JPH04149160A - Production of 1-amino-4-alkoxybenzene compounds - Google Patents
Production of 1-amino-4-alkoxybenzene compoundsInfo
- Publication number
- JPH04149160A JPH04149160A JP2270444A JP27044490A JPH04149160A JP H04149160 A JPH04149160 A JP H04149160A JP 2270444 A JP2270444 A JP 2270444A JP 27044490 A JP27044490 A JP 27044490A JP H04149160 A JPH04149160 A JP H04149160A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alcohol
- indium
- sulfuric acid
- compound
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- -1 nitrobenzene compound Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 abstract 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract 3
- HAOKAUSLWSQQKU-UHFFFAOYSA-N [C].[In] Chemical compound [C].[In] HAOKAUSLWSQQKU-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 description 5
- 238000006665 Bamberger reaction Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- CDGNLUSBENXDGG-UHFFFAOYSA-N meta-Cresidine Chemical compound COC1=CC=C(N)C(C)=C1 CDGNLUSBENXDGG-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000005224 alkoxybenzenes Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
【発明の詳細な説明】
（産業上の利用分野）
本発明は、染料、医薬、農薬等の中間体として有用な１
−アミン−４−アルコキシベンゼン類の製造方法に関す
る。さらに詳しくは、イリジウム触媒の存在下、低級ア
ルコールと硫酸の混合溶媒中で水素により接触還元して
、対応するｌ−アミン−４−アルコキシベンゼン類を製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides 1
-Regarding a method for producing amine-4-alkoxybenzenes. More specifically, it relates to a method for producing the corresponding l-amine-4-alkoxybenzenes by catalytic reduction with hydrogen in a mixed solvent of lower alcohol and sulfuric acid in the presence of an iridium catalyst.
（従来の技術）
１−アミン−４−アルコキシベンゼン類は、染料、医薬
、農薬等の重要な中間体であり、従来、ニトロベンゼン
類から多くの工程を経て製造されている。しかしながら
、従来法においては全収率が低く経済的にも満足すべき
ものではなかった。(Prior Art) 1-Amine-4-alkoxybenzenes are important intermediates for dyes, medicines, agricultural chemicals, etc., and have conventionally been produced from nitrobenzenes through many steps. However, the conventional method has a low overall yield and is not economically satisfactory.
近年、Ｂａｍｂｅｒｇｅｒ反応を応用し、ニトロベンゼ
ン類をアルコールと硫酸の混合溶媒中、白金またはパラ
ジウム触媒存在下に接触還元することにより、１−アミ
ン−４−アルコキシベンゼン類を一段階で製造する方法
が報告されている（例えば、日本化学会誌、、 １９８
０ （２） ２４５頁。Recently, a method for producing 1-amine-4-alkoxybenzenes in one step by applying the Bamberger reaction and catalytically reducing nitrobenzenes in a mixed solvent of alcohol and sulfuric acid in the presence of a platinum or palladium catalyst has been reported. (e.g., Journal of the Chemical Society of Japan, 198
0 (2) 245 pages.
特開昭６０−１１５５５６ および 特開昭６１−１
０９７５９）。 また、これらとは別にオルト置換ベン
ゼン類の電解還元による合成も試みられている（例えば
、特開昭５５−１５４５９０）。JP-A-60-115556 and JP-A-61-1
09759). In addition to these, attempts have also been made to synthesize ortho-substituted benzenes by electrolytic reduction (for example, JP-A-55-154590).
（発明が解決しようとする課題）
このようにＢａｍｂｅｒｇｅｒ反応を応用し、白金また
はパラジウム触媒存在下、接触還元することによりニト
ロベンゼン類より一段階で対応する１−アミン−４−ア
ルコキシベンゼン類を得る方法は公知であるが、これら
の方法は、いずれもジメチルスルホキシド、水及び／ま
たは低級脂肪族カルボン酸等の添加を必要とするのみな
らず、Ｂａｍｂｅｒｇｅｒ転位が進行せずにニトロ基の
みが還元されたアミノベンゼン類の副生が多く、まだ満
足できる還元反応選択性は得られていない。(Problems to be Solved by the Invention) As described above, a method of applying the Bamberger reaction to obtain the corresponding 1-amine-4-alkoxybenzenes from nitrobenzenes in one step by catalytic reduction in the presence of a platinum or palladium catalyst. are known, but all of these methods not only require the addition of dimethyl sulfoxide, water and/or lower aliphatic carboxylic acids, but also reduce only the nitro group without Bamberger rearrangement proceeding. Many aminobenzenes are produced as by-products, and satisfactory reduction reaction selectivity has not yet been obtained.
また、オルト置換ニトロベンゼン類の電解還元による方
法は、製造装置、廃液処理方法（施設）、経済性等長（
の問題を有する。In addition, the method of electrolytic reduction of ortho-substituted nitrobenzenes requires manufacturing equipment, waste liquid treatment method (facility), economic efficiency, etc.
have a problem.
（課題を解決するための手段）
本発明者らは、上記課題を解決するために高収率、高選
択性の１−アミン−４−アルコキシベンゼン類の製造方
法について、特にＢａｍｂｅｒｇｅｒ反応を応用する一
段階合成法における水素化触媒について鋭意検討した結
果、従来公知の白金またはパラジウム触媒に比べ、一般
に接触還元反応において触媒能が低く適用範囲が狭いと
されているイリジウム触媒が、本反応において特異な挙
動を示すことを見出した。(Means for Solving the Problems) In order to solve the above problems, the present inventors particularly applied the Bamberger reaction to a method for producing 1-amine-4-alkoxybenzenes with high yield and high selectivity. As a result of intensive studies on hydrogenation catalysts in one-step synthesis methods, we found that iridium catalysts, which are generally considered to have lower catalytic ability and a narrower range of application in catalytic reduction reactions than conventionally known platinum or palladium catalysts, have a unique feature in this reaction. It was found that this behavior was observed.
即ち本発明はニトロベンゼン類をイリジウム触媒の存在
下、ジメチルスルホキシド、水、低級脂肪族カルボン酸
などの添加物をなんら加えることなく、所定量のアルコ
ールおよび硫酸の混合溶媒中、きわめて温和な温度、圧
力条件下で、水素を通人して接触還元することにより高
転化率、高選択性で高純度の対応する１−アミン−４−
アルコキシベンセン類が得られる方法を完成した。That is, the present invention deals with the treatment of nitrobenzenes in the presence of an iridium catalyst in a mixed solvent of a predetermined amount of alcohol and sulfuric acid at extremely mild temperatures and pressures without adding any additives such as dimethyl sulfoxide, water, or lower aliphatic carboxylic acids. High conversion, high selectivity and high purity of the corresponding 1-amine-4-
A method for obtaining alkoxybenzenes has been completed.
本発明において使用されるニトロベンゼン類としては、
ニトロベンゼン、オルト及び／またはメタ位にハロゲン
、Ｃ６〜Ｃ６の低級アルキル基、Ｃ１〜Ｃ６の低級アル
コキシ基、５Ｏ２Ｒ’ （Ｒ’ はＣ３〜Ｃ６の低級
アルキル基をあられす） 、Ｃｏ２Ｒ’ （Ｒ２はＣ
１〜Ｃ８の低級アルキル基をあられす） 、ＣＯＲ’
（Ｒ’はＣ１〜Ｃ６の低級アルキル基をあられす）な
どの通常の接触還元反応において不活性な置換基を有す
るニトロベンゼン類を挙げることができる。The nitrobenzenes used in the present invention include:
Nitrobenzene, halogen at the ortho and/or meta position, C6 to C6 lower alkyl group, C1 to C6 lower alkoxy group, 5O2R'(R' is a C3 to C6 lower alkyl group), Co2R' (R2 is C
1-C8 lower alkyl group), COR'
Examples include nitrobenzenes having substituents that are inactive in ordinary catalytic reduction reactions, such as (R' is a lower alkyl group of C1 to C6).
本発明において使用される触媒は、イリジウムの（不活
性固体）担持触媒及びこれと他の貴金属の担持触媒の混
合物である。イリジウムの担持量は担体に対して０．１
Ｘ〜２０Ｘ程度であり、１〜５Ｘのイリジウムカーボン
が好ましい。また、反応させるニトロベンゼン類１モル
に対するイリジウム触媒の使用量は０．１〜５００ｍｇ
、好ましくは１０〜１００ｍｇである。The catalyst used in the present invention is a (inert solid) supported catalyst of iridium and mixtures thereof with supported catalysts of other precious metals. The amount of iridium supported is 0.1 to the carrier
It is about X to 20X, and 1 to 5X iridium carbon is preferable. In addition, the amount of iridium catalyst used per mole of nitrobenzene to be reacted is 0.1 to 500 mg.
, preferably 10 to 100 mg.
用いられるアルコール類は、炭素数１〜４の低級アルコ
ールであり、メタノール、エタノール、ノルマルプロパ
ツールおよびイソプロパツール等を例示できる。用いら
れるアルコールは、原料のニトロベンゼン類に対して５
〜２００倍モル、より好ましくは２０〜１００倍モルで
ある。用いられる硫酸は、原料のニトロベンゼン類に対
して０．１〜２０倍モル、より好ましくは１〜５倍モル
である。反応に使用される混合溶媒は、アルコールに対
して硫酸濃度が１〜５０重量％のものである。The alcohol used is a lower alcohol having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, normal propatool, and isopropanol. The alcohol used is 5% based on the raw material nitrobenzene.
~200 times the mole, more preferably 20 to 100 times the mole. The amount of sulfuric acid used is 0.1 to 20 times, more preferably 1 to 5 times, the amount of nitrobenzene used as a raw material. The mixed solvent used in the reaction has a sulfuric acid concentration of 1 to 50% by weight relative to alcohol.
反応は常圧からｌＯ気圧の範囲において、０℃から還流
温度内で、好ましくは常圧、３０〜６０℃において円滑
に進行する。The reaction proceeds smoothly in the range from normal pressure to 1O atm, at 0°C to reflux temperature, preferably at normal pressure and 30 to 60°C.
反応後、触媒を濾別し、アルコールを減圧留去したのち
、常法により中和し、ベンセン、トルエンなとの適当な
有機溶媒で抽出して、有機層を減圧蒸留することにより
目的とする１−アミン−４−アルコキノベンセン類を単
離することができる。After the reaction, the catalyst is filtered off, the alcohol is distilled off under reduced pressure, neutralized by a conventional method, extracted with an appropriate organic solvent such as benzene or toluene, and the organic layer is distilled under reduced pressure to obtain the desired product. 1-Amine-4-alcoquinobenzenes can be isolated.
以上のように、本発明の方法はニトロベンゼン類よりイ
リジウム触媒の存在下、何らの添加物を加えることなく
、きわめて温和な条件で、高転化率、高選択率で高純度
の１−アミン−４−アルコキシベンセン類を得る工業的
に有利なものである。As described above, the method of the present invention produces high conversion, high selectivity, and high purity 1-amine-4 from nitrobenzenes in the presence of an iridium catalyst, without adding any additives, and under extremely mild conditions. - It is industrially advantageous for obtaining alkoxybenzenes.
以下に実施例をあげて本発明をさらに具体的に説明する
。The present invention will be explained in more detail with reference to Examples below.
（実施例）
実施例１
容量１１の４０フラスコに攪拌機、温度計、水素吹き込
み管及び冷却器をつけた反応器に、０−ニトロトルエン
３４．３ｇ（０，２５モル）、メチルアルコール４８０
ｍ１ （１１，８８モル） 、９５Ｘ硫酸６２゜０ｇ
（０，６０モル）及び５Ｘイリジウムカーボン触媒０、
２５ｇを入れた。攪拌下、反応溶液中に水素ガスを６０
ｍ１／ｍｉｎの速度で連続的に吹き込んで反応を行い、
その間温度は５０℃に保った。ガスクロマトグラフィー
分析によって原料の０−ニトロトルエンが消失したこと
が確認されたところで反応を終了した。この間４時間を
要した。反応終了後、触媒を濾別したのちメタノールを
減圧留去した。濃縮液を常法により中和し、トルエンで
抽出した後、抽出液をガスクロマトグラフィーにて分析
した結果、２−メチル−４−メトキシアニリンが８５．
４Ｘ 、ｏ−トルイジンが１３．１Ｘであった。(Example) Example 1 34.3 g (0.25 mol) of 0-nitrotoluene and 480 g of methyl alcohol were placed in a reactor equipped with a 40 flask with a capacity of 11 and equipped with a stirrer, a thermometer, a hydrogen blowing tube, and a condenser.
m1 (11,88 mol), 95X sulfuric acid 62゜0g
(0,60 mol) and 5X iridium carbon catalyst 0,
25g was added. While stirring, add 60% hydrogen gas into the reaction solution.
The reaction is carried out by continuously blowing at a rate of m1/min,
During this time, the temperature was maintained at 50°C. The reaction was terminated when it was confirmed by gas chromatography analysis that the raw material 0-nitrotoluene had disappeared. This took 4 hours. After the reaction was completed, the catalyst was filtered off, and methanol was distilled off under reduced pressure. After neutralizing the concentrated solution using a conventional method and extracting it with toluene, the extracted solution was analyzed by gas chromatography. As a result, 2-methyl-4-methoxyaniline was found to be 85.
4X, o-toluidine was 13.1X.
実施例２
５％イリジウムカーボン触媒０．２５ｇのかわりに３％
イリジウムカーボン触媒０．２５ｇを用いた以外は実施
例１と全く同様の操作を行ってガスクロマトグラフィー
にて分析した結果、２−メチル−４−メトキシアニリン
が８６．９Ｘで〇−トルイジンは１１．６Ｘであった。Example 2 3% instead of 0.25g of 5% iridium carbon catalyst
The same procedure as in Example 1 was carried out except that 0.25 g of iridium carbon catalyst was used, and analysis by gas chromatography revealed that 2-methyl-4-methoxyaniline was 86.9X and 〇-toluidine was 11X. It was 6X.
比較例
５％イリジウムカーボン触媒０．２５ｇの替わりに、３
％プラチナカーボン触媒０．２５ｇを用いた以外は実施
例１と全く同様の操作を行ってガスクロマトグラフィー
の分析の結果、２−メチル−４−メトキシアニリンが７
６、０％で〇−トルイジンは２１．５Ｎであった。Comparative Example Instead of 0.25 g of 5% iridium carbon catalyst, 3
The same procedure as in Example 1 was carried out except that 0.25 g of % platinum carbon catalyst was used, and as a result of gas chromatography analysis, 2-methyl-4-methoxyaniline was found to be 7.
At 6.0%, 0-toluidine was 21.5N.
（発明の効果）
本発明は、ニトロベンゼン類からイリジウム触媒を用い
る接触還元によって従来法に比べ、高転化率、高選択性
で高純度の１−アミン−４−アルコキシベンゼン類を得
るものであり、経済性にもすぐれ、その産業的意義は、
きわめて大きいものである。(Effects of the Invention) The present invention obtains 1-amine-4-alkoxybenzenes with higher conversion, higher selectivity, and higher purity than conventional methods by catalytic reduction of nitrobenzenes using an iridium catalyst. It has excellent economic efficiency, and its industrial significance is
It is extremely large.
Claims (1)
触還元することを特徴とする１−アミン−４−アルコキ
シベンゼン類の製造方法(1) A method for producing 1-amine-4-alkoxybenzenes, which comprises catalytically reducing nitrobenzenes in the presence of an iridium catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2270444A JP2984047B2 (en) | 1990-10-11 | 1990-10-11 | Method for producing 1-amino-4-alkoxybenzenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2270444A JP2984047B2 (en) | 1990-10-11 | 1990-10-11 | Method for producing 1-amino-4-alkoxybenzenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149160A true JPH04149160A (en) | 1992-05-22 |
| JP2984047B2 JP2984047B2 (en) | 1999-11-29 |
Family
ID=17486374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2270444A Expired - Fee Related JP2984047B2 (en) | 1990-10-11 | 1990-10-11 | Method for producing 1-amino-4-alkoxybenzenes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2984047B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100349035B1 (en) * | 2000-07-01 | 2002-08-17 | 한국과학기술연구원 | Method for the allkylation of aldehyde and reduction of nitro group in one-pot using indium and acid |
| KR100362706B1 (en) * | 2000-04-21 | 2002-12-11 | 한국과학기술연구원 | A method for reducing nitro group to amine group using indium |
| KR100530345B1 (en) * | 2002-10-30 | 2005-11-22 | 한국과학기술연구원 | Method for preparing amine compound from nitro compound using indium metal wire |
| WO2006054491A1 (en) * | 2004-11-17 | 2006-05-26 | Eisai R & D Management Co., Ltd. | Process for producing n-(3-chloro-1h-indol-7-yl)-4-sulfamoylbenzenesulfonamide |
| CN103193660A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Synthetic method of 4-alkoxy phenylamine compound |
| CN112812027A (en) * | 2021-01-06 | 2021-05-18 | 湘潭大学 | Methoxyaniline compound and synthetic method thereof |
-
1990
- 1990-10-11 JP JP2270444A patent/JP2984047B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100362706B1 (en) * | 2000-04-21 | 2002-12-11 | 한국과학기술연구원 | A method for reducing nitro group to amine group using indium |
| KR100349035B1 (en) * | 2000-07-01 | 2002-08-17 | 한국과학기술연구원 | Method for the allkylation of aldehyde and reduction of nitro group in one-pot using indium and acid |
| KR100530345B1 (en) * | 2002-10-30 | 2005-11-22 | 한국과학기술연구원 | Method for preparing amine compound from nitro compound using indium metal wire |
| WO2006054491A1 (en) * | 2004-11-17 | 2006-05-26 | Eisai R & D Management Co., Ltd. | Process for producing n-(3-chloro-1h-indol-7-yl)-4-sulfamoylbenzenesulfonamide |
| CN103193660A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Synthetic method of 4-alkoxy phenylamine compound |
| CN112812027A (en) * | 2021-01-06 | 2021-05-18 | 湘潭大学 | Methoxyaniline compound and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2984047B2 (en) | 1999-11-29 |
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