# Patent

## Title
4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture

## Abstract

A new agricultural and horticultural fungicide having an excellent control effect is provided.
4-Quinolinol derivatives represented by the following formula:




or agriculturally and horticulturally acceptable acid addition salts thereof.

## Background
This application is a continuation of U.S. application Ser. No. 09/424,257 filed on Mar. 21, 2000 now U.S. Pat. No. 6,680,282, now allowed, which is a 371 of PCT/JP98/02434, filed Jun. 2, 1998.


FIELD OF THE INVENTION
The present invention relates to 4-quinolinol derivatives and agricultural and horticultural fungicides containing them as active ingredients.
BACKGROUND OF THE INVENTION
JP-01246263A, JP-05202032A, JP-05271222A and JP-07285.938A, which were published prior to the filing date of the present application, disclose that quinoline derivatives having a substituent, such as aryloxy, arylthio, amino, pyrimidyloxy, pyrimidylthio or benzoyl group, at 4-position of quinoline skeleton are effective against plant pathogenic fungi and useful as agricultural and horticultural fungicides. However, it has never known that a quinoline derivative having an acyloxy group at 4-position of quinoline skeleton has an excellent fungicidal activity.
And, JP-03128355A discloses 4-acyloxyquinoline derivatives structurally similar to the compound of the present invention and insecticidal and acaricidal agents containing them as active ingredients. However, it has never known that these compounds are effective against plant pathogenic fungi.
DISCLOSURE OF THE INVENTION
Many active agents having control effect against various plant diseases were discovered and various agricultural and horticultural fungicides containing them as active ingredients have been developed. Due to some problems, such as an appearance of resistant fungi, however, fungicides having higher control effect are needed.
Thus, an object of the present invention is to provide a new agricultural and horticultural fungicide having higher control effect.
The present inventors concentrated on solving the above-mentioned problem. As the result, it was found that among 4-quinolinol derivatives, 4-quinolinol derivatives having specific substituents at all of the 2, 3 and 5 to 8 positions of quinoline skeleton and their acid addition salts show excellent fungicidal activity against various plant pathogenic fungi causing blast of rice, brown spot of rice, powdery mildew of Cucurbitaceae, anthracnose of potato and the like, and thereby the present invention was completed.
Accordingly, the present invention relates to a 4-quinolinol derivative represented by the general formula (I):




wherein

    R1 represents
    
        a hydrogen atom,
        an alkali metal,
        an alkaline earth metal, or
        COR4 in which R4 is
        
            a hydrogen atom,
            an optionally substituted C1–C18 alkyl group,
            an optionally substituted C2–C18 alkenyl group,
            an optionally substituted C3–C10 cycloalkyl group,
            an optionally substituted phenyl lower alkyl group,
            an optionally substituted phenoxy lower alkyl group,
            an optionally substituted aryl group,
            OR5 in which R5 is an optionally substituted lower alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl lower alkyl group or an optionally substituted phenoxy lower alkyl group, or
            NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
        
        
    
    
    R2 represents an optionally substituted lower alkyl group;
    R3 represents
    
        an optionally substituted C11–C18 alkyl group,
        an optionally substituted lower alkenyl group, or
        an optionally substituted lower alkoxy group; or
    
    
    R2 and R13 together represent —(CH2)m— in which m is 3 or 4; and
    W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
    
        a halogen atom,
        an optionally substituted C1–C10 alkyl group,
        an optionally substituted lower alkenyl group,
        an optionally substituted lower alkynyl group,
        an optionally substituted C1–C10 alkoxy group,
        an optionally substituted C3–C10 cycloalkyl group,
        an optionally substituted aryl group,
        an optionally substituted aryloxy group,
        NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
        COR10 in which R10 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
        COOR11 in which R11 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
        a nitro group or
        a cyano group,

and acid addition salts thereof as well as an agricultural and horticultural fungicide containing at least one of them.

    
    


In the 4-quinolinol derivatives represented by the aforementioned general formula (I),

    R1 represents
    
        a hydrogen atom,
        an alkali metal, such as preferably sodium and potassium,
        an alkaline earth metal, such as magnesium, calcium and barium, in which magnesium and calcium are preferable, or
        COR4 in which R4 is
        
            a hydrogen atom,
            an optionally substituted C1–C18 alkyl group, preferably an optionally substituted C1–C8 alkyl group, more preferably a C1–C4 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,
            an optionally substituted C2–C18 alkenyl group, preferably an optionally substituted C2–C8 alkenyl group, more preferably a C2–C4 alkenyl group, such as vinyl group CH2═CH—, allyl group CH2═CHCH2— and 2-butenyl group CH3CH═CHCH2—,
            an optionally substituted C3–C10 cycloalkyl group, preferably an optionally substituted C3–C6 cycloalkyl group,
            an optionally substituted phenyl lower alkyl group,
            an optionally substituted phenoxy lower alkyl group,
            an optionally substituted aryl group,
            OR5 in which R5 is an optionally substituted lower alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl lower alkyl group or an optionally substituted phenoxy lower alkyl group, or
            NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
        
        
    
    
    R2 represents an optionally substituted C1–C4 alkyl group;
    R3 represents
    
        an optionally substituted C1–C18 alkyl group, preferably an optionally substituted C1–C6 alkyl group, more preferably a C1–C4 alkyl group, such as methyl ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,
        an optionally substituted lower alkenyl group, or
        an optionally substituted lower alkoxy group; or
    
    
    R2 and R3 together represent —(CH2)m— in which m is 3 or 4; and
    W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
    
        a halogen atom,
        an optionally substituted C1–C10 alkyl group,
        an optionally substituted lower alkenyl group,
        an optionally substituted lower alkynyl group,
        an optionally substituted C1–C10 alkoxy group,
        an optionally substituted C3–C10 cycloalkyl group,
        an optionally substituted aryl group,
        an optionally substituted aryloxy group,
        NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
        COR10 in which R10 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
        COOR11 in which R11 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
        a nitro group, or
        a cyano group.
    
    


Agriculturally and horticulturally acceptable acid addition salts of the 4-quinolinol derivative represented by the aforementioned general formula (I) mean salts generally usable in agriculture and horticulture, such as hydrochloride, nitrate, sulfate, phosphate and acetate.
The 4-quinolinol derivative represented by the aforementioned general formula (I) may be in the form of hydrate or solvate. Such hydrate and solvate of the compound represented by the general formula (I) are also included in the present invention.
Substituents which optionally present on the 4-quinoline derivative represented by the aforementioned general formula (I) include a halogen atom, such as fluorine, bromine and chlorine, a C1–C4 alkyl group, a C1–C4 alkoxy group, a hydroxyl group, a nitro group, a formyl group, a cyano group and the like.
The term “lower alkyl group” as used herein means an alkyl group containing about 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl.
The term “lower alkenyl group” as used herein means an alkenyl group containing about 2 to 4 carbon atoms, such as vinyl, (1- or 2-)propenyl or (1-, 2- or 3-)butenyl.
The term “lower alkynyl group” as used herein means an alkynyl group containing about 2 to 4 carbon atoms, such as ethynyl, (1- or 2-)propynyl or (1-, 2- or 3-)butynyl.
The term “lower alkoxy group” as used herein means an alkoxy group containing about 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxy or butyloxy.
The term “C1–C18 alkyl group” as used herein means an alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
The term “C2–C18 alkenyl group” as used herein means, for example, vinyl, (1- or 2-)propenyl, (1-, 2- or 3-)butenyl, (1-, 2-, 3- or 4-)pentenyl, (1-, 2-, 3-, 4- or 5-)hexenyl, (1-, 2-, 3-, 4-, 5- or 6-)heptenyl, (1-, 2-, 3-, 4-, 5-, 6- or 7-)octenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-)nonenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-)decenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-)undecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- or 11-)dodecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-)tridecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13-)tetradecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 14-)pentadecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- or 15-)hexadecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- or 16-)heptadecenyl, or (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- or 17-)octadecenyl.
The term “C3–C10 cycloalkyl group” as used herein means, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.
The term “C1–C10 alkoxy group” as used herein means, for example, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy or decyloxy.
The term “phenyl lower alkyl group” as used herein means a phenylalkyl group having a C1–C4 alkyl moiety, such as benzyl, (1- or 2-)phenylethyl, (1-, 2- or 3-)phenylpropyl or (1-, 2-, 3- or 4-)phenylbutyl.
The term “phenoxy lower alkyl group” as used herein means a phenoxyalkyl group having a C1–C4 alkyl moiety, such as phenoxymethyl, (1- or 2-)phenoxyethyl, (1-, 2- or 3-)phenoxypropyl or (1-, 2-, 3- or 4-)phenoxybutyl.
The following Table 1 specifically illustrates the compounds within the scope of the 4-hydroxyquinoline derivatives represented by the general formula (I) of the present invention.
Abbreviations used in Table 1 and Examples have following meanings.
iso-C3H7 isopropyl
t-C4H9 tertiary butyl
s-C4H9 secondary butyl
c-C5H9 cyclopentyl
c-C6H11 cyclohexyl
n-pentyl, normal pentyl











TABLE 1





com-






pound


No.
R1
R2
R3
W



















1
H
CH3
CH3
6-CH3


2
CH3CO
CH3
CH3
6-CH3


3
C6H5CO
CH3
CH3
6-CH3


4
CH3OCO
CH3
CH3
6-CH3


5
H
CH3
CH3
6-CH3O


6
CH3CO
CH3
CH3
6-CH3O


7
C6H5CO
CH3
CH3
6-CH3O


8
CH3OCO
CH3
CH3
6-CH3O


9
H
CH3
CH3
6-C2H5


10
CH3CO
CH3
CH3
6-C2H5


11
C6H5CO
CH3
CH3
6-C2H5


12
CH3OCO
CH3
CH3
6-C2H5


13
H
CH3
CH3
6-C3H7


14
CH3CO
CH3
CH3
6-C3H7


15
C6H5CO
CH3
CH3
6-C3H7


16
CH3OCO
CH3
CH3
6-C3H7


17
(C2H5)2NCO
CH3
CH3
6-C3H7


18
H
CH3
CH3
6-iso-C3H7


19
CH3CO
CH3
CH3
6-iso-C3H7


20
C6H5CO
CH3
CH3
6-iso-C3H7


21
CH3OCO
CH3
CH3
6-iso-C3H7


22
(C2H5)2NCO
CH3
CH3
6-iso-C3H7


23
H
CH3
CH3
6-iso-C3H7O


24
CH3CO
CH3
CH3
6-iso-C3H7O


25
C6H5CO
CH3
CH3
6-iso-C3H7O


26
CH3OCO
CH3
CH3
6-iso-C3H7O


27
C6H5OCO
CH3
CH3
6-iso-C3H7O


28
H
CH3
CH3
6-C4H9


29
CH3CO
CH3
CH3
6-C4H9


30
C2H5CO
CH3
CH3
6-C4H9


31
c-C3H5CO
CH3
CH3
6-C4H9


32
t-C4H9CO
CH3
CH3
6-C4H9


33
C6H5CO
CH3
CH3
6-C4H9


34
4-CH3O—C6H4CO
CH3
CH3
6-C4H9


35
4-Cl—C6H4CO
CH3
CH3
6-C4H9


36
CH3OCO
CH3
CH3
6-C4H9


37
C2H5OCO
CH3
CH3
6-C4H9


38
C8H17OCO
CH3
CH3
6-C4H9


39
C6H5OCO
CH3
CH3
6-C4H9


40
4-CH3O—C6H4CO
CH3
CH3
6-C4H9


41
4-Cl—C6H4OCO
CH3
CH3
6-C4H9


42
(C2H5)2NCO
CH3
CH3
6-C4H9


43
(C6H5)2NCO
CH3
CH3
6-C4H9


44
CH3CO
C2H5
CH3
6-C4H9


45
CH3CO
C3H7
CH3
6-C4H9


46
CH3CO
C4H9
CH3
6-C4H9


47
CH3CO
CH3
C2H5
6-C4H9


48
CH3CO
CH3
C3H7
6-C4H9


49
CH3CO
CH3
C4H9
6-C4H9










50
H
—(CH2)4—
6-C4H9


51
CH3CO
—(CH2)4—
6-C4H9


52
C2H5CO
—(CH2)4—
6-C4H9


53
C6H5CO
—(CH2)4—
6-C4H9











54
H
CH3
CH3
6-s-C4H9


55
CH3CO
CH3
CH3
6-s-C4H9


56
C2H5CO
CH3
CH3
6-s-C4H9


57
c-C3H5CO
CH3
CH3
6-s-C4H9


58
t-C4H9CO
CH3
CH3
6-s-C4H9


59
t-C4H9CH2CO
CH3
CH3
6-s-C4H9


60
C8H17CO
CH3
CH3
6-s-C4H9


61
C6H5CO
CH3
CH3
6-s-C4H9


62
4-CH3O—C6H4CO
CH3
CH3
6-s-C4H9


63
4-Cl—C6H4CO
CH3
CH3
6-s-C4H9


64
2,6-di-CH3O—C6H3CO
CH3
CH3
6-s-C4H9


65
CH3OCO
CH3
CH3
6-s-C4H9


66
C2H5OCO
CH3
CH3
6-s-C4H9


67
C8H17OCO
CH3
CH3
6-s-C4H9


68
C6H5OCO
CH3
CH3
6-s-C4H9


69
4-CH3O—C6H4OCO
CH3
CH3
6-s-C4H9


70
4-Cl—C6H4OCO
CH3
CH3
6-s-C4H9


71
(CH3)2NCO
CH3
CH3
6-s-C4H9


72
(C2H5)2NCO
CH3
CH3
6-s-C4H9


73
CH3(C6H5)NCO
CH3
CH3
6-s-C4H9


74
(C6H5)2NCO
CH3
CH3
6-s-C4H9


75
H
CH3
CH3O
6-t-C4H9


76
CH3CO
CH3
CH3O
6-t-C4H9


77
H
CH3
CH3O
6-s-C4H9


78
CH3CO
CH3
CH3O
6-s-C4H9


79
CH3CO
CH3
CF3
6-s-C4H9


80
H
CH3
CF3
6-s-C4H9


81
CH3CO
CH3
CF3
6-t-C4H9


82
H
CH3
CF3
6-t-C4H9


83
H
CH3
CH3
6-t-C4H9


84
CH3CO
CH3
CH3
6-t-C4H9


85
C2H5CO
CH3
CH3
6-t-C4H9


86
c-C3H5CO
CH3
CH3
6-t-C4H9


87
C6H5CO
CH3
CH3
6-t-C4H9


88
CH3OCO
CH3
CH3
6-t-C4H9


89
C2H5OCO
CH3
CH3
6-t-C4H9


90
C6H5OCO
CH3
CH3
6-t-C4H9


91
(C2H5)2NCO
CH3
CH3
6-t-C4H9


92
H
CH3
CH3
6-iso-C4H9


93
CH3CO
CH3
CH3
6-iso-C4H9


94
C6H5CO
CH3
CH3
6-iso-C4H9


95
CH3OCO
CH3
CH3
6-iso-C4H9


96
C6H5OCO
CH3
CH3
6-iso-C4H9


97
H
CH3
CH3
6-C5H11


98
CH3CO
CH3
CH3
6-C5H11


99
C6H5CO
CH3
CH3
6-C5H11


100
CH3OCO
CH3
CH3
6-C5H11


101
C6H5OCO
CH3
CH3
6-C5H11


102
H
CH3
CH3
6-c-C5H9


103
CH3CO
CH3
CH3
6-c-C5H9


104
C6H5CO
CH3
CH3
6-c-C5H9


105
CH3OCO
CH3
CH3
6-c-C5H9


106
(C2H5)2NCO
CH3
CH3
6-c-C5H9


107
H
CH3
CH3
6-C6H13


108
CH3CO
CH3
CH3
6-C6H13


109
C6H5CO
CH3
CH3
6-C6H13


110
CH3OCO
CH3
CH3
6-C6H13


111
H
CH3
CH3
6-c-C6H11


112
CH3CO
CH3
CH3
6-c-C6H11


113
C2H5CO
CH3
CH3
6-c-C6H11


114
C6H5CO
CH3
CH3
6-c-C6H11


115
4-CH3O—C6H4CO
CH3
CH3
6-c-C6H11


116
4-Cl—C6H4CO
CH3
CH3
6-c-C6H11


117
CH3OCO
CH3
CH3
6-c-C6H11


118
C6H5CO
CH3
CH3
6-c-C6H11


119
(C2H5)2NCO
CH3
CH3
6-c-C6H11


120
H
CH3
CH3
6-C7H15


121
CH3CO
CH3
CH3
6-C7H15


122
C6H5CO
CH3
CH3
6-C7H15


123
CH3OCO
CH3
CH3
6-C7H15


124
C6H5OCO
CH3
CH3
6-C7H15


125
H
CH3
CH3
6-C8H17


126
CH3CO
CH3
CH3
6-C8H17


127
C6H5CO
CH3
CH3
6-C8H17


128
CH3OCO
CH3
CH3
6-C8H17


129
C2H5OCO
CH3
CH3
6-C8H17


130
C6H5OCO
CH3
CH3
6-C8H17


131
H
CH3
CH3
6-CF3


132
CH3CO
CH3
CH3
6-CF3


133
C6H5CO
CH3
CH3
6-CF3


134
CH3OCO
CH3
CH3
6-CF3


135
H
CH3
CH3
6-C6H5O


136
CH3CO
CH3
CH3
6-C6H5O


137
C6H5CO
CH3
CH3
6-C6H5O


138
H
CH3
CH3
5-C2H5


139
H
CH3
CH3
5-C3H7


140
H
CH3
CH3
7-C2H5


141
H
CH3
CH3
7-C3H7


142
H
CH3
CH3
8-C2H5


143
H
CH3
CH3
8-C3H7


144
H
CH3
CH3
6-C4H9, 8-CH3


145
CH3CO
CH3
CH3
6-C4H9, 8-CH3


146
H
CH3
CH3
6-C4H9, 8-F


147
CH3CO
CH3
CH3
6-C4H9, 8-F


148
H
CH3
CH3
6-C4H9, 7-CH3


149
CH3CO
CH3
CH3
6-C4H9, 7-CH3


150
H
CH3
CH3
6-C4H9, 7-F


151
CH3CO
CH3
CH3
6-C4H9, 7-F.










152
H
—(CH2)3—
6-s-C4H9


153
CH3CO
—(CH2)3—
6-s-C4H9











154
H
CH3
CH3
6-N(CH2CH3)2


155
CH3CO
CH3
CH3
6-N(CH2CH3)2


156
H
CH3
CH3
6-Morpholino


157
CH3CO
CH3
CH3
6-Morpholino










158
H
—(CH2)4—
6-iso-C4H9


159
CH3CO
—(CH2)4—
6-iso-C4H9


160
C2H5CO
—(CH2)4—
6-iso-C4H9


161
C6H5CO
—(CH2)4—
6-iso-C4H9


162
H
—(CH2)4—
6-s-C4H9


163
CH3CO
—(CH2)4—
6-s-C4H9


164
C2H5CO
—(CH2)4—
6-s-C4H9


165
C6H5CO
—(CH2)4—
6-s-C4H9


166
H
—(CH2)4—
6-N(CH3)2


167
CH3CO
—(CH2)4—
6-N(CH3)2


168
C2H5CO
—(CH2)4—
6-N(CH3)2


169
C6H5CO
—(CH2)4—
6-N(CH3)2











170
c-C6H11CO
CH3
CH3
6-s-C4H9


171
4-NO2—C6H4CO
CH3
CH3
6-s-C4H9


172
C6H5CH2CO
CH3
CH3
6-s-C4H9


173
C6H11CO
CH3
CH3
6-s-C4H9


174
C6H13CO
CH3
CH3
6-s-C4H9


175
CH2═CHCH2CO
CH3
CH3
6-s-C4H9


176
iso-C4H9CO
CH3
CH3
6-s-C4H9


177
2,6-diCl—C6H3CO
CH3
CH3
6-s-C4H9


178
H
CH3
CH3
6-(1-c-pentenyl)


179
C4H9OCO
CH3
CH3
6-s-C4H9


180
C7H15CO
CH3
CH3
6-s-C4H9


181
H
CH3
CH3
6-Br


182
CH3CO
CH3
CH3
5-C2H5


183
CH3CO
CH3
CH3
7-C2H5


184
CH3CO
CH3
CH3
8-C2H5


185
CH3CO
CH3
CH3
6-Br


186
H
CH3
CH3
6-C4H9, 8-Br


187
CH3CO
CH3
CH3
6-C4H9, 8-Br


188
H
CH3
C8H17
6-s-C4H9


189
CH3CO
CH3
C8H17
6-s-C4H9


190
H
CH3
CH3
6-Br, 8-CH3


191
H
CH3
CH3
5-CH3, 6-Br


192
H
CH3
CH3
6-Br, 7-CH3


193
H
CH3
CH3
6-Br, 8-F


194
H
CH3
CH3
6-F, 8-CH3


195
CH3CO
CH3
CH3
6-Br, 8-CH3


196
CH3CO
CH3
CH3
6-Br, 7-CH3


197
CH3CO
CH3
CH3
5-CH3, 6-Br


198
CH3CO
CH3
CH3
6-F, 8-CH3


199
H
CH3
CH3
6-CH3CH═C(CH3)


200
CH3CO
CH3
CH3
6-CH3CH═C(CH3)


201
H
CH3
CH3
5-CH3, 6-s-C4H9


202
CH3CO
CH3
CH3
5-CH3, 6-s-C4H9


203
H
CH3
CH3
6-s-C4H9, 7-CH3


204
CH3CO
CH3
CH3
6-s-C4H9, 7-CH3


205
H
CH3
CH3
6-s-C4H9, 8-CH3


206
CH3CO
CH3
CH3
6-s-C4H9, 8-CH3


207
H
CH3
CH3
5-F, 6-s-C4H9


208
CH3CO
CH3
CH3
5-F, 6-s-C4H9


209
H
CH3
CH3
6-s-C4H9, 7-F


210
CH3CO
CH3
CH3
6-s-C4H9, 7-F


211
H
CH3
CH3
6-s-C4H9, 8-F


212
CH3CO
CH3
CH3
6-s-C4H9, 8-F


213
H
CH3
CH3
6-s-C4H9, 8-Cl


214
CH3CO
CH3
CH3
6-s-C4H9, 8-Cl


215
H
CH3
CH3
6-n-C4H9, 8-Cl


216
CH3CO
CH3
CH3
6-n-C4H9, 8-Cl


217
H
CH3
CH3
6-t-C4H9, 8-Cl


218
CH3CO
CH3
CH3
6-t-C4H9, 8-Cl


219
H
CH3
CH3
6-s-C4H9, 8-CH3O


220
CH3CO
CH3
CH3
6-s-C4H9, 8-CH3O


221
H
CH3
CH3
6-n-C4H9, 8-CH3O


222
CH3CO
CH3
CH3
6-n-C4H9, 8-CH3O


223
H
CH3
CH3
6-t-C4H9, 8-CH3O


224
CH3CO
CH3
CH3
6-t-C4H9, 8-CH3O


225
H
CH3
CH3
6-s-C4H9, 5-Cl


226
CH3CO
CH3
CH3
6-s-C4H9, 5-Cl


227
H
CH3
CH3
6-t-C4H9, 5-Cl


228
CH3CO
CH3
CH3
6-t-C4H9, 5-Cl


229
H
CH3
CH3
6-n-C4H9, 5-Cl


230
CH3CO
CH3
CH3
6-n-C4H9, 5-Cl


231
H
CH3
CH3
6-s-C4H9, 5-CH3O


232
CH3CO
CH3
CH3
6-s-C4H9, 5-CH3O


233
H
CH3
CH3
6-n-C4H9, 5-CH3O


234
CH3CO
CH3
CH3
6-n-C4H9, 5-CH3O


235
H
CH3
CH3
6-t-C4H9, 5-OCH3


236
CH3CO
CH3
CH3
6-t-C4H9, 5-OCH3


237
H
CH3
CH3
6-s-C4H9, 7-Cl


238
CH3CO
CH3
CH3
6-s-C4H9, 7-Cl


239
H
CH3
CH3
6-t-C4H9, 7-Cl


240
CH3CO
CH3
CH3
6-t-C4H9, 7-Cl


241
H
CH3
CH3
6-n-C4H9, 7-Cl


242
CH3CO
CH3
CH3
6-n-C4H9, 7-Cl


243
H
CH3
CH3
6-s-C4H9, 7-CH3O


244
CH3CO
CH3
CH3
6-s-C4H9, 7-CH3O


245
H
CH3
CH3
6-n-C4H9, 7-CH3O


246
CH3CO
CH3
CH3
6-n-C4H9, 7-CH3O


247
H
CH3
CH3
6-t-C4H9, 7-CH3O


248
CH3CO
CH3
CH3
6-t-C4H9, 7-CH3O


249
H
CH3
CH3
6-t-C4H9, 8-CH3


250
CH3CO
CH3
CH3
6-t-C4H9, 8-CH3


251
H
CH3
CH3
6-t-C4H9, 8-F


252
CH3CO
CH3
CH3
6-t-C4H9, 8-F


253
H
CH3
CH3
6-t-C4H9, 5-CH3


254
CH3CO
CH3
CH3
6-t-C4H9, 5-CH3


255
H
CH3
CH3
6-t-C4H9, 5-F


256
CH3CO
CH3
CH3
6-t-C4H9, 5-F


257
H
CH3
CH3
6-t-C4H9, 7-CH3


258
CH3CO
CH3
CH3
6-t-C4H9, 7-CH3


259
H
CH3
CH3
6-t-C4H9, 7-F


260
CH3CO
CH3
CH3
6-t-C4H9, 7-F


261
H
CH3
CH3
6-CH3, 8-CH3


262
CH3CO
CH3
CH3
6-CH3, 8-CH3


263
H
CH3
CH3
5-CH3, 6-CH3


264
CH3CO
CH3
CH3
5-CH3, 6-CH3


265
H
CH3
CH3
6-CH3, 7-CH3


266
CH3CO
CH3
CH3
6-CH3, 7-CH3


267
H
CH3
CH3
6-C2H5, 8-C2H5


268
CH3CO
CH3
CH3
6-C2H5, 8-C2H5


269
H
CH3
CH3
5-C2H5, 6-C2H5


270
CH3CO
CH3
CH3
5-C2H5, 6-C2H5


271
H
CH3
CH3
6-C2H5, 7-C2H5


272
CH3CO
CH3
CH3
6-C2H5, 7-C2H5


273
H
CH3
CH3
6-iso-C3H7,






8-iso-C3H7


274
CH3CO
CH3
CH3
6-iso-C3H7,






8-iso-C3H7


275
H
CH3
CH3
5-iso-C3H7,






6-iso-C3H7


276
CH3CO
CH3
CH3
5-iso-C3H7,






6-iso-C3H7


277
H
CH3
CH3
6-iso-C3H7,






7-iso-C3H7


278
CH3CO
CH3
CH3
6-iso-C3H7,






7-iso-C3H7


279
H
CH3
CH3
6-s-C4H9,






8-s-C4H9


280
CH3CO
CH3
CH3
6-s-C4H9,






8-s-C4H9


281
H
CH3
CH3
5-s-C4H9,






6-s-C4H9


282
CH3CO
CH3
CH3
5-s-C4H9,






6-s-C4H9


283
H
CH3
CH3
6-s-C4H9,






7-s-C4H9


284
CH3CO
CH3
CH3
6-s-C4H9,






7-s-C4H9


285
H
CH3
CH3
6-t-C4H9,






8-t-C4H9


286
CH3CO
CH3
CH3
6-t-C4H9,






8-t-C4H9


287
H
CH3
CH3
5-t-C4H9,






6-t-C4H9


288
CH3CO
CH3
CH3
5-t-C4H9,






6-t-C4H9


289
H
CH3
CH3
6-t-C4H9,






7-t-C4H9


290
CH3CO
CH3
CH3
6-t-C4H9,






7-t-C4H9


291
H
CH3
CH3
6-c-C3H4(CH3)


292
CH3CO
CH3
CH3
6-c-C3H4(CH3)


293
H
CH3
CH3
6-c-C3H4(CH3),






8-CH3


294
CH3CO
CH3
CH3
6-c-C3H4(CH3),






8-CH3


295
H
CH3
CH3
6-c-C3H4(CH3),






8-Cl


296
CH3CO
CH3
CH3
6-c-C3H4(CH3),






8-Cl


297
H
CH3
CH3
6-c-C3H5—CH2


298
CH3CO
CH3
CH3
6-c-C3H5—CH2


299
H
CH3
CH3
6-c-C3H5—CH2,






8-CH3


300
CH3CO
CH3
CH3
6-c-C3H5—CH2,






8-CH3


301
H
CH3
CH3
6-c-C3H5—CH2,






8-Cl


302
CH3CO
CH3
CH3
6-c-C3H5—CH2,






8-Cl


303
H
CH3
CH3
6-C6H5


304
CH3CO
CH3
CH3
6-C6H5


305
H
CH3
CH3
6-C6H5, 8-CH3


306
CH3CO
CH3
CH3
6-C6H5, 8-CH3


307
H
CH3
CH3
6-C6H5, 8-Cl


308
CH3CO
CH3
CH3
6-C6H5, 8-Cl


309
H
CH3
CH3
6-(p-Cl)—C6H4


310
CH3CO
CH3
CH3
6-(p-Cl)—C6H4


311
H
CH3
CH3
6-(p-Cl)—C6H4,






8-CH3


312
CH3CO
CH3
CH3
6-(p-Cl)—C6H4,






8-CH3


313
H
CH3
CH3
6-(p-Cl)—C6H4,






8-Cl


314
CH3CO
CH3
CH3
6-(p-Cl)—C6H4,






8-Cl


315
H
CH3
CH3
6-(p-CH3)—C6H4


316
CH3CO
CH3
CH3
6-(p-CH3)—C6H4


317
H
CH3
CH3
6-(p-CH3)—C6H4,






8-CH3


318
CH3CO
CH3
CH3
6-(p-CH3)—C6H4,






8-CH3


319
H
CH3
CH3
6-(p-CH3)—C6H4,






8-Cl


320
CH3CO
CH3
CH3
6-(p-CH3)—C6H4,






8-Cl


321
H
CH3
CH3
6-C6H5—CH2


322
CH3CO
CH3
CH3
6-C6H5CH2


323
H
CH3
CH3
6-C6H5—CH2,






8-CH3


324
CH3CO
CH3
CH3
6-C6H5—CH2,






8-CH3


325
H
CH3
CH3
6-C6H5—CH2,






8-Cl


326
CH3CO
CH3
CH3
6-C6H5—CH2,






8-Cl


327
H
CH3
CH3
6-C6H5—C(CH3)2


328
CH3CO
CH3
CH3
6-C6H5—C(CH3)2


329
H
CH3
CH3
6-C6H5—C(CH3)2,






8-CH3


330
CH3CO
CH3
CH3
6-C6H5—C(CH3)2,






8-CH3


331
H
CH3
CH3
6-C6H5—C(CH3)2,






8-Cl


332
CH3CO
CH3
CH3
6-C6H5—C(CH3)2,






8-Cl


333
H
CH3
CH3
6-t-C4H9—CH2


334
CH3CO
CH3
CH3
6-t-C4H9—CH2


335
H
CH3
CH3
6-t-C4H9—CH2,






8-CH3


336
CH3CO
CH3
CH3
6-t-C4H9—CH2,






8-CH3


337
H
CH3
CH3
6-t-C4H9—CH2,






8-Cl


338
CH3CO
CH3
CH3
6-t-C4H9—CH2,






8-Cl


339
H
CH3
CH3
6-s-C4H9,






8-CH2OH


340
CH3CO
CH3
CH3
6-s-C4H9,






8-CH2OH


341
H
CH3
CH3
6-t-C4H9,






8-CH2OH


342
CH3CO
CH3
CH3
6-t-C4H9,






8-CH2OH


343
H
CH3
CH3
6-s-C4H9,






8-CH2Cl


344
CH3CO
CH3
CH3
6-s-C4H9,






8-CH2Cl


345
H
CH3
CH3
6-t-C4H9,






8-CH2Cl


346
CH3CO
CH3
CH3
6-t-C4H9,






8-CH2Cl


347
H
CH3
CH3
6-s-C4H9,






8-C2H5


348
CH3CO
CH3
CH3
6-s-C4H9,






8-C2H5


349
H
CH3
CH3
6-t-C4H9,






8-C2H5


350
CH3CO
CH3
CH3
6-t-C4H9,






8-C2H5


351
H
CH3
CH3
6-c-C5H9,






8-CH3


352
CH3CO
CH3
CH3
6-c-C5H9,






8-CH3


353
H
CH3
CH3
6-c-C5H9,






8-Cl


354
CH3CO
CH3
CH3
6-c-C5H9,






8-Cl


355
H
CH3
CH3
6-s-C4H9,






8-CHO


356
CH3CO
CH3
CH3
6-s-C4H9,






8-CHO


357
H
CH3
CH3
6-t-C4H9,






8-CHO


358
CH3CO
CH3
CH3
6-t-C4H9,






8-CHO


359
H
CH3
CH3
6-CH3CH═C(CH3),






8-CH3


360
CH3CO
CH3
CH3
6-CH3CH═C(CH3),






8-CH3


361
H
CH3
CH3
6-CH3CH═C(CH3),






8-F


362
CH3CO
CH3
CH3
6-CH3CH═C(CH3),






8-F


363
H
CH3
CH3
6-s-C4H9,






8-CN


364
CH3CO
CH3
CH3
6-s-C4H9,






8-CN


365
H
CH3
CH3
6-t-C4H9,






8-CN


366
CH3CO
CH3
CH3
6-t-C4H9,






8-CN


367
H
CH3
CH3
6-s-C4H9,






8-NO2


368
CH3CO
CH3
CH3
6-s-C4H9,






8-NO2


369
H
CH3
CH3
6-t-C4H9,






8-NO2


370
CH3CO
CH3
CH3
6-t-C4H9,






8-NO2


371
H
CH3
CH3
6-s-C4H9,






8-CH3OCO


372
CH3CO
CH3
CH3
6-s-C4H9,






8-CH3OCO


373
H
CH3
CH3
6-t-C4H9,






8-CH3OCO


374
CH3CO
CH3
CH3
6-t-C4H9,






8-CH3OCO









Compounds of the general formula (I)′ which comprise a part of 4-quinolinol derivatives represented by the general formula (I) can be prepared by the known method as described in JP-03128355A according to the following scheme.




Thus, a compound of the general formula (I)′ was synthesized by reacting a compound represented by the general formula (II) with a reagent represented by the general formula (III) or (IV) in the presence or absence of a base and by, if necessary, replacing a substituent of the thus obtained compound with a desired substituent. In the above formulae, R1 to R4 and W are as defined above. Example of the usable base includes organic amines, such as triethylamine and pyridine, or inorganic alkalis, such as sodium carbonate, potassium carbonate and sodium hydride. A compound of the general formula (II) as one of the starting materials was synthesized by a known method as described in J. Am. Chem. Soc., 70, 2402 (1948); Tetrahedron Lett., 27, 5323 (1986) using as a starting material, a substituted aniline which was commercially available or prepared by a known method. And, the reagent represented by the general formula (III) or (IV) is desirably used in an amount of 1 to 50 equivalents, preferably 1 to 10 equivalents with respect to the compound of the general formula (II). The reaction can be carried out in an inert organic solvent, such as dimethylformamide or dimethyl sulfoxide, at the temperature ranging from 0 to 140° C.
Compounds represented by the aforementioned general formula (I) have an excellent fungicidal effect against blast of rice, brown spot of rice, powdery mildew of Cucurbitaceae, anthracnose of potato and the like.
When the present compound represented by the general formula (I) is used as an active ingredient of an agricultural and horticultural fungicide, it can be used as such. However, the present compound is generally used in any formulation, such as emulsifiable concentrate, solution, wettable powder, dust formulation, granule, oil solution, aerosol or flowable, which is prepared by combining the present compound with suitable adjuvants, such as solid carrier, liquid carrier, gaseous carrier, surfactant, dispersant and other additives.
Example of the solid carrier includes talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate and the like. Example of the liquid carrier includes alcohols, such as methanol, n-hexanol and ethylene glycol; ketones, such as acetone, methyl ethyl ketone and cyclohexanone; aliphatic hydrocarbons, such as n-hexane, kerosine and kerosene; aromatic hydrocarbons, such as toluene, xylene and methylnaphthalene; ethers, such as diethyl ether, dioxane and tetrahydrofuran; esters, such as ethyl acetate; nitriles, such as acetonitrile and isobutyronitrile; acid amides, such as dimethylformamide and dimethylacetamide; vegetable oils, such as soybean oil and cottonseed oil; dimethyl sulfoxide; water; and the like. And, example of the gaseous carrier includes LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.
Example of the surfactant or dispersant used for emulsification, dispersion and wetting includes alkyl sulfate esters, alkyl(aryl) sulfonate salts, polyoxyalkylene alkyl(aryl) ethers, polyhydric alcohol esters, lignin sulfonate salts and the like.
And, example of the adjuvant used for improving properties of a formulation includes carboxymethylcellulose, gum arabic, polyethylene glycol, calcium stearate and the like.
The above carrier, surfactant, dispersant and adjuvant may be used alone or in combination, if necessary.
Suitable amount of the active ingredient is generally 1 to 75% by weight in emulsifiable concentrate, generally 0.3 to 25% by weight in dust formulation, generally 1 to 90% by weight in wettable powder, or generally 0.5 to 10% by weight in granule.
Each of these formulations may be used as such or after dilution. Further, each of these formulations may be used in admixture with any other-fungicide, insecticide, acaricide, herbicide, plant growth regulator, fertilizer and the like.
The application methods of the agricultural and horticultural fungicide of the present invention includes foliar application, paddy water application, soil treatment, nursery box application, seed disinfection and the like. Other application methods which are generally employed by those skilled in the art, however, can also show the desired effect of the present invention.


EXAMPLES
Syntheses of the 4-quinolinol derivatives represented by the general formula (I) will be specifically illustrated by way of the following examples which are not intended to limit the invention.
Example 1
Synthesis of 4-hydroxy-2,3-dimethyl-6-n-pentyl-quinoline (Compound No. 97)
1.63 Grams of 4-n-pentylaniline and 1.44 g of ethyl 2-methylacetoacetate were refluxed in benzene in the presence of a Lewis acid catalyst for 3 hours. The reaction mixture was washed with a saturated sodium hydrogencarbonate solution and a saturated brine and dried over-anhydrous sodium sulfate. After the solvent was evaporated, the resultant intermediate was refluxed in diphenyl ether for 30 minutes and allowed to cool to produce precipitates, which were collected by filtration under reduced pressure to obtain 1.01 g of 4-hydroxy-2,3-dimethyl-6-n-pentyl-quinoline (yield 42%). Its NMR spectral data are shown in the following Table 2.
Example 2 to 9
The following compounds were synthesized in the same way as that described in Example 1. NMR spectral data of the thus-obtained compounds are shown in the following Table 2.
Example 2
Compound No. 107 (yield 64%)
Example 3
Compound No. 111 (yield 56%)
Example 4
Compound No. 125 (yield 22%)
Example 5
Compound No. 131 (yield 25%)
Example 6
Compound No. 135 (yield 24%)
Example 7
Compound No. 152 (yield 34%)
Example 8
Compound No. 154 (yield 52%)
Example 9
Compound No. 156 (yield 52%)
Example 10
Synthesis of 4-acetoxy-2-3-dimethyl-6-n-pentyl-qunoline (Compound No. 98)
100 Milligrams of 4-hydroxy-2,3-dimethyl-6-n-pentyl-quinoline (Compound No. 97) was stirred in 2 ml of acetic anhydride at 120° C. for 4 hours. After the solvent was evaporated, 20 ml of ethyl acetate was added and the reaction mixture was washed with an aqueous saturated sodium hydrogencarbonate solution and a saturated brine and dried over anhydrous sodium sulfate. After the solvent was evaporated under reduced pressure, the resultant crude product was purified by column chromatography on silica gel (WAKOGEL® C-100) eluting with n-hexane/ethyl acetate (5:1) to obtain 87.4 mg of 4-acetoxy-2,3-dimethyl-6-n-pentyl-quinoline (yield 74%). Its NMR spectral data are shown in the following Table 2.
Examples 11 to 18
The following compounds were synthesized in the same way as that described in Example 10. NMR spectral data of the thus-obtained compounds are shown in the following Table 2.
Example 11
Compound No. 108 (yield 62%)
Example 12
Compound No. 112 (yield 68%)
Example 13
Compound No. 126 (yield 74%)
Example 14
Compound No. 132 (yield 8%)
Example 15
Compound No. 136 (yield 76%)
Example 16
Compound No. 153 (yield 59%)
Example 17
Compound No. 155 (yield 94%)
Example 18
Compound No. 157 (yield 87%)
Example 19
Synthesis of 4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinoline (Compound No. 360)
26.6 Grams of 6-bromo-4-hydroxy-2,3,8-trimethylquinoline synthesized in the same way as that described in Example 1 was suspended in 70 ml of dimethylformamide, to which 4.4 g of 60% sodium hydride was added under cooling with ice and then the mixture was stirred at room temperature for 30 minutes. 19 Grams of benzyl bromide was added dropwise to the reaction mixture under cooling with ice and the mixture was allowed to react at room temperature overnight. After 50 ml of water was added, the reaction mixture was extracted with ethyl acetate and the organic layer was washed with a saturated brine and dried over anhydrous sodium sulfate overnight. After the solvent was evaporated under reduced pressure, the resultant crude product was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (6:1) to obtain 24.3 g of 4-benzyloxy-6-bromo-2,3,8-trimethylquinoline.
4 Grams of the thus-obtained 4-benzyloxy-6-bromo-2,3,8-trimethylquinoline was dissolved in 40 ml of anhydrous tetrahydrofuran and cooled to −78° C., to which 5 ml of a 2.5 M solution of n-butyllithium in n-hexane was added dropwise and the mixture was stirred for 10 minutes. A solution of 1.2 g of 2-butanone dissolved in 4 ml of anhydrous tetrahydrofuran was added dropwise to the reaction mixture, which was then stirred at 0° C. for 20 minutes. After 30 ml of water was added, the reaction mixture was extracted with ethyl acetate and the organic layer was washed with a saturated brine and dried over anhydrous sodium sulfate overnight. After the solvent was evaporated under reduced pressure, the residue was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (7:1) to obtain 3.5 g of 4-benzyloxy-6-(2-hydroxybutyl-2-yl)-2,3,8-trimethylquinoline.
To 2.8 g of the thus-obtained 4-benzyloxy-6-(2-hydroxybutyl-2-yl)-2,3,8-trimethylquinoline was added 10 ml of 20% sulfuric acid and the mixture was stirred at 100° C. for 80 minutes. The reaction mixture was cooled to room temperature and then neutralized with an aqueous saturated sodium carbonate solution. Precipitates were washed with water and n-hexane and then dried under reduced pressure to obtain 2.3 g of a crude product. 2.0 Grams of the crude product was suspended in 10 ml of dimethylformamide, to which 0.37 g of 60% sodium hydride was added under cooling with ice. After stirring at room temperature for 30 minutes, 0.72 g of acetyl chloride was added dropwise under cooling with ice and the mixture was stirred at room temperature for 20 hours. After 15 ml of water was added, the reaction mixture was stirred and then extracted with ethyl acetate. The organic layer was washed with a saturated brine and then dried over anhydrous sodium sulfate overnight. After the solvent was evaporated under reduced pressure, the crude product was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (9:1) to obtain 1.6 g of 4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinoline (yield 42%). Its-NMR spectral data are shown in the following Table 2.
Example 20
Synthesis of 4-acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline (Compound No. 362)
4-Acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline was synthesized in the same way as that described in Example 19 using 6-bromo-4-hydroxy-8-fluoro-2,3-dimethylquinoline as a starting material (yield 17%). NMR spectral data of the thus-obtained compounds are shown in the following Table 2.
Example 21
Synthesis of 4-acetoxy-6-s-butyl-2,3,8-trimethylquinoline (Compound No. 206)
To 0.41 g of 4-acetoxy-6-(2-buten-2-yl)-2,3,8-trimethylquinoline obtained in the same way as that described in Example 19 and 0.06 g of 10% palladium-carbon, 6 ml of methanol was added and hydrogen was passed therethrough to react for 16 hours at room temperature with stirring. The reaction mixture was filtered and the residue was washed twice with 2 ml of methanol. The solvent was evaporated under reduced pressure to obtain 0.37 g of 4-acetoxy-6-s-butyl-2,3,8-trimethylquinoline (yield 90%). Its NMR spectral data are shown in the following Table 2.
Example 22
Synthesis of 4-acetoxy-6-s-butyl-8-fluoro-2,3-dimethylquinoline (Compound No. 212)
0.27 Grams of 4-acetoxy-6-s-butyl-8-fluoro-2,3-dimethylquinoline was obtained using 0.37 g of 4-acetoxy-6-(2-buten-2-yl)-8-fluoro-2,3-dimethylquinoline obtained in Example 20 as a starting material in the same way as that described in Example 21 (yield 72%). Its NMR spectral data are shown in the following Table 2.
Example 23
Synthesis of 4-acetoxy-6-c-pentyl-8-methyl-2,3-dimethylquinoline (Compound No. 352)
4-Acetoxy-6-c-pentyl-8-methyl-2,3-dimethylquinoline was obtained in the same way as that described in Example 21 (yield 37%).
Example 24
Synthesis of 4-acetoxy-6-s-butyl-8-chloro-2,3-dimethylquinoline (Compound No. 214)
4.9 Grams of 4-s-butyl-aniline was dissolved in dimethylformamide, to which 4 g of N-chloro-succinimide dissolved in 20 ml of dimethylformamide was added dropwise at room temperature and the mixture was stirred overnight. The reaction mixture was poured into 100 ml of water, which was extracted with n-hexane. The organic layer was washed with a saturated brine, dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. Using the resultant crude 4-s-butyl-2-chloroaniline in the same way as that described in Example 1,4-hydroxy-6-s-butyl-8-chloro-2,3-dimethylquinoline was obtained. Using it as a starting material, 287.5 mg of 4-acetoxy-6-s-butyl-8-chloro-2,3-dimethylquinoline was obtained in the same way as that described in Example 10 (yield 17%). Its NMR spectral data are shown in the following Table 2.
Examples 25 and 26
The following compounds were synthesized in the same way as that described in Example 23. NMR spectral data of the thus-obtained compounds are shown in the following Table 2.
Example 25
Compound No. 216 (yield 31%)
Example 26
Compound No. 218 (yield 8%)
Example 27
Synthesis of 4-acetoxy-6-s-butyl-8-methoxy-2,3-dimethylqunoline (Compound No. 220)
4-s-Butyl-2-methoxyaniline was obtained using 3-methoxyacetophenone as a starting material according to various known reactions. Using 530 mg of the thus-obtained 4-s-butyl-2-methoxyaniline, 264 mg of 4-acetoxy-6-s-butyl-8-methoxy-2,3-dimethylquinoline was obtained in the same way as that described in Examples 1 and 10 (yield 40%). Its NMR spectral data are shown in the following Table 2.
Examples 28 to 32
The following compounds were synthesized in the same way as that described in Example 26. NMR spectral data of the thus-obtained compounds are shown in the following table 2.
Example 28
Compound No. 262 (yield 53%)
Example 29
Compound No. 268 (yield 42%)
Example 30
Compound No. 274 (yield 49%)
Example 31
Compound No. 280 (yield 39%)
Example 32
Compound No. 348 (yield 40%)
Example 33
Synthesis of 4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinoline (Compound No. 356)
Grams of 4-hydroxy-6-s-butyl-8-bromo-2,3-dimethylquinoline synthesized in the same way as that described in Example 1 was suspended in 20 ml of dimethylformamide, to which 700 mg of 60% sodium hydride was added under cooling with ice and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture was added dropwise 3 g of benzyl bromide under cooling with ice and the mixture was allowed to react at room temperature overnight. After the addition of 50 ml of water, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with a saturated brine and dried over anhydrous sodium sulfate overnight. After the solvent was evaporated under reduced pressure, the resultant crude product was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane to obtain 2.5 g of 4-benzyloxy-6-s-butyl-8-bromo-2,3-dimethylquinoline. 2.5 Grams of the thus-obtained 4-benzyloxy-6-s-butyl-8-bromo-2,3-dimethylquinoline was dissolved in 25 ml of anhydrous tetrahydrofuran and cooled to −78° C., to which 2.8 ml of a 2.5 M solution of n-butyl lithium in n-hexane was added dropwise and the mixture was stirred for 10 minutes. One ml of methyl formate dissolved in 2 ml of anhydrous tetrahydrofuran was added dropwise to the reaction mixture and the mixture was stirred at 0° C. for 30 minutes. After the addition of 50 ml of water, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with an aqueous saturated ammonium chloride solution and a saturated brine and then dried over anhydrous sodium sulfate. After the solvent was evaporated under reduced pressure, the residue was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (20:1) to Obtain 800 mg of 4-benzyloxy-6-s-butyl-8-formyl-2,3-dimethylquinoline.
800 Milligrams of the resultant 4-benzyloxy-6-s-butyl-8-formyl-2,3-dimethylquinoline was dissolved in 2.5 ml of 20% sulfuric acid and stirred at 100° C. for 1 hour. After cooling to room temperature, the reaction mixture was neutralized with an aqueous saturated sodium hydrogencarbonate solution to produce precipitates, which were washed with water and n-hexane and then dried under reduced pressure to obtain 490 mg of 4-hydroxy-6-s-butyl-8-formyl-2,3-dimethylquinoline. 440 Milligrams of 4-hydroxy-6-s-butyl-8-formyl-2,3-dimethylquinoline was suspended in a mixture of 3 ml of acetic anhydride and 0.5 ml of pyridine and the mixture was stirred at 120° C. for 1.5 hours. The reaction mixture was cooled to room temperature, neutralized with an aqueous saturated sodium hydrogencarbonate solution and extracted with ethyl acetate. The resultant organic layer was washed with a saturated brine and dried over anhydrous sodium sulfate. After the solvent was evaporated, the resultant crude product was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (10:1) to obtain 220 mg of 4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinoline (yield 13%). Its NMR spectral data are shown in the following Table 2.
Example 34
Synthesis of 4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline (Compound No. 340)
210 Milligrams of 4-acetoxy-6-s-butyl-8-formyl-2,3-dimethylquinoline obtained in Example 33 was dissolved in 4 ml of methanol, to which 7 mg of sodium borohydride dissolved in 4 ml of methanol was added dropwise and the mixture was stirred at room temperature for 1 minute. After the addition of 20 ml of water, the reaction mixture was extracted with ethyl acetate. The resultant organic layer was washed with a saturated brine and dried over anhydrous sodium sulfate. After the solvent was evaporated under reduced pressure, the resultant crude product was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (10:1) to obtain 186 mg of 4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline (yield 84%). Its NMR spectral data are shown in the following Table 2.
Example 35
Synthesis of 4-acetoxy-6-s-butyl-8-chloromethyl-2,3-dimethylquinoline (Compound No. 344)
50 Milligrams of 4-acetoxy-6-s-butyl-8-hydroxymethyl-2,3-dimethylquinoline obtained in Example 34 was dissolved in 0.3 ml of thionyl chloride and stirred at room temperature for 4.5 hours. After thionyl chloride was evaporated under reduced pressure, 0.5 ml of acetic anhydride was added to the resultant crude product and the mixture was stirred at 120° C. for 2 hours. After acetic anhydride was evaporated under reduced pressure, the resultant residue was purified by column chromatography on silica gel (WAKOGEL® C-200) eluting with n-hexane/ethyl acetate (20:1) to obtain 12.5 mg of 4-acetoxy-6-s-butyl-8-chloromethyl-2,3-dimethylquinoline (yield 23.5%). Its NMR spectral data are shown in the following Table 2.








TABLE 2





compound



No.
NMR spectral data
















97
11.37(1H, s), 7.83(1H, s), 7.42(1H, dd, J1=8.6, J2=1.6),



7.39(1H, d, J=8.6), 2.65(2H, t, J=7.4), 2.36(3H, s),



1.96(3H, s), 1.59(2H, m), 1.29(4H, m), 0.85(3H, t, J=6.8) solvent: DMSO-d6


98
7.94(1H, d, J=8.7), 7.49(1H, dd, J1=8.7, J2=1.7),



7.42(1H, s), 2.75(2H, m), 2.71(3H, s), 2.52(3H, s),



2.25(3H, s), 1.68(2H, m), 1.34(4H, m), 0.90(3H, t, J=6.7)



solvent: CDCl3


107
11.36(1H, s), 7.83(1H, br.s), 7.39(2H, m), 2.65(2H, m),



2.35(3H, s), 1.95(3H, s), 1.58(2H, m), 1.27(6H, m),



0.85(3H, t, J=6.9) solvent: DMSO-d6


108
7.92(1H, d, J=8.6), 7.49(1H, d, J=8.6), 7.42(1H, s),



2.75(2H, t, J=7.8), 2.71(3H, s), 2.52(3H, s), 2.24(3H, s),



1.67(2H, m), 1.39~1.28(6H, m), 0.88(3H, t, J=7.6)



solvent: CDCl3


111
11.32(1H, s), 7.85(1H, d, J=2.0), 7.44(1H, dd, J1=8.5,



J2=2.2), 7.38(1H, d, J=8.6), 2.60(1H, m), 2.34(3H, s),



1.95(3H, s), 1.81(4H, m), 1.70(1H, m), 1.39(4H, m),



1.25(1H, m) solvent: DMSO-d6


112
8.18(1H, d, J=2.0), 7.93(1H, d, J=8.8), 7.53(1H, dd,



J1=8.8, J2=2.0), 2.86(3H, s), 2.72(1H, m), 2.70(3H, s),



2.52(3H, s), 1.80(4H, m), 1.77(1H, m), 1.46(4H, m),



1.31(1H, m) solvent: CDCl3


125
11.35(1H, s), 7.83(1H, br.s), 7.40(2H, m), 2.65(2H, m),



2.35(3H, s), 1.95(3H, s), 1.58(2H, m), 1.27~1.23(10H, m),



0.84(3H, t, J=6.6) solvent: DMSO-d6


126
7.93(1H, d, J=8.8), 7.49(1H, dd, J1=8.8, J2=1.9),



7.42(1H, d, J=1.2), 2.75(2H, t, J=7.8), 2.71(3H, s),



2.52(3H, s), 2.24(3H, s), 1.71~1.25(10H, m),



0.87(3H, t, J=6.9) solvent: CDCl3


131
11.78(1H, s), 8.33(1H, br.s), 7.86(1H, dd, J1=8.8,



J2=2.0), 7.66(1H, d, J=8.8), 2.40(3H, s), 1.98(3H, s)



solvent: DMSO-d6


132
8.12(1H, d, J=9.0), 8.00(1H, br.s), 7.82(1H, dd, J1=9.0,



J2=2.0), 2.54(3H, s), 2.30(3H, s), 2.28(3H, s)



solvent: CDCl3


135
11.53(1H, s), 7.54(1H, d, J=9.0), 7.47(1H, d, J=3.1),



7.41(2H, dd, J1=8.6, J2=7.5), 7.37(2H, dd, J1=9.0,



J2=3.1), 7.16(1H, t, J=7.5), 7.04(2H, dd, J1=8.6, J2=1.0),



2.37(3H, s), 1.94(3H, s) solvent: DMSO-d6


136
7.98(1H, d, J=9.4), 7.38(2H, br.d, J=8.6), 7.35(1H, d,



J=2.7), 7.18(1H, d, J=2.7), 7.14(1H, br.d, J=6.7),



7.06(2H, br.dd, J1=8.6, J2=0.8), 2.71(3H, s), 2.40(3H, s)



solvent: CDCl3


152
11.83(1H, s), 7.90(1H, s), 7.43(2H, s), 2.97(1H, t),



2.68(3H, m), 2.04(2H, t), 1.60(2H, t), 1.23(3H, d),



0.77(3H, t) solvent: DMSO-d6


153
7.97(1H, d, J=8.8), 7.54(1H, d, J=1.9), 7.51(1H, dd,



J1=8.8, J2=1.9), 3.19(2H, t, J=7.7), 2.95(2H, t, J=7.4),



2.76(1H, m), 2.49(3H, s), 2.20(2H, quint, J=7.4),



1.67(2H, quint, J=7.4), 1.31(3H, d, J=6.9), 0.84(3H, t,



J=7.3) solvent: CDCl3


154
11.20(1H, s), 7.36(1H, d, J=8.7), 7.21(1H, d, J=2.0),



7.10(1H, dd, J1=8.7, J2=2.0), 3.38(4H, q, J=6.9),



2.34(3H, s), 1.97(3H, s), 1.11(6H, t, J=6.9)



solvent: DMSO-d6


155
8.56(1H, d, J=2.8), 7.85(1H, d, J=9.3), 7.20(1H, dd, J1=9.3,



J2=2.8), 3.44(4H, q, J=7.0), 2.64(3H, s), 2.48(3H, s),



2.21(3H, s), 1.21(6H, t, J=7.0) solvent: CDCl3


156
11.23(1H, s), 7.40(3H, s), 3.86(4H, m), 3.11(4H, m),



2.35(3H, s), 2.06(3H, s) solvent: DMSO-d6


157
8.85(1H, d, J=2.7), 7.90(1H, d, J=9.2), 7.39(1H, dd,



J1=9.2, J2=2.7), 3.90(4H, m), 3.26(4H, m), 2.67(3H, s),



2.50(3H, s), 2.23(3H, s) solvent: CDCl3


206
7.31(1H, s), 7.24(1H, s), 2.74(3H, s), 2.69(3H, s), 2.67(1H, m)



2.48(3H, s), 2.21(3H, s), 1.63(2H, m), 1.27(3H, d, J=7.0)



0.81(3H, t, J=7.0) solvent: CDCl3


212
7.21(1H, m), 7.19(1H, m), 2.74(1H, m), 2.73(3H, s), 2.50(3H, s)



2.24(3H, s), 1.62(2H, m), 1.27(3H, d, J=7.0), 0.82(3H, t, J=7.0)



solvent: CDCl3


214
7.63(1H, d, J=2.0), 7.34(1H, d, J=2.0), 2.77(3H, s), 2.73(1H, m),



2.51(3H, s), 2.25(3H, s), 1.65(2H, m), 1.30(3H, d, J=6.9),



0.84(3H, t, J=7.3) solvent: CDCl3


216
7.62(1H, d, J=1.9), 7.35(1H, d, J=1.7), 2.77(3H, s), 2.73(2H, t, J=7.8)



2.51(3H, s), 2.25(3H, s), 1.66(2H, m), 1.39(2H, m), 0.95(3H, t, J=7.3)



solvent: CDCl3


218
7.83(1H, d, J=2.0), 7.51(1H, d, J=1.9), 2.77(3H, s), 2.51(3H, s)



2.25(3H, s), 1.39(9H, s) solvent: CDCl3


220
7.01(1H, d, J=1.5), 6.84(1H, d, J=1.5), 4.06(3H, s), 2.75(3H, s)



2.71(1H, m), 2.50(3H, s), 2.24(3H, s), 1.66(2H, m),



1.30(3H, d, J=6.8), 0.85(3H, t, J=7.5) solvent: CDCl3


262
7.31(1H, s), 7.27(1H, s), 2.74(3H, s), 2.70(3H, s), 2.50(3H, s),



2.46(3H, s), 2.23(3H, s) solvent: CDCl3


268
7.34(1H, s), 7.28(1H, s), 3.25(2H, q, J=7.5), 2.77(2H, q, J=7.5)



2.70(3H, s), 2.23(3H, s), 1.35(3H, t, J=7.5), 1.30(3H, t, J=7.6)



solvent: CDCl3


274
7.40(1H, d, J=2.0), 7.28(1H, d, J=1.9), 4.31(1H, m), 3.04(1H, m)



2.69(3H, s), 2.50(3H, s), 2.23(3H, s), 1.36(6H, d, J=6.8),



1.31(6H, d, J=7.0) solvent: CDCl3


280
7.30(1H, d, J=1.7), 7.24(1H, d, J=1.7), 4.13(1H, m), 2.73(1H, m),



2.69(3H, s), 2.51(3H, s), 2.22(3H, s), 1.61~1.84(4H, m)



1.31(3H, d, J=7.0), 1.30(3H, d, J=7.3), 0.87(3H, t, J=7.3),



0.83(3H, t, J=7.0) solvent: CDCl3


334
7.90(1H, d J=8.5), 7.44(1H, dd J1 =8.5, J2 =2.0), 7.37(1H, d J=2.0),



2.71(3H, s), 2.65(2H, s), 2.51(3H, s), 2.56(3H, s), 0.93(9H, s)



solvent: CDCl3


338
7.58(1H, d J=1.7), 7.31(1H, d J=1.7), 2.78(3H, s), 2.63(2H, s),



2.51(3H, s), 2.27(3H, s), 0.95(9H, s) solvent: CDCl3


340
7.34(1H, d, J=1.7), 7.33(1H, d, J=1.7), 5.64(1H, br.s), 5.12(2H, s)



2.75(1H, m), 2.70(3H, m), 2.51(3H, s), 2.25(3H, s), 1.65(2H, m)



1.29(3H, d, J=6.8), 0.83(3H, t, J=7.3) solvent: CDCl3


344
7.64(1H, d, J=2.0), 7.39(1H, d, J=1.9), 5.32(2H, s), 2.75(1H, m),



2.71(3H, s), 2.51(3H, s), 2.24(3H, s), 1.66(2H, m), 1.31(3H, d =, J=6.8),



0.84(3H, t, J=7.3) solvent: CDCl3


348
7.33(1H, d, J=2.0), 7.25(1H, d, J=2.0), 3.25(2H, q, J=7.4),



2.73(1H, m), 2.70(3H, s), 2.50(3H, s), 2.23(3H, s), 1.65(2H, m),



1.36(3H, t, J=7.6), 1.29(3H, d, J=7.0), 0.84(3H, t, J=7.4)



solvent: CDCl3


352
7.37(1H, s), 7.29(1H, s), 3.08(1H, m), 2.73(3H, s), 2.69(3H, s),



2.48(3H, s), 2.09(3H, s), 1.7~2.2(8H, m) solvent: CDCl3


356
11.43(1H, s), 8.12(1H, d, J=2.2), 7.69(1H, d, J=2.0), 2.82(1H, m),



2.76(3H, s), 2.54(3H, s), 2.28(3H, s), 1.69(2H, m), 1.32(3H, d, J=6.8),



0.83(3H, t, J=7.3) solvent: CDCl3


360
7.53(1H, s), 7.40(1H, s), 5.95(1H, m), 2.74(3H, s), 2.69(3H, s), 2.50



(3H, s), 2.22(3H, s), 2.07(3H, s), 1.82(3H, d, J=6.8)



solvent: CDCl3


362
7.39–7.47(2H, m), 5.98(1H, m), 2.73(3H, s), 2.49(3H, s), 2.24



(3H, s), 2.06(3H, s), 1.83(3H, d, J=7.1) solvent: CDCl3









In the above tables, s, d, t, q, quint and m mean singlet, doublet, triplet, quartet, quintet and multiplet, respectively.
And, DCDl3 and DMSO-d6 mean deuterium chloroform and deuterium DMSO, respectively.
Formulation Example 1 (Wettable Powder)
The following ingredients:
















the present compound (Compound No. 29)
25% by weight



clay
30% by weight



diatomaceous earth
35% by weight



calcium lignin sulfonate
 3% by weight



polyoxyethylene alkyl aryl ether
 7% by weight







were uniformly mixed and pulverized to obtain a wettable powder.









Formulation Example 2 (Dust Formulation)
The following ingredients:
















the present compound (Compound No. 29)
 2% by weight



clay
60% by weight



talc
37% by weight



calcium stearate
 1% by weight







were uniformly mixed to obtain a dust formulation.









Formulation Example 3 (Emulsifiable Concentrate)
The following ingredients:
















the present compound (Compound No. 29)
20% by weight



N,N-dimethylformamide
20% by weight



xylene
50% by weight



polyoxyethylene alkyl aryl ether
10% by weight







were added, uniformly mixed and dissolved


to obtain an emulsifiable concentrate.









Formulation Example 4 (Granule)
The following ingredients:
















the present compound (Compound No. 29)
 5% by weight



bentonite
40% by weight



talc
53% by weight



calcium lignin sulfonate
 2% by weight







were uniformly mixed with grinding, to which water was added,


well kneaded, granulated and then dried to obtain a granule.









Test Example 1 (Test for Control Effect Against Rice Blast)
A spray liquid comprising a test compound whose concentration was adjusted to be 100 ppm by dilution with water was sprayed to a rice seedling (variety: Jikkoku) of 4-leaf stage grown id a vinyl pot of 5 cm in diameter by means of a spray gun. The air-dried rice seedling was inoculated with a conidium suspension of Pyricularia oryzae on the day of said application. For 40 hours after the inoculation, the rice seeding was under moist condition to complete infection with Pyricularia oryzae and then grown in an air-conditioned greenhouse. 6 Days after the inoculation, the lesion number on the fourth-leaf was counted. The protective value was calculated by comparing the lesion number in a treated area with that in an untreated area. Then, control effect was ranked according to the following criterion.

    
    
        A; protective value ≧80%
        B; protective value 50 to 79%
        C; protective value <50%
    
    


Results are shown in Table 3.










TABLE 3







compound




No.
rank



















2
B



9
A



10
A



13
A



14
A



23
B



24
B



28
A



29
A



31
A



44
A



45
A



46
A



47
A



48
A



49
A



54
A



55
A



56
A



57
A



61
A



62
A



63
A



65
A



66
A



67
A



68
A



69
A



70
A



72
B



83
A



84
A



92
B



93
A



97
B



98
A



107
A



108
A



111
B



112
A



125
B



126
A



131
B



136
A



153
B



170
A



171
B



172
A



173
A



179
A



180
A



182
B



183
B



185
B



186
B



190
B



191
A



192
A



193
A



195
A



197
A



198
B



199
A



200
A



206
A



212
A



214
A



216
A



218
A



220
A



262
B



268
A



274
A



340
A



344
A



348
A



352
A



356
A



360
A



362
A










Test Example 2 (Test for Control Effect Against Powdery Mildew) of Cucurbitaceae)
A spray liquid comprising a test compound whose concentration was adjusted to be 200 ppm by dilution with water was sprayed to a cucumber grown in a vinyl pot of 3 cm in diameter when its first foliage leaf was developed. The air-dried cucumber seedling was inoculated with a conidium suspension of Sphaerotheca fuliginea. Thereafter, the cucumber seedling was transferred in an air-conditioned greenhouse. 10 Days after the inoculation, the disease severity was observed. The protective value was calculated by comparing the disease severity in a treated area with that in an untreated area. Then, control effect was ranked according to the following criterion.

    
    
        A; protective value ≧80%
        B; protective value 50 to 79%
        C; protective value <50%
    
    


Results are shown in Table 4.










TABLE 4







compound




No.
rank



















24
A



29
B



45
B



55
A



56
A



61
B



65
A



66
A



67
A



68
A



71
A



72
A



93
A



112
A



136
A



153
A



175
A



176
A



185
A



195
A



196
A



197
A



214
A



216
B



218
A



268
B



340
A



344
A



348
A



356
A










Test Example 3 (Test for Antifungal Activity)
A test compound dissolved in acetone was mixed in a potato dextrose agar medium (manufactured by Nissui Seiyaku K.K.) so that the final concentration of the test compound was 100 ppm and then poured in a Petri dish. To this Perti dish after the agar was completely solidified, a cylindrical section prepared by punching a mycelial colony of each of plant pathogenic fungi cultured in another Petri dish by means of a cork borer was inoculated and cultured at 28 or 22° C. 48 Hours after the inoculation, the diameter of the mycelial colony was determined. Control percentages were calculated by comparing the diameter of the mycelial colony in a treated area with that in an untreated area. And, antifungal effect was ranked according to the following criterion.

    
    
        A; control percentage ≧80%
        B; control percentage 50 to 79%
        C; control percentage <50%
    
    


Results are shown in Table 5.










TABLE 5









Compoud No.














Plant pathogen
10
28
29
31







Pyricularia oryzae
A
B
A
A



Rhizoctonia solani
C
C
C
C



Cochioborus miyabeanus
B
C
B
A



Gibberella fujikuroi
C
C
B
A



Botrytis cinerea
C
C
B
A



Fusarium oxysporum f. sp. lycopersici
C
C
B
A



Glomerella cingalata
B
B
A
A



Sclerotinia minor
C
C
C
B



Colletotrichum atramentarium
B
B
B
A



Alternaria alternata Japanese
C
C
C
A



pear pathotype



Verticillium aibo-atrum
C
A
A
A










EFFECT OF THE INVENTION
The new 4-quinolinol derivatives represented by the general formula (I) of the present invention have an effective action as an agricultural and horticultural fungicide.

## Claims

1. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein
R1 represents
an alkali metal,
an alkaline earth metal, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1–C18 alkyl group,
an optionally substituted C2–C18 alkenyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted phenyl C1–C4 alkyl group,
an optionally substituted phenoxy C1–C4 alkyl group,
an optionally substituted aryl group,

OR5 in which R5 is an optionally substituted C1–C4 alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl C1–C4 alkyl group or an optionally substituted phenoxy C1–C4 alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R1 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C1–C18 alkyl group; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R1 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

2. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents
an alkali metal,
an alkaline earth metal, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1–C18 alkyl group,
an optionally substituted C2–C18 alkenyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted phenyl C1–C4 alkyl group,
an optionally substituted phenoxy C1–C4 alkyl group,
an optionally substituted aryl group,

OR5 in which R5 is an optionally substituted C1–C4 alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl C1–C4 alkyl group or an optionally substituted phenoxy C1–C4 alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C2–C4 alkenyl group; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

3. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents
an alkali metal,
an alkaline earth metal, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1–C18 alkyl group,
an optionally substituted C2–C 18 alkenyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted phenyl C1–C4 alkyl group,
an optionally substituted phenoxy C1–C4 alkyl group,
an optionally substituted aryl group,

OR5 in which R5 is an optionally substituted C1–C4 alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl C1–C4 alkyl group or an optionally substituted phenoxy C1–C4 alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C1–C4 alkoxy group; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1–C10 alkyl group,
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C1–C10 alkoxy group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl, C1–C4 alkoxy group and hydroxyl.

4. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents
an alkali metal,
an alkaline earth metal, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1–C18 alkyl group,
an optionally substituted C2–C 18 alkenyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted phenyl C1–C4 alkyl group,
an optionally substituted phenoxy C1–C4 alkyl group,
an optionally substituted aryl group,

OR5 in which R5 is an optionally substituted C1–C4 alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl C1–C4 alkyl group or an optionally substituted phenoxy C1–C4 alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 and R3 together represent —(CH2)m- in which m is 3 or 4; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl, C1–C4 alkoxy group and hydroxyl.

5. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C1–C18 alkyl group; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

6. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C2–C4 alkenyl group; and
W represents 1 substituents on the nucleus which may be
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

7. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C2–C4 alkenyl group; and
W represents 2 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

8. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C2–C4 alkenyl group; and
W represents 3 to 4 substituents on the nucleus which may be identical or different and each of which is
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

9. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 represents an optionally substituted C1–C4 alkyl group;
R3 represents an optionally substituted C1–C4 alkoxy group; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1–C10 alkyl group,
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C1–C10 alkoxy group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

10. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 and R3 together represent —(CH2)m- in which m is 3 or 4; and
W represents 1 substituent on the nucleus which is
a halogen atom,
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C1–C10 alkoxy group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

11. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof wherein R1 represents a hydrogen atom;
R2 and R3 together represent —(CH2)m- in which m is 3 or 4; and
W represents 2 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1–C10 alkyl group,
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C1–C10 alkoxy group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

12. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 represents a hydrogen atom;
R2 and R3 together represent —(CH2)m- in which m is 3 or 4; and
W represents 3 to 4 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1–C10 alkyl group,
an optionally substituted C2–C4 alkenyl group,
an optionally substituted C2–C4 alkynyl group,
an optionally substituted C1–C10 alkoxy group,
an optionally substituted C3–C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,

NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1–C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted C1–C4 alkyl group or an optionally substituted C2–C4 alkenyl group,
a nitro group, or
a cyano group;
wherein when optionally substituents present, the optional group is selected from the group consisting of halogen, C1–C4 alkyl group, C1–C4 alkoxy group and hydroxyl.

13. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-s-C4H9 and 8-CH2OH.

14. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-s-C4H9 and 8-CH2OH.

15. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-t-C4H9 and 8-CH2OH.

16. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-t-C4H9 and 8-CH2OH.

17. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-s-C4H9 and 8-CH2Cl.

18. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-t-C4H9 and 8-CH2Cl.

19. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-c-C5H9 and 8-methyl.

20. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-c-C5H9 and 8-methyl.

21. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-c-C5H9 and 8-Cl.

22. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-c-C5H9 and 8-Cl.

23. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-s-C4H9 and 8-CHO.

24. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-s-C4H9 and 8-CHO.

25. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-t-C4H9 and 8-CHO.

26. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-t-C4H9 and 8-CHO.

27. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-CH3CH═C(CH3) and 8-methyl.

28. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-CH3CH═C(CH3) and 8-methyl.

29. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is a hydrogen atom; R2 and R3 are each methyl; and W are 6-CH3CH═C(CH3) and 8-F.

30. A 4-quinolinol compound represented by the formula (I):



or an agricultural and horticulturally acceptable acid addition salt thereof, wherein R1 is CH3CO; R2 and R3 are each methyl; and W are 6-CH3CH═C(CH3) and 8-F.