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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.
Synonyms: Anthracen-9(10H)-one
4.5
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| CAS No. : | 90-44-8 |
| Formula : | C14H10O |
| M.W : | 194.23 |
| SMILES Code : | O=C1C2=C(C=CC=C2)CC3=CC=CC=C13 |
| Synonyms : |
Anthracen-9(10H)-one
|
| English Name : | Anthracen-9(10H)-one |
| MDL No. : | MFCD00001187 |
| InChI Key : | RJGDLRCDCYRQOQ-UHFFFAOYSA-N |
| Pubchem ID : | 7018 |
* 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 |
|---|---|---|
| 93% | First, 9-anthrone (5 g, 26 mmol), zinc powder (8.5 g, 129 mmol), zinc chloride (7 g, 56 mmol) were added to a three-necked flask, and a certain percentage of 100 ml of a mixed solvent of tetrahydrofuran and water was added. The magnet was stirred for more than 8 hours at room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, spin-dried and dried to give 4.8 g of a yellow solid. The yellow solid was added to the three-necked flask and a small amount of p-toluenesulfonic acid was added. (PTS) using toluene as solvent, refluxing until the solvent becomes clear, extracting with solvent dichloromethane, drying with anhydrous magnesium sulfate as a drying agent, filtering, spin-drying, and purifying by silica gel column to obtain white crystalline solid 4.3 g, yield 93%. | |
| With hydrogenchloride; tin; In acetic acid; | Example 1 Preparation of 1:1 [9,9']Bianthracenyl/Toluene adduct Anthrone (40.00 g, 206 mmol) was refluxed in a mixture of glacial acetic acid (200 ml) and concentrated hydrochloric acid (80 ml). To this refluxing solution granulated tin (80 g, 674 mmol) was cautiously added. The reaction was refluxed for 15 h during which time a white precipitate formed. The mixture was cooled to room temperature and the solution was carefully filtered under vacuum to isolate the precipitate but left unreacted in the reaction vessel. The precipitate was washed with water (100 ml) and dried in a vacuum oven. This solid was then recrystallized from the minimum amount of hot toluene (approximately 500 ml) to yield light yellow crystals of the 1:1 [9,9']Bianthracenyl/Toluene adduct (37 g, 81% yield). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 70% | Stage #1: anthracen-9(10H)-one; vinyl magnesium bromide In tetrahydrofuran at 55℃; for 4h; Stage #2: With hydrogenchloride; water In tetrahydrofuran | Synthesis of 9-olefin appended anthracenes (6a-c); generalprocedure (b) Grignard reaction: A solution of anthrone (15.0 g, 0.08mol) dissolved in dry THF (200 mL), was added to a mixture ofvinylmagnesium bromide (11.80 g, 0.09 mol) in dry THF (80 mL),maintained at 55 oC. The mixture was refluxed for 4h, cooledand then hydrolysed with 4N HCl (50mL). The organic layer wasextracted with benzene (70 mL). The extract was washed with waterand dried with anhydrous Na2SO4. The filtrate was added at roomtemperature to P2O5 (10 g) in anhydrous benzene (250 mL) withstirring over a 40 h period. Subsequently the filtrate was evaporatedto dryness, giving a crude solid, which was purified by columnchromatography over silica gel using hexane as eluent to give 6a inpure form. Yield 70%; m.p. 65 °C; IR vmax (KBr) 3075 cm-1 (=CH2),3043 cm-1 (=CH), 1625 cm-1 (C=C); UV lmax (CH3CN) 250 (e73,000), 330 (e 2,500), 385 (e 4,900); 1H NMR (CDCI3) d 5.66 (1H,dd, Jtrans = 17.7 Hz, Jgem = 2.1 Hz, vinylic), 6.04 (1H, dd, Jtrans = 11.4Hz, Jgem = 2.1 Hz, vinylic), 7.46-8.40 (l0H, m, aromatic and vinylic).Anal. calcd for C16H12:C, 94.08; H, 5.92; found: C, 94.3l; H, 5.72%. |
| 61% | In tetrahydrofuran for 3.5h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 62% | With potassium hydroxide; tetra-(n-butyl)ammonium iodide In water; benzene 1.) RT, 2 h, 2.) reflux; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 33% | With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In toluene at 50℃; for 18h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With ethanol; sodium hydride 1.) THF, RT, 2.) THF, benzene, RT, 3 h; Yield given. Multistep reaction; | ||
| 121 g | Stage #1: anthracen-9(10H)-one With lithium tert-butoxide In tetrahydrofuran at 15 - 30℃; Stage #2: 2-fluoro-4-(iodomethyl)-pyridine In tetrahydrofuran at 40 - 50℃; for 2.66667h; Further stages.; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 68.8% | Stage #1: 3,5-dibromo-2-methylthiophene With n-butyllithium In diethyl ether at -78℃; for 0.5h; Stage #2: anthracen-9(10H)-one In diethyl ether; toluene at -78 - 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 53% | Stage #1: 4-t-butyl-2,6-dimethylbromobenzene With tert.-butyl lithium In diethyl ether; pentane at -78 - 20℃; Stage #2: anthracen-9(10H)-one In diethyl ether; toluene; pentane Heating; | |
| 44% | Stage #1: 4-t-butyl-2,6-dimethylbromobenzene With tert.-butyl lithium In diethyl ether; pentane at -78℃; for 1h; Stage #2: anthracen-9(10H)-one In diethyl ether; toluene; pentane Heating; | |
| 44% | Stage #1: 4-t-butyl-2,6-dimethylbromobenzene With tert.-butyl lithium In diethyl ether; pentane at -78 - 20℃; Stage #2: anthracen-9(10H)-one In diethyl ether; toluene; pentane Heating; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Stage #1: anthracen-9(10H)-one With lithium tert-butoxide In tetrahydrofuran at 15 - 30℃; Stage #2: 2-fluoro-pyridin-4-ylmethyl chloride In tetrahydrofuran at 40 - 50℃; Further stages.; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 75% | With sodium iodide In tetrahydrofuran; n-heptane | 5 Example 5 Example 5 10,10-Bis[(2-fluoro-4-pyridinyl)methyl]-9(10H)-anthracenone (I) Two solutions are prepared. For one, 1.0 M lithium t-butoxide in THF (1.00 L, 1.00 mol) was added to a solution of anthrone (70.0 g, 0.36 mol) in THF (0.70 L) at 15-30° C. to form lithio anthrone. The second solution was prepared by mixing sodium iodide (45.0 g, 0.30 mol) VI-i (150.0 g, 0.73 mol) and THF (1.60 L) at 40° C. for 3 h to form a mixture of VI-i/VII-i. The lithio anthrone solution was added dropwise over 100 min at 40-50° C. to the iodide/mesylate solution. The reaction was aged for 1 h (the HPLC peak area of VII-i was <1%). The solution was washed with saturated aqueous brine (2*0.90 L). Volatiles were removed in vacuo and the residue was diluted with toluene (1.3 L). The solution was heated to 100° C., cooled to 90° C. and stirred with basic alumina (120 g) for 30 min. The solution was filtered through a Celite pad, concentrated by atmospheric distillation to 500 mL and cooled to 25° C. to crystallize I. Further crystallization was induced by the dropwise addition of n-heptane (0.60 L) followed by cooling to 0° C. for 2 h. The crystals were collected by filtration, washed with n-heptane (0.2 L) and dried at 60° C. in vacuo to yield 121 g of I (75% yield from anthrone, 92 HPLC wt % purity versus a reference standard). |
[ 90-44-8 ]
[ 13380-67-1 ]

[ 1041480-19-6 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea; In toluene; at 20℃; for 14h; | General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. | |
| With (1R,2R)-N,N-dimethyl-N'-phthaloyl-1,2-diaminocyclohexane; In 1,2-dichloro-ethane; at -10℃; for 12h; | General procedure: A mixture of maleimide 3 (0.24 mmol), anthrone 2 (0.2 mmol), and the catalyst (20 mol %) in 1,2-dichloroethane (0.6 mL) at -10 C was stirred for 12 h (monitored by TLC). After evaporation under reduced pressure, the residue was purified through column chromatography on silica gel (petroleum ether/ethyl acetate=3/1) to yield pure products. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 94% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | |
| 94% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 92% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 90% | With 1-{3,5-bis(trifluoromethyl)phenyl}-3-{(1R,2R)-2-(dimethylamino)cyclohexyl}thiourea In toluene at 20℃; for 14h; optical yield given as %ee; enantioselective reaction; | 4.5. General experimental procedure for the addition of anthrones to maleimides General procedure: To a stirred solution of catalyst (R,R)-V (10 mg, 0.025 mmol) in toluene (1 mL) were added the maleimide (0.30 mmol) and the anthrone (1a or 1b, 0.25 mmol). The reaction mixture was vigorously stirred at room temperature during 14 h, and the crude product was directly purified by column chromatography on silica gel (hexane/ethyl acetate mixtures) to afford the Diels-Alder or the Michael adduct. Racemic products were obtained from the corresponding substrates by catalysis with DABCO in toluene at room temperature. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 37% | With hydrogenchloride In ethanol for 3.5h; Reflux; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 72% | With trimethylsilylazide; diphenyl phosphoryl azide; water; 2,3-dicyano-5,6-dichloro-p-benzoquinone; iron(II) chloride In trifluoroacetic acid at 100℃; for 96h; Inert atmosphere; | |
| Multi-step reaction with 2 steps 1: sodium nitrite; hydrogenchloride / ethanol; water / 12 h / 20 °C / Cooling with ice 2: chlorosulfonic acid / acetonitrile / 10 h / 20 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 43 % ee | With (1R,2R)-N,N-dimethyl-N'-phthaloyl-1,2-diaminocyclohexane In 1,2-dichloro-ethane at -10℃; for 12h; Overall yield = 85 %; enantioselective reaction; | Representative experimental procedure for D-A reaction General procedure: A mixture of maleimide 3 (0.24 mmol), anthrone 2 (0.2 mmol), and the catalyst (20 mol %) in 1,2-dichloroethane (0.6 mL) at -10 °C was stirred for 12 h (monitored by TLC). After evaporation under reduced pressure, the residue was purified through column chromatography on silica gel (petroleum ether/ethyl acetate=3/1) to yield pure products. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 62% | Stage #1: anthracen-9(10H)-one With potassium carbonate In acetone for 0.166667h; Stage #2: ethyl 10-bromo-decanoate In acetone for 24h; Reflux; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 26% | General procedure: All reactions were run in closed 50 mL polyethylene vessels. To a solution of anthrone (0.15-0.60 mmol) in CH2Cl2or other solvents (abs., 8 mL) at -40 C, the catalyst 10 (0.1 equiv) was added. After stirring for 15 minutes, maleimide was added to the mixture in one portion. The solution was allowed to warm up to -15 C overnight and stirred for two more days at this temperature. After warming up to room temperature the reaction mixture was purified by flash column chromatography (c-hexane/EtOAc 10:1) to afford the different products as crystalline solids. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With lithium perchlorate; triethylamine; In chloroform; at 20℃; for 168h; | General procedure: All reactions were run in closed 50 mL polyethylene vessels. To a solution of anthrone (0.15-0.60 mmol) in CH2Cl2or other solvents (abs., 8 mL) at -40 C, the catalyst 10 (0.1 equiv) was added. After stirring for 15 minutes, maleimide was added to the mixture in one portion. The solution was allowed to warm up to -15 C overnight and stirred for two more days at this temperature. After warming up to room temperature the reaction mixture was purified by flash column chromatography (c-hexane/EtOAc 10:1) to afford the different products as crystalline solids. The racemic Diels-Alder products rac-25-rac-27 were prepared with triethylamine (1.0 equiv) instead of guanidine 10. After stirring for 24 hours at room temperature the reaction mixture was also purified by flash column chromatography (c-hexane/EtOAc 10:1).The racemic retro-aldol products rac-28-rac-31 were prepared with triethylamine (1.0 equiv.) instead of guanidine in the presence of a small amount of LiClO4acting as Lewis acid. After stirring for 7 days at room temperature the reaction mixture was also purified by flash column chromatography (c-hexane/EtOAc 10:1). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 2 steps 1.1: sodium t-butanolate; palladium diacetate; tri-tert-butyl phosphine / toluene / 3 h / 100 °C / Inert atmosphere 2.1: n-butyllithium / tetrahydrofuran; hexane / 1 h / -78 °C / Inert atmosphere; Cooling with acetone-dry ice 2.2: 2.5 h / -78 - 20 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 35% | Stage #1: <2-(trifluoromethyl)pyridin-4-yl>methanol With sodium iodide In tetrahydrofuran at 50℃; for 2.5h; Inert atmosphere; Stage #2: With 18-crown-6 ether In tetrahydrofuran for 1h; Inert atmosphere; Molecular sieve; Stage #3: Anthrone With potassium <i>tert</i>-butylate In tetrahydrofuran for 12h; Inert atmosphere; | 10,10-bis([2-(trifluoromethyl)pyridin-4-yl]methyl})-9,10-dihydroanthracen-9-one (5). Mesylate S2 (0.132 g, 0.464mmol) was placed in an oven dried 20 mL vial followed by sodium iodide (0.034 g, 0.222 mmol). The vial was sealed andpurged with nitrogen before anhydrous THF (8.0 mL) was added. The solution was heated to 50 °C for 2.5 h. 18-crown-6(0.367 g, 1.36 mmol) was dissolved in THF (3.0 mL) in a separate nitrogen purged 4 mL vial containing 4 Å molecularsieves. The solution was stirred for 1 h before being added by syringe to a 20 mL vial containing anthrone (0.040 g,0.202 mmol) in THF (2.5 mL). Next, potassium tert-butoxide (0.070 g, 0.605 mmol) was added as a solution in THF (2.5mL). The anthrone anion solution was added to the mesylate/iodide solution dropwise over 10 min. at 50 °C, and the reactionwas stirred for 12 h. A sample aliquot was taken from the reaction, dissolved in 1 mL HPLC grade MeCN, and analyzedwith LC-MS to confirm the completion of the reaction. The reaction was diluted with EtOAc (50 mL) and washed withbrine (5 x 20 mL). The organic layer was condensed to give an orange oil, then dissolved with DCM and purified by flashchromatography (5 g SiO2 cartridge; 0-60% EtOAc/hexanes gradient) to give the title compound as a clear oil (0.036 g,35%). 1H NMR (300 MHz, CDCl3) δ = 3.84 (s, 4H), 6.35 (d, J = 5.0 Hz, 2H), 6.59 (s, 2H), 7.51 (t, J = 7.6 Hz, 2H), 7.87 (t,J = 7.6 Hz, 2H), 8.04 (d, J = 8.2 Hz, 2H) 8.09 - 8.18 (m, 4H); 13C NMR (75 MHz, CDCl3) d = 48.2, 49.4, 119.45, 121.5,121.6, 121.6, 121.6, 123.1, 126.8, 127.1, 128.4, 128.6, 132.7, 134.0, 142.8, 146.7, 147.4, 147.8, 149.3, 181.5; 19F NMR(376 MHz, CDCl3) δ = -69.1; ; IR (film) 1661, 1602, 1326, 1178, 1135, 1117, 1088, 707, 687 cm-1; HRMS (ESI+) calcdfor C28H18F6N2O [M+H]+ 513.1396, found 513.1383. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 92% | With potassium hydroxide In tetrahydrofuran at 75℃; for 24h; | 1.2 Step 2: 100 parts of anthrone were dissolved in 300 parts of tetrahydrofuran, 20 parts of potassium hydroxide and 120 parts of the product synthesized in step 1 were added, and stirred at 75 ° C. for 24 hours under reflux. After the reaction was completed, the temperature of the solution was lowered to 25 ° C. and then filtered, and then the filtrate was subjected to rotary evaporation. The product was dissolved in chloroform and washed three times with distilled water. The chloroform solution was dried under vacuum for 3 hours to obtain a yellow liquid with a yield of 92%. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 62% | Stage #1: anthracen-9(10H)-one With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: 2,5-difluoroanisole With n-butyllithium In tetrahydrofuran; hexane; mineral oil at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 41% 2: 15% | Stage #1: anthracen-9(10H)-one With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: 1,2-difluoro-4-methoxy-benzene With n-butyllithium In tetrahydrofuran; hexane; mineral oil at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 36% 2: 25% | Stage #1: anthracen-9(10H)-one With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: 1,4-difluoro-2,5-dimethoxybenzene With n-butyllithium In tetrahydrofuran; hexane; mineral oil at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 58% | Stage #1: anthracen-9(10H)-one With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: 3,5-dimethoxyfluorobenzene With n-butyllithium In tetrahydrofuran; hexane; mineral oil at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 87% | With triethylamine In 1,4-dioxane at 32℃; for 24h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 33 % | Stage #1: 5-bromo-2-iodo-1,3-dimethylbenzene With n-butyllithium In diethyl ether; hexane at 0℃; Inert atmosphere; Stage #2: Anthrone In diethyl ether; hexane at 0 - 24℃; Inert atmosphere; Stage #3: With toluene-4-sulfonic acid In toluene at 110℃; |