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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
Synonyms: 3-Methoxysalicylaldehyde
4.5
*For Research Use Only !
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Vanillin based phthalonitrile and acetylene bifunctional resins
James D. Sitter ; Tyler Richardson ; Jean M. Wallace ; Clair Lusk ; Loren C. Brown ; Matthew Laskoski
Abstract: The renewable and biosynthetic molecule, vanillin, were used in the preparation of new phthalonitrile (PN) and ethynylbenzene (EB) bifunctional resins without pre-modification of the vanillin structure. This PN resin was characterized by differential scanning calorimetry, thermogravimetric analysis, nuclear magnetic resonance spectroscopy, rheometry, and single crystal x-ray diffraction. The monomers exhibited excellent rheometric viscosities below 250 Cp at processing temperatures and a good pot life. After complete curing, the PN polymers exhibited thermal stability above 500℃, a glass transition temperature (Tg) above the final postcure temperature of 380℃, and exceptional retention of structural integrity over a large temperature range. These results suggest that vanillin derived EBPN based resins are excellent candidates for use in a variety of applications where high temperature and mechanical stability is critical.
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Keywords: biopolymers and renewable polymers ; resins ; thermosets
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CAS No. : | 148-53-8 |
Formula : | C8H8O3 |
M.W : | 152.15 |
SMILES Code : | O=CC1=CC=CC(OC)=C1O |
Synonyms : |
3-Methoxysalicylaldehyde
|
MDL No. : | MFCD00003322 |
InChI Key : | JJVNINGBHGBWJH-UHFFFAOYSA-N |
Pubchem ID : | 8991 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrogen;5%-palladium/activated carbon; In acetic acid; ethyl acetate; at 20℃; for 84h; | A 3-liter three-necked flask equipped with a thermometer and a mechanical stirrer was charged with 300 g (1.97 moles) of o-vaniline, 100 g of palladium-carbon supporting 5% by weight of palladium, 2 liters of ethyl acetate and 500 ml of acetic acid. The contents were stirred under a hydrogen atmosphere and at room temperature, for 84 hours. The reaction mixture thus obtained was filtered and the filtrate was condensed. To the condensate, 2 liters of ethyl acetate was added again, and the mixture was washed with 1 liter of water three times. The obtained organic layer was condensed and cooled, to yield 259 g of colorless crystal of 2-hydroxy-3-methoxytoluene having the following properties. The yield was 95% based on the o-vaniline.1H-NMR (270 MHz, deuterated benzene, TMS, ppm) delta : 2.28 (s, 3H. Ar-CH3), 3.19 (s. 3H, Ar-O-CH3), 5.78(s. 1H, Ar-OH), 6.38 (d, 1H), 6.63-6.80 (m. 2H). |
With hydrogen;5%-palladium/activated carbon; In methanol; at 20℃; for 72h;Inert atmosphere; | EXAMPLES[0099] Preparation of 2-methoxy-6-methylphenol from hydrogenation of o-vanillin [00100] This reaction is performed inside a drybox for safety precautions because hydrogen gas is used. During the procedure, the drybox is purged periodically with nitrogen to ensure no build up of hydrogen gas. An adaptor with a balloon on one end is attached to a 250 mL flask with a side arm and a magnetic stir bar. One gram of Pd on carbon (5% Pd) is charged slowly into the flask. Then, 7.6 g of o-vanillin and 100 ml of methanol are added. Through the side-arm, hydrogen gas is introduced into the flask system until the balloon is inflated to a volume of about 250 ml. The reaction is allowed to stir at room temperature for 3 days. Hydrogen gas is added when the balloon deflates due to the reaction and diffusion. GC samples are taken to monitor the reaction. When reaction is complete, as evidenced by the appearance of the intermediate first and then by the appearance of the product, the gas inside the balloon and flask is released slowly. The reaction is stirred openly inside the dry box for another 10 minutes to ensure complete dissipation of hydrogen inside the flask into the dry box. The dry box is also purged several times with nitrogen. The flask is taken out of the drybox. The reaction mixture is filtered to separate off the catalyst. The solvent is removed to yield the crude product. The GC and NMR data are compared with the authentic sample to be 2-methoxy-6-methylphenol. Yield is 7.3 g or 95% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With iron(III) chloride; hydroxylamine hydrochloride; In N,N-dimethyl-formamide; for 3.0h;Reflux; | General procedure: Aldehyde(1 mmol) and hydroxylamine hydrochloride (1.2 mmol) were added successively toa solution of anhydrous ferric chloride (0.5 mmol) in 5 ml dry DMF. The mixturewas reflux for appropriate time (Table 2). The progress of the reaction wasmonitored by TLC. After completion of the reaction, the solution was pouredinto 100 ml water and extract with ethyl acetate washed several times withwater. The combined organic mixture was dried over anhydrous Na2SO4,concentrated and the residue was purified by column chromatography on silicagel 60-120 mesh using petroleum ether/ethyl acetate (96:4) as eluent to affordthe pure nitrile. All the products were characterized by IR, 1H NMRand 13C NMR. |
94% | With hydroxylamine hydrochloride; In N,N-dimethyl-formamide; for 1.0h;Reflux; | General procedure: Aldehyde (0.5 mmol) and hydroxylamine hydrochloride (0.75 mmol) were added successively to a solution of Fe3O4-CTAB NPs (5.7 mg) i.e Fe3O4 (1.8 mol%) in 5 ml dry DMF. The mixture was refluxed for appropriate time (table 3). The progress of the reaction was monitored by TLC. After completion of the reaction, the solution was poured into 100 ml water and extract with ethyl acetate, washed several times with water. The combined organic mixture was dried over anhydrous Na2SO4, concentrated and the residue was purified by column chromatography on silica gel 60-120 mesh using petroleum ether/ethyl acetate (95:5) as eluent to afford the pure nitrile. All the products were characterized by IR, 1H NMR and 13C NMR. |
88% | With sodium azide; silica gel; toluene-4-sulfonic acid; at 120℃; for 3.0h;Green chemistry; | General procedure: Aldehyde (1 mmol) , sodium azide (2 mmol) and p-toluene sulphonic acid (3 mmole) were finely mixed with silica gel 60-120 mesh (1g) in mortar and pestle. The resultant solid mixture was poured into a round-bottom flask (50ml) and allowed to stir on magnetic stirrer at 120 for an appropriate time. The progress of the reaction was monitored by TLC. After completion of the reaction, the solution was poured into 100 ml water and extract with ethyl acetate, washed several times with water. The combined organic mixture was dried over anhydrous Na2SO4, concentrated and the residue was purified by column chromatography on silica gel 60-120 mesh using petroleum ether/ethyl acetate as eluent to afford the pure nitrile. All the products were characterized by IR, 1H NMR and 13C NMR. |
4816 g (77%) | With hydroxylamine hydrochloride; sodium formate; In P2O5; formic acid; water; | Example 1 2-Hydroxy-3-methoxy-benzonitrile A suspension of 6375 g (41.94 mol) of o-vanillin, 3823 g (55 mol) of hydroxylamine hydrochloride and 6375 g (93.75 mol) of sodium formate in 14 l of formic acid was heated to about 90 to 95 C. with stirring. Increased evolution of gas and exothermic reaction commenced in this temperature range (heating was turned off). the exothermic reaction lasted for about 10 to 15 minutes (temperature rise to about 115 C.). The mixture was then stirred under reflux for a further 45 minutes. After completion of the reaction, the mixture was cooled to about +6 C. and stirred into a mixture of 6 kg of ice and 25 l of water. After 1 h, the solid was filtered off with suction and washed with about 12 l of water. It was then dried for 24 h at room temperature in a fresh air drying oven and for 120 h over P2O5 in a vacuum drying oven (room temperature). Yield: 4816 g (77%) of crystals, m.p. 54 C., Rf: 0.34 (toluene-ethyl acetate 3:1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; triethylamine; In acetic acid butyl ester; ethyl acetate; at 120℃; | General procedure: T3P mediated synthesis of coumarins: To a mixture of 2-hydroxyaryl aldehyde/ketone (1, 0.01 mol) and appropriate acetic acid (2, 0.01 mol) in n-BuOAc (10 mL) was added T3P (0.02 mol, 50% soln in EtOAc) followed by triethylamine (0.02 mol). The resulting reaction mixture was stirred at 120 C for 6-10 h under conventional heating. When the reaction was completed (monitored by TLC), the mixture was cooled and washed with saturated NaHCO3 solution (1 × 10 mL), water and brine. The organic phase was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was passed through a small plug of silica to afford the coumarins (3) in good purity and yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58%; 19% | General procedure: To a stirring solution of 2-hydroxybenzaldehyde derivative 1 (1.0 mmol), styrenesulfonyl chloride (0.20 g, 1.0 mmol), and K2CO3 (0.14 g, 1.0 mmol) in H2O (15 mL) for 2 h was added 4-hydroxycoumarin derivative 2 (1.2 mmol) or 4-hydroxyquinolinone (0.19 g, 1.2 mmol) and EDDA (20 mmol%) and the mixture was heated at reflux for 12 h. After completion of the reaction as indicated by TLC, the mixture was cooled to room temperature and the organics were extracted using CH2Cl2 (30 mL). Evaporation of the solvent under reduced pressure followed by column chromatography on silica gel using hexane-ethyl acetate (3:1), afforded products 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid; In ethanol; at 20℃; for 8h; | General procedure: To a solution of aryl-aldehydes (5.0 mmol) and the corresponding phenylhydrazines (5.0 mmol)in ethanol (25 mL), was added one drop of acetic acid. The reaction mixture was stirred at roomtemperature for 8 h. After removing of the solvent, the residue was dissolved in CH2Cl2 (DCM) (20 mL),washed by water (10 mL), dried over Na2SO4, filtered and concentrated to give the hydrazones M2that were used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With hydrogenchloride; In 1,4-dioxane; ethanol; at 150℃; for 0.5h;Microwave irradiation; Sealed tube; | General procedure: 3-Amino-1,2,4-triazole 8a?f (1.0 mmol), o-hydroxybenzaldehyde9a?e (1.0 mmol), acetone (10) (0.22 ml,3.0 mmol), and abs. EtOH (2 ml) were mixed in amicrowave process vial, and then 4 N solution of HCl indioxane (0.07 ml, 0.3 mmol) was added. The mixture wasirradiated at 150°C for 30 min. The reaction mixture wascooled by an air flow and stirred for 24 h at roomtemperature for complete precipitation of the product. Theprecipitate was filtered off, washed with EtOH (1 ml) andEt2O (3×1 ml), and dried. Compounds 1a?w were obtainedin a form of white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In ethanol; for 5h;Reflux; | Weigh 2.58 g of <strong>[66640-86-6]biotin hydrazide</strong> and 1.52 g of o-vanillin in a container.Add 150 mL of ethanol and reflux for 5 h to obtain a yellow solid product.The yield was 78percent. |
Tags: o-Vanillin | 3-Methoxysalicylaldehyde | Benzene Compounds | Aryls | Ethers | Aldehydes | Phenols | Fluorinated Building Blocks | Organic Building Blocks | By Structure | 148-53-8
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