New anilides, their method of preparation and agents microbicides the container.

The present invention relates to compounds of formula I

wherein R is hydrogen or a methyl group, a process for preparing these compounds, microbicides are containing these compounds as active ingredients, and the application of these compounds as microbicides, preferably for combating phytopathogenic fungi..

The bacterial and fungal disease in plants useful sono-promoted by two factors. Firstly in crops sought primarily yield enhancement and improved quality. Frequently, is lost thereby a portion of the natural force of resistance against parasites. Secondly, experience has shown that the bacteria and fungus acquire largely over the years to a resistance against known pesticides. The result is an urgent need in microbicidal well supported by crop plants and destroying their parasitic direct.

Crop plants which are within the scope of this invention are for example cereals, corn, rice, vegetables, sugar beet, soybean, peanut, fruit trees, ornamental plants, and especially of the grapevines, hops, cucurbit (cucumber, pumpkin, watermelon), the solanaceous plants such as potato, tobacco and tomatoes, and bananas, cocoa and natural rubber.

It has been found surprisingly that with the active substances of the formula I may be combated or destroy fungi that exist on plants or parts of plants (fruit, flowers, foliage, stems, tubers, roots), on these crop plants or other analogs and the parts of plants that appear subsequently are protected against fungi of the genus. The active substances are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Zrysiphaceae); Basidiomycetes, as especially the anti-rust-; Fungi; but also especially against Gcmycètes belonging to the class of Phycomycetes, as Phytophthora, Peromospora, willwill pseudoperonospora, Pythium or pathogen. The more the compounds of formula I have a systemic action.

They may further serve as mordants for treating seeds (fruit, tubers, grain) and plant cuttings to protect against fungal infections and act against phytopathogenic fungi exist in the ground.

The methyl esters of Tl - (substituted phenyl) - n furanoj L-alanine of formula I are a class heretofore unknown novel microbicides, YES are markedly superior in their field of use to known compositions of commerce.

The compounds of formula I are prepared by a process according to the invention, for example by acylating a compound of formula II

(II)

by acid furan - (2) - carboxylic, its acid halide, anhydride or ester thereof, or, in particular cases, by a furan - (2) - carboxamido (transamidation reaction).

In another method according to the invention the compounds of formula I can also be obtained from the acylanilices of formula III

that Mft 'elm with butyl lithium or sodium hydride in the corresponding alkali salt which results then with has a-halopropionate methyl at desired end product or also with 1 'a-to-halopropionate methyl in the presence of an alkali metal carbonate such as potassium carbonate as proton acceptor, preferably with the addition of catalytic amounts of an alkali metal iodide, such as potassium iodide.

In formulae II and III, 'R represents hydrogen or methyl, expression acid halide preferably signifies the chloride or bromide acid and the halogen atom of 1 'a-to-halopropionate methyl is preferably chlorine or bromine.

The reactions can be conducted in the presence or in the absence of solvents or diluents inert towards the reactants. It consists for example of the following solvents: aliphatic or aromatic hydrocarbons such as benzene, toluene, the Xylole, petroleum ether; hydrocarbons such as halogens chlcrobenzene, methylene chloride, ethylene chloride, chloroform; ethers and ether as the compounds of the genus dialcoyl ethers, dioxane, tetrahydrofuran; nitriles as 1' acetonitrile derivative, of H, as the ITdialcoylamides dimethylfomamide solvate, anhydrous acetic acid, dimethylsulfoxide, ketones such as methyl ethyl ketone and mixtures of these solvents by themselves.

The reaction temperatures are between 0° and 18g °C, preferably between 20^I and 120° g. In many cases the use of acid scavengers or condensation agents is advantageous. As such include tertiary amines as the trialcoylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases as oxides, hydroxides, bicarbonates and alkali metal carbonates and alkaline earth, as well as sodium acetate. Acid acceptor as another alternative is to use an excess of the aniline derivative implemented.

The method of preparation starting from compounds of - zu, slipper II can also be driven without acid acceptor and in some casj it is then indicated a current, nitrogen to flush the hydrohalic acid formed. In other ' case, it is advantageous to add the. aiméthylformanide catalyze the reaction.

Details for the preparation of intermediates of formula II can be found based on the methods that have been published in the organs publish the following for the preparation of acid esters aniiino-alkanoic acids:

J Qrg. Mal. 30, 4101 (1965)

Tetrahedron1967 , 487,

Tetrahedron1967 , 495 ·

The compounds of formula I have in their chain propionic ester an asymmetric carbon atom, and can be solved in a known way to the optical antipodes. It is the enantiomeric form d which has the strongest microbicidal activity.

In the context of the invention it is preferred accordingly the compounds, agents and their use, which rest on the D configuration of formula i. these forms d are in ethanol or 1'.acétone a rotation angle negative.

To obtain the antipodes with optically active d-prepared racémicue e.g. the compound of formula IV

(IV)

then ά℮ known way is followed by reaction with a nitrogen base optically active to obtain the corresponding salt. By fractional crystallization of the salt and subsequent freedom in OD of acid of formula IV ' enriched the antipode of d and optionally (if necessary several times) salt-forming operations, crystallization and brought freedom of a-anilinopropi YES that of formula IV, is obtained by steps purification and neat. From thereof, is may, conventionally, e.g. in the presence of hydrochloric acid or sulfuric acid, obtained with methanol the optical configuration L of the ester of formula II. As optically active organic base it consists for example of dc-phenylethylamine.

Instead of the fractional crystallization, can also be achieved the form d-enantiomer of formula IV by exchange of the hydroxyl group existing in L (+) - lacticue (which exists in nature) for halogen and reacting this product with reversing of the configuration with the 2.6 to-dimsthylaniline or the 2, 5, 6 a-Trimethylaniline desired.

Confectioneries side of the optical isomerism occurs in the

case where s=CH2 -, with the furanoylation of compound II (or with

P

reacting the compound III with has-HAs-to-lopropionate methyl)

a atropisomery about the axis phenyl, conditioned by the steric hindrance of the two radicals additionally introduced on the nitrogen atom of the Trimethylaniline._:

As far as is not synthesis is expected for the isolation of pure isomers, the compound consumption called farther from the compound t7 degrees 2 forms in the preparation as a mixture of e - isomers. The fungicidal activity more favorable shape d-enantiomer (as compared to the shape of d-L or L) is however maintained and not influenced appreciably by 1¹ the ATR IPO e adorned Rl th.

The preparation of active compound of formula I is illustrated by the examples 1 and 2 (temperatures in degrees Celsius).

Example 1 '

Obtaining

Has 1s, 2 g of L - (1 - scrambled thoxycarbonyléthyi) - 2.6-dimethylaniline in 10 ml of anhydrous toluene and 0.2 ml of dimethylforremide, is added dropwise with stirring 12.6 g chloride acid furancarboxamide 2-carboxylic. - ^ hen the reaction low exotherm subsided, is heated to reflux for five hours and completely removed the hydrochloric acid formed by a nitrogen stream. After removal of the solvent is distilled under vacuum: d.w.=166 - d68 degrees/0, 06 forr. The final product solidified melts, after recrystallization from toluene/petroleum ether, between 81 and 84°. The diagram shows that the Eontgen powder compound is polymoi ' to Phe. A modifications 85° to bottom.

The configuration enantiomer b and its precursors have the following physical constants:

Apple (b.)

(α) ¾⁰ +=10.7 + 0.3 DEGREES;

C=1.56 p/v in ethanol

(D.) Porme

(has)=+ j° 29.8 + 0.5 degrees;

C=1.55 % p/v in methanol form (D.) 657 1c2 - 1c3⁰ (gFOC=g=1.73 c/o p/v - 47.0 + 0.7 degrees in 1' acetone

hence he - (C'a-msthoxycarbonyl-ethyl)~~n-(GBP uranium oxide - (2") - carbonyl-) - 2, 3, 6 and .aniline.

a) a suspension of 51.5 grams (0,382 moles) of 2, 3, 6 and trimcthylaniline, 35.3 s of lïaHCO - and 126 ml (1.15 moles) of 2 tert-methyl is stirred for 6 hours at a temper ATs ERUs/ie bath 130 degrees, and then cooled, freed of salt by filtration and distilled: 67.3 s has - (2, 3, 6 and triméthylanilino) - methyl propionate boiling/144 - 146° to 9 Torr or less.

b) a suspension of 33.5 seconds (0,152 mol) of the ester obtained in a) and 18 grams (0.17 moles) of sodium carbonate in 200 ml absolute benzene is added drop-wise to 16.7 ml (0.17 moles) of acid chloride furancarboxamide 2 a-carboxyiic to 60 -? 0° - and further kept during 4 - hours. After cooling, filtering and concentrating the filtrate product is recrystallized in 1' isopropyl ether. PP.F, 98 102°.

When the D-form of acyl 1 · α - (2, 3, 6 and triméthylanilino) - methyl propionate with acid furan - (2) - carboxylioue or a reactive derivative thereof, is: obtains the form d of the compound 2 as a mixture of atropisomers (=compound 2a). The percentage of each of these isomers depends on particular operating conditions.

The compounds of formula I may, in order to enlarge their spectrum of action, be implemented with other suitable pesticides or with growth promoting substances.

The compounds of formula I may be employed alone or with carriers and other suitable additives. The supports and suitable additives may be solid or liquid and correspond to the customary substances employed in formulation, such as natural or mineral substances. regenerated, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The active substance content in the agents, is between 0.1 and commercial 90%.

For the application, the compounds of formula I may be in the following forms (the percentages shown in parenthesis are most advantageous):

solid forms: dusting powders and spreading (up to

10>-) 5 granules, coated granules, impregnated granules and homogeneous granules (1 to 80 %) VBE1forms liquid:

a) concentrates of active water dispersible; powders for spraying (wettable powders) and pastes (25 to 90 % in the packaging marketed, 0.01 to 15 % in the ready to use solution);

concentrated emulsions and solutions (10 to 50 c/o ; 0.01 to 15 % in the ready to use solution;

b) solution (0.1 to 20%).

The active compounds of formula I may for example be formulated as follows:

jam Nur dusting : give the dusting has) to 5, 2 and b) to 2 c/o used the following substances:

a) 5 parts of active substance l° 2,

95 parts of talc;

b) 2 parts of active substance 1t 1 degrees,

1 part of finely divided silica,

97 parts of talc.

The active substances are mixed and milled with the holders may be employed sound this form.

C rannl - 1 : 5 To obtain a granule is used the following substances:

5 parts of active substance ii ' 1 degrees,

0.25 part of epichlorohydrin,

0.25 part cétylpoiyglycol ether,

3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3 -

0.8 nm).

The active compound is mixed with epichlorohydrin and dissolved in 6 parts of acetone, followed by adding polyethylene glycol and cétylpoiyglycol ether. The solution thus obtained is sprayed onto kaolin, and then vacuum-dried, microgranulate such is advantageously employed for combatting fungi soil.

- Nur powder spray : To obtain a spray powder has) to 70 b.) to 40 C.) and d) to 2ÿ c/o and e) 10 to % employed the following components:

has) 70 parts of 17 - (1^, - methoxycarbonyl-ethyl) - K [furan (2") - carbonyl-] and 2.6-dimethylaniline, active substance № 1a (D-form), according to the invention,

5 parts sodium dibutylnaphtylsulfonate

3 parts condensate acids naphtalênesuifouiquesacides phenylsulfonic-to-formaidéhyde ^ 3 2:1,

10 parts of kaolin,

12 parts chalk champagne.

b) 40 parts of active substance 17° 2,

5 parts of sodium salt of ligninesulf0 -

nor that,

1 part acid sodium salt uioutylnaphtalenesulfonic,

54 silicioue acid portions;

c.) 25 parts of active ingredient I ' degrees 2 (D-form)

4.5 parts of calcium lignosulfonate,

1.9 mixing part champagne chalk (1:1)/hydroxyàthylcellulose,

1.5 part dibutyl naphthalene sulfonate sodium, 17.5 parts of silicic acid,

' 19.5 parts chalk champagne,

26.1 parts of kaolin;

d) 25 parts of active substance it° 2,

2.5 parts a'a' isooctylphénoxy-polyoxyethylene ethanol, 1.7 parts of mixture/champagne chalk - hydroxyl ethyl cellulose (1:1)•

8.3 parts of sodium silicate and aluminum, 16, 5 parts of kieselgur,

46 parts of kaolin;

e) 10 parts active substance 17° 1a (D-form)

3 parts. mixing of sodium salts of alcohol sulfate_C. saturated fatty,

5 parts naphtalenesuifonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are mixed intimately with the additives and ground on mills and corresponding rollers. For spraying powders are obtained having excellent wetting and suspending, which can be diluted with water by giving all suspensions. desired concentrations and are useful per 1 'application on the sheets.

For obtaining an emulsifiable concentrate to 55 % employed the following substances:

25 parts of active substance 17° 1

2.5 parts of epoxidized vegetable oil

1C alcoylarylsulfonate/parts of a mixture of fatty alcohol polyglycol ether

5 parts of dimethylformamide

57.5 parts of xylene

it from such concentrates, can, by dilution with water, emulsions of any desired concentrations, YES are suitable for foliar application,

Example 5

Activity against Phytophthora infestans on Colanum willwill hprtoohthora. Iqcouersicnm(=tomatoes)

the) Waste preventative action

Plants Solanun lycopersicum histidine e ' roughened " Brownie iOUi ' th " are, three weeks after being sprayed with a slurry containing c, c5 % active substance (obtained from active substance which is formed under iorme a spray powder) and dried, infested with a suspension zoospores of Phytophthora infestans. 6 Maintained during the days in a conditioned room to 18 - 20° to high humidity obtained by an artificial mist. After said time observed stains on the sheets. Their number and their extent of a scale for the examined substance,

Lb) Curative action

Tomato plants of ' the species "Brownie red" are, three weeks after being sprayed, infested with a suspension of zoospores fungus and incubated in each car at 18 - 1:0 ° in air saturated with water. Release of the humidifying after 14 - hours. After drying plants, these are sprayed using a slurry that contains the active substance formulated in spray powder at a concentration of 0.05 (greatly accelerated. After the drying of the slurry plants are held again in the humidification chamber during 4 days. The number and size of typical stain on the sheets express activity substances examined.

II) Systemically active preventative.

The active substance formulated in spray powder is added at a concentration of 0.05 % (calculated on the volume of the soil) on the ground surface of three pot of tomatoes. three weeks of the species "Brownie red". After three days of rest the underside of the plants is sprayed with a suspension zoospores of Phytophthora infestans. They are then stored in a fluidized spray booth 18 - 20° and in water saturated atmosphere. After this time it the stain removal caractéristioues whose number and the tee is to express the activity of the substances.

In these three tests, the compounds of formula I showed strong antifungal activity on the sheets, it is to say that fungal attacks are less than 5 * In the d-compounds, it is to say for the compounds 1a and 2a fungal attacks are always lower than 5 λ even for an application rate of 0.02

/5 Χ℮ηρ ℮ 4 1

Activity against willwill liasnonara viticola (with Bert, and Curt.) (- and Β℮ γ 1. The curly DePorhf ν ;τ· β 1

has) WTA is rréventive residual

5 Is raised in greenhouses of vine cuttings of the ES

- article having "Chasselas". At stage 10 sheets, three plants were sprayed with a slurry obtained from an active substance formulated in spray powder, after drying, the plances infested are on the bottom surface of the sheet 10 with. suspensions of fungal spores in a uniform layer. The plants are then maintained for 8 days in wet chamber. After this time are shown large symptoms of disease on the control plants. The number and size of infections on the treated plants serve to ex 1p basecoating activity to specific materials used.

b.) curative action

Of vine cuttings of the species "Chasselas" are elevated in the greenhouse and, at the stage of 10 sheets, infested to the underside of the sheets with a spore suspension of TO pathogen viticola. After 24 hours in humid conditions plants are sprayed with a slurry of active substance, obtained from a spray powder.

Is then held the plants during 7 days in the car wet. After said time appear disease symptoms

-5 on the log sheets. The number and the size of the infected areas on the treated plants is to express

5C

the activity of the substances

In these two E:

of formula I show a

concentration:

examined.

periences of the example 4 the compounds high fungicidal activity for the

Compound № concentration of fungal accident

L_ POS ' -? a), and b the j _ 0.05% 0 the c - 5;

100 %

2a

Control

wander... against " 3;31Ur.on the beta vulgaris is iebarvanum<1 (white beet kohlrabi

Acting anres:: L-οη on the ground

the fungus is cultured on oat seeds and added to a sterile soil-. sand, soil and infested is seeded with pots and sugar beet seeds.. immediately after 1' seed preparations from experience are poured onto the ground state of aqueous suspensions (0,002 2 active substance calculated on.

the volume of the earth), the pots are subsequently left during 2 to 3 weeks in a greenhouse at 20 and 24 and degrees Celsius. During this time the earth is maintained uniformly wet by slight watering th 1 'water " for exploiting 1' experience is determining the number of beets and the number of normal and diseased sheets, and b) aerial acre ann11cation mordant

The tank onion. is cultivated on U-grainesy ' oat sterile and added to a mixture of soil and sand. Infested soil and is potted had sown with sugar beet seeds that were mordanted with preparations from experience formulated BO1 (0.1 active substance to the seeds). The pots seeded are held in greenhouse for 2 to 3 weeks to 2c-to-°0 14. During this time the earth is maintained uniformly wet by water spray. For 1¹ operation of the experiment determined the crimped of sugar beet plants and the number of normal and diseased plants.

Under the conditions of both the experiment) that b), 85 F..^: beets are output after treatment with active substances 1, the, 2 or 2a and appearance uniformly healthy. Controls as non-- processed less 20' 2 plants come out and look sick.