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A. Kertmen et al.
PAPER
Bis(11-hydroxyundecyl) Trisulfide (5b)
Chromatography (CHCl3–MeOH, 25:1), white solid; yield: 84%;
mp 61–63 °C.
tered, and evaporated under vacuum. The residue was purified by
column chromatography; this gave 5a–f. The yields are reported in
Table 2.
1H NMR (200 MHz, CDCl3): d = 1.20–1.46 (m, 28 H, CH2), 1.39 (s,
2 H, OH), 1.46–1.65 (m, 4 H, CH2), 1.65–1.82 (m, 4 H, CH2), 2.87
(t, J = 7.3 Hz, 4 H, SCH2), 3.64 (t, J = 6.5 Hz, 4 H, OCH2).
Acknowledgment
We gratefully acknowledge the Polish Ministry of Science and
Higher Education for financial support (grant No. N N204 4511 33).
13C NMR (50 MHz, CDCl3): d = 63.0, 38.8, 32.7, 29.5, 29.4, 29.1,
28.8, 28.5, 25.7. Signals: expected, 11; observed, 9.
HRMS (ESI): m/z [M + Na]+ calcd for C22H46NaO2S3: 461.2558;
found: 461.2556.
References
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Bis(10-carboxydecyl) Trisulfide (5c)
Chromatography (CHCl3–MeOH, 25:1), white solid; yield: 92%;
mp 79–81 °C.
1H NMR (200 MHz, CDCl3): d = 1.24–1.50 (m, 24 H, CH2), 1.54–
1.84 (m, 8 H, CH2), 2.36 (t, J = 7.3 Hz, 4 H, CH2COO), 2.88 (t,
J = 7.3 Hz, 4 H, SCH2), 8.90 (br s, 2 H, COOH).
13C NMR (50 MHz, CDCl3): d = 180.2, 38.8, 34.0, 29.3, 29.3, 29.1,
29.1, 29.0, 28.8, 28.4, 24.6. Signals: expected, 11; observed, 11.
(4) Schöberl, A.; Wagner, A. In Houben-Weyl, 4th ed., Vol. 9;
Müller, E., Ed.; Georg Thieme Verlag: Stuttgart, 1955, 87–
90.
HRMS (ESI): m/z [M + Na]+ calcd for C22H42NaO4S3: 489.2143;
found: 489.2151.
(5) (a) Zysman-Colman, E.; Harpp, D. N. J. Org. Chem. 2003,
68, 2487. (b) Clayton, J. O.; Etzler, D. H. J. Am. Chem. Soc.
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Bis(2-hydroxyethyl) Trisulfide (5d)15,28
Chromatography (CHCl3–MeOH, 25:1), colorless oil; yield: 81%.
1H NMR (200 MHz, CDCl3): d = 2.16 (s, 2 H, OH), 3.09 (t, J = 5.7
Hz, 4 H, SCH2), 3.99 (t, J = 5.7 Hz, 4 H, OCH2).
13C NMR (50 MHz, CDCl3): d = 59.5, 41.7. Signals: expected, 2;
observed, 2.
HRMS (ESI): m/z [M + Na]+ calcd for C4H10NaO2S3: 208.9741;
found: 208.9736.
Ber. 1963, 96, 38.
(9) Buckman, J. D.; Field, L. J. Org. Chem. 1967, 32, 2.
(10) Mott, A. W.; Barany, G. Synthesis 1984, 657.
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Chem. Pharm. Bull. 1967, 15, 1310.
(12) Capozzi, G.; Capperucci, A.; Degl’Innocenti, A.; Del Duce,
R.; Menichetti, S. Tetrahedron Lett. 1989, 30, 2991.
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Lett. 2005, 46, 4797. (b) Hou, Y.; Abu-Yousef, I. A.;
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D. A. J. Phys. Chem. 1982, 86, 4417.
Bis[(R)-2-(tert-butoxycarbonylamino)-2-(ethoxycarbonyl)eth-
yl] Trisulfide (5e)
Chromatography (CH2Cl2–EtOAc, 25:1), white solid; yield: 92%;
mp 74–77 °C.
1H NMR (200 MHz, CDCl3): d = 1.30 (t, J = 7.1 Hz, 6 H,
COOCH2CH3), 1.46 (s, 18 H, Boc), 3.37 (d, J = 4.8 Hz, 4 H, SCH2),
4.23 (q, J = 7.1 Hz, 4 H, COOCH2), 4.56–4.72 (m, 2 H, CH), 5.44
(d, J = 7.8 Hz, 2 H, BocNH).
13C NMR (50 MHz, CDCl3): d = 170.3, 155.0, 80.2, 61.9, 52.9,
41.1, 28.3, 14.1. Signals: expected, 8; observed, 8.
HRMS (ESI): m/z [M + Na]+ calcd for C20H36N2NaO8S3: 551.1531;
found: 551.1527.
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(21) Antoniow, S.; Witt, D. Synthesis 2007, 363.
(22) Kowalczyk, J.; Barski, P.; Witt, D.; Grzybowski, B. A.
Langmuir 2007, 23, 2318.
Bis(4-tolyl) Trisulfide (5f)
Chromatography (CH2Cl2–PE, 1:2), bright yellow solid; yield:
87%; mp 76–77 °C (Lit.5a 78–79 °C).
1H NMR (200 MHz, CDCl3): d = 2.36 (s, 6 H, CH3), 7.12 (d, J = 7.9
Hz, 4 H, Ar), 7.45 (d, J = 7.9 Hz, 4 H, Ar).
13C NMR (50 MHz, CDCl3): d = 138.6, 131.0, 129.8, 128.5, 21.2.
Signals: expected, 5; observed, 5.
(23) Szymelfejnik, M.; Demkowicz, S.; Rachon, J.; Witt, D.
HRMS (ESI): m/z [M + Na]+ calcd for C14H14NaS3: 301.0155;
Synthesis 2007, 3528.
found: 301.0160.
(24) Demkowicz, S.; Rachon, J.; Witt, D. Synthesis 2008, 2033.
(25) Pappo, D.; Kashman, Y. Org. Lett. 2006, 8, 1177.
(26) Edmundson, R. S. Tetrahedron 1965, 21, 2379.
(27) Carmona, E.; Contreras, L.; Sanches, L. J.; Gutierrez-
Puebla, E.; Monge, A. J. Chem. Soc., Dalton Trans. 1989,
2003.
Symmetrical Trisulfides 5 from 4a–f; General Procedure Using
Method B
Solid thioacetamide (83 mg, 1.1 mmol) was added to a soln of 4a–f
(2.0 mmol) and Et3N (0.293 mL, 2.1 mmol) in CH2Cl2 (20 mL) at
0 °C under air atmosphere. The mixture was stirred at 0 °C for 30
min, and evaporated under vacuum. Then Et2O (100 mL) was added
and mixture was washed with H2O (50 mL), dried (MgSO4), fil-
(28) Kohama, Y.; Iida, K.; Semba, T.; Mimura, T.; Inada, A.
Chem. Pharm. Bull. 1992, 40, 2210.
Synthesis 2009, No. 9, 1459–1462 © Thieme Stuttgart · New York