Synthesis utilizing reducing ability of carbon monoxide: a new method for selective synthesis of diorgano selenides and diselenides using selenium-carbon monoxide-water reaction system

Microwave-assisted one-pot synthesis of symmetrical diselenides, ditellurides and disulfides from organoyl iodides and elemental chalcogen catalyzed by CuO nanoparticles

“…After the optimization of the best solvent and base, other important parameters were studied, such as the reaction time, microwave irradiation (power) and temperature (Table 2, entries [10][11][12][13][14][15][16]. When the reaction time was reduced from 10 to 7 min of irradiation no significant decline in the yield was observed (entries 1 and 10).…”

“…Several methods have been described for the synthesis of diorganoyl diselenides and ditellurides [9][10][11][12][13][14][15][16][17][18] which include the reaction of metal diselenides or ditellurides with organoylhalides [19][20][21], the well established reaction of Grignard reagents with elemental selenium or tellurium, the reduction of selenocyanates [22][23][24][25] and the oxidation of both selenols and selenolates [26,27]. Several methodologies have been described for the synthesis of diorganoyl disulfides generally obtained by oxidation of thiols [28][29][30][31][32][33] or even, according to Taniguchi, from elemental sulfur and aryl iodides catalyzed by Cu-bpy, aluminum and sodium carbonate [34].…”

“…61-62 • C), yield: 70%; 1 H NMR (CDCl 3 , 200 MHz) (ı, ppm) 7.61 (m, 4H), 7.25-7.21 (m, 6H); 13 C NMR (CDCl 3 , 50 MHz) (ı, ppm) 131.5, 130.9, 129.1, 127.7; GC-MS: m/z (%) 314(34), 312(33), 310(16), 234(18), 232(10), 230(5), 159(16), 158(25), 157 (80), 155(48), 153(22), 117(16), 78 (78), 77 (100), 51(61), 50(29).Bis(4-methylphenyl) diselenide (2b):[27,47] orange solid, mp 42-43 • C (lit. 44-45 • C), yield: 71%; 1 H NMR (CDCl 3 , 200 MHz) (ı, ppm) 7.49 (d, J = 8.2 Hz, 4H), 7.07 (d, J = 8.2 Hz, 4H), 2.34 (s, 6H); 13 C NMR (CDCl 3 , 50 MHz) (ı, ppm) 139.Bis(3-methoxyphenyl) diselenide (2d): [47] orange solid, mp 191-193 • C (lit.…”

Highly Efficient Route to Diselenides from the Reactions of Imines and Selenium in the Presence of Carbon Monoxide and Water

“…Oxidation of selenols with 30% hydrogen peroxide [11] and reduction of aldehydes and ketones with hydrogen selenide [12,13] in the presence of an amine afforded diselenides. Sonoda et al used the Se/CO/H 2 O system for the preparation of diselenides from a very limited number of aliphatic ketones and aldehydes, [14] or acyl chlorides [15] under rather harsh conditions, while aromatic ketones were reduced to hydrocarbons with the same method. [16] Recently, we reported the synthesis of symmetrical diselenides from aldehydes by means of a modified Se/ CO/H 2 O system.…”

Efficient Reductive Selenation of Aromatic Aldehydes to Symmetrical Diselenides with Se/CO/H2O under Atmospheric Pressure.

“…11 However, most of the known methods for preparation of diselenides suffer from disadvantages such as use of strong reducing agents and highly toxic gas, harsh reaction conditions, low yields, or complicated manipulations. Sonoda et al discovered that elemental selenium can be readily reduced by carbon monoxide and water in the presence of base to produce hydrogen selenide, which was successfully applied to the synthesis of aliphatic diselenides from both aliphatic ketones and aldehydes 12 or from alkyl chlorides and acyl chlorides, 13 respectively. Although Sonoda's method is relatively convenient and can be easily manipulated, 12,13 the process is subject to relatively high pressure of CO (0.5-3.0 MPa), high temperature (120°C), and long reaction times (e.g., 24 h), and when aromatic ketones ArC(dO)R′ were used as the substrates, only reduction products ArCH 2 R′ instead of diselenides were obtained.…”