酞菁鋅高效催化以二氧化碳、含氫硅烷和有機(jī)胺為原料合成甲酰胺類衍生物（英文）
發(fā)布時(shí)間：2018-10-30 06:27
【摘要】：目前為了有效地利用好CO_2,主要策略有以下幾種:(1)"水平途徑"——無價(jià)態(tài)及能量變化,譬如生成尿素、環(huán)狀碳酸酯、聚碳酸酯及VA唑烷酮類衍生物等;(2)"垂直途徑"——有價(jià)態(tài)及能量變化,譬如直接加氫轉(zhuǎn)化成碳一產(chǎn)品(甲酸、甲醛、甲醇、甲烷)等;(3)"對角線途徑"——有價(jià)態(tài)及能量變化,即結(jié)合石油化工原料將CO_2還原生成醇、醚、羧酸、亞胺、酰胺、酯等系列高附加值的精細(xì)有機(jī)化工產(chǎn)品.其中以二氧化碳和含氫硅烷為原料,通過有機(jī)胺的N-甲酰化反應(yīng)合成甲酰胺類衍生物符合綠色化學(xué)和可持續(xù)發(fā)展的要求.基于仿生催化CO_2分子活化的基本理論,我們借鑒強(qiáng)極性的有機(jī)溶劑可有效活化硅氫鍵的性質(zhì),創(chuàng)新性地將廉價(jià)易得的酞菁鋅(Zn Pc)作為類酶催化劑,并以化學(xué)計(jì)量的N,N’-二甲基甲酰胺(DMF)為添加劑,構(gòu)成組分新穎并高效綠色的類酶協(xié)同催化體系,實(shí)現(xiàn)了在溫和反應(yīng)條件下高效高選擇性地合成甲酰胺類衍生物.研究發(fā)現(xiàn):以苯硅烷作為還原劑,當(dāng)加入0.5mol%Zn Pc和2 mmol DMF,在25 ℃和0.5 MPa下僅需反應(yīng)6 h,可得到收率為99%的N-甲基甲酰苯胺.更值得注意的是,當(dāng)以更易得的聚甲基氫硅烷(PMHS)為還原劑時(shí),加入5 mol%Zn Pc和1 mL DMF,在80 ℃和1 MPa下反應(yīng)8 h,N-甲基甲酰苯胺的收率也高達(dá)99%.實(shí)驗(yàn)結(jié)果表明:添加劑DMF可以通過溶劑化和強(qiáng)極性作用高效活化含氫硅烷中的Si-H鍵,然后具有親電性的金屬活性中心能夠穩(wěn)定氫負(fù)離子生成高活性鋅氫中間體.即Zn Pc/DMF之間的協(xié)同催化作用能夠促進(jìn)氫化物從含氫硅烷轉(zhuǎn)移到CO_2分子,進(jìn)而有利于CO_2分子的高效活化.綜上所述,利用類酶催化劑反應(yīng)專一性的特點(diǎn),通過有機(jī)胺的N-甲�；磻�(yīng),實(shí)現(xiàn)了以CO_2和含氫硅烷為原料在溫和條件下甲酰胺類衍生物的綠色高效合成.這對于設(shè)計(jì)和開發(fā)更加高效的催化體系具有一定的指導(dǎo)作用和借鑒意義.
[Abstract]:At present, the main strategies of CO_2, are as follows: (1) "horizontal pathway"-non-valency and energy change, such as the formation of urea, cyclic carbonate, polycarbonate and VA azolone derivatives; (2) "vertical pathway"-there are valence states and energy changes, such as direct hydrogenation into carbon-products (formic acid, formaldehyde, methanol, methane); (3) the "diagonal pathway", in which CO_2 is reduced to alcohol, ether, carboxylic acid, imine, amide, ester and other high value-added fine organic chemical products combined with petrochemical raw materials. The synthesis of formamide derivatives from carbon dioxide and hydrosilane by N-formylation of organic amines meets the requirements of green chemistry and sustainable development. Based on the basic theory of bionic catalytic CO_2 molecular activation, we can use the strong polar organic solvent to activate the hydrosilyl bond effectively, and creatively use the cheap and easily available zinc phthalocyanine (Zn Pc) as the enzyme catalyst, and use stoichiometric N as an enzyme catalyst. N-dimethylformamide (DMF) was used as additive to form a novel and efficient green catalytic system for the synthesis of formamide derivatives under mild reaction conditions. It was found that the yield of N-methylformylaniline was 99% when 0.5mol%Zn Pc and 2 mmol DMF, were added for 6 h at 25 鈩，
本文編號：2299184
[Abstract]:At present, the main strategies of CO_2, are as follows: (1) "horizontal pathway"-non-valency and energy change, such as the formation of urea, cyclic carbonate, polycarbonate and VA azolone derivatives; (2) "vertical pathway"-there are valence states and energy changes, such as direct hydrogenation into carbon-products (formic acid, formaldehyde, methanol, methane); (3) the "diagonal pathway", in which CO_2 is reduced to alcohol, ether, carboxylic acid, imine, amide, ester and other high value-added fine organic chemical products combined with petrochemical raw materials. The synthesis of formamide derivatives from carbon dioxide and hydrosilane by N-formylation of organic amines meets the requirements of green chemistry and sustainable development. Based on the basic theory of bionic catalytic CO_2 molecular activation, we can use the strong polar organic solvent to activate the hydrosilyl bond effectively, and creatively use the cheap and easily available zinc phthalocyanine (Zn Pc) as the enzyme catalyst, and use stoichiometric N as an enzyme catalyst. N-dimethylformamide (DMF) was used as additive to form a novel and efficient green catalytic system for the synthesis of formamide derivatives under mild reaction conditions. It was found that the yield of N-methylformylaniline was 99% when 0.5mol%Zn Pc and 2 mmol DMF, were added for 6 h at 25 鈩，
本文編號：2299184
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