2004
Helvetica Chimica Acta – Vol. 89 (2006)
30.62; 31.37; 34.61; 37.17; 118.95; 124.10; 125.46; 126.12; 128.89; 129.16; 129.53; 129.60; 130.83; 135.14;
135.25; 149.36; 151.27; 162.16; 163.22; 193.31. MALDI-TOF-MS: 921.3207 (M+, C S4þ ; calc.
52A 46A 2A 6A
CTHREUNGH CHTREUNGN CHTREUNGO CHTREUNG
922.2233). Anal. calc. for C52H46N2O6S4 (923.18): C 67.65, H 5.02, N 3.03; found: C 67.48, H 5.07, N 3.12.
S,S’-{[4,9-Bis({[4-(1,1-dimethylethyl)phenyl]methyl}selanyl)-1,3,6,8-tetrahydro-1,3,6,8-tetraoxoben-
zo[lmn][3,8]phenanthroline-2,7-diyl]dibenzene-4,1-diyl} Diethanethioate (6). To a soln. of 19 (0.0666 g,
0.064 mmol) in CH2Cl2 (10 ml), toluene (4 ml), and AcCl (4 ml), a soln. of BBr3 in CH2Cl2 (0.2 ml)
was added dropwise at 08. The mixture was stirred for 1 h at r.t., poured into H2O, and extracted with
CH2Cl2. The combined org. phases were concentrated at reduced pressure, and the residue was purified
by CC (SiO2; CH2Cl2). Yield: 0.0387 g (59%). Pink solid. M.p. 320–3228. UV/VIS (CH2Cl2): 553 (23400),
1
515 (13000), 375 (20700), 357 (17100), 308 (51700). Fluorescence spectrum (CH2Cl2): lmax 594 nm. H-
NMR (C
H); 7.65 (d, 3J=7.8, 4 H); 8.90 (s, 2 H). 13C-NMR (C
125.25; 127.69; 128.13; 130.77; 131.26; 131.34; 132.94; 133.58; 136.69; 136.97; 149.04; 152.49; 163.92;
165.53; 194.67. MALDI-TOF-MS: 1016.4682 (M+, C Se2þ ; calc. 1016.1145). Anal. calc. for
52A 46A 2A 6A 2A
D2Cl4, 508): 1.32 (s, 6 Me); 2.52 (s, 2 Me); 4.34 (s, 2 CH2); 7.38 (s, 8 H); 7.43 (d, 3J=7.8, 4
2ACHTREUNG
2ACHTRENUDG 2Cl4, 508): 32.18; 32.67; 33.03; 36.23; 123.00;
CTHREUNGH THCREUNGN CHTREUNGO CHTRNUGSE CHTREUNG
C52H46N2O6S2Se2 (1016.98): C 61.41, H 4.56, N 2.75; found: C 61.23, H 4.61, N 2.96.
S,S’-{[4-({[4-(1,1-Dimethylethyl)phenyl]methyl}amino)-9-({[4-(1,1-dimethylethyl)phenyl]methyl}sul-
fanyl)-1,3,6,8-tetrahydro-1,3,6,8-tetraoxobenzo[lmn][3,8]phenanthroline-2,7-diyl]dibenzene-4,1-diyl}
Diethanethioate (7). To a soln. of 20a (0.2352 g, 0.252 mmol) in CH2Cl2 (20 ml), toluene (5 ml), and AcCl
(10 ml), a soln. of BBr3 in CH2Cl2 (1 ml) was added dropwise at 08. The mixture was stirred for 1 h at r.t.,
poured into H2O, and extracted with CH2Cl2. The combined org. phases were concentrated at reduced
pressure, and the residue was purified by CC (SiO2; CH2Cl2/AcOEt 1:0 ! 20 :1). Yield: 0.1380 g
(60.5%). Violet solid. M.p. 298–2998. UV/VIS (CH2Cl2): 567 (24300), 529 (14500), 366 (14600), 351
1
(13600), 289 (48700), 274 (45900). Fluorescence spectrum (CH2Cl2): lmax 596 nm. H-NMR (C
2A
3
1.31 (s, 3 Me); 1.32 (s, 3 Me); 2.51 (s, Me); 2.53 (s, Me); 4.19 (s, SCH2); 4.63 (d, J=5.1, NCH2); 7.31
(d, J=8.4 2 H); 7.34–7.43 (m, 8 H); 7.46 (d, 3J=8.4, 2 H); 7.59 (d, J=8.4, 2 H); 7.62 (d, 3J=8.4, 2
3
3
3
H); 8.30 (s, 1 H); 8.56 (s, 1 H); 9.98 (t, J=5.1, NH). 13C-NMR (C
D2Cl4): 32.29; 32.32; 33.07; 33.08;
36.28; 38.64; 48.98; 102.26; 121.06; 122.12; 123.06; 124.96; 127.70; 127.92; 128.22; 128.71; 129.28;
129.82; 130.81; 130.87; 131.01; 131.34; 131.47; 132.86; 134.68; 136.81; 136.87; 137.06; 137.53; 145.82;
152.68; 152.73; 152.99; 163.86; 164.35; 165.09; 167.53; 195.04; 195.21. Anal. calc. for
C52H47N3O6S3 ·H2O (924.16): C 67.58, H 5.34, N 4.55; found: C 67.82, H 5.50, N 4.39. MALDI-TOF-
MS: 904.1173 (M+, C Sþ3 ; calc. 905.2622).
52CAHTREUNGH47ACHTERUNNG 3ACHTRENUOG 6ACHTREUNG
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