Modified coumarins. 24. Synthesis of cycloheptane-annellated tetracyclic furocoumarins

Article abstract of DOI:10.1007/s10600-006-0246-8

Substituted 2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-ones, modified psoralen analogs containing a cycloheptane ring annellated to the 5,6-positions of a furo[3,2-g]chromen-7-one, were synthesized from 3-hydroxy-8,9,10,11-tetrahydrocyclohepta[c]

Full text of DOI:10.1007/s10600-006-0246-8

Chemistry of Natural Compounds, Vol. 42, No. 6, 2006
MODIFIED COUMARINS. 24. SYNTHESIS OF CYCLOHEPTANE-
ANNELLATED TETRACYCLIC FUROCOUMARINS
Ya. L. Garazd,1 M. M. Garazd,2 A. S. Ogorodniichuk,2 and V. P. Khilya1
UDC 547.814.5
c
g
Substituted 2,3,4,5-tetrahydrocyclohepta[ ]furo[3,2- ]chromen-6-ones, modified psoralen analogs
g
containing a cycloheptane ring annellated to the 5,6-positions of a furo[3,2- ]chromen-7-one, were
c
synthesized from 3-hydroxy-8,9,10,11-tetrahydrocyclohepta[ ]chromen-6-ones.
Key words: comarins, furocoumarins, psoralen, 3-hydroxy-8,9,10,11-tetrahydrocyclohepta[ ]chromen-6-one.
c
Furocoumarins comprise natural compounds with a variety of structures that in most instances are derivatives of the
linear furocoumarin psoralen [1]. Natural furocoumarins and their synthetic analogs have various physiological activities that
depend on the chemical structure. Thus, furocoumrains with carbocycles annellated at the 5,6-positions exhibit
photoantiproliferative [2-5] and cardiotropic [6] activities and act as CNS stimulants [6].
In continuation of research on the synthesis and properties of furocoumarins [6-9], herein we report the preparation
of tetracyclic psoralen-type furocoumarins containing a cycloheptane ring annellated to the 5,6-positions of a furo[3,2-
]chromen-7-one.
g
3-Hydroxy-8,9,10,11-tetrahydrocyclohepta[ ]chromen-6-one (1) and its 4-methyl analog (2) that were necessary for
c
further transformations were prepared by Pechmann condensation of resorcinol and 2-methylresorcinol, respectively, with
methyl-2-oxo-1-cycloheptanecarboxylate in the presence of conc. H SO at 0°C [10, 11].
2
4
R
R
R
4
O
R
O
O
O
O
O
O
O
O
HO
O
1
R COCH Hal
3
R COCHR Hal
1
2
2
1
7
R
1
R
2
K CO
K CO
2
3
2
3
1
11
3 - 6, 11 - 22
1, 2
7 - 10
9
1. NaOH
2. HCl
O
1. NaOH
2. HCl
K CO
2
3
Cl
O
R
8
R
R
R
10
8
O
O
O
1. NaOH
2. HCl
O
O
O
O
O
O
O
O
11
10
R
1
5
5
O
11
12
13
14
R
1
R
1
1
2
3
3
25 - 28, 33 - 44
23, 24
45, 46
29 - 32
1 23 45:
2 24 46:
R = H; ,
3 25:
R = Me; ,
4 26:
R = H, R1 = Me; ,
5 27:
R = R1 = Me, ,
t
6 28:
t
7
,
,
,
R = H, R1 = -Bu; ,
R = Me, R = -Bu; ,
29:
8 30:
9 31:
R = R1 = R2 = Me, ,
10 32:
R = H, R1 = Me, R2 = Ph; ,
11 33:
16 38:
R = H, R1 = R2 = Me; ,
13 35:
R = R1 = Me, R2 = Ph;
,
R = H, R1 = Ph;
R = Me, R1 = 4-ClPh
R = Me, R1 = 4-MeOPh
12 34:
14 36:
15 37:
,
,
R = Me, R1 = Ph,
,
R = H, R1 = 4-FPh;
18 40:
,
R = H, R1 = 4-FPh;
R = H, R1 = 4-ClPh;
,
17 39:
19 41:
,
20 42:
,
,
R = H, R1 = 4-BrPh;
,
R = Me, R1 = 4-BrPh;
22 44:
R = Me, R1 = 3-MeOPh
R = H, R1 = 4-MeOPh;
21 43:
,
R = H, R1 = 3-MeOPh;
,
1)TarasShevchenkoKievNational University, 01033, Ukraine, Kiev, ul. Vladimirskaya, 64; 2) InstituteofBioorganic
and Petroleum Chemistry, National Academy of Sciences of Ukraine, 02094, Ukraine, Kiev, ul. Murmanskaya, 1, e-mail:
gmm@i.com.ua. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 534-540, November-December, 2006. Original
article submitted August 28, 2006.
0009-3130/06/4206-0656 ©2006 Springer Science+Business Media, Inc.
656

Of the many approaches to the construction of furocoumarins [12-15], we selected the MacLeod method for forming
the psoralen system that is based on cyclization in alkaline medium of 7-(2-oxoethyl)coumarins. In most instances this leads
exclusively to linear furocoumarins (psoralen-type furocoumarins) because the 6-position of the coumarin ring is more highly
activated than the 8-position [16, 17].
Reaction of 1 and 2 with α-haloketones under Williamson reaction conditions produced in high yields (65-93%) the
corresponding substituted oxoethers 3-24. The alkylating agents in this synthesis were chloroacetone (3, 4), 1-chloropinacolone
(5, 6), 3-chloro-2-butanone (7, 8), 2-bromopropiophenone (9, 10), phenacylbromide (11, 12), 4-fluorophenacylchloride
(13, 14), 4-chlorophenacylbromide (15, 16), 4-bromophenacylbromide (17, 18), 4-methoxyphenacylbromide (19, 20),
3-methoxyphenacylbromide (21, 22), and 2-chlorocyclohexanone (23, 24). PMR spectra of 3-24 typically had signals
characteristic of the corresponding alkyl substituents and coumarin system. IR spectra of 3-24 had two absorption bands in the
-1
range 1690-1725 cm due to stretching vibrations of the coumarin C=O bond and the carbonyl in the oxoalkyl substituent [18].
The UV spectra of 3-24 contained two strong maxima at 204-211 and 321-324 nm that were characteristic of the coumarin
ring [18].
Ketones 3-24 were heated with NaOH solution (1 N). Subsequent acidolysis of the reaction mixture led smoothly and
in high yields (79-94%) to cyclization and formation of the corresponding substituted 2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-
g]chromen-6-ones 25-46, tetracyclic analogs of psoralen-type furocoumarins containing an annellated cycloheptane ring. The
linear addition of the furan ring to the 2,3-positions of the 8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one was confirmed by
PMR spectroscopy. The PMR spectra of 25-46 contained a simplified splitting pattern for the aromatic protons compared with
the starting ketones due to a lack of coupling with the H-2 proton of the 8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one. For
8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-ones, the H-12 proton was observed as a singlet at 7.63-7.99
ppm. Protons H-8 and H-12 in spectra of furocoumarins without an 8-methyl resonated as two singlets at 7.37-8.16 ppm.
Furthermore, proton H-10 in furocoumarins 25-28 and 32-44 that were unsubstituted at the 10-position of the 2,3,4,5-
tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one was observed as a singlet. This is also a characteristic signature of
furocoumarin formation. The singlet for H-10 in 2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g[chromen-6-ons with an 11-alkyl
substituent (25-28) was located at 7.64-7.73 ppm. An aryl substituent in the 11-position (32-44) shifted the signal for H-10 to
weaker field (8.18-8.39 ppm). UV spectra of 25-46 exhibited a stronger absorption in the range 246-257 nm than the long-
wavelength band (290-310 nm).
This is also proof of addition of the furan ring to the 8,9,10,11-
tetrahydrocyclohepta[c]chromen-6-one system [18].
EXPERIMENTAL
The course of reactions and the purity of products were monitored by TLC on Merck 60 F254 plates using
CHCl :CH OH (9:1 and 95:5) as eluent. IR and UV spectra were measured on a Nicolet FTIR Nexus 475 spectrometer and
3
3
Specord M40 spectrophotometer, respectively; PMR spectra, on a Varian VXR-300 spectrometer relative to TMS (internal
stanard). Elemental analyses of all compounds agreed with those calculated.
3-Hydroxy-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (1). A cold (0°C) solution of resorcinol (11.0 g,
100 mmol) and methyl-2-oxo-1-cycloheptanecarboxylate (15.6 mL, 100 mmol) in absolute CH OH (20 mL) was stirred
3
vigorously, cooled, and treated dropwise with conc. H SO (10 mL). The reaction mixture was stirred until congealed, left
2
4
overnight at room temperature, and poured into icewater (200 mL). The resulting precipitate was filtered off and crystallized
from propan-2-ol (60%). Yield 59%, mp 188-189°C (lit. [10] mp 188.5-189.5°C, [11] 189-190°C), C H O .
14 14
3
-1
IR spectrum (KBr, cm ): 3219, 2929, 1679, 1614, 1568, 1514, 1385, 1324, 1311, 1236, 1150, 1097, 1075, 867, 779.
UV spectrum (CH CN, nm, log ε): 219 (4.20), 324 (4.20).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.61 (2H, m, CH -10), 1.86 (2H, m, CH -8),
6
2
2
2
2.74 (2H, m, CH -11), 2.90 (2H, m, CH -7), 6.65 (1H, d, J = 2.4, H-4), 6.73 (1H, dd, J = 2.4, 8.7, H-2), 7.60 (1H, d, J = 8.7,
2
2
H-1), 10.23 (1H, s, OH-3).
3-Hydroxy-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (2) was prepared analogouslyto 1 starting
with 2-methylresorcinol (12.4 g, 100 mmol) and methyl-2-oxo-1-cycloheptanecarboxylate (15.6 mL, 100 mmol). Yield 64%,
mp 224-225°C, C H O .
15 16
3
-1
IR spectrum (KBr, cm ): 3221, 2912, 1675, 1604, 1569, 1508, 1457, 1376, 1321, 1271, 1248, 1102, 1086, 808, 778.
657

UV spectrum (EtOH, nm, log ε): 206 (4.81), 223 (4.41), 331 (4.32).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.59 (2H, m, CH -10), 1.86 (2H, m, CH -8),
6
2
2
2
2.17 (3H, s, CH -4), 2.74 (2H, m, CH -11), 2.90 (2H, m, CH -7), 6.81 (1H, d, J = 8.7, H-2), 7.45 (1H, d, J = 8.7, H-1), 10.15
3
2
2
(1H, s, OH-3).
Ketones 3-24. A hot solution of 1 or 2 (4 mmol) in absolute acetone (30 mL) was treated with freshly calcined potash
(1.38 g, 10 mmol), stirred vigorously, heated (50-56°C), and treated with the appropriate α-haloketone (4.2 mmol). The
reaction mixture was held for 1-5 h with heating and vigorous stirring (course of reaction monitored by TLC) and poured into
H SO solution (100 mL, 1 N). The resulting precipitate was filtered off and crystallized from aqueous propan-2-ol.
2
4
3-(2-Oxopropoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (3). Yield 86%, mp 147-148°C, C H O .
17 18
4
-1
IR spectrum (KBr, cm ): 2913, 1712, 1607, 1446, 1390, 1291, 1269, 1232, 1170, 1148, 1104, 874.
UV spectrum (CH CN, nm, log ε): 206 (4.67), 220 (4.25), 322 (4.23).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.62 (2H, m, CH -10), 1.85 (2H, m, CH -8),
6
2
2
2
2.18 (3H, s, CH -3′), 2.76 (2H, m, CH -11), 2.96 (2H, m, CH -7), 4.90 (2H, s, CH -1′), 6.89 (2H, m, H-2, H-4), 7.72 (1H, d,
3
2
2
2
J = 8.7, H-1).
4-Methyl-3-(2-oxopropoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (4). Yield 85%, mp 151-152°C,
C H O .
18 20
4
-1
IR spectrum (KBr, cm ): 2918, 1727, 1692, 1601, 1572, 1375, 1301, 1242, 1126.
UV spectrum (CH CN, nm, log ε): 207 (4.58), 222 (4.13), 324 (4.14).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.60 (2H, m, CH -10), 1.89 (2H, m, CH -8),
6
2
2
2
2.17 (3H, s, CH -3′), 2.27 (3H, s, CH -4), 2.78 (2H, m, CH -11), 2.94 (2H, m, CH -7), 4.89 (2H, s, CH -1′), 6.83 (1H, d,
3
3
2
2
2
J = 8.7, H-2), 7.59 (1H, d, J = 8.7, H-1).
3-(3,3-Dimethyl-2-oxobutoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (5). Yield 82%, mp 171-172°C,
C H O .
20 24
4
-1
IR spectrum (KBr, cm ): 2919, 1725, 1694, 1617, 1606, 1427, 1385, 1255, 1236, 1178, 1094, 1076, 1009, 865.
UV spectrum (CH CN, nm, log ε): 205 (4.58), 220 (4.19), 324 (4.12).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.20 [9H, s, (CH ) ], 1.51 (2H, m, CH -9), 1.62 (2H, m, CH -10),
6
3 3
2
2
1.87 (2H, m, CH -8), 2.77 (2H, m, CH -11), 2.95 (2H, m, CH -7), 5.18 (2H, s, CH -1′), 6.86 (2H, m, H-2, H-4), 7.69 (1H, d,
2
2
2
2
J = 8.7, H-1).
3-(3,3-Dimethyl-2-oxobutoxy)-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (6). Yield84%,mp184-
185°C, C H O .
20 24
4
-1
IR spectrum (KBr, cm ): 2918, 1722, 1683, 1600, 1569, 1502, 1463, 1373, 1304, 1242, 1211, 1141, 1076, 998, 779.
UV spectrum (CH CN, nm, log ε): 207 (4.74), 221 (4.29), 326 (4.31).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.19 [9H, s, (CH ) ], 1.51 (2H, m, CH -9), 1.60 (2H, m, CH -10),
6
3 3
2
2
1.88 (2H, m, CH -8), 2.26 (3H, s, CH -4), 2.80 (2H, m, CH -11), 2.95 (2H, m, CH -7), 5.24 (2H, s, CH -1′), 6.78 (1H, d,
2
3
2
2
2
J = 8.7, H-2), 7.56 (1H, d, J = 8.7, H-1).
3-(1-Methyl-2-oxopropoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (7). Yield 81%, mp 113-114°C,
C H O .
18 20
4
-1
IR spectrum (KBr, cm ): 2912, 1709, 1608 1460, 1389, 1287, 1255, 1236, 1180, 1150, 1100, 876.
UV spectrum (CH CN, nm, log ε): 205 (4.57), 221 (4.15), 323 (4.15).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.48 (1H, d, J = 7.2, CH -1′), 1.51 (2H, m, CH -9), 1.62 (2H,
6
3
2
m, CH -10), 1.87 (2H, m, CH -8), 2.19 (3H, s, CH -3′), 2.75 (2H, m, CH -11), 2.93 (2H, m, CH -7), 5.06 (1H, q, H-1′), 6.83
2
2
3
2
2
(1H, d, J = 2.4, H-4), 6.86 (1H, dd, J = 2.4, 8.7, H-2), 7.72 (1H, d, J = 8.7, H-1).
4-Methyl-3-(1-methyl-2-oxopropoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (8). Yield 83%, mp 140-
141°C, C H O .
19 22
4
-1
IR spectrum (KBr, cm ): 2928, 1698, 1603, 1464, 1445, 1369, 1282, 1270, 1245, 1136, 1112.
UV spectrum (CH CN, nm, log ε): 208 (4.57), 225 (4.16), 326 (4.10).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.49 (1H, d, J = 7.2, CH -1′), 1.51 (2H, m, CH -9), 1.62 (2H,
6
3
2
m, CH -10), 1.87 (2H, m, CH -8), 2.18 (3H, s, CH -3′), 2.28 (3H, s, CH -4), 2.78 (2H, m, CH -11), 2.92 (2H, m, CH -7), 5.03
2
2
3
3
2
2
(1H, q, H-1′), 6.79 (1H, d, J = 8.7, H-2), 7.57 (1H, d, J = 8.7, H-1).
658

3-(1-Methyl-2-oxo-2-phenylethoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (9). Yield 85%, mp 115-
116°C, C H O .
23 22
4
-1
IR spectrum (KBr, cm ): 2925, 1704, 1692, 1613, 1558, 1451, 1295, 1270, 1230, 1154, 1135, 1095, 1074, 964, 853.
UV spectrum (CH CN, nm, log ε): 204 (4.85), 225 (4.35), 243 (4.40), 324 (4.30).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.60 (3H, d, J = 6.4, Me-2′), 1.62 (2H, m,
6
2
CH -10), 1.84 (2H, m, CH -8), 2.74 (2H, m, CH -11), 2.90 (2H, m, CH -7), 6.11 (1H, q, H-1′), 6.85 (1H, d, J = 2.4, H-4), 6.88
2
2
2
2
(1H, dd, J = 2.4, 8.7, H-2), 7.55 (2H, t, J = 7.6, H-3″, H-5″), 7.67 (1H, m, H-4″′), 7.71 (1H, d, J = 8.7, H-1), 8.07 (2H, d,
J = 8.0, H-2″, H-6″).
4-Methyl-3-(1-methyl-2-oxo-2-phenylethoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (10). Yield83%,
mp 184-185°C, C H O .
24 24
4
-1
IR spectrum (KBr, cm ): 2948, 1742, 1706, 1678, 1642, 1627, 1579, 1468, 1401, 1337, 1154, 1116.
UV spectrum (dioxane, nm, log ε): 211 (4.78), 227 (4.35), 245 (4.32), 327 (4.22).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.54 (2H, m, CH -9), 1.60 (2H, m, CH -10), 1.62 (3H, d, J = 6.4,
6
2
2
Me-2′), 1.84 (2H, m, CH -8), 2.27 (3H, s, CH -4), 2.77 (2H, m, CH -11), 2.88 (2H, m, CH -7), 6.09 (1H, q, H-1′), 6.79 (1H,
2
3
2
2
d, J = 8.7, H-2), 7.54 (2H, t, J = 7.6, H-3″, H-5″), 7.56 (1H, d, J = 8.7, H-1), 7.67 (1H, m, H-4″′), 8.05 (2H, d, J = 8.0, H-2″,
H-6″).
3-(2-Oxo-2-phenylethoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (11). Yield 86%, mp 166-167°C,
C H O .
22 20
4
-1
IR spectrum (KBr, cm ): 2934, 1704, 1688, 1615, 1561, 1426, 1330, 1300, 1233, 1167, 1102, 1008, 967, 852.
UV spectrum (CH CN, nm, log ε): 204 (4.80), 224 (4.29), 242 (4.26), 325 (4.20).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.62(2H, m, CH -10), 1.85 (2H, m, CH -8),
6
2
2
2
2.79 (2H, m, CH -11), 2.96 (2H, m, CH -7), 5.65 (2H, s, CH -1′), 6.96 (1H, dd, J = 2.4, 8.7, H-2), 7.01 (1H, d, J = 2.4, H-4),
2
2
2
7.55 (2H, t, J = 7.5, H-3″, H-5″), 7.67 (1H, t, J = 7.5, H-4″), 7.72 (1H, d, J = 8.7, H-1), 8.03 (2H, d, J = 7.5, H-2″, H-6″).
4-Methyl-3-(2-oxo-2-phenylethoxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (12). Yield 89%, mp 198-
199°C, C H O .
23 22
4
-1
IR spectrum (KBr, cm ): 2923, 1689, 1601, 1569, 1459, 1372, 1305, 1225, 1211, 1140, 1127, 970.
UV spectrum (CH CN, nm, log ε): 206 (4.86), 225 (4.30), 244 (4.33), 326 (4.32).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.60 (2H, m, CH -10), 1.85 (2H, m, CH -8),
6
2
2
2
2.30 (3H, s, CH -4), 2.79 (2H, m, CH -11), 2.93 (2H, m, CH -7), 5.67 (2H, s, CH -1′), 6.92 (1H, d, J = 8.7, H-2), 7.55 (2H,
3
2
2
2
t, J = 7.5, H-3″, H-5″), 7.58 (1H, d, J = 8.7, H-1), 7.67 (1H, t, J = 7.5, H-4″), 8.02 (2H, d, J = 7.5, H-2″, H-6″).
3-[2-(4-Fluorophenyl)-2-oxoethoxy]-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (13). Yield 89%, mp 163-
164°C, C H FO .
22 19
4
-1
IR spectrum (KBr, cm ): 2933, 1711, 1686, 1615, 1599, 1561, 1510, 1414, 1328, 1298, 1230, 1207, 1169, 1157, 1101,
1007, 839.
UV spectrum (EtOH, nm, log ε): 204 (4.65), 225 (4.09), 246 (4.00), 328 (4.01).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.53 (2H, m, CH -9), 1.64 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.79 (2H, m, CH -11), 2.96 (2H, m, CH -7), 5.63 (2H, s, CH -1′), 6.96 (1H, dd, J = 2.4, 8.7, H-2), 7.02 (1H, d, J = 2.4, H-4),
2
2
2
7.34 (2H, t, J = 9.0, H-3″, H-5″), 7.73 (1H, d, J = 8.7, H-1), 8.12 (2H, m, H-2″, H-6″).
3-[2-(4-Fluorophenyl)-2-oxoethoxy]-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (14). Yield90%,
mp 199-200°C, C H FO .
23 21
4
-1
IR spectrum (KBr, cm ): 2926, 1710, 1690, 1600, 1570, 1505, 1447, 1373, 1308, 1230, 1142, 1130, 979, 841.
UV spectrum (CH CN, nm, log ε): 206 (4.75), 226 (4.12), 245 (4.19), 326 (4.19).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.50 (2H, m, CH -9), 1.61 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.30 (3H, s, CH -4), 2.77 (2H, m, CH -11), 2.92 (2H, m, CH -7), 5.65 (2H, s, CH -1′), 6.92 (1H, d, J = 8.7, H-2), 7.34 (2H,
3
2
2
2
t, J = 9.0, H-3″, H-5″), 7.57 (1H, d, J = 8.7, H-1), 8.11 (2H, m, H-2″, H-6″).
3-[2-(4-Chlorophenyl)-2-oxoethoxy]-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (15). Yield 92%, mp 184-
185°C, C H ClO .
22 19
4
-1
IR spectrum (KBr, cm ): 2920, 1698, 1610, 1592, 1426, 1390, 1256, 1227, 1174, 1092, 1008, 986, 969, 818.
UV spectrum (CH CN, nm, log ε): 206 (4.75), 225 (4.18), 252 (4.28), 326 (4.20).
3
659

PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.53(2H, m, CH -9), 1.65 (2H, m, CH -10), 1.90 (2H, m, CH -8),
6
2
2
2
2.78 (2H, m, CH -11), 2.96 (2H, m, CH -7), 5.62 (2H, s, CH -1′), 6.96 (1H, dd, J = 2.4, 8.7, H-2), 7.02 (1H, d, J = 2.4, H-4),
2
2
2
7.58 (2H, d, J = 8.4, H-3″, H-5″), 7.72 (1H, d, J = 8.7, H-1), 8.04 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(4-Chlorophenyl)-2-oxoethoxy]-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (16). Yield87%,
mp 206-207°C, C H ClO .
23 21
4
-1
IR spectrum (KBr, cm ): 2924, 1712, 1689, 1601, 1571, 1446, 1372, 1301, 1227, 1143, 1130, 1093, 976.
UV spectrum (dioxane, nm, log ε): 253 (4.03), 327 (3.95).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.61 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.30 (3H, s, CH -4), 2.78 (2H, m, CH -11), 2.91 (2H, m, CH -7), 5.66 (2H, s, CH -1′), 6.93 (1H, d, J = 8.7, H-2), 7.56 (1H,
3
2
2
2
d, J = 8.7, H-1), 7.59 (2H, d, J = 8.4, H-3″, H-5″), 8.03 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(4-Bromophenyl)-2-oxoethoxy]-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (17). Yield 89%, mp 182-
183°C, C H BrO .
22 19
4
-1
IR spectrum (KBr, cm ): 2915, 1699, 1608, 1587, 1426, 1390, 1256, 1224, 1176, 1100, 1074, 1007, 985, 969, 815.
UV spectrum (CH CN, nm, log ε): 205 (4.77), 218 (4.35), 256 (4.32), 326 (4.22).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.62 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.76 (2H, m, CH -11), 2.95 (2H, m, CH -7), 5.64 (2H, s, CH -1′), 6.96 (1H, dd, J = 2.4, 8.7, H-2), 7.02 (1H, d, J = 2.4, H-4),
2
2
2
7.71 (1H, d, J = 8.7, H-1), 7.74 (2H, d, J = 8.4, H-3″, H-5″), 7.96 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(4-Bromophenyl)-2-oxoethoxy]-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (18). Yield87%,
mp 205-206°C, C H BrO .
23 21
4
-1
IR spectrum (KBr, cm ): 2922, 1710, 1689, 1601, 1588, 1571, 1444, 1372, 1299, 1227, 1143, 1130, 1072, 974, 809,
776.
UV spectrum (dioxane, nm, log ε): 212 (4.86), 258 (4.45), 326 (4.32).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.61 (2H, m, CH -10), 1.88 (2H, m, CH -8),
6
2
2
2
2.30 (3H, s, CH -4), 2.77 (2H, m, CH -11), 2.91 (2H, m, CH -7), 5.65 (2H, s, CH -1′), 6.94 (1H, d, J = 8.7, H-2), 7.56 (1H,
3
2
2
2
d, J = 8.7, H-1), 7.75 (2H, d, J = 8.4, H-3″, H-5″), 7.94 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(4-Methoxyphenyl)-2-oxoethoxy]-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (19). Yield93%, mp189-
190°C, C H O .
23 22
5
-1
IR spectrum (KBr, cm ): 1697, 1602, 1574, 1425, 1292, 1268, 1242, 1182, 1135, 1028, 984, 834.
UV spectrum (CH CN, nm, log ε): 207 (4.67), 219 (4.38), 284 (4.28), 326 (4.21).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.62 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.79 (2H, m, CH -11), 2.93 (2H, m, CH -7), 3.87 (3H, s, OCH -4″), 5.56 (2H, s, CH -1′), 6.94 (1H, dd, J = 2.4, 8.7, H-2), 6.97
2
2
3
2
(1H, d, J = 2.4, H-4), 7.04 (2H, d, J = 8.7, H-3″, H-5″), 7.72 (1H, d, J = 8.7, H-1), 8.00 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(4-Methoxyphenyl)-2-oxoethoxy]-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (20). Yield89%,
mp 192-193°C, C H O .
24 24
5
-1
IR spectrum (KBr, cm ): 2924, 1697, 1602, 1574, 1507, 1425, 1292, 1268, 1242, 1183, 1135, 1027, 984, 834.
UV spectrum (CH CN, nm, log ε): 206 (4.73), 221 (4.42), 286 (4.31), 324 (4.26).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.62 (2H, m, CH -10), 1.87 (2H, m, CH -8),
6
2
2
2
2.30 (3H, s, CH -4), 2.79 (2H, m, CH -11), 2.93 (2H, m, CH -7), 3.87 (3H, s, OCH -4″), 5.59 (2H, s, CH -1′), 6.89 (1H, d,
3
2
2
3
2
J = 8.7, H-2), 7.06 (2H, d, J = 8.4, H-3″, H-5″), 7.55 (1H, d, J = 8.7, H-1), 7.98 (2H, d, J = 8.4, H-2″, H-6″).
3-[2-(3-Methoxyphenyl)-2-oxoethoxy]-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (21). Yield83%, mp140-
141°C, C H O .
23 22
5
-1
IR spectrum (KBr, cm ): 2912, 1710, 1692, 1612, 1560, 1466, 1426, 1333, 1300, 1265, 1239, 1158, 1099, 1040, 1014,
843, 786.
UV spectrum (EtOH, nm, log ε): 205 (4.91), 221 (4.77), 250 (4.27), 322 (4.43).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.53 (2H, m, CH -9), 1.65 (2H, m, CH -10), 1.89 (2H, m, CH -8),
6
2
2
2
2.78 (2H, m, CH -11), 2.95 (2H, m, CH -7), 3.85 (3H, s, OCH -3″), 5.62 (2H, s, CH -1′), 6.95 (1H, dd, J = 2.4, 8.7, H-2), 7.00
2
2
3
2
(1H, d, J = 2.4, H-4), 7.22 (1H, dd, J = 2.7, 8.4, H-4″), 7.45 (1H, t, J = 8.4, H-5″), 7.51 (1H, dd, J = 2.7, H-2″), 7.62 (1H, d,
J = 8.4, H-6″), 7.72 (1H, d, J = 8.7, H-1).
3-[2-(3-Methoxyphenyl)-2-oxoethoxy]-4-methyl-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (22). Yield87%,
mp 197-198°C, C H O .
24 24
5
660

-1
IR spectrum (KBr, cm ): 2918, 1691, 1601, 1572, 1462, 1428, 1335, 1298, 1269, 1248, 1131, 1077, 782.
UV spectrum (CH CN, nm, log ε): 208 (4.80), 221 (4.72), 248 (4.19), 321 (4.33).
3
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.51 (2H, m, CH -9), 1.62 (2H, m, CH -10), 1.85 (2H, m, CH -8),
6
2
2
2
2.31 (3H, s, CH -4), 2.77 (2H, m, CH -11), 2.91 (2H, m, CH -7), 3.85 (3H, s, OCH -3″), 5.66 (2H, s, CH -1′), 6.91 (1H, d,
3
2
2
3
2
J = 8.7, H-2), 7.23 (1H, dd, J = 2.7, 8.4, H-4″), 7.45 (1H, t, J = 8.4, H-5″), 7.49 (1H, dd, J = 2.7, 2.7, H-2″), 7.58 (1H, d, J = 8.7,
H-1), 7.61 (1H, d, J = 8.4, H-6″).
3-(2-Oxocyclohexyloxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (23). Yield 65%, mp 187-188°C,
C H O .
20 22
4
-1
IR spectrum (KBr, cm ): 2922, 1725, 1689, 1604, 1509, 1385, 1288, 1255, 1234, 1209, 1178, 1147, 1096, 1076, 858,
781.
UV spectrum (EtOH, nm, log ε): 204 (4.67), 226 (4.28), 328 (4.23).
PMRspectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.62-2.68(12H, m, CH -8, CH -10, CH -3′,
6
2
2
2
2
CH -4′, CH -5′, CH -6′), 2.77 (2H, m, CH -11), 2.95 (2H, m, CH -7), 5.13 (1H, m, H-2′), 6.85 (2H, m, H-2, H-4), 7.67 (1H,
2
2
2
2
2
d, J = 8.7, H-1).
4-Methyl-3-(2-oxocyclohexyloxy)-8,9,10,11-tetrahydrocyclohepta[c]chromen-6-one (24). Yield 69%, mp 200-
201°C, C H O .
21 24
4
-1
IR spectrum (KBr, cm ): 2930, 1711, 1599, 1572, 1501, 1463, 1449, 1368, 1313, 1286, 1269, 1244, 1123, 1106, 1076,
777.
UV spectrum (EtOH, nm, log ε): 207 (4.55), 227 (4.09), 328 (4.06).
PMRspectrum (300MHz, DMSO-d , δ, ppm, J/Hz): 1.52 (2H, m, CH -9), 1.60-2.68 (12H, m, CH -8, CH -10, CH -3′,
6
2
2
2
2
CH -4′, CH -5′, CH -6′), 2.24 (3H, s, CH -4), 2.78 (2H, m, CH -11), 2.92 (2H, m, CH -7), 5.13 (1H, m, H-2″), 6.79 (1H, d,
2
2
2
3
2
2
J = 8.7, H-2), 7.51 (1H, d, J = 8.7, H-1).
2,3,4,5-Tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-ones25-46. Asolution or suspension ofketone3-24(2mmol)
in propan-2-ol (10 mL) was treated with NaOH solution (10 mL, 1 N). The reaction mixture was heated for 3-4 h (course of
reaction monitored by TLC) and poured into H SO solution (100 mL, 1 N). The resulting precipitate was filtered off and
2
4
crystallized from propan-2-ol.
11-Methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (25). Yield81%, mp166-167°C, C H O .
17 16
3
-1
IR spectrum (KBr, cm ): 2923, 1703, 1627, 1574, 1454, 1393, 1331, 1136, 1101, 1077, 1063, 996, 875.
UV spectrum (CH CN, nm, log ε): 212 (4.52), 246 (4.44), 295 (4.17), 305 (4.13), 331 (4.00).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.29 (3H, s, CH -11), 2.83 (2H, m, CH -1), 3.07 (2H, m, CH -5), 7.46 (1H, s, H-8), 7.73 (1H, s, H-10), 7.99 (1H, s, H-12).
3
2
2
8,11-Dimethyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (26). Yield 83%, mp 183-184°C,
C H O .
18 18
3
-1
IR spectrum (KBr, cm ): 2918, 1690, 1588, 1446, 1397, 1353, 1304, 1191, 1122, 1078.
UV spectrum (EtOH, nm, log ε): 215 (4.62), 252 (4.42), 314 (4.19).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.66 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.28 (3H, s, CH -11), 2.47 (3H, s, CH -8), 2.85 (2H, m, CH -1), 3.06 (2H, m, CH -5), 7.73 (1H, s, H-10), 7.83 (1H, s, H-12).
3
3
2
2
11-(t-Butyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (27). Yield85%, mp168-169°C, C H O .
20 22
3
-1
IR spectrum (KBr, cm ): 2934. 1712, 1626, 1575, 1454, 1389, 1204, 1130, 1096, 1079, 836, 779.
UV spectrum (CH CN, nm, log ε): 223 (4.84), 250 (4.41), 312 (4.13).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.44 [9H, s, (CH ) ], 1.55 (2H, m, CH -3), 1.72 (2H, m, CH -2),
6
3 3
2
2
1.89 (2H, m, CH -4), 2.86 (2H, m, CH -1), 3.09 (2H, m, CH -5), 7.51 (1H, s, H-8), 7.67 (1H, s, H-10), 8.04 (1H, s, H-12).
2
2
2
11-(t-Butyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (28). Yield87%,mp228-229°C,
C H O .
21 24
3
-1
IR spectrum (KBr, cm ): 2928, 1709, 1590, 1449, 1379, 1351, 1204, 1118, 1071, 997, 779.
UV spectrum (CH CN, nm, log ε): 213 (4.44), 252 (4.29), 296 (4.06), 311 (4.06), 338 (3.84).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.44 [9H, s, (CH ) ], 1.56 (2H, m, CH -3), 1.69 (2H, m, CH -2),
6
3 3
2
2
1.90 (2H, m, CH -4), 2.49 (3H, s, CH -8), 2.85 (2H, m, CH -1), 3.09 (2H, m, CH -5), 7.64 (1H, s, H-10), 7.87 (1H, s, H-12).
2
3
2
2
10,11-Dimethyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (29). Yield 79%, mp 185-186°C,
C H O .
18 18
3
661

-1
IR spectrum (KBr, cm ): 2919, 1707, 1639, 1578, 1456, 1395, 1272, 1157, 1142, 1123, 1100, 998, 858.
UV spectrum (EtOH, nm, log ε): 215 (4.57), 256 (4.51), 300 (4.20), 344 (4.02).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.20 (3H, s, CH -11), 2.40 (3H, s, CH -10), 2.80 (2H, m, CH -1), 3.05 (2H, m, CH -5), 7.37 (1H, s, H-8), 7.83 (1H, s, H-12).
3
3
2
2
8,10,11-Trimethyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (30). Yield 84%, mp 200-201°C,
C H O .
19 20
3
-1
IR spectrum (KBr, cm ): 2923, 1693, 1641, 1587, 1453, 1406, 1354, 1271, 1174, 1139, 1112, 997, 850.
UV spectrum (CH CN, nm, log ε): 213 (4.49), 256 (4.49), 301 (4.14), 311 (4.11), 348 (3.82).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.65 (2H, m, CH -2), 1.89 (2H, m, CH -4),
6
2
2
2
2.17 (3H, s, CH -11), 2.40 (3H, s, CH -10), 2.45 (3H, s, CH -8), 2.83 (2H, m, CH -1), 3.05 (2H, m, CH -5), 7.63 (1H, s, H-12).
3
3
3
2
2
10-Methyl-11-phenyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (31). Yield86%, mp201-202°C,
C H O .
23 20
3
-1
IR spectrum (KBr, cm ): 2914, 1709, 1623, 1578, 1498, 1439, 1394, 1303, 1194, 1149, 1098, 1077, 997, 842, 773.
UV spectrum (EtOH, nm, log ε): 214 (4.59), 230 (4.40), 257 (4.49), 302 (4.20), 343 (3.93).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.54 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.91 (2H, m, CH -4),
6
2
2
2
2.48 (3H, s, CH -10), 2.81 (2H, m, CH -1), 3.04 (2H, m, CH -5), 7.44 (1H, m, H-4′, 7.56 (4H, m, H-2′, H-3′, H-5′, H-6′), 7.59
3
2
2
(1H, s, H-8), 7.64 (1H, s, H-12).
8,10-Dimethyl-11-phenyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (32). Yield 83%, mp 224-
225°C, C H O .
24 22
3
-1
IR spectrum (KBr, cm ): 2911, 1709, 1630, 1588, 1440, 1398, 1307, 1273, 1169, 1115, 996, 750.
UV spectrum (dioxane, nm, log ε): 212 (4.58), 256 (4.45), 299 (4.16), 314 (4.05), 342 (3.82).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.50 (3H, s, CH -8), 2.54 (3H, s, CH -10), 2.80 (2H, m, CH -1), 3.05 (2H, m, CH -5), 7.43 (1H, m, H-4′), 7.49 (1H, s, H-12),
3
3
2
2
7.54 (4H, m, H-2′, H-3′, H-5′, H-6′).
11-Phenyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (33). Yield92%, mp177-178°C, C H O .
22 18
3
-1
IR spectrum (KBr, cm ): 2920, 1707, 1628, 1608, 1576, 1451, 1390, 1333, 1154, 1100, 1079, 998, 847, 759.
UV spectrum (EtOH, nm, log ε): 204 (4.66), 211 (4.66), 229 (4.50), 251 (4.47), 305 (4.29).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.89 (2H, m, CH -4),
6
2
2
2
2.82 (2H, m, CH -1), 3.07 (2H, m, CH -5), 7.40 (1H, m, H-4′), 7.52 (2H, t, J = 7.5, H-3′, H-5′), 7.60 (1H, s, H-8), 7.73 (2H,
2
2
d, J = 7.5, H-2′, H-6′), 8.14 (1H, s, H-12), 8.30 (1H, s, H-10).
8-Methyl-11-phenyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (34). Yield 89%, mp 199-200°C,
C H O .
23 20
3
-1
IR spectrum (KBr, cm ): 2934, 1698, 1605, 1586, 1565, 1452, 1384, 1121, 1103, 996, 751.
UV spectrum (EtOH, nm, log ε): 201 (4.64), 216 (4.58), 253 (4.42), 310 (4.31).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.91 (2H, m, CH -4),
6
2
2
2
2.54 (3H, s, CH -8), 2.84 (2H, m, CH -1), 3.06 (2H, m, CH -5), 7.40 (1H, m, H-4′), 7.52 (2H, t, J = 7.5, H-3′, H-5′), 7.72 (2H,
3
2
2
d, J = 7.5, H-2′, H-6′), 7.99 (1H, s, H-12), 8.30 (1H, s, H-10).
11-(4-Fluorophenyl)-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (35). Yield 86%, mp 178-179°C,
C H FO .
22 17
3
-1
IR spectrum (KBr, cm ): 2921, 1692, 1627, 1574, 1504, 1475, 1391, 1336, 1218, 1156, 1110, 1087, 838, 802.
UV spectrum (CH CN, nm, log ε): 204 (4.53), 214 (4.48), 229 (4.33), 252 (4.36), 298 (4.17), 325 (3.91).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.85 (2H, m, CH -1), 3.12 (2H, m, CH -5), 7.31 (2H, t, J = 7.5, H-3′, H-5′), 7.67 (1H, s, H-8), 7.80 (2H, m, H-2′, H-6′), 8.16
2
2
(1H, s, H-12), 8.34 (1H, s, H-10).
11-(4-Fluorophenyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (36). Yield91%, mp217-
218°C, C H FO .
23 19
3
-1
IR spectrum (KBr, cm ): 2918, 1714, 1703, 1608, 1583, 1505, 1387, 1265, 1215, 1121, 1095, 840.
UV spectrum (CH CN, nm, log ε): 214 (4.41), 252 (4.32), 298 (4.12), 340 (3.73).
3
662

PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.65 (2H, m, CH -2), 1.89 (2H, m, CH -4),
6
2
2
2
2.52 (3H, s, CH -8), 2.83 (2H, m, CH -1), 3.04 (2H, m, CH -5), 7.29 (2H, t, J = 7.5, H-3′, H-5′), 7.75 (2H, m, H-2′, H-6′), 7.94
3
2
2
(1H, s, H-12), 8.28 (1H, s, H-10).
11-(4-Chlorophenyl)-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (37). Yield89%, mp 211-212°C,
C H ClO .
22 17
3
-1
IR spectrum (KBr, cm ): 2917, 1692, 1628, 1579, 1487, 1393, 1354, 1160, 1107, 1092, 1080, 1015, 885, 825, 780.
UV spectrum (CH CN, nm, log ε): 204 (4.57), 214 (4.46), 242 (4.40), 253 (4.39), 298 (4.21), 305 (4.19), 336 (3.90).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
3
2.84 (2H, m, CH -1), 3.08 (2H, m, CH -5), 7.53 (2H, d, J = 8.4, H-3′, H-5′), 7.62 (1H, s, H-8), 7.76 (2H, d, J = 8.4, H-2′, H-6′),
2
2
8.14 (1H, s, H-12), 8.36 (1H, s, H-10).
11-(4-Cchlorophenyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (38). Yield 92%, mp
228-229°C, C H ClO .
23 19
3
-1
IR spectrum (KBr, cm ): 2928, 1702, 1589, 1571, 1491, 1443, 1382, 1353, 1121, 1095, 997, 843, 798.
UV spectrum (dioxane, nm, log ε): 217 (4.41), 243 (4.35), 248 (4.38), 253 (4.39), 300 (4.15), 311 (4.09), 334 (3.90).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.65 (2H, m, CH -2), 1.87 (2H, m, CH -4),
6
2
2
2
2.52 (3H, s, CH -8), 2.83 (2H, m, CH -1), 3.06 (2H, m, CH -5), 7.52 (2H, d, J = 8.4, H-3′, H-5′), 7.73 (2H, d, J = 8.4, H-2′,
3
2
2
H-6′), 7.95 (1H, s, H-12), 8.32 (1H, s, H-10).
11-(4-Bromophenyl)-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (39). Yield 89%, mp 215-216°C,
C H BrO .
22 17
3
-1
IR spectrum (KBr, cm ): 1692, 1628, 1579, 1482, 1452, 1392, 1354, 1205, 1159, 1106, 1079, 1011, 885, 822.
UV spectrum (EtOH, nm, log ε): 203 (4.52), 219 (4.22), 254 (4.21), 298 (4.06), 316 (4.00).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.83 (2H, m, CH -1), 3.08 (2H, m, CH -5), 7.66 (1H, s, H-8), 7.68 (2H, d, J = 8.4, H-3′, H-5′), 7.71 (2H, d, J = 8.4, H-2′, H-6′),
2
2
8.16 (1H, s, H-12), 8.39 (1H, s, H-10).
11-(4-Bromophenyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (40). Yield93%,mp250-
251°C, C H BrO .
23 19
3
-1
IR spectrum (KBr, cm ): 2927, 1701, 1590, 1577, 1487, 1454, 1382, 1353, 1296, 1200, 1121, 1096, 1075, 1008, 997,
829, 798.
UV spectrum (CH CN, nm, log ε): 205 (4.42), 212 (4.32), 247 (4.27), 251 (4.26), 298 (4.06), 307 (4.03), 337 (3.74).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.65 (2H, m, CH -2), 1.88 (2H, m, CH -4),
6
2
2
2
2.52 (3H, s, CH -8), 2.81 (2H, m, CH -1), 3.05 (2H, m, CH -5), 7.66 (2H, d, J = 8.4, H-3′, H-5′), 7.69 (2H, d, J = 8.4, H-2′,
3
2
2
H-6′), 7.96 (1H, s, H-12), 8.35 (1H, s, H-10).
11-(4-Methoxyphenyl)-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (41). Yield86%, mp162-163°C,
C H O .
23 20
4
-1
IR spectrum (KBr, cm ): 2921, 1694, 1627, 1582, 1507, 1452, 1393, 1273, 1248, 1174, 1159, 1108, 1080, 1036, 886,
823.
UV spectrum (CH CN, nm, log ε): 207 (4.53), 233 (4.34), 251 (4.37), 307 (4.18).
3
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.68 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.84 (2H, m, CH -1), 3.07 (2H, m, CH -5), 3.84 (3H, s, OCH -4′), 7.06 (2H, d, J = 8.4, H-3′, H-5′), 7.60 (1H, s, H-8), 7.64 (2H,
2
2
3
d, J = 8.4, H-2′, H-6′), 8.11 (1H, s, H-12), 8.20 (1H, s, H-10).
11-(4-Methoxyphenyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (42). Yield94%, mp
216-217°C, C H O .
24 22
4
-1
IR spectrum (KBr, cm ): 2615, 1702, 1586, 1509, 1439, 1388, 1303, 1266, 1251, 1180, 1121, 1092, 1033, 840, 793.
UV spectrum (dioxane, nm, log ε): 216 (4.39), 242 (4.41), 253 (4.44), 303 (4.27).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.66 (2H, m, CH -2), 1.88 (2H, m, CH -4),
6
2
2
2
2.52 (3H, s, CH -8), 2.83 (2H, m, CH -1), 3.04 (2H, m, CH -5), 3.83 (3H, s, OCH -4′), 7.06 (2H, d, J = 8.4, H-3′, H-5′), 7.61
3
2
2
3
(2H, d, J = 8.4, H-2′, H-6′), 7.93 (1H, s, H-12), 8.18 (1H, s, H-10).
11-(3-Methoxyphenyl)-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (43). Yield91%,mp153-154°C,
C H O .
23 20
4
-1
IR spectrum (KBr, cm ): 2933, 1690, 1627, 1602, 1575, 1466, 1341, 1239, 1221, 1162, 1100, 1084, 863, 839, 792.
663

UV spectrum (dioxane, nm, log ε): 212 (4.74), 251 (4.33), 298 (4.32), 309 (4.28), 342 (3.98).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.56 (2H, m, CH -3), 1.71 (2H, m, CH -2), 1.89 (2H, m, CH -4),
6
2
2
2
2.83 (2H, m, CH -1), 3.07 (2H, m, CH -5), 3.86 (3H, s, OCH -3′), 6.95 (1H, dd, J = 2.7, 8.4, H-4′), 7.22 (1H, dd, J = 2.7, 2.7,
2
2
3
H-2′), 7.30 (1H, d, J = 8.4, H-6′), 7.42 (1H, t, J = 8.4, H-5′), 7.60 (1H, s, H-8), 8.14 (1H, s, H-12), 8.29 (1H, s, H-10).
11-(3-Methoxyphenyl)-8-methyl-2,3,4,5-tetrahydrocyclohepta[c]furo[3,2-g]chromen-6-one (44). Yield89%, mp
192-193°C, C H O .
24 22
4
-1
IR spectrum (KBr, cm ): 2936, 1693, 1604, 1586, 1467, 1388, 1251, 1223, 1210, 1158, 1123, 1105, 1034, 856, 838,
793.
UV spectrum (dioxane, nm, log ε): 215 (4.54), 252 (4.33), 301 (4.21), 313 (4.16).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.90 (2H, m, CH -4),
6
2
2
2
2.56 (3H, s, CH -8), 2.83 (2H, m, CH -1), 3.5 (2H, m, CH -5), 3.85 (3H, s, OCH -3′), 6.95 (1H, dd, J = 2.7, 8.4, H-4′), 7.21
3
2
2
3
(1H, dd, J = 2.7, 2.7, H-2′), 7.30 (1H, d, J = 8.4, H-6′), 7.42 (1H, t, J = 8.4, H-5′), 7.99 (1H, s, H-12), 8.32 (1H, s, H-10).
2,3,4,5,10,11,12,13-Octahydro[1]benzofuro[3,2-g]cyclohepta[c]chromen-6-one (45). Yield 86%, mp 230-231°C,
C H O .
20 20
3
-1
IR spectrum (KBr, cm ): 2934, 1692, 1628, 1575, 1455, 1398, 1306, 1141, 1112, 1074, 1004, 879, 836.
UV spectrum (EtOH, nm, log ε): 214 (4.50), 257 (4.45), 302 (4.14), 340 (3.95).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.55 (2H, m, CH -3), 1.67 (2H, m, CH -2), 1.80-2.00 (6H, m,
6
2
2
CH -4, CH -11, CH -12), 2.61 (2H, m, CH -13), 2.73 (2H, m, CH -10), 2.81 (2H, m, CH -1), 3.06 (2H, m, CH -5), 7.40 (1H,
2
2
2
2
2
2
2
s, H-8), 7.82 (1H, s, H-14).
8-Methyl-2,3,4,5,10,11,12,13-octahydro[1]benzofuro[3,2-g]cyclohepta[c]chromen-6-one (46). Yield 83%, mp218-
219°C, C H O .
21 22
3
-1
IR spectrum (KBr, cm ): 2933, 1699, 1589, 1458, 1411, 1325, 1314, 1180, 1129, 1114, 1090, 998, 848, 775.
UV spectrum (EtOH, nm, log ε): 213 (4.58), 257 (4.48), 307 (4.21), 341 (4.02).
PMR spectrum (300 MHz, DMSO-d , δ, ppm, J/Hz): 1.54 (2H, m, CH -3), 1.64 (2H, m, CH -2), 1.80-2.00 (6H, m,
6
2
2
CH -4, CH -11, CH -12), 2.46 (3H, s, CH -8), 2.63 (2H, m, CH -13), 2.73 (2H, m, CH -10), 2.80 (2H, m, CH -1), 3.04 (2H,
2
2
2
3
2
2
2
m, CH -5), 7.65 (1H, s, H-14).
2
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