Photodeoxygenation of phenanthro[4, 5-bcd]thiophene S-oxide, triphenyleno[1, 12-bcd]thiophene S-oxide and perylo[1, 12-bcd]thiophene S-oxide. (3rd September 2019)

• Record Type: Journal Article
• Authors: Chintala, Satyanarayana M.; Petroff II, John T.; Barnes, Andrew; McCulla, Ryan D.
• Is Part Of: Journal of sulfur chemistry. Volume 40:Number 5(2019)
• Page Start: 503
• Page End: 515
• Publication Date: 2019-09-03
• Subjects: Photodeoxygenation -- sulfoxides -- reactive oxygen species -- triplet oxygen -- toluene oxidation -- 1-octene oxidation -- polycyclic sulfoxide; Sulfur -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.72305
• DOI: 10.1080/17415993.2019.1615065
• Languages: English
• ISSNs: 1741-5993

Abstract

ABSTRACT: Sulfoxides, upon irradiation with ultraviolet (UV) light undergo α-cleavage, hydrogen abstraction, photodeoxygenation, bimolecular photoreduction, and stereo-mutation. The UV irradiation of dibenzothiophene S -oxide (DBTO) yields dibenzothiophene (DBT) as a major product along with ground-state atomic oxygen [O( 3 P)]. This is a common method for generating O( 3 P) in solution. The low quantum yield of photodeoxygenation and the requirement of UVA light are drawbacks of using this method. The sulfoxides benzo[ b ]naphtho-[1, 2, d ]thiophene S -oxide, benzo[ b ]naphtho [2, 1, d ]thiophene S -oxide, benzo[ b ] phenanthro[9, 10- d ]thiophene S -oxide, dinaphtho- [2, 1- b :1', 2'- d ]thiophene S -oxide, and dinaphtho[1, 2- b :2', 1'- d ]thiophene S -oxide have shown to deoxygenate up to three times faster than DBTO upon UVA irradiation; however, the photodeoxygenation of these sulfoxides does not appear to be limited to the production of O( 3 P). In this work, phenanthro[4, 5- bcd ]thiophene S -oxide, triphenyleno[1, 12- bcd ]thiophene- S -oxide, and perylo[1, 12- bcd ]thiophene- S -oxide were synthesized and their photodeoxygenation was studied. Phenanthro[4, 5- bcd ]thiophene- S -oxide, triphenyleno[1, 12- bcd ]thiophene- S -oxide, and perylo[1, 12- bcd ]thiophene- S -oxide deoxygenated upon UVA irradiation. However, the common intermediate experiments did not conclusively identify the photodeoxygenation mechanism of these sulfoxides. GRAPHICAL ABSTRACT: