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Title:
NOVEL &agr -OXYGENATED OR &agr -THIOLATED CARBOXYLIC ACID PHENETHYLAMIDE DERIVATIVES
Document Type and Number:
WIPO Patent Application WO/2003/042168
Kind Code:
A1
Abstract:
The invention relates to &agr -oxygenated or &agr -thiolated carboxylic acid phenethylamide derivatives of general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein A stands for optionally substituted aryl or optionally substituted heteroaryl; X is oxygen or sulfur; Y is oxygen or sulfur; R¿1?, is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl or halocycloalkyl; R¿2? is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy-alkyl, alkoxy-alkenyl, alkoxy-alkynyl, whereof all alkyl- alkenyl-, alkynyl-, or cycloalkyl-groups may be optionally substituted by halogen; or optionally substituted arylalkyl, optionally substituted aryl-alkenyl, optionally substituted aryl-alkynyl or optionally substituted aryloxy-alkyl; R¿3? is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, alkoxy-alkyl, alkoxy-alkenyl, alkoxy-alkynyl, whereof all alkyl- alkenyl-, alkynyl-, or cycloalkyl-groups may be optionally substituted by halogen; or is optionally substituted aryl-alkyl, optionally substituted aryl-alkenyl, optionally substituted aryl-alkynyl, optionally substituted aryloxy-alkyl, optionally substituted heteroaryl-alkyl, optionally substituted heteroaryl-alkenyl or optionally substituted heteroaryl-alkynyl; R¿4? is alkyl, alkenyl, alkynyl, alkoxy-alkyl, alkoxy, alkenyloxy, alkenyloxy, alkylthio, alkanoyl, alkylamino, dialkylamino, alkoxycarbonyl, whereof all alkyl- alkenyl or alkynyl-groups may be optionally substituted by halogen; or is halogen, cyano, nitro, amino, formyl or carboxyl; R¿5? is hydrogen, alkyl, alkenyl or alkynyl; n is an integer 0,1, 2, 3, or 4; B, represents a bridge member -CR¿10?R¿11?-, wherein R¿10? and R¿11? independently of each other are hydrogen or alkyl; and B¿2? is an alkylene bridge. These compounds possess useful plant protecting properties and may advantageously be employed in agricultural practice for controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

Inventors:
ZELLER MARTIN (CH)
LAMBERTH CLEMENS (CH)
Application Number:
PCT/EP2002/012846
Publication Date:
May 22, 2003
Filing Date:
November 15, 2002
Export Citation:
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Assignee:
SYNGENTA PARTICIPATIONS AG (CH)
ZELLER MARTIN (CH)
LAMBERTH CLEMENS (CH)
International Classes:
A01N37/18; A01N37/36; C07C231/12; C07C235/34; C07D237/08; C07C253/30; C07C255/59; C07C319/20; C07C323/62; C07C327/44; C07D213/30; C07D213/61; C07D215/14; C07D237/12; C07D239/26; C07D239/30; C07D241/12; C07D261/08; C07D277/24; C07D307/42; C07D307/44; C07D317/54; C07D319/18; C07D333/16; (IPC1-7): C07C235/34; C07C327/44; C07C323/22; A01N37/18
Domestic Patent References:
WO1994029267A11994-12-22
WO1996017840A11996-06-13
WO2001087822A12001-11-22
WO1999033810A11999-07-08
Other References:
PATENT ABSTRACTS OF JAPAN vol. 017, no. 391 (C - 1087) 22 July 1993 (1993-07-22)
PETTIT G R ET AL: "Isolation and Structure of Hemibastadinols 1-3 from the Papua New Guinea Marine Sponge Ianthella basta", JOURNAL OF NATURAL PRODUCTS, vol. 59, no. 10, 1996, pages 927 - 934, XP001146001
Attorney, Agent or Firm:
Bastian, Werner c/o Syngenta Participations AG Intellectual Property P.O. Box Basel . (CH)
Download PDF:
Claims:
What is claimed is:
1. A composition for controlling and protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of the general formula including the optical isomers thereof and mixtures of such isomers, wherein A stands for optionally substituted aryl or optionally substituted heteroaryl ; X is oxygen or sulfur ; Y is oxygen or sulfur ; R, is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl or halocycloalkyl ; R2 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxy alkenyl, alkoxyalkynyl, whereof all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or optionally substituted arylalkyl, optionally substituted arylalkenyl, optionally substituted arylalkynyl or optionally substituted aryloxyalkyl ; R3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalke nyl, alkoxyalkynyl, whereof all alkylalkenyl, alkynyl, or cycloalkylgroups may be optio nally substituted by halogen ; or is optionally substituted arylalkyl, optionally substituted aryl alkenyl, optionally substituted arylalkynyl, optionally substituted aryloxyalkyl, optionally substituted heteroarylalkyl, optionally substituted heteroarylalkenyl or optionally substituted heteroarylalkynyl R4 is alkyl, alkenyl, alkynyl, alkoxyalkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkanoyl, alkylamino, dialkylamino, alkoxycarbonyl, whereof all alkylalkenyl or alkynylgroups may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; R5 is hydrogen, alkyl, alkenyl or alkynyl ; n is an integer 0,1, 2,3, or 4; B, represents a bridge memberCR10R 1, wherein Rio and Rt independently of each other are hydrogen or alkyl ; and B2 is an alkylen bridge; together with a suitable carrier.
2. A compositon according to claim 1 wherein A is phenyl, naphthyl, 1, 3biphenyl, 1, 4biphenyl, fluorenyl, tetralinyl, indanyl, methylendi oxyphenyl, (1, 2ethylene) dioxyphenyl, furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyri dyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, indazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, quinolinyl or isoquinolinyl, each optionally substituted by one or more substituents selected from the group comprising CiCioalkyl, C2C10alkenyl, C2C10alkynyl, C1C8cycloalkyl, C1C8cycloalkylC1C10alkyl, phenyl, <BR> <BR> <BR> phenylCiCioalkyl, C,Cioalkoxy, C3C, oalkenyloxy, C3Cioalkynyloxy, CiCioalkylthio, C1C10alkylsulfonyl, C1C10alkoxyC1C10alkyl, C1C10alkanoyl, C1C10alkoxycarbonyl, C3C10alkenyloxycarbonyl, C3C10alkynyloxycarbonyl, C1C10alkylamino, diC1C10al kylamino, hydroxy, halogen, cyano, nitro, amino and formyl radicals, wherein in turn the alkylalkenyl, alkynyland cycloalkylgroups may be optionally substituted by one or more halogen atoms; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R, stands for hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl or C3C8cycloalkyl, wherein each alkylalkenyl, alkynyland cycloalkylgroup may be optionally substituted by halogen ; and R2 is hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl, C3C8cycloalkyl, C3C3cycloal kylC1C6alkyl, C1C6alkoxyC1C6alkyl, C1C6alkoxyC3C10alkenyl or C1C6alk oxyC3_Cioalkynyl, wherein all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or stands for optionally substituted arylCiC6alkyl, optionally substituted arylC3Ct0alkenyl, optionally substituted arylC3Cioalkynyl or optionally substituted aryloxyC1C6alkyl ; and R3 is hydrogen, CiCioalkyl, C3C1oalkenyl, C3C10alkynyl, C3C8cycloalkyl, C3C8cycloalkylC1C6alkyl, C1C6alkoxyC1C6alkyl, CiC6alkoxyC3Cioalkenyl or C1C6alkoxyC3C10alkynyl, wherein all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or is optionally substituted arylCtC6alkyl, optionally substituted arylC3Cioalkenyl, optionally substituted arylC3Cioalkynyl, optionally substituted aryloxyC1C6alkyl, optionally substituted heteroarylCiC6alkyl, optionally substituted heteroarylC3C10alkenyl or optionally substituted heteroarylC3C10alkynyl ; and R4 is C1C6alkyl, C3C6alkenyl, C3C6alkynyl, C1C6alkoxyC1C6alkyl, C1C6alkoxy, C3C6alkenyloxy, C3C6alkynyloxy, C1C6alkylthio, CtC6alkanoyl, CtC6alkylamino, diC1C6alkylamino or C1C6alkoxycarbonyl, wherein all alkylalkenyl or alkynylgroups may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; and R5 is hydrogen, CiC6alkyl, C3C6alkenyl or C3C6alkynyl ; and B2 is an CiC6alkylenebridge ; and n is an integer from 0 to 2.
3. A compositon according to claims 1 or 2 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2ethy lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising C1C, oalkyl, CiCiohaloalkyl, C2Cioal kenyl, C2C10haloalkenyl, C2C10alkynyl, benzyl, C1C10alkoxy, C1C10haloalkoxy, C3C10alkenyloxy, C3C10alkynyloxy, C1C10alkylthio, C1C10haloalkylthio, C1C10al kylsulfonyl, CiC6alkoxyC,C6alkyl, C,Cioalkanoyl, CiC, oalkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl.
4. A compositon according to claim 1 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2ethy lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising C1C10alkyl, C1C10haloalkyl, C2C10alke nyl, C2C10haloalkenyl, C2C10alkynyl, benzyl, C1C10alkoxy, C1C10haloalkoxy, C3C10al kenyloxy, C3C10alkynyloxy, C1C10alkylthio, C1C10haloalkylthio, C1C10alkylsulfonyl, C1C6alkoxyC1C6alkyl, C1C10alkanoyl, CiC, oalkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R, is hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl, C1C10haloalkyl, C3C10haloalkenyl or C3C10ha loalkynyl ; and R2 is hydrogen, C1Cioalkyl, C3C, oalkenyl, C3Coalkynyl, C3C8cycloalkyl, C3C$cycloalkylCiC6alkyl, C3C8cycloalkylC3. C6alkenyl, C3C8cycloalkylC3C6alkynyl,<BR> ClC6alkoxyClC6alkyl, ClC6alkoxyC3C6alkenyl, ClC6alkoxyC3C6alkynyl, C1C10haloalkyl, C3C10haloalkenyl, C3C10haloalkynyl, phenylC1C6alkyl, phenylC1C5al kenyl or phenylCiC6alkynyl, wherein phenyl may optionally be monoor disubstituted by substituents selected from the group comprising CiC6alkyl, C2C6alkenyl, C2C6alkynyl, CtC6alkoxy, CiC6haloalkoxy, CiC6alkylthio, CiC6haloalkylthio, CiC6alkanoyl, CiC6alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R3 is hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl, C3C8cycloalkyl, C3C8cycloalkylC1C6alkyl, C3C8cycloal kylC3C6alkenyl, C3C8cycloalkylC3 C6alkynyl, CiC6alkoxyCiC6alkyl, CiC6alk oxyC3C6alkenyl, C1C6alkoxyC3C6alkynyl, C1C10haloalkyl, C3C10haloalkenyl, C3Clohaloalkynyl, phenylClC6alkyl, phenylCiC6. alkenyl or phenylClC6alkynyl, wherein the phenyl groups are optionally monoor disubstituted by radicals selected from the group comprising CiC6alkyl, C2C6alkenyl, C2C6alkynyl, ClC6alkoxy, ClC6haloalkoxy, CiC6alkylthio, C,C6haloalkylthio, C,C6alkanoyl, C, _C6alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R4 is CiC6alkyl, Ci_C6haloalkyl, CiC6alkoxy, C3C6alkenyloxy, C3C6alkynyloxy, C1C6alkylthio, halogen, cyano or nitro; and R5 is hydrogen, C1C6alkyl, C3C6alkenyl or C3C6alkynyl ; and n is an integer from 0 to 2; and B2 is an alkylenebridge of the formulaCH (R20) (CH2) p, wherein R20 stands for hydrogen or CiC4alkyl and p is an integer 0,1 or 2.
5. A compositon according to claim 1 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, thienyl, each optionally substituted by one, two or three substituents selected from the group comprising C1C10alkyl, C1C10haloalkyl, C2C10alkenyl, C2C10alkynyl, benzyl, C1C10alkoxy, C1C10haloalkoxy, C1C10alkylthio, C1C10haloalkylthio, C1C10haloalkylthio, C1C10alkanoyl, C1C10alkoxycar bonyl, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and Ri is hydrogen, C1C8alkyl, C3C8alkenyl or C3C8alkynyl ; and R2 stands for hydrogen, C1C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl, C,C4alkoxyC3C4 alkynyl, C1C8haloalkyl or C3C8haloalkynyl ; and R3 is hydrogen, C1C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl, C1C4alkoxyC3C4alkynyl, C1C8haloalkyl or C3C8haloalkynyl ; and R4 is C1C6alkoxy, C3C6alkenyloxy, C3C6alkynyloxy or halogen ; and R5 is hydrogen or C1 C4 alkyl ; and Bi stands forCH2,CH (CH3) or C(CH3)2 ; and n is the integer 0 or 1; and B2 is an alkylenebridge of the formulaCH (R20)(CH2)p , wherein R20 stands for hydrogen or C,C4alkyl and p is an integer 0,1 or 2.
6. A compositon according to claim 1 wherein; or wherein A is phenyl or thienyl, optionally substituted by one or two substituents selected from the group comprising C1C4alkyl, C1C4haloalkyl, C2C4alkenyl, C1C4alkoxy, C1C10alkylthio, C1C4alkanoyl, halogen and cyano; and X is oxygen; and Y is oxygen; and R, is hydrogen, C,C8alkyl, C3C8alkenyl or C3C8alkynyl ; and R2 is hydrogen, C1C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl or CC4alkoxyC3C4alkynyl ; and R3 is hydrogen, C1C8alkyl, C3C$alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl or CtC4alkoxyC3C4alkynyl ; and R4 is 3CiC6alkoxy ; and R5 is hydrogen or methyl ; and B1 is selected fromCH2,CH (CH3) andC (CH3) 2 ; and n is the integer 0 or 1; and B2 is CH2CH2, CH2, CH (CH3)CH2 or CH (CH3).
7. A compositon according to claim 1, wherein A is phenyl, optionally substituted by one or two substituents selected from the group comprising CiC4alkyl, CiC4haloalkyl, halogen and cyano; and X and Y are both oxygen; and Ri is hydrogen; and R2 is hydrogen, C,C4alkyl, C3C4alkenyl or C3C4alkynyl ; and R3 is CiC4alkyl, C3C4alkenyl or C3C4alkynyl ; and R4 is 3methoxy or 3ethoxy; and R5 is hydrogen; and B, is selected fromCH2,CH (CH3) andC (CH3) 2 ; and n is the integer 1; and B2 isCH2CH2.
8. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting a) reacting the phenol of formula VI wherein A, Ri, R2, R4, R5, B1, B2 and n are as defined for formula I with a compound of formula V ZR3 (V) wherein R3 is as defined for formula I and wherein Z is a leaving group yielding the subgroup IA b) reacting the acid of formula 11 with an amine of formula Vil wherein A, Ri, R2, R3, R4, R5, B1, Bs and n are as defined for formula 1, or c) reacting the ahydroxycar of formula XIV with an etherifying agent of formula XV ZR2 (XV) wherein A, Ri, R2, R3, R4, R5, B1, B2 and n are as defined for formula I and wherein Z is a leaving group; yielding the subgroup IB and optionally (IB) converting the amide function of the compound of subgroup IA into a thioamide function as in the subgroup IC by treatment with a sulfurating agent.
9. The use of a compound of formula I according to claim 1 for protecting cultivated crop plants against infestation by phytopathogenic microorganisms.
10. A method of controlling and preventing an infestation of crop plants by phytopatho genic microorganisms, which comprises the application of a compound of formula I accor ding to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof.
11. A method according to claim 11, wherein the phytopathogenic microorganisms are fungal organisms.
12. A compound of the general formula including the optical isomers thereof and mixtures of such isomers, wherein A stands for optionally substituted aryl or optionally substituted heteroaryl ; X is oxygen or sulfur ; Y is oxygen or sulfur ; R, is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl or halocycloalkyl ; R2 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxy alkenyl, alkoxyalkynyl, whereof all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or optionally substituted arylalkyl, optionally substituted arylalkenyl, optionally substituted arylalkynyl or optionally substituted aryloxyalkyl ; R3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkenyl, alkoxyalkynyl, whereof all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or is optionally substituted arylalkyl, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted aryloxyalkyl, optionally substituted heteroarylalkyl, optionally substituted heteroarylalkenyl or optionally substituted heteroarylalkynyl R4 is alkyl, alkenyl, alkynyl, alkoxyalkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkanoyl, alkylamino, dialkylamino, alkoxycarbonyl, whereof all alkylalkenyl or alkynylgroups may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; R5 is hydrogen, alkyl, alkenyl or alkynyl ; n is an integer 0,1, 2,3, or 4; B1 represents a bridge memberCR10R11, wherein Rio and Rn independently of each other are hydrogen or alkyl ; and B2 is an alkylen bridge; with the exception of the compounds 2hydroxyN [2 (3bromo4hydroxyphenyl)ethyl]3 (3bromo4hydroxyphenyl) propionamide, 2hydroxyN [2 (3bromo4methoxyphenyl)ethyl]3 (3bromo4methoxyphenyl) propionamide, 2hydroxyN [2 (3bromo4methoxyphenyl)ethyl]3 (3, 5dibromo4hydroxyphenyl) propionamide, 2hydroxyN [2 (3, 5dibromo4hydroxyphenyl)ethyl]3 (3bromo4hydroxyphenyl) propionamide, 2hydroxyN [2 (3, 5dibromo4methoxyphenyl)ethyl]3 (3bromo4methoxyphenyl) propionamide, and 2hydroxyN [2 (3bromo4methoxyphenyl)ethyl]3 (3, 5dibromo4methoxyphenyl) propionamide.
13. A compound according to claim 13 wherein A is phenyl, naphthyl, 1, 3biphenyl, 1, 4biphenyl, fluorenyl, tetralinyl, indanyl, methylendi oxyphenyl, (1, 2ethylene) dioxyphenyl, furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, indazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, quinolinyl or isoquinolinyl, each optionally substituted by one or more substituents selected from the group comprising C1C10alkyl, C2Cioalkenyl, C2C10alkynyl, C1C8cycloalkyl, C1C8cycloalkylC1C10alkyl, phenyl, phenylCiCioalkyl, C1C10alkoxy, C3C10alkenyloxy, C3C10alkynyloxy, C1C10alkylthio, CiCioalkylsulfonyl, CiCioalkoxyCiCioalkyl, CiCioalkanoyl, C,Cioalkoxycarbonyl, C3Cioalkenyloxycarbonyl, C3C10alkynyloxycarbonyl, C1C10alkylamino, diC1C10al kylamino, hydroxy, halogen, cyano, nitro, amino and formyl radicals, wherein in turn the alkylalkenyl, alkynyland cycloalkylgroups may be optionally substituted by one or more halogen atoms; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and Ri stands for hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl or C3C8cycloalkyl, wherein each alkylalkenyl, alkynyland cycloalkylgroup may be optionally substituted by halogen ; and R2 is hydrogen, CiC, oalkyl, C3Cioalkenyl, C3Cioalkynyl, C3C8cycloalkyl, C3C8 cycloal kylC1C6alkyl, C1C6alkoxyC1C6alkyl, C1C6alkoxyC3C10alkenyl or C1C6alk oxyC3C10alkynyl, wherein all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen ; or stands for optionally substituted arylCiC6alkyl, optionally substituted arylC3Cioalkenyl, optionally substituted arylC3Cioalkynyl or optionally substituted aryloxyC1C6alkyl ; and R3 is hydrogen, CiCioalkyl, C3Cioalkenyl, C3Cioalkynyl, C3C8cycloalkyl, C3C8 cycloalkylCtC6alkyl, CC6alkoxyC C6alkyl, C1C6alkoxyC3Cioalkenyl or CiC6alkoxyC3Cioalkynyl, wherein all alkylalkenyl, alkynyl, or cycloalkylgroups may be optionally substituted by halogen; or is optionally substituted arylC,C6alkyl, optionally substituted arylC3C10alkenyl, optionally substituted arylC3C 0alkynyl, optionally substituted aryloxyC1C6alkyl, optionally substituted heteroarylC1C6alkyl, optionally substituted heteroarylC3C10alkenyl or optionally substituted heteroarylC3Cioalkynyl ; and R4 is CiC6alkyl, C3C6alkenyl, C3C6alkynyl, C1C6alkoxyC1C6alkyl, C1C6alkoxy, C3C6alkenyloxy, C3C6alkynyloxy, C1C6alkylthio, C1C6alkanoyl, C1C6alkylamino, diCiC6alkylamino or CiC6alkoxycarbonyl, wherein all alkylalkenyl or alkynylgroups may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; and R5 is hydrogen, CiC6alkyl, C3C6alkenyl or C3C6alkynyl ; and B2 is an C1C6alkylenebridge; and n is an integer from 0 to 2.
14. A compound according to claim 13 or 14 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2ethy lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising CiCi0alkyl, C1C10haloalkyl, C2C10alke nyl, C2Ciohaloalkenyl, C2Cioalkynyl, benzyl, CiCioalkoxy, CiCiohaloalkoxy, C3Cioal kenyloxy, C3C10alkynyloxy, C1C10alkylthio, C1C10haloalkylthio, C1C10alkylsulfonyl, C1C6alkoxyC1C6alkyl, CiCioalkanoyl, C1C10alkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl.
15. A compound according to claim 13 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2ethy lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising C1C10alkyl, C1C10haloalkyl, C2C10al kenyl, C2C10haloalkenyl, C2C10alkynyl, benzyl, C1C10alkoxy, C1C10haloaloxy, C3C10alkenyloxy, C3C10alkynyloxy, C1C10alkylthio, C1C10haloalkylthio, C1C10al kylsulfonyl, C1C6alkoxyC1C6alkyl, C1C10alkanoyl, C1C10alkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and Ri is hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl, C1C10haloalkyl, C3C10haloal kenyl or C3C10haloalkynyl ; and R2 is hydrogen, CiCioalkyl, C3C1oalkenyl, C3C10alkynyl, C3C8cycloalkyl, C3C$_cycloalkylCiC6alkyl, C3C8cycloalkylC3 C6alkenyl, C3C8cycloal kylC3C6alkynyl, C1C6alkoxyC1C6alkyl, CiC6alkoxyC3C6alkenyl, CiC6alkoxyC3C6 alkynyl, C1C10haloalkyl, C3C10haloalkenyl, C3C10haloalkynyl, phenylC1C6alkyl, phenylC1C6alkenyl or phenylC1C6alkynyl, wherein phenyl may optionally be monoor disubstituted by substituents selected from the group comprising C1C6alkyl, C2C6alkenyl, C2C6alkynyl, C1C6alkoxy, C1C6haloalkoxy, C1C6alkylthio, C1C6haloalkylthio, C1C6alkanoyl, C1C6alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R3 is hydrogen, C1C10alkyl, C3C10alkenyl, C3C10alkynyl, C3C8cycloalkyl, C3C8cycloalkylC1C6alkyl, C3C8cycloalkylC3C6alkenyl, C3C$cycloalkylC3C6alkynyl, CiC6alkoxyCiC6alkyl, CiC6aikoxyC3C6alkenyl, C1C6alkoxyC3C6alkynyl, C1C10haloalkyl, C3C10haloalkenyl, C3Clohaloalkynyl, phenylClC6alkyl, phenylClCralkenyl or phenylCC6alkynyl, wherein the phenyl groups are optionally monoor disubstituted by radicals selected from the group comprising C,C6alkyl, C2C6alkenyl, C2C6alkynyl, CiC6alkoxy, CiC6haloalkoxy, CiC6alkylthio, CiC6haloalkylthio, CiC6alkanoyl, Ci_C6alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R4 is C1C8alkyl, C1C6haloalkyl, C1C6alkoxy, C3C6alkenyloxy, C3C6alkynyloxy, C1C6alkylthio, halogen, cyano or nitro; and R5 is hydrogen, CiC6alkyl, C3C6alkenyl or C3C6alkynyl ; and n is an integer from 0 to 2; and B2 is an alkylenebridge of the formulaCH (R2o) (CH2) p, wherein R20 stands for hydrogen or CiC4alkyl and p is an integer 0,1 or 2; or wherein.
16. A compound according to claim 13 wherein A is phenyl, naphthyl, 1, 4biphenyl, tetralinyl, indanyl, methylendioxyphenyl, thienyl, each optionally substituted by one, two or three substituents selected from the group comprising C1C10alkyl, C1C10haloalkyl, C2C10alkenyl, C2C10alkynyl, benzyl, C1C10alkoxy, C1C10haloalkoxy, C1C10alkylthio, C1C10haloalkylthio, C1C10alkanoyl, C1C10alk oxycarbonyl, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R1 is hydrogen, C1C8alkyl, C3C8alkenyl or C3C8alkynyl ; and R2 stands for hydrogen, C1C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl, C1C4al koxyC3C4alkynyl, CiC8haloalkyl or C3C8haloalkynyl ; and R3 is hydrogen, CiC8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl, C1C4alkoxyC3C4alkynyl, C1C8haloalkyl or C3C8haloalkynyl ; and R4 is CiC6alkoxy, C3C6alkenyloxy, C3C6alkyn yloxy or halogen ; and R5 is hydrogen or CiC4alkyl ; and B1 stands forCH2,CH (CH3)or C (CH3) 2 ; and n is the integer 0 or 1; and B2 is an alkylenebridge of the formulaCH (R20) (CH2) p, wherein R20 stands for hydrogen or C1C4alkyl and p is an integer 0,1 or 2.
17. A compound according to claim 13 wherein A is phenyl or thienyl, optionally substituted by one or two substituents selected from the group comprising CiC4alkyl, CiC4haloalkyl, C2C4alkenyl, C1C4alkoxy, C1C10alkylthio, C1C4alkanoyl, halogen and cyano; and X is oxygen; and Y is oxygen; and Ri is hydrogen, C1C8alkyl, C3C8alkenyl or C3C8alkynyl ; and R2 is hydrogen, C1C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkylC3C4alkynyl or CC4alkoxyC3C4alkynyl ; and R3 is hydrogen, C,C8alkyl, C3C8alkenyl, C3C8alkynyl, C3C6cycloalkyiC3C4alkynyl or CiC4alkoxyC3C4alkynyl ; and R4is 3C1C6alkoxy ; and R5 is hydrogen or methyl ; and B is selected fromCH2,CH (CH3) and c (CH3) 2 ; and n is the integer 0 or 1; and B2 is CH2CH2, CH2, CH (CH3)CH2 or CH (CH3).
18. A compound according to claim 13 wherein A is phenyl, optionally substituted by one or two substituents selected from the group comprising C1C4alkyl, CiC4haloalkyl, halogen and cyano; and X and Y are both oxygen; and R, is hydrogen; and R2 is hydrogen, C1C4alkyl, C3C4alekynl or C3C4alkynyl ; and R3 is CiC4alkyl, C3C4alkenyl or C3C4alkynyl ; and R4 is 3methoxy or 3ethoxy; and R5 is hydrogen; and B1 is selected fromCH2, CH (CH3) andC (CH3) 2 ; and n is the integer 1; and B2 isCH2CH2.
19. A compound according to claim 13 selected from the group comprising 2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> 2ethoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenyi2prop2ynyloxypropionamide,<BR> 3 (4chlorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, 3 (4chlorophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, 3 (4chlorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, 3 (4fluorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, 2ethoxy3(4fluorophenylN[2(3methoxy4prop2ynyloxyphenyl)ethyl]propionamide, 3(4fluorophenyl)N[2(3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, 3 (4bromophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, 3 (4bromophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, 3 (4bromophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, 3 (4bromophenyl)2ethoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy3ptolylpropionamide,<BR> <BR> <BR> 3 (4ethylphenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, <BR> <BR> <BR> 2ethoxy3 (4ethylphenyl)N [2 (3methoxy4prop2ynyioxyphenyl)ethyl]propionamide,<BR> <BR> <BR> (R)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> <BR> <BR> (R)2ethoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> <BR> <BR> (R)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenyl2prop2ynyloxy propionamide, <BR> <BR> <BR> (R)3 (4chlorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (R)3 (4chlorophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (R)3 (4chlorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (R)3 (4fluorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (R)2ethoxy3 (4fluorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> (R)3 (4fluorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (R)3(4bromophenyl)2hydroxyN[2(3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> (R)3 (4bromophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (R)3 (4bromophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (R)3 (4bromophenyl)2ethoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (R)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy3ptolyl propionamide, <BR> <BR> <BR> (R)3 (4ethylphenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (R)2ethoxy3 (4ethylphenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> (S)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (S)2ethoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenylpropionamide,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (S)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]3phenyl2prop2ynyloxy propionamide, <BR> <BR> <BR> (S)3 (4chlorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (S)3 (4chlorophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (S)3 (4chlorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (S)3 (4fluorophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (S)2ethoxy3 (4fluorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> <BR> (S)3 (4fluorophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (S)3 (4bromophenyl)2hydroxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, <BR> <BR> <BR> <BR> (S)3 (4bromophenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, (S)3 (4bromophenyl)2methoxyN [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (S)3(4bromophenyl)2ethoxyN[2(3methoxy4prop2ynyloxyphenyl)ethyl] propionamide, (S)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy3ptolyl propionamide, <BR> <BR> <BR> <BR> (S)3 (4ethylphenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl]2prop2ynyloxy propionamide, and (S)2ethoxy3 (4ethylphenyl)N [2 (3methoxy4prop2ynyloxyphenyl)ethyl] propionamide.
Description:
Novel a-Oxvgenated or a-Thiolated Carboxylic Acid Phenethvlamide Derivatives The present invention relates to novel agrochemical compositions comprising as active in- gredients at least one compound of the a-oxygenated or a-thiolated carboxylic acid phen- ethylamide derivatives of formula 1. It relates to the preparation of the active ingredients and to the novel compounds encompassed by the general formula 1. The invention further relates to the preparation of the agrochemical compositions and to the use of the compounds of formula I, or the use of the compositions for controlling or preventing the infestation of cultivated crop plants by phytopathogenic microorganisms, especially fungi.

The invention relates to microbiocidal a-oxygenated or a-thiolated carboxylic acid phenethylamide derivatives of the general formula I including the optical isomers thereof and mixtures of such isomers, wherein A stands for optionally substituted aryl or optionally substituted heteroaryl ; X is oxygen or sulfur ; Y is oxygen or sulfur ; Ri is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl or halocycloalkyl ; R2 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, alkoxy-alkyl, alkoxy- alkenyl, alkoxy-alkynyl, whereof all alkyl-alkenyl-, alkynyl-, or cycloalkyl-groups may be optionally substituted by halogen ; or optionally substituted aryl-alkyl, optionally substituted aryl-alkenyl, optionally substituted aryl-alkynyl or optionally substituted aryloxy-alkyl ; R3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, alkoxy-alkyl, alkoxy-alke- nyl, alkoxy-alkynyl, whereof all alkyl-alkenyl-, alkynyl-, or cycloalkyl-groups may be optio- nally substituted by halogen ; or is optionally substituted aryl-alkyl, optionally substituted aryl- alkenyl, optionally substituted aryl-alkynyl, optionally substituted aryloxy-alkyl, optionally substituted heteroaryl-alkyl, optionally substituted heteroaryl-alkenyl or optionally substituted heteroaryl-alkynyl ; R4 is alkyl, alkenyl, alkynyl, alkoxy-alkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkanoyl, alkylamino, dialkylamino, alkoxycarbonyl, whereof all alkyl-alkenyl or alkynyl-groups may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; R5 is hydrogen, alkyl, alkenyl or alkynyl ; n is an integer 0,1, 2,3, or 4; B, represents a bridge member-CR10R11-, wherein Rio and R1 independently of each other are hydrogen or alkyl ; and B2 is an alkylen bridge.

In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl like 1, 3-biphenyl and 1, 4-biphenyl, with phenyl being preferred. The same definition applies where aryl is part of aryloxy.

Heteroaryl stands for aromatic ring systems comprising mono-, bi-or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quin- oxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.

The above aryl and heteroaryl groups may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three sub- stituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy ; alkenyloxy ; alkynyloxy ; alkoxyalkyl ; haloalkoxy, alkylthio ; haloal- kylthio ; alkylsulfonyl ; formyl ; alkanol ; hydroxy; halogen ; cyano; nitro; amino; alkylamin ; dialkylamino ; carboxyl ; alkoxycarbonyl ; alkenyloxycarbonyl ; or alkynyloxycarbonyl. Typical examples include 4-chlorophenyl, 4-bromophenyl, 3, 4-dichlorophenyl, 4-chloro-3-fluorophe- nyl, 3-chloro-4-fluorophenyl, 4-methylphenyl, 4-ethylphenyl, 4-propargyloxyphenyl, 1-naph- thyl, 2-naphthyl, 4-biphenylyl, 4'-chloro-4-biphenylyl, 5-chloro-thien-2-yl, 5-methyl-thien-2-yl, 5-methyl-fur-2-yl, 5,6, 7, 8-tetrahydro-1-naphthyl, 5,6, 7, 8-tetrahydro-2-naphthyl, 3,4-dioxome- thylenyl-phenyl, 3, 4-dioxoethylenyl-phenyl, 6-benzothienyl, 7-benzothienyl, 3-methylphenyl, 4-fluorophenyl, 4-ethenylphenyl, 4-ethynylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-ethoxyphenyl, 4-ethynyloxyphenyl, 4-phenoxyphenyl, 4-methylthiophe- nyl, 4-methylsulfonylphenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxycarbonyl-phenyl, 3-bromophenyl, 3-chlorophenyl, 2-chlorophenyl, 2, 4-dichlorophenyl, 3,4, 5-trichlorophenyl, 3, 4-difluorophenyl, 3, 4-dibromophenyl, 3, 4-dimethoxyphenyl, 3, 4-dimethylphenyl, 3-chloro- 4-cyanophenyl, 4-chloro-3-cyanophenyl, 3-bromo-4-methylphenyl, 4-methoxy-3-methylphe- nyl, 3-fluoro-4-methoxyphenyl, 4-chloro-3-methylphenyl, 4-chloro-3-trifluoromethyl-phenyl, 4-bromo-3-chlorophenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-methoxyphe- nyl, 4'-methyl-4-biphenylyl, 4'-trifluoromethyl-4-biphenylyl, 4'-bromo-4-biphenylyl, 4'-cyano- 4-biphenylyl, 3'4'-dichloro-4-biphenylyl, etc.

Again, the same optional substituents may be present when aryl is part of aryloxy or arylthio.

Optionally substituted alkyl, alkenyl or alkynyl groups may carry one or more substituents selected from halogen, alkyl, alkoxy, alkylthio, cycloalkyl, phenyl, nitro, cyano, hydroxy, mer- capto, alkylcarbonyl or alkoxycarbonyl. This also applies where alkyl, alkenyl or alkynyl is part of another substituent like alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenylyoxy, alke- nylthio, alkenylsulfinyl, alkenylsufonyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl.

Preferably, the number of substituents is no more than three with the exception of halogen, where the alkyl groups may be perhalogenated.

In the above definitions"halo"or"halogen"includes fluorine, chlorine, bromine and iodine.

The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl-or alkynyl-containing groups.

Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.

Cycloalkyl for example is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, cycloheptyl, bicycloheptyl, cyclooctyl or bicyclooctyl.

Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a struc- tural element of other groups is to be understood as being, for example -CH=CH2,-CH2-CH=CH2,-CH=CH-CH3,-CH2-CH=CH-CH3,-CH2-CH2-CH=CH 2, -CH2-CH (CH3)-CH=CH2,-CH2-C (CH3) =CH2,-CH=CH- (CH2) 2-CH3, -CH2-CH2-CH=CH-CH3, -CH2-CH2-C (CH3) =CH-CH3, -CH (CH3)-CH2-CH=CH-CH3,-CH2-CH2-CH=CH-CH2-CH3, - CH=CH- (CH2) 3-CH3, -CH2-CH2-CH=C (CH3)-CH3,-CH2-CH2-CH=C (CH3)-CH2-CH3, -C (CH3) =CH2, -CH (CH3) -CH=CH2,-CH (CH3)-CH=CH-CH3,-CH (CH3)-CH2-CH=CH2, -CH2-CH (CH3) -C (CH3) =CH2,-CH2-C (CH3) =CH-CH3,-C (CH3) =CH- (CH2) 2-CH3, - CH (CH3) -CH2-C (CH3) =CH-CH3,-CH (CH3)- (CH2) 2-CH=CH2, -C (CH3) =CH- (CH2) 3-CH3, - CH (CH3)-CH2-CH=CH-CH2-CH3,- (CH2) 3-CH=CH2, -C (CH3) =CH-CH3, - CH (CH3) -CH2-C (CH3) =CH-CH3, or-CH (CH3)-CH2-CH=CH-CH2-CH3.

Alkynyl as a group or as a structural element of other groups is, for example -C-CH,-CH2-C_CH,-C_C-CH3,-CH2-C_C-CH3,-CH2-CH2-C--CH,-C--C-C H2-CH3, - CH2-CH (CH3)-C=CH,-C=C- (CH2) 2-CH3,-CH2-CH2-C=C-CH3,-CH (CH3)-CH2-C=C-CH3, <BR> <BR> <BR> <BR> -CH2-CH2-C_C-CH2-CH3,-C--C-(CH2) 3-CH3,-C_C-(CH2) 4-CH3, -CH (CH3)-C#CH,<BR> <BR> <BR> <BR> <BR> <BR> -CH(CH3)-C#C-CH3, -ch(C2H5)-C#C-CH3, -CH(CH3)-CH2-C#CH,-CH(CH3)-5CH2)2-C#CH, -CH(CH3)-CH2-C#C-CH2-CH3, -(CH2)3-C#CH, or-CH (CH3)-CH2-C-C-CH2-CH3, depending on the number of carbon atoms present.

A haloalkyl, haloalkenyl, haloalkynyl or halocycloalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCI2, CH2F, CCI3, CH2CI, CHF2, CF3, CH2CH2Br, C2CI5, CH2Br, CHCIBr, CF3CH2, CH2CH2CI, CH2CH2F, CH2CHF2, CH2-C=CHCI, CH=CCI2, CH=CF2, CH2-C=-CCI, CH2-C=C-CF3, etc.

B1 and B2 Characterize bivalent portions of the molecular structure of formula 1, which have the function of bridging members. Typically, these portions have a linear structure, but may also be branched and may carry further substituents. Examples include the bridge members of the formula-CH (R20)-(CH2)p- , wherein R20 stands for hydrogen or Ct-C4-alkyl and p is an integer 0 or 1 for the bridge B2, which belong to the generic group of alkylenes. Exam- ples for the Bu-bridge stand for an Ci-C4-alkylene bridge which links the adjacent part of the molecule of formula I to one single carbon atom. Typical examples for B2 include include -CH2- , -CH2-CH2- , -CH (CH3) -CH2-, -CH (CH3)-,-CH2-CH2-CH2-,-CH (CH3)-CH2- or -CH2-CH (CH3) -. Examples for the linking members for Bt include the linking members having only a single carbon atom as linking member. Typical examples encompass-CH2-, - CH (CH3) -,-CH (C2H5)- and-C (CH3) 2-.

The presence of at least one asymmetric carbon atom in the compounds of formula I means that the compounds may occur in optically isomeric and enantiomeric forms. As a result of the presence of a possible aliphatic C=C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof. Where no specific isomer is specified the mixtures of diastereomers or racemat is meant, as obtainable from the synthesis methods.

Preferred subgroups of compounds of formula I are those wherein A is phenyl, naphthyl, 1, 3-biphenyl, 1, 4-biphenyl, fluorenyl, tetralinyl, indanyl, methy- lendioxyphenyl, (1, 2-ethylene) dioxyphenyl, furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, indazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, quinolinyl or isoquinolinyl, each optionally sub- stituted by one or more substituents selected from the group comprising C1-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C1-C$-cycloalkyl, Cl-C8-cycloalkyl-C,-Co-alkyl, phenyl, phe- nyl-C1-C, o-alkyl, C,-C1o-alkoxy, C3-Cio-alkenyloxy, C3-Cio-alkynyloxy, C1-Cio-alkylthio, C1-C10-alkylsulfonyl, C1-C10-alkoxy-C1-C10-alkyl, C1-C10-alkanoyl,C1-C10-alkoxycarbonyl, C3-Cio-alkenyloxycarbonyl, C3-C10-alkynyloxycarbonyl, C1-C10-alkylamino, di-C1-C10-al- kylamino, hydroxy, halogen, cyano, nitro, amino and formyl radicals, wherein in turn the alkyl-alkenyl-, alkynyl-and cycloalkyl-groups may be optionally substituted by one or more halogen atoms; or A is phenyl, naphthyl, 1, 4-biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2-ethy- lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alke- nyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, benzyl, Ci-Cio-alkoxy, C1-Cio-haloalkoxy, C3-Cio-al- kenyloxy, C3-Cio-alkynyloxy, C1-C10-alkylthio, C1-C10-haloalkylthio, C1-C10-alkylsulfonyl, C1-C6-alkoxy-C1-C6-alkyl, Ci-Cio-alkanoyl, Ci-Cio-alkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl ; or A is phenyl, naphthyl, 1, 4-biphenyl, tetralinyl, indanyl, methylendioxyphenyl, thienyl, each optionally substituted by one, two or three substituents selected from the group comprising C1-Cio-alkyl, C1-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, benzyl, C1-Cio-al- koxy, C1-Cio-haloalkoxy, Ci-C1o-alkylthio, C1-Cio-haloalkylthio, Ci-Cio-alkanoyl, C1-Cio-al- koxycarbonyl, halogen, cyano, nitro and formyl ; or A is phenyl or thienyl, optionally substituted by one or two substituents selected from the group comprising C1-C4-alkyl, C1-C10-haloalkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-C10-al- kylthio, Ci-C4-alkanoyl, halogen and cyano; or A is phenyl, optionally substituted by one or two substituents selected from the group comprising Ct-C4-alkyl, Ci-C4-haloalkyl, halogen and cyano; or X is oxygen; or Y is oxygen; or R1 stands for hydrogen, C1-Cio-alkyl, C3-Cio-alkenyl, C3-Cio-alkynyl or C3-C8-cycloalkyl, wherein each alkyl-alkenyl-, alkynyl-and cycloalkyl-group may be optionally substituted by halogen ; or R1 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl, C1-C10-haloalkyl, C3-C10-ha- loalkenyl or C3-Cio-haloalkynyl ; or R1 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl or C3-C8-alkynyl ; or R1 is hydrogen; or R2 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl, C3-C8-cycloalkyl, C3-C8-cy- cloalkyl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C10-alkenyl or C1-C6-alk- oxy-C3-C10-alkynyl, wherein all alkyl- alkenyl-, alkynyl-, or cycloalkyl-groups may be optio- nally substituted by halogen ; or stands for optionally substituted aryl-Ct-C6-alkyl, optionally substituted aryl-C3-Cio-alkenyl, optionally substituted aryl-C3-Cio-alkynyl or optionally substituted aryloxy-C1-C6-alkyl ; or R2 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl, C3-C8-cycloalkyl, C3-C8-cy- <BR> <BR> <BR> cloalkyl-Ci-C6-alkyl, C3-C8-cycloalkyl-C3-C6-alkenyl, C3-C8-cycloalkyl-C3-C6-alkynyl, C1-C6-al- koxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C6-alkenyl, C1-C6-alkoxy-C3-C6-alkynyl, C1-C10-haloalkyl, C3-Cio-haloalkenyl, C3-C1o-haloalkynyl, phenyl-C1-C6-alkyl, phenyl-Ci-C6-alkenyl or phenyl- C1-C6-alkynyl, wherein phenyl may optionally be mono-or disubstituted by substituents selected from the group comprising C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkanoyl, C1-C6-alkoxycarbonyl, halogen, cyano, nitro and formyl ; or R2 stands for hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloal- kyl-C3-C4-alkynyl, C1-C4-alkoxy-C3-C4-alkynyl, C1-C8-haloalkyl or C3-C8-haloalkynyl ; or R2 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl-C3-C4-alkyl- nyl or Ci-C4-alkoxy-C3-C4-alkynyl ; or R2 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl or C3-C4-alkynyl ; or R3 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl, C3-C8-cycloalkyl, C3-C8-cy- cloalkyl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C10-alkenyl or C1-C6-alk- ixy-C3-C10-alkynyl, wherein all alkyl-alkenyl-, alkynyl-, or cycloalkyl-groups may be optio- nally substituted by halogen ; or is optionally substituted aryl-C1-C6-alkyl, optionally substi- tuted aryl-C3-Cio-alkenyl, optionally substituted aryl-C3-Cio-alkynyl, optionally substituted aryloxy-C1-C6-alkyl, optionally substituted heteroaryl-Ci-C6-alkyl, optionally substituted heteroaryl-C3-Cio-alkenyl or optionally substituted heteroaryl-C3-C10-alkynyl ; or R3 is hydrogen, C1-Cio-alkyl, C3-Cio-alkenyl, C3-C1o-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Ci-C6-alkyl, C3-C8-cycloalkyl-C3-C6-alkenyl, C3-C8-cycloalkyl-C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C6-alkenyl, C1-C6-alkoxy-C3-C6-alkynyl, C1-C10-ha- loalkyl, C3-C10-haloalkenyl, C3-C10-haloalkynyl, phenyl-C1-C6-alkyl, phenyl-C1-C6-alkenyl or phenyl-Ct-C6-alkynyl, wherein the phenyl groups are optionally mono-or disubstituted by radicals selected from the group comprising C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkanoyl, C1-C6-alkoxycarbonyl, halogen, cyano, nitro and formyl ; or R3 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl-C3-C4-alky- nyl, C1-C4-alkoxy-C3-C4-alkynyl, C1-C8-haloalkyl or C3-C8-haloalkynyl ; or R3 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl-C3-C4-alky- nyl or Ct-C4-alkoxy-C3-C4-alkynyl ; or R3 is C1-C4-alkyl, C3-C4-alkenyl or C3-C4-alkynyl ; or R4 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, Ci-C6-alkylthio, C1-C6-alkanoyl, C1-C6-alkylamino, dl-C1-C6-alkylamino or C1-C6-alkoxycarbonyl, wherein each alkyl-alkenyl or alkynyl-group may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; or R4 is Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6alkylthio, halogen, cyano or nitro; or R4 is C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or halogen ; or R4is 3-Ct-C6-alkoxy ; or R4 is 3-methoxy or 3-ethoxy; or R5 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl ; or R5 is hydrogen or C1-C4-alkyl ; or R5 is hydrogen or methyl ; or R5 is hydrogen; or B1 stands for a bridge member-CR10R11-, wherein Rio and R11 independently of each other are hydrogen or Ci-C4-alkyl ; or B1 is selected from-CH2-, -CH (CH3)- and-C (CH3) 2- ; or n is an integer from 0 to 2; or n is the integer 0 or 1; or n is the integer 1; or B2 is an Ci-C6-alkylene-bridge ; or B2 is an alkylene-bridge of the formula-CH(R20)-(CH2)p- , wherein R20 stands for hydrogen or Ci-C4-alkyl and p is an integer 0,1 or 2; or B2 is -CH2-CH2-, CH2-, CH (CH3)-CH2- or CH (CH3)- ; or B2 is -CH2-CH2-.

Further preferred subgroups are those wherein A is phenyl, naphthyl, 1, 3-biphenyl, 1, 4-biphenyl, fluorenyl, tetralinyl, indanyl, methy- lendioxyphenyl, (1, 2-ethylene) dioxyphenyl, furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, indazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, quinolinyl or isoquinolinyl, each optionally substituted by one or more substituents selected from the group comprising Ci-C1o-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, d-Cs-cyctoatkyt, C1-C8-cycloalkyl-C1-C10-alkyl, phenyl, phe- nyl-C1-C10-alkyl, C1-C10-alkoxyl, C3-C10-alkenyloxy, C3-C10-alkynyloxy, C1-C10-alkylthio, C, C10-alkylsulfonyl, C1-C10alkoxy-C1-C10-alkyl, C1-C10-alkanoyl, C1-C10-alkoxycarbonyl, C3-Cio-alkenyloxycarbonyl, C3-Cio-alkynyloxycarbonyl, C1-C10-alkylamino, di-C1-C10-al- kylamino, hydroxy, halogen, cyano, nitro, amino and formyl radicals, wherein in turn the alkyl-alkenyl-, alkynyl-and cycloalkyl-groups may be optionally substituted by one or more halogen atoms; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R, stands for hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl or C3-C8-cycloalkyl, wherein each alkyl-alkenyl-, alkynyl-and cycloalkyl-group may be optionally substituted by halogen ; and R2 is hydrogen, C1-Cio-alkyl, C3-C1o-alkenyl, C3-Cio-alkynyl, C3-Cs-cycloalkyl, C3-C8-cycloal- kyl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C10-alkenyl or C1-C6-alk- oxy-C3-C10-alkynyl, wherein all alkyl-alkenyl-, alkynyl-, or cycloalkyl-groups may be optio- nally substituted by halogen ; or stands for optionally substituted aryl-C1-C6-alkyl, optionally substituted aryl-C3-C10-alkenyl, optionally substituted aryl-C3-Cio-alkynyl or optionally substi- tuted aryloxy-C-C6-alkyl ; and R3 is hydrogen, C1-Cio-alkyl, C3-Cio-alkenyl, C3-C, o-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C1-C6-alkoxy-C3-C10- alkenyl or C1-C6-alkoxyl-C3-C10-alkynyl, wherein each alkyl-alkenyl-, alkynyl-, or cycloalkyl- group may be optionally substituted by halogen ; or is optionally substituted aryl-C1-C6-alkyl, optionally substituted aryl-C3-C10-alkenyl, optionally substituted aryl-C3-Ct0-alkynyl, optio- nally substituted aryloxy-Ci-C6-alkyl, optionally substituted heteroaryl-Ci-C6-alkyl, optionally substituted heteroaryl-C3-C10-alkenyl or optionally substituted heteroaeyl-C3-C10-alkynyl ; and R4 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkylthio, Ci-C6-alkanoyl, C1-C6-alkylamino, di-C1-C6-alkylamino or C1-C6-alkoxycarbonyl, wherein each alkyl-alkenyl or alkynyl-group may be optionally substituted by halogen ; or is halogen, cyano, nitro, amino, formyl or carboxyl ; and R5 is hydrogen, Ci-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl ; and and B2 is an C1-C6-alkylene-bridge ; and n is an integer from 0 to 2.

Among these compounds those are preferred wherein A is phenyl, naphthyl, 1,4-bi- phenyl, tetralinyl, indanyl, methylendioxyphenyl, (1, 2-ethylene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising Ci-Cio-alkyl, C1-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, benzyl, C1-C10-alkoxy, C1-C10-haloalkoxy, C3-C10-alkenyloxy, C3-C10-alky- <BR> <BR> <BR> nyloxy, C1-C1o-alkylthio, Ci-Cio-haloalkylthio, Ci-C1o-alkylsulfonyl, C1-C6-alkoxy-C,-C6-alkyl, C1-Cio-alkanoyl, C1-C10-alkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl.

Further preferred subgroups are those wherein A is phenyl, naphthyl, 1, 4-biphenyl, tetralinyl, indanyl, methylendioxyphenyl, (1,2-ethy- lene) dioxyphenyl, furanyl, thienyl or pyridyl, each optionally substituted by one, two or three substituents selected from the group comprising Ci-Cjo-alkyl, Ci-Cio-haloalkyl, C2-Cio-al- kenyl, C2-C, o-haloalkenyl, C2-Cio-alkynyl, benzyl, Ci-Cio-alkoxy, C1-Cio-haloalkoxy, <BR> <BR> <BR> C3-Cio-alkenyloxy, C3-Cio-alkynyloxy, C1-C1o-alkylthio, Ci-Cio-haloalkylthio, C1-Cio-alkylsul- fonyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C10-alkanoyl, C1-C10-alkoxycarbonyl, hydroxy, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R1 is hydrogen, C1-Cio-alkyl, C3-C1o-alkenyl, C3-C, o-alkynyl, Ci-Cio-haloalkyl, C3-Cio-haloalkenyl or C3-Cio-haloalkynyl ; and R2 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-lakynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C3-C8-cycloalkyl-C3-C6-alkenyl, C3-C8-cycloal- kyl-C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, Ci-C6-alkoxy-C3-C6-alkenyl, C1-C6-alkoxy- <BR> <BR> <BR> C3-C6-alkynyl, C1 Cio-haloalkyl, C3-Cio-haloalkenyl, C3-C1o-haloalkynyl, phenyl-Ci-C6-alkyl, phenyl-C1-C6-alkenyl or phenyl-Ci-C6-alkynyl, wherein phenyl may optionally be mono-or disubstituted by substituents selected from the group comprising C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-al- kanoyl, C1-C6-alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R3 is hydrogen, C1-C10-alkyl, C3-C10-alkenyl, C3-C10-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, C3-C8-cycloalkyl-C3-C6-alkenyl, C3-C8-cycloalkyl-C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C3-C6-alkenyl, C,-C6-alkoxy-C3-C6-alkynyl, Ci-Cio-haloalkyl, C3-Cio-haloalkenyl, C3-C10-haloalkynyl, phenyl-C1-C6-alkyl, phenyl-C1-C6-alkenyl or phenyl-C1-C6-alkynyl, wherein the phenyl groups are optionally mono-or disubstituted by radicals selected from the group comprising C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyluhio, C1-C6-haloalkylthio, C1-C6-alkanoyl, C1-C6-alkoxycarbonyl, halogen, cyano, nitro and formyl ; and R4 is C1-C6-alkyl, Ci-C6-haloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6alkylthio, halogen, cyano or nitro; and R5 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl ; and n is an integer from 0 to 2; and B2 is an alkylene-bridge of the formula-CH (R20)-(CH2)p- , wherein R20 stands for hydrogen or Ci-C4-alkyl and p is an integer 0,1 or 2; or wherein A is phenyl, naphthyl, 1, 4-biphenyl, tetralinyl, indanyl, methylendioxyphenyl, thienyl, each optionally substituted by one, two or three substituents selected from the group comprising C1-C10-lkyl, C1-C10-haloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, benzyl, C1-C10-al- koxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkanoyl, C1-Cio-al- koxycarbonyl, halogen, cyano, nitro and formyl ; and X is oxygen or sulfur ; and Y is oxygen or sulfur ; and R, is hydrogen, C1-C8-alkyl, C3-C8-alkenyl or C3-C8-alkynyl ; and R2 stands for hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl-C3-C4-alkynyl, C1-C4-alkoxy-C3-C4-alkynyl, Ci-C8-haloalkyl or C3-C8-haloalkynyl ; and R3 is hydrogen, C1-C8-alkyl, C3-C8-alkynyl, C3-C8-alkynyl, C3-C8-cycloalkyl-C3-c4-alkynyl, C1-c4-al- koxy-C3-C4-alkynyl, C,-C8-haloalkyl or C3-C8-haloalkynyl ; and R4 is C1-c6-alkoxy, C3-C6-al- kenyloxy, C3-C6-alkynyloxy or halogen ; and R5 is hydrogen or C, C4 alkyl ; and B, stands for -CH2-,-CH (CH3)-or-C (CH3) 2- ; and n is the integer 0 or 1; and B2 is an alkylene-bridge of the formula-CH (R20)-(CH2) p-, wherein R20 stands for hydrogen or C-C4 alkyl and p is an integer 0,1 or 2; or wherein A is phenyl or thienyl, optionally substituted by one or two substituents selected from the group comprising C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-c10-al- kylthio, C,-C4-alkanoyl, halogen and cyano; and X is oxygen; and Y is oxygen; and Ri is hydrogen, C1-c8-alkyl, C3-C8-alkenyl or C3-C8-alkynyl ; and R2 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynykl, C3-C6-cycloalkyl-C3-C4-alkynyl or C1-c4-alkoxy-C3-C4-alkynyl ; and R3 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl-C3-C4-alkynyl or C-C4-alkoxy-C3-C4-alkynyl ; and R4 is 3-C,-C6-alkoxy ; and R5 is hydrogen or methyl ; and B, is selected from-CH2-,-CH (CH3)- and-C (CH3) 2- ; and n is the integer 0 or 1; and B2 is - CH2-CH2-, CH2-, CH (CH3)-CH2- or CH (CH3)- ; or wherein A is phenyl, optionally substituted by one or two substituents selected from the group comprising C1-C4-alkyl, C1-C4-haloalkyl, halogen and cyano; and X and Y are both oxygen; and Ri is hydrogen; and R2 is hydrogen, Ci-C4-alkyl, C3-C4-alkenyl or C3-C4-alkynyl ; and R3 is Ci-C4-alkyl, C3-C4-alkenyl or C3-C4-alkynyl ; and R4 is 3-methoxy or 3-ethoxy; and R5 is <BR> <BR> <BR> hydrogen; and Bi is selected from-CH2-, -CH (CH3)- and-C (CH3) 2- ; and n is the integer 1; and B2 is-CH2-CH2-- Preferred individual compounds are: <BR> <BR> <BR> 2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-propiona mide,<BR> <BR> <BR> <BR> <BR> 2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-propiona mide,<BR> <BR> <BR> <BR> N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-2-prop-2 -ynyloxy-propionamide,<BR> <BR> <BR> <BR> <BR> 3- (4-chloro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, 3- (4-chloro-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, 3- (4-chloro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, 3- (4-fluoro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, <BR> <BR> <BR> 2-ethoxy-3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-propionamide,< BR> <BR> <BR> <BR> 3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, 3- (4-bromo-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, 3- (4-bromo-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, 3- (4-bromo-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, 3- (4-bromo-phenyl)-2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, <BR> <BR> <BR> N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- 3-p-tolyl-propionamide,<BR> <BR> <BR> <BR> <BR> 3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, and <BR> <BR> <BR> 2-ethoxy-3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-propionamide.

The optically pure enantiomers of these compounds are mostly obtained as mixtures of the R-and S-forms. It is however possible to obtain the pure enantiomers either by classical separation methods or by stereoselective synthesis methods. In practical preparation enantio-enriched mixture of both forms may be obtained, while on laboratory scale analytically pure enatiomers may be obtained, such as: <BR> <BR> <BR> <BR> <BR> (R)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyi-propiona mide,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (R)-2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-propiona mide,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> (R)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-2-prop-2 -ynyloxy- propionamide, <BR> <BR> <BR> <BR> <BR> (R)-3- (4-chloro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyi)-ethyl]-2-prop-2-ynyloxy- propionamide, (R)-3- (4-chloro-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (R)-3- (4-chloro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (R)-3- (4-fluoro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (R)-2-ethoxy-3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, <BR> <BR> <BR> <BR> <BR> (R)-3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (R)-3- (4-bromo-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, <BR> <BR> <BR> <BR> <BR> (R)-3- (4-bromo-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (R)-3- (4-bromo-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (R)-3- (4-bromo-phenyl)-2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (R)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- 3-p-tolyl- propionamide, <BR> <BR> <BR> <BR> <BR> (R)-3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (R)-2-ethoxy-3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide.

(S)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-propiona mide, (S)-2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-propiona mide,<BR> (S)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-2-prop-2 -ynyloxy- propionamide, (S)-3- (4-chloro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (S)-3- (4-chloro-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-3- (4-chloro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-3- (4-fluoro-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-2-ethoxy-3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-3- (4-fluoro-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (S)-3- (4-bromo-phenyl)-2-hydroxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-3- (4-bromo-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, (S)-3- (4-bromo-phenyl)-2-methoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-3- (4-bromo-phenyl)-2-ethoxy-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide, (S)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- 3-p-tolyl- propionamide, (S)-3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy- propionamide, and (S)-2-ethoxy-3- (4-ethyl-phenyl)-N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]- propionamide.

Certain mandelic acid derivatives have been proposed for controlling plant-destructive fungi (for example in WO 94/29267 in WO 96/17840 and in PCT/EP01/05530). The action of those preparations is not, however, satisfactory in all aspects and needs of the agricultural practices. Surprisingly, with the compound structure of formula 1, new kinds of microbiocides having a high level of activity have been found.

Some of the compounds of formula I are described in the literature as pharmacologi- cally active compounds. Though they have now been found to be useful as plant protec- tants, these compounds will not be subject of the group of claimed novel compounds. The known pharmacologically active compounds falling within the scope of formula I have been isolated as natural products and disclosed by G. R. Pettit et al. in J. Nat. Prod, 1996, (59), pp. 927-934. In this disclosure the compounds are designated as Hemibastadinols, and have the chemical designations follows. : 2-hydroxy-N- [2- (3-bromo-4-hydroxy-phenyl)-ethyl]-3- (3-bromo-4-hydroxy-phenyl)- propionamide, 2-hydroxy-N- [2- (3-bromo-4-methoxy-phenyl)-ethyl]-3- (3-bromo-4-methoxy-phenyl)- propionamide, 2-hydroxy-N- [2- (3-bromo-4-methoxy-phenyl)-ethyl]-3- (3, 5-dibromo-4-hydroxy-phenyl)- propionamide, 2-hydroxy-N- [2- (3, 5-dibromo-4-hydroxy-phenyl)-ethyl]-3- (3-bromo-4-hydroxy-phenyl)- propionamide, 2-hydroxy-N- [2- (3, 5-dibromo-4-methoxy-phenyl)-ethyl]-3- (3-bromo-4-methoxy-phenyl)- propionamide, and 2-hydroxy-N- [2- (3-bromo-4-methoxy-phenyl)-ethyl]-3- (3, 5-dibromo-4-methoxy-phenyl)- propionamide.

The compounds of formula I may be obtained according to one of the processes of Schemes 1 to 5: Scheme 1: R2 (R4) n Y O /i \ AB+LOH + H-i-B2/\ O-H R5 (III) step A 2 (Rn R 1 r (R4) n lR2 1 2 1 1 A-B--u-O-H , Ri (IV) R, R Z4\tep B steH + (R4) n step B step C 3 v O-Rs IR2 (R4) n R5 (Vl I) Y O 0 -Bi- N-B-6-0-R I Ri Rs (IA) Step A: An acid of formula 11 or a carboxy-activated derivative of an acid of formula 11 wherein A, Bi, R1, R2 and Y are as defined for formula I is reacted with an amine of formu- la III wherein B2, R4 and R5 are as defined for formula 1, optionally in the presence of a base and optionally in the presence of a diluting agent.

Carboxy-activated derivatives of the acid of formula 11 are all compounds having an activa- ted carboxyl group like an acid halide, such as an acid chloride; like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates ; like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, or even normal esters, such as methyls- ters, ethylesters, n-propylesters, iso-propylesters, n-butylesters, tert-butylesters, neo-pen- tylesters or iso-amylesters ; as well as in-situ-formed activated forms of the acid of formula 11 with condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazole, benzotri- azol-1-yloxy-tris (dimethylamino) phosphonium hexafluorophosphate, O-benzotriazol-1- yl-N, N, N', N'-bis (pentamethylene) uronium hexafluorophosphate, O-benzotriazol-1-yl- N, N, N', N'-bis (tetramethylene) uronium hexafluorophosphate, O-benzotriazol-1-yl-N, N, N', N'- tetramethyluronium hexafluorophosphate or benzotriazol-1-yloxy-tripyrrolidinophosphonium hexafluorophosphate. The mixed anhydrides of the acids of the formula 11 may be prepared by reaction of an acid of formula 11 with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N, N-diisopropyl- ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.

The present reaction is preferably performed in a solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e. g. dichloromethane or toluene ; ketones e. g. acetone; esters e. g. ethyl acetate; amides e. g. N, N-dimethylformamide ; nitriles e. g. acetonitrile ; or ethers e. g. diethylether, tert-butyl-methylether, dioxane or tetrahydro- furan or water. It is also possible to use mixtures of these solvents. The reaction is perfor- med optionally in the presence of an organic or inorganic base like a tertiary amine, e. g. triethylamine, N, N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-mor- pholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from-80°C to +150 °C, preferentially at temperatures ranging from - 40°C to +40°C.

Step B: The compounds of formula IA may be prepared as final product by reacting a phenol of formula IV wherein A, B1, B2, Ri, R2, R4, R5 and Y are as defined for formula I with a compound of formula V wherein R3 is as defined for formula I and wherein Z is a leaving group like a halide such as chloride or bromide or a sulfonic ester such as a tosylat, mesylate or triflate.

The reaction is advantageously performed in a solvent like aromatic, non-aromatic or halo- genated hydrocarbons, such as chlorohydrocarbons e. g. dichloromethane or toluene; ketones e. g. acetone or 2-butanone; esters e. g. ethyl acetate, ethers e. g. diethylether, tert- butyl-methylether, dioxane or tetrahydrofuran ; amides e. g. N, N-dimethylformamide ; nitriles e. g. acetonitrile ; alcohols e. g. methanol, ethanol, isopropanol, n-butanol or tert-butanol ; sulf- oxides e. g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents.

The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N, N-diisopropyl-ethylamine, pyridine, N-methyl-piperi- dine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbo- nate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from-80°C to +200°C, preferentially at temperatures ranging from 0°C to +120°C.

Step C: Alternatively to step A and step B, an acid of formula 11 or a carboxy-activated derivative of an acid of formula II wherein A, Bt, Ri, R2 and Y are as defined for formula I is reacted with an amine of formula VII wherein B2, R3, R4 and R5 are as defined for formula I under the same conditions as defined for step A, optionally in the presence of a base and optionally in the presence of a diluting agent.

Scheme 2: xu ll R (R4) n o OH R43 _ (R4) n (XI) O O O-R3 ste F A Bi H-B2 O-Rs (Xlil) ( ) i (X) Ri (Xl) step I step G R4n tR4O o X OH O (IX) Rr (XIV) H \/"stepH H \/ R (XIV) j step D Z-R3 (V) step K Z-R2 (XV) ZOZO 0 L 0 0 ! 0 0 0 H 11 N-B2-6-OH A-B N-B2-6-0-R3 (Vlil) 1 s (IB) Step D: A compound of formula VIIl wherein B2 and R4 are as defined for formula I is alkylated with a compound of formula V (see Scheme 1) wherein R3 and Z are as defined for Scheme 1 under the same conditions as defined for step B in Scheme 1.

Step E: A compound of formula IX wherein B2, R3 and R4 are as defined for formula I is dehydrated to an isocyanide of formula X wherein B2, R3 and R4 are as defined for formula I under conditions known perse (D. Seebach, G. Adam, T. Gees, M. Schiess, W. Weigang, Chem. Ber. 1988, 121, 507).

Step F: An isocyanide of formula X wherein B2, R3 and R4 are as defined for formula I is reacted in a three-component Passerini reaction (J. March, Advanced Organic Chemistry, 5th ed., Wiley, 2001, p. 1252) with an aldehyde or ketone of formula XI, wherein A, B, and Ri are as defined for formula I in the presence of a carboxylic acid XII wherein R6 is hydrogen or lower alkyl, typically acetic acid, to give a 0-acyl-a-hydroxy amide of formula XIII, wherein A, B1, B2, Ri, R3 and R4 are as defined for formula I and R6 is hydrogen or lower alkyl.

Step G: Alternatively to step F, an isocyanide of formula X wherein B2, R3 and R4 are as defined for formula I is reacted with an aldehyde or ketone of formula XI wherein A, B, and R1 are as defined for formula I in the presence of titanium tetrachloride to give an a-hydroxy amide of the formula XIV (where A, Bl, B2, R1, R3 and R4 have the same meaning as defined above) under conditions known per se (D. Seebach, G. Adam, T. Gees, M. Schiess, W. Weigang, Chem. Ber. 1988, 121, 507; O. Ort, U. D6 ! ! er, W. Reissel, S. D. Lindell, T. L.

Hough, D. J. Simpson, J. P. Chung, Pesticide Sci. 1997,50, 331).

Step H: Alternatively to step E and step F, a compound of formula IX, wherein B2, R3 and R4 are as defined for formula I is treated with one phosgene equivalent (e. g. triphosgene) and a base (e. g. triethylamine) and in a second step, without isolation of the isocyanide intermediate, is further treated with titanium tetrachloride and an aldehyde or ketone of formula Xi, wherein A, B1 and Ri are as defined for formula I under conditions known perse (WO 96/17840) to give an a-hydroxy amide of the formula XIV, wherein A, B1, B2, Ri, R3 and R4 are as defined for formula 1.

Step) : An 0-acyl-a-hydroxy amide of formula XIII wherein A, B1, B2, Ri, R3 and R4 are as defined above and R6 is hydrogen or lower alkyl is hydrolyzed to an a-hydroxy amide of formula XIV, wherein A, B1, B2, Ri, R3 and R4 are as defined for formula I under classical conditions (J. March, Advanced Organic Chemistry, 4th ed., Wiley, 1992).

Step K: An a-hydroxy amide of formula XIV wherein A, B1, B2, R1, R3 and R4 are as defined for formula I is reacted with a compound XV wherein R2 is alkyl, alkenyl or alkynyl and Z is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylat, mesylate or triflate to a compound of formula IB wherein A, B1, B2, R1, R2, R3 and R4 are as defined for formula I and under the same conditions as defined for step B in Scheme 1.

Scheme 3: Preparation of a-hydroxy-acids (examples of formula ll) : H O (XVIII) H2c=o-R, H O A-NH2 A O-R (XIX) (XVII) step L H CL step M H 0 H 0 A OH (XX) H OH Step L: An amine of formula XVII wherein A is as defined for formula I is reacted with an acrylic acid derivative of formula XVIII, wherein R7 is hydrogen or lower alkyl in the pre- sence of sodium nitrate, hydrochloric acid and a copper salt such as copper (l) bromide or copper (l) iodide to give an a-chloro-acid derivative of formula XIX, wherein A is as defined for formula I and R7 is hydrogen or lower alkyl under conditions known per se (D. Haigh, L.

J. Jefcott, K. Magee, H. McNab, J. Chem. Soc., Perkin Trans. I 1996, 2895).

Step M: An a-chloro-acid derivative of formula XIX wherein A is as defined for formula I and R7 is hydrogen or lower alkyl is then hydrolyzed to an a-hydroxy-acid of formula XX wherein A is as defined for formula I with a strong alkali base like sodium hydroxide or potassium hydroxide in the presence of a weaker base such as sodium bicarbonate, sodium carbo- nate, potassium carbonate or calcium carbonate under conditions known perse (D. Haigh, L. J. Jefcott, K. Magee, H. McNab, J. Chem. Soc. , Perkin Trans. I 1996, 2895).

Scheme 4: R2 (R4) 11 Y O I g- -g2 -R3 (IC) Pi H5 Sulfurating agent step S vs A-B oR3 (ID) Y S A ! Ruz K5 Ri Rs Step S: An amid of formula VI wherein A, Bi, B2, Ri, R2, R3, R4, and Rs are as defined above is transformed to a thioamide of formula XXX, wherein A, B1, B2, Ri, R2, R3, R4, and R5 are as defined for formula I with a sulfurating agent, like a phosphorus sulfur compound, e. g. phosphorus pentasulfide or 2,4-bis (4-methoxyphenyl)-1, 3-dithia-2,4-diphosphetane-2, 4- disulfide (Lawesson's reagent), in an inert diluting agent, like an inert organic solvent such as aromatic, non aromatic or halogenated hydrocarbons, e. g. benzene, toluene, xylene, chlorobenzene or chloroform, at temperatures ranging from-80 °C to +200 °C, preferably at temperatures ranging from 0 to +100 °C.

Scheme 5: n Y O /I \ A-B -u-i-B2/\ O-R3 (XXXI) . I R, Rs stepT | ZR2 (XV) (R 4). zozo A-B N-B O-R 3 (IB) 2 1 Z-R 2 (V) V=XV step U z-R3 (XV) I (R 4). Y 0 A-Bi-1--y'-i-B2 OH (XXXII) Ri R 5 Step T: An amid of formula IB wherein A, B1, B2, Ri, R2, R3, R4, R5 and Y are as defined for formula I may be obtained by reaction of an amide of formula XXXI, wherein A, Bi, B2, Ri, R3, R4, R5 and Y are as defined for formula I with a compound of formula XV wherein R2 is as defined for formula I and wherein Z is a leaving group like a halide such as chloride or bromide or a sulfonic ester such as a tosylat, mesylate or triflate under the same conditions as defined for step B in Scheme 1.

Step U: An amide of formula XXXII wherein A, Bi, B2, Ri, R4 and Y are as defined for formula I is reacted with a compound XV wherein R2 is as defined for formula I and Z is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylat, mesylate or triflate and which is equal to a compound V wherein R3 is as defined for formula I and Z is also a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylat, mesylate or triflate to a compound of formula IB wherein A, Bi, B2, Ri, R2, R3, R4 and Y are as defined for formula I and under the same conditions as defined for step B in Scheme 1.

The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related fields preventatively and curatively in the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concen- tration not only by outstanding microbiocidal, especially fungicidal, activity but also by being especially well tolerated by plants.

Surprisingly, it has now been found that the compounds of formula I have for practical purposes a very advantageous microbiocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. They possess very advantageous curative and preventive properties and are used in the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phytopathogenic fungi.

The novel compounds of formula I prove to be effective against specific genera of the fungus class Fungi imperfecti (e. g. Cercospora), Basidiomycetes (e. g. Puccinia) and Ascomycetes (e. g. Erysiphe and Venturia) and especially against Oomycetes (e. g.

Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phytopathogenic fungi. The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.

The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agri- cultural sector or related fields.

In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distin- guished by the application of the novel compounds of formula I or of the novel compositions.

Target crops to be protected within the scope of this invention comprise, for example, the following species of plants : cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and black- berries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbi- taceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.

The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application- promoting adjuvants customarily employed in formulation technology.

The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Such mixtures are not limited to two active ingredients (one of formula I and one of the list of other fungicides), but to the contrary many comprise more than one active ingredient of the component of formula I and more than one other fungicide. Mixing components which are particularly suited for this purpose include e. g. azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebucon- azole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole ; pyrimidinyl carbi- noles, such as ancymidol, fenarimol, nuarimol ; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol ; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil ; pyrroles, such as fenpiclonil, fludioxonil ; phenylamides, such as benalaxyl, furalaxyl, meta- laxyl, R-metalaxyl, ofurace, oxadixyl ; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole ; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline ; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide ; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metomi- nostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostro- bin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid ; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine- copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl ; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-me- thyl ; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazof- amid), kasugamycin, methasulfocarb, metrafenone, nicobifen (new proposal: boscalid), pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

In the above mentioned mixtures, the mixture ratio of the active ingredients is so selected that it reaches optional control of the phytopathogenic microorganism on the host plants.

This ratio is in general between 100: 1 and 1: 100, more preferably between 10: 1 and 1: 10 of a compound of formula I vis-a-vis the second fungicide. The mixtures may not only comprise one of the listed combinational active ingredients, but may comprise more than one additional active ingredients selected from that specified group, thus forming for example 3-way-or even 4-way-mixtures.

Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e. g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.

A preferred method of applying a compound of formula 1, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e. g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e. g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended object- ives and the prevailing circumstances.

Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a. i.) per hectare (ha), preferably from 10 g to 1 kg a. i. /ha, especially from 25 g to 750 g a. i./ha.

When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.

The formulations, i. e. the compositions, preparations or mixtures comprising the com- pound (s) (active ingredient (s) ) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e. g. by homogeneously mixing and/or grinding the active ingredient with extenders, e. g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.

The agrochemical compositions usually comprise 0.01 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula 1, 99.99 to 1 % by weight, preferably 99.9 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples illustrate the described invention, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius. Ph stands for phenyl.

Preparation Examples : Example E1 : N-[2-(3-Methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-2-p rop-2-ynyloxy. butyramide a) N-f2- (4-Hydroxv-3-methoxv-phenvl)-ethvll-formamide Formic acid (230 g, 5.0 mol) is added dropwise to acetic anhydride (383 g, 3.75 mol) at 0°C.

This mixture is stirred for 2 hours at +55°C and subsequently cooled again to 0°C. Tetrahy- drofuran (500 ml) is added at this temperature followed by 4- (2-amino-ethyl)-2-methoxy- phenol hydrochloride (50 g, 0.25 mol). The resulting white suspension is stirred for 18 hours at +75 °C, changing into a yellow solution. The reaction mixture is evaporated and the resi- due is submitted to flash-chromatography to yield N [2- (4-hydroxy-3-methoxy-phenyl)-ethyl]- formamide.

'H-NMR (300 MHz, CDC13) : 2.85 (t, 2H, CH2CH2), 3.57 (t, 2H, CH2CH2), 3.82 (s, 3H, OCH3), 5.69 (bs, 1H, NH), 6.67-7. 09 (m, 3H, CH arom. ), 8.12 (s, 1H, CHO). b) N-f2- (3-Methoxy-4-prop-2-vnvloxv-phl)-ethvll-formamide Sodium methoxide (32 ml of a 5.4 M solution in methanol, 0.17 mol) is added to a solution of N- [2- (4-hydroxy-3-methoxy-phenyl)-ethyl]-formamide (32g, 0. 16 mol) in methanol (400 ml). Propargyl bromide (20 g, 0.17 mol) is added and the mixture is refluxed for 4 hours.

After evaporation the residue is taken up in ethyl acetate (400 ml) and washed with water (2 x 200 ml). The organic layer is dried over magnesium sulfate and evaporated. The residue is submitted to flash-chromatography to give the N [2- (3-methoxy-4-prop-2-ynyloxy- phenyl)-ethyl]-formamide. 'H-NMR (300 MHz, CDCI3) : 2.44 (t, 1H, C=CH), 2.73 (t, 2H, CH2CH2), 3.51 (t, 2H, CH2CH2), 3.82 (s, 3H, OCH3), 4.69 (m, 2H, OCH2), 5.53 (bs, 1 H, NH), 6.62-6. 95 (m, 3H, CH arom.), 8.09 (s, 1 H, CHO). c) 2-Hvdroxv-111 f2- (3-methoxv-4-prop-2-vnvloxv-phenyl)-ethvll-3-phenvl-butvrami de N [2- (3-Methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-formamide (8.0 g, 34 mmol) and triethyl- mine (8.3 g, 82 mmol) are dissolved in dichloromethane (80 ml). Bis (trichloromethyl) carbo- nate (triphosgene, 4.0 g, 14 mmol) in dichloromethane (40 ml) is added at +5°C. The mix- ture is stirred for 4 hours at +5°C and then cooled to-78°C. A solution of titanium tetrachlo- ride (7.0 g, 38 mmol) in dichloromethane (70 ml) is added and the mixture is stirred for 2 hours at-40°C. 2-Phenylpropionaldehyde (4.8 g, 36 mmol) in dichloromethane (50 ml) is added dropwise and the mixture is stirred for 17 hours at room temperature. The mixture is hydrolyse with 5N HCI (25 ml), stirred 30 minutes at room temperature and washed with water. After evaporation of the organic layer the residue is submitted to flash-chromatogra- phy (ethyl acetate/hexane 6: 3) to give 2-hydroxy-N [2- (3-methoxy-4-prop-2-ynyloxy- phenyl)-ethyl]-3-phenyl-butyramide (E1. 23).

'H-NMR (300 MHz, CDCI3) : 1.26 (d, 3H, CH3), 2.52 (t, 1H, C=CH), 2.76 (t, 2H, CH2CH2), 3.36-3. 61 (m, 3H, CH, CH2CH2), 3.90 (s, 3H, OCH3), 4.19 (m, 1 H, CHO), 4.78 (d, 2H, OCH2), 6.71-7. 38 (m, 9H, NH, CH arom.). c) A 80 % solution of propargyl bromide in toluene (1.2 g, 7.8 mmol) is added slowly at room temperature to a mixture of 2-hydroxy-N [2- (3-methoxy-4-prop-2-ynyloxy-phenyl)- ethyl]-3-phenyl-butyramide (2.4 g, 6.5 mmol), 30 % sodium hydroxide solution (6.0 ml, 33 mmol) and catalytic amounts of tetrabutylammonium bromide (50 mg) in 25 mi of dichloro- methane. The reaction is stirred for 16 hours at +40°C. Subsequently the mixture is evapo- rated and the residue is diluted with water and dichloromethane. The phases are separated and the aqueous phase is extracted three times with dichloromethane. The combined orga- nic layer is washed with brine, dried over sodium sulfate and evaporated. The remaining oil is purified by chromatography on silica gel (ethyl acetate/hexane 1: 1) to yield N [2- (3- methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-phenyl-2-prop-2-yn yloxy-butyramide (E1. 24).

1H-NMR (300 MHz, CDCI3) : 1.02 (d, 3H, CH3), 2.08 (t, 1H, C#CH), 2.27 (t, 1H, C=CH), 2.53 (q, 2H, CH2CH2), 3.18 (dq, 1H, CH), 3.30 (q, 2H, CH2CH2), 3.41 (dd, 1 H, OCH2), 3.65 (s, 3H, OCH3), 3.72 (dd, 1 H, OCH2), 3.90 (q, 1H, CHO), 4.51 (d, 2H, OCH2), 6.49-7. 10 (m, 9H, NH, CH arom.).

Example E2: 2-Allyloxy-N-[2-(3-methoxy-4-prop-2-ynylocy-phenyl)-ethyl]-3 -p-tolyt- propionamide a) 2-Chloro-3-p-tolyl-propionic acid methyl ester.

A solution of sodium nitrite (16.5 g, 0.24 mol) in 50 ml of water is slowly added to a mecha- nically stirred, acetone-dry ice cooled suspension of p-toluidine (23.5 g, 0.22 mol), 250 ml of acetone and 50 ml of concentrated hydrochloric acid in such manner, that the reaction tem- perature does not exceed +5°C. The mixture is stirred for 1 hour at +5°C and then 100 ml of methyl acrylate are added. The suspension is then warmed to +30°C. Copper (l) iodide (1 g, 5 mmol) is added portionwise over 30 minutes such that the temperature of the reaction mixture does not exceed +35°C, and the stirring is continued for an additional 30 minutes at this temperature. The solvent is evaporated under reduced pressure, the residue is diluted with water and extracted with dichloromethane. The combined organic layer is washed with water, dried over magnesium sulfate and evaporated. The residue is purified by chromato- graphy on silica gel (ethyl acetate/hexane 9: 1) to obtain 2-chloro-3-p-tolyl-propionic acid methyl ester.

1H-NMR (300 MHz, CDCl3) : 2.14 (s, 3H, CH3), 2.94 (dd, 1 H, CH2), 3.15 (dd, 1H, CH2), 3.56 (s, 3H, OCH3), 4.23 (t, 1 H, CHCI), 6.89-6. 97 (m, 4H). b) 2-Hvdroxy-3-p-tolyl-propionic acid A mechanically stirred suspension of 2-chloro-3-p-tolyl-propionic acid methyl ester (23 g, 0.1 mol), calcium carbonate (11 g, 0.1 mol), sodium hydroxide (5.5 g, 0.11 mol), 200 ml of dioxane and 300 ml of water is heated at reflux for 16 hours. After cooling to room tempera- ture, 1.3 ! of 2 N hydrochloric acid are added and the mixture is extracted with ethyl acetate.

The combined organic layer is washed with brine, dried over magnesium sulfate and evapo- rated to yield 2-hydroxy-3-p-tolyl-propionic acid, which is sufficiently pure to be used in the next step.

1H-NMR (300 MHz, CDCI3) : 2.25 (s, 3H, CH3), 2.89 (dd, 1 H, CH2), 3.10 (dd, 1 H, CH2), 4.40 (q, 1 H, CHCI), 7.00-7. 07 (m, 4H). c) 2-Hvdroxv-N-f2- (3-methoxv-4-prop-2-vnvloxv-phenvl)-ethyll-3-p-tolyl-propion amide 2- (3-Methoxy-4-prop-2-ynyloxy-phenyl)-ethylamine hydrochloride (11.5 g, 47 mmol) and N, N-diisopropylethylamine (23 g, 0.18 mol) are dissolved in 100 ml of N, N-dimethylform- amide. To this solution 2-hydroxy-3-p-tolyl-propionic acid (8.1 g, 45 mmol) and (benzotria- zol-1-yloxy)-tris- (dimethylamino)-phosphonium hexafluorophosphate (22 g, 49 mmol) are added successively. The reaction mixture is stirred for 16 hours at room temperature, subsequently poured on ice-water and extracted several times with ethyl acetate. The com- bined organic layer is washed with brine, dried over sodium sulfate and evaporated in vacuum. The remaining oil is purified by chromatography on silicagel (ethyl acetate/ hexane 1: 1) to afford 2-hydroxy-N-[2-(3-methOxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3- p-tolyl- propionamide (E1. 16).

'H-NMR (300 MHz, CDCI3) : 2.32 (s, 3H, CH3), 2.50 (t, 1 H, C---CH), 2.73 (dt, 2H, CH2CH2), 2.86 (dd, 1 H, CH2), 3.19 (dd, 1H, CH2), 3.51 (q, 2H, CH2CH2), 3.85 (s, 3H, OCH3), 4.25 (q, 1H, CHOH), 4.74 (d, 2H, OCH2), 6.59 (bs, 1 H, NH), 6.67-7. 29 (m, 7H, CH arom. ). M. p.: 85°C. d) Allyl bromide (1.2 g, 10 mmol) is added slowly at room temperature to a mixture of 2-hydroxy-N-[2- (3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-3-p-tolyl-propion amide (3.0 g, 8.2 mmol), 30 % sodium hydroxide solution (6.5 ml, 41 mmol) and catalytic amounts of tetrabutylammonium bromide (50 mg) in 30 ml of dichloromethane. The reaction is stirred for 16 hours at +40°C. Subsequently the mixture is evaporated and the residue is diluted with water and dichloromethane. The phases are separated and the aqueous phase is extracted three times with dichloromethane. The combined organic layer is washed with brine, dried over sodium sulfate and evaporated. The remaining oil is purified by chroma- tography on silica gel (ethyl acetate/hexane 1: 1) to give 2-allyloxy-N [2- (3-methoxy-4- prop-2-ynyloxy-phenyl)-ethyl]-3-p-tolyl-propionamide (E1. 17).

1H-NMR (300 MHz, CDCI3) : 2.32 (s, 3H, CH3), 2.51 (t, 1H, C_CH), 2. 70 (dt, 2H, CH2CH2), 2.89 (dd, 1 H, CH2), 3.12 (dd, 1 H, CH2), 3.50 (q, 2H, CH2CH2), 3.86 (s, 3H, OCH3), 3.99 (q, 1 H, CHOH), 4.73 (d, 2H, OCH2), 5. 08-5. 15 (m, 2H, C=CH2), 5.69 (dt, 1 H, CH=C), 6.52 (bs, 1 H, NH), 6.62-7. 15 (m, 7H, CH arom.).

According to the procedures of Examples E1 and E2 the compounds listed in table E1 are obtained.

Table E1: (Ph designates phenyl) No. A B Rz'H-NMR E1. 01 Ph-CH2-H 2. 49 (t, 1H), 2.72 (dt, 2H), 2.86 (dd, 1H), 3.20 (dd, 1 H), 3.48 (q, 2H), 3.84 (s, 3H), 4.27 (q, 1 H), 4.72 (d, 2H), 6.63-7. 34 (m, 8H). E1. 02 Ph-CH2-CH2CH3 0.96 (t, 3H), 2.42 (t, 1 H), 2.60 (m, 2H), 2.80 (dd, 1H), 3.06 (dd, 1 H), 3.23-3. 41 (m, 4H), 3.79 (s, 3H), 3.82 (q, 1H), 4.66 (d, 2H), 6.55-7. 23 (m, 8H). E1. 03 Ph-CH2-CH2C---CH 2.40 (t, 1 H), 2.51 (t, 1 H), 2.68 (m, 2H), 2.96 (dd, 1H), 3.20 (dd, 1 H), 3.49 (q, 2H), 3.88 (s, 3H), 3.93 (dd, 1H), 4.05 (dd, 1H), 4.18 (q, 1H), 4.77 (d, 2H), 6.65-7. 31 (m, 8H). E1. 04 4-F-Ph-CH2-H 2.43 (t, 1 H), 2.62 (dt, 2H), 2.78 (dd, 1H), 3.07 (dd, 1H), 3.40 (q, 2H), 3.78 (s, 3H), 4.17 (q, 1H), 4.66 (d, 2H), 6.59-7. 13 (m, 7H). E1. 05 4-F-Ph-CH2-CH2CH3 0.97 (t, 3H), 2.42 (t, 1 H), 2.61 (m, 2H), 2.79 (dd, 1H), 3.02 (dd, 1 H), 3.28 (q, 2H), 3.40 (q, 2H), 3.78-3. 82 (m, 4H), 4.67 (d, 2H), 6. 57-7. 12 (m, 7H). E1. 06 4-F-Ph-CH2-CH2C=CH 2.32 (t, 1 H), 2.43 (t, 1 H), 2.62 (m, 2H), 2.88 (dd, 1 H), 3.05 (dd, 1 H), 3.39 (q, 2H), 3.80 (s, 3H), 3.88 (dd, 1 H), 3.97 (dd, 1 H), 4.06 @ 1H), 4.68 (d, 2H), 6.58-7. 14 (m, 7H). E1. 07 4-CI-Ph-CH2-H 2.31 (t, 1 H), 2.54 (dt, 2H), 2.68 (dd, 1 H), 2.97 (dd, 1 H), 3.30 (q, 2H), 3.68 (s, 3H), 4.07 (q, 1H), 4.54 (d, 2H), 6.48-7. 10 (m, 7H). E1. 08 4-CI-Ph-CH2-CH3 2.50 (t, 1 H), 2.69 (m, 2H), 2.89 (dd, 1 H), 3.09 (dd, 1 H), 3.27 (s, 3H), 3.48 (q, 2H), 3.82 (q, 1 H), 3.90 (s, 3H), 4.75 (d, 2H), 6.62-7. 28 m. 7H). E1. 09 4-Cl-Ph | -CH2- | CH2CH-CH2 2.67 (t, 1 H), 2.85 (m, 2H), 3.05 (dd, 1 H), 3.24 (dd, 1 H), 3.63 (q, 2H), 4.03 (s, 3H), 4.12 (q, 1 H), 4.92 (d, 2H), 5.26-5. 32 (m, 2H), 5.82 (dt, 1 H), 6.78-7. 43 m, 7H). E1. 10 4-Cl-Ph | -CH2- | CH2C#CH 2.40 (t, 1H), 2.51 (t, 1H), 2.71 (m, 2H), 2.95 (dd, 1H), 3.14 (dd, 1H), 3.49 (q, 2H), 3.89 (s, 3H), 3.99 (dd, 1H), 4.06 (dd, 1H), 4.15 (q, 1H), 4.75 (d, 2H), 6.62-7. 28 (m, 7H). E1. 11| 4-Br-Ph | -CH2- | H |2. 52 (t, 1 H), 2.72 (dt, 2H), 2.83 (dd, 1 H), 3.14 (dd, 1H), 3.50 (q, 2H), 3.85 (s, 3H), 4.28 (q, 1 H), 4.76 (d, 2H), 6.68-7. 48 (m, 7H). E1. 12 4-Br-Ph-CH2-CH3 2.43 (t, 1H), 2.62 (m, 2H), 2.80 (dd, 1H), 2.99 (dd, 1H), 3.18 (s, 3H), 3.40 (dq, 2H), 3.73 (q, 1 H), 3.81 (s, 3H), 4.70 (d, 2H), 6.57-7. 33 (m, 7H). E1. 13 4-Br-Ph-CH2-CH2CH3 1.10 (t, 3H), 2.32 (t, 1H), 2.52 (dt, 2H), 2.67 (dd, 1 H), 2.98 (dd, 1 H), 3.27-3. 44 (m, 4H), 3.70 (s, 3H), 4.08 (m, 1 H), 4.58 (d, 2H), 6. 48-7. 28 m, 7H). E1. 14 4-Br-Ph-CH2-CH2CH=CH2 2.42 (t, 1H), 2.61 (m, 2H), 2.80 (dd, 1H), 2.98 (dd, 1 H), 3.40 (q, 2H), 3.78 (s, 3H), 3.89 (q, 1 H), 4.68 (d, 2H), 5.02-5. 10 (m, 2H), 5.59 (dt, 1 H), 6.55-7. 34 m, 7H). E1. 15 4-Br-Ph-CH2-CH2C=CH 2.41 (t, 1H), 2.51 (t, 1H), 2.68 (m, 2H), 2.91 (dd, 1H), 3.10 (dd, 1H), 3.47 (q, 2H), 3.88 (s, 3H), 3.96 (dd, 1H), 4.07 (dd, 1H), 4.13 (m, 1 H), 4.78 (d, 2H), 6.68-7. 42 (m, 7H). E1. 16 4-CH3-Ph-CH2-H 2.32 (s, 3H), 2.50 (t, 1 H), 2.73 (dt, 2H), 2.86 (dd, 1H), 3.19 (dd, 1H), 3.51 (q, 2H), 3.85 (s, 3H), 4.25 (q, 1 H), 4.74 (d, 2H), 6.67-7. 29 (m, 7H). E1. 17 4-CH3-Ph-CH2-CH2CH=CH2 2.32 (s, 3H), 2.51 (t, 1 H), 2.70 (dt, 2H), 2.89 (dd, 1H), 3.12 (dd, 1H), 3.50 (q, 2H), 3.86 (s, 3H), 3.99 (q, 1 H), 4.73 (d, 2H), 5.08-5. 15 (m, 2H), 5.69 (dt, 1H), 6.62- 7.15 (m, 7H). E1. 18 4-CH3-Ph-CH2-CH2C=-CH 2.33 (s, 3H), 2.40 (t, 1H), 2.52 (t, 1H), 2.79 (m, 2H), 2.93 (dd, 1H), 3.15 (dd, 1H), 3.48 (q, 2H), 3.87 (s, 3H), 3.93 (dd, 1 H), 4.04 (dd, 1 H), 4.16 (m, 1 H), 4.75 (d, 1 H), 6.66- 7.16 (m, 7H). E1. 19 4-CH3CH2-Ph-CH2-H 1. 25 (t, 3H), 2. 51 (t, 1 H), 2.60-2. 84 (m, 5H), 3.21 (dd, 1 H), 3.53 (q, 2H), 3.87 (s, 3H), 4.28 (q, 1 H), 4.74 (d, 2H), 6. 65-7. 27 (m, 7H). E1. 20 4-CH3CH2-Ph-CH2-CH2CH3 0.86 (t, 3H), 1.08 (t, 3H), 2.33 (t, 1H), 2.48 (q, 2H), 2.57 (t, 2H), 2.69 (dd, 1 H), 2.95- 3.07 (m, 3H), 3.33 (q, 2H), 3.70 (s, 3H), 4.09 (q, 1 H), 4.60 (d, 2H), 6.49-7. 10 (m, 7H). E1. 21 4-CH3CH2-Ph-CH2-CH2CH=CH2 1.24 (t, 3H), 2.51 (t, 1 H), 2.57-2. 76 (m, 4H), 2.90 (dd, 1H), 3.12 (dd, 1H), 3.48 (q, 2H), 3.85 (s, 3H), 3.99 (q, 1 H), 4.76 (d, 2H), 5.07-5. 15 (m, 2H), 5.68 (dt, 1H), 6.61- 7. 28 (m, 7H). E1. 22 4-CH3CH2-Ph-CH2-CH2C--CH 1.22 (t, 3H), 2.40 (t, 1H), 2.51 (t, 1H), 2.58 - 2. 71 (m, 4H), 2.93 (dd, 1H), 3.16 (dd, 1 H), 3.49 (q, 2H), 3.88 (s, 3H), 3.94 (dd, 1H), 4.06 (dd, 1H), 4.18 (q, 1H), 4.75 (d, 2H), 6.63-7. 18 (m, 7H). E1. 23 Ph-CH (CH3)- H 1.26 (d, 3H), 2.52 (t, 1 H), 2.76 (t, 2H), 3.36 - 3. 61 (m, 3H), 3. 90 (s, 3H), 4.19 (m, 1H), 4.78 (d, 2H), 6.71-7. 38 (m, 8H). E1. 24 Ph-CH (CH3)-CH2C_CH 1. 02 (d, 3H), 2.08 (t, 1 H), 2.27 (t, 1 H), 2.53 (q, 2H), 3.18 (dq, 1H), 3.30 (q, 2H), 3.41 (dd, 1 H), 3.65 (s, 3H), 3.72 (dd, 1 H), 3.90 @ 1H), 4.51 (d, 2H), 6.49-7. 10 (m, 8H). Analogously to the above examples the compounds of tables 1 to 3 are obtained.

Table 1: Compounds represented by the Formula 1. 01 wherein the combination of the groups A, Ri, Rz, Rs, R4 and X corresponds each to one row in table A.

Table 2: Compounds represented by the Formula 1. 02 wherein the combination of the groups A, Ri, R2, R3, R4 and X corresponds each to one row in table A.

Table 3: Compounds represented by the Formula 1. 03 wherein the combination of the groups A, R1. R2, R3, R4 and X corresponds each to one row in table A.

Table A : (Ph designates phenyl) No. A R1 R2 R3 R4 X 001 Ph H H CH2C=CH OCH3 O 002 Ph H CH3 CH2C_CH OCH3 O 003 Ph H CH2CH3 CH2C2CH OCH3 O 004 Ph H CH2C#CH CH3 OCH3 O 005 Ph H CH2C#CH CH2CH3 OCH3 O 006 Ph H CH2C=CH CH2C=CH OCH3 O 007 Ph CH3 CH2C=CH CH2C=CH OCH3 O 008 Ph H CH2C=CH CH2C=CH CH3 O 009 Ph H CH2C#CH CH2C#CH OCH3 S 010 4-F-Ph H H CH2C_CH OCH3 O 011 4-F-Ph H CH3 CH2C=CH OCH3 O 012 4-F-Ph H CH2CH3 CH2C=CH OCH3 O 013 4-F-Ph H CH2C#CH CH3 OCH3 O 014 4-F-Ph H CH2C=-CH CH2CH3 OCH3 0 015 4-F-Ph H CH2C#CH CH2C=CH OCH3 O 016 4-F-Ph CH3 CH2C#CH CH2C=CH OCH3 O 017 4-F-Ph H CH2C#CH CH2C=CH OCH3 O 018 4-F-Ph H CH2C_CH CH2C--CH OCH3 S 019 4-Cl-Ph H H CH2C-CH OCH3 O 020 4-CI-Ph H CH3 CH2C-CH OCH3 O 021 4-Cl-Ph H CH2CH3 CH2C=CH OCH3 O 022 4-Cl-Ph H CH2C#CH CH3 OCH3 O 023 4-Cl-Ph H CH2C#CH CH2CH3 OCH3 O 024 4-Cl-Ph H CH2C#CH CH2C#CH OCH3 O 025 4-Cl-Ph CH3 CH2C#CH CH2C#CH OCH3 O 026 4-CI-Ph H CH2C=CH CH2C=CH CH3 O 027 4-Cl-Ph H CH2C#CH CH2C#CH OCH3 S 028 4-Br-Ph H H CH2C=-CH OCH3 O 029 4-Br-Ph H CH3 CH2C#CH OCH3 O 030 4-Br-Ph H CH2CH3 CH2C#CH OCH3 O 031 4-Br-Ph H CH2C-CH CH3 OCH3 O 032 4-Br-Ph H CH2C#CH CH2CH3 OCH3 O 033 4-Br-Ph H CH2C#CH CH2C#CH OCH3 O 034 4-Br-Ph CH3 CH2C#CH CH2C#CH OCH3 O 035 4-Br-Ph H CH2C#CH CH2C#CH CH3 O 036 4-Br-Ph H CH2C#CH CH2C#CH OCH3 S 037 4-CH3-Ph H H CHsC=CH OCH3 O 038 4-CH3-Ph H CH3 CH2C#CH OCH3 O 039 4-CH3-Ph H CH2CH3 CH2C#CH OCH3 O 040 4-CH3-Ph H CH2C#CH CH3 OCH3 O 041 4-CH3-Ph H CH2C#CH CH2CH3 OCH3 O 042 4-CH3-Ph H CH2C#CH CH2C#CH OCH3 O 043 4-CH3-Ph CH3 CH2C#CH CH2C#CH OCH3 O 044 4-CH3-Ph H CH2C#CH CH2C#CH CH3 O 045 4-CH3-Ph H CH2C#CH CH2C#CH OCH3 S 046 4-CF3-Ph H H CH2C#CH OCH3 O 047 4-CF3-Ph H CH3 CHcC#CH OCH3 O 048 4-CF3-Ph H CH2CH3 CH2C#CH OCH3 O 049 4-CF3-Ph H CH2C#CH CH3 OCH3 O 050 4-CF3-Ph H CH2C#CH CH2CH3 OCH3 O 051 4-CF3-Ph H CH2C=-CH CH2C=-CH OCH3 O 052 4-CF3-Ph CH3 CH2C#CH CH2C#CH OCH3 O 053 4-CF3-Ph H CH2C#CH CH2C#CH CH3 O 054 4-CF3-Ph H CH2C#CH CH2C#CH OCH3 S 055 4-CH3CH2-Ph H H CH2C#CH OCH3 O 056 4-CH3CH2-Ph H CH3 CH2C#CH OCH3 O 057 4-CH3CH2-Ph H CH2CH3 CH2C#CH OCH3 O 058 4-CH3CH2-Ph H CH2C#CH CH3 OCH3 O 059 4-CH3CH2-Ph H CH2C#CH CH2CH3 OCH3 O 060 4-CH3CH2-Ph H CH2C#CH CH2C#CH OCH3 O 061 4-CH3CH2-Ph CH3 CH2C#CH CH2C=-CH OCH3 O 062 4-CH3CH2-Ph H CH2C#CH CH2C-CH CH3 O 063 4-CH3CH2-Ph H CH2C#CH CH2C#CH OCH3 S 064 4-CH30-Ph H H CH2C#CH OCH3 O 065 4-CH30-Ph H CH3 CH2C#CH OCH3 O 066 4-CH30-Ph H CH2CH3 CH2C#CH OCH3 O 067 4-CH30-Ph H CH2C_CH CH3 OCH3 O 068 4-CH30-Ph H CH2C#CH CH2CH3 OCH3 O 069 4-CH30-Ph H CH2C#CH CH2C#CH OCH3 O 070 4-CH30-Ph CH3 CH2C=-CH CH2C=CH OCH3 O 071 4-CH30-Ph H CH2C#CH CH2C#CH CH3 0 072 4-CH30-Ph H CH2C#CH CH2C#CH OCH3 S 073 3,4-Cl2-Ph H H CH2C#CH OCH3 O 074 3,4-Cl2-Ph H CH3 CH2C#CH OCH3 O 075 3,4-Cl2-Ph H CH2CH3 CH2C#CH OCH3 O 076 3,4-Cl2-Ph H CH2C#CH CH3 OCH3 O 077 3, 4-CI2-Ph H CH2C-CH CH2CH3 OCH3 O 078 3, 4-CI2-Ph H CH2C=CH CH2C=CH OCH3 O 079 3,4-Cl2-Ph CH3 CH2C#CH CH2C#CH OCH3 O 080 3, 4-Cl2-Ph H CH2C=-CH CH2C=-CH CH3 O 081 3, 4-Cl2-Ph H CH2C#CH CH2C--CH OCH3 S 082 2-F-Ph H H CH2C#CH OCH3 O 083 2-F-Ph H CH3 CH2C#CH OCH3 O 084 2-F-Ph H CH2CH3 CH2C=-CH OCH3 0 085 2-F-Ph H CH2C_CH CH3 OCH3 O 086 2-F-Ph H CH2C=-CH CH2CH3 OCH3 0 087 2-F-Ph H CH2C#CH CH2C#CH OCH3 O 088 2-Cl-Ph H H CH2C#CH OCH3 0 089 2-Cl-Ph H CH3 CH2C#CH OCH3 O 090 2-Cl-Ph H CH2CH3 CH2C#CH OCH3 O 091 2-Cl-Ph H CH2C#CH CH3 OCH3 O 092 2-Cl-Ph H CH2C#CH CH2CH3 OCH3 O 093 2-Cl-Ph H CH2C#CH CH2C#CH OCH3 O 094 2-CH3-Ph H H CH2C#CH OCH3 O 095 2-CH3-Ph H CH3 CH2C#CH OCH3 O 096 2-CH3-Ph H CH2CH3 CH2C_CH OCH3 O 097 2-CH3-Ph H CH2C#CH CH3 OCH3 O 098 2-CH3-Ph H CH2C#CH CH2CH3 OCH3 O 099 2-CH3-Ph H CH2C#CH CH2C#CH OCH3 O 100 2-CF3-Ph H H CH2C=CH OCH3 O 101 2-CF3-Ph H CH3 CH2C#CH OCH3 O 102 2-CF3-Ph H CH2CH3 CH2C-CH OCH3 O 103 2-CF3-Ph H CH2C=-CH CH3 OCH3 0 104 2-CF3-Ph H CH2C#CH CH2CH3 OCH3 O 105 2-CF3-Ph H CH2C-CH CH2C-CH OCH3 O 106 2-CN-Ph H H CH2C#CH OCH3 O 107 2-CN-Ph H CH3 CH2C#CH OCH3 O 108 2-CN-Ph H CH2CH3 CH2C#CH OCH3 O 109 2-CN-Ph H CH2C=-CH CH3 OCH3 0 110 2-CN-Ph H CH2C-CH CH2CH3 OCH3 O 111 2-CN-Ph H CH2C#CH CH2C#CH OCH3 O 112 2-CH30-Ph H H CH2C#CH OCH3 O 113 2-CH30-Ph H CH3 CHzC=CH OCH3 O 114 2-CH30-Ph H CH2CH3 CH2C-CH OCH3 O 115 2-CH30-Ph H CH-CH3 OCH3 0 116 2-CH30-Ph H CH2C-CH CH2CH3 OCH3 O 117 2-CH30-Ph H CH2C#CH CH2C#CH OCH3 O 118 3-F-Ph H H CH2C-=CH OCH3 0 119 3-F-Ph H CH3 CH2C=CH OCH3 O 120 3-F-Ph H CH2CH3 CH2C#CH OCH3 O 121 3-F-Ph H CH2C#CH CH3 OCH3 O 122 3-F-Ph H CH2C#CH CH2CH3 OCH3 O 123 3-F-Ph H CH2C#CH CH2C#CH OCH3 O 124 | 3-Cl-Ph | H H CH2C_CH OCH3 O 125 3-Cl-Ph H CH3 CH2C#CH OCH3 O 126 3-Cl-Ph H CH2CH3 CH2C#CH OCH3 O 127 3-Cl-Ph H CH2C#CH CH3 OCH3 O 128 3-Cl-Ph H CH2C#CH CH2CH3 OCH3 O 129 3-Cl-Ph H CH2C#CH CH2C#CH OCH3 O 130 3-Br-Ph H H CH2C#CH OCH3 O 131 3-Br-Ph H CH3 CH2C=-CH OCH3 0 132 3-Br-Ph H CH2CH3 CH2C#CH OCH3 O 133 3-Br-Ph H CH2C#CH CH3 OCH3 O 134 3-Br-Ph H CH2C#CH CH2CH3 OCH3 O 135 3-Br-Ph H CH2C#CH CH2C#CH OCH3 O 136 3-CH3-Ph H H CH2C=-CH OCH3 O 137 3-CH3-Ph H CH3 CH2C#CH OCH3 O 138 3-CH3-Ph H CH2CH3 CH2C#CH OCH3 O 139 3-CH3-Ph H CH2C#CH CH3 OCH3 O 140 3-CH3-Ph H CH2C#CH CH2CH3 OCH3 O 141 3-CH3-Ph H CH2C=-CH CH2C=-CH OCH3 0 142 3-CF3-Ph H H CH2C=CH OCH3 O 143 3-CF3-Ph H CH3 CH2C#CH OCH3 O 144 3-CF3-Ph H CH2CH3 CH2C#CH OCH3 O 145 3-CF3-Ph H CH2C#CH CH3 OCH3 O 146 3-CF3-Ph H CH2C#CH CH2CH3 OCH3 O 147 3-CF3-Ph H CH2C#CH CH2C#CH OCH3 O 148 3-CN-Ph H H CH2C#CH OCH3 O 149 3-CN-Ph H CH3 CH2C#CH OCH3 O 150 3-CN-Ph H CH2CH3 CH2C=-CH OCH3 0 151 3-CN-Ph H CH2C#CH CH3 OCH3 O 152 3-CN-Ph H CH2C_CH CH2CH3 OCH3 O 153 3-CN-Ph H CH2C#CH CH2C#CH OCH3 O 154 3-CH3O-Ph | H | H | CH2C#CH | OCH3 | O 155 3-CH30-Ph H CH3 CH2C#CH OCH3 O 156 3-CH30-Ph H CH2CH3 CHzC=CH OCH3 O 157 3-CH30-Ph H CH2C#CH CH3 OCH3 O 158 3-CH30-Ph H CH2C#CH CH2CH3 OCH3 O 159 3-CH30-Ph H CH2C#CH CH2C-CH OCH3 O 160 3-CF30-Ph H H CH2C#CH OCH3 O 161 3-CF30-Ph H CH3 CH2C-CH OCH3 O 162 3-CF30-Ph H CH2CH3 CH2C_CH OCH3 O 163 3-CF30-Ph H CH2C#CH CH3 OCH3 O 164 3-CF30-Ph H CH2C#CH CH2CH3 OCH3 O 165 3-CF30-Ph H CH2C#CH CH2C#CH OCH3 O 166 4-CH2=CH-Ph H H CH2C#CH OCH3 O 167 4-CH2=CH-Ph H CH3 CH2C#CH OCH3 O 168 4-CH2=CH-Ph H CH2CH3 CHzC=CH OCH3 O 169 4-CH2=CH-Ph H CH2C#CH CH3 OCH3 O 170 4-CH2=CH-Ph H CH2C#CH CH2CH3 OCH3 O 171 4-CH2=CH-Ph H CH2C#CH CH2C#CH OCH3 O 172 4-CH#C-Ph H H CH2C#CH OCH3 O 173 4-CH#C-Ph H CH3 CH2C=CH OCH3 O 174 4-CH=C-Ph H CH2CH3 CH2C#CH OCH3 O 175 4-CH=C-Ph H CH2C#CH CH3 OCH3 O 176 4-CH=C-Ph H CH2C#CH CH2CH3 OCH3 O 177 4-CH=C-Ph H CH2C#CH CH-OCH3 0 178 4-CH3CH2CH2-Ph H H CH2C#CH OCH3 O 179 4-CH3CH2CH2-Ph H CH3 CH2C#CH OCH3 O 180 4-CH3CH2CH2-Ph H CH2CH3 CH2C#CH OCH3 O 181 4-CH3CH2CH2-Ph H CH2C-CH CH3 OCH3 O 182 4-CH3CH2CH2-Ph H CH2C#CH CH2CH3 OCH3 O 183 4-CH3CH2CH2-Ph H CH2C#CH CH2C#CH OCH3 O 184 4- (CH3) 2CH-Ph H H CH2C#CH OCH3 O 185 4-(CH3) 2CH-Ph H CH3 CH2C#CH OCH3 O 186 4-(CH3)2CH-Ph H CH2CH3 CHsC=CH OCH3 O 187 4-(CH3) 2CH-Ph H CH2C#CH CH3 OCH3 O 188 4-(CH3) 2CH-Ph H CH2C#CH CH2CH3 OCH3 O 189 4-(CH3) 2CH-Ph H CH2C#CH CH2C#CH OCH3 O 190 4-(CH3)3C-Ph H H CH2C#CH OCH3 O 191 4-(CH3) 3C-Ph H CH3 CH2C#CH OCH3 O 192 4-(CH3)3C-Ph H CH2CH3 CH2C_CH OCH3 O 193 4-(CH3) 3C-Ph H CH2C#CH CH3 OCH3 O 194 4-(CH3) 3C-Ph H CH2C#CH CH2CH3 OCH3 O 195 4- (CH3) 3C-Ph H CH2C#CH CH2C#CH OCH3 O 196 4-CN-Ph H H CH2C#CH OCH3 O 197 4-CN-Ph H CH3 CH2C#CH OCH3 O 198 4-CN-Ph H CH2CH3 CH2C#CH OCH3 O 199 4-CN-Ph H CH2C#CH CH3 OCH3 O 200 4-CN-Ph H CH2C#CH CH2CH3 OCH3 O 201 4-CN-Ph H CH2C#CH CH2C#CH OCH3 O 202 4-CF30-Ph H H CH2C#CH OCH3 O 203 4-CF30-Ph H CH3 CH2C#CH OCH3 O 204 4-CF30-Ph H CH2CH3 CH2C#CH OCH3 O 205 4-CF3O-Ph H CH2C#CH CH3 OCH3 O 206 4-CF30-Ph H CH2C#CH CH2CH3 OCH3 O 207 4-CF30-Ph H CH2C#CH CH2C-CH OCH3 O 208 4-CH3S-Ph H H CH2C#CH OCH3 O 209 4-CH3S-Ph H CH3 CH2C#CH OCH3 O 210 4-CH3S-Ph H CH2CH3 CH2C#CH OCH3 O 211 4-CH3S-Ph H CH2C#CH CH3 OCH3 O 212 4-CH3S-Ph H CH2C#CH CH2CH3 OCH3 O 213 4-CH3S-Ph H CH2C#CH CH2C#CH OCH3 O 214 4-CF3S-Ph H H CH2C#CH OCH3 O 215 4-CF3S-Ph H CH3 CH2C#CH OCH3 O 216 4-CF3S-Ph H CH2CH3 CH2C#CH OCH3 O 217 4-CF3S-Ph H CH2C=-CH CH3 OCH3 O 218 4-CF3S-Ph H CH2C#CH CH2CH3 OCH3 O 219 4-CF3S-Ph H CH2C#CH CH2C#CH OCH3 O 220 4-CH3CH20-Ph H H CH2C#CH OCH3 O 221 4-CH3CH20-Ph H CH3 CH2C#CH OCH3 O 222 4-CH3CH20-Ph H CH2CH3 CH2C_CH OCH3 O 223 4-CH3CH20-Ph H CH2C#CH CH3 OCH3 O 224 4-CH3CH20-Ph H CH2C#CH CH2CH3 OCH3 O 225 4-CH3CH20-Ph H CH2C#CH CH2C#CH OCH3 O 226 4-CH3CH2CH20-Ph H H CH2C=CH OCH3 O 227 4-CH3CH2CH20-Ph H CH3 CH2C#CH OCH3 O 228 4-CH3CH2CH20-Ph H CH2CH3 CH2C#CH OCH3 O 229 4-CH3CH2CH2O-Ph H CH2C#CH CH3 OCH3 O 230 4-CH3CH2CH20-Ph H CH2C#CH CH2CH3 OCH3 O 231 4-CH3CH2CH20-Ph H CH2C#CH CH2C#CH OCH3 O 232 3, 4-Br2-Ph H H CH2C#CH OCH3 O 233 3,4-Br2-Ph H CH3 CH2C#CH OCH3 O 234 3, 4-Br2-Ph H CH2CH3 CH2C-CH OCH3 O 235 3,4-Br2-Ph H CH2C#CH CH3 OCH3 O 236 3,4-Br2-Ph H CH2C#CH CH2CH3 OCH3 O 237 3, 4-Br2-Ph H CH2C#CH CH2C#CH OCH3 O 238 3,5-Br2-Ph H H CH2C#CH OCH3 O 239 3,5-Br2-Ph H CH3 CH2C#CH OCH3 O 240 3,5-Br2-Ph H CH2CH3 CH2C#CH OCH3 O 241 3,5-Br2-Ph H CH2C#CH CH3 OCH3 O 242 3,5-Br2-Ph H CH2C#CH CH2CH3 OCH3 O 243 3, 5-Br2-Ph H CH2C#CH CH2C#CH OCH3 O 244 2, 3-CI2-Ph H H CH2C#CH OCH3 O 245 2, 3-CI2-Ph H CH3 CH2C#CH OCH3 O 246 2, 3-CI2-Ph H CH2CH3 CH2C#CH OCH3 O 247 2,3-Cl2-Ph H CH2C#CH CH3 OCH3 O 248 2,3-Cl2-Ph H CH2C#CH CH2CH3 OCH3 O 249 2,3-Cl2-Ph H CH2C#CH CH2C#CH OCH3 O 250 2, 4-CI2-Ph H CH2C_CH OCH3 O 251 2,4-Cl2-Ph H CH3 CH2C#CH OCH3 O 252 2, 4-CI2-Ph H CH2CH3 CH2C#CH OCH3 O 253 2,4-Cl2-Ph H CH2C#CH CH3 OCH3 O 254 2, 4-CI2-Ph H CH2C_CH CH2CH3 OCH3 O 255 2, 4-CI2-Ph H CH2C=-CH CH2C--CH OCH3 O 256 3,5-Cl2-Ph H H CH2C#CH OCH3 O 257 3,5-Cl2-Ph H CH3 CH2C#CH OCH3 O 258 3,5-Cl2-Ph H CH2CH3 CH2C#CH OCH3 O 259 3,5-Cl2-Ph H CH2C#CH CH3 OCH3 O 260 3,5-Cl2-Ph H CH2C#CH CH2CH3 OCH3 O 261 3,5-Cl2-Ph H CH2C#CH CH2C#CH OCH3 O 262 2, 4-F2-Ph H H CH2C=CH OCH3 O 263 2,4-F2-Ph H CH3 CH2C#CH OCH3 O 264 2, 4-F2-Ph H CH2CH3 CH2C_CH OCH3 O 265 2,4-F2-Ph H CH2C#CH CH3 OCH3 O 266 2,4-F2-Ph H CH2C#CH CH2CH3 OCH3 O 267 2,4-F2-Ph H CH2C#CH CH2C#CH OCH3 O 268 3,4-F2-Ph H H CH2C#CH OCH3 O 269 3,4-F2-Ph H CH3 CH2C#CH OCH3 O 270 3,4-F2-Ph H CH2CH3 CH2C#CH OCH3 O 271 3,4-F2-Ph H CH2C#CH CH3 OCH3 O 273 3,4-F2-Ph H CH2C#CH CH2CH3 OCH3 O 274 3, 4-F2-Ph H CH2C=CH CH2C-CH OCH3 O 275 3, 5-F2-Ph H H CH2C#CH OCH3 O 276 3,5-F2-Ph H CH3 CH2C#CH OCH3 O 277 3,5-F2-Ph H CH2CH3 CH2C#CH OCH3 O 278 3,5-F2-Ph H CH2C#CH CH3 OCH3 O 279 3,5-F2-Ph H CH2C#CH CH2CH3 OCH3 O 280 3,5-F2-Ph H CH2C#CH CH2C#CH OCH3 O 281 3-Br-4-F-Ph H H CH2C#CH OCH3 O 282 3-Br-4-F-Ph H CH3 CH2C#CH OCH3 O 283 3-Br-4-F-Ph H CH2CH3 CH2C#CH OCH3 O 284 3-Br-4-F-Ph H CH2C#CH CH3 OCH3 O 285 3-Br-4-F-Ph H CH2C_CH CH2CH3 OCH3 O 286 3-Br-4-F-Ph H CH2C#CH CH2C#CH OCH3 O 287 3-CI-4-F-Ph H H CH2C#CH OCH3 O 288 3-CI-4-F-Ph H CH3 CH2C=CH OCH3 O 289 3-CI-4-F-Ph H CH2CH3 CH2C#CH OCH3 O 290 3-CI-4-F-Ph H CH2C#CH CH3 OCH3 O 291 3-CI-4-F-Ph H CH2C#CH CH2CH3 OCH3 O 292 3-Cl-4-F-Ph H CH2C#CH CH2C#CH OCH3 O 293 3-F-4-CI-Ph H H CH2C#CH OCH3 O 294 3-F-4-Cl-Ph H CH3 CH2C#CH OCH3 O 295 3-F-4-CI-Ph H CH2CH3 CH2C#CH OCH3 O 296 3-F-4-CI-Ph H CH2C#CH CH3 OCH3 O 297 3-F-4-CI-Ph H CH2C#CH CH2CH3 OCH3 O 298 3-F-4-CI-Ph H CH2C#CH CH2C#CH OCH43 O 299 3-CF3-4-CI-Ph H CH2C--CH OCH3 O 300 3-CF3-4-CI-Ph H CH3 CH2C-CH OCH3 O 301 3-CF3-4-CI-Ph H CH2CH3 CH2C---CH OCH3 O 302 3-CF3-4-CI-Ph H CH2C=CH CH3 OCH3 O 303 3-CF3-4-CI-Ph H CH2C=CH CH2CH3 OCH3 O 304 3-CF3-4-CI-Ph CH2C-CH CH2C_CH OCH3 O 305 3, 4-(CH3) 2-Ph CH2C_CH OCH3 O 306 3, 4- (CH3) 2-Ph CH3 CH2C_CH OCH3 O 307 3, 4- (CH3) 2-Ph CH2CH3 CH2C_CH OCH3 O 308 3, 4- (CH3) z-Ph H CHaCsCH CHs OCHs 0 309 3, 4- (CH3) 2-Ph H CH2C=-CH CH2CH3 OCH3 O 310 3, 4-(CH3) 2-Ph H CH2C=CH CH2C=-CH OCH3 O 311 3, 5- (CH3) 2-Ph H H CH2C-CH OCH3 O 312 3, 5- (CH3) 2-Ph H CH3 CH2C=CH OCH3 O 313 3, 5- (CH3) 2-Ph H CH2CH3 CH2C=CH OCH3 O 314 3, 5- (CH3) 2-Ph H CH2C=-CH CH3 OCH3 O 315 3, 5- (CH3) 2-Ph H CH2C=-CH CH2CH3 OCH3 0 316 3, 5-(CH3) 2-Ph CH2C-CH CH2C_CH OCH3 O 317 3, 4- (CH30) 2-Ph H H CH2C-CH OCH3 O 318 3, 4- (CH30) 2-Ph H CH3 CH2C_CH OCH3 O 319 3, 4- (CH30) 2-Ph H CH2CH3 CH2C=-CH OCH3 O 320 3, 4- (CH30) 2-Ph H CH2C=CH CH3 OCH3 O 321 3, 4- (CH30) 2-Ph H CH2C=CH CH2CH3 OCH3 O 322 3, 4- (CH30) 2-Ph H CH2C=-CH CH2C=CH OCH3 O 323 3, 5- (CH30) 2-Ph H H CH2C---CH OCH3 O 324 3, 5- (CH30) 2-Ph H CH3 CH2C=CH OCH3 O 325 3, 5- (CH30) 2-Ph H CH2CH3 CH2C_CH OCH3 O 326 3, 5- (CH30) 2-Ph H CH2C--CH CH3 OCH3 O 327 3, 5- (CH30) 2-Ph H CH2C---CH CH2CH3 OCH3 O 328 3, 5- (CH30) 2-Ph H CH2C=-CH CH2C_CH OCH3 O 329 3-CH3-4-CH30-Ph H H CH2C-CH OCH3 O 330 3-CH3-4-CH30-Ph H CH3 CH2C=-CH OCH3 O 331 3-CH3-4-CH30-Ph H CH2CH3 CH2C_CH OCH3 O 332 3-CH3-4-CH30-Ph H CH2C-CH CH3 OCH3 O 333 3-CH3-4-CH30-Ph H CH2C=CH CH2CH3 OCH3 O 334 3-CH3-4-CH30-Ph H CH2C_CH CH2C=CH OCH3 O 335 3-F-4-CH30-Ph H H CH2C--CH OCH3 O 336 3-F-4-CH30-Ph H CH3 CH2C_CH OCH3 O 337 3-F-4-CH30-Ph H CH2CH3 CH2C---CH OCH3 O 338 3-F-4-CH30-Ph H CH2C=CH CH3 OCH3 O 339 3-F-4-CH30-Ph H CH2C---CH CH2CH3 OCH3 O 340 3-F-4-CH30-Ph H CH2C=-CH CH2C_CH OCH3 O 341 ~ H H CH2C_CH OCH3 O 0 342 H CH3 CH2C=CH OCH3 O 0 343 H CH2CH3 CH2C-=CH OCH3 O 0 344/9 H CH2C_CH CH3 OCH3 O o- 345 H CH, CiC H CH2CH3 OCH3 O 0 346 H CH2C_CH CHzC-CH OCH3 O 0 347 H3C H H CH2C_CH OCH3 O 3 0 348 H CH3 CH2C=-CH OCH3 0 Hic 0 349 H3C X H CH2CH3 CH2C-CH OCH3 O H3 0 350 H3CX H CH2C_CH CH3 OCH3 O H3C O 351 H3Cg3 H CH2C_CH CH2CH3 OCH3 O Hic 352 H3CX H CH2C_CH CH2C_CH OCH3 O H3C O 353 H H CH2C_CH OCH3 O zu 354 H CH3 CH2C_CH OCH3 O 355 o H CHCH3 CH2C--_CH OCH3 O U 356 69 H CH2C---CH CH3 OCH3 O 357 H C HaC=CH CH2CH3 OCH3 O / 358 o H CH2C---CH CH2C---CH OCH3 O 359/FHHCHsC=CHOCHs0 s 380 Q H CH, CH2C-CH OCH3 O s 361/- H CHsCHs CH2C=CH OCHs 0 s 362 H CH, C=CH CH3 OCH3 O s 363 O H OH, C=CH CH2CH3 OCH3 O s 364 H CH2C=-CH CH2C=-CH OCH3 0 s 365 H H CH2C=CH OCH3 O H3 s 366 H CH3 CH2C=-CH OCH3 0 H3C S 367 H CH2CH3 CH2C=CH OCH3 O H3C S 368/- H CHzCsCH CHs OCHs 0 H3 s 369HCH2C=CH CHgCHs OCHs0 Hazes 370 H CH2C=CH CH2C---CH OCH3 O H3 s 371 H H CH2C_CH OCH3 O tJ 372 H CH3 CH2C_CH OCH3 O 373 s H CH2CH3 CH2C=-CH OCH3 0 U 374 6) H CH2C_CH CH3 OCH3 O U 375 s H CH2C=-CH CH2CH3 OCH3 0 U 376 \S/H CH2C---CH CH2C---CH OCH3 O tj 377 H H CH2c=-CH OCH3 0 Hr-'N 3 Q 378 H CH3 CH2C=-CH OCH3 0 H3c 0' 379 H CH2CH3 CH2C=CH OGH3 O O, N 380 H CH2C=CH CH3 OCH3 O H3 0' "3C 0 381 H CH2C=CH CH2CH3 OCH3 O H3 0' 382 H3C v H CH2C_CH CH2C-CH OCH3 O H3 0' "sC"0 383 H H CH2C---CH OCH3 O s 384 H CH3 CH2C=CH OCH3 O s 385 N7 H CHaCHw CH2C_CH OCH3 O asz 386 t3 H CH2C-CH CH3 OCH3 O s 387NHCHsCCHCHsCHsOCHs0 (ils 7 388 (3 H CH2C=CH CH2C=-CH OCH3 O "-su 389 e H H CH2C_CH OCH3 O \CON N 390 H CH3 CH2C_CH OCH3 O \COR 391 H CH2CH3 CH2C=-CH OCH3 0 -N N 392 H CH2C-CH CH3 OCH3 O -N N 393 H CH2C=CH CHZCH3 QCH3 O zon N 394 H CH2C_CH CH2C_CH OCH3 O -N N 395 t3 H H CH2C_CH OCH3 O NQ-\- 396 H CH3 CH2C--CH OCH3 O Nu-\- 397 \N H CH2CH3 CH2C=-CH OCH3 0 Nu-\- 398 H CH2C_CH CH3 OCH3 O N 399 \1 H CH2C=-CH CH2CH3 OCH3 0 NQ-\- 400 H CH2C-CH CH2C-CH OCH3 O NQ-\- 401 Clv H H CH2C--CH OCH3 O N 402 H CH3 CH2C_CH OCH3 O Clv 403 Cl e H CHzC H, CH2C_CH OCH3 O Nu-\ N 404 Clv H CH2C_CH CH3 OCH3 O C'-f)- N 405./-\HCH2C=CHCHsCHsOCHs0 - nu-\- N 406 Cl v H CH, C=CH CHzC=CH OCH3 O -N-\ 407 Nt 3 H H CH2C-CH OCH3 O Nez 408/=\HCHsCHzC=CHOCHs (7" N 409 N//H CH2CH3 CH2C=-CH OCH3 0 N 410 N 9 H CH2C_CH CH3 OCH3 O 'xi- 411 nu H CH2C-CH CH2CH3 OCH3 O Nez 412 f--H CH2C=-CH CH2C=-CH OCH3 0 N/ 413 N=N H H CH2C--CH OCH3 O N=N 414/-\HCHsCHsCCHOCHs0 N=N 415 N=N H CH, C Hs CH2C-CH OCH3 O N=N 416 N=N H CH, 4=CH CH3 OCH3 O N=N 417 N=N H CHzC=CH CH2CH3 OCH3 O Non 418 N=N H CH, C-C11 CH2C_CH OCH3 O N=N 419/-\HHCH2C=CHOCHs0 N=N N=N 420 ClA H CH3 CH2C_CH OCH3 O N=N N=N 421 ClA H CH2CH3 CH2C_CH OCH3 O N=N N=N 422 4 H CH2C-CH CH3 OCH3 O N=N N=N 423 C H CH2C---CH CH2CH3 OCH3 O N=N N=N 424 ! CH2C=CHCH2C=CHOCHsC) N=N N=N 425/HHCH2C=CHOCHg'"0 N \=N 426 Ne H CH3 CH2C=CH OCH3 O N N 427 N H C HzC HB CH2C_CH OCH3 O N lyi \N zon 428 NW H CHzCCH CH3 OCH3 O N \=N 429 H CH2C-CH CH2CH3 OCH3 O Nez ZON 430 H CH2C=CH CH2C_CH OCH3 O Nez N 431 N< N H H CH2C-CH OCH3 O NON 432 Clo H CH3 CH2C-CH OCH3 O II-i NN 433 C) H CH2CH3 CH2C=CH OCH3 O NON NN 434 HCH2C=CHCHsOCHs0 Y Non 435 ciw H CH2C---CH CH2CH3 OCH3 O NN NvN 436 Clmx H CH2C--CH CH2C--CH OCH3 O NON 437-NHHCHzC=CHOCHs0 N 438 (NF H C H, CH2C_CH OCH3 O N 439 t N H CH2CH3 CH2C_CH OCH3 O N 440 tN H CH2C-CH CH3 OCH3 O N 441 t N H CH>CH CH2CH3 OCH3 O N 442 t N H CH, çCH CH2C--CH OCH3 O N 443 tS H d CH2C_CH OCH3 O N 444 tF H CH3 CH2C_CH OCH3 O N 445 N H CH2CH3 CH2C---CH OCH3 0 N 446 tS H CH2C_CH CH3 OCH3 O N 447N-HCH2C=CHCHsCHsOCHs0 N 448 H CH2C=CH CH2C---CH OCH3 O -0- 449 H H CH2C=-CH OCH3 0 WNJo 450 H CH3 CH2C_CH OCH3 O INK 451 H CH2CH3 CH2C=-CH OCH3 0 N 452 H CH2C=-CH CH3 OCH3 0 CC'N-- 453 H CH2C--_CH CH2CH3 OCH3 O N 454 I H CH2C--_CH CH2C=CH OCH3 O i N 455 rOm H H CH2C-CH OCH3 O 0 O 456 H CH3 CH2C=-CH OCH3 0 0 457 Co ^/H CH2CH3 CH2C--_CH OCH3 O 0 45 C H CH2C_CH CH3 OCH3 O 0 459 Co H CH2C=CH CH2CH3 OCH3 O co 460 H H CH2C_CH CH2C--CH OCH3 O 0 O 461 p H H CH2C--CH OCH3 O 0- 462 p H CH3 CH2C=CH OCH3 O 0- 463 Ow H CH2CH3 CH2C_CH OCH3 O o : o 464 p H CH2C=CH CH3 OCH3 O 0 465 0 H CH2C=CH CH2CH3 OCH3 O 0 466 °>~ H CH2C--CH CH2C-CH OCH3 O o : o 467 H H CH2C=-CH OCH3 0 i 0 468 H CH3 CH2C=-CH OCH3 0 zizi 0 469/< H CH2CH3 CH2C-CH OCH3 O i 0 470 H CH2C_CH | CH3 OCH3 O oU 0 471 H CH2C=-CH CH2CH3 OCH3 0 RoU 0 472 < H CH2C_CH CH2C_CH OCH3 O buzz 0 473/~ H H CH2C-CH OCH3 O _ _ 474 H CH3 CH2C-CH OCH3 O 475/1 H CH2CH3 CH2C--CH OCH3 O W 476/t H CH2C_CH CH3 OCH3 O 477 H CH2C=-CH CH2CH3 OCH3 0 -A 478 H CH2C_CH CH2C_CH OCH3 O \ 479 H H CH2C=-CH OCH3 0 __ _ 480 H CH3 CH2C--CH OCH3 O . 481 H CH2CH3 CH2C=-CH OCH3 0 482 H CH2C=-CH CH3 OCH3 0 /\ _ 483 < H CH2C-CH CH2CH3 OCH3 O 484 H CH2C=CH CH2C=CH OCH3 0 485 H H CH2C=-CH OCH3 0 i 486 H CH3 CH2C_CH OCH3 O < 487 H CH2CH3 CH2C_CH OCH3 O kjk 488 H CH2C_CH CH3 OCH3 O kJL 489 9 1/H CH2C_CH CH2CH3 OCH3 O kjk 490 H CH2C_CH CH2C_CH OCH3 O (i 491 CH3 CH2C_CH CH2C_CH OCH3 O i 492 H CH2C_CH CH2C_CH CH3 O kj 493 H CH2C=-CH CH2C=-CH OCH3 s i 494HHCH2C=CHOCHs0 i i 495 H CH3 CH2C--CH OCH3 O i i 496 H CH2CH3 CH2C=-CH OCH3 0 w 497 H CH2C=-CH CH3 OCH3 0 i i 498 H CH2C=-CH CH2CH3 OCH3 O i i 499 H CH2C=-CH CH2C=-CH OCH3 0 i i 500 CH3 CH2C=-CH CH2C=-CH OCH3 0 i i 501 H CH2C=-CH CH2C=-CH CH3 0 W 502 H CH2C=-CH CH2C=-CH OCH3 s i i 503 Ph w H H CH2C_CH OCH3 O Ph 504 Ph H CH3 CH2C---CH OCH3 O Ph- - 505 Ph H CH2CH3 CH2C---CH OCH3 O Ph- - 506 n H CH2C_CH CH3 OCH3 O Ph < 507 n H CH2C--CH CH2CH3 OCH3 O Ph < 508 Ph < H CH2C_CH CH2C-CH OCH3 O Ph-0- 509 Ph < CH3 CH2C_CH CH2C_CH OCH3 O Ph- - 510 H CH2C=-CH CH2C=-CH CH3 0 Ph < 511 H CH2C_CH CH2C_CH OCH3 S Ph < 512 Ph H H CH3 Cl O 513 Ph H CH3 CH3 Cl O 514 Ph H CH2CH3 CH3 Cl O 515 Ph H CH2C_CH CH3 CI O 516 Ph H H CH2CH3 CI O 517 Ph H CH3 CH2CH3 ci O 518 Ph H CH2CH3 CH2CH3 CI O 519 Ph H CH2C=CH CH2CH3 CI O 520 Ph H H CH2C_CH CI O 521 Ph H CH3 CH2C--CH ci 522 Ph H CH2CH3 CH2C#CH Cl O 523 Ph H CH2C#CH CH2C#CH Cl O 524 | 4-Cl-Ph | H H CH3 Cl O 525 4-Cl-Ph H CH3 CH3 Cl O 526 4-Cl-Ph H CH2CH3 CH3 Cl O 527 4-Cl-Ph H CH2C#CH CH3 Cl O 528 | 4-Cl-Ph | H H CH2CH3 Cl O 529 4-Cl-Ph H CH3 CH2CH3 Cl O 530 4-Cl-Ph H CH2CH3 CH2CH3 Cl O 531 4-Cl-Ph H CH2C#CH CH2CH3 Cl O 532 | 4-Cl-Ph | H H CH2C#CH Cl O 533 4-Cl-Ph H CH3 CH2C#CH Cl O 534 4-Cl-Ph H CH2CH3 CH2C#CH Cl O 535 4-Cl-Ph H CH2C#CH CH2C#CH Cl O 536 4-Cl-Ph H H CH3 Br O 537 4-Cl-Ph H CH3 CH3 Br O 538 4-Cl-Ph H CH2CH3 CH3 Br O 539 4-Cl-Ph H CH2C#CH CH3 Br O 540 4-Cl-Ph H H CH2CH3 Br O 541 4-Cl-Ph H CH3 CH2CH3 Br O 542 4-Cl-Ph H CH2CH3 CH2CH3 Br O 543 4-Cl-Ph H CH2C#CH CH2CH3 Br O 544 4-Cl-Ph H H CH2C#CH Br O 545 4-Cl-Ph H CH3 CH2C#CH Br O 546 4-Cl-Ph H CH2CH3 CH2C#CH Br O 547 4-Cl-Ph H CH2C#CH CH2C#CH Br O 548 4-Cl-Ph H H CH3 CN O 549 4-Cl-Ph H CH3 CH3 CN O 550 4-Cl-Ph H CH2CH3 CH3 CN O 551 4-Cl-Ph H CH2C#CH CH3 CN O 552 4-Cl-Ph H H CH2CH3 CN O 553 4-Cl-Ph H CH3 CH2CH3 CN O 554 4-Cl-Ph H CH2CH3 CH2CH3 CN O 555 4-Cl-Ph H CH2C#CH CH2CH3 CN O 556 4-Cl-Ph H H CH2C#CH CN O 557 4-Cl-Ph H CH3 CH2C#CH CN O 558 4-Cl-Ph H CH2CH3 CH2C#CH CN O 559 4-Cl-Ph H CH2C#CH CH2C#CH CN O 560 Ph H H CH2C#CH Br O 561 Ph H CH3 CH2C#CH Br O 562 Ph H CH2CH3 CH2C#CH Br O 563 Ph H CH2C#CH CH2C#CH Br O 564 Ph H H CH2C#CH CN O 565 Ph H CH3 CH2C#CH CN O 566 Ph H CH2CH3 CH2C#CH CN O 567 Ph H CH2C#CH CH2C#CH CN O 568 4-Br-Ph H H CH2C#CH Cl O 569 4-Br-Ph H CH3 CH2C#CH Cl O 570 4-Br-Ph H CH2CH3 CH2C#CH Cl O 571 4-Br-Ph H CH2C#CH CH2C#CH Cl O 572 4-Br-Ph H H CH2C=-CH Br O 573 4-Br-Ph H CH3 CH2C-CH Br O 574 4-Br-Ph H CH2CH3 CH2C#CH Br O 575 4-Br-Ph H CH2C#CH CH2C#CH Br O 576 4-Br-Ph H H CH2C=CH CN O 577 4-Br-Ph H CH3 CH2C=CH CN O 578 4-Br-Ph H CH2CH3 CH2C#CH CN O 579 4-Br-Ph H CH2C#CH CH2C#CH CN O 580 4-CH3-Ph H H CH2C#CH CI O 581 4-CH3-Ph H CH3 CH2C#CH Cl O 582 4-CH3-Ph H CH2CH3 CH2C#CH Cl O 583 4-CH3-Ph H CH2C#CH CH2C#CH Cl O 584 4-CH3-Ph H H CH2C=CH Br O 585 4-CH3-Ph H CH3 CH2C#CH Br O 586 4-CH3-Ph H CH2CH3 CH2C=-CH Br O 587 4-CH3-Ph H CH2C#CH CH2C#CH Br O 588 4-CH3-Ph H H CH2C=CH CN O 589 4-CH3-Ph H CH3 CH2C#CH CN O 590 4-CH3-Ph H CH2CH3 CH2C#CH CN O 591 4-CH3-Ph H CH2C#CH CH2C#CH CN O 592 Ph H CH2C#CH CH2C#CCH3 OCH3 O 593 4-Cl-Ph H CH2C#CH CH2C#CCH3 OCH3 O 594 4-Br-Ph H CH2C#CH CH2C#CCH3 OCH3 O 595 4-CH3-Ph H CH2C=CH CH2C=CCH3 OCH3 O 596 Ph H CH2C#CH CH2C#C-C2H5 OCH3 O 597 4-Cl-Ph H CH2C#CH CH2C#C-C2H5 OCH3 O 598 4-Br-Ph H CH2C#CH CH2C#C-C2H5 OCH3 O 599 4-CH3-Ph H CH2C#CH CH2C#C-C2H5 OCH3 O Formulations may be prepared analogously to those described in, for example, WO 95/30651.

Biological Examples D-1: Action against Plasmopara viticola on vines a) Residual-protective action Vine seedlings are sprayed at the 4-to 5-leaf stage with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation for 6 days at 95-100 % relative humidity and +20°C. b) Residual-curative action Vine seedlings are infected at the 4-to 5-leaf stage with a sporangia suspension of the fungus. After incubation for 24 hours in a humidity chamber at 95-100 % relative humidity and +20°C, the infected plants are dried and sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After the spray coating has dried, the treated plants are placed in the humidity chamber again.

Fungus infestation is evaluated 6 days after infection.

Compounds of Tables 1 to 3 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds E1. 03, E1. 10, E1. 15, E1. 18 and E1. 22 at 200 ppm inhibit fungal infestations in both tests D-1 a) and D-1 b) by 80-100 %. At the same time untreated plants showed pathogen attack of 80-100 %.

D-2: Action against Phytophthora on tomato plants a) Residual-protective action After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 5 days at 90-100 % relative humidity and +20°C. b) Systemic action After a cultivation period of 3 weeks, tomato plants are watered with a spray mixture (0.02 % active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above the ground. After 96 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100 % relative humidity and +20°C.

Compounds of Tables 1 to 3 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds E1. 03, E1. 06, E1. 10, E1. 15 and E1. 22 at 200 ppm inhibit fungal infestations in both tests D-2a) and D-2b) by 80-100 %. At the same time untreated plants showed pathogen attack of 80-100 %.

D-3: Action against Phytophthora on potato plants a) Residual-protective action 2-3 week old potato plants (Bintje variety) are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100 % relative humidity and +20°C. b) Systemic action 2-3 week old potato plants (Bintje variety) are watered with a spray mixture (0.02 % active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above the ground. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation of the infected plants for 4 days at 90-100 % relative humidity and +20°C.

Fungal infestation is effectively controlled with compounds of Tables 1 to 3. Compounds E1. 03, E1. 06, E1. 10 and E1. 15 at 200 ppm inhibit fungal infestations in both tests D-3a) and D-3b) by 80 to 100%. At the same time untreated plants showed pathogen attack of 80 to 100%.