GB2220656A

GB2220656A - Plant fungicidal azoles

Info

Publication number: GB2220656A
Application number: GB8914737A
Authority: GB
Inventors: Paul Anthony Worthington; Christopher John Urch; Patrick Jeff Crowley; Jeremy Robert Godwin
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1988-07-13
Filing date: 1989-06-27
Publication date: 1990-01-17
Also published as: FR2634482A1; GB8816672D0; GB8914737D0; FR2644162A1; DK348789D0; DK348789A; DE3923202A1

Abstract

Novel compounds having plant fungicidal activity have the general formula: <IMAGE> wherein R<1> is C1-6alkyl (when R<5> is other than H) or is -C IDENTICAL C-R<7> or -CR<8>=CR<9>R<10> in which R<7> to R<10> are H, C1-4alkyl, C2-4 alkenyl, C2-4alkynyl or halogen; R<2> is H, C1-6alkyl, C3-6alkenyl, C3-6alkynyl; R<3> to R<6> are H, C1-4alkyl, C2-4alkenyl, C2-4 alkynyl; X, Y and Z are H, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy; Az is imidazol-l-yl or 1,2,4-triazol-l-yl provided that when R<3> and R<4> are both methyl, R<5> and R<6> are both hydrogen and Az is 1,2,4-triazol-l-yl then R<1> is not -C IDENTICAL C-alkyl, and provided that when R<3> and R<4> are both alkyl, R<5> is hydrogen and R<6> is one of alkyl, alkenyl or alkynyl then R<8>, R<9> and R<10> are not all hydrogen, or are stereoisomers, salts or metal complexes thereof. Novel intermediates used in the preparation of the fungicidal compounds have the formula: <IMAGE>

Description

HETEROCYCLIC COMPOUNDS This invention relates to heterocyclic compounds which are useful as fungicides, to processes for preparing the compounds, to fungicidal compositions containing them, and to methods of using them to combat fungi, especially fungal infections in plants.

The invention provides compounds having the general formula (I):

and stereoisomers thereof, wherein R1 is alkyl (when R5 is other than hydrogen), is a group of general formula (II): - C C- R7 (II) or is a group of general formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; R2 is hydrogen, alkyl, alkenyl or alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any u.isara ion); Rj, w4, @ and PS are independently hydrogen, alkyl, alkenyl or alkynyl;X, Y and Z are independently selected from the group comprising hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, haloalkoxy, optionally substituted aryloxy or optionally substituted aralkoxy; Az is imidazol-l-yl or 1,2,4-triazol-1-yl; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl then R1 is not -C-C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.

The compounds of the invention are generally obtained in the form of mixtures of geometric isomers such as diastereoisomers and E and Z double bonds, including cis and trans double bonds, these and other mixtures of optical isomers can be separated into individual isomers by methods in the art and such isomers constitute a part of the present invention.

Alkyl groups conta-ining from 1 to 4 carbon atoms represented by R3 to R10 are either straight or branched chain groups, for example methyl, ethyl, n propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl. Alkyl groups containing from 1 to 6 carbon atoms represented by R1 or R2 are either straight or branched chain groups for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, pentyl (straight or branched chain) or hexyl (straight or branched chain).Alkyl groups and the alkyl moieties of alkoxy, haloalkyl, haloalkoxy, aralkyl and aralkoxy represented by X, Y and Z are either straight or branched chain groups containing from 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, including any of the specific isomers mentioned above.

Alkenyl groups containing from 2 to 4 carbon atoms represented by R3 to 70, which are the same or different, may be alk-l-enyl, alk-2-enyl or alk-3enyl, for example vinyl, 2-prop-l-enyl, l-prop-lenyl, allyl, 2-but-2-enyl, 1- ( 2-methylprop-l-enyl), l-but-l-enyl, 2-but-2-enyl, 1- ( l-methylprop-2-enyl), l-(2-methylprop-2-enyl), l-but-2-enyl, or l-but-3enyl. Alkenyl groups containing from 3 to 6 carbon atoms represented by R2 which may be either E or Z geometry (including cis and trans), may be alk-2enyl, alk-3-enyl, alk-4-enyl or alk-5-enyl, for example allyl, l-(l-methylprop-2-enyl), 1-(2- methylprop-2-enyl, l-but-2-enyl, l-but-3-enyl, pent2-enyl, pent-3-enyl, pent-4-enyl, hex-2-enyl, hex-3enyl, hex-4-enyl or hex-5-enyl.Alkenyl groups represented by X, Y and Z, which may be the same or different, which may be E or Z geometry (including cis and trans), may be either straight or branched chain groups containing from 2 to 6 carbon atoms, for example vinyl or allyl, or any of the examples mentioned above.

Alkynyl groups containing from 2 to 4 carbon atoms represented by R3 to R10, which are the same or different, may be, for example ethynyl, prop-l-ynyl, propargyl, 2-but-3-ynyl, but-l-ynyl, but-2-ynyl or but-3-ynyl. Alkynyl groups containing from 3 to 6 carbon atoms represented by R2 may be alk-2ynyl, alk-3-ynyl, alk-4-ynyl or alk-5-ynyl, for example propargyl or but-2-ynyl. Alkynyl groups represented by x, Y and Z may be either straight or branched chain groups containing from 2 to 6 carbon atoms, for example ethynyl or propargyl, or any of the examples mentioned above.

Cycloalkyl groups represented by X, Y and Z may be C3-C7 cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl groups.

Cycloalkylalkyl groups represented by X, Y and Z may be C3? cycloalkyl(C16)alkyl groups, for example cyclopropylmethyl, cyclohexylmethyl or 1cyclopropylethyl.

Examples of X, Y and Z when these are aryl, aralkyl, aryloxy or aralkoxy are phenyl, benzyl, phenoxy and benzyloxy. These rings may be substituted with halogen (fluorine, chlorine or bromine), C16 alkyl (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tertbutyl), C16 alkoxy (eg, methoxy, ethoxy, propoxy or butoxy), halo-C16-a1kyl (eg, trifluoromethyl), halo- C1~6-alkoxy (eg, trifluoromethoxy), nitro, phenyl or phenoxy.

Halogen atoms are fluorine, chlorine, bromine or iodine atoms.

In another aspect the invention provides compounds having the general formula (I):

and stereoisomers thereof, wherein R1 represents an alkyl group containing from 1 to 6 carbon atoms (for cases where R5 is other than hydrogen), or a group of general formula (II);

or a group of general formula (III)::

wherein R7 to R10 which can be the same or different each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atom. s or a halogen atom (fluorine, chlorine, bromine or iodine), R2 represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, or an alkenyl or alkynyl group containing from 3 to 6 carbon atoms (providing that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation), R3 to R6, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms, X, Y and Z, which can be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy group, and Az represents l-imidazole or 1,2,4-triazole; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4triazol-l-yl then R1 is not -C=C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.

In a further aspect the invention provides compounds having the general formula (I):

and stereoisomers thereof, wherein R1 is C16 alkyl (when R5 is other than hydrogen), or is a group of general formula (II): - C-C- R7 (II) or is a group of general formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, C1-4 alkyl, C2-4 alkenyl, C2-4 alkenyl; R2 is hydrogen, C1-6 alkyl, C3-6 alkenyl or C3-6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3 to R6 are independently hydrogen, C1-4 alkyl, C2-4 alkenyl or C2-4 alkynyl;X, Y and Z are independently selected from the group comprising hydrogen, halogen, C1-6 alkyl, halo(C1-6)alkyl, C3-7 cycloalkyl, C3-7 cycloalkyl (C1-6)alkyl, C2-6 alkenyl, C2-6 alkynyl, phenyl, phenyl (C1-6)alkyl, C1-6 alkoxy, halo (C1-6)alkoxy, phenoxy or phenyl (C1-6)alkoxy; Az is imidazol-1-yl or 1,2,4-triazol-1yl; wherein any of the foregoing phenyl moieties are optionally substituted with halogen, C1-6 alkyl, C1-6 alkoxy, halo(C1-6)alkyl, halo (C1-6)alkoxy, nitro, phenyl or phenoxy; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen, and Az is 1,2,4-triazol-1-yl then R is not -C#C-alkyl and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts ana metal complexes thereof.

In a yet another aspect the invention provides compounds having the general formula (I):

and stereoisomers thereof, wherein R1 is C34 alkyl, R2, R3 and R6 are independently hydrogen or C1-4 alkyl; R4 is hydrogen; R5 is C1-4 alkyl; X, Y and Z are independently hydrogen, halogen, C1-4 alkyl, C14 alkoxy, phenoxy or phenyl; Az is imidazol-l-yl or 1,2,4-triazol-1-yl, and salts and metal complexes thereof.

In yet a further aspect the invention provides compounds of formula (I) wherein R1 is C3-4 alkyl, R2 is hydrogen or methyl; R3, R4 and R6 are all hydrogen, R5 is C12 alkyl; Az is 1,2,4-triazol-1-yl, X, Y and Z are independently hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.

In yet another aspect the invention provides compounds having the general formula (I):

and stereoisomers thereof, wherein R1 is a group of general formula (II): - C#C-R7 (II) or is a group of general formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, C1-4 alkyl, C2-4 alkenyl or C2-4 alkynyl; R2 is hydrogen, C1-4 alkyl, C3-6 alkenyl or C3-6 alkynyl (provided that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R , R4, R5 and R6 are independently hydrogen, C1-6 alkyl, C2-4 alkenyl or C2-4 alkynyl;X, Y and Z are independently hydrogen, chlorine or fluorine atoms; Az is imidazol-1-yl or 1,2,4-triazol-1-yl; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl then R is not-C#C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.

In yet a further aspect the invention provides compounds having the general formula (XXXIV):

and stereoisomers thereof, wherein R1 is a group of formula (II): C#C-R7 (II) or is a group of formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen or C1-4 alkyl; R2 is hydrogen, C1-4 alkyl, allyl or propargyl; X, Y and Z are independently hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.

In a still further aspect the invention provides compounds having the general formula (XXXV):

and stereoisomers thereof, wherein R1 is a group of formula (II): - C#C-R7 (II) or a group of formula (III):

wherein R7 is C14 alkyl, R8 is hydrogen, one of R9 and R10 is hydrogen whilst the other is C14 alkyl; R2 is hydrogen or methyl; X and Y are hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.

In yet another aspect the invention provides the compound:

(compound 233 of Table I) and its stereoisomers; and salts and metal complexes thereof.

In Table I the significance of the abbreviations is as follows: Me represents methyl Et represents ethyl npr represents normal propyl iPr represents iso-propyl nBu represents normal butyl iBu represents iso-butyl sBu represents secondary butyl tBu represents tertiary butyl Tr represents 1,2,4-triazol-l-yl All melting points in Table I below are expressed 2 n degrees centigrade.

Whilst the azole (Az) in column 11 of Table I is given as Tr (ie, 1,2,4-triazol-l-yl) it should be understood that it could equally be Im (ie, imidazol-l-yl) and this specification should be read as comprising, in each instance, the imidazol-l-yl corresponding to the precise 1,2,4-triazol-1-yl specified.

TABLE I

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 1 2-Cl 4-Cl H C#CH H H H H H Tr 2 2-Cl 4-Cl H C#CH Me H H H H Tr 3 2-Cl 4-Cl H C#CH Et H H H H Tr 4 2-Cl 4-Cl H C#CH nPr H H H H Tr 5 2-Cl 4-Cl H C#CH CH2-CH=CH2 H H H H Tr 6 2-Cl 4-Cl H C#CH CH2-C#CH H H H H Tr 7 2-Cl 4-Cl H C#C-Me H H H H H Tr 110-113 C 8 2-Cl 4-Cl H C#C-Me Me H H H H Tr oil 9 2-Cl 4-Cl H C#C-Me Et H H H H Tr 10 2-Cl 4-Cl H C#C-Me nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 11 2-Cl 4-Cl H C#C-Me CH2-CH=CH2 H H H H Tr 12 2-Cl 4-Cl H C#C-Me CH2-C#CH H H H H Tr 13 2-Cl 4-Cl H C#C-Et H H H H H Tr 69-71 C 14 2-Cl 4-Cl H C#C-Et Me H H H H Tr oil 15 2-Cl 4-Cl H C#C-Et Et H H H H Tr 16 2-Cl 4-Cl H C#C-Et nPr H H H H Tr 17 2-Cl 4-Cl H C#C-Et CH2-CH=CH2 H H H H Tr 18 2-Cl 4-Cl H C#C-Et CH2-C#CH H H H H Tr 19 2-Cl 4-Cl H CH=CH2 H H H H H Tr 20 2-Cl 4-Cl H CH=CH2 Me H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 21 2-Cl 4-Cl H CH=CH2 Et H H H H Tr 22 2-Cl 4-Cl H CH=CH2 nPr H H H H Tr 23 2-Cl 4-Cl H CH=CH2 CH2-CH=CH2 H H H H Tr 24 2-Cl 4-Cl H CH=CH2 CH2-C#CH H H H H Tr 25 2-Cl 4-Cl H CH=CHMe H H H H H Tr oil E 26 2-Cl 4-Cl H CH=CHMe H H H H H Tr Z 27 2-Cl 4-Cl H CH=CHMe Me H H H H Tr 45-47 Cc E 28 2-Cl 4-Cl H CH=CHMe Me H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 29 2-Cl 4-Cl H CH=CHMe Et H H H H Tr E 30 2-Cl 4-Cl H CH=CHMe Et H H H H Tr Z 31 2-Cl 4-Cl H CH=CHMe nPr H H H H Tr E 32 2-Cl 4-Cl H CH=CHMe nPr H H H H Tr Z 33 2-Cl 4-Cl H CH=CHMe CH2-CH=CH2 H H H H Tr E 34 2-Cl 4-Cl H CH=CHMe CH2-CH=CH2 H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 35 2-Cl 4-Cl H CH=CHMe CH2-C#CH H H H H Tr E 36 2-Cl 4-Cl H CH=CHMe CH2-C#CH H H H H Tr Z 37 2-Cl 4-Cl H CMe=CH2 @H H H H H Tr 38 2-Cl 4-Cl H CMe=CH2 Me H H H H Tr 39 2-Cl 4-Cl H CMe=CH2 Et H H H H Tr 40 2-Cl 4-Cl H CMe=CH2 nPr H H H H Tr 41 2-Cl 4-Cl H CMe=CH2 CH2-CH=CH2 H H H H Tr 42 2-Cl 4-Cl H CMe=CH2 CH2-C#CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 43 2-Cl 4-Cl H CH=CHEt H H H H H Tr oil E 44 2-Cl 4-Cl H CH=CHEt H H H H H Tr Z 45 2-Cl 4-Cl H CH=CHEt Me H H H H Tr E 46 2-Cl 4-Cl H CH=CHEt Me H H H H Tr Z 47 2-Cl 4-Cl H CH=CHEt Et H H H H Tr E 48 2-Cl 4-Cl H CH=CHEt Et H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 49 2-Cl 4-Cl H CH=CHEt nPr H H H H Tr E 50 2-Cl 4-Cl H CH=CHEt nPr H H H H Tr Z 51 2-Cl 4-Cl H CH=CHEt CH2-CH=CH2 H H H H Tr E 52 2-Cl 4-Cl H CH=CHEt CH2-CH=CH2 H H H H Tr Z 53 2-Cl 4-Cl H CH=CHEt CH2-C#CH H H H H Tr E 54 2-Cl 4-Cl H CH=CHEt CH2-C#CH H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 55 2-Cl 4-Cl H CH=CMe2 H H H H H Tr 56 2-Cl 4-Cl H CH=CMe2 Me H H H H Tr 57 2-Cl 4-Cl H CH=CMe2 Et H H H H Tr 58 2-Cl 4-Cl H CH=CMe2 nPr H H H H Tr 59 2-Cl 4-Cl H CH=CMe2 CH2-CH=CH2 H H H H Tr 60 2-Cl 4-Cl H CH=CMe2 CH2-C#CH H H H H Tr 61 2-Cl H H C#CH H H H H H Tr 62 2-Cl H H C#CH Me H H H H Tr 63 2-Cl H H C#CH Et H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 64 2-Cl H H C#CH nPr H H H H Tr 65 2-Cl H H C#CH CH2-CH=CH2 H H H H Tr 66 2-Cl H H C#CH CH2-C#CH H H H H Tr 67 2-Cl H H C#C-Me H H H H H Tr 90 C 68 2-Cl H H C#C-Me Me H H H H Tr oil 69 2-Cl H H C#C-Me Et H H H H Tr 70 2-Cl H H C#C-Me nPr H H H H Tr 71 2-Cl H H C#C-Me CH2-CH=CH2 H H H H Tr 72 2-Cl H H C#C-Me CH2-C#CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 73 2-Cl H H C#C-Et H H H H H Tr 45-48 C 74 2-Cl H H C#C-Et Me H H H H Tr oil 75 2-Cl H H C#C-Et Et H H H H Tr 76 2-Cl H H C#C-Et nPr H H H H Tr 77 2-Cl H H C#C-Et CH2-CH=CH2 H H H H Tr 78 2-Cl H H C#C-Et CH2-C#CH H H H H Tr 79 2-Cl H H CH=CH2 H H H H H Tr 80 2-Cl H H CH=CH2 Me H H H H Tr 81 2-Cl H H CH=CH2 Et H H H H Tr 82 2-Cl H H CH=CH2 nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 83 2-Cl H H CH=CH2 CH2-CH=CH2 H H H H Tr 84 2-Cl H H CH=CH2 CH2-C#CH H H H H Tr 85 2-Cl H H CH=CHMe H H H H H Tr oil E 86 2-Cl H H CH=CHMe H H H H H Tr Z 87 2-Cl H H CH=CHMe Me H H H H Tr oil E 88 2-Cl H H CH=CHMe Me H H H H Tr Z 89 2-Cl H H CH=CHMe Et H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 90 2-Cl H H CH=CHMe Et H H H H Tr Z 91 2-Cl H H CH=CHME nPr H H H H Tr E 92 2-Cl H H CH=CHMe nPr H H H H Tr Z 93 2-Cl H H CH=CHMe CH2-CH=CH2 H H H H Tr E 94 2-Cl H H CH=CHMe CH2-CH=CH2 H H H H Tr Z 95 2-Cl H H CH=CHMe CH2-C#CH H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 96 2-Cl H H CH=CHMe CH2-C#CH H H H H Tr Z 97 2-Cl H H CMe=CH2 H H H H H Tr 98 2-Cl H H CMe=CH2 Me H H H H Tr 99 2-Cl H H CMe=CH2 Et H H H H Tr 100 2-Cl H H CMe=CH2 nPr H H H H Tr 101 2-Cl H H CMe=CH2 CH2-CH=CH2 H H H H Tr 102 2-Cl H H CMe=CH2 CH2-C#CH H H H H Tr 103 2-Cl H H CH=CHEt H H H H H Tr oil E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 104 2-Cl H H CH=CHEt H H H H H Tr Z 105 2-Cl H H CH=CHEt Me H H H H Tr oil E 106 2-Cl H H CH=CHEt Me H H H H Tr Z 107 2-Cl H H CH=CHEt Et H H H H Tr E 108 2-Cl H H CH=CHEt Et H H H H Tr Z 109 2-Cl H H CH=CHEt nPr H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 110 2-Cl H H CH=CHEt nPr H H H H Tr Z 111 2-Cl H H CH=CHEt CH2-CH=CH2 H H H H Tr E 112 2-Cl H H CH=CHEt CH2-CH=CH2 H H H H Tr Z 113 2-Cl H H CH=CHEt CH2-C#CH H H H H Tr E 114 2-Cl H H CH=CHEt CH2-C#CH H H H H Tr Z 115 2-Cl H H CH=CMe H H H H H Tr 116 2-Cl H H CH=CMe Me H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 117 2-Cl H H CH=CMe2 Et H H H H Tr 118 2-Cl H H CH=CMe2 nPr H H H H Tr 119 2-Cl H H CH=CMe2 CH2CH=CH2 H H H H Tr 120 2-Cl H H CH=CMe2 CH2-C=CH H H H H Tr 121 4-Cl H H C=CH H H H H H Tr 122 4-Cl H H C=CH Me H H H H Tr 123 4-Cl H H C=CH Et H H H H Tr 124 4-Cl H H C=CH nPr H H H H Tr 125 4-Cl H H C=CH CH2-CH=CH2 H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 126 4-Cl H H =CH CH2-C=CH H H H H Tr 127 4-Cl H H C=C-Me H H H H H Tr 99.5-101.5 C 128 4-Cl H H C=C-Me Me H H H H Tr oil 129 4-Cl H H C=C-Me Et H H H H Tr 130 4-Cl H H C=C-Me nPr H H H H Tr 131 4-Cl H H C=C-Me CH2-CH=CH2 H H H H Tr 72 C 132 4-Cl H H C=C-Me CH2-O=CH H H H H Tr 133 4-Cl H H C=C-Et H H H H H Tr oil 134 4-Cl H H C=C-Et Me H H H H Tr oil TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 135 4-Cl H H C=C-Et Et H H H H Tr 136 4-Cl H H C=C-Et nPr H H H H Tr 137 4-Cl H H C=C-Et CH2-CH=CH2 H H H H Tr 138 4-Cl H H C=C-Et CH2-C=CH H H H H Tr 139 4-Cl H H CH=CH2 H H H H H Tr 140 4-Cl H H CH=CH2 Me H H H H Tr 141 4-Cl H H CH=CH2 Et H H H H Tr 142 4-Cl H H CH=CH2 nPr H H H H Tr 143 4-Cl H H CH=CH2 CH2-CH=CH2 H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 144 4-Cl H H CH=CH2 CH2-C=CH H H H H Tr 145 4-Cl H H CH=CHMe H H H H H Tr 116.5-117.5 C E 146 4-Cl H H CH=CHMe H H H H H Tr Z 147 4-Cl H H CH=CHMe Me H H H H Tr oil E 148 4-Cl H H CH=CHMe Me H H H H Tr Z 149 4-Cl H H CH=CHMe Et H H H H Tr E 150 4-Cl H H CH=CHMe Et H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 151 4-Cl H H CH=CHMe nPr H H H H Tr E 152 4-Cl H H CH=CHMe nPr H H H H Tr Z 153 4-Cl H H CH=CHMe CH2-CH=CH2 H H H H Tr oil E 154 4-Cl H H CH=CHMe CH2-CH=CH2 H H H H Tr Z 155 4-Cl H H CH=CHMe CH2-C=CH H H H H Tr E 156 4-Cl H H CH=CHMe CH2-C=CH H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 157 4-Cl H H CMe=CH2 H H H H H Tr 158 4-Cl H H CMe=CH2 Me H H H H Tr 159 4-Cl H H CMe=CH2 Et H H H H Tr 160 4-Cl H H CMe=CH2 nPr H H H H Tr 161 4-Cl H H CMe=CH2 CH2-CH=CH2 H H H H Tr 162 4-Cl H H CMe=CH2 CH2-O=CH H H H H Tr 163 4-Cl H H CH=CHEt H H H H H Tr E 164 4-Cl H H CH=CHEt H H H H H Tr oil Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 165 4-Cl H H CH=CHEt Me H H H H Tr oil E 166 4-Cl H H CH=CHEt Me H H H H Tr Z 167 4-Cl H H CH=CHEt Et H H H H Tr E 168 4-Cl H H CH=CHEt Et H H H H Tr Z 169 4-Cl H H CH=CHEt nPr H H H H Tr E 170 4-Cl H H CH=CHEt nPr H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 171 4-Cl H H CH=CHEt CH2-CH=CH2 H H H H Tr oil E 172 4-Cl H H CH=CHEt CH2-CH=CH2 H H H H Tr Z 173 4-Cl H H CH=CHEt CH2-C=CH H H H H Tr E 174 4-Cl H H CH=CHEt CH2-C=CH H H H H Tr Z 175 4-Cl H H CH=CMe2 H H H H H Tr 176 4-Cl H H CH=CMe2 Me H H H H Tr 177 4-Cl H H CH=CMEt Et H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 178 4-Cl H H CH=CMe2 nPr H H H H Tr 179 4-Cl H H CH=CMe2 CH2-CH=CH2 H H H H Tr 116.5-117.5 C 180 4-Cl H H CH=CMe2 CH2-C=CH H H H H Tr 181 2-Cl 4-F H C=CH H H H H H Tr oil 182 2-Cl 4-F H C=CH Me H H H H Tr 183 2-Cl 4-F H C=CH Et H H H H Tr 184 2-Cl 4-F H C=CH nPr H H H H Tr 185 2-Cl 4-F H C=CH CH2-CH=CH2 H H H H Tr 186 2-Cl 4-F H C=CH CH2-C=CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 187 2-Cl 4-F H C=C-Me H H H H H Tr 188 2-Cl 4-F H C=C-Me Me H H H H Tr 189 2-Cl 4-F H C=C-Me Et H H H H Tr 190 2-Cl 4-F H C=C-Me nPr H H H H Tr 191 2-Cl 4-F H C=C-Me CH2-CH=CH2 H H H H Tr 192 2-Cl 4-F H C=C-Me CH2-C=CH H H H H Tr 193 2-Cl 4-F H C=C-Et H H H H H Tr oil 194 2-Cl 4-F H C=C-Et Me H H H H Tr 195 2-Cl 4-F H C=C-Et Et H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 196 2-Cl 4-F H C=C-Et nPR H H H H Tr 197 2-Cl 4-F H C=C-Et CH2-CH=CH2 H H H H Tr 198 2-Cl 4-F H C=C-Et CH2-C=CH H H H H Tr 199 2-Cl 4-F H CH=CH2 H H H H H Tr 200 2-Cl 4-F H CH=CH2 Me H H H H Tr 201 2-Cl 4-F H CH=CH2 Et H H H H Tr 202 2-Cl 4-F H CH=CH2 nPr H H H H Tr oil 203 2-Cl 4-F H CH=CH2 CH2-CH=CH2 H H H H Tr 204 2-Cl 4-F H CH=CH2 CH2-C=CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 205 2-Cl 4-F H CH=CHMe H H H H H Tr E 206 2-Cl 4-F H CH=CHMe H H H H H Tr Z 207 2-Cl 4-F H CH=CHMe Me H H H H Tr E 208 2-Cl 4-F H CH=CHMe Me H H H H Tr Z 209 2-Cl 4-F H CH=CHMe Et H H H H Tr E 210 2-Cl 4-F H CH=CHMe Et H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 211 2-Cl 4-F H CH=CHMe nPr H H H H Tr E 212 2-Cl 4-F H CH=CHMe nPr H H H H Tr Z 213 2-Cl 4-F H CH=CHMe CH2-CH=CH2 H H H H Tr E 214 2-Cl 4-F H CH=CHMe CH2-CH=CH2 H H H H Tr Z 215 2-Cl 4-F H CH=CHMe CH2-C=CH H H H H Tr E 216 2-Cl 4-F H CH=CHMe CH2-C=CH H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 217 2-Cl 4-F H CMe=CH2 H H H H H Tr 218 2-Cl 4-F H CMe=CH2 Me H H H H Tr 219 2-Cl 4-F H CMe=CH2 Et H H H H Tr 220 2-Cl 4-F H CMe=CH2 nPr H H H H Tr 221 2-Cl 4-F H CMe=CH2 CH2-CH=CH2 H H H H Tr 222 2-Cl 4-F H CMe=CH2 CH2-C=CH H H H H Tr 223 2-Cl 4-F H CH=CHEt H H H H H Tr E 224 2-Cl 4-F H CH=CHEt H H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 225 2-Cl 4-F H CH=CHEt Me H H H H Tr E 226 2-Cl 4-F H CH=CHEt Me H H H H Tr Z 227 2-Cl 4-F H CH=CHEt Et H H H H Tr E 228 2-Cl 4-F H CH=CHEt Et H H H H Tr Z 229 2-Cl 4-F H CH=CHEt nPr H H H H Tr E 230 2-Cl 4-F H CH=CHEt nPr H H H H Tr Z 231 2-Cl 4-F H CH=CHEt CH2-CH=CH2 H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 232 2-Cl 4-F H CH=CHEt CH2-CH=CH2 H H H H Tr Z 233 2-Cl 4-F H CH=CHEt CH2-C=CH H H H H Tr E 234 2-Cl 4-F H CH=CHEt CH2-C=CH H H H H Tr Z 235 2-Cl 4-F H CH=CMe2 H H H H H Tr 236 2-Cl 4-F H CH=CMe2 Me H H H H Tr 237 2-Cl 4-F H CH=CMe2 Et H H H H Tr 238 2-Cl 4-F H CH=CMe2 nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az METING COMMENTS NO POINT 239 2-Cl 4-F H CH=CMe2 CH2-CH=CH2 H H H H Tr 240 2-Cl 4-F H CH=CMe2 CH2-C=CH H H H H Tr 241 2-F 4-Cl H C=CH H H H H H Tr 242 2-F 4-Cl H C=CH Me H H H H Tr 243 2-F 4-Cl H C=CH Et H H H H Tr 244 2-F 4-Cl H C=CH nPr H H H H Tr 245 2-F 4-Cl H C=CH CH2-CH=CH2 H H H H Tr 246 2-F 4-Cl H C=CH CH2-C=CH H H H H Tr 247 2-F 4-Cl H C=C-Me H H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 248 2-F 4-Cl H C#C-Me Me H H H H Tr 249 2-F 4-Cl H C#C-Me Et H H H H Tr 250 2-F 4-Cl H C#C-Me nPr H H H H Tr 251 2-F 4-Cl H C#C-Me CH2-CH2=CH2 H H H H Tr 252 2-F 4-Cl H C#C-Me CH2-C#CH H H H H Tr 253 2-F 4-Cl H C#C-Et H H H H H Tr 254 2-F 4-Cl H C#C-Et Me H H H H Tr 255 2-F 4-Cl H C#C-Et Et H H H H Tr 256 2-F 4-Cl H C#C-Et nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 257 2-F 4-Cl H C#C-Et CH2-CH=CH2 H H H H Tr 258 2-F 4-Cl H C#C-Et CH2-C#CH H H H H Tr 259 2-F 4-Cl H C#C-CH2 H H H H H Tr 260 2-F 4-Cl H C#C-CH2 Me H H H H Tr 261 2-F 4-Cl H C#C-CH2 Et H H H H Tr 262 2-F 4-Cl H C#C-CH2 nPr H H H H Tr 263 2-F 4-Cl H C#C-CH2 CH2-CH=CH2 H H H H Tr 264 2-F 4-Cl H C#C-CH2 CH2-C#CH H H H H Tr 265 2-F 4-Cl H C#C-CHMe H H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 266 2-F 4-Cl H CH=CHMe H H H H H Tr Z 267 2-F 4-Cl H CH=CHMe Me H H H H Tr E 268 2-F 4-Cl H CH=CHMe Me H H H H Tr Z 269 2-F 4-Cl H CH=CHMe Et H H H H Tr E 270 2-F 4-Cl H CH=CHMe nPr H H H H Tr Z 271 2-F 4-Cl H CH=CHMe H H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 272 2-F 4-Cl H CH=CHMe nPr H H H H Tr Z 273 2-F 4-Cl H CH=CHMe CH2-CH=CH2 H H H H Tr E 274 2-F 4-Cl H CH=CHMe CH2-CH=CH2 H H H H Tr Z 275 2-F 4-Cl H CH=CHMe CH2-C#CH H H H H Tr E 276 2-F 4-Cl H CH=CHMe CH2-C#CH H H H H Tr Z 277 2-F 4-Cl H CMe=CH2 H H H H H Tr 278 2-F 4-Cl H CMe=CH2 Me H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 279 2-F 4-Cl H CHe=CH2 Et H H H H Tr 280 2-F 4-Cl H CHe=CH2 nPr H H H H Tr 281 2-F 4-Cl H CHe=CH2 CH2-CH=CH2 H H H H Tr 282 2-F 4-Cl H CHe=CH2 CH2-C#CH H H H H Tr 283 2-F 4-Cl H CH=CHEt H H H H H Tr E 284 2-F 4-Cl H CH=CHEt H H H H H Tr Z 285 2-F 4-Cl H CH=CHEt Me H H H H Tr E 286 2-F 4-Cl H CH=CHEt Me H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 287 2-F 4-Cl H CH=CHEt Et H H H H Tr E 288 2-F 4-Cl H CH=CHEt Et H H H H Tr Z 289 2-F 4-Cl H CH=CHEt nPr H H H H Tr E 290 2-F 4-Cl H CH=CHEt nPr H H H H Tr Z 291 2-F 4-Cl H CH=CHEt CH2-CH=CH2 H H H H Tr E 292 2-F 4-Cl H CH=CHEt CH2-CH=CH2 H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 293 2-F 4-Cl H CH=CHEt CH2-C#CH H H H H Tr E 294 2-F 4-Cl H CH=CHEt CH2-C#CH H H H H Tr Z 295 2-F 4-Cl H CH=CMe2 H H H H H Tr 296 2-F 4-Cl H CH=CMe2 Me H H H H Tr 297 2-F 4-Cl H CH=CMe2 Et H H H H Tr 298 2-F 4-Cl H CH=CMe2 nPr H H H H Tr 299 2-F 4-Cl H CH=CMe2 CH2-CH=CH2 H H H H Tr 300 2-F 4-Cl H CH=CMe2 CH2-C#CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 301 2-F 4-F H C#CH H H H H H Tr 302 2-F 4-F H C#CH Me H H H H Tr 303 2-F 4-F H C#CH Et H H H H Tr 304 2-F 4-F H C#CH nPr H H H H Tr 305 2-F 4-F H C#CH CH2-CH#CH2 H H H H Tr 306 2-F 4-F H C#CH CH2-C#CH H H H H Tr 307 2-F 4-F H C#C-Me H H H H H Tr 308 2-F 4-F H C#C-Me Me H H H H Tr 309 2-F 4-F H C#C-Me Et H H H H Tr 310 2-f 4-F H C#C-Me nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 311 2-F 4-F H C#C-Me CH2-CH#CH2 H H H H Tr 312 2-F 4-F H C#C-Me CH2-C#CH H H H H Tr 313 2-F 4-F H C#C-Et H H H H H Tr 314 2-F 4-F H C#C-Et Me H H H H Tr 315 2-F 4-F H C#C-Et Et H H H H Tr 316 2-F 4-F H C#C-Et nPr H H H H Tr 317 2-F 4-F H C#C-Et CH2-CH=CH2 H H H H Tr 318 2-F 4-F H C#C-Et CH2-C#CH H H H H Tr 319 2-F 4-F H CH=CH2 H H H H H Tr 320 2-f 4-F H CH=CH2 Me H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 321 2-F 4-F H CH=CH2 Et H H H H Tr 322 2-F 4-F H CH=CH2 nPr H H H H Tr 323 2-F 4-F H CH=CH2 CH2-CH=CH2 H H H H Tr 324 2-F 4-F H CH=CH2 CH2-C#CH H H H H Tr 325 2-F 4-F H CH=CHMe H H H H H Tr E 326 2-F 4-F H CH=CHMe H H H H H Tr Z 327 2-F 4-F H CH=CHMe Me H H H H Tr E 328 2-F 4-F H CH=CHMe Me H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 329 2-F 4-F H CH=CHMe Et H H H H Tr E 330 2-F 4-F H CH=CHMe Et H H H H Tr Z 331 2-F 4-F H CH=CHMe nPr H H H H Tr E 332 2-F 4-F H CH=CHMe nPr H H H H Tr Z 333 2-F 4-F H CH=CHMe CH2-CH=CH2 H H H H Tr E 334 2-F 4-F H CH=CHMe CH2-CH=CH2 H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 335 2-F 4-F H CH=CHMe CH2-C#CH H H H H Tr E 336 2-F 4-F H CH=CHMe CH2-C#CH H H H H Tr Z 337 2-F 4-F H CMe=CH2 H H H H H Tr 338 2-F 4-F H CMe=CH2 Me H H H H Tr 339 2-F 4-F H CMe=CH2 Et H H H H Tr 340 2-F 4-F H CMe=CH2 nPr H H H H Tr 341 2-F 4-F H CMe=CH2 CH2-CH=CH2 H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 342 2-F 4-F H CMe=CH2 CH2-C#CH H H H H Tr 343 2-F 4-F H CH=CHEt H H H H H Tr E 344 2-F 4-F H CH=CHEt H H H H H Tr Z 345 2-F 4-F H CH=CHEt Me H H H H Tr E 346 2-F 4-F H CH=CHEt Me H H H H Tr Z 347 2-F 4-F H CH=CHEt Et H H H H Tr E 348 2-F 4-F H CH=CHEt Et H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 349 2-F 4-F H CH=CHEt nPr H H H H Tr E 350 2-F 4-F H CH=CHEt nPr H H H H Tr Z 351 2-F 4-F H CH=CHEt CH2-CH=CH2 H H H H Tr E 352 2-F 4-F H CH=CHEt CH2-CH=CH2 H H H H Tr Z 353 2-F 4-F H CH=CHEt CH2-C#CH H H H H Tr E 354 2-F 4-F H CH=CHEt CH2-C#CH H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 355 2-F 4-F H CH=CMe2 H H H H H Tr 356 2-F 4-F H CH=CMe2 Me H H H H Tr 357 2-F 4-F H CH=CMe2 Et H H H H Tr 358 2-F 4-F H CH=CMe2 nPr H H H H Tr 359 2-F 4-F H CH=CMe2 CH2-CH#CH2 H H H H Tr 360 2-F 4-F H CH=CMe2 CH2-C#CH H H H H Tr 361 2-Cl 4-Cl 6-Cl C#CH H H H H H Tr 362 2-Cl 4-Cl 6-Cl C#CH Me H H H H Tr 363 2-Cl 4-Cl 6-Cl C#CH Et H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 364 2-Cl 4-Cl 6-Cl C#CH nPr H H H H Tr 365 2-Cl 4-Cl 6-Cl C#CH CH2-CH#CH2 H H H H Tr 366 2-Cl 4-Cl 6-Cl C#CH CH2-C#CH H H H H Tr 367 2-Cl 4-Cl 6-Cl C#C-Me H H H H H Tr 368 2-Cl 4-Cl 6-Cl C#C-Me Me H H H H Tr 369 2-Cl 4-Cl 6-Cl C#C-Me Et H H H H Tr 370 2-Cl 4-Cl 6-Cl C#C-Me nPr H H H H Tr 371 2-Cl 4-Cl 6-Cl C#C-Me CH2-CH=CH2 H H H H Tr 372 2-Cl 4-Cl 6-Cl C#C-Me CH2-C#CH H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 373 2-Cl 4-Cl 6-Cl C#C-Et H H H H H Tr 374 2-Cl 4-Cl 6-Cl C#C-Et Me H H H H Tr 375 2-Cl 4-Cl 6-Cl C#C-Et Et H H H H Tr 376 2-Cl 4-Cl 6-Cl C#C-Et nPr H H H H Tr 377 2-Cl 4-Cl 6-Cl C#C-Et CH2-CH=CH2 H H H H Tr 378 2-Cl 4-Cl 6-Cl C#C-Et CH2-C#CH H H H H Tr 379 2-Cl 4-Cl 6-Cl CH=CH2 H H H H H Tr 380 2-Cl 4-Cl 6-Cl CH=CH2 Me H H H H Tr 381 2-Cl 4-Cl 6-Cl CH=CH2 Et H H H H Tr 382 2-Cl 4-Cl 6-Cl CH=CH2 nPr H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 383 2-Cl 4-Cl 6-Cl CH=CH2 CH2-CH=CH2 H H H H Tr 384 2-Cl 4-Cl 6-Cl CH=CH2 CH2-C#CH H H H H Tr 385 2-Cl 4-Cl 6-Cl CH=CHMe H H H H H Tr E 386 2-Cl 4-Cl 6-Cl CH=CHMe H H H H H Tr Z 387 2-Cl 4-Cl 6-Cl CH=CHMe Me H H H H Tr E 388 2-Cl 4-Cl 6-Cl CH=CHMe Me H H H H Tr Z 389 2-Cl 4-Cl 6-Cl CH=CHMe Et H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 390 2-Cl 4-Cl 6-Cl CH=CHMe Et H H H H Tr Z 391 2-Cl 4-Cl 6-Cl CH=CHMe nPr H H H H Tr E 392 2-Cl 4-Cl 6-Cl CH=CHMe nPr H H H H Tr Z 393 2-Cl 4-Cl 6-Cl CH=CHMe CH2-CH=CH2 H H H H Tr E 394 2-Cl 4-Cl 6-Cl CH=CHMe CH2-CH=CH2 H H H H Tr Z 395 2-Cl 4-Cl 6-Cl CH=CHMe CH2-C#CH H H H H Tr E TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 396 2-Cl 4-Cl 6-Cl CH=CHMe CH2-C#CH H H H H Tr Z 397 2-Cl 4-Cl 6-Cl CMe=CH2 H H H H H Tr 398 2-Cl 4-Cl 6-Cl CMe=CH2 Me H H H H Tr 399 2-Cl 4-Cl 6-Cl CMe=CH2 Et H H H H Tr 400 2-Cl 4-Cl 6-Cl CMe=CH2 nPr H H H H Tr 401 2-Cl 4-Cl 6-Cl CMe=CH2 CH2-CH=CH2 H H H H Tr 402 2-Cl 4-Cl 6-Cl CMe=CH2 CH2-C#CH H H H H Tr 403 2-Cl 4-Cl 6-Cl CH=CHEt H H H H H Tr E 404 2-Cl 4-Cl 6-Cl CH=CHEt H H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 405 2-Cl 4-Cl 6-Cl CH=CHEt Me H H H H Tr E 406 2-Cl 4-Cl 6-Cl CH=CHEt Me H H H H Tr Z 407 2-Cl 4-Cl 6-Cl CH=CHEt Et H H H H Tr E 408 2-Cl 4-Cl 6-Cl CH=CHEt Et H H H H Tr Z 409 2-Cl 4-Cl 6-Cl CH=CHEt nPr H H H H Tr E 410 2-Cl 4-Cl 6-Cl CH=CHEt nPr H H H H Tr Z TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 411 2-Cl 4-Cl 6-Cl CH=CHEt CH2-CH=CH2 H H H H Tr E 412 2-Cl 4-Cl 6-Cl CH=CHEt CH2-CH=CH2 H H H H Tr Z 413 2-Cl 4-Cl 6-Cl CH=CHEt CH2-C#CH H H H H Tr E 414 2-Cl 4-Cl 6-Cl CH=CHEt CH2-C#CH H H H H Tr Z 415 2-Cl 4-Cl 6-Cl CH=CMe2 H H H H H Tr 416 2-Cl 4-Cl 6-Cl CH=CMe2 Me H H H H Tr 417 2-Cl 4-Cl 6-Cl CH=CMe2 Et H H H H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 418 2-Cl 4-Cl 6-Cl CH=CMe2 nPr H H H H Tr 419 2-Cl 4-Cl 6-Cl CH=CMe2 CH2-CH=CH2 H H H H Tr 420 2-Cl 4-Cl 6-Cl CH=CMe2 CH2-C#CH H H H H Tr 421 2-Cl 4-Cl H tBu H H H Me H Tr oil 422 2-Cl 4-Cl H tBu Me H H Me H Tr 423 4-Cl H H tBu H H H Me H Tr 116.5-117 C 424 2-Cl H H tBu H H H Me H Tr oil 425 2-Cl H H tBu Me H H Me H Tr 426 2-F H H tBu H H H Me H Tr solid TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 427 4-Me H H tBu H H H Me H Tr 75.5-76 C 428 4-F H H tBu H H H Me H Tr 139-141 C 429 H H H tBu H H H Me H Tr 105-108 C 430 2-Cl 4-F H tBu H H H Me H Tr oil 431 2-Cl 4-F H tBu Me H H Me H Tr 432 2-Cl 4-OMe H tBu H H H Me H Tr oil 433 2-F 4-F H tBu H H H Me H Tr 434 2-Cl 4-Me H tBu H H H Me H Tr 435 4-Ph H H tBu H H H Me H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 436 4-Pho H H tBu H H H Me H Tr 437 2-Cl 4-Cl H tBu H Me H Me H Tr 438 2-Cl H H tBu H Me H Me H Tr 439 2-Cl 4-Cl H tBu H H H Me Me Tr 440 2-Cl H H tBu H H H Me Me Tr 441 2-Cl 4-Cl H tBu H H H Me H Tr 442 2-Cl H H tBu H H H Me H Tr 443 2-Cl 4-Cl H ipr H H H Me H Tr 444 2-Cl H H ipr H H H Me H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 445 2-Cl 4-Cl H iBu H H H Me H Tr 446 2-Cl H H iBu H H H Me H Tr 447 2-Cl 4-Cl H sBu H H H Me H Tr 448 2-Cl H H sBu H H H Me H Tr 449 2-Cl H H nPr H H H Me H Tr 450 4-Cl H H nPr H H H Me H Tr TABLE I CONTINUED

COMPOUND X Y Z R R R R4 R5 R6 Az MELTING COMMENTS NO POINT 451 2-Cl 4-Cl H CMe=CHMe H H H H H Tr 452 2-Cl H H CMe=CHMe H H H H H Tr 88 C 453 2-Cl H H CMe=CHMe Me H H H H Tr 454 4-Cl H H CMe=CHMe H H H H H Tr 455 2-Cl 4-F H CMe=CHMe H H H H H Tr TABLE II PROTON NMR DATA Table II shows proton nmr data for certain compounds described in Table I and characterised therein as oils. Chemical shifts are measured in ppm downfield from tetramethylsilane and deuterochloroform was used as solvent throughout.

The following abbreviations are used: br = broad t = triplet s = singlet q = quartet d = doublet m = multiplet dd = doublet of doublets J = coupling constant HZ = Hertz

COMPOUND NO.

8 8.20 (lH,s), 7.92 (lH,s), 7.41 (2H,m), 7.20 (lH,m), 4.38 (lH, ,J 12Hz), 4.29 (lH,d,J 12Hz), 3.39 (3H,s), 3.11 (2H,s), 1.80 (3H,s).

14 8.14 (lH,s), 7.85 (lH,s), 7.38 (lH,m), 7.34 (1H,m), 7.13 (lH,m), 4.32 (lH,d, J 12Hz), 4.24 (lH,d, J 12Hz), 3.32 (3H,s), 3.04 (2H,s), 2.09 (2H,q, J 7Hz), 0.99 (3H,t,J 7Hz).

COMPOUND NO.

25 8.08 (lH,s), 7.93 (lH,s), 7.36 (2H,m), 7.21 1 (1H,m), 5.46 (2H,m), 4.28 (lH,d,J 13Hz), 4.18 (lH,d, J 13Hz), 3.45 (lH,s), 3.00 (2H,m), 1.56 (3H,d, J 7Hz).

43 8.05 (1H, br s), 7.81 (1H, br s), 7.30 (2H,m), 7.10 (lH,m), 5.43 (lH,dd, J 15 and 7Hz), 5.33 (1H,d, J 15Hz), 2.96 (lH,d, J 12Hz), 2.89 (1H,d, J 12Hz), 2.88 (lH,s), 1.83 (2H, quintet, J 7Hz), 0.75 (3H,t, J 7Hz).

68 68 8.21 (1H,s), 7.91 (lH,s), 7.48 | (1H,m), 7.38 (lH,m), 7.22 (2H,m), 4.39 (lH,d, J 13Hz), 4.29 (lH,d, J 13Hz), 3.40 (3H,s), 3.19 (2H,m), 1.79 (3H,s).

74 8.21 (lH,s), 7.90 (lH,s), 7.49 (1H,m), 7.37 (lH,m), 7.21 (2H,m), 4.39 (lH,d, J 13Hz), 4.30 (lH,d, J 13Hz), 3.41 (3H,s), 3.18 (2H,s), 2.14 (2H,q, J 7Hz), 1.05 (3H,t, J 7Hz

COMPOUND NO.

85 85 8.12 (1H, br s), 7.92 (1H, br r s), 7.38 (2H,m), 7.20 (2H,m), 5.50 (2H,m), 4.31 (lH,d, J 13Hz), 4.19 (lH,d, J 13 Hz), 3.32 (1H, br r s), 3.05 (2H,m), 1.56 (3H,d, J 7Hz).

87 8.18 (1H, br s), 7.91 (1H, br s 7.30 (2H,m), 7.22 (2H,m), 5.55 (lH,m), 5.19 # (1H, d, J 16Hz), 4.34 (1H,d, J 13Hz), 4.21 (lH,d, J 13Hz), 3.32 (3H,s), 3.15 (lH,d, J 13Hz), 3.06 (lH,d, J 13Hz), 1.67 3H,d, J 7Hz).

103 8.11 (1H, br s), 7.91 (1H, br s 7.38 (2H,m), 7.20 (2H,m), 5.57 (2H,m), 4.31 (lH,d, J 13Hz) 4.20 (1H, d, J 13Hz), 3,39 (1H, br s 3.10 (lH,d, J 12Hz), 3.02 (lH,d, J 12Hz), 1.89 (2H,m), 0.83 (3H,t, J 7Hz).

105 8.17 (1H, br s), 7.89 (1H, br s 7.30 (2H,m), 7.21 (2H,m), 5.52 (1H, m), 5.16 (1H, d, J 16Hz), 4.

(lH,d, J 13Hz), 4.24 (lH,d, J J 13Hz), 3.32 (3H, , s), 3.10 (2H, m), 2.01 (2H, quintet, J 7Hz), 0.91 (3H,t, J ~~~~~

COMPOUND ! NO.

128 8.20 (lH,s), 7.94 (lH,s), 7.28 (4H,m), 4.30 (lH,d, J 12Hz), 4.20 (lH,d, J 12Hz), 3.39 (3H,s), 2.87 (2H,s), 1.82 (3H,s).

133 8.18 (lH,s), 7.94 (lH,s), 7.28 (4H,m), 4.30 (2H,m), 3.69 (1H, br s), 2.94 (2H;m), 2.09 (2H,q, J 7Hz), 1.03 (3H, t, J 7Hz).

134 | 8.19 (lH,s), 7.93 (lH,s), 7.29 (4H,m), 4.33 (lH,d, J 13Hz), 4.21 (lH,d,J 13Hz), 3.39 (3H,s), 2.21 (2H,q, J 7Hz), 1.09 (3H,t, J 7Hz).

147 | 8.13 (1H,s), 7.92 (lH,s), 7.27 (4H,m), 5.54 (lH,m), 5.17 (lH,d, J | 16Hz), 4.20 (lH,d, J 13Hz), 4.10 (1H,d, J 13Hz), 3.31 (3H,s), 2.95 (1H, d, J 13Hz), 2.76 (lH,d, J 13Hz), 1.70 (3H, d, J 7Hz).

153 @ 8.16 (lH,s), 7.93 (lH,s), 7.25 (4H,m), 5.88 (1H,m), 5.56 (lH,m), 5.21 (3H,m), 4.23 (2H,m), 4.01 (2H,m), 2.95 (lH,d, J 12Hz), 2.80 (1H, d, J 12Hz), 1.70 (3H,d, J 7Hz).

COMPOUND NO.

163 8.09 (lH,s), 7.92 (lH,s), 7.27 (2H,m), 7.14 (2H,m), 5.50 (lH,m), 5.34 (lH,d, J 16Hz), 4.19 (2H,m), 3.15 (lH,s), 2.86 (lH,d, J 12Hz), 2.73 (1H,d, J 12Hz), 1.92 (2H, quintet, J 7Hz), 0.84 (3H,t, J 7Hz).

165 8.13 (1H,s), 7.91 (1H,s), 7.28 (2H,m), 7.20 (2H,m), 5.56 (1H,m), 5.17 (lH,d, J 16Hz), 4.22 (lH,d, J 12Hz), 4.15 (1H,d, J 12Hz), 3.31 (3H,s), 2.96 (1H,d, J 12Hz), 2.79 (lH,d, J 12Hz), 2.04 (2H,m), 0.93 (3H,t, J 7Hz).

193 8.21 (1H, s), 7.99 (1H, s), 7.54 (lH,m), 7.14 (1H,m), 6.98 (lH,m), 4.33 (2H,m), 3.28 (lH,d, J 12Hz), 3.14 (1H,d, J 12Hz), 2.08 (2H,a, J 7Hz), 1.00 (3H,t, J 7Hz).

223 8.24 and 8.22 (1H, 2xs), 7.99 and 7.96 (1H, 2xs), 7.45 (2H,m), 7.14 (lH,m), 6.99 (lH,m), 5.49 (2H R1 is CH=CHCH2CH3, m), 4.40-4.00 (2H,m), 3.00 (2H,m), 1.92 (2H R1 is CH=CHCH2CH3, quintet, J 7Hz), 1.45-1.25 (6H compound R1 is nBu,m), 0.91 and 0.85 (3H,2xt, J 7Hz)

COMPOUND NO.

421 8.15 (lH,s), 7.91 (lH,s), 7.81 (lH,m), 7.36 (1H, m), 7.19 (lH,m), 4.48 (1H, q, J 7Hz), 4.29 (lH,s), 3.43 (lH,d, J 13Hz), 3.17 (lH,d, J 13Hz), 1.71 (3H,d, J 7Hz), 1.91 (9H,s).

424 Major Diastereoisomer 8.15 (lH,s), 7.88 (lH,s), 7.80 (lH,m), 7.34 (lH,m), 7.18 (2H,m), 4.54 (1H, q, J 7Hz), 4.16 (lH,s), 3.45 (lH,d, J 13Hz), 3.23 (lH,d, J 13Hz), 1.72 (3H,d, J 7Hz), 0.92 (9H,s).

Minor Diastereoisomer 7.96 (lH,s), 7.80 (lH,m), 7.63 (lH,s), 7.40-7.00 (3H,m), 4.79 (lH,s), 4.66 (lH,q, J 7Hz), 3.35 (1H,d, J 13Hz), 3.05 (lH,d, J 13Hz), 1.81 (3H,d, J 7Hz), 1.11 (9H,s).

426 Major Diastereoisomer 8.17 (lH,s), 7.90 (lH,s), 7.57 (lH,m), 7.25-6.80 (3H,m), 4.50 (lH,q, J 7Hz), 3.86 (lH,s), 3.34 (lH,d, J 12Hz), 3.09 (1H,d, J 12Hz), 1.68 (3H,d, J 7Hz) and 0.89 (9H,s).

COMPOUND NO.

426 (cont/d) Minor Diastereoisomer 7.95 (1H,s), 7.62 (1H,s), 7.57 | (1H, m), 7.25-6.80 (3H,m), 4.65 (lH,q, J 7Hz), 4.23 (lH,s), 3.05 (lH,d, J 12Hz), 2.91 (lH,d, J 12Hz), 1.79 (3H,d, J 7Hz), 1.10 (9H,s).

430 8.15 (lH,s), 7.89 (lH,s), 7.82 (lH,m), 7.09 (lH,m), 6.94 (lH,m), 4.48 (lH,q, J 7Hz), 4.24 (lH,s), 3,41 (1H,d, J 13Hz), 3.15 (1H,d 13Hz), 1.70 (1H,d, J 7Hz), 0.91 (9H,s).

432 8.09 (lH,s), 7.81 (1H,s), 7.62 | (1H,m), 6.82 (lH,m), 6.70 (lH,m), 4.44 (lH,q, J 7Hz), 3.98 (lH,s), 3.69 (3H,s), 3.30 (lH,d, J 13Hz), 3.07 (lH,d, J 13Hz), 1.64 (3H,d, J 7Hz), 0.81 (9H,s).

Compounds of general formula (I):

wherein Az, R1 to R6, X, Y and Z are as defined above, except that R2 is not hydrogen, can be prepared from compounds of general formula (IV) [compounds of formula (I) wherein R2 is hydrogen].

wherein Az, R1, K3 to R6, X, Y and Z are as defined above, by treatment with a base, such as sodium hydride and an alkyl halide, an alkenyl halide or an alkynyl halide, R2Hal wherein Hal can be chlorine, bromine or iodine in a suitable solvent such as tetrahydrofuran.

Compounds of general formula (IV) wherein R1 is a group of general formula (III) wherein R8 and R9 or R8 and R10 are hydrogen can be prepared by reduction of compounds of general formula 7) compounds of general formula (IV) wherein R1 is a group of general formula (Il)]:

wherein Az, R3 to R7, X, Y and Z are as defined above.In cases where both R8 and R9 are hydrogen (a trans double bond) this can be achieved by an aluminium hydride reducing agent such as sodium bis (2-methoxyethoxy)aluminium hydride or lithium aluminium hydride in an appropriate solvent such as tetrahydrofuran. In cases where both R8 and R10 are hydrogen (a cis double bond) this can be achieved by catalytic hydrogenation over a suitable catalyst, such as palladium on barium sulphate.

Compounds of general formula (V) can be prepared by treatment of compounds of general formula (VI):

wherein Az, R3 to R6, X, Y and Z are as defined above, with a metal acetylide of general formula (VII)

wherein R7 is as defined above, and M represents a metal such as lithium, magnesium or titanium or M can be silicon, in the presence of an appropriate fluoride catalyst.

As an alternative compounds of general formula (IV) wherein R1 is a group of general formula (III) can be prepared by treatment of compounds of general formula (VI) with compounds of general formula (VIII):

wherein R8 to R10 are as defined above and M is magnesium (a Grignard reagent) or lithium in an appropriate solvent such as tetrahydrofuran.

Compounds of general formula (IV) wherein R1 is an alkyl group (and R5 is not hydrogen) can be prepared by treatment of compounds of general formula (VI) with compounds of general formula R1M wherein R1 is as defined above and M is a metal such as lithium or magnesium.

Compounds of general formula (VI) can be prepared by treatment of compounds of general formula (IX)

wherein Hal, R3 to R6, X, Y and Z are as defined above, with an azole (imidazole or 1,2,4-triazole) in the presence of an appropriate base, such as potassium carbonate, in a suitable solvent such as dimethyl formamide.

As an alternative compounds of general formula (V) can be prepared by treatment of compounds of general formula (IX) with compounds of general formula (VII) wherein M is lithium, magnesium or titanium followed by treatment with an azole (imidazole or 1,2,4-triazole).

As a further alternative compounds of general formula (IV) wherein R1 is a group of general formula (III) can be prepared by treatment of compounds of general formula (IX) with a compound of general formula (VIII) wherein M is lithium or magnesium followed by treatment with an azole (imidazole or 1,2,4-triazole).

Compounds of general formula (IX) can be prepared by oxidation of compounds of general formula (X):

wherein Hal, R3 to R6, X, Y and Z are as defined above, with a suitable oxidizing agent such as Jones reagent.

Compounds of general formula (X) wherein R5 and R6 are hydrogen can be prepared by treatment of compounds of general formula (XI):

wherein R3, R4, X, Y and Z are as defined above, with a solution of the appropriate halogen, for instance bromine, in water.

Compounds of general formula (XI) wherein R3 and R4 are hydrogen can be prepared by treatment of Grignard reagents of general formula (XII):

wherein Hal, X, Y and Z are as defined above, with allyl bromide, optionally in the presence of a copper (I) catalyst, in a suitable solvent such as diethyl ether.

Compounds of general formula (XII) can be prepared by methods set out in the literature.

As an alternative compounds of general formula (IX) can be prepared by treatment of Grignard reagents of general formula (XIII):

wherein Hal, R3, R4, X, Y and Z are as defined above, with an acid chloride of general formula (XIV):

wherein Hal, R5 and R6 are as defined above, in a suitable solvent such as diethyl ether or tetrahydrofuran at low temperature.

Compounds of general formula (XIII) and (XIV) can be prepared by methods set out in the literature.

As a further alternative compounds of general formula (VI) can be prepared by oxidation of compounds of general formula (xV):

wherein Az, R3- to R6, X, Y and Z are as defined above. An appropriate method of oxidation is the Swern modification of the Moffat oxidation (dimethyl sulphoxide, oxalyl chloride and triethylamine in dichloromethane), Qr the Moffat oxidation (dimethyl sulphoxide, acetic anhydride and triethylamine in dichloromethane) or the use of Jones reagent.

Compounds of general formula (Xv) wherein R5 and R6 are hydrogen can be prepared by treatment of an epoxide of general formula (XVI):

wherein R3, R4, X, Y and Z are as defined above, with an azole (imidazole or 1,2,4-triazole) in an appropriate solvent such as ethanol.

Compounds of general formula (XVI) can be prepared by epoxidation of compounds of general formula (XI) with an appropriate peracid such as peracetic acid or m-chloroperbenzoic acid.

As an alternative compounds of general formula (XVI) can be prepared by treatment of compound of general formula (X) (wherein R5 and R6 are hydrogen) with an appropriate base such as sodium hydroxide in a suitable solvent such as methanol or ethanol.

As an alternative compounds of general formula (IV) wherein R6 is hydrogen can be prepared by treatment of compounds of general formula (XVII):

wherein R1, R3 to R5, X, Y and Z are as defined above, with an azole (imidazole or 1,2,4-triazole) in a convenient solvent such as ethanol.

Compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XVIII):

wherein R1, R3, R4, X, Y and Z are as defined above with a sulphur ylid of general formula (XIX): ## R2S-CHR5 (XIX) wherein R5 is as defined above and R is methyl if R5 is hydrogen or R is phenyl if R5 is not hydrogen, in a convenient solvent such as dimethyl sulphoxide.

Sulphur ylids of general formula (XIX) can be prepared by methods set out in the literature.

Compounds of general formula (XVIII) wherein R1 is a group of general formula (II) can be prepared by methods set out in the literature. For instance, by the treatment of compounds of general formula (XX):

wherein R3, R4, X, Y and Z are as defined above, with a compound of general formula (VII) wherein R2 is as defined above and M is copper (I) or M is trialkyltin or hydrogen in the presence of a palladium catalyst.

As an alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (II) can be prepared by treatment of compounds of general formula (XXI):

wherein R3, R4, X, Y and Z are as defined above, with a compound of general formula (VII) wherein M is lithium or magnesium followed by oxidation with a suitable oxidizing agent such as chromium trioxide.

As a further alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (II) can be prepared by treatment of a compound of general formula (XXII):

wherein R3, R4, X, Y and Z are as defined above and NR2 is a convenient amide group such as NMeOMe with a group of general formula (VII) wherein M is lithium or magnesium in a convenient solvent such as tetrahydrofuran.

Compounds of general formula (XVIII) wherein K1 is a group of general formula (III) can be prepared by methods set out in the literature. For instance, by the treatment of compounds of general formula (Xx) with compounds of general formula (VII) wherein M is copper(I) or manganese (I) or tributyltin or magnesium in the presence of a palladium catalyst in a suitable solvent such as tetrahydrofuran.

As an alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (III) can be prepared by treatment of compounds of general formula (XXII) or of general formula (XXIII):

wherein R3, R4, X, Y and Z are as defined above, with a compound of general formula (VIII) wherein M is lithium in a suitable solvent such as ether.

As a further alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (III) can be prepared by treatment of compounds general formula (XXI) with compounds of general formula (VIII) wherein R is lithium or magnesium followed by oxidation with a suitable oxidizing agent such as chromium trioxide or manganese dioxide.

As a further alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (III) and R10 is not hydrogen can be prepared by treatment of a compound of general formula (XXI) with compounds of general formula (XXIV):

wherein Hal, R5 and R9 are as defined above. and RCH2=R10 followed by oxidation with a suitable oxidizing agent such as chromium trioxide and then acid catalysed rearrangement.

As a further alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (III) can be prepared by treatment of a compound of general formula (xx) with a compound of general formula (VIII) wherein M is trialkylsilyl (eg, trimethylsilyl) in the presence of a suitable Lewis acid such as aluminium trichloride.

As a further alternative compounds of general formula (XVIII) wherein R1 is a group of general formula (III) wherein R8 and R9 or R8 and R10 are hydrogen can be prepared by hydrogenation of compounds of general formula (XVIII) wherein R1 is a group of general formula (II). In cases where R8 and R9 are hydrogen (a trans double bond) a suitable reducing agent is lithium or sodium in liquid ammonia. In cases where R8 and R10 are hydrogen (a cis double bond) a suitable reducing agent is hydrogen over a suitable catalyst, for instance palladium on barium sulphate.As an alternative cases where R8 and R9 are hydrogen (a trans double bond) can be prepared by isomerisation of cases where R8 and R10 are hydrogen (a cis double bond) with a suitable catalyst such as iodine.

Compounds of general formula (XVIII) wherein R1 is an alkyl group can be prepared by methods set out in the literature. For instance, by the treatment of compounds of general formula (XX) with compounds of general formula R1M wherein R1 is as defined above and M is copper (I) or M is magnesium (at low temperature) in a suitable solvent such a tetrahydrofuran.

As an alternative compounds of general formula (XVIII) wherein R1 is an alkyl group can be prepared by treatment of compounds of general formula (XXI) with compounds of general formula R1M wherein R1 is as defined above and M is lithium or magnesium followed by oxidation with a suitable oxidising agent such as chromium trioxide.

As a further alternative compounds of general formula (XVIII) wherein R1 is an alkyl group can be prepared by treatment of compounds of general formula (XXII) or of general formula (XXIII) with compounds of general formula R1M wherein R1 is as defined above and M is lithium in a suitable solvent such as ether.

As a further alternative compounds of general formula (XVII) wherein R1 is an appropriate alkyl group can be prepared by hydrogenation of compounds of general formula (XVIII) wherein R1 is a group of general formula (II) or a group of general formula (III).

As an alternative compounds of general formula (VIII) wherein R1 is an alkyl group can be prepared by treatment of compound of general formula (XXV)

wherein R1 s as defIned above wIth compounds of general formula (XIII), optionally in the presence of a copper (I) catalyst in a suitable solvent such as ether.

As a further alternative compounds of general formula (XVIII) wherein R1 is an alkyl group can be prepared by treatment of compounds of general formula (XXVI) :

wherein R1 is as defined above, with compounds of general formula (XIII) or compounds of general formula (XXVII)

wherein R3, R4, X, Y and Z are as defined above, in a suitable solvent such as diethyl ether followed by oxidation with suitable oxidizing agent such as chromium trioxide.

As a further alternative compounds of general formula (XVIII) wherein R1 is an alkyl group can be prepared by treatment of compounds of general formula (XXVIII)

wherein R1 is as defined above, or compounds of general formula (XXIX)

wherein R1 and NR2 are as defined above (eg. NR2 is NMeOMe), with compounds of general formula (XXVII) in a suitable solvent such as diethyl ether.

Compounds of general formula (Xx), (XXI), (XXIII), (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XXVIII) and (XXIX), can be prepared by methods set out in the literature.

As a further alternative compounds of general formula (IV) can be prepared by treatment of compounds of general formula (XXX):

wherein Az, R, R5 and R6 are as defined above, with Grignard reagent of general formula (XIII) in a suitable solvent such as diethyl ether.

Compounds of general formula (XXX) can be prepared by treatment of compounds of general formula (XXXI) :

wherein Hal, R1, R5 and R6 are as defined above, with an azole (imidazole or 1,2,4-triazole) in the presence of a suitable base such as potassium hydride, in a suitable solvent such as dimethyl formamide.

Compounds of general formula (XXXI) wherein K1 is an alkyl group can be prepared by treatment of compounds of general formula (XIV) with compounds of general formula R1M wherein R1 is as defined above (an alkyl group) and M is copper (I) or M is magnesium (at low temperature) in a suitable solvent such as tetrahydrofuran.

As an alternative when R1 is a tertiary alkyl group (eg. tertiary butyl) compounds of general formula (XXXI) can be prepared by treatment of compounds of general formula (XXXII)

wherein R1, R5 and R6 are as defined above, with a suitable halogen (such as chlorine or bromine) as described in the literature.

Compounds of general formula (XXXII) can be prepared by methods set out in the literature.

As a further alternative compounds of general formula (IV) wherein R3 and R4 are hydrogen can be prepared by treatment of compounds of general formula

wherein Az, R1, R5 and R6 are as defined above, with a Grignard reagent of general formula (XII) in the presence of a copper (I) catalyst.

Compounds of general formula (XXXIII) can be prepared by treatment of compounds of general formula (XXX) with the sulphur ylid of formula Me2S + CH2.

The compounds, their salts and metal complexes are active fungicides, particularly against the diseases Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, apples, vegetables and ornamental plants.

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fuliqinea on cucurbits (e.g.

cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines Helminthosporium spp., e.g. Pyrenophora teres, Pseudocercospurella herpotrichoides, Rhynchosçorium.

spp., Septoria spp. and Rhizoctonia spp. e.g. R.

cereal is Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans Venturia inaequalis (scab) on apples.

Some of the compounds have also shown a broad range of activities against fungi in vitro. They have activity against various post-harvest diseases on fruit (e.g. Penicillium diaqatum and italicum on oranges Gloeosporium musarum on bananas and Botrytis cinerea on grape). Further some of the compounds are active as seed dressings against : Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilaqo spp. and Helminthosporium spp. on cereals.

The compounds can move acropetally in the plant tissue. Moreover, the compounds can be volatile enough to be active in the vapour phases against fungi on the plant.

They may also be useful as industrial (as opposed to agricultural) fungicides, e.g. in the prevention of fungal attack on wood, hides, leather and especially paint films.

The compounds of the invention also possess useful pharmaceutical activity as aromatase inhibitors. Aromatase is an enzyme which effects the aromatisation of ring A in the metabolic formation of various steroid hormones. Certain tumours are dependent for their maintenance or growth upon circulating steroids containing an aromatic ring A, and a chemical agent which inhibits the aromatisation of ring A in the precursors of such steroids is likely to be effective in inhibiting the growth of such hormone dependent tumours.

The compounds may be used as such for fungicidal purposes but are more conveniently formulated into compositions for such usage. The invention thus provides a fungicidal composition comprising a compound of general formula (I) as hereinbefore defined, a salt, or a complex thereof; and, optionally, a carrier or diluent.

The invention also provides a method of combating a fungi, which comprises applying to a plant, to seed of a plant, or to the locus of the plant or seed, a compound, salt, or complex thereof, as hereinbefore defined.

The compounds and their complexes and salts can be applied in a number of ways, for example they can be applied, formulated or unformulated, directly to the foliage of a plant, or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour; or as slow release granules.

Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted; or to the soil generally, to paddy water or to hydroponic culture systems. The invention compounds may also be injected into plants or trees and they may also be sprayed onto vegetation using electrodynamic spraying techniques.

The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or be pelleting a mixture of the active ingredient and powder filler. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methyl-pyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (e.g. 2ethoxy-ethanol and 2-butoxyethanol).

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the pres-ence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving the distribution, adhesive powder and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound are preferred.

Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising the compound of general formula (I) a salt or metal complex thereof.

The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s); or which are spray formulations of the kind suitable for use in electrodynamic spraying techniques. The foregoing agents can be cationic, anionic or non-ionic agents. Suitable cat ironic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonate aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydride, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), and the concentrate is to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional and electrodynamic spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient(s).These concentrates suitably contain organic acids (e.g. alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecyl benzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s) having biological activity, e.g. compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal activity.

The other fungicidal compound can be, for example, one which is capable of combating ear diseases of cereals (e.g. wheat such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple etc.

These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula (I) alone; further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound are carbendazim, benomyl, thiophanatemethyl, thiabendazole, fuberidazole, etridazole, dichlorofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminium, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, R0151297, pyrazophos, ethirimol, ditalimofos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz, flutriafol, hexaconazole i.e. the chemical 1-(1,2,4 triazol-1-yl)-2-(2,4-dichlorophenyl)hexan-2-ol, flusilazole ie, DPX H6573 (l-((bis-4 fluorophenyl)methylsilyl)methyl)-lH-1,2,4-triazole, triadimefon, triadimenol, diclobutrazol, terbuconazole, furconazole, cis-furconazole, cyproconazole, fenpropimorph, fenpropidin, chlorozolinate, diniconazole, imazilil, fenfuram, carboxin, oxycarboxin, dithianon, methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos, kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, pyroquilan, chlorbenzthiazone, neoasozin, polyoxin D, validamycin A, repronil, fluotolanil, pencycuron, diclomezine, phenazin oxide, nickel dimethyldithiocarbamate, techlorthalem, bitertanol, bupirimate, etaconazole, strptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, 1-(2-cyano2-methoxyimino-acetyl)-3-ethyl urea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, binapactryl, nitrothalisopropyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, and organomercury compounds.

The compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

Suitable insectclQes which may be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenothoate, chlorpyrifos, isoxathion, propaphos, monocrotophos, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds for use in the invention compositions are compounds which control weeds or seedhead formation, or selectively control the growth of less desirable plants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with the invention compositions are the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g. chlorfluoroecol), maleic hydrazide, glyphosate, glphosine, long chain fatty alcohols and acids, dikegulac, paclobutrazol, flurprimidol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (e.g. chloromequat chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl3,6-dichloroanisate, daminozide, asulam, abscisic acid, isopyrimil, l-(4-chlorophenyl)-4,6-dimethyl-2oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat, benzoylpropethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide, triapenthenol and tecnazene.

The following Examples illustrate the invention.

Temperatures are given in degrees Centigrade (OC), and reactions involving water sensitive intermediates were performed under atmospheres of dry nitrogen.

EXAMPLE 1 This Example illustrates the preparation of 1 (2,4-dichlorophenyl )-2-(1,2,4-triazolyl)methylpent-3- yn-2-ol (Compound No. 7 of Table 1).

2,4-Dichlorobenzyl chloride (20g, 102 mmol) in dry diethyl ether (20 ml) was added dropwise to a stirred mixture of magnesium turnings (2.5g, 102 mmol) in dry diethyl ether (20 ml) at such a rate so as to maintain steady reflux. Dry tetrahydrofuran (40 ml) was then added as di ethyl ether was removed by distillation. The mixture was then cooled to room temperature and added dropwise over 30 minutes to a stirred solution of chloroacetyl chloride (23g, 204 mmol) in dry tetrahydrofuran (100 ml) at -780C. The mixture was allowed to warm to room temperature over 1 hour and water added. The mixture was extracted with diethyl ether and the combined extracts washed with 2M aqueous sodium hydroxide solution and brine, dried (MgSO4) and evaporated in vacuo.

Chromatography [SiO2, ethyl acetate-hexane (5:95) to (10:90] gave 1-chloro-3-(2,4-dichlorophenyl)acetone (3.5g, 14%). MP. 620C.

l-Chloro-3-(2,4-dichlorophenyl)acetone (6.0g, 25 mmol) in acetonitrile (10 ml) was added dropwise to a stirred mixture of 1,2,4-triazole (3.5g, 50 mmol) and potassium carbonate (7.0g, 50 mmol) in dry acetontrile (40 ml) at 500C. After 4 hours the mixture was added to water. The mixture was extracted with ethyl acetate and the combined extracts washed with brine (until neutral), dried (MgSO4) and evaporated in vacuo. Trituration (isopropyl alcohol and hexane) gave 1-(1,2,4- triazolyl)-3-(2,4-dichlorophenyl)acetone (3.5g, 52%) MP. 1100C.

n-Butyllithium (3 ml of a 1.55 M solution in hexane, 4.6 mmol) was added slowly to a stirred solution of propyne (0.18g, 4.6 mmol) in dry tetrahydrofuran (9 ml) at -780C. After 30 minutes chlorotitanium triisopropoxide (5.1 ml of a 1.0 M solution in hexane, 5.1 mmol) was added dropwise.

After 20 minutes 1-(1,2,4-triazolyl)-3-(2,4dichlorophenyl)acetone (1.0g, 4.0 mmol) in dry tetrahydrofuran (20 ml) was added dropwise and the mixture allowed to warm to room temperature and poured into saturated aqueous ammonium chloride solution. The resulting mixture was filtered and the precipitate washed with water and ethyl acetate. The filtrate was washed with water and brine, dried (MgSO4) and evaporated in vacuo. Chromatography (SiO2, ethyl acetate) gave l-(2,4-dichlorophenyl)-2 (1,2,4-triazolyl)methylpent-3-yn-2-ol (Compound No. 7 of Table 1) (0.21g, 17%). MP. 110-1130C.

EXAMPLE 2 This Example illustrates the preparation of 1 (4-chlorophenyl)-2-(1,2,4-triazolyl)methylpent-3-yn2-ol (Compound No. 127 of Table 1).

4-Chlorobenzyl chloride (32.8g, 204 mmol) in dry diethyl ether (30 ml) was added dropwise to a stirred mixture of magnesium turnings (5.0g, 204 mmol) in dry diethyl ether (50 ml) at such a rate so as to maintain steady reflux. Dry tetrahydrofuran (80 ml) was then added as diethyl ether was removed by distillation. The mixture was then cooled to room temperature and added dropwise over 1 hour to a stirred solution of chloroacetyl chloride (46g, 408 mmol) in dry tetrahydrofuran (200 ml) at -780C. The mixture was allowed to warm to room temperature over 1 hour and then poured into water. The mixture was extracted with diethyl ether and the combined extracts were washed with 2M aqueous sodium hydroxide solution and brine, dried (MgSO4) and evaporated in vacuo. Chromatography [SiO2, hexane-ethyl acetate (95:5)] gave 1-chloro-3-(4-chlorophenyl)acetone (16.8g, 40%). MP. 47-490C.

l-Chloro-3-(4-chlorophenyl)acetone (6.0g, 30 mmol) in acetonitrile (5 ml) was added dropwise to a stirred mixture of 1,2,4-triazole (4.2g, 60 mmol) and potassium carbonate (8.8g, 60 mmol) in dry acetonitrile (50 ml) at 500C. After 3d hours the mixture was cooled and filtered. The filtrate was poured into water and the mixture extracted with ethyl acetate. The combined extracts were washed with brine (until neutral), dried (MgsO4) and evaporated in vacuo. Chromatography [SiO2, ethyl acetate-hexane (50:50) to (100:0)] gave 1-(1,2,4- triazolyl)-3-(4-chlorophenyl)acetone (3.23g, 46%).

n-Butyllithium (24 ml of a 2.4 M solution in hexane, 60 mmol) was added dropwise to propyne (2.4g, 60 mmol) in dry tetrahydrofuran (100 ml) at -780C under nitrogen. After 30 minutes chlorotitanium triisopropoxide (67 ml of 1.0 M solution in hexane, 67 mmol) was added dropwise. After 20 minutes 1 (1,2,4-triazolyl)-3-(4-chlorophenyl)acetone (10.75g, 50 mmol) in dry tetrahydrofuran (200 ml) was added dropwise. The mixture was allowed to warm to room temperature and then poured into saturated aqueous ammonium chloride solution. The mixture was filtered and the precipitate was washed with water and ethyl acetate. The filtrate was separated and the organic fraction washed with brine, dried (MgSO4) and evaporated in vacuo. Chromatography [SiO2, ethyl acetate-hexane (50:50)] gave 1 (4-chlorophenyl)-2 (1,2,4-triazolyl)methylpent-3-yn-2-ol (Compound No.

127 of Table 1) (5.25g, 41%). MP. 99.5-101.50C.

EXAMPLE 3 This Example illustrates the preparation of 1 (4-chlorophenyl)-2-methoxy-2-(1,2,4triazolyl)methylpent-3-yne (Compound No. 128 of Table 1).

1-(4-Chlorophenyl)-2-(1,2,4-triazolyl)methylpent-3yn-2-ol (1.Og, 3.63 mmol) in dry tetrahydrofuran (12 ml) was added dropwise to a stirred suspension of hexane-washed sodium hydride (0.17g of a 55% dispersion in oil, 3.9 mmol) in dry tetrahydrofuran (12 ml). After 20 minutes iodomethane (1.19, 7.75 mmol) was added dropwise. After 2b hours the mixture was poured into water and the resulting mixture extracted with ethyl acetate. The combined extracts were washed with brine, dried (MgSO4) and evaporated in vacuo. Chromatography (SiO2, ethyl acetate) gave l-(4-chlorophenyl)-2-inethoxy-2-(l,2,4-triaDy1) methylpent-3-yne (Compound No. 128 of Table 1) (0.79g, 75%).

EXAMPLE 4 This Example illustrates the preparation of E-l- (4-chlorophenyl)-2-(1,2,4-triazolyl)methylpent-3-en2-ol (Compound No. 145 of Table 1).

l-(4-Chlorophenyl ) -2-( 1,2,4- triazolyl)methylpent-3-yn-2-ol (2.0g, 7.26 mmol) in dry tetrahydrofuran (15 ml) was added dropwise to a stirred solution of sodium bis (2methoxyethoxy)aluminium hydride (8.5 ml of a 3.4 M solution in toluene, 29 mmol) in dry tetrahydrofuran (24 ml) at OOC under nitrogen. The mixture was warmed to room temperature and after 4d hours cooled to OOC and water added cautiously. The mixture was extracted with ethyl acetate and the combined extracts washed with brine, dried (MgSO4) and evaporated in vacuo. Chromatography (SiO2, ethyl acetate) gave E-1-(4-chlorophenyl-2-(1,2,4-triazolyl) methylpent-3-en-2-ol (Compound No. 145 of Table 1) (1.50g, 74%). MP. 116.5-117.50C.

EXAMPLE 5 This Example illustrates the preparation of E-1-(4chlorophenyl)-2-allyloxy-2-(1,2,4triazolyl)methylpent-3-ene (Compound No. 153 of Table 1).

1-(4-Chlorophenyl)-2-(1,2,4triazolyl)methylpent-3-en-2-ol (0.56g, 2.02 mmol) in dry tetrahydrofuran (6 ml) was added dropwise to a stirred suspension of hexane-washed sodium hydride (0.lg of a 55% dispersion in oil, 2.3 mmol) in dry tetrahydrofuran (6 ml) under nitrogen. After 20 minutes allyl bromide (0.49g, 4.0 mmol) was added and the mixture heated under reflux. After 2 hours the mixture was cooled and poured into water. The resulting mixture was extracted with ethyl acetate and the combined extracts were washed with brine, dried (MgSO4) and evaporated in vacuo.

Chromatography (SiO2, ethyl acetate) gave E-1-(4chlorophenyl)-2-allyloxy-2-(1,2,4triazolyl)methylpent-3-ene (Compound No. 153 of Table 1) (0.41g, 64%).

EXAMPLE 6 This Example illustrates the preparation of 1 (2-chloro-4-fluorophenyl)-2-(1,2,4triazolyl)methylhex-3-yn-2-ol (Compound No. 193 of Table 1).

2-Chloro-4-fluoroiodobenzene (50g, 200 mmol) in dry diethyl ether (100 ml) was added to a stirred mixture of magnesium turnings (4.9g, 200 mmol) in dry diethyl ether (30 ml) at such a rate so as to maintain steady reflux. After the resultant mixture had been heated under reflux for a further 45 minutes allyl bromide (27.2 ml, 200 mmol) was added dropwise at such a rate so as to maintain steady reflux. After a further 30 minutes at reflux the mixture was poured onto ice and 2M hydrochloric acid was added to dissolve the precipitate. The mixture was extracted with ether and the combined extracts were dried (MgSO4) and evaporated in vacuo. Chromatography (SiO2, hexane) gave 3-(2-chloro-4-fluorophenyl)prop-1-ene (25g, 74%).

m-Chloroperoxybenzoic acid (13.3g, 85%, 89 mmol) was added to a stirred solution of 3-(2-chloro4-fluorophenyl)-prop-l-ene (13.3g, 78 mmol) in dry dichloromethane (150-ml) at OOC. After 6 hours the mixture was washed with aqueous sodium sulphite solution and then 2M aqueous sodium hydroxide solution. The mixture was then dried (MgSO4) and evaporated in vacuo to give l,2-epoxy-3-(2-chloro-4- fluorophenyl)propane (12.5g, 86%) which was used without further purification.

A stirred mixture of l,2-epoxy-3-(2-chloro-4- fluorophenyl)propane (lug, 6 mmol), potassium carbonate (0.8g, 6 mmol) and 1,2,4-triazole (0.5g, 8 mmol) in industrial methylated spirit (10 ml) was heated under reflux. After 3 hours the mixture was poured into water and the resultant mixture extracted witn ethyl acetate. The combined extracts were washed (water), dried (MgSO4), and evaporated in vacuo. Chromatography [SiO2, iso-propyl alcoholdichloromethane (20:80)] gave 1-(1,2,4-triazolyl)-3 (2-chloro-4-fluorophenyl)propan-2-ol (0.8g, 52%).

Jones reagent (9.6 ml) (J. Chem. Soc., 1946, 39) was added dropwise over 45 minutes to a stirred solution of l-(l,2,4-triazolyl)-3-(2-chloro-4- fluorophenyl)propan-2-ol (1.lug, 4.3 mmol) in 8N sulphuric acid (22 ml) at 150C. After 30 minutes the mixture was cooled to 100C and iso-propanol (6 ml) added. 2N Sodium hydroxide solution was added to basify the reaction mixture which was then extracted with ethyl acetate (x3). The combined extracts were dried (MgSO4) and evaporated in vacuo to give 1 (1,2,4-triazolyl)-3-(2-chloro-4-fluorophenyl)acetone (0.76g, 70%) mp. 600C.

n-Butyilithium (1.4 ml of a 2.5M solution in hexane, 3.5 mmol) was slowly added to a stirred solution of but-l-yne (0.2g, 3.5 mmol) in dry tetrahydrofuran (7 ml) at -780C. After 30 minutes chlorotitanium triisopropoxide (3.8 ml of a 1.OM solution in hexane, 3.8 mmol) was added dropwise.

After 20 minutes l-(1,2,4-triazolyl)-3-(2-chloro-4fluorophenyl)acetone (0.76g, 3 mmol) in dry tetrahydrofuran (7 ml) was added dropwise and the mixture allowed to warm to room temperature and poured into saturated aqueous ammonium chloride solution. The mixture was filtered and the precipitate washed with water and ethyl acetate. The filtrate was separated and the organic fractions were washed with water and brine, dried (MgS04) and evaporated in vacuo. Chromatography (SiO2, ethyl acetate) gave l-(2-chloro-4-fluorophenyl)-2-(1,2,4- triazolyl)methylhex-3-yn-2-ol (Compound No. 193 of Table 1) (0.088g, 10%).

EXAMPLE 7 This example illustrates an alternative preparation of l-(2-chloro-4-fluorophenyl)-2-(1,2,4- triazolyl)methylhex-3-yn-2-ol (compound No. 193 of Table 1).

Ethyl magnesium bromide (3.0ml of a 3M solution in diethyl ether, 9.0 mmol) was added dropwise to a solution of but-1-yne (0.61g llmmol) in dry tetrahydrofuran (14ml) at OOC. After more but-l-yne had been bubbled through the mixture l-chloro-3-(2chloro-4-fluorophenyl)acetone (l.Og, 4.5mmol) in dry tetrahydrofuran (6ml) was added dropwise and the mixture was stirred at room temperature for two hours. Water (approximately 50ml) was then added and the resulting mixture was extracted with ethyl acetate. The combined extracts were wash-d with brine, dried (MgS04) and evaporated in vacuo.Chromatography [SiO2, ethyl acetate-hexane (50:50)] gave l-(2-chloro-4-fluorophenyl)-2chloromethylhex-3-yn-2-ol (1.18g, 99%).

1,2,4-Triazole (0.93g, 14mmol), 1-(2-chloro-4fluorophenyl)-2-chloromethylhex-3-yn-2-ol (1.18g, 4.5mmol) and potassium carbonate (1.25g 9mmol) were added to dimethylformamide (25ml) and the mixture was refluxed. After 3 hours the mixture was cooled and added to water. The resulting mixture was extracted with ethyl acetate and the combined extracts were washed with water and brine, dried (MgS04) and evaporated in vacuo. Chromatography [SiO2, ethyl acetate] gave l-(2-chloro-4-fluorophenyl)-2-(1,2,4triazolyl)methylhex-3-yn-2-ol (compound No. 193 of Table 1) (0.60g, 43%).

EXAMPLE 8 This example illustrates the preparation of Z-1- (2-chloro-4-fluorophenyl)-2-(1,2,4triazolyl)methylhex-3-en-2-ol (compound No. 224 of Table 1).

1-(2-Chloro-4-fluorophenyl)-2-(1,2,4triazolyl)methylhex-3-yn-2-ol (0.20g, 0.65mmol) and palladium on charcoal (lOOmg) in ethanol (2ml) were hydrogenated at room temperature. After 18ml of hydrogen had been taken up the reaction mixture was filtered (celite) and evaporated in vacuo to give an approximately 80:20 mixture of Z-1-(2-chloro-4- fluorophenyl)-2-(1,2,4-triazolyl)methylhex-3-en-2-ol aad t CF;,\ LG eny . } triazolyl)methylhexan-2-ol (compound No. 224 of Table 1) (0.061g, 30%). MP 830C.

EXAMPLE 9 This Example illustrates the preparation of 1 (2-chloro-4-fluorophenyl)-2-t-butyl-3-(1,2,4triazolyl)butan-2-ol (Compound No. 430 of Table 1).

2-Chloro-4-fluorobenzyl chloride (4.0g, 22 mmol) in dry diethyl ether (10 ml) was added dropwise to a stirred mixture of magnesium turnings (0.54g, 22 mmol) and iodine (approximately lmg) in dry diethyl ether (10 ml) at such a rate so as to maintain steady reflux. The mixture was then added dropwise to a stirred mixture of 2,2-dimethyl-4 (1,2,4-triazolyl)pntan-3-one (2.5g, 13.8 mmol) in dry diethyl ether (20 ml) at approximately 100C. The mixture was then heated under reflux for 2 hours.

After cooling to room temperature the mixture was decanted from any unreacted magnesium and washed with saturated aqueous ammonium chloride solution. The aqueous layer was separated and extracted with ether.

The combined organic extracts were washed with brine, dried (MgSO4) and evaporated in vacuo.

Chromatography [SiO2, ethyl acetate-hexane (50:50)] gave 1-(2-chloro-4-fluorophenyl)-2-t-butyl-3-(1,2,4triazolyl)butan-2-ol (Compound No. 430 of Table 1) (1.2g, 27%).

EXAMPLE 10 This example illustrates the preparation of 1 (2-chlorophenyl)-2-(1,2,4-triazolyl)methyl-3- methylpent-3-en-2-ol compound No. 452 of Table 1).

2,4-Dichlorobenzyl chloride (20.0g, 102mmol) in dry diethyl ether (20ml) was added dropwise to a stirred suspension of magnesium turnings in dry diethyl ether (20ml) at such a rate so as to maintain steady reflux. Dry tetrahydrofuran (40ml) was then added a such a rate so as to maintain a constant volume as solvent was removed by distillation. The mixture was then added to chloroacetyl chloride (23g, 204 mmol) in dry tetrahydrofuran (lOOml) at -780C over approximately 30 minutes. The mixture was warmed to room temperature over approximately 1 hour and water (200ml) added.The resulting mixture was extracted with ether (3x50ml) and the combined extracts washed with 2M sodium hydroxide and brine, dried (MgS04) and evaporated in vacuo.

Chromatography [SiO2, hexane-ethyl acetate (95:5) to (90:10)] gave 1-chloro-3-(2-chlorophenyl)acetone (3.5g, 14%). mp 620C.

2-Bromobut-2-ene (1.35g, lOmmol) in dry tetrahydrofuran (20ml) was added to a stirred suspension of magnesium turnings (0.24g, lOmmol) in dry tetrahydrofuran (20ml) at such a rate so as to maintain steady reflux. After refluxing for 1d hours the mixture was cooled to OOC and 1-chloro-3-(2chlorophenyl)acetone (1.Og, Smmol) in dry tetrahydrofuran (lOml) was added dropwise. The mixture was warmed to room temperature and poured into saturated aqueous ammonium chloride.

The resulting mixture was extracted with diethy ether and the combined extracts were washed with brine, dried (MgS04) and evaporated in vacuo to give 1- ( 2-chlorophenyl ) -2-Chloromethyl-3-methylpent-3-en- 2-ol (1.3g) which was used without further purification. l-(2-Chlorophenyl)-2-chloromethyl-3methylpent-3-en-2-ol (1.3g, from previous reaction), 1,2,4-triazole (1.04g, 15mmol) and potassium carbonate (1.38g, lOmmol) were stirred under reflux in dimethyl formamide (25ml) for 3 hours. The mixture was then cooled, poured into water and extracted with ethyl acetate. The combined extracts were washed with water and brine, dried (MgS04) and evaporated in vacuo. Chromatography (SiO2, ethyl acetate) gave l-(2-chlorophenyl)-2-(1,2,4triazolyl)methyl-3-methylpent-3-en-2-ol (compound No 452 of Table 1) (0.012g, 1% based on 1-chloro-3-(2chlorophenyl)acetone). MP 880C.

EXAMPLE 11 An emulsifiable concentrate was made up by mixing the ingredients, and stirring the mixture until all the constituents were dissolved.

Compound No. 223 of Table I 10% Ethylene dichloride 40% Calcium dodecylbenzenesulphate 5% "Lubrol" L 10% "Aromasol" H 35% EXAMPLE 12 A composition in the form of grains readily dispersible in a liquid, e.g. water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodium acetate. The resultant mixture was dried and passed through a British Standard mesh sieve, size 44-100, to obtain the desired size of grains.

Compound No. 223 of Table I 50% "Dispersol" T 25% "Lubrol" APN5 1.5% Sodium acetate 23.5% EXAMPLE 13 The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.

Compound No. 223 of Table I 45% "Dispersol" T 5% "Lissapol" NX 0.5% ',Cellofas" B600 2% Sodium acetate 47.5% EXAMPLE 14 The active ingredient was dissolved in a solvent and the resultant liquid was sprayed on to the granules of China clay. The solvent was then allowed to evaporate to produce a granular composition.

Compound No. 223 of Table I 5% China clay granules 95% EXAMPLE 15 A composition suitable for use as a seed dressing was prepared by mixing the three ingredients.

Compound NO. 223 of Table I 50% Mineral oil 2% China clay 48% EXAMPLE 16 A dusting powder was prepared by mixing the active ingredient with talc.

Compound No. 223 of Table I 5% Talc 95% EXAMPLE 17 A Col formulation was prepared by ball-milling the constituents set out below and then forming an aqueous suspension of the ground mixture with water.

Compound No. 223 of Table I 40% "Dispersol" T 10% "Lubrol" APN5 1% Water EXAMPLE 18 A dispersible powder formulation was made by mixing together the ingredients set out below and then grinding the mixture until all were thoroughly mixed.

Compound No. 223 of Table I 25% "Aerosol" OT/B 2% "Dispersol" AC 5% China clay 28% Silica 40% EXAMPLE 19 This Example illustrates the preparation of a dispersible powder formulation. The ingredients wered mixe and the mixture then ground in a comminution mill.

Compound No. 223 of Table I 25% "Perminal" BX 1% "Dispersol" I 5% Polyvinylpyrrolidone 10% Silica 25% China clay 34% EXAMPLE 20 The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredients.

Compound No. 223 of Table I 25% "Aerosol" OT/B 2% "Dispersol" AC 5% China clay 68% In Examples 11 to 20 the proportions of the ingredients given are by weight.

The remaining compounds set out in Table I were similarly formulated as specifically described in Examples 11 to 20.

There now follows an explanation of the compositions or substances represented by the various Trade Marks mentioned above.

LUBROL L : a condensate of nonyl phenol 1 mole) with ethylene oxide (13 moles) AROMASOL H : a solvent mixture of alkylbenzenes DISPERSOL T & AC : a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthalene sulphonate LUBROL APN5 : a condensate of nonyl phenol (1 mole) with naphthalene oxide (5.5 moles) CELLOFAS B600 : a sodium carboxymethyl cellulose thickener LISSAPOL NX : a condensate of nonyl phenol (1 mole) with ethylene oxide (8 moles) AEROSOL OT/B : dioctyl sodium sulphosuccinate PERMINAL BX : a sodium alkyl naphthalene sulphonate EXAMPLE 21 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or aceLone/ethnol wricn was listed te tne requires concentration immediately before use. For the foliage diseases, the formulations (100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the disease. An exception was the test on Erysiphe qraminis in which the plants were inoculated 24 hours before treatment. Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.

The disease control was recorded by the following grading: 4 = no disease 3 = trace - 5% of disease on untreated plants 2 = 6-25% of disease on untreated plants 1 = 26-59% of disease on untreated plants 0 = 60-100% of disease on untreated plants The results are shown in Table III.

TABLE III

COMPOUND PUCCINIA ERYSIPHE VENTURIA CERCOSPORA PYRICULARIA NUMBER RECONDITA GRAMINIS INAEQUALIS ARACHIDICOLA ORYZAE (WHEAT) HORDEI (APPLE) (PEANUT) (RICE) (BARLEY) 7 3 4 0 4 0 8 3 4 4 2 4 13 4 4 4 4 2 14 3 4 4 0 0 25 4 4 4 0 0 27 4 4 0 0 0 43 3 4 3 4 1 67 0 4 4 0 0 68 0 4 4 0 0 73 4 4 4 3 2 74 3 4 4 0 2 85 4 4 4 4 3 87 4 4 4 4 3 103 4 4 4 4 1 105 4 4 4 4 3 127 3 4 0 0 0 128 2 4 3 4 3 131 0 4 0 3 3 TABLE III (continued)

COMPOUND PUCCINIA ERYSIPHE VENTURIA CERCOSPORA PYRICULARIA NUMBER RECONDITA GRAMINIS INAEQUALIS ARACHIDICOLA ORYZAE (WHEAT) HORDEI (APPLE) (PEANUT) (RICE) (BARLEY) 133 4 4 4 4 0 134 3 4 0 4 2 145 4 4 4 4 2 147 3 3 4 3 1 153 3 4 4 3 0 163 4 4 4 4 0 165 3 4 3 4 0 193 4 3 4 4 2 223 4* 3* 4* 2* 0* 224 4 4 4 4 3 421 4 4 4 4 1 423 4 4 4 1 0 424 3 4 4 4 3 426 3 4 4 4 3 427 3 4 2 3 0 428 3 4 4 3 3 429 4 4 4 4 0 430 3 4 4 3 3 432 3 4 4 1 0 452 1* 4* 3* 3* 0* * Results ar rate of 25 ppm - protectant tect only.

HGHA/maa P 34837 MAIN AA017 17 May 1989

Claims

CLAIMS 1. Compounds having the general formula (I):

and stereoisomers thereof, wherein R1 is alkyl (when R5 is other than hydrogen), or is a group of general formula (II): -C- C-K7 (II) or is a group of general formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; R2 is hydrogen, alkyl, alkenyl or alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3, R4, R5 and R6 are independently hydrogen, alkyl, alkenyl or alkynyl;X, Y and Z are independently selected from the group comprising hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, arylo, haloalkoxy or aralkoxy: Az is imidazol-1-yl or 1, 2, 4-triazol-1-yl; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1, 2, 4-triazol-1-yl then R1 is not -C=C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.
2. Compounds as claimed in claim 1 having the general formula (I):

and stereoisomers thereof, wherein R1 represents an alkyl group containing from 1 to 6 carbon atoms (for cases where R5 is other than hydrogen), or a group of general formula (II):

or group of general formula (III)::

wherein R7 to R10 which can be the same or different each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine, bromine or iodine), R2 represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms, (providing that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation), R3 to R6, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms, X, Y and Z which can be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy group, and Az represents l-imidazole or 1, 2, 4-triazole; provided that when R3 and K4 are both methyl, R5 and R6 are both hydrogen and Az is 1, 2, 4-triazol-l-yl then R1 is not -C=C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R1O are not all hydrogen; and salts and metal complexes thereof.
3. Compounds as claimed in claim 1 having the general formula (I):

and stereoisomers thereof, wherein R1 is C1-6 alkyl (when R5 is other than hydrogen) or is a group of general formula (II): C#C-R7 (II) or is a group of general formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, C1-4 alkyl, C2-4 alkenyl, C24 alkynyl; R2 is hydrogen, C1-6 alkyl, C36 alkenyl or C36 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R to R6 are independently hydrogen, C14 alkyl, C2-4 alkenyl or C2-4 alkynyl;X, Y and Z are independently selected from the group comprising hydrogen, halogen, C1-6 alkyl, halo(C1-6)alkyl, C3-7 cycloalkyl, C3-7 cycloalkyl(C1-6)alkyl, C2-6 alkenyl, C2-6 alkynyl, phenyl, phenyl(C1-6) alkyl, C1-6 alkoxy, halo(C1-6)alkoxy, Phenoxy or phenyl(C1-6)alkoxy; Az is imidazol-1-yl or l,2,4-triazol-1-yl; wherein any of the foregoing phenyl moieties are optionally substituted with halogen, C1-6 alkyl, C1-6 alkoxy, halo(C1-6) alkyl, halo(C1-6)alkoxy, nitro, phenyl or phenoxy; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl then R is not -C#C-alkyl, and provided that when R3 and R4 are both alkyl, K5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.
4. Compounds as claimed in any of claims 1, 2 or 3 and having the general formula (I):

and stereoisomers thereof, wherein R1 is C3-4 alkyl; R, R3 and R6 are independently hydrogen or C1-4 alkyl; R4 is hydrogen; R5 is C1-4 alkyl; X, Y and Z are independently hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, phenoxy or phenyl; Az is imidazol-l-yl or 1,2,4 triazol-l-yl; and salts and metal complexes thereof.
5. Compounds as claimed in claim 4 wherein R1 is C3-4 alkyl; R2 is hydrogen or methyl; R , R4 and K6 are all hydrogen, R5 is C12 alkyl; Az is 1,2,4-triazol-1-yl, X, Y and Z are independently hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.
6. Compounds as claimed in any of claims 1, 2 or 3 and having the general formula (I):

and stereoisomers thereof, wherein R1 is a group of general formula (II): -CE C R7 (II) or is a group of formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen, halogen, C1-4 alkyl, C2-4 alkenyl or C2-4 alkynyl; R2 is hydrogen, C1-4 alkyl, C36 alkenyl or C3-6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3, R4, R5 and R6 are independently hydrogen, C1-6 alkyl, C2-4 alkenyl or C2-4 alkynyl; X, Y and Z are independently hydrogen, chlorine or fluorine atoms;Az is imidazol-l-yl or 1,2,4-triazol-1 yl; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl then R1 is not -C#C-alkyl, and provided that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is one of alkyl, alkenyl or alkynyl then R8, R9 and R10 are not all hydrogen; and salts and metal complexes thereof.
7. Compounds as claimed in any of claims 1,2,3 or 6 and having the general formula (XXXIV):

and stereoisomers thereof, wherein R1 is a group of formula (II): -C#C-R7 (II) or is a group of formula (III):

wherein R7, R8, R9 and R10 are independently hydrogen or C1-4 alkyl; R2 is hydrogen, C1-4 alkyl, allyl or propargyl; X, Y and Z are independently hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.
8. Compounds as claimed in any of claims 1,2,3,6 or 7 and having the general formula XXXV):

and stereoisomers thereof, wherein R1 is a group of formula (II): - C#C-R7 (II) or a group of formula (III):

wherein R7 is C1-4 alkyl, R8 is hydrogen, one of K9 and K10 is hydrogen whilst the other is C14 alkyl; R2 is hydrogen or methyl; X and Y are hydrogen, chlorine or fluorine atoms; and salts and metal complexes thereof.
9. The compound

(compound 223 in Table I) and its stereoisomers; and salts and metal complexes thereof.
10. A process for preparing compounds of general formula (I):

which comprises etherifying an alcohol of formula (IV):

wherein Az, R1, R3 to R6, X, Y and Z are as defined in claim 1, by treatment with a base, such as sodium hydride and an alkyl halide, R2 Hal, wherein Hal can be chlorine, bromine or iodine and R2 is as defined in claim 1 in a suitable solvent, wherein the compounds of general formula (IV) are prepared by treatment of compounds of general formula (VI):

wherein Az, R3 to R6, X, Y and Z are as defined in claim 1, with a metal acetylide of general formula (VII):: M - C # C - R7 (VII) wherein R7 is as defined in claim 1 and M represents a metal such as lithium, magnesium or titanium or M can be silicon, in the presence of an appropriate fluoride catalyst [for cases where R1 is a group of general formula (II)] or a compound of general formula (VIII)::

wherein R8 to R10 are as defined in claim 1 and M is magnesium (a Grignard reagent) or lithium in an appropriate solvent such as tetrahydrofuran [for cases where R1 is a group of general formula (III)j or a compound of general formula R1M wherein R1 is an alkyl group as defined in claim 1 and M is a metal such as lithium or magnesium [for cases where R1 is an alkyl group and R5 is not hydrogen].
11. A fungicidal composition comprising, as an ingredient, a compound as claimed in claim 1 or a stereoisomer, salt or metal complex thereof, and, optionally a carrier or diluent.
12. A method of combatting fungi which comprises applying to a plant or seed, a compound as claimed in claim 1 or a stereoisomer, salt or metal complex thereof, or a composition as claimed in claim 11.
13. As novel intermediates compounds of formulae IV, V and XVI wherein R1, R2, R3, R4, K5, R6, X, Y, Z and Az are as defined in claim 1.