IL98743A - Methyl 2-(substituted methyl)-alpha-oxobenzeneacetate intermediates for fungicides - Google Patents

Description

METHYL INTERMEDIATES FOR FUNGICIDES It relates to derivatives of keto esters useful as Intermediates the preparation of Application 85122 describes compounds having the formula stereoisomers wherein R is a heteroaryl moiety which 1s optionally substituted by one or more oft hydroxy cycloalkyl alkyl which the alkyl moiety optionally substituted heteroaryl heteroaryloxy or or substituents on the heteroaryl moiety of when they are in adjacent may Join to form a or fused phenyl or heteroaryl moieties comprised any of the foregoing substituents are optionally substituted by one or more hydr alke alky 1n which the alkyl moiety 1s optionally substituted heteroaryl phenoxy or wherein phenyl or heteroaryl moieties comprised in any of these substituents are optionally substituted by one or more hydroxy eye or and are cycloalkyl phenyl or the phenyl or groups being optionally substituted alkyl or the heteroaryl moieties or or Y 1s sulphur or N and which may be the same or are alkyl or X or is 0 or an of 1 to and sodium or implicitly discloses the methyl and the corresponding compounds in which oxymethylene linking group is substituted with one or two methyl The compounds of the present invention differ in that they are They are useful as intermediates for preparing the improved fungicides described in tho above mentioned Application No This as Intermediate chemicals for the preparation of the compounds of formula a compound of formula 3 wherein R R R Y and n have the meanings defined in one aspect the Invention provides a compound of formula wherein Y In another aspect the Invention provides a compound of the formula above which X The compounds of formula contain at least one double and are sometimes obtained the form of mixtures of geometric these mixtures can be separated Individual and A licat o c proportions including those which consist substantially of the and those which consist of the The which result from the substituted double bond of the propenoate group are by the commonly used terms and These terms are defined according to the system which is fully described in the literature for J Organic 3rd page et Usually one isomer 1s more active than the the more active being the one wherein the groups and are on opposite sides of the bond of the propenoate group which may be present on the optionally substituted heteroaryl moiety one or more of the methyl and alkenyl alkynyloxy and and alkyl heteroaryl pyrldinyl or heteroaryloxy or phenethyl and phenyl in which the alkyl moiety 1s optionally substituted heteroaryl or or or or or which and are phenyl or substiutents which may be present the phenyl and heteroaryl moieties Include one or more of heteroaryl substltuents described Immediately and the heteroaryl moieties are as defined When any of the substltuents R or the alkyl moiety can be the form of straight or branched that the moiety may be or or or Other references herein to alkyl and alkoxy carry the same 4 When any of the substltuents R R R and X are these groups can be in the form of straight or branched chains where may have either the or the Examples of such groups are and Other references herein to alkenyl carry the same It preferred that and are both hydrogen and that hydrogen or When n is 2 or the substltuents X may be the same or It is generally that n 1s 0 or In another aspect the provides compounds of the formula 1n which B is N or Y has the meaning given p 1s 0 or an of 1 to 3 when B or 0 or an integer of 1 to 4 when B is and A halo fluoro or alkyl methyl or particularly fluoroethyl or alkoxy or Compounds are preferred 1n which the basicity of the nitrogen the heterocyclic Accordingly it 1s preferred that Y is attached to a position to a nitrogen or a substltuent A is attached to a position ortho to a ring nitrogen or When p 1s 2 or 1t Is preferred that the which may be the same or are methoxycarbonyl or Examples of combinations of the substltuents A when p 1s 2 or more are and when B and The compounds listed In Table I which follows are of the compounds of formula which may be prepared from the compounds of the X R2 R3 1 H H E 2 H H H E E 3 H H 4 H H E 5 H H H E H H E H H H E 8 H H E 9 H H H E H H H E H E 12 R H H E H H E H H H E H H H E I I TABLE I I I I X Is n 102 H H H E H 104 H E 105 H Chenical shift of singlet olefinic proton on group Solvent unless otherwise Geanetry of Also illustrative of compounds which may be prepared from the compounds of the invention are the compounds of the in which R2 and X have the same combinations of meanings as each of the corresponding linked compounds in Table I when Y of Compound is compound of Table II corresponds to 10 Compound i Of Table I respect to their meanings of R3 and TABLE Chemical shift of singlet from olefinic proton on from tetramethylsilane Solvent CDCI3 unless otherwise Geometry of Further illustrative of compounds which may be prepared from the compounds of the invention are the compounds of the in which and X have the same combinations of meanings as each of the corresponding compounds in Table I where Y of Compound and hydrogen and SELECTED PROTON DATA Table HI shows selected proton NMR data for certain described in Tables I and Unless otherwise are from Table Chemical shifts are measured in from and deu used as solvent The following abbreviations are used ι br broad t triplet ppm parts per s q quartet million d doublet multiplet COMPOUND 87 TABLE The compounds of formula may be prepared by the steps shown in Scheme Throughout this Scheme the terms y and n are as defined Each of the transformations described in Scheme I is performed at a suitable temperature and though not in a suitable As shown in Scheme the compounds of formula can be prepared by treatment of ketoesters of formula with reagents such as i henylphosphor ane for w G T Anke and F EP Ketoesters of formula may be prepared by methods described in the Particularly useful methods include the reaction of appropriate phenylmagnesium halides or species with dimethyl oxalate using the method described by and A V 1 943 and references oxidation of phenylacetates of formula using selenium generally in the absence of a and generally at a temperature above and oxidation of mandelic acid esters for manganese oxide in a suitable Reference is made to which discloses the compound and other methyl also discloses their method of preparation from the esponding keto esters and the preparation of the keto ester9 25 insufficientOCRQuality

Claims (1)

1. A compound of the formula wherein is a heteroaryl moiety which is optionally substituted by or more in which the alkyl moiety 1s optionally substituted heteroaryl phenyl heteroaryl or or substltuents on the heteroaryl moiety of when they are adjacent may to form a thianthrenyl or phenoxathllnyi fused phenyl or heteroaryl moieties comprised 1n any of the foregoing substltuents are optionally substituted by one or more cycloalkyl in which the alkyl moiety Is optionally substituted with phenyl heteroaryl phenyl or wherein phenyl or heteroaryi moieties comprised 1n any of these substituents are optionally substituted by one or more koxy cycloalkyi or and are cycloalkyi phenyl or phenyl alkyi the phenyl or groups being optionally substituted alkyi or the heteroaryi moieties or or Y Is sulphur or and which may be the same or are X is nitro or n is 0 or an integer of 1 to A compound according to claim 1 1n which Y 1s A compound according to claim 1 or 2 which R 1s heteroaryi optionally substituted by one or more or which and are independently cycloalkyi phenyl or phenyl the phenyl or heteroaryi of any of the foregoing substltuents being optionally substituted 1n the same way as and heteroaryl or or A compound according to claim 1 which X A co which B 1s N or Y has the meaning given claim p Is 0 or an integer of 1 to 3 when Θ or 0 or an Integer of 1 to 4 when B 1s and A acetyl ami or alkyl A compound according to claim 5 1n which Y Is attached to a position ortho to a ring nitrogen or a substituent A attached to a position ortho to a ring nitrogen or AGENT FOR THE APPLICANT insufficientOCRQuality