JPS6245216B2 - - Google Patents
Info
- Publication number
- JPS6245216B2 JPS6245216B2 JP56151571A JP15157181A JPS6245216B2 JP S6245216 B2 JPS6245216 B2 JP S6245216B2 JP 56151571 A JP56151571 A JP 56151571A JP 15157181 A JP15157181 A JP 15157181A JP S6245216 B2 JPS6245216 B2 JP S6245216B2
- Authority
- JP
- Japan
- Prior art keywords
- dihydroxybenzaldehyde
- cyclodextrin
- reaction
- selectivity
- chloroform
- 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
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims description 12
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- AYZFTYFURGCPEJ-UHFFFAOYSA-N 2,4-dihydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1C=O AYZFTYFURGCPEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TWADJGWUKGOPFG-UHFFFAOYSA-N 2-methoxy-5-methyl-1,3-diphenylbenzene Chemical compound COC1=C(C=2C=CC=CC=2)C=C(C)C=C1C1=CC=CC=C1 TWADJGWUKGOPFG-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- -1 cyclic oligosaccharide Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000003567 photophosphorylation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002786 root growth Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は２・４−ジヒドロキシベンズアルデヒ
ドの合成法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for the synthesis of 2,4-dihydroxybenzaldehyde.
２・４−ジヒドロキシベンズアルデヒド（）
は、制ガン作用、植物根の生長促進作用、抗菌作
用および葉緑体における光リン酸化の抑制作用な
ど興味ある挙動を示し、その重要性が最近とみに
増している。 2,4-dihydroxybenzaldehyde ()
They exhibit interesting behaviors such as anticancer activity, plant root growth promotion activity, antibacterial activity, and inhibition of photophosphorylation in chloroplasts, and their importance has recently increased.
すでに、アルカリの存在下に１・３−ジヒドロ
キシベンゼンとクロロホルムを反応せしめること
により２・４−ジヒドロキシベンズアルデヒドを
合成する方法は公知であつた。しかしながら、後
述の比較例１に見られるように、この反応では、
二個のホルミル基を有する２・４−ジヒドロキシ
−３−ホルミルベンズアルデヒド（）が大量に
副生し、目的物である２・４−ジヒドロキシベン
ズアルデヒドの収率および選択率は低い。従つ
て、この方法で２・４−ジヒドロキシベンズアル
デヒドを得るには、大量の原料が必要であると同
時に、分離操作を必要とした。 A method for synthesizing 2,4-dihydroxybenzaldehyde by reacting 1,3-dihydroxybenzene and chloroform in the presence of an alkali has already been known. However, as seen in Comparative Example 1 below, in this reaction,
A large amount of 2,4-dihydroxy-3-formylbenzaldehyde (2) having two formyl groups is produced as a by-product, and the yield and selectivity of the target product, 2,4-dihydroxybenzaldehyde, are low. Therefore, in order to obtain 2,4-dihydroxybenzaldehyde by this method, a large amount of raw materials and separation operations were required.
本発明は、上記の反応系に環状オリゴ糖である
シクロデキストリンを添加することにより、目的
生成物である２・４−ジヒドロキシベンズアルデ
ヒドの収率および選択性を顕著に向上させ、省原
料と分離操作の簡素化を実現したものである。 The present invention significantly improves the yield and selectivity of the target product 2,4-dihydroxybenzaldehyde by adding cyclodextrin, which is a cyclic oligosaccharide, to the above reaction system, thereby saving raw materials and separation operation. This simplification has been realized.
すなわち、本発明者らは、１・３−ジヒドロキ
シベンゼンと水酸化ナトリウムまたは水酸化カリ
ウムの水溶液にシクロデキストリンを加え、溶解
せしめた後にクロロホルムを加えることにより、
２・４−ジヒドロキシベンズアルデヒドを高収
率、高選択性で合成することに成功した。本発明
における目的物である２・４−ジヒドロキシベン
ズアルデヒドの収率および選択率はいずれもほぼ
100％である。 That is, the present inventors added cyclodextrin to an aqueous solution of 1,3-dihydroxybenzene and sodium hydroxide or potassium hydroxide, dissolved it, and then added chloroform.
We succeeded in synthesizing 2,4-dihydroxybenzaldehyde with high yield and high selectivity. The yield and selectivity of 2,4-dihydroxybenzaldehyde, which is the target product of the present invention, are approximately
It is 100%.
シクロデキストリンとしては、α−シクロデキ
ストリンとβ−シクロデキストリンのいずれも用
いることができる。シクロデキストリンの添加量
としては、ほぼ100％に近い選択率で２・４−ジ
ヒドロキシベンズアルデヒドを得るためには、反
応系中に存在するクロロホルムに対するモル比で
0.5以上が望ましいが、これ以下の量のシクロデ
キストリン使用量でも２・４−ジヒドロキシベン
ズアルデヒドの生成の選択性の向上は達成され
る。 As the cyclodextrin, both α-cyclodextrin and β-cyclodextrin can be used. In order to obtain 2,4-dihydroxybenzaldehyde with a selectivity close to 100%, the amount of cyclodextrin added must be adjusted to the molar ratio to the chloroform present in the reaction system.
Although 0.5 or more is desirable, even if the amount of cyclodextrin used is less than 0.5, an improvement in the selectivity in the production of 2,4-dihydroxybenzaldehyde can be achieved.
本発明における水酸化ナトリウムあるいは水酸
化カリウムの水溶液の濃度は0.1〜50重量％、好
ましくは５〜20％である。また、反応温度は30〜
120℃、好ましくは50〜80℃である。 The concentration of the aqueous solution of sodium hydroxide or potassium hydroxide in the present invention is 0.1 to 50% by weight, preferably 5 to 20%. Also, the reaction temperature is 30~
The temperature is 120°C, preferably 50-80°C.
シクロデキストリンは反応中に変化せず、反応
後そのまま再使用が可能である。反応後、反応系
を酸性にすると溶解度の減少のためにシクロデキ
ストリンが沈殿する。この簡便な方法でシクロデ
キストリンの８割以上は回収され、回収されたシ
クロデキストリンは完全に再使用にたえる。 Cyclodextrin does not change during the reaction and can be reused as is after the reaction. After the reaction, when the reaction system is made acidic, cyclodextrin precipitates due to decreased solubility. More than 80% of the cyclodextrin can be recovered using this simple method, and the recovered cyclodextrin can be completely reused.
つぎに本発明を具体的に実施例をあげて説明す
るが、これにより本発明を制限するものではな
い。 Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例 １
1.0ｇ（9.1ミリモル）の１・３−ジヒドロキシ
ベンゼン（東京化成工業株式会社製、特級試薬）
と8.0ｇ（7.0ミリモル）のβ−シクロデキストリ
ン（半井化学薬品株式会社製、特級試薬）を60ml
の10％水酸化ナトリウム水溶液に溶かした。ここ
に５ml（62.3ミリモル）のクロロホルム（東京化
成工業株式会社製、特級試薬）を徐徐に滴下しつ
つ、反応液を磁気かくはん機を用いてかくはん
し、60℃で４時間反応せしめた。反応後、反応液
を塩酸で酸性にした後、50mlのエーテルで３回抽
出し、エーテル層を水洗した後に乾燥し、1.2ｇ
の生成物を得た。大倉理化学研究所製、701型ガ
スクロマトグラフ（充填剤、ガスクロ工業株式会
社製、Tenax GC；カラム長、２ｍ；カラム温度
300℃；キヤリヤーガス、ヘリウム）で分析した
結果、生成物はすべて２・４−ジヒドロキシベン
ズアルデヒドであり、２・４−ジヒドロキシ−３
−ホルミルベンズアルデヒドは検出されなかつ
た。すなわち、目的物の収率は96モル％であり、
選択率は100％であつた。Example 1 1.0 g (9.1 mmol) of 1,3-dihydroxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent)
and 8.0 g (7.0 mmol) of β-cyclodextrin (manufactured by Hani Chemical Co., Ltd., special grade reagent) in 60 ml.
was dissolved in a 10% aqueous sodium hydroxide solution. While 5 ml (62.3 mmol) of chloroform (manufactured by Tokyo Kasei Kogyo Co., Ltd., special grade reagent) was slowly added dropwise thereto, the reaction solution was stirred using a magnetic stirrer and allowed to react at 60°C for 4 hours. After the reaction, the reaction solution was made acidic with hydrochloric acid, extracted three times with 50 ml of ether, and the ether layer was washed with water and dried.
of product was obtained. Gas chromatograph type 701 manufactured by Okura Rikagaku Kenkyusho Co., Ltd. (filling material, Tenax GC manufactured by Gas Kuro Kogyo Co., Ltd.; column length, 2 m; column temperature
As a result of analysis at 300℃; carrier gas, helium), all the products were 2,4-dihydroxybenzaldehyde, and 2,4-dihydroxy-3
- Formylbenzaldehyde was not detected. That is, the yield of the target product is 96 mol%,
The selection rate was 100%.
比較例 １
試薬はすべて実施例１に記載したものと同一の
ものを使用した。1.0ｇ（9.1ミリモル）の１・３
−ジヒドロキシベンゼンを60mlの10％水酸化ナト
リウム水溶液に溶かし、ここに５ml（62.3ミリモ
ル）のクロロホルムを徐徐に滴下しつつ、反応液
を磁気かくはん機を用いてかくはんし、60℃で４
時間反応せしめた。反応後、反応液を塩酸で酸性
にした後、50mlのエーテルで３回抽出し、エーテ
ル層を水洗した後に乾燥し、0.9ｇの生成物を得
た。大倉理化学研究所製、701型ガスクロマトグ
ラフで分析した結果、生成物は0.3ｇの２・４−
ジヒドロキシベンズアルデヒドと0.6ｇの２・４
−ジヒドロキシ−３−ホルミルベンズアルデヒド
との混合物であつた。すなわち、目的物の収率は
24モル％であり、選択率は38％であつた。Comparative Example 1 All reagents were the same as those described in Example 1. 1.3 of 1.0g (9.1 mmol)
- Dihydroxybenzene was dissolved in 60 ml of 10% sodium hydroxide aqueous solution, and 5 ml (62.3 mmol) of chloroform was slowly added dropwise thereto, while the reaction solution was stirred using a magnetic stirrer and heated to 60°C for 4 hours.
I let it react over time. After the reaction, the reaction solution was made acidic with hydrochloric acid, extracted three times with 50 ml of ether, and the ether layer was washed with water and dried to obtain 0.9 g of product. As a result of analysis using a 701 gas chromatograph manufactured by Okura Rikagaku Kenkyusho, 0.3 g of the 2,4-
Dihydroxybenzaldehyde and 0.6g of 2.4
-dihydroxy-3-formylbenzaldehyde. In other words, the yield of the target product is
It was 24 mol%, and the selectivity was 38%.
Claims (1)
在下に、１・３−ジヒドロキシベンゼンに対して
クロロホルムを反応させるにあたり、シクロデキ
ストリンを触媒として用いることにより、２・４
−ジヒドロキシベンズアルデヒドを高選択的に製
造する方法。1. In the presence of sodium hydroxide or potassium hydroxide, 1,3-dihydroxybenzene is reacted with chloroform by using cyclodextrin as a catalyst.
- A method for highly selectively producing dihydroxybenzaldehyde.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56151571A JPS5855441A (en) | 1981-09-25 | 1981-09-25 | Synthesizing method of 2,4-dihydroxybenzaldehyde |
| PCT/JP1982/000066 WO1982003073A1 (en) | 1981-03-09 | 1982-03-09 | Process for introducing substituent to p-position of phenols |
| DE8282900665T DE3274104D1 (en) | 1981-03-09 | 1982-03-09 | Process for selectively producing para-substituted derivatives of phenols |
| DE8484112783T DE3276858D1 (en) | 1981-03-09 | 1982-03-09 | A process for producing a para-substituted phenol derivative |
| EP19840112783 EP0158709B1 (en) | 1981-03-09 | 1982-03-09 | A process for producing a para-substituted phenol derivative |
| EP82900665A EP0073837B1 (en) | 1981-03-09 | 1982-03-09 | Process for selectively producing para-substituted derivatives of phenols |
| US06/530,157 US4523037A (en) | 1981-03-09 | 1983-09-07 | Process for selectively producing para-substituted derivatives of phenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56151571A JPS5855441A (en) | 1981-09-25 | 1981-09-25 | Synthesizing method of 2,4-dihydroxybenzaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5855441A JPS5855441A (en) | 1983-04-01 |
| JPS6245216B2 true JPS6245216B2 (en) | 1987-09-25 |
Family
ID=15521430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56151571A Granted JPS5855441A (en) | 1981-03-09 | 1981-09-25 | Synthesizing method of 2,4-dihydroxybenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5855441A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103519U (en) * | 1987-12-26 | 1989-07-13 | ||
| JPH0252723U (en) * | 1988-10-07 | 1990-04-16 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204768A (en) * | 2013-03-12 | 2013-07-17 | 西北大学 | Synthetic method for hydroxybenzaldehyde |
-
1981
- 1981-09-25 JP JP56151571A patent/JPS5855441A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103519U (en) * | 1987-12-26 | 1989-07-13 | ||
| JPH0252723U (en) * | 1988-10-07 | 1990-04-16 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5855441A (en) | 1983-04-01 |
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