JP3775883B2 - Protocatecaldehyde production method - Google Patents
Protocatecaldehyde production method Download PDFInfo
- Publication number
- JP3775883B2 JP3775883B2 JP07223997A JP7223997A JP3775883B2 JP 3775883 B2 JP3775883 B2 JP 3775883B2 JP 07223997 A JP07223997 A JP 07223997A JP 7223997 A JP7223997 A JP 7223997A JP 3775883 B2 JP3775883 B2 JP 3775883B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxybenzaldehyde
- protocatecaldehyde
- acid
- alkoxy
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、３−アルコキシ−４−ヒドロキシベンズアルデヒドからプロトカテキュアルデヒド（３，４−ジヒドロキシベンズアルデヒド）を高収率で容易に製造する方法に関する。プロトカテキュアルデヒドは医薬や農薬の合成原料、更にはマイクロフォトレジスト等の電子材料の原料として有用な化合物である。
【０００２】
【従来の技術】
３−アルコキシ−４−ヒドロキシベンズアルデヒドを脱アルキルしてプロトカテキュアルデヒド（３，４−ジヒドロキシベンズアルデヒド）を製造する方法としては、バニリン（３−メトキシ−４−ヒドロキシベンズアルデヒドを三塩化アルミニウムで処理した後に加水分解する方法が知られている〔Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２７，２０３７（１９６２）〕。
【０００３】
しかし、この方法では、目的物の収率が低い上に、反応を円滑に進行させるために大過剰のピリジンを用いることから、工業的には不経済であるという問題がある。更に、アルミニウムが目的物に配位するために精製が煩雑になるという問題も存在する。
【０００４】
また、上記文献には、バニリンを、（１）塩酸で処理する方法、（２）臭化水素酸と酢酸で処理する方法、及び（３）五塩化リンで処理する方法も記載されているが、いずれも目的物の収率が５０％以下で好ましい方法ではない。
【０００５】
【発明が解決しようとする課題】
前記のような技術背景に鑑み、本発明は、３−アルコキシ−４−ヒドロキシベンズアルデヒドを脱アルキルしてプロトカテキュアルデヒド（３，４−ジヒドロキシベンズアルデヒド）を製造する方法において、プロトカテキュアルデヒドを高收率で容易に製造することができる、工業的に好適なプロトカテキュアルデヒドの製法を提供することを課題とする。
【０００６】
【課題を解決するための手段】
本発明の課題は、３−アルコキシ−４−ヒドロキシベンズアルデヒドを脱アルキルしてプロトカテキュアルデヒドを製造する方法において、３−アルコキシ−４−ヒドロキシベンズアルデヒド（但し、アルコキシ基は少なくとも２個の炭素原子を有する）の脱アルキル反応を非ハロゲン化酸の存在下で行うことを特徴とするプロトカテキュアルデヒドの製造方法によって達成される。
【０００７】
【発明の実施の形態】
以下に、本発明を詳細に説明する。
３−アルコキシ−４−ヒドロキシベンズアルデヒドとしては、該アルコキシ基が少なくとも２個の炭素原子を有する化合物、即ち、該アルコキシ基が炭素数２〜１０、好ましくは炭素数２〜８のアルキル基からなるアルコキシ基である化合物が使用される。
このアルキル基としては、例えば、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基などの低級アルキル基や、シクロペンチル基、シクロヘキシル基などのシクロアルキル基が挙げられる。
【０００８】
３−アルコキシ−４−ヒドロキシベンズアルデヒドとして、具体的には、３−エトキシ−４−ヒドロキシベンズアルデヒド、３−ｎ−プロポキシ−４−ヒドロキシベンズアルデヒド、３−イソプロポキシ−４−ヒドロキシベンズアルデヒド、３−ｎ−ブトキシ−４−ヒドロキシベンズアルデヒド、３−イソブトキシ−４−ヒドロキシベンズアルデヒド、３−ｓｅｃ−ブトキシ−４−ヒドロキシベンズアルデヒド、３−ｔｅｒｔ−ブトキシ−４−ヒドロキシベンズアルデヒドなどが挙げられる。
３−アルコキシ−４−ヒドロキシベンズアルデヒドの中では、３−エトキシ−４−ヒドロキシベンズアルデヒドが安価で、工業的に好ましい。
【０００９】
非ハロゲン化酸としては、非ハロゲン化オキシ酸又は非ハロゲン化スルホン酸が好適に使用される。
非ハロゲン化オキシ酸としては、例えば、硫酸、ピロ硫酸などが挙げられ、非ハロゲン化スルホン酸としては、メタンスルホン酸、エタンスルホン酸、エタンジスルホン酸、ベンゼンスルホン酸、ベンゼンジスルホン酸、トルエンスルホン酸、ナフタレンスルホン酸、ナフタレンジスルホン酸などが挙げられる。これら非ハロゲン化酸の中では、硫酸が最も好ましい。
非ハロゲン化酸は、３−アルコキシ−４−ヒドロキシベンズアルデヒド１モルに対して５〜２０モル、好ましくは５〜１０モル使用される。非ハロゲン化酸の使用量が少ない場合は反応が非常に遅くなり、使用量が多い場合は副生物が多く生成して目的物の選択率を低下させるので好ましくない。なお、使用する非ハロゲン化酸は水を含有していてもよいが、その場合、非ハロゲン化酸の濃度は７０〜１００重量％、特に８５〜１００重量％であることが好ましい。
【００１０】
本発明では、３−アルコキシ−４−ヒドロキシベンズアルデヒドの脱アルキル反応は、非ハロゲン酸の存在下、２５〜１００℃、好ましくは２５〜７０℃で行われる。反応圧力は特に制限されるものではなく、例えば、常圧下で反応が行われる。なお、反応雰囲気は、原料や目的物の参加を防ぐために、不活性ガス（アルゴン、窒素等）雰囲気とすることが好ましい。
【００１１】
反応終了後、脱アルキル反応で得られた反応液は水で処理される。この処理は０〜７０℃、好ましくは０〜４０℃で行われる。このとき、圧力、雰囲気などは脱アルキル反応の際と同様である。なお、水は、例えば、仕込みの３−アルコキシ−４−ヒドロキシベンズアルデヒド１モルに対して０．５〜１０Ｌ（リットル）、好ましくは０．５〜５Ｌ（リットル）使用される。
次いで、水処理された前記反応液から、プロトカテキュアルデヒドが抽出、晶析などによって回収される。
【００１２】
【実施例】
次に、実施例を挙げて本発明を具体的に説明する。なお、プロトカテキュアルデヒドの収率（モル％）は３−アルコキシ−４−ヒドロキシベンズアルデヒドに対して求めた。
【００１３】
実施例１
アルゴン気流中、室温下で、２５ｍＬ容フラスコに９６重量％硫酸（６０．２０ｍｍｏｌ）を入れて、攪拌しながら温度を５℃に下げた後、この温度で３−エトキシ−４−ヒドロキシベンズアルデヒド（６．０２ｍｍｏｌ）を添加した。次いで、温度を６５〜７０℃に上げ、同温度で２時間加熱攪拌した後、反応液を室温まで冷却した。そして、得られた反応液を攪拌下で氷水（２０ｍｌ）に添加して、１時間攪拌した。
得られた水溶液を高速液体クロマトグラフィーで分析したところ、３−エトキシ−４−ヒドロキシベンズアルデヒドの転化率は９７％で、プロトカテキュアルデヒドの収率は９１％であった。なお、以上の操作は全て常圧下で行った。
【００１４】
実施例２
９６重量％硫酸の量を１１６．１９ｍｍｏｌに変え、反応時間を１時間に変えたほかは、実施例１と同様の操作を行った。
その結果、３−エトキシ−４−ヒドロキシベンズアルデヒドの転化率は９９％で、プロトカテキュアルデヒドの収率は９６％であった。
【００１５】
実施例３
９６重量％硫酸の量を３０．１５ｍｍｏｌに変え、反応時間を１１時間に変えたほかは、実施例１と同様の操作を行った。
その結果、３−エトキシ−４−ヒドロキシベンズアルデヒドの転化率は９１％で、プロトカテキュアルデヒドの収率は８４％であった。
実施例の結果を表１に示す。
【００１６】
【表１】
【発明の効果】
本発明により、３−アルコキシ−４−ヒドロキシベンズアルデヒドを脱アルキルしてプロトカテキュアルデヒドを製造する方法において、プロトカテキュアルデヒドを高收率で容易に製造することができる。また、コスト的にも安価にプロトカテキュアルデヒドを製造できる。この結果、本発明により、工業的に好適なプロトカテキュアルデヒドの製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for easily producing protocatecaldehyde (3,4-dihydroxybenzaldehyde) from 3-alkoxy-4-hydroxybenzaldehyde in a high yield. Protocatecaldehyde is a useful compound as a raw material for synthetic materials for pharmaceuticals and agricultural chemicals, and for electronic materials such as microphotoresists.
[0002]
[Prior art]
As a method for producing protocatecaldehyde (3,4-dihydroxybenzaldehyde) by dealkylating 3-alkoxy-4-hydroxybenzaldehyde, after treating vanillin (3-methoxy-4-hydroxybenzaldehyde with aluminum trichloride, A method for hydrolysis is known [J. Org. Chem., 27, 2037 (1962)].
[0003]
However, this method has a problem that it is industrially uneconomical because the yield of the target product is low and a large excess of pyridine is used to facilitate the reaction. Furthermore, there is a problem that the purification becomes complicated because aluminum is coordinated to the target product.
[0004]
The above document also describes (1) a method of treating vanillin with (1) hydrochloric acid, (2) a method of treating with hydrobromic acid and acetic acid, and (3) a method of treating with phosphorus pentachloride. In either case, the yield of the target product is 50% or less, which is not a preferable method.
[0005]
[Problems to be solved by the invention]
In view of the above technical background, the present invention relates to a method for producing protocatecaldehyde (3,4-dihydroxybenzaldehyde) by dealkylating 3-alkoxy-4-hydroxybenzaldehyde. It is an object of the present invention to provide an industrially suitable method for producing protocatecaldehyde that can be easily produced at a high yield.
[0006]
[Means for Solving the Problems]
An object of the present invention is to produce protocatecaldehyde by dealkylating 3-alkoxy-4-hydroxybenzaldehyde, wherein 3-alkoxy-4-hydroxybenzaldehyde (wherein the alkoxy group has at least 2 carbon atoms). The dealkylation reaction is carried out in the presence of a non-halogenated acid.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
As 3-alkoxy-4-hydroxybenzaldehyde, a compound in which the alkoxy group has at least 2 carbon atoms, that is, an alkoxy group in which the alkoxy group is an alkyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The radical compound is used.
Examples of the alkyl group include lower alkyl groups such as ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group, cyclopentyl group, And cycloalkyl groups such as cyclohexyl group.
[0008]
Specific examples of 3-alkoxy-4-hydroxybenzaldehyde include 3-ethoxy-4-hydroxybenzaldehyde, 3-n-propoxy-4-hydroxybenzaldehyde, 3-isopropoxy-4-hydroxybenzaldehyde, 3-n-butoxy. Examples include -4-hydroxybenzaldehyde, 3-isobutoxy-4-hydroxybenzaldehyde, 3-sec-butoxy-4-hydroxybenzaldehyde, 3-tert-butoxy-4-hydroxybenzaldehyde, and the like.
Among 3-alkoxy-4-hydroxybenzaldehydes, 3-ethoxy-4-hydroxybenzaldehyde is inexpensive and industrially preferable.
[0009]
As the non-halogenated acid, a non-halogenated oxyacid or a non-halogenated sulfonic acid is preferably used.
Examples of non-halogenated oxyacids include sulfuric acid and pyrosulfuric acid. Non-halogenated sulfonic acids include methanesulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, and toluenesulfonic acid. , Naphthalene sulfonic acid, naphthalene disulfonic acid and the like. Of these non-halogenated acids, sulfuric acid is most preferred.
The non-halogenated acid is used in an amount of 5 to 20 mol, preferably 5 to 10 mol, relative to 1 mol of 3-alkoxy-4-hydroxybenzaldehyde. When the amount of non-halogenated acid used is small, the reaction becomes very slow. When the amount used is large, a large amount of by-products are produced, which lowers the selectivity of the target product. The non-halogenated acid to be used may contain water. In that case, the concentration of the non-halogenated acid is preferably 70 to 100% by weight, particularly preferably 85 to 100% by weight.
[0010]
In the present invention, the dealkylation reaction of 3-alkoxy-4-hydroxybenzaldehyde is performed at 25 to 100 ° C., preferably 25 to 70 ° C. in the presence of a non-halogen acid. The reaction pressure is not particularly limited, and for example, the reaction is performed under normal pressure. The reaction atmosphere is preferably an inert gas (argon, nitrogen, etc.) atmosphere in order to prevent the participation of raw materials and objects.
[0011]
After completion of the reaction, the reaction solution obtained by the dealkylation reaction is treated with water. This treatment is performed at 0 to 70 ° C, preferably 0 to 40 ° C. At this time, the pressure, atmosphere, and the like are the same as in the dealkylation reaction. Water is used, for example, in an amount of 0.5 to 10 L (liter), preferably 0.5 to 5 L (liter), based on 1 mol of charged 3-alkoxy-4-hydroxybenzaldehyde.
Next, protocatecaldehyde is recovered from the water-treated reaction solution by extraction, crystallization, and the like.
[0012]
【Example】
Next, the present invention will be specifically described with reference to examples. In addition, the yield (mol%) of protocatecaldehyde was calculated | required with respect to 3-alkoxy-4-hydroxybenzaldehyde.
[0013]
Example 1
96 wt% sulfuric acid (60.20 mmol) was added to a 25 mL volumetric flask in an argon stream at room temperature, and the temperature was lowered to 5 ° C. with stirring. At this temperature, 3-ethoxy-4-hydroxybenzaldehyde (6 0.02 mmol) was added. Next, the temperature was raised to 65 to 70 ° C., and the mixture was heated and stirred at the same temperature for 2 hours, and then the reaction solution was cooled to room temperature. And the obtained reaction liquid was added to ice water (20 ml) under stirring, and stirred for 1 hour.
When the obtained aqueous solution was analyzed by high performance liquid chromatography, the conversion of 3-ethoxy-4-hydroxybenzaldehyde was 97%, and the yield of protocatecaldehyde was 91%. All the above operations were performed under normal pressure.
[0014]
Example 2
The same operation as in Example 1 was carried out except that the amount of 96 wt% sulfuric acid was changed to 116.19 mmol and the reaction time was changed to 1 hour.
As a result, the conversion of 3-ethoxy-4-hydroxybenzaldehyde was 99%, and the yield of protocatecaldehyde was 96%.
[0015]
Example 3
The same operation as in Example 1 was performed, except that the amount of 96% by weight sulfuric acid was changed to 30.15 mmol and the reaction time was changed to 11 hours.
As a result, the conversion of 3-ethoxy-4-hydroxybenzaldehyde was 91%, and the yield of protocatecaldehyde was 84%.
The results of the examples are shown in Table 1.
[0016]
[Table 1]
【The invention's effect】
According to the present invention, in a method for producing protocatecaldehyde by dealkylating 3-alkoxy-4-hydroxybenzaldehyde, protocatecaldehyde can be easily produced with high yield. Also, protocatecaldehyde can be produced at low cost. As a result, according to the present invention, an industrially suitable method for producing protocatecaldehyde can be provided.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07223997A JP3775883B2 (en) | 1997-03-25 | 1997-03-25 | Protocatecaldehyde production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07223997A JP3775883B2 (en) | 1997-03-25 | 1997-03-25 | Protocatecaldehyde production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10265428A JPH10265428A (en) | 1998-10-06 |
| JP3775883B2 true JP3775883B2 (en) | 2006-05-17 |
Family
ID=13483548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07223997A Expired - Lifetime JP3775883B2 (en) | 1997-03-25 | 1997-03-25 | Protocatecaldehyde production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3775883B2 (en) |
-
1997
- 1997-03-25 JP JP07223997A patent/JP3775883B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10265428A (en) | 1998-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH10279506A (en) | Production of bishydroxymethyl compound | |
| JP3775883B2 (en) | Protocatecaldehyde production method | |
| JPH06298670A (en) | Preparation of aromatic olefin | |
| CN108689874B (en) | Method for preparing 2-aryl malonamide and application thereof | |
| EP0650952B1 (en) | Process for 3,5-di-tert-butylsalicylaldehyde | |
| JP3923677B2 (en) | Process for producing 2-alkyl-2-cyclopentenone | |
| GB2103216A (en) | Process for the preparation of N-substituted methacrylamides and acrylamides | |
| JPH07300445A (en) | Preparation of 4-halo-2'-nitrobutyrophenone compound | |
| EP1731499A1 (en) | Process for producing 1,2-cis-2-fluorocyclopropane-1carboxylic ester compound | |
| JP3521672B2 (en) | Method for producing 3,4-dihydroxy-5-nitrobenzaldehyde | |
| JP4066544B2 (en) | Method for producing cyclopentenone | |
| JP2531708B2 (en) | Method for separating and purifying 3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionic acid ester | |
| JP4032861B2 (en) | Process for producing β-oxonitrile derivative or alkali metal salt thereof | |
| JP3640319B2 (en) | Method for producing benzamide derivative | |
| JP3823385B2 (en) | Process for producing 2,4,5-trifluoro-3-iodobenzoic acid and esters thereof | |
| JP3726315B2 (en) | Purification method of ketonic ester | |
| US6921832B2 (en) | Optically active fluorine-containing compounds and processes for their production | |
| JPH04234358A (en) | Process for producing 2,6-t-butyl-4-mercapto- phenol | |
| JP3814943B2 (en) | Production method of dialkyl carbonate | |
| US6667422B2 (en) | Process for the preparation of α-haloketones | |
| CA1128948A (en) | Production of pyridoxine | |
| JP4421153B2 (en) | Method for producing trialkanoyloxyboron | |
| JP2882057B2 (en) | Method for producing benzoyl acetates | |
| JPS6317869A (en) | Production of 2-lower alkyl-4-amino-5-formylpyrimidine | |
| US6180801B1 (en) | Method for manufacturing 3-isochromanone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040113 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040308 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040420 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20040426 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20040528 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060221 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100303 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110303 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120303 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120303 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120303 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130303 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130303 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130303 Year of fee payment: 7 |