T. Torroba et al.
FULL PAPERS
fied by flash column chromatography (silica, dichloromethane to di-
chloromethane/ethyl acetate, 95:5 v/v), to give 3c (Z/E, 1/1, 30 mg, 48%)
as a dark purple solid, m.p.: 94–958C. 1H NMR (300 MHz, CDCl3): d=
acetate, 80:20 v/v), to give 4c (35 mg, 45%) as a dark reddish purple
solid, m.p.: 105–1068C. 1H NMR (300 MHz, CDCl3): d=5.85 (s, 0.4H, =
CH), 5.82 (s, 0.6H, =CH), 5.56 (s, 0.6H, =CH), 5.53 (s, 0.4H, =CH),
3.88–3.77 (m, 8H, 4ꢅCH2), 3.20–3.17 (m, 8H, 4ꢅCH2), 3.10–3.08 (m,
2H, CH2), 1.67–1.59 (m, 1H, CH), 1.38–1.28 (m, 4H, 2ꢅCH2), 0.78 ppm
(t, J=6.75 Hz, 6H, 2ꢅCH3); 13C NMR (75 MHz, CDCl3): d=190.43,
189.96 and 189.50 (C=S), 164.14, 163.69, 151.84, 151.03, 134.28, 133.22,
94.41, 92.72, 66.07, 58.55, 51.12, 50.84, 39.02, 25.49, 25.34, 11.12 ppm; IR
(KBr): n˜ =2956, 2921, 2852, 1644, 1544 (C=S), 1415, 1372, 1272, 1201,
1114 cmÀ1; EM (FAB+): m/z (%): 618 (M+·+1, 100), 532 (70); HRMS
(FAB+): calcd for M++1, C24H32N3O2S7+: 618.0534; found: 618.0543; ele-
mental analysis calcd (%) for C24H31N3O2S7: C 46.65, H 5.06, N 6.80;
found: C 46.79, H 5.14, N 6.67.
7.81–7.79 (m, 2H, C6H4), 7.71–7.69 (m, 2H, C6H4), 5.86 (s, 1= H, =CH),
2
1
5.68 (s, = H, =CH), 4.00–3.95 (m, 2H, CH2), 3.85–3.81 (m, 4H, 2ꢅCH2),
2
3.74–3.64 (m, 2H, CH2), 3.23–3.20 ppm (m, 4H, 2ꢅCH2); 13C NMR
(75 MHz, CDCl3): d=184.7 and 184.2 (C=S), 183.2 (C=O), 167.9 (C=O),
152.9, 152.4, 134.0, 131.9, 130.7, 125.0, 123.3, 123.1, 94.2, 93.6, 66.2, 66.0,
50.9, 49.4, 49.1 ppm; IR (KBr): n˜ =2924, 2855, 1710 and 1635 (C=O),
1538 (C=S), 1358, 1112, 1069 cmÀ1; MS (EI): m/z (%): 579 (M+, 36), 405
(100); HRMS: calcd for C22H17N3O4S6: 578.9543; found: 578.9542; ele-
mental analysis calcd (%) for C22H17N3O4S6: C 45.58, H 2.96, N 7.25;
found: C 45.69, H 3.13, N 7.34.
Titration Techniques
4-Ethyl-3,5-bis(4-morpholino-1,3-dithiol-2-ylidene)thiomorpholine-2,6-
Perchlorate salts were used for cations: Ag+, Ni2+, Cd2+, Pb2+, Cu2+
,
dithione, 4a
Fe3+, Al3+, and Hg2+, and triflate salts for the rest of cations: Sn2+, Zn2+
, and Sc3+. 5ꢅ10À2 m, 5ꢅ10À3 m, 5ꢅ10À4 m solutions of every salt were pre-
pared, and then a 10À4 m solution of the compound under study was pre-
pared. For qualitative experiments, 2 mL solutions of the compound
under study were measured and the corresponding amount of salt was
4-[(Trimethylsilyl)ethynyl]morpholine (80 mL, 75 mg, 0.40 mmol) and Sc-
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(50 mg, 0.15 mmol) in dichloromethane (10 mL) at room temperature
and the mixture was stirred for twenty minutes. Then the solvent was
evaporated and the crude product was purified by flash column chroma-
tography (silica, petroleum ether (40–608C) to dichloromethane/ethyl
acetate, 80:20 v/v), to give 4a (43 mg, 52%) as a dark reddish purple
solid, m.p.: 100–1018C (decomp). 1H NMR (400 MHz, CDCl3): d=5.84
(s, 0.4H, =CH), 5.82 (s, 0.6H, =CH), 5.57 (s, 0.6H, =CH), 5.54 (s, 0.4H, =
CH), 3.87–3.81 (m, 8H, 4ꢅCH2), 3.34–3.28 (m, 2H, CH2ethyl), 3.22–3.18
(m, 8H, 4ꢅCH2), 1.23–1.19 ppm (m, 3H, CH3); 13C NMR (100 MHz,
CDCl3): d=190.5, 190.0 and 189.4 (C=S), 164.6, 164.2, 151.9, 151.4,
151.3, 133.4, 132.5, 94.4, 92.9, 66.1, 51.1, 50.8, 49.3, 49.2, 14.2 ppm; IR
(KBr): n˜ =2926, 2854, 1652 (C=O), 1575 and 1539 (C=S), 1455, 1261,
1112, 1023 cmÀ1; MS (EI) m/z (%): 561 (M+·, 90), 532 (64); HRMS:
calcd for C20H23N3O2S7: 560.9835; found: 560.9824; elemental analysis
calcd (%) for C20H23N3O2S7: C 42.75, H 4.13, N 7.48; found: C 42.64,
H 4.25, N 7.36.
added by micropipette, but for microsamples of 500 mL volume, 5ꢅ10À4
m
solutions were used to get a deeper color. Quantitative measures were
performed with a Varian, Cary 300 Bio UV spectrophotometer. As a gen-
eral procedure, to a 5000 mL solution of complex, the corresponding
amount (mL) of solution of the corresponding salt (5ꢅ10À2 m, 5ꢅ10À3 m,
5ꢅ10À4 m solutions) was added, using the minor amount of solvent.
Calculations
DFT calculations were performed with the hybrid method known as
B3LYP, in which the Becke three-parameter exchange functional[17] and
the Lee–Yang–Parr correlation functional were used,[18] implemented in
the Gaussian 03 (Revision C.02) program suite.[11] The effective core po-
tentials (ECPs) of Hay and Wadt with a double-z valence basis set
(Lanl2DZ)[19] were used in describing Hg. The basis set for the main
group elements was split-valence and included polarization and diffuse
functions in all atoms [C, N, O, S, and H, abbreviated as 6-311G+
(d,p)].[20] The structures were optimized and the energies of the struc-
tures were calculated at the level described above and transition states
were confirmed by a vibrational analysis (one imaginary frequency) and
IRC calculations.[21]
4-Dodecyl-3,5-bis(4-morpholino-1,3-dithiol-2-ylidene)thiomorpholine-2,6-
dithione, 4b
4-[(Trimethylsilyl)ethynyl]morpholine (51 mL, 49 mg, 0.26 mmol) and Sc-
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(50 mg, 0.10 mmol) in dichloromethane (10 mL) at room temperature
and the mixture was stirred for twenty minutes. Then the solvent was
evaporated and the crude product was purified by flash column chroma-
tography (silica, petroleum ether (40–608C) to dichloromethane/ethyl
acetate, 80:20 v/v), to give 4b (41 mg, 56%) as a dark reddish purple
solid, m.p.: 115–1168C. 1H NMR (300 MHz, CDCl3): d=5.85 (s, 0.4H, =
CH), 5.82 (s, 0.6H, =CH), 5.55 (s, 0.6H, =CH), 5.51 (s, 0.4H, =CH),
3.86–3.80 (m, 8H, 4ꢅCH2), 3.21–3.16 (m, 10H, 5ꢅCH2), 1.67–1.64 (m,
2H, CH2), 1.25–1.19 (m, 18H, 9ꢅCH2), 0.87 ppm (t, J=6.6 Hz, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d=190.6, 190.0, 189.3, 164.3, 163.8,
151.9, 151.2, 133.8, 132.8, 94.4, 92.8, 66.1, 55.1, 55.1, 51.1, 50.9, 31.9, 29.7,
29.6, 29.5, 29.4, 29.3, 28.3, 27.5, 22.7, 14.1 ppm; IR (KBr): n˜ =2920, 2850,
1637, 1543 (C=S), 1410, 1370, 1267, 1200, 1112, 1024 cmÀ1; MS (FAB+);
m/z (%): 702 (M++ 1, 90), 532 (85), 188 (100); HRMS (FAB+): calcd for
Crystal Structure Determination for Compound 2b
A single crystal of 2b was coated in glue and mounted on a glass fiber.
X-ray measurements were made using a Bruker SMART CCD area-de-
tector diffractometer with MoKa radiation (l=0.71073 ꢇ).[22] Intensities
were integrated[23] from several series of exposures, each exposure cover-
ing 0.38 in w, and the total data set being a sphere. Absorption correc-
tions were applied, based on multiple and symmetry-equivalent measure-
ments.[24] The structure was solved by direct methods and refined by least
squares on weighted F2 values for all reflections.[25] All non-hydrogen
atoms were assigned anisotropic displacement parameters and refined
without positional constraints. All hydrogen atoms were constrained to
ideal geometries and refined with fixed isotropic displacement parame-
ters. Refinement proceeded smoothly to give the residuals. Complex neu-
tral-atom scattering factors were used.[26] Crystal data for 2b, C18H25NS7,
M=479.81, monoclinic, P21/c, a=18.472(2) ꢇ, b=9.2865(11) ꢇ, c=
13.0854(15) ꢇ, a=908, b=90.027(2)8, g=908; V=2244.7(4) ꢇ3, Z=4,
M
+ +1, C30H44N3O2S7+: 702.1473; found: 702.1464; elemental analysis
calcd (%) for C30H43N3O2S7: C 51.32, H 6.17, N 5.98; found: C 51.39,
H 6.11, N 5.90.
ACTHNUTRGNEUNG
1calcd =1.420 gcmÀ3, m(MoKa)=0.707 mmÀ1. Dark red needle, 0.60ꢅ0.30ꢅ
0.02 mm, 22729 measured reflections, 4405 independent (Rint =0.0494),
3534 observed (I>2s(I)). R1 =0.0589, wR2 =0.1220 (all data).
CCDC 762858 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
4-(2-Ethylbutyl)-3,5-bis(4-morpholino-1,3-dithiol-2-
ylidene)thiomorpholine-2,6-dithione, 4c
4-[(Trimethylsilyl)ethynyl]morpholine (50 mL, 46 mg, 0.25 mmol) and Sc-
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2c (50 mg, 0.13 mmol) in dichloromethane (10 mL) at room temperature
and the mixture was stirred for twenty minutes. Then the solvent was
evaporated and the crude product was purified by flash column chroma-
tography (silica, petroleum ether (40–608C) to dichloromethane/ethyl
1698
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1692 – 1699