by column chromatography on silica (1 : 10 acetone–CH2Cl2)
to afford the product as a pale oil which crystallised upon
standing for several days (0.190 g, 79%). Found C% 63.9, H%
8.03, N% 3.63%; calculated for C21H33NO2S2 C% 63.8, H%
8.36, N% 3.54. 1H NMR (250.13 MHz, CDCl3): d~0.86 (3H, t,
CH3), 1.27 (8H, m, CH2CH2CH2CH2CH3), 1.42 (2H, m,
OCH2CH2CH2), 1.76 (2H, tt, OCH2CH2), 2.89, 2.98, 3.09,
3.33, 3.68, 3.91 (2H, br s, CH2 ring), 3.94 (2H, t, OCH2), 6.87
and 7.44 ppm (2H, AA’XX’, ArH); 13C NMR (62.89 MHz,
CDCl3): d~13.94 (CH3), 22.47, 25.83, 28.97, 29.04, 29.15,
31.61, (OCH2CH2CH2CH2CH2CH2CH2CH3), 32.03, 32.13,
32.64, 37.54, 50.82, 53.00 (CH2, ring), 67.90 (OCH2), 114.04
(aromatic CH), 128.32 (aromatic quaternary), 128.77 (aromatic
CH), 160.01 (aromatic quaternary) and 172.35 ppm (NCO); IR
(KBr disc): nCO~1631 cm21; EI-MS: m/z(%): 395 (Mz), 233
[C(O)C6H4OC8H17].
128.38, 121.94, 121.60, 114.15 (CH), 68.12, 52.73, 50.81, 37.63,
32.60, 32.07, 31.94, 31.53, 29.06, 28.95, 28.81, 25.71, 22.40
(CH2), 13.88 (CH3); IR(KBr): n~1733 (CLO), 1630 (OLCN),
1603 (CLCar), 1260, 1200, 1160 (C–O) cm21; ES-MS: m/z(%):
636 (43) [M]z, 284 (100).
Synthesis of 4a
Compound 7 (0.049 g, 0.185 mmol), 4’-[3,4-bis(butyloxyben-
zoyloxy)]benzoic acid (0.058 g, 0.185 mmol), N,N’-dicyclo-
hexylcarbodiimide (0.038 g, 0.185 mmol) and 4-pyrrolidino-
pyridine (2 mg) were dissolved in freshly distilled CH2Cl2
(10 cm3) and the reaction mixture stirred for 16 h. The solvent
was removed in vacuo and the resulting colourless solid purified
by column chromatography (silica, 1061 cm, CH2Cl2–MeOH,
100 : 1) to give a colourless solid which was recrystallised
several times from toluene–n-hexane (yield 73 mg, 61%).
Found C% 63.02, H% 6.21, N% 1.91; calculated for
C35H41NO7S2 C% 64.49, H% 6.34, N% 2.15. 1H NMR
(300 MHz, CDCl3): d~8.29 (d, 2 H, 3J(H,H)~8.81 Hz,
CHar), 7.85 (dd, 1 H, 3J(H,H)~8.44 Hz, 4J(H,H)~2.06 Hz,
Synthesis of 2
4’-(4-Octyloxybenzoyloxy)benzoic acid was converted to its
acid chloride following the method described for the synthesis
of 1a. The acid chloride (0.272 g, 0.0007 mol) was reacted with
[9]aneNS2 (0.120 g, 0.00074 mol) and dimethylaminopyridine
(DMAP) (0.098 g, 0.0008 mol) in CH2Cl2 (10 cm3) overnight.
The solution was then diluted to 30 cm3, washed with
4
CHar), 7.69 (d, 1 H, J(H,H)~2.07 Hz, CHar), 7.63 (d, 2 H,
3J(H,H)~8.69 Hz, CHar), 7.39 (d, 2 H, 3J(H,H)~8.88 Hz,
3
CHar), 7.31 (d, 2 H, J(H,H)~8.64 Hz, CHar), 6.96 (d, 1 H,
3J(H,H)~8.56 Hz, CHar), 4.11 (two overlapping triplets, 4 H,
OCH2), 3.98 (m, 2 H, CH2), 3.71 (m, 2 H, CH2), 3.42 (m, 2 H,
CH2), 3.18 (m, 2 H, CH2), 3.06 (m, 2 H, CH2), 2.95 (m, 2 H,
CH2), 1.85 (two overlapping quintets, 4 H, OCH2CH2), 1.56
(two overlapping quintets, 4 H, OCH2CH2CH2CH3), 1.02 (two
overlapping triplets, 6 H, CH3); 13C NMR (75 MHz, CDCl3):
d~171.88, 164.45, 164.18, 155.69, 154.38, 151.82, 148.95,
134.39, 126.68, 121.00 (Cq), 131.88, 128.68, 124.68, 122.24,
121.88, 115.01, 112.24 (CH), 69.28, 68.94, 32.46, 31.31, 31.17,
19.27, 19.24 (CH2), 13.87, 13.85 (CH3); IR(KBr): n~1734
hydrochloric acid (1 mol dm23
) and water, then dried
(MgSO4) and concentrated in vacuo. The residue was purified
by column chromatography on silica (1 : 10 acetone–CH2Cl2)
to afford the product as a white solid (0.190 g, 51%). The
product could be further purified by recrystallisation from hot
MeOH–water. Found: C% 65.2, H% 7.18, N% 2.72%,
1
calculated for C28H37NO4S2 C% 65.9, H% 7.16, N% 2.68. H
NMR (250.13 MHz, CDCl3): d~0.87 (3H, t, CH3), 1.30 (8H,
m, CH2CH2CH2CH2CH3), 1.37 (2H, m, OCH2CH2CH2), 1.77
(2H, tt, OCH2CH2), 2.90, 3.00, 3.12, 3.38, 3.65, 3.93 (2H, br s,
CH2 ring), 4.01 (2H, t, OCH2), 6.94, 7.26, 7.59 and 8.01 (2H, m,
AA’XX’, ArH); 13C NMR (62.89 MHz, CDCl3): d~13.97
(CH3), 22.49, 25.82, 28.91, 29.06, 29.16, 31.64
(OCH2CH2CH2CH2CH2CH2CH2CH3), 32.09, 32.22, 32.76,
37.76, 50.89, 52.84 (CH2, ring), 68.19 (OCH2), 114.19 (aromatic
CH), 120.97 (aromatic quaternary), 121.79, 128.39, 132.18
(aromatic CH), 133.80, 151.76, 163.53 (aromatic quaternary),
164.45 and 171.76 ppm (CO quaternary); IR (KBr disc):
n~1735 (CO-ester) and 1630 cm21 (CO-amide); EI-MS:
m/z(%): 515 (Mz), 233 [C(O)C6H4OC8H17].
(CLO), 1635 (OLCN), 1599 (CLCar), 1272, 1187 (C–O) cm21
;
FAB-MS: m/z(%): 652 (15) [M]z, 249 (100) [OCC6H3-
(OC4H9)2]z.
Synthesis of 4b
This compound was synthesised according to the same
general procedure described for 4a. Amounts used:
7
(0.050 g, 0.189 mmol), 4’-[3,4-bis(octyloxybenzoyloxy)benzoic
acid (0.097 g, 0.189 mmol) N,N’-dicyclohexylcarbodiimide
(0.039 g, 0.189 mmol) and 4-pyrrolidinopyridine (2 mg). The
crude reaction product was purified by column chromatogra-
phy (silica, 1262 cm, CH2Cl2–acetone, 20 : 1) to give a
colourless solid which was recrystallised several times from
toluene–n-hexane (yield 79 mg, 55%). Found C% 68.80, H%
7.76, N% 1.91; calculated for C43H57NO7S2 C% 67.60, H%
Synthesis of 3
4@-[4’-(4-Octyloxybenzoyloxy)benzoyloxy]benzoic acid anhy-
dride (0.145 g, 0.151 mmol), prepared from the parent acid,
was added to a solution of [9]aneNS2 (0.016 g, 0.098 mmol) and
pyridine (7.9 ml, 0.1 mmol) in freshly distilled CH2Cl2 (10 cm3)
and the reaction mixture stirred for 12 h. The resulting reaction
mixture was filtered, the solvent removed in vacuo and the
crude solid was purified by column chromatography (silica,
1561 cm, CH2Cl2–acetone, 10 : 1) to give a colourless solid
which was crystallised from toluene–n-hexane (yield 53 mg,
85%). Found C% 66.04, H% 6.62, N% 2.20; calculated for
C35H41NO6S2 C% 66.11, H% 6.50, N% 2.20). 1H NMR
(300 MHz, CDCl3): d~8.29 (d, 2 H, 3J(H,H)~8.63 Hz, CHar),
8.17 (d, 2 H, 3J(H,H)~8.80 Hz, CHar), 7.63 (d, 2 H,
3J(H,H)~8.45 Hz, CHar), 7.39 (d, 2 H, 3J(H,H)~8.64 Hz,
1
7.52, N% 1.83. H NMR (300 MHz, CDCl3): d~8.30 (d, 2 H,
3J(H,H)~8.86 Hz, CHar), 7.85 (dd, 1 H, 3J(H,H)~8.46 Hz,
4J(H,H)~2.06 Hz, CHar), 7.68 (d, 1 H, 4J(H,H)~2.04 Hz,
3
CHar), 7.63 (d, 2 H, J(H,H)~8.70 Hz, CHar), 7.39 (d, 2 H,
3J(H,H)~8.84 Hz, CHar), 7.31 (d, 2 H, 3J(H,H)~8.68 Hz,
CHar), 6.96 (d, 1 H, 3J(H,H)~8.58 Hz, CHar), 4.09 (two
overlapping triplets, 4 H, OCH2), 3.98 (m, 2 H, CH2), 3.71 (m,
2 H, CH2), 3.42 (m, 2 H, CH2), 3.18 (m, 2 H, CH2), 3.06 (m, 2
H, CH2), 2.95 (m, 2 H, CH2), 1.88 (two overlapping quintets, 4
H, OCH2CH2), 1.52 (pseudo-quintet, 4 H, OCH2CH2CH2),
1.42–1.27 (m, 16 H, CH2), 0.91 (two overlapping triplets, 6 H,
CH3); 13C NMR (63 MHz, CDCl3): d~171.61, 169.74, 164.21,
155.41, 151.66, 148.52, 134.06, 133.16, 126.25, 120.64 (Cq),
131.65, 128.17, 124.37, 122.03, 121.84, 114.37, 111.71 (CH),
69.16, 68.87, 52.78, 50.87, 37.71, 32.70, 32.13, 32.04, 31.60,
29.11, 28.90, 27.61, 25.77, 22.46 (CH2), 13.91 (CH3); IR(KBr):
n~1734 (CLO), 1631 (OLCN) cm21. ES-MS: m/z(%): 764 (22)
[M]z, 658 (20) [OCC6H3-(OC8H17)2]z.
3
CHar), 7.31 (d, 2 H, J(H,H)~8.49 Hz, CHar), 7.01 (d, 2 H,
3J(H,H)~8.87 Hz, CHar), 4.07 (t, 2 H, 3J(H,H)~6.54 Hz,
OCH2), 3.98 (m, 2 H, CH2), 3.71 (m, 2 H, CH2), 3.43 (m, 2 H,
CH2), 3.42 (m, 2 H, CH2), 3.18 (m, 2 H, CH2), 3.06 (m, 2 H,
CH2), 2.95 (m, 2 H, CH2), 1.85 (quintet, 2 H, OCH2CH2), 1.53–
1.27 (m, 10 H, CH2), 0.92 (pseudo-triplet, 3 H, CH3); 13C NMR
(62.89 MHz, CDCl3): d~171.53, 163.99, 163.85, 163.56,
155.25, 151.41, 133.99, 126.24, 120.57 (Cq), 132.16, 131.58,
1016
J. Mater. Chem., 2001, 11, 1011–1018