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V. Karapetyan et al. / Tetrahedron 65 (2009) 6211–6217
3.3.3. Methyl 6-formyl-2-hydroxy-3-isopropyl-benzoate (4c)
Starting with 3c (0.200 g, 0.7 mmol), NaOMe (0.117 g, 2.2 mmol)
in dry MeOH (4 mL), 4c was obtained as a yellow oil (0.107 g, 67%).
(40), 105 (21), 77 (24). HRMS (EI): calcd for C15H20O4 (Mþ) 264.13561,
found 264.135677.
1H NMR (250 MHz, CDCl3):
d
¼1.23 (d, 3J¼6.9 Hz, 6H, CH(CH3)2),
3.3.7. Methyl 6-formyl-2-hydroxy-3-octyl-benzoate (4g)
Starting with 3h (0.290 g, 0.8 mmol), NaOMe (0.135 g, 2.5 mmol)
in dry MeOH (4 mL), 4g was obtained as a colourless solid (0.178 g,
3.39 (m, 1H, CH(CH3)2), 4.01 (s, 3H, OCH3), 7.30 (d, 3J¼7.8 Hz, 1H,
CHAr), 7.47 (d, 3J¼7.8 Hz, 1H, CHAr), 10.41 (s, 1H, CHO), 11.20 (s, 1H,
OH). 13C NMR (62.9 MHz, CDCl3):
d
¼22.1 (CH(CH3)2), 27.2
73%); mp 48–50 ꢁC. 1H NMR (250 MHz, CDCl3):
d
¼0.87 (t, 3J¼6.5 Hz,
(CH(CH3)2), 53.0 (OCH3), 110.7 (CAr), 119.9, 131.2 (CHAr), 136.3, 142.8,
3H, CH2CH3), 1.24–1.35 (m, 10H, CH3(CH2)5CH2CH2), 1.60 (m, 2H,
CH2CH2CAr), 2.68 (t, 3J¼7.6 Hz, 2H, CH2CH2CAr), 4.01 (s, 3H, OCH3),
7.27 (d, 3J¼7.7 Hz, 1H, CHAr), 7.39 (d, 3J¼7.7 Hz, 1H, CHAr), 10.42 (s,
159.4 (CAr), 170.6 (C]O), 192.1 (CHO). IR (ATR, cmꢀ1):
n
¼ 2960ðwÞ;
~
2873 (w), 1738 (w), 1669 (br s), 1612 (w), 1576 (w), 1493 (w), 1438
(m), 1418 (m), 1384 (w), 1335 (br m), 1277 (m), 1231 (br s), 1196 (m),
1153 (s), 1132 (s), 1066 (w), 1009 (w), 978 (m), 920 (w), 838 (w), 783
(m), 726 (m), 624 (w). MS (GC, 70 eV): m/z (%)¼222 (Mþ, 68), 207
(29), 190 (51), 175 (100), 162 (45), 147 (43), 134 (76), 119 (23), 91
(52), 77 (24). HRMS (EI): calcd for C12H14O4 (Mþ) 222.08866, found
222.088498.
1H, CHO), 11.12 (s, 1H, OH). 13C NMR (62.9 MHz, CDCl3):
d
¼14.1
(CH2CH3), 22.6, 29.0, 29.2, 29.4, 29.5, 30.3, 31.9 (CH2), 53.0 (OCH3),
110.8 (CAr), 119.7 (CHAr), 134.6 (CHAr), 136.5, 137.4, 160.0 (CAr), 170.5
(C]O), 192.1 (CHO). IR (ATR, cmꢀ1):
¼ 3037ðwÞ; 2950 (w), 1217
~
n
(m), 2849 (m), 1745 (w), 1689 (s), 1661 (s), 1575 (w), 1494 (w), 1439
(m), 1419 (m), 1392 (w), 1341 (m), 1292 (m), 1243 (s), 1147 (s), 1121
(w), 1092 (w), 1014 (w), 980 (w), 878 (w), 939 (w), 813 (w), 780 (m),
757 (m), 724 (m), 587 (w), 549 (w). MS (GC, 70 eV): m/z (%)¼292
(Mþ, 22), 277 (19), 263 (23), 233 (12), 194 (24), 162 (100), 147 (13),
134 (36), 105 (16), 77 (17). HRMS (EI): calcd for C17H24O4 (Mþ)
292.16691, found 292.166507.
3.3.4. Methyl 3-butyl-6-formyl-2-hydroxy-benzoate (4d)
Starting with 3d (0.259 g, 0.9 mmol), NaOMe (0.144 g,
2.7 mmol) in dry MeOH (5 mL), 4d was obtained as a yellow oil
(0.168 g, 81%). 1H NMR (300 MHz, CDCl3):
d
¼0.93 (t, 3J¼7.3 Hz, 3H,
CH2CH3), 1.37 (m, 2H, CH2), 1.58 (m, 2H, CH2), 2.69 (t, 3J¼7.6 Hz, 2H,
CH2CAr), 4.01 (s, 3H, OCH3), 7.26 (d, 3J¼7.6 Hz, 1H, CHAr), 7.39 (d,
3J¼7.6 Hz, 1H, CHAr), 10.42 (s, 1H, CHO), 11.11 (s, 1H, OH). 13C NMR
3.3.8. Ethyl 6-formyl-2-hydroxy-3-octyl-benzoate (4h)
Starting with 3i (0.370 g, 1.0 mmol), NaOEt (0.208 g, 3.1 mmol)
in dry EtOH (5 mL), 4h was obtained as a yellow oil (0.238 g, 76%).
(75.5 MHz, CDCl3):
d
¼13.9 (CH2CH3), 22.5, 29.9, 31.2 (CH2), 53.0
(OCH3), 110.8 (CAr), 119.7, 134.5 (CHAr), 136.5, 137.4, 160.0 (CAr), 170.5
1H NMR (250 MHz, CDCl3):
d
¼0.86 (t, 3J¼6.4 Hz, 3H, CH2CH3), 1.24–
(C]O), 192.1 (CHO). IR (ATR, cmꢀ1):
n
¼ 2956ðwÞ; 2929 (w), 2860
1.33 (m, 10H, CH3(CH2)5CH2CH2), 1.42 (t, 3J¼7.2 Hz, 3H, OCH2CH3),
1.57 (m, 2H, CH2CH2CAr), 2.68 (t, 3J¼7.6 Hz, 2H, CH2CH2CAr), 4.49 (q,
3J¼7.2 Hz, 2H, OCH2CH3), 7.24 (d, 3J¼7.7 Hz, 1H, CHAr), 7.38 (d,
3J¼7.7 Hz, 1H, CHAr), 10.45 (s, 1H, CHO), 11.19 (s, 1H, OH). 13C NMR
~
(w), 1742 (w), 1670 (s), 1514 (w), 1577 (w), 1438 (m), 1421 (s), 1379
(w), 1337 (m), 1290 (m), 1240 (s), 1196 (s), 1141 (s), 981 (br w), 917
(w), 873 (w), 812 (w), 781 (s), 581 (m), 541 (w). MS (GC, 70 eV): m/z
(%)¼236 (Mþ, 31), 221 (20), 207 (22), 175 (22), 162 (100), 148 (22),
134 (55), 105 (28), 77 (34). HRMS (EI): calcd for C13H16O4 (Mþ)
236.10431, found 236.104421.
(62.9 MHz, CDCl3):
d¼14.1 (CH2CH3), 14.2 (CH2CH3), 14.1, 14.2
(CH2CH3, OCH2CH3), 22.6, 29.0, 29.2, 29.4, 29.5, 30.2, 31.8 (CH2),
62.7 (OCH2CH3), 111.0 (CAr), 119.6 (CHAr), 134.4 (CHAr), 136.7, 137.3,
160.0 (CAr), 170.1 (C]O), 192.0 (CHO). IR (ATR, cmꢀ1):
n
¼ 2934ðwÞ;
~
3.3.5. Methyl 6-formyl-2-hydroxy-3-pentyl-benzoate (4e)
2854 (m), 1744 (w), 1690 (s), 1666 (s), 1578 (w), 1443 (w), 1422 (m),
1396 (w), 1372 (m), 1324 (m), 1240 (s), 1175 (m), 1142 (s), 1096 (w),
1017 (m), 914 (br w), 860 (w), 836 (w), 814 (w), 781 (m), 750 (m),
722 (m). MS (GC, 70 eV): m/z (%)¼306 (Mþ, 19), 277 (85), 260 (10),
233 (22), 208 (17), 162 (100), 134 (27), 105 (14), 77 (15). HRMS (EI):
Calcd for C18H26O4 (Mþ) 306.18256, found 306.182417.
Starting with 3f (0.280 g, 0.9 mmol), NaOMe (0.149 g, 2.8 mmol)
in dry MeOH (5 mL), 4e was obtained as a yellow oil (0.179 g, 78%). 1H
NMR (300 MHz, CDCl3):
d
¼0.88 (t, 3J¼6.9 Hz, 3H, CH2CH3), 1.30–1.35
(m, 4H, CH3(CH2)2CH2CH2CAr), 1.61 (m, 2H, CH3(CH2)2CH2CH2CAr),
2.68 (t, 3J¼7.7 Hz, 2H, CH2CAr), 4.01 (s, 3H, OCH3), 7.26 (d, 3J¼7.7 Hz,
1H, CHAr), 7.39 (d, 3J¼7.7 Hz,1H, CHAr),10.42 (s,1H, CHO),11.11 (s,1H,
OH). 13C NMR (75.5 MHz, CDCl3):
d¼14.0 (CH2CH3), 22.5, 28.7, 30.2,
3.3.9. Methyl 3-allyl-6-formyl-2-hydroxy-benzoate (4i)
31.6 (CH2), 53.0 (OCH3), 110.8 (CAr), 119.7, 134.5 (CHAr), 136.5, 137.4,
Starting with 3j (0.233 g, 0.9 mmol), NaOMe (0.137 g, 2.5 mmol)
160.0 (CAr), 170.5 (C]O), 192.1 (CHO). IR (ATR, cmꢀ1):
¼ 2955ðwÞ;
in dry MeOH (4 mL), 4i was obtained as yellow oil (0.152 g, 81%). 1H
~
n
2927 (w), 2859 (w), 1744 (w), 1670 (s), 1578 (w), 1439 (m), 1421 (m),
1240 (s), 1196 (s), 1141 (s), 1095 (w), 986 (w), 929 (w), 869 (w), 835
(w), 813 (w), 781 (s), 759 (m), 581 (w). MS (GC, 70 eV): m/z (%)¼250
(Mþ, 23), 236 (7), 205 (26), 180 (64), 165 (100), 137 (34), 91 (15), 77
(11). HRMS (EI): calcd for C14H18O4 (Mþ) 250.13561, found
250.135677.
NMR (250 MHz, CDCl3):
d
¼3.46 (d, 3J¼6.7 Hz, 2H, CH2CAr), 4.01 (s,
3H, OCH3), 5.09 (m, 2H, CH2CHCH2), 5.98 (m,1H, CH2CHCH2), 7.28 (d,
3J¼7.6 Hz, 1H, CHAr), 7.42 (d, 3J¼7.6 Hz, 1H, CHAr), 10.43 (s, 1H, CHO),
11.16 (s, 1H, OH). 3C NMR (62.9 MHz, CDCl3):
d¼34.1 (CH2CAr), 53.0
(OCH3), 110.9 (CAr), 116.8 (CH2CH), 119.8 (CHAr), 134.5 (CAr), 134.6
(CHAr), 135.0 (CH2CHCH2), 137.0, 159.7 (CAr), 170.4 (C]O), 192.0
(CHO). R (ATR, cmꢀ1):
n
¼ 3079ðwÞ; 2956 (w), 2921 (w), 1669 (s),
~
3.3.6. Methyl 6-formyl-3-hexyl-2-hydroxy-benzoate (4f)
1577 (w),1486 (w),1437 (m),1421 (s),1336 (m),1303 (br m),1241 (s),
1196 (s),1139 (s), 989 (m), 916 (m), 872 (w), 836 (m), 813 (m), 781 (s),
746 (br m), 587 (m). MS (GC, 70 eV): m/z (%)¼220 (Mþ, 55), 205 (19),
173 (38), 159 (49), 145 (16), 131 (100), 115 (15), 103 (48), 77 (60).
HRMS (EI): calcd for C12H12O4 (Mþ) 220.07301, found 220.072813.
Starting with 3g (0.300 g, 0.9 mmol), NaOMe (0.152 g, 2.8 mmol)
in dry MeOH (5 mL), 4f was obtained as a yellow oil (0.170 g, 69%). 1H
NMR (300 MHz, CDCl3):
d
¼0.87 (t, 3J¼6.8 Hz, 3H, CH2CH3), 1.27–1.37
(m, 6H, CH3(CH2)3CH2CH2CAr), 1.61 (m, 2H, CH3(CH2)3CH2CH2CAr),
2.69 (t, 3J¼7.7 Hz, 2H, CH2CAr), 4.01 (s, 3H, OCH3), 7.27 (d, 3J¼7.7 Hz,
1H, CHAr), 7.39 (d, 3J¼7.7 Hz,1H, CHAr),10.42 (s,1H, CHO),11.11 (s,1H,
3.3.10. Methyl 7-dichloromethyl-chroman-8-carboxylate (6a)
Starting with 5a (0.335 g, 1.1 mmol), NaOMe (0.233 g, 4.3 mmol)
in dry MeOH (5 mL), 6a was obtained as colourless solid (0.198 g,
OH). 13C NMR (75.5 MHz, CDCl3):
d¼14.1 (CH2CH3), 22.6, 29.0, 29.1,
30.3, 31.7 (CH2), 53.0 (OCH3), 110.8 (CAr), 119.7, 134.5 (CHAr), 136.5,
137.4, 160.0 (CAr), 170.5 (C]O), 192.1 (CHO). IR (ATR, cmꢀ1):
83%). 1H NMR (250 MHz, CDCl3):
d
¼2.04 (m, 2H, CH2CH2O), 2.86 (t,
n
¼ 2955ðwÞ; 2926 (w), 2856 (w), 1738 (w), 1670 (s), 1614 (w), 1578
3J¼6.5 Hz, 2H, CArCH2), 3.95 (s, 3H, OCH3), 4.26 (t, 3J¼5.3 Hz, 2H,
CH2O), 7.23 (d, 3J¼7.8 Hz, 1H, CHAr), 7.33 (d, 3J¼7.8 Hz, 1H, CHAr),
~
(w), 1492 (w), 1439 (m), 1420 (m), 1336 (m), 1288 (m), 1239 (s), 1196
(m), 1141 (s), 1099 (w), 1053 (w), 1011 (w), 982 (w), 875 (w), 812 (w),
781 (m), 747 (m), 582 (w). MS (GC, 70 eV): m/z (%)¼264 (Mþ, 23),
249 (18), 235 (21), 205 (13), 194 (17),175 (13),162 (100),147 (14),134
9.87 (s, 1H, CHO). 13C NMR (62.9 MHz, CDCl3):
(CH2CH2CH2O), 52.8 (OCH3), 67.1 (CH2O), 122.7 (CAr), 122.7 (CHAr),
130.1 (CAr),131.0 (CHAr),132.5,152.2 (CAr),167.5 (C]O),190.1 (CHO).
d¼21.4, 25.4