CH3), 1.76 (s, six H, CH3), 1.82 (s, six H, CH3), 1.85 (s, six H, CH3) ppm. 13C NMR (one hundred MHz, [D6]DMSO): = 29.95 (CH3), 28.27 (CH3), 30.45 (CH3), 31.18 (CH3), 33.35 (CH3), 34.52 (CH3), 60.97 (SCS), 61.67 (SCS), 62.63 (SCS), 127.30 (C), 128.49 (C), 131.29 (C), 137.08 (C), 138.European J Org Chem. Author manuscript; readily available in PMC 2014 April 24.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptRogozhnikova et al.Page(C), 140.44 (C), 141.79 (C), 142.89 (C), 157.40 (C), 169.07 (CO), 171.55 (CO) ppm. 13C NMR (150 MHz, CD3OD): = 29.50 (CH3), 31.08 (CH3), 32.24 (CH3), 33.25 (CH3), 34.66 (CH3), 62.86 (SCS), 63.77 (SCS), 64.00 (SCS), 129.30 (C), 130.44 (C), 131.01 (C), 139.22 (C), 140.36 (C), 140.99 (C), 141.59 (C), 143.82 (C), 145.54 (C), 157.39 (C), 173.96 (CO), 174.63 (CO) ppm. Spectra of quinoide 7 are given in Supporting Info.[Acr-Mes]+(ClO4)- Order Tris(2,two,six,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dithiol-4-yl)methyl (11) and Quinone Methide 12 A answer of 3 (0.200 g, 0.226 mmol) in anhydrous dichloromethane (two mL) and freshly distilled TFA (two mL)[26] was stirred at space temp. overnight below argon. The deep green solution was concentrated in vacuo to provide a black cake. The cake was dissolved in dichloromethane (four mL), and then water (two mL) was added. The mixture was stirred for 7 h beneath argon, as well as the green organic remedy gradually changed to a deep brown colour.Methyl 5-bromo-3-fluoro-2-methylbenzoate web The organic phase was separated, and water phase was extracted with DCM (three ?two mL).PMID:22664133 The combined organic extracts had been filtered by way of a quick cotton plug and concentrated in vacuo. Column chromatography on silica gel (dichloromethane/hexane, from 1:1 to five:1) afforded trityl 11 (0.115 g, 58.6 ) as a greenish-black powder (green in DCM answer) and quinoide 12 (0.054 g, 27.0 ) as a reddish-black powder. Information for 11: MS (ESI): calcd. for C37H39S12 [M]+ 866.970; discovered 866.964. MALDI-TOF: m/z = 867.04. IR (KBr): = 2974 (m), 2954 (m), 2920 (m), 2910 (m), 1452 (m), 1363 (s), 1342 (m), 1248 (s), 1169 (m), 1148 (s), 1103 (m), 849 (m), 644 (m)cm-1. UV/Vis (CH2Cl2): max (, Lmol-1cm-1) = 273 (55300), 325 (22300), 443 (21500) nm. ESR: 1:3:three:1 quartet H = 2.27 G; linewidth, 258 mG for 1 mM remedy in DCM; g = two.0055. Spectra of trityl 11 are given within the Supporting Facts. Data for 12: m.p. 260 (decomposition). MS (ESI): calcd. for C37H39OS12 [M + H]+ 882.965; found 882.964. IR (KBr): = 2957 (m), 2920 (s), 2912 (m), 1605 (s), 1468 (s), 1452 (s), 1364 (s), 1252 (m), 1150 (s), 1090 (m), 1030 (m), 733 (m) cm-1. UV/Vis (CH2Cl2): max (, Lmol-1cm-1) = 273 (47600), 517 (18000) nm. 1H NMR (600 MHz, CDCl3): = 1.70 (s, six H, CH3), 1.74 (s, 6 H, CH3), 1.77 (s, six H, CH3), 1.79 (s, six H, CH3), 1.87 (s, 6 H, CH3), 1.89 (s, six H, CH3), 7.07 (s, 2 H, CH) ppm. 13C NMR (150 MHz, CDCl3): = 29.66 (CH3), 30.07 (CH3), 31.42 (CH3), 31.66 (CH3), 31.88 (CH3), 33.63 (CH3), 62.81 (SCS), 64.72 (SCS), 65.86 (SCS), 119.08 (CH), 127.74 (C), 129.45 (C), 136.50 (C), 137.66 (C), 138.85 (C), 139.04 (C), 141.22 (C), 144.05 (C), 153.20 (C), 172.85 (CO) ppm. Spectra of quinoide 12 are presented in the Supporting Facts. Tris(2,2,six,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dithiol-4-yl)methyl (11) and Trityl 15 A remedy of three (0.134 g, 0.150 mmol) in anhydrous dichloromethane (2 mL) and freshly distilled TFA (two mL) was stirred at area temp. overnight below argon. The deep green option was concentrated in vacuo to give a black cake. The cake was dissolved in dichloromethane (four mL), and also the flask was flushed wi.
