Fungicidal compositions containing fungicidal monoaminophosphites.

The present invention relates to fungicidal compositions based on mono substituted amino-derivatized phosphite *

the invention particularly relates to pine compositions to be used for combating fungi plant pests, including mildews, and oomme active material containing a compound of general formula:

* And b - b.₀ the same or different each represents a

1 £,

alooyle radical is linear or branched, optionally hydroxylated or halogen, containing 1 to 10 carbon atoms, the chain can be interrupted by oxygen or sulfur, or an alkenyl group of 2 to 5 aloynyle or carbon atoms, hh.j and Hg may also form with the oxygen atoms and phoiphore cycle to 5 or 6 membered optionally substituted by radicals alkyls containing 1 to 3 carbon atoms optionally halogenated, halogen or 1 to 5 alcoxyalooyles of carbon atoms, the cycle may also be adjoined by a carbon-carbon bond to a phenyl radical,

^ - ^ Of b and b, the same or different, each represent 1' hydrogen, alkyl, alkenyl, aloynyle, aleoxy, hydrocarbon part of CEE radicals containing 1 to 5 carbon atoms,

or fommer may together with the nitrogen atom to 6 membered hétéroeyele a.

The invention also relates to compositions containing as an active ingredient a fongieides metal complex of one of the compounds defined El above: among the metals usable in such complexes, these would include alkali metals and alkaline earth metals, zinc, manganese, magnesium and copper.

These compounds are per se eonnus, but the literature does not indicate that they have fungicidal properties. The general methods of synthesis of these compounds are described in Heuben-to the Weil MECT XII., flight. 2, p 99 to 102.

The most commonly used synthesis comprises reacting an optionally cyclic diester of phosphorous acid on a primary or secondary amine in a solvent medium according to the method of-Lucas, the Mitchell, the Scully (j pieces.

The AM. Mal. Share. 72, 5491 - 6/1950 p)•thus can be, for example, prepare the 2 (m-dimethylamino) 1, 3, 2 subcontract.

Is dissolved 23.5 grams (0.2 meters) of 2-chloro-phospholaae in 100 ml 1, 3, 2 a-dioxabicyclo of petroleum ether. The solution is cooled to 20 °c and 18 grams (0.4 meters) in solution in 50 ml of dimethylamine of petroleum ether are eoulés with stirring while maintaining the temperature between -20 and -10 °c. After the end of the casting, the temperature is allowed to rise, the dimethylammonium hydrochloride is filtered. Petroleum ether is expelled, it remains an oil which is vacuum distilled water to the horn.

The EH ^ theS: 64 and 66° the n ^=1.4715 yield: 67 $# n-c-analysis1 W #

whose characteristics are shown in the following table

These compounds can give complexes with certain metal salts, complexes including the application fungicide is also part of the invention. It is and has been prepared a complex die cuprous chloride and 2 (to nn-diethylamino) 1.3 " 2 subcontract.

Under atmosphere of COGs, 1, 0g added cuprous chloride to I, 6g of 2 (NAN diethylamino) 1.3 " 2 subcontract. The temperature of the mixture rises i00 °C. After recrystallization from alcohol, there is obtained an O, 9 g of a white product.

Yield: 35 1

Melting point 9.ï i2i - I22 °C

Centesimal analysis for hCG - ^ ClCuNOgP

$P-LC

Calculated 13.53 ll, 81

Found 13.48 12.04

In addition, the applicant has found that aminophosphites provide guidance by hydrolysis monoalcoylphosphites ammonium salts according to the scheme:

These salts of ^ - hydroxyethyl phosphite are themselves fungicides and are the subject of the request French Certificate of addition no. 73 - 37,994.

The following compounds illustrate illustratively the fungicidal properties of compounds hereinafter 9.ï

1 To nn 0 O-substituted dimethyl phosphite such as diethylamino

2 2 (ΔNn diethylamino) 1, 3, 2 subcontract

3, 2 (To nn diethylamino) 1.3 " subcontract 2

4 complex of compound 2 with cuprous chloride

5, 2 (N-phenylisobutyrate) 1, 3, 2 subcontract

6 2 (ΔNn phenylpropyl) 1, 3, 2 subcontract

7, 2 1, 3, 2 (To nn and diallyl amine) subcontract

8, 2 1, 3, 2 (I-piperidyl) subcontract

9, 2 (I-morpholinylethyl) 1, 3, 2 subcontract

10, 2 (To nn diethylamino) 4-methyl 1, 3, 2 (I-morpholinylethyl) subcontract 11, 2 4-methyl 1, 3, 2 subcontract 12 2 (ΔNn diethylamino) 4 a-methoxymethyl-1, 3, 2 subcontract

13, 2 (To nn diethylamino) 4.5 benzo subcontract 14, 2 1, 3, 2 1, 3, 2 dioxaphosphorinane (ΔNn diéthylamio).

Example 1 In vivo testing on pathogen viticola on vines

has) Preventive treatment

Is^? milking plants by spraying with a spray gun

vine (cultivar g amay) grown in pots, on the underside of the sheets with an aqueous suspension of a powder mouillabue having the following composition by weight:

20 $- active material to be tested

- deflocculant (calcium lignosulfonate) 5 $

- wetting (alcoylarylsulfonate sodium) 1°

- load (aluminum silicate)⁷ 4 $to the dilution, comprising the active compound to be tested to the dose considered; each test object of three repetitions.

After 48 hours, the contamination is performed by spraying on the underside of the sheets of an aqueous suspension of 80,000 units/cm to about ^ spores of the fungus.

Then the pots are placed during 48 hours in cell incubation to 100 $relative humidity and 20 °c.

We monitor plants nine days after 1' attack.

Under these conditions, it is observed that at the dose of 0.5 g/l, the compounds 1, 2, 3, 4, 5, 6, 7, 9, 11 and 14 exert a total protection and compounds 8, and 13 good protection.

Further, it is seen that none of the products tested showed the least phytotoxicity.

b.) Treatment of initial

Operation is carried out as referred to in paragraph), but differs in that initially made the contamination and then the treatment with the active material to be tested, the observation is made 9 days after contamination.

Under these conditions, it is observed that at the dose of

1 g/l, the compounds 1 and 4 cause a complete growth arrest mildew on grape plants.

Sprayed with more vines (cultivar Fleurie), each being in a bucket containing vermiculite and a nutrient solution, with 40 cms ^ a solution to 0.5 g/l EC to the material being tested. After two days, the vine is contaminated with an aqueous suspension containing 100,000/cm in spore ^ of Plasaoparafviticola. Incubated for 48 hours, in a chamber at 20 °c and 100 $relative humidity. The observation of the degree of infestation takes place after 9 days about, relative to a control infested which has been sprinkled with^40 cm in distilled water.

Under these conditions, it is observed that, the amount of 0.5 g/l, the compounds 2 to 14 absorbed by the roots exert a protective total leaf vine downy mildew, which shows well the systemic character of these compounds.

Is treated at stage 7 sheets of vines (cultivar Fleurie), each being placed in a bucket containing a mixture of dead ground and sand "

The treatment is effected by spraying onto the underside of the lowermost sheet 4 a wettable powder containing 2.5 g/l of the active material to be tested.

After 2 days, the vine is contaminated with an aqueous suspension containing 100,000/cm to about ^ spore Pathogen vitieola. Incubated for 48 hours in a chamber 100 and 20 °c $> relative humidity, the monitoring of the level of infestation takes place after 9 days about on the 7th to 5 sheets from below, with respect to a TiN cookie that has been treated with distilled water.

Under these conditions, it is observed that the compounds 1, 2, 3 * 4, 5, 8, 9 and 14 exert a total protection and compounds 7, 13 and t1 good protection of the sheets high vine downy mildew.

Example 4 : Outdoor test on downy

Grape vines groups (Camay) are infested naturally at the beginning of the month of August heavy rain and frequent watering. These groups of plants are then processed after 8, 14, and 23 days respectively using slurries of wettable powders to #50 respectively containing as an active ingredient the compound η⁰ The I, ethylene bis-1.2, dithiocarbamate maneb and manganese or the mixture of these two compounds.

The following table gives the results of observations respectively 2, 8, 20, 35 and 45 days after the last treatment. These results are expressed in percentage protection against a control untreated but contaminated.

This figure shows ii

- on the one hand, the excellent immediate action of the compound no. 1

- on the other hand " the remarkable persistence of the mixture than the maneb alone;

- finally, the non-phytotoxicity of the compound η⁰ I on vine.

Example 5 : Mycelial growth in vitro test

Studied the action of the products according to the invention on mycelial growth following fungi:

- Rhizoctonia solani or, responsible for necrosis of the collar,

- Rosarium oxysporum was, responsible for tracheomycoses,

- The Fusarium snow, is cast iron seedlings of cereals,

- Rusarium roseum fed, responsible for the blight cereals,

- Solerotinia delusion, responsible for Sclerotirum,

- Solerotinia sclerotionum, responsible for Sclerotirum,

- GenusPythium Baryanum of. seedling is cast iron,

- Phomopaisviticola, responsible for Phomopsis Leaf,

- Septoria Stagonospora nodorum, septoria responsible for cereals,

- With Helminthosporium, responsible for leaf blight resistance protein,

- Vertieillium, responsible for Verticillium wilt,

- Cercospora diseases beticola, responsible for banana tree,

For each test, approach is used of I ' "agar agar diluting flat". In a petri dish, is poured, at a temperature of about 50 °c, a mixture of agar and an acetonic solution or a wettable powder containing the material to be tested at a concentration of 0.25 g/l.

The wettable powder is prepared by mixing during I-Mn in a knife mill the following ingredients:

20 - active material to be tested %

- (calcium lignosulfonate) défloeulant 5%

- (sodium aleoylarylsulfate) wetting the I %

- load (aluminum silicate) ^ 4# this wettable powder is then mixed with an amount of water for application to the desired dose.

The mixture is allowed to solidify and then agar provides washers mycelial culture of the myeète.

Taken as a control like a petri dish

to the previous one, but whose agar medium does not contain active material.

After 4 days * to 20 °c, estimation of the zone of inhibition observed and expressed in terms of ratio to the test area.

Example 6 : In vivo testing on organ survival: testing tomato late blight, Willwill phytophora

On tomato leaf freshly deposited a drop of a mixture of a suspension reason of 80,000 units/cm to about ^, and a dilution desired a wettable powder of the same the one described in example 1 in the case of a product or solution acétoniaue.

Under these conditions, there is a

for the product I at the dose of 0.5 g/l.

5 Parcels of tobacco plants (91 bp) 0 15 are processed using a wettable powder containing an active ingredient made respectively to 80 with fo by the maneb to 160 g/l, to 50 % by the compound no. I to 200 g/l. A parcel is left without treatment as a control.

After 48 hours, the plants are contaminated artificially (infestation Peromospora tabaoina) and then subjected to mist. The treatments are subsequently taken once a week.

We monitor 0 12 by counting the number of spots per parcel mildew. The results are recorded in the following table:

Other testing shows that the compound of the invention is also active on this same fungus into curative treatment and has a systemic action.

Plantlets avocado (variety Perseamdica) are planted in soil infested Phytophthora cinnamomi, then the earth is irrigated with a solution containing 3 g/l of the compound no. I few plantlets are left unprocessed as controls. Under these conditions, it is observed after 20 days that the roots of the witnesses are completely destroyed while 90 $of plantlets treated is sound.

Of pineapple seedlings are contaminated by Phytophthora Endothia parasitica, then treated after 48 hours by spraying with a solution of the compound to 0.5 g/l No

After 30 days, there is a complete inhibition of the fungus on the plantlets treated, while the controls are infested.

Ten strawberry plants (variety amazing wharehouses) are treated by soaking the I hour in an aqueous solution containing 0.2 $of compound I, and then dried and subcultured, the H June, soil which artificially contaminated with Derived Phytophthora cactorum. Immediately after, and then at a rate of once every eight days, up to 18 July, the plants are sprayed with the same solution which means that the total delivery 0.5 g of active material/seedling.

Plants are treated by dipping and spraying with water to serve as controls.

Under these conditions, it is found, 0 24, that the protection of strawberry is total while⁷ 6 C/o of indicators are dead.

Ten of plants peppers (varieties Yobo waving) are transplanted 0 27 press pots in artificially contaminated with Derived Phytophthora capsici. The plants are then dressed, immediately followed by all eight days to 18 July, with an aqueous solution containing compound No, so as to provide 0.5 gm/treatment/seedling.

Plants are irrigated with with water to serve as controls.

Under these conditions, it is observed that the plants are intact at the end August while the indicators are all dead upon 0 25.

All these examples clearly show the remarkable fungicidal activity of the compounds according to the invention which acts both to prevent that to stop the development of fungi belonging to various families such as, in particular, the Ascomycetes (Pusarium in SP...), the Basidiomycêtes (Bhizoctonia ground...) and especially the phycoœycètes with in particular mildews vine, tobacco and hops, Phytophthora but also fungi of the sol as genusPythium in SP.

The protection can be achieved for tropical or temperate crops such as hops, vegetable gardens, ornamental plants, soybean, citrus trees, caeaoier, coconut palm, tree species Hevea been issued...

Further, these compounds can be advantageously used in admixture with each other or with other fungicides known as metal dithiocarbamates (maneb, zineb, mancozeb), basic salts or hydroxides of copper (oxychloride, oxysulphate) the (tetrahydro) phthalimide (captan, captafol, folpel), n (dl-butylcarbamoyl) 2-benzimidazole derivatives of methyl carbamate (benomyl), the 1.2 di - (3 methoxy or ethoxy) carbonyl 2 a-thioureido benzenes (thiophanates), the 2-benzimidazol carbamate methyl, andc... either to complete the spectrum of activity of the compounds according to the invention, to either increase their remanence.

The applicant has also found that these compounds may be mixed with other fungicides anti mildews phosphors derivatives, especially 2 hydroxy optionally substituted 1, 3, 2 a-dioxaphospholanes olignucleotides 73 - 01,803 French Patent requests 73 - 37,994 and as well as phosphorous acid and its salts, objects Patent French 73 - 43,081, the monoesters phosphonic acids and their salts, 73 - 45,627 request objects, and the diestersphosphoniques, objects of the request 74 - 08, 995.

The doses of use may vary within wide limits in accordance with of the mushroom and the climatic conditions. Generally, between 0.01 and 5 g/l compositions of active material are well suited.

For their use in practice, the compound according to the invention are rarely used alone. Most often, they are part of formulations generally include, in addition to the active material according to the invention, a support and/or teneio-active agent.

The term "carrier" in the sense of the present specification denotes a material, organic or inorganic, natural or synthetic, with which the active material is associated for ease of application to the plant, on ' seeds or soil, or transportation, or handling. The carrier may be solid (clays, natural silicates or synthetic, resins, waxes, solid fertilizers...) or fluid (water, alcohols, eétones, petroleum fraction, chlorinated hydrocarbons, liquefied gas).

The surfactant can be an emulsifier, dispersant or wetting, which may be ionic or nonionic. It may be mentioned, for example, salts of polyacrylic acids, lignin sulfonic acid, eondensats of ethylene oxide to fatty alcohols, fatty acids or fatty amines.

The compositions of the invention can be prepared in the form of wettable powders, powders for powderings, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.

Wettable powders are usually prepared so that they contain from 20 to 95 wt. # and they usually contain, in addition to a solid support, of 0 to 5^by weight of wetting agent, of 3 to 10 $by weight of a dispersing agent, and, when necessary, of 0 to 10 $by weight of one or stabilizers and/or other additives, such as penetration agents, adhesives or caking agents, dyes, c... For example, the guidelines for a wettable powder:

50 $- active material

- calcium lignosulfonate (deflocculation) 5 c/o

1 - anionic wetting agent

5 - silica anti-caking °1°

kaolin clay (load)- 39 i° Aqueous emulsions and dispersions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention are included within the general framework of the present invention. These emulsions may be of the water-in-'huile 1 or of the oil-in-water and they may have a thick consistency like that of a "mayonnaise-type".

The compositions of the invention may contain other ingredients, such as protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestering agents as well as other active materials well known to pesticidal properties, especially acaricides or insecticides.