Abstract:
A selenating reagent obtained by reacting lithium aluminum hydride with selenium powder in an organic solvent. In addition, a method for preparing a selenating reagent includes reacting lithium aluminum hydride with selenium powder in an organic solvent. Also, a method of preparing a selenium-containing product includes reacting the selenating reagent, prepared as stated, with at least one second compound which may be acyl chloride.

Description:
BACKGROUND OF THE INVENTION 
     The present invention is related to a selenating reagent. 
     Recently many syntheses of compounds containing selenium have been studied and reported because of the interesting reactivities and their potential pharmaceutical significance. Several methods for the synthesis of selenium-containing compounds using various types of selenating reagents have been developed. The alkali metal salts of hydrogen selenide, which can be readily prepared in situ by the reaction of elemental selenium and a reducing reagent (such as Li, LiBEt 3 H, Na, NaBH 4 , NaBEt 3 H, and iBu 2 AlH) have often been used as selenating reagents for the introduction into organic molecules. 
     However, the use of these salts as selenating reagents has been limited to the synthesis of dialkyl diselenides, dialkyl selenides, selenothiocarbamates, selenoamides, and certain other applications. A selenating reagent, capable of preparing a wide range of selenium-containing compounds, has not been reported. 
     The synthesis of diacyl selenides has been infrequently reported. Jensen, K. A.; Bøje, L.; Henriksen, L.  Acta Chem. Scand.,  1972, 26, 1465 reported the existence of unstable benzoyl selenide, which was obtained by the elimination of hydrogen selenide from selenobenzoic acid at room temperature. The benzoyl selenide was in turn transformed into dibenzoyl diselenide and bis(selenobenzoate). Kageyama, H.; Kido, K.; Kato, S.; Murai, T. J.  Chem. Soc., Perkin Trans.  1, 1994, 1083 reported the preparation of diacyl selenides by the reaction of O-silyl selenocarboxylates with acyl chorides. Ishihara, H.; Sato, S.; Hirabayashi, Y.  Bull. Chem. Soc. Jpn,  1977, 50, 3007 described the preparation of diacyl selenides. However, these methods all required many steps, while the present method is a one-pot reaction from which could be easily isolated diacyl selenides in very high yields using silica gel flash column chromatography. Until now it has been relatively difficult to be obtain aliphatic diacyl selenides because of their instability. 
     Synthesis examples of diacyl diselenides include: (a) Ishihara, H.; Hirabayashi, Y.  Chem. Lett.,  1976, 203. (b) Wang, J.-X.; Cui, W.-F.; Hu, Y.-L.; Zang, S.-S.  J. Chem. Res . (S), 1990, 230. (c) Nishiyama, Y.; Katsuura, A.; Negoro, A.; Hamanaka, S.; Miyoshi, N.; Yamana, Y.; Ogawa, A.; Sonoda, N.  J. Org. Chem.,  1991, 56, 3776. (d) Niyomura, O.; Tani, K.; Kato, S.,  Heteroatm Chem.,  1999, 10, 373. (e) Niyomura, O.; Kato, S.; Inagaki, S.,  J. Am. Chem. Soc.,  2000, 122, 2132 
     Synthesis of glutaric selenoanhydride was reported in Koketsu, M.; Hiramatsu, S.; Ishihara, H. Chem. Lett., 1999, 485. 
     There is only one additional example of the synthesis of a γ-Selenobutyrolactone in the literature. That is Günther, W. H. H.  J. Org. Chem.,  1966, 31, 1202. 
     An example of N-alkyl diselenocarbamate synthesis; Henriksen, L.  Int. J. Sulfur Chem.,  1973, 8, 389. Carbodiimide was obtained via oxidation of selenourea using NaIO 4  in quantitative yield. This method involved the reverse reaction. 
     Selenoureas and selenothiocarbamates bearing limited types of functional groups has been synthesized by using sodium hydrogen selenide. Klayman, D. L.; Shine, R. J.  J. Org. Chem.,  1969, 34, 3549. 
     SUMMARY OF THE INVENTION 
     Accordingly, it is an objective of the present invention to provide a selenating reagent that is applicable for preparing various kinds of selenium-containing compounds. 
     To achieve the foregoing and other objectives and in accordance with the purpose of the present invention, a novel selenating reagent is provided. The selenating reagent is obtained by reacting lithium aluminum hydride with selenium powder in an organic solvent. The selenating reagent is represented by a chemical formula of LiAlHSeH. 
     It is preferable that the organic solvent is tetrahydrofuran or diethyl ether. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     A method for preparing a selenating reagent will now be described. 
     One equivalent of lithium aluminum hydride was added with stirring to one equivalent of black selenium powder suspended in tetrahydrofuran (THF) under an argon atmosphere at 0° C. for thirty minutes. Considerable hydrogen gas was immediately evolved and the black selenium powder was consumed in less than ten minutes. One equivalent of hydrogen gas was recovered in the present reaction. The reaction mixture became a heterogeneous grayish suspension. 
     In  1 H NMR spectrum of the product, two proton peaks of different circumstances, 1.86 and 3.75 ppm, were observed. These chemical shifts are close to the literature&#39;s ones of similar compounds. From these facts, it was determined that the product generated in the present reaction was LiAlHSeH. The product formed in situ was ready for further reaction without concentration. 
     Various kinds of solvents investigated and two solvents were found that could be used in this reaction: THF and diethyl ether. 
     The selenating reagent was applied to syntheses of many kinds of selenium-containing products by the reaction with a second compound. 
     Reaction of the selenating reagent with two equivalents of acyl chloride gave diacyl selenide in excellent yield. Both aromatic and aliphatic diacyl selenides were obtained in excellent yields by using the selenating reagent. 
     Reaction of the selenating reagent with acyl chloride (1 equivent) and a mixture of iodine and potassium iodine (1.0 equivent/0.2 equivent) yielded diacyl diselenide in 75–86% yield. 
     Reaction of the selenating reagent with glutaryl chloride formed glutaric selenoanhydride in 66% yield. This method gave glutaric selenoanhydride in better yield than the first reported synthesis of glutaric selenoanhydride. 
     γ-Selenobutyrolactone was obtained by adding 4-chlorobutyryl chloride into the selenating reagent n 71%. The present method has less steps than the previously reported method. Reaction of the selenating reagent with N,N-diethyl amide and oxalyl chloride gave N,N-diethyl selenoamide in 68%. 
     Reaction of the selenating reagent with carbodiimide afforded selenourea in 62%. 
     Se-methyl N-phenylcarbamate was obtained by the reaction of the selenating reagent with phenyl isocyanate and methyl iodide. In contrast, the Se-methyl N-phenylcarbamate could not be prepared using lithium selenide obtained by lithium triethylborohydride reduction of selenium because of being unable to supply the hydrogen. 
     N,N-Dimethyl selenocarbamoyl chloride (CH 3 ) 2 NC(═Se)Cl, easily prepared in situ from reaction of the selenating reagent with dichloromethylenedimethyliminium chloride [Cl 2 C═N(CH 3 ) 2 ]Cl, and can be trapped with various nucleophiles such as amines, lithium alkylthiolates and lithium alkylselenolates, to give the corresponding selenoureas, S-alkyl selenothiocarbamates, and Se-alkyl diselenocarbamates in good to high yields. This is the first reported syntheses of N,N-dialkyl diselenocarbamates. 
     Because the present study can use various carbodiimides, isocyanates, amines, lithium alkylthiolates or lithium alkylselenolates as nucleophiles, a variety of selenium-containing compounds bearing various kinds of alkyl groups are readily prepared. 
     According to the present invention, the potential wide ranging utility of the selenating reagent is provided by the preparation of various organic selenium compounds. 
     EXAMPLES 
     The invention will be further illustrated by following examples, which set forth particularly advantageous method embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it. 
     General Methods 
     Tetrahydrofuran was distilled from sodium-benzophenone immediately prior to use. The  77 Se chemical shifts were expressed in ppm deshielded with respect to neat Me 2 Se in CDCl 3 . All spectra of selenium-containing products (Examples 2 through 19) were identical with authentic samples or the published spectra data. All new compounds gave satisfactory spectral and microanalytical data. 
     Example One 
     LiAlHSeH Selenating Reagent 
     To a solution of selenium powder (0.80 g, 10.0 mmol) in dry THF (100 mL) was added lithium aluminium hydride (0.38 g, 10.0 mmol) at 0° C. under an argon atmosphere. The mixture was stirred for thirty minutes. Lithium hydrogen selenide was formed in situ and was then ready for further reaction without concentration. The mixture was evaporated for NMR analysis.  1 H NMR (CDCl 3 ) δ 1.86 (1H, t, J=6.8 Hz), 3.75 (1H, t, J=6.8 Hz);  1 H NMR (DMSO-d6) δ 1.76 (1H, t, J=6.8 Hz), 3.60 (1H, t, J=6.3 Hz). 
     Example Two 
     Dibenzoyl Selenide 
     Benzoyl chloride (0.23 mL, 2.0 mmol) was added to the solution of LiAlHSeH (1.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at 0° C. for two hours. The mixture was extracted with diethyl ether and washed with a saturated NaCl solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane:n-hexane (1:1) to give 0.25 grams (86%) of dibenzoyl selenide as a white powder; mp 60.6–61.4° C.; C 14 H 10 O 2 Se; IR (KBr) 1722, 1669 cm −1 ;  1 H NMR (CDCl 3 ) δ 7.49 (4H, t, J=8.0 Hz, Ar), 7.63 (2H, t, J=7.2 Hz, Ar), 7.95 (4H, dd, J=1.6, 8.8 Hz, Ar);  13 C NMR (CDCl 3 ) δ 128.4, 128.9, 134.4, 138.5, 188.6;  77 Se NMR (CDCl 3 ) δ 746.2; MS (CI): m/z= 291 [M   + +1]. 
     Example Three 
     Di-p-Toluoyl Selenide 
     This example was prepared following the same procedure as Example Two except using p-toluoyl chloride (0.26 mL, 2.0 mmol) instead of benzoyl chloride. 0.29 grams (86%) of di-p-toluoyl selenide was obtained by flash chromatography on silica gel as a yellow powder; mp 109.6–111.2° C.; C 16 H 14 O 2 Se; IR (KBr) 1704, 1744 cm −1 ;  1 H NMR (CDCl 3 ) δ 2.40 (6H, s, CH 3 ), 7.26 (4H, d, J=8.0 Hz, Ar), 7.83 (4H, d, J=8.0 Hz, Ar);  13 C NMR (CDCl 3 ) δ 21.7, 128.5, 129.6, 136.0, 145.5, 188.1;  77 Se NMR (CDCl 3 ) δ 740.5; MS (CI): m/z=319 [M + +1]. 
     Example Four 
     Diphenylacetyl Selenide 
     This example was prepared following the same procedure as Example Two except using phenylacetyl chloride (0.26 mL, 2.0 mmol) instead of benzoyl chloride. 0.31 milligrams (97%) of diphenylacetyl selenide was obtained by flash chromatography on silica gel as a yellow powder; mp 53.0–53.4° C.; C 16 H 14 O 2 Se; IR (KBr) 1699, 1760 cm −1 ;  1 H NMR (CDCl 3 ) δ 3.95 (4H, s, CH 2 ), 7.12 (4H, dd, J=2.0, 7.6 Hz, Ar), 7.23 (6H, m, Ar);  13 C NMR (CDCl 3 ) δ 55.2, 127.8, 128.8, 129.8, 131.8, 195.3;  77 Se NMR (CDCl 3 ) δ 818.8; MS (CI): m/z=319 [M + +1]. 
     Example Five 
     Distearoyl Selenide 
     This example was prepared following the same procedure as Example Two except using stearoyl chloride (0.68 mL, 2.0 mmol) instead of benzoyl chloride. 0.60 grams (97%) of distearoyl selenide was recrystallized from benzene as a white crystal; mp 75.0–75.6° C.; C 36 H 70 O 2 Se; IR (KBr) 1718, 1774 cm −1 ;  1 H NMR (CDCl 3 ) 0.88 (t, J=6.4 Hz, 6H, CH 3 ) 1.26 (56H, s, CH 2 ), 1.64 (4H, m), 2.81 (4H, t, J=7.2 Hz, CH 2 );  13 C NMR (CDCl 3 ) δ 14.1, 22.7, 24.8, 28.7, 29.2, 29.3, 29.5, 29.7, 31.9, 49.5, 198.1;  77 Se NMR (CDCl 3 ) δ 809.8; MS (CI): m/z=615 [M + +1]. 
     Example Six 
     Dibenzoyl Diselenide 
     Benzoyl chloride (0.23 mL, 2 mmol) was added to a solution of LiAlHSeH (2.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at 0° C. for 30 minutes. Iodine (0.25 grams, 2.0 mmol) and potassium iodide (0.07 g, 0.40 mmol) in THF (10 mL) was added to the reaction mixture. The reaction mixture was stirred at 0° C. for 1.5 hour. The mixture was extracted with dichloro methane and washed with 1% sodium hydrogensulfite and water. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane:n-hexane (1:1) to give 0.30 grams (81%) of dibenzoyl diselenide as a yellow powder; mp 131.0–133.6° C.; C 14 H 10 O 2 Se 2 ; IR (KBr) 1686, 1740 cm −1 ;  1 H NMR (CDCl 3 ) δ 7.50 (4H, t, J=7.6 Hz, Ar), 7.65 (2H, t, J=7.2 Hz, Ar), 8.01 (4H, dd, J=1.6, 8.8 Hz, Ar);  13 C NMR (CDCl 3 ) δ 128.1, 129.1, 134.3, 136.7, 187.3;  77 Se NMR (CDCl 3 ) δ 615.0; MS (CI): m/z=371 [M + +1]. 
     Example Seven 
     Di-p-Toluoyl Diselenide 
     This example was prepared following the same procedure as Example Six except using p-toluoyl chloride (0.26 mL, 2.0 mmol) instead of benzoyl chloride. 0.34 grams (85%) of di-p-toluoyl diselenide was obtained by flash chromatography on silica gel as a yellow powder; mp 75.0–75.6° C.; C 16 H 14 O 2 Se 2 ; IR (KBr) 1702, 1743 cm −1 ;  1 H NMR (CDCl 3 ) 2.42 (s, 6H, CH 3 ) 7.28 (4H, d, J=8.0 Hz, Ar), 7.90 (4H, d, J=8.0 Hz, Ar);  13 C NMR (CDCl 3 ) δ 21.8, 128.2, 129.7, 134.1, 145.5, 186.8;  77 Se NMR (CDCl 3 ) δ 608.2; MS (CI): m/z=399 [M + +1]. 
     Example Eight 
     Diphenylacetyl Diselenide 
     This example was prepared following the same procedure as Example Six except using phenylacetyl chloride (0.26 mL, 2.0 mmol) instead of benzoyl chloride. 0.30 grams (75%) of diphenylacetyl diselenide was obtained by flash chromatography on silica gel as a yellow powder; mp 85.6–87.2° C.; C 16 H 14 O 2 Se 2 ; IR (KBr) 1724, 1736 cm −1 ;  1 H NMR (CDCl 3 ) δ 4.00 (s, 4H, CH 2 ) 7.34 (10H, m, Ar);  13 C NMR (CDCl 3 ) δ 52.0, 128.3, 128.9, 130.2, 132.0, 193.0;  77 Se NMR (CDCl 3 ) δ 644.2; MS (CI): m/z=399 [M + +1]. 
     Example Nine 
     Glutaric Selenoanhydride 
     Glutaryl chloride (0.20 g, 1.0 mmol) was added to the solution of LiAlHSeH (1.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at room temperature for 2 hours. The mixture was extracted with dichloromethane and washed with saturated sodium carbonate solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane:n-hexane (1:1) to give 0.12 grams (66%) glutaryl chloride as an orange oil; mp 60.6–61.4° C.; C 5 H 6 O 2 Se; IR(KBr) 1698 cm −1 ;  1 H NMR (CDCl 3 ) δ 2.16 (2H, q, J=17.6 Hz), 2.77 (4H, t, J=12.0 Hz),;  13 C NMR (CDCl 3 ) δ 9.2, 43.6, 200.7;  77 Se NMR (CDCl 3 ) δ 827.4; MS (CI): m/z=179 [M + +1] 179; Anal. Calcd for C 5 H 6 O 2 Se: C, 33.92; H, 3.42. found: C, 33.98; H, 3.49%. 
     Example Ten 
     γ-Butyroselenolactone 
     4-chlorobutyryl chloride (0.22 mL, 2.0 mmol) was added to the solution of LiAlHSeH (2.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at 0° C. for fifteen minutes. The mixture was extracted with diethyl ether and washed with saturated NaCl solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane: n-hexane (1:1) to give 0.21 grams (71%) of γ-butyroselenolactone as a pale yellow oil; C 4 H 6 OSe; IR (KBr) 1709 cm −1 ;  1 H NMR (CDCl 3 ) δ 2.25 (2H, q, J=6.8 Hz), 2.46 (2H, t, J=6.8 Hz), 3.52 (2H, t, J=6.8 Hz);  13 C NMR (CDCl 3 ) δ 26.6, 29.9, 46.8, 212.1;  77 Se NMR (CDCl 3 ) δ 463.3; MS (CI): m/z=151[M + +1]; HRMS: m/z=149.9584 calcd for C 4 H 6 OSe, found 149.9576. 
     Example Eleven 
     N,N-Diethylbenzselenoamide 
     To a solution of N,N-diethylbenzamide (0.18 g, 1.0 mmol) in dry diethylether (5 mL), oxalyl chloride (1.0 mmol, 0.09 mL) was added. The mixture was stirred at 0° C. for one hour under an argon atmosphere. Moreover, the reaction mixture was stirred for three hours at room temperature. The mixture was added to the solution of LiAlHSeH (1.2 mmol), prepared as described above in Example One. The reaction mixture was stirred at room temperature for three hours. The mixture was extracted with diethyl ether and washed with water. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane to give 0.16 grams (68%) of N,N-diethylbenzselenoamide as a yellow crystal; mp 53–54° C.; C 11 H 15 NSe;  1 H NMR (CDCl 3 ) δ 1.15 (3H, t, J=6.8 Hz, CH 3 ), 1.45 (3H, t, J=6.8 Hz, CH 3 ), 3.43 (2H, q, J=6.8 Hz, CH 2 ), 4.25 (2H, q, J=6.8 Hz, CH 2 ), 7.21 (2H, d, J=7.6 Hz, Ar), 7.28 (1H, d, J=6.8 Hz, Ar), 7.33 (2H, t, J=7.2 Hz, Ar);  13 C NMR (CDCl 3 ) δ 11.2, 13.2, 48.3, 49.7, 123.7, 127.8, 128.0, 146.5, 204.0;  77 Se NMR (CDCl 3 ) δ 705.3; MS (CI): m/z=242 [M + +1]; HRMS: m/z=241.0369 calcd for C 11 H 15 NSe, found 241.0368. 
     Example Twelve 
     N,N′-Diisopropylselenourea 
     N,N′-diisopropylcarbodiimide (0.15 mL, 1.0 mmol) was added to the solution of LiAlHSeH (1.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at 0° C. for one hour. The mixture was extracted with diethyl ether and washed with saturated NaCl solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane:n-hexane (40:1) to give 0.13 grams (62%) N,N′-diisopropylselenourea as a white crystal; mp 142.6–148.2° C.; C 7 H 16 N 2 Se; IR (KBr) 1515, 1570, 3195, 3246 cm −1 ;  1 H NMR (CDCl 3 ) δ 1.19 (12H, d, J=6.4 Hz, CH 3 ), 4.21 (2H, br s), 6.10 (2H, br s);  13 C NMR (CDCl 3 ) δ 22.4, 47.9,176.2; MS (EI): m/z=208 [M + ]; HRMS: m/z=208.0478 calcd for C 7 H 16 N 2 Se, found 208.0503. 
     Example Thirteen 
     Se-methyl N-phenylselenocarbamate 
     Phenyl isocyanate (0.11 mL, 1.0 mmol) was added to a solution of LiAlHSeH (1.0 mmol) prepared as described above in Example One. The reaction mixture was stirred at room temperature for one hour. Methyl iodide (0.06 mL, 1.0 mmol) was added to the reaction mixture. The reaction mixture was stirred at room temperature for two hours. The mixture was extracted with diethyl ether and washed with water. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane:n-hexane (4:1) to give 0.09 grams (70%) of Se-methyl N-phenylselenocarbamate as a yellow crystal; Mp. 90.8–93.0° C.; C 8 H 9 NOSe; IR (KBr) 1646 cm −1 ;  1 H NMR (CDCl 3 ); δ 2.31 (3H, s, CH 3 ), 7.08–7.42 (5H, m, Ar), 7.79 (1H, br s, NH);  13 C NMR (CDCl 3 ); δ 6.2, 119.8–137.5 (Ar), 162.2;  77 Se NMR (CDCl 3 ) δ 334.1; MS (EI): m/z=214 [M + ]; Anal. Calcd for C 8 H 9 NOSe: C, 44.87; H, 4.24; N, 6.54. found: C, 45.13; H, 4.09; N, 6.56%. 
     Example Fourteen 
     N-benzyl-N,N′,N′-trimethylselenourea 
     Dichloromethylenedimethyliminium chloride (0.16 g, 1.0 mmol) was added to a solution of LiAlHSeH (1.0 mmol), prepared as described above in Example One, at 0° C. under an argon atmosphere. The reaction mixture was stirred at 0° C. for 1.5 hours. To the solution, N-methylbenzylamine (0.26 mL, 2.0 mmol) was added and was stirred at room temperature for two hours. The mixture was extracted with dichloromethane (100 mL) and washed with water (30 mL). The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane to give 0.19 grams (75%) of N-benzyl-N,N′,N′-trimethylselenourea as a yellow oil; C 11 H 16 N 2 Se; IR (Neat) 1508 cm −1 ;  1 H NMR (CDCl 3 ) δ 2.93 (3H, s, CH 3 ), 3.19 (6H, s, CH 3 ), 4.93 (2H, s, CH 2 ), 7.26–7.36 (5H, m, Ar);  13 C NMR (CDCl 3 ) δ 41.9, 44.8, 60.9, 127.4, 127.7, 128.5, 136.4, 195.3;  77 Se NMR (CDCl 3 ) δ 341.6; MS (CI): m/z=257 [M + +1]; Anal. Calcd for C 11 H 14 N 2 Se: C, 52.18; H, 5.57; N, 11.06. found: C, 52.11; H, 5.54; N, 11.12%. 
     Example Fifteen 
     1-(N,N-Dimethylselenocarbamoyl) piperidine 
     This example was prepared following the same procedure as Example 14 except using piperidine (0.20 mL, 2.0 mmol) instead of dichloromethylenedimethyliminium chloride. 0.20 grams (95%) of 1-(N,N-dimethylselenocarbamoyl) piperidine was obtained by flash chromatography on silica gel as a pale yellow oil; C 8 H 16 N 2 Se; IR (neat) 1506 cm −1 ;  1 H NMR (CDCl 3 ) δ 1.66 (6H, br s, CH 2 ), 3.18 (6H, s, CH 3 ), 3.52 (4H, br s, CH 2 );  13 C NMR (CDCl 3 ) δ 24.2, 25.7, 44.7, 54.0, 194.7;  77 Se NMR (CDCl 3 ) δ 333.0; MS (CI): m/z=221 [M + +1]. 
     Example Sixteen 
     S-phenyl N,N-dimethylselenothiocarbamate 
     To the solution of LiAlHSeH (2.0 mmol) prepared as described above in Example One, was added dichloromethylenedimethyliminium chloride (0.32 grams, 2.0 mmol) at 0° C. under an argon atmosphere. The reaction mixture was stirred at 0° C. for 1.5 hours. This solution was added to the solution of PhS − Li +  (1.0 mmol), which was prepared by the reaction of lithium aluminium hydride (0.046 g, 1.2 mmol) with diphenyl disulfide (0.12 g, 0.5 mmol) in dry THF (10 mL) at 0° C. under an argon atmosphere. The reaction mixture was stirred at 0° C. for two hours. The mixture was extracted with dichloromethane (100 mL) and washed with water (30 mL). The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with dichloromethane to yield of 0.19 grams (74%) of S-phenyl N,N-dimethylselenothiocarbamate was obtained by flash chromatography on silica gel as a yellow crystal; mp 84.5–85.3° C.; C 9 H 11 NSSe;  1 H NMR (CDCl 3 ) δ 3.45 (3H, s, CH 3 ), 3.66 (3H, s, CH 3 ), 7.43–7.51 (5H, m, Ar);  13 C NMR (CDCl 3 ) δ 43.0, 49.6, 128.9, 130.1, 132.9, 136.8 199.5;  77 Se NMR (CDCl 3 ) δ 607.5; MS (CI): m/z=246 [M + +1]; HRMS: m/z=244.9778 calcd for C 9 H 11 NSSe, found 244.9762. 
     Example Seventeen 
     S-benzyl N,N-dimethylselenothiocarbamate 
     This example was prepared following the same procedure as Example Sixteen except using Ph CH 2 S − Li +  (1.0 mmol) instead of PhS − Li + . 0.17 grams (65%) of S-Benzyl N,N-dimethylselenothiocarbamate was obtained by flash chromatography on silica gel as a yellow crystal; mp 47.2–48.1° C.; C 10 H 13 NSSe;  1 H NMR (CDCl 3 ) δ 3.31 (3H, s, CH 3 ), 3.67 (3H, s, CH 3 ), 4.62 (2H, s, CH 2 ), 7.26–7.42 (5H, m, Ar);  13 C NMR (CDCl 3 ) δ 42.5, 46.4, 49.1, 127.5, 128.5, 129.2, 135.2 198.3;  77 Se NMR (CDCl 3 ) δ 547.9; MS (CI): m/z=260 [M + +1]; HRMS: m/z=258.9933. calcd for C 10 H 13 NSSe, found 258.9923; Anal. Calcd for C 10 H 13 NSSe: C, 46.32; H, 5.05; N, 5.40. found: C, 46.51; H, 5.24; N, 5.58%. 
     Example Eighteen 
     Se-phenyl N,N-dimethyldiselenocarbamate 
     This example was prepared following the same procedure as Example Sixteen except using PhSe − Li +  (1.0 mmol) instead of PhS − Li + . 0.28 grams (95%) of Se-phenyl N,N-dimethyldiselenocarbamate was obtained by flash chromatography on silica gel as a yellow crystal; mp 126.4–127.3° C.; C 9 H 11 NSe 2 ;  1 H NMR (CDCl 3 ) δ 3.45 (3H, s, CH 3 ), 3.67 (3H, s, CH 3 ), 7.44 (2H, t, J=7.2 Hz, Ar), 7.50 (1H, t, J=7.2 Hz, Ar), 7.59 (2H, d, J=8.4 Hz, Ar);  13 C NMR (CDCl 3 ) δ 44.9, 49.7, 129.4, 129.9, 132.3, 137.8 197.0;  77 Se NMR (CDCl 3 ) δ 670.5, 725.5; MS (CI): m/z=294 [M + +1]; HRMS: m/z=292.9221 calcd for C 9 H 11 NSe 2 , found 292.9236; Anal. Calcd for C 9 H 11 NSe 2 : C, 37.13; H, 3.81; N, 4.81. found: C, 37.02; H, 3.66; N, 4.82%. 
     Example Nineteen 
     Se-(4-methylphenyl) N,N-Dimethyldiselenocarbamate 
     This example was prepared following the same procedure as Example Sixteen except using 4-MePhSe − Li +  (1.0 mmol) instead of PhS − Li + . 0.25 grams (83%) of Se-(4-methylphenyl) N,N-dimethyldiselenocarbamate was obtained by flash chromatography on silica gel as a yellow crystal; mp 92.6–93.2° C.; C 10 H 13 NSe 2 ;  1 H NMR (CDCl 3 ) δ 2.40 (3H, s, CH 3 ), 3.42 (3H, s, CH 3 ), 3.65 (3H, s, CH 3 ), 7.24 (2H, d, J=8.0 Hz, Ar), 7.46 (2H, d, J=8.0 Hz, Ar);  13 C NMR (CDCl 3 ) δ 21.4, 44.8, 49.6, 128.8, 130.2, 137.5, 140.0, 197.4;  77 Se NMR (CDCl 3 ) δ 663.5, 716.9; MS (CI): m/z=308 [M + +1]; HRMS: m/z=306.9358 calcd for C 10 H 13 NSe 2 , found 306.9378; Anal. Calcd for C 10 H 13 NSe 2 : C, 39.36; H, 4.19; N, 4.59. found: C, 39.16; H, 4.16; N, 4.61%. 
     While the present invention has been described with reference to specific embodiments, this application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.