A number of spiro[cyclopentane (cyclohexane, and cycloheptane)-1,4-perhydro- [1,3,2]diazaphosphole] derivatives (3a–c, 5a–c, 11a–c, and 12a–c) and spiro-[cyclopentane (cyclohexane, and cycloheptane)-1,4-perhydro[1,3,2]oxaazaphos-phole] derivatives (7a–c) were prepared via an interaction of 2,4-bis-(4-methoxy-phenyl)- 1,3,2,4-dithiaphosphetane-2,4-disulphide (1) with substances containing two functional groups.