6.55 (d, J = 9.1 Hz, 1H), 6.06 (dd, J = 9.2, six.2 Hz, 1H), 5.98 (d, J = six.1 Hz, 1H), four.19-4.41 (m, 2H), 2.41 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H). 13C NMR (one hundred MHz): 153.six, 144.six, 138.5, 134.5, 132.5, 129.2, 128.9, 128.1, 128.0, 127.7, 126.8, 126.6, 125.9, 125.9, 125.2, 124.four, 124.two, 78.0, 67.eight, 62.5, 44.three, 21.7, 14.five. Anal. Calcd for C27H24N2O4S: C, 68.62; H, five.12; N, 5.93. Located: C, 68.82; H, 5.36; N, 5.66. N-Ethoxycarbonyl-1,2-dihydro-2-(N-phenyl-N-tosylaminoethynyl)-4,7-dichloroquinoline, 17. The reaction in between the ynamide (54.2 mg, 0.20 mmol) and 4,7-dichloroquinoline (47.5 mg, 0.24 mmol) was completed right after 20 h. Chromatographic purification (1:6 Et2O/hexanes) gave 95.0 mg (0.18 mmol, 88 ) of a slightly yellow oil. 1H NMR (400 MHz): 7.63 (s, 1H), 7.58 (d, J = eight.4 Hz,dx.doi.org/10.1021/jo500365h | J. Org. Chem. 2014, 79, 4167-The Journal of Organic Chemistry1H), 7.20-7.30 (m, 6H), 7.15-7.20 (m, 2H), six.92-6.97 (m, 2H), six.20 (d, J = six.9 Hz, 1H), 6.00 (d, J = six.eight Hz, 1H), 4.19-4.46 (m, 2H), 2.45 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H). 13C NMR (one hundred MHz) 152.7, 144.9, 138.three, 135.8, 134.7, 132.5, 129.three, 128.9, 128.2, 128.1, 125.9, 125.eight, 124.six, 124.2, 123.eight, 122.4, 79.three, 66.four, 63.1, 45.3, 21.7, 14.4. Anal. Calcd for C27H22Cl2N2O4S: C, 59.89; H, 4.10; N, 5.17. Located: C, 60.08; H, 4.N-(2-Hydroxyethyl)methacrylamide web 49; N, 5.28. N-Ethoxycarbonyl-1,2-dihydro-2-(N-phenyl-N-tosylaminoethynyl)-4-chloro-6-methoxyquinoline, 18. The reaction involving the ynamide (54.two mg, 0.20 mmol) and 4-chloro-6methoxyquinoline (46.five mg, 0.24 mmol) was completed soon after 2.five h. Chromatographic purification (1:four Et2O/hexanes) gave 88.1 mg (0.16 mmol, 82 ) of a slightly yellow oil. 1H NMR (400 MHz): 7.47 (s, 1H), 7.13-7.32 (m, 8H), 6.92-7.00 (m, 2H), six.90 (dd, J = 8.NH2-PEG1-CH2CH2-Boc Chemscene 9, 3.PMID:23381601 0 Hz, 1H), six.21 (d, J = 6.eight Hz, 1H), 6.01 (d, J = 7.0 Hz, 1H), 4.18-4.36 (m, 2H), three.87 (s, 3H), 2.43 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz): 156.six, 144.7, 138.five, 132.7, 130.0, 129.3, 128.9, 128.two, 128.1, 126.5, 125.9, 114.9, 109.7, 78.7, 66.7, 62.7, 55.7, 45.two, 21.7, 14.five. Anal. Calcd for C28H25ClN2O5S: C, 62.62; H, 4.69; N, 5.22. Discovered: C, 62.69; H, 5.02; N, five.28. N-Ethoxycarbonyl-5,6-dihydro-6-(N-phenyl-N-tosylaminoethynyl)phenanthridine, 19. The reaction amongst the ynamide (54.2 mg, 0.20 mmol) and phenanthridine (43.0 mg, 0.24 mmol) was completed right after three h. Chromatographic purification (1:three Et2O/ pentanes) gave 99.five mg (0.19 mmol, 95 ) of a colorless oil. 1H NMR (400 MHz): 7.76 (dd, J = 7.0 Hz, 7.0 Hz, 2H), 7.58 (m, 1H), 7.42 (m, 1H), 7.24-7.37 (m, 4H), 7.00-7.21 (m, 7H), six.71 (d, J = 7.7 Hz, 2H), 6.48 (s, 1H), four.16-4.37 (m, 2H), 2.41 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H). 13C NMR (one hundred MHz): 153.1, 144.four, 138.5, 135.0, 132.two, 130.7, 129.two, 128.8, 128.7, 128.1, 128.0, 127.eight, 125.7, 125.6, 125.1, 123.9, 78.9, 68.5, 62.5, 48.1, 21.7, 14.five. Anal. Calcd for C31H26N2O4S: C, 71.24; H, 5.01; N, 5.36. Identified: C, 70.89; H, five.26; N, 5.57.NoteASSOCIATED CONTENTS * Supporting InformationNMR spectra and crystallographic details. This material is obtainable free of charge of charge via the world wide web at http://pubs.acs.org.AUTHOR INFORMATIONCorresponding Author Notes*E-mail: [email protected]. The authors declare no competing economic interest.ACKNOWLEDGMENTS We gratefully acknowledge economic assistance in the National Institutes of Wellness (GM106260).
THE JOURNAL OF BIOLOGICAL CHEMISTRY VOL. 288, NO. 20, pp. 14068 ?4079, Might 17, 2013 ?2013 by The American Society for Biochemistry and Molecular Biology, Inc. Published inside the U.S.A.The Hyaluronan.