JPH04283541A - Production of pentadienal derivative - Google Patents
Production of pentadienal derivativeInfo
- Publication number
- JPH04283541A JPH04283541A JP3074596A JP7459691A JPH04283541A JP H04283541 A JPH04283541 A JP H04283541A JP 3074596 A JP3074596 A JP 3074596A JP 7459691 A JP7459691 A JP 7459691A JP H04283541 A JPH04283541 A JP H04283541A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- pentadienal
- methyl
- glucofuranurono
- derivative
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- PPXGQLMPUIVFRE-UHFFFAOYSA-N penta-2,4-dienal Chemical class C=CC=CC=O PPXGQLMPUIVFRE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 150000007514 bases Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VLGCEXZSQMHPDM-RFFZZTLGSA-N [(3R,3aS,6S,6aS)-6-acetyloxy-2-methoxy-5-oxo-3,3a,6,6a-tetrahydro-2H-furo[3,2-b]furan-3-yl] acetate Chemical compound C(C)(=O)O[C@H]1C(OC)O[C@H]2[C@@H]1OC([C@H]2OC(C)=O)=O VLGCEXZSQMHPDM-RFFZZTLGSA-N 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 21
- IJQPHZAJRLKOSH-UHFFFAOYSA-N (1-methoxy-5-oxopenta-1,3-dien-2-yl) acetate Chemical compound COC=C(OC(C)=O)C=CC=O IJQPHZAJRLKOSH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002304 perfume Substances 0.000 abstract description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OGLCQHRZUSEXNB-VGASXLIASA-N (3r,3ar,6s,6ar)-2,3,6-trihydroxy-3,3a,6,6a-tetrahydro-2h-furo[3,2-b]furan-5-one Chemical compound O[C@@H]1C(=O)O[C@@H]2[C@@H](O)C(O)O[C@@H]21 OGLCQHRZUSEXNB-VGASXLIASA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- JBXFFCVIQJCKLE-GRXFLCFDSA-N [(3r,3as,6s,6as)-2,6-diacetyloxy-5-oxo-3,3a,6,6a-tetrahydro-2h-furo[3,2-b]furan-3-yl] acetate Chemical compound CC(=O)OC([C@@H]1OC(C)=O)O[C@H]2[C@@H]1OC(=O)[C@H]2OC(C)=O JBXFFCVIQJCKLE-GRXFLCFDSA-N 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005858 glycosidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明に関わる化２で示されるペ
ンタジエナール誘導体は、香料や医薬品の中間体として
価値ある化合物である。[Industrial Field of Application] The pentadienal derivative represented by chemical formula 2 related to the present invention is a valuable compound as an intermediate for perfumes and pharmaceuticals.
【０００２】0002
【従来の技術】当該化合物の製造法に関しては、Ｄ−グ
ルコフラヌロノ−６，３−ラクトントリアセテートをア
ルコールと塩基共存下で反応させる方法に関して既に特
許を出願している。BACKGROUND OF THE INVENTION Regarding a method for producing this compound, a patent has already been filed for a method in which D-glucofuranurono-6,3-lactone triacetate is reacted with an alcohol in the presence of a base.
【０００３】0003
【発明が解決しようとする課題】解決しようとする問題
点は、当該化合物のより簡便な製造法の開発にある。The problem to be solved lies in the development of a simpler method for producing the compound.
【０００４】0004
【発明が解決しようとする手段】本発明は、化１で示さ
れる１−Ｏ−メチル−Ｄ−グルコフラヌロノ−６，３−
ラクトンジアセテートの塩基化合物共存下での反応を検
討したところ、簡便な操作で化２で示される４−アセト
キシ−５−メトキシペンタジエナールが得られることを
見いだし、本発明を完成するに至った。Means to be Solved by the Invention The present invention provides 1-O-methyl-D-glucofuranurono-6,3-
After studying the reaction of lactone diacetate in the presence of a basic compound, the inventors discovered that 4-acetoxy-5-methoxypentadienal represented by the formula 2 can be obtained by a simple operation, and the present invention was completed. .
【０００５】すなわち、本発明の要旨は、化１で示され
る１−Ｏ−メチル−Ｄ−グルコフラヌロノ−６，３−ラ
クトンジアセテートを有機溶媒中塩基化合物の共存下で
反応させることを特徴とする化２で示されるペンタジエ
ナール誘導体の製造方法である。That is, the gist of the present invention is characterized in that 1-O-methyl-D-glucofuranurono-6,3-lactone diacetate represented by Chemical Formula 1 is reacted in the presence of a basic compound in an organic solvent. This is a method for producing a pentadienal derivative represented by Chemical Formula 2.
【０００６】かかる反応は、本発明者によって初めて明
らかにされた新規な反応である。[0006] Such a reaction is a novel reaction revealed for the first time by the present inventor.
【０００７】この反応において、原料として用いられる
化１で示される１−Ｏ−メチル−Ｄ−グルコフラヌロノ
−６，３−ラクトンジアセテートは、市販されているＤ
−グルコフラヌロノ−６，３−ラクトンを、メタノール
中酸触媒共存下等の通常のグリコシド化反応条件下で反
応させて１位をメチル化した後、無水酢酸−ピリジン系
等の通常のアセチル化条件下で反応させることによって
容易に合成することが出来る。In this reaction, 1-O-methyl-D-glucofuranurono-6,3-lactone diacetate shown by formula 1 used as a raw material is commercially available D
- Glucofuranurono-6,3-lactone is reacted under normal glycosidation reaction conditions such as in the presence of an acid catalyst in methanol to methylate the 1-position, and then under normal acetylation conditions such as an acetic anhydride-pyridine system. It can be easily synthesized by reacting with
【０００８】化１で示される１−Ｏ−メチル−Ｄ−グル
コフラヌロノ−６，３−ラクトンジアセテートの塩基化
合物共存下での反応は、有機溶媒中で実施される。The reaction of 1-O-methyl-D-glucofuranurono-6,3-lactone diacetate represented by Formula 1 in the presence of a basic compound is carried out in an organic solvent.
【０００９】有機溶媒としては、通常使用される有機溶
媒を用いることが出来るが、反応の基質である化１で示
される１−Ｏ−メチル−Ｄ−グルコフラヌロノ−６，３
−ラクトンジアセテートの溶解度が高い、クロロホルム
、アセトン、アセトニトリル、またはジクロロメタンを
用いることが望ましい。As the organic solvent, commonly used organic solvents can be used, but 1-O-methyl-D-glucofuranurono-6,3 shown in formula 1, which is the substrate for the reaction, can be used.
- It is desirable to use chloroform, acetone, acetonitrile or dichloromethane, in which the lactone diacetate has a high solubility.
【００１０】塩基化合物としては、１，８−ジアザビシ
クロ［５．４．０］−ウンデカ−７−エン（ＤＢＵ）、
トリエチルアミン、Ｎ−メチルピロリジン、Ｎ，Ｎ−ジ
メチルベンジルアミン、Ｎ，Ｎ−ジエチルアニリン、ト
リ−ｎ−ブチルアミン等の通常の有機塩基化合物が例示
されるが、特にトリエチルアミンが望ましい。As the basic compound, 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU),
Common organic basic compounds such as triethylamine, N-methylpyrrolidine, N,N-dimethylbenzylamine, N,N-diethylaniline, and tri-n-butylamine are exemplified, and triethylamine is particularly preferred.
【００１１】塩基化合物の使用量は、通常、原料の化１
で示される化合物に対して、２〜１０倍モルであるが、
特に３〜４倍モルが適当である。[0011] The amount of the basic compound used is usually determined by
2 to 10 times the molar amount of the compound represented by
In particular, 3 to 4 times the molar amount is suitable.
【００１２】反応温度は、０〜１００℃の間で任意であ
るが、６０〜８０℃付近が望ましい。反応時間は反応温
度により、３〜３０時間の間で任意である。[0012] The reaction temperature is arbitrary between 0 and 100°C, but preferably around 60 to 80°C. The reaction time is arbitrary between 3 and 30 hours depending on the reaction temperature.
【００１３】このような反応によって、本発明の化合物
である化２で示されるペンタジエナール誘導体が容易に
得られ、通常の分離手段、例えば抽出、分液、濃縮、薄
層クロマトグラフィー、カラムクロマトグラフィー等に
より反応混合物から単離精製することができる。Through such a reaction, the pentadienal derivative represented by formula 2, which is the compound of the present invention, can be easily obtained, and can be subjected to conventional separation methods such as extraction, separation, concentration, thin layer chromatography, and column chromatography. It can be isolated and purified from the reaction mixture by photography or the like.
【００１４】[0014]
【実施例１】１−Ｏ−メチル−Ｄ−グルコフラヌロノ−
６，３−ラクトントジセテート０．２７４ｇにアセトニ
トリル５ｍｌ、及びトリエチルアミン０．４２ｍｌを加
え、６０℃に於て２４時間攪拌し反応させる。反応終了
後、反応混合物を減圧下に濃縮し、エーテルで抽出して
得られた油状物から薄層クロマトグラフィーによって４
−アセトキシ−５−メトキシペンタジエナールを単離し
た。（収率２１．５％）[Example 1] 1-O-methyl-D-glucofuranurono-
5 ml of acetonitrile and 0.42 ml of triethylamine were added to 0.274 g of 6,3-lactone todicetate, and the mixture was stirred at 60° C. for 24 hours to react. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and extracted with ether. The resulting oil was subjected to thin layer chromatography to obtain 4
-acetoxy-5-methoxypentadienal was isolated. (Yield 21.5%)
【００１５】[0015]
【実施例２】１−Ｏ−メチル−Ｄ−グルコフラヌロノ−
６，３−ラクトントジセテート０．２７４ｇにアセトニ
トリル５ｍｌ、及びトリエチルアミン０．４２ｍｌを加
え、還流下１６時間攪拌し反応させる。反応終了後、反
応混合物を減圧下に濃縮し、エーテルで抽出して得られ
た油状物から薄層クロマトグラフィーによって４−アセ
トキシ−５−メトキシペンタジエナールを単離した。
（収率 １５．８％）[Example 2] 1-O-methyl-D-glucofuranurono-
5 ml of acetonitrile and 0.42 ml of triethylamine are added to 0.274 g of 6,3-lactone todicetate, and the mixture is stirred and reacted under reflux for 16 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and extracted with ether. From the resulting oil, 4-acetoxy-5-methoxypentadienal was isolated by thin layer chromatography. (Yield 15.8%)
【００１６】[0016]
【実施例３】１−Ｏ−メチル−Ｄ−グルコフラヌロノ−
６，３−ラクトントジセテート０．２７４ｇにクロロホ
ルム５ｍｌ、及びトリエチルアミン０．４２ｍｌを加え
、室温に於いて１６８時間攪拌し反応させる。反応終了
後、反応混合物を減圧下に濃縮し、エーテルで抽出して
得られた油状物から薄層クロマトグラフィーによって４
−アセトキシ−５−メトキシペンタジエナールを単離し
た。（収率８．９％）[Example 3] 1-O-methyl-D-glucofuranurono-
5 ml of chloroform and 0.42 ml of triethylamine were added to 0.274 g of 6,3-lactone todicetate, and the mixture was stirred and reacted at room temperature for 168 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and extracted with ether. The resulting oil was subjected to thin layer chromatography to obtain 4
-acetoxy-5-methoxypentadienal was isolated. (yield 8.9%)
【００１７】[0017]
【実施例４】１−Ｏ−メチル−Ｄ−グルコフラヌロノ−
６，３−ラクトントジセテート０．２７４ｇにトルエン
５ｍｌ、及びトリエチルアミン０．４２ｍｌを加え、９
０℃に於て２４時間攪拌し反応させる。反応終了後、反
応混合物を減圧下に濃縮し、エーテルで抽出して得られ
た油状物から薄層クロマトグラフィーによって４−アセ
トキシ−５−メトキシペンタジエナールを単離した。
（収率 ８．９％）[Example 4] 1-O-methyl-D-glucofuranurono-
Add 5 ml of toluene and 0.42 ml of triethylamine to 0.274 g of 6,3-lactone todicetate,
The mixture was stirred and reacted at 0°C for 24 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and extracted with ether. From the resulting oil, 4-acetoxy-5-methoxypentadienal was isolated by thin layer chromatography. (yield 8.9%)
Claims (1)
−６，３−ラクトンジアセテートを塩基化合物の共存下
に反応させることを特徴とする化２で示されるペンタジ
エナール誘導体の製造方法。 【化２】[Claim 1] [Chemical 1] A compound represented by chemical formula 2, characterized in that 1-O-methyl-D-glucofuranurono-6,3-lactone diacetate represented by chemical formula 1 is reacted in the presence of a basic compound. A method for producing a pentadienal derivative. [Case 2]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3074596A JP2904603B2 (en) | 1991-03-13 | 1991-03-13 | Method for producing pentadienal derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3074596A JP2904603B2 (en) | 1991-03-13 | 1991-03-13 | Method for producing pentadienal derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04283541A true JPH04283541A (en) | 1992-10-08 |
| JP2904603B2 JP2904603B2 (en) | 1999-06-14 |
Family
ID=13551693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3074596A Expired - Lifetime JP2904603B2 (en) | 1991-03-13 | 1991-03-13 | Method for producing pentadienal derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2904603B2 (en) |
-
1991
- 1991-03-13 JP JP3074596A patent/JP2904603B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2904603B2 (en) | 1999-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111533745A (en) | Process for preparing tert-butyl-3- (aminomethyl) dihydro-5H-triazolodiazepine-8 (9H) -carboxylic acid ester | |
| JP6676146B2 (en) | Novel production method of chromanol derivative | |
| JPH04283541A (en) | Production of pentadienal derivative | |
| JPH0768163B2 (en) | Process for producing cyclopentenone derivative | |
| CN111018779B (en) | 2- (3-isoquinolyl) -ethyl propionate derivative and synthetic method thereof | |
| CN112624957A (en) | Synthetic method of 3-alkyl isoindolinone derivatives | |
| JP2639549B2 (en) | Pentadienal derivatives and their production | |
| JPH03261741A (en) | Production of 4-phenyl-3-buten-2-one | |
| CN112778199B (en) | Compound containing nitrate functional group and synthetic method thereof | |
| CN107459530A (en) | A kind of 1,3 isoquinolin derovatives of novel silicon base substitution and preparation method thereof | |
| CN108558974A (en) | A kind of preparation and application of the derivative pyridine triazole Raney nickel of sugar | |
| CN113651715B (en) | Method for synthesizing coumaroyl dopamine by one-pot method | |
| CN114539107B (en) | Aromatic sulfonyl modified difluoromethyl reaction building block and synthesis method thereof | |
| JP2663295B2 (en) | Hexadienoic acid derivative and method for producing the same | |
| JPH07252189A (en) | Hexadienone derivative and its production | |
| JPH04283598A (en) | Production of l-idofuranyurono-6,3-lactone derivative | |
| CN108129357B (en) | Preparation method of anamorelin intermediate | |
| JPH07252190A (en) | Hexadienone derivative and its production | |
| JPH06263718A (en) | 5-hydroxy-2-oxovaleric acid derivative and its production | |
| JP2832480B2 (en) | 1,3-pentadiene derivative and method for producing the same | |
| JP2736916B2 (en) | Manufacturing method of cibeton | |
| JPH09241251A (en) | Pyran derivative and its production | |
| CN115611760A (en) | Chemical synthesis method suitable for large-scale production of (S) -2-amino-5-alkynyl caproic acid | |
| JPH06271529A (en) | Pentadienal derivative and its production | |
| JPH09110787A (en) | Acetylation of primary alcohol and phenol by solvent-free reaction |