FR2460110A1 - NOVEL FUNGICIDAL AGENTS AND BACTERICIDES BASED ON HALOGENOACETAMIDES - Google Patents

Abstract

THE INVENTION CONCERNS THE APPLICATION OF HALOGENOACETAMIDES OF FORMULA: (CF DRAWING IN BOPI) IN WHICH X MEANS A CHLORINE OR BROMINE ATOM AND R REPRESENTS HYDROGEN OR AN ALKYL GROUP, AGENTS FOR PREVENTION OR FIGHT AGAINST FUNGI AND PHYTOPATHOGENIC BACTERIA.

Description

The subject of the present invention is the application

  haloacetamides as fungicidal and bacterial agents

  cides. The invention relates more particularly to the application, as fungicidal and bactericidal agents, of haloacetamides corresponding to formula I

CH R (I)

|, CH-N - CO - CH2X

2

  wherein R represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, and X represents a chlorine or bromine atom, X to represent a bromine atom when R is

  an alkyl group containing from 1 to 4 carbon atoms.

  The invention also relates to a method for

  to prevent or combat fungi and phyto-

  pathogens, the process by which an effective fungicidal or bactericidal quantity is applied to the fungi or bacteria or to the place where they are found

  a compound of formula I as defined above.

  The method of the invention is particularly suitable for preventing or controlling fungi and bacteria on plants, seeds or

floor.

  By "soil" is meant a growth medium

  conventional, natural or artificial.

  The amount of compounds of formula I to be applied depends on various factors such as the place to be treated, for example whether it is a plant, the soil or seeds, the species of fungus or bacteria, the mode application, for example by spraying on the leaves or by treatment of the soil or seeds, the time of application, that is to say if the treatment is preventive or curative, the compound used etc ... Of a In general, good results are obtained when treating the plants or the soil at a dose of between about 0.1 and 10, preferably between 0.2 and 5 kg of active substance per hectare. If desired, the treatment can be repeated, for example, at intervals of

  8 to 30 days. When using the compounds of the invention

  to treat seeds, it is

  to apply the active substance at a rate of approximately 0.05 to

  0.5, preferably about 0.1 to 0.3 g / kg of seed.

  When in the compounds of formula I R

  has an alkyl group containing from 1 to 4 carbon atoms, it is a branched alkyl group, for example a sec-butyl group, or a linear group, for example a methyl, n-propyl or n-butyl group, especially a group

n-propyl.

  When X represents a bromine atom, R

  preferably means a hydrogen atom.

  Particularly preferred compounds such as

  fungicidal and bactericidal agents are 2-bromo-N-

  cyclopropyl-acetamide and 2-bromo-N-cyclopropyl-N-n-

  propyl-acetamide. The compounds of formula Ia ## STR4 ## CH (Ia) ICH-N-CO-CH 2 Br CH 2

AT... ---..

  wherein R 1 represents a hydrogen atom, a linear alkyl group containing 2 to 4 carbon atoms or a branched alkyl group containing 4 carbon atoms, are new; they are part of the present invention

  as well as their preparation process.

  To prepare the compounds of formula Ia, a compound of formula II is reacted

CH2 (II)

I --CH - NH - R

  CH2 in which R1 has the meaning already given,

with 2-bromoacetyl bromide.

  The reaction can be carried out according to the methods usually used for the preparation of haloacetamides. For example, it is possible to operate in an inert organic medium, preferably in the presence of an acid-accepting agent, for example a trialkylamine.

such as triethylamine.

  The preparation of the compound of formula la wherein R 1 represents a hydrogen atom, i.e. 2-bromo-N-cyclopropylacetamide, is preferably carried out at a low temperature, for example at a

  temperature between about -10 and +50, preferably

at about 0.

  In order to prepare the compounds of formula la in which R 1 is other than hydrogen, the reaction is preferably carried out at a moderate temperature, for example at a temperature of

  between about 150 and 350, in particular

between 20 and 250.

  The reaction is preferably carried out under anhydrous conditions. As a suitable inert organic medium, a halogenated hydrocarbon such as methylene chloride or, where

  taken into account or the acid-accepting agent are

  at the reaction temperature, an excess of these products. The compounds of formula la thus obtained can

  then be isolated and purified by the usual methods

  tual. The compounds of formula I other than the compounds of formula la are known intermediates used for the preparation of pharmaceutical products

  (see U.S. Patent No. 3,532,749).

  The compounds of formula II as well as 2-bromoacetyl bromide are known or can be prepared according to known methods used for the preparation

similar products.

  The compounds of formula I are particularly suitable for combating fungi of the genus Fusarium spp., Such as, for example, F. oxysporum f. sp.lycopersici in tomato crops, F.oxysporum f.sp.vasinfectum in cotton, F.oxysporum f.sp.cubense in banana plantations, F.solani in vegetables, F.culmorum in cereals, F .graminearum in cereals, Verticillium spp., for example V.albo-atrum in a large number of crops such as cotton, hops,

  alfalfa and nightshades; V.theobromae in planting

  banana plants, Colletotrichum spp., eg C. lindemuthianum in beans, Phytophthora spp., for example Ph.cactorum, Ph. parasitica, and Ph. cinnamomi in susceptible plants, Pythium spp., for example Paphanidermatum in plants. sugar beet, Thielaviopsis basicola in a large number of crops, Stereum spp., for example Stereum purpureum in fruit trees (pips or stones), of the order Ustilaginales, eg U.maydis in mals, Venturia spp., for example V.inaequalis in apples, Phoma spp., for example Ph.betae in sugar beets, and

  Pyricularia spp., For example P.oryzae in rice.

  The bacteria against which the compounds of formula I are particularly effective are those of the genus Xanthomonas spp., Such as X.malvacearum in cotton, X.pelargonii in Pelargonium and Pseudomonas spp., For example P.tomato in tomato cultures. , and

  P.syringae in sensitive plants.

  Fungi and bacteria of the above kind cause considerable damage in agriculture, for example in tomato, cotton and cereal crops, as well as in arboriculture and ornamentals. In addition, it is difficult to fight prophylactically or to

  fight these fungi or bacteria.

  The compounds of formula I are particularly useful for combating Fusarium, Phytophthora, Ustilaginales, Pythium, Colletotrichum, Stereum, Thielaviopsis, Verticillium, Phoma, Venturia, Pyricularia, Pseudomonas

and Xanthomonas.

  For their application, the compounds of formula I can be converted according to known methods into

  a fungicidal and bactericidal composition. Such com-

  positions comprising a compound of formula I and a

  inert pest from a fungicidal or bactericidal point of view

  are also part of the invention.

  In general, the compositions of the invention contain between about 0.01 and 90% by weight of active product, preferably between about 0.1 and 60% by weight of active product. They may be in the form of concentrates which are diluted before use or in diluted ready-to-use form. Particular formulations include wettable powders, emulsifiable concentrates, dusts, spray liquids, granules and delayed action compositions. These formulations may contain, in addition to the compound of formula I, the solid supports, the diluents and / or the usual adjuvants in agrochemistry. Emulsifiable concentrates generally contain between about 10 and 70%, preferably between about 20 and 60% by weight of active substance. Solid compositions, more precisely in the form of particles, are preferred. The compositions intended for spraying

  include a surfactant such as a polyglycerol ether

  liquid, a fatty alkyl sulphate or a lignin sulphonate.

  The compositions of the invention may further contain other fungicidal, bactericidal or other agents.

  active products such as insecticides.

  The concentrated fungicidal compositions

  generally between 2 and 80%, preferably

  from 5 to 70% by weight of a compound of formula I.

  The ready-to-use forms of these compositions

  are generally between about 0.01 and 10% by weight of a compound of formula I. The fungicidal and bactericidal action of the compounds of formula I has been demonstrated by known methods, for example as described below:

  Test-A: in vivo test on Fusarium oxysporun f.sp.

lycopersici -

  Lycopersicon esculentum cv tomatoes are grown for 10 days. (Rheinland's Ruhm) in

  bins containing a mixture of peat and sand. We are

  festure of previously steam-sterilized peat with an inoculum of Fusarium and then treat this soil by mixing the substance to be tested in order to obtain concentrations of 160, 40 and 10 ppm of substance per volume of soil. After filling plastic pots

  6 cm in diameter with this infested soil, it is

  plant the tomato plants grown above. We are

  cube the plants for 21 days at 270 and under a humi-

  60-70% relative. The effectiveness of the test substance is determined by comparing the inhibition on Fusarium observed on the soil treated with plants

  inoculated in the same way but not treated.

  A clear fungicidal activity is observed using the compounds of Examples 1 to 4, in particular

  with the compounds of Examples 1 and 3.

  The same test is repeated by infesting cucumber plants with Pythium aphanidermatum and beets

  sugar with Phoma betae; we obtain the same results

  States. Test B: In vitro test on Ustilago maydis Different concentrations of test substance are incorporated into agar-maltose plates so as to obtain concentrations of 0.8 to 200 ppm of substance to be tested. These plates are then inoculated by spraying a U. maydis spore suspension or by placing in the center of the plate a piece of agar containing U. maydis. These plates are incubated for 2 to 5 days at room temperature. Effectiveness is determined

  of the substance by comparing the development of the

  pinion observed on the treated plates with the result

  obtained on untreated plates.

  A significant fungicidal effect is obtained when

  active substance, one of the compounds of Examples 1 to 4, in particular the compounds of

Examples 1 and 3.

  Similar results are obtained when treating the following fungi and bacteria: Venturia inaequalis, Pyricularia oryzae, Phytophthora cactorum, Stereum purpureum, Thielaviopsis basicola, Verticilium alboatrum, Colletotrichum lindemuthianum, Pseudomonas

tomato and Xanthomonas pelargonii.

  In addition to the carriers and surface-active agents, the compositions of the invention may also contain particular adjuvants, for example stabilizing agents, deactivating agents (in the case of solid formulations on surface-active carriers), aimed at improving the grip on

  plants, corrosion inhibitors, anti-

foam and dyes.

  The examples of the following formulations are of course not limiting in nature. a) Granule 5 g of a compound of formula I are dissolved by

  for example 2-bromo-N-cyclopropylacetamide or 2-bromo-

  N-cyclopropyl-N-n-propyl-acetamide in 10 g of an aromatic solvent preferably having a boiling point between 185 and 213. The solution is then sprayed by known methods on 90 g of pumice stones which have been crushed and carefully sieved (dimensions of

grains 0.3-1 mm).

  b) Emulsifiable concentrate 25 parts by weight of a compound of formula I, for example 2-bromo-N-cyclopropylacetamide or 2-bromo-N-cyclopropyl-N-n-propyl-acetamide, are mixed with

  parts by weight of an octaglycolic ether of iso

  octylphenol and 45 parts by weight of a petroleum fraction having a boiling point between 210-280 (D20 = 0.92). Before use, dilute the concentrate

  with water until the desired concentration.

  c) Wettable powder 50 parts by weight of a compound of formula I, for example 2-bromo-N-cyclopropyl-acetamide or 2-bromo-N-cyclopropyl-Nn-propyl-acetamide, are mixed with 2 parts by weight of sodium lauryl sulphate, 3 parts by weight of sodium lignosulfonate and 45 parts by weight of kaolinite. Before use, this mixture can be

  diluted in water to the desired concentration.

  d) Seed treatment powder 45 parts by weight of a compound of formula I are mixed, for example 2-bromo-N-cyclopropyl-acetamide or 2-bromo-N-cyclopropyl-Nn-propyl-acetamide, with 1.5 parts of decantyl ether of dipentyl phenol, 2 parts of light oil, 51 parts of finely divided talc and 0.5 part of Rhodamine B dye. This mixture is milled in a Contraplex mill operating at a temperature of speed of 10,000 rpm until a mean granularity of less than 20 percent is reached. The powder thus obtained has good adhesion and can be used for the treatment of seeds, for example by mixing with seeds during 2-5 days.

  minutes in a drum spinning at low speed.

  The fungicidal and bactericidal agents can also be incorporated into the coatings intended for the

  treatment of plant injuries.

  The following examples illustrate the present invention without in any way limiting its scope. The

  all temperatures are in degrees Celsius.

  The ambient temperature is between 20 and 300,

unless otherwise stated.

Example 1

2-bromo-N-cyclopropyl acetamide

  6.92 ml (0.1 mole) of cyclopropyl-

  amine with 13.9 ml (0.1 mole) of triethylamine in 250 ml of methylene chloride and cooled to 0. While maintaining the temperature at 0 with the aid of a cooling bath, a solution of 8.75 ml (0.1 mole) of bromide is added dropwise with stirring over a period of 45 minutes. 2-bromoacetyl in ml methylene chloride. The mixture is allowed to warm to room temperature and stirred for another 18 hours. The reaction mixture is then washed twice with 50 ml of saturated aqueous sodium bicarbonate solution each time, washed twice with 50 ml of sodium chloride solution each time and dried over sulphate. of anhydrous sodium, filtered and evaporated. The title compound is thus obtained in the form of a brownish solid product; it melts at 114-116 after crystallization in

  a 9: 1 mixture of hexane and methylene chloride.

Example 2

  2-chloro-N-cyclopropyl-acetamide Using the procedure described in Example 1, but using an approximately equivalent amount

  of 2-chloroacetyl chloride, 2-chloroacetyl

  N-cyclopropylacétamide; he melts at 84-85.

Example 3

  2-bromo-N-cyclopropyl-N-n-propylacetamide In a three-necked flask equipped with a stirrer, a gas inlet tube and a dropping funnel,

  6 g (0.06 mol) of N-cyclopropyl-n-propyl-

  amine and 6.12 g (8.6 ml, 0.06 mole) of triethylamine in about 150 ml of methylene chloride. Under a dry nitrogen atmosphere, a solution of 12.3 g (5.3 ml, 0.06 mole) of α-bromo bromide is added at 20 ° to 25 minutes with stirring. acetyl in 20 ml of methylene chloride and continued for a further hour. The mixture is then washed 3 times with 30 ml of 10% hydrochloric acid each time, three times each with 30 ml of a 10% aqueous solution of sodium bicarbonate and then twice with each

  30 ml of an aqueous solution of sodium chloride.

  The reaction mixture is then dried over sodium sulphate

  anhydrous magnesium and the solvent is removed by evaporation

  tion. This gives the title compound which is purified by distillation at 100 under 0.2 mmHg in a

ball tube.

  NMR spectrum (in CDCl 2): 0.80 (m, 7H); 1.52 (m, 2H);

3.26 (t, 2H); 4.04 (s, 2H).

  N-cyclopropyl-n-propylamine, used as a starting material, can be obtained by reacting cyclopropylamine with propionyl chloride and reducing the N-cyclopropylpropylamide thus obtained.

  (F = 39-41) using borane in tetrahydrofuran.

he

Example 4

  Proceeding as described in Example 3, but replacing Ncyclopropyl-n-propylamine by an approximately equivalent amount of a) N-cyclopropyl-methylamine, b) N-cyclopropyl-ethylamine, c) Ncyclopropyl-n-butylamine, or d) N-cyclopropyl-sec-butylamine, the following compounds are obtained respectively: a) 2-bromo-N-cyclopropyl-N-methyl-acetamide, b) 2-bromo-N-cyclopropyl-N-ethyl-acetamide, c) 2bromo-N-cyclopropyl-Nn-butylacetamide, and

  d) 2-bromo-N-cyclopropyl-N-sec.-butyl-acetamide.

  Spectrum RMI (I in CDCl2): 4.13 (s, 2H); 3.20 (d, coupling

  constant 1.16; 2H); 2.80 (m, 1H); 0.7-1.0 (d and m, 10H).

Claims (8)

  1. Application of haloacetamides corresponding to formula I CH2 R (I) C C | ilH- CO - CH X -   CH 2 in which R represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, and X represents a chlorine or bromine atom, X to represent a bromine atom when R is an alkyl group containing 1 at 4 carbon atoms,   as fungicidal and bactericidal agents.   2. A method for preventing or combating phytopathogenic fungi and bacteria, characterized in that a fungicidal or bactericidal amount of a haloacetamide of formula I is applied to the fungi, bacteria or the place where they occur ( I) CH R I CH - N - CO - CH2X   wherein R represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, and X represents a chlorine or bromine atom, X to represent a bromine atom when R is   an alkyl group containing from 1 to 4 carbon atoms.   3. A process according to claim 2, characterized   characterized in that the haloacetamide of formula I is applied to plants, seeds or soil. 4. A process according to any one of   claims 2 and 3, characterized in that   preventive title or one fights Phytophlhor.a mushrooms, Ustilaginales, Fusarium, Pythium, Stereum, Thielaviopsis,   Phoma, Venturia, Pyricularia or Verticillium.   5.- An agent of prevention and fight against   fungi and phytopathogenic bacteria, which are   in that it contains as active substance a haloacetamide of formula I CH R () CH-N- CO - CH2X   Wherein R represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, and X represents a chlorine or bromine atom, X to represent a bromine atom when R is   an alkyl group containing from 1 to 4 carbon atoms.   6. A preventive and control agent according to claim 5, characterized in that it contains, as active substance, a haloacetamide corresponding to the formula Ia CH2 Rl (Ia) CH2 1   Wherein R1 represents a hydrogen atom, a linear alkyl group containing from 2 to 4 carbon atoms or a branched alkyl group containing 4 atoms of carbon,.   7. A prevention and control agent according to claim 5, characterized in that it contains,   active substance, a haloacetamide selected from   2-chloro-N-cyclopropyl-acetamide, 2-bromo-N-   cyclopropyl-N-methylacetamide, 2-bromo-N-cyclopropyl-   N-ethylacetamide, 2-bromo-N-cyclopropyl-N-n-butyl-   acetamide and 2-bromo-N-cyclopropyl-N-sec-butyl-   acetamide. 8. A prevention and control agent according to claim 5, characterized in that it contains,   as the active substance, 2-bromo-N-cyclopropyl-   acetamide. 9. A prevention and control agent according to claim 5, characterized in that it contains,   as the active substance, 2-bromo-N-cyclopropyl-N-n-   propyl-acetamide. 10. A composition for the prevention and control of phytopathogenic fungi and bacteria, characterized in that it contains the active substance specified in any one of the   Claims 5 to 9, in association with solid and / or liquid.   A composition according to claim 10, characterized in that it contains 0.01 to 90% by weight of active substance specified in any one of Claims 5 to 9.   12. New haloacetamides, characterized in that they correspond to the formula Ia CH2 - (Ia) | CH - N - CO - CH Br CH ^^ 2   wherein R1 represents a hydrogen atom, a linear alkyl group containing from 2 to 4 carbon atoms or a branched alkyl group containing 4 atoms of carbon.   13. A process for the preparation of halogens   acetamides of formula Ia CH2 | in which R1 represents a hydrogen atom, a linear alkyl group containing from 2 to 4 carbon atoms or a branched alkyl group containing 4 carbon atoms, characterized in that reacting a compound of formula II ## STR1 ## in which R has the meaning already given, with 2-bromoacetyl bromide.