2-amino-4-methylbenzonitrile

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

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

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

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

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

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-methylanthranilonitrile (4.46 g) and freshly fused zinc chloride (6.8 g) in 20 ml of nitrobenzene was heated at 50° C. for 1 hour. To this was added tetrahydrothiopyran-4-one (5.1 g) and the mixture was heated to 130° C. for 1.5 hours. After cooling, the zinc complex was filtered, rinsed with ethyl ether and partitioned between 2-butanone (MEK) and NH4OH. The aqueous phase was extracted with MEK and the organics were washed with water and dried (saturated NaCl, MgSO4). This was concentrated to give 4.76 g of an off-white powder, m.p. 239°-245° C. d., which was recrystallized from ethyl acetate to give 2.95 g of an off-white powder, m.p. 243°-246° C. d. the mixture was heated to 130° C. for 1.5 hours After cooling the zinc complex was filtered rinsed with ethyl ether partitioned between 2-butanone (MEK) and NH4OH The aqueous phase was extracted with MEK the organics were washed with water dried (saturated NaCl, MgSO4) This was concentrated

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

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-methylanthranilonitrile (4.46 g) and freshly fused zinc chloride (6.8 g) in 20 ml of nitrobenzene was heated at 50° C. for 1 hour. To this was added tetrahydrothiopyran-4-one (5.1 g) and the mixture was heated to 130° C. for 1.5 hours. After cooling, the zinc complex was filtered, rinsed with ethyl ether and partitioned between 2-butanone (MEK) and NH4OH. The aqueous phase was extracted with MEK and the organics were washed with water and dried (saturated NaCl, MgSO4). This was concentrated to give 4.76 g of an off-white powder, m.p. 239°-245° C. d., which was recrystallized from ethyl acetate to give 2.95 g of an off-white powder, m.p. 243°-246° C. d. the mixture was heated to 130° C. for 1.5 hours After cooling the zinc complex was filtered rinsed with ethyl ether partitioned between 2-butanone (MEK) and NH4OH The aqueous phase was extracted with MEK the organics were washed with water dried (saturated NaCl, MgSO4) This was concentrated

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-methylanthranilonitrile (4.46 g) and freshly fused zinc chloride (6.8 g) in 20 ml of nitrobenzene was heated at 50° C. for 1 hour. To this was added tetrahydrothiopyran-4-one (5.1 g) and the mixture was heated to 130° C. for 1.5 hours. After cooling, the zinc complex was filtered, rinsed with ethyl ether and partitioned between 2-butanone (MEK) and NH4OH. The aqueous phase was extracted with MEK and the organics were washed with water and dried (saturated NaCl, MgSO4). This was concentrated to give 4.76 g of an off-white powder, m.p. 239°-245° C. d., which was recrystallized from ethyl acetate to give 2.95 g of an off-white powder, m.p. 243°-246° C. d. the mixture was heated to 130° C. for 1.5 hours After cooling the zinc complex was filtered rinsed with ethyl ether partitioned between 2-butanone (MEK) and NH4OH The aqueous phase was extracted with MEK the organics were washed with water dried (saturated NaCl, MgSO4) This was concentrated

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-methylanthranilonitrile (4.46 g) and freshly fused zinc chloride (6.8 g) in 20 ml of nitrobenzene was heated at 50° C. for 1 hour. To this was added tetrahydrothiopyran-4-one (5.1 g) and the mixture was heated to 130° C. for 1.5 hours. After cooling, the zinc complex was filtered, rinsed with ethyl ether and partitioned between 2-butanone (MEK) and NH4OH. The aqueous phase was extracted with MEK and the organics were washed with water and dried (saturated NaCl, MgSO4). This was concentrated to give 4.76 g of an off-white powder, m.p. 239°-245° C. d., which was recrystallized from ethyl acetate to give 2.95 g of an off-white powder, m.p. 243°-246° C. d. the mixture was heated to 130° C. for 1.5 hours After cooling the zinc complex was filtered rinsed with ethyl ether partitioned between 2-butanone (MEK) and NH4OH The aqueous phase was extracted with MEK the organics were washed with water dried (saturated NaCl, MgSO4) This was concentrated

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-methylanthranilonitrile (4.46 g) and freshly fused zinc chloride (6.8 g) in 20 ml of nitrobenzene was heated at 50° C. for 1 hour. To this was added tetrahydrothiopyran-4-one (5.1 g) and the mixture was heated to 130° C. for 1.5 hours. After cooling, the zinc complex was filtered, rinsed with ethyl ether and partitioned between 2-butanone (MEK) and NH4OH. The aqueous phase was extracted with MEK and the organics were washed with water and dried (saturated NaCl, MgSO4). This was concentrated to give 4.76 g of an off-white powder, m.p. 239°-245° C. d., which was recrystallized from ethyl acetate to give 2.95 g of an off-white powder, m.p. 243°-246° C. d. the mixture was heated to 130° C. for 1.5 hours After cooling the zinc complex was filtered rinsed with ethyl ether partitioned between 2-butanone (MEK) and NH4OH The aqueous phase was extracted with MEK the organics were washed with water dried (saturated NaCl, MgSO4) This was concentrated

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

Procedure: A solution of 2-bromo-4-methylbenzonitrile (2.0 g, 10.7 mmol) and CuCN (1.92 g, 21.4 mmol) in NMP (10 mL) was reacted in a microwave for 20 min at 200° C. Upon completion the reaction was cooled to 0° C., and 15% aqueous NH4OH (215 mL) was slowly added. The mixture was stirred at rt for 30 min, then extracted with CH2Cl2. The organic layer was washed with H2O, brine, dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography (3:1 Hexane:EtOAc) to provide 2-amino-4-methylbenzonitrile (1.24 g, 88%). 1H NMR (400 MHz, CDCl3) δ 1.45 (s, 3H), 5.70 (m, 1H), 5.84 (m, 1H), 6.41 (d, J=8.0 Hz, 1H). extracted with CH2Cl2 The organic layer was washed with H2O, brine dried over MgSO4 filtered concentrated The residue was purified by flash chromatography (3:1 Hexane:EtOAc)