DRAUZ KARLHEINZ (DE)
LOTTER HERMANN (DE)
SCHAEFER MATTHIAS (DE)
DRAUZ KARLHEINZ (DE)
LOTTER HERMANN (DE)
| FR1415594A | 1965-10-29 | |||
| EP0401059A1 | 1990-12-05 | |||
| FR2165831A1 | 1973-08-10 | |||
| US2954315A | 1960-09-27 |
DATABASE WPI Week 4373, 1973 Derwent Publications Ltd., London, GB; AN 73-65325U U43] & JP,B,48 034 205 (TANABE SEIYAKU) 1973
CHEMICAL ABSTRACTS, vol. 81, no. 13, 30 September 1974 Columbus, Ohio, US; abstract no. 73384k, & JP-A-49 012 028 (KUMIAI CHEMICAL INDUSTRIES CO., LTD.) 2 February 1974 cited in the application
DATABASE WPI Week 0676 1976 Derwent Publications Ltd., London, GB; AN 76-10204X [06] & JP-A-50 105 824 (NAGANO PREFECTURE) , 20 August 1975
INORGANIC CHEMISTRY, vol. 17, no. 1, 1978 EASTON, PA.,US;, pages 34-40, C.-C. OU ET AL. 'Molecular Structure and Magnetic Properties of Trans-Bis(L-methioninato)copper(II), Cu(C5H10NO2S)2'
DATABASE WPI Week 8342 Derwent Publications Ltd., London, GB; AN 83-792998 & RO-A-81 906 (COMB PETROCH PITEST) , 30 May 1983
HOPPE-SEYLER'S ZEITSCHRIFT F]R PHYSIOLOGISCHE CHEMIE, vol. 163, 1927 BERLIN,GE, pages 94-119, E. ABDERHALDEN & E. SCHNITZLER 'Kupersalze von Aminos{uren und Polypetiden'
ANNALES PHARMACEUTIQUES FRANÇAISES, vol. 45, no. 6, 1987 - 1988 PARIS,FR, pages 453-457, C.ARNAUD ET AL. 'Activité anti-inflammatoire de quatre complexes de cuivre d'alpha-aminoacides'
DATABASE WPI Week 9417 Derwent Publications Ltd., London, GB; AN 94-142637 & SU-A-1 794 940 (VOLG POLY) , 15 February 1993
CHEMICAL ABSTRACTS, vol. 86, no. 16, 18 April 1977 Columbus, Ohio, US; abstract no. 111733, N.N.SALEEVA ET AL. 'Solubility in copper(II)arsenate-methionine-water and copper(II)chloride-methionine-water systems at 25ŸC' & DEPOSITED DOC. 1974, VINITI 22-74,
| 1. | Use of a 2amino4methylmercaptobutyric acidcopper complex compound having formula I as fungicide in viticulture. |
| 2. | A process for the fungicidal treatment of vines, characterised in that an agent containing a 2amino4 methylmercaptobutyric acidcopper complex compound having formula I is applied to vines. |
| 3. | Use according to claim 1 for controlling perenospora. |
| 4. | A process according to claim 2, characterised in that it is used to control perenospora. |
| 5. | A process according to claim 2 and 4, characterised in that the formulation contains the active ingredient and diluent and/or surfactants. A process according to claim 2, in which the formulation is applied in quantities such that 0. |
| 6. | 01 kg/ha to 10 kg/ha of active ingredient are applied. |
| 7. | A process for the preparation of a 2amino4 methylmercaptobutyric acidcopper complex compound having formula I characterised in that methionine having formula II is reacted with copper oxychloride or the hydrates thereof having formula III Cu(OH)Cl (III) in the presence of a diluent . |
| 8. | A process according to claim 7, characterised in that water or an alcohol is used as diluent. |
| 9. | A process according to claim 7 or 8, characterised in that the reaction is carried out in the diluent at least for part of the time at a temperature above 50 °C, particularly above 80 °C. |
| 10. | A process according to one of claims 7 to 9, characterised in that the reaction mixture is adjusted to a pH of 4 to 8, particularly at a temperature of 0 to 45 °C. |
The invention relates to the use of the 2-amino-4- ethylmercaptobutyric acid-copper complex compounds having formula I
as fungicide in viticulture, and to a process for the preparation of the complex compounds and processes for applying the formulation containing active ingredient to vines.
It has already become known that compounds having formula I have a fungicidal effect (JP 49-12028, EP 0 482 410, DD 299 695) and have plant-regulating properties (DE 22 17 896 C, EP 0 073 391 A) . The compound having formula I may thus be used for controlling rice, tomato and citrus diseases (JP 49-12028) . The effect, however, particularly if small quantities are applied, is not always satisfactory in every respect.
It is also known that inorganic Cu compounds (e.g. oxides, hydroxides) are used to control perenospora (plasmopara viticola) on vines (EP 0 080 226 B) . The effect of said substances is not always satisfactory in every respect because large application quantities (>50 g/hl active copper) are required to control the vine disease, which means considerable ecological pollution of the area under cultivation.
The object of the invention is to propose the use of a new fungicide in viticulture which is suitable in particular for controlling perenospora on vines. A further object is a process for the fungicidal treatment of vines and a process for the preparation of the compound having a fungicidal effect.
According to the invention, it has now been found that the compound having formula I exhibits an outstanding fungicidal effect on vines, particularly for controlling perenospora, in application quantities which are at the same time very low (<30 g/hl active copper) . The invention relates, therefore, to the use of a 2-amino-4- methylmercaptobutyric acid-copper complex compound having formula I
as fungicide in viticulture, particularly for the control of perenospora.
The invention also contains a process for the fungicidal treatment of vines by the application to vines of a composition containing a 2-amino-4-methylmercaptobutyric acid-copper complex compound having formula I
The invention also includes a process for the preparation of the fungicidal compounds having formula I, wherein methionine having formula II
is reacted with copper oxychloride or the hydrates thereof having formula III
Cu(0H)Cl III
in the presence of a diluent. The diluents considered in preference are protonic polar solvents. These include in, particular, water and alcohols such as methanol, ethanol and propanol, and mixtures thereof, optionally with other solvents. Water is particularly preferred as solvent.
The reaction temperature may be varied within a relatively wide range in the process according to the invention. Generally, operations are carried out at temperatures between 0 and 100 °C, preferably between 20 and 100 °C.
The process according to the invention is generally carried out at normal pressure.
Between 0.4 and 1 mole, preferably about 0.5 mole of starting compound having formula (III) is generally used per mole of starting compound having formula (II) in order to carry out the process according to the invention. The starting substances are mixed with the diluent and optionally stirred at elevated temperature until the end of the reaction. Work-up is carried out according to customary methods. The procedure is generally such that the still hot reaction mixture is cooled and adjusted with an acid acceptor to a pH of between pH 4 and pH 8,
preferably to pH 6 - pH 7. The bases used are preferably inorganic bases, for example, inorganic bases such as sodium hydroxide or potassium hydroxide. The product is optionally precipitated by the addition of an organic diluent such as, for example, acetone, and isolated by customary means, e.g. by suction or centrifuging.
As mentioned already, compounds having formula I are characterised by a strong effect on perenospora on vines.
The compounds to be used according to the invention may be used as individual stereoisomers having formula I or as mixtures of said isomers.
The formulation to be used according to the invention is prepared by mixing a 2-amino-4-methylmercaptobutyric acid- copper complex compound having formula I
with diluents and/or surfactants.
The active ingredients may be converted to the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrafine encapsulations in polymer substances and in encapsulating compounds for seed, and ULV formulations.
Said formulations are prepared in the known way, e.g. by mixing the active ingredients with diluents, i.e. liquid solvents, pressurised liquefied gases and/or solid supports, optionally with the use of surfactants, i.e. emulsifiers and/or dispersing agents and/or foaming agents. If water is used as diluent, organic solvents, for example, may also be used as auxiliary solvents. The liquid
7 Method of preparation of D-L-Cu methioninate:
A suspension is prepared in an 800 1 boiler at 20 °C from 50.0 kg (335 mole) of D, -methionine, bas. copper chloride 18.3 kg (167 mole) (Cu content approx. 58%) and 500 1 of water, which suspension is heated slowly, with stirring (approx. 1 h) to 90-95 °C.
A high stirring speed is required for an optimum procedure. After 2 h at 90-95 °C, full cooling is applied and the batch is adjusted at 30 °C to pH 6.5 with cone, sodium hydroxide solution. Cooling is continued to approx. 15 °C and the product centrifuged.
The product is washed in the centrifuge with a total of
150 ml of water and dried in the drying cabinet at 60-80 °C under vacuum until the weight is constant.
Yield: 60 kg (99%)
Examples of formulation
Example 1: Preparation of a powder formulation
50 parts by weight of the amino acid metal complex compound according to the invention are mixed with 2 parts by weight of calcium lignin sulphonate, 2 parts by weight of alkyl naphthalene sulphonate, 1 part by weight of polyvinyl alcohol and 45 parts by weight of attapulgite, and ground finely to a particle fineness essentially below μm. Said preparation is suspended in water and applied in a spraying process in a concentration of 0.4%.
Example 2: Preparation of a suspension concentrate
500 g of the amino acid complex compound according to the invention with 60 g of monoethylene glycol, 40 g of
emulsifier and 1 g of defoaming agent are made up to a volume of 995 ml with water and then ground in a suspension mill to a particle size of less than 5 μm. 5 ml of a thickener are then added, with stirring. Said preparation is suspended in water and applied in a spraying process in a concentration of 0.4%.
Biological results
Example 1: Comparison of effect on plasmopara viticola (perenospora viticola) on vines in a greenhouse
Application: Spraying process, 0.4% with a single application 4 h before artificial infection
Evaluation: 10 days after application
Attack in Efficacy in Phyto- toxicity
Agent according to the invention 0.22 99.7
Comparative agent (50 g Cu/hl) 1.50 97.7
Control
(untreated) 64.60
Method of preparation of D-L-Cu methioninate:
A suspension is prepared in an 800 1 boiler at 20 °C from 50.0 kg (335 mole) of D,L-methionine, bas. copper chloride 18.3 kg (167 mole) (Cu content approx. 58%) and 500 1 of water, which suspension is heated slowly, with stirring (approx. 1 h) to 90-95 °C.
A high stirring speed is required for an optimum procedure. After 2 h at 90-95 °C, full cooling is applied and the batch is adjusted at 30 °C to pH 6.5 with cone, sodium hydroxide solution. Cooling is continued to approx. 15 °C and the product centrifuged.
The product is washed in the centrifuge with a total of
150 ml of water and dried in the drying cabinet at 60-80 °C under vacuum until the weight is constant.
Yield: 60 kg (99%)
Examples of formulation
Example 1: Preparation of a powder formulation
50 parts by weight of the amino acid metal complex compound according to the invention are mixed with 2 parts by weight of calcium lignin sulphonate, 2 parts by weight of alkyl naphthalene sulphonate, 1 part by weight of polyvinyl alcohol and 45 parts by weight of attapulgite, and ground finely to a particle fineness essentially below μm. Said preparation is suspended in water and applied in a spraying process in a concentration of 0.4%.
Example 2: Preparation of a suspension concentrate
500 g of the amino acid complex compound according to the invention with 60 g of monoethylene glycol, 40 g of
emulsifier and 1 g of defoaming agent are made up to a volume of 995 ml with water and then ground in a suspension mill to a particle size of less than 5 μm. 5 ml of a thickener are then added, with stirring. Said preparation is suspended in water and applied in a spraying process in a concentration of 0.4%.
Biological results
Example 1 Comparison of effect on plasmopara viticola (perenospora viticola) on vines in a greenhouse
Application: Spraying process, 0.4% with a single application 4 h before artificial infection
Evaluation: 10 days after application
Attack in Efficacy in % Phyto- toxicity in
Agent according to the invention 0.22 99.7
Comparative agent (50 g Cu/hl) 1.50 97.7
Control
(untreated) 64.60
Example 2 : Comparison of effect on plasmopara viticola (perenospora viticola) on vines in the open
Application: Spraying method 0.4% with 5 applications as from 7.6. at approx. 14 day intervals
Evaluation: 3 weeks after the final application
Attack in Phyto- toxicity in %
Leaves Grapes
Agent according to the invention 24.8 1.2
Comparative agent (50 g Cu/hl) 26.3 1.5
Control (untreated) 48.8
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