C. Stanciu, Alexander R. Fox, A. F. Richards
May 15, 2006
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0
Influential Citations
6
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Journal
Journal of Organometallic Chemistry
Abstract
Abstract The synthesis and characterization of several ipso-functionalized derivatives of the bulky terphenyl group C 6 H 3 - 2 , 6 ( C 6 H 3 - 2 ′ , 6 ′ - Pr 2 i ) 2 ( Ar ′ ) are described. These include the primary alcohol Ar′CH2OH (1), the bromo derivative Ar′CH2Br (2), and the terphenyl formate Ar′CH2OC(O)H (3). The alcohol 1 was obtained by treatment of LiAr′ with formaldehyde, and 1 was readily converted to the bromo derivative 2 using HBr. The reaction of 1 with formic acid afforded 3 in good yield. Attempts to form the Grignard derivative of 1, i.e., Ar′CH2MgBr, resulted in a head-to-tail reaction of the terphenyl benzyl units to yield an unusual coupled product 4. An approach to the avoidance of this coupling involved the synthesis of the terphenyl derivatives 1 - I - C 6 H 2 - 2 , 6 ( C 6 H 3 - 2 ′ , 6 ′ - Pr 2 i ) 2 - 4 - Me ( 5 ) and 1 - I - C 6 H 2 - 2 , 6 ( C 6 H 2 - 2 ′ , 4 ′ , 6 ′ - Pr 3 i ) 2 - 4 - Me ( 6 ) , bearing methyl groups in the para positions of the central aryl ring, which could be prepared in good yield, and converted to their respective lithium salts 7 and 8 without complication . The compounds were characterized by 1H and 13C NMR spectroscopy, IR spectroscopy (1) and X-ray crystallography (2, 4, 5 and 6).