# Patent

## Title
Pyrindamycins A and B and duocarmycin A antibiotics derived from certain

## Abstract

This is a continuation of application Ser. No. 06/687,933, filed Dec. 31, 1984 which is, a division of Ser. No. 525,483, filed Aug. 22, 1983, which both now abandoned.

## Background
This invention relates to organic compounds having 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 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-[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 Pat. No. 464 655 and its equivalents such as U.K. Pat. No. 1 461 170 and U.S. Pat. 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-on e) was announced. This compound is disclosed in Australian Patent Application No. AU-A1-35,314/78 and its equivalents.

It has now been found that a new group of cyclohexane-1,3-dione derivatives which have a 5-pyrimidyl substituent exhibit particularly useful herbicidal activity.

Accordingly the invention provides a compound of formula I: ##STR2## wherein:

X, which may be the same or different, are independently selected from the group consisting of: halogen; nitro; cyano; C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 alkyl substituted with a substituent selected from the group consisting of halogen, nitro, hydroxy, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.1 to C.sub.6 alkoxy; C.sub.1 to C.sub.6 alkoxy substituted with a substituent selected from halogen and C.sub.1 to C.sub.6 alkoxy; C.sub.2 to C.sub.6 alkenyloxy; C.sub.2 to C.sub.6 alkynyloxy; C.sub.2 to C.sub.6 alkanoyloxy; (C.sub.1 to C.sub.6 alkoxy)carbonyl; C.sub.1 to C.sub.6 alkylthio; C.sub.1 to C.sub.6 alkylsulfinyl; C.sub.1 to C.sub.6 alkylsulfonyl; sulfamoyl; N-(C.sub.1 to C.sub.6 alkyl)sulfamoyl; N,N-di(C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 haloalkyl; the group NR.sup.5 R.sup.6 wherein R.sup.5 and R.sup.6 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.6 alkyl, C.sub.2 to C.sub.6 alkanoyl, benzoyl and benzyl; the groups formyl and C.sub.2 to C.sub.6 alkanoyl and the oxime, imine and Schiff base derivatives thereof;

R.sup.1 is selected from the group consisting of: hydrogen; C.sub.1 to C.sub.6 alkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; substituted C.sub.1 to C.sub.6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; C.sub.1 to C.sub.6 (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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; an acyl group; and an inorganic or organic cation;

R.sup.2 is selected from the group consisting of: C.sub.1 to C.sub.6 alkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 haloalkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.2 to C.sub.6 haloalkynyl; substituted C.sub.1 to C.sub.6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halogen, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio;

R.sup.3 is selected from the group consisting of: C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 fluoroalkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; and phenyl;

R.sup.4 is selected from the group consisting of: hydrogen; halogen; cyano; C.sub.1 to C.sub.6 alkyl; and (C.sub.1 to C.sub.6 alkoxy)-carbonyl; and

n is an integer selected from 1 to 2.

When in the compound of formula I X is chosen from the groups formyl and C.sub.2 to C.sub.6 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 X is formyl or C.sub.2 to C.sub.6 alkanoyl. Suitable values for the groups formyl and C.sub.2 to C.sub.6 alkanoyl and the oxime, imine and Schiff base derivatives thereof include groups of the formula -C(R.sup.7)=NR.sup.8 wherein R.sup.7 is chosen from hydrogen and C.sub.1 to C.sub.5 alkyl, and R.sup.8 is chosen from hydrogen, C.sub.1 to C.sub.6 alkyl, phenyl, benzyl, hydroxy, C.sub.1 to C.sub.6 alkoxy, phenoxy and benzyloxy.

When in the compound of formula I R.sup.1 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 R.sup.1 is acyl the acyl group may be removed in the plant by hydrolysis to give the corresponding compound of formula I in which R.sup.1 is hydrogen. Suitable acyl groups include: alkanoyl, for example C.sub.2 to C.sub.6 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, C.sub. to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; and heteroaroyl, for example 2-furoyl, 3-furoyl, 2-thenoyl and 3-thenoyl.

When in the compound of formula I R.sup.1 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 R.sup.1 is a cation the cation may be removed in the plant to give a compound of formula I wherein R.sup.1 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 R.sup.9 R.sup.10 R.sup.11 R.sup.12 N.sym. wherein R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are independently chosen from the group consisting of: hydrogen; C.sub.1 to C.sub.10 alkyl; substituted C.sub.1 to C.sub.10 alkyl wherein the alkyl group is substituted with a substituent chosen from the group consisting of hydroxy, halogen and C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio.

The compounds of the invention may exist in two isomeric forms as shown, below wherein .phi. represents the group ##STR3##

It should be recognized that when R.sup.1 is hydrogen, the compounds of the invention may exist in any one of four tautomeric forms as shown below. ##STR4##

Suitable X include C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkylthio, halogen, C.sub.1 to C.sub.6 haloalkyl, amino, C.sub.1 to C.sub.6 alkylamino and di(C.sub.1 to C.sub.6 alkyl)amino.

Suitable R.sup.1 include: hydrogen; C.sub.1 to C.sub.6 alkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; substituted C.sub.1 to C.sub.6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; C.sub.1 to C.sub.6 (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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkyltio; and acyl group; and an inorganic or organic cation.

Suitable R.sup.2 include: C.sub.1 to C.sub.6 alkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 haloalkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.2 to C.sub.6 haloalkynyl; substituted C.sub.1 to C.sub.6 alkyl wherein the alkyl group is substituted with substituent selected from the group consisting of halogen, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio.

Suitable R.sup.3 include: C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 fluoroalkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; and phenyl.

Suitable R.sup.4 include hydrogen.

Suitable n include the integers 1 and 2.

Preferred compounds of the invention include those compounds of formula I wherein:

X are independently selected from the group consisting of C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkylthio, C.sub.1 to C.sub.6 alkylsulfinyl, C.sub.1 to C.sub.6 alkylsulfonyl, halogen, amino, N-(C.sub.1 to C.sub.6 alkyl)amimo and N,N-di(C.sub.1 to C.sub.6 alkyl)amino;

R.sup.1 is selected from the group consisting of: hydrogen; C.sub.2 to C.sub.6 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, C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy; benzenesulfonyl and substituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy; and an inorganic or an organic cation selected from the alkali metals such as lithium, potassium and sodium, the alkaline earth metals such as magnesium, calcium and barium, the transition metals such as manganese, copper, zinc, iron, nickel, cobalt and silver, the ammonium ion and the tri- and tetra-(alkyl)ammonium ions wherein alkyl is selected from C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 hydroxyalkyl;

R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.6 alkyl, C.sub.2 to C.sub.6 alkenyl, C.sub.2 to C.sub.6 alkynyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.2 to C.sub.6 haloalkenyl and C.sub.2 to C.sub.6 haloalkynyl;

R.sup.3 is selected from C.sub.1 to C.sub.6 alkyl;

R.sup.4 is selected from hydrogen and halogen; and

n is an integer selected from 1 and 2.

More preferred compounds of the invention include those compounds of formula I in which the pyrimidine ring is linked through the 5-position to the cyclohexane ring. That is, compounds of formula III: ##STR5## wherein:

X are independently selected from the group consisting of C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkylthio, C.sub.1 to C.sub.6 alkylsulfinyl, C.sub.1 to C.sub.6 alkylsulfonyl, halogen, amino, N-(C.sub.1 to C.sub.6 alkyl)amino and N,N-di(C.sub.1 to C.sub.6 alkyl)amino;

R.sup. is selected from the group consisting of hydrogen, C.sub.2 to C.sub.6 alkanoyl, benzoyl, the alkali metals, the transition metals, the ammonium ion and the tri- and tetra-(alkyl)ammonium ions wherein alkyl is selected from C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 hydroxyalkyl;

R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl, C.sub.1 to C.sub.3 haloalkyl, allyl and haloallyl;

R.sup.3 is selected from C.sub.1 to C.sub.3 alkyl;

R.sup.4 is hydrogen; and

n is an integer selected from 1 to 2.

Included among the more preferred compounds of the invention are those 5-pyrimidyl compounds of formula III wherein:

X are independently selected from the group consisting of C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkylthio and N,N-di(C.sub.1 to C.sub.6 alkyl)amino;

R.sup.1 is selected from the group consisting of hydrogen, C.sub.2 to C.sub.6 alkanoyl and the alkali metals;

R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl, alyl and haloallyl;

R.sup.3 is selected from C.sub.1 to C.sub.3 alkyl;

R.sup.4 is hydrogen; and

n is the integer 1.

Also included among the more preferred compounds of the invention are those 5-pyrimidyl compounds which are substituted in the 2-position of the pyrimidine ring. That is, compounds of formula IIIa ##STR6## wherein:

X is independently selected from the group consisting of C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkxoy, C.sub.1 to C.sub.6 alkylthio,

C.sub.1 to C.sub.6 alkylsulfinyl and N,N-di(C.sub.1 to C.sub.6 alkyl)amino;

R.sup.1 is selected from the group consisting of hydrogen, C.sub.2 to C.sub.6 alkanoyl and the alkali metals;

R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl, allyl and haloallyl;

R.sup.3 is selected from C.sub.1 to C.sub.3 alkyl; and

R.sup.4 is hydrogen.

Particularly preferred values for X include methyl, methoxy, methylmercapto and N,N-dimethylamino.

Particularly preferred values for R.sup.1 include hydrogen, C.sub.2 to C.sub.6 alkanoyl, sodium and potassium.

Particularly preferred values for R.sup.2 include ethyl, n-propyl, allyl and chloroallyl;

Particularly preferred values for R.sup.3 include ethyl and n-propyl.

Examples of compounds embraced by the invention include: ##STR7##

Specific examples of the compounds of the invention include those compounds detailed in Tables 1a and 1b. ______________________________________ ##STR8## Com- pound No    (X).sub.n R.sup.1     R.sup.2    R.sup.3 ______________________________________ 1     2-CH.sub.3 H           C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 2     2-CH.sub.3 S H           C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 3     2-CH.sub.3 O H           C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 4     2-CH.sub.3 S H           C.sub.2 H.sub.5 C.sub.2 H.sub.5 5     2-CH.sub.3 S Na          C.sub.2 H.sub.5 C.sub.2 H.sub.5 6     2-CH.sub.3 S(O) H           C.sub.2 H.sub.5 C.sub.2 H.sub.5 7     2-CH.sub.3 H           CH.sub.2 CHCHCl n-C.sub.3 H.sub.7 8     2-CH.sub.3 O COC(CH.sub.3).sub.3 C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 9     2-(CH.sub.3).sub.2 N H           C.sub.2 H.sub.5 C.sub.2 H.sub.5 ______________________________________ ______________________________________ ##STR9## Compound No  (X).sub.n R.sup.1   R.sup.2 R.sup.3 ______________________________________ 10           5-CH.sub.3 H         C.sub.2 H.sub.5 C.sub.2 H.sub.5 ______________________________________

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.

Conventiently 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 VIa or VIb respectively; and reacting, preferably in the presence of a base, a ketone derivative of formula VIa with a malonic acid ester derivative of formula VIIa 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, or reacting, preferably in the presence of a base, a ketone derivative of formula VIa with an alkanoic acid ester of formula VIIc 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 VIIb to give an aryloethylidenemalonate derivative of formula VIc which is in turn reacted, preferably in the presence of a base, with an acetoacetic acid ester derivative of formula VIId to give an intermediate of formula VIIIc 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 derivataive of formula V with an acetic acid ester of formula IVc to give a 2-arylalkenoate derivative of formula VId which is in turn reacted, preferably in the presence of a base, with an acetoacetic acid ester derivative of formula VII d to give an intermediate 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-acyl-5-arylcyclohexan-1,3-dione of formula XIII. 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 IX or an alkoxide salt of formula XII, wherein M is an alkali metal ion and R is C.sub.1 to C.sub.6 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 R.sup.1 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 L is a leaving group such as, for example, chloride, bromide, iodide, sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, methanesulfonate, fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate.

Part D involves the formation of a compound of the invention of formula I wherein R.sup.1 is a substituent other than hydrogen.

Compounds of the invention of formula I, wherein R.sup.1 forms an ether, acyl or sulfonyl derivative of a compound of formula II, may be prepared from the corresponding compounds of the invention of formula II by reacting with an etherification, acylation or sulfonylation reagent of formula XX.

Compounds of the invention of formula I wherein R.sup.1 is an inorganic or organic cation may be prepared from the compounds of the invention of formula I wherein R.sup.1 is hydrogen, that is, compounds of formula II, by reacting said compounds of formula II with an inorganic or organic salt. For example, the compounds of formula I wherein R.sup.1 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 R.sup.1 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 R.sup.1 is a transition metal ion or an organic cation may be prepared by reacting the appropriate compound of formula I wherein R.sup.1 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 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 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 XX, wherein L is a leaving group, to give a compound of the invention of formula I.

The structure of the compounds described above are detailed on the following pages wherein .phi. represents the group ##STR10##

Certain of the intermediate compounds of formulae V, VIa, VIb, VIc, VId, VIIIa, VIIIb, VIIIc, IX, XIII, XVI and XVIII are novel compounds and therefore in further embodiments the invention provides novel compounds of formulae V, VIa, VIb, VIc, VId, VIIIa, VIIIb, VIIIc, IX, XIII, XVI and XVIII and processes for the preparation thereof.

For example, none of the pyrimidinecarboxaldehydes of formula V used in the preparation of the compounds of the invention of formula I has previously been described.

Accordingly, in a further aspect the invention provides a compound of formula V ##STR11## wherein X and n are as hereinbefore defined.

A preferred group of compounds of the invention of formula I may be prepared from novel 2-substituted-pyrimidine-5-carboxaldehydes. Accordingly in a further aspect the invention provides pyrimidine-5-carboxaldehydes of formula Va ##STR12## wherein X is as hereinbefore defined.

The compound 2,4,6-trimethoxypyrimidine-5-carboxaldehyde may be prepared by Vilsmeyer formylation of 2,4,6-trimethoxypyrimidine using N,N-dimethylformamide and phosphorus oxychloride. However, Vilsmeyer formulation is only effective with aromatic compounds which are very reactive towards electrophillic aromatic substitution and the reaction works in this instance because of the presence of three strongly electron donating groups in the pyrimidine ring.

It is not possible to use the Vilsmeyer formylation reaction to prepare pyrimidine carboxaldehydes in which the pyrimidine ring is not activated by strongly electron donating groups. For example, it was necessary to find a new process to prepare the novel 2-substituted-pyrimidine-5-carboxaldehydes used in the preparation of a preferred goup of compounds of the invention of formula I. This new process involves reacting a 2-(methylene)propanediylidene derivative, such as for example {2-[(dimethylamino)methylene]-propanediylidene}bis[dimethylammonium perchlorate], with an amidine derivative. Accordingly, in a further aspect the invention provides a process for the preparation of a pyrimidine-5-carboxaldehyde derivative of formula Va ##STR13## which process comprises reacting a 2-(methylene)-propanediylidene derivative of formula XXI wherein R is selected from C.sub.1 to C.sub.6 alkyl with an amidine derivative of formula XXII wherein X is as hereinbefore defined, or a salt thereof. ##STR14##

In a further embodiment the invention provides a compound of formula IX ##STR15## wherein X, R.sup.4 and n are as hereinbefore defined.

In a still further embodiment the invention provides a compound of formula XIII ##STR16## wherein X, R.sup.3, R.sup.4 and n are as hereinbefore defined.

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 relatively unaffected by rates of application of the compounds of the invention which are severely damaging or lethal to other planat species.

Accordingly in a further aspect the invention provides a process for selectively controlling the growth of monocotyledonous weeds in dicotyledonous crops which process comprises applying to the crop, or to the growth medium of the crop, a compound of formula I in an amount sufficient to severely damage or kill said weeds but insufficient to substantially damage said crop.

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 I as hereinbefore defined and an agriculturally acceptable 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, 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 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 agriculturally acceptable carrier therefor.

The compositions of the present invention may be in the form of solids, liquids or pastes. The compositions include both dilute compositions which are ready for immediate use and concentrated compositions which may require dilution before use. Therefore, the concentration of the active ingredient in the compositions of the present invention will vary depending on the types of formulation and whether the composition is ready for use such as, for example, a dust 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 9% 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 ingredient 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, powdered magnesia, magnesium oxide, magnesium sulfate, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicates and silica gels; 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 surface active agents which act as wetting, emulsifying and/or dispersing agents to facilitate the dispersion of the active ingredient in liquid.

Examples of surface active agents include those of the cationic, anionic and non-ionic type. Cationic surface active agents include quaternary ammonium compounds, for 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 arylsulfonic acids including the salts of naphthalenesulfonic acids such as butylnaphthalenesulfonic acid, the di- and tri-isopropylnaphthalenesulfonic acids, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with phenol and formaldehyde, and the salts of alkylarylbenzenesulfonic 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 surface active agents include: the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol; the condensation products of 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 solution or dispersion of the active ingredient in a liquid carrier optionally containing one or more surface 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 naphta, 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 propylene glycol; ketones such as, for example, cyclohexanone and isophorone; and strongly polar organic solvents such as, for example, dimethylformamide, dimethylsufloxide, N,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 compositions are generally prepared by mixing concentrated compositions with water. Suitable concentrated compositions 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 preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates conveniently contain from 20 to 99%, preferably 20 to 60%, by weight of active ingredient.

Emulsion or emulsifiable concentrates are conveniently prepared by dissolving the active ingredient in an organic solvent containing one or more surface active agents. Pastes may be prepared by blending the finely divided active ingredient with a finely divided solid carrier, one or more surface active agents and optionally an oil. Oil dispersions may be prepared by grinding together the active ingredient, 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 ingredient, water, at least one surfacae 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 example, montmorillonite, beidellite, nontronite, hectorite, saponite, sauconite and bentonite; other cellulose derivatives; and poly(vinyl alcohol). Wettable powder concentrates may conveniently be prepared b 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 suspensions, dispersions or emulsions may be prepared from the concentrated compositons 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 R.sup.1 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 an employing the compounds of formula I in the form of their salts either the salts per se, that is the compounds of formula I wherein R.sup.1 is an inorganic or an organic cation, may be used in the formulation or the compounds of formula I wherein R.sup.1 is hydrogen may be use in the formulation and the salts generated in situ by the used 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 hectare is suitable while from 0.01 to 5.0 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 in general substantially more effective against monocotyledonous plants or grass species than against dicotyledonous plants or broad-leaved species. As a result, in certain applications the herbicidal 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 hereinbefore 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 preferred class is of mixtures comprising a herbicide active against broad-leaved weeds. A second preferred class is of mixtures comprising a contact herbicide.

Example of useful complementary herbicides include:

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

B. hormone herbicides and in particular the phenoxyalkanoic acids such as 4-chloro-2-methylphenoxy acetic acid (common name MCPA), 2-(2,4-dichlorophenoxy)propionic acid (common name dichlorprop), 2,4,5-trichlorophenoxyacetic acid (common name 2,4,5-T), 4-(4-chloro-2-methylphenoxy)butyric acid common name MCPB), 2,4-dichlorophenoxyacetic acid (common name 2,4-D), 4-(2,4-dichlorophenoxy)butyric acid (common name 2,4-DB), 2-(4-chloro-2-methylphenoxy)propionic acid (common name mecoprop), and their derivatives (e.g. salts, esters, amides and the like);

C. 3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (common name chloroxuron);

D. dinitrophenols and their derivatives (e.g. acetates) such as 2-methyl-4,6-dinitrophenol (common name DNOC), 2-tertiarybutyl-4,6-dimitrophenol (common name dinoterb), 2-secondarybutyl-4,6-dinitrophenol (common name dinoseb) and its ester dinoseb acetate;

E. dinitroaniline herbicides such as N',N'-diethyl2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (common name dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline (common name trifluralin) and 4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin);

F. phenylurea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (common name diruon) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (common name fluometuron);

G. phenylcarbamoyloxyphenylcarbamates such as 3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)-carbamate (common name phenmedipham) and 3-[(ethoxycarbonylamino]phenyl phenylcarbamate (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-chylohexyl-5,6-trimethyleneuracil (common name lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil) and 3-tert-butyl-5-chloro-6-methyluracil (common name terbacil);

J. triazine herbicides such as 2-chloro-4-ethylamino-6-(iso-propylamino)-1,3,5-triazine (common name 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. 1-alkoxy-2-alkyl-3-phenylurea herbicides such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron), 3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron) and 3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common name chlorobromuron);

L. thiocarbamate herbicides such as S-propyl dipropylthiocarbamate (common name verolate);

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-triazin-5-one (common name metribuzin);

N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (common name 2,3,6-TBA), 3,6-dichloro-2-methyoxybenzoic acid (common name dicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben);

O. anilide herbicides such as N-butoxymethyl-.alpha.-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-hydroxybenzonitrile (common name bromoxynil) and 3,5diiodo-4-hydroxybenzonitrile (common name ioxynil).

Q. Haloalkanoic herbicides such as 2,2-dichloropropionic acid (common name dalapon), trichloroacetic acid (common name TCA) and salts thereof;

R. diphenylether herbicides such as 4-nitrophenyl 2-nitro-4-trifluorometylphenyl ether (common name fluorodifen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common 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 2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesu lfonamide (commonly known as DPX 4189); and

T. miscellaneous herbicides including N,N-dimethyldiphenylacetamide (common name diphenamid), N-(1-naphthyl)phthalamic acid (common name naptalam) and 3-amino-1,2,4-triazole.

Examples of useful contact herbicides include:

U. bipyridylium herbicides such as those in which the active entity is the 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and those in which the active entity is the 1,1'-ethylene-2,2'-dipryidylium ion (common name diquat);

V. organoarsenical herbicides such as monosodium methanearsonate (common name MSMA); and

W. amino acid herbicides such as N-(phosphonomethyl)-glycine (common name glyphosate) and its salts and esters.

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

This Example details the preparation of the mono-substituted pyrimidine-5-carboxaldehydes of formula V used in the preparation of compounds of the invention.

(i) {2-[(Dimethylamino)methylene]propanediylidene} bis[dimethylammonium perchlorate] was prepared by formylation of bromoacetic acid following the procedure of Arnold (Collect. Czech. Chem. Comm., 30, 2125 (1965)).

(ii) A suspension of the above perchlorate salt (14.8 g) and acetamidine hydrochloride (4.0 g) in methanol (200 ml) was stirred at 40.degree. C. during the gradual addition of a solution of sodium (1.0 g) in methanol(50 ml). After 3 hours the solution was neutralized with acetic acid and evaporated under reduced pressure. The residue was diluted with water (50 ml) and extracted with chloroform (2.times.100 ml). The chloroform extracts were dried and evaporated to give 2 -methylpyrimidine-5-carboxaldehyde (2.5 g, 49%). The product was characterized by proton nuclear magnetic resonance spectroscopy and the spectrum is recorded in Table 2 below.

The mono-substituted pyrimidine-5-carboxaldehydes of formula V listed in Table 2 below were prepared from {2-[(dimethylamino)methylene]propanediylidene}bis-[dimethylammonium perchlorate] and the appropriate amidine hydrochloride following the procedure described above for the preparation of 2-methylpyrimidine-5 -carboxaldehyde. The products were characterized by proton nuclear magnetic resonance spectroscopy and the spectroscopic data are recorded in Table 2 below. ______________________________________ ##STR17## Position of   Proton Chemical Shift .delta. in X        CHO Group     ppm (CDCl.sub.3) ______________________________________ 2-CH.sub.3 5-            2.90(3H,s); 9.02(2H,s); 10.06(1H,s). 2-CH.sub.3 S 5-            2.60(3H,s); 8.87(2H,s); 9.96(1H,s). 2-CH.sub.3 O 5-            4.10(3H,s); 8.92(2H,s); 9.95(1H,s). ______________________________________ one (1)

(i) A solution of 2-methylpyrimidine-5-carboxaldehyde (4 g) in acetone (50 ml) and water (30 ml) was treated with a solution of aqueous sodium hydroxide (2%, 5 ml) with stirring at 20.degree. C. The solution was allowed to stand at room temperature overnight and then concentrated under reduced pressure and neutralized with dilute hydrochloric acid. The mixture was extracted dried over anhydrous magnesium sulphate and evaporated under reduced pressure to give 1-[5-(2-methylpyrimidyl)]but-1-en-3-one (2.3 g, 43%) as a pale brown oil.

(ii) Diethylmalonate (3.9 ml) was added to a stirred solution of sodium metal (0.56 g) in absolute ethanol (40 ml) and the solution was heated under reflux. 1-[5-(2-Methylpyrimidyl]but-1-en-3-one (2.3 g) was added and the mixture was heated under reflux for a period of 2 hours. An aqueous solution of sodium hydroxide (2.0 g, 30 ml water) was added and the solution was refluxed for a further 5 hours. The hot solution was acidified to pH 4 with concentrated hydrochloric acid (carbon dioxide evolution) and then made alkaline by the addition of sodium bicarbonate. Evaporation of the solution to dryness gave the sodium salt of 3-hydroxy-5-[2-methylpyrimidyl)]cyclohex-2-en-1-one (2.3 g, 72%) as a pale brown solid, mp>200.degree. C.

(iii) The sodium salt of 3-hydroxy-5-[5-(2-methylpyrimidyl)]chclohex-2-en-1-one (2.0 g) was dissolved in diemthylformamide (10 ml) with stirring at 90.degree. C. Butyric anhydride (1.4 ml) was added to the solution and the heating was continued at 110.degree. C. for 1 hour. The dimethylformamide was evaporated under reduced pressure and the residue was dissolved in water (20 ml) and chloroform (40 ml). The chloroform layer was separated, dried over anhydrous magnesium sulphate and evaporated to give an oil which was purified by column chromatography over silica gel (eluant chloroform) to give 2-butyryl-3-hydroxy-5-[5-(2-methylpyrimidyl)]cyclohex-2-en-1-one (800 mg; 30%) as an oil.

(iv) Ethoxyamine hydrochloride (240 mg, 2.5 mmol) and then sodium hydroxide (100 mg) in water (1 ml) were added to a solution of 2-butyryl-3-hydroxy-5-[5-(2-methylpyrimidyl)]cyclohex-2-en- 1-one (600 mg; 2.2 mmol) in ethanol (50 ml) with stirring at room temperature. After 20 hours the ethanol was removed by evaporation under reduced pressure. The residue was dissolved in chloroform, washed with water and then the organic layer was separated, dried over anhydrous magnesium sulphate and evaporated to give 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-[5-(2-methylpyrimidyl)]cyclohex-2-en- 1-one (600 mg; 87%) as a pale brown oil.

The product and each of the intermediates were characterized by proton nuclear resonance spectroscopy and the spectra for the intermediates and final product are recorded in Examples 11, 12 and 13, Tables 3, 4 and 5.

2-[1-(Ethoxylimino)butyl]-3-hydroxy-5-[5-(2-methylthiopyrimidyl)]cyclohex-2 -en-1-one (2) and 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-[5-(2-methoxypyrimidyl)]-cyclohex-2-e n-1one (3) were prepared from the appropriate pyrimidine-5-carboxaldehyde following essentially the same procedure as that described in Example 2 parts (i) to (iv).

Each of the products and intermediates were characterized by proton nuclear magnetic resonance spectroscopy and spectroscopic data are recorded in Examples 11, 12 and 13, Tables 3, 4 are 5.

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-[5-(2-mehtylthiopyrimidyl)]cyclohex-2 -en-1-one (4) was prepared following essentially the same procedure as that described in Example 2 parts (i) to (iv) except for the use of propionic anhydride in part (iii) instead of butyric anhydride. The product and intermediate were characterized by proton magnetic resonance spectroscopy and the spectra are recorded in Examples 12 and 13, Tables 4 and 5. -en-1-one sodium salt (5)

To a solution of 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[5-(2-methylthiopyrimidyl)]cyclohex- 2-en-1-one (180 mg) in methanol (30 ml) was added a solution of sodium hydroxide in methanol (1.1 ml of a solution of 1.0 g in 50 ml methanol). The solution was evaporated under reduced pressure to give the sodium salt (5) of 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[5-(2-methylthiopyrimidyl)]cyclohex- 2-en-1-one as a pale brown solid, mp>200.degree. C. ex-2-en-1-one (6)

A solution of 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[5-(2-methylthiopyrimidyl)]cyclohex- 2-en-1-one (600 mg) in dichloromethane (10 ml) was treated at 5.degree. C. with a solution of 3-chloroperbenzoic acid (400 mg) in dichloromethane (30 ml). The solution was allowed to warm to room temperature and to stand for 24 hours. The solvent was removed under reduced pressure and the residue was purified by column chromatography over silica gel (eluant chloroform) to give 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[5-(2-methylsulfinylpyrimidyl)]cyclo hex-2-en-lone (6) (300 mg, 46%) as a nearly colourless solid. The product was characterized by proton magnetic resonance spectroscopy and the spectrum is recorded in Example 13, Table 5.

2-[1-(3-Chloroallyloxy)butyl]-3-hydroxy-5-[5-(2-methylpyrimidyl)]cyclohex-2 -en-1-one (7) was prepared from 2-butyryl-3-hydroxy-5-[5-(2-methylpyrimidyl)]-cyclohex-2-en-1-one and 3-chloroallyloxyamine following essentially the same procedure as that described in Example 2, part (iv). The product was characterized by proton magnetic resonance specroscopy and the spectrum is recorded in Example 13, Table 5. lohex-2-en-1-one (8)

Trimethylacetylchloride (0.10 g) was added with stirring to a solution of 2-[1-(ethoxyimino)-butyl]-3-hydroxy-5-[5-(2-methoxypyrimidyl)]cyclohex-2-e n-1-one (3) (0.15 g) and 3-picoline (0.10 g) in dichloromethane (10 ml) at room temperature. After 2 hours at room temperature the solution was washed with dilute hydrochloric acid (1M, 10 ml), separated, dried over anhydrous magnesium sulphate and evaporated under reduced pressure to give 3-trimethylacetyloxy-2-[1-(ethoxyimino)butyl]-5-[5-(2-methoxypyrimidyl)]-c yclohex-2-en-1-one (8) as a colourless oil 150 mg). The product was characterized by proton magnetic resonance spectroscopy and the spectroscopic data is recorded in Table 5, Example 13. x-2-en-1-one (9) was isolated by chromatography during the purification of 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[5-(2-methylthiopyrimidyl]cyclohex-2 -en-1-one (4) Presumably the dimethylamino group was introduced during the acylation step (Example 2 part (iii)) which is carried out in dimethylformamide at 110.degree. C.

The compound was characterized by proton nuclear magnetic resonance spectroscopy and the spectrum is recorded in Example 13, Table 5. 1-one (10)

(i) 2-Hydroxymethyl-5-methylpyrimidine was prepared by the reaction of 3-ethoxy-2-methyl acrolein and hydroxyacetaridine hydrochloride following a similar procedure to that described by Kim and McKee (J. Org. Chem., 35, 455 (1970). Proton magnetic resonance spectrum (CDCl.sub.3 ; .delta. in ppm): 2.32 (3H,s); 3.6 (1H,bs); 4.80 (2H,s); 8.54 (2H,s).

(ii) 5-Methylpyrimidine-2-carboxaldehyde was prepared from 2-hydroxymethyl-5-methylpyrimidine by oxidation with excess manganese dioxide in boiling chloroform. The product was obtained as colourless crystals and was characterized by proton nuclear magnetic resonance spectroscopy. Proton nuclear magnetic resonance spectrum (CDCl.sub.3 ; .delta. in ppm): 2.44 (3H,s); 8.80 (2H,s); 10.06 (1H,s).

(iii) 2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-[2-(5-methylpyrimidyl)]cyclohex-2-en -1-one (18) was prepared from 5-methylpyrimidine-2-carboxaldehyde following essentially the same procedure as that described in Example 2 parts (i) to (iv). Each intermediate and the product was characterized by proton magnetic resonance spectroscopy and these are recorded in Example 11, 12 and 13, Table 3, 4 and 5.

The 1-(mono-substituted pyrimidyl)but-1-en-3-ones of formula VIa used in the preparation of the compounds of formula I were characterized by their proton nuclear magnetic resonance (pmr) spectra. For convenience the pmr data are recorded in Table 3 below. ______________________________________ ##STR18##                    VIa Position of   Proton Chemical Shift (X).sub.n enone group   .delta. in ppm (CDCl.sub.3) ______________________________________ 2-CH.sub.3 5             2.39(3H,s); 2.75(3H,s); 7.08 (2H,dofd); 8.74(2H,s). 2-CH.sub.3 S 5             2.35(3H,s); 2.55(3H,s); 7.04 (2H,dofd); 8.61(2H,s). 2-CH.sub.3 O 5             2.38(3H,s); 4.04(3H,s); 7.04 (2H,dofd); 8.65(2H,s). 5-CH.sub.3 2             2.35(3H,s); 2.43(3H,s); 7.2- 7.8(2H,m); 8.57(2H,s). ______________________________________

The 2-acyl-5-(mono-substituted pyrimidyl)cyclohexan-1,3-diones of formula XIII used in the preparation of compounds of formula I were characterized by their proton nuclear magnetic resonance spectra. For convenience the pmr data are recorded in Table 4 below. The majority of the compounds were obtained as oils or low-melting point solids and were generally colourless or pale brown. ______________________________________ ##STR19## Position of Pyrimidine   Proton Chemical Shift Substituents Link         .delta. in ppm (CDCl.sub.3) ______________________________________ (X).sub.N = 2-CH.sub.3 5            1.00(3H,t); 1.7(2H,m); R.sup.3 = n-C.sub.3 H.sub.7 2.71(3H,s); 2.6-3.6(7H,m); 8.52(2H,s); 18.27(1H,s) (X).sub.n = 2-CH.sub.3 S 5            0.99(3H,t); 1.7(2H,m); R.sup.3 = n-C.sub.3 H.sub.7 2.55(3H,s); 2.5-3.6(7H,m); 8.39(2H,s); 18.27(1H,s). (X).sub.n = 2-CH.sub.3 O 5            0.99(3H,t); 1.7(2H,m); R.sup.3 = n-C.sub.3 H.sub.7 2.6-3.6(7H,m); 3.98(3H,s); 8.39(2H,s); 18.2(1H,s). (X).sub.n = 5-CH.sub.3 2            1.13(3H,t); 2.30(3H,s); R.sup.3 = C.sub.2 H.sub.5 2.4-3.9(7H,m); 8.50(2H,s); 18.16(1H,s). (X).sub.N = 2-CH.sub.3 S 5            1.16(3H,t); 2.53(3H,s); R.sup.3 = C.sub.2 H.sub.5 2.5-3.6(7H,m); 8.40(2H,s); 18.2(1H,s). ______________________________________

The majority of the mono-substituted pyrimidyl compounds of the invention were obtained as colourless or light brown oils or low-melting point solids and were characterized by and can be identified by their nuclear magnetic resonance spectra. For convenience proton nuclear magnetic resonance spectroscopic (pmr) data are recorded in Table 5 below. ______________________________________ Compound Proton Chemical Shift No       .delta. in ppm (CDCl.sub.3) ______________________________________ 1        0.99(3H,t); 1.34(3H,t); 1.7(2H,m); 2.70 (3H,s); 2.6-3.6(7H,m); 4.11(2H,q); 8.50 (2H,s); 15.6(1H,bs). 2        0.98(3H,t); 1.33(3H,t); 1.7(2H,m); 2.56 (3H,s); 2.5-3.7(7H,m); 4.12(2H,q); 8.44 (2H,s); 15.5(1H,bs). 3        0.99(3H,t); 1.33(3H,t); 1.6(2H,m); 2.5-3.6 (7H,m); 4.00(3H,s); 4.12(2H,q); 8.43(2H,s); 15.5(1H,bs). 4        1.16(3H,t); 1.34(3H,t); 2.56(3H,s); 2.5-3.6 (7H,m); 4.13(2H,q); 8.44(2H,s); 15.0(1H,bs). 5        Not recorded 6        1.16(3H,t); 1.33(3H,t); 2.5-3.7(7H,m); 2.98(3H,s); 4.12(2H,q); 8.77(2H,s); 15.0 (1H,bs). 7        0.98(3H,t); 1.6(2H,m); 2.72(3H,s); 2.6- 3.6(7H,m); 4.67(2H,dofd); 5.8-6.4(2H,m); 8.48(2H,s); 15.0(1H,bs). 8        0.98(3H,t); 1.25(9H,s); 1.34(3H,t); 1.6 (2H,m); 2.5-3.6(7H,m); 4.00(3H,s); 4.12 (2H,q); 8.45(2H,s). 9        1.15(3H,t); 1.34(3H,t); 2.5-3.6(7H,m); 3.17 (6H,s); 4.12(2H,q); 8.25(2H,s); 15.0(1H,bs) 10       1.12(3H,t); 1.33(3H,t); 2.33(3H,s); 2.5- 3.8(7H,m); 4.12(2H,q); 8.47(2H,s); 14.8 (1H,bs). ______________________________________

This non-limiting Example illustrates the preparation of formulations of the compounds of the invention.

Compound No. 1 was dissolved in toluene containing 7% v/v "Teric" N13 and 3% v/v "Kemmat" SC15B 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" SC15B is a formulation of calcium dodecylbenzenesulfonate.)

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 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.)

Compound No.1(10 parts by weight), "Teric" N13 (5 parts by weight) and "Kemmat" SC15B (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.)

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 concensate; "Aerosol" is a Trade Mark and "Aerosol" OT/B is a formulation of the dioctyl ester of sodium sulfosuccinic acid.)

Compound No. 1 (99 parts by weight), silica aerogel (0.5 parts by weight) and synthetic amorphous 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.

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 15 and 16, in the evaluation of the pre-emergence and post-emergence herbicidal activity of the compounds.

The pre-emergence herbicidal activity of the compounds of the invention formulated as described in Example 14 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 placed 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 6 where the damage to plants is rated on a scale of form 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 ______________________________________ ______________________________________ PRE-EMERGENCE HERBICIDAL ACTIVITY Com- pound APPLICATION  TEST PLANT No    Rate (kg/ha) Wh     Ot   Rg  Jm  P   Ip  Ms  Sf ______________________________________ 1     1.0          4      4    5   5   0   0   0   0 3     1.0          4      5    5   5   0   0   0   0 3     0.25         2      3    4   3   0   0   0   0 4     1.0          3      5    5   5   0   0   0   0 5     1.0          5      5    5   5   0   0   0   0 ______________________________________

The post-emergent herbicidal activity of the compounds of the invention formulated as described in Example 14 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 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 contols. The results are represented in Table 7 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 ______________________________________ ______________________________________ POST-EMERGENCE HERBICIDAL ACTIVITY Com- pound APPLICATION  TEST PLANT No    Rate (kg/ha) Wh     Ot   Rg  Jm  P   Ip  Ms  Sf ______________________________________ 1     1.0          5      5    5   5   0   0   0   0 1     0.25         5      5    5   5   0   0   0   0 1     0.06         3      5    5   5   0   0   0   0 2     1.0          0      5    5   4   0   0   0   0 2     0.25         0      4    4   3   0   0   0   0 3     1.0          5      5    5   5   0   0   0   0 3     0.25         4      5    5   5   0   0   0   0 3     0.06         2      5    4   4   0   0   0   0 4     1.0          5      5    5   5   0   0   0   0 4     0.25         5      5    5   5   0   0   0   0 4     0.06         3      4    5   5   0   0   0   0 5     1.0          5      5    5   5   0   0   0   0 5     0.25         5      4    5   5   0   0   0   0 5     0.06         3      3    4   4   0   0   0   0 10    1.0          3      5    5   5   0   0   0   0 10    0.25         1      3    4   3   0   0   0   0 ______________________________________

The compounds were formulated for test by mixing an appropriate amount with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.9 g per liter of "Span" 80 and 78.2 per liter 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 8 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 a 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 8 below. A dash (-) means that no experiment was carried out.

The names of the test plants were as follows: Sb             Sugar beet Rp             Rape Ct             Cotton Sy             Soy bean Mz             Maize Ww             Winter wheat Rc             Rice Sn             Senecio vulgaris Ip             Ipomea purpurea Am             Amaranthus retroflexus Pi             Polygonum aviculare Ca             Chenopodium album Ga             Galium aparine Xa             Xanthium pensylvanicum Ab             Abutilon theophrasti Co             Cassia obtusifolia Av             Avena fatua Dg             Digitaria sanguinalis Al             Alopecurus myosuroides St             Setaria viridis Ec             Echinochloa crus-galli Sh             Sorghum halepense Ag             Agropyron repens Cn             Cyperus rotundas ______________________________________ __________________________________________________________________________ PART A Com- APPLICATION pound Method Rate TEST PLANT No  (kg/ha)  Sb Rp Ct Sy Mz Ww Rc Sn Ip Am Pi Ca __________________________________________________________________________ 1   POST 0.1   -- -- -- 5  4  4 -- -- -- -- -- 1   POST 0.02 -- -- -- -- 3  3  3 -- -- -- -- -- 2   PRE  0.4 -- -- -- -- -- 0  -- -- -- -- -- -- 2   POST 0.05 -- -- -- -- 1  0  0 -- -- -- -- -- 3   POST 0.05 -- -- -- -- 3  0  4 -- -- -- -- -- 3   POST 0.02 -- -- -- -- 2  0  0 -- -- -- -- -- __________________________________________________________________________ __________________________________________________________________________ PART B Com- APPLICATION pound Method Rate TEST PLANT No  (kg/ha)  Ga Xa Ab Co Av Dg Al St Ec Sh Ag Cn __________________________________________________________________________ 1   POST 0.1 -- -- -- -- 4  4  5 5 4 4 4 -- 1   POST 0.02 -- -- -- -- 4  4  4 4 3 4 0 -- 2   PRE  0.4 -- -- -- -- 3  -- 5 -- -- -- -- -- 2   POST 0.05 -- -- -- -- 4  3  4 4 4 3 0 -- 3   POST 0.05 -- -- -- -- 4  4  4 4 5 4 4 -- 3   POST 0.02 -- -- -- -- 3  3  4 4 4 3 0 -- __________________________________________________________________________

## Claims

1. A compound of formula Va ##STR20## wherein X is methyl or methoxy.

2. A compound of formula IX ##STR21## wherein X is methyl or methoxy.

3. A compound of formula XIII ##STR22## wherein X is methyl or methoxy and R.sup.3 is ethyl.