N-(substituted benzyloxy) imine derivatives and method of use thereof

Compound of the general formula (I), which is useful as an agricultural and horticultural fungicide, an agricultural and horticultural fungicidal composition containing said compound, use of said composition for controlling plant disease, and process for the production of said compound: ##STR1## wherein ##STR2## shows a case in which R.sup.3 and R.sup.4 together form a cyclic substituent, and R.sup.1 and R.sup.4 are substituents disclosed in the specification.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to N-(substituted benzyloxy)imine derivatives, 
agricultural and horticultural fungicides containing them as an active 
ingredient, a process for the production thereof, and a controlling 
method. 
2. Related Art 
JP-A-61-280452 and JP, A-61-28045 disclose compounds which are structurally 
similar to the compound of this invention, and describe that such 
compounds are useful as a agricultural fungicide or insecticide. However, 
their activities cannot not necessarily be said to be satisfactory. 
The compounds of this invention are novel compounds which have different 
substituents from those of these known compounds and have remarkable 
fungicidal activity over these known compounds.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
This invention relates to N-(substituted benzyloxy)imine derivatives of 
general formula 
##STR3## 
wherein R.sup.1 and R.sup.2 each independently represent a lower alkyl 
group, R.sup.3 and R.sup.4 each independently represent a hydrogen atom; a 
cyano group; a nitro group; an alkyl group; a haloalkyl group; a 
cycloalkyl group; an alkoxy group; a haloalkoxy group; an alkylthio group: 
a haloalkylthio group; an alkylsulfonyl group; an alkylsulfinyl group; an 
alkenylthio group; an alkynylthio group; an alkoxyalkyl group; an 
alkylthioalkyl group; a cycloalkylthio group; a lower 
alkoxycarbonylalkylthioalkyl group; phenyl group having 1 to 5 
substituents which are independently selected from the class consisting of 
hydrogen atoms, halogen atoms, cyano groups, nitro groups, lower alkyl 
groups, lower haloalkyl groups, lower alkoxy groups, lower haloalkoxy 
groups, lower alkylthio groups, lower haloalkylthio groups, amino groups 
having a substituent or substituents which are independently selected from 
hydrogen atoms, formyl groups, lower alkyl groups and lower alkylcarbonyl 
groups, lower alkoxycarbonyl groups, mono- or di-lower alkylaminocarbonyl 
groups, mono- or di-lower alkylaminocarbonyloxy groups, methylenedioxy 
groups, phenyl groups having 1 to 5 substituents which are independently 
selected from hydrogen atoms, halogen atoms, lower alkyl groups and lower 
haloalkyl groups, phenoxy groups having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, cyano groups, 
nitro groups, lower alkyl groups and lower haloalkyl groups, morpholino 
group which may have a substituent or substituents which are independently 
selected from lower alkyl groups, pyrimidyloxy groups which may have a 
substituent or substituents which are independently selected from lower 
alkyl groups, and morpholinocarbonyl groups which may have a substituent 
or substituents which are independently selected from lower alkyl groups; 
a phenoxyalkyl group having 1 to 5 substituents which are independently 
selected from hydrogen atoms, halogen atoms, lower alkyl groups and lower 
haloalkyl groups; a phenylthio group having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, lower alkyl 
groups and lower haloalkyl groups; a phenylalkylthio group having 1 to 5 
substituents which are independently selected from hydrogen atoms, halogen 
atoms, lower alkyl groups and lower haloalkyl groups; a phenylsulfonyl 
group having 1 to 5 substituents which are independently selected from 
hydrogen atoms, halogen atoms, lower alkyl groups and lower haloalkyl 
groups; a phenylthioalkyl group having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, lower alkyl 
groups and lower haloalkyl groups; a phenylalkylthioalkyl group having 1 
to 5 substituents which are independently selected from hydrogen atoms, 
halogen atoms, lower alkyl groups and lower haloalkyl groups; an 
aminoalkyl group having a substituent or substituents which are 
independently selected from hydrogen atoms, lower alkyl groups, lower 
haloalkyl groups, phenyl groups and benzyl groups; a furfurylthio group; a 
furfurylthioalkyl group; a morpholinoalkyl group which may have a 
substituent or substituents which are independently selected from lower 
alkyl groups; a --CO--R.sup.5 group (in which R.sup.5 represents a lower 
alkyl group; a lower haloalkyl group; a lower alkoxy group; a lower 
haloalkoxy group; a lower alkylthio group; a lower haloalkylthio group; an 
amino group having a substituent or substituents which are independently 
selected from hydrogen atoms, lower alkyl groups, lower haloalkyl groups 
and phenyl groups; a phenyl group having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, cyano groups, 
nitro groups, lower alkyl groups, lower haloalkyl groups, lower alkoxy 
groups, lower haloalkoxy groups, lower alkylthio groups, lower 
haloalkylthio groups, lower alkylsulfinyl groups, lower haloalkylsulfinyl 
groups, lower alkylsulfonyl groups, lower haloalkylsulfonyl groups, lower 
alkoxyalkyl groups, amino groups having a substituent or substituents 
which are independently selected from hydrogen atoms, lower alkyl groups, 
lower alkylcarbonyl groups, lower haloalkylcarbonyl groups, lower 
alkylsulfonyl groups, lower haloalkylsulfonyl groups, lower alkoxycarbonyl 
groups and lower haloalkoxycarbonyl groups, phenyl groups having 1 to 5 
substituents which are independently selected from hydrogen atoms, halogen 
atoms, lower alkyl groups and lower haloalkyl groups, phenoxy groups 
having 1 to 5 substituents which are independently selected from hydrogen 
atoms, halogen atoms, cyano groups, nitro groups, lower alkyl groups and 
lower haloalkyl groups, benzyl groups having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, lower alkyl 
groups and lower haloalkyl groups, benzyloxy groups having 1 to 5 
substituents which are independently selected from hydrogen atoms, halogen 
atoms, lower alkyl groups and lower haloalkyl groups, pyridyloxy groups 
having 1 to 4 substituents which are independently selected from hydrogen 
atoms, halogen atoms, lower alkyl groups and lower haloalkyl groups, 
methylenedioxy groups, and alkylene groups having 3 to 4 carbon atoms 
being attached to an adjacent carbon atoms; a benzyloxy group having 1 to 
5 substituents which are independently selected from hydrogen atoms, 
halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy 
groups, lower haloalkoxy groups, lower alkylthio groups and lower 
haloalkylthio groups; a naphthyl group; or a five- or six-membered hetero 
ring having 1 to 3 hetero atoms which are independently selected from 
oxygen atoms, sulfur atoms and nitrogen atoms and having, on the ring, a 
substituent or substituents selected from lower alkyl groups, lower 
haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups); an 
amino group having a substituent or substituents which are independently 
selected from hydrogen atoms, lower alkyl groups, lower haloalkyl groups, 
lower alkenyl groups, lower alkynyl groups, lower alkoxyalkyl groups, 
lower dialkoxyalkyl groups, mono- or di-lower substituents which are 
independently selected from hydrogen atoms, halogen atoms, lower alkyl 
groups and lower haloalkyl groups, pyridylalkyl groups and morpholinoalkyl 
groups; a phenylalkyl group having 1 to 5 substituents which are 
independently selected from hydrogen atoms, halogen atoms, lower alkyl 
groups, lower haloalkyl groups, lower alkoxy groups, lower haloalkoxy 
groups, lower alkylthio groups and lower haloalkylthio groups; a 
phenylalkenyl group having 1 to 5 substituents which are independently 
selected from hydrogen atoms, halogen atoms, lower alkyl groups and lower 
haloalkyl groups; a naphthyl group; a lower dialkylphosphonyl group; or a 
5 to 7 membered hetero ring having 1 to 3 hetero atoms which are 
independently selected from oxygen atoms, sulfur atoms and nitrogen atoms 
and having a substituent or substituents which are independently selected 
from hydrogen atoms, halogen atoms, cyano groups, nitro groups, lower 
alkyl groups, lower alkoxy groups, lower haloalkoxy groups, lower 
alkylthio groups, lower haloalkylthio groups, lower alkoxycarbonyl groups, 
phenyl groups having 1 to 5 substituents which are independently selected 
from hydrogen atoms and halogen atoms, benzyl groups, pyridyl groups, 
pyrimidyl groups and dioxolane groups, or a hetero ring thereof which is 
fused with benzene or cycloalkane or R.sup.3 and R.sup.4 together 
represent an alkylene or alkenylene group which may be interrupted with 1 
to 3 atoms or groups selected from oxygen atoms, sulfur atoms, nitrogen 
atoms, carbonyl groups or nitrogen atoms having a substituent of a lower 
alkyl group or a phenyl group, and said group may have, on the alkylene or 
alkenylene chain, a substituent or substituents which are independently 
selected from lower alkyl groups, lower haloalkyl groups, lower alkoxy 
groups and lower haloalkoxy groups, and may be fused with a benzene ring 
to form a fused ring. 
Preferred substituents on the N-(substituted benzyloxy)imine derivative of 
the general formula (I) are as follows. A methyl group is preferred as 
R.sup.1 and R.sup.2. Examples of R.sup.3 and R.sup.4 are preferably lower 
alkyl groups such as methyl and ethyl; lower alkoxy groups such as 
methoxy, ethoxy and propoxy; lower alkylthio groups such as methylthio, 
ethylthio and propylthio; lower alkoxyalkyl groups such as methoxymethyl, 
methoxyethyl and ethoxyethyl; phenyl groups having a substituent or 
substituents which are independently selected from halogen atoms such as 
chlorine, bromine and fluorine, lower alkyl groups such as methyl, ethyl 
and propyl, and lower haloalkyl groups such as difluoromethyl, 
trifluoromethyl and tetrafluoroethyl; phenylcarbonyl groups having, on the 
phenyl ring, a substituent or substituents which are independently 
selected from halogen atoms such as chlorine, bromine and fluorine, lower 
alkyl groups such as methyl, ethyl and propyl, lower haloalkyl groups such 
as difluoromethyl, trifluoromethyl and tetrafluoroethyl, and lower 
haloalkoxy groups such as difluoromethoxy, trifluoromethoxy and 
tetrafluoroethoxy; and morpholine having a substituent of a lower alkyl 
group such as methyl or ethyl. 
As an illustrative example of the preferred N-(substituted benzyloxy)imine 
derivative the following compounds can be given. Those whose R.sup.1 and 
R.sup.2 are independently lower alkyl groups, and one of R.sup.3 and 
R.sup.4 is a lower alkyl group, a lower haloalkyl group or a lower 
alkoxyalkyl group and the other is a 5 to 7-membered hetero ring having 1 
to 3 hetero atoms which are independently selected from oxygen atoms, 
sulfur atoms and nitrogen atom and having a 1 to 3 substituents which are 
independently selected from a hydrogen atom, a halogen atom, a cyano 
group, a nitro group, a lower alkyl group, a lower alkoxy group, a lower 
haloalkoxy group, a lower alkylthio group, a lower haloalkylthio group, a 
lower alkoxycarbonyl group, a phenyl group which may have 1 to 5 
substituents selected independently from halogen atoms, benzyl groups, 
pyridyl groups, pyrimidyl groups and dioxolane groups, or a hetero ring 
thereof which is fused with benzene or cycloalkane. 
As a more preferred compound having a hetero ring the followings can be 
given: Those whose hetero ring or said hetero ring thereof which is fused 
with benzene or cycloalkane is a pyrrolidine, piperidine, morpholine, 
thiomorpholine, piperazine, hexamethyleneimine, tetrahydroquinoline, 
tetrahydroisoquinoline, 2,3-dihydro-1,4-benzoxazine and the nitrogen atom 
in said hetero rings always forms the bond as a substituent of either 
R.sup.3 or R.sup.4. As a most preferred compound amongs N-(substituted 
benzyloxy)imine derivatives can be illustrated those having as R.sup.3 or 
R.sup.4 a morphino group which may be substituted with a lower alkyl group 
and the other is a lower alkyl group, a lower haloalkyl group, a lower 
alkoxyalkyl group, a phenyl group or a benzyl group. 
Further preferred compounds are N-(substituted benzyloxy)imine derivatives 
having as the rest of either R.sup.3 or R.sup.4 a lower alkyl group or a 
lower haloalkyl group. 
In this invention, the term "lower" defining substituents such as lower 
alkyl usually means that the substituent has 1 to 6 carbon atoms. For 
example, it should be understood that a "lower 
alkoxycarbonylalkylthioalkyl group" means an alkoxycarbonylalkylthioalkyl 
group having 4 to 19 carbon atoms (including carbon of the carbonyl 
group). 
This invention, however, shall not be limited to the above-specified 
substituents. 
The N-(substituted benzyloxy)imine derivative of this invention is present 
as an isomer having an E-form or Z-form with regard to the carbon-nitrogen 
double bonds and carbon-carbon double bonds, and these isomers and the 
mixture of them are included in the scope of this invention. 
When a nitrogen atom is present in R.sup.3 or R.sup.4, the N-(substituted 
benzyloxy)imine derivative of this invention can be isolated as a 
quaternary salt thereof, e.g. as a salt of tosylate, etc. 
The N-(substituted benzyloxy)imine derivative of the general formula (I) 
can be produced according to the following reaction scheme. 
##STR4## 
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined above, and X 
is halogen. 
That is, the N-(substituted benzyloxy)imine derivative of the general 
formula can be produced by reacting a compound of the general formula (II) 
with a compound of the general formula (III) in the presence of a base or 
a silver compound and in the presence of an inert solvent. 
Any inert solvent that does not prevent the present reaction can be used in 
this invention. Examples of such a solvent are alcohols such as 
isopropanol, tertbutanol and diethylene glycol; ketones such as acetone, 
methyl ethyl ketone and cyclohexanone, ethers such as diethyl ether, 
diisopropyl ether, tetrahydrofuran, dioxane, monoglyme, diglyme; 
halogenated hydrocarbons such as a dichloroethane, chloroform, carbon 
tetrachloride and tetrachloroethane; aromatic hydrocarbons such as 
benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as 
acetonitrile; dimethylformamide; dimethylsulfoxide; water and a mixed 
solvent of these. 
When a two-phase reaction is carried out in the mixed solvent, a phase 
transfer catalyst such as triethylbenzylammonium chloride, 
trioctylmethylammonium chloride or the like can be used. 
Inorganic bases and organic bases are usable as a base. Examples of the 
inorganic bases are carbonates of alkali metals or alkaline earth metals 
such as sodium carbonate, potassium carbonate, calcium carbonate and 
sodium hydrogencarbonate; hydroxides of alkali metals or alkaline earth 
metals such as sodium hydroxide, potassium hydroxide and calcium 
hydroxide; and hydrides of alkali metals such as lithium hydride and 
sodium hydride. Examples of the organic bases are alkoxides of alkali 
metal atoms such as sodium methoxide and potassium tertbutoxide, 
diethylamine, triethylamine, pyridine, and benzyltrimethylammonium 
hydroxide. 
As a silver compound, silver oxide and the like can be used. 
The reaction temperature is suitably between -70.degree. C. and the boiling 
point of the solvent, and it is preferably between -40.degree. C. and 
30.degree. C. The reaction time varies depending upon the reaction 
temperature and the reaction scale. It is, in general, from 30 minutes to 
12 hours. 
The present reaction is an equimolar reaction, and a compound of the 
general formula (II) and a compound of the general formula (III) can be 
therefore used in equimolar amounts. However, one of these compounds may 
be used in an excess amount. 
The base can be used in an equimolar amount based on a compound of the 
general formula (III). However, it may be used in an excess amount. 
After completion of the reaction, the intended product is isolated by an 
ordinary method and, optionally, purified, e.g. by column chromatography 
or a recrystalization method. 
The compound of the general formula (II) can be produced according to the 
process disclosed in JP, A 61-280452. The compound of the general formula 
(III), the scope of which includes some novel compounds, can be produced 
according to a process for the production of known compounds [e.g. Org. 
Syn. Coll. Vol. 2, 313 (1943), ditto, 363 (1943), and J. Org. Chem., 1980, 
45. 4198]. 
Table 1 shows typical examples of the N-(substituted benzyloxy)imine 
derivative of the general formula (I). This invention, however, shall not 
be limited to these examples. 
TABLE 1 
__________________________________________________________________________ 
##STR5## (I) 
Compound No. 
R.sup.1 
R.sup.2 
##STR6## index)or refractive (melting 
pointpropertiesPhysical 
shiftChemical*.sup.1 H-NMR 
__________________________________________________________________________ 
1 CH.sub.3 
CH.sub.3 
##STR7## nD 1.5905 (18.9.degree. C.) 
7.55 
2 CH.sub.3 
CH.sub.3 
##STR8## nD 1.5895 (23.3.degree. C.) 
7.52 
3 CH.sub.3 
CH.sub.3 
##STR9## nD 1.5905 (23.4.degree. C.) 
7.53 
4 CH.sub.3 
CH.sub.3 
##STR10## nD 1.5685 (23.5.degree. C.) 
7.53 
5 CH.sub.3 
CH.sub.3 
##STR11## mp. 99.8- 102.3.degree. C. 
7.56 
6 CH.sub.3 
CH.sub.3 
##STR12## nD 1.5845 (23.9.degree. C.) 
7.56 
7 CH.sub.3 
CH.sub.3 
##STR13## mp. 137.7- 141.2.degree. C. 
7.50 
8 CH.sub.3 
CH.sub.3 
##STR14## mp. 157.8- 160.6.degree. C. 
7.56 
9 CH.sub.3 
CH.sub.3 
##STR15## mp. 106.9- 111.8.degree. C. 
7.56 
10 CH.sub.3 
CH.sub.3 
##STR16## mp. 95.4- 96.6.degree. C. 
7.54 
11 CH.sub.3 
CH.sub.3 
##STR17## nD 1.5919 (25.3.degree. C.) 
7.61 
12 CH.sub.3 
CH.sub.3 
##STR18## mp. 108.7- (dec.) 
7.57 
13 CH.sub.3 
CH.sub.3 
##STR19## nD 1.5856 (21.0.degree. C.) 
7.51 
14 CH.sub.3 
CH.sub.3 
##STR20## mp. 1.5726 (21.2.degree. C.) 
7.54 
15 CH.sub.3 
CH.sub.3 
##STR21## nD 1.5827 (21.3.degree. C.) 
7.53 
16 CH.sub.3 
CH.sub.3 
##STR22## nD 1.5978 (20.8.degree. C.) 
7.54 
17 CH.sub.3 
CH.sub.3 
##STR23## nD 1.5890 (20.1.degree. C.) 
7.57 
18 CH.sub.3 
CH.sub.3 
##STR24## mp. 111.6- 113.2.degree. C. 
7.57 
19 CH.sub.3 
CH.sub.3 
##STR25## nD 1.5778 (22.7.degree. C.) 
7.40 
20 CH.sub.3 
CH.sub.3 
##STR26## nD 1.6016 (19.9.degree. C.) 
7.53 
21 CH.sub.3 
CH.sub.3 
##STR27## nD 1.5869 (19.2.degree. C.) 
7.57 
22 CH.sub.3 
CH.sub.3 
##STR28## nD 1.5613 (23.9.degree. C.) 
7.49 
23 CH.sub.3 
CH.sub.3 
##STR29## nD 1.5815 (24.0.degree. C.) 
7.52 
24 CH.sub.3 
CH.sub.3 
##STR30## mp. 106.1- 112.5.degree. C. 
7.48 
25 CH.sub.3 
CH.sub.3 
##STR31## nD 1.5717 (20.4.degree. C.) 
7.51 
26 CH.sub.3 
CH.sub.3 
##STR32## nD 1.5765 (20.2.degree. C.) 
7.55 
27 CH.sub.3 
CH.sub.3 
##STR33## nD 1.5757 (20.5.degree. C.) 
7.52 
28 CH.sub.3 
CH.sub.3 
##STR34## nD 1.5690 (23.3.degree. C.) 
7.53 
29 CH.sub.3 
CH.sub.3 
##STR35## nD 1.5780 (25.0.degree. C.) 
7.53 
30 CH.sub.3 
CH.sub.3 
##STR36## nD 1.5880 (24.9.degree. C.) 
7.53 
31 CH.sub.3 
CH.sub.3 
##STR37## nD 1.5788 (25.3.degree. C.) 
7.55 
32 CH.sub.3 
CH.sub.3 
##STR38## nD 1.5735 (21.8.degree. C.) 
7.53 
33 CH.sub.3 
CH.sub.3 
##STR39## nD 1.5690 (21.8.degree. C.) 
7.56 
34 CH.sub.3 
CH.sub.3 
##STR40## nD 1.5670 (24.0.degree. C.) 
7.53 
35 CH.sub.3 
CH.sub.3 
##STR41## nD 1.5745 (24.0.degree. C.) 
7.53 
36 CH.sub.3 
CH.sub.3 
##STR42## nD 1.5770 (22.1.degree. C.) 
7.53 
37 CH.sub.3 
CH.sub.3 
##STR43## mp. 111- 130.degree. C. 
7.47 
38 CH.sub.3 
CH.sub.3 
##STR44## mp. 118.1- 122.6.degree. C. 
7.56 
39 CH.sub.3 
CH.sub.3 
##STR45## nD. 1.5767 (22.7.degree. C.) 
7.50 
40 CH.sub.3 
CH.sub.3 
##STR46## nD. 1.5949 (20.8.degree. C.) 
7.51 
41 CH.sub.3 
CH.sub.3 
##STR47## nD. 1.5697 (22.2.degree. C.) 
7.54 
42 CH.sub.3 
CH.sub.3 
##STR48## nD. 1.5778 (22.7.degree. C.) 
7.57 
43 CH.sub.3 
CH.sub.3 
##STR49## nD. 1.5877 (23.0.degree. C.) 
7.58 
44 CH.sub.3 
CH.sub.3 
##STR50## nD. 1.5716 (20.2.degree. C.) 
7.55 
45 CH.sub.3 
CH.sub.3 
##STR51## mp. 102.1- 105.3.degree. C. 
7.63 
46 CH.sub.3 
CH.sub.3 
##STR52## nD. 1.6091 (23.8.degree. C.) 
7.52 
47 CH.sub.3 
CH.sub.3 
##STR53## nD. 1.5815 (25.5.degree. C.) 
7.63 
48 CH.sub.3 
CH.sub.3 
##STR54## nD. 1.5748 (25.5.degree. C.) 
7.64 
49 CH.sub.3 
CH.sub.3 
##STR55## nD. 1.5719 (25.2.degree. C.) 
7.53 
50 CH.sub.3 
CH.sub.3 
##STR56## nD. 1.5763 (25.4.degree. C.) 
7.51 
51 CH.sub.3 
CH.sub.3 
##STR57## nD. 1.5642 (25.5.degree. C.) 
7.53 
52 CH.sub.3 
CH.sub.3 
##STR58## mp. 82.7- 84.6.degree. C. 
7.63 
53 CH.sub.3 
CH.sub.3 
##STR59## mp. 91.9- 94.8.degree. C. 
7.65 
54 CH.sub.3 
CH.sub.3 
##STR60## nD 1.5238 (25.2.degree. C.) 
7.65 
55 CH.sub.3 
CH.sub.3 
##STR61## mp. 111.5- 113.0.degree. C. Rf. 
7.61 
56 CH.sub.3 
CH.sub.3 
##STR62## nD. 1.5895 (22.8.degree. C.) Rf. 
7.61 
57 CH.sub.3 
CH.sub.3 
##STR63## nD. 1.5698 (22.9.degree. C.) Rf. 
7.59 
58 CH.sub.3 
CH.sub.3 
##STR64## mp. 77.3- 81.3.degree. C. Rf. 
7.53 
59 CH.sub.3 
CH.sub.3 
##STR65## nD. 1.5924 (18.6.degree. C.) 
7.59 
60 CH.sub.3 
CH.sub.3 
##STR66## nD. 1.5846 (18.4.degree. C.) 
7.63 
61 CH.sub.3 
CH.sub.3 
##STR67## nD. 1.5748 (20.1.degree. C.) 
7.55 
62 CH.sub.3 
CH.sub.3 
##STR68## nD. 1.5868 (20.2.degree. C.) 
7.54 
63 CH.sub.3 
CH.sub.3 
##STR69## Paste 7.57 
64 CH.sub.3 
CH.sub.3 
##STR70## nD. 1.6140 (20.0.degree. C.) 
7.55 
65 CH.sub.3 
CH.sub.3 
##STR71## nD. 1.6162 (20.0.degree. C.) 
7.53 
66 CH.sub.3 
CH.sub.3 
##STR72## nD. 1.5996 (20.1.degree. C.) 
7.55 
67 CH.sub.3 
CH.sub.3 
##STR73## mp. 99.8- 105.3.degree. C. 
7.50 
68 CH.sub.3 
CH.sub.3 
##STR74## mp. 114.3- 117.5.degree. C. 
7.57 
69 CH.sub.3 
CH.sub.3 
##STR75## nD 1.6073 (23.1.degree. C.) 
7.52 
70 CH.sub.3 
CH.sub.3 
##STR76## nD 1.5917 (23.0.degree. C.) 
7.54 
71 CH.sub.3 
CH.sub.3 
##STR77## nD 1.5730 (20.1.degree. C.) 
7.53 
72 CH.sub.3 
CH.sub.3 
##STR78## nD 1.5561 (26.1.degree. C.) 
7.53 
73 CH.sub.3 
CH.sub.3 
##STR79## mp. 105.2- 113.5.degree. C. 
7.54 
74 CH.sub.3 
CH.sub.3 
##STR80## nD 1.5960 (21.2.degree. C.) 
7.58 
75 CH.sub.3 
CH.sub.3 
##STR81## nD 1.5912 (23.8.degree. C.) 
7.49 
76 CH.sub.3 
CH.sub.3 
##STR82## nD 1.6158 (25.9.degree. C.) 
7.58 
77 CH.sub.3 
CH.sub.3 
##STR83## mp. 139.1- 143.3.degree. C. 
7.50 
78 CH.sub.3 
CH.sub.3 
##STR84## nD 1.5899 (24.4.degree. C.) 
7.55 
79 CH.sub.3 
CH.sub.3 
##STR85## nD 1.5973 (25.0.degree. C.) 
7.58 
80 CH.sub.3 
CH.sub.3 
##STR86## mp. 108- 110.degree. C. 
7.58 
81 CH.sub.3 
CH.sub.3 
##STR87## mp. 90- 92.degree. C. 
7.58 
82 CH.sub.3 
CH.sub.3 
##STR88## nD 1.5920 (25.0.degree. C.) 
7.58 
83 CH.sub.3 
CH.sub.3 
##STR89## nD 1.5752 (24.9.degree. C.) 
7.58 
84 CH.sub.3 
CH.sub.3 
##STR90## nD 1.5572 (23.3.degree. C.) 
7.60 
85 CH.sub.3 
CH.sub.3 
##STR91## nD 1.5786 (23.8.degree. C.) 
7.59 
86 CH.sub.3 
CH.sub.3 
##STR92## nD 1.5755 (23.5.degree. C.) 
7.57 
87 CH.sub.3 
CH.sub.3 
##STR93## Paste 7.58 
88 CH.sub.3 
CH.sub.3 
##STR94## Paste 7.53 
89 CH.sub.3 
CH.sub.3 
##STR95## Paste 7.50 
90 CH.sub.3 
CH.sub.3 
##STR96## Paste 7.52 
91 CH.sub.3 
CH.sub.3 
##STR97## Paste 7.53 
92 CH.sub.3 
CH.sub.3 
##STR98## Paste 7.50 
93 CH.sub.3 
CH.sub.3 
##STR99## nD 1.5770 (18.9.degree. C.) 
7.58 
94 CH.sub.3 
CH.sub.3 
##STR100## nD 1.5665 (18.0.degree. C.) 
7.53 
95 CH.sub.3 
CH.sub.3 
##STR101## Paste 7.47 
96 CH.sub.3 
CH.sub.3 
##STR102## nD 1.5917 (18.6.degree. C.) 
7.53 
97 CH.sub.3 
CH.sub.3 
##STR103## Paste 7.55 
98 CH.sub.3 
CH.sub.3 
##STR104## nD 1.5990 (22.1.degree. C.) 
7.53 
99 CH.sub.3 
CH.sub.3 
##STR105## mp. 131.4- 134.8.degree. C. 
7.65 
100 CH.sub.3 
CH.sub.3 
##STR106## mp. 131.4- 134.8.degree. C. 
7.65 
101 CH.sub.3 
CH.sub.3 
##STR107## mp. 117.6- 121.5.degree. C. 
7.67 
102 CH.sub.3 
CH.sub.3 
##STR108## mp. 108.9- 114.7.degree. C. 
7.53 
103 CH.sub.3 
CH.sub.3 
##STR109## mp. 141.9- 145.6.degree. C. 
7.53 
104 CH.sub.3 
CH.sub.3 
##STR110## mp. 149.0- 153.0.degree. C. 
7.53 
105 CH.sub.3 
CH.sub.3 
##STR111## mp. 130.2- 153.0.degree. C. 
7.53 
106 CH.sub.3 
CH.sub.3 
##STR112## mp. 84.6- 90.0.degree. C. 
7.50 
107 CH.sub.3 
CH.sub.3 
##STR113## nD 1.5401 (24.5.degree. C.) 
7.50 
108 CH.sub.3 
CH.sub.3 
##STR114## nD 1.5351 (25.6.degree. C.) 
7.53 
109 CH.sub.3 
CH.sub.3 
##STR115## nD 1.5570 (23.5.degree. C.) 
7.53 
110 CH.sub.3 
CH.sub.3 
##STR116## nD 1.5586 (22.5.degree. C.) 
7.50 
111 CH.sub.3 
CH.sub.3 
##STR117## nD 1.5192 (23.5.degree. C.) 
7.49 
112 CH.sub.3 
CH.sub.3 
##STR118## nD 1.5304 (26.6.degree. C.) 
7.50 
113 CH.sub.3 
CH.sub.3 
##STR119## nD 1.5218 (22.7.degree. C.) 
7.52 
114 CH.sub.3 
CH.sub.3 
##STR120## nD 1.5179 (22.2.degree. C.) 
7.50 
115 CH.sub.3 
CH.sub.3 
##STR121## nD 1.5014 (26.7.degree. C.) 
7.55 
116 CH.sub.3 
CH.sub.3 
##STR122## nD 1.5100 (22.8.degree. C.) 
7.48 
117 CH.sub.3 
CH.sub.3 
##STR123## nD 1.5068 (22.9.degree. C.) 
7.48 
118 CH.sub.3 
CH.sub.3 
##STR124## nD 1.5090 (20.8.degree. C.) 
7.49 
119 CH.sub.3 
CH.sub.3 
##STR125## nD 1.6110 (20.3.degree. C.) 
7.52 
120 CH.sub.3 
CH.sub.3 
##STR126## nD 1.5587 (21.8.degree. C.) 
7.50 
121 CH.sub.3 
CH.sub.3 
##STR127## nD 1.5788 (23.3.degree. C.) 
7.54 
122 CH.sub.3 
CH.sub.3 
##STR128## nD 1.5806 (23.4.degree. C.) 
7.48 
123 CH.sub.3 
CH.sub.3 
##STR129## nD 1.5592 (19.8.degree. C.) 
7.49 
124 CH.sub.3 
CH.sub.3 
##STR130## nD 1.5169 (18.8.degree. C.) 
7.46 
125 CH.sub.3 
CH.sub.3 
##STR131## nD 1.5217 (18.7.degree. C.) 
7.44 
126 CH.sub.3 
CH.sub.3 
##STR132## mp. 51.1- 54.6.degree. C. 
7.52 
127 CH.sub.3 
CH.sub.3 
##STR133## nD 1.5324 (19.4.degree. C.) (cis-form) 
8 7.52 
128 CH.sub.3 
CH.sub.3 
##STR134## nD 1.5575 (17.5.degree. C.) 
7.50 
129 CH.sub.3 
CH.sub.3 
##STR135## nD 1.5450 (25.4.degree. C.) 
7.50 
130 CH.sub.3 
CH.sub.3 
##STR136## Yellow paste 
7.53 
131 CH.sub.3 
CH.sub.3 
##STR137## nD 1.5465 (25.0.degree. C.) 
7.50 
132 CH.sub.3 
CH.sub.3 
##STR138## nD 1.5450 (21.8.degree. C.) 
7.53 
133 CH.sub.3 
CH.sub.3 
##STR139## nD 1.5875 (25.8.degree. C.) 
7.53 
134 CH.sub.3 
CH.sub. 3 
##STR140## nD 1.5810 (21.7.degree. C.) 
7.56 
135 CH.sub.3 
CH.sub.3 
##STR141## nD 1.5580 (21.4.degree. C.) 
7.56 
136 CH.sub.3 
CH.sub.3 
##STR142## nD 1.5350 (28.5.degree. C.) 
7.50 
137 CH.sub.3 
CH.sub.3 
##STR143## nD 1.5195 (18.6.degree. C.) 
7.53 
138 CH.sub.3 
CH.sub.3 
##STR144## Brown paste 
7.56 
139 CH.sub.3 
CH.sub.3 
##STR145## nD 1.5400 (25.8.degree. C.) 
7.56 
140 CH.sub.3 
CH.sub.3 
##STR146## nD 1.5551 (21.2.degree. C.) 
7.50 
141 CH.sub.3 
CH.sub.3 
##STR147## nD 1.5775 (21.3.degree. C.) 
7.53 
142 CH.sub.3 
CH.sub.3 
##STR148## mp. 122.5- 127.1.degree. C. 
7.56 
143 CH.sub.3 
CH.sub.3 
##STR149## Yellow paste 
7.56 
144 CH.sub.3 
CH.sub.3 
##STR150## Colorless paste 
7.53 
145 CH.sub.3 
CH.sub.3 
##STR151## mp. 122.5- 126.4.degree. C. 
7.53 
146 CH.sub.3 
CH.sub.3 
##STR152## mp. 116.8- 121.3.degree. 
7.53 
147 CH.sub.3 
CH.sub.3 
##STR153## Colorless paste 
7.53 
148 CH.sub.3 
CH.sub.3 
##STR154## Green paste 
7.53 
149 CH.sub.3 
CH.sub.3 
##STR155## m.p. 55.6- 72.1.degree. C. 
7.50 
##STR156## 
In compounds described in Table 1, a combination, e.g. of compounds 55 and 
56, compounds 57 and 58, or the like is a combination of an isomer having 
a Z form with an isomer having a E form. 
Further, in Table 1, the terms of "high" and "low" Rf mean a high Rf value 
and a low Rf value in silica gel thin layer chromatography (n-hexane-ethyl 
acetate). 
The following Examples illustrate typical embodiments of the N-(substituted 
benzyloxy)imine derivative of the general formula (I), to which, however, 
this invention shall not be limited. 
EXAMPLE 1 
Methyl 2-(2-benzylideneaminooxymethylphenyl)-3-methoxyacrylate (Compound 
No. 1) 
##STR157## 
0.57 Gram of methyl 2-(2-bromomethylphenyl)-3-methoxyacrylate and 0.36 g of 
benzaldoxime were dissolved in 10 ml of dimethyl sulfoxide, and 0.19 g of 
potassium hydroxide powder was added. The resultant mixture was stirred at 
room temperature for 6 hours. 
After standing overnight, the mixture was poured into ice water, to wash 
with brine, and extracted twice with ethyl acetate. The extracts were 
dried over magnesium sulfate, filtered and concentrated under reduced 
pressure, and the resultant residue was purified by silica gel dry column 
chromatography to give 0.2 g of the intended product. 
Yield: 31%, Properties: nD 1.5905 (18.9.degree. C.) 
EXAMPLE 2 
Methyl 2-{2-(3-oxo-2-butylideneaminooxymethyl)-phenyl}-3-methoxyacrylate 
(Compound No. 52) 
##STR158## 
0.86 Gram of methyl 2-(2-bromomethylphenyl)-3-methoxyacrylate and 0.33 g of 
diacetyl monooxime were dissolved in 20 ml of dimethylformamide, and the 
mixture was cooled to 5.degree. C. 0.22 Gram of potassium hydroxide powder 
was added, and the mixture was stirred for 10 minutes and further stirred 
for 1 hour at room temperature to carry out the reaction. After completion 
of the reaction, the reaction mixture was poured into ice water, and 
extracted with ethyl acetate. The extracts were washed with a 5% sodium 
hydroxide aqueous solution and salt water, and dried over magnesium 
sulfate. The extracts were filtered and concentrated under reduced 
pressure, and the resultant residue was purified by silca gel dry column 
chromatography to give 0.81 g of the intended product. 
Yield: 89%, Properties: mp. 82.7.degree.-84.6.degree. C. 
EXAMPLE 3 
Methyl 
2-{2-(.alpha.-methylthiobenzylideneaminooxymethyl)phenyl}-3-methoxyacrylat 
e (Compound No. 59) 
##STR159## 
0.33 Gram of potassium hydroxide powder was added to 10 ml of a dimethyl 
sulfoxide solution containing 0.85 g of benzhydroxamyl methyl thioether, 
and the mixture was stirred for 10 minutes. Then, 1.45 g of methyl 
2-(2-bromomethylphenyl)-3-methoxyacrylate was added, and the resultant 
mixture was allowed to react with stirring for 4 hours. 
After completion of the reaction, the reaction mixture was poured into ice 
water and extracted with ether. The extracts were washed with water and 
brine, and dried over sodium sulfate. The extract liquid was filtered and 
then concentrated under reduced pressure, and the resultant residue was 
purified by silica gel dry column chromatography to give 1.50 g of the 
intended product. 
Yield: 81%, Properties: nD 1.5924 (18.6.degree. C.) . 
Methyl 
2-{2-(.alpha.-morpholinobenzylideneaminooxymethyl)phenyl}-3-methoxyacrylat 
e (Compound No. 88) 
##STR160## 
0.44 Gram of .alpha.-morpholinobenzaldoxime was dissolved in 5 ml of 
dimethyl sulfoxide, and 0.14 g of potassium hydroxide powder was added. 
The mixture was stirred for 30 minutes. Then, 0.55 g of methyl 
2-(2-bromomethylphenyl)-3-methoxyacrylate was added, and the mixture was 
allowed to react with stirring for 2 hours. 
After the completion of the reaction, 10 ml of ice water was added to the 
reaction mixture, and the resultant was extracted with ethyl acetate. The 
extracts were washed with water, and dried over sodium sulfate. The 
extracts were filtered and concentrated under reduced pressure, and the 
resultant residue was purified by silica gel dry column chromatography to 
give 0.29 g of the intended product. 
Yield: 33%, Properties: paste . 
EXAMPLE 5 
Methyl 
2-{2-(1,3-dithiolan-2-ylideneaminooxymethyl)phenyl}-3-methoxyacrylate (Com 
pound No. 96) 
##STR161## 
0.44 Gram of 2-hydroxyimino-1,3-dithiolane was dissolved in 5 ml of 
dimethyl sulfoxide, and 0.18 g of potassium hydroxide powder was added. 
The resultant mixture was stirred at room temperature for 30 minutes. 
Then, 0.86 g of methyl 2-(2-bromomethylphenyl)-3-methoxyacrylate was 
added, and the resultant mixture was allowed to react with stirring for 2 
hours. 
After completion of the reaction, ice water was added to the reaction 
mixture which was extracted with ethyl acetate. The extracts were washed 
with water, and dried over magnesium sulfate. The extracts were filtered 
and concentrated under reduced pressure, and the resultant residue was 
purified by silica gel dry column chromatography to give 0.56 g of the 
intended product. 
Yield: 55%, Properties: nD 1.5917 (18.6.degree. C.). 
EXAMPLE 6 
Methyl 
2-[2-{1-(cis-2,6-dimethylmorpholino)ethylideneaminooxymethylphenyl]-3-meth 
oxyacrylate (Compound No. 357) 
##STR162## 
1.72 Gram of 1-(cis-2,6-dimethylmorpholino)acetoaldoxime was dissolved in 
30 ml of dimethylformamide, and 0.66 g of potassium hydroxide powder was 
added thereto, and the mixture was stirred for 10 minutes at 0.degree. C. 
2.85 Grams of methyl 2-(2-bromomethylphenyl)-3-methoxyacrylate was added 
thereto and the resultant mixture was further stirred for 1 hour at room 
temperature to carry out the reaction. After completion of the reaction, 
the reaction mixture was poured into ice water, and extracted with ethyl 
acetate. The extracts were washed with water, and dried over magnesium 
sulfate. The extracts were filtered and concentrated under reduced 
pressure, and the resultant residue was purified by silica gel dry column 
chromatography to give 0.4 g of the intended product. 
Yield: 10.6%, Properties: 107.degree.-109.degree. C. 
The N-(substituted benzyloxy)imino derivatives of the general formula (1) 
are useful as agricultural and horticultural fungicides, and are very 
effective in controlling various plant diseases such as rice blast 
(Pyricularia oryzae), rice sheath blight (Rhizoctonia solani), rice brown 
spot (Cochliobolus miyabeanus), powdery mildew of barley (Frysiphe 
graminis f.sp. hordei) and other plants, rust of various plants, and the 
diseases caused by Oomycetes fungi such as tomato late blight 
(Phytophthora infestans) and cucumber downy mildw (Pseudoperonaspora 
cubensis). 
The present inventive compounds have excellent activity in controlling 
diseases of paddy field crops, upland field crops, fruit trees, 
vegetables, other crops and flowering plants by the application to crop 
foliage, irrigation water or soil before or after disease appearance. 
This invention however should not be limited to the these embodiments. 
When the N-(substituted benzyloxy)imine derivative of the general formula 
(I) is used as an agricultural or horticultural fungicide, it is generally 
prepared into conveniently usable forms according to an ordinary manner 
for preparation of agrochemicals. 
That is, the N-(substituted benzyloxy)imine derivative of the general 
formula (I) and, optionally, an adjuvant are blended with a suitable inert 
carrier and prepared into a suitable preparation form such as a 
suspension, emulsifiable concentrate, soluble concentrate, wettable 
powder, granules, dust or tablet through dissolution, dispersion, 
suspension, mixing, impregnation, adsorption or sticking. 
The inert carrier in this invention may be solid or liquid. Examples of the 
solid carrier are soybean flour, cereal flour, wood flour, bark flour, saw 
dust, powdered tobacco stalks, powdered walnut shells, bran, powdered 
cellulose, extraction residues of vegetables, powdered synthetic polymers 
or resins, clays (e.g. kaolin, betonite, nd acid clay), talcs (e.g. talc 
and pyrophyllite), silica powders or flakes (e.g. diatomaceous earth, 
silica sand, mica and white carbon, i.e. synthetic, high-dispersion 
silicic acid, called finely divided hydrated silica or hydrated silicic 
acid), activated carbon, powdered sulfur, powdered pumice, calcined 
diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, 
calcium phosphate powder and other inorganic or mineral powders, chemical 
fertilizers (e.g. ammonium sulfate, ammonium nitrate, urea and ammonium 
chloride), and compost. These carriers may be used alone or in 
combination. 
The liquid carrier is that which itself has solubility or which is without 
such solubility but is capable of dispersing an active ingredient with the 
aid of an adjuvant. The following are typical examples of the liquid 
carrier and can be used alone or in combination. Water; alcohols such as 
methanol, ethanol, isopropanol, butanol and ethylene glycol; ketones such 
as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone 
and cyclohexanone; ethers such as ethyl ether, dioxane, Cellosolve, 
dipropyl ether and tetrahydrofuran; aliphatic hydrocarbons such as 
gasoline and mineral oils; aromatic hydrocarbons such as benzene, toluene, 
xylene, solvent naphtha and alkylnaphthalene; halogenated hydrocarbons 
such as dichloroethane, chloroform, carbon tetrachloride and 
chlorobenzene; esters such as ethyl acetate, diisopropyl phthalate, 
dibutyl phthalate and dioctyl phthalate; amides such as dimethylformamide 
and dimethylacetamide; nitriles such as acetonitrile; and dimethyl 
sulfoxide. 
The following are typical examples of the adjuvant, which are used 
depending upon purpose and used alone or in combination in some cases, or 
may not be used at all. 
To emulsify, disperse, dissolve and/or wet an active ingredient, a 
surfactant is used. Examples of the surfactant are polyoxyethylene alkyl 
ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene higher fatty 
acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan 
monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, 
naphthalenesulfonic acid condensation products, ligninsulfonates and 
higher alcohol sulfate esters. 
Further, to stabilize the disersion of an active ingredient, tackify it 
and/or bind it, an adjuvant may be used. Example of such an adjuvant are 
casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum 
arabic, polyvinyl alcohol, turpentine, bran oil, bentonite and 
ligninsulfonates. 
To improve the flowability of a solid product, an adjuvant may be used. 
Examples of such an adjuvant are waxes, stearates and alkyl phosphates. 
Adjuvants such as naphthalenesulfonic acid condensation products and 
polycondensates of phosphates may be used as a peptizer for dispersible 
products. 
Adjuvants, e.g. silicone oils, may be also used as a defoaming agent. 
The content of the active ingredient may be varied as required. In dusts or 
granules, the suitable content thereof is from 0.1 to 50% by weight. In 
emulsifiable concentrates, flowable wettable powders, it is from 0.1 to 
90% by weight. 
An agricultural or horticultural fungicide containing the N-(substituted 
benzyloxy)imine derivative of the general formula (I) as an active 
ingredient is used to control a variety of crop diseases in the following 
manner. That is, it is applied to a crop on which diseases is estimated to 
occur or a site where occurrnece of diseases is undesirable directly or by 
suitably diluting it with water or suspending it in water in such an 
amount that is effective to control the diseases. 
The amount of the agricultural or horticultural fungicide containing the 
N-(substituted benzyloxy)imine derivative of the general formula (I) as an 
active ingredient varies depending upon various factors such as a purpose, 
diseases to be controlled, a growth state of a plant, tendency of diseases 
occurrence, weather, environmental conditions, a preparation form, an 
application method, an application site and an application time. It is, 
however, used in an amount of 0.1 g to 1,000 g per 10 ares as an active 
ingredient depending upon a purpose. 
The agricultural or horticultural fungicide containing the N-(substituted 
benzyloxy)imine derivative of the general formula (I) as an active 
ingredient may be used as a mixture thereof with an agrochemical, 
fertilizer and/or plant nutrient which are usable at its application time, 
or just in combination with these. 
When the agricultural or horticultural fungicide containing the compound of 
this invention as an active ingredient is used to control crop diseases, 
it may be mixed with some other controller(s) to control other crop damage 
which occurs concurrently with crop diseases to be controlled by the 
present fungicide, and the mixture can be used as a multi-purpose 
controller. Examples of such other controller are as follows. 
O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate (Fenitrothion) 
O,O-dimethyl O-(3-methyl-4-methylthiophenyl)phosphorothioate (Fenthion) 
S-.alpha.-ethoxycarbonylbenzyl O,O-dimethyl phosphorodithioate 
(Phenthioate) 
O,O-diethyl O-(2-isopropyl-6-methyl-4-pyrimidinyl)phosphorothioate 
(Diazinon) 
dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate (Trichlorphon) 
O-4-cyanophenyl O-ethyl phenylphosphonothioate (Cyanophenphos) 
O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN) 
4-(methylthio)phenyl dipropylphosphate (Propaphos) 
O,O-dimethyl S-phthalimidomethyl phosphorodithioate (Phosmet) 
2,2-dichlorovinyl dimethyl phosphate (DDVP) 
O,O-dimethyl S-methylcarbamoylmethyl phosphorodithioate (Dimethoate) 
S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethyl phosphorodithiate (Malathion) 
1-naphthyl methylcarbamate (Carbaryl) 
m-tolyl methylcarbamate (Metocarb) 
2-isopropoxyphenyl methylcarbamate (propoxur) 
S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O,O-diethylphosphorodithioate 
(Mecarbam) 
3,4-xylyl methylcarbamate (Xylylcarb) 
2-sec-butylphenyl methylcarbamate (BPMC) 
2-isopropylphenyl methylcarbamate (Isoprocarb) 
2-chlorophenyl methylcarbamate (CPMC) 
3,5-xylyl methylcarbamate (XMC) 
2-(1,3-dioxolan-2-yl)phenyl methylcarbamate (Dioxacarb) 
3-tert-butylphenyl methylcarbamate (Terbam) 
4-diallylamino-3,5-xylyl methylcarbamate (Allyxycarb) 
S-methyl N-(methylcarbamoyloxy)thioacetimidate (Methomyl) 
N-(4-chloro-o-tolyl)-N,N-dimethylformamidine hydrochloride (Chlorodimeform) 
1,3-bis-(carbamoylthio)-2-dimethylaminopropane hydrochloride (Cartap) 
Diisopropyl 1,3-dithiolan-2-ylidenemalonate (Isoprothiolane) 
S-benzyl O,O-diisopropyl phosphorothioate (IBP) 
Following are typical Formulation Examples and Test Examples of this 
invention, which however shall not limit this invention. 
In Formulation Examples, "part" stands for "part by weight". 
FORMULATION EXAMPLE 1 
______________________________________ 
Compound No. 21 50 parts 
Clay-white carbon mixture mainly 
45 parts 
containing clay 
Polyoxyethylene nonylphenyl ether 
5 parts 
______________________________________ 
The above components were homogeneously mixed and pulverized to give a 
wettable powder. 
FORMULATION EXAMPLE 2 
______________________________________ 
Compound No. 44 5 parts 
Bentonite-clay mixture 
90 parts 
Calcium lignin sulfonate 
5 parts 
______________________________________ 
The above components were homogeneously mixed, and the mixture was kneaded 
together with a suitable amount of water. The mixture was granulated and 
dried to give granules. 
FORMULATION EXAMPLE 3 
______________________________________ 
Compound No. 96 50 parts 
Xylene 40 parts 
Mixture of polyoxyethylene nonyl- 
10 parts 
phenyl ether with calcium alkyl- 
benzenesulfonate 
______________________________________ 
The above components were homogeneously mixed and dissolved to give an 
emulsifiable concentrate. 
FORMULATION EXAMPLE 4 
______________________________________ 
Compound No. 201 3 parts 
Powdered clay 82 parts 
Powdered diatomaceous earth 
15 parts 
______________________________________ 
The above components were homogeneously mixed and pulverized to give a 
dust. 
FORMULATION EXAMPLE 5 
______________________________________ 
Compound No. 272 5 parts 
Polyoxyethylene (10 moles) 
1.4 parts 
nonylphenyl ether 
Polyoxyethylene styrenated phenol 
2 parts 
ether 
Propylene glycol 3 parts 
Defoaming agent 0.5 part 
Heteropolysaccharide 0.15 part 
Water 87.95 parts 
______________________________________ 
The above components were homogeneously mixed and pulverized to give a 
flowable preparation. 
TEST EXAMPLE 1 
Controlling effect on powdery mildew of barley (Erysiphe graminis f.s. 
hordei) 
Barley seedlings at 2-leaf stage were sprayed with test compound (200 ppm) 
one day after inoculation with conidia of Erysiphe graminis f.sp. hordei. 
The seedlings were held in a constant-temperature room at 25.degree. C. 
for one week and the percentage of the infected area per leaf was 
examined. Disease controlling activity was estimated in comparison with 
the untreated plot as follows. 
______________________________________ 
A: control rate 
100-95% 
B: control rate 
94-80% 
C: control rate 
79-60% 
D: control rate 
59-0% 
______________________________________ 
TABLE 2 
______________________________________ 
Compound No. Fungicidal effect 
______________________________________ 
1 A 
2 C 
3 B 
4 A 
5 C 
6 A 
7 A 
9 A 
10 A 
11 A 
12 A 
13 A 
14 A 
15 A 
16 A 
17 A 
21 A 
22 A 
23 A 
24 A 
25 A 
26 A 
27 A 
28 A 
29 A 
30 A 
31 A 
32 A 
33 A 
34 A 
35 A 
36 A 
38 A 
39 A 
40 A 
41 A 
42 A 
43 A 
44 A 
47 A 
48 A 
49 A 
50 B 
51 A 
52 A 
55 A 
56 A 
57 C 
59 A 
60 A 
61 C 
65 C 
66 A 
67 A 
68 A 
69 A 
70 A 
71 B 
72 B 
74 A 
75 A 
78 B 
79 A 
80 C 
81 A 
82 A 
83 B 
84 B 
87 A 
88 A 
89 B 
91 A 
92 A 
93 A 
94 A 
95 A 
96 A 
97 C 
98 A 
102 A 
103 B 
105 B 
106 B 
107 A 
108 A 
109 A 
110 A 
111 B 
112 B 
113 A 
114 A 
115 A 
116 A 
117 A 
118 A 
119 A 
120 A 
121 A 
122 A 
123 A 
124 A 
125 A 
126 A 
127 A 
128 B 
129 A 
130 A 
131 A 
132 A 
133 A 
134 A 
135 A 
137 A 
139 A 
141 B 
142 A 
143 A 
144 A 
145 C 
146 A 
147 A 
148 A 
149 A 
150 A 
151 A 
152 A 
153 B 
154 A 
155 A 
156 B 
157 A 
158 A 
159 A 
160 A 
161 A 
162 A 
163 A 
164 A 
165 A 
166 A 
167 A 
168 A 
169 A 
170 C 
171 A 
172 A 
173 A 
174 A 
175 C 
176 A 
177 A 
178 A 
179 C 
180 A 
181 B 
182 A 
183 A 
184 A 
185 A 
186 A 
187 C 
188 A 
189 A 
190 A 
191 A 
192 A 
193 A 
194 A 
197 A 
198 A 
199 A 
200 B 
201 A 
202 A 
203 A 
204 A 
205 C 
206 A 
207 B 
208 A 
209 B 
210 A 
211 A 
212 A 
213 A 
215 B 
216 B 
217 A 
218 A 
219 A 
220 B 
221 C 
223 A 
225 A 
226 A 
227 A 
228 A 
229 A 
230 A 
231 A 
232 A 
233 A 
234 A 
235 A 
236 A 
237 B 
238 A 
239 A 
240 A 
241 A 
242 A 
243 A 
244 A 
245 A 
246 A 
247 A 
248 C 
249 A 
253 A 
254 A 
255 A 
256 A 
257 A 
258 A 
259 C 
260 C 
265 C 
268 C 
271 A 
272 A 
273 A 
274 A 
275 A 
276 A 
277 A 
278 A 
279 A 
280 A 
281 B 
282 A 
283 A 
284 A 
285 A 
286 A 
287 A 
288 A 
289 A 
290 A 
291 A 
292 A 
293 A 
294 A 
295 A 
296 A 
297 A 
298 A 
299 A 
300 A 
301 A 
302 A 
303 A 
304 A 
305 C 
306 C 
307 A 
308 A 
309 B 
310 C 
311 B 
312 A 
313 A 
314 A 
315 A 
316 A 
317 B 
318 A 
319 C 
321 A 
322 B 
323 A 
326 C 
327 A 
327 C 
328 C 
329 A 
330 A 
331 A 
332 A 
333 A 
334 A 
335 A 
336 A 
337 C 
338 A 
339 A 
340 A 
341 A 
342 A 
343 A 
344 C 
345 A 
346 A 
347 A 
348 A 
349 A 
350 A 
351 B 
351 B 
352 A 
353 A 
354 A 
355 A 
356 A 
357 A 
358 A 
359 A 
360 A 
361 A 
362 A 
363 A 
365 A 
366 C 
368 A 
369 A 
370 A 
371 A 
372 A 
374 B 
379 A 
380 A 
381 A 
382 A 
383 A 
384 A 
385 A 
386 A 
387 A 
388 A 
389 A 
390 A 
391 A 
392 A 
393 A 
394 A 
396 A 
397 A 
398 A 
399 A 
400 A 
401 B 
402 A 
403 A 
400 A 
404 A 
405 A 
406 A 
407 A 
Reference D 
Compound A 
Reference D 
Compound B 
Reference C 
Compound C 
______________________________________ 
Note: 
Reference Compound A: Compound of JP, A 61280452 
##STR163## 
Reference Compound B: Compound of JP, A 61106538 
##STR164## 
Reference Compound D: Compound of JP, A 61106538 
##STR165## 
TEST EXAMPLE 2 
Controlling effect on downy mildew of cucumber (Pseudoperonospora cubensis) 
Cucumber plants at 2-leaf stage were sprayed with test compound (200 ppm) 
one day before inoculation with zoospores of Pseudoperonospora cubensis. 
After the plants were held in a humid room at 25.degree. C. for one day 
and then in a greenhouse for 6 days, the degree of infection per leaf was 
examined. Disease controlling activity was estimated in the same manner as 
in Test example 1. The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Compound Fungicidal 
No. effect 
______________________________________ 
1 A 
2 B 
3 A 
5 B 
6 C 
9 C 
10 A 
11 B 
12 A 
13 B 
14 A 
15 A 
16 B 
17 B 
20 A 
21 A 
22 A 
23 A 
24 A 
25 A 
27 A 
28 B 
29 A 
30 A 
31 A 
32 A 
33 A 
34 A 
35 A 
40 A 
41 A 
42 B 
43 B 
44 A 
45 C 
47 C 
48 A 
49 B 
52 B 
53 C 
55 A 
56 C 
58 C 
59 A 
61 B 
62 C 
66 A 
67 A 
68 A 
69 B 
70 A 
71 B 
74 C 
75 B 
77 C 
78 B 
79 A 
80 C 
81 A 
82 A 
83 A 
86 B 
91 B 
92 A 
93 A 
95 B 
96 B 
97 A 
104 C 
105 A 
106 A 
107 B 
109 A 
110 A 
111 A 
112 B 
114 A 
115 B 
118 A 
119 A 
120 A 
122 A 
124 A 
125 A 
126 A 
127 A 
128 A 
129 C 
131 C 
132 C 
133 A 
134 A 
135 A 
137 A 
139 B 
142 C 
143 A 
144 A 
145 B 
146 A 
147 A 
148 A 
149 A 
150 A 
151 A 
152 A 
153 A 
154 A 
155 A 
156 A 
157 A 
158 A 
159 A 
160 A 
161 A 
162 C 
163 A 
164 A 
165 A 
167 A 
168 A 
169 A 
170 C 
172 A 
174 A 
175 A 
176 A 
177 A 
178 A 
179 A 
181 A 
185 A 
186 A 
187 B 
188 A 
190 A 
193 C 
198 A 
199 A 
200 A 
201 A 
202 C 
203 A 
204 A 
205 B 
206 A 
207 A 
208 A 
216 B 
218 C 
219 A 
220 A 
221 A 
222 A 
223 A 
224 A 
225 A 
226 A 
227 A 
228 A 
229 A 
230 A 
231 A 
232 A 
233 A 
234 A 
235 A 
236 A 
237 A 
238 A 
239 A 
240 A 
241 A 
242 C 
243 A 
244 A 
245 A 
246 A 
247 C 
248 A 
249 A 
250 A 
255 A 
256 A 
257 B 
258 B 
259 A 
260 A 
261 C 
262 C 
263 C 
264 B 
266 B 
269 B 
271 A 
272 A 
273 A 
274 A 
275 B 
276 B 
277 A 
278 A 
279 A 
281 A 
282 A 
283 A 
284 A 
285 A 
286 A 
287 A 
288 B 
289 C 
290 A 
291 A 
292 A 
293 A 
294 A 
295 A 
296 A 
298 B 
299 C 
300 A 
301 A 
302 A 
303 A 
304 A 
306 C 
307 A 
308 C 
309 B 
313 A 
314 A 
315 A 
316 A 
317 B 
318 A 
319 A 
321 A 
323 A 
324 A 
325 B 
326 A 
329 B 
330 A 
331 B 
332 A 
333 C 
334 A 
336 A 
338 A 
339 A 
340 A 
341 A 
342 A 
343 B 
344 A 
345 A 
347 A 
348 A 
349 A 
350 A 
351 A 
352 A 
353 A 
354 A 
355 A 
356 A 
357 A 
358 A 
360 A 
361 A 
363 A 
364 B 
365 A 
366 B 
367 C 
368 A 
370 A 
371 A 
372 C 
374 C 
379 B 
380 B 
381 B 
384 A 
385 A 
386 A 
387 A 
388 A 
389 A 
391 A 
392 A 
393 A 
394 B 
396 A 
397 A 
399 A 
400 A 
401 C 
______________________________________ 
TEST EXAMPLE 3 
Controlling effect on rice blast (Pyricularia oryzae) 
Rice seedling at 5-leaf stage were sprayed with test compound (200 ppm) one 
day before inoculation with conidia of Pyricularia oryzae. After the 
seedlings were held in a humid room at 25.degree. C. for one day and then 
held in a greenhouse for 6 days, the number of lesions appeared per leaf 
was examined. Disease controlling activity was estimated in the same 
manner as in Test example 1. The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Compound Fungicidal 
No. effect 
______________________________________ 
1 A 
2 B 
3 A 
4 C 
6 A 
9 C 
10 B 
11 A 
12 B 
13 A 
14 A 
15 A 
16 A 
17 C 
19 B 
20 C 
21 A 
22 C 
23 A 
24 A 
25 A 
26 A 
27 A 
28 A 
29 A 
30 A 
31 A 
32 B 
33 A 
34 A 
35 A 
36 A 
39 B 
40 A 
41 A 
42 A 
43 A 
44 A 
46 C 
47 C 
48 A 
49 A 
50 B 
51 B 
52 A 
53 C 
55 A 
56 C 
57 C 
59 A 
60 C 
66 C 
67 A 
68 A 
69 B 
70 C 
71 C 
72 A 
73 C 
75 A 
77 C 
78 B 
79 A 
80 A 
81 A 
82 A 
83 A 
84 A 
86 A 
87 C 
88 C 
89 A 
90 C 
92 A 
93 A 
94 B 
96 A 
97 B 
98 A 
101 C 
102 B 
103 A 
104 C 
105 A 
106 A 
107 A 
109 A 
110 A 
111 A 
112 A 
113 A 
114 A 
115 A 
116 B 
118 A 
119 A 
120 A 
121 B 
122 A 
123 A 
124 A 
125 A 
126 A 
127 A 
128 A 
129 A 
130 A 
131 A 
132 A 
133 A 
134 A 
135 A 
136 A 
137 A 
138 A 
139 A 
140 A 
141 A 
142 A 
143 A 
144 A 
145 A 
146 A 
147 A 
148 A 
149 A 
150 A 
151 A 
152 A 
153 A 
154 A 
155 A 
156 A 
157 A 
158 A 
159 A 
160 B 
161 B 
162 C 
163 A 
164 A 
165 A 
166 A 
167 A 
168 A 
169 A 
170 A 
171 A 
172 A 
173 C 
174 A 
175 B 
176 A 
177 A 
178 A 
179 A 
180 A 
181 A 
182 B 
183 A 
184 A 
185 A 
186 A 
187 A 
188 A 
189 A 
190 A 
191 A 
192 A 
193 C 
194 A 
197 A 
198 A 
199 A 
200 A 
201 A 
202 A 
203 A 
204 A 
205 B 
206 A 
207 A 
208 A 
209 A 
210 A 
211 A 
212 A 
213 A 
214 C 
215 B 
216 A 
217 B 
218 A 
219 A 
220 A 
221 B 
222 C 
223 A 
224 A 
225 A 
226 A 
227 A 
228 A 
229 A 
230 A 
231 A 
232 A 
233 A 
234 B 
235 A 
236 A 
237 A 
238 A 
239 B 
240 A 
241 A 
242 A 
243 A 
244 A 
245 A 
246 A 
247 A 
248 B 
249 A 
250 A 
253 A 
254 A 
255 A 
256 A 
257 A 
258 A 
259 A 
260 A 
261 C 
263 C 
265 A 
266 A 
271 B 
272 A 
273 A 
274 A 
275 A 
276 A 
277 A 
278 A 
279 A 
280 A 
281 B 
282 A 
283 A 
284 A 
285 A 
286 A 
287 A 
288 A 
289 A 
290 A 
292 A 
293 A 
294 A 
295 A 
296 A 
297 B 
298 A 
299 A 
300 A 
301 A 
302 A 
303 A 
304 A 
305 A 
306 A 
307 A 
308 A 
309 A 
310 A 
311 C 
312 A 
313 A 
314 A 
315 A 
316 A 
317 C 
318 A 
319 A 
320 A 
321 A 
322 A 
323 A 
324 B 
327 A 
328 B 
329 A 
330 A 
331 A 
332 A 
333 C 
334 A 
335 A 
336 A 
337 B 
338 A 
339 A 
340 A 
341 A 
342 A 
343 A 
344 A 
345 A 
346 A 
347 A 
348 A 
349 A 
350 A 
351 B 
352 A 
353 A 
354 B 
355 A 
356 A 
357 A 
358 A 
359 A 
360 A 
361 A 
362 A 
363 A 
364 A 
365 A 
366 A 
369 A 
370 A 
371 A 
372 A 
373 B 
374 B 
375 B 
376 B 
379 A 
380 A 
381 A 
382 A 
383 A 
385 B 
386 A 
387 A 
388 A 
389 C 
391 A 
392 A 
393 A 
394 A 
396 A 
397 A 
398 A 
399 A 
400 A 
401 A 
402 A 
403 A 
404 A 
405 A 
406 B 
407 A 
408 C 
Reference D 
Compound A 
Reference D 
Compound B 
Reference C 
Compound C 
______________________________________