IL31307A - O-halophenylcarbamates,their preparation and use as fungicides - Google Patents

Description

O-halophenylcarbamateo, their preparation and use as fungicides Fi fflI3in?ABHIICaii BAYER A&T IENGESELLSCHAPT C. 29577 - 2 - 31307/2 ^ The present invention relates to certain new 0-halo-phenylcarbamates9 to a process for their production and to their use as fungitoxic compounds 0 ° It is known that trichloroiaethylthio compounds, in particular ti-trichloromethylthiotetrahydrophthalimldes, can o used as fungicidal active compounds (German .Patent Specification 912290).

S e present invention provides new O-halophenylcarbamatos of the formula 2 in which R~ ^a bromine or iodine,, R is chlorine p bro_nin©„ iodine, fluorines, trifluoroiaethylj loweralkylj carboxylic aeyl-amino, or dialkylaminocarbonyl, one R is chlorine p bromine 9 ipdine or hydrogen, and the other is chlorine, bromine, or 4 2 is not chlorine or bromine p is alkyl with 1 to 8 carbon atoms (optionally substituted by halog®-¾9 eyano, alkosy or cycloalkyl) 9 hydrox s cycloalkyl, alkonyl, haloalkenyl9 aralkyl or aryl which may be substituted by alogen, alkyl or alkojsy, or R is alkylono or arylene attsched to no her radical of the fo£_aula J a a a The present Invention also provides a process for the production of an P-halophenylcarbamates of formula (l) in which (a) a phenol of the formula in which R1 to R^ have the meanings stated above is reacted with an isocyanate of the formula 0»C«-a5 (IV) in which .

R^ has the meaning stated above or (b) a phenol of the formula (3) is reacted with excess phosgene to form a chloroformlc acid halophenyl ester which is reacted with an amine of the general formula H2N-R5 (V) in which R^ has the meaning stated above or (c) a phenol of the formula (5) is reacted with the approximately equimolar amount of phosgene to give the appropriate bis-halo-phenylcarbonate which is reacted with an amine of the formula (7).

Surprisingly, the active compounds according to the invention show a higher fungitoxic effectiveness than the previously known N-trichloromethylthiotetrahydrophthalimtde.

Takin 3-chloro-2 4 6-tribromo henol and henlisoc anate - 4 - 31307/2 and 3~chloro-2,4,6-trlbromophenylchloroformic acid ester and aniline as examples of starting materials in variant (b), and bis-(3-chloro-2il4,6-tribromopheiiyl)-carbonate and aniline as examples of starting materials in variant (c), then the reaction courses are represented by the following scheme: The starting materials to be used are known. 2 In the above formulae, R is preferably chlorine, bromine, iodine, fluorine, . trifluoromethyl, lower alkyl with 1 to 4 carbon atoms, carboxylic acylamino with 2 to 5 carbon atoms, or dialkyl- c: aminocarbonyl with 3 to 7 carbon atoms. R is preferably (i) alkyl with 1 to b carbon atom3 which may be substituted by chlorine, bromine, fluorine, cyano, alkoxy with 1 to 4 carbon atoms, cyclo-, alkyl with 5, or 6 carbon atoms and/or- nltro, or (ii) hydroxy, cycloalkyl with 5 or 6 carbon atoms, alkenyl with 2 or 3 carbon atoms, haloalkenyl with 2 or 3 carbon atoms and 1 to 5 halogen atoms (preferably chlorine, bromine and fluorine) ,· phenylalkyl with 1 to 3 carbon atoms in the alkyl group or phenyl, especially nalophenyl, or (iii) phenylene or alkylene with 1 to 6 carbon atoms attached to another radical as described above.

As examples of phenols which may be used as starting materials , there are mentioned: 3-methy1-2,4,6-tribromophenol, 3-methyl-4-bromo-2,6-diiodo-phenol, 3-chloro-2,4-dibromophenol, 3-chloro-4,6-dibromophenol, 3-chloro-2,4-dibromo-6-iodophenolf 3,6-dichloro-2,4-dibromophenol, 3,6-dichloro-2,4*l.iiodophenol, 2-chloro-4,5»6-tribJ?omo-phenol, 2,4,5,6-tetrabromo henol, 2-iodo-4,5 »6-tribromophenol, 3-fluoro-2 ,4, 6-tribromophenol, 3-fluoro-2 ,4,6-triiodophenol, 3-acetylamino-2,4,6-tribromophenol, 3 hydroxy-2»4,6-tribromo-benaoic aoid methyl ester-) 3-hydroxy-2,4,6-tribromobenzoic acid dimethylamide and 2-chloro-4,6-dibromo-5-trifluoromethylphenol.

As examples of amines and isocyanates, there are mentioned: methyl, ethyl, isopropyl, propyl, butyl, isobutyl, 2-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-octyl, ω-cyanopentyl, 6-chloro-n-hexyl, methoxymethyl, ethoxymethyi, propoxymethyl, butoxy-methyl, isobutoxy-methyl, 3-methoxypropyl, 3-propoxypropyl, 3-butoxypropyl, cyclohexyl, 4-methylcyclohexyl, allyl, 3-chloro-allyl, benzyl, a-naphthylmethyl, β-phenylethyl, phenyl, penta-chlorophenyl, m-tolyl, p-isopropoxyphenyl, hexamethylene-1,6-bis, p-phenylene-bis, naphthylene-1,5-bis, p^'-diphenyl-methane-bis and toluylene-2,4-bis isocyanate or amine.

Variant (a) of the process is expediently carried out in the presence of an inert organic solvent at a temperature of -50 to +120°C, preferably 0-60°C. A basic substance, preferably a tertiary amine, such as trieth lamine , pyridine, dimethy1-cyclohexylamine, dimethylanlline and dimethylbenzylamine, may be added as catalyst. The resulting carbamates are compounds which crystallise well and which are liable to decompose at elevated temperature, in most cases, even above 100°C, so that generally In the first step of variant (b) of the process, the phenol^ may be phosgenated in an inert solvent in the presence of a hydrogen-chloride-binding base, such as dimethylaniline, pyridine, triethylaml ne I, dimethylcyclohexylamine or dimethylbenzyl-amine, at a temperature of about -70 to +100°C, preferably -30 to +20°C, or phosgene and a hydrogen-chloride-binding base, preferably a solution of alkali, may be added to a mixture of the phenol to be phosgenated, water and an inert, water-immiscible solvent, the temperature being kept between the freezing point of the aqueous solution and about +50°C, phosgene and base expediently being used in excess in order to achieve as high a yield of chloroformic acid halophenyl ester as possible.

In the second step of variant (b), the chloroformic acid halophenyl ester may be reacted with the amine in the presence of an inert organic solvent in the absence of water at a temperature of about -100 to +50°C or in the presence of water and a water-immiscible inert organic solvent at a temperature between the freezing point of the aqueous solution and about +50°C, excess amine or a tertiary amine, such as dimethylaniline , dimethylcyclohexylamine, pyridine or triethylam1ne or, in the case of reaction in the presence of water, an alkali metal hydroxide or carbonate or an alkaline earth metal hydroxide or carbonate being used as hydrogen-chloride-binding base. Furthermore, it is possible to distribute the chloroformic acid halophenyl ester finely, in water with the aid of an emulsifier or dispersing agent and to react it with the amine in the absence of an organic solvent. It is, however, also possible to work without any solvent.

In the first step of variant (c) of the process, 2 moles of the phenol may be reacted with about 1 mole of phosgene in the presence of excess tertiary amine, as stated above, at a a re of - 0 to +1 0°C in an inert or anic solvent or the reaction may be carried out in aqueous suspension or in a one-phase, or two-phase mixture of water and an inert organic solvent with an acid-binding agent, usually with the. addition of a tertiary amine or of an inorganic acid acceptor and a catalytic amount of a tertiary amine, at a temperature between the freezing point of the aqueous solution and about +100°C. In the second step, the reaction is expediently carried out in the presence of an inert organic solvent at a temperature of +50 to +100°C.

The reaction products of the three variants may be worked up by known methods.

Suitable , inert organic solvents include hydrocarbons, such as benzine and benzene; chlorinated hydrocarbons, such as methylene chloride, ethylene chloride, carbon tetrachloride and dichlorobenzene; ethers, such as diethyl ether, dibutyl ether and dioxan; ketones, such as acetone, cyclohexanone and methyl-ethyl ketone? and acetonitrile and dimethyl formamide.

The active compounds according to the invention exhibit a strong fungitoxic activity and are distinguished by a broad spectrum of activity. Their low toxicity to warm-blooded animals and their good compatibility with higher plants permits their use as plant protection agents against fungal plant diseases. In the concentrations normally used for the control of fungi, they dp not damage cultivated plants..

Fungitoxic agents in plant protection are used for the control of fungi from the most diverse classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Pungi Imperfect!.

The active compounds according to the invention can be used against parasitic fungi, on above-the-soil parts of plants, fungi which cause tracheomycosis which attack the plant from B reason of their excellent properties mentioned above, the active compounds according to the invention can also be used with good results against fungal diseases which hitherto had to be controlled with fungicidal agents containing arsenic and mercury.

The active compounds have given particularly good results in the control of rice diseases. Thus, they show an excellent activity against .the f ngi Piricularia oryzae and Pellicularia sasakii, so that they can be used for the joint control of these two diseases. That is a substantial advantage, since up to now agents from different chemical groups had usually be used against these two fungi* Surprisingly, the active compounds show not only a protective activity, but also a curative effect.

However, the active compounds according to the invention also act against other fungi which infest rice or other cultivated plants, such as Cochliobolus miyabeanus, Mycosphaerella musicola, Cercospora personata, Botrytis cinerea and Alternaria, species Venturia species (causative organisms of apple scab and pear scab) , Plasmopara viticola. In addition, some of the compounds according to the invention show a very distinct activity against powdery mildew fungi, such as Podosphaera leucotricha (powdery mildew of apples) and Erysiphe polyphaga (powdery mildew of cucumbezs) .

The active compounds according to the present invention can be converted into, the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active ■compounds with extenders, that is, liquid or solid diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as a extender, organic solvents can, for examle also be used as auxiliary solvents, As liquid diluents or. carriers, there are preferably used aromatic hydrocarbons, such as xylenes or benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, paraffins, such as mineral oil fractions, alcohols, such as methanol or butanol, or strongly, polar solvents, such as dimethyl formamide or dimethyl sulphoxide, as well as water.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc or chalk, or ground synthetic minerals, such as highly-dispersed silicic acid or silicates. ' Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkyl-arylpolyglycol ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of dispersing agents include lignin, sulphite- waste liquors and methyl cellulose.

The active compounds may be used as such, in the form of their formulations or of the application forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates. Application may take place in the usual manner, for example by squirting, spraying, dusting, scattering, watering, dressing or incrustation.

The compositions may be diluted for use, and the concentration of active compound in the ready-to-use preparations can be varied within fairly wide ranges. In general, they are from 0.001 to 100#, preferably 0.05 to 10$.

The invention therefore provides a fungicidal composition containing as active ingredient a compound according to the invention in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. pests which comprises applying to the fungi or a fungus habitat a compound according tb the invention alone or in the form of a composition containing as active ingredient a compound according to the invention in admixture with a solid or liquid diluent or carrier.

The invention also provides crops protected from damage by fungus pests by being grown in areas in which, immediately prior to and/or during the time of the growing, a compound according to the invention was applied alone or in admixture with a solid or liquid diluent or carrier.

The activity of the compounds according to the invention is illustrated by the following Examples A-D. In these examples the compounds are identified by numbers corresponding to the numbers in Table 5.

Example A Piricularia and Pellicuiaria test Solvent: 4 parts by weight acetone Dispersing agent: 0.05 part by weight sodium oleate Water 95*75 parts by weight Other additives: 0.20 part by weight gelatin The amount of active compound required for the desired concentration of active compound in the spray liquor is mixed with the stated amount of solvent,, and the concentrate is diluted with the stated amount of water containing the stated additives. 2 batches each consisting of 30 rice plants about 2-4 weeks old are sprayed with the spray liquor until dripping wet.

The plants remain in a greenhouse at temperatures of 22 to 24°C and a relative atmospheric humidity of about 70^ until they are dry. One batch of the plants is then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Piricularia ory- atmospheric humidity. The other. batch of the plants is infected with a culture of Pellicularia sasakii, grown on malt agar and placed at 28-30°C and lOOfi relative atmospheric humidity. to 8 days after inoculation, the infestation of all the leaves present at "the time of inoculation with Piricularia is determined as a percentage of the untreated but also inoculated control plants. In the case of the plants infected with Pellicularia sasakii the infestation on the leaf sheaths after the same time is also determined in proportion to the untreated but infected control. Qfo means no infestation; 100 means that the infestation is exactly as great in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from Table 1.

Additional test/curative fungicidal activity In order to ascertain the curative fungicidal activity, the test is repeated, but the active compound is applied not before, but only 16 hours after, inoculation.

The active compounds , the concentrations of active compounds and the results can be seen from Table 1.

Ie A 11 252 - 11 - (1) pr. 0 (5) pr. 0 (6) pr. 0 0 cur. 16 (7) pr. 0 0 (8) pr, 0 0 cur. 13 (9) pr. 0 50 cur. 29 (10) pr. 8 (11) pr. 17 33 (12) pr. 0 cur. 21 (13) - pr. 5 cur. 9 (17) pr. 14 (18) pr. 0 0 (20) pr. 0 cur. 19 (22) pr. 25 Example B Hycelium growth test Nutrient medium used: parts by weight agar-agar parts by weight malt extract 950 parts by weight distilled water Proportion of solvent to nutrient medium: 2 parts by weight acetone 100 parts by weight agar nutrient medium The amount of active compound required for the desired concentration of active compound in the nutrient medium is mixed with the stated amount of solvent. The concentrate is thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which has been cooled to 42°C) and is then poured into Petri dishes of 9 cm diameter. Control dishes to which the preparation has not been added are also set up.

When the nutrient medium has cooled and solidified, the dishes are inoculated with the species of fungi stated in the Table and incubated at about 21°C.

Evaluation is carried out after 4-10 days, dependent upon the speed of growth of the fungi. When evaluation is carried out the radial growth of the mycelium on the treated nutrient media is compared with the growth on the control nutrient media. In the evaluation of the fungus growth, the following characteristic values are used: 0 no fungus growth 1 very strong inhibition of growth 2 medium inhibition of growth 3 slight inhibition of growth 4 growth equal to that of untreated control. The active compounds, their concentrations and the results . Table 2 ifycelium growth test H ir-1 (known) (2) 10 0 (3) 10 0 (5) 10 0 (6) 10 0 (7) 10 0 (8) 10 0 (9) 10 0 (10) 10 0 Mycelium growth test Active compounds Concentration of H active compound ppm (11) 10 I H (12) 10 VJl (13) 10 I (14) 10 (15) 10 (16) 10 (17) 10 (18) . 10 (19) 10 (20) . 10 (21) 10 (22) 10 (23) 10 Example C Fusicladium test (apple scab) (Protective) Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part b weight alkylaryl pol l col ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Young apple seedlings in the 4 - 6 leaf stage are sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70 . They are then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fus-icladium dendriticum Puck) and incubated for 18 hours in a humidity chamber at 18 - 20°C and at a relative atmospheric humidity of 100%. .

The plants then again come into a greenhouse for 14 days. days after inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants, 0% means no infestation; 100 means that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from Table 3. (14) Le A 11 252 - 17 - Example D Podosphaera test (powdery mildew of apples) [Protective] Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part b weight alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Young apple seedlings in the 4 - 6 leaf stage are sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse for 24 hours at 20°C and at a relative atmospheric humidity of 70%.. They are then inoculated by dusting with conidia of the apple powder/ mildew causative organism (Podosphaera leucotricha Salm.) and placed in a greenhouse at a temperature of 21 - 23°C and at a relative atmospheric humidity of about 70 .

Ten days after the inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants. means no infestation; . 100% means that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active com pounds and the results can be seen from Table 4.

Table 4· Podosphaera test/protective Infestation as a percentage of the in¬ Active compound festation of the untreated control with a concentration of active compound (in io) of 0.025 0.0062 0 (known) (6) (7) (20) 51 (8) 8 14 (9) 16 (13) 43 Example 1 36.5 g 3-chloro-2,4,6-tribromophenol (0.1 mole), 10 ml toluene and 11 ml pyridine are provided, and 12 g phenylisocyanate (0.1 mole) dissolved in 10 ml toluene are added dropwise. The temperature is kept to 40°C for 4 hours, dilution is effected with 200 ml petroleum ether and with water, the crystals formed are filtered off with suction, and this is followed by. washing with greatly diluted acetic acid and with water, and drying at 70°C in a vacuum. Yield: 38.5 g (=79.5$ of the theory) of N-phenylcarbamic acid 3-chloro-2 , 4 , 6-tribromophenyl ester; m.p. 141°G. .

Example 2 1065 g 3-chloro-2,4,6-tribromophenol (2.91 moles), 2.5 litres methylene chloride and 2 litres of water are provided at about 0°C, and 320 g phosgene (3.24 moles) are introduced with rapid stirring and, simultaneously, 167 g sodium hydroxide dissolved in 2 litres of water are added dropwise. The phases are. separated, the organic phase is dried with calcium chloride and distilled. Yield: 1148 g 3-chloro-2,4, 6-tribromophenyl-chloroformic acid ester (=92 of the theory); b.p. 120°C/0.2 mm Hg to 132°C/0.35 mm Hg. 944.5 g 3-chloro-2,4,6-tribromophenylchloroformic acid ester (2.21 moles) dissolved at -20°C in 2 litres of acetone are provided, and 324 g n-butylamine (4.42 moles) diluted with the reaction mixture is finely diluted with 3.1 k of water, and the separated carbamate is filtered off with suction and washed with 200 g of 50$ acetone and with water. The carbamate is rapidly dissolved in 2 litres of boiling acetone, the solution is filtered off from the chlorotribromophenylcarbonate formed, and 800 g of ice are added. The carbamate which crystallises out is, after washing in water, dried at 70°C in a vacuum. Yield: 790 g N-butylcarbamic acid 3-chloro-2,4,6-tribromophenyl ester; m.p. 127-130°C with decomposition.

In analogous manner with that described in Examples 1 and 2, the carbamates listed in Table 5 may be prepared.

Example 3 According to variant (b) of the process of the invention,, 16 g (0.04 mole) 2,4,6-tribromo-3-hydroxybenzoic acid dimethyl-amide and 5.2 g dimethylaniline, dissolved in 100 ml ethylene chloride, are added. at -20°C to a solution of 10 g phosgene in 100 ml ethylene chloride. After 30 minutes the reaction mixture is stirred through at 0°C with 10$ hydrochloric acid, the organic phase is separated, washed once with 10$ hydrochloric acid and twice with water; 6.5 g butylamine are added at 0°C in the presence of water and the mixture is adjusted to pH 8.4 with sodium carbonate solution. After 5 minutes the organic phase is separated, washed with water, dried over calcium chloride and evaporated, and the residue is heated to 60°C/0.1 mm Hg. Yield: 15.5 g l^-butylcarbamic acid 2,4,6-tribromo-3-(N^j^-dimethylaminocarbonyl)-phenyl ester, m.p. 133. °C, re-crystallised twice from methylethylketone-petroleum ether.

(Berichte 10, p. 145), 400 ml ohlorobenzene, 2 g antimony trichloride and 72 g thi nyl chloride are kept to 90°0 for 8 hours. Excess thionyl chloride is then expelled in a water-jet vacuum and about 100 ml ohlorobenzene are distilled off. 1 mole of di-methyiamine is introduced, with cooling, into the reaction product with the benzoic acid chloride and evaporation to dryness is then effected in a water-jet vacuum; the residue is treated with 1 litre of water. The aqueous solution is separated from undissolved products, and concentrated hydrochloric acid is added dropwise.: 2,,4,6-tribromo-3-hydroxybenzoic acid dimethylamide crystallises out. The crystals are washed with water and thereafter with greatly diluted sodium bicarbonate solution. Yield: 62 g, m.p. 161-164°C after recrystallisation from an acetone-water mixture 4:3. N found 3.56$, calc. 3.48$.

Table 5 (continued) -NH- (32 m.p. 133°C (decomp.) Le A 11 252 - 26 - • 27 - 31307/2

Claims (1)

1. CLAIMS 1, 0-Ealop¾nylcarbamates of the formula 2 in which is bromine or iodine, R is chlorine, bromine, iodine, fluorine, trifluoromethyl, lower alkyl, carbox lio 3 acylamino, or dialkylaminocarbonyl, one R is chlorine, bromine, iodine or hydroge and the other is chlorine, bromine, or iodine, R^ is hydrogen or, when ^ is not chlorine or bromine, A 5 R is also chlorine, bromine, iodine or fluorine, and R is alkyl of 1 to Θ carbon atoms (optionally substituted by halogen, cyano, alkoxy or cycloalkyl), hydroxy, cycloalkyl, alkenyl, halo-alkenyl, aralkyl or aryl, optionally substituted by halogen 5 alkyl or alkoxy, or is alkylene or arylene attached to another radical of the formula 2 2. Compounds according to Claim 1, in which R is chlorine, bromine, iodine, fluorine, trifluoromethyl, alkyl with 1 to 4 carbon atoms, carboxylic acylamino with 2 to 5 carbon atoms or dialkylaminocarbonyl with 3 to 7 carbon atoms, and R is (i) alkyl with 1 to 6 carbon atoms which may be substituted by chlorine, bromine, fluorine, cyano, alkoxy with 1 to 4 carbon atoms, cycloalkyl with 5 or 6 carbon atoms ami/or ultra, or (ii) hydroxy/, cycloalkyl with 5 or 6 carbon atoms, alkenyl with 2 or 3 carbon atoms, haloalkenyl with 2 or 3 carbon atoms and 1 to 5 halogen atoms, phenylalkyl with halo 1 to 3 carbon atoms in the alkyl group or pooolbly substituted phenyl, or (iii) phenylene or alkylene with 1 to 6 carbon atoms attached to another radical of formula (II). 3. The' compound of the formula:- 4. The compound of the formula:- 5. The c The compound of the formula:- The. compound of the formula:- 8. The compound of the formula:- 6. The compound of the formula:- 17. 20, The c The 22 The compound of the formula: 3. The compound of the formula:- The compound of the fprmula:- The compound of the formula 26. The compound of the formula:- 27. 28. 29. 30. 31. The compound of the formula:- 32, The compound of the formula:- The compound of the formula:- 35. ording to an formula: - 0=C=N-R' (IV) or (to) a phenol of. the formula given in (a) is reacted with excess phosgene to form a chloroformic acid halophenyl ester which is reacted with an amine of the formula:- B^N-R5 (V) or (c) a phenol of the formula given in (a) is reacted bis-halophenylcarbonate which is reacted with an amine of the formula given in (b), 36. A process according to claim 35 (a) in which the reaction is effected at -50 to +120°C. 37. A process according to claim 35 (a) or claim 36. in which sty the reaction, s carried out in the presence of a solvent. 38. A process according to claim 35 (b) in which the first reaction is carried out in an inert solvent . in the presence of a hydrogen-chloride-binding base at -70 to+100°C. 39. A process according to claim 35 (b) in which the first reaction, is carried out with the addition of phosgene and a hydrogen-chloride-binding base to a mixture of the phenol, water and an inert, water-immiscible solvent, the temperature being kept between the freezing point of the aqueous solution and 50°C. 40. A process according to claim 35 (b), 38 or 39 in which the second reaction,, is carried out in the presence of an inert organic solvent in the absence of water at -100 to +50°C. 41. A process according to claim 35 (b), 38 or 39 in which itu, the second reaction is carried out in the presence of water and an inert, water-immiscible solvent at a temperature between the freezing point of the aqueous solution and 50°C. 42. A process. according to claim 35 (b), 38 or 39 in which the second reaction is carried out with fine distribution ·· ·. , of the chloroformic acid halophenyl ester in water and reaction of such ester with the amine in the absence of, an organic solvent. < 3; A process according to claim 35 (c) in which the first " ' reaction< is carried out with an excess of the amine at -50 to +150°C in the presence of an organic solvent. 44. A rocess accordin to claim 35 c in which the first or two phase mixture of water and an inert organic solvent, in the presence of an acid-binding agent at a temperature between the freezing point of the aqueous solution and 100°C. 45. A process according to claim 35 (c), 43 or 44 in which the second reaction^ is carried out in the presence of an inert organic solvent at 50 to 100°C . . . 46. A process according to any of claims 35-45 in which the phenol is one of those hereinbefore mentioned. .47. A process for the production of a compound according to claim 1 substantially as hereinbefore described in any of Examples 1-3. 48. Compounds according to claim 1 whenever prepared by a process according to any of claims 35-47. 49. A fungicidal composition containing as active ingredient a compound accordin to any of claims 1-34 or 48 in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. 50. A composition according to claim 49 containing from 0.1 to 9 of the active compound by weight. 51. A method of combating fungus pests which comprises applying to the fungus or a fungus habitat a compound according to any of claims 1-34 or 48 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1-34 or 48 in admixture with a solid or liquid diluent or- carrier. 52. A method according to claim 51 in which a composition is used containing from 0.001 to 10 of the active compound, by weight. 53. Crops protected from damage by fungus pests by being grown in areas in which, immediately prior to and/or during the time of the growing, a compound according to any of claims 1-34 or 48 was applied alone or in admixture with a