1,8-ジアザビシクロ[5.4.0]-7-ウンデセン 化学特性,用途語,生産方法
外観
無色～うすい黄色, 澄明の液体
溶解性
水、エタノール及びアセトンに極めて溶けやすい。
解説
1,8-ジアザビシクロ[5.4.0]-7-ウンデセン
ジアザビシクロウンデセン．略称DBU．ε-カプロラクタムとアクリロニトリルとの反応により生成する．沸点80～83 ℃(80 Pa)．1.018．1.5219．ハロゲン化アルカンに等モル量のDBUを加えると脱ハロゲン化水素が起こりアルケンが生成する．この反応の収率は，類似の1,5-ジアザビシクロ[4.3.0]-5-ノネン(DBN)を用いた場合より高く，ピリジン，キノリンなどの通常の第三級アミンでは満足な結果は得にくい．DBUは活性C-Hをもつ化合物のハロゲン化アルキルによるジアルキル化反応や，クネベナーゲル反応に用いられる．
用途
有機合成(和光試薬時報Vol.63 No.2,p.26(1995))。
ようと
ジアザビシクロウンデセン (1,8-diazabicyclo[5.4.0]undec-7-ene) とは、有機合成化学で用いられる反応試剤のひとつ。
説明
DBU is a bicyclic amidine base. It is non-nucleophilic, sterically hindered, tertiary amine base in organic chemistry. It is reported to be superior to amine catalyst in Baylis-Hillman reaction.It promotes the methylation reaction of phenols, indoles and benzimidazoles with dimethyl carbonate under mild conditions.
化学的特性
Colorless to yellow liquid
天然物の起源
Although all commercially available DBU is produced synthetically, it may also be isolated from the sea sponge Niphates digitalis.The biosynthesis of DBU has been proposed to begin with 1,6-hexanedial and 1,3-diaminopropane.
使用
DBU may be used:
- as catalyst for carboxylic acid esterification with dimethyl carbonate
- in the synthesis of duocarmycin and CC-1065 analogs
- as catalyst in aza-Michael addition and Knovenegal condensation reaction
- as base for dehalogenation of halogenated Diels-Alder adducts and the resulting activated 2,4-dienones were subjected to regio- and stereo-directed Michael additions, using Yamamoto′s reagent (CH3Cu · BF3)
- in a new synthesis of the ABCD ring system of Camptothecin
- DBU may be used as an catalyst for the dissolution and activation of cellulose by a reversible reaction of its hydroxyl groups with carbon dioxide. This dissolved cellulose system can be derivatized to form cellulose mixed esters.
- Used in a new synthesis of the ABCD ring system of Camptothecin.
一般的な説明
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合成
The synthesis of DBU is as follows:As a base, sodium hydroxide was used at a concentration of 25% by weight and 2.3 times molar equivalent. A stirrer was placed in a 100 mL screw tube, and 11.5 g (50 mmol) of DBU hydrochloride, 8.5 g of toluene and 18.5 g (116 mmol) of 25% sodium hydroxide aqueous solution were charged at room temperature. It was placed on a magnetic stirrer and mixed for 1 hour with stirring. The mixture was separated with a 100 mL separatory funnel to obtain 18.8 g of the upper layer containing DBU and 18.4 g of the lower layer of the aqueous layer. The upper layer portion was analyzed by gas chromatography and contained 31.9% by weight of DBU, and the yield was 6.0 g (39.4 mmol) in a yield of 78.8%.
純化方法
Fractionally distil DBU under vacuum. Also purify it by chromatography on Kieselgel and eluting with CHCl3/EtOH/25% aqueous NH3 (15:5:2) and checking by IR and MS. [Oediger et al. Chem Ber 99 2012 1962, Angew Chem, Int Ed Engl 6 76 1967, Guggisberg et al. Helv Chim Acta 61 1057 1978, Beilstein 23/5 V 271.]
1,8-ジアザビシクロ[5.4.0]-7-ウンデセン 上流と下流の製品情報
原材料
準備製品