Molecules 2021, 26, 2334
11 of 15
for C132H192N O S C, 66.74; H, 8.44; N, 6.77; S, 7.75; Found: C, 66.68; H, 8.16; N, 6.71; S,
8
16 4
2
+
3+
4+
4+
7
.39. HRMS: calculated [M + 2H] m/z = 1137.6743, [M + 3H] m/z = 758.7852, [M + 4H]
m/z = 569.3408, found [M + 2H] m/z = 1137.6723, [M + 3H] m/z = 758.7846, [M + 4H]
m/z = 569.3409.
2+
3+
3
.2.2. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis[N-(6-(4,6-di-tert-butyl-2,3-
dihydroxybenzylideneamino)hexyl)carbamoylmethoxy]-2,8,14,20-tetrathiacalix[4]arene
in partial cone Conformation (9)
◦
1
Yellow-orange powder, yield: 308 mg (91%). M.p. 117 C. H NMR (CDCl , δ,
3
ppm, J/Hz): 1.02 (s, 18H, (CH ) C), 1.26 (s, 9H, (CH ) C), 1.29 (s, 9H, (CH ) C), 1.37 (s,
3
3
3 3
3 3
3
6H, (CH ) C), 1.41 (s, 36H, (CH ) C), 1.42–1.48 (m, 16H, NH(CH ) (CH ) (CH ) N=CH),
3 3 3 3 2 2 2 2 2 2
1
.59–1.67 (m, 8H, NHCH2 CH2(CH ) N=CH), 1.72–1.76 (m, 8H, NH(CH ) CH2CH N=CH),
2 4 2 4 2
3
.27–3.42 (m, 8H, NHCH (CH ) N=CH), 3.61 (m, 8H, NH(CH ) CH2N=CH), 4.26 (d of AB
2
2 5
2 5
2
2
system, 2H, OCH CO, J = 14.4), 4.86 (d of AB system, 2H, OCH CO, J = 14.4), 4.44
2
HH
2
HH
(
s, 2H, OCH CO), 4.96 (s, 2H, OCH CO), 6.53 (s, 4H, ArH(C H )), 7.05 (d of AB system, 2H,
2 2 6 1
4
4
ArH, J = 2.4), 7.45 (d of AB system, 2H, ArH, J = 2.4), 7.53 (br.t, 1H, NH), 7.61 (C, 2H,
HH
HH
1
3
ArH), 7.76 (C, 2H, ArH), 7.88 (br.t, 2H, NH), 8.64 (br.t, 1H, NH), 8.83 (s, 4H, CH=N).
NMR (CDCl3, , ppm): 168.8, 168.5, 168.1, 163.9, 159.4, 158.0, 155.9, 147.6, 146.6, 143.8, 139.9,
39.8, 139.8, 136.4, 135.2, 135.1, 133.4, 127.9, 127.4, 125.9, 125.8, 112.5, 109.7, 74.3, 73.8, 70.2,
C
δ
1
5
2
4.5, 54.3, 54.3, 39.3, 39.2, 38.9, 35.5, 35.3, 33.3, 31.4, 31.2, 31.1, 30.6, 30.5, 29.7, 29.6, 29.2, 26.9,
−
1
6.6, 26.5, 26.5, 26.4. FTIR ATR (
616 (C=N), 1532 (C(O)NH, amide II), 1088 (CArOCH ). Elemental analysis. Calculated for
ν, cm ): 3312 (NH), 3062 (NH), 1673 (C(O)NH, amide I),
1
2
C132H192N O S C, 66.74; H, 8.44; N, 6.77; S, 7.75; Found: C, 66.72; H, 8.54; N, 6.43; S, 7.79.
8
16 4
2+
3+
4+
4+
HRMS: calculated [M + 2H] m/z = 1137.6743, [M + 3H] m/z = 758.7852, [M + 4H]
m/z = 569.3408, found [M + 2H]2+ m/z = 1137.6745, [M + 3H] m/z = 758.7857, [M + 4H]
m/z = 569.3418.
3+
3
.2.3. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis[N-(6-(4,6-di-tert-butyl-2,3-
dihydroxybenzylideneamino)hexyl)carbamoylmethoxy]-2,8,14,20-tetrathiacalix[4]arene
in 1,3-alterate Conformation (10)
◦
1
Yellow-orange powder, yield: 324 mg (96%). M.p. 115 C. H NMR (CDCl ,
δ
, ppm,
3
J/Hz): 1.18 (s, 36H, (CH ) C), 1.38 (s, 36H, (CH ) C), 1.41 (s, 36H, (CH ) C), 1.35–1.43
3
3
3 3
3 3
(
m, 16H, NH(CH ) (CH ) (CH ) N=CH), 1.60 (m, 8H, NHCH2 CH2(CH ) N=CH), 1.74
2 2 2 2 2 2 2 4
(
m, 8H, NH(CH2)4CH2CH N=CH), 3.24 (m, 8H, NHCH2(CH ) N=CH), 3.61 (m, 8H,
2
2 5
NH(CH2)5CH2N=CH), 4.06 (s, 8H, OCH CO), 6.60 (s, 4H, ArH(C H )), 7.52 (s, 8H, ArH),
2
6
1
13
7
.75 (br.t, 4H, NH), 8.84 (s, 4H, CH=N). C NMR (CDCl3,
δ, ppm): 168.2, 164.0, 156.9, 147.5,
1
2
43.8, 133.3, 127.2, 115.3, 112.8, 110.1, 71.2, 54.6, 39.4, 35.6, 35.3, 34.4, 33.8, 33.4, 31.2, 30.6,
9.6, 29.2, 29.0, 26.8, 26.5. FTIR ATR (ν, cm ): 3319 (NH), 3065 (NH), 1668 (C(O)NH, amide
−
1
I), 1618 (C=N), 1531 (C(O)NH, amide II), 1085 (CArOCH ). Elemental analysis. Calculated
2
for C132H192N O S C, 66.74; H, 8.44; N, 6.77; S, 7.75; found: C, 66.52; H, 8.64; N, 6.63; S,
8
16 4
2
+
3+
4+
4+
7
.74. HRMS: calculated [M + 2H] m/z = 1137.6743, [M + 3H] m/z = 758.7852, [M + 4H]
m/z = 569.3408, found [M + 2H] m/z = 1138.1733, [M + 3H] m/z = 758.7826, [M + 4H]
m/z = 569.3399.
2+
3+
3.3. Procedure for the Synthesis of Compound 11 (Monomer)
A mixture of 4,6-di-tert-butyl-1,2-dihydroxybenzaldehyde (163.4 mg, 0.6527 mmol)
and N-(6-aminohexyl)-2-(4-tert-butylphenoxy)acetamide [44] (200 mg, 0.6527 mmol) in
methanol (5 mL) was stirred at room temperature. The precipitate formed was then filtrated.
The residue was washed with methanol (3
and dried under reduced pressure over phosphorus pentoxide.
×
15 mL), isolated as orange crystalline powders,
2
-(4-tert-Butylphenoxy)-N-(6-(4,6-di-tert-butyl-2,3-
dihydroxybenzylideneamino)hexyl)acetamide (11)
◦
1
Yellow-orange powder, yield: 316 mg (90%). M.p. 55 C. H NMR (CDCl , δ,
3
ppm, J/Hz): 1.29 (s, 9H, (CH ) C), 1.40 (s, 9H, (CH ) C), 1.42 (s, 9H, (CH ) C), 1.33–1.48
3
3
3 3
3 3