First synthesis and characterization of isolable thioselenenic acid, triptycene-9-thioselenenic acid

Article abstract of DOI:10.1039/b207810d

Triptycene-9-thioselenenic acid was synthesized by hydrolysis of acetyl triptycene-9-thioselenenate, the structure of which was determined by spectroscopic data and X-ray diffraction analysis.

Full text of DOI:10.1039/b207810d

First synthesis and characterization of isolable thioselenenic acid,
triptycene-9-thioselenenic acid†
Akihiko Ishii,* Takeshi Takahashi, Akira Tawata, Aki Furukawa, Hideaki Oshida and Juzo
Nakayama*
Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan.
E-mail: ishiiaki@chem.saitama-u.ac.jp; Fax: +81 48 858 3700; Tel: +81 48 858 3394
Received (in Cambridge, UK) 9th August 2002, Accepted 11th October 2002
First published as an Advance Article on the web 25th October 2002
Triptycene-9-thioselenenic acid was synthesized by hydroly-
sis of acetyl triptycene-9-thioselenenate, the structure of
which was determined by spectroscopic data and X-ray
diffraction analysis.
Hydrodichalcogenides R–X–Y–H, where X and Y are the same
or different Group 16 elements, have drawn considerable
interest from various points of view. While hydroperoxides (R–
O–O–H) are compounds with a long history, the chemistry of
sulfenic acids (R–S–O–H)1 and selenenic acids (R–Se–O–H)2,3
Scheme 1 Reagents and conditions: i, MCPBA, CH2Cl2, 0 °C; ii,
CH3C(O)SH, 0 °C, and then rt; iii, HClO4, EtOH, CH2Cl2, refl., 6 h; iv,
PPh3, PhH, rt, 2 h.
are of current interest. On the other hand, hydrodisulfides (R–S–
S–H)4,5 and selenosulfenic acids (R–S–Se–H)6 have been
claimed to be intermediates in enzymatic reactions of cystein
and selenocystein with their lyases. A hydrodisulfide was found
to be a key intermediate in thiol-mediated DNA-damage by
leinamycin and its model compounds.7 Thioselenenic acids, R–
Se–S–H, are a member of this group and have not been isolated
yet. To our knowledge, there are only two reports on the
observation of Cys–SeSH [1, Cys = (HO2C)(H2N)CHCH2] by
UV–vis spectroscopy8a and RSeSLi (R = Bu, Ph) in THF by
77Se NMR spectroscopy.8b We report herein the isolation and
structure determination of triptycene-9-thioselenenic acid (2).
1H NMR spectrum, and an absorption due to the S–H stretching
vibration was observed at 2520 cm21 in the IR spectrum.
Thioselenenic acid 2 was stable under acidic conditions, as is
evident from the preparation conditions, whereas it decomposed
to selenol 5 and a small amount of diselenenyl sulfide 615 by
treatment with triethylamine followed by neutralization4e
[Scheme 2, (a)]; when a solution of 2 was evaporated to dryness
in the presence of triethylamine, diselenenyl sulfide 6 and
diselenide 4 were formed [Scheme 2, (b)]. Treatment of 2 with
triphenyltin chloride in the presence of triethylamine yielded
stannyl thioselenenate 716 and stannyl selenide 816 [Scheme 2,
(c)].
Polidoro and coworkers reported that treatment of (Cys–Se)2
with Na2S in an aqueous NaOH solution 1(131023 M)
generated Cys–Se–SH that exhibited an absorption maximum at
375 nm in the UV–vis spectrum.8 Fig. 2 shows UV–Vis spectra
of thioselenenic acid 2 and diselenenyl sulfide 6 in dichloro-
Acetyl triptycene-9-thioselenenate (3) was prepared using a
method analogous to that for the synthesis of acetyl alkyl
disulfides (R–S–S–Ac).9 Thus, di-9-triptycyl diselenide (4)3c
was treated with MCPBA and then with thioacetic acid to give
310 in 91% yield; it is not essential to isolate the intermediary
formed selenoseleninate (Trip–Se(O)Se–Trip3c,11). The acetyl
thioselenenate 3 was hydrolyzed with 60% perchloric acid in
refluxing ethanol–dichloromethane to furnish the desired thio-
selenenic acid 2 in 63% yield. The sulfur atom of 2 was removed
readily by treatment with triphenylphosphine to give the selenol
53c and triphenylphosphine sulfide almost quantitatively
(Scheme 1).
The structure of thioselenenic acid 2 was determined by
spectroscopic data and X-ray diffraction analysis.12 An ORTEP
drawing is depicted in Fig. 1 with relevant bond lengths and
angles data. The Se1–S1 bond length was 2.1796(9) Å,
indicating the single bond character, and the C1–Se1–S1 bond
angle was 103.85(7)°. The SH proton appeared at d 2.64 in the
Fig. 1 ORTEP drawing of triptycene-9-thioselenenic acid (2) (50%
ellipsoidal probability). Relevant bond lengths (Å) and angles (deg) data:
Se1–C1 1.975(2); Se1–S1 2.1796(9); C1–C14 1.536(3); C1–C2 1.537(3);
C1–C15 1.538(3); S1–H1 1.24(6); C1–Se1–S1 103.85(7); C14–C1–C2
106.19(17); C14–C1–C15 105.15(17); C2–C1–C15 105.31(17); C14–C1–
Se1 115.62(15); C2–C1–Se1 115.27(15); C15–C1–Se1 108.37(15).
† Electronic supplementary information (ESI) available: experimental
section. See http://www.rsc.org/suppdata/cc/b2/b207810d/
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CHEM. COMMUN., 2002, 2810–2811
This journal is © The Royal Society of Chemistry 2002

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Scheme 2 Reagents and conditions: i, Et3N, PhH, rt, 5 min; ii, aq. NH4Cl;
iii, evaporation in the presence of Et3N; iv, Ph3SnCl, Et3N, PhH, rt, 1 h.
Yields are calculated from 1H NMR integral ratios.
8 (a) G. Polidoro, P. De Cicco, S. Di Luzio and G. Federici, Boll. Soc. Ital.
Biol. Sper., 1979, 55, 2346; (b) C. Köllemann, D. Obendorf and F.
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1
10 3: mp 177–180 °C (CH2Cl2–hexane). H NMR (CDCl3, 400 MHz) d
2.50 (s, 3H), 5.37 (s, 1H), 6.98–7.05 (m, 6H), 7.35–7.40 (m, 3H),
7.47–7.51 (m, 3H); 13C NMR (CDCl3, 100.6 MHz) d 29.8, 54.1, 64.9,
123.5, 123.7, 125.0, 125.9, 144.1, 145.2, 192.1; IR (KBr) 1700 (CNO)
cm21. Anal. Calc. for C22H16OSSe: C, 64.86; H, 3.96. Found: C, 64.80;
H, 3.92%.
11 In this one-pot reaction, we have prepared (1-Ad)CH2SeSAc and
(1-Ad)CH(CH3)SeSAc (1-Ad = 1-adamantyl).
12 2: pale yellow plates, mp 170–172 °C decomp (CH2Cl2–hexane). 1H
NMR (CDCl3, 400 MHz) d 2.64 (s, 1H, SH), 5.38 (s, 1H), 7.00–7.08 (m,
6H), 7.36–7.42 (m, 3H), 7.49–7.54 (m, 3H); 13C NMR (CDCl3, 100.6
MHz) d 54.0, 61.1, 123.6, 123.8, 125.0, 125.7, 144.1, 145.8; IR (KBr)
2520 cm21. Anal. Calc. for C20H14SSe: C, 65.75; H, 3.86. Found: C,
65.73; H, 3.89%. Crystal data: C20H14SSe, Mw 365.36, pale yellow
¯
plate, 0.24 3 0.16 3 0.08 mm3, triclinic, space group P1, a = 8.181(2),
Fig. 2 UV-vis spectra of triptycene-9-thioselenenic acid (2) and di-
(triptycene-9-selenenyl) sulfide (6).
b = 8.217(1), c = 13.175(3) Å, a = 82.53(1), b = 72.58(1), g =
67.82(1)°, V = 782.4(2) Å3, Z = 2, rcalc = 1.551 g cm23, m(CuKa) =
4.42 mm21. Mac Science MXC3KHF diffractometer with graphite-
monochromated CuKa radiation (l = 1.54178 Å), q/2q scans method
in the range 3° < 2q < 140° (29 @h @9, 0 @k @10, 215 @l @16),
2994 independent reflections. The structure was solved with direct
methods (SIR9213), and refined with full-matrix least-squares
(SHELXL-9714) using all independent reflections for 256 parameters.
Absorption correction was done by a psi-scan method. The non-
hydrogen atoms were refined anisotropically: R1 = 0.0303 (I > 2s(I),
2822 reflections), wR2 = 0.0860 (for all), GOF = 1.05; max/min
residual density = 0.454/20.452 e Å23. CCDC reference number
191691. See http://www.rsc.org/suppdata/cc/b2/b207810d/ for crys-
tallographic data in CIF or other electronic format.
methane. The absorption of 2 ceased approximately at 360 nm,
while 6 has a broad absorption from 285 to 360 nm with the
molecular absorption coefficient (e/103 cm2 mol21) ≈ 1000.
Anyway, we did not observe an explicit absorption maximum
around 375 nm. This might be attributed to the contrasting
character of the substituents: the more sterically demanding,
hydrophobic 9-tripycyl group and the much less sterically
demanding, hydrophilic 2-amino-3-propionyl (Cys) group. We
are therefore now investigating the preparation of thioselenenic
acids having groups derived from the Cys group or alkyl
substituents structurally simpler than the 9-triptycyl group.
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14 G. M. Sheldrick, SHELXL-97, Program for Crystal Structure Refine-
ment, Göttingen University, Germany, 1997.
Notes and references
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15 6: pale yellow crystals, mp 345–346 °C decomp (hexane–CH2Cl2). 1H
NMR (CDCl3, 300 MHz) d 5.46 (s, 2H), 7.11 (pseudo d of quintet, J =
1.5, 7.4 Hz, 12H), 7.46 (dd, J = 1.5, 7 Hz, 6H), 7.76 (dd, J = 1.5, 8 Hz,
6H); 13C NMR (CDCl3, 100.6 MHz) d 54.2, 65.2, 123.7, 124.4, 125.1,
125.9, 144.7, 145.6. Anal. Calc. for C40H22SSe2: C, 68.96; H, 3.76.
Found: C, 68.31; H, 3.68%.
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16 The structures of 7 and 8 were determined by X-ray crystallography.
CCDC reference numbers 191692 (7) and 191693 (8). 7: yellow
crystals, mp 176–178 °C decomp (Et2O–hexane). 1H NMR (CDCl3, 200
MHz) d 5.29 (s, 1H), 6.74 (dt, J = 1, 8 Hz, 3H), 6.93 (dt, J = 1, 7 Hz,
3H), 7.30 (dd, J = 1, 7 Hz, 3H), 7.43–7.55 (m, 12H), 7.74–7.84 (m, 6H,
accompanying satellite signals, J = 55 Hz, due to 117Sn and 119Sn); 13
C
NMR (CDCl3, 75.5 MHz) d 54.0, 61.7, 123.1, 124.6, 124.8, 125.4,
129.1, 130.2, 137.0, 137.1, 144.4, 145.4. Anal. Calc. for C38H28SSeSn:
C, 63.89; H, 3.95. Found: C, 63.71; H, 3.90. 8: colorless cubes, mp
253–255 °C (hexane–CH2Cl2). 1H NMR (CDCl3, 400 MHz) d 5.28 (s,
1H), 6.64 (dt, J = 1, 8 Hz, 3H), 6.87 (dt, J = 1, 8 Hz, 3H), 7.20—7.34
(m, 12H), 7.40 (dd, J = 1, 8 Hz, 6H, accompanying satellite signals, J
= 55 Hz, due to 117Sn and 119Sn), 7.79 (d, J = 7.5 Hz, 3H); 13C NMR
(CDCl3, 100.6 MHz) d 54.1, 61.7, 122.6, 124.5, 125.36, 125.41, 128.6,
129.4, 136.8, 138.2, 144.8, 146.4. Anal. Calc. for C38H28SeSn: C, 66.89;
H, 4.14. Found: C, 66.65; H, 4.04%.
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