Difluoroboron Chelation to Quinacridonequinone: A Synthetic Method for Air‐Sensitive 6, 13‐Dihydroxyquinacridone via Boron Complexes. Issue 9 (3rd April 2019)

• Record Type: Journal Article
• Authors: Moriya, Koichiro; Shimada, Ryohei; Ono, Katsuhiko
• Is Part Of: Chemistry, an Asian journal. Volume 14:Issue 9(2019)
• Page Start: 1452
• Page End: 1456
• Publication Date: 2019-04-03
• Subjects: boron -- chelates -- dyes/pigments -- hydrolysis -- reduction; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201900219
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: This study aims to perform the chelation of difluoroboron (BF2 ) to quinacridonequinone (QQ). The resulting dark green solid was determined to be QA‐BF2, which is a BF2 complex of 6, 13‐dihydroxyquinacridone (QA‐OH), and not QQ‐BF2, which is a BF2 complex of QQ. This result indicated that QQ‐BF2 was first generated as an O, O ‐bidentate chelate, which immediately underwent a two‐electron reduction to produce QA‐BF2 . This compound was converted to air‐sensitive QA‐OH by undergoing hydrolysis in argon. Since QA‐OH has a strong electron‐donating property, it easily produced QQ via air oxidation in the solution. QA‐OH also acts as a reducing reagent for quinones. The crystal packing of QA‐OH is a herringbone type with short π⋅⋅⋅π contacts, and a good hole mobility has been suggested by theoretical calculations. Herein, a new synthetic method from QQ to QA‐OH using BF2 chelation and hydrolysis was proposed. QA‐BF2 and QA‐OH are useful organic functional pigments and reducing reagents. Abstract : BF2 chelation to quinacridonequinone (QQ) was performed. The resulting dark green solid was a BF2 complex of 6, 13‐dihydroxyquinacridone (QA‐OH) and was determined to be QA‐BF2 . This compound underwent hydrolysis in argon to produce QA‐OH as a dark purple solid. Furthermore, QA‐OH was converted to QQ by air oxidation or in the presence of benzoquinone. In this study, a new synthetic method from QQ to QA‐OH via BF2 complexes was found.