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GB2220655A - Plant fungicidal azoles - Google Patents

Plant fungicidal azoles Download PDF

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Publication number
GB2220655A
GB2220655A GB8914693A GB8914693A GB2220655A GB 2220655 A GB2220655 A GB 2220655A GB 8914693 A GB8914693 A GB 8914693A GB 8914693 A GB8914693 A GB 8914693A GB 2220655 A GB2220655 A GB 2220655A
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alkyl
general formula
alkenyl
alkynyl
compounds
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GB8914693D0 (en
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Christopher John Urch
Paul Anthony Worthington
Patrick Jeff Crowley
Jeremy Robert Godwin
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

-1,v, -C 6 r HETEROCYCLIC COMPOUNDS This invention relates to
heterocyclic compounds which are useful as fungicides, to processes for preparing the compounds, to fungicidal compositions containing them, and to methods of using them to combat fungi, especially fungal infections in plants.
According to the invention there are provided compounds having the general formula (I):
X R 3 OR 2 R 5 Y I I I __ C C Az (I) I R 1 Z 04 Q R and stereoisomers thereof, wherein Ri represents a group of general formula (II):
C C R 7 (II) or a group of general formula (III):
C = (III) R 8/ \R 10 o wherein R 7 to R 10 are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; R 2 is hydrogen, alkyl, alkenyl or alkynyl (providing that the carbon atoms adjacent to the oxygen is not involved in any unsaturation); R 3 to R 6 are independently hydrogen, alkyl, alkenyl or alkynyl; X, 2 - Y and Z are independently hydrogen, halogen, alkyl cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, optionally substituted aryloxy or optionally substituted aralkoxy; Az represents imidazol-l-yl or 1, 2, 4-triazol-l-yl; Q is a bridging group having one of the following values Q 1 Q 2, Q 3 or Q Rll I Q 1 -C- R 12 Rll R 13 I I Q 2 _ C C I i R 12 R 14 Rll R 13 R 15 I i f Q 3 = C C C I IJ R 12 R 14 R 16 R 11 R 13 R 15 R 17 I I L Q 4 = C C CC C R 12 114 16 R 18 3 - wherein R 11 to R 18 are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl,R 5 is hydrogen, R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R 1 is not CH=CH 2.
The compounds of the invention are generally obtained in the form of mixtures of geometric isomers such as diastereoisomers and E and Z double bonds, including cis and trans double bonds, these and other mixtures of optical isomers can be separated into individual isomers by methods in the art and such isomers constitute a part of the present invention.
Alkyl groups containing from 1 to 4 carbon atoms represented by R 3 to R 18 are either straight or branched chain groups, for example methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl Alkyl groups containing from 1 to 6 carbon atoms represented by R 2 may be either straight or branched chain groups for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, pentyl (straight or branched chain) or hexyl (straight or branched chain) Alkyl groups and the alkyl moieties of alkoxy, haloalkyl and haloalkoxy represented by X, Y and Z are either straight or branched chain groups containing from 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, including any of the specific isomers mentioned above.
Alkenyl groups containing from 2 to 4 carbon atoms represented by R 3 to R 18, which are the same or different, are alk-l-enyl, alk-2-enyl or alk-3enyl, for example vinyl, 2-prop-l-enyl, l-prop-l-enyl, 4 - allyl, 2-but-2-enyl, 1-( 2-methylprop-l-enyl), 1-but- 1-enyl, 2-but-2-enyl, 1-( 1-methylprop-2-enyl), 1-( 2- methylprop-2-enyl), 1-but-2-enyl, or 1-but-3-enyl.
Alkenyl groups containing from 3 to 6 carbon atoms represented by R 2 which are either E or Z geometry (including cis and trans), are alk-2-enyl, alk-3- enyl, alk-4-enyl or alk-5-enyl, for example allyl, l-( 1-methylprop-2-enyl), 1-( 2- methylprop-2-enyl), 1-but-2-enyl, 1-but-3-enyl, pent- 2-enyl, pent-3-enyl, pent-4-enyl, hex-2-enyl, hex-3enyl, hex-4-enyl or hex-5-enyl Alkenyl groups represented by X, Y and Z, which are the same or different which are E or Z geometry (including cis and trans), are either straight or branched chain groups containing from 2 to 6 carbon atoms, for example vinyl or allyl, or any of the specific isomers mentioned above.
Alkynyl groups containing from 2 to 4 carbon atoms represented by R 3 to R 18, which are the same or different and are, for example ethynyl, prop-lynyl, propargyl, 2-but-3-ynyl, but-l-ynyl, but-2-ynyl or but-3-ynyl Alkynyl groups containing from 3 to 6 carbon atoms represented by R 2 may be alk-2-ynyl, alk-3-ynyl, alk-4-ynyl or alk-5-ynyl, for example propargyl or but-2-ynyl Alkynyl groups represented by X, Y and Z are either straight or branched chain groups containing from 2 to 6 carbon atoms, for example ethynyl or propargyl, or any of the examples mentioned above.
Cycloalkyl groups represented by X, Y and Z are C 3-C 7 cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl groups.
Cycloalkylalkyl groups represented by X, Y and Z are C 3 _ 7 cycloalkyl(Cl_ 6)alkyl groups, for example cyclopropylmethyl cyclohexylmethyl, or 1- cyclopropylethyl.
Examples of X, Y and Z when these are aryl, aralkyl, aryloxy or aralkoxy are phenyl, benzyl, phenoxy and benzyloxy These rings are optionally substituted with halogen (fluorine, chlorine or bromine), C 1 _ 6 alkyl (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert- butyl), C 1 _ 6 alkoxy (eg, methoxy, ethoxy, propoxy or butoxy), halo(Cl_ 6)alkyl (eg, trifluoromethyl), halo (Cl_ 6)alkoxy (eg, trifluoromethoxy), nitro, phenyl or phenoxy.
Halogen atoms are fluorine, chlorine, bromine or iodine atoms.
In another aspect the invention provides compounds having the general formula (I):
X R 3 OR 2 R 5 Y I I I Q C C C C C Az (I) I Z R 4 6 Z R O and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C C R 7 (II) or a group of general formula (III):
6 - R 9 C C (III) RS \ R 10 wherein R 7 to Rio which can be the same or different each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine, bromine or iodine), R 2 represents a hydrogen atom, an aikyl group containing from 1 to 6 carbon atoms, or an alkenyl or alkynyl group containing from 3 to 6 carbon atoms (providing that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation), R 3 to R 6, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms, X, Y and Z, which can be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy group, Az represents 1-imidazole or 1,2,4-triazole and Q is a bridging group having one of the following values Q 1, Q 2 3 or Q 4:
Q Q or Q 7 - Rll Q 1= C R 12 R 11 R 13 I I Q 2 = C C I I R 12 R 14 R 11 R 13 R 15 i I I Q 3 = C C C I I I R 12 R 14 R 16 R 1 R 13 R 15 R 17 I 11 I I Q 4 = C C _ C I Ii R 12 R 14 R 6 R 18 wherein R 11 to R 18, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine or bromine); and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl, R 5 is hydrogen, R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R 1 is not -CH=CH 2.
In yet another aspect the invention provides compounds having the general formula (I):
X R 3 OR 2 R 5 Y 1 II I C C C Az (I) I i I Z R 4 Q R 6 i R 1 and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C_ C R 7 (II) or a group of general formula (III):
9 R C = C (III) R 8 J \R 10 wherein R 7 to R 10 are independently hydrogen, halogen, Cl_ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; R 2 is hydrogen, Cl_ 6 alkyl, C 3-6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 to R 6 are independently hydrogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; X, Y and Z are independently hydrogen, halogen, C 1 _ 6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl_ 6)alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, phenyl, phenyl(Cl_ 6)alkyl, C 1 _ 6 alkoxy, phenoxy or phenyl(Cl_ 6)alkoxy; Az represents imidozol-l-yl or 1, 2, 4-triazol-l-yl; Q is a binding group having one of the following values Q 1 I, Q 2, Q 3 or Q 4:
9 - -9 Rll Q 1 = C R 12 R 11 l R 13 Q 2 = C C c II R 12 R 14 R 1 lR 13 R 15 I I I Q 3 = C C C-_ C I i 1 R 12 R 14 R 16 R 1 l R 13 Rl 5 R 17 I i I'l Q 4 = C C _ C C R 12 R 14 R 16 R 18 - wherein R 1 l to R 18 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; wherein any of the foregoing aryl moieties are optionally substituted by halogen, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, halo(Cl_ 6)alkoxy, halo(Cl_ 6)alkyl, nitro, phenvl or phenoxy; and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl, R 5 is hydrogen, R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R 1 is not CH=CH 2.
In a further aspect the invention provides compounds having the general formula (IA):
X R 3 OR 2 Y I I CH C CH 2 Az (IA) J i Z Q I R 1 and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
Cm C-R 7 (II) or a group of general formula (III):
R 9 C=C \C = C I R 8 \R 10 o wherein R 7 and R 10 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; R 2 is hydrogen, C 1 _ 6 alkyl, C 3 _ 6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; X, Y and Z are independently hydrogen, halogen, C 1 _ 6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl-6)alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, phenyl, phenyl(Cl_ 6) alkyl, Cl_ 6 alkoxy, phenoxy or phenyl(Cl_ 6)alkoxy, Az represents imidazol-l-yl or 1, 2, 4-triazol-1-yl; Q is a bridging group having one of the following values Q 1 or Q 2:
Rll t Q 1 =-C k 12 R R 11 R 13 I i Q 2 =-C C 11 142 R 1 wherein R 1 to R 14 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; wherein any of the foregoing aryl moieties are optionally substituted by halogen, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, halo(Cl_ 6)alkoxy, halo(Cl_ 6) alkyl, nitro, phenyl or phenoxy; and salts and metal complexes thereof.
In yet a further aspect the invention provides compounds having the general formula (IA):
X R 3 OR 2 I 1 I Y /CH C CH 2-Az (IA) IA Q Z I R 1 12 - and stereoisomers thereof; wherein R 1 represents a group of general formula (II):
C C R 7 (II) or a group of general formula (III):
R 9 C C R 8 \R 10 wherein R 7 to R 1 o are independently hydrogen, halogen or C 1 _ 4 alkyl; R 2 is hydrogen, C 1 _ 6 alkyl, C 3-6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen or C 1 _ 4 alkyl; X, Y and Z are independently hydrogen, fluorine, chlorine, bromine, C 1-6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl-6)alkyl, C 2-6 alkenyl, C 2-6 alkynyl or C 1 _ 6 alkoxy; Az represents imidazol-l-yl or 1,2,4-triazol-l-yl; Q is a bridging group having one of the following values Q 1 or Q 2:
Q 1 = _ CR 1 1 I R 12 Rll R 13 Q C C- I I Q 2 = __ CC R 12 R 14 wherein R 1 l to R 14 are independently hydrogen, halogen or C 1 _ 4 alkyl; and salts and metal complexes 13 - thereof.
In a still further aspect the invention provides compounds having the general formula (IB):
X R 3 OR 2 i I Y CH-C-CH 2 N-/N (IB) Z QR N and stereoisomers thereof; wherein R 1 represents a group of general formula (II):
C CR 7 (II) or a group of general formula (IIIA):
R 9 C = C/ (IIIA) H -/ R 10 wherein R 7, R 9 and R 10 are independently hydrogen, methyl or ethyl, R 2 is hydrogen, methyl, propenyl or propynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen or methyl; X, Y and Z are independently hydrogen, chlorine or fluorine; Q is a bridging group having one of the following values Q 1 or Q 2:
Rll Rll R 13 I I I Q 1 _ C Q 2 = C C I I l R 12 R 12 R 14 wherein R 11 to R 14 are independently hydrogen or methyl; and salts and metal complexes thereof.
14 - In yet a further aspect the invention provides compounds having the general formula (IC):
X R 3 OH Yg CH C CH 2 N N (IC) I I CH If CH 2 and stereoisomers thereof, wherein R 3 is hydrogen or methyl; Q is a bridging group having one of the following values Q 1 or Q 2 Rll I Q 1 = C Q 2 = CH 2 CH 2 112 wherein R 1 l and R 12 are independently hydrogen or methyl; X and Y are independently hydrogen or chlorine; and salts and metal complexes thereof.
In another aspect the invention provides the compound:
Cl OH CH 2 C CH 2 N N CH 3 CH N I CH il CH 2 (compound 431 of Table I) and its stereoisomers; and salts and metal complexes thereof.
- In a still further aspect the invention provides the compound:
C 1 OH I CH 2 C CH 2 N/-N H 3 C-C CH 3 N I CH LH 2 (compound 437 of Table-I) and its stereoisomers; and salts and metal complexes thereof.
In Table I the significance of the abbreviationss is follows:
Me represents methyl Et represents ethyl npr represents normal propyl Tr represents 1,2,4-triazol- 11-yl All melting points in Table I below are expressed in degrees centigrade.
Whilst the azole (Az) in column 11 of Table I is given as Tr (ie, 1, 2, 4-triazol-l-yl) it should be understood that it could equally be Im (ie, imidazol-l-yl) and this specification should be read as comprising, in each instance, the imidazol-l-yl corresponding to the precise 1,2, 4-triazol-l-yl specified.
TABLE I
COMPOUND MELTING NO X Y Z Q RI R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 1 2-Cl 4-Cl H CH 2 CICH H H H Ht H Tr 2 2-CI 4-Cl H CH 2 C-CH Me H H H H Tr 3 2-C 1 4-C 1 H CH 2 C-C Me H H H H Tr Oil 4 2-C 1 4-C 1 H CH 2 C-C Me Me H H H H Tr 2-C 1 4-C 1 H CH 2 C-C Me Et H H H H Tr 6 2-C 1 4-C 1 H CH 2 C-C Me n Pr H H H H Tr 7 2-C 1 4-C 1 H CH 2 C=C Me CH 2-CH=CH 2H H H H Tr 8 2-C 1 4-C 1 H CH 2 C-C Me CH 2-C=CH H H H H Tr 9 2-C 1 4-C 1 H CH 2 CC Et H H H H H Tr 2-C 1 4-C 1 H CH 2 C-C Et Me H H H H Tr 11 2-C 114-C 1 H CH 2 CH=C 112 H H H H H Tr 12 2-C 1 4-C 1 H CH 2 CH=CH 2 Me H H H H Tr 13 2-C 1 4-C 1 H CH 2 CH=CH Me H H H H H Tr E 14 2-C 1 4-C 1 H CH 2 CH=CH Me H H H H H Tr z TABLE I (Cont/d) COMPOUND MELTING NO X Y Z R R 2 R 3R 4R 5R 6Az POINT ( C) 2-1 4 CI H e H H H H T 2-Cl4-C 1H CH 2 CH=CH MeMe H H H H Tr E 16 2-C 14-C 1H CH 2 CH=CH MeMe H H H H Tr z 17 2-C 14-ClH CH 2 CH=CH Me Et H H H H Tr z 19 2-Cl4-Cl H CH 2 CH=CH Met Pr H H H H Tr E E 2-Cl4-Cl H CH 2 CH=CH Men Pr H H H H Tr 2 z 21 2-C 14-C 1H CH 2 CH=CH MeCH 2-CH=CH 2HH H H Tr E 22 2-Cl4-Cl H CH 2 CH=CH MeCH 2-CH=CH 2HH H H Tr z 23 2-C 14-C 1H CH 2 CH=CH MeCH 2-CFCHHH H H Tr E 24 2-Cl4-C 1H CH 2 CH=CH MeCH 2-C=CHHH H H Tr z 2-Cl4-Cl H G 2 CH=CH EtH H H H H Tr E TABLE I (Cont/d) (XIPOUND METING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 26 2-Cl 4-Cl H CH 2 CH=CH Et H H H H H Tr z 27 2-Cl 4-C 1 H CH 2 CHCH Et Me H H H H Tr E 28 2-Cl 4-C 1 H CH 2 CH=CH Et Me H H H H Tr z 29 2-C 1 4-C 1 H CH 2 Cl=e 2 H 11 H H H H Tr 2-C 1 4-C 1 H CH 2 CH=C Me 2 Me H H H H Tr 31 2-Cl 4-Cl H CH 2 CH 2CH H H H H H Tr 32 2-Cl 4-Cl H CH 2 CH 2CCH Me H H H H Tr 33 2-C 1 4-C 1 H CH 2 CH 2C-=Me H H H H H Tr 34 2-Cl 4-Cl H C 2 CH 2 l QC Me Me H H H H Tr 2-C 1 4-Cl H CI 2 CH 2 C Ce Et H H H H Tr 36 2-Cl 4-C 1 H CH 2 CH 2 He nprH H H H Tr 37 2-C 1 4-Cl H CH 2 CH 2 C CH 2-CH=CH 2H H H H Tr 38 2-Cl 4-Cl H C 2 CH 2 C G 1 e CH 2-CCH H H H H Tr 39 2-Cl 4-Cl H CH 2 CH 2 C-CF=t H H H H H Tr TABLE I (Cont/d) CCIPOUNDM MELTING NO X Y Z Q R 1 R 2 R 3R 4 R 5R 6 Az POINT ( C) 2-C 14-C 1H CH 2 CH 2COC Et Me H H H H Tr 41 2-C 14-C 1H CH 2 CH 2CHO t 2 H H H H H Tr 42 2-Cl 4-C 1H CH 2 CH 2CH=G 2 Me H H H H Tr 43 2-C 14-C 1H CH 2 CH 2CH=CE Me H H H H H Tr E 44 2-Cl 4-Cl H CH 2 C 2CH=C Ue H H H H H Tr z 2-Cl 4-Cl H CH 2 CH 2CH-C He Me H H H H Tr E 46 2-C 14-C 1H CH 2 CH 2CH=CH Me Me H H H H Tr z 47 2-C 14-C 1H CH 2 CH 2CH=CI Me Et H H H H Tr E 48 2-Cl 4-C 1H CH 2 CH 2CH=C He Et H H H H Tr z 49 2-C 14-C 1H CH 2 CH 2CH=CM Menpr H H H H Tr E 2-C 14-C 1H CH 2 CH 2CR=CIH Menpr H H H H Tr z TABLE I (Cont/d) CMPOUND ' MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 51 2-C 1 4-C 1 H CH 2 CH 2 CH=Cte C t 2-CH=CH 2H H H H Tr E 52 2-C 1 4-C 1 H CH 2 CH 2 CH=;We CH 2-CH=CH, H H H H Tr z 53 2-C 1 4-C 1 H CH 2 CH 2 af Z CH 2-C-CH H H H H Tr E 54 2-C 1 4-C 1 H Ct 2 CH 2 CH=t Me CH 2-Ca Cl H H H H Tr z 2-C 1 4-C 1 H CH 2 CH 2 C H=CH Et H H H H Tr E 56 2-Cl 4-Cl H CH 2 CH 2 CH=CH Et H 1 t H H H Tr z 57 2-C 1 4-C 1 H CH 2 CH 2 CH=CH Et Me H H H H Tr E 58 2-C 1 4-C 1 H Ct 2 CH 2 CH=Cl Et Me H H H H Tr z 59 2-C 1 4-C 1 H CH 2 CH 2 CH=C Me 2 H H H H H Tr 2-C 1 4-Cl H Ci 2 CH 2 CH=C Me 2 Me H H H H Tr 61 2-C 1 H H C( 2 CCH H H H H H Tr TABLE I (Cont/d) COOMPOUND, b MELTING NO X Y Z Q RI R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 62 2-C 1 H H CH 2 CH Me H H H H Tr 63 2-C 1 H H CH 2 C 3 Me H H H H H Tr 64 2-C 1 H H CH 2 (QC 4 e Me H H H H Tr 2-C 1 H H CH 2 CQC Me Et H H H H Tr 66 2-C 1 H H CH 2 C(C Me n Pr H H H H Tr 67 2-C 1 lH H CH 2 CC Me CH 2-CH=CH 2 H H H H Tr 68 2-C 1 H H CH 2 Ca C Me C 12-C-C H H H H Tr 69 2-C 1 H H CH 2 C-C Et H H H H H Tr Oil 2-C 1 H H CH 2 C=OC Et Me H H H H Tr 71 2-C 1 lH H CH 2 Ct=CH 2 H H H H H Tr 72 2-C 1 H H CH 2 CH=CH 2 Me H H H H Tr 73 2-C 1 lH H CH 2 =CC Me H H H H H Tr E 74 2-C 1 H H CH 2 CH=CH Me H H H H H Tr z 2-C 1 H H CH 2 CHC Me Me H H H H Tr E TABLE I (Cont/d) C(OMUNEC MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 76 2-Cl H H CH 2 CH=te Me H H H H Tr z 77 2-C 1 H H CH 12 G(=t Me Et H H H H Tr E 78 2-C 1 H H CH 12 CH=Lawe Et H H H H Tr z 79 2-C 1 H H CH 2 C=-Mae npr H H H H Tr E 2-C 1 H H ( t 2 CI=C Ie n Pr 11 H H H Tr 2 z 81 2-C 1 H H 1 CH 2 CH=Ctl WeCH 2-CH=CH 2H H H H Tr E 82 2-C 1 H H CH 2 1 i CH WeCH 2-CH=CH 2H H H H Tr z 83 2-C 1 H H CH 2 CHCH-e CH 2-C= 01 H H H H Tr E 84 2-Cl H H CH 2 CH=CR Ie C 02-CCH H H H H Tr z 2-Cl H H CH 2 CH=C O Et H H H H H Tr E TABLE I (Cont/d) (fl POUND I 235 RMELTING NO X Y Z Q R 1 R 2R 3R 4R 5R 6 Az POINT ( C) 86 2-C 1 H H CH 2 CH=CH Et H H H H H Tr z 87 2-C 1 H H CH 2 CH=CH Et Me H H H H Tr E 88 2-C 1 H H CH 2 CH=CH Et Me H H H Tr z 89 2-C 1 H H CH 2 CH-C Me 2 H H H H H Tr 2-C 1 H H CH 2 CH=C 2 Me H H H H Tr 91 2-C 1 H H CH 2 CH 2 C CH H H H H H Tr 92 2-C 1 H H CH 2 CH 2 C=JH Me H H H H Tr 93 2-C 1 H H CH 2 CH 2 C-C Me H H H H H Tr 94 2-Cl H H CH 12 CH 2C O C Me Me H H H H Tr 2-C 1 H H CH 2 CH 2 Cm G Me Et H H H H Tr 96 2-Cl H H CH 2 CH 2 C C Me n Pr H H H H Tr 97 2-Cl H H 12 CH 02 CC MfeCH 2-CH=CH 2H H H H Tr 98 2-C 1 H H CH 2 CH 2 CC Me CH 2-C-m CHH H H H Tr TABLE I (Cont/d) OOM 4 POUND ' MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 99 2-C 1 H H CH 2 CH 2 Ce C Et H H H H H Tr 2-C 1 H H CH 2 CH 2 C C Et Me H H H H Tr 101 2-Cl H H CH 2 CH 2 a 2 H H H H H Tr oil 102 2-C 1 H H CH 2 CH 2 (H=Ct 2 Me H H H H Tr 103 2-C 1 H H CH 2 CH 2 Cl=t C He H H H H H Tr E 104 2-C 1 H H CH 2 CH 2 CH=C Le H H H H H Tr z 2-C 1 H H CH 2 CH 2 C Haf Me Me H H H H Tr E 106 2-C 1 H H CH 2 CH 2 CH=C Hte Me H H H H Tr z 107 2-Cl H H H 2 { 2 CH=CH{e Et H H H HI Tr E 108 2-C 1 H H CH 2 CH 2 CH =Oe Et H H H H Tr z 109 2-Gl H H CH 2 CH 2 CH= 6 l{ npr H H H I Tr E TABLE I (Cont/d) CXNPOUND 1 FMELTING NO X Y Z Q R R 2 R 3 R 4 R 5 R 6 AZ POINT ( C) 2-Cl H H CH 2 CH 2 CH=CR 4 e n Pr H H H H Tr z 111 2-C 1 H H CH 2 CH 2 E= CH 2-CH=CH 2H H H H Tr E 112 2-Cl H H CH 2 CH 2 CH=ae CH 2-CH=CH 2H H H H Tr z 113 2-Cl H H CH 2 CH 2 CHl=a CH 2-C-CH H H H H Tr E 114 2-C 1 H H CH 2 CH 2 CH=CH 4 e CH 2=CH H H H H Tr z 2-C 1 H H CH 2 CH 2 CH=CH Et H H H H H Tr E 116 2-C 1 H H CH 2 CH 2 CH=CH Et H H H H H Tr z 117 2-C 1 H H CH 2 CJ 2 CH=CH Et Me H H H H Tr E 118 2-C 1 H H 2 CH 2 CH=CH Et Me H H H H Tr z 119 2-Cl H H CH 2 CH 2 CH H H H H Tr TABLE I (Cont/d) O 14 IOJUND IMELTING NO X Y Z Q R ' R 2 R 3 R 4 R 5 R 6 Az PINT ( C) 2-C 1 H H CH 2 CH 2 CH=Me 2 Me H H H H Tr 121 4-C 1 H H CH 2 C-CH H H H H H Tr 122 4-Cl H H CH 2 CCH Me H H H H Tr 123 4-C 1 H H CH 2 CLe H H H H H 11 Tr Oil 124 4-Cl H H CH 2 14 e Me H H H H Tr 4-C 1 H H CH 2 CG 1 e Et H H H H Tr 126 4-C 1 H H CH 2 OCO'e n Pr H H H H Tr 127 4-C 1 H H CH 2 C:4 e CH 2-CH=CH 2H H H H Tr 128 4-C 1 H H CH 2 CO 4 e CH 2-C-=CH H H H H Tr 129 4-C 1 H H CH 2 CC Et H H H H H Tr Oil 4-C 1 H H CH 2 OC=Et Me H H H H Tr Oil 131 4-Cl H H CH 2 CO 12 H H H H H Tr Oil 132 4-Cl H H CU 2 (CH 2 Me H H H H Tr 133 4-Cl H H CH 2 CH=C Me H H H H H Tr E 134 4-Cl H H CH 2 CIC Re H H H H H Tr z TABLE I (Cont/d) O MPOUND I MELTING NO X Y Z Q R 1 R 2 R 3R 4R 5 R 6 Az POINT ( C) 4-C 1 H H CH 2 CH=CH Mte Me H H H H Tr E 136 4-C 1 H H CH 2 CH=C He Me H H H H Tr z 137 4-C 1 H H CH 2 CH=C He Et H H H H Tr E 138 4-C 1 H H H CH 2 =CH 4 e Et H H H H Tr 2 z 139 4-C 1 H H CH 2 CH=C Hte npr H H H H Tr E 4-C 1 H H CH 2 CH=CI He npr H H H H Tr z 141 4-C 1 H H CH 2 G Ct E=H CH 2-CH=CH 2H H H H Tr E 142 4-C 1 H H CH 2 CH=C Ht CH 2-CECH H IH H H Tr z 143 4-Cl H H CH 2CHI=C 4 e CH 2-C-=CH H H H H Tr E 144 4-Cl H H CH 2 CH=C W CH 2 -C( 1 H H H H Tr z TABLE I (Cont/d) NO X Y Z QR 2 R 3 R 4 R 5 R 6 Az POINT ( C) 4-C 1 H H CH 2 CH=CH Et H H H H H Tr E 146 4-C 1 H H Ct 2 CH=CH Et H H H H H Tr z 147 4-C 1 H H C 12 Ci=CH Et Me H H H H Tr E 148 4-C 1 H H CH 2 CH=CH Et Me H H H H Tr z 149 4-Cl H H CH 2 CH=C Me 2 H H H H H Tr 4-C 1 H H CH 2 C=(le 2 Me H H H H Tr 151 4-Cl H H CH 2 CH 2 L Cl M H H H H H Tr 152 4-C 1 H H CH 2 CH 2 e M Me H H H H Tr 153 4-C 1 H H CH 2 CH 2 -CM 4 e H H H H H Tr 154 4-Cl H H CH 2 CH 2 Cmlel Me H H u H Tr 4-Cl H H cu 2 CH 2 GEC Me Et H H H H Tr 156 4-Cl H H C 2 CH 2 C-1 Me npr H H H H Tr 157 4-C 1 H H CH 2 CH 2 GEL 4 eCH 2-CH=CH 2H H H H Tr TABLE I (Cont/d) Mf PO)UND MELTIG NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT( C) 158 4-Cl H H 12 C 2 1 e C H 2 = O HH H Tr 159 4-C 1 H H CH 2 CH 2 C-C Et H H H H H Tr 4-C 1 H H CH 2 CH 2 C C Et Me H H H H Tr 161 4-C 1 H H C 12 CH 2 CHCH 2 H H H H H Tr 162 4-C 1 H H 1 CH 2 C 2CH=CH 2 Me H H H H Tr 163 4-Cl H H CH 2 CH 2 CH=Ct 4 e H H H H H Tr E 164 4-C 1 H H O CH 2 C 2CH=CH Me H H H H H Tr z 4-C 1 H H CH 2 CH 2 CS=Cle Me H H H H Tr E 166 4-Cl H H 1 CH 2 C 12C=C Me Me H H H H Tr z 167 4-C 1 H H C 12 CH 2 EC-t= Et H H H H Tr E 168 4-Cl H H C 12 C 12 CH=CH Me Et H H H H Tr z 169 4-Cl H H CU 2 CH 12CCI-C 4 e npr H H H H Tr E TABLE I (Cont/d) OMPOUND MELTING NO x Y Z Q R R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 4-C 1 H H CH 2 CH 2 CHCH n Pr H H H H Tr Z 171 4-C 1 H H CH 2 CH 2 CH 2-CH=CH 2 H H H H Tr E 172 4-C 1 H H CHI 2 CH 2 H CH 2-CH=C 2 H H II H Tr z 173 4-Cl H H CH 2 CH 2 CH=C He CH 2-0 =CH H H H H Tr E _ O O 174 4-C 1 H H CH 2 CH 2 CH=CH Me C% 2-C(CH H H H H Tr z 4-Cl H H CH 2 CQ 2 CH=CI Et H H H H H Tr E 176 4-C 1 H H CH 2 CH 2 CH=CH Et H H H H H Tr z 177 4-Cl H H CH 2 CH 2 CH=CH Et Me H H H H Tr E 178 4-Cl H H CH 2 CH 2 CH=-CH Et Me H H H H Tr z 179 4-Cl H H CCH 22 CH=C( 2 H It H H H Tr TABLE I (Cont/d) (XCU Mf UND MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( O C) 4-C 1 l H H C-2 = 2 e H H H H Tr 181 2-C 1 4-F H CH 2 C-CH H H H H H Tr 182 2-Cl 4-F H CH 2 C Me H H H H Tr 183 2-Cl 4-F H CH 2 C-=C Me H H H H Tr 184 2-C 1 4-F H CH 2 Coe Me H H H H Tr 2-C 1 4-F H CH 2 C-={Me Et H H H H Tr 186 2-Cl 4-F H CH 2 CC Me n Pr H H H H Tr 187 2-Cl 4-F H CU 2 CC Me CH 12-CHC H H H H Tr 188 2-Cl 4-F H CH 2 (>Q Me CH 2-Ca CH H H H H Tr 189 2-Cl 4-F H CH 2 C-Et H H H H H Tr 2-C 1 4-F H CH 2 C 3 C Et Me H H H H Tr 191 2-C 1 4-F H CH 2 CH O = 2 H H H H H Tr 192 2-C 1 4-F H CH 2 CH=CH 2 Me H H H H Tr 193 2-Cl 4-F H CH 2 CH=CH Me H H H H H Tr E 194 2-Cl 4-F H CH 2 CH=Cl H H H H H H Tr z TABLE I (Cont/d) ODKP Ol O UND I MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 2-C 1 4-F H CH 2 1 CH Me Me 11 H H H Tr E 196 2-C 1 4-F H CHH 2l Me e H H H H Tr z 197 2-C 1 4-F H CH 2 CHR=Ge Et II H H H Tr E 198 2-C 1 4-F H CH 2 CHCH Me Et H H H H Tr z 199 2-C 1 4-F H CH 2 =Ce n Pr H H H H Tr E 2-C 1 4-F H CH 2 a n Pr H H H H Tr z 201 2-Cl 4-F H Cm 2 b= CH 2-CHCH 2 H H H H Tr E 202 2-Cl 4-F H 012 QC=Cle CH 2-{ 1C 2H H H H Tr z 203 2-C 1 4-F H CH 2 CHM CH 2-C-=H H H H H Tr E 204 2-Cl 4-F H 012 (l=Cf CH 2- O H H H H Tr Z TABLE I (Cont/d) COMPOUND I 25 RMELTING NO X Y Z Q R R 2 R 3 R 4R 5 R 6 Az POINT (C) 205 2-C 14-F R CH 2 CH=CH Et H H H H H Tr E 206 2-Cl 4-F H CH 2 CH-CH Et H H H H H Tr z 209 2-C 14-F H C 2 C= 2 HH H H H T 211 -C 1 4-FCHCH 2 e CHH H H H H Tr 207 2-C 14-F H CH 2 C Ht=CH EtMe H H H H Tr E 208 2-C 14-F H C 2 CH=CH Et Me H H H H Tr z 209 2-Cl 4-F H C( 2 CH=O(e 2 H H H H H Tr 210 2-Cl 4-F H CU 2 C Hu=(e 2 me H H H H Tr 211 2-Cl 4-F H CH 2 CH 2CICH H H H H H Tr 212 2-C 14-F H CH 2 CH 2C=CH Me H H H H Tr 213 2-Cl 4-F H C 2 CH 2 ( 3 (le H H H H H Tr 214 2-Cl 4-F H CH 2 CH 2O =Q Ce Me H H H H Tr 215 2-C 14-F H CH 2 CH 2Ct C Me Et H H H H Tr 216 2-C 14-F H CH 2 C 62C Me npr H H H H Tr 217 2-C 14-F H C" 2 CH 2 C Li MeCH 2-CH=CH 2H H H H Tr TABLE I (Cont/d) OMPOMUND 3 MNELTN G 14 NO X Y Z Q R 1 R 2 R 3R R 5R Az POINT ( C) 218 2-Cl 4-F H 2 m 2 CEC Me CH H H H H Tr 219 2-Cl 4-F H CH 2 CH 2C-=C Et H H H H H Tr 220 2-C 14-F H CH 2 CH 2C-OC Et Me H H H H Tr 221 2-Cl 4-F H C" 2 CH 2CH=CH 2 H H H H Tr 222 2-C 14-F H CH 2 CH 2CH=CH 2 Me H H H H Tr 223 2-C 14-F H C{ 2 CH 2CH=CH 1 eH H H H H Tr E 224 2-Cl 4-F H CH 2 CH 2CH=CH Me H H H H H Tr z 225 2-Cl 4-F H CH 2 CH 2CH Ce Me H H H H Tr E 226 2-C 14-F H CH 2 C" 2CH=C HteMe H H H H Tr z 227 2-C 14-F H CH 2 CH 2CHCH Me Et H H H H Tr E 228 2-Cl 4-F H l} 2 CH 2CH=C Hle Et H H H H Tr z 229 2-C 14-F H H 2 CH 2CH=Clt npr H H H H Tr E TABLE I (Cont/d) COMPO NMELTING NO X Y Z Q R 1 R 2 R 3 R 4R 5 R 6 Az POINT ( C) 230 2-Cl 4-F H CH 2 CH 2CH=Ci Me npr H H H H Tr z 231 2-C 14-F H CH 2 C( 2 =-e CH 2-CH=CH,H H H H Tr E 232 2-C 14-F H CH 2 CH 2CH e CH 2-CH=CHH H H H Tr z 233 2-C 14-F H CH 2 CH 2CH=C IaeCH 2-Gs MH H H H Tr 233 2-Cl 4-F H C" 2 C 2 CHI H H H H H Tr E 234 2-Cl 4-F H CH 2 C 2CHCE CH 2-CH H H H H Tr z 235 2-Cl 4-F H CH 2 CH 2CH=l(Et H H H H H Tr E 236 2-Cl 4-F H CH 2 CH 2CH=HM Et H H H H H Tr z 237 2-Cl 4-F H CH 2 CH 2CH"=H Et Me H H H H Tr E 238 2-Cl 4-F H CH 2 CH 2CH=CH Et Me H H H H Tr z 239 2-Cl 4-F H C 2 CH 2 ( 3 =(Me 2H H H H H Tr 240 2-Cl 4-F H CH 2 CH 2 Me H H H Tr TABLE I (Cont/d) OOMPOUND MELTING NO X Y Z Q RI R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 241 2-F 4-F H CH 2 C=CH H H H H H Tr 242 2-F 4-F H CH 2 C-c O Me H H H H Tr 243 2-F 4-F H CH 2 C=C Me H H H H H Tr 244 2-F 4-F H CH 2 C-=Ce Me H H H H Tr 245 2-F 4-F H CH 2 Ca C Me Et H H H H Tr 246 2-F 4-F H CH 2 Ccwe n Pr H H H H Tr 247 2-F 4-F H CH 2 (CQ(e CH 2-CH=CH 2H H H H Tr 248 2-F 4-F H CH 2 C C Me CH 2 CCl H H H H Tr 249 2-F 4-F H ( 1 CH 2 OCC Et H H H H H Tr 250 2-F 4-F H CH 2 C C Et Me H H H H Tr 251 2-F 4-F H CH 2 CH=CH 2 H H H H Tr 252 2-F 4-F H CH 2 CH=CH 2 Me H H H H Tr 253 2-F 4-F H CH 2 CH=C He H H H H H Tr E 254 2-F 4-F H CH 2 CH=C We H H H H H Tr z r 2I I I I I Ir I IN 51 I+e N vr IN,rz I ISN Ir MI E c:
LE - TABLE I (Cont/d) C()POUND MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 265 2-F 4-F H O CH 2 CH=CH Et H H H H H Tr E 266 2-F 4-F H CH 2 CH=CH Et H H H H H Tr z 267 2-F 4-F H CH 2 CH=C Ht Me H H H H Tr E 268 2-F 4-F H CH 2 C Hu= t Me H H H H Tr z 269 2-F 4-F H CH 2 CR=C Me 2 H H H H H Tr 270 2-F 4-F H CH 2 CC Me H H H H Tr 271 2-F 4-F H CH 22 C=CH H H H H H Tr 272 2-F 4-F H C" 2 C 02 CG=e Me H H H H Tr 273 2-F 4-F H C 12 CR 2 C Me H H H H H Tr 274 2-F 4-F H CH 20 CH 2 C Me Me H H H H Tr 275 2-F 4-F H C 02 C" 2 C(C Me Et H H H H Tr 276 2-F 4-F H CH 2 C 02 Ce=Ce C Pnrc H H H H Tr 277 2-F 4-F H CH 2 CH 2 Oe C 4 eCH 2-MCH H H H H Tr TABLE I (Cont/d) COMPOUND MELTING NO x Y Z Q RI R 2 R 3 R 4 R 5 R 6 Az P Or INT( C) 278 2-F 4-F H CH 2 CH 2 C C(e CH 2-G-CH H H H H Tr 279 2-F 4-F H CH 2 CH 2 C-C Et H H H H H Tr 280 2-F 4-F H CH 2 CH 2 CC Et Me H H H H Tr 281 2-F 4-F H CH 2 C 2 c H=H 2 H H H H H Tr 282 2-F 4-F H CH 2 C CHCH 2 Me H H H H Tr 283 2-F 4-F H CH 2 CH 2 E H H H H H Tr E 284 2-F 4-F H CH 2 CH 2 CH(WI H H H H H Tr z 285 2-F 4-F H CH 2 CH 2 a'=He Me H H H H Tr E 286 2-F 4-F H CH 2 CH 2 CH=Ctie Me H H H H Tr z 287 2-F 4-F H CH 2 CH 2 a=C-Mb Et H H H H Tr E 288 2-F 4-F H CH 2 CH 2 c Hale Et H H H H Tr z TABLE I (Cont/d) OOMPOUND METING NO X Y Z Q R 1 R 2 R 3R 4R 5R 6Az POINT ( O C) 289 2-F 4-F H CH 2 CH 224 e n Pr H H H H Tr E 290 2-F 4-F H CH 2 CH 2CICH Menpr H H H H Tr z 291 2-F 4-F H CH 2 CH 2CH EaCH 2-CH=CH 2HH H H Tr E 2922-F 4-F H CI 2 CH 2CH{=IleCH 2-CH=CH 2HH H H Tr z 293 2-F 4-F H CH 2 CH 2CH=a CeCH 2-COCHHH H H Tr E 294 2-F 4-F H CR 2 C 2C b 2-CCH H H H H Tr z 295 2-F 4-F H CR 2 CH 2C=QCH EtH H H H H Tr E 296 2-F 4-F H CH 2 CH 2CH=CH EtH H H H H Tr z 297 2-F 4-F H CH 2 CH 2CH=C HtMe H H H H Tr E 298 2-F 4-F H CH 2 CH 2CH=CH Et Me H H H H Tr z TABLE I (Cont/d) OMPOUND MELTIN NO X Y Z Q RI R 2 R 3 R 4 R 5 R 6 Az POINT (C) 299 2-F 4-F H CH 2 CH 2 CH= 2 Me 2 H H H H H Tr 300 2-F 4-F H CH 2 C" 2 C Me 2 Me H H H H Tr 301 2-C 1 4-C 1 6-C 1 CH 2 e CH H H H H H Tr 302 2-C 1 4-C 1 6-C 1 CH 2 COCH Me H H H H Tr 303 2-C 1 4-C 1 6-C 1 CH 2 Ca 4 e H H H H H Tr 304 2-C 1 4-Cl 6-C 1 CH 2 C Me Me H H H H Tr 305 2-C 1 4-C 1 6-C 1 CH 2 COI 2 e Et H H H H Tr 306 2-C 1 4-C 1 6-C 1 CH 2 C)C Me n Pr H H H H Tr 307 2-C 1 4-C 1 6-C 1 CH 2 CEC Me CH 2-CH=CH 2H H H H Tr 308 2-C 1 4-C 1 6-C 1 CH 2 CC Me CH 2-C(CH H H H H Tr 309 2-C 1 4-C 1 6-C 1 CH 2 C=C Et H H H H H Tr 310 2-C 1 4-C 1 6-C 1 CH 2 C-C Et Me H H H H Tr 311 2-C 1 4-C 1 6-C 1 CH 2 C{=CH 2 H H H lH H Tr 312 2-C 1 4-C 1 6-C 1 CH 2 CH=CH 2 Me H H,H H Tr 313 2-C 1 4-C 1 6-C 1 CH 2 CH=Ct E H H H H r E I HI I TABLE I (Cont/d) OMIPOUND 246 MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5R 6 Az POINT ( C) 314 2-Cl 4-Cl 6-Cl CH 2 QH Me i H H H H Tr z 315 2-C 14-Cl 6-C 1 C 2 CH=d C t Me H H H H Tr E 316 2-C 14-C 1 6-C 1 CH 2 CH=C Me Me H H H H Tr z 317 2-C 14-C 1 6-C 1 CH 2 CQ Me Et H H H H Tr E 318 2-C 14-C 1 6-C 1 CH 2 Qic HteEt H H H H Tr 2 z 319 2-C 14-C 1 6-C 1 CH 2 CM=C He npr H H H H Tr E 320 2-Cl 4-Cl 6-Cl CH 2 QC Hte n Pr H H H H Tr 2 z 321 2-Cl 4-Cl 6-Cl CH 2= 1 (T Me CH 2-CRH=O 2H H H H Tr E 322 2-Cl 4-Cl 6-Cl C{ 2 CH=a Jt C -CH=CH 2H H H H Tr z 323 2-Cl 4-Cl 6-Cl Ci 2 H CH 2-C-5 (CHH H H H Tr E TABLE I (Cont/d) CNMPIOND MELTING NO X Y z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 324 2-C 1 4-C 1 6-C 1 CH 2 CH-C}{ 7 e CH 2-C-CH H H H H Tr z 325 2-C 1 4-C 1 6-Cl CH 2 CH=CH Et H H H H H Tr E 326 2-Cl 4-C 1 6-C 1 CH 2 CH=CH Et H H H H H Tr z 327 2-C 1 4-Cl 6-C 1 CH 2 CH=CH Et Me H H H H Tr E 328 2-C 1 4-Cl 6-Cl CH 2 CH=CH Et Me H H H H Tr z 329 2-C 1 4-C 1 6-Cl CH 2 CH=C Me 2 H H H H H Tr 330 2-C 1 4-C 1 6-C 1 CH 2 CH=(Me 2 Me H H H H Tr 331 2-C 1 4-Cl 6-C 1CH 2 CH 2 C=-=H H H H H H Tr 332 2-Cl 4-C 1 6-C 1CH 2 CH 2 C=CH Me H H H H Tr 333 2-Cl 4-C 1 6-C 1CH 2 CH 2 Cf C Me H H H H H Tr 334 2-C 1 4-C 1 6-C 1CH 2 CH 2 C-=l 4 e Me H H H H Tr 335 2-C 1 4-C 1 6-C 1CH 2 CH 2 C 74 Et H HI H H Tr TABLE I (Cont/d) OMPOUND MELTING NO x Y Z Q R R 2 R 3 R 4 R 5 R 6 Az p INT ( C) 336 2-C 14-Cl 6-C 1 CH 2 CH 2Cle npr H 11 H H Tr 337 2-C 14-C 1 6-Cl CH 2 C 2 C-41 e CH 2-CCH 2 H H H H Tr 338 2-C 14-C 1 6-C 1 CH 2 CH 2(e CH 2-C-CH H H H H Tr 339 2-C 14-C 1 6-C 1 CH 2 CH 2C-C Et H H H H H Tr 340 2-C 14-C 1 6-Cl CH 2 CH 2 COC Et Me H H H H Tr 341 2-C 14-C 1 6-C 1CH 2 CH 2 e=CH 2 H H H H Tr 342 2-C 14-C 1 6-C 1 CH 2 CH 2CH=CH 2 Me H H H H Tr 343 2-C 14-Cl 6-C 1CH 2 CH 2CHH H H H H H Tr E 344 2-C 14-C 1 6-C 1 CH 2 CH 2CH=CI 4 e H H H H H Tr z 345 2-C 14-Cl 6-Cl C CH 2 H 2a C Me Me H H H H Tr E 346 2-C 14-C 1 6-Cl CH 2 CH 2 R Cle Me H H H H Tr z 347 2-C 14-C 1 6-Cl CH 2 CH 2C'CH Me Et H H H H Tr E 348 2-Cl 4-Cl 6-Cl CH 2 CH 2C Ht=I 4 e Et H H H H Tr z TABLE I (Cont/d) OC 1 MPOUND 4 MELTING NO X Y Z Q R 1 R R 3 R 4 R 5 R 6 Az Po INT ( C) 349 2-C 1 4-Cl 6-Cl CH 2 CH 2 CH=CH Me n Pr H H H H Tr E 350 2-C 1 4-C 1 6-C 1 CH 2 CH 2 CH=C He n Pr H H H H Tr z 351 2-C 1 4-C 1 6-C 1CH 2 CH 2 CH=;e Ct 2-CH=CH 2 H H H H Tr E 352 2-C 1 4-C 1 6-C 1 CH 2 C 12 C=E CH 2-CH=CH 2H H H H Tr Z 353 2-C 1 4-C 1 6-Cl CH 2 CH 2 CH=CH"e CH 2-C-CH H H H H Tr E 354 2-C 1 4-C 1 6-C 1CH 2 CH 2 CHC Re CH 2-C-CH H H H H Tr z 355 2-C 1 4-C 1 6-C 1 CH 2 CH 2 CH=CH Et H H H H H Tr E 356 2-Cl 4-C 1 6-C 1 CH 2 CH 2 CH=CH Et H H H H H Tr z 357 2-C 1 4-C 1 6-C 1 CH 2 CH 2 CH=C Hl Et Me H H H H Tr E 358 2-C 1 4-C 1 6-C 1 C 22 CH 2 CH=CH Et Me H H H H Tr Z TABLE I (Cont/d) C(IMPOUND 23 6 ' IN NO X Y Z Q R 1 R 2 R 3 R 4 R R 6 Az POINT( C) 359 2-C 1 4-C 1 6-C 1 CH 2 CH 2 C=C Me 2 H H H H H Tr 360 2-C 1 4-C 1 6-C 1 CH 2 CH 2 CH=C Me 2 Me H H H H Tr 361 2-C 1 6-C 1 H CH 2 C-CH H H H H H Tr 362 2-C 1 6-C 1 H CH 2 CH Me H H H H Tr 363 2-C 1 6-C 1 H CH 2 C Me H H H H H Tr l 364 2-C 1 6-C 1 H 6 12 Cl C Me H H H H Tr 365 2-C 1 6-C 1 H J 2 C=e Et 'H H H H Tr 366 2-C 1 6-C 1 H CH 2 C-C Me n Pr H H H H Tr 367 2-C 1 6-C 1 H CH 2 Oz Cle CH 2-CH=CH 2H H H H Tr 368 2-C 1 6-C 1 H CH 2 C-=C Me C H 2-C H H HH H Tr 369 2-C 1 6-Cl H CH 2Ce=Et H H H t H Tr CH 2 H 370 2-C 1 6-C 1 H CH C-=e C Et Me H H H H Tr 371 2-C 1 6-C 1 H CH 2 CH=CH 2 H H H H H Tr 100 372 2-C 1 6-C 1 H CH 2 C-=CH 2 Me H H H H Tr 373 2-Cl 6-Cl H CH Cfe HH H H;H Tr 373 2-C 1 6-C 1 H CH 2 CH=C Hte H H H H H Tr E TABLE I (Cont/d) COMPOUND I MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 374 2-Cl 6-Cl H CH 2 CH=CR Ie H H H H H Tr z 375 2-C 1 6-C 1 H CH 2 CHCH Me Me H H H H Tr E 376 2-Cl 6-C 1 H CH 2 CH=Mme Me H 11 H H Tr z 377 2-C 1 6-C 1 H CH 2 CH=I Me Et H H H H Tr E - - 378 2-Cl 6-C 1 H OH 2 Cle Et H H H H Tr z 379 2-C 1 6-C 1 H CH 2 CH=a C Me n Pr H H H H Tr E 380 2-C 1 6-C 1 H CH 2 CH:CI 4 e n Pr H H H H Tr z 381 2-Cl 6-Cl H CH 2 CH=CI Me CH 2-CH=CH 2H H H H Tr E 382 2-Cl 6-Cl H CH 2 =Ce CH 2-CH=CH 2H H H H Tr z 383 2-C 1 6-Cl H CH 2 CH=C Ie CH 2-CCH H H H H Tr E I _ TABLE I (Cont/d) COM POUND ' LTING NO X Y Z Q R R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 384 2-C 1 6-C 1 H CH 2 C 11 CH 2-CCH HI H H H Tr z 385 2-C 1 6-Cl H CH 2 CH=CH Et H H H H H Tr E 386 2-C 1 6-C 1 H CH 2 C=CH Et H H H H H Tr z 387 2-C 1 6-C 1 H CH 2 C=CH Et Me H H H H Tr E 03 E oo 388 2-C 1 6-C 1 H CH 2 CH=CH Et Me H H H H Tr z 389 2-C 1 6-C 1 H CH 2 CH=C Me 2 H H H H H Tr 390 2-C 1 6-C 1 H CH 2 CH=C Oe 2 Me H H H H Tr 391 2-C 1 6-C 1 H CH 2 CH 2 CCH H H H H H Tr 392 2-Cl 6-C 1 H CH 2 CH 2 C-=CH Me H H H H Tr 393 2-C 1 6-C 1 H CH 2 CH 2 C(C Me H H H H H Tr 394 2-C 1 6-C 1 H CH 2 CH 2 C-C Me Me H H H H Tr 395 2-C 1 l6-C 1 H CH 2 CH 2 C Me Et H H H H Tr 396 2-Cl 6-Cl H CH 2 CH 2 C C Me n Pr H H H H Tr I TABLE I (Cont/d) COMPOUND ts 23 " R ALT(NG NO X Y Z Q R R R R 4 R 5R 6 AZ POINT ( C) 397 2-Cl6-Cl H C 2 CH 2 Co C CH 2-C=CH 2HH H H Tr 398 2-C 16-Cl H CH 2 CH 2Ce CH 2-C-H H H H H H Tr 399 2-C 16-C 1H CH 2 CH 2C=C Et H H H H H Tr 400 2-Cl6-C 1 H CH 2 CH 2C-C Et Me H H H H Tr 401 2-Cl6-Cl H 2 CH 2 CH=CH 2 H H H H H Tr 402 2-Cl6-Cl H CH 2 CH 2CH=CH 2 Me H H H H Tr 403 2-C 16-C 1H CH 2 CH 2CH=CH 4 eH H H H H Tr E 404 2-Cl6-Cl H CH 2 CH 2CHC H H H H H Tr Z 405 2-Cl 6-C 1H CH 2 CH 2CH=CH Me Me H H H H Tr E 406 2-C 16-C 1H CH 2 CH 2CHCH Me Me H H H H Tr z 407 2-C 16-C 1H CH 2 CH 2CH=CH We Et H H H H Tr E 408 2-C 16-C 1H CH 2 CH 2CH=C He Et H H H H Tr z TABLU I (Cont/d) OMPOUKD mg Z,l MLING X Y Z Q | R 1 R 2 R 3R 4 i R 5R 6AzPOINT ( C) I 409 2-C 16-C 1H CH 2 CH 2C Hte npr H 11HH H Tr E 410 2-C 16-ClH CH 2 CQ 12CH=i Ien Pr H H H H Tr z 411 2-Cl6-ClH Q 12 CH 2CHCI Iea 12-CH=C 112HH H H Tr Zo 411 2-C 16-C 1H C% 2 CH 2CH=I MeCH 2-CH 2HH H H Tr E 412 2-Cl6-ClH CH 2 C{ 2C Hi=C IteCH 2-CH= 2HH H H Tr z 0 413 2-C 16-C 1H CH 2 CH 2C Hl CtCH 2-CHHH H H Tr E 414 2-C 16-C 1H CH 2 CH 2CH=CtftCH 2-0 m OHHH H H Tr z 415 2-C 16-C 1H CH 2 CH 2CH=CH EtH H H H H Tr E 416 2-Cl6-ClH CH 2 CH 2C 11 =tttH H H H H Tr z 417 2-Cl6-ClH 2 CH=CH Et He ttHH H Tr E 418 2-C 16-C 1H CH 2 CH 2CH=CH EtMe H H H H Tr z i-I TABLE I (Cont/d) (XMIOUIJND P MELTING NO X Y Z Q R 2 R 3 R 4 R 5 R 6 Az POINT ( O C) 419 2-C 1 6-C 1 H CH 2 CH 2 CH=Ie 2 H H H H H Tr 420 2-C 1 6-C 1 H CH 2 CH 2 CHA= 4 e 2 Me H H H H Tr 421 2-C 1 4-C 1 H CH Me CH=CH 2 H H H H H Tr 422 2-Cl 4-C 1 H CH Me CH=CH 2 Me H H H H Tr 423 2-Cl 4-Cl H CH Me Cl-CH 2 Et H H H H Tr 424 2-Cl 4-Cl H CH Me C=CH 2 CH 2-CH=CH 2 H H H H Tr 425 2-C 1 4-C 1 H CH Me CH=CI Me H H H H H Tr 426 2-C 1 4-Cl H CH Me CCH Me Me H H H H Tr 427 2-C 1 4-C 1 H C Me 2 CH=CH 2 H H H H H Tr 428 2-C 1 4-C 1 H C Me 2 CH=CH 2 Me H H H H Tr 429 2-C 1 4-C 1 H Catle C-=e H H H H H Tr 430 2-C 1 4-Cl H CH Me C 2 M e H H H H Tr 431 2-C 1 l H H Cti Me CICH 2 H H H H H Tr Oil 432 2-C 1 H H C Me CH=CH 2 Me H H H H Tr 433 2-C 1 H H C He CH=CH 2 Et H H H H Tr TABLE I (Cont/d) j O CMPOUND ' ' w icr? 4 ldu ND' r MELTING NO X, Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 434 2-Cl H H CH Me CHCH 2 CH 2-CH=CH 2H H H H Tr 435 2-C 1 lH H Ce CH-= e H H H H H Tr 436 2-Cl H H clwe CH=C Hle Me H H H H Tr 437 2-Cl H H OC Me 2 CH=CH 2 H H H H H Tr Oil 438 2-Cl H H G Me 2 CH=CH 2 Me H H H H Tr 439 2-Cl H H C Me CQC Me H H H H H Tr 440 2-Cl H H CI Me C=O Me Me H H H H Tr on 441 4-C 1 H H CH Me CH=CH 2 H H H H H Tr Oil 442 4-Cl H H CH 4 e CH=CH 2 Me H H H H Tr 443 4-C 1 H H Cae CH=CH 2 Et H H H H Tr 444 4-Cl H H CH Me CH=CH 2 CH 2-CH=CH 2H H H H Tr 445 4-Cl H H Ce CH=CH 4 e H H H H H Tr 446 4-Cl H H C 4 e CH Ci=ae Me H H H H Tr 447 4-Cl H H C Me 2 C=CH 2 H H H H H Tr 448 4-Cl H H C Me 2 -=C{ 2 Me H H H H Tr TABLE I (Cont/d) Ct IIPOUND' MELTING NO X Y Z Q R R 3 R 4 R 5 6 Az POINT ( C) 449 4-C 1 H H CH Me ( 4 e H H H H H Tr 450 4-C 1 H H C C Me Me H H H H Tr 451 2-Cl 4-F H C Me CH=CH 2 H H H H H Tr Oil 452 2-Cl 4-F H CB 14 e CHCH 2 Me H H H H Tr 453 2-C 1 4-F H C Me CH=CH 2 Et H H H H Tr 454 2-C 1 4-F H C CH=CH 2CH 2-C=CH 2H H H H Tr TrU 455 2-Cl 4-F H CH Me CH=C He H H H H H Tr 456 2-Cl 4-F H C Rle Cl=C It 4 e Me H H H H Tr 457 2-C 1 4-F H (Ce 2 =CH 2 H H H H H Tr 458 2-Cl 4-F H C Me 2 CH=CH 2 Me H H H H Tr 459 2-C 1 4-F H CH Me Ct)4 e H H H H H Tr 460 2-Cl 4-F H C Me C e Me H H H H Tr 461 2-C 1 6-Cl H Ct Me CH=CH 2 H H H H H Tr 123-125 TABLE I (Cont/d) FCOMPOUND f MELTING NO X Y Z Q R 1 R 2 R 3 R 4 R 5 R 6 Az POINT ( C) 462 2-Cl H H C Me 2 CH 2 H Me H H H Tr oil 463 2-C 1 H H Ole 2 C Hutle H H H H H Tr E 464 2-C 1 H H C Me 2 CH-CH Ee H H H H H Tr z 465 2-C 1 H 1 I C Me 2 CH=tl Et H H H H H Tr E 466 2-C 1 H H C Me 2 CH=CH Et t 11 H H H H Tr Z - TABLE II: PROTON NMR DATA Table II shows proton nmr data for certain compounds described in Table I and characterised therein as oils Chemical shifts are measured in ppm from tetramethylsilane and deuterochloroform was used as solvent throughout The following abbreviations are used:
br = broad t = triplet s = singlet q = quartet d = doublet m = multiplet dd = doublet of doublets J = coupling constant Hz = Hertz.
56 - Compound NMR DATA No.
3 8 19 ( 1 H,s), 7 98 ( 1 H,s), 7 47 ( 1 H,m), 7.40 ( 1 H,m), 7 23 ( 1 H,m), 4 49 ( 1 H,d,J 13 Hz), 4 14 ( 1 H,d,J 13 Hz), 3 55 ( 1 H, br s), 3 18 ( 1 H,d, J 13 Hz), 3 05 ( 1 H,d, J 13 Hz), 2 20 ( 1 H, m), 2 05 ( 1 H,m), 1 84 ( 3 H,m).
69 8 20 ( 1 H,m), 7 96 ( 1 H,m), 7 51 ( 1 H,m), 7.38 ( 1 H,m), 7 21 ( 2 H,m), 4 53 ( 1 H,d,J 12 Hz), 4 15 ( 1 H, d, J 12 Hz), 3 47 ( 1 H br s), 3 27 ( 1 H, d, J 12 Hz), 3 10 ( 1 H,d, J 12 Hz), 2 4 2 0 ( 4 H,m), 1.18 ( 3 H, t, J 7 Hz).
101 8 11 ( 1 H,s), 7 94 ( 1 H,s), 7 39 ( 2 H,m), 7.20 ( 2 H, m), 5 76 ( 1 H, m), 4 99 ( 2 H,m) 4.35 ( 1 H, d, J 12 Hz), 4 08 ( 1 H,d, J 12 Hz), 3 31 ( 1 H,s), 3 02 ( 2 H,s), 2 22 ( 2 H,m), 1 49 ( 2 H,m).
123 8 20 ( 1 H,s), 7 97 ( 1 H,s), 7 27 ( 4 H,m), 4.39 ( 1 H, d, J 12 Hz), 4 19 ( 1 H,d,J 12 Hz), 3 30 ( 1 H, br s), 2 94 ( 1 H,d,J 12 Hz), 2 78 ( 1 H, d, J 12 Hz), 2 15 ( 1 H, d, J 16 Hz), 1 97 ( 1 H, d, J 16 Hz) 1.87 ( 3 H,s).
57 - Compound NMR DATA No.
129 8 19 ( 1 H,s), 7 98 ( 1 H,s), 7 28 ( 4 H,m), 4.40 ( 1 H, d, J 11 Hz), 4 19 ( 1 H, d, J 11 Hz), 3 31 ( 1 H, br s), 2 95 ( 1 H, d, J 11 Hz), 2 78 ( 1 H, d, J 11 Hz), 2 21 ( 3 H, m), 1 96 ( 1 H, m), 1 19 ( 3 H, t, J 7 Hz).
8 19 ( 1 H, s), 7 95 ( 1 H,s), 7 28 ( 4 H,m), 4.35 ( 1 H, d, J 13 Hz), 4 26 ( 1 H,d,J 13 Hz), 3 40 ( 1 H,s), 2 93 ( 1 H, d, J 12 Hz), 2 81 ( 1 H,d, J 12 Hz), 2 22 ( 4 H, m), 1 18 ( 3 H, t, J 7 Hz).
131 8 13 ( 1 H,s), 7 99 ( 1 H,s), 7 26 ( 4 H,m), 5.87 ( 1 H,m), 5 22 ( 1 H, d, J 9 Hz), 5.10 ( 1 H, d, J 15 Hz), 4 19 ( 1 H, d, J 12 Hz), 4 08 (IH, d, J 12 Hz), 3 18 ( 1 H, br s), 2 80 ( 1 H, d, J 11 Hz), 2.70 ( 1 H, d, J 1 l Hz), 2 11 ( 2 H, d, J 7 Hz).
431 8 00 ( 2 H, br s), 7 55-7 15 ( 4 H, m), 5.90 ( 1 H,m), 5 30-4 90 ( 2 H,m), 4 49 ( 1 H, m), 3 88 ( 1 H, m), 3 25-2 87 ( 3 H, m), 2 05 ( 1 H, m), 1 19 ( 3 H, m).
58 - Compound NMR DATA No.
437 7 77 ( 1 H, s), 7 75 ( 1 H,s), 7 48 (l H,m), 7.33 ( 1 H,m), 7 14 ( 2 H, m), 6 09 ( 1 H, dd J 16 and 10 Hz), 5 07 ( 1 H, d, J 10 Hz), 5 06 ( 1 H, d, J 16 Hz), 4 44 ( 1 H,s), 4.41 ( 1 H, d, J 14 Hz), 4 04 ( 1 H, d, J 14 Hz), 3 40 ( 1 H, d, J 13 Hz), 3.04 ( 1 H, d, J 13 Hz), 1 18 ( 3 H,s), 1.13 ( 3 H,s).
441 8 20 and 8 08 ( 1 H, 2 xs), 7 94 ( 1 H,s), 7.35-7 10 ( 4 H,m), 5 95-5 70 ( 1 H,m), 5.20-4 90 ( 2 H,m), 4 24 ( 1 H,m), 3 96 ( 1 H,m), 3 30-2 57 ( 2 H,m), 2 10 ( 1 H,m), 1.14 ( 3 H, d, J 7 Hz).
451 8 08 and 8 01 ( 1 H, 2 xs), 7 92 and 7 91 ( 1 H, 2 xs), 7 58-7 35 ( 1 H,m), 7 11 ( 1 H,m),j 6.97 ( 1 H,m), 6 02-5 75 ( 1 H,m), 5 25-4 91 ( 2 H,m), 4 43 ( 1 H,m), 3 83 ( 1 H,m), 3 11 ( 1 H,m), 2 90 ( 1 H,m), 2 04 ( 1 H,m), 1 19 ( 3 H,m).
462 8 08 ( 1 H,s), 7 92 ( 1 H,s), 7 35 ( 1 H,m), 7.10 ( 2 H, m), 6 90 ( 1 H,m), 6 10 (dd, J 16 and 10 Hz), 5 03 ( 2 H,m), 4 65 ( 2 H,m), 4.05 ( 1 H, q, J 7 Hz), 3 08 ( 1 H,s), 1 43 ( 3 H,d,J 7 Hz), 1 18 ( 3 H,s), 1 08 ( 3 H,s).
59 - Compounds of general formula (I):
R 3 OR 2 R 5 X I I I C C C __ Az (I) I I I i Y R 4 Q R 6 z Z I R 1 wherein Az, Q, R 1 to R 6, X, Y and Z are as defined above except that R 2 is not the same as hydrogen can be prepared from compounds of general formula (IV) lcompounds of formula (I) wherein R 2 is hydrogenl:
R 3 OH R 5 x I I C C C AZ (IV) Y I I I Z R 4 Q R 6 R 1 wherein Az, Q, R 1, R 3 to R 6, X, Y and Z are as defined above, by treatment with a base, such as sodium hydride, and an alkyl halide, an alkenyl halide or an alkynyl halide, R 2 Hal wherein Hal can be chlorine, bromine or iodine in a suitable solvent such as tetrahydrofuran.
Compounds of general formula (IV) wherein R 1 is a group of general formula (III) wherein R 8 and R 9 or R 8 and R 10 are hydrogen can be prepared by hydrogenation of compounds of general formula (V) - lcompounds of general formula (IV) wherein R 1 is a group of general formula (II)l:
R 3 OH R 5 X._ I CO 9 C C C Az (V) Y</ l l Z R 4 Q R 6 C C 17 R wherein Az, Q, R 3 to R 7, X, Y and Z are as defined above In cases where both R 8 and Rio are hydrogen (a cis double bond) this can be achieved by catalytic hydrogenation over a suitable catalyst, such as palladium on barium sulphate Compounds in which both R 8 and R 9 are hydrogen (a trans double bond) can be prepared by isomerisationo bf compounds in which both R 8 and R 10 are hydrogen (a cis double bond), for instance by iodine or diphenyl disulphide.
Compounds of general formula (IV) can be prepared by treatment of compounds of general formula (VI):
61 - R 3 O R 5 XI I) I 1 C C C Az (VI) y i Z R 4 R 6 wherein Az, R 3 to R 6, X, Y and Z are as defined above with compounds of general formula (VII):
M Q R 1 (VII) wherein Q and R 1 are as defined above and M is a metal such as magnesium, lithium or titanium.
Compounds of general formula (VI) can be prepared by treatment of compounds of general formula (VIII):
R 3 O R 5 x O C C C Hal (VIII) Z R 4 R 6 wherein Hal, R 3 to R 6, X, Y and Z are as defined above an azole (imidazole or 1,2,4-triazole) in the presence of an appropriate base, such as potassium carbonate, in a suitable solvent, such as dimethyl formamide.
As an alternative compounds of general formula (V) can be prepared by treatment of compounds of general formula (VIII) with compounds of general formula (VII) followed by treatment with an azole (imidazole or 1,2,4-triazole).
62 - Compounds of general formula (VIII) can be prepared by oxidation of compounds of general formula (IX):
R 3 OH R 5 X I I <C C C C Hal (IX) Yowl/ Il Z R 4 H R 6 wherein Hal, R 3 to R 6, X, Y and Z are as defined above with a suitable oxidizing agent such as Jones reagent.
Compounds of general formula (IX) wherein R 5 and R 6 are hydrogen can be prepared by treatment of compounds of general formula (X):
R 3 H C C C (X) |R 4 H Z H wherein R 3, R 4, X, Y and Z are as defined above, with a solution of the appropriate halogen, for instance bromine, in water.
Compounds of general formula (X) wherein R 3 and R 4 are hydrogen can be prepared by treatment of Grignard reagents of general formula (XI):
63 - X Mg Hal (XI) z wherein X, Y and Z are as defined, above with allyl bromide, optionally in the presence of a copper (I) catalyst, in a suitable solvent such as diethyl ether.
Compounds of general formula (XI) can be prepared by methods set out in the literature.
As an alternative compounds of general formula (VIII) can be prepared by treatment of Grignard reagents of general formula (XII):
R 3 R X I C Mg Hal (XII) y.
wherein Hal, R 3, R 4, X, Y and Z are as defined above, with an acid chloride of general formula (XIII):
0 R 5 1 I I Cl C C Hal (XIII) R 6 wherein Hal, R 5 and R 6 are as defined above, in a suitable solvent such as diethyl ether or tetrahydrofuran at low temperature.
Compounds of general formula (VII), (XII) and (XIII) may be prepared by methods set out in the literature.
As a further alternative compounds of general formula (VI) can be prepared by oxidation of compounds of general formula (XIV):
X R 3 OH R 5 Y O -C C C Az (XIV) I I I Z R 4 H R 6 R 4 6 wherein Az, R to R 6, X, Y and Z are as defined above An appropriate method of oxidation is the Swern modification of the Moffat oxidation (dimethyl sulphoxide, oxalyl chloride and triethylamine in dichloromethane), or the Moffat oxidation (dimethyl sulphoxide, acetic anhydride and triethylamine in dichloromethane) or the use of Jones reagent.
Compounds of general formula (XIV) wherein R 5 and R 6 are hydrogen can be prepared by treatment of an epoxide of general formula (XV):
X R 3 0 H C C (XV) Y I I\ Z R 4 H H wherein R 3, R 4, X, Y and Z are as defined above, with an - azole (imidazole or 1,2,4-triazole) in an appropriate solvent such as ethanol.
Compounds of general formula (XV) can be prepared by epoxidation of compounds of general formula (X) with an appropriate peracid such as peracetic acid or m-chloroperbenzoic acid.
As an alternative compounds of general formula (XV) can be prepared by treatment of compound of general formula (IX) (wherein R 5 and R 6 are hydrogen) with an appropriate base such as sodium hydroxide in a suitable solvent such as methanol or ethanol.
As an alternative compounds of general formula (IV) wherein R 6 is hydrogen can be prepared by treatment of compounds of general formula (XVI):
X R 3 O R 5 Q C C C (XVI) Y R 4 Q Z H R 1 wherein Q, R 1, R 3 to R 5, X, Y and Z are as defined above, with an azole (imidazole or 1,2,4-triazole) in a convenient solvent such as ethanol.
Compounds of general formula (XVI) can be prepared by treatment of compounds of general formula (XVII):
66- R 3 O OC C Q R |R 4 (XVII) z wherein Q, R 1, R 3, R 4, X, Y and Z are as defined above, with a sulphur ylid of general formula (XVIII):
R 2 S-CHR 5 (XVIII) wherein R 5 is as defined above, and either (a) if R 5 is hydrogen then R is methyl or (b) if R 5 is not hydrogen then R is phenyl, in a convenient solvent such as dimethyl sulphoxide Sulphur ylids of general formula (XVIII) can be prepared by methods set out in the literature.
Compounds of general formula (XVII) can be prepared by methods set out in the literature, for instance, by the treatment of compounds of general formula (XIX):
R 3 0 (XIX) x I 1 i C C -Cl y/ I /z R 4 z 67 - wherein R 3, R 4, X, Y and Z are as defined above, with a compound of general formula (VII) wherein M is copper (I) or M is magnesium (at low temperature).
As an alternative compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XX):
R 3 O X c C H (XX) 4 Z R wherein R 3, R 4, X, Y and Z are as defined above, with a compound of general formula (VII) wherein M is lithium or magnesium followed by oxidation with a suitable oxidising agent such as chromium trioxide.
As a further alternative compounds of general formula (XVII) can be prepared by treatment of a compound of general formula (XXI):
R 3 0 i C C C NR 2 (XXI) Y I Z R 4 wherein R 3, R 4, X, Y and Z are as defined above, and NR 2 is a convenient amide group such as N Me O Me with a group of general formula (VII) wherein M is lithium or 68 - magnesium in a convenient solvent such as tetrahydrofuran.
As a further alternative compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XXII):
R 3 0 0 C C ow (XXII) Y I Z R wherein R 3, R 4, X, Y and Z are as defined above, and W is hydrogen or lithium with a compound of general formula (VII) wherein M is lithium in a suitable solvent such as ether.
As a further alternative compounds of general formula (XVII) wherein Rl is a group of general formula (III) wherein R 8 and R 9 or Ra and Rio are hydrogen, can be prepared by hydrogenation of compounds of general formula (XVII) wherein R 1 is a group of general formula (II) In cases where R 8 and Rio are hydrogen (a cis double bond) a suitable reducing agent is hydrogen over a suitable catalyst, for instance palladium on barium sulphate Cases where R 8 and R 9 are hydrogen (a trans double bond) can be prepared by isomerisation of cases where R 8 are Rio are hydrogen (a cis double bond) with a suitable catalyst such as iodine.
As an alternative compounds of general formula (XVII) can be prepared by treatment of compound of general formula (XXIII):
69 - il C 1 C Q R 1 (XXIII) wherein Q and R 1 are as defined above, with compounds of general formula (XII), wherein M is copper (I) or M is magnesium (at low temperature) in a suitable solvent such as ether.
As a further alternative compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XXIV):
H C Q R 1 (XXIV) wherein Q and Ri are as defined above, with compounds of general formula (XII) or compounds of general formula (XXV):
X R 3 Y C Li (XXV) I Z R 4 wherein R 3, R 4, X, Y and Z are as defined above, in a suitable solvent such as ether followed by oxidation with a suitable oxidising agent such as chromium trioxide.
As a further alternative compounds of general formula (XVII) can be prepared by treatment of compounds of general formula (XXVII):
- O wherein Q, R 1 and W are as defined above, or compounds of general formula (XXVII):
O R 2 N C Q R 1 (XXVII) wherein Q, R 1 and NR 2 are as defined above (eg NR 2 N Me O Me), with compounds of general formula (XXV) in a suitable solvent such as diethyl ether.
Compounds of general formula (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI) and (XXVII) can be prepared by methods set out in the literature.
As a further alternative compounds of general formula (IV) can be prepared by treatment of compounds of general formula (XXVIII):
O R 5 11 I R 1 Q C C -Az (XXVIII) R 6 wherein Az, Q, R 1, R 5 and R 6 are as defined above, with a Grignard reagent of general formula (XII) in a suitable solvent such as ether.
71 - Compounds of general formula (XXVIII) can be prepared by treatment of compounds of general formula (XXIX):
0 R 5 11 I R 1 _Q C C Hal (XXIX) wherein Hal, Q, R 1, R 5 and R 6 are as defined above, with an azole (imidazole or 1,2,4-triazole) in the presence of a suitable base such as potassium carbonate, in a suitable solvent such as dimethyl formamide.
Compounds of general formula (XXIX) can be prepared by treatment of compounds of general formula (XIII) with compounds of general formula (VII) M is copper (I) or M is magnesium (at low temperature) in a suitable solvent such as tetrahydrofuran.
As an alternative when both R 11 and R 12 are alkyl groups compounds of general formula (XXIX) can be prepared by treatment of compounds of general formula (XXX):
O R 5 11 R 1 Q C -C H (XXX) 16 R 6 72 - wherein Q, R 1, R 5 and R 6 are as defined above with a suitable halogen (such as chlorine or bromine) as described in the literature.
Compounds of general formula (XXX) can be prepared by methods set out in the literature.
As a further alternative compounds of general formula (IV) wherein R 3 and R 4 are hydrogen can be prepared by treatment of compounds of general formula (XXXI):
0 R 5 /\ H 2 C' C C Az (XXXI) R R wherein Az, R 1, R 5 and R 6 are as defined above, with a Grignard reagent of general formula (XI) in the presence of a copper (I) catalyst.
As a further alternative compounds of general formula (IV) wherein Q is Q 1 (and R 11 is hydrogen and R 12 is hydrogen or an alkyl group) can be prepared by treatment of compounds of general formula (XXXII):
X R 3 R 5 I I < C C C Az Z HC-R 4\ R 6 (xxx I)2 (XXXII) wherein AZ, R 3 to R 6, R 12, X, Y and Z are as defined above, with a compound of general formula (XXXIII):
MC _ C R 7 (XXXIII) wherein R 7 is as defined above and M is magnesium lfor cases where R 1 is a group of general formula (II)l, or with a compound of general formula (XXXIV):
M R 9 C C (XXXIV) R 8 / \ Ri O wherein R 8 to R 10 are as defined above and M is copper (I) lfor cases where R 1 is a group of general formula (III)l.
As an alternative compounds of general formula (IV) wherein Q is not the same as Q 1 (and R 1 l is hydrogen and R 12 is hydrogen or an alkyl group) can be prepared by treatment of compounds of general formula (XXXII) with the appropriate organocuprate (i.e Cu LR 1 wherein L is Q lacking CR 11 R 12 and R 1 is as defined above).
Compounds of general formula (XXXII) can be prepared by treatment of compounds of general formula (VI) with a sulphur ylid of general formula (XXXV):
R 2 S CGHR 12 (XXXV) wherein R 12 is as defined above, and either (a) if R 12 is hydrogen then R is methyl or (b) if R 12 is not hydrogen then R is phenyl.
74 - As a further alternative compounds of general formula (V) (wherein R 7 is alkyl, alk-2-enyl, alk-3- enyl, alk-2-ynyl or alk-3-ynyl) can be prepared by treatment of compounds of general formula (V) (wherein R 7 is hydrogen) with a suitable base followed by a compound of general formula R 7 Hal wherein Ha' is as defined above and R 7 is as defined immediately above.
Compounds of general formula (XXXIII) can be prepared by treatment of compounds of general formula (XXX) with the sulphur ylid of formula Me 252 CH?.
Compounds of general formula (XXXI), (XXXIII), (XXXIV) and (XXXV) can be prepared by methods set out in the literature.
The compounds, their salts and metal complexes are active fungicides, particularly against the diseases Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e g coffee, apples, vegetables and ornamental plants.
Erysiphe qraminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fuliqinea on cucurbits (e g.
cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines.
Helminthosporium spp, e g Pyrenophora teres, Pseudocercosporella herpotrichoides, Rhynchosporium spp, Septoria spp and Rhizoctonia spp e g R.
cerealis Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans Venturia inaequalis (scab) on apples.
Some of the compounds have also shown a broad range of activities against fungi in vitro They have activity against various post-harvest diseases on fruit (e g Penicillium diaqatum and italicum on oranges Gloeosporium musarum on bananas and Botrytis cinerea on grapes) Further some of the compounds are active as seed dressings against:
Fusarium spp, Septoria spp, Tilletia spp (i e.
bunt, a seed borne disease of wheat), Ustilaqo spp.
and Helminthosporium spp on cereals.
The compounds can move acropetally in the plant tissue Moreover, the compounds can be volatile enough to be active in the vapour phases against fungi on the plant.
They may also be useful as industrial (as opposed to agricultural) fungicides, e g in the prevention of fungal attack on wood, hides, leather and especially paint films.
The compounds may be used as such for fungicidal purposes but are more conveniently formulated into compositions for such usage The invention thus provides a fungicidal composition comprising a compound of generalformula (I) as hereinbefore defined, a salt, or metal complex thereof; and, optionally, a carrier or diluent.
The invention also provides a method of combatting a fungi, which comprises applying to a plant, to seed of a plant, or to the locus of the plant or seed, a compound, salt, or metal complex thereof as hereinbefore defined.
The compounds of the invention also possess useful pharmaceutical activity as aromatase inhibitors Aromatase is an enzyme which effects the 76 aromatisation of ring A in the metabolic formation of various steroid hormones Certain tumours are dependent for their maintenance or growth upon circulating steroids containing an aromatic ring A, and a chemical agent which inhibits the aromatisation of ring A in the precursors of such steroids is likely to be effective in inhibiting the growth of such hormone dependent tumours.
The compounds, their salts and their metal complexes can be applied in a number of ways, for example they can be applied, formulated or unformulated, directly to the foliage of a plant, or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour; or as slow release granules Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted; or to the soil generally, to paddy water or to hydroponic culture systems The invention compounds may also be injected into plants or trees and they may also be sprayed onto vegetation using electrodynamic spraying techniques.
The term "plant" as used herein includes seedlings, bushes and trees Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition The type of composition used in 77 any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay Such granules can be preformed granules suitable for application to the soil without further treatment These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methylpyrrolidone or dimethylformamide).
The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also containg wetting, dispersing or emulsifying agent(s) Suitable organic solvents are ethylene dichloride, isopropyl alcohol, 78 propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (eg 2- ethoxyethanol and 2-butoxyethanol).
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, eg fluorotrichloromethane or dichlorodifluoromethane.
The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.
Alternatively, the compounds may be used in micro-encapsulated form They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.
By including suitable additives, for example additives for improving the distribution, adhesive powder and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The compounds can be used as mixtures with fertilisers (e g nitrogen-, potassium or phosphorus-containing fertilisers) Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound are preferred.
Such granules suitably contain up to 25 % by weight of the compound The invention therefore also provides a fertiliser composition comprising the compound of general formula (I) or a salt thereof.
The compositions may also be in the form of liquid preparations for use as dips or sprays which 79 - are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants e g wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s); or which are spray formulations of the kind suitable for use in electrodynamic spraying techniques The foregoing agents can be cationic, anionic or non-ionic agents Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonate aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl and triisopropyl- naphthalene sulphonates).
Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl or nonyl-phenol and octylcresol Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydride, the condensation products of the said partial esters with ethylene oxide, and the lecithins Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a - concentrate containing a high proportion of the active ingredient(s), and the concentrate is to be diluted with water before use These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional and electrodynamic spray equipment The concentrates may conveniently contain up to 95 %, suitably 10-85 %, for example 25-60 %, by weight of the active ingredient(s) These concentrates suitably contain organic acids (e g alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecyl benzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005 % or 0 01 % to 10 % by weight of active ingredient(s) may be used.
The compositions of this invention can comprise also other compound(s) having biological activity, e.g compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal activity.
The other fungicidal compound can be, for example, one which is capable of combating ear 81 - diseases of cereals (e g wheat) such as Septoria, Gibberella and Helminthosporium spp, seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple etc.
These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula (I) alone; further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I) Examples of the other fungicidal compound are carbendazim, benomyl, thiophanatemethyl, thiabendazole, fuberidazole, etridazole, dichlorofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminium, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, R 0151297, pyrazophos, ethirimol, ditalimofos, tridemor;ph, triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz, flutriafol, hexaconazole i e the chemical l-( 1,2,4-triazol-1- yl)-2-( 2,4-dichlorophenyl)hexan-2-ol, flusilazole i.e the chemical (l-(bis-4fluorophenyl)methylsilyl)methyl)-l H-1,2,4-triazole, triadimefon, triadimenol, diclobutrazol, furconazole, cis-furconazole, cyproconazole, terbuconazole, systhane, fenpropimorph, fenpropidin, chlorozolinate, diniconazole, imazilil, fenfuram, carboxin, oxycarboxin, dithianon, methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos, kitazin P, cycloheximide, phthalide, probenzazole, isoprothiolane, tricyclazole, pyroquilan, chlorbenzthiazone, neoasozin, polyoxin D, validamycin A, repronil, fluotolanil, pencycuron, diclomezine, 82 phenazin oxide, nickel, dimethyldithiocarbamate, techlorthalem, bitertanol, bupirimate, etaconazole, strptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, l-( 2-cyano-2-methoxyimino-acetyl)-3- ethyl urea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maeb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, binapactryl, nitrothalisopropyl, dodine dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, and organomercury compounds.
The compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Suitable insecticides which may be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-5-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenothoate, chlorpyrifos, isoxathion, propaphos, monocrotophos, buprofezin, ethroproxyfen and cycloprothrin.
Plant growth regulating compounds for use in the invention compositions are compounds which control weeds or seedhead formation, or selectively control the growth of less desirable plants (e g grasses).
Examples of suitable plant growth regulating compounds for use with the invention compositions are the gibberellins (e g GA 3, GA 4 or GA 7), the auxins (e g.
indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e g.
kinetin, diphenylurea, benzimidazole, benzyladenine or 83 benzylaminopurine), phenoxyacetic acids (e g 2,4-D or MCPA), substituted benzoic acids (e g.
triiodobenzoic acid), morphactins (e g.
chlorfluoroecol), maleic hydrazide, glyphosate, glphosine, long chain fatty alcohols and acids, dikegulac, paclobutrazol, flurprimidol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (e g chloromequat chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl- 3,6-dichloroanisate, daminozide, asulam, abscisic acid, isopyrimil, l-( 4-chlorophenyl)-4,6-dimethyl-2oxo-l,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e g bromoxynil), difenzoquat, benzoylpropethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide, triapenthenol and tecnazene.
The following Examples illustrate the invention.
Temperatures are given in degrees Centigrade ( C), and reactions involving water-sensitive intermediates were performed under atmospheres of nitrogen.
EXAMPLE 1
This Example illustrates the preparation of 1- ( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methylpent-4-en- 2-ol (Compound No 131 of Table I).
4-Chlorobenzyl chloride ( 32 8 g, 204 mmol) in dry diethyl ether ( 30 ml) was added dropwise to a stirred mixture of magnesium turnings ( 5 O g, 204 mmol) in dry diethyl ether ( 50 ml) at such a rate so as to maintain steady reflux Dry tetrahydrofuran ( 80 ml) was then added as diethyl ether was removed by 84 - distillation The mixture was then cooled to room temperature and added dropwise over 1 hour to a stirred solution of chloroacetyl chloride ( 46 g, 408 mmol) in dry tetrahydrofuran ( 200 ml) at -78 C The mixture was allowed to warm to room temperature over 1 hour and then poured into water The mixture was extracted with diethyl ether and the combined extracts were washed with 2 M aqueous sodium hydroxide solution and brine, dried (Mg SO 4) and evaporated in vacuo Chromatography lSi O 2, hexane-ethyl acetate ( 95:5)l gave 1-chloro-3-( 4-chlorophenyl)-acetone ( 16 8 g, 40 %) MP 47-49 C.
l-Chloro-3-( 4-chlorophenyl)acetone ( 6 O g, 30 mmol) in dry acetonitrile ( 5 ml) was added dropwise to a stirred mixture of 1,2,4-triazole ( 4 2 g, 60 mmol) and potassium carbonate ( 8 8 g, 60 mmol) in dry acetonitrile ( 50 ml) at 50 C After 3 hours the mixture was cooled and filtered The filtrate was poured into water and the mixture extracted with ethyl acetate The combined extracts were washed with brine (until neutral), dried (Mg SO 4) and evaporated in vacuo Chromatography lSi O 2, ethyl acetate-hexane ( 50:50) to ( 100:0)l gave 1-( 1,2,4- triazolyl)-3-( 4-chlorophenyl)acetone ( 3 23 g, 46 %).
Allyl magnesium bromide ( 8 8 ml of a 1 0 M solution in ether, 8 8 mmol) was added dropwise to a stirred solution of l-( 1,2,4-triazolyl)-3-( 4chlorophenyl)acetone ( 1 39 g, 5 9 mmol) in dry diethyl ether, ( 10 ml) After 1 hour the mixture was refluxed for 3 hours, cooled to room temperature and poured into saturated aqueous ammonium chloride solution.
The mixture was extracted with ethyl - acetate and the extracts were washed with brine, dried (Mg 504) and evaporated in vacuo.
Chromatography (Si O 2, ethyl acetate) gave 1-( 4- chlorophenyl)-2-( 1,2,4-triazolyl)methylpent-4-en-2- ol (Compound No 131 of Table I) ( 0 36 g, 22 %).
EXAMPLE 2
This Example illustrates the preparation of 1- ( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methyl-3- methylpent-4-en-2-ol (Compound No 441 of Table I).
Crotyl chloride ( 1 2 g, 13 mmol) in dry tetrahydrofuran ( 4 ml) was added dropwise to a suspension of magnesium turnings ( 0 35 g, 14 mmol) in dry tetrahydrofuran ( 5 ml) at such a rate so as to maintain steady reflux The mixture was then heated under reflux for 1 hour and then cooled to O C 1( 1,2,4-Triazolyl)-3-( 4-chlorophenyl)acetone ( 1 5 g, 6.37 mmol) in dry tetrahydrofuran ( 7 ml) was added dropwise over 30 minutes After 4 hours at room temperature the mixture was poured into saturated aqueous ammonium chloride solution and the resulting mixture extracted with ethyl acetate The extracts were washed with brine, dried (Mg SO 4) and evaporated in vacuo Chromatography (Si O 2, ethyl acetate) gave 1-( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methyl-3- methylpent-4-en-2-ol (Compound No 441 of Table I) ( 0 25 g, 13 %).
EXAMPLE 3
This Example illustrates the preparation of 1- ( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methylhex-4-yn-2- 86 - ol (Compound No 123 of Table I).
Trimethylsulphoxonium iodide ( 5 32 g, 24 mmol) and tetrabutylammonium bromide ( 0 2 g) were added to a suspension of 1-( 1,2,4-triazolyl)-3-( 4chlorophenyl)acetone ( 5 O g, 20 mmol) in toluene ( 33 ml) Potassium hydroxide ( 12 ml of a 50 % solution in water was added dropwise and the resulting mixture heated at 70 C for 1 hours The mixture was cooled to room temperature and poured into saturated aqueous sodium bicarbonate solution The resulting mixture was extracted with ethyl acetate and the extracts were washed with brine, dried (Mg SO 4) and evaporated in vacuo Chromatography (Si O 2, ethyl acetate) gave 1-( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methyl-2,3- epoxypropane ( 3 22 g, 65 %).
Propyne was bubbled through stirred dry tetrahydrofuran ( 12 ml) for 10 minutes Ethyl magnesium bromide ( 4 ml of a 3 OM solution in ether, 12 mmol) was added dropwise at 0 C Propyne was then bubbled through the mixture for another 30 minutes at 0 C 1-( 4-Chlorophenyl)-2-( 1,2,4-triazolyl)methyl- 2,3-epoxypropane ( 1 5 g, 6 3 mmol) in dry tetrahydrofuran ( 6 ml) was then added dropwise at 0 C After 30 minutes at O C the mixture was heated under reflux for 1 hour and then cooled to room temperature and poured into water The mixture was extracted with ethyl acetate and the extracts washed with brine, dried (Mg SO 4) and evaporated in vacuo.
Chromatography (Si O 2, ethyl acetate) gave a mixture of 1-( 4-chlorophenyl)-2-( 1,2,4-triazolyl)methyl-4-yn- 2-ol and 1-( 4-chlorophenyl)-2-( 1,2,4- triazolyl)methyl-2,3-expoxypropane This mixture was added to 1,2,4-triazole ( 0 7 g, 3 9 mmol) 87 - and potassium carbonate ( 0 4 g, 2 9 mmol) in industrial methylated spirit ( 40 ml) and heated under reflux for 3 hours The mixture was then cooled to room temperature and poured into water The resulting mixture was extracted with ethyl acetate and the extracts were washed with brine, dried (Mg SO 4) and evaporated in vacuo Chromatography (Si O 2, ethyl acetate) gave 1-( 4-chlorophenyl)-2- ( 1,2,4-triazolyl)methylhex-4-yn-2-ol (Compound No.
123 of Table I) ( 0 36 g, 21 %).
EXAMPLE 4
This example illustrates the preparation of 1- ( 2-chlorophenyl)-2-( 1,2,4-triazolyl)methyl-3,3- dimethylpent-4-en-2-01 (compound No 437 of Table I).
2-Chlorophenylacetyl chloride ( 11 3 g, 60 mmol) and aluminium trichloride ( 8 0 g, 60 mmol) in dichloromethane ( 30 ml) was added dropwise to a stirred solution of 3-methyl-l-trimethylsilylbut-2- ene ( 12 6 ml, 65 mmol), in dichloromethane ( 60 ml) at -78 C over 45 minutes After 10 minutes the mixture was warmed to room temperature and poured into an iced solution of aqueous ammonium chloride The resulting mixture was extracted with dichloromethane and the combined extracts dried (Mg SO 4) and evaporated in vacuo Chromatography lSi O 2, petroleum ether ( 40-60) -ethyl acetate ( 100:0) to ( 95:5)l gave 1-( 2-chlorophenyl)-3,3-dimethylpent-4-en-2-one ( 4 O g, %).
n-Butyllithium ( 11 3 ml of a 1 6 M solution in hexane, 18 mmol) was added dropwise to a stirred solution of thioanisole ( 2 O g, 15 mmol) and 1,4diazabicyclol 2 2 2 loctane( 2 O g, 18 mmol) 88 - in dry tetrahydrofuran ( 30 ml) The reaction was cooled by the use of an ice/salt bath After approximately 15 minutes a precipitate formed and after a further 45 minutes 1-( 2-chlorophenyl)-3,3- dimethylpent-4-en-2-one ( 3 0 g, 13 5 mmol) in dry tetrahydrofuran ( 15 ml) was added dropwise The mixture was warmed to room temperature and after 24 hours was poured into dilute hydrochloric acid and the resulting mixture extracted with diethyl ether.
The combined extracts were washed with water, dried (Mg SO 4) and evaporated in vacuo Chromatography lSi O 2, hexane -ethyl acetate ( 100:0) to ( 95:5)l gave 1-( 2-chlorophenyl)-2-phenylthiomethyl-3,3dimethylpent-4-en-2-ol ( 2 6 g 56 %).
* 1-( 2-Chlorophenyl)-2-phenylthiomethyl-3,3- dimethylpent-4-en-2-ol (l Og, 3 Ommol) was added to a stirred solution of triethyloxonium tetrafluoroborate ( 3.3 ml of a l O M solution in dichloromethane, 3 3 mmol) in dichloromethane ( 10 ml) After 2 hours the mixture was evaporated in vacuo, disolved in dimethyl formamide ( 6 ml) and added to a solution of sodium 1,2,4-triazole lformed by adding 1,2,4-triazole ( 0.46 g, 6 6 mmol) to petroleum ether-washed sodium hydride ( 0 3 g of a 50 % dispersion in oil, 6 3 mmol) in dimethylformamide ( 4 ml)l After heating under reflux for 6 hours the mixture was cooled to room temperature and poured into water The resulting mixture was extracted with ethyl acetate ( 3 x 50 ml) and the combined extracts dried (Mg SO 4) and evaporated in vacuo Chromatography lSi O 2, hexane-ethyl acetate ( 90:10) to ( 70:30)l gave 1-( 2-chlorophenyl)-2-( 1,2,4triazol-l-yl)methyl-3,3-dimethylpent-4-en-2-ol (compound No 437 of Table I) ( 0 158 g, 17 %).
89 - EXAMPLE 5
An emulsifiable concentrate was made up by mixing the ingredients, and stirring the mixture until all the constituents were dissolved.
Compound No 431 of Table I 10 % Ethylene dichloride 40 % Calcium dodecylbenzenesulphate 5 % "Lubrol" L 10 % "Aromasol" H 35 % EXAMPLE 6
A composition in the form of grains readily dispersible in a liquid, e g water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodium acetate The resultant mixture was dried and passed through a British Standard mesh sieve, size 44-100, to obtain the desired size of grains.
Compound No 437 of Table I 50 % "Dispersol" T 25 % "Lubrol" APN 5 1 5 % Sodium acetate 23 5 % EXAMPLE 7
The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.
Compound No 431 of Table I 45 % "Dispersol" T 5 % "Lissapol" NX 0 5 % "Cellofas" B 600 2 % Sodium acetate 47 5 % - EXAMPLE 8
The active ingredient was dissolved in a solvent and the resultant liquid was sprayed on to the granules of China clay The solvent was then allowed to evaporate to produce a granular composition.
Compound No 437 of Table I 5 % China clay granules 95 % EXAMPLE 9
A composition suitable for use as a seed dressing was prepared by mixing the three ingredients.
Compound No 431 of Table I 50 % Mineral oil 2 % China clay 48 % EXAMPLE 10
A dusting powder was prepared by mixing the active ingredient with talc.
Compound No 437 of Table I 5 % Talc 95 % EXAMPLE 11
A Col formulation was prepared by ball-milling the constituents set out below and then forming an aqueous suspension of the ground mixture with water.
91 - Compound No 431 of Table I 40 % "Dispersol" T 10 % "Lubrol" APN 5 1 % Water EXAMPLE 12
A dispersible powder formulation was made by mixing together the ingredients set out below and then grinding the mixture until all were thoroughly mixed.
Compound No 437 of Table I 25 % "Aerosol" OT/B 2 % "Dispersol" AC 5 % China clay 28 % Silica 40 % EXAMPLE 13
This Example illustrates the preparation of a dispersible powder formulation The ingredients were mixed and the mixture then ground in a comminution mill.
Compound No 431 of Table I 25 % "Perminal" BX 1 % "Dispersol" T 5 % Polyvinylpyrrolidone 10 % Silica 25 % China clay 34 % 92 - EXAMPLE 14
The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredients.
Compound No 437 of Table I 25 % "Aerosol" OT/B 2 % "Dispersol" AC 5 % China clay 68 % In Examples 5 to 14 the proportions of the ingredients given are by weight.
The remaining compounds set out in Table I were similarly formulated as specifically described in Examples 5 to 14.
There now follows an explanation of the compositions or substances represented by the various Trade Marks mentioned above.
AROMASOL H a solvent mixture of alkylbenzenes DISPERSOL T & AC a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthalene sulphonate.
LUBROL APN 5 a condensate of nonyl phenol (lmole) with naphthalene oxide ( 5.5 moles) CELLOFAS B 600 a sodium carboxymethyl cellulose thickener 93 LISSAPOL NX a condensate of nonyl phenol ( 1 mole) with ethylene oxide ( 8 moles) AEROSOL OT/B: dioctyl sodium sulphosuccinate PERMINAL BX a sodium alkyl naphthalene sulphonate EXAMPLE 15
The compounds were tested against a variety of foliar fungal diseases of plants The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use For the foliage diseases, the formulations ( 100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the plants in the soil The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a i /dry soil Tween 20, to give a final concentration of 0 05 %, was added when the sprays were applied to cereals.
For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with 94 - the disease An exception was the test on Erysiphe qraminis in which the plants were inoculated 24 hours before treatment Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.
The disease control was recorded by the following grading:
4 = no disease 3 = trace 5 % of disease on untreated plants 2 = 6-25 % of disease on untreated plants 1 = 26-59 % of disease on untreated plants 0 = 60-100 % of disease on untreated plants The results are shown in Table II.
TABLE III
COMPOUND PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA NO RECONDITA GRAMINIS INAEQUALIS ORYZAE ARACHIDICOLA (WHEAT) (BARLEY) (APPLE) (RICE) (PEANUT) 3 1 4 4 0 2 69 0 4 3 0 2 101 3 4 4 3 4 123 O 2 0 O O 129 0 3 4 0 2 0 4 0 1 131 4 4 4 3 4 371 0 4 4 0 0 431 0 4 4 1 1 TABLE III continued COMPOUND PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA NO RECONDITA GRAMINIS INAEQUALIS ORYZAE ARACHIDICOLA (WHEAT) (BARLEY) (APPLE) (RICE) (PEANUT) 437 4 3 4 2 441 4 4 4 O 1 451 O 3 4 0 O 461 3 4 4 1 462 4 4 4 3 results at rate of 25 ppm protectant test only.
P 34893 MAIN AA 016 11 May 1989 97 -

Claims (13)

1 Compounds having the general formula (I):
X R 3 OR
2 R 5 y I II C C C Az (I) z I I I Q R 4 Q R 6 and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C C-R 7 (II) or a group of general formula (III) R 9 / C = C (III) R 8 \ R 10 R R wherein R 7 to R Io O are independently hydrogen, halogen, alkyl, alkenyl, or alkynyl; R 2 is hydrogen, alkyl, alkenyl or alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 to R 6 are independently hydrogen, alkyl, alkenyl or alkynyl; X, Y and Z are independently hydrogen, halogen, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, optionally substituted aryloxy or optionally substituted aralkoxy; Az represents imidazol-l- yl or l,2,4-triazol-l-yl; Q is a bridging group having one of the following values Q 1, Q 2, Q 3 or Q 4.
Rll Q 1 = C I R 12 Rll R 13 I I Q 2 = C I I R 12 R 14 R 11 R 13 R 15 I I I Q 3 = C C_ C I I I R 12 R 14 R 16 R 1 R 1 R' Rll R 13 R 15 R 17 Ii I I Q 4 _ C C C C_ R 12 R 14 R 6 R wherein R 11 to R 18 are independently hydrogen, halogen, alkyl, alkenyl or alkynyl; and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl, R 5 is hydrogen, R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R 1 is not CH=CH 2.
99 - 2 Compounds having the general formula (I):
X R 3 OR 2 R 5 Y I I I C C AZ (I) I I I Z R 4 Q R 6 IR 1 and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C C R 7 (II) or a group of general formula (III):
R 9 C C (III) R 8/ RR 10 wherein R 7 to R 10 which can be the same or different each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine, bromine or iodine), R 2 represents a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, or an alkenyl or alkynyl group containing from 3 to 6 carbon atoms - (providing that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation), R 3 to R 6, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms, X, Y and Z, which can be the same or different, represent a hydrogen atom, a halogen atom (fluorine, chlorine or bromine), an alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy group, Az represents 1-imidazole or 1,2,4-triazole and Q is a bridging group having one of the following values Q 1, Q 2, Q 3 or Q 4:
Rll Q 1 C I R 12 R 1 l R 13 I Q 2 = C C I R 12 R 14 Rll R 13 R 15 Q 3 = C C C R 1 R 1 R 1 101 - Rll R 13 R 15 R 17 I I I I Q 4 = C C C C R 12 R 14 R 16 R 18 wherein Rl to R 18, which can be the same or different, each represent a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms or an alkenyl or alkynyl group containing from 2 to 4 carbon atoms or a halogen atom (fluorine, chlorine or bromine); and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl, R 5 is hydrogen, R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R is not -CH=CH 2.
3 Compounds having the general formula (I):
X R 3 OR 2 R 5 s\ II I Y C C C _ Az (I) I I I Z R 4 Q R 6 and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C C R 7 (II) 102 - or a group of general formula (III):
R 9 C = C (III) R 8 \R 1 o wherein R 7 to R 1 o are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; R 2 is hydrogen, C 1 _ 6 alkyl, C 3 _ 6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 to R 6 are independently hydrogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; X, Y and Z are independently hydrogen, halogen, C 1 _ 6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl_ 6)alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, phenyl, phenyl(C 1 l_ 6)alkyl, C 1 _ 6 alkoxy, phenoxy or phenyl(C 1 l_ 6)alkoxy; Az represents imidozol-l-yl or 1, 2, 4-triazol-l-yl; Q is a bridging group having one of the following values Q 1, Q 2, Q 3 or Q 4:
R Q 1 = _ C I I R 1 l R 13 Q 2 _ C C R 12 R 14 103 - Rll R 13 R 15 I I I Q 3 C C C R 12 R 14 R 16 Rll R 13 R 15 R 17 Q 4 C -C-C C C I I Ii R 12 R 14 R 16 R 18 wherein R 11 to R 18 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; wherein any of the foregoing aryl moieties are optionally substituted by halogen, e 5 C 1 _ 6 alkyl, C 1 _ 6 alkoxy, halo(Cl_ 6)alkoxy, halo(Cl_ 6)alkyl, nitro, phenyl or phenoxy; and salts and metal complexes thereof; provided that when R 3 and R 4 are both alkyl R 5 is hydrogen R 6 is one of alkyl, alkenyl or alkynyl and Q is CH 2 then R 1 is not CH=CH 2.
4 Compounds as claimed in any of claims 1,2 or 3 and having the general formula:
X R 3 OR 2 I I Y CH C CH 2 Az (IA) I Z Q { 104 - and stereoisomers thereof, wherein R 1 represents a group of general formula (II):
C C-R 7 (II) or a group of general formula (III):
9 R C =C R 8 Z \R 10 wherein R 7 and R 10 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; R 2 is hydrogen, C 1 _ 6 alkyl, C 3 _ 6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon atom adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; X, Y and Z are independently hydrogen, halogen, C 1 _ 6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl_ 6)alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, phenyl, phenyl(Cl_ 6) alkyl, Cl_ 6 alkoxy, phenoxy or phenyl(Cl_ 6) alkoxy, Az represents imidazol-l-yl or 1, 2, 4- triazol-l-yl; Q is a bridging group having one of the following values Q 1 or Q 2:
Rll I Q 1 =_ C R 12 Rll R 13 I I Q 2 =_ C C I I R 12 R 14 - wherein R 11 to R 14 are independently hydrogen, halogen, C 1 _ 4 alkyl, C 2 _ 4 alkenyl or C 2 _ 4 alkynyl; wherein any of the foregoing aryl moieties are optionally substituted by halogen, C 11 _ 6 alkyl, Cl_ 6 alkoxy, halo(Cl_ 6)alkoxy, halo(Cl_ 6)alkyl, nitro, phenyl or phenoxy; and salts and metal complexes thereof.
Compounds as claimed in any of claims 1,2, 3 or 4 and having the general formula (IA):
R 3 OR 2 Y CH-C CH 2Az (IA) / Q and stereoisomers thereof; wherein R 1 represents a group of general formula (II):
C C R 7 (II) or a group of general formula (III):
R 9 \ / R 9 C = C C=C R 8/ \R 10 wherein R 7 to R 10 are independently hydrogen, halogen or Cl_ 4 alkyl; R 2 is hydrogen, C 1 _ 6 alkyl, C 3 _ 6 alkenyl or C 3 _ 6 alkynyl (providing that the carbon adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen or 106 - C 1 _ 4 alkyl; X, Y and Z are independently hydrogen, fluorine, chlorine, bromine, Cl_ 6 alkyl, C 3 _ 7 cycloalkyl, C 3 _ 7 cycloalkyl(Cl_ 6) alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl or Cl_ 6 alkoxy; Az represents imidazol-l-yl or 1,2,4- triazol-l-yl; Q is a bridging group having one of the following values Q 1 or Q 2:
Rll R 1 Q 1 _ C I R 12 Rll R 13 I I Q 2 = _ C C l 4 R 12 R 14 wherein R 11 to R 14 are independently hydrogen, halogen or C 1 _ 4 alkyl; and salts and metal complexes thereof.
6 Compounds as claimed in any of the proceeding claims and having the general formula (IB):
X R 3 OR 2 /< I' I Y CH C -CH 2 _N N (IB) QR 1 and stereoisomers thereof; wherein Rl represents a group of general formula (II):
107 - C CR 7 (II) or a group of general formula (IIIA) R 9 C = C (IIIA) H \R 10 wherein R 7, R 9 and R 1 are independently hydrogen, methyl or ethyl, R 2 is hydrogen, methyl, propenyl or propynyl (providing that the carbon atoms adjacent to the oxygen is not involved in any unsaturation); R 3 is hydrogen or methyl; X, Y and Z are independently hydrogen, chlorine or fluorine; Q is a bridging group having one of the following values Q 1 or Q 2 Rll Rll R 13 I I I Q 1 _ C Q 2 =-C C II I R 12 R 12 R 14 wherein R 11 to R 14 are independently hydrogen or methyl; and salts and metal complexes thereof.
7 Compounds as claimed in any of the proceeding claims and having the general formula (IC):
X R 3 OH Y /, CH C CH 2 _ N N (IC) Q I N CH itl CH 2 108 - and stereoisomers thereof, wherein R 3 is hydrogen or methyl; Q is a bridging group having one of the following values Q 1 or Q 2 Rll I Q 1 = _ C _Q 2 = CH 2 CH 2 R 12 wherein Rl and R 12 are independently hydrogen or methyl; X and Y are independently hydrogen and chlorine; and salts and metal complexes thereof.
8 The compound:
Cl OH A\ I CH 2 C, CH 2 N N CH 3 CH N CH II CH 2 (compound 431 of Table I) and its stereoisomers; and salts and metal complexes thereof.
9 The compound:
C 1 OH /CH 2 C CH 2 N CH 3 C -CH 3 N CH lit II CH 2 (compound 437 of Table I) and its stereoisomers; and salts and metal complexes thereof.
109 - A process for preparing compounds of general formula (I):
R 3 OR 2 R 5 x I I I C C C Az (I) Z 4 Q R 6 which comprises etherifying an alcohol of formula:
R 3 OH R 5 x I \ I C C C Az (I) Z R 4 Q R 6 I R 1 wherein Az, Q, R 1, R 3 to R 6, X, Y and Z are as defined in claim 1, by treatment with a base, such as sodium hydride and an alkyl halide, R 2 Hal, wherein Hal can be chlorine, bromine or iodine and R 2 is as defined in claim 1, in a solvent and wherein the compounds of general formula (IV) are prepared either by treatment of compounds of general formula (VI):
- X R 3 O R 5 I II l Y ( 7 C C C_ C-Az (VI) I I Z R 4 R 6 wherein Az, R 3 to R 6, X, Y and Z are as defined in claim 1, with compounds of general formula (VII):
M Q R 1 (VII) wherein Q and R 1 are as defined in claim 1 and M is a metal such as magnesium, lithium or titanium, or by treatment of compounds of general formula (VIII):
X R 3 O R 5 Y -C C Hal I I Z R 4 R 6 (VIII) wherein R 3 to R 6, X, Y and Z are as defined in claim 1 and Hal is a chlorine bromine or iodine atom, with compounds of general formula (VII); M Q R 1 (VII) wherein Q and R 1 are as defined in claim 1 and M is a metal such as magnesium, lithium or titanium, followed by treatment with an azole (imidazole or 1,2,4-triazole).
11 A fungicidal composition comprising as an active ingredient a compound as claimed in claim 1 or a stereoisomer, salt or metal complex thereof, and, optionally, a carrier or diluent.
12 A method of combatting fungi which comprises applying to a plant, to seed of a plant, or to the locus of the plant or seed, a compound as claimed in claim 1 or a stereoisomer, salt or metal complex thereof or a composition as claimed in claim 11.
13 As novel intermediates compounds of formula IV,V and XVI, wherein X, Y, Z, R 1, R 3, R 4, R 5, R 6, Az, Q and R 7 are as defined in any of claims 1 to 7.
Published 1989 at The Patent Office, State House 66 '71 High Holborn, London WC 1 R 4 TP Further copies maybe obtained from The Patent Office.
Sales Branch, St Mary Cray, Orpingtor, Kent BR 5 3RD Printed by Multiplex techniques Itd St Mary Cray, Kent, Con 1/87
GB8914693A 1988-07-14 1989-06-27 Plant fungicidal azoles Withdrawn GB2220655A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015756A1 (en) * 1979-03-07 1980-09-17 Imperial Chemical Industries Plc Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them
EP0047594A2 (en) * 1980-08-18 1982-03-17 Imperial Chemical Industries Plc Triazole compounds, a process for preparing them, their use as plant fungicides and plant growth regulators and compositions containing them
GB2110684A (en) * 1981-11-27 1983-06-22 Ciba Geigy Ag Substituted azolyl-ethyl ethers and microbicidal compositions thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3222191A1 (en) * 1982-06-12 1983-12-15 Bayer Ag, 5090 Leverkusen HYDROXYALKINYL-AZOLYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015756A1 (en) * 1979-03-07 1980-09-17 Imperial Chemical Industries Plc Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them
EP0047594A2 (en) * 1980-08-18 1982-03-17 Imperial Chemical Industries Plc Triazole compounds, a process for preparing them, their use as plant fungicides and plant growth regulators and compositions containing them
GB2110684A (en) * 1981-11-27 1983-06-22 Ciba Geigy Ag Substituted azolyl-ethyl ethers and microbicidal compositions thereof

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DK348889A (en) 1990-01-15
GB8816772D0 (en) 1988-08-17

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