JP3744019B2 - Process for producing 1,3-diamino-4,6-dialkoxybenzene and salts thereof - Google Patents
Process for producing 1,3-diamino-4,6-dialkoxybenzene and salts thereof Download PDFInfo
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- JP3744019B2 JP3744019B2 JP08678795A JP8678795A JP3744019B2 JP 3744019 B2 JP3744019 B2 JP 3744019B2 JP 08678795 A JP08678795 A JP 08678795A JP 8678795 A JP8678795 A JP 8678795A JP 3744019 B2 JP3744019 B2 JP 3744019B2
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
【０００１】
【産業上の利用分野】
本発明は、１，３−ジアミノ−４，６−ジアルコキシベンゼン及びその塩の製造方法に関する。
更に詳しくは、次式で表される様に一般式〔Ｉ〕の１−アルコキシ−２，４−ジニトロベンゼンを還元によって、１，３−ジアミノ−４，６−ジアルコキシベンゼン及びその塩を製造する方法に関する。
【０００２】
【化３】
（式中、ＲとＲ′は炭素数１〜４のアルキル基を示し、同一であっても異っていても良い。）
１，３−ジアミノ−４，６−ジアルコキシベンゼンは、脱アルキル化して得られる４，６−ジアミノレゾルシンが、種々の優れた特徴を持つポリベンゾビスオキサゾール（ＰＢＯ）のモノマーとなるので、その原料として重要である。
【０００４】
ＰＢＯは、強度、弾性率、耐熱性、耐薬品性等の諸点に於て、従来のスーパー繊維より優れて居り、超スーパー繊維として開発が待望されている（特表昭６１−５０１４５２号公報）。
【０００５】
【従来の技術】
従来、１，３−ジアミノ−４，６−ジメトキシベンゼンの製造方法は、１，３−ジメトキシベンゼンをジニトロ化した後、還元して得られる方法が知られている（テトラヘドロン ２０巻 １２号 ２９７７〜２９８３頁（１９６４年）〔Tetrahedron 20(12),2977-2983(1964)]
しかしこの方法では、原料の１，３−ジメトキシベンゼンが高価で工業的製法とはなりえない。
【０００６】
【発明が解決しようとする課題】
本発明者は、安価な原料から１，３−ジアミノ−４，６−ジメトキシベンゼンを得る方法を鋭意検討した。
その結果、１−クロル−２，４−ジニトロベンゼン（ＣＤＮＢ）を原料とし塩基の存在下、アルコールと反応させて得られる１−アルコキシ−２，４−ジニトロベンゼン（ＡＤＮＢ）を原料とし、酸−アルコール系で、触媒の存在下に還元することで、還元転位〔バンバーガー（Bamberger)転位〕させ１，３−ジアミノ−４，６−ジメトキシベンゼン（ＤＡＤＭＢ）が得られることを見出し本発明を完成させた。
【０００７】
【化４】
本発明の目的は、１−アルコキシ−２，４−ジニトロベンゼンより１，３−ジアミノ−４，６−ジアルコキシベンゼンの製造方法の提供にある。
【０００９】
【課題を解決するための手段】
即ち、本発明は、
一般式〔Ｉ〕
【００１０】
【化５】
（式中、Ｒは炭素数１〜４のアルキル基を表す。）
で表される１−アルコキシ−２，４−ジニトロベンゼンを炭素数１〜４のアルコール、酸及び第VIII族の還元触媒の存在下に水素で還元することを特徴とする一般式〔II〕
【００１２】
【化６】
（式中、ＲとＲ′は炭素数１〜４のアルキル基を表し、同一であっても異なっていても良い。）
で表される１，３−ジアミノ−４，６−ジアルコキシベンゼン及びその塩の製造方法に関する。
以下、本発明を詳細に説明する。
【００１４】
まず、本発明の原料である一般式〔Ｉ〕で示される１−アルコキシ−２，４−ジニトロベンゼンの、Ｒは炭素数１〜４のアルキル基で、具体的には、１−メトキシ−ジニトロベンゼン、１−エトキシ−ジニトロベンゼン、１−ｎ−プロポキシ−ジニトロベンゼン、１−イソプロポキシ−ジニトロベンゼン、１−ｎ−ブトキシ−ジニトロベンゼン、１−ｓｅｃ−ブトキシ−ジニトロベンゼン、１−ｔｅｒｔ−ブトキシ−ジニトロベンゼンが挙げられる。これらの化合物は、１−クロル−２，４−ジニトロベンゼンを原料とし塩基の存在下、対応するアルコールと反応させて容易に得られる。
【００１５】
反応に用いるアルコールとしては、炭素数１〜４で、具体的にはメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール等が挙げられる。アルコールの使用量は、原料の１−アルコキシ−２，４−ジニトロベンゼン（ＡＤＮＢ）に対して１当量以上、溶媒を兼ねて使用することができる。通常は原料のＡＤＮＢに対して２〜２０重量倍程度使用する。
【００１６】
反応に用いる酸としては、酸が硫酸、塩酸、燐酸、蟻酸、酢酸、プロピオン酸及びメタスルホン酸の中ら選ばれた少なくとも１種の酸が使用できる。これらの酸の中で特には、硫酸が好ましい。酸の濃度は、２０〜１００重量％（８０〜０重量％：水）が好ましく、その使用量は、原料のＡＤＮＢに対して０．５〜１０当量が好ましい。
【００１７】
反応に用いる還元触媒としては、ニッケル、コバルト、鉄、パラジウム、ロジウム、ルテニウム、白金等の第VIII族の金属単身あるいは炭素、アルミナ、シリカ、ゼオライト及びその他の担体に担持した触媒が使用できる。これらの触媒の中で特に白金−炭素及びパラジウム−炭素の担持触媒が好ましい。触媒の使用量は、原料のＡＤＮＢに対して１〜５％金属−担持触媒として０．１〜３０重量％が好ましい。水素圧は大気圧から１０ｋｇ／ｃｍ2 程度で反応は進行するが、特には１〜３Ｋｇ／ｃｍ2 が好ましい。
【００１８】
本反応では、ジメチルスルホキシド（ＤＭＳＯ）を加えることにより目的物の選択率を上げることができる。その添加量は原料のＡＤＮＢに対して０．１〜１０重量％が好ましい。
反応温度は、０℃〜１５０℃で可能であるが、好ましくは２０〜１２０℃の範囲が良い。反応時間は水素吸収量から決定することができる。反応は回分あるいは連続でも行うことが出来る。
【００１９】
反応終了後の後処理は、例えば以下の様にして行うことが出来る。即ち、反応終了後の反応液をろ過し触媒を回収した後、ろ液を濃縮し、必要ならば水を加えてｐＨ７〜８まで中和する。この中和液に酢酸エチルまたは１，２−ジクロロエタンを加えて抽出し、油層を濃縮する。得られた粗物を再結晶又はカラムクロマトグラフィーで精製することにより目的とする１，３−ジアミノ−４，６−ジアルコキシベンゼンの単品が得られる。
【００２０】
以下、実施例を持って本発明を更に詳細に説明するが、これらによって本発明は限定されるものではない。
【００２１】
【実施例】
実施例１
２，４−ジニトロアニソール１．９８ｇ（１０ミリモル）、メタノール１５．２ｇ、７６重量％硫酸（９７重量％硫酸２．５ｇ＋水０．７ｇ）及び２％白金／炭素０．０５ｇを１００ｍｌオートクレーブに仕込み、水素圧２ｋｇ／ｃｍ2 、５０℃で３時間攪拌した。
【００２２】
反応後、室温に戻し脱圧した後、反応物を取り出した。反応液中の触媒をろ過により除いてから、濃縮すると黒色結晶２．３ｇが得られた。この結晶は、液体クロマトグラフィー（ＬＣ）分析の結果、主に２成分からなることが判った。この結晶を中和後、酢酸エチルで抽出してから、シリカゲルによるカラムクロマトグラフィーをかけ両成分を分離した。これらのＭＡＳＳ及び 1Ｈ−ＮＭＲで分析した結果、主成分は、１，３−ジアミノ−４，６−ジメトキシベンゼン（ＤＡＤＭＢ）であり、副生成物は、２，４−ジアミノアニソール（ＤＡＡ）であることが判った。
【００２３】
上記粗結晶を定量の結果、ＤＡＤＭＢの収率は５１％で、ＤＡＡ収率が４２％であった。
【００２４】
実施例２〜５及び比較例１
表１に示す条件を変えた他は、実施例１と同様に行った。その結果を併せて表１に示す。
【００２５】
【表１】
【発明の効果】
一般式〔Ｉ〕で示されるで表される１−アルコキシ−２，４−ジニトロベンゼンを炭素数１〜４のアルコール、酸及び還元触媒の存在下に水素で還元することで、選択率よく１，３−ジアミノ−４，６−ジアルコキシベンゼンを得ることができるようになった。[0001]
[Industrial application fields]
The present invention relates to a method for producing 1,3-diamino-4,6-dialkoxybenzene and a salt thereof.
More specifically, 1,3-diamino-4,6-dialkoxybenzene and a salt thereof are produced by reducing 1-alkoxy-2,4-dinitrobenzene of the general formula [I] as represented by the following formula: On how to do.
[0002]
[Chemical 3]
(In the formula, R and R ′ represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different.)
In 1,3-diamino-4,6-dialkoxybenzene, 4,6-diaminoresorcin obtained by dealkylation becomes a monomer of polybenzobisoxazole (PBO) having various excellent characteristics. It is important as a raw material.
[0004]
PBO is superior to conventional super fibers in terms of strength, elastic modulus, heat resistance, chemical resistance, and the like, and development as a super super fiber is awaited (Japanese Patent Publication No. 61-501452). .
[0005]
[Prior art]
Conventionally, as a method for producing 1,3-diamino-4,6-dimethoxybenzene, a method obtained by dinitrating 1,3-dimethoxybenzene and then reducing it is known (Tetrahedron Vol. 20, No. 12, 2777). ~ 2983 (1964) [Tetrahedron 20 (12), 2977-2983 (1964)]
However, in this method, 1,3-dimethoxybenzene as a raw material is expensive and cannot be an industrial production method.
[0006]
[Problems to be solved by the invention]
The inventor has intensively studied a method for obtaining 1,3-diamino-4,6-dimethoxybenzene from an inexpensive raw material.
As a result, 1-alkoxy-2,4-dinitrobenzene (ADNB) obtained by reacting 1-chloro-2,4-dinitrobenzene (CDNB) with alcohol in the presence of a base as a raw material, acid- The present invention was completed by finding that 1,3-diamino-4,6-dimethoxybenzene (DADMB) is obtained by reduction rearrangement (Bamberger rearrangement) by reduction in the presence of a catalyst in an alcohol system. I let you.
[0007]
[Formula 4]
An object of the present invention is to provide a method for producing 1,3-diamino-4,6-dialkoxybenzene from 1-alkoxy-2,4-dinitrobenzene.
[0009]
[Means for Solving the Problems]
That is, the present invention
Formula [I]
[0010]
[Chemical formula 5]
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
Wherein the 1-alkoxy-2,4-dinitrobenzene represented by the general formula [II] is reduced with hydrogen in the presence of a C 1-4 alcohol, acid and a Group VIII reduction catalyst.
[0012]
[Chemical 6]
(In the formula, R and R ′ represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different.)
The manufacturing method of 1,3-diamino-4,6-dialkoxybenzene represented by these, and its salt.
Hereinafter, the present invention will be described in detail.
[0014]
First, R of the 1-alkoxy-2,4-dinitrobenzene represented by the general formula [I] as a raw material of the present invention is an alkyl group having 1 to 4 carbon atoms, specifically, 1-methoxy-di- Nitrobenzene, 1-ethoxy-dinitrobenzene, 1-n-propoxy-dinitrobenzene, 1-isopropoxy-dinitrobenzene, 1-n-butoxy-dinitrobenzene, 1-sec-butoxy-dinitrobenzene, 1-tert-butoxy- Dinitrobenzene is mentioned. These compounds can be easily obtained by reacting 1-chloro-2,4-dinitrobenzene with a corresponding alcohol in the presence of a base.
[0015]
As alcohol used for reaction, it is C1-C4, Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol etc. are mentioned. The amount of alcohol used may be 1 equivalent or more with respect to 1-alkoxy-2,4-dinitrobenzene (ADNB) as a raw material, and also serve as a solvent. Usually, it is used in an amount of about 2 to 20 times the weight of the raw material ADNB.
[0016]
As the acid used for the reaction, at least one acid selected from sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, propionic acid and metasulfonic acid can be used. Of these acids, sulfuric acid is particularly preferable. The concentration of the acid is preferably 20 to 100% by weight (80 to 0% by weight: water), and the amount used is preferably 0.5 to 10 equivalents relative to the raw material ADNB.
[0017]
As a reduction catalyst used in the reaction, a single group VIII metal such as nickel, cobalt, iron, palladium, rhodium, ruthenium, platinum, or a catalyst supported on carbon, alumina, silica, zeolite, and other supports can be used. Of these catalysts, platinum-carbon and palladium-carbon supported catalysts are particularly preferred. The amount of the catalyst used is preferably 0.1 to 30% by weight as a metal-supported catalyst of 1 to 5% with respect to the raw material ADNB. Hydrogen pressure is the reaction at 10 kg / cm 2 approximately from atmospheric pressure to proceed, particularly preferably 1 to 3 kg / cm 2.
[0018]
In this reaction, the selectivity of the target product can be increased by adding dimethyl sulfoxide (DMSO). The addition amount is preferably 0.1 to 10% by weight with respect to ADNB as a raw material.
The reaction temperature can be 0 ° C. to 150 ° C., preferably 20 to 120 ° C. The reaction time can be determined from the amount of hydrogen absorbed. The reaction can be carried out batchwise or continuously.
[0019]
Post-treatment after completion of the reaction can be performed, for example, as follows. That is, after completion of the reaction, the reaction solution is filtered to recover the catalyst, and then the filtrate is concentrated, and if necessary, neutralized to pH 7-8 by adding water. The neutralized solution is extracted with ethyl acetate or 1,2-dichloroethane, and the oil layer is concentrated. The target crude 1,3-diamino-4,6-dialkoxybenzene is obtained by refining the resulting crude product by recrystallization or column chromatography.
[0020]
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.
[0021]
【Example】
Example 1
A 100 ml autoclave was charged with 1.98 g (10 mmol) of 2,4-dinitroanisole, 15.2 g of methanol, 76 wt% sulfuric acid (2.5 g of 97 wt% sulfuric acid + 0.7 g of water) and 0.05 g of 2% platinum / carbon. The mixture was stirred for 3 hours at 50 ° C. under a hydrogen pressure of 2 kg / cm 2 .
[0022]
After the reaction, the reaction product was taken out after returning to room temperature and depressurizing. The catalyst in the reaction solution was removed by filtration and then concentrated to obtain 2.3 g of black crystals. As a result of liquid chromatography (LC) analysis, this crystal was found to consist mainly of two components. The crystals were neutralized, extracted with ethyl acetate, and then subjected to column chromatography on silica gel to separate both components. As a result of analysis by these MASS and 1 H-NMR, the main component is 1,3-diamino-4,6-dimethoxybenzene (DADMB), and the by-product is 2,4-diaminoanisole (DAA). It turns out that there is.
[0023]
As a result of quantitative determination of the crude crystals, the yield of DADMB was 51% and the DAA yield was 42%.
[0024]
Examples 2 to 5 and Comparative Example 1
The same procedure as in Example 1 was performed except that the conditions shown in Table 1 were changed. The results are also shown in Table 1.
[0025]
[Table 1]
【The invention's effect】
1-alkoxy-2,4-dinitrobenzene represented by the general formula [I] is reduced with hydrogen in the presence of an alcohol having 1 to 4 carbon atoms, an acid, and a reduction catalyst, so that the selectivity is 1 , 3-diamino-4,6-dialkoxybenzene can be obtained.
Claims (5)
で表される１−アルコキシ−２，４−ジニトロベンゼンを炭素数１〜４のアルコール、酸及び第VIII族の金属触媒の存在下に水素で還元することを特徴とする一般式〔II〕
で表される１，３−ジアミノ−４，６−ジアルコキシベンゼン及びその塩の製造方法。Formula [I]
Wherein the 1-alkoxy-2,4-dinitrobenzene represented by the general formula [II] is reduced with hydrogen in the presence of an alcohol, an acid and a group VIII metal catalyst having 1 to 4 carbon atoms.
A method for producing 1,3-diamino-4,6-dialkoxybenzene represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08678795A JP3744019B2 (en) | 1995-04-12 | 1995-04-12 | Process for producing 1,3-diamino-4,6-dialkoxybenzene and salts thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08678795A JP3744019B2 (en) | 1995-04-12 | 1995-04-12 | Process for producing 1,3-diamino-4,6-dialkoxybenzene and salts thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08283216A JPH08283216A (en) | 1996-10-29 |
| JP3744019B2 true JP3744019B2 (en) | 2006-02-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP08678795A Expired - Fee Related JP3744019B2 (en) | 1995-04-12 | 1995-04-12 | Process for producing 1,3-diamino-4,6-dialkoxybenzene and salts thereof |
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| JP (1) | JP3744019B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ATE405542T1 (en) | 2001-06-22 | 2008-09-15 | Ajinomoto Kk | METHOD FOR PRODUCING AMINO STYLBENDER DERIVATIVES |
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| Publication number | Publication date |
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| JPH08283216A (en) | 1996-10-29 |
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