Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1<i>H</i>-pyrazol-1-yl)methyl)-3<i>H</i>-1,2,4-triazole-3-thione Schiff Base

Citation: WANG Zi-Jian, SUN Xiao-Hong, LIU Yuan-Fa, CHEN Bang, JIN Ru-Yi, SHEN Sheng-Qiang, MA Hai-Xia. Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base[J]. Chinese Journal of Structural Chemistry, 2016, 35(2): 212-218. doi: 10.14102/j.cnki.0254-5861.2011-0892 shu

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

1.
a Chemical Research Institute, Northwest University, Xi'an 710069, China;
2.
b School of Chemical Engineering, Northwest University, Xi'an 710069, China;
3.
c College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China
基金项目:
This project was supported by the National Natural Science Foundation of China (No. 21373161) (No. 21373161)

Technological Projects of Shaanxi Province (No. 2013K02-25) (No. 2013K02-25)

摘要: The target compound 1,2,4-triazole Schiff base containing pyrazole ring was synthesized by 4-amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3- thione and 3,4,5-trimethoxy benzaldehyde. The structure was confirmed by IR, ¹H NMR, H RMS, elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.8772(17), b = 8.2986(18), c = 15.392(3) Å, α = 93.360(4), β = 94.609(4), γ = 93.584(4)°, C₁₈H₂₂N₆O₃S, M_r = 402.47, V = 998.9(4) Å³, Z = 2, F(000) = 422, D_c = 1.335 g/cm³, μ = 0.194 mm^-1, the final R = 0.0533 and wR = 0.1329 for 3517 observed reflections with I > 2σ(I). The preliminary bioassay results indicate that the target compound has good fungicidal activity against Gibberlla nicotiancola in EC₅₀ value and F. O. f. sp. niveum in EC₉₅ value.

关键词:

English

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

1.
a Chemical Research Institute, Northwest University, Xi'an 710069, China;
2.
b School of Chemical Engineering, Northwest University, Xi'an 710069, China;
3.
c College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China
Received Date: 11 July 2015
Fund Project:

Abstract: The target compound 1,2,4-triazole Schiff base containing pyrazole ring was synthesized by 4-amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3- thione and 3,4,5-trimethoxy benzaldehyde. The structure was confirmed by IR, ¹H NMR, H RMS, elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.8772(17), b = 8.2986(18), c = 15.392(3) Å, α = 93.360(4), β = 94.609(4), γ = 93.584(4)°, C₁₈H₂₂N₆O₃S, M_r = 402.47, V = 998.9(4) Å³, Z = 2, F(000) = 422, D_c = 1.335 g/cm³, μ = 0.194 mm^-1, the final R = 0.0533 and wR = 0.1329 for 3517 observed reflections with I > 2σ(I). The preliminary bioassay results indicate that the target compound has good fungicidal activity against Gibberlla nicotiancola in EC₅₀ value and F. O. f. sp. niveum in EC₉₅ value.

Key words:

1. [1]
  (1) Harshita, S.; Diksha, D.; Kapil, A.; Sarita, K.; Rekha, S. Synthesis, anti-inflamematory activity, and QSAR study of some Schiff bases derived from 5-mercapto-3-(40-pyridyl)-4H-1,2,4-triazol-4-yl-thiosemicarbazide. Med. Chem. Res. 2013, 22, 4953-4963.(1) Harshita, S.; Diksha, D.; Kapil, A.; Sarita, K.; Rekha, S. Synthesis, anti-inflamematory activity, and QSAR study of some Schiff bases derived from 5-mercapto-3-(40-pyridyl)-4H-1,2,4-triazol-4-yl-thiosemicarbazide. Med. Chem. Res. 2013, 22, 4953-4963.
2. [2]
  (2) Almasirad, A.; Tabatabai, S. A.; Faizi, M.; Kebriaeezadeh, A.; Mehrabi, N.; Dalvandia, A.; Shafiee, A. Synthesis and anticonvulsant activity of new 2-substituted-5-[2-(2-fluorophenoxy)phenyl]-1,3,4-oxadiazoles and 1,2,4-triazoles. Bioorg. Med. Chem. Lett. 2004, 14, 6057-6059.(2) Almasirad, A.; Tabatabai, S. A.; Faizi, M.; Kebriaeezadeh, A.; Mehrabi, N.; Dalvandia, A.; Shafiee, A. Synthesis and anticonvulsant activity of new 2-substituted-5-[2-(2-fluorophenoxy)phenyl]-1,3,4-oxadiazoles and 1,2,4-triazoles. Bioorg. Med. Chem. Lett. 2004, 14, 6057-6059.
3. [3]
  (3) Nikalje, A. P. G.; Ghodke, M. S.; Khan, F. A. K.; Sangshetti, J. N. CAN catalyzed one-pot synthesis and docking study of some novel substituted imidazole coupled 1,2,4-triazole-5-carboxylic acids as antifungal agents. Chin. Chem. Lett. 2015, 26, 108-112.(3) Nikalje, A. P. G.; Ghodke, M. S.; Khan, F. A. K.; Sangshetti, J. N. CAN catalyzed one-pot synthesis and docking study of some novel substituted imidazole coupled 1,2,4-triazole-5-carboxylic acids as antifungal agents. Chin. Chem. Lett. 2015, 26, 108-112.
4. [4]
  (4) Siddiqui, S. M.; Salahuddin, A.; Azam, A. Thiosemicarbazone fragment embedded within 1,2,4-triazole ring as inhibitors of Entamoeba histolytica. Bioorg. Med. Chem. Lett. 2012, 22, 2768-2771.(4) Siddiqui, S. M.; Salahuddin, A.; Azam, A. Thiosemicarbazone fragment embedded within 1,2,4-triazole ring as inhibitors of Entamoeba histolytica. Bioorg. Med. Chem. Lett. 2012, 22, 2768-2771.
5. [5]
  (5) Özdemir, A.; Turan-Zitouni, G.; Asim, Kaplancikli. Z. Synthesis of some 4-arylidenamino-4H-1,2,4-triazole-3-thiols and their antituberculosis activity. J. Enzym. Inhib. Med. Chem. 2007, 22, 511-516.(5) Özdemir, A.; Turan-Zitouni, G.; Asim, Kaplancikli. Z. Synthesis of some 4-arylidenamino-4H-1,2,4-triazole-3-thiols and their antituberculosis activity. J. Enzym. Inhib. Med. Chem. 2007, 22, 511-516.
6. [6]
  (6) Kumar, G. V. S.; Rajendraprasad, Y.; Mallikarjuna, B. P. Synthesis of some novel 2-substituted-5-[isopropylthiazole] clubbed 1,2,4-triazole and 1,3,4-oxadiazoles as potential antimicrobial and antitubercular agents. Eur. J. Med. Chem. 2010, 45, 2063-2074.(6) Kumar, G. V. S.; Rajendraprasad, Y.; Mallikarjuna, B. P. Synthesis of some novel 2-substituted-5-[isopropylthiazole] clubbed 1,2,4-triazole and 1,3,4-oxadiazoles as potential antimicrobial and antitubercular agents. Eur. J. Med. Chem. 2010, 45, 2063-2074.
7. [7]
  (7) Lin, R.; Connolly, P. J.; Huang, S.; Wetter, S. K.; Lu, Y.; Murray, W. V.; Emanuel, S. L.; Gruninger, R. H.; Robert, H. 1-Acyl-1H-[1,2,4]triazole-3,5-diamine analogues as novel and potent anticancer cyclin-dependent kinase inhibitors: synthesis and evaluation of biological activities. J. Med. Chem. 2005, 48, 4208-4211.(7) Lin, R.; Connolly, P. J.; Huang, S.; Wetter, S. K.; Lu, Y.; Murray, W. V.; Emanuel, S. L.; Gruninger, R. H.; Robert, H. 1-Acyl-1H-[1,2,4]triazole-3,5-diamine analogues as novel and potent anticancer cyclin-dependent kinase inhibitors: synthesis and evaluation of biological activities. J. Med. Chem. 2005, 48, 4208-4211.
8. [8]
  (8) Witkowski, J. T.; Robins, R. K.; Sidwell, R. W.; Simon, L. N. Design, synthesis, and broad spectrum antiviral activity of 1-D-ribofuranosyl-1,2,4-triazole-3- carboxamide and related nucleosides. J. Med. Chem. 1972, 15, 1150-1154.(8) Witkowski, J. T.; Robins, R. K.; Sidwell, R. W.; Simon, L. N. Design, synthesis, and broad spectrum antiviral activity of 1-D-ribofuranosyl-1,2,4-triazole-3- carboxamide and related nucleosides. J. Med. Chem. 1972, 15, 1150-1154.
9. [9]
  (9) Sim, K. M.; Loo, S. T.; Teo, K. C. Synthesis, characterization, antibacterial and free radical scavenging activities of some new 1,2,4-triazole Schiff bases and Mannich bases. Lett. Org. Chem. 2014, 11, 564-572.(9) Sim, K. M.; Loo, S. T.; Teo, K. C. Synthesis, characterization, antibacterial and free radical scavenging activities of some new 1,2,4-triazole Schiff bases and Mannich bases. Lett. Org. Chem. 2014, 11, 564-572.
10. [10]
  (10) Chohan, Z. H.; Hanif, M. Synthesis and characterization of biologically active new Schiff bases containing 3-functionalized 1,2,4-triazoles and their zinc(II) complexes: crystal structure of 4-bromo-2-[(E)-(1H-1,2,4-triazol-3-ylimino)-methyl]phenol. Appl. Org. Chem. 2011, 25, 753-760.(10) Chohan, Z. H.; Hanif, M. Synthesis and characterization of biologically active new Schiff bases containing 3-functionalized 1,2,4-triazoles and their zinc(II) complexes: crystal structure of 4-bromo-2-[(E)-(1H-1,2,4-triazol-3-ylimino)-methyl]phenol. Appl. Org. Chem. 2011, 25, 753-760.
11. [11]
  (11) Sun, X. H.; Bai, Y.; Liu, Y. F.; Chen, B. Synthesis, structure and biological activities of 3-substituted phenoxymethyl-4-amino- 1,2,4-triazol-5-thione Schiff bases. Acta Chim. Sinica 2010, 68, 788-792.(11) Sun, X. H.; Bai, Y.; Liu, Y. F.; Chen, B. Synthesis, structure and biological activities of 3-substituted phenoxymethyl-4-amino- 1,2,4-triazol-5-thione Schiff bases. Acta Chim. Sinica 2010, 68, 788-792.
12. [12]
  (12) Altalbawy, F. M. A.; Mohamed, G. G.; Mohamed, M. I. A. Synthesis, characterization and biological activity of some transition metals complexes with Schiff base derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol and p-methoxysalicyldehyde. Asian. J. Chem. 2010, 22, 7291-7307.(12) Altalbawy, F. M. A.; Mohamed, G. G.; Mohamed, M. I. A. Synthesis, characterization and biological activity of some transition metals complexes with Schiff base derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol and p-methoxysalicyldehyde. Asian. J. Chem. 2010, 22, 7291-7307.
13. [13]
  (13) Bekhit, A. A.; Hassan, A. M.; Abd EI Razik, H. A.; EI-Miligy, M. M.; EI-Agroudy, E. J.; Bekhit, A. A. New heterocyclic hybrids of pyrazole and its bioisosteres: design, synthesis and biological evaluation as dual acting antimala-rial-antileishmanial agents. Eur. J. Med. Chem. 2015, 94, 30-44.(13) Bekhit, A. A.; Hassan, A. M.; Abd EI Razik, H. A.; EI-Miligy, M. M.; EI-Agroudy, E. J.; Bekhit, A. A. New heterocyclic hybrids of pyrazole and its bioisosteres: design, synthesis and biological evaluation as dual acting antimala-rial-antileishmanial agents. Eur. J. Med. Chem. 2015, 94, 30-44.
14. [14]
  (14) Selvam, T. P.; Kumar, P. V.; Saravanan, G.; Prakash, C. R. Microwave-assisted synthesis, characterization and biological activity of novel pyrazole derivatives. J. Saudi. Chem. Soc. 2014, 18, 1015-1021.(14) Selvam, T. P.; Kumar, P. V.; Saravanan, G.; Prakash, C. R. Microwave-assisted synthesis, characterization and biological activity of novel pyrazole derivatives. J. Saudi. Chem. Soc. 2014, 18, 1015-1021.
15. [15]
  (15) Mert, S.; Kasimogullari, R.; Lca, T.; Colak, F.; Altun, A.; Ok, S. Synthesis, structure-activity relationships, and in vitro antibacterial and antifungal activity evaluations of novel pyrazole carboxylic and dicarboxylic acid derivatives. Eur. J. Med. Chem. 2014, 78, 86-96.(15) Mert, S.; Kasimogullari, R.; Lca, T.; Colak, F.; Altun, A.; Ok, S. Synthesis, structure-activity relationships, and in vitro antibacterial and antifungal activity evaluations of novel pyrazole carboxylic and dicarboxylic acid derivatives. Eur. J. Med. Chem. 2014, 78, 86-96.
16. [16]
  (16) Nitulescu, G. M.; Draghici, C.; Olaru, O. T. New potential antitumor pyrazole derivatives: synthesis and cytotoxic evaluation. Int. J. Mol. Sci. 2013, 14, 21805-21818.(16) Nitulescu, G. M.; Draghici, C.; Olaru, O. T. New potential antitumor pyrazole derivatives: synthesis and cytotoxic evaluation. Int. J. Mol. Sci. 2013, 14, 21805-21818.
17. [17]
  (17) Pinna, G.; Loriga, G.; Pinna, G. A.; Chelucci, G. Synthesis of tricyclic condensed rings incorporating the pyrazole or isoxazole moieties bonded to 4-piperidinyl substituent. Molecules 2013, 18, 8147-8159.(17) Pinna, G.; Loriga, G.; Pinna, G. A.; Chelucci, G. Synthesis of tricyclic condensed rings incorporating the pyrazole or isoxazole moieties bonded to 4-piperidinyl substituent. Molecules 2013, 18, 8147-8159.
18. [18]
  (18) Ma, H. J.; Zhang, J. H.; Xia, X. D.; Xu, M. H.; Ning, J.; Li, J. H. Design, synthesis and herbicidal activities of novel 4-(1H-pyrazol-1-yl)-6-(alkynyloxy) pyrimidine derivatives as potential pigment biosynthesis inhibitors. Pest. Manag. Sci. 2014, 70, 946-952.(18) Ma, H. J.; Zhang, J. H.; Xia, X. D.; Xu, M. H.; Ning, J.; Li, J. H. Design, synthesis and herbicidal activities of novel 4-(1H-pyrazol-1-yl)-6-(alkynyloxy) pyrimidine derivatives as potential pigment biosynthesis inhibitors. Pest. Manag. Sci. 2014, 70, 946-952.
19. [19]
  (19) Sun, N. B.; Tong, J. Y.; Wu, H. K. Synthesis and fungicidal activity of 1,3,4-oxadiazole derivatives containing pyrazole moiety. Chin. J. Org. Chem. 2013, 33, 101-105.(19) Sun, N. B.; Tong, J. Y.; Wu, H. K. Synthesis and fungicidal activity of 1,3,4-oxadiazole derivatives containing pyrazole moiety. Chin. J. Org. Chem. 2013, 33, 101-105.
20. [20]
  (20) Sheldrick, G. M. SHELXS-97. Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997.(20) Sheldrick, G. M. SHELXS-97. Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997.
21. [21]
  (21) Sheldrick, G. M. SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997.(21) Sheldrick, G. M. SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997.
22. [22]
  (22) Sun, X. H.; Bai, Y.; Liu, Y. F.; Chen, B.; Jia, Y. Q. Synthesis and biological activities of derivatives of 3,6-diphenoxymethyl-1,2,4-triazolo [3,4-b]-1,3,4-thiadiazoles. Chem. J. Chin. U. 2011, 32, 1312-1317.(22) Sun, X. H.; Bai, Y.; Liu, Y. F.; Chen, B.; Jia, Y. Q. Synthesis and biological activities of derivatives of 3,6-diphenoxymethyl-1,2,4-triazolo [3,4-b]-1,3,4-thiadiazoles. Chem. J. Chin. U. 2011, 32, 1312-1317.
23. [23]
  (23) Pan, X. Q.; Huang, S. S.; Wang, F.; Fan, H.; Leng, H.; Zhang, H. L.; Diao, Y. P. Synthesis, crystal structure and antibacterial activity of two hydrazones derived from 2-fluorobenzhydrazide. Chin. J. Struct. Chem. 2013, 32, 142-148.(23) Pan, X. Q.; Huang, S. S.; Wang, F.; Fan, H.; Leng, H.; Zhang, H. L.; Diao, Y. P. Synthesis, crystal structure and antibacterial activity of two hydrazones derived from 2-fluorobenzhydrazide. Chin. J. Struct. Chem. 2013, 32, 142-148.
24. [24]
  (24) Jin, R. Y.; Sun, X. H.; Liu, Y. F.; Chen, B.; Shen, S. Q.; Ma, H. X. Synthesis, structure and biological activity of 5-benzyl-4-amino-1,2,4-triazole- 3-thione Schiff base. Chin. J. Struct. Chem. 2014, 33, 253-257.(24) Jin, R. Y.; Sun, X. H.; Liu, Y. F.; Chen, B.; Shen, S. Q.; Ma, H. X. Synthesis, structure and biological activity of 5-benzyl-4-amino-1,2,4-triazole- 3-thione Schiff base. Chin. J. Struct. Chem. 2014, 33, 253-257.

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 1828
HTML全文浏览量: 37

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

English

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

English

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs