JP3430786B2 - 1-amino-1,2,3-triazole derivative, method for producing the same, and gas generating agent containing the compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 1-amino-1,2,3-triazole derivative useful as a gas generating agent.

[0002]

2. Description of the Related Art At present, a gas generating agent containing sodium azide as a main component is mainly used for an inflator (gas generating device) of an air bag for an automobile. Since sodium azide has a high thermal decomposition temperature of 400 ° C. or higher, it is excellent in thermal stability, and when decomposed, a large amount of nitrogen gas is instantaneously generated. Therefore, sodium azide is preferable as a gas generating agent. However, sodium azide is a compound with many problems in its use, such as being highly toxic and forming an unstable explosive substance in contact with heavy metals. Under such circumstances, a gas generating agent having high gas generating efficiency, which does not use sodium azide, has been earnestly desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a gas generating agent having a high gas generating efficiency, which does not use a compound such as sodium azide, which is highly toxic and may generate an explosive substance. This is an issue.

[0004]

The object of the present invention is to provide a 1-amino-1,2,3-triazole derivative represented by the following structural formula,

[0005]

[Chemical 2] (In the formula, X is a hydrogen atom, a -COOR group or -COCOO.
Represents a R group, and Y represents a -COOR group or a -COCCOOR group. However, R represents an alkyl group. ), A method for producing the same, and a gas generating agent containing the compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION 1-Amino-1,2,3 of the present invention
-The triazole derivative is a novel compound represented by the above structural formula. In this structural formula, X is a hydrogen atom,
Represents a COOR group or a -COCOOR group, and Y represents -COO
It represents an R group or a -COCOOR group. However, R represents an alkyl group, particularly an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the above-COOR group (alkoxycarbonyl group) include alkoxycarbonyl groups having an alkyl group having 1 to 5 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and butoxycarbonyl group. Examples of the -COCOOR group (alkoxyoxalyl group) include an alkoxyoxalyl group having an alkyl group having 1 to 5 carbon atoms such as a methoxallyl group, an ethoxallyl group, a propoxallyl group, and a butoxaryl group.

Examples of the 1-amino-1,2,3-triazole derivative of the present invention include 1-methoxallylamino-1,2,3-triazole and 1-ethoxalylamino-1,2,3-triazole. 1-alkoxyoxalylamino-1,2,3-triazole, 1-bis (methoxycarbonyl) amino-1,2,3-triazole, 1-bis (ethoxycarbonyl) amino-1,
1-bis (alkoxycarbonyl) amino-1,2,3-triazole such as 2,3-triazole, 1-methoxycarbonylamino-1,2,3-triazole, 1
1-alkoxycarbonylamino-1,2,3-such as ethoxycarbonylamino-1,2,3-triazole
Triazole is preferred.

These compounds are 1-amino-1,2,
It is easily produced from 3-triazole as a raw material as follows. In addition, 1-amino-1,2,3-triazole is a method of reacting 1H-1,2,3-triazole with hydroxylamine-O-sodium sulfonate in the presence of potassium hydroxide [J. Org. Chem. US
SR (Engl. Transl.), 28 (199
2), 1042] or 1H-1,2,3-triazole with hydroxylamine-O-sulfonic acid in the presence of potassium carbonate [WO 9200981].

The above-mentioned 1-alkoxyoxalylamino-
1,2,3-triazole is 1-amino-1,2,3
Can be obtained by reacting a triazole with an alkyloxalyl halide. Examples of the halogenated alkyloxalyl include alkyloxalyl chloride having an alkoxy group having 1 to 5 carbon atoms such as methyloxalyl chloride and ethyloxalyl chloride.

The reaction of 1-amino-1,2,3-triazole with alkyl oxalyl halide is usually carried out in the presence of a solvent inert to the reaction such as acetonitrile and tetrahydrofuran, usually at -30 to 50 ° C, preferably at -10 to 3
It is carried out at a temperature of 0 ° C. and normal pressure. At this time, the halogenated alkyloxalyl is usually used in an amount of 0.5 to 10 times, preferably 0.5 to 5 times the mol of 1-amino-1,2,3-triazole. The 1-alkoxyoxalylamino-1,2,3-triazole thus produced is separated and purified by a usual method such as extraction and recrystallization.

The above-mentioned 1-bis (alkoxycarbonyl)
Amino-1,2,3-triazole is 1-amino-
It can be obtained by reacting 1,2,3-triazole with a haloformate ester. As the haloformate, a chloroformate having an alkoxy group having 1 to 5 carbon atoms such as methyl chloroformate, ethyl chloroformate, propyl chloroformate and butyl chloroformate is used.

The reaction of 1-amino-1,2,3-triazole with a haloformate is usually carried out in the presence of a solvent inert to the reaction such as acetonitrile, tetrahydrofuran or the like, usually at -30 to 50 ° C, preferably at -0. It is carried out at a temperature of 10 to 30 ° C. under normal pressure. At this time, the haloformate is usually used in an amount of 1 to 10 times, preferably 1 to 5 times the mol of 1-amino-1,2,3-triazole. In order to accelerate the reaction, alkali such as alkali metal carbonates (sodium carbonate, potassium carbonate, etc.) and alkali metal hydrogencarbonates (sodium hydrogencarbonate, potassium hydrogencarbonate, etc.) are added to 1-amino-1,2-amino-1,2- It is preferable to add 1- to 10-fold molar amount of 1,3-triazole to the reaction system. The produced 1-bis (alkoxycarbonyl) amino-1,2,3-triazole is separated and separated by a usual method such as extraction, distillation and chromatography.
Refined.

The above-mentioned 1-alkoxycarbonylamino-
1,2,3-triazole is 1-bis (alkoxycarbonyl) amino-1,2,2 obtained as described above.
It can be obtained by heating 3-triazole in the presence of a protic organic solvent and activated carbon.

In this heat treatment, as described above, 1-amino-1,2,3-triazole is reacted with a haloformate ester to prepare 1-bis (alkoxycarbonyl) amino-1,
After generating 2,3-triazole, for example, the product obtained by distilling off the solvent (1-bis (alkoxycarbonyl) amino-1,2,3-triazole) is used as a protic organic solvent (methanol, ethanol). 1 to 5 carbon atoms
1-bis (alkoxycarbonyl) amino-1,2,
It is carried out by adding about 10 mg to 1 g to 1 g of 3-triazole and heating under reflux for 0.5 to 10 hours. The heating reflux is usually performed under normal pressure. At this time, it is preferable to use an alcohol having the same alkoxy group as the haloformic acid ester, and the activated carbon is preferably a powder. The 1-alkoxycarbonylamino-1,2,3-triazole thus produced is separated and purified by a usual method such as distillation or chromatography.

The gas generating agent of the present invention is 1-amino-1,
It is characterized by containing a 2,3-triazole derivative as a gas generating base. According to the present invention, 1-amino-
A gas generating agent containing a 1,2,3-triazole derivative as a gas generating base and also containing an inorganic oxidizing agent can be constituted.

The gas generating agent of the present invention may contain at least one known gas generating agent other than the 1-amino-1,2,3-triazole derivative as the gas generating agent. For example, a guanidine compound such as guanidine nitrate, aminoguanidine nitrate, diaminoguanidine nitrate, an amine compound such as ethylenediamine dinitrate, hexamethylenetetramine dinitrate, a known tetrazole compound or a known triazole compound may be contained as a gas generating base. Good. The shape and particle size of the gas generating base are not particularly limited, but normally finely pulverized one is preferable.

As the inorganic oxidant, a known inorganic oxidant contained in the gas generating agent can be used.
At least one oxidizing agent selected from oxohalogenates and nitrates is used. Examples of oxohalogenates include alkali metal perchlorates such as potassium perchlorate and sodium perchlorate, alkali metal chlorates such as potassium chlorate and sodium chlorate, and ammonium perchlorate. Examples of the nitrate include potassium nitrate, nitrates of alkali metals such as sodium nitrate, and
Nitrate of alkaline earth metal such as strontium nitrate,
Ammonium nitrate etc. are mentioned. Among these oxidizing agents, perchlorates and nitrates are preferable, and alkali metal salts thereof are particularly preferable, and potassium perchlorate is further preferable.
Potassium nitrate is preferred.

Transition metal oxides can also be used as the inorganic oxidant. Examples of the transition metal oxide include ferric oxide, cupric oxide, zinc oxide, chromium oxide, molybdenum oxide, tungsten oxide, cobalt oxide, nickel oxide and the like. The shape and particle size of the oxidizing agent are not particularly limited, but normally finely crushed ones are preferable.

The mixing ratio of the gas generating base and the inorganic oxidizing agent is
A stoichiometric amount that can completely burn the gas generating base material based on the oxygen amount may be used, but a suitable ratio is selected according to the combustion temperature, the combustion gas composition, and the like. For example, 20 to 400 parts by weight, preferably 30 to 200 parts by weight, of the inorganic oxidizer is mixed with 100 parts by weight of the gas generating base.

The gas generating agent can be used as a powdery mixture of a gas generating base and an inorganic oxidizing agent, or can be used as a molded body by adding a binder and compressing / molding. The binder is not particularly limited, and a general organic or inorganic binder is used in an amount of 10% by weight or less, preferably about 0.2 to 5% by weight. Examples of the organic binder include polycarbonate, nitrocellulose, polysaccharides, polyvinylpyrrolidone, and the like, and examples of the inorganic binder include molybdenum disulfide, graphite, sodium silicate, talc, bentonite, montmorillonite, and the like. The gas generating agent of the present invention described above can be preferably used in an inflator (gas generating device) of an automobile-mounted airbag.

[0022]

EXAMPLES Next, the 1-amino-1,2,3-triazole derivative of the present invention and the gas generating agent containing the same will be specifically described with reference to Examples. The yield (mol%)
Was determined on the basis of 1-amino-1,2,3-triazole.

Example 1 [Production of 1-methoxallylamino-1,2,3-triazole] 1-amino-1,2,3-triazole 1.0
Acetonitrile 5 in which g (11.89 mmol) was dissolved
To 0 ml of methyl oxalyl chloride under stirring at 0 ° C.
5 g (11.82 mmol) was added dropwise. This solution was stirred at the same temperature for 1 hour, 100 ml of ethyl acetate was added, and saturated aqueous sodium hydrogen carbonate was added until the precipitated solid was dissolved. The above operation was performed in an argon stream under normal pressure.
Then, the organic layer and the aqueous layer were separated, the pH of the aqueous layer was adjusted to 2.3 with 6N hydrochloric acid, and the aqueous layer was extracted twice with 200 ml of ethyl acetate. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure to obtain 1.17 g of the desired product (yield: 58%).

The physical properties are shown below. [Melting Point] 140 to 145 ° C. [ ¹ H-NMR] (DMSO-d ⁶ ) δ: 3.885 (3H, s), 7.873 (1H, d,
J = 0.97), 8.284 (1H, d, J = 0.9
7), 13.261 (1H, brs) [Elemental analysis] (as C ₅ H ₆ N ₄ O ₃ ) Theoretical value: C 35.30%, H 3.55%, N 3
2.93% Found: C 35.28%, H 3.55%, N 3.
3.20%

Example 2 [1-bis (methoxycarbonyl) amino-1,2,3
-Production of triazole] 150 g of acetonitrile in which 4.2 g (0.05 mol) of 1-amino-1,2,3-triazole was dissolved, and potassium carbonate 27.
6 g (0.2 mol) was added. In this solution, with stirring,
Under the same temperature, 18.9 g (0.2 mo of methyl chloroformate)
After 50 ml of acetonitrile mixed with 1) was added dropwise and stirred for 2 hours, the mixture was further stirred at room temperature for 2 hours. The above operation was performed in an argon stream under normal pressure. Then, the insoluble matter was filtered off, 100 ml of water was added, and then 300 ml of ethyl acetate was added.
Extracted with ml. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure to obtain 6.5 g of the desired product (yield: 65%).

The physical properties are shown below. [Melting point] 149 to 151 ° C [ ¹ H-NMR] (CDCl ₃ ) δ: 3.882 (6H, s), 7.691 (1H, d,
J = 0.98), 7.795 (1H, d, J = 0.9
8) [Elemental analysis] (as C ₆ H ₈ N ₄ O ₄ ) Theoretical value: C 36.01%, H 4.03%, N 2
7.99% Found: C 35.86%, H 4.01%, N 2.
8.05%

Example 3 [Production of 1-methoxycarbonylamino-1,2,3-triazole] 1-bis (methoxycarbonyl) amino-1,2,3-triazole 10 obtained in the same manner as in Example 2 0.9 g was dissolved in methanol, 0.3 g of activated carbon was added thereto, and the mixture was heated and refluxed for 2 hours in an argon stream under normal pressure. Next, the activated carbon was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 4) to obtain 4.9 g of the desired product. (Yield:
63%).

The physical properties are shown below. [Melting point] 83 to 86 ° C. [ ¹ H-NMR] (CDCl ₃ ) δ: 3.809 (3 H, s), 7.688 (1 H,
s), 7.691 (1H, s), 9.704 (1H, b
rs) [Elemental analysis] (as C ₄ H ₆ N ₄ O ₂ ) Theoretical value: C 33.81%, H 4.26%, N 3
9.42% Found: C 33.62%, H 4.23%, N 3.
8.41%

Example 4 [Deflagration test of 1-methoxallylamino-1,2,3-triazole] 1-methoxallylamino-1,2,3-triazole obtained in Example 3 (gas generating base material) ) And potassium perchlorate (oxidizing agent) are uniformly mixed so that the compounding ratio (weight ratio of the gas generating base material to the oxidizing agent) is 32.9: 67.1, and then a tablet molding machine is used. A 6 mmφ tablet was molded and used as a gas generant sample. When 0.50 g of the obtained gas generant sample was placed in a small deflagration test apparatus (see Disaster Research, Vol. 26, pp. 231-245) with an internal volume of 13 ml, it was hermetically sealed and ignited. The maximum pressure and the maximum pressure generation rate were measured. As a result, the maximum pressure generation rate (Pmax) was 7.0 MPa, and the maximum pressure generation rate ((dP / dt) max) was 8.8 × 10 MPa.
Was / s.

Example 5 [1-bis (methoxycarbonyl) amino-1,2,3
-Deflagration test of triazole] 1-obtained in Example 2
The compounding ratio of bis (methoxycarbonyl) amino-1,2,3-triazole (gas generating base) and potassium perchlorate (oxidizing agent) (weight ratio of gas generating base to oxidizing agent) is 32.5: After uniformly mixing so as to be 67.5, it was molded into a 6 mmφ tablet using a tablet molding machine, and this was used as a gas generant sample. The obtained gas generant sample 0.
A deflagration test was conducted in the same manner as in Example 4 using 50 g.
As a result, the maximum generated pressure (Pmax) is 4.9 MPa
And the maximum pressure generation rate ((dP / dt) max) is 3.
It was 5 × 10 MPa / s.

Example 6 [Deflagration test of 1-methoxycarbonylamino-1,2,3-triazole] 1-methoxycarbonylamino-1,2,3-triazole obtained in Example 1 (gas-generating base material) ) And potassium perchlorate (oxidizing agent) in a mixing ratio (weight ratio of the gas generating base material to the oxidizing agent) of 31.3: 6.
After uniformly mixing the mixture to 8.7, it was molded into a 6 mmφ tablet using a tablet molding machine, which was used as a gas generant sample. A deflagration test was conducted in the same manner as in Example 4 using 0.50 g of the obtained gas generant sample. As a result, the maximum generated pressure (Pmax) was 5.4 MPa and the maximum pressure generation rate ((dP / dt) max) was 5.4 × 10 MPa / s.

Comparative Example 1 As a gas generating agent sample, a gas generating agent (AS) containing sodium azide as a gas generating base and potassium nitrate as an oxidizing agent was used.
-82: manufactured by Nippon Kayaku Co., Ltd.) A deflagration test was conducted in the same manner as in Example 4 except that 0.5 g was used. As a result, the maximum generated pressure (Pmax) was 5.1 MPa and the maximum pressure generation rate ((dP / dt) max) was 6.8 × 10 MPa / s. The results of Examples 4 to 6 and Comparative Example are shown in Table 1.

[0033]

[Table 1]

[0034]

INDUSTRIAL APPLICABILITY The 1-amino-1,2,3-triazole derivative of the present invention is a compound having high gas generation efficiency and excellent properties as a gas generating base. Among the 1-amino-1,2,3-triazole derivatives of the present invention, 1-alkoxyoxalylamino-1,2,3-triazole such as 1-methoxalylamino-1,2,3-triazole is azide. It has a higher gas generation efficiency than sodium and is an excellent gas generation base. Since the compound of the present invention has excellent properties as a gas generating base, the present invention can provide a gas generating agent having higher gas generation efficiency and safer than conventional gas generating agents using sodium azide. it can. The gas generating agent of the present invention can be used not only as an airbag for automobiles but also as an airbag for ships and aircrafts.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Furuya 5 1978, Kogushi, Ube City, Yamaguchi Prefecture, Ube Institute of Industrial Manufacturing, Ube Laboratory (56) Reference JP-A-5-213687 (JP, A) 4-265292 (JP, A) JP-A 5-117070 (JP, A) JP-A 7-206569 (JP, A) JP-A 8-333353 (JP, A) Special Table 8-500813 (JP , A) Patent 3178336 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 249/04 C06D 5/00 C06B 43/00 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A 1-amino- having the following structural formula:
1,2,3-triazole derivative. [Chemical 1] (In the formula, X is a hydrogen atom, a -COOR group or -COCOO.
Represents a R group, and Y represents a -COOR group or a -COCOOR group. However, R represents an alkyl group. ) 2. 1-amino-1,2,3 according to claim 1.
-A gas generant characterized by containing a triazole derivative. 3. 1-alkoxyoxalylamino-1,
A gas generating agent containing 2,3-triazole. 4. A gas generating agent containing 1-bis (alkoxycarbonyl) amino-1,2,3-triazole. 5. 1-Alkoxycarbonylamino-1,
A gas generating agent containing 2,3-triazole. 6. A 1-alkoxyoxalylamino-1,2,3, characterized in that 1-amino-1,2,3-triazole is reacted with an alkyloxalyl halide.
-Method for producing triazole. 7. A 1-amino-1,2,3-triazole is reacted with a haloformate ester.
Process for producing bis (alkoxycarbonyl) amino-1,2,3-triazole. 8. A 1-alkoxycarbonylamino-1,2,3, characterized in that 1-bis (alkoxycarbonyl) amino-1,2,3-triazole is heated in the presence of a protic organic solvent and activated carbon. -Method for producing triazole.