JPH10218868A - Production of 5-methyltetrazole - Google Patents
Production of 5-methyltetrazoleInfo
- Publication number
- JPH10218868A JPH10218868A JP9042987A JP4298797A JPH10218868A JP H10218868 A JPH10218868 A JP H10218868A JP 9042987 A JP9042987 A JP 9042987A JP 4298797 A JP4298797 A JP 4298797A JP H10218868 A JPH10218868 A JP H10218868A
- Authority
- JP
- Japan
- Prior art keywords
- acetonitrile
- methyltetrazole
- water
- aluminum chloride
- azide salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗生物質の修飾剤
等に有用な５ーメチルテトラゾールを、容易、安全、安
価に製造する方法に関する。The present invention relates to a method for easily, safely and inexpensively producing 5-methyltetrazole, which is useful as a modifier for antibiotics.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】５−メチ
ルテトラゾールを製造する方法は過去に種々検討されて
おり、アセトニトリル、チオアセトアミド、アセトアミ
ドラゾン塩酸塩または１ーエトキシー１,１ージアジド
エタンからの製造方法が公知である。これらの製造方法
は一般的に収率が低く、入手困難な出発原料を使用した
ものもあり、工業的に不利な方法である。2. Description of the Related Art Various methods for producing 5-methyltetrazole have been studied in the past, and include methods for producing 5-methyltetrazole from acetonitrile, thioacetamide, acetamidrazone hydrochloride or 1-ethoxy-1,1-diazidoethane. Methods are known. These production methods are generally industrially disadvantageous because of low yields and use of starting materials that are difficult to obtain.
【０００３】比較的安価な出発原料としてアセトニトリ
ルに着目すると、例えば、アセトニトリルとアジ化水素
酸とを、１５０℃でベンゼン溶媒中で反応させている
［Ｊ．Ｏｒｇ．Ｃｈｅｍ．，１５（１９５０年），１０
８２，１０８５，１０８８］。この方法においては、収
率は７６％であるが、爆発性を有し、毒性の高いアジ化
水素酸を使用し、しかも、高温、高圧下で反応させるた
め、工業的に危険性が高く非常に不利である。Focusing on acetonitrile as a relatively inexpensive starting material, for example, acetonitrile and hydrazoic acid are reacted at 150 ° C. in a benzene solvent [J. Org. Chem. , 15 (1950), 10
82, 1085, 1088]. In this method, the yield is 76%, but since explosive, highly toxic hydrazic acid is used, and the reaction is carried out at high temperature and high pressure, it is industrially dangerous and very dangerous. Disadvantageous.
【０００４】近年、［Ｃａｎ．Ｊ．Ｃｈｅｍ．，６５
（１９８７年），１６６−１６９］によれば、アセトニ
トリルとアジ化ナトリウムとを、塩化アルミニウム触媒
の存在下、テトラヒドロフラン溶媒中で反応させてい
る。この方法は高価な溶媒を使用し、収率は３４％と低
い。また、ドイツ特許３６３４７１７（１９８８年）に
よれば、アセトニトリルとアジ化ナトリウムとを、トリ
エチルアミン塩酸塩触媒の存在下、トリエチルアミン溶
媒中で反応させている。この方法では高収率、高純度の
５ーメチルテトラゾールが得られているが、高価な溶媒
を使用し、テトラゾール合成条件としては高圧、高温を
用いており、製造上危険性が高く工業的に不利である。Recently, [Can. J. Chem. , 65
(1987), 166-169], acetonitrile and sodium azide are reacted in a tetrahydrofuran solvent in the presence of an aluminum chloride catalyst. This method uses expensive solvents and the yield is as low as 34%. According to German Patent 3,634,717 (1988), acetonitrile and sodium azide are reacted in a triethylamine solvent in the presence of a triethylamine hydrochloride catalyst. Although high yield and high purity of 5-methyltetrazole are obtained by this method, expensive solvents are used, and high pressure and high temperature are used as tetrazole synthesizing conditions. Disadvantageous.
【０００５】本発明の課題は、上記のような従来技術の
問題を解決し得て、反応の制御が容易で、安価な原料
で、５−メチルテトラゾールを高収率、容易且つ安全に
製造することのできる方法を提供することにある。An object of the present invention is to solve the above-mentioned problems of the prior art, to easily control the reaction and to produce 5-methyltetrazole easily, safely and inexpensively with high yield. It is to provide a method that can do it.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記問題を
解決するために、工業的に有利な方法を鋭意研究したと
ころ、アセトニトリルと無機アジ化塩とを、特定量の微
量水分を含有するアセトニトリル溶媒中、塩化アルミニ
ウム触媒の存在下で反応させることにより、５ーメチル
テトラゾールが、高純度、高収率で、しかも、高温、高
圧でない系で容易に製造できることを見い出し、本発明
を完成するに至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied an industrially advantageous method, and found that acetonitrile and an inorganic azide salt contained a specific amount of trace water. Completed the present invention by finding that 5-methyltetrazole can be easily produced in a high-purity, high-yield, yet high-temperature, non-high-pressure system by reacting in an acetonitrile solvent in the presence of an aluminum chloride catalyst. I came to.
【０００７】なお、従来、アセトニトリルと無機アジ化
塩とを、塩化アルミニウム触媒存在下で合成する際にア
セトニトリルを溶媒として使用した例はなく、しかも、
塩化アルミニウムを触媒として使用する際は、微量の水
分は反応に不利とされていたものを、本発明では特定量
の微量水分を添加することで、収率の向上に寄与してい
ることを見い出した。[0007] Heretofore, there has been no example of using acetonitrile as a solvent when acetonitrile and an inorganic azide salt are synthesized in the presence of an aluminum chloride catalyst.
When using aluminum chloride as a catalyst, trace amounts of water were disadvantageous to the reaction, but in the present invention, it has been found that by adding a specific amount of trace amounts of water, it contributes to the improvement of the yield. Was.
【０００８】本発明の方法は、アセトニトリルと無機ア
ジ化塩から５ーメチルテトラゾールを製造する方法であ
って、塩化アルミニウム触媒の存在下、特定量の微量水
分を含有するアセトニトリル溶媒中において反応させる
ことを特徴とする。The process of the present invention is a process for producing 5-methyltetrazole from acetonitrile and an inorganic azide salt, wherein the reaction is carried out in the presence of an aluminum chloride catalyst in an acetonitrile solvent containing a specific amount of trace water. It is characterized by.
【０００９】また、本発明の方法は、アセトニトリルと
下記式（１）で表される無機アジ化塩とを、塩化アルミ
ニウム触媒の存在下、特定量の微量水分を含有するアセ
トニトリル溶媒中で反応させることを特徴する下記式
（２）で表される５−メチルテトラゾ−ルの製造方法。 Ｍ（Ｎ3）n （１） （式中、Ｍはアルカリ金属またはアルカリ土類金属であ
り、ｎは１または２である。）In the method of the present invention, acetonitrile is reacted with an inorganic azide salt represented by the following formula (1) in an acetonitrile solvent containing a specific amount of trace water in the presence of an aluminum chloride catalyst. A method for producing 5-methyltetrazole represented by the following formula (2): M (N 3 ) n (1) (wherein M is an alkali metal or an alkaline earth metal, and n is 1 or 2)
【化２】 （２）Embedded image (2)
【００１０】[0010]
【発明の実施の形態】本発明において、原料であり溶媒
でもあるアセトニトリルは、市販のものを用いても差し
支えない。それに含有される水分として、通常０．４〜
１．０重量％の範囲、好ましくは０．６〜０．８重量
％の範囲である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, commercially available acetonitrile as a raw material and a solvent may be used. As the water contained therein, usually 0.4-
It is in the range of 1.0% by weight, preferably in the range of 0.6 to 0.8% by weight.
【００１１】無機アジ化塩としては、ナトリウム、カリ
ウム、リチウム、カルシウム、マグネシウム等のアルカ
リ金属またはアルカリ土類金属のアジ化物が挙げられる
が、アジ化ナトリウムが工業的に好適である。これらの
無機アジ化塩の使用量は、触媒の塩化アルミニウム１モ
ルに対して、通常１．０〜２．０モルの範囲、好ましく
は１．３〜１．８モルである。Examples of the inorganic azide include alkali metal or alkaline earth metal azides such as sodium, potassium, lithium, calcium, and magnesium, and sodium azide is industrially suitable. The amount of the inorganic azide salt to be used is generally in the range of 1.0 to 2.0 mol, preferably 1.3 to 1.8 mol, per 1 mol of aluminum chloride of the catalyst.
【００１２】反応温度は、特に限定されず、通常５０〜
１２０℃、好ましくは７０〜９０℃の範囲である。The reaction temperature is not particularly limited and is usually 50 to
120 ° C, preferably in the range of 70 to 90 ° C.
【００１３】反応時間は、触媒の添加量、反応温度によ
り影響を受けるが、通常１〜１２０時間、好ましくは３
０〜５０時間である。Although the reaction time is affected by the amount of the catalyst added and the reaction temperature, it is usually 1 to 120 hours, preferably 3 hours.
0-50 hours.
【００１４】反応後、濃塩酸で中和処理することによ
り、フリー体の５ーメチルテトラゾールが得られる。
なお、その時、有毒なアジ化水素が副生するが、亜硝酸
ナトリウム水溶液を添加することにより、系内で完全に
分解することが可能である。亜硝酸ナトリウム水溶液は
３０〜４０重量％のものを使用し、その使用量は、原料
のアジ化ナトリウム１モルに対し、亜硝酸ナトリウムで
０．１０〜０．２０モルに相当する量を添加すればよ
い。After the reaction, a free form of 5-methyltetrazole is obtained by neutralizing with concentrated hydrochloric acid.
At that time, toxic hydrogen azide is by-produced, but can be completely decomposed in the system by adding an aqueous solution of sodium nitrite. The aqueous solution of sodium nitrite is used in an amount of 30 to 40% by weight. The amount of sodium nitrite used is 0.10 to 0.20 mol of sodium nitrite per mol of sodium azide as a raw material. I just need.
【００１５】副生する塩化ナトリウムと塩化アルミニウ
ム６水塩は、遠心分離による濾過方法で濾別でき、濾過
液を濃縮乾固することにより、５ーメチルテトラゾール
を高純度、高収率で得ることができる。The by-produced sodium chloride and aluminum chloride hexahydrate can be separated by filtration by centrifugation, and the filtrate is concentrated to dryness to obtain 5-methyltetrazole with high purity and high yield. Can be.
【００１６】以上のように、本発明は、工業的に５ーメ
チルテトラゾールを製造するのに非常に有利な方法であ
る。As described above, the present invention is a very advantageous method for industrially producing 5-methyltetrazole.
【００１７】[0017]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、本発明はこれらに限定されるものではな
い。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【００１８】実施例１ 還流冷却器、温度計、滴下ロ−トおよび撹拌機を設けた
５００ｍｌフラスコに、アセトニトリル２９３ｇ（７．
１５モル）と水２．０ｇを入れ、氷冷撹拌下に塩化アル
ミニウム６０．０ｇ（０．４５モル）を投入する。 発
熱により内温が約５０℃まで上がるので、発熱がおさま
ってからアジ化ナトリウム４０ｇ（０．６２モル）を投
入し、８４℃（還流）まで昇温し同温度で４０時間反応
せた。反応終了後、室温まで冷却し、３４％塩酸７４．
１ｇを滴下し、水０．５ｇでライン洗浄して、３０℃で
０．５時間撹拌した。次いで、３５％亜硝酸ナトリウム
水溶液１２．３ｇを滴下し、水０．５ｇでライン洗浄し
て、３０℃で２時間熟成した。吸引濾過し、ケーキをア
セトニトリル１２０ｇで洗浄した。濾別した副生塩は２
１３ｇ（固形分７０％）であった。濾過母液をエバポレ
ーターにより濃縮乾固し、６０℃で減圧乾燥した。その
結果、５−メチルテトラゾ−ル４８．８ｇ（純度９４．
７％）を得た。これは収率８９．４％（アジ化ナトリウ
ム基準）に相当した。Example 1 In a 500 ml flask equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer, 293 g of acetonitrile (7.
15 mol) and 2.0 g of water, and 60.0 g (0.45 mol) of aluminum chloride are added under ice-cooling and stirring. Since the internal temperature rises to about 50 ° C. due to the heat generation, 40 g (0.62 mol) of sodium azide was added after the heat generation was stopped, the temperature was raised to 84 ° C. (reflux), and the reaction was carried out at the same temperature for 40 hours. After the completion of the reaction, the mixture was cooled to room temperature, and 34% hydrochloric acid
1 g was added dropwise, the line was washed with 0.5 g of water, and stirred at 30 ° C. for 0.5 hour. Subsequently, 12.3 g of a 35% aqueous sodium nitrite solution was added dropwise, the line was washed with 0.5 g of water, and aged at 30 ° C. for 2 hours. After suction filtration, the cake was washed with 120 g of acetonitrile. By-product salt filtered out is 2
13 g (solid content 70%). The filtered mother liquor was concentrated to dryness by an evaporator and dried at 60 ° C. under reduced pressure. As a result, 48.8 g of 5-methyltetrazole (purity 94.5 g) was obtained.
7%). This corresponded to a yield of 89.4% (based on sodium azide).
【００１９】実施例２ 実施例１と同様な装置に、アセトニトリル２９３ｇ
（７．１５モル）と水１．７ｇを入れ、氷冷撹拌下に塩
化アルミニウム６０．０ｇ（０．４５モル）を投入す
る。 発熱により内温が約５０℃まで上がるので、発熱
がおさまってからアジ化ナトリウム４０ｇ（０．６２モ
ル）を投入し、８４℃（還流）まで昇温し同温度で４０
時間反応せた。反応終了後、室温まで冷却し、３４．０
％塩酸７４．１ｇを滴下し、水０．５ｇでライン洗浄し
て、３０℃で０．５時間撹拌した。次いで、４０％亜硝
酸ナトリウム水溶液１０．８ｇを滴下し、水０．５ｇで
ライン洗浄して、３０℃で２時間熟成した。吸引濾過
し、ケーキをアセトニトリル１２０ｇで洗浄した。濾別
した副生塩は２２９ｇ（固形分６５％）であった。濾過
母液をエバポレーターにより濃縮乾固し、６０℃で減圧
乾燥した。その結果、５−メチルテトラゾ−ル４７．８
ｇ（純度９６．４％）を得た。これは収率８９．１％
（アジ化ナトリウム基準）に相当した。Example 2 293 g of acetonitrile was added to the same apparatus as in Example 1.
(7.15 mol) and 1.7 g of water are added, and 60.0 g (0.45 mol) of aluminum chloride is added under ice-cooling and stirring. Since the internal temperature rises to about 50 ° C. due to the heat generation, 40 g (0.62 mol) of sodium azide is added after the heat generation has subsided, and the temperature is raised to 84 ° C. (reflux).
Reacted for hours. After the completion of the reaction, the resultant was cooled to room temperature, and 34.0
74.1 g of hydrochloric acid was added dropwise, the line was washed with 0.5 g of water, and the mixture was stirred at 30 ° C. for 0.5 hour. Next, 10.8 g of a 40% aqueous sodium nitrite solution was added dropwise, the line was washed with 0.5 g of water, and aged at 30 ° C. for 2 hours. After suction filtration, the cake was washed with 120 g of acetonitrile. The by-product salt separated by filtration was 229 g (solid content: 65%). The filtered mother liquor was concentrated to dryness by an evaporator and dried at 60 ° C. under reduced pressure. As a result, 57.8-methyltetrazole 47.8
g (purity 96.4%). This is a yield of 89.1%
(Based on sodium azide).
【００２０】実施例３ 実施例１と同様な装置に、アセトニトリル２９３ｇ
（７．１５モル）と水２．６ｇを入れ、氷冷撹拌下に塩
化アルミニウム６０．０ｇ（０．４５モル）を投入す
る。 発熱により内温が約５０℃まで上がるので、発熱
がおさまってからアジ化ナトリウム４０ｇ（０．６２モ
ル）を投入し、８４℃（還流）まで昇温し同温度で４０
時間反応せた。反応終了後、室温まで冷却し、３３．４
％塩酸７５．５ｇを滴下し、水０．５ｇでライン洗浄し
て、３０℃で１時間撹拌した。次いで、３５％亜硝酸ナ
トリウム水溶液１２．３ｇを滴下し、水０．５ｇでライ
ン洗浄して、３０℃で２時間熟成した。吸引濾過し、ケ
ーキをアセトニトリル１２０ｇで洗浄した。濾別した副
生塩は２０１ｇ（固形分７４％）であった。濾過母液を
エバポレーターにより濃縮乾固し、６０℃で減圧乾燥し
た。その結果、５−メチルテトラゾ−ル４７．７ｇ（９
３．３％）を得た。これは収率８６．１％（アジ化ナト
リウム基準）に相当した。Example 3 In a device similar to that of Example 1, 293 g of acetonitrile was added.
(7.15 mol) and 2.6 g of water are added, and 60.0 g (0.45 mol) of aluminum chloride is added under ice-cooling and stirring. Since the internal temperature rises to about 50 ° C. due to the heat generation, 40 g (0.62 mol) of sodium azide is added after the heat generation has subsided, and the temperature is raised to 84 ° C. (reflux).
Reacted for hours. After the completion of the reaction, the resultant was cooled to room temperature, and 33.4.
75.5 g of hydrochloric acid was added dropwise, the line was washed with 0.5 g of water, and the mixture was stirred at 30 ° C. for 1 hour. Subsequently, 12.3 g of a 35% aqueous sodium nitrite solution was added dropwise, the line was washed with 0.5 g of water, and aged at 30 ° C. for 2 hours. After suction filtration, the cake was washed with 120 g of acetonitrile. The by-product salt filtered off was 201 g (solid content: 74%). The filtered mother liquor was concentrated to dryness by an evaporator and dried at 60 ° C. under reduced pressure. As a result, 47.7 g of 5-methyltetrazole (9
3.3%). This corresponded to a yield of 86.1% (based on sodium azide).
【００２１】比較例１ 実施例１において、アセトニトリル２９３ｇ（７．１５
モル）に水を添加せずに、以下、実施例１と同様の操作
を行った。その結果、５ーメチルテトラゾール３３．７
ｇ（純度９７．０％）を得た。これは収率６３．２％
（アジ化ナトリウム基準）に相当した。Comparative Example 1 In Example 1, 293 g of acetonitrile (7.15)
Mol), and the same operation as in Example 1 was carried out without adding water. As a result, 5-methyltetrazole 33.7
g (purity 97.0%) was obtained. This is a yield of 63.2%.
(Based on sodium azide).
【００２２】[0022]
【発明の効果】本発明によって、反応の制御が容易で、
安価な原料で、５ーメチルテトラゾールを高純度、高収
率、容易、且つ安全に製造できる。According to the present invention, the reaction can be easily controlled,
5-Methyltetrazole can be produced with high purity, high yield, easily and safely using inexpensive raw materials.
Claims (4)
れる無機アジ化塩とを、塩化アルミニウム触媒の存在
下、特定量の微量水分を含有するアセトニトリル溶媒中
で反応させることを特徴とする下記式（２）で表される
５−メチルテトラゾ−ルの製造方法。 Ｍ（Ｎ3）n （１） （式中、Ｍはアルカリ金属またはアルカリ土類金属であ
り、ｎは１または２である。） 【化１】 （２）1. A method comprising reacting acetonitrile with an inorganic azide salt represented by the following formula (1) in an acetonitrile solvent containing a specific amount of trace water in the presence of an aluminum chloride catalyst. A method for producing 5-methyltetrazole represented by the formula (2). M (N 3 ) n (1) (wherein M is an alkali metal or an alkaline earth metal, and n is 1 or 2) (2)
ることを特徴とする請求項１に記載の製造方法。2. The method according to claim 1, wherein the inorganic azide salt is sodium azide.
用モル比（無機アジ化塩／塩化アルミニウム）は１.０
〜２.０、好ましくは１.３〜１.８である請求項１また
は請求項２に記載の製造方法。3. The molar ratio of the inorganic azide salt to aluminum chloride (inorganic azide salt / aluminum chloride) is 1.0.
The production method according to claim 1 or 2, wherein the number is from 2.0 to 2.0, preferably from 1.3 to 1.8.
１．０重量％であり、好ましくは０.６〜０.８である、
請求項１または請求項２に記載の製造方法。4. The water content in acetonitrile is from 0.4 to 4.
1.0% by weight, preferably 0.6 to 0.8,
The manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9042987A JPH10218868A (en) | 1997-02-12 | 1997-02-12 | Production of 5-methyltetrazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9042987A JPH10218868A (en) | 1997-02-12 | 1997-02-12 | Production of 5-methyltetrazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10218868A true JPH10218868A (en) | 1998-08-18 |
Family
ID=12651395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9042987A Pending JPH10218868A (en) | 1997-02-12 | 1997-02-12 | Production of 5-methyltetrazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10218868A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7943647B2 (en) | 2003-07-15 | 2011-05-17 | Novartis Ag | Process for the preparation of tetrazole derivatives from organo aluminium azides |
| CN103351353A (en) * | 2013-07-25 | 2013-10-16 | 浙江海蓝化工有限公司 | Aqueous phase synthesis method of 5-methyl tetrazole |
| CN110330462A (en) * | 2019-08-07 | 2019-10-15 | 宁夏大学 | A kind of preparation method of 5- methyl tetrazolium metal complex containing energy |
-
1997
- 1997-02-12 JP JP9042987A patent/JPH10218868A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7943647B2 (en) | 2003-07-15 | 2011-05-17 | Novartis Ag | Process for the preparation of tetrazole derivatives from organo aluminium azides |
| US8569528B2 (en) | 2003-07-15 | 2013-10-29 | Novartis Ag | Process for the preparation of tetrazole derivatives from organo boron and organo aluminium azides |
| CN103351353A (en) * | 2013-07-25 | 2013-10-16 | 浙江海蓝化工有限公司 | Aqueous phase synthesis method of 5-methyl tetrazole |
| CN110330462A (en) * | 2019-08-07 | 2019-10-15 | 宁夏大学 | A kind of preparation method of 5- methyl tetrazolium metal complex containing energy |
| CN110330462B (en) * | 2019-08-07 | 2022-05-17 | 宁夏大学 | Preparation method of energetic metal coordination compound of 5-methyltetrazole |
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