环糊精衍生物制备及催化水相碳-碳交联偶合反应
|
摘要
以β-环糊精为原料,通过磺酰化、叠氮化以及氨基化反应得到单(6-氨基-6-去氧)-β-环糊精,应用红外光谱、质谱和元素分析等手段,对反应中间产物及最终产物的结构进行了分析和表征。在水相中,以单(6-氨基-6-去氧)-β-环糊精、2,6-二溴甲基吡啶及醋酸钯(Pd(OAc)2)反应制得催化剂体系,用于催化水相Suzuki交联偶合反应。考察了温度、缚酸剂和反应时间等条件对催化反应产率的影响。试验结果表明:当卤代芳烃为1.0 mmol,芳基硼酸为1.5 mmol,催化剂为0.05%mmol时,50℃下反应6 h,联芳烃的产率可达97%。
Taking β-cyclodextrin as raw material,mono( 6-amino-6-deoxy)-β-cyclodextrin was synthesized by sulfonylation,azidation and amination. The structures of the reaction intermediates and final product were characterized by elemental analysis,infrared spectrum and mass spectrum. The catalytic system which was synthesized by reacting mono( 6-amino-6-deoxy)-β-cyclodextrin with 2,6-dibromomethylpyridine and palladium acetate in water,was used to catalyze Suzuki cross-coupling reaction. The effects of temperature,acid binding agent and reaction time on the yield of catalytic reaction were investigated. The experimental results show that when the aryl halide,aryl boronic acid and catalysts is 1. 0 mmol,1. 5 mmol and 0. 05% mmol respectively,the yield of biaryl can reach 97% at 50 ℃ for 6 h.
Taking β-cyclodextrin as raw material,mono( 6-amino-6-deoxy)-β-cyclodextrin was synthesized by sulfonylation,azidation and amination. The structures of the reaction intermediates and final product were characterized by elemental analysis,infrared spectrum and mass spectrum. The catalytic system which was synthesized by reacting mono( 6-amino-6-deoxy)-β-cyclodextrin with 2,6-dibromomethylpyridine and palladium acetate in water,was used to catalyze Suzuki cross-coupling reaction. The effects of temperature,acid binding agent and reaction time on the yield of catalytic reaction were investigated. The experimental results show that when the aryl halide,aryl boronic acid and catalysts is 1. 0 mmol,1. 5 mmol and 0. 05% mmol respectively,the yield of biaryl can reach 97% at 50 ℃ for 6 h.
引文
[1]杨黎燕,谢婷婷,邢壮壮,等.β-环糊精聚合物在药学领域的应用研究[J].化工科技,2016,24(1):78-82.
[2]马水仙,赵雪秋,王淑惠,等.山姜素与甲基化β-环糊精的包合行为研究[J].云南民族大学学报(自然科学版),2016,25(1):29-33.
[3]沈海民,方红果,武宏科,等.环糊精衍生物的分子形态及其构筑策略研究进展[J].化工进展,2015,34(2):430-446.
[4]MA D Y,ZHANG Y M,XU J N.The synthesis and process optimization of sulfobutyl etherβ-cyclodextrin derivatives[J].Tetrahedron,2016,72(22):3105-3112.
[5]MIHAILIASA M,CALDERA F,LI J,et al.Preparation of functionalized cotton fabrics by means of melatonin loadedβ-cyclodextrin nanosponges[J].Carbohydrate polymers,2016,142:24-30.
[6]赵美霞,李洋.L-精氨酸-β-环糊精的合成和结构表征[J].河南大学学报(自然科学版),2013,43(4):402-404.
[7]彭彩云,张耿,陈文明,等.羟丙基-β-环糊精的合成及其表征[J].中国医药导报,2010,7(36):30-31,51.
[8]SUZUKI A.Cross-coupling reactions of organoboranes:an easy way to construct C—C bonds(Nobel lecture)[J].Angewandte chemie international edition,2011,50(30):6722-6737.
[9]栾玉新.新型水溶性钯催化剂:设计、制备及其在Suzuki-Miyaura交叉偶联反应中的应用[D].杭州:浙江工业大学,2014.
[10]KABOUDIN B,SALEMI H,MOSTAFALU R,et al.Pd(II)-β-cyclodextrin complex:synthesis,characterization and efficient nanocatalyst for the selective Suzuki-Miyaura coupling reaction in water[J].Journal of organometallic chemistry,2016,29(3):229-242.
[11]DINDULKAR S D,JEONG D,KIM H,et al.Functionalizedβ-cyclodextrin as supramolecular ligand and their Pd(OAc)2complex:highly efficient and reusable catalyst for Mizoroki-Heck cross-coupling reactions in aqueous medium[J].Carbohydrate research,2016,430:85-94.
[12]KAIROUZ V,SCHMITZER A R.Chem Inform abstract:imidazolium-functionalizedβ-cyclodextrin as a highly recyclable multifunctional ligand in water[J].Chem Inform,2014,45(47):3117-3124.
[13]DECOTTIGNIES A,FIHRI A,AZEMAR G,et al.Ligandless Suzuki-Miyaura reaction in neat water with or without nativeβ-cyclodextrin as additive[J].Catalysis communications,2013,32:101-107.
[2]马水仙,赵雪秋,王淑惠,等.山姜素与甲基化β-环糊精的包合行为研究[J].云南民族大学学报(自然科学版),2016,25(1):29-33.
[3]沈海民,方红果,武宏科,等.环糊精衍生物的分子形态及其构筑策略研究进展[J].化工进展,2015,34(2):430-446.
[4]MA D Y,ZHANG Y M,XU J N.The synthesis and process optimization of sulfobutyl etherβ-cyclodextrin derivatives[J].Tetrahedron,2016,72(22):3105-3112.
[5]MIHAILIASA M,CALDERA F,LI J,et al.Preparation of functionalized cotton fabrics by means of melatonin loadedβ-cyclodextrin nanosponges[J].Carbohydrate polymers,2016,142:24-30.
[6]赵美霞,李洋.L-精氨酸-β-环糊精的合成和结构表征[J].河南大学学报(自然科学版),2013,43(4):402-404.
[7]彭彩云,张耿,陈文明,等.羟丙基-β-环糊精的合成及其表征[J].中国医药导报,2010,7(36):30-31,51.
[8]SUZUKI A.Cross-coupling reactions of organoboranes:an easy way to construct C—C bonds(Nobel lecture)[J].Angewandte chemie international edition,2011,50(30):6722-6737.
[9]栾玉新.新型水溶性钯催化剂:设计、制备及其在Suzuki-Miyaura交叉偶联反应中的应用[D].杭州:浙江工业大学,2014.
[10]KABOUDIN B,SALEMI H,MOSTAFALU R,et al.Pd(II)-β-cyclodextrin complex:synthesis,characterization and efficient nanocatalyst for the selective Suzuki-Miyaura coupling reaction in water[J].Journal of organometallic chemistry,2016,29(3):229-242.
[11]DINDULKAR S D,JEONG D,KIM H,et al.Functionalizedβ-cyclodextrin as supramolecular ligand and their Pd(OAc)2complex:highly efficient and reusable catalyst for Mizoroki-Heck cross-coupling reactions in aqueous medium[J].Carbohydrate research,2016,430:85-94.
[12]KAIROUZ V,SCHMITZER A R.Chem Inform abstract:imidazolium-functionalizedβ-cyclodextrin as a highly recyclable multifunctional ligand in water[J].Chem Inform,2014,45(47):3117-3124.
[13]DECOTTIGNIES A,FIHRI A,AZEMAR G,et al.Ligandless Suzuki-Miyaura reaction in neat water with or without nativeβ-cyclodextrin as additive[J].Catalysis communications,2013,32:101-107.