US3678046A - N-acyl-3,4-dihydro-oxazine-(1,3) compounds for controlling phytopathogenic fungi - Google Patents

N-acyl-3,4-dihydro-oxazine-(1,3) compounds for controlling phytopathogenic fungi Download PDF

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Publication number
US3678046A
US3678046A US32415A US3678046DA US3678046A US 3678046 A US3678046 A US 3678046A US 32415 A US32415 A US 32415A US 3678046D A US3678046D A US 3678046DA US 3678046 A US3678046 A US 3678046A
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formula
dihydro
compounds
acyl
oxazine
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US32415A
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English (en)
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Helmut Huber-Emden
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BASF Schweiz AG
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Ciba AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4

Definitions

  • R is especially a fused-on substituted benzene residue, though heterocyclic ring systems are also suitable, for example, quinoline derivatives of the formula in which R has the meaning defined above, X represents a halogen atom, for example, a chlorine, bromine or iodine atom and R represents a hydrogen atom or a methyl group.
  • Preferred N-acyl-3,4-dihydro-oxazines of the formula (I) are compounds of the formula I 0 v Nii-Rr Us M. M .11!.
  • U-substituents preferably U represents a halogen atom, a possibly halogen-substituted alkyl group containing one to four carbon atoms, a hydroxyl or nitro group or an alkoxy or alkenyloxy group containing up to four carbon atoms or a possibly halogen-substituted phenyl group which is bound to the fused-on benzene residue either directly or through an azo group and the other U-substituents each represents a hydrogen atom or one of the afore-mentioned substituents, and R represents an aliphatic or aromatic residue bound to the carbonyl group through a carbon atom.
  • the term aliphatic residue as used above and hereinafter describes an alkyl, halogenoalkyl, cyanoalkyl, thiocyanoalkyl, alkenyl or halogenoalkenyl group containing one to five carbon atoms, an ethylmercaptomethyl or morpholinomethyl group, while an aromatic residue is a phenyl group which may be unsubstituted or preferably substituted by halogen or nitro.
  • the present invention also provides a method of controlling phytopathogenic fungi which comprises applying to a crop area a compound of the general formula (I) or a preparation comprising as active ingredient a compound of the general formula (I), together with a carrier and/or other additive.
  • the invention also provides the compounds of the formula r or... V)
  • U represents an alkoxy or alkenyloxy group containing one to four carbon atoms
  • the substituents U,', U, and U represent hydrogen atoms or at most two of them represent a halogen atom, an alkyl group containing one to four carbon atoms (preferably methyl or ethyl) and/or a nitro group
  • R represents an aliphatic or aromatic residue as defined above which is bound to the carbonyl group through a carbon atom and pesticidal preparations that contain a compound of the formula (IV) as active ingredient in conjunction with one or more further additives.
  • N-acyl-3,4-dihydro-oxazine-(1,3) derivatives of the formula (l), a compound of the formula in which R, and R, have the meanings defined above, is reacted in an anhydrous medium that contains an inert organic' solvent or concentrated sulphuric acid, with formaldehyde or a formaldehyde donor in the presence of an acidic catalyst and, if desired, performing further reactions in the acyl residue.
  • Preferred starting materials methylphenols of the formula C Hz-NH-C 0-182 are ortho-acylaminois reacted with an anhydrous inert organic solvent or in concentrated sulphuric acid as reaction medium with formaldehyde or a formaldehyde donor in the presence of an acid catalyst and, when R, contains an alkenyl group, if desired halogen is added on or, if desired, hydrogen halide is eliminated.
  • N-acyl-3,4-dihydro-oxazine-( 1,3) derivatives of the formula (1) or (IV) obtained by the methods described above may be used. for example. in the following reactions without affecting the oxuzine system:
  • C1 or Br can be added on to R, when R contains an alkenyl bond, and from the resulting N- di-haloalkyl-dihydro-oxazine-( 1,3) derivatives HCl or l-lBr can be eliminated in the usual manner with formation of a chloroor bromo-alkenyl group.
  • N-acyl-3,4-dihydro-benzoxazines-(1,3) of the formula (III) or IV) can be manufactured in the known manner from a corresponding phenol with at least one free ortho-position according to the two-stage process:
  • the phenol is reacted with an N-methylol-
  • This reaction is carried out in a solvent, preferably in alcohol or glacial acetic acid, in the presence of a strongly acidic catalyst, for example, concentrated hydrochloric acid, HCl gas, phosphoric acid or pyrophosphoric acid.
  • a strongly acidic catalyst for example, concentrated hydrochloric acid, HCl gas, phosphoric acid or pyrophosphoric acid.
  • reaction stages (1) and (2) are carried out in concentrated sulphuric acid as reaction medium, the isolation of the intermediate product (B) can be dispensed with, and the two stages are performed successively in the same starting mixture as illustrated by the two examples of manufacture described below.
  • the active substances of the formula (I) display a very good activity against representatives of the class Phycomycetes, for example, phytopathogenic fungi, for example, Botrytis and Piricularia, and also against various other pathogenic fungi affecting grain crops, soyabean, corn, rice, vegetables, fruit and other cultures.
  • the present invention also provides preparations which comprise as active ingredient a compound of the general formula (I), together with a carrier.
  • the active substances of this invention also display a toxic activity towards fungi that attack plants in the soil and partially cause tracheomycoses, for example, Fusarium cubense, Fusarium dianthi, Verticillium alboatrum and Phialophora cinerecens.
  • the active substances of the formula (I) can be used as such to control harmful fungi; for this purpose devices are used that produce extremely fine sprays or dusts to prevent overdosages as far as possible. It is of advantage to apply the products by spraying from aircraft, for which purpose suitable fungicidal preparations may be used instead of the pure substances.
  • the active substances may be formulated as liquid or solid, dry or moist products, containing 0.1 to percent by weight of active substance, being in the form of solutions, emulsions, suspensions, concentrates, wettable powders, dusting agents or granulates.
  • the amount to be applied varies as. a rule from 0.01 to 5 kg of active substance per hectare.
  • the sprays for direct use contain, for example, mineral oil fractions having a high to medium-high boiling range, especially above C, for example, Diesel oil or kerosene, or coal tar oil or oils of a vegetable or animal origin, also hydrocarbons, for example, alkylated naphthalenes, tetrahydronaphthalene, xylene mixtures, cyclohexanols or if desired furthermore ketones, chlorinated hydrocarbons, for example, tetrachloroethane, trichloroethylene or triand tetrachlorobenzenes.
  • mineral oil fractions having a high to medium-high boiling range especially above C
  • Diesel oil or kerosene or coal tar oil or oils of a vegetable or animal origin
  • hydrocarbons for example, alkylated naphthalenes, tetrahydronaphthalene, xylene mixtures, cyclohexanols or if desired furthermore ketones,
  • emulsion concentrates for use in the form of aqueous preparations there are used emulsion concentrates, pastes or wettable powders with addition of water.
  • Suitable emulsifiers or dispersants are non-ionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon residue of about 10 to 30 carbon atoms with ethylene oxide, for example, the condensation product of octadecyl alcohol with 25 to 30 mols of ethylene oxide, or of soyabean fatty acid with 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide.
  • condensation products of ethylene oxide with hydro-aromatic polycyclic carboxylic acids or amines From among suitable anionic emulsifiers there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these two acids, or the sodium salt of a petroleumsulphonic acid.
  • Suitable cationic dispersants are quaternary ammonium and phosphonium compounds, for example, cetyl pyridinium chloride or dioxyethylbenzyl-dodecyl ammonium chloride.
  • the new preparations When the new preparations are to be used in the form of dusting or casting agents, they may contain as solid vehicles talcum, kaolin, bentonite, sand, calcium carbonate, calcium phosphate, or coal, cork meal or wood meal or other materials of vegetable origin.
  • the various preparations may contain the usual additives that improve the distribution, adhesion or penetration; such substances are, for example, fatty acids, resins, glue, casein or, for example, alginates. It is also very advantageous to use the preparations in granulated form.
  • the pesticidal preparations may contain the new compounds as the only active substance or in form of a combination with other insecticides, acaricides, nematocides, fungicides, herbicides or fertilizers, for example also trace elements.
  • the active substance is dissolved in an organic solvent, this solution is absorbed on a granulated mineral, for example, attapulgite, granicalcium, pumice stone or silica, and the solvent is then expelled.
  • a granulated mineral for example, attapulgite, granicalcium, pumice stone or silica
  • the granulates can also be manufactured by mixing the active substance of the formula (I) with a polymerizable compound and polymerizing this mixture in such manner that the active substance is left unaffected and at the stage of the gel formation granulation is carried out.
  • fungicidal compounds which can be mixed with the active substances of the formulas (l) to (1V) there may be mentioned: Nabam, zineb, maneb, amobam, ziram, ferbam, thiram, urbazide, tetmosol, thioneb, glyodine, captan, oxine, cyclohexamide, DHA, omadin, dyrene, gliotoxin, vanicide, diamthazole, rhodamine, griseofulvin, karathan, dichlor, chloranil, techmazene, quintozene, botram, nirite, cerenox, dithionanone, dexone, bulbosan, caprocol, kresatin, dichlorophene, orthoxenol, shirlan, penchloral, preventol, hexachlorophene, dodin, zephiran, tin compounds
  • reaction solution was then poured into a mixture of 200 ml of chloroform, 200 ml of water and 60 g of ice, the organic phase separated, extracted with 100 ml of ZN-sodium hydroxide solution, washed neutral with water, treated with sodium sulphate and a small quantity of active carbon and the solvent was distilled off, at the end under vacuum.
  • the substance could be recrystallized from methanol and in the analytically pure form melted at 1 15 to l 16C.
  • Readily soluble active substances can also be formulated U as emulsion concentrates by mixing: 0

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US32415A 1969-04-29 1970-04-27 N-acyl-3,4-dihydro-oxazine-(1,3) compounds for controlling phytopathogenic fungi Expired - Lifetime US3678046A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH655969A CH508343A (de) 1969-04-29 1969-04-29 Verwendung von Oxazin-Derivaten zur Bekämpfung von pflanzenpathogenen Pilzen

Publications (1)

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US3678046A true US3678046A (en) 1972-07-18

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US (1) US3678046A (de)
CH (1) CH508343A (de)
ZA (1) ZA702783B (de)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1555544A (de) * 1966-07-16 1969-01-31
US3519624A (en) * 1966-07-20 1970-07-07 Ciba Ltd Antimicrobial preparations containing n-acyl-3,4-dihydro-oxazines-(1,3)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1555544A (de) * 1966-07-16 1969-01-31
US3519624A (en) * 1966-07-20 1970-07-07 Ciba Ltd Antimicrobial preparations containing n-acyl-3,4-dihydro-oxazines-(1,3)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
McDonagh et al. J. Org. Chem. Vol. 33, pages 1 8 (1968). QD241.J6 *

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CH508343A (de) 1971-06-15
ZA702783B (en) 1971-01-27

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