3-芳胺基丁-2-烯酸酯和酰胺的无溶剂合成与表征
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摘要
β-酮基丁酸酯和N-芳基取代的β-酮基丁酰胺通过双乙烯酮与ROH(R=烷基或芳基)或N-甲基苯胺的反应以及乙酰乙酸乙酯的芳胺解反应制备得到。两类化合物与2～3倍物质的量的芳香胺在无溶剂条件于室温下以质子酸为催化剂反应,以中高收率得到一系列的目标化合物,并对它们进行了1HNMR、13CNMR、IR和ESI-MS表征。其中两个还通过X-射线单晶衍射测定了其分子结构。实现了此类化合物无溶剂无金属催化条件下的简单合成。
Acetylacetic esters and N-aryl acetylacetamides were synthsized by the reaction of diketene with alcohols or N-methylaniline and by treatment of ethyl acetylacetate with arylamines,respectively.The title compounds were obtained in moderate to high yield by facial condensation of acetylacetic esters and N-aryl acethlacetamide with 2 ～ 3 folds of various arylamines catalyzed by concentrate protic acid at room temperature and in solvent-free condition.The samples were readily purified by recrystallization or by column chromatolography,and were confirmed by1 HNMR,13 CNMR,IR and ESI-MS.The crystal structures of two compounds were determined by X-ray single crystal diffraction analysis.A simple synthesis method of such compounds under solvent-free and metal-free catalysis was achieved.
Acetylacetic esters and N-aryl acetylacetamides were synthsized by the reaction of diketene with alcohols or N-methylaniline and by treatment of ethyl acetylacetate with arylamines,respectively.The title compounds were obtained in moderate to high yield by facial condensation of acetylacetic esters and N-aryl acethlacetamide with 2 ～ 3 folds of various arylamines catalyzed by concentrate protic acid at room temperature and in solvent-free condition.The samples were readily purified by recrystallization or by column chromatolography,and were confirmed by1 HNMR,13 CNMR,IR and ESI-MS.The crystal structures of two compounds were determined by X-ray single crystal diffraction analysis.A simple synthesis method of such compounds under solvent-free and metal-free catalysis was achieved.
引文
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[34]王英磊,刘学国,杜朝军,等.磺酸功能化壳聚糖催化合成氧杂蒽二酮衍生物[J].化学试剂,2018,40(3):295-298.
[35]曾鸿耀,张杰.无溶剂氨基磺酸催化二芳基乙醇酮的乙酰化[J].化学试剂,2016,38(3):263-267.
[36]VIRSODIA V,PISSURLENKAR R R,MANVAR D,et al.Synthesis,screening for antitubercular activity and3D-QSAR studies of substituted n-phenyl-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxam-ides[J].Eur.J.Med.Chem.,2008,43(10):2 103-2 115.
[37]RALL K B,PEREKALIN V V.Reactions of diketene.Ⅲ.reaction of diketene with some aromatic hydroxy compounds.synthesis of phenyl acetoacetates[J].Zhur.Obsh.Khim.,1955,25:259-264.
[38]YAMAMOTO T,NIWA S,OHNO S,et al.Structure-activity relationship study of 1,4-dihydropyridine derivatives blocking n-type calcium channels[J].Bioorg.&Med.Chem.Lett.,2006,16(4):798-802.
[39]RALL K B,PEREKALIN V V.Reactions of diketene.Ⅳ.reaction of diketene with some aromatic hydroxy compounds.synthesis of methylcoumarin derivatives[J].Zhur.Obsh.Khim.,1955,25:781-786.
[40]MAITI A,REDDY P V,STURDY M,et al.Synthesis of casimiroin and optimization of its quinone reductase and aromatase inhibitory activities[J].J.Med.Chem.,2009,52(7):1 873-1 884.
[2]WANG C M,FRIEDRICH S,YOUNKIN T R,et al.Neutral nickel(Ⅱ)-based catalysts for ethylene polymerization[J].Organometallics,1998,17(15):3 149-3 151.
[3]YOUNKIN T R,CONNOR E F,HENDERSON J I,et al.Neutral,single-component nickel(Ⅱ)polyolefin catalysts that tolerate heteroatoms[J].Cheminform,2000,31(15):460-462.
[4]AZOULAY J D,ITIGAKI K,WU G,et al.Influence of steric and electronic perturbations on the polymerization activities ofα-iminocarboxamide nickel complexes[J].Organometallics,2008,27(10):2 273-2 280.
[5]黄庆东,李春兰,张宇,等.桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性[J].高等学校化学学报,2014,35(3):524-530.
[6]ZHOU M,XUE Z J,CAO M,et al.Rhodium-catalyzed asymmetric hydrogenation of unprotectedβ-enamine phosphonates[J].Org.Chem.,2016,14(20):4 582-4 584.
[7]HAO H J,HAN X M.Synthesis and application of carbonlinked bis(β-ketiminato)aluminum complexes:CN 101302 230[P].2008-11-12.
[8]张发良.碳桥联双β-酮二亚胺基铝、锌和镍配合物及碳桥联双β-酮二亚胺二氯化镍配合物的合成和结构表征[D].北京:北京化工大学,2006.
[9]LIU Y H,WANG P,CHENG G T.A general and efficient method for synthesis of enaminones and enamino esters catalyzed by Nb Cl5under solvent-free conditions[J].Monatsh.Chem.,2013,144(2):191-196.
[10]LIU J Y,CAO G E,XU W,et al.Ni(OAc)2:a highly efficient catalyst for the synthesis of enaminone and enamino ester derivatives under solvent-free conditions[J].Appl.Organomet.Chem.,2010,24(10):685-689.
[11]SHENDAGE S S,NAGARKAR J M.Ultrasound assisted synthesis of enaminones using nickel oxide[J].Curr.Chem.Lett.,2013,2(3):145-152.
[12]LASKAR R A,BEGUM N A,HEDAYETULLAH M M,et al.Vanadium(Ⅳ)acetylacetonate catalyzed stereoselective synthesis ofβ-enaminoesters andβ-enaminones[J].Cheminform,2013,54(5):436-440.
[13]FENG C L,ZHANG S G,CAI J,et al.Zinc triflate catalyzed synthesis ofβ-enamino keton-es(esters)under solvent-free conditions[J].J.Chem.Res.,2013,37(10):626-629.
[14]ZHANG M,ABLIMIT A,FU Y,et al.Efficient synthesis ofβ-enaminones andβ-enaminoesters catalyzed by gold(Ⅰ)/silver(Ⅰ)under solvent-free conditions[J].Molecules,2012,17(3):2 812-2 822.
[15]ESHGHI H,SEYEDI S M,SAFAEI E,et al.Silica supported Fe(HSO4)3as an efficient,heterogeneous and recyclable catalyst for synthesis ofβ-enaminones andβ-enamino esters[J].J.Mol.Catal.A:Chem.,2012,(363/364):430-436.
[16]MURTHY Y L N,VENU R,GOVINDH B,et al.Solventfree synthesis ofβ-enamino compounds promoted by ferric(Ⅲ)ammonium nitrate[J].Asian J.Chem.,2010,22(4):3 047-3 053.
[17]FENG C L,CHU N N,ZHANG S G,et al.Solvent-free synthesis ofβ-enamino ketones and esters catalyzed by recyclable iron(Ⅲ)triflate[J].Chem.Pap.,2014,68(8):1 097-1 103.
[18]BABU S G,THOMAS B,NIJAMUDHEEN A,et al.Cu/Al O(OH)-catalyzed formation ofβ-enamino ketones/esters under solvent,ligand and base free conditions-experimental and computational studies[J].Catal.Sci.Tech.,2012,2(9):1 872-1 878.
[19]HARRAD M A,OUTTOUCH R,AIT A M,et al.Ca(CF3COO)2:an efficient Lewis acid catalyst for chemoand regio-selective enamination ofβ-dicarbonyl compounds[J].Catal.Commun.,2010,11(5):442-446.
[20]HARRAD M A,BOUALY B,FIRDOUSSI L E,et al.Aluminum phosphate catalyzed free solvent preparation ofβ-enamino esters[J].Am.J.Chem.,2012,2(5):271-276.
[21]HASANINEJAD A,ZARE A,MOHAMMADIZADEH MR,et al.Silica-supported Li HSO4as a highly efficient,heterogeneous and reusable catalytic system for the solvent-free synthesis ofβ-enaminones andβ-enamine esters[J].J.Iran.Chem.Soc.,2010,7(1):69-76.
[22]GAO H,JIA X D,DUAN H F,et al.Highly efficient and recyclable catalyst HBF4·Si O2catalyzed synthesis ofβ-enamino compounds under solvent-free conditions[J].Chem.Res.Chin.Univ.,2011,27(5):792-794.
[23]KARIMI-JABERI Z,TAKMILIFARD Z.Efficient synthesis ofβ-enaminones andβ-enamino esters using tris(hydrogensulfato)boron or trichloroacetic acid as catalysts[J].Eur.Chem.Bull.,2013,2(4):211-213.
[24]CHEN J X,ZHANG C F,GAO W X,et al.B2O3/Al2O3as a new,highly efficient and reusable heterogeneous catalyst for the selective synthesis ofβ-enamino ketones and esters under solvent-free conditions[J].J.Braz.Chem.Soc.,2010,21(8):1 552-1 556.
[25]ADUDE R N,TIGOTE R M,BHUSARE S R.3-Nitrophenylboronic acid-catalyzed synthesis ofβ-enaminones under solvent-free conditions[J].Der Chemica Sinica,2012,3(1):231-235.
[26]HASANINEJAD A,ZARE A,MOHAMMADIZADEH MR,et al.A green solventless protocol for the synthesis ofβ-enaminones andβ-enamino esters using silica sulfuric acid as a highly efficient,heterogeneous and reusable catalyst[J].E-J.Chem.,2015,7(4):1 546-1 554.
[27]KAMBLE V T,JOSHI N S,ATKORE S T.Cyanuric chloride-catalysed rapid conversion ofβ-keto esters intoβ-enamino esters under mild and solvent-free conditions[J].J.Iran.Chem.Soc.,2011,8(3):616-621.
[28]BHATTE K D,TAMBADE P J,DHAKE K P,et al.Silver nanoparticles as an efficient,heterogeneous and recyclable catalyst for synthesis ofβ-enaminones[J].Catal.Commum.,2010,11(15):1 233-1 237.
[29]NARSAIAH A V,REDDY A R,REDDY B V S,et al.Amberlyst-15:an efficient,cost-effective and recyclable hetero geneous solid acid catalyst for the synthesis ofβ-enaminones andβ-enamino esters[J].J.Open Catal.,2011,4:43-46.
[30]SHEKHAR A,PATHAK D D.Zeolite(ZSM-5)as a highly efficient and heterogeneous catalyst for the synthesis ofβ-enaminones andβ-enamino esters[J].E-J.Chem.,2011,8(4):1 632-1 637.
[31]SHIM J,JANG W,JEON K,et al.Petroleum like biodiesel production by catalytic decarboxylation of oleic acid over Pd/Ce-ZrO2under solvent-free condition[J].Appl.Catal.,2018,563:163-169.
[32]WAGH G D,PATHARE S P,AKAMANCHI K G.Sulfated-tungstate-catalyzed synthesis of ureas/thioureas via transamidation and synthesis of forchlorofenuron[J].Chemistry Select,2018,3(25):7 049-7 053.
[33]XING M M,XU H,HOU L F,et al.AlCl3-catalyzed[3+3]cycloaddition of chalcones andβ-enamine ketones(esters):a highly efficient access to multisubstituted cyclohexa-1,3-dienamines[J].RSC Adv.,2016,6(13):10 943-10 948.
[34]王英磊,刘学国,杜朝军,等.磺酸功能化壳聚糖催化合成氧杂蒽二酮衍生物[J].化学试剂,2018,40(3):295-298.
[35]曾鸿耀,张杰.无溶剂氨基磺酸催化二芳基乙醇酮的乙酰化[J].化学试剂,2016,38(3):263-267.
[36]VIRSODIA V,PISSURLENKAR R R,MANVAR D,et al.Synthesis,screening for antitubercular activity and3D-QSAR studies of substituted n-phenyl-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxam-ides[J].Eur.J.Med.Chem.,2008,43(10):2 103-2 115.
[37]RALL K B,PEREKALIN V V.Reactions of diketene.Ⅲ.reaction of diketene with some aromatic hydroxy compounds.synthesis of phenyl acetoacetates[J].Zhur.Obsh.Khim.,1955,25:259-264.
[38]YAMAMOTO T,NIWA S,OHNO S,et al.Structure-activity relationship study of 1,4-dihydropyridine derivatives blocking n-type calcium channels[J].Bioorg.&Med.Chem.Lett.,2006,16(4):798-802.
[39]RALL K B,PEREKALIN V V.Reactions of diketene.Ⅳ.reaction of diketene with some aromatic hydroxy compounds.synthesis of methylcoumarin derivatives[J].Zhur.Obsh.Khim.,1955,25:781-786.
[40]MAITI A,REDDY P V,STURDY M,et al.Synthesis of casimiroin and optimization of its quinone reductase and aromatase inhibitory activities[J].J.Med.Chem.,2009,52(7):1 873-1 884.