GB2119652A - A process for the production of oil-based agricultural preparations - Google Patents

Abstract

The present invention provides a process for producing oil-based compositions for treating plants and agricultural land, the process consists of forming the active compound in the oily medium of the composition in the presence of a surfactant.

Description

SPECIFICATION A process for the production of oil-based agricultural preparations Background of the Invention The invention concerns the process for the production of oily preparations in such a manner that the reaction partners are reacted together in paraffin-like hydrocarbon oil, in given cases in the presence of surfactants and other additives.

The known field of utilisation of the preparation according to the invention is agricuiture.

Currently, ground protecting and plant protection agents are produced by first making the active materials, auxiliary materials etc. and then these are mixed together, homogenised and shaped (Van Valkenburg, Pesticide formulation, New York, 1973). This conventional method requires quite a lot of energy or power, labour and time. The technological solutions are generally environment-polluting.

Our invention is based on the discovery that if materials participating in certain types of reactions are dispersed in an oil, in the presence of additives, an oily suspension is obtained which can be diluted with water in accordance with the desired application for use.

The materials that may be produced according to our invention belong to that essential group of pesticides, plant growth regulating materials, insecticides, and fungicides the production of which takes place with similar or approximately similar technological parameters and in essentially identical operational steps. Such products are e.g.

the N-aryl-phthalic imide derivatives, carbamate derivatives, certain urea derivatives, etc.

The most important characteristics of the current production technology of active agents that can be produced by the process according to the invention and the essential background from the point of view of the aim of the present invention is best illuminated by describing the production of N-aryl-phthalamides which are plant regulating materials.

Amongst the N-aryl-phthalamides there are several valuable biologically active compounds such as active materials promoting the binding of the produce, promoting the formation of sugar, weed kiliers, fungicidal agents, inflammation inhibiting agents and bactericidal agents.

These compounds are generally produced from an aromatic amine and phthalic anhydride.

The above addition of phthalic anhydride to the aniline was formerly carried out in various solvents - aromatic hydrocarbons, chlorinated hydrocarbons, acetic acid, aromatic amines and, further, in the presence of water.

Of the aromatic hydrocarbons, principally benzene has been used as the solvent and the phthalamides used as plant growth regulating agents were first produced at room temperature in benzene; refer to e.g. U.S. Patent Specification No.

2556664, Canadian Patent Specification No.

519684, SUBBA, RAO N. V. - RATNAM, C. V.

J. Sci. Ind. Res. (India); 218 (1) 47 (1962) C.A. 56.

14994 (1962); GRAMMATICAKIS, P. Compt.

Rend. 251.1790-2 (1960), C.A. 56.2375 (1962) AUWERS, M., OSWALD, A.--THORPE, J. F. Lieb.

Ann. Chem. 285.29. (1895). See: Z. Anal. Chem.

148.259-66 (1955); Alternatively, the process was carried out at the boiling point of the solvent (DATTA. S. M.: Z. Anal. Chem. 148. 259-66 (1955)). In place of benzene, xylene may also be used. However, both of these aromatic solvents are strong poisons and their use involve an increased fire and explosion hazard. The drying of products containing such solvents can only be carried out in very special conditions or circumstances.

Amongst the chlorinated hydrocarbons, chloroform (South African Patent Specification No. 6802762, Sherill, M. L.-Schaffer, F. L.-Shoyer, E. P. J. Am. Chem. Soc. 50.

474-85 (1928)) and methylene chloride (West German Patent Specification 2040578) have been used.

Reference may also be found to the use of petroleum but the authors do not provide details (U.S. Patent Specification No. 2566664).

Petroleum and certain low boiling point aliphatic hydrocarbons cannot be regarded as suitable solvents because they represent fire risk and their removal from the product requires complicated apparatus. The addition may also be carried out with acetic acid but the removal of that is also cumbersome and in addition it is strongly corrosive. (Vanags, G.-Veinbergs, A. Ber.

758-725-36(1942) C.A. 37.103(1943).) Reaction of phthalic anhydride and aniline in N-methyi- and N,N-dimethyl-aniline has also been examined: Poraj-Kosic, B. A. Anilinokrasochyan Prom. 4,295-303 (1934), C.A. 31, 5787 (1937). The main product in each case is N-phenyl-phthalamide (N-phenyi-phthalic acid amine) because on the one hand the aniline reacts four times as quickly with the phthalic anhydride than with an N-methyl-aniline while at the same time the N,N-dimethyl-aniline may not react at all, and on the other hand the aniline displaces the N-methyl-aniline from the N-methyl-N-phenylphthalamide. This process is actually the laboratory method of separating N-substituted anilines.

All the processes known from the literature are characterised in that the phthalic anhydride is reacted in some organic solvent with an aromatic amine and the crystalline produce formed is filtered and dried.

The considerable amount of organic solvent remaining in the product causes industrial-scale drying to represent a difficulty; due to the environment-polluting effect and high cost of the solvent it cannot be allowed to pass into the atmosphere while its recovery requires complicated operational steps as well as appreciable energy consumption.

When the phthalic anhydride is reacted in water as the reaction medium, its particle size has a decisive influence on the rate of reaction, see Hungarian Patent Specification No. 1 76582.

It may be seen from the foregoing that in all known production methods a filtering step and a drying step are required to be performed. Yet drying is a delicate operation because between 80-1 400C N-aryl-phthalamides dissociate by losing water. Furthermore, the N-arylphthalamides made by the known processes cannot be utilised without shaping.

Summary of the Invention The invention is based on the discovery that, for instance, some substituted phthalic anhydrides when dispersed in a hydrocarbon oil (e.g. in 'vaseline' oil) react, in dependence on the degree of dispersion, with some substituted aromatic amines in the presence of additive materials (e.g.

wetting, dispersing, concentrating agents) and in this manner an oily suspension is formed which can be diluted with water as desired.

The preparations according to the invention also possess very considerable advantages as regards their application technology in comparison with preparations made with known processes.

The application of the preparation enables not only agricultural spray technology to be used on a field but also aerial spraying technologies such as the so-called low-volume (LV) and ultra-lowvolume (ULV) spraying technologies.

Since the main reaction takes place in a nonaqueous and non-conventional solvent medium, the side reactions described in the known processes, such as esterification, hydrolysis and condensation, do not arise here.

According to our invention oily preparations can be obtained by reacting aliphatic, cycloaliphatic, aromatic or substituted aromatic hydroxyl-, hydroxylamine- or a primary aminecontaining compound with aliphatic, or aromatic, cycloaliphatic or substituted aromatic, or aryl isocyanates or isothiocyanates. Similarly, oily preparations can be obtained starting from aliphatic or aromatic, cycloaliphatic or substituted aromatic oximes by reacting them with aliphatic or aromatic or substituted aromatic or acyl isocyanates or isothiocyanates, furthermore by reacting aromatic, aliphatic or substituted aromatic hydrazines and aromatic, aliphatic or substituted aromatic or acyl isocyanates and isothiocyanates.

Still further, oily preparations may also be obtained by reacting aliphatic, aromatic heterocyclic amines, substituted aromatic amines with aromatic, aliphatic, substituted aromatic or acyl isocyanates or isothiocyanates.

An oily preparation can be obtained by reacting aliphatic, aromatic, or substituted aromatic amines with acid anhydrides, or aliphatic or aromatic acid amides, substituted aromatic acid amides with aliphatic or aromatic isocyanates, substituted aromatic or acyl isocyanates or isothiocyanates as described above.

In a similar manner dithiocarbanic acid suspensions can be formed in the course of a reaction of aliphatic amines and diamines with carbon disulphide from which preparations containing derivatives of the usual composition can be obtained with zinc and manganese compounds, e.g. oxides, carbonates and sulphates.

Still further, phthalimide-type preparations can be obtained by reacting aromatic dicarboxylic acid imides or their salts with trichloromethyl sulfonyl chloride or with the conventional reagents therefor.

In the same manner oil preparations can be obtained from materials containing an -NHgroup in the heterocyclic ring (e.g.

benzimidazocarbamate) with aliphatic, aromatic, substituted aromatic or acyl isocyanates or isothiocyanates.

Expediently, the paraffin-like hydrocarbon oil is a refined mineral oil product known for cosmetics as 'vaseline' (Trade Mark) oil the quality factors or parameters of which are contained in Hungarian Standard MSz-1 3244-53. For the practical realization of the reaction one can proceed also by adding the reagents and the auxiliary materials to the whole or a portion of the quantity of the oil required for the product, under stirring.

One can proceed also by mixing to one part of the oil required for the product one of the reaction components while adding to its other part the other reaction component, in which case the additives can be passed into a mixer system together with any one of the reagents, as regards the time sequence, even at the end of the reaction.

The above-mentioned reactions generally take place in a heterogeneous phase. The progress or course of the reactions can be monitored by analytical control of the decrease of the reagent concentration and of the increase in the product concentration. Reactions always take place at atmospheric pressure, in a temperature range of 0--1400C and in a reaction time of 0.1-24 hours. Following the course of the reaction, the required or expedient dispersed state of the product is brought about by further mixing.

The oily preparation obtained in this way may, whatever the active agent, be diluted with water in accordance with the desired technology.

The proportion of the reaction components is expediently so determined that the concentration of the compounds that form in the reaction should be 5-50 wt. %, expediently 20-30 wt. %.

Henceforth in this specification all percentages given are calculated on weight.

The conventionally used surfactant material concentration is 130%, expediently 1 5-28% and they may be alkyl sulfonates, salts of carboxylic acids, alkyl sulfates, salts of aliphatic sulfonic acids, salts of aromatic sulfonic acids, phosphates, fatty acid esters of polyvalent alcohols, ethylene oxide adducts of fatty acid esters of polyvalent alcohols, fatty acidpolyethylene glycol esters, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of alkyl amines, ethylene oxide adducts of polypropylene glycols, ethylene oxide adducts of mercaptans, ethylene glycol ethers of alkyl aryl polyethylene glycol (alkylarylpolyethylene glycol ether), orthophosphoric acid triesters of alkyl polyethylene glycol ethers.

As concentrating or densifying component, 15%, expediently 12%, of micronised, high specific area silicic acid gels, or bentonites may be used.

The composition may also include up to 20% of water and/or an organic solvent e.g. benzene and N,N dimethylformamide.

Description of Preferred Embodiments EXAMPLE 1 N-Phenyl-Phthalic Acid Amine (N-Phenyl Phthalamide) In apparatus provided with a stirrer or agitator 55.26 g phthalic anhydride are added to 120 g cosmetic 'vaseline' oil and under stirring 34.74 g aniline, 30 g of a wetting agent of the fatty alcohol polyglycol ether type, 12 g wetting agent of the nonylphenyl polyglycol ether type and 3 g of micronised silicic acid gel mixture dispersed in 45 g cosmetic 'vaseline' oil are added. At the end of the addition there is obtained a product containing 30% phthalamide that can be dispersed in water.

EXAMPLE 2 N-Naphthyl (N-Methyl) Carba mate In an apparatus provided with a stirrer and a cooler 40 g of a fatty alcohol polyglycol ether type of wetting agent and 43 g of 1-naphthol and 8 g of micronised silicic acid gel are added to 90 g of cosmetic 'vaseline' oil. To the thus formed suspension 1 8 g of methylisocyanate are fed at room temperature. After the reaction 2 g of aryl polyglycol ether type of wetting agent are added and in this way an oily preparation dispersible in water is obtained which contains 30% of active ingredient.

EXAMPLE 3 N(1 )-Butyl-Carbamoyl-2-Benzimidazole- Carbamate 21 g of 2-(methoxycarbonyl-amino)benzimidazole are measured into an apparatus provided with a stirrer and cooler, then 20 g of surfactant of the fatty alcohol polyglycol ether type and 103 g cosmetic 'vaseline' oil are added and the benzimidazole is dispersed at 600 C.

10.5 g of butylisothiocyanate are added and stirred at this temperature. After a reaction time of 8 hours 5 g of DMF are added to the mixture thereby to obtain a water-dispersible oily preparation with an active ingredient content of 20%. DMF stands for dimethyl formamide.

EXAMPLE 4 N-(Trichloromethyl)-Thio-Phthalimide 75 g of cosmetic 'vaseline' oil are measured into an apparatus provided with a stirrer. 10 g of a fatty alcohol polyglycol ether type surfactant, 6 g of a wetting agent of nonyl-phenyl-polyglycolether type and 31.5 g of phthalimide are added.

To the well dispersed suspension are added 12 g potassium hydroxide dissolved in 25.27 g of water. The suspension is cooled to OOC and to 36.12 g of trichloro-methyl-sulfonyl chloride are added to it. At the end of the reaction an oily preparation is obtained which contains 30 wt. % trichloromethyl-sulphonyl-phthalic imide.

EXAMPLE 5 Preparation of a Composition Containing 2,3 Dihydro-2,2-Di methyl-Benzofuran-7-yl-N Methylcarbamate 67 7 2 ,3-dihydro-2 2-di methyl-7-benzofuranol, 1 74 g te,chnical grade 'vaseline' oil, 1 5 g wetting agent of the fatty alcohol-polyglycol-ether type and 0.2 g triethylamine were charged into a mixer.

While stirring, a mixture of 23 g methyl isocyanate and 20 g technical grade 'vaseline' oil are added.

The temperature was maintained at 200 C. After one hour's stirring, there was obtained a preparation dispersible in water and containing 30 parts by weight of 2,3-dihydro-2,2-dimethyl benzofuran-7-yl-N-methylcarbamate.

EXAMPLE 6 Preparation of a Composition Containing N,N Dimethyl-N'-Phenyl-Urea 45.33 g phenylisocyanate, 181.67 g technical grade 'vaseline' oil, 79 sorbite-mono-oleate surfactant and 23 g oxy-ethylated sorbitetetraoleate surfactant were charged into a mixer.

Then under stirring and at 200C 43 g of a 40 wt. % aqueous solution of dimethylamine were added over a period of 10 minutes. After stirring for one hour, there was obtained a preparation dispersible in water and containing 20 parts by weight of N,N-dimethyl-N-phenyl-urea.

EXAMPLE 7 Preparation of a Composition Containing (3 Methyl-Phenyl)-N-Methylcarbamate 59 g meta-cresol, 149 g technical grade, 'vaseline' oil, 30 g surfactant of the fatty alcoholpolyglycol-ether type and 0.2 g trimethylamine are charged into a mixer, then under stirring a mixture of 30 g technical purity 'vaseline' oil and 31 g methylisocyanate are added, with the temperature being maintained at 200C. After stirring for one hour, there was obtained a preparation dispersible in water and containing 30 parts by weight of (3-methyl-phenyl)-N-methylcarbamate.

EXAMPLE 8 Preparation of a Composition Containing N(m Tolyl)-Phthalamide 52.23 g phthalic anhydride, 1 70 g technical grade 'vaseline' oil, 7 g sorbite-mono-oleate and 23 g oxyethylated sorbite-tetraoleate surfactants were charged into a mixer. Then 37.77 g metatoluidine were added under stirring. The temperature was maintained at 200C. After one hour's stirring, 3 g xylene and 3 g organophilic bentonite were added to the mixture and further stirred for one hour. There was obtained an oily preparation containing 30 parts by weight of N(M-tolyl)-phthalamide.

EXAMPLE 9 Preparation of a Composition Containing Zn-Bis Isopropyl-Dithiocarbamate 37.22 g ZnO, 51.5 g isopropylamine, 39 g surfactant of the fatty aicohol-polyglycol ether type, 99.5 g 'vaseline' oil and 25 g xylene were charged into a mixer. While stirring and maintaining the temperature at 200 C, 66.2 g carbon disulphide were added to the mixture.

After stirring for 3 hours, 6 g surfactant and 5 g organophilic bentonite were added and the mixture was further stirred for 1 hour. There was obtained a preparation dispersible in water and containing 40 parts by weight Zn-bis-isopropyldithiocarbamate.

The main advantages of our invention are: By using the process from the starting material a final product is obtained in a very simple manner which can be directly packaged and which also contains the conventionally employed wetting, dispersing and concentrating components.

The product is obtained in a single step and by means of a technology which is harmless to the environment and which requires minimal energy input; the product is dilutable with water as required by the intended application; thus by using conventional spraying technology or any spraying technology, such as LV or ULV, can be directed at the target plant together with compatible plant protecting agents or fertilisers.

Claims (12)

1. A process for the production of oil-based land-protecting compositions, characterised in that: a) an aliphatic, cycloaliphatic, aromatic, substituted aliphatic, substituted aromatic, hydroxy or hydroxylamine group or a primary amine group or an acid amine group or an -NH group in a heterocyclic ring compound is reacted with an aliphatic, aromatic or substituted aromatic isocyanate or isothiocyanate or acylisocyanate or isothiocyanate, b) an aliphatic or substituted aliphatic amine or aromatic or a substituted aromatic amine is reacted with an aliphatic or aromatic, substituted aromatic or substituted aliphatic acid anhydride, c) an aliphatic amine or aliphatic diamine is reacted with carbon disulfide, or d) a phthalic imide is reacted with trichloro methyl-sulfonylchloride in the presence of surface active or other dispersing materials in an oily medium in such a manner that by mixing, at 0140o C, with a reaction time of 0.1-24 hours, at atmospheric pressure, and in a single step an oily plant protecting composition is formed which contains 5-50 weight percent of the active compounds, 1-30 weight percent surfactant, and the oily medium.

2. A process as claimed in claim 1, wherein the oily medium is a hydrocarbon oil.

3. A process as claimed in claim 1 or claim 2, wherein the composition contains approximately 30% by weight of the active compound.

4. A process as claimed in any one of claims 1 to 3, wherein the composition contains from 1 5 to 20% by weight of a surfactant.

5. A process as claimed in any one of claims 1 to 4, which also includes from 0 to 20% of water and/or an organic solvent.

6. A process as claimed in claim 5, wherein the organic solvent is an aromatic solvent or dimethyl formamide.

7. A process substantially as hereinbefore described in any one of Examples 1 to 9.

8. An oil-based composition made by the process as claimed in any one of claims 1 to 6.

9. An oil-based composition for application to plants and agricultural land, the composition containing 5 to 50% of an active compound, 1 to 30% of a surfactant, 0 to 20% of water and/or organic solvents, the remainder being an oily medium, wherein the active compound was formed in the oily medium in the presence of the surfactant.

10. A composition as claimed in claim 9, wherein the active compound is produced by one of the following reactions: a) an aliphatic, cycioaliphatic, aromatic, substituted aliphatic, substituted aromatic, hydroxy or hydroxylamine group or a primary amine group or an acid amide group or an -NHgroup in a heterocyclic ring compound is reacted with an aliphatic, aromatic or substituted aromatic isocyanate or isothiocyanate or acylisocyanate or isothiocyanate, b) an aliphatic, substituted aliphatic amine aromatic, a substituted aromatic amine is reacted with an aliphatic or aromatic, substituted aromatic or substituted aliphatic acid anhydride, c) aliphatic amine or aliphatic diamine is reacted with carbondisulfide, or d) a phthalic imide is reacted with trichloromethyl-sulfonylchloride.

11. A composition as claimed in claim 9 or claim 10 which contains approximately 30% of the active compound.

12. A composition as claimed in any one of claims 9 to 11 which contains 1 5 to 20% surfactant.

1 3. A composition substantially as hereinbefore described in any one of Exampies 1 to 9.