2-(benzenesulfonyl)acetonitrile

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

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 (phenylsulfonyl)acetonitrile (10.5 g, 0.089 mol) in triethyl orthoformate (21 mL, 0.14 mol) and acetic anhydride (21 mL, 0.2 mol) was heated at 160° C. with removal of ethyl acetate (35 mL). The dark oily residue was dissolved in methanol (60 mL) and the solution was concentrated and recrystallized from hexanes/ethyl acetate to yield (11.98 g, 78%) of the desired product. the solution was concentrated recrystallized from hexanes/ethyl acetate

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

Procedure: M33 was prepared with 3,5-di-t-butyl-4-hydroxybenzaldehyde and phenylsulfonly acetonitrile under similar conditions as described for M26.

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

Procedure: Reaction of 3-phenoxythiophen-2-carboxaldehyde and phenylsulfonylacetonitrile as in Example 1 gave (E)-3-(3-phenoxythien-2-yl)-2-(phenylsulfonyl)acrylonitrile.

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

Procedure: 2-Nitrothiophen-5-carboxaldehyde (0.157 g) and phenylsulfonyl acetonitrile (0.199 g) were stirred in 2 mL of ethanol containing 0.01 mL piperidine for four hours at 100 C. The mixture was cooled to room temperature and water was added for crystalization. The crude product was filtered and recrystalized from ethanol and water to give 0.16 g of (E)-3-(2-nitrothien-5-yl)-2-(phenylsulfonyl)acrylonitrile. Alternatively, the crude product was purified on a silica gel column with a mixture of ethylacetate and hexane as eluent. The crude product was filtered recrystalized from ethanol and water

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

Procedure: A solution of 4-(2-methylallyloxy)-benzaldehyde (7.03 g, 40 mmol) and of (phenylsulfonyl)acetonitrile (7.24 g, 40 mmol) in 70 ml absolute ethanol is heated under reflux in the presence of a catalytic quantity of piperidine (0.5 ml) for 48 hours. The reaction medium is cooled to room temperature and the precipitate formed is filtered and washed with cold ethanol. After drying in a dessicator, 10.45 g (yield 77%) of 2-benzenesulfonyl-3-[4-(2-methylallyloxy)phenyl]acrylonitrile are obtained in the form of a very pale yellow solid which is used as it is in the next step. the precipitate formed is filtered washed with cold ethanol

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

Procedure: A solution of 4-(2-methylallyloxy)-benzaldehyde (7.03 g, 40 mmol) and of (phenylsulfonyl)acetonitrile (7.24 g, 40 mmol) in 70 ml absolute ethanol is heated under reflux in the presence of a catalytic quantity of piperidine (0.5 ml) for 48 hours. The reaction medium is cooled to room temperature and the precipitate formed is filtered and washed with cold ethanol. After drying in a dessicator, 10.45 g (yield 77%) of 2-benzenesulfonyl-3-[4-(2-methylallyloxy)phenyl]acrylonitrile are obtained in the form of a very pale yellow solid which is used as it is in the next step. the precipitate formed is filtered washed with cold ethanol

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 9.4 g (0.052 mol) of benzenesulfonyl-acetonitrile in 200 mL of DME at −50° C., 7.8 mL (0.052 mol, 1 eq) of TMEDA and 32.4 mL (0.052 mL, 1 eq) of nBuLi (1.6M in hexane) were added and stirring was continued for 45 min. To the resulting white suspension, 4.98 g (0.052 mol, 1 eq) of cyclohex-2-enone were added and the temperature was raised to −10° C. within 4 hours. The reaction mixture was poured into 180 mL of 1M HCl, extracted with EtOAc, and the combined organic phases dried over Na2SO4. Evaporation of the solvent and recrystallisation from AcOEt/Et2O yielded 8.25 g (57%) of benzenesulfonyl-(3-oxo-cyclohexyl)-acetonitrile as a racemic mixture of diastereomers, white crystals, MS: 278 (MH+) (in analogy to: E. Hatzigrigoriou, L. Wartski, Synth. Comm., 1983, 14(4), 319-235). extracted with EtOAc the combined organic phases dried over Na2SO4 Evaporation of the solvent and recrystallisation from AcOEt/Et2O

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

Procedure: M33 was prepared with 3,5-di-t-butyl-4-hydroxybenzaldehyde and phenylsulfonly acetonitrile under similar conditions as decribed for M26.

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

Procedure: M33 was prepared with 3,5-di-t-butyl-4-hydroxybenzaldehyde and phenylsulfonly acetonitrile under similar conditions as decribed for M26.

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzene sulfinic acid sodium salt, 49.2 g. (0.3 mole) was combined with 400 ml. of dimethyl formamide in a 1 liter flask. The mixture was stirred at 40° C. Chloroacetonitrile, 22.5 g. (0.3 mole) was added over a period of 5 minutes. The resulting mixture was stirred and heated at 40°-45° C. for 2 hours. The reaction mass was then poured into 600 ml. of water, and the solid insoluble product was collected by suction filtration and dried. There was obtained a yield of 29.8 g. of the title compound, m.p. 111°-112° C. (0.3 mole) was added over a period of 5 minutes The resulting mixture was stirred heated at 40°-45° C. for 2 hours The reaction mass was then poured into 600 ml of water, and the solid insoluble product was collected by suction filtration dried There was obtained a yield of 29.8 g