SYNTHESIS OF THE NOVEL HETEROCYCLIC SYSTEM 12Н-CHROMENO[3’,2’:3,4]PYRROLO[1,2-a]PYRIMIDIN-12-ONE
UDC 547.853
Keywords:
acylation, 2-chloromethyl-3-(4,6-dimethyl-2-pyrimidinyl)-6-ethyl-7-hydroxy-4H-4-chromenone, intramolecular cyclization, 2-pyrimidinylacetonitriles, α-pyrimidinyl-2,4-dihydroxyacetophenones, 12Н-chromeno[3',2':3,4]pyrrolo[1,2-a]pyrimidin-12-one.Abstract
The behavior of 2-pyrimidinylacetonitriles, such as 2-(4,6-dimethyl-2-pyrimidinyl)acetonitrile and 2-(2,6-dimethyl-4-pyrimidinyl)acetonitrile in Houben-Hoesch reaction was investigated. It was found that the result of the reaction depends on the structure of the starting nitrile. The reaction of 2-(4,6-dimethyl-2-pyrimidinyl)acetonitrile and resorcinol or 4-ethylresorcinol in BF3*Et2O with hydrogen chloride, followed by hydrolysis resulted in α-(4,6-dimethyl-2-pyrimidinyl)-2,4-dihydroxyacetophenones, while 2-(2,6-dimethyl-4-pyrimidinyl)acetonitrile in this reaction failed to give α-(2,6-
dimethyl-4-pyrimidinyl)-2,4-dihydroxyacetophenone because of the pyrimidine ring-opening. The interaction of α-(4,6-dimethyl-2-pyrimidinyl)-2,4-dihydroxyacetophenones with chloroacetyl chloride in acetonitrile in the presence of pyridine was investigated. α-(4,6-Dimethyl-2-pyrimidinyl)-2,4-dihydroxyacetophenones underwent acylation with chloroacetyl chloride, followed by cyclization to give 2-chloromethyl-7-chloroacetoxy-3-(4,6-dimethyl-2-pyrimidinyl)-4H-4-chromenones, which can undergo subsequent intramolecular cyclization with annelation of pyrrolopyrimidine ring to chromone core. A result of this reaction starting from α-(4,6-dimethyl-2-pyrimidinyl)-2,4-dihydroxyacetophenone is 2,4-dimethyl-12-oxo-12Н-chromeno[3’,2’:3,4]pyrrolo[1,2-a]pyrimidin-9-yl 2-chloroacetate, which is the derivative of the new heterocyclic system 12H-chromeno[3',2':3,4]pyrrolo[1,2-a]pyrimidin-12-one.
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