JPH072805A - Production of 5-((1,1'-biphenyl)-1h-tetrazoles - Google Patents
Production of 5-((1,1'-biphenyl)-1h-tetrazolesInfo
- Publication number
- JPH072805A JPH072805A JP5108734A JP10873493A JPH072805A JP H072805 A JPH072805 A JP H072805A JP 5108734 A JP5108734 A JP 5108734A JP 10873493 A JP10873493 A JP 10873493A JP H072805 A JPH072805 A JP H072805A
- Authority
- JP
- Japan
- Prior art keywords
- biphenyl
- tetrazole
- formula
- alkali metal
- reaction
- 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.)
- Granted
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は〔化３〕で示される５−
（１，１′−ビフエニル）−１Ｈ−テトラゾ−ル類の製
造法に関するものである。更に詳しくは、本発明は４′
−アルキル−１，１′ビフエニル−２−カルボニトリル
類又は、４′−ハロゲン化メチル−１，１′，ビフエニ
ル−２−カルボニトリル類（以下ニトリル類と略称す
る）とアルカリ金属アザイドとの反応による５−〔４′
−アルキル−（１，１′−ビフエニル）−２−イル〕−
１Ｈ−テトラゾ−ル又は、５−〔４′−ハロゲン化メチ
ル−（１，１′−ビフエニル）−２−イル〕−１Ｈ−テ
トラゾ−ル（以下テトラゾ−ル類と略称する）の製造を
工業的に有利に行う方法に関するものである。本発明の
テトラゾ−ル類とその誘導体は、医薬の中間体として有
用な化合物である。The present invention relates to 5-
The present invention relates to a method for producing (1,1'-biphenyl) -1H-tetrazole. More specifically, the present invention provides a 4 '
-Reaction of alkyl-1,1 'biphenyl-2-carbonitriles or 4'-halogenated methyl-1,1', biphenyl-2-carbonitriles (hereinafter abbreviated as nitriles) with alkali metal azide By 5- [4 '
-Alkyl- (1,1'-biphenyl) -2-yl]-
Industrial production of 1H-tetrazole or 5- [4'-methyl halide- (1,1'-biphenyl) -2-yl] -1H-tetrazole (hereinafter abbreviated as tetrazole) The present invention relates to a method that can be advantageously performed. INDUSTRIAL APPLICABILITY The tetrazole and its derivative of the present invention are useful compounds as intermediates for medicines.
【０００２】[0002]
【化３】 （ここにＲはＨ又はハロゲン化メチル又はＣ1 〜Ｃ4 の
アルキルである。）[Chemical 3] (Wherein R is H or methyl halide or C 1 -C 4 alkyl).
【０００３】[0003]
【従来の技術】従来テトラゾ−ル類の製造法としては以
下に記載の方法が知られている。即ち(イ) 下記の〔反応
式（１）〕に示すように、ニトリル類とアルカリ金属ア
ザイドとを原料として塩化アンモニウムの様なアンモニ
ウム塩を触媒として使用する方法がある。〔特開昭63−
23868.J.Org.Chem.80,3908(1958)〕この場合の収率は88
％である。2. Description of the Related Art Conventionally, the following method is known as a method for producing tetrazole. That is, (a) As shown in the following [Reaction formula (1)], there is a method in which an nitrile and an alkali metal azide are used as raw materials and an ammonium salt such as ammonium chloride is used as a catalyst. [JP 63-
23868.J.Org.Chem.80,3908 (1958)] In this case, the yield is 88.
%.
【０００４】[0004]
【反応式（１）】 （注、ＤＭＦ＝ジメチルホルムアミド）[Reaction formula (1)] (Note, DMF = dimethylformamide)
【０００５】(ロ) 又は下記の〔反応式（２）〕で示すよ
うに、ニトリル類とトリアルキル錫アザイドを原料とし
てテトラゾ−ル類を製造する方法がある。〔特開平３−
74369.J.Org.Chem.56,2395(1991)〕この場合のテトラゾ
−ルの収率は76％に止まっていた。There is a method for producing tetrazole using nitriles and trialkyltin azide as raw materials, as shown in (b) or the following [Reaction formula (2)]. [JP-A-3-
74369.J.Org.Chem.56,2395 (1991)] In this case, the yield of tetrazole was only 76%.
【０００６】[0006]
【反応式（２）】 [Reaction formula (2)]
【０００７】[0007]
【発明が解決しようとする課題】前記の〔反応式
（１）〕で示したように従来の塩化アンモニウムを触媒
に使用してテトラゾ−ル類を製造する方法は収率が88％
であるが、反応速度が著しく遅く反応温度が120 ℃で11
日間も反応を行う必要があり、工業的製造方法としては
不適である。また〔反応式（２）〕で示すトリアルキル
錫アザイドを原料として使用する方法はトリアルキル錫
アザイドが高価であるほか、これを原料として使用する
方法は110 ℃で24時間の反応で収率が76％で低い。As shown in the above [Reaction formula (1)], the conventional method for producing tetrazole using ammonium chloride as a catalyst has a yield of 88%.
However, the reaction rate is extremely slow and the reaction temperature is 11 ° C at 120 ° C.
It is necessary to carry out the reaction for a day, which is not suitable as an industrial production method. In addition, the method of using the trialkyltin azide shown in [Reaction formula (2)] as a raw material is expensive as well as the method of using this as a raw material has a yield of 24 hours at 110 ° C. Low at 76%.
【０００８】本発明者等はこれらの点について鋭意研究
した結果、本発明を完成するに至ったもので、本発明は
〔反応式（３）〕に示すようにニトリル類とアルカリ金
属アザイドとの反応によるテトラゾ−ル類の製造におい
て、塩酸トリエチルアミンなどのアルキルアミン塩類を
触媒として使用することによつてアルキルアミン塩類の
優れた触媒効果によつてテトラゾ−ル類を製造すること
を目的とするものである。この場合還流状態の反応によ
つて90％の収率が得られ、そのため簡単に有機溶媒によ
つて洗浄することにより未反応のニトリル類を除去可能
となり高収率、高品質のテトラゾ−ル類の工業的生産が
可能になつた。The present inventors have conducted intensive studies on these points, and as a result, have completed the present invention. The present invention is based on the reaction formula (3) with nitriles and alkali metal azides. In the production of tetrazole by reaction, the object is to produce tetrazole by the excellent catalytic effect of alkylamine salt by using alkylamine salt such as triethylamine hydrochloride as a catalyst. Is. In this case, a 90% yield can be obtained by the reaction in the reflux state, so that unreacted nitriles can be removed by simply washing with an organic solvent, and high yield and high quality tetrazole can be obtained. Has become possible for industrial production.
【０００９】[0009]
【反応式（３）】 [Reaction formula (3)]
【００１０】[0010]
【問題を解決するための手段】本発明は〔化４〕で示さ
れるビフエニル−２−カルボニトリル類とアルカリ金属
アザイドとの反応をアルキルアミン塩類を触媒として使
用することを特徴とする〔化２〕で示される５−（１，
１′−ビフエニル）−１Ｈ−テトラゾ−ル類の製造法に
関するものである。The present invention is characterized in that the reaction of biphenyl-2-carbonitriles represented by [Chemical formula 4] with an alkali metal azide is performed by using an alkylamine salt as a catalyst. ] 5- (1,
The present invention relates to a method for producing 1'-biphenyl) -1H-tetrazole.
【００１１】[0011]
【化４】 （ここにＲはＨ又はハロゲン化メチル又はＣ1 〜Ｃ4 の
アルキル基である。）[Chemical 4] (Here, R is H or a halogenated methyl or a C 1 -C 4 alkyl group.)
【００１２】上記の如くアルキルアミン塩類を触媒とし
て使用することによつて、上記従来法に比較して経済的
にテトラゾ−ル類を製造することが可能になつた。かつ
反応率が上記の様に高いため、出発原料である未反応の
ニトリル類が有機溶剤によつて洗浄することにより簡単
に除去可能であり、高収率、かつ高品質のテトラゾ−ル
類を製造することが可能になつた。By using the alkylamine salt as a catalyst as described above, it has become possible to produce tetrazole economically as compared with the conventional method. And since the reaction rate is high as described above, unreacted nitriles that are starting materials can be easily removed by washing with an organic solvent, and high yield and high quality tetrazole can be obtained. It has become possible to manufacture.
【００１３】本発明の方法を詳細説明するとＤＭＦ溶媒
の存在下でニトリル類とソジウムアザイド及び塩酸アル
キルアミン触媒を混合して還流温度まで昇温して反応せ
しめる。しかる後反応液に水及びトルエンを加え、数時
間撹拌した後、トルエン層を除去する。水層に塩酸を添
加し、析出した白色結晶を濾別し、乾燥して本発明のテ
トラゾ−ル類を得た。The method of the present invention will be described in detail. Nitriles, sodium azide and an alkylamine hydrochloride catalyst are mixed in the presence of a DMF solvent, and the mixture is heated to a reflux temperature for reaction. After that, water and toluene are added to the reaction solution, the mixture is stirred for several hours, and then the toluene layer is removed. Hydrochloric acid was added to the aqueous layer, and the precipitated white crystals were filtered off and dried to obtain the tetrazole of the present invention.
【００１４】使用する触媒のアルキルアミン塩類として
はＣ1 〜Ｃ4 で示されるアルキル基を有する一級から三
級アミンの塩類であり、その中でも三級アミンの塩類が
好適であり、特にトリエチルアミン塩類が最も有利に使
用される。塩としては塩酸塩、硫酸塩などが好ましい。
アルカリ金属アザイドの使用量はニトリルに対して1.02
モル以上、好ましくは1.05〜1.30モルの範囲である。触
媒としてのトリアルキルアミン塩類の使用量はアルカリ
金属アザイドに対して1.02モル以上あればよいが、好ま
しくは1.05〜1.10モルの範囲である。反応温度はアルカ
リ金属アザイドの溶解性から80℃以上必要であり、好適
には110 〜130 ℃である。反応時間は触媒の種類や量な
どによつて異るが、一般的には約24時間必要である。The alkylamine salt of the catalyst used is a salt of a primary to tertiary amine having an alkyl group represented by C 1 to C 4 , and among them, a salt of a tertiary amine is preferable, and a triethylamine salt is particularly preferable. Most advantageously used. The salt is preferably hydrochloride, sulfate or the like.
The amount of alkali metal azide used is 1.02 with respect to nitrile
It is at least mol, preferably in the range of 1.05 to 1.30 mol. The amount of the trialkylamine salt used as a catalyst may be 1.02 mol or more with respect to the alkali metal azide, but is preferably in the range of 1.05 to 1.10 mol. The reaction temperature is required to be 80 ° C. or higher in view of the solubility of alkali metal azide, and is preferably 110 to 130 ° C. The reaction time varies depending on the type and amount of the catalyst, but generally it takes about 24 hours.
【００１５】次に実施例によつて本発明を説明する。The present invention will be described below with reference to examples.
【実施例１】ＤＭＦ250ml 、４′−メチル−１，１′−
ビフエニル−２−カルボニトリル106.8g(0.55 モル）、
ソジウムアザイド46.7g 、塩酸トリエチルアミン98.6g
を仕込み、115 ℃まで昇温し22時間反応した。ついで室
温まで冷却後、トルエン100ml 、水400ml 、48％NaOHを
加えた。分液してトルエン層を除去した後、水層に36％
塩酸114.0gを滴下した。10℃まで冷却後、結晶を濾別
し、真空乾燥を行い、白色結晶の５−〔４′−メチル−
（１，１′−ビフエニル）−２−イル〕−１Ｈ−テトラ
ゾ−ル、108.8g（収率83.2％、純度99.8％）を得た。Example 1 DMF 250 ml, 4'-methyl-1,1'-
Biphenyl-2-carbonitrile 106.8 g (0.55 mol),
Sodium azide 46.7g, triethylamine hydrochloride 98.6g
Was charged, the temperature was raised to 115 ° C., and the reaction was performed for 22 hours. Then, after cooling to room temperature, 100 ml of toluene, 400 ml of water and 48% NaOH were added. After separating and removing the toluene layer, 36% was added to the water layer.
114.0 g of hydrochloric acid was added dropwise. After cooling to 10 ° C., the crystals were separated by filtration and vacuum dried to give white crystals of 5- [4′-methyl-
108.8 g (yield 83.2%, purity 99.8%) of (1,1'-biphenyl) -2-yl] -1H-tetrazole was obtained.
【００１６】[0016]
【実施例２】ＤＭＦ50ml、４′−クロロメチル−１，
１′−ビフエニル−２−カルボニトリル22.9g(0.1 モ
ル）、ソジウムアザイド7.8g、塩酸トリエチルアミン1
6.5g を仕込み、120 ℃まで昇温し25時間反応した。室
温まで冷却後、トルエン20ml、水80ml、48％NaOHを加え
た。分液してトルエン層を除去した後、水層に36％塩酸
22.8g を滴下した。10℃まで冷却後、結晶を濾別し、真
空乾燥を行い、白色結晶の５−〔４′−クロロメチル−
（１，１′−ビフエニル）−２−イル〕−１Ｈ−テトラ
ゾ−ル、22.9g （収率84.5％、純度99.0％）を得た。Example 2 DMF 50 ml, 4'-chloromethyl-1,
1'-Biphenyl-2-carbonitrile 22.9 g (0.1 mol), sodium azide 7.8 g, triethylamine hydrochloride 1
6.5 g was charged, the temperature was raised to 120 ° C., and the reaction was performed for 25 hours. After cooling to room temperature, 20 ml of toluene, 80 ml of water and 48% NaOH were added. After separating the liquid and removing the toluene layer, 36% hydrochloric acid is added to the aqueous layer.
22.8 g was added dropwise. After cooling to 10 ° C, the crystals were separated by filtration and dried in vacuum to give white crystals of 5- [4'-chloromethyl-
22.9 g (yield 84.5%, purity 99.0%) of (1,1'-biphenyl) -2-yl] -1H-tetrazole was obtained.
【００１７】[0017]
【実施例３】ＤＭＦ50ml、４′−クロロメチル−１，
１′−ビフエニル−２−カルボニトリル22.9g(0.1 モ
ル）、ソジウムアザイド7.8g、塩酸トリプロピルアミン
21.5g を仕込み、120 ℃まで昇温し25時間反応した。室
温まで冷却後、トルエン20ml、水80ml、48％NaOHを加え
た。分液してトルエン層を除去した後、水層に36％塩酸
22.8g を滴下した。10℃まで冷却後、結晶を濾別し、真
空乾燥を行い、白色結晶の５−〔４′−クロロメチル−
（１，１′−ビフエニル）−２−イル〕−１Ｈ−テトラ
ゾ−ル、20.6g （収率76.2％、純度99.1％）を得た。Example 3 DMF 50 ml, 4'-chloromethyl-1,
1'-Biphenyl-2-carbonitrile 22.9 g (0.1 mol), sodium azide 7.8 g, tripropylamine hydrochloride
After charging 21.5 g, the temperature was raised to 120 ° C. and the reaction was performed for 25 hours. After cooling to room temperature, 20 ml of toluene, 80 ml of water and 48% NaOH were added. After separating the liquid and removing the toluene layer, 36% hydrochloric acid is added to the aqueous layer.
22.8 g was added dropwise. After cooling to 10 ° C, the crystals were separated by filtration and dried in vacuum to give white crystals of 5- [4'-chloromethyl-
There were obtained 20.6 g (yield 76.2%, purity 99.1%) of (1,1'-biphenyl) -2-yl] -1H-tetrazole.
【００１８】[0018]
【発明の効果】本発明の効果を纏めると下記の通りであ
る。本発明の方法によつて製造されたテトラゾ−ル類は
色相、融点等を充分満足するものが得られた。また反応
速度が従来の方法に比較して著しく速く、生産効率がよ
い。即ち本発明の方法は従来の方法に比較して出発原料
である未反応のニトリル類が有機溶剤で洗浄することに
よつて簡単に除去可能であり、そのため短時間に高純度
のテトラゾ−ル類を高収率で経済的に得ることができ、
本発明は工業的に著しく効果が大である。The effects of the present invention are summarized as follows. As the tetrazole produced by the method of the present invention, one having a sufficiently satisfactory hue, melting point and the like was obtained. Further, the reaction rate is remarkably faster than the conventional method, and the production efficiency is good. That is, in the method of the present invention, unreacted nitriles as a starting material can be easily removed by washing with an organic solvent as compared with the conventional method, and therefore high-purity tetrazole compounds can be obtained in a short time. Can be obtained economically with high yield,
The present invention is extremely effective industrially.
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【手続補正書】[Procedure amendment]
【提出日】平成５年６月３０日[Submission date] June 30, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】[0006]
【反応式（ＩＩ）】 [Reaction formula (II)]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】[0009]
【反応式（ＩＩＩ）】 [Reaction formula (III)]
Claims (1)
−カルボニトリル類とアルカリ金属アザイドとの反応を
アルキルアミン塩類を触媒として使用することを特徴と
する〔化２〕で示される５−（１，１′−ビフエニル）
−１Ｈ−テトラゾ−ル類の製造方法。 【化１】 （ここにＲはＨ又はハロゲン化メチル又はＣ1 〜Ｃ4 の
アルキルである。） 【化２】 （ここにＲはＨ又はハロゲン化メチル又はＣ1 〜Ｃ4 の
アルキルである。）1. Biphenyl-2 represented by the following [Chemical Formula 1]
-(1,1'-biphenyl) represented by [Chemical Formula 2] characterized in that the reaction of carbonitriles with an alkali metal azide is carried out by using an alkylamine salt as a catalyst.
-1H-The manufacturing method of tetrazole. [Chemical 1] (Wherein R is H or methyl halide or C 1 -C 4 alkyl). (Wherein R is H or methyl halide or C 1 -C 4 alkyl).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10873493A JP3419819B2 (en) | 1993-03-19 | 1993-03-19 | Method for producing 5- (1,1'-biphenyl) -1H-tetrazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10873493A JP3419819B2 (en) | 1993-03-19 | 1993-03-19 | Method for producing 5- (1,1'-biphenyl) -1H-tetrazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH072805A true JPH072805A (en) | 1995-01-06 |
| JP3419819B2 JP3419819B2 (en) | 2003-06-23 |
Family
ID=14492176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10873493A Expired - Fee Related JP3419819B2 (en) | 1993-03-19 | 1993-03-19 | Method for producing 5- (1,1'-biphenyl) -1H-tetrazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3419819B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031445A1 (en) * | 1994-05-16 | 1995-11-23 | Sumitomo Chemical Company, Limited | Process for producing tetrazole compound and intermediate therefor |
| EP0796852A1 (en) * | 1996-03-21 | 1997-09-24 | Toyo Kasei Kogyo Company Limited | Process for preparation of 5-substituted tetrazoles |
| KR100354802B1 (en) * | 1994-10-20 | 2002-12-26 | 한국화학연구원 | Process for preparing tetrazole derivatives |
| WO2007014412A1 (en) * | 2005-08-04 | 2007-02-08 | Sanochemia Pharmazeutika Ag | Method for isolating 5-substituted tetrazoles |
| WO2007125585A1 (en) * | 2006-04-27 | 2007-11-08 | Toyo Kasei Kogyo Co., Ltd. | Method for producing bitetrazolamine compound |
| CN110041281A (en) * | 2019-05-20 | 2019-07-23 | 浙江华海致诚药业有限公司 | A kind of diovan foreign matter and preparation method thereof |
| WO2022009968A1 (en) | 2020-07-09 | 2022-01-13 | 丸善石油化学株式会社 | Composition for cancer cell adhesion, filter for capturing cancer cells, and method for detecting cancer cells |
-
1993
- 1993-03-19 JP JP10873493A patent/JP3419819B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031445A1 (en) * | 1994-05-16 | 1995-11-23 | Sumitomo Chemical Company, Limited | Process for producing tetrazole compound and intermediate therefor |
| US5874593A (en) * | 1994-05-16 | 1999-02-23 | Sumitomo Chemical Company, Limited | Production process and intermediate of tetrazole compound |
| US6191289B1 (en) | 1994-05-16 | 2001-02-20 | Sumitomo Chemical Company, Limited | Production process and intermediate of tetrazole compound |
| US6277998B1 (en) | 1994-05-16 | 2001-08-21 | Sumitomo Chemical Company, Limited | Production process and intermediate of tetrazole compound |
| KR100354802B1 (en) * | 1994-10-20 | 2002-12-26 | 한국화학연구원 | Process for preparing tetrazole derivatives |
| EP0796852A1 (en) * | 1996-03-21 | 1997-09-24 | Toyo Kasei Kogyo Company Limited | Process for preparation of 5-substituted tetrazoles |
| US5744612A (en) * | 1996-03-21 | 1998-04-28 | Toyo Kasei Kogyo Company Limited | Process for preparation of 5- substituted tetrazoles |
| US6040454A (en) * | 1996-03-21 | 2000-03-21 | Toyo Kasei Kogyo Company Limited | Process for preparation of a 1-(tetrazolylbiphenylmethyl)-imidazole derivative |
| WO2007014412A1 (en) * | 2005-08-04 | 2007-02-08 | Sanochemia Pharmazeutika Ag | Method for isolating 5-substituted tetrazoles |
| WO2007125585A1 (en) * | 2006-04-27 | 2007-11-08 | Toyo Kasei Kogyo Co., Ltd. | Method for producing bitetrazolamine compound |
| CN110041281A (en) * | 2019-05-20 | 2019-07-23 | 浙江华海致诚药业有限公司 | A kind of diovan foreign matter and preparation method thereof |
| WO2022009968A1 (en) | 2020-07-09 | 2022-01-13 | 丸善石油化学株式会社 | Composition for cancer cell adhesion, filter for capturing cancer cells, and method for detecting cancer cells |
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| Publication number | Publication date |
|---|---|
| JP3419819B2 (en) | 2003-06-23 |
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