CA1287837C - Herbicidal acylamino 5-mesityclclohexane-1,3-dione - Google Patents

Abstract

ABSTRACT

Herbicidal Acylamino 5-Mesitylcyclohexane-1,3-dione Derivatives The invention concerns novel compounds of the formula I

I

wherein:

Z is selected from hydrogen, alkyl, alkanoyl, sulfamoyl, carboxy and trifluoroacetamido;

Y is selected from various carboxy or thiocarboxy groups, haloalkanoyl, alkylsulfonyl and haloalkyl-sulfonyl;

R1 is selected from hydrogen, acyl and an inorganic or organic cation:

R2 is selected from alkyl, substituted alkyl, alkenyl, haloalkenyl and alkynyl R3 is selected from alkyl; and R4 is selected from hydrogen, alkyl, and alkoxy-carbonyl.

The compounds of the invention show herbicidal properties and plant growth regulating properties and in further embodiments and the invention provides pro-cesses for the preparation of compounds of formula I, intermediates useful in the preparation of the com-pounds of formula I, compositions containing as active ingredient a compound of formula I, and herbicidal and plant growth regulating processes utilizing compounds of formula I.

Description

TITLE

Herbicidal Acylamlno 5-Mesitylcyclohexane-1,3-dione Derivatives This invention relates ~o organic compounds hav-ing biological activity and in particular to organic compounds having herbicidal properties and plant growth regulating properties, to processes for the preparation of such compounds, to intarmediates useful in the preparation o such compounds ~nd to herbicidal compositions and processes utilizing such compounds and processes utilizing such compounds.
The use of certain c~clohexane-1,3-dione derivatives ~s grass herbicides is known.in the art.
For example, the "Pesticide Manual" (C R Worthing Editor, The Bri tish Crop Protection Council, 6th Edition 1979) describes the cyclohexane-1,3-dione derivative known co~mercially as alloxydim-sodium (methyl 3-~1-(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 464 655 and its equivalents such as UK Patent No 1 461 170 and US Pa~ent No 3 950 420.

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. . ' '' ' ~ ' ' " "; ' ' '',' ' ~ ~ . ' . ~ '' '' ' ', .
' .

A variety of herbicidal compounds containing 5-(substituted phenyl) cyclohexane-1,3-diones are des-cribed in the art. For example, French Patent 2,518l990, as well as the published British Patent application equivalent thereto, viz., No 2,116,544 describe various 5-(4-substituted phenyl) cyclohexane-1,3-diones and European Patent Application 085,529 describes various 5-(polysubstituted phenyl) cyclo-hexane-1,3-diones and their herbicidal properties.
It has now been found that a new group of cyclo-hexan-1,3-dione derivatives which have a 5-mesityl substituent which is in turn substituted with a particular kind of functionalized amino group, exhibit exceptionally high general grass-killing activity.
Accordingly the invention provides a compound of formula I

c~3 i ~ ~C

wherein Y is selected from the group consisting of:

Cl to C6 alkylsulfonyl; Cl to C6 haloalkylsulfonyl, C2 to C6 haloalkanoyl: R5Co and R5CS wherein R5 is selected from the group consisting of: hydroxy, Cl to C6 alkoxy, amino, Cl to C6 alkylamino and di(C
to C6 alkyl)amino;

' ' ' ' ,:
, . .

-P~37~

Z is selected from the group consisting of hydrogen, halogen, Cl to C4 alkyl, Cl to C4 alkanoyl, sulfamoyl, Cl to C4 alkylsulfamoyl, di(Cl to C4 alkyl)sulfamoyl, carboxy and trifluoroacetylamino, Rl is selected from the group consisti.ng of:
hydrogen; an acyl group; and an inorganic or organic cation;

R2 is selected from the group consisiing of:
Cl to C6 alkyl; C2 to C6 alkenyl; C2 to C6 halo~
alkenyl; C3 to C6 alkynyl; and substituted Cl to C6 alkyl wherein the alkyl group is sub~tituted with a substituent selected from the group consisting of halogen, phenyl, and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, and Cl to C6 alkyl;

R3 is selected from the group consisting of: Cl to C6 alkyl; and R4 is selected from the group consisting of:
hydrogen; Cl to C6 alkyl, and (Cl to C6 alkoxy) carbonyl.

When in the compound of formula I Rl is chosen from acyl the nature of the acyl group is not narrowly cri~ical. Although not intending to be bound by theory, it is believed that when Rl i9 acyl the acyl group may be removed in the plant by hydrolysis to give the corresponding compound of formula I in which Rl is hydrogen. Suitable acyl groups incIude:
alkanoyl, for example C2 to C6 alkanoyl; aroyl, for example benzoyl and substituted benzoyl wherein the benzene ring is ~ubstituted with from one to three ,:

.

P~3~7~;37 substituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 halo-alkyl, Cl to C6 alkoxy and Cl to C6 alkylthio.
When in the compound of formula I R1 is chosen from an inoryanic or organic cation the nature of the cation is not narrowly critical. Although not intend-ing to be bound by theory, it is believed that when is a cation the cation may be removed in the plant to give a compound of formula I wherein Rl 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 R6R7R8R9N~ wherein R6, R7, R8 and R9 are in-dependently chosen from the group consisting of:hydrogen; Cl to Clo alkyl; substituted Cl to Clo alkyl wherein the alkyl group is substituted with a sub-stituent chosen from the group consisting of hydroxy, halogen and Cl to C6 alkoxy; phenyl; benzyl; and the groups substituted phenyl and substituted benzyl w~lere-in the benzene ring is substituted with from one to three suhstituents chosen from the group consisting of halogen, nitro, cyano, Cl to C6 alkyl, Cl to C6 haloalkyl, Cl to C6 alkoxy and Cl to C6 alkylthio.
The compounds of the invention may exist in two isomeric forms as shown below, wherein 0 represents the group Z~ /CH3 CH ~3~

, . .
, .

12~ 3~

\ R3 0 ~ \ R3 Ia Id It ~hould be recognized that when Rl is hydrogen the compounds of the invention may exist in any one of four tautomeric forms as shown below where-in 0 represents the group CH3 ~ \ / ~
A

~ .
' ' ' ' " ~',, ' , ~" ' : .
-.',, ~ , : , .
~.
- - , ~ " ' ' . ~ .
, 37~

0 ~ C ~ _ p ~ \ R3 lIa IIb ~N-OR2 ~f ,~ N-OR2 \ R3 IIc IId Preferred compounds of the invention include those compounds of formula I wherein:

the substituent Y is chosen from the group trifluoro-acetyl, trifluoromethanesulfonyl, alkoxycarbonyl;
carbamoyl and N-alkyl(thio)carbamoyl;

Z is selected from hydrogen, methyl, C2 to C4 alkanoyl, halogen, sulfamoyl, dimethylsulfamoyl and trifluoro-acetylamino; :

Rl is selected from hydrogenj the alkali metal cations,C2 to C6 alkanoyl, benzoyl and substituted benzoyl wherein -the benzoyl ring is substituted with from one to three substituents chosen from halogen, nitro and cyano, ~ .
, , . . .: .

- - . .. , , . - .:

.:: : ~ . ' . . . : : .
: . .
.

7~

R2 is selected from the group consisting of Cl to C4 alkyl, C2 to C4 alkenyl, C3 to C4 alkynyl, Cl to C4 haloalkyl and C2 to C4 halo alkenyl;

R3 is selected from Cl to C6 alkyl; and R4 is hydrogen.

More preferred compounds of the invention include those compounds of formula I wherein;

Y is trifluoroacetyl, trifluoromethanesulfonyl or N-alkylcarbamoyl;

Z is selected from hydrogen, methyl or acetyl:

Rl is selected from hydrogen and the alkali metal cations;

R2 is selected from methyl, ethyl, n-propyl, allyl, propargyl and 3-chloroallyl;

R3 is selected from methyl, ethyl and n-propyl;

R4 is hydrogen.

Examples of compounds embraced by the invention include:

. . . . .. . . .
, .
, ':: ' ~ ' ' C) C~3 H 2 C~ 3 )~` \--6 CH2~3 .~
O

N-C)021~ =~ H--C I
~C (b) (CH3) 2NCNH t) H2NsO~ , O Na CH2~H2~
/ \ ~ ~2CH3 , .
(CH3 ) 2NC,NH
S

Specific examples of the compounds of the invention include those compounds detailed in Table 1 below.

CH3~ C~-OCH2~H3 o 2 3 ,-'' .

.. ' ' :. . : - :

~ ~3~7~337 Compound No Y Z

2 CONE~2 H

7 . Co(cF2)2cF3 H
8 . CoNH(cH2)2cH3 H

The compounds of the invention may be prepared by a variety of methods and in a ~urther aspect the in-vention provides methods for the preparation of com-pounds of formula I.
Conveniently the preparation of the invention can be considered in four or five parts.

Part A involves the formation of a 5-arylcyclo-hexan-1,3-dione of formula IX. This reaction may be carried out in a two step process by:

(i~ reacting, pref2rably in the presence of a base:, an aldehyde derivative of forrnula V with acetone ~IVa) or an acetone derivative of formula IVb to form a ketone derivative of formula V:Ia or VIb respectively: and reacting, preferably in the presence of a base, a ketone derivative of :

. . ` :

~ ~fi~3~7~3 7 formula VIa with a malonic acid ester derivative of formula ~JIIa or a ketone derivative of formula VIb with a malonic acid ester of formula VIIb, to give an intermediate of formula VIIIa or VIIIb 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.

~ii) 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 VIc which is in turn reacted, preferably in the presence of a base, with an acetoacetic acid ester derivative of formula VIIc to give an inter-mediate of formula VIIIa 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-acylcyclohexane-1,3-dione derivative of formula Xa. Alternatively Part B in-volves the acylation of a compound of formula VIIIa or VIIIb to give a 2-acy]cyclohexane-1,3-dione ~5 derivative of formula XIa or XIb respectiv ly which may be hydrolysed, preferably in the presence of a base, to give a 2-acylcyclohexane-1,3-dione of formula Xa. The acylation reaction may be carried out by re-acting a cyclohexane-1,3-dione~derivative of formula 30 VIII or IX with: -i) an acid anhydride of formula XII in the presence of either an alkali metal salt of the corres-ponding acid of formu1a XV or an alkoxide salt .
- . . -.
, . ' . . . ~ . , : , ' '''. "' ' ' ~

of formula XIV, wherein M is an alkali metal ion and R is Cl to C6 alkyl; or ii) an acid anhydride of formula XII in the presence of the corresponding acid of formula XV, pre-ferably in the presence of a Lewis acid or strong proton acid catalyst; or iii) with an alkali or alkaline earth metal hydride followed by reaction with an acid anhydride of formula XII or an acid halide of formula XVI:
or iv) an acid anhydride of formula XII in the presence of a strong organic base ~uch as 4-dimethyl-aminopyridine or imidazole.

Alternatively, this acylation reaction may be carried out by:

v) reacting a cyclohexane-1,3-dione derivative of formula VIII or ormula IX with an acid halide of formula XVI in the presence of a base to give an intermediate Q-acyl derivatiYe of the type of formula XVII; and vi) reacting the intermediate of formula XVII with a Lewis acid or strong proton acid catalyst; or vii) reacting the intermediate of formula XVII with a suitable strong organic base such as 4-~5 dimethylaminopyridine.

Part C involves the reaction of a compound of formula Xa by electrophilic aromatic nitration to give a compound of formula Xb which may readily be " . , . . :
~. .

, . ~ ' , , ~, -, ~ ~7~37~7 converted to a compound of formula Xc by reduction and N-acylation.

Part D involves the formation of a compound of the invention of formula I wherein Rl is hydrogen, that is a compound of formula II. This reaction may be carried out either by reacting a 2-acyl cyclohexane-1,3-dione of formula Xc with:

i) an alkoxyamine derivative of formula XVIII, or ii) hydroxylamine to give an intermediate oxime derivative of formula XIX and reacting that intermediate oxime derivative of formula XIX
with an alkylating agent of formula XX, wherein L is a leaving group such as, for example, chloride, bromide, iodide, sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoro-borate, hexafluorophosphate, hexafluoro-antimonate, methanesulfonate, fluorosulfonate, fluoromethanesulfonate and trifluoromethane-sulfonate.

Part E involves the formation of a compound of the invention of formula I wherein Rl is a substituent other than hydrogen.
Compounds of the invention of formula I, wherein Rl forms an acyl derivative of a compound of formula II, may be prepared from the corresponding compounds of the invention of formula II by reacting with an acylation reagent of formula XXI, wherein L is a leav-ing group preferably a halogen.
Compo1lnds of the invention of formula I wherein Rl is an inorganic or organic cation may be prepared from the compounds of the invention of formula I where~
in Rl is hydrogen, that is, compounds of formula II, by ' ' .

7~3~5~

reacting said compounds of formula II with an in-organic or organic salt. For example, the compounds of formula I wherein Rl is an alkali meta] ion ~ay be prepared by reacting the appropriate compound of formula II with the appropriate alkali metal hydroxide or alkoxylateO The compounds of formula I wherein is a transition metal ion or an organic cation may similarly be prepared by reacting the appropriate com-pound of formula II with an appropriate transition metal salt or organic base. Alternatively, the com-pounds of formula I wherein Rl is a transition me~al ion or an organic cation may be prepared by reacting the appropriate compound of formula I wherein Rl is an alkali metal 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 hereinbeore defined, which process com-prises:

reacting a 2~acylcyclohexane-1,3-dione deriva-tive of formula Xc with an alkoxyamine derivative of formula XVIII to give a compound of the invention of formula II or reacting the 2-acylcyclohexane-1,3-dione derivative of formula Xc with hydroxylamine and alkylating the oxime intermediate of formula XIX with an alkylating agent of formula XX, wherein L is a 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 XXI wherein L is a leaving group, to give a compound of the invention of formula I.

,: . ' : '`' , -,, , - ~ ,' ' ', ,:, ,, :
., , ~

Certain of the intermediate compounds of formula Xc, are novel compounds and therefore in further embodiments the invention provides novel compounds of formula Xc, and processes for the preparation thareof.
The structures of the compounds described above are detailed on the following pages.

oRl OH
~N-OR2 ~ ~rJ_oR2 I Il IVa IVb IVc . , ' : . ': -,. . ': ~ . ' ''. : ' . , ~ - , :
' ~
'' ~ ''; ' , ~', ' :

7~37 3 ~ CHO V
C~3 Z CH3 Z ~H3 3~CH=CH-COCHCH~H=CR COCH3 Vl a VIh ~ CH3 CH3--~~ CH=CH-C0 CH~

VIc R4CH ( CO2R) 2H2 ( C2R) 2 VIIa VIIb ., : , . . ':

. , ' ~ , . , ~

3~ 7 CH3CoCHR4Co2R VI:[c CH~ CH~

VIIIa VIIIb CH ~ ~ IX

X

' .. . . .. .

- . ~ --': '' , : .

37~

CH ~R3 Xb ~CH3 ~f CH ~< R3 Xc X I a CH3 o CH~ ~ R3 ~3 CO2R O

tR3co) 2 R3co ~M ROM

XI I XI I I XIV

R3Co2H R3COhal XV ~1 ,, .

-' : ' "' , . :

: ' ', , ' -t7~3~

CH ~ XVII

C 3 CoR3 H2NOR2 R2L RlL
:
XVIII XX XXI

R4 OH R4 OH ~ 0R2 N-O~

XIX II

The compounds of formula I are active as herbi-cides and therefore, in a further aspect the invention provides a process for severely damaging or killing un-wanted plants which process comprises applying to theplants, or to the growth medium of the plants, an effective amount of a compound of formula I as herein-before defined.
Generally speaking the compounds of formula I
are herbicidally effective against monocotyledono~s plants, dicotyledonous plants being r latively un-affected by rates of application of the compounds of , - , : . , : .
.

37~3~37 the invention which are severely damaging or lethal to most grass species.
Accordinyly, in yet a further aspect the in-vention provides a process for controlling mono~
cotyledonous weeds in cultivated crops, which process comprises applying to the crop, or to the growth medium of the crop, a compound of formula I, as here-inbefore 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 direc~ly 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, severly damage, or kill plants but are preferably used in the form o a com-position comprising a compound of the invention in ad-mixture with a carrier comprising a solid or liquid diluent. Therefore, in yet a further aspect the in-vention provides growth inhibiting, plant damaging, or plant killing compositions comprising a compound of formula I as 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 sele~tivity 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 mani-fested in a number of ways. For example, raising the sugar content of plants, suppression of apical dominance, stimulation of auxiliary bud growth, stimulation of - , - ' ' ' ~

3~337 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 o the invention may include, for example, tillering and stem shortening in crops such as wheat and barley, and increasing the sugar content of sugar cane.
Accordingly in a still further aspect the in-vention provides a process or regulating the growth of a plant which process comprises applying to the plant, to the seed of the plant, or to 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 applica-tio~) 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.
The compositions of the present invention may be in the form of solids, liquids or pastes. The com-positions include both dilute compositions which areready for immediate use and concentrated compositions which may require dilution beore use. Therefore, the concentration of the active ingredient in the com-positions o the present invention will vary depending on the types of formulation and whether the composi-tion is ready for use such as, for example, a dust .
. .

~ ~37~3;3~7 formulation or an aqueous emulsion or whether the composition is a concentrate such as, for example, an emulsifiable concentrate or a wettable powder, which is suitable for dilution before use. In general the compositions of the present invention comprise from 1 ppm to 99~ by weight of active ingredient.
The solid compositions may be in the form of powders, dusts, pellets~ grains, and granules wherein the active ingredient is mixed with a solid diluent.
Powders and dusts may be prepared by mixing or grinding the active ingredient with a solid carrier to give a finely divided composition. Granules, grains and pellets may be prepared by bonding the active ingred-ient to a solid carrier, for example, by coating or impregnating the preformed granular solid carrier with the active ingredient or by agglomeration techniques.
Examples of solid carriers include- mineral earths and clays such as, for example, kaolin, bentonite, kieselguhr, Fuller's earth, Attaclay, diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime, calcium carbonate, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicates and silica yels; fertilizers such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate and urea, natural products of vegetable origin such as, for example, grain meals and flours, bark meals, wood meals, nutshell meals and cellulosic powders; and synthetic polymeric materials such as, for example, ground or powdered plastics and resins.
Alternatively, the solid compositions may be in the form of dispersible or wettable dusts, powders, granules or grains wherein the active ingredient and the solid carrier are combined with one or more sur-face active agents which act as wetting, emulsifying and/or dispersing agents to facilitate the dispersion of the active ingredient in liquid.

, , , .. ,:
. . .. . . .
- , .
' ~
.

~r~7~37 Examples of surface active agents include those of the cationic, anionic and non-ionic type. Cationic surface active agents include quaternary ammonium com-pounds, or example, the long chain alkylammonium salts such as cetyltrimethylammonium bromide. Anionic surface active agents include: soaps or the alkali metal, alkaline earth metal and ammonium salts of fatty acids;
the alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of aryl-sulfonic acids including the salts of naphthalene-sulfonic acids such as butylnaphthalenesulfonic acids, the di- and tri- isopropylnaphthalene-sulfonic acids, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives wi~h formaldehyde, the salts of the con-densation products of sulfonated naphthalene and naphthalene derivatives with phenol and formaldehyde, and the salts of alkylarylben7enesulfonic acids such as dodecylbenzenesulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of the long chain mono esters of sulfuric acid or alkylsulfates such as laurylsulfate and the mono esters of sulfuric acid with fatty alcohol glycol ethers. Nonionic sur-face active agents include: the condensation productsof ethylene oxide with phenols and alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the condensation products of ethylene oxide with castor oil; the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate, and their condensation products with ethylene oxide; ethylene oxide/propylene oxide block copolymers; lauryl alcohol polyglycol ether acetal;
and the lecithins.
The liquid compositions may comprise a 901u-tion or di6persions of the active ingredient in a .

. ' ~ . .

~ ~r~37~3~7 liquid carrier optionally containing one or more sur-face active agents which act as wetting, emulsifying and/or dispersing agents. Examples of liquid carriers include: water, mineral oil fractions such as, for example, kerosene, solvent naphtha, petroleum, coal tar oils and aromatic petroleum fractions; aliphatic, cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin, cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylated naphthalenes;
alcohols such as, for example, methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and propy-lene glycol; ketones such as, for example, cyclo-hexanone and isophorone; and strongly polar organic solvents such as, for example, dimethylformamide, dimethylsulfoxide, ~-methylpyrrolidone and sulfolane.
A preferred liquid composition comprises an aqueous suspension, dispersion or emulsion of the active ingredient which is suitable for application by spraying, atomizing or watering. Such aqueous com-postions are generally prepared by mixing concentratedcomposi~ions with water. Suitable concentrated com-positions include emulsion concentrates, pastes, oil dispersions, aqueous suspensions and wettable powders.
The concentrates are usually required to withstand storage for prolonged periods and after such storage to be capable of dilution with water to form aqueous pre-parations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates conveniently contain from 10 to 99%, preferably 10 to 60~, by weight of active ingredient.
Emulsion or emulsifiable concentrates are con-veniently prepared by dissolving the active ingredient in an organic solvent containing one or more surface active agents and optionally an oil. Oil disper~ions may be prepared by grinding together the active in-.
' .' ' , ' ' ," . ' , ' , ~' '', ' "' , ' ' ' ~I ?~r^37~3~

gredient, a hydrocarbon oil, and one or more surface active agents. Aqueous suspension concentrates may conveniently be prepared by ball milling a mixture of the active agent and preferably at least one suspending agent. Suitable suspending agents include:
hydrophilic colloids such as, for example, poly(N-vinylpyrrolidone), sodium carboxymethylcellulose and the vegetable gums, gum acacia and gum tragacanth;
hydrated colloidal mineral silicates such as, for ex-ample, montmorillonite, beidellite, nontronite,hectorite, saponite, sauconite and bentonite; other cellulose derivatives; and poly(vinyl alcohol). Wett-able powder concentrates may conveniently be prepared by blending together the active ingredient, one or more surface active agents, one or more solid carriers and optionally one or more suspending agents and grinding the mixture to give a powder having the required particle size.
The aqueous suspens.ions, dispersions or emulsions may be prepared from the concentrated com-positions by mixing the concentrated compositions with water optionally containing surface active agents and/or oils.
It should be noted that the compounds of the invention of formula I wherein Rl is hydrogen are acidic. Therefore, the compounds of formula I may be formulated and applied as the salts of organic or inorganic bases. In formulating and employing the com-pounds of formula I in the form of their salts either the salts per se, that is the compounds of formula I whereîn Rl is an inorganic or an organic cation, may be used in the formulation or the compounds of formula I wherein Rl is hydrogen may be used in the formulation and the salts generated in situ by the use of the appropriate organic or inorganic base.
The mode of application of the compositions of ,, . . ~

,. . .
.. .

the invention will depend to a large extent on the type of composition used and the facilities available for its application. Solid compositions may be applied by dusting or any other suitable means for broadcasting or spreading the solid. Liquid compositions may be applied by spraying, atomizing, watering, introduction into the irrigation water, or any other suitable means for broadcasting or spreading the liquid.
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 whose growth is to be inhibited the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however~ an application rate of from 0.005 to 20 kilograms per hectate is suitable while from 0.01 to 5.0 kilograms per hectare may be pre~
ferred.
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 herein-before indicated the compounds of the invention are in general substantially more effective against mono-cotyledonous plants or grass species than against di-cotyledonous plants or broad-leaved species. As a result, in certain applications the h~rbicidal use of the compounds of the invention alone may not be sufficient to protect a crop. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula I as herein-before defined with at least one other herbicide.
The other herbicide may be any herbicide not having the formula I. It will generally be a herbicide having a complementary action. For example, one pre-. .

ferred class is of mixtures comprising a herbicide active against broad-leaved weeds. A second preferred class is of mixtures comprising a contact herbicide.
Examples of useful complementary herbicides S include.

A. benzo-2,1,3,-thiadiazin-4-one-2,2-dioxides ~uch as 3-isopropylbenzo-2,1,3~thiadiazin-4-one-2,2-dioxide ~common name bentazon);

B. hormone herbicides and in particular the phenoxy-alkanoic acids such as 4-chloro-2-methylphenoxy acetic aoid ~common name MCPA), 2-(2,4-dichloro-phenoxy)propionic acid ~common name dichlorprop), 2,4-dichlorophenoxy acetic acid ~common name 2,4,-D) 2,4,5-trichlorophenoxyacetic acid ~common name 2,4,5-T~, 4-(4-chloro-2 methylphenoxy)butyric acid ~common name MCPB), 4-~2,4-dichlorophenoxy)butyric acid (common name 2,4-DB), 2-~4-chloro-2-methyl-phenoxy)propionic acid ~common name mecoprop), and their derivatives ~eg salts, ester~, amides and the like);

C. 3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as 3-t4-~4-chlorophenoxy)phenyl] l,l-dime~hylurea (common name chloroxuron);

D. dinitrophenols and their derivatives (eg acetates) such as 2-methyl-4,6-dinitrophenol (common name D~OC), 2-tertiarybutyl-4,6-dintrophenol (common name dinoterb), 2-secondarybutyl-4,6~dinitrophenol (common name dinoseb) and its ester dinoseb acetate;

E. dinitroaniline herbicides such as N',N'-diethyl-2,6-dinitro-4-trifluoromethyl-_-phenylenediamine - - . . : ...... :. . . . .
.
. ~
' ~ . :, . ,, ' ~ ., .
' .3~3~

(common name dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline (common name tri-fluralin) and 4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin~;

F. phenylurea herbicides such as N'-(3,4-dichloro-phenyl)-N,N-dimethylurea (common name diuron) and N,~-dimethyl-N'-[3-(trifluoromethyl)phenyl~ urea (common name fluometuron), G. phenylcarbamoyloxyphenylcarbamates such as 3-[tmethoxycarbonyl)amino]phenyl (3-methylphenyl)-carbamate (common name phenmedipham) and 3-~(ethoxycarbonylamino]phenyl p~enylcarbamate (common name desmedipham~;

H. 2-phenylpyridazin-3-ones such as 5-amino-4-chloro-2-phenylpyridazin-3-one (common name pyrazon);

I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (common name lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil) and 3-tert-butyl-5-chloro-6-methyluracil (co~non name t~rbacil);

J. triaæine herbicides such as 2-chloro~4-ethylamino-6-(1~o-propylamino)-1,3,5-triazine (common nam~
atrazine). 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common name simazine) and 2-azido-4-(iso-propylamino)-6-methylthio-1,3,5-triazine (common name aziproptryne);

K. l-alkoxy-2-alkyl-3-phenylurea herbicides such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron~, 3-(4-chlorophenyl)-1-:., , 2~37~3~3~

methoxy-l-methylurea Icommon name monolinuron) and 3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common name chlorobromuron);

L. Pyridine herbicides such as 3,6-dichloropicolinic acid (common name clopyralid) and 4-amino-3,5,6-trichloropicolinic acid (common name picloram);

M. 1,2,4-triazin-5-one herbicides such as 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (common name metamitron) and 4-amino-6-tert-butyl 4,5-dihydro-3-methylthio-1,3,4-tria2in-5-one (common name metribuzin), N. benzoic acid herbicides such as 2,3,6-trichloro-benzoic acid (common name 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common name dicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben);

0. anilide herbicides such as N-butoxymethyl- -chloro-2',6'-diethylacetanilide (common name butachlor), the corresponding N-methoxy compound (common name alachlor), the corresponding N-iso-propyl compound (common name propachlor) and 3',4'-dichloropropionanilide (common name propanil);

P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile (common name dichlobenil), 3,5-dibromo-4-hydroxyben7.onitrile (common name - -bromoxynil) and 3,5-diiodo-~-hydroxybenzonitrile ~common name ioxynil);

Q. haloalkanoic he bicides such a~ 2,2-dichloro-propionic acid ~common name dalapon), trichloro-- : . ' ., ~ ' , .

.

3~2~ 337 acetic acid (common name TCA) and salts thereof;

R. diphenylether herbicides such as 4 nitrophenyl 2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate tcommon name bifenox), 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether, S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as ~-chloro-N-[(4-methoxy-6-methyl-1,3,5 triazin-2-yl)aminocarbonyl]benzenesulfonamide (commonly known as DPX 4189);

T. Aryloxyphenoxypropionate herbicides such as butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy~
propionate (common name flua~ifop) and methyl 2-t4-(2,4-dichlorophenoxy)phenoxy]propionate (common name diclofop); and U. miscellaneous herbicides including N,N-dimethyl-diphenylacetamide (common name diphenamid), N-(l~
naphthyl)phthalamic acid (common name naptalam) and 3-amino-1,2,4-tria~ole.

Examples of useful contact herbicides include:

. bipyridylium herbicides such as those in which the active entity is the l,l'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and those in which the active entity is the l,l'-ethylene-2,2'-dipyridylium ion:~common name diquat), W. organoarsenical herbicides such as monosodium methanearsonate (common name MSMA); and ' , .. ..

37t337 X. amino acid herbicides such as N-(phosphonomethyl)-glycine (common name glyphosate) and its saltc and esters.

The invention is now illustrated by, but in no way limited to, the following Examples.

The invention is now illustrated by but in no way limited to the following Examples.

Example 1 2-tl-(Ethoxylmino)propyl]-3-hydroxy-5-~3-methane-10 sulfonamido-2,4,6-trimeth~lphenyl]cyclohex-2-en-1-one (1) i) A solution of fuming nitric acid (2.17 ml), glacial acetic acid (1 98 ml) and acetic anhydride (1.94 ml) was added dropwise to a solution of 2-propionyl-3-hydroxy-5-mesityl-cyclohex-2-en-1-one (10 g, 34.9 mmol) in acetic anhydride (23.3 ml) at 5. Stirring was con-tinued at 5 for 1 hr, then at 20 for 2 hr and 50 for 10 min. The mixture was then cooled and pourea into ice water. The aqueous solution was extracted with methylene chloride. The organic layer was washed with water; saturated sodium bicarbonate solution and then further water, dried over anhydrous sodium sulfate and con-centrated under reduced pressure to yield 2-propionyl-3-hydroxy-5-(3-nitro-2,4,S-trimethyl-phenyl)cyclohex-2-en-1-one as a pale yellow solid (9,59 g, 83%). The compound was characterized by proton magnetic resonance spectroscopy (CDC13; ~ in ppm): 1.15 (3H,t), 2.18 (3H,s~; 2.24 (3E~,s); 2.38 (3H,s); 2.4-4.1 .

3~7~337 (7H,m); 6.88 (lH,s); 18.20 (lH,s).

ii) Sodiu~ dithionite (27.74 g, 159 mmol~ was added over a period of 30 min to a refluxing solution of 2-propionyl-3-hydroxy-5-(3-nitro-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (9.59 g, 28.9 mmol) and sodium hydroxide (1.10 g, 27.5 mmol) in 50% aqueous ethanol (350 ml). Re-fluxing was continued for 1 hr. The hot mixtur~ was filtered, neutralized with dilute hydrochloric acid and extracted with methylene chloride. The organic layer was washed with water, dried ov~r anhydrous magnesium sulfate and evaporated under reduced pressure to yield the crude 2-propionyl-3-hydroxy-5-(3-amino-2,4,6-trimethylphenyl)cyclohex-2-en-1-one as a brown oil (3.0 g, 34~). The compound was characterized by proton magnetic resonance spectroscopy (CDC13; S in ppm): 1.17 (3H,t);
2.12 (3H,s); 2.20 (3H,s); 2.25 (3H,s); 2.3-4.2 (7H,m); 6.72 (lH,s).

iii) Pyridine (0.53 ml, 6.6 ~nol) followed by methane sulfonyl chloride (0.52 ml, 6.6 mmol) was added to a stirred solution of 2-propionyl-3-hydroxy-5-(3-amino-2,4,6-trimethylphenyl)-cyclohex-2-en-1-one (1.0 g, 3.3 mmol)in methy-lene chloride (10 ml). Stirring was continued at 20 for 8 hr. The organic layer was washed with water, dilute hydrochloric acid and further water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to yield the crude product. The crude material was purified by column chromatography on silica gel (elution with an increasing gradient of methanol in methylene chloride) to give 2-propionyl-3-, -: , ' .: . ' ' ' ' ' ~ '. . . ' .

3~

hydroxy-5-(3-methylsulphonamido-2,4,6-trimethyl-phenyl)cyclohex-2-en-1-one as a yellow waxy solid (0.6 g, 50%). The compound was characterized by proton magnetic resonance spectroscopy (C~C13, ~ in ppm): 1.17 (3H,t), 2.35 (6H, s); 2.46 ~3H,s); 3.0 (3H,s); 2.4-4.1 (7H,m); 6.78 (lH,s):
6.89 (lH,s); 18.15 (lH,brs).

iv) Sodium acetate (0.19 g, 2.29 mmol) and ethoxyamine hydrochloride (0.22 g, 2.29 mmol~
were added to a solution of 2-propionyl-3-hydroxy-5-(3-methylsulphonamido-2,4,6-tri-methylphenyl)cyclohex-2-en-1-one (0.58 g, 1.53 mmol) in ethanol (25 ml) and methylene chloride (25 ml). Stirring was continued at 20 for 18 hrs. The solvent was removed under reduced pressure and the residue partitioned between chloroform and water. The organic layer was washed with water, dried over anhydrous mag-nesium sulfate and concentrated under reduced pressure to yield 2-[1-(ethoxyimino)propyl~-hydroxy-5-~3-(methylsulphonamido)-2,4,6-tri~
methylphenyl]cyclohex-2-en-1-one as a brown oil (0.27 g, 42%). The compound was characteri-zed by proton magnetic resonance spectroscopy.
The spectroscopic data are recorded in Table 2.

Example 2 2-[l~(Ethox~imino)propyl~-3-h~droxy-5-(3-ethylthio-ureido-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (3) .
i) Ethylisothiocyanate (0.35 g, 3.98 mmol) was added to a solution of 2-propionyl-3-hydroxy-5-(3-amino-2j4,6-trimethylphenyl)cyclohex 2-en-1-one (1.0 ~, 3.32 mmol) in ethanol (5 ml).

, .

. ~ . : ::, .

Stirring was continued at 20 for 4 days. Dilute acid and methylene chloride were added. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated.
The crude product was purified by chromatography on silica gel (elution with an increasing gradient of methanol in methylene chloride) to yield 2-propionyl-3-hydroxy-5-(3-ethylthio-ureido-2,4~6-trimethylphenyl)cyclohex-2-en-1-one as an oil (0.4 g, 33%). The compound was characterized by proton magnetic resonance spectroscopy (CDC13, ~ in ppm): 1.12 (6H,t);
2.18 (3H,s); 2.28 (3H,s); 2.39 (3H,s); 2.4-4.2 (9H,m); 5.4 (lH,brs), 6.29 (lH,s); 8.34 (lH,brs).

lS ii) 2~ ethoxyimino)propyl-3-hydroxy-5-(3-ethyl-thioureido-2,4,6-trimethylphenyl)cyclohex-2-en-1-one was prepared from the above compound as des-cribed in ~xample 1, part (iv). The compound was characterized by proton magnetic resonance spectroscopy and the spectroscopic data are re-corded in Table 2.

Example 3 2-[1-(Ethoxyimlno)propyl]-3-hydroxy-5-(3-ureido-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (2) 25 ~i) A solution of potassium cyanate (0.54 g, 6.S6 mmol) in water (3 ml) was added cautiously to a solu tion of ~-propionyl-3-hydroxy-5-(3-amino-2, 4,6-trimethylphenyl)cyclohex-2-en-1-one (1.0 g, 3.3~ mmol) in acetic acid (9 ml~ and water (3.2 ml). Stirring was continued for 1 hr then allowed to stand for 15 hr. Water and ethyl ace~ate were added. The organic layer was ,; . ~ , ,- , .. . . . .
,, ~ , , . , ' . , . ' ' .
.
. . . : ~. : . :. , -, ,. . : .

3~7~33~

washed with water, dried over anhydrous maynesium sulfate and evaporated under reduced pressure to yield 2~propionyl-3-hydroxy-5-(3-ureido 2,4,6-trimethylphenyl)cyclohex-2-en-1-one aa a brown semi solid (0.96 g, 84%). The compound was characterized by proton magnetic resonance spectroscopy (CDC13, ~ in ppm): l.ll (3H,t);
2.20 (3H,s~; 2.32 (6H,s); 2.4-4.1 (7H,m);

5.12 (2H,brs) 6.82 (lH,s), 7.25 (lH,brs).
lO ii) 2-Cl-(Ethoxyimino)propyl]-3-hydroxy-5-(3-ureido-2,4,6-trimethylphenyl)cyclohex-2-en-l-one was prepared from the corresponding trione as described in Example 1, part (iv). The com-pound was characterized by proton magnetic resonance spectroscopy and the spectroscopic data are recorded in Tab}e 2.

Example_4 2-[1-(Ethoxyimino)~ropyl]-3~hydroxy-5-(3-trifluoro-acetamido~2,4,6-trimethylphenyl)cy~lohex-2--en-1-one (4) i) A solution of 2-propionyl-3-hydroxy-5-(3-amino-2,4,6-trimethylphenyl~cyclohex-2-en-l-one (0.5 g, 1.66 mmol) in trifluoroacetic anhydride (2 ml) was stirred at 20~ for 48 hr. Water was then added and the aqueous layer extracted with chloroform. The organic layer was washed ex-tensively with water, dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromato-sraphy on silica gel (elution with an increasing gradient of ethylacetate in dichloromethane) to yield 2 propionyl-3-hydroxy-5-(3-trifluoro-acetamido-2,4,6-trimethylphenyl)cyclohex-2-en-,, ~ , ~, ~ ' ' ' ' 7~ 7 l-one as a yellow solid (0.29 g, 44%). The com-pound was characterized by proton magnetic resonance spectroscopy (CDC13, ~ in ppm): 1.16 (3H,t), 2.16 (3H,s); 2.21 (3H,s); 2.26 t3H,s);
2.4-4.1 (7H,m); 6.89 (lH,s); 8.50 (lH,s); lB.15 (lH,s).

ii) 2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(3-tri-fluoroacetamido-2,4,6-trimethyl~henyl)cyclohex-2-en-1-one was prepared from the above precursor as describ~d in Example 1, part (iv). The com-pound was characterized by proton magnetic resonance spectroscopy and the spectroscopic data are recorded in Table 2.

Example 5 2-Cl-(Ethoxyimino)propyIJ-3-hydroxy-5 [3-acetyl-5-trifluoroacetamido-2,4,6-trimethylphenyl~cyclohex 2-en-l-one (5) i) 2--Propionyl-3-hydroxy-5-~3 acetyl-5-nitro-2,4,6-trimethylphenyl]cyclohex-2-en-1-one was prepared from 2-propionyl-3-hydroxy-5-~3-acetyl-~,4,6 trimethy]phenyl]cyclohex-2 en-l-one. The compound was characterized by proton magnetic resonance spectroscopy (CDC13, S in ppm); 1.14 (3H,t); ~.08 (3H,s); 2.29 (6H,s); 2.46 (3H,s);
3.03 (2H,q); 2.4-4.1 (5H,~); lB.00 (lH,s).

ii) A stirred solution of 2-propionyl-3-hydroxy-5-[3-acetyl-5-nitro 2,4,6-trimethylp~enyl]cyclo-hex-2-en-1-one (4.2 g, 11.3 mmol) and 60dium methoxide (0.61 g, 11.3 mmol) in methanol (80 ml) was hydrogenated at atmospheric pressure over 10% palladium on charcoal (0. 3 g). After ., , ; ' uptake of hydrogen ceased the solution was neutralized and the methanol was removed under reduced pressure. The residue was partitioned between water and methylene chloride. The organic layer was washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The crude product was puri-fied by chromatography on silica gel (elution with an increasing gradient of methanol in methylene chloride) to yield 2-propionyl-3-hydroxy-5-(3-acetyl-5-amino-2,4,6-trimethyl-phenyl)cyclohex-2-en-1-one as a red brown solid (3.28 g, 85%) the compound was characterized by proton magnetic resonance spectroscopy (CDC13/ ~ in ppm): 1.18 (3H,t); 2.0 (3H,s);
2.12 (3H,s); 2.18 (3H,s); 2.40 (3H,s); 2.4-4.1 (5H,m); 3.07 (2H,q); 3.6 (2H, brs); 18.05 (lH,brs).

iii) A solution of 2-propionyl-3-hydroxy-5-(3-acetyl-5-amino-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (0.46 g, 1.34 mmol) in trifluoroacetic anhydride (2 ml) was stirred at 20 for 1 hr.
Water and ether were then added. The organic layer was washed extensively with water, once with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate and con-centrated under reduced pressure. The crude product was purified by chromatography on silica gel (elution with 10% ethyl acetate in methyIene chloride) to yield 2-propionyl-3-hydroxy-5-(3-acetyl-5-trifluoroacetamido-2,4,6-trimethyl-phenyl)cyclohex-2-en-1-one as a brown solid tO.37 g, 63%). The compound was characterized ~ by proton magnetic resonance ~pectroscopy (CDC13, ~ in ppm): 1.12 (3H,t~ 73 (3H,s);
' ' , , : : . ' .
.

.

2.22 (3H,s); 2.26 (3H,s), 2.46 (3H,s); 2.4-4.1 (5H,m); 3.08 (2H,q); 9.29 ~lH,s~; 18.33 ~lH,s).

iv) 2-~1-(Ethoxyimino)propyl]-3-hydroxy-5-[3-acetyl-5-trifluoroacetamido 2,4,6-trimethyl-phenyl3cyclohex-2-en-1-one was prepared from the corresponding compound detailed above as described in ~xample 1, part (iv). The com-pound was characterized by proton magnetic resonance spectroscopy. The spectroscopic data are reported in Table 2.

Example 6 Compounds Nos 8 and 11 were prepared by a similar procedure to that described in Example 2 and starting with the appropriate isocyanate. The compounds were characterized by their behaviour on thin-layer chromatography and their proton magnetic resonance spectra. The spectroscopic data is summarized in Table 2, Example 8 below.

Example 7 Compounds Nos 6, 7, 9 and 10 were prepared by a similar procedure to that described in Example 4 and starting with the appropriate acyl or sulfonic anhydride.
The compounds were each characterized by their proton magnetic resonance spectra, together with their behaviour on thin-layer chromatography. The spectroscopic data is summarized in Table 2, Example 8 below.

Example 8 The majority of the compounds of the invention were obtained as oils and were characteri~ed by, and . .
.~ , ' ' ' ' , ' . .

can be identified by, their nuclear magnetic resonance spectra. For convenience proton nuclear magnetic resonance (pmr) spectroscopic data is recorded in Table 2 below.

Compound Proton Chemical Shift No Appearance ~ in ppm ~CDC13) 1 brown oil 1.18(3H,t); 1.33(3H,t); 2.35 (6H,s); 2.44(3H,s); 3.04(3H, s); 2.4-4.2(7H,m); 4.13(2H,q);

6.85(1H,s); 6.92 (lH,s)~

2 brown solid 1.18(3H,t); 1.33(3H,t); 2.19 (3H,s); 2.35(6H,s); 2.4-4.2 (7H,m); 4.13(2H,q); 5.12(2H, brs); 6.89(1H,s); 7.3(1H,brs).

3 pale yellow 1.0-1.42(9H,m~; 2.20(3H,s);
solid/foam 2.31(3H,s); 2.40(3H,s);
2.4-4.20(9H,m); 4.13(2H,q);
5.32(1H,brs); 6.98(1H,s);
8.19(1H,brs).

4 yellow oil 1.20(3H,t); 1.27~3H,t); 2.11 (3H,s); 2.17(3H,s); 2.20(3H, s); 2.40-3O90~7H,m); 4.12 (2H,q); 7.85(1H,s); 9.85(1H, s).
.
__ __ ''-, ': '' ' ' ' :

~ 7 TABLE 2 Continued Compound Proton Chemical Shift No Appearance ~ in ppm ~CDC13) yellow/ 1.19(3H,t); 1.34(3H,t~; 1.83 brown solid (3H,s); 2.16(3H,s); 2.22(3H, s); 2.44(3H,s); 2.4-4.1(5H, m): 2.94(2H,q); 4.13(2H,q);
9.86~1H,s); 15.37(1H,brs).

6 white solid 1.20(3H,t); 1.34(3H,t); 2.21 (3H,s); 2.29(3H,s); 2.35 (3H,s); 2.4-3.9(7H,m~; 4.13 (2H,q); 6.95( lH,s); 8.30 (lH,m), 15.0(lH,b) 7 yellow-brown 1.19(3H,t); 1.34(3H,t); 2.11 solid (3H,s): 2.15(3H,~); 2.18 (3H,s); 2.2-3.9(7H,mj; 4.12 ~2H,q); 6.88(1H,s); 9.8 (lH,8); 15.2(1H,b) 8 pale brown 0.82(3H,t); 1.0-1.5(8H,m):
foam 2.18(3H,s); 2.33(6H,s); 2.3 3.9(9H,m); 4.13(2H,q~; 4.6 (lHjbs); 6.6(1H,s); 6.89 (lH,s); 15.0(1H,bs) ' ' . , - ~ . . . . . .
~ ~ .
. ',. ' ' , ~
- . . ~
- . .. . .

TABLE 2 Continued -_ Compound Proton Chemical Shift No Appearance ~ in ppm (CDC13) ~_ .

9 pale yellow 1020(3H,t); 1.34(3H,t~;
oil 2.25~9H,bs~; 2.3-3~9(7H,m);
4.12(2H,q); 6.90(lH,s) 9.1(1H,s); 15.4(1H,bs) pale brown 1.19(3H,t); 1.34(3H,t); 2.15 foam ~9H,s): 2.2-3.8(7H,m); 4.12 (2H,q~; 6.88(1H,s) 9.83 (lH,s); 15.4(1H,bs) 11 pale brown 1.19(3H,t); 1.33(3H,t); 2.18 foam (3H,s): 2.31(3H,s); 2.36 (3H,s) 2.3-4.0(7H,m) 2.72~3H,d); 4.13(2H,q);
4.5(lH,bs); 6.62(lH,s);
6.90(1H,s); 15.0 (lH,b) .. . . _ .

Example 9 This non-limiting Example illustrates the pre-paration of formulations of the compounds of the in-ven~ion.

a) Emulsifiable Concentrate Compound No 2 was dissolved in toluene containing 7% v/v "Teric" ~13 and 3~ v/v "Kemmat" SC15B to '' .: . ;
", 3t~33~

give an emulsifiable concentrate which may be di-luted wi~h wat0r 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, I'Kemmat'' is a Trade Mark ana "Kemmat" SC15B is a formulation of calcium dodecylbenzenesulfonate.) b) A~ueous Suspension Compound No 8 t5 parts by weight and "Dyapol" PT
(1 part by weight) were added to a 2% aqueous solu-tion (94 parts by weight) of "Teric" ~8 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 sus-pension which may be diluted with water to the re-quired concentration to give an a~ueous suspension which may be applied by spraying.

("Dyapol" is a Trade mark and "Dyapol" PT is an anionic suspending agent; "Teric" N8 is a product of ethoxylation of nonylphenol.) i c~ Emulsifiable Concentrate _ Compound No 2 (10 parts by weight), "Teric" N13 (5 parts by weight~ and "Kemmat" SC15B (5 parts by weight) were dissolved in "Solveseo" 150 (80 parts by weight) to give an emulsifiable concentrate which may be diluted with water to the required concentration to give an a~ueous emulsion which may be applied by spraying.

.. : - - :
''.' ' -. .
- ' ~ : ' !, . ~ , .
' ~ ~7~37 ~"Solvess~" is a Trade Mark and "Solvesso" 150 is a high boiling point aromatic petroleum fraction.) d) Dispersible Powder Compound No l tl0 parts by weight), "Matexil" DA/AC
(3 parts by weight), "Aerosol" OT/B (l part by weight) and china clay 298 (86 parts by weight) were blended and then milled to give a powder com-position 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" i5 a Trade Mark and "Aerosol" OT/B is a formulation of the dioctyl ester of sodium sulfosuccinic acid.) e) Dusting Powder Compound No l (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 essen-tially 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 10 to 12, in the evaluation of the pre-emergence and po~t-~mergence herbicidal activity of the compounds~

. ' , .
' ' ' ' ' , ' : ' ' -. .
, ~l2.~37~

Exam~le 10 The pre-emergent herbicidal activity of the compounds of the invention formulated as described in Example 9 was assessed by the following procedure:

The seeds of the test species were sown in rows 2 cm deep in 50il contained in seed boxes. The mono-cotyledonous plants and the dicotyledonous plants were sown in separate boxes and after sowing the two box~s were sprayed with the required quantity of a com-position 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 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 three weeks the boxes were removed from the glass house and the effec-t of the treatment was visually assessed. The results are pre-sented in Table 3 where the damage to plants i5 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% damaye, 3 represents from 61 to 80% damage, 4 represents from 81 to 99% damage and 5 reprsents 100% kill. A dash (-) means that no experi-ment was carried out.

The names of the test plants are as follows:

Wh Wheat Ot Wild Oats Rg Ryegrass Jm Japanese millet B Barley P Peas :

,. '' ' ' ', ., " ' ,' , , , . : . ' ' . ' . , . : , ';~' -- ' ' ' . ' ' ," ~ ' ' "' ;

-- 4~ --Ip Ipomea Ms Mustard Sf Sunflower Pre-emergent Herbicidal Activity Appli- TEST PLANT
Com- cation pound ~ate No kg/~a Wh Jm Rg Ot B P Ip Ms Sf 1 1.0 2 5 5 3 5 0 0 0 0 2 1.0 3 ~ 4 3 2 0 0 0 0 3 1.0 5 5 5 5 5 0 0 0 0 3 0.25 4 5 ~ 4 2 - - - -4 1.0 5 5 5 5 5 0 0 0 0 4 0.25 5 5 5 5 5 1.0 5 5 5 $ 5 G O O
0.~5 5 5 5 5 5 6 1.0 5 5 5 5 4 0 5 5 4 7 1.0 2 5 5 5 1 0 0 ~ O
:
' -~ ' . ' " - ' , ' :' ' ,. ' " ' ,, ' ~
-' ' ~ . ' ,' ' ' , ' ' , ~' ' ~" '~,, ," .

.

7~

~5 TABLE 3 Conti ued Pre-emer~ent Herbicidal Activity Appli- TEST PLANT
Com- cation 5 pound Rate No kg/ha Wh Jm Rg Ot B P Ip Ms Sf 8 1.0 5 5 5 5 5 1 0 8 0.25 5 5 5 5 5 - - - -9 1.0 5 5 5 - 5 4 2 0 9 0.25 3 5 5 - 5 ~

1.0 5 5 5 5 5 0 0 0 o 0.25 5 4 5 5 5 11 1.0 5 5 5 5 5 0 0 0 0 11 0.25 5 5 5 5 5 , Example 11 The post-emergent herbicidal activity of the compounds of the invention formulated as described in Example 9 was assessed by the following procedure.

The seeds of the test specie~ 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 . . , .: . . .

,~ , t ' ~

~ ~ ~t~3 watered with an overhead spr~y to initiate germination and then sub-irrigated as required for optimum plant growth. After the plants had grown to a height of ahout 10 to 12.5 cm one box of each of the mono-cotyledonous plants and the dicotyledonous plants wasremoved from the glass house and sprayed with the re-quired 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 treat-ment was visually assessed by comparison with the un-~reated controls. The results are presented in Table 4 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% damag2, 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 ~m Japanese millet B Barley P Peas Ip Ipomea Ms Mustard Sf Sunflower ' ~x~

Post-emergent Herbicidal Ac_ivity Appli- TEST PLANT
Com- cation 5 pound Rate No kg/haWh Jm Rg Ot B P Ip Ms Sf l 0.25 5 5 5 5 5 0.0625 3 5 4 5 4 2 l.0 5 5 5 5 5 0 0 ~ 0 0.25 4 5 5 5 4 3 1.0 5 5 5 5 5 0 0 0 0 0.25 4 5 5 5 5 - - - -0.0625 ~ 5 4 5 5 - - -4 1.0 5 5 5 5 5 0 0 0 0 0.25 5 5 5 5 5 0.0625 5 5 5 5 5 - - - -l.0 5 5 5 5 5 0 3 3 2 0.25 5 5 5 5 ~ - - - -0.0625 5 5 5 5 5 - - - -6 1.0 5 5 5 5 5 0 0 o 0 0.25: 2 5 4 4 5 0~0625 3 5 3 4 5 - - - -.
:

., ,, ~ . -Post ~mergent Herbicidal Activity _ . _ . . ...

Appli- TEST PLANT
Com- cation .
pound Rate No kg/ha Wh Jm Rg Ot B P Ip Ms Sf , 7 1.0 4 5 5 5 4 0 0 o 8 1.0 5 5 5 5 5 5 0 1 3 0. 25 5 5 5 5 5 0. 0625 5 5 5 5 5 - - - -9 1.0 5 5 5 5 ~ 3 3 4 2 0. 25 5 5 5 5 5 0. 0625 5 5 5 ~ 5 - - - _ 1.0 5 5 5 5 5 0 0 - 0 lS 0. 25 5 5 5 5 5 11 1.0 5 5 5 5 5 0 0 - 2 0. 25 5 5 5 5 S - - - --.. . _ _ . . _ _ , . : -, . . ..
.. . . . .
. .. , ,, .: .

7f~

- 49 ~

Example 12 The compounds were formulated for test by mixing an appropriate amount with 5 rnl 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 5 below.
Damage to test plants was assessed after 14 days on a scale of 0 to 5 where 0 is 0 to 20~ damage and 5 is complete kill. The degree of herbicidal damage was assessed by comparison with untreated control plants.
The results are given in Table 5 below. A dash (-) means that no experiment was carried out.

The names of the test plants were as follows:

Mz Maize Ww Winter wheat Rc Rice Br Barley ~v Avena fatua ___ _ Dg Digitaria sanguinalis Al Alopecurus myosuroides St Setaria viridis :
~c Echinochloa crus-galli Sh Sorghum ~
-Ag Agropyron repens .
.~ . .

: ' ' 3 '~7~7 -- 50 ~

. .. . . .. _ _ A~pli-TEST PLANT
Com- cati.on pound Rate No ( Kg/ha ) Mz Ww Rc Br Av Dg A1 St Ec Sh Ag 0.2 4 - - 4 5 4 4 4 4 4 0. 1 3 - - 4 4 4 4 4 4 3 0.25 4 2 0 4 4 4 4 4 4 3 2 2 0.2 5 4 4 4 4 4 4 4 5 4 4 2 0.1 4 4 4 3 4 4 4 4 5 3 3 3 0.2 5 4 4 4 4 4 5 4 5 4 4 3 1).1 4 4 2 4 4 3 4 3 5 3 3 4 0.2 4 3 3 5 5 4 4 2 5 4 4 4 0.1 3 1 1 4 5 3 ~ 2 5 4 3 4 0.05 0 1 0 4 4 3 3 1 4 0 0 0.2 5 4 4 5 5 5 5 5 5 5 ~
0.05 5 4 1 4 5 4 5 5 5 4 4 6 0.2 4 4 4 4 5 4 4 4 5 4 4 6 0.1 4 4 3 4 5 3 4 4 5 4 3 7 0.2 4 3 3 4 4 4 4 3 4 3 1 8 - 0.12 4 4 3 4 5 5 5 5 5 5 4 8 0.02 - - - - 4 5 ~ 3 5 2 2 0.1 0 2 1 2 4 4 4 3 4 2 0 11 0.15 5 4 3 5 5 5 5 4 5 ~ 4 11 0. 05 2 4 2 4 5 4 4 4 5 2 3 _ ~. .. . . .
, - , .
.

Claims (12)

1. A compound of formula I

I

wherein Y is selected from the group consisting of :
C1 to C6 alkylsulfonyl; C1 to C6 haloalkylsulfonyl;
C2 to C6 haloalkanoyl; R5CO and R5CS wherein R5 is selected from the group consisting of: hydroxy, C1 to C6 alkoxy, amino, C1 to C6 alkylamino and di(C1 to C6 alkyl)amino;

Z is selected from the group consisting of hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkanoyl, sulfamoyl, C1 to C4 alkylsulfamoyl, di(C1 to C4 alkyl)sulfamoyl, carboxy and trifluoroacetylamino;

R1 is selected from the group consisting of:
hydrogen; 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 halo-alkenyl; C3 to C6 alkynyl; and substituted C1 to C6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halogen, phenyl, and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, and C1 to C6 alkyl;

R3 is selected from the group consisting of: C1 to C6 alkyl; and R4 is selected from the group consisting of:
hydrogen C1 to C6 alkyl; and (C1 to C6 alkoxy) carbonyl.

2. A compound according to claim 1 wherein:

Y is selected from the group consisting of:

C1 to C6 alkylsulfonyl; C1 to C6 haloalkylsulfonyl;
C2 to C6 haloalkanoyl; R5CO and R5CS wherein R5 is selected from the group consisting of: hydroxy, C1 to C6 alkoxy, amino, C1 to C6 alkylamino and di(C1 to C6 alkyl)amino;

Z is selected from the group consisting of hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkanoyl, sulfamoyl, C1 to C4 alkylsulfamoyl, di(C1 to C4 alkyl) sulfamoyl, carboxy and trifluoroacetylamino:

R1 is selected from the group consisting of: hydrogen;
C2 to C6 alkanoyl; benzoyl and substituted benzoyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, C1 to C6 alkyl and C1 to C6 alkoxy;
and an inorganic or an organic cation selected from the alkali metals, the alkaline earth metals the transition metals the ammonium ion and the tri- and tetra(alkyl) ammonium ions wherein alkyl is selected from C1 to C6 alkyl and C1 to C6 hydroxyalkyl;
R2 is selected from the group consisting of:
C1 to C6 alkyl; C2 to C6 alkenyl; C2 to C6 haloalkenyl;
C3 to C6 alkynyl, and substituted C1 to C6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halogen, phenyl, and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, and C1 to C6 alkyl;

R3 is selected from the group consisting of: C1 to C6 alkyl; and R4 is selected from the group consisting of:
hydrogen; C1 to C6 alkyl; and (C1 to C6 alkoxy) carbonyl.

3. A compound according to claim 2 wherein:

Y is selected from the group consisting of:

C1 to C6 alkylsulfonyl; C1 to C6 haloalkylsulfonyl;
C2 to C6 haloalkanoyl; R5CO and R5CS wherein R5 is selected from the group consisting of: hydroxy, C1 to C6 alkoxy, amino, C1 to C6 alkylamino and di(C1 to C6 alkyl)amino;

Z is selected from the group consisting of hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkanoyl, sulfamoyl, C1 to C4 alkylsulfamoyl, di(C1 to C4 alkyl)sulfamoyl, carboxy and trifluoroacetylamino;

R1 is selected from the group consisting of:

hydrogen; C2 to C6 alkanoyl and the alkali metal cations;

R2 is selected from the group consisting of:
C1 to C6 alkyl; C1 to C6 haloalkyl; C2 to C6 alkenyl;
C2 to C6 haloalkenyl and C3 to C6 alkynyl;

R3 is selected from the group consisting of:
C1 to C6 alkyl; and R4 is selected from the group consisting of:
hydrogen; C1 to C6 alkyl; and (C1 to C6 alkoxy) carbonyl.

4. A compound according to claim 3 wherein:

Y is selected from the group consisting of:
C1 to C6 alkylsulfonyl; C1 to C6 haloalkylsulfonyl;
C2 to C6 haloalkanoyl; R5CO and R5CS wherein R5 is selected from amino, C1 to C6 alkylamino and di(C1 to C6 alkyl) amino;

Z is selected from the group consisting of:
hydrogen, halogen, C1 to C4 alkyl and C2 to C4 alkanoyl;

R1 is selected from the group consisting of:
hydrogen; C2 to C6 alkanoyl and the alkali metal cations;

R2 is selected from the group consisting of:
C1 to C6 alkyl C2 to C6 alkenyl and C3 to C6 alkynyl;

R3 is selected from the group consisting of:
C1 to C6 alkyl;

R4 is hydrogen.

5. A compound according to claim 4 wherein:

Y is selected from the group consisting of:
C1 to C4 haloalkylsulfonyl; C2 to C4 haloalkanoyl;
carbamoyl; thiocarbamoyl; C1 to C4 alkylcarbamoyl;
C1 to C4 alkylthiocarbamoyl;

Z is selected from the group consisting of:
hydrogen, halogen, methyl and C2 to C4 alkanoyl, R1 is selected from hydrogen and the alkali metal cations;

R2 is selected from C1 to C4 alkyl; C2 to C4 alkenyl and C3 to C4 alkynyl;

R3 is selected from C1 to C4 alkyl, R4 is hydrogen.

6. A compound according to claim 5 wherein:

Y is selected form the group consisting of:
trifluoromethanesulfonyl, trifluoroacetyl, trichloro-acetyl, carbamoyl, ethylthiocarbamoyl, methylcarbamoyl and propylcarbamoyl;

Z is hydrogen or acetyl;

R1 is hydrogen;

R2 is selected from ethyl, allyl and propargyl;

R3 is methyl, ethyl or propyl;

R4 is hydrogen.

7. A compound according to claim 6 selected from the group consisting of:

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethyl-3-trifluoroacetylaminophenyl)cyclohex-2-en-1-one;

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-[3-acetyl-2,4,6-trimethyl-5-trifluoroacetylaminophenyl)cyclohex-2-en-1-one;

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-[3-(N'-methylureido)-2,4,6-trimethylphenyl]cyclohex-2-en-1-one;

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-[3-(N'-n-propylureido)-2,4,6-trimethylphenyl]cyclohex-2-en-1-one;

8. A herbicidal composition comprising as active ingredient a compound as defined according to claim 1 and a carrier therefor.

9. 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 claim 1.

10. 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 claim 1¦in an amount sufficient to severely damage or kill said weeds but insufficient to substantially damage said crop.

11. A process according to claim 9 or claim 10 wherein the compound is applied at a rate in the range of from 0.005 to 20 kilograms per hectare.

12. A process for the synthesis of a compound of formula I as defined according to claim 1 which process comprises reacting a 2acyl cyclohexane-1,3-dione derivative of formula Xc with an alkoxyamine derivative of formula XVIII to give a compound of the invention of formula II or reacting the 2-acyl cyclohexane-1,3-dione derivative of formula Xc with hydroxylamine and alkylating the oxime intermediate of formula XIX with an alkylating agent of formula XX, wherein L is a leaving group, to give as compound of the invention of formula II; and optionally XC

H2NOR2 XVIII
II

R2L

XX

XIX

reacting the compound of the invention of formula II
with a compound of formula XXI wherein L is a leaving group, to give a compound of the invention of formula I.

I R1L
XXI