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4H; NH-CO), 9.01 (s, 2H; Ar-H), 7.99 (s, 2H; Ar-H) 7.24 (s, 2H; Ar-H),
(brs, 2H; NH-CO), 9.10 (s, 2H; Ar-H), 9,08 (brs, 4H; Ar-NH-Ar), 7.36
(s, 2H; Ar-H), 7.16 (s, 2H; Ar-H), 4.99 (s, 2H; Ar-H), 3.49 (t, J(H,H)=
3
3
5.40 (s, 2H; Ar-H), 2.24 (t, J(H,H)=6.5 Hz, 8H; COCH2), 1.52 (m, 8H;
3
CH2CH3), 0.88 ppm (t, J(H,H)=7.3 Hz, 12H; CH3); HRMS (ESI): m/z
8.6 Hz, 8H; NCH2), 1.83 (m, 8H; NCH2CH2), 1.45 (m, 8H; CH2CH3),
calcd for C40H48N13O12+: 902.3540 [M+NH4]+; found: 902.3539.
1.13 (s, 36H; COC(CH3)3), 0.98 ppm (t, J(H,H)=7.31 Hz, 12H; CH3);
3
C60H88ClN13O12·H2O (1236.89): calcd C 58.26, H 7.33, N 14.72; found
4,6,16,18-Tetranitro-10,12,22,24-tetra(pentylamido)-2,8,14,20-
tetraazacalix[4]arene (9): A solution of azacalixarene 6 (100 mg,
16 mmol) and valeroyl chloride (79 mL, 0.66 mmol, 4 equiv) in aceto-
nitrile (150 mL) was stirred under argon for 1 h at RT before N-eth-
yldiisopropylamine (0.11 mL, 0.66 mmol, 4 equiv) was added drop-
wise. The mixture was heated to reflux overnight. The solvent was
evaporated to dryness and the residue was dissolved in CH2Cl2.
The organic phase was washed with water, dried over MgSO4, fil-
tered, and evaporated under vacuum. Chromatography on silica
gel (MeOH/CH2Cl2, 1:9; Rf =0.47) followed by crystallization from
a mixture of CH2Cl2 and n-hexane afforded pure 9 (112 mg, 12
mmol, 72%) as a yellow solid. M.p.>3008C; 1H NMR (400 MHz,
[D6]DMSO, 258C): d=9.56 (brs, 4H; Ar-NH-Ar), 9.31 (brs, 4H; NH-
CO), 9.01 (s, 2H; Ar-H), 7.92 (s, 2H; Ar-H) 7.22 (s, 2H; Ar-H), 5.33 (s,
2H; Ar-H), 2.24 (t, 3J(H,H)=7.1 Hz, 8H; COCH2), 1.43 (m, 8H;
COCH2CH2), 1.92 (m, 8H; CH2CH3), 0.80 ppm (t, 3J(H,H)=7.3 Hz,
12H; CH3); HRMS (ESI): m/z calcd for C44H56N13O12+: 958.4166
[M+NH4]+; found: 958.4167.
À
C 58.42, H 7.39, N 14.48; MS (ESI): m/z calcd for C44H51N12O12
:
939.5 [MÀH]À and for C44H52ClN12O12À: 975.4 [M+Cl]À; found 939.4
and 975.4.
Host–guest complex 13: A solution of tetraamido-tetraazacalixar-
ene 10 (15 mg, 16 mmol) and tetra-n-butylammonium bromide
(5.65 mg, 17 mmol, 1.1 equiv) in acetone (2 mL) was heated to
reflux for 24 h. The resulting yellow precipitate was filtered off,
washed with acetone, and dried under vacuum to give 13 (14 mg,
11 mmol, 68%). M.p.> 3008C; 1H NMR (250 MHz, [D6]acetone,
258C): d=9.45 (brs, 4H; NHCO), 9.13 (brs, 4H; Ar-NH-Ar), 9.11 (s,
2H; Ar-H) 7.49 (s, 2H; Ar-H), 7.21 (s, 2H; Ar-H), 5.09 (s, 2H; Ar-H),
3
3.49 (t, J(H,H)=8.6 Hz, 8H; NCH2), 1.84 (m, 8H; NCH2CH2), 1.48 (m,
3
8H; CH2CH3), 1.14 (s, 36H; COC(CH3)3), 0.98 ppm (t, J(H,H)=7.3 Hz,
12H; CH3); C60H88BrN13O12·1.5H2O (1290.35): calcd C 55.85, H 7.11, N
14.11; found C 55.97, H 7.11, N 13.90; MS (ESI): m/zÀcalcd for
À
C44H51N12O12
:
939.5 [MÀH]À, and for C44H52BrN12O12
: 1021.4
[M+Br]À; found: 939.4 and 1021.4.
4,6,16,18-Tetranitro-10,12,22,24-tetra(2,2-dimethylpropionami-
do)-2,8,14,20-tetraazacalix[4]arene (10): A solution of azacalixar-
ene 6 (190 mg, 0.31 mmol) and trimethylacetyl chloride (0.38 mL,
3.1 mmol, 10 equiv) in acetonitrile (200 mL) was stirred under nitro-
gen for 1 h at RT before N-ethyldiisopropylamine (0.55 mL,
3.1 mmol, 10 equiv) was added dropwise. The mixture was heated
to reflux overnight. The reaction was monitored by TLC (cyclohex-
ane/EtOAc, 2:3; Rf =0.35). The solvent was evaporated to dryness
and the residue was dissolved in CH2Cl2. The organic phase was
washed with water, dried over MgSO4, filtered and evaporated
under vacuum. The crude residue was purified by chromatography
on silica gel (cyclohexane/ethyl acetate, 2:3) to give 10 (94 mg,
Host–guest complex 14: A solution of tetraamido-tetraazacalixar-
ene 10 (7 mg, 7.4 mmol) and tetra-n-butylammonium iodide (3 mg,
8.1 mmol, 1.1 equiv) in acetone (1.5 mL) was heated to reflux over-
night. The resulting yellow precipitate was filtered and dried under
1
vacuum to give 14 (4.6 mg, 3.5 mmol, 46%). M.p.> 3008C; H NMR
(250 MHz, [D6]acetone, 258C): d=9.30 (brs, 4H; NHCO), 9.13 (s,
2H; Ar-H), 8.72 (brs, 4H; Ar-NH-Ar), 7.84 (s, 2H; Ar-H), 7.32 (s, 2H;
Ar-H), 5.47 (s, 2H; Ar-H), 3.50 (t, 3J(H,H)=8.6 Hz, 8H; NCH2), 1.81
(m, 8H; NCH2CH2), 1.46 (m, 8H; CH2CH3), 1.17 (s, 36H; COC(CH3)3),
0.98 ppm (t, 3J(H,H)=7.3 Hz, 12H; CH3); C60H88IN13O12·H2O
(1328.35): calcd C 54.25, H 6.83, N 13.71; found C 54.65, H 6.91, N
13.60; MS (ESI): m/z calcd for C44H51N12O12À: 939.5 [MÀH]À, and for
C44H52IN12O12À: 1067.1 [M+I]À; found: 939.4 and 1067.1.
0.10 mmol, 32%) as
a
yellow solid. M.p.>2608C; 1H NMR
(250 MHz, [D6]DMSO, 258C): d=9.30 (brs, 4H; Ar-NH-Ar), 9.00 (brs,
6H; Ar-H, NH-CO), 7.57 (s, 2H; Ar-H), 7.41 (s, 2H; Ar-H), 5.61 (s, 2H;
Ar-H), 1.09 ppm (s, 36H; C(CH3)3); 1H NMR (250 MHz, [D6]acetone,
258C): d=9.34 (brs, 4H; Ar-NH-Ar), 9.13 (s, 2H; Ar-H), 8.47 (brs,
4H; NHCO), 7.98 (s, 2H; Ar-H), 7.35 (s, 2H; Ar-H), 5.61 (s, 2H; Ar-H),
1.18 ppm (s, 36H; C(CH3)3); C44H52N12O12·2H2O (976.99): calcd C
54.09, H 5.78, N 17.2; found C 54.35, H 5.31, N 17.10; HRMS (ESI):
m/z calcd for C44H56N13O12+: 958.4166 [M+NH4]+; found: 958.4166.
Host–guest complex 15: A solution of tetraamido-tetraazacalixar-
ene 10 (20 mg, 21 mmol) and tetra-n-butylammonium acetate
(6.2 mg, 21 mmol, 1 equiv) in acetone (2 mL) was heated to reflux
for 24 h. The resulting yellow precipitate was filtered off, washed
with acetone and dried under vacuum to give 15 (16 mg, 12 mmol,
59%). M.p. (dec.)> 1658C; 1H NMR (250 MHz, [D6]acetone, 258C):
d=9.90 (brs, 4H; Ar-NH-Ar) 9.08 (s, 2H; Ar-H), 7.72 (s, 2H; Ar-H),
3
7.15 (s, 2H; Ar-H), 5.34 (s, 2H; Ar-H), 3.44 (t, J(H,H)=8.3 Hz, 8H;
Host–guest complex 11: A solution of tetraamido-tetraazacalixar-
ene 10 (10 mg, 10 mmol) and tetra-n-butylammonium fluoride
(2.7 mg, 10 mmol, 1 equiv) in acetone (1.5 mL) was heated to reflux
for 24 h. The resulting precipitate was filtered, washed with ace-
tone and dried under vacuum to give the host–guest complex 11
(7.4 mg, 6.1 mmol, 60%). M.p. (dec.)>1008C; 1H NMR (250 MHz,
[D6]acetone, 258C): d=9.02 (s, 2H; Ar-H), 7.74 (s, 2H; Ar-H), 7.14 (s,
2H; Ar-H), 5.36 (s, 2H; Ar-H), 3.44 (t, 3J(H,H)=8.6 Hz, 8H; NCH2),
1.86 (m, 8H; NCH2CH2), 1.45 (m, 8H; CH2CH3), 1.15 (s, 36H;
NCH2), 1.79 (m, 8H; NCH2CH2), 1.41 (m, 8H; CH2CH3), 1.15 (s, 36H;
COC(CH3)3),
0.98 ppm
(t,
3J(H,H)=7.3 Hz,
12H,
CH3);
C62H91N13O14·H2O (1260.49): calcd C 59.08, H 7.44, N 14.45; found C
59.11, H 7.59, N 14.30; MS (ESI): m/z calcd for C44H51N12O12À: 939.5
[MÀH]À; found: 939.5.
Host–guest complex 16: A solution of tetraamido-tetraazacalixar-
ene 10 (20 mg, 21 mmol) and N-benzyl-4-(dimethylamino) pyridini-
um bromide (6.2 mg, 21 mmol, 1 equiv) in acetone (2 mL) was
heated to reflux for 24 h under argon. The resulting precipitate
was filtered, washed with acetone, and dried under vacuum to
give 16 (12 mg, 10 mmol, 46%). M.p.> 3008C; 1H NMR (250 MHz,
[D6]acetone, 258C): d=9.44 (s, 4H; NHCO), 9.13 (brs, 4H; Ar-NH-
COC(CH3)3),
0.98 ppm
(t,
3J(H,H)=7.3 Hz,
12H;
CH3);
C60H88FN13O12·3H2O (1256.47): calcd C 57.35, H 7.54, N 14.49; found
2À
C 57.39, H 7.05, N 14,31; MS (ESI): m/z calcd for C44H50N12O12
:
469.2 [MÀ2H]2À and for C44H51N12O12À: 939.5 [MÀH]À; found: 469.3
3
and 939.4.
Ar), 9.12 (s, 2H; Ar-H), 8.45 (d, J(H,H)=7.9 Hz, 2H; Ar-Hpy), 7.50 (s,
3
Host-guest complex 12: A solution of tetraamido-tetraazacalixar-
ene 10 (18 mg, 19 mmol) and tetra-n-butylammonium chloride
(5.8 mg, 21 mmol, 1.1 equiv) in acetone (1.5 mL) was heated to
reflux for 24 h. The resulting precipitate was filtered, washed with
acetone and dried under vacuum to give 12 (18 mg, 14 mmol,
2H; Ar-H), 7.44 (m, 5H; Ar-H), 7.20 (s, 2H; Ar-H), 7.16 (d, J(H,H)=
7.9 Hz, 2H; Ar-Hpy), 5.56 (s, 2H; N+CH2), 5.08 (s, 2H; Ar-H), 3.34 (s,
6H; N(CH3)2), 1.14 ppm (s, 36H; C(CH3)3); C58H69BrN14O12·2H2O
(1270.20): calcd C 54.84, H 5.79, N 15.44; found C 54.67, H 5.61, N
15.32; MS (ESI): m/z calcd for C44H51N12O12À: 939.5 [MÀH]À, and for
C44H52BrN12O12À: 1021.4 [M+Br]À; found 939.4 and 1021.3.
1
75%). M.p.> 3008C; H NMR (250 MHz, [D6]acetone, 258C): d=9.86
Chem. Eur. J. 2016, 22, 5756 – 5766
5764
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