Biocidal compounds of the formula (A): where R'is H or CH3, and their isolation from a fermentation broth of a strain of micro- organism from the species Streptomyces malaysiensis are described in International patent application No. PCT/GB2003/000063. The compounds of formula (A) have six asymmetric centres and may exist in the form of one or more isomers. Particularly mentioned in PCT/GB2003/000063 are the compounds of formulae (B) and (C), which are named Malayamycin A and Desmethylmalayamycin A, respectively.

These compounds are biocidal agents, showing antiviral and anti-cancer properties.

They are, however, of particular interest as antifungal agents, especially against plant pathogenic fungi.

The present invention provides alternative biocidal agents.

Thus according to the present invention there is provided a 2, 7-dioxo-bicyclo [4.3. 0] non-5-yl- urea derivative of the general formula (I) : wherein R is H or C1-6alkyl (for example, methyl), the RO group is cis-or trans-to the NH2CONH group, R'is H, formyl, C1-8alkylcarbonyl, C3-8cycloalkylcarbonyl, or optionally substituted benzoyl, and X is a N-linked heterocyclic group of the formula (II) or of the formula (III), wherein R2 is H, C 4alkyl (especially methyl) or halo, or of the formula (IV) : For the avoidance of doubt, the groups of the formulae (II), (III) and (IV) are linked to the remainder of the molecule (I) by the nitrogen atom shown with a valency deficiency.

Within this document the formula (I) comprises the subformulae wherein R, R'and R2 have the definitions as stated for formula (I).

Halo includes fluoro, chloro, bromo and iodo.

In one particular aspect the invention includes a compound of the general formula (I) wherein R is H or methyl, the RO group is cis or trans to the NH2CONH group, R'is H or COCH3, and X is a N-linked heterocyclic group of the formula (II) wherein R2 is H, C1-4alkyl (especially methyl) or halo, or of the formula (il), or of the formula (IV).

In another aspect the invention includes a compound of the general formula (I) wherein (a) R is methyl, the RO group is cis to the NH2CONH. group, R'is H, and X is a N-linked heterocyclic group of the formula (II) wherein R2 is H; or (b) R is methyl, the RO group is trans to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (II) wherein R2 is H; or (c) R is H, the RO group is cis to the NH2CONH group, Rut ils H, and X is a N-linked heterocyclic group of the formula (III) ; or (d) R is H, the RO group is trans to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (III) ; or (e) R is methyl, the RO group is cis to the NH2CONH group, Ri is H, and X is a N-linked heterocyclic group of the formula (II) wherein R2 is methyl ; or (f) R is methyl, the RO group is trans to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (II) wherein R2 is methyl ; or (g) R is methyl, the RO group is cis to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (III) wherein R2 is H; or (h) R is methyl, the RO group is trans to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (III) wherein R2 is H; (i) R is methyl, the RO group is cis to the NH2CONH group, R'is COCH3 and X is a N-linked heterocyclic group of the formula (II) wherein R2 is H; (j) R is methyl, the RO group is cis to the NH2CONH group, R'is H, and X is a N-linked heterocyclic group of the formula (IV).

Throughout this specification, the number of carbon atoms that alkyl moieties may contain is usually stated. Where not stated otherwise, alkyl moBeties may contain from 1 to 8, suitably from 1 to 6 and typically from 1 to 4, carbon atoms. In all cases they may be in the form of straight or branched chains. Examples are methyl, ethyl, n-and iso-propyl, n-, sec-, iso-and tert-butyl, n-pentyl and n-hexyl. Suitable optional substituents of alkyl moieties include halo (e. g. chloro, bromo and fluoro), C16alkoxy and Ct 6alkylthio.

Alkylcarbonyl includes acetyl, propionyl, isopropionyl, butyryl, isobutyryl, s-butyryl, t-butryryl, valeryl, isovaleryl, pivaloyl or the isomeric hexanoyl moieties. Cycloalkylcarbonyl for example designates cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, bicyclo [2.1. 1] hexylcarbonyl, bicyclo [2.1. 1] hexylcar- bonyl, bicyclo [2.2. 0] hexenylcarbonyl, bicyclo [2.2. 1] heptylcarbonyl, bicyclo [2.2. 1] heptenylcar- bonyl, bicyclo [3.1. 1] heptylcarbonyl, bicyclo [3.2. 1] octylcarbonyl, bicyclo [2.2. 2] octylcarbonyl or bicyclo [2.2. 2] octenylcarbonyl. Common optional substituents, being included in this definition are halo, especially chloro, or alkyl, especially methyl, which often are found as two identical radicals attached to the same ring member carbon atom in geminal positions.

Aryl, where later referred to, is usually phenyl. Optional substituents of aryl and of moieties comprising a aryl element such as benzyl and the benzoyl value of R'include halo (especially fluoro and chloro), Ci-salkyl, C2_salkenyl, C2-6alkynyl, Ci-6alkoxy, C2_salkenyloxy, C2-6alkynyloxy, halo (C1-6)alkyl, halo(C1-6)alkoxy, C1-6alkylthio, halo(C1-6)alkylthio, C1-4alkoxy- (C1-6)alkyl, C3-6cycloalkyl, C3-6cycloalkyl(C1-4)alkyl, phenoxy, benzyloxy, benzoyloxy, cyano, nitro,-CONR'R",-S02R',-OS02R',-COR',-CR=NR"or-N=CR'R", in which R'and R"are independently hydrogen, C1-4alkyl, halo(C1-4)alkyl, C1-4alkoxy, halo(C1-4)alkoxy, C1-4alkylthio, C36cycloalkyl, C3-6cycloalkyl (Ci-4) alkyl, phenyl or benzyl.

Where phenyl is optionally substituted in R9, these substituents do not contribute to the final structure of the biologically active compounds of formula (I), but may have a beneficial effect on the synthesis steps in which these radicals are employed. Typical examples of such optional substituents are halo or lower alkyl, i. e. C 4alkyl, such as fluoro, chloro, bromo, methyl, ethyl, propyl, isopropyl or butyl.

Compounds that form part of the invention are illustrated in Table 1 below. These compounds are of the general formula (I) where R, R'and X have the values shown in the table and the orientation of the RO group to the NH2CONH group is as indicated.

Table 1: Compounds of formula I Compound R R'Orientation of RO X No. to NH2CONH- 1 N -N 2 CH3 H trans O N -N 3 H H cis OZL-N -N V 4 N - ,--NH U 5 - -NLL-, 0 CH3 6 CH3 H trans N - =-CH, 7 CH3 H cis -N U 8 CH3 H trans -N 9 NH2 - - NN 10 N - 11 - N N 0 12 H H trans N N 13 CH3 COCH3 cis - \ 14 -N N 0 15 CH3 COCU. cis N N CH3 16 CH3 COCH3 cis NU2 - 17 CH3 N zon -N 18 CH3 OCOCH3 trans -N 19 CH3 - CH3 20 CH3 OCOCH3 trans N -NH Noy5N 21 -N CHa 22 CH3 H trans eN - NH2 \+CH3 23 CH3 OCOCH3 trans -N CH 24 H H trans OZ,-N - \>NH2 CH The compounds of the invention may be obtained from intermediates which have especially been designed and developed for the synthesis of the compounds of formula (I) as shown in the following Scheme Scheme A 0 R H H R 'G NHH R'4 O e. g. MeNH2, g. CH3COCI, O- OCOR9 R wherein (V) C1 opt. C3, Compounds of general formula (1 H) representing the compounds of formula (I) wherein R'is H, may be prepared as shown in Scheme A, from the intermediate compounds of formula (V), wherein R9 is Cul-alkyl or optionally substituted phenyl and R13 is Chalky) optionally substituted with halo, such as chloro or bromo, and R and X are as defined for formula (I), by cleaving off the protective groups R9 and R13 by reacting the compounds of formula (V) with an amine Rt4-NH2, where R14 is C16alkyl, such as methylamine, in a suitable aqueous solvent such as a mixture of methanol and water. The optional substituents of phenyl in R9 being halo or C14alkyl.

Optionally, the compounds of formula (IR), corresponding to the compounds of general formula (1) where R'is formyl, C1_8alkylcarbonyl, C3_8cycloalkylcarbonyl, or optionally substituted benzoyl, may be prepared as also shown in Scheme A, from compounds of formula (IH) by reaction with R'-LG, where R1 is formyl, C18alkylcarbonyl, C38cycloaikylcar- bonyl, or optionally substituted benzoyl, and LG is a leaving group such as chlorine, in the presence of a base such as triethylamine, in a suitable solvent such as dichloromethane (DCM).

The starting materials for the preparation of the active compounds of formula (I), or the encompassed subformuiae (IA), (IB) and (IC) may be obtained by series of consecutive reaction steps, which have all been designed for the present invention, though the single reactions per se are in general selected from conventional reaction types. The following Schemes 1 to 7 display the pathways to prepare the intermediates of formula (V). In this document formula (V) encompasses the displayed subformulae (23), (28) and (47), while the formula (IH) encompasses the subformulae (27), (29) and (47).

The starting materials for the synthesis as shown in Schemes 1 and 5 are either readily available commercially, for example D-ribose, or can be made by methods known in the literature, for example the 2, 4-disilyloxypyrimidines and 2-silyloxy-4-alkyl/arylcarbonyl-4- silylaminopyrimidines. The starting materials for the synthesis sequences of the other Schemes (2) to (4), (6) and (7) may be obtained as shown in the respective preceding Schemes.

Scheme 1 Acid catalyst 4 Oxidising agent, pH HO/'ft%- HO HO e. g. CrO3, py, DCM 0 R sXs (1) R w H Wittig R40H e. 0 n-BuLi, THF 0 RsJ R6) Base, OR solvant R HO p (5) Halogen source, Grubb's 5 - \S OCH2R'Et20 Hat Basa, solvent HO,,, p H 0 e. g. OR4 (9) t (1°) N3 HO,, cl 905 (11) R As shown in Scheme 1, D-ribose (1) can be converted into compounds of general formula (2) by reaction with ketones of general formula R3COR3, where R3 is C1. 4alkyl, and with catalysis by an acid, such as hydrochloric acid, in an alcohol as solvent of general formula R40H, where R4 is C14alkyl. Compounds of general formula (3) can be formed by reaction of compounds of general formula (2), with an oxidising agent, for example chromi- um trioxide and pyridine in a suitable solvent such as dichloromethane (DCM). Compounds of general formula (4) can be formed from compounds of general formula (3) by reaction with a Wittig reagent, such as methylene triphenylphosphorane, which can be generated by reacting methyl triphenylphosphonium bromide with a strong base, such as n-butyl lithium, in a suitable solvent, such as THF, at a temperature of between-78°C and-20°C (preferably at-78°C) and then allowing to warm to room temperature. Compounds of general formula (5) can be formed by subjecting compounds of general formula (4) to catalysis by an acid, such as p-toluene sulphonic acid, in an alcohol R40H as solvent, for example methanol, at a temperature of between room temperature and reflux, preferably at reflux.

Compounds of general formula (6) can be formed from compounds of general formula (5) by reaction with R5CH=CHCH2-LG, where R5 is hydrogen or C1. 4alkyl, and LG is a leaving group such as chlorine or bromine, in the presence of a dialkyl tin reagent (R6) 2SnO, where R6 is a Chalky) group, and a base such as tetrabutylammonium iodide, in a suitable solvent such as acetonitrile at a temperature between-20°C and room temperature (preferably at room temperature).

Compounds of general formula (7) can be formed from compounds of general formula (6), by reaction with R7CH2-LG, where Ff is an optionally substituted phenyl group, such as phenyl or 4-methoxyphenyl, and LG is a leaving group as defined above, in the presence of a base such as sodium hydride, in a suitable solvent such as DMF, at a temperature between-40°C and +40°C, but preferably at 0°C.

Compounds of general formula (8) can be formed from compounds of general formula (7) in a ring-closing metathesis reaction by treatment with a Grubbs catalyst, for example [(cyclohexyl) 3P] 2CIRu=CHPh, in a suitable solvent such as DCM, at a temperature between room temperature and +40°C. Compounds of general formula (9), where Hal is a halogen atom such as chlorine, bromine or iodine, can be formed by reaction of compounds of general formula (8) with a halogen source such as N-bromosuccinimide, in the presence of water and an organic solvent such as diethyl ether.

Compounds of general formula (10) can be formed from compounds of general formula (9) by reaction with a base such as sodium hydroxide in a suitable solvent, such as THF, at between room temperature and reflux, but preferably at reflux.

Compounds of general formula (11) can be formed by treatment of compounds of general formula (10) with a metal azide, such as sodium azide, in a suitable solvent such as methoxyethanol, at between +50°C and reflux, but preferably at reflux.

Scheme 2 N3 H Oxidising agent N3 solvent ho.,,, /OR4 0 e. Ot* '9'Dess-Martin nt (11) H OCH2R R'Periodinane z OCHZR Base, RLG Reducing agent, e9 e. g NaH, Mel, DMF solvent NaBH4, MeOH N3 3H OR Base, R-LG OR t (14) e. g (14) e. g. RuC13. Oxidising agent Na) solvent MeCN, zu N3 Lewis RO OR e. (15) H oCOR'DCM 3 RO >wSR 8 e. g. NBS, DCM ) As shown in Scheme 2, compounds of general formula (13) where the RO group is cis to the azide group, can be formed from compounds of general formula (11) in three steps.

Compounds of general formula (12) can be formed from compounds of general formu- la (11) by oxidation with a suitable oxidising agent such as [1,1, 1-tris (acetyloxy)-1, 1-dihydro- 1, 2-benzodioxol-3- (1 H) -one] (Dess-Martin periodinane) in a suitable solvent such as DCM.

Compounds of general formula (13) can be formed from compounds of general formula (12) by reduction with a suitable reducing agent such as sodium borohydride, in a suitable solvent such as methanol.

Compounds of general formula (14), where the RO group is cis to the azide group, can be formed by reaction of compounds of general formula (13) with a base such as sodium hydride, and a compound of general formula R-LG, where R and LG are defined as above, such as methyl iodide.

Compounds of general formula (15), where the RO group can be either cis or trans to the azide group, can be formed from compounds of general formula (14) by oxidation with an oxidising agent such as ruthenium tetroxide, generated in situ by reaction with ruthenium trichloride, sodium periodate in a suitable solvent, such as a mixture of acetonitrile, carbon tetrachloride and water.

Compounds of general formula (16), where the RO group can be either cis or trans to the azide group, can be formed from compounds of general formula (15) by reaction with thiophenols R8-SH, where R is an optionally substituted phenyl group, such as phenyl, in the presence of a Lewis acid such as boron trifluoride etherate, in a suitable solvent such as DCM, at a temperature between-20°C and-78°C, but preferably at-78°C.

Compounds of general formula (17), where the RO group can be either cis or trans to the azide group, can be formed from compounds of general formula (16) by reaction with a base such as potassium carbonate in a suitable solvent such as methanol.

Compounds of general formula (18) where the RO group can be either cis or trans to the amino group can be formed by reaction of compounds of general formula (17) by reaction with a halogen source such as N-bromosuccinimide in a suitable solvent such as DCM, at a temperature between-30°C and room temperature, but preferably at +5°C.

Scheme 3 N source, N3 RO base R°< e. g. NIS, Tf20, DCM SR , e. 0t (18) H (19) H --N bH (20) 2 R H2N N3 RO 0 I . O e. g. Me3P, (21) O'I JLH-LH H N Ria_NHZ _H RO N) g. MeNH2, 2g O H As shown in Scheme 3, compounds of general formula (19) can be formed from compounds of general formula (18) by reaction with an acid chloride R9-COCI, where R9 is C alkyl or optionally substituted phenyl, in the presence of a base such as 4-dimethyl- aminopyridine and triethylamine.

Compounds of general formula (21) can be formed from compounds of general formula (19) by reaction with compounds of general formula (20), where R2 is as defined above and R10, R"and Rt2 are C14alkyl or phenyl, in the presence of N-iodosuccinimide and triflic acid in a suitable solvent such as DCM, at a temperature between-30°C, and +40°C, but preferably at room temperature.

Compounds of general formula (20) can be made by the methods in the literature, for example, I. lwai, B. Shimizu, T. Nishimura, Chem. Pharm. Bull., 11, p. 1470 (1963).

Compounds of general formula (22) can be prepared by treatment of compounds of general formula (21) with a reducing agent such as trimethylphosphine, in a suitable aqueous solvent such as a mixture of water and THF.

Compounds of general formula (23), where the RO group is cis or trans to the R13CONHCONH group can be formed by reacting compounds of general formula (22) with an isocyanate R13-CO-N=C=O, where R'3 is C18alkyl optionally substituted with halo, such as chloro or bromo, for example trichloroacetyl isocyanate, or an optionally substituted aryl group, in a suitable solvent such as DCM.

Compounds of general formula (IA), which are examples of compounds of general formula (I), where X is the group of formula (II) and R'is H, can be made from compounds of general formula (23), where the RO group is cis or trans to the NH2CONH group, by cleaving off the protective groups R9-CO-and R13-CO-by deprotection with an amine R14- NH2, where R is Ci_salkyl, such as methylamine, in a suitable aqueous solvent such as a mixture of methanol and water.

Compounds of general formula (IB) which are examples of compounds of general formula (I) where X is the group of formula (III), can be made as shown in Scheme 4.

Compounds of general formula (26) can be formed from compounds of general formula (19) by reaction with compounds of general formula (25), where R10, R11, R12 and R15 are C14alkyl or phenyl, in the presence of N-iodosuccinimide and triflic acid in a suitable solvent such as DCM, at a temperature between-30°C and +40°C, but preferably at room temperature.

Compounds of general formula (25) can be made by methods in the literature such, for example 1. Iwai, B. Shimizu, T. Nishimura, Chem. Pharm. Bull., 11, p. 1470 (1963).

Compounds of general formula (27) can be prepared by treatment of compounds of general formula (26) with a reducing agent such as trimethylphosphine, in a suitable solvent such as a mixture of water and THF.

Compounds of general formula (28), where the RO group is cis or trans to the R13CoNHCONH group can be formed by reacting compounds of general formula (27) with an isocyanate R'3-CO-N=C=O, where R13 is C18alkyl optionally substituted with halo, such as chloro or bromo, for example trichloroacetyl isocyanate, or an optionally substituted aryl group, in a suitable solvent such as DCM.

Compounds of general formula (IB), which are examples of compounds of general formula (I), where X is the group of formula (III), can be made from compounds of general formula (28), where the RO group is cis or trans to the NH2CONH group, by cleaving off the protective groups R13-CO- and R15 -CO- by deprotection with an amine R14-NH2, where R14 is Chalky), such as methylamine, in a suitable aqueous solvent such as a mixture of methanol and water.

Scheme 4 Halogen Lewis solvent N3 ROh - plio O-1 -o O R-SI-0 R Hv R OCOR Nf > Rio Reducing N s a- agent -- -N e. g. CC13CONCO, e. g. Me3P, DCM THF, H20 H OCOR9 O) O R ROw tN ° e. g. MeNH2, N H H An alternative route to intermediates of general formula (17) is shown in Schemes 5 and 6. Compounds of general formula (32) can be made from compounds of general formula (30), where R3 is as defined above, and R'6 is C18alkyl or aryl, which are commercially available when R3 and R16 are both CH3, or which can be made by methods in the literature, by reaction with an compound of formula (31) where R17 is C1-4alkyl, in the presence of a base, for example with aqueous sodium hydroxide and tetrabutylammonium iodide, in a suitable solvent such as DCM.

Compounds of general formula (33) can be made from compounds of formula (32) by treatment with an acid such as aqueous acetic acid.

Compounds of general formula (34) can be made by reaction of compounds of formula (33) with sulphonyl chlorides R18SO2CI, where R8 is Cri-alkyl or optionally substituted phenyl, for example methanesulphonyl chloride, in the presence of base such as triethylamine, in a suitable solvent such as DCM.

Compounds of general formula (35) can be made by reaction of compounds of formula (34) with a metal iodide such as sodium iodide, in a suitable solvent such as N, N-dimethylacetamide, at a temperature of +50°C to +150°C, but preferably at +80°C to +120°C.

Compounds of general formula (36) can be made by reaction of compounds of formula (35) in a ring-closing metathesis reaction by treatment with a Grubbs catalyst, for example [(cyclohexyl) 3P] 2CIRu=CHPh, in a suitable solvent such as DCM, at a temperature between room temperature and +40°C.

Compounds of general formula (37) where Hal is a halogen atom such as chlorine, bromine or iodine, can be formed by reaction of compounds of general formula (36) with a halogen source such as N-bromosuccinimide, in the presence of water and an organic solvent such as diethyl ether.

Compounds of general formula (38) can be formed from compounds of general formula (37) by reaction with a base such as sodium hydroxide in a suitable solvent, such as THF, at between room temperature and reflux, but preferably at reflux.

Compounds of general formula (39) can be formed by treatment of compounds of general formula (38) with a metal azide, such as sodium azide, in a suitable solvent such as methoxyethanol, at between +50°C and reflux, but preferably at reflux.

Compounds of general formula (42) can be formed from compounds of general formula (39) in three steps. Compounds of general formula (40) can be formed from compounds of general formula (39) by oxidation with a suitable oxidising agent such as [1, 1, 1-tris (acetyloxy)-1, 1-dihydro-1, 2-benzodioxol-3- (1 H)-one] (Dess-Martin periodinane) in a suitable solvent such as DCM.

Compounds of general formula (41) can be formed from compounds of general formula (40) by reduction with a suitable reducing agent such as sodium borohydride, in a suitable solvent such as methanol.

Compounds of general formula (42) can be formed by reaction of compounds of general formula (41) with a base such as sodium hydride, and a compound of general formula R-LG, where R and LG are defined as above, such as methyl iodide.

Compounds of general formula (17) can be formed by reaction of compounds of formula (42) by reaction with thiophenols R8-SH, in a the presence of an acidic catalyst such as Amberlyst acidic ion exchange resin.

Scheme 5 17 R3 R 7L (31) R37L° is ""p ' s _ (30) Bu4N+I-R H20 allyl bromide H H HO R'BSO solvent, is ' s R 1', R 0 s ts e. g. Nal (33) Et3N acetamid Grubb's source, 0 0 H2C H s R16 g. DCM 'R R O 9 (35) H Hal o, H HO,,, MN3, HO,,, ""O g '. s e. g. NAOS, (38) N3 HO,,,. ho,,,, (39) 0", Ris Scheme 6 N3 H Oxidising agent, N3 HO,,,, solvent 0 solvent 04/"X R e. g. Dess-Martin % 6 H O'6 N R N3 Base, H t-10 e. g. 0 H (42) H Ng 3H RO OH S (17) H-SU OH Compounds of general formula (47), which are examples of compounds of general formula (I) where X is the group of formula (IV), can be made as shown in Scheme 7.

Compounds of general formula (44) can be formed from compounds of general formula (19) by reaction with compounds of general formula (43), where R10, R", R12 and R15 are C14alkyl or phenyl, in the presence of N-iodosuccinimide and triflic acid in a suitable solvent such as DCM, at a temperature between-30°C and +40°C, but preferably at room temperature.

Compounds of general formula (43) can be made by methods in the literature such, for example H. Vorbrueggen, K. Krolikiewicz, B. Bennua, Chemische Berichte, 114, p. 1234 (1981).

Compounds of general formula (45) can be prepared by treatment of compounds of general formula (44) with a reducing agent such as trimethylphosphine, in a suitable solvent such as a mixture of water and THF.

Compounds of general formula (46), where the RO group is cis or trans to the R 3CoNHCONH group can be formed by reacting compounds of general formula (45) with an isocyanate R'3-CO-N=C=O, where R 13 is Cl-Balkyl optionally substituted with halo, such as chloro or bromo, for example trichloroacetyl isocyanate, or an optionally substituted aryl group, in a suitable solvent such as DCM.

Compounds of general formula (IC), which are examples of compounds of general formula (1), where X is the group of formula (IV), can be made from compounds of general formula (46), where the RO group is cis or trans to the NH2CONH group, by cleaving off the protective groups R9-CO-, R13-Co-and R15-Co-by deprotection with an amine R14-NH2, where R14 is C16alkyl, such as methylamine, in a suitable solvent such as a mixture of methanol and water.

Scheme 7 N3 Halogen RO H Acid, solvent N3 N SR e. g. NIS, Tf20, DCM ROW oO o, "0-1"-------------- L i/*\. ° (19) H H -N OCOR si_ . O , R H s, O ROt H N\/N NNH 4-NH 15 Ru e_9. N e. g. MeNH2, °A o M DCM Oi : MeOH H OCOR OCOR (46) o H t H \ RO NN (IC) H OH source,In a further aspect the invention includes the intermediate compounds (8) to (19), (21) to (23), (26) to (28), and (36) to (42), and (44) to (46) as defined above.

The compounds of formula (1) may be active antiviral agents showing for example antiviral activity against the Human Immunodeficiency Virus associated with the disease AIDS. The compounds of formula (1) may also have anti-cancer properties, for example showing an in inhibitory effect on the cell proliferation of cancer cells. As used herein the term biocidal is used to cover activity against pathogens and includes antiviral, antifungal and anticancer activity. The use of the compounds as antifungal agents, particularly against plant pathogenic fungi, is of particular interest.

The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia triticina (or recondita), Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants) ; Erysiphe cichoracearum on cucurbits (for example melon) ; Blumeria (or Erysiphe) graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca maculais on hops, Sphae- rotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp. , Helminthosporium spp. , Drechslera spp.

(Pyrenophora spp. ), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercospo- rella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab) ) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp. (Pleospora spp. ) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella pomi), Cedar apple rust (Gymnosporangium juniperi-virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) and white rot (Botryosphaeria dothidea) ) on apples and pears; Plasmopara viticola on vines; other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperono- spora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp.

(including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables ; Laetisaria fuciformis on turf; Mycosphaerelia spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp. , Typhula spp. , Microdochium nivale, Ustilago spp. , Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophodermium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp. , Ophiostoma piceae, Penicillium spp. , Tricho- derma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans ; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV) and Polymyxa betae on sugar beet as the vector of rhizomania).

A compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.

The invention therefore provides a method of combating or controlling phytopatho- genic fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other plant growth medium, e. g. nutrient solution.

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

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

In order to apply a compound of formula (I) to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other growth medium, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).

SFAs are chemicals that are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of fungi such that a compound of formula (I) is applied at a rate of from 0.1 g to1 Okg per hectare, preferably from 1 g to 6kg per hectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at a rate of 0. 0001 g to 10g (for example 0.001 g or 0.05g), preferably 0.005g to 10g, more preferably 0.005g to 4g, per kilogram of seed.

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

In a still further aspect the invention provides a method of combating and controlling fungi at a locus which comprises treating the fungi or the locus of the fungi with a fungicidally effective amount of a composition comprising a compound of formula (I).

The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water disper- sible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable con- centrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO) ), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

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

Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccha- ride) and, optionally, one or more wetting agents, one or more dispersing agents or a mix- ture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

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

Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclo- hexanone), alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may sponta- neously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room tempera- ture, it may be melted at a reasonable temperature, typically below +70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.

Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents that have a low solubility in water.

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

An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.

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

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

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

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous disper- sion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

A composition may include one or more additives to improve the biological perfor- mance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

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

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylen oxides, such as ethylene oxide, propylene oxide, butylen oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonyl- phenol or octylcresol) ; partial esters derived from long chain fatty acids or hexitol anhydri- des; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides ; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithin.

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

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

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

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

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

The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).

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

By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).

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

Examples of fungicidal compounds which may be included in the composition of the invention are AC 382042 (N- (l-cyano-1, 2-dimethylpropyl)-2- (2, 4-dichlorophenoxy) pro- pionamide), acibenzolar-S-methyl, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol, blasticidin S, boscalid (new name for nicobifen), bromuconazole, bupirimate, captafol, captan, carbenda- zim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cyamidazosulfamid, cyazofamid (IKF-916), cyflufena- mid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethyl (Z)-N-benzyl-N ([methyl (methyl-thioethylideneaminooxyCarbonyl)- amino] thio)-p-alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil (AC 382042), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexacon- azole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY 248908, man- cozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc, metominostrobin, metrafenone, MON65500 (N-allyl-4, 5-dimethyl-2- trimethylsilylthiophene-3-carboxamide), myclobutanil, NTN0301, neoasozin, nickel dimethyl- dithiocarbamate, nitrothale-isopropyl, nuarimol, ofurace, organomercury compounds, orysastrobin, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, poly- oxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON 65500), S-imazalil, simeconazole, sipconazole, sodium pentachlorophenate, spiroxa- mine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabend- azole, thifluzamide, 2-(thiocyanomethylthio) benzothiazole, thiophanate-methyl, thiram, tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, valida- mycin A, vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of the formulae : The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

Some mixtures may comprise active ingredients that have significantly different physi- cal, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspen- sion (using a preparation analogous to that of an SC) but dispersing the liquid active ingre- dient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is further illustrated by the following Examples.

(Glossary: Me is methyl, Ph is phenyl, DCM is dichloromethane, THF is tetrahydrofuran and DMF is N, N-dimethylformamide) EXAMPLE 1 This Example illustrates the preparation of Compound No. 1 of Table 1 Step 1 The preparation of: A mixture of D-ribose (30g, 0. 2mol), anhydrous methanol (120ml), anhydrous acetone (120ml) and concentrated hydrochloric acid (3ml) is refluxed for 18 hours under argon. After cooling to room temperature, pyridine (2ml) is added, and the mixture is concentrated under reduced pressure, and then extracted with diethyl ether (200ml x 3). The combined organic layers are washed with saturated copper sulphate (60ml) and dried over magnesium sulphate, filtered and concentrated to give the desired product as colourless oil (20g).

[α]D20=-64. 0 (c = 0.8, CHC13).

IR (thin film, KBr): v 3465,2942, 2889, 1458, 1374,1211 cm-1.

1H-NMR (400 MHz, CDCl3) # ppm : 1. 24 (s, 3H, CH3), 1.40 (s, 3H, CH3), 3.24 (m, 1 H), 3.35 (s, 3H,-O CH3), 3.58 (m, 2H), 4.33 (m, 1 H), 4.50 (d, 1 H, J = 6.0 Hz), 4.74 (d, 1 H, J = 6.0 Hz), 4.89 (s, 1 H).

Step 2: The preparation of: An oven dried 2 L round-bottomed flask with a magnetic stir bar is charged with dry dichloro- methane (DCM, 900ml) and pyridine (58mut, 0. 72mol). To this solution is added chromium trioxide (36g, 0. 36mol) portionwise. After stirring for 30 minutes, a solution of the product from Step 1 (6g, 30mmol) in 100mol dry DCM is added over 30 minutes, and the mixture is left to stir for 30 minutes. The mixture is poured into cooled saturated sodium bicarbonate (1000mi) and stirred for 10 minutes. The organic phase is separated and the mixture is extracted with DCM (200mi x 3). The combined organic layer is dried over anhydrous magnesium sulphate, filtered and concentrated. The brown solution obtained is co-evapora- ted three times with toluene (10 ml). The residue is dissolved in dry DCM (100ml), activated charcoal (1 g) and silica gel (6g) are added, and the mixture is stirred for 2 hours, and filtered through Celite. The Celite is washed with DCM (100ml). Concentration under vacuum gives a colourless oil (4.3g).

1H-NMR (400 MHz, CDCI3) 8 ppm: #. 27 (s, 3H, CH3), 1.43 (s, 3H, CH3), 3.39 (s, 3H,-O CH3), 4.41 (s, 1H, H-2), 4.44 (d, 1H, J = 6.0 Hz, H-3), 4.98 (d, 1H, J = 6.0 Hz, H-4), 5.02 (s, 1H, H- 1), 9.52 (s, 1H,-CHO).

13C-NMR (100 MHz, CDCl3) 8 ppm: 24.7, 26.0, 55.6, 80.6, 83.8, 89.3, 108.9, 112.5, 200.6.

Step 2 (alternative procedure): To a solution of the product from Step 1 (2. 0g, 1 Ommol) in 70 ml acetonitrile is added 2-iodoxybenzoic acid (IBX, 5.64g, 20mol), and then the mixture is refluxed for 2 hours at +80°C. After the starting material disappeared (TLC monitoring), the mixture is cooled to room temperature and filtered. The solvent is removed under vacuum to afford the desired aldehyde (1.83g, 9. 24mol).

'H-NMR (400 MHz, CDCI3) 8 ppm : 1.27 (s, 3H, CH3), 1.43 (s, 3H, CH3), 3.39 (s, 3H,-O CH3), 4.41 (s, 1H, H-2), 4.44 (d, 1 H, J = 6. 0 Hz, H-3), 4.98 (d, 1H, J=6.0Hz, H-4), 5.02 (s, 1H, H- 1), 9.52 (s, 1 H,-CHO).

13C-NMR (100 MHz, CDCl3) 8 ppm: 24.7, 26.0, 55.6, 80.6, 83.8, 89.3, 108.9, 112.5, 200.6.

Step 3: The preparation of: To a suspension of methyltriphenylphosphonium bromide (12.9g, 36mmol) in anhydrous THF (350ml) is added dropwise 2.5M of n-butyl lithium solution in hexanes (14. 4moi, 36mmol) at-78 °C under argon. After addition is completed, the resulting mixture is stirred at 0 °C for 30 minutes, and then cooled to-78°C again. A solution of the product from Step 2 (6.06g, 30mmol) in anhydrous THF (60mi) is added to this solution over 30 minutes. The mixture is warmed to room temperature and stirred for 3 hours, and is then quenched by adding saturated ammonium chloride (400moi). The mixture is extracted with diethyl ether (200ml x 3). The combined organic layer is washed with saturated sodium bicarbonate, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords a colourless oil (5.1g, 25. 5mmol), yield 85%.

[a] D20=-57. 6 (c = 1.15, CHCI3).

IR (thin film, KBr): v 2989, 2939,1461, 1425,1373, 1211, 1105, 868cm'\ 1H-NMR (400 MHz, CDCl3) 8 ppm : 1.31 (s, 3H, CH3), 1.48 (s, 3H, CH3), 3.33 (s, 3H,-O CH3), 4.46 (m, 3H), 4.97 (s, 1H, H-1), 5.14 (d, 1H, J =10. 3 Hz), 5.25 (d, 1H, J = 16.7 Hz), 5.85 (m, 1 H).

13C-NMR (100 MHz, CDOs) 8ppm : 24.8, 26. 3,54. 5,84. 39, 85.4, 88.3, 109. 1,112. 2,117. 2, 137. 5.

HRMS (FAB). Calculated for CioHi704 (M + H+) 201.1127. Found 201.1126.

Step 4 The preparation of: The mixture of the product from Step 3 (4.5g, 22. 5mmol) and p-toluenesulphonic acid (0.5g) in dry methanol (500ml) is refluxed for 24 hours, and pyridine (0. 5ml) is added and the mixture is concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 2: 1) affords a mixture of alpha and beta diols (3. 0g, 18. 7mmol) as a colourless oil with the ratio of 1: 7, yield : 83.3%.

[a] D=-24. 2, (c = 2. 18, CHCl3).

IR (thin film, KBr): v 3402,2936, 1646,1426, 1196, 1124, 1030,933 cm-1.

1 H-NMR (400 MHz, CDCl3) S ppm: 2.38 (d, 1 H, J = 6.66 Hz, -OH), 2.40 (d, 1 H, J = 3.67 Hz, - OH), 3.40 (s, 3H,-O CH3), 4.14 (m, 1H, H-2), 4.17 (m 1H, H-4), 4.33 (t, 1H, J = 6.8 Hz, H-3), 4.87 (s, 1H, H-1), 5.21 (d, 1H, J=12.8 Hz), 5.36 (d, 1H, J=17. 1 Hz), 5.90 (m, 1H). C- NMR (100 MHz, CDCI3) 8 ppm: 55.2, 75.2, 75.3, 85.2, 107.9, 117.4, 136.9.

HRMS (FAB). Calculated for C7H1204 (M+) 160.0736. Found: 160.0734.

Step 5: The preparation of: To a solution of the product from Step 4 (2.62g, 16. 4mol) in dry acetonitrile (200ml) is added dibutyltin oxide (4.9g, 19. 7mmol), tetrabutylammonium iodide (4.84g, 13. 1 mmol), allyl bromide (1.42g, 16. 4mol) and 4A molecular sieves (1 7. 0g) at room temperature under argon. The mixture is refluxed for 5 hours, and then the solvent removed by evaporation. To the residue is added diethyl ether (200ml) and water (200ml), and the organic layer is separated. The water layer is extracted with diethyl ether (100ml x 2). The combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords the desired product (1.9g, 9. 5mmol) as colourless oil, yield : 58%.

[α]D20=+82.5, (c = 0.2, CHCI3).

IR (thin film, KBr): v 3557,3083, 2987,2918, 2850,1733, 1646 cm-1.

'H-NMR (400 MHz, CDCI3) 8 ppm 2.74 (d, 1 H, J = 8.9 Hz, -OH), 3.41 (s, 3H,-O CH3), 3.61 (dd, 1 H, J = 7.0, 3.7 Hz), 4.17 (m, 3H, H-2 and-CH20-), 4.44 (t, 1 H, J = 5.1 Hz, H-4), 4.91 (d, 1 H, J = 4.6 Hz, H-1), 5.2-5. 4 (m, 4H, CH2=CH-), 5.80-5. 95 (m, 2H, H-5 and CH2=CH-).

13C-NMR (100 MHz, CDCI3) 8 ppm: 55.5, 71.1, 72.2, 79.4, 82.9, 102.4, 116. 8, 117.7, 134.1, 135.7.

Step 6: The preparation of: To a solution of the product from Step 5 (1.9g, 9. 5mmol) in dry DMF (40ml) is added sodium hydride (60% dispersion in mineral oil) (0.751 g, 18. 8mmol) and benzyl bromide (1.93g, 11. 3mmol) at 0°C under argon. After stirring overnight, the reaction is quenched by adding saturated sodium bicarbonate (1 00moi), and the mixture is extracted with DCM (50moi x 3).

The combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered, and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords the product (2.5g, 8. 6mmol) as colourless oil, yield : 91%.

[a] D20 = +8. 8, (c = 0. 5, CHCI3).

IR (thin film, KBr): v 3402,2936, 1646,1426, 1196,1124, 1030,933 cm-'.

1H-NMR (400 MHz, CDCI3) 8 ppm: 3.37 (s, 3H,-O CH3), 3.87 (m, 2H, H-2 and H-3), 4.00 (m, 2H), 4.52 (t, 1 H, J = 3 Hz), 4.65 (d, 1 H, J = 11.0 Hz, PhCH2-), 4.72 (d, 1 H, J = 11.0 Hz, PhCH2-), 4.91 (s, 1H), 5.1-5. 2 (m, 4H), 5.87 (m, 2H), 7.2-7. 4 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCl3) 8 ppm: 55.5, 72.0, 72.8, 80.2, 82.3, 82.5, 106.6, 117.9, 128.2, 128.4, 128. 8, 134.8, 138.1, 138.2.

HRMS (FAB). Calculated for C17H2204 (M+) 290.1518. Found: 290.1518.

Step 7: The preparation of: To a solution of the product from Step 6 (0.014. 5g, 0. 05mmol) in 5 ml dry degassed DCM is added 5% mol Grubbs catalyst [(cyclohexyl) 3P] 2CIRu=CHPh (0.002g) under argon atmosphere at room temperature, and then the mixture is heated to reflux for 8 hours until the starting material disappeared. The mixture is concentrated and purified by flash chromatography (hexane: ethyl acetate, 5: 1) to afford the desired product (0.0092g) as colourless oil, yield : 70.2%.

[a] D20=-49. 7 (c = 0.3, CHCI3).

IR (neat) 2933,1730, 1454,1367, 1100,1027, 926,689.

'H-NMR (400 MHz, CDCl3) 8 ppm: 3.38 (s, 3H, O CH3), 3.57 (dd, 1H, J = 8.9, 4.3 Hz), 3.94 (d, 1 H, J = 4. 3 Hz), 4.43 (m, 2H), 4.54 (d, 1 H, J = 8.9 Hz), 4.64 (d, 1 H, J = 12. 0 Hz, PhCH2-), 4.84 (d, 1H, J = 12.0 Hz, PhCH2-), 4.95 (s, 1H), 5.66 (m, 1H), 6.24 (d, 1H, J = 10.3 Hz), 7.29-7. 39 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCl3) 8 ppm: 55.8, 68.6, 71.3, 72.0, 78.3, 79.6, 109.3, 126.6, 127.5, 127.6, 127.7, 128.3, 137.7.

HRMS (FAB). Calculated for C15H18O4(M+) 262.1205. Found 262.1202.

Step 8 : The preparation of: To a solution of the product from Step 7 (0.070g, 0. 298mmol) in THF-water (1: 1) is added N-bromosuccinimide (0. 10g, 0. 562mmol) at room temperature. The mixture is stirred vigorously for 2 hours, and then poured into water (20moi) containing sodium thiosulphate (0.5g) and extracted with ethyl acetate (20ml x3). The combined organic layers are dried over anhydrous sodium sulphate, filtered and concentrated, and the crude residue used in Step 9 without further purification.

Step 9: The preparation of: To a solution of the crude product from Step 8 in THF (1 Oml) is added 1 N sodium hydroxide (5ml) and then refluxed for 1 hour. The mixture is poured into water (20moi) and then extracted with ethyl acetate (20ml x3). The combined organic layers are washed with brine, dried over anhydrous sodium sulphate, filtered and concentrated. The crude residue is used in Step 10 without further purification.

Step 10: The preparation of: The product from Step 9 is dissolved in 2-methoxyethanol (15ml) and sodium azide (0.36g) is added. The mixture is heated to +126°C for 2 hours. The mixture is poured into saturated brine (50mut) and extracted with ethyl acetate (20mix3). The combined organic layers are dried over anhydrous sodium sulphate, filtered and concentrated. The residue is purified by flash silica chromatography (hexanes: ethyl acetate, 4: 1) to afford the desired product (0.05g, 0.16mmol) as white powder, yield: 52.6%, m.p. 120-122°C.

[α]D20=-3.05 (c = 1.8, CHCl3).

IR (KBr) 3067,2911, 2101,1454, 1124,1061, 1022,903 cm-'.

1H-NMR (400 MHz, CDCI3) 8 ppm: 2.3 (d, 1 H, J = 6.9 Hz, -OH), 3.39 (s, 3H, O CH3), 3.70 (m, 1 H, H-6), 3.77-3. 90 (m, 3H, H-5 and H-8), 3.96 (d, 1 H, J = 4.3 Hz, H-3), 4.29 (m, 1 H, H-7), 4.46 (dd, 1H, J = 10.3, 3.2 Hz, H-9), 4.65 (d, 1H, J = 12.0 Hz, PhCH2-), 4.79 (d, 1H, J = 12.0 Hz, PhCH2-), 4.90 (s, 1 H, H-2), 7.3-7. 39 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCI3) 8 ppm : 56.2, 61.4, 69.0, 70.3, 72.7, 74.7, 74.8, 91.1, 107.6, 128.2, 128.4, 128.9, 137.9.

HRMS (FAB). Calculated for C15HrgN304 (M+) 321.1325. Found 321.1323.

Step 11: The preparation of: To a solution of the product from Step 10 (0.040g, 0. 1246mol) in dry DCM (10ml) is added 1,1, 1-tris (acetyloxy)-1, 1-dihydro-1, 2-benziodoxol-3-(1 H)-one (Dess-Martin periodinane, 0. 16g) at room temperature under argon, and then the mixture is stirred for 2.5 hours. After the starting material has disappeared, saturated sodium bicarbonate solution (5ml) and saturated sodium thiosulphate solution (5ml) are added. The mixture is stirred for 10 minutes, extracted with DCM, dried over anhydrous sodium sulphate, filtered and concentrated. The crude product is used in Step 12 without further purification.

Step 12: The preparation of: To a solution of the crude product from Step 11 in methanol (5ml) is added NaBH4 (0.040g) at 0°C. The resulting mixture is stirred for 1 hour, and concentrated. The residue is extracted with ethyl acetate (20moi x 3). The combined organic layers are dried over anhydrous sodium sulphate, filtered and concentrated to afford the desired product as an oil, which is used in Step 13 without further purification.

Step 13: The preparation of: To a solution of the crude product from Step 12 in dry DMF (5ml) is added sodium hydride (60% suspension in oil, 0. 010g, 0. 25mol). After stirring for 30 minutes at 0°C under argon, methyl iodide (0.020g) is added, and the mixture is stirred for 3 hours. The reaction is quenched by adding water (1 Oml), and the mixture is extracted with ethyl acetate (20ml x 3).

The combined organic layers are washed with saturated brine, dried over anhydrous sodium sulphate, filtered and concentrated. The residue is purified by flash silica chromatography (hexanes: ethyl acetate, 10: 1) to afford the desired product (0.035g. 0. 11 mmol) as colourless oil, yield : 83.8%.

Me =-11.6 (c = 2.4, CHC13).

IR (neat) 2989,2101, 1125,1062 cm-'.

1H-NMR (400 MHz, CDCI3) 8 ppm: 3.39 (s, 3H, O CH3), 3.45 (s, 3H,-O CH3), 3.51 (dd, 1 H, J = 2.7, 1.1 Hz, H-6), 3.73 (t, 1 H, J = 10.4 Hz, H-5), 3.9-4. 0 (m, 3H, H-3, H-5 and H-8), 4.08 (dd, 1 H, J = 9.8, 2.6 Hz, H-9), 4.58 (t, 1 H, J = 2.8 Hz, H-7), 4.62 (d, 1 H, J = 12. 0, PhCH2-), 4.76 (d, 1 H, J = 12.0 Hz, PhCH2-), 4.92 (s, 1 H, H-2), 7.2-7. 4 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCI3) 8 ppm: 55.6, 57.3, 59.2, 66.0, 72.1, 74.2, 75.9, 78.9, 108.6, 127.6, 127.7, 128.3, 137.5.

HRMS (FAB). Calculated for C16H21N305 (M+) 335.1481. Found: 335.1481.

Step 14: The preparation of: To a solution of the product from Step 13 (0.20g, 0. 6mmol) in CH3CN-CCI4-H2O (1: 1: 1.5, 8ml) is added ruthenium trichloride trihydrate (0.0284g, 0. 12mol), and then sodium periodate (0. 153g, 0.71 mmol) at +16°C under argon. The mixture is stirred for 24 hours at this temperature and further sodium periodate (0.392g) is added in portions. After the starting material has disappeared, excess isopropyl alcohol (5ml) and water (20mi) are added. The mixture is extracted with DCM (30ml x 3), dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) afforded the desired product (0. 165g, 0. 47mmol) as white solid, yield : 79.2%.

[α]D20= +2.36 (c = 0.57, CHC13).

IR (neat, cm-1): X 2929, 2108,1726, 1583,1439, 1268, 1108.

'H-NMR (400 MHz, CDCI3) 8 ppm: 3.44 (s, 3H,-O CH3) ; 3.48 (s, 3H,-O CH3) ; 3.50 (m, 1H, H-6); 3.60 (dd, 1 H, J = 11.1, 10.5 Hz, H-5); 3.94 (dd, 1 H, J = 11.1, 5.0 Hz, H-5); 4.05 (dd, 1H, J = 10.0, 2.7 Hz, H-9); 4.17 (dd, 1H, J = 10.0, 4.3 Hz, H-8); 4.61 (t, 1H, J = 2.7 Hz, H-7); 5.08 (s, 1 H, H-2); 5.37 (d, 1 H, J = 4.3 Hz, H-3); 7.42-8. 05 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCI3) 8 ppm: 55.9, 57.4, 59.1, 66.1, 72.4, 73.9, 75.5, 76.2, 108.3, 128.3, 129.1, 129.7, 133.3, 165.1.

FAB-MS m/z (relative intensity): 350 (M++ H, 32), 318 (M+-OMe, 30).

HR-MS (FAB). Calculated for C16H20N306 (M + H+) 350.1352. Found: 350.1358.

Step 15: The preparation of: To a solution of the product of Step 14 (0.165g, 0. 47mmol) in dry DCM (10mi) is added benzenethiol (0. 15ml, 1. 42mol), and then boron trifluoride etherate (0. 1 ml, 0. 79mmol) at -78°C under argon. After stirring for 3.5 hours at this temperature, the mixture is quenched by adding saturated sodium bicarbonate (10ml), warmed to room temperature and extracted with DCM (20moi x 3). The combined organic layers are washed with brine, dried over anhydrous sodium sulphate, filtered and concentrated. The residue is purified by flash silica chromatography (hexanes: ethyl acetate, 5: 1) to afford the desired product (0.245g, 0. 46mmol) as colourless oil, yield : 96.6%.

[a] D20 = +20.6 (c = 0.33, CHCI3).

IR (neat, cm~1) : 2926,2104, 1728,1602, 1452,1272, 1112.

1H-NMR (400 MHz, CDCI3) 6 ppm: 2.56 (d, 1H, J = 8.6 Hz, -OH) ; 3.47 (s, 3H,-O CH3) ; 3.50 (m, 1 H, H-5); 3.53 (dd, 1 H J = 11.2, 9.5 Hz, H-6); 3.60 (m, 1 H, H-2); 3.75 (m, 1 H, H-6); 4.08 (m, 2H, H-3 and H-4); 4.96 (d, 1 H, J = 3.4 Hz, H-2'); 5.63 (dd, 1 H, J = 3.4, 2., 5 Hz, H-1'), 7.30-8. 10 (m, 15H, Ph-).

3C-NMR (100 MHz, CDCI3) 8 ppm: 57.1, 60.3, 61.1, 62.2, 63.1, 68.8, 74.5, 76.6, 127.7, 128.1, 128.3, 128.9, 129.0, 129.4, 129.9, 132.3, 133.2, 133.4, 133.5, 134.4, 165.9.

FAB-MS m/z (relative intensity): 537 (M+, 2), 428 (M+-PhS, 15).

Step 16: The preparation of: To a solution of the product from Step 15 (0.245g, 0. 46mmol) in methanol (20ml) is added potassium carbonate (0. 01 Og) at room temperature. After stirring for 30 minutes, the mixture is evaporated under reduced pressure, and the residue is purified by flash silica chromatography (hexanes: ethyl acetate, 2: 1) to afford the desired product (0.184g, 0. 43mmol) as colourless oil, yield : 93.2%. <BR> <BR> <BR> <P> 20<BR> [«] D20 = + 28.3 (c = 0.79, CHC13).

1H-NMR (400 MHz, CDCI3) 8 ppm: 3.22 (t, 1 H, J = 10. 6 Hz, H-6), 3.35 (ddd, 1 H, J = 10.6, 4.8, 3.0 Hz, H-5), 3.40 (s, 3H,-O CH3), 3.63 (ddd, 1 H, J = 10.6, 4.8, 1.1 Hz, H-6), 3.69 (dd, 1 H, J = 9. 1,3. 2 Hz, H-3), 3.76 (t, 1 H, J = 9. 1 Hz, H-2), 3.90 (dd, 1 H, J = 8. 2,2. 2 Hz, H-1'), 4.26 (t, 1 H, J = 2.2 Hz, H-4), 4.87 (d, 1 H, J = 2.2 Hz, H-2'), 7.26-7. 50 (m, 1 OH,-Ph).

13C-NMR (100 MHz, CDCI3) 8 ppm: 56.9, 62.4, 63.2, 71.9, 72.7, 75.6, 76.0, 127.9, 128.0, 128.9, 129.1, 132.3.

FAB-MS m/z (relative intensity): 433 (M+, 25), 324 (M+-PhS, 80).

HR-MS (FAB). Calculated for C2oH23N304S2 (M+) 433. 1130. Found: 433. 1132.

Step 17: The preparation of: To a solution of the product from Step 16 (0.184g, 0. 43mmol) in dry DCM (20ml) is added N- bromosuccinimide (0.080g, 0. 45mmol) cooled in an ice-bath under argon. After stirring for 20 minutes, the mixture is quenched by adding saturated sodium thiosulphate, and then stirred for 10 minutes. The mixture is extracted with DCM (30mi x 4), the combined organic layers are washed with brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexane: ethyl acetate, 3: 1) affords the desired product (0.104g, 0. 32mmol) as colourless oil, yield : 76.2%.

H-NMR (400 MHz, CDCI3) 8 ppm: 2.50 (d, 1H, J = 2.2 Hz, -OH), 3.48 (s, 3H,-O CH3), 3.58 (ddd, 1 H, J = 10. 4,5. 1,3. 0 Hz, H-6), 3.69 (dd, 1 H, J = 11. 0,10. 6 Hz, H-5), 3.80 (dd, 1 H, J = 9.8, 4. 8 Hz, H-8), 4.0 (dd, 1 H, J = 11.0, 5.1 Hz, H-5), 4.06 (dd, 1 H, J = 9.8, 2.8 Hz, H-9), 4.55 (dd, 1 H, J = 6.1, 4.1 Hz, H-3), 4.64 (dd, 1 H, J = 3.0, 2.8 Hz, H-7), 5.80 (d, 1 H, J = 4.1 Hz, H-2), 7.26-7. 53 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCI3) 8 ppm: 57.4, 58.8, 65.6, 69.5, 73.9, 74.1, 76.2, 93.8, 127.1, 128.9, 130.9, 134.4.

FAB-MS m/z (relative intensity): 323 (M+, 20).

HRMS (FAB). Calculated for C14H18N304S (M++1) 324.1018. Found 324.1008.

Step 18: The preparation of: To a solution of the product from Step 17 (0.104g, 0. 32mmol) in dry pyridine (5ml) is added 4-dimethylaminopyridine (DMAP, 0.20g), and then pivaloyl chloride (0. 15ml) at room temperature under argon. The mixture is stirred overnight, and pyridine is removed under reduced pressure. The residue is dissolved with DCM (50ml) and washed with saturated sodium bicarbonate, brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexane: ethyl acetate, 5: 1) affords the desired product (0.130g, 0. 32mmol) as colourless oil, yield : 100%.

[a] D 20 =+187. 3 (c = 0.41, CHCI3).

IR (neat, cm-1) : 2977,2107, 1741,1480, 1279,1146, 1059.

1H-NMR (400 MHz, Ceci3) 8 ppm: 1.30 (s, 9H,-OCOC (CH3) 3); 3.47 (s, 3H,-O CH3) ; 3.51 (m, 1H, H-6); 3.61 (dd, 1H, J=11. 6,10. 0, H-5); 3.84 (dd, 1 H, J = 10.0, 3.4 Hz, H-8); 3.92 (dd, 1 H, J = 11. 6,4. 4 Hz, H-5); 3.97 (dd, 1 H, J = 10. 0,3. 4 Hz, H-9); 4.62 (t, 1 H, J = 3. 2 Hz, H-7); 5.68 (t, 1 H, J = 3.4 Hz, H-2); 7.27-7. 51 (m, 5H, Ph-).

3C-NMR (100 MHz, CDCI3) 8 ppm: 27.6, 39.8, 57.9, 59.2, 66.0, 70.4, 73.9, 75.3, 76.8, 92.3, 127.8, 129.5, 131.6, 134.8, 177.1.

FAB-MS m/z (relative intensity): 408 (M++ H, 60), 407 (M+, 15), 298 (M+-PhS, 100).

HR-MS (FAB). Calculated for CigH26N305S (M + H+) 408.1601. Found: 408.1586.

Step 19: The preparation of: To a solution of the product of Step 18 (0.040g, 0. 1mmol) in dry DCM (2ml) is added bis-O- trimethylsilyluracil (0.040g, 0. 16mol), N-iodosuccinimide (0.045g, 0. 2mmol) and then triflic acid (10µl, 0.1 mmol) at room temperature under argon. After stirring for 2 hours, the reaction is quenched by adding saturated sodium thiosulphate (1 Oml). The mixture is extracted with DCM (30moi x 3), and the combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (DCM: methanol, 40: 1) affords the desired N-nucleoside (0. 016g, 0. 039mmol) along with the iodo-N-nucleoside (0.025g, 0. 046mmol), with a combined yield of 85%.

N-Nucleoside : [a] D20 = +85. 5 (c = 0.6, CHCI3).

IR (neat, cm-1) : 2932,2109, 1693,1459, 1277,1149, 1059.

'H-NMR (400 MHz, CDCI3) 8 ppm : 1.23 (s, 9H,-OCOC (CH3) 3), 3.49 (s, 3H,-O CH3), 3.58 (m, 1 H, H-6), 3.66 (dd, 1 H, J = 11.0, 10.7 Hz, H-5), 3.79 (dd, 1 H, J = 10.1, 2.7 Hz, H-9), 3.84 (dd, 1H, J = 10.1, 5.0 Hz, H-8), 3.99 (dd, 1H, J = 11.0, 5.1 Hz, H-5), 4.68 (brs, 1H, H-7), 5.28 (d, 1 H, J = 5.0 Hz, H-3), 5.81 (d, 1 H, J = 8.1 Hz, H-5'), 5.91 (s, 1 H, H-2), 7.58 (d, 1 H, J = 8.1 Hz, H-6'), 8.42 (brs, 1 H,-NH). t3C-NMR (100 MHz, CDCl3) 8 ppm: 27.5, 39.3, 58.1, 59.3, 66.4, 72.4, 73.0, 76.2, 77.1, 91.2, 103.4, 139.7, 149.9, 163.0, 177.0.

FAB-MS m/z (relative intensity): 410 (M+ H+, 20), 298 (M+-PhS, 35). lodonucleoside : [a] D = +76. 6 (c = 0.95, CHCl3).

IR (neat, cm-1) : 2977, 2110, 1693,1609, 1439,1275, 1138.

'H-NMR (400 MHz, CDCI3, ppm): 5 1.24 (s, 9H,-OCOC (CH3) 3), 3.50 (s, 3H,-O CH3), 3.59 (ddd, 1H, J = 10. 7,5. 0,3. 0 Hz, H-6), 3.68 (dd, 1H, J = 11. 1,10. 7, H-5), 3.86 (m, 2H, H-8 and H-9), 3.99 (dd, 1 H, J = 11.1, 5.0 Hz, H-5), 4.72 (brs, 1 H, H-7), 5.32 (d, 1 H, J = 4.1 Hz, H-3), 5.86 (s, 1 H, H-2), 8.24 (s, 1 H, H-6'), 8.76 (brs, 1 H,-NH). t3C-NMR (100 MHz, Ceci3) 8 ppm: 27.5, 39.3, 58.1, 59.4, 60.8, 66.5, 68.7, 72.2, 72.9, 76.6, 91.2, 144. 7, 149. 6, 159. 9, 176. 8 FAB-MS m/z (relative intensity): 536 (M + H+, 5), 298 (M+-PhS-I, 15).

HRMS (FAB). Calculated for C17H23N5O71 (M+) 536.0642. Found 536.0664.

Step 20: The preparation of To a solution of the N-nucleoside product from Step 19 (0. 008g, 0. 02mmol) in anhydrous THF (2ml) is added trimethylphosphine (1 M in toluene) (50µl, 0.05mmol) at room temperature under argon. After stirring for 30 minutes, water (3go) is added, and the mixture refluxed for 40 minutes, and then evaporated. The residue is dried under reduced pressure (1 mm Hg) for 1.5 hours to give the desired crude product, which is used for Step 21 without further purification.

Step 21: The preparation of: The crude product from Step 20 is dissolved in dry DCM (2ml), and to this solution is added trichloroacetyl isocyanate (10µl) at room temperature under argon. After stirring for 60 minutes, DCM is removed and the crude product is used for Step 22 without further purification.

Step 22: The preparation of: The crude product from Step 21 is dissolved in methanol (2ml) and 40% methylamine in water (2ml), and is stirred over 3 days. The mixture is evaporated and purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound (0.0034g, 0.01 mmol) as white solid, yield : 50%.

[α]D20=+27. 5 (c = 0.08, CH30H). tH-NMR (400 MHz, CD30D) 8 ppm: 3.37 (s, 3H,-O CH3), 3.46 (dd, 1 H, J = 11.9, 11.0 Hz, H- 5), 3.54 (m, 1 H, H-6), 3. 67 (dd, 1 H, J = 11.0, 5.4 Hz, H-5), 3.97 (dd, 1 H, J = 11.4, 5.4 Hz, H- 8), 4.01 (dd, 1 H, J = 11.4, 5.4 Hz, H-9), 4.25 (d, 1 H, J = 5. 4 Hz, H-3), 4.95 (m, 1 H, H-7), 5.66 (d, 1 H, J = 8.3 Hz, H-5'), 5.68 (s, 1 H, H-2), 7.67 (d, 1 H, J = 8.3 Hz, H-6').

13C-NMR (100 MHz, CD30D, ppm): 8 48.3, 55.2, 66.0, 72.3, 73.8, 74.2, 77.6, 94.1, 101.2, 10.8, 150.9, 161.3, 164.8.

HRMS (FAB). Calculated for C13Hl8N407Na (M + Na+) 365.1073. Found: 165.1064.

EXAMPLE 2 This Example illustrates the preparation of Compound No. 5 of Table 1 Step 1: The preparation of: To a solution of the product of Example 1, Step 18, (0.0182g, 0. 045mmol), bis-trimethylsilyl- thymine (0.0241 g, 0. 089mmol) and N-iodosuccinimide (0.0201 g, 0. 089mmol) in dry DCM (2ml), is added triflic acid (6, 1) over several minutes. After stirring for 3 hours, the mixture is quenched by adding saturated sodium thiosulphate, extracted with DCM, washed with saturated sodium bicarbonate, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (DCM: methanol, 20: 1) affords the desired compound (0. 0165g, 0. 039mmol) as colourless oil, yield : 86%.

[α]D20=+80. 8 (c = 0.7, CHC13).

IR (neat, cm~1) : 2930,2109, 1711, 1463,1278, 1151.

1H-NMR (400 MHz, CDCI3) 8 ppm : 1.23 (s, (H,-OCOC (CH3) 3); 1.95 (s, 3H,-CH3) ; 3.49 (s, 3H,-O CH3) ; 3.56 (m, 1H, H-6); 3.66 (dd, 1H, J = 10.1, 2.4 Hz, H-9); 3.77 (dd, 1H, J = 10.1, 2.6 Hz, H-8); 3.92 (m, 1 H, H-5); 3.96 (m, 1 H, H-5), 4.68 (d, 1 H, J = 2.4 Hz, H-7); 5.28 (d, 1 H, J = 2.6 Hz, H-3); 5.92 (s, 1 H, H-2); 7.37 (s, 1 H, H-6'); 8.8 (s, 1 H,-NH).

13C-NMR (100 MHz, CDCI3, ppm): 8 13. 1,27. 5,39. 3,58. 1,59. 4,66. 2,72. 5,73. 0,76. 2,76. 9, 93.0, 111. 9, 135. 5, 150. 0, 163. 8, 177. 9.

FAB-MS m/z (relative intensity): 424 (M + H+, 18), 408 (M+-Me, 10), 298 (M+-thymine, 35).

Step 2: The preparation of: To a solution of the product of Step 1 (0. 0160g, 0. 039mmol) in anhydrous THF (2ml) is added trimethylphosphine (1M in toluene) (150R1, 0. 15mmol) at room temperature under argon atmosphere. After stirring for 30 min, water (5111) is added to the mixture. The resulting mixture is refluxed for 40 minutes, and then evaporated. The residue is dried under reduced pressure (1 mmHg) for 1.5 hours, and used without further purification for Step 3: The preparation of: The crude product from Step 2 is dissolved in dry DCM (2ml) and to this solution is added trichloroacetyl isocyanate (10µl) at room temperature under argon. After stirring for 60 minutes, DCM is removed, and the crude product is used for Step 4 without further purification.

Step 4: The preparation of: The crude product from Step 3 is dissolved in methanol (2ml) and 40% methylamine in water (2ml), and stirred over 3 days. The mixture is evaporated and purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound (0. 0102g, 0. 029mol) as white solid, yield : 75.7%.

[a] D = +72. 0 (c = 0.125, CH30H).

'H-NMR (400 MHz, CD30D, ppm): 8 1. 90 (s, 3H,-CH3) ; 3.37 (s, 3H,-O CH3) ; 3.50 (m, 2H, H-5 and H-6); 3.69 (m, 1H, H-5); 3.95 (dd, 2H, J = 10.5, 5.4 Hz, H-8); 4.02 (dd, 1H, J = 10.5, 3.4 Hz, H-9); 4.21 (d, 1 H, J=5.4 Hz, H-3); 4.96 (m, 1 H, H-4); 5.68 (s, 1 H, H-2); 7.52 (s, 1 H, H-6').

13C-NMR (100 MHz, CD30D, ppm): 8 11.7, 48.6, 55.8, 66.6, 72.6, 73.7, 74.0, 76.9, 93.9, 106.0, 139.0, 151.2, 161.0, 163.0.

FAB-MS m/z (relative intensity): 379 (M + Na+, 40), 357 (M + H+, 100).

HRMS (FAB). Calculated for C14H21N407 (M + H+) 357.1410. Found 357.1418.

EXAMPLE 3 This Example illustrates the preparation of Compound No. 7 of Table 1 Step 1: The preparation of: To a solution of the product of Example 1, Step 18 (0.0152g, 0. 037mmol), bis-trimethylsilyl- N-4-acetyl-cytosine (0.027g, 0. 089mmol) and N-iodosuccinimide (0.020g, 0. 089mmol) in dry DCM (2ml), is added triflic acid (6go) over several minutes. After stirring for 5 hours, the mixture is quenched by adding saturated sodium thiosulphate, extracted with DCM, washed with saturated sodium bicarbonate, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (DCM: methanol, 10: 1) affords the desired product (0.012g, 0. 027mol) as colourless oil, yield : 71.4%.

[a] D 20 =+98. 8 (c = 0.8, CHC13).

IR (neat, cm-1) : 2934, 2110, 1712,1666, 1562,1493, 1385,1277, 1151.

'H-NMR (400 MHz, CDCl3) S ppm : 1.21 (s, (H, -OCOC (CH3) 3); 2.25 (s, 3H,-CO CH3) ; 3.46 (s, 3H,-O CH3) ; 3.56 (m, 1 H, H-6); 3.58 (t, 1 H, J = 10.6 Hz, H-5); 3.77 (dd, 1 H, J = 10.0, 4.5 Hz, H-8); 3.87 (dd, 1H, J = 10.0, 2.8 Hz, H-5); 3.95 (dd, 1H, J = 10.6, 4.3 Hz, H-5), 4.70 (s, 1H, H-7); 5.32 (d, 1H, J = 4.5 Hz, H-3); 5.99 (s, 1H, H-2); 7.48 (d, 1H, J = 7.5 Hz, H-5'); 8.15 (d, 1H, J = 7.5 Hz, H-6'); 10.1 (brs, 1H,-NH).

13C-NMR (100 MHz, CDCI3) 8 ppm: 26.9, 29.4, 38.7, 57.6, 58.8, 65.8, 71.6, 72.3, 75.9, 76.6, 91.1, 96.8, 143.8, 154.3, 162.9, 170.9, 178.2.

LC-MS m/z (relative intensity): 350 (M+, 100).

Step 2 : The preparation of: To a solution of the product of Step 1 (0.012g, 0. 027mmol) in anhydrous THF (2ml) is added trimethylphosphine (1 M in toluene) (50, u1, 0. 05mmol) at room temperature under argon atmosphere. After stirring for 30 minutes, water (5ll1) is added to the mixture. The resulting mixture is refluxed for 40 minutes, and then evaporated to give the crude desired product, which is dried under reduced pressure (1 mmHg) for 1.5 hours and then used in Step 3 without further purification.

Step 3 : The preparation of: The crude product from Step 2 is dissolved in dry DCM (2ml). To this solution is added trichloroacetyl isocyanate (20gel) at room temperature under argon atmosphere. After stirring for 60 minutes, DCM is removed and the crude product is used in Step 4 without further purification.

Step 4: The preparation of: The crude product from Step 3 is dissolved in methanol (2ml) and 40% methylamine in water (2ml), and stirred over 3 days. The mixture is evaporated and purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound (0.0045g, 0. 013mmol) as white powder, yield : 50%.

[a] D 20 = +91. 7 (c = 0.06, CH30H).

'H-NMR (400 MHz, CD30D) 8 ppm: 3.35 (m, 1H, H-6), 3.37 (s, 3H,-O CH3), 3.50 (m, 2H, H- 5 annd H-7), 3.66 (dd, 1 H, J = 10.6, 5.3 Hz, H-9), 3.96 (dd, 1 H, J = 11.6, 5.4 Hz, H-5), 4.05 (dd, 1H, J = 10.6, 2.3 Hz, H-8), 4.19 (d, 1H, J = 4.3 Hz, H-3), 4.97 (m, 1H, H-7), 5.67 (s, 1H, H-2), 5.87 (d, 1H, J=7. 5Hz, H-5'), 7.73 (d, 1H, J=7.5 Hz, H-6').

3C-NMR (100 MHz, CD30D) 8 ppm: 48.8, 55.8, 66.6, 72.6, 73.5, 74.1, 76.9, 94.7, 94.8, 140.7, 156.9, 161.3, 166.7.

FAB-MS m/z (relative intensity): 364 (M + Na+, 35), 342 (M + H+, 18), 325 (M+-NH2, 8).

EXAMPLE 4 This Example illustrates the preparation of Compound No. 2 of Table 1 Step 1: The preparation of: To a solution of the product of Example 1, Step 10, (0.60g, 1. 9mmol) in dry DMF (30moi) is added sodium hydride (60% dispersion in mineral oil) (0.20g, 5. 0mmol), and methyl iodide (0. 5ml, 8. Ommol) at 0°C under argon. After stirring overnight, the reaction is quenched by adding saturated sodium bicarbonate and extracted with ethyl actetate (30ml x 4). The combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords the desired product as colourless oil (0.60g, 1. 8mmol), yield : 96%.

[a] D20=-16. 0 (c = 1.36, CHCI3).

IR (neat, cm-1) : 2960,2098, 1490.

'H-NMR (400 MHz, CDCI3, ppm): 8 3.22 (m, 1 H, H-6); 3.38 (s, 3H,-O CH3) ; 3.41 (s, 3H,-O CH3) ; 3.64 (d, 1H, J = 12.8 Hz, H-5); 3.86 (dd, 1H, J = 10. 0,4. 2 Hz, H-8); 3.95 (d, 1H, J = 4. 2 Hz, H-2); 4.03 (d, 1H, J=12.8 Hz, H-5); 4.40 (d, 1H, J = 3.0 Hz, H-7); 4.45 (dd, 1H, J= 10.0, 3.1 Hz, H-9); 4.62 (d, 1H, J = 12.2 Hz, PhCH2-) ; 4.84 (d, 1H, J = 12.2 Hz, PhCH2-); 4.86 (s, 1 H, H-2); 7.26-7. 38 (m, 5H, Ph-).

13C-NMR (100 MHz, CDCI3, ppm): # 56. 1,57. 7,59. 3,66. 9,72. 7,74. 8,75. 1,77. 8,79. 8, 128.1, 128.2, 128.8, 138.4.

FAB-MS m/z (relative intensity): 335 (M+, 15), 275,184 (100).

HRMS (FAB). Calculated for C16H21N305 (M+), 335.1481, found: 335.1481.

Step 2: The preparation of: To a solution of the product of Step 1 (0.590g, 1. 84mmol) in CCI4-MeCN-H2O (25ml, 1: 1: 1.5) is added ruthenium trichloride trihydrate (0.087. 5g, 0. 35mmol) and sodium periodate (0.464g, 2. 2mmol) at +16 °C under argon, and then further sodium periodate (1.2g) is added in portions over 24 hours. After stirring over 24 hours, the reaction is quenched by adding isopropanol (3ml). The mixture is extracted with DCM (50moi x 3) and the combined organic layers are washed with saturated sodium bicarbonate and brine, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords the desired product (0.50g, 1. 43mmol), yield : 82%.

[a] D=+0. 78 (c = 1. 15, CHCl3).

IR (neat, cm-') : 2916,2103, 1727,1452, 1269, 1199, 1115.

'H-NMR (400 MHz, CDCI3) 8 ppm: 3.22 (m. 1 H, H-6); 3.36 (s, 3H,-O CH3) ; 3.47 (s, 3H,-O CH3) ; 3.65 (d, 1H, J = 12.9 Hz, H-5); 4.0 (d, 1H, J = 12.9 Hz, H-5); 4.03 (dd, 1H, J = 10.0, 4.4 Hz, H-8); 4.40 (m, 2H, H-7 and H-9); 5.03 (s, 1 H, H-2); 5.40 (d, 1 H, J = 4.4 Hz, H-3), 7.42 -8. 05 (m, 5H, Ph-).

3C-NMR (100 MHz, CDCI3) 8 ppm: 56.4, 57.7, 59.5, 66.7, 72.6, 75.0, 75.5, 77.9, 107.6, 128.8, 129.6, 130.4, 133.7, 170.0.

FAB-MS m/z (relative intensity): 349 (M+, 10) Step 3: The preparation of: To a solution of the product from Step 2 (0.39g, 1. 1 mmol) in dry DCM (10mi) is added benzenethiol (0.49g, 4. 5mmol), and then boron trifluoride etherate (0. 17ml, 1. 34mmol) at -78°C under argon. The mixture is stirred for 3 hours and then warmed to 0°C. The reaction is quenched by adding saturated sodium bicarbonate. The mixture is extracted with DCM (30ml x 3), and the combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 5: 1) affords the desired product (0.473g, 0. 88mmol) as colourless oil, yield : 80%.

[a] D 20 =+41. 0 (c = 0.56, CHC13).

IR (neat, cm~1) : # 2918,2109, 1723,1439, 1268.

'H-NMR (400 MHz, CDCI3) 8 ppm: 2.54 (d, 1 H. J = 5. 6 Hz, -OH) ; 3.35 (s, 3H,-O CH3) ; 3.40 (m, 1H, H-5); 3.49 (dd, 1H, J = 12.5, 3.5 Hz, H-6), 3.56 (dd, 1H, J = 12.5, 2.4 Hz, H-6); 3.94 (t, 1 H, J = 4.2 Hz, H-4); 4.07 (m, 1 H, H-3); 4.18 (t, 1 H, J = 7.6 Hz, H-7), 4.95 (d, 1 H, J = 2.5 Hz, H-2'); 5.73 (dd, 1 H, J = 7.6, 2.5 Hz, H-1') ; 7.25-8. 08 (m, 15H, Ph-).

3C-NMR (100 MHz, Ceci3, ppm): 6 57. 1,61. 5,62. 3,63. 6,67. 9,74. 6,74. 7,76. 7,127. 7, 128.3, 128.33, 128.9, 129.0, 129.3, 130.1, 132.3, 133.3, 133.7, 134.5, 166.2.

FAB-MS m/z (relative intensity): 537 (M+, 3), 428 (M+-PhS, 16).

HRMS (FAB). Calculated for C27H28N305S2 (M + H+) 538.1470. Found 538.1453.

Step 4: The preparation of: To a solution of the product from Step 3 (0.42g, 0. 78mmol) in methanol (1 Oml) is added anhydrous potassium carbonate (0.005g) at room temperature and the mixture is stirred for 30 minutes. The mixture is evaporated under vacuum and the residue is purified by flash silica chromatography (hexanes: ethyl acetate, 3: 1) to afford the desired product as colourless oil (0.335g, 0. 77mmol), which is used in Step 5 without further purification.

Step 5: The preparation of: To a solution of the product of Step 4 in dry DCM (1 Oml) is added N-bromosuccinimide (0.205g, 1. 16mmol) at room temperature under argon. After stirring for 30 minutes, the reaction is quenched by adding saturated sodium thiosulphate (1 Oml), and the mixture is extracted with DCM (20ml x 3). The combined organic layers are washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 10: 1) affords the desired product (0. 19g, 0. 59mmol) as colourless oil, yield: 77%.

[α] o2° = +150. 5 (c = 0.54, CHCI3).

IR (neat, cm-1) : 3402,2918, 2103,1584, 1482,1069.

1H-NMR (400 MHz, CDCI3) 8 ppm: 2.59 (d, 1 H, J = 2.0 Hz, -OH) ; 3.31 (dd, 1 H, J = 2.4, 1.3 Hz, H-6); 3.73 (m, 1H, H-7); 3.78 (dd, 1H, J = 12.9, 1.6 Hz, H-5); 4.06 (d, 1H, J = 12.9 Hz, H- 5); 4.46 (m, 2H, H-8 and H-9), 4.58 (m, 1 H, H-3); 5.77 (d, 1H, J=4. 0 Hz, H-2).

13C-NMR (100 MHz, CDCI3) 8 ppm: 57.6, 58.7, 66.7, 70.6, 70.61, 73.4, 74.7, 92.8, 127.3, 129.4, 130,8, 132.5.

FAB-MS m/z (relative intensity): 323 (M+, 25).

HRMS (FAB). Calculated for C14H18N304S (M+ H+) 324.1018. Found 324.1012.

Step 6: The preparation of: To a solution of the product of Step 5 (0.17g, 0. 53mmol) in dry pyridine (5ml) is added DMAP (0.20g), and then pivaloyl chloride (0. 2ml) at room temperature under argon. The mixture is stirred overnight, and pyridine is removed under reduced pressure. The residue is dissolved in DCM (50mi) and washed with saturated sodium bicarbonate, and brine, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (hexanes: ethyl acetate, 5: 1) affords the desired product (0.214g, 0. 53mmol) as colourless oil, yield : 100%.

[a] D20 = +149. 6 (c = 0.51, CHCI3).

IR (neat, cm'') : 2977,2931, 2104,1742, 1480,1146.

'H-NMR (400 MHz, CDCI3) 8 ppm : 1.30 (s, 9H, -OCOC (CH3) 3); 3.28 (m. 1 H, H-6); 3.37 (s, 3H,-O CH3) ; 3.63 (d, 1 H, J = 12.0 Hz, H-5), 3.73 (d. 1 H, J =10. 0,4. 3 Hz, H-8); 3.98 (d, 1 H, J = 12.0 Hz, H-5); 4.42 (m, 2H, H-7 and H-9); 5.69 (t, 1 H, J = 4.3 Hz, H-3); 5.82 (d. 1 H, J = 4.3 Hz, H-2), 7.24-7. 51 (m, 5H, Ph-).

13 C-NMR (100 MHz, CDCl3) 6 ppm: 26.9, 39.2, 56.6, 58.5, 65.0, 70.5, 73.5, 73.6, 76.9, 89.9, 126.9, 128.9, 130.5, 134.8, 176.8.

FAB-MS m/z: 408 (M + H+, 20), 298 (M+-PhS, 100).

HRMS (FAB). Calculated for C19H26N305S (M+ H+) 408.1593. Found 408.1601.

Step 7 ; The preparation of: To a solution of the product from Step 6 (0. 041 g, 0. 1 mmol), bis-trimethylsilyl-uracil (0.040g, 0. 16mmol) and N-iodosuccinimide (0.045g, 0. 2mmol) in dry DCM (4ml) is added triflic acid (10111) over several minutes. After stirring for 5 hours, the mixture is quenched by adding saturated sodium thiosulphate, and extracted with DCM (30ml x 3). The combined organic layers are washed with saturated sodium bicarbonate, dried over anhydrous sodium sulphate, filtered and concentrated. Purification by flash silica chromatography (DCM: methanol, 10: 1) affords the desired N-nucleoside product (0.020g) and iodo-N- nucleoside (0.008g) as colourless oils, the combined yield is 80% based on recovered starting material (0. 010g).

N-Nucleoside : [a] D = +114. 5 (c = 1.6, CHCI3).

IR (neat, cm"') : 2971,2106, 1695,1458, 1147.

1H-NMR (400 MHz, CDCl3) S ppm : 1.25 (s, 9H, -OCOC (CH3) 3); 3.39 (m, 1 H, H-6); 3.40 (s, 3H, -O CH3) ; 3.68 (d, 1H, J = 13.4 Hz, H-5); 3.80 (dd, 1H, J = 9.8, 5.1 Hz, H-9); 4.08 (d, 1H, J = 13.4 Hz, H-5); 4.21 (dd, 1 H, J = 9.8, 3.0 Hz, H-8); 4.45 (m, 1 H, H-7); 5.30 (d, 1 H, J = 3.0 Hz, H-3); 5.79 (d, 1H, J = 8. 1HZ, H-5'); 5.85 (s, 1H, H-1); 7.44 (d, 1H, J =8.1 Hz, H-6'); 8.29 (s, 1H, -NH).

13C-NMR (100 MHz, CDCl3) 8 ppm: 26.9, 38.8, 56.8, 59.2, 65.2, 71.9, 73.0, 74.4, 76.6, 89.6, 102.9, 139.4, 149.4, 162.5, 176.9.

FAB-MS m/z (relative intensity): 410 (M + H+, 10), 391 (M+-H20, 16), 298 (M+-uracilyl, 16).

HRMS (FAB). Calculated for C17H24N507 (M+ H+) 410. 1675. Found 410. 1662. lodonucleoside : [a] D = +123. 4 (c = 0.87, CHCI3).

IR (neat, cm-1) : 2978,2104, 1691, 1611, 1136.

'H-NMR (400 MHz, CDCI3) 8 ppm : 1.25 (s, 9H, -OCOC (CH3) 3); 3.40 (s, 3H,-O CH3) ; 3.42 (m, 1 H, H-6); 3.72 (d, 1 H, J = 13.1 Hz, H-5); 3.79 (dd, 1 H, J = 10.1, 5.0 Hz, H-8); 4.08 (d, 1 H, J = 13. 1, H-5); 4.25 (dd, 1H,J=10. 1,2. 4 Hz, H-9); 4.47 (s, 1H, H-7); 5.36 (d, 1 H, J = 5. 0 Hz, H-3); 5.80 (s, 1 H, H-2); 8.03 (s, 1 H, H-6'); 8.59 (s, 1 H,-NH).

13C-NMR (100 MHz, CDCl3)# ppm: 27.5, 39.4, 57.4, 59.9, 65.8, 68.8, 72.2, 73.4, 75.4, 77. 3, 90.3, 144. 7, 149. 5, 159. 8, 177. 2.

FAB-MS m/z (relative intensity): 536 (M + H+, 10), 298 (M+-iodouracilyl, 26).

HRMS (FAB). Calculated for C17H23N5071 (M+) 536.0642. Found: 536.0664.

Step 8: The preparation of: To a solution of the N-nucleoside product of Step 7 (0.037g, 0. 09mmol) in anhydrous THF (4ml) is added trimethylphosphine (1 M in toluene) (250µl, 0. 25mmol) at room temperature under argon. After stirring for 30 minutes, water (10µl) is added to the mixture, which is refluxed for 40 minutes, and then evaporated. The residue is dried under reduced pressure (1 mmHg) for 1.5 hour to give the crude desired product which is used for Step 9 without further purification.

Step 9: The preparation of: The crude product from Step 8 is dissolved in dry DCM (2ml). To this solution is added trichloroacetyl isocyanate (20µl) at room temperature under argon. After stirring for 60 minutes, DCM is removed and the crude product is used for Step 10 without further purification.

Step 10: The preparation of: The crude product from Step 9 is dissolved in methanol (3ml) and 40% methylamine in water (3ml), and stirred over 3 days. The mixture is evaporated and purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound (0.025g, 0. 073mmol) as white solid, yield : 77%.

[a] D20=+30. 0 (c = 0.45, CH30H).

'H-NMR (400 MHz, CD30D) 8 ppm: 3.39 (m, 1 H, H-6'); 3.44 (s, 1 H,-O CH3) ; 3.59 (dd, 1 H, J = 10.7, 5.2 Hz, H-8); 3.79 (d, 1H, J = 13.2 Hz, H-5); 4.12 (d, 1H, J = 13.2 Hz, H-5); 4.22 (dd, 1H, J = 10. 7,4. 2 Hz, H-9); 4.31 (d, 1H, J= 5.2 Hz, H-3); 4.65 (m, 1H, H-7); 5.62 (s, 1H, H- 2); 5.70 (d, 1H, J=8. 1 Hz, H-5'); 7.62 (d, 1H, J=8. 1 Hz, H-6').

13C-NMR (100 MHz, CD30D) 8 ppm: 48.7, 56.4, 66.6, 72.6, 73.5, 74.1, 78.7, 93.8, 101.7, 141. 7, 150.9, 160.6, 165.2.

FAB-MS m/z (relative intensity): 343 (M + H+, 5) EXAMPLE 5 This Example illustrates the preparation of Compound No. 13 from Table 1 To a solution of compound 1 from Table 1 (0.003g) in dry pyridine (2ml) is added acetic anhydride (3RI) at room temperature under argon atmosphere. The mixture is stirred over night and then the pyridine removed under reduced pressure. The residue is purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound as a gum (0.0028g).

[a] D = +78. 0 (c = 0.1, CH30H) ; 1H-NMR (400 MHz, CD30D) 8 ppm: 2.12 (s, 3H,-CO CH3) ; 3.35 (m, 1H, H-7); 3.37 (s, 1H,-O CH3) ; 3.48 (t, 1 H, J = 11.6 Hz, H-5); 3.66 (m, 1 H, H-6); 3.83 (dd, 1 H, J = 10.6, 4.8 Hz, H-9); 3. 88 (dd, 1 H, J = 10. 6,2. 8 Hz, H-8); 3.94 (dd, 1H, J=11. 6,5. 4 Hz, H-5); 5.42 (d, 1 H, J = 4.8 Hz, H-3); 5.68 (d, 1 H, J = 8.02 Hz, H-5'); 5.72 (s, 1 H, H-2), 7.59 (d, 1 H. J = 8.02 Hz, H-6'); 3C-NMR (100 MHz, CD30D) 8 ppm : 19.5, 55.8, 66.7, 72.5, 73.1, 73.9, 77.2, 92.7, 101.6, 141.5, 150.6, 161.3, 165.0, 170.1.

EXAMPLE 6 This Example illustrates the preparation of compound No. 17 from table 1 To a solution of compound No. 2 from Table 1 (0. 003g) in dry pyridine (2 ml) is added acetic anhydride (3gel) at room temperature under argon atmosphere. The mixture is stirred overnight and then the pyridine removed under reduced pressure. The residue is purified by flash silica chromatography (DCM: methanol, 9: 1) to afford the title compound (0.0027g).

[a] D 20 =+38. 0 (c = 0.1, CH30H) ; 'H-NMR (400 MHz, CD30D) 8 ppm: 2.13 (s, 3H,-CO CH3) ; 3.43 (m, 1 H, H-7); 3.45 (s, 1 H,- O CH3) ; 3.75 (dd, 1 H, J = 13.3, 1.5 Hz, H-5); 3.90 (dd, 1 H, J = 10.6, 5.8 Hz, H-8); 4.07 (m, 2H, H-7 and H-9); 4.57 (m, 1 H, H-5); 5.43 (d, 1 H, J = 5.9 Hz, H-3); 5.61 (s, 1 H, H-2); 5.70 (d, 1 H, J = 8.0 Hz, H-5'); 7.56 (d, 1 H. J = 8.0 Hz, H-6'); 3C-NMR (100 MHz, CD30D) 8 ppm: 19.6, 56.5, 66.9, 72.1, 73.4, 74.2, 78.3, 93.2, 101.9, 143. 0, 150.8, 160.6, 164.9, 170.7.

EXAMPLE 7 This Example illustrates an alternative preparation of compound No. 17 in Scheme 2 Step 2: The preparation of In a reactor equipped with a mechanical stirrer, a solution of 1,2, 5, 6-di-o-isopropylidene- alpha-D-allofuranose (commercially available from Aldrich, 100 g, 364 mmol) in of DCM (1. 6 I) is treated sequentially with allyl bromide (55 ml, 653 mmol) and aqueous sodium hydroxide (50%, 1.6 I) and tetrabutylamonium iodide (14.2 g, 38.4 mmol). After stirring vigorously at +23°C for 5 hours, the phases are separated. The aqueous layer is extracted with TBME (2 x 500 ml). The organic extracts are combined, washed with aqueous saturated ammonium chloride (1 1 + addition of solid ammonium chloride for the neutrali- zation of sodium hydroxide), dried over magnesium sulphate and concentrated in vacuo to give the crude allyl ether (122 g) as a mixture of oil and crystalline material. Purification by recrystallization in hexane affords the allyl ether as colorless crystals (106.3 g, 92%).

1 H-NMR (300 MHz, CDCI3) 5 ppm: 1.38 (s, 3H); 1.59 (s, 3H), 1.48 (s, 3H); 1.37 (s, 3H); 3.93 - 3. 85 (m, 1H) ; 4.13-3. 96 (m, 4H); 4.28-4. 15 (m, 1 H) ; 4.45-4. 35 (m, 1H) ; 4.68-4. 59 (m, 1 H); 5.27-5. 19 (dd, 1 H); 5.48-5. 28 (dd, 1 H); 5.77 (d, 1 H); 6.05-5. 89 (m, 1 H).

Step 3: The preparation of: A solution of the product from Step 2 (106 g, 353 mmol) in acetic acid/water 75: 25 v/v (700 ml) is kept at +23°C for 15 hours, then concentrated in vacuo at +30°C. TBME and satura- ted aqueous sodium bicarbonate (30 ml) are added to the residue. The aqueous layer is extracted with TBME (3 x 200 ml). The organic extracts are combined, washed with aqueous saturated sodium chloride (30 ml), dried over magnesium sulphate and concentrated in vacuo to give the diol as a colorless solid (83 g, 91 %) which does not require further purification.

1 H-NMR (300 MHz, CD03) 6 ppm: 1.38 (s, 3H); 1.59 (s, 3H); 2.65-2. 48 (two br m, 2H); 3.80-3. 65 (br m, 2H); 3.98-3. 88 (m, 1 H); 4.15-4. 00 (m, 3H); 4.31-4. 20 (m, 1 H); 4.68- 4.62 (m, 1 H); 5.28-5. 22 (dd, 1 H); 5.48-5. 30 (dd, 1 H); 5.77 (d, 1 H); 6.05-5. 89 (m, 1 H).

Step 4: The preparation of: To a solution of the product from Step 3 (83 g, 319 mmol) and triethylamine (111 ml, 798 mmol) in DCM (400 ml) at 0°C under an atmosphere of argon is added dropwise methane- sulfonyl chloride (54 ml, 702 mmol). After 30 min at 0°C, water (200 ml) is added to the white suspension. The phases are separated. The aqueous layer is extracted with DCM (2 x 200 ml). The organic extracts are combined, washed with aqueous saturated sodium bicarbonate (50 ml), dried over magnesium sulphate and concentrated in vacuo to give the crude bis-mesylate (129g, quantitative) as a pale yellowish oil which does not require further purification.

1 H-NMR (300 MHz, CDCI3) 6 ppm: 1.38 (s, 3H); 1.59 (s, 3H); 3.10 (s, 3H); 3.11 (s, 3H); 3.97-3. 89 (m, 1 H); 4.28-4. 02 (m, 3H); 4.48-4. 37 (m, 2H); 4.69-4. 52 (m, 1 H); 5.16- 5. 08 (m, 1 H); 5.28-5. 22 (dd, 1 H); 5.40-5. 29 (dd, 1 H); 5.77 (d, 1 H); 6.05-5. 89 (m, 1 H).

Step 5: The preparation of: A solution of the product from Step 4 (10.5 g, 25.2 mmol) in N, N-dimethylacetamide (260 m) under an atmosphere of argon is treated with Nal (24.6 g, 164 mmol). The resulting suspen- sion is stirred at +100°C for 2.5 hours while a dark-brown coloration characteristic to the formation of iodine develops gradually. The reaction mixture is cooled down to room temperature is diluted with water (250 mi) and treated with aqueous sodium thiosulphate (1 M, 130 ml). After stirring for 10 minutes, hexane (350 mi) is added. The aqueous layer is extracted with hexane (2 x 350 ml). The organic extracts are combined, washed with aqueous saturated sodium chloride (2 x 350 ml), dried over magnesium, sulphate and concentrated in vacuo to give the crude olefin. Purification by Kugelrohr distillation under reduced pressure affords pure product (5.3 g, 93%) as a colorless oil.

1 H-NMR (300 MHz, CDCI3) 5 ppm: 1.38 (s, 3H); 1.59 (s, 3H); 3.55-3. 46 (m, 1 H); 4.22- 4.05 (m, 2H); 4.47-4. 37 (m, 1 H); 4.65-4. 55 (m, 1 H); 5.35-5. 18 (m, 3H); 5.52-5. 40 (dd, 1 H); 5.77 (d, 1 H); 5.58-5. 75 (m, 2H).

Step 6: The preparation of: A solution of the product from Step 5 (10.0 g, 44.2 mmol) and Grubbs catalyst (1.45 g, 1.77 mmol) in dry DCM (880 ml) saturated with argon is refluxed under a slight flow of argon for 8 hours. The reaction mixture is washed with water (200 ml), dried with magnesium sulphate and concentrated in vacuo. Purification of the residue by filtration over a pad of silica gel (elution with DCM) followed by Kugelrohr distillation under reduced pressure affords pure product as a pale brown solid (7.4 g, 85%).

1 H-NMR (300 MHz, CDCI3) 5 ppm: 1.38 (s, 3H); 1.59 (s, 3H); 3.35-3. 25 (m, 1 H); 4.50- 4.38 (m, 3H); 4.70-4. 54 (m, 1 H) ; 5.72-5. 53 (m, 1 H) ; 5.77 (d, 1 H) ; 6.25-6. 15 (m, 1 H).

Step 7: The preparation of: To a solution of the product from Step 6 (0.0595 g, 0.300 mmol) in 13 ml of THF/water (1: 1) at room temperature is added N-bromosuccinimide (0.0651 g, 0.355 mmol). The mixture is stirred vigorously for 2 hours, and then diluted with water (20 ml) containing sodium thiosulphate (0.5 g) and extracted with ethyl acetate (3 x 20 ml). The combined organic layer is dried over magnesium sulphate, filtered and concentrated in vacuo. The colorless crystalline residue (0.126 g) is used in the next reaction without further purification.

Step 8: The preparation of: A solution of the crude product from Step 7 in THF (12.5 ml) is treated with sodium hydroxide (1 N, 3.23 ml) and then refluxed for 1 hour. The mixture is poured into water (20 mi) and then extracted with ethyl acetate (3 x 20 ml). The combined organic layer is washed with aqueous saturated sodium chloride, dried over magnesium sulphate and concentrated in vacuo to give a yellowish crystalline residue (0.064 g), which is used in the next reaction without further purification.

Step 9: The preparation of: The crude product from Step 8 is dissolved in 2-methoxyethanol (10 ml) and sodium azide (0.293 g, 4.51 mmol) is added. The mixture is heated at +130°C for 2 hours, diluted with saturated aqueous sodium hydroxide (30 mi) and extracted with ethyl acetate (3 x 20 ml).

The combined organic layer is dried over magnesium sulphate and concentrated in vacuo.

The residue (0.090 g) is purified by flash chromatography (Si02, 3 x 16 cm, cyclohexane/EtOAc 2: 1--+ 1 : 1, gradient) to afford of the desired azide (0.043 g, 56 % yield) as a white crystalline solid.

1 H-NMR (300 MHz, CDCI3) 5 ppm: 1.30 (s, 3H); 1.54 (s, 3H); 2.27-2. 20 (m, 1 H); 3.55- 3.47 (m, 1 H); 3.90-3. 70 (m, 3H); 4.33-4. 20 (m, 2H); 4.67-4. 58 (m, 1 H); 5.78 (d, 1 H).

Step 10: The preparation of: To a solution of the product from Step 9 (0.40 g, 1.55 mmol) in dry DCM (60 ml) at room temperature under argon atmosphere is added 1,1, 1-tris (acetyloxy)-1, 1-dihydro-1, 2-benzio- doxol-3- (1 H)-one (the Dess-Martin periodinane, 1.61 g). The mixture is stirred for 2.5 hours.

After the starting material disappeared, aqueous saturated sodium bicarbonate (50 ml) and aqueous saturated sodium thiosulphate (50 ml) solution are added sequentially. The mixture is stirred for 10 minutes, extracted with DCM, dried over magnesium sulphate and concentrated in vacuo. The crude ketone is used in the next reaction without further purification.

Step 11: The preparation of: To a solution of the product of Step 10 in dry MeOH (50 ml) is added sodium borohydride (0.50 g) at 0°C. The resulting mixture is stirred for 1 hour, and concentrated in vacuo without heating. The residue is taken up with ethyl acetate (20 ml) and washed with water (20 ml).

The aqueous layer is extracted with ethyl acetate (2 x 20 ml). The organic extracts are combined, dried over magnesium sulphate and concentrated in vacuo to afford a crude oil that used for the next reaction without further purification.

Step 12: The preparation of: To a solution of the crude product from Step 11 in dry DMF (50 ml) at 0°C under an atmosphere of argon are added sequentially sodium hydride (60% suspension in oil, 0.10 g, 2.50 mmol) and methyl iodide (0.20 g). After stirring for 3 hours, the reaction is quenched by adding saturated aqueous ammonium chloride (100 ml). The mixture is extracted with ethyl acetate (3 x 20 ml). The combined organic layer is washed with aqueous saturated sodium chloride, dried over magnesium sulphate and concentrated in vacuo. The residue is purified by flash silica chromatography (cyclohexane/ethyl acetate 10: 1) to afford the desired methyl ether as a colorless oil (0.346 g, 82% yield).

Step 13: The preparation of: To a solution of the product from Step 12 (0.064 g, 0. 24 mmol) in dry DCM (5 ml) is added thiophenol (0.15 ml, 1.42 mmol), and then H+-Amberlyst resin (0.025 g) at +23°C. After stirring for 1 hour at this temperature, the mixture is quenched by adding saturated sodium bicarbonate (10 ml) and extracted with DCM (2 x 10 ml). The combined organic layers are washed with brine, dried over anhydrous magnesium sulphate and concentrated in vacuo.

The residue is purified by flash silica chromatography (hexanes: ethyl acetate 4: 1) to afford the desired product as colorless oil, ( (0. 068 g, yield: 65%).

EXAMPLE 8 This Example illustrates the fungicidal properties of certain of the novel compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants.

The technique employed was as follows.

Plants were grown on an artificial, cellulose based growing medium. The test compounds were individually diluted in reverse osmosis water to a final concentration of 100ppm in water (that is, 1mg of compound in a final volume of 10ml) immediately before use. TWEEN 20 (at a final concentration of 0.05% by volume) was added with the water to improve retention of the spray deposit. TWEEN is a registered trade mark.

The compounds were applied to the foliage of the test plants by spraying the plant to maximum droplet retention.

These tests were carried out against Stagonospora nodorum (LEPTNO), Blumeria graminis f. sp. tritici (ERYSGT), and Puccinia triticina (PUCCRT) on wheat. Two replicates, each containing 3 plants were used for each treatment. The plants were inoculated with either a calibrated fungal spore suspension or a"dusting"with dry spores 6 hours or one day after chemical application.

After chemical application and inoculation, the plants were incubated under high humidity conditions (except those inoculated with Blumeria graminis f. sp. tritici) and then put into an appropriate environment to allow infection to proceed until the disease was ready for assessment. The time period between chemical application and assessment varied from six to nine days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds.

Assessments were carried out collectively on the plants in each replicate and averaged to give one result per replicate.

The disease level present (the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed (see formula below) to calculate a PRCO (Percentage Disease Reduction from Control) value.

BANDED ASSESSMENT METHOD AND CALCULATION OF PRCO VALUES The mean disease values are banded in the manner shown below. If the disease level value falls exactly mid-way between two of the points, the result will be the lower of the two points.

0 = 0% disease present 10 = 5.1-10% disease present 1 = 0. 1-1% disease present 20 = 10.1-20% disease present 3 = 1.1-3% disease present 30 = 20.1-30% disease present 5 = 3.1-5% disease present 60 = 30.1-60% disease present 90 = 60.1-100% disease present An example of a typical banded calculation is as follows : Mean disease level for treatment A = 25% Therefore banded mean disease level for treatmen A = 30 Mean disease level on untreated controls = 85% Therefore banded mean disease level on untreated controls = 90 PRCO =100-{Banded mean disease level for treatment A} x 100 {Banded mean disease level on untreated controls} = (30/90 x 100) = 66.7 The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67.

It is possible for negative PRCO values to be obtained.

PRCO results obtained from Compounds of this invention are shown in Table 2 below.

TABLE 2 COMPOUND NO. ERYSGT PUCCRT LEPTNO (Table 1) 6hour 1 day 1 day Protectant Protectant Protectant 1 83 100 0 2 N 0 50 5 50 0 0 7 100 100 83 9 N 100 0 13 N 100 0 17 0 50 0 Key to Table I ERYSGT = Blumeria graminis tritici PUCCRT = Puccinia triticina LEPTNO = Stagonospora nodorum N = Not tested