JP3000731B2 - Process for producing oxyflavans - Google Patents
Process for producing oxyflavansInfo
- Publication number
- JP3000731B2 JP3000731B2 JP3186182A JP18618291A JP3000731B2 JP 3000731 B2 JP3000731 B2 JP 3000731B2 JP 3186182 A JP3186182 A JP 3186182A JP 18618291 A JP18618291 A JP 18618291A JP 3000731 B2 JP3000731 B2 JP 3000731B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- oxyflavans
- mol
- reaction
- resorcinol
- 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
-
- 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
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、下記一般式（Ｉ）The present invention relates to a compound represented by the following general formula (I):
【０００２】[0002]
【化２】 Embedded image
【０００３】（式中、Ｒ1 、Ｒ2 およびＲ5 はそれぞれ
独立に、アルキル基、アルケニル基、シクロアルキル
基、アラルキル基もしくはアリール基を表し、Ｒ3 およ
びＲ4 はそれぞれ独立に、水素原子、アルキル基、アル
ケニル基、シクロアルキル基、アラルキル基もしくはア
リール基を表すか、またはＲ1 とＲ2 およびＲ4 とＲ5
がそれぞれ独立に、環を形成する）で示されるオキシフ
ラバン類を、高純度で製造する方法に関するものであ
る。(Wherein R 1 , R 2 and R 5 each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R 3 and R 4 each independently represent a hydrogen atom , An alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, or R 1 and R 2 and R 4 and R 5
, Each independently forming a ring) with high purity.
【０００４】[0004]
【従来の技術】上記一般式（Ｉ）で示されるオキシフラ
バン類の製造法として、例えば、英国特許第 822,659号
明細書、特開昭 55-139375号公報および特開昭 61-2798
0 号公報には、水を反応溶媒とし、ケトン類とレゾルシ
ンを酸触媒の存在下に反応させる方法が開示されてい
る。2. Description of the Related Art As a method for producing oxyflavans represented by the above general formula (I), for example, British Patent No. 822,659, JP-A-55-139375 and JP-A-61-2798
No. 0 discloses a method in which ketones and resorcin are reacted in the presence of an acid catalyst using water as a reaction solvent.
【０００５】[0005]
【発明が解決しようとする課題】しかし、この方法で
は、多量の酸触媒が必要であり、また生成物中の未反応
レゾルシンおよび副生成物（特にポリマー成分）が除去
しきれず、純度の高いオキシフラバン類が得られなかっ
た。本発明の目的は、レゾルシンとケトン類との反応に
よりオキシフラバン類を製造するにあたり、酸触媒量の
低減を可能にするとともに、未反応レゾルシンおよび副
生成物が除去された高純度のオキシフラバン類を製造す
る方法を提供することにある。However, in this method, a large amount of an acid catalyst is required, and unreacted resorcin and by-products (particularly, polymer components) in the product cannot be completely removed, so that high purity oxysulfate cannot be removed. Flavans could not be obtained. An object of the present invention is to reduce the amount of an acid catalyst in producing oxyflavans by reacting resorcinol and ketones, and to reduce the amount of unreacted resorcinol and by-products of high-purity oxyflavans It is to provide a method of manufacturing the.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために鋭意検討を行った結果、反応溶媒にメ
タノールを用い、酸触媒としてｐ−トルエンスルホン酸
を用いることで、この目的が達成されることを見出し
た。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, using methanol as a reaction solvent and p-toluenesulfonic acid as an acid catalyst, I found that my goal was achieved.
【０００７】すなわち本発明は、レゾルシンとケトン類
を、メタノール反応溶媒中で、ｐ−トルエンスルホン酸
触媒の存在下に反応させることにより、前記一般式
（Ｉ）で示されるオキシフラバン類を製造する方法を提
供するものである。That is, according to the present invention, oxyflavans represented by the above general formula (I) are produced by reacting resorcinol and ketones in a methanol reaction solvent in the presence of a p-toluenesulfonic acid catalyst. It provides a method.
【０００８】一般式（Ｉ）において、Ｒ1 〜Ｒ5 で表さ
れるアルキル基は分岐していてもよく、例えば炭素数１
〜５のものを挙げることができる。アルケニル基として
は、例えば炭素数２〜５のものを挙げることができる。
アラルキル基のアルキル部位としては、例えば炭素数１
〜３のものを挙げることができる。また、アリール基と
しては、例えばフェニル基およびナフチル基を挙げるこ
とができる。In the general formula (I), the alkyl groups represented by R 1 to R 5 may be branched, for example, having 1 carbon atom.
To 5 can be mentioned. Examples of the alkenyl group include those having 2 to 5 carbon atoms.
As the alkyl moiety of the aralkyl group, for example,
To 3 can be mentioned. In addition, examples of the aryl group include a phenyl group and a naphthyl group.
【０００９】一般式（Ｉ）で示されるオキシフラバン類
の具体例としては、例えば、以下の化合物が挙げられ
る。Specific examples of the oxyflavans represented by the general formula (I) include the following compounds.
【００１０】[0010]
【化３】 Embedded image
【００１１】本発明の反応に用いられるケトン類として
は、目的とする式（Ｉ）のオキシフラバン類に対応する
ものを選択すればよいが、例えば、アセトン、メチルエ
チルケトン、ジエチルケトン、エチルプロピルケトン、
シクロペンタノン、シクロヘキサノン、ベンジルアセト
ンなどが挙げられる。特に、ケトン類としてアセトンを
用い、上記式（１）で示される２，４，４−トリメチル
−２−（２，４−ジヒドロキシフェニル）−７−ヒドロ
キシクロマンを製造する反応に、本発明の方法は好適で
ある。As the ketones used in the reaction of the present invention, those corresponding to the desired oxyflavans of the formula (I) may be selected. For example, acetone, methyl ethyl ketone, diethyl ketone, ethyl propyl ketone,
Cyclopentanone, cyclohexanone, benzylacetone and the like can be mentioned. In particular, the method of the present invention is used for a reaction for producing 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman represented by the above formula (1) using acetone as a ketone. Is preferred.
【００１２】また、この反応に用いられる酸触媒として
は、例えば、塩酸や硫酸などの無機酸および、ｐ−トル
エンスルホン酸やベンゼンスルホン酸、メタンスルホン
酸などの有機酸が考えられるが、本発明では特にｐ−ト
ルエンスルホン酸を用いる。酸触媒の使用量は、ケトン
類に対して、通常０.0０１〜１モル当量、好ましくは
０.0０１〜０.1モル当量である。レゾルシンとケトン類
の使用割合は、ケトン類１モルに対し、レゾルシンが通
常１〜２０モル、好ましくは２〜１０モルの範囲であ
る。また、反応溶媒であるメタノールは、レゾルシン１
００重量部に対し、通常２５〜３００重量部、好ましく
は２５〜４５重量部の範囲で用いられる。Examples of the acid catalyst used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid and organic acids such as p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid. In particular, p-toluenesulfonic acid is used. The amount of the acid catalyst to be used is generally 0.001 to 1 molar equivalent, preferably 0.001 to 0.1 molar equivalent, relative to the ketones. The ratio of resorcinol to ketones used is usually 1 to 20 mol, preferably 2 to 10 mol, for 1 mol of ketones. In addition, the reaction solvent methanol is resorcinol 1
It is used in an amount of usually 25 to 300 parts by weight, preferably 25 to 45 parts by weight based on 00 parts by weight.
【００１３】本発明の反応方法としては、例えば、レゾ
ルシン、酸触媒およびメタノールの混合物中に、ケトン
類を連続的または間欠的、好ましくは連続的に供給する
方法が挙げられる。この場合、ケトン類の供給速度は特
に制限されないが、レゾルシン１モルあたり０.1〜０.5
モル／hrが好ましい。反応は、通常２０℃から還流温度
の範囲で行うことができるが、高温側では副生成物の生
成が促進されてオキシフラバン類の収率が低下し、一
方、低温側では反応に長時間を要するため、４５〜７０
℃の範囲が好ましい。反応時間は、触媒の種類や使用量
などによっても異なるが、通常は１〜１２時間である。The reaction method of the present invention includes, for example, a method in which ketones are supplied continuously or intermittently, preferably continuously, to a mixture of resorcinol, an acid catalyst and methanol. In this case, the feed rate of ketones is not particularly limited, but is 0.1 to 0.5 per mol of resorcinol.
Mol / hr is preferred. The reaction can be carried out usually at a temperature in the range of 20 ° C. to the reflux temperature. However, on the high temperature side, the generation of by-products is promoted, and the yield of oxyflavans decreases. 45 to 70
C. is preferred. The reaction time varies depending on the type and amount of the catalyst used, but is usually 1 to 12 hours.
【００１４】反応の進行とともに、オキシフラバン類の
結晶が析出し、反応溶液はスラリー状になる。反応終了
後は、常法により反応生成物を濾別し、精製する。例え
ば、反応に使用したメタノール１００重量部あたり、５
０〜５００重量部、好ましくは１５０〜３００重量部の
水を、スラリー状になった反応溶液に添加し、所定時間
攪拌後、濾過などにより固体を分取する。得られた固体
は、水で洗浄し、未反応のレゾルシンと副生成物を除去
する。その後乾燥することにより、目的物である一般式
（Ｉ）のオキシフラバン類を得ることができる。As the reaction proceeds, oxyflavan crystals precipitate, and the reaction solution becomes a slurry. After completion of the reaction, the reaction product is separated by filtration and purified by a conventional method. For example, per 100 parts by weight of methanol used in the reaction, 5
0 to 500 parts by weight, preferably 150 to 300 parts by weight of water is added to the reaction solution in a slurry state, and after stirring for a predetermined time, a solid is collected by filtration or the like. The resulting solid is washed with water to remove unreacted resorcin and by-products. Thereafter, by drying, the oxyflavans of the general formula (I) as the target substance can be obtained.
【００１５】[0015]
【実施例】次に、実施例を挙げて本発明をさらに具体的
に説明するが、本発明はこれらの実施例によってなんら
限定されるものではない。例中の％は、特にことわらな
いかぎり重量基準である。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The percentages in the examples are on a weight basis unless otherwise specified.
【００１６】 実施例１ 攪拌器、冷却器、滴下ロートおよび温度計を装着した四
つ口フラスコに、レゾルシン２００ｇ（１.8２モル）、
ｐ−トルエンスルホン酸１.3８ｇ（０.0０７モル）、お
よびメタノール６６ｇを仕込み、５５℃で攪拌下、アセ
トン３５.1６ｇ（０.6１モル）を１時間かけて滴下し
た。滴下終了後６５℃で３時間反応させ、次に１４５ｇ
の水を加えて、５５℃でさらに３時間攪拌した。反応生
成物を濾別し、得られたウェットケーキを水洗後、乾燥
して、２，４，４−トリメチル−２−（２，４−ジヒド
ロキシフェニル）−７−ヒドロキシクロマンを得た。結
果は表１に示す。Example 1 A four-necked flask equipped with a stirrer, a cooler, a dropping funnel and a thermometer was charged with 200 g (1.82 mol) of resorcinol.
1.38 g (0.007 mol) of p-toluenesulfonic acid and 66 g of methanol were charged, and 35.16 g (0.61 mol) of acetone was added dropwise at 55 ° C. with stirring over 1 hour. After the completion of the dropwise addition, the mixture was reacted at 65 ° C. for 3 hours.
Was added, and the mixture was further stirred at 55 ° C. for 3 hours. The reaction product was separated by filtration, and the obtained wet cake was washed with water and dried to obtain 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman. The results are shown in Table 1.
【００１７】 実施例２ 実施例１におけるアセトンの量を４２.3ｇ（０.7３モ
ル）とした以外は、実施例１と同様にして、２，４，４
−トリメチル−２−（２，４−ジヒドロキシフェニル）
−７−ヒドロキシクロマンを得た。結果は表１に示す。Example 2 2,4,4 in the same manner as in Example 1 except that the amount of acetone in Example 1 was changed to 42.3 g (0.73 mol).
-Trimethyl-2- (2,4-dihydroxyphenyl)
-7-Hydroxychroman was obtained. The results are shown in Table 1.
【００１８】 比較例１ 攪拌器、冷却器、滴下ロートおよび温度計を装着した四
つ口フラスコに、 レゾルシン２００ｇ（１.8２モ
ル）、３６％塩酸９１.2ｇ（０.9モル）、および水３３
０ｇを仕込み、４２℃で攪拌下、アセトン３５.2ｇ
（０.6１モル）を１時間かけて滴下した。滴下終了後、
５０℃で３時間反応させた。次に反応生成物を濾別し、
得られたウェットケーキを水洗後、乾燥して、２，４，
４−トリメチル−２−（２，４−ジヒドロキシフェニ
ル）−７−ヒドロキシクロマンを得た。結果は表１に示
す。Comparative Example 1 In a four-necked flask equipped with a stirrer, a cooler, a dropping funnel and a thermometer, 200 g (1.82 mol) of resorcinol, 91.2 g (0.9 mol) of 36% hydrochloric acid, and water 33
0 g, 35.2 g of acetone was stirred at 42 ° C.
(0.61 mol) was added dropwise over 1 hour. After dropping,
The reaction was performed at 50 ° C. for 3 hours. Then the reaction product is filtered off,
After washing the obtained wet cake with water, and drying it,
4-Trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman was obtained. The results are shown in Table 1.
【００１９】 比較例２ 比較例１におけるアセトンの量を４２.3ｇ（０.7３モ
ル) とした以外は、比較例１と同様にして、２，４，４
−トリメチル−２−（２，４−ジヒドロキシフェニル）
−７−ヒドロキシクロマンを得た。結果は表１に示す。Comparative Example 2 In the same manner as in Comparative Example 1, except that the amount of acetone in Comparative Example 1 was 42.3 g (0.73 mol), 2, 4, and 4 were used.
-Trimethyl-2- (2,4-dihydroxyphenyl)
-7-Hydroxychroman was obtained. The results are shown in Table 1.
【００２０】 比較例３ 比較例１における３６％塩酸９１.2ｇ（０.9モル）をｐ
−トルエンスルホン酸１０ｇ（０.0５モル）に変えた以
外は、比較例１と同様にして、２，４，４−トリメチル
−２−（２，４−ジヒドロキシフェニル）−７−ヒドロ
キシクロマンを得た。結果は表１に示す。Comparative Example 3 91.2 g (0.9 mol) of 36% hydrochloric acid in Comparative Example 1 was added to p
-2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman was obtained in the same manner as in Comparative Example 1 except that toluene sulfonic acid was changed to 10 g (0.05 mol). Was. The results are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】1) 純度およびレゾルシン含量は、液体クロマトグラフィー（ＨＰＬＣ）絶対検 量線法で求めた。 装 置：（株）島津製作所製 LC-4A カラム：Sumipax ODS A-212 (5μm) 6 mmφ×150 mm 溶離液：Ａ液 0.5%ギ酸／水；Ｂ液 0.5%ギ酸／アセトニトリル Ｂ液濃度 10%→100%（3%／min.） 流 量：1.5 ml/min. 検出器：UV 280 nm 2) ポリマー含量は、ゲル浸透クロマトグラフィー（ＧＰＣ）面積百分率法で求 めた。 装 置：東ソー（株）製 HLC-8020 カラム：TSKgel G4000HXL＋G2000HXL 移動相：テトラヒドロフラン 40℃ 流 量：1 ml/min. 検出器：UV 254 nm 1) Purity and resorcin content were determined by liquid chromatography (HPLC) absolute calibration curve method. Apparatus: LC-4A made by Shimadzu Corporation Column: Sumipax ODS A-212 (5 μm) 6 mmφ × 150 mm Eluent: Solution A 0.5% formic acid / water; Solution B 0.5% formic acid / acetonitrile B solution concentration 10% → 100% (3% / min.) Flow rate: 1.5 ml / min. Detector: UV 280 nm 2) The polymer content was determined by gel permeation chromatography (GPC) area percentage method. Apparatus: HLC-8020 manufactured by Tosoh Corporation Column: TSKgel G4000H XL + G2000H XL Mobile phase: tetrahydrofuran 40 ° C Flow rate: 1 ml / min. Detector: UV 254 nm
【００２３】[0023]
【発明の効果】本発明の方法によれば、一般式（Ｉ）で
示されるオキシフラバン類を工業的有利に、高純度で製
造することができる。According to the method of the present invention, the oxyflavans represented by the general formula (I) can be industrially advantageously produced with high purity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 桑名 耕治 大阪府大阪市此花区春日出中３丁目１番 98号 住友化学工業株式会社内 (72)発明者 富岡 淳 大阪府大阪市此花区春日出中３丁目１番 98号 住友化学工業株式会社内 (56)参考文献 特開 昭59−157113（ＪＰ，Ａ) 特開 昭61−27980（ＪＰ，Ａ) 特開 平５−139375（ＪＰ，Ａ) 国際公開91／9346（ＷＯ，Ａ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 311/60 - 311/96 B01J 31/02 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Koji Kuwana 3-1-198 Kasuganaka, Konohana-ku, Osaka City, Osaka Prefecture Inside Sumitomo Chemical Co., Ltd. No. 3-98 No. 98, Sumitomo Chemical Co., Ltd. (56) References JP-A-59-157113 (JP, A) JP-A-61-27980 (JP, A) JP-A-5-139375 (JP, A) International Publication No. 91/9346 (WO, A1) (58) Fields investigated (Int. Cl. 7 , DB name) C07D 311/60-311/96 B01J 31/02 CA (STN)
Claims (1)
溶媒中で、ｐ−トルエンスルホン酸触媒の存在下に反応
させることを特徴とする、下記一般式（Ｉ） 【化１】 （式中、Ｒ1 、Ｒ2 およびＲ5 はそれぞれ独立に、アル
キル基、アルケニル基、シクロアルキル基、アラルキル
基もしくはアリール基を表し、Ｒ3 およびＲ4 はそれぞ
れ独立に、水素原子、アルキル基、アルケニル基、シク
ロアルキル基、アラルキル基もしくはアリール基を表す
か、またはＲ1 とＲ2 およびＲ4 とＲ5 がそれぞれ独立
に、環を形成する）で示されるオキシフラバン類の製造
法。1. A resorcinol and a ketone are reacted in a methanol reaction solvent in the presence of a p-toluenesulfonic acid catalyst, wherein the compound is represented by the following general formula (I): (Wherein, R 1 , R 2 and R 5 each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group Or an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group, or R 1 and R 2 and R 4 and R 5 each independently form a ring).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3186182A JP3000731B2 (en) | 1991-07-25 | 1991-07-25 | Process for producing oxyflavans |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3186182A JP3000731B2 (en) | 1991-07-25 | 1991-07-25 | Process for producing oxyflavans |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0532654A JPH0532654A (en) | 1993-02-09 |
| JP3000731B2 true JP3000731B2 (en) | 2000-01-17 |
Family
ID=16183828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3186182A Expired - Lifetime JP3000731B2 (en) | 1991-07-25 | 1991-07-25 | Process for producing oxyflavans |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3000731B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710510B2 (en) * | 1986-06-03 | 1995-02-08 | フアナツク株式会社 | Industrial robot arm structure |
| JP3528242B2 (en) | 1994-06-23 | 2004-05-17 | 住友化学工業株式会社 | Method for producing hydroxyflavan compound |
| US5726257A (en) * | 1994-08-30 | 1998-03-10 | Sumitomo Chemical Company, Ltd. | Esterified resorcinol-carbonyl compound condensates and epoxy resins therewith |
-
1991
- 1991-07-25 JP JP3186182A patent/JP3000731B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0532654A (en) | 1993-02-09 |
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