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Green Chemistry
4
4JH H = 2.8 Hz, 1H, H6); 6.54 (d, JH H = 2.8 Hz, 1H, H2); 6.83 Procedures for acid functionalization (20, 21, 22)
6
2
2
6
(d, 3JH H = 8.8 Hz, 1H, H5).
5
6
Allylated compound 11, 12 or 13 (1.0 eq.) and 3-mercaptopro-
pionic acid (6.0 eq.) were mixed without adding any solvent.
The solution was irradiated in the UV reactor. The reactions
were monitored by 1H NMR.
13C NMR (100.6 MHz, DMSO-d6, ppm) δ: 27.50 (s, C15); 27.52
(s, C10); 29.14 (s, C14); 29.30 (s, C9); 35.23 (s, C16); 35.25 (s,
C11); 41.55 (s, C17); 41.57 (s, C12); 55.56 (s, C7); 66.34 (s, C13);
67.85 (s, C8); 101.00 (s, C2); 104.26 (s, C6); 114.98 (s, C5); 142.12
(s, C4); 150.27 (s, C3); 153.42 (s, C1).
HRMS (m/z, ES+, [M + H+]): calculated: 375.1779; found:
375.1776.
Product
20:
3,3′-((((3-methoxy-1,4-phenylene)bis(oxy))bis-
(propane-3,1-diyl))bis(sulfanediyl))dipropionic acid (68%, pale
yellow liq.).
Product 18: 3-((2-aminoethyl)thio)propyl-4-(3-((2aminoethyl)
thio) propoxy)-3-methoxybenzoate (93%, pale yellow liq.).
1H NMR (400.1 MHz, DMSO-d6, ppm) δ: 1.97 (m, 4H, H9,
H16); 2.52 (2*t, 4H, H11, H18); 2.63 (2*t, 4H, H10, H17); 2.68 (t,
4H, H12, H19); 3.82 (s, 3H, H14); 4.11 (t, 2H, H15); 4.30 (t, 2H,
1H NMR (400.1 MHz, DMSO-d6, ppm) δ: 1.91 (q, 4H, H9, H16);
2.51 (m, 4H, H13, H20); 6.66 (m, 8H, H10, H11, H17, H18); 3.73
3
(s, 3H, H7); 3.93 (t, 2H, H8); 3.96 (t, 2H, H15); 6.39 (dd, JH H
=
6
5
4
4
8.8 Hz, JH H = 2.8 Hz, 1H, H6); 6.56 (d, JH H = 2.8 Hz, 1H,
H2); 6.84 (d, JH H = 8.8 Hz, 1H, H5); 12.28 (broad s, 2H,
6
2
2
6
3
3
4
5
6
H8); 7.09 (d, JH H = 8.6 Hz, 1H, H5); 7.45 (d, JH H = 2.0 Hz,
5
6
2
6
H14, H21).
1H, H2); 7.58 (dd, 3JH H = 8.6 Hz, 4JH H = 2.0 Hz, 1H, H6).
13C NMR (100.6 MHz, DMSO-d6, ppm) δ: 26.36, 26.39 (2*s,
C11, C18); 27.59, 27.62 (2*s, C10, C17); 28.92, 29.08 (2*s, C9, C16);
34.45, 34.49 (2*s, C12, C19); 55.55 (s, C7); 66.33 (s, C8); 67.85 (s,
C15); 101.04 (s, C2); 104.31 (s, C6); 115.06 (s, C5); 142.11 (s, C4);
150.30 (s, C3); 153.44 (s, C1); 172.66 (s, C13, C20).
6
5
6
2
13C NMR (100.6 MHz, DMSO-d6, ppm) δ: 27.28 (s, C10); 27.47
(s, C17); 28.52 (s, C9); 28.83 (s, C16); 35.14, 35.16 (2*s, C11, C18);
41.52 (s, C12, C19); 55.59 (s, C14); 63.19 (s, C15); 66.87 (s, C8);
111.94 (s, C5); 112.09 (s, C2); 121.95 (s, C1); 123.13 (s, C6);
148.55 (s, C3); 152.20(s, C4); 165.44 (s, C7).
HRMS (m/z, ES+, [M + H+]): calculated: 433.1357; found:
433.1355.
HRMS (m/z, ES+, [M + H+]): calculated: 403.1721; found:
403.1725.
Product 19: 2-((3-((4-(3-((2-aminoethyl)thio)propoxy)-3-methoxy- Product 21: 3-((3-((4-(3-((2-carboxyethyl)thio)propoxy)-3-meth-
benzyl)oxy)propyl)thio)ethan-1-amine (88%, pale yellow liq.).
oxybenzoyl)oxy)propyl)thio)propanoic acid (92%, m.p. 68 °C).
1H NMR (400.1 MHz, DMSO-d6, ppm) δ: 1.76 (tt, 2H, H9);
1H NMR (400.1 MHz, (DMSO-d6, ppm) δ: 1.97 (m, 4H, H10,
1.94 (tt, 2H, H16); 2.52 (m, 3H, H10, H11, H18); 2.66 (m, 3H, H17); 2.51 (m, 4H, H13, H20); 2.67 (m, 8H, H11, H12, H18, H20);
H12, H17, H19); 3.46 (t, 1H, H8); 3.75 (s, 3H, H14); 4.01 (t, 1H, 3.81 (s, 3H, H7); 4.10 (t, 2H, H16); 4.29 (t, 2H, H9); 7.06 (d,
3
4
4
H15); 4.36 (s, 2H, H7); 6.81 (dd, JH H = 8.0 Hz, JH H = 1.2 Hz, 3JH H = 8.6 Hz, 1H, H5); 7.45 (d, JH H = 2.0 Hz, 1H, H2); 7.58
6
5
6
2
5
6
2
6
4
3
1H, H6); 6.90 (d, JH H = 1.2 Hz, 1H, H2); 6.91 (d, JH H
=
(dd, 3JH H = 8.6 Hz, 4JH H = 2.0 Hz, 1H, H6).
13C NMR (100.6 MHz, (DMSO-d6, ppm) δ: 26.31, 26.34 (2*s,
13C NMR (100.6 MHz, DMSO-d6, ppm) δ: 27.41 (s, C17); 27.78 C12, C19); 27.39, 27.63 (2*s, C11, C18); 28.34, 28.64 (2*s, C10
2
6
5
6
6
5
6
2
8.0 Hz, 1H, H5).
,
(s, C10); 29.10 (s, C16); 29.57 (s, C9); 35.19 (s, C18); 35.26 (s, C17); 34.42, 34.46 (2*s, C13, C20); 55.60 (s, C7); 63.22 (s, C9);
C11); 41.54 (s, C12, C19); 55.49 (s, C14); 66.91 (s, C15); 67.88 (s, 63.8 (s, C16); 111.94, 112.09 (2*s, C5, C2); 121.99 (s, C1); 123.18
C8); 71.77 (s, C7); 111.72 (s, C5); 113.11 (s, C2); 119.93 (s, C6); (s, C6); 148.57 (s, C3); 152.20 (s, C4); 165.49 (s, C7); 173.03
131.25 (s, C1); 147.33 (s, C4); 148.96 (s, C3).
HRMS (m/z, ES+, [M + H+]): calculated: 389.1932; found:
399.1933.
(s, C14, C21).
HRMS (m/z, ES+, [M + H+]): calculated: 461.1302; found:
461.1304.
1996 | Green Chem., 2014, 16, 1987–1998
This journal is © The Royal Society of Chemistry 2014