* 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.
With trichlorosilane In chlorobenzene at 20℃; for 24 h; Inert atmosphere
Compound 2 (4 g, 19.03 mmol) was dissolved in chlorobenzene (20 mL) at room temperature, protected with nitrogen, and trichlorosilane (6.6 g 49.47 mmol) was slowly added dropwise; the mixture was heated at reflux for one day and the chlorobenzene was separated by rotary evaporation. The mixture was dissolved in ImoL/L hydrochloric acid (50 mL), extracted with ethyl acetate, and after-treated, and was purified by silica gel column chromatography to give a pale yellow solid 3 (2.1 g, 12.7 mmol). The yield was 66.9percent.
Reference：
[1] Patent: CN107935982, 2018, A, . Location in patent: Paragraph 0023; 0024
[2] Bioorganic and Medicinal Chemistry Letters, 2010, vol. 20, # 13, p. 3872 - 3875
2
[ 1818-28-6 ]
[ 1818-27-5 ]
Yield
Reaction Conditions
Operation in experiment
75.87%
With aluminum (III) chloride In chlorobenzene at 20℃; for 12 h;
A solution of 2,4,5-trimethoxyacetophenone (4.00 g,19.03 mmol) in chlorobenzene (20 mL) was treated with AlCl3(6.60 g, 49.47 mmol) at room temperature and then refluxed for12 h. The solvent was evaporated and the residue was hydrolyzedwith cooled 1 M HCl (50 mL) and extracted with ethyl acetate(3 50 mL). The organic layer was washed with water (2 50 mL), dried over sodium sulfate anhydrous and then filtered.After evaporation, the crude product was purified by column chromatography(methanol/dichloromethane [0.5:9.5]) to provide2,4,5-trihydroxyacetophenone as the pale yellow solid (2.42 g,75.87percent); m.p. 206–207 C; FTIR (KBr) (cm1): 3405, 3238 (OAHst.), 1634 (CO st.) 1589, 1536 (CC st.), 1300, 1211, 1135 (CAOst.); 1H NMR 300 MHz (CD3OD): d 2.46 (s, 3H, CH3), 6.27 (s, 1H,H3), 7.14 (s, 1H, H6); HRMS (ESI) m/z calculated for C8H8O4,168.0428 [M]+, 167.0350 [MH]+; found 167.0356 [MH]+.
Reference：
[1] Gazzetta Chimica Italiana, 1910, vol. 40 II, p. 349[2] Gazzetta Chimica Italiana, 1913, vol. 43 I, p. 165,167 Anm.
[3] Journal of the Chemical Society, 1933, p. 1073,1075
[4] Patent: US2763691, 1952, ,
[5] Patent: US2763691, 1952, ,
[6] Patent: US2763691, 1952, ,
[7] Gazzetta Chimica Italiana, 1910, vol. 40 II, p. 349[8] Gazzetta Chimica Italiana, 1913, vol. 43 I, p. 165,167 Anm.
[9] Gazzetta Chimica Italiana, 1910, vol. 40 II, p. 349[10] Gazzetta Chimica Italiana, 1913, vol. 43 I, p. 165,167 Anm.
[11] Journal of the Chemical Society, 1934, p. 1625,1628
[12] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 136, p. 205,209
[13] Journal of the Chemical Society, 1934, p. 1625,1628
4
[ 108-24-7 ]
[ 106-51-4 ]
[ 1818-27-5 ]
Reference：
[1] Bioorganic and Medicinal Chemistry, 2009, vol. 17, # 18, p. 6692 - 6698
[2] Patent: US2763691, 1952, ,
5
[ 533-31-3 ]
[ 1818-27-5 ]
Reference：
[1] Patent: CN107935982, 2018, A,
6
[ 533-73-3 ]
[ 108-24-7 ]
[ 64-19-7 ]
[ 1818-27-5 ]
Reference：
[1] Journal of the Chemical Society, 1933, p. 1073,1075
7
[ 533-73-3 ]
[ 75-05-8 ]
[ 1818-27-5 ]
Reference：
[1] Journal of the Chemical Society, 1933, p. 1073,1075
[2] Journal of the Chemical Society, 1934, p. 1625,1628
[3] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 136, p. 205,209
8
[ 89-84-9 ]
[ 1818-27-5 ]
Reference：
[1] Gazzetta Chimica Italiana, 1913, vol. 43 I, p. 170
9
[ 613-03-6 ]
[ 64-19-7 ]
[ 1818-27-5 ]
Reference：
[1] Journal of the Chemical Society, 1932, p. 2420,2422
[2] Journal of the Chemical Society, 1934, p. 1625,1628
10
[ 7446-70-0 ]
[ 613-03-6 ]
[ 1818-27-5 ]
[ 2999-24-8 ]
Reference：
[1] Journal of the Chemical Society, 1934, p. 1625,1628
[2] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 136, p. 205,209
[3] Gazzetta Chimica Italiana, 1951, vol. 81, p. 553,556,557
(F) (2,4,5-Trihydroxyphenyl)ethanone A mixture of triacetoxybenzene (25.2 g, 0.10 mol) and p-toluenesulfonic acid (19.0 g, 0.10 mol) was heated at 140 C. with stirring under nitrogen for 15 minutes. Then water (150 ml) was added, and the reaction was refluxed for 10 minutes. The solution was cooled to 5 C. for 16 hours. The solid was filtered, washed with water (2*40 ml), and dissolved in ethyl acetate (200 ml). The organic solution was dried over sodium sulfate and filtered through silica gel (60-200 mesh, 200 ml). The desired material was eluted with ethyl acetate (4*200 ml). The fractions were combined and the solvent removed in vacuo to give 11.0 g of the title compound.
With acetic anhydride; In pyridine; (2S)-N-methyl-1-phenylpropan-2-amine hydrate; hexane; chloroform; ethyl acetate;
(G) [4,5-Bis(acetyloxy)-2-hydroxyphenyl]ethanone To a solution of <strong>[1818-27-5](2,4,5-trihydroxyphenyl)ethanone</strong> (4.0 g, 0.0238 mol) in pyridine (12 ml) at 0 C. was added acetic anhydride (4.5 ml, 0.0476 mol) in pyridine (1 ml) over 2 minutes. After 10 minutes of stirring, ice water (100 ml) was added and the product oiled out. The water layer was decanted and the product was washed with water and the water decanted (3*30 ml). The residue was dissolved in chloroform (100 ml) and the organic layer was washed with water (20 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The residue was chromatographed twice on silica gel 60-200 mesh (100 ml) in ethyl acetate:hexane (4:1 to 1:1) to give 2.25 g of the desired product.
4,5-Bis(ethoxycarbonyloxy)-2-hydroxyacetophenone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With pyridine; sodium chloride; In ethyl acetate;
(a) 4,5-Bis(ethoxycarbonyloxy)-2-hydroxyacetophenone <strong>[1818-27-5]2,4,5-Trihydroxyacetophenone</strong> (3.36 g) was dissolved in 150 ml of ethyl acetate, and 3.24 ml of pyridine was added at about -5 C. with stirring. Then, 50 ml of a solution of 3.8 ml of ethyl chloroformate in ethyl acetate was added dropwise over 30 minutes. The mixture was stirred for 10 minutes at the same temperature. The resulting precipitate was collected by filtration and washed three times with 10 ml of ethyl acetate. The washings and the filtrate were combined, and the mixture was washed with water (once) and a saturated aqueous solution of sodium chloride (three times) and dried over magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from ethyl ether-ethanol. The crystals were collected by filtration, and washed with ethanol and n-hexane and dried to afford 4.60 g of the desired product. Melting point: 58-60 C.
2-Hydroxy-4,5-bis(2,2,2-trichloroethoxycarbonyloxy)-acetophenone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With pyridine; sodium chloride; In ethyl acetate;
(a) 2-Hydroxy-4,5-bis(2,2,2-trichloroethoxycarbonyloxy)-acetophenone <strong>[1818-27-5]2,4,5-Trihydroxyacetophenone</strong> (16.8 g) was dissolved in 500 ml of ethyl acetate, and 15.98 ml of pyridine was added at about -5 C. with stirring. Then, a solution of 26.82 ml of 2,2,2-trichloroethyl chloroformate in 70 ml of ethyl acetate was added dropwise over the course of 2.5 hours. The mixture was stirred at the same temperature for 15 minutes. The precipitate formed was collected by filtration and washed with ethyl acetate. The washing and the filtrate were combined, and the mixture was washed with water (once) and a saturated aqueous solution of sodium chloride (twice), and dried over magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from ethyl ether-ethanol. The crystals were collected by filtration, washed with ethanol and n-hexane and dried to afford 43.6 g of the desired product. Melting point: 107.5-108 C.
With trichlorosilane; In chlorobenzene; at 20℃; for 24h;Inert atmosphere;
Compound 2 (4 g, 19.03 mmol) was dissolved in chlorobenzene (20 mL) at room temperature, protected with nitrogen, and trichlorosilane (6.6 g 49.47 mmol) was slowly added dropwise; the mixture was heated at reflux for one day and the chlorobenzene was separated by rotary evaporation. The mixture was dissolved in ImoL/L hydrochloric acid (50 mL), extracted with ethyl acetate, and after-treated, and was purified by silica gel column chromatography to give a pale yellow solid 3 (2.1 g, 12.7 mmol). The yield was 66.9%.
With boron tribromide; In dichloromethane; at 20℃;Inert atmosphere;
Step C: Compound 128 was dissolved in dichloromethane (20mL), N2 protection, was added dropwise under ice-cooling BBr3,After the addition was completed, the mixture was stirred at room temperature overnight. Pour the reaction solution into crushed ice and adjust the pH to 4-5 with 2N NaOH solution.Add ethyl acetate (50 mL × 2) for extraction.The combined organic phases were washed with saturated brine.Dry over anhydrous sodium sulfate. Evaporate the solvent under reduced pressure.The product is purified by column chromatography (200-300 mesh silica gel,Ethyl acetate: dichloromethane = 1:5 to 1:1 elution),1-(2,4,5-Trihydroxyphenyl)ethanone (129) (1.41 g),The yield was 76.6%.
75.87%
With aluminum (III) chloride; In chlorobenzene; at 20℃; for 12h;
A solution of 2,4,5-trimethoxyacetophenone (4.00 g,19.03 mmol) in chlorobenzene (20 mL) was treated with AlCl3(6.60 g, 49.47 mmol) at room temperature and then refluxed for12 h. The solvent was evaporated and the residue was hydrolyzedwith cooled 1 M HCl (50 mL) and extracted with ethyl acetate(3 50 mL). The organic layer was washed with water (2 50 mL), dried over sodium sulfate anhydrous and then filtered.After evaporation, the crude product was purified by column chromatography(methanol/dichloromethane [0.5:9.5]) to provide2,4,5-trihydroxyacetophenone as the pale yellow solid (2.42 g,75.87%); m.p. 206-207 C; FTIR (KBr) (cm1): 3405, 3238 (OAHst.), 1634 (CO st.) 1589, 1536 (CC st.), 1300, 1211, 1135 (CAOst.); 1H NMR 300 MHz (CD3OD): d 2.46 (s, 3H, CH3), 6.27 (s, 1H,H3), 7.14 (s, 1H, H6); HRMS (ESI) m/z calculated for C8H8O4,168.0428 [M]+, 167.0350 [MH]+; found 167.0356 [MH]+.
With aluminum (III) chloride; In toluene; for 24h;Reflux;
A mixture of l-(2,4,5-trimethoxyphenyl)ethanone (10 g, 47.6 mmol, 1 eq) and AICI3 (16.5 g, 124 mmol, 2.6 eq) in toluene (48 mL) is stirred at reflux for 24 h. The mixture is concentrated to dryness and quenched with cooled 1 N HC1. The mixture is extracted with ethyl acetate. The organic layer is dried (Na2S04) and concentrated. The residue is purified by flash column chromatography (S1O2, dichloromethane/methanol 100:0 to 95:5) to afford the desired product.
To a solution of 2,4,5-trihydroxyacetophenone (1.50 g,8.93 mmol) in acetone (24 mL) was added anhydrous potassiumcarbonate (2.22 g, 16.07 mmol). The mixture was stirred at roomtemperature for 10 min. Then benzyl bromide (2.75 g, 16.08 mmol)was added and the reaction mixture was refluxed for 5 h. Aftercooling to room temperature, the solvent was evaporated andwater was added to the residue. The aqueous mixture wasextracted with ethyl acetate (3 40 mL). The combined organiclayer was washed with water (2 40 mL) and dried over sodiumsulfate anhydrous, then filtered. After removing the solvent, thecrude product was purified by column chromatography (ethyl acetate/hexane [1:4]) to provide 4,5-bis(benzyloxy)-2-hydroxyacetophenoneas the white solid (2.18 g, 70.19%); m.p. 99-100 C; FTIR(KBr) (cm1): 3065, 3037 (aromatic CAH st.), 2867 (aliphaticCAH st.), 1633 (CO st.), 1510, 1455 (CC st.), 1370 (CAH bending),1263, 1210, 1166 (CAO st.); 1H NMR 300 MHz (CDCl3): d 2.48 (s, 3H, CH3), 5.10 (s, 2H, CH2-Ph), 5.21 (s, 2H, CH2-Ph), 6.54 (s,1H, H3), 7.19 (s, 1H, H6), 7.34-7.48 (m, 10H, H20, H30, H40, H50, H60 ,H200, H300, H400, H500, H600); LRMS (ESI) m/z [M+Na]+ 371.29 (46.0),280.20 (100.0), 189.29 (10.0).
With potassium carbonate; In acetone; at 60℃; for 4h;Reflux; Inert atmosphere;
To a stirred solution of benzophenone 6 (103 mg, 0.613 mmol) in acetone (3.0 mL) were added K2CO3 (172 mg, 1.25 mmol) and MeI (40 muL, 0.64 mmol) at room temperature. After being stirred at reflux for 4 h, the reaction mixture was concentrated. The resultant mixture was dissolved in H2O (1.0 mL), diluted with 2 M HCl (0.3 mL) to pH 3, and extracted with EtOAc (3 × 12 mL). The combined extracts were washed with brine, dried (Na2SO4), filtered, and concentrated to give a crude monomethyl benzophenone 7 (110 mg), which was used for the next reaction without further purification. To a stirred solution of the crude monomethyl benzophenone 7 (110 mg) in MeCN (3.0 mL) were added K2CO3 (165 mg, 1.19 mmol), BnCl (80 muL, 0.70 mmol), and n-Bu4NI (329 mg, 0.891 mmol) at room temperature. After being stirred at room temperature for 8.5 h, the reaction mixture was filtrated with Celite, and this Celite was rinsed with EtOAc (4 × 10 mL). The filtrate and rinse were concentrated. The residual solid was purified by column chromatography on silica gel (10 g, hexane-EtOAc 16:1 ? 14:1 ? 12:1 ? 2:1) to give acetophenone 8 (57.3 mg, 35% in two steps) as a white solid; mp 147-149 C; IR (CHCl3) 3025, 3012, 1633, 1508, 1444, 1374, 1329 cm-1; 1H NMR (400 MHz, CDCl3) delta 12.59 (s, 1H), 7.45-7.32 (m, 5H), 7.09 (s, 1H), 6.46 (s, 1H), 5.08 (s, 2H), 3.92 (s, 3H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3) delta 202.1, 160.4, 157.7, 140.4, 136.8, 128.6 (2C), 128.1, 127.6 (2C), 116.2, 111.7, 100.6, 72.6, 56.1, 26.2; HRMS (ESI) m/z 271.1001, calcd for C16H15O4 [M-H]- 271.0975.
Chloromethyl methyl ether (0.14 mL, 1.79 mM) was added to a stirred solutionof 2,4,5-trihydroxyacetophenone (50.00 mg, 0.30 mM) and N,Ndiisopropylethylamine(0.31 mL, 1.79 mM) in acetonitrile. The mixture wasstirred overnight. In a separate flask, a mixture of 4-hydroxybenzaldehyde(37.00 mg, 0.30 mM), N,N-diisopropylethylamine (0.11 mg, 0.60 mM), andchloromethyl methyl ether (0.05 mL, 0.60 mM) in acetonitrile was stirred for3 h. After the given reaction time, volatiles in the each of the flasks wereremoved under reduced pressure, and the residues were each dissolved inethanol (1.00 mL each). The ethanolic solutions were mixed together, and asolution of KOH (168.00 mg, 3.00 mM) in water (0.10 mL) was added. Thecombined mixture was stirred overnight, and then diluted with ethyl acetate.The mixture was then treated with 1 N-HCl and extracted with ethyl acetate.Volatiles were removed under the reduced pressure, and the residue wasdissolved in methanol (2.00 mL). 2 N-HCl (0.30 mL) was added and thereaction mixture was refluxed for 1 h. The resulting mixture was dilutedwith water and extracted with ethyl acetate. Volatiles were removed underthe reduced pressure, and the residue was purified with preparative HPLC(YMC-Actus Triart C18, gradient, acetonitrile/water with 0.1% acetic acid) toyield 2',4,4',5'-tetrahydroxychalcone (2) as a yellow solid (38.00 mg, 47%); Rf0.3 (acetone:n-hexane = 1:1); IR (ATR-IR) mmax 3333, 3224, 1512, 1160 cm-1;HR-MS calculated for C15H12O5 272.0685, found 272.0683.
With N-Bromosuccinimide; sulfuric acid; In tetrahydrofuran; at 20℃; for 48h;
Compound 3 (100 mg, 06 mmol) was dissolved in 3 mL of tetrahydrofuran, then N-bromosuccinimide (100 mg, 56 mmol) was added, and a mixture of tetrahydrofuran and concentrated sulfuric acid (1 mL: lyL) was slowly added dropwise to react at room temperature. 48 hours, add cold water to quench the reaction, extract after treatment, and obtain a yield of more than 90% 4
With potassium carbonate; In acetonitrile; at 90℃; for 17h;
A mixture of l-<strong>[1818-27-5](2,4,5-trihydroxyphenyl)ethanone</strong> (6.44 g, 38.3 mmol, 1 eq), bromomethylbenzene (CAS: 100-39-0, 4.56 mL, 38.3 mmol, 1 eq) and K2CO3 (5.3 g, 38.3 mmol, 1 eq) in acetonitrile (103 mL) is stirred at 90 C for 1 h and at room temperature for 16 h. The mixture is concentrated and the residue is purified by flash column chromatography (S1O2, petroleum ether/ethyl acetate 100:0 to 0:100) to afford the desired product.
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