Medium-Sized Cyclophanes, 29. Synthesis and Desulfurization of 2,11-Dithia[3]metacyclo- and 2,11-Dithia[3]paracyclo[3](4,9)pyrenophanes

✍ Scribed by Yamato, Takehiko ;Miyazawa, Akira ;Tashiro, Masashi

• Publisher: Wiley (John Wiley & Sons)
• Year: 1993
• Tongue: English
• Weight: 629 KB
• Volume: 126
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19931261126

✦ Synopsis

Cyclophanes 1 Benzenopyrenophane, 4,g-bridged 1 Sulfones, pyrolysis of Photodesulfurization [2]Naphthaleno[2]paracyclophane, 1,5-bridged 2,11-Dithia[3]metacyclo-(14 b) and 2,11-dithia[3]paracyclo[3]-extrusion by vapor-phase pyrolysis of the corresponding di-(4,g)pyrenophane (14c) were obtained by the coupling reac-sulfone 18 to the highly strained 19 clearly demonstrates the tions of 4,9-bis(chloromethyl)pyrene (12) with the correspond-limits of these preparative ring contraction method. The phoing bis(mercaptomethy1)benzenes (13b, c). Attempted pyroly-tolytic desulfurization of 14c afforded the 2naphthal- sis of the disulfones 18b, 18c to afford [2]metacyclo-(19b) and eno[2]paracyclophane analogue 21 instead of [2]paracyclo[l]-[2]paracyclo2pyrenophane (19c) failed. Only the ring (4,9)pyrenophane 21'. The mechanism of the pyrolysis and phocleavage products 16 and 20 were obtained. The sulfur dioxide tolysis reactions is discussed.

ortho-17% 2,7-di-tert-butylpyrene (7) in 10% yield. No I-acetylated 29% meta-trace compound was formed. 34% para-trace