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CAS No. :70424-94-1 MDL No. :MFCD03425302
Formula : C29H26O5 Boiling Point : -
Linear Structure Formula :C6H6O3CO2CH2(C7H6)3 InChI Key :MAUSJTNDKNFSEU-UHFFFAOYSA-N
M.W : 454.51 Pubchem ID :352181
Synonyms :

Safety of [ 70424-94-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 70424-94-1 ]

* 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.

  • Downstream synthetic route of [ 70424-94-1 ]

[ 70424-94-1 ] Synthesis Path-Downstream   1~14

  • 1
  • [ 70424-94-1 ]
  • [ 1486-48-2 ]
YieldReaction ConditionsOperation in experiment
97% With sodium hydroxide; In methanol; for 4h;Reflux; General procedure: Gallic acid (1.5 g,8.83 mmol) was dissolved in 9 cm3 methanol, conc.0.45 cm3 sulfuric acid was added thereto, and the mixturewas stirred under reflux for 5 h. The reaction vessel wascooled down to room temperature and the reaction mixturewas neutralized with saturated sodium bicarbonate solutionat 0 C. Then, the organic solvent was removed at reducedpressure, and the residue dissolved in ethyl acetate, washedwith saturated sodium bicarbonate solution, dried overanhydrous sodium sulfate, and concentrated to give methyl1.39 g 3,4,5-trihydroxybenzoate (7.55 mmol, 86% yield)as white solid. This compound was used in the next stepreaction without further purification.Gallic acid (1.5 g,8.83 mmol) was dissolved in 9 cm3 methanol, conc.0.45 cm3 sulfuric acid was added thereto, and the mixturewas stirred under reflux for 5 h. The reaction vessel wascooled down to room temperature and the reaction mixturewas neutralized with saturated sodium bicarbonate solutionat 0 C. Then, the organic solvent was removed at reducedpressure, and the residue dissolved in ethyl acetate, washedwith saturated sodium bicarbonate solution, dried overanhydrous sodium sulfate, and concentrated to give methyl1.39 g 3,4,5-trihydroxybenzoate (7.55 mmol, 86% yield)as white solid. This compound was used in the next stepreaction without further purification.A mixture of methyl 2.114 g 3,4,5-tris(benzyloxy)benzoate(4.66 mmol), sodium hydroxide (96 mmol), 6 cm3MeOH, and 12 cm3 dioxane was heated at reflux for 4 h.The solvent was removed and the resulting residue waspartitioned between water and ethyl acetate. The combinedorganic layers were washed with brine, dried (Na2SO4),and concentrated at reduced pressure to give the titlecompound (1.984 g, 4.51 mmol, 97% yield) as a whitesolid. Spectral data were in accordance with those previouslyreported
86% With potassium hydroxide; isopropyl alcohol; for 1h;Heating / reflux; To a mixture of methyl 3,4,5- tribenzyloxybenzoate (15) (20.60 g, 45.30 mmol) in 2-propanol (200 mL) was added a solution of potassium hydroxide (3.50 g, 85%, 53.00 mmol) in 2-propanol (25 mL). The mixture was refluxed for 1 h, cooled, and water was added (250 niL). A white precipitate appeared, and the mixture was filtered. Recrystallisation from ethyl acetate afforded the desired compound as white crystals, m.p. 194-195 0C Yield: 17.2 g (86%). 1H NMR (300 MHz, OMSO-d6): delta = 5.05 (2H, s), 5.18 (4H, s), 7.24-7.50 (17H, m), 13.4 (IH, s, broad); 13C NMR (75 MHz): delta = 70.3, 74.3, 108.3, 126.1, 127.7, 128.0, 128.2, 128.3, 128.5 , 136.9, 137.5, 141.0, 152.1, 167.0.
75% With water; sodium hydroxide; In 1,4-dioxane; methanol; at 120℃; for 6h;Inert atmosphere; To the stirred solution of compound 13 (1.93 g, 4.25 mmol) in MeOH (5 mL): dioxane (10 mL): H2O(4 mL), NaOH (0.8 g, 4.25 mmol) was added. The reaction mixture was heated under reflux for 6 h at 120 C, and evaporated. The residual mass was taken in water (20 mL) and extracted with chloroform. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuum to afford compound 14 as white solid (1.77 g, 75%); mp = 274- 276 C, 1HNMR (CDCl3, 400 MHz); delta 5.12 (s, 6H), 7.26 (s, 2H), 7.37- 7.45 (m,15H); 13C NMR (CDCl3, 100 MHz) delta 71.2, 73.2, 109.5, 127.6(s), 127.9, 128 (s), 128.2 (s), 128.5 (s),136.5, 140.4, 152.6, 169.8; HRMS (ESI) m/z [C28H24NaO5] calcd for 463.1521 found 463.1536.
3.30 g With sodium hydroxide; In tetrahydrofuran; methanol; water; at 80℃; for 1h; To a solution of 8c (60.0 g, 0.318 mol) in MeOH (638 mL) was added SOCl2 (23.2 mL, 0.319 mol) fordropwise at 60 C. The reaction mixture was stirred at 60 C for 8 h. Then, the reaction mixture wasevaporated under reduced pressure. The crude mixture was applied to following reaction without furtherpurification.To a mixture of crude material (2.00 g, 10.9 mmol) and K2CO3 (6.78 g, 49.0 mmol) in DMF (36.0 mL)were added benzyl bromide (4.10 mL, 35.9 mmol) and TBAI (1.60 g, 4.33 mmol) at room temperature.The reaction mixture was stirred at room temperature for 11 h. Then, the reaction mixture was filteredthrough a pad of Celite, diluted with H2O, and extracted with CH2Cl2. The organic layer was washed withwater and brine, dried over anhydrous MgSO4, and evaporated under reduced pressure. The crude mixturewas applied to following reaction without further purification.To a stirred solution of crude residue in MeOH/THF (1/1, 36.3 mL) was added 4 M NaOH aq. (9.50 mL,38.0 mmol) at 80 C. The reaction mixture was stirred at 80 C for 1 h. Then, the reaction mixture wasquenched with 6 M HCl aq., and filtered. The filtrate was washed with H2O to give 9c (3.30 g, 7.49 mmol,68%) as a white solid.Spectral data for 9c were in good agreement with those reported in reference.16

Reference： [1]Monatshefte fur Chemie,2018,vol. 149,p. 1293 - 1300
[2]Zeitschrift fur Naturforschung, B: Chemical Sciences,2009,vol. 64,p. 464 - 466
[3]Bioorganic and Medicinal Chemistry Letters,2002,vol. 12,p. 1567 - 1570
[4]Journal of Medicinal Chemistry,2018,vol. 61,p. 1609 - 1621
[5]Organic and Biomolecular Chemistry,2012,vol. 10,p. 2590 - 2593
[6]New Journal of Chemistry,2011,vol. 35,p. 1541 - 1548
[7]Phytochemistry,1999,vol. 52,p. 759 - 767
[8]Patent: WO2006/134352,2006,A1 .Location in patent: Page/Page column 18;26-27
[9]Bulletin of the Korean Chemical Society,2012,vol. 33,p. 2051 - 2054
[10]Chemistry - A European Journal,2012,vol. 18,p. 9063 - 9074
[11]Tetrahedron Letters,2002,vol. 43,p. 8185 - 8189
[12]Synthetic Communications,2006,vol. 36,p. 587 - 597
[13]Tetrahedron Letters,2016,vol. 57,p. 2652 - 2654
[14]Journal of the American Chemical Society,2013,vol. 135,p. 15609 - 15616
[15]Journal of the American Chemical Society,1943,vol. 65,p. 85
[16]Helvetica Chimica Acta,1962,vol. 45,p. 270 - 276
[17]Chemical and Pharmaceutical Bulletin,2003,vol. 51,p. 1085 - 1088
[18]Journal of Medicinal Chemistry,2006,vol. 49,p. 2829 - 2837
[19]Bioorganic and Medicinal Chemistry,2008,vol. 16,p. 7975 - 7982
[20]Chemical and Pharmaceutical Bulletin,2009,vol. 57,p. 190 - 194
[21]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 2191 - 2194
[22]Journal of Agricultural and Food Chemistry,2010,vol. 58,p. 11081 - 11089
[23]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 631 - 636,6
[24]Tetrahedron Letters,2014,vol. 55,p. 275 - 278
[25]Journal of Medicinal Chemistry,2014,vol. 57,p. 3724 - 3736
[26]Heterocycles,2014,vol. 8,p. 1371 - 1396
[27]European Journal of Medicinal Chemistry,2019,vol. 163,p. 560 - 568
  • 2
  • [ 70424-94-1 ]
  • [ 404852-31-9 ]
YieldReaction ConditionsOperation in experiment
93% With hydrazine hydrate; In tetrahydrofuran; methanol; at 70℃; for 12h; Compound (AB)3G1-COOCH3 (4 g, 0.0088 mole) and hydrazine monohydrate (22 mL, 0.44 mole) were dissolved in MeOH (30 mL) and THF (15 mL). The reaction mixture was stirred at 70 C. for 12 hours. After the heating was stopped, the reaction mixture was allowed to cool to room temperature, and the volatiles were removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with H2O. The organic layer was then dried over anhydrous Na2SO4, and the solvent was evaporated to get crude product, which was purified by column chromatography using silica gel as the stationary phase and 5% MeOH in CH2Cl2 as the eluent to get the pure product as a white powder (3.75 g, 93%); 1H NMR (400 MHz, CDCl3) delta: 5.03 (s, ArCH2O, 6H), 6.96 (s, ArH, 2H), 7.18-7.30 (m, PhH, 15H); 13C NMR (100 MHz, CDCl3) delta: 71.54, 75.31, 106.96, 127.60, 128.09, 128.19, 128.32, 128.69, 136.70, 137.52, 141.72, 142.57, 153.03, 168.44; IR(KBr) nu=3282, 3195, 3110, 3089, 3063, 3030, 3007, 2940, 2870, 1631, 1583, 1518, 1498, 1455, 1423, 1153 and 779 cm-1; HRMS (ES+): m/z Calcd. for C24H26N2O4: 454.1893. found: 455.1964 [M+H]+; m.p. 122 C.
93% With hydrazine hydrate; In tetrahydrofuran; methanol; at 70℃; for 12h; Compound 3 (1 g, 2.2 mmol) and hydrazine monohydrate (5.5 mL, 110 mmol) were mixed up in MeOH (20 mL) and THF (10 mL) mixture. The reaction mixture was stirred at 70C for 12 h. After completion of the reaction, the reaction mixture was allowed to cool at room temperature, and the volatiles were removed under reduced pressure. The residue was dissolved in CHCl3 and washed with H2O. The organic layer was then dried over anhydrous Na2SO4, and the solvent was evaporated to get crude product, which was purified by column chromatography using silica gel as the stationary phase and 2% MeOH in CHCl3 as the eluent to get the pure product as a white powder (0.93 g, yield 93 %); 1H NMR (CDCl3, 400 MHz): 7.42-7.33 (m, 11H), 7.28-7.25 (m, 5H), 7.03 (s, 2H ), 5.12 (s, 4H), 5.09 (s, 2H), 4.05 (s, 2H);
91% With hydrazine hydrate; In tetrahydrofuran; methanol; at 70℃; for 12h;Inert atmosphere; As described in a previous study [48], 1.84 g (10 mmol) Methyl-3, 4, 5-trihydroxybenzoate and 5.52 g (40 mmol) potassium carbonate were dissolved in 30mL 1, 4-dioxane, than 3.78 g(30 mmol) benzyl chloride and trace amounts of tertiary butylammonium iodide were added, and then the mixturewas heated toreflux for 24 h. After that, the mixture was filtered and the solventwas removed under reduced pressure. The crude product wasrecrystallized from methanol, and 1.5 g (3.30 mmol) white solid 2was obtained with 88% yield and a melting point of 91.9 C.2.0 g (4.4 mmol) solid 2 and 11 mL (220 mmol) hydrazinemonohydrate were dissolved in 15 mL MeOH and 7mL THF, andthen the mixture was heated to 70 C for 12 h. After that, themixture was cooled to room temperature and the solvent wasremoved under reduced pressure. The residue was dissolved inCH2Cl2 and washed with water, and dried over anhydrous Na2SO4.The crude product obtained was purified by column chromatographyon silica gel (eluent: CH2Cl2/MeOH 95:5), and 1.82 g(4 mmol) white solid 3 was obtained with a 91% yield and a meltingpoint of 121.5-121.7 C.
  • 3
  • [ 99-24-1 ]
  • [ 100-44-7 ]
  • [ 70424-94-1 ]
YieldReaction ConditionsOperation in experiment
94% With potassium carbonate;potassium iodide; In dimethyl sulfoxide; at 20℃;Product distribution / selectivity; Methyl 3,4,5-trihydroxybenzoate (16) (55.24 g, 0.3 mol), benzyl chloride (113.93 g, 0.9 mol), potassium carbonate (124.39 g, 0.9 mol) and potassium iodide (catalytic amount) were mechanically stirred in dry DMSO (200 mL) at room temperature overnight. Water (200 mL) was added and the crude product isolated by filtration. Evaporation of residual solvents in a vacuum desiccator left a pale yellow solid which was essentially pure product. Yield: 128.2 g (94%).
90.5% With tetra-(n-butyl)ammonium iodide; potassium carbonate; In 1,4-dioxane; for 24h;Reflux; Preparation of (AB)3G1-CH2OH (c) Lithium aluminum hydride (0.809 g, 0.0213 mole) was suspended in 40 mL of freshly distilled THF in a dry three-neck round-bottom flask under nitrogen atm. (AB)3 G1-COOCH3 (9 g, 0.0198 mole) was dissolved in 50 mL of freshly distilled THF and added drop wise to the lithium aluminum hydride solution. The reaction mixture was refluxed with stirring for 2 hours. The THF solution was cooled to room temperature and transferred to a beaker. Water was added drop wise to the vigorously stirred THF solution until the gray color of the lithium aluminum hydride was disappeared and a white solid was formed which is filtered and washed with THF. Excess solvent was removed under reduced pressure and the crude product was recrystallized from 95% methanol/water mixture to get the pure product ((AB)3 G1-CH2OH) (7.6 g, 90%); 1H NMR (400 MHz, CDCl3) delta: 4.6 (s, CH2OH, 2H), 5.09 (s, ArCH2O, 2H), 5.15 (s, ArCH2O, 4H), 6.72 (s, ArH, 2H), 7.30-7.48 (m, PhH, 15H); 13C NMR (100 MHz, CDCl3) delta: 65.42, 71.22, 75.26, 106.46, 127.45, 127.83, 127.90, 128.18, 128.52, 128.62, 136.66, 137.13, 137.81, 137.87, 153.02.
89% With potassium carbonate;potassium iodide; In acetone; for 12h;Product distribution / selectivity; Methyl 3,4,5-trihydroxybenzoate (16) (55.24 g5 0.3 mol), benzyl chloride (113.93 g, 0.9 mol), dry potassium carbonate (124.39 g, 0.9 mol) and potassium iodide (catalytic amount) were stirred in refluxing dry acetone (600 mL) for 12 h. After cooling, the acetone was evaporated, and the solution was dissolved in water (250 mL). The water phase was extracted with diethyl ether (4 x 100 mL), the organic phase was washed with brine (2 x 50 mL), dried (MgSO4) and the solvent was removed in vacuo. Recrystallisation from petroleum ether and ethyl acetate gave the titled compound as white crystals, m.p. 102-103 0C. Yield: 121.4 g (89%). Spectroscopic data were in accordance with the literature (J. Barbera, R. Iglesias, J. L. Serrano, T. Sierra, M. R. de Ia Fuente, B. Palacios, M. A. Perez- Jubindo, J. T. Vazquez, J. Am. Chem. Soc. 1998, 120, 2908).
88% With t-butyl ammonium iodide; potassium carbonate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; As described in a previous study [48], 1.84 g (10 mmol) Methyl-3, 4, 5-trihydroxybenzoate and 5.52 g (40 mmol) potassium carbonate were dissolved in 30mL 1, 4-dioxane, than 3.78 g(30 mmol) benzyl chloride and trace amounts of tertiary butylammonium iodide were added, and then the mixturewas heated toreflux for 24 h. After that, the mixture was filtered and the solventwas removed under reduced pressure. The crude product wasrecrystallized from methanol, and 1.5 g (3.30 mmol) white solid 2was obtained with 88% yield and a melting point of 91.9 C.2.0 g (4.4 mmol) solid 2 and 11 mL (220 mmol) hydrazinemonohydrate were dissolved in 15 mL MeOH and 7mL THF, andthen the mixture was heated to 70 C for 12 h. After that, themixture was cooled to room temperature and the solvent wasremoved under reduced pressure. The residue was dissolved inCH2Cl2 and washed with water, and dried over anhydrous Na2SO4.The crude product obtained was purified by column chromatographyon silica gel (eluent: CH2Cl2/MeOH 95:5), and 1.82 g(4 mmol) white solid 3 was obtained with a 91% yield and a meltingpoint of 121.5-121.7 C.
With potassium iodide; sodium carbonate; In water; acetone; EXAMPLE 5a 3.4,5-Trisbenzyloxybenzoic Acid Methyl Ester 105 g (0.83 mol) of benzyl chloride are added dropwise at 56 C., under reflux, over a period of 10 minutes, to 18.4 g (0.1 mol) of 3,4,5-trihydroxybenzoic acid methyl ester, 50.0 g (0.48 mol) of sodium carbonate and 10.0 g (0.06 mol) of potassium iodide in 200 ml of acetone. After a further 20 hours at reflux, 500 ml of water are added at room temperature and the mixture is then extracted with ether. The crude product is worked up in customary manner, excess benzyl chloride is removed by distillation, and the residue is recrystallized from hexane/ethyl acetate. Colourless crystals, yield 45.0 g (98% of theory) 1H-NMR (CDCl3): 3.85 (s,3H, OCH3), 5.05 (s, 2H, OCH2), 5.10 (s, 4H, OCH2), 7.15-7.45 (m, 17H, arom. H)

  • 4
  • [ 70424-94-1 ]
  • [ 6552-73-4 ]
  • deuteromethyl tri-O-benzylgallate [ No CAS ]
  • 5
  • [ 70424-94-1 ]
  • [ 79831-88-2 ]
YieldReaction ConditionsOperation in experiment
97.5% With aluminum (III) chloride; sodium tetrahydroborate; In tetrahydrofuran; at 10 - 30℃;Large scale; Tetrahydrofuran (177.6 liters) is charged to a reactor and A1C13 (6.5 kg, 1.0 eq.) is charged at 10-15 C. 2. To the resulting mixture is charged compound IIIa-13-1 (22.2 kg, 1.0 eq.) and then NaBH4 (1.78 kg, 1.0 eq.) at 10-25 C. 3. The resulting reaction mixture is aged for 10 hours at 20-30 C and then additional NaBH4 is charged (1.78 kg, 1.0 eq.) and the mixture stirred for an additional 12 hours. 4. A further 2 equivalents of NaBH4 are charged with subsequent aging of the reaction mixture (12-14 hours) at which time HPLC analysis shows that 5. The reaction mixture is cooled to about 15 C and water is added slowly (55.5 liters). 6. After addition of water, 2 M HCl is added to the mixture and the resulting mixture stirred for a suitable amount of time at 20 C. 7. The layers are settled, the organic layer is separated and the aqueous layer back-extracted with ethyl acetate. 8. The combined organic layers are washed with 6% NaHC03 and then 20% brine. 9. The combined organic layer and wash is then concentrated to about 2.5 volumes under vacuum at 40-50 C and heptane is charged (about 67 liters). 10. The mixture is further concentrated to about 3 volumes under vacuum. 11. The mixture is filtered and the cake washed with heptane. 12. The cake is dried under vacuum at 35-45 C to obtain 20.1 kg of IIIa-13-1-2 as an off-white sold in 97.5% yield and 96.5% purity.
95% With lithium aluminium tetrahydride; In tetrahydrofuran; for 2h;Heating / reflux; A mixture of methyl gallate 9 (10 g, 53 mmol) and potassium carbonate (45 g, 320 mmol) in DMF (120 mL) was treated with benzyl bromide (210 mmol, 25.7 mL) and stirred at 40 C. under an argon atmosphere for 24 h. The reaction mixture was filtered and the filtrate evaporated to dryness. The residue was dissolved in minimum amount of methylene chloride and diluted with an equal volume of hexanes and loaded onto a short silica gel pad in a sintered glass funnel. The silica was eluted with hexanes (300 mL) to remove excess benzyl bromide and the eluant discarded. The product was then eluted with methylene chloride: hexanes (1:1, 300 mL) followed by methylene chloride (500 mL) and the eluants combined and evaporated to afford pure benzyl product 10 as an off-white solid (100% yield). 1H NMR (300 MHz, CDCl3): delta 3.88 (s, 3H, CH3), 5.11 and 5.13 (2s, 6H, OCH2), 7.35-7.41 (m, 17H, Ar-H). [0119] To a solution of 3,4,5-tribenzyl-methyl gallate 10 (10 g, 22 mmol) in dry tetrahydrofuran (75 mL) was added solid lithium aluminum hydride (1.25 g, 33 mmol) in small portions. The suspension was heated to reflux under argon for 2 h. The reaction was cooled to 0 C. and carefully quenched with the dropwise addition of water. The slurry was then extracted with ethylacetate/hexanes. The organic solution was dried with saturated brine, followed by anhydrous magnesium sulfate, filtered and evaporated to afford the pure alcohol 11 as a white solid (8.9 g, 95% yield). 1H NMR (300 MHz, CDCl3): delta 4.6 (d, 2H, CH2), 5.04 and 5.11 (2s, 6H, OCH2), 6.67 (s, 2H, 2,6-Ar-H), 7.25-7.43 (m, 15H, Ar-H). [0120] To a solution of 3,4,5-tribenzyloxy-benzyl alcohol 11 (8.9 g, 21 mmol) in methylene chloride (200 mL) at 0 C. was added pyridinium chlorochromate (5.43 g, 25 mmol) in small portions with vigorous stirring. The cooling was discontinued and reaction stirred at room temperature for 4 h. The dark brown suspension was filtered over a long pad of silica gel in a sintered glass funnel, and eluted with methylene chloride, until all the pure product eluted out. The organic filtrate was evaporated down to give the pure product 12 as a soft white solid (8.1 g, 91.5% yield). 1H NMR (300 MHz, CDCl3): delta 5.16 (s, 6H, OCH2), 7.18 (s, 2H, 2,6-Ar-H), 7.26-7.41 (m, 15H, Ar-H), 9.80 (s, 1H, CHO).
90% With lithium aluminium tetrahydride; In tetrahydrofuran; for 2h;Inert atmosphere; Reflux; Lithium aluminum hydride (0.809 g, 0.0213 mole) was suspended in 40 mL of freshly distilled THF in a dry three-neck round-bottom flask under nitrogen atm. (AB)3 G1-COOCH3 (9 g, 0.0198 mole) was dissolved in 50 mL of freshly distilled THF and added drop wise to the lithium aluminum hydride solution. The reaction mixture was refluxed with stirring for 2 hours. The THF solution was cooled to room temperature and transferred to a beaker. Water was added drop wise to the vigorously stirred THF solution until the gray color of the lithium aluminum hydride was disappeared and a white solid was formed which is filtered and washed with THF. Excess solvent was removed under reduced pressure and the crude product was recrystallized from 95% methanol/water mixture to get the pure product ((AB)3 G1-CH2OH) (7.6 g, 90%); 1H NMR (400 MHz, CDCl3) delta: 4.6 (s, CH2OH, 2H), 5.09 (s, ArCH2O, 2H), 5.15 (s, ArCH2O, 4H), 6.72 (s, ArH, 2H), 7.30-7.48 (m, PhH, 15H); 13C NMR (100 MHz, CDCl3) delta: 65.42, 71.22, 75.26, 106.46, 127.45, 127.83, 127.90, 128.18, 128.52, 128.62, 136.66, 137.13, 137.81, 137.87, 153.02.
With lithium aluminium tetrahydride; In tetrahydrofuran; EXAMPLE 5b 3,4,5-Trisbenzyloxybenzyl Alcohol A solution of 20.0 g (0.044 mol) of <strong>[70424-94-1]3,4,5-trisbenzyloxybenzoic acid methyl ester</strong> in 100 ml of THF is added dropwise with vigorous stirring, over a period of 60 minutes at room temperature, to a suspension of 4.00 g (0.11 mol) of lithium alanate in 100 ml of THF, in the course of which the temperature rises to 65 C. (reflux). After a further 2 hours at reflux, excess lithium alanate is cautiously hydrolyzed, and the product is isolated in customary manner by extraction with methylene chloride. Amorphous powder, yield 12.0 g (64% of theory). 1H-NMR (CDCl2): 1.70 (t, 1H, OH), 4.45 (d, 2H, CH2OH), 4.95 (s, 2H, OCH2), 5.00 (s, 4H, OCH2), 6.55 (s, 2H, arom. H), 7.15-7.40 (m, 15H, arom. H)

  • 6
  • [ 99-24-1 ]
  • [ 100-39-0 ]
  • [ 70424-94-1 ]
YieldReaction ConditionsOperation in experiment
100% With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 7h; Potassium carbonate (63.31 g, 400 mmol) and benzyl bromide (59.47 mL, 500 mmol) were added to a solution of 3,4,5-trihydroxybenzoate methyl ester (compound 60) (18.41 g, 100 mmol) in DMF (70 mL). This reaction mixture was stirred at 120C for seven hours, and then poured into water. The mixture was extracted with ethyl acetate. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The title compound 61 (3,4,5-tribenzyloxybenzoate methyl ester) (47.19 g) was obtained in a quantitative yield. The NMR spectrum of compound 61 is shown in Table 29. Table 29 NMR spectrum of compound 61400 MHz 1H NMR (CDCl3) delta 7.45-7.24 (17H, m, Ar-H), 5.14 (4H, s, ArCH2O), 5.11 (2H, s, ArCH2O), 3.89 (3H, s, CO2CH3).
100% With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 40℃; for 24h; A mixture of methyl gallate 9 (10 g, 53 mmol) and potassium carbonate (45 g, 320 mmol) in DMF (120 mL) was treated with benzyl bromide (210 mmol, 25.7 mL) and stirred at 40 C. under an argon atmosphere for 24 h. The reaction mixture was filtered and the filtrate evaporated to dryness. The residue was dissolved in minimum amount of methylene chloride and diluted with an equal volume of hexanes and loaded onto a short silica gel pad in a sintered glass funnel. The silica was eluted with hexanes (300 mL) to remove excess benzyl bromide and the eluant discarded. The product was then eluted with methylene chloride: hexanes (1:1, 300 mL) followed by methylene chloride (500 mL) and the eluants combined and evaporated to afford pure benzyl product 10 as an off-white solid (100% yield). 1H NMR (300 MHz, CDCl3): delta 3.88 (s, 3H, CH3), 5.11 and 5.13 (2s, 6H, OCH2), 7.35-7.41 (m, 17H, Ar-H). [0119] To a solution of 3,4,5-tribenzyl-methyl gallate 10 (10 g, 22 mmol) in dry tetrahydrofuran (75 mL) was added solid lithium aluminum hydride (1.25 g, 33 mmol) in small portions. The suspension was heated to reflux under argon for 2 h. The reaction was cooled to 0 C. and carefully quenched with the dropwise addition of water. The slurry was then extracted with ethylacetate/hexanes. The organic solution was dried with saturated brine, followed by anhydrous magnesium sulfate, filtered and evaporated to afford the pure alcohol 11 as a white solid (8.9 g, 95% yield). 1H NMR (300 MHz, CDCl3): delta 4.6 (d, 2H, CH2), 5.04 and 5.11 (2s, 6H, OCH2), 6.67 (s, 2H, 2,6-Ar-H), 7.25-7.43 (m, 15H, Ar-H). [0120] To a solution of 3,4,5-tribenzyloxy-benzyl alcohol 11 (8.9 g, 21 mmol) in methylene chloride (200 mL) at 0 C. was added pyridinium chlorochromate (5.43 g, 25 mmol) in small portions with vigorous stirring. The cooling was discontinued and reaction stirred at room temperature for 4 h. The dark brown suspension was filtered over a long pad of silica gel in a sintered glass funnel, and eluted with methylene chloride, until all the pure product eluted out. The organic filtrate was evaporated down to give the pure product 12 as a soft white solid (8.1 g, 91.5% yield). 1H NMR (300 MHz, CDCl3): delta 5.16 (s, 6H, OCH2), 7.18 (s, 2H, 2,6-Ar-H), 7.26-7.41 (m, 15H, Ar-H), 9.80 (s, 1H, CHO).
96% With potassium carbonate; In acetone; for 24h;Heating / reflux; Methyl 3,4,5-Tribenzyloxybenzoate. Benzyl bromide (10.6 mL, 89.7 mmol) was added to a solution of methyl 3,4,5-trihydroxybenzoate (5.0 g, 27 mmol) and potassium carbonate (oven dried, 12.4 g, 89.7 mmol) in 250 mL of acetone. This solution was heated to reflux under Ar for 24 h. The reaction mixture was cooled, treated with triethylamine (7.6 mL, 54 mmol), and extracted with EtOAc. The organic layer washed sequentially with 10% H2SO4, H2O, and brine, and dried over Na2SO4. After filtration and concentration, 11.8 g (96%) of methyl 3,4,5-tribenzyloxybenzoate was collected as an off white solid.
95.4% With potassium carbonate; In N,N-dimethyl-formamide; at 10 - 60℃; for 4h;Large scale; 3,4,5-trihydroxybenzoate (9.6 kg, 1.0 eq.) and DMF (76.8 liters) are charged to a reactor at 10-25 C. 2. To the reactor is charged K2C03 (25.1 kg, 3.5 eq.) at the same temperature. 3. Benzyl bromide (28.4 kg, 3.2 eq.) is then added slowly to the mixture at a temperature of from 20-45 C and the mixture aged at about 60 C for about 4 hours. 4. Analysis of the reaction mixture shows that 5. The solids are filtered off and the cake washed with DMF twice (1 vol.). 6. The filtered solution and wash is added to water (115 liters) at 5 C and the mixture stirred for 2 hours at 5-15 C. 7. The resulting mixture was filtered and the cake washed with water. 8. The isolated solid was dried for 12 hours under vacuum at 45 C to obtain the product (22.6 kg as an off-white solid. 9. In this alternate process IIIa-13-1-1 is obtained as an off-white solid with 99.4% purity in a 95.4% yield.
94.2% With potassium carbonate; In N,N-dimethyl-formamide; at 40℃; Step A: A solution containing methyl gallate (20.0g, 109mmol), potassium carbonate (90.1g, 652mmol), DMF (120mL), a mixture of benzyl (74.3g, 434mmol) bromide was stirred overnight at 40 ,After the addition of water (240 mL), EtOAc (EtOAc m. The solvent was distilled off under reduced pressure to give 3,4,5 - benzyloxy - benzoic acid methyl ester (68) (46.5g), yield 94.2%.
90% With potassium carbonate; In N,N-dimethyl-formamide; at 60℃; for 15h;Inert atmosphere; To a stirred solution of methyl 3,4,5-trihydroxybenzoate 12 (0.94 g, 5.15 mmol) and potassium carbonate (6.56 g, 25.7 mmol)in DMF (20 mL), benzyl bromide (4.4 g, 25.7 mmol) was added. The reaction mixture was stirred at 60 C under N2 atmosphere. After 15 h, water was added, and the whole was extracted with chloroform. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuum to obtain methyl 3,4,5-tri(benzyloxy)benzoate 13 (1.93g, 90%).
89% With potassium carbonate; In N,N-dimethyl-formamide; for 6h; Compound 2 (1 g, 5.43 mmol) was taken in dry DMF (60 mL) and was stirred in presence of K2CO3 (10 g , 54.34 mmol). Benzyl bromide (4 mL, 16.70 mmol) was added to the stirred solution and stirring was continued for 6h. The progress of reaction was monitored by TLC. After completion of reaction, the reaction mixture was extracted with EtOAc and washed with water. The organic layer was then dried over anhydrous Na2SO4, and the solvent was evaporated to get the crude product, which was purified by column chromatography using using 5% EtOAc in petroleum ether as the eluent to get the pure product 3 as white powder (2.2 g, yield 89 %). 1H NMR (CDCl3, 400 MHz): 7.37-7.35 (m, 4H), 7.33-7.24 (m, 10H), 7.20-7.17 (m, 3H), 5.06 (s, 4H), 5.04 (s, 2H), 3.82 (s, 3H); FTIR (KBr, cm-1 ): 3411, 3044, 3031, 2948, 2878, 1715, 1589, 1499, 1453, 1110 and 754 cm-1 ; mp. 94C
85% With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 6h; General procedure: Gallic acid (1.5 g,8.83 mmol) was dissolved in 9 cm3 methanol, conc.0.45 cm3 sulfuric acid was added thereto, and the mixturewas stirred under reflux for 5 h. The reaction vessel wascooled down to room temperature and the reaction mixturewas neutralized with saturated sodium bicarbonate solutionat 0 C. Then, the organic solvent was removed at reducedpressure, and the residue dissolved in ethyl acetate, washedwith saturated sodium bicarbonate solution, dried overanhydrous sodium sulfate, and concentrated to give methyl1.39 g 3,4,5-trihydroxybenzoate (7.55 mmol, 86% yield)as white solid. This compound was used in the next stepreaction without further purification.Gallic acid (1.5 g,8.83 mmol) was dissolved in 9 cm3 methanol, conc.0.45 cm3 sulfuric acid was added thereto, and the mixturewas stirred under reflux for 5 h. The reaction vessel wascooled down to room temperature and the reaction mixturewas neutralized with saturated sodium bicarbonate solutionat 0 C. Then, the organic solvent was removed at reducedpressure, and the residue dissolved in ethyl acetate, washedwith saturated sodium bicarbonate solution, dried overanhydrous sodium sulfate, and concentrated to give methyl1.39 g 3,4,5-trihydroxybenzoate (7.55 mmol, 86% yield)as white solid. This compound was used in the next stepreaction without further purification.A mixture of methyl 2.114 g 3,4,5-tris(benzyloxy)benzoate(4.66 mmol), sodium hydroxide (96 mmol), 6 cm3MeOH, and 12 cm3 dioxane was heated at reflux for 4 h.The solvent was removed and the resulting residue waspartitioned between water and ethyl acetate. The combinedorganic layers were washed with brine, dried (Na2SO4),and concentrated at reduced pressure to give the titlecompound (1.984 g, 4.51 mmol, 97% yield) as a whitesolid. Spectral data were in accordance with those previouslyreported
With potassium carbonate; In acetone; [00102] Scheme 1. Synthesis of the benzyloxybenzoyl chlorides 5 [00103] In terms of the core aromatic ring, pyrogallol 8 (present in 2a) and 3- methoxycatechol 6a (X = OMe, Y = H, present in la) were chosen. Two halogen substituted phenols, 6b (X = H, Y = CI) and 6c (X = F, Y = H) were chosen to provide a p-donor (similar to the methoxy group) but electron withdrawing group. An unsubstituted catechol 6d (X, Y = H) was included. As shown in Scheme 2, each of these phenols was then coupled to each of the acid chlorides 5a-f and several methoxy-substituted benzoyl chlorides. After coupling, the benzyloxy esters were deprotected via catalytic hydrogenation. The overall yields are shown in Table 2.
With tetra-(n-butyl)ammonium iodide; potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 11h;Inert atmosphere; To a solution of 8c (60.0 g, 0.318 mol) in MeOH (638 mL) was added SOCl2 (23.2 mL, 0.319 mol) fordropwise at 60 C. The reaction mixture was stirred at 60 C for 8 h. Then, the reaction mixture wasevaporated under reduced pressure. The crude mixture was applied to following reaction without furtherpurification.To a mixture of crude material (2.00 g, 10.9 mmol) and K2CO3 (6.78 g, 49.0 mmol) in DMF (36.0 mL)were added benzyl bromide (4.10 mL, 35.9 mmol) and TBAI (1.60 g, 4.33 mmol) at room temperature.The reaction mixture was stirred at room temperature for 11 h. Then, the reaction mixture was filteredthrough a pad of Celite, diluted with H2O, and extracted with CH2Cl2. The organic layer was washed withwater and brine, dried over anhydrous MgSO4, and evaporated under reduced pressure. The crude mixturewas applied to following reaction without further purification.To a stirred solution of crude residue in MeOH/THF (1/1, 36.3 mL) was added 4 M NaOH aq. (9.50 mL,38.0 mmol) at 80 C. The reaction mixture was stirred at 80 C for 1 h. Then, the reaction mixture wasquenched with 6 M HCl aq., and filtered. The filtrate was washed with H2O to give 9c (3.30 g, 7.49 mmol,68%) as a white solid.Spectral data for 9c were in good agreement with those reported in reference.16

Reference： [1]Patent: EP1870403,2007,A1 .Location in patent: Page/Page column 95
[2]Patent: US2004/110790,2004,A1 .Location in patent: Page 14
[3]Bioscience, Biotechnology and Biochemistry,2003,vol. 67,p. 2584 - 2590
[4]Patent: US7288273,2007,B1 .Location in patent: Page/Page column 38
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[6]Patent: WO2017/176948,2017,A1 .Location in patent: Page/Page column 117; 118; 121
[7]Patent: CN110183431,2019,A .Location in patent: Paragraph 0191-0192; 0194
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  • 7
  • [ 99-24-1 ]
  • [ 100-44-7 ]
  • [ 70424-94-1 ]
  • [ 91925-82-5 ]
  • [ 136805-24-8 ]
  • 8
  • [ 79831-86-0 ]
  • [ 100-44-7 ]
  • [ 70424-94-1 ]
  • 9
  • [ 27628-06-4 ]
  • [ 70424-94-1 ]
  • (Z)-3-(3,4-Bis-benzyloxy-phenyl)-3-hydroxy-1-(3,4,5-tris-benzyloxy-phenyl)-propenone [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 90℃; for 12h; General procedure: Methyl 3,4,5-tris(octadecyloxy)benzoate (Compound 2a) was prepared according to the following general procedure, designated general procedure A. To a stirredsolution of methyl 3,4,5-trihydroxybenzoate Ia (5 g, 27.0 mmol) and 1-bromooctadecane (32.6 g, 97.8 mmol) in DMF (100 mL) was added K2C03 (14.9 g,108.0 mmol) and KI (0.45 g, 2.7 mmol) and the resulting mixture stirred at 90 C for12h. The reaction mixture was cooled, diluted with CHCI3 (200 mL), washed withH20 (3 x 50 mL), dried over anhydrous Mg504, filtered and the filtrate concentratedunder reduced pressure. The residue was redissolved in smallest possible amountof warm CHCI3 and mixed with MeOH to induce the precipitation. The precipitate was collected by filtration and dried. The precipitation was repeated to obtain analytically pure methyl 3,4,5-tris(octadecyloxy)benzoate 2a (22.8 g, 90 %). White solid.
  • 11
  • [ 70424-94-1 ]
  • [ 675616-37-2 ]
YieldReaction ConditionsOperation in experiment
100% With bromine; In acetonitrile; at -10 - 0℃; for 5h; Bromine (20.5 mL, 400 mmol) was added dropwise to a solution of the compound 61 that was obtained in Reference Example 25 (47.19 g, 100 mmol) in CH3CN (300 mL) at -10C. This solution was stirred at 0C for five hours and then a saturated aqueous Na2SO3 solution was added thereto. After extraction with ethyl acetate, the organic layer was washed with saturated saline, dried over Na2SO4, and concentrated under reduced pressure. The title compound 62 (2-bromo-3,4,5-tribenzyloxybenzoate methyl ester) (53.5 g, 100 mmol) was obtained in a quantitative yield. The NMR spectrum of compound 62 is shown in Table 30. Table 30 NMR spectrum of compound 62400 MHz 1H NMR (CDCl3) delta 7.45-7.24 (16H, m, Ar-H), 5.05 (6H, m, ArCH2O), 3.99 (3H, s, CO2CH3).
  • 12
  • [ 70424-94-1 ]
  • [ 675616-38-3 ]
  • 13
  • [ 70424-94-1 ]
  • [ 1486-47-1 ]
YieldReaction ConditionsOperation in experiment
[00102] Scheme 1. Synthesis of the benzyloxybenzoyl chlorides 5 [00103] In terms of the core aromatic ring, pyrogallol 8 (present in 2a) and 3- methoxycatechol 6a (X = OMe, Y = H, present in la) were chosen. Two halogen substituted phenols, 6b (X = H, Y = CI) and 6c (X = F, Y = H) were chosen to provide a p-donor (similar to the methoxy group) but electron withdrawing group. An unsubstituted catechol 6d (X, Y = H) was included. As shown in Scheme 2, each of these phenols was then coupled to each of the acid chlorides 5a-f and several methoxy-substituted benzoyl chlorides. After coupling, the benzyloxy esters were deprotected via catalytic hydrogenation. The overall yields are shown in Table 2.
  • 14
  • [ 70424-94-1 ]
  • C14H10O9 [ No CAS ]
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; ;