144
Y. Q. YE et al.
5,6-Bis(methoxymethoxy)benzo[1,3]dioxole-4,7-diyl bis(trifluoro-
1H-NMR (400 MHz, CDCl3) ꢁ: 7.54 (4H, d, J ¼ 8:5 Hz), 6.98 (4H, d,
J ¼ 8:5 Hz), 5.92 (2H, s), 4.87 (4H, s), 3.85 (6H, s), 3.06 (6H, s);
13C-NMR (100 MHz, CDCl3) ꢁ: 159.0, 142.0, 141.2, 131.5, 124.7,
117.7, 113.6, 101.0, 99.3, 57.2, 55.3; HRMS (ESI) m=z: calcd. for
C
66.08; H, 5.82%. Calcd. for C25H26O8: C, 66.07; H, 5.77%.
methanesulfonate) (21). To a stirred solution of 20 (1.09 g, 3.97 mmol)
in pyridine (40 ml) was added dropwise triflic anhydride (1.47 ml,
8.74 mmol) at 0 ꢁC and the mixture was stirred at the same temperature
for 2.5 h. After adding ice-cooled water, the resulting mixture was
stirred for 1 h and then extracted with ether. The extract was
successively washed with cold aqueous HCl, water, saturated aqueous
NaHCO3, water and brine, dried and concentrated. The residue was
chromatographed on silica gel (n-hexane-ethyl acetate ¼ 50 : 1) to
give 21 (1.89 g, 89%) as a white solid; mp 58.5–59.0 ꢁC (methanol);
IR ꢂmax (ZnSe) cmꢀ1: 3013, 1474, 1422, 1200, 1132, 1037, 995, 969;
1H-NMR (400 MHz, CDCl3) ꢁ: 6.14 (2H, s), 5.14 (4H, s), 3.60 (6H, s);
13C-NMR (125 MHz, CDCl3) ꢁ: 138.3, 137.6, 126.4, 118.5 (q,
JCF ¼ 320:9 Hz), 104.5, 100.1, 58.1; HRMS (ESI) m=z: calcd. for
C13H12F6NaO12S2 ½M þ Naꢂþ, 560.9572; found, 560.9573.
25H26O8Na ½M þ Naꢂþ, 477.1525; found, 477.1539. Anal. Found: C,
5,6-Bis(methoxymethoxy)-4-(p-(benzyloxy)phenyl)benzo[1,3]dioxole
(26) and 4,5,6-tris(methoxymethoxy)-7-(p-(benzyloxy)phenyl)benzo[1,3]-
dioxole (29). Tetrakis(triphenylphosphine)palladium (2.3 mg, 1.9 mmol)
was added to a stirred mixture of 8 (36.5 mg, 0.16 mmol), 21 (21.5 mg,
0.04 mmol), and cesium carbonate (52.1 mg, 0.16 mmol) in toluene
(1.5 ml), and the mixture was stirred at 100 ꢁC for 20 h. The treatment
described for the preparation of 22 yielded 24 (15.1 mg, 62%), 26
(3.8 mg, 22%), and 29 (1.4 mg, 7%).
26. Light yellow solid; IR ꢂmax (ZnSe) cmꢀ1: 2923, 1451, 1239,
1154, 1039, 984, 947; 1H-NMR (500 MHz, CDCl3) ꢁ: 7.47 (2H, d,
J ¼ 8:6 Hz), 7.45–7.31 (5H, m), 7.06 (1H, s), 7.02 (2H, d, J ¼ 8:6 Hz),
5.95 (2H, s), 5.12 (2H, s), 5.11 (2H, s), 4.72 (2H, s), 3.65 (3H, s), 3.11
(3H, s); 13C-NMR (125 MHz, CDCl3) ꢁ: 158.0, 142.5, 141.4, 137.0,
135.6, 133.4, 131.4, 131.1, 128.6, 128.0, 127.5, 124.9, 114.6, 110.6,
101.5, 100.4, 99.3, 70.0, 57.4, 57.1; HRMS (ESI) m=z: calcd. for
5,6-Bis(methoxymethoxy)-4,7-bis-(p-(t-butyldimethylsilyloxy)phen-
yl)-benzo[1,3]dioxole (22). To
a stirred mixture of 7 (1.93 g,
7.65 mmol), 21 (1.03 g, 1.91 mmol), potassium bromide (0.49 g,
4.11 mmol) and potassium phosphate (1.68 g, 7.91 mmol) in dioxane
(12 ml) was added tetrakis(triphenylphosphine)palladium (110 mg,
0.10 mmol), and the mixture was stirred at 100 ꢁC for 26 h, cooled,
and then diluted with water. The resulting mixture was extracted with
ether. The extract was successively washed with water and brine, dried,
and concentrated. The residue was chromatographed on silica gel
(n-hexane-ethyl acetate ¼ 200 : 1) to give 22 (1.20 g, 96%) as a white
solid; mp 174.5–175.5 ꢁC (ethanol); IR ꢂmax (ZnSe) cmꢀ1: 1515, 1438,
1250, 1169, 1044; 1H-NMR (400 MHz, CDCl3) ꢁ: 7.47 (4H, d,
J ¼ 8:6 Hz), 6.90 (4H, d, J ¼ 8:6 Hz), 5.93 (2H, s), 4.86 (4H, s), 3.02
(6H, s), 1.00 (18H, s), 0.21 (12H, s); 13C-NMR (100 MHz, CDCl3) ꢁ:
155.1, 141.9, 141.1, 131.5, 125.3, 119.7, 117.8, 101.0, 99.2, 57.1, 25.7,
18.2, ꢀ4:4. Anal. Found: C, 64.25; H, 7.75%. Calcd. for C35H50O8Si2:
C, 64.19; H, 7.69%.
C
24H24O7Na ½M þ Naꢂþ, 463.1369; found, 463.1354.
29. Light yellow solid; IR ꢂmax (ZnSe) cmꢀ1: 2920, 1609, 1435,
1236, 1156, 1088, 1058, 1037, 923, 888; 1H-NMR (600 MHz, CDCl3)
ꢁ: 7.47 (2H, d, J ¼ 8:5 Hz), 7.44 (2H, d, J ¼ 7:4 Hz), 7.38 (2H, dd,
J ¼ 7:4, 7.4 Hz), 7.32 (1H, t, J ¼ 7:4 Hz), 7.02 (2H, d, J ¼ 8:5 Hz),
5.91 (2H, s), 5.26 (2H, s), 5.13 (2H, s), 5.09 (2H, s), 4.78 (2H, s), 3.64
(3H, s), 3.59 (3H, s), 3.00 (3H, s); 13C-NMR (150 MHz, CDCl3) ꢁ:
158.1, 142.5, 142.1, 137.6, 136.9, 134.9, 133.3, 131.5, 128.6, 128.0,
127.5, 124.8, 114.6, 114.1, 101.3, 99.4, 99.3, 97.5, 70.0, 57.5, 57.1,
57.0; HRMS (ESI) m=z: calcd. for C26H28O9Na ½M þ Naꢂþ, 507.1631;
found, 507.1630.
5,6-Bis(methoxymethoxy)-4,7-bis-(p-hydroxyphenyl)benzo[1,3]dioxole
(23). A mixture of 7 (23.2 mg, 91.9 mmol) and 21 (21.5 mg, 39.9 mmol)
in 1-propanol (1.0 ml) was stirred at rt for 30 min, allowing the solids
to dissolve. The resulting solution was treated with palladium acetate
(0.5 mg, 2.23 mmol), triphenylphosphine (1.6 mg, 6.10 mmol), 2 M
sodium carbonate (0.06 ml, 0.12 mmol) and water (0.19 ml), heated
at 100 ꢁC while stirring for 4 h, and then cooled to rt. After adding
water, the resulting mixture was stirred at rt for 1 h and then extracted
with ethyl acetate. The extract was successively washed with water and
brine, dried and concentrated. The residue was chromatographed
on silica gel (n-hexane-ethyl acetate ¼ 50 : 1 ! 10 : 1) to give 23
(15.7 mg, 92%) as a white solid; mp 198.5–199.5 ꢁC (n-hexane-ethyl
acetate); IR ꢂmax (ZnSe) cmꢀ1: 3391, 3296, 1518, 1400, 1270, 1204,
1170, 1041, 986, 951; 1H-NMR (400 MHz, acetone-d6) ꢁ: 8.46 (2H, s),
7.45 (4H, d, J ¼ 8:3 Hz), 6.92 (4H, d, J ¼ 8:3 Hz), 5.95 (2H, s), 4.84
(4H, s), 3.05 (6H, s); 13C-NMR (100 MHz, acetone-d6) ꢁ: 157.7, 142.9,
141.9, 132.5, 124.5, 118.4, 115.6, 101.6, 99.8, 57.1; HRMS (ESI) m=z:
calcd. for C23H22O8Na ½M þ Naꢂþ, 449.1212; found, 449.1225. Anal.
5,6-Bis(methoxymethoxy)-4-(p-(benzyloxy)phenyl)benzo[1,3]dioxole-
7-yl trifluoromethanesulfonate (27). Treatment of
8 (36.5 mg,
0.16 mmol) and 21 (21.5 mg, 0.04 mmol) as described for the
preparation of 22 yielded 21 (12.7 mg, 59%) and 27 (2.0 mg, 9%) as
a syrup; IR ꢂmax (ZnSe) cmꢀ1: 2908, 2831, 1426, 1375, 1206, 1136,
1052, 1023, 976; 1H-NMR (500 MHz, CDCl3) ꢁ: 7.50 (2H, d,
J ¼ 8:8 Hz), 7.45–7.32 (5H, m), 7.05 (2H, d, J ¼ 8:8 Hz), 6.01 (2H,
s), 5.20 (2H, s), 5.11 (2H, s), 4.77 (2H, s), 3.65 (3H, s), 3.02 (3H, s);
13C-NMR (125 MHz, CDCl3) ꢁ: 158.6, 142.6, 142.1, 137.9, 136.7,
136.0, 131.4, 128.6, 128.0, 127.4, 125.5, 123.5, 119.1, 118.6 (q,
JCF ¼ 320:5 Hz), 114.7, 102.6, 99.7, 99.4, 70.0, 57.9, 57.3; HRMS
(ESI) m=z: calcd. for C25H23F3O10NaS ½M þ Naꢂþ, 595.0862; found,
595.0862.
4,5,6-Tris(methoxymethoxy)-7-(p-(t-butyldimethylsilyloxy)phenyl)-
benzo[1,3]dioxole (28). Treatment of 7 (40.4 mg, 0.16 mmol) and 21
(21.5 mg, 0.04 mmol) as described for the preparation of 26 yielded 22
(18.2 mg, 70%) and 28 (2.1 mg, 10%) as an amorphous solid; IR ꢂmax
(ZnSe) cmꢀ1: 2927, 1607, 1514, 1434, 1252, 1157, 1057, 1035, 909;
1H-NMR (600 MHz, CDCl3) ꢁ: 7.40 (2H, d, J ¼ 8:5 Hz), 6.87 (2H, d,
J ¼ 8:5 Hz), 5.91 (2H, s), 5.26 (2H, s), 5.13 (2H, s), 4.77 (2H, s), 3.63
(3H, s), 3.59 (3H, s), 3.00 (3H, s), 0.99 (9H, s), 0.20 (6H, s); 13C-NMR
(150 MHz, CDCl3) ꢁ: 155.0, 142.5, 142.1, 137.6, 135.0, 133.2, 131.4,
125.1, 119.7, 114.3, 101.3, 99.4, 99.3, 97.5, 57.5, 57.1, 57.0, 25.7, 18.2,
.
Found: C, 64.31; H, 5.25%. Calcd. for C23H22O8 0.5H2O: C, 64.63;
H, 5.42%.
5,6-Bis(methoxymethoxy)-4,7-bis-(p-(benzyloxy)-phenyl)benzo[1,3]-
dioxole (24). Treatment of 8 (21.0 mg, 0.09 mmol) and 21 (21.5 mg,
0.04 mmol) as described for the preparation of 23 yielded 24 (18.5 mg,
76%) as colorless needles; mp 165–165.5 ꢁC (ethanol); IR ꢂmax (ZnSe)
cmꢀ1: 2904, 2826, 1436, 1246, 1051, 976, 956, 922, 828; 1H-NMR
(400 MHz, CDCl3) ꢁ: 7.54 (4H, d, J ¼ 8:8 Hz), 7.46–7.31 (10H, m),
7.05 (4H, d, J ¼ 8:8 Hz), 5.92 (2H, s), 5.11 (4H, s), 4.86 (4H, s), 3.02
(6H, s); 13C-NMR (100 MHz, CDCl3) ꢁ: 158.2, 142.0, 141.1, 136.9,
131.5, 128.6, 128.0, 127.5, 125.0, 117.7, 114.6, 101.0, 99.3, 70.0, 57.1;
HRMS (ESI) m=z: calcd. for C37H34O8Na ½M þ Naꢂþ, 629.2151;
found, 629.2162. Anal. Found: C, 73.15; H, 5.67%. Calcd. for
ꢀ4:4; HRMS (ESI) m=z: calcd. for
C
25H36O9SiNa ½M þ Naꢂþ,
531.2026; found, 531.2024.
5,6-Bis(phenylacetoxy)-4,7-bis-(p-(methoxy)phenyl)benzo[1,3]dioxole
(31). To a stirred solution of 25 (137 mg, 0.30 mmol) in dichloro-
methane (2.0 ml) was added a 10% HCl solution in methanol (2.0 ml),
and the mixture was stirred at rt for 11 h and then concentrated. The
residue was passed through a short column of silica gel (n-hexane-ethyl
acetate ¼ 50 : 1 ! dichloromethane) to give a syrup (93 mg) which
was treated with sodium dithionite (177 mg, 1.02 mmol) in ethyl
acetate-methanol-water (4:1:1; 6.0 ml) at rt for 1 h. The resulting
mixture was extracted with ethyl acetate. The extract was successively
washed with cold aqueous HCl, water and brine, dried, concentrated
and co-evaporated with dry benzene (ꢃ5) to give 30 as an amorphous
solid which was employed for the next step without further
C
37H34O8: C, 73.25; H, 5.65%.
5,6-Bis(methoxymethoxy)-4,7-bis-(p-(methoxy)-phenyl)benzo[1,3]-
dioxole (25). Treatment of 9 (14.0 mg, 0.09 mmol) and 21 (21.5 mg,
0.04 mmol) as described for the preparation of 23 yielded 25 (16.6 mg,
91%) as a white solid; mp 145.5–147 ꢁC (ethyl acetate); IR ꢂmax
(ZnSe) cmꢀ1: 2934, 2836, 1517, 1434, 1288, 1251, 1156, 1049, 1029;