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US3468895A - 2,6-dichloro-3,5-dicyano-4-aryl pyridines - Google Patents

2,6-dichloro-3,5-dicyano-4-aryl pyridines Download PDF

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US3468895A
US3468895A US568137A US3468895DA US3468895A US 3468895 A US3468895 A US 3468895A US 568137 A US568137 A US 568137A US 3468895D A US3468895D A US 3468895DA US 3468895 A US3468895 A US 3468895A
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dicyano
dichloro
pyridine
phenyl
compound
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Gunther Mohr
Konrad Niethammer
Sigmund Lust
Gerhart Schneider
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Merck KGaA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3

Definitions

  • NC CN wherein R is selected from the group consisting of phenyl, naphthyl, pyridyl, substituted phenyl where the substituted moiety is at least one member of the group consisting of CH C H CH O, C H O, OCH O, HO, F, Cl, Br, N0 NH and dialkyl amino containing 1-6 carbon atoms per alkyl group.
  • This invention relates to novel fungicides having a wide range of activity.
  • R is any one of alkyl containing 1-8 carbon atoms, phenyl, naphthyl or pyridyl group, said aromatic compounds being optionally substituted in one or more places CH3, C2H5, CH30, C H O, H0, F, Cl, Br, N0 NH or dialkylarnino (alkyl u to C have a pronounced fungicidal action.
  • the 2,6-dichlor0-3,5- dicyano-4-phenyl-pyridine (I) is especially effective.
  • the fungicidal activities of these compounds are characterized especially by their wide range, besides being very effective against those fungi which can also be fought with the usual fungicidal agents of average range, these new agents also have a definite inhibiting eifect on the powdery mildew.
  • the mildew fungi have heretofore been fought successfully only with sulfur preparations or with the specific mildew fungicide 2,4-dinitro-6-sec.-octylphenylcrotonate, although the latter is practically inefiective against other fungi.
  • the compounds of this invention are characterized by only slight toxicity
  • the LD of I for oral application to rate is above 5 g./ kg.
  • the amount of the active agent is that which is necessary to prevent 50 to of the spores from germinating (DL to DL s average value from 3 tests).
  • Each recorded value is an average of three separate tests and represents the percentage of inoculated places where infection was prevented by the sprayed coating.
  • the table gives the infection results in percent infected.
  • the new compounds are also characterized by good plane compatibility.
  • the 4 substituted 2,6 dichloro-3,S-dicyano-pyridines can be produced from the corresponding 4-substituted 3,5-dicyano-6-hydroxy-Z-pyridones by reaction with a chlorinating agent without or with the addition of a solvent.
  • consideraiton can be given e.g., to 4-phenyl-,4-o-, 4-mor 4 p-tolyl-, 4-o-, 4mor 4-p-methoxyphenyl-, 4-o-, 4-m, or 4-phydroxyphenyl-, 4-a-naphthyl-, 4-5-naphthyl-, 4 0-, 4-m or 4 p-halogenphenyl-, 4-o-, 4-mor 4-p-nitro-phenyl-, 4-o-, 4-mor 4-p-aminoor -dialkylaminophenyl-3,5-dicyano-6-hydroxy-Z-pyridone.
  • Suitable chlorinating agents are e.g.
  • phosphorus pentachloride phosphorus oxychloride, phosphorus trichloride, thionyl chloride, sulfuryl chloride or mixtures thereof with or without the addition of solvents.
  • Suitable solvents are inert organic liquids such as benzene, chlorinated benzene, dimethyl-formamide, tertiary bases such as pyridine, quinoline, triethylamine, tributylamine, dimethylaniline or mixtures of those alone or with other inert solvents.
  • the reaction will occur at room temperature, but it is advantageous to warm or boil the mixture for a while.
  • the reaction is generally completed after 0.5 to 10 hours, depending on the conditions.
  • the 4-aryl-3,S-dicyano-6-hydroxy-2-pyridones are in part known (see Jour. Chem. Soc., vol. 117, (1920), p 1473). They can be produced by condensation of 2 molecules cyanacetamide with suitable aromatic aldehydes in the presence of a basic condensation agent.
  • the cyanacetamide can be prepared from cyanoacetic ester and ammonia, or can be produced in situ from chloroacetic ester, potassium or sodium cyanide and ammonia.
  • Suitable condensation agents are e.g. ammonia, sodium or potassium hydroxide or sodium or potassium alcoholates.
  • Suitable aldehydes are acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 3-methylbutane-aldehyde, benzaldehyde, o-, mand p-tolylaldehyde, o-, mand p-methoxybenzaldehyde, o-, mand p-hydroxybenzaldehyde, o-, mand p-chlorobenzaldehyde, o-, m and pbromobenzaldehyde, o-, mand p-nitrobenzaldehyde, o-, mand p-arninoor -dialkylaminobenzaldehyde wherein alkyl C l-naphthaldehyde, 2-naphthaladehyde and 2-, 3- and 4-pyridine-aldehyde.
  • Particularly suitable fungicidal agents according to this invention are 2,6-dichloro-3,5-dicyano-4-methy1-, -4-ethyl-, -4-propyl-, -4-isopropyl-, -4-butyl-, -4 isobutyl-, -4-amyl-, -4-isoamyl, -4-hexyl, -4-heptyl-, -4-octyl-, -4-phenyl-, -4-o-tolyl-, -4-m-tolyl-, -4-p-tolyl-, -4-(o-ethylphenyl)-, -4-(m-ethylphenyl), -4-(p-cthylphenyl-, -4-(o-methoxyphenyl) -4-(m-methoxyphenyl) -4-(p-methoxyphenyl) -4-(,4-
  • the fungicidal compounds of this invention can be incorporated in the forms generally used.
  • the usual carrier and/or filler substances it is possible to produce spraying or dusting materials which can be mixed with other substances such as dispersing or wetting agents.
  • solution or emulsions therefrom which can be applied e.g. by atomization after the addition of suitable agents.
  • suitable solvents for this purpose are especially certain hydrocarbons such as gasoline, petroleum, benzene, toluene, xylene, tetralin, decalin, or mixtures thereof.
  • the fungicidal agents of this invention in mixtures with other fungicidal agents.
  • the preparations generally contain from 1 to of the active agent.
  • fungicidal agents to be used in mixtures with the compounds of this invention are for instance:
  • octylphenyl-crotonate manganese-ethylene-bis-dithio-carbamate pentachloro-nitrobenzene 2,3,5,6-tetrachloro-nitrobenzene tetramethyl-thiuram-disulfide zinc-ethylene-bis-(dithiocarbamate) zinc-N,N-dimethyl-dithiocarbamate 2-heptadecyl-Z-imidazoline acetate griseofulvin N-trichloromethylthio-phthalimide furthermore salts and organometallic compounds of mercury, copper, and arsenic such as phenylmercuric acetate or basic cupric chloride as well as the usual sulfur fungicides such as barium sulfide.
  • the preparations may generally contain 1 to 95% of the known fungicide in addition to the fungicide according to the invention.
  • EXAMPLE 1 23.7 g. dry 3,5-dicyano-6-hydroxy-4-phenyl-2-pyridone (produced according to Journal of the Chemical Society (London) vol. 117 (1920), p. 1473) or 25.5 g. of its ammonium salt in 150 ml. chlorobenzene are reacted with 41.7 g. phosphorus pentachloride and boiled two hours. The dark red reaction mixture is poured over ice, the organic phase separated, washed to neutrality with sodium 'bicarbonate solution, dried over sodium sulfate and concentrated. The yield is 12.0 g.
  • EXAMPLE 2 20 g. 3,5 dicyano 6 hydroxy 4 phenyl 2 pyridone or 21.5 g. of its ammonium salt and 6 ml. pyridine in 150 ml. dry benzene are heated over night under reflux with 20 ml. phosphorus oxychloride and are then poured into 200 ml. benzene and 300 ml. ice water. The benzene phase is washed with water and sodium bicarbonate solution, dried over sodium sulfate, and evaporated to dryness. The yield is 14.5 g. (63% theoretical of I. M.P. 202- 204" C.
  • EXAMPLE 3 20 g. 3,5 dicyano 6 hydroxy 4 p tolyl pyridone (produced according to Le.) or 21.5 g. of its ammonium salt are mixed with 80 g. phosphorus pentachloride and heated one hour to 130-140 C. After cooling, the mixture is poured into ice water and the precipitate recrystallized several times from ethanol or benzene. The 2,6- dichloro-3,S-dicyano-4-p-tolyl-pyridine thus obtained melts at 240-242 C. Yield 90%.
  • the powder thus obtained can be sprayed in the form of dilute aqueous suspensions or applied with a suitable duster.
  • Bentonite 4O Sulfite liquor powder 7 Sodium salt of the condensation product from oleic acid and methyltaurine (technical grade 32%) 3 are ground intimately. The resulting powder can be sprayed or atomized as a dilute aqueous suspension.
  • R is selected from the group consisting of phenyl, naphthyl, pyridyl, substituted phenyl where the substituted moiety is at least one member of the group Consisting of CH3, C2H5, CHgO, CZH5O, "OCH2O', H0, F, Cl, Br, N0 NH and dialkyl amino containing 1-6 carbon atoms per alkyl group.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-phenyl-pyridine.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-p-tolyl-pyridine.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,S-dicyano-4-(p-ch1orophenyl)- pyridine.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-(m-nitrophenyl)- pyridine.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,S-dicyano-4(p-nitrophenyl)- pyridine.
  • a compound as defined by claim 1 wherein said compound is 2,6-dichloro 3,5 dicyano-4-(3-pyridyl)- pyridine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

United States Patent 3,468,895 2,6-DICHLORO-3,5-DICYANO-4-ARYL PYRIDINES Giinther Mohr, Darmstadt, Konrad Niethammer, Traisa, and Sigmund Lust and Gerhart Schneider, Darmstadt, Germany, assignor to E. Merck Aktiengesellschaft, Darmstadt, Germany No Drawing. Original application Mar. 30, 1964, Ser. No. 355,929, now Patent No. 3,284,293, dated Nov. 8, 1966. Divided and this application July 27, 1966, Ser. No. 568,137 Claims priority, application Germany, Apr. 2, 1963, M 56,343 Int. Cl. C07d 31/46; AOln 9/22 US. Cl. 260-2943 8 Claims ABSTRACT OF THE DISCLOSURE Compounds of the following formula exhibit fungicidal activity:
NC CN wherein R is selected from the group consisting of phenyl, naphthyl, pyridyl, substituted phenyl where the substituted moiety is at least one member of the group consisting of CH C H CH O, C H O, OCH O, HO, F, Cl, Br, N0 NH and dialkyl amino containing 1-6 carbon atoms per alkyl group.
This is a divisional application of parent application Ser. No. 355,929, filed Mar. 30, 1964, and claims priority through said parent application of German patent application, Ser. No. M 56,343, filed Apr. 2, 1963, now Patent No. 3,284,293.
This invention relates to novel fungicides having a wide range of activity.
It has been found that 4-substituted 2,6-dichloro-3,5- dicyano-pyridines of the formula J:CN
wherein: R is any one of alkyl containing 1-8 carbon atoms, phenyl, naphthyl or pyridyl group, said aromatic compounds being optionally substituted in one or more places CH3, C2H5, CH30, C H O, H0, F, Cl, Br, N0 NH or dialkylarnino (alkyl u to C have a pronounced fungicidal action. The 2,6-dichlor0-3,5- dicyano-4-phenyl-pyridine (I) is especially effective.
The fungicidal activities of these compounds are characterized especially by their wide range, besides being very effective against those fungi which can also be fought with the usual fungicidal agents of average range, these new agents also have a definite inhibiting eifect on the powdery mildew. The mildew fungi have heretofore been fought successfully only with sulfur preparations or with the specific mildew fungicide 2,4-dinitro-6-sec.-octylphenylcrotonate, although the latter is practically inefiective against other fungi.
The compounds of this invention are characterized by only slight toxicity For example, the LD of I for oral application to rate is above 5 g./ kg.
Patented Sept. 23, 1969 (a) Prior art compounds:
A Zinc-dimethyl-dithiocarbamate B Tetramethyl-thiuram-disulfide C N-trichloromethylthio-tetrahydro-phthalimide D 2,4-dinitro-6-sec.-octylphenyl-crotonate E Zinc-ethylene-bis-(dithiocarbamate) F N-trichloromethylthio-phthalimide (b) Compounds of this invention:
I 2,6-dichloro-3,5 dicyano-4-phenyl-pyridine II 2,6-dichl0ro-3,5-dicyano-4-rnethyl-pyridine III 2,6-dichloro-3,S-dicyano-4-isopropyl-pyridine IV 2,6-dichloro-3,5-dicyano-4-(p-nitrophenyl)- pyridine V 2,6-dichloro-3,5-dicyano-4-(m-nitrophenyl)- pyridine VI 2,6-dichloro-3,5-dicyano-4-ethyl-pyridine VII 2,6-dichloro-3,5dicyano-4-propyl-pyridine (I) SPORE GERMINATION TESTS The action in vitro upon conidicspores of Venturia inaequalis (apple scab), Alternaria spec. (leaf spot fungus), Cladosporium fulvum (brown and stain spots on tomatoes), and Barrytis cinerea (brown fungus rot) was tested by the known spore germination testing process. The results of these tests are given in the following Tables 1 to 4. The amount of the active agent is that which is necessary to prevent 50 to of the spores from germinating (DL to DL s average value from 3 tests).
TABLE 1.SLIDES, SPORE GERMINATION TEST Test fungus: Ventun'a inaequalis In mgJlOO em.
Active Agent DL D11 I 0. 010 0. 022 II 0. 010 0. 017 III 0. 010 0. 020 IV 0. 0019 0. 0038 V -1 0. 0026 0. 0065 TABLE 2.SLIDES, SPORE GERMINATION TEST Test fungus: Alternaria spec.
In mg./ em.
Active Agent DL 50 DL 95 TABLE 3.SLIDES, SPORE GEMINATION TEST Test fungus: Cladosporium fulvum In mg./100 cm.
(II) ACCELERATED SIMULATED FIELD TESTS FOR ORIENTATION The excellent fungicidal action in vitro of compound I was confirmed in some experiments on hosts infected with important pathogenic fungi and was compared with known fungicidal agents.
(1) Prevention of infection with Plasmopara viticola in vine leaves Method.-The active agents were suspended in water with the help of 1 part by weight of polyoxy-ethylenesorbitan-mono-oleate. Isolated vine leaves of the silvaner variety were sprayed on their under sides with this suspension. After the suspension had dried, drops of a spore suspension of the tested fungus were deposited on the intercostal areas of the leaf surface. After 24 hours the drops were removed by suction. The leaves were then stored in a damp chamber at room temperature under illumination until used.
Each recorded value is an average of three separate tests and represents the percentage of inoculated places where infection was prevented by the sprayed coating.
(x) Denotes phytotoxic, the attack being impossible to judge perfectly.
(2) Spraying of tomatoes against infection by Phytophthora infestans Method.Tomato plants (Lukullus) are sprayed in their 3-sequence leaf stage with polyoxyethylene-sorbitan-mono-oleate in a 1:1 water suspension. After the suspension has dried the leaves are sprayed with a zoospore supsension of Phytophthora infestans and allowed to stand 24 hours at 12 to 50 C. in a 100% moisture saturated atmosphere.
The table gives the infection results in percent infected.
TABLE 6 Test fungus: Phytophthora infealane Concentrations of active agent in suspension Active agent Percent infected, control=100 (3) Spraying of wheat plants against Erysiphe graminis forrna specialis tritici Method.-Wheat seed-plants were infected with conidia of erys iphe and were kept in a greenhouse at 20 to 25 C. 2, 4, and 6 days after the infection some of the experimental plants were sprayed with a suspension of the active agent in water (polyethylene-sorbitan-monooleate, 1:1). They were evaluated 10 and 14 days after infection. Infection of the leaves and of the coleoptiles was recorded separately.
TABLE 7 Test fungus: Erysiphe graminie f. sp. triticz' Percent infection reduction in concentration range 0.20.02%
Areas of 5 n1 each, covered with vines of the Riesling, Silvaner and Miiller-Thurgau varieties were sprayed 9 times in 9 weeks with suspensions of the active agents. One week after the last spraying the leaves were evaluated. Those which had more than three infected places were considered as being infected, and their percentage of the total number of leaves was recorded.
TABLE 8 Concentration, percent Infected Kind of vine percent Riesling Active Agent Silvaner Untreated The results show that agent I of this invention is more effective than agents E and F with which it was compared.
5 iv PLANT TOLERANCE (1) Drop-application test on the primary leaves of beans Method.The upper sides of the primary leaves of almost completely developed bush beans (potted Saxa plants) were wetted with an aqueous suspension of the fungicidal agent (2 drops per leaf). The agent was used with polyoxyethylene sorbitan-mono-oleate 1: 1. Then the leaf was punctured from below into the drop with a needle.
TABLE 9.PHYTOTOXICITY OF FUNGICIDAL AGENTS TOWARD LEAF TISSUES OF BEAN PLANTS [Formation of dark zones around the punctured places one Week after treatment; diameter in mm. (average of four places) for various concentrations] Concentration of active ingredient, percent Active agent 5. 2. 0 1. 0 0. 5 0. 2
Control (Water drop)--. 0 0 0 0 0 (2) Plant spraying Young plants of oats, wheat, pumpkin, bush beans and tomatoes, as well as vine cuttings and apples were sprayed with an aqueous polyoxyethylene-sorbitan-mono-oleate suspension of the fungicidal agent (1:1) until they were dripping Wet. The tolerance for I Was generally very good, even in the highest concentration of 0.4 to 0.5%, especially in comparison with agent D.
In addition to their wide range of applicability and their effectiveness for preventing mildew infection, the new compounds are also characterized by good plane compatibility.
The 4 substituted 2,6 dichloro-3,S-dicyano-pyridines can be produced from the corresponding 4-substituted 3,5-dicyano-6-hydroxy-Z-pyridones by reaction with a chlorinating agent without or with the addition of a solvent. As a starting material, consideraiton can be given e.g., to 4-phenyl-,4-o-, 4-mor 4 p-tolyl-, 4-o-, 4mor 4-p-methoxyphenyl-, 4-o-, 4-m, or 4-phydroxyphenyl-, 4-a-naphthyl-, 4-5-naphthyl-, 4 0-, 4-m or 4 p-halogenphenyl-, 4-o-, 4-mor 4-p-nitro-phenyl-, 4-o-, 4-mor 4-p-aminoor -dialkylaminophenyl-3,5-dicyano-6-hydroxy-Z-pyridone. Suitable chlorinating agents are e.g. phosphorus pentachloride, phosphorus oxychloride, phosphorus trichloride, thionyl chloride, sulfuryl chloride or mixtures thereof with or without the addition of solvents. Suitable solvents are inert organic liquids such as benzene, chlorinated benzene, dimethyl-formamide, tertiary bases such as pyridine, quinoline, triethylamine, tributylamine, dimethylaniline or mixtures of those alone or with other inert solvents.
The reaction will occur at room temperature, but it is advantageous to warm or boil the mixture for a while. The reaction is generally completed after 0.5 to 10 hours, depending on the conditions.
2,6-dichloro-3,5-dicyano-4-methyl-pyridine and the corresponding 4-ethyl-compound are known, (collection of Czechoslovak chemical communications, 25, 2173 (1960)), but not their prominent fungicidal activity.
The 4-aryl-3,S-dicyano-6-hydroxy-2-pyridones are in part known (see Jour. Chem. Soc., vol. 117, (1920), p 1473). They can be produced by condensation of 2 molecules cyanacetamide with suitable aromatic aldehydes in the presence of a basic condensation agent. The cyanacetamide can be prepared from cyanoacetic ester and ammonia, or can be produced in situ from chloroacetic ester, potassium or sodium cyanide and ammonia. Suitable condensation agents are e.g. ammonia, sodium or potassium hydroxide or sodium or potassium alcoholates. Suitable aldehydes are acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 3-methylbutane-aldehyde, benzaldehyde, o-, mand p-tolylaldehyde, o-, mand p-methoxybenzaldehyde, o-, mand p-hydroxybenzaldehyde, o-, mand p-chlorobenzaldehyde, o-, m and pbromobenzaldehyde, o-, mand p-nitrobenzaldehyde, o-, mand p-arninoor -dialkylaminobenzaldehyde wherein alkyl C l-naphthaldehyde, 2-naphthaladehyde and 2-, 3- and 4-pyridine-aldehyde.
Particularly suitable fungicidal agents according to this invention are 2,6-dichloro-3,5-dicyano-4-methy1-, -4-ethyl-, -4-propyl-, -4-isopropyl-, -4-butyl-, -4 isobutyl-, -4-amyl-, -4-isoamyl, -4-hexyl, -4-heptyl-, -4-octyl-, -4-phenyl-, -4-o-tolyl-, -4-m-tolyl-, -4-p-tolyl-, -4-(o-ethylphenyl)-, -4-(m-ethylphenyl), -4-(p-cthylphenyl-, -4-(o-methoxyphenyl) -4-(m-methoxyphenyl) -4-(p-methoxyphenyl) -4-(,4-dimethoxyphenyl)-, -4-(p-ethoxyphenyl), -4-(3,4- methylendioxyphenyl)-, -4-(o-hydroxyphenyl)-, -4-(mhydroxyphenyl)-, -4-(p-hydroxyphenyl)-, -4-(2,4-dihydroxyphenyl)-, -4-(o fiuorophenyl)-, 4 (m fluorophenyl)-, -4-(p-fluorophenyl)-, -4-(o-chlorophenyl)-, -4- (m chlorophenyl)-, -4-(p chlorophenyl)-, -4-(2,4 dichlorophenyl)-, -4-(o bromophenyl)-, -4-(m bromophenyl)-, -4(p-bromophenyl)-, -4-(2,4-dibromophenyl)-, -4-(o-nitrophenyl)-, -4-(m nitrophenyl)-, -4-(p nitropheny1)-, -4-(o-aminophenyl)-, -4-(m-aminophenyl)-, -4- (p-aminophenyl)-, -4-(o-dimethylaminophenyl)-, -4-(mdimethylaminophenyl)-, -4-(p dimethylaminophenyl)-, -4-(p diethylaminophenyl)-, -4-(p di n hexylaminophenyl)-, -4-(l-naphthyl)-, -4-(2-naphthyl)-, -4-(2-pyridyl)-, -4-(3-pyridyl)- and -4-(4-pyridyl)-pyridine.
The fungicidal compounds of this invention can be incorporated in the forms generally used. By the addition of the usual carrier and/or filler substances it is possible to produce spraying or dusting materials which can be mixed with other substances such as dispersing or wetting agents. It is also possible to prepare solution or emulsions therefrom which can be applied e.g. by atomization after the addition of suitable agents. Suitable solvents for this purpose are especially certain hydrocarbons such as gasoline, petroleum, benzene, toluene, xylene, tetralin, decalin, or mixtures thereof. It is also possible to use the fungicidal agents of this invention in mixtures with other fungicidal agents. The preparations generally contain from 1 to of the active agent.
Other fungicidal agents to be used in mixtures with the compounds of this invention are for instance:
N-trichloromethylthio-tetrahydro-phthalimide 2,3-dicyano-1,4-dithiaanthraquinone n-dodecylguanidine acetate dipyrrolidyl-thiuram-disulfide triphenyltin-acetate ferric N,N-dimethyl-dithio-carbamate 2,4-dinitro-6-sec. octylphenyl-crotonate manganese-ethylene-bis-dithio-carbamate pentachloro-nitrobenzene 2,3,5,6-tetrachloro-nitrobenzene tetramethyl-thiuram-disulfide zinc-ethylene-bis-(dithiocarbamate) zinc-N,N-dimethyl-dithiocarbamate 2-heptadecyl-Z-imidazoline acetate griseofulvin N-trichloromethylthio-phthalimide furthermore salts and organometallic compounds of mercury, copper, and arsenic such as phenylmercuric acetate or basic cupric chloride as well as the usual sulfur fungicides such as barium sulfide.
The preparations may generally contain 1 to 95% of the known fungicide in addition to the fungicide according to the invention.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the specification and claims in any way whatsoever.
EXAMPLE 1 23.7 g. dry 3,5-dicyano-6-hydroxy-4-phenyl-2-pyridone (produced according to Journal of the Chemical Society (London) vol. 117 (1920), p. 1473) or 25.5 g. of its ammonium salt in 150 ml. chlorobenzene are reacted with 41.7 g. phosphorus pentachloride and boiled two hours. The dark red reaction mixture is poured over ice, the organic phase separated, washed to neutrality with sodium 'bicarbonate solution, dried over sodium sulfate and concentrated. The yield is 12.0 g. (44% of the theoretical) 2,6-dichloro-3,5-dicyano-4-phenyl pyridine (I) melting at 192196 C. After recrystallization from benzene or ethanol, colorless crystals melting at 203204 C. are obtained.
EXAMPLE 2 20 g. 3,5 dicyano 6 hydroxy 4 phenyl 2 pyridone or 21.5 g. of its ammonium salt and 6 ml. pyridine in 150 ml. dry benzene are heated over night under reflux with 20 ml. phosphorus oxychloride and are then poured into 200 ml. benzene and 300 ml. ice water. The benzene phase is washed with water and sodium bicarbonate solution, dried over sodium sulfate, and evaporated to dryness. The yield is 14.5 g. (63% theoretical of I. M.P. 202- 204" C.
EXAMPLE 3 20 g. 3,5 dicyano 6 hydroxy 4 p tolyl pyridone (produced according to Le.) or 21.5 g. of its ammonium salt are mixed with 80 g. phosphorus pentachloride and heated one hour to 130-140 C. After cooling, the mixture is poured into ice water and the precipitate recrystallized several times from ethanol or benzene. The 2,6- dichloro-3,S-dicyano-4-p-tolyl-pyridine thus obtained melts at 240-242 C. Yield 90%.
By analogy the following compounds can be obtained:
2,6-dichloro-3,5-dicyano-4- (p-chlorophenyl)-pyridine,
F. 282284 2,6-dichloro-3,5-dicyano-4-(m-nitrophenyl)-pyridine,
F. 214216 2,6-dichloro-3 ,5 dicyano-4- p-nitrophenyl) -pyridine,
P. 206-207" 2,6-dichloro-3 ,5 -dicyano-4- 3-pyridy1) -pyridine,
F. 183l85 2,6-dichloro-3,5-dicyano-4-(4-pyridyl)-pyridine,
F. 196-198" 2,6-dichloro-3,5-dicyano-4-propyl-pyridine, F, 104-106 2,6-dichloro-3,S-dicyano-4-isopropyl-pyridine,
F. 120-122 2,6-dich1oro-3,5-dicyano-4-disobutyl-pyridine,
EXAMPLE 4 By analogy to Example 3, from the corresponding 4- substituted 3,S-dicyano-6-hydroxy-2-pyridones or their ammonium salts, the following compounds can be obtained.
2,6-dichloro-3,5-dicyano-4-butyl-pyridine 2,6-dichloro-3,5-dicyano-4amyl-pyridine 2,6-dichloro-3,S-dicyano-4-isoamyl-pyridine 2,6-dichloro-3,S-dicyano-4-hexyl-pyridine 2,6-dichloro-3,S-dicyano-4-heptyl-pyridine 2,6-dichloro-3,5-dicyano-4-octyl-pyridine 2,6-dichloro-3,5-dicyano-4-(o-tolyl)-pyridine 2,6-dichloro-3,5-dicyano-4- (m-tolyl)-pyridine 2,6-dichloro-3,5-dicyano-4-(o-ethylphenyl)-pyridine 2,6-dichloro-3,5-dicyano-4-(p-ethylphenyl)-pyridine 2,6-dichloro-3,5-dicyano-4-(o-methoxyphenyl)-pyridine 2,6-dichloro-3 ,5 -dicyano-4- (m-methoxyphenyl) -pyridine 2,6-dichloro-3,5-dicyano-4-(p-methoxyphenyD-pyridine 2,6-dichloro-3,5-diCyan-4 (3,4-dimethoxyphenyl) pyridine 8 2,6-dichloro-3,5-dicyano-4- (p-ethoxyphenyl) -pyridine 2,6-dichloro-3,5-dicyano-4- 3,4-methylendioxyphenyl) pyridine 2,6-dichloro-3,5-dicyano-4- (o-hydroxyphenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (m-hydroxyphenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (p-hydroxyphenyl) -pyridine 2,6-dichloro-3,5-dicyano-4- (2,4-dihydroxyphenyl) pyridine 2,6-dichloro-3 ,5-dicyano-4- (4-hydroxy-3-methoxyphenyl) pyridine 2,6-dichloro-3,5-dicyano-4- (o-fluorophenyl -pyridine 2,6-dichloro-3,5dicyano-4-(m-fluorophenyl)-py1idine 2,6-dichloro-3,5-dicyano-4- (p-fiuorophenyl) -pyridine 2,6-dichloro-3,5-dicyano-4- o-chlorophenyl -pyridine 2,6-dichloro-3,5-dicyauo-4- (m-chlorophenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (2,4-dichlorophenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (o-bromophenyl -pyridine 2,6-dichloro-3 ,5 -dicyano-4- m-bromophenyl) -pyridine 2,6-dichloro-3 ,5 -dicyano-4- p-bromophenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (2,4-dibromophenyl) -pyridine 2,6-dichloro-3 ,5-dicyano-4- (o-nitrophenyl) -pyridiue 2,6-dichloro-3,5-dicyano-4- (o-aminophenyl -pyridine 2,6-dichloro-3,5-dicyano-4- (m-aminophenyl) -pyridine 2,6-dichloro-3 ,5-dicyano-4- (p-aminophenyl) -pyridine 2 5 2,6-dichloro-3,5-dicyano-4- (o-dimethylaminophenyl) pyridine 2,6-dichloro-3,5-dicyano-4- m-dimethylaminophenyl) pyridine 2,6-dichloro-3,5-dicyano-4- (p-dimethylaminophenyl) pyridine 2,6-dichloro-3,5-dicyano-4- (p-diethylaminophenyl) pyridine 7 2,6-dichloro-3,5-dicyano-4- (p-di-n-hexylaminophenyl) pyridine 5 2,6-dichloro-3,5-dicyano-4-( 1-naphthyl)-pyridine 2,6-dichloro-3,5-dicyano-4- Z-naphthyl -pyridine 2, 6-dichloro-3,5 -dicyano-4- (2-pyridyl) -pyridine.
The following examples are preparations suitable to Sodium-isobutyl-naphthaline sulfonate (technical) Bolus or chalk fungicidal purposes. Instead of the specific active agent 0 are ground intimately together. The resulting powder can be sprayed or atomized as a dilute aqueous suspension.
EXAMPLE '6 A wettable powder:
Percent 2,6-dichloro-3,5-dicyano-4-methyl-pyridine B0 Oleic-acid-N-methyl-tauride 5 Fullers earth 15 are ground to the necessary fineness. By dilution with water a finely divided emulsion is obtained which is suitable for spraying or atomizing.
EXAMPLE 7 A dusting material:
Percent 2,6-dichloro-3,5-dieyano-4-(p-nitrophenyl)-pyridine Talcum are intimately ground and applied with a suitable duster.
EXAMPLE 8 A spraying solution:
A solution of 3% 2,6-dichloro-3,5-dicyano-4-(3 manner through a nozzle.
pyridyl)-pyridine in chloroform is atomized in the usual 9 EXAMPLE 9 An emulsion concentrate:
Percent 2,6-dichloro-3,S-dicyano-4-octyl-pyridine 10 Dimethyl-formamide 45 Xylene Fatty acid-polyglycol-ester 30 are mixed. The resulting solution is emulsified in water and is sprayed or atomized.
EXAMPLE 10 A wettable or dust powder:
are ground to the required fineness. The powder thus obtained can be sprayed in the form of dilute aqueous suspensions or applied with a suitable duster.
EXAMPLE 11 A wettable powder:
Percent N-trichloromethylthiotetrahydrophthalimide 2,6-dichloro-3,5-dicyano-4-phenyl-pyridine 30 Bentonite 4O Sulfite liquor powder 7 Sodium salt of the condensation product from oleic acid and methyltaurine (technical grade 32%) 3 are ground intimately. The resulting powder can be sprayed or atomized as a dilute aqueous suspension.
EXAMPLE 12 A wettable powder:
Percent Zinc-ethylene-bis-(dithiocarbamate) 40 2,6-dichloro-3,S-dicyano-4-phenyl-pyridine 10 Bolus 40 Sulfite liquor powder 8 Isobutyl naphthalene sulfonates 2 are ground intimately. The resulting powder can be sprayed or atomized as a dilute aqueous suspension.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Consequently, such changes and modifications are properly, equitably, and intended to be, within the full range of equivalence of the following claims.
What is claimed is:
1. A compound of the formula:
wherein R is selected from the group consisting of phenyl, naphthyl, pyridyl, substituted phenyl where the substituted moiety is at least one member of the group Consisting of CH3, C2H5, CHgO, CZH5O, "OCH2O', H0, F, Cl, Br, N0 NH and dialkyl amino containing 1-6 carbon atoms per alkyl group.
2. A compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-phenyl-pyridine.
3. A compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-p-tolyl-pyridine.
4. A compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,S-dicyano-4-(p-ch1orophenyl)- pyridine.
5. A compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,5-dicyano-4-(m-nitrophenyl)- pyridine.
6. A compound as defined by claim 1 wherein said compound is 2,6-dichloro-3,S-dicyano-4(p-nitrophenyl)- pyridine.
7. A compound as defined by claim 1 wherein said compound is 2,6-dichloro 3,5 dicyano-4-(3-pyridyl)- pyridine.
8. A compound as defined by claim 1 wherein said compound is 2,6-dichloro 3,5 dicyano-4-(4-pyridyl)- pyridine.
References Cited Lukes et al.: Chemical Abstracts, vol. 55, par. 1605-h;
January 1961.
HENRY R. JILES, Primary Examiner A. L. ROTMAN, Assistant Examiner U.S. Cl. X.R. 424-263
US568137A 1963-04-02 1966-07-27 2,6-dichloro-3,5-dicyano-4-aryl pyridines Expired - Lifetime US3468895A (en)

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US3496274A (en) * 1963-04-02 1970-02-17 Merck Ag E Synergistic fungicidal mixture
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US4835279A (en) * 1984-11-06 1989-05-30 Monsanto Company 2,6-substituted pyridine compounds
PE20061119A1 (en) * 2005-01-19 2006-11-27 Aventis Pharma Sa PYRAZOLO PYRIDINES SUBSTITUTED AS INHIBITORS OF FAK, KDR AND Tie KINASES
US8557866B2 (en) * 2007-04-13 2013-10-15 Dow Agrosciences, Llc. Isomeric mixtures of dinitro-octylphenyl esters and synergistic fungicidal mixtures therefrom
US8110208B1 (en) 2009-03-30 2012-02-07 Biolife, L.L.C. Hemostatic compositions for arresting blood flow from an open wound or surgical site

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