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Synthesis of linear and angular furocoumarins with new skeleton structure of potential photobiological feature interest was carried out through Williamson reaction of hydroxycoumarins with 3-chloro-2-butanone followed by with polyphosphoric acid or by heating in a strongly alkaline solution. The reactions of synthesized furocoumarins were performed in chloroform and in the presence of tetraphenylporphyrin as singlet oxygen sensitizer (1O2). The reactions afforded the photocleaved product through [2 + 2] and the photooxygenated products through and [4 + 2] . The photoproducts were isolated and fully characterized by spectral analyses. [ABSTRACT FROM AUTHOR]