Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2000-02-08
2002-09-03
Kumar, Shailendra (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C514S464000, C514S532000, C514S534000, C514S617000, C514S620000, C549S442000, C560S015000, C560S016000, C560S056000, C560S060000, C560S061000, C564S182000
Reexamination Certificate
active
06444850
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel fungicidal compounds having a fluorovinyloxyphenyl moiety, a process for preparing same and a fungicidal composition containing same as an active ingredient.
DESCRIPTION OF THE PRIOR ART
A number of fungicidal compounds have been in practical use to protect crops from various pathogenic fungi; and they may be classified into several groups having similar structural features. However, the repetitive use of a fungicide over a long period induces the appearance of new fungal strains resistant not only to the particular fungicide but also to related fungicides having common structural features. For this reason, continuous efforts have been undertaken to develop fungicides having new structures.
Such efforts have led to the development of new fungicides, e.g., propenoic ester derived from strobilurin (U.S. Pat. No. 4,994,495; WO 94/19331; and U.S. Pat. No. 5,003,101). However, these propenoic ester derivatives have the problem of limited fungicidal activity.
SUMMARY OF THE INVENTION
Accordingly, it is a primary object of the present invention to provide a novel compound having a superior fungicidal activity against a wide spectrum of plant pathogenic fungi.
It is another object of the present invention to provide a process for the preparation of said compound.
It is a further object of the present invention to provide a fungicidal composition containing said compound.
In accordance with one aspect of the present invention, there are provided a novel compound of formula (I) and stereoisomers thereof:
wherein:
X is CH or N; Y is O or S;
Z is O or NH;
R
1
is hydrogen or CF
3
; and
R
2
is hydrogen, a C
1-10
alkyl, naphthyl, thiophenyl or phenyl group optionally carrying one or more substituents selected from the group consisting of C
1-6
alkyl, halogen-substituted c
1-6
alkyl, C
1-6
alkoxy, phenoxy, halogen and methylenedioxy radicals.
DETAILED DESCRIPTION OF THE INVENTION
The structure of the compound of formula (I) of the present invention is characterized by the fluorovinyloxyphenoxy moiety, but depending on whether X is CH or N, it may also be classified as a propenoic acid derivative (X═CH) or as an iminophenylacetic acid derivative (X═N).
The compound of the present invention has four stereoisomers resulting from two unsymmetrically substituted double bonds, and according to the terminology defined in the Cahn-Ingold-Prelog system(J. March,
Advanced Organic Chemistry
, 3rd Ed., Wiley-Interscience), these four stereoisomers may be expressed as (E,E), (E,Z), (Z,E) and (Z,Z) isomers, which are included within the scope of the present invention.
Among the compounds of the present invention, preferred are those wherein Y is O; Z is O; R
1
is hydrogen; and R
2
is a naphthyl or phenyl group optionally substituted with methyl, methoxy or halogen; and those wherein Y is O; R
1
is CF
3
; and R
2
is a phenyl group optionally substituted with methyl, methoxy or halogen.
The compound of the present invention may be prepared by the steps of (a) reacting a compound of formula (II) with 3-hydroxyphenol (Resorcinol) in the presence of a base to obtain a compound of formula (III); and (b) reacting the compound of formula (III) with a compound of formula (IV) in the presence of a base, as shown in Reaction Scheme A:
wherein, X, Y, Z, R
1
and R
2
have the same meanings as defined in formula (I) above.
Representative compounds of formula (II) are those of formula (II-a) (X═CH, Y═O and Z═O), formula (II-b) (X═N, Y═O, Z═O) and formula (II-c) (X═CH, Y═S, Z═O):
A compound of formula (II-a) may be prepared by esterification, formylation, methylation and bromination of o-tolylacetic acid according to a conventional method(Yamada, K. et al.,
Tetrahedron Lett
., 2745(1973); Vyas, G. N. et al.,
Org. Syn. Coll
., 4, 836(1963); and Kalir, A.,
Org. Syn. Coll
., 5, 825(1973)), as shown in Reaction Scheme B:
A compound of formula (II-b) may be prepared by Grignard reaction, oxalylation, condensation and bromination of o-bromotoluene according to a conventional method (Rambaud, M. et al.,
Synthesis
, 564(1988); Korean Patent No. 88,673; and PCT/KR 95/00020), as shown in Reaction Scheme C:
A compound of formula (II-c) may be prepared by sulfonylation, nucleophilic substitution and bromination of methyl 3-hydroxy-2-(2′-methyl)phenyl-2-propenoate according to a conventional method (Korean Patent Application No. 95-37559), as shown in Reaction Scheme D:
wherein, MsO represents a methansulfonyloxy group.
Representative compounds of formula (III) are those of formula (III-a) (X═CH, Y═O and Z═O), formula (III-b) (X═N, Y═O, Z═O) and formula (III-c) (X═CH, Y═S, Z═O):
A compound of formula (II) is reacted with 3-hydroxyphenol in the presence of a base to produce a compound of formula (III). The compound of formula (II) and 3-hydroxyphenol may be used in equimolar amounts and the base may be used in twice the molar amount. The base may be an inorganic base, e.g., sodium hydride, potassium t-butoxide, sodium carbonate or potassium carbonate; or an organic base, e.g., triethylamine or pyridine. The solvent which may be used in the reaction includes acetone, benzene, toluene, tetrahydrofuran, acetonitrile, dichloromethane or dimethylformamide, and the reaction may be conducted at a temperature ranging from room temperature to 100° C. The progress of the reaction is conveniently followed by measuring the disappearance of the compound of formula (II) with thin layer chromatography(TLC).
A compound of formula (IV) is reacted with a compound of formula (III) to produce a compound of formula (I), as in Reaction scheme A.
A compound of formula (IV-a), i.e. a compound of formula (IV) wherein R
1
is hydrogen, may be prepared by a Grignard reaction, reduction, halogenation, dehalogenation of a halide of R
2
according to a conventional method (Herkes, F. E. et al.,
J. Org. Chem
., 32, 1311(1967); and Nemeth, G. et al.,
J. fluorine Chem
., 76, 91(1996)), as shown in Reaction Scheme E:
wherein R
2
has the same meaning as defined in formula (I) above; and W represents a halogen.
A compound of formula (IV-b), i.e. a compound of formula (IV) wherein R
1
is CF
3
, may be prepared by a Grignard reaction and Wittig reaction of a halide of R
2
according to a conventional method (Herkes, F. E. et al.,
J. Org. Chem
., 32, 1311(1967); and Wheatman. G. A. et al.,
J. Org. Chem
., 48, 917(1983)), as shown in Reaction Scheme F:
wherein R
2
and W have the same meanings as above.
The compound of the present invention may be prepared by reacting a compound of formula (III) with a compound of formula (IV) in the presence of a base. The compounds (III) and (IV) may be used in equimolar amounts and the base may be used in one to two equivalent amounts. The base may be an inorganic base, e.g., sodium hydride, potassium t-butoxide, sodium carbonate or potassium carbonate; or an organic base, e.g., triethylamine or pyridine. The solvent which may be used in the reaction is benzene, toluene, tetrahydrofuran, acetonitrile, dichloromethane or dimethylformamide, and the reaction temperature is in the range of room temperature to 100° C.
In case a mixture of E and Z isomers of compound of formula (II-a-4), (II-b-3) or (II-c-3) is used in the reaction(Reaction Scheme A), the compound of the present invention is obtained as a mixture of four isomers wherein the (E,E) and (E,Z) isomers predominate with minor amounts of the (Z,E) and (Z,Z) isomers. The structures of the four stereoisomers of the compound of the present invention are illustrated below:
In case R
1
is hydrogen
wherein, X, Y, Z, R
1
and R
2
have the same meanings as defined in formula (I) above.
In case only the E isomer of the compound of formula (II-a-4), (II-b-3) or (II-c-3) is used, the compound of the present invention is obtained as a mixture of the (E,E) and (E,Z) isomers, as is confirmed by
1
H-NMR or
19
F-NMR analysis.
According to the
1
H-NMR analysis(reference compound, TMS) of the compoun
Choi Gyung-Ja
Kim Bum-Tae
Kim Heung-Tae
Pak Chwang-Siek
Park No-Kyun
Korea Research Institute of Chemical Technology
Kumar Shailendra
Rosenman & Colin LLP
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