Substituted valinamide derivatives.
Abstract
There are described novel valinamide derivatives of the formula (I) <IMAGE> in which R<1> represents i-propyl or s-butyl and R<2> represents chlorine, methyl, ethyl or methoxy, their preparation, and their use as pesticides.
Term
No projected expiry on record.
- Priority
- Filed
- Granted
- Today
11 claims: 7 independent, 4 dependent
- 1CLAIMS:REIVINDICAÇÕES: la. - Processo para a preparação de derivados de valinamida substituídos de fórmula (I) na qual r! representa i-propilo ou s-butilo e 2 there. A process for the preparation of substituted valinamide derivatives of formula (I) wherein represents i-propyl or s-butyl and 2 R representa cloro, metilo, etilo ou metoxi, nomeadamente, de derivados de valinamida substituídos de fórmula (I) eir que o aminoácido que lhes serve de base é ipropiloxicarbonil-L-valina ou s-butoxicarbonil-L-valina, e a fenetilamina empregada, na qual 2 R represents chloro, methyl, ethyl or methoxy, namely, substituted valinamide derivatives of formula (I) and the amino acid that serves as their base is ipropyloxycarbonyl-L-valine or s-butoxycarbonyl-L-valine, and the phenethylamine employed where 2 R representa cloro, metilo, etilo ou metoxi, ou é racémica, ou tem a configuração R(+) ou a configuração S(-), no centre de assimetria, e especialmente de derivados de valinamida substituídos de fórmula (I) em que o aminoácido que lhes serve de base é i-propiloxicarbonil-L-valina ou sbutoxicarbonil-L-valina, e a fenetilamina empregada, na qual 2 R represents chlorine, methyl, ethyl or methoxy, or is racemic, or has the R (+) or S (-) configuration at the center of asymmetry, and especially substituted valinamide derivatives of formula (I) wherein A base amino acid is i-propyloxycarbonyl-L-valine or butoxycarbonyl-L-valine, and the phenethylamine employed, in which 2 R representa cloro, metilo, etilo ou metoxi, ou é racémica ou tem a configuração R( + ) no centro de assimetria com propriedades fungicidas, caracterizado pele facto de se fazer reagir um aminoácido substituído de fórmula (II) η3ν^ / 3 <ρϊΓ R represents chlorine, methyl, ethyl or methoxy, or is racemic or has the R (+) configuration at the center of asymmetry with fungicidal properties, characterized in that a substituted amino acid of formula (II) η is reacted.3ν ^ / 3 <ρϊΓ R1-O-CO-NH-CH-COOH (II) in which R1-O-CO-NH-CH-COOH (II) na qual R1 representa i-propilo ou sec.-butilo, ou um dos seus derivados carboxiactivados, eventualmente em presença de um catalisador, eventualmente em presença de um agente de ligação de ácido e eventualmente em presença de um diluente com uma amina de fórmula (III) na qual 2 R1 represents i-propyl or sec.-butyl, or one of its carboxy-activated derivatives, optionally in the presence of a catalyst, optionally in the presence of an acid-binding agent and optionally in the presence of a diluent with an amine of formula (III) in which 2 R representa cloro, metilo, etilo ou metoxi. R represents chloro, methyl, ethyl or methoxy.
- 33a. - Processo de acordo com as reivindicações 1 e 2, caracterizado pelo facto de como dissolventes, se empregarerr acetona, etilmetilcetona, acetato de etilo, acetato de metilo, dimetilformamida, acetonitrilo, cloreto de metileno, tetracloreto de carbono, tolueno, tetra-hidrofurano, assin como eventualmente água e as suas misturas. 3rd 2. A process according to claims 1 and 2 wherein acetone, ethyl methyl ketone, ethyl acetate, methyl acetate, dimethylformamide, acetonitrile, methylene chloride, carbon tetrachloride, toluene, tetrahydrofuran are used as solvents. as possibly water and mixtures thereof.
- 44a. - Processo de acordo com as reivindicações 1, 2 e 3, caracterizado pelo facto de, como agentes de ligação de ácidos, se empregarem tritilamina, piridina, Nmetilpiperidina, hidróxido de sódio, hidróxido de potássio, carbonato de sódio ou carbonato de cálcio. 4th 6. A process according to any one of claims 1, 2 and 3, characterized in that, as acid binding agents, tritylamine, pyridine, Nmethylpiperidine, sodium hydroxide, potassium hydroxide, sodium carbonate or calcium carbonate are employed.
- 6
- 77a. - Processo para a preoaração duma composição fungicida com base em derivados de valinamida susbtituídos, caracterizado pelo facto de se misturarem derivados de valinamida substituídos de fórmula (I) de acordo com qualquer das reivindicações anteriores com diluentes e/ou agentes tensioactivos. 7a. A process for preparing a fungicidal composition based on substituted valinamide derivatives, wherein the substituted valinamide derivatives of formula (I) according to any of the preceding claims are mixed with diluents and / or surfactants.
- 99a. - Processo de acordo com as reivindicações 6 e 7, caracterizado pelo facto de se empregarem as seguintes substancias auxiliares:9a. A process according to claims 6 and 7, characterized in that the following auxiliary substances are employed: as solvents, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, alcohols and their esters and ethers, ketones, strongly polar solvents and water;como dissolventes, hidrocarbonetos aromáticos, hidrocarbonetos aromáticos clorados, hidrocarbonetos alifáticos clorados, hidrocarbonetos alifáticos, álcoois e seus ésteres e éteres, cetonas, dissolventes fortemente polares e água;as liquefied gaseous diluents or carriers, aerosol entraining agents;como diluentes ou portadores gasosos liquefeitos, agentes de arrastamento de aerossóis;as solid carriers, pulverized natural and synthetic mineral products and granulated natural and synthetic mineral and organic products;como substancias veiculares sólidas, produtos minerais naturais e sintéticos pulverizados e produtos minerais e orgânicos naturais e sintéticos granulados;as emulsifying and / or foaming agents, nonionic and anionic emulsifying agents;como agentes emulsionantes e/ou espumificantes, agentes emulsionantes não ionogénios e aniónicos;as dispersing agents, lignin sulfite and methyl cellulose leachates;como agentes dispersantes, lixivias de ligninasulfito e metil-celulose;as adhesives, carboxymethyl cellulose, natural and synthetic polymers in the form of powder, granules or latex, or natural phospholipids;and mineral and vegetable oils. como agentes adesivos, carboximetil-celulose, polímeros naturais e sintéticos sob a forma de pó, de grânulos ou de látex, ou fosfolipidos naturais;e ainda óleos minerais e vegetais.
Independent claims7
480 paragraphs in 51 sections, as filed
DESCRIPTION
GIVES
PATENT OF INVENTION
No. 98,696
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APPLICANT; BAYER AKTIENGESELLSCHAFT, German, Industrial, established in 5090 Leverkusen, Federal Republic of Germany
EPIGRAPH: PROCESS FOR PREPARING FUNGICIDE REPLACED VALINAMIDE DERIVATIVES
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INVENTORS: Dr. THOMAS SEITZ, Dr. DETLEF WOLLWEBER, Dr. WILHELM BRANDES and Dr. HEINZ-WILHELM DEHNE
Claim of right of priority under Article 4 of the Paris Convention of 20 March 1883.
Germany on 25 August 1990 under the N<sup>The</sup> P 40 26 966.3
INPI MOO RF 16732
V
<img file="PT98696B_D0003.tif" />
R, .Ε SUMQ
The invention relates to the process for the preparation of substituted fungicidal valinamide derivatives of formula (I) no.<sub>3</sub>TV
CH h<sub>3</sub>ç<sub>x</sub> ^ ch<sub>3</sub>
R<sup>1</sup>-O-CO-NH-CH-CO-NH-CH * I
CH-
<img file="PT98696B_D0004.tif" />
// (I)
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wherein R is claims, substituted of formula (II)
R has the meanings mentioned as comprising the reaction of an amino acid <sup>H</sup>3<sup>Ç</sup> x ^<sup>CH:</sup>
R<sup>1</sup>-O-CO-NH-CH-COOH (II) or a carboxy-activated derivative thereof having an amine of formula (III)
<img file="PT98696B_D0006.tif" />
H<sub>2</sub>n-ch <sup>CH</sup>3 <sub>(IIl</sub>) optionally in the presence of a catalyst, optionally in the presence of an acid binding agent and optionally in the presence of a diluting agent.
The invention also relates to the process for the preparation of fungicidal compositions containing the compounds of formula (I) as an active and plant protection ingredient against reaction of fungi with such fungicidal compositions.
The invention relates to novel valinamide derivatives, a process for their preparation as well as their use as pesticidal agents, in particular as fungicides.
The substances according to the invention have excellent pest control activity, in particular they can be employed as fungicides, especially in plant protection.
Certain aminic acid amides are already known (see
<img file="PT98696B_D0007.tif" />
BP-A 236 874). A use of said compounds in pesticidal compositions is not, however, described.
New valinamide derivatives of formula (I) h have now been discovered.<sub>3</sub>with CH, <sup>3</sup>
GH
<img file="PT98696B_D0008.tif" />
, 1 H-O-CO-NH-CH-CO-EH-CH— *
CH-,
5K
<img file="PT98696B_D0009.tif" />
• R (D in which
R<sup>1</sup> represents i-propyl or sec.-butyl, and 2
R represents chloro, methyl, ethyl or methoxy.
<img file="PT98696B_D0010.tif" />
The compounds of formula (I) contain two centers of chirality and, therefore, may exist in various enantiomer and diastereomer mixtures, which may optionally be separated in conventional manner. Both pure enantiomers and diastereomers as well as mixtures according to the present invention are claimed.
In the following, and for the sake of simplicity, reference will always be made to the compounds of formula (I), although not only pure compounds but also mixtures of various proportions of isomers, enantiomers and diastereomers are to be referred to.
Valinamide derivatives of formula (I) are obtained:
<img file="PT98696B_D0011.tif" />
<img file="PT98696B_D0012.tif" />
in which
R<sup>1</sup> represents i-propyl or s-butyl, and 2
R represents chloro, methyl, ethyl or methoxy when reacting a substituted amino acid of formula (II) h<sub>3</sub>ç
CHCHr-o-co-nh-AhGOOH (II) in which
<img file="PT98696B_D0013.tif" />
R 4 represents i-propyl or s-butyl, or carboxy-activated derivatives thereof, optionally in the presence of a catalyst, optionally in the presence of an acid-binding agent and optionally in the presence of a diluent, with an amine of formula (III). )
H
<img file="PT98696B_D0014.tif" />
CH<sub>3</sub> (III)
<img file="PT98696B_D0015.tif" />
in which
R represents chloro, methyl, ethyl or methoxy.
If, for example, i-propyloxycarbonyl-L-valine and 4-chlorophenethylamine are used as starting materials, then the course of the process according to the invention can be reproduced by the following formula scheme.
<img file="PT98696B_D0016.tif" />
GH3. ^<sup>Ci</sup>3
CH (CHj<sub>?</sub>CH-O-CO-NH-CH-COOH + M-CH-
<img file="PT98696B_D0017.tif" />
—Cl
CH<sub>3</sub> ch<sub>3</sub>
CH
<img file="PT98696B_D0018.tif" />
(CH-,) <sub>?</sub>CH- 0-CO-0H- CH-
<img file="PT98696B_D0019.tif" />
—Cl
Preferred are those compounds of formula (I), wherein the base amino acid of formula (II) is i-propyloxycarbonyl-L-valine or s-butoxycarbonyl-L-valine, and the phenethylamine employed of formula ( III), in which
R represents chlorine, methyl, ethyl or methoxy, or racemic O, or has the R (+) configuration, or has the S (-) configuration, and appears at the asymmetric center.
Especially preferred are the compounds of formula (i) in the
<img file="PT98696B_D0020.tif" />
which amino acid it is in base is i-propyloxycarbonyl-L-valine or s-butoxycarbonyl-L-valine, and the phenethylamine used, in which
R represents chloro, methyl, ethyl or methoxy, is a racemic compound or has, at the asymmetric center, the R (+) configuration.
Amino acid derivatives to be employed as starting materials in carrying out the process according to the invention are generally defined by formula (II). This formula R and R preferably have the meanings already mentioned as being preferred with respect to the description of the substances of formula (I) according to the invention.
Amino acid derivatives of formula (II) are generally known (see, for example, Houben-Y / eyl, Methoden der organischen Chemie, Volume XV, parts 1 and 2, sheet 46 and following and sheet 112 and following, C-eorg Thieme Verlag, Stuttgart 1974; D. Keller et al., Org. Synth. 60, 2145 (1981) or RC Sheppard, Aspecialist Periodical Report, Amino-acids, Peptids and Proteins, The Royal Society of Ohemistry, Burlington House London 1978, or IP G-reenstein and M. Winitz, Ohemistry of Amino Acids, I. Yiley Olson Inc., New York, London 1961; or
E. Schroder and K. Lttbke, the Peptides, Volume I, Academic Press New York, London, 1965; or they may be obtained by the processes mentioned in those works.
Carboxy-activated derivatives of the amino acid of formula (II) are also generally known to be employed as starting materials for carrying out the process according to the invention.
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I
I
The carboxy-activated derivatives of the amino acids of formula (II) include all carboxy-activated derivatives, such as acid halides, such as acid chloride, acid azides, and symmetric and mixed anhydrides, such as mixed anhydrides. O-alkyl carboxylic acid, and further activated esters, such as p-nitrophenyl ester or l-hydroxysuccinimide ester, as well as with condensing agents, as for example dicyclohexyl carbodiimide or carbonyldiimidazole, form of activated amino acids produced in situ ”.
Preferably the acid chlorides and mixed anhydrides corresponding to the amino acids of formula (III) are used. They may be prepared by reacting the amino acids of formula (II) or their salts with a halogenating agent or one of the generally known agents for the preparation of mixed anhydrides such as phosphorus pentachloride, thionyl chloride. oxalyl chloride and isobutyl ester of chloroform acid, generally in a conventional manner. The application of isobutyl ester of chloroform acid is preferred.
<img file="PT98696B_D0023.tif" />
The reaction may be carried out in the presence of inert diluents such as aromatic, non-aromatic or halogenated hydrocarbons such as ketones such as acetone; esters, such as ethyl acetate; amides, such as dimethylformamide; nitriles, such as acetonitrile; chlorinated hydrocarbons, such as methylene chloride; hydrocarbons, such as toluene; or ethers, such as tetrahydrofuran; or mixtures thereof, and / or in the presence of an acid-binding agent, such as preferably from a tertiary amine, such as triethylamine, pyridine or N-methylpiperidine, at temperatures in the range of from 1 to 6 ° C.<sup>2</sup>C and 100<sup>2</sup>C, preferably between -60<sup>2</sup>C and 25-20.
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In addition, the amines to be employed as starting materials for carrying out the process according to the invention are generally defined by formula (III).
R has the meanings already mentioned above.
The amines of formula (III) are compounds generally known from organic chemistry.
The diluents of interest for the process according to the invention are inert organic solvents such as: ketones, such as acetone or ethyl methyl ketone; esters, such as ethyl acetate or methyl acetate; amides, such as dimethylformamide; nitriles, such as acetonitrile; chlorinated hydrocarbons, such as methylene chloride or carbon tetrachloride; hydrocarbons, such as itoluene; or ethers, such as tetrahydrofuran, as well as optionally water or mixtures thereof.
Acid binding agents of interest to the process according to the invention are the usual organic or inorganic acid binding agents. These preferably include tertiary amines such as triethylamine, pyridine or N-methylpiperidine as well as inorganic bases, for example metal hydroxides such as sodium hydroxide or potassium hydroxide; or metal carbonates, such as sodium carbonate or calcium carbonate.
The process according to the invention is carried out possibly in the presence of a catalyst. For example, 4'-dimethylamino pyridine, 1-hydroxybenzotriazole or dimethylformamide are mentioned.
Temperatures during the process may vary within a larger range. Generally work at a temperature of -78 ° C to + 120 ° C, preferably between
<img file="PT98696B_D0027.tif" />
tre -602 and +40<sup>and</sup>Ç.
In carrying out the process according to the invention, preferably in equimolar amounts, preferably.
In this case the amino acid derivatives of formula (II) are employed as pure optical isomers (L or L forms) or as racemates.
The invention comprises both pure isomers as well as mixtures. These mixtures may be separated according to conventional procedures, for example by selective crystallization from appropriate solvents or by silica gel or aluminum oxide chromatography on their components. Racemates may be separated according to conventional procedures in their isolated enantiomers, as well as for example by salt formation with optically active acids, such as canfersulfonic acid or dibenzyl tartaric acid, and by selective crystallization or derivatization with suitable optically reagents. active agents, separation, diastereomeric derivatives and redissociation or separation in optically active column material.
The active substances of formula (I) according to the invention have a strong effect against pests and can be used in practice to combat harmful organisms. For application as plant protection agents, the active substances are especially suitable as fungicidal compositions.
Plant protection fungicidal compositions are used to combat the following microorganisms: plasmodioforomycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes and deuteromycetes.
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By way of example, but without being limiting in any way, some microorganisms that cause phytogenic diseases in plants and which belong to the families mentioned above may be mentioned:
Pythium species, such as Pythium ultimum;
Phytoph.th.ora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cuhense;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or Peronospora hrassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuligjnea Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or Pyrenophora graminea (conidial form: Erechslera, synonym: Helminthosporium);
Gochlioholus species, such as Cochlioholus sativus (conidial form: Erechslera, synonym: Helminthosporium); Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia orizae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum, for example;
Cercospora species, such as Oercospora canescens;
Alternaria species, such as Alternaria brassicae; and Pseudocercosporella species, such as Pseudocercosporella herpotrichoides,
The good compatibility with plants of the active substances in the concentrations necessary for the treatment of their diseases allows for the treatment of the aerial parts of plants, plants and seeds and soil.
In this case the active substances according to the invention can be employed with particularly great success in combating Ph.ytoph.th.ora species in tomatoes and Plasmopara species in<sub>: </sub>vines.
In addition, the active substances are also shown to have insecticidal activity on the leaves.
Depending on their respective physical and / or chemical properties, the active substances may be transformed into the usual formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, polymeric microcapsules and seed treatment pastes. as well as in cold and hot ULV nebulizer formulations.
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These formulations are prepared in a known manner, for example by mixing the active substances with diluents, therefore liquid solvents, pressure liquefied gases and / or solid carriers, optionally with the application of surfactants, hence emulsifiers and / or dispersants, and / or foaming compounds. If water is used as a diluent, for example, organic solvents may also be employed as auxiliaries for dissolving. Liquid solvents essentially include: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes, or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins, for example, petroleum distillation fractions, alcohols such as butanol or glycol, as well as ethers and esters thereof; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water; diluents or carriers in the form of liquefied gas means those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide; solid carriers include: for example, finely ground rocks such as kaolin, clay soil, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, fine and synthetic powders such as highly dispersed silicic acid, aluminum dioxide and silicates; solid carriers for granulates include: broken and fractionated natural rocks such as calcite, marble, plaster, sepiolite, dolomite, as well as synthetic granules made from organic and inorganic flours as well as granules made from an organic material such as sawdust, coconuts, corncobs and stem
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<img file="PT98696B_D0031.tif" />
of tobacco; emulsifying and / or foaming agents include, for example, anionic and nonionic emulsifying agents, for example polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolic ether, alkylsulfonates, alkylsulfates, arylsulfonates, as well as as albumin hydrolysates. Dispersants include: for example sulfite-lignin and methylcellulose leaches.
Adhesive compounds such as carboxymethylcellulose, natural or synthetic polymers in powder, grain or latex forms such as gum arabic, polyvinyl alcohol, polyvinyl acetate as well as natural phospholipids such as cephalin and lecithin may be employed in the formulations. , and synthetic phospholipids *! toxic. Other additives may be mineral and vegetable oils.
Dyes such as inorganic pigments may be used, for example iron oxide, titanium oxide, Prassian blue and organic dyes such as alizarin and azo d metallo-phthalocyanine dyes, and trace elements such as iron salts, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally contain from 0.1 to 95 percent by weight of active substance, preferably from 05 to 90%.
The active substances according to the invention may exist in formulations in admixture with other known active substances, such as fungicidal, insecticidal, acaricidal and herbicidal agents, as well as in admixture with fertilizers and growth regulating agents.
The active substances may be employed as such, in the form of the respective formulations and in the application forms prepared from said formulations, as ready-made solutions.
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<img file="PT98696B_D0034.tif" />
for use, emulsifiable concentrates, emulsions, foams, suspensions, spray powders, pastes, soluble powders, fine powders and granules. Application is customary, for example by watering, splashing, spraying, spreading, dusting, foaming, coating and the like. Beyond . In addition, the active substances may be formulated using the ultra low volume process and the soil prepared with the active substance or the active substance itself may be injected into the soil. The seeds of these plants can also be treated.
For the treatment of plant parts, the concentrations of the active substances in the application forms may vary over a wide range. They are generally between 1 and 0.0001 / by weight, preferably between 0.5 and 0.001 /.
For seed treatment, in general, quantities of active substances between 0.001 and 50 g per kg of seed, preferably 0.01 to 10 g, are required.
In the case of soil treatment, active substance concentrations of from 0.0001 to 0.1% by weight, preferably from 0.0001 to 0.02% at the site of action, are required.
In the case of treatment of animal parasites, the concentrations of active substances generally range from 0.000 000 1 to 95% of the active substance, preferably from 0.0001 to 1%.
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Preparation Examples:
Example 1
<img file="PT98696B_D0036.tif" />
<img file="PT98696B_D0037.tif" />
CH<sub>0</sub> 0 'CH 0 CH' 3
<img file="PT98696B_D0038.tif" />
—OCH
To 4.67 g of i-propoxycarbonyl-1-valine (0.023 mol) dissolved in 50 ml of CH was added<sub>2</sub>C1<sub>2</sub>at -20 ° C, 2.3 g (0.023 mol) of N-methylpiperidine. Then add by dripping at a temperature of ~ 2 ° C<sup>s</sup>C, 3.2 g (0.023 mol) of chloroform acid isobutyl ester, then stirred at the same temperature for 10 minutes, cooled to -60 ° C<sup>2</sup>C and 4 g (0.023 mol) of 4-methoxy-1-phenylethylamine are allowed to flow in so that the temperature remains below -15 ° C. After 2 hours at -15 ° C<sup>2</sup>O, stir continuously for 15 hours at room temperature, filter off solid, wash with CH<sub>2</sub>C1<sub>2</sub>Concentrate, add water to the residue, extract 2 times with acetic ester, wash the combined acetic ester phases with a NaHCO 3 solution and water, dry and concentrate. 4.64 g (60% of theory) of N- (i-propyloxycarbonyl) -L-valin-4-methoxyphenylethylamide having a melting point of 167 ° C is obtained.
Similarly to Example 1, the following compounds of formula (I) are obtained.
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<td>α</td><td>ΗΗ ι-Μ</td><td>Α</td>
<td>ο</td><td>ο</td><td>ο</td>
III
CQ 'ό ιη
LO
Α
Ο .ο
<img file="PT98696B_D0043.tif" />
Table 1 - (Continued)
Amino Acid Constant Example
<td></td><td colspan="2">Λ</td><td>Λ</td>
<td></td><td>• d</td><td></td><td>• d</td>
<td></td><td>rf</td><td></td><td>rf</td>
<td></td><td>O</td><td></td><td>O</td>
<td></td><td>P</td><td></td><td>P</td>
<td></td><td>rf</td><td></td><td>rf</td>
<td></td><td>d</td><td></td><td>rf</td>
<td></td><td>O</td><td></td><td>O</td>
<td></td><td>• d</td><td></td><td>• d</td>
<td>O</td><td>M</td><td>rf</td><td>M</td>
<td>Ό</td><td>O</td><td>rf</td><td>O</td>
<td>d</td><td>rd</td><td>• d</td><td>THE</td>
<td>bQ</td><td>d</td><td>THE</td><td>• d</td>
<td>ω</td><td>THE</td><td> «3</td><td> +<sup>3</sup></td>
<td>rf</td><td>rf</td><td>í></td><td>rf</td>
<td>THE</td><td>THE</td><td> 1</td><td>THE</td>
<td>The</td><td> 1</td><td>THE</td><td> 1</td>
<td>O</td><td>m</td><td> 1</td><td>m</td>
<td></td><td>O</td><td></td><td>O</td>
<td></td><td>O</td><td></td><td>O</td>
<td>d</td><td>fO</td><td></td><td>m</td>
<td>O</td><td>THE·</td><td></td><td>Lf \</td>
<td>• d</td><td>rd</td><td></td><td>THE</td>
<td>frog</td><td></td><td></td><td></td>
<td>M</td><td> ··</td><td></td><td> ««</td>
<td>THE</td><td> •</td><td></td><td> •</td>
<td></td><td>THE</td><td></td><td>THE</td>
<td></td><td>THE</td><td></td><td>Pd</td>
<td> 1</td><td>rf rrf</td><td>Λ</td>
<td>THE</td><td>•H</td><td>♦ H</td>
<td>• d</td><td>The</td><td>rf</td>
<td>rf</td><td></td><td>O</td>
<td>O</td><td></td><td>P</td>
<td>P</td><td>X * X</td><td>rf</td>
<td>rf</td><td> +</td><td>rf</td>
<td>rf</td><td>THE</td><td>O</td>
<td>O</td><td></td><td>• d</td>
<td>♦ rd</td><td></td><td>H</td>
<td>M</td><td>rf</td><td>O</td>
<td>O</td><td>rf</td><td>THE</td>
<td>THE</td><td>• d</td><td>• d</td>
<td>• d</td><td>THE</td><td>THE</td>
<td>THE</td><td>rf</td><td>O</td>
<td>rf</td><td>i></td><td>rf</td>
<td>THE</td><td> 1</td><td>THE</td>
<td> 1</td><td>THE</td><td> 1,</td>
<td>frog</td><td> 1</td><td>• d</td>
<td>O</td><td></td><td>O</td>
<td>O</td><td> 1</td><td>O</td>
<td>GO</td><td>r — Í</td><td>CM</td>
<td>co</td><td>OJ</td><td>CM</td>
<td>i — 1</td><td>í— |</td><td>THE 1</td>
<td> ··</td><td> ««</td><td> 1</td>
<td> •</td><td> •</td><td></td>
<td>THE</td><td>THE</td><td></td>
<td>THE</td><td>THE</td><td></td>
ro
CM o
xó xó
<img file="PT98696B_D0044.tif" />
CM
ΓΟ
To
<-x
THE
O
I ol co troo cn rf rf • d
The rf
J,
I la ~ Bela 1 - (Continued)
Constant Example
<img file="PT98696B_D0045.tif" />
<td>O nj</td><td colspan="3">Jl</td><td colspan="2">Λ • r |</td><td>d XS • rl</td><td>1 ft</td><td>c3 ft ft</td>
<td>ni</td><td></td><td> 6</td><td></td><td></td><td> 6</td><td>B</td><td>• rl</td><td>s</td>
<td>bO</td><td></td><td>O</td><td></td><td></td><td>O</td><td> «?</td><td> 8</td><td></td>
<td>ω</td><td></td><td>THE</td><td></td><td></td><td>THE</td><td></td><td>O</td><td></td>
<td></td><td></td><td>THE</td><td></td><td></td><td>THE</td><td></td><td>ft</td><td> ,—,</td>
<td>ft</td><td></td><td>right</td><td></td><td></td><td> 8</td><td> +</td><td>THE</td><td> +</td>
<td>B</td><td></td><td>O</td><td></td><td></td><td>O</td><td>ft</td><td>right</td><td>ft</td>
<td>Φ</td><td></td><td>• rl</td><td></td><td></td><td>ft</td><td> -—,</td><td>O</td><td></td>
<td></td><td></td><td>N</td><td>d</td><td></td><td>N</td><td></td><td>'rl</td><td></td>
<td>O</td><td></td><td>O</td><td>fl</td><td></td><td>O</td><td>d</td><td>K</td><td>d</td>
<td>ft</td><td></td><td> <—1</td><td>•H</td><td></td><td>ϊ — 1</td><td>fl</td><td>O</td><td>d</td>
<td>•H</td><td></td><td>•H</td><td>ft</td><td></td><td>ft</td><td>ft</td><td>ft</td><td>ft</td>
<td>O</td><td></td><td> +=</td><td>d</td><td></td><td>ft</td><td>ft</td><td>• rl</td><td>ft</td>
<td>* oJ</td><td></td><td>Pi</td><td> !></td><td></td><td>O</td><td>d</td><td>-P</td><td></td>
<td>O</td><td></td><td>THE</td><td> 1</td><td></td><td></td><td> ></td><td>Pi</td><td rowspan="2"> > »</td>
<td></td><td></td><td> 1</td><td>THE</td><td></td><td>ft</td><td> 1</td><td>ft</td>
<td>•H</td><td></td><td>frog</td><td> 1</td><td></td><td>1 • rl</td><td>THE 1</td><td>1 frog</td><td>THE 1 O</td>
<td></td><td></td><td>O</td><td></td><td></td><td>O</td><td></td><td> 1</td><td>O</td>
<td></td><td> 1</td><td>O</td><td></td><td> 1</td><td>O</td><td></td><td>O</td><td>CM</td>
<td> «5</td><td>rH</td><td>CM</td><td></td><td></td><td>grandfather</td><td></td><td></td><td>ft ·</td>
<td>O</td><td></td><td>r-1</td><td></td><td>m</td><td>m</td><td></td><td><—I</td><td>ft</td>
<td>• rl</td><td>H</td><td>ft</td><td></td><td>J — J</td><td>ft</td><td></td><td></td><td> 1</td>
<td>frog</td><td></td><td>I</td><td></td><td></td><td> 1</td><td></td><td> «·</td><td></td>
<td>Ή</td><td> ·«</td><td></td><td></td><td> ««</td><td></td><td></td><td> «</td><td></td>
<td> 41</td><td> «</td><td></td><td></td><td>ft</td><td></td><td></td><td>ft</td><td></td>
<td></td><td>ft</td><td></td><td></td><td> «</td><td></td><td></td><td> ♦</td><td></td>
<td></td><td>ft</td><td></td><td></td><td>ft</td><td></td><td></td><td>ft</td><td></td>
CM
Pd
<img file="PT98696B_D0046.tif" />
<img file="PT98696B_D0047.tif" />
<img file="PT98696B_D0048.tif" />
<img file="PT98696B_D0049.tif" />
hi f-5 »
CM
H (D
-P
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O
<img file="PT98696B_D0050.tif" />
O
The ethiT
0) laughs
A to
oo
THE
THE
O '0
O
At
«Laughs the
The ra
A «H
<td></td><td> 1</td><td>laugh</td><td></td><td>laugh</td><td>l</td><td>laugh</td><td></td><td>laugh</td>
<td></td><td>i — 1</td><td>THE</td><td> 1</td><td>THE</td><td>1 — I</td><td>THE</td><td> 1</td><td>THE</td>
<td></td><td>THE</td><td>Ή</td><td>THE</td><td>THE</td><td>THE</td><td>THE</td><td>THE</td><td>THE</td>
<td></td><td>laugh</td><td>s</td><td>THE</td><td>The</td><td>laugh</td><td>The</td><td>THE</td><td>s</td>
<td></td><td>O</td><td> <3</td><td>laugh</td><td><s</td><td>O</td><td>«Laughs</td><td>laugh</td><td>«Laughs</td>
<td></td><td>THE</td><td></td><td>O</td><td></td><td>THE</td><td></td><td>O</td><td></td>
<td></td><td>laugh</td><td>X ---</td><td>THE</td><td></td><td>laugh</td><td></td><td>THE</td><td>x—</td>
<td></td><td>d</td><td> +</td><td>laugh</td><td> +</td><td>laugh</td><td> +</td><td>laugh</td><td> +</td>
<td></td><td>O</td><td>Pl</td><td>laugh</td><td>Pl</td><td>O</td><td>THE</td><td>laugh</td><td>THE</td>
<td></td><td>THE</td><td>* __ y</td><td>O</td><td></td><td>THE</td><td></td><td>O</td><td></td>
<td></td><td>H</td><td></td><td>THE</td><td></td><td>N</td><td></td><td>THE</td><td></td>
<td></td><td>O</td><td>laugh</td><td>M</td><td>laugh</td><td>O</td><td>laugh</td><td></td><td>laugh</td>
<td></td><td>THE</td><td>Ci</td><td>O</td><td>laugh</td><td>THE</td><td>laugh</td><td>O</td><td>laugh</td>
<td></td><td>THE</td><td>THE</td><td> —1</td><td>THE</td><td>THE</td><td>THE</td><td>THE</td><td>THE</td>
<td></td><td>P,</td><td>i — 1</td><td>THE</td><td>• —i</td><td>THE</td><td>* —I</td><td>THE</td><td> —1</td>
<td></td><td>O</td><td>Ass</td><td>-P</td><td>laugh</td><td>O</td><td>laugh</td><td>THE</td><td>laugh</td>
<td></td><td>laugh</td><td>i></td><td></td><td>i></td><td>laugh</td><td>i></td><td>laugh</td><td>t></td>
<td></td><td>PM</td><td> 1</td><td>why</td><td> 1</td><td>THE</td><td>l</td><td>PQ</td><td> 1</td>
<td></td><td> 1</td><td>THE</td><td> 1</td><td>THE</td><td> 1</td><td>THE</td><td> 1</td><td>THE</td>
<td></td><td>• Γ-Ι</td><td> 1</td><td>frog</td><td> 1</td><td>•H</td><td> 1</td><td>frog</td><td> 1</td>
<td></td><td></td><td></td><td>O</td><td></td><td>O</td><td></td><td>O</td><td></td>
<td></td><td></td><td></td><td>O</td><td></td><td>O</td><td></td><td>O</td><td></td>
<td> 1</td><td>O</td><td></td><td>THE</td><td></td><td>m</td><td></td><td>O</td><td></td>
<td>ç-</td><td>O</td><td></td><td>Ç-</td><td></td><td>co</td><td></td><td> 00</td><td></td>
<td>ç-</td><td>cn</td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td><td></td>
<td>THE</td><td> !></td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td></td>
<td></td><td>THE</td><td></td><td>cn</td><td></td><td>m</td><td></td><td>CO</td><td></td>
<td> ·«</td><td> 1</td><td></td><td>grandfather</td><td></td><td>ω</td><td></td><td>t></td><td></td>
<td> •</td><td></td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td><td></td>
<td>THE</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>PM</td><td></td><td></td><td> ··</td><td></td><td> «.</td><td></td><td> ♦ ·</td><td></td>
<td></td><td></td><td></td><td> •</td><td></td><td> »</td><td></td><td> •</td><td></td>
<td></td><td></td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td><td></td>
<td></td><td></td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td colspan="2">m</td><td>m</td><td></td>
<td colspan="2">m</td><td></td><td colspan="2">ΓΩ</td><td>tri</td><td></td><td>tri</td><td></td>
<td></td><td></td><td></td><td>tq</td><td></td><td>O</td><td></td><td>O</td><td></td>
<td>O</td><td></td><td></td><td>O</td><td></td><td>O</td><td></td><td>O</td><td></td>
CM
The Gabela 1 - (Gontinuagão)
To
<img file="PT98696B_D0051.tif" />
O
1-1
THE
The fc) ra
Hi laugh
AAA
<img file="PT98696B_D0052.tif" />
<img file="PT98696B_D0053.tif" />
Table 1 - (Pont inuation)
<img file="PT98696B_D0054.tif" />
I β
rf
O • rJ
<td></td><td>L</td><td></td><td>X</td><td></td><td>L</td><td></td><td>l</td><td></td><td>ι</td>
<td>Ο</td><td>Α</td><td></td><td>O</td><td></td><td>THE</td><td></td><td>M</td><td></td><td>THE</td>
<td>Α</td><td>«T</td><td></td><td>laugh</td><td></td><td> *»</td><td></td><td>♦ k</td><td></td><td> ·%</td>
<td>rf</td><td>Α</td><td></td><td>• laughs</td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td>
<td>ko</td><td> 1</td><td></td><td>THE</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td>
<td> 0)</td><td>Η</td><td></td><td>O</td><td></td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td>
<td>THE</td><td>• laughs</td><td></td><td>β</td><td></td><td>• laughs</td><td></td><td>• laughs</td><td></td><td>• laughs</td>
<td>THE</td><td>β</td><td></td><td>Pt</td><td></td><td>β</td><td></td><td>β</td><td></td><td>β</td>
<td>ε</td><td>Ο</td><td></td><td> 1</td><td>rf</td><td>O</td><td></td><td>O</td><td></td><td>O</td>
<td>ω</td><td>Α</td><td></td><td>• laughs</td><td>β</td><td>THE</td><td></td><td>THE</td><td></td><td>THE</td>
<td></td><td>β</td><td></td><td></td><td>• laughs</td><td>β</td><td></td><td>β</td><td></td><td>β</td>
<td>Ο</td><td>rf</td><td></td><td>ω</td><td>laugh</td><td>rf</td><td></td><td>rf</td><td></td><td>rf</td>
<td>THE</td><td>Ο</td><td></td><td>THE</td><td>rf</td><td>O</td><td></td><td>O</td><td></td><td>O</td>
<td>• laughs</td><td>• laughs</td><td></td><td></td><td></td><td>• laughs</td><td></td><td>• laughs</td><td></td><td>• laughs</td>
<td>Ο</td><td>Μ</td><td></td><td>rf</td><td></td><td>M</td><td></td><td></td><td></td><td>M</td>
<td>* rf</td><td>ο</td><td></td><td>THE</td><td>THE</td><td>O</td><td></td><td>O</td><td></td><td>O</td>
<td>Ο</td><td>laugh</td><td></td><td>• laughs</td><td>• k</td><td>laugh</td><td></td><td>THE</td><td></td><td>THE</td>
<td>β</td><td>• laughs</td><td>rf,</td><td>ε</td><td>THE</td><td>• laughs</td><td>rf</td><td>• laughs</td><td>rf</td><td>• laughs</td>
<td>• laughs</td><td>Pt</td><td>β</td><td>"The</td><td> 1</td><td>THE</td><td>β</td><td>Pt</td><td>β</td><td>Pt</td>
<td>ε</td><td>Ο</td><td>• laughs</td><td> 1</td><td>laugh</td><td>O</td><td>• laughs</td><td>O</td><td>• rl</td><td>O</td>
<td> <</td><td>THE</td><td>laugh</td><td></td><td>• laughs</td><td>β</td><td>laugh</td><td>β</td><td>laugh</td><td>β</td>
<td></td><td>Α</td><td>rf</td><td> +</td><td>β</td><td>THE</td><td>rf</td><td>THE</td><td>rf</td><td>THE</td>
<td></td><td> 1,</td><td> ></td><td>THE</td><td>O</td><td> 1</td><td> ></td><td> 1</td><td> ></td><td> 1,</td>
<td></td><td>• laughs</td><td> 1</td><td></td><td> &</td><td>• laughs</td><td> 1</td><td>• laughs</td><td> 1</td><td></td>
§ •H
A rf>
I * r4
H o
A laughs
Pt
O
THE
A • A <D nrf rf 'd • ri ε
C +
to ω
<td> §</td><td>rf</td><td>Ο</td><td>Ο</td><td>Ο</td><td>Ο</td><td>ο</td><td>Ο</td>
<td>-P</td><td>ο</td><td>ο</td><td>Ο</td><td>Ο</td><td>Ο</td><td>ο</td><td>Ο</td>
<td>ω</td><td>• laughs</td><td>CM</td><td> 00</td><td>Ο</td><td> 00</td><td>ο</td><td> 0—</td>
<td>β</td><td>ω</td><td> 30</td><td> 30</td><td>Μ *</td><td>ρο</td><td>οο</td><td></td>
<td>ο</td><td>'laughs</td><td>laugh</td><td>Α</td><td>Η</td><td>ι — 1</td><td>laugh</td><td>Η</td>
<td>ο</td><td><Η</td><td></td><td></td><td></td><td></td><td></td><td></td>
CM w
O
THE
The s et po fcd o
powder
5-o
po «-rt
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CM iw
Bonil-D, I — valine po
Hm
Ο
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td>
<td>X—</td><td>χ'— χ</td><td>x — x</td><td></td><td> ,—</td><td>x- ~ X</td>
<td>POWDER</td><td>m</td><td></td><td>POWDER</td><td>POWDER</td><td>m</td>
<td>B</td><td>hm B</td><td>Q</td><td>ίβ O</td><td>ffi O</td><td>«—Ι</td>
<td></td><td>K -> *</td><td></td><td></td><td></td><td></td>
<td>Hm</td><td>Oq O</td><td>s</td><td>Hrt t O</td><td>hrt THE</td><td>B</td>
<td> 1</td><td>I</td><td> 1</td><td>I</td><td> 1</td><td> 1</td>
ΓΗ co
Cn
THE
O
CM
THE
CM
CM
CM 'Application Examples
Example A
Ph.ytoph.th.ora (tomato) test / protective action
Solvent: 4.7 parts by weight of acetone
Emulsifying agent: 0.3 parts by weight of alkylaryl polyglycolic ether
For the preparation of a convenient composition containing the active substance, 1 part by weight of the active substance is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
To test the protective action, young plants are sprayed with the composition containing the active substance until wet. After the spray layer has dried, the plants are inoculated with an aqueous suspension of Phytophthora infestans spores.
The plants are placed in an incubation booth at 100 ° C relative humidity and about 20 ° C.
days after inoculation the evaluation is performed.
In this assay, for example compounds according to examples (D, (2), (3), (4), (5), (6), (7), (8), (9), (10), ( 11), (12), (13), (14), (15) ® (16) showed excellent fungicidal activity.
<img file="PT98696B_D0055.tif" />
Example Β
Plasmopara (vine) assay / protective action
Solvent: 4.7 parts by weight of acetone
Smulsant: 0.3 parts by weight of alkylaryl polyglycol ether
<img file="PT98696B_D0056.tif" />
To prepare a convenient composition containing the active substance, 1 part by weight of the active substance is mixed with the indicated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
<img file="PT98696B_D0057.tif" />
To test the protective action, young plants are sprayed with the composition containing the active substance until wet. After the pulverized layer has dried, the plants are inoculated with an aqueous suspension of Plasmopara viticola spores and then left for 1 day in a humid chamber at 20 ° C.<sup>s</sup>G-22<sup>s</sup>C and 100% relative humidity. The plants are then placed in a greenhouse for 5 days at 22 ° C and about 80% relative humidity. The plants are then moistened and placed for 1 day in a humid chamber.
days after inoculation the attack is evaluated by the disease.
In this assay they have been found to have excellent fungicidal activity, for example compounds according to the following preparation examples: (1), (2), (3), (4), (5), (6), (7) , (8), (9), (10), (11), (12), (13), (14), (15) and (16).
Contents51
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| HU912775D0 | Hungary | D0 | |
| IE912997A1 | Ireland | A1 | |
| DE4026966A1 | Germany | A1 | |
| EP0472996A1 | European Patent Office (EPO) | A1 | |
| KR920004338A | Republic of Korea | A | |
| MX9100720A | Mexico | A | |
| HUT59082A | Hungary | A | |
| BR9103637A | Brazil | A | |
| ZA916691B | South Africa | B | |
| PT98696A | Portugal | A | |
| JPH04230652A | Japan | A | |
| PL291508A1 | Poland | A1 | |
| PL294789A1 | Poland | A1 | |
| EP0550788A1 | European Patent Office (EPO) | A1 | |
| HU209456B | Hungary | B | |
| RU2015962C1 | Russian Federation | C1 | |
| PL165204B1 | Poland | B1 | |
| EP0472996B1 | European Patent Office (EPO) | B1 | |
| DE59104468D1 | Germany | D1 | |
| ES2067813T3 | Spain | T3 | |
| GR3015191T3 | Greece | T3 | |
| JPH0768200B2 | Japan | B2 | |
| US5453531A | United States of America | A | |
| PL167500B1 | Poland | B1 | |
| IE66012B1 | Ireland | B1 | |
| PT98696BThis record | Portugal | B | |
| KR100190298B1 | Republic of Korea | B1 |
Numbers
- Publication, DOCDB
- 98696
- Publication, EPODOC
- PT98696
- Application
- 98696
- Application, DOCDB
- 9869691
- Application, EPODOC
- PT19910098696
Titles2
- English
- PROCESS FOR valinamide replaced DERIVATIVES PREPARATION WITH EFFECT FUNGICIDE
- Portuguese
- PROCESSO PARA A PREPARACAO DE DERIVADOS DE VALINAMIDA SUBSTITUIDOS COM EFEITO FUNGICIDA
Classification
- CPC, 2
- C07C271/22
- A01N47/12