JPH0136815B2 - - Google Patents
Info
- Publication number
- JPH0136815B2 JPH0136815B2 JP57051072A JP5107282A JPH0136815B2 JP H0136815 B2 JPH0136815 B2 JP H0136815B2 JP 57051072 A JP57051072 A JP 57051072A JP 5107282 A JP5107282 A JP 5107282A JP H0136815 B2 JPH0136815 B2 JP H0136815B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- hydroxychalcone
- derivatives
- reaction
- manufactured
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229920000858 Cyclodextrin Polymers 0.000 claims description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- UDOOPSJCRMKSGL-UHFFFAOYSA-N 3-(2-hydroxyphenyl)-1-phenylprop-2-en-1-one Chemical compound OC1=CC=CC=C1C=CC(=O)C1=CC=CC=C1 UDOOPSJCRMKSGL-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- PWWCDTYUYPOAIU-DHZHZOJOSA-N 4-hydroxychalcone Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)C1=CC=CC=C1 PWWCDTYUYPOAIU-DHZHZOJOSA-N 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 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 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JTWHVBNYYWFXSI-UHFFFAOYSA-N 2-nitro-1-phenylethanone Chemical compound [O-][N+](=O)CC(=O)C1=CC=CC=C1 JTWHVBNYYWFXSI-UHFFFAOYSA-N 0.000 description 1
- OESPNJQIRRMMGU-UHFFFAOYSA-N 2-oxo-2-phenylethanesulfonic acid Chemical compound OS(=O)(=O)CC(=O)C1=CC=CC=C1 OESPNJQIRRMMGU-UHFFFAOYSA-N 0.000 description 1
- HXUIDZOMTRMIOE-UHFFFAOYSA-N 3-oxo-3-phenylpropionic acid Chemical compound OC(=O)CC(=O)C1=CC=CC=C1 HXUIDZOMTRMIOE-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 208000002699 Digestive System Neoplasms Diseases 0.000 description 1
- 206010061459 Gastrointestinal ulcer Diseases 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 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
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940124597 therapeutic agent Drugs 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
Description
【発明の詳細な説明】
本発明はヒドロキシカルコンおよびその誘導体
の合成法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing hydroxychalcone and its derivatives.
ヒドロキシカルコンおよびその誘導体は、胃腸
潰瘍や腫瘍の治療薬、消炎剤、および種々の医
薬、農薬などの合成中間体として、その重要性が
最近とみに増している。 Hydroxychalcone and its derivatives have recently become increasingly important as therapeutic agents for gastrointestinal ulcers and tumors, anti-inflammatory agents, and synthetic intermediates for various pharmaceuticals and agricultural chemicals.
すでに、アルカリの存在下にフエノールとハロ
ホルムとを反応させてヒドロキシベンズアルデヒ
ドを合成し、これをアセトフエノンおよびその誘
導体と反応させてヒドロキシカルコンおよびその
誘導体を合成する方法は公知であつた。しかしな
がら、後述の比較例に見られるように、上述の方
法で合成を実施すると、目的物の収率は非常に小
さく、しかも多量の副生成物が副生する。 A method has already been known in which hydroxybenzaldehyde is synthesized by reacting phenol and haloform in the presence of an alkali, and hydroxychalcone and its derivatives are synthesized by reacting this with acetophenone and its derivatives. However, as seen in the Comparative Examples described below, when the synthesis is carried out by the above method, the yield of the target product is very small, and moreover, a large amount of by-products are produced.
本発明は、上記の反応系にシクロデキストリン
を添加することにより、目的生成物であるヒドロ
キシカルコンおよびその誘導体を高収率および高
選択的に合成し、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 synthesizes the target product hydroxychalcone and its derivatives in high yield and with high selectivity by adding cyclodextrin to the above reaction system, thereby saving raw materials and simplifying the separation operation. It is something.
すなわち、本発明者らは、フエノールと水酸化
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、ハロ
ホルムおよびアセトフエノンまたはその誘導体を
順次加えることによりヒドロキシカルコンおよび
その誘導体を高収率、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ヒドロキ
シカルコンまたはその誘導体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 phenol and sodium hydroxide or potassium hydroxide, dissolved it, and then sequentially added haloform and acetophenone or its derivative, thereby producing hydroxychalcone and its derivative in high yield. , were successfully synthesized with high selectivity. Both the yield and selectivity of hydroxychalcone or its derivative, which is the object of the present invention, are approximately 100%.
明細書に記載するアセトフエノン誘導体とは、
たとえばヒドロキシアセトフエノン、メチルアセ
トフエノン、ニトロアセトフエノン、カルボキシ
アセトフエノン、スルホアセトフエノン、カルボ
キシアルコキシアセトフエノンおよびスルホアル
コキシアセトフエノンなどである。 The acetophenone derivatives described in the specification are:
Examples include hydroxyacetophenone, methylacetophenone, nitroacetophenone, carboxyacetophenone, sulfoacetophenone, carboxyalkoxyacetophenone and sulfoalkoxyacetophenone.
本発明においては、反応試薬の添加順序が、生
成するヒドロキシカルコンおよびその誘導体の構
造に重要な影響をもたらす。すなわち、実施例１
に見られるように、シクロデキストリンを含むフ
エノールのアルカリ水溶液に、ハロホルム、アセ
トフエノンまたはその誘導体をこの順序に加えて
反応せしめると、４−ヒドロキシカルコンまたは
その誘導体がほぼ100％の選択率で得られる。た
だし、反応試薬の添加の際には、それ以前に加え
た異種の反応試薬とフエノールあるいはそれに由
来する反応中間体との反応の反応率が50〜100％、
好ましくは95〜100％であることが、本発明の実
施には望ましい。 In the present invention, the order of addition of reaction reagents has an important effect on the structure of the hydroxychalcone and its derivatives produced. That is, Example 1
As shown in , when haloform, acetophenone, or a derivative thereof is added in this order to an alkaline aqueous solution of phenol containing cyclodextrin and reacted, 4-hydroxychalcone or a derivative thereof is obtained with almost 100% selectivity. However, when adding a reaction reagent, the reaction rate of the reaction between the previously added different reaction reagent and phenol or a reaction intermediate derived from it is 50 to 100%.
Preferably 95-100% is desirable for practicing the present invention.
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％に近い選択率でヒドロキシ
カルコンまたはその誘導体を得るためには、反応
系中に存在するハロホルムおよびアセトフエノン
またはその誘導体に対するモル比で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
用量でもヒドロキシカルコンまたはその誘導体の
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 hydroxychalcone or its derivatives with a selectivity close to 100%, the amount of cyclodextrin added is preferably 0.5 or more in terms of molar ratio to haloform and acetophenone or its derivatives present in the reaction system. Even with the following amounts of cyclodextrin used, improved selectivity in the production of hydroxychalcone or its derivatives is 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。 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%.
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
ストリンが沈澱する。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
1.0ｇ（10.6ミリモル）のフエノール（東京化
成工業株式会社製、特級試薬）と2.4ｇ（2.1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80mlの10％水酸化ナト
リウム水溶液に溶かした。ここに1.5ml（18.7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）を滴下しつつ、反応液を磁気撹拌
機を用いて撹拌し、70℃で10時間反応せしめた。
次に反応液を氷で十分に冷却した後に、1.3ｇ
（10.8ミリモル）のアセトフエノン（東京化成株
式会社製、特級試薬）を徐々に加え、室温で10時
間反応せしめた。その後、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、2.0ｇの生成物を得た。
大倉理化学研究所製、710型ガスクロマトグラフ
（充填剤、ガスクロ工業株式会社製、ユニポート
HP；カラム長２ｍ；カラム温度120℃；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４−ヒドロキシカルコンであつた。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 1.0 g (10.6 mmol) of phenol (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent) and 2.4 g (2.1 mmol) of β-cyclodextrin (manufactured by Hanui Chemical Co., Ltd., special grade reagent) were added to 80 ml of 10% water. Dissolved in aqueous sodium oxide solution. While 1.5 ml (18.7 mmol) of chloroform (manufactured by Tokyo Kasei Kogyo Co., Ltd., special grade reagent) was added dropwise thereto, the reaction solution was stirred using a magnetic stirrer and allowed to react at 70°C for 10 hours.
Next, after cooling the reaction solution sufficiently with ice, 1.3 g
(10.8 mmol) of acetophenone (manufactured by Tokyo Kasei Co., Ltd., special grade reagent) was gradually added, and the mixture was allowed to react at room temperature for 10 hours. Thereafter, the reaction solution was acidified with hydrochloric acid, extracted three times with 50 ml of ether, and the ether layer was washed with water and dried to obtain 2.0 g of product.
Manufactured by Okura Rikagaku Kenkyusho, 710 type gas chromatograph (filler, manufactured by Gascro Industries Co., Ltd., Uniport
As a result of HP analysis (column length: 2 m; column temperature: 120° C.; carrier gas, helium), all of the products were 4-hydroxychalcone. That is, the yield of the target product is 96 mol%, and the selectivity is
It was 100%.
比較例
2.4ｇのβ−シクロデキストリンを使用しない
点以外は、実施例１と同様の操作を行い、1.4ｇ
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、ユニポートHP；カラム長２ｍ；カラム温
度140℃；キヤリヤーガス、ヘリウム）で分析し
た結果、生成物は４−ヒドロキシカルコン、２−
ヒドロキシカルコン、４−ヒドロキシベンズアル
デヒドおよび２−ヒドロキシベンズアルデヒドの
混合物であつた。目的物の収率は10モル％であ
り、選択率は16％であつた。Comparative Example The same operation as in Example 1 was carried out except that 2.4 g of β-cyclodextrin was not used.
of product was obtained. As a result of analysis using a model 701 gas chromatograph manufactured by Okura Rikagaku Kenkyusho (filling material, Uniport HP manufactured by Gascro Industries Co., Ltd.; column length 2 m; column temperature 140°C; carrier gas, helium), the products were 4-hydroxychalcone, 2 −
It was a mixture of hydroxychalcone, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde. The yield of the target product was 10 mol%, and the selectivity was 16%.
Claims (1)
在下に、フエノールに対してハロホルムおよびア
セトフエノンまたはその誘導体を順次反応させる
にあたり、シクロデキストリンを触媒として用い
ることによりヒドロキシカルコンおよびその誘導
体を高選択的に製造する方法。1. A method for highly selectively producing hydroxychalcone and its derivatives by using cyclodextrin as a catalyst in the sequential reaction of phenol with haloform and acetophenone or its derivatives in the presence of sodium hydroxide or potassium hydroxide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57051072A JPS58170729A (en) | 1982-03-31 | 1982-03-31 | Synthetic method of hydroxychalcone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57051072A JPS58170729A (en) | 1982-03-31 | 1982-03-31 | Synthetic method of hydroxychalcone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58170729A JPS58170729A (en) | 1983-10-07 |
| JPH0136815B2 true JPH0136815B2 (en) | 1989-08-02 |
Family
ID=12876600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57051072A Granted JPS58170729A (en) | 1982-03-31 | 1982-03-31 | Synthetic method of hydroxychalcone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58170729A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU576457B2 (en) * | 1984-02-14 | 1988-08-25 | Hirai, Hidefumi | Process for preparing p-substituted phenol derivatives |
-
1982
- 1982-03-31 JP JP57051072A patent/JPS58170729A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| DIE MARKROMOLEKULARE CHEMIE RAPID DOMMUNICATIONS=1981 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58170729A (en) | 1983-10-07 |
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