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CAS No. : | 54-21-7 | MDL No. : | MFCD00002440 |
Formula : | C7H5NaO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ABBQHOQBGMUPJH-UHFFFAOYSA-M |
M.W : | 160.10 | Pubchem ID : | 16760658 |
Synonyms : |
Salicylic acid sodium salt;2-Hydroxybenzoic acid sodium salt;Magsalyl;Kerosal;Kerasalicyl
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 33.48 |
TPSA : | 60.36 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.67 cm/s |
Log Po/w (iLOGP) : | -5.28 |
Log Po/w (XLOGP3) : | 2.26 |
Log Po/w (WLOGP) : | -0.24 |
Log Po/w (MLOGP) : | 0.99 |
Log Po/w (SILICOS-IT) : | 0.74 |
Consensus Log Po/w : | -0.31 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.59 |
Solubility : | 0.408 mg/ml ; 0.00255 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.16 |
Solubility : | 0.11 mg/ml ; 0.000686 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.17 |
Solubility : | 10.9 mg/ml ; 0.0681 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
96.36% | With potassium fluoride; at 150℃; for 2h; | A new method of solid-liquid phase transfer catalytic synthesis of benzyl salicylate: take sodium salicylate 320.22g (2mol), benzyl chloride 126.6g (1mol), PEG-4000 (0.1mol) and potassium fluoride (0.001mol), Add neck round bottom flask at a temperature of 150 reaction 2h, after completion of the reaction, water was added to make the reaction liquid stratification, the organic layer separated, the organic layer was washed with distilled water again, and then mass percent concentration of 5% NaHCO3Aqueous solution was washed twice with distilled water and washed twice.Followed by dehydration and vacuum distillation, collecting 164-165 / 725Pa of distillate, benzyl salicylate product, the product is a colorless transparent liquid, low temperature as white needles.Detected by gas chromatography, the purity 99.54%, product yield was 96.36%.Benzyl chloride conversion rate of 99.19%, 97.15% selectivity of the reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In ethanol; at 20℃; | 2.8 g of salicylic acid was dissolved in 50 mL of ethanol, at room temperature; an aqueous solution 4 g/60 ml of sodium hydroxide was added to prepare and 300 mL ethanol solution of salicylic acid sodium for the following use |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In DMF (N,N-dimethyl-formamide); at 140℃; for 1h; | Sodium salicylate (0.5g) in dry DMF [(10MI)] was added to the above prepared phytostanyl monochloroacetate (1.5g), the mixture was heated to [140C] with stirring for an hour. After cooling down to room temperature, the mixture was poured into water (100ml), the off-white solid was collected, dried and weighed (1.8g, yield 93.4%). After recrystallization in [MEOH,] a white powder was obtained, (1.5g). [1H] NMR [(CDCI3)] : 10.4 [(1H,] s), 7.90 (1H, d), 7.46 (1H, t), 7.00 [(1H,] d), 6.90 (1H, t), 4.80 [(1 H,] m), 4.80 (2H, s). 13C NMR (CDCI3) : 169.3, 166.8, 161.7, 136.1, 130.3, 131.96, 119.3, 117.6, [111.] 7, 75.5, 61.4. MS (El) : 594 (M+Sitostanol ester), 580 (M+Campestanol ester). [IR (CM-1)] : 2934.0 [(C-H),] 1755.9 [(C=O),] 1680.6 [(C=O).] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In DMF (N,N-dimethyl-formamide); at 140℃; for 1h; | Sodium [O-ACETYLSALICYLATE] (0.5g) in dry DMF [(10MUT)] was added to the above prepared cholestanyl [MONOCHLOROACETATE] (1.5g), the mixture was heated to [140C] with stirring for an hour. After cooling down to room temperature, the mixture was poured into water (100ml), and extracted with hexanes [(150MI),] dried over sodium sulfate (20g), concentrated to remove the solvent, and the waxy solid was collected. After drying, the crude product (2.8g) was [RECRYSTALLIZED] in EtOAc: MeOH solvents, to afford a white powder (2.2g). [1H] NMR (CDCl3) : 10.4 (1H, s), 7.90 (1H, d), 7.50 (1H, t), 7.00 (1H, d), 6.90 (1H, t), 4.80 (1H, m), 4.80 (2H, s). 13C NMR (CDCI3) : 169.3, 166.8, 161.71, 136.1, 130.2, 119.3, 126.02, 117.6, 111.8, 75.5, 61.4. MS (El) : 566 (M+). [IR (CM-1)] : 2930.5 (C-H), 1759 [(C=O),] 1687.4 [(C=O).] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4-Aminobenzyl cyanide (24.8mmol) is suspended in water (75mL) and concentrated hydrochloricacid (8mL) is added. The solution is cooled to 0C in an ice bath with rapid stirring. Sodium nitrite(26.1mmol) in water (20mL) is added dropwise to the 4-aminophenylacetic acid solution with rapidstirring. It is preferred to keep the temperature between 0-5 C at all times, especially during theNaNO2 addition. The reaction is stirred for an additional 20 minutes. In the meantime, salicylic acid,sodium salt (74.4mmol) is dissolved in an aqueous NaOH solution (1 ISmmol NaOH in lOOmL H2O).The solution is vigorously stirred at 17C and at pH 13.3. The diazonium salt solution is addeddropwise to the salicylic acid solution. It can be extremely important to keep the temperature of thesalicylic acid solution between 17-18C and the pH between 13.2-13.3 at all times, especially duringthe diazonium salt addition. The temperature is regulated by adding ice and the pH regulated byadding NaOH, for example, 8M NaOH. After the addition is complete, the solution is allowed towarm room temperature and stirred for an additional period of time, such as about 30 minutes. Thereaction mixture can be suction filtered to remove any undissolved particulates or unwanted sideproducts, and the filtrate can be acidified with aqueous HCI (lOmL cone. HCI in 20mL H2O) toproduce a dark red precipitate. The precipitate can be collected by suction filtration and washedseveral times with cold H2O, until the filtrate is clear. The collected solid can be air dried overnight |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4-Aminophenethyl alcohol (24.8mmol) is suspended in water (75mL) and concentrated hydrochloricacid (8mL) is added. The solution is cooled to 0C in an ice bath with rapid stirring. Sodium nitrite(26.1mmol) in water (20mL) is added dropwise to the 4-aminophenylacetic acid solution with rapidstirring. It may be important to keep the temperature between 0-5C at all times, especially duringthe NaNO2 addition. The reaction is stirred for an additional period of time, for example, about 20minutes. In the meantime, salicylic acid, sodium salt (74.4mmol) is dissolved in an aqueous NaOHsolution (113mmol NaOH in lOOmL H2O). The solution is vigorously stirred at 17C and at pH 13.3.The diazonium salt solution is added dropwise to the salicylic acid solution. It can be important tokeep the temperature of the salicylic acid solution between 17-18C and the pH between 13.2-13.3 atall times, especially during the diazonium salt addition. The temperature can be regulated by addingice and the pH regulated by adding NaOH, for example, 8M NaOH. After the addition is complete,the solution is allowed to warm room temperature and stirred for an additional period of time, forexample, about 30 minutes. The reaction mixture is then suction filtered to remove any undissolvedparticulates or unwanted side products. The filtrate is acidified with aqueous HC1 (lOmL cone. HC1in 20mL H2O) which produces a dark red precipitate. The precipitate is collected by suction filtrationand washed several times with cold H2O, until the filtrate is clear. The collected solid can be airdried overnight. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
While the diazonium salt solution stirred, a 2L beaker fitted with a stir bar, thermometer, and pH probe (Orion model 420A with Orion semimicro pH probe) was charged with salicylic acid, sodium salt (31.8 g, 198 mmol) dissolved in sodium hydroxide (11.9 g, 230 mmol) and water (200 mL). Using an ice bath, the salicylic acid solution was cooled to 17 C. and the diazonium salt solution was slowly added in 25 mL portions. Throughout the addition, the pH was maintained at 13.2-13.3 with the addition of aqueous sodium hydroxide, and the temperature kept between 17-18 C. with the addition of ice. After the addition was complete, the resulting dark red solution was allowed to warm to ambient temperature and stirring was continued for an additional 30 min. Upon acidification to pH 3 with concentrated HCl (~50 mL, 36.5-38%), a brown solid precipitated and was collected by suction filtration. The crude product was purified by flash chromatography (SiO2: ethyl acetate/hexanes, 1:1). On a column packed with 70-230 mesh, 60 A silica gel with BET surface area of ~500 m2/g and pore volume of 0.75 cm3/g, the crude product (11.5 g, 38.2 mmol) in DMF (~12 mL) was loaded. Fractions were collected and combined based on color. The first band was yellow in color and contained excess salicylic acid as well as traces of the desired product. The second band was orange and contained the desired product, and the third band was red and contained unknown impurities. All fractions were combined and concentrated under reduced pressure and dried under vacuum. The purified product was obtained as an orange solid in 28% yield (2.75g): mp 204 C.; 1H NMR (DMSO-d6), d 3.67 (2H, s), 7.11 (IH, d, J=9.0 Hz), 7.44 (2H, d, J=8.4 Hz), 7.79 (2H, d, J=8.4 Hz), 8.02 (1H, d of d, J=2.4 Hz, 9.0 Hz), 8.29 (1H, s); IR (KBr) 3098, 1696, 1614, 1458, 1345, 1195, 838 cm-; UV-Vis (MeOH)?max=350 nm, e=25,700 mol-1 cm-1 L; positive FAB-MS (NBA) m/z 301 (M+H)+, negative FAB-MS(NBA) m/z 299 (M)-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
While the diazonium salt solution stirred, an 800-mL beaker fitted with a stir bar, thermometer, and pH probe (Orion model 420A with Orion semimicro pH probe) was charged with salicylic acid, sodium salt (11.3 g, 20.8 mmol) dissolved in sodium hydroxide (4.25 g, 106 mmol) and H2O (100 mL). Using an ice bath, the salicylic acid solution was cooled to 17 C. and the diazonium salt solution was slowly added in 10 mL portions. Throughout the addition, the pH was maintained at 13.2-13.3 with the addition of aqueous sodium hydroxide, and the temperature was kept between 17-18 C. with the addition of ice. After the addition was complete, the resulting dark red solution was allowed to warm to ambient temperature and stirring was continued for 90 min. Upon acidification to pH 3.5 with concentrated HCl (20 mL, 36.5-38%), a dark red solid precipitated and was collected by vacuum filtration. The crude product (8.49 g, 27.0 mmol) was suspended in H2O (300 mL) and heated at 70 C. for 30 min. to remove excess salicylic acid. The suspension was cooled to 50 C. and a solid was collected by suction filtration. The collected solid was then purified by flash chromatography (SiO2: ethyl acetate/hexanes, 1:1). The crude product (2.50 g. 7.95 mmol) in DMF (4.5 mL) was loaded and yellow colored fractions were collected, combined, and concentrated under reduced pressure. After drying under vacuum, the purified product was obtained as an orange solid in 55% yield (1.38 g): mp 147 C., 1H NMR (DMSO-d6): d 1.38 (3H, s), 1.39 (3H, s), 3.76 (1H, s), 3.78 (1H, s), 7.11 (1H, d, J=8.4 Hz), 7.46 (2H, d, J=7.8 Hz), 7.80 (2H, d, J=8.4 Hz), 8.03 (1H, d, J=9.0 Hz), 8.30 (1H, s); IR (KBr) 2973, 1921, 1708, 1652, 1577, 1477, 1339, 1289, 1226, 1164, 1101, 1013, 857, 663 cm-1; UV-Vis (MeOH) ?max=355 nm, e=23,700 mol-1cm-1L; FAB-MS (NBA) m/z 313 (M)-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In water; at 40℃; for 1h; | Didecyldimethylammonium chloride (0.03 mol) was dissolved in 50 mL distilled water and sodium salicylate (0.04 mol) was added to solution. The mixture was stirred at 40 C. i for 1 h. After cooling to room temperature, 60 mL of chloroform was added. The chloroform phase was separated and washed with distilled water until chloride ions were no longer detected using AgNO3. The didecyldimethylammonium salicylate was obtained in 95% yield. The product is insoluble in water and was dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In water; at 60℃; for 2h; | The stechiometric amounts of didecyldimethylammonium saccharinate and <strong>[54-21-7]sodium salicylate</strong> were mixed in distilled water and stirred at 60 C. for 2 h. After that time the solution was cooled to room temperature. The product was extracted from the aqueous solution with chloroform. The chloroform phase was removed and solvent was evaporated. Synthesized didecyldimethylammonium salicylate (90% yield) was dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water; for 0.25h; | In a typical synthesis to produce [Ag(HSal)] precursor, 3 mol of AgNO3 was dissolved in 40 mL of distilled water, and then <strong>[54-21-7]sodium salicylate</strong> solution (3 mol of <strong>[54-21-7]sodium salicylate</strong> dissolved in 40 mL of distilled water) was added gradually into the above solutions with vigorous stirring. After stirring for 15 min, the as-synthesized white precipitate was isolated and washed with distilled water and ethanol several times to remove impurities, and dried at 50 C in vacuum. The [Ag(HSal)] precursor was characterized by FT-IR, 1H NMR, and TGA/DTA. | |
In water; for 0.5h; | Silver(I) salicylate, [Ag(HSal)], was synthesized according to this procedure: 2mol of AgNO3 was dissolved in 40mL of distilled water. A stoichiometric amount of <strong>[54-21-7]sodium salicylate</strong> dissolved in an equal volume of distilled water was added dropwise into the above solution under magnetic stirring. The solution was stirred about 30min and a white precipitate was isolated and washed with distilled water and ethanol several times to remove impurities and dried at 50C. | |
In water; for 0.5h; | Silver(I) salicylate, [Ag(HSal)], was prepared according to theprocedure described previously.[29] 2 mmol of AgNO3 wasdissolved in 40 mL of distilled water. A stoichiometricamount of <strong>[54-21-7]sodium salicylate</strong> dissolved in an equal volume ofdistilled water was added dropwise into the solution undermagnetic stirring. The solution was stirred about 30 min anda white precipitate was obtained, isolated, and washed withdistilled water and ethanol several times to remove impurities,and then dried at 50C in vacuum. |
In water; for 0.5h; | Silver(I) salicylate, [Ag(HSal)], was synthesized according to this procedure: 2 mol of AgNO3 was dissolved in 40 mL of distilled water. A stoichiometric amount of <strong>[54-21-7]sodium salicylate</strong> dissolved in an equal volume of distilled water was added dropwise into the above solution under magnetic stirring. The solution was stirred about 30 min and a white precipitate was obtained, isolated, washed with distilled water and ethanol several times to remove impurities, and then dried at 50C under vacuum condition. The [Ag(HSal)] complex was characterized by FT-IR, TGA/DTA, and1H-NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 21 - 23℃; | [Example 1] Synthesis of l,l'-oxalyldi-2-sodiumbenzoate; [66] l,l'-oxalyldisodium-2-hydroxybenzoate was synthesized from the reaction between10.0 mM sodium 2-hydroxybenzoate and 1.0 mM <strong>[1165-91-9]TCPO</strong> in a quartz cell (1.0 cm width x 4.0 cm length) at room temperature (21-23 0C). 2,4,6-trichlorophenol(TCP) was formed as a byproduct in this reaction.[67] TCP formation vs. time profile at 290 nm using a UV- Visible spectrometer with photodiode array detector was provided in order to indentify the formation of the l,l'-oxalyldisodium-2-hydroxybenzoate indirectily. The rate constant for TCP formation was 0.12 +/- 0.008 s" . Also, using H-NMR, the formation of l,l'-oxalyldisodium-2-benzoate was indentified directly as shown below:[68] 1H-NMR (CD CN): delta 6.7, 7.2, 7.6, 7.8 ppm (phenyl hydrogens, multiplet) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.1% | In water; at 20 - 62℃; for 19.95h; | Example 8; Preparation of Imipramine SalicylateSodium Salicylate (16.4 g) in USP water (118.0 g) was stirred at 20 C. in a 1 L reactor. After 15 min, the solution was checked and exhibited pH 6.23. In a Imipramine HCl (31.7 g) in USP water (320.0 g) was stirred at 22 C. in a 500 mL reactor until a solution was observed (>20 min). The Imipramine HCl solution was checked and exhibited a pH 4.54. The Imipramine HCl solution was added via metered addition funnel to the sodium salicylate solution at 20 C. over 1.75 h. The reactor and addition funnel was rinsed to the reaction with USP water (20.0 g). The reaction mixture was heated from about 20 C. to about 50 C. for 1.2 h. The mixture was heated to about 62 C. for 17 h. Solids were collected by filtration of the mixture at 50 C. Residue was rinsed from the reactor to the filter with USP water (4×110.0 g). After drying on the filter for 1 h, solids were dried at about 65 C. to about 78 C. for approximately a day. Imipramine salicylate, mp 141-143.6 C. (39.8 g, 95.1%). Recrystallization of imipramine salicylate from a solution of ethanol-water (98/2) provided solid, mp 142.2-144.2 C. The DSC thermogram (FIG. 16), FTIR analysis (FIG. 17) and 1H NMR spectra (FIG. 18) were consistent with the expected structure. |
95.1% | In water; at 20 - 62℃; for 19.95h; | Sodium Salicylate (16.4 g) in USP water (118.0 g) was stirred at 20 C. in a 1 L reactor. After 15 min, the solution was checked and exhibited pH 6.23. In a Imipramine HCl (31.7 g) in USP water (320.0 g) was stirred at 22 C. in a 500 mL reactor until a solution was observed (>20 min). The Imipramine HCl solution was checked and exhibited a pH 4.54. The Imipramine HCl solution was added via metered addition funnel to the sodium salicylate solution at 20 C. over 1.75 h. The reactor and addition funnel was rinsed to the reaction with USP water (20.0 g). The reaction mixture was heated from about 20 C. to about 50 C. for 1.2 h. The mixture was heated to about 62 C. for 17 h. Solids were collected by filtration of the mixture at 50 C. Residue was rinsed from the reactor to the filter with USP water (4×110.0 g). After drying on the filter for 1 h, solids were dried at about 65 C. to about 78 C. for approximately a day. Imipramine salicylate, mp 141-143.6 C. (39.8 g, 95.1%). Recrystallization of imipramine salicylate from a solution of ethanol-water (98/2) provided solid, mp 142.2-144.2 C. The DSC thermogram (FIG. 16), FTIR analysis (FIG. 17) and 1H NMR spectra (FIG. 18) were consistent with the expected structure |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In water; acetone; at 20℃; | Cetylpyridinium chloride monohydrate (20.64 g, 56 mmol) and sodium salicylate(8.96 g, 56 mmol) were dissolved in 100 ml of acetone/H2O 1:1 and stirred overnight at room temperature. The remaining suspension was diluted with 100 ml of H2O and extracted with dichloromethane. The organic layer was washed successively with water until no more chloride ions could be detected in the washings (checked by addition OfAgNO3 solution), dried over MgSO4 and the solvent was evaporated. Remaining volatile material was removed under reduced pressure (0.01 mbar) to give cetylpyridinium salicylate [6] in 56% yield as colourless waxy solid. 1H-NMR (300 MHz, d6-DMSO) delta(ppm) = 9.12 (d, J = 6.08 Hz, 2H), 8.59 (t, J = 8.29 Hz, IH), 8.16 (t, J = 7.27 Hz, 2H), 7.64 (d, 7.54 Hz, IH), 7.12 ( t, J = 7.54, IH), 6.57 (m, 2H), 4.59 (t, J = 7.44 Hz, 2H), 1.88 (m, 2H), 1.22 (s, 27H), 0.84 (t, J = 7.14 Hz, 3H). 13C-NMR (75 MHz, d6-DMSO) delta(ppm) = 171.8, 163.4, 145.8, 145.2, 131.4, 130.2,128.4, 121.1, 116.1, 160.0, 61.2, 31.7, 31.2, 29.4, 29.3, 29.2, 29.1, 28.8, 25.8, 22.5, 14.2. mp57 C, T5o/oOnset 206 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; acetone; at 20℃; | Procainamide hydrochloride (2.718 g, 10 mmol) and <strong>[54-21-7]sodium salicylate</strong> (1.601 g, 10 mmol) were dissolved in 10 ml of acetone/H2O 1 : 1 and stirred overnight at room temperature. The clear solution was evaporated and the residue dissolved in anhydrous acetone. The suspension was filtered over celite and the filtrate was evaporated. Remaining volatile material was removed under reduced pressure (0.01 mbar) to give procainamide salicylate [15] as pale yellow viscous oil. 1H-NMR (300 MHz, d6-DMSO) delta(ppm) = 8.47 (t, J= 5.6 Hz, IH), 7.72 (dd, J1 = 7.7 Hz, J2 = 1.9 Hz, IH), 7.60 (d, J = 8.7 Hz, 2H), 7.23 (m, IH), 6.71 (m, 2H), 6.54 (d, J - 8.6 Hz, 2H), 3.60 (s, 2H), 3.19 (m, 6H), 1.23 (t, J = 7.1 Hz, 6H). 13C-NMR (75 MHz, d6-DMSO) delta(ppm) = 172.5, 166.9, 162.2, 152.0, 132.2, 130.2, 128.8, 120.4, 119.1, 116.8, 1160.0, 112.5, 50.0, 46.7, 34.3, 8.6. T5o/o0nset 199 C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; acetone; at 20℃; | <strong>[121-54-0]Benzethonium chloride</strong> (4.481 g, 10 mmol) and sodium salicylate (1.601 g, 10 mmol) were dissolved in 50 ml of acetone/H2O 1:1 and stirred overnight at room temperature. The remaining suspension was diluted with 50 ml OfH2O and extracted with dichloromethane. The organic layer was washed successively with water until no more chloride ions could be detected in the washings (checked by addition OfAgNO3 solution), dried over MgSO4 and the solvent was evaporated. Remaining volatile material was removed under reduced pressure (0.01 mbar) to give benzethonium salicylate [6] as yellow glass. 1H-NMR (300 MHz, d6- DMSO) delta(ppm) = 7.65 (m, IH), 7.53 (m, 5H), 7.26 (d, J = 8.9 Hz, 2H), 7.10 (s, IH), 6.82 (d, J = 8.9 Hz, 2H), 6.57 (m, 2H), 4.61 (s, 2H), 4.11 (s, 2H), 4.00 (m, 2H), 3.82 (s, 2H), 3.39 (m, 2H), 3.02 (s, 6H), 1.67 (s, 2H), 1.28 (s, 6 H), 0.66 (s, 9H). 13C-NMR (75 MHz, d6-DMSO) delta(ppm) = 171.0, 168.3, 141.0, 128.2, 127.4, 125.8, 69.7, 66.2, 61.5, 59.1, 38.2, 34.1, 30.7,29.8, 29.6, 28.4, 23.2, 23.0, 22.5, 13.9, 10.8, 9.2. Tg -14 0C, T5o/o0nset 180 C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | In water; acetone; at 20℃;Product distribution / selectivity; | Lidocaine hydrochloride monohydrate (23.105 g, 80 mmol) and <strong>[54-21-7]sodium salicylate</strong>(8.962 g, 80 mmol) were dissolved in 10 ml of acetone/H2theta 1:1 and stirred overnight at room temperature. The remaining suspension was diluted with 100 ml OfH2O and extracted with dichloromethane. The organic layer was washed successively with water until no more chloride ions could be detected in the washings (checked by addition OfAgNO3 solution), dried over MgSO4 and the solvent was evaporated. Remaining volatile material was removed under reduced pressure (0.01 mbar) to give lidocainium salicylate [8] in 54% yield as pale yellow viscous oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In water; acetone; at 20℃; | Tramadolium hydrochloride (1.499 g, 5 mmol) and <strong>[54-21-7]sodium salicylate</strong> (0.801 g, 5 mmol) were dissolved in 50 ml of acetone/H2O 1:1 and stirred overnight at room temperature. The obtained suspension was chilled to 0 C, the precipitate was collected via filtration, washed with H2O and dried under reduced pressure (0.01 mbar) to isolate tramadolium salicylate as colourless solid in 79 % yield. 1H-NMR (300 MHz, d-DMSO) delta(ppm) = 7.69 (dd, J1 = 7.6 Hz, J2 = 1.8 Hz, IH), 7.27 (t, J = 8.1 Hz, IH), 7.19 (m, IH), 7.08 (m, 2H), 6.79 (m, IH), 6.66 (m, 2H), 3.76 (s, 3H), 3.56 (br s, IH), 2.83 (t, J = 11.9 Hz, IH), 2.52 (s, 6H), 2.33 (d, 13.0 Hz, IH), 2.24 (m, IH), 1.89 (m, IH), 1.64 (m, 7H).13C-NMR (75 MHz, d6-DMSO) delta(ppm) = 172.0, 262.3, 159.2, 150.0, 131.9, 120.1, 129.1, 119.5, 117.2, 116.5, 117.2, 116.5, 115.9, 111.5, 111.1, 73.9, 59.4, 55.0, 43.0, 40.5, 40.4, 25.7, 24.6, 21.2. mp 183 C, T5o/oonset 220 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41.6% | In N,N-dimethyl-formamide; at 20℃; for 65h;Inert atmosphere; | A stirred mixture of <strong>[54-21-7]sodium salicylate</strong> 19b (600.0 mg, 3.75 mmol) and compound 10 (541.6 mg, 4.09 mmol) in anhydrous DMF (15 mL), whilst maintained under nitrogen, was set-aside at room temperature for ?65 h. Then the mixture was processed in the same manner as described above. The resultant solid was crystallised from di-isopropyl ether to give 20b as pure white crystals, 365.4 mg (41.6%), mp 80-81 C; 1H NMR (CDCl3, 400 MHz): delta 10.28 [s, 1H, OH (hydrogen bonding)], 7.81-7.00 (m, 4H, ArH + CH + OCHO), 2.04 (m, 3H, CH3); 13C NMR, (CDCl3, 100 MHz), delta 170.8 (CO), 168.4 (CO), 162.2, 141.6, 136.9, 135.0, 130.1, 119.5, 117.9, 110.9, 92.8, 10.7; MS [EI m/z, rel. intensity (%)]: 235 ([M+1]+, 11.2); 234 ([M]+, 73.9); 138 ([M++1]-97, [C7H5O3]+, 91.2); 97 ([M+-137, [C5H5O2]+, 100); HRMS/EI: m/z calcd for C12H10 O5: 234.0528. Found: 234.05289. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In benzene; for 5h;Reflux; | General procedure: The solution of toluene-3,4-dithiolatoarsenic(III) chloride (0.29 gm, 1.12 mmol) in benzene (~30 ml) was added drop wise to <strong>[54-21-7]sodium salicylate</strong> (0.17 gm, 1.12 mmol) suspension in benzene (~25 ml) in 1:1 molar ratio. The contents were heated under reflux for ~5 h. Precipitated sodium chloride (0.06 gm) was removed by filtration. On removing the solvent from the filtrate, yellow semi solid obtained, was recrystallized from n-hexane. Yield 364 mg; 88%; M.P. = 48 C (Scheme A.1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; at 90℃; for 24h;Green chemistry; | Mesoporous material (0.60 g), aqueous sodium salicylate solution (1.50 g, 4.68 mmol), and <strong>[19692-45-6]4-tert-butylbenzyl chloride</strong> (0.90 g, 4.93 mmol) were added in that order into a round bottomed flask fitted with a magnetic stirrer. The slurry was heated in an oil bath under a condenser at 90 ?C. Aliquots were taken at various intervals during 24 h and analysed with 1H NMR and 13C NMR for the reaction products. Sodium 3-(4-tert-butylbenzyl)-2-hydroxybenzoate was characterized by the following NMR pattern: 1H NMR (400 MHz, CDCl3) ? (ppm): 1.35 (s, 3H), 3.96 (s, 2H), 6.96-7.04 (d/t, H), 7.15 (d, H), 7.34 (d, H), 7.40 (d, H), 7.75-7.85 (d, H). 13C NMR (400 MHz, CDCl3) ? (ppm): 31.3, 34.2, 35.1, 120.9, 123.3, 125.5, 128.8, 130.0, 132.2, 135.3, 138.4, 148.8, 162.5, 171.0. Sodium 5- (4-tert-butylbenzyl)-2-hydroxybenzoate was characterized by the following NMR pattern: 1H NMR (400 MHz, CDCl3) ? (ppm): 1.35 (s, 3H), 3.96 (s, 2H), 6.96-7.04 (d/t, H), 7.15 (d, H), 7.34 (d, H), 7.40 (d, H), 7.75-7.85 (s, H). 13C NMR (400 MHz, CDCl3) ? (ppm): 31.3, 34.2, 41.3, 119.7, 123.3, 125.5, 128.8, 132.2, 133.8, 134.2, 148.8, 162.7, 171.0. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; at 25 - 60℃;pH 5 - 6;Inert atmosphere; | General procedure: For spectrophotometric TRLFS titrations 2.5 mL of 5 × 10-6, 1 × 10-5 or 3 × 10-5 m Eu3+ at 0.1 or 1 m NaClO4 (pH between 5.0 and 6.0) were titrated with aliquots (5, 10 or 20 muL) of 5 × 10-3, 5 × 10-2, 0.1 m or 0.5 m salicylate solution (pH between 5.0 and 6.0, the overall ionic strength was adjusted with additional NaClO4 to 0.1 or 1 m). About 20 titration steps up to a salicylate concentration of 0.01 m were performed; every mixture was allowed to equilibrate for at least 15 min. The mixtures with salicylate concentration >0.01 m were prepared separately with an appropriate amount on NaClO4 to reach an overall ionic strength of 0.1 or 1 m, respectively. For every complexation mixture both a static and a time-resolved luminescence spectrum was measured. The temperature was adjusted to different values between 25 and 60 C (see Table 2) using a stirred temperature-controlled cuvette holder (Flash 300, Quantum Northwest, USA). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; at 25 - 60℃;pH 5 - 6;Inert atmosphere; | For spectrophotometric TRLFS titrations 2.5 mL of 5 × 10-6, 1 × 10-5 or 3 × 10-5 m Eu3+ at 0.1 or 1 m NaClO4 (pH between 5.0 and 6.0) were titrated with aliquots (5, 10 or 20 muL) of 5 × 10-3, 5 × 10-2, 0.1 m or 0.5 m salicylate solution (pH between 5.0 and 6.0, the overall ionic strength was adjusted with additional NaClO4 to 0.1 or 1 m). About 20 titration steps up to a salicylate concentration of 0.01 m were performed; every mixture was allowed to equilibrate for at least 15 min. The mixtures with salicylate concentration >0.01 m were prepared separately with an appropriate amount on NaClO4 to reach an overall ionic strength of 0.1 or 1 m, respectively. For every complexation mixture both a static and a time-resolved luminescence spectrum was measured. The temperature was adjusted to different values between 25 and 60 C (see Table 2) using a stirred temperature-controlled cuvette holder (Flash 300, Quantum Northwest, USA). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; at 25 - 60℃;pH 5 - 6;Inert atmosphere; | For spectrophotometric TRLFS titrations 2.5 mL of 5 × 10-6, 1 × 10-5 or 3 × 10-5 m Eu3+ at 0.1 or 1 m NaClO4 (pH between 5.0 and 6.0) were titrated with aliquots (5, 10 or 20 muL) of 5 × 10-3, 5 × 10-2, 0.1 m or 0.5 m salicylate solution (pH between 5.0 and 6.0, the overall ionic strength was adjusted with additional NaClO4 to 0.1 or 1 m). About 20 titration steps up to a salicylate concentration of 0.01 m were performed; every mixture was allowed to equilibrate for at least 15 min. The mixtures with salicylate concentration >0.01 m were prepared separately with an appropriate amount on NaClO4 to reach an overall ionic strength of 0.1 or 1 m, respectively. For every complexation mixture both a static and a time-resolved luminescence spectrum was measured. The temperature was adjusted to different values between 25 and 60 C (see Table 2) using a stirred temperature-controlled cuvette holder (Flash 300, Quantum Northwest, USA). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37.8% | In dimethyl sulfoxide; at 20℃; | General procedure: Appropriately substituted sodium carboxylate (1.0mmol) was added in a solution of compound (c1 or c2) (0.5mmol) in dry DMSO (15mL). The mixture was then stirred for 8-12h at room temperature (monitored by TLC). After 30mL of water was added, the precipitate was collected, which was purified by column chromatography on silica gel, eluting with AcOEt/petroleum ether. 4-(2-(2-hydroxyphenylformyloxyl)ethoxy)-3-phenylfuran-2(5H)-one (d13) White powder, 37.8%, mp 132-134 C; 1H NMR (CDCl3): 4.43 (s, 2H, CH2); 4.66 (d, J = 4.2 Hz, 2H, CH2); 4.87 (s, 2H, CH2); 6.90 (t, J = 7.6 Hz, 1H, ArH); 7.01 (d, J = 8.4 Hz, 1H, ArH); 7.30-7.40 (m, 3H, ArH); 7.50 (t, J = 7.8 Hz, 1H, ArH); 7.81 (t, J = 6.7 Hz, 3H, ArH); 10.50 (s, 1H, OH); EIMS m/z 340 (M+). Anal. Calcd for C19H16O6: C, 67.05; H, 4.74; O, 28.21; Found: C, 67.17; H, 4.68; O, 28.15. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In N,N-dimethyl-formamide; at 20℃; for 18h;Inert atmosphere; | General procedure: To a stirred solution of bromobutenolide (0.48 g, 2.71 mmol) in anhydrous DMF (4 ml) was added solid sodium benzoate (5) (0.325 g, 2.26 mmol) under argon and the mixture was set aside at room temperature for 18 h. Sodium benzoate slowly dissolved when the reaction progressed and ultimately a clear solution was obtained. TLC indicated complete consumption of brombutenolide. The mixture was concentrated in vacuo, the residue was treated with a mixture of water (20 ml) and ethyl acetate (2 × 20 ml), and the combined organic layers were washed with water, brine, dried (Na2SO4) and concentrated in vacuo. The resultant crude product was crystallized from ethyl acetate/heptane to afford pure 9a as colorless tiny crystals (0.395 g, 81%). For physical and spectral data, see Ref. 27 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In benzene; for 5h;Reflux; | General procedure: Bis(diethyldithiocarbamato)antimony(III)chloride (1.5 g; 0.33 mmol) dissolved in benzene (?40 mL) was added to sodium acetate (0.27 g; 0.33 mmol) drop by drop in a round bottom flask. The reaction mixture was refluxed for ?5 h. It was cooled and precipitated sodium chloride was filtered off. The solvent was removed under reduced pressure to get the product. Finally, the compound was crystallized in dichloromethane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In hexane; for 5h;Reflux; | General procedure: Chlorobis(N,N-dimethyldithiocarbamato-S,S')antimony(III) (1.9 g; 4.8 mmol) dissolved in hexane (~40 ml) was added to sodium benzoate 1 (0.7 g; 4.8 mmol) drop-wise. The reaction mixture was refluxed for ~5 h. It was then cooled and precipitated sodium salt was filtered off. The filtrate was reduced under vacuumto obtain the product (Scheme 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile; at 20℃; | The ionic liquid, 1-butyl-3-methylimidazolium salicylate,[BMIM][SAL] was prepared from 1-butyl-3-methylimidazoliumchloride [BMIM][Cl] and <strong>[54-21-7]sodium salicylate</strong>. 1-Butyl-3-methylimidazolium chloride synthesized and purified accordingto standard procedures reported in the literature [23-26]. Inbrief [BMIM][Cl] was synthesized by direct alkylation of N-methylim idazole, 0.05 mol (freshl y distilled) with an excess of 1-chlorobutane (0.06 mol) which added dropwise over 1 h intopowerfully stirring of N-methylimidazole in a two-necked roundbottom flask in ice bath. Then mixture, already turbid, was refluxedfor 72 h under a nitrogen atmosphere and at 343 K. The crudeproduct was decanted from hot solution in a separator funnel,washed four times with 50 ml ethyl acetate. The product was driedin at 353 K using a rotary evaporator for at least 5 h at reducedpressure (0.7 kPa) which was used after high vacuum desiccated(0.1 Pa) for at least 12 h to remove trace amount of moisture.Water contents found by Karl Fischer method in ionic liquidswas less than 0.05% in mass fraction. Ionic liquid were analyzedby1H NMR and IR spectra to confirm the absence of any majorimpurities and they were detected to be in good agreement withthose reported in the literature [25]. The purity of obtained ionicliquid was 98% in mass fraction. The 1-butyl-3-methylimidazoliumsalicylate ionic liquid [BMIM][SAL] was subsequent prepared byfollowing the similar metathesis reaction used for the preparationof 1-butyl-3-methylimidazolium dicyanamide IL [BMIM][DCA][27,28]. However, dried acetonitrile was used as the solvent ratherthan acetone. For the synthesis of 1-butyl-3-methylimidazoliumsalicylate, (0.4 mol) <strong>[54-21-7]sodium salicylate</strong> salt dissolved in driedacetonitrile and added slowly to (0.4 mol) [BMIM][Cl] whichwas dissolved in a minimum amount of dried acetonitrile. Theresulting mixture was stirred overnight at the room temperature.The solution was concentrated under reduced pressure. Theresidue was dried in a vacuum oven and then dissolved in a largeamount of anhydrous dichloromethane. The organic solution wasallowed to stand at 253.15 K overnight until precipitate sodiumchloride and the excess of <strong>[54-21-7]sodium salicylate</strong> [26]. Addition of drieddichloromethane was renovated until no further precipitation ofNaCl could be found. After filtration and evaporation of the solventfrom the filtrate, the reminder (a yellowish solid) was further driedat 343.15 K [27]. The water content of the API-IL was determinedusing a coulometric Karl-Fischer titrator (Metrohm 756 KF) andthe value was approximately 0.1% in mass fraction. The synthesizedAPI-IL was characterized by1H,13C NMR (Brucker Av-400) and IR(Brucker, tensor27).1HNMR spectrum of [BMIm][SAL] can be seenin Supporting information as Fig. S1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With Aliquat336; In chloroform; for 4h; | Aliquat 336 (Aldrich; the 2:1 mol/mol mixture of methyltrioctyl- and methyltridecylammonium chloride) was mixed with 30% excess of <strong>[54-21-7]sodium salicylate</strong> in 200 mL of chloroform. The mixture was shaken for 4 h and then was rinsed with a large amount of distilled water. The solvent was evaporated and the liquid residue was heated up to 100 C under reduced pressure for 5 h. After cooling to room temperature a white solid matter was obtained with a density 0.943 g cm-3; Tmelt = 32.8 ± 0.4 C, Tf = 14 ± 2 C. Yield: 90%.The NMR spectra indicated: 1H NMR (500 MHz, Bruker DRX500, solvent CDCl3, TMS) 0.88 (9 H), 1.24 (30 H), 1.59 (6 H), 3.19 (3H), 3.27 (6 H), 7.20 (1 H), 7.92 ppm (1 H); 13C NMR (126 MHz, solvent DMSO-D6, TMS) 13.80 (CCH3), 21.93 (CH2CH3), 21.25, 25.68,28.27, 28.32, 31.04 (various CH2CH2 fragments); 47.41 (CH3N);60.50 (CH2N); 115.35, 115.62, 120.73, 129.73, 130,88 (aromatic C); 163.17 (COH); 171.00 ppm (COO). Anal. Calc.: C, 76.49; H,11.89; N, 2.62. Found: C, 76.06; H, 11.64; N, 2.62% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7.2-Hydroxy-5-phenylazo-benzoic acid (3a). Yield 56%, orange to brownish crystals, m.p. 218-220 oC. Rf 0.31 (CHCl3/CH3OH/CH3COOH 8:1:1). IR (KBr): numax 3425 (phenolic -OH str), 3063 (aromatic CH str), 1585 (C=O str), 1483 (N=N str), 1286 (CH bend aromatic ring), 1251(C-O str), 1174 cm-1(C-N str). 1H-NMR (400 MHz, DMSO-d6): delta (ppm) 16.6 (s, 1H), 8.42 (d,J= 2.4 Hz, 1H), 7.8 (m, 3H), 7.46 (t, J= 7.6 Hz, 2H), 7.38 (t, J= 7.2 Hz, 1H), 6.78 (d, J= 8.80 Hz, 1H), 3.82 (s, 3H). 13C-NMR (100 MHz, DMSO-d6): delta(ppm) 171.8, 166.9, 152.17, 143.14, 129.85, 129, 126.6, 126, 121.9, 119, 117.2, 78.8, 39.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | General procedure: Synthetic procedures. Aromatic amine (1a-i) (0.01 mol) was dissolved in 1:1 ratio of conc. HCl and water. Sodium nitrite solution (0.02 mol/mL) was added to the reaction mixture dropwise with continuous stirring. The reaction mixture was stirred for 45 min. at a temperature of 0-5 oC. The diazotization step was followed by coupling of the diazotized amines by drop wise addition to the solution of <strong>[54-21-7]sodium salicylate</strong> (0.01 mole of salicylic acid dissolved in 0.02 mol/mL solution of sodium hydroxide). The reaction was stirred at 0-5 oC for 2 hours under alkaline conditions. The conjugates of salicylic acid and aromatic amines (3a-i) were obtained as orange to red powders after the pH was neutralized to 6-7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: The complexes were prepared in the following steps. Isoniazid furalacylhydrazone (0.5 mmol) was dissolved in 10 mL ofethanol. A solution of Ln(NO3)3 ¢6H2O (0.5mmol) in 5 mL ofmethanol were successively added to the solution of isoniazidfuralacylhydrazone. The mixture was heated to 70C understirring. After 2 h, 0.5 mmol <strong>[54-21-7]sodium salicylate</strong> in 10 mL ethanol solution was added in the mixture dropwise under stirring and the solution was heated to 70C for 3 h. The solventwas removed by rotary evaporation.The excess of unbounded complex was washed away withwater and ethanol three times and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: The complexes were prepared in the following steps. Isoniazid furalacylhydrazone (0.5 mmol) was dissolved in 10 mL ofethanol. A solution of Ln(NO3)3 ¢6H2O (0.5mmol) in 5 mL ofmethanol were successively added to the solution of isoniazidfuralacylhydrazone. The mixture was heated to 70C understirring. After 2 h, 0.5 mmol <strong>[54-21-7]sodium salicylate</strong> in 10 mL ethanol solution was added in the mixture dropwise under stirring and the solution was heated to 70C for 3 h. The solventwas removed by rotary evaporation.The excess of unbounded complex was washed away withwater and ethanol three times and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: The complexes were prepared in the following steps. Isoniazid furalacylhydrazone (0.5 mmol) was dissolved in 10 mL ofethanol. A solution of Ln(NO3)3 ¢6H2O (0.5mmol) in 5 mL ofmethanol were successively added to the solution of isoniazidfuralacylhydrazone. The mixture was heated to 70C understirring. After 2 h, 0.5 mmol <strong>[54-21-7]sodium salicylate</strong> in 10 mL ethanol solution was added in the mixture dropwise under stirring and the solution was heated to 70C for 3 h. The solventwas removed by rotary evaporation.The excess of unbounded complex was washed away withwater and ethanol three times and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: The complexes were prepared in the following steps. Isoniazid furalacylhydrazone (0.5 mmol) was dissolved in 10 mL ofethanol. A solution of Ln(NO3)3 ¢6H2O (0.5mmol) in 5 mL ofmethanol were successively added to the solution of isoniazidfuralacylhydrazone. The mixture was heated to 70C understirring. After 2 h, 0.5 mmol <strong>[54-21-7]sodium salicylate</strong> in 10 mL ethanol solution was added in the mixture dropwise under stirring and the solution was heated to 70C for 3 h. The solventwas removed by rotary evaporation.The excess of unbounded complex was washed away withwater and ethanol three times and dried in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10.4 g | In ethanol; water; at 50℃; for 0.333333h; | In a flask equipped with a magnetic stirrer, 13.2 g of Sildenafil citrate was dissolved in a mixture of ethanol (100 mL) and water (30 mL), an ethanol solution of salicylic acid sodium was added then reacted at 50 C for 20 mins. After cooling, a white precipitate was obtained and the sodium citrate was removed by filtration. The solvent 100 mL of methanol was added to resolve the precipitate under room temperature and incubated overnight for re-crystallization. The Sildenafil salicylate complex (10.4 g) was obtained after filtering the crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | CrCl36H2O (0.5506 g, 2.06 mmol) was added to ethanol (20 ml)and stirred under reflux for 10 min to give a greenepurple solution.Then, <strong>[54-21-7]sodium salicylate</strong> (NaO2C(OH)Ph) (0.6613 g, 4.13 mmol) wasadded and the reflux continued for another 3 h to give a deep greensolution. After cooling of the solution at room temperature, Et2O(30 ml) was added and the precipitated NaCl was removed byfiltration. The final solution was evaporated to produce a greenpowder, which was dissolved in cold ethanol (15 ml). Green crystals,suitable for X-ray structure analysis, were grown by slowevaporation at room temperature of the green ethanol solutionafter two weeks. The crystals were filtered off and dried in vacuo.Yield: 1.58 g (68%). The dried solid analyzed as solvent-free, i.e.,Anal. Calc. for C49 H39 Cr3 O24(%): C, 50.34; H, 3.34. Found: C, 49.72;H, 3.48 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 20℃; for 72h; | General procedure: Fig. 1 illustrates the general synthesis of salicylate and thiosalicylatebased ILs [39-41]. Firstly, 20 mmol of 1-bromobutane, 1-bromohexane,or 1-bromooctane was added to 20 mmol of N-methylimidazole, andthe mixture was refluxed while being stirred at 140 C for 30 minuntil a yellow liquid with high viscosity was obtained. The preparedILs ([BMIM][Br], [HMIM][Br], or [OMIM][Br]) were extracted with10 mL diethyl ether and washed with DDW, respectively, dried overanhydrous sodium sulfate and evaporated under vacuum. Secondly, becausethe halide salts underwent metathesis reaction to give the desiredionic liquid, 20 mmol of <strong>[54-21-7]sodium salicylate</strong> was added to the obtained ILinwater, and the mixturewas stirred at roomtemperature for 72 h untilthe anion-exchange process was done. The water was removed withrotary evaporator and the by-product salt of NaBr was removed byfiltration after addition of methanol. Finally, salicylate based IL as ayellow liquid was dried under vacuum |
Yield | Reaction Conditions | Operation in experiment |
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at 20℃; for 72h; | General procedure: Fig. 1 illustrates the general synthesis of salicylate and thiosalicylatebased ILs [39-41]. Firstly, 20 mmol of 1-bromobutane, 1-bromohexane,or 1-bromooctane was added to 20 mmol of N-methylimidazole, andthe mixture was refluxed while being stirred at 140 C for 30 minuntil a yellow liquid with high viscosity was obtained. The preparedILs ([BMIM][Br], [HMIM][Br], or [OMIM][Br]) were extracted with10 mL diethyl ether and washed with DDW, respectively, dried overanhydrous sodium sulfate and evaporated under vacuum. Secondly, becausethe halide salts underwent metathesis reaction to give the desiredionic liquid, 20 mmol of <strong>[54-21-7]sodium salicylate</strong> was added to the obtained ILinwater, and the mixturewas stirred at roomtemperature for 72 h untilthe anion-exchange process was done. The water was removed withrotary evaporator and the by-product salt of NaBr was removed byfiltration after addition of methanol. Finally, salicylate based IL as ayellow liquid was dried under vacuum |
Yield | Reaction Conditions | Operation in experiment |
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at 20℃; for 72h; | General procedure: Fig. 1 illustrates the general synthesis of salicylate and thiosalicylatebased ILs [39-41]. Firstly, 20 mmol of 1-bromobutane, 1-bromohexane,or 1-bromooctane was added to 20 mmol of N-methylimidazole, andthe mixture was refluxed while being stirred at 140 C for 30 minuntil a yellow liquid with high viscosity was obtained. The preparedILs ([BMIM][Br], [HMIM][Br], or [OMIM][Br]) were extracted with10 mL diethyl ether and washed with DDW, respectively, dried overanhydrous sodium sulfate and evaporated under vacuum. Secondly, becausethe halide salts underwent metathesis reaction to give the desiredionic liquid, 20 mmol of <strong>[54-21-7]sodium salicylate</strong> was added to the obtained ILinwater, and the mixturewas stirred at roomtemperature for 72 h untilthe anion-exchange process was done. The water was removed withrotary evaporator and the by-product salt of NaBr was removed byfiltration after addition of methanol. Finally, salicylate based IL as ayellow liquid was dried under vacuum |
Yield | Reaction Conditions | Operation in experiment |
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In acetonitrile;Heating; | The 2?,3? epoxy propyl N methyl 2 oxopyrrolidinium salicylate (II)ionic liquid was synthesized and characterized according to reportedmethods [31-33]. The percentage of moisture in IL was determined byKarl-Fischer method and itwas found to be 0.003%.Schemefor synthesisof ionic liquid. |
Yield | Reaction Conditions | Operation in experiment |
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17% | General procedure: Erbium(III) nitrate pentahydrate (0.125mmol), the sodium carboxylate salt (4 mmol; 1: trimethylacetate hydrate based on an assumption of three waters of hydration; 2: sodium benzoate; 3: sodium salicylate), and <strong>[89-73-6]salicylhydroxamic acid</strong> (2mmol) were mixed in 10 mL of DMF resulting in a cloudy, white mixture for 1 and 2 or a clear, colorless solution for 3. In a separate beaker, manganese(II) acetate tetrahydrate (2 mmol) was dissolved in 10mL of DMF resulting in an orange/red solution. The two solutions were mixed resulting in a dark brown solution and then allowed to stir overnight. The solution was then filtered to remove a dark brown precipitate, which was discarded. The filtrate was then prepared for crystal growth (details below). |
Yield | Reaction Conditions | Operation in experiment |
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Ni-based MOF nanorods were prepared by a complexationreaction of Ni2+ and HOC6H4COO- followed by a hydrothermalprocess. Firstly, an aqueous 28 mL Ni(NO3)2 solution (0.02 mol L-1)was slowly added to 42 mL o-HOC6H4COONa solution (0.02 molL-1) drop by drop under continuous stirring at room temperature.Then, the pH value of the above solution was regulated to 7 with1 mol L-1 NaOH solution. Subsequently, the mixture was put into aTeflon-lined steel autoclave with a capacity of 80 mL andhydrothermally treated at 95 C for 48 h. Finally, the resultinggreen product was separated by centrifugation, washed repeatedlywith distilled water, and directly dried in a vacuum oven at 80 Cfor 24 h. |
Yield | Reaction Conditions | Operation in experiment |
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78% | pH 5; | To LaCl3 (1.51 g, 6.14 mmol) inwater (20 ml) was added Na(salH) (2.95 g, 18.42 mmol) in water(30 ml) to give a white precipitate which was filtered off. The filtrate(pH 5) was stored at 5 C and deposited a microcrystallinepowder only suitable for X-ray powder diffraction after 21 d standing.Precipitate: Yield: 2.72 g (78%). Found: La, 24.62%. C21H17O10La(568.26): Calc. La 24.44; found La 24.62. IR of both precipitate andmicrocrystalline powder were similar to 1Ce. XRPD (precipitate):d-spacing (rel. intensity) 12.70 (33), 10.99 (100), 10.53 (37), 5.94(18), 5.59 (8), 5.51 (8), 5.28 (8), 4.93 (8), 4.56 (7), 4.29 (6), 4.19(11), 3.94 (9), 3.52 (11), 3.38 (11), 3.14 (7), 2.89 (7) A. XRPD ofthe deposited powder (Yield 0.11 g; 3%) was similar to that ofthe precipitate; |
Yield | Reaction Conditions | Operation in experiment |
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21% | at 5℃; for 0.166667h;pH 5; | effect of crystallization at5 C and 25 C. To ErCl3 (0.72 g, 2.62 mmol) in water (20 ml) wasadded Na(salH) (1.26 g, 7.83 mmol) in water (20 ml) to give a pinkprecipitate. Yield: 0.44 g (26%). IR (nu/cm1): 3630 m, 3514 m,33334 m br, 1665 m (sh), 1622 s, 1593 s, 1584 s, 1545 vs, 1534vs, 1483 vs, 1462 vs, 1401 vs, 1339 s, 1309 m, 1239 s, 1212 s,1160 m, 1146 s, 1034 m, 960 w, 932 w, 874 m, 823 m, 807 m,760 s, 702 m, 668 m. XRPD: d-spacing (rel. intensity) 10.84 (100),7.934 (16), 7.42 (15), 6.75 (8), 5.42 (16), 4.98 (8), 4.80 (11), 4.72(15), 4.53 (11), 4.19 (12), 4.03 (5), 3.97 (6), 3.86 (5), 3.79 (6),3.48 (6), 3.41 (11), 3.37 (13), 3.26 (4). C21H23O13Er (650.66): Calc.Er 25.71%; found: Er 25.81. The filtrate (pH 5) was divided andstored at (i) 5 C and (ii) 25 C and deposited pink crystals. Method(i) Yield: 0.36 g (21%) after 21 d. C21H23O13Er (650.66): Calc. C,38.76; H, 3.56; Er 25.71; found C, 38.84; H, 3.52; Er, 25.69%. Method (ii) Yield: 0.29 g (17%) after 10 d. IR and XRPD of all productswere similar. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | for 0.166667h;pH 5; | To CeCl37H2O (81.08 g,217.6 mmol) in water (200 ml) was added Na(salH) (104.5 g,652.8 mmol) in water (400 ml) to give a white precipitate. The filtrate(pH 5) was stored at 5 C and deposited a microcrystallinepowder unsuitable for X-ray structural determination after2 months standing. Precipitate: Yield: 120.02 g (95%). IR: (nu/cm-1): 3317 m, 1676 w, 1623 m, 1605 m, 1598 m, 1583 m, 1560vs, 1548 m, 1508 m, 1480 m, 1465 m, 1436 m, 1422 m, 1406 s,1381 vs, 1351 m, 1330 w, 1308 m, 1245 m, 1232 m, 1220 m,1174 w, 1160 m, 1148 m, 1107 m, 1032 m, 970 w, 960 w, 945 w,881 w, 851 m, 804 m, 790 w, 754 s, 703 m, 663 m. XRPD: d-spacing(rel. intensity) 12.81 (64), 11.12 (100), 10.65 (57), 10.05 (5), 6.39(6), 5.99 (19), 5.79 (5), 5.59 (11), 5.31 (10), 4.94 (18), 4.78 (7),4.68 (7), 4.58 (12), 4.31 (10), 4.20 (21), 4.11 (3), 3.93 (13), 3.83(7), 3.69 (3), 3.62 (7), 3.52 (12), 3.40 (22), 3.34 (7), 3.24 (6), 3.14(15), 3.07 (5), 3.03 (6), 3.00 (7), 2.92 (7), 2.89 (11). A. C21H17O10Ce(569.47): Calc. C, 44.29; H, 3.01; Ce, 24.60; found C, 44.42, H, 3.15;Ce, 24.32%. Deposit from filtrate: Yield: 0.31 g (<1%). IR: Similar tothe precipitate. C21H17O10Ce (569.47): Calc. Ce 24.60; found Ce24.43. After many unavailing attempts single crystals of (1Ce) wereeventually obtained using a ?H?-tube with one side containingCeCl37H2O (0.20 g, 0.54 mmol) in a 50 vol% water/ethanol mixture(20 ml) and the other a solution of Na(salH) (0.26 g, 1.61 mmol) also in 50 vol% water/ethanol (20 ml). The tube was filled to allowboth reaction solutions to just make contact in the bottom ?H? sectionof the tube. Slow crystallisation at 5 C over 2 months gavesingle crystals which were amenable to structure elucidation usinga Synchrotron. |
Yield | Reaction Conditions | Operation in experiment |
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70% | 1.0M NaOH (0.35mL, 0.35mmol) was added to a brick-red suspension of [RuCl(mu-Cl)(eta6-p-cymene)]2 (105mg, 0.171mmol) and Na[salCO2] (55mg, 0.344mmol) in MeOH (10mL) and the mixture was stirred at reflux temperature for 3h. The resulting orange solution was allowed to cool to room temperature then volatiles were removed under vacuum. The residue was suspended in CHCl3 and insoluble NaCl was filtered over celite. The filtrate solution was treated with PPh3 (91mg, 0.347mmol) and stirred at reflux temperature for 3.5h. The progress of reaction was checked by 31P NMR then the orange solution was allowed to cool to room temperature and filtered over celite. The filtrate was taken to dryness under vacuum and the residue was suspended in 71 Et2O (2-3mL). The suspension was filtered and the resulting orange-brown 29 solid was washed with Et2O (2mL) then dried under vacuum (40C). Yield: 152mg, 70%. Compound 5 is soluble in DMSO, CH2Cl2, CHCl3, less soluble in MeOH, poorly soluble in Et2O and insoluble in hexane, H2O. Anal Calcd. For C20H29Cl3Ru2: C, 66.34; H, 5.25. Found: C, 66.18; H, 5.35. IR (solid state): /cm1=3904w, 3853w, 3837w, 3801w, 3748w, 3675w, 3649w, 3054w, 2967w, 2924w, 2868w, 1600s, 1581s (nuas, CO2), 1571s-sh, 1505w, 1482m, 1460s, 1445s, 1434s, 1379m, 1331s (nus, CO2), 1248m, 1186w, 1129m, 1117m-sh, 1094s, 1030m, 999w, 874m, 855m, 823w, 799w, 758s, 750s, 696s, 667w-sh, 663w-sh. 1H NMR (CDCl3): delta/ppm=7.86 (d, 3JHH=7.6Hz, 1H, C10-H), 7.67 (pseudo-t, 3JHH=3JHP=8.8Hz, 6H, C16-H), 7.41-7.31 (m, 9H, C17-H+C18-H), 6.98 (t, 3JHH=7.3Hz, 1H, C12-H), 6.68 (d, 3JHH=8.1Hz, 1H, C13-H), 6.45 (t, 3JHH=7.1Hz, 1H, C11-H), 5.26 (d, 3JHH=6.0Hz, 1H, C4-H), 5.17 (d, 3JHH=5.8Hz, 1H, C4?-H), 5.05 (d, 3JHH=5.7Hz, 1H, C3-H), 4.70 (d, 3JHH=5.7Hz, 1H, C3?-H), 2.50 (hept, 3JHH=6.6Hz, 1H, C6-H), 1.87 (s, 3H, C1-H), 1.18 (d, 3JHH=7.2Hz, 3H, C7-H), 1.14 (d, 3JHH=6.9Hz, 3H, C7?-H). No change in the 1H spectrum was observed after 24hat room temperature whereas degradations products were observed after 6 days. 13C{1H} NMR (CDCl3): delta/ppm=171.7 (C8), 170.9 (C14), 134.1 (d, 2JCP=10Hz, C16), 133.3 (C10), 132.2 (d, 1JCP=44Hz, C15), 131.0 (C12),130.5 (d, 4JCP=2Hz, C18), 128.4 (d, 3JCP=10Hz, C17), 122.5 (C9), 121.9 (C13), 114.4 (C11), 106.5 (C5), 98.0 (C2), 88.5 (d, 2JCP=5Hz, C4), 87.3 (d, 2JCP=5Hz, C3/C3?), 87.2 (d, 2JCP=3Hz, C3/C3?), 85.8 (d, 2JCP=3Hz, C4?), 30.7 (C6), 23.0 (C7?), 21.9 (C7), 17.4 (C1). 31P{1H} NMR (CDCl3): delta/ppm=26.7.31P{1H} NMR (CH3OD): delta/ppm=27.0. |
Yield | Reaction Conditions | Operation in experiment |
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In water; acetone; | The API-IL benzalkonium salicylate was prepared from benzyldimethyldodecylammoniumchloride (benzalkonium chloride) and sodium salicylate according to a procedure similar tothat described in the literature [8]. Sodium salicylate (0.93 g, 5.8 mmol) and benzyldimethyldodecylammoniumchloride (2.05 g, 5.8 mmol) were dissolved in 20 mL of acetone/H2O(1:1). The reaction mixture was stirred overnight at room temperature. The remaining suspensionwas diluted with 20 mL of distilled water. The product was extracted with dichloromethane.Sodium chloride as a byproduct was removed by washing the dichloromethane phase successivelywith water. The presence of chloride ions in the washings was detected using AgNO3solution. The dichloromethane was evaporated under reduced pressure. The obtained API-ILwas further dried at 343 K in vacuum for 8 h. The water content of the API-IL was determinedby a Karl-Fischer measurement, and the value was about 350 ppm. The synthesized API-ILwas characterized by 1H NMR (Bruker DPX) and IR (Nicolet IR-470).The characterization values obtained are: IR (KBr, cm-1): 3437(s), 3027(w), 2921(s),2852(s), 1638(s), 1590(s), 1484(s), 1456(s), 1219(s), 1137(m), 758(m), 735(m);1H NMR:(400 MHz, CDCl3)delta in ppm: delta 7.97 (dd, J = 7.7, 1.7 Hz, 1H), 7.48 (m, 6H), 6.87 (d,J = 8.2 Hz, 1H), 6.76 (t, J = 7.4 Hz, 1H), 4.82 (s, 2H), 3.36 (m, 2H), 3.21 (s, 6H), 1.74 (s, 2H),1.24 (d, J = 7.4 Hz, 18H), 0.88 (t, J = 6.8 Hz, 3H). The 1H NMR spectra of BaSal is presentedin Fig. S1 of the Supplementary Material.Thermal stability was measured on a STA 409 PC simultaneous thermal analyzer (Germany)in the range of 303-773 K at a heating rate of 10 K·min-1 under an air environment. Itcan be seen from Supplementary Fig. S2 that BaSal has good thermal stability with the lowdecomposition temperature of 454 K. |
Yield | Reaction Conditions | Operation in experiment |
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In acetonitrile; at 20℃; | General procedure: The two new API-ILs, 1-octyl-3-methylimidazolium salicylate,[OMIm][Sal] and 1-octyl-3-methylimidazolium ibuprofenate, [OMIm][Ibu] (see the structure of API-IL in Fig. 1) were prepared from the1-octyl-3-methylimidazolium chloride [OMIm][Cl] and sodiumsalicylateand sodium ibuprofenate, respectively. 1-octyl-3-methylimidazoliumchloride was synthesized and purified according to the standardmethods reported in the references [24-27]. The water content of preparedionic liquid, [OMIm][Cl] determined by Karl Fischer method wasb0.05% in mass fraction. Characterization of the ionic liquid by 1HNMRspectroscopy showed good agreement as compared with the literatureand confirmed the absence of any significant impurity [26]. The purityof prepared ionic liquid was 98% in mass fraction. To synthesize the1-octyl-3-methylimidazolium salicylate ionic liquid [OMIm][Sal],(0.4 mol) <strong>[54-21-7]sodium salicylate</strong> was dissolved in dried acetonitrile andadded slowly to (0.4 mol) [OMIm][Cl] dissolved in a minimum amountof dried acetonitrile. The resulting mixture was stirred overnigth atroomtemperature then the rotary evaporator at 350 K and then reducedpressurewas used to extract thewater in themixture. The resultingmixturewas subsequently dissolved in a large amount of dichloromethaneto observe white precipitate containing sodium chloride. The white precipitatewas then filtered and this process was continued until no whitesolid observed with the addition of dichloromethane [23-25]. The silvertest confirmed the lack of sodium chloride. The obtained product (a yellowishsolid) was further evaporated at 343.15 K by rotary evaporator[26]. The procedure for synthesis of 1-octyl-3-methylimidazoliumibuprofenate, [OMIm][Ibu] is similar to [OMIm][Sal] and the only differenceis applying the ethanol as solvent and heating at 353.15 K for 3 h at the beginning of the reaction. The water content of the [OMIm][Sal]and [OMIm][Ibu] determined using coulometric Karl Fischer titrator(Metrohm 756 KF) was approximately 0.1% in mass fraction. The 1HNMR (Brucker Av-400) spectroscopy was applied to characterize theprepared API-ILs (see Figs. S1 and S2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20%; 12% | In N,N-dimethyl-formamide; at 20℃; for 5h; | Salicylic acid sodium salt (162 mg, 1.01 mmol) was added to a solution of 2 (200 mg, 0.668 mmol) and DMF (10 mL) at room temperature and stirred for 5 h. The progress of the reaction was monitored by TLC (hexane / ethyl acetate=5/1). The DMF solution was extracted with ethyl acetate (3×30 mL) and the combined organic extracts were washed with brine (2×30 mL), dried over Na2SO4, and concentrated on a rotary evaporator. Chromatography on silica gel, eluting with a 10:1?8:1?6:1?2:1 mixture of hexane and ethyl acetate, afforded 3 as a white solid and 4 as a white oil in 20 % and 12 % yield, respectively. 4.1.1.1 Compound 3 Yield (20 %: white solid). Mp: 130.0-131.5 C. IR (KBr): 3413, 2959, 1674, 1640 cm-1. 1H NMR (CDCl3, 400 MHz): delta 1.13 (br s, 3H, CH3 at C4?), 1.26 (br s, 3H, CH3 at C4?), 1.73 (s, 3H, CH3 at C8?), 1.95-2.84 (br m, 6H, CH2 at C3?, C10?, and C11?), 4.71 (br d, J=9.5 Hz, 1H, CH at CH2OCO), 4.97 (br d, J=9.5 Hz, 1H, CH at CH2OCO), 5.54 (t, 1H, J=8.3 Hz, CH at C2?), 5.87 (d, 1H, J=16.5 Hz, CH at C5?), 6.02 (d, 1H, J=16.5 Hz, CH at C6?), 6.06 (br m, 1H, CH at C9?), 6.88 (ddd, 1H, J=8.1, 7.0, 1.0 Hz, CH at C5 of Ph), 7.00 (dd, 1H, J=8.4, 1.0 Hz, CH at C3 of Ph), 7.47 (ddd, 1H, J=8.4, 7.0, 1.7 Hz, CH at C4 of Ph), 7.81 (dd, 1H, J=8.1, 1.7 Hz, CH at C6 of Ph), 10.70 (s, 1H, OH at Ph); 13C NMR (CDCl3, 100 MHz): delta 12.0 (CH3 at C8?), 24.1 (CH3 at C4?), 24.8 (C10?), 29.4 (CH3 at C4?), 35.5 (C11?), 37.5(C4?), 42.4 (C3?), 61.7 (CH2OCO), 112.2 (C2 of Ph), 117.8 (C3 of Ph), 119.3 (C5 of Ph), 127.4 (C6?), 129.7 (C6 of Ph), 132.0 (C2?), 134.0 (C1?), 136.0 (C4 of Ph), 138.6 (C8?), 149.0 (C9?), 159.6 (C5?), 161.8 (C1 of Ph), 170.0 (COO at Ph), 203.6 (C7?); HRMS m/z [M+ Na]+ Calcd for C22H26NaO4+ 377.1723; Found 377.1742. 4.1.1.2 Compound 4 Yield (12 %: white oil). IR (KBr): 2961, 1732, 1655 cm-1. 1H NMR (CDCl3, 400 MHz): delta 1.12 (br s, 3H, CH3 at C4?), 1.12 (br s, 3H, CH3 at C4?), 1.25 (br s, 3H, CH3 at C4?), 1.25 (br s, 3H, CH3 at C4?), 1.69 and 1.78 (s, 3H, CH3 at C8?, C8?), 1.94-3.02 (br m, 12H, CH2 at C3?, C3?, C10?, C10?, C11?, and C11?), 4.27 (br m, 1H, CH at CH2O), 4.70 (br m, 1H, CH at CH2OCO), 4.75-5.00 (br m, 2H, CH at CH2OCO and CH2O), 5.46-5.55 (m, 1H, CH at C2? and C2?), 5.79 and 5.87 (d, 1H, J=16.5, 16.4 Hz, CH at C5? and C5?), 6.01 and 6.03 (d, 1H, J=16.5, 6.4 Hz, CH at C6? and C6?), 6.06 (m, 2H, CH at C9? and C9?), 6.94-7.05 (m, 2H, CH at C3 and C5 of Ph), 7.47 (ddd, 1H, J=8.4, 6.7, 1.8 Hz, CH at C4 of Ph), 7.78 (dd, 1H, J=7.7, 1.8 Hz, CH at C6 of Ph), 13C NMR (CDCl3, 100 MHz): delta 11.9 (CH3 at C8), 11.9 (CH3 at C8?), 24.1 (CH3 at C4?), 24.1 (CH3 at C4?), 24.6 and 24.8 (C10?, C10?), 29.4 (CH3 at C4?), 29.4 (CH3 at C4?), 34.9 and 35.6 (C11?, C11?), 37.4 and 37.6 (C4?, C4?), 42.4 (C3?), 42.4 (C3?), 61.3 (CH2OCO), 65.3 (CH2O), 113.5 (C3 of Ph), 120.6 (C2 of Ph), 120.7 (C5 of Ph), 127.3 and 127.5 (C6?, C6?), 129.5 (C2?), 131.2 (C2?), 131.7 (C6 of Ph), 133.6 (C4 of Ph), 134.7 and 135.9 (C1?, C1?), 138.5 and 138.6 (C8?, C8?), 149.1 and 149.6 (C9?, C9?), 158.2 (C1 of Ph), 159.3 and 159.8 (C8?, C8?), 165.9 (COO at Ph), 203.7 and 203.8 (C7?, C7?); HRMS m/z [M+ Na]+ Calcd for C37H46NaO5+ 593.3237; Found 593.3224. |
19.5%; 11.6% | In N,N-dimethyl-formamide; at 20℃; for 5h;Darkness; | Put 200 mg (0.67 mmol) of Compound 2 in a lightproof bottle,Add 10 mL of DMF and stir.Add <strong>[54-21-7]sodium salicylate</strong> 1.5 eq (162 mg, 1.01 mmol),Stir at room temperature for 5 hours. After completion of the reaction was confirmed by TLC (Hexane / AcOEt = 5/1), the reaction was stopped."TLC" is "Thin-Layer-Chromatography", "Hexane" is hexane,"AcOEt" is ethyl acetate. The reaction solution is extracted three times with ethyl acetate,It was washed three times with saturated saline.Then, it was dried over anhydrous sodium sulfate, concentrated under reduced pressure using a rotary evaporator, and dried under vacuum.The resulting product is separated and purified by open column chromatography (Hexane / AcOEt = 10/1 ? 8/1 ? 6/1 ? 2/1).Compound 3 (Rf = 0.35) in a yield of 19.5% at 46.6 mg,Compound 4 (Rf = 0.075) in a yield of 11.6% 22.4 mg, 66.5 mg of compound 3a (Rf = 0.425),Compound 3b (Rf = 0.275) 10.5 mg,2.6 mg of compound 3c (Rf = 0.55) was obtained. Compound 3a, Compound 3b,The structure of compound 3c is undetermined. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In acetonitrile; for 6h;Reflux; | General procedure: Thiophenol (0.32 g, 2.91 mmol) in acetonitrile solution(25 mL) was added to the acetonitrile solution (30 mL)of bis(diisobutyldithiophosphato)antimony(III) chloride(1.9 g; 2.91 mmol) in equimolar ratio. The reaction mixturewas refluxed for 6 h and libration of HCl gas wasobserved. After cooling, the solvent was removed underreduced pressure. The yellow color powder, thus obtained,was recrystallized from dichloromethane.All the synthesized derivatives are light yellow-orangecolored solids and are soluble in common organic solventslike benzene, acetonitrile, chloroform, ether etc. All theother bis(diisobutyldithiophosphato)antimony(III) derivativeswith thio and oxo donor ligands were synthesized by applyingan analogous method and their analytical data and spectraldata are summarized below |
Tags: 54-21-7 synthesis path| 54-21-7 SDS| 54-21-7 COA| 54-21-7 purity| 54-21-7 application| 54-21-7 NMR| 54-21-7 COA| 54-21-7 structure
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P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
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 |
Sorry,this product has been discontinued.
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