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"N Alkynyl 2 [Substituted Phenoxy] Alkylamides And Their Use As Fungicides"

Abstract: Fungicidal compounds of the general formula (1) wherein X, Y, Z, R1, R2, R3, R4 and R5 have the definitions given in claim 1.

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Patent Information

Application #
Filing Date
05 April 2005
Publication Number
19/2007
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application

Applicants

SYNGENTA LIMITED
EUROPEAN REGIONAL CENTRE, PRIESTLEY ROAD, SURREY RESEARCH PARK, GUILDFORD SURREY GU2 7YH, UK

Inventors

1. ROGER SALMON
SYNGENTA LIMITED, JEALOTT'S HILL RESEARCH STATION, BRACKNELL, BERKS RG42 6EY, UK
2. DAVID WILLIAM LANGTON
SYNGENTA LIMITED, JEALOTT'S HILL RESEARCH STATION, BRACKNELL, BERKS RG42 6EY, UK

Specification

N-ALKYNYL-2- (SUBSTITUTED PHENOXY) ALKYLAMIDES AND THEIR USE AS FUNGICIDES This invention relates to novel ;V-alkynyl-2-(substituted phenoxy)alkylamides, to processes for preparing them, to compositions containing them and to methods of using them to combat fungi, especially fungal infections of plants. Certain A^-alkynyl-2-(substituted phenoxy)alkylamides are described in US 4,083,867 and US 4,116,677 as being useful as herbicides. Others are described in US 4,168,319 as being useful as mildewicides. The present invention is concerned with the provision of particular W-alkynyl-2- (substituted phenoxy)alkylamides for use as plant fungicides. Thus according to the present invention there is provided a compound of the general formula (1): (Figure Removed) wherein X, Y and Z are independently H, halogen, CM alkyl (e.g. methyl), halo(Cu)alkyl (e.g. trifluoromethyl), C2-4 alkenyl, halo(C2t)alkenyl, C2-4 alkynyl, halo(Czwi)alkynyl, CM alkoxy (e.g. methoxy), halo(Ci-4)alkoxy (e.g. trifluoromethoxy), -S(0)n(C|.4)alkyl where n is 0,1 or 2 and the alkyl group is optionally substituted with fluoro (e.g. methylthio, trifluoromethylsulphonyl), -OS02(Ci-4)alkyl where the alkyl group is optionally substituted with fluoro (e.g. trifluoromethylsulphonyloxy), cyano, nitro, CM alkoxycarbonyl, -CONR'R", -COR1, -NR'COR" or -NR'COOR1" where R1 and R" are independently H or CM alkyl and R1" is CM alkyl (e.g. acetyl, -NHCOCH3 and -NHC02CH3), provided that at least one of X and Z is other than H; RI is alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl or alkylsulphonyl alkyl in which the total number of carbon atoms is 2 or 3 (e.g. methoxymethyl, methylthiomethyl, ethoxymethyl, 2-methoxyethyl and 2-methylthioethyl); R2 is H, CM alkyl, CM alkoxymethyl or benzyloxymethyl in which the phenyl ring of the benzyl moiety is optionally substituted with CM alkoxy; R3 and R4 are independently H, Ci-3 alkyl, C2-3 alkenyl or C2.3 alkynyl provided that both are not H and that when both are other than H their combined total of carbon atoms does not exceed 4, or R3 and R4 join with the carbon atom to which they are attached to form a 3 or 4 membered carbocyclic ring optionally containing one O, S or N atom and optionally substituted with halo or CM alkyl; and RS is H, CM alkyl or C3-6 cycloalkyl in which the alkyl or cycloalkyl group is optionally substituted with halo, hydroxy, C\-6 alkoxy, cyano, d-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di(Ci-4)alkylaminocarbonyloxy, -S(O)n(Ci-6)alkyl where n is 0,1 or 2, triazolyl (e.g. 1,2,4-triazol-l-yl), tri(Ci.,|)alkyIsilyloxy, optionally substituted phenoxy, optionally substituted thienyloxy, optionally substituted benzyloxy or optionally substituted thienylmethoxy, or RS is optionally substituted phenyl, optionally substituted thienyl or optionally substituted benzyl, in which the optionally substituted phenyl and thienyl rings of the RS values are optionally substituted with one, two or three substituents selected from halo, hydroxy, mercapto, CM alkyl, €2-4 alkenyl, C2-4 alkynyl, CM alkoxy, C2J» alkenyloxy, C2.4 alkynyloxy, halo(CM)alkyl, halo(Ci.4)alkoxy, CM alkylthio, halo(Ci)alkylthio, hydroxy(Ci-4)alkyl, CMalkoxy(CM)alkyl, C3-6 cycloalkyl/C3.6 cycloalkyl(CM)alkyl, phenoxy, benzyloxy, benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, -NRmRn, -NHCOR"1, -NHCONRmR", -CONR11, -SO2Rm, -OS02Rm, -CORm, -CRm=NRn or -N=CRmRn, in which Rm and Rn are independently hydrogen, CM alkyl, halo(Ci.)alkyl, CM alkoxy, halo(CM)alkoxy, CM alkylthio, C3-6 cycloalkyl, C3.6 cycloalkyl CM)alkyl, phenyl or benzyl, the phenyl and benzyl groups being optionally substituted with halogen, CM alkyl or CM alkoxy. The compounds of the invention contain at least one asymmetric carbon atom (and at least two when R3 and R are different) and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such. However, these mixtures may be separated into individual isomers or isomer pairs, and this invention embraces such isomers and mixtures thereof in all proportions. It is to be expected that for any given compound, one isomer may be more fungicidally active than another. Except where otherwise stated, alkyl groups and alkyl moieties of alkoxy, alkylthio, etc., suitably contain from 1 to 4 carbon atoms in the form of straight or branched chains. Examples are methyl, ethyl, n-and wo-propyl and «-, sec-, iso- and tertbutyl. Where alkyl moieties contain 5 or 6 carbon atoms, examples are n-pentyl and nhexyl. Alkenyl and alkynyl moieties also suitable contain from 2 to 4 carbon atoms in the form of straight or branched chains. Examples are allyl, ethynyl and propargyl. Halo includes fluoro, chloro, bromo and iodo. Most commonly it is fluoro, chloro or bromo and usually fluoro or chloro. The substituents X, Y and Z on the phenyl ring of formula (1) may provide a 3-, 3, 5- or 3, 4, 5- substituted phenyl ring. Typically X, Y and Z are all chloro or methyl, or X and Z are both chloro or bromo and Y is H or methyl, or X and Z are both methyl or methoxy and Y is H, chloro, bromo or alkylthio, or X is methoxy, Y is H and Z is cyano or chloro, or X is methyl, Y is H and Z is ethyl, or X is chloro, bromo or trifluoromethyl and both Y and Z are H. Typically, RI is methoxymethyl, methylthiomethyl, ethoxymethyl, 2-methoxyethyl and 2-methylthioethyl. Methoxymethyl is a preferred value of Rj. Typically R2 is H and at least one, but preferably both of Rj and R4 are methyl. When one of R3 and RA is H, the other may be methyl, ethyl or n- or wo-propyl. When one of RS and R4 is methyl, the other may be H or ethyl but is preferably also methyl. R2 also includes Ci-4 alkoxymethyl and benzyloxymethyl in which the phenyl ring of the benzyl group optionally carries an alkoxy substituent, e.g. a methoxy substituent. Such values of R2 provide compounds of formula (1) that are believed to be pro-pesticidal compounds. Typically RS is H, methyl, hydroxymethyl, methoxymethyl, 1-methoxyethyl, tertbutyldimethylsiloxymethyl, 3-cyanopropyl, 3-methoxypropyl, 3-(l,2,4-triazol-l-yl)- propyl, 3-methylthiopropyl, 3-methanesulphinylpropyl or 3-methanesulphonylpropyl. Of particular interest are compounds where R5 is methyl, methoxymethyl or cyanopropyl. In one aspect the invention provides a compound of the general formula (1) wherein X, Y and Z are independently H, halogen, CM alkyl (e.g. methyl), halo(CM)alkyl (e.g. trifluoromethyl), C2-4 alkenyl, halo(C2-4)alkenyl, 2-4 alkynyl, haIo(C2-4)alkvnyl, CM alkoxy (e.g. methoxy), halo(CM)alkoxy (e.g. trifluoromethoxy), -S(0)n(CM)alkyl where n is 0, 1 or 2 and the alkyl group is optionally substituted with fluoro (e.g. methylthio, tri- fluoromethylsulphonyl), -OSO2(CM)alkyl where the alkyl group is optionally substituted with fluoro (e.g. trifluoromethylsulphonyloxy), cyano, nitro, CM alkoxycarbonyl, -CONR'R", -COR' or -NR'COR" where R1 and R" are independently H or CM alkyl (e.g. -NHCOCH3), provided that at least one of X and Z is other than H; RI is alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl or alkylsulphonylalkyl in which the total number of carbon atoms is 2 or 3 (e.g. methoxymethyl, methylthiomethyl, ethoxymethyl, 2-methoxyethyl and 2-methylthioethyl); RZ is H, CM alkyl, CM alkoxymethyl or benzyloxymethyl in which the phenyl ring of the benzyl moiety is optionally substituted with CM alkoxy; R3 and Rj are independently H, C\.i alkyl, C2-3 alkenyl or Cao alkynyl provided that both are not H and that when both are other than H their combined total of carbon atoms does not exceed 4, or R3 and R4 join with the carbon atom to which they are attached to form a 3 or 4 membered carbocyclic ring optionally containing one O, S or N atom and optionally substituted with halo or CM alkyl; and RS is H, CM alkyl or C3-6 cycloalkyl in which the alkyl or cycloalkyl group is optionally substituted with halo, hydroxy, Ci-e alkoxy, C^ alkylthio, cyano, CM alkylcarbonyloxy, aminocarbonyloxy or mono- or di(C|_4)alkylaminocarbonyloxy, tri(Ci-4)alkylsilyloxy, optionally substituted phenoxy, optionally substituted thienyloxy, optionally substituted benzyloxy or optionally substituted thienylmethoxy, or RS is optionally substituted phenyl, optionally substituted thienyl or optionally substituted benzyl, in which the optionally substituted phenyl and thienyl rings of the RS values are optionally substituted with one, two or three substituents selected from halo, hydroxy, mercapto, CM alkyl, C2-4 alkenyl, C^ alkynyl, CM alkoxy, C2-4 alkenyloxy, C2-4 alkynyloxy, halo(CM)alkyl, halo(CM)alkoxy, CM alkylthio, halo(CM)alkylthio, hydroxy(CM)alkyl, CMalkoxy(Ci-4)alkyl, C3-6 cycloalkyl, C3.6 cycloalkyl(CM)alkyl, phenoxy, benzyloxy, benzoyloxy^ cyano, isocyano, thiocyanato, isothiocyanato, nitro, -NRmR", -NHCOR™ -NHCONRmRn, -CONRmRn, -SO2Rm, -OSO2Rm, -CORm, ~CRm=NR" or -N=CRmR", in which Rm and Rn are independently hydrogen, CM alkyl, halo(CM)alkyl, CM alkoxy, halo(CM)alkoxy, CM alkylthio, C3_6 cycloalkyl, C3.6 cycloalkyl( CM)alkyl, phenyl or benzyl, the phenyl and benzyl groups being optionally substituted with halogen, CM alkyl or CM alkoxy. In another aspect the invention provides a compound of the general formula (1) wherein X, Y and Z are all chloro or methyl, or X and Z are both chloro or bromo and Y is H or methyl, or X and Z are both methyl or methoxy and Y is H, chloro, bromo or alkylthio, or X is methoxy, Y is H and Z is cyano or chloro, or X is methyl, Y is H and Z is ethyl, or X is chloro, bromo or trifluorornethyl and both Y and Z are H; R) is methoxymethyl, methylthiomethyl, ethoxymethyl, 2-methoxyethyl or 2-methythioethyl; R2 is H; R3 and R4 are both methyl; and R5 is H, methyl, hydroxymethyl, methoxymethyl, l-methoxyethyl, terf-butyldimethylsiloxymethyl, 3-cyanopropyl, 3-methoxypropyl, 3- (l,2,4-triazol-l-yl)propyl, 3-methylthiopropyl, 3-methanesulphinylpropyl or 3- methanesulphonylpropyl. Preferably R! is methoxymethyl. Preferably R5 is methyl, methoxymethyl or 3-cyanopropyl. Compounds that form part of the invention are illustrated in Tables 1 to 41 below. Characterisation data are given in Table 42 and later in the Examples. The compounds in Table 1 are of the general formula (1) where R] is methoxymethyl, R2 is H, R3 and R4 are both methyl, R$ is methyl and X, Y and Z have the values given in the table. (Table Removed)Table 2 consists of 134 compounds of the general formula (1), where RI is ethoxymethyl, R2 is hydrogen, Ra and R« are both methyl, RS is methyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 2 is the same as compound 1 of Table 1 except that in compound 1 of Table 2 RI is ethoxymethyl instead of methoxymethyl. Similarly, compounds 2 to 134 of Table 2 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 2 RI is ethoxymethyl instead of methoxymethyl. Table 3 Table 3 consists of 134 compounds of the general formula (1), where R] is methylthiomethyl, R2 is hydrogen, Ra and R4 are both methyl, and Rj is methyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 3 is the same as compound 1 of Table 1 except that in compound 1 of Table 3 Rj is methylthiomethyl instead of methoxymethyl. Similarly, compounds 2 to 134 of Table 3 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 3 RI is methylthiomethyl instead of methoxymethyl. Table 4 Table 4 consists of 134 compounds of the general formula (1), where RI is 2- methoxyethyl, R2 is hydrogen, RS and R4 are both methyl, RS is methyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 4 is the same as compound 1 of Table 1 except that in compound 1 of Table 4 RI is 2-methoxyethyl instead of methoxymethyl. Similarly, compounds 2 to 134 of Table 4 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 4 RI is 2- methoxyethyl instead of methoxymethyl. TableS Table 5 consists of 134 compounds of the general formula (1), where RI is 2-methylthioethyl, RZ is hydrogen, Ra and R4 are both methyl, RS is methyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 5 is the same as compound 1 of Table 1 except that in compound 1 of Table 5 R] is 2-methylthioethyl instead of methoxymethyl. Similarly, compounds 2 to 134 of Table 5 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 4 R| is 2- methylthioethyl instead of methoxymethyl. Table 6 Table 6 consists of 134 compounds of the general formula (1), where R| is methoxymethyl, R2 is hydrogen, RB and R4 are both methyl, RS is H and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 6 is the same as compound 1 of Table 1 except that in compound 1 of Table 6 RS is H instead of methyl. Similarly, compounds 2 to 134 of Table 6 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 6 RS is H instead of methyl. Table 7 Table 7 consists of 134 compounds of the general formula (1), where R] is ethoxymethyl, R2 is hydrogen, Rj and Rj are both methyl, R5 is H and X, Y and Z have the values listed in Table 1 for compounds 1 to 134. Thus compound 1 of Table 7 is the same as compound 1 of Table 2 except that in compound 1 of Table 7 RS is H instead of methyl. Similarly, compounds 2 to 134 of Table 7 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 7 RS is H instead of methyl. Table 8 Table 8 consists of 134 compounds of the general formula (1), where R\ is methylthiomethyl, R2 is hydrogen, RS and R4 are both methyl, and RS is H and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 8 is the same as compound 1 of Table 3 except that in compound 1 of Table 8 RS is H instead of methyl. Similarly, compounds 2 to 134 of Table 8 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 8 RI is H instead of methyl. Table 9 Table 9 consists of 134 compounds of the general formula (1), where RI is 2-methoxyethyl, R2 is hydrogen, R3 and Rj are both methyl, R5 is H and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 9 is the same as compound 1 of Table 4 except that in compound 1 of Table 9 RS is H instead of methyl. Similarly, compounds 2 to 134 of Table 9 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 9 RS is H instead of methyl. Table 10 Table 10 consists of 134 compounds of the general formula (1), where RI is 2- methylthio-ethyl, R2 is hydrogen, R3 and R4 are both methyl, R5 is H and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 10 is the same as compound 1 of Table 5 except that in compound 1 of Table 10 RS is H instead of methyl. Similarly, compounds 2 to 134 of Table 10 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 10 RS is H instead of methyl. Table 11 Table 11 consists of 134 compounds of the general formula (1), where R\ is methoxymethyl, R2 is hydrogen, RS and R4 are both methyl, RS is hydroxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 11 is the same as compound 1 of Table 1 except that in compound 1 of Table 11 RS is hydroxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 11 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 11 RS is hydroxymethyl instead of methyl. Table 12 Table 12 consists of 134 compounds of the general formula (1), where RI is ethoxymethyl, R2 is hydrogen, RS and R4 are both methyl, RS is hydroxymethyl and X, and Z have the values listed in Table 1. Thus compound 1 of Table 12 is the same as compound 1 of Table 2 except that in compound 1 of Table 12 RS is hydroxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 12 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 12 RS is hydroxymethyl instead of methyl. Table 13 Table 13 consists of 134 compounds of the general formula (1), where RI is methylthiomethyl, R2 is hydrogen, RS and R4 are both methyl, and RS is hydroxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 13 is the same as compound 1 of Table 3 except that in compound 1 of Table 13 RS is hydroxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 13 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 13 RI is hydroxymethyl instead of methyl. Table 14 Table 14 consists of 134 compounds of the general formula (1), where RI is 2-methoxyethyl, R2 is hydrogen, RS and R4 are both methyl, RS is hydroxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 14 is the same as compound 1 of Table 4 except that in compound 1 of Table 14 RS is hydroxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 14 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 14 R5 is hydroxymethyl instead of methyl. Table 15 Table 15 consists of 134 compounds of the general formula (1), where RI is 2- methylthioethyl, Ra is hydrogen, R3 and R4 are both methyl, RS is hydroxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 15 is the same as compound 1 of Table 5 except that in compound 1 of Table 15 RS is hydroxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 15 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 15 RS is hydroxymethyl instead of methyl. Table 16 Table 16 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, R2 is hydrogen, R3 and R4 are both methyl, R5 is methoxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 16 is the same as compound 1 of Table 1 except that in compound 1 of Table 16 RS is methoxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 16 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 16 RS is methoxymethyl instead of methyl. Table 17 Table 17 consists of 134 compounds of the general formula (1), where RI is ethoxymethyl, R2 is hydrogen, RS and R4 are both methyl, RS is methoxymethyl and X, and Z have the values listed in Table 1. Thus compound 1 of Table 17 is the same as compound 1 of Table 2 except that in compound 1 of Table 17 RS is methoxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 17 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 17 RS is methoxymethyl instead of methyl. Table 18 Table 18 consists of 134 compounds of the general formula (1), where R\ is methylthiomethyl, R2 is hydrogen, R$ and R4 are both methyl, and RS is methoxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 18 is the same as compound 1 of Table 3 except that in compound 1 of Table 18 RS is methoxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 18 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 18 Rj is methoxymethyl instead of methyl. Table 19 Table 19 consists of 134 compounds of the general formula (1), where R| is 2-methoxyethyl, Rj is hydrogen, Rj and R^ are both methyl, RS is methoxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 19 is the same as compound 1 of Table 4 except that in compound 1 of Table 19 RS is methoxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 19 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 19 RS is methoxymethyl instead of methyl. Table 20 Table 20 consists of 134 compounds of the general formula (1), where RI is 2- methylthioethyl, R2 is hydrogen, R3 and R* are both methyl, RS is methoxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 20 is the same as compound 1 of Table 5 except that in compound 1 of Table 20 RS is methoxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 20 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 20 RS is methoxymethyl instead of methyl. Table 21 Table 21 consists of 134 compounds of the general formula (1), where R\ is methoxymethyl, Rj is hydrogen, Ra and R4 are both methyl, RS is /erf-butyldimethylsilyloxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 21 is the same as compound 1 of Table 1 except that in compound 1 of Table 21 RS is tertbutyldimethylsilyloxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 21 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 21 RS is /erf-butyldimethylsilyloxymethyl instead of methyl. Table 22 Table 22 consists of 134 compounds of the general formula (1), where Ri is ethoxymethyl, R2 is hydrogen, R3 and R4 are both methyl, RS is ter/-butyldimethylsilyloxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 22 is the same as compound 1 of Table 2 except that in compound 1 of Table 22 R5 is /er/-butyldimethylsilyloxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 22 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 22 RS is /er/-butyldimethylsilyloxymethyl instead of methyl. Table 23 Table 23 consists of 134 compounds of the general formula (1), where RI methylthiomethyl, R: is hydrogen, Rj and R4 are both methyl, and RS is /er/-butyldimethylsilyloxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 23 is the same as compound 1 of Table 3 except that in compound 1 of Table 23 R5 is tertbutyldimethylsilyloxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 23 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 23 RI is terf-butyldimethylsilyloxymethyl instead of methyl. Table 24 Table 24 consists of 134 compounds of the general formula (1), where RI is 2-methoxyethyl, R2 is hydrogen, R$ and R4 are both methyl, RS is fer/-butyldimethyisilyloxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 24 is the same as compound 1 of Table 4 except that in compound 1 of Table 24 RS is tert-butyldimethylsilyloxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 24 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 24 R5 is /m-butyldimethylsilyloxymethyl instead of methyl. Table 25 Table 25 consists of 134 compounds of the general formula (1), where RI is 2- methylthioethyl, R2 is hydrogen, RI and R4 are both methyl, R5 is tert-butyldimethylsilyloxymethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 25 is the same as compound 1 of Table 5 except that in compound 1 of Table 25 RS is ferr-butyldimethylsilyloxymethyl instead of methyl. Similarly, compounds 2 to 134 of Table 25 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 25 R5 is /er/-butyldimethylsilyloxymethyl instead of methyl. Table 26 Table 26 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, R2 is hydrogen, R3 and R4 are both methyl, R5 is 1-methoxyethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 26 is the same as compound 1 of Table 1 except that in compound 1 of Table 26 RS is 1-methoxyethyl instead of methyl. Similarly, compounds 2 to 134 of Table 26 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 26 RS is 1-methoxyethyl instead of methyl. Table 27 Table 27 consists of 134 compounds of the general formula (1), where RI is ethoxymethyl, R2 is hydrogen, RS and R4 are both methyl, RS is 1-methoxyethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 27 is the same as compound 1 of Table 2 except that in compound 1 of Table 27 RS is 1-methoxyethyl instead of methyl. Similarly, compounds 2 to 134 of Table 27 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 27 RS is 1- methoxyethyl instead of methyl. Table 28 Table 28 consists of 134 compounds of the general formula (1), where RI is methylthiomethyl, R2 is hydrogen, R3 and R« are both methyl, and RS is 1-methoxyethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 28 is the same as compound 1 of Table 3 except that in compound 1 of Table 28 RS is 1-methoxyethyl instead of methyl. Similarly, compounds 2 to 134 of Table 28 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 28 RI is 1- methoxyethyl instead of methyl. Table 29 Table 29 consists of 134 compounds of the general formula (1), where RI is 2-methoxyethyl, R2 is hydrogen, R3 and Rj are both methyl, RS is 1-methoxyethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 29 is the same as compound 1 of Table 4 except that in compound 1 of Table 29 RS is 1-methoxyethyl instead of methyl. Similarly, compounds 2 to 134 of Table 29 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 29 R5 is 1-methoxyethyl instead of methyl. Table 30 Table 30 consists of 134 compounds of the general formula (1), where RI is 2- methylthioethyl, R2 is hydrogen, R3 and R4 are both methyl, R5 is 1-methoxyethyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 30 is the same as compound 1 of Table 5 except that in compound 1 of Table 30 R5 is 1-methoxyethyl instead of methyl. Similarly, compounds 2 to 134 of Table 30 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 30 RS is 1- methoxyethyl instead of methyl, Table 31 Table 31 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, Ra is hydrogen, R3 and R are both methyl, RS is 3-cyanopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 31 is the same as compound 1 of Table 1 except that in compound 1 of Table 31 RS is 3-cyanopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 31 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 31 RS is 3-cyanopropyl instead of methyl. Table 32 Table 32 consists of 134 compounds of the general formula (1), where RI is ethoxymethyl, R2 is hydrogen, R3 and R4 are both methyl, RS is 3-cyanopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 32 is the same as compound 1 of Table 2 except that in compound 1 of Table 32 RS is 3-cyanopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 32 are the same as compounds 2 to 134 of Table 2, respectively, except that in the compounds of Table 32 RS is 3- cyanopropyl instead of methyl. Table 33 Table 33 consists of 134 compounds of the general formula (1), where RI is methylthiomethyl, R? is hydrogen, R3 and R« are both methyl, and RS is 3-cyanopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 33 is the same as compound 1 of Table 3 except that in compound 1 of Table 33 RS is 3-cyanopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 33 are the same as compounds 2 to 134 of Table 3, respectively, except that in the compounds of Table 33 Rt is 3- cyanopropyl instead of methyl. Table 34 Table 34 consists of 134 compounds of the general formula (1), where R| is 2-methoxyethyi, R2 is hydrogen, R3 and R,, are both methyl, R5 is 3-cyanopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 34 is the same as compound 1 of Table 4 except that in compound 1 of Table 34 RS is 3-cyanopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 34 are the same as compounds 2 to 134 of Table 4, respectively, except that in the compounds of Table 34 RS is 3-cyanopropyl instead of methyl. Table 35 Table 35 consists of 134 compounds of the general formula (1), where RI is 2- methylthioethyl, R2 is hydrogen, RI and R4 are both methyl, RS is 3-cyanopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 35 is the same as compound 1 of Table 5 except that in compound 1 of Table 35 RS is 3-cyanopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 35 are the same as compounds 2 to 134 of Table 5, respectively, except that in the compounds of Table 35 RS is 3- cyanopropyl instead of methyl. Table 36 Table 36 consists of 134 compounds of the general formula (1), where R\ is methoxymethyl, R2 is hydrogen, R3 and R« are both methyl, RS is 3-chloropropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 36 is the same as compound 1 of Table 1 except that in compound 1 of Table 36 RS is 3-chloropropyl instead of methyl. Similarly, compounds 2 to 134 of Table 36 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 36 RS is 3-chloropropyl instead of methyl. Table 37 Table 37 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, R2 is hydrogen, R3 and R« are both methyl, RS is 3-methylthiopropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 37 is the same as compound 1 of Table 1 except that in compound 1 of Table 37 RS is 3-methylthiopropyl instead of methyl. Similarly, compounds 2 to 134 of Table 37 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 37 RS is 3- methylthiopropyl instead of methyl. Table 38 Table 38 consists of 134 compounds of the general formula (1), where RI is rnethoxymethyl, R2 is hydrogen, Rj and R4 are both methyl, RS is 3-methanesulphinylpropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 38 is the same as compound 1 of Table 1 except that in compound 1 of Table 38 RS is 3- methanesulphinylpropyl instead of methyl. Similarly, compounds 2 to 134 of Table 38 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 38 RS is 3-methanesulphinylpropyl instead of methyl. Table 39 Table 39 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, RI is hydrogen, R^ and R* are both methyl, RS is 3-methanesulphonylpropyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 39 is the same as compound 1 of Table 1 except that in compound 1 of Table 39 RS is 3- methanesulphonylpropyl instead of methyl. Similarly, compounds 2 to 134 of Table 39 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 39 RS is 3-methanesulphonylpropyl instead of methyl. Table 40 Table 40 consists of 134 compounds of the general formula (1), where RI is methoxymethyl, R2 is hydrogen, R3 and R4 are both methyl, RS is 3-(l,2,4-triazol-l-yl)propyl and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 40 is the same as compound 1 of Table 1 except that in compound 1 of Table 40 RS is 3-(l,2,4-triazol-lyl) propyl instead of methyl. Similarly, compounds 2 to 134 of Table 40 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 40 R5 is 3-(l,2,4-triazol-l-yl)propyl instead of methyl. Table 41 Table 41 consists of 134 compounds of the general formula (1), where R\ is methoxymethyl, R2 is hydrogen, R} and R4 are both methyl, RS is 3-methoxypropyI and X, Y and Z have the values listed in Table 1. Thus compound 1 of Table 41 is the same as compound 1 of Table 1 except that in compound 1 of Table 41 R5 is 3-methoxypropyl instead of methyl. Similarly, compounds 2 to 134 of Table 41 are the same as compounds 2 to 134 of Table 1, respectively, except that in the compounds of Table 41 R$ is 3- methoxypropyl instead of methyl. (Table Removed)'H NMR chemical shifts in ppm point in degrees centigrade from IMS (solvent) or melting 108-111°C The compounds of formula (1) maybe prepared as outlined in Schemes 1 to 7 below in which X, Y, Z, RI, R2, RS, R4 and R$ have the meanings given above, R is alkyl, L is a leaving group such as a halide, for example iodide, or an alkyl or aryl sulphonyloxy group, for example methylsulphonyloxy and tosyloxy or a triflate, Hal is halogen, Ra is hydrogen or do alkyl, Rb is hydrogen or Ci-3 alkyl, provided that the total number of carbon atoms in Ra and Rb do not exceed three, RC is Ci-6 alkyl, optionally substituted benzyl or optionally substituted thienylmethyl and R

Documents

Application Documents

# Name Date
1 1373-DELNP-2005_EXAMREPORT.pdf 2016-06-30
1 abstract.jpg 2011-08-21
2 1373-delnp-2005-pct-notification.pdf 2011-08-21
2 1373-delnp-2005-abstract.pdf 2011-08-21
3 1373-delnp-2005-pct-308.pdf 2011-08-21
3 1373-delnp-2005-claims.pdf 2011-08-21
4 1373-delnp-2005-correspondence-others.pdf 2011-08-21
4 1373-delnp-2005-gpa.pdf 2011-08-21
5 1373-delnp-2005-form-5.pdf 2011-08-21
5 1373-delnp-2005-description (complete).pdf 2011-08-21
6 1373-delnp-2005-form-3.pdf 2011-08-21
6 1373-delnp-2005-form-1.pdf 2011-08-21
7 1373-delnp-2005-form-2.pdf 2011-08-21
7 1373-delnp-2005-form-18.pdf 2011-08-21
8 1373-delnp-2005-form-2.pdf 2011-08-21
8 1373-delnp-2005-form-18.pdf 2011-08-21
9 1373-delnp-2005-form-3.pdf 2011-08-21
9 1373-delnp-2005-form-1.pdf 2011-08-21
10 1373-delnp-2005-description (complete).pdf 2011-08-21
10 1373-delnp-2005-form-5.pdf 2011-08-21
11 1373-delnp-2005-correspondence-others.pdf 2011-08-21
11 1373-delnp-2005-gpa.pdf 2011-08-21
12 1373-delnp-2005-pct-308.pdf 2011-08-21
12 1373-delnp-2005-claims.pdf 2011-08-21
13 1373-delnp-2005-pct-notification.pdf 2011-08-21
13 1373-delnp-2005-abstract.pdf 2011-08-21
14 abstract.jpg 2011-08-21
14 1373-DELNP-2005_EXAMREPORT.pdf 2016-06-30