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Chemical Structure| 121-32-4 Chemical Structure| 121-32-4
Chemical Structure| 121-32-4

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Ethylvanillin is a flavorant, about three times as potent as vanillin and is used in the production of chocolate.

4.5 *For Research Use Only! Not for Human Use. We Do Not Sell to Patients.

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Product Details of Ethylvanillin

CAS No. :121-32-4
Formula : C9H10O3
M.W : 166.17
SMILES Code : O=CC1=CC=C(O)C(OCC)=C1
English Name :3-Ethoxy-4-hydroxybenzaldehyde
MDL No. :MFCD00006944
InChI Key :CBOQJANXLMLOSS-UHFFFAOYSA-N
Pubchem ID :8467

Safety of Ethylvanillin

Application In Synthesis of Ethylvanillin

* 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 [ 121-32-4 ]

[ 121-32-4 ] Synthesis Path-Downstream   1~41

  • 1
  • [ 121-32-4 ]
  • [ 5438-38-0 ]
YieldReaction ConditionsOperation in experiment
27% Stage #1: 4-hydroxy-3-ethoxybenzaldehyde With sodium hydroxide; silver nitrate In water at 20℃; for 2.33333h; Heating / reflux; Stage #2: With sulfuric acid In water 46.1 A solution of silver nitrate (45.0 g, 265.0 mmol, 1.0 equiv) in water (230 mL) was treated with NaOH (10.6 g, 265 mmol, 1.0 equiv) and stirred for 20 min at rt. The formed precipitate was filtered off, washed with water (3×200 mL) and directly suspended in water (260 mL). To this suspension was added 3-ethoxy-4-hydroxy-benzaldehyde (20.0 g, 120.4 mmol, 0.45 equiv) and NaOH (26.5 g, 662.5 mmol, 2.5 equiv) the reaction mixture heated to reflux for 2 h. The reaction mixture was filtered, acidified to pH 2 by addition of sulfuric acid and the solution extracted with ethyl acetate (3×100 mL). The combined organic phases were dried over MgSO4, the solvent removed by evaporation under reduced pressure and the crude material purified over a plug of silica eluting with dichloromethane/methanol/acetic acid (97:2:1) to give 5.8 g (27%) of the title compound. 1H NMR (300 MHz, DMSO): δ 1.32 (t, J=7.0 Hz, 3H), 4.04 (q, J=7.0 Hz, 2H), 6.88 (d, J=8.0 Hz, 1H), 7.46 (s, 1H), 7.48 (d, J=8.0 Hz, 1H), 9.67 (br s, 1H), 12.42 (br s, 1H). 13C NMR (75 MHz, DMSO): δ 14.52, 63.93, 114.09, 115.11, 121.68, 123.49, 146.29, 151.32, 167.22. MS (ISN): 181.0 [M-H]-.
With sodium hydroxide; silver nitrate
With sodium hydroxide; silver perchlorate
Multi-step reaction with 3 steps 1: aqueous KOH 2: potassium permanganate; aqueous acetone 3: aqueous KOH-solution
With sodium hydroxide; potassium hexacyanoferrate(III) In ethanol; water at 30℃; for 8h; EXPERIMENTAL Kinetic measurements: All kinetic measurements were performed under pseudo first-order conditions where [ethylvanillin] was always in excess over hexacyanoferrate(III), at a constant ionic strength in alkaline medium at a constant temperature of (30 ± 0.1) °C, respectively, unless otherwise stated. The reaction was initiated by mixing the thermostatted solutions of hexacyanoferrate(III) and ethyl vanillin, which also contained the required concentration of NaOH and KCl. The progress of the reaction was followed by observing the disappearance of hexacyanoferrate(III), titrimetrically. Pseudofirst-order rate constants, kobs, were obtained (Tables 1 and 2) from the slopes of plots of log10 [Fe(CN)63-] versus time; the plots were linear and the kobs values were reproducible to within ±5 %. Stoichiometry and products analysis: Reaction mixtures with different sets of concentrations of reactants where [Fe(CN)63-] was in excess over [ethyl vanillin] at a constant ionic strength and alkali were kept for about 8 h at 30 °C in a closed vessel.

  • 2
  • [ 121-32-4 ]
  • [ 108-24-7 ]
  • [ 72207-94-4 ]
YieldReaction ConditionsOperation in experiment
95% With N-ethyl-N,N-diisopropylamine; bis(trifluoromethane)sulfonimide lithium In dichloromethane at 20℃; for 18h; chemoselective reaction;
With potassium hydroxide
With pyridine In dichloromethane Ambient temperature;
In acetone at 20℃;

  • 3
  • [ 121-32-4 ]
  • [ 100-44-7 ]
  • [ 60186-33-6 ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide; In water; N,N-dimethyl-formamide; at 20 - 60℃; for 3.5h; To the solution of 3-ethoxy-4-hydroxy-benzaldehyde (83g) in N,N-dimethylformamide (400ml) was gradually added 10 M sodium hydroxide (55 ml) and then benzyl chloride (60ml) was added at a temperature under 40C. The mixture was stirred at room EPO <DP n="30"/>temperature for a half an hour and for 2 hours at 6O0C. The solution was poured into ice- cold water (2 1) and extracted with diethyl ether. The organic phase was washed with water and 5M sodium hydroxide and then it was dried and evaporated. The product was recrystallized from toluene-heptane. 1H NMR (DMSOd6): delta = 1.34 (t, 3H), 4.12 (q, 2H), 5.24 (s, 2H), 7.26 (d, IH), 7.34-7.53 (m, 7H), 9.83 (s, IH).
  • 6
  • [ 7647-01-0 ]
  • [ 60186-33-6 ]
  • [ 121-32-4 ]
  • 7
  • [ 121-32-4 ]
  • [ 75-36-5 ]
  • [ 72207-94-4 ]
YieldReaction ConditionsOperation in experiment
100% With triethylamine In dichloromethane at 0℃; for 0.5h; 8 Example 8 N-[1-cyano-2-(7-ethoxy-1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yloxy)-1-methylethyl]-4-trifluoromethoxybenzamide Example 8 N- [ 1 -Cyano-2-(7-ethoxy- 1 -hydroxy- 1.3 -dihydro-benzo [c] [ 1.2]oxaborol-6-yloxy )- 1 -meth yl-ethyl -4-trifluoromethoxy-benzamide To a solution of 3-ethoxy-4-hydroxy-benzaldehyde (50.0 g, 0.30 mol) and Et3N (39.2 g, 54 mL, 0.39 mol) in DCM (500 mL) at 0 °C is added CH3COCl (30.6 g, 28 mL, 0.39 mol) at 0°C. After the addition is complete, the reaction mixture is stirred at 0°C for 30 min. Then the filter cake washed with DCM, and the combined filtrate is washed with water and brine, the organic layer is dried over Na2S04 and evaporated to give the desired product (62.0 g, 100% yield) as a yellow solid.
87% With pyridine In dichloromethane for 1h; Heating;
With pyridine In dichloromethane for 1h; Heating;
  • 9
  • [ 121-32-4 ]
  • [ 89-75-8 ]
  • [ 444110-64-9 ]
YieldReaction ConditionsOperation in experiment
90% With pyridine In benzene at 20 - 23℃;
  • 10
  • [ 121-32-4 ]
  • [ 569646-79-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: acetone; aq. NaOH solution 2: sodium-amalgam; water
Multi-step reaction with 2 steps 1: sodium hydroxide / water / 48 h / 20 °C 2: hydrogen; Pd/C / methanol / 2 h / 20 °C
Multi-step reaction with 2 steps 1: sodium hydroxide / water / 13 h / 15 - 30 °C 2: palladium-carbon; hydrogen; sodium hydrogencarbonate / water; 2-methyltetrahydrofuran / 100 - 150 °C
  • 11
  • [ 121-32-4 ]
  • [ 42149-74-6 ]
  • [ 307303-17-9 ]
YieldReaction ConditionsOperation in experiment
With sodium iodide; sodium chloride; potassium carbonate In water; N,N-dimethyl-formamide R.137 Reference Example 137 Reference Example 137 A mixture of ethyl vanillin (5.0 g), 2-chloroethyl propyl ether (4.6 ml), sodium iodide (5.46 g), potassium carbonate (6.23 g) and DMF (50 ml) was stirred at 90° C. for 3 days. The reaction mixture was mixed with water and was extracted with ethyl acetate. The organic layer was washed with water and an aqueous saturated solution of sodium chloride, and was dried with magnesium sulfate. After concentration under reduced pressure, the residue was subjected to separation and purification using column chromatography (ethyl acetate:hexane 1:2) to obtain 3-ethoxy-4-(2-propoxyethoxy)benzaldehyde (7.34 g) as a light yellow, oily substance. 1H-NMR (200 MHz, CDCl3) δ0.93 (3H, t, J=7.4 Hz), 1.47 (3H, t, J=7.0 Hz), 1.53-1.70 (2H, m), 3.53 (2H, t, J=6.7 Hz), 3.86 (2H, t, J=5.0 Hz), 4.14 (2H, q, J=7.0 Hz), 4.26 (2H, t, J=5.0 Hz), 7.02 (1H, d, J=8.0 Hz), 7.40-7.45 (2H, m), 9.84 (1H, s). IR (neat) 1686, 1586, 1508, 1435, 1395, 1265, 1132, 1042 cm-1.
7.34 g With potassium carbonate; sodium iodide In N,N-dimethyl-formamide at 90℃; for 72h;
  • 12
  • [ 121-32-4 ]
  • [ 100-39-0 ]
  • [ 60186-33-6 ]
YieldReaction ConditionsOperation in experiment
85% With potassium carbonate; In N,N-dimethyl-formamide; at 20 - 40℃; for 2h; To a solution of3-ethoxy-4-hydroxy-benzaldehyde (830 mg, 5 mmol) in N'N-dimethylforrnemide (5 mL)was gradually added K2CO3 (20 mg) and then PmBr (6 mmol) was added ata temperature under 40 C. The mixture was stirred at room temperature for 2 h.The solution was poured into ice-cold water (10 mL) and extracted with diethylether. The organic phase was washed with water and sodium hydroxide and then itwas dried and evaporated to obtain 18 (1.1g, 85%). Compound 18 was reacted with sophoridine using same proceduredescribed in synthesis of 11-16 to obtain 14-(4-(benzyloxy)-3-ethoxyphenylmethylene)sophoridine (20) (120 mg, 30%)
With potassium carbonate; In acetonitrile; for 3h;Heating / reflux; 25 g of 3-ethoxy-4-hydroxybenzaldehyde, 27 g of benzyl bromide, 25 g of potassium carbonate and 250 ml of acetonitrile were mixed, and stirred under condition of reflux for 3 hours. Then the reaction mixture was cooled to room temperature. Ethyl acetate was added to it, and solid was filtered off. The obtained organic layer was concentrated under reduced pressure, the residue was washed bymethyl=tert-butylether and hexane to obtain 36 g of 4-benzyloxy-3-ethoxybenzaldehyde.1H-NMR (CDCl3, TMS) delta (ppm): 9.82 (1H, s), 7.28-7.44 (7H, m), 6.98 (1H, d, J=8.2 Hz), 5.24 (2H, s), 4.18 (2H, q, J=7.0 Hz), 1.49 (3H, t, J=7.0 Hz)
With potassium carbonate; In acetonitrile; for 3h;Heating / reflux; Reference Example 5 25 g of 3-ethoxy-4-hydroxybenzaldehyde, 27 g of benzyl bromide, 25 g of potassium carbonate and 250 ml of acetonitrile were mixed and stirred under reflux for 3 hours. After the reaction mixture was allowed to cool to room temperature, ethyl acetate was added and the mixture was filtered. The resulting filtrate was concentrated under reduced pressure. The residue was washed with tert-butyl methyl ether and hexane to obtain 36 g of 4-benzyloxy-3-ethoxybenzaldehyde. 1H-NMR (CDCl3, TMS) delta (ppm): 9.82 (1H, s), 7.28-7.44 (7H, m), 6.98 (1H, d, J = 8.2 Hz), 5.24 (2H, s), 4.18 (2H, q, J = 7.0 Hz), 1.49 (3H, t, J = 7.0 Hz)
  • 13
  • [ 121-32-4 ]
  • [ 558-42-9 ]
  • 3-ethoxy-4-(2-hydroxy-2-methyl-propoxy)-benzaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
67.1 In analogy to Example 64.1, from 3-ethoxy-4-hydroxy-benzaldehyde and 1-chlor-2-methyl-2-propanol there was obtained 3-ethoxy-4-(2-hydroxy-2-methyl-propoxy)-benzaldehyde.
  • 14
  • [ 121-32-4 ]
  • [ 5292-43-3 ]
  • [ 51264-76-7 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate; In N,N-dimethyl-formamide; 91d 4-Formyl-2-ethoxyphenoxyacetic acid 4-Hydroxy-3-ethoxybenzaldehyde (5.0 g, 36 mmol), potassium carbonate (5.0 g, 36 mmol), and t-butyl bromoacetate (5.9 mL, 36 mmol) were heated to 55 C. overnight in DMF (35 mL). After removal of solvent, the mixture was extracted with EtOAc and water, then brine. After drying (Na2 SO4), solvent was removed to yield a white solid (9.7 g). mp 90-92.6 C. MS (NH3): 298 (base, M+NH4).
  • 15
  • [ 121-32-4 ]
  • [ 178686-24-3 ]
YieldReaction ConditionsOperation in experiment
With nitric acid; In water; acetic acid; for 17.0h; a). 3-Ethoxy-4-hydroxy-5-nitro-benzaldehyde To a solution of 3-ethoxy-4-hydroxybenzaldehyde (5 g) in acetic acid (50 ml) was added nitric acid (1.4 ml) in 2 portions. The resulting suspension was stirred for 17 h. The solid was collected by filtration, washed with water and dried in vacuo.Yield: 5.07 g.
With nitric acid; acetic acid; for 17.0h; Example 14; Propane- 1 -sulfonic acid r5-(3-cvano-2-methyl-5-oxo-7-propyl-l,4,5,6,7,8-hexahvdro- quinolin-4- vD-3 -ethoxy-2-(3 -methoxy-benzyloxy) -phenyll -amide(a). 3-Ethoxy-4-hvdroxy-5-nitro-benzaldehvdeTo a solution of 3-ethoxy-4-hydroxybenzaldehyde (5 g) in acetic acid (50 ml) was added nitric acid (1.4 ml) in 2 portions. The resulting suspension was stirred for 17 h. The solid was collected by filtration, washed with water and dried in vacuo.Yield: 5.07 g.
  • 16
  • [ 121-32-4 ]
  • [ 92138-20-0 ]
  • [ 956291-33-1 ]
  • 17
  • [ 121-32-4 ]
  • [ 774-55-0 ]
  • [ 1289514-07-3 ]
YieldReaction ConditionsOperation in experiment
80% With sodium hydroxide In ethanol at 20 - 40℃; for 12.1667h;
  • 18
  • [ 121-32-4 ]
  • [ 70842-33-0 ]
YieldReaction ConditionsOperation in experiment
43% With chlorine; acetic acid at 25℃; for 0.5h;
2.59 g Stage #1: 4-hydroxy-3-ethoxybenzaldehyde With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Stage #2: With N-chloro-succinimide In tetrahydrofuran; mineral oil at 20℃; 41.A A) 3-cWom-5-ethoxy-4-hydroxybenzaldehyde [0521] Sodium hydroxide (60% dispersion in oil, 1.43 g) was added to a solution of 3-ethoxy-4-hydroxybenzaldehyde (5.41 g) in THF (100 mL) at 0°C, the resultant was stirred for 30 minutes at the same temperature. A solution of N-cWorosuccinimide (4.56 g) in THF (100 mL) was added dropwise thereto, and the resultant was stirred for 48 hours at room temperature. An aqueous saturated ammonium chloride solution was added to the reaction mixture, and the precipitated solid was washed with a mixed solution in which ethyl acetate and hexane was mixed at a ratio of 1 : 1. Extraction was performed on the obtained washing solution using a mixed solution in which ethyl acetate and hexane was mixed at a ratio of 1 : 1. The obtained organic layer was washed with a saturated saline solution, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by a silica gel column chromatography (hexane/ethyl acetate), thereby obtaining the title compound (2.59 g). 1H NMR (400 MHz, DMSO-de) δ 1.38 (3H, t, J = 6.8 Hz), 4.17 (2H, q, J = 6.8 Hz), 7.39 (1H, s), 7.58 (1H, s), 9.77 (1H, s), 10.44 (1H, his).
  • 19
  • [ 121-32-4 ]
  • [ 1668-54-8 ]
  • [ 1465740-01-5 ]
  • 20
  • [ 121-32-4 ]
  • [ 62674-12-8 ]
  • [ 1558784-87-4 ]
YieldReaction ConditionsOperation in experiment
37.1% With acetic acid; 2-Methylpiperidin In toluene at 130℃; for 2h; Inert atmosphere; 5.1.2 General procedure for synthesis of 3,4-dihalo-5-(4-hydroxybenzylidene)furan- 2(5H)-one intermediates (A1B1) General procedure: Benzaldehyde derivatives (B1, 1.0mmol) and halogenated furanones (A1, 1.0mmol) were dissolved in anhydrous toluene (30mL), and then a catalytic amount of 2-methyl piperidine and glacial acetic acid were slowly dropped to the solution under the atmosphere of nitrogen. The reaction mixture was refluxed at 130°C for 2h until the disappearance of starting materials (TLC analysis), and then cooled to room temperature. The toluene was removed under reduced pressure and the residue was dissolved in methanol. This solution was concentrated and purified by silica gel column chromatography with ethyl acetate-petroleum (1:12) as eluent to produce resultant intermediates.
  • 21
  • [ 121-32-4 ]
  • [ 88491-44-5 ]
  • [ 1698886-38-2 ]
YieldReaction ConditionsOperation in experiment
98% With acetic anhydride; triethylamine at 110℃; for 6h;
  • 22
  • [ 121-32-4 ]
  • [ 79-11-8 ]
  • [ 51264-76-7 ]
  • 23
  • [ 121-32-4 ]
  • [ 102169-52-8 ]
  • [ 1520078-26-5 ]
YieldReaction ConditionsOperation in experiment
95.3% With acetic acid In methanol at 79℃; for 0.05h; Microwave irradiation; Sealed tube; Green chemistry; Microwave heating General procedure: In a dry sealed tube, the appropriate aromatic aldehydes (12 mmol) were added to a mixture of compound 3 (10 mmol) and 1 mL methanol:acetic acid (9:1). The resulting mixture was subjected to microwave irradiation for 2-4 min at ~85 C.At the end of this period, the crude products were cooled to RT and poured into ice cold distilled water (10 mL). The resulting products (5a-r) were filtered and dried in vacuum. After that, all the derived products were purified by crystallization from methanol.
  • 24
  • [ 121-32-4 ]
  • [ 6761-52-0 ]
  • N'-(3-ethoxy-4-hydroxybenzylidene)-3-aminopyrazine-2-carbohydrazide [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% for 0.15h;Microwave irradiation; General procedure: Second step consists of condensation of <strong>[6761-52-0]3-aminopyrazine-2-carbohydrazide</strong> (0.5 gm, 0.003 mol) with aromatic aldehydes (0.5 gm, 0.008 mol) using microwaveirradiation (8 - 10 min, 350 W). After cooling and filtration,the product was recrystallized using ethanol [6, 9] (Fig. 1).
In ethanol;Microwave irradiation; General procedure: Asolution of aromatic/substituted aldehydes (0.008 mole, 0.9gm) in 25ml ethanolwas added to a solution of compound 2(0.003 mol, 0.5gm) in 10 ml ethanol and wasirradiated in a microwave oven for 8-10 min (350 W). The resultanthydrazone was precipitated by addition of water (30 ml). The product wasfiltered and purified using ethanol.
  • 25
  • [ 121-32-4 ]
  • [ 56517-30-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sodium hydroxide / water / 4 h / 98 °C / Large scale 2.1: activated carbon / toluene / 0.5 h / 65 - 70 °C / Large scale 2.2: 3.5 h / 15 - 45 °C / Autoclave; Large scale
  • 26
  • [ 121-32-4 ]
  • [ 7169-35-9 ]
  • [ 2093335-75-0 ]
YieldReaction ConditionsOperation in experiment
73% With aluminum oxide In dichloromethane at 20℃; Inert atmosphere; 4.1.1. General procedure for the synthesis of 2-benzylidenebenzofuran-3(2H)-one (method A) General procedure: To a solution of benzofuran-3(2H)-one (1.0 mmol) and benzaldehyde(1.0 mmol) in dichloromethane (6 mL) was addedaluminum oxide (30.0 mmol) at room temperature. After stirringfor 6 h, the reaction mixture was filtered off. The filtrate wasconcentrated under vacuum and the residue was purified by flash chromatography on silica gel to give the desired compound.
  • 27
  • [ 121-32-4 ]
  • [ 6272-26-0 ]
  • [ 120-05-8 ]
YieldReaction ConditionsOperation in experiment
44% With potassium hydroxide In methanol; water for 3h; Reflux; Inert atmosphere; 4.1.2. General procedure for synthesis of 2-benzylidenebenzofuran-3(2H)-one (method B) General procedure: To a solution of 3,4-dihydroxybenzaldehyde (1.0 mmol) and the benzofuran-3(2H)-one derivatives (1.0 mmol) in methanol (20 mL)was added an aqueous solution of 50% potassium hydroxide (15.0 mmol). After refluxing for 3 h, the reaction mixture was cooled to rt and concentrated under vacuum. The residue was diluted with water (40 mL) and extracted with ethyl acetate(3 50 mL). The combined organic phases were washed with brine,dried over anhydrous Na2SO4 and concentrated under vacuum. The residue was purified by flash chromatography on silica gel to provide the desired compound.
  • 28
  • [ 121-32-4 ]
  • [ 15832-09-4 ]
  • [ 2092922-65-9 ]
YieldReaction ConditionsOperation in experiment
72% With aluminum oxide In dichloromethane at 20℃; Inert atmosphere; 4.1.1. General procedure for the synthesis of 2-benzylidenebenzofuran-3(2H)-one (method A) General procedure: To a solution of benzofuran-3(2H)-one (1.0 mmol) and benzaldehyde(1.0 mmol) in dichloromethane (6 mL) was addedaluminum oxide (30.0 mmol) at room temperature. After stirringfor 6 h, the reaction mixture was filtered off. The filtrate wasconcentrated under vacuum and the residue was purified by flash chromatography on silica gel to give the desired compound.
  • 29
  • [ 121-32-4 ]
  • [ 7169-37-1 ]
  • [ 2092922-67-1 ]
YieldReaction ConditionsOperation in experiment
69% With aluminum oxide In dichloromethane at 20℃; Inert atmosphere; 4.1.1. General procedure for the synthesis of 2-benzylidenebenzofuran-3(2H)-one (method A) General procedure: To a solution of benzofuran-3(2H)-one (1.0 mmol) and benzaldehyde(1.0 mmol) in dichloromethane (6 mL) was addedaluminum oxide (30.0 mmol) at room temperature. After stirringfor 6 h, the reaction mixture was filtered off. The filtrate wasconcentrated under vacuum and the residue was purified by flash chromatography on silica gel to give the desired compound.
  • 30
  • [ 121-32-4 ]
  • [ 608141-42-0 ]
  • [ 608142-27-4 ]
  • 31
  • [ 7560-65-8 ]
  • [ 121-32-4 ]
  • [ 2539-53-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: molybdenum hexacarbonyl; di-α-phenethyl peroxide / 45 °C 2.1: sodium hydrogen sulfate / 50 °C 2.2: 50 h / 250 °C / 7500.75 Torr 2.3: 70 °C
  • 32
  • [ 121-32-4 ]
  • [ 57-55-6 ]
  • [ 68527-76-4 ]
YieldReaction ConditionsOperation in experiment
98% With mixture of acetic anhydride and phosphoric acid composite catalyst In toluene for 20h; Reflux; Industrial scale; 1-9 Example 1 a. Into a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 5.0 g of phosphoric acid and 45.0 g of acetic anhydride were placed, and the mixture was heated and kept at 35 ° C for 24 hours to obtain 50.0 g of a composite catalyst.b. In a three-necked flask equipped with a thermometer, a stirrer, a water-oil separator and a reflux condenser, 1.0 kg (6.0 mol) of ethyl vanillin, 0.92 kg (12.0 mol) of 1,2-propanediol, and 50.0 g of a composite catalyst were placed. And 2.0 kg of toluene, stirred and heated to reflux for dehydration, and the dehydration time was 20 hours.After the reaction, the system was lowered to room temperature.The reaction solution was washed with saturated brine, and then a small amount of 20% by mass of Na was added to the system.2CO3The solution was adjusted to pH = 8-9.Then, toluene and unreacted 1,2-propanediol are distilled off under normal pressure, and then distilled under reduced pressure to collect a fraction of 150-152 ° C / 0.2 kPa, which is the target product ethyl vanillin 1,2-propanediol acetal, and the product is obtained. 0.98 kg, as shown in Fig. 1, was found to have a content of 99.1% and a yield of 98%.
  • 33
  • [ 121-32-4 ]
  • [ 41764-74-3 ]
  • (E)-N'-(3-ethoxy-4-hydroxybenzylidene)-3,4-dimethoxybenzohydrazide [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% In ethanol; for 6h;Reflux; General procedure: A mixture of methyl 3,4-dimethoxybenzoate (1mmol) and corresponding benzaldehyde (1mmol) was refluxed in ethanol (7ml) for 6h. Reaction completion was checked by TLC. The mixture was cooled to room temperature and the resulted precipitate was collected and washed with diethyl ether to yield the final pure products. Moreover, in some cases, recrystallization in appropriate solvents was done in order to obtain the pure derivatives. 2.4.1 (E)-3,4-dimethoxy-N'-(4-nitrobenzylidene)benzohydrazide (D1) Yellow solid; yield: 82%; M.P: 208-210C. 1H NMR (300MHz, DMSO-d6): δ (ppm) 3.85 (s, 6H, OCH3), 7.09 (d, 1H, Ar-H-5, J=6.5Hz), 7.42-7.58 (m, 2H, Ar-H-2, 6), 7.96 (d, 2H, Ar-H-2′,6′), 8.28 (d, 2H, Ar-H-3′,5′), 8.55 (s, 1H, N=CH), 12.00 (s, 1H, NH). 13C NMR (75MHz, DMSO-d6): δ (ppm) 56.10 (OCH3), 56.14 (OCH3), 111.46, 121.66, 121.70, 124.52, 125.53, 128.32, 141.26, 145.06, 148.20, 148.86, 152.45, 163.24 (C=O). MS (EI, 70eV): m/z (%)=329 (M+, 10), 165 (100). Anal. Calcd for C16H15N3O5: C 58.36, H 4.59, N 12.76%, found: C 58.44, H 4.61, N 12.72%.
  • 34
  • [ 121-32-4 ]
  • [ 568556-77-4 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate In N,N-dimethyl-formamide at 25℃; General Method for the Synthesis of 3 General procedure: A mixture of 2 (10 mmol), the corresponding halogenated hydrocarbons (8 mmol), K2CO3 (2.07 g, 15 mmol) in DMF(5 mL) was stirred in a 50 mL round bottom flask at 25°C for 8-12 h. Saturated brine was added when the reaction was over,and the mixture was extracted with DCM (25 mL × 2). The combined organic layers were washed with a saturated solution of potassium carbonate, until the spot of 2 was invisibleon the TLC plate, and with water, and dried with anhydrous sodium sulfate. Solvent was removed in vacuo to furnish a white solid and the product can be used for the next step without further purification.
  • 35
  • [ 121-32-4 ]
  • [ CAS Unavailable ]
  • [ 57409-51-5 ]
  • [ 939331-23-4 ]
YieldReaction ConditionsOperation in experiment
25% In 1,4-dioxane at 20℃; General procedure for the synthesis of 5-(het)-aryl-3-hydroxy-1-hydroxyethyl-4-(thienyl-2-carbonyl)-3-pyrrolin-2-ones 1a-1s. General procedure: 0.01 mol of 2-thienylcarbonylpyruvic acid methyl ester was dissolvedin 15 mL of dioxane upon heating. A mixture of0.01 mol of ethanolamine and 0.01 mol of the correspondingaromatic aldehyde was added to the solution. Themixture was stirred and then kept at room temperatureovernight. The precipitate was fi ltered off and recrystallizedfrom ethyl alcohol.
  • 36
  • [ 121-32-4 ]
  • [ 41697-08-9 ]
  • [ 862675-28-3 ]
YieldReaction ConditionsOperation in experiment
60% With acetic acid In ethanol at 50℃;
  • 37
  • [ 121-32-4 ]
  • [ 62-53-3 ]
  • [ 3421-08-7 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 4-hydroxy-3-ethoxybenzaldehyde With cyclohexylamine; acetic acid In methanol at 20℃; Stage #2: aniline In methanol at 20℃; 2.2. Synthesis of symmetric & unsymmetric 2,5-diamino 1,4-benzoquinones General procedure: 15 symmetric and unsymmetric ABQs were synthesized by the previouslyreported method [22] via Scheme 1.Ethyl vanillin (10 mmol) and cyclohexylamine (10 mmol) were mixedin 10 mL methanol along with addition of a trace amount of glacial aceticacid and allowed for slow evaporation under open air at room temperature.After complete evaporation of methanol, the resulting residue wasredissolved in 10 mL of methanol and added two equivalents of aromatic/alicyclic primary amines and allowed to evaporate at room temperature.Complete evaporation of the reaction mixture followed bypurification by column chromatography using hexane/ethyl acetategradient afforded ABQs.
  • 38
  • [ 39549-22-9 ]
  • [ 121-32-4 ]
YieldReaction ConditionsOperation in experiment
76.6% With oxygen; sodium hydroxide In water at 20℃; for 5h; Irradiation;
  • 39
  • [ 121-32-4 ]
  • [ 126-58-9 ]
  • [ 2982771-96-8 ]
YieldReaction ConditionsOperation in experiment
91.5 % With toluene-4-sulfonic acid In tetrahydrofuran; toluene at 50℃; 6.1 Example 6 (1) Dissolve 25.4g dipentaerythritol, 33.24g 4-hydroxy-3-ethoxybenzaldehyde, and 0.33g p-toluenesulfonic acid in 120g tetrahydrofuran, add 60g toluene, react at 50°C for 30 hours, cool to room temperature, and separate the liquids Remove the petroleum ether, use 5wt% sodium bicarbonate aqueous solution for sedimentation, precipitate a white precipitate, filter it, wash it several times with a small amount of deionized water, and then dry it to obtain bicyclic acetal diphenol intermediate 6, whose structural formula is as follows As shown in formula (II-VI), the yield is 91.5%.
  • 40
  • [ 121-32-4 ]
  • [ 1585-17-7 ]
  • [ 3077884-95-5 ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: 4-hydroxy-3-ethoxybenzaldehyde With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 1h; Inert atmosphere; Stage #2: 2,4-bis(chloromethyl)mesitylene In N,N-dimethyl-formamide at 150℃; for 5h; Inert atmosphere; 2.2. Synthesis of dialdehyde monomers General procedure: The procedure for the synthesis of dialdehyde monomers is illustrated in Scheme 1. For this purpose, 1.22 g (10 mmol) of 4-hydroxybenzaldehyde, 1.52 g (10 mmol) of 3-methoxy-4-hydroxybenzaldehyde, and 1.66 g (10 mmol) of 3-ethoxy-4-hydroxybenzaldehyde compounds were dissolved in 20 mL of DMF in three different reaction flasks. They were stirred at 150 °C under an argon atmosphere for 1 h with the addition of 3.45 g (25 mmol) of K2CO3. Subsequently, solutions of 5 mmol of 2,4-bis(chloromethyl)-1,3,5-trimethylbenzene compound in 10 mL of DMF were added dropwise and refluxed for 5 h at 150 °C. The mixtures cooled to room temperature were poured into 200 mL of ice-cold distilled water and allowed to form precipitates. The precipitates were filtered, washed three times with 100 mL of distilled water to remove K2CO3 from the reaction mixtures and recrystallized from ethanol. The reaction yields were calculated to be 63 %, 70 %, and 82 % for DIAL-1, DIAL-2, and DIAL-3, respectively.
  • 41
  • [ 121-32-4 ]
  • [ 220239-69-0 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
98% In acetonitrile Reflux;
 

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