I_2负载蒙脱土催化Mannich反应
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摘要
以蒙脱土负载I_2为催化剂,芳香醛、苯乙酮、苯胺为原料进行Mannich反应.单因素法筛选最优催化剂、溶剂、反应时间、温度及原料摩尔比.获得的最优条件为:反应时间5 h,温度25℃,原料芳香醛(1)-苯乙酮(2)-芳香胺(3)摩尔比为1.0∶1.0∶0.9,产率在85.1%~98.8%之间,产物通过红外、核磁、熔点进行表征.
Mannich reaction catalyzed by ioaded Iodine use aromatic aldehyde,acetophenone,aniline as starting materials.The effects of catalyst,solvent,reaction time,temperature and quivalency of starting materials on yield were investigated by single factor method.The optimal conditions are: reaction temperature is 25 ℃,the reaction time is 5 h,the molar ratio of raw materials was 1 ∶ 1 ∶ 0.9.The yields range from 85.1% to 98.8% and the product is characterized by IR,NMR and melting point.
Mannich reaction catalyzed by ioaded Iodine use aromatic aldehyde,acetophenone,aniline as starting materials.The effects of catalyst,solvent,reaction time,temperature and quivalency of starting materials on yield were investigated by single factor method.The optimal conditions are: reaction temperature is 25 ℃,the reaction time is 5 h,the molar ratio of raw materials was 1 ∶ 1 ∶ 0.9.The yields range from 85.1% to 98.8% and the product is characterized by IR,NMR and melting point.
引文
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[19]YI L,ZOU J H,LEI H S,et al.The Mannich reaction of butanone,aromatic aldehydes and aromatic amines[J].Synthetic Communications,1991,21(20):2 109-2 117.
[20]CELINE F,FLORENT M,ANNE L,et al.Pronounced catalytic effect of a micellar solution of sodium dodecylsulfate(SDS)upon a three-component reaction of aldehydes,amines,and ketones under neutral conditions?[J].European Journal of Organic Chemistry,2010,2009(8):1 249-1 255.
[2]AKIYAMA T,ITOH J,YOKOTA K,et al.Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid[J].Advanced Synthesis&Catalysis,2004,43(12):1 566-1 568.
[3]AREND M,WESTERMANN B,RISCH N.Modern variants of the mannich reaction[J].Angewandte Chemie International Edition,2010,37(37):1 044-1 070.
[4]JOSHI N S,WHITAKER L R,FRANCIS M B.A threecomponent Mannich-type reaction for selective tyrosine bioconjugation[J].Journal of the American Chemical Society,2015,126(49):15 942.
[5]陈君丽,解正峰,邢烨.水相中磷钨酸催化苯乙酮、芳香醛和芳香胺的Mannich反应[J].有机化学,2011,31(10):1 714-1 718.CHEN J L,XIE Z F,XING Y.Mannich reaction of acetophenone,aromatic aldehydes and aro-matic amines catalyzed by tungstophosphoric acid in water[J].Organic Chemistry,2011,31(10):1 714-1 718.
[6]宋志国,王敏,姜恒,等.稀土甲基磺酸盐催化苯乙酮、芳香醛和芳香胺的Mannich反应[J].合成化学,2009,17(6):692-695.SONG Z G,WANG M,JIANG H,et al.Rare Earth methanesulfonate catalyzed Mannich reaction of acetophenone aromatic aldehyde and aromatic amine[J].Synthetic Chemistry,2009,17(6):692-695.
[7]张丽军,周永青,夏静,等.无溶剂条件下稀土胺基化合物催化Mannich反应的研究[J].安徽师范大学学报:自然科学版,2009,32(5):445-447.ZHANG L J,ZHOU Y Q,XIA J,et al.Studies on the Mannich reaction catalyzed by lanthanide amide[J].Anhui Normal University:Natural Science,2009,32(5):445-447.
[8]王利民,韩建伟,盛佳,等.Yb(OTf)3催化苯乙酮、芳香醛和芳香胺的Mannich反应:三组分“一锅法”合成β-氨基酮衍生物[J].有机化学,2005,25(5):591-594.WANG L M,HAN J W,SHENG J,et al.Yb(OTf)3catalyzed Mannich reaction of acetophenone with aromatic aldehydes and aromatic amines:Three component onepot synthesis ofβ-amino ketone derivatives[J].Organic Chemistry,2005,25(5):591-594.
[9]ROMAN G.Mannich bases in medicinal chemistry and drug design[J].European Journal of Medicinal Chemistry,2015,89(6):743-816.
[10]MOVASSAGH B,TAHERSHAMSI L,MOBARAKI A.A magnetic solid sulfonic acid modified with hydrophobic regulators:an efficient recyclable heterogeneous catalyst for one-pot aza-Michael-type and Mannich-type reactions of aldehydes,ketones,and amines[J].Tetrahedron Letters,2015,56(14):1 851-1 854.
[11]VISWANADHAM K K,PRATHAP R M,SATHYANARAYANA P,et al.Iodine-mediated oxidative annulation for one-pot synthesis of pyrazines and quinoxalines using a multipathway coupled domino strategy[J].Chemical Communications,2014,50(88):13 517-20.
[12]SAH K B,BANERJEE M,GHOSH S,et al.I2catalyzed Friedel-Crafts alkylation reaction of substituted anilines with ninhydrin:formation of novel products and their antimicrobial evaluation[J].Medicinal Chemistry Research,2012,22(4):2 023-2 037.
[13]HARIKRISHNA K,MUKKAMALA R,HINKELMANN B,et al,Iodine-Promoted oxidative conversion of oVinyl diaryl ketones into o-Acetyl diaryl ketones,synthesis of 1-Methyl-4-arylphthalazines as analogues of podophyllotoxin[J].European Journal of Medicinal Chemistry,2014,2014(5):1 066-1 075.
[14]李风起.蒙脱土负载三氯化铁氧化苯偶姻制备苯偶酰[J].应用化工,2011,40(3):459-461.LI F Q.Preparation of benzil from benzoin by ferric chloride supported on montmorillonite K10 as oxidant[J].Applied Chemical Industry,2011,40(3):459-461.
[15]吴伟,吴小云,吴江,等.负载型蒙脱土催化芦竹碱的微波合成.[J].合成化学,2015,23(6):543-546.WEI W,WU X Y,WU J,et al.Catalytic synthesis of gramine by immobilized montmorillonite under microwave irradiation[J].Synthetic Chemistry,2015,23(6):543-546.
[16]吴小云,尹晓刚,龚维,等.醋酸锌催化串联反应合成2-氨基-3-氰基-4H-吡喃衍生物[J].化学通报,2016,79(12):1 156-1 160.WU X Y,YIN X G,GONG W,et al.Syntheses of 2-Amino-3-cyano-4H-pyran derivatives catalyzed by zinc acetate[J].Chemistry Bulletin,2016,79(12):1 156-1160.
[17]尹晓刚,吴小云,王野,等.超声辅助蒙脱土负载碘催化Knoevenagel反应[J].化学试剂,2016,38(11):1 036-1 040.YIN X G,WU X Y,WANG Y,et al.Knoevenagel reaction catalyzed by I2loaded montmorillonite under ultrasonic conditions[J].Chemistry Reagents,2016,38(11):1 036-1 040.
[18]吴小云,王野,尹晓刚,等.微波辅助法合成双吲哚甲烷衍生物[J].化学试剂,2016,38(3):273-276.WU X Y,WANG Y,YIN X G,et al.Synthesis of bis(indolyl)methanes under microwave irradiation[J].Chemistry Reagents,2016,38(3):273-276.
[19]YI L,ZOU J H,LEI H S,et al.The Mannich reaction of butanone,aromatic aldehydes and aromatic amines[J].Synthetic Communications,1991,21(20):2 109-2 117.
[20]CELINE F,FLORENT M,ANNE L,et al.Pronounced catalytic effect of a micellar solution of sodium dodecylsulfate(SDS)upon a three-component reaction of aldehydes,amines,and ketones under neutral conditions?[J].European Journal of Organic Chemistry,2010,2009(8):1 249-1 255.