1-chloro-1,2,2-trifluoroethene

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:-80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 200 ml of freshly distilled dry Et2O is added to a 500 ml vessel (under an argon atmosphere). The vessel is cooled down to −80° C. and 15 g (0.129 mol) of CF2═CFCl gas is bubbled to Et2O. 100 ml (0.13 mol) of sec-BuLi is added dropwise during three hours. The temperature of the solution is kept below −60° C. all the time. The solution is stirred for 15 minutes and 29 ml (27.08 g, 0.130 mol) of Si(OEt)4 is added in small portions. The solution is stirred for over night allowing it to warm up to room temperature. Formed red solution is filtered and evaporated to dryness to result crude trifluorovinyltriethoxysilane, CF2═CFSi(OEt)3. 200 ml of freshly distilled dry Et2O is added to a 500 ml vessel (under an argon atmosphere) is kept below −60° C. The solution is stirred for over night to warm up to room temperature Formed red solution is filtered evaporated to dryness

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: At 25 bis 30° C. and while stirring, 5.9 g (0.093 mol) of 88% strength potassium hydroxide powder was added over a period of 5 minutes to a solution of 28.4 g (0.164 Mol) of 2-hydroxybenzenesulfonamide in 200 ml of acetone. At 40° to 50° C. and while stirring, 29.6 g (0.254 mol) of chlorotrifluoroethylene was gassed in over a period of 12 hours. The precipitate was filtered off under such and washed with acetone. The filtrate was evaporated down under reduced pressure, stirred into 700 ml of water, suction filtered, washed and dried. There was obtained 28.8 g (60.7%) of the title compound of m.p. 113° to 116° C. At 40° to 50° C. and while stirring was gassed in over a period of 12 hours The precipitate was filtered off under such and washed with acetone The filtrate was evaporated down under reduced pressure stirred into 700 ml of water, suction filtered washed dried

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 450 mL capacity PARR® reactor, 1,.4-cyclohexanedimethanol vinyl ether (50 g, 294 mmol), acetonitrile (100 mL), and Cs2CO3 (2 g, 6 mmol) were added. The PARR® reactor was cooled to ˜30° C., partially evacuated and chlorotrifluoroethylene (34 g, 294 mmol) was condensed and the resultant mixture was heated at ˜50-60° C with stirring for 3 hours. After this, the PARR® reactor was cooled to room temperature, vented in the fume hood and the reaction mixture was poured into ˜150 mL water and the lower layer containing the crude product separated, and was concentrated under reduced pressure 0.05 mmHg) at 25-30° C. to afford the desired product as a colorless viscous liquid (49 g, 58% yield) which is a mixture of cis/trans isomers in the ratio 73:18; refractive index of 1.415 at 23.7° C.; GC/MS (EI mode): m/z at 286 for M+; 19F and 1H NMR spectral data are consistent with the structure. partially evacuated condensed After this, the PARR® reactor was cooled to room temperature separated was concentrated under reduced pressure 0.05 mmHg) at 25-30° C.

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

Procedure: 3-Carboethoxy-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxypyrazole (2.0 g) was added to a stirred suspension of sodium hydride (80% dispersion in oil; 0.2 g) in dry dioxan (20 ml). When the resultant effervescence had subsided, the solution was heated to 80°-900 °C. and stirred while 2-chloro-1,1,2-trifluoroethylene was passed through. After 6 hours, the reaction was complete and the solvent was evaporated to dryness. The residue was dissolved in dilute hydrochloric acid (2M; 10 ml) and dichloromethane (20 ml) and the layers were separated. The aqueous layer was extracted with dichloromethane (30 ml) and the combined organic layers were washed with water (20 ml), dried over magnesium sulfate, filtered and evaporated. The residue was purified by dry-column chromatography (eluant ether:hexane 1:3) to give (RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (1.0 g). This was recrystallised from hexane to yield colorless needles, m.p. 105°-106.5° C. the solution was heated to 80°-900 °C. the solvent was evaporated to dryness The residue was dissolved in dilute hydrochloric acid (2M; 10 ml) dichloromethane (20 ml) and the layers were separated The aqueous layer was extracted with dichloromethane (30 ml) the combined organic layers were washed with water (20 ml) dried over magnesium sulfate filtered evaporated The residue was purified by dry-column chromatography (eluant ether:hexane 1:3)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a specially designed Kel-F reactor (cylindrical shape 1.25"od×3"h equipped with a screw cap and N2 inlet-outlet) was placed hydrogen fluoride-pyridine 6:4 solution (10 mL, prepared by diluting commercially available hydrogen fluoride-pyridine 7:3 solution with dry pyridine). 7-amino-tetralone (644 mg, 4.0 mmol), (Example 35, Step A) was added under N2 and the solution was cooled to 0°. Sodium nitrite (304 mg, 4.4 mol, 1.1 eq) was added in portions and the mixture was stirred for 30 minutes. The mixture was then heated at 90° C. for 1 hour with stirring. The reaction mixture was quenched with approx. 60 mL of ice/water and the solid that separated extracted with methylene chloride (3×30 mL). The combined extracts were washed with water and brine, dried over magnesium sulfate, filtered and evaporated to dryness under vacuum at room temperature. Purification by flash chromatography on silica, eluting with ethyl acetate/hexane (5:95), afforded pure 7-fluoro- 1-tetralone (367 mg, 2.2 mmol, 56%). 1H NMR (300MHz, CDCl3): 2.13 (m,2H), 2.65 (t,7Hz,2H), 2.94 (t,7Hz,2H), 7.1-7.3 (m,2H), 7.69 (dd;2,8Hz;1H). FAB-MS: calculated for C10H9FO 164; found 164 (M+,71%). ×3"h equipped with a screw cap N2 inlet-outlet) was placed the solution was cooled to 0° with stirring The reaction mixture was quenched with approx. 60 mL of ice/water the solid that separated extracted with methylene chloride (3×30 mL) The combined extracts were washed with water and brine dried over magnesium sulfate filtered evaporated to dryness under vacuum at room temperature Purification by flash chromatography on silica eluting with ethyl acetate/hexane (5:95)

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

Procedure: 0.572 g of cuprous oxide and 20 ml of hydrogen fluoride were placed in a Daiflon reaction vessel connected to a carbon monoxide buret, and reacted with carbon monoxide at 5° C. under 1 atm to form a copper carbonyl catalyst solution. 9.1 ml (100 mmol) of 1,3-butanediol and 3.0 g (100 mmol) of paraformaldehyde were slowly added to the catalyst solution at 5° C. and the mixture was stirred to conduct the reaction with carbon monoxide under 1 atm. 85 molar %, based on 1,3-butanediol, of carbon monoxide was reacted. The product was separated from the catalyst layer to obtain 9.1 g (yield: 70%) of 5-methyl-1,4-dioxepan-2-one. was reacted The product was separated from the catalyst layer