JPH11228496A - Production of polyene derivative - Google Patents
Production of polyene derivativeInfo
- Publication number
- JPH11228496A JPH11228496A JP10026077A JP2607798A JPH11228496A JP H11228496 A JPH11228496 A JP H11228496A JP 10026077 A JP10026077 A JP 10026077A JP 2607798 A JP2607798 A JP 2607798A JP H11228496 A JPH11228496 A JP H11228496A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- polyene
- derivative
- group
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、医薬中間体として
重要なポリエン誘導体の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing a polyene derivative which is important as a pharmaceutical intermediate.
【０００２】[0002]
【従来の技術】従来、下記一般式（２）で示されるポリ
エン誘導体の製造法としてはＣ１３のアルデヒド（β―
ヨノン）を鍵中間体として、側鎖を増炭する手法が用い
られてきた。しかし選択的にポリエン誘導体（２）を製
造する方法は知られていない。また、β―ヨノンの合成
には多段階のプロセスを経ており、市場では非常に高価
な原料である。2. Description of the Related Art Conventionally, as a method for producing a polyene derivative represented by the following general formula (2), a C13 aldehyde (β-
Yonone) has been used as a key intermediate to increase the carbon content of the side chain. However, a method for selectively producing the polyene derivative (2) is not known. Further, the synthesis of β-yonone is a multi-step process, and is a very expensive raw material on the market.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、β―ヨノン
を経由せず安価な原料を用いてＣ１０とＣ１０のカップ
リングからなる中間体を経てポリエン誘導体（２）の選
択的かつ工業的有利な製造法を提供しようとするもので
ある。DISCLOSURE OF THE INVENTION The present invention provides a selective and industrially advantageous polyene derivative (2) via an intermediate consisting of C10 to C10 coupling using an inexpensive raw material without passing through β-yonone. It is intended to provide a simple manufacturing method.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果本発明に至った。す
なわち、本発明は一般式（１） （式中、Ｒは水酸基の保護基を示す。）で示されるポリ
エンアルコール誘導体を脱水反応に供することを特徴と
する一般式（２） （式中、Ｒは水酸基の保護基を示す。）で示されるポリ
エン誘導体の工業的有利な製造法を提供するものであ
る。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to general formula (1) Wherein R represents a hydroxyl-protecting group. The polyene alcohol derivative represented by the general formula (2) is subjected to a dehydration reaction. (Wherein, R represents a protecting group for a hydroxyl group).
【０００５】[0005]
【発明の実施の形態】以下、本発明について詳細に説明
する。一般式（１）または（２）で示される化合物にお
いて、水酸基の保護基としてはアセチル、ピバロイル、
ベンゾイル、ｐ−ニトロベンゾイルなどのアシル基、ト
リメチルシリル、ｔ―ブチルジメチルシリル、ｔ−ブチ
ルジフェニルシリルなどのシリル基、テトラヒドロピラ
ニル、メトキシメチル、メトキシエトキシメチル、１−
エトキシエチルなどのアルコキシメチル基、ベンジル
基、ｐ−メトキシベンジル基、ｔ−ブチル基、トリチル
基、メチル基、トリクロロエトキシカルボニル基、アリ
ルオキシカルボニル基等が挙げられ、アセチル基が好ま
しく用いられる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (1) or (2), acetyl, pivaloyl,
Acyl groups such as benzoyl and p-nitrobenzoyl; silyl groups such as trimethylsilyl, t-butyldimethylsilyl and t-butyldiphenylsilyl; tetrahydropyranyl, methoxymethyl, methoxyethoxymethyl, 1-
Examples thereof include an alkoxymethyl group such as ethoxyethyl, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a trityl group, a methyl group, a trichloroethoxycarbonyl group, an allyloxycarbonyl group, and an acetyl group is preferably used.
【０００６】上記脱水反応としては、酸触媒反応、チュ
ガエフ（ Chugaev）反応、ブルゲス（Burgess）反応等
が挙げられる。The dehydration reaction includes an acid catalyzed reaction, a Chugaev reaction, a Burgess reaction and the like.
【０００７】まず、酸触媒反応について説明する。酸触
媒としては、イオン交換樹脂、ヘテロポリ酸、 ルイス
酸、プロトン酸、アルカリ金属の硫酸水素塩、酸塩化物
等が挙げられる。具体的にはイオン交換樹脂としては末
端にスルホン酸基を有する強酸性タイプのものが好まし
い。ルイス酸としては、四塩化チタン、塩化亜鉛、三弗
化ホウ素エーテル錯体、希土類のトリフレート等、プロ
トン酸としては、臭化水素酸、塩酸、硫酸、無水トリフ
ルオロメタンスルホン酸等のスルホン酸類、安息香酸
等、酸塩化物としては塩化チオニル、オキシ塩化燐等が
挙げられる。酸触媒の使用量はポリエンアルコール誘導
体（１）に対して、0.01〜２モル倍もしくは0.01〜２重
量倍が好ましく用いられる。First, the acid catalyzed reaction will be described. Examples of the acid catalyst include an ion exchange resin, a heteropoly acid, a Lewis acid, a proton acid, an alkali metal hydrogen sulfate, and an acid chloride. Specifically, as the ion exchange resin, a strongly acidic type having a sulfonic acid group at a terminal is preferable. Examples of the Lewis acid include titanium tetrachloride, zinc chloride, boron trifluoride ether complex, and rare earth triflate. Examples of the protic acid include sulfonic acids such as hydrobromic acid, hydrochloric acid, sulfuric acid, and trifluoromethanesulfonic anhydride, and benzoic acid. Acids and acid chlorides include thionyl chloride, phosphorus oxychloride and the like. The amount of the acid catalyst to be used is preferably 0.01 to 2 times by mole or 0.01 to 2 times by weight based on the polyene alcohol derivative (1).
【０００８】酸触媒反応には、通常、有機溶媒単一もし
くは水との混合溶媒が用いられ、かかる有機溶媒として
は、 ｎ−ヘキサン、シクロヘキサン、n−ペンタン、ト
ルエン、キシレン等の炭化水素系溶媒、ジエチルエーテ
ル、テトラヒドロフラン、アニソール等のエーテル系溶
媒、 クロロホルム、ジクロロメタン、1,2-ジクロロエ
タン、モノクロロベンゼン、ｏ−ジクロロベンゼン等の
ハロゲン系溶媒、またはＮ，Ｎ−ジメチルホルムアミ
ド、ジメチルスルホキシド、Ｎ、Ｎ−ジメチルアセトア
ミド、ヘキサメチルホスホリックトリアミド等の非プロ
トン性極性溶媒が挙げられる。In the acid catalyzed reaction, a single organic solvent or a mixed solvent with water is usually used, and examples of such organic solvents include hydrocarbon solvents such as n-hexane, cyclohexane, n-pentane, toluene and xylene. , Diethyl ether, tetrahydrofuran, anisole and other ether solvents; chloroform, dichloromethane, 1,2-dichloroethane, monochlorobenzene, o-dichlorobenzene and other halogen solvents, or N, N-dimethylformamide, dimethyl sulfoxide, N, N -Aprotic polar solvents such as dimethylacetamide and hexamethylphosphoric triamide.
【０００９】反応温度は、通常、−78℃から使用する溶
媒の沸点の範囲であり、好ましくは−３０℃〜５０℃の
範囲である。また、反応時間は、反応で用いる触媒の種
類ならびに反応温度によって異なるが、通常１時間から
２４時間程度の範囲である。反応後、通常の後処理操作
をすることによりポリエン誘導体（２）を得ることがで
きる。The reaction temperature is generally in the range of -78 ° C to the boiling point of the solvent used, preferably in the range of -30 ° C to 50 ° C. The reaction time varies depending on the type of catalyst used in the reaction and the reaction temperature, but is usually in the range of about 1 to 24 hours. After the reaction, the polyene derivative (2) can be obtained by performing ordinary post-treatment operations.
【００１０】必要に応じて、シリカゲルクロマトグラフ
ィーなどにより精製することができる。また原料のポリ
エンアルコール誘導体（１）はＥまたはＺ幾何異性体の
いずれであっても、またその混合物であってもよい。ま
た、ラセミ体でも光学活性体であってもよい。なお、原
料のポリエン誘導体はゲラニオールより数ステップで合
成することができる。[0010] If necessary, it can be purified by silica gel chromatography or the like. The raw material polyene alcohol derivative (1) may be either E or Z geometric isomer or a mixture thereof. Further, it may be a racemic body or an optically active body. The raw material polyene derivative can be synthesized from geraniol in several steps.
【００１１】チュガエフ反応を用いる場合にはTetrahed
ron Letters ,28 , 2795,(1987)に記載の方法に準じて
脱水反応を実施すればよい。チュガエフ反応は、例え
ば、ポリエンアルコール誘導体（１）に水素化ナトリウ
ム等の塩基（約１〜２モル倍）、二硫化炭素（約１〜５
モル倍）を加え、さらにアルキルハライドを添加し、通
常、０〜５０℃で加熱した後、得られたキサンテートを
通常、１００〜２５０℃で１〜１０時間加熱することに
より実施することができる。When the Chugaev reaction is used, Tetrahed
The dehydration reaction may be performed according to the method described in Ron Letters, 28, 2795, (1987). The Chugaev reaction is carried out, for example, by adding a base such as sodium hydride (about 1 to 2 times by mole) to a polyene alcohol derivative (1) and carbon disulfide (about 1 to 5 times).
Mol times), further adding an alkyl halide, and generally heating at 0 to 50 ° C, and then heating the obtained xanthate at 100 to 250 ° C for 1 to 10 hours.
【００１２】ブルゲス反応を用いる場合にはTetrahedro
n, 23 , 4677,(1992)に記載の方法に準じて脱水反応を
実施すればよい。ブルゲス反応は、例えば、ポリエンア
ルコール誘導体（１）に水素化ナトリウム等の塩基（約
１〜２モル倍）を加え、通常、１０〜７０℃で、ブルゲ
ス試薬（ＣＨ3Ｏ2ＣＮＳＯ2Ｎ（Ｃ2Ｈ5））を通常、１〜
２モル倍加え同温で３〜２４時間反応させることにより
実施することができる。When the Burgess reaction is used, Tetrahedro
The dehydration reaction may be carried out according to the method described in n, 23, 4677, (1992). In the Burgess reaction, for example, a base such as sodium hydride (about 1 to 2 times by mole) is added to the polyene alcohol derivative (1), and the Burgess reagent (CH 3 O 2 CNSO 2 N (C 2 H 5 )) is usually 1 to
The reaction can be carried out by adding 2 mole times and reacting at the same temperature for 3 to 24 hours.
【００１３】[0013]
【発明の効果】本発明によれば、安価な原料を用いてポ
リエン誘導体（２）を工業的有利に製造することができ
る。According to the present invention, the polyene derivative (2) can be produced industrially advantageously using inexpensive raw materials.
【００１４】[0014]
【実施例】以下、実施例により、本発明をさらに詳細に
説明するが、本発明はこれらにより限定されるものでは
ない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００１５】（実施例１）乾燥したフラスコに窒素雰囲
気下、１−アセトキシ−５−ヒドロキシ−３，７ジメチ
ル−９−（２，６，６−トリメチルシクロヘキセン−１
−イル）−ノナ２，６，８−トリエン（以下、化合物
（ａ）） 70 mg（0.202mmol）とＴＨＦ3mlを仕込み、攪
拌下、無水トリフルオロメタンスルホン酸23mg(0.202mm
ol)を仕込み、室温で１２時間攪拌した。TLCにて原料が
消失したのを確認して反応液を5%の炭酸水素ナトリウム
水溶液に注加し、エーテルにて抽出した。有機層は飽和
食塩水で洗浄し、無水硫酸マグネシウムにて脱水後、溶
媒を留去することにより粗製物を得た。得られた粗製物
は、シリカゲルカラムクロマトグラフィーで精製し、１
−アセトキシ−３，７−ジメチル−９−（２，６，６−
トリメチルシクロヘキセン−２−イル）−ノナ−２，
５，７，９−テトラエン（以下、化合物（ｂ））を収率
85.1％で得た。(Example 1) 1-acetoxy-5-hydroxy-3,7dimethyl-9- (2,6,6-trimethylcyclohexene-1) was placed in a dried flask under a nitrogen atmosphere.
-Yl) -nona 2,6,8-triene (hereinafter referred to as compound (a)) 70 mg (0.202 mmol) and THF 3 ml were charged, and trifluoromethanesulfonic anhydride 23 mg (0.202 mm
ol) and stirred at room temperature for 12 hours. After confirming the disappearance of the starting materials by TLC, the reaction solution was poured into a 5% aqueous sodium hydrogen carbonate solution, and extracted with ether. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The obtained crude product was purified by silica gel column chromatography,
-Acetoxy-3,7-dimethyl-9- (2,6,6-
Trimethylcyclohexen-2-yl) -nona-2,
5,7,9-Tetraene (hereinafter, compound (b)) in yield
Obtained at 85.1%.
【００１６】（実施例２）実施例１の無水トリフルオロ
メタンスルホン酸を三弗化ホウ素エーテル錯体に替え同
様に室温で３時間反応させ同様の後処理・精製をするこ
とにより、化合物（ｂ）と１−アセトキシ−３，７−ジ
メチル−９−（２，６，６−トリメチルシクロヘキセン
−１−イル）−ノナ−２，４，６，８−テトラエン（以
下、化合物（ｃ））との５：１の混合物を収率80.6％で
得た。(Example 2) The compound (b) was reacted with the compound (b) by subjecting the trifluoromethanesulfonic anhydride of Example 1 to a boron trifluoride etherate complex and reacting at room temperature for 3 hours to carry out the same post-treatment and purification. 1-acetoxy-3,7-dimethyl-9- (2,6,6-trimethylcyclohexen-1-yl) -nona-2,4,6,8-tetraene (hereinafter referred to as compound (c)) 1 was obtained in a yield of 80.6%.
【００１７】（実施例3）Chugaev反応 乾燥した４つ口フラスコに窒素雰囲気下、THF１０ｍｌ
と６０％水素化ナトリウム0.04g(0.96mmol)を仕込み、
０℃に冷却した。冷却後、化合物（ａ）0.3g(0.87mmol)
を二硫化炭素1.5mlに溶解した液をゆっくりと滴下し
た。滴下後還流下、３０分間攪拌して室温に冷却する。
その後、よう化メチル0.15g(1.04mmol)を滴下し、滴下
後３０分間還流下攪拌した。反応液は氷水にあけエーテ
ルで抽出し、飽和塩化アンモニウム水溶液で洗浄し、無
水硫酸マゲネシウムで乾燥後、溶媒を留去することによ
り粗製物を得た。得られた粗製物はシリカゲルカラムク
ロマトグラフィーにて精製し、Xanthateを得、さらにこ
の精製物をフラスコに仕込みDMF５ｍｌに溶解し、１５
０℃で６時間加熱した。原料の消失をTLCにて確認し、
冷却後炭酸水素ナトリウム水溶液に注加し、エーテルで
抽出した。さらに有機層は飽和食塩水にて洗浄し、無水
硫酸マグネシウムで脱水後、溶媒を留去することにより
粗製物を得た。得られた粗製物はシリカゲルカラムクロ
マトグラフィーにて精製し、化合物（ｂ）を収率79.1%
で得た。(Example 3) Chugaev reaction In a dry four-necked flask, 10 ml of THF was placed under a nitrogen atmosphere.
And 0.04 g (0.96 mmol) of 60% sodium hydride
Cooled to 0 ° C. After cooling, 0.3 g (0.87 mmol) of compound (a)
Was dissolved slowly in 1.5 ml of carbon disulfide. After the dropwise addition, the mixture is stirred for 30 minutes under reflux and cooled to room temperature.
Thereafter, 0.15 g (1.04 mmol) of methyl iodide was added dropwise, and the mixture was stirred under reflux for 30 minutes after the addition. The reaction solution was poured into ice water, extracted with ether, washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain Xanthate. This purified product was further charged in a flask and dissolved in 5 ml of DMF.
Heat at 0 ° C. for 6 hours. Confirm the disappearance of raw materials by TLC,
After cooling, the mixture was poured into an aqueous sodium hydrogen carbonate solution and extracted with ether. Further, the organic layer was washed with saturated saline, dehydrated with anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to give compound (b) in a yield of 79.1%.
I got it.
【００１８】（実施例４）Burgess反応 乾燥した４つ口フラスコに窒素雰囲気下、THF６ｍｌと
６０％水素化ナトリウム0.０２g(0.38mmol)を仕込み、
その後化合物（ａ）0.13g(0.38mmol)を滴下した。室温
で１時間攪拌後Burgess試薬0.10g(0.42mmol)を仕込み、
室温で１２時間攪拌後さらに５０℃で１時間加熱した。
原料の消失はTLCにて確認して反応液は水に注加し、エ
ーテルで抽出した。さらに有機層は飽和食塩水にて洗浄
し、無水硫酸マグネシウムで脱水後、溶媒を留去するこ
とにより粗製物を得た。得られた粗製物はシリカゲルカ
ラムクロマトグラフィーにて精製し、化合物（ｂ）を収
率30.5%で得た。Example 4 Burgess Reaction A dry four-necked flask was charged with 6 ml of THF and 0.02 g (0.38 mmol) of 60% sodium hydride in a nitrogen atmosphere.
Thereafter, 0.13 g (0.38 mmol) of the compound (a) was added dropwise. After stirring at room temperature for 1 hour, 0.10 g (0.42 mmol) of Burgess reagent was charged,
After stirring at room temperature for 12 hours, the mixture was further heated at 50 ° C. for 1 hour.
The disappearance of the raw materials was confirmed by TLC, and the reaction solution was poured into water and extracted with ether. Further, the organic layer was washed with saturated saline, dehydrated with anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain compound (b) at a yield of 30.5%.
【００１９】その他の実施例を以下の表に示す。すべて
実施例１に記載の方法に準じた。Other examples are shown in the following table. All methods were according to the method described in Example 1.
【表１】 [Table 1]
【００２０】註） IER：強酸性イオン交換樹脂 Duolite CC-265H Ｎａｆｉｏｎ−Ｈ：イオン交換樹脂（市販品） ＰＷ６Ｍｏ６：ヘテロポリ酸（市販品） Ｔｆ：トリフルオロメチルスルホニルNote) IER: Strongly acidic ion exchange resin Duolite CC-265H Nafion-H: Ion exchange resin (commercially available) PW6Mo6: Heteropolyacid (commercially available) Tf: trifluoromethylsulfonyl
【００２１】上記の化合物（ｂ）および（ｃ）は既知化
合物であるので文献値および標品のNMRデータとの比較
により構造決定した。以下に実施例で用いた化合物の構
造式を示す。 Since the above compounds (b) and (c) are known compounds, their structures were determined by comparison with literature values and NMR data of a standard. The structural formulas of the compounds used in the examples are shown below.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 31/22 Ｂ０１Ｊ 31/22 Ｘ Ｃ０７Ｃ 67/297 Ｃ０７Ｃ 67/297 403/12 403/12 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 6 Identification code FI B01J 31/22 B01J 31/22 X C07C 67/297 C07C 67/297 403/12 403/12 // C07B 61/00 300 C07B 61/00 300
Claims (4)
エンアルコール誘導体を脱水反応に供することを特徴と
する一般式（２） （式中、Ｒは水酸基の保護基を示す。）で示されるポリ
エン誘導体の製造法。1. The general formula (1) Wherein R represents a hydroxyl-protecting group. The polyene alcohol derivative represented by the general formula (2) is subjected to a dehydration reaction. (Wherein, R represents a hydroxyl-protecting group).
１に記載の製造法。2. The method according to claim 1, wherein the protecting group for the hydroxyl group is an acetyl group.
aev）反応またはブルゲス（Burgess）反応である請求項
１に記載の製造法。3. The dehydration reaction is an acid-catalyzed reaction, Chugaev
2. The process according to claim 1, wherein the process is aev) or Burgess reaction.
テロポリ酸、 ルイス酸、プロトン酸、酸無水物、アル
カリ金属の硫酸水素塩または酸塩化物である請求項３に
記載の製造法。4. The process according to claim 3, wherein the acid catalyst in the acid-catalyzed reaction is an ion exchange resin, a heteropoly acid, a Lewis acid, a protonic acid, an acid anhydride, an alkali metal hydrogen sulfate or an acid chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10026077A JPH11228496A (en) | 1998-02-06 | 1998-02-06 | Production of polyene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10026077A JPH11228496A (en) | 1998-02-06 | 1998-02-06 | Production of polyene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11228496A true JPH11228496A (en) | 1999-08-24 |
Family
ID=12183591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10026077A Withdrawn JPH11228496A (en) | 1998-02-06 | 1998-02-06 | Production of polyene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11228496A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184407A (en) * | 2007-01-29 | 2008-08-14 | Tsumura & Co | Method for producing (z)-ligustilide |
-
1998
- 1998-02-06 JP JP10026077A patent/JPH11228496A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184407A (en) * | 2007-01-29 | 2008-08-14 | Tsumura & Co | Method for producing (z)-ligustilide |
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| A761 | Written withdrawal of application |
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