| 100% |
With 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate; HNO3 In acetonitrile at 20℃; for 2h; |
4.5 General procedure for the catalytic oxidation on a 1.0mmol scale
A mixture of nitrosotetrazolium salt (1, 17.0mg, 0.0500mmol), concentrated HNO3 (76.1μL, 1.00mmol), and alcohols 3a or 3g (1.00mmol) was stirred in MeCN (10.0mL) at room temperature for 1.0-1.5h. The solvent was evaporated under reduced pressure and the residue was passed through a SiO2 column (eluting with CH2Cl2) to give the corresponding ketones 4a or 4g. |
| 100% |
With 1,3-Dichloro-5,5-dimethyl-2,4-imidazolidinedione In acetonitrile at 50℃; for 0.5h; Sonication; |
|
| 99% |
With sodium chlorine monoxide; nickel (II) chloride In dichloromethane; lithium hydroxide monohydrate at 0 - 20℃; for 4h; |
|
| 99% |
With oxygen In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 120℃; for 1h; Flow reactor; Green chemistry; |
|
| 99% |
With 5,10,15,20-tetraphenyl-21H,23H-porphine manganese(III) chloride; oxygen; cis-cyclohexene at 60℃; for 1.5h; |
|
| 99% |
With cerium(III) bromide; dihydrogen peroxide In 1,4-dioxane; lithium hydroxide monohydrate at 20℃; |
|
| 98% |
With sodium chlorine monoxide; 2-azaadamantane N-oxyl; tetrabutylammonium bromide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.333333h; Inert atmosphere; |
|
| 98% |
With sodium chlorine monoxide; 2-azaadamantane N-oxyl; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.333333h; Inert atmosphere; |
|
| 98% |
With 1-methyl-1H-imidazole; tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate; 4,4'-Dimethoxy-2,2'-bipyridin; 9-azabicyclo[3.3.1]nonane N-oxyl; oxygen In acetonitrile at 20℃; for 1h; |
|
| 98% |
With 9-azabicyclo<3.3.1>nonane-N-oxyl; oxygen; glacial acetic acid; NaNO2 at 20℃; for 3h; |
|
| 98% |
With 4-iodyl-9-phenylacridine In chlorobenzene at 20℃; for 20h; Irradiation; |
|
| 97% |
With Dess-Martin periodane In dichloromethane for 0.333333h; |
|
| 97% |
With dihydrogen peroxide In lithium hydroxide monohydrate; propan-2-one at 56℃; for 2h; chemoselective reaction; |
|
| 97% |
With sodium chlorine monoxide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane at 0℃; for 1h; chemoselective reaction; |
|
| 97% |
With trifluorormethanesulfonic acid; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In 1,4-dioxane at 20℃; for 0.25h; |
General Procedure for the IBX-TfOH mediated oxidation of alcohols
General procedure: To the suspension of IBX (1.1 equiv., or 1.1 mmol) and TfOH (2-5 mol %, or 0.02-0.05 mmol) in 3 mL 1,4-dioxane, alcohol (1.0 equiv., 1.0 mmol in 2 mL 1,4-dioxane) was added at room temperature, and the reaction mixture was vigorously stirred till the complete consumption of alcohol, as indicated by TLC. The solvent was evaporated under reduced pressure, and the resulting residue was diluted with 10 mL of dichloromethane. The heterogeneous mixture was stirred for 5 minutes and filtered. The residue was washed with dichloromethane (3×3 mL) and the filtrate was evaporated to dryness to obtain the desired product in sufficiently pure form. |
| 97% |
With sodium chlorine monoxide; tetrabutylammonium bromide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.333333h; Schlenk technique; |
|
| 96% |
With dihydrogen peroxide; bromine In dichloromethane; lithium hydroxide monohydrate at 20℃; for 2h; |
|
| 96% |
With 12-molybdophosphoric acid; oxygen; tetra-n-butylammonium acetate; palladium diacetate In ethyl acetate at 100℃; for 1h; |
|
| 96% |
With 4-dimethylaminopyridine; [2,2]bipyridinyl; 2-azaadamantane N-oxyl; copper(I) trifluoromethanesulfonate benzene complex In acetonitrile at 20℃; for 13h; |
|
| 96% |
With 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate; oxygen; HNO3 In acetonitrile at 20℃; for 7.5h; |
|
| 95% |
With potassium bromate; perchloric acid; mercury (II) acetate In glacial acetic acid at 45℃; further temperature, further objects of study: energy of activation, ΔH(activ.), ΔS(activ.); |
|
| 95% |
With iron (ΙΙΙ) nitrate nonahydrate; 9-azabicyclo<3.3.1>nonane-N-oxyl In acetonitrile at 20℃; for 6h; |
|
| 95% |
With 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxoammonium nitrate; mesoporous silica In dichloromethane at 20℃; for 1h; |
GENERAL PROCEDURE FOR ALCOHOL OXIDATION
General procedure: Alcohol (7, 2 mmol, 1 eq.), silica gel (1 wt. equiv. to 7), and CH2Cl2 (50 mL, 0.04 M in 7) were added to a round-bottom flask equipped with a magnetic stir bar and the mixture stirred at r.t. for 5 min before adding 5 (0.275 g, 1 mmol, 0.5 eq.). The reaction mixture was stirred at r.t. until the oxidation was deemed complete by 1H-NMR spectroscopy monitoring. Upon completion, the product mixture was filtered through a pad of silica, the silica washed with dichloromethane to elute any remaining product. The solvent was then removed from the filtrate under vacuum, affording the pure product. |
| 94% |
With benzotrifluoride; oxygen at 60℃; for 2h; atmospheric pressure; |
|
| 94% |
With aluminium(III) chloride; 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate In acetonitrile for 5h; Heating; |
|
| 94% |
With sodium chlorine monoxide; 1-methyl-2-azaadamantane N-oxyl; tetrabutylammonium bromide In dichloromethane; Sodium hydrogenocarbonate at 0℃; for 0.333333h; |
|
| 94% |
With 1-decyl-4-aza-1-azoniabicyclo[2.2.2]octane chlorochromate at 20℃; for 0.25h; |
|
| 94% |
With 1‐methyl‐2‐azaadamantane‐N‐oxyl; sodium chlorine monoxide; tetrabutylammonium bromide; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.333333h; |
|
| 94% |
With tert.-butylnitrite; oxygen; glacial acetic acid In toluene at 50℃; for 5h; |
|
| 93% |
With L-alanine; mesoporous silica; chloro-hydroxy-dioxo-chromium In dichloromethane at 20℃; for 3.5h; |
|
| 92% |
With 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; orthoperiodic acid In dichloromethane at 20℃; for 0.5h; |
|
| 92% |
With NaBrO3; Nafion-Cr(III); Nafion-H In lithium hydroxide monohydrate; acetonitrile for 2h; Heating; |
|
| 92% |
With NBS; β‐cyclodextrin In methanol; lithium hydroxide monohydrate; propan-2-one at 20℃; for 12h; |
|
| 92% |
With 9-azanoradamantane-N-oxyl; glacial acetic acid; NaNO2 at 20℃; for 22h; air; |
|
| 92% |
With sodium hydrogen sulphate monohydrate; iodic acid In lithium hydroxide monohydrate; acetonitrile for 4h; Reflux; |
|
| 92% |
With 9-azanoradamantane N-oxyl; oxygen; glacial acetic acid; NaNO2 In acetonitrile at 20℃; for 22h; |
6.l Example 6: Oxidation of alcohols using air as bulk oxidant; (1) Oxidation of 2-adamantanol
A solution of 2-adamantanol (101.1 mg, 0.664 mmol) and Nor-AZADO (0.92 mg, 6.64 µmol) in acetic acid (2.0 ml) was added with sodium nitrite (9.2 mg, 0.133 mmol), and the mixture was stirred at room temperature for 22 hours under an air atmosphere. The reaction mixture was added with saturated aqueous sodium carbonate (10 ml), and the mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the objective compound (91.8 mg; yield, 92.0%).1H-NMR (400 MHz, CDCl3): δ 2.55 (s,2H), 2.10-1.94 (m, 12H).13C-NMR (100 MHz, CDCl3): δ 218.4, 47.0, 39.2, 36.1, 27.4.IR (neat, cm-1): 1719.EI-MS m/z: 150 (M+).HRMS (EI): Calcd. for C10H14O: 150.1045, Found: 150.1049. ; A solution of 4-phenylbutan-2-ol (104.3 mg, 0.694 mmol), Nor-AZADO (0.96 mg, 6.94 µmol), and acetic acid (79.5 µl, 1.389 mmol) in acetonitrile (0.69 ml) was added with sodium nitrite (9.58 mg, 0.139 mmol), and the mixture was stirred at room temperature for 4 hours under an air atmosphere. The reaction mixture was added with saturated aqueous sodium carbonate (2 ml), and the mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the objective compound (101.1 mg; yield, 98.3%). The spectrum data were found to be the same as those obtained in Example 5, (b). |
| 91% |
With sulfuric acid; Sodium sulfate [anhydrous] at 40 - 55℃; for 40h; |
|
| 91% |
With sodium chlorine monoxide; sodium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 1h; |
General procedure of the selective oxidation of alcohols
General procedure: Alcohol (0.8 mmol), NaBr (1.25 mol%), and TEMPO-P(MEO2MA-co-OEGMA) (109 mg, 0.008 mmol) were added to the mixed solution of NaClO (1.0 mmol, 1.25 mol equil., 2 mL) and CH2Cl2 (2 mL) at 0 °C. The resulting mixture was vigorously stirred at 0 °C. After the reaction was completed, ether was added to extract CH2Cl2, unreacted alcohol and product. The conversion was analyzed by GC-MS. The catalyst was left in aqueous phase and recovered by heating/centrifugation, which was used for next run after thoroughly washing with cold ether. |
| 91% |
With tert.-butylhydroperoxide In neat (no solvent) at 70℃; for 1.5h; |
|
| 91% |
With IBX; (+/-)-camphor sulfonic acid In 1,4-dioxane; dichloromethane at 20℃; Inert atmosphere; |
General procedure
General procedure: Under nitrogen atmosphere, 1.1-1.5 mmol IBX and 10 to 20 mol% (±)-CSA monohydrate was added in round bottom flask already charged with magnetic bar and 2 mL DCM:1,4-Dioxane. Stirred the mixture for 10 minutes at room temperature and added the solution of alcohol dropwise for 5 minutes. Stirred the solution at room temperature till complete consumption of alcohol. Strip off the solvent and dilute the reaction mass with DCM. Filter the suspension through sintered funnel and wash the residue properly with DCM. This residue (white powdered solid, reduced part of IBX) was successfully used for preparation of IBX. Concentrate the filtrate on rotavapor and purify the product by column chromatography. |
| 90% |
With N-bromo-N-sodiopolystyrenesulphonamide; sulfuric acid In chloroform for 6h; Heating; |
|
| 90% |
With manganese(III) tris(acetylacetonate); acetonitrile In Carbon tetrachloride at 200℃; for 3h; |
|
| 90% |
With ammonium dichromate(VI); aluminum hydrogen sulfate; mesoporous silica at 20℃; for 3h; |
|
| 90% |
With potassium bromate; zirconium(IV) oxychloride In acetonitrile for 2.5h; Heating; |
|
| 90% |
With trinitratocerium(IV) bromate for 0.5h; Heating; |
|
| 90% |
With tris[trinitratocerium(IV)] paraperiodate at 90℃; for 1.5h; |
|
| 90% |
With Sodium hydrogenocarbonate; sodium bromide In dichloromethane at 20℃; Electrochemical reaction; |
|
| 90% |
With sodium chlorine monoxide; 3-methyl-4-oxa-5-azahomoadamantane; Sodium hydrogenocarbonate; potassium bromide In dichloromethane; lithium hydroxide monohydrate at 0℃; for 0.333333h; Inert atmosphere; |
|
| 90% |
With 2-azaadamantane-N-oxyl; oxygen In aq. acetate buffer at 20℃; for 8h; Green chemistry; Enzymatic reaction; chemoselective reaction; |
|
| 90% |
With pyridine; Tributylphosphine oxide; oxygen; palladium diacetate In toluene at 80℃; for 24h; Molecular sieve; |
|
| 90% |
With sodium hypochlorite pentahydrate; 4-acetamido-2,2,6,6-tetramethylpiperidine-N-hydroxyammonium tetrafluoroborate In lithium hydroxide monohydrate; acetonitrile at 20℃; for 1.5h; |
|
| 90% |
With (NH4)4[CuMo6O18(OH)6]·5H2O; oxygen; anhydrous sodium sulphite In lithium hydroxide monohydrate; acetonitrile at 60℃; for 16h; |
|
| 89% |
With tetra-n-butylammonium acetate; palladium diacetate; 8-hydroxyquinoline-2-sulfonic acid In toluene at 100℃; for 6h; |
|
| 89% |
With 1-methyl-1H-imidazole; copper (I) iodide; 9-azabicyclo[3.3.1]nonane N-oxyl; oxygen In 1-methyl-pyrrolidin-2-one at 60℃; for 2h; |
|
| 89% |
With Burgess Reagent; dimethyl sulfoxide at 20℃; for 0.0833333h; Schlenk technique; Inert atmosphere; |
|
| 89% |
With double-atom catalyst FeCo-DAC In n-octane at 160℃; for 48h; Inert atmosphere; Sealed tube; |
|
| 88% |
With oxygen; Cs2CO3 In lithium hydroxide monohydrate for 3h; Reflux; |
General procedure
General procedure: All reactions were performed in a glass flask slurry reactor connected to an O2 tube for atmosphere control and a condenser for reflux condition. A mixture of alcohol (1mmol), Cs2CO3 (0.5mmol) and 2Au/1CuO-ZnO (0.05g) in water was stirred under oxygen atmosphere in a slurry reactor at total reflux condition. Then the catalyst was recovered by filtration, washed two times with 5ml hot EtOAc, and dried for consecutive reaction runs. The filtrate was quenched with 2M HCl aqueous solution, extracted with EtOAc three times and dried over anhydrous MgSO4. Evaporation of the solvent followed by column chromatography on silica gel afforded the pure products (Table3). |
| 88% |
With ICl; Cs2CO3 In dichloromethane at 0 - 20℃; for 8h; Green chemistry; |
General Procedure for the Study of the Substrate Scope of ICl as Oxidant
General procedure: Starting alcohols (1.00 g, 1.0 eq) specified in Table 3 were dissolved in 10 mL of dried CH2Cl2 (for substrates in entries 8-20 in Table 3, 30 mL of dried CH2Cl2 was used), and the resulting mixture was stirred in an ice-water bath, followed by addition of Cs2CO3 (3.0 eq). The suspension was stirred at this temperature, and ICl (1.5 eq) dissolved in 2 mL of CH2Cl2 was added dropwise. After addition, the reaction mixture was stirred at room temperature until the reaction completed as indicated by TLC analysis, which was conducted at 0.5-h intervals.The reaction mixture was subjected to aqueous workup described previously to yield the pure carbonyl compounds specified in Table 3. |
| 87% |
With ferric(III) bromide; dihydrogen peroxide In acetonitrile at 20℃; for 36h; |
|
| 87% |
With ruthenium(III) trichloride hydrate; oxygen; C25H44NO2PS In 1,2-dichloro-ethane at 60℃; for 17h; |
|
| 86% |
With Nitrous oxide In 1,2-dichloro-ethane at 150℃; for 7.5h; |
|
| 86% |
With polystyrene-supported hypervalent iodine(V) reagent In 1,2-dichloro-ethane at 85℃; for 1h; |
|
| 86% |
With Nitrous oxide In 1,2-dichloro-ethane at 150℃; for 7.5h; |
|
| 86% |
With bis(chlorine)-1,4-diazabicyclo[2.2.2]octane at 180℃; for 0.0666667h; microwave irradiation; |
|
| 86% |
With N-(2-iodylphenyl)glutarylamide supported on amonomethylpolystyrene resin In 1,2-dichloro-ethane at 85℃; for 1h; |
|
| 86% |
With pyridine; sodium peroxodisulphate; tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate; 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinoxy In acetonitrile at 30℃; for 24h; Sealed tube; Irradiation; Green chemistry; |
|
| 84% |
With 2,6-dichloropyridine N-oxide; trans-dioxo(5,10,15,20-tetramesitylporphirinato)ruthenium(VI); 4 A molecular sieve; hydrogen bromide In benzene for 24h; Ambient temperature; |
|
| 84% |
With sodium chlorine monoxide; tetrabutylammonium bromide; potassium bromide In dichloromethane at 0℃; for 0.333333h; |
3.2.1
Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (%). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols. |
| 83% |
With sodium chlorine monoxide; tetrabutylammonium bromide; potassium bromide In dichloromethane at 0℃; for 0.333333h; |
3.2.1
Then, using 1-methyl-AZADO synthesized, the activities thereof as an oxidation catalyst were estimated in the same manner using various secondary alcohols specified in Tables 2 and 3. As for the reaction conditions, the catalyst amount was 0.01 eq. in CH2Cl2, and KBr (0.1 eq.), n-Bu4NBr (0.05 eq.) and NaOCl (1.4 eq.) were further added, and the reaction was carried out under ice cooling. The reaction time was 20 minutes. After completion of the reaction, the percent yield of each product was determined. The percent yield was calculated by the formula: (actual yield, i.e., the amount of product)/(theoretical yield, i.e., calculated from the amount of consumed starting material) x 100 (%). For comparative examples, runs were carried out under the same reaction conditions using TEMPO, and each comparative yield was calculated. The results thus obtained are shown in Tables 2 and 3. Table 2 [Show Image] Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-1[Show Image] 84 83 2-2[Show Image] 91 5 2-3[Show Image] 99 16 2-4[Show Image] 93 15 2-5[Show Image] 100 8 2-6[Show Image] 100 12Table 3 Test No. Alcohol species Yield (%) Catalyst Me-AZADO (Invention) TEMPO (Compar. Ex.) 2-7[Show Image] 99 84 2-8[Show Image] 92 68 2-9[Show Image] 89 0 2-10[Show Image] 88 0 2-11[Show Image] 91 5 In the case of secondary alcohols having a relatively simple steric configuration (e.g. Test No. 2-1 and No. 2-7), the use of 1-methyl-AZADO of the invention as an oxidation catalyst and the use of TEMPO for comparison both gave target products in high yields. On the other hand, in the case of secondary alcohols having a sterically bulky, complicated structure, it was found that the use of 1-methyl-AZADO of the invention resulted in rapid oxidation, giving target products in high yields, whereas the use of TEMPO for comparison gave target products only in low yields. In view of such results, it is evident that 1-methyl-AZADO is a catalyst useful as an oxidation catalyst not only for primary alcohols but also secondary alcohols. |
| 83% |
Stage #1: 2-adamantanol With copper(II) bromide In acetonitrile at 20℃; for 0.05h; Inert atmosphere;
Stage #2: With N,N'-di-tert-butyldiaziridin-3-one In chloroform-d1 at 60℃; for 8h; |
|
| 83% |
With 2-azaadamantane N-oxyl; sodium hypochlorite pentahydrate; Sodium hydrogenocarbonate; potassium bromide In lithium hydroxide monohydrate for 1h; Milling; |
General procedure for the oxidation of secondary alcohols11a-19a (procedure B)
General procedure: NaOCl·5H2O (247 mg 1.5 mmol), NaHCO3 (185 mg, 2.2 mmol), and KBr (3.6mg, 0.03 mmol, 3 mol %) were placed in an Ertalyte jar (15 mL, 41.2 g) equippedwith six zirconia balls (5 mm ). The jar was ball-milled at 1800 rpm for 1 min.Following this initial grinding period, secondary alcohol 11a-19a (1.0 mmol),and 2-aza-adamantane-N-oxyl (AZADO, 1.6 mg, 0.01 mmol, 1 mol %), wereadded and the reaction mixture was milled at 30 Hz for further 30 minutes. Theprogress of the reaction was monitored by TLC (heptane/AcOEt 9:1, v/v) andGC-MS analysis of an aliquot of the crude. The milling was stopped, Na2SO3(189 mg, 1.5 mmol) added to the jar. Then, milling was continued at 30 Hz forfurther 3 minutes. AcOEt (2 × 1.5 mL) was added into the jar and the crude wastransferred to a round-bottomed flask together with silica gel (350 mg). Thecombined organic layers were concentrated in vacuo. The resulting residue waspurified through a short column on silica gel with ethyl acetate/hexane 1:9 (v/v)as the eluent to yield the target ketones 11b-19b |
| 81% |
With 3 A molecular sieve; oxygen; triethylamine In tetrahydrofuran; toluene at 25℃; for 12h; |
|
| 81% |
With palladium diacetate; oxygen; triethylamine In tetrahydrofuran; toluene at 20℃; for 12h; |
|
| 81% |
With 1-iodylbenzene In dichloromethane at 20℃; for 17h; Irradiation; Inert atmosphere; |
|
| 80% |
With γ-picolinium chlorochromate In dichloromethane at 20℃; for 2.5h; |
|
| 80% |
With air In acetonitrile at 20℃; for 24h; |
|
| 80% |
With Carbon tetrachloride; manganese(III) tris(acetylacetonate); acetonitrile at 200℃; for 3h; |
|
| 80% |
With potassium peroxomonosulfate; 2-Iodobenzoic acid In lithium hydroxide monohydrate; acetonitrile at 70℃; for 6h; |
|
| 79% |
With potassium hydroxide In neat (no solvent) at 140℃; for 24h; |
Condition C
A mixture of the substrate (250 μmol), KOH(15.4 mg, 275 μmol) and 10% Ru/C (12.6 mg, 12.5 μmol) wasstirred at 160 °C using a test tube equipped with air balloon.After the corresponding reaction time, the mixture was filteredthrough a membrane filter (pore size: 0.2 μm). The catalyst onthe filter was washed with H2O and CH2Cl2 and extracted withCH2Cl2 (5 mL × 3). The combined organic layers were driedover Na2SO4 and concentrated in vacuo. The residue was furtherpurified by silica-gel column chromatography |
| 78% |
With C29H20N4O4Ru; dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 25℃; for 1.5h; |
|
| 76% |
With C26H16N6O4Ru; dihydrogen peroxide at 60℃; for 1h; |
General procedure: The catalytic oxidation of alcohol was carried out in a magnetically stirredglass reaction tube fitted with a reflux condenser. A typical procedure was asfollows using benzyl alcohol as model substrate: benzyl alcohol (2 mmol) andRu(bbp)(pydic) (2 103 mmol, 0.1 mol % based substrate) were added into areaction tube. The reactor containing this mixture was heated to 60 C in an oilbath under vigorous stirring, and then 30% H2O2 (10 mmol) was slowlydropped in. The resulting system was stirred at 60 C for 60 min. At the end ofreaction, the resulting products and unreacted substrate were extracted bydichloromethane three times. The extracted liquid mixture was analyzed byGC and GC-MS. GC analyses were performed on a Shimadzu GC-2010 pluschromatography equipped with Rtx-5 capillary column(30 m 0.25 mm 0.25 lm). GC-MS analyses were recorded on a ShimadzuGCMS-QP2010 equipped with Rxi-5 ms capillary column(30 m 0.25 mm 0.25 lm). |
| 76% |
With 2',3',4',5'-tetra-O-acetylriboflavin; lithium trifluoromethanesulphonate; 1,3-diisopropylthiourea In lithium hydroxide monohydrate; acetonitrile at 22℃; for 24h; Inert atmosphere; Sealed tube; Irradiation; |
|
| 72% |
With 1,3,5,7-tetrakis[4-(diacetoxyiodo)phenyl]adamantane; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In dichloromethane at 20℃; |
|
| 71% |
With [MnIII(2-((2-(2-(2-(2-hydroxybenzylideneamino)phenylamino)propylamino)phenylimino)methyl)phenolato)]Cl; dihydrogen peroxide In acetonitrile for 4.3h; Reflux; |
|
| 68% |
With C26H30F6MnN6O6S2; dihydrogen peroxide; glacial acetic acid In acetonitrile at 20℃; for 1h; chemoselective reaction; |
|
| 65% |
With aluminum(III) oxide In N,N-dimethyl-formamide at 120℃; for 8h; Inert atmosphere; |
|
| 62% |
With diisopropyl-carbodiimide In toluene at 120℃; for 24h; Inert atmosphere; Sealed tube; |
|
| 60% |
With di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)]; triethylamine In propan-2-one; toluene at 150℃; Flow reactor; |
|
| 58% |
With pyridine; oxygen In toluene at 80℃; |
|
| 56% |
With oxygen In hexane at 68.84℃; for 24h; Molecular sieve; |
2.4. Catalytic test
General procedure: Pd-STO (12.5 mg), 1-phenylethanol (25 mg, 0.204 mmol), n-decaneas an internal standard and n-hexane (2 mL) as the solvent were placedin a Schlenk flask equipped with reflux condenser, mechanical stirrerand balloon. The reaction was carried out at approximately the refluxtemperature of n-hexane (342 K) under an O2 atmosphere (0.1 MPa) for24 h. In some cases, molecular sieves 3A (MS3A) were placed into thereaction mixture. |
| 32% |
With potassium peroxymonosulfate; C18H17IN2O7PolS(1-)*Na(1+); tetrabutylammonium hydrogensulfate In propan-2-one at 70℃; for 72h; Sealed tube; Green chemistry; |
|
| 31% |
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In acetonitrile at 80℃; for 8h; |
2.7 General Procedure forAerobic Oxidationofbenzyl alcohols
General procedure: To a mixture of benzyl alcohol (0.125mmol) and [MNPChs/TAETA-Cu(II)] nanocomplex (0.003g) in MeCN(0.5mL) was added TEMPO (12mol %) and the reactionmixture was stirred under O2stream (5-7mL min-1) at80°C for the required time. The reaction progress was monitoredby TLC and the yields of products were determined byGC analysis. The pure product was secured by plate silicachromatography using n-hexane/EtOAc (10:3). |
| 26% |
With NHPI In ethyl acetate at 70℃; for 2h; Irradiation; |
|
| 10% |
With oxygen; sodium hydroxide In lithium hydroxide monohydrate at 90℃; for 24h; |
|
|
With cyclohexanone In benzene at 80℃; |
|
|
With cyclohexanone In benzene at 80℃; ΔGox; |
|
|
With 3,3-dimethyldioxirane In propan-2-one at 0℃; relative rate, competition kinetic with adamantane-1,2-diol; |
|
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
