Structure of 131401-54-2
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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CAS No. : | 131401-54-2 |
Formula : | C14H6F2O4 |
M.W : | 276.19 |
SMILES Code : | O=C1C2=C(C(O)=CC=C2O)C(C3=C(F)C=CC(F)=C13)=O |
MDL No. : | MFCD12913385 |
* 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 |
---|---|---|
92% | With aluminum (III) chloride; sodium chloride; at 220℃; for 3h; | Reference Example 17; 1, 4-Difluoro-5, 8-Dihydroxyanthraquinone (C) A mixture of ground AtCtg (2.955 g, 22.16 mmol), NaCI (432 mg, 7.39 mmol), 1,4-dihydroxybenzene (224 mg, 2.03 mmol) and 3, 6-difluorophthalic dry (340 mg, 1.85 mmol) were stirred vigorously in a round bottom flask and heated to 220 °C in an oil-bath for 3 h. The oil-bath was removed and the reaction quenched by addition of ice and concentrated hydrochloric acid (10 mL). The final aqueous solution was filtered under suction and the precipitated material was washed with water followed by freeze-drying. No further work-up was required, as the brown title-compound (470 mg, 92 percent) was pure as observed by TLC and confirmed by NMR and MS: (250 MHz; Ceci3) ; 7.3 (s, 2H), 7.55 (m, 2H), 12.9 (s, 2H) ; FAB MS, m/z (M+H) + 277. |
77% | With aluminum (III) chloride; In sulfolane; at 165℃; for 16h; | A mixture of 4,7-difluoroisobenzofuran-1 ,3-dione (8.50 g, 46.2 mmol), hydroquinone (5.64 g, 51.3 mmol), aluminium trichloride (36.9 g, 277 mmol) and sulfolane (10 mL) was stirred together for 16 hours at 165°C. The reaction was effectively a melt as the mixture does not become a viscous red syrup until ~ 150°C. To minimise the risk of a sudden exotherm and evolution of HCI gas, the reaction was stirred in portions, cooled in an ice bath and stirred again until mixing was sufficient. Only then was the mixture heated. The mixture was poured carefully into ice and 2M HCI added (50 mL). The mixture was stirred, then filtered, washing the resultant slurry with further 2M HCI. The solid was re- slurried a further 3 times with 2M HCI to reduce the aluminium content of the product. A final slurry was washed with ether twice; drying in a round bottom flask at 60°C until constant weight afforded 1 ,4-difluoro-5,8-dihydroxyanthracene-9,10-dione (9.82 g, 35.6 mmol, 77 percent yield). 1 6 H NMR (DMSO-d ) was clean and consistent with the desired material. |
~ 68% | aluminum (III) chloride; In sulfolane; at 155 - 180℃; for 12h; | 0.3 kg (1.63 mol) of DFPA, 0.2 kg (1.82 mol) of p- hydroquinone, 1.1 kg (8.25 mol) of powdered anhydrous A1C13 and tetramethylene sulfone (1.8 L) were stirred for approximately 12 hours at a temperature of 155°C to 180°C. The reaction mixture was then quenched with ice cold water (1.0 L) and treated with aqueous 2M hydrochloric acid (1.0 L). The suspension was filtered and the resulting solid was dried at 45°C under vacuum. A fine red powder (crude DDA) was obtained after drying. This reaction was performed on several batches of the same scale and yields of around 68percent were obtained. The isolated DDA was contaminated with aluminium containing impurities, where the aluminium content in the isolated product ranged from 3290 ppm to 975 ppm, see Table 1. All batches used 300 g as one molar equivalent of DDA with the exception of batch 5A, which used 200 g. Batch Yield (g) Analytical data Number (percent yield) Al (ppm) 1A 302 (67percent) 975 2A 296 (66percent) 1150 3A 305 (68percent) 3290 4A 310 (69percent) 1165 5A 256 (85percent) 1640 Table 1 : Yield and purity of crude DDA The organic components of the product were determined to be pure by using HPLC. Purification of crude DDA The solid, crude DDA, obtained using the previous method, was treated with aqueous 2M hydrochloric acid (1.0 L) to form a slurry. Filtration of the suspension resulted in the isolation of a solid. The solid was slurried and filtered several times before drying the solid at 45°C under vacuum to leave a fine red powder. The mass recovery for this procedure was typically 90percent. This procedure resulted in a reduction of the aluminium content in the crude DDA for all the batches, see Table 2. Batch Yield (g) Analytical data Number (percent recovery) Al (ppm) 1A 283 (94percent) 714 2A 276 (93percent) 801 3A 268 (88percent) 875 4A 280 (90percent) 865 5A 229 (89percent) 526 Table 2: Yield and purity after slurrying crude DDA The organic components of the product were determined to be pure by using HPLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; hydroquinone; sodium chloride;AlCl3; | 1,4-Difluoro-5,8-dihydroxyanthracene-9,10-dione (4). This compound was prepared by modifications to the literature method of Synth. Comm., 1990, 20, 2139. A mixture of the sublimed product (9) from the above reaction (100 g, 0.55 moles), hydroquinone (63.7 g, 0.58 moles), NaCl (127 g, 2.22 moles) and powdered anhydrous AlCl3 (833 g, 6.26 moles) was placed in a 5 L flask equipped with a condenser. The reactants were well-mixed by shaking, then heated over 1-2 hours to 200+-5° C. (bath) under a nitrogen atmosphere (there was very large gas evolution during the heating process). After a further 2 hours at 200+-5° C., the melt was poured onto ice and conc. HCl (1.6 L) was added. The mixture was stirred at room temperature overnight, and the reddish brown precipitate was collected, washed with H2O and dried to give crude 1,4-difluoro-5,8-dihydroxyanthracene-9,10-dione (4) (151 g, 98percent), m.p. 301-304° C. (lit. m.p. 318-319° C.). This crude product was virtually insoluble in all solvents, and showed (by TLC in EtOAc/petroleum ether 1:3) only one minor impurity (probably 1-chloro-4-fluoro-5,8-dihydroxyanthracene-9,10-dione). 1H NMR agreed well with literature. This material was used for the next step without further purification. 1,4-Bis[[2-(dimethylamino)ethyl]amino]-5,8-dihydroxyanthracene-9,10-dione (3: AQ4). |
Tags: 131401-54-2 synthesis path| 131401-54-2 SDS| 131401-54-2 COA| 131401-54-2 purity| 131401-54-2 application| 131401-54-2 NMR| 131401-54-2 COA| 131401-54-2 structure
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