Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to a S-mercapto-1,2,3-thiadiazoles
composition having reduced the explosiveness of
S-mercapto-1,2,3-thiadiazoles (1,2,3-thiadiazole-5-
thiols) and a process for preparing the same.
A 5-mercapto-1,2,3-thiadiazole is a chemical material
having a wide application and has an important
application as an intermediate, particularly for
pharmaceuticals, agricultural chemicals and so on.
However, a 5-mercapto-1,2,3-thiadiazole is explosive so
that there is a high possibility that it causes an
unexpected accident during manufacturing, storage and
transportation thereof, and hence it is a compound
accompanied by difficulties in handling thereof.
Therefore, there has conventionally been a disadvantage
that serious attention should necessarily be paid in the
handling thereof and that the compound cannot be used for
various applications with a sense of security.
In view of such circumstances, the present inventors have
made extensive studies for the purpose of reducing
remarkably the explosiveness of a 5-mercapto-1,2,3-
thiadiazole to make its hand:Ling easy and to make itusable for various applications with a sense of security.
As a result, the present inventors have found that the
purpose can be attained by combining a 5-mercapto-
1,2,3-thiadiazole with a specific compound or compounds
and that it can be used without any difficulty for
various applications, for example, for manufacturing
pharmaceuticals and agricultural chemicals, and have
accomplished the present invention.
This invention relates to a 5-mercapto-1,2,3-thiadiazoles
composition having reduced the explosiveness of a
5-mercapto-1,2,3-thiadiazole comprising a 5-mercapto-
1,2,3-thiadiazole combined with (A) one or more compounds
selected from the group consisting of water, an alcohol,
an aromatic hydrocarbon and a halogenated hydrocarbon and
(B) a halide of an alkali metal, and a process for
preparing the same.
In the present specification, the term "5-mercapto-1,2,3-
thiadiazole" includes, needless to say, a 5-mercapto-
1,2,3-thiadiazole and its salt of an alkali metal such as
sodium salt, potassium salt and the like as well as its
hydrate and so on.
The amounts of the compound of (A) and the compound of
(B) to be combined with the 5-mercapto-1,2,3-thiadiazole
may freely be varied depending upon the purpose of use of
the 5-mercapto-1,2,3-thiadia~oleO However, in order to
make a composition which has sufficiently low
explosiveness for the use of many chemical reactions, the
content in the composition of the compound of (A) is
typically 5 to 25 % by weight, preferably 10 to 20 % by
weight, and the content of the compound of (B) is 10 to
30 % by weight, preferably 15 to 25 % by weight. If the
contents of the compound of (A) and the compound of (B)
~2;~8329
are excesslvely hlgh, there sometlmes causes dlfflcultles In
uslng the 5-mercapto-1,2,3-thladlazole for the same appllcatlons
as mentloned above, and If the contents thereof are excesslvely
low, the reductlon of the exploslveness sometImes becomes Insuf-
fIclent. Therefore, It Is deslrable that the contents of thecompound of (A) and the compound of (B) to be comblned wlth the
5-mercapto-1,2,3-thladlazole should be wlthin the range mentloned
above.
In the present Inventlon, there may advantageously be
used a saturated allphatlc alcohol, preferably a lower alcohol
havlng 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol,
n-propyl alcohol, Isopropyl alcohol, n-butyl alcohol, sec-butyl
alcohol, t-butyl alcohol for the alcohol In the compound of (A);
benzene or a lower-alkylbenzene such as toluene, ethylbenzene,
xylene mesltylene for the aromatlc hydrocarbon; and methylene
chlorlde, chloroform, carbon tetrachlorlde and the llke for the
halogenated hydrocarbon. The compound of (A) may be used In
slngle or In comblnatlon of two ~r more klnds thereof. Among the
compounds of (A), water and/or a saturated alIphatlc alcohol may
especlally preferably be used.
As the halIdes of an alkall metal In the compound of
(B), there may advantageously be used In a chlorlde and a bromlde
such as sodlum chlorlde, potasslum chlorlde, sodlum bromlde and
potasslum bromlde. The hallde of an alkall metal may also be
used In slngle or In comblnatlon of two or more klnds thereof,
and among the hallde of an alkall metal, sodlum chlorlde and
potasslum chlorlde may preferably be used.
In the preparatlon of the 5-mercapto-1,2,3-thladlazoles
composltlon accordlng to the present Inventlon, It may be pre-
pared by a method In whlch, a 5-mercapto-1,2,3-thladlazole Is
once Isolated from the manufacturlng step of the 5-mercapto-
1,2,3-thladlazole to obtaln the same followed by comblnlng the
compound of (A) and the compound of (B); and may also be prepared
~,;~3Z9
by a method In whlch the 5-mercapto~ ,2,3-thladlazole Is not Iso-
lated from the manufacturlng step followed by comblnlng the com-
pound of (A) and the compound of (B). The tIme, means and so on
for comblnlng the compound of (A) and the compound of (B) are not
partlcularly llmlted and the 5-mercap~o-1,2,3-thladlazoles compo-
sltlon accordlng to the present Inventlon may be prepared by any
method. Further, the 5-mercapto-1,2,3-thladlazole to be used for
manufacturlng the composltlon accordlng to thls Inventlon may be
any one prepared by any method.
As the method for preparlng the 5-mercapto-1,2,3-thla-
dlazole to be used In the present Inventlon, there may be men-
tloned, for example, a method In whlch a trlhaloacetaldehyde and
a hydrazlne are subJected to condensatlon reactlon In a solvent,
followed by the reactlon of the resultlng reactlon product wlth a
sulfIde, a hydrosulfIde and a comblnatlon of a base and hydrogen
sulflde (see Japanese Unexamlned Patent Publlcatlons No.
95282/1984 and No. 51271/1984); a method and subsequent optlonal
addltlon of a halogen to the resultlng reactlon mlxture (see
Japanese Patent ApplIcatlon No. 167577/1983 publIshed Aprll 5,
1985 under No. 58971/1985) In whlch a trlhaloacetaldehyde and a
carboalkoxyhydrlazlne or a dlthlocarboalkoxyhydrazlne are sub-
Jected to reactlon In a solvent, followed by the reactlon of the
resultlng product wlth a sulflde, a hydrosulflde and a comblna-
tlon of hydrogen sulfIde and a base (see Japanese Patent ApplIca-
tlon No. 157234/1983 publlshed March 22, 1985 under No.
51187/1985); a method dlsclosed In Japanese Unexamlned Patent
PublIcatlon No. 39884/1984; a method dlsclosed In Japanese Unex-
amlned Patent PublIcatlon No. 23974/1978;
1-
~23~8329
and a method disclosed in J. Heterocyclic Chem. 15, 1295
(1978), a method disclosed in Tetrahedron Letters, 26,
2398(1973).
As a concrete example for a method of manufacturing the
5-mercapto-1,2,3-thiadiazoles composition according to
the present invention, there may be mentioned, for
example, a method which comprises mixing a 5-mercapto-
1,2,3-thiadiazole and a halide of an alkali metal of the
compound of (B), subsequently adding an excess amount of
the compound of (A), condensing the mixture to remove the
excess amount of the compound of (A) by evaporation to
dryness. This method, however, is accompanied by danger
of explosion during the operation such as condensation
and evaporation to dryness. Therefore, this method
cannot be said to be quite a good method for
manufacturing the composition according to the present
invention.
Further, there may be mentioned a method in which a
5-mercapto-1,2,3-thiadiazole and the halide of an alkali
metal of (B) are dissolved in the compound of (A); the
resulting solution is concentrated as occasion demands
and then cooled to cause precipitation. According to
this method, however, there is a small disadvantage that
the yield of the composition according to this invention
obtained by the precipitation is low.
Then the present inventors have made extensive studies to
develop a suitable manufacturinq method capable of
producing industrially and advantageously the composition
according to this invention with safety and in high
yield. As the result, present inventors have found that
the composition according to this invention can easily
and advantageously be isolated and obtained with safety
by adding the halide of an alkali metal of (B) to a
~23~
solution containing a 5-mercapto-1,2,3-thiadiazole in the
compound of (A) followed by salting out to precipitate
the present composition according to this invention.
In a preferable and suitable manufacturing method for the
composition according to this in~ention, the solution
containing a 5~mercapto-1,2,3-thiadiazole in the compound
of (~) may be prepared by way of any method. ~or
instance, the composition may be prepared by a method ~
in which the compound of (A) is added to the 5-mercapto-
1,2,3-thiadiazole for dissolution~ However, it is
particularly preferable to prepare the composition by a
method ~ which comprises reacting a trihaloacetaldehyde
with a hydrazine using as a solvent the compound of (A),
preferably water and/or an aliphatic saturated alcohol;
adding a sulfide, hydrosulfide or a base and hydrogen
sulfide to the resulting reaction mixture to cause
cyclization reaction; removing, from the thus obtained
reaction mixture containing a 5-mercapto-1,2,3-
thiadiazole, impurities, for example, an inorganic salt
and the like formed and precipitat~d by side reactions to
obtain a solution containing a 5-mercapto-1,2,3-
thiadiazole in the compound of (A), since there are great
advantages in that the starting material for preparing
the 5-mercapto-1,2,3-thiadiazole has higher chemical
stability and is less expensive as compared with
conventional raw materials for preparing a 5-mercapto-
1,2,3-thiadiazole; the 5-mercapto-1,2,3-thiadiazole can
easily and simply be produced; there is no loss of the
reaction product which loss accompanies the isolation
operation; and the solvent used for manufacturing the
5-mercapto-1,2,3-thiadiazole can effectively be utilized
for the composition according to this invention. Be
noted that the 5-mercapto-1,2,3-thiadiazole obtained by
the above mentioned method ~ is contained in the form of
a salt.
In the above-mentioned method ~, as a trihalo-
acetaldehyde, chloral, chloral hydrate, tribromo-
acetaldehyde, triiodoacetaldehyde and the like are
effective, and among these the trichloroacetaldehydes
such as chloral and chloral hydrate are preferred. As
the hydrazine, are effective a hydrazine compound having
an arylsulfonyl group such as p-toluenesulfohydrazide,
benzenesulfohydrazide, p-xylenesulfohydrazide and the
like; a hydrazine compound having an alkyl sulfonyl group
such as methanesulfohydrazide, ethanesulfohydrazide and
the like; and a hydrazine compound having a nitro-
substituted aryl group such as 2,4-dinitrophenyl-
hydrazine.
The condensation reaction of the trihaloacetaldehyde and
the hydrazine proceeds quantitatively and a trihalo-
acetaldehyde hydrazone compound of the following formula
is produced:
X C-C=N-N
3 1 \
H R
wherein X is a halogen atom in the trihaloacetaldehyde
used; and R is an arylsulfonyl group, and an alkyl-
sulfonyl group, a nitro-substituted aryl group and the
like in the hydrazine used.
Equimolar amounts of the trihaloacetaldehyde and the
hydrazine may be used. However, in order to complete the
reaction, it is preferable to use a slightly excess
amount of the hydrazine, generally around 1.1 molar times
of the amount of trihaloacetaldehyde. The reaction
temperature is between -20 and 50C, preferably between 0
and 10C, and the reaction time is not particularly
limited but it is generally between 0.5 and 3 hours. As
the solvent, the above-mentioned compound of (A) may
-- 8 --
advantageously be employed.
It is preferable that the reaction product obtained by
the condensation reaction of a trihaloacetaldehyde and a
hydrazine in a solvent is subjected to, without isolation
of the reaction product from the reaction mixture, to
cyclization reaction by adding a sulfide salt, a
hydrosulfide salt or a base and hydrogen salfide to the
reaction mixture containing the reaction product, since
the operation can be simplified; there is no loss of the
reaction product accompanying the isolation operation;
and the solvent used in the condensation reaction becomes
as such the solvent for a cyclization reaction to be
utilized as one component for the composition according
to this invention. In the cyclization reaction, in cases
where a sulfide, a hydrosulfide and the like are used, a
base is not particularly needed, the cyclization reaction
(formation of a 5-mercapto-1,2,3-thiadiazole) may be
carried out by adding a base. The reaction temperature
at the time when the cyclization reaction is conducted is
20 not higher than 100C, preferably between -10 and 40C.
Generally the cyclization reaction is completed in 2 to 5
hours and a 5-mercapto-1,2,3-thiadiazole salt is formed.
As the sulfide salt, there may be mentioned a sulfide
salt of an alkali metal and an alkaline earth metal such
as sodium sulfide, potassium sulfide, rubidium sulfide,
A~7 ~ lithium sulfide, calcium sulfide, barrlu~ sulfide,
strontium sulfide, magnesium sulfide and the like,
ammonium sulfide and so on. As the hydrosulfide salt,
there may be mentioned a hydrosulfide salt of an alkali
metal and an alkali earth metal such as sodium
hydrosulfide, potassium hydrosulfide, calcium
hydrosulfide and the like, ammonium hydrosulfide and so
on. The amount of the sulfide salt or the hydrosulfide
salt to be used is typically 1 to 5 moles, preferably 2
to 3 moles per one mole of the reaction product of the
condensation reaction (a trihaloacetaldehyde hydrazone
~.23133Z~
compound). The base is necessarily used when hydrogen
sulfide is us~d. As the base, there may be mentioned an
alkali metal salt such as sodium hydroxide and potassium
hydroxide; a metal alcoholate such as sodium methoxide~
sodium ethoxide, potassium methoxide, potassium ethoxide,
calcium ethoxide and aluminium ethoxide; a metal amide
such as sodium amide, lithium amide, potassium amide and
rubidium amide; an amine compound such as hexamethylene-
tetramine and so on. The base may suitably be used in an
10 amount of 2 to 10 moles, preferably 3 to 5 moles per one
mole of the reaction product obtained by the condensation
reaction.
The amount to be used of the hydrogen sulfide may
suitably be 2 to 15 moles in general, preferably 2.5 to
10 moles per one mole of the reaction product obtained by
the condensation reaction.
When such an impurity as by-product is removed from the
reaction mixture containing a 5-mercapto-1,2,3-
thiadiazole by way of a method known per se such as
filtration, and as occasion demands insolublés are
removed by further condensing to obtain a solution
containing the 5-mercapto-1,2,3-thiadiazole combined with
the compound of (A) can be obtained. A solution
containing a 5-mercapto-1,2,3-thiadiazole in the compound
of (A) which may be more preferably used, can be obtained
when the reaction mixture is treated with an activated
carbon after removal of impurities at the time of
obtaining a solution containing a 5-mercapto-1,2,3-
thiadiazole in the compound of (A) according to the
method ~. The treatment with an activated carbon may be
carried out either before or after concentration. With
respect to a method for preparing a 5-mercapto-1,2,3-
thiadiazole according to the method ~, the present
applicant proposed a process for preparing a 5-mercapto-
~23B329
-- 10 --
1,2,3-thiadiazole in Japanese Unexamined Patent Publica-
tion No. 95282/1984.
In the preferred method for preparing the composition
according to the present invention, it is desirable that
5 the concentration of the solution containing the
5-mercapto-1,2,3-thiadiazole in the compound of tA) may
be adjusted to 3 to 20 % by weight, preferably 5 to 15 %
by weight, since the composition according to this
invention can efficiently be salted out in such a
10 concentration. While the temperature at the time of
salting out by the addition of the halide of an alkali
metal oc (B) may preferably be as low as possible, a
temperature between around 0 and 10C is typically
adopted. And, when an excess amount of a halide of an
15 alkali metal of tB) is added thereto, a preferred
composition according to this invention precipitates.
The composition precipitated by salting out can easily be
isolated and obtained by a method known per se such as
filtration and centrifugal separation. The thus obtained
20 composition is low explosive and can be employed in the
same manner for the application of conventional
5-mercapto-1,2,3-thiadiazoles without any danger. The
thus obtained composition may be washed by the compound
of (A) as occasion demands.
25 The composition according to the present invention may be
prepared by a process which comprises producing a
reaction mixture containing a 5-mercapto-1,2,3-
thiadiazole formed by conventionally known process for
preparing a 5-mercapto-1,2,3-thiadiazole, for instance a
30 method in which chloroacetaldehyde ethoxycarbonyl-
hydrazone is reacted with thionyl chloride followed by
mercaptization (Japanese Unexamined Patent Publication
No. 23974/1978); a method in which diazomethane and
carbon disulfide or its analogue (J. Heterocyclic Chem.,
15 1295 (1978)) and other methods; adding optionally to
the thus obtained reaction mixture the compound of (A)
and/or the halide of an alkali metal of (B); and applying
a general precipitating method, for instance, cooling and
salting out to precipitate the composition according to
this invention. However, in any methods, it is
preferable to prepare the composition by a method which
comprises obtaining a solution containing a 5-mercapto-
1,2,3-thiadiazole in the compound of (A) followed by the
addition of the halide of an alkali metal of (B) to salt
out the composition according to the present invention.
The composition according to the present invention may be
used, for instance, as a raw material for preparing a
cepharosporanic acid derivative (see Japanese Unexamined
Patent Publication No. 59895/1982 corresponding to U.S.
Patent No. 4,399,132 and British Patent No. 2,083,461)
replacing the 5-mercapto-1,2,3-thiadiazole or its salt
per se by the present composition.
Next, Synthesis Examples for preparing 5-mercapto-1,2,3-
thiadiazoles and Examples of the present invention will
be shown below.
In each of the Examples, the hammer-drop sensitivity test
and the rubbins sensitivity test were conducted according
to JIS-K-4810 testing methods.
Synthesis Example 1
After 1 mole (165 g) of chloral hydrate was dissolved in
2 Q of methanol, 1 mole (186 g) of p-toluenesulfo-
hydrazide in the form of powder was added to the
resulting solution under stirring at room temperature
over around 2 minutes, followed by further stirring for 1
hour at room temperature to subject the chloral hydrate
~29
to reaction with the p-toluenesulfohydrazide.
Next, while stirring the resulting reaction mixture
vigorously, 2.2 moles (528 g) of sodium sulfide
nonahydrate was added thereto over around 15 minutes,
followed by further stirring for 3 hours to conduct the
reaction. Since the addition of sodium sulfide caused
generation of heat, the reaction was carried out under
ice-cooling so that the reaction temperature might not be
more than 40C. The color of the reaction mixture was
reddish brown and sodium chloride was precipitated
therein.
After filtration of the precipitated sodium chloride, the
filtrate was concentrated to remove the solvent, and the
crystals precipitated in the concentrate was collected by
filtration followed by recrystallization from a mixed
solvent of methanol and methylene chloride to obtain 70 g
of sodium salt of 5-mercapto-1,2,3-thiadiazole.
Synthesis Example 2
In 200 m~ of methanol was dissolved 16.5 g of chloral
hydrate. To the resulting stirred solution was added, at
around 25C, 18.6 g of p-toluenesulfohydrazide in the
form of powder, followed by further stirring at around
25C for 1 hour to subject the chloral hydrate to
reaction with the p-toluenesulfohydrazine.
After reaction, while the reaction mixture was stirred
vigorously without any isolation of the reaction product,
72.0 g of sodium sulfide nonahydrate was added thereto
over around 15 minutes, followed by further stirring at 1
hour at around 25C for reaction.
Next, after the reaction mixture was cooled to around
~23~33Z9
-5C, 4.8 g of bromine was added thereto and the
temperature was raised gradually followed by stirring at
20C for 40 minutes. The reaction mixture thus stirred
presented reddish brown color, and such inorganic salts
as sodium chloride, potassium chloride and the like
precipitated.
After removal of the precipitated inorganic salt, the
solvent was removed from the reaction mixture by
distillation under reduced pressure. The thus obtained
crude product was recrystallized from a mixed solvent of
water, methanol and methylene chloride to obtain 11.4 g
of sodium salt of 5-mercapto-1,2,3-thiadiazole dihydrate,
of which the yield was 64.7 % based on the amount of the
starting chloral hydrate~
Synthesis Example 3
A reaction was conducted in the same manner as in
Synthesis Example 2, except that 2.2 g of chlorine was
used in place of the bromine in Synthesis Example 2, to
obtain 11.3 g of sodium salt of 5-mercapto-1,2,3-
thiadiazole dihydrate. The yield was 64.2 % based on thestarting chloral hydrate.
Synthesis Example 4
A reaction was conducted in the same manner as in
Synthesis Example 2, except that 10.9 g of methane-
sulfohydrazide was used in place of the p-toluenesulfo-
hydrazide in Synthesis Example 2, to obtain 10.2 g of
sodium salt of 5-mercapto-1,2,3-thiadiazole dihydrate.
The yield was 57.9 % based on the starting chloral
hydrate.
~,2383~
- 14 -
Synthesis Example 5
In 200 mQ of methanol was dissolved 16.5 g of chloral
hydrate. To the stirred solution was added, at around
25C, 15.4 g of carboethoxyhydrazine hydrochloride in the
form of powder, followed by further stirring at around
25C for 1 hour to subject the chloral to reaction with
the carboethoxyhydrazine~
After reaction, while stirring the reaction mixture
vigorously, 60.0 g of sodium sulfide nonahydrate was
added thereto over around 15 minutes followed by further
stirring at around 45C for 1 hour to carry out the
reaction.
In order to control the drastic heat generation, the
reaction was conducted under ice-cooling. The color of
the resuLting reaction mixture was blackish brown, and
sodium chloride was precipitated in the reaction mixture.
After removal of the precipitated-sodium chloride, the
solvent was removed from the reaction system, and the
thus obtained crude product was recrystallized from a
mixed solvent of methanol, water and methylene chloride
to obtain 9.7 g of sodium salt of 5-mercapto-1,2,3-
thiadiazole dihydrate. The yield was 55.1 % based on the
starting chloral hydrate.
Synthesis Example 6
A reaction was conducted in the same manner as in
Synthesis Example 5, except that 28.0 g of K2S was used
in place of the sodium sulfide nonahydrate in Synthesis
Example 5, to obtain 10.2 g of sodium salt of
5-mercapto-1,2,3-thiadiazole dihydrate. The yield was
53.0 ~ based on the starting chloral hydrate.
~2:3~329
- 15 -
Example 1
In 500 mQ of methanol, there were heated under reflux
24.0 g of 5-chloro-1,2,3-thiadiazole and 48.0 g of sodium
sulfide (Na2S-9H2O) to obtain a reaction mixture
containing 20.0 g of sodium salt of 5-mercapto-1,2,3-
thiadiazole.
From the thus o~tained reaction mixture were removed, by
filtration, the by-produced precipitate of sodium
chloride and the unreacted sodium sulfide; the reaction
mixture was further treated with an activated carbon; and
then concentrated to 100 mQ.
After filtration of the precipitated inorganic salt, 50 mQ
of water was added to the reaction mixture, and the
water-methanol solution containing sodium salt of
5-mercapto-1,2,3-thiadiazole was cooled to 5C followed
by the addition of 14.9 g of sodium chloride. Upon
filtration of the produced precipitate, it was found that
the precipitate was a composition containing 22.6 g (70%
by weight) of sodium salt of 5-mercapto-1,2,3-thiadiazole
dihydrate, 4.9 g (15 % by weight) of methanol and water
and 4.9 g (15 % by weight) of sodium chloride.
In order to know the extent of the explosiveness of the
thus obtained composition, the hammer-drop sensitivity
test and the rubbing sensitivity test were conducted with
respect to the composition according to this invention
and the single compound of sodium salt of 5-mercapto-
1,2,3-thiadiazole dihydrate. The results are shown in
Table 1.
Example 2
In 2 Q of methanol was dissolved 1 mole (165 g) of
123~13Z9
- 16 -
chloral hydrate. To the resulting solution under
stirring was added 1 mole (186 g) of p-toluenesulfo-
hydrazide in the form of powder at roo~ temperature over
around 2 minutes followed by further stirring at room
temperature for one hour to subject the chloral hydrate
and the p-toluenesulfohydrazide to reaction.
Next, with vigorous stirring of the reaction mixture, 2.2
mole (528 g) of sodium sulfide nonahydrate was added
thereto over around 15 minutes and then the stirring was
continued for further 3 hours to carry out the reaction.
Since the addition of sodium sulfide caused generation of
heat, the reaction system was subjected to reaction under
ice-cooling so that the reaction temperature during the
reaction might not exceed 40C. The thus obtained
reaction mixture colored reddish brown and sodium
chloride was precipitated in the reaction mixture.
After removal of the ~-rc~Patet sodium chloride by
filtration, the reaction mixture was concentrated and
filtered again to obtain a filtrate. To the filtrate was
added S00 mQ of an aqueous methanolic solution having a
concentration of 6 % by weight of methanol to obtain 880
mQ of a solution having a concentration of 10 % by weight
of sodium salt of 5-mercapto-1,2,3-thiadiazole. Next,
the solution was treated with an activated carbon, cooled
to 5C followed by addition thereto of 303 g of sodium
chloride. Upon collection by filtration of the
precipitate, 114.0 g of a composition consisting of 77.0
g t67 % by weight) of sodium salt of 5-mercapto-1,2,3-
thiadiazole dihydrate, 17.0 g (15 % by weight) of sodium
chloride and 20.0 g (18 % by weight) of methanol and
water.
The results of the hammer-drop sensitivity test and the
rubbing test are shown in Table 1.
~.23B329
Example 3
In 200 mQ of a mixed solution of isopropyl alcohol and
water (the content of isopropyl alcohol: 5 % by weight)
was dissolved 20.0 g of sodium salt of 5-mercapto-1,2,3-
thiadiazole dihydrate at 30C. While cooling the thus
obtained solution at 3C, 69.1 g of sodium chloride was
added. Upon addition of the sodium chloride, precipitate
was formed which was collected by filtration. It was
found that the precipitate is a composition consisting of
17.0 g (70 % by weight) of sodium salt of 5-mercapto-
10 1,2,3-thiadiazole dihydrate, 3.16 g (13 % by weight) of
isopropyl alcohol and water and 4.13 g (17 % by weight)
of sodium chloride.
The results of the hammmer-drop sensitivity test and the
rubbing sensitivity test are shown in Table 1.
Example 4
An experiment was run in the same manner as in Example 3
except that 55.5 g of potassium chloride was used in
place of the sodium chloride in Example 3 and 200 mQ of a
mixed solution of ethyl alcohol and water (the content of
the ethyl alcohol: 5 ~ by weight) in place of the mixed
solution of isopropyl alcohol and water to obtain a
composition (27.6 g) consisting of 18.0 g (65.0 % by
weight) of sodium salt of 5-mercapto-1,2,3-thiadiazole,
4.1 g (15 % by weight) of ethyl alcohol and water and 5.5
g (20 ~ by weight) of potassium chloride.
The results of the hammer-drop sensitivity test and the
rubbing sensitivity test are shown in Table 1.
~23~29
-- 18 --
_
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-- 19 --
Example 5
In 2 Q of methanol was dissolved 1 mole (165 g) of
chloral hydrate. To the resulting solution with stirring
was added 1 mole (186 g) of p-toluenesulfohydrazide in
the rorm of powder at room temperature over around 2
minutes, and the mixture was further stirred at room
temperature for 1 hour to subject the chloral hydrate and
the p-toluenesulfohydrazide to reaction. Next, while
stirring vigorously the reaction mixture, a solution of
2.2 mole (242 g) of potassium sulfide in 400 mQ of water
was added thereto over around 15 minutes and then the
stirring was continued for further 2 hours to carry out
the reaction. Since the addition of potassium sulfide
caused generation of heat, the reaction was carried out
under ice-cooling so that the reaction temperature might
not exceed 40C. After reaction, potassium chloride
precipitated and the resultant precipitate was collected
by filtration and treated in the same manner as in
Example 2 to obtain 126 g of a composition consisting of
86 g (68 % by weight) of potassium salt of 5-mercapto-
1,2,3-thiadiazole dihydrate, 21 g (17 % by weight) of
sodium chloride and 19 g (15 ~ by weight) of methanol and
water. The results of hammer-drop sensitivity test and
the rubbing sensitivity test are shown in Table 2.
Example 6
In 2 Q of methanol was dissolved 1 mole (146 g) of
chloral. To the stirred resulting solution was added 1
mole (186 g~ of p-toluenesulfohydrazide in the form of
powder at room temperature over around 5 minutes followed
30 by further stirring at room temperature for 1 hour to
subject the chloral and the p-toluenesulfohydrazide to
reaction. Next, with vigorous stirring of the resultant
reaction mixture, 2.2 moles (172 g) of powdery anhydrous
~ 20 -
sodium sulfide prepared from hydrogen sulfide and sodium
metho~ide was added thereto over around 5 minutes
followed by stirring for further 2 hours to carry out the
reaction. The reaction was carried out under ice-cooling
so that the reaction temperature during the reaction
might not exceed 40C. The precipitated sodium chloride
in the reaction mixture was removed by filtration and the
reaction mixture was concentrated to 600 mQ. Filtration
was carried out again to remove the precipitate and the
obtained reaction mixture was treated with an activated
carbon followed by cooling at 10C and the addition of 28
g of sodium chloride. The formed precipitate was removed
by filtration, the precipitate was washed with n-butyl
alcohol to obtain 90 g of a composition consisting 63 g
(70 ~ by weight) of 5-mercapto-1,2,3-thiadiazole sodium
salt, 18 g (20 % by weight) of sodium chloride and 9 g
(10 % by weight) of n-butyl alcohol. The results of the
hammer-drop sensitivity test and the rubbing sensitivity
test are shown in Table 2.
Example 7
After 10 g of potassium salt of 5-mercapto-1,2,3-
thiadiazole was dissolved in 400 m~ of isopropyl alcohol
at 30C, 2.6 g of sodium chloride was added to the
resultant solution while cooling at 5C. The formed
precipitate was filtered to obtain 12.4 g of a
composition consisiting of 8.5 g (69 % by weight) of
potassium salt of 5-mercapto-1,2,3-thiadiazole, 2.5 g (20
~ by weight) of sodium chloride and 1.4 g (11 % by
weight) of isopropyl alcohol. The results of the
hammer-drop sensitivity test and the rubbing sensitivity
test for the present composition are shown in Table 2.
Z~
- 21 -
Example 8
After 10.0 g of 5-mercapto-1,2,3-thiadiazole dihydrate
was dissolved in 50 mQ of water at room temperature, 28.1
g of potassium bromide was added thereto while cooling to
S 0C. The formed precipate was filtered to obtain 7.6 g
of a composition consisting of 5.0 g (66 % by weight) of
5-mercapto-1,2,3-thiadiazole dihydrate, 1.4 g (18 ~ by
weight) of potassium bromide and 1.2 g (16 ~ by weight)
of water. The results of the hammer-drop sensitivity
test and the rubbing sensitivity test for the present
composition are shown in Table 2.
Example 9
After 5.0 g of sodium salt of 5-mercapto-1,2,3-
thiadiazole dihydrate was dissolved in 170 m~ of methanol
at room temperature, 3.4 g of sodium chloride was added
thereto while cooling the mixture at 5C. The formed
precipitate was filtered and washed with 50 ~
methanol-toluene solution to obtain 6.5 g of a
composition consisting of 4.5 g (67 % by weight) of
sodium salt of 5-mercapto-1,2,3-thiadiazole dihydrate,
1.0 g (15 % by weight) of sodium chloride and 1.2 g (18 %
by weight) of methanol and toluene. The results of the
hammer-drop sensitivity test and the rubbing sensitivity
test for the present composition are shown in Table 2.
Example 10
An experiment was run in the same manner as in Example 9
except that a 50 ~ methanol-carbon tetrachloride solution
was used for washing in place of the 50 % methanol-
toluene solution to obtain 6.1 g of a composition
consisting of 4.3 g (70 ~ by weight) of sodium salt of
5-mercapto-1,2,3-thiadiazole dihydrate, 1.2 g (20 % by
Z9
- 22 -
weight) of sodium chloride and 0.6 g (10 % by weight) of
methanol and carbon tetrachloride. The results of the
hammer-drop sensitivity test and the rUbbing sensitivity
test for the present composition are shown in Table 2.
~2383,Z~
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- 24 -
Example ll
In a lO0 mQ of a mixed solvent of isopropyl alcohol and
water (content o~ isopropyl alcohol: 5 % by weight) was
dissolved, at 30C, 10 g of sodium salt of 5-mercapto-
1,2,3-thiadiazole obtained by Synthesis Example 2. While
cooling the resulting solution to 3C, there was added
thereto 35 g of sodium chlorlde. Upon addition of the
sodium chloride, there was formed a precipitation which
was then collected by filtration to afford 12.1 g of a
composition consisting of 8.5 g (70 % by weight) of
sodium salt of 5-mercapto-1,2,3-thiadiazole dihydrate,
1. 6 g ( 13 % by weight) of isopropyl alcohol and water,
and 2.0 g t17 % by weight) of sodium chloride.
Example 12
In a 200 mQ of a mi~ed solvent of isopropyl alcohol and
water (content of isopropyl alcohol: 5 % by weight) was
dissolved, at 30C, 20 g of sodium salt of 5-mercapto-
1,2,3-thiadiazole obtained by Synthesis Example 5. While
cooling the resulting solution to 3C, there was added
thereto 69 g of sodium chloride. Upon addition of the
sodium chloride, there was formed a precipitation which
was then collected by filtration to afford 24~3 g of a
composition consisting of 17.0 g (70 ~ by weight) of
sodium salt of 5-mercapto-1,2,3-thiadiazole dihydrate,
3.2 g tl3 % by weight) of isopropyl alcohol and water,
and 4.1 g ~17 % by weight) of sodium chloride.
