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CAS No. : | 701-49-5 | MDL No. : | MFCD00032531 |
Formula : | C8H8FNO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PIHJUDHVYWCZLS-UHFFFAOYSA-N |
M.W : | 153.15 | Pubchem ID : | 4074247 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P264-P270-P280-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
56% | With trichlorophosphate for 5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 45.5% 2: 12.4% | In chloroform-d1 for 6h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73 % Spectr. | With 1,4-diaza-bicyclo[2.2.2]octane In chloroform-d1 | |
With triethylamine In methanol; diethyl ether at 20℃; for 1h; Inert atmosphere; Schlenk technique; | ||
With triethylamine In ethanol at 20℃; for 3h; Inert atmosphere; Cooling with ice; |
With triethylamine In methanol; diethyl ether at 25℃; for 1h; | ||
With triethylamine In methanol; diethyl ether at 20℃; for 1h; Inert atmosphere; Schlenk technique; | ||
With triethylamine In dichloromethane; water monomer at 0 - 20℃; for 1h; | 2.1 Preparation of N-alkylbenzamide substrates from benzoyl chloride1: General procedure: Triethylamine (15 mmol), 33.3% methylamine in water (20 mmol) were added tothe solution of acid chloride (10 mmol) in CH2Cl2 (20 mL) at 0°C. The reactionmixture was stirred at room temperature for 1 h and monitored by TLC until thereaction was completed. Then water (50 mL) was added to the mixture and extractedwith CH2Cl2 (30 mL). The organic phase was dried over anhydrous Na2SO4 andconcentrated under reduced pressure. The residue can be purified by silica gel flashchromatography or recrystallization, and the corresponding benzamide products canbe obtained with a yield of 80-95%. | |
With potassium carbonate In water monomer; ethyl acetate at 0 - 20℃; | General procedure for the synthesis of benzamide C: General procedure: A 100-mL round bottom flask was charged with primary amine B (15 mmol), K2CO3 (20 mmol) in ethyl acetate (20 mL) and H2O (10 mL). Then, arylformyl chloride A (10 mmol) was added slowly to the reaction mixture at 0. After that, the residue was stirred at room temperature for 4-6 h. The reaction was completed by TLC monitoring, the organic phase was separated, dried over Na2SO4, and concentrated under vacuum. The residue was subjected to column chromatography on SiO2 with petroleum ether and ethyl acetate as an eluent to give the desired product C. | |
With potassium carbonate In water monomer; ethyl acetate at 0 - 20℃; | 1.1 General procedure for the synthesis of benzamide C: General procedure: A 100-mL round bottom flask was charged with primary amine B (15 mmol), K2CO3 (20mmol) in ethyl acetate (20 mL) and H2O (10 mL). Then, arylformyl chloride A (10 mmol) wasadded slowly to the reaction mixture at 0. After that, the residue was stirred at roomtemperature for 4-6 h. The reaction was completed by TLC monitoring, the organic phase wasseparated, dried over Na2SO4, and concentrated under vacuum. The residue was subjected tocolumn chromatography on SiO2 with PE-EtOAc as an eluent to give the desired product C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | at 20℃; for 70h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84 % Chromat. | With potassium metaperiodate In water at 100℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With N-Bromosuccinimide In chloroform at 20℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate In dimethyl sulfoxide at 230℃; for 0.5h; Microwave irradiation; | 6 Example 6 4- (4- [ (L-CYCLOBUTYL-4-PIPERIDINYL) OXY]-L-PIPERLDINYL)-N-METHYLBENZAMIDE HVDROCHLORIDE (E6) 1-CYCLOBUTYL-4- (4-PIPERIDINYLOXY) PIPERIDINE (D6) (0. 100g), 4-fluoro-N-methyl benzamide (D8) (0.088g) and anhydrous potassium carbonate (0.121g) were added to a 5ML Personal Chemistry microwave vial, to which DMSO (2ML) was added. The vial was sealed and heated at 230°C for 30min in an EMRYS OPTIMIZER microwave reactor. The crude reaction mixture was passed through an SCX cartridge [20g, MeOH (80ML) then 2N NH3 in MeOH (80ML)]. Purification by chromatography [silica gel, eluting with (10% NH3 in MeOH)/DCM, 0-10%] and treatment of the free base product dissolved in DCM (5ML) with HCI (1 ml, 1 M in diethyl ether), followed by evaporation and co- evaporation from acetone (3x) gave the title compound (E6) as a crystalline solid (0.074g). MS electrospray (+ion) 372 (MH+). 1H NMR 8 (DMSO-d6) : 8.17 (1H, s), 7.72 (dd, 2H, J=9.2, 2. 8), 7.04 (2H, s), 4.32-2. 81 (11 H, m, obscured by H2O), 2.74 (3H, s), 2.34 (2H, m), 2.15 (2H, m), 2.00-1. 40 (10H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With thionyl chloride for 1.5h; Heating / reflux; | 57(D) 57 (D) 4-Fluoro-N-methyl-benzimidoyl chloride A suspension of 4-fluoro-N-methyl-benzamide (CAS: 701-49-5,0. 106 g, 0.69 mmol) in thionyl chloride (202 mL, 2.78 mmol) was refluxed for lh 30min. The solvent was removed under reduced pressure, then toluene was added and the solvent was evaporated under reduced pressure to afford a yellow oil used immediately for the next step. | |
With thionyl chloride at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In dimethyl sulfoxide; at 140℃; for 48h; | To a solution of <strong>[189333-49-1]3-benzyl-3,9-diazaspiro[5.5]undecane</strong> (3.3 mmol) in anhydrous DMSO (5 mL) is added 4-fluoro-N-methylbezamide (3.9 mmol) and potassium carbonate (3.9 mmol). The resulting mixture is heated at 140 C. for 2 days. The reaction mixture is allowed to cool to rt, poured into cold water (10 mL), and extracted with EA (10 mL×3). The combined organic layers are washed with water and brine, dried over sodium sulfate, and concentrated. The crude product is purified through PTLC (4% TEA in EA) to give the title compound as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | Stage #1: 4-Fluorobenzoic acid; methylamine With triethylamine In tetrahydrofuran; 1,2-dichloro-ethane at 20℃; for 0.166667h; Stage #2: With benzotriazol-1-ol; dicyclohexyl-carbodiimide In tetrahydrofuran; 1,2-dichloro-ethane at 70℃; for 3h; | 4.D; D To a stirred solution of 4-fluorobenzoic acid (200 mg, 1.43 mmol) in DCE (3 ml) at RT, was added a solution of methyl amine in THF (2 M, 1.43mmol) and NEt3 (198 μl, 1.43 mmol) and allowed to stir for ca. 10 mins. HOBt (221 mg, 1.43 mmol) and DCC (295 mg, 1.43 mmol) were added and the reaction mixture heated at 70 0C for 3 h. After cooling to RT, the reaction mixture was washed with sat. NaHCO3 (5 ml) and the aqueous back extracted with DCM. The organics were combined, dried (MgSO4), filtered and concentrated under reduced pressure. Purification by silica flash column chromatography (eluting with DCM/MeOH gradient 100:0 to 80:20) provided the title compound as off-white solid (137 mg, 63%).LCMS data: Calculated MH+ (154); Found 100% (MH+) m/z 154.2, Rt = 1.11 min. |
Stage #1: 4-Fluorobenzoic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: methylamine With 4-methyl-morpholine In N,N-dimethyl-formamide at 0 - 20℃; | ||
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 0 - 20℃; | Method B: (A3-A5, A7-A13, A15-A23, A28) General procedure: To a solution of 4-fluorobenzoic acid (1.40 g, 10 mmol), n-propylamine (0.71 g, 12 mmol), and Et3N (2.23 g, 22 mmol) in CH2Cl2 (30 mL), was added 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) (2.31 g, 12 mmol) and 1-hydroxybenzotriazole (HOBT) (1.62 g, 12 mmol). Next, the reaction mixture was stirred at room temperature overnight. After the completion, the mixture was washed with NaHCO3 (3 times) and brine, and dried over MgSO4. Then, the organic layer was concentrated and recrystallized by adding PE, affording the 4-fluoro-N-propylbenzamide (1ab) (1.52g, yield 84%). |
Stage #1: 4-Fluorobenzoic acid With 1,1'-carbonyldiimidazole In dichloromethane at 20℃; for 0.333333h; Inert atmosphere; Stage #2: methylamine In dichloromethane; water at 20℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.7% | In dimethyl sulfoxide at 23 - 120℃; Inert atmosphere; | 11.B.11A To a solution of 4-fluoro-N-methylbenzamide (6 g, 39.2 mmol) in DMSO (Volume: 24.0 mL) was added piperazine (16.87 g, 196 mmol) at 23° C. The reaction was stirred at 120° C. for 68 hr. The reaction mixture was poured into ice (261 g) and the reaction vessel was rinsed with H2O (50 mL). Next, celite (30 g) was added to aid the filtration. The resulting suspension was warmed to 100° C., cooled to 40° C., filtered, and rinsed with warm H20 (4×50 mL). The resulting solid was dried in vacuo. The filtrate was stirred at room temperature overnight affording a suspension. The suspension was filtered, rinsed with H2O (3×25 mL), and the resulting solid was dried in vacuo. The cloudy filtrate was filtered once again through a medium fitted funnel and rinsed with H2O (3×10 mL). Added NaCl (200.1 g) to the filtrate, cooled on ice, filtered, rinsed with cold H2O (3×25 mL), and dried the resulting solid in vacuo. Re-suspended the purified product in H2O (30 mL), stirred for 30 min at 23° C., filtered, rinsed with H2O (3×5 mL), and dried the resulting solid in vacuo. The purified product was re-suspended in ACN (25 mL), agitated for 10 min, and dried in vacuo. This procedure was repeated three times to provide N-methyl-4-(piperazin-1-yl)benzamide (5.64 g, 25.7 mmol, 65.7% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.29 (br. s., 1H) 2.74 (d, J=4.55 Hz, 3H) 2.77-2.86 (m, 4H) 3.08-3.18 (m, 4H) 6.91 (m, 2H) 7.69 (m, 2H) 8.13 (q, J=4.04 Hz, 1H). ESI-MS: m/z 220.2 (M+H)+. mp=153.9-156.5° C. |
65.7% | In dimethyl sulfoxide at 23 - 120℃; for 68h; | 0601] General Procedure for nucleophilic aromatic substitution reactions with piperazine: Synthesis of 7V-methyl-4-(piperazin-l-yl)benzamide (282). To a solution of 4- fluoro-iV-methylbenzamide (6 g, 39.2 mmol) in DMSO (24.0 mL) was added piperazine (16.87 g, 196 mmol) at 23 0C. The reaction was stirred at 120 0C for 68 hr. The reaction mixture was poured into ice (261 g) and the reaction vessel was rinsed with H2O (~50 mL). Next, Celite (30 g) was added to aid the filtration. The resulting suspension was warmed to 100 0C, cooled to ~40 0C, filtered, and rinsed with warm H2O (4 x 50 mL). The resulting solid was dried in vacuo. The filtrate was stirred at room temperature overnight affording a suspension. The suspension was filtered, rinsed with H2O (3 x 25 mL), and the resulting solid was dried in vacuo. The cloudy filtrate was filtered once again through a medium fritted funnel and rinsed with H2O (3 x 10 mL). Added NaCl (200.Ig) to the filtrate, cooled on ice, filtered, rinsed with cold H2O (3 x 25 mL), and dried the resulting solid in vacuo. Re-suspended the purified product in H2O (30 mL), stirred for 30 min at 23 0C, filtered, rinsed with H2O (3 x 5 mL), and dried the resulting solid in vacuo. The purified product was re-suspended in ACN (25 mL), agitated for 10 min, and dried in vacuo. This procedure was repeated three times to provide the title compound as a white solid (5.64g, 25.7 mmol, 65.7% yield). 1H NMR (400 MHz, DMSO-J6) δ ppm 2.29 (br. s., 1 H) 2.74 (d, J=4.55 Hz, 3 H) 2.77 - 2.86 (m, 4 H) 3.08 - 3.18 (m, 4 H) 6.91 (m, 2 H) 7.69 (m, 2 H) 8.13 (q, J=4.04 Hz, 1 H). ESI-MS: m/z 220.2 (M+H)+. mp=153.9-156.5 0C. |
65.7% | In dimethyl sulfoxide at 120℃; for 68h; | To a solution of 4-fluoro-N- methylbenzamide (6 g, 39.2 mmol) in DMSO (Volume: 24.0 mL) was added piperazine (16.87 g, 196 mmol) at 23 0C. The reaction was stirred at 120 0C for 68 hr. The reaction mixture was poured into ice (261 g) and the reaction vessel was rinsed with H2O (50 rnL). Next, celite (30 g) was added to aid the filtration. The resulting suspension was warmed to 100 0C, cooled to 40 0C, filtered, and rinsed with warm H2O (4 x 50 mL). The resulting solid was dried in vacuo. The filtrate was stirred at room temperature overnight affording a suspension. The suspension was filtered, rinsed with H2O (3 x 25 mL), and the resulting solid was dried in vacuo. The cloudy filtrate was filtered once again through a medium fritted funnel and rinsed with H2O (3 x 10 mL). Added NaCl (200.Ig) to the filtrate, cooled on ice, filtered, rinsed with cold H2O (3 x 25 mL), and dried the resulting solid in vacuo. Re-suspended the purified product in H2O (30 mL), stirred for 30 min at 23 0C, filtered, rinsed with H2O (3 x 5 mL), and dried the resulting solid in vacuo. The purified product was re-suspended in ACN (25 mL), agitated for 10 min, and dried in vacuo. This procedure was repeated three times to provide N-methyl-4-(piperazin-l-yl)benzamide (5.64g, 25.7 mmol, 65.7 % yield) as a white solid. 1U NMR (400 MHz, DMSO-J6) δ ppm 2.29 (br. s., 1 H) 2.74 (d, J=4.55 Hz, 3 H) 2.77 - 2.86 (m, 4 H) 3.08 - 3.18 (m, 4 H) 6.91 (m, 2 H) 7.69 (m, 2 H) 8.13 (q, J=4.04 Hz, 1 H). ESI-MS: m/z 220.2 (M+H)+. mp=153.9-156.5 0C. |
65.7% | In dimethyl sulfoxide at 120℃; for 68h; | General Procedure for nucleophilic aromatic substitution reactions with piperazine General procedure: Synthesis of N-methyl-4-(piperazin-1-yl)benzamides (6a). To a solution of 4-fluoro-N-methylbenzamide (6 g, 39.2 mmol) in DMSO (Volume: 24.0 mL) was added piperazine (16.87 g, 196 mmol) at 23 °C. The reaction was stirred at 120 °C for 68 hr. The reaction mixture was poured into ice (261 g) and the reaction vessel was rinsed with H2O (~50 mL). Next, celite (30 g) was added to aid the filtration. The resulting suspension was warmed to 100 °C, cooled to ~40 °C, filtered, and rinsed with warm H20 (4 x 50 mL). The resulting solid was dried in vacuo. The filtrate was stirred at room temperature overnight affording a suspension. The suspension was filtered, rinsed with H2O (3 x 25 mL), and the resulting solid was dried in vacuo. The cloudy filtrate was filtered once again through a medium fritted funnel and rinsed with H2O (3 x 10 mL). Added NaCl (200.1g) to the filtrate, cooled on ice, filtered, rinsed with cold H2O (3 x 25 mL), and dried the resulting solid in vacuo. Re-suspended the purified product in H2O (30 mL), stirred for 30 min at 23 °C, filtered, rinsed with H2O (3 x 5 mL), and dried the resulting solid in vacuo. The purified product was re-suspended in MeCN (25 mL), agitated for 10 min, and dried in vacuo. This procedure was repeated three times to provide N-methyl-4-(piperazin-1-yl)benzamide ( 5.64g, 25.7 mmol, 65.7 % yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) ppm 2.29 (br. s., 1 H) 2.74 (d, J=4.55 Hz, 3 H) 2.77 - 2.86 (m, 4 H) 3.08 - 3.18 (m, 4 H) 6.91 (m, 2 H) 7.69 (m, 2 H) 8.13 (q, J=4.04 Hz, 1 H). ESI-MS: m/z 220.2 (M+H)+. mp=153.9-156.5 °C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18.67% | Stage #1: 2-methyl-6-(piperazin-1-ylmethyl)-8-propyl-2H-benzo[b][1,4]oxazin-3(4H)-one; 4-fluoro-N-methylbenzamide In dimethyl sulfoxide at 120℃; for 4h; Stage #2: With 1,8-diazabicyclo[5.4.0]undec-7-ene In dimethyl sulfoxide at 120℃; for 18h; Stage #3: With potassium carbonate In dimethyl sulfoxide at 120℃; | [0690] 7V-Methyl-4-(4-((2-methyl-3-oxo-8-propyl-3,4-dihydro-2H-benzo[6] [l,4]oxazin-6-yl)methyl)piperazin-l-yl)benzamide (358): In a 20 mL scintillation vial was added 2- methyl-6-(piperazin-l-ylmethyl)-8-propyl-2H-benzo[δ][l,4]oxazin-3(4H)-one 358E (67 mg, 0.221 mmol) and 4-fluoro-JV-methylbenzamide (50.7 mg, 0.331 mmol) in DMSO (1.104 mL) and stirred at 120 0C for 4 h. DBU (0.133 mL, 0.883 mmol) was added and the reaction mixture was stirred at 120 0C for 18h. The reaction was concentrated in vacuo to remove DBU, and then K2CO3 (61.0 mg, 0.442 mmol) was added. The mixture was heated overnight at 120 0C. The reaction was subsequently filtered and the crude material was purified by prep ΗPLC 20-45% acetonitrile in water. The appropriate fractions were collected and concentrated in vacuo to give the title compound as a yellow solid (18 mg, 0.041 mmol, 18.67 % yield). 1H NMR (DMSO-de, 400MHz): δ = 10.89 (s, 1 H), 10.73 (br. s., 1 H), 8.04 (br. s., 1 H), 7.75 (d, J=8.8 Hz, 1 H), 7.24 (s, 1 H), 7.11 (s, 1 H), 6.95 - 7.04 (m, 2 H), 6.87 (d, J=2.0 Hz, 1 H), 4.66 - 4.72 (m, 1 H), 4.64 (d, J=6.6 Hz, 2 H), 3.26 (t, J=7.1 Hz, 2 H), 3.03 (q, J=6.7 Hz, 2 H), 2.30 - 2.45 (m, 3 H), 1.61 - 1.67 (m, 2 H), 1.55 (d, J=6.8 Hz, 5 H), 1.40 (d, J=6.8 Hz, 3 H), 0.86 - 0.93 ppm (m, 3 H). ESI-MS: m/z 437 '.4 (M + H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22.85% | With potassium carbonate In dimethyl sulfoxide at 120℃; for 72h; | 7V-Methyl-4-(4-(2-methyl-3-oxo-3,4-dihydro-2H-benzo[][l,4]oxazin-6-yloxy)piperidin-l- yl)benzamide (395): In a 4 mL screw cap vial, 2-methyl-6-(piperidin-4-yloxy)-2H- benzo[6][l,4]oxazin-3(4H)-one 394E (0.054 g, 0.206 mmol), K2CO3 (0.142 g, 1.029 mmol), and 4-fluoro-iV-methylbenzamide (0.038 g, 0.247 mmol) were suspended in DMSO (0.412 mL) to give a brown suspension. The reaction was stirred at 1200C for 72 hr. The crude material was purified by prep ΗPLC-MS (40-75% MeCN in water). The fractions were collected and concentrated in vacuo affording the product as a tan solid (0.0186 g, 22.85% yield). 1U NMR (400 MHz, DMSO-Je) δ ppm 1.34 - 1.47 (m, 3 H) 1.59 - 1.74 (m, 2 H) 1.93 - 2.07 (m, 2 H) 2.71 - 2.82 (m, 3 H) 3.09 - 3.23 (m, 2 H) 3.61 (br. s., 2 H) 4.38 - 4.50 (m, 1 H) 4.58 (q, J=6.65 Hz, 1 H) 4.68 (d, J=6.57 Hz, 1 H) 6.50 (d, J=2.78 Hz, 1 H) 6.53 - 6.62 (m, 1 H) 6.67 (dd, J=8.72, 2.91 Hz, 1 H) 6.88 (d, J=8.84 Hz, 1 H) 6.94 - 7.06 (m, 2 H) 7.71 (d, J=8.84 Hz, 2 H) 7.81 - 7.88 (m, 1 H) 8.10 - 8.20 (m, 1 H) 10.57 (s, 1 H). ESI-MS: m/z 396.3 (M + H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dimethyl sulfoxide / 68 h / 120 °C 2: (cyanomethyl)trimethyl-phosphonium iodide; N-ethyl-N,N-diisopropylamine / propiononitrile / 2 h / 95 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; cyclopentylmagnesium chloride; cobalt acetylacetonate In diethyl ether at 20℃; for 12h; Cooling with ice; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; cyclohexylmagnesiumchloride; cobalt(III) acetylacetonate In diethyl ether at 0 - 25℃; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 69 %Spectr. 2: 12 %Spectr. | With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; cobalt acetylacetonate In tetrahydrofuran at 25℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In tert-Amyl alcohol at 100℃; for 22h; Inert atmosphere; | |
41% | With sodium iodide dihydrate; palladium 10% on activated carbon; potassium acetate; caesium carbonate In N,N-dimethyl-formamide at 120℃; for 36h; Schlenk technique; | 3.2. General procedure General procedure: A mixture of a substituted benzamide (1) (0.3 mmol, 1.0 equiv),an alkyne (2) (0.6 mmol or 0.9 mmol, 2.0 equiv or 3.0 equiv),10% Pd/C (0.03 mmol, 10 mol%, Alfa Aesar, No. 044696, eggshell,reduced), NaI·2H2O (0.6 mmol, 2.0 equiv), Cs2CO3 (0.3 mmol, 1.0equiv), and KOAc (0.6 mmol, 2.0 equiv) was weighted in a Schlenktube equipped with a stir bar. DMF (1.0 mL) was added and themixture was stirred at 120 °C for 36 h under air. Afterwards, themixture was filtered and washed with H2O (30 mL) and extractedwith CH2Cl2 (3×30 mL). The combined organic phase was driedwith anhydrous Na2SO4. After removal of solvents under reducedpressure, the residue was absorbed to small amounts of silica. Thepurification was performed by flash column chromatography onsilica gel with EA:PE (Petroleum ether) = 1:5 or 1:10 as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In tert-Amyl alcohol at 100℃; for 22h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium carbonate In diethyl ether at 20℃; | |
With potassium carbonate In water; ethyl acetate at 0 - 20℃; | ||
With triethylamine In dichloromethane at 0 - 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hexafluorophosphate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In tert-Amyl alcohol at 100℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62% 2: 6% | With potassium hexafluorophosphate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In water at 100℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 67% 2: 9% | With [RhCl2(p-cymene)]2; copper(II) acetate monohydrate In tert-Amyl alcohol at 100℃; for 22h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With trifluoroacetic acid In acetonitrile at 92℃; for 0.25h; Inert atmosphere; UV-irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With rhenium(I) pentacarbonyl bromide; phenylmagnesium bromide In tetrahydrofuran at 150℃; for 18h; Inert atmosphere; Schlenk technique; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With rhenium(I) pentacarbonyl bromide; phenylmagnesium bromide In tetrahydrofuran at 120℃; for 24h; Inert atmosphere; Schlenk technique; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: thionyl chloride / dichloromethane; N,N-dimethyl-formamide / 3 h / 60 °C / Inert atmosphere; Schlenk technique 2: triethylamine / diethyl ether; methanol / 1 h / 20 °C / Inert atmosphere; Schlenk technique | ||
Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / dichloromethane / 3 h / 60 °C / Inert atmosphere; Schlenk technique 2: triethylamine / diethyl ether; methanol / 1 h / 20 °C / Inert atmosphere; Schlenk technique | ||
Multi-step reaction with 2 steps 1: oxalyl dichloride / dichloromethane 2: triethylamine / dichloromethane / 8 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With copper(l) chloride In chlorobenzene at 130℃; for 12h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 23℃; for 3h; | General Procedure for coupling of amines to carboxylic acids General procedure: To a suspension of 3-chloro-4-fluorobenzoic acid (25.0 g, 143 mmol), Methylamine hydrochloride (11.60 g, 172 mmol), N1-((ethylimino)methylene)-N3,N3-dimethylpropane-1,3-diamine hydrochloride (41.2 g, 215 mmol), and 1H-benzo[d][1,2,3]triazol-1-ol hydrate (32.9 g, 215 mmol) in DMF (Volume: 150 mL) was added 4-methylmorpholine (79 mL, 716 mmol) at 23 °C. The reaction was stirred at 23 °C for 3 hr. The reaction mixture was diluted with water (500 mL) to furnish a yellow-orange solution. The solution was stirred overnight at 23°C affording a suspension. The suspension was filtered, washed with H2O (3 x 100 mL), and the resulting solid was dried in vacuo at 30 °C to provide 3-chloro-4-fluoro-N-methylbenzamide ( 14.24 g, 76 mmol, 53.0 % yield) as an off-white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 4-fluoro-N-methylbenzamide With 2,6-dimethylpyridine; trifluoromethylsulfonic anhydride In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: 2-Fluoroaniline In dichloromethane at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 2,6-dimethylpyridine; trifluoromethylsulfonic anhydride / dichloromethane / 1 h / 0 - 20 °C / Inert atmosphere 1.2: 20 °C / Inert atmosphere 2.1: potassium hydroxide / dimethyl sulfoxide / 16 h / 120 °C / Inert atmosphere; Sealed tube |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With ammonium peroxydisulfate; silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 In 1,2-dichloro-ethane at 100℃; for 24h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80 %Spectr. | With [RuCl2(Ph2PCH2CH2NH2)2]; potassium <i>tert</i>-butylate; hydrogen; zinc(II) trifluoroacetate In 1,4-dioxane at 100℃; for 18h; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; silver(I) acetate In 1,2-dichloro-ethane at 60℃; for 13h; Inert atmosphere; regioselective reaction; | 4 General procedure: To a dried screw-capped vial were added benzamide 2 (0.10mmol), ethyl acrylate 3 (0.15mmol), 1b (4.8mg, 0.01mmol), AgSbF6 (6.8mg, 0.02mmol), AgOAc (41.7mg, 0.25mmol), and 1,2-dichloroethane (1.0mL) under Ar atmosphere. The vial was capped and the mixture was heated at 60°C for 13h with stirring. After the mixture was cooled to room temperature, saturated EDTA·2Na aqwas added following dilution with CH2Cl2. Organic layer was separated and aqueous layer was extracted with CH2Cl2 (×2). Combined organic layers were dried over Na2SO4. After filtration and evaporation, obtained crude mixture was purified by silica gel column chromatography (CH2Cl2/EtOAc) to give product3.4.1.1 _4.1.4 (E)-Ethyl 3-(5-fluoro-2-(methylcarbamoyl)phenyl)acrylate (4d) A colorless solid; IR (KBr) ν 3082, 2984, 1721, 1635, 1558, 1321, 1182, 1034, 971, 855 cm-1; 1H NMR (CDCl3, 400 MHz) δ 1.30 (t, J=6.8 Hz, 3H), 2.99 (d, J=5.0 Hz, 3H), 4.24 (q, J=6.8 Hz, 2H), 5.95 (br s, 1H), 6.34 (d, J=16.5 Hz, 1H), 7.04 (ddd, J=2.8, 8.7, 8.7 Hz, 1H), 7.25 (dd, J=2.8, 10.1 Hz, 1H), 7.44 (dd, J=6.0, 8.7 Hz, 2H), 7.91 (d, J=16.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 60.9, 113.9 (d, J=22.9 Hz), 116.8 (d, J=22.9 Hz), 122.1, 130.6 (d, J=9.5 Hz), 133.4 (d, J=2.9 Hz), 135.5 (d, J=7.6 Hz), 140.8 (d, J=2.9 Hz), 163.5 (d, J=254.7 Hz), 166.3, 168.6; HRMS (ESI): m/z calculated for [M+Na]+: 274.0850, found: 274.0844. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | Stage #1: 4-fluoro-N-methylbenzamide With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; cobalt(II) aceylacetonate; 1,3-dicyclohexyl-1H-imidazol-3-ium chloride at 0℃; for 0.0833333h; Stage #2: para-chlorotoluene With cyclohexylmagnesiumchloride In tetrahydrofuran at 0 - 60℃; for 0.5h; Inert atmosphere; Schlenk technique; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; acetic acid In 1,2-dichloro-ethane at 20℃; for 24h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With silver hexafluoroantimonate; [RhCl2(p-cymene)]2 In 1,2-dichloro-ethane at 120℃; for 20h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine; dmap / dichloromethane / 35 °C 2: 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; potassium phosphate / N,N-dimethyl-formamide / 100 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine; dmap / dichloromethane / 35 °C 2: potassium phosphate; copper(l) iodide; oxygen / N,N-dimethyl-formamide / 90 °C / 760.05 Torr |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dmap; triethylamine In dichloromethane at 35℃; | ||
With dmap; triethylamine In dichloromethane at 0 - 20℃; | ||
With dmap; triethylamine In dichloromethane at 35℃; | General procedure for the preparation of N-alkyl-N-methacryloyl benzamides 1 General procedure: Methacryloyl chloride (2 equiv.) was added to a mixture of amide (1 equiv.), triethylamine (2 equiv.) and DMAP (0.1 equiv.) in dichloromethane (20 mL). The resulted mixture was stirred at 35 oC for 10-12 h. The reaction was quenched with saturated aqueous Na2CO3 (5 mL), and then the mixture was extracted with dichloromethane (3 x 5 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate as the eluent) affording the corresponding N-alkyl-N-methacryloyl benzamides 1. |
With dmap; triethylamine In dichloromethane at 0 - 20℃; | ||
With dmap; triethylamine In dichloromethane at 0 - 20℃; | 3.2 General procedure for synthesis of acryloylbenzamides 1: General procedure: A 100-mL round bottom flask was charged with benzamide C (10 mmol), 4-dimethylaminopyridine (DMAP) (1mmol), triethylamine (20 mmol) in dichloromethane (20 mL) and methacryloyl chloride D (15mmol) was added slowly to the reaction mixture at 0. After that, the residue was stirred at room temperature for 4-6 h. The reaction was completed by TLC monitoring, the organic phase was separated, dried over Na2SO4, and concentrated under vacuum. the residue was subjected to column chromatography on SiO2 with petroleum ether and ethyl acetate as an eluent to give the desired products 1. | |
With dmap; triethylamine In dichloromethane at 0 - 20℃; | 1.2 General procedure for synthesis of acryloylbenzamides 1: General procedure: A 100-mL round bottom flask was charged with benzamide C (10 mmol), DMAP(1mmol), triethylamine (20 mmol) in dichloromethane (20 mL) and methacryloyl chloride D(15mmol) was added slowly to the reaction mixture at 0. After that, the residue was stirredat room temperature for 4-6 h. The reaction was completed by TLC monitoring, the organicphase was separated, dried over Na2SO4, and concentrated under vacuum. the residue wassubjected to column chromatography on SiO2 with PE-EtOAc as an eluent to give the desiredproducts 1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In dichloromethane at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: triethylamine; titanium tetrachloride / dichloromethane / 0 °C 2.1: toluene / 12 h / Reflux 3.1: copper(l) chloride; (S)-(+)-5,5’-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3-benzodioxole; sodium methylate / dichloromethane / 0.17 h / 20 °C / Inert atmosphere 3.2: 18 h / 10 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine; titanium tetrachloride / dichloromethane / 0 °C 2: toluene / 12 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine; titanium tetrachloride / dichloromethane / 0 °C 2: toluene / 12 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: triethylamine; titanium tetrachloride / dichloromethane / 0 °C 2.1: toluene / 12 h / Reflux 3.1: copper(l) chloride; sodium t-butanolate; (S)-(-)-(6,6’-dimethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) / tetrahydrofuran / 0.17 h / 20 °C / Inert atmosphere 3.2: 12 h / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With titanium tetrachloride; triethylamine In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With palladium diacetate; trifluoroacetic acid In 1,2-dichloro-ethane at 25℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With rhenium(I) pentacarbonyl bromide; lithium tert-butoxide at 140℃; for 36h; Schlenk technique; Inert atmosphere; | 2 Example 2 3-Ethyl-3-benzyl-5-fluoro-N-methylisoindolinone (Formula I-b) To a 25 mL Schlenk bottle, under N2 protection,5-fluoro-N-methylbenzamide (formula II-b) (1 mmol, 153.1 mg)1-phenyl-1-butyne (formula III-a) (1 mmol, 130 mg)Catalyst pentacarbonyl rhenium bromide (0.025 mmol, 10.2 mg),Lithium tert-butoxide (0.3 mmol, 24 mg) andSolvent anisole (4 mL),At 140 ° C,After 36 h the reaction was quenched with saturated NaHCO3 solution (10 mL)And then extracted with methylene chloride, the organic phase was combined, dried with anhydrous sodium sulfate, filtered and dried.Purification by column chromatography (eluent: petroleum ether: ethyl acetate = 5/1, v / v) gave 261 mg of the desired product (Formula I-a) in 92% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 0 - 20 °C 2: toluene-4-sulfonic acid; oxygen / 1,2-dichloro-ethane / 12 h / 60 °C / Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With silver hexafluoroantimonate; [RhCl2(p-cymene)]2; oxygen; copper(II) acetate monohydrate In acetic acid at 120℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tert.-butylhydroperoxide; iodine In water; acetonitrile at 70℃; for 18h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; 1-Adamantanecarboxylic acid In 1,2-dichloro-ethane at 100℃; for 1h; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium peroxymonosulfate sulfate; water; potassium bromide In dichloromethane at 40℃; for 12h; Sealed tube; Irradiation; | N-Propionylbenzamide (B1); Typical Procedure General procedure: N-Propylbenzamide (A1) (40.8 mg, 0.25 mmol, 1.0 equiv), Oxone(307.8 mg, 0.50 mmol, 2.0 equiv), KBr (8.9 mg, 0.075 mmol, 0.3equiv), H2O (198.2 mg, 44 equiv, 0.2 mL) and CH2Cl2 (1.5 mL) wereadded to a 15 mL sealed tube containing a magnetic stir bar. The reaction mixture was stirred at room temperature for 7 hours under irradiation with an 8 W white LED. After completion of the reaction, saturated Na2SO3 (5.0 mL) was added and the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined organics were washed with brine(10 mL), dried over Mg2SO4, filtered and concentrated. The residue was purified by flash column chromatography on silica gel (EtOAc/PE,1:6) to afford N-propionylbenzamide (B1). 3b White solid; yield: 37.7 mg (85%); mp 93-94 °C (Lit. 3b 93-94 °C).1 H NMR (400 MHz, CDCl 3 ): δ = 8.54 (br s, 1 H), 7.84 (d, J = 7.2 Hz, 2 H),7.61 (t, J = 7.6 Hz, 1 H), 7.51 (t, J = 8.0 Hz, 2 H), 3.04 (q, J = 7.2 Hz, 2 H),1.23 (t, J = 7.6 Hz, 3 H).13 C NMR (100 MHz, CDCl 3 ): δ = 177.8, 166.0, 133.3, 133.0, 129.1,128.0, 31.5, 8.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide In 1,2-dichloro-ethane at 120℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide In 1,2-dichloro-ethane at 120℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With di-tert-butyl peroxide; Methyltriphenylphosphonium bromide; caesium carbonate; nickel dichloride at 130℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With C30H24Cl2N3O2PPd2S; caesium carbonate In methanol at 60℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With C30H24Cl2N3O2PPd2S; caesium carbonate In methanol at 60℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With C30H24Cl2N3O2PPd2S; caesium carbonate In methanol at 60℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C30H24Cl2N3O2PPd2S; caesium carbonate In methanol at 60℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; manganese(III) triacetate dihydrate; silver(l) oxide In 1,2-dichloro-ethane at 110℃; for 15h; Sealed tube; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With silver tetrafluoroborate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In 1,2-dichloro-ethane at 110℃; for 32h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: ortho-tolylmagnesium bromide With C9H21NO4Ti In tetrahydrofuran at 20℃; Inert atmosphere; Stage #2: With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #3: 4-fluoro-N-methylbenzamide Further stages; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: (2-isopropylphenyl)magnesium bromide With C9H21NO4Ti In tetrahydrofuran at 20℃; Inert atmosphere; Stage #2: With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #3: 4-fluoro-N-methylbenzamide Further stages; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: 4-flourophenylmagnesium bromide With C9H21NO4Ti In tetrahydrofuran at 20℃; Inert atmosphere; Stage #2: With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #3: 4-fluoro-N-methylbenzamide Further stages; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: 4-fluoro-N-methylbenzamide; 2-methylphenyl aldehyde With rhenium(I) pentacarbonyl bromide; dimethyl zinc(II); zinc dibromide In 1,2-dimethoxyethane; toluene at 130℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: With hydrogenchloride In 1,2-dimethoxyethane; water; toluene at 80℃; for 3h; Inert atmosphere; Schlenk technique; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.6% | With dmap In dichloromethane at 25℃; for 16h; | 5.1 (1) 5-1 (153 mg, 1 mmol) was dissolved in CH2Cl2 (5 mL), to which was added DMAP (244 mg, 2 mmol) under stirring, followed by addition of Boc anhydride (436 mg, 2 mmol). The resultant mixture was allowed to react 16 h at room temperature, till the reaction was completed by TLC detection. The reaction system was washed with 0.1 N HCl aqueous solution until DMAP was cleaned off. The organic layer was washed with saturated NaHCO3 aqueous solution and NaCl aqueous solution, respectively, then dried with anhydrous Na2SO4, rotatory evaporated, and purified by thin-layer column chromatography (PE/EA=2:1), to obtain white solid product (5-2, 200 mg), with a yield of 93.6%. (0100) MS (ESI) m/z 198.2 ([M-56+H]+). |
77% | With dmap In dichloromethane at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 0 - 20 °C 2: ammonium peroxydisulfate; eosin B disodium salt / dimethyl sulfoxide / 12 h / 20 °C / Irradiation; Sealed tube |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With 2-fluoropyridine; silver trifluoromethanesulfonate; Selectfluor; cesium fluoride In dichloromethane; chlorobenzene at 20℃; for 24h; Schlenk technique; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; zinc diacetate In 2,2,2-trifluoroethanol at 100℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; sodium pivalate In tert-Amyl alcohol; water at 100℃; for 18h; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; 1,1,1,3',3',3'-hexafluoro-propanol; 1-Adamantanecarboxylic acid; copper(II) acetate monohydrate at 60℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With [{Ru(CH3CN)3(p-cymene)}{SbF6}2]; Trimethylacetic acid In 1,4-dioxane at 120℃; for 48h; Inert atmosphere; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92 %Spectr. | With La(CH2C6H4NMe2-o)3 on SBA-15 In benzene-d6 at 120℃; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With palladium diacetate; trifluoroacetic acid In 1,2-dichloro-ethane at 25℃; for 24h; Inert atmosphere; | 4.1 General procedure for the chlorodifluoroethylation: General procedure: To a 25 mL screw-capped tube with a magnetic stir bar was added the amidederivatives (1 mmol), Pd(OAc)2 (10 mol%,), 2-chloro,2,2-difluoroethyl(mesityl)iodonium triflate (1.0-1.2 equiv). Then, under a nitrogen atmosphere, 2.5 mldichloroethane was added as a solvent, followed by the addition of TFA (1.2-1.5equiv.), the resulting mixture was stirred at room temperature for 24 h. Thecompletion of the reaction was detected by TLC analysis (DCM/MeOH). When thereaction was accomplished, the reaction mixture was extracted with dichloromethane(15 mL). The organic layer was dried with anhydrous sodium sulfate Na2SO4 and wasconcentrated under reduced pressure. The crude residue was purified by columnchromatography to delivered the desired products(DCM/MeOH=200:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0 - 20 °C 2: triethylamine; 3C12H16O8S2(2-)*6Na(1+)*C58H42N2 / water / 24 h / 20 °C / Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With La(CH<SUB>2</SUB>C<SUB>6</SUB>H<SUB>4</SUB>NMe<SUB>2</SUB>-o)<SUB>3</SUB> In benzene-d6 at 120℃; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 0 - 20 °C 2: eosin Y disodium salt; sodium peroxodisulphate / water monomer; dimethyl sulfoxide / 15 h / 20 °C / Schlenk technique; Inert atmosphere; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 0 - 20 °C 2: potassium peroxodisulfate; tris(2,2′-bipyridine)ruthenium(II) dichloride hexahydrate / 1,2-dichloro-ethane; water monomer / 36 h / 20 °C / Inert atmosphere; Schlenk technique; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 0 - 20 °C 2: [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine-N1,N1']bis[2-(2-pyridinyl-N)phenyl-C]iridium(III) hexafluorophosphate / water monomer; dimethyl sulfoxide / 12 h / 20 °C / Schlenk technique; Inert atmosphere; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In Carbon tetrachloride at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With C20H25Cl2CoN3; sodium triethylborohydride In 1,2-dimethoxyethane at 100℃; for 6h; Inert atmosphere; | 2 Example 2: Reduction of N-methyl-4-fluorobenzamide to N-methyl-4-fluorobenzylamine: Under an inert atmosphere, the substrate N-methyl-p-fluorobenzamide (153 mg, 1 mmol), polymethyl hydrosiloxane (668 μL, 3 mmol), and Co-2 catalyst (9.0 mg, 0.02 mmol) were sequentially added to the reaction tube. ), sodium triethylborohydride (40 μL, 0.04 mmol) and ethylene glycol dimethyl ether (2 mL), and the resulting mixture was stirred well.The reaction was carried out in an oil bath at 100 °C for 6 h, the reaction system was cooled to room temperature, ethyl acetate and saturated NaOH aqueous solution were added to dilute and quench, the layers were separated, the organic phase was taken, dried and concentrated. 92mg yellow Oily liquid, yield: 66%. |
Tags: 701-49-5 synthesis path| 701-49-5 SDS| 701-49-5 COA| 701-49-5 purity| 701-49-5 application| 701-49-5 NMR| 701-49-5 COA| 701-49-5 structure
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P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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