The Friedel-Crafts t-butylation of 2-naphthol

Stereospecific Ring-Opening Metathesis Polymerization of 3-Methyl-3-phenylcylopropene by Molybdenum Alkylidene Initiators

“…A THFfree version of 3a (3a′) could be prepared by reacting Mo(NAr)-(CHCMe 2 Ph)(2,5-Me 2 NC 4 H 2 ) 2 (Ar ) 2,6-diisopropylphenyl; 2,5-Me 2 NC 4 H 2 ) 2,5-dimethylpyrrolide) with 1 equiv of H 2 [Binaph C6F5 ] in CH 2 Cl 2 . 5 The 1 H and 13 C NMR spectra of poly(1) prepared using 3a′ were identical to those prepared using 3a, although the PDI of the polymer was somewhat higher. So at least in the case of the molybdenum initiator that contains the [Binaph C6F5 ] 2ligand, the presence of 1 equiv of THF or 2 equiv of 2,5-dimethylpyrrole during polymerization had no * To whom correspondence should be addressed.…”

“…Analogous biphenolate species 9 and 10 are isolated as THF-free species. 9 The 1 H NMR spectra of all polymers prepared with initiators 6-14 contained a broad olefinic proton resonance, while the 13 C NMR spectra revealed quaternary carbon resonances in the region between 46 and 47 ppm (as shown for several samples in Figure 4) and olefinic carbon resonances between 135 and 139 ppm. IR spectra of poly(1) prepared with 6, 7, 9, 11, and 14 again reveal IR absorptions at 963 and/or 982 cm -1 that are believed to be characteristic of trans CdC linkages; in poly(1) prepared with 6 or 9 the 982 cm -1 absorption dominates (see Supporting Information).…”

“…4 In Figure 1 are shown several recently reported molybdenum species 5 that contain new biphenolate or binaphtholate ligands. Polymerization of 1 6 using 2a yielded a polymer whose 13 C NMR spectrum (Figure 2) is characteristic of a relatively longrange order. In particular, a single sharp resonance is observed for the quaternary carbon atom at 46.05 ppm and for the olefinic carbon atom at 137.23 ppm.…”

“…An IR spectrum of poly(1) reveals absorbances at 963 and 982 cm -1 of approximately equal intensity that are not present in the spectrum of 1 and that are most consistent with the presence of trans CdC bonds in the polymer 7 (see Supporting Information). Therefore, we propose that poly(1) prepared with 2a has a trans and highly tactic (>99%) microstructure and that the 46.05 and 137.23 ppm resonances in the 13 C NMR spectrum are characteristic of that structure. The 1 H NMR spectrum of this polymer is also sharp and well-resolved.…”

“…Initiator 3a also afforded tactic trans-poly(1) with a relatively low PDI on the basis of 13 C NMR and GPC studies. A THFfree version of 3a (3a′) could be prepared by reacting Mo(NAr)-(CHCMe 2 Ph)(2,5-Me 2 NC 4 H 2 ) 2 (Ar ) 2,6-diisopropylphenyl; 2,5-Me 2 NC 4 H 2 ) 2,5-dimethylpyrrolide) with 1 equiv of H 2 [Binaph C6F5 ] in CH 2 Cl 2 .…”