催化学报
催化學報
최화학보
CHINESE JOURNAL OF CATALYSIS
2014年
3期
319-323
,共5页
铜催化剂%还原开环%1-氨基-2-乙酰基蒽醌%3-甲基蒽醌-1,2-c-异噁唑%清洁合成
銅催化劑%還原開環%1-氨基-2-乙酰基蒽醌%3-甲基蒽醌-1,2-c-異噁唑%清潔閤成
동최화제%환원개배%1-안기-2-을선기은곤%3-갑기은곤-1,2-c-이오서%청길합성
Copper catalyst%Reductive ring-cleavage%1-Amino-2-acetyl anthraquinone%3-Methylanthra[1,2-c]isoxazol-6,11-dione%Clean synthesis
以水为反应介质,水合肼为还原剂,研究了痕量铜催化3-甲基蒽醌-[1,2-c]-异噁唑还原开环反应以清洁高效合成1-氨基-2-乙酰基蒽醌,考察了不同种类过渡金属硝酸盐的催化性能,发现Cu(NO3)2性能最好.加入2.6%的催化剂和1.3倍的水合肼,在室温反应2 h,底物转化率和目标产物选择性分别可达到97.2%和95%, TON达到38.产品结构经氢核磁谱和质谱得以确证,主要副产为羟基取代的1-氨基-2-乙酰基蒽醌.此外,提出了铜催化3-甲基蒽醌-[1,2-c]-异噁唑还原开环反应合成1-氨基-2-乙酰基蒽醌的可能反应机理.
以水為反應介質,水閤肼為還原劑,研究瞭痕量銅催化3-甲基蒽醌-[1,2-c]-異噁唑還原開環反應以清潔高效閤成1-氨基-2-乙酰基蒽醌,攷察瞭不同種類過渡金屬硝痠鹽的催化性能,髮現Cu(NO3)2性能最好.加入2.6%的催化劑和1.3倍的水閤肼,在室溫反應2 h,底物轉化率和目標產物選擇性分彆可達到97.2%和95%, TON達到38.產品結構經氫覈磁譜和質譜得以確證,主要副產為羥基取代的1-氨基-2-乙酰基蒽醌.此外,提齣瞭銅催化3-甲基蒽醌-[1,2-c]-異噁唑還原開環反應閤成1-氨基-2-乙酰基蒽醌的可能反應機理.
이수위반응개질,수합정위환원제,연구료흔량동최화3-갑기은곤-[1,2-c]-이오서환원개배반응이청길고효합성1-안기-2-을선기은곤,고찰료불동충류과도금속초산염적최화성능,발현Cu(NO3)2성능최호.가입2.6%적최화제화1.3배적수합정,재실온반응2 h,저물전화솔화목표산물선택성분별가체도97.2%화95%, TON체도38.산품결구경경핵자보화질보득이학증,주요부산위간기취대적1-안기-2-을선기은곤.차외,제출료동최화3-갑기은곤-[1,2-c]-이오서환원개배반응합성1-안기-2-을선기은곤적가능반응궤리.
A clean and highly efficient synthesis of 1-amino-2-acetylanthraquinone via reductive isoxazole ring cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione catalyzed by trace copper using hy-drazine hydrate as a clean reducing agent and water as a green reaction medium under mild reac-tion conditions was investigated. Various transition-metal catalysts were screened for the reduc-tive ring-opening reaction, and Cu(NO3)2 was shown to be an excellent catalyst. A conversion of 97.2% and 1-amino-2-acetylanthraquinone selectivity greater than 95% were obtained in the presence of 2.6 mol% Cu(NO3)2 (turnover number 38) with 1.3 equiv. of hydrazine hydrate for 2 h in water. The structure of the product was confirmed by 1H nuclear magnetic resonance spectros-copy and mass spectrometry; the main byproduct was hydroxyl-substituted 1-amino-2- acetylan-thraquinone. A possible reaction mechanism for the copper-catalyzed ring cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione with hydrazine hydrate was proposed.