CA1121376A - Microbicides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Novel acylated N-(substituted) phenylalanine esters of the formula I:

(I)

Description

~ ~ Z ~ 37 ~

The present invention relates ~o compounds of the fo~nula I

~ 1 ' 3 4 ~ C-CH~ R8 (I) R2 ~ R6 R7 wherein Rl represents Cl-C4alkyl, Cl-C4alkoxy or halogen, R2 represents hydrogen, Cl-C3alkyl, Cl-C4alkoxy or halogen, R3 represents hydrogen, Cl-C3alkylJ Cl-C4alkoxy or halogen, represents hydrogen or methyl, with the proviso that the total number of carbon atoms of the substituents Rl, R2, R3 and R~ in the phenyl ring does not exceed 8, R~ represents -COOR', -COSR', in which R' represents methyl or ethyl, R6 represents hydrogen, methyl~ Cl-C3alkoxy, R7 represents hydrogen or methyl, and ..
R8 represents Cl-C3alkoxy.

By alkyl or as alkyl moiety of an alkoxy group are meant the following groups~ depending on the sta~ed number of carbon atoms: methyl, ethyl, pxopyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. The term 1'halogen" denotes fluorine, chlorine, bromine or iodine.

~, ~ ~ 2~ ~7 ~

The invention furthermore relates to microbicidal compositions which contain a compound of the formula I as active component, and also to a process ~or controlling ungi which comprises the use of compounds of the formula I.

Surprisingly, it has now been found that compounds having the structure of the formula I possess for practical purposes a very advantageous microbicidal structure for protecting culti-vated plants. Examples of cultivated plants within the scope of the present invention are: cereals, maize, rice 9 vegetables, sugar-beet, soya, ground nuts, fruit trees, ornamentals, and in particular vines, hops, cucumber plants (cucumber, marrows, melons), solanaceae, such as potatoes, tobacco plants and tomatoes, and also banana, cocoa and natural rubber plants.

With the active compounds of the formula I it is possible to inhibit or destroy the fungi which occur in plants or parts of plants (fruit, blossoms, leaves, st~ms, tubers~ roo~s) in these and also related crops of useful plants, and also to protect from attack by such fungi the parts of plants which grow later. The active compounds are effective against the phytopathogenic fungi which belong to the follow;ng classes Ascomycetes (e.g. Erysiphaceae); Basidiomycetes, in parti~u-lar rust fungi; fungi imperfecti (e.g. Moniliales );
and especially against the Oomycetes belonging to the class of the Phycomycetes, such as Phytophthora, Pythium or Plasmopara. In addition, the compounds of the formula I possess a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings from fungus infections and from phytopathogenic fungi which occur in the soil.

One of the preferred subgroups of compounds comprises those of the formula I, wherein Rl represents methyl, R2 is in the ortho-position to the amino group and represents methyl, ethyl, chlorine or bromine, R3 represents hydrogen, halogen, p-(Cl-C4) alkoxy or methyl, and R4 represents hydrogen or methyl, whilst R5 to R8 have the given meanings and R' represents methyl This group of compounds will be designated Ia.

Among these compounds of the group Ia, compounds to be high-lighted on account of their action are those in which R5 re-presents the group -COOCH3. This subgroup will be designated Ib.
A preferred compound of this subgroup is that listed in the-subsequent table as compound 43.

ven when used in high concentrations, compounds of the formula I
are in general well tolerated by cultivated plants, although chloroacetanilides of similar structure have been proposed as herbicides in the literature (cf. US patent specification 3,780,090 and German Offenlegungsschrift 2j3117897).

In a further aspect of the invention, the compounds of the formula I are produced as follows:

~Z~l3~6 A) if ~-alkoxy-acylated or ~ alkoxy-acylated compounds are desired, by acy]ating a compound of the formula II

R

NH-CH-R5 ~II3 ~4 with a carboxylic acid of the formula III

HO-CO-CH-CH-R8 (III) or with the acid anhydride or acid halide thereof~
- or B~ if ~-alkoxy-acylated compounds in which R6 is hydrogen or methyl and R7 is hydrogen or methyl and R8 is Cl-C3alkoxy are desired, by replacing the halogen atom in an intermediate of the formula R3 Rl CH3 R4 ~ / CH-R5 (IV) CO-CH~ halogen " ~D I I
~`2 6 7 : with an alcohol or alkali (or alkaline earth) alcohola~e of the formula V

M - R8 ~V) or ~- 5 --~ 3~ ~

C) if the ~-alkoxy-acylated compound type referred to in B) is desired, also by Michael addition o-f the alcohol or its alcoholate V to the ~ unsaturated anilide of the formula VI

R3 R , 3 -\ ~ 1 CH-R

R4 ~ CO-C-CH (V~) or D) if a,~-bis(alkoxy)acylated compounds are desired in which R6 and R8 are identical and represen~ Cl-C3alkoxy, and R7 is hydrogen or CH37 by addition of elementary halogen, preferably chlorine, bromine or iodine, to a substituted acrylanilide of the formula VII

3 ~ / CH-R5 R4 CO-CH=CH

and further replacement of the two halogen atoms in the side chain 3L~Z3 37B

\ C0 - CH - CH - Hal' Hal R7 with at least 2 moles o an alcohol (or its alcoholate) of the formula V, in which in this case R6 has the same meaning as R8-In the formulae II to VII, Rl to R8 are as defined in formula I,Hal' represents halogen, and M represents hydrogen or the metal cation referred to.

The reactions may be carried out in the presence or absence of solvents or diluents which are inert to the reactants.
Examples of suitable solvents or diluents are: aliphatic or aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons, such as chloro-benzene, methylene chloride, ethylene chloride, chloroform;
ether and ethereal compounds~ such as dialkyl ethers, dioxane 7 tetrahydrofurane; nitriles~ such as acetonitrile; N,N,-di-alkylated amides, such as dimethyl formamide, dimethyl sul-phoxide, and mixtures of such solvents.
The reaction temperatures are between 0 and 180C, preferably between 20~ and 120C. In many cases the use of acid acceptors or condensation agents is advantageous, for example tertiary amines~ such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali metals ' ~ ' ~ ~ 2 ~ 3~

and alkalille earth metals~ as well as sodium acetate.
Process A,sta~ting from compounds of the formula II, can also be carried out without acid acceptors, whilst in some cases (use oE the acid halide) the introduction of ni~rogen to expel hydrogen halide is expedien~. In other cases it is very advan-tageous to add dimethyl formamide as reaction catalyst.

Particulars relating to the manufacture of the intermediates of the forrnulae II, IV, VI and VII are known for example from the herbicide literature referred to above.

As is evident~ the compounds of the formula I possess in the vicinal position to R5 an asymmetrical carbon atom in the side chain and can be separated into the optical antipodes in con-ventional manner. (Fractional crystallisation or column chroma-tography optionally with compounds of the formula I or of the intermediates of the formula II and further reaction of the separated antipodes). The antipodes I have di~fering micro-bicidal action.

-¢ne or two additional ~symmetrical carbon atoms are also presentin the acyl side chain. l~e position isomerism of the substi-tuents R6, R7 and R8 also has an influence on the s~rength of the microbicidal action.

Irrespective of the optical isomerism referred to, an atropi-somerism is observed as a rule about the phenyl N " axis in those cases in which the phenyl ring is substituted at least ;

~ 3~ ~

in the 2,G-position and at the same time unsymmetrically to this axis (i.e. optionally also on account o~ tl~e presence of additional substituents).

Provided a synthesis with the object of isolating pure ;somers is not carried out, a product of the formula I will normally be obtained as a mixture of these possible isomers.

The followlng Examples illustrate the invention in more detail but imply no restriction. Unless otherwise stated, an active substance of the formula I is always to be understood as meaning the racemic mixture.

- g _ ~ ~ 2 ~ 3~ ~

Example 1 (according ~o process variant A) C~l CH3 r--~ 3 / ~ C~l-COOCH3 Preparation oE ~ - N \
CH3 CCH2CH20C~13 O

N~ methoxycarbonylethyl)-N-3"methoxypropionyl-2,6-dimethyl-aniline ~Compound 1]

13 5 g of 3-methoxypropionyl chloride are added at room temperature to 20.7 g of N-(l'-methoxycarbonyl.ethyl)-2,6-dimethylaniline in 150 ml of toluene. Ater re1uxing for 16 hours and simultaneously introducing nitrogen, the reaction solution is cooled, washed with dilute aqueous sodium carbonate sclution, dried over sodium sulphate and filtered The solven. is evaporated and the oily residue purified by distillation. Boiling point: 128-136C/O.l torr.

, ~

3~7~ -~xampl _ (according to process variant C) Preparation of N~ methoxycarbonylcthyl)-N-3l'-methoxypro-pionyl-2,6-dimethylanili.ne 0,23 g of sodium (0.01 mole) is dissolved in 100 ml of methanol, A solu~,ion of 13 g (0,05 mole) of N-(l'-me~hoxy-carbonylethyl)-N-acryl-2,6-dimethy'laniline in 50 ml of methanol is added dropwise to the above solution at roo~
temperature. The reaction mixture is refluxed for 20 hours, cooled, and concentrated. The oily residue is taken up in methylene chloride and washed wi~h water. The methylene chloride solution is dried over sodium sulphate, filtered and concen-trated. The oily residue is fractionated. The desired product boils at 130-136C/0.1 torr.

' s Example_3 (according to process variant B) Preparation of N~ methoxycarbonylethyl)-N-3"-methoxy-propiony:l-2~-dimethylaniline

2,3 g (0.1 mole) of sod:ium are dissolved in 100 ml of methanol and 17.1 g (0.05 mole) oE N-(l'-methoxycarbonylethyl)-N-3"-bromopropionyl-2,6-dimethylaniline, dissolved in 50 ml o methanol, are added dropwise at room temperature. The reaction mixture is stirred at this temperature overnight. After con-centration by rotary evapora~ion, the oily residue is dissolved in ether and washed with water. The ether solution is dried over sodium sulphate, fi1tered and concentrated, The desired product distills at 129-135~C/O.l torr.

~L~Z~L376 Rxample 4 ~l3 C~l3 ,~13 Preparation of ~ / CH-COOCH3 Cll C C~ C~120C~13 N~ methoxycarbonylethyl)-N-3"-methoxybutyryl-2,3,5,6-tetra-methylaniline [Compound 43~

..
7.05 g (0.03 mole) of N-(2,3~5,6-tetramethylphenyl)-alanine methyl ester are added to 90 ml of ~oluene and 4.5 g (0.033 mole) of 3-methoxybutyryl chloride, dis~olved in 10 ml of toluene, are added dropwise at room temperature. The reaction mixture is refluxed for 16 hours whil~ slowly introducing nitrogen. After cooling and concentrating the solu~ion in yacuo, the semi-solid residue is taken up in 60 ml of methylene chloride and this solution is washed with 30 ml of lN-~aOH
solution and then twice with 100 ml of water. The organic phase is then separated, dried over Na2S04, filtered, and freed from methylene chloride in a weak vacuum. The end pro-duct is a dark brown oil, which is purified by molecular di-stillation. Boiling point: 131-135C/0.06 torr. The following compounds are obtained in analogous manner or by one of the methods described above: -. ~

~2~37~

R R ,CH3

3 ~ 1 CH-COOCH3(I c ) N`
R4 r c z(Rl = 2-pogition) _ . _ . _ Com- R R2 3 R4 Z Physical ~ound 1 __ _ constarlt C
~. __ ~ _ . __ 1 CH3 6-CH3 H H -CH2-CH20CH3 b. p :l28-136l 2 CH3 6-CL H H -CH2CH20CH3 b, p 132-140/
3 C3}17 (i) 6-C3H7 (i) H H -CH2CH20C~I3 oil

4 CH33-CHC33 6-CH3 H -CHCH20CH3 b. p 120-123/

CH 34 -O -CHC2H5 H H -CH2CH20CH3 oil 6 CH36-C~13 H H -CH2cH2c2HS O. 06 torr 7 CH36-CI. H H -CH2CHOCH3 b.p 137 142/

8 CH3 6-Cl H H ~CH2CH20C2H5 b . p 145-152 ~

9 CH 3 ~ . 3 H H CH C~l 2 C~l 3 __~__ .

.

: , :

~Z~3~
_ _____ Com-- ~ R2 R RL Z Physical pouTld 1 3 ~ . constant C
_ _ ~ _ . ...
3 7 ( ) 3 7 ( ) ¦ H -Cl-l2cH2c2HS 0 03 tor-. . . C~H3 11 C~13 6-C1~3 H H -CH2CHOCH3 b, p 119-122 /

. C,H3 12 CH3 6-C1 U H CllCH20CH3b . p 123-135/

13 CE13 6-CH3 H H -CH2CH20C3H7 (i) 0 1 to-rr 14 CH3 3-CH3 5~( H 6-CH3 CH2CH20CH3m, p. 89-91 CH3 4-C1 5-CH H -CH2CH20CH3m. p. 64-66~
16 CH3 3 C~13 6-CH H -CH2CH20CH3m. p. 35-37 17 CH3 6-C~13 H H -CH2CH20C3H7(n)b,p 160-180/

18 C3H7 (i) 4-Br ~ 3 7 ( ) H CH2~2CH3 19 3 3-C~3 5-CH3 6-CH3 2 20C31 5 b.p 140-144/

CH3 4~Br 6-CH3 H -CH2C~120C2H5b.p 160-165/

. . ~C,~13 21 C~13 6-CH3 H H 2 2 5 .
22 CH3 3-CH3 6-CH3 H -CH2CH2C2H.; 0 08 tor.

: . CH 3 23 CH 3-Cl 6-CH H ~ HCH OCH3b.p.128-132/
3 . 3 2 O. 05 torr 24 OGll3 6-CH3 H H -CH2CH20CH3 l~

2 5 CH 3 ~ - CH 3 6 - CH ~ 11 0 1 t orr , _~ _ _ __ ~

~12~3~ Ei _ _, ~

p~lmd Rl R2 R3 ~4 ~constant C
. ~_ _ 2 6 O CH 3 CH 3 H ~l CH

27 CH3 6-C2~15 H H CH CH3CH b 0 08 Lorr 28 CH3 6-C2H5 H ~l 2CH20C~13 b p- 131~133/
û . 08 torr . CH3 CH3 4 -Cl 6 -CH3 H CH2CH2C2H5 C,H3 ~ .
31 CH34-~C~-~C H ¦ H H -CH2CH20C2~5 3~ CH3 3-Cl 6 CH H -CH2CH20CH3 ~,p.123-130 /
. . I 0.04 torr 33 CH3 6-OCH3 H H -Cl12CH20C3H7 (i) 34 CH 32 5 H H 2 Cll 20C2H 5 b . p 13O- 1 32 /
. ¦ . CH3 CH36-C2H5 H H CHCH20CH3 b . p .117-123 /
. . I 0. 05 torr 36 (~ 3 3-Cl 6-CH3 H 2 2 2 5 1 o 05 torr 37 C3H7 (i )4 -Br -C3H7 ~i ) H 2 2 2 5 1 o 04 ~orr 38 C~3 4-Br 6-C~3 H 2 2 1 0 1 torr 39 3 4~CH3 6-CH3 H -~H2CH2C2H5 Po 15 torr . CH3 CU3 3-CH3 6-C~3 H -CH2CIIOCH3 bl p ~34 138 ___ -~ .:

' ~l~Z~37~

___ _ ~ _........... _ __ . _ _, ~
Com- Rl R2 3 R4 z Physical p ound __ ~ ~.__ __ ~ C, 113 c o~ ~ e ~n e ~:

41 CH 3-Cl 6-CH H -CH2CHOCH~ b .p. 118-125 . 3 3 . 0. 05 torr 4 2 l C 1 4 -Br ¦ 6 -Br ~ H ¦ -CH2CH20CH ~ b, p 1 / 0-1 43 CH3 3-C~3 5 Clt13 6-C~I3 ~CH2CHOCH3 0. 06 torr 44 CH3 3-CH3 6-CH3 H -CH2CH20C3H7 (i) viscous CH3 3-CH3 5~CH3 6-CH3 -CH2CII20C3H7 (i) viscous 4 6 CH 3 6 -C 1 H H -CH 2CH20C 3~I 7 ( i ) oil 47 3 7 ( ) 4-Br C3H7 (i) H -CH2CH20C3H7 (i) i800/

. ~ ¦ 0. 2 to~r as well as the compound ~H 3 ~ 3 ~J~ CH - COOCH3 No. 48 <~--N \ - b.p. 163-164/0,8 torr - . CH3 C0-CH-CH2-0cH3 ~ ~ Z ~ 37 ~
The following c~mpounds are also prepared in analogous mamler:

R CH3 (I d) 3 ~< 1 / C11COS CH 3 ~N
P.2 C-Z (R1 = 2-POSitiOn) Com- : ~ R2 R3 R4 ~ Physlcal pound l constant C
. _ _ _._ _~_ _ 4 9 CH 3 6 -CH 3 H H -CH 2CH20CH3 m . P 7 1 - 7 3

5~ CH3 3~CH3 6-CH3 H CH2CH2CH3 O 05 tOrr 51- CH3 4-BL- 6-CH3 H CH~CI12CH3 b po350l 52 CH3 3-CH3 5-CH3 6-CH3 -CH C~l OCH m.p. 76-78 53 CH3 6 -CH3 H H ~CH2C~2 ~C 2~15m.p.73-75 54 CX3 3~CH3 6-CH3 H CH2CH2 2 5 . 05 tOrr CH3 3~CH3 5-CH3 6-CH3~C~2CH20C2H5m. P. 79-80 56 CH3 4-Br 6-CH3 H CH2CH2 2 5 O. i torr . C~l3 I
57 CH3 6 -CH3 H H -CHCH20CH3 o 13 t r 58 CH3 3-C1 6-CH3 H -CH2CH20C2~15 b ~- 8-~30/
5~ . CH3 3-C1 6-CH3 H -CH2CE12OCEI3 0 05 tOrr CH3 4~C1 6-~3 H ~ -CH2CH~CH3 b P 128-131 61 CU3 4-Cl 6 ~1~ H -CH2CH20C2H5 0 0~ t .

... . . . ,. ~ . . . . . ...... ~ . . .... . .... ............ . .

.

2~3~ ~

T~le compolmds of ~he ~ormula I can be used by ~llemselves or ~ogether with suitable carriers a.nd/or other additives.
Suitable carriers and additives can be solid or liquid and corre.spond to the substances normally use~l in the art of fol~ulation~ for example na~ural or regenerated mineral sub-stances, solvents, dispetsants, wetting agents, tackifiers, thickener~, blrlders or fertilisers.

The content of active substance in commercial compositions is between 0,1 and 9C%.
For application the compounds of the fo~ula I may be processed to the ollowing ormulations (in which the parts by weight reer to advan~ageous amounts of active substance):

Solid formulations:
dusts, tracking agents (up to 10%);granules ~coa~ed granules, impregnated granules and homogeneous granules), pellets (1 to 80%);
.
.Liquid formulations:
a3 active substance concentrates which are dispersible in water: wettable powders, pastes, (25-90~/o in commercial packs, 0.01 to 15% in ready-for-use solutions);concen trated emulsions and solutions ~10 to 50%; 0.01 to 15%
~n ready-for-use solutiotls).
b) Solutions (0.1 to ~0~/O); aerosolsO

~ 3~ 6 The aetive su~stances of ~lle ~oLnlula I of the present inventior~
can be o~ulated for ex~(~ple as follows-Dusts: The ~ollowing s~lbstances are used to preparea) 5% a.nd b) a 2% dust:
a) 5 parts of active su~stance 95 parts of talc 9 b) 2 par~s o~ active su~stance 1 part of highly dispersed sil~.cic acid 97 parts o~ talc.

The active substances are mixed with the carriers and gro~mcl and in ~his form can be processed to dusts for application.

Granulate: The ~ollowing substances are used ~o prepare a 5% granulate:

S parts of active substances - 0.25 part of epic~lorohydrin ~ 0.25 part o cetyl polyglycol ether 3,25 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol etller are added. The resultant solution is sprayed on kaolin and the acetone is evapora~ed in vacuo~ Such a microgranula~e is advan~ageousl.y ~Ised or ~1 3 combating soil ~ungi.

We~table powd~rs~ T~e ~ollowill~ constltuents are used to prepare a) a 70%, b) a 40%, c) alld d) a 25% and e) a 10%
we~table powder:

a) 7~ parts of active subs~allcc S parts of sodi~ dibutylnaphthylsulphonate 3 pa~ts of naptltllalenes-llphonic acid/phenolsulphonic nci~/formaldellycle con~lensate ~3 :2 :1) parts of kaolin 12 par~s o$ Challlpagne c~lalk b) 40 part s o~ ac t ive sub ~; t 11lC e parts of sodi~ Ligninsulphonate part of sodium dibul:ylnaphthalenesulphonic acid - 54 parts o~ silicic aci~

c~ 2S parts of active su~s~atlce 4.5 part~ of calcium li~ninsuIphona~e 1. 9 paxts o Champagne c~lalk/hydroxyethyl cellulose m~xture (l:lj 1. 5 parts o sodium dibuty~naphthalenesulphona~e 19.5 parts of sil~cic acid l9.S parts o ChalDpagne chalk 28.1 par~s o~ kaolin d~ 25 parts o act~ve su~stance 2.5 parts of isooctylpllelloxy-polyethyLe{le-ethanol 1,7 parLs o a Chalupagne chalk/hydroxyethyl cellulos~
mixture (1:1) 8~ 3 parts of sodium alului~lium silicate 16 . 5 parts of kieselguhr 46 par~s o~ kaolin e) - 10 parts o~ active sul~stance par~s o~ a mi.x~ure c ~he sodi~um salts o saturat~d atty at cohol sulp~ates 5 parts s~ naphthalerlesulphonic acid/formaldehyde condellsate 82 parts of kaolin, The act~ve substances are in~uately mixed in sui~abLe ~nixers Wi~l the additives and ground ill appropriate mills and rollers.
~ett~ble powders o excellen~ wet~ability and suspension po~dcr are obtained. These we~ctablë powders ran be diluted wLth water t5:~ give suspensions of the desi~ed concentratlon and can be - used in particular for lea~ application.

Emulsifiable concentra~es: Th~ ~ollowing substances are used .
to prepare a ~5% e~ulsifiable collcentrate parts of active subs~ance .S parts of epoxLdised.~egetable oil L37~

10 part:s o~ an all~ylarylsulpllonate/~atty alcohol polyglycol ether mi~Lure 5 pal'l~S of di~net:hyl ~oLIn~uide 57, 5 parts of xylene.
By dilutillg such a concentrate with wat:~r it is poss~ble to prepare emtllsions o~ tlle desired concentration, which are e~pecially suit:able or lea~ applicat:ion.

.

~ .3 Example 5 ction against Cerco~s~o ~ per.so~ a ~ r ~ on ground nut plants Three-week-old ground nut plan~s were sprayed with a spray mixture (containing 0.02~/~ of ac~ive substance) prepared rom a wettable powder of the active substance. After about 12 hours the treated plants were infected by dusting with a conidia suspension of the fungus. The infected plants were then incu-bated for about 24 hours at ~ 90V/o relative humidity and then stood in a greenhouse at about 22C, The fungus attack was evaluated after 12 days..
In comparison to the untreated control, plants treated with active substances of the formula I exhibited a slight or almost no attaclc by fungus.

~ - 24 --~2~37~
Example 6 Act-ion a~ inst Plasmo~ viticola (Bert. et Curt.) (Berl. et de Toni) on v nes a) Residual preventive action Vine cuttings of the variety "Cllasselas" were reared in a greenhouse. Three plants in the 10-leaf stage were sprayed with a spray mix~ure (colltaining o.o6% of active substance) prepared from the active substance ancl fonmulated as a wett~
able powder, After the coa~ing layer had dried, the plants were in~ected on the underside of the leaves with the spore suspension of the fungu.,, The plants were subsequently kept in a humid chamber for 8 days~ a~ter wllich time s~nptoms of the disease were visible on the control plan~s. The effective-ness o~ the tested substances was assessed by detennining the number and size of the infected areas on the treated plants.

In this test, the compounds of the formula I were highly effect- -ive against powdery mildew on vines without detrimental effect to the plants. Fungus attack was completely inhibited with compounds 1, 14, 16; 32, 43 and 52.

: . :
.

~ ~ Z ~ 3 Example 7 Actio~ a~inst Phyto~hthora infes _ns on tomatoes I) Curatlve Action .
"Ro~er G~om" ~oma~o plants were sprayed when 3 ~Jeeks old with a ~oospore suspension of` tlle fullgus and lncubated in a clima-tic chamber at 18 to 20C and saturated hwnidlty. The humi~
difying was interrupted after 2b hours. After the plants had dried, they were sprayed with a spray mixture containing the active substance formulated as a wettable powder in a concen~
~ration of 0.06%. A~ter the spray coa~ing had dried, the plants were again kept in the humid chamber for 4 days. The efectiveness o the tested substances was assessed by deter-mining the size and number ~f the typical leaf specks wllich had occured during this time.

II) Preventive-systemic action The active substance fo~nulated as a wettable powder was applied in a concentration o 0.006% (referred to the volume of the soil) to the surace of the soil of 3 ~eek-old "Roter Gnom" tomatoes in pots. ~tree days later the underside of the leaves of the plants was sprayed with zoospore suspension of Phytophthora infestans, The plants were then kept in a spray chamber at 18 to 20C and saturated humidity for 5 days, after which ~ime typical leaf specks formed. The efectiveness of the tested substance was assessed by determining the size and number Gf .the specks.

~L~2~1L3~

In both these tests, the compounds of the formula I exhibited a good leaf-fungicidal action.

Test I: Fungus attack was completely controlled by compounds 2, 14, 16, 19, 32, 41 and 43, and with compo-mds 19 and 43 also in a concentration of 0.02%.

Test II- Fungus attack was completely controlled with compounds 1, 2, 6, 7, 8, 9, 11, 12, 14, 15, 16g 22, 23, 27, 2~, 32~ 34, 36, 40, 41~ 43, 48, 49, 52, S9, and also with compounds 1, 2, 7, 8, 9; 14, 16, 28, 40 and 43 in a concentration of 0.002%, .
, :~ .

.

37~
Example 8 -Action on Eri~ rami1:lis on l~lrley Residual rotective action . P - _ _ Barley plants approx. 8 cm i.n h~i.ght were sprayed wlth a spray mixture (o.o6% of active su~stance) prepared from a wettable powder of the active substanceO AEter 48 hours t~!e treated plants were dusted with conidia of the fungus. The infected b~rley plants were sto~d in a greenhouse at approx.
22~C,and the fungus infection was evaluated af~er 10 days.

.A large number of compounds o-E the formula I effected in this test a reduction of the fungus attack to markedly less than 10%, e.g. compounds 6, 16, 43 and 59. The fungus attack was completely con~olled with compounds 20 and 34.

~ 2~ -

Claims (9)

WHAT IS CLAIMED IS:

1. A compound o the formula I

(I) wherein R1 represents C1-C4alkyl, C1-C4alkoxy or halogen, R2 represents hydrogen, C1-C3alkyl, C1-C4alkoxy or halogen, R3 represents hydrogen, C1 C3alkyl, C1-C4alkoxy or halogen, R4 represents hydrogen or methyl, with the proviso that the total number of carbon atoms of the substituents R1, R2, R3 and R4 in the phenyl ring does not exceed 8, R5 represents -COOR', -COSR', in which R' represents methyl or ethyl, R6 represents hydrogen, methyl, C1-C3alkoxy, R7 represents hydrogen or methyl, and R8 represents C1-C3alkoxy.

2. A compound of the formula I according to claim 1, wherein R1 represents methyl, R2 is in the ortho-position to the amino group and represents methyl, ethyl, chlorine or bromine, R3 represents hydrogen, halogen, para(C1-C4)alkoxy or methyl, and R4 represents hydrogen or methyl, whilst R5 to R8 have the given meanings and R' represents methyl.

3. A compound of the formula I according to claim 2, wherein R5 represents the group -COOCH3.

4. N-(l'-methoxycarbonylethyl)-N-3"-methoxybutyryl-2,3,5,5,6-tetramethylaniline according to claim 1.

5. A process for the production of a compound of the formula I according to claim 1, which comprises reacting a compound of the formula II

(II) with a carboxylic acid of the formula III

(III) or with the acid anhydride or acid halide thereof.

6. A method of controlling phytopathogenic fungi and of preventing attack by fungus, which comprises treating plants, parts of plants or their environment with a compound of the formula I of claim 1.

7. A method according to claim 6 which comprises the use of a compound as claimed in claim 2 as active component.

8. A method according to claim 6 which comprises the use of a compound as claimed in claim 3 as active component.

9. A method according to claim 6 which comprises the use of a compound as claimed in claim 4 as active component.