COMMONWEALTH CF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION FOR OFFICE USE 61Form588 Form Short Title: Int. Cl: Application Number: Lodged: 9 0 0 0 Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT 9

D

9 Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: AGRIMONT S.r.l.

31, Foro Buonaparte, Milan, Italy Roberto COLLE, Giovani CAMAGGI, Franco GOZZO, Giuseppina RATTI, Carlo GARAVAGLIA, and Luigi MIRENNA GRIFFITH HASSEL FRAZER 71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the invention entitled: FUNGICIDE AZOLYL-DERIVATIVES The following statement is a full description of this invention, including the best method of performing it known to me/us:- 7114A -2 94 9 I #94 I 9.

4 *tt 4 44 94 9 *i *4 4.

4 49 q 94$ it 0 4 4 .9 44 9 4 4 49 94*444 9 4 49 44 4. 4 4 *4 4 *4 -The present invention relates to azolyl-derivatives having high fungicide and phytogrowth cegulating activity, to the process for their preparation and to the corresponding employ of such compounds in agricultural field.

From German Patent No 2.654.890 triazolylcarbinols are known, having general formula: OH Y n ,N -L H-C N R' 3 Oj o o 000 0 0a 0e e 00 0 0* 0 *r 00 0r 0 0; *0 wherein:: R and R 2 are H or a hydrocarbyl group; with the expression hydrocarbyl a saturated or unsaturated, linear or branched chain or a single or condensed ring is meant and, when the hydrocarbyl radical is or contains an aryl group, this latter may be substituted; Y is, for instance, a halogen atom.

From European patent No 150036 azolyl-derivatives are also known, having formula:

OR

N--CH-C-

-(CH--Q

N 2 CHn Ar wherein Ar is a substituted aromatic group; A is CH, N; 1 n, 2 12; R an alkyl, alkenyl, alkynyl, or benzyl ra- 2 3 2 3 dical; Q R or OR in which R R are an alkyl, 1-2 cycloalkyl, alkenyl or aryl radical independently.

Moreover from European patent application No 145.294 the compounds are known, having formula: N

CN

R

00 or r ooo 0 o a 00 0 0 0 00 0 OP P l 0 00 te 0 op I 6«0 0 0 0 0 0 0 0 wherein R is a C 3 -Cg alkyl radical, on condition that, when R is a C 3

-C

6 branched alkyl radical, the branch has not to be on carbon atom Okof group R; X is a halogen atom.

We have now found a class of azolyl-derivatives, which differ from the prior art and are endowed with a higher fungicide activity and with phytogrowth regulating properties.

C Therefore a-t -ej-o the present invention concerns o a the compounds having general formula:

R

C (CH) X (CH Rf "n 2 m (I) 1 0 R

*N

C2

C

I

S R is selected from the group comprising F, Cl, Br, CF, a 3 phenyl, aC 1

-C

2 alkoxy, a C-C 2 haloalkoxy, an alkylthio, a haloalkylthio radical, in which the halogen is F, Cl, Br; S R 2 is selected from the group comprising H, F, Cl, Br, CF 3

R

3 is H, aC -C 4 alkyl or a C3-C cycloalkyl radical; Y is selected from the group comprising H, CH 3 OH, CN, F; n is 2, 3, 4 or 1 as well, when Y is OH; YT io n is2, 4 r 1as wllwhenY i OH I _Ir .4 4 (t 64 t 6r 1 4 S 6r i

I

I 6* 5 m is 0 or 1.

X is O or S; Rf is selected from the group consisting of C -C 5 polyfluoroalkyl, C 2

-C

4 polyfluoroalkenyl, polyfluoroalkoxyalkyl and polyfluoroalkoxyalkenyl radicals, everyone of them containing at least two fluorine atoms and, optionally, other halogen atoms selected from Cl and Br; Z is CH or N.

The compounds having general formula are endowed, as above mentioned, with a higher fungicide activity and with phytogrowth regulating properties and may be employed advanta= geously in agricultural, medical and veterinary field.

The compounds of the present invention contain at least a k l centre and are generally obtained in the form of racemic mixtures.

The single enantiomers can be separated from these mixtures by methods, known in literature.

Both the single enantiomers and the possible diastereoisomers or geometric isomers, generated by several ea c\ Q\ centres or by possible double bonds, form an object of the present invention.

V Vr *r I V jt V 41 4l It ii~

V"

*s S *S**St 6 The following compounds form also an object of the present invention: the salts of the compounds having formula coming from an inorganic acid such as a hydrohalogenic acid, for instance hydroiodic, hydrobromic, hydrochloric acid; sulphuric, nitric, thiocyanic and phosphoric acid: or from an organic acid such as acetic, propanoic, ethanedionic, propanedionic, benzoic, methanesulphonic, 4-methylbenzenesulphonic acid and the like; -the metal complexes obtained by complexation reaction between the derivatives of type with an inorganic or organic metal salt such as halogenide, nitrate, sulphate, phosphate of, for instance, copper, manganese, zinc or iron.

of the present invention The compounds having formula (I)/can be obtained by different processes according to the value of n, m and Y.

1) A general process for the preparation of the compounds having formula when m is 0, consists in carrying out an addition reaction of the compounds having formula: 7-

R

2 Y3

I

c -(CH)-XH 0 n R 1 /I

/Z

CH -N, 2 (II) 1 2 3 wherein R R R Y, X and Z have the meanings,, as specified hereinbefore, to a fluoroolefin having formula: t r xl It1 t I( CF C :2 tA n 1 i wherein X is F, Cl, CF 3

X

2 is F, Cl, CF 3 or S- OX in which X/a polyfluoroalkyl radical having from 1 to 3 carbon atoms, containing at least three fluorine atoms and optionally other halogen atoms selected from Cl and Br, in the presence of aprotic so].- 4 vents, such as, for instance, DMF, DMSO, THF, dioxane or pyridine, or in an alcoholic solvent, such as, for instance terbutanol, in the presence of catalytic or stoichiometric amounts of a strong organic or inorganic base, such as, for instance, sodium hydride, potassium terbutilate and potassium hydroxide, at temperatures ranging from -20 0 C to 100 0 C, to yield the -8compounds having formula:

R

2

Y

RR

I I -1 2 C X-CF -CHX X n 2 R1 CH---N (Ia) r t S By subsequent dehydrofluorination reaction of the compounds of formula which reaction may also take place spontaneously during the above described reaction, an unsaturation may be introduced in the Sk-position of group Rf, thereby obtaining the unsaturated compounds having formula: 2 o Y RR3 x

RR

3 C (CH) X--CF C (T n 2 i H CH N (Ib) rj 2) Another process for the preparation of the compounds having formula when X is 0 and m is 1, consist, in carrying out a reaction of nucleophil substitution on the reactive ester having formula: I i: _L -C1 i -9f~T 9

R

2

Y

R 3 C (CH Y' /0 n 1 =1 CN (III) CH -N 7 wherein Y' represents a halogen atom or a mesyl or tosyl group, by means of an alkaline salt of a polyfluorinated alcohol of formula (IV),according to the reaction scheme: RI 2

Y

R3 t base C OH O n 2 I (IV)

CH-N

R2

Y

R R 3 C O-CH -Rf SCH N (Ic) 2 N The reaction is carried out preferably in aprotic dipolar solvents,such as DMF, DMSO or ethereal solvents, such as, for instancer diethylether, THF or dioxane, in the presence of stoichiometric amounts of a strong base, such as, for instance, sodium hydride or potassium terbutylate.

The reactive ester of formula (III) can be obtained 10 easily by treating the corresponding primary alcohol of formula wherein X is 0, with a halogenation, tosylation or mesylation agent.

3) Another process for the preparation of the compounds having formula when m is O, consists in reacting an alkaline salt of a compound of formula (II) with a polyfluoro-alkyl-halogenide having formula: 4 4 Rf-X 4 in which X is a halogen atom, such as chlorine, S bromine or fluorine, according to the reaction scheme:

R

2 y R3

R

3 4 base C*C. C XH Rf-X 4 0( n -HX 4* 1> O-

IR

C R CH 2-N (Id) The reaction is carried out in conditions similar to the ones indicated hereinbefore for process 2).

4) Another process for the preparation of the compounds 11 having formula when Y is -OH, consists in reacting a.polyfluorinated oxirane of formula (XI) with an alkaline salt of an azole,according to the reaction scheme:

R

2 CH 3

H

2 0 R

I

N-base i C CH)n--X--(CH 2 Rf Z 1, (XI) SiR 2

OH

R

3 -(CH )-Rf n 2 m It /Y 1 Z

R

SCH-N Y OH) *2 N The reaction is generally carried out in an aprotic di-

A

polar solventr such as DMSO o DMF, in the presence of S*t stoichiometric amounts of a strong base, such as sodium or KOH, hydride, potassium terbutylate /at temperatures ranging from the room temperature to the reflux temperature of the solvent.

The intermediate compounds of formula when R 3 is H, employed in processes 1) and may be prepared by reduction of the esters having formula: 12 212 R n-Y C C 1 22 COOR

CH--N

wherein R R 2 Y and Z have the meanings, as specified hereinbefore and R represents an ethyl or a methyl radical, by using mixed hydrides, such as, for instance, LiAlH 4 LiB-H 4 NaBH 4 in solvents of ethereal kind, such as, for instance, diethylether, THF, at temperatu- Sa res ranging from 0 0 C to 30 0

C.

The intermediate compounds of formula can, in their turn, be prepared by different methods, according to the nature of Y and the value of n.

When Y OH the intermediate compounds of formula 4 can be prepared by conversion of the compounds 4 having formula (VI) into the correspondin oxiranes of formula (VII) and subsequent conversion of the oxiranes of formula (VII) into carbinols (Y=OH), by reaction with an alkaline salt of azole, according the reaction schemes: i i 13- (0)0, (CH -COOR (CH 3)2- -S=CH2> 2 n-I 2 (VI (CH COOR VI I) .'Na' 9 Ofobase I* z 04 t R 2

H

0 C (H 2 n-i

COOR

R 1 1 Y OH CHT-N *0 00 0 fOf 9 *4 0 0 f~ to 9 0 4* 0*0*04 4 *4 *4 0 09 t 4 II 0* The compounds having formula (VI) are known in the prior art, for instance, from: Kindler, Metzendorf, Chem, Benichte 46 (1943) 308; Johnson, J.C.S. (1946)895; Jur'ev et 0 al., 2, obs, chim. 24 (1954)1568; Dauben, Tilles, J. Org.

Chem. 15 (1950)785; Bertachio, Dreux, Bulletin Soc. Chim.

Fr. (1962)823.

The conversion reaction of compounds (VI) into oxiranes (VII) is carried out according to a known methodology, for instance from: Corey, Chaykovsky, J.A.C.S. 87 (1965)1353and J.A.C.S.

84 (1962)3782.

i rr 14 The conversion reaction of oxiranes (VII) into carbihols is generally carried out, in an aprotic dipolar solvent, such as, for instance, DMSO or DMF, in the presence of stoichiometric amounts of a strong base, such as sodium hydride, potassium terbutylate or potassium hydroxide, at temperatures ranging from the room temperature and the reflux temperature of the solvent.

b) When Y OH and n 1, the intermediate compounds of formula can be prepared by subjecting to alcoholysis the cyanhydrines having formula (VIII) according to the reaction I t It I It I l I 42 lt 41- 44

R

2

OH

C- CN 1 R CH- N S (VIII) 2 R' OH C -COOR 1 °I Z CH- N

N

(Y OH, n 1) 7-

N

The alcoholysis reaction is generally carried out in an alcoholic solvent, such as ethanol or methanol, saturated with gaseous HC1, or in the presence of another mineral acid, such as sulphuric acid, at temperatures ranging from OC to the boiling point of the solvent.

15 The cyanohydrines of formula (VIII) can, in their turn, be prepared by addition of HCN to the suitable azolylacetophenones or starting from nitryls of formula known, for instance, from Dreux, Regeand, Bull. Soc.

Chem. Fr. (1959)1244, through the following set of reactions: R H -CH2 2 2

R

2 SCN NaC10 C CN S' c h4 foalartIcFiT. 0olvent Aneutral pH

R

S i

(IX)

Na 41 (IX)

(VIII)

N

c) When Y is different from OH, the intermediate compounds of formula can be prepared by known methods, for instance, when Y=CN, they can be prepared from nitryls having formula:

R

2

CN

CH-- (CH2)ni 1

COOR

R (XII) 16 by hydroxymethyiation in the alpha position with respect to nitryl, by means of bases and formaldehyde, followed by mesylation and displacement of mesylate by means of an alkaline salt of azole.

d) When Y=F, the intermediate compounds of formula can be prepared from carbinols of formula wherein Y=OH, by treatment with diethylaminosulfotrifluoride (DAST), in f 2CI an inert solvent, such as, for instance CH 2 C1 2 at temperatures ranging from -70 0 C to 0°C.

Another method for preparing the compounds of formula when Y=H, consists in dehydrating the compounds of formula wherein Y=OH and subsequently in hydrogenating catalytically the resultant olefin.

t i t S3 The intermediate oxiranes of formula (XI) when R is H, 4 employed in process 4) can be prepared by reacting ketones a a *a (XIII) with a sulfonium h a 1 i d e or sulfoxonium hylide, by using a methodology known, for instance, from Corey, and Chaykovsky, J.A.C.S. 87 (1965)1353 J.A.C.S. 84 (1962)3782, according to the reaction scheme: r 4 ij -at i 17 (CH X-(C-H Rf 2 n 2 m

(XIII)

(0) T 0,1 (CH3)2-S CH 2 32 2

(XI)

The ketones of formula (XIII) can, in their turn, be prepared by Friedel-K.raft condensation, starting from acid chlorides of formula (XIV), according to the following reaction: ttA tl L t~ I A1C1 II 3 0 CI-c-(CH2n X-(CH2)--Rf

(XIII)

R2 'v (XIV) This reaction, already known, is carried out by using as solvent the s'me benzenic derivative, used as starting compound at temperatures ranging? from the room temperature and the boiling temperature of the mixture.

For the synthesis of the acid chlorides having formula (XIV), it is convenient to start from a .J-hydroxy (or mercapto) ester of formula afterwards, by following the reaction schemes previously described with methods 2) and 3) for the preparation of the compounds of formula fluorina- 1 18 ted esters (XVI)* are obtained.

The esters of formula (XVI), thus obtained, are then hydrolyzed, in an alkaline aqueous medium, to yield the corresponding acids (XVII), that, in their turn, are converted into the acid chlorides of formula (XIV), by means of a chlorination agent, for instance thionyl chloride, optionally in the presence of a catalyst, such as DMF, at temperatures rane F* a.ging from 200 to 60 0 C, according to the reaction schemes: HX-(CH -COOR methods >Rf-(CH 2 )m X-(CH 2

-COOR

S1) or 3) S.0 (XV) (XVI) S" SOC1 NaOH SO 2 (XVI) Rf-(CH 2

-X-(CH

2 -COOH (XIV)

DMF

(XVII)

In particular, the compounds of formula (XVI), when S*o 1 2 1 2 m=O and Rf X X CH-CF 2 in which X and X have the meanings, as specified hereinbefore, are prepared by reacting esters (XV) 6 0 o0° with a fluoroolefin having formula: °1 9

CF

2 CX X 2 in the presence cf aprotic solvents, such as for instance, DMF, DMSO, THF, dioxane or pyridine, or in an alcoholic solvent, such as for instance terbutanol, in the presence of catalytic or stoichiometric amounts of a strong organic or inorganic base, such as, for instance, sodium hydride, po- 19 2% II t

I

I 2'~ 22 2 2 t t%~ I I I II CI I I I

C

I

II It I I C 1 2 II I I I I

II

tassium terbutylAte, -at temperatures ranging from -201C to 1001C, according to-the reaction scheme: HX-(CH 2 )n-COOR+CF 2= CX 1X 2 bas 1 x2 HC2-X( 2nCR (XV) (XVI a) Examples of compounds having general formula according to the present invention, are reported in Table 1.

TABLE I R 2YR3 C )-Rf (1) 0n 2 M CH-N Comnpoufd N. IY I R 11R 3 1R 21Z IX In ImI Rf 1 I-OH I CI I H I C1 I NI_ 0 1 1 1 0 1 -CF -CF,)H 1 2 2 1-OHII C1 I H I C1 N 1 0 1 2 10 1 -CF,-CF, 2 -2 The compounds having general formula are endowed with fungicide activity and phytogrowth regulating activity and may be used advantageously both in agricultural field and in the medical-veterinary one.

Their fungicide activity proves to be particularly ~I 20 high against phytopathogenous fungi infesting cereal cultivations, fruit-growing, industrial and horticultural cultivations.

Examples of plant diseases that can be fought by using the compounds of the present inventions are the following ones: Erysiphe graminis on cereals 9 Sphaeroteca fuliginea on cucurbitaceae (for inst.cucumber) Puccinia, on cereals #9 0 Septoria on cereals 9 t Helminthosporium on cereals S- Rhynchosporium on cereals S Podosphaera leucotricha on apple-trees L ,4 Uncinula necator on vines Venturia inaequalis on apple-trees Piricularia aryzae on rice 04 Botrytis cinerea Fusarium on cereals and still other deseases.

Moreover the compounds of formula possess other positive characteristics, such as a fungicide action having 21 both curative and preventive character and la complete compatibility towards the plants, which have to be protected against the fungus infection.

Besides the high fungicide activity, due to preventive and curative applications, the compounds of formula (I) are characterized by systemic properties.

These properties allow the products to enter the vaj scular systems and to act even in sites (for instance leaves), c that are very far away from the ones they have been applied c- in (for instance, roots).

For the practical uses in agriculture it is often ad- S"s- vantageous to make use of fungicide compositions containing one or more compounds of formula as active substance.

The application of these compositions can take place on every part of the plant, for instance, leaves, stalks, branches and roots or on the seeds themselves, before the sowing, or on the soil adjoning-,the plant as well. The composivy tions may be used, in the form of dry powders, wettable powders, emulsifiable concentrates, pastes, granulates, solutions, suspensions and the like: the choice of the kind of composition will depend on the specific use. The compositions 22 are prepared, according, to a known way, for instance, by dia luting or dissolving the active substance by means of/solvent medium and/or a solid diluent, optionally in the presence of surfactants. The following compounds may be used as solid diluents or carriers: silica, kaolin, bentonite, talc, diatomite, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, sepiolite. Besides of course, water, several kinds of solvents may be used as **r 9 liquid diluents, for instance, aromatic solvents (benzene, xylenes, or mixtures of alkylbenzenes), chloroaromatic solvents (chlorobenzene), paraffins (oil cuts), alcohols (methanol, pro panol, butanol), amines, amides (dimethylformamide), ketones (cyclohexanone, acetophenone, isophorone, ethyl-amyl-ketone), esters (isobutylacetate).. As surfactants: sodium salt, calalkylsulfates, cium salts or triethanolamine of/alkylsulfonates, alkyl-arylc r Ssulfonates, polyethoxylated alkylphenols, fatty alcohols condensed with ethylene oxide, polyoxyethylated fatty acids, po Sr lyoxyethylated sorbitol esters, polyoxyethylated fats, ligninsulfonates. The compositions may also contain special additives for particular purposes, for instance adhesive agents such as gum-arabic, polyvinyl alcohol, polyvinylpyrrolidone.

1 1 23 If desired, other compatible active substances may be also added to the compositions, object of the present invention, such as fungicides, phytodrugs, phytogrowth regulators, herbicides, insecticides, fertilizers.

The concentration of active substance in the aforesaid compositions can vary within a wide range, according to the active compound, the cultivation, the pathogen, environmental conditions and the kind of formulation, that has been used. The concentration of active substance generally ranges from 0.1 to 95, preferably from 0.5 to 90% by weight.

The invention will now be illustrated by the following examples.

EXAMPLE 1 Preparation of 1-(1,2,4-triazolyl)-2-hydroxy-2-(2,4- -dichlorophenyl)-4-(1,1,2,2-tetrafluoroethoxy)butane (compound No 2).

Potassium terbutylate (0.2 g) was added to 1-(1,2,4- -triazolyl)-2-(2,4-dichlorophenyl)-2,4-dihydroxy-butane (1.9 g) dissolved in anhydrous THF (10 ml), anhydrous DMSO (20 ml), ml) anhydrous terbutanol, in a nitrogen atmosphere, at -10 0

C.

SAfter having produced the vacuum in the apparatus, 24 tetrafluoroethylene was introduced there and the whole was maintained in an atmosphere of this gas overnight, at room temperatur.

Then the reaction mixture was poured into water and extracted by means of ethyl acetate.

The extract was washed with water, dried on anhydrous sodium sulfate and evaporated. The crude product thus obtained, was analyzed by silica gel chromatography, by elur r ting with 1:1 n-hexane-ethyl acetate.

0.8 g of a whitish solid were isolated, having a melting point of 70-71 0 C, which was characterized as being IIt ,r in keeping with the structure indicated in the title, on the Sground of the following spectroscopic data.

I.R. (V cm 1 3150, 1590, 1520, 1280, 1200, 1120, t I N.M.R. H (90 MHz) TMS in CDC1 3 'i 2.10-2.45 1H); 2.55-2.95 1H); 3.80-4.30 2H); 4.55 1H); 5.20 1H); 5.20 1H); 5.60 (tt, 1H); 7.30 (dd, 1H); 7.40 1H); 7.75 1H); 7.90 1H); 8.10 1H).

EXAMPLE 2 Preparation of 1-(1,2,4-triazolyl)-2-hydroxy-2-(2,4ti I- m 25 -dichlorophenyl)--3- 2-tetrafluoroethoxy)'-propane (compound No 1).

This compound was prepared by a.process similar to the one described in example 1, starting from 1-(1,2,4-tri azolyl)-2-(2,4-dichlorophenyl)-2,3-dihydroxy-propane.

The compound was characterized by the following spectroscopic data.

i a o NMR H (60 MHz) TMS in CDC1 S 4.10 (s.broad, 2H); 4.85 broad, 2H) 5.10 1H); 5.55 00 0 o (tt, 1H); 7.35-7.70 3H); 7.90 1H) 8.10 1H).

0 00 EXAMPLE 3 Determination of the fungicide activity against cucumber oidium (Sphaerotheca fuliginea (Schlech) Salmon).

o Preventive activity: 0 0 Cucumber plants c.v. Marketer, grown in pots in a a* 00 conditioned environment, weresprayed on their lower leaf faces with the product being tested in a water-acetone solution, containing 20% of acetone (vol.vol.). Then the plants were kept in a.conditioned environment for 1 day, afterwards they were sprayed on their upper leaf faces with an aqueous suspension of conidia of Sphaerotheca fuliginea 4 *4,4 40 4, 4,4, 4,4,4, 4, 44 44 4P 4 4, 44 4 4D 4 4 4,4 26 (200.000 conidia/ml). The plants were then carried back to a conditioned environment.

At the end of the incubation period of the fungus indexes of (8 days) the infection degree was valued according to/a valuation scale ranging from 100 sound plant) to 0 completely infected plant) Curative activity: Cucumber plants cv. Marketer, grown in pots in a conditioned environment, were sprayed on their upper leaf faces with an aqueous suspension of conidia of Sphaerotheca fuliginea (200.000 conidia/ml.). 24 hours after the infection .the plants were treated with the products being tested in a water-acetone solution containing 20% of acetone (vol.

/vol.) by spraying both leaf faces.

At the end of the incubation period of the fungus (8 days), during which time the plants were kept a suitably conditioned environment, the infection degree was valued according to indixes of a valuation scale ranging from 100 sound plant) to 0 completely infected plant) The results are recorded in Table 2 EXAMPLE 4 27 Determination of the fungicide activity against wheat oidium (Erysipe Graminis Preventive activity: Leaves of wheat cv. Irnerio, grown in pots in a conditioned environment, were treated, by spraying both leaf faces with the products being tested, in a water-acetone solution containing 20% of acetone (vol./vol.).

After a stay time of 1 day in a conditioned environment at 200C and 70% of relative humidity, the plants wc::e sprayed on both leaf faces with an aqueous suspension of Erysiphe Graminis (200.000 conidia/cc.). After a stay time <t Sof 24 hours in an environment saturated with moisture, at Si 210C, the plants were kept in a conditioned environment for the fungus incubation.

At the end of said period of time (12 days), the I i Sinfection degree was valued according to indexes of a scale ranging from 100 (sound plant) to 0 (completely infected plant).

Curative activity: Leaves of wheat cv. Irnerio, grown in pots in a conditioned environment, were sprayed on both leaf faces with ~rr

-L

28 an aqueous suspension of Erysiphe Graminis (200.000 conidia/ cc). After a stay time of 24 hours in an environment saturated with moisture, at 21 0 C, the leaves were treated with the products being tested, in a water acetone solution containing 20% of acetone (vol/vol), by spraying both leaf faces.

At the end of the incubation period (12 days), the Sinfection degree was valued at sight, according to indixes of a valuation scale ranging from 100 sound plant) to 0 completely infected plant) The results are recorded in Table 2.

4 EXAMPLE

I,

Determination of the fungicide activity against S wheat linear rust (Puccinia Graminis Pers.) i S Preventive activity: oLeaves of wheat cv. Irnerio, grown in pots in a conditioned environment, were treated by spraying both leaf faces with the products being tested in an aqueous water-acetone solution containing 20% of acetone (vol/vol). After a stay time of 1 day in a conditioned environment, at 230C and 70% of relative humidity, the plants were sprayed on

-I

29 both leaf faces with a mixture of spores of Puccinia Graminis in talc (100 mg of spores/5 mg of talc).

After a stay time of 48 hours in an environment saturated with moisture, at 21 0 C, the plants were kept in a conditioned environment for the fungus incubation.

At the end of said period of time (14 days), the infection degree was valued at sight, according to indexes t of a scale ranging from 100 (sound plant) to 0 (completelyinfected plant).

f.till Curative activity: Leaves of wheat cv. Irnerio, grown in pots in a con- «diti6ned environment, were sprayed on both leaf faces with S, a mixture of spores of Puccinia Graminis in talc (100 mg of spores/5mg of talc); after a stay time of 48 hours in an environment saturated with moisture, at 21 0 C, the leaves were treated with the products being tested in a water-acetone solution containing 20% of acetone (vol/vol), by spraying both leaf faces.

At the end of the incubation period (14 days) the infection degree was valued at sight, according to indexes of a valuation scale ranging from 100 sound plant) to 0

B

r i a «O C *B o° o 0 0 0 e 11e So O O o 0 ,0 00 8 0I 00 00Q ~a 0 0 0 0 oQ 0 II 0 00 0 0 0 0 -«0 0 0 0 04 0 0 30 (completely infected plant).

The results are recorded in Table 2.

EXAMPLE 6 Determination of the fungicide activity against apple- -tree Ticchiolatura (Venturia inaequalis (CKe) Wint).

Preventive activity: Leaves of apple-trees cv. Starking, grown in pots in a glasshouse, were treated by spraying both leaf faces with the products being tested, in a water-acetone solution containing.

20% of acetone (vol/vol). After a stay time of 1 day in a conditioned environment, at 20°C and 79% of relative humidity, the plahts were sprayed uniformly with an aqueous suspension of conidia of Venturia inaequalis (200.000 conidia/cc). After a stay time of 2 days in an environment saturated with moisture, at 21 0 C, the plants were kept in a conditioned environment for the fungus incubation.

At the end of this period (14 days) the infection degree was valued at sight, according to indexes of a valuation scale ranging from 100 (sound plant) to 0 (completely infected plant).

Curative activity: Leaves of apple-trees cv. Starking, grown in pots in a

*J

I~ -31 glasshouse, were sprayed uniformly with an aqueous suspension of conidia of Venturia inaequalis (200.000 conidia/cc); after a stay time of 2 days in an environment saturated with moistu re, said leaves were treated with the products being tested, in a water-acetone solution containing 20% of acetone (vol/ vol), by spraying both leaf faces. At the end of the incubation period (14 days) the infection degree was valued at sight, according to indexes of a valuation scale ranging from 100 (sound plant) to 0 (completely infected plant).

4 The results are recorded in Table 2.

i t f 1 t t t tI -li

I^

T AB LE 2 Cblipound Dose Sphaerotheca fuli- Erysiphe graminis Puccinia gra- Venturia inae- No. g/l ginea/cucumber trit./wheat mnswet qualis /appie-tree Preventive Curative Preventive Curative Preventive Curative Preventive Curative activity activity activity activity activity activity activity 1 0.5 100 100 100 100 100 100 100 100 0.125 100 100 100 100 100 100 100 100 2 0.15 100, 100 100 100 100 100 100 100 2 0.5 100 100 100 100 100 100 100 100 0.125 100 100 100 100 100 100 100 100

Claims

6. Fungicide compositions having as active ingredient one or more compounds according to claims 1-3, together with a solid or liquid carrier and optionally other additives.
7. Compounds having general formula (I) substantially as herein described with reference to Examples 1 or 2. 15 8. A process for the preparation of the compounds #Va :of formulae (Ia) and (Ib) substantially as herein described with reference to Examples 1 or 2.
9. Fungicide compositions substantially as herein described with reference to any one of Examples 3 to 6. 0 0 *0 DATED this 30th day of July 1991 D* AGRIMONT SRL By their Patent Attorney GRIFFITH HACK CO. 20038A/428