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+
+
2 2 3 2
respectively. Remaining pure compound was ltered and dried 42.72 (N–CH ), 50.99 (N –CH ), 52.74 (N –CH ), 60.51 (Ar–CH ),
ꢂ
ꢀ1
to yield with 33%. Mp: 206–208 C. FTIR (ATR): 1612 cm (C] 112.05 (ArC), 117.14 (ArC), 117.26 (ArC), 145.74 (ArC), 145.83
1
O). H NMR (400 MHz CDCl ): d 2.43 (brs, 16H, –CH –), 3.30 (ArC), 145.90 (ArC), 146.45 (ArC), 146.50 (ArC–O), 158.69 (C]O).
3
2
(
brs, 8H, Ar–CH –N), 3.49–3.54 (m, 4H, Ar–CH –Ar), 3.79 (brs, Anal. calcd for C108
H
I N O : C, 49.12; H, 4.77; N, 6.37.
125 6 12 18
2
2
1
6H, –CH
2
–), 4.24 (d, 4H, J ¼ 12.4 Hz, Ar–CH
2
–Ar), 6.46–6.47 Found (%): C, 48.98; H, 4.68; N, 6.25.
The synthesis of 2,4-di-tert-butyl-6-[(4-piperazin-1-yl)(furan-
12: C, 2-yl)methanone]methylene phenol (9). To a solution of 2,4-di-
8.44; H, 6.08; N, 9.39. Found (%): C, 68.47; H, 6.18; N, 9.22. tert-butyl phenol (1 g, 4.85 mmol) in 60 mL of THF was added
The synthesis of 5,11,17,23-tetra-[(4-methylpiperazinium-1- 2 mL of formaldehyde, 6 mL of AcOH and 1-(2-furoyl)piper-
yl)(furan-2-yl)methanone]methylene-25,26,27,28-tetra-hydroxy- azine (1.1 g, 6.30 mmol). The mixture was stirred at rt for 24
(m, 4H, ArH), 6.97–7.01 (m, 12H, ArH), 7.46 (brs, 4H, ArH),
72 8
10.08–10.28 (m, 4H, –OH). Anal. calcd for C68H N O
6
calix[4]arene tetraiodide (4). 9.14 g of methyl iodide (64.358 h, and then the volatile components were removed by rotary
mmol) was added to a solution of 3 (0.2 g, 0.168 mmol) in 20 mL evaporation. The remaining crude material was washed with
of DCM. The mixture was stirred at rt for 6 days. The solvent was water to adjust to pH 7, and recrystalizated from MeOH to
ꢂ
ꢀ1
evaporated and residue was then treated with Et
impurities. The solvent was evaporated to produce 4 in 77% (nC]O). H-NMR (400 MHz, CHCl
2
O to remove afford 9 in 42% yield. Mp: 161–163 C. FTIR (ATR): 1649 cm
1
t
3
): d 1.28 (s, 9H, Bu), 1.43
–), 3.73 (s, 2H, Ar–CH –N),
2
–), 6.47–6.49 (m, 1H, ArH), 6.84 (brs,
ꢂ
ꢀ1
1
t
yield. Mp >350 C. FTIR (ATR): 1651 cm (C]O). H-NMR (400 (s, 9H, Bu), 2.63 (brs, 4H, –CH
2
2
MHz, DMSO-d
6
): d 2.33 (s, 12H, –CH
3
), 2.46 (t, 16H, J ¼ 5.2 Hz, 3.80–3.99 (m, 4H, –CH
–
CH –), 3.28–3.31 (m, 8H, Ar–CH –N), 3.79–3.83 (m, 20H, –CH – 1H, ArH), 7.02 (d, 1H, J ¼ 3.6 Hz, ArH), 7.24 (brs, 1H, ArH), 7.
2
2
2
and Ar–CH –Ar), 4.14–4.23 (m, 4H, Ar–CH –Ar), 6.48 (q, 4H, J ¼ 47 (s, 1H, ArH), 10.50 (s, 1H, –OH). Anal. calcd for
2
2
2
.0 Hz, ArH), 6.99 (d, 4H, J ¼ 3.6 Hz, ArH), 7.26 (s, 8H, ArH), 7.55 C24H34N O : C, 72.33; H, 8.60; N, 7.03. Found (%): C, 72.39;
2
3
13
(brs, 4H, ArH). C-NMR (100 MHz, DMSO-d
6
): d 31.12 (Ar–CH
), 60.55 (Ar–CH
2
–
H, 8.77; N, 7.11.
+
+
Ar), 51.02 (N–CH
2
, N –CH
2
, and N –CH
3
2
),
The synthesis of 2,4-di-tert-butyl-6-[(4-methylpiperazinium-
1
(
12.04 (ArC), 117.25 (ArC), 145.88 (ArC), 145.91 (ArC), 146.46 1-yl)(furan-2-yl)methanone]methylene phenol (10). A mixture of
ArC), 146.49 (ArC–O), 158.71 (C]O). Anal. calcd for 9 (0.5 g, 1.25 mmol) and MeI (1.8 g, 12.55 mmol) in 30 mL of
12: C, 49.10; H, 4.81; N, 6.36. Found (%): C, 48.97; DCM was stirred at rt for 5 days. The reaction mixture was
H, 4.78; N, 6.35. evaporated and MeOH was added to give 10. Yield: 55%. Mp:
The synthesis of 5,11,17,23,29,35-hexa-[(piperazine-1- 147–150 C. FTIR (ATR): 1648 cm (n
72 84 4 8
C H I N O
ꢂ
ꢀ1
1
). H-NMR (400 MHz,
C]O
t
t
yl)(furan-2-yl)methanone]methylene-37,38,39,40,41,42-hexa- CDCl ): d 1.28 (s, 9H, Bu), 1.42 (s, 9H, Bu), 2.11 (s, 3H, –CH ),
3
3
hydroxy-calix[6]arene (7). Formaldehyde (1.3 mL) and AcOH 2.66 (brs, 4H, –CH
2
–), 3.72 (s, 2H, Ar–CH
2
–N), 3.79–4.02 (m, 4H,
(
3.8 mL) were added to a solution of calix[6]arene (1 g, 1.568 –CH
2
–), 6.48 (q, 1H, J ¼ 1.6 Hz, ArH), 6.84 (d, 1H, J ¼ 2.0 Hz,
mmol) in 75 mL of THF. 1-(2-Furoyl)piperazine was then added ArH), 7.02 (d, 1H, J ¼ 3.2 Hz, ArH), 7.25 (d, 1H, J ¼ 2.0 Hz, ArH),
to the mixture, which was stirred at rt. Aer 24 h, the volatile 7. 47 (q, 1H, J ¼ 0.8 Hz, ArH), 10.48 (s, 1H, –OH). Anal. calcd for
components were removed under reduced pressure, and
C
25
H
37IN
2
O
3
: C, 55.56; H, 6.90; N, 5.18. Found (%): C, 55.42; H,
100 mL deionized water was added and extracted with CHCl3 7.06; N, 5.05.
(
3 ꢃ 100 mL). The combined organic phase was washed with
water to neutralize it, dried over MgSO and concentrated to
form a precipitate from MeOH. Yield: 59%. Mp: 219–222 C.
4
ꢂ
General procedure for Mannich reaction in the presence of a
catalyst
ꢀ1
1
FTIR (ATR) cm : 3310 (nOH), 1615 (nC]O). H NMR (400 MHz
CDCl ): d 2.46 (brs, 24H, –CH –), 3.41 (s, 12H, Ar–CH
brs, 36H, Ar–CH –Ar, and –CH –), 6.45–6.46 (m, 6H, ArH), 6.97– dure.
3
2
2
–N), 3.79 The reaction was carried out according to the literature proce-
15,16
(
2
2
Typically, to a mixture of the catalysts (listed in the
6
1
6
.98 (m, 6H, ArH), 7.12 (brs, 12H, ArH), 7.45 (brs, 6H, ArH), tables with molar equivalents) and NaOH in water was added
0.39–10.54 (m, 6H, –OH). Anal. calcd for C102H108N O : C, aldehyde, aniline and acetophenone, respectively. The mixture
12
18
8.44; H, 6.08; N, 9.39. Found (%): C, 68.42; H, 6.20; N, 9.13.
was stirred at rt for the period of time given in the tables. The
The synthesis of 5,11,17,23,29,35-hexa-[(4-methylpiper- obtained crude was puried by column chromatography (SiO ,
2
ꢂ
ꢂ
16
1
azinium-1-yl)(furan-2-yl)methanone]methylene-37,38,39,40,41,42- EtOAc–n-hexane). Mp: 171–172 C (lit. 170–172 C); H-NMR
hexa-hydroxy-calix[6]arene hexaiodide (8). Methyl iodide (9.52 (400 MHz CDCl ): d 3.27 (dd, 1H, J ¼ 4.8, 12.4 Hz, –CH –), 3.62
3
2
g, 67.05 mmol) was added to a solution of 7 (0.4 g, 0.224 mmol) (dd, 1H, J ¼ 9.2, 8.0 Hz, –CH –), 4.95–5.00 (m, 1H, –CH–), 6.22
2
in 30 mL of DCM. The reaction mixture was stirred at rt for 6 (d, 1H, J ¼ 7.6 Hz, Ar–NH–), 6.42–6.49 (m, 3H, ArH), 6.95 (t, 2H,
days. The solvent was removed under reduced pressure and J ¼ 8.4 Hz, ArH), 7.16 (t, 1H, J ¼ 7.6 Hz, ArH), 7.27 (t, 2H, J ¼ 7.6
precipitated from MeOH and ltered. The ltrate was triturated Hz, ArH), 7.44 (d, 2H, J ¼ 7.2 Hz, ArH), 7.50 (t, 2H, J ¼ 8.0 Hz,
with Et O to form a precipitate, and ltered. 8 was obtained in ArH), 7.62 (t, 1H, J ¼ 7.6 Hz, ArH), 7.95 (d, 2H, J ¼ 6.8 Hz, ArH).
2
ꢂ
ꢀ1
13
8
2% yield. Mp: 179–182 C. FTIR (ATR) cm : 3408 (nOH), 1633
3 2
C-NMR (100 MHz, CDCl ): d 46.23 (–CH), 54.92 (–CH ), 113.96
1
(n
C]O). H-NMR (400 MHz, CDCl
.52 (m, 24H, –CH –), 3.53–3.61 (m, 24H, –CH
–), 4.16–4.19 (m, 12H, –CH –), 6.46–6.47 (m, 6H, ArH), 7.08 (ArC), 142.77 (ArC), 146.72 (N–CAr), 198.24 (C]O). Anal. calcd
19NO (%): C, 83.69; H, 6.35; N, 4.65. Found (%): C,
3 2
H, ArH). C-NMR (100 MHz, CDCl ): d 31.86 (Ar–CH –Ar), 83.59; H, 6.48; N, 4.51.
3
): d 2.11 (s, 18H, –CH
3
), 3.40– (ArC), 117.95 (ArC), 126.41 (ArC), 127.40 (ArC), 128.21 (ArC),
–), 3.69 (brs, 12H, 128.71 (ArC), 128.83 (ArC), 129.12 (ArC), 133.47 (ArC), 136.58
3
2
2
–
CH
2
2
(
6
d, 6H, J ¼ 3.6 Hz, ArH), 7.19 (brs, 18H, ArH, and –OH), 7.45 (brs, for C21
H
1
3
2224 | RSC Adv., 2014, 4, 2219–2225
This journal is © The Royal Society of Chemistry 2014