Structure of 81982-54-9
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CAS No. : | 81982-54-9 |
Formula : | C6H9F2NO2 |
M.W : | 165.14 |
SMILES Code : | O=C(OCC)/C=C(N)/C(F)F |
MDL No. : | MFCD27940574 |
InChI Key : | UVDSFXKVWRRSQT-ARJAWSKDSA-N |
Pubchem ID : | 97627690 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With ammonium acetate; In methanol; | (A) Preparation of: Ethyl 4,4-difluoro 3-amino-2-butenoate STR44 Ammonium acetate (62 g, 805 mM) is added at room temperature to a solution of ethyl 4,4-difluoro acetoacetate (7.400 g, 44.5 mM) in anhydrous methanol (120 ml). Stirring is continued at room temperature for 40 hours; the mixture is then poured into 5% sodium bicarbonate solution (200 ml), and extracted with ether (2*150 ml). The organic layer is dried over anhydrous magnesium sulfate. The solvent is evaporated in vacuo, yielding the expected compound as a yellowish oil. 4.700 g (yield 65%). IR (CHCl3): 3500, 1680, 1640 cm-1. NMR (CDCl3) 1.27 (t,JHH =7 Hz, 3H); 4.14 (q, JHH =7 Hz, 2H); 4.83 (s, broad, 1H); 5.95 (t, JHF =55 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With pyridine; In 1,2-dichloro-ethane; at 20.0℃; for 16.0h;Reflux; | General procedure: Acid chloride (66.7 mmol) was added in one portion to asolution of the corresponding enamine 17, 21 (60.6 mmol) in 1,2-dichloroethane (200 mL) at RT. Pyridine (8.6 mL, 106 mmol) wasadded thereto also in one portion, and the mixture was stirred atreflux temperature for 16 h. The solvent was evaporated in vacuo,and the residue was partitioned between water (200 mL) and ethylacetate (200 mL). The organic layer was separated and washedsequentially with water (2150 mL), saturated aqueous NaHCO3(100 mL), and brine (100 mL), and dried (MgSO4). Evaporation ofthe extract in vacuo afforded crude compounds 18a-f, 22a-f asoils, which were used in the next step without purification.Analytical samples of the materials were purified by columnchromatography on silica gel eluting with ethyl acetate - hexane(1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In 1,4-dioxane; for 24.0h;Reflux; | General procedure: Chloroacetyl or 2-chloropropionyl chloride (106 mmol) wasadded in one portion to a solution of the corresponding enamine17, 21 (60.6 mmol) in anhydrous dioxane (100 mL) at RT, and theformed mixture was stirred at reflux temperature for 24 h. Thesolvent was evaporated in vacuo, and the residue was partitionedbetween water (150 mL) and ethyl acetate (150 mL). The organiclayer was separated and washed sequentially with water (100 mL),saturated aqueous NaHCO3 (2100 mL), and brine (100 mL), anddried (MgSO4). Evaporation of the extract in vacuo furnished crudecompounds 18 g,h, 22 g,h as oils, which were used in the next stepwithout purification. Analytical samples of the materials werepurified by column chromatography on silica gel eluting with ethylacetate - hexane (1:3, v/v) mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In 1,4-dioxane; for 24.0h;Reflux; | General procedure: Chloroacetyl or 2-chloropropionyl chloride (106 mmol) wasadded in one portion to a solution of the corresponding enamine17, 21 (60.6 mmol) in anhydrous dioxane (100 mL) at RT, and theformed mixture was stirred at reflux temperature for 24 h. Thesolvent was evaporated in vacuo, and the residue was partitionedbetween water (150 mL) and ethyl acetate (150 mL). The organiclayer was separated and washed sequentially with water (100 mL),saturated aqueous NaHCO3 (2100 mL), and brine (100 mL), anddried (MgSO4). Evaporation of the extract in vacuo furnished crudecompounds 18 g,h, 22 g,h as oils, which were used in the next stepwithout purification. Analytical samples of the materials werepurified by column chromatography on silica gel eluting with ethylacetate - hexane (1:3, v/v) mixture. |
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