FR2634482A1 - NOVEL 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 radical, R ** 2 to R ** 6 represent hydrogen or organic radicals; X, Y and Z represent hydrogen, halogen or organic radicals; Az is a 1-imidazole or 1,2,4-triazole radical; and their stereoisomers as well as their salts and metal complexes. It also relates to a process for preparing these compounds. The compounds of the invention are endowed with fungicidal activity. They can be incorporated into fungicidal compositions intended for combating fungi, in particular fungal infections of plants.

Description

The present invention relates to heterocyclic compounds which are

  useful as fungicides, methods for obtaining them, compositions

  fungicides which contain them and their processes for

  to combat fungi, especially

  fungal infections of plants.

  The invention provides compounds which have the general formula (I): X p3 oFS p, O C-C -Az (I)

I I

  and wherein R 1 is an alkyl group (when R 5 is other than hydrogen), a group of general formula (II):

- CC - R7 (II)

  or a group of general formula (III):

R / R (III)

C C

R8 R10

  wherein R7, R8, R9 and R10 are, independently, hydrogen, halogen, alkyl, alkenyl or alkynyl; R2 is hydrogen, an alkyl, alkenyl or alkynyl radical (with the proviso that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R3, R4, R5 and R6 are, independently, hydrogen, alkyl, alkenyl or alkynyl; X, Y and Z are independently selected from the group consisting of hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, haloalkoxy, optionally substituted aryloxy or optionally substituted aralkoxy; Az is imidazol-1-yl or 1,2,4-triazol-1-yl; with the proviso that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl, then R1 is not a -C group -C alkyl, and with the proviso that when R 3 and R 4 are both alkyl, R 5 is hydrogen and R 6 is alkyl, alkenyl or alkynyl, R 8, R 9 and R 10 are then not all hydrogen; and their salts

and metal complexes.

  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, and these mixtures as well as other mixtures of optical isomers can be separated into isomers

  by operations known in the art.

  and these isomers form part of the

present invention.

  Alkyl groups containing 1 to 4 carbon atoms represented by R 3 to R 10 are straight chain or branched chain groups, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, dry butyl or tert-butyl. Alkyl groups containing 1 to 6 carbon atoms represented by R 1 or R 2 are straight-chain or branched-chain groups, for example methyl,

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

  butyl, tert-butyl, pentyl (straight or branched chain) or hexyl (straight or branched chain). Alkyl groups and alkyl portions of the alkoxy, haloalkyl, haloalkoxy, aralkyl and aralkoxy 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 all the particular isomers mentioned above. Alkenyl groups containing 2 to 4 carbon atoms represented by R3 to R10, which are identical or

  different, may be alc-1-enyl groups, alc-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)

  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 may have the geometry E

  or Z (including cis and trans) may be subgroups

  2-enyl, 3-enyl-enyl, 4-enyl or 5-enyl-enyl, by

  example allyl, 1- (1-methylprop-2-enyl), 1- (2-methylpropyl)

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

  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 may be the same or different, and may have E or Z geometry (including cis and trans), may be straight or branched chain groups containing 2 to 6 atoms carbon, for example

  vinyl or allyl, or any of the examples

born above.

  Alkynyl groups containing 2 to 4 carbon atoms represented by R 3 to R 10, which are identical or different, may be, for example, ethynyl groups,

  prop-1-ynyl, propargyl, 2-but-3-ynyl, but-1-ynyl, but-

  2-ynyl or but-3-ynyl. Alkynyl groups containing 3 to 6 carbon atoms represented by R2 may be

  alc-2-ynyl, alk-3-ynyl, alc-4-ynyl or alc-5- groups

  ynyl, for example propargyl or but-2-ynyl. Alkynyl groups represented by X, Y and Z may be straight or branched chain groups containing 2 to 6 carbon atoms, for example ethynyl or propargyl, or one

  any of the examples mentioned above.

  Cycloalkyl groups represented by X, Y and Z may be C3-C7 cycloalkyl groups,

  cyclopropyl groups, cyclobutyl groups, cyclopenyl

tyl, cyclohexyl or cycloheptyl.

  Cycloalkylalkyl groups represented by X,

  Y and Z may be (C3-C7) cycloalkyl groups -

  (C1-C6) alkyl, for example cyclopropylmethyl,

  cyclohexylmethyl or 1-cyclopropylethyl.

  Examples illustrating X, Y and Z when these groups are aryl, aralkyl, aryloxy or aralkoxy are phenyl, benzyl, phenoxy and benzyloxy. These rings may be substituted with a halogen (fluorine, chlorine or bromine), a C1 to

  C6 (eg methyl, ethyl, n-propyl, iso-propyl, n-

  butyl, iso-butyl, sec-butyl or tert-butyl), C 1 -C 6 alkoxy (for example methoxy, ethoxy, propoxy or

  butoxy), C1-C6 haloalkyl (e.g. trifluoromethyl)

  thyl, C1-C6 haloalkoxy (for example trifluoromethyl)

  thoxy), nitro, phenyl or phenoxy.

  Halogen atoms are the atoms of

fluorine, chlorine, bromine or iodine.

  According to another aspect, the invention provides compounds corresponding to the general formula (I):

2

X R3 OR2 R5

I I

  [i t C C C-Az

1 1 R6

  Embedded image in which R 1 represents an alkyl group containing 1 to 6 carbon atoms,

  carbon dioxide (for cases where R5 is something other than hydrogen

  ne) or a group of general formula (II):

C C - R7 (II)

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

C C

R8 R10

  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 alkoxy, aryloxy or aralkoxy, and Az represents 1-imidazole or 1,2,4-triazole, with the proviso that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl, then R1 is not -CC-alkyl and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is an alkyl, alkenyl or alkynyl group, R8, R9 and R10 are then not all hydrogen; and their salts and metal complexes.

  According to yet another of its aspects, the invention

  It proposes compounds of general formula (I):

X R3 OR2 R5

  wherein R5 is a C1-C6 alkyl group (when R5 is other than hydrogen) or is a heterocyclic group; group of general formula (II):

C = C - R7 '(II)

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

C._ C (III)

c: c R8 \ RlO

  R7, R8, R9 and R10 independently represent hydrogen.

  ne, halogen, C1-C4 alkyl, C2-C4 alkenyl, 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 to R6 are, independently, hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z are independently selected from the group consisting of hydrogen, halogen, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C7 cycloalkyl (C3 to C7 cycloalkyl) - (alkyl) C1 to C6), C2 to C6 alkenyl, C2 to C6 alkynyl, phenyl, phenyl (C1 to C6) alkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, phenoxy

  or phenyl- (C1-C6) alkoxy; Az is an imidazole group

  1-yl or 1,2,4-triazol-1-yl; all groupings

  phenyl mentioned above are optionally subs-

  halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, nitro, phenyl or phenoxy, with the proviso that when R3 and R4 are both methyl groups , R5 and

  R6 are both hydrogen and Az is a group 1,2,4-

  triazol-1-yl, R 1 is not then a -CeC-alkyl group and provided that when R3. and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, and R8, R9 and R10 are not all hydrogen; and their salts and metal complexes.

  According to yet another of its aspects, the invention

  It proposes compounds of general formula (I):

X R3 OR2 R-

  C - C _ C Az () 4 tI p zR R1! and their stereoisomers, wherein R 1 is C 3 or C 4 alkyl, R 2, R 3 and R 6 are, independently, hydrogen or C 1 -C 4 alkyl; R4 is hydrogen; R5 is C1-C4 alkyl; X, Y and Z independently represent hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, phenoxy or phenyl; Az is an imidazole-1-yl group or

  1,2,4-triazol-l-yl; and their salts and metal complexes

c.

  According to yet another of its aspects, the invention

  This invention provides compounds of formula (I) wherein R 1 is C 3 or C 4 alkyl, R 2 is hydrogen or methyl; R3, R4 and R6 are all hydrogen, R5

  is a C1 or C2 alkyl group; Az is a group 1,2,4-

  triazol-1-yl, X, Y and Z independently represent hydrogen, chlorine or fluorine atoms; and their salts

and their metal complexes.

  According to yet another of its aspects, the invention

  The invention provides compounds of the general formula (I): ## STR2 ##

Z R4 R1 R6

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

C = C R- 7 (II)

  or a group of general formula (III): R9

C - C 11 (III)

C ---. C

R10

R8 R

  formulas wherein R7, R8, R9 and R10 independently represent hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R2 is hydrogen, C1-C4 alkyl, C3-C4 alkenyl or C3-C6 alkynyl (with the proviso that the adjacent carbon atom & oxygen is not involved in any

  unsaturated); R3, R4, R5 and R6 independently represent

  hydrogen, C1-C6 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z independently represent hydrogen, chlorine or

  fluorine; Az is an imidazole-1-yl or 1,2,4-triazole group

  1-yl; with the proviso that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl, then R1 is not -CC-alkyl and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, then R8, R9 and R10 are not all hydrogen; salts

and their metal complexes.

  According to yet another of its aspects, the invention

  It proposes compounds corresponding to the general formula

(XXXIV):

OR 2

CH2C-CH2-NN

(XXXIV)

  x and their stereoisomers, in which formula R1 is a group of formula (II):

- CC R7 (II)

  or a group of formula (III): R9c C (III) R8 Rio

  R7, R8, R9 and R10 independently represent hydrogen.

  ne or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl, allyl or propargyl; X, Y and Z O10 independently represent hydrogen, chlorine or fluorine atoms; and their salts and metal complexes.

  According to yet another of its aspects, the invention

  It proposes compounds corresponding to the general formula

(XXXV):

  ## STR2 ## and their stereoisomers, in which R1 is a group of formula (II): ## STR2 ##

C = C R7 (II)

  or a group of formula (III) R9 c = c / (III)

R8. R \ 10

  R7 is C1-C4alkyl, R8 is hydrogen, one of R9 and R10 is hydrogen while the other is C1-C4alkyl; R2 is hydrogen or methyl; X and Y represent hydrogen, chlorine or fluorine atoms; and their salts and metal complexes.

  According to yet another of its aspects, the invention

proposes the compound:

F C '

> ss OH

CH2- C -CH2- NO

CH N

HC

CH2- CH3

  (Compound No. 233 of Table I) and its stereoisomers, its

salts and its metal complexes.

  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 ipr represents the iso-propyl group nBu represents the normal butyl group iBu represents the isobutyl group SBu represents the secondary butyl group tBu represents the tert-butyl group

  Tr is 1,2,4-triazol-1-yl.

  All the melting points in Table I below

  after are expressed in degrees centigrade.

  Although the azole (Az) in column 11 of Table I is indicated by the symbol Tr (that is, 1,2,4-triazol-11-yl), it should be noted that it could also be an Im group (i.e., imidazole-1-yl), and this designation should be considered

  as including, in each case, the imidazole-1 group

  yle corresponding to the precise 1,2,4-triazole-1-yl group specified. ## STR2 ## wherein: ## STR2 ## wherein: ## STR2 ## ) -Z 8

  S9.t11-011.11 H H H H H 4-3D H 1> 9 ID-

  r. ## STR1 ## ## STR2 ## H H Ht! ## EQU1 ## H H5E H Z A X -SOdWOD S321nIVJNawNO SG iNIOd 2v 9 ú, Z nGoN n n n n 1 tl:> taa i A1 _ __ _ _ 1> 1IJJLZZ & L il H t l! ## STR2 ## wherein: ## STR1 ## wherein: ## STR2 ## H 4a M3-0DHID [c'ID-Z91 k! Il. IIH H H TA D% D H ID-V, ID-Z51 D. I -69 ilUH 33 -o. 11H-IIID 9ID-U1 ALHH II 11IWiJD 4-3D11 HI- ID-ZZ I U Hiiii it tiiNii> ZiJD ± DeDH1D-9-ID 111 Sd iIVJ.NdWWOD3NOI I [H 8 -H 5H -Hz A X o h. NolflVA 3oNI D'Jxr ', v A1.H H li | ## STR1 ## ## STR2 ## H1 11H11H110I140: ll109 ID-7S-J. ## EQU1 ## ID-Z ID-HtL11 HII Hdd 1HD4U H 0-9 ID-1 ZZ

H 11 H, H, T 71? 04 I 1 3- 1I-Z

  NOa1V1:; <(, i] t "zV ,," 1 u ... .. .V_A "t1, CI.

  AI. Jv *., L, oo Co J1. XI Il lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

I Z

  TAL It A 4ii Iil: -r 9I; DII IZ 0c 4JL l - tHH HH 449 it ID-TD-Z 6Z sd Noii NH USOCWOD -1 \ LLN "4JNUDSU LNILd f9S z AX (041ns) JnV1'1iV oo cm (' ## STR2 ## ## STR1 ## ## STR1 ## wherein: ## STR1 ## ## STR1 ## wherein: ## STR1 ## .INNOD ".H l ,. L {.! IOD

D _

H Z

  ## STR1 ## wherein: ## STR1 ## wherein: ## STR2 ## wherein: ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## where ## STR2 ## E 48 2-CI 4-C1 IO! -CHntEt tl H Il H l Tr zii Js, oo ru CoII iG ALdH HHH Hn ON HID-tId: 7S l J AL [l Hl El IK> - 't4H ") RUX> L) U- 1; I 1a c ú ú I l A: L11 '1111 1tl D? I'EEID: EtLMD111:) - 9I :: - Zi 7,

  ò AL iltl It II HH1 1 H 3- HIS IDUIW> kttIO'1! IO-gI-

  AL H111 l {-1of4H9 {$ A {HI'-ID - ;: OS AL! ## EQU1 ## where: ## EQU1 ## where: ## STR2 ## ] .._. _... 1: 2-IU9, 1111, 1111, 1111, and 11: 1). ## STR1 ## ## STR1 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## 2.dnrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrr

  NI0DURX y z R 2 R3 4 R5 R6 Az DECOMING POINT-

X Y Z R4 2R R 'R

_COMPOSE RR RFUSION RES

  ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## ## STR1 ## wherein: ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## where ## STR1 ## HH 13-Z úL SsuIVi NOI Sfk4 SI -NSoWNODl92 8h ZL 91 ZAX IIo -N3G0Daa I ^ NIOd 5 * 1 E: _ nG TABLE I (continued)

NO. 2 36POINT OF COMMENT

  COMPOSEXY Z R 'R2 R R4 R5 R6 AZFUSIONRES

-.X. COMMNTA

  83 2-CIIlHClK: IHCi9-01'C1t2HH J 11 Tr 84 2-CIHH Qf-CH2CH2-CiCHHH HH Tr 2CIHH C1 = CleH H H1 HH Tr oil E 86 2 -CliHHQClH1 HH lI TrI z 87 2-ClHH e HHHHT oil E 88 2-CIttl! Hf "He" 1! "i HIv z I

89 2C1 H8 E H H H H W

  2, - 1H-1H 2 O -H 2 HH I-1 6 AL HHHH JdH2 = flD_40 HH ID-Z ZH ItH HHH II HD-Hlu, 3.1) I) HH! D-: -u6 the? 16 J H 11 H H II H Tg 41-t9 H H ITD-Z Z6 (j 3 Sad'4 I N O I S * i, :) 16

-_ _ _ _ M H H I 0Z

  -IV.NSWWOD 3G LNIOd _u 9_i ZAX n oN (atzns) I lvqUVL (Co Pe% O 04- o <J OTTn4_L HHH _ H Mi.9'4H HHI lD-ZTOI ALH HH li 1ND-ÉIID1I HH IDZ ZOI ## STR1 ## ## STR1 ##, ## STR1 ##, ## STR2 ## l H IH-Z L6

JJL H HH H1 H SOZD; I) DH H1 I-Z 96

  ## EQU1 ## in which: ## STR1 ## is a reference to the present invention, wherein: ## STR1 ## is a compound of the present invention, wherein: ## STR1 ## ## STR1 ## in which: ## STR1 ## in which: ## STR2 ## a HH! IDRID HH lD-Z lO! H>: It 1'3 [NOISnf SodwoD I-IV.LNzw1OD30 INIOdI Z91ú8 AX

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ [_ O _ _ O _

  (etfs) IOV'IV CO ND R '' 11 11 H H H 1: = i H! 1 i ID-Z911 U H H H H I Z1. H1 H1 H1 H1 H1 H1 H1 H1

## EQU1 ##

  ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ##

(OyrflS) Ha oN3IH.

  ## STR2 ## ## STR2 ## where: ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## x SOdWOD - IVLNaWNWOD 3a LNIOd 9 fOn (, 4ns I l1V TABLE I (continued)

Nude FROM 2 3 4 5, POINT OF COMMAND-

  COMPOSEX YZRRR R4 RR a FUSION 1ARIs 126 4-ClH 1H (CI CH2-C (HHHHH Tr 127 4-C1 HH EC-MeH IIIH IIH 99! 5-1O1 5'Cl 128 4-C1 HH cc-Me ## STR1 ## ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## wherein the oil is used to prepare the oil, and the oil is used to prepare the oil. ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## HH? 'LiD = liDH H ISFq 8.1

HD "06E!

  ## STR2 ## ## STR1 ## ## STR2 ##

q. _I I l I u -.

  ## STR2 ## wherein: ## STR1 ## TABLE T (continued)

NO. 3 4 [5 POINT OF I COMMEN-

  COMPOUND x YZ R1 R FUSION: TAXES 144 4-cI H It CH-d.2 c.2-0m i HI HI {I Te 4-C1 H Il 01C0% HHHHH Tr 1l &, 9-117,5'CE 146 4 -c- HIH CH = CIe II. H H H H Tr w

Z {,

  147 4-C H H H H H H H H H H Tr oil E 148 4-cl H H OCCRICHMe3 i H lU Il Tr} z 149 4-c1 H I HC And H i {HJTr

I I

  ## EQU1 ## and ## EQU1 ## ## STR1 ##, ## STR2 ## he - IV N W 0INlIl g 9U 5 é tut A j X | O nal (nd) I nv3rlGvL

- I

  eTTnq 'J HL! 1 U H H t tD - ZID adi..Ot H H [1D-'9 úC z

he H 4U3-IfII H the-he -

  ## STR1 ## ## EQU1 ## , XI! ## EQU1 ## where ## EQU1 ## where ## STR2 ## t I lt i l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l H H H H H 11 D 4 D I H 11 IT 091 IT. Hl Hl Hl Hi | ## STR1 ## iSOdWOD 1VIN21JWWOD iU INIOd 9 '] l oN o cO 0, {Il It H' d, 1I3 "OIlIl19-18011 HH 11 H Idu 13: 1O = IHH IDN691 J] UHHH 1 Ta 1:) - IH H l I- ## STR2 ## wherein: ## STR1 ## wherein R1 is ## STR2 ## wherein R1 is ## STR2 ## wherein R1 is ## STR2 ## -IV.LNWWOD 3a INIOc98 111, ú It 8 2 to 5 lU- oN HTS tlH H 3aVll: H "% Io c% 'T - __ __________ ___ _D = IIDHi__ I> t, ILI | IHH l. H | H [IIt9

| 11H H HH 4ï 4 O H HID- | 911

  -q HI H H, HgD. z | L tr | 4 H H H H at 13-% IDfH H1D-q | ú11

M. H1 H H H11 | = ID-'IDH H

-% LH H H H | -FH 3 H H I 1I

  ## STR1 ## ## STR1 ## ## STR2 ## [## STR2 ## ## STR1 ## wherein: HD &H;## EQU1 ## where ## STR1 ##

U 1 H H HI HI SD-M) H H I> 0 6LI

  ## EQU1 ## where: ## STR1 ##, ## STR1 ##, ## STR2 ## ## EQU1 ## where: ## EQU1 ##, ## STR2 ##, ## STR2 ## ## STR2 ## ## STR1 ## wherein R 1 is H 2 H 3 HH-H-qID-Z681; ## EQU1 ## where: ## STR2 ## FAT I (continued)

  N ° OF X Y RI R2 R3 R4 R5 R6 OINTDE CC) MMENTAL-

COMPOUND USION RES

  196 2-C1 4-FH 02C-And npr HHHH Tr 197 2-C41 4-F It (& C-And CH2-CU-Cl2 1 H III Tr 198 2-Cl 4-F Hl C-Et ci2 - (li ## STR2 ## He IH Tr 202 2-Cl 4-F He Q-CH2 Ih 11 HHHI IY

203 2-C 4-F 1! CH 2 CH 2 -CH = 12 H! H H T

CII-CH2 CH2-CFK

204 2-Cl 4-F Ci-2 Ci This 1 H H Tv r

  I I _ _ _ __} _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

r> TABLE T (site)

N OF 5 6 COMMENT POINT-

  Compounds YZRRRRRRR FUSION RES 205 2-Cl 4-IF {CII = HHHH tr Tr 206 2-Cl 4-FH Z-cit} eH I Il H Hl Trw Z 207 2 {: 1 4 -FH E10i fi tl ## STR1 ## 2-C1 4-FH QCIKCt! Ie H H H H TrI E: 8 2-Cl 4-FH! ## STR2 ## ru, II! l It It tl'R. '.......... O- i D% L! O, 4 Hg it, -9 id "Z 9I Z j -4% L -,. 40H ID- ## STR2 ## wherein R 1 is embedded in the formula (## STR2 ## ## STR5 ##

; I - I

  It is possible to use the following table:

L H H H ZH Z F II '

  | .I i H H H II B x H-OHD VIZOZZ 1HH% H 3 ZI It li, i9DID-6n Z O1H H H = ll a'dx1H3 1HAT-t10Z81Z B H H B ___ HA 3 - S ZL1Z wuvç ANOISf. Od w gd 5E Z A _ dSOdWOD ilIllo -I ........., LIdY Qe uo TAILEAU I (continued)

  N ° OF X Y 7 R] R2 R R4 R5 R6 i ICOMMENTAL POINT

COMPOSITION R R R R R FUSION RES

  ## STR2 ## ## STR2 ## 227 ## STR2 ## -CI 4-F It CZC! TF: FtH IH Hl IH | Y Z 229 2-CI 4-FH CCHFT "Pr HHH IY E 230 2-CI 4-FH TIP H n H H 11 H z 2 31. 2-CI 4-F l! = CIlE C12-CI-'ct2 He lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

I II- - L

  ] H | 11 i1 | dul4ZfflH ff A - T | - 1 / ZiZ | A1 HH H1 Ht | j83 Hs_D-ZLúZ j. ## STR2 ## HH1H1H2H1H2H1H2H1H2H2H2H2H1H2H1H2HHH1H2HHHH1H1HHH1H1HHH1H1HHHH1H1HHH1HHHH1HHHH1H2HHH1H2HHH1 ## STR1 ##, ## STR1 ##, ## STR2 ##, ## STR1 ##, ## STR1 ## 1H-NMR (CDCl3) 3H-NMR (CDCl3) 3H-NMR (CDCl3); ltl,., Jai t UH HHH H1 Hs> lI3-8A-Zr "

3LH HZH H W; OHIO'A.-rÀ -

  X G H HHHH H4HN3 IO-a S-ZrtZ -IVNWWOD.U INICl NLZ oN 91t -IVJ.NWWOD / Ic {jRIOgi lHZAX 'FIGON il-Hua-ti XIII {HQZ (' J 4J H | Hi-R I: S 1Xx, OH 1 H IIG> Z0 -Oo HN 1Dt AZ j ZS u H HHH H UI -MuHlNq.zOZ ot.4 -._, _

: 3- l O - o H I- -

  'OS -IVINSWWOD) U LNIOd 9 ,! 1 9t! ## STR2 ## wherein: ## STR2 ## ## STR5 ## wherein Y 1: ZH 2 H 2 O 3 H 2 H (H 2 HI 3) H 1 JLNqNOD3UlId9 1 i (104fs LNIOd 9H gH oc (j

  A.H1111 H H 4410.410H4 ID-9.4Z59Z

  ## STR1 ## wherein nH H1H H111q> DH ID "-v.-Z6S9% L i H 1H0-% - nHH! t -Z_tZ

-U HH. 114- H -DHID - ZLSZ

  ## STR2 ## wherein 1U13M0H1K-9d_lit IIh H H.! 4. IDID -.-, d.-Z89Z I XLHHHl11D 40 HI3-td-z69Z ALHH HH i W OHIID-t! S-H Z99Z QYou It Hi 14 AAs 19wo J.HH H utl tt0 It tCd-9 9

AZ. _-

  -3U IN tO NO II NN; N HIN tlzHZ-A X 9dWoN -INIWWO, = IU.LNTOd 9 SúI100

9 {9 I U I Z

  oC -: _ 3- <H 11 H || -i | -4 | ## STR1 ## ## STR1 ## where: ## STR2 ## ## STR2 ## ## STR2 ## wherein: embedded image ## EQU1 ## where: ## STR1 ## ## STR2 ## where: ## STR2 ## -7 & -_ 1 / 8Z | JL Hl H1 1H JdU4r H H 1 - ID - the _ 8 H1 HHHW> OW Zfl8Â'H1ID -, l-68Z SdNOISnal HH {| H ZSOdWOD -IVLNNWWOD [3a LNIOd9 May 11 oN -. 4 u 'o

('J 6

  i i S AL i H, it! H H H H H H H H H H H H H H H H H H H H H H H O H H H H H IduuH: .4DH19-. I-Z 06Z - iJ. ## EQU1 ## ## STR1 ## 8 S3d NOISOA 3SOdNoD -IVLN3WOWOD aS (.NIOdz% 9S 5H lu Zo {lu ZX n N (a; ins) I rnV31SV AL _ _ _ ilD-ZH: D Z40 = m | 1:) - 7 d- Z_o Il ## EQU1 ## where: ## STR1 ## tl HH. HID-VA-Z16Z-H1H1H-1H1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H-1H; 4z5p6Z oI Xl HHH H IDH :) HI:) - V-ZV6Z J.HHH HIID-9a-Z-6Z

AL H11 H H HWZDGN H ID-A-ZE6Z

  S3I 'NOTSi ssodwo [-IVU.NEWNOD C I iNIOd ZV9I 5 _ Z fiG oN (a:, ns) I lsV'lisl co o

% 0 0

  cm-1 1 I - H il of the A-O IH U.I-q i-z 'OIC -'J. 1h Hi Hi Hl as 4-S H I-t to-Z 60C H H H! ## STR2 ## wherein: ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## ## STR1 ## ## EQU1 ## where ## STR2 ## {| 2i 5/8 __ 2 {z2 12 Z A 3SOdWOD -IVINZWWi I NO0 a a, ta - o {-IVJ. N3WWO3JaCI LNIOdI 'ú ú10n oN (, J oo:, r 1 <, ro Cu CIl H _. H - -Z Oz it tl i Ht, lt. - *,. 4-zOgú U n HH, H ## STR2 ## wherein: ## STR2 ## wherein: ## STR2 ## ## STR2 ## UIL HHH HI z3 3-DrDH A-t3-Z! Ic

t1 H H H: TJ T "-D ', H -

* H H H Il {i :: rA l A-, - il}. H H H H ZH: rJ H -. EI-HH H II II -D aHk. i-Hl q1- - {ZIE SSUNOI snswX. X EE zE _ __ ^ X ESOdiWOD -IVT.NNwwOD 30 LNIOd. ## STR1 ## wherein 4 9 Z.4.i ALHH0HH H iWI> VH.4 -4qw Z s U H HHIIH-u 1C) HA - IZ HHHH H. H = H 'H. H .. H -HW.Nil 0H H HexodjL 9 H A-VA-Z AL HHHH HHH B-SIA-HHA- 8- Z ICI su IVLNai2JH HHH HHHHHHHHHHHHQWHUH

> I

  4 11H H H | ## STR2 ## wherein IVLNaWoD NIOD _ tH H HHH ZI Z1D4 H l A - X | SOdClD (aRTns) _ I I Id sudNoisilà ilZI To- H ASJ-wo -IVILNSWWOD sa.LNIOd LIU N (n;. TflS \ l N o ", O

: l he ilIl Idu%> :) H to-qAz -

AT H H H H 3 Z1D-4H.I-, -: 0.6E

  q HH H H H 1-1A-Z Zúú H H H H: H. 1H. = HAlz LCú tn AL HHilH HtlI; D-.H H_-z ú __. 1 H H H H HStY-% 40 H. 4-lA-zS-ú

1 -:

  ## EQU1 ## ## STR1 ## ## STR1 ## ## STR2 ## I HL 4 H 11 Hl Hd ZI3 H J_ @ a- 9 E t1 ii 1 H He l3Jtlk50 = Di - atZ M; 9 ta X

I, _ ...... _

  save NOIsnf, I! SOdWOD -IVWNS WWOD 23QNIOd. IM'tZZ [HERE aoND atts .. VWI. ## EQU1 ## ## STR1 ## ## STR1 ## ## STR1 ## SJ, H he HI IJdI: 13t-D *: H3-1q -Z 671

$ .q H H% H- HU-o H $ n.

  ## EQU1 ## 1 ## EQU1 ## 1 ## EQU1 ## JH TA Il1I ID-913-VI I-ZC9C HJ 1J HH IDR) 1-91-V13-ZZ9c! H HHH 1 'HH Ili.O 1D-9 ID-V 13-Z19u tl IH t tH l R Hit> - Z 1, O 1 HA-AD-ZO9E AL H HH HNZ111DZ1Za.), HA-VA-Z 65 u so H1 Ht HtJdZ4D | 4H A-VA-Z 85 V Az L6S

HLHil H H1 to ZID = tH A-V _ "_z- 9A-

  qH H H H H H H H =) H AJ-A-Z 9 sauNOISflAZ read a a z X'x psodwoD IVILNNWWOD Ci ILNIOd9 A (d4ttls) Il oNVU

I -

  ## STR5 ## wherein: ## STR1 ## in which: ## STR1 ## ## STR1 ## VID-Z6 9c JU HHHH HD; O-% HID-) tD-91D-913-Z99 4L HHHH iuD-AoHDo 13-9ID-9ID-Zs9E HHH II Id 1 [-R) I-913-9 II-ZV9u S3dNOISl1 H US H z 1 X SOdWOD -II VLN3WWODG INIOd99. ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## ID-ZOsH H lt64H HN {UI | 10-9 Toq ID-Z08f ú HH HHH Hl it? 1l041-9lD- / IO-Z 6L1 Il HH it H {11! :: - 3-DQD 10-9 ID- v ID-Z8Lú

  -J, H H H H ZH00H3 - ID-9 10-ID-Z LLu

  ## STR1 ## ## STR1 ## ## STR2 ## ## STR1 ## ## STR1 ## where ## STR1 ## > I (414ODV co NII O c ~ l. - ___3 JI |! L H11 HI i I * -4 D1> -91 DI> -Z68E IH HHHHHHHHHHHHHHHHHHHQH D1 [-910-ID-ZL8E HL HHH 41U1339j # 109 1D-ZggE JH 11 Il1 | HR3 - %% Io 13-9 10-9 10-98E JH 11 HH% 43-% 4 109 I: 3 ##################################################################################### EXAMPLE 4 ## EQU1 ## where: ## STR1 ##, ## STR1 ##, ## STR2 ## [IV3rIEJVJ TABLEAU T (continued)

ND R3 R R5 R6 DCOMPOSMENTAL-

X Z, z

COMPOUND 2I FUSIONERS

  397 2-CI4-Cl6-CICH2 HH he H Tri 398 2-Cl4-Cl6-ClO2H-HHHH Tr '401 2-Cl4-Cl6-Cla * -CF2EH HHHH Tr 400 2-Cl4-Cl6-Clc2 CH2pr HHH II Tr. 401 2-Cl-Cl-Cl-CHCl 3 CHCl 3 -Cl 4 Cl 6 ClCl 2 CH 2 Cl 2 HCl

tI ..........

  403 2-CI! ## STR2 ## H H H Tr 399; 2-el 4-el Z-c. ## STR1 ## ## STR1 ## where: ## STR2 ## where: ## STR1 ## Hi.ku: 3IL'i 1> - 9 lt 'ID-Z Ot IL - H tl tl HH :: El 33t1,4D = 13> 9 I3-t / 1-Z 90q inn H1 * 1 AIr3 ID-9 1D ## EQU1 ##

I to '.

H tt: = U t3-910-v a / O

33 0

  ! lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

  S3IV.L1-- NOISf- I 3S0dWO I -N3NWOD QJ.NIOd 2 ZAX t (a4IH oo - o - i ALHH H tJ J3 1> 913t-10-ri é H Hl H H H 4 14l31z3-9ID-iîo-r917 - ULH HH uH: 4S ID0-9 ID-, ID-, | HHH Hl ua ZilT: 3.1> -9 I: - 1I-Z | 9LHH 0HHH H3 Z'O10-9 la-1 ## STR2 ## wherein -9 ', lu-v luz; SSHNOISfln. [{{SOdWOD -IVl.N3WWOD G.LNIOdv9ON H 1 / ú1 1 (onTns) [nlvqHvi TABLE I (continued)

  N "OF X Y Z R1 R2 R3 R4 AR RI A POINT DECOMMEN

FUSION TAIRES COMPOUND

  Z 418 2-C1 4-Cl 6-Cl 2-Cl 4-Cl 6-CClC e2t CH 2 -CH = CH 2 H H H! ## STR2 ## H MeI H Tr oil 422 2-Cl 4-Ci H BU 'II 422 2-CI 4-Cl H t I e H m He Tr 423 4-Cl He H tBu H II H Me H Tr IL6,5-11PC 424 2-CI 11 HHHH I Me Tr oil 1; 425 2-CI IH rd bed it e tIl Tr 426 2-FIHH IH It | t solid matter oo TABLFAU T (cont.)

  I NO OF X Y l Z | R1 R2 U3 R4 R5! RI Az POINT OF COMMEN-

  COMPOUND X y Z R1 RI R R4 R R6>, FUSION TAIRES

t 1 - - -

I.

427 4- D - H I 557 "

  432 2-Cl 4-F H. ti u H! ## STR1 ## wherein: ## STR1 ## wherein ## STR2 ## ## STR2 ## ## STR4 ## ## STR2 ## ## STR2 ## 4-1 HH HH H H H H H H O U O CO TABLE I (cont.) No. OF I 2 ii, POINT OF COMMAND _ COMPOS EYZ R1 R2 R3 R4 R 6 Az FUSION TAIRES ....... i 436 4-Pfl HH tBu 1 I H H M H Tr 437 2-Cl 4-C1 I t IU H Me I I Tr 438 2-C1 HH! tlJ i I i H M H Tr 439 2-Cl 4 -Cl t Bu H H H Me Tr Y 440 2-CI HH tH I Hi HM Me Tr 441 2-CI 4-Cl Hl nalij Hl HH Me IJ Tr n 442 2-CI I 11 ## EQU1 ## ## STR1 ## 11 IHH 'ku HH 1-ti OV H He 1 HH JIu H 1l 1D-i 6t1 vo' J. H1 4 HH Hl Wi HH IDZi j 989

lI _D-.

II-

## EQU1 ##

  3). LNIOdI 9 flC oN (a-4 [ns) I IVa'IUVL - IH !! - Il Xot H! DX 3

IH I

  S.HIVJNOISflAH I: z 3SOdWOD 1-NaNWOD SUl úNIOdnc] oN

  TABLE II: RESONANCE CHARACTERISTICS

MAGNETIC PROTONS

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

N COMPOUND

  IE 6 88120 (1H, s), 7.92 (1H, s), 7.41 (2H, m, 7.20 (1H, m), 4.38 (1H, d, J = 112Hz), 4.29 (1H, d, J 12Hz), 3.39

(3H, s), 3.11 (2H, s), 1.80 (3H, s).

  L 48.14 (1H, s), 7.85 (iH, s), 7/38 (H, m), 7.34 (1H, mr), 7.13 (1H, m), 4, 32 (1H, d, J 12Hz), 4.24 (1H, d, J 12Hz), 3; 32 (3H, s), 3.04 (2H, s), 2> 09 (2H, q, J 7Hz) ), 0.99 (3H, t, J 7Hz).

N COMPOUND

  8.08 (1H, s), 7.93 (1H, s), 7.36 (2H, m), 7.21 (1H, m), 5.46 (2H, m), 4.28 (1H, m.p. , d, J 13Hz), 4.18 (1H, d, J 13Hz), 3.45 (1H, s), 3.00 (2H, m),

1756 (3H, d, J 7Hz).

  8H05 (iH, 1 s), 7.81 (1H, 1 s), 7.30 (2H, m), 7.10 (1H, m), 5.43 (iH, dd, J and 7Hz), 5.33 (1H, d, J Hz), 2.96 (1H, d, 12Hz), 2t89 (1H, d, 12Hz), 2.88 (1H, s), 1> 83 12H , Ln upiet, J 7H-), 0.75 (3H, t,

J 7Hz ,.

  8.21 (1H, s), 7.91 (1He, s), 7/48 (1H, m), 7.38 (1H, m), 7.22 (2H, mr), 4.39 (1H, m.p. d, J 13Hz), 4.29 (1H, d, J 13Hz), 3.40 (3H, s); 3.19 (2H, m),

1.79 (3H, s).

  74δt21 (1H, s), 7t90 (11H, s), 7.49 (1H, m), 7.37 (1H, M), 7.21 (2H, m), 4.39 (1H, d, J 13Hz), 4.30 (1H, d, J 13Hz), 3.41 (3H, s), 3.18 (2H, s), 2.14 (2H, q, J 7Hz), 1.05 ( 3H, t, J 7Hz). (zHL! 'HE) 16'0' (ZHL ú -'aidn: utnb 'HZ) TO' Z '(W' HZ) O l 'Hú) Zú'ú l (ZHEI' P'HI) VZ ' '(ZHúl r' P'HT) tCt '(ZH9I r' P 'HI) 91'S' (U'HI) zsE '' (W'HZ) IZ / L '(' HZ) Where / L (SI 'Hl) 68'L '(s I' HT) LT'8 SOI (ZHL r 'the HE) úE80' (O'HZ) 68'ti '(ZHZI

P'HT) ZO'ú '(ZHZTI' P'HI) OTEú

  (s T 'H4T) 6E'u' (ZHUT 'P'HQ) OZ0' '(ZHEI T' P'HI) TU'E '(u'H1) The S' ('HZ) O?' L '(u HZ) 8E L (s 1 'H) t6L (s <rT' Hl) 1'8 EOT

L9'1 '(ZHú1' P'HT) 90'E '(ZHUI

  I 'P'HI) STU' (s'HE) ZE 'E' (ZHEI r 'P'H) T' '(ZHEI r' P'HT) 9''E '(ZH91 r' P 'HT) 6t' 5 '(W'HI) S'5 "' HU'Z) Z'L '(r'HZ) O [t' ('I' HI) 16L '(Si' il) 8e89 L8 * ZHL r 'P' Hú) 951 '(UI'HZ) SO <f (SI' HI) ZEfE '(ZH AND r' P'HI) 6T'b '(ZHETI' P'HT). * ÚlT '(J'HZ)

0O '(9'H) OZ' '(' HZ) 8EL

  (s T 'Hl) Z6tL' (5 1 'HT) Zt'9 G8 3SOdwOD faoN EL! Compound No. 128: 8.20 (1H, s), 7594 (1H, s), 7.28 (4H, m), 4.30 (1H, d, J 12HZ), 4.20 (1H, d, J 12Hz), 3.39 (3H, s), 2.87

(2H, s), 1.82 (3H, s).

  8.18 (1H, s, 7.94 (1H, s), 7t28 (4H, m), 430 (2H, rm), 3- (69H, 1H), 2.94 (2H, m.p. m), 2> 09 (2H, q, J 7Hz),

1.03 (3H, t, 7Hz).

  ! 13A, 48; 19 (! H, s), 7.93 (! H, s), 7.29 (4H, m), 4> 3 (H ,, J 13Hz), 4.21H, d, 13Hz -3.9 (3H, s), 2e21 (2H, q, J 7Hz), 1.09 (3H, t, 37Hz) | 47d 8.13 (1H, s), 7192 (1H, s), 7.27 (4H, m), 5.54 (H, m), 5.17 (! H, d, J 16Hz), 4.20 (1H, d, J 13Hz), 4.10 (! H, d, J 13Hz), 3.31 (3H, s), 2.95 (1H, d, J 13Hz), 2.76H (1H, d, J).

13Hz), 1170 (3H, d, J 7Hz).

  153 8.16 (1H, s), 7; 93 (1H, s), 7.25 (4H, m), 5.88 (1H, m), 5.56 (1H, m), 21 (3H); , m), 4.23 (2H, m), 4.01 (2H, m), 2.95 (1H, d, J 12Hz), 2.80 (1H, d, J 12Hz), 1.70 (m.p. 3H, d, J 7Hz).

N COMPOUND

  163 8.09 (1H, s), 7; 92 (1H, s), 7.27 (2H, m), 7.14 (2H, m), 5.50 (1H, m), 34 (1H, m.p. , d, J-16Hz), 4.19 (2H, m), 3.15 (1H, s), 2.86 (1H, d, J 12Hz), 2> 73 (1H, d, J 12Hz), 1.92 (2H,

  quintuplet, J 7 Hz), 0.84 (3H, t, J 7 Hz).

  8.13 (11H, s), 7.91 (1H, s), 7.28 (2H, m), 7.20 (2H, m), 5.56 (1H, m), 5117 (1H, d), , J 16Hz), 4.22 (1H, d, J 12Hz), 4.15 (1H, d, J 12Hz), 3.31 (3H, s), 2.96 (1H, d, J 12Ez), 2779 ( 1H, d, J 12Hz), 2.04 (2H, m), 0.93

(3H, t, J 7Hz).

  8.21 (1H, s), 7.99 (1H, s), 7r54 (1H, m), 7 (14 (1H, m), 6.98 (1H, m), 4.33 (2H, m.p. m), 3.28 (1H, d, J 12Hz), 3.14 (1H, d, J 12Hz), 2.08 (2H, q, J)

7Hz), 1.00 (3H, t, J 7Hz).

  8.24 and 8.22 (1H, 2xs), 799 and 7196 (1H, 2xs), 7.45 (2H, m), 714 (1H, m), 6.99 (1H, m), , 49 (2H R1 represents CH = CHCH2CH3, m), 4,4C-4, O0 3. 23 (2H, m), 3.00 (2H, m), 1, .92. (2H R represents C = CHCH2CH3 , quintuplet, J 7 Hz), 1.45-1.25 (6H R1 represents nBu, m), 0.91 and 0.85 (3H, 2xt, J 7Hz)

N COMPOUND

  42i 8.15 (1H, s), 7.91 (1H, s), 7.81 (1H, m), 7; 36 (1H, m), 7.19 (1H, m), 4; 48 (1H, q, J 7Hz), 4.29 (1H, s), 3.43 (1H, d, J 13Hz), 3.17 (1H, d, J 13Hz), 1.71 (3H, d , J 7Hz), 1.91 (9H, s). 424 Diastereol-major sorb 8.15 (1H, s), 7.88 (1H, s), 780 (1H, m), 7j34 (1H, m), 7.18 (2H, m), 4.54 ( 1H, q, J 7Hz), 4t16 (1H, s), 3.45 (1H, d, J 13Hz), 3.23 (1H, d, J 13Hz), 1; 72 (3H, d, J 7Hz) , 0 ,. 92 (9H, s). Diastereoison: secondary re 7.96 (1H, s), 7.80 (1H, m), 7.63 (1H, s), 7.40-7.00 (3H, m), 4.79 ( 1H, s), 4t66 (1H, q, J 7Hz), 3, 35 (1H, d, J 13Hz), 3.05 (1H, d, J 13Hz),

1; 81 (3H, d, J 7Hz), 1.11 (9H, s).

  426 Primary diastereoisor 8,17 (1H, s), 7.90 (1H, s), 7.57 (1H, m), 7, 25-6.80 (3H, m), 4.50

(1H, q, J 7Hz), 3.86 (1H, s), 3f34.

  (1H, d, J 12Hz), 310q (1H, d, J 12Hz),

1168 (3H, d, J 7Hz) and 0.89 (9H, s).

  (s'H6) 1 tO '(ZHL P'HE) 9t I' (ZHEIT 'P'HI) LO'E (ZHETI' P'HT) OEútú '(s'Hú) 691E (S'HI) 86rE' ( ZHL r 'b'HI) 9't', (U '') OL19 '(uI'HI) Z8'9' ('"' HI) Z9tL '(S'HI) TS'tL' (s'HI) ## EQU1 ## where: ## STR2 ## wherein: ## STR5 ## (ZHL r 'b'Hi) 8t (W'HT),' 6t9 '(' HT) 60 L '(U''HI)

Z8'L '(S'HT) 689L' (S'HI) ST'8 0ºE

  (S'H6) 01It '(ZHL r' P'Hú) 6LtI (ZHZI r 'P'HT) T6 Z' (ZHZTI 'P'HTI) 0oúE' (s'Hi) úEZt '(ZHL r' b'HI) ) 594t '(W:' Hú) 08 J9-SZ The (u1'HI) LstL '(S'HI) Z9'L' (s'HRT) 6'L aat! Puosas a; auIosToga2z9seiC! {(aTns) 9E ESOdWOD) nG LL Compounds of the general formula (I):

X R3 OR2 R5

\ g \ II I

_C C C C AZ

<y / I I I

Y | R4 R1 R6

Z (I :)

  in which Az, R 1 to R 6, X, Y and Z are as defined above, except that R 2 is not hydrogen, can be prepared from compounds of general formula (IV) [compounds of formula (I in which R2 is hydrogen]:

X P3 OH R5

Q c c C Az R6

Z (TV)

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

  in a suitable solvent such as tetrahydrofuran.

  Compounds of the general formula (IV) wherein R 1 is a group of the general formula (III) wherein R 8 and R 9 or R 8 and R 10 are hydrogen may be prepared by reduction of compounds of the general formula (V) general formula (IV) wherein R1 is a group of general formula (II): x R3 CH R5 QO CC Az yi

/ Re C R6

i

  o Az, R3 to R7, X, Y and Z are as defined above.

  In the cases where R8 and R9 are both hydrogen (trans double bond), this can be achieved by using an aluminum hydride reducing agent such as sodium hydride-bis (2-methoxyethoxy) aluminum. or lithium aluminum hydride in a suitable solvent such as tetrahydrofuran. In the cases where R8 and R10 are both hydrogen (cis double bond), this can be achieved by catalytic hydrogenation over a suitable catalyst such as palladium on

barium sulfate.

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

R '0 Eé

x 1 N o e ffi _ICAz

Y R. R6

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

M C X C R7 (VII)

  in which R7 is as defined above and M represents a metal such as lithium, magnesium or titanium,

  or M can be silicon, in the presence of a catalyst

  appropriate type of fluoride.

  Alternatively, compounds of the general formula (IV) in which R 1 is a group of the general formula (III) can be prepared by treating compounds of the general formula (VI) with compounds of the general formula

(VIII):

R9

/ C - C (VIII)

  wherein R8 to R10 are as defined above and M is magnesium (Grignard reagent) or lithium, in

  a suitable solvent such as tetrahydrofuran.

  Compounds of general formula (IV) in

  which R 1 is an alkyl group (and R 5 is not hydro-

  gene) can be prepared by treating compounds of general formula (VI) with compounds of general formula R1M wherein R1 is as defined above and M is

  a metal such as lithium or magnesium.

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

R3 0 R5

X i 1 11 t C C C Hal (IX)

Y 1

  Wherein R 1, R 3 to R 6, 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 (IX) with compounds of the general formula (VII) in which M is lithium, magnesium or titanium and by carrying out then a treatment with a

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

  As another variant, it is possible to prepare compounds of general formula (IV) in which R 1 is a group of general formula (III) by treatment of compounds of general formula (IX) with a compound of general formula (VIII) in which M is lithium or magnesium, followed by treatment with an azole (imidazole

or 1,2,4-triazole).

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

X R3 OH R5

0 C - C - C Hal (X)

Y I I I

  wherein R 1, R 3 to R 6, X, Y and Z are as defined above, with a suitable oxidizing agent such as

Jones's reagent.

  Compounds of general formula (X) in which R5 and R6 represent hydrogen may be prepared by treatment of compounds of general formula (XI):

X R3 H

in _- C __ C (XI)

Y - 4 \

R4 H

H

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

  above, with a solution of the appropriate halogen, by

bromine, in water.

  Compounds of general formula (XI) in which R 3 and R 4 are hydrogen may be prepared by treatment of Grignard reagents of general formula x (XII) mc M ar (XII) y

  wherein Hal, X, Y, and Z are as defined above.

  above, with allyl bromide, optionally - in the presence of a copper (I) catalyst, in a solvent

  suitable such as diethyl ether.

  Compounds of the general formula (XII) can

  be prepared by methods indicated in the literature.

  ture. Alternatively, compounds of general formula (IX) can be prepared by treatment of Grignard reagents of general formula (XIII): ## STR1 ## wherein Hal, R3, R4, X, Y and Z are as defined above, with an acid chloride of general formula

(XIV):

RI CI C C - Hal (XIV) 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 formulas (XIII) and (XIV) can be prepared by methods described in

Literature.

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

X R3 OH R

o__ 0CC _ _ (X) y I i

R4 H R6

  in which Az, R3 to R6, X, Y and Z are as defined above. A suitable oxidation process is the variant

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

  foxide, oxalyl chloride and triethylaminin in the

  dichloromethane), or the oxidation of Moffat (dimethyl

  foxide, acetic anhydride and triethylamine in the

  dichloromethane), or the use of Jones's reagent.

  Compounds of general formula (XV) in which R5 and R6 are hydrogen may be prepared by treatment of an epoxide of general formula (XVI):

R3 0 H

X c-c c (XVI) y 4

1 4.H H

z

  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 (XVI) may be prepared by epoxidation of compounds of general formula (XI) with a suitable peracid such as

  peracetic acid or m-chloroperbenzoic acid.

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

X R3 0 R5

X _ c (XVII) y | R4 R1

Z R1

  in which R 1, R 3, R 5, X, Y and Z are as defined above, with an azole (imidazole or 1,2,4-triazole) in

  a suitable solvent such as ethanol.

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

R3 0

  wherein R1, R3, R4, X, Y and Z are as defined above, with a sulfide ylide of the general formula

(XIX):

R2S-CHR 5

  (XIX) wherein R5 is as defined above and R is methyl if R5 is hydrogen, or R is phenyl if R5 is not hydrogen, in a suitable solvent such as dimethylsulfoxide. Sulphide ylides of general formula (XIX) can be prepared

  by procedures described in the literature.

  Compounds of general formula (XVIII) in which R 1 is a group of general formula (II) can

  be prepared by methods described in the literature.

  For example, it is possible by treatment of the compounds of general formula (XX):

X3 '

Q Rl 4 (XX) z 4

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

  above, with a compound of the general formula (VII) wherein R2 is such that defined above and M is copper- (I) or M is a trialkyltin or hydrogen in the presence of a palladium catalyst. Alternatively, compounds of the general formula (XVIII) wherein R 1 is a group of the general formula (II) can be prepared by treating compounds of the general formula (XXI):

R3 0

(XXI)

IOC C H (XXI R4 z

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

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

chromium.

  In another variant, compounds of the general formula (XVIII) in which R 1 is a group of the general formula (II) can be prepared by treating a compound of the general formula (XXII):

X (XXII)

O, C C NR2 Y R4

  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.

  Compounds of the general formula (XVIII) wherein R 1 is a group of the general formula (III) can be prepared by methods described in the literature. For example, it is possible to work by treating compounds of general formula (XX) with compounds of general formula (VII) in which M is copper (I) or manganese (I) or tributyltin or magnesium in the presence of a palladium catalyst in a suitable solvent such as

tetrahydrofuran.

  Alternatively, compounds of the general formula (XVIII) in which R 1 is a group of the general formula (III) can be prepared by treatment of compounds of the general formula (XXII) or of the general formula (XXIII): x R 3 0 N. OH (XXIII) OH R4

than ether.

  According to another variant, it is possible to prepare compounds of general formula (XVIII) in which R 1 is a group of general formula (III) by treatment of compounds of general formula (XXI) with compounds of general formula (VIII) in which R is lithium or magnesium, followed by oxidation with a suitable oxidizing agent such as chromium trioxide or manganese dioxide. As another variant, it is possible to prepare

263'4482

  compounds of general formula (XVIII) wherein R1 is a group of general formula (III) and R10 is not hydrogen by treatment of a compound of general formula (XXI) with compounds of general formula (XXIV): H R9 RI t CC MgCal (XXIV) C === C - C Mg Hal

I 1I

R8 H

  in which Hal, R8 and R9 are as defined above and R11CH2 = R10, followed by oxidation with a suitable oxidizing agent such as chromium trioxide and then a

  acid catalyzed transposition.

  As another variant, it is possible to prepare compounds of general formula (XVIII) in which R 1 is a group of general formula (III) by treatment of a compound of general formula (XX) with a compound of formula

  (VIII) in which M is a trialkyl-

  silyl (for example trimethylsilyl) in the presence of an acid

  of suitable Lewis such as aluminum trichloride.

  According to another variant, it is possible to prepare compounds of general formula (XVIII) 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 ( XVIII) in which R 1 is a group of general formula (II). In cases where R8 and R9 are hydrogen (trans double bond), a suitable reducing agent is lithium or sodium in liquid ammonia. In cases where R 8 and R 10 are hydrogen (cis double bond), a suitable reducing agent is hydrogen over a suitable catalyst, for example palladium on barium sulfate. Alternatively, 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. Compounds of general formula (XVIII) wherein R 1 is an alkyl group may be prepared by methods described in the literature. For example, it is possible to treat compounds of general formula (XX) with compounds of general formula R 1 M in which R 1 is as defined above and M is copper (I) or M is magnesium (at low temperature). temperature)

  in a suitable solvent such as tetrahydrofuran.

  Alternatively, compounds of the general formula (XVIII) in which R 1 is alkyl can be prepared by treating compounds of the general formula (XXI) with compounds of the general formula R 1 M wherein R 1 is as defined above and M is lithium or magnesium, followed by oxidation with an oxidizing agent

  suitable such as chromium trioxide.

  According to another variant, it is possible to prepare compounds of general formula (XVIII) in which R 1 is an alkyl group by treatment of compounds of general formula (XXII) or of general formula (XXIII) with compounds of general formula R 1 M in which R 1 is as defined above and M is lithium, in a solvent

suitable such as ether.

  According to another variant, it is possible to prepare compounds of general formula (XVII) in which R 1 is an appropriate alkyl group by hydrogenation of compounds of general formula (XVIII) in which R 1 is a group of general formula (II) or a group of general formula

(III).

  As another variant, it is possible to prepare compounds of general formula (VIII) in which R 1 is an alkyl group by treatment of compounds of general formula (XXV): 9.0 CI-R

C1- C R1

  (XXV) wherein R 1 is as defined above, with compounds of general formula (XIII), optionally in the presence of a copper (I) catalyst in a suitable solvent such as ether. As another variant, compounds of general formula (XVIII) in which R 1 is an alkyl group can be prepared by treatment of compounds of general formula (XXVI): ## STR2 ## in which R 1 is as defined above, with compounds of general formula (XIII) or compounds of general formula (XXVII) X Rd

C (XXVII).

R4

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

  above, in a suitable solvent such as diethyl ether, followed by oxidation with oxidizing agents

  suitable such as chromium trioxide.

  As another variant, it is possible to prepare compounds of general formula (XVIII) in which R 1 is an alkyl group by treatment of compounds of general formula (XXVIII):

HO - R (XXVIII)

  wherein R 1 is as defined above, or compounds of general formula (XXIX): wherein R 1 and NR 2 are as defined herein; above (for example NR2 is a NMeOMe group), with compounds of general formula (XXVII) in a suitable solvent such

than diethyl ether.

  Compounds of general formula (XX), (XXI),

  (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XXVIII)

  and (XXIX) can be prepared by methods described

in the litterature.

  As another variant, compounds of general formula (IV) can be prepared by treating compounds of general formula (XXX):

GOLD

  _ _ _ _ _ _ _ 1__ _ _ _ _ _ _ c _ _ _ _ _ _ _ _ (X X X) 2- c C. AZ i D

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

  above, with a Grignard reagent of formula (XIII) in

  a suitable solvent such as diethyl ether.

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

3 R5

___l _I (XXXI) R1 --- C '-Hal R6

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

  above, with an azole (imidazole or 1,2,4-triazole) in the presence of a suitable base such as hydride of

  potassium, in a suitable solvent such as dimethyl

  formamide. Compounds of general formula (XXXI) in which R 1 is an alkyl group can be prepared by treating compounds of general formula (XIV) with compounds of general formula R 1 M wherein R 1 is as defined above (alkyl group) and M is copper- (I) or M is magnesium (at low temperature) in a solvent

  suitable such as tetrahydrofuran.

  Alternatively, when R 1 is a tertiary alkyl group (for example tert-butyl), compounds of general formula (XXXI) can be prepared by treating compounds of general formula (XXXII):

0 R5

R (XXXII)

R.L.H

  Wherein R1, R5 and R6 are as defined above, with a suitable halogen (such as chlorine or bromine)

as described in the literature.

  Compounds of general formula (XXXII) can be prepared by methods described in the literature. As another variant, it is possible to prepare compounds of general formula (IV) in which R 3 and R 4 are hydrogen by treatment of compounds of general formula

0 R5

H2 -: C hz (XXXIII) C --Az I

Ri 6.

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

  top, with a Grignard reagent of general formula

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

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

  general (XXX) with the sulfurized ylide of formula Me2S + CH2-.

  The compounds, their salts and their metal complexes are active fungicides, particularly against the pathogenic agents Puccinia recondita, Puccinia striiforis and other wheat-attacking rusts, Puccinia hordei, Puccinia striiformis and other rusts attacking barley, and attacking rusts. other hosts, eg coffee, apple, vegetables and ornamentals, Erysiphe graminis (white) attacking barley and wheat and other whites growing on

  various hosts such as Sphaerotheca fuliginea on cucur-

  bitaceae (eg cucumber), Podosphaera leucotricha growing on the apple tree and Uncinula necator

  on the vine, species of the genus Helmn -.-

  thosporium spp., Pvrenophora teres, Pseudocercospurella herpotrichoides, RhvnchosDorium spp., Septoria spp. and Phizoctonia spp., for example R. cerealis, Cercospora arachidicola developing on peanut and other species of the genus Cercospora developing for example on sugar beet, bananas and soya, Venturia

  inaecqua> lily (scab) developing on apples.

  Some of the compounds also showed a strong field of activity against fungi in vitro. is

  activity against various diseases develop-

  on fruits after harvest (eg Penicill

  lium diacatum and italicum on oranges, Gloeosporium

  musaru on bananas and Botrytis cinerea on grapes}.

  Some other compounds are active for seed disinfection against: Fusarium spp., Sentoria spp. Tilletia spp. (ie, decay, seed-borne wheat disease), Ustilago spp. and Helminthosporium spp. himself

developing on cereals.

  The compounds can move in the acropetal direction in the plant tissue. In addition, the compounds can be sufficiently volatile to be vapor phase active against fungi growing on plants. They can also be useful as fungicides

  (as opposed to fungicides for agriculture).

  ture), for example to prevent a fungal attack

  wood, skins, leather and especially paint films.

  The compounds of the invention also possess

  a pharmaceutical activity as aromatase inhibitors.

  Aromatase is an enzyme that aromatizes the A-ring in the metabolic formation of various steroid hormones. Some tumors are dependent, for their persistence or growth, on circulating steroids containing an aromatic ring A, and a chemical agent which inhibits the aromatization of the nucleus A in the precursors of these steroids is likely to be effective in inhibiting the growth of these tumors to

hormonal dependence.

  The compounds can be used as such for fungicidal purposes, but they are advantageously 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 complex of this compound; and optionally, a support

or diluent.

  The invention also proposes a method for combating fungi, which consists in applying to a plant, to its seeds or to the place where the plant or the seed is located, a compound, a salt or a complex of this compound,

as defined above. -

  The compounds and their complexes and salts can be applied in a variety of 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 shrubs. trees, seeds or other medium in which plants, shrubs or trees grow or are to be planted, or they may be applied by spraying, dusting or in a form formulated into cream or paste, or we can apply them

  in the vapor state: or in slow release granules.

  Application can be made to 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,

  paddy water or hydroponics systems

  than. The compounds of the invention can also be injected into plants or trees or they can

  also be sprayed on the plant

  t: ion using electrodynamic techniques of

2C spray.

  The term "plant" used in this

  memory covers ponds, shrubs and trees.

  In addition, the fungicidal method of the invention includes a treatment for prevention, protection, prophylaxis and

eradication.

  Compounds are advantageously used in agriculture and horticulture in the form of a composition. The type of composition that is used in

  each case depends on the particular goal sought.

  The compositions may be in the form of

  powder for powders or granules

  an active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and kaolinite. These granules can be preformed granules that can be applied to the ground without further treatment. They can be prepared either by impregnating filler pellets with the active ingredient or by granulating a mixture of the active ingredient and the filler powder. Seed disinfection compositions, for example, may include an agent (eg mineral oil) to promote 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-methyl-

  pyrrolidone or dimethylformamide).

  The compositions can also be under

  form of powders, granules or dispersible grains

  taking 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 dissolving the ingredient or.

  active ingredients in an organic solvent optionally containing one or more wetting, dispersing or emulsifying agents, then adding 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, methyl naphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like. glycol ethers (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 dry with a pyrotechnic mixture to form a composition which is suitable for generating in a closed space a smoke containing the compounds. Alternatively, the compounds can be used in the microencapsulated form. They can also be formulas in biodegradable polymeric formulations for

  obtain a slow controlled release of the active substance.

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

  be better suited to different applications.

  The compounds can be used in mixtures with fertilizers (eg fertilizers containing nitrogen, potassium or phosphorus). It is preferred compositions containing only granules of fertilizers containing the compound, for example coated with compound 2C. These granules advantageously contain up to 1% by weight of the compound. The invention also proposes a fertilizer composition comprising the compound of general formula (I), a salt or a metal complex of

this compound.

  The compositions may also be in the form of liquid preparations for use in baths or sprays, which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants. for example one or more wetting agents, dispersants, emulsifiers or suspending agents; or which are sprayable formulations of the type that one can

  use in electro-spraying techniques

  nomic. The agents mentioned above may be cationic, anionic or nonionic agents. Suitable cationic agents are ammonium compounds

  quaternary, for example cetyltrimethyl bromide

  monium. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulphate) and salts of aromatic sulphonates (for example sodium dodecylbenzenesulphonate, lignosulphonate, sodium butylnaphthalenesulphonate, calcium or ammonium and a mixture of diisopropyl- and

  sodium triisopropylnaphthalenesulfonates).

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

  hydrophilic colloids (for example polyvinylpyrrolidine

  rolidone and sodium salt of carboxymethylcellulose) and vegetable gums (eg gum arabic and gum tragacanth). The compositions for use in aqueous dispersions or emulsions are generally presented in the form of a concentrate containing a high proportion of one or more active ingredients, and the

  concentrate should be diluted with water before use.

  tion. These concentrates must often be able to withstand storage for extended periods of time and after this storage they must be diluted with water to form aqueous preparations which remain homogeneous for long enough for they can be applied using conventional electrodynamic spray equipment. The concentrates may contain up to 95%, preferably 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, because the presence of these acids can increase the solubility of the active ingredient or ingredients in the solvents. often used in concentrates.

  also advantageously a high proportion of surfactants

  active ingredients, which makes it possible to obtain sufficiently stable aqueous emulsions. After dilution to form aqueous preparations, these preparations may contain varying amounts of the ingredient or. active ingredients, according to the intended purpose, but an aqueous preparation containing 0.0005 or 0.01% to 10% by weight of one or

  several active ingredients can be used.

  The compositions of the present invention may also include one or more other compounds having biological activity, for example, compounds having similar or complementary fungicidal activity or compounds influencing plant growth, having herbicidal activity or insecticidal activity. The other fungicidal compound may be for example a compound which is capable of combating diseases of the ears of cereals (for example wheat) such as Septcria,

  Gibberella and Helminthosporium spp., Trans-

  seeds and soil and various forms of white and mildew developing on the vine and white and apple scab, etc. These fungicide mixtures may have a broader spectrum of activity than the compounds of the general formula (I) used alone: in addition, the other fungicide may produce a synergistic effect on the fungicidal activity of the compound of the general formula (I). ). Examples illustrating the other fungicidal compound are carbendazim, benomyl, thiophanatemethyl,

  thiabendazole, fuberidazole, etraidazole, dichloro-

  fluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminum, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, R 0 151 297, pyrazophos, ethirimol, ditalimofos, tridemorph, triforine, nuarimol, triazbutyl, guazatine,

  propiconazole, prochloraz, flutriafol, hexaconazole

  1G le, that is to say 1- (1,2,4-triazol-1-yl) -2- (2,4-

  dichlorophenyl) hexane-2-ol, flusilazole, i.e.

  DPX H6573 or (1 - ((bis-4-fluorophenyl) methylsilyl) methyl) -

  1H-1,2,4-triazole, triadimefon, triadimenol,

  diclobutrazol, terbuconazole, furconazole, cis-

  furconazole, cyproconazole, fenpropimorph,

  fenpropidine, chlorozolinate, diniconazole,

  zilil, fenfuram, carboxin, oxycarboxin, dithianon, methfuroxam, dodemorph, EAS 454, blasticidine S, kasugamycin, edifenphos, kitazine

  P, cycloextrimide, phthalide, probenazole, isopropyl

  thiolane, tricyclazole, pyroquilan, chlorobenzene

  zosterazone, neoasozine, polyoxin D, validamycin

  A, repronil, fluotolanil, pencycuron,

  diclomezine, phenazine oxide, dimethyldithiocar-

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

  biloxazol, quinomethionate, dimethirimol, 1-

  (2-cyano-2-methoxyiminoacetyl) -3-ethylurea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb,

  sulfur, dinocap, binapactryl, nitrothalisopropane

  pyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichlorane, copper-containing compounds such as copper oxychloride, copper sulfate, and

  Bordeaux mixture, and organomercury compounds.

  The compounds of the general formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against fungal diseases transmitted by seeds, by the

  soil, or fungal diseases of the foliage.

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

  fenitrothion, phenothoate, 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 inhibit the

  grasses or ear formation, or that selectively inhibit

  the development of less desirable plants (eg

example of grasses).

  Examples of compounds influencing plant growth that can be used with the compositions of the invention are gibberellins (eg GA3, GA4 or GA7), auxins (eg, acid

  indolacetic acid, indolbutyric acid, naphthoxyacetic acid

  or naphthylacetic acid), cytokinins (eg, kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (eg 2,4-D or MCPA), substituted benzoic acids (eg tri-iodobenzoic acid) ), morphactins (eg chlorflurecol), maleic hydrazide, glyphosate, glyphosine, alcohols and fatty acids

  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, the hydroxybenzenes

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

  fenpentesol, inabenfide, triapenthenol and tec-

nazène.

  The following examples illustrate the invention.

  Temperatures are expressed in degrees centigrade ('C') and reactions involving water-sensitive intermediate compounds have been conducted under atmospheres

anhydrous nitrogen.

EXAMPLE 1

  This example illustrates the preparation of 1- (2,4-

  dichlorophenyl} -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol

(Compound N: 7 of the Table).

  2,4-dichlorobenzyl chloride (20 g ,.

  102 mmol) in anhydrous diethyl ether (20 ml) was added dropwise to a stirred mixture of magnesium turn (2.5 g, 102 mmol) in anhydrous diethyl ether (20 ml). at a chosen speed of

  to maintain a constant reflux. Tetrahydrofuran

  Anhydrous form (40 ml) was then added as diethyl ether was distilled off. The mixture was then cooled to room temperature and added dropwise over 30 minutes to a stirred solution of chloroacetyl chloride (23 g, 204 mmol) in dry tetrahydrofuran (100 mL) at -78 ° C. the mixture warmed to room temperature over one hour and water was added. The mixture was extracted with diethyl ether and the combined extracts were washed with 2 M aqueous sodium hydroxide solution and brine (MgSO 4) and dried (MgSO 4).

evaporated under vacuum.

  Chromatography [SiO2, ethyl acetate-

  hexane (5:95) a (10:90)] gave 1-chloro-3- (2,4-

  dichlorophenyl) acetone (3.5 g, 14%). Mp 62 ° C. 1-Chloro-3- (2,4-dichlorophenyl) acetone (6.0 g, 25 mmol) in acetonitrile (10 ml) was added dropwise to a stirred mixture of 1 ml. 2,4-triazole (3.5 g, 50 mmol) and potassium carbonate (7.0 g, 50 = roles) in anhydrous acetonitrile (40 ml) at 50 ° C. After 4 hours, the mixture was added to water. The mixture was extracted with ethyl acetate and the combined extracts were washed with brine (until neutral), dried (MgSO 4)

  and evaporated under vacuum. By trituration (isopropyl alcohol)

  and hexane), 1- (1,2,4-triazolyl) -3- (2,4-

  dichlorophenyl) acetone (3.5 g, 52%), mp 110 C.

  N-Butyllithium (3 ml of 1.55 Y solution in hexene, 4.6 moles) was slowly added to a stirred solution of propyne (0.18 g, 4.6 mmol) in anhydrous tetrahydrofuran (m.p. ) at -78'C. After minutes, chlorotitanium tri-isopropoxide (5.1 milliliters of 1.0 M solution in hexane, 1 mmol) was added dropwise. After 20 minutes, we added drop to

  drop of 1- (2,2,4-triazolyl) -3- (2,4-dichlorophenyl) -

  acetone (1.0 g, 4.0 mmol) in dry tetrahydrofuran (20 ml) and the mixture was allowed to warm to room temperature and poured into a saturated aqueous ammonium chloride solution. The resulting mixture was filtered and the precipitate was washed with water and ethyl acetate. The filtrate was washed with water and brine, dried (MgSO4) and evaporated in vacuo. It was obtained by chromatography (SiO2, acetate

  of ethyl) 1- (2,4-dichlorophenyl) -1-2- (1,2,4-triazolyl) methyl

  ethylpent-3-yn-2-ol (Compound No. 7 of Table I) (0.21 g,

17%) melting at 110-113 ° C.

EXAMPLE 2

  This example illustrates the preparation of 1- (4-

  chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-yn-2-ol (Compound N 127 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. The mixture was extracted with diethyl ether and the combined extracts were washed with 2 M aqueous sodium hydroxide solution and brine (MgSO 4) and dried (MgSO 4).

  evaporated under vacuum. By chromatography [SiO 2, hexane

  ethyl acetate (95: 5)], 1-chloro-3- (4-

  chlorophenyl) acetone (16.8 g, 40%) melting at 47-49 ° C. 1-Chloro-3 (4-chlorophenyl) acetone (6.0 g, 30 mmol) in acetonitrile (5 ml). was added dropwise to a stirred mixture of 1,2,4-triazole (4.2 g, 60 mmol) and potassium carbonate 3d (8.8 g, 60 mmol) in dry acetonitrile (50 ml) After 3.5 hours, the mixture was cooled and filtered, the filtrate was poured into water and the mixture was extracted with ethyl acetate and the combined extracts were washed with water. salt solution (until neutral), dehydrated (MgSO4) and evaporated under vacuum.

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  chromatography [SiO2, ethyl acetate-hexane (50:50)

  (100: 0)], 1- (1,2,4-triazolyl) -3- (4-chloro) was obtained.

phenyl) acetone (3.23 g, 46%).

  N-Butyllithium (24 ml) of a 2.4 M solution in hexane, 60 mmol) was added dropwise to propyl (2.4 g, 60 mmol) in anhydrous tetrahydrofuran (100 ml). at -78 ° C under nitrogen. After 30 minutes,

  chlorotriary triisopropylate was added dropwise.

  tane (67 ml of 1.0 M solution in hexane, 67 mmol). the

  After 20 minutes, we added drop by drop

  (1,2,4-triazolyl) -3- (4-chlorophenyl) acetone (10.75 g, mmol) in dry tetrahydrofuran (200 mL). The mixture was allowed to warm to room temperature and then poured into a saturated aqueous solution of ammonium chloride. The mixture was filtered and the precipitate was washed with water and ethyl acetate. The filtrate was separated and the organic fraction was washed with brine, dried (MgSO4) and evaporated in vacuo. It was obtained by chromatography [SiO 2, acetate

  of ethyl-hexane (50:50)] 1- (4-chlorophenyl) -2- (1,2,4-

  triazolyl) methylpent-3-yn-2-ol (Compound N 127

  Table I) (5.25 g, 41%) melting at 99.5-101.5 C.

EXAMPLE 3

  This example illustrates the preparation of 1- (4-

  chlorophenyl) -2-methoxy-2- (1,2,4-triazolyl) methylpent-3-yne

(Compound N 128 of Table I).

  1- (4-Chlorophenyl) -2- (1,2,4-triazolyl) methyl

  ethylpent-3-yn-2-ol (1.0 g, 3.63 mmol) in tetrahydryl

  Anhydrous drofuran (12 ml) was added dropwise to a stirred suspension of hexane-washed sodium hydride (0.17 g of 55% dispersion in oil, 3.9 mmol) in tetrahydrofuran. (12 ml). After minutes, iodomethane (1.1 g, 7.75 mmol) was added dropwise. After 2.5 hours, the mixture was poured into water and the resulting mixture was extracted with ethyl acetate. The combined extracts were washed with brine, dried (MgSO4) and evaporated in vacuo. By chromatography (SiO2, ethyl acetate),

  1- (4-chlorophenyl) -2-methoxy-2- (1,2,4-

  triazolyl) methylpent-3-yne (Compound No. 128 of Table I)

(0.79 g, 75%).

EXAMPLE 4

  This example illustrates the preparation of E-1- (4-

  chlorophenyl) -2- (1,2,4-triazolyl) methylpent-3-en-2-ol

(Compound N 145 of Table I).

  1- (4-Chlorophenyl) -2- (1,2,4-triazolyl) methyl

  3-ethyl-3-yn-2-ol (2.0 g, 7.26 mmol) in tetrahydryl

  Anhydrous drofuran (15 ml) was added dropwise to

  a stirred solution of sodium hydride and bisphenol

  (2-methoxyethoxy) aluminum (8.5 ml of a 3.4 M solution in toluene, 29 mmol) in dry tetrahydrofuran (24 ml) at 0 ° C. under nitrogen. The mixture was allowed to warm to room temperature and after 4.5 hours, cooled to 0.degree. C. and water added carefully. The mixture was extracted with ethyl acetate and the combined extracts were washed with

  salt solution, dried (MgSO4) and evaporated under vacuum.

  By chromatography (SiO 2, ethyl acetate),

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

  2-ol (Compound N 145 of Table I) (1.50 g, 74%). Mp

126.5-117.5 C.

EXAMPLE 5

  This example illustrates the preparation of E-1- (4-

  chlorophenyl) -2-allyloxy-2- (1,2,4-triazolyl) methylpent-3-

  ene (Compound N 153 of Table I).

  1- (4-Chlorophenyl) -2- (1,2,4-triazolyl) -methyl

  3-ethyl-3-en-2-ol (0.56 g, 20 mmol) in tetrahydro-

  anhydrous drofuran (6 ml) was added dropwise to a stirred suspension of hexane washed sodium hydride (0.1 g of a 55% dispersion in oil, 2.3 mmol) in anhydrous tetrahydrofuran (6 ml) under nitrogen. After 20 minutes, allyl bromide (0.49 g, 4.0 mmol) was added and the mixture heated to reflux. After 2 hours, the mixture was cooled and poured into water. The resulting mixture was extracted with ethyl acetate and the combined extracts were washed with brine, dried (MgSO 4) and evaporated.

under vacuum.

  By chromatography (SiO2, ethyl acetate),

  E-1- (4-chlorophenyl) -2-allyloxy-2- (1,2,4-allyloxy) was obtained.

  triazolyl) methylpent-3-ene (Compound N 153 of Table I)

(0.41 g, 64%).

EXAMPLE 6

  This example illustrates the preparation of 1- (2-

  chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-yne

2-ol (Compound No. 193 of Table I).

  2-Chloro-4-fluoro-iodobenzene (50 g, mmol) in anhydrous diethyl ether (100 ml) was added to a stirring mixture of magnesium turn (4.9 g, 200 mmol) in 500 ml. anhydrous diethyl ether (30 ml) at a rate selected to maintain a constant reflux. After refluxing the resulting mixture for a further 45 minutes, allyl bromide (27.2 mL, 200 mmol) was added dropwise at a rate selected to maintain a constant reflux. After maintaining the mixture for a further 30 minutes under reflux, it was poured on ice and 2M hydrochloric acid was added to dissolve the precipitate. The mixture was extracted with ether and the combined extracts were dried (MgSC4) and evaporated in vacuo. Chromatography (SiO 2, hexane) afforded 3 (2-chloro-4-fluorophenyl) prop-1-ene (25 g,

* 74%).

  M-Chloroperoxybenzoic acid (13.3 g, 85%, 89 mmol) was added to a stirred solution of 3- (2-chloro-4-fluorophenyl) prop-1-ene (13.3 g). ,

  78 mmol) in anhydrous dichloromethane (150 ml) & 40 C.

  After 6 hours, the mixture was washed with an aqueous solution of sodium sulphite and then with a 3M aqueous solution of sodium hydroxide. The mixture was then dried (MgSO 4) and evaporated in vacuo to give 1 °. 2-epoxy-3- (2-chloro-4-fluorophenyl) propane

  (12.5 g, 86%) which was used without further purification.

  A stirring mixture of 1,2-epoxy-3- (2-

  chloro-4-fluorophenyl) propane (1 g, 6 mmol), potassium carbonate (0.8 g, 6 mmol) and 1,2,4-triazole (0.5 g, 8 mmol) in Industrial methyl alcohol (10 ml) was refluxed. After 3 hours, the mixture was poured into water and the resulting mixture was extracted with ethyl acetate. The combined extracts were washed (water), dried (MgSO4) and evaporated in vacuo. By chromatography [SiO2, isopropyl alcohol-dichloromethane

  (20:80)], 1- (1,2,4-triazolyl) -3- (2-chloro-4-) was obtained.

  fluorophenyl) propan-2-ol (0.8 g, 52%).

  Jones' reactant (9.6 ml) (J. Chem Soc., 1946, 39) was added dropwise in 45 minutes to a

  stirred solution of 1- (1,2,4-triazolyl) -3- (2-chloro)

  4-fluorophenyl) propan-2-ol (1.1 g, 4.3 mmol) in

  8N sulfuric acid (22 ml) at 15 ° C. After 30 minutes

  The mixture was cooled to 10 ° C. and added with isopropanol (6 ml). 2N sodium hydroxide solution was added to alkalinize the reaction mixture which was then extracted with ethyl acetate (x3). The combined extracts were dehydrated (MgSO4) and evaporated under

  empty giving 1- (1,2,4-triazolyl) -3- (2-chloro-4-

  fluorophenyl) acetone (0.76 g, 70%), m.p.

  N-Butyllithium (1.4 ml of a 2.5 M solution in hexane, 3.5 mmol) was slowly added to a stirred solution of but-1-yne (0.2 g, 3%). 5 mmol) in anhydrous tetrahydrofuran (7 ml) at -78 ° C. After 30 minutes, chlorotitanium triisopropylate (3.8 ml of a 1.0 M solution in hexane, 3.8 mmol) been added drop by drop. After 20 minutes, we added

  dropwise 1- (1,2,4-triazolyl) -3- (2-chloro-4-

  fluorophenyl) acetone (0.76 g, 3 mmol) in anhydrous tetrahydrofuran (7 ml) and the mixture was allowed to warm to room temperature and poured into a saturated aqueous solution of sodium chloride. ammonium. The mixture was filtered and the precipitate was washed with water and ethyl acetate. The filtrate was separated and the organic fractions were washed with water and brine, dried (MgSO4) and evaporated in vacuo. It was obtained by chromatography (SiO2, acetate

  ethyl) 1- (2-chloro-4-fluorophenyl) -2- (1,2,4-trifluoromethyl) -2-

  azolyl) methylhex-3-yn-2-ol (Compound No. 193 of Table I)

(0.088 g, 10%).

EXAMPLE 7

  This example illustrates a variant of

  1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl)

  thylhex-3-yn-2-ol (Compound No. 193 of Table I).

  Ethylmagnesium bromide (3.0 ml of a 3M solution in diethyl ether, 9.0 mmol) was added dropwise to a solution of butylen (0.61 g,

  11 mmol) in anhydrous tetrahydrofuran (14 ml) at 0 ° C.

  After bubbling a complement of but-l-yne in

  the mixture, 1-chloro-3- (2-chloro-4-fluorophenyl) -

  Acetone (1.0 g, 4.5 mmol) in anhydrous tetrahydrofuran (6 ml) was added dropwise and the mixture was stirred at room temperature for 2 hours. Water (about 50 ml) was then added and the resulting mixture was extracted with ethyl acetate. The combined extracts were washed with a salt solution,

  dehydrated (MgSO4) and evaporated under vacuum. By chromatogra-

  [SiO 2, ethyl acetate-hexane (50:50)] gave 1- (2-chloro-4-fluorophenyl) -2-chloromethylhex-3-yn-2-ol.

(1.18 g, 99%).

  1,2,4-Triazole (0.93 g, 14 mmol), 1- (2-

  chloro-4-fluorophenyl) -2-chloromethylhex-3-yn-2-ol (1.18 g), 4.5 mmol) and potassium carbonate (1.25 g, 9 mmol) were added to dimethylformamide (25 ml) and the mixture was heated to reflux. After 3 hours, the mixture was cooled and added to water. The resulting mixture was extracted with ethyl acetate and the combined extracts were washed with water and with a

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

  By chromatography [SiO 2, ethyl acetate],

  1- (2-chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methyl-

  hex-3-yn-2-ol (compound N 193 of Table I) (0.60 g,

43%).

EXAMPLE 8

  This example illustrates the preparation of Z-1- (2-

  chloro-4-fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-ene

  2-ol (Compound No. 224 of Table I;

  The - (2-chloro-4-fluorophenyl) -2- (1,2,4

  triazolyl) methylhex-3-yn-2-ol (0.20 g, 0.65 mmol) and palladium on charcoal (100 mg) in ethanol (2 ml) were hydrogenated at room temperature. After 18 ml of hydrogen had been absorbed, the reaction mixture was filtered (Celite) and evaporated in vacuo.

  giving a mixture of about 80:20 of Z-1- (2-chloro-4-

  fluorophenyl) -2- (1,2,4-triazolyl) methylhex-3-en-2-ol and

  1- (2-chloro-4-fluorophenyl) -2- (i, 2,4-triazolyl) methyl

  hexane-2-ol (Compound N 224 of Table I) (0.061 g, 30%).

Mp 83 C.

EXAMPLE 9

  This example illustrates the preparation of 1- (2-

  chloro-4-fluorophenyl) -2-tert-butyl-3- (1,2,4-triazolyl) -

  butan-2-ol (Compound No. 430 of Table I).

  2-Chloro-4-fluorobenzyl chloride (4.0 g, 22 mmol) in anhydrous diethyl ether (10 ml) a

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  to a stirred mixture of magnesium turn (0.54 g, 22 mmol) and iodine (about 1 mg) in anhydrous diethyl ether (10 ml) was added dropwise at a rate selected to give maintain a constant reflux. The mixture was then added dropwise to

  stirring mixture of 2,2-dimethyl-4- (1,2,4-dimethyl) -2-

  triazolyl) pentan-3-one (2.5 g, 13.8 mmol) in anhydrous diethyl ether (20 ml) at about 10 ° C. The

  The mixture was then refluxed for 2 hours.

  After cooling to room temperature, the mixture was decanted off any unreacted magnesium and washed with a saturated aqueous solution of armonium chloride. The aqueous phase was separated and extracted with ether. The combined organic extracts were washed with brine, dried (MgSO 4) and evaporated in vacuo. Chromatography [SiO2, acetate

  ethyl-hexane (50:50) gave 1- (2-chloro-4-fluoro)

  pnényl) -2-tert-buts1-3- (1,2,4-triazolyl) butane-2-ol

  (Compound K, 430 of Table I) (1.2 g, 27%).

EXEMPT 10

  This example illustrates the preparation of 1- (2-

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

  2-ol, Compound No. 452 of Table I. 2,4-Dichlorobenzyl chloride (20.0 g, 102: iols) in dry diethyl ether (20 ml) was added dropwise to a suspension. with stirring of magnesium tetram in anhydrous diethyl ether (20 ml) at a rate selected to maintain a constant reflux. Anhydrous tetrahydrofuran (40 ml) was then added at a rate selected to maintain a constant volume as the solvate was distilled off. The mixture was then added to chloroacetyl chloride (23 g, 204 mmol) in dry tetrahydrofuran (100 mL) at -78 ° C in about 30 minutes. The mixture was warmed to room temperature in about one hour and water (200 ml) was added. The resulting mixture was extracted with ether (3 x 50 ml) and the combined extracts were washed with 2 N sodium hydroxide and brine, dried (MgSO 4) and evaporated in vacuo. Chromatography [SiO2, hexane-acetate

  ethyl (95: 5) to (90:10)] gave 1-chloro-3- (2-

  chlorophenyl) acetone (3.5 g, 14%), mp 620C.

  2-Bromobut-2-ene (1.35 g, 10 mmol) in anhydrous tetrahydrofuran (20 ml) was added to a stirred suspension of magnesium turn (0.24 g, mmol) in anhydrous tetrahydrofuran ( 20 ml) at a

  speed chosen so as to maintain a constant reflux.

  After refluxing for one hour and a half, the mixture was cooled to 0 ° C. and 1-chloro-3- (2-chlorophenyl) ace (1.0 g, 5 mmol) in anhydrous tetrahydrofuran (10 ml) was added. added drop by drop. The mixture was warmed to room temperature and poured into a saturated aqueous solution of ammonium chloride. The resulting mixture was extracted with diethyl ether and the combined extracts were washed with brine, dried (MgSO 4)

  and evaporated under vacuum to give 1- (2-chlorophenyl) -2-

  chloromethyl-3-methylpent-3-en-2-ol (1.3 g) which was

  used without further purification. 1- (2-chlorophenyl) -2-

  chloromethyl-3-methylpent-3-en-2-ol (1.3 g), from the previous reaction), 1,2,4-triazole (1.04 g, 15 moles) and potassium carbonate ( 1.38 g, 10 mm) were stirred under reflux in dimethylformamide (25 ml) for 3 hours. The mixture was then cooled, poured into water and extracted with ethyl acetate. The combined extracts were washed with water and brine, dried (MgSO4) and evaporated in vacuo. By

  chromatography (SiO2, ethyl acetate), the resulting

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

  en-2-ol (Compound N 452 of Table I) (0.012 g, 1% on

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  base of 1-chloro-3- (2-chlorophenyl) acetone). Mp 88 ° C.

EXAMPLE 11

  An emulsifiable concentrate was prepared by mixing the ingredients and stirring the mixture until all the components had dissolved. Compound No. 223 of Table I 10% Dichlorethylene 40% Calcium Dodecylbenzenesulfate 5% "Lubrol" L 10% "Aromasol" H 35%

EXAMPLE 12

  A composition in the form of easily dispersible grains in a liquid, for example water, was prepared by grinding together the first three ingredients in the presence of added water, and then stirring the sodium acetate. The resulting mixture was dried and sieved to 0.152 to 0.353 mm in size so that

  obtain the desired grain diameter.

  Compound No. 223 of Table I 50% "Dispersol" T 25% "Lubrol" APN5 1.5% Sodium Acetate 23.5%

EXAMPLE 13

  The ingredients were all crushed correctly-

  to produce a powdered formulation

  easily dispersible in liquids.

  Compound N 223 of Table I 45% "Dispersol '" T 5% "Lissapol" NX 0.5% "Cellofas" B600 2% Sodium acetate 47.5%

EXAMPLE 14

  The active ingredient was dissolved in a solvent and the resulting liquid was sprayed onto the kaolinite granules. The solvent was then allowed to evaporate to produce a granular composition. Compound N 223 of Table I 5% kaolinite granules 95%

EXAMPLE 15

  A composition that can be used for seed disinfection has been prepared by mixing the

three ingredients.

  Compound No. 223 of Table I 50% Mineral Oil 2% Kaolinite 48%

EXAMPLE 16

  A powder for dusting was prepared by

  mixing the active ingredient with talc.

  Compound N 223 of Table I 5% Talc 95%

EXAMPLE 17

  A colloidal formulation was prepared by grinding in a ball mill the constituents indicated 2G below, and then forming an aqueous suspension of

ground mixture with water.

  Compound N 223 of Table I 40% "Dispersol" T 10% "Lubrol" APN5 1% Water

EXAMPLE 18

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

  everything has been properly mixed.

  Compound No. 223 of Table I 25% tAerosol "OT / B 2%" Dispersol "AC 5% Kaolinite 28% Silica 40%

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EXAMPLE 19

  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 223 of Table I 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% Kaolinite 34%

EXAMPLE 20

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

of these ingredients.

  Compound N 223 of Table I 25% "Aerosol" OT / B 2% "Dispersol" AC 5% Kaolinite 68% 2C In Examples II to 20, the proportions of

  ingredients are indicated by weight.

  The remaining compounds listed in Table I were formulated as described particularly in

Examples 11 to 20.

  An explanation of the composi-

  tions or substances represented by the various

  trademarks mentioned above.

  LUBROL L: condensation product of nonyl

  phenol (1 mole) with ethylene oxide (13 moles) AROMASOL H: mixture of alkylbenzenes used as solvent DISPERSOL T and AC: mixture of sodium sulphate and a

formaldehyde condensation product

  dehyde with sodium naphthalenesulfonate

  LUBROL APN5: condensation product of nonyl

  phenol (1 mole) with ethylene oxide (5.5 moles) CELLOFAS B600: sodium salt of carboxymethylcellulose 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 21

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

used was the following.

  The plants were grown in John Innes jar compost (N s 1 and 2) 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 an acetone / ethanol mixture which was diluted to the desired concentration immediately before the reaction. use. For

  diseases developing on the foliage, the formulas

  (100 mg / l of active ingredient) were applied by foliar spraying and applied to plant roots in the soil. Sprays were applied to maximum retention and root watering to a final concentration equivalent to approximately

  millionths of active ingredient compared to dry soil.

  Tween 20 has a final concentration of 0.05% added, and then the sprays were applied to cereals. For most tests, the compound has been

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

  one or two days before the plant has been

E634482

  inoculated with the disease. The test on Erysiphe graminis, in which the plants were inoculated

  24 hours before treatment was an exception.

  Foliar pathogens were applied by spraying as spore suspensions onto the leaves of the test plants. After inoculation, the plants were installed in a

  appropriate environment so as to allow the infection to

  to grow, then incubated until

  that the disease is at a stage allowing estimation.

  The time elapsed between inoculation and estimation varied from four to fourteen days according to the disease

and the environment.

  Inhibition of the disease was assessed according to the following rating scale: 4 = no disease 3 = traces up to 5% disease on untreated plants 2 6-25% disease on non-disease plants treated i = 26-59% disease on untreated plants C = 60-100% disease on untreated plants.

  The results are shown in Table III.

  The following is a description of the above-mentioned methods of the application of the present invention. APA (HI DI COLA RYZAE

  (BI, E) (01 (,; 1). (POMMI.ER) (ARACH I DE) (P IZ)

7 3 4 0 4 O

8 3 4 4 2 0

13 4 4 4 4 2

14 3 4 4 0 O

41 4

2.7 4 4 (30 H

43 3 4 3 4

67 04 '4 0 0

6 8 41 4

73 4 4 4 3 2

74 3 4 4 0 2

R5 4 4 4 4 3

87 4 4 4 4 3

103 4 4 4 4 I

4 4 4 4 3

127 3 4 0 0 0

1 28 2 4 3 4 3

131 O 4 0 3 3

ow

_, __ _ r ^ .-

TABLE III (continued)

  N OF THE PUCCINIA ERYSIPHE VENTURIA CERCOSPORA PYRICULARIA

  RECONDITA GRAMINIS COMPOUND INAEQUALIS ARACHIDICOLA ORYZAE

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

133 4 4 4 4 O

134 3 4 O 4 2

4 4 4 4 2

147 3 3 4 3 1

153 3 4 4, 3 0

163 4 4 4 4 0

3 4 3 4 0

193 4 3 4 4 2

223 4 * 3 * 4 * 2 * 0 *

224 4 4 4 4 3

421 4 4 4 4 1

423 4 4 4 1 0

424 3 4 4 4 3

426 3 4 4 4 3

427 3 4 2 3 0

428 3 4 4 3 3

429 4 4 4 4 0

430 3 4 4 3 3

432 3 4 4 1 0

452 1 * 4 * 3 * 3 * 0 *

  r * * Results obtained for a rate of 25 millionths - protection test only. Ch co r>

Claims (13)

  1. Compounds characterized in that they correspond to the general formula (I): R3 OR2 R5 Yx I I i Q C - C - C - AZ M1 Y R4 R1 F6   Z and their stereoisomers, wherein R1 is a   alkyl group (when R5 is other than hydrogen   ne), or is a group of general formula (II): C-C - R7 (II)   or is a group of general formula (III): R9 C / (III) R8 10   R7, R8, R9 and R10 are, 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, R4, R5 and R6 are independently hydrogen, alkyl, alkenyl or alkynyl; X, Y and Z are   independently selected from the group consisting of hydrogen   n, halogen, alkyl, haloalkyl, cycloalkyl-   cycloalkylalkyl, alkenyl, alkynyl, aryl   substituted, optionally substituted aralkyl, alkoxy, aryloxy, haloalkoxy or aralkoxy; Az is an imidazol-1-yl group or a 1,2,4-triazol-1-yl group, with the proviso that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is a 1,2,4-triazol-1-yl group, then R1 is not -CeC-alkyl and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, then R8, R9 and R10 are not all hydrogen; and their salts and metal complexes.   2. Compounds according to claim 1, characterized in that they correspond to the general formula (I): X R3 OR2 R5   embedded image and their stereoisomers, wherein R 1 represents an alkyl group containing 1 to 6 carbon atoms, and   carbon dioxide (for cases where R5 is something other than hydrogen   ne) or a group of general formula (II): C. C - R7 (II)   or a group of general formula (III): i // R9 (III) C C R / R10   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 2 to 4 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 and Az is 1-imidazole or 1,2,4-triazole; provided that when R3 and R4 are both methyl, R5 and   R6 are both hydrogen and Az is a group 1,2,4-   triazol-1-yl, then R1 is not a -C1-alkyl group and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, R8, R9 and R10 are then not all hydrogen; and their salts and their complexes metal.   3. Compounds according to claim 1, characterized in that they correspond to the general formula (I): X R3 OF2 R5 y '_ t - - C _ zAz (I) R4 R1 R6   and their stereoisomers, wherein R1 is C1-C6 alkyl (when R5 is other than hydrogen) or is a group of the general formula (II): i, CC C R7 (II) or represents a group of general formula (III): R9 R9 (III) R8 R0   R7, R8, R9 and R10 independently represent hydrogen.   n, halogen, C1-C4 alkyl, C2-C4 alkenyl, 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-R6 are, independently, hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z are independently selected from the group consisting of hydrogen, halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C7cycloalkyl (C3-C7cycloalkyl) - (C1-C4) alkyl; C6 to C6), C2 to C6 alkenyl, C2 to C6 alkynyl, phenyl, phenyl (C1 to C6) alkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, phenoxy   or phenyl- (C1-C6) alkoxy; Az is an imidazole group   1-yl or 1,2,4-triazol-1-yl; all of the above phenyl groups are optionally substituted with halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, nitro, phenyl or phenoxy; provided that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl, then R1 is not a group - CECalkyl, and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, R8, R9 and R10 are not all hydrogen;   and their salts and metal complexes.   4. Compounds according to any of   claims 1 to 3, characterized in that they respond to the general formula (I): X R3 OR2 R5 R i R6 (1) Cc) c C C - c Az Z R4 R1 R6   and their stereoisomers, wherein R 1 is a C 3 or C 4 alkyl group; R2, R3 and R6 are independently hydrogen or C1-C4 alkyl; R4 is hydrogen, R5 is C1-C4 alkyl; X, Y and Z are independently hydrogen, halogen, C1 to C4 alkyl, C1 to C4 alkoxy, phenoxy or phenyl; Az is imidazol-1-yl or 1,2,4-triazol-1-yl; and their salts and metal complexes. 5. Compounds according to claim 4, characterized in that R1 is a C3 or C4 alkyl group; R2 is hydrogen or methyl; R3, R4 and R6 are all hydrogen, R5 is C1- or C2-alkyl; Az is 1,2,4-triazolyl, X, Y and Z independently represent hydrogen, chlorine or fluorine; and their salts and metal complexes. 6. Compounds according to any of   claims 1 to 3, characterized in that they respond to the general formula (I): - P 3 RI F 5 CC _-C _ _C AZ (I)   | R: p6 z and stereoisomers thereof, wherein R1 is a group of general formula (II): C C = CR7 (II)   or is a group of formula (III): R9 C C (III) - R8 in   R7, R8, R9 and R10 independently represent hydrogen.   ne, halogen, C1-C4alkyl, C2-C4alkenyl or C2-C4alkynyl; R2 is hydrogen, C1-C4 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, R4, R5 and R6 are independently hydrogen, C1-C6 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; X, Y and Z independently represent hydrogen, chlorine or fluorine atoms; Az is imidazol-1-yl or 1,2,4-triazol-1-yl; with the proviso that when R3 and R4 are both methyl, R5 and R6 are both hydrogen and Az is 1,2,4-triazol-1-yl, R1 is not -CC- alkyl and with the proviso that when R3 and R4 are both alkyl, R5 is hydrogen and R6 is alkyl, alkenyl or alkynyl, then R8, R9 and R10 are not all hydrogen; and their salts and their metal complexes.   7. Compounds according to any of   claims 1, 2, 3 and 6, characterized in that   correspond to the general formula (XXXIV): OR2 y 1i. CH- C- CH2- N N ZX R 1 N (XXXIV ')   and stereoisomers thereof, wherein R1 is a group of formula (II): CC C R7 (II)   or is a group of formula (III): R9 C C (II) R8 R10   R7, R8, R9 and R10 independently represent hydrogen.   ne or a C1-C4 alkyl group; R2 is hydrogen, C1-C4 alkyl, allyl or propargyl; X, Y and Z independently represent hydrogen, chlorine or fluorine atoms; and their salts and metal complexes. 8. Compounds according to any of   claims 1, 2, 3, 6 and 7, characterized in that   correspond to the general formula (XXXV): OR2 Y / CH 2 - C - CH 2 --N N (XXXV) / _ / hi ____ X N   and stereoisomers thereof, wherein R1 is a group of formula (II): C - C R7 (II)   or a group of formula (III): ## STR2 ## is a C 1 -C 4 alkyl group, R 8 is hydrogen, one of R 9 and R 10 is hydrogen, while the other is C1-C4 alkyl; R2 is hydrogen or a methyl group; X and Y are hydrogen, chlorine or   fluorine; and their salts and metal complexes. 9. The compound of formula F Ci. OH CH2- C _ CH2 t N CH N He HC CH2-CH3   and its stereoisomers; and their salts and metal complexes. Process for the preparation of compounds of general formula (I) X R3 OR2 R5 I I I -3- C - C- C --- Az () Z R4 R1 R6   characterized in that it co-onsists to etherify an alcohol of formula (IV): X R3 OH R5 X R3 OH R5 I I I   Wherein Az, 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 a sodium halide; alkyl of formula R2Hal in which Hal may be chlorine, bromine or iodine and R2 is as defined in claim 1 excluding hydrogen, in a suitable solvent, the compounds of general formula (IV ) being prepared by treatment of compounds of general formula (VI) X R3 R5 <1 II 1 CCC - Az VI) Y R4 R6   Z, Az, R3 to R6, X, Y and Z are as defined in claim 1, with a metal acetylide of general formula (VII): M CC - R7 (VII)   in which R7 is as defined in claim 1 and M represents a metal such as lithium, magnesium or titanium or M may be silicon, in the presence of a suitable fluoride-type catalyst [for cases where R1 is a group of general formula (II)] or a compound of general formula (VIII): M R9   wherein R8 to R10 are as defined in claim 1 and M is magnesium (Grignard reagent) or lithium, in a suitable solvent such as tetrahydrofuran [for the cases]. R1 is a group of general formula (III)] or a compound of general formula R1M wherein R1 is an alkyl group as defined in claim 1 and M is a metal such as lithium or magnesium [for cases where R1 is an alkyl group and R5 is not hydrogen].   11. A fungicidal composition, characterized in that it comprises as an ingredient a compound according to claim 1 or a stereoisomer, a salt or a metal complex of this compound and, optionally, a carrier. or a diluent.   A method of controlling fungi which comprises applying to a plant or a seed a compound according to claim 1 or a stereoisomer, a   salt or a metal complex thereof, or a composition according to claim 11.   13. New intermediate compounds, characterized in that they correspond to one of the formulas: X R3 OH R5   0 I I i C C C Az IV) I. (R4 V R4 R6) X R3 OH R5 QC C - C / z R4 C R6 z iSl R7 R3 O H C C (XVI) y [4 T H H   in which R1, R2, R3, R4, R5, R6, X; Y, Z and Az are   as defined in claim 1.