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CAS No. : | 615-47-4 | MDL No. : | MFCD00016619 |
Formula : | C6H11Cl2N3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RKMFFOLUBJFMBQ-UHFFFAOYSA-N |
M.W : | 196.08 | Pubchem ID : | 94179 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
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 |
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With ethanol; water |
Yield | Reaction Conditions | Operation in experiment |
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With 50percent PPA at 230 - 250℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
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With 50percent PPA at 180℃; for 2h; Yields of byproduct given; | ||
With 50percent PPA at 180℃; for 2h; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
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With triethylamine In N,N-dimethyl acetamide for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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90% | With pyridine; lithium chloride In various solvent(s) at 180℃; |
Yield | Reaction Conditions | Operation in experiment |
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92.6% | In methanol; diethyl ether | 2,3-Bis(3-hydroxyphenyl)quinoxalin-6-ylamine dihydrochloride salt 2,3-Bis(3-hydroxyphenyl)quinoxalin-6-ylamine dihydrochloride salt 40.4 mg (0.206 mmol) of 1,2,4-benzenetriamine dihydrochloride and 50 mg (0.20 mmol) of 3,3'-dihydroxybenzil were dissolved in 2 mL of 1:1 mixture of dioxane-water. The reaction was refluxed for 3 hours. Then solvent was removed in vacuo. The residue was dissolved in 2 mL of methanol and this solution was added dropwise to 40 mL of diethyl ether. The formed dark-red precipitate was collected, washed with ether and dried in vacuo to give 69.8 mg (92.6% yield) of the product. 97.6% purity by LC/MS (230 DAD). Mass-spec [ES+]=330.8. 1H NMR (500 MHz, MeOH-d4) 6.81-6.87 (2H, m), 6.96-6.98 (4H, m), 7.10 (1H, m), 7.13-7.16 (1H, t), 7.28-7.31 (1H, t), 7.56-7.58 (1H, m), 8.04-8.06 (1H, d). |
Yield | Reaction Conditions | Operation in experiment |
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83.7% | In methanol; diethyl ether; | 2,3-Bis(4-hydroxyphenyl)quinoxalin-6-ylamine dihydrochloride salt 98.04 mg (0.5 mmol) of 1,2,4-benzenetriamine dihydrochloride and 121.2 mg (0.5 mmol) of <strong>[33288-79-8]4,4'-dihydroxybenzil</strong> were dissolved in 2 ml of 1:1 mixture of dioxane-water. The reaction was refluxed for 3 hours. Then solvent was removed in vacuo. The residue was dissolved in 2 ml of methanol and this solution was added dropwise to 40 ml of diethyl ether. The formed dark-red precipitate was collected, washed with ether and dried in vacuo to give 168.3 mg (83.7% yield) of the product. 98.7% purity by LC/MS (230 DAD). Mass-spec [ES+]=330.8. 1H NMR (500 MHz, MeOH-d4) 6.76-6.77 (2H, d), 6.87-6.89 (2H, d), 7.05-7.06 (1H, d), 7.29-7.31 (2H, d), 7.38-7.40 (2H, d), 7.50-7.52 (1H, m), 7.99-8.01 (1H, d). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.7% | In methanol; diethyl ether | 2,3-Bis(3,4-dihydroxyphenyl)quinoxalin-6-ylamine dihydrochloride salt 2,3-Bis(3,4-dihydroxyphenyl)quinoxalin-6-ylamine dihydrochloride salt 98.0 mg (0.5 mmol) of 1,2,4-benzenetriamine dihydrochloride and 137.1 mg (0.5 mmol) of 3,3',4,4'-tetrahydroxybenzil were dissolved in 3 ml of MeOH. The reaction was refluxed for 6 hours. Then the reaction mixture was cooled to r.t. and added dropwise to 40 ml of diethyl ether. The formed dark-red precipitate was collected, washed with ether and dried in vacuo to give 184.0 mg (84.7% yield) of the product. 97.7% purity by LC/MS (230 DAD). Mass-spec [ES+]=362.8. 1H NMR (MeOH-d4) 6.73-6.75 (1H, d), 6.78-6.80 (1H, m), 6.88-6.89 (1H, m), 6.94-6.97 (3H, m), 7.03 (1H, d), 7.49-7.51 (1H, dd), 7.97-7.99 (1H, d). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane; water for 3h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: Et3N / N,N-dimethyl-acetamide / 1 h 2: 90 percent / 0.17 h / 300 - 330 °C 3: aq. H2SO4 / 12 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Et3N / N,N-dimethyl-acetamide / 1 h 2: 90 percent / 0.17 h / 300 - 330 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: Et3N / N,N-dimethyl-acetamide / 1 h 2: 90 percent / 0.17 h / 300 - 330 °C 3: aq. H2SO4 / 12 h / Heating 4: 75 percent / N,N-dimethyl-acetamide 5: 72 percent / H2 / Pd/C / dimethylacetamide contg. 3percent LiCl, ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Et3N / N,N-dimethyl-acetamide / 1 h 2: 2 percent / 0.17 h / 300 - 330 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: Et3N / N,N-dimethyl-acetamide / 1 h 2: 90 percent / 0.17 h / 300 - 330 °C 3: aq. H2SO4 / 12 h / Heating 4: 75 percent / N,N-dimethyl-acetamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: water; Na2CO3 2: pyridine 3: water; ethanol; HCl |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: water; ethanol |
Yield | Reaction Conditions | Operation in experiment |
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78% | In methanol; chloroform; sodium carbonate | 68 Example 68 Example 68 To a suspension of 1,2,4-triaminobenzene dihydrochloride (5.0 g) in a 10% aqueous Na2CO3 solution (60 mL) was added a 40% aqueous pyruvic aldehyde solution (4.59 g) at room temperature. The reaction solution was heated under reflux for 2 hours, and extracted with chloroform (60 mL*3). The organic layers were combined, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (2-3% methanol in chloroform) to give 2-methyl-7-aminoquinoxaline (3.17 g, 78%) as yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.46 (s, 1H), 7.83 (d, 1H, J=8.8 Hz), 7.11 (dd, 1H, J=8.8, 2.6 Hz), 7.06 (d, 1H, J=2.6 Hz), 2.69 (s, 3H). |
78% | In methanol; chloroform; sodium carbonate | 68.1 (68-1) (68-1) To a suspension of 1,2,4-triaminobenzene dihydrochloride (5.0g) in a 10 % aqueous Na2CO3 solution (60 mL) was added a 40 % aqueous pyruvic aldehyde solution (4.59 g) at room temperature. The reaction solution was heated under reflux for 2 hours, and extracted with chloroform (60 mL x 3). The organic layers were combined, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (2-3 % methanol in chloroform) to give 2-methyl-7-aminoquinoxaline (3.17 g, 78 %) as yellow solid. 1H NMR (300MHz, CDCl3) δ 8.46 (s, 1H), 7.83 (d, 1H, J=8.8Hz), 7.11 (dd, 1H, J=8.8, 2.6Hz), 7.06 (d, 1H, J=2.6Hz), 2.69 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In water; sodium carbonate; | 6-Aminoquinoxaline Glyoxal sodium bisulfite adduct (Aldrich, 14.3g, 50 mmol) was added in small portions to a solution of 1,2,4-triaminobenzene dihydrochloride (9.8 g, 50 mmol) in 200 ml of 10% by weight sodium carbonate in water. The reaction mixture was heated to 100 C. for two hours and then cooled to 0 C. The crystals formed were filtered off and dried in vacuo to give a crude yield of 7.06 g (a yield of 97%) of brown crystals. Recrystallization from benzene gave 6.32 g (a yield of 87%) yellow crystals, m.p. 157-8 C. Using various analytical procedures, these yellow crystals were determined to be 6-aminoquinoxaline. |
87% | In water; sodium carbonate; | 6-Aminoquinoxaline Glyoxal sodium bisulfite adduct (Aldrich, 14.3g, 50 mmol) was added in small portions to a solution of 1,2,4-triaminobenzene dihydrochloride (9.8 g, 50mmol) in 200 ml of 10% by weight sodium carbonate in water. The reaction mixture was heated to 100 C. for two hours and then cooled to 0 C. The crystals formed were filtered off and dried in vacuo to give a crude yield of 7.06 g (a yield of 97%) of brown crystals. Recrystallization from benzene gave 6.32 g (a yield of 87%) yellow crystals, m.p. 157-8 C. Using various analytical procedures, these yellow crystals were determined to be 6-aminoquinoxaline. |
87% | In water; sodium carbonate; | 6-Aminoquinoxaline Glyoxal sodium bisulfite adduct (Aldrich, 14.3 g, 50 mmol) was added in small portions to a solution of 1,2,4-triaminobenzene dihydrochloride (9.8 g, 50 mmol) in 200 ml of 10% by weight sodium carbonate in water. The reaction mixture was heated to 100 C. for two hours and then cooled to 0 C. The crystals formed were filtered off and dried in vacuo to give a crude yield of 7.06 g (a yield of 97%) of brown crystals. Recrystallization from benzene gave 6.32 g (a yield of 87%) yellow crystals, m.p. 157-8 C. Using various analytical procedures, these yellow crystals were determined to be 6-aminoquinoxaline. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrogenchloride In ethanol | 1 1,2,4-Triaminobenzene dihydrochloride 1,2,4-Triaminobenzene dihydrochloride To a suspension of 4-nitrophenylenediamine (Aldrich, 10 g, 65.3mmol) in absolute ethanol (240 ml) was added 600 mg of 10% by weight palladium on charcoal catalyst. The container including the suspension was evacuated and filled with hydrogen three times and the suspension was hydrogenated at 18 psi until hydrogen uptake ceased. The reaction was slightly exothermic and one refill of hydrogen was required. The resulting light yellow solution, which darkens rapidly on contact with air, was filtered and concentrated to about 150 ml. Concentrated hydrochloric acid (12 ml) was added and the solid formed was filtered off. After drying in vacuo overnight, 12 g (a yield of 93%) of purple solid was obtained, m.p. 224°-5° C. Using various analytical procedures, this solid was determined to be 1,2,4-triaminobenzene dihydrochloride. |
93% | With hydrogenchloride In ethanol | 1 1,2,4-Triaminobenzene dihydrochloride 1,2,4-Triaminobenzene dihydrochloride To a suspension of 4-nitrophenylenediamine (Aldrich, 10 g, 65.3 mmol) in absolute ethanol (240 ml) was added 600 mg of 10% by weight palladium on charcoal catalyst. The container including the suspension was evacuated and filled with hydrogen three times and the suspension was hydrogenated at 18 psi until hydrogen uptake ceased. The reaction was slightly exothermic and one refill of hydrogen was required. The resulting light yellow solution, which darkens rapidly on contact with air, was filtered and concentrated to about 150 ml. Concentrated hydrochloric acid (12 ml) was added and the solid formed was filtered off. After drying in vacuo overnight, 12 g (a yield of 93%) of purple solid was obtained, m.p. 224-5° C. Using various analytical procedures, this solid was determined to be 1,2,4-triaminobenzene dihydrochloride. |
93% | With hydrogenchloride In ethanol | 1 1,2,4-Triaminobenzene dihydrochloride 1,2,4-Triaminobenzene dihydrochloride To a suspension of 4-nitrophenylenediamine (Aldrich, 10 g, 65.3 mmol) in absolute ethanol (240 ml) was added 600 mg of 10% by weight palladium on charcoal catalyst. The container including the suspension was evacuated and filled with hydrogen three times and the suspension was hydrogenated at 18 psi until hydrogen uptake ceased. The reaction was slightly exothermic and one refill of hydrogen was required. The resulting light yellow solution, which darkens rapidly on contact with air, was filtered and concentrated to about 150 ml. Concentrated hydrochloric acid (12 ml) was added and the solid formed was filtered off. After drying in vacuo overnight, 12 g (a yield of 93%) of purple solid was obtained, m.p. 224°-5° C. Using various analytical procedures, this solid was determined to be 1,2,4-triaminobenzene dihydrochloride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In water for 3h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | for 3h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: benzene-1,2,4-triamine dihydrochloride; trifluoroacetic acid for 3h; Heating; Stage #2: With hydrogenchloride for 1h; Heating; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 2,4-Dinitroanilin In ethanol at 50℃; Stage #2: With hydrazine hydrate In ethanol at 50℃; for 0.5h; Reflux; Stage #3: With hydrogenchloride In water | To a suspension of 2,4-nitroaniline (2) (22.0 g, 120.1 mmol) in ethanol (350 ml), freshly activated Raney nickel catalyst was added and the resulting suspension was heated to 50 °C. Then hydrazine hydrate (40 ml) was added dropwise at this temperature to ensure a gentle foaming of the reaction mixture. After the addition was complete, the reaction mixture was refluxed for 30 min. to decompose the excess of hydrazine hydrate. After completion of the reaction (TLC, eluent CHCl3:MeOH = 100:1), reaction mixture was cooled in an ice bath and filtered into ice cold concentrated HCl (60 ml). Formed precipitate was separated by suction, washed with ethanol and dried to afford dihydrochloride 3 as a slightly violet solid. Hydrochloride 3 (21.8 g, 111.1 mmol) was dissolved in water (400 ml), charcoaled and filtered into a beaker. To the filtrate, solution of SeO2 (12.3 g, 111.1 mmol) in water (30 ml) was added dropwise at room temperature. The reaction mixture was stirred for 10 min. and formed dark red suspension was subsequently alkalized with 20% NaOH solution while cooling in an ice bath. The resulting precipitate was collected by suction, washed with water and dried to yield 5-amino-2,1,3-benzoselenadiazole (4) as orange solid (20.0 g, 91%), mp 147-148 °C (lit.,13,14 149-150 °C). 1H NMR (300 MHz, DMSO-d6): δH 6.59 (1H, d, 4J = 2.2 Hz, 4-H), 7.16 (1H, dd, 3J = 9.5 Hz, 4J = 2.2 Hz, 6-H), 7.55 (1H, d, 3J = 9.5 Hz, 7-H); 13C NMR (300 MHz, DMSO-d6): δC 97.0, 123.8, 126.5, 149.4, 155.8, 159.3. |
81% | With hydrogenchloride; hydrogen In methanol at 50℃; for 4h; | |
78% | Stage #1: 2,4-Dinitroanilin With Degussa F101 catalyst; hydrogen In ethanol at 70℃; for 2h; Autoclave; Inert atmosphere; Stage #2: With hydrogenchloride In ethanol; water at 15℃; | 1,2,4-triaminobenzene dihydrochloride 1,2,4-triaminobenzene and its mineral and organic acid salts are susceptible to oxidation and should be handled in an inert atmosphere. To a 2 gallon autoclave was added 350 g of 2,4-dinitroaniline and 7.0 g of Degussa F101 Pt/C catalyst. The clave was then sealed, purged with nitrogen, and had added to it 1750 mL of nitrogen sparged ethanol. The clave was heated to 70° C. and pressurized to 100 psi with hydrogen and then kept at 70° C. and 100 psi for 2 h. After 2 h the claves contents were pushed through a solids filter and into a precipitation vessel where they were cooled to 15° C. and the product precipitated with the addition 595 mL of 12.1M HCl. The precipitated solids were collected, washed with 12.1M HCl, and partially dried on the filter at 65° C. with nitrogen and vacuum. This afforded 362.3 g of wet (with ethanol) 1,2,4-triaminobenzene dihydrochloride. [0072] The 1,2,4-triaminobenzene dihydrochloride was further purified by crystallization from aqueous with concentrated hydrochloric acid. From the 362.3 g of the crude (wet with ethanol) 1,2,4-triaminobenzene dihydrochloride, 315.42 g dried, crystallized product was recovered, or 78% yield from the hydrogenation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / 16 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / 16 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 3 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / Reflux 3: diphenylether / 260 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: benzene-1,2,4-triamine dihydrochloride With selenium(IV) oxide In water at 20℃; for 0.166667h; Stage #2: With sodium hydroxide In water | To a suspension of 2,4-nitroaniline (2) (22.0 g, 120.1 mmol) in ethanol (350 ml), freshly activated Raney nickel catalyst was added and the resulting suspension was heated to 50 °C. Then hydrazine hydrate (40 ml) was added dropwise at this temperature to ensure a gentle foaming of the reaction mixture. After the addition was complete, the reaction mixture was refluxed for 30 min. to decompose the excess of hydrazine hydrate. After completion of the reaction (TLC, eluent CHCl3:MeOH = 100:1), reaction mixture was cooled in an ice bath and filtered into ice cold concentrated HCl (60 ml). Formed precipitate was separated by suction, washed with ethanol and dried to afford dihydrochloride 3 as a slightly violet solid. Hydrochloride 3 (21.8 g, 111.1 mmol) was dissolved in water (400 ml), charcoaled and filtered into a beaker. To the filtrate, solution of SeO2 (12.3 g, 111.1 mmol) in water (30 ml) was added dropwise at room temperature. The reaction mixture was stirred for 10 min. and formed dark red suspension was subsequently alkalized with 20% NaOH solution while cooling in an ice bath. The resulting precipitate was collected by suction, washed with water and dried to yield 5-amino-2,1,3-benzoselenadiazole (4) as orange solid (20.0 g, 91%), mp 147-148 °C (lit.,13,14 149-150 °C). 1H NMR (300 MHz, DMSO-d6): δH 6.59 (1H, d, 4J = 2.2 Hz, 4-H), 7.16 (1H, dd, 3J = 9.5 Hz, 4J = 2.2 Hz, 6-H), 7.55 (1H, d, 3J = 9.5 Hz, 7-H); 13C NMR (300 MHz, DMSO-d6): δC 97.0, 123.8, 126.5, 149.4, 155.8, 159.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: methanol / Reflux 3: diphenylether / 260 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux 3: diphenylether / 260 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: selenium(IV) oxide / water / 0.17 h / 20 °C 2: ethanol / Reflux 3: diphenylether / 260 °C 4: hydrogenchloride; water / 1 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
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With methanesulfonic acid; tin(II) chloride dihdyrate; In para-xylene; water; for 8.25h;Dean-Stark; Reflux; Inert atmosphere; | General procedure: Example 4 This example demonstrates the synthesis of 2-(4-aminophenyl)-5-amino-benzimidazole from 1,2,4-triaminobenzene dihydrochloride and 4-aminobenzoic acid in methanesulfonic acid, with p-xylene as an azeotroping solvent. To a round bottomed flask equipped with a mechanical stirrer, a graduated Dean-Stark trap, and a reflux condenser and was added 350 mg of SnCl2 dihydrate, 6.57 g 1,2,4-triaminobenzene dihydrochloride, and 4.59 g 4-aminobenzoic acid. Added to the flask were 30 mL of methanesulfonic acid and 50 mL of p-xylene. The receiving arm of the Dean Stark trap was prefilled with p-xylene. The reaction was heated at reflux temperature, under nitrogen, for 8.25 h. To the reaction mixture was added 90 mL water. The mixture was then heated to 85 C. and 25 mL of 12.1M HCl was added. Crystalline solids appeared on cooling. The solids were filtered and washed with fresh 12.1M HCl. A small second crop was obtained on the addition of additional HCl to the filtrate. The solids were combined and dissolved in 70 mL hot water. After the solution cooled to 30 C., the mixture was brought to pH 9 using ammonium hydroxide. A light green solid (5.86 g) was isolated by filtration. The structure of the product was confirmed by 1H NMR and Mass Spectrometry. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: benzene-1,2,4-triamine dihydrochloride; 4-amino-benzoic acid With methanesulfonic acid; tin(II) chloride dihdyrate In octane for 17h; Dean-Stark; Reflux; Stage #2: With hydrogenchloride In water | 5 Example 5 Example 5 This example demonstrates the synthesis of 2-(4-aminophenyl)-5-amino-benzimidazole from 1,2,4-triaminobenzene dihydrochloride and 4-aminobenzoic acid in methanesulfonic acid, with octane as an azeotroping solvent. To a flask equipped with a Dean-Stark trap filled to capacity with octane, was added 12 mL of octane, 4 mL of methanesulfonic acid, 60 mg of SnCl2 dihydrate, 1.31 g 1,2,4-triaminobenzene dihydrochloride, and 0.919 g 4-aminobenzoic acid. The solution was slowly heated to reflux and continued heating at reflux for 17 hours, at which time 2.0 mL of water was added to hydrolyze a small amount of amide which formed, the amide being the 1:1 condensation product of the desired product and 4-aminobenzoic acid. The reaction was removed entirely from heat 1 hour after the addition of water. Upon cooling the methanesulfonic acid layer solidified into a light blue solid mass. The remaining octane was decanted from the solids and the solids added to 16 mL of water which was then brought to 85° C. with added activated carbon. After ten minutes of stirring at 85° C. with the activated carbon, the solution was filtered and washed with 2 mL of water. The filtrate was brought back to 85° C. and 12.1 M HCl was added to it, causing precipitation of colorless product which continued upon solution cooling. The solids were collected through filtration and washed with 12.1 M HCl and isopropanol then allowed to air dry (1.51 g recovered, 68% yield from this crop). A second crop of hydrochloride crystallized from the filtrate as it was being diluted with HCl and isopropanol (193 mg, which combined with crop 1 brought the overall yield to 76%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2 g | With triethylamine In acetonitrile at 20℃; for 72h; Inert atmosphere; | 12 Synthesis example 1.2: Nl, 2,N4-tris(di(piperidin-l-yl)methylene)bcn/cncyl,2,4-trianiine (C8) 19.6 g (78 mmol) l -(chloro(piperidin-l -yl)methylene)piperidin-l-ium. chloride (14) in 150 mL acetonitrile and 65 mL triethylamine were added to a suspension of 5.1 g (26 mmol) benzene- 1,2,4-triamine dihydrochloride in 160 mL acetonitrile and 22 mL triethylamine under argon atmosphere. The mixture was stirred for 72 hours at room temperature. The precipitate was filtrated and the solvent distilled off. The residue was purified by column chromatography in chloroform/methanol and by precipitation in hexane from a dichlorome hane solution, to give 2 g (3.04 mmol; 12 %) foamy solid. The product was purified, by gradient sublimation for analytical characterisation. |
Yield | Reaction Conditions | Operation in experiment |
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49% | With triethylamine In acetonitrile at 0 - 20℃; for 72h; Inert atmosphere; | 13 Synthesis example I3: N 2JN4-tris(1.3-dimethy-lH-benzo[dj^ (C9) 1 1.7 g (35.83 mmol) 2-chloro-l ,3-dimethyl-lH-benzo[d]imidazol-3-i.um hexafluoro phosphate (13) in 25 mL acetonitrile were added to a suspension of 1.79 g (9.13 mmol) benzene-l,2,4-triamine dihydrochloride in 40 mL acetonitrile and 12.7 mL triethylamine under argon atmosphere at 0 °C. The mixture was stirred for 72 hours at room temperature. The precipitate was filtered, washed with acetonitrile, suspended in 2 M sodium hydroxide solution and stiixed for 5 minutes at 45 °C. 2.5 g (4.5 mmol; 49 %) grey solid were obtained after filtration, washing with water and acetonitrile and drying in vacuo. The product was purified by gradient sublimation for analytical characterisation. |
Yield | Reaction Conditions | Operation in experiment |
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75.2% | Example 3(1) under the conditions of the protection of nitrogen, in the 1000 ml flask are added respectively in three 78.43g (0.4mol) 1, 2, 4-triaminobenzene hydrochloride, 700gP2O5content is 80% poly phosphoric acid, 1.19g (0.01mol) tin powder, in the 100 C stirring under 6h, to obtain 1, 2, 4-triaminobenzene of the mixed solution of 2nd(2) in the mixed solution to the above-mentioned 2nd 42.57g (0.3mol) P2O5, 39.62g (0.2mol) 2,5-dihydroxy terephthalic acid, in 190 C reaction under 8h, a reaction mixture is obtained(3) lowering the temperature to the above reaction mixture to 100 C, then poured into ice water stirring 2h, through filtering, the distilled water is washed, after the filter cake is taken out, by adding a small amount of water, and of saturation Na2CO3solution to adjust the pH value to 7, through filtering, the distilled water is washed, the last 120 C vacuum drying 24h, obtained crude product containing hydroxy benzimidazole diamine(4) using N-methyl pyrrolidone as a solvent, the crude product containing hydroxy benzimidazole diamine performing recrystallization, to obtain light yellow powder, and then sequentially through filtering, methanol washing, 120 C vacuum drying 24h, containing hydroxy benzimidazole diamine obtained, HPLC purity is 97.8%, the yield is 75.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.4% | Stage #1: benzene-1,2,4-triamine dihydrochloride With tin(II) chloride dihdyrate; phosphorus pentoxide at 80℃; for 8h; Inert atmosphere; Stage #2: 4-Aminosalicylic acid With phosphorus pentoxide at 210℃; for 8h; Inert atmosphere; | 1 Example 1 Example 1(1) under nitrogen conditions, 1000mL three-necked flask were added 58. 82g (0. 3mol) 1,2, 4-triaminobenzene hydrochloride, 600g P2O5 content of 80% polyphosphoric acid, 1. 35g (0. 006mol) SnCl 2 · 2H20, at 80 ° C underStirred for 8h, to obtain a first mixed solution of 1,2,4-triamino benzene (2) in the mixed solution to the above-mentioned 1st 60g (0.42mol) P2O5, 46.84g (0.33mol) 4-amino salicylic acid, in 210 °C reaction under 8h, a reaction mixture is obtained(3) lowering the temperature to the above-mentioned reaction mixture 120 °C, then poured into ice water stirring 2h, through filtering, the distilled water is washed, after the filter cake is taken out, by adding a small amount of water, using saturated NaHCO3solution to adjust the pH value to 8, through filtering, the distilled water is washed, the last 120 °C vacuum drying 24h, obtained crude product containing hydroxy benzimidazole diamine(4) using dimethyl sulfoxide as solvent, the crude product containing hydroxy benzimidazole diamine performing recrystallization, to get the yellow crystal, and then sequentially through filtering, methanol washing, 100 °C vacuum drying 24h, containing hydroxy benzimidazole diamine obtained, HPLC purity of 98.2%, the yield is 81.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.2% | Stage #1: benzene-1,2,4-triamine dihydrochloride With tin; phosphorus pentoxide at 100℃; for 6h; Inert atmosphere; Stage #2: 5-Aminosalicylic Acid With phosphorus pentoxide at 200℃; for 6h; Inert atmosphere; | 2 Example 2 Example 2(1) under the conditions of the protection of nitrogen, in the 1000 ml flask are added respectively in three 58.82g (0.3mol) 1, 2, 4-triaminobenzene hydrochloride, 650gP2O5content is 80% poly phosphoric acid, 0.36g (0.003mol) tin powder, in the 100 °C stirring under 6h, to obtain 1, 2, 4-triaminobenzene of the mixed solution of 1st(2) in the mixed solution to the above-mentioned 1st 42.57g (0.3mol) P2O5, 45.34g (0.3mol) 5-amino salicylic acid, in 200 °C reaction under 6h, a reaction mixture is obtained(3) lowering the temperature to the above-mentioned reaction mixture 120 °C, then poured into ice water stirring 2h, through filtering, the distilled water is washed, after the filter cake is taken out, by adding a small amount of water, using saturated NaHCO3solution to adjust the pH value to 8, through filtering, the distilled water is washed, the last 120 °C vacuum drying 24h, obtained crude product containing hydroxy benzimidazole diamine(4) the above-mentioned crude product containing hydroxy benzimidazole diamine in the 330 °C sublimation under, containing hydroxy benzimidazole diamine obtained, HPLC purity of 99.8%, to yield 71.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.7% | With sodium hydrogensulfite In ethanol for 4h; Reflux; Inert atmosphere; | 1.3 Synthesis of 2-amino-3- (3-amino-1H-benzo [d] imidazole)-pyridine The sodium bisulfite (0.8678, 0.08111001) was placed in a 5011 ^ three-necked flask and then 1011 ^ of absolute ethanol was added and the mixture was pulverized by sonication. Weigh the 1,2,4-triaminobenzene dihydrochloride (0.317g, 0.003m1), add the reaction flask, evacuate three times, argon protection, adjust the pH to neutral. Compound 2 (0.362g, 0.003m1), dissolved in anhydrous ethanol and transferred to a constant pressure dropping funnel, quickly transferred to three bottles, slowly dropping aldehydes. Heated to reflux, 4h after the reaction. Filtered, washed with absolute ethanol, the filtrate under pressure vacuum steam, pale yellow solid. Column chromatography (ethyl acetate / triethylamine = 1: 1) gave product 1, dried in vacuo, yield: 86.7% |
Tags: 615-47-4 synthesis path| 615-47-4 SDS| 615-47-4 COA| 615-47-4 purity| 615-47-4 application| 615-47-4 NMR| 615-47-4 COA| 615-47-4 structure
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