CA2072134A1 - Heterocyclic dione derivatives as pesticides and plant growth regulators - Google Patents
Heterocyclic dione derivatives as pesticides and plant growth regulatorsInfo
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- CA2072134A1 CA2072134A1 CA002072134A CA2072134A CA2072134A1 CA 2072134 A1 CA2072134 A1 CA 2072134A1 CA 002072134 A CA002072134 A CA 002072134A CA 2072134 A CA2072134 A CA 2072134A CA 2072134 A1 CA2072134 A1 CA 2072134A1
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- 8alkyl
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-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (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)
Abstract
ABSTRACT OF THE DISCLOSURE
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.
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.
Description
2~72~3~
HETEROCYCLIC DION~S AS P~STICIDES AND
PLANT GROWT~ RRGULATORS
The present invention concerns substituted 3,5-dioxo-3,4,5,6-tetrahydrooxazines as herbicides, processes and intermediates for thelr preparation, compositions containing them and ~heir use as herbicides and a~aricldes.
USP 4,695,673 describes a wide range of acylated 1,3-dicarbonyl compounds and their use as herbicides but makes no rePerence to or sugg~stion of the 3,5-dioxotetrahydrooxa~ine ring characterizing the '.0 compounds of the present invention.
More particul~rly, the invention concerns compounds of formula I
~R5 wherein, each of Rl, R2 and R3 is independently hydrogen, Cl8alkyl, carboxyl, Cl0alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or Rl and Rz together form a C3~alkylene bridge R4 is hydrogen, C~aalkyl, Claalkylcarbonyl, Claalkoxycarbonyl, C(O)NR7R~, Cl~alkylsulphonyl, P(O)-(OR~)2, R7P(O)-ORg, benzoyl or a cation.
R is Cl8alkyl optionally substituted by 1 to 6 halogen atoms, Cl8-alkoxy opt~onally substituted by 1 to 6 halogen atoms, Cl~alkyl-carbonyl, Claalkoxycarbonyl, NR7R8, Ons(o)~Rlo~ NR7S02R8, halogen, cyano or nitro.
R5 is Cl9alko~y substituted by 1 to 6 halogen atoms;
R~ is hydrogen or select~d from the maanings given for R;
each of R7 and R8 is independently hydrogen or Cl8alkyl;
R~ is Cl~alkyl;
Rlo is Cl~alkyl optionally substituted by 1 to 6 halogen atoms;
n is O or l;
n' is 0, 1 or 2;
providet that when Rl, R2 and R3 are methyl, R~ and Rff are hytrogen and R is nitro, R~ is not difluoromethoxy.
In the above definltions, halogen ~ 3 con~eniently selected from chloro, bromo and fluoro, Cl8alkyl moietie3, preferably have l to 4 carbon atoms.
Each of Rl, R~ snd R3 is preferably hydrogen, Cl~alkyl especially hydrogen or Cl3alkyl.
R conveniently si~ni~ies Cl~alkyl optionally substitut~d wlth ' ' .
~,~7213~
~3- 133-0659/B
halogen, -(O)n-S(O)n,-Cl4alkyl, halogen or nitro. It is preferably methyl, CF3, Cl3alkylsulfenyl, Cl3alkylsulfonyloxy, chloro, broma or nit~o.
R5 is preferably fluoroalkoxy, more preferably OCF3.
R6 is preferably hydrogen, Cl4alXyl, Cl~alkoxy, bromo, chloro; it is S more preferably hydrogen, methoxy or chloro.
R4 is con~eniently hydrogen, Cl4alkyl, C~3alkylcarbonyl, benzoyl, Cl~alkylsulfonyl or a cation. It is preferably hydrogen, methyl, ethyl, t-butylc~rbonyl, isobutylcarbonyl, benzoyl or methylsulfonyl. As a cation R4 is preferably an alkali metal such as Na~, K~, Li~ or an } onium cation.
Examples of particularly preferred substituents are for Rl and R2 each a) H, Cl4alkyl, phenyl or phenyl substituted by one to three groups as R
b) H, Cl4alkyl phenyl or phenyl substituted by one to three groups as R
c) H, Cl3alkyl d) H, CH3 e) Cl3alkyl R3 - a) Cl~alkyl b) C~4alkyl c) CH3, C2Hs R a) NO2, Cl, CF3 b) NO2, Cl C ) NO2 Rs - OCF3 Combinations of these substituent meanings are especially preferred.
A particularly preferret ~ingle compound is 2,6,6-trimethyl-4-(4-tri-iluoromathoxy-2-nitrobenzyl)-2H-1,2-oxa7ine-3,5-(4H,6H)-d~one.
The compounds of the present inYention of formula I are new substances which can be prepared by m~thods analogous to methods known in the art, such as those described in European Patent Applicat~on EP 186,117 and references cited therein. ~ore particularly, they can be obtained by, for example: rearranging an enol ester of formula (II) ~2 ~ II
wherein R~, R2, R3, R, R5 and R~ are a~ previously defined to give a co~pound of formula I wherein R~ H.
Thi~ rearrangement i5 con~eniently ef~ected by reacting the compound .
.
20r~2~34 of formula II with a cyanide source and a moderate base.
For example, the reaction may 'oe carried out in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with 2 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 chlorlde, ethyl acetate, dimethylforma~ide ~DMF) and methyl isobutyl kecone (MIBK). In general, depending on the nature of the reactants and tho cyanide source, the rearrangement may be conduc~ed at temperatures up to about 800C. In som~ cases, for instanCQ when there is a possible problem of excessive by-product formation, the temperatures should be kept at about 400C maximum.
Preferred cyanlde sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the al~yl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2-C~ aliphatic aldehydes such as acetaldehyd~, proplonaldehyde, 8tC., cyanohydrins; zinc cyanide;
tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin. The cy~nide source is used in an amount up to about 50 mole percent based on the enol ester. Generally about 1^10 mole % of the cyanids source is preferred.
By the term "moderaee base" i9 meant a substance which acts as a base yet whose strength or activity as a base lie~ between that of stron~ bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (whlch 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, trialkanola~ines such as triathanol-amine, and pyridine. Suitable lnorganic 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.
When the cyanida source is an alkal~ metal yanide, part~cularly potassium cyanide, a phase trAnsfer catalyst ~ay be included in the reaction. Particularly suitable phas~ transfer catalyst3 are the Crown ethers.
Compounds of formula I where R~ is other than hydro~en can be prepared by reacting a compount o~ ~ormula I wherein R~ is hydrogen with either a) the group R40-OH and a catalyst, or b) the group R40~Q and a moderate bsse, wheroin Q i5 8 halogen atom, to give a compound of formula I where R~o i~ the de~ired substituent.
~72~3~
The above reaction a) is carried out in the presence of a catalyst such as concentra~ed sulfuric acid. The reaction is conveniently carried out in a solvent which is also the reactant such as methanol, and at an elevated temperature.
The above reaction b) is carried out in the presence of a moderate base such as triethylamine or pyridine and oonveniently at RT or below.
The compounds of formula I may be recovered from the reaction mixture in which they are formed by working up by es~ablished procedures.
The compounds of fo~ula II may be prep~red by reacting a compound lO of formula III R
with a compound of formula IV
Hal - C~Rs IV
R
This reaction is carried out in the presence of a base such as triethylamine, potasslum carbona~e, pyridine, preferably triethylamine and in an iner~ solvent such as tichloromethane, acetonitrile, toluene, tetrahydrofuran, dimethylformamide. The reaction i~ conveniently carried out at RT or below.
The remaining compounds of for~ula II may be prepared analogously.
The compounds of for~la III are new and also form part of the invention.
They may be prepared by decarboxylating a compound of formula V
R2~ R20 v ~ .
wherein R20 is alkoxy, especially ethoxy or me~hoxy and Rl, R2 and R3 are as defined above. The reaction may be carried out at elsvated temperatur~s e.g. 80 90~ and in an inert solvent such a~ e.g. wet dimethylsuloxlde.
The compounds of formula V may be prepared analogously to known methods e.g. accordlng to the ollowing reaction scheme.
.
-, - 2072~3~
R3NHOC(RlR2)COR20 + ClOCCHzCOR20 VI ~ VII
~ (a) R3NOC(RlR2)cOR2o COCH2cOR2o VIII
~ (b) V
Reaction (a) may be carrled out in an inert solvent such as dichloro-methane and aqueous ether and in the presence of a base such as triethyl-amine or sodium carbon~te at RT.
Rsaction (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.
The remaining starting materials and reagents employed in the process described herein are either known or, insofar as they are not known, may be produced in a manner analogou~ to the processes dsscribed herein or to known processes [cf for compounds VI Kornowski et.al. Bull. Soc. Chim : France 1966(2)683].
The compound 2-nitro-4-trifluoromethoxy-benzoic acid is new and also forms par~ of the in~ention.
The compounds of this in~ention wherein R~ is H can have four structural formulae b~cause of tautomerism as illustrated ~5 follows:
2 ~ = 2 ~ ~
N ~ O~N 5 I~
Ic R2 ~ = R2 ~
R3 R6 IJ o ~N OH 5 .
:
'.
20 ~2134 It will of course be readily appr~ciated that whers R4 is other than hydrogen such co~pounds may exis~ in forms Ib, Ic and Id or as mixtures of these forms.
The 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. T*e compounds can be applied in the form of dusts, granules, solutions, emulsions1 wettable powders, flowableg and suspension~. Application of a compound of the present in~ention as herbicide~ ;s made according to conventional procedure to the weeds or their locus using an herbicidally effective amount of the compounds, usually from abou~ one-ten~h or les~ to ten pounds per acre. Th application of a compound of the present invantion to the nlocus~ of the weed includes application to the seeds, the plant (weed) or parts of the plant, or the soil.
Applicatlon of 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.
The term "herbicide," as used herein, refers to an active ingredient ~0 which modifies the growth of plants becaus~ of phytotoxic or plant growth regulatin~ 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-emer~ents, demonstrate high levels of herbicidal acti~ity on broadleaf, ~rass and sedge weeds. They also exhibit s~lectivity in wheat, corn, cotton, some varieties of soybean and in some case~, ric~.
In the use of the compounds of formula I for combatting weeds and acari, a compound of formula I, or mixtures thereo~, can conveniently be employed as composltions in association with acceptable diluent(s) for application to the weed, acarl or their loci. Such compositions also form part of the present invention.
Methods of preparing suitable formulations which can be used with a compound of the present invention are described in the lieer~ture along with suitable liquid and solid carriers, such a~ in U.S. Patent 4,192,669 and 4,163,661, which are incorporated herein by reference. The optimum usage of a compound of the present inven~ion is readily determinablP by one of ordinary skill in the art using routine testing such a~ ~reenhouse tes~ing and small plot testing.
Sui~able ~ormulations contain from 0.01 ~o 99% by weight o active ingredient, from 0 to 20~ of ~ur~actant and fzom 1 to 99.99~ of qolld or liquid diluent(s). Higher ratio~ of surfactant to active ingredient are sometimes deairable and are achieved by incorporation into the formulation or by tank mixlng. Application forms oP a composition generally contain between 0.01 and 254 by weight of activs ingredient. Lower or higher ~ ' ' ' ' ' ~07~3~
levels of active ingredient can, of course, be present depending on the intended use, the physlcal properties of the compound and the mode of application. Concen~rate forms of a compositlon intended to be diluted before use generally contain between 2 and 90~, preferably between 5 and 81~ by weight of active ingredient.
Useful formula~ions 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.
Alternatively, the compounds of formula I may be used in micro-encapsulated form.
The compounds of for~ula I can be combined with a cycLodextrin to make a cyclodextrin inclusi~n complex for apylication to the weed, acari or their loci.
Agriculturally acceptable additives may be employed in the herbicidal compositions ~o i~prove the perform~nce of the actlve ingredient and to reduce foaming, ca~ing and corrosion, for example.
"Surfactant" as used herein means an agriculturally acceptable material which imparts emulsifiability, spreading, wetting, dlspersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.
"Diluent" as used herein means a liquid or solid agriculturally acceptable material used to dilute a concentratsd material to a usable or desirable strength. For dusts or granule~ it can be e.g. talc, kaolin or diatomaceous earth, for liquid concentrate for~s for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid application forms e.g. water or diesel oil.
The compositions of this inventio~ can also compris~ other compounds having biological activity, e.g, compounds having similar or complementary acaricidal or herbicidal activity for broadsyectrum weed control or compounds having an~idotal, fungicidal, insecticidal or insect attractant activity.
The following examples are provided to illustrate the practice of ths present invention. Temperature is giYen in degrees Centigrade. RT means ~5 room temperature. Parts and percen~a~es are by weigh~.
2~7~3~
E~AMpT.F 1 Preparation of 2,6,6-trimethyl-4-(2-nitro-4-trifluoromethoxybenzoyl)-2H-1,2-oxazine-3,5(4H, 6H)-dione (Formula I Rl~R2-R3~CH3; R"-R~ H;
R~NOz; R5 OCF3: Compound No. 1) 71.4 g of 2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybenzoyloxy)-6H-1,2-oxazine-3-one is dissolved in 300 ml of acetonitrile and 49 ml of triethylamine. To this solu~ion, cooled in a water bath, is add0d 3.2 ml of ace~one cyanohydrin. The resul~in~ solution is stirred at r.t., under nitrogen, overnight. The reaction mixture ls concentrated to a syrup an~
the syrup is portioned between 400 ml of water and 150 ml of dlchloro methoxy. The combined extracts are washed with 2N HCl, brine, dri0d and evaporated to dryness to give oily residue. The crude product is then crystsllized from ethanol to yield 2,6,6-trimethyl-4-(2-nitro-4-trirlu~ro-methoxybenzoyl)-2H-1,2-oxazine-3,5(4H, 6H)-dione, m.p. 73-75.5.
Proceeding analogously to Exa~ple 1 the following compounds of formula I are obtainPd.
~ABLE A
Cpd Rl R2 ~3 R4 R Rs R6 m.~.
1 CH3 CH3 CH3 H NO2 4-OCF3 H 73-75.5 2 CH3 CH3 CH3 ~ Cl 4-OCHF2 H 95-970 E~AMPLE 2 Preparation of 2-nitro-4-trifluoromethoxybenzonitrile To a stirred solution of 64.30 g of 2-nitro-4-trifluoromethoxyaniline (Zhur. Obshchei. Khim 31, 915-24 (1961)) in 72 ml of concPntrated hydrochloric acid and 190 ml of water, cooled to 0 i9 added dropwise over 3S min. a solution of 20.0 g of sodium nitrite in 75 ml of water. After stirrlng at 0C for an addition~l 45 min., the diazonium salt solution is added dropwise, in portions, over 75 min. to a ~tirred solution of 82.69 g o~ potassium cyande and 46.62 g of cupric sulfate in 400 ml of water at 60-65C. The gray-greenish mixture is stirred and heated at 60-65C for an additional 30 min and then allowed to cool to r.t. The mixture is filtered through celite and the precipita~e is washed with dichloromethane (3 x 200 ml). The dichloromethane washings ~re used to sxtract the aqueous solutlon. The combined sx~racts are washed with water, br~ne, dried and evaporated to dryness to give an oily resldu~ which i~ chro~atographed on silica gel to give 31.44 g of 2-nitro-4-trifluoromethoxybenzonitrile.
.
!
2~P~2~13~
E~AMPLE 3 Preparation of 2-nitro-4-trifluoromethoxy benzoic acid A stirred solution of 40.96 g of 2-nitro-4-trlfluorobenzonitrilz in 90 ml of concentrated sulfuric acid and 125 ml of water is refluxed for 45 hrs. The reaction mixture is cooled and dlluted with 200 ml of cold water.
The aqueous supernatant is decanted from th0 brown cryust~lline gu~. 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 wlth ether. The combined extracts are dried and evaporated to dryness to give crystalline 2-nitro-4-trifluoromethoxybenzoic acid m.p. 119C.
E~AMPLE 4 Preparationof2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybenzoyl-oxy)-6H-1,2-oxazine 3-one (Formula II Rl-R2-R3-CH3; R4-R6-~H; R-N02;
A stirred solution of 43.98 g of 2-nitro-4-trifluoromethoxybenzoic acid in 100 ml of thionyl chloride is refluxed for 2 hrs and then concentrated to dryness to give oily 2-nitro-4-tr~fluoromethoxybenzoyl chloride. To a stirred solution of 27.53 g of 2,6,6-trimethyl-2H-1,2-oxazine-3,5(4H, 6H)-dione and 35 ml (25/mm) of triethylamine in 290 ml of dichloromethane, cooled in an ice bath, under nitrogen, is added dropwise a solution of 2-nitro-4-trifluoromethoxybenzoyl chloride in 100 ml of di-chloromethane. After s~irring at 0C at r.t. for 2 hrs., the 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.
HETEROCYCLIC DION~S AS P~STICIDES AND
PLANT GROWT~ RRGULATORS
The present invention concerns substituted 3,5-dioxo-3,4,5,6-tetrahydrooxazines as herbicides, processes and intermediates for thelr preparation, compositions containing them and ~heir use as herbicides and a~aricldes.
USP 4,695,673 describes a wide range of acylated 1,3-dicarbonyl compounds and their use as herbicides but makes no rePerence to or sugg~stion of the 3,5-dioxotetrahydrooxa~ine ring characterizing the '.0 compounds of the present invention.
More particul~rly, the invention concerns compounds of formula I
~R5 wherein, each of Rl, R2 and R3 is independently hydrogen, Cl8alkyl, carboxyl, Cl0alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or Rl and Rz together form a C3~alkylene bridge R4 is hydrogen, C~aalkyl, Claalkylcarbonyl, Claalkoxycarbonyl, C(O)NR7R~, Cl~alkylsulphonyl, P(O)-(OR~)2, R7P(O)-ORg, benzoyl or a cation.
R is Cl8alkyl optionally substituted by 1 to 6 halogen atoms, Cl8-alkoxy opt~onally substituted by 1 to 6 halogen atoms, Cl~alkyl-carbonyl, Claalkoxycarbonyl, NR7R8, Ons(o)~Rlo~ NR7S02R8, halogen, cyano or nitro.
R5 is Cl9alko~y substituted by 1 to 6 halogen atoms;
R~ is hydrogen or select~d from the maanings given for R;
each of R7 and R8 is independently hydrogen or Cl8alkyl;
R~ is Cl~alkyl;
Rlo is Cl~alkyl optionally substituted by 1 to 6 halogen atoms;
n is O or l;
n' is 0, 1 or 2;
providet that when Rl, R2 and R3 are methyl, R~ and Rff are hytrogen and R is nitro, R~ is not difluoromethoxy.
In the above definltions, halogen ~ 3 con~eniently selected from chloro, bromo and fluoro, Cl8alkyl moietie3, preferably have l to 4 carbon atoms.
Each of Rl, R~ snd R3 is preferably hydrogen, Cl~alkyl especially hydrogen or Cl3alkyl.
R conveniently si~ni~ies Cl~alkyl optionally substitut~d wlth ' ' .
~,~7213~
~3- 133-0659/B
halogen, -(O)n-S(O)n,-Cl4alkyl, halogen or nitro. It is preferably methyl, CF3, Cl3alkylsulfenyl, Cl3alkylsulfonyloxy, chloro, broma or nit~o.
R5 is preferably fluoroalkoxy, more preferably OCF3.
R6 is preferably hydrogen, Cl4alXyl, Cl~alkoxy, bromo, chloro; it is S more preferably hydrogen, methoxy or chloro.
R4 is con~eniently hydrogen, Cl4alkyl, C~3alkylcarbonyl, benzoyl, Cl~alkylsulfonyl or a cation. It is preferably hydrogen, methyl, ethyl, t-butylc~rbonyl, isobutylcarbonyl, benzoyl or methylsulfonyl. As a cation R4 is preferably an alkali metal such as Na~, K~, Li~ or an } onium cation.
Examples of particularly preferred substituents are for Rl and R2 each a) H, Cl4alkyl, phenyl or phenyl substituted by one to three groups as R
b) H, Cl4alkyl phenyl or phenyl substituted by one to three groups as R
c) H, Cl3alkyl d) H, CH3 e) Cl3alkyl R3 - a) Cl~alkyl b) C~4alkyl c) CH3, C2Hs R a) NO2, Cl, CF3 b) NO2, Cl C ) NO2 Rs - OCF3 Combinations of these substituent meanings are especially preferred.
A particularly preferret ~ingle compound is 2,6,6-trimethyl-4-(4-tri-iluoromathoxy-2-nitrobenzyl)-2H-1,2-oxa7ine-3,5-(4H,6H)-d~one.
The compounds of the present inYention of formula I are new substances which can be prepared by m~thods analogous to methods known in the art, such as those described in European Patent Applicat~on EP 186,117 and references cited therein. ~ore particularly, they can be obtained by, for example: rearranging an enol ester of formula (II) ~2 ~ II
wherein R~, R2, R3, R, R5 and R~ are a~ previously defined to give a co~pound of formula I wherein R~ H.
Thi~ rearrangement i5 con~eniently ef~ected by reacting the compound .
.
20r~2~34 of formula II with a cyanide source and a moderate base.
For example, the reaction may 'oe carried out in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with 2 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 chlorlde, ethyl acetate, dimethylforma~ide ~DMF) and methyl isobutyl kecone (MIBK). In general, depending on the nature of the reactants and tho cyanide source, the rearrangement may be conduc~ed at temperatures up to about 800C. In som~ cases, for instanCQ when there is a possible problem of excessive by-product formation, the temperatures should be kept at about 400C maximum.
Preferred cyanlde sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the al~yl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C2-C~ aliphatic aldehydes such as acetaldehyd~, proplonaldehyde, 8tC., cyanohydrins; zinc cyanide;
tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin. The cy~nide source is used in an amount up to about 50 mole percent based on the enol ester. Generally about 1^10 mole % of the cyanids source is preferred.
By the term "moderaee base" i9 meant a substance which acts as a base yet whose strength or activity as a base lie~ between that of stron~ bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (whlch 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, trialkanola~ines such as triathanol-amine, and pyridine. Suitable lnorganic 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.
When the cyanida source is an alkal~ metal yanide, part~cularly potassium cyanide, a phase trAnsfer catalyst ~ay be included in the reaction. Particularly suitable phas~ transfer catalyst3 are the Crown ethers.
Compounds of formula I where R~ is other than hydro~en can be prepared by reacting a compount o~ ~ormula I wherein R~ is hydrogen with either a) the group R40-OH and a catalyst, or b) the group R40~Q and a moderate bsse, wheroin Q i5 8 halogen atom, to give a compound of formula I where R~o i~ the de~ired substituent.
~72~3~
The above reaction a) is carried out in the presence of a catalyst such as concentra~ed sulfuric acid. The reaction is conveniently carried out in a solvent which is also the reactant such as methanol, and at an elevated temperature.
The above reaction b) is carried out in the presence of a moderate base such as triethylamine or pyridine and oonveniently at RT or below.
The compounds of formula I may be recovered from the reaction mixture in which they are formed by working up by es~ablished procedures.
The compounds of fo~ula II may be prep~red by reacting a compound lO of formula III R
with a compound of formula IV
Hal - C~Rs IV
R
This reaction is carried out in the presence of a base such as triethylamine, potasslum carbona~e, pyridine, preferably triethylamine and in an iner~ solvent such as tichloromethane, acetonitrile, toluene, tetrahydrofuran, dimethylformamide. The reaction i~ conveniently carried out at RT or below.
The remaining compounds of for~ula II may be prepared analogously.
The compounds of for~la III are new and also form part of the invention.
They may be prepared by decarboxylating a compound of formula V
R2~ R20 v ~ .
wherein R20 is alkoxy, especially ethoxy or me~hoxy and Rl, R2 and R3 are as defined above. The reaction may be carried out at elsvated temperatur~s e.g. 80 90~ and in an inert solvent such a~ e.g. wet dimethylsuloxlde.
The compounds of formula V may be prepared analogously to known methods e.g. accordlng to the ollowing reaction scheme.
.
-, - 2072~3~
R3NHOC(RlR2)COR20 + ClOCCHzCOR20 VI ~ VII
~ (a) R3NOC(RlR2)cOR2o COCH2cOR2o VIII
~ (b) V
Reaction (a) may be carrled out in an inert solvent such as dichloro-methane and aqueous ether and in the presence of a base such as triethyl-amine or sodium carbon~te at RT.
Rsaction (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.
The remaining starting materials and reagents employed in the process described herein are either known or, insofar as they are not known, may be produced in a manner analogou~ to the processes dsscribed herein or to known processes [cf for compounds VI Kornowski et.al. Bull. Soc. Chim : France 1966(2)683].
The compound 2-nitro-4-trifluoromethoxy-benzoic acid is new and also forms par~ of the in~ention.
The compounds of this in~ention wherein R~ is H can have four structural formulae b~cause of tautomerism as illustrated ~5 follows:
2 ~ = 2 ~ ~
N ~ O~N 5 I~
Ic R2 ~ = R2 ~
R3 R6 IJ o ~N OH 5 .
:
'.
20 ~2134 It will of course be readily appr~ciated that whers R4 is other than hydrogen such co~pounds may exis~ in forms Ib, Ic and Id or as mixtures of these forms.
The 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. T*e compounds can be applied in the form of dusts, granules, solutions, emulsions1 wettable powders, flowableg and suspension~. Application of a compound of the present in~ention as herbicide~ ;s made according to conventional procedure to the weeds or their locus using an herbicidally effective amount of the compounds, usually from abou~ one-ten~h or les~ to ten pounds per acre. Th application of a compound of the present invantion to the nlocus~ of the weed includes application to the seeds, the plant (weed) or parts of the plant, or the soil.
Applicatlon of 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.
The term "herbicide," as used herein, refers to an active ingredient ~0 which modifies the growth of plants becaus~ of phytotoxic or plant growth regulatin~ 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-emer~ents, demonstrate high levels of herbicidal acti~ity on broadleaf, ~rass and sedge weeds. They also exhibit s~lectivity in wheat, corn, cotton, some varieties of soybean and in some case~, ric~.
In the use of the compounds of formula I for combatting weeds and acari, a compound of formula I, or mixtures thereo~, can conveniently be employed as composltions in association with acceptable diluent(s) for application to the weed, acarl or their loci. Such compositions also form part of the present invention.
Methods of preparing suitable formulations which can be used with a compound of the present invention are described in the lieer~ture along with suitable liquid and solid carriers, such a~ in U.S. Patent 4,192,669 and 4,163,661, which are incorporated herein by reference. The optimum usage of a compound of the present inven~ion is readily determinablP by one of ordinary skill in the art using routine testing such a~ ~reenhouse tes~ing and small plot testing.
Sui~able ~ormulations contain from 0.01 ~o 99% by weight o active ingredient, from 0 to 20~ of ~ur~actant and fzom 1 to 99.99~ of qolld or liquid diluent(s). Higher ratio~ of surfactant to active ingredient are sometimes deairable and are achieved by incorporation into the formulation or by tank mixlng. Application forms oP a composition generally contain between 0.01 and 254 by weight of activs ingredient. Lower or higher ~ ' ' ' ' ' ~07~3~
levels of active ingredient can, of course, be present depending on the intended use, the physlcal properties of the compound and the mode of application. Concen~rate forms of a compositlon intended to be diluted before use generally contain between 2 and 90~, preferably between 5 and 81~ by weight of active ingredient.
Useful formula~ions 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.
Alternatively, the compounds of formula I may be used in micro-encapsulated form.
The compounds of for~ula I can be combined with a cycLodextrin to make a cyclodextrin inclusi~n complex for apylication to the weed, acari or their loci.
Agriculturally acceptable additives may be employed in the herbicidal compositions ~o i~prove the perform~nce of the actlve ingredient and to reduce foaming, ca~ing and corrosion, for example.
"Surfactant" as used herein means an agriculturally acceptable material which imparts emulsifiability, spreading, wetting, dlspersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.
"Diluent" as used herein means a liquid or solid agriculturally acceptable material used to dilute a concentratsd material to a usable or desirable strength. For dusts or granule~ it can be e.g. talc, kaolin or diatomaceous earth, for liquid concentrate for~s for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid application forms e.g. water or diesel oil.
The compositions of this inventio~ can also compris~ other compounds having biological activity, e.g, compounds having similar or complementary acaricidal or herbicidal activity for broadsyectrum weed control or compounds having an~idotal, fungicidal, insecticidal or insect attractant activity.
The following examples are provided to illustrate the practice of ths present invention. Temperature is giYen in degrees Centigrade. RT means ~5 room temperature. Parts and percen~a~es are by weigh~.
2~7~3~
E~AMpT.F 1 Preparation of 2,6,6-trimethyl-4-(2-nitro-4-trifluoromethoxybenzoyl)-2H-1,2-oxazine-3,5(4H, 6H)-dione (Formula I Rl~R2-R3~CH3; R"-R~ H;
R~NOz; R5 OCF3: Compound No. 1) 71.4 g of 2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybenzoyloxy)-6H-1,2-oxazine-3-one is dissolved in 300 ml of acetonitrile and 49 ml of triethylamine. To this solu~ion, cooled in a water bath, is add0d 3.2 ml of ace~one cyanohydrin. The resul~in~ solution is stirred at r.t., under nitrogen, overnight. The reaction mixture ls concentrated to a syrup an~
the syrup is portioned between 400 ml of water and 150 ml of dlchloro methoxy. The combined extracts are washed with 2N HCl, brine, dri0d and evaporated to dryness to give oily residue. The crude product is then crystsllized from ethanol to yield 2,6,6-trimethyl-4-(2-nitro-4-trirlu~ro-methoxybenzoyl)-2H-1,2-oxazine-3,5(4H, 6H)-dione, m.p. 73-75.5.
Proceeding analogously to Exa~ple 1 the following compounds of formula I are obtainPd.
~ABLE A
Cpd Rl R2 ~3 R4 R Rs R6 m.~.
1 CH3 CH3 CH3 H NO2 4-OCF3 H 73-75.5 2 CH3 CH3 CH3 ~ Cl 4-OCHF2 H 95-970 E~AMPLE 2 Preparation of 2-nitro-4-trifluoromethoxybenzonitrile To a stirred solution of 64.30 g of 2-nitro-4-trifluoromethoxyaniline (Zhur. Obshchei. Khim 31, 915-24 (1961)) in 72 ml of concPntrated hydrochloric acid and 190 ml of water, cooled to 0 i9 added dropwise over 3S min. a solution of 20.0 g of sodium nitrite in 75 ml of water. After stirrlng at 0C for an addition~l 45 min., the diazonium salt solution is added dropwise, in portions, over 75 min. to a ~tirred solution of 82.69 g o~ potassium cyande and 46.62 g of cupric sulfate in 400 ml of water at 60-65C. The gray-greenish mixture is stirred and heated at 60-65C for an additional 30 min and then allowed to cool to r.t. The mixture is filtered through celite and the precipita~e is washed with dichloromethane (3 x 200 ml). The dichloromethane washings ~re used to sxtract the aqueous solutlon. The combined sx~racts are washed with water, br~ne, dried and evaporated to dryness to give an oily resldu~ which i~ chro~atographed on silica gel to give 31.44 g of 2-nitro-4-trifluoromethoxybenzonitrile.
.
!
2~P~2~13~
E~AMPLE 3 Preparation of 2-nitro-4-trifluoromethoxy benzoic acid A stirred solution of 40.96 g of 2-nitro-4-trlfluorobenzonitrilz in 90 ml of concentrated sulfuric acid and 125 ml of water is refluxed for 45 hrs. The reaction mixture is cooled and dlluted with 200 ml of cold water.
The aqueous supernatant is decanted from th0 brown cryust~lline gu~. 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 wlth ether. The combined extracts are dried and evaporated to dryness to give crystalline 2-nitro-4-trifluoromethoxybenzoic acid m.p. 119C.
E~AMPLE 4 Preparationof2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybenzoyl-oxy)-6H-1,2-oxazine 3-one (Formula II Rl-R2-R3-CH3; R4-R6-~H; R-N02;
A stirred solution of 43.98 g of 2-nitro-4-trifluoromethoxybenzoic acid in 100 ml of thionyl chloride is refluxed for 2 hrs and then concentrated to dryness to give oily 2-nitro-4-tr~fluoromethoxybenzoyl chloride. To a stirred solution of 27.53 g of 2,6,6-trimethyl-2H-1,2-oxazine-3,5(4H, 6H)-dione and 35 ml (25/mm) of triethylamine in 290 ml of dichloromethane, cooled in an ice bath, under nitrogen, is added dropwise a solution of 2-nitro-4-trifluoromethoxybenzoyl chloride in 100 ml of di-chloromethane. After s~irring at 0C at r.t. for 2 hrs., the 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.
Claims (9)
1. A compound of formula I
wherein, each of R1, R2 and R3 is independently hydrogen, C1-8alkyl, carboxyl, C1-8alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or R1 and R2 together form a C3-6alkylene bridge R4 is hydrogen, C1-8alkyl, C1-8alkylcarbonyl, C1-8alkoxycarbonyl, C(O)NR7R8, C1-8alkylsulphonyl, P(O)-(OR9)2, R7P(O)-OR9, benzoyl or a cation;
R is C1-8alkyl optionally substituted by l to 6 halogen atoms, C1-8-alkoxy optionally substituted by 1 to 6 halogen atoms, C1-8alkyl-carbonyl, C1-8alkoxycarbonyl, NR7R8, OnS(O)n,R10, NR7SO2R8, halogen, cyano or nitro;
R5 is C1-8alkoxy substituted by 1 to 6 halogen atoms;
R8 is hydrogen or selected from the meanings given for R;
each of R7 and R8 is independently hydrogen or C1-8alkyl;
R9 is C1-8alkyl;
R10 is C1-9alkyl optionally substituted by 1 to 6 halogen atoms;
n is 0 or l;
n' is 0, 1 or 2;
provided that when R1, R2 and R3 are methyl, R4 and R6 are hydrogen and R is nitro, R5 is not difluoromethoxy.
wherein, each of R1, R2 and R3 is independently hydrogen, C1-8alkyl, carboxyl, C1-8alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or R1 and R2 together form a C3-6alkylene bridge R4 is hydrogen, C1-8alkyl, C1-8alkylcarbonyl, C1-8alkoxycarbonyl, C(O)NR7R8, C1-8alkylsulphonyl, P(O)-(OR9)2, R7P(O)-OR9, benzoyl or a cation;
R is C1-8alkyl optionally substituted by l to 6 halogen atoms, C1-8-alkoxy optionally substituted by 1 to 6 halogen atoms, C1-8alkyl-carbonyl, C1-8alkoxycarbonyl, NR7R8, OnS(O)n,R10, NR7SO2R8, halogen, cyano or nitro;
R5 is C1-8alkoxy substituted by 1 to 6 halogen atoms;
R8 is hydrogen or selected from the meanings given for R;
each of R7 and R8 is independently hydrogen or C1-8alkyl;
R9 is C1-8alkyl;
R10 is C1-9alkyl optionally substituted by 1 to 6 halogen atoms;
n is 0 or l;
n' is 0, 1 or 2;
provided that when R1, R2 and R3 are methyl, R4 and R6 are hydrogen and R is nitro, R5 is not difluoromethoxy.
2. A compound according to Claim 1 wherein each of R1, R2, R3 is selected from hydrogen or C1-4alkyl;
R is selected from C1-4alkyl optionally substituted with chloro, bromo, or fluoro, -(O)n-S(O)n,-C1-4alkyl, halogen or nitro;
R5 is fluoroalkoxy;
R6 is selected from hydrogen, C1-4alkyl, C1-4alkoxy, bromo, chloro;
R4 is selected from H, C1-4alkyl, C4-8alkylcarbonyl, benzoyl, C1-4alkyl-sulphonyl or a cation.
R is selected from C1-4alkyl optionally substituted with chloro, bromo, or fluoro, -(O)n-S(O)n,-C1-4alkyl, halogen or nitro;
R5 is fluoroalkoxy;
R6 is selected from hydrogen, C1-4alkyl, C1-4alkoxy, bromo, chloro;
R4 is selected from H, C1-4alkyl, C4-8alkylcarbonyl, benzoyl, C1-4alkyl-sulphonyl or a cation.
3. A compound according to Claim 2 wherein each of R1-R2 and R3 is selected from H, C1-3alkyl R4 is H;
R is selected from NO2, Cl, CF3.
R is selected from NO2, Cl, CF3.
4. A compound according to Claim 3 wherein R1, R2 and R3 are each methyl, R4 and R6 are each hydrogen, R is nitro and R5 is OCF3.
5. A pesticidal composition comprising the compound of formula I
as defined in Claims 1-4, in association with an agriculturally acceptable carrier.
as defined in Claims 1-4, in association with an agriculturally acceptable carrier.
6. A method of controlling weeds comprising applying to the weeds or their locus herbicidally effective amount of a compound of formula I as defined in Claims 1-4.
7. A method of controlling acari comprising applying to the acari or their locus an acaricidally effective amount of a compound of formula I as defined in Claims 1-4.
8. A process for preparing a compound of formula I as defined in Claim 1 which comprises a) rearranging an enol ester of formula (II) II
wherein R1, R2, R3, R, R5 and R6 are as defined in claim 1 to give a compound of formula I wherein R4 is H
b) when R4 is other than hydrogen reacting a compound of formula I
wherein R4 is hydrogen with either a) the group R40-OH and a catalyst, or b) the group R40-Q and a moderate base, wherein Q is a halogen atom, to give a compound of formula I where R40 is the desired substituent.
wherein R1, R2, R3, R, R5 and R6 are as defined in claim 1 to give a compound of formula I wherein R4 is H
b) when R4 is other than hydrogen reacting a compound of formula I
wherein R4 is hydrogen with either a) the group R40-OH and a catalyst, or b) the group R40-Q and a moderate base, wherein Q is a halogen atom, to give a compound of formula I where R40 is the desired substituent.
9. 2-nitro-4-trifluoromethoxy benzoic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60470890A | 1990-10-25 | 1990-10-25 | |
| US604,708 | 1990-10-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2072134A1 true CA2072134A1 (en) | 1992-04-26 |
Family
ID=24420699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002072134A Abandoned CA2072134A1 (en) | 1990-10-25 | 1991-10-23 | Heterocyclic dione derivatives as pesticides and plant growth regulators |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0506907A1 (en) |
| JP (1) | JPH05503106A (en) |
| KR (1) | KR927003554A (en) |
| AU (1) | AU642052B2 (en) |
| BR (1) | BR9106194A (en) |
| CA (1) | CA2072134A1 (en) |
| CS (1) | CS193492A3 (en) |
| HU (1) | HUT61534A (en) |
| IL (1) | IL99834A0 (en) |
| PL (1) | PL295411A1 (en) |
| WO (1) | WO1992007837A1 (en) |
| ZA (1) | ZA918535B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5895774A (en) * | 1993-02-18 | 1999-04-20 | Fenderson; John M. | Herbicidal compositions comprising dimethenamid and ethofumesate |
| ES2207637T3 (en) | 1993-02-18 | 2004-06-01 | Basf Aktiengesellschaft | HERBICIDE COMPOSITIONS. |
| US5716901A (en) * | 1993-02-18 | 1998-02-10 | Sandoz Ltd. | Synergistic herbicidal compositions of dimethenamid, sulcotrione, and atrazine |
| WO2001066522A1 (en) * | 2000-03-09 | 2001-09-13 | Syngenta Participations Ag | Acylated phenyl or pyridine herbicides |
| GT200100103A (en) | 2000-06-09 | 2002-02-21 | NEW HERBICIDES | |
| DE10117503A1 (en) | 2001-04-07 | 2002-10-17 | Bayer Cropscience Gmbh | Derivatives of benzoylcyclohexanediones and their use as herbicides |
| WO2003011298A1 (en) * | 2001-08-03 | 2003-02-13 | Chirologix Pharmaceuticals Inc. | Antibacterial oxazinones and methods for their use and synthesis |
| DE10144529A1 (en) * | 2001-09-11 | 2003-03-27 | Bayer Cropscience Gmbh | New aminocarbonylalkyl-substituted 3-benzoyl-cyclohexane-1,3-dione derivatives, useful as broad-spectrum herbicides for selective pre- or post-emergence weed control, especially in wheat, maize or rice |
| DE10160007A1 (en) * | 2001-12-06 | 2003-06-18 | Bayer Cropscience Ag | [1.2] oxazine-3,5-dione |
| DE10215723A1 (en) | 2002-04-10 | 2003-10-30 | Bayer Cropscience Gmbh | 3-keto or 3-oxime ether substituted benzoylcyclohexanediones |
| BRPI1008949B1 (en) | 2009-03-11 | 2018-07-10 | Bayer Intellectual Property Gmbh | HALOALKYLMETHYLENEXY-PHENYL-SUBSTITUTED KETOENOLS AND THEIR USE, COMPOSITION, USE AND METHOD OF PRODUCTION, METHODS FOR COMBATING ANIMAL PEST AND / OR GROWTH OF UNWANTED PLANTS |
| DE102010008644A1 (en) | 2010-02-15 | 2011-08-18 | Bayer Schering Pharma Aktiengesellschaft, 13353 | Cyclic ketoenols for therapy |
| AU2013211636B2 (en) | 2012-01-26 | 2016-09-29 | Bayer Intellectual Property Gmbh | Phenyl-substituted ketoenols for controlling fish parasites |
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| DE3382601T2 (en) * | 1982-03-25 | 1993-01-07 | Stauffer Chemical Co | 2- (2-SUBSTITUTED BENZOYL) -1,3 CYCLOHEXANDIONE. |
| IL77350A (en) * | 1984-12-20 | 1991-01-31 | Stauffer Chemical Co | Production of acylated diketonic compounds |
| TR24452A (en) * | 1989-04-25 | 1991-11-01 | Sandoz Ltd | HETERCYCIC DIONS AS PESTICIDES AND PLANT BUEYUEME REGULATORS |
-
1991
- 1991-10-23 CA CA002072134A patent/CA2072134A1/en not_active Abandoned
- 1991-10-23 IL IL99834A patent/IL99834A0/en unknown
- 1991-10-23 BR BR919106194A patent/BR9106194A/en unknown
- 1991-10-23 KR KR1019920701501A patent/KR927003554A/en not_active Application Discontinuation
- 1991-10-23 JP JP3517054A patent/JPH05503106A/en active Pending
- 1991-10-23 PL PL29541191A patent/PL295411A1/en unknown
- 1991-10-23 EP EP91918021A patent/EP0506907A1/en not_active Withdrawn
- 1991-10-23 AU AU87442/91A patent/AU642052B2/en not_active Ceased
- 1991-10-23 WO PCT/EP1991/002014 patent/WO1992007837A1/en not_active Application Discontinuation
- 1991-10-23 HU HU922107A patent/HUT61534A/en unknown
- 1991-10-25 ZA ZA918535A patent/ZA918535B/en unknown
-
1992
- 1992-06-23 CS CS921934A patent/CS193492A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS193492A3 (en) | 1992-10-14 |
| EP0506907A1 (en) | 1992-10-07 |
| ZA918535B (en) | 1993-04-26 |
| JPH05503106A (en) | 1993-05-27 |
| PL295411A1 (en) | 1993-06-28 |
| AU642052B2 (en) | 1993-10-07 |
| BR9106194A (en) | 1993-03-23 |
| HUT61534A (en) | 1993-01-28 |
| IL99834A0 (en) | 1992-08-18 |
| KR927003554A (en) | 1992-12-18 |
| AU8744291A (en) | 1992-05-26 |
| WO1992007837A1 (en) | 1992-05-14 |
| HU9202107D0 (en) | 1992-10-28 |
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