JPS6034925A - Preparation of 2-hydroxyisophthalaldehydes - Google Patents
Preparation of 2-hydroxyisophthalaldehydesInfo
- Publication number
- JPS6034925A JPS6034925A JP14307983A JP14307983A JPS6034925A JP S6034925 A JPS6034925 A JP S6034925A JP 14307983 A JP14307983 A JP 14307983A JP 14307983 A JP14307983 A JP 14307983A JP S6034925 A JPS6034925 A JP S6034925A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- hydroxyisophthalaldehydes
- reaction
- manganese
- preparation
- 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)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は機能性高分子化合物の原料として有用な２−ヒ
ドロキシイソフタルアルデヒド類の新規な製造法に関す
る。従来、ニーヒドロキシイソフタルアルデヒド類の製
造法としては、により保護し、クロム酸酸化後再び水酸
基を再生させる方法（例えばＦ、 ｔｌｌｌｍａｎｎ
ａｎａ Ｋ、 Ｂｒ１ｔｔｎ’ｅｒ。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 2-hydroxyisophthalaldehydes useful as raw materials for functional polymer compounds. Conventionally, the method for producing dihydroxyisophthalaldehydes has been to protect them with chromic acid and then regenerate the hydroxyl group after oxidation with chromic acid (for example, F, tlllmann
ana K, Br1ttn'er.
Ｏｈｅｍ、Ｂ８ｒ、、 ’１２．２１３９ （〕９０９
））が知られていた。この方法では煩雑な操作と有害な
りロム化合物を含む多量の廃棄物を必要とし、実用的で
はなり０
本発明者はニーヒドロキシイソフタルアルデヒド類の簡
便で高収率な製造方法ン開発するために種々検討した結
果１本発明に到達したものであり、その賛点は、コーヒ
ドロキシイソフタルアルデヒド類ン製造するにあたり、
コ、６−ビス（ヒドロギシメチルノフェノール類乞、二
酸化マンガンと接触させることにある。本発明方法の有
利な点は、精製のための後処理か極めて簡単であること
であり、通常、過剰のマンガン化合物ｋＷ別し、溶媒を
留去するのみにて実用上支障ない純度のノーヒドロキシ
イソフタルアルデヒド類を得ることができる。Ohem, B8r,, '12.2139 (]909
)) was known. This method requires complicated operations and a large amount of waste containing harmful ROM compounds, making it impractical. As a result of our studies, we have arrived at the present invention, and its merits are that in producing co-hydroxyisophthalaldehydes,
The advantage of the process according to the invention is that the work-up for purification is very simple and usually an excess of By simply separating the manganese compound kW and distilling off the solvent, it is possible to obtain non-hydroxyisophthalaldehyde with a purity that is acceptable for practical use.
一般に、フェノール性水酸基を有する物質を二酸化マン
ガンと接触させるとしばしばフェノール性水酸基が反応
し、酸化、縮合等の反応を起こすことが知られている。Generally, it is known that when a substance having a phenolic hydroxyl group is brought into contact with manganese dioxide, the phenolic hydroxyl group often reacts, causing reactions such as oxidation and condensation.
本発明方法のようにフェノール性水酸基の存在下ヒドロ
キシメチル基のみを選択的にアルデヒド基に酸化できる
ことは極めて興味深い。It is extremely interesting that only hydroxymethyl groups can be selectively oxidized to aldehyde groups in the presence of phenolic hydroxyl groups as in the method of the present invention.
本発明方法により製造できるλ−ヒドロキシイソフタル
アルデヒド類は、一般式
（式中、Ｒは水素またばｃ１〜ｃ６のアルキル基を表わ
す。）
で示される化合物であり、対応する原料は、一般式
（式中、Ｒは前記定義に同じ）
で示される化合物が用いられ、通常、一般式（式中、Ｒ
は前記定義に同じ）
で示されるフェノール類とホルムアルデヒドをアルカリ
触媒の存在下公知の方法に従って製造される。The λ-hydroxyisophthalaldehyde that can be produced by the method of the present invention is a compound represented by the general formula (wherein R represents hydrogen or an alkyl group of C1 to C6), and the corresponding raw material is a compound represented by the general formula ( A compound represented by the general formula (wherein R is the same as defined above) is used, and usually, a compound represented by the general formula (wherein R is the same as the above definition) is used.
is the same as the above definition) and formaldehyde is produced according to a known method in the presence of an alkali catalyst.
酸化剤の二酸化マンガンとしてはどのような形態のもの
でも用いうるが、特に、いわゆる活性二酸化マンガンを
用いると良い結果が得られる。活性二酸化マンガンは炭
酸マンガンあるいはシュウ酸マンガンの熱分解、あるい
は過マンガン酸カリウムと硫酸マンガンからの沈澱法等
、公知の方法によって製造し得る。Although any form of manganese dioxide can be used as the oxidizing agent, particularly good results are obtained when so-called activated manganese dioxide is used. Activated manganese dioxide can be produced by known methods such as thermal decomposition of manganese carbonate or manganese oxalate, or precipitation from potassium permanganate and manganese sulfate.
反応を行なうに際しては溶媒を用いるのが好ましい。溶
媒としてはクロロホルム、アセトン、エーテル、炭化水
素等の酸化を受けに（い溶媒が用いられる。It is preferable to use a solvent when carrying out the reaction. As the solvent, oxidizable solvents such as chloroform, acetone, ether, and hydrocarbons are used.
反応温度は室温程度の低温で十分である。A reaction temperature as low as room temperature is sufficient.
反応時間は数時間から数日間の範囲で行なわれる。The reaction time ranges from several hours to several days.
二酸化マンガンは重量で被酸化物のＳ倍〜３０倍程度が
使用される。The amount of manganese dioxide used is about S to 30 times the weight of the oxidized material.
反応終了後、反応液’＆濾過してマンガン化合物を除き
、溶媒を留去することにより、通常実用上十分な純度の
２−ヒドロキシイソフタルアルデヒド類が残渣として得
られる。After the reaction is completed, the reaction solution is filtered to remove the manganese compound, and the solvent is distilled off to obtain 2-hydroxyisophthalaldehyde as a residue with a purity sufficient for practical use.
次に本発明を更に具体的に説明するが５本発明はその要
旨を逸脱しない限り以下の実施例に限定されるものでは
ない。Next, the present invention will be explained in more detail, but the present invention is not limited to the following examples unless it departs from the gist thereof.
実施例１
コツ６−ビス（ヒドロキシメチル）−ターメチルフェノ
ール１０．Ｏｆｌ’Ｊｉ二酸化マンガンｇｏ１！ととも
にｒｏｏｍｌ三角フラスコに入れ、クロロホルム３ｏｏ
ｍｔ’ｉ、Ｈ加え栓をし、室温でコ日間マグネチックス
ターラーにより撹拌した。反応の進行とともに溶媒にと
けなかったジアルコールフェノールは約３時間で溶解し
た。反応終了後二酸化マンガンＹ濾過し、更にこの二酸
化マンガンをクロロホルムλｏｏｍｌでａ同士分洗浄し
−た。反応涙液および洗浄液をあわせ、蒸発すること
により純度のよい淡黄色固体（２−ヒドロキシ−３−メ
チルイソフタルアルデヒド）６．ＳＩＩを得た。収率６
７％。融点／３０℃。ＭＥ！分子ピーク／＆４’ＱＩＨ
ｎｍｒ（ＴＭＳ基準、ＣＤＣｌ３中）、ｃ Ｈ３ｓ、
３ｔ ｐｐｍ Ｃ３］、ａｒｏｍａｔｉｃ Ｈ７，７３
ｐｐｍ （コ〕、ａＨｏ ／ ｏ、ｌｓ ｐｐｍ ［２
〕、ＯＨ／／、３ｋｐｐｍ ［／］ Ｃ積分比〕。Example 1 Tip 6-bis(hydroxymethyl)-termethylphenol 10. Ofl'Ji manganese dioxide go1! Put it in a room Erlenmeyer flask and add 30 ml of chloroform.
mt'i, H was added, the mixture was stoppered, and the mixture was stirred with a magnetic stirrer for several days at room temperature. As the reaction progressed, the dialcohol phenol that was not dissolved in the solvent was dissolved in about 3 hours. After the reaction was completed, the mixture was filtered with manganese dioxide Y, and the manganese dioxide was further washed with chloroform λooml. The reaction tear fluid and washing fluid are combined and evaporated to produce a pale yellow solid (2-hydroxy-3-methylisophthalaldehyde) with good purity.6. Obtained SII. Yield 6
7%. Melting point/30°C. ME! Molecular peak/&4'QIH
nmr (TMS standard, in CDCl3), c H3s,
3t ppm C3], aromatic H7,73
ppm (ko), aHo / o, ls ppm [2
], OH//, 3 kppm [/] C integral ratio].
実施側御
占６−ビス（ヒドロキシメチル）−４１−ｔ−ブチルフ
ェノール１０．０９ｆｆ二酸化マンガンｔｒｏｇととも
に！ｆ、ｏｏｎｒｔｔ：三角フラスコに入れ、クロロホ
ルム３ｏｏｍｌを加え栓をし上記と同様の処理を行った
。得られた淡黄色固体（コーヒドロキシー、１−ｔ−プ
チルイノフタルアルデヒド）Ａ、９ｆｊを得た。収率７
０％。ｒｎｐ、ＩＯ！ｒ℃、ＭＳ分子ピーク２０４゜Ｉ
Ｈｎｍｒ（ＴＭＳ内部標準、ＣＤＣｌ３中） Ｂｕ ／
、ｓ ！ｌｐｐｍ ［ｙ’ｌ 、 ａｒｏｍａｔｉｃＨ
？、 ｇ 、？ ｐｐｍ ［−２’）、 ＣＨＯ／ ０
．０ ？ ｐｐｍ ［！］、ＯＨ／ ／、、２ ｇ ｐ
ｐｍ ［／’：Ｉ Ｃ積分比〕。Implementation side fortune telling 6-bis(hydroxymethyl)-41-t-butylphenol 10.09ff with manganese dioxide trog! f, oonrtt: It was placed in an Erlenmeyer flask, 3 ooml of chloroform was added, the stopper was sealed, and the same treatment as above was performed. A pale yellow solid (cohydroxy, 1-t-butylinophthalaldehyde) A, 9fj was obtained. Yield 7
0%. rnp, IO! r℃, MS molecular peak 204゜I
Hnmr (TMS internal standard, in CDCl3) Bu /
,s! lppm [y'l, aromaticH
? , g,? ppm [-2'), CHO/0
．． 0? ppm [! ], OH/ /,, 2 g p
pm [/': I C integral ratio].
出 願 人 三菱化成工業株式会社 代理人弁理士 長谷用 − ほか／名Sender: Mitsubishi Chemical Industries, Ltd. Representative patent attorney Haseyo - Others/names
Claims (1)
す。） で示される化合物を二酸化マンガンにより酸化すること
を特徴とする一般式 （式中、Ｒは前記定義に同じ） で表わされるニーヒドロキシイソフタルアルデヒド類の
製造法。(1) General formula (wherein R represents hydrogen or an alkyl group of 01 to C6) characterized by oxidizing the compound represented by manganese dioxide with manganese dioxide (wherein R is the same as defined above) ) A method for producing dihydroxyisophthalaldehydes represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14307983A JPS6034925A (en) | 1983-08-04 | 1983-08-04 | Preparation of 2-hydroxyisophthalaldehydes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14307983A JPS6034925A (en) | 1983-08-04 | 1983-08-04 | Preparation of 2-hydroxyisophthalaldehydes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6034925A true JPS6034925A (en) | 1985-02-22 |
| JPH0443059B2 JPH0443059B2 (en) | 1992-07-15 |
Family
ID=15330420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14307983A Granted JPS6034925A (en) | 1983-08-04 | 1983-08-04 | Preparation of 2-hydroxyisophthalaldehydes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6034925A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6881423B2 (en) | 1996-02-27 | 2005-04-19 | Teijin Limited | Powdery composition for nasal administration |
| BG64919B1 (en) * | 1998-04-21 | 2006-09-29 | Teijin Ltd. | Pharmaceutical composition for mucous membrane application |
-
1983
- 1983-08-04 JP JP14307983A patent/JPS6034925A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6881423B2 (en) | 1996-02-27 | 2005-04-19 | Teijin Limited | Powdery composition for nasal administration |
| US7731990B2 (en) | 1996-02-27 | 2010-06-08 | Teijin Limited | Powdery composition for nasal administration |
| US8206748B2 (en) | 1996-02-27 | 2012-06-26 | Teijin Limited | Powdery composition for nasal administration |
| BG64919B1 (en) * | 1998-04-21 | 2006-09-29 | Teijin Ltd. | Pharmaceutical composition for mucous membrane application |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0443059B2 (en) | 1992-07-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |