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CAS No. : | 367-57-7 | MDL No. : | MFCD00000427 |
Formula : | C5H5F3O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SHXHPUAKLCCLDV-UHFFFAOYSA-N |
M.W : | 154.09 | Pubchem ID : | 73943 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.6 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 5.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 26.74 |
TPSA : | 34.14 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.59 cm/s |
Log Po/w (iLOGP) : | 0.99 |
Log Po/w (XLOGP3) : | 0.92 |
Log Po/w (WLOGP) : | 2.36 |
Log Po/w (MLOGP) : | 0.53 |
Log Po/w (SILICOS-IT) : | 1.6 |
Consensus Log Po/w : | 1.28 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.18 |
Solubility : | 10.3 mg/ml ; 0.0665 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.22 |
Solubility : | 9.22 mg/ml ; 0.0599 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -1.44 |
Solubility : | 5.59 mg/ml ; 0.0363 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.28 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P280 | UN#: | 1224 |
Hazard Statements: | H225-H302-H312-H332 | Packing Group: | Ⅲ |
GHS Pictogram: |
* 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 |
---|---|---|
95% | With hydrazine In methanol at 0 - 20℃; for 16 h; | Example 127: Preparation of 5-methyl-3-trifluoromethyl-l/jr-pyrazoleTo a solution of trifluoroacetyl acetone (4.62 g, 30 mmol) in methanol (20 ml), was added slowly at O0C a solution of hydrazine (945 μl, 30 mmol). The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 16 hours. <n="90"/>The reaction mixture was concentrated to give 5-methyl-3-trifluoromethyl-lH-pyrazole as a yellow solid (4.5 g, 95percent yield).1H-NMR (400 MHz, CDCl3): 2.35 (s, 3H, Me), 6.32 (s, IH, CH), 9.88 (bs, IH, NH) ppm. |
90% | Stage #1: With hydrazine hydrate In chloroform for 1 h; Reflux Stage #2: With phosphorus pentoxide In chloroform for 3 h; Reflux |
General procedure: 1.00 equiv. (40.0 mmol) of β-diketones (2a-h) and 30 mL chloroform were introduced in a two-necked reaction flask. 1.00 equiv. (40.0 mmol) of 100percent hydrazine monohydrate was added dropwise to the solution. After refluxing for one hour the reaction mixture was cooled to room temperature and 6 g of P4O10 was added followed by heating to reflux for additional three hours. After cooling, the reaction mixture was slowly mixed with 30 mL of H2O until all residues of P4O10 were diluted. The organic layer was separated and the aqueous layer was washed twice with 20 mL of CHCl3. The solutions were combined, dried with MgSO4, and the containing pyrazoles were crystallized at -36 °C for two days. The pyrazoles were further purified via sublimation to receive pyrazoles 1a-h as colorless crystals. |
82% | With hydrazine hydrate In ethanol at 0℃; for 6 h; Reflux; Inert atmosphere | Hydrazine monohydrate (13.22 g, 12.8 mL, 264.2 mmol) was added to 2-chloropyridine (3 g, 2.5 mL, 26.42 mmol) in a two necked round-bottom flask. The resultinghomogeneous mixture was refluxed for 6 h under argon atmosphere. Then it was allowed tocome to room temperature and extracted with Et2O three times before the remaining aqueouslayer was evaporated under reduced pressure. Water (60 mL) and solid KOH (3 g) was thenadded and resulting mixture was further extracted with diethyl ether (4 x 15 mL). Finally thereaction mixture was washed with brine, dried over anhydrous Na2SO4 and titled compoundwas afforded as brown low melting solid by solvent removal under reduced pressure (1.96 g,68percent). |
61% | With hydrazine hydrate In ethanol for 3 h; Reflux | [0149] A mixture of methyl l,l,l-trifluoropentane-2,4-dione (10 g, 65 mmol, 1 eq) in hydrazine hydrate (3.5 g, 65 mmol, 1 eq) and EtOH (30 mL) was stirred at reflux for 3 h. TLC (petroleum ether/EtOAc = 1 : 1) analysis showed the reaction was completed. The reaction was concentrated in vacuum to give 5-methyl-3-(trifluoromethyl)-lH-pyrazole (6.0 g, yield: 61percent); LC/MS: m/z (M++l) = 151. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40.1% | Stage #1: ethyl trifluoroacetate,; acetone With sodium ethanolate In ethanol at 50℃; for 4h; Stage #2: With sulfuric acid | 2 In a 1000 mL three-necked flask,Add 500mL ethanol,204 g (3 moles) of sodium ethoxide are added with stirring,Ethyl trifluoroacetate 142g (1mol) and 174g (3mol) of acetone,The reaction was heated to 50 ° C and reacted for 4 hours at a vacuum of 0.01 MPaNext, the ethanol is distilled off by heating to 50 ° C,To the reaction mixture was added 294 g (3 mol) of sulfuric acid,Trifluoroacetylacetone was distilled off under reduced pressure at a pressure of 0.09 MPa,31 ~ 33 collected fractions,63.6 g of a colorless liquid was obtained,Trifluoroacetylacetone GC content99.1%, yield 40.1% |
With sodium ethanolate | ||
With potassium <i>tert</i>-butylate |
With sodium hydride In tetrahydrofuran Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With hydrogenchloride In acetonitrile for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrazine; In methanol; at 0 - 20℃; for 16h; | Example 127: Preparation of 5-methyl-3-trifluoromethyl-l/jr-pyrazoleTo a solution of trifluoroacetyl acetone (4.62 g, 30 mmol) in methanol (20 ml), was added slowly at O0C a solution of hydrazine (945 mul, 30 mmol). The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 16 hours. <n="90"/>The reaction mixture was concentrated to give 5-methyl-3-trifluoromethyl-lH-pyrazole as a yellow solid (4.5 g, 95% yield).1H-NMR (400 MHz, CDCl3): 2.35 (s, 3H, Me), 6.32 (s, IH, CH), 9.88 (bs, IH, NH) ppm. |
90% | General procedure: 1.00 equiv. (40.0 mmol) of beta-diketones (2a-h) and 30 mL chloroform were introduced in a two-necked reaction flask. 1.00 equiv. (40.0 mmol) of 100% hydrazine monohydrate was added dropwise to the solution. After refluxing for one hour the reaction mixture was cooled to room temperature and 6 g of P4O10 was added followed by heating to reflux for additional three hours. After cooling, the reaction mixture was slowly mixed with 30 mL of H2O until all residues of P4O10 were diluted. The organic layer was separated and the aqueous layer was washed twice with 20 mL of CHCl3. The solutions were combined, dried with MgSO4, and the containing pyrazoles were crystallized at -36 C for two days. The pyrazoles were further purified via sublimation to receive pyrazoles 1a-h as colorless crystals. | |
82% | With hydrazine hydrate; In ethanol; at 0℃; for 6h;Reflux; Inert atmosphere; | Hydrazine monohydrate (13.22 g, 12.8 mL, 264.2 mmol) was added to 2-chloropyridine (3 g, 2.5 mL, 26.42 mmol) in a two necked round-bottom flask. The resultinghomogeneous mixture was refluxed for 6 h under argon atmosphere. Then it was allowed tocome to room temperature and extracted with Et2O three times before the remaining aqueouslayer was evaporated under reduced pressure. Water (60 mL) and solid KOH (3 g) was thenadded and resulting mixture was further extracted with diethyl ether (4 x 15 mL). Finally thereaction mixture was washed with brine, dried over anhydrous Na2SO4 and titled compoundwas afforded as brown low melting solid by solvent removal under reduced pressure (1.96 g,68%). |
61% | With hydrazine hydrate; In ethanol; for 3h;Reflux; | [0149] A mixture of methyl l,l,l-trifluoropentane-2,4-dione (10 g, 65 mmol, 1 eq) in hydrazine hydrate (3.5 g, 65 mmol, 1 eq) and EtOH (30 mL) was stirred at reflux for 3 h. TLC (petroleum ether/EtOAc = 1 : 1) analysis showed the reaction was completed. The reaction was concentrated in vacuum to give 5-methyl-3-(trifluoromethyl)-lH-pyrazole (6.0 g, yield: 61%); LC/MS: m/z (M++l) = 151. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | In ethanol; at 20℃; for 72h;Heating; | General procedure: Compound 1 or 2, 3 mmol, was slowlyadded dropwise to a solution of 3 mmol of carbonic hydrazide 3 in a minimum volume of anhydrousethanol (compound 3 was dissolved on heating). Themixture was kept for 3 days at room temperature. Inthe synthesis of 4, the solvent was removed at roomtemperature, and the residue was recrystallized fromhexane. Compound 5 separated from the reaction mixtureand was filtered off and washed with anhydrous ethanol. 5-Hydroxy-3-methyl-5-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-1-<strong>[497-18-7]carbohydrazide</strong> (4). Yield60%, mp 165C; published data: mp 161-162C [3],158-159C [8]. 1H NMR spectrum, delta, ppm: 1.96 s(3H, Me), 2.99 d and 3.35 d (1H each, 4-H, 2J =19.0 Hz), 4.07 br.s (2H, NH2), 7.38 br.s (1H, NH),7.87 br.s (1H, OH). 13C NMR spectrum, deltaC, ppm:15.98 (Me), 48.56 (C4), 91.36 q (C5, 2JCF = 33.1 Hz),124.27 q (CF3, 1JCF = 285.1 Hz), 152.60 (C3), 156.02(C=O). Found, %: C 31.97; H 3.89; N 24.29.C6H9F3N4O2. Calculated, %: C 31.86; H 4.01; N 24.77. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 70% 2: 25% | In methanol for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With air at 20℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With acetic acid;sulfuric acid; at 100℃; for 0.166667h;microwave irradiation; | To a stirred solution of 50 mg (0.19 mmol) (2-amino-4,5,6,7-tetrahydro- benzo[b]thiophen-3-yl)-thiophen-2-yl-methanone in 1.5 ml acetic acid was added 0.024 ml (0.20 mmol) of l,l,l-trifiuoro-pentane-2,4-dione and one drop of sulfuric acid. The mixture was then stirred at 100 0C for 10 minutes in a microwave and then concentrated in vacuo. Flash chromatography (heptane / ethyl acetate 9:1) afforded 17 mg (23 %)2,2,2-trifiuoro-l-(2-methyl-4-thiophen-2-yl-5,6>7,8-tetrahydro-benzo[4,5]thieno[2,3-b] pyridin-3-yl)- ethanone as an orange oil. ES-MS m/e (%): 382 (M+ H+, 100). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With chlorosulfonic acid; thionyl chloride; In methanol; ethanol; acetic acid; toluene; | EXAMPLE 63 1,5-Dimethyl-3-(trifluoromethyl)-4-pyrazolesulfonyl chloride A: 1,5-Dimethyl-3-(trifluoromethyl)pyrazole To a solution 25.0 grams of 1,1,1,-trifluoro-2,4-pentanedione in 150 ml of ethanol (anhydrous, 5% methanol) at 10 C. was added dropwise over 35 minutes a solution 8.3 grams of methyl hydrazine in 25 ml of ethanol. The reaction temperature did not exceed 20 C. After an additional 30 minutes of stirring, the cooling bath was removed and the reaction was allowed to stir for one hour. Then five ml of glacial acetic acid was added and the reaction was refluxed for four hours. The reaction was then concentrated under reduced pressure and 100 ml of toluene was added to help azeotrope the residual acetic acid during a second concentration under reduced pressure. High vacuum was pulled on the sample for one hour at 50 C. to yield 25.3 g of the desired product as an oil. B: 1,5-Dimethyl-3-(trifluoromethyl)--4-pyrazolesulfonyl chloride To 53 mls of chlorosulfonic acid at 10 C. was added dropwise over fifteen minutes <strong>[79080-31-2]1,5-dimethyl-3-(trifluoromethyl)pyrazole</strong> (24.0 grams). No significant exotherm resulted and after 15 minutes the cooling bath was removed and the reaction was heated to 110 C. for three hours. After standing overnight, the reaction was heated to 110 C. for an additional four hours and allowed to cool to 50 C. Then 19.0 g of thionyl chloride was dropwise over fifteen minutes. The reaction was then heated to 80 C. for twenty minutes and 110 C. for one hour. After cooling, the reaction was cautiously added to 600 g of ice. The aqueous phase was extracted with two 250 ml portions of ether. The combined organic extracts were dried with MgSO4 and concentrated under reduced pressure to yield 7.8 g of the desired product as a tan oil. Using the procedure described in Example 63B, except the use of thionyl chloride was omitted, the following sulfonyl chloride was prepared from the indicated pyrazole: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; ethanol; acetic acid; toluene; | A: 1,5-Dimethyl-3-(trifluoromethyl)pyrazole To a solution 25.0 grams of 1,1,1-trifluoro-2,4-pentanedione in 150 ml of ethanol (anhydrous, 5% methanol) at 10 C. was added dropwise over 35 minutes a solution 8.3 grams of methyl hydrazine in 25 ml of ethanol. The reaction temperature did not exceed 20 C. After an additional 30 minutes of stirring, the cooling bath was removed and the reaction was allowed to stir for one hour. Then five ml of glacial acetic acid was added and the reaction was refluxed for four hours. The reaction was then concentrated under reduced pressure and 100 ml of toluene was added to help azeotrope the residual acetic acid during a second concentration under reduced pressure. High vacuum was pulled on the sample for one hour at 50 C. to yield 25.3 g of the desired product as an oil. | |
Step 1. A solution of l,l,l-trifluoropentane-2,4-dione (4.00 mL, 32.4 mmol) and methylhydrazine (1.80 mL, 33.5 mmol) in hexafluoroisopropanol (35 mL) was warmed to 45 C for 10 hours, then cooled and the solvent removed by short-path distillation. The crude product l,5-dimethyl-3-(trifluoromethyl)-lH-pyrazole (5.26 g, 32.0 mmol, 99%) was used directly in the next step without further purification. ]H NMR (500 MHz, CDC13): δ 6.28 (1H, s), 3.81 (3H, s), 2.30 (3H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In pyridine; water; for 24h;Reflux; | To a stirred solution of 2-chlorobenzothiazole (1.0 mL, 8.1 mmol) and malononitrile (534 mg; 8.1 mmol) in acetonitrile (4 mL) was added sodium ethoxide (3.0 mL of 21 wt % solution in ethanol, 8.0 mmol). The mixture was stirred at room temperature for 4 d, then acidified with 2M hydrochloric acid. The solid was collected by filtration, washed with acetonitrile, and dried under vacuum to give 2-(benzothiazol-2(3H)-ylidene)malononitrile (770 mg) as a white solid.A suspension of 2-(benzothiazol-2(3H)-ylidene)malononitrile (0.45 g, 2.25 mmol) in dioxane (10 mL) and ethanol (10 mL) was cooled to 0 C. and hydrogen chloride gas was bubbled into the mixture for 10 min. The mixture was allowed to warm to room temperature, then heated to 50 C. overnight. The resulting precipitate was collected by filtration, washed with acetonitrile, and dried under vacuum to give 2-[benzothiazol-2(3H)-ylidene]-2-cyanoacetimidate (0.43 g) as a white solid.A suspension of 2-[benzothiazol-2(3H)-ylidene]-2-cyanoacetimidate (0.4 g, 1.6 mmol) in ethanol (5 mL) was placed in a pressure tube, cooled to -78 C., and gaseous ammonia was bubbled into the tube. The mixture was allowed to warm to room temperature and stirred for 3 d. The solvent was removed under vacuum to give 2-[benzothiazol-2(3H)-ylidene]-2-cyanoacetamidine as a beige solid.2-[Benzothiazol-2(3H)-ylidene]-2-cyanoacetamidine (0.2 g, 0.92 mmol) was dissolved in dimethylsulfoxide (1 mL), and 1,1,1-trifluoro-5,5,-dimethyl-2,4-hexanedione (320 muL, 1.84 mmol) and sodium ethoxide (0.6 mL of 21 wt % solution in ethanol, 1.84 mmol) were added. The solution was heated to 180 C. under microwave irradiation for 20 min, dissolved in EA, and washed with 1N hydrochloric acid and then water. Removal of the solvent gave 2-[benzothiazol-2(3H)-ylidene]-2-[4-tert-butyl-6-(trifluoromethyl)pyrimidin-2-yl]acetonitrile as a beige solid.2-[Benzothiazol-2(3H)-ylidene]-2-[4-tert-butyl-6-(trifluoromethyl)pyrimidin-2-yl]acetonitrile (150 mg, 0.39 mmol) was dissolved in concentrated sulfuric acid (1.5 mL) and stirred at room temperature overnight. The mixture was cooled to 0 C., poured over ice, and neutralized with 50% aqueous sodium hydroxide. The product was partially extracted into chloroform, and dried to a brown solid (57 mg), which was purified by reverse phase preparative HPLC to give 2-[benzothiazol-2(3H)-ylidene]-2-[4-tert-butyl-6-(trifluoromethyl)pyrimidin-2-yl]acetamide (13 mg) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With Preyssler heteropoly acid supported on silica coated nickel ferrite nanoparticles In ethanol for 0.833333h; Reflux; | 2.2. Synthesis of bis(dihydropyrimidinone)benzene derivatives (5a-5h) General procedure: The NFS-PRS catalyst (0.02 g) was added to a solution of terephthalic aldehyde (1.0 mmol), urea (2.5 mmol) and 1,3-dicarbonyl compound (2.0 mmol) in ethanol (10 mL) and refluxed for 45-60 min. Upon completion, the reaction mixture was allowed to cool to room temperature and the NFS-PRS wasseparated from the reaction mixture by an external magnet and thoroughly washed and dried to be reused in the next run. Cold water (20 mL) was added to the reaction mixture (without acatalyst) and after stirring for a few minutes, the solid product formed was filtered off and washed several times with cold ethanol and water. The resulting crude product was recrystallized from ethanol and gave compounds 5a-5h in high yields. |
85% | With chloro-trimethyl-silane at 100℃; for 0.0666667h; Microwave irradiation; | |
83% | With ethanol at 80℃; for 0.916667h; |
81% | With nanosilica at 100℃; for 0.05h; Microwave irradiation; Neat (no solvent); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With piperidine In dichloromethane at 20℃; for 4.5h; stereoselective reaction; | |
With piperidine In dichloromethane at 20℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With triethyl borate In acetonitrile at 20℃; for 0.166667h; | 4.2. General procedure for synthesis of tridentate β-aminoenones 2a-c General procedure: o-Phenylenediamine (0.55 g, 5.1 mmol), B(OEt)3 (0.75 g, 5.14 mmol) and 1,3-diketone 1a-c (5.0 mmol) in CH3CN (20 mL) were stirred 10-15 min, diluted with water (50 mL) and stirred until solidification of a precipitated oil. The solid was collected, washed with water, dried in the air, dissolved in CHCl3 (3 mL), and passed through silica gel bed (2 cm). Silica gel was washed with CHCl3 (3 × 5 mL). Combined chloroform solutions were evaporated. The residue was recrystallized from hexane-CH2Cl2 (3:1) solution. Yields of 2a-c are collected in the Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15%; 34% | With manganese(III) triacetate dihydrate; acetic acid; at 60 - 80℃;Inert atmosphere; | A solution of manganese(III) acetate dihydrate (5 mmol, 1.35 g) in 20 mL in glacial acetic acid was heated under nitrogen atmosphere at 80 C until it dissolved. After Mn(OAc)3 dissolved completely, the solution was cooled down to 60 C. A solution of trifluoromethyl-1,3-dicarbonyl compound (2.5 mmol) and alkene (2 mmol) in 5 mL acetic acid was added to this mixture and the temperature was raised to 80 C. The reaction was complete when the dark brown colour of the solution disappeared. Acetic acid was evaporated under reduced pressure. Water was added to the residue and extraction was performed with CHCl3 (3 x 20 mL). The combined organic extracts were neutralized with satd. NaHCO3 solution, and dried over anhydrous Na2SO4 and evaporated. Crude products were puried by column chromatography or preparative TLC (20 cm x 20 cm plates, 2 mm thickness) using n-hexane/EtOAc (5:1) as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | General procedure: Equimolar amounts of appropriate 2-hydrazinobenzothiazole1a-b, alpha-cyanoacetophenone 2a-c, and PTSA were mixed thoroughly in pestle mortar and heated on water bath for 4-5 min and then equimolar amount of appropriate trifluoromethyl beta-diketones 3a-d was added to it and mixed thoroughly. The reaction mixture was again heated 80-90 ° C for 15 min on water bath. The solid was obtained by addition of aq. ethanol, filtered and crystallized from the mixture of ethanol and chloroform to give pure 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 1,3-benzothiazol-2-ylhydrazine; p-chlorobenzoylacetonitrile With toluene-4-sulfonic acid for 0.0833333h; Heating; Neat (no solvent); Stage #2: 1,1,1-Trifluoro-2,4-pentanedione at 80 - 90℃; for 0.25h; Neat (no solvent); regiospecific reaction; | 4.1. General procedure for three-component solvent-free synthesis of 1-(benzothiazol-2'-yl)-3-aryl-4-substituted-6-trifluoromethyl-1Hpyrazolo[3,4-b]pyridines 4a-h. General procedure: Equimolar amounts of appropriate 2-hydrazinobenzothiazole1a-b, α-cyanoacetophenone 2a-c, and PTSA were mixed thoroughly in pestle mortar and heated on water bath for 4-5 min and then equimolar amount of appropriate trifluoromethyl β-diketones 3a-d was added to it and mixed thoroughly. The reaction mixture was again heated 80-90 ° C for 15 min on water bath. The solid was obtained by addition of aq. ethanol, filtered and crystallized from the mixture of ethanol and chloroform to give pure 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With diethylamine In ethanol for 2.5h; Reflux; | |
82% | With diethylamine In ethanol Schlenk technique; Reflux; | |
82% | With 1,4-diaza-bicyclo[2.2.2]octane In ethanol; water at 40℃; for 10h; |
68% | With piperidine In ethanol Reflux; | Typical Procedure for the Synthesis of 3-cyano-4-trifluoromethyl-6-phenyl/methyl-2-(1H)pyridone General procedure: To a solution of cyano acetamide 2 (0.02 mol) in 95%ethanol (10ml) was added 1,1,1-trifluoro-4-phenyl-2,4-butanedione 1a or 1,1,1-trifluoro-2,4-pentanedione 1b(0.02mol) with stirring. To the homogenous mixture,Piperidine (0.02mol) was then added drop wise and the reaction mixture was refluxed for 6-8 hrs. After completion of the reaction, the mixture was cooled to room temperature.The resulting solid was filtered, washed with small portions of cold ethanol to remove remaining residues and dried at85°C (Purity >99%). |
52% | With potassium carbonate In water at 23℃; for 15h; | [0900] 6-Methyl-2-oxo-4-(trifluoromethyl)-l,2-dihydropyridine-3-carbonitriIe [0901 ] To a solution of 2-cyanoacetamide (14.0 g, 166 mmol) and trifluoroacetylacetone (20.0 ml, 166 mmol) in H20 (332 ml) was added K2C03 (6.60 g, 47.9 mmol). The mixture was stirred at 23°C for 15 h. The precipitated solid was filtered with Buchner funnel, washed with ice cold H20, and dried with hot air (60 °C, 16 h) to give the titled compound (17.6 g, 52%). NMR (400 MHz, DMSO-d6): δ ppm 2.38 (s, 3H), 6.66 (s, 1 H). |
With piperidine In ethanol Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With sodium hydroxide In methanol; water at 40℃; | 9 2.9 [Eu(dptz)(acacF3)3] (9) General procedure: A methanolic solution (10 mL) of 1,1,1-trifluoro-2,4-pentanedione (0.308 mL, 2.55 mmol) and NaOH (2.55 mL, 1 M aqueous solution) were dropwise added to a methanolic solution (7 mL) of complex 1 (0.78 g, 0.85 mmol). The resulting solution was stirred overnight at 40 °C. Water was added into the solution resulting in precipitation of a pale pink solid which was isolated by filtration. The solid was recrystallized from 2-propanol/nitromethane. The solid was allowed to dry in vacuum to yield 0.36 g, (63%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sodium hydroxide In methanol; water at 40℃; | 8 2.8 [Eu(124-tptz)(acacF3)3] (8) General procedure: A methanolic solution (10 mL) of 1,1,1-trifluoro-2,4-pentanedione (0.308 mL, 2.55 mmol) and NaOH (2.55 mL, 1 M aqueous solution) were dropwise added to a methanolic solution (7 mL) of complex 1 (0.78 g, 0.85 mmol). The resulting solution was stirred overnight at 40 °C. Water was added into the solution resulting in precipitation of a pale pink solid which was isolated by filtration. The solid was recrystallized from 2-propanol/nitromethane. The solid was allowed to dry in vacuum to yield 0.36 g, (63%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.4% | With diethylamine In ethanol at 70℃; for 8h; | 12 Example 12: Preparation of 2-hydroxy-6-methyl-4-(trifluoromethyl)nicotinonitrile (I-26) To a solution of 2-cyanoacetamide (10 g, 0.119 mol) and 1,1,1-trifluoropentane-2,4-dione (16.6 g, 0.108 mol) in EtOH (70 mL) was added diethylamine (3.95 g, 0.054 mol). The reaction mixture was stirred for 8 h at 70 °C. After cooling, the mixture was allowed to stand overnight at 0 °C. The yellow crystals formed were collected on a filter and dried at 80 °C to give the title compound (21 g, 96.4%): mp 234.7-236.4 °C; 1H NMR (300 MHz, DMSO-d6) δ 6.560 (s, 1H), 2.358 (s, 3H); ESIMS m/z 201 ([M-1]-). |
96.4% | With diethylamine In ethanol at 70℃; for 8h; | 12 Preparation of 2-hydroxy-6-methyl-4-(trifluoromethyl)nicotinonitrile (I- 26) o a solution of 2-cyanoacetamide (10 g, 0.119 mol) and l,l,l-trifluoropentane-2,4- dione (16.6 g, 0.108 mol) in EtOH (70 mL) was added diethylamine (3.95 g, 0.054 mol). The reaction mixture was stirred for 8 h at 70 °C. After cooling, the mixture was allowed to stand overnight at 0 °C. The yellow crystals formed were collected on a filter and dried at 80 °C to give the title compound (21 g, 96.4%): mp 234.7-236.4 °C; ]H NMR (300 MHz, OMSO-d6) δ 6.560 (s, 1H), 2.358 (s, 3H); ESIMS m/z 201 ([M-l] ). |
With diethylamine In ethanol at 70℃; for 12h; | a Intermediate 1 : 2-Chloro-6-methyl-4-(trifluoromethyl)nicotinonitrile Step a. To a solution of 1,1,1-trifluoropentane-2,4-dione (25 g, 162 mmol) and 2-cyano- acetamide (15 g, 178 mmol) in EtOH (200 ml_) was added diethylamine (5.93 g, 81.1 mmol). The mixture was stirred at 70°C for 12 h. On completion, white solid was precipitated from EtOH. The reaction mixture was filtered and solid was collected, further dried under vacuum to afford 2-hydroxy-6-methyl-4-(trifluoromethyl)pyridine-3-carbonitrile (24.5 g, 121 mmol, crude) as a white solid. m/z ES+ [M+H]+203.0;1H NMR (400 MHz, DMSO-d6) d ppm 6.51 (s, 1 H), 2.33 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With ammonium acetate In ethanol; water for 3.5h; Reflux; chemoselective reaction; | General Procedure for the Synthesis of Substituted Pyrroles General procedure: To a mixture of benzoin derivative (2 mmol) and 1,3-dicarbonyl compound (2 mmol) in H2O-EtOH (2 mL, 50:50)was added NH4OAc (4 mmol), and the mixture was stirred under reflux for the requisite time. After completion of the reaction (TLC), ice was added, and the product was isolated by filtration. |
88% | With C31H68N2O(2+)*2Cl4Fe(1-); ammonium acetate In neat (no solvent) at 80℃; for 0.583333h; | 2.4.2. General procedure for the MGSFe-catalyzed synthesis of pyrroles General procedure: For improved synthesis of pyrroles, MGSFe (10mol%) was added to amixture of the corresponding 1,3-dicarbonyl (5mmol), ammonium acetate(6 mmol), and benzoin derivatives (5 mmol) and the mixture was stirred under the solvent-free conditions at 80 °C. After the completion of this step (detected by TLC monitoring), the catalyst and product were isolated by two different procedures. In the first work-up, cold water(5 mL) was added, aqueous phase of surfactant-based MGSFe was keptby magnet, the precipitated pyrrole product was isolated, and the MGSFe catalyst was recovered in 99.9% yield after the vacuum evaporation of water from the aqueous phase and reused. In the second alternative work-up, ethyl acetate (50mL) was added to dissolve the pyrrole product, the viscous catalyst was isolated bymagnet, and the product was obtained in pure form by evaporation of the EtOAc from the organic phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: 1,1,1-Trifluoro-2,4-pentanedione With sodium hydroxide In methanol; water Stage #2: [Sm2(N-(pyridin-2-ylmethylene)picolinohydrazonate)2(NO3)4(CH3OH)] In methanol; water at 50℃; | Synthesis of [Sm2phzp2(acacF3)4] (8) General procedure: A methanol solution(10 mL) containing 1,1,1-trifluoro-2,4-pentanedione (0.46 g, 3.0 mmol) and NaOH (3.0 mL, 3.0 mmol,1.0 M aqueous solution) was added dropwise to a methanol solutionof complex 1 (0.51 g, 0.50 mmol) under stirring. The resultingsolution was stirred overnight at 50 C. H2O (10 mL) was addedinto the solution resulting in the precipitation of a pale green solid.The solid was filtered and dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: 1,1,1-Trifluoro-2,4-pentanedione With sodium hydroxide In methanol; water Stage #2: [Eu2(N-(pyridin-2-ylmethylene)picolinohydrazonate)2(NO3)4(CH3OH)] In methanol; water at 50℃; | Synthesis of [Eu2phzp2(acacF3)4] (9) General procedure: A methanol solution(10 mL) containing 1,1,1-trifluoro-2,4-pentanedione (0.46 g, 3.0 mmol) and NaOH (3.0 mL, 3.0 mmol,1.0 M aqueous solution) was added dropwise to a methanol solutionof complex 1 (0.51 g, 0.50 mmol) under stirring. The resultingsolution was stirred overnight at 50 C. H2O (10 mL) was addedinto the solution resulting in the precipitation of a pale green solid.The solid was filtered and dried under vacuum. Yield 73%. KM at298 K in methanol: 23.4 (X1 cm2 mol1). Anal. Calc. for C44H34N8-O10F12Pr2: C, 39.30; H, 2.55; N, 8.33. Found: C, 39.22; H, 2.65; N,8.22% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: 1,1,1-Trifluoro-2,4-pentanedione With sodium hydroxide In methanol; water Stage #2: [Gd2(N-(pyridin-2-ylmethylene)picolinohydrazonate)2(NO3)4(CH3OH)] In methanol; water at 50℃; | Synthesis of [Gd2phzp2(acacF3)4] (10) General procedure: A methanol solution(10 mL) containing 1,1,1-trifluoro-2,4-pentanedione (0.46 g, 3.0 mmol) and NaOH (3.0 mL, 3.0 mmol,1.0 M aqueous solution) was added dropwise to a methanol solutionof complex 1 (0.51 g, 0.50 mmol) under stirring. The resultingsolution was stirred overnight at 50 C. H2O (10 mL) was addedinto the solution resulting in the precipitation of a pale green solid.The solid was filtered and dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | In ethanol; for 7.0h;Reflux; | General procedure: An ethanolic solution (25 mL) of <strong>[23906-13-0]2-hydrazino-4,6-dimethylpyrimidine</strong> 1 (0.27 g, 2 mmol) and trifluoromethyl-bdiketones 2a-c (2 mmol) was refluxed for 7 h. The reaction was monitored by tlc. On completion of reaction, solvent was evaporated in vacuo and the solid obtained was recrystallized from ethanol. The tlc and 1H NMR of the reaction mixture showed the formation of a single product 3a-c. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
485.6 mg | With acetic acid; In 2-methoxy-ethanol; for 1.66667h;Reflux; | 300 mg of <strong>[6971-45-5]2-methoxyphenylhydrazine hydrochloride</strong> was dissolved in 1.3 ml of 2-methoxyethanol, and 2.5 ml of acetic acid and 208 mul of 1,1,1-trifluoro-2,4-pentanedione were added, followed by heating to reflux for 1 hour and 40 minutes. The solvent was distilled off under reduced pressure, 50 ml of ethyl acetate was added, the organic layer washed with 50 ml of saturated sodium hydrogen carbonate solution and 50 ml of saturated brine was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to afford 485.6 mg of the title compound. 1H-NMR (CDCl3); delta (ppm) 2.14 (3H, s), 3.78 (3H, s), 6.40 (1H, s), 7.00-7.07 (2H, m), 7.31-7.33 (1H, m), 7.41-7.45 (1H, m). MS (ESI); m/z 257 (M+H)+ |
485.6 mg | With acetic acid; In 2-methoxy-ethanol; for 1.67h;Reflux; | [0188] 300 mg of <strong>[6971-45-5]2-methoxyphenylhydrazine hydrochloride</strong> was dissolved in 1.3 ml of 2-methoxyethanol, and 2.5 ml of acetic acid and 208 mul of 1,1,1-trifluoro-2,4-pentanedione were added, followed by heating to reflux for 1 hour and 40 minutes. The solvent was distilled off under reduced pressure, 50 ml of ethyl acetate was added, the organic layer washed with 50 ml of saturated sodium hydrogen carbonate solution and 50 ml of saturated brine was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to afford 485.6 mg of the title compound. [0189] 1H-NMR (CDCl3); delta (ppm) 2.14 (3H, s), 3.78 (3H, s), 6.40 (1H, s), 7.00-7.07 (2H, m), 7.31-7.33 (1H, m), 7.41-7.45 (1H, m). [0190] MS (ESI); m/z 257 (M+H)+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With cesium fluoride In acetonitrile for 6h; Reflux; | Reaction of 4,4,4-trifluoro-1-phenylbutan-1,3-dione with triflate 1a in refluxing acetonitrile General procedure: To a solution of 4,4,4-trifluoro-1-phenylbutan-1,3-dione (108 mg, 0.50 mmol) and CsF (228 mg, 1.50 mmol) in acetonitrile (7 mL) was added triflate 1a (253 mg, 0.85 mmol) in acetonitrile (3 mL). After refluxing for 6h, the reaction mixture was washed with water, dried over MgSO4, filtered, and evaporated to give pale yellow oil, which was chromatographed over silica gel by elution with hexane-dichloromethane (1:1) to afford 3-phenylisocoumarin 3b (71.1 mg, 0.32 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In dichloromethane; at -15℃; for 0.5h; | To a stirred solution of 3(5)-amino-4-phenyl-1H-pyrazole 1 (1.0 g, 6.2 mmol) in DCM (15 ml) was added 1,1,1-trifluoromethyl-pent-2,4-dione (3b) (0.7 g, 6.2 mmol) at -15 C. The reaction mixture was stirred for 0.5 h. The reaction was monitored by TLC carried out on pre-coated silica gel glass plates. The solid mass separated on stirring was filtered off and washed with cold dichloromethane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol; for 6h;Reflux; | General procedure: To a warm solution of 3(5)-amino-4-phenyl-1H-pyrazole 1 (1.0 g, 6.2 mmol) in ethanol (20 ml) was added 1,1,1,5,5,5-hexafluoropentan-2,4-dione 3a (1.3 g, 6.2 mmol) and the mixture was refluxed for 6 h. The reaction was monitored by TLC carried out on pre-coated silica gel glass plates. The pale yellow solid obtained on cooling was recrystallised from ethanol. All other compounds, 4b-l, were synthesized according to procedure mentioned for 4a using 1-2 with fluorinated-b-diketones 3a-f. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With iodine; In water; at 25℃; for 0.166667h;Sonication; Green chemistry; | General procedure: A 50mL flask was charged with aldehyde (1 mmol), malononitrile (1 mmol), 1,3-diketone (1 mmol) and iodine (0.2 mmol) in water (3 mL). The mixture was sonicated (35 kHz, constant frequency) at 25 C for 10 min. After completion of the reaction [monitored by TLC, using hexane:ethyl acetate (9:1) as eluent], the reaction mixture was quenched with ice and the precipitate formed was filtered, washed, dried and recrystallized from ethanol to get the pure product. The structures of all the products were confirmed by IR, 1H NMR, 13C NMR, ESI-MS and CHN analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With iron(III) chloride hexahydrate In water at 100℃; for 24h; Green chemistry; | 2. Typical Procedure for the Synthesis of 2-Substitued Quinazolinones General procedure: A flask was charged with 2-aminobenzamide (1a; 27.2 mg, 0.2 mmol), pentane-2,4-dione (2A;30.0 mg, 0.3 mmol), FeCl3·6H2O (10.8 mg, 0.04 mmol), and PEG-400/H2O (1.0 mL, 1:9 (v/v)).The reaction was stirred at 100 °C for 24 h. When the reaction was complete monitored by TLC,the mixture was cooled to room temperature, extracted with EtOAc (3×20 mL). The combined organic phase was washed with water, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give the product 3aA (29.3 mg, 91%) as white solid. |
54% | With camphor-10-sulfonic acid In water at 100℃; for 16h; Green chemistry; | |
68 %Chromat. | With ytterbium(III) triflate In 1,3,5-trimethyl-benzene at 60℃; for 12h; Inert atmosphere; | General procedure for the synthesis of 2-substituted 4(3H)-quinazolinones 3 General procedure: 2-aminobenzamide (1, 1.0 mmol), 1,3-diketone (2, 1.5 mmol), Yb(OTf)3 (0.050 mmol, 5.0 mol%),and mesitylene (2.0 mL) was placed in a 20-mL Pyrex flask equipped with a magnetic stirring bar and a reflux condenser under a flow of argon. The reaction was carried out at 60°C (bath temp.) for 24 h with stirring. The reaction mixture was then cooled to room temperature and analyzed by GLCand GC-MS. The product 3 was isolated by medium-pressure column chromatography on silica gel(eluent: EtOAc/hexane = 30/70 ~ EtOAc 100%. For 3j, eluent: MeOH/CHCl3 = 30/70 ~ 50/50) andrecrystallization from MeOH/hexane. The products 3l and 3m were isolated by recrystallizationfrom EtOAc/hexane. 1H NMR spectra were recorded at 400 MHz, and 13C NMR spectra wererecorded at 100 MHz in DMSO-d6 (For 3j, in a mixture of DMSO-d6 and methanol-d4). Elemental analyses were performed at the Microanalytical Center of Kyoto University. The analytical and spectral data of 3a,10 3b-c,11 3d,12 3e,13 3f,14 3g-h,10 and 3j-l,7 are fully consistent with those reported previously. The products 3i,15 and 3m16 were characterized below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | 1,1,1-Trifluoropentane-2,4-dione (15 mmol) and boric anhydride (10.5 mmol) were mixed in dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of <strong>[348-27-6]2-fluoro-4-hydroxybenzaldehyde</strong> (15 mmol) and tributyl borate (22.5 mmol) in dry ethyl acetate (7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (15 mmol) in dry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 C for 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then added to the solution at 50 C, and the system was stirred for 1 h. After cooling, the organic layer was separated from the aqueous layer and extracted with 3 9 15 mL of ethyl acetate. The organic layer was washed with water (10 mL, 2 times) and dried (Na2SO4), and the solvent was evaporated under vacuum. The crude product was purified by column chromatography with dichloromethane/ethanol (95:5) as eluent, m.p. 151.2 C (ethanol/dichloromethane) (1.35 g, yield 33 %). C12H8F4O3 (276.18): calcd. C 52.19,H 2.92; found C 52.08, H 3.09. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17% | 1,1,1-Trifluoropentane-2,4-dione (15 mmol) and boric anhydride (10.5 mmol) were mixed in dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of<strong>[192927-69-8]2,4-difluoro-3-hydroxybenzaldehyde</strong> (15 mmol) and tributyl borate (22.5 mmol) in dry ethyl acetate (7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (15 mmol) in dry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 C for 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then added to the solution at 50 C, and the system was stirred for 1 h. After cooling, the organic layer was separated from the aqueous layer and extracted with 3 9 15 mL of ethyl acetate. The organic layer was washed with water (10 mL, 2 times) and dried (Na2SO4), and the solvent was evaporated under vacuum. The crude product was purified by column chromatography with dichloromethane/ethanol (95:5) as eluent, m.p. 129.1 C (ethanol/dichloromethane) (733.12 mg, yield 17 %). C12H7F5O3 (294.18): calcd. C48.99, H 2.40; found C 49.28, H 2.66. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | 1,1,1-Trifluoropentane-2,4-dione (15 mmol) and boric anhydride (10.5 mmol) were mixed in dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of 2,5-difluoro-3-hydroxybenzaldehyde (15 mmol) and tributyl borate (22.5 mmol) in dry ethyl acetate (7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (15 mmol) in dry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 C for 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then added to the solution at 50 C, and the system was stirred for 1 h. After cooling, the organic layer was separated from the aqueous layer and extracted with 3 9 15 mL of ethyl acetate. The organic layer was washed with water (10 mL, 2 times) and dried (Na2SO4), and the solvent was evaporated under vacuum. The crude product was purified by column chromatography with ethyl acetate/hexane (80:20) as eluent, m.p. 190.8 C (ethanol/dichloromethane) (900 mg, yield 20 %). C12H7F5O3 (294.18): calcd. C 48.99,H 2.40; found C 48.82, H 2.36. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11% | 1,1,1-Trifluoropentane-2,4-dione (15 mmol) and boric anhydride (10.5 mmol) were mixed in dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of <strong>[128495-46-5]4-fluoro-3-methoxybenzaldehyde</strong> (15 mmol) and tributyl borate (22.5 mmol) in dry ethyl acetate (7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (15 mmol) in dry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 C for 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then added to the solution at 50 C, and the system was stirred for 1 h. After cooling, the organic layer was separated from the aqueous layer and extracted with 3 9 15 mL of ethyl acetate. The organic layer was washed with water (10 mL,2 times) and dried (Na2SO4), and the solvent was evaporated under vacuum. The crude product was purified by column chromatography with ethyl acetate/hexane (30:70)as eluent, m.p. 110.8 C (ethyl acetate/hexane) (499.7 mg,yield 11 %). C13H10F4O3 (290.21): calcd. C 53.80, H 3.47;found C 53.75, H 3.37. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | 1,1,1-Trifluoropentane-2,4-dione (15 mmol) and boric anhydride (10.5 mmol) were mixed in dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of <strong>[405-05-0]3-fluoro-4-hydroxybenzaldehyde</strong> (15 mmol) and tributyl borate (22.5 mmol) in dry ethyl acetate (7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (15 mmol) in dry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 C for 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then added to the solution at 50 C, and the system was stirred for 1 h. After cooling, the organic layer was separated from the aqueous layer and extracted with 3 9 15 mL of ethyl acetate. The organic layer was washed with water (10 mL, 2 times) and dried (Na2SO4), and the solvent was evaporated under vacuum. The crude product was purified by column chromatography with dichloromethane/ethanol (95:5) as eluent, m.p. 134.4 C (ethanol/dichloromethane) (1.1 g, yield 26 percent). C12H8F4O3 (276.18): calcd. C 52.19, H2.92; found C 52.14, H 2.88. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With acetic acid In methanol at 60 - 70℃; for 2h; | Hot methanolic solutions of 4-chlorobenzhydrazide (2.49mmol, 500mg) and 1,1,1-trifluoryl-2,4-pentanedione (2.49 mmol, 0.4ml) and acetic acid were added and refluxed for 2h at 60-70°C. The obtained yellow reaction mixture was evaporated and the white colored crystalline product obtained was washed with petroleum ether and dried. L1=Yield: 85%, White solid. m.p.: 90°C. Anal calc. For C12H10ClF3N2O2: C: 47.00, H: 3.29, N: 9.13. Found: C: 46.97, H: 3.28, N: 9.15. UV-Vis (methanol): λmax (MeOH)/nm (ε,dm-3mol-1cm-1) 210(67,000), 240(35,666). FT-IR (KBr, νmax/cm-1): 1662.64 (C=O), 1643.35 (C=N), 3360 (NH). 1H NMR (400MHz, CDCl3): δH, ppm 2.053 (3H, s, CH3), 7.396, 7.417, 7.839, 7.860 (Ar-H, 4H), 3.113, 3.160, 3.278, 3.325 (CH2 protons, 2H)·13C NMR (100MHz, CDCl3): δC ppm 15.86 (CH3), 46.89 (CH2), 92.49, 92.89 (CF3), 122.07, 124.93, 128.31, 131.48, 131.79 (Ar C), 138.59 (Ar C- Cl), 155.23 (C=N), 170.01 (C=O) GC-MS Calc. for C12H10ClF3N2O2: 306.6 Found: 306.14. Chromatogram: RT- 16.38min, Purity: 99.19%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid; at 110℃; for 0.666667h; | [00534] To a solution of ethyl 2-amino-lH-pyrrole-3-carboxylate (500 mg, 3.2 mmol) in HOAc (10 mL) was added l, l,l-trifluoropentane-2,4-dione (600 mg, 3.9 mmol) at 110 C and the mixture was stirred at this temperature for 40 min, then cooled and concentrated in vacuo. The resulting residue was purified by silica gel column chromatography (PE/EA; 3/1) to afford ethyl 4-methyl-2-(trifluoromethyl)pyrrolo[l,2-a]pyrimidine-8-carboxylate (100 mg, 1 1.5%) as a brown oil and ethyl 2-methyl-4-(trifluoromethyl)pyrrolo[l,2-a]pyrimidine-8-carboxylate (160 mg, 18.4%) as a brown solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid; at 100℃; for 2h; | Ethyl 5-amino-1H-imidazole-4-carboxylate (600 mg, 3.87 mmol) and 1,1,1- trifluoropentane-2,4-dione (655 mg, 4.25 mmol) in AcOH (10 mL) was stirred at 100 C for 2 h until the reaction was complete (LC-MS). The reaction mixture was concentrated in vacuo and the residue was purified by silica gel column (PE/EA: 2/1) to obtain ethyl 4-methyl-2- (trifluoromethyl)imidazo[1,5-a]pyrimidine-8-carboxylate (220 mg, 20%) as a white solid. LC- MS m/z: 274.1 [M+H]+. LC-MS purity (214 nm): 83%; tR = 1.68 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With ammonium hydroxide; In ethanol; at 20℃; for 5h; | General procedure: A solution of Htfaa (1.0g, 6.48mmol) in ethanol (5mL) was added to a 0.48mL (0.108g, 6.48mmol) 25% ammonia solution. This mixture was covered in 50mL beaker until all the ammonia vapors dissolved. To this mixture was added a 5mL ethanol solution of bpy (0.3371g, 2.16mmol) and a 5mL ethanol solution of SmCl3·6H2O (0.7879g, 2.16mmol). The reaction mixture was stirred at room temperature for 5h. A white precipitate of NH4Cl (which does not melt up to 300C) appeared during stirring, which was filtered off repeatedly. The filtrate was covered and left for slow solvent evaporation at room temperature. A powder appeared after three days, which was filtered off and washed with CHCl3 several times. The product thus obtained was recrystallized twice from ethanol to get the pure compound and dried under vacuum over P4O10. A similar method was used to synthesize [Sm(tfaa)3phen]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 1. 4-(5-Methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile and 4-(3-methyl-5- (trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile (0988) [00318] A mixture of <strong>[17672-27-4]4-hydrazinylbenzonitrile</strong> (2 g, 15.02 mmol), l,l, l-trifruoropentane-2,4- dione (3.1 g, 20.12 mmol), sodium acetate (2.5 g, 30.48 mmol) and acetic acid (10 mL) was stirred for 1 h at 120 C. After cooling to ambient temperature, the reaction mixture was concentrated under vacuum and purified by silica gel chromatography (eluting with a gradient of 10-30% EtOAc/PE) to afford 2 g (53%) of a -2: 1 mixture of 4-(5-methyl-3-(trifluoromethyl)- lH-pyrazol-l-yl)benzonitrile and 4-(3-methyl-5-(trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile as a yellow solid. MS (ESI) m/z 252.0 [M+H]+ Step 2. (4-(5-Methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl)phenyl)methanamine and (4-(3- methyl-5-(trifluoromethyl)-lH-pyrazol-l-yl)phenyl)methanamine (0990) [00319] A -2: 1 mixture of (4-(5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl)phenyl)methanamine and (4-(3-methyl-5-(trifluoromethyl)-lH-pyrazol-l- yl)phenyl)methanamine was synthesized from a -2: 1 mixture of 4-(5-methyl-3-(trifluoromethyl)- lH-pyrazol-l-yl)benzonitrile and 4-(3-methyl-5-(trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile according to Step 2 of Example 4. MS (ESI) m/z 256.0 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate; In acetic acid; at 120℃; for 1h; | Step 1. 4-(5-Methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile and 4-(3-methyl-5- (trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile (0988) [00318] A mixture of <strong>[17672-27-4]4-hydrazinylbenzonitrile</strong> (2 g, 15.02 mmol), l,l, l-trifruoropentane-2,4- dione (3.1 g, 20.12 mmol), sodium acetate (2.5 g, 30.48 mmol) and acetic acid (10 mL) was stirred for 1 h at 120 C. After cooling to ambient temperature, the reaction mixture was concentrated under vacuum and purified by silica gel chromatography (eluting with a gradient of 10-30% EtOAc/PE) to afford 2 g (53%) of a -2: 1 mixture of 4-(5-methyl-3-(trifluoromethyl)- lH-pyrazol-l-yl)benzonitrile and 4-(3-methyl-5-(trifluoromethyl)-lH-pyrazol-l-yl)benzonitrile as a yellow solid. MS (ESI) m/z 252.0 [M+H]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.64 g | In aq. acetate buffer; at 20℃; for 24h;pH 5.9; | General procedure: To a solution of the appropriate amino ester hydrochloride 2a?f (5.4 mmol) in acetate buffer (pH5.9) (1.5 mL) trifluoromethyl 1,3-dicarbonyl compound 1a?c (2.7 mmol) and formaldehyde 33percent aqueoussolution (11 or 40 mmol) were added. The resulting mixture was stirred for 24 h at room temperature, then itwas extracted with CH2Cl2 (3 x 10 mL) and the combined organic layers were dried over Na2SO4 andevaporated in vacuo. The product was purified by column chromatography on Kieselgel 60 (chloroform?MeOH10:0?9:1 or hexane?EtOAc 10:0?7:3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | 4.0 g (11.0 mmol) of iridium trichloride trihydrate,And 43 ml of pure water were placed in a three-necked flask, stirred under an argon atmosphere,Subsequently, 5.26 g (34.11 mmol) of trifluoroacetylacetone was added and the mixture was refluxed for 1 hour under an argon atmosphere.Further, 4.52 g (45.11 mmol) of <strong>[298-14-6]potassium hydrogencarbonate</strong> was added and reacted at 90 C. for 5 hours.After the reaction overnight, unreacted trifluoroacetylacetone was extracted and removed from the supernatant aqueous layer with chloroform, and then the iridium compound (Ir-23) was extracted with ethyl acetate, and the extract was concentrated to dryness And solidified to obtain 1.8 g of brown iridium compound (Ir-23) crude product.Further, the crude product was subjected to column purification to obtain 1.5 g of an orange iridium compound (Ir-23) solid. The isolated yield was 20%. | |
20% | In water; at 95℃; for 6h;Inert atmosphere; | 4.0 g (11.0 mmol) of iridium trihydrate trihydrate,And 43 ml of pure water were placed in a three-necked flask,Stir under an argon atmosphere,Subsequently, 5.26 g (34.11 mmol) of trifluoroacetylacetone was added,Under an argon atmosphere,And refluxed for 1 hour.Further, 4.52 g (45.11 mmol) of <strong>[298-14-6]potassium hydrogen carbonate</strong> was added,And reacted at 90 C. for 5 hours.After reacting overnight, from the supernatant aqueous layer,Unreacted trifluoroacetylacetone was extracted and removed with chloroform,The iridium compound (Ir-3) was extracted with ethyl acetate,The extract was concentrated to dryness to obtain 1.8 g of a brown iridium compound (Ir-3) crude product.The crude product was subjected to column purification to obtain 1.5 g of an orange iridium compound (Ir-3) solid.The isolated yield was 20%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20%; 20% | 1,1,1-Trifluoropentane-2,4-dione (1.8 mL, 15 mmol) and boric anhydride (731.1 mg, 10.5 mmol) were mixedin dry ethyl acetate (11.25 mL) at 50 C for 30 min. After that, a mixture of <strong>[676500-39-3]2,3-difluoro-4-hydroxybenzaldehyde</strong> (2.37 g, 15 mmol) and tributyl borate (4.0 mL, 15 mmol) in dry ethyl acetate(7.5 mL) was added, with stirring for 30 min at 50 C. A solution of butylamine (1.5 mL, 15 mmol) indry ethyl acetate (7.5 mL) was added slowly over 15 min. The reaction mixture was stirred at 50 Cfor 90 min and then overnight at room temperature. Hydrochloric acid (1 M, 30 mL) was then addedto the solution at 50 C, and the system was stirred for 1.5 h. After cooling, the organic layer wasseparated from the aqueous layer and extracted with 3 × 15 mL of ethyl acetate. The organic layerwas washed with water (2 × 10 mL) and dried (Na2SO4), and the solvent was evaporated undervacuum. The crude product was purified by column chromatography with dichloromethane aseluent, obtaining two products: the desired beta-diketone 7b (Figure 15), from crystallization inhexane/acetyl acetate, as yellow crystals (882 mg, 20%), and the enamine 8 (1.05 g, 20%) resultingfrom the addition of butylamine to 7b. Enamine 8 was characterized by 1H-NMR (CDCl3): delta 11.33(1H, s, NH), 7.32 (1H, d, 3JH4 = 16.2 Hz, H5), 7.21-7.14 (1H, m, H6?), 6.90 (1H, d, 3JH5 = 16.1 Hz, H4),6.90-6.80 (1H, m, H5?), 6.16 (1H, bs, OH), 5.69 (1H, s, H2), 3.46 (2H, m, -CH2-NH-), 1.69 (2H, m, -CH2-CH2-CH2-), 1.47 (2H, m, -CH2-CH2-CH3), 0.97 (3H, m, CH3); 13C-NMR (CDCl3): delta 175.2 (q, 2JCF3 = 32.6Hz, C1), 166.0 (C3), 150.0 (dd, 1JF2 = 254.5 Hz, 2JF3 = 11.3 Hz, C2?), 146.9 (dd, 2JF3 = 10.8 Hz, 3JF2 = 2.8 Hz,C4?), 140.4 (dd, 1JF3 = 241.6 Hz, 2JF2 =15.0 Hz, C3?), 132.8 (d, 3JF2 = 3.2 Hz, C5), 123.8 (t, 3JF2 = 4JF3 = 3.9 Hz, C6'), 119.9 (d, 4JF2=8.3Hz,C4), 118.0(d,1J=271.0Hz, CF3), 116.6 (d, 2JF2 = 8.1 Hz, C1?), 112.9 (d, 3JF3 =3.3 Hz, C5?), 85.2 ( 116.6 (d, 2JF2 = 8.1 Hz, C1?), 112.9 (d, 3JF3 =3.3 Hz, C5?), 85.2 (C2), 43.8 (-CH2-NH-), 31.8 (-CH2-CH2-CH2-), 19.9 (-CH2-CH2-CH3), 13.6 (CH3); 15N-NMR (CDCl3): delta 253.9. As (3Z,5E)-4-(butylamino)-6-(2,3-difluoro-4-hydroxyphenyl)-1,1,1-trifluorohexa-3,5-dien-2-one8 needs stronger hydrolysis conditions to yield 7b, 12 N HCl (2.5 mL) was added and the solutionwas stirred for 30 min at 50 C. After cooling, the aqueous layer was extracted with 3 × 3 mL of ethylacetate. The organic layer was then washed with water (2 × 2 mL) and dried (Na2SO4), and the solventwas evaporated under vacuum. The yield for the hydrolysis was 90%, and the global yield for thesynthesis of 7b after crystallization in hexane/ethyl acetate was (1.67 g, yield 38%): m.p. 162.7 C (fromhexane/ethyl acetate); 1H-NMR (CDCl3): delta 14.15 (1H, br, OH-enol), 7.75 (1H, d, 3JH4 = 16.0 Hz, H5),7.24 (1H, ddd, 3JH5? = 8.9 Hz, 4JF2 = 7.3 Hz, 5JF3 = 2.1 Hz, H6?), 6.85 (1H, ddd, 3JH6? = 8.9 Hz, 4JF3 = 7.6 Hz,5JF2 = 2.0 Hz, H5?), 6.60 (1H, d, 3JH5 = 16.0 Hz, H4), 6.02 (1H, s, H2), 5.59 (1H, bs, OH-phenol); 1H-NMR(0.7 CDCl3 + 0.1 DMSO-d6): delta 10.41 (1H, s, OH), 7.67 (1H, d, 3JH4? = 15.9 Hz, H5), 7.10 (1H, ddd, 3JH5? =9.5 Hz, 4JF2 = 7.7 Hz, 5JF3 = 2.2 Hz, H6?), 6.71 (1H, ddd, 3JH6? = 9.2 Hz, 4JF3 = 7.7 Hz, 5JF2 = 1.9 Hz, H5?), 6.51(1H, d, 3JH5? = 15.9 Hz, H4), 5.96 (1H, s, H2); 13C-NMR (0.7 CDCl3 + 0.1 DMSO-d6): delta 180.6 (C3), 179.3(d, 2JCF3 = 36.1 Hz, C1), 150.3 (dd, 1JF2 = 254.9 Hz, 2JF3 = 10.9 Hz, C2?), 149.3 (dd, 2JF3 = 9.7 Hz, 3JF2 = 3.4Hz, C4?), 140.0 (1JF3 = 244.4 Hz, 2JF2 = 13.9 Hz, C3?), 135.7 (t, 3JF2 = 4JF3 = 2.8 Hz, C5), 123.4 (t, 3JF2 = = 4JF3 = 3.8 Hz, C60), 120.3 (d, 4JF2 = 7.5 Hz, C4), 116.1 (d,1J = 285.7 Hz, CF3), 114.1 (d, 2JF2 = 8.9 Hz, C10), 113.0 (t, 3JF3 = 4JF2 = 2.5 Hz, C50), 95.0 (d, 3JCF3 = 1.9 Hz,C2); 19F-NMR (0.7 CDCl3 + 0.1 DMSO-d6): delta 77.6 (CF3), 138.4 (dd, 3JFF = 19.0 Hz, 4JH6 = 7.7 Hz,F20), 161.3 (ddd, 3JFF = 19.0 Hz, 4JH5 = 7.7 Hz, 5JH6 = 2.2 Hz, F30); 13C-NMR (CPMAS): d 182.6 (C1and C3), 151.0 (C20 and C40), 141.4 (C30), 136.6 (C5), 120.8 (C60), 118.4 (CF3 and C4), 114.2 (C10 andC50), 96.3 (C2); 19F-NMR (MAS): delta 74.2 (CF3), 133.9 (F2), 159.3 (F3). Anal. Calc. for C12H7F5O3:C, 49.0; H, 2.4. Found: C, 49.0; H, 2.35%. |
Tags: 367-57-7 synthesis path| 367-57-7 SDS| 367-57-7 COA| 367-57-7 purity| 367-57-7 application| 367-57-7 NMR| 367-57-7 COA| 367-57-7 structure
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