Benzoxazole-2-thiones

Benzoxazole (L) derivatives of the stoichiometry M(XCN)2L2 (M = Zn or Cd X = S or Se) and Cd(NCSe)L have been prepared the former are pseudotetrahedral while the latter is polymeric. The ligand is N-bonded in all cases.460 Benzoxazole-2-thione (L) forms the similar MX2L2 complexes (M = Zn, Cd, Hg X = Cl, Br, I) and CdI2L coordination is through nitrogen, and not sulfur or oxygen.461... 

The tetrahydro-derivatives of the oxazole and isoxazole system are unstable. As a consequence, only acyclic products have been reported from the reductions with complex metal hydrides. 2,5-Diphenyl-oxazole (119) gave 2-benzylamino-l-phenylethanol (120),141 and 3,5-diphenyl-2-isoxazoline (121) was converted to 3-amino-l,3-diphenylpropanol (122)142 on reduction with lithium aluminum hydride. 3-Phenylbenzisoxazole was resistant to reduction with lithium aluminum hydride and sodium borohydride,143 but benz-oxazole (123), benzoxazol-2-one (124), and benzoxazol-2-thione (125) have been reported 141 to yield 2-methylaminophenol (126) on reduction with lithium aluminum hydride. 

The 2- and 5-aminooxazoles afford normal acyl and arenesulfonyl derivatives but attempts to diazotize the amino group have been unsuccessful. Oxazoles with a free amino group in position 4 are unknown, as are hydroxyoxazoles. 2-Methylthiooxazoles are produced when oxazole-2-thiones are methylated in alkaline solution. For the alkylation and benzoylation of benzoxazole-2-thione, see Section 4.18.3.1.4(ii). 

As shown in Equation (112), the photolytic reaction of benzoxazole-2-thione 132 with unsubstituted benzo[ ]furan 82 was utilized to make 2-benzofuryl-benzoxazole 133, but the yield is relatively low <2003HCA3255>. 

The complex reaction of dimethyl acetylenedicarboxylate with 2-methyl-benzoxazole in ethanol yields, inter alia, the benzoxazoloazepine (427), Both the S- and the A -acyl derivatives of benzoxazole-2-thione are effective acylating agents for amines and alcohols. ... 

Oxazolidine-2-thione Benzoxazole-2-thione 3-Methylbenzoxazole-2 -thione Benzothiazole-2 -thione 3-Methylbenzothiazole-2 -thione... 

Several thioureas have been synthesized by ring-opening reactions of heterocyclic compounds such as l,3-dithiolan-2-thiones, 5-arylimino-l,2,4-dithiazolidine-3-thiones, benzoxazole-2-thiones, and 3,1-benzo-thiazine-4-thione derivatives. Similarly, the action of triphenylphosphine on 5-amino-l,2,4-dithiazolo-3-thiones gave thiocarbamoyl isothiocyanates (304). Other thioureas have been obtained by thermolytic decarbonylation of 2-amino-5(4H)-thiazolones and by treatment of 4,5,6,7-tetrahydro-cyclopenta-l,3-dioxin-4-one" and 3-nitrophthalic anhydride with thiourea. ... 

Nishio, T, Mori Y., lida I., and Hosomi A., Photoaddition of benzoxazole-2-thiones with alkenes, /. Chem. Soc., Perkin Trans. 1, 921,1996. 

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