JPH08333353A - New tetrazole compound - Google Patents

Abstract

PURPOSE: To obtain a new inexpensive tetrazole compound causing an atoxic and odorless decomposition gas, having low friction sensitivity, low drop hammer sensitivity, etc., being safe, sensitively decomposing only by temperature, generat ing a clean gas, useful as a blowing agent, a smoking agent, etc. CONSTITUTION: This tetrazole derivative is shown by formula I [R is CH3 (CH2 )n , ((n) is 3-10 and 12, 14, 15, 16), (CH2m ((m) is 2-8), cyclopropyl, cyclohexyl, etc.] such as N-[1H-tetrazol-5-yl]-N-valeramide of formula II. The compound of formula I is readily and inexpensively synthesized by modifying the amino group at the 5-position of 5-aminotetrazole with an alkyl, allyl or an aryl. In the reaction, an acid anhydride or an organic acid chloride is preferably used as a reaction agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a foaming agent for precision molding of resin or weight reduction of molded products, an inflator for airbags as a safety device for automobiles, or pesticides such as insecticides and bactericides. The present invention relates to a novel tetrazole derivative used as a smoke agent for efficiently diffusing agents such as stain agents and fragrance agents.

[0002]

2. Description of the Related Art Generally, crystalline resin naturally undergoes crystallization in the cooling process after molding and shrinks, so that it is difficult to obtain a molded product as a mold. Experience has avoided apparent contraction. However, complete precision molding is extremely difficult with the conventional methods as described above, and therefore, a gas is physically blown into the core of the molded article to prevent the above-mentioned shrinkage.
-41264, JP-A-53-12864, JP-A-5
6-61435, USP 4871861) or the use of expensive chemical blowing agents has been proposed (JP-A-50).
No. 129563, JP-A No. 53-12864, JP-A No. 56-61435, and US Pat. No. 4,871,861). Further, conventionally, there has been no excellent foaming agent for a high melting point thermoplastic resin, and therefore, there has been no high quality foamed molded product. Further, as an automobile safety device, the conventional inflation for airbags has been
Conventionally, soda azide has been mainly used for the water heater.

[0003]

The soda azide used as a gas generating agent has a problem that it is highly toxic. As a countermeasure against this, conventionally, as a tetrazole-based gas generating agent (JP-A-46-906, DE2150465).
JP-A-49-87583, JP-A-50-7559
No. 2, JP-A-57-123885, JP-A-57-12
3886, JP-A-2-225159, JP-A2-1
84590, USP4948439, JP-A 2-2
21179, JP-A-2-225389, USP50
No. 35757). However, these described tetrazole-based gas generating agents have problems such as sublimation at low temperature or high physical sensitivity such as friction sensitivity, and lack of safety when used on work or in an apparatus. All of the conventional tetrazole gas generating agents have a problem in that they are expensive as compared with chemical soda. Further, it is an essential requirement that the smoke agent is harmless to humans and animals and is odorless, but there is a problem that it is difficult to say that the smoke agent currently used satisfies these essential requirements. INDUSTRIAL APPLICABILITY The present invention is that the decomposed gas is non-toxic, has no odor, has low physical sensitivity such as friction sensitivity and drop hammer sensitivity, is safe for use, sensitively decomposes only by temperature to generate clean gas, and is inexpensive and novel The purpose is to develop a novel tetrazole derivative.

[0004]

The first aspect of the present invention relates to a novel tetrazole derivative in which the amino group at the 5-position of 5-aminotetrazole represented by the general formula of the following [Chemical formula 1] is derived by an acid bond. It is a thing.

[0005]

[Chemical 1]

The second is the novel tetrazo-form described in the first.
It is a gas generating agent using a derivative.

The third is the novel tetrazo-form described in the first.
The present invention relates to a gas generating agent used as a foaming agent for resin moldings, an inflator for airbags as a safety device for automobiles, or a smoke agent for efficiently diffusing chemicals.

All the novel tetrazole derivatives of the present invention are comprehensively described by the general formula of [Chemical Formula 1]. Therefore, in terms of chemical structure, as shown by the general formula of [Chemical Formula 1], R is different, but the characteristics of chemical structure are the same, and the same effect can be obtained by using it as a foaming agent or smoke agent. It plays.

The tetrazole derivative of the present invention can be synthesized by modifying the 5-position amino group of 5-aminotetrazole with an alkyl group, an allyl group or an aryl group in order to inexpensively produce them. Thus, a novel tetrazole derivative having a performance as a gas generating agent of 5-aminotetrazole or more can be easily and inexpensively synthesized. In order to easily and inexpensively synthesize the tetrazole derivative of the present invention, an amide bond using an acid anhydride or an organic acid chloride as a reaction reagent was selected.

Examples of the reaction agent of the present invention include valeric acid chloride, caproic acid chloride, hebutanoic acid chloride,
Octanoic acid chloride, nonanoic acid chloride, decanoic acid chloride, undecanoic acid chloride, dodecanoic acid chloride, myristic acid chloride, palmitic acid chloride, heptadecanoic acid chloride or stearic acid chloride, and acid chlorides having two substituents include, for example, succine. Examples include acid chloride, glutaric acid chloride, adipic acid dichloride, pimelic acid chloride, suberic acid chloride, azelaic acid chloride and sebacic acid chloride. Examples of aromatic compounds include benzoyl chloride, phenylaceto chloride, phenylpropionic acid chloride, phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride, trimellitic acid chloride, isonicotinic acid chloride, and cyclopropanoic acid chloride. And acid chlorides of saturated ring compounds such as cyclohexanoic acid chloride.

The method for synthesizing the tetrazole derivative of the present invention is a conventional method, and a typical synthetic method is as follows. That is, in the reaction with an organic acid anhydride, the organic acid anhydride is used in a large excess as a solvent and a raw material, and 5-aminotetrazole is added thereto, and the target product is obtained in several tens of degrees under stirring for several hours. . The crystalline substance is filtered off from the solvent organic acid anhydride. The reaction with the organic acid chloride is carried out by adding an equivalent amount of a base, such as triethylamine, for supplementing the hydrochloric acid produced in the reaction to a solvent that dissolves 5-aminotetrazole, such as DMF (dimethylformamide), to dissolve it.
When a stoichiometric amount of organic acid chloride is added dropwise or added, the reaction immediately occurs to obtain the desired product. The crystals are filtered off and optionally purified by recrystallization. The fact that the novel tetrazole derivative produced has the chemical structural formula shown in [Chemical formula 1] of the present invention is confirmed by elemental analysis [FIG. 1], infrared spectroscopic analysis [FIG. 2] and NMR analysis [FIG. 3]. It has been determined. The melting point and the decomposition temperature were measured by the results of differential thermal analysis. The results are shown in [Table 1].

[0012]

[Figure 1]

[0013]

FIG. 2

[0014]

FIG. 3

[0015]

[Table 1]

[0016]

Example 1 A method for producing N- [1H-tetrazol-5-yl] -N-valeramide (MW: 120.58). 17.64 g (0.207 mol) of 5-aminotetrazole was weighed into a 500 ml four-necked flask equipped with a stirrer, and then DMF was added.
300 ml was charged and dissolved with stirring. Then 20.98 g (0.207 mol) of triethylamine was added. Valeroyl chloride (25 g, 0.207 mol) was added dropwise from the dropping funnel to the above solution at room temperature with stirring. Simultaneously with the dropwise addition, the solution became cloudy due to the by-produced triethylamine hydrochloride, and the solution temperature rose to about 50 ° C. or higher at the reaction temperature. DMF 2
The mixture was transferred to a 1 L beaker containing double the amount of water, the hydrochloride of triethylamine was dissolved under strong stirring for about 1 hour, and the desired crystal product was washed with double the amount of water and then filtered off. The crystals were dried at room temperature and then dried under reduced pressure at 100 ° C. overnight. 19.1 g
White fine powder crystals (yield 54.5% based on 5-aminotetrazole) were obtained. The melting point and decomposition temperature of the obtained N- [1H-tetrazol-5-yl] -N-valeramide [Chemical Formula 2] by differential thermal analysis are shown in [Table 1], the elemental analysis results are shown in [Fig. 1], The results of infrared spectroscopic analysis are shown in FIG. 2 and the results of NMR analysis are shown in FIG.

[0017]

Embedded image

[0018]

Example 2 N, N'-bis- [1H-tetrazol-5-yl]-
A method for producing adipamide (MW: 280.254). 23.25 g (0.274 mol) of 5-aminotetrazole was weighed into a 500 ml four-necked flask equipped with a stirrer, and then DMF was added.
300 ml was charged and dissolved with stirring. Then 27.64 g (0.274 mol) of triethylamine was added. 25 g (0.137 mol) of adipoyl chloride was added dropwise from the dropping funnel to the above solution at room temperature with stirring. At the same time as the dropping, the solution became cloudy due to by-produced triethylamine hydrochloride, and the reaction solution was left under stirring at room temperature for 1 hour while cooling with ice so that the solution temperature did not rise above about 40 ° C at the reaction temperature. Was transferred to a 1L beaker containing twice the amount of water of DMF, the hydrochloride of triethylamine was dissolved with vigorous stirring for about 1 hour, and the desired crystalline substance was washed with twice the amount of water and then filtered. Separated The crystals were dried at room temperature and then dried under reduced pressure at 100 ° C. overnight. 15.22 g (yield based on 5-aminotetrazole of 39.6%) of white waxy crystals was obtained. Obtained N,
The melting point and decomposition temperature of N'-bis- [1H-tetrazol-5-yl] -adipamide [Chemical Formula 3] by differential thermal analysis are shown in [Table 1].

[0019]

Embedded image

[0020]

Example 3 A method for producing N- [1H-tetrazol-5-yl] -benzamide (MW: 189.179). 5.015 g of 5-aminotetrazole in a 300 ml beaker
(0.0589 mol) was weighed out, and then 100 g of DMF was charged and dissolved while stirring with a magnetic stirrer. Then 6.00 g (0.0593 mol) of triethylamine was added. Benzoyl chloride (8.33 g, 0.0593 mol) was weighed in a dropping funnel and added dropwise to the above solution at room temperature with stirring for about 5 minutes. Simultaneously with the dropwise addition, the solution became cloudy due to the by-produced triethylamine hydrochloride, and the solution temperature rose to about 30 ° C. at the reaction temperature. The reaction solution was left under stirring for 1 hour, and then DMF of 5 was added.
Double the amount of water was added to dissolve the triethylamine hydrochloride, and at the same time, the desired crystalline substance was precipitated, washed with double the amount of water, and then filtered. The crystals were dried at room temperature and then dried under reduced pressure at 100 ° C. overnight. 5.07 g (yield based on 5-aminotetrazole 45.2%) was obtained. Obtained N-
The melting point and decomposition temperature of [1H-tetrazol-5-yl] -benzamide [Chemical Formula 4] by differential thermal analysis are shown in [Table 1].

[0021]

[Chemical 4]

[0022]

EXAMPLE 4 All the novel tetrazole derivatives described in [Chemical Formula 1] were synthesized according to the synthetic methods described in [Example 1], [Example 2] and [Example 3]. The melting point and decomposition temperature of each of the obtained tetrazole derivatives by differential thermal analysis are shown in [Table 1].

The results of elemental analysis of the compounds of the present invention synthesized in Examples 1 to 4 are shown in [Table 2].

[0024]

[Table 2]

The infrared spectroscopic analysis results of the compounds of the present invention synthesized in Examples 1 to 4 are shown in Table 3.
The infrared spectrophotometer used SHIMAZU-C under the following analysis conditions. Aperture: Auto, Number of integrations: 40 Detector: standard, Apotize function: H
app resolution: 4.0, moving mirror speed: 2.8 sample: individual

[0026]

[Table 3]

N of the compounds synthesized in Examples 1 to 4
The results of MR analysis are shown in [Table 4].

[0028]

[Table 4]

The results of differential thermal analysis of the compounds synthesized in Examples 1 to 4 are shown in [Table 5]. In the differential thermal analysis, the results obtained by increasing the temperature of the synthesized compound by 10 ° C. per minute are shown.

[0030]

[Table 5]

[0031]

INDUSTRIAL APPLICABILITY According to the present invention, a synthetic resin foam having excellent thermal properties, an inflator for an airbag as a safety device for automobiles, or various agents are manufactured by an inexpensive synthetic method of a novel tetrazole derivative. It has become possible to provide an excellent smoke agent that is harmless to humans and odorless for diffusing odors, and opened the way to the practical application of these new compounds.

[Brief description of drawings]

The differential thermogravimetric analysis curve, infrared absorption spectrum and NMR curve of the compound obtained in Example 1 are shown in FIGS. 1, 2 and 3, respectively.

[Table 1]

[Table 1]

[Table 2]

[Table 2]

[Table 3]

[Table 3]

[Table 3]

[Table 4]

[Table 4]

[Table 4]

[Table 5]

[Table 5]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 30, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a plan view of a differential thermogravimetric analysis curve of the compound obtained in Example 1.

FIG. 2 is a plan view showing an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 3 is a plan view of the NMR curve of the compound obtained in Example 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08J 9/06 C08J 9/06 C08K 5/3445 KBJ C08K 5/3445 KBJ C09K 3/00 111 C09K 3/00 111B // C08L 101: 00

Claims (3)

[Claims] 1. A novel tetrazole derivative represented by the general formula of [Chemical Formula 1] shown below. Embedded image 2. The novel tetrazole derivative according to claim 1, which is used as a gas generating agent. 3. The use of the tetrazole derivative according to claim 1 as a foaming agent for resin moldings, an inflator for airbags as a safety device for automobiles, or a smoke agent for diffusing chemicals. The novel tetrazole derivative according to claim 1, characterized in that