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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.
Vanillin, 4-hydroxy-3-methoxybenzaldehyde, is a food additive, and a modulator candidate for renal injury induced by cisplatin in experimental rats.
Synonyms: p-Vanillin; m-Methoxy-p-hydroxybenzaldehyde; NSC 48383
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Gendron, David ; Labrecque, Josée ;
Abstract: This report discusses the synthesis of a biosourced divanillin derivative obtained by Knoevenagel condensation. The compound was fully characterized by proton (1H), carbon (13C), heteronuclear single quantum coherence (HSQC), homonuclear correlation spectroscopy (COSY), and heteronuclear multiple bond correlation (HMBC) NMR, as well as high-resolution mass spectroscopy (HRMS). We also investigated the optical properties through UV-visible spectroscopy and Fourier-transform infrared (FTIR) spectroscopy. At last, the thermal properties of this divanillin derivative were evaluated by thermogravimetric analysis (TGA) as well as differential scanning calorimetry (DSC).
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Keywords: vanillin ; biosourced ; Knoevenagel condensation ; dyes ; organic pigments
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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. : | 121-33-5 |
Formula : | C8H8O3 |
M.W : | 152.15 |
SMILES Code : | C1=C(OC)C(=CC=C1C=O)O |
Synonyms : |
p-Vanillin; m-Methoxy-p-hydroxybenzaldehyde; NSC 48383
|
MDL No. : | MFCD00006942 |
InChI Key : | MWOOGOJBHIARFG-UHFFFAOYSA-N |
Pubchem ID : | 1183 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H319-H412 |
Precautionary Statements: | P273-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 |
---|---|---|
86% | With potassium carbonate In N,N-dimethyl-formamide; acetonitrileReflux | General procedure: A mixture of the corresponding halide (0.010 mol), hydroxybenzaldehyde (0.011 mol), and potassium carbonate (2.00 g, 0.0145 mol) in a mixture of acetonitrile-DMF (20 mL, 8 : 2, v/v) was refluxed for 5-7 h with stirring (TLC monitoring). After evaporation of the solvents, the residue was treated with water, a precipitate formed was filtered off, washed with 30percent aqueous methanol, and dried in air. Yields and physicochemical characteristics of aldehydes 9-12 are given in Table 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In isopropyl alcohol; for 3h;Heating / reflux; | Added 10 mg huperzine A and 8 mg vanillin in 5 mL isopropanol; stirred at reflux for 3 hours; stripped solvent in vacuo to yield 16 mg product. MS:377(M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h; | General Procedure A: A solution of an appropriate substituted benzaldehyde (1.65 g, 10.86 mmol) and aryl fluoride (10.26 mmol) in DMF (15 ml_) was treated with K2CO3 (2.83 g, 21.72 mmol), and the mixture was heated in an oil bath at 80 0C for 12 h. The reaction was cooled to RT and partitioned between EtOAc and H2O. The organic phase was washed with water (3x), dried over Na2SO4 and concentrated in vacuo. Silica gel chromtagraphy (EtOAc/hexanes) afforded the pure product.Example 1; 4-r4-(2,4-Dioxo-thiazolidin-5-ylidenemethyl)-2-methoxy-phenoxy1-3- trifluoromethvl-benzonitrileA. 4-(4-Formyl-2-methoxy-phenoxy)-3-trifluoromethyl-benzonitrile was prepared from vanillin and <strong>[67515-59-7]4-fluoro-3-trifluoromethylbenzonitrile</strong> following General Procedure A. 1H NMR (400 Hz, CDCI3) £10.00 (s, 1 H), 8.00 (m, 1 H), 7.68 (dd, 1 H), 7.58-7.53 (m, 2H), 7.29 (d, 1 H), 6.75 (d, 1 H), 3.83 (s, 3H); LC/MS (m/z) [M+1]+ 322.1 (calculated for CI6HH F3NO3, 322.06). | |
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h; | General Procedure A: A solution of an appropriate substituted benzaldehyde (1.65 g, 10.86 mmol) and aryl fluoride (10.26 mmol) in DMF (15 mL) was treated with K2CO3 (2.83 g, 21.72 mmol), and the mixture was heated in an oil bath at 80 C. for 12 h. The reaction was cooled to RT and partitioned between EtOAc and H2O. The organic phase was washed with water (3×), dried over Na2SO4 and concentrated in vacuo. Silica gel chromtagraphy (EtOAc/hexanes) afforded the pure product.; A. 4-(4-Formyl-2-methoxy-phenoxy)-3-trifluoromethyl-benzonitrile was prepared from vanillin and <strong>[67515-59-7]4-fluoro-3-trifluoromethylbenzonitrile</strong> following General Procedure A. 1H NMR (400 Hz, CDCl3) delta 10.00 (s, 1H), 8.00 (m, 1H), 7.68 (dd, 1H), 7.58-7.53 (m, 2H), 7.29 (d, 1H), 6.75 (d, 1H), 3.83 (s, 3H); LC/MS (m/z) [M+1]+322.1 (calculated for C16H11F3NO3, 322.06). | |
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h; | A solution of vanillin (1.65 g, 10.86 mmol) and <strong>[67515-59-7]4-fluoro-3-trifluoromethyl-benzonitrile</strong> (10.26 mmol) in DMF (15 mL) was treated with K2CO3 (2.83 g, 21.72 mmol), and the mixture was heated in an oil bath at 80 C. for 12 h. The reaction was cooled to RT and partitioned between EtOAc and H2O. The organic phase was washed with water (3×), dried over Na2SO4 and concentrated in vacuo. Silica gel chromtagraphy (EtOAc/hexanes) afforded the title compound. 1H NMR (400 Hz, CDCl3) delta 10.00 (s, 1H), 8.00 (m, 1H), 7.68 (dd, 1H), 7.58-7.53 (m, 2H), 7.29 (d, 1H), 6.75 (d, 1H), 3.83 (s, 3H); LC/MS (m/z) [M+1]+ 322.1 (calculated for C16H11F3NO3, 322.06). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | General procedure: To a solution of the corresponding aromatic aldehyde (0.27 mmol) in EtOH (0.5 mL) was added urea (0.54 mmol) and CuSO4·5H2O (0.054 mmol). The mixture was stirred at 80 °C for 15 minutes before tetrahydrocurcumin or tetrahydrodemethoxycurcumin (0.27 mmol) was added. The reaction mixture was continued stirring for 24 hours and quenched with water (2 mL). The solution was washed with water (10 mL) and extracted with EtOAc (415 mL). The combined organic phases were washed with brine, dried over MgSO4 and concentrated under reduced pressure to afford crude product as a yellow brown oil. Purification was accomplished by column chromatography eluting with 60percent-75percent EtOAc/hexane to furnish compounds 8-17. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With acetic acid; In ethanol; at 80℃; for 0.166667h;Microwave irradiation; | General procedure: A mixture of compound 2 (0.0549 g, 0.0003 mol), the appropriate aromatic aldehyde (0.00033 mol) and glacial acetic acid (0.1 mL) in ethanol (5 mL) was heated under microwave (20 W) at 80 °C for 10 min. On cooling, the precipitated solid was collected by filtration, washed with water, dried and crystallized to give compounds 3-29. |
In ethanol; at 70 - 80℃; for 3h; | General procedure: The mixture of <strong>[78364-55-3]6-fluoro-2-hydrazinylbenzo[d]thiazole</strong> (2) (0.01 mol) and benzalde-hyde/substituted benzaldehyde (0.01 mol) was reuxed in ethanol (15 ml) at 70?80 °C for 3 h. The separated product obtained was ltered off, washed withdistilled water and recrystallized from methanol to give the correspondinghydrazone. The product obtained was further dissolved in acetic acid (20 ml) atroom temperature followed by the addition of sodium acetate (0.5 g). Bromine(2 mmol) in acetic acid (10 ml) was added dropwise to the reuxing reactionmixture. After 1 h, the mixture was poured onto crushed ice (100 g). The precipitateobtained was ltered off and crystallized from ethanol-dimethylformamide (1:1) togive crystals of (3a?3t). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With hydrogen; at 20℃; under 7500.75 Torr; for 18h;Industrial scale; | 1 kg of vanillin, 13.1 liters of n-butanol (vanillin concentration of 0.5 mol / L), 0.2 kg of catalyst A and 0. 05 kg of catalyst E were added to the reactor and charged with IMPa hydrogen, Heated to 20 C reaction 18h, the detection of vanillin reaction is complete, stop heating, until the reaction tank after cooling the catalyst, the catalyst directly dry and then use. The filtrate was subjected to rotary evaporation to excess excess butanol, To give vanillin butyl ether 1. 33 kg, yield 96%, purity> 98%. |
68.55% | 100.00 g of vanillin was dissolved in 243.59 g of n-butanol,Stirring and stirring, the metal catalyst Pb-C 2.97g was charged.Filled with 1.8MPa hydrogen, heated to 60 ~ 70 C reaction for 8 hours,The vanillin reaction is completely detected, the heating is stopped, and after the reaction liquid is cooled, the metal catalyst Pb-C is recovered by filtration, and the filtrate is put into the reaction tank.14.87 g of aluminum trichloride was added, and the temperature was raised to 60 to 70 C for 12 hours.After cooling to room temperature, the solid in the reaction liquid was removed by filtration, the residue was washed, and the washing liquid was combined with the filtrate, and the mixture was distilled under reduced pressure to obtain a crude colorless liquid.After washing with 100 g of water, the organic phase was separated and vacuum distilled at 165 C.94.74 g of vanillyl butyl ether was obtained in a yield of 68.55% and a purity of >98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In acetonitrile; at 100℃; for 8h; | General procedure: Hydroxyl aldehyde dissolved in acetonitrile (ACN; 5.0 mL) was addedto a solution of intermediate 2 (1.0mmol) and potassium carbonate(1.2mmol) in ACN (25.0 mL) by dripping funnel (1.0mmol), refluxed for8 h, filtered, and concentrated under vacuum. The crude compound waspurified by flash chromatography on silica gel with n-hexane/EtOAc(3:1, v/v) to obtain the desired intermediate 3 as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 25℃; for 16h;Inert atmosphere; | o a solution of (l-methylpyrazol-4-yl) methanol (300 mg, 2.68 mmol, 1.00 equiv.), 4-hydroxy-3-methoxybenzaldehyde (448 mg, 2.95 mmol, 1.10 equiv.) and triphenylphosphine (773 mg, 2.95 mmol, 1.10 equiv.) in tetrahydrofuran (3 mL) was added diisopropylazodicarboxylate (573 uL, 2.95 mmol, 1.10 equiv.) drop-wise maintaining the temperature at 0°C under a nitrogen atmosphere and the reaction mixture was stirred at 25 °C for 16 hours. The reaction mixture was diluted with water (20 mL) and the aqueous layer extracted with ethyl acetate (20 mL x3). The combined organic layer was washed with brine (20 mL), dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by preparative HPLC to afford the desired product as a brown solid. MS (ESI+) m/z 247.0 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66.43% | With potassium carbonate; In acetone; for 4h;Reflux; | General procedure: To a solution of various substituted phenols (1 mmol) in dry acetone (30 mL) K2CO3 (1 mmol)and compound 3 or 4 (1 mmol) were added. After being stirred for 4 h at reflux temperature, thereaction mixture was cooled, filtered, and concentrated under vacuum. Then the residue was dilutedwith 30 mL ethyl acetate and sequentially washed with 30 mL 1 M HCl, aq. NaHCO3 solution andbrine in order. The organic layer was dried over MgSO4 and concentrated in vacuo. Purification of theresidue by chromatography on silica gel furnished target compounds. 1H-NMR, 13C-NMR and massspectroscopy (MS) of compounds 5a-m and 6a-m are shown in Supplementary Materials. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.51% | With potassium borohydride; In ethyl acetate; at 30 - 40℃; for 3h; | 100.00 g of vanillin was dissolved in 231.65 g of ethyl acetate.Stir and dissolve, and add 28.36 g of potassium borohydride and 60.85 g of chlorobutane.The reaction was carried out at 30 to 40 C for 4 hours.After cooling to normal temperature, the solid in the reaction liquid was removed by filtration, and the residue was washed, and the washing liquid was combined with the filtrate, and the mixture was distilled under reduced pressure to obtain a crude colorless liquid.Vacuum distillation at 165 C,125.09 g of vanillyl butyl ether was obtained in a yield of 90.51% and a purity of >99%. This example differs from Example 1 in that the alkylating agent is chlorobutane and the rest are the same as in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.13% | With potassium borohydride; In ethyl acetate; at 30 - 40℃; for 3h; | 100.00 g of vanillin was dissolved in 231.65 g of ethyl acetate.Stirring and stirring, and adding 28.36 g of potassium borohydride,108.07 g of bromobutane was reacted at 30 to 40 C for 3 hours.After cooling to normal temperature, the solid in the reaction liquid was removed by filtration, and the residue was washed, and the washing liquid was combined with the filtrate, and the mixture was distilled under reduced pressure to obtain a crude colorless liquid.Vacuum distillation at 165 C gave 135.62 g of vanillyl butyl ether in a yield of 98.13% and a purity of >99%. The difference between this embodiment and the embodiment 1 is that the reaction time is 3 hours.The molar ratio of vanillin to bromobutane was 1:1.2, and the others were the same as in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | for 0.2h;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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Dissolve vanillin in acetonitrile, add K2CO3 (2.0 eq.) and stir at room temperature for 30 min, add intermediate A (1.0 eq.) and potassium iodide (0.2 eq.), heat to reflux and stir for 4-6 h, TLC monitor the progress of the reaction. After the reaction was completed, extract with ethyl acetate, recrystallize from ethanol, or separate and purify by silica gel column chromatography to obtain intermediates B. |
Tags: 121-33-5 synthesis path| 121-33-5 SDS| 121-33-5 COA| 121-33-5 purity| 121-33-5 application| 121-33-5 NMR| 121-33-5 COA| 121-33-5 structure
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H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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The concentration of the dissolution solution you need to prepare is mg/mL