Guanidine derivatives, their production and insecticides

An insecticidal composition containing a guanidine derivative of the formula: ##STR1## wherein R.sup.1 is an optionally substituted homocyclic or heterocyclic group, n is 0 or 1, R.sup.2 is a hydrogen atom or an optionally substituted hydrocarbon group, R.sup.3 is a primary, secondary or tertiary amino group, X is an electron attractive group such as nitro or trifluoroacetyl group, provided that when n is 0, R.sup.1 is an optionally substituted heterocyclic group or a salt thereof.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to guanidine derivatives or salts thereof 
useful as insecticides, their production methods and insecticidal 
compositions containing the guanidine derivatives or salts thereof. 
2. Prior Art 
Various synthetic compounds possessing pest controlling effects have been 
used as insecticides. Most of the compounds belong to organic phosphates, 
carbamates, organic chlorine-containing compounds or pyrethroid compounds. 
It is well known that frequent use of such limited categories of compounds 
causes such harmful influence as increased resistance of pest insects 
which presently brings on public discussion at various places. Some 
compounds among the above-mentioned insecticides exert potent insecticidal 
activities but show unsatisfactory effects on practical use, such as high 
toxicity on human beings, animals and fishes, eventual toxicity on enemies 
of pest insects and a high residual property in soil or the like. 
On the other hand, with respect to guanidine derivatives or salts thereof, 
3-nitro-1-(3-pyridylmethyl)guanidine, for example, is described in 
Chemical & Pharmaceutical Bulletin 23, 2744 (1975) and guanidine compounds 
possessing antiulcer activity such as cimetidine are reported in various 
articles or patents. However, there is no report of guanidine derivatives 
or salts thereof as insecticide. 
SUMMARY OF THE INVENTION 
Under such circumstances, the present invention is aimed to provide an 
insecticidal composition comprising a guanidine derivative or its salt 
which is low in toxicity on human beings, animals, fishes and natural 
enemies of pest insects, besides safety and potent pest controlling effect 
and is useful in agricultural, horticultural and/or home gardening fields. 
Thus, it provides 
(1) an insecticidal composition comprising a guanidine derivative of the 
formula (I) 
##STR2## 
wherein R.sup.1 is an optionally substituted homocyclic or heterocyclic 
group, n is 0 or 1, R.sup.2 is a hydrogen atom or an optionally 
substituted hydrocarbon group, R.sup.3 is a primary, secondary or tertiary 
amino group and X is an electron attractive group, provided that when X is 
a cyano group, R.sup.1 is a halogenopyridyl group, and when n is 0, 
R.sup.1 is an optionally substituted heterocyclic group, or salt thereof; 
(2) a guanidine derivative of the formula (I.sup.a) 
##STR3## 
wherein R.sup.1a is an optionally substituted heterocyclic group, R.sup.2a 
is a hydrogen atom or an optionally substituted hydrocarbon group, 
R.sup.3a is a primary, secondary or tertiary amino group, provided that 
when R.sup.2a is a hydrogen atom, R.sup.3a is a secondary or tertiary 
amino group, and X.sup.a is a nitro group or trifluoroacetyl group, or 
salt thereof; 
(3) a process for the preparation of the guanidine derivative (I.sup.a) or 
salt thereof which comprises reacting a compound of the formula (II) 
##STR4## 
wherein R.sup.1a R.sup.2a and X.sup.a have the same meanings as defined 
above and Y is a leaving group, or salt thereof with ammonia, or a primary 
or secondary amine or salt thereof; 
(4) a process for the preparation of the guanidine derivative (I.sup.a) or 
salt thereof which comprises reacting a compound of the formula (III) 
##STR5## 
wherein the symbols have the same meanings as defined above, or salt 
thereof, with a compound of the formula (IV) 
##STR6## 
wherein the symbols have the same meanings as defined above, or salt 
thereof; 
(5) a process for the preparation of the guanidine derivative (I.sup.a) or 
salt thereof which comprises reacting a compound of the formula (V) 
##STR7## 
wherein the symbols have the same meanings as defined above, or salt 
thereof, with a compound of the formula (VI) 
EQU R.sup.1a --CH.sub.2 --Y (VI) 
wherein the symbols have the same meanings as defined above; 
(6) a process for the preparation of the guanidine derivative (I.sup.a) or 
salt thereof which comprises reacting a compound of the formula (VII) 
##STR8## 
wherein R.sup.1a and X.sup.a have the same meanings as defined above, 
R.sup.2b is hydrogen atom or an optionally substituted hydrocarbon group, 
R.sup.3b is a primary, secondary or tertiary amino group, provided that 
when R.sup.3b is a tertiary amino group, R.sup.2b is a hydrogen atom, or 
salt thereof, with a compound of the formula (VIII) 
EQU Y--R (VIII) 
wherein Y has the same meaning as defined above, and R is an optionally 
substituted hydrocarbon group, 
(7) a process for the preparation of the guanidine derivative (I.sup.a) or 
salt thereof which comprises reacting a compound of the formula (IX) 
##STR9## 
wherein the symbols have the same meanings as defined above, or salt 
thereof, with a compound of the formula (X) 
EQU Y--X.sup.a (X) 
wherein the symbols have the same meanings as defined above, or a nitrating 
agent. 
In the above-mentioned formulae, R.sup.1 denotes an optionally substituted 
homocyclic or heterocyclic group. The homocyclic or heterocyclic group of 
R.sup.1 is a cyclic group containing the same atoms only or a cyclic group 
containing two or more different atoms, i.e., a cyclic hydrocarbon group 
or a heterocyclic group, respectively. R.sup.1a denotes an optionally 
substituted heterocyclic group, to which the definition of R.sup.1 is 
applicable. 
The cyclic hydrocarbon groups of R.sup.1 include a C.sub.3-8 cycloalkyl 
group such as cyclopropyl, cyclobutyl, cyclo pentyl or cyclohexyl; a 
C.sub.3-8 cycloalkenyl group such as cyclopropenyl, 1-cyclopentenyl, 
1-cyclohexenyl, 2-cyclo hexenyl, 1,4-cyclohexadienyl; and a C.sub.6-14 
aryl group such as phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthryl, 1-, 2-, 
3-, 4- or 9-phenanthryl or 1-, 2-, 4-, 5- or 6azulenyl. The preferred 
cyclic hydrocarbon groups are aromatic ones, e.g., C.sub.6-14 aryl groups 
such as phenyl, etc. 
The heterocyclic groups of R.sup.1 or R.sup.1a include a 5-8 membered ring 
containing one to five hetero atoms of oxygen atom, sulfur atom and 
nitrogen atom and its condensed ring. Examples of the heterocyclic groups 
are 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 
2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- 
or 5imidazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 
5-(1,2,4-oxadiazolyl), 1,3,4-oxadiazolyl, 3- or 5-(1,2,4-thiadiazolyl), 
1,3,4-thiadiazolyl, 4- or 5-(1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 
1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxido-2-, 3- or 
4-pyridyl, 2-, 4- or 5pyrimidinyl, N-oxido-2-, 4- or 5-pyrimidinyl, 3- or 
4pyridazinyl, pyrazinyl, N-oxido-3- or 4-pyridazinyl, benzofuryl, 
benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl, tetrazolo[ 
1,5-b]pyridazinyl, triazolo [4,5-b]pyridazinyl, oxoimidazinyl, 
dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 
1,4oxadinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperadinyl, 
benzoimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, 
quinazolinyl, quinoxalinyl, indolizinyl, quinolizinyl, 1,8-naphthyridinyl, 
purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, 
phenanthridinyl, phenazinyl, phenothiadinyl or phenoxazinyl. The preferred 
heterocyclic groups are 5- or 6-membered nitrogen-containing heterocyclic 
groups such as 2-, 3- or 4-pyridyl or 2-, 4- or 5-thiazolyl. The 
homocyclic or heterocyclic groups of R.sup.1 and the heterocyclic groups 
of R.sup.1a may possess one to five (preferably one) substituents which 
are the same or different. Examples of the substituents are a C.sub.1-15 
alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 
s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 
dodecyl, tridecyl, tetradecyl or pentadecyl; a C.sub.3-10 cycloalkyl group 
such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a C.sub.2-10 
alkenyl group such as vinyl, allyl, 2-methylallyl, 2-butenyl, 3-butenyl or 
3-octenyl; a C.sub.2-10 alkynyl group such as ethynyl, 2-propynyl or 
3-hexynyl; a C.sub.3-10 cycloalkenyl group such as cyclopropenyl, 
cyclopentenyl or cyclohexenyl; a C.sub.6-10 aryl group such as phenyl or 
naphthyl; a C.sub.7-10 aralkyl group such as benzyl or phenylethyl; nitro 
group; hydroxy group; mercapto group; oxo group; thioxo group; cyano 
group; carbamoyl group; carboxyl group; a C.sub.1-4 alkoxycarbonyl group 
such as methoxycarbonyl or ethoxycarbonyl; sulfo group; a halogen atom 
such as fluorine, chlorine, bromine or iodine; a C.sub.1-4 alkoxy group 
such as methoxy, ethoxy, propoxy, isoporpoxy, butoxy, isobutoxy, s-butoxy 
or t-butoxy; a C.sub.6-10 aryloxy group such as phenoxy; a C.sub.1-4 
alkylthio group such as methylthio, ethylthio, n-propylthio, 
isopropylthio, n-butylthio or t-butylthio; a C.sub.6-10 arylthio group 
such as phenylthio; a C.sub.1-4 alkylsulfinyl group such as methylsulfinyl 
or ethylsulfinyl; a C.sub.6-10 arylsulfinyl group such as phenylsulfinyl; 
a C.sub.1-4 alkylsulfonyl group such as methylsulfonyl or ethylsulfonyl; a 
C.sub.6-10 arylsulfonyl group such as phenylsulfonyl; amino group; a 
C.sub.2-6 acylamino group such as acetylamino or propionylamino; a mono- 
or di-C.sub.1-4 alkylamino group such as methylamino, ethylamino, 
n-propylamino, isopropylamino, n-butylamino, dimethylamino or 
diethylamino; a C.sub.3-6 cycloalkylamino group such as cyclohexylamino; a 
C.sub.6-10 arylamino group such as anilino; a C.sub.2-4 acyl such as 
acetyl; a C.sub.6-10 arylcarbonyl group such as benzoyl; and a 5- or 
6-membered heterocyclic group containing one to four hetero atoms selected 
from oxygen, sulfur and nitrogen, such as 2or 3-thienyl, 2- or 3-furyl, 
3-, 4- or 5-pyrazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 
2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5imidazolyl, 
1,2,3- or 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, 2-, 3- or 4-pyridyl, 2-, 
4- or 5pyrimidinyl, 3- or 4-pyridazinyl, quinolyl, isoquinolyl or indolyl. 
One to five substituents selected from the above exemplified substituents 
can carry on the above-mentioned homocyclic or heterocyclic groups. When 
the substituent is e.g., the C.sub.6-10 aryl, C.sub.7-10 aralkyl, 
C.sub.3-10 cycloalkyl, C.sub.3-10 cycloalkenyl, C.sub.6-10 aryloxy, 
C.sub.6-10 arylthio, C.sub.6-10 aryl-sulfinyl, C.sub.6-10 arylsulfonyl, 
C.sub.6-10 arylamino or heterocyclic group, it may be further substituted 
by one to five of the above-mentioned halogen atom; hydroxy group; 
C.sub.1-4 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, s-butyl or t-butyl; C.sub.2-4 alkenyl group such as vinyl, allyl 
or 2methylallyl; C.sub.2-4 alkynyl group such as ethynyl or 2-propynyl; 
C.sub.6-10 aryl group; C.sub.1-4 alkoxy group; phenoxy group; C.sub.1-4 
alkylthio group or phenylthio group. When the substituent is the 
C.sub.1-15 alkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, C.sub.1-4 
alkoxy, C.sub.1-4 alkylthio, C.sub.1-4 alkylsulfinyl, C.sub.1-4 
alkylsulfonyl, amino, mono- or di-C.sub.1-4 alkylamino, C.sub.3-6 
cycloalkylamino or C.sub.6-10 arylamino group, it may be further 
substituted by one to five of the above-mentioned halogen atom, hydroxy 
group, C.sub.1-4 alkoxy group or C.sub.1-4 alkylthio group. 
Preferred examples of R.sup.1 are 5- or 6-membered nitrogen-containing 
heterocyclic groups such as pyridyl or thiazolyl which may be substituted 
by one or two halogens. 
The symbol "n" denotes 0 or 1, preferably 1. 
The hydrocarbon group in the "optionally substituted hydrocarbon group" of 
R.sup.2, R.sup.2a R.sup.2b and R includes the C.sub.1-15 alkyl, C.sub.3-10 
cycloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, C.sub.3-10 
cycloalkenyl, C.sub.6-10 aryl and C.sub.7-10 aralkyl groups which are 
mentioned with respect to R.sup.1. Those mentioned as the substituents on 
the homocyclic or heterocyclic group of R.sup.1 are applicable to the 
substituents on the "optionally substituted hydrocarbon group". 
Preferred examples of R.sup.2, R.sup.2a and R.sup.2b are hydrogen atom and 
a C.sub.1-4 alkyl group such as methyl, ethyl or propyl. Preferred example 
of R is the above-mentioned C.sub.1-4 alkyl group. 
R.sup.3, R.sup.3a and R.sup.3b denote a primary, secondary or tertiary 
amino group, which can be represented by the formula: 
##STR10## 
, wherein R.sup.4 and R.sup.5 are, the same or different, a hydrogen atom 
or an optionally substituted hydrocarbon group or both R.sup.4 and R.sup.5 
are combined with the adjacent nitrogen atom to form a cyclic amino group. 
(Here, the primary amino group is an unsubstituted amino group in case 
where R.sup.4 and R.sup.5 of the above formula are a hydrogen atom, the 
secondary amino group is mono-substituted amino group in case where either 
one of R.sup.4 and R.sup.5 is hydrogen atom and the tertiary amino group 
is disubstituted amino group in case where both of R.sup.4 and R.sup.5 are 
not hydrogen atom.) The optionally substituted hydrocarbon groups 
mentioned with respect to R.sup.2, R.sup.2a, R.sup.2b and R are applicable 
to those of R.sup.4 and R.sup.5. 
Examples of the cyclic amino groups which are formed from R.sup.4 and 
R.sup.5 together with the adjacent nitrogen atom are aziridino, azetidino, 
pyrrolidino, morpholino and thiomorpholino groups. Preferred examples of 
R.sup.3, R.sup.3a and R.sup.3b are an unsubstituted amino group; a 
mono-C.sub.1-4 alkylamino group such as methylamino, ethylamino or 
propylamino; a di-C.sub.1-4 alkylamino group such as dimethylamino or 
ethylmethylamino and a C.sub.1-4 acylamino group such as formamido, 
N-methylformamido or acetamido. 
Examples of the electron attractive groups of X are cyano, nitro, an 
alkoxycarbonyl (e.g., C.sub.1-4 alkoxycarbonyl such as methoxycarbonyl or 
ethoxycarbonyl), hydroxycarbonyl, a C.sub.6-10 aryloxycarbonyl (e.g., 
phenoxycarbonyl), a heterocycle-oxycarbonyl (the abovementioned 
heterocyclic group being applicable to this group, thus specifically 
pyridyloxycarbonyl or thienyloxycarbonyl), a C.sub.1-4 alkylsulfonyl which 
may be substituted by a halogen such as chlorine, bromine or fluorine 
(e.g., methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl), sulfamoyl, 
a di-C.sub.1-4 alkoxyphosphoryl (e.g., diethoxyphosphoryl), a C.sub.1-4 
acyl which may be substituted by a halogen such as chlorine, bromine or 
fluorine (e.g., acetyl, trichloroacetyl or trifluoroacetyl), C.sub.6-10 
aryl-carbonyl (e.g., benzoyl), carbamoyl or a C.sub.1-4 
alkylsulfonylthiocarbamoyl (e.g., methylsulfonythiocarbamoyl). Preferred 
example of the electron attractive group is a nitro group. X.sup.a denotes 
a nitro or trifluoroacetyl group. 
Examples of the leaving groups of Y are a halogen atom such as chlorine, 
bromine, iodine or fluorine; a C.sub.1-4 alkylsulfonyloxy group which may 
be substituted by one to three halogen atoms (e.g., Cl, Br or F) such as 
methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy or 
trifluoromethanesulfonyloxy; a C.sub.6-10 arylsulfonyloxy group which may 
be substituted by one to four halogen atoms (e.g., Cl, Br or F) such as 
benzenesulfonyloxy, p-toluenesulfonyloxy, p-bromobenzenesulfonyloxy or 
mesitylenesulfonyloxy; a Cl-6 acyloxy group which may be substituted by 
one to three halogen atoms(e.g., Cl, Br or F) such as acetyloxy, 
propionyloxy or trifluoroacetyloxy; a C.sub.6-10 arylcarbonyloxy group 
such as benzoyloxy; hydroxy group; a C.sub.1-4 alkoxy group such as 
methoxy or ethoxy; a C.sub.1-4 alkylthio group such as methylthio or 
ethylthio; a C.sub.1-4 alkylsulfinyl group such as methylsulfinyl; a 
C.sub.1-4 alkylsulfonyl group such as methylsulfonyl; a C.sub.6-10 aryloxy 
group which may be substituted by one to three of a halogen (e.g., Cl, Br 
or F) or nitro, such as phenoxy, p-chlorophenoxy or p-nitrophenoxy; a 
heterocycleoxy group such as 2-pyridyloxy or 2-benzoxazolyloxy; a 
C.sub.6-10 arylthic group which may be substituted by one or two of nitro 
or the like such as phenylthio or p-nitrophenylthio; a C.sub.7-12 
aralkylthio group which may be substituted by one or two of nitro or the 
like such as benzylthio or p-nitrobenzylthio; a heterocyclethio group such 
as 2-pyridylthio or 2-benzothiazolylthio; amino group; a mono- or 
di-C.sub.1-4 alkylamino group such as methylamino, ethylamino or 
dimethylamino and a 5-membered nitrogen-containing heterocycle group such 
as 1-imidazolyl or 1,2,4-triazol-1-yl. 
Preferred examples of Y in the compounds (II) and (III) are a C.sub.1-4 
alkylthio group such as methylthio or ethylthio, a C.sub.7-12 aralkylthio 
group such as benzylthio, a C.sub.1-4 alkoxy group such as methoxy or 
ethoxy, amino group and a mono- or di-C.sub.1-4 alkylamino group such as 
methylamino, ethylamino or dimethylamino. Those of Y in the compounds 
(VI), (VIII) and (X) are a halogen atom such as chlorine or bromine, a 
C.sub.1-4 alkylsulfonyloxy group which may be substituted by one to three 
halogen atoms such as methanesulfonyloxy or trifluoromethanesulfonyloxy, a 
C.sub.6-10 arylsulfonyloxy group such as benzenesulfonyloxy or 
p-toluenensulfonyloxy, hydroxyl group and a C.sub.1-4 acyloxy group which 
may be substituted by one to three halogen atoms such as acetyloxy or 
trifluoroacetyloxy. 
Preferred example of the guanidine derivative (I) or its salt is the 
compound of the formula (I.sup.b) 
##STR11## 
wherein R.sup.1b is a pyridyl, a halogenopyridyl or halogenothiazolyl 
group, R.sup.2C, R.sup.4a and R.sup.5a are, the same or different, 
hydrogen atom, or a methyl, ethyl, formyl or acetyl group, or its salt. 
Specifically, R.sup.1b of the formula (I.sup.b) includes 3-pyridyl, a 
halogenopyridyl such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl or 
5-bromo-3pyridyl or a halogenothiazolyl such as 2-chloro-5thiazolyl or 
2-bromo-5-thiazolyl. 
The guanidine derivatives (I) or their salts form cis and trans-isomers 
with respect to the position of X and also can theorethically form 
tautomers in the case of R.sup.2 being hydrogen or R.sup.3 being primary 
or secondary amino. These isomers of the guanidine derivatives (I) or 
their salts are included in the present invention. 
##STR12## 
In the above formulae, the symbols have the same meanings as defined above. 
Examples of the salts of the guanidine derivatives (I), (I.sup.a) and 
(I.sup.b) are the salts with an inorganic acid such as hydrochloric acid, 
hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid or 
perchloric acid, or an organic acid such as formic acid, acetic acid, 
tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, 
benzoic acid, picric acid or p-toluenesulfonic acid. 
The guanidine derivatives (I) or their salts can be used as insecticide in 
any application form suited for general agricultural chemicals. That is, 
one, two, or more than two kinds of the compounds (I) or their salts are 
used in the form of preparation such as emulsifiable concentrates, oil 
solution, wettable powders, dusts, granules, tablets, sprays or ointment, 
according to the purpose of use, by dissolving or dispersing them in 
suitable liquid carriers, or mixing them with or absorbing them on 
suitable solid carriers. These preparations may contain, if necessary, 
emulsifying agent, suspending agent, spreading agent, penetrating agent, 
wetting agent, thickening agent or stabilizer, and can be prepared by any 
conventional method known per se. 
The rate of the compound (I) or a salt thereof contained in an insecticidal 
preparation is suitably about 10 to 90% by weight in the case of 
emulsifiable concentrates or wettable powders, about 0.1 to 10% by weight 
in the case of oil solution or dusts and about 1 to 20% by weight in the 
case of granules. However, such concentration may be changed properly, 
depending on the purpose of use. Emulsifiable concentrates, wettable 
powders or the like is suitably diluted or extended (for example, to 100 
to 100000 times) with water or the like, on the occasion of use, and then 
scattered. 
Suitable examples of the liquid carriers (solvents) include solvents such 
as water, alcohols (for example, methanol, ethanol, n-propanol, 
isopropanol or ethylene glycol), ketones (for example, acetone or methyl 
ethyl ketone), ethers (for example, dioxane, tetrahydrofuran, ethylene 
glycol monomethyl ether, diethylene glycol monomethyl ether or propylene 
glycol monomethyl ether), aliphatic hydrocarbons (for example, kerosene, 
kerosene oil, fuel oil or machine oil), aromatic hydrocarbons (for 
example, benzene, toluene, xylene, solvent naphtha or methylnaphthalene), 
halogenated hydrocarbons (for example, dichloromethane, chloroform or 
carbon tetrachloride), acid amides (for example, dimethylformamide or 
dimethyl-acetamide), esters (for example, ethyl acetate, butyl acetate or 
fatty acid glycerol ester) or nitriles (for example, acetonitrile or 
propionitrile). These solvents are used individually or as a suitable 
mixture of two, or more, of them. 
Suitable examples of the solid carriers (diluents or dust carrier) include 
vegetable powder (for example, soybean meal, tobacco meal, wheat flour or 
wood flour), mineral powders (for example, clays such as kaolin, 
bentonite, or acid clay, talcs such as talc powder or pyrophyllite 
powder), silicas (for example, diatomaceous earth or mica powder), 
aluminas, sulfur powder or active carbon. They are used individually or as 
a suitable mixture of two, or more, of them. 
Also, suitable examples of bases for ointments include polyethylene glycol, 
pectin, polyalcohol esters of higher aliphatic acids (for example, 
glycerin monostearate), cellulose derivatives (for example, methyl 
cellulose), sodium alginate, bentonite, higher alcohols, polyalcohols (for 
example, glycerin), vaseline, white petrolatum, liquid paraffin, lard, 
various vegetable oils, lanolin, dehydrated lanolin, hard oil or resins. 
They are used individually, or as a suitable mixture of two, or more, of 
them or together with surface active agents mentioned below. 
As surface active agents used as the emulsifying agent, spreading agent, 
penetrating agent or dispersing agent, nonionic or anionic surface active 
agents such as soaps; polyoxyethylene alkyl aryl ethers (e.g., Noigen.RTM. 
and EA 142.RTM. from Dai-ichi Kogyo Seiyaku K.K., Japan, and Nonal.RTM. 
from Toho Chemical Japan); alkyl sulfates (e.g., Emal 10.RTM. and Emal 
40.RTM. from Kao K.K., Japan); alkyl sulfonates (e.g., Neogen.RTM. and 
Neogen T.RTM. from Dai-ichi Kogyo Seiyaku K.K., and Neopellex.RTM. from 
Kao K.K.); polyethylene glycol ethers (e.g., Nonipol 85.RTM., Nonipol 
100.RTM., Nonipol 160.RTM. from Sanyo Kasei K.K., Japan); or polyhydric 
alcohol esters (e.g., Tween 20.RTM. and Tween 80.RTM. from Kao K.K.) are 
used, if necessary. 
The guanidine derivatives (I) or their salts can also be used, as occasion 
demands, in combination with or as an admixture with other insecticides 
(for example, pyrethroid insecticides, organophosphorus insecticides, 
carbamate insecticides or natural insecticides), acaricides, nematicides, 
herbicides, plant hormones, plant growth regulators, fungicides (for 
example, copper fungicides, organic chlorine fungicides, organic sulfur 
fungicides or phenol fungicides), synergistic agents, attractants, 
repellents, pigments and/or fertilizers. 
The guanidine derivatives (I) or their salts are effective in preventing 
sanitary or horticultural insect pests and animal and plant parasites and 
can exert potent insecticidal activities when they are directly contacted 
with insects, e.g., by applying to their living animals or plants. An 
interesting characteristic property of the compounds is found in that 
potent insecticidal activities can be achieved by once absorbing the 
compounds in plants through their root, leave or stem which are then 
sucked or bitten by insects or contacted with insects. Such property is 
advantageous for preventing suctorial type or mandible type insecticides. 
Moreover, the compounds (I) and their salts possess safe and advantageous 
properties as agents for preventing agricultural injurious insects, such 
as no substantial damage on plants and less toxicity against fishes. 
Specifically, the preparations containing the guanidine derivatives (I) or 
their salts are especially effective in preventing Hemiptera injurious 
insects such as Eurydema rugosum, Scotinophara lurida, Riptortus clavatus, 
Stephanitis nashi, Laodelphax striatellus, Nilaparvata Nephotettix 
cincticeps, Unaspis yanonensis, Aphis glycines, Lipaphis erysimi, 
Brevicoryne brassicae, Aphis gossypii; Lepidoptera injurious insects such 
as Spodoptera litura, Plutella xylostella, Pieris rapae crucivora, Chilo 
suppressalis, Autographa nigrisigna, Helicoverpa assulta, Pseudaletia 
separata, Mamestra brassicae, Adoxophyes orana fasciata, Notarcha 
derogata, Cnaphalocrocis medinalis, Phthorimaea operculella; Coleoptera 
injurious insects such as Epilachna vigintioctopunctata, Aulacophora 
femoralis, Phyllotreta striotata, Oulema oryzae, Echinocnemus squameus; 
Diptera injurious insects such as Musca domestica, Culex pipiens pallens, 
Tabanus trigonus, Delia antiqua, Delia platura; Orthosptera injurious 
insects such as Locusta migratoria, Gryllotalpa africana; Diotyoptera 
injurious insects such as Blattella germanica, Periplaneta fuliginosa; 
Tetranychidaes such as Tetranychus urticae, Panonychus citri, Tetranychus 
kanzawai, Tetranychus cinnabarinus, Panonychus ulmi, Aculops pelekassi; 
and Nematodes such as Aphelenchoides besseyi. 
The insecticidal composition comprising the quanidine derivative (I) or its 
salt of the present invention is an excellent agricultural product having 
fairly low toxicity and good safety. It can be used in a similar way to 
the conventional insecticidal composition and can exert excellent effects 
in comparison with the conventional composition. For example, the 
insecticidal composition of the present invention can be applied to the 
target insects, by treatment in nursery box, application for stem and leaf 
of crop, spraying for insects, application in water of a paddy field or 
soil treatment of a paddy field. The amount of application may broadly 
vary depending on the season, place and method of application, and so 
forth. However, the active ingredient (the guanidine derivative (I) or its 
salt) is used in general, in an amount of 0.3g to 3,000g, preferably 50g 
to 1,000g per hectare. When the insecticidal composition of the present 
invention is in a wettable powder, it can be used by diluting it so as to 
be 0.1-1000 ppm, preferably 10-500 ppm as the final concentration of the 
active ingredient. 
The guanidine derivatives (I.sup.a) or salts thereof can be prepared by 
Methods (A)-(F) mentioned below. Besides, when the compound (I.sup.a) is 
obtained in its free form or salt form, it can be converted into the 
corresponding salt (already mentioned salt form) or free form by the 
conventional methods. Also, any compound of the compounds (I.sup.a) may be 
in any of free or salt form when it is used as a raw material for 
preparing another compound of the compounds (I.sup.a). Other raw materials 
than the compounds (I.sup.a) which can form salts can be employed as any 
of free or salt form. Accordingly, raw materials to be employed and 
products in the below-mentioned Methods include their respective salts 
[e.g., salts with the acids as mentioned in the compound (I)]. (A) In the 
present invention, the guanidine derivative (I.sup.a) or its salt can be 
prepared by reacting a compound (II) or its salt with ammonia, a primary 
or secondary amine or its salt. 
The ammonia, primary or secondary amines or salts thereof to be employed 
are amines represented by the formula 
EQU R.sup.3a --H (XI) 
wherein R.sup.3a has the same meaning as defined above, or salts thereof. 
In the reaction, it is especially preferred to use the compound (II) in 
which Y is a C.sub.1-4 alkylthio such as methylthio, or amino. The 
compound (XI) or its salt is preferably employed in about 0.8-2.0 
equivalents, to the compound (II) or its salt but may be employed in about 
2.0-20 equivalents as far as the reaction is not impeded. 
The reaction is usually conducted in a suitable solvent, although it may be 
conducted without solvent. Examples of the solvents are water, alcohols 
such as methanol, ethanol, n-propanol or isopropanol; aromatic 
hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons 
such as dichloromethane or chloroform; saturated hydrocarbons such as 
hexane, heptane or cyclohexane; ethers such as diethyl ether, 
tetrahydrofuran (hereinafter abbreviated as THF) or dioxane; ketones such 
as acetone; nitriles such as acetonitrile; sulfoxides such as 
dimethylsulfoxide (hereinafter abbreviated as DMSO); acid amides such as 
dimethylformamide (hereinafter abbreviated as DMF), esters such as ethyl 
acetate or carboxylic acids such as acetic acid or propionic acid. These 
solvents can be used singly or in admixture of two or more kinds, in an 
appropriate ratio such as 1:1-1:10. When the reaction mixture is not 
homogenous, the reaction may be conducted in the presence of a phase 
transfer catalyst such as a quaternary ammonium salt (e.g., 
triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, 
trimethyldecylammonium chloride, tetramethylammonium bromide) or crown 
ethers. 
The reaction may be accelerated by addition of a base or metallic salt in 
an amount of 0.01-10 equivalents, preferably 0.1-3 equivalents. Examples 
of the bases are inorganic bases such as sodium hydrogen carbonate, 
potassium hydrogen carbonate, sodium carbonate, potassium carbonate, 
sodium hydroxide, potassium hydroxide, calcium hydroxide, phenyl lithium, 
butyl lithium, sodium hydride, potassium hydride, sodium methoxide, sodium 
ethoxide, metallic sodium or metallic potassium; and organic bases such as 
triethylamine, tributylamine, N,N-dimethylaniline, pyridine, lutidine, 
collidine, 4-(dimethylamino) pyridine or DBU 
(1,8-diazabicyclo[5,4,0]undecene-7). The above organic bases themselves 
can be used as a solvent, too. Examples of the metallic salts are copper 
salts such as copper chloride, copper bromide, copper acetate or copper 
sulfate; or mercury salts such as mercury chloride, mercury nitrate or 
mercury acetate. 
Usually, the reaction temperature is in the range of -20.degree. C. to 
150.degree. C., preferably 0.degree. C. to 100.degree. C. and the reaction 
time is 10 minutes to 50 hours, preferably 1 to 20 hours. 
(B) The compound (I.sup.a) or its salt can be prepared by reacting a raw 
material (III) or its salt with a compound (IV) or its salt. 
Preferred examples of Y and the reaction conditions are the same as those 
stated in Method (A). (C) The compound (I.sup.a) or its salt can be also 
prepared by reacting a compound (V) or its salt with a compound (VI). 
The leaving group represented by Y of the compound (VI) is preferably a 
halogen such as chlorine or bromine; a C.sub.1-4 alkylsulfonyloxy such as 
methanesulfonyloxy; a C.sub.6-10 arylsulfonyloxy such as 
p-toluenesulfonyloxy; or a C.sub.1-4 acyloxy which may be substituted by 
one to three halogens such as acetyloxy or trifluoroacetyloxy. 
The compound (VI) is preferably used in about 0.8-1.5 equivalents, to the 
compound (V), although a large excess amount may be used as far as it does 
not impede the reaction. In order to accelerate the reaction, it may be 
conducted in the presence of a base, to which those stated in Method (A) 
are applicable. The base can be used in about 0.5 equivalents to a large 
excess amount, preferably about 0.8 to 1.5 equivalents, to the compound 
(V). The organic base when used as the base can serve as the solvent, too. 
The reaction is preferably conducted in a solvent as mentioned in Method 
(A) and if the reaction system is not homogeneous, may be conducted in the 
presence of a phase-transfer catalyst as mentioned in Method (A). The 
reaction temperature is usually in the range of -20.degree. C.-150.degree. 
C., preferably 0.degree. C.-80.degree. C. The reaction time is usually in 
the range of 10 minutes to 50 hours, preferably 2 hours-20 hours. 
(D) The compound (I.sup.a) or its salt can be prepared by reacting a 
compound (VII) or its salt with a compound (VIII). 
In the reaction, preferred examples of Y and the reaction conditions are 
the same as those stated in Method (C). 
(E) The compound (I.sup.a) or its salt can be prepared by reacting a 
compound (IX) or its salt with a compound (X). 
In the reaction, preferred examples of Y are a halogen such as bromine or 
chlorine; or a C.sub.1-4 acyloxy which may be substituted by one to three 
halogens such as acetyloxy or trifluoroacetyloxy. The reaction can be 
conducted under the same condition as stated in Method (C). 
The compound (I.sup.a) in which X.sup.a is nitro, i.e., which can be 
represented by the formula 
##STR13## 
wherein R.sup.1a R.sup.2a and R.sup.3a have the same meanings as defined 
above, or salt thereof can be prepared by any of Method (A)-(E) as stated 
above but also prepared by the following method. 
(F) The compound (I.sup.a) or its salt can be prepared by nitrating a 
compound (IX) or its salt. 
60-100% nitric acid is frequently used as a nitrating agent. Other 
nitrating agents such as an alkali metal nitrate (e.g., sodium nitrate or 
potassium nitrate), an alkyl nitrate (e.g., ethyl nitrate or amyl 
nitrate), nitronium tetrafluoroborate (NO.sub.2 BF.sub.4) or nitronium 
trifluoromethanesulfonate (NO.sub.2 CF.sub.3 SO.sub.3) may be used. 
The nitrating agent can be used in 1.0-20 equivalents to the compound (IX) 
or its salt, preferably 2.0-10 equivalents in the case of nitric acid. 
The reaction may be conducted without any solvent but is usually conducted 
in sulfuric acid, acetic acid, acetic anhydride, trifluoroacetic anhydride 
or trifluoromethanesulfonic acid as the solvent. Depending upon 
circumstances, the solvents mentioned in Method (A) or mixture thereof can 
be used. The reaction temperature is in the range of -50.degree. C. to 
100.degree. C., preferably -20.degree. C. to 60.degree. C. and the 
reaction time is 10 minutes to 10 hours, preferably 30 minutes to 2 hours. 
The compound (I.sup.a) or its salt thus obtained can be isolated and 
purified, e.g., by a conventional method such as concentration, 
concentration under reduced pressure, distillation, fractional 
distillation, extraction by solvent, change of basicity, redistribution, 
chromatography, crystallization, recrystallization or the like. 
The compounds (II) and (III) or salts thereof to be employed as the raw 
materials of the methods in the present invention are partially known and 
can be prepared e.g., by the methods described in J. Med. Chem. 20, 901 
(1977), Chem. Pharm. Bull. 23, 2744 (1975) and GB-A-2,201,596 or analogues 
methods thereto. 
The primary or secondary amines (XI) [to be employed in the above-mentioned 
Method (A)], the compounds (IV) or their salts can be prepared by the 
methods described in e.g., "SHIN JIKENKAGAKU KOZA (New Experimental 
Chemistry Handbook)" issued by Maruzen Publishing Co., Ltd. of Japan, Vol. 
14-III, pp. 1332-1339 and analogues ones thereto. 
The compound (V) and (IX) or their salts can be prepared by the methods 
described in e.g., Rodd's Chemistry of Carbon Compounds, Vol. 1, Part C, 
pp. 341-353 or Chemical Reviews, 51, 301(1952) and analogous ones thereto. 
The compounds (VII) or their salts can be prepared e.g., by any of Methods 
(A), (B), (C), (E) and (F), because they are included in the compounds 
(I.sup.a) or their salts. 
The compounds (VI), (VIII) and (X) can be prepared by the methods described 
in "SHIN JIKENKAGAKU KOZA (New Experimental Chemistry Handbook)" issued by 
Maruzen Publishing Co., Ltd. of Japan, Vol. 14-I, pp. 307-450 and Vol. 
14-II, pp. 1104-1133 or analogues method thereto. 
Activity 
As will be clear from the following tests, the guanidine derivatives (I) 
and salts thereof possess excellent insecticidal activities

TEST EXAMPLE 1 
Effect against Nilaparvata lugens 
5mg of each of test compounds (shown by Compound No. obtained in Example as 
stated hereinafter) was dissolved in 0.5ml of acetone containing Tween 
20.RTM. and diluted to a predetermined concentration (500 ppm) by addition 
of Dyne (a spreader produced by Takeda Chemical Industries, Ltd. of 
Japan}diluted 3000 times with water. The solution at a rate of 10 ml/pot 
was sprayed on leaf and stem of rice seedlings at the second leaf stage 
raised in a nursery box. The treated rice seedlings were put into a test 
tube containing water at the bottom, to which 10 larvae at 3 instar of 
Nilaparvata lugens were released. After being sealed with an aluminum 
stopper, the test tube was kept in an incubator adjusted to 25.degree. C. 
Death number was counted 7 days after release. The mortality rate was 
calculated by the following formula and shown in Table 1. 
TABLE 1 
______________________________________ 
##STR14## 
Compound No. Mortality (%) 
______________________________________ 
1 100 
2 100 
3 100 
4 100 
5 100 
6 100 
7 100 
8 100 
9 100 
10 100 
11 100 
13 100 
14 100 
15 100 
16 100 
17 100 
18 100 
19 100 
20 100 
21 100 
22 100 
23 100 
24 100 
25 100 
26 100 
27 100 
28 100 
29 100 
30 100 
31 100 
32 100 
33 100 
34 100 
______________________________________ 
Table 1 clearly reveals that the quanidine derivatives (I) or salts thereof 
have an excellent insecticidal effect on Nilaparvate lugens. 
TEXT EXAMPLE 2 
Effect on Spodoptera litura 
1 mg of each of these compounds (shown by Compound No. of Example as 
mentioned below) was dissolved in 0.5 ml of acetone containing Tween 
20.RTM. and diluted to a predetermined concentration (500 ppm) by addition 
of 3000 folds diluted Dyne-water. The solution at a rate of 20 ml/pot was 
sprayed on a soy seedling at the simple leaf unfolding stage. After the 
solution having dried, two simple leaves of the soy seedling were cut off 
and put into an ice cream cup, to which 10 larvae at 3 instar of 
Spodoptera litura were released. After released, the cup was kept in an 
incubator adjusted to 25.degree. C. Death number was counted 2 days after 
release. The mortality rate was calculated by the formula written in Test 
Example 1, and shown in Table 2. 
TABLE 2 
______________________________________ 
Compound No. Mortality (%) 
______________________________________ 
5 100 
7 100 
16 100 
18 100 
19 100 
23 100 
25 100 
26 100 
27 100 
31 100 
______________________________________ 
Table 2 proves that the quanidine derivatives (I) or salts thereof have an 
excellent insecticidal effect on Spodoptera litura. 
EXAMPLES 
This invention is illustrated in further detail in the Reference Examples 
and Examples, which are only examples, and do not limit this invention. 
Modifications within the scope of this invention are permissible. 
Elution in a column chromatography in the Reference Examples and Examples 
was conducted while monitoring with TLC (Thin Layer Chromatography). In 
the TLC monitoring, the TLC plate used was Kieselgel.RTM. 60F.sub.254 
manufactured by Merck Co. (70-230 mesh), the developing solvent was the 
same as the one used for eluting in the column chromatography, and the 
detection was conducted with a UV detector. The silica gel for the column 
was Kieselgel 60 manufactured by Merck Co. (West Germany) (70-230 mesh). 
NMR spectra indicate .sup.1 H-NMR and were measured using 
tetramethylsilane as an internal standard with a spectrometer Varian EM390 
(90MHz) and all .delta. values are expressed in ppm. The value shown in () 
for a mixed solvent as the developing solvent is a mixing ratio in volume 
of constituent solvents. The abbreviations used in examples and Table 3 
have the following meanings. 
Me : methyl group 
Et : ethyl group 
ph : phenyl group 
s : singlet 
br : broad 
d : doublet 
t : triplet 
q : quartet 
m : multiplet 
dd : doublet of doublets 
J : coupling constant 
Hz : Hertz 
CDCl.sub.3 : deutero-chloroform 
DNSO-d.sub.6 : deutero-dimethylsulfoxide 
% : percentage by weight 
m.p. : melting point 
Further, room temperature means 15-20.degree. C., and all of melting points 
and temperature were shown on the centigrade. 
REFERENCE EXAMPLE 1 
A mixture of 70.3g of 2-chloro-5-(hydroxymethyl) pyridine and 50ml of 
1,2-dichloroethane was dropwise added to a mixture of 87.4g of thionyl 
chloride and 100ml of 1,2-dichloroethane during 30 minutes in a water bath 
of 5-20.degree. C. The mixture was stirred for an hour and a half at room 
temperature and for 4 hours and a half under refluxing. After 
concentrating, to the residue were added 200ml of chloroform and 60ml of 
water and then added portionwise 20g of sodium hydrogen carbonate under 
stirring. The organic phase was separated, treated with active carbon and 
concentrated to obtain 75.9g of 2-chloro-5-(chloromethyl)pyridine as a 
yellowish brown solid. 
.sup.1 H NMR(CDCl.sub.3) 4.57(2H,s), 7.34(1H,d,J=8.5Hz), 7.72(1H,dd,J=8.5, 
2.5Hz), 8.40(1H,d,J=2.5Hz) 
By the same method, 5-(chloromethyl)thiazole, 
5-chloromethyl-2-methylthiazole and 5-chloromethyl-2-phenylthiazole were 
obtained. 
REFERENCE EXAMPLE 2 
A mixture of 14.99g of 2-chloro-5-(chloromethyl) pyridine, 63.01g of 25% 
ammonia water and 60ml of acetonitrile in a stainless steel autoclave was 
stirred for 2 hours in an oil bath of 80.degree. C. After adding 12.3g of 
30% sodium hydroxide aqueous solution, the reaction mixture was 
concentrated. The residue to which 200ml of ethanol were added was dried 
over anhydrous magnesium sulfate and, filtered to remove insoluble 
materials. The filtrate was concentrated and purified by a column 
chromatography [developing solvent: dichloromethane-methanol (4:1)] to 
afford 7.66g of 5-(aminomethyl)-2- chloropyridine as a yellow solid. 
.sup.1 H NMR(CDCl.sub.3): 1.60(2H,s), 3.90(2H,s), 7.28(1H,d,J=8.5Hz), 
7.67(1H,dd,J=8.5, 2.5Hz), 
8.33(1H,d,J=2.5Hz). 
By the same method, 5-(aminomethyl)-2-bromopyridine, 
5-(aminomethyl)-2-chlorothiazole, 3-cyanobenzylamine, 
5-(aminoethyl)thiazole, 5-(aminomethyl)-2-methylthiazole, 
5-(aminomethyl)-2-phenylthiazole and 
5-(aminomethyl)-2-(trifluoromethyl)thiazole were obtained. 
REFERENCE EXAMPLE 3 
A mixture of 15.05g of 2-chloro-5-(chloromethyl) pyridine and 50ml of 
acetonitrile was dropwise added to a mixture of 36g of 40% methylamine 
aqueous solution and 200ml of acetonitrile during an hour at room 
temperature and stirred for an hour and a half. The reaction mixture was 
concentrated. The resulting residue to which 100ml of water was added, was 
neutralized by sodium hydrogen carbonate, saturated with sodium chloride 
and extracted with dichloromethane (200ml.times.2). The organic layer was 
dried over anhydrous magnesium sulfate, concentrated and purified by a 
column chromatography [developing solvent: dichloromethane-methanol (4:1)] 
to afford 8.77g of 2-chloro-5(methylaminomethyl)pyridine as a yellowish 
brown liquid. 
.sup.1 H NMR(CDCl.sub.3) 1.30(1H,br.s), 2.44(3H,s), 3.75(2H,s), 
7.30(1H,d,J=8.4Hz), 7.68(1H,dd,J=8.4, 2.4Hz), 8.35(1H,d,J=2.4Hz). 
REFERENCE EXAMPLE 4 
To a solution of 3.15g of S,S'-dimethyl dithioiminocarbonate.hydrochloride 
and 30ml of pyridine was dropwise added 6.30g of triluoroacetic anhydride 
during 30 minutes in a water bath of 20.degree. C., followed by stirring 
for 5 hours. The reaction mixture was concentrated. The residue to which 
20ml of water were added was extracted with dichloromethane (30ml). The 
organic layer was dried over anhydrous magnesium sulfate and concentrated. 
The residue was purified by a column chromatography (developing solvent: 
dichloromethane) to afford 2.33g of S,S'-dimethyl 
N-trifluoroacetyldithioiminocarbonate as a yellow liquid. 
.sup.1 H NMR(CDCl.sub.3): 2.66(s). 
REFERENCE EXAMPLE 5 
A solution of 0.89g of 5-aminomethyl-2-chloropyridine in 5ml of isopropyl 
alcohol was dropwise added to a mixture of 1.0g of S,S'-dimethyl 
N-cyanodithioiminocarbonate in 15 ml of isopropyl alcohol during 30 
minutes, under refluxing. The mixture was further refluxed for an hour and 
a half and then ice-cooled. The resulting white solid was collected by 
filtration, by which 1.35g of 
1-(6-chloro-3-pyridylmethyl)-3-cyano-2-methylisourea were obtained. 
.sup.1 H NMR(CDCl.sub.3): 2.63(3H,s), 4.51(2H,d,J=6Hz), 7.51(1H,d,J=8Hz), 
7.83(1H,dd,J=8.3Hz), 8.38(1H,d,J=3Hz), 8.95(1H,br.s). 
By the same method, 
1-(6-chloro-3-pyridylmethyl)2-methyl-3-trifluoroacetylisothiourea, 
1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-trifluoroacetylisothiourea and 
1-(2-chloro-5-thiazolylmethyl)-3-cyano-2methylisothiourea were obtained. 
REFERENCE EXAMPLE 6 
60% sodium hydride (in mineral oil) (0.80g) was washed with petroleum ether 
and suspended in 20ml of dimethylformamide (DMF). To the suspension was 
dropwise added a solution of 2.58g of 3-cyano-1,2-dimethylisothiourea in 
10ml of DMF during 10 minutes at room temperature. After stirring for an 
hour, 3.24g of 2-chloro-5-(5-chloromethyl)pyridine were added to the 
reacting mixture in 5 ;minutes, followed by stirring for 15 hours at room 
temperature. DMF was distilled off under reduced pressure, and the residue 
to which 100ml of dichloromethane were added was washed with water. The 
organic layer was dried over anhydrous magnesium sulfate, concentrated and 
purified by a column chromatography [developing solvent: 
chloroform-ethanol (20:1)] to afford 3.50g of 
1-(6-chloro-3-pyridyl-methyl)-3-cyano-1,2-dimethylisothiourea as a yellow 
liquid. 
.sup.1 H NMR(CDCl.sub.3): 2.84(3H,s), 3.20(3H,s), 4.82(2H,s), 
7.35(1H,d,J=8Hz), 7.63(1H,dd,J=8.2Hz), 8.31(1H,d,J=2Hz). 
By the same method, 1-(6-chloro-3-pyridylmethyl)- 
3-cyano-1-ethyl-2-methylisothiourea, 
1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-nitroisothiourea, 
1-(6-chloro-3-pyridylmethyl)-1-ethyl-2-methyl-3-nitroisothiourea, 
1-(2-chloro-5-thiazolylmethyl)-1-ethyl-2-methyl3-nitroisothiourea and 
1-(2-chloro-5-thiazolylmethyl)-1,2-dimethyl-3-nitroisothiourea were 
obtained. 
REFERENCE EXAMPLE 7 
A mixture of 4.07g of 2-chloro-5-aminopyridine, 2.55g of methyl 
isothiocyanate and 30ml of acetonitrile was refluxed for 13.5 hours, to 
which 0.70g of additional methyl isothiocyanate was added and the mixture 
was refluxed for 3.5 hours. The reaction mixture was concentrated, and the 
residue was purified by a column chromatography [developing solvent: 
dichloromethaneethyl acetate (1: 1)] to afford 4.51g of 
1-(6-chloro-3-pyridyl)-3-methylthiourea. 
mp 164-164.5.degree. C. (recrystallized from acetonitrile). 
.sup.1 H NMR(CDCl.sub.3): 3.12(3H,d,J=4.8Hz), 6.86(1H,br.q,J=4.8Hz), 
7.33(1H,d,J=8.5Hz), 7.86(1H,dd,J=8.5, 2.8Hz), 8.31(1H,d,J=2.8Hz), 
8.63(1H,br.s), 
REFERENCE EXAMPLE 8 
A mixture of 4.45g of 2-bromo-5-methylthiazole, 4.89g of 
N-bromosuccinimide, 0.2g of benzoyl peroxide and 50ml of carbon 
tetrachloride was refluxed for 50 minutes and then cooled to room 
temperature. An insoluble substance was removed by filtration and the 
filtrate was concentrated. The residue was purified by a column 
chromatography [developing solvent: hexanedichloromethane (2:3)] to afford 
4.53g of 2-bromo-5(bromomethyl) thiazole as a yellow solid. 
.sup.1 HNMR(CDCl.sub.3) 4.64(2H,s), 7.54(1H,s) 
By the same method, 5-(bromomethyl)-3-(difluoromethyl)-2-thiazolone was 
obtained. 
REFERENCE EXAMPLE 9 
To a mixture of 1.85g of potassium phthalimide and 20ml of dry DMF were 
added 2.57g of 2-bromo-5-(bromomethyl)thiazole by portions at room 
temperature, taking for 20 minutes, followed by stirring for an hour. An 
insoluble substance was removed by filtration and the filtrate was 
concentrated. To the residue were added 30ml of ethanol to which 0.60g of 
hydrazine hydrate were dropwise added within 2 minutes in an oil bath of 
20.degree. C. The reaction mixture was refluxed for an hour and 
concentrated. After adding 20ml of water and 10ml of conc. hydrobromic 
acid, the mixture was further refluxed for 30 minutes. After cooling, the 
mixture was neutralized with 20% aqueous sodium hydroxide solution and 
concentrated. To the residue were 50ml of acetonitrile, and an insoluble 
substance was removed by filtration. The filtrate was concentrated and the 
residue was purified by a column chromatography [developing solvent: 
dichloromethane-methanol (5:1)] to afford 0.76g of 
5-(aminomethyl)-2-bromothiazole as a brown oil. 
.sup.1 HNMR(CDCl.sub.3) 1.59(2H,s), 4.06(2H,d,J=1.2Hz), 7.40(1H,t,J=1.2Hz). 
REFERENCE EXAMPLE 10 
To a mixture of 1.35g of S-methyl-N-nitroisothiourea and 5ml of 
acetonitrile was added 0.88g of diethylamine, followed by stirring for 6 
hours in an oil bath of 60.degree. C. The reaction mixture was 
concentrated and the residue was purified by a column chromatography 
[developing solvent: dichloromethanemethanol (20:1)] to afford 0.85g of 
N,N-diethyl-N'-nitroguanidine as a white solid. 
mp 96.degree.-97.degree. C. 
.sup.1 HNMR(CDCl.sub.3) 1.23(6H,t,J=7.2Hz), 3.47(4H,q,J=7.2Hz), 
7.93(2H,br.s). 
REFERENCE EXAMPLE 11 
To a mixture of 1.0g of S-methyl-N-nitroisothiourea and 15ml of 
acetonitrile was dropwise added 0.61g of pyrrolidine within 2 minutes, 
followed by stirring for 30 minutes. The reaction mixture was 
concentrated. The resulting precipitate was washed with ethyl ether to 
afford 1.09g of 1-(N-nitroamidino)pyrrolidine as white crystals. 
mp 188-191.degree. C. 
.sup.1 HNMR(DMSO-d.sub.6): 1.7-2.1(4H,m), 3.2-3.5(4H,m), 8.19(2H,br.s). 
By the same method, N-ethyl-N-methyl-N'-nitroguanidine, mp 124-125.degree. 
C., was obtained. 
REFERENCE EXAMPLE 12 
To a mixture of 5.0g of S-methyl-N-nitroisothiourea and 25ml of pyridine 
was dropwise added 11.3g of acetic anhydride at room temperature, taking 
for 10 minutes, followed by stirring for 5 hours at the same temperature. 
The reaction mixture was concentrated, and the residue was poured into 
50ml of 2N-hydrochloric acid. The resulting solid was collected by 
filtration and dried to obtain 5.lg of 
N-acetyl-S-methyl-N'-nitroisothiourea. mp. 109-110.degree. C. 
.sup.1 HNMR(CDCl.sub.3) 2.30(3H,s), 2.42(3H,s), 11.20-12.00(1H,br.). 
REFERENCE EXAMPLE 13 
To a mixture of 11.5g of 2-hydroxy-5-methylthiazole 
(5-methyl-2-thiazolone), 100ml of dioxane and 100g of 40% sodium hydroxide 
aqueous solution was bubbled chlorodifluoromethane (gas) in an oil bath of 
80.degree. C. for an hour. The reaction mixture was poured into 500ml of 
water and extracted twice with ethyl ether. The combined ethyl ether layer 
was dried over anhydrous magnesium sulfate and concentrated. The residue 
was subjected to a column chromatography [developing solvent: 
dichloromethane-hexane (1:1)], to separate 2.0g of 
2-(difluoromethoxy)-5-methylthiazole [.sup.1 HNMR (CDCl.sub.3) 
2.35(3H,d,J=1.5Hz), 6.88(1H,br.q,J=1.5Hz), 7.18(1H,t,J=72.0Hz)] and 4.0g 
of 3-(difluoromethyl)-5-methyl-2-thiazolne [.sup.1 HNMR(CDCl.sub.3): 
2.16(3H,d,J=1.5Hz), 6.51(1H,br.q,J=1.5Hz), 7.07(1H,t,J=60.0Hz)], both 
being pale yellowish liquid. 
REFERENCE EXAMPLE 14 
A mixture of 11.22g of 2,2,2,-trifluorothioacetamide and 10.14g of ethyl 
2-chloro-2-formylacetate was stirred for 30 minutes in an oil bath of 
70.degree. C. and then for 1.5 hours in an oil bath of 100.degree. C., to 
which 100ml of dichloromethane were added. After removing an insoluble 
substance, the mixture was concentrated and the residue was subjected to a 
column chromatography [developing solvent: hexane-ethyl acetate (10:1)], 
to obtain 3.74g of ethyl 2-(trifluoromethyl)-5-thiazolecarboxylate as 
yellow liquid. 
.sup.1 HNMR(CDCl.sub.3) 1.41(3H,t,J=7.2Hz), 4.43(2H,q,J=7.2Hz), 8.50(1H,s). 
A solution of 2.51g of the above product in 10ml of dry THF was dropwise 
added to a mixture of 0.50g of lithium aluminum hydride in 80ml of dry THF 
at room temperature, taking for 45 minutes, followed by stirring for 30 
minutes. To the reaction mixture which was cooled by a freezing mixture 
were dropwise added in turn 0.5ml of water, 0.5ml of 10% sodium hydroxide 
aqueous solution and 1.5ml of water. Then the mixture was stirred for 10 
minutes in an ice bath and for 30 minutes at room temperature, and 
filtered through celite to remove an insoluble substance. The filtrate was 
concentrated. The residue to which 100ml of chloroform were added was 
dried over anhydrous magnesium sulfate and concentrated to obtain 1.24g of 
5-(hydroxymethyl)-2-(trifluoromethyl)thiazole as brown liquid. 
.sub.1 HNMR(CDCl.sub.3): 3.45(1H,br.s), 4.93(2H,s), 7.77(1H,s). 
A solution of 0.80g of the above produce in 2ml of 1,2-dichloroethane was 
dropwise added to a mixture of 0.4ml of thionyl chloride and lml of 
1,2-dichloroethnae at 40.degree. C., taking for 10 minutes, followed by 
stirring for an hour at the same temperature. Dichloromethane (2ml) and 
water (2ml) were added to the reaction mixture, which was adjusted to pH 7 
(in the aqueous layer) by addition of sodium bicarbonate under stirring. 
The organic layer was separated and the aqueous layer was extracted with 
dichloromethane. The combined organic layers were filtered to remove an 
insoluble substance. The resulting layer was washed with a saturated 
saline solution, dried over anhydrous magnesium sulfate and concentrated 
to obtain 0.74g of 5-(chloromethyl)-2-(trifluoromethyl)thiazole as red 
brown liquid. 
.sup.1 HNMR(CDCl.sub.3) 4.84(2H,s), 7.90(1H,s). 
EXAMPLE 1 
To a mixture of 0.42g of 
1-(6-chloro-3-pyridylmethyl)-3-cyano-1-ethyl-2-methylisothiourea and 5ml 
of acetonitrile was added each 0.5g of 40% methylamine aqueous solution at 
an hour interval in total six time (3.0g), while refluxing and stirring. 
The reaction mixture was stirred for 6 hours in total. Then, the mixture 
was concentrated to afford 0.32g of 
1-(6-chloro-3-pyridylmethyl)-2-cyano-1-ethyl-3-methylguanidine (Compound 
No. 3). 
mp 122-123.degree. C. 
.sup.1 H NMR(DMSO-d.sub.6) 1.07(3H,t,J=7Hz), 3.00(3H,d,J=5Hz), 
3.35(2H,q,J=7Hz), 4.62(2H,s), 7.23(1H,br.s), 7.50(1H,d,J=8Hz), 
7.78(1H,dd,J=8, 3Hz), 8.33(1H,d,J=3Hz). 
EXAMPLE 2 
To a suspension of 0.44g of 60% sodium hydride (in mineral oil) in 10ml of 
DMF was added 1.32g of N,N-dimethyl-N'-nitroguanidine during 20 minutes at 
room temperature. After stirring for 10 minutes, 1.62g of 
2-chloro-5-(chloromethyl)pyridine was added to the mixture in 5 minutes, 
and stirred for 2 hours at room temperature and for 4 hours in an oil bath 
of 60.degree. C. After filtering insoluble materials off, the filtrate was 
concentrated. The resulting residue was purified by a column 
chromatography [developing solvent: dichloromethane-ethyl acetate 
(5:1-3:1)] to obtain 0.82g of 
1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2nitroguanidine (Compound No. 
6). 
mp 160.5-162.5.degree. C. 
Elemental analysis (C.sub.9 H.sub.12 N.sub.5 O.sub.2 Cl) calculated: C; 
41.95, H; 4.69, N; 27.18, found : C; 41.73, H; 4.59, N; 26.94, 
.sup.1 H NMR(CDCl.sub.3) 3.10(6H,s), 4.49(2H,br.s), 7.27(1H,d,J=8.5Hz), 
7.70(1H,dd,J=8.5, 2.5Hz), 8.2-8.5(2H,m). 
EXAMPLE 3 
A mixture of 0.45g of 1,2-dimethyl-3-nitroisothiourea, 0.43g of 
5-(aminomethyl)-2-chloropyridine and 25ml of ethanol was refluxed for 6 
hours and concentrated. The residue was purified by a column 
chromatography [developing solvent: chloroform-ethanol (5:1)] to afford 
0.25g of 1-(6-chloro-3-pyridylmethyl)-3-methyl-2-nitroguanidine (Compound 
No. 5). 
mp 150-152.degree. C. 
Elemental analysis (C.sub.8 H.sub.10 N.sub.5 O.sub.2 Cl) calculated: C; 
39.44, H; 4.14, N; 28.74, found: C; 39.92, H; 4.12, N; 28.91. 
.sup.1 H NMR(CDCl.sub.3 -DMSO-d.sub.6) 2.94(3H,d,J=5Hz), 4.51(2H,d,J=5Hz), 
7.32(1H,d,J=8Hz), 7.75(1H,dd,J=8, 2Hz), 7.82(1H,br.s), 8.37(1H,d,J=2Hz), 
8.90(1H,br.s). 
EXAMPLE 4 
A mixture of 0.676g of S-methyl-N-nitroisothiourea, 0.783g of 
2-chloro-5-(methylaminomethyl)pyridine and 6ml of acetonitrile was 
refluxed for 17 hours, and concentrated. The residue was recrystallized 
from ethanol to obtain 0.38g of 
1-(6-chloro-3-pyridylmethyl)-1-methyl-2-nitroguanidine (Compound No. 7). 
mp 167-170.degree. C. 
Elemental analysis (C.sub.8 H.sub.10 N.sub.5 O.sub.2 Cl) calculated: C; 
39.44, H; 4.14, N; 28.74 found: C; 39.89, H; 4.07, N; 28.85. 
.sup.1 H NMR(DMSO-d.sub.6) 3.01(3H,s), 4.70(2H,s), 7.48(1H,d,J=8.4Hz), 
7.78(1H,dd,J=8.4, 2.2Hz), 8.37(1H,d,J=2.2Hz), 8.56(2H,br.s) 
EXAMPLE 5 
A mixture of 0.82g of 
1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-nitroisothiourea, 0.464g of 
40% methylamine aqueous solution and 10ml of acetonitrile was stirred for 
2 hours at 70.degree. C., and concentrated. The residue was purified by a 
column chromatography [developing solution: dichloromethane-methanol 
[10:1]) to afford 0.56g of 
1-(6-chloro-3-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine (Compound No. 
8). 
mp 136-137.degree. C. 
Elemental analysis (C.sub.9 H.sub.12 N.sub.5 O.sub.2 Cl) calculated: C; 
41.95, H; 4.69, N; 27.18, found : C; 41.89, H; 4.75, N; 27.15. 
.sup.1 H NMR(CDCl.sub.3): 2.96(3H,d,J=4.8Hz), 3.05(3H,s), 4.67(2H,s), 
7.33(1H,d,J=8.3Hz), 7.68(1H,dd,J=8.3, 2.4Hz), 7.96(1H,br.q,J=4.8Hz), 
8.30(1H,d,J=2.4Hz). 
EXAMPLE 6 
A mixture of 0.53g of nitroguanidine, 0.61g of 3-(aminomethyl)pyridine and 
10ml of water was stirred for 1.5 hours at 70-80.degree. C. and allowed to 
stand over night at room temperature. The precipitate collected by 
filtration was washed with ethanol to obtain 0.48g of 
N-nitro-N'-(3-pyridylmethyl)guanidine (Compound No. 12). 
mp 185-190.degree. C. 
.sup.1 H NMR(DMSO-d.sub.6): 4.47(2H,d,J=5Hz), 7.40(1H,dd,J=6, 4Hz), 
7.67-7.85(1H,m), 7.85-8.30(2H,br.s), 8.47-8.67(2H,m). 
EXAMPLE 7 
To a mixture of 0.24g of 
1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (Compound No. 
6) and 6ml of dry tetrahydrofuran (THF) was added 0.045g of 60% sodium 
hydride (in mineral oil) at room temperature, followed by stirring for 30 
minutes. A solution of 0.16g of iodomethane in lml of THF was added to the 
reaction mixture and allowed to react for 3 days. After adding 0.lml of 
acetic acid, the mixture was filtered to remove insoluble materials and 
the filtrate was concentrated. The residue was purified by a column 
chromatography [developing solvent: dichloromethanemethanol (20:1)] to 
obtain 0.17g of 
1-(6-chloro-3-pyridylmethyl)-1,3,3-trimethyl-2-nitroguanidine (Compound 
No. 14) as a white solid. 
mp 99-101.degree. C. 
.sup.1 H MNR (CDCl.sub.3) 2.90(3H,s), 3.02(6H,s), 4.03(2H,s), 
7.38(1H,d,J=8.5Hz), 7.79(1H,dd,J=8.5, 2.7Hz), 8.37(1H,d,J=2.7Hz). 
EXAMPLE 8 
To a mixture of 0.26g of 
1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (Compound No. 
6) and 3ml of dry THF was added 0.08g of 60% sodium hydride (in mineral 
oil) in a water bath of 20.degree. C., followed by stirring for 30 
minutes. A solution of 0.26g of acetic formic anhydride in 0.5ml of THF 
was added to the reaction mixture in one minute, and then stirred for 12 
hours after the bath was removed. After adding 0.5ml of acetic: acid, the 
reaction mixture was concentrated. The residue was purified by a column 
chromatography [developing solvent: dichloromethanemethanol (30:1)] to 
obtain 0.10g of 1-(6-chloro-3-pyridylmethyl)-1-formyl-3, 
3-dimethyl-2-nitroguanidine (Compound No. 22) as a syrup. 
.sup.1 H NMR(CDCl.sub.3) 3.03(6H,s), 4.70(2H,s), 7.36(1H,d,J=8.7Hz), 
7.74(1H,dd,J=8.7, 2.7Hz), 8.40(1H,d,J=2.7Hz), 8.44(1H,s). 
EXAMPLE 9 
A mixture of 0.20g of 1-(6-chloro-3-pyridylmethyl) 
3,3-dimethyl-2-nitroguanidine (Compound No. 6), 0.095g of acetic anhydride 
and lml of dry pyridine was stirred for 2 hours at 60.degree. C. and for 5 
hours at 100.degree. C., and then concentrated. The residue was purified 
by a column chromatography [developing solvent: dichloromethanemethanol 
(40:1)] to obtain 0.12g of 1-acetyl-1-(6-chloro-3-pyridylmethyl)-3, 
3-dimethyl-2-nitroguanidine (Compound No. 23) as a syrup (mixture of cis- 
and trans-isomers). 
.sup.1 H NMR(CDCl.sub.3) 2.10+2.16(3H,S+S), 2.6-3.3(6H,m), 4.1-5.2(2H,m), 
7.23-7.45(1H,m), 7.67-7.90(1H,m), 8.30-8.50(1H,m) 
EXAMPLE 10 
A mixture of 1.03g of 1-(6-chloro-3-pyridyl)-3methylthiourea, 0.32g of 
cyanamide, 1.58g of dicyclohexylcarbodiimide, 3 drops of ethyl 
diisopropylamine and 10ml of acetonitrile was stirred for 34 hours at room 
temperature and filtered to collect an insoluble substance. The insoluble 
substance was recrystallized from a mixed solvent cf acetonitrile and 
methanol, and then from acetonitrile to obtain 0.31g of 
1-(6-chloro-pyridyl)-2-cyano-3-methylguanidine (Compound No. 24). 
mp 227-228.degree. C. 
Elemental analysis (C.sub.8 H.sub.8 N.sub.5 Cl) calculated: C; 45.84, H; 
3.85, N; 33.41, found: C; 46.12, H; 3.68, N; 33.37. 
.sup.1 H NMR(DMSO-d.sub.6) 2.85(3H,d,4.8Hz), 7.2-7.65(2H,m), 
7.83(1H,dd,J=8.5, 3.0Hz), 8.36(1H,d,J=3.0Hz), 9.06(1H,br.s) 
EXAMPLE 11 
A mixture of 0.39g of 5-(aminomethyl)-2-bromothiazole, 0.30g of 
1,2-dimethyl-3-nitroisothiourea, 0.58g of cuprous bromide, 0.55g of 
anhydrous potassium carbonate and 4ml of dry acetonitrile was stirred in 
an oil bath of 60.degree. C. for 45 minutes. The reaction mixture was 
purified by a column chromatography [developing solvent: 
dichloromethane-methanol (10:1)] to obtain 
1-(2-bromo-5-thiazolylmethyl)-3-methyl-2-nitroguanidine (Compound No. 39), 
as white solid. 
mp 170.degree. C. 
.sup.1 HNMR(DMSO-d.sub.6) 2.81(3H,d,J=5.0Hz), 4.51(2H,s), 7.60(1H,s), 
8.08(1H,br.s), 8.93(1H,br.s). 
EXAMPLE 12 
To a mixture of 0.5g of N-acetyl-S-methyl-N'-nitroisothiourea and 5ml of 
acetonitrile was dropwise added a solution of 0.44g of 
5-(aminomethyl)-2-chloropyridine in 3ml of acetonitrile under ice-cooling, 
followed by stirring for 30 minutes under ice-cooling. The reaction 
mixture was concentrated and the residue was recrystallized from ethanol 
to afford 0.59g of 
N-acetyl-N'-(6-chloro-3-pyridylmethyl)-N"-nitroguanidine (Compound No. 42) 
as white crystals. 
mp 125-126.degree. C. 
.sup.1 HNMR(CDCl.sub.3) 2.33(3H,s), 4.60(2H,d,J=6.0Hz), 7.33(1H,d,J=7.8Hz), 
7.50-7.87(1H,m), 8.37(1H,d,J=2.5Hz), 9.70(1H,br.s), 11.85(1H,br.s). 
The compound shown in Table 3 were prepared in accordance with the 
above-mentioned Examples 1-12 and the production method of the present 
invention. Besides, the compounds of the above-mentioned Examples are 
included in Table 3. 
TABLE 3 
__________________________________________________________________________ 
##STR15## 
Preparation method 
Compound (corresponding 
No. R.sup.1 n R.sup.2 
R.sup.3 X Mp (.degree.C.) 
Example 
__________________________________________________________________________ 
No.) 
1 
##STR16## 1 H MeNH CN 196-197 1 
2 
##STR17## 1 Me MeNH CN 121-122 1 
3 
##STR18## 1 Et MeNH CN 122-123 1 
4 
##STR19## 1 Me 
##STR20## CN (Syrup) (a) 
2 
5 
##STR21## 1 H MeNH NO.sub.2 
150-152 3 
6 
##STR22## 1 H Me.sub.2 N NO.sub.2 
160.5-162.6 
2 
7 
##STR23## 1 Me NH.sub.2 NO.sub.2 
167-170 4 
8 
##STR24## 1 Me MeNH NO.sub.2 
136-137 5 
9 
##STR25## 1 H EtNH NO.sub.2 
137.5- 138 
3 
10 
##STR26## 1 H 
##STR27## NO.sub.2 
213-215.5 
2 
11 
##STR28## 1 H MeNH COCF.sub.3 
121-122 5 
12 
##STR29## 1 H H.sub.2 N NO.sub.2 
185-190 6 
13 
##STR30## 1 Et MeNH NO.sub.2 
114.5-115 
5 
14 
##STR31## 1 Me Me.sub.2 N NO.sub.2 
99-101 7 
15 
##STR32## 1 H H.sub.2 N NO.sub.2 
195-197 6 
16 
##STR33## 1 Et H.sub.2 N NO.sub.2 
137-139 5 
17 
##STR34## 1 H MeNH NO.sub.2 
169-171 3 
18 
##STR35## 1 H MeNH NO.sub.2 
(amorphous) 
3b) 
19 
##STR36## 1 H MeNH NO.sub.2 
172-173 3 
20 
##STR37## 1 H MeNH NO.sub.2 
188-190.5 
3 
21 
##STR38## 1 H MeNH NO.sub.2 
133-135 3 
22 
##STR39## 1 CHO Me.sub.2 N NO.sub.2 
(syrup) (c) 
8 
23 
##STR40## 1 COMe 
Me.sub.2 N NO.sub.2 
(syrup) (d) 
9 
24 
##STR41## 0 H MeNH CN 227-228 10 
25 
##STR42## 1 H Me.sub.2 N NO.sub.2 
154-159 2 
26 
##STR43## 1 Et MeNH NO.sub.2 
(syrup) (e) 
5 
27 
##STR44## 1 COMe 
Me.sub.2 N NO.sub.2 
127-129 9 
28 
##STR45## 1 Me H.sub.2 N COCF.sub.3 
181-184 5 
29 
##STR46## 1 Me MeNH NO.sub.2 
(syrup) (f) 
5 
30 
##STR47## 1 Me H.sub.2 N NO.sub.2 
121-122 5 
31 
##STR48## 1 H MeNH NO.sub.2 
157-166 3, 11 
32 
##STR49## 1 H Me.sub.2 N NO.sub.2 
173-174 2 
33 
##STR50## 1 H MeNH NO.sub.2 
175-179 3, 11 
34 
##STR51## 1 H MeNH NO.sub.2 
171-173 3, 11 
35 
##STR52## 1 H Me(Et)N NO.sub.2 
(syrup) (g) 
2 
36 
##STR53## 1 H Me(Et)N NO.sub.2 
165-167 2 
37 
##STR54## 1 H 
##STR55## NO.sub.2 
185-188 2 
38 
##STR56## 1 Me Me.sub.2 N NO.sub.2 
103-104 7 
39 
##STR57## 1 H MeNH NO.sub.2 
170 11 
40 
##STR58## 1 H Me.sub.2 N NO.sub.2 
185-187 2 
41 
##STR59## 1 H MeNH CN 171-173 1 
42 
##STR60## 1 H MeCONH NO.sub.2 
125-126 12 
43 Ph 1 H MeCONH NO.sub.2 
107-109 12 
44 
##STR61## 1 H MeCONH NO.sub.2 
132-133 12 
45 
##STR62## 1 Et MeCONH NO.sub.2 
175-176 12 
46 
##STR63## 1 H Me.sub.2 N NO.sub.2 
(syrup) (h) 
2 
47 
##STR64## 1 H MeNH NO.sub.2 
119-121 11 
48 
##STR65## 1 H MeNH NO.sub.2 
178-180 3 
__________________________________________________________________________ 
(a) .sup.1 HNMR(CDCl.sub.3): 2.87(6H, s), 4.59(4H, s), 7.37(2H, d, J=8Hz) 
7.72(2H, dd, J=8, 2Hz), 8.37(2H, d, J=2Hz). 
(b) .sup.1 HNMR(CDCl.sub.3): 3.00(3H, d, J=4Hz), 4.53(2H, d, J=6Hz), 
6.76(1H, br.s), 7.46(1H, d, J=8Hz), 7.67(1H, dd, J=8, 3Hz), 8.20(1H, d, 
J=3Hz), 8.83(1H, br.s). 
(c) .sup.1 HNMR(CDCl.sub.3): mentioned in Example 8 
(d) .sup.1 HNMR(CDCl.sub.3): mentioned in Example 9 
(e) .sup.1 HNMR(CDCl.sub.3): 1.26(3H, t, J=7Hz), 2.98(3H, d, J=2Hz), 
3.47(2H, q, J=7Hz), 4.70(2H, s), 7.50(1H, s,), 7.96(1H, br.s). 
(f) .sup.1 HNMR(CDCl.sub.3): 3.00(3H, d, J=4Hz), 3.09(3H, s), 4.69(2H, s) 
7.50(1H,s), 8.00(1H, br.s). 
(g) .sup.1 HNMR(CDCl.sub.3): 1.23(6H, t, J=7Hz), 3.46(4H, q, J=7.2Hz), 
4.60(2H, br.s), 7.44(1H, s), 8.30(1H, br.s). 
(h) .sup.1 HNMR(CDCl.sub.3): 3.11(6H, s), 4.42(2H, d, J=6.0Hz), 6.86(1H, 
s), 7.07(1H, t, J=60.0Hz), 7.78(1H, br.t, J=6.0Hz). 
EXAMPLE 13 
An emulsifiable concentrate was prepared by well-mixing 20 wt% of Compound 
No. 1, 75 wt% of xylene and 5 wt% of polyoxyethylene glycol ether (Nonipol 
85.RTM.). 
EXAMPLE 14 
Wettable powders were prepared by well-mixing 30 wt% of Compound No. 6, 5 
wt% of sodium ligninsulfonate, 5 wt% of polyoxyethylene glycol ether 
(Nonipol 85.RTM.). 30 wt% of white carbon and 30 wt% of clay. 
EXAMPLE 15 
A dust was prepared by well mixing 3 wt% of Compound No. 7, 3 wt% of white 
carbon and 94 wt% of clay. 
EXAMPLE 16 
Granules were prepared by thoroughly pulverizing and mixing 10 wt% of 
Compound No. 8, 5 wt% of sodium ligninsulfonate and 85 wt% of clay, 
kneading the mixture with water, granulating and drying the resultant.