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3 protocols using 2 2 6 6 tetramethyl 3 5 heptanedione

1

Synthesis of Pyrazolone Derivatives

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All reactions were carried out in air unless otherwise stated. All solvents used were reagent grade, purchased from Sigma Aldrich and dried under nitrogen before use. 4-(Chloromethyl)benzoic acid, thionyl chloride, 1,3-diphenyl-1,3-propanedione, hydrazine monohydrate, sodium hydride, 2,2,6,6-tetramethyl-3,5-heptanedione, potassium hydroxide, benzyl bromide, benzyl chloride, sodium hydroxide, sodium bicarbonate, potassium tert-butoxide, ethyl acetate and glacial acetic acid were purchased from Sigma Aldrich and used without further purification. PdCl2 was purchased from Heraeus South Africa and used as received. [PdCl2(MeCN)2],22 3,5-di-tert-butylpyrazole,23 (link) 3,5-diphenylpyrazole24 (link) and methyl-4-(chloromethyl)benzoate25 (link) were synthesized according to literature procedures.
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2

Synthesis of 1,2,4-Triazolo[1,5-a]pyrimidine Derivatives

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The reagents: 3-amino-1,2,4-triazole, acetylacetone, 1,3-diphenyl-1,3-propanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, diphenyl sulfoxide, tetrahydrothiophene-1-oxide, and K2PtCl4 were purchased from Sigma Aldrich (St. Louis, MO, United States), whereas the inorganic salts and solvents of analytical grade from Avantor Performance Materials Poland S.A. (Gliwice, Poland). All chemicals and solvents obtained commercially were used without further purification.
The 5,7-disubstituted derivatives of 1,2,4-triazolo[1,5-a]pyrimidine were obtained according to the Bülow and Haas [19 (link),20 (link)] method by the condensation of 3-amino-1,2,4-triazole with corresponding diketones such as: acetylacetone for (dmtp), 6-methyl-2,4-heptanedione for (ibmtp), 2,2,6,6-tetramethyl-3,5-heptanedione for (dbtp) and 3,5-diphenyl-1,3-propanedione for (dptp).
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3

Synthesis of 1,2,4-Triazolo[1,5-a]pyrimidine Derivatives

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K2PtCl4, 3-amino-1,2,4-triazole (98%), 6-methyl-2,4-heptanedione (99%), 2,2,6,6-tetramethyl-3,5-heptanedione (98%), malonic acid and cyclobutane-1,1-dicarboxlic acid were purchased from Sigma Aldrich (Merck, St. Louis, MO, USA), whereas inorganic salts and solvents of analytical grade were purchased from Avantor Performance Materials Poland S.A (Gliwice, Poland).
5,7-Disubstituted derivatives of 1,2,4-triazolo[1,5-a]pyrimidines were prepared according to the Bülow and Haas method by the reaction of 3-amino-1,2,4-triazolewith 6-methyl-2,4-heptanedione for ibmtp and 2,2,6,6-tetramethyl-3,5-heptanedione for dbtp [28 (link)]. Disilver malonate (Ag2C3H2O4) and disilver cyclobutane-1,1-dicarboxylate (Ag2C6H6O4) were prepared by the reaction of AgNO3 with malonic or cyclobutane-1,1-dicarboxylic acid by a known method [29 (link)].
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