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Synthesis and antifungal activity of novel pyrazolecarboxamide derivatives containing a hydrazone moiety.

Wu J, Wang J, Hu D, He M, Jin L, Song B - Chem Cent J (2012)

Bottom Line: Their structures were characterized by 1 H-NMR, 13 C-NMR, IR, and elemental analysis.The activity of compounds 7a, 7f, 7g, 7h, 7i, 7j, 7l and 7q were 40.82%, 47.78%, 50.32%, 40.82%, 49.05%, 48.73%, 40.19% and 45.89%, respectively, and the synthesized compounds showed certain antifungal activities against F. oxysporum and C.mandshurica.A practical synthetic route to pyrazole amide derivatives containing a hydrazone moiety were synthesized by the condensation of intermediates 5-chloro-N-(4-subsititued-2-(hydrazinecarbonyl)-6-methylphenyl)-1,3-dimethyl-1 H-pyrazole-4-carboxamide with different aldehydes or ketones in ethanol at room temperature is presented, the results of the study suggested that the pyrazole amide derivatives containing hydrazone moieties could inhibit the growth of G. zeae, F. oxysporium and C. mandshurica to a certain extent.

View Article: PubMed Central - HTML - PubMed

Affiliation: State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang, China. basong@gzu.edu.cn.

ABSTRACT

Background: The plant pathogenic fungus (such as Gibberella zeae, Fusarium oxysporum and Cytospora mandshurica) causes devastating disease in agriculture. The pathogenic fungus is responsible for billions of dollars in economic losses worldwide each year. In order to discover new fungicidal molecule with good fungicidal activity against G. zeae, F. oxysporum, and C. mandshurica, we sought to combine the active sub-structure of hydrazone and pyrazole amide derivatives together to design and synthesize novel pyrazole amide derivatives containing a hydrazone moiety.

Results: A series of novel pyrazole amide derivatives bearing hydrazone moiety were synthesized. Their structures were characterized by 1 H-NMR, 13 C-NMR, IR, and elemental analysis. The preliminary biological assays revealed that most of the synthesized compounds exhibit favorable antifungal activities against G. zeae. The activity of compounds 7a, 7f, 7g, 7h, 7i, 7j, 7l and 7q were 40.82%, 47.78%, 50.32%, 40.82%, 49.05%, 48.73%, 40.19% and 45.89%, respectively, and the synthesized compounds showed certain antifungal activities against F. oxysporum and C.mandshurica.

Conclusion: A practical synthetic route to pyrazole amide derivatives containing a hydrazone moiety were synthesized by the condensation of intermediates 5-chloro-N-(4-subsititued-2-(hydrazinecarbonyl)-6-methylphenyl)-1,3-dimethyl-1 H-pyrazole-4-carboxamide with different aldehydes or ketones in ethanol at room temperature is presented, the results of the study suggested that the pyrazole amide derivatives containing hydrazone moieties could inhibit the growth of G. zeae, F. oxysporium and C. mandshurica to a certain extent.

No MeSH data available.


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Synthetic route to target compounds 7a-7s.
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C1: Synthetic route to target compounds 7a-7s.

Mentions: The synthetic route to the title compounds is outlined in Scheme1 [see Additional file1. Intermediates 4 were prepared using 1,3-dimethyl-1 H-pyrazol-5(4 H)-one as starting materials. 1,3-dimethyl-1 H-pyrazol-5(4 H)-one was firstly subjected to Vilsmeier-Haack chloroformylation using N,N-dimethylformamide (DMF) and phosphorus oxychloride (POCl3) to yield 5-chloro-1,3-dimethyl-1 H-pyrazole-4-carbaldehyde 1[9], which was further oxidized by potassium permanganate and following chlorinated with thionyl chloride (SOCl2) to provide the intermediates 3, then intermediates 4 were prepared by treating 5-chloro-1,3-dimethyl-1 H-pyrazole-4-carbonyl chloride with 2-amino-3-methylbenzoic acid or 5-chloro-2-amino-3-methylbenzoic acid in CH2Cl2 in present of triethylamine in good yields, 2-(5-chloro-1,3-dimethyl-1 H-pyrazol-4-yl)-8-methyl-4 H-benzod[1,3]oxazin-4-one 5 can be easily synthesized by reaction of acetic anhydride with 4 in excellent yield[21], however, it also can be prepared in a single step by the reaction of 3 with substituted 2-amino-3-methylbenzoic acid as describing in the literature[21,22]. Finally, compounds 6 were conveniently obtained with excellent yield (>90%) by treatment of 5 with 80% hydrazine hydrate, subsequent treatment of 6 with different ketones and aldehydes (or hemiacetals) in ethanol at room temperature afforded the desired compounds (7a to 7s) with excellent yields. The structures of all new compounds were confirmed by their spectra (IR, 1 H NMR, 13 C NMR) and elemental analytical data. Additional file shows the structures, yields and elemental analysis data for title compounds in more detail [see Additional file2. Moreover, hydrazone derivatives have two configurations due to the existence of double bond (C = N), for the title compounds, E and Z configuration can be observed in the 1 H-NMR spectra, and the E isomer was found predominantly, and the ratio between E and Z configuration can be calculated based on the integral area of E and Z isomers in 1 H-NMR spectra. Take compound 7k as an example, the E isomer of -CONHN proton can be found at δ 9.59, and the proton of Z isomer was appeared at δ 9.08, and the ratio of E isomer and Z isomer for 7k is 3.43, approximately.


Synthesis and antifungal activity of novel pyrazolecarboxamide derivatives containing a hydrazone moiety.

Wu J, Wang J, Hu D, He M, Jin L, Song B - Chem Cent J (2012)

Synthetic route to target compounds 7a-7s.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC3539435&req=5

C1: Synthetic route to target compounds 7a-7s.
Mentions: The synthetic route to the title compounds is outlined in Scheme1 [see Additional file1. Intermediates 4 were prepared using 1,3-dimethyl-1 H-pyrazol-5(4 H)-one as starting materials. 1,3-dimethyl-1 H-pyrazol-5(4 H)-one was firstly subjected to Vilsmeier-Haack chloroformylation using N,N-dimethylformamide (DMF) and phosphorus oxychloride (POCl3) to yield 5-chloro-1,3-dimethyl-1 H-pyrazole-4-carbaldehyde 1[9], which was further oxidized by potassium permanganate and following chlorinated with thionyl chloride (SOCl2) to provide the intermediates 3, then intermediates 4 were prepared by treating 5-chloro-1,3-dimethyl-1 H-pyrazole-4-carbonyl chloride with 2-amino-3-methylbenzoic acid or 5-chloro-2-amino-3-methylbenzoic acid in CH2Cl2 in present of triethylamine in good yields, 2-(5-chloro-1,3-dimethyl-1 H-pyrazol-4-yl)-8-methyl-4 H-benzod[1,3]oxazin-4-one 5 can be easily synthesized by reaction of acetic anhydride with 4 in excellent yield[21], however, it also can be prepared in a single step by the reaction of 3 with substituted 2-amino-3-methylbenzoic acid as describing in the literature[21,22]. Finally, compounds 6 were conveniently obtained with excellent yield (>90%) by treatment of 5 with 80% hydrazine hydrate, subsequent treatment of 6 with different ketones and aldehydes (or hemiacetals) in ethanol at room temperature afforded the desired compounds (7a to 7s) with excellent yields. The structures of all new compounds were confirmed by their spectra (IR, 1 H NMR, 13 C NMR) and elemental analytical data. Additional file shows the structures, yields and elemental analysis data for title compounds in more detail [see Additional file2. Moreover, hydrazone derivatives have two configurations due to the existence of double bond (C = N), for the title compounds, E and Z configuration can be observed in the 1 H-NMR spectra, and the E isomer was found predominantly, and the ratio between E and Z configuration can be calculated based on the integral area of E and Z isomers in 1 H-NMR spectra. Take compound 7k as an example, the E isomer of -CONHN proton can be found at δ 9.59, and the proton of Z isomer was appeared at δ 9.08, and the ratio of E isomer and Z isomer for 7k is 3.43, approximately.

Bottom Line: Their structures were characterized by 1 H-NMR, 13 C-NMR, IR, and elemental analysis.The activity of compounds 7a, 7f, 7g, 7h, 7i, 7j, 7l and 7q were 40.82%, 47.78%, 50.32%, 40.82%, 49.05%, 48.73%, 40.19% and 45.89%, respectively, and the synthesized compounds showed certain antifungal activities against F. oxysporum and C.mandshurica.A practical synthetic route to pyrazole amide derivatives containing a hydrazone moiety were synthesized by the condensation of intermediates 5-chloro-N-(4-subsititued-2-(hydrazinecarbonyl)-6-methylphenyl)-1,3-dimethyl-1 H-pyrazole-4-carboxamide with different aldehydes or ketones in ethanol at room temperature is presented, the results of the study suggested that the pyrazole amide derivatives containing hydrazone moieties could inhibit the growth of G. zeae, F. oxysporium and C. mandshurica to a certain extent.

View Article: PubMed Central - HTML - PubMed

Affiliation: State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang, China. basong@gzu.edu.cn.

ABSTRACT

Background: The plant pathogenic fungus (such as Gibberella zeae, Fusarium oxysporum and Cytospora mandshurica) causes devastating disease in agriculture. The pathogenic fungus is responsible for billions of dollars in economic losses worldwide each year. In order to discover new fungicidal molecule with good fungicidal activity against G. zeae, F. oxysporum, and C. mandshurica, we sought to combine the active sub-structure of hydrazone and pyrazole amide derivatives together to design and synthesize novel pyrazole amide derivatives containing a hydrazone moiety.

Results: A series of novel pyrazole amide derivatives bearing hydrazone moiety were synthesized. Their structures were characterized by 1 H-NMR, 13 C-NMR, IR, and elemental analysis. The preliminary biological assays revealed that most of the synthesized compounds exhibit favorable antifungal activities against G. zeae. The activity of compounds 7a, 7f, 7g, 7h, 7i, 7j, 7l and 7q were 40.82%, 47.78%, 50.32%, 40.82%, 49.05%, 48.73%, 40.19% and 45.89%, respectively, and the synthesized compounds showed certain antifungal activities against F. oxysporum and C.mandshurica.

Conclusion: A practical synthetic route to pyrazole amide derivatives containing a hydrazone moiety were synthesized by the condensation of intermediates 5-chloro-N-(4-subsititued-2-(hydrazinecarbonyl)-6-methylphenyl)-1,3-dimethyl-1 H-pyrazole-4-carboxamide with different aldehydes or ketones in ethanol at room temperature is presented, the results of the study suggested that the pyrazole amide derivatives containing hydrazone moieties could inhibit the growth of G. zeae, F. oxysporium and C. mandshurica to a certain extent.

No MeSH data available.


Related in: MedlinePlus