6
Tetrahedron
.5, MAN
13
ppm. C NMR (100 MHz, CDCl ): δ = 19
A
0.2
C
,
C
15
E
7.6
P
,
T
14
E
4
D
2
U
-M
S
et
C
ho
R
xy
I
-6-(tetrahydro-2H-pyran-2-yloxy) benzaldehyde
P
T
3
9
a,3g
1
1
2
33.1, 124.9, 124.4, 115.5, 102.8, 68.5, 34.2, 32.7, 31.2 (3C),
3.4 ppm.
(3t) : (27 mg, 70% yield). Yellow liquid. H NMR (400 MHz,
CDCl ): δ = 10.58 (s, 1H), 7.42 (t, J = 8.4 Hz 1H), 6.83 (d, J =
3
8
3
.4 Hz, 1H), 6.60 (d, J = 8.4 Hz, 1H), 5.56 (s, 1H), 3.90 (s, 3H),
.87−3.83 (m, 1H), 3.65−3.61 (m, 1H), 1.93−1.88 (m, 2H),
3
-Methoxy-2-(tetrahydrofuran-2-yloxy)
benzaldehyde
3n) : (24 mg, 68% yield). Yellow liquid. H NMR (400 MHz,
CDCl ): δ = 10.34 (s, 1H), 7.43 (t, J = 4.6 Hz, 1H), 7.14 (d, J =
13
9a
1
1.72−1.55 (m, 4H) ppm. C NMR (100 MHz, CDCl ): δ = 189.4,
1
2
3
(
61.3, 160.0, 135.7, 115.7, 107.6, 104.5, 96.3, 61.9, 56.0, 30.0,
5.1, 18.2 ppm.
3
4
3
.6 Hz, 2H), 5.87 (d, J = 4.4 Hz, 1H), 4.12−4.07 (m, 1H),
.97−3.87 (m, 1H), 3.90 (s, 3H), 2.39−1.98 (m, 4H) ppm.
13
C
NMR (100 MHz, CDCl ): δ = 190.8, 152.7, 148.6, 131.3, 124.4,
4-(Diethylamino)-2-(tetrahydro-2H-pyran-2-yloxy)
benzaldehyde (3u): (13 mg, 37% yield). Yellow liquid. H NMR
3
1
1
19.0, 117.7, 106.1, 69.0, 56.0, 32.9, 23.4 ppm.
(
400 MHz, CDCl ): δ = 10.22 (s, 1H), 7.75 (d, J = 9.0 Hz, 1H),
3
6
.38 (s, 1H), 6.35 (d, J = 9.0, 1H), 5.55 (s, 1H), 3.98−3.91 (m,
4
-Methoxy-2-(tetrahydrofuran-2-yloxy)
benzaldehyde
1
9a
1H), 3.68−3.62 (m, 1H), 3.40 (q, J = 7.0 Hz, 4H), 2.06−1.56 (m,
(
3o) : (30 mg, 82% yield). Colourless liquid. H NMR (400
MHz, CDCl ): δ = 10.25 (s, 1H), 7.79 (d, J = 8.8 Hz, 1H), 6.77
d, J = 2.4 Hz, 1H), 6.59 (dd, J = 2.4, 8.8 Hz, 1H), 5.88 (t, J = 3.6
Hz, 1H), 4.11−3.96 (m, 2H), 3.86 (s, 3H), 2.28−2.14 (m, 3H),
.08−1.97 (m, 1H) ppm. C NMR (100 MHz, CDCl ): δ = 188.4,
66.9, 161.5, 129.9, 119.5, 107.7, 102.8, 101.0, 68.6, 55.6, 32.7,
3.3 ppm.
13
6
H), 1.20 (t, J = 7.0 Hz, 6H) ppm. C NMR (100 MHz, CDCl3):
δ = 187.1, 161.8, 153.8, 129.8, 114.7, 105.2, 96.3, 96.1, 61.9,
4.8 (2C), 30.2, 25.1, 18.3, 12.5 (2C) ppm. FT IR (KBr pellet,
3
(
4
-
1
13
cm ) 2928, 2852, 1665, 1599, 1521, 1403, 1356, 1270, 1201,
1
HRMS (ESI): m/z = [M + Na] calcd. for C H NO Na
3
2
1
2
3
+
121, 1100, 1036, 909, 766. MS (ESI): m/z = 278 [M + H] .
+
16
23
3
00.1576; found 300.1574.
9
a
3
-Methyl-2-(tetrahydrofuran-2-yloxy) benzaldehyde (3p) :
1
2-(Tetrahydro-2H-pyran-2-yloxy)-5-(trifluoromethoxy)
benzaldehyde (3v): (30 mg, 85% yield). Colorless liquid. H
(
36 mg, 95% yield). Colourless liquid. H NMR (400 MHz,
1
CDCl ): δ = 10.26 (s, 1H), 7.69 (d, J = 7.2 Hz, 1H), 7.45 (d, J =
7
4
3
NMR (400 MHz, CDCl ): δ = 10.50 (s, 1H), 7.69 (s, 1H), 7.38 (d,
3
.2 Hz, 1H), 7.15 (t, J = 7.2 Hz, 1H), 5.42 (d, J = 4.4 Hz, 1H),
.19−4.14 (m, 1H), 3.95 (q, 7.4 Hz, 1H), 2.41−2.36 (m, 1H), 2.32
J = 9.2 Hz, 1H), 7.29 (t, J = 9.8 Hz, 1H), 5.57 (d, J = 2.8 Hz 1H),
1
3
3.89−3.83 (m, 1H), 3.70−3.65 (m, 1H), 1.97−1.92 (m, 2H),
(s, 3H), 2.24−2.17 (m, 2H), 2.05−1.99 (m, 1H) ppm. C NMR
13
1
1
1
2
1
.76−1.60 (m, 4H) ppm. C NMR (125 MHz, CDCl ): δ = 188.4,
3
(100 MHz, CDCl ): δ = 191.2, 158.0, 137.1, 132.5, 130.4, 126.1,
3
57.8, 143.3, 128.6, 125.9, 121.5 (q, J = 256 Hz, CF ), 120.3,
3
1
24.5, 107.9, 68.9, 33.0, 23.7, 16.3 ppm.
-
1
17.0, 96.9, 62.1, 30.0, 24.9, 18.3 ppm. FT IR (KBr pellet, cm )
947, 2857, 1693, 1611, 1489, 1430, 1250, 1223, 1199, 1157,
4
-(Diethylamino)-2-(tetrahydrofuran-2-yloxy)
benzaldehyde (3q): (32 mg, 94% yield). Dark liquid. H NMR
400 MHz, CDCl ): δ = 10.01 (s, 1H), 7.7 (d, J = 9.2 Hz, 1H),
+
038, 955, 875, 771. MS (ESI): m/z = 313 [M + Na] . HRMS
1
+
(
3
ESI): m/z = [M + Na] calcd. for C H F O Na 313.0664; found
13
13
3
4
(
3
13.0662.
6
4
7
.39 (s, 1H), 6.32 (d, J = 9.2 Hz, 1H), 5.86 (d, J = 3.6 Hz, 1H),
.11−4.06 (m, 1H), 4.00 (q, J = 6.0 Hz, 1H), 3.43−3.40 (q, J =
.0 Hz, 4H), 2.27−1.96 (m, 4H), 1.26−1.21 (t, J = 7.0, 6H) ppm.
C NMR (100 MHz, CDCl ): δ = 187.2, 162.1, 153.7, 129.9,
14.8, 105.3, 102.8, 96.5, 68.4, 44.7 (2C), 32.8, 23.4, 12.6 (2C)
2
-(1,2-Dimethoxyethoxy) benzaldehyde (3w): (37 mg, 86%
1
13
yield). Colorless liquid. H NMR (400 MHz, CDCl ): δ = 10.53
3
3
(
s, 1H), 7.85 (d, J = 8.4 Hz, 1H), 7.55 (t, J = 8.4 Hz, 1H), 7.21 (d,
1
-
1
J = 8.4 Hz, 1H), 7.12 (t, J = 8.4 Hz, 1H), 5.41 (t, J = 5.2 Hz, 1H),
ppm. FT IR (KBr pellet, cm ) 2927, 2854, 1634, 1595, 1523,
1
2
1
3
3
.74−3.63 (m, 2H), 3.48 (s, 3H), 3.42 (s, 3H) ppm. C NMR
405, 1340, 1269, 1134, 1112, 1074, 980, 789. MS (ESI): m/z =
64 [M + H] . HRMS (ESI): m/z = [M + Na] calcd. for
+
+
(100 MHz, CDCl ): δ = 189.8, 159.6, 135.7, 128.2, 126.3, 122.4,
3
-
1
1
2
1
16.8, 102.1, 72.1, 59.4, 54.4 ppm. FT IR (KBr pellet, cm )
932, 2862, 1690, 1599, 1481, 1458, 1285, 1237, 1195, 1121,
C H NO Na 286.1419; found 286.1417.
1
5
21
3
+
039, 948, 761. MS (ESI): m/z = 233 [M + Na] . HRMS (ESI):
2
-(Tetrahydrofuran-2-yloxy)-5-trifluoromethoxy)
+
m/z = [M + Na] calcd. for C H O Na 233.0790; found
9a
1
11 14
4
benzaldehyde (3r) : (27 mg, 81% yield). Colourless liquid. H
NMR (400 MHz, CDCl ): δ = 10.4 (s, 1H), 7.67 (s, 1H),
2
33.0788.
3
7
2
1
1
.39−7.33 (m, 2H), 5.89 (t, J = 2.8 Hz, 1H), 4.11−4.00 (m, 2H),
13
5-Tert-butyl-2-(1,2-dimethoxyethoxy) benzaldehyde (3x):
29 mg, 78% yield). Colorless liquid. H NMR (400 MHz,
.31−2.02 (m, 4H) ppm. C NMR (125 MHz, CDCl ): δ = 188.5,
3
1
(
58.0, 143.3, 128.4, 126.1, 121.5 (q, J = 256 Hz, CF ), 120.3,
3
CDCl ): δ = 10.51 (s, 1H), 7.86 (s, 1H), 7.57 (d, J = 8.4 Hz, 1H),
3
17.3, 103.3, 68.7, 32.8, 23.3 ppm.
7
2
.13 (d, J = 8.4 Hz, 1H), 5.38 (t, J = 5.2 Hz, 1H), 3.73−3.62 (m,
13
H), 3.48 (s, 3H), 3.43 (s, 3H), 1.32 (s, 9H) ppm. C NMR (100
5
-Bromo-2-(tetrahydro-2H-pyran-2-yloxy) benzaldehyde
1
MHz, CDCl ): δ = 190.1, 157.5, 145.3, 133.1, 125.6, 124.6,
3
(3s): (27 mg, 76% yield). Colorless solid, m. p. 63−65 °C. H
1
16.4, 102.1, 72.2, 59.4, 54.3, 34.3, 31.2 (3C) ppm. FT IR (KBr
NMR (400 MHz, CDCl ): δ = 10.46 (s, 1H), 7.93 (d, J = 2.6 Hz,
1
-1
3
pellet, cm ) 2961, 2862, 1686, 1606, 1493, 1365, 1264, 1239,
H), 7.61 (dd, J = 2.6, 8.8 Hz, 1H), 7.16 (d, J = 8.8 Hz, 1H), 5.55
+
1
(
2
195, 1130, 1038, 819. MS (ESI): m/z = 289 [M + Na] . HRMS
(d, J = 2.8 Hz, 1H), 3.87−3.80 (m, 1H), 3.68−3.65 (m, 1H),
+
ESI): m/z = [M + Na] calcd. for C H O Na 289.1416; found
13
15 22 4
1
.94−1.93 (m, 2H), 1.74−1.62 (m, 4H) ppm. C NMR (100
89.1415.
-(1,2-Dimethoxyethoxy)-3-methoxybenzaldehyde (3y): (22
MHz, CDCl ): δ = 188.4, 158.4, 138.2, 130.6, 126.6, 117.5,
3
-
1
1
2
9
14.4, 96.7, 62.1, 29.9, 24.9, 18.3 ppm. FT IR (KBr pellet, cm )
944, 2854, 1673, 1590, 1470, 1391, 1278, 1179, 1122, 1036,
55, 874, 828, 713, 623. MS (ESI): m/z = 307 [M + Na] . HRMS
2
1
+
mg, 45% yield). Yellow liquid. H NMR (400 MHz, CDCl ): δ =
3
+
10.50 (s, 1H), 7.47−7.44 (m, 1H), 7.19−7.14 (m, 2H), 5.36 (t, J =
(ESI): m/z = [M + Na] calcd. for C H BrO Na 306.9946; found
12
13
3
5
3
.6, 1H), 3.91 (s, 3H), 3.73−3.58 (m, 2H), 3.45 (s, 3H), 3.42 (s,
3
06.9944.
13
H) ppm. C NMR (100 MHz, CDCl ): δ = 190.9, 152.2, 148.6,
3