JPH101451A - Production of 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde - Google Patents
Production of 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehydeInfo
- Publication number
- JPH101451A JPH101451A JP15459796A JP15459796A JPH101451A JP H101451 A JPH101451 A JP H101451A JP 15459796 A JP15459796 A JP 15459796A JP 15459796 A JP15459796 A JP 15459796A JP H101451 A JPH101451 A JP H101451A
- Authority
- JP
- Japan
- Prior art keywords
- catechol
- substituted
- dihydroxybenzaldehyde
- vilsmeier reagent
- alkyloxy
- 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
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 title claims description 20
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- -1 (substituted)-catechol Chemical class 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、食品添加物、医薬
品及び電子材料などの中間体として有用な３，４−ジヒ
ドロキシベンツアルデヒド又は３−アルキルオキシ−４
−ヒドロキシベンツアルデヒドを高純度、高収率で且つ
簡単な方法で合成する方法を提供するものである。The present invention relates to 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4 useful as an intermediate for food additives, pharmaceuticals and electronic materials.
-A method for synthesizing hydroxybenzaldehyde with high purity, high yield and a simple method.
【０００２】[0002]
【従来の技術】従来、３，４−ジヒドロキシベンツアル
デヒド又は３−アルキルオキシ−４−ヒドロキシベンツ
アルデヒドは、カテコールとクロロホルムを使用したＲ
ｅｉｍｅｒ−Ｔｉｅｍａｎｎ反応により合成されている
（Ｂｅｒ．９，１２６８（１８７６））。しかし、この
反応は通常フェノール性水酸基を有するものの反応に使
用される物であり、カテコールのｏ−位にアルデヒド基
が優先的に付加導入されるため、ｐ−位にアルデヒド基
が付加した本発明の化合物を得るためには、カテコール
のｏ−位にアルデヒド基が導入した副生成化合物を分離
する必要があった。しかし、この分離方法が煩雑であ
り、従って本発明の化合物の収率が低く選択的に合成す
るのは困難であった。2. Description of the Related Art Conventionally, 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde has been prepared by using catechol and chloroform.
It is synthesized by the Eimer-Tiemann reaction (Ber. 9, 1268 (1876)). However, this reaction is usually used for the reaction having a phenolic hydroxyl group, and the aldehyde group is preferentially added to the o-position of catechol. In order to obtain the compound (1), it was necessary to separate a by-product compound in which an aldehyde group was introduced at the o-position of catechol. However, this separation method is complicated, so that the yield of the compound of the present invention is low and it has been difficult to selectively synthesize it.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記の問題
点のない３，４−ジヒドロキシベンツアルデヒド又は３
−アルキルオキシ−４−ヒドロキシベンツアルデヒドを
高純度、高収率で且つ簡単な方法で合成する新規な方法
を提供することを目的とするものである。DISCLOSURE OF THE INVENTION The present invention is directed to a process for preparing 3,4-dihydroxybenzaldehyde or 3
An object of the present invention is to provide a novel method for synthesizing -alkyloxy-4-hydroxybenzaldehyde with high purity, high yield and a simple method.
【０００４】[0004]
【課題を解決するための手段】上記の目的は、本発明に
なる、（１）ジメチルホルムアミドおよびオキシ塩化リ
ンから調製したＶｉｌｓｍｅｉｅｒ試薬と下記一般式
（ＩＩ）で示されるカテコール又は置換カテコールとを
反応させることを特徴とする下記一般式（Ｉ）で示され
る３，４−ジヒドロキシベンツアルデヒド又は３−アル
キルオキシ−４−ヒドロキシベンツアルデヒドの製造方
法、The object of the present invention is to react (1) a Vilsmeier reagent prepared from dimethylformamide and phosphorus oxychloride with a catechol or a substituted catechol represented by the following general formula (II). A process for producing 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde represented by the following general formula (I),
【０００５】[0005]
【化２】 Embedded image
【０００６】式中、Ｒは水素原子又はアルキル基を表
す、（２）反応温度が８０〜１５０°Ｃであることを特
徴とする上記（１）記載の３，４−ジヒドロキシベンツ
アルデヒド又は３−アルキルオキシ−４−ヒドロキシベ
ンツアルデヒドの製造方法、によって達成される。In the formula, R represents a hydrogen atom or an alkyl group. (2) The reaction temperature of 80 to 150 ° C., wherein the 3,4-dihydroxybenzaldehyde or 3- A process for producing alkyloxy-4-hydroxybenzaldehyde.
【０００７】[0007]
【発明の実施の形態】本発明を更に詳細に説明する。本
発明で使用されるＶｉｌｓｍｅｉｅｒ試薬は、Ｎ，Ｎ−
ジメチルホルムアミドと塩化ホスホリルとを１：１のモ
ル比で、また必要に応じＮ，Ｎ−ジメチルホルムアミド
を過剰に使用し溶媒として用いて作用させることによっ
て得られ、通常Ｖｉｌｓｍｅｉｅｒ錯体と呼ばれるメチ
レンイミニウム化合物である。本発明においては、この
ようにして調製したＶｉｌｓｍｅｉｅｒ試薬と上記一般
式（II）で示されるカテコール又は置換カテコールを反
応させることにより、目的の化合物を得る。反応温度は
余り低いと反応しにくく、また高すぎると副生成物が生
成するので、通常８０〜１５０°Ｃ、好ましくは１００
〜１２０℃が適用される。Ｖｉｌｓｍｅｉｅｒ試薬とカ
テコール又は置換カテコールとは通常１〜２：１のモル
比で反応させる。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. The Vilsmeier reagent used in the present invention is N, N-
A methyleneiminium compound which is obtained by reacting dimethylformamide and phosphoryl chloride in a molar ratio of 1: 1 and using N, N-dimethylformamide in excess as required and using it as a solvent, usually called a Vilsmeier complex It is. In the present invention, the desired compound is obtained by reacting the thus-prepared Vilsmeier reagent with the catechol or substituted catechol represented by the above general formula (II). If the reaction temperature is too low, it is difficult to react, and if it is too high, a by-product is formed.
~ 120 ° C is applied. The Vilsmeier reagent and catechol or substituted catechol are usually reacted in a molar ratio of 1 to 2: 1.
【０００８】前記一般式(I) において、Ｒは水素原子ま
たはメチル基、エチル基、プロピル基等のアルキル基で
あり、好ましくは水素原子、メチル基、エチル基であ
る。In the general formula (I), R is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group or a propyl group, preferably a hydrogen atom, a methyl group or an ethyl group.
【０００９】次に、本発明の化合物の製造方法の一例を
述べる。ジメチルホルムアミドとオキシ塩化リンを１：
１に調整したＶｉｌｓｍｅｉｅｒ試薬にカテコールまた
は置換カテコールを添加し、８０〜１２０°Ｃで４時間
反応し冷却後、水に注入しクロロホルムで抽出、濃縮
後、ｎ−ヘキサンで再結晶し目的物である３，４−ジヒ
ドロキシベンツアルデヒド又は３−アルキルオキシ−４
−ヒドロキシベンツアルデヒドを高収率、且つ高純度で
得ることができる。Next, an example of a method for producing the compound of the present invention will be described. Dimethylformamide and phosphorus oxychloride:
Catechol or substituted catechol was added to the Vilsmeier reagent adjusted to 1, reacted at 80 to 120 ° C. for 4 hours, cooled, poured into water, extracted with chloroform, concentrated, and recrystallized with n-hexane to obtain the desired product. 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4
-Hydroxybenzaldehyde can be obtained in high yield and high purity.
【００１０】[0010]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はこれに限定されるものではない。 実施例１ ３，４−ジヒドロキシベンツアルデヒドの合成：ジメチ
ルホルムアミド５０ミリリットルにオキシ塩化リン１
５．３ｇ（０．１モル）を１０°Ｃにて滴下する。滴下
後カテコール１１．０ｇ（０．１モル）を添加し、１２
０°Ｃに昇温し同温度で４時間反応する。反応終了後室
温まで冷却し反応液を水５００ミリリットル中に注入し
１時間攪拌する。次にクロロホルム２００ミリリットル
を添加し抽出濃縮する。濃縮液にｎ−ヘキサン１００ミ
リリットルを添加し、５０°Ｃで完溶させ、冷却晶析、
濾別、乾燥し目的物１１．０ｇ（収率８０％）を得た。
純度９９％以上、融点１５２．０〜１５５．０°Ｃ元素
分析の結果は次の通りである。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 Synthesis of 3,4-dihydroxybenzaldehyde: Phosphorus oxychloride 1 in 50 ml of dimethylformamide
5.3 g (0.1 mol) are added dropwise at 10 ° C. After dropping, 11.0 g (0.1 mol) of catechol was added, and 12
The temperature is raised to 0 ° C. and the reaction is carried out at the same temperature for 4 hours. After completion of the reaction, the reaction solution is cooled to room temperature, poured into 500 ml of water, and stirred for 1 hour. Next, 200 ml of chloroform is added and the mixture is extracted and concentrated. 100 ml of n-hexane was added to the concentrate, and the solution was completely dissolved at 50 ° C.
The crystals were separated by filtration and dried to obtain 11.0 g (yield: 80%) of the desired product.
The results of elemental analysis with a purity of 99% or more and a melting point of 152.0 to 155.0 ° C are as follows.
【００１１】実施例２ ４−ヒドロキシ−３−メトキシベンツアルデヒドの合
成：ジメチルホルムアミド５０ミリリットルにオキシ塩
化リン１５．３ｇ（０．１モル）を１０°Ｃにて滴下す
る。その中に２−メトキシフェノール１２．４ｇ（０．
１モル）を添加し、１２０°Ｃに昇温し同温度で４時間
反応する。反応終了後室温まで冷却し反応液を水５００
ミリリットル中に注入し１時間攪拌する。次にクロロホ
ルム２００ミリリットルを添加し抽出濃縮し、ｎ−ヘキ
サン１００ミリリットルを添加し５０°Ｃで完溶させ冷
却晶析、濾別、乾燥し目的物１０．６ｇ（収率７０％）
を得た。融点８０．０〜８４．０°Ｃ元素分析の結果は
次の通りである。 Example 2 Synthesis of 4-hydroxy-3-methoxybenzaldehyde: To 50 ml of dimethylformamide, 15.3 g (0.1 mol) of phosphorus oxychloride is added dropwise at 10 ° C. 12.4 g of 2-methoxyphenol (0.
1 mol), heated to 120 ° C., and reacted at the same temperature for 4 hours. After completion of the reaction, the reaction solution is cooled to room temperature,
Inject into milliliter and stir for 1 hour. Next, 200 ml of chloroform was added, and the mixture was extracted and concentrated. 100 ml of n-hexane was added, and the mixture was completely dissolved at 50 ° C.
I got Melting point: 80.0 to 84.0 ° C The results of elemental analysis are as follows.
【００１２】実施例３ 反応温度を５０℃に変え、他は実施例１と同様にして反
応させたところ反応完結までに２０時間以上を要した。Example 3 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 50 ° C., and it took more than 20 hours to complete the reaction.
【００１３】[0013]
【発明の効果】本発明によれば、３，４−ジヒドロキシ
ベンツアルデヒド又は３−アルキルオキシ−４−ヒドロ
キシベンツアルデヒドを、高収率且つ高純度でしかも簡
単な方法で効率的に製造することができる。According to the present invention, 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde can be efficiently produced in a high yield, a high purity and a simple method. it can.
Claims (2)
リンから調製したＶｉｌｓｍｅｉｅｒ試薬と下記一般式
（ＩＩ）で示されるカテコール又は置換カテコールとを
反応させることを特徴とする下記一般式（Ｉ）で示され
る３，４−ジヒドロキシベンツアルデヒド又は３−アル
キルオキシ−４−ヒドロキシベンツアルデヒドの製造方
法。 【化１】 式中、Ｒは水素原子又はアルキル基を表す。1. A method of reacting a Vilsmeier reagent prepared from dimethylformamide and phosphorus oxychloride with a catechol or a substituted catechol represented by the following general formula (II): A method for producing 4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde. Embedded image In the formula, R represents a hydrogen atom or an alkyl group.
を特徴とする請求項１記載の３，４−ジヒドロキシベン
ツアルデヒド又は３−アルキルオキシ−４−ヒドロキシ
ベンツアルデヒドの製造方法。2. The method for producing 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde according to claim 1, wherein the reaction temperature is 80 to 150 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15459796A JP3874452B2 (en) | 1996-06-14 | 1996-06-14 | Method for producing 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15459796A JP3874452B2 (en) | 1996-06-14 | 1996-06-14 | Method for producing 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH101451A true JPH101451A (en) | 1998-01-06 |
| JP3874452B2 JP3874452B2 (en) | 2007-01-31 |
Family
ID=15587671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15459796A Expired - Fee Related JP3874452B2 (en) | 1996-06-14 | 1996-06-14 | Method for producing 3,4-dihydroxybenzaldehyde or 3-alkyloxy-4-hydroxybenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3874452B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627491A (en) * | 2018-12-17 | 2019-04-16 | 江苏三吉利化工股份有限公司 | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof |
-
1996
- 1996-06-14 JP JP15459796A patent/JP3874452B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627491A (en) * | 2018-12-17 | 2019-04-16 | 江苏三吉利化工股份有限公司 | It is a kind of using catechol as the phosphate flame retardant of skeleton and its environment-friendly preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3874452B2 (en) | 2007-01-31 |
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