Structure of 5348-42-5
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CAS No. : | 5348-42-5 |
Formula : | C6H6Cl2N2 |
M.W : | 177.03 |
SMILES Code : | NC1=CC(Cl)=C(Cl)C=C1N |
MDL No. : | MFCD00007723 |
InChI Key : | IWFHBRFJOHTIPU-UHFFFAOYSA-N |
Pubchem ID : | 79297 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302+H312+H332-H315-H319-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; at 108℃; for 18h; | 4,5-Dichloro-benzene-1,2-diamine (2.01 g; 11.4 mmoles) and 2,2,3,3,3- pentafluoro-propionic acid (1.80 mL; 17.3 mmoles) were suspended in 6N HCl (10 ml 60 mmoles) under a nitrogen atmosphere. The reaction was stirred vigorously and heated to 108°C for 18 hrs, then cooled to room temperature. The reaction was diluted with water (60 mL) and with ethyl acetate (60 mL), then sodium bicarbonate (7.59g; 90.3 mmoles) was added slowly and in portions to quench the reaction. The aqueous layer was separated and extracted with ethyl acetate (3x30 mL). The extracts were combined, washed with water (30 mL) and brine (30 mL), then dried over Na2SO4. The filtrate was concentrated in vacuo to yield a crude brown solid which was then purified by column chromatography (SiO2; 100percent CH2Cl2) to yield the title compound as a light tan solid. 1H NMR (400 MHz, CD3CN) delta 7.94 (s, 2H) MS calculated for C9H3Cl2F5N2: 303.96 MS measured: 305, 307 (M+H); 303, 305 (M-H). | |
4,5-Dichloro-benzene-1 , 2-diamine (2.01 g; 11.4 mmoles) and 2,2,3,3,3- pentafluoro-propionic acid (1.80 ml 17.3 mmoles) were suspended in 6N HCI (10 ml 60 mmoles) under a nitrogen atmosphere. The reaction was stirred vigorously and heated to 1080C for 18 hrs, then cooled to room temperature. The reaction was diluted with water (60 ml_) and with ethyl acetate (60 mL), then sodium bicarbonate (7.59g; 90.3 mmoles) was added slowly and in portions to quench the reaction. The aqueous layer was separated and extracted with ethyl acetate (3x30 mL). The extracts were combined, washed with water (30 mL) and brine (30 mL), then dried over Na2SO4. The filtrate was concentrated in vacuo to yield a crude brown solid which was then purified by column chromatography (SiO2; 100percent CH2CI2) to yield the title compound as a light tan solid.1H NMR (400 MHz, CD3CN) delta 7.94 (s, 2H) MS calculated for C9H3CI2F5N2: 303.96 MS measured: 305, 307 (M+H); 303, 305 (M-H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; In toluene; for 3h;Reflux; | Example 2 5,6-Dichloro-1,2-Dimethyl-Benzoimidazole (2) Triethyl orthoacetate (4.6 g, 1 eq) was added drop wise to a refluxing mixture of 4,5-dichloro-1,2-phenylenediamine (5 g, 1 eq) and a catalytic amount of p-toluenesulfonic acid in toluene (40 mL). The mixture was refluxed for 3 hrs and 5.7 g black solid was collected after evaporation of the solvents under reduced pressure and used directly in the following step without further purification. ESI-MS (m/z) calcd (found): 200.0 (201.1) for [M+H]+. To the crude 5,6-dichloro-2-methyl-benzoimidazole (5.7 g, 1 eq) (see ) and grinded potassium hydroxide (4.8 g, 3 eq) in acetone (50 mL) was added iodomethane (5.2 g, 1.4 eq) drop wise and the mixture was stirred overnight. The solvent was evaporated under reduced pressure and the residue was partitioned between dichloromethane (200 mL) and water (200 mL). The aqueous phase was washed two times with dichloromethane (200 mL) and the combined organic phase was dried over Na2SO4 and evaporated to dryness. The crude product was recrystallized from ethyl acetate. 5.5 g product was collected as pale flakes with 90.6% yield for two steps. 1H NMR: (CDCl3) 2.55 (s, 3H), 3.63 (s, 3H), 7.28 (s, 1H), 7.68 (s, 1H). 13C NMR: (CDCl3): 13.82, 30.05, 110.20, 120.00, 125.58, 125.75, 134.97, 141.83, 153.93. ESI-MS (m/z) calcd (found): 214.0 (215.1) for [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The 1,2-diaminobenzene (1) (30.0 mmol, 1 equiv.) is dissolved in DMF (25 ml). Acetic acid (3.0 ml) is added followed by the appropriate α-ketoester (30.0 mmol, 1 equiv.). The solution is stirred at ambient temperature for 30 min. The reaction volume is reduced to one-third by evaporation in vacuo. Water (20 ml) is added, and the resulting suspension is chilled on an ice bath for 20 min. The precipitated 3-substituted quinoxaline-2-one (2) is collected by filtration, and dried in vacuo overnight. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In 1,4-dioxane; at 40℃;Cooling with ice; | The solution of commercial 4,5-dichloro-l,2-phenylenediamine (0.36 g) and triethyl amine (0.32 ml) in 1,4-dioxane (1.5 ml) was added to a solution of 3-(4- chlorophenyl)glutaric anhydride (0.45 g) in 1,4-dioxane (1 ml) with ice cooling. The resulting mixture was stirred at rt for 0.5 h and at 400C for 0.5 h. Again under ice cooling IM HCI (3 ml) was added dropwise. A gummy precipitate is formed. After 0.5 h of cooling the aqueous layer is removed by decantation and the residue is dissolved in methanol. The dark solution is decolourised with activated carbon, filtered, and the filtrate concentrated in vacuo. The amorphous solid is redissolved in ethanol (6 ml) and cone. HCI (2 ml) and stirred at reflux for 16 h. After cooling to rt the pH is adjusted to 8 by addition of first NaOH solution, then sat. sodium bicarbonate solution. The aqueous layer is extracted with dichloromethane (40 ml) and the organic layer is washed with sat. sodium chloride solution and dried (sodium sulfate). After concentration the crude (0.46 g) is purified by flash chromatography ((dichloromethane/2% methanol/1% triethyl amine) on silica gel to afford ethyl 4-(5,6-dichloro-2-benzimidazolyl)-3-(4-chlorophenyl)butanoate (0.33 g) as yellowish, amorphous solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The solution of commercial 4,5-dichloro-l,2-phenylenediamine (0.38 g) and 3- phenylglutaric anhydride (0.4 g) in THF (1 ml) was heated shortly and kept at rt for 0.5 h. The solvent was removed in vacuo and the residue redissolved in acetic acid (3 ml). The dark solution was heated to reflux overnight. Then all volatiles were removed in vacuo and the residue was heated with ethanol (5 ml). After reccoling to rt the precipitate was collected by filtration, washed with ethanol, and dried to give a crude (0.39 g). The crude was decolourised in boiling acetone solution with activated carbon and filtered over Celite. Concentration of the filtrate and drying of the residue afforded 7,8-dichloro-3-phenyl-3,4-dihydropyrido[l,2-a]benzimidazol- l(2H)-one (0.13 g) as colourless crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The solution of commercial 4,5-dichloro-1,2-phenylenediamine (0.36 g) and triethyl amine (0.32 ml) in 1,4-dioxane (1.5 ml) was added to a solution of <strong>[53911-68-5]3-(4-chlorophenyl)glutaric anhydride</strong> (0.45 g) in 1,4-dioxane (1 ml) with ice cooling. The resulting mixture was stirred at rt for 0.5 h and at 40 C. for 0.5 h. Again under ice cooling 1M HCl (3 ml) was added dropwise. A gummy precipitate is formed. After 0.5 h of cooling the aqueous layer is removed by decantation and the residue is dissolved in methanol. The dark solution is decolourised with activated carbon, filtered, and the filtrate concentrated in vacuo. The amorphous solid is redissolved in ethanol (6 ml) and conc. HCl (2 ml) and stirred at reflux for 16 h. After cooling to rt the pH is adjusted to 8 by addition of first NaOH solution, then sat. sodium bicarbonate solution. The aqueous layer is extracted with dichloromethane (40 ml) and the organic layer is washed with sat. sodium chloride solution and dried (sodium sulfate). After concentration the crude (0.46 g) is purified by flash chromatography ((dichloromethane /2% methanol /1% triethyl amine) on silica gel to afford ethyl 4-(5,6-dichloro-2-benzimidazolyl)-3-(4-chlorophenyl)butanoate (0.33 g) as yellowish, amorphous solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With gadolinium(III) chloride hexahydrate; at 80℃; for 5.5h; | General procedure: To a mixture of o-aromatic diamines (200 mg, 1.85 mmol) and 1,3-dicarbonyl compound (722 mg, 5.55 mmol), GdCl3*6H2O (25 mg, 0.09 mmol) was added and the mixture was stirred at 80C for 3.0 hr. After completion of the reaction (TLC), the reaction mixture was poured into ice cold water and extracted with ethyl acetate. The organic layer was dried over sodium sulphate and concentrated under reduced pressure to afford the corresponding 2-methyl benzimidazole. The crude material was further purified by through column chromatography by using 10% ethyl acetate in hexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With Imidazole hydrochloride; In 5,5-dimethyl-1,3-cyclohexadiene;Heating; | General procedure: A mixture of 1a (0.54 g, 5 mmol), imidazolium chloride (0.09 g, 0.5 mmol) and N, N-dimethylbenzamide (0.55 g, 7.5 mmol) in 5mL xylene was heated to 140 C and stirred at this temperature for 8 h. When the reaction was completed, 50mL water was added and the resulting mixture was extracted with 50 mL ethyl acetate twice. The combined organic layer was successively washed with H2O (50 mL) and then brine (50 mL), then dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using petroleum ether and ethyl acetate as the eluent or recrystallized from petroleum ether/EA to give the desired products. |
69% | With Imidazole hydrochloride; In 5,5-dimethyl-1,3-cyclohexadiene; for 6h;Heating; | General procedure: A mixture of 1a (0.54 g, 5 mmol), imidazole hydrochloride (0.09 g, 0.5 mmol) and N,N-dimethylbenzamide (0.55 g, 7.5 mmol) in 5 mL of xylene was heated to 140 C and the reaction was stirred at this temperature, TLC spot plate was taken, and when the reaction was completed, 50 mL of water was added, and the obtained mixture was extracted twice with 50 mL of ethyl acetate. The combined organic layers were washed sequentially with EtOAc (50 mL) then brine.It was then dried over anhydrous Na2SO4, filtered and evaporated.The residue was purified by silica gel column chromatography. Recrystallization from petroleum ether/EA using petroleum ether and ethyl acetate as eluent gave the desired product. |
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