JP3575705B2 - Method for producing gingerol and shogaol - Google Patents
Method for producing gingerol and shogaol Download PDFInfo
- Publication number
- JP3575705B2 JP3575705B2 JP18157394A JP18157394A JP3575705B2 JP 3575705 B2 JP3575705 B2 JP 3575705B2 JP 18157394 A JP18157394 A JP 18157394A JP 18157394 A JP18157394 A JP 18157394A JP 3575705 B2 JP3575705 B2 JP 3575705B2
- Authority
- JP
- Japan
- Prior art keywords
- gingerol
- shogaol
- present
- base
- solution
- 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 - Fee Related
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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
【0001】
【産業上の利用分野】
本発明は、ジンゲロールおよびショーガオールの改良された製造法に関する。これらの化合物は香料組成物などとして有用である。
【0002】
【従来の技術およびその問題点】
ジンゲロールやショーガオールはショウガの辛味成分として存在するが、微量しか含有されていないため工業的には化学合成によって製造される。
従来、ジンゲロールの製造法としては、例えばデヒドロジンゲロン(V)にアルデヒドを作用させて得たアルドール化合物(VI)のアルケニル基を還元して得る方法が知られている(特開平2−250846)。
【0003】
【化6】
(R′は水素原子、炭素数1〜11のアルキル基またはフェニル基を示す)
【0004】
さらに、ショーガオールは、ジンゲロールを酸触媒存在下で脱水反応させることによって得られる(特開昭61−137834)。
しかし、上記の方法では縮合生成物であるアルドール化合物(VI)のアルケニル基の還元反応を行う必要が生ずる。水素ガスを用いる還元反応は通常、専用の耐圧装置が必要となるため一般の常圧反応装置では製造が困難であり満足できるものではない。
【0005】
また、上記とは別にジンゲロンのフェノール性水酸基をトリメチルシリル基で保護した化合物(VII)を得た後、アルデヒドと縮合反応させる方法も知られている(J.C.S. Perkin I 82 (1981))。
【化7】
しかし、高価で、微量の水分で不活性化しやすいハロゲン化トリメチルシリルを用いることと、保護、縮合、脱保護という多段階工程を考慮すると、工業的規模での製造法としては適当とはいえない。
【0006】
【課題を解決するための手段】
本発明者はかかる問題点を克服すべく鋭意検討した結果、本発明を完成したものである。
本発明によれば、式(III)
【化8】
(式中、nは0〜10の整数を示す)を有するジンゲロールは、式(I)
【化9】
で表わされるジンゲロンを塩基および不活性溶媒の存在下で式(II)
【化10】
(式中、nは前述したものと同じ意義を有する)で表わされるアルデヒドと反応させることによって製造される。
【0007】
さらに本発明によれば、前記ジンゲロール(III)を酸触媒および不活性溶媒の存在下で加熱することにより、式(IV)
【化11】
(式中nは前述したものと同じ意義を有する)で表わされるショーガオールが製造される。
【0008】
本発明のジンゲロール(III)の製造法で使用される塩基は特に制限はないが、ナトリウムt−ブトキシド、カリウムt−ブトキシドのようなアルカリ金属アルコラート、リチウムジイソプロピルアミド、リチウムジシクロヘキシルアミドなどの立体的に嵩高い強塩基が好ましい。
塩基性物質はジンゲロン(I)に対して2〜5当量、好ましくは3〜4当量用いられる。
アルデヒド(II)はジンゲロン(I)に対して1〜4当量、好ましくは2〜3当量用いられる。
【0009】
不活性溶媒は、例えばテトラヒドロフラン、ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、1,2−ジメトキシエタン、ジエチレングリコールジメチルエーテル、N,N′−ジメチルホルムアミド、N,N′−ジメチルアセトアミド、1,3−ジメチル−2−イミダゾリジノンなどの極性非プロトン溶媒が望ましく、これらの1種または2種以上が混合して用いられる。
反応は通常−100〜0℃、好ましくは−78〜−35℃で、5分間〜6時間行われる。所望の生成物は減圧蒸留もしくはシリカゲルクロマトグラフィーによって精製する。
【0010】
本発明においてショーガオール(IV)を製造する際に使用される酸触媒としては、p−トルエンスルホン酸、硫酸等が使用され、不活性溶媒としては、トルエン、キシレン等が使用される。反応は通常100〜150℃で1〜2時間実施される。
【0011】
【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限定されるものではない。
実施例1
ジンゲロン5gとn−ヘキサナール5.2gをテトラヒドロフラン50gに溶解し、この溶液をカリウムt−ブトキシド10.5gのテトラヒドロフラン(100g)溶液中に−78℃にて滴下した。そのまま5分間撹拌した後、反応溶液を水に加えた。エーテルを加え分液し、水層を得た後、1規定塩酸水溶液を加え酸性にした。次いで、エーテルを加え、飽和食塩水、飽和重曹水、飽和食塩水の順に洗浄した後、分液しエーテル層を得た。無水硫酸マグネシウムで乾燥後、減圧濃縮し粗油5.1gを得た。シリカゲルクロマトグラフィーで分離精製し、(6)−ジンゲロール3.6g(収率:48%)を得た。
【0012】
これをトルエン36gに溶解した後、p−トルエンスルホン酸0.05gを入れ加熱還流した。飽和重曹水、飽和食塩水で洗浄した後、分液して得られたトルエン溶液を減圧濃縮した。粗油をシリカゲルクロマトグラフィーで精製すると(6)−ショーガオール3.1g(収率:90%)が得られた。
【0013】
実施例2
ナトリウムt−ブトキシド5gをジエチレングリコールジメチルエーテル40gに溶かし、−60℃に冷却した。これにジンゲロン2gとn−オクタナール3.2gのジエチレングリコールジメチルエーテル(20g)溶液を滴下した。1時間撹拌した後、反応溶液を水に入れた。塩酸を入れた後、エーテルを加え抽出し有機層を得た。飽和重曹水、次いで飽和食塩水で乾燥した後、シリカゲルクロマトグラフィーで精製し、(8)−ジンゲロール1.3g(収率:39%)を得た。
【0014】
これをトルエン13gに溶解した後、p−トルエンスルホン酸0.03gを入れ加熱還流した。飽和重曹水、飽和食塩水で洗浄した後、分液して得られたトルエン溶液を減圧濃縮した。粗油をシリカゲルクロマトグラフィーで精製すると(8)−ショーガオール1.1g(収率:90%)が得られた。
【0015】
【発明の効果】
本発明の製造法によれば、フェノール性水酸基を保護することなくジンゲロン(I)をアルデヒド(II)の末端の炭素に選択的に縮合させてジンゲロールを製造することができる。かくして得られたジンゲロールを酸触媒の存在下で脱水処理することによりショーガオールが収率よく得られる。
【0016】
本発明の製造法により得られたジンゲロールおよびショーガオールはショウガ特有の辛味感を有しており、ショウガなどの食品だけでなく、化粧品、トイレタリー製品に添加する香料組成物として有用である。さらに、皮膚外用剤、解熱剤、鎮痛剤、鎮咳剤、抗酸化剤などの種々の薬剤に使用することができる。[0001]
[Industrial applications]
The present invention relates to an improved method for producing gingerol and shogaol. These compounds are useful as perfume compositions and the like.
[0002]
[Prior art and its problems]
Gingerol and shogaol are present as pungent components of ginger, but are industrially produced by chemical synthesis because they contain only trace amounts.
Conventionally, as a method for producing gingerol, for example, a method is known in which an aldehyde is allowed to act on dehydrogingerone (V) to reduce the alkenyl group of an aldol compound (VI) (JP-A-2-250846).
[0003]
Embedded image
(R ′ represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms or a phenyl group)
[0004]
Further, shogaol can be obtained by subjecting gingerol to a dehydration reaction in the presence of an acid catalyst (JP-A-61-137834).
However, in the above method, it is necessary to carry out a reduction reaction of the alkenyl group of the aldol compound (VI), which is a condensation product. Since the reduction reaction using hydrogen gas usually requires a dedicated pressure-resistant device, it is difficult to produce with a general normal-pressure reactor and it is not satisfactory.
[0005]
In addition, a method is also known in which, apart from the above, a compound (VII) in which the phenolic hydroxyl group of gingerone is protected with a trimethylsilyl group is obtained, followed by a condensation reaction with an aldehyde ( JCS Perkin I 82 (1981)). ).
Embedded image
However, considering the use of trimethylsilyl halide, which is expensive and is easily deactivated by a very small amount of water, and considering the multi-step process of protection, condensation, and deprotection, it is not suitable as a production method on an industrial scale.
[0006]
[Means for Solving the Problems]
The inventor of the present invention has intensively studied to overcome such a problem, and as a result, has completed the present invention.
According to the present invention, formula (III)
Embedded image
(Wherein n is an integer of 0 to 10) has the formula (I)
Embedded image
(II) in the presence of a base and an inert solvent
Embedded image
(Wherein n has the same meaning as described above).
[0007]
Furthermore, according to the present invention, the above-mentioned gingerol (III) is heated in the presence of an acid catalyst and an inert solvent to obtain a compound of the formula (IV)
Embedded image
(Where n has the same meaning as described above) is produced.
[0008]
The base used in the method for producing gingerol (III) of the present invention is not particularly limited, but may be sterically selected from alkali metal alcoholates such as sodium t-butoxide and potassium t-butoxide, lithium diisopropylamide, and lithium dicyclohexylamide. A bulky strong base is preferred.
The basic substance is used in an amount of 2 to 5 equivalents, preferably 3 to 4 equivalents, based on zingerone (I).
Aldehyde (II) is used in an amount of 1 to 4 equivalents, preferably 2 to 3 equivalents, based on zingerone (I).
[0009]
Inert solvents include, for example, tetrahydrofuran, diethyl ether, diisopropyl ether, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, N, N'-dimethylformamide, N, N'-dimethylacetamide, 1,3-dimethyl-2- A polar aprotic solvent such as imidazolidinone is desirable, and one or more of these are used in combination.
The reaction is carried out usually at -100 to 0C, preferably at -78 to -35C, for 5 minutes to 6 hours. The desired product is purified by vacuum distillation or silica gel chromatography.
[0010]
In the present invention, p-toluenesulfonic acid, sulfuric acid, or the like is used as an acid catalyst used for producing shogaol (IV), and toluene, xylene, or the like is used as an inert solvent. The reaction is usually carried out at 100 to 150 ° C for 1 to 2 hours.
[0011]
【Example】
Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Example 1
5 g of gingerone and 5.2 g of n-hexanal were dissolved in 50 g of tetrahydrofuran, and this solution was added dropwise to a solution of 10.5 g of potassium t-butoxide in 100 g of tetrahydrofuran at -78 ° C. After stirring for 5 minutes as it was, the reaction solution was added to water. Ether was added and the mixture was separated to give an aqueous layer. After that, a 1N aqueous hydrochloric acid solution was added to make the mixture acidic. Next, ether was added, and the mixture was washed with saturated saline, saturated aqueous sodium bicarbonate, and saturated saline in this order, and then separated to obtain an ether layer. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure to obtain 5.1 g of a crude oil. Separation and purification were performed by silica gel chromatography to obtain 3.6 g of (6) -gingerol (yield: 48%).
[0012]
After dissolving this in 36 g of toluene, 0.05 g of p-toluenesulfonic acid was added and heated under reflux. After washing with a saturated aqueous solution of sodium bicarbonate and a saturated saline solution, the toluene solution obtained by liquid separation was concentrated under reduced pressure. The crude oil was purified by silica gel chromatography to obtain 3.1 g (yield: 90%) of (6) -shogaol.
[0013]
Example 2
5 g of sodium t-butoxide was dissolved in 40 g of diethylene glycol dimethyl ether and cooled to -60 ° C. A solution of 2 g of zingerone and 3.2 g of n-octanal in diethylene glycol dimethyl ether (20 g) was added dropwise thereto. After stirring for 1 hour, the reaction solution was poured into water. After adding hydrochloric acid, ether was added and extracted to obtain an organic layer. After drying with saturated aqueous sodium hydrogen carbonate and then with saturated saline, purification was performed by silica gel chromatography to obtain 1.3 g of (8) -gingerol (yield: 39%).
[0014]
After dissolving this in 13 g of toluene, 0.03 g of p-toluenesulfonic acid was added and heated under reflux. After washing with a saturated aqueous solution of sodium bicarbonate and a saturated saline solution, the toluene solution obtained by liquid separation was concentrated under reduced pressure. The crude oil was purified by silica gel chromatography to obtain 1.1 g of (8) -shogaol (yield: 90%).
[0015]
【The invention's effect】
According to the production method of the present invention, gingerol can be produced by selectively condensing gingerone (I) to the terminal carbon of aldehyde (II) without protecting the phenolic hydroxyl group. By dehydrating the thus obtained gingerol in the presence of an acid catalyst, shogaol can be obtained in good yield.
[0016]
The gingerol and shogaol obtained by the production method of the present invention have a pungency peculiar to ginger, and are useful as a fragrance composition to be added to not only food such as ginger but also cosmetics and toiletry products. Further, it can be used for various agents such as skin external preparations, antipyretics, analgesics, antitussives, antioxidants and the like.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18157394A JP3575705B2 (en) | 1994-08-02 | 1994-08-02 | Method for producing gingerol and shogaol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18157394A JP3575705B2 (en) | 1994-08-02 | 1994-08-02 | Method for producing gingerol and shogaol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0840970A JPH0840970A (en) | 1996-02-13 |
JP3575705B2 true JP3575705B2 (en) | 2004-10-13 |
Family
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Application Number | Title | Priority Date | Filing Date |
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JP18157394A Expired - Fee Related JP3575705B2 (en) | 1994-08-02 | 1994-08-02 | Method for producing gingerol and shogaol |
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JP (1) | JP3575705B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10159268B2 (en) | 2013-02-08 | 2018-12-25 | General Mills, Inc. | Reduced sodium food products |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU758911B2 (en) * | 1997-10-21 | 2003-04-03 | Zingotx Pty Ltd | Medicinal uses of phenylalkanols and derivatives |
US6518315B1 (en) | 1997-10-21 | 2003-02-11 | The University Of Sydney | Medicinal uses of phenylaikanols and derivatives |
AUPO990097A0 (en) * | 1997-10-21 | 1997-11-13 | University Of Sydney, The | Medicinal uses of phenylalkanols and derivatives (gingerol analogues) |
US6887898B1 (en) | 1999-10-22 | 2005-05-03 | Darrick S. H. L. Kim | Pharmaceutical compositions useful in prevention and treatment of beta-Amyloid protein-induced disease |
US7728043B2 (en) | 1999-10-22 | 2010-06-01 | Kim Darrick S H L | Methods for treatment of beta-amyloid protein-induced ocular disease |
JP4819635B2 (en) * | 2006-09-28 | 2011-11-24 | 株式会社バスクリン | Method for producing processed ginger with high content of shogaol |
FR2950884B1 (en) * | 2009-10-01 | 2011-11-11 | Oreal | USE OF VANILLIN DERIVATIVES AS A PRESERVATIVE, METHOD OF PRESERVATION, COMPOUNDS AND COMPOSITION |
JP5829225B2 (en) * | 2013-02-07 | 2015-12-09 | 長谷川香料株式会社 | Method for producing ginger extract with high gingerol content |
-
1994
- 1994-08-02 JP JP18157394A patent/JP3575705B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10159268B2 (en) | 2013-02-08 | 2018-12-25 | General Mills, Inc. | Reduced sodium food products |
US11540539B2 (en) | 2013-02-08 | 2023-01-03 | General Mills, Inc. | Reduced sodium food products |
Also Published As
Publication number | Publication date |
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JPH0840970A (en) | 1996-02-13 |
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