WO2002028183A1 - Fungicides - Google Patents

Abstract

This invention relates to the use as plant fungicides of certain coumarin, quinolinone and benzothiinone derivatives and the corresponding thiones. It also relates to plant fungicidal compositions containing these compounds and to certain of the compounds themselves.

Description

FUNGICIDES This invention relates to the use as plant fungicides of certain coumarin, quinolinone and benzothiinone derivatives and the corresponding thiones. It also relates to plant fungicidal compositions containing these compounds and to certain of the compounds themselves.

It is known from WO 97/13762 that a range of substituted chromones and coumarins can be used as plant fungicides. It is also known from B S Verma et al in Chimica Acta Turcica, 17 (1989), 433-439 that some substituted 2,3-dihydrocyclopenta [c][l] benzopyran- 4(lH)-ones show activity against certain phytopathogenic fungi. The chemical literature contains many references to substituted 7,8,9, 10-tetrahydro-

6H-dibenzo[b,d]pyran-6-ones and like compounds but there is no indication that they show plant fungicidal activity. Such compounds have been prepared for academic studies, as intermediates for making other compounds and for pharmaceutical applications. For example, the preparations of the compounds l-hydroxy-3-methyl-7,8,9,10-tetrahydro- 6H-dibenzo[b,d]pyran-6-one, l-hydroxy-3,9-dimethyl-7,8,9J0-tetrahydro-6H-dibenzo[b,d]- pyran-6-one, their-3-n-amyl analogues and certain of their acetate derivatives are variously described by J B Chazan et al in Bull Soc Chim Fr, 4, (1968), 1374-1393, P R Bovy et al in J. Med Chem (1991), 34(8), 2410-2414, R Adams et al in J. Am Chem Soc (1940), 62, 2401-2408 and U Kraatz and F Korte in Chem Ber (1973), 106, 62-68, and the preparations of the compounds l-hydroxy-3-methyl-5, 6, 7, 8, 9, 10-hexahydrophenanthridinone-6, 1- hydroxy-3,5-dimethyl-5, 6, 7, 8, 9, 10-hexahydrophenanthridinone-6, l-hydroxy-3-methyl-5- ethyl-5, 6, 7, 8, 9, 10-hexahydrophenanthridinone-6 and l-hydroxy-5-methyl-3-τ.-pentyl-5, 6, 7, 8, 9, 10-hexahydrophenanthridinone-6 are described by U.Kraatz and F Korte in Chem Ber (1973), 106, 62-68. According to the present invention there is provided the use as a plant fungicide of a compound of the general formula (I):

wherein

M, L and K are independently O, S(O)_n where n is 0, 1 or 2, NR₅ or CHRg, provided that at least one is CHRg, that when two are O, L is CHRg and that when two are NR₅ or two or three are CHRg, the values of R₅ and the values of Rg are the same or different;

X is hydroxy, cyclohexanon-2-yloxy, C_w alkylcarbonyloxy, halo(C₁.₆)alkylcarbonyloxy, Cι_₆ alkoxycarbonyloxy, C ₆ alkoxycarbonyl(C₁.₆)alkoxy, halo(C₁.₆)alkoxycarbonyloxy, C_λ_₆ alkoxycarbonyl(phenyl)(C₁.₆)alkoxy, cyclo(C₃.₆)-alkylcarbonyloxy, arylcarbonyloxy, heterocyclylcarbonyloxy, arylcarbonyl(C₁.₆)alkoxy, aryl(C₁.₆)alkoxycarbonyl(Cι.₆)alkoxy, aminocarbonyloxy, mono- or di-(C₁.g)alkyl-aminocarbonyloxy, C ₆ alkoxycarbonyl- carbonyloxy, C^ alkylsulphonyloxy, haloalkylsulphonyloxy, arylsulphonyloxy, heterocyclylsulphonyloxy, di^C^alkoxyphosphonyloxy, dihydroxyphosphonyloxy, cyano(C₁.₆)alkoxy, carboxy(C₁.₆)alkoxy, carboxyhalo(C₁.₆)alkoxy,

alkylcarbonyl- (C^alkoxy, C ₆ alkoxycarbony^C^alkoxy, Cj.₆ alkoxycarbonylhalo(Cι.₆)alkoxy, amino- carbony^C^alkoxy, mono- or di-(Cj.₆)alkylaminocarbonyl(C_M)alkoxy, hydrazinocarbonyl-

Cι_.6 alkylsulphonylamino or X may be H when R₄ is hydroxy, oxo, hydroximino, amino, mono- or di- (C₁.₆)alkylamino, C^ alkylcarbonylamino or C,.₆ alkylsulphonylamino; Y is O, S orNR₇; Z is O or S;

Ri, R₂, and R₃ are independently H, halo, hydroxy, C^ alkyl, halo(C₁.₈)alkyl, hydroxy^_j-_g)- alkyl,

alkoxy(C_1.5)alkoxy(C_1.6)- alkoxy, cyclo(C₃.₆)alkyl, C_M alkylcyclo(C_3.6)alkyl, cyclo(C₃.₆)alkoxy, C_2.6 alkenyl, C₂.₁₂ alkenyloxy, C₂.₆ alkynyl, C₂.₆ alkynyloxy, C_w alkoxycarbonyl, C^ alkylcarbonyloxy- (C₁.₈)alkyl, C_M alkoxycarbonyl(C₁.₈)alkyl, C_x_₆

carboxy(C₁.₆)- alkoxy, cyano, nitro, aryl, heterocyclyl, aryloxy, heterocyclyloxy, aryl(C_j._]0)alkyl or heterocyclyl(C )alkyl, or R_j and R₂ or R₂ and R₃ join to form optionally C ₆ alkyl substituted C₂ alkylenedioxy;

R₄ and Rg are independently H, hydroxy, oxo, hydroximino amino, mono-or-di-(C₁.₆)- alkylamino, C ₆ alkylcarbonylamino, .g alkylsulphonylamino, C ₆ alkyl, C ₆ alkoxy, C₂ alkylenedioxy, cyclo(C_3.6)alkyl, cyclo(C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C_2.6 alkynyl, C_2.6 alkynyloxy, C_w alkylcarbonyloxy, aryl, heterocyclyl, aryloxy or heterocyclyloxy; and Rs and R₇ are independently H, an acid addition salt, C ₆ alkyl, C₂.₄ alkenyl, C₂.₄ alkynyl, C_M alkylcarbonyl, ₂ alkenylcarbonyl, aryl, aryl(C_M)alkyl, arylcarbonyl, C_w alkylsulphonyl or arylsulphonyl; any of the foregoing aryl, heterocyclyl, cycloalkyl and cycloalkoxy groups or moieties being optionally substituted.

Except where otherwise stated, alkyl moieties, including the alkyl moieties of haloalkyl, alkoxy, alkylsulphonyl, etc., suitably contain from 1 to 6, typically from 1 to 4, carbon atoms in the form of straight or branched chains. Examples are methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and tert-butyl, /.-pentyl and «-hexyl.

Halo includes fluoro, chloro, bromo and iodo. Most commonly it is fluoro, chloro or bromo.

Haloalkyl is typically trifluoromethyl and haloalkoxy is typically trifluoromethoxy.

By cycloalkyl (and the cycloalkyl moiety of cycloalkoxy) is meant a saturated carbocyclic ring suitably containing 3 to 6 carbon atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

By oxo is meant a carbonyl oxygen atom. For example, where R₄ is oxo it is an oxygen atom joined to the ring carbon atom by a double bond.

Aryl is usually phenyl but also includes naphthyl, anthryl and phenanthryl. Heterocyclyl includes aromatic heterocyclic groups, referred to as heteroaryl groups, and non-aromatic heterocyclic groups. Typically they are 5- or 6-membered aromatic or non-aromatic rings containing one or more O, N or S heteroatoms which may be fused to one or more other aromatic or heteroaromatic or other heterocyclic rings, such as a benzene ring. Examples are thienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, oxadiazolyl, pyrazolyl, imidazolyl, triazolyl, isothiazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, benzofuryl, benzothienyl, dibenzofuryl, benzothiazolyl, benzoxazolyl, benzimidazolyl, indolyl, quinolinyl, quinoxalinyl, pyrrolidinyl, morpholinyl, thio- morpholinyl and morpholino groups and, where appropriate, N-oxides thereof. Other examples include fully and partially hydrogenated thienyl, furanyl, pyrrolyl, thiazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl and azepinyl. Any of the aryl, heterocyclyl, cycloalkyl and cycloalkoxy values are optionally substituted. Substituents which may be present include one or more of the following: halo, oxo, hydroxy, mercapto, Cι._g alkyl (especially methyl and ethyl), C₂.₆ alkenyl (especially allyl), C₂.₆ alkynyl (especially propargyl), Cj-g alkoxy (especially methoxy), C₂-₆ alkenyloxy (especially allyloxy), C₂.₆ alkynyloxy (especially propargyloxy), halo(C₁.₈)alkyl (especially trifluoromethyl), halo(C₁.₆)alkoxy (especially trifluoromethoxy), Cι-₆ alkylthio (especially methylthio), hydroxy(C_j.₆)alkyl, C_M alkoxy(C_M)alkyl, C_]_₄alkoxy(C₁.₄)alkoxy, C₃.₆ cycloalkyl, C₃-₆ cycloalkyl(C_M)alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heteroaryl (especially optionally substituted pyridyl or pyrimidinyl), optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heteroaryloxy (especially optionally substituted pyridyloxy or pyrimidinyloxy), optionally substituted arylthio (especially optionally substituted phenylthio), optionally substituted heteroarylthio (especially optionally substituted pyridylthio or pyrimidinylthio), optionally substituted aryl(C_M)alkyl (especially optionally substituted benzyl, optionally substituted phenethyl and optionally substituted phenyl n-propyl) in which the alkyl moiety is optionally substituted with hydroxy, optionally substituted heteroaryl(C₁_₄)alkyl (especially optionally substituted pyridyl- or pyrimidinyl- (C_j^alkyl), optionally substituted aryl(C₂.₄)alkenyl (especially optionally substituted phenylethenyl), optionally substituted heteroaryl(C₂.₄)alkenyl (especially optionally substituted pyridylethenyl or pyrimidinylethenyl), optionally substituted

(especially optionally substituted benzyloxy and phenethyloxy), optionally substituted

(especially optionally substituted pyridyl- or pyrimidinyl(C_M)alkoxy), optionally substituted aryloxy^. alkyl (especially phenoxymethyl), optionally substituted heteroaryloxy-(C_M)alkyl (especially optionally substituted pyridyloxy or pyrimidinyloxy- (Cι.₄)alkyl), optionally substituted aryl(C₁ )alkylthio (especially optionally substituted benzylthio and phenethylthio), optionally substituted heteroaryl(C_M)alkylthio (especially optionally substituted pyridyl or pyrimidinyl(C_w)alkylthio), optionally substituted arylthio(C_w)alkyl (especially phenylthio- methyl), optionally substituted heteroarylthio- (C^alkyl (especially optionally substituted pyridylthio- or pyrimiαϋnyltMo(C_1.4)alkyl), acyloxy, including C_M alkanoyloxy (especially acetyloxy) and benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -SO₂R', -OSO₂R', -COR', -CR'=NR" or -N=CR'R" in which R* and R" are independently hydrogen, C_M alkyl, halo(C_M)alkyl, C_M alkoxy, halo(C_M)alkoxy, C_j.₄ alkylthio, C₃.₆ cycloalkyl, C₃.₆ cycloalkyl(Cι.₄)alkyl, phenyl or benzyl, the phenyl and benzyl groups being optionally substituted with halogen, C_M alkyl or C_M alkoxy.

Substituents which may be present in the aryl or heteroaryl rings of any of the foregoing substituents include one or more of the following: halo, hydroxy, mercapto, C_M alkyl, C₂.₄, alkenyl, C_M alkynyl, C_M alkoxy, C₂.₄ alkenyloxy, C_M alkenyloxy, halo- (C_M)alkyl, halo(C_w)alkoxy, C_M alkylthio, halo(C_M)alkylthio, hydroxy(C_w)alkyl, C_1.4alkoxy(Cι-₄)alkyl, C₃.₅ cycloalkyl, C₃.₆ cycloalkyl(C_M)alkyl, alkanoyloxy, phenoxy, benzyloxy, benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, -NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -SO₂R', -OSO₂R', -COR', -CR'=NR" or -N=CR'R", in which R' and R" have the meanings given above.

Typically R_j is H, halo, C_M alkyl, C_M alkoxycarbonyl or nitro. Usually it is H.

Typically R₃ is H, halo, C_l alkyl, aryl(C_M)alkyl or nitro. Usually it is H.

Typically R₄ is H, hydroxy or oxo. Usually it is H. Typically R₅ is H, an acid addition salt (such as -CI, -SO₂(C_M)alkyl or -SO₂phenyl),

Cι_₄ alkyl, C ₄ alkylcarbonyl, G^alkenylcarbonyl or aryl(C_M)alkyl.

Typically Rg is H or Cι-₄ alkyl. Usually it is H.

Typically R₇ is H or C alkyl, for example, methyl.

Typically K is CH₂, O, S, SO, SO₂, NH or an acid addition salt thereof, N-C_w alkyl, N-C_M alkylaryl or CH-C_W alkyl. Usually it is CH₂.

Typically L is CH₂, O, S SO, SO₂, NH or an acid addition salt thereof, N-C_w alkyl, N-CO(C_w)alkyl, N-CO (C₂.₄)alkenyl or N-C_M alkylaryl. Usually it is CH₂.

Typically M is CH₂, NH or an acid addition salt thereof, N-C_M alkyl, N-C^ alkylaryl, or CH-C₁ alkyl. Usually it is CH₂. Typically Y and Z are both O. In one aspect the invention provides the use as a plant fungicide of a compound the of general formula (I) wherein R_]} R₃, R₄, R₅, Rg, R₇, K, L, M, Y and Z have the typical values given above and R₂ and X have the meanings given hereinbefore.

In another aspect the invention provides the use as a plant fungicide of a compound of the general formula (I) wherein K is O, S, SO, SO₂, NH or an acid addition salt thereof, N- C_M alkyl, N-C₁ alkylaryl, CH-C_M alkyl or, typically CH₂ and R-, R₂, R₃, R₄, L, M, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (I) wherein K is CH₂, R₄ is hydroxy, oxo or, typically, H and R_], R₂, R₃, L, M, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (I) wherein K is CH₂, R₄ is H, M is NH or an acid addition salt thereof, N-C_M alkyl, N-C_M alkylaryl, CH-C_M alkyl or, typically, CH₂ and R_l5 R₂, R₃, L, X, Y and Z have the meanings given hereinbefore. In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (I) wherein K and M are both CH₂, R₄ is H, L is O, S, SO, SO₂, NH or an acid addition salt thereof, N-C_M alkyl, N-CO(C_M)alkyl, NCO(C₂.₄)alkenyl, N-C_j-₄ alkylaryl or, typically, CH₂ and R_l5 R₂, R₃, X, Y and Z have the meanings given hereinbefore. In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (I) wherein one of M, L and K is O, S(O)_n where n is 0, 1 or 2, or NR₅ and the other two are CH₂, and R_ls R₂, R₃, R₄, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la):

wherein

R_l5 R₂, and R₃ are independently H, halo, C^ alkyl, C ₆ alkoxy, cyclo(C₃.₆)alkyl, cyclo- (C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C₂.₆ alkynyl, C₂.₆ alkynyloxy,

alkoxycarbonyl, cyano, nitro, aryl, heterocyclyl, aryloxy, heterocyclyloxy, aryl(C_w)alkyl or heterocyclyl- (C_M)alkyl;

R₄, R_g, Rg and R₁₀ are independently H, hydroxy, oxo, C_w alkyl, Cι.₆ alkoxy, cyclo(C₃.₆)- alkyl, cyclo(C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C₂.₆ alkynyl, C₂.₆ alkynyloxy, aryl, heterocyclyl, aryloxy or heterocyclyloxy; X is hydroxy,

alkylcarbonyloxy, halo(C₁.₆)alkylcarbonyloxy,

alkoxycarbonyloxy,

cyclo(C₃.₆)alkylcarbonyloxy, arylcarbonyloxy, aminocarbonyloxy, mono- or di-(C₁-₅)alkylaminocarbonyloxy, C_w alkoxycarbonyl- carbonyloxy, C ₆ alkylsulphonyloxy, arylsulphonyloxy, di-(C_w)alkoxyphosphonyloxy, cyano^_j^alkoxy, carboxy(C₁.₆)alkoxy, carboxyhalo^^alkoxy, C_j-g alkoxy- carbonyl(Cι.₆)alkoxy, C_w alkoxycarbonylhalo(Cι.₆)alkoxy, aminocarbonyl(C,_₆)alkoxy, or mono- or di-(C₁.g)alkylaminocarbonyl(C,.₆)alkoxy or X is H when R₄ is hydroxy or oxo; Y is O, S or NR₇ wherein R₇ is H, C ₆ alkyl, aryl or aryl(C_M)alkyl; and Z is O or S.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein R₈ is H and R_1} R₂, R₃, R₄, Rg, Rι₀, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein R₄ is H, hydroxy or oxo, R₈ is H and R_l3 R₂, R₃,

Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein R₄is H, hydroxy or oxo, R₈ is H, Rg is H, alkyl or phenyl and R_1? R₂, R₃, R₁₀, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein Rj is H, halo, C_M alkyl, nitro or C_M alkoxycarbonyl, R₃ is H, halo, C_M alkyl, benzyl or nitro, s H, hydroxy or oxo, R_s is H, R_g is H, alkyl or phenyl and R₂, Rι₀, X, Y and Z have the meanings given hereinbefore. In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein Rj is H, halo, C_w alkyl, nitro or _l alkoxycarbonyl, R₃ is H, halo, C_M alkyl, benzyl or nitro, R₄ is H, hydroxy or oxo, R_g is H, Rg is H, alkyl or phenyl, R_]0 is H or C alkyl and R₂, X, Y and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein Z is O and R_l5 R₂, R₃, R,, R₈, Rg, R₁₀, X and Y have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein Y is O or NR₇, R₇ is H or C^ alkyl, preferably C]_₄ alkyl, and R R₂, R₃, R₄, R_s, Rg, Rι₀, X and Z have the meanings given hereinbefore.

In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein R, is H, halo, C_M alkyl, nitro or C_M alkoxycarbonyl, R₃ is H, halo, C_M alkyl, benzyl or nitro, R₄ is H, hydroxy or oxo, R₈ is H, Rg is H, alkyl or phenyl, R₁₀ is H or C_M alkyl, Y is O or NR₇, R₇ is H or C_μ6 alkyl, preferably C_j^ alkyl, Z is O and R₂ and X have the meanings given hereinbefore. Typically R₂ is C_M alkyl, for example methyl or z^'_?o-propyl, and X is OH, C₁ alkylcarbonyloxy, carboxy^. - alkoxy, Cι_₄ alkoxycarbonyl(C_lJ()alkoxy, mono- or di-(C₁.₄)alkylaminocarbonyl(C_M)alkoxy or C_M alkoxy carbonyl-carbonyloxy, and typically OH. In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein Rj is H, halo, C_M alkyl, nitro or C_M alkoxycarbonyl; R₂ is H, hydroxy, C^ alkyl, C^ alkoxy, C₂.₄ alkenyloxy or cyano; R₃ is H, halo, Cι_₄ alkyl, benzyl or nitro; R₄ is H, hydroxy or oxo; R_g is H; Rg is H, C_M alkyl or phenyl; R_j0 is H or C_w alkyl; X is hydroxy, C_M alkylcarbonyloxy, C_M alkoxycarbonyloxy, halo(C_M)-alkoxycarbonyloxy, cyclohexanonylcarbonyloxy, nitro substituted phenylcarbonyloxy, C_M alkylaminocarbonyloxy, C_M alkoxycarbonylcarbonyloxy, di^C_{j. 4})alkoxyphosphonyloxy, cyanoalkoxy, carboxy(C_w)alkoxy, carboxyhalo(C₁.₄)alkoxy, C_μ4 alkoxycarbonyl(C_M)alkoxy, C_w alkoxycarbonylhalo(C₁.₄)alkoxy or aminocarbony^C_!. ₄)alkoxy or X is H when R₄ is hydroxy or oxo; Y is O or NR₇, wherein R₇ is H or C_M alkyl; and Z is O. In yet another aspect the invention provides the use as a plant fungicide of a compound of the general formula (la) wherein R_l5 R₄ and R₈ are all H; R₂ is C₁ alkyl, C_M alkoxy, C₂.₄ alkenyl or C₂.₄ alkenyloxy; R₃, Rg and R₁₀ are independently H or C_M alkyl; X is hydroxy, C_M alkylcarbonyloxy, carboxy(C₁.₄)alkoxy, C ₄ alkoxycarbonyl(C_j.4)alkoxy, mono- or di-(C_M)alkylaminocarbonyl(Cι.₄)alkoxy or C_M alkoxycarbonylcarbonyloxy; Y is O or NR₇, wherein R₇ is C₁ alkyl; and Z is O.

In yet another aspect the invention provides a compound of the general formula (la) wherein R_l5 R₄ and R₈ are all H; R₂ is C_w alkyl, C alkoxy, C₂ alkenyl or C₂.₄ alkenyloxy; R₃, Rg and R₁₀ are independently H or C_M alkyl; X is hydroxy, C_M alkylcarbonyloxy, carboxy-(C_M)alkoxy, C_w alkoxycarbonyl(C₁.₄)alkoxy, C_Malkylaminocarbonyl(C,.₄)alkoxy or C_M alkoxycarbonylcarbonyloxy; Y is O or NR₇, wherein R₇ is C_w alkyl; and Z is O; provided that R₂ is not methyl when R₃ and Rg are both H, Rι₀ is H or methyl, X is OH or methylcarbonyloxy and Y is 0 or when R₃, Rg and R₁₀ are all H, X is OH and Y is N-methyl or N-ethyl, that R₂ is not rc-propyl when R₃ and Rg are both H, R₁₀ is methyl, X is OH and Y is O and that R₂ is not rø-butoxy when R₃, Rg and R₁₀ are all H, X is OH and Y is O or N- methyl.

Compounds which may be used in the invention are illustrated in Tables 1 and 2 below. The compounds in Table 1 have the general formula (la) with the values of R_l5 R₂, R₃, R₄, R₈, Rg, R₁₀, X, Y and Z given in the table. The compounds in Table 2 have the general formula (I) with the values of R_l5 R₂, R₃, R₄, K, L, M, X, Y and Z given in the table.

Table 1 continued

Table I continued

Table 1 continued

Table 1 continued

Comp'd i R₂ R- 4 R_* Rg R„ X Melting Point No O

92 H CH₃ H H H H H OCH(plιenyl)C(0)OC₂H₅ O O

93 H CH, H H ^"H^" H H OCH₂C(0)nap ιyl O O

94 H CH, H H H H H OCH₂C(0)-4-CH₃-p-ιenyl O O

95 H CH. H H H H H 0CH₂C(0)-4-biplιenyl O

96 H CH, H H H H H OC(0)-2-furyl

97 H CH, H H H H H OCH₂C(0)C(CH₃)₃ O O

98 H CH, H H H H H OC(0)cyclolιexyl O O

99 H CH. H H H H H 0(0)cyclopropyl

The compounds of formula (I) which can be used in the invention may be prepared as follows.

A compound of formula (I) where Y and Z are both O may be prepared by reacting a phenol of general formula (II):

wherein R_l5 R₂, R₃ and X have the meanings hereinbefore defined, with a cyclohexanone of general formula (III) or a cyclohexanone acetal of general formula (IN):

wherein R₄, R_s, Rg and R₇ have the meanings hereinbefore defined and R₈ and Rg are independently Cj.₆ alkyl.

Compounds of the general formula (II), (III) and (IN) are known from the chemical literature or may be made by known methods.

A compound of formula (I) where X is OH and Y and Z are O may be prepared by reacting a resorcinol of general formula (V) :

wherein R_]5 R₂ and R₃ have the meanings hereinbefore defined, with a cyclohexanone of general formula (III) or a cyclohexanone acetal of general fomula (IN). Some compounds of formula (I) where X is OH, Y and Z are O, R_l5 R₃, R₄, R₅ and R₇ are H, Rg is H or methyl and R₂ is alkyl are described in the literature (P.R Bovy et al, JMed Chem 1991, 34, 2410-2414; U.Kraatz and F Korte, Chem Ber 1973, 106, 2-68 and J B Chazan et al, Bull Soc Chim Fr, 4, (1968), 1374-1793 and R Adams et al, JAm Chem Soc (1940), 62, 2401-2408).

A compound of formula (I) where X is other than OH and Y and Z are O may be prepared by reacting a phenol of general formula (VI):

wherein R_l3 R₂, R₃ R₄, R₅ Rg and R₇ have the meanings hereinbefore defined, with a reactive halide (Nil):

R₁₀L (VII). wherein R₁₀ is C ₆ alkyl, C^ cycloalkyl, C₂.₆ alkenyl, C₂.₆ alkynyl, C ₆ alkylcarbonyl, C_w alkylsulphonyl, arylsulphonyl or substituted alkyl and L is halo.

A compound of formula (I) where Y is ΝR_g may be prepared by reacting a lactone of general formula (VIII) :

where R_l5 R₂, R_3ιR₄, R_5,Rg, R₇ and X have the meanings hereinbefore defined, with an amine of general formula (IX):

R₈NH₂ (IX) wherein R₈ is H, (C_j.₆)alkyl, aryl or aralkyl. Some of these compounds of formula (I) where Y is NR₈ and R₈ is H or alkyl are described in the literature (U.Kraatz and F Korte, Chem Ber 1973, 106, 62-68).

A compound of formula (I) where Z is S may be prepared by reacting a lactone or lactam of general formula (X):

wherein R R₂, R₃ R₄, R₅ Rg, R₇, X and Y have the meanings hereinbefore defined, with a thiolating agent such as phosphorus pentasulphide or Lawesson's reagent (2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diρhosphetane-2,4-disulphide). The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe griseά) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia triticina (or reconditά), Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Blumeria (or Erysiphe) graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerothecafusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp.,

Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergϊllus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp. (Pleospora spp.) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusd), Brooks fruit spot (Mycosphaerella pomi), Cedar apple rust (Gymnosporangiumjuniperi-virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) and white rot (Botryosphaeria dothided) on apples and pears; Plasmopara viticola on vines; other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pyihium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberellafujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticϊllium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophoderniium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMN) and Polymyxa betae on sugar beet as the vector of rhizomania).

A compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant. The invention therefore provides a method of combating or controlling phytopathogenic fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other growth medium, e.g. nutrient solution.

The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.

The compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.

In order to apply a compound of formula (I) to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other plant growth medium, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of fungi such that a compound of formula (I) is applied at a rate of from OJg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare. When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to lOg (for example 0.00 lg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.

In another aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.

In a still further aspect the invention provides a method of combating and controlling fungi at a locus which comprises treating the fungi or the locus of the fungi with a fungicidally effective amount of a composition comprising a compound of formula (I). The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula

(I)-

Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of - said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG). Wettable powders (WP.) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank). Emulsifϊable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially i either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or i EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a icroemulsion or forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example w-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial poly condensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound. A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)) .

A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier). Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- wopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3 -sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of all ylene oxides, such as ethylene oxide, propylene Oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

A compound of formula (I) may be applied by any of the known means of applying fungicidal compounds. For example, it may be applied, formulated or unformulated, to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I). The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).

The compositions of this invention may contain other compounds having biological activity, for example micromitrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.

By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I). The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition.

Examples of fungicidal compounds which may be included in the composition of the invention are AC 382042 (N-(l -cyano- l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) pro- pionamide), acibenzolar, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chiiiomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cyamidazosulfamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide l,l'-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, didecyl dimethyl ammonium chloride, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,0-di-t-.o-pro-pyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxain, ethirimol, ethyl (-^-N-beιx-yl-N([methyl(me l-mioethylideneamino- oxycarbonyl)amino]1hio)-β-alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide_. fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fiiberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LYl 86054, LY211795, LY 248908, man- cozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, MON65500 (N-allyl-4,5-dimethyl-2-trimethylsilyl- thiophene-3 -carboxamide) , my clobutanil, ΝTΝ0301 , neoasozin, nickel dimethyldithio- carbamate, nitrothale-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazbate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamqcarb hydrochloride, propiconazole, propineb, propionic acid, pyraclostrobin (methyl N-(2-[N -(4-chlorophenyl)- pyrazolyl-3-oxymethyl]phenyl)-N-methoxycarbamate; BAS500), pyrazophos, pyrifenox, pyrimethanϋ, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, 2-(thiocyanomemylthio)benzothiazole, thiophanate-methyl, thira , tiadinil, timibenconazole, tolclofos-methyl, tolylfluaήid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb, ziram. zoxamide and compounds of the formulae:

The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases. Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation. The preparation of the compounds used in the invention are illustrated in Examples 1 to 19 and their use as plant fungicides is illustrated in Example 20. The following abbreviations are used: g — grammes ml = millilitres m.p. = melting point

M Molar

EXAMPLE 1

This Example illustrates the preparation of l-hydroxy-3-methyl-7,8,9,10-tetrahydro- 6H-dibenzo[b,d]pyran-6-one (Compound No. 5 in Table 1).

Phosphorus oxychloride (3.9g, 2.35ml) was added dropwise to a stirred solution of orcinol monohydrate (4g) and ethyl-2-cyclohexanone carboxylate (5.3g) in dry toluene under a nitrogen atmosphere. After refluxing for 2 hours, the mixture was cooled to give a crystalline solid. Recrystallisation of the solid from methanol gave l-hydroxy-3-methyl- 7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one as an off-white solid m.p. 245-247°C.

EXAMPLE 2 This Example illustrates the preparation of l-methyloxalyloxy-3-methy 1-7, 8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 51 in Table 1).

A solution of l-hydroxy-3-methyl-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (0.2g) (see Example 1; Compound No. 5 in Table 1), triethylamine (0J3ml) and methyl oxalyl chloride (0.08ml) in dichloromethane (15ml) was stirred at room temperature for 8 hours. The solution was washed with 2M ΗC1, water, sodium bicarbonate and dried over anhydrous magnesium sulphate. Removal of the solvent gave a yellow solid which recrystallised from ethanol to give the title compound as a white solid m.p. 156-158°C

(ME.⁺=317).

EXAMPLE 3

This Example illustrates the preparation of 1 ,3-dihydroxy-7,8,9, 10-tetrahydro-6H- dibenzo[b,d]pyran-6-one (Compound No. 16 in Table 1). Phosphorus oxychloride (12.9 g) was added dropwise to a stirred solution of phloroglucinol dihydrate (15.0 g) and ethyl 2-cyclohexanone carboxylate (17.3 g) in dry toluene (100 ml) at ambient temperature. The resulting solution was heated at reflux for 7 hours, then allowed to cool and the solvent evaporated under reduced pressure to leave an orange solid. Trituration, with ethyl acetate/hexane provided l,3-dihydroxy-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one as a pink solid. Η nmr δ 1.7 (4Η, m), 2.4 (2H, m), 3.1 (2H, m), 6.2 (2H, m).

EXAMPLE 4

This Example illustrates the preparation of 3-allyloxy-l-hydroxy-7,8,9,10-tetrahydro-

6H-dibenzo[b,d]ρyran-6-one (Compound No. 15 in Table 1).

A mixture of l,3-dihydroxy-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (500 mg) (see Example 3; Compound No. 16 in Table 1), allyl bromide (260 mg), potassium carbonate (297 mg) and acetone (20 ml) was stirred at ambient temperature for 4 hours, then heated to reflux for 6 hours. After cooling the mixture was filtered and the filtrate evaporated under reduced pressure to provide an orange gum. Purification by flash chromatography (with ethyl acetate/hexane as eluant) provided 3-allyloxy-l-hydroxy-

7,8,9, 10-tetrahydro-6H-dibenzo[b,d]pyran-6-one as a cream solid. Η nmr δ l .74 (4Η, m), 2.43 (2H, m), 3.12 (2H, m), 4.56 (2H, m), 5.29 (1H, m), 5.42 (1H, m), 6.05 (1H, m), 6.27 (1H, d), 6.32 (1H, d).

EXAMPLE 5

This Example illustrates the preparation of 3,8-dimethyl-l-hydroxy-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 24 in Table 1).

Preparation of 2-carbethoxy-4-methylcyclohexanone

A solution of lithium diisopropylamide (2.0M solution in hept-me/tefrahydrofuran/ethylbenzene; 25 ml) was added dropwise to a stirred solution of 4- methylcyclohexanone (5.0 g) and diethyl carbonate (38 g) in dry tetrahydrofuran (30 ml) under nitrogen at -78°C. The rate of addition was adjusted to maintain the reaction temperature below -70°C. After the addition was complete the reaction mixture was allowed to warm to ambient temperature and stirred for a further 20 hours. Dilute aqueous acetic acid was added to neutralise the reaction mixture, which was then extracted with ether. The combined organic phases were dried over magnesium sulphate, filtered and the filtrate evaporated under reduced pressure to leave an orange oil. This was purified by flash chromatography (with ether hexane as eluant) to yield 2-carbethoxy-4-methylcyclohexanone. 'H nrnr δ 0.86 (1H, q), 0.96 (3H, d), 1.08 (3H, t), 1.55-1.80 (4H, m).2.25-2.40 (2H, m), 4J7 (2H, q).

Preparation of 3,8-⁽hmemyl-l-hydroxy-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 24 in Table 1)

Phosphorus oxychloride (1.05 g) was added dropwise to a stirred solution of orcinol monohydrate (1.05 g) and 2-carbethoxy-4-methylcyclohexanone (1.49 g) in dry toluene (30 ml) at ambient temperature. The resulting solution was heated at reflux for 3 hours, then allowed to cool. The solvent was decanted, and the resulting solid purified by crystallisation from methanol to provide 3,8-dimethyl-l-hydroxy-7,8,9,10-tetrahydro-6H- dibenzo[b,d]pyran-6-one as a pale yellow solid. m.p. 242-243°C.

EXAMPLE 6

This Example illustrates the preparation of 3,5-dimethyl-l-hydroxy-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyrid-6-one (Compound No. 12 in Table 1).

A mixture of l-hydroxy-3-me1hyl-7,8,9,l0-tefrahydro-6H-dibenzo[b,d]pyran-6-one (920 mg) (see Example 1; Compound No. 5 in Table 1), and methylamine (40% aqueous solution; 35ml) was heated at 190°C under pressure (395 psi) in an autoclave for 40 hours. After cooling and pressure release the reaction mixture was acidified by the addition of concentrated hydrochloric acid and the resulting solid removed by filtration. The solid was recrystallised from ethanol to provide 3,5-dimethyl-l-hydroxy-7,8,9,10-tetrahydro-6H- dibenzo[b,d]pyrid-6-one as a brick red solid. m.ρ. 310-315°C (decomposes).

EXAMPLE 7

This Example illustrates the preparation of l-hydroxy-3-methyl-7,8,9,i0-tetrahydro- 6H-dibenzo[b,d]pyrid-6-one (Compound No. 10 in Table 1).

Preparation of 6-carbethoxy-l,4-dioxaspiro[4,5]decane

A solution of 2-carbethoxycyclohexanone (5.0 g), ethane- 1,2-diol (4.9 g) and camphor sulphonic acid (0J g) in toluene (100 ml) was heated at reflux in a Dean-Stark apparatus for 4 hours, then allowed to cool. Ether (70 ml) was added and the solution washed with saturated aqueous sodium hydrogen carbonate and brine, dried over sodium sulphate, and filtered. The filtrate was concentrated under reduced pressure to provide 6- carbethoxy-l,4-dioxaspiro[4,5]decane as a yellow oil.

Η nmr δ 1.25 (3Η, t), 1.43-1.57 (5H, m), 1.81-1.99 (3H, m), 2.65 (1H, dd), 3.84-4.00 (4H, m), 4J5 (2H, q).

Preparation of l,4-dioxaspiro[4,5]decane 6-carboxylate

A solution of sodium hydroxide (0.57 g) in water (40 ml) was added to a solution of 6-carbethoxy-l,4-dioxaspiro[4,5]decane (3.04 g) in methanol (80 ml). The solution was then heated at reflux until reaction was complete, cooled and the methanol evaporated under reduced pressure. 2N Hydrochloric acid was added to bring the solution pH to 3, and the solution extracted with ether three times. The combined ether extracts were dried over sodium sulphate, filtered and the filtrate evaporated under reduced pressure to yield 1,4- dioxaspiro[4,5]decane 6-carboxylate as a pale yellow solid. ^!H rrmr δ 1.3 (1H, ), 1.4 (1H, m), 1.7 (3H, ), 1.9 (3H, m), 2.7 (1H, m), 4.0 (4H, m). Preparation of N-(3-hydroxy-5-me ylphenyl)-l,4-dioxaspiro[4,5]decane 6-carboxarnide

Oxalyl chloride (2 ml) was added to a stirred solution of l,4-dioxaspiro[4,5]decane 6- carboxylate (1.36 g) and dimethylformamide (1 drop) in dichloromethane (7 ml). The reaction mixture was stirred at ambient temperature for 2 hours and the solvent then evaporated under reduced pressure. The residue was dissolved in dichloromethane (5 ml) and added to a stirred solution of 3-amino-5-methylphenol (2.7 g) and friethylamine (3 ml) in dichloromethane (8 ml). The resulting solution was stirred overnight at ambient temperature, 2Ν hydrochloric acid added and the mixture extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate, filtered and the filtrate evaporated under reduced pressure to provide a brown gum. This was purified by flash chromatography (with ethyl acetate/hexane as eluant) to yield N-(3-hy droxy-5-methylphenyl)- 1,4- dioxaspiro[4,5]decane 6-carboxamide as a brown solid. Ηnmr δ 1.3-2.1 (8H, m), 2.26 (3H, s), 2.64 (1H, dd), 4.00 (4H, m), 6.40 (1H, s), 6.47 (1H, s), 7.64 (lH, s), 8.38 (lH, br s).

Preparation of l-hydroxy-3-memyl-7,8,9,10-tefrahyά^o-6H-dibenzo[b,d]pyrid-6-one (Compound No. 10 in Table 1).

Trifluoromethanesulphonic acid (0.96 ml) was added dropwise to a stirred suspension of N-(3-hydroxy-5-methylphenyl)-l,4-dioxaspiro[4,5]decane 6-carboxamide (0.63 g) in dichloromethane (8 ml). The mixture was stirred at ambient temperature for 15 minutes, then added with caution to saturated aqueous sodium hydrogen carbonate (40 ml). The resulting mixture was stirred for 45 minutes, then filtered to provide a beige solid. This was purified by column chromatography (with ethyl acetate as eluant) to provide l-hydroxy-3- methyl-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyrid-6-one as pale beige solid, m.p. 270-284°C (decomposes). EXAMPLE 8

This Example illustrates the preparation of 4-benz l-l-hydroxy-7,8,9,10-tetrahydro- 6H dibenzo[b,d]pyran-6-one (Compound No. 14 in Table 1).

Preparation of 2-benzyl-5-(t-butyldimethylsiloxy)phenol

A solution of 4-benzyhesorcinol (500 mg), t-butyldimethylsilyl chloride (170 mg) and imidazole (380 mg) in dry dimethylformamide (10 ml) was heated at 90°C for 3 hours, then allowed to cool and the solvent evaporated under reduced pressure to leave an orange oil. This was purified by flash chromatography (with ethyl acetate/hexane as eluant) to provide 2-benzyl-5-(t-butyldimethylsiloxy)phenol. 'Η rnnr δ 0.0 (6Η, s), 0.8 (9H, s), 3.75 (2H, s), 6.2 (2H m), 6.8 (1H, d), 7.0 (5H, m).

Preparation of 2-benzyl-5-(t-butyldimethylsiloxy)phenyl l,4-dioxaspiro[4,5]decane 6- carboxylate

A solution of 2-benzyl-5-(t-butyldimethylsiloxy)phenol (360 mg), dicyclohexylcarbodiimide (260 mg) and 4-dimethylanιinopyridine (catalytic) in dry dichloromethane (15 ml) was stirred at ambient temperature for 15 minutes. A solution of l,4-dioxaspiro[4,5]decane 6-carboxylate (210 mg) (see Example 7) in dry dichloromethane (5 ml) was added and stirring continued for 4 hours. Water was added to the mixture, which was then filtered through Hyflo® and extracted with ethyl acetate. The organic extracts were dried over magnesium sulphate, filtered and the filtrate evaporated under reduced pressure to leave a white solid. This was purified by flash chromatography (with ethyl acetate/hexane as eluant) to provide 2-benzyl-5-(t-butyldimethylsiloxy)phenyl l,4-dioxaspiro[4,5]decane 6- carboxylate.

Η nmr δ 0.00 (6H, s), 0.76 (9H, s), 1.0-1.8 (8H, m), 2.70 (1H, dd), 3.02 (1H, m), 3.6-3.8 (5H, ), 6.36 (1H, d), 6.44 (1H, dd), 6.76 (1H, d), 6.9-7J (5H, m). Preparation of 4-benzyl-l-hydroxy-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 14 in Table 1)

Trifluoromethanesulphonic acid (600 mg) was added to a stirred solution of 2-benzyl- 5-(t-butyldimethylsiloxy)phenyl l,4-dioxaspiro[4,5]decane 6-carboxylate (400 mg) in dry dichloromethane (10 ml) at ambient temperature. The resulting solution was stirred at ambient temperature for 3 hours, then poured with caution into saturated aqueous sodium hydrogen carbonate. The resulting mixture was stirred for 1 hour, then extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate, filtered and the filtrate evaporated under reduced pressure to leave a white solid. This was purified by flash chromatography (with ethyl acetate/hexane as eluant) to provide 4-benzyl-l-hydroxy- 7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one.

Η nmr δ 1.25 (2Η, m), 1.76 (4H, m), 2.50 (2H, m), 4.03 (2H, s), 6.63 (1H, d), 7.05-7.30 (6H, m).

EXAMPLE 9

This Example illustrates the preparation of 3-meth i- 1 - trifluoromemanesulphonyloxy-7,8,9,10-tefrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 6 in Table 1).

Trifluoromethanesulphonic anhydride (0.43 ml) was added to a stirred suspension of l-hydroxy-3-methyl-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (500 mg) (see Example 1; Compound No. 5 in Table 1) and 2,6-di-t-butyl-4-methylpyridine (0.63 g) in dry dichloromethane (10 ml) at 0°C. The resulting mixture was allowed to warm to ambient temperature and stirred for 5.5 hours. Ether was added and the mixture filtered, the solid being washed with further ether. The filtrate was evaporated- under reduced pressure to provide an orange solid. This was purified by column chromatography (with ethyl acetate/hexane as eluant) to provide 3-methyl-l-trifluoromethanesulphonyloxy-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one as a pale yellow oil.

Η nmr δ 1.80 (4Η, m), 2.46 (3H, s), 2.61 (2H, m), 2.98 (2H, m), 7.05 (1H, d), 7.17 (1H, d). EXAMPLE 10

This Example illustrates the preparation of 3-methyl-10-oxo-7,8,9,10-tetrahydro-6H- dibenzo[b,d]pyran-6-one (Compound No. 13 in Table 1).

Preparation of 3-methyl-7,8,9,10-tetrahydro-6H-dibenzoj ,d]py an-6-one

Formic acid (0.04 ml) was added to a stirred solution of 3 -methyl- 1- trifluoromethanesulphonyloxy-7,8,9, 10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (190 mg) (see Example 9; Compound No. 6 in Table 1), palladium acetate (2 mg), 1,1 '- bis(diphenylphosphino)ferrocene (11 mg) and triethylamine (0.22 ml) in dimethylformamide (1 ml). The resulting orange solution was heated at 60°C for 2 hours, then allowed to cool and brine added. The resulting mixture was extracted with ether, and the combined organic extracts washed with brine, dried over sodium sulphate, filtered arid the filtrate evaporated under reduced pressure to leave a brown gum. This was purified by column chromatography (with ethyl acetate/hexane as eluant) to provide 3-methyl-7,8,9,10-tetrahydro-6H- dibenzo[b,d]pyran-6-one as a pale yellow waxy solid. m.p. 105-107°C.

Preparation of 3-methyl-10-oxo-7, 8, 9, 10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 13 in Table 1).

Chromium trioxide (0.46 g) was added to a stirred solution of 3-methyl-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (250 mg) and acetic anhydride (0.33 ml) in glacial acetic acid (6.2 ml). The resulting mixture was kept at ambient temperature for 3 days, then poured into water and extracted with dichloromethane. The organic extracts were washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulphate, filtered and the filtrate evaporated under reduced pressure to leave an orange gum. This was purified by column chromatography (with ethyl acetate/hexane as eluant) to provide 3 -methyl- 10- oxo-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one as a white solid. EXAMPLE 11

This Example illustrates the preparation of 10-hydroxy-3-methyl-7,8,9, 10-tetrahydro-

6H-dibenzo[b,d]pyran-6-one (Compound No. 18 in Table 1).

Cerium chloride heptahydrate (30 mg) was added to a stirred solution of 3-methyl- 10-oxo-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (19 mg) (see Example 10; Compound No. 13 in Table 1) in methanol (2 ml). The mixture was stirred until homogeneous and then sodium borohydride (31 mg) was added. The resulting mixture was stirred at ambient temperature for 1 hour, then saturated aqueous ammonium chloride was added and stirring continued for 30 minutes. The mixture was then partitioned between saturated aqueous ammonium chloride and ether. The phases were separated, the organic washed with brine and the combined aqueous phases extracted with ether. The combined organic extracts were dried over sodium sulphate, filtered and the filtrate evaporated under reduced pressure to provide a yellow gum. This was purified by column chromatography (with ethyl acetate/hexane as eluant) to yield 10-hydroxy-3-methyl-7,8,9,10-tetrahydro-6H- dibenzo[b,d]pyran-6-one as a white solid. m.p. 153-156°C

EXAMPLE 12

This Example illustrates the preparation of l-carboxymethyloxy-3-methyl-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 29 in Table 1). Potassium carbonate (1.20g) and sodium chloroacetate (0.38g) were added portionwise to a solution of l-hydroxy-3-methyl-7, 8,9,10-tetrahydro-6H-dibenzo [b,d]pyran- 6-one (0.50g) (see Example 1; Compound No. 5 in Table 1) in acetone (15ml) and the resulting mixture refluxed for 8 hours. After cooling to room temperature, the solvent was evaporated, the resulting solid taken up in water. The aqueous layer was washed with ethyl acetate, acidified with 2M ΗC1 until pΗ 2 and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulphate and the solvent removed to give the title compound as a pink solid (0.21g) m.p. 234-236°C (MH⁺=289). Η nmr δ 1.70 (4H, m), 2.25 (3H, s), 2.40 (2H, m), 3.15 (2H, m), 4.15 (2H, m), 6.45 (1H, s), 6.55 (lH, s) ppm.

EXAMPLE 13

This Example illustrates the preparation of l-ethylcarboxy-3-methyl-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 30 in Table 1). To a solution of l-hydroxy-3-me yl-7,8,9,10-tetrahydrp-6H-dibenzo[b,d]pyran-6- one (0.50g) (see Example 1; Compound No. 5 in Table 1) in dichloromethane (20ml) under nitrogen were added sequentially, pyridine (0.88ml), propionyl chloride (l.Og, 0.9ml) and 4-dimemylaminopyridine (0.08g). The mixture was stirred for 1 hour at room temperature and poured into ice-cold 2M ΗC1 (150ml). The organic phase was washed with saturated sodium bicarbonate solution (2 x 30ml), saturated sodium chloride (2 x 30rήl) and dried over anhydrous magnesium sulphate. Removal of the solvent gave a yellow solid which was recrystallised from ethanol to give the title compound as colourless needles (0.48g) m.p. 120- 122°C (MΗ =287)

EXAMPLE 14

This Example illustrates the preparation of l-hydroxy-3-methyl-4-nitro-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 40 in Table 1) and l-hydroxy-3- memyl-2-mfro-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 44 in Table

1). A solution of c. ΗNO₃ (0.27g) and c. H₂SO₄ (0.42g) was added dropwise with caution to a solution of l-hydroxy-3-methyl-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (0.50g; see Example 1, Compound No. 5 in Table 1) in diethyl ether (30ml) and c. Η₂SO₄ (0.42g) at 0°C. After stirring at 0°C for 30 minutes, the reaction was allowed to warm up to room temperature, poured onto ice and the yellow-brown solid filtered off. The solid was purified by column chromatography (silica eluted with dichloromethane) to give the title compounds: l-hyd-roxy-3-memyl-4-ιιifro-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one as a pale yellow solid (0.035g) m.p. 224-226°C (MΗ^|-=276) (Compound No. 40 in Table 1).

Η nmr δ 1.60 (4H, m), 2.20 (3H, s), 2.30 (2H, m), 3.00 (2H, m), 6.60 (IH, s), 11.70 (IH, bs) ppm.

1 -hydroxy-3-methyl-2-nitro-7,8,9, 10-tetrahydro-6H-dibenzo[b,d]pyran-6-one as a pale yellow solid (0.059g) m.p. 164-165°C (MΗ^1"=276) (Compound No. 44 in Table 1). Η nmr d 1.80 (4H, m), 2.55 (2H, m), 2.70 (3H, s), 3.20 (2H, m), 6.75 (IH, s), 12.2 (IH, bs) ppm.

EXAMPLE 15

This Example illustrates the preparation of l-me1hylcarboxymethyloxy-3-methyl- 7,8,9, lO-tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 45 in Table 1). Potassium carbonate (0.44g) was added portionwise to a solution of l-hydroxy-3- methyl-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyran-6-one (0.25g; see Example 1, Compound No. 5 in Table 1) and methyl chloroacetate (0J4ml) in dry acetone (12ml). The mixture was refluxed for 2 hours, cooled to room temperature and filtered. The filtrate was evaporated to give a white solid which was recrystallised from ethanol to give the title compound as white needles (0.22g) m.pJ33-135°C (MΗ"=303).

EXAMPLE 16

This Example illustrates the preparation of l-carboxymethyloxy-3,5-dimethyl- 7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyrid-6-one (Compound No. 11 in Table 1). Sodium chloroacetate (0.039g) was added portionwise to a mixture of 3,5-dimetbyl- l-hydroxy-7,8,9,10-tetrahydro-6H-dibenzo[b,d]pyrid-6-one (0.055g) (see Example 6; Compound No. 12 in Table 1) and potassium carbonate (0J2g) in acetone (15ml). The mixture was refluxed for 4 hours, cooled to room temperature and evaporated to dryness. The solid residue was dissolved in water, acidified with 2M ΗC1 until pΗ 3 and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulphate and the solvent removed to give a yellow solid. Recrystalhsation from ethanol gave the title compound as an orange solid (0.01 Og) m.p. 298-300°C.

EXAMPLE 17

. This Example illustrates the preparation of 2-chloro-l-hydroxy-3-methyl-7,8,9,10- tetrahydro-6H-dibenzo[b,d]pyran-6-one (Compound No. 17 in Table 1).

A mixture of l-hydroxy-3-methyl-7,8,9,10-tetrahydro-6Η-dibenzo[b,d]pyran-6_:one (0.30g; see Example 1, Compound No. 5 in Table 1), N-cMorosuccinimide (0J8g) and benzoyl peroxide (0.025g) in fluorobenzene (7ml) was refluxed for 6 hours. The reaction mixture was cooled to room temperature, the white crystalline solid filtered off and purified by column chromatography (silica eluted with ethyl acetate/hexane 1:1) to give the title compound as a white solid (0J2g) m.ρ. 198-199°C (MET=265). Η nmr δ 1.75 (4H, m), 2.40 (3H, s), 2.50 (2H, m), 3.20 (2H, m) 6.80 (IH, s) ppm.

EXAMPLE 18

This Example illustrates the preparation of l-hydroxy-3-methyl-9,10-dihydro-6H- benzo-7H-pyrano-pyran-6-one (Compound No. 8 in Table 2).

Stage 1 : Preparation of 3 -carboxymethyl-tetrahydro-4H-ρyran-4-one

A solution of tetrahydro-4H-pyran-4-one (3.00g) and dimethyl carbonate (10ml) were added dropwise with caution to sodium hydride (1.44g) with stirring. After complete addition, the reaction mixture was heated at 80°C for 3 hours, cooled to room temperature, quenched with 10% ΗC1 and extracted with ethyl acetate. The ethyl acetate extracts were washed, dried, and the solvent removed to give a colourless oil. Purification by column chromatography (silica eluted with ethyl acetate hexane 1:1) gave 3-carboxymethyl- tetrahydro-4H-pyran-4-one (0J9g) as a colourless liquid. Η nmr δ 2.40 (2Η, m), 3.75 (3H, s), 3.85 (2H, m), 4.30 (2H, ), 12.00 (IH, s) ppm. Stage 2 : Preparation of l-hydroxy-3-methyl-9,10-dihydro-6H-benzo-7H-pyrano-pyran-6- one (Compound No. 8 in Table 2).

Phosphorus oxychloride (0.33g, 0.20ml) was added dropwise to a stirred solution of orcinol monohydrate (0.30g) and 3-carboxymethyl-tetrahydro-4H-pyran-4-one (0J7g) in dry toluene (5ml) under a nitrogen atmosphere. The reaction mixture was heated at 80°C for 5 hours, cooled to room temperature and the solvent removed to give an orange solid. Recrystalhsation from ethyl acetate gave the title compound as an orange powder (0.22g) m.p. 200-201°C (MΗ+=233). Η nmr δ 2.15 (3H, s), 2.70 (2H, m), 3.25 (2H, m), 4.40 (2H, m), 6.25 (IH, s), 6.45 (IH, s) ppm.

EXAMPLE 19

This Example illustrates the preparation of l-hydroxy-3-methyl-9,10-dihydro-6H- benzo-8H-pyrano-pyran-6-one (Compound No. 10 in Table 2).

Stage 1 : Preparation of dimethy 1-3 -oxy-pimelate

Methyl glycolate (1.50g) and methyl-4-bromobutyrate (3.0g) were added dropwise to a slurry of sodium hydride (0.42g) in dry TΗF (20ml) under a nitrogen atmosphere. The resulting mixture was heated at reflux for 5 hours, cooled to room temperature, poured into 10%) ΗC1 (20ml), extracted with ethyl acetate and dried over anhydrous magnesium sulphate. Removal of the solvent gave a colourless oil which was purified by column chromatography (silica eluted with ethyl acetate/hexane 1 : 1) to give dimethy 1-3 -oxy-pimelate as a colourless liquid (0.80g).

Η nmr δ 1.95 (2Η, m), 2.45 (2H, m), 3.60 (2H, m), 3.70 (3H, s), 3.80 (3H, s), 4.10 (2H, m) ppm.

Stage 2 : Preparation of 2-carboxymethyl-tetrahydro-3H-pyran-3-one Sodium methoxide (0.57g) was added portionwise to a solution of dimethyl-3-oχy- pimelate (l.OOg) in toluene (5ml) and the reaction mixture refluxed for 2 hours. The mixture was poured into 10% HC1 (10ml), extracted with ethyl acetate, dried over anhydrous magnesium sulphate, and the solvent removed to give a colourless oil. Purification by column chromatography (silica eluted with ethyl acetate/hexane 2:1) gave 2-carboxymethyl- tetrahydro-3H-pyran-3-one as a colourless liquid (0J3g). 1H nmr δ 2.40 (2H, m), 3.80 (2H, m), 3.80 (3H, s), 4.20 (2H, m), 12.00 (IH, s) ppm.

Stage 3 : Preparation of l-hydroxy-3-methyl-9,10-dihydro-6H-benzo-8H-pyrano-pyran-6- one (Compound No. 10 in Table 2).

Phosphorus oxychloride (OJOg, 0.06ml) was added dropwise to a stirred solution of orcinol monohydrate (0.09g) and 2-carboxymethyl-tetrahydro-3H-pyran-3-one (0J2g) in dry toluene (5ml). The reaction mixture was heated at 80°C for 2 hours, cooled to room temperature and the solvent removed to give an orange solid. Recrystallisation from ethyl acetate gave the title compound as an orange powder (0J2g) m.p. 248-249°C (MΗ⁺=233). Η nmr δ 2.30 (3H, s), 2.60 (2H, m), 3.90 (2H, m), 5.05 (2H, m), 6.50 (IH, s), 6.70 (IH, s) ppm.

EXAMPLE 20

This Example illustrates the plant fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows. Plants were either grown in John Innes Potting Compost (No.l or 2) in 4cm diameter,

3.5cm depth minipots or on an artificial, cellulose based growing medium. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1 : 1 by volume) which was diluted in reverse osmosis water to a concentration of 75 or lOOppm (that is, 0.75 or lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.05% by volume) was added. TWEEN is a registered trade mark. Individual compounds of formula (I) were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention); as a systemic (Syst) application (where the chemical solution, 10ml, was applied as a root drench treatment) or as a stem (Stem) application (where the chemical solution was applied to the stems of the test plants by spraying the plants to run off).

These tests were carried out against Plasmopara viticola (PLASNI) on vines; Phytophthora infestans lycopersici (PHYTIΝ) on tomatoes; and Blumeria graminis f.sp. tritici (ERYSGT), Stagonospora nodorum (LEPTΝO) and Puccinia triticina (PUCCRT) on wheat. Each treatment was applied to two or more replicate plants for Plasmopara viticola and Phytophthora infestans lycopersici and in all tests where the cellulose growing medium was employed. In mini pot tests on Blumeria graminis f.sp. tritici, Stagonospora nodorum and, Puccinia triticina. two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated with a calibrated fungal spore suspension one or two days before (Erad) or 6hours, one day or two days after (Prot) chemical application.

After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. The Blumeria graminis f.sp. tritici plants were inoculated using a 'shake' inoculation technique. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24hours prior to assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed

treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner.

The following are examples of the compounds tested that showed plant fungicidal activity against one or more of the diseases: compounds 1, 2, 4-7, 9, 13, 15, 17, 24, 29-32, 36, 37, 39-42, 44-46, 49, 51, 58-61, 63, 68 and 71 of Table 1, and compounds 1, 3, 4, 7, 8 and 10 of Table 2.

Claims

The use as a plant fungicide of a compound of the general formula (I):

wherein

M, L and K are independently O, S(O)_n where n is 0, 1 or 2, NR_S or CHR_g, provided that at least one is CHRg, that when two are O, L is CHRg and that when two are NR₅ or two or three are CHRg, the values of R₅ and the values of Rg are the same or different;

X is hydroxy, cyclohexanoh-2-yloxy, C_x_₆ alkylcarbonyloxy, halo(C₁.₆)alkylcarbonyl- oxy,

alkoxycarbonyloxy, Cι-₅ alkoxycarbonyl(C₁.₅)alkoxy, halo(C₁.₅)alkoxy- carbonyloxy, C ₆ alkoxycarbonyl(phenyl)(C₁.₆)alkoxy, cyclo(C₃.₆)-alkylcarbonyloxy, arylcarbonyloxy, heterocyclylcarbonyloxy, arylcarbonyl(C₁.₆)alkoxy, ary^C^_g)- alkoxycarbony C^alkoxy, aminocarbonyloxy, mono- or di-(C₁.₆)alkylamino- carbonyloxy, C ₆ alkoxycarbonylcarbonyloxy, Cj.₆ alkylsulphonyloxy, haloalkyl- sulphonyloxy, arylsulphonyloxy, heterocyclylsulphonyloxy, di-(C_M)alkoxy- phosphonyloxy, dihydroxyphosphonyloxy,

alkoxy,

alkoxycarbonylhalo(Cι.₆)alkoxy, aminocarbonyl(Cι.₆)alkoxy, mono- or

amino, C_M alkylcarbonylamino, Cι-₆ alkoxycarbonylamino or Cι_₅ alkylsiύphonylamino or X may be H when R₄ is hydroxy, oxo, hydroximino, amino, mono-or di-(C_1.6)-alkylamino, C_j.₆ alkylcarbonylamino or alkylsulphonylamino; Y is O, S or R₇;

Z is O or S; Ri, R₂, and R₃ are independently H, halo, hydroxy, C_w4 alkyl, halo(C₁.₈)alkyl, hydroxy(C₁.₈)alkyl, C_x.₈ alkoxy, halo(Cι.₈)alkoxy, C,.₆ alkoxy(C₁.₆)alkoxy, C_M alkoxy(Cι.₆)alkoxy(Cι.₆)alkoxy, cyclo(C₃.₆)alkyl, C_M alkylcyclo(C₃.₆)alkyl, cyclo(C₃. ₆)alkoxy, C₂.₆ alkenyl, C₂.₁₂ alkenyloxy,. C₂.₆ alkynyl, C₂.₆ alkynyloxy, C^ alkoxycarbonyl,

alkoxycarbonyl- (C^alkoxy, carboxy(C₁_₆)alkoxy, cyano, nitro, aryl, heterocyclyl, aryloxy, heterocyclyloxy, aryl(C_M0)alkyl or heterocyclyl(C,.₄)alkyl, or R_j and R₂ or R₂ and R₃ join to form optionally

alkyl substituted C₂ alkylenedioxy; R₄ and Rg are independently H, hydroxy, oxo, hydroximino, amino, mono-or-di- (Ci_₆)all<ylamino,

Cι.₆ alkylsulphonylamino, C ₆ alkyl, Cι.₆ alkoxy, C_M alkylenedioxy, cyclo(C₃.₆)alkyl, cyclo(C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C₂.₆ alkynyl, C₂.₆ alkynyloxy, C_M alkylcarbonyloxy, aryl, heterocyclyl, aryloxy or heterocyclyloxy; and R_s and R₇ are independently H, an acid addition salt,

alkynyl, C_M alkylcarbonyl, C_ΪA alkenylcarbonyl, aryl, aryl(C_M)alkyl, arylcarbonyl,

Cj_₄ alkylsulphonyl or arylsulphonyl; any of the foregoing aryl, heterocyclyl, cycloalkyl and cycloalkoxy groups or moieties being optionally substituted.

2. The use as a plant fungicide of a compound of the general formula (I) according to claim 1, wherein R_x is H, halo, C_l alkyl, C_l alkoxycarbonyl or nitro;

R₃ is H, halo, C_M alkyl, aryl(Cι_₄)alkyl or nitro;

R₄ is H, hydroxy or oxo;

K is CH₂, 0, S, SO, SO₂, NH or an acid addition salt thereof, N-C_M alkyl, N-C_M alkylaryl or CH-C_M alkyl;

L is CH₂, 0, S SO, SO₂, NH or an acid addition salt thereof, N-C_M alkyl, N-CO-

(C_M)alkyl, N-CO (C_M)alkenyl or N-C_M alkylaryl;

M is CH₂, NH or an acid addition salt thereof, N-C_M alkyl, N-C_M alkylaryl, or CH-

C_w alkyl; Y and Z are both O; and

R₂ and X have the meanings given in claim 1.

3. The use as a plant fungicide of a compound of the general formula (I) according to claim 1, wherein K and M are both CH₂; R₄ is H; L is CH₂, 0, S, SO, SO₂, NH or an acid addition salt thereof, N-C_M alkyl, N-CO(Cι.₄)alkyl, NCO(C_M)alkenyl or N-C₁ alkylaryl; and R_l5 R₂, R₃, X, Y and Z have the meanings given in claim 1.

4. The use as a plant fungicide of a compound of the general formula (I) according to claim 1, wherein one of M, L and K is O, S(O)_n where n is 0, 1 or 2, or NR₅ and the other two are CH₂, and R_l9 R₂, R₃, R₄, X, Y and Z have the meanings given in claim 1.

5. The use as a plant fungicide of a compound of the general formula (la) :

wherein

R_j, R₂, and R₃ are independently H, halo, C_w alkyl, C_w alkoxy, cyclo(C₃.₆)alkyl, cyclo(C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C₂.₆ alkynyl, C₂.₆ alkynyloxy, C^ alkoxycarbonyl, cyano, nitro, aryl, heterocyclyl, aryloxy, heterocyclyloxy, aryl(C_M)- alkyl or heterocyclyl(Cι.₄)alkyl;

R₄, R_g, Rg and R_]0 are independently H, hydroxy, oxo, Cj.g alkyl, -g alkoxy, cyclo(C₃.₆)-alkyl, cyclo(C₃.₆)alkoxy, C₂.₆ alkenyl, C₂.₆ alkenyloxy, C₂-₆ alkynyl, C₂.₆ alkynyloxy, aryl, heterocyclyl, aryloxy or heterocyclyloxy;

X is hydroxy,

alkylcarbonyloxy, halo(Cι.₆)alkylcarbonyloxy, C_w alkoxycarbonyloxy, halo(C₁.₆)alkoxycarbonyloxy, cyclo(C₃.₆)-ukylcarbonyloxy, arylcarbonyloxy, aminocarbonyloxy, mono- or di-(C₁.g)alkylaminocarbonyloxy, C_w alkoxycarbonylcarbonyloxy, C ₆ alkylsulphonyloxy, arylsulphonyloxy, di-(C )- alkoxyphosphonyloxy, cyano(C₁.₆)alkoxy, carboxy^^alkoxy, carboxyhalo(Cι.₆)- alkoxy,

alkoxycarbonyl(C₁.₆)alkoxy, alkoxycarbonylhalo(Cι_.6)alkoxy, amino- carbonyl(Ci.₆)alkoxy, or mono- or di-(Cι.g)alkylaminocarbonyl(Cι.₆)alkoxy or X is H when R₄ is hydroxy or oxo;

Y is O, S or NR₇ wherein R₇ is H, Cj.₆ alkyl, aryl or aryl(C_M)alkyl; and Z is O or S.

6. The use a plant fungicide of a compound of the general formula (la) according to claim 5, wherein R, is H, halo, C_M alkyl, nitro or C_M alkoxycarbonyl; R₃ is H, halo, C_w alkyl, benzyl or nitro; R₄ is H, hydroxy or oxo; R_g is H; Rg is H, alkyl or phenyl; R₁₀ is H or C_M alkyl; and R₂, X, Y and Z have the meanings given in claim 5.

7. The use as a plant fungicide of a compound of the general formula (la) according to claim 5, wherein R_t is H, halo, C_w alkyl, nitro or C_M alkoxycarbonyl; R₃ is H, halo, C_M alkyl, benzyl or nitro; R₄is H, hydroxy or oxo; R₈ is H; Rg is H, alkyl or phenyl; R₁₀ is H or C_M alkyl; Y is O or NR₇; R₇ is H or C_w alkyl; Z is O; and R₂ and X have the meanings given in claim 5.

8. The use as a plant fungicide of a compound of the general formula (la) according to claim 5, wherein Rj is H, halo, Cι.₄ alkyl, nitro or C_M alkoxycarbonyl; R₂ is H, hydroxy, C^ alkyl, C^ alkoxy, C_2A alkenyloxy or cyano; R₃ is H, halo, C_M alkyl, benzyl or nitro; R₄ is H, hydroxy or oxo; R₈ is H; Rg is H, C_M alkyl or phenyl; Rι₀ is

H or C_M alkyl; X is hydroxy, C_w alkylcarbonyloxy, C_M alkoxycarbonyloxy, halo- (C^alkoxycarbonyloxy, cyclohexanonylcarbonyloxy, nitro substituted phenyl- carbonyloxy, C_M alkylaminocarbonyloxy, C_M alkoxycarbonylcarbonyloxy, di- (C_w)alkoxyphosphonyloxy, cyanoalkoxy, carboxy(C₁ )alkoxy, carboxyhalo- (C_M)alkoxy, C_lA

C_M alkoxycarbonylhalo(C_M)alkoxy or aminocarbonyl(C_M)alkoxy or X is H when R₄ is hydroxy or oxo; Y is O or NR₇, wherein R₇ is H or C_w alkyl; and Z is O.

9. The use as a plant fungicide of a compound of the general formula (la) according to claim 5, wherein R_l3 R₄ and R₈ are all H; R₂ is C_l alkyl, C_M alkoxy, C₂.₄ alkenyl or

C₂.₄ alkenyloxy; R₃, R, and R₁₀ are independently H or C_w alkyl; X is hydroxy, C_l alkylcarbonyloxy, carboxy^-^alkoxy, C alkoxycarbony^C^^alkoxy, mono- or di- (Cj-^alkylaminocarbony^Cj^alkoxy or C₁ alkoxycarbonylcarbonyloxy; Y is O or NR₇, wherein R₇ is C_M alkyl; and Z is O.

10. plant ftmgicidal composition comprising a fungicidally effective amount of a compound as defined in claim 1 or claim 5 and a suitable carrier or diluent therefor.

11. A method of combating or controlling phytopathogenic fungi which comprises applying to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or to any other plant growth medium a fungicidally effective amount of a compound according to claim 1 or claim 5 or a composition according to claim 10.

12. A compound of the formula (la) as defined in claim 5 wherein R_Iy R₄ and R₈ are all H; R₂ is Cι_₄ alkyl, C_M alkoxy, C₂-₄ alkenyl or C₂ alkenyloxy; R₃, Rg and R₁₀ are independently H or C_w alkyl; X is hydroxy, C_w alkylcarbonyloxy, carboxy- (C_M)alkoxy, C_M alkoxycarbonyl(Cι.₄)alkoxy, C_lA alkylaminocarbonyl(C_M)alkoxy or C_l alkoxycarbonylcarbonyloxy; Y is O or NR₇, wherein R₇ is C^alkyl; and Z is O; provided that R₂ is not methyl when R₃ and Rg are both H, Rι₀ is H or methyl, X is

OH or methoxycarbonyloxy and Y is 0 or when R₃, Rg and R₁₀ are all H, X is OH and Y is N-methyl or N-ethyl, that R₂ is not n-propyl when R₃ and Rg are both H, R₁₀ is methyl, X is OH and Y is O and that R₂ is not «-butoxy when R₃, Rg and R₁₀ are all H and Y is O or N-methyl.