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CAS No. : | 702-23-8 | MDL No. : | |
Formula : | C9H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AUWDOZOUJWEPBA-UHFFFAOYSA-N |
M.W : | 152.19 | Pubchem ID : | 69705 |
Synonyms : |
p-Methoxyphenylethanol
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.33 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 43.87 |
TPSA : | 29.46 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.7 cm/s |
Log Po/w (iLOGP) : | 1.95 |
Log Po/w (XLOGP3) : | 0.75 |
Log Po/w (WLOGP) : | 1.23 |
Log Po/w (MLOGP) : | 1.53 |
Log Po/w (SILICOS-IT) : | 2.0 |
Consensus Log Po/w : | 1.49 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.46 |
Solubility : | 5.26 mg/ml ; 0.0345 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.95 |
Solubility : | 17.1 mg/ml ; 0.113 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.74 |
Solubility : | 0.276 mg/ml ; 0.00181 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.01 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | 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 |
---|---|---|
97.4% | Production Example 7 Synthesis of 4-methoxyphenethyl bromide 4-Methoxyphenethyl alcohol (0.61 g) was treated as in Production Example 1 to give the title compound (0.838 g) as a pale yellow oil (yield: 97.4%). 1H-NMR (400 MHz, CDCl3): delta(ppm) 3.10(2H, t, J=7.6Hz), 3.53(2H, t, J=7.6Hz), 3.80(3H, s), 6.86(2H, d, J=8.2Hz), 7.13(2H, d, J=8.2Hz). | |
97% | With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 20℃;Inert atmosphere; | In a three-neckflask, <strong>[702-23-8]2-(4-methoxyphenyl)ethanol</strong> (2a, 3.00 g, 1 eq.) andtriphenylphosphine (6.72 g, 1.3 eq.) were dissolved in dryCH2Cl2 (25 ml). In an addition funnel, carbon tetrabromide(8.50 g, 1.3 eq.) was dissolved in dry CH2Cl2 (15 ml) andadded dropwise under inert atmosphere at 0 C until theaddition was complete. The reaction was allowed to stirat room temperature for an additional 4 h, or until completedisappearance of starting materials from thin-layerchromatography (TLC). The solvent was removed underreduced pressure, and the residue was purified by column chromatography using hexane and EtOAc to yield 3a as aclear oil. Yield: 4.11 g (97 %). 1H NMR (CDCl3) delta (ppm):3.08-3.12 (t, 2H), 3.51-3.55 (t, 2H), 3.79 (s, 3H), 6.85-6.87 (d, 2H), 7.12-7.14 (d, 2H). |
With phosphorus tribromide; In benzene; | PREPARATION F 4-(3-[p-Methoxyphenyl]propyl)pyridine To a stirred solution of 3.04 g. of <strong>[702-23-8]2-(p-methoxyphenyl)ethanol</strong> in 10 ml. of benzene, is added dropwise, a solution of 0.72 ml. of phosphorus tribromide in 10 ml. of benzene, at ambient temperature. The mixture is then heated at 60C. for 1 hour. After being cooled to ambient temperature again, the reaction mixture is poured onto 50 g. of crushed ice. A small amount of ether is added, and then the organic phase is separated off, washed sequentially with 0.5N sodium hydroxide and water, and evaporated to dryness. This affords 2.8 g. of 2-(p-methoxyphenyl)ethyl bromide as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With phosphorus pentachloride; calcium carbonate; In toluene; at 0 - 20℃; for 3.66667h;Inert atmosphere; | 6 (2.0 g, 13.1 mmol) was dissolved in dry toluene (50mL), dry CaCO3 (3.94 g, 39.4 mmol), PCl5 (5.47 g, 26.3 mmol) were added slowly over a period of 40 min under argon atmosphere at 0 C; temperature in the mixture was allowed to reach RT and stirred for another 3 h. The mixture was poured into ice-cold saturated NaHCO3 solution (20 mL) and extracted twice with diethyl ether (100 mL). The organic layer was dried with Na2SO4 and evaporated. Purification by silica gel column chromatography (n-hexane-ethyl acetate 9:1 (v/v)) yielded a yellow oil:7 (1.95 g, 87 %). |
With methanesulfonyl chloride; triethylamine; In dichloromethane; at 0 - 20℃; for 12.08h;Inert atmosphere; | MsCl (270 mg, 2.36 mmol) was added dropwise into a mixture of 2-(4- methoxyphenyl)ethan-l-ol (300 mg, 1.97 mmol), dichloromethane (10 mL), and TEA (596.9 mg, 5.90 mmol) at 0C in 5 min under nitrogen. The resulting solution was stirred for 12h at room temperature. The resulting mixture was concentrated under vacuum. This resulted in the title compound (430 mg, crude) as a white solid, which was used for the next step without any further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C30H34Cl2N2P2Ru; potassium methanolate; hydrogen; In tetrahydrofuran; at 100℃; under 38002.6 - 76005.1 Torr; for 5h;Glovebox; Autoclave; | General procedure: In a glove box, add a ruthenium complex Ia (0.3 to 0.7 mg, 0.0002 to 0.001 mmol) to a 300 mL autoclave,Potassium methoxide (35-700 mg, 0.5-10 mmol), tetrahydrofuran (4-60 mL), and ester compounds (10-200 mmol).After sealing the autoclave, take it out of the glove box and fill it with 50 100atm of hydrogen.The reaction kettle was heated and stirred in an oil bath at 100 C for 10 to 336 hours.After the reaction kettle was cooled in an ice-water bath for 1.5 hours, the excess hydrogen was slowly released.The solvent was removed from the reaction solution under reduced pressure, and the residue was purified with a short silica gel column to obtain an alcohol compound. The results are shown in Table 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.3% | With sodium tetrahydroborate; boron trifluoride diethyl etherate; In tetrahydrofuran; at 20℃; | P-methoxy phenylacetic acid (90.0g, 542mmol), tetrahydrofuran (700 ml of), sodium borohydride (31.0g, 819mmol) and boron trifluoride etherate (108.5g, 894mmol) added to the reaction flask and the reaction was stirred at room temperature, the reaction was complete after adding an appropriate amount of water to provide an alkaline pH, extraction, washing, drying, the organic phase was concentrated under reduced pressure to give nearly colorless oil methoxybenzyl alcohol (81.0 g of), a yield of 98.3%. |
63% | With 1,1,3,3-Tetramethyldisiloxane; copper(II) bis(trifluoromethanesulfonate); In toluene; at 80℃; for 16h;sealed tube; | General procedure: In a sealed tube, 29 mg Cu(OTf)2 (0.08 mmol, 8 mol %) and 0.7 mL TMDS (537 mg, 4 mmol, 8 Si-H mol/mol substrate) were introduced to a solution of aliphatic carboxylic acid (1 mmol) in 1.5 mL toluene. After stirring 16 h at 80 C, the reaction mixture was cooled to room temperature and quenched with 4 mL H2O. The organic layer was extracted with CH2Cl2, dried with anhydrous MgSO4, and evaporated under reduced pressure. The crude was purified by silica gel column chromatography to obtain the alcohol. |
To a THF solution (0.2 M) of 4-methoxyphenylacetic acid (1 eq.) was added borane- methylsulfide complex (1.25 eq.) dropwise at 0 0C. The resulting solution was allowed to warm slowly to RT over 1 h. The reaction mixture was then diluted with ether and carefully quenched with 10% HCl. The organic layer was separated, washed further with 1 N aq. NaOH, dried over Na2SO4 and filtered. Concentration of the filtrate in vacuo afforded the title compound as a colorless oil that solidified upon standing. |
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0℃; for 4.5h;Reflux; | General procedure: To a mixture of LiAlH4 (15 mmol) in anhydrous THF (25 mL) in an ice-bath was added dropwise a solution of phenylacetic acids (15 mmol) in THF (8 mL). This mixture was stirred at room temperature for 30 min, and then heated to reflux for 4 h. After it was cooled to room temperature, water (0.5 mL) was added, and then NaOH (15%, 0.5 mL) and water (1.5 mL) were added in sequence. After stirring for another 30 min, the mixture was filtered, dried over anhydrous Na2SO4 and concentrated to give crude products. Pure phenylethyl alcohols were obtained in 50-85% yield by column chromatography. Alternative method: To a solution of phenylacetic acids (15 mmol) in MeOH (30 mL) was added SOCl2 (30 mmol). This mixture was heated to reflux for 3 h before evaporation. The residue was dissolved in DCM (30 mL), washed with aqueous NaHCO3, water and brine, dried over anhydrous Na2SO4, and concentrated to give 100% yield of crude methyl phenylacetates which were used to next step without further purification. To a solution of the methyl phenylacetates in THF (30 mL) was added NaBH4 (60 mmol). When the mixture was heated to gently reflux, MeOH (1.0 mL) was added dropwise from a syringe over 5 min. After refluxing for another 6 h, the mixture was cooled to room temperature and poured into 30 mL ice water, and extracted with EtOAc (30 mL × 2). The combined organic phase was washed with brine, dried over anhydrous Na2SO4, and concentrated to give crude products. Pure phenylethyl alcohols were obtained in 70-85% yield by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; trifluorormethanesulfonic acid; R,R-3,4-dimethyl-5-phenyl-1,3,2-oxazaborolidine; rhodium complex with 1,1-bis(diphenylphosphino)ferrocene; dihydrogen peroxide; bicyclo[2.2.1]hepta-2,5-diene other multistep reaction, mechanism of hydroboration; | ||
With sodium hydroxide; (1,5-cyclooctadiene)(2,4-pentadionato)rhodium(I); (R)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine); dihydrogen peroxide; benzo[1,3,2]dioxaborole Yield given. Multistep reaction. Yields of byproduct given; | ||
With sodium hydroxide; (1,5-cyclooctadiene)(2,4-pentadionato)rhodium(I); (R)-(6,6'-difluorobiphenyl-2,2'-diyl)bis(diphenylphosphine); dihydrogen peroxide; benzo[1,3,2]dioxaborole Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts; |
Stage #1: 4-Methoxystyrene With benzo[1,3,2]dioxaborole In toluene at 20℃; for 2h; Stage #2: With sodium hydroxide; water; dihydrogen peroxide In toluene at 20℃; for 2h; Title compound not separated from byproducts; | ||
Stage #1: 4-Methoxystyrene With (S)-quinazolinap rhodium; benzo[1,3,2]dioxaborole In tetrahydrofuran at 20℃; for 2h; Stage #2: With sodium hydroxide; dihydrogen peroxide In tetrahydrofuran; ethanol at 0 - 20℃; Title compound not separated from byproducts; | ||
Stage #1: 4-Methoxystyrene With (R)-2-tert-butyl-quinazolinap rhodium; benzo[1,3,2]dioxaborole In tetrahydrofuran at 20℃; for 2h; Stage #2: With sodium hydroxide; dihydrogen peroxide In tetrahydrofuran; ethanol at 0 - 20℃; Title compound not separated from byproducts; | ||
Stage #1: 4-Methoxystyrene With diethoxymethylane In toluene at 50℃; for 72h; Stage #2: With potassium fluoride; dihydrogen peroxide; potassium carbonate In tetrahydrofuran; methanol at 0℃; | ||
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 1-(2-(diphenylphosphaneyl)naphthalen-1-yl)-4-((R)-1-phenylethoxy)phthalazine; benzo[1,3,2]dioxaborole In toluene at 20℃; for 2h; | ||
Stage #1: 4-Methoxystyrene With pinacol borane; 4 A molecular sieve; chiral TADDOL-based reagent In 1,2-dimethoxyethane at 0 - 20℃; Stage #2: With sodium hydroxide; dihydrogen peroxide In methanol; 1,2-dimethoxyethane; water at 0 - 20℃; Title compound not separated from byproducts; | ||
Stage #1: 4-Methoxystyrene With benzo[1,3,2]dioxaborole In tetrahydrofuran at 25℃; for 2h; Stage #2: With sodium hydroxide; dihydrogen peroxide In tetrahydrofuran at 20℃; for 1h; Further stages. Title compound not separated from byproducts.; | ||
Stage #1: 4-Methoxystyrene With trimethylsilyl trifluoromethanesulfonate; benzo[1,3,2]dioxaborole In tetrahydrofuran at 0℃; for 2h; Stage #2: With sodium hydroxide; dihydrogen peroxide In tetrahydrofuran at 20℃; for 1h; Further stages. Title compound not separated from byproducts.; | ||
Stage #1: 4-Methoxystyrene With (S)-di(3,5-xylyl)(1-(2-isopropyl-quinazolin-4-yl)(2-naphthyl))phosphine rhodium(1,5-cyclooctadeine) trifluoromethanesulfonate; benzo[1,3,2]dioxaborole In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Stage #2: With water; dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; ethanol at 0 - 20℃; Inert atmosphere; optical yield given as %ee; | ||
Stage #1: 4-Methoxystyrene With CF3O3S(1-)*C45H39N2OPRh(1+); benzo[1,3,2]dioxaborole In tetrahydrofuran at 0℃; Inert atmosphere; Stage #2: With dihydrogen peroxide; sodium hydroxide In ethanol; water at 0 - 20℃; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: 4-Methoxystyrene With CF3O3S(1-)*C41H38ClN2PRh(1+); benzo[1,3,2]dioxaborole In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Stage #2: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran; ethanol; water at 0 - 20℃; for 1h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With triethylamine; In toluene; at 0 - 20℃; for 48h; | Reactant: 6. To a stirred solution of compound 6 (1.0 g, 6.57 mmol) in toluene (40 mL) triethylamine(2.0 mL, 19.71 mmol) was added at 0 C. TsCl (1.5 g, 7.88 mmol) was added slowly and the reaction mixture stirred 48 h at RT. The solution was diluted with diethyl ether and washed with saturatedaqueous NaHCO3 (20 mL). The residue of unreacted precipitated TsCl was filtered out and organiclayer was dried, filtered and concentrated to give light yellow crystals: 29 (2.0 g, 99 %). |
With pyridine; at 0 - 20℃; for 4h; | General procedure: 5.1.57.3. Step 3. To a solution of 2-(3-fluorophenyl)ethanol(25.26 g, 180 mmol) in pyridine (180 mL) was added TsCl(36.49 g, 186 mmol) at 0 C with silica gel blue tube. After stirringat rt for 4 h, the reaction was quenched by the addition of 2 N HCl (750 mL) at 0 C. This mixture was extracted with EtOAc (300 mL).The separable organic layer was washed with 2 N HCl (250 mL),H2O (200 mL), brine (100 mL), and dried over MgSO4, filtered, concentratedunder reduced pressure. The residue was purified by columnchromatography (SiO2, n-hexane/EtOAc = 10/1-5/1) to obtain2-(3-fluorophenyl)ethyl 4-methylbenzenesulfonate (38.54 g, 73%)as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 2.B.72.1 Example 72 Preparation of Intermediate 72 Step 1: To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) in CH2Cl2 (50 mL) at 0° C. was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for 1 hour. Washed with sat. Na2S2O3 (aq) and 1M NaOH, brine respectively. Dried over MgSO4, filtered, and concentrated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 41.1 To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) in CH2Cl2 (50 mL) at 0° C. was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for 1 h. Washed with sat. Na2S2O3 (aq) and 1M NaOH, brine respectively. Dried over MgSO4, evaporated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | B.III.3.1 Example 3: Preparation of Compound 3.; Step 1: To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) inCHzCI2 (50 mL) at0 C was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for1 h. Washed with sat. Na2S203 (aq) and 1M NaOH, brine respectively. Dried overMgS04, evaporated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 41.1 Step 1: To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) in CH2Cl2 (50 mL) at 00 C was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for 1 h. Washed with sat. Na2S2O3 (aq) and 1M NaOH, brine respectively. Dried over MgSO4, evaporated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 2h; | 99.c c) 2-(4-methoxyphenyl)acetaldehyde (I-55) c) 2-(4-methoxyphenyl)acetaldehyde (I-55) [0300] Dess-Martin periodinane (5.8 g; 13.79 mmol; 1.05 eq) was added to a solution of 2-(4-methoxyphenyl)ethan-1-ol (2 g; 13.14 mmol; 1 eq) in dichloromethane (90 mL) at 0°C. The reaction mixture was stirred at 0°C for 30 minutes and at room temperature for 1.5 hours. Dichloromethane (100 mL) was added and the organic layer was washed with sodium thiosulfate 10% in water (100 mL) and sodium hydroxide 1M (100 mL), dried over sodium sulfate, filtrated and concentrated to dryness. The title compound, 2-(4-methoxyphenyl)acetaldehyde was obtained in quantitative yield (2.1 g) as a colorless oil. 1H NMR (CDCl3): δ 3.68 (s, 2H), 3.87 (s, 3H), 6.97 (d, 2H), 7.19 (d, 2H), 9.78 (s, 1H). |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 2h; | 99.c c) 2- (4-methox yphen yl) acetaldeh yde (1-55) c) 2- (4-methox yphen yl) acetaldeh yde (1-55) Dess-Martin periodinane (5.8 g; 13.79 mmol; 1.05 eq) was added to a solution of 2- (4-methoxyphenyl)ethan- l-ol (2 g; 13.14 mmol; 1 eq) in dichloromethane (90 mL) at 0°C. The reaction mixture was stirred at 0°C for 30 minutes and at room temperature for 1.5 hours. Dichloromethane (100 mL) was added and the organic layer was washed with sodium thiosulfate 10% in water (100 mL) and sodium hydroxide 1M (100 mL), dried over sodium sulfate, filtrated and concentrated to dryness. The title compound, 2-(4-methoxyphenyl)acetaldehyde was obtained in quantitative yield (2.1 g) as a colorless oil. 1H NMR (CDC13): δ 3.68 (s, 2H), 3.87 (s, 3H), 6.97 (d, 2H), 7.19 (d, 2H), 9.78 (s, 1H). |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 41.1 To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) in CH2Cl2 (50 mL) at 0° C. was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for 1 h. Washed with sat. Na2S2O3 (aq) and 1M NaOH, brine respectively. Dried over MgSO4, evaporated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
100% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 41.1 To a solution of 4-methoxyphenethyl alcohol (1.52 g, 10.0 mmol) in CH2Cl2 (50 mL) at 0° C. was added Dess-Martin reagent (4.45 g, 10.5 mmol) in one portion. The formed mixture was allowed to warm to the ambient temperature for 1 h. Washed with sat. Na2S2O3 (aq) and 1M NaOH, brine respectively. Dried over MgSO4, evaporated in vacuo to give 1.50 g (100%) of the desired aldehyde as a viscous oil. This product was used as crude without any further purification. |
95% | With 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; trichloroisocyanuric acid; Sodium hydrogenocarbonate In lithium hydroxide monohydrate; propan-2-one at 20℃; for 6h; | |
95% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1.25h; | |
90% | With Dess-Martin periodane In dichloromethane at 20℃; for 2h; Inert atmosphere; | |
88% | With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 80℃; for 2h; | |
86% | With tert.-butylnitrite; 9-azanoradamantane-N-oxyl In acetonitrile at 20℃; for 9h; chemoselective reaction; | |
85% | With Dess-Martin periodane In dichloromethane for 2h; Reflux; | 7 4.1.7 2-(4-Methoxyphenyl)acetaldehyde 2-(4-Methoxyphenyl)ethan-1-ol (300µL, 2mmol) was dissolved in 139 CH2Cl2 (30mL). Dess-Matin 140 periodinane (975mg, 2.25mmol) was added and the resulting reaction mixture was refluxed for 2 h. The solvents were removed under reduced pressure, and subjected to flash column chromatography to give the 141 product 2-(4-methoxyphenyl)acetaldehyde (250mg, 85%). 1H NMR (300MHz, CDCl3) δ=9.69 (t, J=2.4Hz, 1H), 7.13-7.09 (m, 2H), 6.92-6.87 (m, 2H), 3.78 (s, 3H), 3.60 (d, J=2.4Hz, 2H)ppm. 13C NMR (75MHz, CDCl3) δ=199.51, 158.82, 130.53, 123.61, 114.29, 55.09, 49.50ppm. |
84% | With pivaloyl chloride; dimethyl sulfoxide; triethylamine In dichloromethane at -78 - 20℃; for 1h; | |
82.4% | With 2-iodoxybenzoic acid In acetonitrile at 80℃; for 2h; Inert atmosphere; | |
79% | Stage #1: 2-(4-Methoxyphenyl)ethanol With bis(trichloromethyl) carbonate; dimethyl sulfoxide In dichloromethane at -78℃; for 0.25h; Stage #2: With triethylamine at -78 - 20℃; for 0.166667h; | |
75% | With pyridinium chlorochromate In dichloromethane at 0 - 20℃; for 4h; | |
75% | With pyridinium chlorochromate In dichloromethane at 20℃; for 4h; cooling; | |
75% | With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile for 3h; Reflux; | Oxidation of 4-methoxyphenylethanol with 2-iodoxybenzoic acid (IBX) 4-Methoxyphenylethanol (0.34 g, 2.24 mmol) was dissolved in acetonitrile (50 mL), then IBX (3.72 g, 6mmol) was added and the solution was refluxed for 3 h. The mixture was cooled to r.t, filtered (Celite) andthe filtrate was evaporated. The residue was purified by column chromatography (10:1 n-pentane/ethylacetate) to give pure 4-methoxyphenylacetaldehyde (0.25 g, 75% yield), identical (H-NMR, ES-MS) to anauthentic sample. |
66% | With pyridine-SO3 complex; triethylamine In dichloromethane; dimethyl sulfoxide for 8h; | 126.1 Example 126 . l-{6-[4-(2-dimethylamino-ethoxy)-phenyl] -5-ethyl-2-thiophen-2-yl-thieno[2,3-d]pyrimidin-4-ylamino}-3-inethyl-pyrrole-2,5-d ione hydrochloride; Step 1. Preparation of (4-methoxy-phenylVacetaldehyde; 4-methoxyphenethylalcohol (2g, 13.14mmol) and triethylamine (7.33ml,52.56mmol) were dissolved in dichloromethane (50ml). Therein, the solution of pyridine sulfide complex (4.18g, 26.28mmol) in dimethylsulfoxide (10ml) was added, and the reaction mixture was stirred for 8 hours. The solvent was removed under reduced pressure. The residue was purified by column chromatography (n-hexane: ethyl acetate = 3:1) to give 1.29g (yield: 66.0%, yellow oil) of the target compound.[1218] 1H-NMR (400D, CDCI) δ 10.03(t, IH, J=2.0Hz), 7.12(d, 2H, J=8.4Hz), 6.86(d, 2H,J=6.4Hz), 3.79(s, 3H), 3.62(d, 2H, J=2.0Hz) |
57% | With Dess-Martin periodane In dichloromethane at 20℃; for 1.5h; | |
55% | With Dess-Martin periodane In dichloromethane at 20℃; for 18h; | |
53% | With sulphur trioxide pyridine complex; N-ethyl-N,N-diisopropylamine In dichloromethane; dimethyl sulfoxide at -15℃; for 0.5h; Inert atmosphere; | |
50% | With mesoporous silica; pyridinium chlorochromate In dichloromethane at 20℃; for 2h; | |
49% | With Dess-Martin periodane In dichloromethane at 0 - 25℃; for 4h; | |
44.4% | Stage #1: 2-(4-Methoxyphenyl)ethanol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -70℃; for 0.333333h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at -70 - 20℃; for 1h; | 20.A [0334] Step A: DMSO (5.2 mL, 72.6 mmol) in dichloromethane (14.5 mL) was added to a solution of oxalyl chloride (3.1 mL, 36.3 mmol) in dichloromethane (83 mL) at -70 °C under nitrogen. After stirring for 5 minutes, 2-(4-methoxyphenyl) ethanol (5.0 g, 33.0 mmol) dissolved in dichloromethane (33 mL) was added drop wise (20 min). Stirring was continued for an additional 20 min. and triethyl amine (9.7mL, 69.3 mmol) was added, and the reaction mixture was stirred and warmed slowly to room temperature for 1 hour. The reaction mixture was diluted with water. The organic layer was separated, dried over sodium sulfate, filtered and concentrated in vacuo to provide 2-(4- methoxyphenyl)acetaldehyde (553) (2.2 g, 44.4%) as an oil residue. |
44.4% | Stage #1: 2-(4-Methoxyphenyl)ethanol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -70℃; for 0.666667h; Stage #2: With triethylamine In dichloromethane at -70 - 20℃; for 1h; | 20.A 0326] Step A: DMSO (5.2 niL, 72.6 mmol) in dichloromethane (14.5 niL) was added to a solution of oxalyl chloride (3.1 rnL, 36.3 mmol) in dichloromethane (83 mL) at -70 0C under nitrogen. After stirring for 5 minutes, 2-(4-methoxyphenyl) ethanol (5.0 g, 33.0 mmol) dissolved in dichloromethane (33 mL) was added drop wise (20 min). Stirring was continued for an additional 20 min. and triethyl amine (9.7mL, 69.3 mmol) was added, and the reaction mixture was stirred and warmed slowly to room temperature for 1 hour. The reaction mixture was diluted with water. The organic layer was separated, dried over sodium sulfate, filtered and concentrated in vacuo to provide 2-(4- methoxyphenyl)acetaldehyde (553) (2.2 g, 44.4%) as an oil residue. |
37% | With N-chloro-succinimide; N-tert-butylbenzenesulfinamide; potassium carbonate In dichloromethane at 0℃; for 2h; Schlenk technique; Molecular sieve; Inert atmosphere; | |
34% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | 91.1 A solution of 4-methoxyphenyl ethanol (15.0 g, 98.2 mmol) in 150 mL of methylene chloride was stirred at 0° C. while Dess-Martin periodinane (50 g, 1.2 eq.) was added in small portions. The ice-bath was removed and the reaction was stirred at rt for 1 h. The reaction mixture was then diluted with methylene chloride (100 mL), washed with 10% sodium thiosulfate, saturated NaHCO3 solution, water, saturated NaCl solution, and dried over Na2SO4. The product was purified using silica gel chromatography (100% hexanes to 20% EtOAC/hexanes) to afford 5.3 g (34%) of 4-methoxyphenyl acetaldehyde. A suspension of glyoxalic acid hydrate (2.45 g, 26.6 mmol) and morpholine hydrochloride (3.28 g, 26.35 mmol) in dioxane (25 mL) was stirred as water (2 mL) was added. The homogeneous solution and 4-methoxyphenyl acetaldehyde (3.8 g, 25.3 mmol) was then added and the solution was stirred at reflux for 24 h. The solvent was evaporated and a solid was formed after addition of 20 mL of water. The solid was collected and washed with water to give 5.1 g (98%) of the product: MS m/z 189 (M-17+H). |
34% | With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; | |
29% | With 1H-imidazole; [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 1h; | |
With chromium trioxide-pyridine complex In dichloromethane | ||
With bis(trichloromethyl) carbonate In dimethyl sulfoxide | ||
With Annogen In hydrogenchloride at 35℃; ΔH(excit.), ΔE(excit.), ΔS(excit.), ΔG(excit.).; | ||
With Annogen In hydrogenchloride at 29.9 - 44.9℃; for 24h; effect of the temperature; | ||
With hydrogenchloride; chloramine-T at 29.9 - 44.9℃; for 24h; activation parameters: ΔH(excit.), ΔS(excit.), ΔG(excit.), and Ea; | ||
With hydrogenchloride; N-bromo-p-toluenesulfonamide; anhydrous sodium perchlorate In methanol; lithium hydroxide monohydrate at 35℃; | ||
With hydrogenchloride; chloramine-T In lithium hydroxide monohydrate at 34.85℃; | ||
With N-tert-butylbenzenesulfinimidoyl chloride; zinc oxide In dichloromethane at 0℃; for 0.5h; | ||
With oxalyl dichloride; dimethyl sulfoxide; triethylamine In dichloromethane cooling; | ||
With Collins reagent In dichloromethane at 25℃; | ||
With pyridinium chlorochromate In dichloromethane for 3h; cooling; | ||
With Dess-Martin periodane In dichloromethane at 20℃; | ||
With Collins reagent In dichloromethane at 25℃; | ||
With Sodium hydrogenocarbonate; Dess-Martin periodane In dichloromethane at 20℃; for 1h; | (4-Methoxy-phenyl)-acetaldehyde; Dess-Martin periodinane (3.2 g, 7.29 mmol, 1.1 equiv) is added in one portion to a mixture of 4-methoxyphenethyl alcohol (1.0 g, 6.63 mmol) and NaHC03 (1. 1 g, 13.2 mmol, 2.0 equiv) in CH2CI2, under an argon atmosphere. The resulting mixture is stirred for 1 h at RT and directly loaded on a silica gel (60 g) column. Flash chromatography purification (CH2CI2/Et2O, 95/5), affords the title compound as a colorless oil : ES-MS: 148.9 [M-H]- ; single peak at tR= 6.12 min (System 1); Rf = 0.74 (CH2CI2/Et2O, 95/5) | |
With Dess-Martin periodane In dichloromethane at 20℃; Inert atmosphere; | General procedure for the synthesis of aromatic and aliphatic acetaldehydes: General procedure: The alcohol (1.0 eq) was added to a suspension of Dess-Martin periodinane (1.2 eq) in CH2Cl2(100 mM) under an argon atmosphere at room temperature. The mixture was allowed to stir for0.5 - 20 hours, while consumption of starting material was monitored by TLC. After the reactionwas complete, 1M Na2S2O3 (equal volume to CH2Cl2) was added. After stirring for 15 minutes,the phases were separated and the aqueous phase was extracted with CH2Cl2 twice. Thecombined organic layers were washed with 5% NaHCO3 and brine, and dried over Na2SO4. Thesolvent was evaporated under reduced pressure and the residue was purified by columnchromatography to afford analytically pure aldehydes.b) alcohol precursors for aldehydes 13, 14, 20 (solid alcohols)The alcohol (1.0 eq) was dissolved in CH2Cl2 (200 mM) and the solution was added to asuspension of Dess-Martin periodinane (1.2 eq) in CH2Cl2 (200 mM) under an argon atmosphereat room temperature. The mixture was allowed to stir for 0.5 - 20 hours (TLC monitoring). Then,Et2O (equal volume to CH2Cl2), 1M Na2S2O3 and saturated NaHCO3 (both equal volume toCH2Cl2) were added. After stirring for 15 minutes, the phases were separated and the aqueousphase was extracted with Et2O twice. The combined organic layers were washed with sat.NaHCO3 and brine, and dried over Na2SO4. The solvent was evaporated under reduced pressureand the residue was purified by column chromatography to afford analytically pure aldehydes. | |
With pyridinium chlorochromate In dichloromethane | ||
185 mg | With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In ethyl acetate at 80℃; for 3h; | 41.A A. To a solution of 4-methoxyphenethyl alcohol (184 mg, 1.21 mmol) in EtOAc (24 mL) was added 2-iodoxybenzoic acid (1 .02 g, 3.64 mmol), and the mixture was heated to 80°C open to air for 3 h. The mixture was cooled to 0°C for 10 mm then filtered through Celite and concentrated to give Compound No. 80 (185 mg) as ayellow oil. |
With Dess-Martin periodane In dichloromethane at 0℃; for 0.25h; | ||
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 80℃; Inert atmosphere; | ||
708 mg | With Dess-Martin periodane In dichloromethane at 0 - 20℃; Inert atmosphere; | |
With Sodium hydrogenocarbonate; Dess-Martin periodane In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere; | ||
With Sodium hydrogenocarbonate In dichloromethane at 20℃; for 3h; Dean-Stark; Inert atmosphere; | ||
With Dess-Martin periodane | ||
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 80℃; for 2.5h; Inert atmosphere; | ||
With Dess-Martin periodane In dichloromethane for 1h; | ||
With Sodium hydrogenocarbonate; Dess-Martin periodane In dichloromethane at 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With SO3H silica gel; In methanol; at 50℃; for 2h;Inert atmosphere; | General procedure: Deprotection using SO3H silica gel was conducted according to our previous reports.[19,20] A solution of substrates with protective groups (0.4 mmol) in the indicated solvent (1 mL) was treated with SO3H silica gel (2 g, 0.2 mmol/g). After shaking for 1 min, resulting powder was left to stand at the indicated temperature. Then, the powder was put on the pad of Celite and eluted with MeOH (30 mL). The obtained eluate was concentrated under reduced pressure to yield the products. No purification process was required when compounds 1b, 1c, 3a, 10a-c and 14 were used as starting materials. In the case of compound 12, although 0.1 mmol/g of SO3H silica gel was used, silyl residues were not completely trapped by silica gel and purification process was required. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With manganese(IV) oxide; In tetrahydrofuran; at 20℃; | 4-Methoxyphenylethanol (0.15 g, 1.0 mmol) was dissolved in dry THF (30 mL), manganese dioxide (1.76g, 30 mmol) was added and the mixture was stirred at r.t overnight, then filtered (Celite) and the filtratewas concentrated. The residue was purified by column chromatography, fractions containing the major product were pooled and concentrated to give material (0.115 g, 77% yield), which, on LC-MS analysis showed a major UV peak with m/z = 137.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-Methoxystyrene; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; (R,R(Fc))-1-diphenylphosphino-2-(1-dicyclohexylphosphinoethyl)ferrocene In 1,2-dichloro-ethane for 24h; Stage #2: With sodium hydroxide; dihydrogen peroxide In diethyl ether at 0 - 20℃; for 2h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With PPh3-polystyrene; diethylazodicarboxylate In tetrahydrofuran at 20℃; | ||
With PPh3-polystyrene; diethylazodicarboxylate In tetrahydrofuran at 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.4% | With triethylamine; In dichloromethane; at 20℃; | Methoxybenzyl alcohol (64.1g, 420mmol), dichloromethane (530 ml), triethylamine (85.2g, 840mmol) and methanesulfonyl chloride (57.9g, 505mmol) added to the reaction flask and the reaction was stirred at room temperature, the reaction was complete pH was adjusted to neutral, extracted, washed, separated, the organic phase was concentrated under reduced pressure to give a pale yellow oil of 2- (4-methoxy - phenyl) - ethanol methanesulfonate (90.6 g), yield 93.4% . |
With N-ethyl-N,N-diisopropylamine; In dichloromethane; for 1h; | Example 13; (R, S)-8-Benzyloxy-l-methyl-2, 3,4, 5-tetrahydro-1H-benzo [d] azepine; 1-2- (4-Methoxy-phenyl)-ethylamizo] propan-2-ol; To a solution of 4-methoxyphenethyl alcohol (6.6 mmol, 1.0 g) in dichloromethane (50 mL) was added diisopropylethyl amine (19.7 mmol, 3.43 mL) and mesylchloride (13.2 mmol, 1.02 mL). This was stirred for 1 h, diluted with dichloromethane (100 mL) and partitioned with water (75 mL). The organics were washed with saturated NaHCO3 (50 mL) and brine (50 mL), dried with Na2S04, filtered and concentrated. The crude material was treated with neat l-amino-2-propanol (5 mL) and heated for 3 h. This was diluted with water (50 mL) and extracted with EtOAc (2 x 75 mL). The combined organics were washed with brine (50 mL), dried with Na2S04, filtered and concentrated. The crude amine was dissolved in dichloromethane (20 ml) and 2.0 M HCl in ether (5 ml) added to form a white precipitate which was collected by filtration. The white solid was partitioned between EtOAc (100 ml) and saturated NaHCO3 (50 mL). The organics were dried with Na2SO4, filtered and concentrated to furnish 900 mg of 1- [2- (4-Methoxy-phenyl)-ethylamino]-propan-2-ol.'H NMR (HC1 salt) (400 MHz, DMSO) 8 9.20 (br. s, 1 H), 8.87 (br. s, 1 H), 7.17 (d, J = 9 Hz, 1 H), 6.89 (d, J = 9 Hz, 1 H), 4.03-3. 99 (m, 1 H), 3.73 (s, 3 H), 3.10-2. 91 (m, 5 H), 2.80-2. 76 (m, 1 H), 1.12 (d, J = 6 Hz, 3 H). | |
With triethylamine; In dichloromethane; at 20℃; | To a solution of 4-methoxyphenethyl alcohol (2.50 g, 16.4 mmol) in DCM (20.0 mL) is added Et3N (2.75 mL, 19.7 mmol) followed by methanesulfonyl chloride (1.53 mL, 19.7 mmol). The mixture is stirred at room temperature overnight then extracted with DCM, washed with brine, dried over MgSO4, and concentrated under reduced pressure to provide 17-1 (3.75). The material is carried without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; ethyl acetate; | 4-Chloro-3-[2-(4-methoxy-phenyl)-ethoxy]-benzoic acid methyl ester g (5.36 mmol) of <strong>[166272-81-7]4-Chloro-3-hydroxy-benzoic acid methyl ester</strong> was dissolved in 40 ml of anhydrous tetrahydrofuran. To this solution was added 0.897 g (5.9 mmol) of 2-(4-Methoxy-phenyl)-ethanol, 5.35 g (equivalent to 16.1 mmol PPh3) of triphenylphosphine derivatized polystyrene and 2.80 g (16.1 mmol) of DEAD. The solution was shaken for 16 h at RT. The polymer was filtered off and washed with ethyl acetate. The solvent was removed under reduced pressure. The residue was taken-up in ethyl acetate and the solution was washed three times with water and twice with saturated aqueous sodium chloride. The organic phase was dried with magnesium sulphate, filtered and the solvent was removed under reduced pressure. The residue was chromatographed on silica gel eluding with ethyl acetate/n-heptane (1/5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 1 Preparation of 2-(4-methoxyphenyl)ethyl chloride 11 g (0.11 mole) of phosgene were added to 4.4 g (0.02 mole) of tri-n-butylphosphine oxide during the course of 15 minutes at a temperature of 80 C. The temperature was then held at 90-100 C. while 108 g (1.09 moles) of phosgene and 152 g (1.00 mole) of 2-(4-methoxyphenyl)ethanol were added over 1 hour. To complete the reaction, the mixture was kept at this temperature for another hour. Excess phosgene was then removed from the product by bubbling nitrogen through the mixture for from 2 to 3 hours at a temperature of 90 C. Subsequent distillation at 127-130 C./20 mbar gave the 2-(4-methoxyphenyl)ethyl chloride in a yield of from 95 to 99% and a purity of 99.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-Methoxystyrene; benzo[1,3,2]dioxaborole With (-)-Diop; (2R,3R,5R,6R)-5,6-bis((diphenylphosphanyl)methyl)-2,3-dimethoxy-2,3-dimethyl<1,4>dioxane In tetrahydrofuran at 20℃; for 4h; Stage #2: With sodium hydroxide; dihydrogen peroxide In tetrahydrofuran; water optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With water; sodium hydroxide; In tetrahydrofuran; at 25℃; for 24h; | 4-Methoxyphenethyl methyl carbonate 9 (0.5 mmol, 105 mg) was solubilised in THF (10 ml), then a 1 N solution of NaOH (2 ml) was added. The mixture was stirred at room temperature and monitored by thin layer chromatography. After 24 h, the solvent was evaporated under vacuum. The residue was neutralised with a 1 N solution of HCl and the aqueous phase was extracted with ethyl acetate (3 × 10 ml). The organic phases were washed with a saturated solution of NaCl (10 ml) and dried over Na2SO4. Following evaporation of the solvent, 2-(4-methoxyphenyl)ethanol 10 was isolated in quantitative yield (0.5 mmol, 76 mg). 1H NMR (CDCl3, 200 MHz): delta 2.79 (t, 2H, J = 6.5 Hz, CH2), 3.77 (s, 3H, OCH3), 3.80 (t, 2H, J = 6.6 Hz, CH2), 6.84 (d, 2H, J = 8.7 Hz, Ph), 7.13 (d, 2H, J = 8.6 Hz, Ph). 13C NMR (CDCl3, 50 MHz): delta 38.3, 55.3, 63.8, 114.0, 129.8, 129.9, 130.4, 158.3. HR-MS m/z: 152.1904 (M+). Anal. Calcd. for C9H12O2: C, 71.03; H, 7.95; O, 21.03. Found: C, 70.89; H, 8.01; O, 21.10. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: triphenylphosphine; carbon tetrabromide / dichloromethane / 0 - 20 °C / Inert atmosphere 2.1: sodium; ethanol / 0.5 h / 0 °C 2.2: 15 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / tetrahydrofuran; water / 15 h / Reflux 4.1: sodium hydroxide; Aspergillus acylase I / aq. phosphate buffer / 37 °C / pH 8 / Enzymatic reaction 5.1: hydrogen iodide / 15 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With ytterbium(III) triflate In nitromethane at 120℃; | Esterification of caffeic acid General procedure: To a mixture of caffeic acid fine powder (1.0 g, 5.56 mmol), various phenethyl alcohols (5.56 mmol) in CH3NO2 (125 mL) was added Yb(OTf)3 (34.4 mg, 0.056 mmol). After 5 min of ultrasonic shake, the mixture was stirred on a 120 °C oil bath for 40-120 min. The reaction mixture was cooled to room temperature, washed with 2% NaHCO3 (30 mL) and brine, dried over anhydrous Na2SO4, and concentrated to give crude products, which were purified by column chromatography to give the compounds 1-26 in 18-61% yields. |
With Escherichia coli strain B-CP1 at 30℃; for 24h; Microbiological reaction; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium hexamethylsilazane; 1,3-bis(mesityl)imidazolium chloride; In toluene; at 45℃; for 16h;Inert atmosphere; Molecular sieve; Sealed tube; | General procedure: To a flame-dried flask containing a stirrer bar and activated 5 A molecular sieves was added IMes·HCl (A1·HCl, 6.8 mg, 0.02 mmol) and toluene (2 mL) under an inert atmosphere. To this stirred suspension 0.5 M KHMDS in toluene (0.04 mL) was added and the mixture stirred for 15 min. An appropriate alcohol (1 mmol) and methyl formate (600mg, 10 mmol) were then added as a solution in toluene (2 mL) and the flask sealed and heated to 45 C for 16 h. The crude mixture was loaded directly on to a chromatography column (silica gel) to give the formates. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With beta-galactosidase from Bacillus megaterium YZ08; magnesium chloride; In aq. phosphate buffer; dimethyl sulfoxide; at 35℃; for 12h;pH 7.4;Enzymatic reaction; | General procedure: The reaction mixture (70 mL Na2PO4/KH2PO4 buffer (50 mM, pH 7.4) + 30 mL DMSO) containing MgCl2 (5 mM), <strong>[63-42-3]lactose</strong> (50 mmol), aromatic alcohols (30-40 mmol), crude enzyme solution (100 U) was prepared in a 250 mL Erlenmeyer flask. The reaction was conducted at 35 C with shaking at 200 rpm for 12 h. AB-8 macroporous resin column and flash column chromatography were used to purify the products. The procedure is detailed in supplementary material. The product structure was determined by NMR (Bruker AV-400 spectrometer, Switzerland). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.6% | With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 20℃; for 27h;Inert atmosphere; | To a solution of 4-methoxyphenethyl alcohol (1.03 g, 6.77 mmol) in dichloromethane (20 mL) were added N,N-diisopropylethylamine (2.3 mL, 14 mmol) and chloromethyl methyl ether (0.82 mL, 11 mmol) at 0 C. The reaction mixture was stirred for 27 h at ambient temperature. The reaction mixture was then concentrated under reduced pressure. Column chromatography (silica gel, 34 g; n-hexane/ethyl acetate, 8:1) gave the title compound (1.19 g, 6.07 mmol, 89.6%) as a pale yellow oil. 1 H NMR (400 MHz, CDCl 3 ): delta 2.85 (t, J = 7.0 Hz, 2H), 3.30 (s, 3H), 3.72 (t, J = 7.0 Hz, 2H), 3.78 (s, 3H), 4.61 (s, 2H), 6.80-6.87 (m, 2H), 7.12-7.19 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ): delta 35.5, 55.3, 55.4, 68.8, 96.5, 113.9, 129.9, 131.1, 158.2. HR-MS (EI): Calcd for C 11 H 16 O 3 [M] + : 196.1099. Found: 196.1093. IR (neat, cm -1 ): 2936, 2836, 1613, 1514, 1247. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium hydride In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; | 4.2.1. General procedure for the preparation of ω-bromoalkylderivatives 10-27 General procedure: To a solution of the phenethyl alcohol (1.82 mmol for 1, 4;0.66 mmol for 2, 3, 5, 6, 1.0 equiv.) in anhydrous DMF (8.0 mL for 1,4; 5.0 mL for 2, 3, 5, 6) were added 95% NaH (8.0 equiv. for 1-4; 6.0equiv. for 5, 6), followed by the corresponding α,ω-dibromoalkane(6.0 equiv. for 1-4; 8.0 equiv. for 5, 6). The mixturewas kept stirringat rt and inert atmosphere for 10 h. Then, it was concentrated todryness under reduced pressure and the residue was subjected to1:1 CH2Cl2-H2O partitioning (30 mL); aqueous layer was furtherextracted with CH2Cl2 (2x15 mL). Combined organic fractions weredried over Na2SO4, filtered and the filtrate was concentrated todryness. The residue was purified by column chromatography, usingthe eluant indicated in each case, to afford derivatives 10-27. |
73% | With sodium hydride In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; | 4.2.1. General procedure for the preparation of ω-bromoalkylderivatives 10-27 General procedure: To a solution of the phenethyl alcohol (1.82 mmol for 1, 4;0.66 mmol for 2, 3, 5, 6, 1.0 equiv.) in anhydrous DMF (8.0 mL for 1,4; 5.0 mL for 2, 3, 5, 6) were added 95% NaH (8.0 equiv. for 1-4; 6.0equiv. for 5, 6), followed by the corresponding α,ω-dibromoalkane(6.0 equiv. for 1-4; 8.0 equiv. for 5, 6). The mixturewas kept stirringat rt and inert atmosphere for 10 h. Then, it was concentrated todryness under reduced pressure and the residue was subjected to1:1 CH2Cl2-H2O partitioning (30 mL); aqueous layer was furtherextracted with CH2Cl2 (2x15 mL). Combined organic fractions weredried over Na2SO4, filtered and the filtrate was concentrated todryness. The residue was purified by column chromatography, usingthe eluant indicated in each case, to afford derivatives 10-27. |
57% | With sodium hydride In dimethyl sulfoxide at 20℃; for 5h; Inert atmosphere; | 4.2.19. 1-{2’-[(5''-Bromopentyl)oxy]ethyl}-4-methoxybenzene (38) To a solution of 2-(4-methoxyphenyl)ethanol (104.0 mg,0.67 mmol) in anhydrous DMSO (4 mL) were added NaH (103.3 mg,4.09 mmol, 6.1 equiv.) and 1.5-dibromopentane (753 mL, 5.36 mmol,8.0 equiv.). The corresponding mixture was stirred at rt and underAr for 5 h. After that, the solvent was removed in vacuo, and theresidue was partitioned between 1:1 CH2Cl2-H2O (30 mL); theaqueous phase was extracted further with CH2Cl2 (2 x15 mL). Thecombined organic fractions were dried over anhydrous Na2SO4,filtrated and concentrated to dryness. The residue was purified bycolumn chromatography (cyclohexane / 1:15 Et2O-cyclohexane1:15). Yield: 114.8 mg, 57%; Rf 0.26 (1:15 Et2O-cyclohexane). 1HNMR (300 MHz, CDCl3) δ 7.14 (m, 2H, H-2, H-6), 6.83 (m, 2H, H-3, H-5), 3.79 (s, 3H, OMe), 3.59 (t, 2H, JH,H 7.0 Hz, CH2), 3.44 (t, 2H,JH,H 7.0 Hz, CH2), 3.39 (t, 2H, JH,H 7.0 Hz, CH2), 2.82 (t, 2H,JH,H 7.0 Hz, CH2), 1.86 (quint., 2H, CH2) 1.54 (m, 4H, 2CH2) ppm;13C NMR (75.5 MHz, CDCl3) δ 158.2 (C-4), 131.2 (C-1), 129.9 (C-2, C-6), 113.9 (C-3, C-5, 72.2 (Ar-CH2-CH2O), 70.7 (CH2-O2-H2), 55.4(OMe), 35.6, 33.9, 32.7, 29.0, 25.1 (CH2) ppm; HRESI-MS calcd. forC14H2179BrNaO2 ([M+Na]+): 323.0617, found: 323.0617; calcd. forC14H2181BrNaO2 ([M+Na]+): 325.0597, found 325.0595. |
Stage #1: 2-(4-Methoxyphenyl)ethanol With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: 1,5-dibromo-pentane In N,N-dimethyl-formamide at 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With dmap; In tetrahydrofuran; at 20℃;Inert atmosphere; | General procedure: To an oven-dried 20 mL vial equipped with a stir bar was added 2-trichloroacetyl-N-methylimidazole (5.0 mmol), DMAP (0.5 mmol), and the corresponding alcohol (10.0 mmol). The mixture was dissolved in THF (10 mL), then stirred overnight at room temperature. The unpurified reaction was concentrated and purified by column chromatography (ethyl acetate/hexanes) to afford imidazole ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 20 °C 2: sodium carbonate; potassium iodide / N,N-dimethyl-formamide / 1 h / 80 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75 %Spectr. | With C28H32IrN4(1+)*I(1-); sodium t-butanolate In tert-Amyl alcohol at 140℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium hydride In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; | 4.2.1. General procedure for the preparation of ω-bromoalkylderivatives 10-27 General procedure: To a solution of the phenethyl alcohol (1.82 mmol for 1, 4;0.66 mmol for 2, 3, 5, 6, 1.0 equiv.) in anhydrous DMF (8.0 mL for 1,4; 5.0 mL for 2, 3, 5, 6) were added 95% NaH (8.0 equiv. for 1-4; 6.0equiv. for 5, 6), followed by the corresponding α,ω-dibromoalkane(6.0 equiv. for 1-4; 8.0 equiv. for 5, 6). The mixturewas kept stirringat rt and inert atmosphere for 10 h. Then, it was concentrated todryness under reduced pressure and the residue was subjected to1:1 CH2Cl2-H2O partitioning (30 mL); aqueous layer was furtherextracted with CH2Cl2 (2x15 mL). Combined organic fractions weredried over Na2SO4, filtered and the filtrate was concentrated todryness. The residue was purified by column chromatography, usingthe eluant indicated in each case, to afford derivatives 10-27. |
83% | With sodium hydride In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; | 4.2.1. General procedure for the preparation of ω-bromoalkylderivatives 10-27 General procedure: To a solution of the phenethyl alcohol (1.82 mmol for 1, 4;0.66 mmol for 2, 3, 5, 6, 1.0 equiv.) in anhydrous DMF (8.0 mL for 1,4; 5.0 mL for 2, 3, 5, 6) were added 95% NaH (8.0 equiv. for 1-4; 6.0equiv. for 5, 6), followed by the corresponding α,ω-dibromoalkane(6.0 equiv. for 1-4; 8.0 equiv. for 5, 6). The mixturewas kept stirringat rt and inert atmosphere for 10 h. Then, it was concentrated todryness under reduced pressure and the residue was subjected to1:1 CH2Cl2-H2O partitioning (30 mL); aqueous layer was furtherextracted with CH2Cl2 (2x15 mL). Combined organic fractions weredried over Na2SO4, filtered and the filtrate was concentrated todryness. The residue was purified by column chromatography, usingthe eluant indicated in each case, to afford derivatives 10-27. |
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
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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