IE40296B1 - Ew hydroxypyridine carbamates and their use as insecticides - Google Patents

Ew hydroxypyridine carbamates and their use as insecticides

Info

Publication number
IE40296B1
IE40296B1 IE9699/74A IE252974A IE40296B1 IE 40296 B1 IE40296 B1 IE 40296B1 IE 9699/74 A IE9699/74 A IE 9699/74A IE 252974 A IE252974 A IE 252974A IE 40296 B1 IE40296 B1 IE 40296B1
Authority
IE
Ireland
Prior art keywords
group
formula
compound
ocon
alkyl
Prior art date
Application number
IE9699/74A
Other versions
IE40296L (en
Original Assignee
Hoechst Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of IE40296L publication Critical patent/IE40296L/en
Publication of IE40296B1 publication Critical patent/IE40296B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
    • 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
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/48—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
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/50—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems 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 carbon atoms of the ring system
    • C07D219/06—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/16—Ring systems of three rings containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Quinoline Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

The insecticide contains, besides at least one carrier material, at least one compound of the formula (I) <IMAGE> in which the substituents are as defined in Patent Claim 1, as active substance. The insecticide is prepared by mixing the active substance with the carrier material. [GB1489906A]

Description

» 4 0 29 G * This invention relates to hydroxypyridine carbamates, to a process for their preparation and to insecticidal compositions containing them.
The present invention provides compounds of the general formula R3 % J. *2 : i . 5 R1 in which one of R^ and R^ is a group of formula O C N II ^*7 and the other is a hydrogen or halogen atom or a (0,-0,)- 1 6 lO alkyl, halomethyl, (C^-C^alkoxy, (C^-C^alkylthio, (C^-C )- alkoxycarbonyl, di-t^-C^alkylaminocarbonyl, phenyl, phenyl (C^-C^alkyl, (C5-C6)cycloalkyl, cyano, phenoxy, phenylthio, (C^-C^alkoxymethyl, mono- or di (C^-C^ )alkylamino, N-morpholino, N-pyrrolidino or N-piperidino group; R_ is a hydrogen atom or a (C.-C Jalkyl, (C -C,)-^ 1 o 2 6 alkenyl, (C2-C&)alkynyl, )alkoxy, -C3)alkylthio, 15 - 2 - 40290 phenyl thio, (0,.-i*()loyrloal ky 1, phony 1 (i*j -r , >.il Kyi. (O -t* t > — alkylcarbonyl, (C^-C^Jalkoxyenrbonyl, benzoyl, di-(C^-Cg)- n 1 ky Inminomethy1, -CN, rN02; -NH2, di(Cj-C3Jalkylamino- «*.»rlH»ny1 , nu»ni»(t*|-i'^ldlkylnmiiio, -V( ).i I ky I •itn I no or *« (<*| -«*/j )n I ky I CftrlMiiiy Imnlno CH2 0 H2C CH 2 - 3 - 4 0 a U«» , ii j,. - ^ each of R& and R? is CH3» C^, CH2C1, CH2OCH3 or CHjSCH^ and X is an oxygen or sulphur atom, with the proviso that R2 and Rj are not both hydrogen atoms. 5 Preferred compounds of the general formula I are those in which X is an oxygen atom and R, and R_ are both o 7 methyl groups, and the group of the formula II is in the R3-position.
Whichever of and R3 is not the group of the formula lO II is preferably a hydrogen or chlorine atom or a ^cx"C3^~ alkyl, CI12C1, CIIC12, CC13# CF3 or (C^-C^Jalkoxymethyl group. More preferably R^ is a hydrogen atom or a (C^-C3)alkyl group and R2 is a hydrogen or fluorine atom or a CN, COCH3 or COOCH3 group. Each of R^ and Rg is preferably a hydrogen 15 or fluorine atom or a methyl group, or R^ and R,. together are a (C3~C5)alkylene group or a group of the formula -CH=CH-CH=CH-. In the latter case, the compounds are quinolines and are either - preferably - non-substituted in the benzene nucleus or substituted by a fluorine or 20 chlorine atom or a (Cj-C^alkyl, (C1-C;JJalkoxy, alkylthio, CN or methylenedioxy group. When R4 and Rg together are a (C3~C5)alkylene group, the compounds are tetrahydroquinolines, trimethylene-pyridines and penta-methylene pyridines; in these compounds the partially 25 hydrogenated nucleus is also preferably non-substituted or - 4 - 4 0 2 9 6 10 substituted by one of the atoms or groups specified for the quinolines or by a CP^ or di)alkylamino group.
An especially preferred group of compounds in accordance with the present invention is that in which one of R^ and R^ is a group of the formula XI and the other is a hydrogen atom or a (C^-C^Jalkyl group, R2 is a hydrogen atom or a (C^-C4)alkoxycarbonyl group, R^ and R,. are both hydrogen atoms or together are a tetramethylene group or a group of the formula -CH=CH-CH=CH- both of which nay be substituted by a halogen atom or a (C^-C^Jalkyl, methoxy or trifluoromethyl group, or together are a group of the formula CH.
CH. s or j H2C -CH, Rf and R? arc both methyl gronps and X is an oxygen atom. 15 The compounds of the general formula I can be prepared from starting compounds of formula Ilia, or Illb OH R„ ra J R-> 4 ^ x 2 1, li Ilia N 1J OH 11 lb The compounds of formulae Ilia and Illb may exist in the tautomeric pyridone form: - 5 - 40396 OH r-> 4 ^ 2 A Ilia \ Ilia' R3 R3 "4 "4 - ^ <^"2 I ji »»>_ || ^ A„A — ANA \ 0H R5 H ° In both cases so-called "ambident" anions are formed in the presence of bases: ,o|(~/1 O i ji. * * 1 Ji v;N ' x \M- R5 R1 R3 " R1 \ which react with alkylating or acylating agents, either at the O- or N-atom. Under suitable conditions, the reaction can be directed so as to produce the O-substituted compounds of the formula I. lO The present invention therefore also provides a process for preparing compounds of the formula I which comprises reacting compounds of formulae Ilia or Illb (a) with carbamoyl halides or thiocarbamoyl halides of the formula * XR6 Hal — C - N IV - 6 - 40296 in which Hal is n chlorine or bromine atom, or (b) with photujcno, th iophomjcne or oh Ioroformir .toiil (thion) i'sIitii and i'iMi'I in«| I h«» prtnltiol nht.ilnoil witli secondary amines of the formula /R6 5 H —-N Xr7 preferably in the presence of a solvent and of a suitable base.
In process (a) it is preferred to use a stoichiometric cxcess of from lO to 100% of the halide of the formula IV. lO The reaction is suitably carried out by dissolving or sus pending the compound of the formula Ilia or Illb in an anhydrous inert solvent or diluent such as chloroform, an aliphatic ketone, acetonitrile or dimethyl formamide, and adding an organic base such as triethylamine, pyridine or 15 quinoline, or an inorganic base for example sodium carbonate, potassium carbonate or calcium carbonate, in at least a stoichiometric amount; subsequently, the N,N-dialkyl-carbamoyl halide is added at a temperature of from about 0° to 80°C. 20 So as to achieve the intended 0-acylation of the ambident anions formed upon addition of the base, polar oolvents are used and tho reaction temperature is advantageously kept as low as possible. Although reaction temperatures above 30°C increase the reaction rate, in some cases 25 the amount of N-acylated product increases with increasing temperature to the detriment of 0-acylated products. - 7 - 40206 The reaction time varies depending on the base used and on the particular substitucnts R, to R_, but tho reaction l s usually requires 4 to 12 hours.
The reaction conditions of process (b) are generally 5 known from similar reactions and are described in detail in the Examples.
Compounds of the formula I in which and R. and/or R. and R_ are a substituted or unsubstituted 2 4 5 alkylene chain may be prepared from the corresponding lO unsaturated compounds by hydrogenation in known manner.
Compounds of the formula I in which R^ and R,. form a group of the formula -CH=CH-CH=CH- which is substituted by an amino group may be prepared from the corresponding nitro compounds by catalytic hydrogenation. 15 The compounds of the formula I can be isolated from the reaction mixture obtained in processes (a) and (b) in known manner by filtering off the precipitated amine hydro-halides, alkali metal halides or alkaline earth metal halides formed as by-products and by concentrating the 20 filtrate containing the reaction product. If catalytic reduction is carried out according as described above, the catalyst is also eliminated by filtration.
For further purification the crude products may be distilled in vacuo if necessary, or they may be recrystall-25 ized from an organic solvent.
Hie compounds of the formula I are colourless to slightly yellowish crystalline solids or highly viscous liquids. They are readily soluble in most organic solvents but only slightly soluble in water. Their aqueous - 8 - 40286 solutions are slightly basic.
The compounds of formula III, which are used as starting compounds for the processes (a) and (b), can be prepared by processes known from the literature or they 5 may be prepared according to analogous processes.
The preparation of such starting compounds is described, for example, in the following publications: U.S. Patent No. 1,147,760; German Offenlegungsschrift (DOS) No. 2,058,002; DOS No. 1,620,066; DOS 2,103,728; lO Chem. Rev. 43. 43-68 (1948); J. Am. Chem. Soc. 68, 2685 (1946); 68, 2686 (1946); 69, 365 (1947); 69, 371 (1947); 69. 374 (1947); Monatshefte fur Chemie lOO, 132-135 (1969).
The compounds of the formula I have a highly selective insecticidal activity which is directed almost exclusively 15 against aphids, and possess excellent systemic properties.
Iftey show the same efficiency whether absorbed via the plant foliage or via the root system. Therefore, aphids living hidden inside galls and other parts of the plants that are difficult to reach can also be combated with good 20 results. They are also active against aphids which have become resistant to phosphoric acid esters.
The present invention therefore also provides aphicidal compositions comprising as active ingredient a compound of the formula I together with a carrier, and a method of 25 combating aphids which comprises applying to their habitat a compound of the formula I.
Examples of aphids which can be combated successfully by the compounds of the invention are Brevicorvne brassicae. Mvzaphis rosarium. Aphis Schneideri? Eriosomatidae such as - 9 - •10 20 6 Eriosoma lanlgerumi gall-forming aphida such aa Pemphigus spec, as well as Mvzodes persicae.
On the other hand, useful coleopters (such as ladybirds), butterflies, orthopterae, dipterae, hyroenopterae (such as ichneumon flies), and predatory mites feeding on insect pests are not or only slightly affected even by high concentrations of the active ingredients. The action on aquatic organisms is insignificant, the compounds having an action on fish only at high concentrations.
The compounds of the present invention or the compositions containing them may be applied in widely varied manners. They may be applied to the foliage and/or affected parts of the plant or, on the other hand, to the earth surrounding the plant.
Marketable compositions containing these compounds may consist of dusting formulations, powders or granules, wherein the active ingredient is present in admixture with solid extenders or carrier materials, such as inert substances in powder or granular form. Generally, these compositions contain from 3 to 7596 by weight of these compounds. Suitable solid extenders or carrier materials arc, for example, kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talcum, ground magnesia (chalk), fuller's earth, plaster or agrillaceous earth. The compositions may also be used as wettable powders which contain, in addition to the active ingredient, known wetting agents and/or dispersing agents and optionally fillers and/or emulsifiers as further additives.
For application in the field these formulations are - lO - 40296 further diluted with suitable solvents, preferably with water. The concentration of active ingredient in such ready-to-use formulations may vary within wide limits depending on the mode of application (foliar or root) and the type of aphid being combated. Generally, the concentration may be between about 0.0002 and \% by weight of active substance.
The compositions may also be formulated as liquid preparations in the form of concentrated emulsions for spray liquors which normally contain the active ingredient together with one or several wetting agents, dispersing auxiliaries or emulsifiers. For liquid preparations organic solvents may also be used.
The wcttablc, dispersing and emulsifying agents may be of the cationic, anionic or non-ionic type.
Hie compounds of formula I may also be used as active ingredients in fumigants.
The following Examples illustrate the invention.
EXAMPLES OF PREPARATION EXAMPLE 1. 0C0N(CH ) [ v X a N ^ "CH3 2-methyl-4-dimethylaminocarbonyloxyquinoline (a) To a suspension of 75 g (0.47 mole) of 2-methyl-4- hy^roxyquinoline in approximately one litre of acetonitrile, / 1'30 g of anhydrous potassium carbonate were added at room - 11 - 40296 temperature. The mixture was heated to reflux temperature ("80°C) while stirring vigorously for about two hours.
After cooling to room temperature, 76.7 g (0.71 mole) of dimethylcarbamic acid chloride were added and the reaction 5 mixture was stirred vigorously at room temperature for about 8 hours. After cooling, the mixture was suction-filtered and .the filter cake was washed with acetonitrile. The filtrates were combined and the acetonitrile was evaporated under water jet vacuum. 10 The residual oil was submitted to fractionation in vacuo. At a temperature from 158°-161°C (O.OS mm Hg) the distillation yielded lOO g of a colourless highly viscous liquid, the elementary analysis values of which corresponded to those obtained for 2-methyl-4-(dimethylaminocarbonyloxy)-15 quinoline; when submitting this liquid to thin-layer chromatography and to NMR spectrum, it proved to be uniform. Besides the results of the NMR spectrum, the presence of a carbamate was further confirmed by IR spectroscopy, (b) 24 g (0.15 mole) of 2-methyl-4-hydroxyquinoline were 20 dissolved in 200 ml of dimethylformamide (anhydrous and free from amine), 23 g (0.22 mole) of triethylamine were added and, subsequently, 24 g (0.22 mole) of dimethylcarbamic acid chloride were added dropwise.
The reaction mixture was heated to 60°C (for about 8 25 hours) until thin-layer chromatography showed the absence of starting material.
Separated amine hydrochloride was suction filtered off, the reaction mixture was cooled to from 0° to 10°C. The filter cake was washed with a minor quantity of cold - 12 - 40296 dimethylformamide, the filtrates were combined and the solvent was evaporated off in vacuo. The oily residue was P _— submitted to fractional distillation.
At 145°C (0.01 mm Hg) 21 g of a colourless and highly 5 viscous liquid were obtained.
EXAMPLE 2. 2-methyl-4-dimethylarninocarbonyloxy-5,6,7,8-tetrahydroquinoline lO (a) 287 g (1.76 mole) of 2-mothy1-4-hydroxy-5,6, 7, 8- tetrahydro-quinoline were dissolved in 1650 ml of chloroform (anhydrous and free from alcohol); to this solution 267 g (2.64 mole) of triethylamine and 284.5 g (2.63 mole) of dimethylcarbamic acid chloride were added successively. 15 The mixture was then heated to a temperature of 50°C until after approximately 6 hours thin-layer chromatography did not show any initial compound.
After cooling to room temperature, about one litre of ice water was added dropwise to the reaction mixture while 20 stirring, until the amine hydrochloride formed in the reaction was dissolved and two liquid phases were obtained. The organic phase was separated, washed with a minor quantity of water, dried and concentrated. At a bath temperature of 100°C and approximately 2-3 mm Hg pressure some ml of an 25 oily by-product distilled off. The remaining oily residue was dissolved in boiling n-hexane. - 13 - 40206 347 g of a colourless product having a melting point from 89°-90°C crystallized from the cooled solution. On thin-layer chromatography this product proved to be uniform and elementary analysis yielded the expected values for 2-methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquino-line. IR spectrographic and NMR spectrographic data confirmed the formation of the expected O-acylation product, (b) 16.3 g (O.l mole) of 2-methyl-4-hydroxy-5,6,7,8-tetra-hydroquinoline were dissolved in 150 ml of chloroform (anhydrous and free from alcohol) and this solution was added dropwise to a previously prepared solution of approximately 20 g (0.2 mole) of phosgene in 100 ml of chloroform at a maximum temperature, of +10°C. After a period of two hours at +10°C, the reaction was completed at room temperature for another hour. Non-reacted phosgene was then blown out of the solution by means of a dry nitrogen current and the solvent was evaporated off in vacuo at room temperature. The semi-solid residue was again dissolved in dry chloroform free from alcohol, the solution was cooled to +10°C and on excess of dimcthylamine was introduced at this temperature. After standing for two days at room temperature, chloroform and excess amine were eliminated by distillation iri vacuo. The residue was digested with ice water, separated from water and dissolved in toluene. After drying and evaporating the toluene a residue of 7 g was obtained which crystallized thoroughly upon being submitted to trituration with n-hexane. Recrystallization from n-hexane yielded 4 g of a uniformly crystalline product having a melting point of from 88-89°C. This product proved to be - 14 - •J o a o IS identical with the product obtained according to Example (2a). (c) 5 g of a nickel catalyst consisting of 50 percent by weight of finely distributed nickel on diatomaceous earth were added to a solution of 20 g of the substance according 5 to example (1) in 1 litre of toluene and the whole was heated at 100°C in a 2 1 steel autoclave with hydrogen at a pressure of 100 atmospheres. After 20 hours the mixture was cooled, the catalyst filtered off, washed with toluene and the filtrates were concentrated. The residue was distilled, 10 11 g of a product (b.p. , „ 130°-142°C) were obtained. 0.1 nun Hg On crystallization this product proved to be identical with the product obtained according to Example (2a).
The following table shows a number of additional compounds prepared according to Example 1. - 15 - TABLE 1 1 1 1 i example nuicber formula base solvent reaction temperature (°C) reaction period (hour s) melting ssir.z °C (solver. -boiling -pz-T.z °C (nar. Hr 1 i ocon(ch3)2 47 °c 1 . ^ N ^ K2C03 80 (cyclohexar.e; 3 • \ ,u ') sS. *-N ch3cn 2 132°c (0.01" i I ocon(c2h5)2 54-55"c 4 N ^ > k2co3 80 (n-hexar.e •X A,- ch3cn 6.5 167-17c"c (0.05 J 1 TABLE (Continued) example number formula base solvent reaction temperature (°C ) reaction period (hours) melting point C (solvent) boiling point °C (mm Hg) ocon(ch3)2 ch, ch. ocon(c2h5)2 K2C03 ch3cn K2C03 ch3cn 80 4 80 9 98-99°C (n-hexane) 139°C (0.01) TABLE (Continued) example number formula base solvent reaction temperature (°C)" reaction period (hours) 1 melting point °C (solvent) boiling point °C (mm Hg) ocon(ch3)2 ' 7 ■ i (c2H5)3n 25 64-65°C I "V X^CH, dmf 65 j (n-hexane) =„3 8 ocon(ch3)2 - . " X V ^ A XN ^CH3 ch, (C2H5)3N chc13 25 65 134-136°C (0.005) i TABLE (Continued) i j example number formula base solvent reaction temperature (°c) reaction period (hours) melting point °C (solvent) boiling point °C (mm Hg) ocon(ch3)2 9 k2co3 80 91-92°c ^ ch3 ch3cn 7 (n-hexane) 0c0n(ch3)2 10 ch, . : ^r^\As t ' ' 1 i K2C°3 80 93-94°C i t v^.^ca, ch3cn 4 (n-hexane) j i C«3 c tv C3 a T A 3 L E (Continued) n; O example number 11 12 formula base solvent h3c ocon(ch3)2 k2co3 ch cn ch. ch(ch3)2 ocon(ch3)2 (C2H5)3N chci_ reaction temperature (°C) reaction period (hours) 80 6 60 6 melting point C (solvent) boiling point °C (mm Hg) 147°c (0.001 69-70°C (n-hexane) c t: c c TABLE (Continued) j 1 example number 1 formula base solvent reaction temperature ] (°c) reaction period (hours) melting point °C (solvent) boiling point C (mm Hg) 13 ocon(ch ) ch(ch_), j 3 2 ! . 1 '; i v JL A n ^ ch3 (c2h5)3n chci3 50 4 62-63°c (n-hexane) 14 ocon(ch ) ; : j j ^A„ACH3 ch(ch3)2 k2c°3 ch3cn 80 6 - 1 1 i J 1 t 99-100 c j 1 (n-hexane) \ TABLE (Continued) example number forzr.ula base solvent reaction temperature (°c) reaction period (hours) melting point c (solvent) boiling point °c (mm Hg) ocon(ch3)2 . 69°c 15 /VXN k2c03 80 (n-hexane) ' ^"X "s, n' ch3 ch(ch3)2 ch3cn 6 139-140°c (0.01) ! 16 ocon(ch,), (ch )_c 3 2 x^x Xs k2c03 80 63°c ch3cn 6 (n-hexane) i i 9 TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling point °C (mm Kg) 17 OCON(CH J (CH,)_ C 3 2 33 .
K2C03 CH3CN 80 6 i I ! j 166°C j (0.03) 18 OCON (CH3) K2C03 80 96-97°C ^s. ' ' CH3CN 7.25 (n-hexane) V X A ^N^\CH3 G ti CJ TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C j (solvent) j boiling point °C (mm Hg) 19 ocon(ch3)2 .-"x X i i ; /J. cf^ \ 7 xn^^ch3 (c2h5)3n dmf 70 65 t 74-75°C (n-hexane) ' 20 0C0N(CH ) f : v- ii J. ni \n-' nch3 %. yk. *1 i k_c0, 2 3 80 104-10;"": °^a„ach3 ch3cn 5 (n-hexar. ^ TABLE (Continued) ex2ur.pl e number formula base solvent reaction temoerature (°cf reaction period (hours) melting point c (solvent) boiling point °c (nar. Hg) ocon(ch,). 3 2 23 k2c03 80 151-152°c i *■ ' ' Br X Ajj ACh3 ch3cn 2 (toluene) j i i ocon(ch3)2 24 ch3° ^ (c2h5)3n 80 49-51°c n' "ch3 chc13 4 (n-hexane) ; TABLE (Continued) example number formula base solvent reaction temperature (°c) reaction period (hours) melting point °c (solventf boiling point c (mm Hg) ocon(c2h5)2 25 CH3° Ok A n ch3 K2C03 ch3cn 80 6.5 160-163°c (0.01) ocon(ch;3)2 26 ch 0 .. (c2h5)3n 90 80-81°c 1 ■ ii X A\n A\ch3 DMF 65 (n-hexane) TABLE (Continued) example number formula base solvent reaction temperature (°c) reaction period (hours) melting point °c (solvent) boiling point °c (mm Hg) ocon(ch3>2 27 • ^ v i (c2h5)3n 70 170-173°c ^ ch30 \ "n' ^ch3 dmf 8 (0.01) ocos(ch3)2 28 k2c°3 80 106-107°c ch3 ch3cn 10 (n-hexane/ toluene) 0ch3 ♦ i TABLE (Continued) example number formula base solvent reaction temperature (°c> reaction period (hours) melting point "°c (solvent) boiling point °c (trar. Hg) 29 ocon(ch3)2 n n ch3 och3 k2c03 ch3cn 80 18 1«>%-170°c * 'r.-hexane/ toluene) i 30 . ocon(ch3)2 n0 •^v^-'x^n^sxch3 (C2H5}3H dmf 40-50 70 :s4-155°c !.*.-hexane/ toluene) TABLE (Continued) example ; nuicber formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling point °C (mm Kg) ocon(ch3)2 i t ! 31 (C2H5,3N dmf 70 10 112-113°C (cyclohexar.ei 1 y" . n ocon(ch3)2 i i 32 \ ^ : 1 *NX A x: ch3 K2C03 ch3cn 80 5 K»2-193°C (0.05) TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling point °C (mm Hg) 33 ocon(ch3)2 C6H5°^X/^ k2c°3 ch3cn in O 00 i 107-108°C I (n-hexane) j i - ! 34 i ocon(ch3)2 ■i j V^/>OL ! i k2co3 ch3cn 80 7.5 ! I 126-127°C j (n-hexane) - | 1 j ! i i 1 1 TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C i (solvent) • boiling point °C (mm Hg) OCOX(CH3)2 58-59°C 35 • <* •» (C2H5)3N 60-70 (n-hexane) C2H5S : • ' N ' CH3 DMF 19 226-228°C (0.01) 36 C2HS N C2H5 ' OCON(CH3)2 ^ > (C2h5)3N 75 66-67°C • .4 > N ^CH3 CH.CN 8 (n-hexane) TABLE (Continued) ! example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling-point °C (mm Hg) 37 OCON(CH ) K2C03 CH3CN 60 2 ' t 153°C (acetonitrile) \ 38 i OCON(CH ) H N 32 Vv^ Hydrieren Toluol 100 5 130-131°C (toluene) TABLE (Continued) example nuicber formula base solvent reaction temperature (oc) reaction period (hours) melting point C (solvent) boiling point °c (mm Hg) N 0c0n(ch ) 39 ► 3 2 1 yr- k2c03 80 78-79°c • N. ' ch3cn 6 (n-hexane) « X ^ N " n ch3 | ocon(ch_) W * • 1 40 n n a*x ch3 K2C03 ch.cn 80 7 o 129-130 c 1 (n-hexane) i TABLE (Continued) 1 example number formula base solvent reaction temperature (°C) reaction period (hours) melting point C (solvent) boiling point °C (mm Hg) 41 ocon(ch3)2 •V N >» % I ji .1 J "«s- K2C03 ch3cn 80 6 1 1 1 116-117°C | (cyclohexane) ! 42 c2h5 ocon(ch3)2 CZ 2 5 Jk .-A x: xn ' ch3 (C2H5)3!. CHC13 25 110 192-193°C (0.05) 1 j TABLE (Continued) exair.pl e number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) * boiling point j N (mm Hg) ^ 43 OCON(CHj)^ y; . .T v . N ^ C2H5 N -N nCH3 C2H5 (C2H5,3N CHC13 60 11 207°C (0.05) 44 . ^ %N "OCON(CH3)2 K2C°3 CH3CN 80 8 130-131°C 1n-hexane/ _ toluene) i TABLE (Continued) ! ! example j number formula base solvent reaction temperature (°c) reaction period (hours) melting poirir. C (solvent, boiling poir.- "z" (mm Hg) t t | i i 45 CH3 ^ XNOCON (CH3) 2 k2C°3 CH3CN 80 3 68-69cc (n-hexar.e/ toluene. 1 i 46 CH3 CH3 I ' ^Ni?:^XOCON(CH3)2 k2C°3 -CH3CN 80 3 91-92°c (n-hexar.e/ toluer.e TABLE (Continued) exsur.pl e number formula base solvent reaction temperature (°C) reaction period (hours) 0 c melting point C ^ (solvent) boiling point °C cs (mm %) 47 CH3 N" : j .
V ^ "N. XN'' OCON(CH3)2 (c2h5)3n chcl, 50 9 151-153°C (0.1) 48 OCSN(CH3)2 . X XN u ^ X. '^N 'XCH3 K2C03 CH3CN 25 8 93-94 .(n-hexane) 1 TABLE (Continued) : example number formula i 1 base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling point °C (mm Hg) 49 ! OCSN(CH3)2 . ' ' n ~ch3 k2c03 CH3CN 80 36 60°C (n-hexane) 162°C (0.1) » 50 OCON(CH3)2 •xj. A "V xCOOC2H5 K2C03 CH3CN 80 6 111°C (n-hexane/ toluene) TABLE (Continued) example number formula base solvent reaction temperature (°c) reaction period (hours) melting point °C (solvent) boiling point C (mm Hg) ocon(ch3)2 51 K2C03 25 102°C 1| > N ch3cn 3.5 (n-hexane) 52 ocon(ch3)2 \/S/ COOC2H5 k2c°3 ch3cn 25 48 71°C (n-hexane) 193°C "(0.005) | TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C ; (solvent) boilir.g point °C (nar. Hg) ocon(ch3)2 53 x. cn ii K2C03 25 121°c ; ^ ^N * ch3cn 27 fr.-hexane) OCON (Cli,) 1 54 1 i 1 k2c°3 80 3>3-94°C ch3cn 7 (r.-hexane) T A 3 L E (Continued) 1 i { example number formula base solvent reaction temperature (°c) reaction period (hours) o melting point c {solvent) boiling point °c (mm Hg) t 1 i i 1 i i i 55 ' 1 ocon(ch3)2 . COOCHj A v ch3' -n ^ch3 (c2h5)3n dmf 60 4 ! j t ! i i ! 149°c ! (0.05) £ i i i j 56 ocon(ot3)2 - ^ cooc2h5 .1 ^ ch3 c«3 (C2H5)3B CH-CN 80 12 1 1 ~ 141°c (0.01) 1 TABLE (Continued) example number formula base solvent reaction temoerature (°c)" reaction period (hours) melting point *: (solvent) boiling poir.r "Z (mm Hg) i 1 57 t » ocon(ch3)2 cooch3 A A ch3 ^ ^ ch3 (c2h5)3n dmf 70 60 131-141°c (0.05) 58 cx:on(ch3)2 c1 cooch3 CH, N CH, (c2h5)3n dmf 70 40 125°c (0.01) TABLE (Continued) example number formula base solvent reaction temperature (°c) reaction period (hour8) melting point °c (solvent) boiling point c (mm Hg) 0c0n(ch3)2 59 Br > - / coch, V V j (c2h5)3n 25 100-101°c ch3 "n • ^ch3 dmf 48 (ethanol) 60 CH3 ocon(ch3)2 k2c°3 80 57°c (n-hexane) ch3cn 6 135°c (0.01) TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hour8) melting point °C (solvent) boiling point °C (mm Hg) 61 0 0 ■' 0-C-N(CH ) H CO-C * triethylamine DMF 40 5 95-98 62 0 0 i' 0-C-N(CH ) H3C-C j * ^ CH3 K2C03 acetonitrile 40 48 123-126 1 i TABLE (Continued) example number formula base solvent reaction temperature (°C) reaction period (hours) melting point C (solvent) boiling point C (mm Hg) 63 0 O-C-N(CH3) N "C6H5 K2C03 acetonitrile 30 6 88-92 64 0 O-C-N(CH3)2 • > » •" • •• *•.
*N " C3H?n K2C03 acetonitrile 40 10 176-180 (0.2) j TABLE (Continued) i ! 1 1 example number formula base solvent reaction temperature (°C) reaction period (hours) melting point °C (solvent) boiling point °C (iot Hg) 0 1 O-C-N(CH3)2 i i 65 H ^ A ■< \ N C3H?-n K2C03 DMF 80 1 170-175 (0.05 mm) 66 0 O-C-N(CH-), H CO 3 * SH,-„ K2C03 DMF 90 1 40-44 t I l © vj j) TABLE (Continued) exareple number formula base solvent reaction temperature (°C) reaction period (hours) o melting point C (solvent) ! O boiling point C ; (mm Hg) | 0 O-C-N(CH,)_ I t H.CO 3 2 ^ 67 •v • • * • K2C03 80 N "C H_-n DMF 1 180-190 i (0.2 mm) : «* U « u o In the sane way the following compounds can be prepared: OCON (CII^ ) ^ \ N "X' i (H*ON(OII ;.v !- n n N ocon(ch ) i 3 2 n n ocon(ch3)2 X i -' J • J / n i' • och_ ocon(ch ) ■ 3 2 t ; \ 'J j-.
N' ch2-och3 ocon(ch_) i 3 2 1 X-U J ocon(ch,)_ ocon(ch-) I J 2 i 3 2 ch ) n-ck=n . J i i •' i;- X l?!.
XN CH^ CH3 ^N ^ CH3 ocon(ch3)2 > N 1 J • • J XN cp.
J ocon(ch3)2 ch. n 'con (ch3 ) 2 ch. - 49 - - OS - "HO ^ N ¥ "s z(£IID)nodo 0zhdodocho TOD. N -V 'r-.r- ! v r ^ ' Z(eHO)NOOO / o n - r y : Z(CHO)NOOO °V ""v ^ r f r' ,1 Z(eHO)NOOO TOx N V V.
Z("HO)NOOO C Q 7 HO HO ^ „NV r. I r 3(£ho)nooo vv z.z.
N\ V""v r f r, : X .N j O CHO I! o Z(CHD)N000 N. N O II M' ! Z(eho)n-o-o II o N r'/r>.t vr " -4 o„ Z(eHD)KOOO CHOv N\ V CdO r . - f [ V V 2(EHO)nooo e2 1 j' J n * sci1. 1 j "*n "n(ch3)2 ocon(ch3)2 y o. n ^ sc _ h- o 3 / \ s —* ^ OCON(CH3>2 J y^y \ ' N . CH o-c-n(ch3)2 o .1 O-C-N(CH3)2 i ; i' ' i J n 1 ' 1 / ' n / FORMULATION EXAMPLES EXAMPLE A.
A wettable powder easily dispersible in water is obtained by grinding together 5 12 g of 2-methyl-4-(dimethylaminocarbonyloxy)quinoline as active ingredient and tr) ) 3 g of Silcasil (highly dispersed synthetic silicic acid), and blending this with 43-45 g of a pre-mix consisting of I.O lO g of cellulose pitch (potassium salt of lignin- sulfonic acid) 49 g of Ca-Mg-Al-silicate 49 g of Ca-Mg-Al-silicate 11.5 g of highly dispersed synthetic silicic acid 15 3.5 g of polypropylene glycol (m.w. 750) - 51 - i o a a o l g of Na-olcylmethyltauride 75 g of preliminary blend Hiat means that 60 g of this wettable powder contain 20 weight % of active ingredient 49 weight % of Ca-Mg-Al-silicate 16.5 wt. % of highly dispersed synthetic silicic acid 3.5 wt. % of polypropylene glycol (m.w. 750) 1 weight % of Na-oleylmethyltauride 10 weight % of cellulose pitch .*) (R) =» Registered Trade Mark EXAMPLE B.
An emulsifiable concentrate consists of: 1.5 g (15% by weight) of 2-methyl-4-dimethylamino- carbonyloxy-5,6,7,O-tetrahydroquinoline 6.5 g (65% by weight) of cyclohexane as solvent and 2.0 g (20% by weight) of ethoxylated nonylphenol (nonyl (ethoxy)^Q phenol) as emulsifier.
BIOLOGICAL EXAMPLES EXAMPLE I.
Potted horse beans (Vicia faba) were infested with 200 specimens each of bean aphids (Doralls fabae) and, after stabilization of the population, sprayed to drip-off with decreasing concentrations of an aqueous dilution of the emulsion concentrate containing the compound described in Example (I) as active ingredient 3 days later the percentage of killed aphids was determined by counting the numberii of surviving and dead innocta. 40296 The following table shows the mortality rate depending on the concentration of active substance (AS) in the aqueous dilution, as compared to the efficiency of two compounds having similar Htructuros of comparable degrees of efficiency.
T A B L E 1 Structural formula Concentration of AS in the spray liquor in % by weight % of mortality Compound of Example (I) (according to the invention) 0.00019 0.000095 100 98 O.000048 80 ! 0.000024 50 1 ^ if > x- ' 1! | 0.006 loo i k u J "S; ' vN 0.003 98 OCON(CH3)2 0.0015 60 Dutch Offenlegung-sschrift No. 6,606,695 (comp. agent I) 0.0006 20 CH(CH.)_ 0 | J * a i (CII3)2N-C-0 y * N 0.005 lOO H 3 0.0025 0.0012 96 60 Isolan (comp. Agent II) 0.0006 20 - 53 - 40296 Similar or identical results were obtained with the compounds of examples 2, 3, 4, 7, 8, 9, 10, 11, 13, 19, 20, 24, 27, 39, 45, 47, 57 and 60.
EXAMPLE II. 5 Potted horse beans (Vicia faba), the root system of which was wrapped in sheet plastic, were infested with bean aphids (Doralis fabae) and treated with gradually decreasing concentrations of the product of Exan$>le 57 in such a way that an aqueous dilution of an emulsion concen-lO trato was uniformly distributed in the root area by means of a glass funnel. 8 days later the percentage of killed aphids was determined by counting the numbers of surviving and dead insects. mg of AS per root system 0.5 0.25 0.125 0.06 0.03 % of mortality lOO 100 94 81 40 Similar or identical data were obtained with the 15 rest of the compounds specified in Biological Example (I).
EXAMPLE III.
The stem of a horse bean plant about 25 cms high was wrapped in cotton (wadding) and covered with cellophane. By means of an injection syringe, 2 ml of an aqueous 20 suspension of wettable powder of the compound of Example (I) having the specified concentration of active substance was uniformly distributed in the cotton pad. At the accordingly administered quantities of active substance, bean aphids living on the leaves of the plant were destroyed 25 as follows after 3 days: - 54 - 40296 ■ concentration of AS in the spray liquor in % by weight 0.25 0.125 r- 0.06 0.03 0.015 % of mortality 100 lOO 86 *J10 20 lo This test shows the capacity of the active substance to penetrate into plant tissue and to circulate within the plant. This same capacity is also characteristic for the other compounds specified in Biological Example I.
EXAMPLE IV.
The compounds according to the present invention, in the gaseous phase, were also efficient against aphids (Doralis fabae).
When a potted plant infested with bean aphids was placed under a glass bell having a volume of 23 1 and a 2 filter paper of 133 cm surface area and containing a given quantity of active substance was suspended in the air-filled volume, the aphids on the test plant were destroyed after 2 days. A test carried out with the compound of Example (3), gave the following results: mg of AS on the filter 0.25 0.125 0.06 0.03 0.015 % of mortality 100 lOO lOO 97 84 /o The other compositions specified in Biological Example I gave similar or identical results.
EXAMPLE V.
Useful insects such as ichneumon flies ( Coccygomimus turionollao (I..)) are not affected by concentrations effective - 55 - 40296 against aphids. This is shown in the following experiment: 2 Rectangular-shaped filter papers (ISO cm ) were sprinkled uniformly by means of a pipet with acetone solutions of active substance in decreasing concentrations. 5 After drying the filter paper was put inside a glass tube in such a way that its total interior wall surface was covered by the filter paper. Subsequently, lO females of ichneumon flies were inserted in each of the glass tvibes thus prepared and, after closing the tubes with a pierced 10 cork, a constant flow of air (lO 1 of air per hour) was passed through (suppressing a possible gaseous phase, imitation of natural flow of air outdoors). The following mortality rates were found after 24 hours for the use of the compound of Example (I). mg of AS on the filter % of mortality Compound of Example (I) 0.012 lOO (as per the invention) 0.006 40 0.003 0 0.0012 0 0.0006 0 | Carbaryl 0.0006 100 • (compar. agent III) i 0.0003 lOO 0.00015 40 0.000075 O : Isolan 0.003 lOO 1 (compar. agent II) l 0.0012 80 i i i i 0.0006 O 40296 The compounds mentioned in Biological Example I gave results similarly or equally favourable to those of Example (I).
KXAMPI.I-: VI .
No action was observed on lady bugs (Coccinellldae) essentially feeding on aphids when the same concentration rates were used as those for combating aphids. The following Example confirms this with respect to Imagines of the species Coccinella septempunctata: 10 On Petri dishes lined with filter paper lO insects cach of the above-mentioned species were placed and then sprayed with decreasing concentrations of an aqueous dilution of the emulsion concentrate of the compound of Example (I) (corresponding to 600 1/lia). The following 15 mortality rates were found after 24 hours: mg of AS on the filter % of mortality 0.003 10 0.0015 0 0.0006 0 0.0003 0 0.00015 0 - 57 -

Claims (1)

1. •i o »\!i) a r l. A l H :: : I. A compound of the ijcncral formula b3 J XI R_ N ' R, 3 X in which one of R^ and R3 is a group of the formula X R 3 / 6 — O -C N II ^ r 7 and the other is a hydrogen or halogen atom or a (C.-C )- x 6 alkyl, halomethyl, (C,-C,Jalkoxy, (C,-C^)alkylthio, lb Id (C^-C^alkoxycarbonyl, di-(C^-Cj)alkylaminocarbonyl, phenyl, phenyl (Cj^-C^)alkyl, (C5-C6)cycloalkyl, cyano, phenoxy, phenylthio, (C^-C4)alkoxymethyl, mono- or di- (C^-C^)alkylamino, N-morpholino, N-pyrrolidino or N- piperidino group; R~ is a hydrogen atom or a (C.-C-)alkyl, (C.-C,)-^ a o 2 d alkenyl, (C2-C&)alkynyl, (^-C^alkoxy, )alkylthio, phenylthio, (C^-C^)cycloalkyl, phenyl(C^-C3>alkyl, (C^-C^alkylcarbonyl, (C^Cgjalkoxycarbonyl, benzoyl, di-(C^-C6)alkylaminomethyl, -CN, -N02, -NH2« di(C^-C3>- alkylaminocarbonyl, mono (c,-C,)alkylamino, di(C-C.)alkyl- i o 16 amino or (C^-C^)alkylcarbonylamino group; or R^ and R2 together are a (C3~Cg)alkylene group or a group of the formula -CH=CH-CH=CH-; each of R4 and R; is a hydrogen or halogen atom or a (Cj-C4)alkyl, chlorosubstituted methyl, (Cj-C^Jalkoxy- - 58 - 10 I o::» u (MtlMMiyl «»r (i'| | >.i I ky I tMi U >iiy I nr R4 and Rg together are a {c3-C5)alkylene group or a group of the formula -CH=CH-CH=CH-, in which one or two of the -CH= groups may be replaced by -N= and which groups may be substituted by a halogen atom or a (C^-C^g)alkyl, (Cj-C3)alkoxy, (C^-C.^) alkyl thio, halo(C^-C^ Jalkoxy, halo-(C^-C^alkylthio, halomethyl, (C,.-C7 )cycloalkyl, phenoxy, phenylthio, NH2, acetylamino, benzoylamino, phenylamino, di-CC^-C^)alkylamino, N02, CN, (C^-C3)alkylcarbonyl, mono-(C^-C3)alkylureido, di(C^-C3)alkylureido, di(C^-C3)alkyl-formamido, (C^ -C3) alkoxycarbonylmethoxy, (C^-Cg)alkoxy-carbonyl, di(C^-Cj)alkylaminocarbonyl, benzthiazol-2-yl or dithiolane group; or R4 and Rg together are a group of the formula 15 U \ \ / CH. nX i 1i-c / ^ CH„ «2C / K K or u V - I each of R, and R_ is CH,, C_H_, CH.Cl, CH^OCH, or o / j z d z 2 3 CH2SCH3, and X is an oxygen or sulphur atom, with the proviso that R^ and R^ are not both hydrogen atoms. - 59 - .| 0 2 0 0 2. A compound as claimed in claim 1, in which the group of formula II is in the R,-position, R. and R_ are j o 7 both methyl groups and X is an oxygen atom. 3. A compound as claimed in claim 1 or claim 2, in 5 which R^ and R^ are both hydrogen atoms. 4. A compound as claimed in claim 1 or claim 2, in which R^ is a hydrogen atom or a (C^-C^)alkyl group and Rj is a hydrogen or fluorine atom or a cyano, acetyl or methoxycarbony1 group. lO 5. A compound as claimed in any one of claims 1 to 4, in which each of R^ and R,. is a hydrogen or fluorine atom or a methyl group. 6. A compound as claimed in any one of claims 1 to 4, in which R^ and R,. together are a (C^-C^)alkylene group 15 or a group of the formula -CH=CH-CH=CH-. 7. A compound as claimed in claim 6, in which the group -CH=CH-CH=CH- is substituted by a fluorine or chlorine atom or a (C^-C^Jalkyl, (C^-C^)alkoxy, alkylthio, CN or methylenedioxy group. 20 8. A compound as claimed in claim 6, in which the (Cj-Cg)alkylene group is substituted by a fluorine or chlorine atom or a (C^-C^Jalkyl, (C^-C^Jalkoxy, (C^-C^)-alkylthio, CN, c?y di-fC^-C^Jalkylamino or methylenedios^ group. 25 9. A compound as claimed in claim 1, in which one of R^ and R^ is a group of the formula II and the other is a hydrogen atom or a (C^-C^)alkyl group, R2 is a hydrogen atom or a (C^-C^Jalkoxycarbonyl group, R^ and Rg are both hydrogen atoms or together are a tetramethylene group or a - 60 - 4 4039 G group of the formula -CH=CH-CH=CH-both of which may be substituted by a halogen atom or a (C^-C^ alkyl, methoxy or trifluoromethyl group, or together are a group of the formula CH_ - y 2 " . \ ' N or / 1 1 ^xch' ' \ H2<\ / x ch2 R6 ant* ^7 are methyl groups and X is an oxygen atom. IO. Tho compound of the formula ooon(cii3). . * V JI 1 '"■3 •° 11. The compound of the formula OCON(CH_) t J £. i A X xn ch3 12. The compound of the formula OCON(CH_)_ i - 61 - The compound of the formula OCON(CH ) CH3 X t 1 * L A *i N XCH. "Hie compound of the formula OCON(CH )_ y $ y CF3 -N CH3 The compound of the formula OCON(CH ) F J z l N " " CH3 The compound of the formula OCON(CH ) CIIO 3 / - /J 1 i i M • < J. N 'CH, The compound of the formula OCON(CH3) I N N - 62 - 40286 18. A process for preparing a compound as claimed in claim 1 which comprises ^reacting a compound of the formula OH R. "4 j. r2 *4 j r2 j ii " i il s " \ »5 "N' OH 5 in which R^, R^, R^, R^ and R,. have the meanings specified in claim 1, (a) with a carbamoyl or thiocarbamoyl halide of the formula II 6 Hal—C-N XR7 lO in which Hal is chlorine or bromine, or (b) with phosgene, thiophosgene or a chloroformic acid (thion) ester and reacting the product obtained with a secondary amine of the formula X 6 H — N ^R7 15 Rg and R^ having the meanings specified in claim 1. 19. A process as claimed in claim 18, wherein reaction (a) is carried out in the presence of a 10 to 100% excess of the carbamoyl or thiocarbamoyl halide. 20. A process as claimed in claim 18, wherein 20 reaction (b) is carried out in a solvent in the presence of a base. - 63
IE9699/74A 1973-12-10 1974-12-09 Ew hydroxypyridine carbamates and their use as insecticides IE40296B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2361438A DE2361438C3 (en) 1973-12-10 1973-12-10 4-Hydroxyquinoline and 4-Hydroxytetrahydroquinoline-N ^ N-dimethylcarbamates, processes for their preparation and insecticidal compositions containing them

Publications (2)

Publication Number Publication Date
IE40296L IE40296L (en) 1975-06-10
IE40296B1 true IE40296B1 (en) 1979-04-25

Family

ID=5900372

Family Applications (1)

Application Number Title Priority Date Filing Date
IE9699/74A IE40296B1 (en) 1973-12-10 1974-12-09 Ew hydroxypyridine carbamates and their use as insecticides

Country Status (31)

Country Link
JP (1) JPS5088073A (en)
AT (1) AT342072B (en)
BE (1) BE823171A (en)
BG (1) BG25977A3 (en)
CA (1) CA1042892A (en)
CH (1) CH611488A5 (en)
CS (1) CS177887B2 (en)
DD (1) DD115421A5 (en)
DE (1) DE2361438C3 (en)
DK (1) DK142113C (en)
EG (1) EG11557A (en)
ES (1) ES432594A1 (en)
FI (1) FI58774C (en)
FR (1) FR2253743A1 (en)
GB (1) GB1489906A (en)
HK (1) HK58178A (en)
HU (1) HU172372B (en)
IE (1) IE40296B1 (en)
IL (1) IL46200A (en)
IT (1) IT1049333B (en)
KE (1) KE2878A (en)
LU (1) LU71438A1 (en)
MY (1) MY7800375A (en)
NL (1) NL7415870A (en)
OA (1) OA04867A (en)
PL (1) PL98709B1 (en)
RO (2) RO65069A (en)
SE (1) SE7415355L (en)
SU (1) SU797544A3 (en)
ZA (1) ZA747735B (en)
ZM (1) ZM17174A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4655816A (en) * 1984-11-06 1987-04-07 Monsanto Company Herbicidal 2-trifluoromethyl 3-pyridine carboxylic acid derivatives
FR2582514B1 (en) * 1985-05-30 1988-02-19 Rhone Poulenc Sante AMIDE DRUGS, NEW AMIDES AND THEIR PREPARATION
US4670045A (en) * 1987-04-07 1987-06-02 The Dow Chemical Company Fungicidal control employing ester derivatives of 4,6-disubstituted 2-pyridinols
WO1996037473A1 (en) * 1995-05-23 1996-11-28 Hoechst Schering Agrevo Gmbh Substituted 2,3-cycloalkenopyridines, process for preparing the same, agents containing the same and their use as pesticides and fungicides
TW521072B (en) * 1997-06-02 2003-02-21 Meiji Seika Kaisha 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture
ES2407813T3 (en) 2004-08-04 2013-06-14 Meiji Seika Pharma Co., Ltd. Quinoline and insecticide derivatives that contain them as active constituents
JP6112724B2 (en) * 2013-10-31 2017-04-12 日本化薬株式会社 1,5-naphthyridine derivative and insecticide comprising the same as an active ingredient
CN110452167B (en) * 2018-04-16 2020-08-21 东莞市东阳光农药研发有限公司 Quinoline derivatives, preparation method and application thereof
CN115124463B (en) * 2022-07-01 2023-11-28 浙江工业大学 Substituted quinoline compound and preparation method and application thereof

Also Published As

Publication number Publication date
ATA980074A (en) 1977-07-15
DE2361438A1 (en) 1975-06-26
FI58774C (en) 1981-04-10
ZA747735B (en) 1975-12-31
RO63735A (en) 1979-01-15
DK142113C (en) 1981-01-26
RO65069A (en) 1978-10-15
ZM17174A1 (en) 1975-08-21
LU71438A1 (en) 1976-11-11
FR2253743A1 (en) 1975-07-04
FI352474A (en) 1975-06-11
HK58178A (en) 1978-10-06
IL46200A (en) 1980-02-29
IL46200A0 (en) 1975-03-13
KE2878A (en) 1978-09-15
FI58774B (en) 1980-12-31
CH611488A5 (en) 1979-06-15
AT342072B (en) 1978-03-10
DK636174A (en) 1975-08-11
SU797544A3 (en) 1981-01-15
FR2253743B1 (en) 1979-02-23
OA04867A (en) 1980-10-31
BE823171A (en) 1975-06-10
SE7415355L (en) 1975-06-11
DE2361438B2 (en) 1979-04-26
IE40296L (en) 1975-06-10
NL7415870A (en) 1975-06-12
CS177887B2 (en) 1977-08-31
EG11557A (en) 1978-06-30
GB1489906A (en) 1977-10-26
HU172372B (en) 1978-08-28
DE2361438C3 (en) 1979-12-13
CA1042892A (en) 1978-11-21
PL98709B1 (en) 1978-05-31
ES432594A1 (en) 1977-04-01
IT1049333B (en) 1981-01-20
JPS5088073A (en) 1975-07-15
DD115421A5 (en) 1975-10-05
MY7800375A (en) 1978-12-31
AU7617474A (en) 1976-06-10
BG25977A3 (en) 1979-01-12
DK142113B (en) 1980-09-01

Similar Documents

Publication Publication Date Title
US4270948A (en) Herbicidal compound, herbicidal composition containing the same, and method of use thereof
KR820001834B1 (en) Process for preparing pridyloxy-phenoxy-a-propionic acid aminoalkyl esters
JPH0116831B2 (en)
JPS6115062B2 (en)
EP0014684A2 (en) 2-Substituted 5-phenoxy-phenylphosphonic acid derivatives, process for preparing them and their use as herbicides
IE40296B1 (en) Ew hydroxypyridine carbamates and their use as insecticides
CS226434B2 (en) Herbicide and method of preparing its active substance
GB2113212A (en) Herbicidal 2-(substituted phenoxy) propionic acid derivatives
US4342778A (en) Insecticidal (2,3-dihydro-2,2-dimethylbenzofuran-7-yloxy-N-methylcarbamoyl)-(N&#39;-alkoxycarbamoyl)-sulphides
US4148902A (en) N-[(optionally substituted phenylamino)carbonyl] pyridine carboxamides and insecticidal use thereof
CS220800B2 (en) Herbicide means and method of making the active substances
CS204960B2 (en) Herbicide means and means for regulation of the plant growth and method of production of active substances
JP3064374B2 (en) Uracil derivative, method for producing the same, and herbicide containing the same as an active ingredient
JP2525199B2 (en) Cyclohexane derivative and herbicide containing it as an active ingredient
US4115583A (en) Pesticidal sulphenylated formamidine compounds
KR100920771B1 (en) New Fluorine-containing Phenylformamidine Derivatives and Their Use as Insecticide
GB1579635A (en) Sulphenamides and their use in pesticidal compositions
CA1036491A (en) Heterocyclic compounds and their use as pesticides
JPS6127905A (en) Herbicide
JPS6365063B2 (en)
US4364959A (en) Imino ether sulfide derivatives and use as insecticides
US4560762A (en) 2-Alkylaminopyridine derivatives
US4451278A (en) 1-Hydroxyanthraquinone aquatic herbicide
USRE32418E (en) Substituted(((phenyl)amino)carbonyl)-benzamides
CA1080742A (en) Pesticidal 1,3,5-triaza-4-sulpha-1-phenylhept-1-ene derivatives