* 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.
Stage #1: With aluminum (III) chloride In carbon disulfide; nitrobenzene at 55℃; for 1 h; Stage #2: at 55℃; for 1 h;
General procedure: AlCl3 (4 equiv) was added to a stirred phloroglucinol suspension (1 equiv) in CS2. Nitrobenzene was added to the solution over 30min. The solution was refluxed at 55°C for 30min. Acyl chloride (1equiv) dissolved in nitrobenzene was added to the reaction mixture over 30min before heating for another 30min. The reaction mixture was allowed to cool with stirring and then poured into an ice-water bath. Afterwards, 3M HCl was added. The organic solvents were removed under a reduced pressure, and the oily residue containing the acylphloroglucinol was extracted with Et2O. After removing the Et2O, the crude product was purified via flash chromatography (PE (bp. 50−70°C)/EtOAc 5:1→3:1) [21].
60%
Stage #1: With aluminum (III) chloride In carbon disulfide; nitrobenzene at 55℃; for 0.5 h; Stage #2: for 0.5 h; Heating
General procedure: Phloroglucinol (3; 10.81 g, 85.8 mmol) in carbon disulphide (50 mL) was transferred into a two-necked round-bottomed flask and allowed to stir while aluminium trichloride (46.43 g, 351.8 mmol, 4.1 equiv) was added. Nitrobenzene (40 mL) was then added to the solution over 30 min. The solution was then heated under reflux at 55 °C for 30 min. A solution of 2-methylbutanoyl chloride (2) (10.89 g, 85.8 mmol) dissolved in 5 mL nitrobenzene was added to the reaction mixture over 30 min, followed by heating for another 30 min. The reaction mixture was allowed to cool with stirring and then poured into an ice-water bath (400 mL). 100 mL of 3 m hydrochloric acid was then added and the mixture extracted with diethyl ether (3 * 500 mL). The organic solvents were removed under reduced pressure. The oily residue containing the acylphloroglucinol was subjected to VLC over SiGel PF254 using hexane and EtOAc of increasing polarity. The VLC fraction eluted with 30-45percent EtOAc in hexane gave (S)-2-methyl-1-(2,4,6-trihydroxyphenyl)butan-1-one as a pale yellow oil (9.71 g, 46.19 mmol, 54percent).
2.81%
Stage #1: With aluminum (III) chloride In dichloromethane at 33 - 40℃; for 0.166667 h; Stage #2: for 0.25 h; Reflux
General procedure: The mixture of phloroglucinol (0.05 mol) and anhydrous aluminum chloride (0.1 mol) were dissolved in dichloromethane (50 mL). Phloroglucinol and aluminum chloride easily dissolved in the solvent and HCl was observed to be produced when the reaction temperature rose to about 33 °C. The mixture was heated for 10 min at 40 °C and the acyl chloride (0.05 mol) was added dropwise. After refluxing for 15 min, 0.05 mol of HCl was added to quench the reaction. The solvent was evaporated off, and the resultant product extracted with ethyl acetate. The ethyl acetate extract was purified using flash column chromatography over silica gel, eluted with petroleum ether/ethyl acetate (10:1) [22].
Reference：
[1] Agricultural and Biological Chemistry, 1985, vol. 49, # 3, p. 719 - 724
[2] European Journal of Medicinal Chemistry, 2014, vol. 85, p. 621 - 628
[3] Australian Journal of Chemistry, 2005, vol. 58, # 7, p. 551 - 555
[4] European Journal of Medicinal Chemistry, 2018, vol. 155, p. 255 - 262
[5] Bioorganic and Medicinal Chemistry, 2006, vol. 14, # 13, p. 4402 - 4409
[6] Phytochemistry Letters, 2012, vol. 5, # 1, p. 144 - 149
[7] Molecules, 2014, vol. 19, # 8, p. 11645 - 11659
[8] Bioscience, Biotechnology, and Biochemistry, 1992, vol. 56, # 12, p. 2062 - 2063
[9] Australian Journal of Chemistry, 2008, vol. 61, # 9, p. 718 - 724
[10] European Journal of Medicinal Chemistry, 2017, vol. 125, p. 492 - 499
[11] Molecules, 2018, vol. 23, # 10,
[12] MedChemComm, 2018, vol. 9, # 10, p. 1698 - 1707
Reference：
[1] Journal of the Chemical Society, 1931, p. 1255,1264
[2] Journal of the American Chemical Society, 1932, vol. 54, p. 2452
[3] Journal of the South African Chemical Institute, 1943, vol. 26, p. 41,45
[4] Yakugaku Zasshi, 1949, vol. 69, p. 431[5] Chem.Abstr., 1950, p. 3457
[6] Phytochemistry (Elsevier), 1983, vol. 22, # 1, p. 243 - 246
4
[ 17397-82-9 ]
[ 2295-58-1 ]
Reference：
[1] Tetrahedron, 1969, vol. 25, p. 707 - 714
5
[ 108-73-6 ]
[ 123-62-6 ]
[ 2295-58-1 ]
Reference：
[1] Journal of the South African Chemical Institute, 1943, vol. 26, p. 41,45
[2] Journal of Heterocyclic Chemistry, 2002, vol. 39, # 6, p. 1251 - 1258
6
[ 108-73-6 ]
[ 802294-64-0 ]
[ 3145-11-7 ]
[ 2295-58-1 ]
Reference：
[1] Bioscience, biotechnology, and biochemistry, 1992, vol. 56, # 11, p. 1769 - 1772
General procedure: AlCl3 (4 equiv) was added to a stirred phloroglucinol suspension (1 equiv) in CS2. Nitrobenzene was added to the solution over 30min. The solution was refluxed at 55C for 30min. Acyl chloride (1equiv) dissolved in nitrobenzene was added to the reaction mixture over 30min before heating for another 30min. The reaction mixture was allowed to cool with stirring and then poured into an ice-water bath. Afterwards, 3M HCl was added. The organic solvents were removed under a reduced pressure, and the oily residue containing the acylphloroglucinol was extracted with Et2O. After removing the Et2O, the crude product was purified via flash chromatography (PE (bp. 50-70C)/EtOAc 5:1?3:1) [21].
60%
General procedure: Phloroglucinol (3; 10.81?g, 85.8?mmol) in carbon disulphide (50?mL) was transferred into a two-necked round-bottomed flask and allowed to stir while aluminium trichloride (46.43?g, 351.8?mmol, 4.1 equiv) was added. Nitrobenzene (40?mL) was then added to the solution over 30?min. The solution was then heated under reflux at 55?C for 30?min. A solution of 2-methylbutanoyl chloride (2) (10.89?g, 85.8?mmol) dissolved in 5?mL nitrobenzene was added to the reaction mixture over 30?min, followed by heating for another 30?min. The reaction mixture was allowed to cool with stirring and then poured into an ice-water bath (400?mL). 100?mL of 3?m hydrochloric acid was then added and the mixture extracted with diethyl ether (3?*?500?mL). The organic solvents were removed under reduced pressure. The oily residue containing the acylphloroglucinol was subjected to VLC over SiGel PF254 using hexane and EtOAc of increasing polarity. The VLC fraction eluted with 30-45% EtOAc in hexane gave (S)-2-methyl-1-(2,4,6-trihydroxyphenyl)butan-1-one as a pale yellow oil (9.71?g, 46.19?mmol, 54%).
2.81%
General procedure: The mixture of phloroglucinol (0.05 mol) and anhydrous aluminum chloride (0.1 mol) were dissolved in dichloromethane (50 mL). Phloroglucinol and aluminum chloride easily dissolved in the solvent and HCl was observed to be produced when the reaction temperature rose to about 33 C. The mixture was heated for 10 min at 40 C and the acyl chloride (0.05 mol) was added dropwise. After refluxing for 15 min, 0.05 mol of HCl was added to quench the reaction. The solvent was evaporated off, and the resultant product extracted with ethyl acetate. The ethyl acetate extract was purified using flash column chromatography over silica gel, eluted with petroleum ether/ethyl acetate (10:1) [22].
General procedure: Aluminum trichloride (1.33 g, 10 mmol) was slowly and carefully added to a solution of phloroglucinol 4 (315 mg, 2.5 mmol) in CH2ClCH2Cl/PhNO2 (1:1, 10 mL) at 0 C. After stirring at this temperature for 10 min under nitrogen atmosphere, acid chloride 5 (3.0 mmol) was added. Then, the ice bath was removed, and the mixture was stirred at 80 C for 3 h. The crude reaction mixture was cooled to room temperature and quenched with water (25 mL). The mixture was extracted with EtOAc (5 × 25 mL), washed with brine, and concentrated in vacuum. The crude product was purified by flash chromatography (silica gel, hexane:EtOAc = 2:l). Their spectra data were referred the reported relative references.
General procedure: Friedel-Crafts acylation: Small amounts of phloroglucinol (0.05 mol) and anhydrous aluminumchloride (0.1 mol) were first dissolved in dichloromethane (50 mL) and kept heated for 1 h at 40 C.Acyl chloride (0.05 mole) was added dropwise into the reaction mixture, reuxed for 8 h, and quenchedwith 0.05 mole of HCl upon completion of the reaction. After the reaction was completed, the reactionmixture was extracted with ethyl acetate and concentrated under reduced pressure. The residueswere subjected to column chromatography using silica gel eluted with hexane/ethyl acetate (10:1) [25].Direct C-alkylation: A well-mixed mixture of acylphloroglucinol (1 mmol), geranyl bromide or prenylbromide (1 mmol), and anhydrous potassium carbonate (0.5 mmol) in dry methanol (3 mL) wasrefluxed for 8 h. After completion of the reaction, excess methanol was removed through high vacuumand the residues were extracted with ethyl acetate. The organic layers were combined, dried, andconcentrated. Column chromatography over silica gel eluted with petroleum ether/ethyl acetate (10:1)gave geranylated/prenylated compounds [11].
Aluminum trichloride (4 g, 40 mmol) at 0 C Slowly and carefully added to a solution of phloroglucin (Compound 3) (1.26 g, 10 mmol) in CH2ClCH2Cl/PhNO2 (1:1, 50 mL). After stirring at this temperature for 10 minutes in nitrogen, The acid chloride (compound 4) (12 mmol) was added. Then, the ice bath was removed, and the mixture was stirred at 80 C for 3 hours. The crude reaction mixture was cooled to room rt and quenched with water (EtOAc). The mixture was extracted with EtOAc (5×100 mL). Wash with brine and concentrate in vacuo. The crude product was purified by flash chromatography (silica gel, hexanes:EtOAc = 2:1) The relative product 5d-5k was obtained in a yield ranging from 60 to 80%.
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