The Sugiyama Diiodination of Lipophilic α, ϖ-Bis-Para-anisylalkanes

References

• Sugiyama , T. 1981 . Bull. Chem. Soc. Jpn. , 54 : 2847
   Web of Science ®Google Scholar
• Nomura , M. , Tokoroyama , T. and Kubota , T. 1974 . J. Chem. Soc. Chem. Comm. , : 65 alnusones, (b) asadanis, Yasue, M. Nippon Mokuzai Gakkaishi, 1965, 11(4), 146, (c) biphenomycins, Uchida, I., Shgematsu, N., Ezaki, M., Hashimoto, M., Aoki, H., Imanaka, H. J. Antibio., 1985, 38(11), 1462, and, Kaiman, R, Williams, D. H. J. Org. Chem., 1987, 52(24), 5435, (d) ellagitannin, Nonaka, G., Ishimaru, K., Watanabe, M, Nishiuka, I., Yamauchi, T., Wan, A. S. C. Chem. Pharm. Bull., 1987, 35(1), 217, (e) herquline, Furusaki, A., Matsumoto, T., Ogura, H., Takayanagi, H., Hirano, A., Omura, S. J. Chem. Soc. Chem. Comm., 1980, 15, 698, (f) lythraceous alkaloids, Fuji, K., Ichikawa, K., Fujita, E. J. Chem. Soc. Perk. Trans. I, 1980, 5, 1066, (g) medellines, Cortes, D., Saez, J., Hocquemiller, R., Cave, A., Cave, A. Heterocycles, 1986, 24(3), 607, (h) porsons, Anthonsen, T., Lorentzen, G. B., Matlerud, K. E. Acta. Chem. Scand., 1975, 29B, 529.
   Google Scholar
• Semmelhack , M. F. , Helquist , P. , Jones , L. D. , Keller , L. , Mendelson , L. , Ryono , L. S. , Smith , J. G. and Stauffer , R. D. 1981 . J. Am. Chem. Soc. , 103 : 6460
   Web of Science ®Google Scholar
• Hart , D. J. and Hong , W. 1985 . J. Org. Chem. , 50 : 3670 [n. 0]-meta-cyclophane couplings have been achieved in high yields only for systems in which the conformational freedom has been restricted, thus moderating the entropy barrier of the cyclization process. For example, see reference 3, and: (a) (b) Whiting, D. A., Wood, A. F. Tetrahedron Lett., 1978, 26, 2335.
   Web of Science ®Google Scholar
• Kadkhodayan , M. , Singleton , T. and Heldrich , F. J. 1984 . Synth. Comm. , 14 : 707 A similar method using CuBr/HMPA has been reported, but the yield of bis-arylation is lower: Nishimura, J., Yamada, N., Horiuchi, Y., Ueda, E., Ohbayashi, A., Oku, A. Bull. Chem. Soc. Jpn., 1986, 59, 2035.
   Web of Science ®Google Scholar
• Compounds isolated were pure by 1H NMR, indicating a purity in excess of 95%.
   Google Scholar
• The previously described method5 was followed up to the point of product purification. The crude product obtained was placed into a 500 mL flask and set in a normal Kugelrohr apparatus at 95–105°C and, 5 Pa. After 3–5 days, the distillate containing 4,4′-dimethoxybiphenyl and mono-arylated compound was removed, and the product isolated from the flask. 6 Further purification by recrystallization (C8) from 95% EtOH or flash chromatography (C7 & C9) with 2.5% EtOAc in hexanes provided analytically pure product.
   Google Scholar
• Still , W. C. , Kahn , M. and Mitra , A. 1978 . J. Org. Chem. , 43 : 2923
   Web of Science ®Google Scholar
• 1H NMR spectra were obtained on a Varian EM360L in CDCl3 solutions and are recorded in ppm (6) as referenced to TMS internal standard. Melting points were obtained on a Fisher-Johns apparatus and are uncorrected. IR spectra were recorded on a Mattson Polaris FT-IR as either oils or thin films deposited on sodium chloride plates by evaporation of CHCl3 solutions. Microanalyses were performed by Atlantic Microlabs, Inc., PO Box 2288, Norcross, Georgia. GC-MS analysis was performed on a HP 5890/HP 5971 A. Unoptimized yields are reported for the isolated, analytically pure materials. Tetra-n-butylammonium iodide and CAN were purchased from Aldrich Chemical Company. Reagent grade acetonitrile, flash silica gel, and dry column activated silica were purchased from Fischer Scientific. All commercial materials were used without purification.
   Google Scholar
• Product characterizations for the bis-arylations are listed below with yields given for isolated, analytically pure compounds. (a) 1,7-bis-para-anisylheptane: (46%) oil crystallized on standing, mp = 22–24°C. NMR, 7.14 (d, J = 8 Hz, 4H), 6.80 (d, J = 8 Hz, 4H), 3.77 (s, 6H), 2.52 (br t, J = 6 Hz, 4H), 1.00–1.88 (m, 10H), IR, 3059, 3029, 2928, 2853, 1612, 1512, 1464, 1441, 1245, 1037, 827 cm-1. Anal. Calcd for C21H28O2: C, 80.73, H, 9.03. Found: C, 80.61, H, 9.04. (b) 1,8-bis-para-anisyloctane: (38%) mp = 58–61°C. NMR, 7.12 (d, J = 10 Hz, 4H), 6.82 (d, J = 10 Hz, 4H), 3.77 (s, 6H), 2.54 (br t, J = 6 Hz, 4H), 1.04–1.89 (m, 12H), IR, 3059, 3038, 2921, 2847, 1612, 1513, 1462, 1441, 1252, 1032, 808 cm-1. Anal. Calcd for C22H30O2: C, 80.94, H, 9.26. Found: C, 80.72, H, 9.29. (c) 1,9-bis-para-anisylnonane: (47%) mp = 34–35°C. NMR, 7.12 (d, J = 10 Hz, 4H), 6.82 (d, J = 10 Hz, 4H), 3.76 (s, 6H), 2.54 (br t, J = 6 Hz, 4H), 1.03–1.88 (m, 14H), IR, 3040, 3013, 2923, 2850, 1611, 1512, 1465, 1245, 1030, 811 cm-1. Anal. Calcd for C23H32O2: C, 81.13, H, 9.47. Found: C, 80.88, H, 9.62.
   Google Scholar
• Merkushev , E. B. 1988 . Synthesis , : 923
   Web of Science ®Google Scholar
• Seoane , C. 1989 . Aldrichimica Acta , 22 ( 2 ) : 41
   Google Scholar
• Asakura , J. and Robbins , M. J. 1988 . Tetrahedron Lett. , 29 : 2855
   Web of Science ®Google Scholar
• Product characterizations for the diiodides with yields of analytical material isolated are listed below. (a) 1,5-bis-(3-iodo-4-methoxyphenyl)pentane: (38%) oil, NMR, 7.63 (d, J = 2 Hz, 2H), 7.12 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.72 (d, J = 8 Hz, 2H), 3.89 (s, 6H), 2.50 (br t, J = 6 Hz, 4H), 1.12–1.89 (m, 6H), IR, 3002, 2930, 2853, 1597, 1487, 1461, 1439, 1254, 1047, 809cm-1. Anal. Calcd for C19H22I2O2: C, 42.56, H, 4.14, I, 47.34. Found: C, 42.62, H, 4.15, I, 47.26. (b) 1,6-bis-(3-iodo-4-methoxyphenyl)hexane: (42%) mp = 100.5–102°C, NMR, 7.67 (d, J = 2 Hz, 2H), 7.20 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.78 (d, J = 8 Hz, 2H), 3.90 (s, 6H), 2.50 (br t, J = 6 Hz, 4H), 1.12–1.82 (m, 8H), IR, 3008, 2928, 2852, 1490, 1458, 1249, 1046, 813 cm-1. Anal. Calcd for C20H24I2O2: C, 43.66, H, 4.40, I, 46.13. Found: C, 43.56, H, 4.41, I, 46.22. (c) 1,7-bis-(3-iodo-4-methoxyphenyl)heptane: (38%) mp = 53–55°C, NMR, 7.68 (d, J = 2 Hz, 2H), 7.19 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.76 (d, J = 8 Hz, 2H), 3.85 (s, 6H), 2.50 (br t, J = 6 Hz, 4H), 1.07–1.85 (m, 10H), IR, 3002, 2926, 2852, 1491, 1461, 1439, 1250, 1048, 808 cm-1. Anal. Calcd for C21H26O2: C, 44.70, H, 4.64, I, 44.98. Found: C, 44.81, H, 4.68, I, 45.07. (d) 1,8-bis-(3-iodo-4-methoxyphenyl)octane: (49%) mp = 78–79°C, NMR, 7.64 (d, J = 2 Hz, 2H), 7.19 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.79 (d, J = 8 Hz, 2H), 3.89 (s, 6H), 2.50 (br t, J = 6 Hz, 4H), 1.14–1.83 (m, 12H), IR, 3013, 3002, 2930, 2851, 1596, 1491, 1459, 1435, 1255, 1045, 814cm-1. Anal. Calcd for C22H28I2O2: C, 45.69, H, 4.88, I, 43.89. Found: C, 45.81, H, 4.91, I, 43.77. (e) 1,9-bis-(3-iodo-4-methoxyphenyl)nonane: (25%) mp = 51–52°C, NMR, 7.76 (d, J = 2 Hz, 2H), 7.27 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.86 (d, J = 8 Hz, 2H), 3.92 (s, 6H), 2.56 (br t, J = 6 Hz, 4H), 1.14–1.89 (m, 14H), IR, 3002, 2926, 2852, 1598, 1492, 1461, 1439, 1252, 1049, 809 cm-1, MS (m/e), 592, 465, 353, 338, 296, 247. Anal. Calcd for C23H30I2O2: C, 46.64, H, 5.11, I, 42.85. Found: C, 46.75, H, 5.14, I, 42.79. (f) 1,10-bis-(3-iodo-4-methoxyphenyl)decane: (31%) mp = 65.5–67°C, NMR, 7.60 (d, J = 2 Hz, 2H), 7.10 (d of d, J = 8 Hz, J = 2 Hz, 2H), 6.70 (d, J = 8 Hz, 2H), 3.84 (s, 6H), 2.48 (br t, J = 6 Hz, 4H), 1.06–1.73 (m, 16H), IR, 3013, 3008, 2921, 2848, 1597, 1489, 1462, 1439, 1249, 1049, 807 cm-1. Anal. Calcd for C24H32I2O2: C, 47.54, H, 5.32, I, 41.86. Found: C, 47.61, H, 5.34, I, 41.92.
   Google Scholar
• Bohen , J. M. , Joullie , M. M. , Kaplan , F. A. and Loev , B. 1973 . J. Chem. Ed. , 50 ( 5 ) : 367
   Web of Science ®Google Scholar
• The two different crystalline forms occasionally will co-precipitate out of the eluent solution. The lower melting form has a mp of 43–44°C. It was not determined if this lower melting form was the result of solvent inclusion in the crystal lattice, although that seems probable.
   Google Scholar