GB2141427A - Herbicidal cyclohexane-1,3-dione derivatives - Google Patents
Herbicidal cyclohexane-1,3-dione derivatives Download PDFInfo
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- GB2141427A GB2141427A GB08412145A GB8412145A GB2141427A GB 2141427 A GB2141427 A GB 2141427A GB 08412145 A GB08412145 A GB 08412145A GB 8412145 A GB8412145 A GB 8412145A GB 2141427 A GB2141427 A GB 2141427A
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
Abstract
Novel compounds of the formula I and isomers thereof <IMAGE> (wherein: X are selected from halogen, nitro, cyano, alkyl, substituted alkyl, hydroxy, alkoxy, substituted alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, acyloxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sulfamoyl, substituted sulfamoyl, alkanoyloxy, benzyloxy, substituted benzyloxy, amino, substituted amino, and the groups formyl and alkanoyl and the oxime, imine and Schiff base derivatives thereof; R<1> is selected from hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, alkylsulfonyl, arylsulfonyl, acyl and an inorganic or organic cation; R<2> is selected from alkyl, substituted alkyl, alkenyl, haloalkenyl, alkynyl and haloalkynyl; R<3> is selected from alkyl, fluoroalkyl, alkenyl, alkynyl, and phenyl; R<4> is selected from halogen, alkyl, cyano and alkoxycarbonyl; and n is an integer selected from 3 to 5).
Description
SPECIFICATION
Herbicidal cyclohexane-1,3-dione derivatives
This invention relates to organic compounds having biological activity and in particularto organic compounds having herbicidal properties and plant growth regulating properties, to processes for the preparation of such compounds, to intermediates useful in the preparation of such compounds and to herbicidal compositions and processes utilizing such compounds and to plant growth regulating compositions and processes utilizing such compounds.
The use of certain cyclohexane-1,3-dione derivatives as grass herbicides is known in the art. For example, the "Pesticide Manual" (C R Worthing Editor, The British Crop Protection Council, 6th Edition 1979) describes the cyclohexane-1,3-dione derivative known commercially as alloxydim-sodium (methyl 3-[l-(allyloxyimino) butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene carboxylate) and its use as a grass herbicide. This compound is disclosed in Australian Patent No 464655 and its equivalents such as UK Patent No 1 461170 and US Patent No 3 950 420.
More recently, at the 1980 British Crop Protection Conference ("1980 British Crop Protection Conference
Weeds, Proceedings Vol 1, Research Reports", pp 39 to 46, British Crop Protection Council, 1980), a new cyclohexane-1,3-dione grass herbicide code named NP 55 (2-N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3 hydroxy-2-cyclohexen-1-one) was announced. This compound is disclosed in Australian Patent No 503917 and its equivalents.
It has now been found that certain 5-phenyl substituted cyclohexane-1,3-dione derivatives in which the phenyl ring is substituted with three or more substituents and the cyclohexane ring is substituted in the 4-position are particularly useful herbicides.
Accordingly the invention provides a compound of formula I or an isomer thereof:
wherein: n is an integer selected from 3 to 5;
X, which may be the same or different, are independently selected from the group consisting of: halogen;
nitro; cyano; C1 to Ce alkyl; C1 to C6 alkyl substituted with a substituent selected from the group
consisting of halogen, nitro, hydroxy, C1 to C6 alkoxy and C1 to C6 alkylthio; C2 to c6 alkenyl; C2 to C6
alkynyl; hydroxy; C1 to C6 alkoxy; C1 to C6 alkoxy substituted with a substituent selected from halogen
and C1 to Ce alkoxy; C2 to C6 alkenyloxy; C2 to C6 alkynyloxy; C2 to C6 alkanoyloxy; (C1 to C6 alkoxy)
carbonyl; C1 to Ce alkythio; C1 to Ce alkylsulfinyl; C1 to C6 alkylsulfonyl; sulfamoyl;N-(C1 to C6
alkyl)sulfamoyl; N,N-di(C1 to Ce alkyl)-sulfamoyl; benzyloxy; substituted benzyloxy wherin the
benzene ring is substituted with from one to three substituents selected from the group consisting of
halogen, nitro, C1 to C6 alkyl, C1 to C6 alkoxy and C1 to C6 haloalkyl; the group NR5R6 wherein R5 and R6 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, C2 to C6 alkanoyl,
benzoyl and benzyl; the groups formyl and C2 to C6 alkanoyl and the oxime, imine and Schiff base
derivatives thereof;
R1 is selected from the group consisting of: hydrogen; C1 to C6 alkyl; C2 to C6 alkenyl;C2 to C6 alkynyl;
substituted C1 to C6 alkyl wherein the alkyl group is substituted with a substituent selected from the
group consisting of C1 to C6 alkoxy, C1 to C6 alkylthio, phenyl and substituted phenyl wherein the
benzene ring is substituted with from one to three substituents selected from the group consisting of
halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to C6 alkylthio; C1 to C6
(alkyl) sulfonyl; benzenesulfonyl; substituted benzenesulfonyl wherein the benzene ring is substituted
with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C1 to
C6 alkyl, C1 to C6 haloalkyl; C1 to C6 alkoxy and C1 to C6 alkylthio; an acyl group; and an inorganic or
organic cation;
R2 is selected from the group consisting of:C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 haloalkenyl; C2 to c6
alkynyl; C2to C6 haloalkynyl; substituted C1 to C6alkyl wherein the alkyl group is substituted with a
substituent selected from the group consisting of halogen, C1 to C6 alkoxy, C1 to C6 alkylthio, phenyl
and substituted phenyl wherein the benzene ring is substituted with from one to three substituents
selected from the group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6
alkoxy and C1 to C6 alkylthio;
R3 is selected from the group consisting of: C1 to C6 alkyl; C1 to C6 fluoroalkyl; C2 to C6 alkenyl; C2 to C6
alkynyl; and phenyl; and
R4 is selected from the group consisting of: halogen; cyano; C1 to C6 alkyl; and (C1 to C6 alkoxy)-carbonyl.
When in the compound of formula I X is chosen from the groups formyl and C2 to C6 alkanoyl and the oxime, imine and Schiff base derivatives thereof, the nature of the oxime, imine and Schiff base derivatives is not narrowly critical. Although not intending to be bound by theory it is believed that in the plant the (substituted) imine group may be removed to give the corresponding compound of formula I in which Xis formyl or C2 to C6 alkanoyl. Suitable values for the groups formyl and C2to C6 alkanoyl and the oxime, imine and Schiff base derivates thereof include groups of the formula -C(R7)=NR8 wherein R7 is chosen from hydrogen and C1 to C5 alkyl, and R6 is chosen from hydrogen, C1 to C6 alkyl, phenyl, benzyl, hydroxy, C1 to C6 alkoxy, phenoxy and benzyloxy.
When in the compound of formula I R1 is chosen from acyl the nature of the acyl group is not narrowly critical. Although not intending to be bound by theory, it is believed that when R1 is acyl the acyl group may be removed in the plant by hydrolysis to give the corresponding compound of formula I in which R1 is hydrogen. Suitable acyl groups include: alkanoyl, for example C2 to C6 alkanoyl; aroyl, for example benzoyl and substituted benzoyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to
C6 alkylthio; and heteroaroyl, for example 2-furoyl, 3-furoyl, 2-then-oyl and 34henoyl.
When in the compound of formula I R1 is chosen from an inorganic or organic cation the nature of the cation is not narrowly critical. Although not intending to be bound by theory, it is believed that when R1 is a cation the cation may be removed in the plant to give a compound of formula I wherein R1 is hydrogen.
Suitable inorganic cations include the alkali and alkaline earth metal ions, heavy metal ions including the transition metal ions, and the ammonium ion. Suitable organic cations include the cation R9R10R11R12N03 wherein R9, R10, R11 and R12 are independently chosen from the group consisting of: hydrogen; C1 to C10 alkyl; substituted C1 to C10 alkyl wherein the alkyl groups is substituted with a substituent chosen from the group consisting of hydroxy, halogen and C1 to C6 alkoxy; phenyl; benzyl; and the groups substituted phenyl and substituted benzyl wherein the benzene ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to
C6 alkylthio.
It should be recognized that when R1 is hydrogen the compounds of the invention may exist in any one of four tautomeric forms as shown below wherein represents the group
Preferred compounds of the invention include those compounds of formula I wherein:
X is selected from the group consisting of: halogen; C2to C6 alkanoyl;C1 to C6 alkyl; and C1 to C6 alkoxy;
R1 is chosen from hydrogen, alkali metal, ammonium, C1 to C10 alkylammonium, C2to C6 alkanoyl,
benzoyl and substituted benzoyl wherein the benzene ring is substituted with from one to three
substituents chosen from halogen, nitro and cyano;
R2 is chosen from methyl, ethyl, n-propyl, allyl and propargyl;
R3 is chosen from methyl, ethyl and n-propyl;
R4 is selected from halogen and (C1 to C6 alkoxy) carbonyl; and n is an integer selected from 3 to 5.
More preferred compounds of the invention include compounds of formula
wherein:
X2, X4, X6 and X are independently selected from the group consisting of methyl, methoxy and acetyl;
R1 is hydrogen;
R2 is ethyl;
R3 is selected from ethyl and n-propyl;
R4 is selected from fluoro and ethoxycarbonyl; and n is selected from zero and the integers 1 and 2.
Particularly preferred X include methyl.
Particularly preferred R1 include hydrogen.
Particularly preferred R2 include ethyl.
Particularly preferred R3 include ethyl and n-propyl.
Particularly preferred R4 is fluoro.
Examples of compounds embraced by the invention include:
2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one (1); 2-[i -(ethoxyimino)propyl]-44luoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one (2); 2-[1-(allyloxyimino)propyl]-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1-one (3); 2-[l-(ethoxyi mino)propyl]-3-hyd roxy-5-mesityl-4-methylcyclohex-2-en-l -one (4); 4-cyano-2-[1 -(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1 More (5); 2-[1-(ethOxyimino)butyl]-4-fluoro-3-hydroxy-5-(2,3,4,6-tetramethylphenyl)cyclohex-2-en-1-one (6); 2-[1-(ethoxyimino)butyl]-4-fluoro-2-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-one (7);; 2-[1-(ethoxyimino)butyl]-4-fluoro-3-hydroxy-5-(2-methoxy-4,6-dimethylphenyl)cyclohex-2-en-1-one (8); 5-(2-chloro-3,4,5,6-tetramethylphenyl)-2-[1 -(ethoxyimino)butyl]-44luoro-3-hydroxycyclohex-2-en-1 -one (9); 5-(2-bromo-3,4,5,6-tetramethylphenyl)-2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxycyclohex-2-en-1 -one (10); 2-[1 -(ethoxyimino)butyl]-4-fluoro-5-(3-fluoro-2,4,6-trimethylphenyl)-3-hydroxyCyclohex-2-en-1-one (11);
2-[1 -(ethoxyimino)butyl]-4-fluoro-5-(3-fluoro-2,4,5,6-tetramethylphenyl)-3-hydroxyCyclohex-2-en-1 -one (12); 5-(3-chloro-2,4,6-trimethylphenyl)-2-[1-(ethoxyimino)-butyl]-4-fluoro-3-hydroxycyclohex-2-en-1-one (13);; 2-[i -(ethoxyimino)butyl]-44luoro-3-hydroxy-5-[2,6-dimethyl-3-(N,N-dimethylsulfamoyl)phenyljcyclohex- 2-en-1-one (14); 2-[1 -(ethoxyim ino)butyl]-4-fl uoro-3-hydroxy-5-[2,4,6-trimethyl-3-(N ,N- dimethylsulfamoyl)phenyl]cyclohex 2-en-l-one(l5); 2-[1 -(ethoxyimino)butyl]-4-fl uoro-3-hydroxy-5-(2,4,6-trimethyl-3-sulfamoylphenyl)cyclohex-2-en-1 -one (16); 5-(3-acetyl-2,4,6-trimethylphenyl)-2-[1 -(ethoxyimino)-butylj-44luoro-3-hydroxycyclohex-2-en-1 -one (17);
5-(3-acetyl-5-ethyl-2,4,6-trimethylphenyl)-2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxycyclohex-2-en-1 -one (18); 5-(3-acetyl-2,4,5,6-tetramethylphenyl)-2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxycyclohex-2-en-1 -one (19);; 5-(3-acetyl-2,4,6-trimethyl phenyl)-2-[1 -(ethoxyimi no)-butyl]-4-fluoro-3-hydroxycyclohex-2-en- 1-one (20); and
the lithium, potassium, sodium, copper, nickel and tetra(n-butyl) ammonium salts thereof;
2-[1 -(ethoxyimino)butyl]-4-fluoro-5-mesityl-3-pivaloyloxycyclohex-2-en- 1 -one (21);
2-[1 -(ethoxyimino)butyl]-4-fluoro-5-(2,3,4,6-tetramethyl phenyl )-3-pivaloyloxycyclohex-2-en-1 -one (22); 2-[1-(ethoxyimino)butyl]-4-fluoro-5-(2,3,4,5,6-pentamethylphenyl)-3-pivaloyloxycyclohex-2-en-1-one (23); 3-benzoyloxy-2-[1 -(ethoxyimino)butyl,]A4luorn-5-mesitylcyclohex-2-en-1 -one (24); 3-benzoyloxy-2-[1 -(ethoxyimino)butylj-4-fluoro-5-(2,3,4,6-tetramethylphenyl)cyclohex-2-en-1 -one (25); and
3-benzoyloxy-2-[1 -(ethoxyimino)butyl]-4-fluoro-5-(2,3,4,5,6-pentamethyl phenyl)cyclohex-2-en-1 -one (26).
The compounds of the invention may be prepared by a variety of methods and in a further aspect the invention provides methods for the preparation of compounds of formula I.
Conveniently the preparation of the compounds of the invention can be considered in three or four parts.
Part A involves the formation of a 5-arylcyclohexan-1 ,3-dione of formula IX. This reaction may be carried out in a two step process by: (i) reacting, preferably in the presence of a base, an aldehyde derivative of formula V with acetone (IVa)
or an acetone derivative of formula IVb to form a ketone derivative of formula Vla or Vlb respectively;;
and reacting, preferably in the presence of a base, a ketone derivative of formula Vla with a malonic
acid ester derivative of formula Vlla or a ketone derivative of formula Vlb with a malonic acid ester of
formula Vllb, to give an intermediate of formula Vllla or Vl I lb respectively which may be isolated or
hydrolysed directly, preferably in the presence of an acid, to give a 5-arylcyclohexan-1,3-dione of
formula IX, or reacting, preferably in the presence of a base, a ketone derivative of formula Via with
an alkanoic acid ester of formula Vole to give a 5-arylcyclohexan-1,3-dione of formula IX;; (ii) reacting, preferably in the presence of a base, an aldehyde derivative of formula V with a malonic acid
ester of formula Vllb to give an arylmethylidenemalonate derivative of formula Vole which is in turn
reacted, preferably in the presence of a base, with an acetoacetic acid ester derivative of formula Vlld to give an intermediate of formula Vllle which may be isolated or hydrolysed directly, preferably in
the presence of an acid, to give a 5-arylcyclohexan-1,3-dione of formula IX; or (iii) reacting, preferably in the presence of a base, an aldehyde derivative of formula V with an acetic acid
ester of formula IVc to give a 2-arylalkenoate derivative of formula Vld which is in turn reacted,
preferably in the presence of a base, with an acetoacetic acid ester derivative of formula Vlld to give
an intermediate of formula VIlla which may be isolated or hydrolysed directly, preferably in the
presence of an acid, to give a 5-arylcyclohexan-1,3-dione of formula IX.
Part B involves the acylation of a compound of formula IX to give a 2-acyl-5-arylcyclohexan-1 ,3-dione of formula Xlil. This reaction may be carried out by reacting a 5-arylcyclohexan-1,3-dione of formula IX with: (iv) an acid anhydride of formula X in the presence of either an alkali metal salt of the corresponding acid
of formula XI or an alkoxide salt of formula XII, wherein M is an alkali metal ion and R is C1 to C6 alkyl; (v) an acid anhydride of formula X in the presence of the corresponding acid of formula XIV; (vi) an acid halide of formula XV, wherein hal represents halogen, in the presence of a Lewis acid catalyst; (vii) a mixture of an acid halide of formula XV and the corresponding acid of formula XIV; or (viii) with an alkali or alkaline earth metal hydride followed by reaction with an acid anhydride of formula X
or an acid halide of formula XV.
Alternatively, this acylation reaction may be carried out by: (ix) reacting a 5-arylcyclohexan-1 3-dione of formula IX with an acid halide of formula XV in the presence
of pyridine to give an intermediate O-acyl derivative of formula XVI; and (x) reacting the intermediate of formula XVI with a Lewis acid catalyst; (xi) reacting the intermediate of formula XVI with the acid of formula XIV; or (xii) reacting the intermediate of formula XVI with imidazole.
Part C involves the formation of a compound of the invention of formula I wherein R7 is hydrogen, that is a compound of formula II. This reaction may be carried out either by reacting a 2-acyl-5-arylcyclohexan-1 3- dione of formula XIII with: (xiii) an alkoxyamine derivative of formula XVII; or (xiv) hydroxylamine to give an intermediate oxime derivative of formula XVIII and reacting that
intermediate oxime derivative of formula XVIII with an alkylating agent of formula XIX wherein Lisa leaving group such as, for example, chloride, bromide, iodide, sulfate, nitrate, methyl sulfate, ethyl
sulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, methanesulfonate, fluoro
sulfonate, fluoromethanesulfonate and trifluoromethanesulfonate.
Part D involves the formation of a compound of the invention of formula I wherein R1 is a substituent other than hydrogen.
Compounds of the invention of formula 1, wherein R1 forms an ether, acyl or sulfonyl derivative of a compound of formula li, may be prepared from the corresponding compounds of the invention of formula Il by reacting with an etherification, acylation or sulfonylation reagent of formula XX.
Compounds of the invention of formula I wherein R1 is an inorganic or organic cation may be prepared from the compounds of the invention of formula I wherein R1 is hydrogen, that is, compounds of formula 11, by reacting said compounds of formula II with an inorganic or organic salt. For example, the compounds of formula I wherein R1 is an alkali metal ion may be prepared by reacting the appropriate compound of formula II with the appropriate alkali metal hydroxide or alkoxylate. The compounds of formula I wherein R1 is a transition metal ion or an organic cation may similarly be prepared by reacting the appropriate compound of formula II with an appropriate transition metal salt or organic base. Alternatively, the compounds of formula I wherein R1 is a transistion metal ion or an organic cation may be prepared by reacting the appropriate compound of formula I wherein R1 is an alkali m-etal ion with an appropriate transition metal salt or organic salt.
Accordingly, in a further aspect the invention provides a process for the preparation of a compound of formula I, as hereinbefore defined, which process comprises:
reacting 2-acyl-5-(aryl)cyclohexane-1 ,3-dione derivative of formula XIII with an alkoxyamine derivative of formula XVII to give a compound of the invention of formula II or reacting the 2-acyl-5-(aryl)cyclohexane-1,3- dione derivative of formula XIII with hydroxylamine and alkylating the oxime intermediate of formula XVIII with an alkylating agent of formula XIX, wherein Lisa leaving group, to give a compound of the invention of formula II; and optionally
reacting the compound of the invention of formula II with a compound of formula XX, wherein Lisa leaving groups, to give a compound of the invention of formula i.
Certain of the intermediate compounds of formulae V, Vla, Vlb, Vlc, Vld, VIlla, Vlllb, Vlilc, IX, XIII, XVI and
XVIII are novel compounds and therefore in further embodiments the invention provides novel compounds of formulae V, Vla, Vlb, Vlc, Vld, VIIIa, Vlllb, Vlllc, IX, XIII, XVI and XVIII and processes for the preparation thereof.
The structures of the compounds described above are detailed on the following pages wherein 3 represents the group
CH3COCH3 CH3COCH2R4 CH3CO2R IVa IVb IVc ki-CHO V -CH=CH-COCHB m-CH=CR4-COCH3
Vla Vlb
Vla
-CH=C(CO2R)2 -CH=CH-CO2R
#CH=C(C02R)2
Vle Vld
Vlc
R4CH(CO2R)2 CH2(CO2R)2
R4CH(Co2R)2
VIIa VIIb
VIIa
R4CH2CO2R CH3COCH R4CO2R
R4CH2CO2R
Vlle Vlld
(R3CO)2O R3Co2M ROM
X XI XII
R3Co2H R3COhal
XIV XV
H2NOR2 R2L R1L
XVII XIX XX
The compounds of formula I are active as herbicides and therefore, in a further aspect the invention provides a process for severely damaging or killing unwanted plants which process comprises applying to the plants, or to the growth medium of the plants, an effective amount of a compound of formula I as hereinbefore defined.
Generally speaking the compounds of formula I are herbicidally effective against a variety of plants.
However, certain of the compounds of the invention are selectively active against monocotyledonous plants, dicotyledonous plants being relativey unaffected by rates of application of the compounds of the invention which are severely damaging or lethal to other plant species.
Moreover, certain of the compounds of formula I are selectively active within the group of monocotyledonous plants and may be used at a rate sufficient to control monocotyledonous weeds in cultivated crops, especially wild grasses in cereal crops. Certain of such compounds of the invention are especially useful in the control of wild grasses such as wild oats and rye grass in crops of cultivated monocotyledonous plants such as wheat, barley and other varieties of cereals.
Accordingly, in yet a further aspect the invention provides a process for controlling monocotyledonous weeds in cultivated crops, especially wild grasses in cereal crops such as wheat, which process comprises applying to the crop, or to the growth medium of the crop, a compound of formula I, as hereinbefore defined, in an amount sufficient to severely damage or kill the weeds but insufficient to damage the crop substantially.
The compounds of formula I may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application). However, the compounds are, in general, more effective when applied to the plant post-emergence.
The compounds of formula I may be used on their own to inhibit the growth of, severely damage, or kill plants but are preferably used in the form of a composition comprising a compound of the invention in admixture with a carrier comprising a solid or liquid diluent. Therefore, in yet a further aspect the invention provides growth inhibiting, plant damaging, or plant killing compositions comprising a compound of formula las hereinbefore defined and an inert carrier therefor.
Certain of the compounds of formula I exhibit useful plant growth regulating activity. For example, while compounds of formula I are selectively active herbicides against wild grasses in crops of cultivated plants at some rates of application they exhibit plant growth regulating effects in said crops.
Plant growth regulating effects may be manifested in a number of ways. For example, suppression of apical dominance, stimulation of auxiliary bud growth stimulation of early flowering and seed formation, enhancement of flowering and increase in seed yield, stem thickening, stem shortening and tillering. Plant growth regulating effects shown in compounds of the invention may include, for example, tillering and stem shortening in crops such as wheat and barley.
Accordingly in a still further aspect the invention provides a process for regulating the growth of a plant which process comprises applying to the plant, to the seed of the plant, orto the growth medium of the plant, an effective amount of a.compound of formula I, as hereinbefore defined.
To effect the plant growth regulating process of the present invention the compounds of formula I may be applied directly to the plant (post-emergence application) or to the seed or soil before the emergence of the plant (pre-emergence) application.
The compounds of formula I may be used on their own to regulate the growth of plants but in general are preferably used in the form of a composition comprising a compound of the invention in admixture with a carrier comprising a solid or liquid diluent. Therefore, in a still further aspect the invention provides plant growth regulating compositions comprising a compound of formula I as hereinbefore defined and an inert carrier therefor.
Compositions according to the invention include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water. Preferably the compositions contain from 1 ppm to 99% by weight of the active ingredient. Dilute compositions ready for use preferably contain from 1 ppm to 2% of active ingredient, while concentrated compositions may contain from 20 to 99% of active ingredient, although from 20 to 70% is usually preferred.
The solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, eg kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
Liquid compositions may comprise a solution or dispersion of an active ingredient in water optionally containing a surface-active agent, or may comprise a solution of dispersion of an active ingredient in a water-immiscible organic solvent which is dispersed as droplets in water.
The rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants to be treated, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an appication rate of from 0.001 to 10 kilograms per hectare is suitable while from 0.01 to 5 kilograms per hectare may be preferred.
The compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. For example, as hereinbefore indicated the compounds of the invention are effective herbicides against monocotyledonous weeds, wild grasses, but have little or no herbicidal effect against dicotyledonous plants, broad-leaved plants. As a result, in certain applications where it is desired to protect a cereal crop against both wild grasses and broad-leaved weeds it may be preferred to use a herbicidal composition comprising a mixture of at least one herbicidal compound of formula las hereinbefore defined and at least one other herbicide active against broad-leaved weeds.
The invention is now illustrated by, but is not limited to, the following Examples.
EXAMPLE 1 2-[1-rEthoxysminoybutyl7-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en- 1-one ( 1 ) (i) Diethyl fluoromalonate (3.44 g; 19 mmole; see J. Chem. Soc., 1959,3286) was added to a solution of
sodium metal (0.44 g; 19 mmole) in absolute thanol (30 ml) and the mixture was heated under reflux
with stirring. 1 -Mesityl-but-1 -en-3-one (3.8 g; 20 mmole) was added and the mixture was heated
under reflux for 2 hours. An aqueous solution of potassium hydroxide (2.5 g in 50 ml) was added and
the mixture was heated under reflux for a further4 hours and most of the ethanol allowed to distill off.
The cooled solution waswashed with toluene (50 ml) to remove coloured material and then the
aqueous layer was reheated to 80"C and carefully acidified with concentrated hydrochloric acid.
4-Fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one precipitated as a nearly colourless solid, mp 150-160 C and was collected by filtration (3.11 g, 73%). Analysis of the proton nuclear magnetic
resonance spectrum of the product indicated that it was a mixture of two geometrical isomers.
(ii) 4-Fluoro-3-hydroxy-5-mesitylcyclohex.2-en-1-one (3.3 g, 15 mmole) was dissolved in dimethylforma
mide (10 ml) at 90"C and sodium hydride (360 mg; 15 mmole) was added with stirring. When the
evolution of hydrogen had ceased (15 min) n-butyric anhydride (2.5 ml; 15 mmole) was added and
heating was continued for 30 minutes at 110"C. The dimethylformamide was removed by distillation
under reduced pressure and the residue was purified by chromatography over silica gel (eluant
dichloromethane) to give 2-butyryl-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1-one (300 mg; 8%) as
a pale yellow oil.The proton nuclear magnetic resonance spectrum of the product [(CDCI3; 8 in ppm):
1.01 (3H, t); 1.6 (2H,m); 2.22 (6H,s); 2.37 (3H,s); 2.5-4.2 (5H,m); 5.17 and 5.72 (total 1 H; d, J = 14Hz);
6.83 (2H, s); 18.10 (1 H,s)] indicated that it was a single geometrical isomer.
(iii) Ethoxyamine hydrochloride (100 mg) and 2-butyryl-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1-one
(300 mg) were dissolved with stirring in ethanol (20 ml) and an aqueous solution of sodium hydroxide
(50 mg in 2 ml) was added at 25"C. The mixture was allowed to stand at room temperature for 18
hours and then the ethanol was removed by distillation under reduced pressure. The residue was
partitioned between chloroform and water (pH 4) and the chloroform layer was separated and dried
over an hydros sodium sulphate and the solvent was removed by evaporation under reduced
pressure to give the product, 2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1- one (320 mg; 95%), as a pale brown oil.Proton nuclear resonance spectrum (CDCI3; 8 in ppm): 1.02
(3H,t); 1.35 (3H,t); 1.60 (2H,m); 2.25 (6H,s); 2.40 (3H,s); 2.5-4.2 5H,m); 4.13 (2H,q); 5.20 and 5.75 (total 1 H,d, J = 14Hz); 6.86 (2H,s); 15.57 (1H,bs).
EXAMPLE 2 2-[1-rEthoxysmino)propyl7-4-fluoro-3-hydroxy-5-mesitylcycohex-2-en- 1-one t2) and t27) (i) A solution of diethyl cyanophosphonate (1.3 g; 8 mmole), triethylamine (0.8 g; 8 mmole) and
propionic acid (0.6 g; 8 mmole) in dimethylformamide (10 ml) was added with stirring to an ice-cold
solution of 4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one (1.86 g; 7 mmole) and triethylamine (1.5
g; 15 mmole) in dimethylformamide (10 ml). The solution was stirred at room temperature for 4 hours
then poured into water (150 ml) and extracted with diethyl ether (2 x 50 ml). The ether layer was
separated, dried over anhydrous magnesium sulphate and evaporated to give a brown oil.
Purification by column chromatography over silica gel (60 g, eluant chloroform: n-hexane (1:1)) gave,
as the fastest moving band, 4-fluoro-3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1 -one (0.48 g,
22%), isolated as a colourless solid. The proton nuclear magnetic resonance spectrum ofthe product [CDCI3; 8 in ppm): 1.15 (3H,t); 2.24 (3H,s); 2.37 (6H,s); 2.4-4.0 (5H,m); 4.72 (1H,d,J=S6Hz); 6.80 (2H,s);
18.22 (1 H,s)) indicated that it was a single geometrical isomer.
(ii) Ethoxyamine hydrochloride (380 mg; 4 mmole) and then sodium acetate (320 mg; 4 mmole) were
added with stirring to a solution of 44luoro-3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1 -one (480
mg; 1.6 mmole) in ethanol (100 ml) at 20"C. After 20 hours at 20"C the ethanol was removed by
distillation under reduced pressure and the residue was diluted with water (100 ml) and extracted
with chloroform (2 x 50 ml). The chloroform layer was dried over anhydrous magnesium sulphate
and the solvent evaporated to give 2-[1-(ethoxyimino)propyl]-4-fluoro-3-hydroxy-5-mesitylcyclohex- 2-en-1-one (450 mg, 88%) as a pale yellow oil.Proton magnetic resonance spectrum (CDCI3; 8 in
ppm): 1.20 (3H,t); 1.34 (3H,t); 2.25 (3H,s); 2.38 (6H,s); 2.3-4.3 (7H,m); 4.80 (1H,d,J=56Hz); 6.86 (2H,s);
15.2 (1H,bs).
(iii) Later fractions from the purification of 4-fluoro-3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1 -one
(Part (i)) gave a-second geometrical isomer which was isolated as a colourless oil (200 mg, 9%). The
proton nuclear magnetic resonance spectrum of the product [(CDCI3; 8 in ppm): 1.16 (3H,t); 2.22
(3H,s); 2.37 (6H,s); 2.4-4.2 (5H,m); 5.55 (1 H,dofd,J=54x 14Hz); 6.84 (2H,s); 18.1(1 H,s)] and thin layer
chromatography indicated that it was a single geometrical isomer.
Reaction of this isomer of 4-fluoro-3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one with ethoxyamine hydrochloride following essentially the same procedure as described in part (ii) gave a second, slower running (silica-CHCI3) isomer of 2-[l-(ethoxyimino) 2-[1 -(ethoxyimino)propylj-44luoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one as a pale yellow oil. Proton magnetic resonance spectrum (CDCI3; 8in ppm): 1.13 (3H,t); 1.35(3H,t); 2.25 (3H,s); 2.39 (6H,s); 2.3-4.1 (5H, m); 4.14(2H,q); 5.55 (1H,dofd,J=54x14Hz); 6.86 (2H,s); OH proton not observed.
EXAMPLE 3 4-Ethoxyearbonyl-2-[1-rethoxysmino)propyl]-3-hydroxy-5-g2,3,4,5,6-pentamethylphenyl)cyclohex-2-en- 1-one (28) (i) 1-(2,3,4,5,6-pentamethylphenyl)but-1-en-3-one (22.0 g) was heated at reflux with sodium diethyl
malonate (2 equiv) in dry absolute ethanol (400 ml) for 24 hr. The cooled mixture was poured into
water (1 litre) and the resulting solution was acidified with dilute acetic acid. The mixture was
extracted with ethyl acetate and the dried (MgSO4) organic fraction was evaporated by distillation
under reduced pressure. The residue was stirred and washed with a little carbon tetrachloride to give 4-ethoxycarbonyl-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1 -one as a white solid,
mp 203 C.
(ii) 4-Ethoxyca rbonyl-3-hydroxy-5-(2,3,4,5,6-penta methyl phenyl )-2-propionylcyclohex-2-en-l -one was
preared from 4-ethoxycarbonyl-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1 -one and propionic anhydride following essentially the same procedure as that described in Example 1 part (ii) and was obtained as an oil. Pmr spectrum (CDCI3; Sin ppm): 0.92 (3H, t); 1.16 (3H, t); 2.22 (9H,s); 2.35 (6H,s); 2.2-4.5 (6H,m); 3.98 (2H,q), 18.31 (1H,s).
(iii) 4-Ethoxycarbonyl-2-[1 -(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2- en-1 -one was prepared from 4-ethoxycarbonyl-3-hydroxy-5-(2,3,4,5,6-pentamethyl phenyl )-2
propionylcyclohex-2-en-1 -one and ethoxyamine hydrochloride following essentially the same
procedure as that described in Example 1 part (iii) and was obtained as an oil. Pmr spectrum (CDCI3; 8 in ppm): 0.90 (3H, t); 1.12-1.41 (6H,2xt); 2.19 (9H,s); 2.34 (6H,s); 2.2-4.3 (6H,m); 3.86-4.28 (4H,2xq);
15.38 (1H,brs).
EXAMPLE 4
The following examples were prepared following essentially the same procedure as that described in
Example 3.
4-Ethoxycarbonyl-2-[1 -(ethoxyimi no)butyl]-5-(2,3,4,6-tetramethyl phenyl )cyclohex-2-en-l -one (29). Pmr spectrum (COCK3; 8 in ppm): 0.84-1.07 (6H,2xt); 1.33 (3H,t); 1.64 (2H,m); 2.13, 2.28 and 2.34 (12H, three apparent singlets); ca 2.2-4.2 (6H,m); ca 3.9-4.2 (4H, 2xq); 6.79 (1H,s); 15.47 (1H,brs).
5-(3-Acetyl-2,4,6-tri methylphenyl )-4-ethoxycarbonyl-2-[1 -(ethoxyimino)butyl]cyclohex-2-en-1 -one (30).
Pmr spectrum (CDCI3; Sin ppm): 0.89-1.06 (6H,2xt); 1.33 (3H,t); 1.62 (2H,m); 2.14,2.42 and 2.43 (12H, three apparent singlets); ca 2.2-4.2 (6H,m); ca 3.9-4.2 (4H,2xq); 6.83(1 H,s); 15.56(1 H,brs).
4-Ethoxycarbonyl-2-[1 -(ethoxyimino) propyl]-5-(2-methoxy-4,6-dimethyl phenyl ]cyclohex9-en-l-one (31).
Pmrspectrum (CDCI3; Sin ppm): 0.97-1.41 (9H,3xt); 2.26 (3H,s); 2.32 (3H,s); ca 2.2-4.6 (6H,m); 3.81 (3H,s); ca 3.9-4.3 (4H,2xq); 6.56 (2H,s); 15.26 (1 H, brs).
EXAMPLE 5
This non-limiting Example illustrates the preparation of formulations of the compounds of the invention.
a) Emulsifiable Concentrate
Compound No 1 was dissolved in toluene containing 7% v/v "Teric" N13 and 3% v/v "Kemmat" SC1SB to give an emulsifiable concentrate which may be diluted with water to the required concentration to give an
aqueous emulsion which may be applied by spraying.
("Teric" is a Trade Mark and "Teric" N13, is a product of ethoxylation of nonylphenol; "Kemmat" is a
Trade Mark and "Kemmat" SC1SB is a formulation of calcium dodecylbenzenesulfonate).
b) Aqueous Suspension
Compound No 1(5 parts by weight) and "Dyapol" PT (1 part by weight) were added to an aqueous solution (94 parts by weight) of "Teric" N8 and the mixture was ball milled to produce a stable aqueous suspension which may be diluted with water to the required concentration to give an aqueous suspension which may be appied by spraying. ("Dyapol" is a Trade Mark and "Dyapol" PT is an anionic suspending agent; "Teric" N8
is a product of ethoxylation of nonylphenol.) c) Emulsifiable Concentrate
Compound No 1 (10 parts by weight), "Teric" N13 (5 parts by weight) and "Kemmat" SC1SB (5 parts by weight) were dissolved in "Solvesso" 150 (80 parts by weight) to give an emulsifiable concentrate which may be diluted with water to the required concentration to give an aqueous emulsion which may be applied by spraying. ("Solvesso" is a Trade Mark and "Solvesso" 150 is a high boiling point aromatic petroleum fraction).
d) Dispersible Powder
Compound No 1 (10 parts by weight, "Matexil" DA/AC (3 parts by weight), "Aerosol" OT/B (1 part by weight) and china clay 298 (86 parts by weight) were blended and then milled to give a powder composition
having a particle size below 50 microns. ("Matexil" is a Trade Mark and "Matexil" DA/AC is the disodium salt of a naphthalenesulfonic acid/formaldehyde condensate; "Aerosol" is a Trade Mark and "Aerosol" OT/B is a formulation of the dioctyl ester of sodium sulfosuccinic acid).
e) High Strength Concentrate
Compound No 1 (99 parts by weight), silica aerogel (0.5 parts by weight) and synthetic amorphous silica silica (0.5 parts by weight) were blended and ground in a hammer-mill to produce a powder having a particle size less than 200 microns.
f) Dusting Powder
Compound No 1 (10 parts by weight), attapulgite (10 parts by weight) and pyrophyllite (80 parts by weight) were thoroughly blended and then ground in a hammer-mill to produce a powder of particle size less than 200 microns.
Emulsifiable concentrates and/or suspensions of the compounds of the invention were prepared essentially as described in part a), b) or c) above and then diluted with water, optionally containing surface active agent and/or oil, to give aqueous compositions of the required concentration which were used, as described in Examples 6 and 7, in the evaluation of the pre-emergence and post-emergence herbicidal activity of the compounds.
EXAMPLE 6
The pre-emergent herbicidal activity of the compounds of the invention formulated as described in
Example 5 was assessed by the following procedure:
The seeds of the test species were sown in rows 2 cm deep in soil contained in seed boxes. The monocotyledonous plants and the dicotyledonous plants were sown in separate boxes and after sowing the two boxes were sprayed with the required quantity of a composition of the invention. Two duplicate seed boxes were prepared in the same manner but were not sprayed with a composition of the invention and were used for comparison purposes. All the boxes were laced in a glasshouse, lightly watered with an overhead spray to initiate germination and then sub-irrigated as required for optimum plant growth. After three weeks the boxes were removed from the glass house and the effect of the treatment was visually assessed. The results are presented in Table 1 where the damage to plants is rated on a scale of from 0 to 5 where 0 represents from 0 to 10% damage, 1 represents from 11 to 30% damage, 2 represents from 31 to 60% damage, 3 represents from 61 to 80% damage, 4 represents from 81 to 99% damage and 5 represents 100% kill. A dash (-) means that no experiment was carried out.
The names of the test plants are as follows:
Wh Wheat
Ot Wild Oats
Rg Ryegrass
Jm Japanese millet
P Peas
Ip Ipomea
Ms Mustard
Sf Sunflower
TABLE 1
TEST PLANT
Compound APPLICATION
No Rate (kg/ha)
Wh Ot Rg Jm P Ip Ms Sf
1 1.0 1 0 4 4 0 0 0 0
0.25 0 0 2 0 0 0 0 0
2 1.0 0 2 5 5 0 0 0 0
2 0.25 0 0 5 5 0 0 0 0
27 1.0 2 3 5 5 0 0 0 0
27 0.25 0 0 5 5 0 0 0 0
28 0.5 0 0 4 5 0 0 0 0
30 1.0 0 0 2 2 0 0 0 0
EXAMPLE 7
The post-emergent herbicidal activity of the compounds of the invention formulated as described in
Example 5 was assessed by the following procedure.
The seeds of the test species were sown in rows 2 cm deep in soil contained in seed boxes. The monocotyledonous plants and the dicotyledonous plants were sown in separate seed boxes in duplicate.
The four seed boxes were placed in a glass house, lightly watered with an overhead spray to initiate germination and then sub-irrigated as required for optimum plant growth. After the plants had grown to a height of about 10 to 12.5 cm one box of each of the monocotyledonous plants and the dicotyledonous plants was removed from the glass house and sprayed with the required quantity of a composition of the invention. After spraying the boxes were returned to the glass house for a further 3 weeks and the effect of treatment was visually assessed by comparison with the untreated controls.The results are presented in
Table 2 where the damage to plants is rated on a scale of from 0 to 5 where 0 represents from 0 to 10% damage, 1 represents from 11 to 30% damage, 2 represents from 31 to 60% damage, 3 represents from 61 to 80% damage, 4 represents from 81 to 99% damage and 5 represents 100% kill. A dash (-) means that no experiment was carried out.
The names of the test plants are as follows:
Wh Wheat
Ot Wild Oats
Rg Ryegrass
Jm Japanese millet
P Peas
Ip Ipomea
Ms Mustard
Sf Sunflower
TABLE 2
TEST PLANT
Compound APPLICATION
No Rate(kg/ha)
Wh Ot Rg Jm P Ip Ms Sf
1 1.0 1 5 5 5 0 0 0 0
1 0.25 0 5 5 5 - - -
1 0.0625 0 1 4 3 - - -
2 1.0 1 5 5 5 0 0 0 0
2 0.25 0 3 2 4 - - -
27 1.0 - 5 4 5 0 0 0 0 27 0.25 0 4 5 5 28 0.5 0 3 5 5 0 0 0 0
28 0.125 0 0 4 3 0 0 0 0
29 1.0 0 4 2 3 0 0 0 0
30 1.0 3 4 4 4 D 0 0 0 30 0.25 1 4 3 4 - - -
31 1.0 0 4 3 3 0 0 0 0
EXAMPLE 8
The compounds were formulated fortest by mixing an appropriate amount with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.9 g per litre of "Span" 80 and 78.2 g per litre of "Tween" 20 in methylcyclohexanone to 500 ml with water. "Span" 80 is a Trade Mark for a surface-active agent comprising sorbitan monolaurate. "Tween" 20 is a Trade Mark for a surface-active agent comprising a condensate of sorbitan monolaurate with 20 molar proportions of ethylene oxide. Each 5 ml emulsion containing a test compound was then diluted to 40 ml with water and sprayed on to young pot plants (post-emergence test) of the species named in Table 3 below. Damage to test plants was assessed after 14 days on a scale of 0 to 5 wherein 0 isO to 20% damage and 5 is complete kill. In a test for pre-emergence herbicidal activity, seeds of the test plants were sown in a shallow slit formed in the surface of soil in fibre trays. The surface was then levelled and sprayed, and fresh soil then spread thinly over the sprayed surface.
Assessment of herbicidal damage was carried out after 21 days using the same scale of 0 to 5 as the post-emergence test. In both cases the degree of herbicidal damage was assessed by comparison with untreated control plants. The results are given in Table 3 below A dash (-) means no experiment was carried out.
The names of the test plants were as follows:
Mz Maize
Ww Winter wheat
Rc Rice
Br Barley
Av Avenafatua Dg Digitaria sanguinalis Al Alopecurus myosuroides
St Setaria viridis
Ec Echinochloa crus-galli
Sh Sorghum halepense
Ag Agropyron rep ends TABLE 3
TEST PLANT
Compound APPLICATION
No Method Rate
(kg/ha) Mz Ww Rc Br Av Dg Al St Ec Sh Ag
2 POST 0.4 4 0 4 1 4 3 1 4 4 4 0
2 POST 0.2 4 0 4 0 2 0 0 3 4 4 0
28 POST 0.5 5 2 4 - 5 4 4 4 5 5 2
28 POST 0.2 4 1 3 - 4 4 4 4 4 3 3
29 POST 2.0 4 0 2 - 4 4 4 4 5 4 1
29 POST 0.4 4 0 0 - 0 3 1 3 4 1 1
Claims (15)
1. Acompoundofformula I
wherein:
X, which may be the same or different, are independently selected from the group consisting of: halogen;
nitro; cyano; C1 to C6 alkyl; C1 to C6 alkyl substituted with a substituent selected from the group
consisting of halogen, nitro, hydroxy, C1 to C6 alkoxy and C1 to C6 alkylthio; C2 to C6 alkenyl; C2 to C6
alkynyl; hydroxy; C1 to C6 alkoxy; C1 to C6 alkoxy substituted with a substituent selected from halogen
and C1 to C6 alkoxy; C2 to C6 alkenyloxy; C2 to C6 alkynyloxy; C2 to C6 alkanoyloxy; (C1 to c6
alkoxy)-carbonyl; C1 to C6 alkylthio; C1 to C6 alkylsulfinyl; C1 to C6 alkylsulfonyl;
sulfamoyl; N-(C1 to C6 alkyl) sulfamoyl;N,N-di(C1 to C6 alkyl) sulfamoyl; benzyloxy; substituted
benzyloxy wherein the benzene ring is substituted with from one to three substituents selected from
the group consisting of halogen, nitro, C1 to C6 alkyl, C1 to C6 alkoxy and C1 to C6 haloalkyl; the group
NR5R6 wherein R5 and R6 are independently selected from the group consisting of hydrogen, C1 to c6
alkyl, C2 to C6 alkanoyl, benzoyl and benzyl; the groups formyl and C2 to C6 alkanoyl and the oxime,
imine and Schiff base derivatives thereof;
R1 is selected from the group consisting of: hydrogen; C1 to C6 alkyl; C2to C6 alkenyl;C2 to C6 alkynyl;
substituted C1 to C6 alkyl wherein the alkyl group is substituted with a substituent selected from the
group consisting of C1 to C6 alkoxy, C1 to C6 alkylthio, phenyl and substituted phenyl wherein the
benzene ring is substituted with from one to three substituents selected from the group consisting of
halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to C6 alkylthio; C1 to C6
alkylsulfonyl; benzenesulfonyl; substituted benzenesulfonyl wherein the benzene ring is substituted
with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C, to
C6 alkyl, C1 to C6 haloalkyl; C1 to C6 alkoxy and C1 to C6 alkylthio; an acyl group; and an inorganic or
organic cation; R2 is selected from the group consisting of:C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 haloalkenyl; C2 to C6
alkynyl; C2 to C6 haloalkynyl; substituted C1 to C6 alkyl wherein the alkyl group is substituted with a
substituent selected from the group consisting of halogen, C1 to C6 alkoxy, C1 to C6 alkylthio, phenyl
and substituted phenyl wherein the benzene ring is substituted with from one to three substituents
selected from the group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6
alkoxy and C1 to C6 alkylthio;
R3 is selected from the group consisting of: C1 to C6 alkyl, C1 to C6 fluoroalkyl; C2 to C6 alkenyl; C2 to C6
alkynyl; and phenyl;
R4 is selected from the group consisting of: hydrogen; halogen; cyano; C1 to C6 alkyl; and (C1 to C6
alkoxy)-carbonyl; and n is an integer chosen from 3 to 5.
2. A compound according to claim 1 wherein:
X, which may be the same or different, are independently selected from the group consisting of: halogen;
nitro; cyano; C1 to C6 alkyl; C1 to C6 alkyl substituted with a substitutent selected from the group
consisting of halogen, nitro, hydroxy, C1 to C6 alkoxy and C1 to C6 alkylthio; C2 to C6 alkenyl; C2 to C6
alkynyl; hydroxy; C1 to C6 alkoxy; C1 to C6 alkoxy substituted with a substituent selected from halogen
and C1 to C6 alkoxy; C2 to C6 alkenyloxy; C2 to C6 alkynyloxy; C2 to C6 alkanoyloxy; (C1 to C6
alkoxy)-carbonyl; C1 to C6 alkylthio; C1 to C6 alkylsulfinyl; Ct to C6 alkylsulfonyl; sulfamoyl;N-(C1 to C6
alkyl)- sulfamoyl; N,N-di(C, to C6 alkyl)sulfamoyl; benzyloxy; substituted benzyloxywherein the
benzene ring is substituted with from one to three substituents selected from the group consisting of
halogen, nitro, C1 toC6 alkyl, C1 to C6 alkoxy and C1 to C6 haloalkyl; the group NR5R6 wherein R5 and R6
are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, C2 and C6 alkanoyl,
benzoyl and benzyl; the groups formyl and C2 to C6 alkanoyl; and the groups of the formula -C(R7)=NR8 wherein R7 is chosen from hydrogen and C1 to C6 alkyl, and R8 is chosen from hydrogen,
C1 to C6 alkyl, phenyl, benzyl, hydroxy, C1 to C6 alkoxy, phenoxy and benzyloxy;
R1 is selected fro the group consisting of: hydrogen; C1 to c6 alkyl;C2 to C6 alkenyl; C2 to C6 alkynyl;
substituted C1 to C6 alkyl wherein the alkyl group is substituted with a substituent selected from the
group consisting of C1 to C6 alkoxy, C1 to C6 alkylthio, phenyl and substituted phenyl wherein the
benzene ring is substituted with from one to three substituents selected from the group consisting of
halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to C6 alkylthio; C1 to C6
alkylsulfonyl; benzenesulfonyl; substituted benzenesulfonyl wherein the benzene ring is substituted
with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C1 to
C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to C6 alkylthio;C2 to C6 alkanoyl; benzoyl, substituted
benzoyl wherein the benzene ring is substituted with from one to three substituents chosen from the
group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C, to C6 alkoxy and C1 to C6
alkylthio; 2-furoyl; 3-furoyl; 2-thenoyl; 3-thenoyl; and an organic or inorganic cation selected from the
alkai metal ions, the alkaline earth metal ions, the transition metal ions and the ammonium ion R9R10R11R'2N+ wherein R9, R10, R" and R12 are independently selected from the group consisting of:
hydrogen;C1 to C10 alkyl; substituted C1 to C10 alkyl wherein the alkyl group is substituted with a
substituent selected from the group consisting of hydroxy, halogen and C1 to C6 alkoxy; phenyl;
benzyl; and the groups substituted phenyl and substituted benzyl wherein the benzene ring is
substituted with from one to three substituents selected from the group consisting of halogen, nitro,
cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 alkoxy and C1 to C6 alkylthio;
R2 is selected from the group consisting of:C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 haloalkenyl; C2to C6
alkynyl; C2 to C6 haloalkynyl; substituted C1 to C6 alkyl wherein the alkyl group is substituted with a
substituent selected from the group consisting of halogen, C to C6 alkoxy, C1 to C6 alkylthio, phenyl
and substituted phenyl wherein the benzene ring is substituted with from one to threee substituents
selected from the group consisting of halogen, nitro, cyano, C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6
alkoxy and C1 to C6 alkylthio;
R3 is selected from the group consisting of:C1 to C6 alkyl; C1 to C6 fluoroalkyl; C2to C6 alkenyl; C2 to C6
alkynyl; and phenyl;
R4 is selected from the group consisting of: hydrogen; halogen; cyano; C1 to C6 alkyl; and (C1 to C6
alkoxy)-carbonyl; and n is an integer selected from 3 to 5.
3. A compound according to claim 1 or claim 2 wherein:
X, which may be the same or different, are independently selected from the group consisting of halogen,
C1 to C6 alkyl, C1 to C6 alkoxy and C2 to C6 alkanoyl;
R1 is selected from the group consisting of hydrogen, the alkali metals, ammonium, C1 to C10 alkylammonium, C2 to C6 alkanoyl, benzoyl and substituted benzoyl wherein the benzene ring is
substituted with from one to three substituents selected from halogen, nitro and cyano;
R2 is selected from the group consisting of methyl, ethyl, n-propyl, allyl and propargyl;
R3 is selected from the group consisting of methyl, ethyl and n-propyl;
R4 is selected from halogen and (C1 to C6 alkoxy)-carbonyl; and n is an integer selected from 3 to 5.
4. A compound according to any one of claims 1 to 3 inclusive offormula
wherein:
X2, X4, X6 and X, which may be the same or different are independently selected from the group consisting
of methyl, methoxy and acetyl;
R' is hydrogen;
R2 is ethyl;
R3 is selected from ethyl and n-propyl;
R4 is selected from fluoro and ethoxycarbonyl; and n is selected from zero and the integers 1 and 2.
5. A compound according to claim 4 wherein:
X2, X4, X6 and X are all methyl;
R1 is hydrogen;
R2 is ethyl;
R3 is selected from ethyl and n-propyl;
R4 fluoro; and n is selected from zero and the integers 1 and 2.
6. The compound 2-[1 -(ethoxyimino)butyl]-4-fluoro-3-hydroxy-5-mesitylcyclohex-2-en-1 -one.
7. A herbicidal composition comprising as active ingredient a compound as defined according to any one of claims 1 to 6 inclusive and a carriertherefor.
8. A process for severely damaging or killing unwanted plants which process comprises applying to said plants, or to the growth medium of said plants, an effective amount of a compound as defined according to any one of claims 1 to 6 inclusive or an effective amount of a composition as defined according to claim 7.
9. A process for selectively controlling the growth of monocotyledonous weeds in dicotyledonous crops which process comprises applying to said crop, or to the growth medium of said crop, a compound as defined according to any one of claims 1 to 6 inclusive or a composition as defined according to claim 7 in an amount sufficient to severely damage or kill said weeds but insufficient to substantially damage said crop.
10. A process according to claim 8 or claim 9 wherein the compound is applied at a rate in the range of from 0.005 to 20 kilograms per hectare.
11. A process for the synthesis of a compound of formula I as defined according to any one of claims 1 to 6 inclusive which process comprises reacting a 2-acyl-5-(aryl)cyclohexane-1 ,3-dione derivative of formula
XIII with an alkoxyamine derivative of formula XVII to give a compound of the invention of formula II or reacting the 2-acyl-5-(aryl)cyclohexane-1 ,3-dione derivative of formula XIII with hydroxylamine and alkylating the oxime intermediate of formula XVIII with an alkylating agent of formula XIX, wherein Lisa leaving group, to give a compound of the invention of formula II; ;
and, optionally, reacting the compound of the invention of formula II with a compound of formula XX, wherein Lisa leaving group, to give a compound of the invention of formula I.
12. A compound of formula I as defined according to any one of claims 1 to 6 inclusive substantially as herein described with reference to any one of Examples 1 to 4 inclusive.
13. A composition as defined according to claim 7 substantially as herein described with reference to any one of Examples 5 to 8 inclusive.
14. A process as defined according to any one of claims 8 to 10 inclusive substantially as herein described with reference to any one of Examples 6 to 8 inclusive.
15. A process as defined according to claim 11 substantially as herein described with reference to any one of Examples 1 to 4 inclusive.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPF940783 | 1983-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8412145D0 GB8412145D0 (en) | 1984-06-20 |
| GB2141427A true GB2141427A (en) | 1984-12-19 |
Family
ID=3770140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08412145A Withdrawn GB2141427A (en) | 1983-05-18 | 1984-05-11 | Herbicidal cyclohexane-1,3-dione derivatives |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2141427A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0202042A1 (en) * | 1985-05-06 | 1986-11-20 | Ici Australia Limited | Cyclohexane-1,3-dione derivatives, compositions containing them, processes for preparing them, and their use as herbicides and plant growth regulators |
| EP0211605A3 (en) * | 1985-08-08 | 1988-01-13 | Ici Australia Ltd | Herbicidal cyclohexane-1,3-dione derivatives |
| US4921524A (en) * | 1987-05-15 | 1990-05-01 | Shell Internationale Research Maatschappij B.V. | Oximino ether compounds |
| EP0450711A1 (en) * | 1990-03-30 | 1991-10-09 | Dowelanco | Substituted cyclohexanediones and their herbicidal uses |
-
1984
- 1984-05-11 GB GB08412145A patent/GB2141427A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0202042A1 (en) * | 1985-05-06 | 1986-11-20 | Ici Australia Limited | Cyclohexane-1,3-dione derivatives, compositions containing them, processes for preparing them, and their use as herbicides and plant growth regulators |
| EP0211605A3 (en) * | 1985-08-08 | 1988-01-13 | Ici Australia Ltd | Herbicidal cyclohexane-1,3-dione derivatives |
| US4921524A (en) * | 1987-05-15 | 1990-05-01 | Shell Internationale Research Maatschappij B.V. | Oximino ether compounds |
| EP0450711A1 (en) * | 1990-03-30 | 1991-10-09 | Dowelanco | Substituted cyclohexanediones and their herbicidal uses |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8412145D0 (en) | 1984-06-20 |
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| Date | Code | Title | Description |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |