3
poured into ice water and stirred for 1 h. After extraction with
CH2Cl2, the combined organic fractions were washed three times
with water before drying over Na2SO4. Evaporation of the
solvent yielded yellow crystals, which were further purified by
recrystallisation from CH2Cl2. Afterwards, monosubstituted by-
product was removed by subsequent boiling the raw product in
methanol and cyclohexane. Filtration and drying yielded a light
yellow solid (0.90 g, 64%).
Har: H-2 and H-6), 7.51 (d, J(1H,1H) ¼ 8.85 Hz, 2H, Har: H-3
and H-5); MS (70 eV, EI): m/z ¼ 366 (51%, M+), 247/246 (26/9, I–
Ph–O–CH2–CH2+), 220 (18), 203 (17, I–Ph+), 147 (35, CH2–
CH2–O–CH2–CH2–O–CH2–CH2–O–CH3+), 120 (25), 103 (26,
CH2–CH2–O–CH2–CH2–O–CH3+), 76 (14, Phc+), 59 (100, CH2–
CH2–O–CH3+), 45 (16, CH2–O–CH3+).
1-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}-4-(N,N-diphenyla-
mino)benzene 10. 9 (10.9 g, 29.8 mmol), copper powder (2.77 g,
43.6 mmol), K2CO3 (12.08 g, 87.4 mmol), 18-crown-6 (577 mg,
2.2 mmol) and diphenylamine (3.7 g, 21.9 mmol) were
consecutively dissolved in dry o-dichlorobenzene (50 mL). The
solution was stirred under dry conditions at 120 ꢁC for 1 h and
then heated to 180 ꢁC for 36 h (the progress of the reaction
was followed by TLC; cyclohexane:ethyl acetate 9:1). After
completion of the reaction, the mixture was cooled to RT,
THF was added and the suspension was filtered. The filtrate
was dried under reduced pressure. The remaining solid was
dissolved in THF and the pure product was precipitated from
methanol (8.40 g, 94%).
UV-Vis (CDCl3): lmax/nm ¼ 363; FT-IR (KBr pellet): nmax
/
cmꢀ1 ¼ 3056, 3024, 2926, 1630, 1583, 1542, 1460, 1417, 1374,
1330, 964, 827, 755, 691; 1H-NMR (250 MHz; CDCl3/
ꢁ
CF3COOD; 20 C; TMS): d/ppm ¼ 8.75 (d, 2H), 8.44 (s, 2H),
7.02–7.69 (m, 28H); MS (70 eV, EI): m/z ¼ 564 (M+); CV
(DMSO, Bu4NPF6): HOMO ¼ ꢀ5.56 eV, LUMO ¼ ꢀ1.88 eV.
{2-[2-(2-Methoxyethoxy)ethoxy]ethyl}-4-methylbenzene-sulfo-
nate 8. Under an inert gas atmosphere, triethylene glycol
monomethyl ether (39.20 mL, 41.00 g, 250 mmol) and pyridine
(10 mL) were cooled to 0 ꢁC. Meanwhile tosyl chloride (51.00 g,
270 mmol) was dissolved in pyridine (40 mL) and added drop-
wise to the alcohol solution over 1 h. This mixture was stirred till
the alcohol was fully used up (TLC control; cyclohexane:ethyl
acetate 1:1). Afterwards, ice was added and the mixture was
extracted with ethyl acetate. The combined organic fractions
were subsequently washed with diluted HCl (20 mL), saturated
Na2CO3 (20 mL) solution and water (50 mL). After drying over
Na2SO4 and evaporation of the solvent, the product was
obtained as a yellow liquid (63.40 g, 80%).
1H-NMR (250 MHz; CDCl3; 20 C; TMS): d/ppm ¼ 3.38 (s,
ꢁ
3H, CH3), 3.55 (t, 3J(1H,1H) ¼ 5.08 Hz, 2H, CH2–O–CH3), 3.59–
3.78 (m, 6H, O–CH2–CH2–O–CH2–CH2–OCH3), 3.85 (t,
3J(1H,1H) ¼ 5.05 Hz, 2H, Ph–O–CH2–CH2), 4.11 (t, 3J(1H,1H) ¼
5.05 Hz, 2H, Ph–O–CH2–CH2), 6.60–7.58 (m, 14H, Har); MS (70
eV, EI): m/z ¼ 407 (12%, M+), 366 (62), 260 (9, Ph2N–Ph–O+),
246 (37), 220 (26, Ph–N–Ph–O–CH2–CH2+), 203 (39), 191 (17),
182 (14), 147 (51, CH2–CH2–O–CH2–CH2–O–CH2–CH2–O–
CH3+), 120 (40, N–Ph–O–CH2+), 103 (35, CH2–CH2–O–CH2–
CH2–O–CH3+), 91 (18, Ph–N+), 77 (13, Ph+), 76 (31, Phc+), 59
(100, CH2–CH2–O–CH3+), 45 (71, CH2–O–CH3+).
1H-NMR (250 MHz; CDCl3; 20 C; TMS): d/ppm ¼ 2.45 (s,
ꢁ
3H, CH3–Ph), 3.37 (s, 3H, O–CH3), 3.48–3.73 (m, 10H, SO2–O–
CH2–CH2–O–CH2–CH2–O–CH2–CH2–OCH3),
4.16
(t,
3J(1H,1H) ¼ 5.05 Hz, 2H, SO2–O–CH2–CH2), 7.34 (d, 3J(1H,1H)
¼ 8.23 Hz, 2H, Har: H-3 and H-5), 7.80 (d, 3J(1H,1H) ¼ 8.20 Hz,
2H, Har: H-2 and H-6); MS (70 eV, EI): m/z ¼ 318 (1%, M+), 303
(14, M–CH3+), 226 (100), 227 (26, M–CH3–Ph+), 199 (21, M–O–
CH2–CH2–O–CH2–CH2–O–CH3+), 183 (9), 172 (11), 155 (16),
106 (26), 93 (74), 91 (40, CH3–Ph+), 80 (36), 79 (36), 59 (80, CH2–
CH2–O–CH3+), 45 (46, C2H5O+).
4-{N-{4-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}phenyl}-N-phe-
nylamino}benzaldehyde 11. Freshly distilled POCl3 (1.40 mL,
2.34 g, 15.25 mmol) was added to DMF (10 mL) under dry
conditions, cooled to 0 ꢁC and stirred at 0–5 ꢁC for 30 min.
Afterwards, the ice bath was removed and the solution was
stirred until the red colour vanished. Meanwhile, 10 (6.11 g,
15.0 mmol) was dissolved in dry CH2Cl2 (50 mL) and cooled
to 0–5 ꢁC. Then the POCl3 containing solution was added
dropwise to the solution of 10 in CH2Cl2. After stirring the
1-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}-4-iodobenzene 9. 4-
Iodophenol (22.00 g, 100 mmol) and K2CO3 (16.58 g, 120 mmol)
were dissolved in dry MEK (50 mL) and heated to reflux under
water- and moisture-free conditions. 8 (38.20 g, 120 mmol) was
also dissolved in dry MEK (50 mL) and slowly added to the
refluxing solution by a dropping funnel. The whole solution was
refluxed for 4 h (TLC control; cyclohexane:ethyl acetate 1:1).
Afterwards, n-hexane (40 mL) was added and the solution was
refluxed for an additional 0.5 h. The reaction was quenched with
ice water (30 mL), the organic phase was isolated, washed with
water (2 ꢄ 40 mL), dried over Na2SO4 and concentrated under
reduced pressure. The raw product was recrystallised from n-
hexane and washed with cold petroleum ether. The pure product
was obtained after drying it for 2 days under vacuum at 40 ꢁC as
light yellow liquid (12.82 g, 35%).
ꢁ
resulting yellow solution for 15 min at 0–5 C, it was heated to
80–85 ꢁC and stirred for 2.5 h (TLC control; CH2Cl2; each
sample was shaken with sodium acetate and diluted with
CH2Cl2). After full conversion of 10, the reaction mixture was
cooled to RT, added dropwise to a strongly stirring solution of
sodium acetate in ice water (ꢂ50 mL) and stirred overnight.
Afterwards, the organic layer was isolated and the aqueous
was extracted with CH2Cl2 (5 ꢄ 70 mL). The combined
organic fractions were dried over Na2SO4 and the solvent was
removed under reduced pressure. The raw product was puri-
fied by column chromatography (silica gel 60; cyclo-
hexane:ethyl acetate 1:1). The pure product was obtained as
a yellow, highly viscous liquid (2.80 g, 43%).
1H-NMR (250 MHz; CDCl3; 20 C; TMS): d/ppm ¼ 3.35 (s,
FT-IR (NaCl plates): nmax/cmꢀ1 ¼ 3063 (w) and 3039 (w) (CH
aromatic), 2877 (br m) (CH aliphatic), 2733 (m), 1695 (m), 1615–
1558 (m), 1506–1436 (m), 1280–1220 (br m), 1070–1064 (br m)
(CO), 946 (w), 826 (m), 759 (w) (CH aromatic out-of-plane), 725
ꢁ
3H, CH3), 3.52 (t, 3J(1H,1H) ¼ 2.55 Hz, 2H, CH2–O–CH3), 3.58–
3.73 (m, 6H, CH2–CH2–O–CH2–CH2–O–CH3), 3.82 (t,
3J(1H,1H) ¼ 2.55 Hz, 2H, Ph–O–CH2–CH2), 4.06 (t, 3J(1H,1H) ¼
3
1
2.55 Hz, 2H, Ph–O–CH2–CH2), 6.67 (d, J(1H,1H) ¼ 8.85, 2H,
(w), 697 (m), 616 (w), 547 (w); H-NMR (250 MHz; DMSO-d6;
This journal is ª The Royal Society of Chemistry 2009
J. Mater. Chem., 2009, 19, 5364–5376 | 5373
Willinger, Katja
