铜催化一锅法合成1,2,4-三唑衍生物
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摘要
以亚胺酯盐酸盐和脒为原料,在铜催化下一锅法合成对称及非称二取代1,2,4-三唑衍生物。之前报道的合成方法仅限于合成对称芳基二取代1,2,4-三唑衍生物,在合成非对称二取代1,2,4-三唑时,由于底物的自聚和混聚造成不对称和对称的1,2,4-三唑产物同时产生,并且由于它们非常接近的R_f值而难以分离。该方法解决了从简单底物出发难以直接合成非对称芳基二取代1,2,4-三唑衍生物的问题,为合成非对称芳基二取代基1,2,4-三唑衍生物提供了一种有效的合成方法。
Symmetric and unsymmetric 3,5-disubstituted 1,2,4-triazole derivatives were synthesized from imidates and amidines under copper-catalyzed one-pot conditions.However,previous synthesis methods were restricted to synthesis of symmetric aryl-disubstituted 1,2,4-triazole derivatives,when unsymmetrical disubstituted 1,2,4-triazoles were synthesized,unsymmetricial and symmetrical 1,2,4-triazole products were simultaneously produced due to homogeneous and heterogeneous of the substrate,and they were difficult to separate due to their very close values of R_f.This paper solved the problem that unsymmetric aryl-disubstituted 1,2,4-triazole derivatives cannot be synthesized from readily available substrates,and provided an effective synthesis method for synthesizing unsymmetric aryl-disubstituted 1,2,4-triazole derivatives.
Symmetric and unsymmetric 3,5-disubstituted 1,2,4-triazole derivatives were synthesized from imidates and amidines under copper-catalyzed one-pot conditions.However,previous synthesis methods were restricted to synthesis of symmetric aryl-disubstituted 1,2,4-triazole derivatives,when unsymmetrical disubstituted 1,2,4-triazoles were synthesized,unsymmetricial and symmetrical 1,2,4-triazole products were simultaneously produced due to homogeneous and heterogeneous of the substrate,and they were difficult to separate due to their very close values of R_f.This paper solved the problem that unsymmetric aryl-disubstituted 1,2,4-triazole derivatives cannot be synthesized from readily available substrates,and provided an effective synthesis method for synthesizing unsymmetric aryl-disubstituted 1,2,4-triazole derivatives.
引文
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[17]Omodei-Salé A,Consonni P,Galliani G.A new class of nonhormonal pregnancy-terminating agents.synthesis and contragestational activity of 3,5-diaryl-s-triazoles[J].J Med Chem,1983,26(8):1 187-1 192.
[2]陈美航,罗兰,朱雪松,等.含1,2,4-三唑的肟酯类衍生物的合成与生物活性研究[J].化学研究与应用,2017,29(7):992-998.
[3]杨艳芳,林娟娟,李雪华,等.1,3-双苯并咪唑银配合物的合成、抗肿瘤活性及与DNA的相互作用研究[J].化学研究与应用,2018,30(7):1 106-1 113.
[4]周勇,张洪健,尹秀梅.7-取代-[1,2,4]三唑[1,5-a]嘧啶-5(4H)-酮衍生物的合成及抗炎活性的研究[J].化学研究与应用,2018,30(2):196-200.
[5]王俊岭,冯书晓,汪小伟,等.微波辅助新型含1,2,3-三唑基的α-氨基膦酸酯类化合物的合成及其晶体结构[J].化学研究与应用,2018,30(9):1 475-1 480.[5]Singh R,Anuja C H.Important methods of synthesis and biological significance of 1,2,4-triazole derivatives[J].J Pharm Pharm Sci,2014,3(8):874-906.
[6]Zhang H,Damu GLV,Cai G X,et al.Current developments in the syntheses of 1,2,4-triazole compounds.[J].Curr Org Chem,2015,18(3):359-406.
[7]米佳丽,周成合,白雪.含三唑的抗微生物药物研究进展[J].中国抗生素杂志,2007,32(10):587-593.
[8]周三女,吴先辉,田妍基,等.侧链含芳基亚甲胺基均三唑硫酮的合成、晶体结构及生物活性研究[J].化学研究与应用,2016,28(12):1 718-1 725.
[9]Bentiss F,Lagrenee M,Vezin H,et al.An improved procedure for the deamination of symmetrical 3,5-disubstituted 4-amino-1,2,4-triazoles[J].J Heterocycl Chem,2002,39(1):93-96.
[10]Li Z L,Zhang Z G,Zhang W,et al.Copper-mediated sequential C-N and N-N bond formation facile synthesis of symmetrical 1,2,4-triazoles[J].Synlett,2014,45(20):2 735-2 739.
[11]Sudheedra K,Schmidt D,Frey W,et al.Facile synthesis of 3,5-diaryl-1,2,4-triazoles via copper-catalyzed domino nucleophilic substitution/oxidative cyclization using amidines or imidates as substrates[J].Tetrahedron,2014,70(8):1 635-1 645.
[12]Ueda S,Nagawawa H.Facile synthesis of 1,2,4-triazoles via a copper-catalyzed tandem addition-oxidative cyclization[J].J Am Chem Soc,2009,131(42):15 080-15 081.
[13]Xu H,Ma S,Xu Y Q,et al.Copper-catalyzed one-pot synthesis of 1,2,4-triazoles from nitriles and hydroxyl-amine[J].J Org Chem,2015,80(3):1 789-1 794.
[14]Inturi S B,Kalita B,Ahamed A J.I2 mediated one-pot synthesis of 1,2,4-triazoles from amidines and imidat-es[J].Tetrahedron Lett,2016,47(37):2 227-2 230.
[15]Wang F,You Q,Wu C,et al.Mild Cu(OAc)2.H2O-catalyzed synthesis of multi-substituted 1,2,4-triazoles from amidines with nitriles via a N-N/C-N coupling[J].RSC Adv,2015,5(96):78 422-78 426.
[16]Samanta S K,Yli-Kauhaluoma J.Polymer-supported 1,3-oxazolium-5-olates:synthesis of 1,2,4-triazoles[J].J Comb Chem,2005,7(1):142-146.
[17]Omodei-Salé A,Consonni P,Galliani G.A new class of nonhormonal pregnancy-terminating agents.synthesis and contragestational activity of 3,5-diaryl-s-triazoles[J].J Med Chem,1983,26(8):1 187-1 192.