3-mercaptopropiononitrile

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A Solution of chlorine in dichloromethane (1.4 mol dm-3, 10.0 cm3, 14.0 mmol) was added dropwise to a stirred solution of 2-cyanoethyl mercaptan, (see, for example, Bauer and Welsh, loc cit), (1.22 g, 14.0 mmol) in dichloromethane (21 cm3) at 0° C. (ice-water bath). After the products had been allowed to warm to room temperature, they were added dropwise to a stirred slurry of phthalimide (1.47 g, 10.0 mmol) and triethylamine (1.94 cm3, 14.0 mmol) in dry DMF (12 cm3) at 0° C. (ice-water bath). The stirred reactants were allowed to warm to room temperature. After 2 h, the products were poured into saturated aqueous sodium hydrogen carbonate (25 cm3) and the resulting mixture was extracted with dichloromethane (2×50 cm3). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure. The residue was crystallized from ethanol to give N-(2-cyanoethylmercapto)phthalimide 21 as colourless needles (1.345 g, 58%) (Found: C, 57.0; H, 3.4; N, 11.8. C11H8 N2O2S requires: C, 56.9; H, 3.5; N, 12.1%), m.p. 162°-164° C.; δH [CDCl3 ] 2.79 (2 H, t, J7.2), 3.12 (2 H, t, J7.2), 7.83 (2 H, m), 7.95 (2 H, m); δC [CDCl3 ] 18.7, 34.5, 117.5, 124.1, 131.7, 134.9, 168.1. to warm to room temperature the resulting mixture was extracted with dichloromethane (2×50 cm3) The combined organic layers were dried (MgSO4) concentrated under reduced pressure The residue was crystallized from ethanol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,5-Trichlorobenzonitrile (9.7 g, 47 mmol) and 3-mercaptopropionitrile (4.9 g, 56 mmol) (L. Bauer, T.L. Welsh, J. Org. Chem., 1443 (1961)) was dissolved in 130 ml of DMF. The mixture was stirred and cooled to 0° C., flushed with a stream of nitrogen, and 25% potassium hydroxide (20 ml) was added dropwise. When the addition was complete the mixture was stirred for 0.5 h and bromonitromethane (3.92 ml, 56 mmol) was added dropwise. The ice bath was removed and the mixture was stirred for a further 16 h. The mixture was poured into ice-water and the precipitate was isolated, washed with water and dried to afford 10.6 g (86%) of 3-amino-5,7-dichloro-2-nitrobenzo[b]-thiophene M.p. 290°-92° C. 1H-NMR (DMSO-d6): 8.02 (d, 1H), 8.54 (d, 1H), 9.00 (br. s, 1H). flushed with a stream of nitrogen, and 25% potassium hydroxide (20 ml) was added dropwise When the addition was stirred for 0.5 h The ice bath was removed the mixture was stirred for a further 16 h The mixture was poured into ice-water the precipitate was isolated washed with water dried

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 8.7 parts of β-mercaptopropionitrile are added to a solution of 2.6 parts of sodium in 175 parts by volume of methanol at 22° C., whilst stirring. After 10 minutes, 15.5 parts of chloroacetophenone at 35° C. is added in the course of 30 minutes and the temperature is maintained at 22° C. The mixture is stirred for a further 30 minutes at 22° C. and is then heated for 2 hours at 65° C. under reflux. When it has cooled, the reaction mixture is neutralized with acetic acid and is poured into 250 parts of ice water, and the batch is extracted with three times 50 parts by volume of chloroform. After evaporating the combined, dried chloroform extracts, an oily residue remains, which is triturated with 50 parts of cold alcohol and hereupon crystallizes. 17.5 parts (85% of theory) of 3-amino-3-benzoyl-dihydrothiophene of melting point 147°-149° C. are obtained. The mixture is stirred for a further 30 minutes at 22° C. is then heated for 2 hours at 65° C. under reflux When it has cooled the batch is extracted with three times 50 parts by volume of chloroform After evaporating the which is triturated with 50 parts of cold alcohol hereupon crystallizes

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 8.7 Parts of β-mercaptopropionitrile are added to a solution of 2.6 parts of sodium in 175 parts by volume of methanol at 22° C., whilst stirring. After 10 minutes, 15.5 parts of chloracetophenone at 35° C. is added in the course of 30 minutes and the temperature is maintained at 22°C. The mixture is stirred for a further 30 minutes at 22° C. and is then heated for 2 hours at 65° C. under reflux. When it has cooled, the reaction mixture is neutralized with acetic acid and is poured into 250 parts of ice water, and the batch is extracted with three times 50 parts by volume of chloroform. After evaporating the combined, dried chloroform extracts, an oily residue remains, which is triturated with 50 parts of cold alcohol and hereupon crystallizes. 17.5 parts (85% of theory) of 3-amino-3-benzoyl-dihydrothiophene of melting point 147°-149° C. are obtained. The mixture is stirred for a further 30 minutes at 22° C. is then heated for 2 hours at 65° C. under reflux When it has cooled the batch is extracted with three times 50 parts by volume of chloroform After evaporating the which is triturated with 50 parts of cold alcohol hereupon crystallizes

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

Procedure: A Solution of chlorine in dichloromethane (1.4 mol dm-3, 10.0 cm3, 14.0 mmol) was added dropwise to a stirred solution of 2-cyanoethyl mercaptan, (see, for example, Bauer and Welsh, loc cit), (1.22 g, 14.0 mmol) in dichloromethane (21 cm3) at 0° C. (ice-water bath). After the products had been allowed to warm to room temperature, they were added dropwise to a stirred slurry of phthalimide (1.47 g, 10.0 mmol) and triethylamine (1.94 cm3, 14.0 mmol) in dry DMF (12 cm3) at 0° C. (ice-water bath). The stirred reactants were allowed to warm to room temperature. After 2 h, the products were poured into saturated aqueous sodium hydrogen carbonate (25 cm3) and the resulting mixture was extracted with dichloromethane (2×50 cm3). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure. The residue was crystallized from ethanol to give N-(2-cyanoethylmercapto)phthalimide 21 as colourless needles (1.345 g, 58%) (Found: C, 57.0; H, 3.4; N, 11.8. C11H8 N2O2S requires: C, 56.9; H, 3.5; N, 12.1%), m.p. 162°-164° C.; δH [CDCl3 ] 2.79 (2 H, t, J7.2), 3.12 (2 H, t, J7.2), 7.83 (2 H, m), 7.95 (2 H, m); δC [CDCl3 ] 18.7, 34.5, 117.5, 124.1, 131.7, 134.9, 168.1. to warm to room temperature the resulting mixture was extracted with dichloromethane (2×50 cm3) The combined organic layers were dried (MgSO4) concentrated under reduced pressure The residue was crystallized from ethanol