CDCl3) 189.8, 160.9, 154.0, 139.0, 135.8, 129.7, 125.5, 121.7, 121.4,
114.1, 100.0, 62.0, 31.2, 16.1.
4 H, Ar H), 7.82 (d, J 7.4 Hz, 4 H, Ar H), 10.52 (s, 4 H, Ar
CHO); dC(100 MHz, CDCl3) 189.8, 161.5, 148.3, 144.4, 138.9,
136.0, 128.2, 124.9, 120.6, 114.2, 112.6, 99.5, 73.0, 68.2, 37.0, 32.1,
29.9, 27.6, 26.8, 25.9, 22.7,14.2.
7,11,15,28-Tetrakis[(2-formylphenoxy)methylene]-1,21,23,25-
tetrapentyl - 2,20:3,19 - dimetheno - 1H,21H,23H,25H - bis[1,3]di -
oxocino[5,4 - i:5¢,4¢ - i¢]benzo[1,2 - d:5,4 - d¢] - bis[1,3]benzodioxocin
stereoisomer (4). Similar procedure as for the preparation of
3, applied to salicylaldehyde (0.36 g, 2.69 mmol) in dry THF
(50 mL) under a nitrogen atmosphere, NaH (60% suspension in
mineral oil, 0.065 g, 2.69 mmol), and tetrabromomethyl cavitand
2 (0.40 g, 0.34 mmol). After 3 days of reflux, TLC showed tri- and
tetra-substituted products. The products were chromatographed
on silica gel using a mobile phase of 1:1 hexane–ethyl acetate.
Fractions containing the desired tetra-substituted product (Rf
0.56) were combined, and concentrated in vacuo to yield a white
solid. The material was then stirred in methanol, before being
filtered and collected to yield 4 (0.33 g, 80%) as a white solid
(Found: C, 74.8; H, 6.7. C84H88O16 requires C, 74.5; H, 6.5%); mp
Tetraaldehyde 15. Application of the general procedure using
tetrol 9 (0.51 g, 0.705 mmol) and aldehyde reagent 12 (1.35 g,
5.55 mmol) gave 15 (0.92 g, 85%) as an off-white solid (Found: C,
72.3; H, 6.9. C92H104O20 requires C, 72.2; H, 6.9%); mp 65 ◦C dec.
n
max(KBr)/cm-1 2919, 2847, 1678, 1597, 1435, 971; dH(400 MHz,
CDCl3) 0.92 (t, J 7.1 Hz, 12 H, CH3), 1.40 (m, 24 H, (CH2)3),
2.16 (m, 16 H, CHCH2(CH2)3CH3 and OCH2CH2CH2O), 4.14
(t, J 5.8 Hz, 8 H, O(CH2)2CH2O) 4.26 (t, J 6.1 Hz, 8 H,
O(CH2)2CH2O), 4.33 (d, J 7.0 Hz, 4 H, inner of OCH2O), 4.64
(t, J 8.0 Hz, 4 H CH(CH2)4CH3), 5.64 (d, J 7.1 Hz, 4 H, outer of
OCH2O), 6.80 (s, 4 H, cavitand Ar H), 7.00 (m, 8 H, Ar H), 7.51 (t,
J 7.5 Hz, 4 H, Ar H), 7.83 (d, J 7.7 Hz, 4 H, Ar H), 10.49 (s, 4 H,
Ar CHO); dC(100 MHz, CDCl3) 189.7, 161.4, 148.1, 144.0, 139.0,
135.9, 128.3, 124.9, 120.6, 114.3, 112.5, 99.4, 76.7, 69.8, 65.2, 37.0,
32.1, 29.9, 29.7, 27.6, 22.7, 14.1.
◦
136–138 C. nmax(KBr)/cm-1 2929, 2859, 1686, 1597, 1476, 1454,
1378, 1283, 1240, 1189, 1151, 1088, 1019, 964, 853, 755, 654, 585,
487, 441; dH(400 MHz, CDCl3) 0.91 (t, J 7.1 Hz, 12 H, CH3), 1.36
(m, 24 H, (CH2)3), 2.26 (m, 8 H, CH2), 4.54 (d, J 7.1 Hz, 4 H,
inner of OCH2O), 4.83 (t, J 8.1 Hz, 4 H, CH(CH2)4CH3), 4.95
(s, 8 H, ArOCH2Ar), 5.77 (d, J 7.0 Hz, 4 H, outer of OCH2O),
7.03 (t, J 7.5 Hz, 4 H, Ar H), 7.14 (d, J 8.4 Hz, 4 H, Ar H),
7.27 (s, 4 H, cavitand Ar H), 7.53 (td, J 8.9 Hz, 4 H, Ar H), 7.73
(dd, J 7.5 Hz, 4 H, Ar H), 10.17 (s, 4 H, Ar CHO); dC(100 MHz,
CDCl3) 189.93, 160.95, 154.44, 138.19, 135.87, 129.70, 125.55,
121.93, 121.41, 114.17, 100.07, 62.11, 36.94, 32.02, 30.12, 27.58,
22.70, 14.13.
Tetraaldehyde 16. Application of the general procedure using
tetrol 9 (0.50 g, 0.705 mmol) and aldehyde reagent 13 (1.28 g,
5.59 mmol) gave 16 (0.93 g, 90%) as a white powder (Found: C,
71.9; H, 6.7. C88H96O20 requires C, 71.7; H, 6.6%); mp 85 ◦C dec.
n
max(KBr)/cm-1 2921, 2855, 1680, 1600, 1435, 970; dH(400 MHz,
CDCl3) 0.92 (t, J 6.9 Hz, 12 H, CH3), 1.41 (m, 24 H, (CH2)3), 2.25
(m, 8 H, CHCH2(CH2)3CH3), 4.35 (m, 20 H, inner of OCH2O and
OCH2CH2O), 4.65 (t, J 7.4 Hz, 4 H CH(CH2)4CH3), 5.75 (d, J
7.0 Hz, 4 H, outer of OCH2O), 6.80 (s, 4 H, cavitand Ar H), 7.00
(m, 8 H, Ar H), 7.52 (t, J 7.5 Hz, 4 H, Ar H), 7.82 (d, J 7.3 Hz,
4 H, Ar H), 10.50 (s, 4 H, Ar CHO); dC(100 MHz, CDCl3) 189.8,
161.3, 148.1, 144.0, 139.0, 135.9, 128.1, 125.1, 120.9, 114.5, 112.8,
99.3, 71.4, 68.2, 36.9, 31.9, 29.4, 27.6, 22.7, 14.2.
General procedure for preparation of tetraaldehyde resor-
cin[4]arene cavitands 14–19. To a stirring solution of oven-dried
(110 ◦C) K2CO3 in dry DMF (40 mL), dry tetrol was added and
stirred until completely dissolved. To the resulting light yellow
solution, the respective aldehyde reagent was added and the
reaction mixture gently heated at 55 ◦C for three days. During
this period, the solution became yellow and cloudy, with a white
deposit on the sides of the reaction vessel. The mixture was cooled
to room temperature, at which time the unreacted K2CO3 and
the white precipitate was gravity-filtered from the solution. The
filtrate was collected, and the DMF removed in vacuo, yielding a
dark yellow, oily residue. Methanol was added to the residue to
remove excess aldehyde reagent and precipitate out the product.
The resultant white suspension was stirred overnight, and the
purified product was obtained by filtration from the methanol
as a solid.
Tetraaldehyde 17. Application of the general procedure using
tetrol 10 (0.51 g, 0.491 mmol) and aldehyde reagent 11 (1.00 g,
3.93 mmol) gave 17 (0.64 g, 76%) as an off-white powder (Found:
C, 75.4; H, 6.1. C108H104O20 requires C, 75.3; H, 6.1%); mp 102–
◦
104 C dec. nmax(KBr)/cm-1 2940, 1681, 1595, 1383, 1288, 1244,
1183, 1157, 1104, 1020, 979, 837; dH(400 MHz, CDCl3) 1.85 (m,
8 H, O(CH2)2CH2CH2O), 2.01 (m, 8 H, O(CH2)2CH2CH2O),
2.42–2.46 (m, 8 H, CH2CH2Ar), 2.61–2.65 (m, 8 H, CH2CH2Ar),
3.99 (t, J 6.1 Hz, 8 H, O(CH2)3CH2O), 4.14 (t, J 5.9 Hz, 8 H,
O(CH2)3CH2O), 4.39 (d, J 7.0 Hz, 4 H, inner of OCH2O), 4.79
(t, J 7.3 Hz, 4 H, CHCH2CH2Ar), 5.78 (d, J 7.2 Hz, 4 H, outer
of OCH2O), 6.82 (s, 4 H, cavitand Ar H), 6.99 (m, 4 H, Ar H),
7.12 (m, 4 H, Ar H), 7.18–7.22 (m, 20 H, CH2CH2C6H5), 7.51 (t,
J 8.5 Hz, 4 H, Ar H), 7.80 (dd, J 7.8 Hz, J 1.8 Hz, 4 H, Ar H),
10.50 (s, 4 H, Ar CHO); dC(100 MHz, CDCl3) 189.9, 161.5, 148.6,
144.6, 141.8, 138.7, 136.0, 128.6, 128.4, 128.3, 126.0, 120.6, 114.0,
112.5, 99.5, 73.8, 68.2, 62.7, 37.1, 34.5, 32.4, 29.7, 26.8, 25.9.
Tetraaldehyde 14. Application of the general procedure using
tetrol 9 (0.50 g, 0.705 mmol) and aldehyde reagent 11 (1.45 g,
5.64 mmol) gave 14 (0.79 g, 71%) as an off-white solid (Found: C,
72.9; H, 7.2. C96H112O20 requires C, 72.7; H, 7.2%); mp 60 ◦C dec.
n
max(KBr)/cm-1 2921, 2851, 1682, 1597, 1436, 972; dH(400 MHz,
Tetraaldehyde 18. Application of the general procedure using
tetrol 10 (0.50 g, 0.490 mmol) and aldehyde reagent 12 (0.95 g,
3.93 mmol) gave 18 (0.66 g, 81%) as an off-white powder (Found:
C, 7◦5.1; H, 5.9. C104H96O20 requires C, 74.9; H, 5.9%); mp 96–
100 C dec. nmax(KBr)/cm-1 2944, 1684, 1598, 1387, 1285, 1240,
1188, 1152, 1103, 1047, 1018, 976, 841; dH(400 MHz, CDCl3)
2.13–2.16 (t, J 6.0 Hz, 8 H, OCH2CH2CH2O), 2.41–2.45 (m, 8 H,
CH2CH2Ar), 2.60–2.64 (m, 8 H, CH2CH2Ar), 4.14 (t, J 5.8 Hz,
CDCl3) 0.93 (t, J 7.0 Hz, 12 H, CH3), 1.39 (m, 24 H, (CH2)3), 1.80
(m, 8 H, O(CH2)2CH2CH2O), 2.03 (m, 8 H, O(CH2)2CH2CH2O),
2.16 (m, 8 H, CHCH2(CH2)3CH3), 3.99 (t, J 6.0 Hz, 8 H,
O(CH2)3CH2O) 4.16 (t, J 5.8 Hz, 8 H, O(CH2)3CH2O), 4.41
(d, J 7.1 Hz, 4 H, inner of OCH2O), 4.70 (t, J 7.6 Hz, 4 H
CH(CH2)4CH3), 5.79 (d, J 6.7 Hz, 4 H, outer of OCH2O), 6.82
(s, 4 H, cavitand Ar H), 6.99 (m, 8 H, Ar H), 7.55 (t, J 7.4 Hz,
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The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 3958–3968 | 3965
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