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[ CAS No. 6702-50-7 ]

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2D
Chemical Structure| 6702-50-7
Chemical Structure| 6702-50-7
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CAS No. :6702-50-7MDL No. :MFCD01321262
Formula : C9H10O4 Boiling Point : 327.7°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :182.17Pubchem ID :4056967
Synonyms :

Computed Properties of [ 6702-50-7 ]

TPSA : 55.8 H-Bond Acceptor Count : 4
XLogP3 : - H-Bond Donor Count : 1
SP3 : 0.22 Rotatable Bond Count : 3

Safety of [ 6702-50-7 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P261-P305+P351+P338UN#:N/A
Hazard Statements:H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 6702-50-7 ]

  • Upstream synthesis route of [ 6702-50-7 ]
  • Downstream synthetic route of [ 6702-50-7 ]

[ 6702-50-7 ] Synthesis Path-Upstream   1~25

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YieldReaction ConditionsOperation in experiment
100% for 18 h; Heating / reflux To a suspension of 3-hydroxy-4- (methyloxy) benzoic acid (25g, 149 mmol. ) in methanol (200 mL) was added concentrated sulfuric acid (1 mL) and the mixture was brought to reflux over 18 hours. The resulting homogeneous solution was cooled to room temperature, concentrated in vacuo and the residual oil taken into ethyl acetate (300 mL). The solution was washed once with water, saturated aqueous sodium hydrogencarbonate then brine and dried over anhydrous magnesium sulfate. Filtration and concentration gave methyl 3- hydroxy-4- (methyloxy) benzoate (27g, 100percent yield) as an OIL.H NMR (400 MHz, CDC13): 7.59 (dd, 1H), 7.57 (d, 1H), 6.85 (d, 1H), 5.72 (s, 1H), 3.93 (s, 3H), 3. 87 (s, 3H).
100% for 18 h; Heating / reflux To a suspension of 3-hydroxy-4- (methyloxy) benzoic acid (25g, 149 mmol. ) in methanol (200 mL) was added concentrated sulfuric acid (1 mL) and the mixture was brought to reflux over 18 hours. The resulting homogeneous solution was cooled to room temperature, concentrated in vacuo and the residual oil taken into ethyl acetate (300 mL). The solution was washed once with water, saturated aqueous sodium hydrogencarbonate then brine and dried over anhydrous magnesium sulfate. Filtration and concentration gave methyl 3- hydroxy-4- (methyloxy) benzoate (27g, 100percent yield) as an OIL.H NMR (400 MHz, CDC13): 7.59 (dd, 1H), 7.57 (d, 1H), 6.85 (d, 1H), 5.72 (s, 1H), 3.93 (s, 3H), 3. 87 (s, 3H).
93% at 65 - 70℃; for 15 h; To a stirred solution of 3-hydroxy-4-methoxy benzoic acid (4.00 g, 23.7 mmol) (commercially available) in methanol, was added sulfuric acid (catalytic amount) and the reaction mixture was heated at 65-70 0C for about 15 hours. Methanol was removed by evaporation; water was added and the reaction mixture was extracted with ethyl acetate. The organic layer was separated, washed with water, dried over anhydrous sodium sulfate, filtered and the solvent was evaporated to yield the title compound. Yield: 4.0 g (93percent)
88.22% at 50 - 55℃; for 4 h; A mixture of 3-hydroxy-4-methoxy benzoic acid 4 (40 g, 0.2378 mol) and methanolic HCl (400 mL) was stirred and heated to 50-55°C for 4 hr. The methanolic HCl was removed by vacuum distillation and the residue was diluted with water 100 mL. The aqueous mixture was extracted with ethyl acetate 2 × 200 mL. The combined organic layers were washed with water and solvent was distilled under vacuum to get light brown compound 5. Which was taken in situ for next step without isolation (38.2 g, yield 88.22percent, purity 98-99percent); m.p. 70-71°C; 1H NMR (DMSO-d6, 300 MHz): δ 9.472 (s, 1H), 7.448-7.476 (d, J = 8.4 Hz, 1H), 7.423 (s, 1H), 7.007-7.035 (d, J = 8.4 Hz, 1H), 3.858 (s, 3H), 3.813 (s, 3H); MS (EI): m/z 183 (M + 1).
85% Cooling with ice To a stirred solution of 3-hydroxy-4-methoxybenzoic acid 19 (1.68 g, 10 mmol) in 15 mL MeOH under ice-cooling, was added SOCl2 (1.09 mL, 15 mmol) dropwise over 10 minutes. After stirring the reaction mixture for 24 h, excess MeOH was distilled out and 10 mL water was added. The mixture was extracted with EtOAc (3 15 mL), and then dried (Na2SO4), evaporated the solvent and the residue was purified by column chromatography (ethyl acetate : petroleum = 1 : 5, v : v) to give product 20 as a white solid (1.56 g, 85percent). Mp: 61-63 °C; 1H NMR (300 MHz, CDCl3): δ = 3.88 (s, 1 H), 3.95 (s, 1 H), 5,67 (s, 1 H), 6.87 (d, J = 8.1 Hz, 1 H), 7.60 (s, 1 H), 7.63 (d, J = 1.5 Hz, 1 H).
83% for 6 h; Heating / reflux b) Preparation of Methyl-2-hydroxy-3-methoxy benzoate; The solid obtained in step a), was refluxed with 10percent methanolic hydrochloric acid solution (250 ml) for 6 hours. The reaction mass was quenched into chilled water (1 It) and repeatedly extracted with methylene chloride (250 ml). The combined methylene <n="27"/>chloride layer was washed with water (100 ml * 2) and methylene chloride distilled out completely at 35-40°C. The residue was stirred in hexane (150 ml), at 25-300C. The solid obtained was filtered, washed with hexane (25 ml) and dried at 40-45°C to yield the title compound (50 gm, 83percent yield).
83.6% at 65℃; To a dry 100 mL three-necked flask, 10 g of 3-hydroxy-4-methoxybenzoic acid, 110 ml of methanol, and 360 uL of concentrated sulfuric acid were successively added, and the mixture was heated to 65 ° C, and reacted under magnetic stirring overnight. The progress of the reaction was judged by thin layer chromatography, and the developing solvent was ethyl acetate: dichloromethane = 1:1. After completion of the reaction, the product was collected, and the product was transferred to a round-bottomed flask to remove methanol under reduced pressure. The residue was extracted with ethyl acetate (25 mL), and neutralized with 15 mL of saturated sodium hydrogencarbonate. Ethyl acetate was evaporated to give a solid product, methyl 3-hydroxy-4-methoxybenzoic acid, 9.06 g,yield: 83.6percent.
54 g for 2 h; Reflux Isovanillic acid (50 g, 0.3 mol), MeOH (500 ml), and thionyl chloride (23.6 ml) were introduced into a reaction vessel, and the mixture was heated at reflux for 2 hours. After cooling, the mixture was neutralized with a 25percent NaOH aqueous solution, and water (250 ml) and activated carbon (2.5 g) were added thereto. After the mixture was stirred at room temperature, insoluble matter was filtrated. The filtrate was concentrated and extracted with AcOEt (350 ml). After the organic layer was separated, it was concentrated by distilling off the solvent to give oily Compound (18a) (54 g) . Compound (18a): 1H NMR (CDCl3, 300 MHz) δ 3.90 (s, 3H) , 3.98 (s, 3H) , 5.63 (s, 1H) , 6.67 (d, J = 8.1 Hz, 1H) , 7.58-7.63 (m, 2H).

Reference: [1] Patent: WO2005/9389, 2005, A2, . Location in patent: Page/Page column 139
[2] Patent: WO2005/9389, 2005, A2, . Location in patent: Page/Page column 139
[3] Journal of Organic Chemistry, 1985, vol. 50, # 2, p. 217 - 231
[4] Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 20, p. 2893 - 2897
[5] Organic and Biomolecular Chemistry, 2016, vol. 14, # 11, p. 3061 - 3068
[6] Patent: WO2006/117653, 2006, A1, . Location in patent: Page/Page column 46
[7] Chemical Communications, 2003, # 10, p. 1170 - 1171
[8] Bioorganic and Medicinal Chemistry Letters, 2010, vol. 20, # 2, p. 718 - 721
[9] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 10, p. 1269 - 1274
[10] Journal of Organic Chemistry, 2017, vol. 82, # 7, p. 3990 - 3995
[11] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 12, p. 3637 - 3640
[12] Patent: WO2008/125867, 2008, A2, . Location in patent: Page/Page column 25-26
[13] Patent: CN108752248, 2018, A, . Location in patent: Paragraph 0036-0038; 0045-0047; 0054-0056
[14] Journal of Heterocyclic Chemistry, 1990, vol. 27, # 7, p. 1957 - 1961
[15] Tetrahedron, 2001, vol. 57, # 2, p. 319 - 329
[16] Journal of the Chemical Society, 1939, p. 1159[17] Journal of the Chemical Society, 1948, p. 265
[18] Journal of the Chemical Society, 1930, p. 817,818
[19] Chemische Berichte, 1941, vol. 74, p. 79,94
[20] Journal of Agricultural and Food Chemistry, 2003, vol. 51, # 24, p. 6953 - 6956
[21] Journal of Medicinal Chemistry, 2005, vol. 48, # 9, p. 3290 - 3312
[22] Patent: WO2007/58338, 2007, A2, . Location in patent: Page/Page column 45
[23] Patent: EP2119702, 2009, A1, . Location in patent: Page/Page column 107
[24] Patent: EP1217000, 2002, A1, . Location in patent: Page 38
[25] ACS Medicinal Chemistry Letters, 2010, vol. 1, # 4, p. 145 - 149
[26] Patent: WO2014/34958, 2014, A1, . Location in patent: Page/Page column 59
[27] Chemistry of Natural Compounds, 2015, vol. 51, # 4, p. 620 - 625[28] Khim. Prir. Soedin., 2015, vol. 51, # 4, p. 536 - 540,5
[29] Angewandte Chemie - International Edition, 2016, vol. 55, # 27, p. 7821 - 7825[30] Angew. Chem., 2016, vol. 128, p. 7952 - 7956,5
[31] Patent: WO2017/199227, 2017, A1, . Location in patent: Page/Page column 9-10
[32] Journal of Medicinal Chemistry, 2017, vol. 60, # 24, p. 10188 - 10204
[33] Journal of Organic Chemistry, 2018, vol. 83, # 17, p. 9667 - 9681
[34] Patent: EP973746, 2003, B1, . Location in patent: Page/Page column 52
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YieldReaction ConditionsOperation in experiment
80%
Stage #1: at 0 - 4℃;
Stage #2: Reflux
3 - hydroxy -4 - methoxybenzaldehyde (10g, 65.7mmol) is dissolved in formic acid (9.1g, 197 . 1mmol) in, solution is cooled to 0 °C, the 35percent hydrogen peroxide (22.3g, 230mmol) slow instillment like in the above solution, keep the 4 °C reaction overnight. Filtering the solid material after completion of the reaction, ice water after washing, drying to obtain solid material. The solid is dissolved in methanol (50 ml) in, slowly adding concentrated sulfuric acid (98percent, 3.2 ml, 59 . 1mmol), heating to reflux, the solvent is removed to obtain the crude product, 10percent methanol aqueous solution by recrystallization to obtain 3 - hydroxy -4 - methoxybenzoic acid methyl ester (II) (9.6g), yield 80percent.
89 %Chromat. at 70℃; for 24 h; General procedure: The reaction of 3,4,5-trimethoxybenzaldehyde (0.01mol)withH2O2(0.04 mol) and methanolwas carried out in 100 mL round bottomflask.The reaction mixture was reflux for 24 h. After completion of the reaction,the reaction mixture pour in distilled water; the aqueous solutionwas the extracted with ethyl acetate (3 × 20 mL) and brine solution toget clear ethyl acetate layer. The organic layerwas driedwith anhydrous sodiumsulfate. It was filtered and vaporized to dryness at reduced pressureto obtained corresponding methyl etster.
Reference: [1] Patent: CN105153065, 2017, B, . Location in patent: Paragraph 0157; 0158; 0159
[2] Organic and Biomolecular Chemistry, 2005, vol. 3, # 12, p. 2271 - 2281
[3] Journal of Molecular Liquids, 2017, vol. 242, p. 1085 - 1095
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YieldReaction ConditionsOperation in experiment
64%
Stage #1: Heating
Stage #2: With sodium hydrogencarbonate In methanol; water at 50℃;
FIGURES 8A-8C are illustrations of the hydroxylation of arenes mediated by 4,5-dichlorophthaloyl peroxide. To examine the scope of the hydroxylation reaction mediated by 4,5-dichlorophthaloyl peroxide (2), two general sets of reaction conditions were developed. The oxidations are carried out using either 1.3 equivalents of 4,5-dichlorophthaloyl peroxide (2) at 50 °C or 2.5 equivalents heated to 75 °C. Operationally the reaction proceeds without the need for special exclusion of air and the use of commercial grade HFIP is sufficient. Thermogravimetric analysis indicates that 4,5-dichlorophthaloyl peroxide has a point of decomposition at 135 °C. Therefore, all reactions reported are conducted at or below 75 °C. While we have not encountered exothermic reactions, appropriate precautions must be used similar to those for all experiments using peroxides. Isolated yields are given below each entry. The yield in parentheses refers to the starting material recovered. The minor regioisomeric positions are labeled with the respective carbon atom number and, after the major isomer, listed sequentially. Reaction conducted at 0°C. Prior to the addition of 4,5-dichlorophthaloyl peroxide (2) p-toluenesulfonic acid monohydrate (1.0 equiv.) was added to the solution of 3(y).
Reference: [1] Patent: WO2014/158209, 2014, A1, . Location in patent: Page/Page column 10
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Reference: [1] Patent: US2002/173656, 2002, A1,
[2] Patent: US2002/198195, 2002, A1,
[3] Patent: US5208247, 1993, A,
[4] Patent: US5603868, 1997, A,
[5] Patent: US6268387, 2001, B1,
[6] Patent: US6384080, 2002, B1,
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Reference: [1] Patent: US6169093, 2001, A,
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Reference: [1] Patent: US6002008, 1999, A,
[2] Patent: US6384051, 2002, B1,
[3] Patent: US6288082, 2001, B1,
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Reference: [1] Patent: EP1263503, 2005, B1,
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Reference: [1] Synlett, 2010, # 19, p. 2947 - 2949
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Reference: [1] Chemische Berichte, 1941, vol. 74, p. 79,94
[2] Monatshefte fuer Chemie, 1966, vol. 97, p. 570 - 578
[3] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 10, p. 1269 - 1274
[4] Chemistry of Natural Compounds, 2015, vol. 51, # 4, p. 620 - 625[5] Khim. Prir. Soedin., 2015, vol. 51, # 4, p. 536 - 540,5
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Reference: [1] Journal of Organic Chemistry, 2017, vol. 82, # 7, p. 3990 - 3995
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Reference: [1] Journal of Organic Chemistry, 2017, vol. 82, # 7, p. 3990 - 3995
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Reference: [1] Patent: US6384080, 2002, B1,
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Reference: [1] Marine Drugs, 2011, vol. 9, # 10, p. 1887 - 1901
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Reference: [1] Journal of Organic Chemistry, 1985, vol. 50, # 2, p. 217 - 231
[2] Chemische Berichte, 1941, vol. 74, p. 79,94
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Reference: [1] Journal of the Chemical Society, 1930, p. 817,818
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Reference: [1] Chemische Berichte, 1941, vol. 74, p. 79,94
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Reference: [1] Chemische Berichte, 1941, vol. 74, p. 79,94
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Reference: [1] Patent: US2007/149523, 2007, A1,
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Reference: [1] Journal of Medicinal Chemistry, 2000, vol. 43, # 17, p. 3244 - 3256
[2] Patent: EP973746, 2003, B1,
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Reference: [1] Patent: US2007/149523, 2007, A1,
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Reference: [1] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 10, p. 1269 - 1274
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Reference: [1] Tetrahedron Letters, 2011, vol. 52, # 10, p. 1053 - 1056
[2] Patent: US2007/149523, 2007, A1,
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YieldReaction ConditionsOperation in experiment
96% With nitric acid; potassium carbonate; acetic acid; sodium sulfate In water; N,N-dimethyl-formamide Production Example 28:
Methyl 5-(benzyloxy)-4-methoxy-2-nitrobenzoate
Commercially available methyl 3-hydroxy-4-methoxybenzoate (10 g) and potassium carbonate (23 g) were dissolved in N,N-dimethylformamide (50 ml).
Benzyl bromide (6.5 ml) was added dropwise to the solution over a period of 10 min.
The mixture was stirred at room temperature overnight.
Water (200 ml) was added thereto, and the mixture was extracted with ethyl acetate.
Saturated brine was then added to the organic layer, followed by extraction with ethyl acetate.
Sodium sulfate was added to the organic layer to dry the organic layer.
Next, the organic layer was filtered, and the solvent was then removed by distillation under the reduced pressure.
The residue was dried through a vacuum pump to give 8.4 g of a white solid.
Subsequently, 7.0 g of the solid was placed in a flask, and 100 ml of acetic acid and 200 ml of nitric acid were added thereto under ice cooling.
The mixture was stirred for 8 hr, and water was then added thereto.
The resultant solid was collected by filtration, was thoroughly washed with water, and was dried through a vacuum pump to give 7.9 g(yield 96percent) of the title compound.
1H-NMR (CDCl3, 400 MHz): δ 3.89 (s, 3H), 3.96 (s, 3H), 5.21 (s, 2H), 7.15 (s, 1H), 7.34 - 7.45 (m, 6H)
Reference: [1] Patent: EP1153920, 2001, A1,
[2] Patent: US2007/149523, 2007, A1,
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Reference: [1] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 10, p. 1269 - 1274
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Reference: [1] Patent: WO2017/199227, 2017, A1,
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