Benzoxadiazocines,benzothiadiazocines and benzotriazocines-IV : Ring closure of 1-(2-[n-(2-chloroethyl and 2-hydroxyethyl)-n-methylamino]phenyl)-3-phenylthioureas. tetrahydroquinoxaline vs.dihydro-3,1,6-benzothiadiazocine and hexahydro-1,3,6-benzotriazocinethione formation

While base induced ring closure of 1-(2-[N-(alkylsulfonyl and arylsulfonyl)-N-(2-chloroethyl)amino]phenyl)-3-phenylthioureas 1 had furnished the corresponding type 2 dihydro-3,1,6-benzothiadiazocine derivatives rather than the isomeric hexahydro-1,3,6-benzotriazocinethiones (3) or tetrahydroquinoxalines (4), base induced ring closure of the related N-(2-chloroethyl)-N-Me derivatives 9a-9c, 10a and lOb furnishes type 14 tetrahydroquinoxalines. 14a is obtained also by treating the N-(2-hydroxyethyl)-N-Me derivative 11 with the triphenylphosphine-diethyl azodicarboxylate (DEAD) reagent. In situ replacement of the chlorine atom of compound 9a by iodine in the absence of base as well as treatment of 1-(2-[N-(2-hydroxyethyl)-N-methylamino]phenyl)-1-methyl-3-phenylthiourea (18) with the triphenyl-phosphine-DEAD reagent furnishes the benzimidazole derivatives 16 and 22, respectively, whose formation may be rationalised by assuming the intermediacy of the dihydro- and tetrahydro-3,1,6-benzothiadiazocine derivatives 12a · HI and 20, respectively, and their subsequent ring contraction.