Pyrazolo pyrimidines with nucleophiles

Similar to haloazoles and haloazines, 7-halo-substituted pyrazolo[l,5-a]-pyrimidine underwent nucleophilic substitution with a variety of nucleophilic reagents to yield substituted pyrazolo[l,5-a]pyrimidines (74GEP2343702 76JAP761789 83AP697). Thus, 7-chloropyrazolo[l,5-a]pyrimidines 228, generally prepared from the 7-oxo derivatives 227 and phosphorus oxychloride, are converted into the 7-thioxo derivative 229 by the action of thio-... 

Bromo-4-chloro-lH-pyrazolo[3,4-d]pyrimidine could be easily fimc-tionalized at C-3 and C-4 in a one-pot two-step microwave-assisted process (Scheme 34) [55]. Ding and Schultz reported that nucleophilic substitution of the addition-elimination type at the C-4 position with amines and anilines smoothly occurred under acidic conditions in dioxane upon irradiation... 

An unusual reaction leading to the formation of 4-thioxopyrazolo[3,4-d]-pyrimidines has been reported. 1-Substituted 4-cyano-5-aminopyrazoles (103, R = H) react with phenyl isothiocyanate in dimethylformamide (DMF) saturated with hydrogen chloride to yield 1-substituted 4(5//)-pyrazolo[3,4-d]-pyrimidinethione (110). A proposed reaction sequence involved an initial nucleophilic addition of phenyl isothiocyanate to the protonated o-amino-nitrile to give an o-aminothioamide (108), followed by formylation by the dimethylformamide-hydrogen chloride mixture affording 109, which then cyclizes to the final product 110 (70MI1). 

N-acylated esters of (cyclohexa-l,4-dienyl)-L-alanine are ozonized aiming at the synthesis of novel uimatural amino acids. The combined reduction and ozonolysis followed by condensation with a suitable nucleophile results in transformation of the aromatic ring of L-Phe to isooxasolyl, N-phenylpyrazolyl and to bicyclic pyrazolo[l,5-a]pyrimidine groups. The preparation of heterocyclic alanine derivatives is reported [89]. 

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