ethanedithioamide

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, and reflux condenser were placed 212 g (1.77 mol) of dithiooxamide (DTO), 2,200 g of methanol, and 224 g of deionized water. The reaction mixture was stirred and heated to reflux. At that point, 126 g (1.18 mol) of benzylamine, i.e., the reactive amine, was added. The progress of the reaction was monitored by thin layer chromatography (TLC) to detect the initial formation of N,N'-dibenzyldithiooxamide. After about 20 minutes, formation of the disubstituted product was detected and the reaction was quenched by the addition of 100 g of concentrated HCl. Into a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, and reflux condenser heated to reflux the reaction was quenched by the addition of 100 g of concentrated HCl

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, and reflux condenser were placed 212 g (1.77 mol) of dithiooxamide (DTO), 2,200 g of methanol, and 224 g of deionized water. The reaction mixture was stirred and heated to reflux. At that point, 126 g (1.18 mol) of benzylamine, i.e., the reactive amine, was added. The progress of the reaction was monitored by thin layer chromatography (TLC) to detect the initial formation of N,N'-dibenzyldithiooxamide. After about 20 minutes, formation of the disubstituted product was detected and the reaction was quenched by the addition of 100 g of concentrated HCl. Into a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, and reflux condenser heated to reflux the reaction was quenched by the addition of 100 g of concentrated HCl

Conditions: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 100 ml round-bottomed flask, equipped with a magnetic stirrer and heating bath, were placed 2.4 g (0.02 mol) of dithiooxamide, 1.8 g (0.02 mol) of aniline, and 40 ml of methanol. The solution was stirred and heated at 35° C. for 30 minutes. The reactive amine, dodecylamine (3.7 g, 0.02 mol), was then added, and the solution was stirred for an additional 3 hours at 35° C. The crude reaction mixture was cooled to 25° C., and the acidity was adjusted to a pH of about 2 by the addition of 37% aqueous HCl. The mixture was filtered, washed with a small amount of methanol, and dried to afford 1.5 g of N,N'-didodecyldithiooxamide. Water (40 ml) was added to the filtrate with stirring, which was continued for 10 minutes. The precipitate was collected by filtration and washed with a minimum amount of a 50:50 mixture of water and methanol. The product was dried to afford 3.2 g (55%) of N-dodecyldithiooxamide. Into a 100 ml round-bottomed flask, equipped with a magnetic stirrer heating bath the solution was stirred for an additional 3 hours at 35° C The crude reaction mixture was cooled to 25° C. The mixture was filtered washed with a small amount of methanol dried

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, 2-formyl-3-(2-butyloctoxy)thiophene (7 g, 23.6 mmol) and rubeanic acid (1.42 g, 11.8 mmol) were added to a flask equipped with Dean-Stark, then heated to 200° C., and stirred for five hours. Then, the reaction mixture was extracted with chloroform, and an organic layer was washed with a saturated saline solution and water. The organic layer was dried with anhydrous magnesium sulfate, and, after filtration, the solvent was distilled off under reduced pressure. By separating and purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform was used as a mobile phase, a target substance was obtained as a yellow solid (29% yield). 1H-NMR (400 MHZ, CDCl3, TMS) δ 7.31 (d, J=5.6 Hz, 1 H), 6.88 (d, J=5.6 Hz, 1 H), 4.13 (d, J=4.8 Hz, 2 H), 1.25 (m, 17 H), 0.88 (m, 6 H) equipped with Dean-Stark Then, the reaction mixture was extracted with chloroform an organic layer was washed with a saturated saline solution and water The organic layer was dried with anhydrous magnesium sulfate after filtration the solvent was distilled off under reduced pressure By separating purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, 3-(2-hexyldecyl)-2thiophenaldehyde (3.00 g, 8.91 mmol) (A3) and rubeanic acid (375 mg, 2.97 mmol) were added to a flask equipped with Dean-Stark, then heated to 200° C., and stirred for five hours. Then, the reaction mixture was extracted with chloroform, and an organic layer was washed with a saturated saline solution and water. The organic layer was dried with anhydrous magnesium sulfate, and, after filtration, the solvent was distilled off under reduced pressure. By separating and purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform was used as a mobile phase, 2,5-bis(3(2-hexyldecyl)thiophene-2-yl)thiazolo[5,4-d]thiazole (A4) was obtained as a yellow solid (630 mg, 28% yield). The product (A4) obtained was identified using a 1H-NMR method. 1H-NMR (400 MHZ, CDCl3, TMS) δ 7.34 (d, J=5.4 Hz, 1 H), 6.95 (d, j=5.4 Hz, 1 H), 2.93 (d, J=7.4 Hz, 2 H), 1.25 (m, 25 H), 0.88 (m, 6 H) equipped with Dean-Stark Then, the reaction mixture was extracted with chloroform an organic layer was washed with a saturated saline solution and water The organic layer was dried with anhydrous magnesium sulfate after filtration the solvent was distilled off under reduced pressure By separating purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, 3-(2-hexyldecyl)-2thiophenaldehyde (3.00 g, 8.91 mmol) (A3) and rubeanic acid (375 mg, 2.97 mmol) were added to a flask equipped with Dean-Stark, then heated to 200° C., and stirred for five hours. Then, the reaction mixture was extracted with chloroform, and an organic layer was washed with a saturated saline solution and water. The organic layer was dried with anhydrous magnesium sulfate, and, after filtration, the solvent was distilled off under reduced pressure. By separating and purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform was used as a mobile phase, 2,5-bis(3(2-hexyldecyl)thiophene-2-yl)thiazolo[5,4-d]thiazole (A4) was obtained as a yellow solid (630 mg, 28% yield). The product (A4) obtained was identified using a 1H-NMR method. 1H-NMR (400 MHZ, CDCl3, TMS) δ 7.34 (d, J=5.4 Hz, 1 H), 6.95 (d, j=5.4 Hz, 1 H), 2.93 (d, J=7.4 Hz, 2 H), 1.25 (m, 25 H), 0.88 (m, 6 H) equipped with Dean-Stark Then, the reaction mixture was extracted with chloroform an organic layer was washed with a saturated saline solution and water The organic layer was dried with anhydrous magnesium sulfate after filtration the solvent was distilled off under reduced pressure By separating purifying the obtained reaction mixture by silica gel column chromatography in which a mixed solvent of hexane and chloroform

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 25 mL flask were added 0.978 g (2.8 mmol) of tetradecyl-2-formylthiophene-3-carboxylate and 110 mg (0.9 mmol) of dithiooxamide. This mixture was heated to 200° C. for 2 hours. The resulting mixture was purified by column chromatography using a mixture of hexane and dichloromethane to give the desired compound. The NMR data were obtained and were consistent with those of the desired compound. The resulting mixture was purified by column chromatography a mixture of hexane and dichloromethane

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 25 mL flask were added 0.978 g (2.8 mmol) of tetradecyl-2-formylthiophene-3-carboxylate and 110 mg (0.9 mmol) of dithiooxamide. This mixture was heated to 200° C. for 2 hours. The resulting mixture was purified by column chromatography using a mixture of hexane and dichloromethane to give the desired compound. The NMR data were obtained and were consistent with those of the desired compound. The resulting mixture was purified by column chromatography a mixture of hexane and dichloromethane

Conditions: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 100 ml round-bottomed flask, equipped with a magnetic stirrer, condenser, and heating bath, were placed 2.4 g (0.02 mol) of dithiooxamide and a solution of pyridine (1.6 g, 0.02 mol) dissolved in methanol (40 ml). The reaction mixture was heated, with stirring, at 35° C. for 30 minutes. Ethanolamine (1.2 g, 0.02 mol) was added, and the solution was stirred for an additional 3 hours at 35° C. The crude reaction mixture was cooled to room temperature, and the acidity was adjusted to a pH of about 2 by the addition of 37% HCl (aqueous). Silica gel (10 g) was added to the solution, and the solvent was removed under reduced pressure. The dry residue of silica gel with absorbed product mixture was added to a chromatography column. The products were eluted with an ethyl acetate/hexane mixture to separate the monosubstituted product, which was eluted first, from the disubstituted dithiooxamide. The yield of N-(2-hydroxyethyl)dithiooxamide was 1.1 g (7.0×10- 3 mol, 34% yield). In addition, 0.8 g (4.0×10-3 mol, 38% yield) of N,N'-di(2-hydroxyethyl)dithiooxamide was isolated. The mole ratio of monosubstituted to disubstituted dithiooxamide was 1.8:1. Into a 100 ml round-bottomed flask, equipped with a magnetic stirrer, condenser heating bath The reaction mixture was heated the solution was stirred for an additional 3 hours at 35° C The crude reaction mixture was cooled to room temperature Silica gel (10 g) was added to the solution the solvent was removed under reduced pressure The dry residue of silica gel with absorbed product mixture was added to a chromatography column The products were eluted with an ethyl acetate/hexane mixture to separate the monosubstituted product, which was eluted first, from the disubstituted dithiooxamide

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,5-bis(2-methoxyphenyl)thiazolo[5,4-d]thiazole was prepared from dithiooxamide and o-methoxybenzaldehyde. o-Methoxybenzaldehyde was purchased from Aldrich Chemical Company, Milwaukee, Wis.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,5-bis(2-methoxyphenyl)thiazolo[5,4-d]thiazole was prepared from dithiooxamide and o-methoxybenzaldehyde. o-Methoxybenzaldehyde was purchased from Aldrich Chemical Company, Milwaukee, Wis.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,5-bis(2-methoxyphenyl)thiazolo[5,4-d]thiazole was prepared from dithiooxamide and o-methoxybenzaldehyde. o-Methoxybenzaldehyde was purchased from Aldrich Chemical Company, Milwaukee, Wis.