AU611221B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU611221B2 – N-cyanomethyl-2-pyridinone insecticides
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AU611221B2 – N-cyanomethyl-2-pyridinone insecticides
– Google Patents
N-cyanomethyl-2-pyridinone insecticides

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Publication number
AU611221B2

AU611221B2
AU24922/88A
AU2492288A
AU611221B2
AU 611221 B2
AU611221 B2
AU 611221B2
AU 24922/88 A
AU24922/88 A
AU 24922/88A
AU 2492288 A
AU2492288 A
AU 2492288A
AU 611221 B2
AU611221 B2
AU 611221B2
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Australia
Prior art keywords
formula
compound according
cyanomethyl
pyridinone
insects
Prior art date
1987-11-10
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Application number
AU24922/88A
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AU2492288A
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Inventor
Gregory A. Bradfisch
James E. Dripps
Ingrid L. Knox
Sudarshan K. Malhotra
Susan Wollowitz
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Dow Chemical Co

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Dow Chemical Co
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1987-11-10
Filing date
1988-11-08
Publication date
1991-06-06

1988-11-08
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Dow Chemical Co

1989-05-11
Publication of AU2492288A
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patent/AU2492288A/en

1991-06-06
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1991-06-06
Publication of AU611221B2
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patent/AU611221B2/en

2008-11-08
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Ceased
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings

C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom

C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member

C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms

C07D211/78—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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

C07D213/62—Oxygen or sulfur atoms

C07D213/63—One oxygen atom

C07D213/64—One oxygen atom attached in position 2 or 6

A—HUMAN NECESSITIES

A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING

A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds

A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom

A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/62—Oxygen or sulfur atoms

C07D213/69—Two or more oxygen atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/62—Oxygen or sulfur atoms

C07D213/70—Sulfur atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals

C07D213/79—Acids; Esters

C07D213/80—Acids; Esters in position 3

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

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

Description

Our Ref 113127 POF Code: 1037/1037 6012q/1
AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Application Number: Lodged: Complete Specification Lodged: Aacepted: Published: O P i °°oPriority 6 1124 Int. Class 0 0 0 o so on,.
0 0 ~0 0 Related Art: C o o0 o o 0 APPLICANT’S REFERENE: 36,094A-F Name(s) of Applicant(s): 0 The Dow Chemical Company Address(es) of Applicant(s): 0 2030 Dow Center, 00 Abbott Road, Midland, Michigan 48640, oUNITED STATES OF AMERICA.
Address for Service is: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: N-CYANMETHYL- 2-PYRIDINONE INSECTICIDES Our Ref 113127 POF Code: 1037/1037 The following statement is a full description of this invention, including tne method of performing it known to applicant(s): 6003q/1 1 N04e: No legalization or ozher witness required
SEAL
To: The Commissioner of Patent’; By: Agent: Phillips Ornonde FitzpP’crick RICHARD G. WATERMAN General Patent Counsel Ievaiiiftiofl or other N-CYANOMETHYL-2-P YRI D INONE INSECTICIDES 00 0 0 0 00 0) 0 0 004 The present invention relates to novel pyridinone compounds and their use in- controlling insects.
5 The contr’ol of insects is critically important in the production of food and fiber and the protection of the public health. New classes Of chemicals that are useful in providing insect control are intensively sought and, when found, highly prized.
Certain substitutid N-pyridinyl-2-pyrid inone compounds and substituted N-phenyl–2-pyridinone compounds have been disclosed to be insecticidal.
SFurther, certain substituted 2-pyridinols (2- -pyr’idinones) are known to be insecticidal and to protect wood from attack by insects.
It has now been found that N~-cyanomethyl-2- -pyrid-inoras are useful in controlling insects. In particular, compounds having the formula 36. 09L4A-F -1- -2-
Y
W 0 (I)
I
CH
2
CN
wherein: W is H, F, Cl, CH 3 or CF 3 g 15 X is H, F, Cl, Br, I, R, OR, OPh, SR, CF 2 Cl, CN, COR, CO 2 R’ or CONR’R’; 0 o» o Y is H, R, OR, SR, OR or OPh; 0 Z is H, F, Cl, Br, I, R, OR, SR, OPh, NO 2 or 0 0 o ,oI CN; R is C-C3 alkyl or C-C3 alkyl partially or /.0o totally substituted with fluorine: 0 aa S» 25 R’ is CI-C4 alkyl; with the proviso that at least one of W, X, Y, and Z is other than H; 30 are novel and control insects when applied to the insects or their locus or to plants upon which insects feed. The compounds are usually applied as components of an insecticidal composition containing an effective amount of at least one such compound of formula in mixture with an agriculturally acceptable carrier.
36,C94A-F -2-
S.
-3- The present compounds can be prepared by combining an appropriately substituted 2-pyridinol having the formula
(II)
wherein W, X, Y, and Z are as defined hereinabove and a base capable of abstracting a proton from a 2- -pyridinol, or a preformed salt of a 2-pyridinol of 3 formula (II) and a base, with monochloroacetonitrile or monobromoacetonitrile in a solvent under conditions conducive to N-alkylation.
the compounds can generally be 0> 20 prepared by combining a 2- or 6-halopyridine having the formula 0 o Qo o C ‘C CCC>
(III)
N’ Q wherein: Q is F, Cl or Br; and W, X, Y, and Z are as defined hereinabove, with an alkali metal hydroxide in a solvent under conditions conducive to the formation of an alkali metal salt of a substituted 2-pyridinol of 36 094A-F I formula (II) and combining this intermediate, without isolation, with monochloroacetonitrile or monobromoacetonitrile under conditions conducive to the formation of the desired novel insecticides of the invention. The desired products can be recovered by conventional means. This process, of course, works best where W does not represent F or C1 because of competing reactions which reduce the yield.
N-cyanomethyl-2-pyridinone compounds containing fluoro, chloro, bromo, iodo, chlorodifluoromethyl, phenoxy, nitro, cyano. alkoxycarbonyl, dialkylarbamoyl, and optionally fluorinated alkyl, alkoxy, alkylthio and acyl substituents are compounds of formula containing designated substituents W, X, o0 Y, and Z and represent the compounds of this invent.ion.
0n Other compounds of formula are those where W .s defined as for formula X and Z independently are H, F, Cl, Br, 1, CH 3 CF3, CF 2 H or CN, and Y is H, CH 3 o CF 3 or CF 2 H. Those N-cyanomethyl-2-pyridinone compounds of formula wherein W is H, or wherein X 0 is Cl, Br, 1, CF3, CF 2 H, C 2
F
5 CN or COR; i.e. (CI-C 4 alkoxy)carbonyl, or wherein Y is H, or wherein Z is H.
F, C1 or CN are preferred. Compounds possessing a S substituent indicated to be preferred at each of positions W, X, Y, and 2 are more preferred.
0 Subs t i tuted-N-cyano-methyl.-2-pyridinones of formula (1) o wherein X is trifluoromethyl are especially preferred a o 30 30 and those wherein W is hydrogen, X is trifluoromethyl, I is hydrogen, and Z is hydrogen, fluoro, chloro or cyano are more especially preferred.
The compounds, N-cyanomethyl-3 -fluoro–(trifluoromethyl)-2-pyridinone, N-cyanomethyl-3-chl0ro-5- -(trifluoromethyl)-2-pyrdinone, and N-cyanomethyl-3uS6.091A-F -4cyano-5-(trifluoromethyl)-2-pyridinone are most especially preferred.
The compounds of the present invention can be prepared by the reaction of an appropriately substituted 2-pyridinol of formula (II) and a base capable of abstracting a proton from said 2-pyridinol, or a preformed salt of said 2-pyridinol and said base, with a monohaloacetonitrile monochloroacetonitrile or monobromoacetonitrile). The reaction is carried out in water or in an organic solvent and under conditions leading to N-alkylation. Typically, the pyridinol, base and monohaloacetonitrile are combined in a solvent and the mixture is agitated and allowed to a 15 o o react at moderate temperatures i:nLil a substantial o0o fraction of the 2-pyridinol of formula (II) has reacted or until a recoverable amount of the substituted No oo cyanomethyl-2-pyridinone of formula has formed.
0 0o °20 Suitable bases are those that form salts with 2-pyridinols, but do not react substantially with monohaloacetonitriles when properly employed in the I oo process. Alkali metal hydroxides or carbonates are S 25 typical. Bases which are somewhat reactive with monohaloaoetonltriles are used in only approximately equimolar or smaller quantities relative to the substituted 2-pyridinols of formula (II) or are used to prepare preformed salts of 2-pyridinols. Bases which 2| 30 are relatively unreactive can be used in excess. For laboratory procedures an excess of potassium carbonate is convenient.
The monohaloacetonitrile and substituted 2-pyridinol are usually employed in approximately equimolar amounts although an excess of one or the 36,C94A-F h* -6other can be used. It is often helpful to employ a small excess of the monchaloacetonitrile to ensure complete reaction of the substituted 2-pyridinol and, thereby, to conserve this starting material.
Either water or an organic solvent or mixtures thereof can be employed as the reaction medium. When water is employed, it is usually helpful to add a phase transfer catalyst, such as benzyltrimethylammonium chloride. Organic solvents which are unreactive under the reaction conditions are suitable. Those in which substituted 2-pyridinol salts have some solubility, are preferred, These include dimethylsulfoxide, tetramethylene sulfone, N,N-dimethylformamide, N-methylo00 15 °o pyrrolidone, acetonitrile, acetone, methyl isobutyl 0″ o ketone, diglyme, and 2-propanol. Dipolar aprotic o 0 ooo solvents are often preferred, especially when W is 0oo hydrogen. When W is fluoro, chloro or trifluoromethyl, 0 0 0 20 alcohols and ketones are often preferred.
o 0 The reactioi. proceeds smoothly at ambient temperatures ard at these temperatures the process oD 000o requires 15 min. to a day. Temperatures of -20°C to 0 25 150°C are typical; temperatures of OC to 120″C are preferred, and temperatures of 2 0 0C to 1000C are ooo especially preferred. A broad range of pressures can ooo.o. be employed as pressure has little influence on the 0 0 process.
o000 The N-cyanomethyl-2-pyridinone product of formula can be recovered from the reaction mixture of the process by conventional means. Water is often added, if not already present, to dissolve the byproduct halide salt. When water-soluble solvents are employed, the addition of water usually causes the 36,094A-F -6- L YLY 1LI IIL~ .i i i -7crude product to precipitate as a solid, which can be recovered by filtration and drying. If water is not added the insoluble by-products are typically removed by filtration and the volatiles are removed by evaporation to obtain the desired product in impure form. Crude products recovered as above can be further purified by conventional means, such as recrystallization from a solvent, such as methanol, toluene, 1,1,1-trichloroethane, and the like. The 1 purified products are crystalline solids.
It must be noted that, since the anions derived from the 2-pyridinols of formula (II) are ambient anions, two different alkylation products are possible, o 5 N-alkyl-2-pyridinones and 2-alkoxypyridines. Bulky o substituents in the 3-position favor N-alkylation whereas bulky substituents in the 6-position favor S0-alkylation. Pyridinate anions unsubstituted in the 20 6 -position (W represents hydrogen) generally give a o preponderance of N-alkylation products. N-alkylation is generally favored by alcohol and ketone solvents. A 0 discussion of 0 vs N-alkylation of 2-pyridinols is presented in Abramovitch, Pyridine and its Derivatives, 25 Supplement Part 3, (1974), pp 745- 7 52.
The requisite substituted 2-pyridinol starting materials of formula which are tautomeric with and functionally equivalent to 2-pyridinones, are known in the art or can be prepared by methods described in the art. They are typically prepared by hydrolysis of an appropriate compound of formula (III), which compounds are also well known in the art or can be prepared by methods described in the art.
36,094A-F i
II
cr=l-rnrra~– urp– il.
-8- 2-Pyridinol starting materials for the compounds of the present invention are also often conveniently prepared by demethylation or debenzylation of appropriately substituted 2-methoxy- and 2-benzyloxypyridines. This can be accomplished by treatment with concentrated aqueous hydrobromic acid or with iodo-trimethylsilane at ambient temperatures. The appropriately substituted 2-methoxy and 2-benzyloxypyridines are known in the art or can be prepared by methods known in the art. Many 2-methoxypyridines having substituents in the 3-position or the and optionally in other positions are conveniently prepared by lithiation of the correspondingly ,o 15 substituted 3-bromo-2-methoxypyridine or 5-bromo-2- -methoxypyridine with an alkyl lithium reagent, such as °o butyl lithium, at low temperatures followed by o treatment with an electrophilic reagent at low o o temperatures. In this way, for example, 3-(or o 2C substituted compounds can be made using alkyl iodides, 3-(or 5-)formyl compounds can be make using dialkylformamides, 3-(or 5-)alkylthio compounds can be I made using dialkyl disulfides, and 3-(or compounds can be made using trimethyl borate and 25 hydrogen peroxide.
It is often convenient to hydrolyze a compound of formula (III) with an alkali metal hydroxide in a solvent under conditions conducive to the formation of S0 an alkali metal salt of a substituted 2-pyridinol of formula (II) and to combine the mixture obtained (a mixture comprising a salt of a compound of formula (II) and a solvent), without recovery of the 2-pyridinate salt, with a monohaloacetonitrile under conditions conducive to the formation of a substituted 36,C94A-F -8- -9- N-cyanomethyl-2-pyridinone compound of formula Conditions conducive to hydrolysis (first step in the process) are well known in the art and conditions conducive to alkylation (second step in the process) are described in detail hereinabove for the identical alkylation using a substituted 2-pyridinol obtained independently.
Many of the substituted N-cyanomethyl-2-pyridinones of formula are useful as intermediates for the preparation of other substituted N-cyanomethyl-2- -pyridinones of formula Thus, compounds wherein X and/or Z are hydrogen can be converted to the corresponding compounds wherein X and/or Z are chloro Sor bromo by halogenation under conditions described in the art for N-methyl-2-pyridinones. Compounds wherein Z is chloro or bromo can be converted to corresponding compounds wherein Z is fluoro, alkoxy, alkylthio, or 20 phenoxy by treatment with potassium fluoride, sodium alkoxide, sodium alkylthiolate, or potassium phenoxide, respectively, in a dipolar aprotic solvent such as dimethyl suifoxide or N-methylpyrrolidone, While it is possible to utilize the substituted U 1 N-cyanomethyl-2-pyridinones of formula directly as insecticides, it is preferable to use them in mixtures containing an insecticidally effective amount of the compound in combination with at least one agriculturally acceptable adjuvant or carrier.
Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations employed in applying the compositions for insect control in the presence of crops, and should not react Schemically with compounds of formula or other composition ingredients. Such mixtures can be designed 36, 9 4A-F I L I I Y for application directly to insects or their locus or to plants upon which insects feed or can be concentrates or formulations which are normally diluted with additional carriers and adjuvants before application. They car be solids, such as, for example, dusts, granules, water dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.
Suitable agricultural adjuvants and carriers that are useful in preparing the insecticidal mixtures of the invention are well known to those skilled in the S art.
o U0~ 0 Liquid carriers that can be employed include o water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroo0 0 2 ethylene, perchloroethylene, ethyl acetate, amyl 0 0 20 acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, isopropyl 0 ‘0 0o'» Calcohol, amnyl alcohol, ethylene glycol, propylene S glycol, glycerine, and the like. Water Is generally the carrier of choice for the dilution of concentrates.
‘Suitable solid carriers include talc, pyro- 0 phyllite clay, silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fullers earth, cotton seed hulls, wheat flour, soybean flour, pumice. wood flour, walnut shell flour, lignin, and the like.
It is frequently desirable to incorporate one Sor more surface-active agents into the compositions of the present invention. Such surface-aotlve agents are 36,094A-F
V
advantageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfatei alkylaryisulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonyipheniol-C, 8 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C 16 ethoxylate; soaps, such as sodium alkylnaphthalenesulfonate salts, such as sodium cibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts* such as sodium di(2-ethylhexyl) sulfosucoinate; sorbit~l esters, such as sorbitol oleate;, quaternary amines, such as lauryl trlmethylamrnonlum chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol. stearate; 0 .0 block copolymers of ethylene oxide and propylene oxide; 0 0 0 0 0 anid salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilkIzed in agricultural compositions include antifoam agentst compatibillilg agenFts, sequestering agents, t I neutralizing agents and buff’ers, corrosion inhibitors, dyes, odorant 4 penetration aids, spreading Aigents, 0 sticking agents4 dispersing agents, thickening :agent4, freeze point depressantsq, antimicrobial agents, and the like, The ^ompositions can also contain other* compatible 6«01?4A-F -12-
‘TII
-13be applied to the foliage or the root zone of plants upon which insects feed. Generally, their application to the foliage or the root zone (the soil in which the plant is grown) is preferred, in which case the compounds of formula generally function as plant systemic insecticides, The compounds of formula are applied in amounts suffic.ient to kill a large fraction of the insects present or invading the treated area within a reasonable time. The actual amount applied will vary depending on factors such as, the compound of formula selected, the insecticidal composition employed, the insect or mite to be controlled, the severity of the insect or mite infestation, the degree of control desired; whether contact or systemic activity is desired, the type of applicator employed, and the climatic conditions at the time of application.
Application rates of 1 g to 10 Kg per hectare are typical; rates of 10 g to 1 Kg per hectare are prefel’red for the more active compounds, Preparation of Starting Materials Example A Preparation of 2.3-Dimethoxy-5-(trifluoromethyl)pyridine Sodium hydride in an oil dispersion (8.0 g of 60 percent, 0.20 mol) was extracted with hexane to remove oil and suspended in 30 ml of te -‘rofuran and to this 5.5 ml (0.14 mol) of anhydrous methanol was added dropwise with stirring. After about 10 min, 9.16 g (0.05 mol) of 2,3-difluoro-5-(trifluoromethyl)pyridine was added, An exothermic reaction ensued which increased the temperature to about 60C The 36,094A-F -13- The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/1 1 J I I I I I I i -i o n ,e -14mixture was then heated at reflux for 6 hours and then a small amount of methanol was added. The mixture was allowed to cool and was thereafter poured onto ice.
The resulting mixture was extracted several times with ether. The combined ether extracts were dried over sodium sulfate and concentrated by evaporation under reduced pressure to obtain 9.0 g (87 percent of theory) of the title compound as a white crystalline solid melting at 22-23.5 C. The proton NMR spectrum was consistent with the assigned structure. consistent with the assigned structure.
Example B Prearation of methyl)-2-ovridinol IPl Pl f ml 2 ,3-Dimethoxy-5-(trifluoromethyl)pyridine (8.8 g, 0.042 mol) was dissolved in 30 ml of glacial acetic acid, the mixture heated to 100’C with stirring, and 14.8 ml of 48 percent aqueous hydrobromic acid (0,13 mol) added. The mixture was allowed to react for mmin and was then poured onto ice, The solid that formed was recovered by filtration, dried, and reorystallized from ethanol to obtain 5.5 g (67 percent of theory) of the title compound as a white powder melting at 115-117°C. The proton NMR spectrum was consistent with the assigned structure.
Anal: ft 0 Calc for C7H 6
F
3 N0 2 43.53; 3.13; 7.25.
43.59; 3.02; 7.19.
Found 36 .094A-F
-J
-1- 36.094A-F rl~~ 7 i Example C Preparation of 3-Bromo-2-methoxy-5-(trifluoromethyl)pyridine A mixture of 7.6 g of 2-chloro-3-bromo-5- -(trifluoromethyl)pyridine, 6.2 ml of 25 percent sodium methoxide in methanol (0.027 mol), and 20 ml of anhydrous methanol was prepared and allowed to react at ambient temperature with stirring for 16 hours. The migture was then poured onto ice and the resulting mixture extracted with ether. The ether extract was extracted with water, dried over sodium sulfate, and concentrated by evaporation under reduced pressure and the residue was purified by distillation under reduced pressure to obtain 4.1 g (65 percent of theory) of the title compound as a colorless oil boiling at 86-88 0 C at 21 mm pressure and having a refractive index at 190C of 1.4816. The proton NMR spectru» -ias consistent with the assigned structure.
Anal: Calc for C 7
H
5 BrF 3 NO 32.84; 1 H, 1.97; N, 5.47.
32.79; 1.95: 5.52. Found a Example D Preparation of 2-Methoxy-3-methyl-5-(trifluoromethyl)pyridine A solution of 5,12 g (0.020 mol) of 3-bromo-2- -methoxy-5-(trifluoromethl)pyridine in 60 ml of ether was cooled to -70″C and blanketed with nitrogen. A solution containing 0.021 mole of butyl lithium (8.4 ml of 2.5 M) was added slowly with stirring keeping the temperature below about -65’C and the mixture allowed to react for another 30 min. Methyl iodide (0.62 ml, 0.01 mol) was added to the mixture and stirring continued at 36,094A-F 36,C94A-F -2- Lw -16for about 30 min. The mixture was allowed to warm to about 20°C and was then poured onto a mixture of ice and saturated aqueous ammonium chloride. The organic layer that formed was recovered. The aqueous layer was extracted with ether and the extract added to the organic layer. The combined organic materials were dried over sodium sulfate and concentrated by evaporation under reduced pressure. The residue was distilled to obtain 2.1 g (54 percent of theory) of the title compound as a colorless oil boiling at 67-69 0 C at 24 mm pressure. The proton NMR spectrum was consistent with the assigned structure.
Example E Preparation of 15 1 methyl)-2-oyridinol Two ml of 48 percent hydrobromic aoid were added with stirring to mixture of 1.38 g (5.5 mol) of 2-methoxy-3-methyl-5-(trifluoromethyl)pyridine and 6 ml 20 Sof glacial acetic acid at 100Q°C and the mixture was allowed to react at about 95’C for 20 min. The mixture t was then cooled and poured onto ice and the solid that S formed was collected by filtration. A second crop of 2 solid was obtained by adding more water to the 25 filtrate. The combined solids were dried to obtain 0.40 g (40 percent of theory) of the title compound as a white powder melting at 141-143’C. The proton NMR spectrum was consistent with the assigned structure.
Anal; Calc for C 7
H
6
F
3 NO 47.47; 3.41; 7.91.
Found 47.18; 3.35; 7.80.
16 36.094A-F -16t! an alkali metal salt of a substituted 2-pyridinol of 36.094A-F -3- -17- Example F Preparation of methyl)-3-pyridinecarboxaldehyde A solution of 5.18 g (0.020 mol) of 3-bromo-2- -methoxy-5-(trifluorcmethyl)pyridine in 50 ml of ether was cooled to -100°C and blanketed with nitrogen. A solution containing 0.024 mole of butyl lithium in hexane (15.0 ml of 1.6 M) was added slowly with stirring keeping the temperature below about -95’C and the mixture was allowed to react for another 15 min.
Dimethylformamide (7.5 ml, 0.097 mol) was added to the mixture at below -95’C and stirring continued for about min. The mixture was allowed to warm to about and was then poured onto a mixture of ice and 1N hydrochloric acid. The mixture that formed was extracted with ether and the extract was dried over sodium sulfate and concontrated by evaporation under reduced pressure. The residue was distilled in a Kugelrohr apparatus to obtain 3.6 g (86 percent of theory) of the title compound as an oil which solidified to a white crystalline solid. The proton NMR spectrum was consistent with the assigned structure, Example G Preparation of methyl)-3-pyridinecarboxaldeh\de Oxime A solution of 1.33 g (0.013 mol) of sodium carbonate in 15 ml of water was added with stirring to a mixture of 4.2 g 0.020 mol) of -(trifluoromethyl)-3-pyridinecarboxaldehyde and 1.74 g ‘0.025 mol) of hydroxylamine hydrochloride in 15 ml of water and the mixture was allowed to react for hours at ambient temperature. It was then extracted several times with ether and ‘he ether extracts were 36.094A-F -17i 1 4 fluoromethyi)-2-pyridinone, -(trifluoromethyl)-2-pyridinone, and N-cyanomethyl-3- 36. 09)A-F i -18combined, dried over sodium sulfate, and concentrated by evaporation under reduced pressure. The residue was triturated with hot hexane, filtered, and dried to obtain 3.1 g (69 percent of theory) of the title compound as a white powder melting at 98-104°C. The proton NMR spectrum was consistent with the assigned structure.
Anal: Calc for C 8
H
7
F
3
N
2 0 2 43.64; 3.21; 12.73.
Found 43.50: 7H, 2.90; 12.53.
on Q 00 0 ,o Example H- Preparation of 3-Cvano-2-methoxv-5-(trio o °oo 1 fluoromethyl)pyridine °oaO 2-Methoxy-5-(trifluoromethyl)-3-pyridineo o’ carboxaldehyde oxime (3.9 g, 0.018 mol) was added to a mixture of 1.9 ml (0.020 mol) of phosphorus oxychloride 20 o O 20 in 20 ml of aoetonitrile and the resulting mixture S heated at reflux with stirring for 1 hour. It was then 0 allowed to cool and was poured onto ice. The mixture S obtained was extracted several times with methylene S chloride and the combined extracts were in turn S 2 extracted with saturated aqueous sodium chloride. The methylene chloride solution was dried over sodium sulfate and concentrated by evaporation under reduced pressure to obtain 3.2 g (89 percent of theory of the title compound as a yellow oil which solidified on standing. The proton NMR spectrum was consistent with the assigned structure.
1 36.094A-F -18-
L
equimolar amounts although an excess of one or the 36.094A-F -19- Examole I Preparation of 2-pyridinol lodotrimethylsilane (6.2 ml, 0.044 mol) was added with stirring to a solution of 3.15 g (0.016 mol) of 3-cyano-2-methoxy-5-(trifluoromethyl)pyridine in ml of chloroform under nitrogen and the mixture was allowed to stir at ambient temperature overnight. It was then concentrated by evaporation under reduced pressure and the residue partitioned between ether and IN aqueous sodium hydroxide. The ethereal phase was extracted with more aqueous sodium hydroxide and the combined alkaline solutinns were cooled and acidified with concentrated aqueous hydrochloric acid. The resulting mixture was extracted with ether severatimes and the combined ether extracts dried over sodium sulfate and concentrated by evaporation under reduced pressure. The residue was triturated with hot hexane, 0filtered, and dried to obtain 1.8 g (62 percent of theory) of the title compound as off-white crystals melting at 177-178.5’C. The proton NMR spectrum was consistent with the assigned structure.
Example J Preparation of 5-Acetyl-3-cyano-6-methyl- -2-pyridinol solution in methanol, 0.027 mol) in 14 ml of ethanol was added with stirring to a solution of 2.28 g (0.027 mol) of cyanoacetamide in 25 ml of warm ethanol and the mixture allowed to react at ambient temperature for 24 hours. The solid that formed was collected by filtration, washed with ether, and dissolved in 60 ml 3 of water. The aqueous solution was acidified to pH 1 with concentrated aqueous hydrochloric acid and the 36,094A-F -19- 36,094A-F -6- ,0LA, 6 I solids that formed were recovered by filtration and recrystallized from ethanol to obtain 2.7 g (60 percent of theory) of the title compound as pale yellow needles melting at 125-127°C. The proton NMR spectrum was consistent with the assigned structure.
Anal: Calc for C 8
H
7
F
3
N
2 0 2 6..36; 4.58; 15.90.
Found 61.21; 4.57; 15,65.
Example K Preparation of 3-Fluoro-2-methoxv-5- -pyridino.
Butyl lithium (8.5 ml of 2.5 M in hexane, 21.2 mmol) was added dropwise with stirring under nitrogen to a solution of 5-bromo-3-fluoro-2-methoxypyridine (4.20 g, 20.4 mmol) in 25 ml of anhydrous ether cooling to keep the temperature below -63°C. The mixture was 20 allowed to react for 15 min and then 2.38 ml (21.0 mmol) of trimethyl borate was added with stirring and the mixture was allowed to warm to -2J’C and stir for 1 hour. Glacial acetic acid (1.85 ml, 32.4 mmol) and then aqueous hydrogen peroxide (2.4 ml, 24 mmol) were carefully added with stirring and the mixture was allowed to react for 20 min at -5 to -20°C. The reaction mixture was then poured into saturated aqueous ferrous ammonium sulfate and the resulting mixture was extracted with 30 ml of ether. The ether extract was extracted twice with the ferrous ammonium sulfate solution and once with saturate- aqueous sodium chloride and was then filtered through sodium sulfate and concentrated by evaporatior, under reduced pressure to obtain 2.28 g of solid material. This appeared to be a borate. rt was taken up in 30 ml of 1N sodium 36,094A-F i
II
36,094A-F
(A
-21hydroxide and treated with 4.0 ml of aqueous hydrogen peroxide and the mixture was allowed to stir at ambient temperature for 4 hours. The reaction mixture was acidified with concentrated hydrochloric acid to pH 4 and then extracted three times with 30 ml portions of methylene chloride. The combined organic extracts were filtered through sodium sulfate and concentrated by evaporation under reduced pressure to obtain 1.85 g of the title compound. This was recrystallized from a mixture of ether and hexane to obtain a purified sample. The proton NMR spectrum was consistent with the assigned structure.
Anal: Cale for C 6
H
6
FNQ
2 50.35; 4.23; 9,79.
Found 49.92; 4.08 9.67.
Example L Preparation of 3-Fluoro-2-methoxv-5- 3-Fluoro-2-methoxy-5-pyridinol (1.60 g, 11.2 mmol) and 0.04 g (0.7 mmol) of potassium hydroxide were addd to 10 ml of dimethylformamide and the mixture blanketed with nitrogen and heated to 70 0 C with stirring, An excess of tetrafluoroethylene was introduced into the liquid by means of a sparge tube.
After stirring 4 hours at 70’C no reaction was observed so another Q.Q4 g of potassium hydroxide was added and the tetrafluoroethylene addition continued. The reaction was indicated to be complete by F 19 NMR after 3 hours, The mixture was allowed to cool and was then poured into a mixture of 50 ml of water and 60 ml of ether. The ethereal layer was extracted with 2-25 ml portions of water and one of saturated aqueous sodium 36,4A-F -21-
LA
conaucive to the formation of a substituted 36.094A-F goo -22chlorida and dried over sodium sulfate. The combined aqueous extracts were extracted with ether and the ethereal layer dried. The combined ethereal solutions were concentrated by evaporation under reduced pressure to obtain 1.65 g of the title compound as a yellow oil.
The proton NMR spectrum was consistent with the assigned structure.
Example M paration of ?-Fluoro-5-(1,1,2,2-tetrafluoroethoxy)-2-pyridinol Sodium iodide (1.80 g, 12.0 mmol) and then chlorotrimethylsilane (1.5 ml, 11.8 mmol) were added to a solution of 3-fluoro-2-methoxy-5-(1,1,2,2-tetrafluoroethoxy)pyridine (1.65 g, 6.79 mmol) in 8 ml of acetonitrile with stirring and under nitrogen and the mixture was heated at reflux for 2.5 hours, it was then allowed to cool and was diluted with 20 ml of methylene chloride. The resulting solution was extracted with water and with saturated aqueous sodium hydroxide, dried over sodium sulfate, and concentrated by evaporation under reduced pressure to obtain the title compound as a solid, This was reorystallized from toluene to obtain 0.95 g of the product as a white solid. The proton NMR spectrum was consistent with the assigned structure.
Cale for C7H4FsNO 2 36,.70; 1.76; b.11.
37.13; 1.68: 5.93.
Found 36,094A-F composition ingredients. Such mixtures can be designed 36,394A-F -F III r l r i I- -23- The following examples are presented to illustrate the invention and should not be construed as limiting the scope.
Preparation of Final Products Example 1 Preparation of N-Cvanomethy1-3-chloro-5- -(trifluoromethyl)-2-pyridinone A mixture of 4.0 g (0.02 mole) of 1 -(trifluoromethyl)-2-pyridinol, 2,6 g (0.022 mole) of monobromoaetonitrile, and 4.0 g of potassium carbonate in 40 ml of dimethyl sultoxide was prepared and stirred at ambient temperature for 3 hours, Water was then 1 added and the light brown solid that formed was separated by filtration and dried to obtain 2.3 g percent of theory) of the title compound: nieting Spoint, 84L-85’Q. This product had infrared and NMR spectra compatible with the assigned structure.
Anal.
Cale for C 8 04QF3N 2 0 %C 4,Q.59t %li 1.69; 11,84.
40.Q46, 1,561 14 11.79.
Found .4 The following compounds were prepared similarly and found to have compatible elemental (CtrN) analyses and NMR spectra: N-oyanomethyl-3-vluoro*g(trifluromethyl)-2 -pyridinne: mp, 142-143Q,: N-cyanomCethyl -3-brom-5-(triflutomethy) -2-pyridinonet mp, 76-181C,- 36. 094A-F -23- Lne present invention. Such surface–active agents are 36 J94A-F N-cyanomethyl-3-iodo-5-(trifluo-‘omethy)2-pyridinone: mp, 100-102’C; trifluoromethyl -pyridinone: mp, 73-75,)C; trif luoromethyl) -2pyridinorie: mp, 122-124’C-, triluoromethyl)-2pyridinone: mp, 88-9 1’C; N-oyanomethY1-3-.oyano-5-(trlfIL Qromethyl)-2-pyridinone* N-cyanomethyi-5broMO-4-(ifuoromethy)-2-pyridfloflO bp, 180-190″‘C at 15-25 mm Ug; N-oyanomethyI.-5-oolro-3-fiuor–PYriiofe; rnp, 120- 20~0Q mp, 101-103 C; 176″C,, N-cyanomethYL-3, 5-cooQ-2-pyr idi none alp, 11701r9’Q; mp, 19 Mp, 99-*00Q0 36 107LA-F UZI IKe dna can ce rormuiatea with solid, particulate 36-094A-E 1 N-cyanomethyl5-bromfo-2-pyidilofe: mp, 103-105″c; N-cyanomethyl-3-bromo-2-pyridiofe; mp, 171-172.5*C; N-cyanomethYl-3-f1Uoro-2-pyridilofe: mp, 126-127’C; hy 2pri oe liquid; N-cyanornethyl-5-methy,-3-flUoro-2-pyridflone rnp. 14l6- 147 N-cyanomethyl-5chloro-4-( trifluoromethiyl -pyridilnone: mp, 86-88’C; N-cyanomethyl3methy ho-5-( rifluoromethyl)- 2 -pyridinone: mp, 132-135 0 5-8 chyl»3 -cyano pyr id inone; mp, 80- 182Ct bp, 220″30’0 at 15-25 mm Hg; mp. 93,5-94,5’C,, -pyriiinonet nip, 107-109″C,, N-yinomethl (2p -e l pip1) abnyI– IOO2 7iinfe 4 09LIA-F 36,094A-.F -2 -12- -26- N-cyanomethyl-5-cyano-3-chloro-2-pyridinone: 17 N-cyanomethyl -5-cyano-3-f luoro-2-pyridinone: N-cyanome thyl-5 -bromo-3 -oyan o-2 -pyr idinone: 162r’C; mp, 173solid; mp, 158- N-oyanomethyl- 1 4-methoxy-3-oyano-2-pyriinonQ. mp, 188- 19 11CC; N-ynm hl–o y oan- mty12pri oe mp, 128-129.5’C;, and N-oyanomhyl-3,5,6-tichloro2pyrijinone; rnp, 173- 17 4 OUQ.
Other compounds which cani be prepared by this general method, using the teachings herein, include the following; N-‘cyanomethyl-6-fluoro-‘-(trilCuoromethyl)- -2-pyridinone, N-ynmt~–roo–ehl2 -pyr’icinone, N-oyanonmethyl-5-ohloro-4-(trif1luoromet hylthio )»?-pyridinone, methyl)-2-pyrillnone, N-ynmty–loo4 (di fiuorome thy1) -2-pyr id !none, -dimethylami oarbonyl.-2-.pyr id !none, N-cyanomethyl-3- -chlnvo-6- ttrifluorome rhy1) -2-pyr idi none, Npyridinone. Ni-cyanom~hy–ntro–(trifluoromethyl-2-pyridinono, and N-‘cyanomethYl-3,6-dif’luor’o-5- 36.094A-r -26- 36.094A-F -13i- -27- Example 2 Preparation of -(trifluoromethyl-2-pyridinone To a solution of 183 g mole) of 2,3-di- -fluoro-5-(trifluoromethyl)pyridine in 1200 ml of N-methyl-2-pyrrolidinone was added rapidly with stirring 750 ml of 10 percent a.queous sodium hydroxide.
An exothermic reaction ensued. The reaction mixture was cooled in an ice bath to bring the temperature down to about 450C, and was stirred for 0.5 hr. It was then treated with 146 g (1.22 mole) of monobromoacetonitrile dissolved in 200 ml of N-methyl-2-pyrrolidinone, and the resulting reaction mixture was stirred for another minutes. The addition of 1.2 1 of water resulted in the separation of a white solid, which was isolated by filtration, washed with water ,d dried. Another crop of a white solid separated out when the mother liquor was allowed to stand overnight. This solid was also separated by filtration and dried. The solids were combined and characterized as the desired product by infrared, NMR, and elemental analysis and found to have a melting point of 141-143 0 C. The overall yield was 200 g (90.7 percent of theory).
The compounds N-cyanomethyl-4-(trifluoromethyl)-2-pyridinone, m.p. 134-136 0 C, and N-cyanomethyl- -3,5-bis(trifluoromethyl)-2-pyridinone, m.p. 88-99°C, were prepared similarly and found to have compatible elemental (CH,N) analyses and NMR and infrared spectra.
36,094A-F -27i
F
i, 36.094A-F -14- -28- Example 3 Preparation of 1 ,2,2-tetrafluoroethoxy)-2-pyridinone Diisopropylethyiamine (0.82 ml, 4.7 mmol) and S0.30 ml (4.3 mmol) of bromoacetonitrile were added consecutively with stirring at ambient temperature to 3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)-2-pyridinol (0.90 g, 3.98 mmol) in 5 ml of methylene chloride and the mixture allowed to react overnight. It was then diluted with 25 ml of methylene chloride, extracted with 25 ml of water and with dilute aqueous sodium carbonate, dried over sodium sulfate, and concentrated by evaporation under reduced pressure to obtain the title compound as a solid. This was recrystallized from toluene to obtain 0.92 g (86 percent of theory) of purified material melting at 75,5-770C. The proton NMR spectrum was consistent with the assigned structure.
Anal: Cal for C 9
H
5
F
5
N
2 0 2 40.31; 1.88; 10.45.
Found 40.28; 1.85; QN, 10-17.
Biology Examples Example I Control of \ster Leafhopper by Systemic Action Rice seedlings grown on vermiculite substrate were removed from the vermiculite and placed in 15 ml of 10 percent Hoagland’s solution in 1 oz. plastic pill cups. Aqueous acetone solutions containing predetermined concentrations of the test compounds were Sprepared and 5 ml injected into each cup. A clear plastic tube was then placed over each plant (and its 36,094A-F -28- 36,094A-F 4cup). Ten adult, aster leafhoppers (Macrosteles severni) were placed within each tube and each tube was covered with a screen cap. Mortality was determined after 3 days. Some of the compounds tested that were active at 200 ppm concentration (in the cup) and the results obtained at this dose are given in the following table.
W X Y Z Mortality, 10 X percent H CF 3 H F 100 H CF 3 H FC 100 H CF 3 H C1 100 H CF 3 H I 100 H CF3 H H 100 H CF 3 H CH 3 100 H CF 3 H SCH 3 H CF 3 H CN 100 H CI H F 98 H Br H F 100 H Cl H Cl 44 H Br H Br 24 H Cl H H 77 H Br H H H I H F 100 H C0 2
C
2
H
5 H F 100 H C02CH(CH3)2 H F H OCF 2
CF
2 H H F H H H CN 100 36,094A-F -29- 36.094A-F -16- Example II Control of Insects by Contact and Systemic Action Aster leafhopper, greenhouse whitefly, and 2-spotted spider mite control by selected compounds was determined. Rice seedlings grown on vermiculite substrate were removed from the vermiculite and placed in 10 percent Hoagland’s solution in 1 oz. plastic pill cups. Suspensions or solutions of the test compounds in aqueous acetone containing a surfactant were prepared and sprayed onto the plants. The foliage was allowed to dry and then a clear plastic tube was placed over each plant (and its cup). Ten adult aster leafhoppers (Maorosteles severni) were placed inside 1 each tube and each tube was covered with a screen cap.
Mortality was determined after three days.
Cotton seedlings, approximately two weeks old and growing individually in 3 inch pots, were trimmed to the first true leaf and infested with adult whiteflies (Trialeuroides vaporarium). Oviposition was allowed to take place for 2-3 days; and the pl.ants were then moved to a greenhouse and held for 5 days during which time most of the eggs hatched. The plants were ‘then sprayed with predetermined concentrations of test compounds in aqueous acetone containing a surfactant and were held in a greenhouse. The degree of control was determined after 9-10 days.
Cotton seedlings approximately 2 weeks old and growing individually in 3 inch pots were trimmed to the first true leaf and infested with 50-’00 2-spotted spider mites. The leaf of each plant was then dipped into an aqueous acetone mixture containing a surfactant 36,094A-F several times with ether and the ether extracts were 36.094A-F -17-
«II
-31and a predetermined concentration of a test compound and 25 ml of the mixture were poured into the pot containing the cotton olant. The plants were placed in a greenhouse and mortality was determined 5 days after treatment. The control was corrected for any natural mortality in the untreated checks.
Some of the active compounds employed, the rates used, and the results obtained in the above tests are given in the following table.
Aster 2- S Y Rate, Leaf- White- Spotted ppm hopper fly Spider Contact Mite i CF 3 H F 25 100 NT NT H CF 3 H Cl 800 100 100 0 H CF 3 H Cl 25 100 NT NT H CF 3 H I 800 100 NT NT H CF 3 H I 25 90 NT NT S CF 3 H H 800 100 100 H CF 3 H CH 3 800 70 NT NT H Cl H F 800 100 0 NT H Br H F 800 100 100 0 H Cl H H 800 NT 95 83 H I H F 800 100 NT NT H OCF 2
CF
2 H H F 800 50 NT NT NT means no test 36.094A-F -31i i
A
36 .094A-F -18- -32- Example III Control of Tobacco BudworM, by Injection Test compounds were dissolved in dimethyl sulfoxide to prepare test solutions containing specific known concentrations. A group of 5 to 10 tobacco budworm (Heliothis virescens) larvae in the 3rd to 4th instar stage (weighing about 50-60 mg each) were injected with 0.5 ml of test solution near the anus along the dorsal midline and then placed individually in petri dishes containing a pinto bean diet. After 24 hours mortality was determined using ability to right as the criterion for death. Some of the active compounds tested, dose rates employed, and results obtained are recorded in the following table.
2 36, 094A-F -32wiln concentrated aqueous hydrochloric acid and the -6,094A-F -19- 33y z Dose Percent W X Z vg/Worm Mortality
HC
3 H H 50 H CF 3 H F 25 100 H CF 3 H Cl 50 H CF 3 H Br 50 H CF 3 H 1 50 H CF 3 H CN 50 H CF 3 H CF 3 50 H C 3 H 0C 6
H
5 50 H CO 2
CH(CH
3 2 H- F 50
CH
3
CH
3 CO H CN 50 H Cl H Cl 50 H Br H Br 50 4 H Br H H 50 H CH 3 H H 50 C 1 Cl H Cl 50 H H H C14 50 H H H Br 50 -33-

Claims (2)

1. An N-cyanoiethyl-2-pyrid.none compound of the formula CH 2 CI4 wherein; W is H, F, Cl, x is H, F, C1,, ON, COR, C0 2 R’ CH 3 or C3 Br, t, R, OR, OPh, SR, CF 2 Cl, or CONHRR t Yis H, R, OR, SR, OR or OPh; Z is F, Cl, Br. I, R. OR, SR, Mh N02 or CN R is C 1 -C 3 alkyl or Cl-C 3 aikyl partially or totally substituted with fluorine; ‘is Cl-C 14 alkylt

36.09J4A-F 36,094A-F -22- with the proviso that at least one of W, X, Y, and Z is other than H. 2. A compound according to claim I wherein: W is defined as in claim 1; X and Z independently are H, F, Cl, Br, I, CH 3 CF3 CF2H or CN; and Y is H, CH 3 CF 3 or CF 2 H. 3. A compound according to claim 1 or 2 wherein W is H. 4. A compound according to claim 1 or 3 wherein X is Cl, Br, I, CF 3 CF 2 H, C 2 F 5 CN or CO R’. A compound according to claim 1, 3 or 4 wherein X is CF3′ 6. A compound according to claim 1, 4 or 5 wherein Y is H. 7. A compound according to claim 1 or 6 wherein Z is H, F, Cl or CN. S: 8. A compound according to claim 1 which is N-cyanomethyl-3-fluoro-5-(trifluoromethyl)-2-pyridinorme. 9. A compound according to claim 1 which is N-cyanomethyl-3-chloro-5-(trifluoromethyl)-2-pyridinone. The compound according claim 1 which is luoromethyl)-2-pyridinone. 11. A composition which comprises an insecticidal amount of a compound according to any one of the preceding claims in combination with at least one agricultural adjuvant or carrier. I i I I DMW/2492U t L~ i 36,094A-F -23- t -36- 12. ‘f~ecomposition f Claim 11 wherein the active ingredient is present from 0.001 to 98 percent by weight. 13, A process for preparing a oompound having the formula CQ2 CN wherein 00 W, X, Y and Z are defined as in Claim 1, which comprises reacting either (1 a 2-pyridinol having the formula (it) wherein W, X. Y and Z are dWfined as in Claim 14 with ;z 4a base oapable of abstraoting a proton from a pyridinol, or 2% a preformed alt of a I-pyridlnol of formula (It) and a base, 0′:O?~I -36– r_ N-cyanomethyl-5-chlor-2-pyridinone: mp, 99-100’C; 36,094A-F -24- p -37- with monochloroacetonitriie or monobromoacetonitrile in a solvent under conditions conducive to N-alkylation; or (0 4-O a 2- or 6-halopyridine having the formula (III) wherein; W, X 1 Y and Z are defined as in Claim 4t Q is F, C1 or Br, with an alkali metal hydroxide in a solvent under coniditions conducive to the formation of 2Q an alkali metal salt of a substituted 2-pyridinol of formula (11) and reacting this intermediate, without isolation, with no?.oachloroacotonitrile or monobromoacetonitrile under conditions conductive to the formation of the desired product of formula -4W, T-4’roeas- -The-r 8of Claim 13 wherein the base S an aikali metal hydroxide or alkali metal carbonate The proaess of Claim 13 wherein the solvent is either water or an orqanic solvent or mixtures thereof. 16. A met-hod of Controlling Insects whioh c(omprises o. ntactingr said inCgCtc, the locus of said 1nsec or th plan ts» upon which aid insoots feaed w-It in ,1 ernpoud oan’ formul1a -l( I %6B~~ 1 36.094A-F -38- 14. A process according to claim 13 wherein the base is an alkali metal hydroxide or alkali metal carbonate. A process according to claim 13 OL claim 14 wherein the solvent is either water or an organic sir. ;ent or mixtures thereof. 16. A method of controlling insects which comprises contacting said insects, the locus of said insects, or the plants upon which said insects feed with an insecticidal amount of a compound of formula as claimed in any one of claims 1 through 9 or a composition thereof as claimed in claims 11 or 12. 17. A compound according to claim 1 substantially as hereinbefore described with reference to any one of the examples. 18. A process according to claim 13 substantially as hereinbetre described with reference to any one of the exampl s. I)ATED: 11 March 1991 PHILLIPS ORMONDE FITZPATRICK Patent Attorneys for: THE DOW CHEMICAL COMPANY DMW/2492t

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(en)

1992-07-20
1994-02-10
Mitsubishi Electric Corp
Output driver circuit

1988

1988-08-24
US
US07/237,014
patent/US4931452A/en
not_active
Expired – Fee Related

1988-10-31
WO
PCT/US1988/003874
patent/WO1989004301A1/en
unknown

1988-10-31
BR
BR888807796A
patent/BR8807796A/en
not_active
Application Discontinuation

1988-10-31
JP
JP63509182A
patent/JPH03500780A/en
active
Pending

1988-11-08
AU
AU24922/88A
patent/AU611221B2/en
not_active
Ceased

1988-11-09
MY
MYPI88001279A
patent/MY103465A/en
unknown

1988-11-10
CN
CN88109187A
patent/CN1034715A/en
active
Pending

1988-11-10
EP
EP88310620A
patent/EP0316185A3/en
not_active
Withdrawn

1989

1989-07-08
KR
KR1019890701288A
patent/KR890701560A/en
not_active
Application Discontinuation

Patent Citations (1)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

AU3892685A
(en)

1984-02-22
1985-08-29
Merck Patent Gmbh
Pyridin-2-one derivatives

Also Published As

Publication number
Publication date

EP0316185A2
(en)

1989-05-17

EP0316185A3
(en)

1990-01-10

AU2492288A
(en)

1989-05-11

BR8807796A
(en)

1990-08-07

CN1034715A
(en)

1989-08-16

MY103465A
(en)

1993-06-30

US4931452A
(en)

1990-06-05

KR890701560A
(en)

1989-12-20

WO1989004301A1
(en)

1989-05-18

JPH03500780A
(en)

1991-02-21

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