FR2634202A1 - HETEROCYCLIC COMPOUNDS, PROCESS FOR THEIR PREPARATION AND FUNGICIDE COMPOSITION CONTAINING SAME - Google Patents

Abstract

The invention relates to novel heterocyclic compounds. The compounds of the invention correspond to the general formula: (CF DRAWING IN BOPI) in which R ** 1 is an organic group, R ** 2 to R ** 6 represent hydrogen or an organic group, X, Y and Z represent hydrogen, a halogen or an organic group, Az is a 1-imidazole or 1,2,4-triazole group and Q is an organic group, their stereoisomers and their salts and metal complexes, provided that when R ** 3 and R ** 4 are both alkyl groups, R ** 5 represents H, R ** 6 is alkyl, alkenyl or alkynyl and Q represents CH2, then R ** 1 is not a CH = CH2 group. It also relates to their method of preparation. Application: Fungicidal compositions for plant protection.

Description

The present invention relates to heterocyclic compounds which are

  useful as fungicides, processes for their production, fungicidal compositions which contain them, and methods for their use in combating fungi, especially fungicides.

  Fungal infections in Plants.

  According to the invention, there is provided compounds corresponding to the general formula (I): x R3 OR-R, C i

, ___ C --C --- C - .. A :: (I)

Z 'R4 R6

  R1 and their stereoisomers, in which R1 represents a group of general formula (II): ## STR2 ## or a group of general formula (III): (III) C = C

R8 R10

  R 7 R 10 independently represent hydrogen, R 7 to R 10 independently represent hydrogen, halogen, alkyl, alkenyl or alkynyl; R2 is hydrogen, alkyl, alkenyl or alkynyl (with the proviso that carbon atoms adjacent to oxygen are not involved in any unsaturation); R3 to R6 are, independently, hydrogen, alkyl, alkenyl or alkynyl; X, Y, and Z independently represent hydrogen, halogen, optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, optionally substituted aralkyl, optionally substituted alkoxy, aryloxy, or optionally substituted aralkoxy; Az represents an imidazol-1-yl or 1,2,4-triazol-1-yl group; Q is a bridging group having one of the following values Q1, Q2, Q3 or Q4: R1

I1 1

R12 R14

RI

R11 R13 R15

I, i Q3 C- C - c I t i

R12 R14 R16

R1 R13 R15 R17

I I I

Q4 = - C C C C C

  R18 to R18 are, independently, hydrogen, halogen, alkyl, alkenyl or alkynyl; and their salts and metal complexes; provided that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is CH2, then R1 is not a group

CH = CH2.

  The compounds of the invention are generally obtained in the form of mixtures of geometric isomers such as diastereoisomers and E and Z double bond isomers, including cis and trans double bonds, these mixtures as well as other mixtures of isomers

  which can be split into the isomers

  by known operations in the prior art and these isomers constituting a part of the present invention. Alkyl groups containing 1 to 4 carbon atoms represented by R 3 to R 18 are straight-chain or branched-chain groups, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and dry. -butyl or tert-butyl. Alkyl groups containing 1 to 6 carbon atoms represented by R 2 can be straight-chain or branched-chain groups, for example methyl, 2-ynyl, alk-3-ynyl, alk-4-ynyl or alk-5-ynyl. for example propargyl or but-2-ynyl. Alkynyl groups represented by X, Y and Z are straight or branched chain groups containing 2 to 6 carbon atoms, for example ethynyl or propargyl or any of

examples mentioned above.

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

cycloheptyl.

  Cycloalkylalkyl groups represented by X, Y and Z are (C 3 -C 7 cycloalkyl) - (alkyl)

  C1 to C6), for example cyclopropylmethyl, cyclohexyl-

methyl or 1-cyclopropylethyl.

  Examples of X, Y and Z groups when these groups are aryl, aralkyl, aryloxy or

  aralkoxy groups are phenyl, benzyl, phenoxy and

  benzyloxy. These rings are optionally substituted with a halogen (fluorine, chlorine or bromine), an alkyl group

  C1 to C6 (for example methyl, ethyl, n-propyl, iso-

  propyl, n-butyl, iso-butyl, sec-butyl- or tertiary

  butyl), C 1 to C 6 alkoxy (for example methoxy, ethoxy, propoxy or butoxy), C 1 to C 6 haloalkyl (for example trifluoromethyl, C 1 to C 6 haloalkoxy (e.g.

  trifluoromethoxy), nitro, phenyl or phenoxy.

  Halogen atoms are the atoms of

flucr, chlorine, bromine or iodine.

  According to another of its aspects, the invention provides compounds that respond to the general formula (I):

  ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-

  butyl, tert-butyl, pentyl (straight chain or chain

  branched) or hexyl (straight chain or branched chain).

  Alkyl groups and the alkyl portions of the alkoxy, haloalkyl and haloalkoxy groups represented by X, Y and Z are straight chain or branched chain groups containing 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, including one

  any of the particular isomers mentioned above.

  Alkenyl groups containing 2 to 4 carbon atoms represented by R3 to R18 which are the same or different are alk-1-enyl, alk-2-enyl or

  alk-3-enyl, for example vinyl, 2-prop-1-enyl, 1-prop-1-

  enyl, allyl, 2-but-2-enyl, 1- (2-methylprop-1-enyl), 1-

  but-1-enyl, 2-but-2-enyl, 1- (1-methylprop-2-enyl), 1- (2-

  methylprop-2-enyl), 1-but-2-enyl or 1-but-3-enyl. Alkenyl groups containing 3 to 6 carbon atoms represented by R2 which have the geometry E or Z (including cis and trans) are alk-2-enyl, alkenyl,

  alc-4-enyl or alc-5-enyl, for example allyl, 1- (1-

  methylprop-2-enyl), 1- (2-methylprop-2-enyl), 1-but-2-

  enyl, 1-but-3-enyl, pent-2-enyl, pent-3-enyl, pent-4-.

  Enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl or hex-5-

  enyl. Alkenyl groups represented by X, Y and Z, which are the same or different and which have the geometry E or Z (including cis and trans are straight or branched chain groups containing 2 to 6 carbon atoms, for example vinyl or allyl, or any of the isomers

particulars mentioned above.

  Alkynyl groups containing 2 to 4 carbon atoms represented by R3 to R18, which are the same or

  different are, for example, ethynyl groups, prop-l-

  ynyl, propargyl, 2-but-3-ynyl, but-1-ynyl, but-2-ynyl or but-3-ynyl. Alkynyl groups containing 3 to 6 atoms

  of carbon represented by R2 may be

X R3 OR2 R5

  Wherein R 1 is a group of general formula (II), wherein R 1 is a group of general formula (II)

- C - C R7 (II)

  or a group of general formula (III):

__, _ / _ (III)

Re / 10

  R 7 to R 10, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl or alkynyl group containing 2 to 4 carbon atoms or a halogen atom ( fluorine, chlorine, bromine or iodine), R2 represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms or an alkenyl or alkynyl group containing 3 to 6 carbon atoms (provided that the adjacent carbon atom at the oxygen atom is not involved in any unsaturation), R3 to R6, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl group or alkynyl containing 2 to 4 carbon atoms, X, Y and Z, which may be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl group, cycloalkyl, cycloalkylalkyl , alkenyl, alkynyl, aryl, aralk yl, alkoxy, aryloxy or aralkoxy, Az is 1-imidazole or 1,2,4-triazole and Q is a group of

  bridging having one of the following values Q1, Q2, Q3 or Q4

your: R-

Q1 - C

R12 R11 R13 R

Q2 = C ---__ C

I I

R12 R14

Rl R13 R15

Q3 = C - C - C

R12 R14 R! 6

R R Pl6

R13 R13 R15 R17.

I i

Q4 = C C _ C _ C

R12 R14 R16 18

  R11 to R18, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl or alkynyl group containing 2 to 4 carbon atoms or a halogen atom ( fluorine, chlorine or bromine); and their salts and complexes of metals; provided that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is a

  CH2 group, then R1 is not a group -CH = CH2.

  According to another of its aspects, the invention proposes compounds corresponding to the general formula (I):

X R3 OR2 R5

_ C- C - Az (I) i I I

Z R4- Q R6

  R1 and stereoisomers thereof, wherein R1 represents a group of general formula (II):

C-C - R7 (II)

  or a group of general formula (III) -: R9

- = C (III>

  R7 to R10 are, independently, hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkenyl or C2 to C4 alkynyl; R2 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3 to R6 are independently hydrogen, C1 to C4 alkyl, C2 to C4 alkenyl or C2 to C4 alkynyl; X, Y and Z independently represent hydrogen, halogen, C1 to C6 alkyl, C3 to C7 cycloalkyl (C3 to C7 cycloalkyl) - (C1 to C6) alkyl, C2 to C6 alkenyl, alkynyl; C2 to C6, phenyl, phenyl (C1 to C6) alkyl, (C1 to C6) alkoxy, phenoxy or phenyl (C1 to C4) alkoxy

  at C6); Az represents an imidazole-1-yl or 1,2,4-group

  triazol-l-yl; Q is a link group having one of the following values Q1, Q2, Q3 or Q4: R11 Q1 = _ r._ R1 2

R1 1 R13

i

02 = "'C -

R12 R14

R1 1 R13 R15

3 = c-C-C

I ', I

Rl 2 R14 R16

R1! R1 3 R1 5 R1 7

I i I I Q4-C - C - C c i I. I

R! 2 R14 R16 R18

  R11 to R18 independently represent hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; any one of the above aryl groups being facu-ltatively substituted with halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, nitro,

  phenyl or phenoxy; and their salts and metal complexes

  c; provided that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is CH2, R1 is

then not a CH = CH2 group.

  According to yet another of its aspects, the invention

  The invention provides compounds of general formula (IA):

X R3 OR2

  wherein R 1 represents a group of the general formula (II): embedded image in which R 1 represents a group of the general formula (II): ## STR5 ##

C C-R7 (II)

  or a group of general formula (III): R9 C = C C = C

R - \ R1O

  R7 to R10 are independently hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkenyl or C2 to C4 alkynyl; R2 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z represent,

  independently, hydrogen, halogen, alkyl group.

  C1 to C6, C3 to C7 cycloalkyl, (C3 to C3 cycloalkyl)

  C7) - (C1-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl, phenyl (C1-C6) alkyl, (C1-C6) alkoxy, phenoxy or phenyl (C1-C6) alkoxy ), Az represents an imidazol-1-yl or 1,2,4-triazol-1-yl group; Q is a bridging group having one of the following Q1 or Q2 values: R_

Q1 = -C

R12 R11 R13

I I

Q2 = -C C -

  R12o R1 to R14 are, independently, hydrogen, halogen, C1 to C4 alkyl, C2 to C4 alkenyl;

  or C2 to C4 alkynyl; all the aryl groups

  optionally substituted by halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, nitro, phenyl or

  phenoxy; and their salts and metal complexes.

  According to yet another aspect of the invention, there is provided compounds having the general formula (IA):

X R3 OR2

I 1 (IA)

Y / CH-C-CH2 -Az Q

Z 1

  R1 and stereoisomers thereof, wherein R1 represents a group of general formula (II):

C C - R7 (II)

  or a group of general formula (III):

R9 (III)

- C

R8 R10

  R7 to R10 are, independently, hydrogen, halogen or C1 to C4 alkyl group; R2 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl (with the proviso that the carbon atom

  adjacent to oxygen is not involved in any

  saturation; R3 is hydrogen or C1-C4 alkyl; X, Y and Z independently represent hydrogen, fluorine, chlorine, bromine, C1-C6 alkyl, C3-C7 cycloalkyl, (C3-C7) cycloalkyl- (C1-C6) alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl or C1 to C6 alkoxy; Az represents an imidazol-1-yl or 1,2,4-triazol-1-yl group; Q is a bridging group having one of the following Q1 or Q2 values:

Q1 = --_ -

I R12 R11 R13

Z I

  oR1 2 R1 4rersnetidpnamn the yogeu 2 _

R12 R14

  R11 to R14 independently represent hydrogen, halogen or C1-C4 alkyl; and their salts and

their metal complexes.

  According to yet another of its aspects, the invention

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

X R3 OR2

Y CH-C-C2 N N (IB)

Z OR N

  and their stereoisomers, wherein R1 represents a group of the general formula (II)

- C = CR7 (II)

  or a group of general formula (IIIA) -: R9

\ R9 (IIIA)

C = C

H R10

  R7, R9 and R10 independently represent hydrogen, methyl or ethyl, R2 is hydrogen, methyl, propenyl or propynyl (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturated); R3 is hydrogen or the group

  methyl; X, Y and Z independently represent hydrogen

  no, chlorine or fluorine; Q is a bridging group having one of the following Q1 or Q2 values: R1l R11 R13

Q! -Q _C C

* I / I I Q = -C _, Q2 = _C -c - C

-1 '12 14

R12 R12 R14

  R11 to R14 independently represent hydrogen or methyl; and their salts and metal complexes.

  According to yet another of its aspects, the invention

  It proposes compounds with the general formula (IC)

X R3 OH

  ## STR2 ## and their stereoisomers, wherein R3 is hydrogen or methyl; Q is a bridging group having one of the following definitions Q1 or Q2; wherein R11 and R12 independently represent hydrogen or methyl; X and Y independently represent hydrogen or chlorine; and their salts and their complexes

of metals.

  According to another of its aspects, the invention proposes the compound Ci OH

CH2 C CH2-N AN

CH3 CH N

  CH 2 CH 2 (Compound No. 431 of Table I) and its stereoisomers; and

their salts and metal complexes.

  According to yet another of its aspects, the invention

It proposes the compound: Cl OH

CH2 - C CH2 _NX N

  H30-C CH3 CH CH2 (Compound No. 437 of Table I) and its stereoisomers; and

  their salts and their complexes of metals.

  In Table I, the abbreviations have the following meanings: Me represents the methyl group Et represents the ethyl group npr represents the normal propyl group

  Tr is 1,2,4-triazol-1-yl.

  All melting points indicated on the

  Table I below are expressed in degrees Centigrade.

  Although the azole (Az) in column 11 of Table I is designated by the symbol Tr (i.e., 1,2,4-triazol-1-yl), it should be noted that it could also be represented by the symbol Im (that is to say imidazol-1-yl), and this designation must therefore be considered as including, in each case, imidazol-1-yl corresponding to 1.2, 4triazole-the-yl

specified precise.

  ## EQU1 ## where ## EQU1 ## where ## EQU1 ## where ## STR2 ## H ZIID'IIDZ \ ilDIlID- \ ID-Z Il L .. II It 11 1 NDz ai:) H ID-1 / ID-1 01] Lll 11 II11 11 4iDiD ZHD H ID-t ID1-Z 6 ("JLHH ## STR1 ## where: ## STR1 ## ## STR1 ## ## STR1 ## ## STR2 ## ## STR2 ## 1-Z 6 -'HH HH azIII) ZIIDH 1D9 Z-ID Z

RD IDV

  (Do) NOdlIi Zi XS (dhO _______ d_ V_] ____H _a _ _ __ ___ _ _ _ __ _ __ _ __ -uI -.iVJ = -aJ c'J alH, Hi H = HD-Z'D HiD ## EQU1 ## where: ## EQU1 ##, ## STR1 ## 1HH3D f3uLD = IIDZID H 1O-tID-Z 81 1LH H il H Il = 3 k ibi = HDZHO it ID-. 91 11HH1H1H1H1H7HloH 13-17 10-Z91 - '. ## STR1 ## SOdWNOD aC LNIOd 92i52 q2 1 2i zfoN, H 11 tilH l-IZ Lú H1 H1 H 11 of the H T-10-Z 9 IL IH HH 11 4IOH Z0 = 1 "[D1'DH ID - 'l0-Z - ## STR1 ## ## STR1 ## ## STR2 ## ## EQU1 ## where: ## STR2 ##

- '/ 1 H H H H 1 ZD0 H IO-1 10-Z

  Z -J. ## STR2 ## ## STR2 ##-1 ## STR2 ##-1, ## STR2 ##, ## STR2 ## ## EQU1 ##

_ _ _ I _ _.

  ## STR1 ## wherein: ## STR2 ## ID-V7 1-Z8V 1 It HHH 410 = 10 11AO0 H 1 0i [-1 10-z -.LH 11 H H1 14l I itD = 011DJH 1 I-1710-ZV OL-1HtH 11 + 'riC llt) H 1171D -Z 9V -4-

H! H / "/ H /! 10O}) H 1-71-

  ## STR2 ##

-J H H H I H = ZIIO H I01 ID-Z ZV

  ## EQU1 ## 1 ## STR1 ##

AT "TP TOINT DE

  COMPOUND X Y Z Q R1 R2 R R1 R5 R6 FUSION (DC)

I IUIN (C

  51 2-CI4-CI ll Q% 2Ql? ## STR2 ## ## STR2 ## ## STR2 ## wherein: ## STR2 ## ## STR2 ## ## STR1 ## 11. 1 Tr 2 -Cl 4 -Cl 2 Q 2 Ql 2 a 2 1 i H lt Tr 61 2-CI H H_ Q12 C0Ct H HH H H H H H C H, H O H H H H H H ElWe OW040D 11 HH ID-Z SL I ll [tiJll [il Z 0Dlit It ID-Z I7 4 11 liH H 11 ifl = U NIO HH ID-1 LUH i1 H Dw ZIWD HD HH ID-Z ZL A1 iH iHH 1 ZD3G 'lo H il ID-Z IOL ## STR2 ## in which: ## STR1 ## in which: ## STR1 ## 99 4IH HHH ZHID HH IG-Z 5 9 CM 4 HHHHH Z30O Ig H 1 -Z69 U4 H1H1H1H: Hd1H1H1H1H1H1H1H1H1H1H1H1H1H1H2H1H1H1HHH1H1 ## EQU1 ## ## STR2 ## l -___ L X (oN

  ## STR1 ## where: ## STR1 ##

  ## STR1 ## where: ## STR1 ## where: ## STR1 ## ## STR2 ## -Z 6-I. H H1l 1 I H} l 3, -qH t OI? RI.D I Il 10: -Z 8L -

  -JHH H H 1U4tJ-1t441340ZIDH H ID-ZLL-

U ililt 1II. % Zin Ct) 9L <'J'

  _ _, ........ __.......................... __.._ _ _. _ _.

  EC, .N * Od J9HH / HH 4, 1b A X N -'J. ## STR2 ## 2 n. TABLE.I (cont.) R1 R34z YN7 POINT R 2 R 5 R 5 R (1) AzFUSION (C) 2-CIH 1 __ __ 87 2-CIIII 2 ) 2 CW'CHEt HH Tr 87 2-CIH H QI2t HHHH Tr E 88 2-ClH H oI <and HH-z 89 2-CIH Hl Q12% QC) l 11 H He ilTr 2-CIH H a (l2 HHHHT 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HClH 2HCl Tr 96 2 -Illllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll r; it)

N FROM R_ R24 - -

  COMPOUND X Y Z Q R2 R3 R4 R5 R6 Az POINT OF

  _____POSEI__ ___.______ I FUSION ('C)

  99 2-CI H It 012012 EIl i 1 1 r 2-C1 H H CH12Q1 C :: And. ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## wherein: ## STR2 ## ## STR2 ## H (12012 0l - (]% nPr Il Il HH 'r 1 E o'

__> ''

_ _ _ _, ____._>

  ## STR1 ## where: ## STR1 ## where: ## STR1 ## ## STR1 ## where ## STR1 ## where ## STR2 ## ## EQU1 ## ## EQU0000 ## ## STR1 ## I) ZA, X 1] o [n) III V, (4Tns) I (1V3'IYsV.L N0 'f YZQ L6 POINT DE

COMPOSEX U RR R3R R SION (C)

  2-CIH H TO L2 (52n-2 K ilH 1 H Tr 121 4-CIll 1H1 (1 tz C = 1 11 H 11 H PTr 122 4-CIHl Hl ni2 nMe Hl fiH I1 IHH [r 123 4-CIH il% ## STR2 ## ## STR2 ## ## STR4 ## ## STR2 ## ## STR2 ## ## STR1 ## wherein: ## STR1 ## wherein: ## STR2 ## ## STR2 ## ## STR1 ## ## STR1 ##

E I

134 4-CIH H 2 Z .. 11HH I Tr z 1 {

_ C_ __ _ _ _ _

  TABLE I (cont'd) ## EQU1 ## HHHI Tr E 136 4-CI H til a awa a-1 M 1 1 1 1 1 1 Tr 136 4-Cl1 HH CQi2 IMe FMe t HH lt Tr 13i 4-CI HH o 12 ao.e And H ill Tr 4- ## STR2 ## HH CH 2 -CHI-I-I-TrI 1384 4-Cl HH a12 = 10n and HHH H1 Tr Z

E M

  142 4-CI HH CH2 -cI n pr H H H H Tr Z 141 4-ClI HHH F l lrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrr Cl HH OL Gt: Oe.ie Ctt2-OGH H Hl I l Tr E 144 4-C1 l! ll Ot = OeA Qt2- i [t H II l Tr, xr

_ _ Z "CI

Z 14>

"'{

  ALllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll ## STR5 ## wherein R 1, R 1, R 1, R 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, H 1, and H, respectively, ## STR1 ## wherein: ## STR2 ## wherein: ## STR2 ## ## EQU1 ## where ## STR1 ## where ## EQU1 ## ## STR1 ## where: ## STR2 ## where ## STR2 ## is a compound of the present invention. ## STR1 ## ## STR2 ## ## STR1 ## ## STR2 ## Z oo% mL HH i 1 Hi 11a 10 HH 10- 991 UHHHH 1 1 awi1> 40% wi 11 H 1D - \ '791 AL11 11H11 N ZHDel t2DZlDH H 1D-dZ91 -' 11 il HH H ZH ZID3 H lH 10-Il191 -U Hl n Id H 11H H ali HH H3I 091

-J.HHH HI HI 6W = IHH 1-I 9

  ## STR1 ## ## STR1 ## ## STR2 ## where ## STR1 ## zA x na oN Tt;) I nv; ijuva \ NODI) 'I__4l6 N0 DUOSFX Y%. Q y R R) R4 R5 R6 A. F'M10! OF

COMPOSF FUSI ON (0C '

  ## STR2 ## wherein: ## STR1 ## wherein: ## STR2 ##

"1 I.

  173 4-CI II H 012012 EbW Ql;, - C Ql1H il he Tr E 174 4-CI Il fi (12 (02 I: M 12 (1 II II I T IYY [[ItC 4-CI 11 11 (l 5 ## EQU1 ## where ## STR1 ## E 178 4-C H H1 Q112 51 QIfEt MHH lH H Tr z 179 4-Cl HH CH2012 CH 'HH T L4lt .- - 6 -1, lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll Z161

-JHHIH I 13Z40II H _7ID-Zú61

I. J lHIlH l ZHa-V1-1061

AI.H11I I HH WZH1DZ10HIA-ID-Z816

-X.LHHHH44D-4 DDIDH "-AV1Z ID6 1

  ## STR1 ## ## STR1 ##

-LHHHH 1H-V 9I-Z991

-ki '' i "1l u 'It 1'

-JHHI HIH 4Z HA 10-ZZ81

  ## STR2 ##

* N0 OF R2 POINT OF

  COMPOUND XYZQRR RI R ION II (2-CI 4-F it ut2 I () I'k'Me H Hl 1 I 'I [r E 196 2-Cl 4-F It c12 (cltî, W7rR 2 il H 1 ## STR2 ## ## EQU1 ## 1 1 2 1 2 1 2 3 1 2 1 2 1 1 2 1 1 2 1 1 2 1 2 1 1 2 1 2 1 1 2 1 1 2 1 2 1 1 2 1 2 1 1 2 1 1 2 1 2 1 2 1 1 2 1 2 1 1 2 1 2 1 1 2 1 2 1 1 2 1 2 1 2 1 1 2 1 2 3 1 2 1 2 3 1 2 1 2 1 1 2 1 2 3 1 2 1 2 1 2 1 2 3 1 2 1 2 1 2 1 2 1 1 2 1 2 3 1 2 1 2 3 1 2 3 1 2 1 2 1 2 1 2 3 2 1 2 1 2 3 2 1 2 3 2 1 2 3 2 1 2 3 2 1 2 3 2 1 2 2 1 0L- Cti1I he he Il Hl 'r E

  204 2-CI 4-F 1 (O12 (1U11t '<12-: 1 H Tr.

u CO c J

o -i- Id 19Z-

  ## STR1 ## where: ## STR2 ## .Iy HH tl II has 1- {: H, -V IDZ oIt JL HHH 1 1 14 D 'tl9H J_ ID-Z IHIZ -At it aw ,, = ID iD H..1ID-Z 01O H it It H> HH? H -17 lo-Z 60Z

  - '. ## STR1 ##

  -M.RTM. O₁H₁₁₁ +O₁ LZ;

  -1MH. 1 11 I HI, T-.1L040 FIZD H1 A-V ID-Z 90Z

  The following are examples of the following: 1, 2, 1, 2, 3, 4, 6, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 7, 8, 7, 8, 7, 8, 7, 7, 8, 7, 7, 8, 7, 7, 8, 7, 7, 7, 7 H iq-t ,. ID-Z Z HH 11 H1 aw a1rit 1 Ha-'j ID-Z SZZ it Dw LHIlH It 44 410 = 1Ul) -itirA Hl 4 -'113) -i sr, z Z J. Il H Hi HH H) ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## EQU1 ## _HK Fa Z 1O 1 aOI H __A - t73 -iZ 8i Z Do) NOIsiln 9V <u ju u It ssodwox (u4.T "> 1 flViUIVL

  __._,. , ................................................. ..,. ,,., 4 ,. ,.

  (u-% hetSVSil8 TABLI.AU I (cont.) N0 OF R1 R2 R3 R4 R R6 POINT OF

_ __COMPOSE __FUSION (C

  230 2-CI 4-F O 02CH 2 aM'e. ## EQU1 ## ## STR2 ## wherein the UH 2 -IlCl 2 HCl 2 H 2 ## STR2 ## 237 2-CI 4-E Hl 01202 (OIl Meh il 11 He Tr E 238 2-CI, 4-F Hl 012il2 01 - HEALTHY HEAD H 'Pr z 239 2-CI 4-F i 012012 Qe2 H 2 HCl Tr 2 O 2 -Cl 4-FHN 1a 22 2 M H11 H | c, r 1 (7 cm -111 -Lllll HI.a.). ul AA-z, z 0J-, tH ## STR2 ## wherein ## STR2 ## ## EQU1 ##, ## STR2 ##, ## STR2 ##, ## STR2 ##, ## STR2 ##, ## STR1 ## ## EQU1 ## ## STR1 ## ## STR2 ## ## STR1 ## ## STR1 ## ## STR5 ## ## STR1 ## ## STR2 ## where: ## STR1 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR1 ## ## STR1 ## .. D Z1Z0H A-. Az 9LZ

JL11 H H H 13 O H A-17A-Z SEZ

H1 H1 HH1 H0 ZIOZ1OH A4-A-Z LUZ

  t he he he he has oo zH3ZD he qt î_z M 1 Z aL He He he Hlow I0D & DZfiDO H A 'i-z ZLZ

  J. H1 11 H1H H WY> D Z10Z) H A-17A-Z ILI

  Hi Hi Hs Hl Z 0. r Ho A-? AdaA-ZOLZ oD <m ..] ji Hj Hi l J I [.lIJ040ku "H: A-'A-Z 69Z

  AZ} lJIllIlJ '"N ::: r. L _ [0gild, .-- + / ... 9-

  ## STR1 ## where ## STR2 ## where ## STR1 ## where ## STR1 ## : I gild hihi HlHi It 2410flk56.0 A4 + M / Z992 .- (Do) NOIS: I.UdO.D knew & NIOD [ONb NIOD __.___ $ 21 '____ IAu bZ AX na oN <_ rns) I IVFA.'. IIVL TAI.EAU I (S Lt e) N OF y.R2 3.4 R5 R6 COMPOSEX POINT y ZNRRR RR6 FUSION (C)

_ _. , ..

  278 2-F 4-EI% l21i2 012-COEQH H Hi H -Tr 279 2-F 4-F H1a2'12 C0F H t H ll HH Tr 280 2-F 4-FH {t22 - And II II ## STR2 ## H H H H H H Tr E

  284 2-F 4 / -F iH O {2CH22CaC'Ie H H ll Hl H IYTr w.

  z 285 2-F 4-F IH 012t2 aK0I '' i1 Il H It Tr E 286 2-F 4-F HI 012012 Z = Me.? ## STR1 ##

Z L

  (cr cr CD CD CD CD CD 6 6 6 6 6 6 6 6 (

he.....

  ## EQU1 ## where: ## STR1 ## ## STR2 ##

  _. I r - i r --- ---- o i -4 ---- 16 ---

  (D o) NOI t lxtSOdWO 2V} 1 i-I14ld (-,,,,,,,,,,,,,,,,,,,

k. -

  !) H IlI Hli li = tD 1ID 1D-910-11-Z ú 4L11 H Hl 11 a1tl qO ic ID-91D-110Z 0 AI.HHI l H iH0I3 {) Z1'ID-91D-710-Z 60t I 4L ## EQU1 ## where: ## STR1 ## where: ## STR2 ## "HoZo EO Su ZD10-910-7Io-Z90C 4L HHHH c00A ') 10-911-, ID-Zgou A.LH I1 H 011 ll010-91D-110-Z' O

  4 H H H H 4 + 0 ZSD10ID-9ID-17 T1-ZZ0u

  HH H He H H H Z1 '10I-91D-7ID-Zzoc iL HHIl H So 10-913-1710-zIO 4 HHH Hl He i4izODit St 10- 10-1710-Z0OC 4 HH / HHH ZDO S / H a-1a -Z 66Z TD) oC) f. N9Od u o Eb Z x Its INIOd O S _. ## EQU1 ## ## STR1 ## where: ## STR1 ## where: ## STR1 ## ## STR1 ## ## STR1 ## wherein ID-Z SEU kL H 11 HH 44 DWOmD ZH O ID-9 1317 13-Z WEE kL he HH H1 H 4) ZOZ10) ID-9 ID-9 ID-Z CCU -U H1 H1 H1 he ow ILtP% Zi ' O ID-9 1i-1 ID-Z ZEE z / 'J "HH H1 1 H1 44 W DZI I1D-9 ID-7 IS-Z IE 1 H1 HH H4 T0 = RJ Z5' 13-9 ID-t1 13 -Z OR ALH ll ll tl as _ ZHDZao = tIi ID-9 ID-t ID-Z 8Zu z11 H ll il DW 191040] FD I-ID, 7 IS-Z 2

  -'J. H H 11 H H J 1 H 3 = RD Z 13 ID-9 13-17 13-Z 9ZE

  ## EQU1 ## ## STR00006 ## where: ## STR1 ## ## STR1 ## ## STR1 ## wherein: ## STR2 ## wherein: ## STR2 ## ## STR2 ## ## STR1 ## 11) 9-91 I-D 9 -Z 6 H, H, H, H, ZnI-913D (71) -Z (1H); 4X7t) IUID-9ID-9ID-Z-1H-1H -H1H19IH1I) 7ID7) 1 9-919) - ID: Z (H1H11H111: 1: 1 (4) (g) ZHD71t) 919-iID-Z 8u JLHHllHll H11% 1a4z) SZio 1D-9 TD- 'ID-Z Lúç (Do) NOISfllZV if NZOD

SU -I) I L1V) 1 V10

  S (IIJNIO _, _ q Lz_L9S t7 X InloN _r LH II HtH 1: r INDA. IiIDgID-9IDq | dzus It iiH11H (tli itA'r 9ID ID-ID-ZL% o -tLHI It ll: ORP t- ## STR2 ## where: ## STR1 ##, ## STR2 ##, ## STR1 ##, ## STR2 ## iDELO3 4i = 4ID-919-17 1D-Z17SC LfHHHtHH Ir-D-3D; ## STR2 ## ## STR2 ## ## EQU1 ## where: ## EQU1 ## where: ## STR1 ## FIG. 1ID} | 11, ID-9ID-zuu -i H AL11111111 43Di0 71U1 1t ID-9ID J-7.69, 1H HHI I l "# 641) i1tJ 11ID91I-Z 69ú I'L1 11ill1 1H -1c1nT 1H) iil 1-gID-Z99 -I (it JII.HHHu%) ID, H: D-910-z99u

JH 11H H H3 ID ID H 1D-9ID-Z 598

  ## STR2 ## ## STR1 ## ## STR2 ## 1-91. HlH H H1 41 te4ChirSo 19-919I9-Z 09ú (9 <>) NOISHri_, _ _ _ x_ CQM IN I Od fi j-ia.uncxxC) qiqi I I Wi] oN j (.i> ii3) j-1V 11UVJ

CMJ ._________-_. 1_ '

in lHU02D) >> D ZDH I-9 ID-Z E8

4- Z 93

  OIH. E {11H X 6 iJuLa4D 7t 11 ID-9ID-1 WC r) a, L} 1It 1t I} jlO-g} Oqd4t = 1i I} '13-91O-Z 61u 1 <1 -'JH HHH ffltD ## EQU1 ## ## STR1 ## where: ## STR1 ## D13-9 1D-ZL9u I.ItI H uH i W - 40 1 HI ID3-93ID-Z09 JH 1 HH 10 iC> 40ZH H 1 -9 13-Z SLE

## STR2 ## 1-1-RYD = tDi) H 1-9

  1 HH 1 11 H H. 4iB I4 = qDED I1 ID-9ID-Z LLu

- H H H T J -, 13-9 1- -

  (Do) NOISfl. _.! S _ z E x DSOdWOD q1._NIOd, _ fl_oN t 7l N'J I 2JLH H4 | II tI H1 4LD0 ZStD H 1D-9 -Z 96E -'i. LHH | H IaD IOI! i ID-9ID-Z56E tl H HH H 11 HODtD1 ID0-9ID-Z6E -j.AHH Hi H1 11 tO7Rz7H | 1D-910T-H H1 ZE6E -JH Hl Ht tD OSLC) H 1D-910-H Ill Z16ú -jLilH 4d.4t) O.) ID-9ID-06u-H1H1H1H1H7H7-O = I) St H ID-910-768E Co v aXL'l'l'l; l.4lL> lt) t) I IiIii 09TD-Z LSK -'I HHt H11 'H1 1) ItSD u ID-9ID-Z 98f -'JH HHHH rOi4) 1 2to H1 10-910-238u LH ## STR5 ## wherein R 10 is H; 0IO _-0 S H 10-91-Z

_.__ _- _- __-.___- _ _

  J (l aNIOd_gY5Y _ <__ J.I1 It? -IDa2lIDS

N U

No L X Y QXy R R Z R6 A PO1NTDE

FUSION COMPOUND (C)

  397 2-CI 6-CI 11 (Zi1Ol7) -> ->>>>>>>>>>>>>> 397 2-CI 6-Cl H 0120L2 C '' U12-Cl, Il 399 2-C1 6 ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## 2-Cl 6 Cl Cl Ci7.1 01% Me 1 H 11 H 1 H 1 R 403 2-Cl 6-Cl 2 a 2 a 2] i Il il il he H r E 404 2-CI 6-CI H L2C, 2 l = ## STR2 ## wherein R 2 is CH 2 Cl 2, and CH 2 Cl 2 ## STR2 ## ## STR2 ## and ## STR2 ## ## STR3 ## to a compound of formula (I): ## STR2 ## wherein: ## STR1 ## : MH H 111144 ID = Z1) ID-Z9I A -M11, JI1111iit4i t I IID9ID - :: =, "Ln 111 1 11 t4CUgi) IlI-9D 5 'ALIl HH-li, 1 I IIDH 19- 1D-ZL1: ## STR2 ## -919-.60 (o) NO'Id | to "H.SOd.OD (J0) V9 HH I ISOdlO9 <j_ _ _ _ _ _ _ __ _IlL__N: 4a.LHJOd9'F nuN AL 11 li HH X 4 71NtD rd4D | ## STR1 ## wherein: ## STR1 ## ## STR1 ## wherein: ## STR2 ## ## STR2 ## 1D ID H ID-ID-Z 6ZC dL H1 HH awD 4 H 10-; ## STR5 ## ## STR2 ## ## STR1 ## ## STR1 ## ## STR1 ## ## STR1 ## 10-Z ú Z9 HHH H D10 = D 41DNID H 1D-7 ID-Z. ## STR1 ## where: ## STR1 ## where: ## STR2 ## -v ID-Z ZZ'7 / 'H H1 HH IID% QH 10-n 10-Z IZ -'1 H Hl li 11 s iD 7o7 H 10-9 I0-Z OZ' UL l HH Il H iIl Z1QiD H ID-9 10-Z 61I J.NIOd _ '9_ ç5E I úH 1 alz AX nUO 0N

_Tf I flV _ _ -

  ## STR1 ## where: ## STR1 ## ## STR1 ## where ## STR1 ## ## STR5 ## ## STR1 ## wherein: ## STR2 ## wherein: ## STR2 ##

ELH 111.1141 z :::: t>) 1I-

  ## STR00006 ## ## STR1 ## ## STR1 ## D "{ID H 19 I1-Z <JG l a.lOd9 t Stlj: I 2_, It_ _ b_ _ _ _ _ _ _ _ _ _ _ NoRDU2 4 6 COPS iPOINT _ z R R2 R3 R4 RS R6 AZ jPOSTD

Q FUSION COMPOUND (OC)

  449 4-CI H il 31e 0C (> 1 H 11 H He H Tr 450 4, Cl H ila II CccI l l H H Tr 451 2-CI 4-FI a] Me Qa = i2 HHHHI Tr oil 452 2-CI 4-FHC] e aI <02 Me HI {I 452 2-CI 4-F ci ci.a otra KT 1S i 1 1S 1 1 TI 454 2-CI 4-FH ac3 Q11-41 And-aO 1il i l1 | 1 1 Tr 453 2-CI 4-FH 0iMe (a = t2 HLH H H Tr 455 2-Cl 4-FI {e aw {, (H e H. It Tr 456 2-Cl 4-F It 011e CI- ## STR2 ## ## STR1 ## wherein: ## STR1 ## wherein: ## STR2 ##

_ __ _ _______

  o'N TABII] .Ai r (: ui t) OMPOSE X Y Z Q R R R2 R3 R4'RS R6 Az DOT DER

FUSION COMPOUND (OC)

  462 2-CI HH me {2 QI 11 Me FHHH Tr huil1 463 2-CI He H (Qe2 (OF <Me HHHH TrE 464 2-CI 11 11 (04e2 aCIF'lie H il HH H1 Tr z 465 2-CIHH 4ke2 OIt he H H H H E H 466 2-CI H, I2 Ce2 2IEt H he HHH Tr z ul IX) 0% rn

  TABLE II: MAGNETIC RESONANCE CHARACTERISTICS

PROTONS

  Table II reproduces the proton magnetic resonance characteristics for certain compounds described in Table I and characterized in this table as oils. Chemical shifts are measured in ppm relative to tetramethylsilane, and deuterochloroform was used as the solvent in all cases. The following abbreviations are used: 1 = wide t = triplet s = singlet q = quadruplet d = doublet m = multiplet dd = doublet of doublets J = coupling constant

Hz = Hertz.

  NO of the MAGNETIC RESONANCE CHARACTERISTICS COMPOUND NUCLEAR COMPOUND 3 8,19 (1H, s), 7.98 (1H, s), 7.47 (1H, m), 7.40 (1H, m), 7.23 ( 1H, m), 4.49 (1H, d, J 13 Hz), 4.14 (1H, d, J 13Hz), 3.55 (1H, 1 s), 3> 18 (1H, d, J 13Hz ), 3.05 (1H, d, J 13Hz), 2.20 (1H, m), 2.05

(1H, m), 1.84 (3H, rm).

  8.20 (tH, m), 7.96 (1H, m), 7.51 (1H, m), 7> 38 (1H, m), 7.21 (2H, m), 4.53 (b.p. 1H, d, J 12Hz), 4.15 (1H, d, J 12Hz), 3/47 (1H 1 s), 3.27 (1H, d, J 12Hz), 3.10 (1H, d, J). 12 Hz), 2) 4 - 2.0 (4H, m),

18 (3H, t, J 7Hz).

  8,11 (1H, s), 7.94 (1H, s), 7.39 (2Hm), 7.20 (2H, m), 5.76 (1H, m), 4.99 (2H, m.p. m) 4.35 (1H, d, J 12Hz), 4.08 (1H, d, 12 Hz), 3.31 (1H, s), 3.02 (2H, s), 2.22

(2H, m), 1.49 (2H, m).

  8.23 (! H, s), 7.97 (1H, s), 7.27 (4H, m), 4.39 (1H, d, J 12Hz), 4.19 (1H, d, J). 12Hz), 3.30 (1H, 1 s), 2.94 (1H, d, 12Hz), 2.78 (1H, d, 12Hz), 2.15 (1H, d, J 16Hz), 1) 97 (1H, d, J 16Hz)

1.87 (3H, s).

  N of MAGNETIC RESONANCE CHARACTERISTICS compound NUCLEAR 129 8.19 (1H, s), 7.98 (1H, s), 7.28 (4H, m), 4.40 (1H, d, J 11Hz), 4, 19 (1H, d, J 11Hz), 3.31 (1H, 1 s), 2.95 (1H, d, J 11Hz), 2.78 (1H, d, J 11Hz), 2.21 (3H). m), 1.96 (1H, m), 1.19 (3H, t, J 7Hz). 8; 19 (1H, s), 7.95 (1H, s), 7, 28 (4H, m), 4.35 (1H, d, J 13Hz), 4.26 (1H, d, J! 3Hz ), 3.40 (1H, s), 2.93 (1H, d, J 12Hz), 2.81 (1H, d, J 12Hz), 2/22

(4H, m), 1.18 (3H, t, J 7Hz).

  131 8.13 (1H, s), 7.99 (1H, s), 7.26 (4H, m), 87 (1H, m), 5.22 (1H, d, J 9Hz), δ (1H, d, J 15Hz), 4.19 (1H, d, J 12Hz), 4.8 (1H, d, J 12Hz), 3.18 (1H, 1 s), 2.80 (1H, d , J 1 Hz), 2.70 (1H, d, J 11Hz), 2.11 (2H, d, J 7Hz). 431 8.00 (2H, s), 7.55-7.15 (4H, m), 90 (1H, m), 5.30-4.90 (2H, m), 4.49 (1H). , m), 3.88 (1H, m), 3.25-2.87 (3H, |

m), 2.05 (1H, m), 1.19 (3H, m).

  N MAGNETIC RESONANCE CHARACTERISTICS NUCLEAR COMPOUND 437 7.77 (1H, s), 7.75 (1H, s), 7.48 (1H, m), 7.33 (1H, m), 7.14 (2H) , m), 6.09 (1H, dd 16 and 0.1Hz), 5.07 (1H, d, J 10Hz), 5.06 (1H, d, J 16Hz), 4.44 (1H, s). , 4141 (1H, d, J 14Hz), 4.04 (1H, d, 14Hz), 3.40 (1H, d, J 13Hz), 3.04 (1H, d, J 13Hz), 1.18 (3H, s),

1.13 (3H, s).

  441, 8.20 and 8.08 (1H, 2xs), 7.94 (iHs), 7.35-7.10 (4H, m), 5.95-5.70 (1H, m), 4.90 (2H, m), 4.24 (1H, m), 3.96 (1H, m, 330-2 / 5 (2H, rrm), 2.10 (1H, m),

1; 14 (3H, d, J 7Hz).

  451 8.08 and 8.01 (1H, 2xs), 7.92 and 7.91 (1H, 2xs), 7> 58-7.35 (iH, m), 7, 11 (1H, m), 6 , 97 (1H, m), 6.02-5.75 (1H, m), 5.25-4.91 (2H, m), 4.43 (1H, m), 3.83 (1H, m), ), 3/11 (1H, m), 2.90 (1H, m), 2; 04 (1H, m), 1.19 (3H, min). 462 8.08 (1H, s), 7.92 (1H, s), 7.35 (1H, m), 7) (2H, m), 6.90 (1H, m), 6> 10 ( dd, J 16 and 10Hz), 5.03 (2H, m), 4.65 (2H, m), 4.05 (1H, q, J 7Hz), 3.08 (1H, s), 1.43

  (3H, d, J 7Hz), 1.18 (3H, s), 1.08 (3H, s).

  The compounds of general formula (I):

R3 OR2 R5

x II C C C. Az

1 1 1

y4R Q R6 z

2 / R4 C: R

  R 1 wherein Az, Q, R 1 to R 6, X, Y and Z are as defined above, except that R 2 is not hydrogen, may be prepared from compounds of the general formula (IV) [ compounds of formula (I) in

which R2 is hydrogen] :.

R3 OH R5

x Az (IV)

R4 R6

  Wherein Az, Q, R 1, R 3 to R 6, X, Yet Z are as defined above, by treatment with a base such as sodium hydride, and with an alkyl halide, an alkenyl halide or an alkynyl halide, R2Hal, o Hal can be chlorine, bromine or iodine, in a

  suitable solvent such as tetrahydrofuran.

  Compounds of general formula (IV) in which R 1 is a group of general formula (III) where R 8 and R 9 or R 8 and R 10 are hydrogen atoms may be prepared by hydrogenation of compounds of general formula (V) compounds of general formula (IV) in which R1 is a group of general formula (II)

-2634202

R3 OH R5

  x i r Q <C C C Az Y i I z R4 Q R6 (V) C -1! 1 c in. which Az, Q, R3 to R7, X, Y and Z are as defined above. In the cases where R 8 and R 10 are both hydrogen (double bond pis), this preparation can be carried out by catalytic hydrogenation on a suitable catalyst such as palladium fixed on barium sulfate. Compounds in which R8 and R9 are both hydrogen (trans double bond) can be prepared by isomerization of compounds wherein R8 and R9 are both hydrogen (double bond

  cis), for example by iodine or diphenyl disulfide.

  Compounds of general formula (IV) may be prepared by treatment of compounds of general formula (VI):

R O R5

X ---- Xa ---- C-C --- Az (V)

(VI)

Z R R

  in which Az, R3 to R6, X, Y and Z are as defined above, with compounds of general formula (VII):

M Q - R1 (VII)

  wherein Q and R 1 are as defined above and M

  is a metal such as magnesium, lithium or titanium.

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

R3 0 R5

C C - C '- Hal (VIII)

Z R4 R6

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

  potassium, in a suitable solvent such as dimethyl

  formamide. Alternatively, compounds of the general formula (V) can be prepared by treating compounds of the general formula (VIII) with compounds of the general formula (VII), followed by treatment with an azole

(imidazole or 1,2,4-triazole).

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

R3 OH R5

  Wherein Hal, R3 to R6, X, Y and Z are as defined above, with a suitable oxidizing agent such as a polyoxycarbonyl ether,

Jones's reagent.

  Compounds of the general formula (IX) in which R 5 and R 6 are hydrogen may be prepared by treatment of compounds of the general formula (X):

R3 H

_ _

X has l C = C x y (? __> c c cX) it I

R4 H

H z

  wherein R3, R4, X, Y and Z are as defined above.

  above, with a solution of the appropriate halogen, by

example of bromine, in water.

  Compounds of general formula (X) in which R 3 and R 4 are hydrogen can be prepared by treatment of Grignard reagents of general formula (XI): Mg Hal (XI) wherein X, Y and Z are such as defined above, with allyl bromide, optionally in the presence of a copper (I) catalyst, in a suitable solvent such as

than diethyl ether.

  Compounds of general formula (XI) can

  be prepared by methods described in the literature.

  Alternatively, compounds of general formula (VIII) may be prepared by treatment of Grignard reagents of general formula (XII): R3

x.y_ ___ (xII).

  In which Hal, R 3, R 4, X, Y and Z are as defined above, with an acid chloride of general formula

(XIII):

0 R5

Cl C C Hal (XIII) R6

  wherein Hal, R5 and R6 are as defined above.

  above, in a suitable solvent such as

  diethyl or tetrahydrofuran at low temperature.

  Compounds of general formula (VII), (XII) and (XIII) can be prepared by methods described

in the litterature.

  As another variant, compounds of general formula (VI) can be prepared by oxidation of compounds of general formula (XIV):

X R3 OH R5

Ri I y C C C Az (XIV)

Z 14 16

Z R H R

  wherein Az, R3 to R6, X, Y and Z are as defined above. An appropriate oxidation process is the version

  modified according to Swern of the oxidation of Moffat (dimethylsul-

  foxide, oxalyl chloride and triethylamine in the

  dichloromethane), or oxidation according to Moffat (dimethyl

  foxide, acetic anhydride and triethylamine in the

  dichloromethane) or the use of Jones's reagent.

  Compounds of general formula (XIV) in which R5 and R6 are hydrogen can be prepared by treating an epoxide of general formula (XV):

X R3 0

O c C (XV) z R4 H H

  wherein R3, R4, X, Y and Z are as defined above.

  above, with an azole (imidazole or 1,2,4-triazole) in a

  suitable solvent such as ethanol.

  Compounds of general formula (XV) may be prepared by epoxidation of compounds of general formula (X) with a suitable peracid such as

  peracetic acid or m-chloroperbenzoic acid.

  Alternatively, compounds of general formula (XV) may be prepared by treating compounds of general formula (IX) wherein R5 and R6 are hydrogen with a suitable base such as sodium hydroxide in a suitable solvent such as than methanol or ethanol. Alternatively, compounds of general formula (IV) wherein R6 is hydrogen may be prepared by treating compounds of general formula (XVI):

X R3 0 R5

  in which Q, R 1, R 3 to R 5, X, Y and Z are such that

  defined above, with an azole (imidazole or 1,2,4-

  triazole) in a suitable solvent such as ethanol.

  Compounds of general formula (XVI) may be prepared by treatment of compounds of general formula (XVII):

R3 0

Xv t C Q- Ri II

R4 (XVII)

  in which Q, R 1, R 3, R 4, X, Y and Z are as defined above, with a sulfurized ylide of general formula (XVIII):

RS-CHR5 (XVIII)

  wherein R5 is as defined above, and (a) if R5 is hydrogen, then R is methyl or (b) if R5 is not hydrogen, then R is phenyl, in which a suitable solvent such as dimethylsulfoxide. Sulphide oxides of the general formula (XVIII) can be

  prepared by methods described in the literature.

  Compounds of general formula (XVII) can be prepared by methods described in the literature, for example by the treatment of compounds of general formula (XIX):

R3 0

  ## STR2 ## wherein R 3, R 4, X, Y and Z are as defined above, with a compound of general formula (VII) in which M is

  copper- (I) or M is magnesium (at low temperature)

ture).

  Alternatively, compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XX): R3 I x}

__ C H (XX)

Z Ré

  wherein R3, R4, X, Yet Z are as defined above.

  above, with a compound of general formula (VII) in which M is lithium or magnesium, followed by oxidation with a suitable oxidizing agent such as

chromium trioxide.

  According to another variant, compounds of

  general formula (XVII) can be prepared by

  of a compound of general formula (XXI):

<O, _C NR2 (XXI)

z Ri

  wherein R3, R4, X, Y and Z are as defined above.

  and NR2 is a suitable amide group such as NMeOMe, with a compound of general formula (VII) wherein M is lithium or magnesium in a solvent

  suitable such as tetrahydrofuran.

  As another alternative, compounds of the general formula (XVII) can be prepared by treating compounds of the general formula (XXII):

R3 0

yx II ___ - c - 4 c _ (XXII)

Z R4

  wherein R3, R4, X, Y and Z are as defined above.

  and W is hydrogen or lithium, with a compound of general formula (VII) in which M is lithium,

  in a suitable solvent such as ether.

  According to another variant, it is possible to prepare compounds of general formula (XVII) in which R 1 is a group of general formula (III) where R 8 and R 9, or R 8 and R 10 are hydrogen, by hydrogenation of compounds of general formula (XVII) wherein R1 is a group of general formula (II). In cases where R 8 and RC 0 are hydrogen (cis double bond), a suitable reducing agent is hydrogen over a suitable catalyst such as fixed palladium over barium sulfate. Compounds in which R 8 and R 9 are hydrogen (trans double bond) can be prepared by isomerization of compounds wherein R 8 and R 10 are hydrogen (cis double bond) with a suitable catalyst such as iodine. Alternatively, compounds of the general formula (XVII) may be prepared by treatment of a compound of the general formula (XXIII): ## STR2 ## and R 1 are as defined above, with compounds of general formula (XII) in which M is copper (I) or M is magnesium (at low temperature),

  in a suitable solvent such as ether.

  According to another variant, compounds of

  general formula (XVII) can be prepared by

  of compounds of general formula (XXIV):

H-C_ (XXIV)

H C (XXIV)

  in which Q and R 1 are as defined above, with compounds of general formula (XII) or compounds of general formula (XXV):

X R3

  Wherein R 4, R 4, X, Y and Z are as defined above, in a suitable solvent such as ether, the treatment being followed by oxidation with a suitable oxidizing agent such as

than chromium trioxide.

  According to another variant, compounds of

  general formula (XVII) can be prepared by

  compounds of the general formula (XXVI):

___ ___ __ _ - R1

(XXVI)

  wherein Q, R 1 and W are as defined above, or compounds of general formula (XXVII): r. in which Q, R 1 and NR 2 are as defined above (for example NR 2 = NMeOMe), with compounds of general formula (XXV) in a suitable solvent such as ether

of diethyl.

  Compounds of general formulas (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI) and (XXVII) can be prepared by methods described in the literature . As another variant, it is possible to prepare compounds of general formula (IV) by treating compounds of general formula (XXVIII):

0 R5

He. I Ri Q C C - Az (XXVIII) R6

  wherein Az, Q, R 1, R 5 and R 6 are as defined above.

  top, with a Grignard reagent of general formula

  (XII) in a suitable solvent such as ether.

  Compounds of the general formula (XXVIII) may be prepared by treatment of compounds of the general formula (XXIX): ## STR5 ## wherein Hal, Q, R 1, R 5 and R 6 are as defined herein above, with an azole (imidazole or 1,2,4-triazole) in the presence of a suitable base such as

  potassium, in a suitable solvent such as dimethyl

  formamide. Compounds of general formula (XXIX) can be prepared by treating compounds of general formula (XIII) with compounds of general formula (VII) where M is copper (I) or M is magnesium (at low temperature), in a suitable solvent such as tetrahydrofuran. Alternatively, when R 11 and R 12 are both alkyl groups, compounds of the general formula (XXIX) can be prepared by treating compounds of the general formula (XXX):

0 R5

R * - l_ 11 t (XXX)

R 1 - Q C - C C H

R6

  wherein Q, R 1, R 5 and R 6 are as defined above.

  above, with a suitable halogen (such as chlorine or

* bromine) as described in the literature.

  Compounds of general formula (XXX) can

  be prepared by methods described in the literature.

  According to another variant, compounds of general formula (IV) in which R 3 and R 4 are hydrogen may be prepared by treatment of compounds of general formula (XXXI):

(XXXI)

_ _ _ _ _ _ _ _ _ _ C C AZ

? - R6

  wherein Az, R 1, R 5 and R 6 are as defined above, with a Grignard reagent of the general formula

  (XI) in the presence of a copper (I) catalyst.

  According to another variant, compounds of general formula (IV) in which Q is equal to Q 1 (and R 11 is hydrogen and R 12 is hydrogen or an alkyl group) may be prepared by treatment of compounds of general formula (XXXII ):

X R3 R5

I It is C_C -Az z R4 H R6 I12

(XXXII)

  wherein Az, R3-R6, R12, X, Y and Z are as defined above, with a compound of the general formula

(XXXIII):

MC C - R7 (XXXIII)

  in which R7 is as defined above and M is magnesium [in cases where R1 is a group of general formula (II)], or with a compound of general formula

(XXXIV)

M - R9

C - C

RP \ (XXXIV)

  R10 wherein R8 to R10 are as defined above and M is copper- (I) [for the cases where R1 is a group of

general formula (III)]. Alternatively, compounds of the general formula (IV) can be prepared in

  which Q is not identical to Q1 (and R11 is hydrogen and R12 is hydrogen or an alkyl group) by treatment of compounds of formula

  (XXXII) with an appropriate organocuprate (ie

  say a compound CuLR1 in which L represents Q without the

  CRllR12 group and R1 is as defined above).

  Compounds of the general formula (XXXII) can be prepared by treating compounds of the general formula (VI) with a sulfur ylide of the general formula

(XXXV):

  R2Se C9HR12 (XXXV) where R12 is as defined above and (a) if R12 is hydrogen, R is then a methyl group or (b) if R12

  is not hydrogen, R is then a phenyl group.

  According to another variant, compounds of general formula (V) (in which R7 is alkyl, alk-2-enyl, alkenyl, alk-2-ynyl or alk-3-ynyl) can be prepared by treatment of compounds of general formula (V) wherein R7 is hydrogen) with a suitable base, followed by treatment with a compound of the general formula R7Hal wherein Hal is as defined

  above and R7 has the definition just given.

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

  General (XXX) with a sulfur ylide of formula Me2S9CH2e.

  Compounds of general formulas (XXXI), (XXXIII), (XXXIV) and (XXXV) may be prepared by

  processes described in the literature.

  The compounds, their salts and their metal complexes are active fungicides, particularly against the pathogens Puccinia recondita, Puccinia striiformis and other rust developing on wheat, Puccinia hordei, Puccinia striiformis and other rusts developing on barley, and rust developing on other hosts, eg coffee trees, apple trees, vegetables and ornamental plants, Ervsiphe qraminis (white) developing on barley and wheat and other whites developing on various hosts, such as Sphaerotheca fuliqinea on cucurbits (eg cucumber), Podosphaera

  leucotricha on the apple tree and Uncifiula necator develops

  pant on the vine; Helminthosporium spp., For example Pyrenophora teres, Pseudocercosporella herDotrichoides, Rhynchosporium spp., Septoria spp. and Rhizoctonia spp., for example R. cerealis; Cercospora arachidicola growing on peanut and other species of the genus Cercospora developing for example on sugar beet, bananas and soybean, Venturia inaecualis (scab) developing on apples. Some of the compounds also showed a

  broad spectrum of activity against in vitro fungi.

  They are active against a variety of post-harvest fruit diseases (eg Penicillium diagatum and Italicum growing on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes). Some other compounds are active as seed disinfectants against Fusarium spp., Septoria spp., Tilletia spp. (ie, decay, wheat disease transmitted by grain), Ustilago spp. and

  Helminthosporium spp. developing on cereals.

  The compounds can progress in the acropetal direction in the plant tissue. In addition, they can be sufficiently volatile to act in the vapor phase against

  fungi growing on the plant.

  They can also be used as fungicides

  (as opposed to fungicides for agriculture).

  cultivation), for example to prevent a fungal attack of

  wood, skins, leather and especially paint films.

  The compounds can be used as such for fungicidal purposes, but are more conveniently formulated into compositions for such use. The invention therefore proposes a fungicidal composition comprising a compound of general formula (I) as defined above, a salt or a metal complex of this compound; and as a

  optional, a carrier or a thinner.

  The invention also proposes a method for combating fungi, which method consists in applying to a plant, to the seed of a plant or at the place of the plant or seed, a compound, a salt or a complex

  metal of a compound as defined above.

  The compounds of the invention also possess pharmaceutical activity useful as aromatase inhibitors. Aromatase is an enzyme that performs the aromatization of A-ring in the metabolic formation of

  various steroid hormones. Maintenance or growth

  Some tumors are dependent on circulating steroids containing an aromatic ring A, and a chemical agent that inhibits the aromatization of nucleus A in the precursors of these steroids is likely to be effective in inhibiting the growth of these tumors.

hormonal dependence.

  The compounds, their salts and their metal complexes can be applied in various ways, for example they can be applied formally or non-formulated directly to the foliage of a plant, or they can also be applied to shrubs and trees, seeds or other medium in which plants, shrubs or trees develop or are to be planted, or they may be applied by spraying, dusting or in a formulated state. cream or paste, or they can be applied in the state

  steam; or in the form of slow release granules.

  The application can be carried out on any part of the plant, shrub or tree, for example foliage, stems, branches or roots, or the soil surrounding the roots, or seeds before they are sown; or on the ground in general, to paddy water or hydroponic systems. The compounds of the invention can also be injected into plants or trees or they can also be sprayed onto vegetation using spraying techniques.

- electrodynamics.

  The term "plant" used in this

  memory includes seedlings, shrubs and trees.

  In addition, the fungicidal method of the invention comprises preventive, protective, prophylactic and eradicative treatments. The compounds are advantageously used for agricultural and horticultural purposes in the form of a composition. The type of composition that we use in each case depends on the particular goal we want to achieve. The compositions may be in the form of

  powder for powders or granules

  active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fulling earth, gypsum, earth Hewitt, diatomaceous earth and kaolinite. These granules may be preformed granules capable of being applied to the ground without further treatment. These granules can be prepared by impregnating filler tablets with the active ingredient or by tabletting a mixture of the active ingredient and powder filler. Seed disinfecting compositions, for example, may include an agent (such as mineral oil) which facilitates adhesion of the composition to the seeds; alternatively, the active ingredient can be formulated for disinfection of seeds in

  using an organic solvent (for example N-methylpyrrolidine

rolidone or ditethylformamide).

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

  be prepared by dissolution of one or more

  active ingredients in an organic solvent containing

  optionally one or more wetting agents,

  then add the mixture to water which may also contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are dichlorethylene, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and ethers. glycol (for example

  2-ethoxyethanol and 2-butoxyethanol).

  The compositions for use in spraying may also be in the form of aerosols, in which case the formulation is contained in a pressure vessel in the presence of a propellant, for example the

  fluorotrichloromethane or dichlorodifluoromethane.

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

the compounds.

  Alternatively, the compounds can be used in a microencapsulated form. They can also be

  embedded in biodegradable polymeric formulations

  in order to obtain a slow regulated release of the

active substance.

  By the inclusion of suitable additives, for example additives intended to improve the distribution, the adhesiveness and the resistance to rain on treated surfaces, the different compositions can

  be better suited to different applications.

  The compounds can be used in the form of mixtures with fertilizers (for example fertilizers containing nitrogen, potassium or phosphorus). Compositions comprising only granules of the fertilizer to which the compound is incorporated for example in the form of a coating are preferred. These granules contain

  advantageously up to 25% by weight of the compound. The inventors

  Thus, a fertilizer composition comprising the compound of general formula (I) or a salt thereof is provided. The compositions may also be in the form of liquid preparations for use in baths or sprays, which are generally

  dispersions or aqueous emulsions containing the

  active ingredient in the presence of one or more surfactants, for example one or more wetting agents, dispersing agents, emulsifiers or delivery agents

  suspension; or they are spray formulations

  of the type that can be used in electrodynamic spraying techniques. The above agents may be cationic agents, anionic or not

  Ionic. Suitable cationic agents are

  quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable ionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulphate) and

  salts of aromatic sulphonates (eg dodecylbenzene)

  sodium zenesulphonate, lignosulphonate, butylnaph-

  sodium talenesulphonate, calcium or ammonium and a

  mixture of diisopropyl- and triisopropylnaphthalenesul-

sodium fonates).

  Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octylphenol or nonylphenol and octylcresol. Other nonionic agents are the partial esters derived from long-chain fatty acids

  chain and hexitol anhydride, the condensate

  said partial esters with ethylene oxide and lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose) and vegetable gums (for example gum arabic and gum tragacanth). Compositions for use in aqueous dispersions or emulsions are generally presented as a concentrate containing a high proportion of one or more active ingredients, and the concentrate should be diluted with water before use. These concentrates must often be able to withstand storage for extended periods of time and, after such storage, must be diluted with water to form aqueous preparations that remain homogeneous for long enough to

  can apply them with the aid of pulverulent equipment

  classic and electrodynamic Concentrates

  can advantageously contain up to 95%, preferably

  this 10 to 85%, for example 25 to 60% by weight of one or more active ingredients. These concentrates advantageously contain organic acids (for example alkaryl or arylsulphonic acids such as xylenesulphonic acid or dodecylbenzenesulphonic acid), since the presence of these acids can raise the viscosity of the active ingredient (s) in the solvents. frequently used in concentrates. The concentrates also advantageously contain a high proportion of surfactants, so that sufficiently stable aqueous emulsions can be obtained. After dilution to form aqueous preparations, these preparations may contain varying amounts of the active ingredient or ingredients for the intended purpose, but an aqueous preparation containing 0.0005% or 0.01 may be used.

  10% by weight of active ingredient (s).

  The compositions of the present invention may also contain one or more other compounds having biological activity, for example compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal activity. The other fungicidal compound may be, for example, a compound which is capable of combating diseases of the ears of cereals (eg wheat) due for example to species of the genera Septoria, Gibberella and Helminthosporium, seed-borne diseases. and the soil and the mildew and the white of the vine and the white and scab of the apple tree, and so on. These fungicide mixtures may have a broader spectrum of activity than the compound of general formula (I) alone; in addition, the other fungicide can have a synergistic effect on

  the fungicidal activity of the compound of general formula (I).

  Examples illustrating the other fungicidal compound include

  include carbendazim, benomyl, thiophanate-methyl, thiabendazole, fuberidazole, etridazole, dichlorofluanid, cymoxanil, oxadixyl, ofurace,

  metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminum

  nium, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, R 0 151 297, pyrazophos, ethirimol, ditalimofos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz, flutriafol,

  hexaconazole, i.e. 1- (1,2,4-triazol-1-yl) -2-

  (2,4-dichlorophenyl) hexan-2-ol, flusilazole, i.e.

  say 1 - ((bis-4-fluorophenyl) methylsilyl) methyl) -1H-

  1,2,4-triazole, triadimefon, triadimenol, dicyclobutrazol, furconazole, cis-furconazole, cyproconazole, terbuconazole, systemic, fenpropimorph, fenpropidine, chlorozolinate, diniconazole, imazilil, fenfuram, carboxin, oxycarboxin, dithianon, methfuroxam, dodemorph, BAS 454, blasticidine S, kasugamycin, edifenphos, kitazine P, cycloheximide, phthalide, probenzazole, isoprothiolane, tricyclazole, pyroquilan, chlorbenzthiazone, neoasozine, polyoxin D, validamycin A, repronil, fluotolanil, pencycuron,

  diclomezine, phenazine oxide, dimethyldithiocar-

  nickel bamate, tchlorthalem, bitertanol, bupirimate, etaconazole, streptomycin, cypofuram,

  biloxazol, quinomethionate, demethirimol, l- (2-

  cyano-2-methoximino-acetyl) -3-ethylurea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozebe, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulfur, dinocap, binapactryl, nitrothalisopropyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichlorane, compounds containing copper such as copper oxychloride, copper sulphate and Bordeaux mixture, and

organomercury compounds.

  The compounds of general formula (I) may be mixed with soil, peat or other rooting media to protect plants from fungal diseases propagated by seed, soil or

by the foliage.

  Suitable insecticides which can be included in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl> formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion,

  fenitrothion, phenotoate, chlorpyrifos, isoxazole

  thion, propaphos, monocrotophos, buprofezin,

  Ethroproxyfen and Cycloprothrin.

  Plant growth influencing compounds which can be used in the compositions of the invention are compounds which destroy weeds and inhibit ear development or which selectively influence growth of less desirable plants.

(eg grasses).

  Examples of suitable compounds influencing

  The growth promoters that can be used with the compositions of the invention are gibberellins (for example GA3, GA4 or GA7), auxins (for example indolacetic acid, indolbutyric acid, naphthoxyacetic acid or naphthylacetic acid, cytokines (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (for example 2,4-D or MCPA), substituted benzoic acids (for example triiodobenzoic acid), morphophtins (for example chlorofluorecol), maleic hydrazide, glyphosate, glyphosine, alcohols and fatty acids to

  long chain, dikegulac, paclobutrazol, flurpri-

  midol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg chlormequat, chlorphonium

  mepiquat), ethephon, carbetamide, 3,6-dichloro-

  Methylamine, daminozide, asulam, abscis

  that isopyrimil, 1- (4-chlorophenyl) -4,6-dimethyl-

  2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzenes

  zonitriles (eg bromoxynil), difenzoquat, benzoylpropethyl, 3,6-dichloropicolinic acid,

  fenpentezol, inabenfid, triapenthenol and tec-

nazene.

  The following examples illustrate the invention.

  Temperatures are expressed in degrees centigrade (C) and reactions involving intermediate compounds

  sensitive to water were conducted in nitrogen atmospheres.

EXAMPLE 1

  This example illustrates the preparation of 1- (4-

  chlorophenyl) -2- (1,2,4-triazolyl) methylpent-4-en-2-ol

(Compound N 131 of Table I).

  4-Chlorobenzyl chloride (32.8 g, 204 mmol) in anhydrous diethyl ether (30 mL) was added dropwise to a stirred mixture of magnesium turn (5.0 g, 204 mmol). in anhydrous diethyl ether (50 ml) at a selected rate of

  to maintain a constant reflux. Tetrahydrofuran

  Anhydrous form (80 ml) was then added as diethyl ether was distilled off. The mixture was then cooled to room temperature and added dropwise over one hour to a stirred solution of chloroacetyl chloride (46 g, 408 mmol) in dry tetrahydrofuran (200 ml) at -78 ° C. The mixture was allowed to warm to room temperature in one hour and then poured into water. It was extracted with diethyl ether and the combined extracts were washed with 2M aqueous sodium hydroxide solution and brine, dried (MgSO 4) and dried.

  evaporated under vacuum. Chromatography [sio2, hexane

  ethyl acetate (95: 5)) gave 1-chloro-3- (4-chloroethyl)

  phenyl) -acetone (16.8 g, 40%) melting at 47-49 C.

  1-Chloro-3- (4-chlorophenyl) acetone (6.0 g, 30 mmol) in anhydrous acetonitrile (5 ml) was added dropwise to a stirred mixture of 1.2. 4-triazole (4.2 g, 60 mmol) and potassium carbonate (8.8 g, 60 mmol) in anhydrous acetonitrile (50 ml) at 50 ° C. After 3.5 hours, the mixture The filtrate was poured into water and the mixture was extracted with ethyl acetate The combined extracts were washed with brine (until neutral), dried (MgSO 4) ) and evaporated under vacuum, chromatographed [SiO 2, ethyl acetate-hexane

  (50:50) to (100: 0)] 1- (1,2,4-triazolyl) -3- (4-chlorophenyl)

nyl) acetone (3.23 g, 46%).

  Allyl magnesium bromide (8.8 ml of a 1.0 M solution in ether, 8.8 mmol) was added

  dropwise to a stirred solution of 1- (1,2,4)

  triazolyl) -3- (4-chlorophenyl) acetone (1.39 g, 5.9 mmol) in anhydrous diethyl ether (10 ml). After one hour, the mixture was refluxed for 3 hours, cooled to room temperature and poured into saturated aqueous ammonium chloride solution. The mixture was extracted with ethyl acetate and the extracts were washed with brine, dried (MgSO4) and evaporated in vacuo. By chromatography (SiO2, acetate

  ethyl), 1- (4-chlorophenyl) -2-

  triazolyl) methylpent-4-en-2-ol (Compound N 131 of Table

I) (0.36 g, 22%).

EXAMPLE 2

  This example illustrates the preparation of 1- (4-

  chlorophenyl) -2- (1,2,4-triazolyl) methyl-3-methylpent-4-ene

  2-ol (Compound N 441 of Table I).

  Crotyl chloride (1.2 g, 13 mmol) in anhydrous tetrahydrofuran (4 ml) was added dropwise to a suspension of magnesium turn (0.35 g, 14 mmol) in dry tetrahydrofuran (5 ml). ) to one

  speed chosen so as to maintain a constant reflux.

  The mixture was then heated under reflux for a period of

  hour then cooled to 0OC. 1- (1,2,4-triazolyl) -3- (4-

  chlorophenyl) acetone (1.5 g, 6.37 mmol) in tetrahy-

  Anhydrous drofuran (7 ml) was added dropwise in minutes. After 4 hours at room temperature, the mixture was poured into saturated aqueous ammonium chloride solution and the resulting mixture was extracted with ethyl acetate. The extracts were washed with

  salt solution, dried (MgSO4) and evaporated in vacuo.

  By chromatography (SiO 2, ethyl acetate),

  1- (4-chlorophenyl) -2- (1,2,4-triazolyl) methyl-3-methyl-

  pent-4-en-2-ol (Compound N 441 of Table I) (0.25 g,

13%).

EXAMPLE 3

  This example illustrates the preparation of 1- (4-

  chlorophenyl) -2- (1,2,4-triazolyl) methylhex-4-yne-2-ol

(Compound N 123 of Table I).

  Trimethylsulfoxonium iodide (5.32 g, 24 mmol) and tetrabutylammonium bromide (0.2 g) were

  added to a suspension of 1- (1,2,4-triazolyl) -3- (4-

  chlorophenyl) acetone (5.0 g, 20 mmol) in toluene (33 ml). Potassium hydroxide (12 ml of 50% solution in water) was added dropwise and the resulting mixture was heated at 70 ° C for 1.5 hours. The mixture was cooled to room temperature and poured

  in a saturated aqueous solution of sodium bicarbonate.

  The resulting mixture was extracted with ethyl acetate and the extraction phases were washed with brine, dried (MgSO4) and evaporated in vacuo. By

  chromatography (SiO2, ethyl acetate), the resulting

  (4-chlorophenyl) -2- (1,2,4-triazolyl) methyl-2,3-epoxypropane

(3.22 g, 65%).

  Propyne was bubbled into tetrahedral

  anhydrous drofuran (12 ml) with stirring for minutes. Ethyl magnesium bromide (4 ml of a 3.0 M solution in ether, 12 mmol) was added dropwise at 0 ° C. Propyne was then bubbled into the mixture for another 30 minutes at 0 ° C. Then we have

  added dropwise 1- (4-chlorophenyl) -2-

  triazolyl) methyl-2,3-epoxypropane (1.5 g, 6.3 mmol) in dry tetrahydrofuran (6 ml) at 0 ° C. After minutes at 0 ° C., the mixture was refluxed for one hour and then cooled to room temperature and poured into water. The mixture was extracted with ethyl acetate and the extraction phases were washed with brine, dried (MgSO4) and evaporated in vacuo. By chromatography (SiO2, acetate

  of ethyl), a mixture of 1- (4-chlorophenyl) -2-

  (1,2,4-triazolyl) methyl-4-yn-2-ol and 1- (4-chlorophenyl)

  2- (1,2,4-triazolyl) mnéthyl-2,3-epoxypropane. This mixture was added to 1,2,4-triazole (0.7 g, 3.9 mmol) and potassium carbonate (0.4 g, 2.9 mmol) in industrial ethyl alcohol (40 g). ml) and refluxed during

  3 hours. The mixture was then cooled to room temperature

  room temperature and poured into the water. The resulting mixture was extracted with ethyl acetate and the extraction phases were washed with brine, dried (MgSO4) and evaporated in vacuo. By chromatography (SiO2,

  ethyl acetate), 1- (4-chlorophenyl) -2-

  (1,2,4-triazolyl) methylhex-4-yn-2-ol (Compound N 123

Table I) (0.36 g, 21%).

EXAMPLE 4

  This example illustrates the preparation of 1- (2-

  chlorophenyl) -2- (1,2,4-triazolyl) methyl-3,3-dimethylpent-4-

  en-2-ol (compound N 437 of Table I). 2- chloride

  chlorophenylacetyl (11.3 g, 60 mmol) and aluminum trichloride (8.0 g, 60 mmol) in dichloromethane (30 ml) were added dropwise to a stirred solution of 3-methyl-1 trimethylsilylbut-2-ene (12.6 ml, mmol) in dichloromethane (60 ml) at -78 ° C. in 45 minutes. After 10 minutes the mixture was warmed to room temperature and poured into an ice-cold solution of aqueous ammonium chloride. The resulting mixture was extracted with dichloromethane and the combined extracts were dried (MgSO4) and evaporated in vacuo. By chromatography [SiO2, petroleum ether (40-60) -acetate

  ethyl (100: 0) to 95: 5)], 1- (2-chlorophen) was obtained.

  nyl) -3,3-dimethylpent-4-en-2-one (4.0 g, 30%).

  N-Butyllithium (11.3 ml of a 1.6 M solution in hexane, 18 mmol) was added dropwise to a stirred solution of thioanisole (2.0 g, mmol) and 1 ml. 4-diazabicyclo [2.2.2] octane (2.0 g, 18 mmol) in anhydrous tetrahydrofuran (30 ml). The reaction mixture was cooled by means of a bath of ice and salt. After about 15 minutes, a precipitate formed and 45 minutes later,

  drop of 1- (2-chlorophenyl) -3,3-dimethylpent-4-ene-2-

  one (3.0 g, 13.5 mmol) in anhydrous tetrahydrofuran (15 ml). The mixture was warmed to room temperature and after 24 hours was poured into dilute hydrochloric acid and the resulting mixture was extracted with diethyl ether. The combined extracts were washed with water, dried (MgSO4) and evaporated in vacuo. By chromatography [SiO2, hexane-ethyl acetate

  (100: 0) to (95: 5)], 1- (2-chlorophenyl) -2- was obtained.

  phenylthiomethyl-3,3-dimethylpent-4-en-2-ol (2.6 g, 56%).

  1- (2-Chlorophenyl) -2-phenyl-

  thiomethyl-3,3-dimethylpent-4-en-2-ol (1.0 g, 3.0 mmol) to a stirred solution of triethyloxonium tetrafluoroborate (3.3 ml of a 1.0 M solution in dichloromethane, 3.3 mmol) in dichloromethane (10 ml). After 2 hours, the mixture was evaporated in vacuo, dissolved in dimethylformamide (6 ml) and the solution added to a 1,2,4-triazole sodium salt solution (formed by addition of 2,4-triazole (0.46 g, 6.6 mmol) to sodium hydride washed with petroleum ether (0.3 g of a 50% dispersion in

  the oil, 6.3 mmol) in dimethylformamide (4 ml)].

  After refluxing for 6 hours, the mixture was

  cooled to room temperature and poured into water.

  The resulting mixture was extracted with ethyl acetate (3 x 50 mL) and the combined extracts were dried (MgSO4) and evaporated in vacuo. Chromatography [SiO 2, hexane-ethyl acetate (90:10) at (70:30)] gave the

  1- (2-chlorophenyl) -2- (1,2,4-triazol-l-yl) methyl-3,3

  dimethylpent-4-en-2-ol (Compound N 437 of Table I)

(0.158 g, 17%).

EXAMPLE 5

  An emulsifiable concentrate was prepared by mixing the ingredients and stirring the mixture until

  all constituents are dissolved.

  Composition N 431 of Table I 10% Dichlorethylene 40% Calcium Dodecylbenzenesulfate 5% "Lubrol" L 10% "Aromasol" H 35%

EXAMPLE 6

  A grain-like composition readily dispersible in a liquid, for example in water, was prepared by grinding the first three ingredients together in the presence of added water, and then incorporating the sodium acetate with stirring. The resulting mixture was dried and sieved to 0.152 to 0.353 mm in order to obtain the desired grain diameter. Compound N 437 of Table I 50% "Dispersol" T 25% I'Lubrol "APN5 1.5% Sodium acetate 23.5%

EXAMPLE 7

  The ingredients were all ground together to produce a dispersing powder formulation

easily in liquids.

  Compound N 431 of Table I 45% "Dispersol" T 5% "Lissapol" NX 0.5% "Cellofas'" B600 2% Sodium acetate 47.5%

EXAMPLE 8

  The active ingredient was dissolved in a solvent and the resulting liquid was sprayed onto the kaolinite granules. The solvent was then allowed to evaporate to produce a granular composition. Compound N 437 of Table I 5% kaolinite granules 95%

EXAMPLE 9

  A composition suitable for use in the disinfection of seeds has been prepared by mixing the

three ingredients.

  Compound N 431 of Table I 50% Mineral oil 2% Kaolinite 48%

EXAMPLE 10

  A powder for dusting was prepared by

  mixing the active ingredient with talc.

  Compound N 437 of Table I 5% Talc 95%

EXAMPLE 11

  A colloidal formulation was prepared by

  ball milling of the constituents indicated below.

  underneath, then formation with water of a suspension

* Aqueous crushed mixture.

  Compound N 431 of Table I 40% "Dispersol" T 10% "Lubrol" APN5 1% Water

EXAMPLE 12

  A dispersible powder formulation was prepared by mixing together the ingredients listed below and then grinding the mixture until all

  the ingredients were intimately mixed.

  Compound N 437 of Table I 25% "Aerosol" OT / B 2% "Dispersol" AC 5% Kaolinite 28% Silica 40%

EXAMPLE 13

  This example illustrates the preparation of a dispersible powder formulation. The ingredients were mixed and the mixture was then milled in a sprayer. Compound N 431 of Table I 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% Kaolinite 34%

EXAMPLE 14

  The ingredients listed below have been formulated into a dispersible powder by mixing and grinding

of these ingredients.

  Compound N 437 of Table I 25% "Aerosol" OT / B 2% "Dispersol" AC 5% Kaolinite 68% In Examples 5 to 14, the proportions

  mentioned ingredients are given by weight.

  The remaining compounds shown in Table I were formulated as described in particular in

Examples 5 to 14.

  An explanation of the composi-

  tions or substances represented by the various

  trademarks mentioned above.

  AROMASOL H: mixture of alkylbenzenes used as solvent DISPERSOL T and AC: mixture of sodium sulphate and a

formaldehyde condensation product

  dehyde with sodium naphthalenesulphonate

  LUBROL APN5 condensation product of nonyl

  phenol (1 mole) with naphthalene oxide (5.5 moles)

  CELLOFAS B600: sodium salt of carboxymethylcellulose

lulose used as a thickener

  LISSAPOL NX: condensation product of nonyl

  phenol (1 mole) with ethylene oxide (8 moles) AEROSOL OT / B: sodium dioctyl sulfosuccinate

  PERMINAL BX: sodium alkylnaphthalenesulphonate.

EXAMPLE 15

  The compounds have been tested against various fungal diseases of plant foliage. The technique

used was the following.

  The plants were grown in a John Innes jar (N 1 or 2) compost in miniature pots 4 cm in diameter. The test compounds were formulated by ball milling with aqueous Dispersol T or as a solution in acetone or in an acetone / ethanol mixture which was diluted to the desired concentration immediately prior to use.

  use. For diseases of the foliage, the formulas

  (at 100 mg / l of active ingredient) were applied by foliar spraying and applied to the plant roots in the soil. Spraying was applied to maximum retention and root watering was carried out at a final concentration equivalent to about 40 millionths of active ingredient relative to dry soil. Tween 20, at a final concentration of 0.05%, was added when the sprays were

applied to cereals.

  For most tests, the compound has been

  applied to the soil (roots) and foliage (by spraying

  one to two days before inoculation of the plant with the pathogen. An exception was made for Erysiphe graminis in which the plants were inoculated 24 hours before the treatment. Foliar pathogens were applied by spraying in the form of

  suspensions of spores on the leaves of the test plants.

  After inoculation, the plants were installed in a

  appropriate environment so as to allow the infection to

  to incubate until the disease is ready for evaluation. The time elapsed between inoculation and evaluation varied

  from 4 to 14 days depending on the disease and the environment.

  The inhibition of the disease was evaluated according to the following scale of notations: 4 = no disease 3 = traces up to 5% of disease on untreated plants 2 = 6 to 25% of disease on plants untreated 1 = 26 to 59% disease on untreated plants 0 = 60 to 100% disease on plants

untreated.

  The results are reproduced in Table 1, Table 1, Table 1. Z û b And O 6ZI

Z.. * 0 E * [* 0 69

  mZ + 0 * t * t * ú (ZI) (IOJ) (DHO) (zqd) VIOD IIHDVUV IULHVVNIS INIWVHVLIONODM SODWOD VUOdSO "DUD VI VIilDIdId VIdfiANSA aHdISAMi vINIDDfd filG oN III OV3'1liVL TABLE 111 (continued )

  N OF THE PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA

  COMPOUND RECONDITA GRAMINIS INAEQUALIS ORYZAE ARACHIDICOLA

  (BLE) (BARLEY) (APPLE) (RICE) (PEANUT)

437 4 3 4 2

441 4 4 4 0, 1

451 0 * 3 * 4 * 0 * 0 *

461 3 4 4 1

462 4 4 4 3

  * Results achieved at the rate of 25 millionths - protection test only.

rO> os Do

Claims (13)

  1. Compounds characterized in that they correspond to the general formula (I): X R3 OR2 R5 y 1 t l I XXP C- C -C Az R4 - Q R6   R1 and stereoisomers thereof, wherein R1 represents a group of general formula (II): - C-C-R7 (II)   or a group of general formula (III) RBR9 \ = (III)   R 7 to R 10 represent, independently, hydrogen, halogen, alkyl, alkenyl or alkynyl; R2 is hydrogen, alkyl, alkenyl or alkynyl (with the proviso that the carbon atom adjacent to oxygen is not involved in any unsaturation); R3 to R6 are independently hydrogen, alkyl, alkenyl or   alkynyl; X, Y and Z independently represent hydrogen   ne, halogen, alkyl, cycloalkyl, cycloalkyl,   alkyl, alkenyl, alkynyl, aryl optionally   substituted, optionally substituted aralkyl, optionally substituted alkoxy, aryloxy or optionally substituted aralkoxy; Az represents an imidazol-1-yl or 1,2,4-triazol-1-yl group; Q is a bridging group having one of the following values Q1, Q2, Q3 or Q4: R11 I Q1 = -C- I R12 R11 R13 I I Q2 = - C - C II. R12 R14 R13 R13 R15 II t Q3 _ C- cC c_ I I I R12 R14 R16 R] 1 R13 R15 R17 1iI I Q4 - C C C c R12 R14 R16 R18   R11 to R18 are, independently, hydrogen, halogen, alkyl, alkenyl or alkynyl; and their salts and metal complexes, provided that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is   CH2 group, then R1 is not a CH = CH2 group.   2. Compounds characterized in that they correspond to the general formula (I): X R3 OR2 R5 Y II C C C Az Z R4 Q R6   R 3 and stereoisomers thereof, wherein R 1 represents a group of general formula (II): C = C - R7 (II)   or a group of general formula (III): P.9 R8 R9 C - C (III) R8 / "'- RI0   R7 to R10, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl or alkynyl group containing 2 to 4 carbon atoms or a halogen atom ( fluorine, chlorine, bromine or iodine), R2 represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms or an alkenyl or alkynyl group containing 3 to 6 carbon atoms (provided that the adjacent carbon atom at the oxygen atom is not involved in any unsaturation, R3 to R6, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl group or alkynyl containing 2 to 4 carbon atoms, X, Y and Z, which may be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl group, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl e, alkoxy, aryloxy or aralkoxy, Az represents a 1-imidazole or 1,2,4-triazole group and Q is a group of   bridging having one of the following values Q1, Q2, Q3 or Q4 R1 R12 RR R1 R13 Q2 = C C R12 R14 R11 R13 R15 I 1. R12 R14 R 17 Joe. R13 R15 R17 I I i Q4 = C _ C _ C _C_ R12 R14 R16 R18   or R11 to R18, which may be the same or different, each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkenyl or alkynyl group containing 2 to 4 carbon atoms or a halogen atom ( fluorine, chlorine or bromine); and their salts and metal complexes; provided that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is a   CH2 group, then R1 is not a group -CH = CH2.   - 3. Compounds characterized in that they correspond to the general formula (I): X R3 OR2 R5   embedded image and stereoisomers thereof, wherein R1 represents a group of the general formula (II): embedded image in which R1 represents a group of the general formula (II): ## STR5 ## * - C _C - R7 (II)   or a group of general formula (III): R9 C - C (III) R8 '\ R10   R 7 to R 10 are, independently, hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl; R2 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3-R6 are, independently, hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z represent, independently, hydrogen,   halogen, C1-C6 alkyl, C3 cycloalkyl.   C7, (C3-C7) cycloalkyl - (C1-C61) alkyl,   C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, phenyl   (C1-C6) alkyl, C1-C6 alkoxy, phenoxy or phenyl-   (C1-C6 alkoxy); Az represents an imidazole group   yl or 1,2,4-triazol-1-yl; Q is a bridging group having one of the following values Q1, Q2, Q3 or Q4: R11 O1 = -C- R12 R1 R13 RR Q2 = _ C- C -. I i R12 R14 Ril R13 R15 Q3-C ! l R12 R14 R16 R11 R13 R15 R17 I I I Q4 = - C c c-C I II i R12 R14 16 R18   or R11 to R18 are, independently, hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; all of the above aryl moieties are optionally substituted with halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, nitro, phenyl or phenoxy; and their salts and metal complexes; with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen, R6 is alkyl, alkenyl or alkynyl and Q is CH2, R1 is then not a CH = CH2 group.   4. Compounds according to any of   claims 1 to 3, characterized in that they respond to the general formula: X R3 OR2   Embedded image in which R 1 represents a group of general formula (II): ## STR2 ## and their stereoisomers, in which R1 represents a group of general formula (II): C = C-R7 (II)   or a group of general formula (III): C = C R8 / R5   R7 and R10 are, independently, hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R2 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z are independently hydrogen, halogen, C1-C6 alkyl, C3-C7 cycloalkyl, (C3-C7) cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, phenyl-C1-C6 alkyl, C1-C6 alkoxy, phenoxy or phenyl-C1-C6 alkoxy, Az represents imidazol-1-yl or 1,2, 4-triazol-1-yl; Q is   a bridging group having one of the values Q1 or Q2 above after: Rll IQ I Q1 = _ c R12 R11 R13 Q2 = _ C C He R12 R14   R11 to R14 are, independently, hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; all the aryl moieties mentioned above are optionally substituted with halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, nitro, phenyl or phenoxy; and their salts and their metal complexes.   5. Compounds according to any of   Claims 1 to 4, characterized in that they respond to the general formula (IA): R3 OR2 CH-C-CH2-Az Q Z I   R! and their stereoisomers, wherein R1 represents a group of the general formula (II): C = C - R7 (II)   or a group of general formula (III): - 9 C = R8 / R10   R7 to R10 represent, independently, hydrogen, a   halogen or C1-C4 alkyl; R2 is hydrogen   C 1 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl (with the proviso that the carbon atom   adjacent to oxygen is not involved in any   saturation); R3 is hydrogen or C1-C4 alkyl; X, Y and Z independently represent hydrogen, fluorine, chlorine, bromine, C1-C6alkyl, C3-C7cycloalkyl, (C3-C7cycloalkyl) -C1-6alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl or C1 to C6 alkoxy; Az represents an imidazol-1-yl or 1,2,4-triazol-1-yl group; Q is a bridging group having one of the following Q1 or Q2 values: -11 R " Q1 = _ C i R 2 RI1 Ri3 I. Q2 _ c _ R12 R14   R11 to R14 are, independently, hydrogen, halogen or C1-C4 alkyl; and their salts and their metal complexes.   6. Compounds according to any of   preceding claims, characterized in that   answer to the general formula (IB): X R3 OR2   and their stereoisomers, in which formula R1 represents a group of general formula (II): ## STR2 ## C = CR7 (II)   or a group of general formula (IIIA) R9 R (IIIA)   c = CH R1o o R7, R9 and R10 represent, independently, hydrogen, methyl or ethyl, R2 is hydrogen, methyl, propenyl or propynyl (provided that the carbon atoms adjacent to the oxygen are not involved in any unsaturation); R3 is hydrogen or methyl; X, Y and Z independently represent hydrogen, chlorine or fluorine; Q is a bridging group having one of the following Q1 or Q2 values: R11 R11 P R R '01 R1 f I i Q1 - C C--, Q2 = - CÀ C He R12 R12 R14   R11 to R14 independently represent hydrogen or   methyl group; and their salts and metal complexes   c. - 7. Compounds according to any of   preceding claims, characterized in that   meet the general formula (IC): X R3 OH y X CH- C - CH2 --N (IC) I (IC-   Q1 N CH CH2 and their stereoisomers, wherein R3 is hydrogen or methyl; Q is a bridging group with one of the following Q1 or Q2 values: Ril R11 L Q1 = - C - Q2 = CH2CH2 I - R12   R11 and R12 represent, independently, hydrogen or methyl group; X and Y are, independently, hydrogen and chlorine; and their salts and metal complexes. 8. Compound characterized in that it corresponds to the formula: ## STR1 ## CH4 N CH3 AH '   CH CH1 CH2 and its stereoisomers, and. their salts and their complexes of metals. 9. A compound characterized in that it meets the formula: C1 OH CH2 C CH2 N N iw C H 2 - -I CH3 - C CH3 N   CH 2 CH 2 and its stereoisomers, and their salts and metal complexes. 10. Process for the preparation of compounds of general formula (I) R3 OR2 R5 x F I I Z C-C C. Az ( 4 Q R6   R1 characterized in that it consists in etherifying an alcohol of formula: R3 (H R5 x t C C C - AZ (IV (IV) Z R4 Q R6   Wherein Az, Q, R 1, R 3 to R 6, X, Y and Z are as defined in claim 1, by treatment with a base such as sodium hydride and an alkyl halide R2Hal in which Hal may be to be chlorine,   bromine or iodine and R2 is as defined in the claim   1 to the exclusion of hydrogen, in a solvent, and the compounds of general formula (IV) are prepared by treatment of compounds of general formula (VI): X R3 0 R5 He (VI) Y) C- C C - Az 1 0 41   in which Az, R3 to R6, X, Y and Z are as defined in claim 1, with compounds of general formula (VII): M Q R1 (VII)   wherein Q and R 1 are as defined in claim 1 and M is a metal such as magnesium, lithium or titanium, or the compounds of general formula (V) are prepared by treating compounds of formula General (VIII): - X R3 O R5 C C - C - Hal (VIII) 1 Z R R6   in which R3 to R6, X, Y and Z are as defined in claim 1 and Hal is a chlorine, bromine or diode atom, with compounds of general formula (VII): M Q R1 (VII)   wherein Q and R 1 are as defined in claim 1, and M is a metal such as magnesium, lithium or titanium, followed by treatment with an azole (imidazole or 1, 2, 4-triazole).   11. Fungicidal composition, characterized in that it comprises as active ingredient a compound according to claim 1 or a stereoisomer, their salt or metal complex, and optionally a carrier or a diluent. 12. Method for controlling fungi, characterized in that it consists in applying to a plant, to the seed of a plant or to the place where the plant or the seed is located, a compound according to Claim 1 or a steroid. isomer, a salt or a metal complex of this   compound or a composition according to claim 11.   13. New intermediate compounds, characterized in that they correspond to one of the formulas R3 OH R5 XC - -C. .C Az (IV) z R4 Q R6 I R1 R3 OH R5 C C C Az (V) Y, Z R4 Q R6 C C R -108- X R3 0 R5 <c c c (XVI) I I   where R, X, Y, Z, R1, R3, R4, R5, R6, Az, Q and R7   are as defined in any one of the claims tions 1 to 7.