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C, 43.50; H, 4.75; O, 5.79; I, 45.96%; UV lmax (CH3CN)/nm 283 (CH3CN)/nm 281(log 3 4.10) and 203 (4.98); FTIR (neat) nmax
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(log 3 3.23), 233 (3.93) and 205.5 (4.46); FTIR (neat) nmax/cmꢀ1 cmꢀ1 3457, 2958, 2926, 2870, 1611, 1391, 1158, 905, 854, 731,
3382, 2962, 2874, 1543, 1463, 1386, 1377, 1295, 1228, 1157, 886, 602; RI (DB-5MS) 2923; EIMS m/z 550 (M+, 100%), 535 (46.9), 393
880, 707, 570; RI (DB-5MS) 1692; EIMS m/z 276 (M+, 79.8%), 262 (20.6), 381 (16.4), 380 (14.2), 260 (15.4), 253 (21.3), 212 (13.8), 211
(9.9), 261 (100), 134 (39.6), 133 (6.1), 116 (7.0), 115 (11.8), 91 (20.4); For 1H and 13C NMR spectra, see Table 2.
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(9.1), 77 (8.6); For H and 13C NMR spectra, see Table 1.
2,4-Diiodo-6-isopropyl-3-methylphenol (o,p-diiodothymol)
(13). White amorphous solid; relative content in aristol: 12.8%;
Methylation of compounds 7, 10–15
elemental analysis found: C, 29.69; H, 2.82. Calc. for C10H12I2O: A phenol (7, 10, 11, 12, 13, 14, or 15, 0.1 mmol) was added to
C, 29.88; H, 3.01; O, 3.98; I, 63.13%; UV lmax (CH3CN)/nm 285 a suspension of anhydrous potassium carbonate (30 mg, 0.2
(log 3 3.45) and 214.5 (4.66); FTIR (neat) nmax/cmꢀ1 3462, 2959, mmol) in DMF (5 mL). Methyl iodide (30 mg, 0.21 mmol) was
2866, 1633, 1581, 1442, 1470, 1386, 1203, 1165, 882, 631, 590; RI then added and the solution was stirred at room temperature
(DB-5MS) 1933; EIMS m/z 402 (M+, 91.2%), 388 (9.8), 387 (100), for 24 h. Aer that, water was added and the reaction mixture
260 (27.8), 133 (9.5), 115 (7.9), 105 (9.7), 103 (6.3), 77 (9.8); For was extracted three times with Et2O. The combined organic
1H and 13C NMR spectra, see Table 1.
extracts were washed excessively with brine, and the DMF-free
3,30-Diiodo-5,50-diisopropyl-2,20-dimethyl-[1,10-biphenyl]-4,40- ether extract was dried over anhydrous MgSO4 and concen-
diol (14). White amorphous solid; relative content in aristol: trated in vacuo. The crude methylation products were directly
1.5%; elemental analysis found: C, 43.82; H, 4.29. Calc. for analysed by GC-MS.32
C
20H24I2O2: C, 43.66; H, 4.40; O, 5.82; I, 46.12%; UV lmax
Spectral characterization of the methylated compounds:
(CH3CN)/nm 282.5 (log 3 3.73) and 208 (4.81); FTIR (neat) nmax
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1-Isopropyl-2-methoxy-4-methylbenzene. RI (DB-5MS) 1237;
cmꢀ1 3473, 2959, 2866, 1728, 1662, 1596, 1458, 1391, 1162, EIMS m/z 164 (M+, 27.3%), 150 (11.0), 149 (100), 134 (7.3), 119
1117, 1020, 884, 800, 609, 570; RI (DB-5MS) 2892; EIMS m/z 550 (11.7), 117 (8.7), 115 (8.0), 105 (5.9), 91 (16.6), 77 (6.4).
(M+, 100%), 536 (15.4), 535 (75.7), 393 (5.6), 380 (7.6), 365 (7.3),
2-Iodo-4-isopropyl-3-methoxy-1-methylbenzene. RI (DB-5MS)
260 (29.2), 196 (6.7), 165 (7.1); For 1H and 13C NMR spectra, see 1517; EIMS m/z 290 (M+, 75.3%), 275 (100), 260 (13.6), 148 (13.2),
Table 2.
133 (11.2), 118 (21.6), 117 (12.5), 115 (12.1), 105 (13.2), 77 (11.0).
5,50-Diiodo-3,30-diisopropyl-6,60-dimethyl-[1,10-biphenyl]-2,20-
1-Iodo-5-isopropyl-4-methoxy-2-methylbenzene. RI (DB-5MS)
diol (7). White amorphous solid; relative content in aristol: 1609; EIMS m/z 290 (M+, 65.4%), 276 (13.2), 275 (100), 260 (9.4),
1.0%; elemental analysis found: C, 43.43; H, 4.61. Calc. for 148 (13.2), 133 (10.0), 118 (14.6), 117 (10.6), 115 (11.1), 77 (8.0).
C20H24I2O2: C, 43.66; H, 4.40; O, 5.82; I, 46.12%; UV lmax
1,3-Diiodo-5-isopropyl-4-methoxy-2-methylbenzene. RI (DB-
5MS) 1956; EIMS m/z 416 (M+, 100%), 401 (56.7), 402 (6.2),
(CH3CN)/nm 282.5 (log 3 3.69) and 208 (4.78); FTIR (neat) nmax
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cmꢀ1 3480, 2952, 2875, 1738, 1657, 1590, 1464, 1168, 880, 806, 386 (14.5), 274 (16.6), 244 (8.2), 117 (13.1), 115 (11.7), 91 (8.8), 77
601, 574; RI (DB-5MS) 2863; EIMS m/z 550 (M+, 100%), 536 (9.8), (8.4).
535 (52.0), 493 (9.1), 393 (8.1), 366 (9.7), 267 (9.8), 260 (24.4), 165
(7.7); For 1H and 13C NMR spectra, see Table 2.
3,30-Diiodo-5,50-diisopropyl-4,40-dimethoxy-2,20-dimethyl-1,10-
biphenyl. RI (DB-5MS) 2894; EIMS m/z 578 (M+, 100%), 564 (7.2),
2-Iodo-4-(4-iodo-2-isopropyl-5-methylphenoxy)-6-isopropyl-3- 563 (31.7), 452 (7.6), 437 (7.1), 274 (16.7), 266 (7.3), 178 (5.8), 165
methylphenol (15). White amorphous solid; relative content in (6.8), 128 (5.6).
aristol: 29.3%; elemental analysis found: C, 43.81; H, 4.26. Calc.
for C20H24I2O2: C, 43.66; H, 4.40; O, 5.82; I, 46.12%; UV lmax biphenyl. RI (DB-5MS) 2824; EIMS m/z 578 (M+, 100%), 563
(CH3CN)/nm 283.5 (log 3 3.61) and 206 (4.72); FTIR (neat) nmax (18.0), 452 (18.5), 437 (14.1), 436 (13.1), 421 (12.8), 394 (10.3), 274
3,30-Diiodo-5,50-diisopropyl-6,60-dimethoxy-2,20-dimethyl-1,10-
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cmꢀ1 3479, 2959, 2921, 2866, 1548, 1465, 1402, 1336, 1237, 1163, (15.6), 165 (7.4), 128 (7.2).
883, 853, 630; RI (DB-5MS) 2801; EIMS m/z 550 (M+, 100%), 535
3-Iodo-1-(4-iodo-2-isopropyl-5-methylphenoxy)-5-isopropyl-4-
(10.0), 393 (22.1), 351 (19.1), 275 (13.5), 274 (18.5), 260 (11.7), 115 methoxy-2-methylbenzene. RI (DB-5MS) 2800; EIMS m/z 564
(13.3), 91 (10.5). For 1H and 13C NMR spectra, see Table 2.
(M+, 100%), 438 (13.9), 407 (12.7), 275 (16.5), 274 (36.2), 148
4-(5-Hydroxy-2-iodo-4-isopropylbenzyl)-2-isopropyl-5-methyl- (29.5), 117 (19.4), 115 (19.4), 91 (19.0), 77 (9.7).
phenol (16). White amorphous solid; relative content in aristol:
1.2%; elemental analysis found: C, 56.80; H, 5.75. Calc. for
Oxidative coupling20 of thymol
C
20H24I2O2: C, 56.61; H, 5.90; O, 7.54; I, 29.95%; UV lmax
(CH3CN)/nm 279 (log 3 3.82) and 202 (4.71); FTIR (neat) nmax
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A solution of iodine (1.78 g, 7.0 mmol) in methanol was drop-
cmꢀ1 3365, 2958, 2926, 2869, 1599, 1394, 1334, 1159, 1098, 894, wise added to a stirred solution of thymol (1 g, 6.7 mmol) in
857, 754, 604; RI (DB-5MS) 2818; EIMS m/z 424 (M+, 100%), 410 methanol (20 mL) containing KOH (20 mmol). The mixture was
(14.4), 409 (70.1), 381 (5.1), 267 (17.1), 255 (11.8), 254 (8.9), 239 further stirred for 10 min, and aerwards concentrated in vacuo.
(14.3), 213 (32.3), 211 (16.4), 197 (22.3), 127 (2.9), 91 (4.4), 77 The reaction mixture was poured into water, neutralized with
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(3.3), 43 (3.9); For H and 13C NMR spectra, see Table 2.
aqueous HCl (1 : 1, v/v) and extracted with diethyl ether. The
3-(4-Hydroxy-5-isopropyl-2-methylbenzyl)-2,4-diiodo-6-isopro- organic layer was washed with aqueous Na2S2O3 solution, dried
pylphenol (17). White amorphous solid; relative content in over anhydrous MgSO4 and the solvent removed on a rotary
aristol: 1.1%; elemental analysis found: C, 43.50; H, 4.59. Calc. evaporator. The obtained cure product (2.3 g) was analysed by
for C20H24I2O2: C, 43.66; H, 4.40; O, 5.82; I, 46.12%; UV lmax GC-MS.
69080 | RSC Adv., 2016, 6, 69067–69082
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