phenyl cyanate

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:0.00; pressure:0.00; stir:

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

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

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: n-BuLi (2.2 M, 69.5 mL, 0.153 mol) was added dropwise to a cooled (-78° C.) solution of 3-dibutylaminopropyne (24.9 g, 0.149 mol) in anhydrous ether (175 mL) at a rate not allowing the temperature to rise above -50° C. The resulting solution was stirred (5minutes, -70° C.), then phenyl cyanate (19.6 g, 0.164 mol) was added dropwise at a rate not allowing the temperature to rise above -60° C. The resulting solution was stirred (45 minutes, -78° C.), then warmed (25° C.). The resulting dark brown solution was diluted with ether (250 mL), washed with 3.0 N NaOH (3×170 mL), washed with brine (1×170 mL), then dried (MgSO4), and concentrated in vacuo. The resulting oil was chromatographed on silica (chloroform) to yield 27.0 g (94.4%) of 4-dibutylamino-2-butynenitrile as a brown liquid. 1H NMR (250 MHz, CDCl3): δ 3.53 (s, 2H), 2.46 (t, 4H), 1.36 (m, 8H), 0.92 (t, 6H). to rise above -50° C to rise above -60° C The resulting solution was stirred (45 minutes, -78° C.) warmed (25° C.) washed with 3.0 N NaOH (3×170 mL) washed with brine (1×170 mL) dried (MgSO4) concentrated in vacuo The resulting oil was chromatographed on silica (chloroform)

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: n-BuLi (2.2 M, 24.3 mL, 53.5 mmol) was added dropwise to a cooled (-78° C.) slurry of tetradecyne (10.3 g, 52.7 mmol) in anhydrous ether (60 mL) at a rate not allowing the temperature to rise above -40° C. The resulting slurry was stirred (5 minutes, 70° C.), then phenyl cyanate (6.9 g, 58.0 mmol) was added dropwise at a rate not allowing the temperature to rise above -60° C. The resulting slurry was stirred (45 minutes, -78° C.) then warmed (25° C.). The resulting solution was diluted with ether (140 mL), washed with 1.5 N NaOH (2×100 mL), washed with brine (1×100 mL), then dried (MgSO4), and concentrated in vacuo. The resulting oil was chromatographed on silica (pentane to 95:5 pentane:ether) to yield 9.0 g (77.8%) of 2-pentadecynenitrile as a pale yellow liquid. to rise above -40° C to rise above -60° C The resulting slurry was stirred (45 minutes, -78° C.) then warmed (25° C.) washed with 1.5 N NaOH (2×100 mL) washed with brine (1×100 mL) dried (MgSO4) concentrated in vacuo The resulting oil was chromatographed on silica (pentane to 95:5 pentane:ether)

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

Procedure: Into a 2-L three neck flask equipped with a drop-in funnel, thermometer, and mechanical stirrer was placed phenol (84.3 g, 0.896 mol), cyanogen bromide (100.0 g, 0.944 mol), anhydrous ether (450 mL), and pentane (450 mL). The resulting solution was cooled (0° C.), and while stirring vigorously triethylamine 131.6 mL, 0.944 mol) was added dropwise at a rate not allowing the temperature to rise above 15° C. The resulting slurry was stirred vigorously (1 hour, 0° C.), then filtered through a glass frit. The filter cake was washed with pentane (2×400 mL), and the combined filtrates were concentrated in vacuo, then distilled to yield 94.1 g (88.2%) of phenyl cyanate as a clear liquid, b.p. 76°-79° C., 15 mm. thermometer, and mechanical stirrer was placed was added dropwise at a rate not to rise above 15° C filtered through a glass frit The filter cake was washed with pentane (2×400 mL) the combined filtrates were concentrated in vacuo distilled

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 750 mg of trans-1-ethynyl-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexane (prepared according to Example 14) in 75 ml of a 4:1 mixture of absolute tetrahydrofuran and hexamethylphosphoric acid triamide was placed at -45° C. in a sulphonation flask under argon gasification and treated within 2 minutes with 3.3 ml of a 1.0N solution of butyl lithium in hexane. The mixture was subsequently stirred at -20° C. for a further 1 hour, then cooled to -78° C. and treated with 490 μl of phenyl cyanate in a single portion. The mixture was then stirred at -78° C. for a further 2.5 hours, poured into 200 ml of water and extracted three times with 150 ml of diethyl ether each time. The organic phases were washed twice with 150 ml of water each time and once with 100 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (2.6 g) on silica gel with hexane gave in sequence 194 mg (25.8%) of trans-1-ethynyl-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexane and 284 mg (34.8%) of trans-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexanepropiolonitrile (purity 98.9%). A recrystallization of the nitrile from methanol yielded colourless crystals (purity 99.4%); m.p. (C-N) 51.4% and cl.p. (N-I) 112.7° C. was placed at -45° C. in a sulphonation flask under argon cooled to -78° C. The mixture was then stirred at -78° C. for a further 2.5 hours extracted three times with 150 ml of diethyl ether each time The organic phases were washed twice with 150 ml of water each time once with 100 ml of saturated sodium chloride solution, dried over magnesium sulphate concentrated