2,2,3,3-tetrafluoro-3-methoxypropanamide

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

Procedure: A solution of 52.5 g (0.30 mol) of the amide from Part A in 200 ml of diglyme was stirred at -10° while 47.5 g (0.60 mol) of pyridine and then 63.0 g (0.30 mol) of trifluoroacetic anhydride were added. The cooling bath was removed, and the mixture was stirred at about 25° for 2 h. Evaporation of volatiles to 40° (4.5 mm) gave 42.7 g of crude product, which was distilled to afford 36.5 g (77%) of 3-methoxytetrafluoropropionitrile, b.p. 53°. IR (neat): 3.36 and 3.48 (sat'd CH), 4.42 (CN), 8-10μ (CF, C--O). NMR: 1H 3.78 ppm (s, OCH3): 19F -93.2 (t, JFF 6.3 Hz, 2F, CH2) and -108.8 ppm (t, JFF 6.3 Hz, 2F, CF2). Elemental analysis was consistent with the formula C4H3F4NO. ##STR54## The cooling bath was removed Evaporation of volatiles to 40° (4.5 mm) gave 42.7 g of crude product, which was distilled

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, m.p. 83° to 85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10μ (CF, C--O). NMR ((CD3)2 (CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3): 19F -1.20.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF, 2.1 Hz, 2F, CF2). Elemental analysis was consistent with the formula C4H5F4NO2. ##STR53## evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10μ (CF, C--O). NMR ((CD3)2CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3); 19F-120.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2.1 Hz, 2F, CF2). evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10μ (CF, C--O). NMR ((CD3)2CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3l ); 19F -120.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2.1 Hz, 2F, CF2). evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10μ (CF, C--O). NMR ((CD3)2CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3); 19F-120.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2.1 Hz, 2F, CF2). evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10μ (CF, C-O). NMR ((CD3)2CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3); 19F-120.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2.1 Hz, 2F, CF2). evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane

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

Procedure: A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionate in 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH3. The resulting viscous mixture was stirred at 25° overnight and evaporated to dryness at 25° (10 mm). The crude residue was then recrystallized from ether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide, mp 78°-80°. An analytical sample was recrystallized from ether/hexane, mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH2), 3.37 and 3.49 (sat'd CH), 5.92 (C=O), 6.19 (NH2), 7.5-10 μ (CF, C-O). NMR ((CD3)2CO): 1H 6.67 (broad, 2H, NH2) and 3.66 ppm (s, 3H, OCH3); 19F-120.6 (t, JFF 4.7 Hz, 2F, CF2) and -121.8 ppm (t, JFF 4.7 Hz, of d, JHF 2.1 Hz, 2F, CF2). evaporated to dryness at 25° (10 mm) The crude residue was then recrystallized from ether/hexane