JP4225600B2 - Production method of chromones - Google Patents
Production method of chromones Download PDFInfo
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- JP4225600B2 JP4225600B2 JP07580598A JP7580598A JP4225600B2 JP 4225600 B2 JP4225600 B2 JP 4225600B2 JP 07580598 A JP07580598 A JP 07580598A JP 7580598 A JP7580598 A JP 7580598A JP 4225600 B2 JP4225600 B2 JP 4225600B2
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- chromones
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- 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
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- Pyrane Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、短時間で工業的に有利にクロモン類を製造し得る方法に関する。
【０００２】
【従来の技術】
クロモン類の中には気管支喘息に代表される呼吸器系疾患の治療薬、メラニン産生抑制剤など優れた生理作用を示すものが多く存在する。当該クロモン類のうち、例えば一般式（３）で表わされるクロモン類の製造法としては、化合物（１）と化合物（２）を水素化ナトリウム等の塩基の存在下で縮合させ、得られる化合物を塩酸、硫酸、ｐ−トルエンスルホン酸等の酸の存在下で加熱して脱水させる方法が知られている（例えば、Lindeman et al:Ann.,456,304(1927)、V.V.Irkar et al:Indian Acd.Sci.,30A,57(1949)、J.H.Richards et al:J.C.S.,1610(1948)、特開平７−１８８２０８号公報、特開平１０−１７５６３号公報）。
【０００３】
【化４】
（式中、Ｒ1 は水素原子、ヒドロキシル基又は炭素数１〜５のアルコキシル基を示し、Ｒ2 は水素原子又は炭素数１〜５のアルキル基を示し、Ｒ3 は炭素数１〜１５のアルキル基を示し、Ｒ4 は炭素数１〜５のアルキル基を示す）
【０００５】
【発明が解決しようとする課題】
しかし、これらの合成法を用いて実製造する場合、縮合反応で得られる中間体の加熱脱水反応時に、反応槽内が著しく着色し、不溶物が発生して反応槽内に付着してしまう。そのため、反応物の移送時に濾過作業が必要となることや、反応槽の洗浄が困難であること等、操作性に問題が多く実製造には不向きなものであった。
【０００６】
従って、本発明は短時間で工業的に有利なクロモン類の製造法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
そこで本発明者らは、加熱脱水反応について検討した結果、縮合後の加熱脱水反応において、特定の酸触媒を用いれば、短時間で収率良くクロモン類を製造できることを見出し、本発明を完成した。
【０００８】
すなわち、本発明は、一般式（１）
【０００９】
【化５】
（式中、Ｒ1 及びＲ2 は前記と同じ）
で表わされるアセトフェノン類に、一般式（２）
【００１１】
【化６】
（式中、Ｒ3 及びＲ4 は前記に同じ）で表わされる脂肪酸エステルを反応させ、得られた成績体をリン酸、活性白土及び硫酸・酢酸混合液からなる群より選ばれる１種以上の酸触媒の存在下に加熱脱水反応させることを特徴とする一般式（３）
【００１３】
【化７】
（式中、Ｒ1 、Ｒ2 及びＲ3 は前記と同じ）
で表わされるクロモン類の製造法を提供するものである。
【００１５】
【発明の実施の形態】
本発明で用いるアセトフェノン類（１）において、Ｒ1 のうち好ましいものとしては、メトキシ基、エトキシ基等が挙げられる。このうちメトキシ基が特に好ましい。Ｒ2 のうち好ましいものとしては、水素原子及びメチル基、エチル基等が挙げられる。このうち水素原子が特に好ましい。
【００１６】
脂肪酸エステル類（２）において、Ｒ3 のうち好ましいものとしては、Ｒ2 において例示した炭素数１〜５のアルキル基に加えて、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−ペンタデシル基等の直鎖アルキル基、ｔ−ブチル基、ｓｅｃ−ヘキシル基、１−エチルペンチル基等の分岐鎖アルキル基が挙げられる。このうち１−エチルペンチル基が特に好ましい。Ｒ4 のうち好ましいものとしては、Ｒ2 において例示したメチル基、エチル基等が挙げられる。
【００１７】
アセトフェノン類（１）と脂肪酸エステル（２）との反応は、例えばトルエン、キシレンなどの炭化水素類溶媒中ポリエチレングリコールなどのポリアルキレングリコール又はそのアルキルエーテル及び水素化ナトリウムの存在下、１１０〜１６０℃程度で又は加熱還流下で行うことが好ましい。反応は約３〜２０時間で終了する。また、この反応は窒素気流下で行うことが好ましい。
【００１８】
縮合反応終了後、縮合生成物を単離することなく、加熱脱水反応を行うのが有利である。例えば必要に応じて水等を加えて反応を停止させ、リン酸等で中和して水層を分離した後、前記特定の酸性触媒の存在下に加熱脱水反応させることにより、目的とするクロモン類（３）を得ることができる。用いる酸性触媒はリン酸、活性白土及び硫酸・酢酸混合液から選ばれる１種又は２種以上である。従来の酸性触媒条件では、耐酸性グラスコーティング（ＧＬ）槽で加熱脱水反応させる必要があるが、リン酸、活性白土又は硫酸・酢酸混合液を酸性触媒とすると、ステンレス（ＳＵＳ）反応槽に対する腐食性が問題ないため、縮合反応から加熱脱水反応までをＳＵＳ反応槽で行えることからより好ましい。活性白土を触媒に用いる場合、反応後に活性白土を除去する濾過工程が必要であるが、リン酸を用いる場合はこのような操作を必要としないことから特に好ましい。
【００１９】
ここで白土とは、カオリンやモンモリロン石を主体とする白色粘土であり、モンモリロン石を主体とするベントナイト、酸性白土が好ましい。活性白土とはかかる白土を酸処理して活性を強めたものをいう。活性白土は市販品を用いうる。また硫酸は濃硫酸でも希硫酸でもよいが、濃硫酸が好ましい。
【００２０】
酸触媒の使用量は、アセトフェノン類（１）に対して、リン酸は０．００５〜２モル％、特に０．０１〜０．５モル％が好ましい。活性白土は０．０５〜５重量％、特に０．１〜１重量％が好ましい。硫酸・酢酸混合液は硫酸量５〜５０重量％、酢酸量５０〜２００重量％、特に硫酸量１０〜３０重量％、酢酸量５０〜１５０重量％が好ましい。
【００２１】
脱水反応の温度は、リン酸触媒では１２０〜２７０℃、特に１６０〜２００℃が好ましい。活性白土触媒では８０〜１８０℃、特に１１０〜１５０℃が好ましい。硫酸・酢酸混合系では６０〜１２０℃、特に８０〜１００℃が好ましい。いずれの酸性触媒を用いる場合でも、１〜２０時間で反応は完結する。また、この反応は窒素気流下で行うことが好ましい。
【００２２】
得られたクロモン類（３）は常法に従って単離することができる。クロモン類（３）は皮膚に対する色素沈着改善効果に優れ、皮膚外用剤等の成分として有用である。
【００２３】
【実施例】
以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２４】
実施例１
窒素気流下、水素化ナトリウム（純分６０％）３２５ｇをキシレン５１８８ｇに加えた。１３０℃に昇温後、２−エチルヘキサン酸メチル７６２ｇを滴下して、ポリエチレングリコール４００を２００ｇ滴下した。２−ヒドロキシ−４−メトキシアセトフェノン５００ｇをキシレン４５０ｇに溶解させたものを滴下した。１３０℃で７時間反応させた後、水を加えて反応を停止させ、リン酸中和を行い水層を分離した。有機層を２回水洗後、低沸点を留去し、残渣を得た。窒素気流下、反応残渣に酸性触媒としてリン酸０．２９ｇを加えて１８０℃で５時間脱水反応させた後、これを蒸留、結晶化により精製して２−（１−エチルペンチル）−７−メトキシクロモン（収率６０％）を得た。反応槽内に着色及び不溶物の発生は認められなかった。
【００２５】
実施例２
実施例１において、２−ヒドロキシ−４−メトキシアセトフェノンを１００ｇとし、酸性触媒としてリン酸の代りに活性白土０．５ｇを用い、１３０℃で１０時間脱水反応させた以外は実施例１と同様にして２−（１−エチルペンチル）−７−メトキシクロモン（収率６２％）を得た。反応槽内に着色及び不溶物の発生は認められなかった。
【００２６】
実施例３
実施例１において、２−ヒドロキシ−４−メトキシアセトフェノンを１００ｇとし、酸性触媒としてリン酸の代りに硫酸２０ｇ及び酢酸１００ｇを用い、９０℃で３時間脱水反応させた以外は実施例１と同様にして２−（１−エチルペンチル）−７−メトキシクロモン（収率６１％）を得た。反応槽内に着色及び不溶物の発生は認められなかった。
【００２７】
比較例１
実施例１において、２−ヒドロキシ−４−メトキシアセトフェノン１００ｇを用いて縮合反応を行った。窒素気流下、低沸分を留去していない反応系にｐ−トルエンスルホン酸−水和物３１ｇを加えて１３０℃で２時間反応させたところ、反応槽内の着色と不溶物の発生が認められた。
【００２８】
【発明の効果】
本発明によれば、反応槽内に着色や不溶物を生じることなく、クロモン類を短時間、かつ高収率で製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method capable of producing chromones industrially advantageously in a short time.
[0002]
[Prior art]
Many chromones exhibit excellent physiological effects such as therapeutic agents for respiratory diseases typified by bronchial asthma and melanin production inhibitors. Among the chromones, for example, as a method for producing chromones represented by the general formula (3), the compound (1) and the compound (2) are condensed in the presence of a base such as sodium hydride, and the resulting compound is obtained. There are known methods for dehydration by heating in the presence of an acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (for example, Lindeman et al: Ann., 456, 304 (1927), VVIrkar et al: Indian Acd. Sci). 30A, 57 (1949), JHRichards et al: JCS, 1610 (1948), JP-A-7-188208, JP-A-10-17563).
[0003]
[Formula 4]
(In the formula, R 1 represents a hydrogen atom, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms, R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 3 has 1 to 15 carbon atoms. Represents an alkyl group, and R 4 represents an alkyl group having 1 to 5 carbon atoms)
[0005]
[Problems to be solved by the invention]
However, in the case of actual production using these synthesis methods, during the heat dehydration reaction of the intermediate obtained by the condensation reaction, the inside of the reaction tank is remarkably colored and insoluble matter is generated and adheres to the reaction tank. For this reason, there are many problems in operability such as the necessity of filtration work when transferring the reactants and the difficulty of cleaning the reaction tank, which are unsuitable for actual production.
[0006]
Accordingly, an object of the present invention is to provide an industrially advantageous method for producing chromones in a short time.
[0007]
[Means for Solving the Problems]
Thus, as a result of examining the heat dehydration reaction, the present inventors have found that chromones can be produced in a high yield in a short time by using a specific acid catalyst in the heat dehydration reaction after condensation, and the present invention has been completed. .
[0008]
That is, the present invention relates to the general formula (1)
[0009]
[Chemical formula 5]
(Wherein R 1 and R 2 are the same as above)
In the acetophenones represented by general formula (2)
[0011]
[Chemical 6]
(Wherein R 3 and R 4 are the same as described above), and the resulting product is one or more selected from the group consisting of phosphoric acid, activated clay and sulfuric acid / acetic acid mixed solution. General formula (3), characterized in that the heat dehydration reaction is carried out in the presence of an acid catalyst.
[0013]
[Chemical 7]
(Wherein R 1 , R 2 and R 3 are the same as above)
The manufacturing method of chromones represented by these is provided.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
In the acetophenones (1) used in the present invention, preferable examples of R 1 include a methoxy group and an ethoxy group. Of these, a methoxy group is particularly preferred. Preferred examples of R 2 include a hydrogen atom, a methyl group, and an ethyl group. Of these, a hydrogen atom is particularly preferable.
[0016]
In the fatty acid esters (2), as preferable among R 3 , in addition to the alkyl group having 1 to 5 carbon atoms exemplified for R 2 , an n-hexyl group, an n-heptyl group, an n-pentadecyl group, etc. Examples include a branched alkyl group such as a linear alkyl group, a t-butyl group, a sec-hexyl group, and a 1-ethylpentyl group. Of these, a 1-ethylpentyl group is particularly preferable. Preferable examples of R 4 include the methyl group and ethyl group exemplified in R 2 .
[0017]
The reaction of acetophenones (1) and fatty acid esters (2) is carried out in the presence of a polyalkylene glycol such as polyethylene glycol or its alkyl ether and sodium hydride in a hydrocarbon solvent such as toluene or xylene. It is preferable to carry out at a moderate temperature or under reflux. The reaction is completed in about 3 to 20 hours. Further, this reaction is preferably carried out under a nitrogen stream.
[0018]
After completion of the condensation reaction, it is advantageous to carry out the heat dehydration reaction without isolating the condensation product. For example, if necessary, water or the like is added to stop the reaction, the aqueous layer is separated by neutralization with phosphoric acid or the like, and then subjected to a heat dehydration reaction in the presence of the specific acidic catalyst, whereby the target chromone is obtained. Class (3) can be obtained. The acidic catalyst to be used is one or more selected from phosphoric acid, activated clay and sulfuric acid / acetic acid mixed solution. Under conventional acidic catalyst conditions, heat dehydration reaction is required in an acid-resistant glass coating (GL) tank. However, when phosphoric acid, activated clay or sulfuric acid / acetic acid mixture is used as an acid catalyst, corrosion on a stainless steel (SUS) reaction tank. Since there is no problem in properties, it is more preferable because the reaction from the condensation reaction to the heat dehydration reaction can be performed in the SUS reaction tank. When activated clay is used as a catalyst, a filtration step for removing the activated clay after the reaction is necessary. However, when phosphoric acid is used, it is particularly preferable because such an operation is not required.
[0019]
Here, the white clay is a white clay mainly composed of kaolin and montmorillonite, and bentonite and acidic white clay mainly composed of montmorillonite are preferable. Activated clay refers to a material obtained by acid treatment of such a clay. Commercially available white clay can be used. The sulfuric acid may be concentrated sulfuric acid or dilute sulfuric acid, but concentrated sulfuric acid is preferred.
[0020]
The amount of the acid catalyst used is preferably 0.005 to 2 mol%, particularly 0.01 to 0.5 mol% of phosphoric acid with respect to the acetophenones (1). The activated clay is preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight. The sulfuric acid / acetic acid mixed solution is preferably 5 to 50% by weight of sulfuric acid, 50 to 200% by weight of acetic acid, particularly 10 to 30% by weight of sulfuric acid and 50 to 150% by weight of acetic acid.
[0021]
The temperature of the dehydration reaction is preferably 120 to 270 ° C., particularly 160 to 200 ° C. for the phosphoric acid catalyst. For an activated clay catalyst, 80 to 180 ° C, particularly 110 to 150 ° C is preferable. In a sulfuric acid / acetic acid mixed system, 60 to 120 ° C., particularly 80 to 100 ° C. is preferable. Even when any acidic catalyst is used, the reaction is completed in 1 to 20 hours. Further, this reaction is preferably carried out under a nitrogen stream.
[0022]
The obtained chromones (3) can be isolated according to a conventional method. The chromones (3) are excellent in the effect of improving pigmentation on the skin and are useful as components for external preparations for skin.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
[0024]
Example 1
Under a nitrogen stream, 325 g of sodium hydride (pure content 60%) was added to 5188 g of xylene. After raising the temperature to 130 ° C., 762 g of methyl 2-ethylhexanoate was added dropwise, and 200 g of polyethylene glycol 400 was added dropwise. A solution prepared by dissolving 500 g of 2-hydroxy-4-methoxyacetophenone in 450 g of xylene was added dropwise. After reacting at 130 ° C. for 7 hours, water was added to stop the reaction, neutralization with phosphoric acid was performed, and the aqueous layer was separated. After washing the organic layer twice with water, the low boiling point was distilled off to obtain a residue. Under a nitrogen stream, 0.29 g of phosphoric acid as an acidic catalyst was added to the reaction residue and subjected to dehydration reaction at 180 ° C. for 5 hours, and then purified by distillation and crystallization to give 2- (1-ethylpentyl) -7- Methoxychromone (yield 60%) was obtained. Neither coloring nor insoluble matter was observed in the reaction vessel.
[0025]
Example 2
In Example 1, 100 g of 2-hydroxy-4-methoxyacetophenone was used, 0.5 g of activated clay was used instead of phosphoric acid as an acidic catalyst, and a dehydration reaction was performed at 130 ° C. for 10 hours. To 2- (1-ethylpentyl) -7-methoxychromone (yield 62%). Neither coloring nor insoluble matter was observed in the reaction vessel.
[0026]
Example 3
In Example 1, 100 g of 2-hydroxy-4-methoxyacetophenone was used, 20 g of sulfuric acid and 100 g of acetic acid were used instead of phosphoric acid as an acidic catalyst, and a dehydration reaction was performed at 90 ° C. for 3 hours. To 2- (1-ethylpentyl) -7-methoxychromone (yield 61%). Neither coloring nor insoluble matter was observed in the reaction vessel.
[0027]
Comparative Example 1
In Example 1, a condensation reaction was performed using 100 g of 2-hydroxy-4-methoxyacetophenone. In a nitrogen stream, 31 g of p-toluenesulfonic acid hydrate was added to the reaction system in which the low boiling point content was not distilled off, and the reaction was carried out at 130 ° C. for 2 hours. As a result, coloring in the reaction tank and generation of insoluble matter occurred. Admitted.
[0028]
【The invention's effect】
According to the present invention, chromones can be produced in a short time and in a high yield without causing coloring or insoluble matter in the reaction vessel.
Claims (2)
で表わされるアセトフェノン類に、一般式（２）
で表わされる脂肪酸エステルを反応させ、得られた縮合生成物をリン酸の存在下に１６０〜２００℃で加熱脱水反応させることを特徴とする一般式（３）
で表わされるクロモン類の製造法。General formula (1)
The acetophenones represented by general formula (2)
And the resulting condensation product is subjected to a heat dehydration reaction at 160 to 200 ° C. in the presence of phosphoric acid.
A method for producing chromones represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07580598A JP4225600B2 (en) | 1998-03-24 | 1998-03-24 | Production method of chromones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07580598A JP4225600B2 (en) | 1998-03-24 | 1998-03-24 | Production method of chromones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11269163A JPH11269163A (en) | 1999-10-05 |
| JP4225600B2 true JP4225600B2 (en) | 2009-02-18 |
Family
ID=13586791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07580598A Expired - Fee Related JP4225600B2 (en) | 1998-03-24 | 1998-03-24 | Production method of chromones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4225600B2 (en) |
-
1998
- 1998-03-24 JP JP07580598A patent/JP4225600B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11269163A (en) | 1999-10-05 |
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