V.O. Iaroshenko et al. / Tetrahedron 67 (2011) 8321e8330
8327
ESI: calcd for C15H11N4F6 (MþHþ) 361.08824, found 361.08803. IR
CDCl3):
d
¼55.7 (OCH3), 109.6 (CHAr), 115.0 (CHAr), 115.3 (CHAr),119.4
(ATR, cmꢁ1): v ¼ 3130 (w), 3091 (w), 3032 (w), 2998 (w), 2946 (w),
(q, J¼276.4 Hz, CCF3), 120.1 (q, J¼276.4 Hz, CCF3), 131.1 (CHAr), 131.7
(C), 134.0 (C), 146.3 (q, J¼38.5 Hz, CCF3), 148.4 (C), 150.3 (q,
J¼38.5 Hz, CCF3), 153.6 (C), 160.9 (NCHN). MS (GC, 70eV): m/z (%)¼
362 (Mþ, 100), 361 (25), 343 (11), 341 (32), 332 (12), 331 (10), 313
(13), 312 (16). HRMS (EI): calcd for C14H8N4F6 (Mþ) 362.05968,
~
2859 (w), 1984 (w), 1955 (w), 1801 (w), 1739 (w), 1680 (w), 1599
(w), 1504 (w), 1452 (w), 1400 (w), 1357 (w), 1302 (w), 1271 (m),
1208 (s), 1199 (s), 1168 (m), 1130 (s), 1080 (m), 1010 (m), 962 (m),
905 (w), 886 (m), 817 (w), 766 (w), 723 (m), 676 (m), 640 (s), 586
(w), 546 (w).
found 362.058868. IR (ATR, cmꢁ1): v ¼ 3119 (w), 3021 (w), 2952
~
(w), 2845 (w), 1610 (w), 1555 (w), 1504 (w), 1450 (w), 1400 (w),
1335 (w), 1276 (w), 1212 (m), 1186 (w), 1136 (m), 1051 (w), 995 (w),
949 (m), 890 (w), 836 (w), 775 (m), 738 (w), 683 (w), 637 (w), 598
(w), 545 (w).
3.2.18. 9-(2-Methoxyphenethyl)-2,6-bis(trifluoromethyl)-9H-purine
(9n). White crystalline isolated by column chromatography (hep-
tane/EtOAc, 10:1); mp 144e126 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼3.19 (t, 2H, J¼6.4 Hz, NCH2CH2), 3.62 (s, 3H, CH3), 4.65 (t, 2H,
J¼6.5 Hz, NCH2CH2), 6.75e6.88 (m, 3H, 3CHAr), 7.16e7.21 (m, 1H,
3.2.22. 2,6-Bis(trifluoromethyl)-9-(3,4-dimethoxyphenyl)-9H-purine
(10b). White solid isolated by column chromatography (heptane/
CHAr), 7.98 (s, 1H, NCHN). 19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.5,
ꢁ65.9. 13C NMR (75.4 MHz, CDCl3):
d
¼31.2 (OCH3), 44.8 (NCH2CH2),
EtOAc, 7:3); mp 136e138 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼3.95 (s,
55.0 (NCH2CH2), 110.5 (C), 119.5 (q, J¼273.6 Hz, CCF3), 120.3 (q,
J¼273.6 Hz, CCF3),120.9 (C),124.6 (CH),129.2 (CH),130.6 (CH),130.9
(CH), 145.1 (q, J¼36.0 Hz, CCF3), 149.6 (q, J¼36.0 Hz, CCF3), 149.9 (C),
154.5 (C), 157.3 (NCHN). MS (GC, 70eV): m/z (%)¼392 (10), 390 (Mþ,
16), 371 (14), 135 (12), 134 (100), 121 (15), 119 (58), 91 (62), 62 (10).
ESI: calcd for C16H13ON4F6 (MþHþ) 391.09881, found 391.0995. IR
3H, OCH3), 3.96 (s, 3H, OCH3), 7.03 (d, 1H, J¼8.3 Hz, CHAr), 7.18 (dd,
1H, J¼8.2, 8.6 Hz, CHAr), 7.27 (d, 1H, J¼2.6 Hz, CHAr), 8.64 (s, 1H,
NCHN). 19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.6, ꢁ65.9. 13C NMR
(62.9 MHz, CDCl3):
d
¼56.2 (2OCH3), 107.5 (CHAr), 111.6 (CHAr),115.9
(CHAr), 119.2 (q, J¼275.7 Hz, CCF3), 120.3 (q, J¼275.7 Hz, CCF3), 125.8
(C), 131.5 (C), 146.2 (q, J¼35.5 Hz, CCF3), 148.7 (C), 150.0 (2C), 150.9
(q, J¼35.5 Hz, CCF3), 153.6 (NCHN). MS (GC, 70eV): m/z (%)¼393
(17), 392 (Mþ, 100), 377 (16), 349 (21), 329 (24). ESI: calcd for
C15H11O2N4F6 (MþHþ) 393.07837, found 393.07837. IR (ATR, cmꢁ1):
(ATR, cmꢁ1): v ¼ 3068 (w), 2975 (w), 2841 (w), 1791 (w), 1717 (w),
~
1673 (w), 1601 (w), 1509 (w), 1455 (w), 1403 (w), 1369 (w), 1303
(w), 1265 (m), 1209 (m), 1167 (m), 1120 (m), 1053 (w), 1018 (w), 959
(w), 912 (w), 858 (w), 803 (w), 757 (m), 686 (w), 636 (m), 577 (w).
~
v ¼ 3140 (w), 2961 (w), 2840 (w), 1603 (w), 1523 (w), 1469 (w),
1403 (w), 1334 (w), 1276 (w), 1212 (m), 1176 (m), 1141 (s), 1012 (m),
954 (m), 891 (w), 858 (m), 794 (m), 739 (m), 669 (w), 603 (w), 527
(w).
3.2.19. 9-(3,4-Dimethoxyphenethyl)-2,6-bis(trifluoromethyl)-9H-pu-
rine (9o). White solid isolated by column chromatography (hep-
tane/EtOAc, 3:7); mp 145e147 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼3.14 (t, 2H, J¼6.9 Hz, CH2), 3.76 (s, 3H, CH3), 3.81 (s, 3H, CH3), 4.63
3.2.23. 2,6-Bis(trifluoromethyl)-9-(3,5-dimethoxyphenyl)-9H-purine
(10c). White crystalline isolated by column chromatography
(heptane/EtOAc, 10:1); mp 150e152 ꢀC. 1H NMR (300 MHz, CDCl3):
(t, 2H, J¼6.9 Hz, CH2), 6.50e6.52 (m, 2H, 2CHAr), 6.72 (d, 1H,
J¼8.7 Hz, CHAr), 8.00 (s, 1H, NCHN). 19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.5, ꢁ65.9. 13C NMR (75.4 MHz, CDCl3):
d
¼35.6 (OCH3), 46.2
d
¼3.86 (s, 6H, 2OCH3), 6.58 (t, 1H, J¼2.1 Hz, CHAr), 6.87 (d, 2H,
(OCH3), 55.8 (CH2), 111.5 (CH), 119.2 (q, J¼276.0 Hz, CCF3), 119.8 (q,
J¼276.0 Hz, CCF3), 120.8 (CH), 128.5 (CH), 130.9 (C), 145.4 (q,
J¼38.8 Hz, CCF3), 148.4 (C), 149.5 (q, J¼38.4 Hz, CCF3), 148.4 (C),
149.4 (C), 14.6 (C), 154.0 (NCHN). MS (GC, 70eV): m/z (%)¼420 (Mþ,
23), 165 (11), 164 (100), 151 (32), 149 (15). ESI: calcd for
C17H15O2N4F6 (MþHþ) 421.10937, found 421.10979. IR (ATR, cmꢁ1):
J¼2.8 Hz, 2CHAr), 8.67 (s, 1H, NCHN). 19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.6, ꢁ65.9. 13C NMR (75.4 MHz, CDCl3):
¼55.7 (2OCH3),
d
100.9 (CHAr), 101.9 (2CHAr), 119.3 (q, J¼275.6 Hz, CCF3), 120.1 (q,
J¼275.6 Hz, CCF3), 131.7 (C), 134.4 (C), 146.3 (q, J¼38.1 Hz, CCF3),
148.4 (C), 150.4 (q, J¼38.1 Hz, CCF3), 153.5 (NCHN), 161.8 (2C). MS
(GC, 70eV): m/z (%)¼393 (Mþ, 40), 392 (100), 391 (52), 373 (23), 371
(39), 362 (11), 361 (11), 343 (46), 341 (28), 313 (10), 312 (12), 69
(11). HRMS (EI): calcd for C15H10ON4F6 (Mþ) 392.07025, found
~
v ¼ 3113 (w), 3089 (w), 3006 (w), 2948 (w), 2849 (w), 1597 (w),
1514 (w), 1469 (w), 1404 (w), 1367 (w), 1307 (w), 1252 (w), 1224
(m), 1190 (w), 1131 (m), 1021 (w), 959 (w), 889 (s), 856 (w), 818 (w),
777 (w), 735 (w), 697 (w), 657 (w), 625 (w), 599 (w), 537 (w).
392.070024. IR (ATR, cmꢁ1): v ¼ 3118 (w), 3024 (w), 2971 (w),
~
2845 (w), 1613 (w), 1585 (w), 1503 (w), 1461 (w), 1404 (w), 1356
(m), 1275 (m), 1235 (w), 1137 (m), 1076 (m), 1024 (w), 958 (m), 891
(w), 833 (m), 784 (w), 714 (w), 663 (w), 604 (w), 570 (w).
3.2.20. 2,6-Bis(trifluoromethyl)-9-((pyridin-4-yl)methyl)-9H-purine
(9p). White crystalline isolated by column chromatography (hep-
tane/EtOAc, 10:1); mp 126e128 ꢀC. 1H NMR (300 MHz, CDCl3):
3.2.24. 2,6-Bis(trifluoromethyl)-9-(2,4-dimethoxyphenyl)-9H-purine
(10d). White solid isolated by column chromatography (heptane/
d
¼5.58 (s, 2H, CH2), 7.20 (d, 2H, J¼6.1 Hz, 2CHAr), 8.44 (s, 1H, NCHN),
8.63 (d, 2H, J¼6.1 Hz, 2CHAr). 19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.6,
EtOAc, 7:3); mp 143e145 ꢀC. 1H NMR (300 MHz, CDCl3):
d¼3.79 (s,
ꢁ65.9. 13C NMR (100.6 MHz, acetone-d6):
d
¼47.3 (CH2), 120.7 (q,
3H, OCH3), 3.90 (s, 3H, OCH3), 6.66e6.70 (m, 2H, J¼2.5, 6.6 Hz,
J¼275.1 Hz, CCF3), 121.5 (q, J¼2775.1 Hz, CCF3), 123.2 (C), 145.0 (q,
J¼37.6 Hz, CCF3), 144.9 (C), 149.7 (q, J¼37.6 Hz, CCF3), 151.4 (C), 153.1
(C), 156.0 (NCHN). MS (GC, 70eV): m/z (%)¼347 (Mþ, 100), 346 (57),
328 (22), 327 (22), 326 (41), 307 (15), 278 (26), 183 (12), 92 (26), 69
(11), 65 (17). ESI: calcd for C13H7N5F6 (MþHþ) 348.06784, found
2CHAr), 7.44 (d, 1H, J¼9.1 Hz, CHAr), 8.54 (s, 1H, NCHN). 19F NMR
(300 MHz, CDCl3):
d
¼ ꢁ68.5, ꢁ65.9. 13C NMR (100.6 MHz, CDCl3):
d
¼55.8 (OCH3), 55.9 (OCH3), 100.4 (CHAr), 105.1 (CHAr),114.2 (C),
118.5 (q, J¼276.3 Hz, CCF3), 121.3 (q, J¼276.3 Hz, CCF3), 128.1 (CHAr),
130.8 (C), 145.5 (q, J¼37.7 Hz, CCF3), 150.1 (q, J¼37.7 Hz, CCF3), 151.1
(C), 154.6 (C), 162.1 (NCHN). MS (GC, 70eV): m/z (%)¼393 (17), 392
(Mþ, 100), 373 (12), 363 (14), 362 (10), 347 (17), 323 (11), 319 (10).
ESI: calcd for C15H11O2N4F6 (MþHþ) 393.07807, found 393.0788. IR
348.06797. IR (ATR, cmꢁ1): v ¼ 3087 (w), 3043 (w), 2983 (w), 1599
~
(w), 1505 (w), 1455 (w), 1416 (w), 1368 (w), 1307 (m), 1271 (m),
1230 (w), 1199 (m), 1120 (m), 1067 (w), 977 (m), 942 (w), 890 (m),
818 (w), 794 (m), 734 (w), 695 (m), 658 (m), 639 (m), 568 (w).
(ATR, cmꢁ1): v ¼ 3079 (w), 2945 (w), 1595 (w), 1523 (w), 1453 (w),
~
1403 (w), 1342 (w), 1304 (w), 1237 (w), 1208 (m), 1190 (m), 1134 (s),
1041 (m), 1025 (m), 938 (m), 887 (w), 816 (m), 739 (w), 672 (m),
646 (m), 587 (w), 534 (w), 468 (w), 412 (w).
3.2.21. 2,6-Bis(trifluoromethyl)-9-(3-methoxyphenyl)-9H-purine
(10a). White solid isolated by column chromatography (heptane/
EtOAc, 10:1); mp 145e147 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼3.90 (s,
3H, OCH3), 7.06e7.09 (m, 1H, CHAr), 7.25e7.28 (m, 1H, CHAr), 7.32 (t,
1H, J¼2.2 Hz, CHAr), 7.53 (t, 1H, J¼8.1 Hz, CHAr), 8.68 (s, 1H, NCHN).
3.2.25. 2,6-Bis(trifluoromethyl)-9-(3,4,5-trimethoxyphenyl)-9H-pu-
rine (10e). White solid isolated by column chromatography (hep-
tane/EtOAc, 7:3); mp 118e120 ꢀC. 1H NMR (300 MHz, CDCl3):
19F NMR (300 MHz, CDCl3):
d
¼ ꢁ68.6, ꢁ65.9. 13C NMR (75.4 MHz,