GB2399754A - Plant protection compositions - Google Patents

Abstract

Compositions, especially fungicidal compositions comprise compounds of formula I: <EMI ID=1.1 HE=50 WI=108 LX=640 LY=674 TI=CF> <PC>wherein m is 0, 1, 2 or 3; n and p are independently of each other 0 or 1; R1 is halogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted thioalkyl optionally substituted aryl, COOR11, CONR12R13, S(O)qR14, SO2NR15R16 or NR15aR16a; q is 1 or 2; and R2, R2a, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R15a and R16a are specified organic groups or a salt thereof, together with a suitable carrier.

Description

FUNGICIDAL COMPOSITIONS

The present invention relates to compositions comprising N-phenyl-[4-(4pyridyl)-pyrimidin-2-yl]-amine derivatives, to a method of protecting plants against attack or infestation by phytopathogenic organisms, such as nematodes or insects or especially microorganisms, preferably fungi, bacteria and viruses, or combinations of two or more of these organisms, by applying a composition comprising a N- phenyl-[4-(4pyridyl)-pyrimidin-2-yl]-amine derivative as specified hereinafter to a part and/or to the site of a plant and to the use of said derivative for protecting plants against said 0 organisms.

Certain N-phenyl-4-(4-pyridyl)-2-pyrimidineamine derivatives have been described in the art as having pharmacological properties e.g. in the PCT patent appli- cations WO 95/09851 and WO 95/09853, as tumor-inhibiting anti-cancer substances and in WO 97/19065 and WO98/18782 for the treatment of immune diseases.

Surprisingly, it has now been found that N-phenyl-[4-(4-pyridyl)pyrimidin-2-yl] amines are effective in plant protection and related areas, showing advantageous properties in the treatment of plant diseases caused by organisms.

The N-phenyl-[4-(4-pyridyl)-pyrimidin-2-yl]-amine derivatives according to the invention are those of the formula I ó1)3 (R)m (a)/ Rio N. / R3:l R4 hi< PR6 R7 R8 wherein misO, 1,2Or3; n and p are independently of each other 0 or 1; Rat is halogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted thioalkyl - 2 optionally substituted aryl, COOR11, CONRI2Rl3, S(O)qRI4' SO2NRI5Rl6 or NRlsaRI6a; when there is more than on Rl group, they may be the same or different; history; R2,R2a, R3, R4, R5, R6, R7, R8 are each independently hydrogen, optionally substituted alkyl, CORI7, COORIg or optionally substituted aryl, and in addition R2 and R3 may also independently be optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, or optionally substituted alkylthio, COORl', CONR20R2l' OH or SH; R6 and R7 may also be independently halogen, optionally substituted alkoxy, optionally o substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkenylamino, optionally substituted alkynylamino, optionally substituted alkylthio, optionally substituted cycloalkyl, optionally substituted heteroaryl, optionally substituted hetrocyclyl, optionally substituted cycloalkyloxy, OH, SH, N3, NR22R23 or N(R24)COR2s; or the ring members CR3R4 or CR2R2A are independently of each other a carbonyl group (C=O) or a thonyl group (C=S); or one or two of the adjacent pairs of groups Rg and R4, R4 and Rg Rs and Rg, or, if p is zero, R2A and R8 may form a bond, provided that if there are 2 double bonds in the ring the double bonds are not adjacent each other; or the pair of groups R7 and R8 or the pair of groups R6 and R7 together with the atom to which they are attached form a C3-C7 saturated ring; Rgis hydrogen, optionally substituted alkyl, optionally substituted alkenyl or optionally Rlois hydrogen, Cl-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, -CH2OR26, CH2SR27 C(0)R28,-C(0)0R29,S02R30, SOR31 or SR32; R26, R27, R28, R29, R30, R31, R32 are independently Cl-C8-alkyl Cl-Ce-alkoxyalkyl, Cl-Ce haloalkyl or phenylCI-C2-alkyl wherein the phenyl may be substituted by up to three groups selected from halo or Cl-C4-alkyl, Rll,Rl2,Rl3,Rl4,Rl5,Rl6Rl5a, Rl6a,Rl7,Rl8,Rl9,R20,R2l,R22,R23,R24,andR25are independently 11 or optionally substituted alkyl; or a salt thereof.

One group of preferred compounds are of those of formula (I') which are compounds of formula I wherein misO, 1,20r3; n and p are independently of each other O or 1; Rl is halogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted thioalkyl optionally substituted aryl, COOR,i, CONR,2R,3, S(O)qRj4' SO2NR,sR,6 or NR'saR6a; when there is more than on R. group, they may be the same or different; q is I or 2; R2, R2a' R3, R4, R5, R6, R7, Rs are each independently hydrogen, optionally substituted alkyl, CORE, COORS or optionally substituted aryl, and in addition R2 and R3 may also independently be optionally substituted alkoxy or optionally substituted alkylthio, COORS, CONR20R2,, OH or SH; lo R6 and R7 may also be independently halogen, optionally substituted alkoxy, optionally substituted alkylthio, OH, SH, N3, NR22R23 or N(R24)COR2s; or the ring members CR3R4 or CR2R2A are independently of each other a carbonyl group (C=O) or a thiocarbonyl group (C=S); or one or two of the adjacent pairs of groups R9 and R4, R4 and R8, Rs and R8, or, if p is zero, R2A and R8 may form a bond, provided that if there are 2 double bonds in the ring the double bonds are not adjacent each other; or the pair of groups R7 and R8 together with the atom to which they are attached form a C3-C7 saturated ring; R9is hydrogen or optionally substituted alkyl; Rio is hydrogen, C-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, -CH20R26, CH2SR279 C(0)R28,-C(0)0R29,SO2R30, SOR3, or SR32; R26' R27,R28, R29, Rae, Rat, R32 are independently C-cs-alkyl C'-Cg-alkoxyalkyl, C-C8 haloalkyl or phenylC- C2-alkyl wherein the phenyl may be substituted by up to three groups selected from halo or C-C4-alkyl, Rll, Rl2, Rid, Rid, Rls' Rl6 Rlsa' Rena, R17, Rig' Rig, R20, R21, R22, R23, R24, and R2s are independently H or optionally substituted alkyl; or a salt thereof.

In the context of the present specification alkyl as a group per se and as a structural element of hydroxyalkyl, thioalkyl, alkoxy, alkenyl, alkenyloxy, alkynyl alkynyloxy or haloalkoxy - is preferably C'-C6-alkyl, more preferably lower alkyl, and is linear i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec.-butyl, tert.-butyl, isopentyl, neopentyl or isohexyl. Lower alkyl is preferably methyl or ethyl. - 4

Specific examples of alkenyl and alkynyl include allyl, 2-butenyl, 3butenyl, propargyl, 2-butinyl and 3 butynyl.

When present, the optional substituents on an alkyl, alkenyl or alkynyl moiety include one or more of halogen, nitro, cyano, oxo (and acetate and ketals formed therefrom), C3 7 cycloalkyl (itself optionally substituted with C' -6 alkyl or halogen), Cs 7 cycloalkenyl (itself optionally substituted with C,-6 alkyl or halogen), hydroxy, C3 lo alkoxy, C3 0 alkoxy(C3 '0)alkoxy, C,-6 alkoxy-carbonyl(C3 '0)alkoxy, C3 0 haloalkoxy, phenyl(C'4)alkoxy (where the phenyl group is optionally substituted by one or more of Cn6 alkyl, C'-6 alkoxy, C-6 haloalkyl, CN, nitro or halogen), C3 7 cycloalkyloxy (where lo the cycloalkyl group is optionally substituted with C-6 alkyl or halogen), C3 lo alkenyloxy, C3 '0 alkynyloxy, SH, C3 '0 alkylthio, C3 0 haloalkylthio, phenyl(C 4)alkylthio (where the phenyl group is optionally substituted by one or more of C-6 alkyl, C'-6 alkoxy, C'-6 haloalkyl, CN, nitro or halogen), C3 7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C-6 alkyl or halogen), trick 4)alkylsilyl(C 6)alkylthio, phenylthio (where the phenyl group is optionally substituted by one or more of C-6 alkyl, C-6 alkoxy, C-6 haloalkyl, CN, nitro or halogen), C-6 alkylsulfonyl, C-6 haloalkylsulfonyl, C'-6 alkylsulfinyl, C'-6 haloalkylsulfinyl, phenylsulfonyl (where the phenyl group is optionally substituted by one or more of C-6 alkyl, C-6 alkoxy, C-6 haloalkyl, CN, nitro or halogen), twitch 4)alkylsilyl, phenyldi(C 4)alkylsilyl, (C'4)alkyldiarylsilyl, triphenylsilyl, C3 '0 alkylcarbonyl, HO2C, C3 0 alkoxycarbonyl, aminocarbonyl, C'-6 alkylaminocarbonyl, di(C' 6 alkyl)-aminocarbonyl, N-(C' 3 alkyl)-N-(C' 3 alkoxy)aminocarbonyl, C-6 alkylcarbonyloxy, phenylcarbonyloxy (where the phenyl group is optionally substituted by one or more of C-6 alkyl, C-6 alkoxy, Cat 6 haloalkyl, CN, nitro or halogen), di(C 6) alkylaminocarbonyloxy, phenyl (itself optionally substituted by one or more of C'-6 alkyl, C'-6 alkoxy, C'-6 haloalkyl, CN, nitro or halogen), naphthyl (itself optionally substituted by C-6 alkyl or halogen), heteroaryl (itself optionally substituted by C'-6 alkyl or halogen), heterocyclyl (itself optionally substituted with C,-6 alkyl or halogen), phenyloxy (where the phenyl group is optionally substituted by substituted by one or more of C'-6 alkyl, C-6 alkoxy, C-6 haloalkyl, CN, nitro or halogen), naphthyloxy (where the naphthyl group is optionally substituted by C-6 alkyl or halogen), heteroaryloxy, (where the heteroaryl group is optionally substituted by C-6 alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with Cal 6 alkyl or halogen), amino, C-6 alkylamino, di (C1 6) alkylamino, Cl 6 alkylcarbonylamino and N-(CI 6)alkylcarbonyl-N- (Cl 6) alkylamino.

Preferred substituents on an alkyl, alkenyl or alkynyl moiety include one or more of halogen, nitro, cyano, C3 7 cycloalkyl (itself optionally substituted with C'-6 alkyl or s halogen), C5 7 cycloalkenyl (itself optionally substituted with C'-6 alkyl or halogen), hydroxy, C3 l0 alkoxy, C3 l0 alkoxy(C3 0)alkoxy, C'-6 alkoxy-carbonyl(C3 l0)alkoxy, C3 0 haloalkoxy, phenyl(C 4)alkoxy (where the phenyl group is optionally substituted by C-6 alkyl or halogen), C3 7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C-6 alkyl or halogen), C3 0 alkenyloxy, C3 '0 alkynyloxy, SH, C3 o o alkylthio, C3 l0 haloalkylthio, phenyl(C4)alkylthio (where the phenyl group is optionally substituted by Cl 6 alkyl or halogen), C3 7 cycloalkylthio (where the cycloalkyl group is optionally substituted with Cl 6 alkyl or halogen), tri(C' 4) alkylsilyl(C' 6)alkylthio, phenylthio (where the phenyl group is optionally substituted by C'-6 alkyl or halogen), C-6 alkylsulfonyl, Cl 6 haloalkylsulfonyl, Cl 6 alkylsulfinyl, Cl 6 haloalkylsulfinyl, phenylsulfonyl (where the phenyl group is optionally substituted by C-6 alkyl or halogen), tri(CI 4)alkylsilyl, phenyldi(C4)alkylsilyl, (Cl 4) alkyldiarylsilyl, triphenylsilyl, C3 0 alkylcarbonyl, HO2C, C3 '0 alkoxycarbonyl, aminocarbonyl, C-6 alkylaminocarbonyl, di(C' 6 alkyl)aminocarbonyl, N-(C' 3 alkyl)-N-(C 3 alkoxy)aminocarbonyl, C'-6 alkylcarbonyloxy, phenylcarbonyloxy (where the phenyl group is optionally substituted by Cl 6 alkyl or halogen), di(C, 6)alkylaminocarbonyloxy, phenyl (itself optionally substituted by C-6 alkyl or halogen), heteroaryl (itself optionally substituted by C'-6 alkyl or halogen), heterocyclyl (itself optionally substituted with Cl 6 alkyl or halogen), phenyloxy (where the phenyl group is optionally substituted by C'-6 alkyl or halogen), heteroaryloxy, (where the heteroaryl group is optionally substituted by C-6 alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C-6 alkyl or halogen), amino, C-6 alkylamino, di(C 6) alkylamino, Cl 6 alkylcarbonylamino and N(C' 6)alkylcarbonyl-N-(C 6)alkylamino.

More preferred substituents on an alkyl, alkenyl and alkynyl moiety include one or more of halogen, nitro, cyano, C3 7 cycloalkyl (itself optionally substituted with C'-6 alkyl or halogen), hydroxy, C3 0 alkoxy, C3 0 alkoxy(C3 0)alkoxy, Cl 6 alkoxy-carbonyl (C3 O)alkoxy, C3 0 haloalkoxy, SH, C3 0 alkylthio, C3 lo haloalkylthio, C- 6 alkylsulfonyl, C'-6 haloalkylsulfonyl, Cl 6 alkylsulfinyl, C'-6 haloalkylsulfinyl, phenylsulfonyl (where the phenyl group is optionally substituted by C'-6 alkyl or - 6 halogen), HO2C, C3 lo alkoxycarbonyl, aminocarbonyl, C1 6 alkylaminocarbonyl, heteroaryl (itself optionally substituted by C'-6 alkyl or halogen), heterocyclyl (itself optionally substituted with C-6 alkyl or halogen), phenyloxy (where the phenyl group is optionally substituted by C-6 alkyl or halogen), amino, C-6 alkylamino and disco 6) alkylamino.

Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.

The term heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O. S and N. Examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, lo pyrazole, thiophene, thiazole, oxazole and isoxazole.

The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O. S and N. Examples of such rings include 1,3dioxolane, tetrahydrofuran and morpholine.

When present, the optional substituents on heterocyclyl include C-6 alkyl as well as those optional substituents given above for an alkyl moiety.

Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.

Cycloalkenyl includes cyclopentenyl and cyclohexenyl.

When present, the optional substituents on heteroaryl and aryl rings are selected, independently, from halogen, nitro, cyano, NCS-, C' -6 alkyl, C6 haloalkyl, C' -6 alkoxy-(C 6)alkyl, C2 6 alkenyl, C2 6 haloalkenyl, C2 6 alkynyl, C3 7 cycloalkyl (itself optionally substituted with C'-6 alkyl or halogen), C5 7 cycloalkenyl (itself optionally substituted with C-6 alkyl or halogen), hydroxy, C' o alkoxy, C o alkoxy(C O)alkoxy, tri(C4) alkyl-silyl(C' 6)alkoxy, C -6 alkoxycarbonyl(C O)alkoxy, C o haloalkoxy, aryl(C,4)alkoxy (where the aryl group is optionally substituted), C3 7 cycloalkyloxy 2s (where the cycloalkyl group is optionally substituted with C'-6 alkyl or halogen), C' o alkenyloxy, C' o alkynyloxy, SH, C o alkylthio, C o haloalkylthio, aryl(C4)alkylthio (where the aryl group may be further optionally substituted), C3 7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C'-6 alkyl or halogen), tri(C'4) alkylsilyl(C' 6)alkylthio, arylthio (where the aryl group is optionally substituted), C'-6 alkylsulfonyl, C'- 6 haloalkylsulfonyl, C' 6 alkylsulfinyl, C-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(C' 4) alkylsilyl, aryldi (C 4)alkylsilyl, (C'4)alkyldiarylsilyl, triarylsilyl, C o alkylcarbonyl, HO2C, C O alkoxycarbonyl, aminocarbonyl, C'-6 alkylaminocarbonyl, di(C 6 alkyl)aminocarbonyl, N-(CI 3 alkyl)-N-(C' 3 alkoxy)aminocarbonyl, C1 6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C' 6)alkylamino- carbonyloxy, aryl (itself optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (itself optionally substituted with C'-6 alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C-6 alkyl or halogen), amino, C'-6 alkylamino, di- (C, 6)alkylamino, C'-6 alkylcarbonylamino and N-(C 6)alkylcarbonyl-N-(C' 6)- alkylamino.

ID For substituted phenyl amd heteroaryl moieties it is preferred that one or more substituents are independently selected from halogen, C-6 alkyl, C'-6 haloalkyl, C,-6 alkoxy(C 6)alkyl, C'-6 alkoxy, C,-6 haloalkoxy, C,-6 alkylthio, C'-6 haloalkylthio, C-6 alkylsulfinyl, C-6 haloalkylsulfinyl, C'-6 alkylsulfonyl, C-6 haloalkylsulfonyl, C2 6 alkenyl, C2 6 haloalkenyl, C2 6 alkynyl, C3 7 cycloalkyl, nitro, cyano, CO2H, C'-6 IS alkylcarbonyl, C'-6 alkoxycarbonyl, R33R34N or R3sR36NC(0); wherein R33, R34, R3s and R36 are, independently, hydrogen or C,-6 alkyl.

ln the context of the specification the term halogen is fluorine, bromine, iodine or preferably chlorine; similarly haloalkyl is preferably C'-C6alkyl, more preferably lower alkyl, that is linear or branched and is substituted by one or more, for example in the case of halo-ethyl up to five, halogen atoms, especially fluorine (an example is trifluoromethyl.

Haloalkoxy is preferably C-C6-alkoxy, more preferably lower alkoxy, that is linear or branched and that is substituted by one or more, for example in the case of halo- ethyl up to five, halogen atoms, especially fluorine; trifluoromethoxy and 1,1,2,2 tetrafluoroethoxy are especially preferred.

The moiety attached to the 2-position of the pyridine ring in the compounds of the invention, namely the moiety R3<Cp_RR56 R7 R8 includes 5and 6-membered ring systems, which are common in the art of heterocycles.

Thus examples of the moieties include 2,4-dihydro-pyrazol-3-ones, 2,4dihydro - 8 pyrazole-3-thione, lH-pyrazoles, 2H-pyridazin-3-ones, 4,5-dihydro-2H- pyridazin-3- ones, 1,2-dihydro-pyrazol-3-ones, 1,2-dihydro-pyrazole-3-thione, pyrazolidin-3-one, pyrazolidine-3-thione, 2H-pyridazin-3-thione and 4,5- dihydro-2H-pyridazin-3-thione.

More preferred ring systems for the moiety positioned at the 2-position of the pyridyl ring are those selected from the group comprising, lH-pyrazoles, 2,4-dihydro- pyrazol-3-ones, 1,2-dihydro-pyrazol-3-ones, 4,5-dihydro-2H-pyridazin-3- ones.

The compounds of formula I can form acid addition salts, for example with inorganic acids, such as hydrochloric acid, sulfuric acid or a phosphoric acid, or with suitable organic carboxylic or sulfonic acids, for example aliphatic mono- or di o carboxylic acids, such as trifluoroacetic acid, acetic acid, propionic acid, glycolic acid, succinic acid, maleic acid, fumaric acid, hydroxymaleic acid, malic acid, tartaric acid, citric acid, oxalic acid or amino acids, such as arginine or lysine, aromatic carboxylic acids, such as benzoic acid, 2-phenoxy-benzoic acid, 2-acetoxybenzoic acid, salicylic acid, 4-aminosalicylic acid, aromatic-aliphatic carboxylic acids, such as mandelic acid or cinnamic acid, heteroaromatic carboxylic acids, such as nicotinic acid or isonicotinic acid, aliphatic sulfonic acids, such as methane-, ethane- or 2-hydroxy-ethane-sulfonic acid, or aromatic sulfonic acids, for example benzene-, p-toluene- or naphthalene-2- sulfonic acid.

The pyridine-N-oxides of formula I can form acid addition salts with strong acids, such as hydrochloric acid, nitric acid, phosphoric acid or sulfonic acids, such as benzenesulfonic acid.

Formula I according to the invention shall include all the possible isomeric forms, as well as mixtures, e.g. racemic mixtures, and any mixtures of rotamers.

In view of the close relationship between the compounds of formula I in free form and in the form of their salts, including also salts that can be used as intermediates, for example in the purification of the compounds of formula I or in order to identify those compounds, herein- before and hereinafter any reference to the (free) compounds is to be understood as including also the corresponding salts, where appropriate and expedient.

Among the compounds of formula I according to the present invention the following groups of compounds are preferred. These groups are in any combination those wherein n is O; p is O or 1; - 9 - m is 1, 2 or 3 or m is 1 and Rat is preferably at the 3- or 4- position of the phenyl ring, preferably at the 3- position.

R' is selected from the group comprising halogen, Cal 3 haloalkoxy, CH(OH) R, COR, SO2NRR', CH(NR'R")R, COORa or CONRbRc where Ra, Rb, Rc, R. R', R" are independently H or lower alkyl or Rat is selected from the group comprising chlorine, fluorine, trifluoromethyl, trifluoromethoxy, or 1,1, 2,2-tetrafluoroethoxy, or Rat is 3-chloro; R2 is selected from the group comprising hydrogen, methyl, ethyl, methoxy, 0 methoxymethyl, ethoxymethyl, or R2 is selected from the group comprising hydrogen, methyl or methoxy or R2 is methyl or the ring members CR2R2A are a carbonyl group (C=O) or a thiocarbonyl group (C=S); R2A is selected from the group comprising hydrogen, methyl, ethyl, methoxymethyl, 1S ethoxymethyl, or R2A is hydrogen, methyl, or R2A forms a bond together with Ra; R3 and R4 are independently selected from the group comprising hydrogen, methyl, ethyl, hydroxy, trifluoromethyl, methoxy, methoxymethyl, ethoxymethyl, or R3 and R4 are independently selected from the group comprising hydrogen methyl or methoxy or R3 and R4 are independently hydrogen or methyl or the ring members CR3R4 are a carbonyl group (C=O) or a thiocarbonyl group (C=S); or R4 together with either R9 or Rx forms a bond; 2s Rs, R6, R7, Rs are each independently hydrogen, methyl, trifluoromethyl, R6 and R7 may also be independently chloro, methoxy, ethoxy, diethylamine R7 may also be formyl or the groups R7 and Re together with the carbon atom to which they are attached form a cyclopropyl ring or Rs together with Re form a bond or R5, R6, R7, Re are each independently hydrogen, methyl; R9 is hydrogen or methyl; Ro is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or - 10 ethoxymethyl, or R'o is hydrogen or methoxymethyl.

In a further group of preferred compounds R2, R2A, R3, R4, RS, R6, R7, Rs and R9 independently of each other are hydrogen or methyl; In a further group of preferred compounds R7 is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or ethoxymethyl, more preferably hydrogen or methoxymethyl.

Preferred individual compounds of the formula I are: (3-Chloro-phenyl){4-[2-(3,4,5-trimethyl-pyrazol- 1 -yl)-pyridin-4-yl] - pyrimidin-2-yl} o amine; (3-Chloro-phenyl)- {4-[2-(5-methoxy-3-methoxymethyl-pyrazol- 1 -yl)- pyridin-4-yl] pyrimidin-2-yl} -amine; (3-Chloro-phenyl){4-[2-(5-methoxy-3-methoxymethyl-4-methyl-pyrazol- 1 - yl)-pyridin 4-yl]-pyrimidin-2-yl} -amine; (3 -Chloro-phenyl)- {4- [2-(5 -methoxy-4-methyl-pyrazol- 1 -yl)-pyridin-4- yl] -pyrimidin-2 yl}-amine; (3-Chloro-phenyl)- {4-[2-(5-ethoxy-3,4-dimethyl-pyrazol- 1 -yl)-pyridin-4yl]-pyrimidin 2-yl}-amine; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -5methoxymethyl- 1,4 dimethyl- 1,2-dihydro-pyrazol-3-one; 2-(4{2-[(3-Chloro-phenyl)-methoxymethyl-amino]-pyrimidin-4-yl} -pyridin2-yl)- 1,5 dimethyl- 1,2-dihydro-pyrazol-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1 -ethyl-4, 5-dimethyl- 1,2 dihydro-pyrazol-3 -one; 2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-1,4-dimethyl1,2 dihydro-pyrazol-3 -one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1,5- dimethyl1,2 dihydro-pyrazol-3 -one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -5methoxymethyl-4,4 dimethyl-2,4-dihydro-pyrazol-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl -4,4dimethyl-2,4 dihydro-pyrazol-3 -one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -4,4,5trimethyl-2,4 - 11 dihydro-pyrazole-3 -thione; 5{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -7-methyl-5, 6-diaza spiro[2.4]hept-6-en-4-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -4-ethyl-4, 5-dimethyl-2,4 dihydro-pyrazol-3-one; (3-Chloro-phenyl){4-[2-(5-methoxy-3-methyl-pyrazol- 1 -yl)-pyridin-4-yl] -pyrimidin-2 yl}-amine; 2- {4- [2-(3 -Chloro-phenylamino)-pyrimidin-4-yl] -pyridin-2-yl} -1,4,5 - trimethyl- 1,2 dihydro-pyrazol-3 -one; lo 2-{4-[2-(3-Chloro-phenylamino)pyrimidin-4-yl]-pyridin-2-yl}-4,4,5-trimethyl-2,4 dihydro-pyrazol-3 -one; 2- {4-[2-(3 -Chloro-phenylamino)-pyrimidin-4-yl] -pyridin-2-yl} -1,5 dimethyl- 1,2 dihydro-pyrazol-3 -one; 4,5-Dichloro-2t4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -2H pyridazin-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -6-methyl2H-pyridazin 3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -6-methyl-4, 5-dihydro 2H-pyridazin-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-6-Phenyl-4, 5-dihydro 2H-pyridazin-3 -one; 4-Chloro-2{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyndin-2-yl}-5- ethoxy-2H pyridazin-3 -one; 4-Chloro-2{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-5ethylsulfanyl 2H-pyridazin-3-one; 5-Azido-4-chloro-2{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin- 2-yl}-2H pyridazin-3 -one; 1t4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -2-methylpyrazolidin-3 one; (3 -Chloro-phenyl)- {4- [2-(5 -methoxy-3,4-dimethyl-pyrazol- 1 -yl)- pyridin-4-yl] pyrimidin-2-yl} -amine; - 12 2- {4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -5- methoxymethyl- 1- methyl- 1,2-dihydro-pyrazol-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1,5dimethyl-3-oxo-2,3- dihydro- 1 H-pyrazole-4-carbaldehyde; 5-Chloro-2{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} 4-(oxetan-3-yloxy)-2H-pyridazin-3-one; and lo 4-Chloro-2- {4-[2-(3-chlorophenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -(tetrahydro-furan-2-ylmethoxy)-2H-pyridazin-3 -one.

The compounds according to the invention may be prepared according to methods per se known in the art (this does mean, however, that, where novel compounds are produced, the respective process of manufacture is also novel). The procedures for the preparation of compounds of formula I may be outlined as follows: A) reacting a compound of the formula (II) N1N N/[3

NH

RgN II (or a salt thereof) with p-ketoester of the formula IIl to V under acid catalysed conditions R3 0' R3 ' R3'R

III IV V

wherein R is H or optionally substituted alkyl and the other moieties in II to V have the meanings given for a compound of formula I thus obtaining a compound of the sub formula la - 13 :ó N:1N ( )n Rlo R NN:O R3Ra Ia Compounds of formula II may be prepared by the methods described in WO 01/93682 and illustrated in Synthesis Example 1.

B) reacting a compound of sublormula Ia with a thionating reagent such as for example Lawesson reagent to obtain a compound of subformula Ib 1N ( ) n RIO R N'N?;S R3R3 R4 R7 Ib C) compounds of sub-formula Ia and Ib can be mono- or bis-alkylated to form compounds of structure I wherein p is O and all the other moieties have the lo meanings given for a compound of formula I D) reacting a compound of the formula II (or a salt thereof) ó1N / Rio

NH

RgN II with a substituted acrylate of formula VI R2A := <WAR R2 R7

VI - 14

or with an alkyl propiolate of formula VII o R2

O-R VII

thus obtaining a compound of subformula Ic wherein the moieties have the meanings given for a compound of formula I ó1 /[(R')m R2A oB Ic E) Conversion of the C=0 group into the corresponding C=S group in subformula Ic can be achieved by reacting Ic with a thionating reagent such as e.g. Lawesson reagent thus producing compounds of subformula Id IN - 1N/[3 kN<R2 SR8 R7 Id F) compounds of subformula Ic and Id can be alkylated to form compounds of structure I wherein p is 0, R3 is optionally substituted alkoxy or optionally substituted alkylthio and all the other moieties have the meanings given for a compound of formula I G) reacting a compound of the formula II (or a salt thereof) - 15 1N/ó3 (0)/ RIO

NH

R9N II with a substituted 1,3 dicarbonyl compound of formula VIII

O O R2/R3

R7 VIII H) reacting a compound of the formula II (or a salt thereof) 7 1N (0)/ RIO

NH

R9N II with a 1,4 dicarbonyl compounds of formula IX or X wherein R is H or optionally

O O O O

R3 R3

IX X

lo I) reacting a compound of the formula I.6 (or a salt thereof) (Rl)m3/ ! 'R3 Cl I.6 With a nucleophile to form compounds of formula I Compounds of forumla 1.6 are prepared by the methods of W Davey and D J Tivey, J - 16 Chem Soc 1958, pl230 and illustrated in Example 7.

J) reacting a compound of the formula XI (or a salt thereof) with a cyclic hydrazine system of formula XII in the presence of a base and a metal catalyst, such as palladium(II) or palladium(O) complexes commonly used for Buchwald -Hartwig aminations R'o,:CI H (R')m 3/ No R37:Cp-R5 Xl Xl1 The R group moieties in compounds VIII, IX, X, XI and XII are as for those defined for compounds of formula I. Compounds of formula III to XII inclusive are known compounds or may be lo prepared by compounds known processes.

The reaction types A to J and additional methods which can be applied per se or as analogous procedures for the synthesis of compounds of formula I are described for

example in:

For 5-membred heterocylces: J. Bernstein; et al.; J. Am. Chem. Soc. 1947, 69, 1157; H. Priewe, A. Poljak; Chem. Ber. 1955, 88, 1932; Patent Application CH 77- 10606 19770831 (1982); EP 0 680 954 A2; For 6 membred heterocycles Francis, John E.; Doebel, Karl. J.; Schutte, Paula M. Bachmann, Ernst F. Can. J. Chem. 1982, 60, 1214-1232. Sauter, Fritz; Stanetty, Peter; Blaschke, Alfred; Vyplel, Hermann J. Chem Miniprint, 4, 1981, 1087-1096. Mikhailovskii, A. Chem. Hetreocycl. Compd.

(Engl. Trans.), 1998, 34, 2, 163-166. J. Med. Chem. 1999, 42, 6, 10881099. Krutosikova, Alzbeta; Dandarova, Miloslava; Konecny, Vaclav; Collect.

Czech.Chem.Commun.; EN; 55; 11; 1990; 2707-2714.

Benjamin, Louis E. Earley James V. Gilman Norman W. J. Heterocyclic. Chem. 1986, 23, 119- 124. . Patent, Chem. Fabr. Schering, DE 406214. Gregory; Wiggins; - 17 J.Chem.Soc.; 1949; 2546, 2549. Lancelot, Jean-Charles; Robba, Max; Chem.Pharm.Bull.

36; 7; 1988; 2381-2385.

Example on Phenylhydrazine: Bourel, Line; Tartar, Andre; Melnyk, Patricia; TELEAY; Tetrahedron Lett.; 37; 24; 1996; 4145-4148. Sawhney, S. N., Bhutani Sanjay, Vir, Indian J.Chem.Sect.B; 26, 5; 1987, 348-350. P. Coudert, J. Couquelet, P. Tronche J. of Heterocyclic. Chem. 1988, 25, 799.

The chloro atoms of formula I.6 can be substituted by aryl groups under palladium catalysed conditions according to procedures described in: Bert U. W. Maes, Omar'kyek, Janez Komrlj, Guy L. F. Lemiere, Eddy Esmans, Jef Rozenski, Roger A. Dommisse and 0 Achiel Haemers Tetrahedron, 2001, 57(7), 1323-1330.

B-Ketoesters of formula III - V are known or can be prepared according to procedures described in: Hyoung R.K. Synlett 1998, 789-791; Freskos J.N. Tetrahedron letters, Vol. 35, No. 6, pp. 835-838 (1994); J. Chem. Soc., Perkin Trans. 1, (4), 839-61 (1988); Bull. Soc. Chim. Belg., 94(7), 449 56 (1985); Collins D.J. Aust. J. Chem., 43, 617-22 (1990); Procedures for the alkylation of compounds of the subformula la to Id are described in the experimental section using Williamson conditions.

Conversion of C=0 groups (in Ia and Ic) into C=S groups (subformulas Ib and Id) is described in the experimental section using Lawesson reagent under standard conditions or according to procedures given in Ley, Steven V.; Leach, Andrew G.; Storer, R. Ian. J. Chem. Soc., Perkin Trans. 1 (2001), (4), 358-361.

Procedures for the palladium catalysed C-N linkage reaction (BurchwaldHartwig amination) of compounds of formula XI with cyclic hydrazine ring systems of formula XII are given in the experimental part and are described in PCT/IB01/02821.

The invention relates to compositions which comprise a compound of formula I, or a salt thereof, as an active component, in particular plantprotecting compositions, and also to their use in the agricultural sector or related areas.

Active compounds of the formula I are used in the form of compositions which may contain additional active compounds. These additional active compounds may be either fertilizers, trace element-supplying agents or other preparations which influence - 18 plant growth. It is also possible, in this context, to use selective herbicides, such as insecticides, fungicides, bactericides, nematicides or molluscicides, or mixtures of several of these preparations, additionally, where appropriate, together with excipients, surfactants or other administration-promoting additives which are customary in s formulation technology (designated collectively as carrier materials herein).

Suitable excipients and additives may be solid or liquid and are those substances which are appropriate in formulation technology, for example natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickening agents, binding agents or fertilizers.

lo A preferred method for applying an agrochemical composition comprising a compound of formula I is administration to the leaves (foliar application). The frequency and rate of administration depend upon the risk of infestation by the corresponding pathogen. The compounds of formula I can, however, also penetrate the plant through the roots via the soil (systemic action). If the locus of the plant is impregnated with a liquid formulation or if the substances are introduced in solid form into the soil, e.g. in the form of granules (soil application). In paddy rice crops, such granules can be applied in metered amounts to the flooded rice fields. In order to treat seeds, the compounds of for mula I can, however, also be applied to the seeds (coating), either by impregnating the grains or tubers with a liquid formulation of the active ingredient, or by coating them with a solid formulation.

Advantageous rates of application are in normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg of a.i.lha, especially from g to 600 g a.i./ha. When the compound are used as seed dressings, dosages of from 10 mg to 1 g of active ingredient per kg seed are advantageous employed. The agrochemical 2s compositions generally comprise 0.1 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant and O to 25% by weight, preferably 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further auxiliaries, such as fertilizers and other active ingredients for obtaining special desirable biological effects.

The compositions comprising a compound of formula I may be used preventatively and/or curatively in the sector of agronomics and related technical areas as - 19 active ingredients for controlling plant pests. The active ingredients of formula I in the compositions according to the invention are notable for their good activity even at low concentrations, for their good plant tolerance and for their environmentally friendly nature. They have very advantageous, especially systemic, properties and may be used to protect a plurality of cultivated plants. Using the active ingredients of formula I on plants or plant parts (fruit, flowers, leaves, stems, tubers, roots) of various crops, the pests appearing can be controlled or destroyed, whereby the parts of plants which grow later also remain protected, e.g. from phytopathogenic microorganisms.

The compositions comprising a compound of formula I may additionally be used lo as a dressing to treat seeds (fruits, tubers, corms) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil.

The compounds I are effective for example against the following classes of related phytopathogenic fungi: Fungi imperfect) (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia); Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).

Target crops for the plant-protecting usage in terms of the invention are for example the following plant cultivars: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pome, stone and berry fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas, soya); oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa, peanut); cucumber plants (squashes, cucumber, melons); citrus fruits (oranges, lemons, grapefruits, mandarines); vegetables (spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes, paprika); laurels (avocado, cinnamonium, camphor) and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamental plants.

Further areas of application for the compositions comprising the active ingredients according to the invention are the protection of stores and material, where the storage matter is protected against putrescence and mould.

Furthermore the fungicidal activity allows the compositions according to present invention to be employed in controlling fungi in related areas, e. g. in protection of technical materials, including wood and wood related technical products, in food storage - 20 and in hygiene management.

The compositions comprising a compound of formula I are formulated with customary excipients in formulation techniques. To this end, they are conveniently processed in known manner e.g. into emulsion concentrates, coatable pastes, directly sprayable or diluable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granules, e.g. by encapsulation into for example polymeric materials. As with the type of medium, the application processes, such as spraying, atomizing, dusting, scattering, coating or pouring are similarly chosen according to the desired aims and the prevailing conditions.

ID Suitable substrates and additives may be solid or liquid and are useful substances in formulation techniques, e.g. natural or regenerated mineral substances, dissolving aids, dispersants, wetting agents, tackifiers, thickeners or binding agents.

The compositions comprising a compound of formula I may be mixed with further active ingredients, e.g. fertilizers, ingredients providing trace elements or other active ingredients used in the plant protection science, especially further fungicides. In doing so, in some cases synergistic enhancement of the biological effects may occur.

Preferred active ingredients advantageous as additives to the compositions comprising the active ingredient of formula I are: Azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazo l e, diniconazole, epoxiconazole, fenbuconazol e, fluquinconazo le.

flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymi done, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolani l, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, - 21 SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-pderivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-Smethyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyfluDenamid, 0 cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

One preferred method of application of a composition comprising an active ingredient of formula I or of an agrochemical composition containing at least one of these active ingredients is foliar application. The frequency and amount of application depend on the severity of the attack by the pathogen in question. However, the active ingredients I may also reach the plants through the root system via the soil (systemic action) by drenching the locus of the plant with a liquid preparation or by incorporating the substances into the soil in solid form, e.g. in the form of granules (soil application). In rice cultivations, these granules may be dispensed over the flooded paddy field. The compounds I may however also be applied to seed grain to treat seed material (coating), whereby the grains or tubers are either drenched in a liquid preparation of the active ingredient or coated with a solid preparation.

The compositions are produced in known manner, e.g. by intimately mixing and/or grinding the active ingredient with extenders such as solvents, solid carriers and optionally surfactants.

Favourable application rates are in general 1 g to 2 kg of active substance (AS) per hectare (ha), preferably 10 g to 1 kg AS/ha, especially 20 g to 600 g AS/ha. For usage - 22 as a seed dressing, it is advantageous to use dosages of 10 mg to 1 g active substance per kg of seed grain.

While concentrated compositions are preferred for commercial usage, the end user normally uses diluted compositions.

Formulations may be prepared analogously to those described for example in

Examples:

The subsequent examples are intended to illustrated the invention, without however limiting the scope thereof.

Synthesis Example 1: (3-Chloro-phenvl!-[4-(2-hvdrazino-pvridin-4-vl!pVrimidin-2-vll a_ I f H () Cl A mixture of (3-chloro-phenyl)-[4-(2chloro-pyridin-4-yl)-pyrimidin-2-yl]-amine (4.8g, 0.015mol) in hydrazine (20ml, 0.41mol) is reflexed for 90 minutes. The reaction is poured into ethanol (300ml) with efficient stirring. The resulting precipitate is filtered with suction to yield the title compound, m.p. 201-203 C.

Svnthesis Example 2: 2-14-[2-(3-Chloro-phenvlamino!-pvrimidin-4-vl]pyridin-2-ylI -methyl-2,4-dihvdro-pyrazol-3 -one <\N'N MAN NCI Nit H (1l) A mixture of (3-Chloro-phenyl)-[4-(2-hydrazinopyridin-4-yl)-pyrimidin-2-yl]-amine (3.14g, 0.01 Omo]) and Methyl acetoacetate (1.28g, 0.01 lmol) in EtOH (30ml) and Acetic acid (30ml) is stirred at reflux for one hour. At room temperature the resulting precipitate is filtered with suction to yield the title compound,(3.50g, 92%) m.p. 149-150 C.

Synthesis Example 3:

A mixture of 2- {4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -5-methyl 2,4-dihydro-pyrazol-3-one (3.42g, 0.009mol), iodomethane (2.52g, 0.018mol) and potassium carbonate anhydrous (3.78g, 0.027mol) in DMF (30ml) is stirred at room temperature for three hours. After stirring the resulting is partitioned between ethyl - 23 acetate and water. The organic phase is separated, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue is purified twice by silicagel chromatography to give all possible Isomers of the title compounds llla to lllf. Illa (0.1 Og, 2.8%)m.p. 185-188 C, 11lb (0.29g, 8.1%) m.p. 163-166 C, lllc (0.52g, 14.1%) m.p. 192-194 C, llld (0.53g, 14.4%) m.p. 89-94 C, llle (0.29g, 8.0%) m.p. 149-150 C, lllf (0.1 1 g, 3.0%) m.p. 149-1 50 C, lo SYnthesis Example llla: 2-14-[2-(3Chloro-phenvlamino!-pyrimidin-4-YI]-pYridin 2-YI -4, 5 -dimethvl-2,4-dihYdro-pYrazol-3 -one N 1NT3\CI (Illa) Synthesis Example Illb: 2-14-r2-(3-Chloro-phenvlamino!-pyrimidin-4-yl]- pyridin 2-vll-4,4.5-trimethYI-2,4-dihYdro-pyrazol-3-one N W1NCI

N H

(Illb) SYnthesis Example Illc: 2-4-[2-(3-Chloro-phenylamino!-pvrimidin-4yl]-pyridin 2-YI) - 1,5-dimethYl- 1,2-dihYdro-pvrazol-3-one ó ,N1N/óCI

N H

(IIIC) Svnthesis Example Illd: 2-4-[2-(3-Chloro-phenylamino!-pyrimidin-4vl]-pyridin 2-yl -1.4.5 -trimethyl- 1,2-dihydro-pyrazol-3-one - 24 NN.:'N'lN/CI (Ilid) Synthesis Example Ille: (3-Chloro-phenyl)-t4-[2-(5-methoxy-3-methyl-pyra yl!-pyridin-4-yl] -pYrimidin-2-yl} -amine N NJ3 (Ille) Synthesis Example lllf: (3-Chloro-phenyl)-14-[2-(5-methoxY-3.4-dimethyl- pvrazol- 1 -yl!-pyridin-4-yl]-pYrimidin-2-yl} -amine NlNCI! N H (Illf)

Synthesis Example 4:

SYnthesis Example IVb: 2-14-[2-(3-Chloro-phenylamino!-pyrimidin-4-yl]pyridin 2-yl} -4.4.5-trimethYl-2.4-dihydro-pYrazole-3 -thione N ó1NJ3\CI N. H (IVb) A mixture of 2- {4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]pyridin-2-yl} -4,4,5 trimethyl-2,4-dihydro-pyrazol-3-one (0.21g, 0. 0005mol) and Lawesson reagent (0.22g 0.0005mol) in toluene (3ml) is stirred at 1 00 C for one hour. After cooling the resulting - 25 solution is directly purified by silicagel column chromatography to the title compounds (IVb) (0.19g, 88.1%) m.p. 167-168 C,

Svnthesis Example 5:

Synthesis Example V: 1 - 14-[2-(3-Chloro-phenylamino!-pvrimidin-4-Yl]pyridin-2-YlI 4,5-dihydro-lH-pYrazol-3-ol ON,N,0.N1 IN/óCI To a mixture of (3-Chloro- phenyl)-[4-(2-hydrazino-pyridin-4-yl)-pyrimidin-2-yl]-amine (7.82g, 0.025mo]) and Methyl acrylate (2.58g, 0.030mol) in tert BuOH (80ml) is added lo Potassium tert-butoxyde (5.6g, 0.05mol) in portions at 25 C. After stirring for two hours the resulting brown solution is poured in water (500ml), acidified with acetic acid and partitioned between ethyl acetate and water. The organic phase is separated, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue is purified by crystallizing from acetone. The resulting precipitate is filtered with suction to yield the title compound. (1.55g, 16.9%) m.p. 222-226 C.

SYnthesis Example 6:

A mixture of 1 - {4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2yl} -4,5 dihydro-lH-pyrazol-3-ol (0.734g, 0.0020mol), iodomethane (1751, 0.0028mol) and potassium carbonate anhydrous (0.497g, 0.0036mol) in acetonitrile (4ml) and DMF (2ml) is stirred at 45 C for seven hours. After stirring the resulting is partitioned between ethyl acetate and water. The organic phase is separated, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue is purified by silicagel chromatography to give both possible Isomers of the title compounds.

Vla (0.192g, 25.2%) mp. 143-144 C Vlb (0.036g, 4.7%) mp. 202-205 C SYnthesis Example Vla: 1 - [4-2-(3-Chloro-phenvlamino!-pYrimidin-4-vl]pyridin 2-vll -2-methvl-pYrazolidin-3-on /N INJC - 26 Synthesis Example Vlb: (3- Chloro-phenyl!-4-[2-(3-methoxy-45-dihydro-pyra 1 -yl!-pyridin-4-yl]-pyrimidin-2-yl3 -amine N' ó1N INCI

N H

Synthesis Example 7:4,5-Dichloro-2-{4-[2-(3-chloro-phenylamino)-pyrimidin4-yl]- pyridin-2-yl 3 -2H-pyridazin-3 -one 10:NCI

ON-N of \>

To a suspension of (3-Chloro-phenyl)-[4-(2-hydrazino-pyridin-4-yl)pyrimidin-2-yl] amine (5g) in acetic acid (80 mL) was added 2.8g of Mucochloric acid. The mixture was heated at 125 C for 4h. The solvent was concentrated and the crude was poured into water (500mL). The suspension was neutralised by addition of solid potassium carbonate until pH 7. The aqueous phase was extracted with ethyl acetate (3x 200 mL). The organic phases were combined, dried over MgS04, and concentrated. Flash silica chromatography, eluting with ethyl acetate-tetrahydrofuran (1-0 to 1 - 1), afforded the title compound as a solid (3.1 la, 44%). Mp 238-240 C, IH NMR (DMSO-d6) 10.3 (1H, s,NH),8.84(1H,d,5Hz),8.76(1H,d,5Hz),8.42(1H,s),8. 38(1H,s),8.28(1H,dd, 2Hz, 5Hz), 8.04(1H, t, 2Hz), 7.74(1H, dd), 7.62(1H, d, 5Hz), 7.32(1H, t, 8Hz), 7.02(1H, dd, 2Hz, 8Hz).13CNMR (DMSO-d6) 160.3, 160.2, 159.9, 155.5, 153.5, 150.2, 146.6, 141.7,136.7, 136.6, 134.0, 132.9, 130.1, 121.9, 121.1, 118.7, 118.2, 117. 3, 109.3.

SYnthesis Example 8: 2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]pyridin-2-yll-6 methyl-2H-pyridazin-3 -one

NCI - 27

To a suspension of (3-Chloro-phenyl)-[4-(2-hydrazino-pyridin-4-yl)pyrimidin-2-yl]- amine (2g) in acetic acid (40 mL) was acetate (3x 200 mL). ). The organic phase were combined, dried over MgS04, and concentrated. Flash silica chromatography, eluting with ethyl acetate-tetrahydrofuran (1-0 to 1 - 1), afforded the title compound as a solid (1.39g, 55%). Mp 187-189 C, 1H NMR (DMSO-d6) 9.8 (1H, s, NH), 8.86 (1H, d, 5Hz), 8.80 (1H, d, 5Hz), 8.35 (1H, s), 8.28(1H, dd, 2Hz, 5Hz), 8.14 (1H, t, 2Hz) , 7.73 (1H, m), 7.7.48(1H, d, 10Hz), 7.36(1H, t, 8Hz), 7.14(1H, d, 10Hz), 7.08(1H, dd, lHz, 7Hz), 2.39 (3H,s), 13CNMR (DMSO-d6) 160.8, 160.5, 160.3, 159.0, 154.8, 150.5, 146.7, 145.4, 142.2, 135.4, 133.3, 130.8, 130.5, 121.5, 119.2, 118.6, 117.7, 109.6,20. 58.

SYnthesis Example 9:2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]pyridin-2-yl}-6 methyl-4,5 -dihydro-2H-pyridazin-3 -one :NCI

N N-N

To a suspension of (3-Chloro-phenyl)-[4-(2-hydrazino-pyridin-4-yl)pyrimidin-2-yl] amine (2g) in n-Butanol (40 mL) was added of 0.744g of levulinic acid. The mixture was heated at reflux. After 3h, the mixture was cooled at 0 C and the 4-( {4-[2-(3-Chloro phenylamino)-pyrimidin-4-yl] -pyridin-2-yl}-hydrazono)-4-methyl-butyric acid (1.92g, 73%) was recovered by filtration. Mp 218-220 C, 1H NMR (DMSO-d6) 12.1 (1H, OHacid), 9.93 (1H, s, NH), 9.48 (1H, s, NH), 8.64 (1H, d, 5Hz), 8.24 (1H, d, 5Hz), 8.0 (lH,s),7.76(2H,m),7.46(1H,d,5Hz),7.38(1H,dd,2Hz,5Hz),7.30(1H,t,8Hz),6.98 28 (1H, dd, lHz, 8Hz), 2.51 (4H, s), 1.92 (3H, s), 13C NMR (DMSO-d6 176.2, 164.6, 161.6, 161.2, 150.5, 150.1, 147.5, 144.0, 134.9, 132.1, 122.97, 120.13, 119.2, 113.7, 111.1, 105.9, 35.33 (CH2), 32.56(CH2), 18.09 (CH3), MS (ES-) 409 (M-1, 100), 819 (2M-1, 30). The 4-({4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2- yl} s hydrazono)-4-methyl-butyric acid (1.5g) was dissolved in acetic acid (40 mL). The solution was stirred at 110 C for 3h then the solution was poured in a mixture of water and ice (250 mL) and neutralised with a solution saturated of sodium hydrogenocarbonate until pH 7. The mixture was extracted with ethyl acetate (3x100 mL). The organic phase were combined, dried over MgS04, and concentrated. Flash 0 silica chromatography, eluting with ethyl acetate-tetrahydrofuran (3-1), afforded the title compound as a solid (0.7263g, 51%). Mp 189-192 C, 1H NMR (DMSO-d6) 10.07(1H, NH), 8.73 (1H, d, 5Hz), 8.69 (1H, d, 5Hz), 8.16 (1H, s), 8.06 (2H, m), 7.73 (1H, dd, 3Hz, 10Hz), 7.60(1H, d, 5Hz), 7.31 (1H, t, 8Hz), 7.03(1H, dd, 3hz, 8Hz), 2.63 (4H, m), 2.07 (3H, s). 13C NMR (DMSO-d6) 165.3, 160.3, 159.6, 159.3, 154.9, 153.9, 149. 0, 141.1, 132.5, 129.7, 120.7, 119.2, 117.8, 117.6, 116.7, 108.66, 26.4, 25.3, 22.0. MS(ES+)393 (MH+, 100), 785 (2MH+, 60).

SYnthesis Example 10: 2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]pyridin-2-yl} 6-Phenyl-4,5-dihydro-2H-pyridazin-3-one

NCI

N-N G

To a suspension of (3-Chloro-phenyl)-[4-(2-hydrazino-pyridin-4-yl)pyrimidin-2-yl] amine (2g) in n-Butanol (40 mL) was added of 1.14g of 3benzoylpropionic acid. The mixture was heated at reflux. After 3h, the mixture was cooled at 0 C and the 4-({4-[2 (3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-hydrazono)-4-phenylbutyric acid (2.19g, 72%) was recovered by filtration. Mp 144-146 C, 1H NMR (DMSO-d6) . 12.0 (lH,OH), 10.4(1H,s,NH), 10.1 (lH,s,NH),8.77(1H,d,5Hz), 8.42 (1H,d,5Hz)8. 12 - 29 (1H, s), 8.06(1H, s), 7.80(3H, m), 7.6 (1H, d, 5Hz) 7.53 (1H, d, SHz), 7. 45 (3H, m), 7.34 (1H, t, 8Hz), 7.08 (1H, m) 3.4 (2H, m), 2.95 (2H, m), MS (ES+) 473 (MH+, 100), . MS (ES-) 471 (M-l, 100). To a solution of 4-({4-[2-(3-Chloro-phenylamino)- pyrimidin-4 yl]-pyridin-2-yl}-hydrazono)-4-phenyl-butyric acid (0.48g) in tetrahydrofuranne (40 mL) was additionned N. N'-dicyclohexylcarbodiimide (0.23g) and 1-Hydroxybenzotriazole (O.1401g). The solution was stirred at reflux for 2h then the solvent was evaporated. The crude was chromatographied, elating with ethyl acetate to gave the title compound as a solid (0.3366g, 78%). Mp 165-167 C, 1H NMR (CDC13) 9.6 (lH,s, NH), 8.76 (1H, d, 5Hz), 8.59 (1H, d, 5Hz), 8.21 (1H, s), 7.86 (4H, m), 7.44 (4H, m), 7. 26(2H, m), 7. 01 (1H, m), 3.18 (2H, t, 8Hz), 2.87 (2H, t, 8Hz). 13C NMR (CDC13) 166.3, 162. 4, 160.4, 159.8, 154.8, 152.9, 150.1, 146.7, 140.9, 135.7, 134.9, 130.5, 130.3, 129. 0, 126.7, 122.9, 120.1, 119.6, 118.8, 117.55, 109.6, 28.4, 23.6. MS (ES+) 455 (MH+, 100), 909 (2MH+, 10).

Synthesis Example 11: 4-Chloro-2-{4-[2-(3-chloro-phenylamino)-pyrimidin-4yl] pyridin-2-yl 3 -5-ethoxy-2H-pyridazin-3 -one N,,N,:<CI

N Cl O:

To a suspension of 4,5-Dichloro-2- {4-[2-(3-chloro-phenylamino)-pyrimidin4-yl] pyridin-2-yl}-2H-pyridazin-3-one (0.3g) in ethanol (10 mL) was added of 0.220 mg of potassium carbonate. The mixture was heated to reflux for 4h. The suspension was poured into water (50 mL) and extracted with ethyl acetate (2xlOOmL). The organic phase were combined, dried over MgSO4, and concentrated. Flash silica chromatography, eluting with ethyl acetate-hexane (9: 1), afforded the title compound as a solid (0.130g, 35%). Mp 196-198 C,, 1H NMR (CDC13) 8.80 (1H, d, 3Hz), 8.60 (1H, d, 6Hz), 8.42 - 30 (IH, s), 8.02 (2H, d, m), 7.93 (1H, s), 7.46 (1H, dd, 6Hz, 3Hz), 7.31 (lH, m), 7.29(1H, d, 3Hz), 7.28(1H, s), 4.43 (2H, q, 6Hz), 1.56 (3H, t, 6Hz).

Synthesis Example 12: 4-Chloro-2-{4-[2-(3-chloro-phenylamino)-pyrimidin-4yl]- pyridin-2-yl}-5-ethylsulfanyl-2H-pyridazin-3-one.

NCI

N-N

To a suspension of 4,5-Dichloro-2- {4-[2-(3-chloro-phenylamino)-pyrimidin4-yl]- pyridin-2-yl}-2H-pyridazin-3-one (0.3g) in acetonitrile (10 mL) was added of 0.15 mL of ethylmercaptan and 0.280 mg of potassium carbonate. The mixture was heated to reflux for 2h. The suspension was filtered and the solid was washed with ethyl acetate to gave the title compound (0.220g, 46%).Mp 80-100 C, 1H NMR (DMSO-d6) 8.8 (1H, d, 3Hz), 859 (1H, d, 6Hz), 8.37 (1H, s, NH), 7.98 (1H, d, 6Hz, 3Hz), 7.92 (1H, t, 3Hz), 7.86 (1H, s), 7.46 (1H, d, 9Hz, 3Hz), 7.40 (lH,s), 7.27(2H, m), 7.04(1H, d, 9Hz), 3.12 (2H, q, 6Hz), 1.47 (3H, t, 6Hz).

SYnthesis Example 13: 5-Azido-4-chloro-2- {4-[2-(3 -chloro-phenylamino)pyrimidin-4 yl]-pyridin-2-yl} -2H-pyridazin-3-one. :NCI

N-N o: \) Cl,N

N

N - 31

To a suspension of 4,5-Dichloro-2- {4-[2-(3-chloro-phenylamino)-pyrimidin4-yl] pyridin-2-yl}-2H-pyridazin-3-one (0.3g) in acetonitrile (10 mL) was added of O.O9g of sodium azide. The mixture was heated to reflux for 4h. The suspension was filtered to give the title compound as a solid (0.280g, 95%). Mp 184-186 C, 1H NMR (DMSO-d6) 10.1 (1H, s, NH), 8.75 (1H, d, 6Hz), 8.67 (1H, d, 3Hz), 8.28 (1H, s), 8. 27 (1H, s), 8.18(1H, dd, IHz, 3Hz), 7.97 (1H, m), 7.65 (lH,dd), 7.57(1H, d, 6Hz), 7. 25(1H, t, 9Hz), 6.94 (1H, dd).

SYnthesis Example 14: 5-Chloro-4-cyclopropylamin-2- {4-[2-(3-chlorophenylamino) pyrimidin-4-yl]-pyridin-2-yl}-2H-pyridazin-3-one and 5Cyclopropylamin -4- chloro -2 o {4-[2-(3-chloro-phenylamino)-pyrimidin-4yl]-pyridin-2-yl}-2H-pyridazin-3-one.

NCI NCI

N-N N-N

[> N Cl Cl N A suspension of 4,5-Dichloro-2-{4-[2-(3-chloro-phenylamino)pyrimidin-4-yl]-pyridin 2-yl}-2H-pyridazin-3-one (0.3g) in cyclopropylamine (10 mL) was heated at reflux for 2h. The solvent was evaporated under vacuum. Flash silica chromatography, eluting with ethyl acetate-hexane (1: 1), afforded the 5-Chloro-4- cyclopropylamin-2-{4-[2-(3 chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2- yl}-2H-pyridazin-3-one as a solid (Mp 117-121 C, 0.082g, 26%) and the 5- cyclopropylamin -4- chloro -2-{4-[2-(3- chloro phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -2H-pyridazin-3-one (Mp 90- 100 C, 0.180g, 58%) as a solid.

SYnthesis Example 15: 5-Chloro-4-butanol-2-{4-[2-(3-chloro-phenylamino)pyrimidin 4-yl]-pyridin-2-yl} -2H-pyridazin-3-one. - 32

NCI in,

N N-N O Cl

To a solution of butanol (0.18 mL) in tetrahydrofuran (40 mL) was added a solution of Lithium diisopropylamide (1.5 M, 1.3 mL) at room temperature. The solution was stirred for 15 minutes followed by the addition of 4,5Dichloro-2- {4-[2-(3-chloro s phenylamino)-pyrimidin-4-yl]-pyridin-2-yll2H-pyridazin-3-one (0.7g). The mixture was heated at 85 C for lh. The suspension was poured into brine (200 mL) and extracted with ethyl acetate (3xlOOmL). The organic phase were combined, dried over MgS04, and concentrated under vacuum. Flash silica chromatography, eluting with ethyl acetate cyclohexane (1:1), afforded the title compound as a solid (0.4128g, 55%). Mp 118 0 127 C.

Synthesis Example 1 6: 1 - {4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yll 2-methyl-tetrahydro-pyridazine-3,6-dione.

NCI IN-N/

To a solution of succinic anhydride (2.16g) in chloroform (60 mL) 1.16 mL of methyl hydrazine were added at room temperature. The solution was stirred 2h at room temperature then heated at reflex for lh. The solvent was evaporated. lg of the obtained solid was dissolved in tetrahydrofuran (10 mL) followed by the addition of 1.55g of N,N'dicyclohexylcarbodiimide and l.Olg of 1-hydroxybenzotriazole. The mixture was heated at reflux for 1 h. The mixture was cooled to 0 C and a solution of oxalic acid (0.617g) in methanol was added. The suspension was filtered and the solvent was evaporated. Flash silica chromatography, elating with ethyl acetate-methanol (5%), - 33 afforded the 1-Methyl-tetrahydro-pyridazine-3, 6-dione as a solid (0.4128g, 24%). 0.014g of Pd(dba)3 and xantphos (0. 018g) were dissolved in toluene (2 mL). The mixture was stirred at room temperature for 20 minutes. Then the 1-Methyl-tetrahydro- pyridazine-3,6- dione, the (3-Chloro-phenyl)-[4-(2-chloro-pyridin-4-yl)-pyrimidin-2-yl]- amine (0.2g) and sodium terbutanolate (0.085g) were added. The mixture was heated at reflux for 2h.

The suspension was poured into water (50 mL) and extracted with ethyl acetate (3xlOOmL). The organic phase was separated, dried over MgS04, filtered and concentrated. Flash silica chromatography, eluting with ethyl acetate, afforded the title compound as a solid (0.169g, 65%). Mp 201-204 C.

lo The compounds in the following Tables further illustrate the invention

Table 1

Compounds of the general structure I.1 wherein Rat to R'o, m, n, and p correspond with a line of table A and B I R10 NO i -l N ( )n R2: R3 R2A R7 R8 1.1

Table 2

Compounds of the general structure I.2 wherein R' to Rio, m, n, and p correspond with a line of table A and B2 R10 [:, N R9 -l N ( )n R2: R2A R7 1.2

Table 3

Compounds of the general structure I.3 wherein Rat to Rio, m, n, and p correspond with a line of table A and B3 - 34 R10 [;,N

N ( )n)

R2 R7 I.3

Table 4

Compounds of the general structure I.4 wherein R' to R'o, m, n, and p correspond with a line of table A and B4 R10

N ^ R9

N -l N N R4 ( )n) - R3 R2 R7 I.4

Table 5

Compounds of the general structure I.5 wherein Rat to Rio, m, n, and p correspond with a line of table A and B5 R10

N (0)R3

Table 6

Compounds of the general structure I.6 wherein Rat to R'o, m, n, and p correspond with a line of table A and B6 -

R

N N-N

(O)n o=( \R3 R6 R7 I.6

Table 7

Compounds of the general structure I.7 wherein Rat to Rio, m, n, and p correspond with a line of table A and B7

IRE

IN-N

(O)n o=( \ - R3 R5,) R8 R6 R7 I.7

Table 8

Compounds ofthe general structure I.8 wherein R1 to Rid, m, n, and p correspond with a line of table A and B8 ( 1) m N_N o ( )n -:R5 R7 R8 I.8 lo Compounds of general structure I are any combination of the definitions given in Table A and the appropriate Table B. wherein n, Rio, m and R' correspond with a line of Table A and wherein R2 - R9 and p correspond with a line of the appropriate Table B. - 36

Table A:

No. n Rlo 2-RI 3-RI 4-RI 5-RI 6-RI | 001 0 CH3 H OH H H F 002 0 CH3 H OH H F H 003 0 CH3 CH3 H H H H 004 0 CH3 H C1 H H F 0 CH3 H C1 H H CH3 006 0 CH3 H CH3 Cl H H 007 0 CH3 F H C1 H H 008 0 CH3 H C1 H H H 009 0 CH3 H C(0)H H H H 0 CH3 H CH2OH H H H 011 0 CH3 H CH(OH)CH3 H H H 012 0 CH3 H F H H H 013 0 CH3 H CH3 H H H 014 0 CH3 H H H CF3 H 0 CH3 H H H OCF3 H 016 0 CH3 H N(CH3)2 H H F 017 0 CH3 H SO2N(CH3)2 H H H 018 0 CH3 H H H CONH2 H 019 0 CH3 H H H OCH2C3CH H 0 CH3 H SC4H9 H H H 021 0 H H OH H F H 022 0 H H OH H H F 023 0 H CH3 H H H H 024 0 H H Cl H H F 0 H H Cl H H CH3 026 0 H H CH3 Cl H H 027 0 H F H Cl H H 028 0 H H Cl H H H 029 0 H H C(0)H H H H 0 H H CH2OH H H H 031 0 H H CH(OH)CH3 H H H 032 0 H H F H H H 033 0 H H CH3 H H H 034 0 H H H H CF3 H 0 H H H H OCF3 H 036 0 H H N(CH3)2 H H F 037 0 H H SO2N(CH3)2 H H H 038 0 H H H H CONH2 H 039 0 H H H H OCH2CCH H 0 H H SC4H9 H H H 041 0 CH2OCH3 H OH H H F 042 0 CH2OCH3 H | OH H F H 043 0 CH2OCH3 CH3 H H H H 044 0 CH2OCH3 H Cl H H F 0 CH2OCH3 H Cl H H CH3 046 0 CH2OCH3 H CH3 Cl H H 047 0 CH20CH3 F H Cl H H 048 0 CH2OCH3 H C! H H H 049 0 CH2OCH3 H C(0)H H H H 0 CH2OCH3 H CH2OH H H H 051 0 CH2OCH3 H CH(OH)CH3 H H H 052 0 CH2OCH3 H F H H H

_

053 0 CH2OCH3 H CH3 H H H 054 0 CH2OCH3 H H H CF3 H 0 CH2OCH3 H H H OCF3 H 056 0 CH20CH3 H N(CH3)2 H H F 057 0 CH2OCH3 H SO2N(CH3)2 H H H 058 0 CH2OCH3 H H H CONH2 H 059 0 CH2OCH3 H H H OCH2C3CH H 0 CH2OCH3 H SC4H9 H H H 061 0 CH2OCH3 H OH H H F 062 0 CH2OCH3 H Cl H H H 063 0 CH2OCH3 H C(0)H H H H 064 0 CH2OCH3 H CH2OH H H H 0 CH2OCH3 H CH(OH)CH3 H H H 066 0 CH2OCH3 H F H H H 067 0 CH2OCH3 H CH3 H H H 068 0 CH2OCH3 H H H CF3 H 069 0 CH2OCH3 H H H OCF3 H 0 CH2OCH3 H N(CH3)2 H H F 071 0 CH2OCH3 H SO2N(CH3)2 H H H 072 0 CH2OCH3 H H H CONH2 H 073 0 CH2SCH3 H OH H H F 074 0 CH2SCH3 H Cl H H H 0 CH2SCH3 H C(0)H H H H 076 0 CH2SCH3 H CH2OH H H H 077 0 CH2SCH3 H CH(OH)CH3 H H H 078 0 CH2SCH3 H F H H H 079 0 CH2SCH3 H CH3 H H H 0 CH2SCH3 H H H CF3 H 08 0 CH2SCH3 H H H OCF3 H 082 0 CH2SCH3 H N(CH3)2 H H F 083 0 CH2SCH3 H SO2N(CH3)2 H H H 084 0 CH2SCH3 H H H CONH2 H 0 CH2CH=CH2 H OH H F 086 0 CH2CH=CH2 H Cl H H H 087 0 CH2CH=CH2 H C(0)H H H H 088 0 CH2CH=CH2 H CH20H H H H 089 0 CH2CH=CH2 H CH(OH)CH3 H H H 0 CH2CH=CH2 H F H H H 091 0 CH2CH=CH2 H CH3 H H H 092 0 CH2CH=CH2 H H H CF3 H 093 0 CH2CH=CH2 H H H OCF3 H 094 0 CH2CH=CH2 H N(CH3)2 H H F 0 CH2CH=CH2 H SO2N(CH3)2 H H H 096 0 CH2CH=CH2 H H H CONH2 H 097 0 CH2C3CH H OH H H F 098 0 CH2C3CH H Cl H H H 099 0 CH2C3CH H C(0)H H H H O CH2C$:CH H CH20H H H H 101 0 CH2CCH H CH(OH)CH3 H H H 102 0 CH2CúCH H F H H H 103 0 CH2C3CH H CH3 H H H 104 0 CH2CúCH H H H CF3 H 0 CH2CCH H H H OCF3 H 106 0 CH2C3CH H N(CH3)2 H H F 107 0 CH2C3CH H SO2N(CH3)2 H H H 108 0 CH2C3CH H H H CONH2 H 109 O CH2C$:CH H OH H H F 0 CH2Ph H Cl H H H 111 0 CH2Ph H C(0)H H H H 112 0 CH2Ph H CH2OH H H H 113 0 CH2Ph H CH(OH)CH3 H H H 114 0 CH2Ph H F H H H 0 CH2Ph H CH3 H H H 116 0 CH2Ph H H H CF3 H 117 0 CH2Ph H H H OCF3 H 118 0 CH2Ph H N(CH3)2 H H F 119 0 CH2Ph H SO2N(CH3)2 H H H 0 H H Cl CH3 H H 121 0 H H Cl CH3 H H 122 0 H H Cl OCH3 H H 123 0 H H F H F H 124 0 H H Cl H Cl H 0 H H Br H H H - 39

Table B-1 R10

N

-l _N ( )n R? g R3 R2A R7 R3 I.1 NO. R2 | R2A R3 R7 Rg R9 01 C=0 CH3 CH3 CH3 02 C=S CH3 CH3 H 03 C=0 CH3 CH3 CH2CH3 = 04 C=0 CH3 CH2-4 H2 C=0 CH3 CH3 Ph 06 C=S CH3 CH3 CH3 = 07 C=0 H CH3 CH3 08 C=0 CH2OCH3 CH3 CH3 = 09 C=0 CH3 CH3 CH2Ph C=0 CH3 CH2CH2OC(0)CHg H 011 C=0 CH3 CO2Et H = 012 C=0 CH3 CHO H 013 C=0 CH3 CF3 H 014 C=0 CF3 CF3 H C=0 CF3 H H 016 C=0 CH2CH3 H H 017 C=0 CH2CH3 CH3 H 018 C=0 n-C4H9 CH3 H 019 C=0 Ph CH3 H _ C=S n-C4H9 CH3 H = 021 C=S CH3 CH3 CH2CH3 022 C=S CH3 CH2- H2 023 C=S CH3 CH3 Ph 024 C=S H CH3 CH3 _ C=S CH20CH3 CH3 CH3 = 026 C=S CH3 CH3 CH2Ph _ 027 C=S CH3 CH2CH2OC(0)CH3 H 028 C=S CH3 CO2Et H 029 C=S CH3 CHO H = C=S CH3 CF3 H 031 C=S CF3 CF3 H 032 C=S CF3 H H _ 033 C=S CH2CH3 H H 034 C=S CH2CH3 CH3 H 40 C=S Ph CH3 H 036 C=0 CH3 CO2Et CH3 037 C=0 CH3 CHO CH3 = 038 C=0 CH3 CF3 CH3 039 C=0 CF3 CF3 CH3 C=0 CF3 CH3 H = 041 C=0 CH2CH3 CF3 H 042 C=0 CH2CH3 CH3 H 043 C=S CH3 CO2Et CH3 = 044 C=S CH3 CHO CH3 C=S CH3 CF3 CH3 046 C=S CF3 CF3 CH3 = 047 C=S CF3 CH3 H 048 C=S CH2CH3 CF3 H 049 ( =S CH2CH3 CH3 H = H H OCH3 H H 051 H H OCH2Ph H H 052 H H OCH2CCH H H 053 H H a2a H _

Table B-2 R10 <,N NR9

/N N iR3 ( )n R2 R7 I.2 No. R2 I R2A R3 R7 R9 01 C=0 CH3 C(O)2Me CH3 02 C=0 CH3 CH3 CH3 03 C=0 CH3 H CH3 04 C=0 CH3 CHO CH3 C=0 H CH3 CH3 06 C=0 CH3 CH3 CH2-CH3 07 C=0 CH3 CH3 CH2PH 08 C=0 CH3 H CH3 09 C=0 CH2OCH3 CH3 CH3 C=0 CH3 CH3 Ac 011 C=0 CH2OCH3 H CH3 012 C=S CH3 H CH3 0 3 C=S CH3 C(O)2Me CH3 - 41

_

014 C=S CH3 CH3 CH3 C=S CH3 CHO CH3 016 C=S H CH3 CH3 017 C=S CH3 CH3 CH2-CH3 018 C=S CH3 CH3 CH2PH 019 C=S CH3 H CH3 C=S CH2OCH3 CH3 CH3 021 C=S CH3 CH3 Ac 022 C=S CH2OCH3 H CH3 023 C=0 CH2Ph CH3 CH3 024 C=0 n-C4Hg CH3 CH3 C=0 CH2CH3 CH3 CH2CH3 026 C=0 CH2CH3 CH3 CH3 027 C=0 CF3 n-C4H' CH3 028 C=0 CH2Ph H CH3 029 C=0 n-C4Hg H CH3 C=0 CH2CH3 CH2Ph CH2CH3 031 C=0 CH2CH3 H CH3 032 C=0 CF3 CH3 CH3 033 C=S CH2Ph CH3 CH3 034 C=S n-C4H, CH3 CH3 C=S CH2CH3 CH3 CH2CH3 036 C=S CH2CH3 CH3 CH3 037 C=S CF3 n-C4H' CH3 038 C=S CH2Ph H CH3 039 C=S n-C4H9 H CH3 C=S CH2CH3 CH2Ph CH2CH3 041 C=S CH2CH3 H CH3 042 C=S CF3 CH3 CH3

Table B-3 R10 :,N h

N -1 NN: ( )n /( R2 R7 I.3 No. R2 R3 R7 01 OCH3 CH3 H 02 Oac CH3 CH3 03 OC2H5 CH3 CH3 04 OC2H5 H CH3 - 42

_

OC2H5 CH3 H 06 OC2H, H Ph 07 OC2H5 CH2OCH3 CH3 08 OC2H5 CH20CH3 CH2CH3 09 OH CH2OCH3 CH3 OH CH2OCH3 CH2CH3 011 OH CH2OCH3 H 012 OCH3 H CH3 013 OCH3 CH2OCH3 CH 014 OCH3 CH2OCH3 H OH CH3 CH2CH3 016 OH H CH3 017 CH3 CH3 CH3 018 OAc CH3 H 019 OH CH3 H OCH2Ph CH3 CH3 021 SCH3 CH3 CH3 022 SCH3 CH3 CH2CH3 023 SCH3 CH3 H 024 SCH3 CH3 CH2CH3 SCH3 H H 026 SCH3 CH3 027 CH3 CH3 028 CH3 CH3 CH3 029 CH3 CH3 C(0)2Et CH(CH3)2 CH(CH3)2 H 031 CH3 CH3 Cl 032 H OCH3 H 033 CH2OCH3 H C(O)2Me 034 CH2OCH3 H CONHMe c-C3H5 CH3 H 036 I-C3H7 CH3 C(0)2Et 037 CH3 CH3 Ph 038 CH3 CF3 H 039 H OH H 2,4-F2-Ph C(O)2Me H 041 2,4-F2-Ph CONHMe H 042 SCH3 CH2OCH3 CH3 043 SCH3 CH2OCH3 H 044 SH CH3 CH2CH3 SH H CH3 046 SCH3 CH3 H 047 SCH2Ph CH3 CH3 048 SC2H5 CH3 cH3 049 SC2H5 H CH3 SC2H5 CH3 H - 43 051 SC2Hs H Ph 052 SC2H5 CH2OCH3 1 CH3 053 SC2Hs CH20CH3 CH2CH3

Table B-4 R10

N IR9

( )n RR43 R2 R7 I.4 No. R2 R3 1 R4 R7 R9 01 H C=0 H CH3 02 H O H CH2óC' 03 H C=0 H Benzyl 04 H C=0 H CH2C3CH CH3 C=0 H CH3 06 CH3 C=0 H CH2CH3 07 CH3 C=0 H n-C4H9 08 CH3 C=0 H CH2Ph 09 CH2CH3 C=0 H CH3 CH2CH3 C=0 H CH3 011 Ph C=0 H CH3 012 Ph C=0 H CH2CH3 013 Ph C=0 H Ph 014 Ph C=0 H n-C4H9 H C=S H CH3 016 H C=S H Benzyl 017 H C=S H CH2CúCH 018 CH3 C=S H CH3 019 CH3 C=S H CH2CH3 CH3 C=S H n-C4Hg 021 CH3 C=S H CH2Ph 022 CH2CH3 C=S H CH3 023 CH2CH3 C=S H CH3 024 Ph C=S H CH3 Ph C=S H CH2CH3 026 Ph C=S H Ph 027 Ph C=S H n-C4H9 - 44

Table B-5 R10

N R8

No. R2 R2A R3 I R4 R7 RS R9 01 H H C=0 H H CH3 02 H H C=0 H H,WN CH2CI 03 H H C=0 H H Benzyl 04 H H C=0 H H CH2CSCH CH3 H C=0 CH3 H CH2Ph 06 CH3 H C=0 CH3 H CH2CSCH 07 CH3 H C=0 CH3 H CH2CH=CH2 08 CH3 H C=0 CH3 H CH3 09 CH3 H C=0 CH3 H CH2CH3 CH3 H C=0 H H CH2Ph 011 CH3 H C=0 H H CH2CSCH 012 CH3 H C=0 H H CH2CH=CH2 013 CH3 H C=0 H H CH3 014 CH3 H C=0 H H CH2CH3 CH3 CH3 C=0 H H CH2Ph 016 CH3 CH3 C=0 H H CH2CSCH 017 CH3 CH3 C=0 H H CH2CH=CH2 018 CH3 CH3 C=0 H H CH3 019 CH3 CH3 C=0 H H CH2CH3 CH3 H C=S H H CH2Ph 021 CH3 H C=S H H CH2CSCH 022 CH3 H C=S H H CH2CH=CH2 023 CH3 H C=S H H CH3 024 CH3 H C=S H H CH2CH3 CH3 CH3 C=S H H CH2Ph 026 CH3 CH3 C=S H H CH2CCH 027 CH3 CH3 C=S H H CH2CH=CH2 028 CH3 CH3 C=S H H CH3 029 CH3 CH3 C=S H H CH2CH3 - 45 | 030 | C=0 | H | H | H | H | CH

Table B-6

R \N-N

(O)n 0 R3 R6 R7 1.6 R3 R6 1 R7 1. H H H 2. H Cl Cl 3. H Cl NHCH3 4. H Cl NHBu 5. H Cl N(CH3)2 6. H Cl NBu2 7. H Cl NCH3Bu 8. H Cl NEt2 9. H Cl NEtBu 10. H Cl SCH3 11. H Cl SBu 12. H Cl OCH3 13. H Cl OBu 14. H Cl CF3 15. H Cl OPh 16. H Cl CH2OCH3 17. H Cl OCF3 18. H Cl OCF2CF3 19. H Ph 20. H Cl N3 21. H H I 22. H H CH3 23. H H Bu 24. H H OCH3 25. H H OBu 26. H H SCH3 - 46 27. H H SBu 28. H H NHCH3 29. H H NHBu 30. H H N(CH3)2 31. H H NBu2 32. H H NCH3Bu 33. H H NEt2 34. H H NEtBu 35. H H CF3 36. H H OPh 37. H H. CH2OCH3 38. H H OCF3 39. H H OCF2CF3 40. H H Ph 41. H H N3 42. H CH3 CH3 43. H CH3 Bu 44. H CH3 OCH3 45. H CH3 OBu 46. H CH3 SCH3 47. H CH3 SBu 48. H CH3 NHCH 49. H CH3 NHBu 50. H CH3 N(CH3)2 51. H CH3 NBu2 52. H CH3 NCH3Bu 53. H CH3 NEt2 54. H CH3 NEtBu _ 55. H CH3 CF3 56. H CH3 OPh 57. H CH3 CH20CH3 58. H CH3 OCF3 59. H CH3 OCF2CF3 60. H CH3 Ph 61. H CH3 N3 62. H nBu CH3 63. nBu Bu 64. H nBu OCH3 65. H nBu OBu 66. H nBu SCH3 67. H nBu SBu 68. H nBu NHCH3 69. H nBu NHBu 70. H nBu N(CH3)2 71. H nBu NBu2 72. H nBu NCH3Bu 73. H nBu NEt2 - 47 74. H nBu NEtBu 75. H nBu CF3 76. H nBu OPh 77. H nBu CH2OCH3 78. H nBu OCF3 79. H nBu OCF2CF3 80. H nBu Ph 81. H nBu N3 82. H I H 83. H CH3 H 84. H Bu 85. H OCH3 H 86. H OBu H 87. H SCH3 H 88. H SBu H 89. H NHCH3 H 90. NHBu H 91. H N(CH3)2 H 92. H NBu2 H 93. H NCH3Bu H 94. H NEt2 H 95. NEtBu H 96. H CF3 H 97. H OPh H 98. H CH2OCH3 H 99. H OCF3 H 100. H OCF2CF3 H 101. H Ph H 102. H N3 H 103. H CH3 CH3 104. H Bu CH3 105. H OCH3 CH3 106. H OBu CH3 107. H SCH3 CH3 108. H SBu CH3 109. H NHCH3 CH3 110. H NHBu CH3 111. H N(CH3)2 CH3 112. H NBu2 CH3 113. H NCH3Bu CH3 114. H NEt2 CH3 115. H NEtBu CH3 116. H CF3 CH3 117. H OPh CH3 118. H CH2OCH3 CH3 119. H OCF3 CH3 120. H OCF2CF3 CH3 - 48 121. H Ph CH3 122. H N3 CH3 123. H CH3 nBu 124. H nBu nBu 125. H OCH3 nBu 126. H OBu nBu 127. H SCH3 nBu 128. H SBu nBu 129. H NHCH3 nBu 130. H NHBu nBu 131. H N(CH3)2 nBu 132. H NBu2 nBu 133. H NCH3Bu nBu 134. H NEt2 nBu 135. H NEtBu nBu 136. H CF3 nBu 137. H OPh nBu 138. H CH2OCH3 nBu 139. H OCF3 nBu 140. H OCF2CF3 nBu 141. H Ph nBu 142. H N3 nBu 143. H NHCH3 Cl 144. H NHBu Cl 145. H N(CH3)2 Cl 146. H NBu2 Cl 147. H NCH3Bu Cl 148. H NEt2 Cl 149. H NEtBu Cl 150. H SCH3 Cl 151. H SBu Cl 152. H OCH3 Cl 153. H OBu Cl 154. H CF3 Cl 155. H OPh Cl 156. H CH2OCH3 C1 157. H OCF3 Cl 158. H OCF2CF3 C1 159. H Ph Cl 160. H N3 Cl 161. H NHCH3 NHCH3 162. H NHBu NHBu 163. H N(CH3)2 N(CH3)2 164. H NBu2 NBu2 165. H NCH3Bu NCH3Bu 166. H NEt2 NEt2 167. H NEtBu NEtBu - 49 168. H SCH3 SCH3 169. H SBu SBu 170. H OCH3 OCH3 171. H OBu OBu 172. H CF3 CF3 173. H OPh OPh 174. H CH20CH3 CH20CH3 175. H OCF3 OCF3 176. H OCF2CF3 OCF2CF3 177. H Ph Ph 178. H N3 N3 179. CH3 H 180. CH3 C1 C1 181. CH3 Cl NHCH3 182. CH3 Cl NHBu 183. CH3 Cl N(CH3)2 184. CH3 Cl NBu2 185. CH3 Cl NCH3Bu 186. CH3 C1 NEt2 187. CH3 Cl NEtBu 188. CH3 Cl SCH3 189. CH3 Cl SBu 190. CH3 Cl OCH3 191. CH3 Cl OBu 192. CH3 Cl CF3 193. CH3 Cl OPh 194. CH3 Cl CH2OCH3 195. CH3 Cl OCF3 196. CH3 Cl OCF2CF3 197. CH3 Cl Ph 198. CH3 Cl N3 199. CH3 H I 200. CH3 H CH3 201. CH3 H Bu 202. CH3 H OCH3 203. CH3 H OBu 204. CH3 H SCH3 205. CH3 H SBu 206. CH3 H NHCH3 207. CH3 H NHBu 208. CH3 H N(CH3)2 209. CH3 H NBu2 210. CH3 H NCH3Bu 211. CH3 H NEt2 212. CH3 H NEtBu 213. CH3 H CF3 214. CH3 H OPh - 50 215. CH3 H CH2OCH3 216. CH3 H OCF3 217. CH3 H OCF2CF3 218. CH3 H Ph 219. CH3 H N3 220. CH3 CH3 CH3 221. CH3 CH3 Bu 222. CH3 CH3 OCH3 223. CH3 CH3 OBu 224. CH3 CH3 SCH3 225. CH3 CH3 SBu 226. CH3 CH3 NHCH3 227. CH3 CH3 NHBu 228. CH3 CH3 N(CH3)2 229. CH3 CH3 NBu2 230. CH3 CH3 NCH3Bu 231. CH3 CH3 NEt2 232. CH3 CH3 NEtBu 233. CH3 CH3 CF3 234. CH3 CH3 OPh 235. CH3 CH3 CH2OCH3 236. CH3 CH3 OCF3 237. CH3 CH3 OCF2CF3 238. CH3 CH3 Ph 239. CH3 CH3 N3 240. CH3 nBu CH3 241. CH3 nBu Bu 242. CH3 nBu OCH3 243. CH3 nBu OBu 244. CH3 nBu SCH3 245. CH3 nBu SBu 246. CH3 nBu NHCH3 247. CH3 nBu NHBu 248. CH3 nBu N(CH3)2 249. CH3 nBu NBu2 250. CH3 nBu NCH3Bu 251. CH3 nBu NEt2 252. CH3 nBu NEtBu 253. CH3 nBu CF3 254. CH3 nBu OPh 255. CH3 nBu CH2OCH3 256. CH3 nBu OCF3 257. CH3 nBu OCF2CF3 258. CH3 nBu Ph 259. CH3 nBu N3 260. CH3 I H 261. CH3 CH3 H - 51 262. CH3 BuH 263. CH3 OCH3H 264. CH3 OBuH 265. CH3 SCH3H 266. CH3 SBuH 267. CH3 NHCH3H 268. CH3 NHBuH 269. CH3 N(CH3)2H 270. CH3 NBu2H 271. CH3 NCH3BuH 272. CH3 NEt2H 273. CH3 NEtBuH 274. CH3 CF3H 275. CH3 OPhH 276. CH3 CH2OCH3H 277. CH3 OCF3H 278. CH3 OCF2CF3H 279. CH3 PhH 280. CH3 N3H 281. CH3 CH3CH3 282. CH3 BuCH3 283. CH3 OCH3CH3 284. CH3 OBuCH3 285. CH3 SCH3CH3 286. CH3 SBuCH3 287. CH3 NHCH3CH3 288. CH3 NHCH3 289. CH3 N(CH3)2CH3 290. CH3 NBu2CH3 291. CH3 NCH3BuCH3 292. CH3 NEt2 CH3 293. CH3 NEtUuCH3 294. CH3 CF3CH3 295. CH3 OPhCH3 296. CH3 CH2OCH3CH3 297. CH3 OCF3CH3 298. CH3 OCF2CF3CH3 299. CH3 PhCH3 300. CH3 N3CH3 301. CH3 CH3nBu 302. CH3 BunBu 303. CH3 Ot: E LnBu 304. CH3 OBunBu 305. CH3 SCH3nBu 306. CH3 SBunBu 307. CH3 NHCH3nBu 308. CH3 NHBunBu - 52 309. CH3 N(CH3)2 nBu 310. CH3 NBu2 nBu 311. CH3 NCH3Bu nBu 312. CH3 NEt2 nBu 313. CH3 NEtBu nBu 314. CH3 CF3 nBu 315. CH3 OPh nBu 316. CH3 CH2OCH3 nBu 317. CH3 OCF3 nBu 318. CH3 OCF2CF3 nBu 319 CH3 Ph nBu 320. CH3 N3 nBu 321. CH3 NHCH3 Cl 322. CH3 NHBu C1 323. CH3 N(CH3)2 Cl 324. CH3 NBu2 C1 325. CH3 NCH3Bu Cl 326. CH3 NEt2 Cl 327. CH3 NEtBu Cl 328. CH3 SCH3 Cl 329. CH3 SBu Cl 330. CH3 OCH3 Cl 331. CH3 OBu Cl 332. CH3 CF3 Cl 333. CH3 OPh Cl 334. CH3 CH20CH3 Cl 335. CH3 OCF3 Cl 336. CH3 OCF2CF3 Cl 337. CH3 Ph Cl 338. CH3 N3 Cl 339. CH3 NHCH3 NHCH3 340. CH3 NHBu NHBu 341. CH3 N(CH3)2 N(CH3)2 342. CH3 NBu2 NBu2 343. CH3 NCH3Bu NCH3Bu 344. CH3 NEt2 NEt2 345. CH3 NEtBu NEtBu 346. CH3 SCH3 SCH3 347. CH3 SBu SBu 348. CH3 OCH3 OCH3 349. CH3 OBu OBu 350. CH3 CF3 CF3 351. CH3 OPh OPh 352. CH3 CH2OCH3 CH2OCH3 353. CH3 OCF3 OCF3 354. CH3 OCF2CF3 OCF2CF3 355. CH3 Ph Ph - 53 356. 1 CH3 1 N3 1 N3 357. nBu H H 358. nBu Cl Cl 359. nBu Cl NHCH3 360. nBu Cl NHBu 361. nBu Cl N(CH3)2 362. nBu Cl NBu2 363. nBu C1 NCH3Bu 364. nBu Cl NEt2 365. nBu Cl NEtBu 366. nBu Cl SCH3 367. nBu Cl SBu 368. nBu Cl OCH3 369. nBu Cl OBu 370. nBu Cl CF3 371. nBu Cl OPh 372. nBu Cl CH2OCH3 373. nBu Cl OCF3 374. nBu Cl OCF2CF3 375. nBu Cl Ph 376. nBu Cl N3 377. nBu H I 378. nBu H CH3 379. nBu H Bu 380. nBu H OCH3 381. nBu OBu 382. nBu H SCH3 383. nBu H SBu 384. nBu H NHCH3 385. nBu NHBu 386. nBu H N(CH3)2 387. nBu H NBu2 388. nBu H NCH3Bu 389. nBu H NEt2 390. nBu H NEtBu 391. nBu H CF3 392. nBu H OPh 393. nBu H CH2OCH3 394. nBu H OCF3 395. nBu H OCF2CF3 396. nBu Ph 397. nBu H N3 398. nBu CH3 CH3 399. nBu CH3 Bu 400. nBu CH3 OCH3 401. nBu CH3 OBu 402. nBu CH3 SCH3 - 54 403. nBu CH3 SBu 404. nBu CH3 NHCH3 405. nBu CH3 NHBu 406. nBu CH3 N(CH3)2 407. nBu CH3 NBu2 408. nBu CH3 NCH3Bu 409. nBu CH3 NEt2 410. nBu CH3 NEtBu 411. nBu CH3 CF3 412. nBu CH3 OPh 413. nBu CH3 CH2OCH3 414. nBu CH3 OCF3 415. nBu CH3 OCF2CF3 416 nBu CH3 Ph 417. nBu CH3 N3 418. nBu nBu CH3 419. nBu nBu Bu 420. nBu nBu OCH3 421. nBu nBu OBu 422. nBu nBu SCH3 423. nBu nBu SBu 424. nBu nBu NHCH3 425. nBu nBu NHBu 426. nBu nBu N(CH3)2 427. nBu nBu NBu2 428. nBu nBu NCH3Bu 429. nBu nBu NEt2 430. nBu nBu.NEtBu 431. nBu nBu CF3 432. nBu nBu OPh 433. nBu nBu CH2OCH3 434. nBu nBu OCF3 435. nBu nBu OCF2CF3 436. nBu nBu Ph 437. nBu nBu N3 438. nBu I H 439. nBu CH3 H 440. nBu Bu H 441. nBu OCH3 H 442. nBu OBu H 443. nBu SCH3 H 444. nBu SBu H 445. nBu NHCH3 H 446. nBu NHBu H 447. nBu N(CH3)2 H 448. nBu NBu2 H 449. nBu NCH3Bu H - 55 450. nBu NEt2 H 451. nBu NEtBu H 452. nBu CF3 H 453. nBu OPh H 454. nBu CH2OCH3 H 455. nBu OCF3 H 456. nBu OCF2CF3 H 457. nBu Ph H 458. nBu N3 H 459. nBu CH3 CH3 460. nBu Bu CH3 461. nBu OCH3 CH3 462._ nBu OBu CH3 463. nBu SCH3 CH 464. nBu SBu CH3 465. nBu NHCH3 CH3 466. nBu NHBu CH3 467. nBu N(CH3)2 CH3 468. nBu NBu2 CH3 469. nBu NCH3Bu CH3 470. nBu NEt2 CH 471. nBu NEtBu CH3 472. nBu CF3 CH3 473. nBu OPh CH3 474. nBu CH20CH3 CH3 475. nBu OCF3 CH3 476. nBu OCF2CF3 CH3 477. nBu Ph CH3 478. nBu N3 CH3 479. nBu CH3 nBu 480. nBu nBu nBu 481. nBu OCH3 nBu 482. nBu OBu nBu 483. nBu SCH3 nBu 484. nBu SBu nBu 485. nBu NHCH3 nBu 486. nBu NHBu nBu 487. nBu N(CH3)2 nBu 488. nBu NBu2 nBu 489. nBu NCH3Bu nBu 490. nBu NEt2 nBu 491. nBu NEtBu nBu 492. nBu CF3 nBu 493. nBu OPh nBu 494. nBu CH2OCH3 nBu 495. nBu OCF3 nBu 496. nBu OCF2CF3 nBu - 56 497. | nBu Ph nBu 498. nBu N3 nBu 499. nBu NHCH3 500. nBu NHBu Cl 501. nBu N(CH3)2 Cl 502. nBu NBu2 Cl 503. nBu NCH3Bu 504. nBu NEt2 Cl 505. nBu NEtBu Cj1 = 506. nBu SCH3 507. nBu SBu Cl 508. _ nBu OCH3 Cl 509. nBu OBu 510. nBu CF3 Cl 511. nBu OPh Cl 512. nBu CH20CH3 Cl 513. nBu OCF3 Cl 514. nBu OCF2CF3 Cl 515. nBu Ph Cl 516. nBu N3 Cl 517. nBu NHCH3 NHCH3 518. nBu NHBu NHBu 519. nBu N(CH3)2 N(CH3)2 520. nBu NBu2 NBu2 521. nBu NCH3Bu NCH3Bu 522. nBu NEt2 NEt2 523. nBu NEtBu NEtBu 524. nBu SCH3 SCH3 525. nBu SBu SBu 526. nBu OCH3 OCH3 527. nBu OBu OBu 528. nBu CF3 CF3 529. nBu OPh OPh 530. nBu CH2OCH3 CH2OCH3 531. nBu OCF3 OCF3 532. nBu OCF2CF3 OCF2CF3 533. nBu Ph Ph 534. nBu N3 N3 535. Ph H H 536. Ph CH3 CH3 537. Ph CH3 H 538. Ph H CH3 539. CH2OCH3 H H 540. CH2OCH3 CH3 CH3 541. CH2OCH3 CH3 H 542. CH20CH3 H CH3 543. CF3 H H - 57 544. 1 CF3 CH3 CH3 545. CF3 CH3 H 546. CF3 H CH3 547. OH H H 548. OH CH3 CH3 549. OH CH3 H 550. OH H CH3 551. OH CHO H 552. OH CHO CH3 553. OH H CF3 554. OH CF3 H 555. OH CF3 CF3 556. OH CH2OCH3 CH3 557. OH CH3 CH2OCH3 558. OH CH2OCH3 H 559. OH H CH2OCH3 560. H CHO H 561. CH3 CHO H 562. CF3 CHO H 563. CH2OCH3 CHO 564. nBu CHO H 565. H CHO CH3 566. CH3 CHO CH3 567. CF3 CHO CH3 568. CH2OCH3 CHO CH3 569. nBu CHO CH3 570. H H CHO 571. CH3 H CHO 572. CF3 H CHO 573. CH2OCH3 H CHO 574. nBu H CHO 575. H CH3 CHO 576. CH3 CH3 CHO 577. CF3 CH3 CHO 578. CH2OCH3 CH3 CHO 579. nBu CH3 CHO 580. H Cl CH3 581. H CH3 C1 582. H CF3 C1 583. H C1 CF3 584. CH3 Cl CH3 585. CH3 CH3 Cl 586. CH3 CF3 C1 587. CH3 C1 CF3 588. CF3 Cl CH3 589. CF3 CH3 Cl 590. CF3 CF3 Cl - 58 591. CF3 Cl lC 592. OCH3 H H 593. OCH3 CH3 CH3 594. OCH3 CH3 H 595. OCH3 H CH3 596. OCH3 CHO H 597. OCH3 CHO CH3 598. OCH3 H CF3 599. OCH3 CF3 H 600. OCH3 CF3 CF3 _.

601. OCH3 CH2OCH3 CH3 602. OCH3 CH3 CH20CH3 603. OCH3 CH2OCH3 H 604. OCH3 H CH20CH3 605. H Cl OCH2CH3 _ 606. H C1 SCH2CH3 607. H Cl Mopholin 608. H Cl Pyperidin 609. H Pyperidin Pyperidin 610. H 0 Cl 611. H h C1 612 H CH3(CH2)130 Cl 613. H OCH2Ph-3-C1 C1 614. H Cl OCH2Ph-3-CI 615. H O(CH2)2 CCH Cl 616. H OCH(CH3)=CH2 Cl 617. H O(CH2)2 CH=CH2 Cl 618. H C1 O(CH2)2CH=CH2 619. Cl 620. H O(CH2)2Ph-4-CN Cl 621. H Cl O(CH2)2Ph-4-CN 622. H OCH2CH2CH3 Cl 623. H O(CH2)2O(CH2)2 OCH3 Cl 624. H CH3CH2CH(CH3)O Cl OCH(CH3)CH2CH3 625 H OCH2 CH=CH2 Cl - 59 626. H Cl OCH2 CH=CH2 627. H C1 OCH2 C8CH 628. H O(CH2)2 C3CCH3 Cl 629. H OCH2 CZCCH3 Cl 630. H Cl OCH2 CZCCH3 631. H ocH(cH3)-cycloprop. Cl 632. H OCH2C(CH3)=CH2 Cl 633. H Cl OCH2C(CH3)=CH2 634. H o Cl 635. H Cl o 636. H O(CH2)20Ph-2-CI Cl 637. H O-CI, m-clphcH(cH3)o Cl 638. H O(CH2)2SCH2Ph-4-CI Cl 639. H O(CH2)2Ph-2-CI Cl 640. H O(CH2)2Ph-3-CF3 Cl 641. H O(CH2)2Ph-4-CH3 Cl 642. H N\\S>_o Cl

N

* 643. H Cl Gl 644. H O (CH2)2 CF3 Cl 645. H C1 Cl o 646. H O (CH2),lC(0)0CH3 Cl 647. H Cl 648. H O(CH2)2SCH3 Cl 649. H O(CH2)7CH3 Cl 650. H OCH2Ph-3-OCH3 Cl 651. . Cl 652. H OC,2H24 Cl 653. H O(CH2)20(CH2)5CH3 Cl 654. H O CloH'8 Cl - 60 655. H o Cl 656. H O(CH2)2SCH2CH3 Cl 657. H SN C1 of \ 658. H OCH2CH=CH(CH2)2CH3 Cl 659. H O(CH2)2Ph-3,4-(OCH3)2 C1 660. H _ O(CH2)2Ph-4-CI Cl 661. H CF3(CF2)5CH2O C1 662. H [to Cl 663. H OCH2Ph-2-I Cl 664. H CH3(CH2)20(CH2)20(CH Cl 2)20(CH2)20 665. H off Cl 666. H O(CH2)3-4-(CsH4N) Cl 667. H ho/ Cl 668. H [=o Cl 669 H o(cH2)l lBr Cl 670. H O(CH2)2S Ph Cl 671. [[ OCI Cl 672. H Cl 673. H o(CH2)6Ph Cl 674. H Ash Cl \\ // of 675. H O(CH2)9CH=CH2 C1 676. H Cl o 677. H o o,N-< Cl 678. H OCH2Ph-3-CF3 Cl - 61 679. H OCH2 3-(C5H4N) Cl 680. H OCH2Si(CH3)3 Cl 681. H O(CH2)4CI Cl 682. H Br Cl 683. H oi> Cl 684. H N Cl s O 685. SEt SEt 686. H Cl OiPr 687. H Cl NH2 688. H Cl N(CH3)NH2 689. H,kN, N 690. H Cl NHPr 691. H Cl NHPh 692. H Cl NHCH(CH2)2 693 NHPr Cl 694. H NHCH(CH2)2 Cl 695. H Cl NH C5H9 696. H NH C5H9 Cl 697. H Cl \ 698. H Cl N(CH3)(0CH3) 699 H Cl NHCH2C3CH 700. H Cl NHCH(CH3)CH2OCH3 701. H Cl NHEt 702. H NHCH2C3CH Cl 703. H NHEt Cl 704. H Br Br 705. H iPr Br 706. H OBu Ph 707. H Ph-3,5-(CF3)2 Ph-3,5-(CF3)2 708. H Ph-4-CH3 Ph-4-CH3 709. H OiPr Ph - 62 710. H OiPr Ph-4-CH3 711. H OiPr Ph-3,5-(CF32 712. H OiPr Ph-4- Si (CH3)3 713. H Ph-4- Si (CH3)3 Ph-4- Si (CH3)3 714. H OCH2CSCH Cl 715. H NHCH2Ph Cl 716. H Cl NHCH2Ph 717. NH2 Cl 718. Cl 719. H Cl W> 720. H 0 Cl of 721. H oo 722. H Cl > 723. H OiPr Cl 724. H OEt Cl 725. H NHCH(CH3)CH2OCH3 C1 726. H SCH2CH3 Cl

Table B-7 ::N

IN-N

(own 0ó \ - R3 R5) R8 R6 R7 I.7 N I R3 R5 R6 R7 I R8 1. |H H H H H 2. H CH3 H H H 3 H nsU H H H 4. H CF3 H H H S. H CF2CF3 H H H 6. H CH2OCH3 H H H 7. H OCH3 H H H 8. H Ph _ H H H 9. H -CH2Ph H H H 10. H H H CH3 H 11. H H H nsU H 12. H H H CF3 H 13. H H H CF2CF3 H 14. H H H CH2OCH3 H 15. H H H OCH3 H 16. H H H Ph H 17 H H H -CH2Ph H 1X. H CH3 CH3 H H 19. H nsU CH3 H H 20. H CF3 CH3 H H 21. H CF2CF3 CH3 H H 22. H CH20CH3 CH3 H H 23. H OCH3 CH3 H H 24. H Ph CH3 H H 25. H -CH2Ph CH3 H H 26. H H H CH3 CH3 27. H H H CH3 nsU 28. H H H CH3 CF3 29. H H H CH3 CF2CF3 30. H H H CH3 CH2OCH3 31. H H H CH3 OCH3 32. H H H CH3 Ph 33. H H H CH3 -CH2Ph 34. H CH3 H H CH3 35. H nsU H H CH3 36. H CF3 H H CH3 37. H CF2CF3 H H CH3 38. H CH20CH3 H H CH3 39. H OCH3 H H CH3 40. H Ph H H CH3 41. H -CH2Ph H H CH3 42. H CH3 nsU H 43. H H CH3 CF3 H 44. H H CH3 CF2CF3 H 45. H H CH3 CH2OCH3 H - 64 46. H H CH3 OCH3 H 47. H H CH3 Ph H 48. H H CH3 -CH2Ph H _ 49. H CH3 H CH3 CH3 50. H nBu H CH3 CH3 51. H CF3 H CH3 CH3 52. H CF2CF3 H CH3 CH3 53. H CH20CH3 H CH3 CH3 54. H OCH3 H CH3 CH3 55. H Ph H CH3 CH3 56. H -CH2Ph H CH3 CH3 57. H CH3 CH3 CH3 H 58. H CH3 CH3 nBu H 59. H CH3 CH3 CF3 H 60. H CH3 CH3 CF2CF3 H 61. H CH3 CH3 CH2OCH3 H 62. H CH3 CH3 OCH3 H 63. H CH3 CH3 Ph H 64. H CH3CH3 -CH2Ph H 65. H nBuCH3 CH3 H 66. H CF3CH3 CH3 H 67. H CF2CF3 CH3 CH3 H 68. H CH20CH3 CH3 CH3 H 69. H OCH3 CH3 CH3 H 70. H Ph CH3 CH3 H 71. H -CH2Ph CH3 CH3 H 72. H CH3 H CH3 nBu 73. H CH3 H CH3 CF3 74. H CH H CH3 CF2CF3 75. H CH3 H CH3 CH2OCH3 76. H CH3 H CH3 OCH3

_

77. H CH3 H CH3 Ph 78. H CH3 H CH3 -CH2Ph 79. H CH3 CH3 CH3 CH3 80. H nBu CH3 CH3 CH3 81. H CF3 CH3 CH3 CH3 82. H CF2CF3 CH3 CH3 CH3 83. H CH20CH3 CH3 CH3 CH3 84. H OCH3 CH3 CH3 CH3 85. H Ph CH3 CH3 CH3 86. H -CH2Ph CH3 CH3 CH3 87. H CH3 CH3 CH3 nBu 88. H CH3 CH3 CH3 CF3 89. H CH3 CH3 CH3 CF2CF3 90. H CH3 CH3 CH3 CH2OCH3 _ H CH3 CH3 CH3 OCH3 92. H CH3 CH3 CH3 Ph - 65 93. H CH3 CH3 CH3 -CH2Ph 94. H nBnu nBu H H 95. H CF3 nBu H H 96. H CF2CF3 nBu H H 97. H CH2OCH3 nBu H H 98. H OCH3 nBu H H 99. H Ph nBu H H 1 0t H -CH2Ph nBu H H 101 H H H Bu nBu 102 H H H CF3 nBu 10: H H H CF2CF3 nBu 104 H H H CH2OCH3 nBu H H H OCH3 nBu 10t H H H Ph nBu 10, H H H -CH2Ph nBu 10E H nBu H H H H nBu H H CH3 11t H nBu H H nBu 11 l H nBu H H CF3 11 H nBu H H CF2CF3 11 H nBu H H CH2OCH3 I 1t H nBu H H OCH3 11' H nBu H H Ph I I H nBu H H -CH2Ph 11, H H H nBu H 11E H H CH3 nBu H 11 H H nBu nBu H 12( H H CF3 nBu H 12] H H CF2CF3 nBu H 12 H H CH2OCH3 nBu H 12- H H OCH3 nBu H 12 H H Ph nBu H 122 H H -CH2Ph nBu H 1 2( H CH3 nBu nBu H 12, H nBu nBu nBu H 12! H CF3 nBu nBu H 12' H CF2CF3 nBu nBu H 13( H CH2OCH3 nBu nBu H 13 H OCH3 nBu nBu H _ 13 H Ph nBu Bu H 13 H -CH2Ph nBu nBu H 13' H CH3 H nBu nBu 13' H nBu H nBu nBu 134 H CF3 H nBu nBu 13 H CF2CF3 H nBu nBu 13! H CH2OCH3 H nBu nBu 13' H OCH3 H nBu nBu - 66 14t H Ph H nBu |nBu 141 H -CH2Ph H nBu nBu 14 H nBu nBu CH3 H 14 H nBu nBu CF3 H 14t H nBu nBu CF2CF3 H 14' H nBu nBu CH2OCH3 H 14( H nBu nBu OCH3 H 14 H nBu nBu Ph H 14 H nBu nBu -CH2Ph H H nBu H CH3 nBu H nBu H CF3 nBu 151 H nBu H CF2CF3 nBu H nBu H CH2OCH3 nBu 15- H nBu H OCH3 nBu 15i H nBu Ph nBu 152 H nBu H -CH2Ph nBu 15( H CH3 nBu nBu nBu H Bu nBu nBu nBu 1 5E H CF3 nBu nBu nBu H CF2CF3 nBu nBu nBu 16( H CH2OCH3 nBu nBu nBu 161 H OCH3 nBu _ nBu nBu 162 H Ph nBu nBu nBu 16- H -CH2Ph nBu nBu nBu 16t H nBu nBu nBu CH3 16' H nBu nBu nBu CF3 16( H nBu nBu nBu CF2CF3 16 H nBu nBu nBu CH20CH3 16E H nBu nBu nBu OCH3 H nBu nBu nBu Ph 17 H nBu Bu nBu -CH2Ph 17i H nBu CH3 nBu CH3 17 H nBu CH3 nBu CF3 17 H nBu CH3 nBu CF2CF3 17' H nBu CH3 nBu CH20CH3 172 H nBu CH3 nBu OCH3 17( H nBu CH3 nBu Ph 17, H nBu CH3 nBu -CH2Ph 17! H CF3 nBu nBu CH3 17 H CF2CF3 nBu nBu CH3 18( H CH2OCH3 nBu nBu CH3 18] H OCH3 nBu nBu CH3 18 H Ph nBu nBu CH3 18 H -CH2Ph nBu nBu CH3 18' H CH3 CH3 nBu nBu 182 H CF3 CH3 nBu nBu 18( H CF2CF3 CH3 nBu nBu - 67 18 H CH2OCH3 CH3 nBu nBu 18E H OCH3 CH3 nBu nBu H _ Ph CH3 nBu nBu l 9C H -CH2Ph CH3 nBu nBu l 9l H nBunBu CH3 CH3 192 H nBunBu CF3 CH3 193 H nBunBu CF2CF3 CH3 194 H nBunBu CH20CH3 CH3 1gc H nBunBu OCH3 CH3 19( H nBunBu Ph CH3 19 / H nBunBu -CH2Ph CH3 19E H nBuCH3 CH3 CF3 H nBuCH3 CH3 CF2CF3 20C H nBuCH3 CH3 CH20CH3 201 H nBuCH3 CH3 OCH3 202 H nBu CH3 CH3 _ Ph 203 H nBu CH3 CH3 -CH2Ph 204 H CF3 CH3 CH3 nBu 205 H CF2CF3 CH3 CH3 nBu 20( H CH2OCH3 CH3 CH3 nBu H OCH3 CH3CH3 nBu 20E H Ph CH3 CH3 u 205 H -CH2Ph CH3 CH3 nBu 21C H CF3 nBu CH3 CH3 211 H CF2CF3 nBu CH3 CH3 212 H CH20CH3 nBu CH3 CH3 213 H OCH3 nBu CH3 CH3 214 H Ph nBu CH3 CH3 215 H -CH2Ph nBu CH3 CH3 21( H _ CH3 CH3 CF3 nBu 219 H CH3 CH3 CF2CF3 u 21 a H CH3 CH3 CH20CH3 nBu 21S H CH3 CH3 OCH3 nBu 22C H CH3 CH3 Ph nBu 221 H CH3 CH3 -CH2Ph nBu 222 H CF3 nBu H CH3 223 H CF2CF3 nBu H CH3 224 H CH2OCH3 nBu H CH3 225 H OCH3 nBu H CH3 22{ H Ph nBu H CH3 22 H -CH2Ph nBu H CH3 22E H H CH3 CF3 nBu 225 H H CH3 CF2CF3 nBu 23C H H CH3 CH2OCH3 nBu 231 H H CH3 OCH3 nBu 23 H H CH3 Ph nBu 233 H H CH3 -CH2Ph u - 68 23' H nBu CH3 CF3 23' H nBu H CH3 CF2CF3 23( H nBu H CH3 CH2OCH3 23, H nBu H CH3 OCH3 23E H nBu H CH3 Ph 23S H nBu H CH3 -CH2Ph 24 H CF3 CH3 nBu H i4] H CF2CF3 CH3 nBu H 24 H CH2OCH3 CH3 nBu H 24H OCH3 CH3 nBu H 24 H Ph CH3 nBu H 24' H -CH2Ph CH3 nBu H 24( H CF3 Bu CH3 H 24, H CF2CF3 Bu CH3 H 24E H CH2OCH3 Bu CH3 H 245 H OCH3 Bu CH3 H 25E H _ Ph Bu CH3 H 251 H -CH2Ph Bu CH3 H H CH3 H CF3 nBu 25' H CH3 H CF2CF3 nBu 254 H CH3 H CH2OCH3 nBu 25' H CH3 H OCH3 nBu 25( H CH3 H Ph nBu 25, H CH3 H -CH2Ph nBu 25E H nBu CH3 H CF3 255 H nBu CH3 H CF2CF3 26( H nBu CH3 H CH2OCH3 26] H nBu CH3 H OCH3 262 H nBu CH3 H Ph 26 H nBu CH3 H -CH2Ph 264 H CF3 H CH3 nBu 26' H CF2CF3 H CH3 nBu 26 H CH2OCH3 H CH3 nBu 26, H _ OCH3 H CH3 nBu 26! H PhH CH3 nBu 265 H -CH2phH CH3 nBu 27( CH3 H_ H H H 271 CH3 CH3H H H 27 CH3 nBuH H H 27 CH3 CF3H H H 27' CH3 CF2CF3H H H 27' CH3 CH2OCH3H H H 27( CH3 OCH3H H H 27', CH3 PhH H H 27t CH3 -CH2PhH H H 27c CH3 HH CH3 H 28( CH3 HH nBu H - 69 28] CH3 H | HCF3 H 282 CH3 H H CF2CF3 H 28: CH3 H HCH20CH3 H 284 CH3 H H OCH3 H 284 CH3_ H H Ph H 28t CH3 H H -CH2Ph H 28 CH3 CH3 CH3 H H 28E CH3 nBu CH3 H H 285 CH3 CF3 CH3 H H 29C CH3 CF2CF3 CH3 H H 291 CH3 CH2OCH3 CH3 H H 292 CH3 OCH3 CH3 H H 29: CH3 Ph CH3 H H 294 CH3 -CH2Ph CH3 H H 29' CH3 H H CH3 CH3 29{ CH3 H H CH3 nBu 29 CH3 H H CH3 CF3 29 CH3 H H CH3 CF2CF3 295 CH3 H _ H CH3 CH2OCH3 30C CH3 H H CH3 OCH3 30] CH3 H H CH3 Ph 30> CH3 H H CH3 -CH2Ph 30: CH3 CH3 H H CH3 304 CH3 Bu H H CH3 30c CH3 CF3 H H CH3 30( CH3 CF2CF3 H H CH3 CH3 CH20CH3 H H CH3 30E CH3 OCH3 H H CH3 CH3 Ph H H CH3 31C CH3 -CH2Ph H H CH3 311 CH3 H CH3 nBu H 312 CH3 H CH3 CF3 H 31 CH3 H CH3 CF2CF3 H 314 CH3 H CH3 CH20CH3 H 31 c CH3 H CH3 OCH3 H 31 CH3 H CH3 Ph H 31, CH3 H CH3 -CH2Ph H 31 CH3 CH3 H CH3 CH3 31' CH3 nBu _ H CH3 CH3 32( CH3 CF3 H CH3 CH3 32 i CH3 CF2CF3 H CH3 CH3 32' CH3 CH2OCH3 H CH3 CH3 32- CH3 OCH3 H CH3 CH3 32' CH3 Ph H CH3 CH3 32' CH3 -CH2Ph H CH3 CH3 32( CH3 CH3 CH3 CH3 H 32, CH3 CH3 CH3 nBu H - 70 324 CH3 1 CH3 CH3 CF3 H 32' CH3 CH3 CH3 CF2CF3 H 33( CH3 CH3 CH3 CH2OCH3 H 331 CH3 CH3 CH3 OCH3 H 33, CH3 CH3 CH3 Ph H 33^ CH3 CH3 CH3 -CH2Ph H 33' CH3 nBu CH3 CH3 H 33 CH3 _ CF3 CH3 CH3 H 33( CH3 CF2CF3 CH3 CH3 H 33, CH3 CH20CH3 CH3 CH3 H 33 CH3 OCH3 CH3 CH3 H 33' CH3 Ph CH3 CH3 H 34( CH3 -CH2Ph CH3 CH3 H 34] CH3 CH3 H CH3 nBu 34' CH3 CH3 H CH3 CF3 34A CH3 CH3 H CH3 CF2CF3 34t CH3 CH3 H CH3 CH20CH3 34' CH3 CH3 H CH3 OCH3 34 CH3 CH3 H _ CH3 Ph 34, CH3 _ CH3 H CH3 -CH2Ph 34t CH3 CH3 CH3 CH3 CH3 34' CH3 nBu CH3 CH3 CH3 35( CH3 CF3 CH3 CH3 CH3 35] CH3 CF2CF3 CH3 CH3 CH3 CH3 CH2OCH3 CH3 CH3 CH3 CH3 OCH3 CH3 CH3 CH3 35' CH3 Ph CH3 CH3 CH3 35' CH3 -CH2PhCH3 CH3 CH3 35( CH3 CH3CH3 CH3 nBu 35, CH3 CH3CH3 CH3 CF3 35t CH3 CH3_ CH3 CH3 CF2CF3 35' CH3 CH3CH3 CH3 CH2OCH3 36( CH3 _ CH3 CH3 CH3 OCH3 36] CH3 CH3 CH3 CH3 Ph 36 CH3 CH3 CH3 CH3 -CH2Ph 36 CH3 nBu nBu H H 36t CH3 CF3 nBu H H 36' CH3 CF2CF3 nBu H H 36t CH3 CH20CH3 nBu H H 36, CH3 OCH3 nBu H H 36! CH3 Ph nBu H H 36 CH3 - -CH2Ph nBu H H 37( CH3 HH nBu nBu 37] CH3 HH CF3 nBu 37 CH3 HH CF2CF3 nBu 37 CH3 H_ H CH2OCH3 nBu 37' CH3 HH OCH3 nBu 71 374 CH3 H H 1Ph |nBu 37( CH, H H -CH2Ph nBu 37 CH3 nBu H H H 37f CH3 nBu H H CH3 37t CH3 nBu H H nBu 38( CH3 nBu H H CF3 38 CH3 nBu H H CF2CF3 38' CH nBu H H CH2OCH3 38 CH3_ nBu H H OCH3 384 CH3 nBu H H Ph 384 CH3 nBu H H -CH2Ph 38t CH3_ H H nBu H 38 CH3 H CH3 nBu H 38E CH3 H Bu nBu H 385 CH3 H CF3 nBu H 39 CH3 H CF2CF3 nBu H 39] CH3 H CH20CH3 nBu H 39 CH3 H OCH3 nBu H 39r CH3 H Ph nBu H 394 CH3 H -CH2Ph nBu H 394 CH3 CH3 nBu nBu H 39( CH3 nBu nBu nBu H 39 CH3 CF3 nBu nBu H 39E CH3 CF2CF3 nBu nBu H 39' CH3 CH20CH3 nBu nBu H 40( CH3 OCH3 nBu nBu H 401 CH3 Ph nBu nBu H 402 CH3 -CH2Ph nBu nBu H 40r CH3 CH3 H nBu nBu 40t CH3 nBu H nBu nBu 40' CH3 CF3 H nBu nBu 40c CH3 CF2CF3 H nBu nBu CH3 CH20CH3 H nBu nBu 40E CH3 OCH3 H nBu nBu CH3 Ph H nBu nBu 41 ( CH3 -CH2Ph H nBu nBu 41] CH3 nBu nBu CH3 H 41 CH3 nBu nBu CF3 H 41 CHa nBu nBu CF2CF3 H 41 CH3 nBu nBu CH20CH3 H 41' CHs nBu nBu OCH3 H 41 ( CH3 nBu nBu Ph H 41, CH3 nBu nBu -CH2Ph H

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41 CH3 nBu H CH3 nBu 41'. CH nBu H CF3 nBu 42 CH3 nBu H CF2CF3 nBu 421 CH nBu H CH20CH3 nBu - 72 422 CH3 nBu H OCH3 nBu 42 CH3 nBu H Ph nBu 424 CH3 nBu H -CH2Ph nBu 424 CH3 CH3 nBu nBu nBu 42( CH3 Bu nBu nBu nBu 42 CH3 CF3 nBu nBu nBu 426 CHa CF2CF3 nBu nBu nBu 425 CH3 CH2OCH3 nBu nBu nBu 43C CH3 OCH3 nBu nBu nBu 431 CH3 Ph nBu nBu nBu 432 CH3 -CH2Ph nBu nBu nBu 439 CH3 nBu nBu nBu CH3 434 CH3 nBu nBu nBu CF3 435 CH3 nBu nBu nBu CF2CF3 43t CH3 nBu nBu nBu CH2OCH3 43: CH3 nBu nBu nBu OCH3 43E CH3 nBu nBu nBu Ph 43S CH3 nBu nBu nBu -CH2Ph 44C CH3 nBu CH3 nBu CH3 441 CH3 nBu CH3 nBu CF3 442 CH3 nBu CH3 nBu CF2CF3 443 CH3 nBu CH3 nBu CH2OCH3 444 CH3 nBu CH3 nBu OCH3 445 CH3 nBu CH3 nBu Ph 44( CH3 nBu CH3 nBu -CH2Ph 441 CH3 CF3 nBu nBu CH3 44E CH3 CF2CF3 nBu u CH3 44S CH3 CH20CH3 nBu nBu CH3 45C CH3 OCH3 nBu nBu CH3 451 CH3 Ph nBu nBu CH3 45Z CH3 -CH2Ph nBu nBu CH3 453 CH3 CH3 CH3 nBu nBu 454 CH3 CF3 CH3 nBu nBu 455 CH3 CF2CF3 CH3 nBu nBu 456 CH3 CH2OCH3 CH3 nBu nBu / CH3 OCH3 CH3 nBu nBu 45E CH3 Ph CH3 nBu nBu 455 CH3 -CH2Ph CH3 nBu nBu 46C CH3 nBu nBu CH3 CH3 461 CH3 nBu nBu CF3 CH3 46Z CH3 nBu nBu CF2CF3 CH3 463 CH3 nBu nBu CH20CH3 CH3 464 CH3 nBu nBu OCH3 CH3 465 CH3 nBu nBu Ph CH3 46( CH3 nBu nBu -CH2Ph CH3 461 CH3 nBu CH3 CH3 CF3 46E CH3 nBu CH3 CH3 CF2CF3 - 73 465 CH3 nBu CH3 47C CH3 nBu CH3 CH3 OCH3 47] CH3 nBu CH3 CH3 Ph 472 CH3 nBu CH3 CH3 -CH2Ph 473 CH3 CF3 CH3 CH3 nBu 474 CH3 CF2CF3 CH3 CH3 nBu 474 CH3 CH20CH3 CH3 CH3 nBu 47( CH3 OCH3 CH3 CH3 nBu 47 / CH3 Ph CH3 CH3 nBu 47E CH3 -CH2Ph CH3 CH3 u 47S CH3 CF3 nBu CH3 CH3 48C CH3 CF2CF3 nBu CH3 CH3 481 CH3 CH2OCH3 nBu CH3 CH3 482 CH3 OCH3 nBu CH3 CH3 483 CH3 Ph nBu CH3 CH3 484 CH3 -CH2Ph nBu CH3 CH3 484 CH3 CH3 CH3 CF3 nBu 48t CH3 - CH3 CH3 CF2CF3 nBu 48 CH3 CH3 CH3 CH20CH3 nBu 48E CH3 CH3 CH3 OCH3 u 485 CH3 CH3 CH3 Ph nBu 49C CH3 CH3 CH3 -CH2Ph nBu 491 CH3 CF3 nBu H CH3 492 CH3 CF2CF3 nBu H CH3 499 CH3 CH20CH3 u H CH3 494 CH3 OCH3 nBu H CH3 494 CH3 Ph nBu H CH3 49( CH3 -CH2Ph nBu H CH3 49 / CH3 H CH3 CF3 nBu 49E CH3 H CH3 CF2CF3 u 49S CH3 H CH3 CH20CH3 nBu SOC CH3 H CH3 OCH3 nBu 501 CH3 H CH3 Ph nBu 502 CH3 H CH3 -CH2Ph nBu 50' CH3 nBu H CH3 CF3 504 CH3 nBu H CH3 CF2CF3 504 CH3 nBu H CH3 CH2OCH3 50( CH3 nBu H CH3 OCH3 50, CH3 nBu H CH3 Ph 50E CH3 nBu H CH3 -CH2Ph 505 CH3 CF3 CH3 nBu H 51 CH3 CF2CF3 CH3 nBu H 511 CH3 CH20CH3 CH3 nBu H 51 CH3 OCH3 CH3 nBu H 51 ' CH3 Ph CH3 nBu H 512 CH3 -CH2Ph CH3 u H 51C CH3 CF3 nBu CH3 H - 74 nBu CH3 H 517| CH3 CH2OCH3 nBu CH3 H 51 CH3 OCH3 u CH3 H 51 CH3 Ph CH3 H 52 CH3 -CH2Ph nBu CH3 H 521 CH3 CH3 H CF3 nBu 52 CH3 CH3 H CF2CF3 nBu 52 CH3 CH3 H CH20CH3 nBu 522 CH3 CH3 H OCH3 u 522 CH3 CH3 _ H Ph nBu 52( CH3 CH3 H -CH2Ph nBu 52, CH3 nBu CH3 H CF3 52! CH3 nBu CH3 H CF2CF3 52' CH3 nBu CH3 H CH2OCH3 53( CH3 nBu CH3 H OCH3 53 CH3 nBu CH3 H Ph 53, CH3 nBu CH3 H -CH2Ph 532 CH3 CF3 H CH3 nBu 53 CH3 CF2CF3 H CH3 nBu 53' CH3 CH2OCH3 H CH3 nBu 534 CH3 OCH3H CH3 nBu 53' CH3 PhH CH3 nBu 534 CH3 -CH2PhH CH3 nBu 53' CF3 HH - H H

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54 CF3 CH3H H H 54 CF3 nBuH H H 54' CF3 CF3H H H 54 CF3 CF2CF3H H H 54 CF3 CH2OCH3H H H 54 CF3 OCH3H H H 54 CF3 PhH H H 54 CF3 -CH2PhH H H 54 CF3 HH CH3 H 54 CF3 HH nBu H CF3 HH CF3 H CF3 HH CF2CF3 H CF3 HH CH20CH3 H

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CF3 H H OCH3 H CF3 H H Ph H CF3 H _ H -CH2Ph H CF3 CH3 CH3 H H CF3 nBu CH3 H H CF3 CF3 CH3 H H CF3 CF2CF3 CH3 H H 56 CF3 CH2OCH3 CH3 H H 56 CF3 OCH3 CH3 H H 56 CF3 Ph CH3 H H 56' CF3 -CH2Ph CH3 H H 56' CF3 H H CH3 CH3 56' CF3 H H CH3 nBu 56( CF3 H H CH3 CF3 56, CF3 H H CH3 CF2CF3 56 CF3 H H CH3 CH2OCH3 56S CF3 H H CH3 OCH3 57( CF3 H H CH3 Ph 57 CF3 H H CH3 -CH2Ph 572 CF3 CH3 H H CH3 57' CF3 nBu H H CH3 57' CF3 CF3 H H CH3 574 CF3 CF2CF3 H H CH3 57( CF3 CH2OCH3 H H CH3 57 CF3 OCH3 H H CH3 57E CF3 Ph H H CH3 575 CF3 -CH2Ph H H CH3 58t CF3 H CH3 u H 581 CF3 H CH3 CF3 H 58 CF3 H CH3 CF2CF3 H 58' CF3 H CH3 CH2OCH3 H 58i CF3 H CH3 OCH3 H 58 CF3 H CH3 Ph H 58( CF3 H CH3 -CH2Ph H 58 CF3 CH3 H CH3 CH3 58t CF3 u H CH3 CH3 58S CF3 CF3 H CH3 CH3 59( CF3 CF2CF3 H CH3 CH3 59 CF3 CH2OCH3 H CH3 CH3 59 CF3 OCH3 H CH3 CH3 59' CF3 Ph H CH3 CH3 592 CF3 -CH2Ph H CH3 CH3 594 CF3 CH3 CH3 CH3 H 59( CF3 CH3 CH3 u H 59, CF3 CH3 CH3 CF3 H 59! CF3 CH3 CH3 CF2CF3 H 59 CF3 CH3 _ - H3 CH2OCH3 H 60( CF3 CH3 CH3 OCH3 H 60] CF3 CH3 CH3 Ph H 60, CF3 H3 CH3 -CH2Ph H CF3 nBu CH3 CH3 H CF3 CF3 CH3 CH3 H 602 CF3 CF2CF3 CH3 CH3 H 60( CF3 CH2OCH3 CH3 CH3 H CF3 OCH3 CH3 CH3 H 60! CF3 Ph CH3 CH3 H 60' CF3 -CH2Ph CH3 CH3 H - 76 61 ( CF CH3 H CH3 nBu 611 CF3 CH3 H CH3 CF3 61, CF3 CH3 H CH3 CF2CF3 612 CF3 CH3 H CH3 CH20CH3 61' CF3 CH3 H CH3 OCH3 61' CF3 CH3 H CH3 Ph 61 CF3 CH3 H CH3 -CH2Ph 61, CF3 CH3 CH3 CH3 CH3 61t CF3 nBu CH3 CH3 CH3 61t CF3 CF3 CH3 CH3 CH3 62( CF3 CF2CF3 CH3 CH3 CH3 62] CF, CH2OCH3 CH3 CH3 CH3 62 CF3 OCH3 CH3 CH3 CH3 6224 CF, Ph CH3 CH3 CH3 62t CF3 -CH2Ph CH3 CH3 CH3 62' CF3 CH3 CH3 CH3 nBu 62( CF3 CH3 CH3 CH3 CF3 62, CF3 CH3 CH3 CH3 CF2CF3 62f CF3 CH3 CH3 CH3 CH20CH3 62' CF3 CH3 CH3 CH3 OCH3 63 CF3 CH3 CH3 CH3 Ph 63] CF3 CH3 CH3 CH3 -CH2Ph 632 CF3 Bu nBu H H 63 CF3 CF3 nBu H H 632 CF3 CF2CF3 nBu H H 634 CF3 CH20CH3 nBu H H 63( CF3 OCH3 nBu H H 63, CF3 Ph nBu H H 63' CF3 -CH2Ph nBu H H 63 CF3 H H nBu nBu 64( CF3 H H CF3 nBu 64] CF3 H H CF2CF3 nBu 64 CF3 H H CH20CH3 nBu 642 CF3 H H OCH3 nBu 64' CF3 H H Ph nBu 64' CF3 H H -CH2Ph nBu 64( CF3 u H H H 64, CF3 nBu H H CH3 64 CF3 nBu H H Bu 64t CF3 nBu H H _ CF3 65( CF3 nBu H H CF2CF3 65] CF3 nBu H H CH2OCH3 CF3 nBu H H OCH3 I CF3 nBu H H Ph 65' CF3 nBu H H -CH2Ph 65' CF3 H H nBu H 65( CF3 H CH3 u H - 77 65' CF3 H Bu nBu H 65: CF3 H CF3 nBu H 65' CF3 H CF2CF3 nBu H 66( CF3 H CH2OCH3 nBu H 66: CF3 H OCH3 nBu H 66, CF3 H Ph nBu H 66 CF3 H -CH2Ph nBu H 66' CF3 CH3 nBu nBu H 662 CF3 Bu nBu nBu H 66 CF3 CF3 nBu nBu H 66, CF3 CF2CF3 nBu nBu. H 66! CF3 CH2OCH3 nBu nBu H 66' CF3 OCH3 nBu nBu H 67( CF3 Ph nBu nBu H 67 CF3 -CH2Ph nBu nBu H 67z CF3 CH3 H nBu nBu 67- CF3 nBu H nBu nBu 67t CF3 CF3 H nBu nBu 67' CF3 CF2CF3 H nBu nBu 67( CF3 CH2OCH3 H nBu nBu 67, CF3 OCH3 H nBu nBu 67! CF3 Ph H nBu nBu 675 CF3 -CH2Ph H nBu nBu 68( CF3 nBu nBu CH3 H 681 CF3 nBu nBu CF3 H 68 CF3 nBu nBu CF2CF3 H 68 CF3 nBu nBu CH2OCH3 H 684 CF3 nBu nBu OCH3 H 684 CF3 nBu nBu Ph H 68( CF3 nBu nBu -CH2Ph H 68, CF3 nBu H CH3 nBu 68 CF3 nBu H CF3 nBu 68' CF3 nBu H CF2CF3 nBu 69( CF3 nBu H CH2OCH3 nBu 691 CF3 nBu H OCH3 nBu 692 CF nBu H Ph nBu 69^ CF3 nBu H -CH2Ph nBu 692 CF3 CH3 nBu nBu nBu 694 CF3 nBu nBu nBu nBu 69( CF3 CF3 nBu nBu nBu 69, CFa CF2CF3 nBu nBu nBu 69E CF3 CH2OCH3 nBu nBu nBu 69' CF3 OCH3 nBu nBu nBu 70( CF3 Ph nBu nBu nBu 701 CF3 -CH2Ph nBu nBu nBu CF nBu nBu nBu CH3 CF3 nBu nBu nBu CF3 - 78 7044 CF3 1 u u u CF2CF3 70$ CF3 1 u u u CH20CH3 70( CF3 u u u OCH3 70, CF3 nBu nBu nBu Ph 70t CF3 u u u -CH2Ph CF3 nBu CH3 nBu CH3 711 CF3 nBu CH3 nBu CF3 _ 71] CF3 nBu CH3 nBu CF2CF3 71z CF3 nBu CH3 nBu CH2OCH3 711 CF3 nBu CH3 nBu OCH3 71t CF3 u CH3 u Ph 712 CF3 nBu CH3 nBu -CH2Ph 71{ CF3 CF3 u u CH3 71, CF3 CF2CF3 nBu nBu CH3 71 CF3 CH20CH3 u u CH3 715 CF3 OCH3 nBu nBu CH3 72C CF3 Ph nBu nBu CH3 72] -CF3 -CH2Ph nBu nBu CH3 722 CF3 CH3 CH3 nBu nBu 729 CF3 CF3 CH3 u u 724 CF3 CF2CF3 CH3 nBu nBu 724 CF3 CH20CH3 CH3 u u 72t CF3 OCH3 CH3 u u 72, CF3 Ph CH3 nBu nBu 72E CF3 -CH2Ph CH3 u u 725 CF3 nBu nBu CH3 CH3 73C CF3 nBu nBu CF3 CH3 731 CF3 nBu nBu F2CF3 CH3 732 CF3 nBu nBu CH2OCH3 CH3 73: CF3 u u OCH3 CH3 73 CF3 nBu nBu h CH3 734 CF3 u u -CH2Ph CH3 73( CF3 u CH3 CH3 CF3 73, CF3 nBu CH3 CH3 CF2CF3 73E CF3 nBu CH3 CH3 CH2OCH3 735 CF3 nBu CH3 CH3 OCH3 74C CF3 nBu CH3 CH3 Ph 74] CF3 nBu CH3 CH3 -CH2Ph 742 CF3 CF3 CH3 CH3 nBu 74. CF3 CF2CF3 CH3 CH3 nBu 74 CF3 CH2OCH3 CH3 CH3 nBu 744 CF3 OCH3 CH3 CH3 nBu 74( .CF3 Ph CH3 CH3 nBu 74, CF3 -CH2Ph CH3 CH3 nBu 74E CF3 CF3 nBu CH3 CH3 74' CF3 CF2CF3 nBu CH3 CH3 75( CF3 CH20CH3 nBu CH3 CH3 - 79 751| CF3 1 OCH3nBu CH3 CH3 752 CF3 Ph_ nBu CH3 CH3 753 CF3 -CH2PhnBu CH3 CH3 754 CF3 CH3CH3 CF3 nBu 755 CF3 CH3CH3 CF2CF3 nBu 756 CF3 CH3CH3 CH2OCH3 nBu 757 CF3 CH3CH3 OCH3 nBu 758 CF3 CH3CH3 Ph u 759 CF3 CH3CH3 -CH2Ph nBu 760 CF3 CF3nBu H CH3 761 CF3 CF2CF3nBu H CH3 762 CF3 CH2OCH3nBu H CH3 763 CF3 OCH3nBu H CH3 764 CF3 PhnBu H CH3 765 CF3 -CH2PhnBu H CH3 766 CF3 HCH3 CF3 nBu 767 CF3 HCH3 CF2CF3 nBu 768 CF3 HCH3 CH2OCH3 nBu 769 CF3 HCH3 OCH3 nBu 770 CF3 HCH3 Ph nBu 771 CF3 HCH3 -CH2Ph nBu 772 CF3 nBuH CH3 CF3 773 CF3 nBuH CH3 CF2CF3 774 CF3 nBuH CH3 CH2OCH3 775 CF3 nBuH CH3 OCH3 776 CF3 nBuH CH3 Ph 777 CF3 _ nBu H CH3 -CH2Ph 778 CF3 CF3 CH3 nBu H 779 CF3 CF2CF3 CH3 nBu H 780 CF3 CH2OCH3 CH3 nBu H 781 CF3 OCH3 CH3 nBu H 78 CF3 Ph CH3 nBu H 78 CF3 -CH2Ph CH3 nBu H 78t CF3 CF3 u CH3 H 78' CF3 CF2CF3 nBu CH3 H 78( CF3 CH2OCH3 nBu CH3 H 78 CF3 OCH3 nBu CH3 _ H 78t CF3 Ph nBu CH3 H 78' CF3 -CH2Ph nBu CH3 H 79( CF3 CH3 H CF3 nBu 79] CF3 CH3 H CF2CF3 nBu 79, CF3 CH3 H CH2OCH3 nBu 79 CF3 CH3 H OCH3 nBu 79t CF3 CH3 H Ph nBu 79' CF3 CH3 H -CH2Ph nBu 794 CF3 nBu CH3 H CF3 79' CF3 nBu CH3 H CF2CF3 - 80 794 CF3 nBu CH3 H CH20CH3 79c CF3 nBu CH3 H OCH3 80( CF3 nBu CH3 H Ph l CF3 nBu CH3 H -CH2Ph 802 CF3 CF3 H CH3 nBu 80: CF3 CF2CF3 H CH3 nBu 804 CF3 CH2OCH3 H CH3 nBu 804 CF3 OCH3 H CH3 nBu 80c CF3 Ph H CH3 nBu 80, CF3 -CH2Ph H CH3 nBu 80E Ph H H H H 80S Ph CH3 H H H 81t Ph H H CH3 H 81] Ph CH3 CH3 H H 812 Ph H H CH3 CH3 819 Ph CF3 H H H 814 Ph H H CF3 H 814 OH H H H H 81( OH CH3 H H H 81 OH H H CH3 H 81 OH CH3 CH3 H H 815 OH H H CH3 CH3 82( OH H H CF3 H 82] OH CF3 H H CH3 822 OH CF3 H H H 82: OH CH3 H CF3 H 824 OH H H CH2OCH3 H 824 OH CH2OCH3 H H H 82( OH CH2OCH3 H CH3 H 82 OH H CH3 CHzOCH3 H 82E OH CH2OCH3 H CH3 H 82S OH H CH3 CH2OCH3 H 83( CH3 H (CH2)4 H

Table B-8 - 81 iR10 gN R9 N -o

R7 R8 1.8 Rs l R6 I R7 Rg 1. H H HH H 2. CH3 H HH H 3. n-Bu H HH H 4. CF3 H HH H 5. CF2CF3 H HH H 6. CH20CH3 H HH H 7. OCH3 H HH I H 8. Ph H HH H 9. -CH2Ph H HH H 10. H H CH3 H H 11. H H n-Bu H H 12. H H CF3 H H 13. H H CF2CF3 H H 14. H H CH2OCH3 H H 15. H H OCH3 H H 16. H H Ph H H 17. H H -CH2Ph H H 18. CH3 CH3 H H H 19. n-Bu CH3 H H H 20. CF3 CH3 H H H 21. CF2CF3 H3 H H H 22. CH20CH3 CH3 H H H 23. OCH3 CH3 H H H 24. Ph CH3 H H H 25. -CH2Ph CH3 H H H 26. H H CH3 CH3 H 27. H H CH3 n-Bu H 28. H H CH3 CF3 H 29. H CH3 CF2CF3 H 30. H H CH3 CH20CH3 H 31. H H CH3 OCH3 H 32. H H CH3 Ph H 33. H H CH3 CH2Ph H 34. CH3 H H CH3 H 35. n-Bu H H CH3 H 36. CF3 H H CH3 H 37. CF2CF3 H H CH3 H 38._ CH20CH3 H H CH3 H 39. OCH3 H H CH3 H 40. Ph H H CH3 H 41. -CH2Ph H H CH3 H 42. H _ CH3 n-Bu H H 43. H CH3 CF3 H H 44. H CH3 CF2CF3 H H 45. H CH3 CH20CH3 H H 46. H CH3 OCH3 H H 47. H CH3 Ph H H 48. H CH3 -CH2Ph H H 49. CH3 H CH3 CH3 H 50. n-Bu H CH3 CH3 H 51. CF3 H CH3 CH3 H 52. CF2CF3 H CH3 CH3 H 53. CH20CH3 H CH3 CH3 H 54. OCH3 H CH3 CH3 H 55. Ph H CH3 CH3 H 56. CH2Ph H CH3 CH3 H

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57. CH3 CH3 CH3 H H 58. CH3 CH3 n-Bu H H 59. CH3 CH3 CF3 H H 60. CH3 CH3 CF2CF3 H H 61. CH3 CH3 CH2OCH3 H H 62. CH3 CH3 OCH3 H H 63. CH3 CH3 Ph H H 64. CH3 CH3 -CH2Ph H H 65. n-Bu CH3 CH3 H H 66. CF3 CH3 CH3 H H 67. CF2CF3 CH3 CH3 H H 68. CH20CH3 CH3 CH3 H H 69. OCH3 CH3 CH3 H H 70. Ph CH3 CH3 H H 71. CH2Ph CH3 CH3 H H 72. CH3 H CH3 n-Bu H 73. CH3 H CH3 _ CF3 H 74. CH3 H CH3 CF2CF3 H 75. CH3 H CH3 CH2OCH3 H 76. CH3 H _ CH3 OCH3 H 77. CH3 H CH3 Ph H 78. CH3 H CH3 CH2Ph H 79. CH3 CH3 CH3 CH3 H 80. n-Bu CH3 CH3 CH3 H 81. CF3 CH3 CH3 CH3 H 82. CF2CF3 CH3 CH3 CH3 H 83. CH20CH3 CH3 CH3 CH3 H 84. OCH3 CH3 CH3 CH3 H 85. Ph CH3 CH3 CH3 H 86. CH2Ph CH3 CH3 CH3 H 87. CH3 CH3 CH3 n-Bu H 88. CH3 CH3 CH3 CF3 H 89. CH3 CH3 CH3 CF2CF3 H 90. CH3 CH3 CH3 CH2OCH3 H 91. CH3 CH3 CH3 OCH3 H 92. CH3 CH3 CH3 Ph H 93. CH3 CH3 CH3 CH2Ph H 94. n-Bu n-Bu H H H 95. CF3 n-Bu H H H 96. CF2CF3 n-Bu H H H 97. CH2OCH3 n-Bu H H H 98. OCH3 n-Bu H H H 99. Ph n-Bu H H H CH2Ph n-Bu H H H 101 H H n-Bu n-Bu H 102 H H CF3 n-Bu H 103 H H CF2CF3 n-Bu H 104. H H CH20CH3 n-Bu H H H OCH3 n-Bu H 106 H H Ph n-Bu H 107 H H -CH2Ph n-Bu H 108. n-Bu H H H H 109. n-Bu H H CH3 H 110. n-Bu H H v H 111 n-Bu H H CF3 H 112. n-Bu H H CF2CF3 H 113 n-Bu H H CH2OCH3 H 114. n-Bu _ H H OCH3 H n-Bu H H Ph H 116 n-Bu H H -CH2Ph H 117. H H n-Bu H H 118 H CH3 n-Bu H H 119. H n-Bu n-Bu H H 120. H CF3 n-Bu H H 121 H CF2CF3 n-Bu H H 122. H CH2OCH3 n-Bu H H 123. H OCH3 n-Bu H H 124. H Ph n-Bu H H H -CH2Ph n-Bu H H 126 CH3 n-Bu n-Bu H H 127 n-Bu n-Bu n-Bu H H 128 CF3 n-Bu n-Bu H H 129 CF2CF3 n-Bu n-Bu H H CH20CH3 n-Bu n-Bu H H 131 OCH3 n-Bu n-Bu H H 132 Ph n-Bu n-Bu H H 133 -CH2Ph n-Bu n-Bu H H 134 CH3 H n-Bu n-Bu H n-Bu H n-Bu n-Bu H 136 CF3 H n-Bu n-Bu H 137 CF2CF3 H n-Bu n-Bu H 138 CH2OCH3 H n-Bu n-Bu H 139 OCH3 H n-Bu n-Bu H Ph H n-Bu n-Bu H 141 -CH2Ph H n-Bu n-Bu H 142 n-Bu n-Bu CH3 H H 143 n-Bu n-Bu CF3 H H 144 n-Bu n-Bu CF2CF3 H H n-Bu n-Bu CH2OCH3 H H 146 n-Bu n-Bu OCH3 H H

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147 n-Bu n-Bu Ph H H 148 n-Bu n-Bu -CH2Ph H H 149 n-Bu H CH3 n-Bu H n-Bu H CF3 n-Bu H 151 n-Bu H CF2CF3 n-Bu H 152 n-Bu H CH2OCH3 n-Bu H 153 n-Bu H OCH3 n-Bu H j154 n-Bu H Ph n-Bu H n-Bu H -CH2Ph n-Bu H 156 CH3 n-Bu n-Bu n-Bu H 157 n-Bu n-Bu n-Bu n-Bu H 158 CF3 n-Bu n-Bu n-Bu H 159 CF2CF3 n-Bu n-Bu n-Bu H CH20CH3 n-Bu n-Bu n-Bu H 161 OCH3 n-Bu n-Bu n-Bu H 162 Ph n-Bu n-Bu n-Bu H 163 -CH2Ph n-Bu n-Bu n-Bu H 164 n-Bu n-Bu n-Bu CH3 H n-Bu n-Bu n-Bu CF3 H 166 n-Bu n-Bu n-Bu CF2CF3 H 167 n-Bu n-Bu n-Bu CH2OCH3 H 168 n-Bu n-Bu n-Bu OCH3 H 169 n-Bu n-Bu n-Bu Ph H n-Bu n-Bu n-Bu -CH2Ph H 171 n-Bu CH3 n-Bu CH3 H 172 n-Bu CH3 n-Bu CF3 H 173 n-Bu CH3 n-Bu CF2CF3 H 174. n-Bu CH3 n-Bu CH20CH3 H 175. n-Bu CH3 n-Bu OCH3 _ 176 n-Bu CH3 n-Bu Ph 177 n-Bu CH3 n-Bu -CH2Ph H

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178 CF3 n-Bu n-Bu CH3 H

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179 CF2CF3 n-Bu n-Bu CH3 H CH2OCH3 n-Bu n-Bu CH3 H 181. OCH3 n-Bu n-Bu CH3 H 182 Ph n-Bu n-Bu CH3 H 183. -CH2Ph n-Bu n-Bu CH3 H 184 CH3 CH3 n-Bu n-Bu H CF3 CH3 n-Bu n H 186. CF2CF3 CH3 n-Bu n H 187. CH2OCH3 CH3 n-Bu n H 188. OCH3 CH3 n-Bu n H 189. Ph CH3 n-Bu n H 190. -CH2Ph CH3 n-Bu n H 191. n-Bu n-Bu CH3 CH3 H 192. n-Bu n-Bu CF3 CH3 H 193. n-Bu n-Bu CF2CF3 CH3 H 194. n-Bu n-Bu CH2OCH3 CH3 H n-Bu n-Bu OCH3 CH3 H 196. n-Bu n-Bu Ph CH3 H 197 n-Bu n-Bu -CH2Ph CH3 H 198. n-Bu CH3 CH3 CF3 H 199. n-Bu CH3 CH3 CF2CF3 H 200. n-Bu CH3 CH3 CH20CH3 H 201. n-Bu CH3 CH3 OCH3 H 202. n-Bu CH3 CH3 Ph H 203. n-Bu CH3 CH3 -CH2Ph H 204. CF3 CH3 CH3 n-Bu H 205. CF2CF3 CH3 CH3 n-Bu H 206. CH2OCH3 CH3 CH3 n-Bu H 207 OCH3 CH3 CH3 n-Bu H 208. Ph CH3 CH3 n-Bu H 209. -CH2Ph CH3 CH3 n-Bu H 210. CF3 n-Bu CH3 CH3 H 211. CF2CF3 n-Bu CH3 CH3 H 212. CH2OCH3 n-Bu CH3 CH3 H 213. OCH3 n-Bu CH3 CH3 H 214. Ph n-Bu CH3 CH3 H 215. -CH2Ph n-Bu CH3 CH3 H 216. CH3 CH3 CF3 n-Bu H 217 CH3 CH3 CF2CF3 n-Bu H 218. CH3 CH3 CH2OCH3 n-Bu H 219. CH3 CH3 OCH3 n-Bu H 86 2201 CH3 CH3 Ph n-Bu H 221 CH3 CH3 -CH2Ph n-Bu H 222 CF3 n-Bu H CH3 H 223 CF2CF3 n-Bu H CH3 H 224 CH2OCH3 n-Bu H CH3 H 225 OCH3 n-Bu H CH3 H 226 Ph n-Bu H CH3 H 227 -CH2Ph n-Bu H CH3 H 228 H CH3 CF3 n-Bu H 229 H CH3 CF2CF3 n-Bu H 230 H CH3 CH2OCH3 n-Bu H 231 H CH3 OCH3 n-Bu H 232 H CH3 Ph n-Bu H 233 H CH3 -CH2Ph n-Bu H 234 n-Bu H CH3 CF3 H 235 n-Bu H CH3 CF2CF3 H 236 n-Bu H CH3 CH2OCH3 H 237 n-Bu H CH3 OCH3 H 238 n-Bu H CH3 Ph H 239 n-Bu H CH3 -CH2Ph H 240 CF3 CH3 n-Bu H H 241 CF2CF3 CH3 n-Bu H H 242 CH2OCH3 CH3 n-Bu H H 243 OCH3 CH3 n-Bu H H 244 Ph CH3 n-Bu H H 245 -CH2Ph CH3 n-Bu H H 246 CF3 n-Bu CH3 H H 247 CF2CF3 n-Bu _ CH3 H H 248 CH2OCH3 n-Bu CH3 H H 249 OCH3 n-Bu CH3 H H 250 Ph n-Bu CH3 H H 251 -CH2Ph n-Bu CH3 H H 252 CH3 H CF3 n-Bu H 253 CH3 H CF2CF3 n-Bu H 254 CH3 H CH2OCH3 n-Bu H 255 CH3 H OCH3 n-Bu H 256 CH3 H Ph n-Bu H

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257 CH3 H -CH2Ph n-Bu H 258 n-Bu CH3 H CF3 H 259 n-Bu CH3 H CF2CF3 H 260 n-Bu CH3 H CH2OCH3 H 261 n-Bu CH3 H OCH3 H 262 n-Bu CH3 H Ph H 263 n-Bu CH3 H -CH2Ph H 264 CF3 H CH3 n-Bu H 265 CF2CF3 H CH3 n-Bu H 266 CH2OCH3 H CH3 n-Bu H - 87 267 OCH3 H | CH3 n-Bu H 268 Ph H CH3 n-Bu H 269 -CH2Ph H CH3 n-Bu H 270 H H H H CH3 271 CH3 H H H CH3 272 n-Bu H H H CH3 273 CF3 H H H CH3 274 CF2CF3 H H H CH3

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275 CH2OCH3 H H H CH3 276 OC 3 H H H CH3 277. Ph H H H CH3 278 -CH2Ph H H H CH3 279 H H CH3 H CH3 280 H H n-Bu H CH3 281 H H CF3 H CH3 282 H H CF2CF3 H CH3 283 H H CH2OCH3 H CH3 284 H H OCH3 H CH3 285. H H Ph H CH3

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286. H= H -CH2Ph H CH3 287. CH3 CH3 H H CH3 288 n-Bu CH3 H H CH3 289. CF3 CH3 H H CH3 290. CF2CF3 CH3 H H CH3 291. CH2OCH3 CH3 H H CH3 292. OCH3 CH3 H H CH3 293. Ph CH3 H H CH3 294. -CH2Ph CH3 H H CH3 295. H H CH3 CH3 CH3 296. H H CH3 n-Bu CH3 297. H H CH3 CF3 CH3 298 H H CH3 CF2CF3 CH3 299. H H CH3 CH2OCH3 CH3 300 H H CH3 OCH3 CH3 301 H H CH3 Ph CH3 302 H H CH3 -CH2Ph CH3 303 CH3 H H CH3 CH3 304 n-Bu H H CH3 CH3 305 CF3 H H CH3 CH3 306 CF2CF3 H H CH3 CH3 307 CH2OCH3 H H CH3 CH3 308 OCH3 H H CH3 CH3 309 Ph H H CH3 CH3 310 -CH2Ph H H CH3 CH3 311 H _ CH3 n-Bu H CH3 312 H CH3 CF3 H CH3 313 H CH3 CF2CF3 H CH3 314 H CH3 1CH2OCH3 |HCH3 315 H CH3 OCH3 HCH3 316 H CH3 Ph HCH3 317 H CH3 -CH2Ph HCH3 318 CH3 H CH3 CH3CH3 319 n-Bu H CH3 CH3CH3 320 CF3 H CH3 CH3 CH3 321 CF2CF3 H CH3 CH3CH3 322 CH2OCH3 H CH3 CH3CH 323 OCH3 H CH3 CH3CH 324 Ph H CH3 CH3CH 325 -CH2Ph H CH3 CH3CH 326 CH3 CH3 CH3 HCH 327 CH3 CH3 n-Bu HCH 328 CH3 CH3 CF3 HCH 329 CH3 CH3 CF2CF3 HCH 330 CH3 CH3 CH2OCH3 H CH 331 CH3 CH3 OCH3 H _ CH 332 CH3 CH3 Ph H CH 333 CH3 CH3 -CH2Ph H CH 334 n-Bu CH3 CH3 H CH 335 CF3 CH3 CH3 H CH 336 CF2CF3 CH3 CH3 H CH 337 CH2OCH3 CH3 CH3 H CH 338 OCH3 CH3 CH3 H CH 339 Ph CH3 CH3 H CH 340 -CH2Ph CH3 CH3 H CH 341 CH3 H CH3 n-Bu CH 342 CH3 H CH3 CF3 CH 343 CH3 H CH3 CP2CF3 CH 344 CH3 H CH3 CH2OCH3 CH 345 CH3 H CH3 OCH3 CH 346 CH3 H __ CH3 Ph CH 347 CH3 H _ CH3 -CH2Ph CH 348 CH3 CH3 CH3 CH3 CH 349 n-Bu CH3 CH3 CH3 CH 350 CF3 CH3 CH3 CH3 CH 351 CF2CF3 CH3 CH3 CH3 CH 352 CH20CH3 CH3 CH3 CH3 CH3 353 OCH3 CH3 CH3 CH3 CH3 354 Ph CH3 CH3 CH3 CH3 355 -CH2Ph CH3 CH3 CH3 CH3 356 CH3 CH3 _ CH3 n-Bu CH3 357 CH3 CH3 CH3 CF3 CH3 358 CH3 CH3 CH3 CF2CF3 CH3 359 CH3 CH3 CH3 CH2OCH3 CH3 360 CH3 CH3 CH3 OCH3 CH3 - 89 361 CH3 CH3 CH3 Ph CH3 362 CH3 CH3 CH3 -CH2Ph CH3 363 n-Bu n-Bu H H CH3 364 CF3 n-Bu H H CH3 365 CF2CF3 n-Bu H H CH3 366 CH2OCH3 n-Bu H H CH3 367 OCH3 n-Bu H H CH3 368 Ph n-Bu H H CH3 369 -CH2Ph n-Bu H H CH3 370 H H n-Bu n-Bu CH3 371 H H CF3 n-Bu CH3 372 H H CF2CF3 n-Bu CH3 373. H H CH20CH3 n-Bu CH3 374. H H OCH3 n-Bu CH3 375 H H Ph n-Bu CH3 376 H H -CH2Ph n-Bu CH3 377. n-Bu H H H CH3 378 n-Bu H H CH3 CH3 379. n-Bu H H n-Bu CH3 380 n-Bu H H CF3 CH3

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381 n-Bu H H CF2CF3 CH3 382. n-Bu H H CH2OCH3 CH3 383 n-Bu H H OCH3 CH3 384. n-Bu H H Ph CH3 385 n-Bu H H -CH2Ph CH3 386. H H n-Bu H CH3 387 H CH3 n-Bu H CH3 388. H n-Bu n-Bu H CH3 389 H CF3 n-Bu H CH3 390 H CF2CF3 n-Bu H CH3 391 H CH2OCH3 n-Bu H CH3 392 H OCH3 n-Bu H CH3 393 H Ph n-Bu H CH3 394 H -CH2Ph n-Bu H CH3 395 CH3 n-Bu n-Bu H CH3 396 n-Bu n-Bu n-Bu H CH3 397 CF3 n-Bu n-Bu H CH3 398 CF2CF3 n-Bu n-Bu H CH3 399 CH2OCH3 n-Bu n-Bu H CH3 400 OCH3 n-Bu n-Bu H CH3 401 Ph n-Bu n-Bu H CH3 402 -CH2Ph n-Bu n-Bu H CH3 403 CH3 H n-Bu n-Bu CH3 404 n-Bu H n-Bu n-Bu CH3 405 CF3 H n-Bu n-Bu CH3 406 CF2CF3 H n-Bu n-Bu CH3 407 CH2OCH3 H n-Bu n-Bu CH3 - 9o - 408. OCH3 H n-Bu n-Bu CH3 409. Ph H n-Bu n-Bu CH3 410. -CH2Ph H n-Bu n-Bu CH3 411 n-Bu n-Bu CH3 H CH3 412. n-Bu n-Bu CF3 H CH3 413. n-Bu n-Bu CF2CF3 H CH3 414. n-Bu n-Bu CH2OCH3 H CH3 415 n-Bu n-Bu OCH3 H CH3

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416. n-Bu n-Bu Ph H CH3 417. n-Bu n-Bu -CH2Ph H CH3 418 n-Bu H CH3 n-Bu CH3

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419 n-Bu H CF3 n-Bu CH3 420. n-Bu H CF2CF3 n-Bu CH3 421. n-Bu H CH2OCH3 n-Bu CH3 422. n-Bu H OCH3 n-Bu CH3 423. n-Bu H Ph n-Bu CH3 424. n-Bu H -CH2Ph n-Bu CH3 425. CH3 n-Bu n-Bu n-Bu CH3 426. n-Bu n-Bu n-Bu n-Bu CH3 427. CF3 n-Bu n-Bu n-Bu CH3 428. CF2CF3 n-Bu n-Bu n-Bu CH3 429. CH20CH3 n-Bu n-Bu n-Bu CH3 430 OCH3 n-Bu n-Bu n-Bu CH3 431. Ph n-Bu n-Bu n-Bu CH3 432. -CH2Ph n-Bu n-Bu n-Bu CH3 433 n-Bu n-Bu n-Bu CH3 CH3 434. n-Bu n-Bu n-Bu CF3 CH3 435. n-Bu n-Bu n-Bu CF2CF3 CH3 436. n-Bu n-Bu n-Bu CH2OCH3 CH3 437. n-Bu n-Bu n-Bu OCH3 CH3 438. n-Bu n-Bu n-Bu Ph CH3 439. n-Bu n-Bu n-Bu -CH2Ph CH3 440. n-Bu CH3 n-Bu CH3 CH3 441. n-Bu CH3 n-Bu CF3 CH3 442. n-Bu CH3 n-Bu CF2CF3 CH3 443. n-Bu CH3 n-Bu CH2OCH3 CH3 444. n-Bu CH3 n-Bu OCH3 CH3 445 n-Bu CH3 n-Bu Ph CH3 446. n-Bu CH3 n-Bu -CH2Ph CH3 447. CF3 n-Bu n-Bu CH3 CH3 448. CF2CF3 n-Bu n-Bu CH3 CH3 449. CH20CH3 n-Bu n-Bu CH3 CH3 450 OCH3 n-Bu n-Bu CH3 CH3 451. Ph n-Bu n-Bu CH3 CH3 452. -CH2Ph n-Bu n-Bu CH3 CH3 453. CH3 CH3 n-Bu n-Bu CH3 454. CF3 CH3 n-Bu n-Bu CH3 91 455 CF2CF3 CH3 n-Bu n-Bu CH3 456 CH20CH3 CH3 n-Bu n-Bu CH3 457 OCH3 CH3 n-Bu n-Bu CH3 458 Ph CH3 n-Bu n-Bu CH3 459 -CH2Ph CH3 n-Bu n-Bu CH3 460 n-Bu n-Bu CH3 CH3 CH3 461 n-Bu n-Bu CF3 CH3 CH3 462 n-Bu n-Bu CF2CF3 CH3 CH3 463 n-Bu n-Bu CH2OCH3 CH3 CH3 464 n-Bu n-Bu OCH3 CH3 CH3 465 n-Bu n-Bu Ph CH3 CH3 46 n-Bu n-Bu -CH2Ph CH3 CH3 467 n-Bu CH3 CH3 CF3 CH3 468 n-Bu CH3 CH3 CF2CF3 CH3 469 n-Bu CH3 CH3 CH2OCH3 CH3 470 n-Bu CH3 CH3 OCH3 CH3 471 -Bu CH3 CH3 Ph CH3 472 n-Bu CH3 CH3 -CH2Ph CH3 473 -CF3 CH3 CH3 n-Bu CH3 474 CF2CF3 CH3 CH3 n-Bu CH3 475 CH20CH3 CH3 CH3 n-Bu CH3 476 OCH3 CH3 CH3 n-Bu CH3 477 Ph CH3 CH3 n-Bu CH3 478 -CH2Ph CH3 CH3 _ n-Bu CH3 479 CF3 n-Bu CH3 CH3 CH3 480 CF2CF3 n-Bu CH3 CH _ CH3 481 CH20CH3 n-Bu CH3 CH3 CH3 482. OCH3 n-Bu CH3 CH3 CH3 483 h n-Bu CH3 CH3 CH3 484 -CH2Ph n-Bu CH3 CH3 CH3 485. CH3 CH3 CF3 n-Bu CH3 486 CH3 CH3 CF2CF3 n-Bu CH3 487 CH3 CH3 CH2OCH3 n-Bu CH3 48 H3 CH3 OCH3 n-Bu CH3 489. CH3 CH3 Ph n-Bu CH3 490. CH3 CH3 -CH2Ph n-Bu CH3 491. CF3 n-Bu H CH3 CH3 492 CF2CF3 n-Bu H CH3 CH3 493 CH2OCH3 n-Bu H CH3 CH3 494. OCH3 n-Bu H CH3 CH3 495 Ph n-Bu H CH3 CH3 496 -CH2Ph n-Bu H CH3 CH3 497. H CH3 CF3 n-Bu CH3 498. H CH3 CF2CF3 n-Bu CH3 499. H CH3 CH2OCH3 n-Bu CH3 500 H CH3 OCH3 n-Bu CH3 501. H CH3 Ph n-Bu CH3 - 92 502i H | CH3 -CH2Ph n-Bu CH3 503 n-Bu H CH3 CF3 CH3 504 n-Bu H CH3 CF2CF3 CH3 505 n-Bu H CH3 CH20CH3 CH3 506 n-Bu H CH3 OCH3 CH3 507 n-Bu H CH3 Ph CH3; 508 n-Bu H CH3 -CH2Ph CH3 509 CF3 CH3 n-Bu H CH3 510 CF2CF3 CH3 n-Bu H CH3 511 CH20CH3 CH3 n-Bu H CH3 512 OCH3 CH3 n-Bu H CH3 513 Ph CH3 n-Bu H CH3 514 -CH2Ph CH3 n-Bu H CH3 515 CF3 n-Bu CH3 H CH3 516 CF2CF3 n-Bu _ CH3 H CH3 517 CH20CH3 n-Bu CH3 H CH3 518 OCH3 n-Bu CH3 H CH3 519 Ph n-Bu CH3 H CH3 520 -CH2Ph n-Bu CH3 H CH3 521 CH3 H CF3 n-Bu CH3 522 CH3 H CF2CF3 n-Bu CH3 523 CH3 H CH2OCH3 n-Bu CH3 524 CH3 H OCH3 n-Bu CH3 525 CH3 H Ph n-Bu CH3 526 CH3 H -CH2Ph n-Bu CH3 527 n-Bu CH3 H CF3 CH3 528 n-Bu CH3 H CF2CF3 CH3 529 n-Bu CH3 H CH2OCH3 CH3 530 n-Bu CH3 H OCH3 CH3 531 n-Bu CH3 H Ph CH3 532 n-Bu CH3 H -CH2Ph CH3 533 CF3 H CH3 n-Bu CH3 534 CF2CF3 H CH3 n-Bu CH3 535 CH2OCH3 H CH3 n-Bu CH3 536 OCH3 H CH3 n-Bu CH3 537 Ph H CH3 n-Bu CH3 538 -CH2Ph H CH3 n-Bu CH 539 H -CH2- H CH3 540 H -(CH2)4- H CH3 s For the following exaTnple compounds physico- chemical data have been obtained and are displayed in order to illustrate the working of the present invention, including the outlined methods of synthesis. The number of given data may not be interpreted as a - 93 limitation ofthe invention. Analysis of compounds 6.610 to 6.684: Reversed-phase was performed on a Waters Alliance 2790 LC equiped with a Waters996 W detector using a YMC CombiScreen ODS-AQ cartridge (30x4.6 mm, S-5 [lm, 12 urn) Mobile phase: A: H2O/CH3CN 10/TFA, B: CH3CN/TFA 0.1, C: MeOH.Gradient: 89% A 11% B. 0-3.5 s mini 90% B 10% C 0.5 min.

Table C

Comp. No. from Melting point [0C] or Table B Table A 'H-NMR [6 in ppm] 1.001 028 122-131 1.002 028 199-201 1.003 028 (DMSO); 0.60(t,3H), l.l9(s,3H), 1.67(q,2H), 2.02(s,3H), 6.93(dd,1H), 7.26(t,1H), 7.47(d,1H), 7.76(dd,1H), 7.83(dd,1H), 7.93(dd,1H), 8.48(d,1H), 8.55(d,1H), 8.63(d,1H), 10.00(s,NH); 1.004 028 187-192 1.005 028 (CDCI3); 1.80(s,3H), 2.14(s,3H), 7.00(dd,1H), 7.22 7.29(m,7H), 7.39(dd,1H), 7.72(s,1H), 7.84(s,1H), 8.52(d,1H), 8.70(dd,1H), 8.77(s,NH); 1.006 028 167-168 1.007 028 90-92 1.008 028 95-99 1.009 028 (DMSO); 1.41(s,3H), 2.18(s,3H), 3.10(s,2H), 7.04(d,1H), 7.14(s,5H), 7.38(t,1H), 7.50(d,1H), 7.85(d,1H), 7.92(d,1H), 7.98(s,1H), 8.42(s,1H), 8.55(d,1H), 8.71(d,1H), 10.09(s,NH); 1.010 028 165-168 1.011 028 215-219 1.012 028 210 1.050 028 202-205 1.051 028 164-167 1.052 028 167-170 1.053 028 189-192 2.002 028 181-185 2.003 028 204-208 - 94 2.004 028 210 2.005 028 190-192 2.006 028 199-203 2.007 028 180-182 2.008 048 127-135 2.009 028 87-83 2.010 028 195-197 2.011 028 187-189 2.012 0.28 218-220 3.001 028 163-166 3.002 028 189-191 3.003 028 158 3.011 028 (DMSoj; 3.32(s,3H),4.35(s,2H),5.66(s,1H),7.03(dd,1H), 7.35(t,1H),7.62(m,1H),7.77(m,1H),8.00(m,1H), 8.20(m,1H),8.48(m,1H),8.62(d,1H),8.74(d,1H), 10.12(s,NH),12.25(s,1H); 3.012 028 158-159 3.013 028 167 3.014 028 141-150

_

3.015 028 (DMSO); 1.74(s,3H),2.15(s,3H),7.01(dd,1H),7.37(t,1H), 7.46(s,1H),7.82(s,1H),7.93(d,2H),8.55(d,1H),8.63(d,1H), 9.21(s,1H),10.07(s,NH),11.5/12.0(s,1H); 3.016 028 (DMSO); 1.85(s,3H),7.02(dd,1H),7.35-7.79(m,7H), 8.61(d,1H),8.74(d,1H),10.12(s,NH)? 11.7/ll.9(s,lH); 3.017 028 185-188 3.018 028 171-174 3.019 028 149-150 3.020 028 155-157 3.027 028 178-180 3.028 028 181-184 3.029 028 199-201 3.030 028 120-125 3.031 028 169-170 3.032 028 184 - 95 3.033 028 171-175 3.034 028 163-167 3.035 028 152-161 3.036 028 115-119 3.037 028 182-1853.038 028 160-163 3.039 028 210 3.040 028 184 3.041 028 210 5.001 028 143-144 5.002 028 151-153 5.003 028 166-168 5.004 028 200-202 1.001 048 (DMSO); 1.31(s,6H), 2.14(s,3H), 3.42(s,3H), 5.49(s,2H), 7.37-7.60(m,5H), 7.88(dd,1H), 8.54(s,1H), 8.61(d,1H), 8.64(d,1H); 6.002 028 238-240 6.003 028 120-125 6.012 028 229-231 6.015 028 173-175 6.020 028 184-186 6.152 028 213-215 6.153 028 118-127 6 177 028 184-186 6.179 028 187-189_ 6.605 028 196 198 6.606 028 79-84 6.607 028 153-156 6.608 028 110-120 6.609 028 213-216 6.610 028 RT 3.3 MS 614.2(Area MS 100%, AreaW 100%) 6.611 028 RT 3.23 MS 564.2 (Area MS100 %, AreaW 100%) 6.612 028 RT 3.9 MS 622.3(Area MS 100%, AreaW 100%) 6.613 028 RT 2.37 MS 550(Area MS 100%, AreaW 100%) 6.614 028 RT 2.37 MS 550(Area MS 100%, AreaW 100%) - 96 6.615 048 RT 2.15 MS 478.1 (Area MS 100%, AreaW 100%) 6.616 028 RT 2.4 MS 480.1 (Area MS 100%, AreaW 84%) 6.617 028 RT 2.37 MS 480.1(Area MS 100%, AreaW 100%) 6.618 028 RT 2.1 MS 480.1(Area MS 100 %, AreaW 88%) 6.619 028 RT 2.32 MS 480.1(Area MS 100%, AreaW 100%) 6.620 028 RT 2.1 MS 555.1 (Area MS 100%, AreaW 90%) 6.621 028 RT 2.1 MS 555.1 (Area MS 100%, AreaW 90%) 6.622 028 RT 2.1 MS 468.1(Area MS 100%, AreaW 85%) 6.623 028 RT 1.54 MS 572.1 (Area MS 100%, AreaW 89%) 6.624 028 RT 2.5 MS 482.1 (Area MS 100%, AreaW 100%) 6.625 028 RT 2.24 MS 466.1(Area MS 100%, AreaW 100%) 6.626 028 RT 1.95 MS 466.1(Area MS 100%, AreaW 100%) 6.627 028 RT 1.85 MS 464.1 (Area MS 100%, AreaW 100%) 6.628 028 RT 2.1 MS 492.1 (Area MS 100%, AreaW 92%) 6.629 028 RT 2 MS 478.1(Area MS 100%, AreaW 100%) 6.630 028 RT 2 MS 478.1(Area MS 100%, AreaW 100%) 6.631 028 RT 2.5 MS 494.1 (Area MS 100%, AreaW 93%) 6.632 028 RT 2.1 MS 480.1 (Area MS 100%, AreaW 74%) 6.633 028 RT 2.1 MS 480.1 (Area MS 100%, AreaW 74%) 6.634 028 RT 2.24 MS 494.1 (Area MS 100%, AreaW 100%) 6.635 028 RT 2.24 MS 494.1(AreaMS 100%, AreaW 100%) 6.636 028 RT 3.1;3.2 MS 580.1(Area MS 70%, AreaW 62%) 6.637 028 RT 4 MS 598(Area MS 77%, AreaW 100%) 6.638 028 RT 3.47 MS 610.1(Area MS 58%, AreaW 100%) - 97 6.639 028 RT 3.5 MS 564.1(Area MS 67%, AreaW 100%) 6.640 028 RT 3.4 MS 598.1 (Area MS 79%, AreaW 80%) 6.641 028 RT 3.22 MS 560.1 (Area MS 69%? AreaW 100%) 6.642 028 RT 3.07 _ MS 660.1 (Area MS 100%, AreaW 100%) 6.643 028 RT 3.1 MS 514(Area MS 59%, AreaW 100%) 6.644 028 RT 2.8 MS 522.1(Area MS 72%, AreaW 100%) 6.645 028 RT 3.07 MS 548(Area MS 80%, AreaW 100%) 6.646 028 RT 4.4 _ MS 638.2(Area MS 90%, AreaW 62%) 6.647 028 RT 3.5 MS 580.1(Area MS 57%, AreaW 100%) 6.648 028 RT 2.81;2.8 MS 500.1 (Area MS 63 %, AreaW 100%) 6.649 028 RT 4 MS 538.2(Area MS 84%, AreaW 100%) 6.650 028 RT 3.11 MS 546.1(Area MS 53%, AreaW 80%) 6.651 028 RT 2.7;2.8 MS 540.1 (Area MS 56%, AreaW 74%) 6.652 028 RT 4.5 MS 592.2(Area MS 62%, AreaW 100%) 6.653 028 RT 3.5 MS 554.2(Area MS 96%, AreaW 100%) 6.654 028 RT 4.3 MS 562.2(Area MS 71%, AreaW 100%) 6.655 028 RT 3.47 MS 494.1 (Area MS 100%, AreaW 100%) 6.656 028 RT 3 MS 514.1(AreaMS 86%, AreaW 100%) 6.657 028 RT 2.2 MS 551.1(Area MS 74%, AreaW 100%) 6.658 028 RT 3.36 MS 508.1 (Area MS 100%, AreaW 100%) 6.659 028 RT 3.22 MS 590.1(Area MS 84%, AreaW 100%) 6.660 028 RT 3.3 MS 564.1(Area MS 69%, AreaW 74%) 6.661 028 RT 3.8 MS 758(Area MS 42%, AreaW 100%) 6.662 028 RT 3.4 MS 566.1(AreaMS 78%, AreaW 100%) 6.663 028 RT 3.4 M S 642( ea M S 80%,/tea W 100%) 6.664 028 RT 3 M S 614.2(xea M S 82%,Aea W 100%) 6.665 028 RT 2.4 M S 512.1(Axea M S 92%,Axea W 82 %) 6.666 028 RT 2.0;2.3 M S 545.1( ea M S 82 %,Axea W 100 %) 6.667 028 RT 3.2 M S 494.1( ea M S 74%,/ea W 1 00%) 6.668 028 RT 3.4 M S 596.1(ea M S 75%,Asea W 100%) 6.669 028 RT 4.4 M S 658.1( ea M S 66%,/xea W 1 %? 6.670 028 RT 3.3 M S 562.1(ea M S 81%,}xea W 100%) 6.671 028 RT 3.1 M S 585( ea M S 70%,Aea W 100%) 6.672 028 RT 2.04;2.1 M S 531.1( ea M S 84 %,}xea W 100%) 6.673 028 RT 3.9 M S 586.2( ea M S 88%,/sea W 100%) 6.674 028 RT 3 M S 522( ea M S 91%,Aea W 100%) 6.675 028 RT 4.3 M S 578.2( ea M S 88%,/ea W 100%) 6.676 028 RT 2.78;2.8 M S 512.1(ea M S 100%,Aea W 100%) 6.677 028 RT 2.7 M S 525.l(Axca M S 95%,Aea W 100%) 6.678 028 RT 3.3 M S 584.1( ea M S 91 %,/ea W 100 %) 6.679 028 RT 1.8;2.1 M S 517.1(Aea M S 72%,Pea W 100%) 6.680 028 RT 3.7 M S 512.1( ea M S 96%,AIea W 100%) 6.681 028 RT 3 M S 516.1( ea M S 54 %,/ea W 38%) 6.682 028 RT 3.5 M S 708(ea M S 71%,Aea W 100%) 6.683 028 RT 3.7 M S 720.1( ea M S 81%,/ea W 100%) 6.684 028 RT 3.1 M S 607.1(xea M S 88%,Aea W 100%) 6.685 028 80-100 6.686 028 183-186 6.687 028 212-215 6.688 028 176-178 - 99 - 6.689 028 183-185 6.690 028 110-115 6.691 028 119-123 6.692 028 117-120 6.693 028 83-89 6.694 028 90-100 6.695 028 73-76 6.696 028 110-120 6.697 028 145-160 6.698 028 84-90 6.699 028 239-242 6.700 028 90-105 6.701 028 232-235 6.702 028 178-182 6.703 028 142-148 6.704 028 222-225 6.705 028 75-85 6.706 028 142-144 6.707 028 235-240 6.708 028 141-144 6.709 028 80-82 6.710 028 82-84 6.711 028 174-176 6.712 028 201-203 6.713 028 120-125 6.714 028 198-200 RT 2.06 MS 464.1(Area MS 100%, AreaW 100%) 6.715_ 028 85-90 6.716 028 87-97 6.717 028 251-253 6.718 028 RT 2.41 MS 512.1 (Area MS 100%, AreaW 0%) 6.719 028 RT 2.63 MS 510.1(AreaMS 88%, AreaW 100%) 6.720 028 RT 2.4 MS 482.1(Area MS 90%, AreaW 82%) 6.721 028 92-96 _ 6.722 028 90-100 6.723 028 110-115 6.724 028 188-190 6.725 028 70-80 6.726 028 182-184 7.001 028 110-130 7 270 028 189-192 7 271 028 207-209 7.277 028 89-93 100 7.303 028 177-179 7.808 028 165-167 7.830 028 90-95 8.270 028 201-204 8.271 028 193-195 8.277 028 105-115 8.279 028 95-100 8.285 028 98-105 8.303 028 105-110 8.539 028 80-85 8.540 028 95-100 In the following, examples of test systems in plant protection are provided which can demonstrate the efficiency of the compounds of the formula I (designated as "active ingredient" or "test compounds"):

Biological Examples

Example B-1: Effect against Puccinia graminis on wheat (brownrust on wheat! a! Residual protective activity 1 week old wheat plants cv. Arina are treated with the formulated test- compound (0.02 % active substance) in a spray chamber. Two days after application wheat plants are lo inoculated by spraying a spore suspension (1 x 105 ureidospores/ml) on the test plants.

After an incubation period of 1 day at +20 C and 95% relative atmospheric humidity (r.

h.) plants are kept for 9 days at +20 C and 60% r.h. in a greenhouse. The disease incidence is assessed 10 days after inoculation.

At the indicated concentration compounds 1.01/028; 2.02/028; 1.03/028; 1. 07/028; 2.03/028; 2.05/028; 2.06/028 exhibited over 70% control of the fungal infection in this test.

Example B-2: Effect against Phvtophthora infestans on tomatoes (late blight on potato! a! Residual protective activity 3 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02 % active substance) in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (2 x 104 sporangialml) on the test plants.

After an incubation period of 4 days at +18 C and 95% r. h. in a growth chamber the disease incidence is assessed.

At the indicated concentration compounds 1.01/028; 1.03/028; 1.04/028; 1. 07/028 exhibited over 70% control of the fungal infection in this test. 101

Example B-3: Effect against PhYtophthora infestans / potato (late blight on potato! week old potato plants cv. Bintje are treated with the formulated test compound (0.02 % active substance) in a spray chamber. Two days after application the plants are inoculated by spraying a sporangia suspension (1.4 x 105 sporangia/ml) on the test plants.

After an incubation period of 4 days at +18 C and 95% r. h. in a growth chamber the disease incidence is assessed.

Example B-4: Effect against Plasmopara viticola on grapevine (grape downy mildew! 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02 % active substance) in a spray chamber. One day after application grape plants are inoculated by spraying a sporangia suspension (4 x 104 sporangia/ml) on the lower leaf side of the test plants. After an incubation period of 6 days at +22 C and 95% r. h. in a greenhouse the disease incidence is assessed.

IS At the indicated concentration compounds 1.01/028;3.01/028; 1.04/028 exhibited over 70% control of the fungal infection in this test.

Example B-5: Residual protective activity against Venturia inacqualis on apples (scab on apple! 4 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02 % active substance) in a spray chamber. One day after application apple plants are inoculated by spraying a spore suspension (4 x 105 conidiaml) on the test plants. After an incubation period of 4 days at + 20 C and 95% r. h. the plants are transferred to standard greenhouse conditions at 20 and 60% r.h. where they stayed for 2 days. After another 4 day incubation period at +20 C and 95% r. h. the disease incidence is assessed.

2s At the indicated concentration compounds 2.03/028; 1.001/028 exhibited over 70% control of the fungal infection in this test.

Example B-6: Effect against Ervsiphe graminis on barleY (powderY mildew on barle a) Residual protective activity Barley plants, cv. Regina of approximately 8 cm height were treated with the formulated test compound (0.02% active substance) in a spray chamber and duste 2 days after inoculation with conidia of the fungus. The infected plants are placed in a greenhouse at +20 C. 6 days after infection, the fungal attack was evaluated. - 102

At the indicated concentration compounds 1.01/028; 1.03/028; 1.04/028, 2. 05/028; 2.09/028; 3.014/028; 3.030/028 exhibited over 70% control of the fungal infection in this test.

Example B-7: Botrytis cinerea / grape (botrytis on grapes! 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active substance) in a spray chamber. Two days after application grape plants are inoculated by spraying a spore suspension (1.5 x 105 conidia/ml) on the test plants. After an incubation period of 3 days at + 21 C and 95% r. h. in a greenhouse the disease incidence is assessed.

lo At the indicated concentration compounds 1.01/028; 1.03/028; 1.04/028, 1.05/028; 1.06/028,1.07/028;2.03/028; 2.05/028; 2.08/048; 2.09/028; 3.012/028; 3.013/028;3.014/028; 2.012/028 exhibited over 70% control of the fungal infection in this test.

Example B-8: Effect against Botrytis cinerea I tomato (botrytis on tomatoes! 4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound 0.02 % active substance) in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension (1 x 105 conidia/ml) on the test plants.

After an incubation period of 4 days at +20 C and 95% r. h. in a greenhouse the disease incidence is assessed.

At the indicated concentration compounds 1.01/028; 2.02/028; 3.01/028; 1. 04/028; 1.06/028; 2.06/028; 2.05/028; 2.08/048; 4.02/028; 7.270/028 exhibited over 70% control of the fungal infection in this test.

Example B-9: Effect against Pyricularia oryzue / rice (rice blast! 3 week old rice plants cv. Sasanishiki are treated with the formulated test compound 2s (0.02 % active substance) in a spray chamber. Two days after application rice plants are inoculated by spraying a spore suspension (I x 105 conidia/ml) on the test plants. After an incubation period of 6 days at +25 C and 95% r. h. the disease incidence is assessed.

At the indicated concentration compounds 1.02/028; 1.04/028; 2.03/028; 2. 06/028; 2.07/028 exhibited over 70% control of the fungal infection in this test.

Example B-10: Effect aainst Pvrenophora teres (HelminthosporiumJ I barley (net blotch on barley! 1 week old barley plants cv. Regina are treated with a formulated test compound (0.02 % active substance) in a spray chamber. Two days after application barley plants are - 103 inoculated by spraying a spore suspension (3 x 104 conidia/ml) on the test plants. After an incubation period of 2 days at +20 C and 95% r.h. the disease incidence is assessed.

At the indicated concentration compounds 1.01/028; 2.02/028; 3.01/028; 5. 01/028; 1.03/028; 1.04/028, 1.01/048; 1.06/028,1.07/028;1.08/028; 2.03/028; 2. 05/028; 2.07/028; 2.08/048; 2.09/028; 3.012/028; 3.013/028;3.014/028; 2.012/028; 2.011/028; 3.016/028; 3.017/0283.027/028; 3.028/028; 7.270/028 exhibited over 70% control ofthe fungal infection in this test. i Example B-11: Effect against Fusarium culmorum /wheat (fusarium head blight on wheat! A conidia suspension of F. culmorum (7 x 105 conidia/ml) is mixed with the formulated test compound (0.002 % active substance)The mixture is applied into a pouch which has been equipped before with a filter paper. After the application wheat seeds (cv.

Orestis) are sown into the upper fault of the filter paper. The prepared pouches are then incubated for 11 days at approx. +10 C to +18 C and a relative humidity of 100% with a light period of 14 hours. The evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.

Example B-12: Effect against Septoria nodorum /wheat (septoria leaf spot on wheat! I week old wheat plants cv. Arina are treated with a formulated test compound (0.02 % active substance) in a spray chamber. One day after application wheat plants are inoculated by spraying a spore suspension (6 x 105 conidia/ml) on the test plants. After an incubation period of 1 day at +22 C and 95% r.h. plants are kept for 7 days at +22 C and 60% r.h. in a greenhouse. The disease incidence is assessed 8 days after inoculation.

At the indicated concentration compounds 1.01/028; 2.02/028; 3.01/028; 5. 01/028; 1.03/028; 1.06/028,1.07/028; 2.03/028;2.04/028; 2.05/028; 2.06/028; 2. 09/028; 3.012/028; 2.012/028; 3.028/028 exhibited over 70% control of the fungal infection in == this test. - 104

Claims (13)

1. A composition for controlling and protecting against fingal organisms, compri s sing a compound of formula I: iN'1N Nit ( )n If Rio ( ) NiR R3><Cp_RRs6 R7 R8 wherein miss, 1,20r3; n and p are independently of each other O or 1; lo R. is halogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted thioalkyl optionally substituted aryl, COOR,,, CONR,2R,3, S(O)qR4, SO2NR, 5R,6 or NR,5aR,6a; when there is more than on R' group, they may be the same or different; q is 1 or 2; R2, R2a, R3, R4, R5, R6, R7, Rx are each independently hydrogen, optionally substituted alkyl, CORE, COORS or optionally substituted aryl, and in addition R2 and R3 may also independently be optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, or optionally substituted alkylthio, COORS, CONR20R2,, OH or SH; R6 and R7 may also be independently halogen, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkenylamino, optionally substituted alkynylamino, optionally substituted alkylthio, optionally substituted cycloalkyl, optionally substituted heteroaryl, optionally substituted hetrocyclyl, optionally substituted cycloalkyloxy, OH, SH, N3, NR22R23 or N(R24)COR25; or the ring members CR3R4 or CR2R2A are independently of each other a carbonyl - 105 group (C=O) or a thonyl group (C=S); or one or two of the adjacent pairs of groups R. and R4, R4 and Ra, R5 and R8, or, if p is zero, R2A and R8 may form a bond, provided that if there are 2 double bonds in the ring the double bonds are not adjacent each other; or the pair of groups R7 and R8 or the pair of groups R6 and R7 together with the atom to which they are attached form a C3-C7 saturated ring; Rg is hydrogen, optionally substituted alkyl, optionally substituted alkenyl or Rio is hydrogen, C- C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, -CH20R26, CH2SR27, -C(0)R2x,-C(0)0R29,SO2R30, SOR3or SR32; R26, R27, R28, R29, R30, Rat, R32 are independently C,-C8-alkyl C,-C8-alkoxyalkyl, C,-C8 haloalkyl or phenylC,-C2-alkyl wherein the phenyl may be substituted by up to three groups selected from halo or C,-C4-alkyl, Rll,RI2, Rl3, R4, R5, R,6 R5a, R,6a, R7,R8, R9, R20, R21, R22,R23, R24, and R25 are independently H or optionally substituted alkyl; or a salt thereof as active ingredient together with a suitable carrier and optonally additional active compounds.

2. A composition according to claim 1, wherein the moiety 1 R2 R321 R4 7< P-R6 R7 RB is a 5- and 6-membered ring selected from 2,4-dihydro-pyrazol3-ones, 2,4 dihydro-pyrazole-3-thione, lH-pyrazoles, 2H-pyridazin-3-ones, 4,5-dihydro-2H pyridazin-3-ones, 1,2-dihydro-pyrazol-3-ones, 1,2-dihydropyrazole-3-thione, pyrazolidin-3-one, pyrazolidine-3-thione, 2H-pyridazin3-thione and 4,5-dihydro 2H-pyridazin-3 -thione.

3. A composition according to claims 1 or 2, wherein R is halogen, C 1-3 haloalkoxy, CH(OH)R, COR, S02NRR', CH(NR'R")R, COORa or CONRbRc where Ra, Rb, Rc, R. R', R" are independently H or lower alkyl. - 106

4. A composition according to any one of claims 1 to 3, wherein R2, R2A, R3, R4, RS, R6, R7, RS and R9 independently of each other are hydrogen or methyl.

5. A composition according to any one of claims 1 to 4, wherein n is zero.

6. A composition according to any one of claims 1 to 5, wherein m is 1 and the R! group is at the 3-position of the phenyl ring.

lo

7. A composition according to any one of claims 1 to 6, wherein R7 is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or ethoxymethyl, more preferably hydrogen or methoxymethyl.

8. A composition according to any one of claims 1 to 7 where Rio is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or ethoxymethyl, preferably hydrogen or methoxymethyl.

9. A composition according to any one of claims 1 to 8, wherein the compound is selected from (3-Chloro-phenyl)- {4-[2-(3,4,5-trimethylpyrazol- 1 -yl)-pyridin-4 yl]-pyrimidin-2-yl}-amine; (3 -Chloro-phenyl){4-[2-(5-methoxy-3-methoxymethyl-pyrazol- 1 -yl)- pyridin-4 yl] -pyrimidin-2-yl} -amine; (3 -Chloro-phenyl){4-[2-(5-methoxy-3-methoxymethyl-4-methyl-pyrazol- 1 - yl) pyridin-4-yl] -pyrimidin-2-yl} -amine; (3-Chloro-phenyl)-{4-[2-(5-methoxy-4-methyl-pyrazol-1-yl)-pyridin-4-yl] pyrimidin-2-yl} -amine; (3-Chloro-phenyl){4-[2-(5-ethoxy-3,4-dimethyl-pyrazol- 1 -yl)-pyridin-4- yl] pyrimidin-2-yl} -amine; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -5 methoxymethyl- 1,4-dimethyl- 1,2-dihydro-pyrazol-3-one; 2-(4{2-[(3-Chloro-phenyl)-methoxymethyl-amino]-pyrimidin-4-yl}-pyridin- 2 yl)1,5 -dimethyl- 1,2-dihydro-pyrazol-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1 -ethyl-4, 5 - 107 dimethyl- I,2-dihydro-pyrazol-3 -one; 2- 4-2-(3 -Chloro-phemilamino)-pyri midin-4-yll-pyridin-2-yl -1.4- dirnethyl- 1,2 dihydro-pyrazol-3 -one, 2- { 4-[2-(3 -Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl -1, 5 - dimethyl- 1,2 dihydro-pyrazol-3-one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl -5 methoxymethyl-4,4-dimethyl-2,4-dihydro-pyrazol-3 -one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -4,4dimethyl-2,4 dihydro-pyrazol-3 -one; lo 2- {4-[2-(3 -Chloro-phenylamino)pyrimidin-4-yl]-pyridin-2-yl} -4,4,5-trimethyl 2,4-dihydro-pyrazole-3 -thione; 5- {4-[2-(3 -Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -7-methyl- 5,6 diaza-spiro[2.4]hept-6-en-4-one, 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -4-ethyl-4, 5 dimethyl-2,4-dihydro-pyrazol-3-one; (3-Chloro-phenyl)-{4-[2-(5-methoxy-3 -methyl-pyrazol- 1 -yl)-pyridin-4-yl] pyrimidin-2-yl} -amine; 2-4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1,4,5trimethyl 1, 2-dihydro-pyrazol-3 -one, 2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-4,4,5trimethyl 2,4-dihydro-pyrazol-3 -one, 2-{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -1,5dimethyl- 1,2 dihydro-pyrazol-3 -one; 4, 5-Dichloro-2-{ 4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2- yl} -2H pyridazin-3-one; 2- { 4-[2-(3 -Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl -6-methyl- 2H pyridazin-3 -one; 2- {4-[2-(3 -Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl -6-methyl-4, 5 dibydro-2H-pyridazin-3 -one; 2{4-[2-(3-Chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl} -6-Phenyl-4, 5 dibydro-2H-pyridazin-3 -one, 4-Chloro-2{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yll-pyridin-2-yl} -5 ethoxy-2H-pyri dazin-3 -one, - 108 4-Chloro-2-{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2-yl}-5 ethylsulfanyl-2H-pyridazin-3-one; and 5-Azido-4-chloro-2-{4-[2-(3-chloro-phenylamino)-pyrimidin-4-yl]-pyridin-2yl} 2H-pyridazin-3 -one. s

10. The use of a composition as defined in claim 1 in protecting plants against infestation by phytopathogenic microorganisms.

11. A method of controlling and preventing an infestation of crop plants by o phytopathogenic microorganisms, which comprises the application of a composition as defined in claim 1 to the plant, to parts of plants or to the locus thereof.

12. A method according to claim 12, wherein the phytopathogenic microorganisms s are fungal organisms.

13. A mixture of a compound of formula (I) as defined in claim 1 with another fungicide selected from azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazo le. cyproconazol e, di fenoconazole, d ini conazo le. epoxi conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as 2s bupiri mate, dimethiri mol. ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, - 109 kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; and acibenzolar-S-methyl, anilazine, o benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflubenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).