JP2002053569A - Method for producing 1,3-azole - Google Patents
Method for producing 1,3-azoleInfo
- Publication number
- JP2002053569A JP2002053569A JP2000241690A JP2000241690A JP2002053569A JP 2002053569 A JP2002053569 A JP 2002053569A JP 2000241690 A JP2000241690 A JP 2000241690A JP 2000241690 A JP2000241690 A JP 2000241690A JP 2002053569 A JP2002053569 A JP 2002053569A
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- halogen
- hydrogen
- group selected
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、酸性または中性ア
ルミナを用いた新規な1,3−アゾール類の製造方法に
関する。The present invention relates to a novel method for producing 1,3-azoles using acidic or neutral alumina.
【0002】[0002]
【従来技術】Tetrahedron 54(199
8)8055〜8064によれば、MnO2/SiO2
触媒を用いて、下記反応式2. Description of the Related Art Tetrahedron 54 (199)
8) According to 8055 to 8064, MnO 2 / SiO 2
Using the catalyst, the following reaction formula
【化4】 (式中、XはNH、OおよびSよりなる群から選ばれた
基であり、R1およびR2は、水素、塩素およびNO2
よりなる群から選ばれた基である。)により1,3−ア
ゾール類を製造する方法が提案されている。Embedded image Wherein X is a group selected from the group consisting of NH, O and S, and R 1 and R 2 are hydrogen, chlorine and NO 2
A group selected from the group consisting of: ) Has been proposed for producing 1,3-azoles.
【0003】しかし、前記反応は80Wの超音波、また
は電磁波をかけて実施するものであるが、このようなエ
ネルギーをかける反応系では、反応温度がたちまち14
0℃またはそれ以上に上昇してしまい、通常10〜12
分間で200〜226℃に達し、種々の副反応を伴う。[0003] However, the above reaction is carried out by applying an ultrasonic wave or an electromagnetic wave of 80 W, and in a reaction system in which such energy is applied, the reaction temperature is rapidly increased.
0 ° C or higher, usually 10-12
It reaches 200-226 ° C. in a minute and involves various side reactions.
【0004】[0004]
【発明が解決しようとする課題】本発明は、前記反応を
130℃以下の低温で実施できる新規な方法を提供する
点にある。An object of the present invention is to provide a novel method capable of carrying out the reaction at a low temperature of 130 ° C. or less.
【0005】[0005]
【課題を解決するための手段】本発明は、下記一般式
(1)Means for Solving the Problems The present invention provides the following general formula (1)
【化5】 (式中、XはNH、OおよびSよりなる群から選ばれた
基であり、R1およびR2は、水素、ハロゲンおよびN
O2よりなる群から選ばれた基である。)で示されるア
ミノベンゼン誘導体に、酸性アルミナ、中性アルミナお
よびシリカゲルよりなる群から選ばれた触媒の存在下
で、下記一般式(2)Embedded image Wherein X is a group selected from the group consisting of NH, O and S, and R 1 and R 2 are hydrogen, halogen and N
It is a group selected from the group consisting of O 2 . In the presence of a catalyst selected from the group consisting of acidic alumina, neutral alumina and silica gel, the aminobenzene derivative represented by the following general formula (2):
【化6】 (式中、Arは芳香族炭化水素基であり、Gは水素、ハ
ロゲン、NO2、水酸基、アルキル基およびアルコキシ
基よりなる群から選ばれた基である。)で示される芳香
族アルデヒド類を反応させることを特徴とする一般式Embedded image (Wherein, Ar is an aromatic hydrocarbon group, and G is a group selected from the group consisting of hydrogen, halogen, NO 2 , hydroxyl group, alkyl group and alkoxy group). General formula characterized by reacting
【化7】 (式中、Xは、NH、OおよびSよりなる群から選ばれ
た基であり、R1およびR2は、水素、ハロゲンおよび
NO2よりなる群から選ばれた基であり、Arは芳香族
炭化水素基であり、Gは、水素、ハロゲン、NO2、水
酸基、アルキル基およびアルコキシ基よりなる群から選
ばれた基である。)で示される1,3−アゾール類の製
造方法に関する。Embedded image (Wherein X is a group selected from the group consisting of NH, O and S, R 1 and R 2 are groups selected from the group consisting of hydrogen, halogen and NO 2 , and Ar is aromatic G is a group selected from the group consisting of hydrogen, halogen, NO 2 , a hydroxyl group, an alkyl group, and an alkoxy group.)
【0006】本発明の実施に当っては、アミノベンゼン
誘導体に対して、芳香族アルデヒド類を過剰量で使用す
ることが好ましく、アミノベンゼン誘導体に対し、芳香
族アルデヒド類を好ましくは1.3当量以上、とくに好
ましくは1.6〜1.8当量の割合で使用する。等モル
で反応させる場合には、副反応生成物として二量体が生
成するが、芳香族アルデヒドを過剰当量使用することに
より、二量体の生成を防止することができる。In practicing the present invention, it is preferable to use an excess amount of aromatic aldehyde with respect to the aminobenzene derivative, and preferably use 1.3 equivalents of the aromatic aldehyde with respect to the aminobenzene derivative. As described above, it is particularly preferably used at a ratio of 1.6 to 1.8 equivalents. When the reaction is carried out in an equimolar amount, a dimer is generated as a by-product, but by using an excess amount of the aromatic aldehyde, the dimer can be prevented.
【0007】本発明に用いる触媒は、酸性アルミナが最
も良好な結果を与える。中性アルミナではやや収率が低
下し、塩基性アルミナではほとんど反応が進まない。シ
リカゲルは中性アルミナと同程度の反応性を示す。酸性
アルミナとしては、カラムクロマトグラフ用の酸性アル
ミナを用いて実験した。As the catalyst used in the present invention, acidic alumina gives the best results. The yield slightly decreases with neutral alumina, and the reaction hardly proceeds with basic alumina. Silica gel shows the same degree of reactivity as neutral alumina. The experiment was performed using acidic alumina for column chromatography as the acidic alumina.
【0008】本発明における芳香族アルデヒド類は、酸
性アルミナ表面上でアルデヒドのカルボニル酸素が酸点
に吸着し、それによりカルボニル炭素が求核攻撃を受け
やすくなったものと考えられるが、何故固体酸のシリカ
ゲルより、酸性アルミナの方が優れているのかは解明で
きていない。The aromatic aldehydes of the present invention are considered to be those in which the carbonyl oxygen of the aldehyde is adsorbed to the acid sites on the surface of the acidic alumina, thereby making the carbonyl carbon more susceptible to nucleophilic attack. It is not clear whether acidic alumina is superior to silica gel.
【0009】本発明の反応は、無溶媒でも溶媒中でも実
施できる。溶媒としてはメタノールなどのアルコール類
や酢酸エチルなどのエステル類など任意の反応に対して
不活性な溶媒を用いることができる。The reaction of the present invention can be carried out without a solvent or in a solvent. As a solvent, a solvent inert to an arbitrary reaction such as an alcohol such as methanol or an ester such as ethyl acetate can be used.
【0010】なお、前記Gとしてのアルキル基やアルコ
キシ基は、格別の制限はないが、通常炭素数1〜4の低
級アルキル基または低級アルコキシ基が好ましい。The alkyl group or alkoxy group as G is not particularly limited, but is usually a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group.
【0011】[0011]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれにより何ら限定されるものではない。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited thereby.
【0012】実施例1〜5 酸性アルミナ2gに、下記一般式(4)Examples 1 to 5 2 g of acidic alumina was added to the following general formula (4)
【化8】 で示される芳香族アルデヒド(対応するGは表1中に示
す)1.8ミリモルを加えて撹拌し、その後、式Embedded image 1.8 mmol of an aromatic aldehyde represented by the following formula (corresponding G is shown in Table 1) was added thereto, followed by stirring.
【化9】 で示されるo−アミノチオフェノール1.0ミリモルを
加え、窒素雰囲気下で、表1中に示す時間100℃に保
って撹拌下に反応した。反応終了後、溶媒15ミリリッ
トルを加え、15分間撹拌し、その後、酸性アルミナを
濾別してガスクロマトグラフィーによる定量(内標準
法)や、単離による定量を行った。生成物の構造は、N
MR、IR、MSスペクトルによって確認した。Embedded image Was added thereto, and the mixture was reacted under a nitrogen atmosphere with stirring at 100 ° C. for the time shown in Table 1. After completion of the reaction, 15 ml of a solvent was added, and the mixture was stirred for 15 minutes. Thereafter, acidic alumina was separated by filtration and quantified by gas chromatography (internal standard method) or quantified by isolation. The structure of the product is N
Confirmed by MR, IR and MS spectra.
【0013】[0013]
【表1】 A:メタノール B:酢酸エチル[Table 1] A: methanol B: ethyl acetate
【0014】[0014]
【発明の効果】(1)本発明により、1,3−アゾール
類の新規な製造方法を提供することができた。 (2)本発明の方法は、必要により無溶媒で実施できる
ので、溶媒による環境汚染がない。 (3)生成物の純度が高い。(1) According to the present invention, a novel method for producing 1,3-azoles can be provided. (2) Since the method of the present invention can be carried out without a solvent if necessary, there is no environmental pollution by the solvent. (3) The purity of the product is high.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 武田 孝 兵庫県神戸市中央区東川崎町1丁目3番3 号 ケミプロ化成株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takashi Takeda 1-3-3 Higashikawasakicho, Chuo-ku, Kobe-shi, Hyogo
Claims (2)
基であり、R1およびR2は、水素、ハロゲンおよびN
O2よりなる群から選ばれた基である。)で示されるア
ミノベンゼン誘導体に、酸性または中性のアルミナの存
在下で、下記一般式(2) 【化2】 (式中、Arは芳香族炭化水素基であり、Gは水素、ハ
ロゲン、NO2、水酸基、アルキル基およびアルコキシ
基よりなる群から選ばれた基である。)で示される芳香
族アルデヒド類を反応させることを特徴とする一般式 【化3】 (式中、Xは、NH、OおよびSよりなる群から選ばれ
た基であり、R1およびR2は、水素、ハロゲンおよび
NO2よりなる群から選ばれた基であり、 Arは芳香族炭化水素基であり、Gは、水素、ハロゲ
ン、NO2、水酸基、アルキル基およびアルコキシ基よ
りなる群から選ばれた基である。)で示される1,3−
アゾール類の製造方法。[Claim 1] The following general formula (1) Wherein X is a group selected from the group consisting of NH, O and S, and R 1 and R 2 are hydrogen, halogen and N
It is a group selected from the group consisting of O 2 . In the presence of acidic or neutral alumina, an aminobenzene derivative represented by the following general formula (2): (Wherein, Ar is an aromatic hydrocarbon group, and G is a group selected from the group consisting of hydrogen, halogen, NO 2 , hydroxyl group, alkyl group and alkoxy group). General formula characterized by reacting (Wherein, X is a group selected from the group consisting of NH, O and S, R 1 and R 2 are groups selected from the group consisting of hydrogen, halogen and NO 2 , and Ar is aromatic And G is a group selected from the group consisting of hydrogen, halogen, NO 2 , a hydroxyl group, an alkyl group, and an alkoxy group.)
A method for producing azoles.
誘導体に対して、一般式(2)で示される芳香族アルデ
ヒド類を過剰モル使用する請求項1記載の1,3−アゾ
ール類の製造方法。2. The production of 1,3-azoles according to claim 1, wherein the aromatic aldehyde represented by the general formula (2) is used in excess molar amount with respect to the aminobenzene derivative represented by the general formula (1). Method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000241690A JP4628528B2 (en) | 2000-08-09 | 2000-08-09 | Method for producing 1,3-azoles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000241690A JP4628528B2 (en) | 2000-08-09 | 2000-08-09 | Method for producing 1,3-azoles |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002053569A true JP2002053569A (en) | 2002-02-19 |
JP4628528B2 JP4628528B2 (en) | 2011-02-09 |
Family
ID=18732846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000241690A Expired - Fee Related JP4628528B2 (en) | 2000-08-09 | 2000-08-09 | Method for producing 1,3-azoles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4628528B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7554000B2 (en) | 2002-02-05 | 2009-06-30 | Sumitomo Chemical Company, Limited | Process for producing biaryl compound |
-
2000
- 2000-08-09 JP JP2000241690A patent/JP4628528B2/en not_active Expired - Fee Related
Non-Patent Citations (4)
Title |
---|
JPN6010044939, Tetrahedron (1998), 54(28), 8055−8064 * |
JPN6010044940, Synthesis (2000), (10), 1380−1390 * |
JPN6010044941, Collection of Czechoslovak Chemical Communications (1981), 46(11), 2703−2708 * |
JPN6010044942, Tetrahedron Letters, 17(39) 3499−3502 (1976) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7554000B2 (en) | 2002-02-05 | 2009-06-30 | Sumitomo Chemical Company, Limited | Process for producing biaryl compound |
US8242278B2 (en) | 2002-02-05 | 2012-08-14 | Sumitomo Chemical Company, Limited | Process for producing biaryl compound |
Also Published As
Publication number | Publication date |
---|---|
JP4628528B2 (en) | 2011-02-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2002053569A (en) | Method for producing 1,3-azole | |
JPH07247289A (en) | Method for producing chromene oxide compounds | |
TWI781128B (en) | Processes for the preparation of pesticidal compounds | |
JPH11180974A (en) | Production of vinylene carbonate | |
CN110627626B (en) | Preparation method of propargyl acetone compound | |
JP4481589B2 (en) | Method for producing bisphosphine | |
JP3788525B2 (en) | Scandium-perfluoroalkanesulfonylimide complex and method for producing the same | |
JPH029013B2 (en) | ||
JP3281916B2 (en) | Method for producing acetal compound and catalyst for the production reaction | |
JPH07215904A (en) | Production of hydroxypivalaldehyde | |
JP3503993B2 (en) | Method for producing N-mono-t-butyloxycarbonylalkylenediamine | |
RU2134255C1 (en) | Method of preparing n-butyl substituted c60. fullerenes | |
RU2135447C1 (en) | Method of synthesis of 1-aryl-(alkyl)-2-hydro[60]-fullerenes | |
JP3765394B2 (en) | Underwater aldol reaction method | |
JP2676105B2 (en) | Method for producing 2,2,6,6-tetramethyl-4-oxopiperidine | |
KR100330026B1 (en) | Method for the preparation of ketone | |
JP2004238368A (en) | Process for aza diels-alder reaction | |
JPS59163352A (en) | Production of serine | |
KR100502707B1 (en) | Method for the preparation of α,β-unsaturated Ketone | |
JP2003286243A (en) | Method for producing n-oxide and catalyst therefor | |
CN114773229A (en) | 1,6 diene compound and preparation method and application thereof | |
JP2003267940A (en) | Method for stereo-selectively producing amine | |
JPH1087530A (en) | Reduction of aldehyde or ketone | |
JP2003246785A (en) | Method for manufacturing 6,7-dihydroxycoumarin | |
JPH01246248A (en) | Reduction of alpha-amino-dicarboxylic acid diester |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070713 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100510 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100728 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100810 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101008 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101102 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101110 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |