Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
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m, 1364 m, 1234 vs, 1166 s, 1152 m, 1070 m, 1024 m, 1000 w, 892
m, 828 m, 812 s, 754 vs, 692 vs, 578 m, 506 m. H NMR (CDCl3,
TMS): δ = 1.400 (s, 6 H, CH3 of 4c), 1.479 (s, 3 H, CH3 attributable
(P.V.I. unpublished) to Me2As-S-OPh (5d)), small singlets at 1.311 and
1.344 ppm and traces of ether. In the aromatic region PhOH was de-
tected.
1
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Reaction of Bunsen’s Disulfide (1) with PhSNa·2H2O:
Preparation of Me2As-SPh (5c) and Me2AsS2Na·2H2O (3b)
To a mixture of 1 (137 mg, 0.5 mmol) and sodium thiophenolate dihy-
drate (84 mg, 0.5 mmol) in a 10 mL round-bottomed flask was added
methanol (4 mL) and the solution stirred at room temp. for 2 h. Evapo-
ration and drying in vacuo gave a white solid that was extracted with
dichloromethane (3 ϫ 2 mL) by stirring at room temp. for 15 min each
time. Drying the solid in vacuo gave Me2AsS2Na·2H2O 3b (107 mg,
94%) as a white solid soluble in methanol and water and insoluble in
dichloromethane, ether and acetone. M.p.: at approx. 170 °C sinters,
at approx. 185 °C shrinks and turns light orange and at 200–203 °C
melts to an opalescent orange oil. Calculated for C2H6AsS2Na·2H2O
(Mr 228.13): C 10.53, H 4.42, S 28.11%; found C 10.95, H 4.07, S
27.97%. IR (KBr): same as Me2AsS2Na·2H2O (3b).[9] 1H NMR
(CD3OD, TMS): δ = 1.906 (s). It resonates exactly at the same position
as Me2AsS2Na·2H2O (3b).[9]
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The dichloromethane extracts were evaporated and dried in vacuo for
a short time to give Me2As-SPh (5c) (95 mg, 88%) as a colorless
mobile liquid having a faint smell, soluble in chloroform, ether and
methanol. TLC (ether/petroleum ether 1:5, Rf 0.75). Calculated for
C8H11AsS (Mr 214.15): C 44.87, H 5.18, S 14.97%; found C 44.40,
H 4.90, S 14.65%. IR (neat): 3070 m, 3056 m, 2990 m, 2906 m, 1580
s, 1476 s, 1436 s, 1416 m, 1302 w, 1254 m, 1084 m, 1066 m, 1024 s,
1000 w, 896 s, 836 s, 740 vs, 690 vs, 578 m. 1H NMR (CDCl3, TMS):
δ = 1.356 (s, 6 H, Me2), 7.25 (m, 3 H, m and p–Ph–H), 7.43 (m, 2 H,
o–Ph–H). 1H NMR (CD3OD, TMS): δ = 1.306 (s, 6 H, Me2), 7.25 (m,
3 H, m and p–Ph–H), 7.40 (m, 2 H, o–Ph–H).
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Acknowledgments
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The authors acknowledge Professor D. Papaioannou of this Depart-
ment for useful comments on the mechanisms reported herein.
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Received: October 26, 2014
Published Online: January 20, 2015
Z. Anorg. Allg. Chem. 2015, 710–714
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