广西师范大学学报（自然科学版） ›› 2015, Vol. 33 ›› Issue (2): 82-87.doi: 10.16088/j.issn.1001-6600.2015.02.013

• • 上一篇    下一篇

5-乙酰胺基-4-(4-氯苯基)-2-甲基-6-氧代-5, 6-二氢-4H-吡喃-3-羧酸乙酯的合成及晶体结构

梁晓龙1,2, 黄婉云3, 潘成学1,2, 苏桂发1,2   

  1. 1.广西师范大学药用资源化学与药物分子工程国家重点实验室培育基地,广西桂林541004;
    2. 广西师范大学化学与药学学院,广西桂林541004;
    3. 桂林医学院药学院,广西桂林541004
  • 收稿日期:2015-01-05 出版日期:2015-02-10 发布日期:2018-09-20
  • 通讯作者: 苏桂发(1963—),男,广西桂林人,广西师范大学教授,博导。E-mail: edward_su75@163.com
  • 基金资助:
    国家自然科学基金资助项目(21262007);广西自然科学基金资助项目(2011GXNSFA018042)

Synthesis and Crystal Structure of Ethyl 5-acetamido-4-(4-chlorophenyl)-2-methyl-6-oxo-5, 6-dihydro-4H-pyran-3-carboxylate

LIANG Xiao-long1,2, HUANG Wan-yun3, PAN Cheng-xue1,2, SU Gui-fa1,2   

  1. 1. State Key Laboratory Cultivation Base for the Chemistry and Molecular Engineering of Medicinal Resources,Guangxi Normal University, Guilin Guangxi 541004, China;
    2. School of Chemistry and Pharmaceutical Sciences,Guangxi Normal University,Guilin Guangxi 541004, China;
    3. Department of Pharmaceutical Sciences, Guilin Medical University, Guilin Guangxi 541004, China
  • Received:2015-01-05 Online:2015-02-10 Published:2018-09-20

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摘要： 乙酰基甘氨酸与对氯苯甲醛通过经典的Erlenmeyer步骤合成了(Z)-2-甲基-4-对氯苯亚甲基-5(4H)-噁唑酮, 然后与乙酰乙酸乙酯在三乙胺催化下发生Michael加成, 之后经酮式烯醇式的互变, 再通过分子内的亲核加成得到5-乙酰胺基-4-(4-氯苯基)-2-甲基-6-氧代-5,6-二氢-4H-吡喃-3-羧酸乙酯,并用IR、NMR、MS及X-单晶衍射法对其结构进行研究。结果表明, 晶体结构属正交晶系,Pbca空间群,晶胞参数:a=1.189 29(13) nm, b=0.968 44(10) nm,c=3.172 1(2) nm,V=3.653 5(6) nm3,Z=8,Mr=351.77,Dc=1.279 Mg/m3,λ=0.071 073 nm,μ (MoKα)=0.234 mm-1,F(000)=1 472,最终偏离因子(对I>2σ (I)的1 413个衍射点)R=0.098 5,wR=0.245 4,化合物中的N—H和氧原子形成的分子间氢键使整个分子连接成一维链状的稳定结构。

关键词: 2-吡喃酮, 合成, 晶体结构

Abstract: Ethyl 5-acetamido-4-(4-chlorophenyl)-2-methyl-6-oxo-5,6-dihydro-4H-pyran-3-carboxylate, C17H18ClNO5, has been synthesized and characterized by IR, NMR, MS and single-crystal X-ray diffraction. The crystal is of orthorhombic, space group Pbca with a=1.189 29(13) nm, b=0.968 44(10) nm, c=3.172 1(2) nm, V=3.653 5(6) nm3, Z=8, Mr=351.77, Dc=1.279 Mg/m3, λ=0.071 073 nm, μ(MoKα)=0.234 mm-1, F (000)=1 472, the final R=0.098 5 and wR=0.245 4 for 141 3 observed reflections with I>2σ(I). The N—H and oxygen atom are involved in intermolecular hydrogen bonds which link the molecules into an one-dimensional chain and stabilize the structure.

Key words: 2-pyrone, synthesis, crystal structure

中图分类号: 

  • O622.5
[1] APPENDINO G, OTTINO M, MARQUEZ N, et al. An anti-inflammatory and anti-HIV-1 phloroglucinol-pyrone from Helichrysum italicum ssp. microphyllum[J]. J Nat Prod, 2007, 70:608-612.
[2] DUARTE F S, DUZZIONI M, MENDES B G, et al. Participation of dihydrostyryl-2-pyrones and styryl-2-pyrones in the central effects of Polygala sabulosa (Polygalaceae), a folk medicine topical anesthetic[J]. Pharmacology, Biochemistry and Behavior, 2007, 86:150-161.
[3] RUBAL J J, MORENO-DORADO F J, GUERRA F M, et al. A pyran-2-one and four meroterpenoids from Thapsia transtagana and their implication in the biosynthesis of transtaganolides[J]. Phytochemistry, 2007, 68:2480-2486.
[4] DIXIT M, RAGHUNANDAN R, KUMAR B, et al. One-pot regioselective synthesis of dihydronaphthofurans and dibenzofurans[J]. Tetrahedron, 2007, 63:1610-1616.
[5] BERTACCHE V, CONTINI A, ERBA E, et al. Synthesis of 4-dialkylaminopyridine derivatives through ring-rearrangement of 3-nitro-2H-pyran-2-one acetamidines[J]. Tetrahedron, 2007, 63:9652-9662.
[6] KUMAR A, SINGH F V, GOEL A. Regioselective synthesis of functionally hindered α-methyl-styrenes through ring transformation of 2H-pyran-2-ones with mesityl oxide[J]. Tetrahedron Lett, 2007, 48:8223-8226.
[7] NELSON H M, STOLTZ B M. Progress toward the synthesis of the basiliolides and transtaganolides:An intramolecular pyrone Diels-Alder entry into a novel class of natural products[J]. Org Lett, 2008, 10:25-28.
[8] SINGH F V, KUMAR A, GOEL A. Synthesis of o,m-cymene-cored biaryls through a carbanion-induced ring transformation strategy[J]. Tetrahedron Lett, 2006, 47:7767-7770.
[9] KIM W S, LEE J H, KANG J, et al. Diels-Alder cycloadditions of 3-phenylamino-5-bromo-2-pyrone for the synthesis of constrained α-amino acid derivatives[J]. Tetrahedron Lett, 2004, 45(8):1683-1687.
[10] MARRISON L R, DICKINSON J M, FAIRLAMB I J. Bioactive 4-substituted-6-methyl-2-pyrones with promising cytotoxicity against A2780 and K562 cell lines[J]. Bioorg Med Chem Lett, 2002, 12:3509-3513.
[11] MARRISON L R, DICKINSON J M, AHMED R, et al. An efficient synthesis of 4-alkenyl/alkynyl-6-methyl-2-pyrones via Pd-catalyzed coupling on 4-bromo-6-methyl-2-pyrone[J]. Tetrahedron Lett, 2002, 43:8853-8857.
[12] MARRISON L R, DICKINSON J M, FAIRLAMB I J. Suzuki cross-coupling approaches to the synthesis of bioactive 3-substituted and 5-substituted-4-methoxy-6-methyl-2-pyrones[J]. Bioorg Med Chem Lett, 2003, 13:2667-2671.
[13] VARA PRASAD J V N, PARA K S, LUNNEY E A, et al. Novel series of achiral, low molecular weight, and potent HIV-1 protease inhibitors[J]. J Am Chem Soc, 1994, 116:6989-6990.
[14] LEE Y S, KIM S N, LEE Y S, et al. Synthesis and HIV protease inhibitory activity of new 4-hydroxy-2-pyrone derivatives[J]. Arch Pharm, 2000, 333:319-322.
[15] SINGH F V, CHAURASIA S, JOSHI M D, et al. Synthesis and in vivo antihyperglycemmic activity of nature-mimicking furanyl-2-pyranones in STZ-S model[J]. Bioorg Med Chem Lett, 2007, 17:2425-2429.
[16] KRISHNA P R, SRINIVAS R. Stereoselective synthesis of (6S)-5,6-dihydro-6-[(2R)-2-hydroxy-6-phenylhexyl]-2H-pyran-2-one[J]. Tetrahedron:Asymmetry, 2007, 18:2197-2200.
[17] FUKUYAMA T, HIGASHIBEPPU Y, YAMAURA R, et al. Ru-catalyzed intermolecular [3+2+1] cycloaddition of α,β-unsaturated ketones with silylacetylenes and carbon monoxide leading to α-pyrones[J]. Org Lett, 2007, 9:587-589.
[18] KOMIYAMA T, TAKAGUCHI Y, TSUBOI S. Novel synthesis of 4-arylsulfenyl-3-hydroxy-2-pyrone:One-pot substitution-rearrangement-cyclization reaction of acetonide-protected 4,5-dihydroxy-2-chloroglycidic ester by sodium arylthiolate[J]. Heterocycles, 2005, 66:503-509.
[19] ZHU Xue-feng, SCHAFFNER A P, LI R C, et al. Phosphine-catalyzed synthesis of 6-substituted 2-pyrones:manifestation of E/Z-Isomerism in the Zwitterionic intermediate[J]. Org Lett, 2005, 7(14):2977-2980.
[20] KOMIYAMA T, TAKAGUCHI Y, GUBAIDULLIN A T, et al. Novel synthesis of 4-halo-3-hydroxy-2-pyrone:one pot rearrangement-cyclization reaction by magnesium halide[J]. Tetrahedron, 2005, 61(9):2541-2547.
[21] CHERRY K, PARRAIN J L, THIBONNET J, et al. Synthesis of isocoumarins and α-pyrones via tandem Stille reaction/heterocyclization[J]. J Org Chem, 2005, 70(17):6669-6675.
[22] PAN Cheng-xue, SU Gui-fa, QIN Jiang-ke. Diastereospecific synthesis of trans-2,3-diaryl-1-aminocyclo-propanecarboxylic acids[J]. Org Prep Proced Int, 2005, 37(3):239-246.
[23] SU Gui-fa, MU Hong-tao, ZA Dan-ming, et al. Stereospecific synthesis of trans-2,3-diaryl substituted 1-aminocyclopropanecarboxylic acid derivatives[J]. Synth Commun, 2003, 33(16):2873-2884.
[24] SHELDRICK G M. SHELXS-97, Program for the solution of crystal structures[CP/CD]. Göttingen, Germany:University of Göttingen, 1997.
[25] SHELDRICK G M. SHELXL-97, Program for the refinement of crystal structures[CP/CD]. Göttingen, Germany:University of Göttingen, 1997.
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