EP0506907A1 - Heterocyclic dione derivatives as pesticides and plant growth regulators - Google Patents

Heterocyclic dione derivatives as pesticides and plant growth regulators

Info

Publication number
EP0506907A1
EP0506907A1 EP91918021A EP91918021A EP0506907A1 EP 0506907 A1 EP0506907 A1 EP 0506907A1 EP 91918021 A EP91918021 A EP 91918021A EP 91918021 A EP91918021 A EP 91918021A EP 0506907 A1 EP0506907 A1 EP 0506907A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
compound
hydrogen
nitro
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP91918021A
Other languages
German (de)
English (en)
French (fr)
Inventor
Shy-Fuh Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Pharma GmbH Austria
Sandoz AG
Original Assignee
Sandoz Erfindungen Verwaltungs GmbH
Sandoz 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 Sandoz Erfindungen Verwaltungs GmbH, Sandoz AG filed Critical Sandoz Erfindungen Verwaltungs GmbH
Publication of EP0506907A1 publication Critical patent/EP0506907A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • 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
    • C07D265/02—1,2-Oxazines; Hydrogenated 1,2-oxazines

Definitions

  • the present invention concerns substituted 3,5-dioxo-3,4,5,6- tetrahydrooxazines as herbicides, processes and intermediates for their preparation, compositions containing them and their use as herbicides and acaricides.
  • each of R 1 , R 2 and R 3 is independently hydrogen, C 1-8 alkyl, carboxyl,
  • R 4 is hydrogen, C 1-8 alkyl, C 1-8 alkylcarbonyl, C 1-8 alkoxycarbonyl, -
  • R is C 1-8 alkyl optionally substituted by 1 to 6 halogen atoms, C 1-8 - alkoxy optionally substituted by 1 to 6 halogen atoms, C 1-8 alkyl- carbonyl, C 1-8 alkoxycarbonyl, NR 7 R 8 , O n S(O) n ,R 10 , NR 7 SO 2 R 8 , halogen, cyano or nitro.
  • R 5 is C 1-8 alkoxy substituted by 1 to 6 halogen atoms
  • R 6 is hydrogen or selected from the meanings given for R;
  • each of R 7 and R 8 is independently hydrogen or C 1-8 alkyl
  • R 9 is C 1-8 alkyl
  • R 10 is C 1-8 alkyl optionally substituted by 1 to 6 halogen atoms
  • n 0 or 1
  • n' 0, 1 or 2;
  • R 1 , R 2 and R 3 are methyl, R 4 and R 6 are hydrogen and R is nitro, R 5 is not difluoromethoxy.
  • halogen is conveniently selected from chloro, bromo and fluoro, C 1-8 alkyl moieties, preferably have 1 to 4 carbon atoms.
  • Each of R 1 , R 2 and R 3 is preferably hydrogen, C 1-4 alkyl especially hydrogen or C 1-3 alkyl.
  • R conveniently signifies C 1-4 alkyl optionally substituted with halogen, -(O) n -S(O) n ,-C 1-4 alkyl, halogen or nitro. It is preferably methyl, CF 3 , C 1-3 alkylsulfonyl, C 1-3 alkylsulfonyloxy, chloro, bromo or nitro.
  • R 5 is preferably fluoroalkoxy, more preferably OCF 3 .
  • R 6 is preferably hydrogen, C 1-4 alkyl, C 1-4 alkoxy, bromo, chloro; it is more preferably hydrogen, methoxy or chloro.
  • R 4 is conveniently hydrogen, C 1-4 alkyl, C 4-8 alkylcarbonyl, benzoyl, C 1-4 alkylsulfonyl or a cation. It is preferably hydrogen, methyl, ethyl, t-butylcarbonyl, isobutylcarbonyl, benzoyl or methylsulfonyl.
  • R 4 is preferably an alkali metal such as Na + , K + , Li + or an ammonium cation.
  • R 3 a) C 1-8 alkyl
  • a particularly preferred single compound is 2,6,6-trimethyl-4-(4-tri- fluoromethoxy-2-nitrobenzyl)-2H-1,2-oxazine-3,5-(4H,6H)-dione.
  • the compounds of the present invention of formula I are new substances which can be prepared by methods analogous to methods known in the art, such as those described in European Patent Application EP 186,117 and references cited therein. More particularly, they can be obtained by, for example: rearranging an enol ester of formula (II)
  • This rearrangement is conveniently effected by reacting the compound of formula II with a cyanide source and a moderate base.
  • the reaction may be carried out in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
  • the reaction is conveniently carried out in a solvent which is inert under the reaction conditions, e.g. 1,2-dichloroethane, toluene, aceto- nitrile, methylene chloride, ethyl acetate, dimethylformamide (DMF) and methyl isobutyl ketone (MIBK).
  • the rearrangement may be conducted at temperatures up t: about 80°C. In some cases, for instance when there is a possible problem of excessive by-product formation, the temperatures should be kept at about 40oC maximum.
  • Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2 -C 5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself.
  • alkali metal cyanides such as sodium and potassium cyanide
  • cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups such as acetone or methyl isobutyl ketone cyanohydrins
  • cyanohydrins the preferred cyanide source is acetone cyanohydrin.
  • the cyanide source is used in an amount up to about 50 mole percent based on the enol ester. Generally about 1-10 mole % of the cyanide source is preferred.
  • Moderate base is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively).
  • Moderate bases suitable for use in this reaction include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates.
  • Suitable tertiary amines include trialkylamines such as triethylamine, trialkanolamines such as triethanol- amine, and pyridine.
  • Suitable inorganic bases include potassium carbonate and trisodium phosphate.
  • the base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 1.3-2 moles per mole.
  • phase transfer catalyst When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
  • reaction a) is carried out in the presence of a catalyst such as concentrated sulfuric acid.
  • the reaction is conveniently carried out in a solvent which is also the reactant such as methanol, and at an elevated temperature.
  • reaction b) is carried out in the presence of a moderate base such as triethylamine or pyridine and conveniently at RT or below.
  • a moderate base such as triethylamine or pyridine
  • the compounds of formula I may be recovered from the reaction mixture in which they are formed by working up by established procedures.
  • the compounds of formula II may be prepared by reacting a compound of formula III
  • This reaction is carried out in the presence of a base such as triethylamine, potassitim carbonate, pyridine, preferably triethylamine and in an inert solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran, dimethylformamide.
  • a base such as triethylamine, potassitim carbonate, pyridine, preferably triethylamine
  • an inert solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran, dimethylformamide.
  • R 20 is alkoxy, especially ethoxy or methoxy and R 1 , R 2 and R 3 are as defined above.
  • the reaction may be carried out at elevated temperatures e.g. 80-90° and in an inert solvent such as e.g. wet dimethylsulfoxide.
  • the compounds of formula V may be prepared analogously to known methods e.g. according to the following reaction scheme.
  • Reaction (a) may be carried out in an inert solvent such as dichloro- methane and aqueous ether and in the presence of a base such as triethylamine or sodium carbonate at RT.
  • an inert solvent such as dichloro- methane and aqueous ether
  • a base such as triethylamine or sodium carbonate at RT.
  • Reaction (b) may be carried out in an inert solvent such as toluene benzene or tetrahydrofuran in the presence of a base such as sodium methoxide or sodium hydride.
  • an inert solvent such as toluene benzene or tetrahydrofuran
  • a base such as sodium methoxide or sodium hydride.
  • the compound 2-nitro-4-trifluoromethoxy-benzoic acid is new and also forms part of the invention.
  • R 4 is other than hydrogen such compounds may exist in forms lb, Ic and Id or as mixtures of these forms.
  • novel compounds of formula I are useful for the control of weeds, using pre- and/or post-emergent treatments.
  • Compounds of formula I are also useful as plant growth regulators (PGRs) and acaricides.
  • PGRs plant growth regulators
  • the compounds can be applied in the form of dusts, granules, solutions, emulsions, wettable powders, flowables and suspensions.
  • Application of a compound of the present invention as herbicides is made according to conventional procedure to the weeds or their locus using an herbicidally effective amount of the compounds, usually from about one-tenth or less to ten pounds per acre.
  • the application of a compound of the present invention to the "locus" of the weed includes application to the seeds, the plant (weed) or parts of the plant, or the soil.
  • a compound of the present invention as an acaricide is made according to conventional procedure to the site of infestation using an acaricidally effective amount of the compound, usually 100 g/ha to 1 kg/ha.
  • herbicide refers to an active ingredient which modifies the growth of plants because of phytotoxic or plant growth regulating properties so as to retard the growth of the plant or damage the plant sufficiently to kill it.
  • Compounds of the present invention when applied as either post or pre-emergents, demonstrate high levels of herbicidal activity on broadleaf, grass and sedge weeds. They also exhibit selectivity in wheat, corn, cotton, some varieties of soybean and in some cases, rice.
  • a compound of formula I in the use of the compounds of formula I for combatting weeds and acari, can conveniently be employed as compositions in association with acceptable diluent(s) for application to the weed, acari or their loci. Such compositions also form part of the present invention.
  • Suitable formulations contain from 0.01 to 99% by weight of active ingredient, from 0 to 20% of surfactant and from 1 to 99.99% of solid or liquid diluent(s). Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing.
  • Application forms of a composition generally contain between 0.01 and 25% by weight of active ingredient. Lower or higher levels of active ingredient can, of course, be present depending on the intended use, the physical properties of the compound and the mode of application. Concentrate forms of a composition intended to be diluted before use generally contain between 2 and 90%, preferably between 5 and 81% by weight of active ingredient.
  • Useful formulations of the compounds of formula I include dusts, granules, suspension concentrates, wettable powders, flowables and the like. They are obtained by conventional manner, e.g. by mixing a compound of formula I with the diluent(s) and optionally with other ingredients.
  • the compounds of formula I may be used in micro-encapsulated form.
  • the compounds of formula I can be combined with a cyclodextrin to make a cyclodextrin inclusion complex for application to the weed, acari or their loci.
  • Agriculturally acceptable additives may be employed in the herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, caking and corrosion, for example.
  • surfactant as used herein means an agriculturally acceptable material which imparts emulsiflability, spreading, wetting, dispersibility or other surface-modifying properties.
  • surfactants are sodium lignin sulfonate and lauryl sulfate.
  • Dusts or granules means a liquid or solid agriculturally acceptable material used to dilute a concentrated material to a usable or desirable strength.
  • talc kaolin or diatomaceous earth
  • liquid concentrate forms for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid application forms e.g. water or diesel oil.
  • compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary acaricidal or herbicidal activity for broadspectrum weed control or compounds having antidotal, fungicidal, insecticidal or insect attractant activity.
  • Temperature is given in degrees Centigrade. RT means room temperature. Parts and percentages are by weight.
  • the aqueous supernatant is decanted from the brown cryustalline gum.
  • the crystalline gum is dissolved in ether and extracted with 0.5 N sodium hydroxide solution.
  • the combined basic aqueous solution is cooled and acidified with concentrated hydrochloric acid and then extracted with ether.
  • the combined extracts are dried and evaporated to dryness to give crystalline 2-nitro-4-trifluoromethoxybenzoic acid m.p. 119°C.
  • reaction mixture is diluted with 150 ml of dichloromethane and the solution is washed with water, brine, dried and evaporated to dryness to give 2,6,6- 2,6,6-trimethyl-5-(2-nitro-4-trifluoromethyoxybenzoyloxy) -6H-1,2-oxazine-3- one.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (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)
EP91918021A 1990-10-25 1991-10-23 Heterocyclic dione derivatives as pesticides and plant growth regulators Withdrawn EP0506907A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US604708 1984-04-27
US60470890A 1990-10-25 1990-10-25

Publications (1)

Publication Number Publication Date
EP0506907A1 true EP0506907A1 (en) 1992-10-07

Family

ID=24420699

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91918021A Withdrawn EP0506907A1 (en) 1990-10-25 1991-10-23 Heterocyclic dione derivatives as pesticides and plant growth regulators

Country Status (12)

Country Link
EP (1) EP0506907A1 (cs)
JP (1) JPH05503106A (cs)
KR (1) KR927003554A (cs)
AU (1) AU642052B2 (cs)
BR (1) BR9106194A (cs)
CA (1) CA2072134A1 (cs)
CS (1) CS193492A3 (cs)
HU (1) HUT61534A (cs)
IL (1) IL99834A0 (cs)
PL (1) PL295411A1 (cs)
WO (1) WO1992007837A1 (cs)
ZA (1) ZA918535B (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2050338A1 (en) 1993-02-18 2009-04-22 Basf Se Herbicidal compositions

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5716901A (en) * 1993-02-18 1998-02-10 Sandoz Ltd. Synergistic herbicidal compositions of dimethenamid, sulcotrione, and atrazine
US5888936A (en) * 1993-02-18 1999-03-30 Sandoz Ltd. Synergistic herbicidal compositions of dimethenamid and phenmedipham
AU2001242451A1 (en) * 2000-03-09 2001-09-17 Syngenta Participations Ag Acylated phenyl or pyridine herbicides
GT200100103A (es) 2000-06-09 2002-02-21 Nuevos herbicidas
DE10117503A1 (de) 2001-04-07 2002-10-17 Bayer Cropscience Gmbh Derivate von Benzoylcyclohexandionen und ihre Verwendung als Herbizide
AU2002322247A1 (en) * 2001-08-03 2003-02-17 Chirologix Pharmaceutical Inc. Antibacterial oxazinones and methods for their use and synthesis
DE10144529A1 (de) * 2001-09-11 2003-03-27 Bayer Cropscience Gmbh 3-Aminocarbonyl substituierte Benzoylcyclohexandione
DE10160007A1 (de) * 2001-12-06 2003-06-18 Bayer Cropscience Ag [1.2]-Oxazin-3,5-dione
DE10215723A1 (de) 2002-04-10 2003-10-30 Bayer Cropscience Gmbh 3-Keto oder 3-Oximether substituierte Benzoylcyclohexandione
BRPI1008949B1 (pt) 2009-03-11 2018-07-10 Bayer Intellectual Property Gmbh Cetoenóis haloalquilmetilenóxi-fenil-substituídos e seu uso, composição, seu uso e seu método de produção, métodos para combate de pestes animais e/ou crescimento de plantas indesejadas
DE102010008644A1 (de) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 Zyklische Ketoenole zur Therapie
AU2013211636B2 (en) 2012-01-26 2016-09-29 Bayer Intellectual Property Gmbh Phenyl-substituted ketoenols for controlling fish parasites

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3382601T2 (de) * 1982-03-25 1993-01-07 Stauffer Chemical Co 2-(2-substituierte benzoyl)-1,3 cyclohexandione.
IL77350A (en) * 1984-12-20 1991-01-31 Stauffer Chemical Co Production of acylated diketonic compounds
TR24452A (tr) * 1989-04-25 1991-11-01 Sandoz Ltd Pestisidler ve bitki bueyueme duezenleyicileri olarak heterosiklik dionlar

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9207837A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2050338A1 (en) 1993-02-18 2009-04-22 Basf Se Herbicidal compositions
EP2272342A2 (en) 1993-02-18 2011-01-12 Basf Se Herbicidal compositions

Also Published As

Publication number Publication date
CS193492A3 (en) 1992-10-14
HUT61534A (en) 1993-01-28
AU642052B2 (en) 1993-10-07
KR927003554A (ko) 1992-12-18
BR9106194A (pt) 1993-03-23
JPH05503106A (ja) 1993-05-27
AU8744291A (en) 1992-05-26
HU9202107D0 (en) 1992-10-28
CA2072134A1 (en) 1992-04-26
WO1992007837A1 (en) 1992-05-14
IL99834A0 (en) 1992-08-18
ZA918535B (en) 1993-04-26
PL295411A1 (en) 1993-06-28

Similar Documents

Publication Publication Date Title
US5089046A (en) Aryl and heteroaryl diones
US5801120A (en) Substituted benzoyl (hetero) cyclic diones
EP0394889B1 (en) Heterocyclic diones as pesticides and plant growth regulators
EP0338992A2 (en) Substituted aryl and heteroaryl bicyclodiones
US5728831A (en) Process for preparing oxazines
EP0090262A2 (en) Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones
WO1992007837A1 (en) Heterocyclic dione derivatives as pesticides and plant growth regulators
US4921526A (en) Substituted bicycloakly-1,3-diones
EP0249149B1 (en) Certain 3-benzoyl-4-oxolactams
US4741755A (en) Certain 4-oxo-3-benzoylvalerolactones and thiolactones
EP0255584B1 (en) Certain substituted 4-bezoyl-3,5-dioxotetrahydropyrans and thiopyrans
GB2205316A (en) Herbicidal benzoyl pyran, thiopyran or piperidine compounds
HU204165B (en) Herbicide compositions containing substituted3-amino-2-benzoyl-cyclohex-2-enone derivatives as active components and process for producing these compounds
US5006150A (en) Substituted heterocyclohexane-3,5-diones
AU619533B2 (en) Substituted aryl and heteroaryl diones
US4708732A (en) 2-(pyrimidinecarbonyl)-1,3-cyclohexanediones and their use as herbicidal agents
US4808733A (en) Certain 4-oxo-3-benzoylvalerolactones and thiolactones
EP0073409B1 (en) N-substituted-tetrahydroisophthalimide derivatives
US4780124A (en) Certain 4-oxo-3-benzoylvalerothiolactones
US4871856A (en) Certain 3-benzoyl-4-oxolactams
US4780123A (en) Certain 4-oxo-3-benzoylvalerolactones and thiolactones
US4871857A (en) Certain 3-benzoyl-4-oxolactams

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920609

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19950503