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Sodium hydroxide was dissolved in an appropriate amount of distilled water. This solution was heated in a water bath at 80–90◦C; agar agar was then slowly added to the hot alkali solution with stirring till a brown transparent viscous solution was obtained. This solution on cooling in ice gave a gel. The quantities of the three components, namely water–NaOH–agar agar, were varied to get different types of gels. Results are plotted on the triangular phase diagram. For the required GEBC a gel with the following composition was prepared: in 6 g of water 1 g of NaOH was dissolved with stirring. This solution was heated in a water bath at a temperature of about 80–90◦C; to this hot solution, 3 g of agar agar powder was slowly added while stirring the mixture homogeneously. The heating and stirring were continued till a translucent brown viscous solution was obtained, which on cooling in ice gave a hard solid gel which could be cut into pieces. To acrylonitrile (10 mmol), in the alcohol (20 ml) taken in excess, 10% NaOH-GEBC pieces (0.1 g) were added. The reaction mixture was stirred at the required temperature. For 1aand 1bthe reactions were moni-tored over GC by drawing samples from the reaction and analyzing them. In case of other alcohols, however, the reaction took at least 3 h. The solution was then filtered, the GEBC was washed with the alcohol used and the filtrate was analyzed by G.C. In the case of benzyl alcohol, the alcohol and acrylonitrile were taken in 1:1 mole ratio in 2-methylpropan-2-ol as solvent (5 ml) and the reaction was carried out at 50◦C. The identity of known cyanoethylated products of methanol, ethanol, cellosolve, and benzyl alcohol was established by their b.p.s and FT-IR spectra. The identity of unreported cyanoethylated products of 1-propanol and 2-methylpropan-1-ol was established with the help of 1H NMR spectra. |

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用適量的蒸餾水溶解氫氧化鈉。將上述溶液置于80-90℃水浴中加熱;然后將瓊脂慢慢添加到熱堿溶液中并攪拌直到變?yōu)樽厣该髡吵砣芤骸T撊芤涸诒欣鋮s后得到凝膠。這三個成分(即水、氫氧化鈉、瓊脂)的數(shù)量不同導致所得凝膠的類型不同。結果繪制在三角相圖中。 所需的凝膠包埋堿催化劑凝膠由以下成分制備: 1g氫氧化鈉在6g水中攪拌溶解。將該溶液置于80-90℃水浴中加熱;將3g瓊脂粉緩慢加入到該熱溶液中,攪拌直到混合均勻。溶液持續(xù)加熱并攪拌直到變?yōu)榘胪该鞯淖厣吵砣芤,在冰中冷卻后得到可切成片的硬固體凝膠。 丙烯腈(10mmol)加入到過量的乙醇(20ml)中,再加入10%的NaOH-凝膠包埋堿催化劑片(0.1g)。反應物在所需溫度下攪拌。1a和1b反應利用氣相層析來檢測,從反應中取樣并分析它們。然而,對于其他醇類,反應至少要進行3h。溶液過濾,用乙醇洗滌凝膠包埋堿催化劑并用氣相層析分析了濾液。 苯甲醇、乙醇和丙烯腈按照摩爾比1:1分別置于溶劑2-甲基丙烷-2-醇(5ml)中在50℃下進行反應。 已知標識的甲醇,乙醇,甲基纖維素和芐醇的氰乙基化產(chǎn)品通過其叔丁基二苯基硅烷基和傅里葉變換紅外光譜加以證明。未知標識的2-甲基丙烷-1-醇和1-丙醇的氰乙基化產(chǎn)品通過核磁氫譜的輔助加以證明。 |
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