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CAS No. : | 1777-82-8 | MDL No. : | MFCD00004606 |
Formula : | C7H6Cl2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DBHODFSFBXJZNY-UHFFFAOYSA-N |
M.W : | 177.03 | Pubchem ID : | 15684 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.14 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 42.59 |
TPSA : | 20.23 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) : | -5.58 cm/s |
Log Po/w (iLOGP) : | 1.93 |
Log Po/w (XLOGP3) : | 2.54 |
Log Po/w (WLOGP) : | 2.33 |
Log Po/w (MLOGP) : | 2.72 |
Log Po/w (SILICOS-IT) : | 2.96 |
Consensus Log Po/w : | 2.5 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.92 |
Solubility : | 0.215 mg/ml ; 0.00121 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.61 |
Solubility : | 0.433 mg/ml ; 0.00244 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.46 |
Solubility : | 0.062 mg/ml ; 0.00035 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.3 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338-P310 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
92% | With phosphorus trichloride In dichloromethane; N,N-dimethyl-formamide at 60 - 80℃; | To a 100 mL round bottom flask was added 2,4-dichlorobenzyl alcohol (17.7 g, 0.1 mol) and dichloromethane (30 mL) andDMF (1 mL), followed by the addition of phosphorus trichloride (4.68 g, 0.034 mol) and slowly warming to reflux (60-80 ° C) Should be 2 ~ 3h, TLC detection shows the disappearance of raw materials, distillation was 2,4-dichlorobenzene 17.99g, yield 92percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With ethyl 2,2-dibromoacetoacetate; triphenylphosphine In dichloromethane at 20℃; for 0.25 h; | General procedure: Ethyl α,α-dibromoacetoacetate 2a (0.41 mmol, 1.2 equiv), alcohols 1a-1s (0.34 mmol, 1.0 equiv) and Ph3P (0.68 mmol, 2.0 equiv) were added under ambient temperature to 3 mL of DCE in air. After stirred at room temperature for appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (3×3 mL). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel with petroleum ether or mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-3s. |
98% | With phosphorus tribromide In dichloromethane; N,N-dimethyl-formamide at 80℃; | To a 100 mL round bottom flask was added 2,4-dichlorobenzyl alcohol (17.7 g, 0.1 mol)And dichloromethane (30 mL) and DMF (1 mL), followed by the addition of phosphorus tribromide (9.2 g, 0.034 mol), slowly warming to 80 ° C, stirring for 2 to 3 hours, Indicating that the raw material point disappeared, distillation was 2,4 - dichloro Bian bromine 23.52g, yield 98percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With silica gel; sodium cyanoborohydride for 0.0125h; Neat (no solvent); Microwave irradiation; regioselective reaction; | |
96% | With sodium tetrahydroborate; pyrographite In tetrahydrofuran; water at 20℃; for 0.0166667h; | |
95% | With Triethoxysilane; C27H42FeP4S In tetrahydrofuran at 50℃; for 2h; Schlenk technique; Green chemistry; |
95% | With cis-[(H)(SePh)Fe(PMe3)4]; sodium t-butanolate In isopropyl alcohol at 60℃; for 24h; | |
94% | With sodium tetrahydroborate; ammonium oxalate In acetonitrile at 20℃; for 0.166667h; | |
94% | With zinc(II) tetrahydroborate In tetrahydrofuran; water at 20℃; for 0.0166667h; | |
94% | With 2BH4(1-)*Zn(2+)*Cl2Na2 In acetonitrile at 20℃; for 0.0333333h; | 2.4. Typical Procedure for the Reduction of Ketones withZn(BH4)2/2NaCl System in CH3CN General procedure: In a round-bottomed flask (10 mL), equipped with a magneticstirrer bar, a solution of acetophenone (0.121 g, l mmol) was prepared in CH3CN(3 mL). To this solution, Zn(BH4)2/2NaCl (0.210 g,1 mmol) was added. The resulting mixture was stirred at room temperature for 60 min. The reaction was monitored by TLC(eluent; Hexane/EtOAc: 10/1). After completion of the reaction, distilled water (5 mL) was added to the reaction mixture and stirred for 5 min. The mixture was extracted with CH2Cl2 (3 ×8 mL) and dried over anhydrous Na2SO4. Evaporation of the solvent followed column chromatography of the resulting crude material over silica gel (eluent; Hexane/EtOAc: 10/1) afforded crystals of 1-phenylethanol (0.l1 g, 93 % yield,Table 2, entry 11). |
94% | With sodium tetrahydroborate In tetrahydrofuran at 20℃; for 0.166667h; | |
94% | With C8H18B2N4O2Zn In acetonitrile at 20℃; for 0.5h; | |
94% | With [Zn(tetrahydroborato)2(acridine)] In acetonitrile at 20℃; for 0.5h; | Reduction of Acetophenone to 1-phenylethanolwith [Zn(BH4)2(acr)], A Typical Procedure General procedure: In a round-bottomed flask (10 mL),equipped with a magnetic stirrer, a solution ofacetophenone (0.120 g, 1mmol) in CH3CN (3 mL)was prepared. The complex reducing agent (0.274g, 1mmol) was then added as a solid and the mixturewas stirred at reflux conditions. TLC monitored theprogress of the reaction (eluent; CCl4/Et2O : 5/2). After completion of the reaction in 90 min, a solutionof 5% HCl (5 mL) was added to the reaction mixtureand stirred for 10 min. The mixture was extractedwith CH2Cl2(3 × 10 mL) and dried over theanhydrous sodium sulfate. Evaporation of thesolvent and short column chromatography of theresulting crude material over silica gel by eluent ofCCl4/Et2O : 5/2 afforded the pure liquid benzylalcohol (0.113 g, 93% yield). |
94% | Stage #1: 2,4-dichlorobenzaldeyhde With Triethoxysilane; [cis-Fe(H)(SPh)(PMe3)4] In tetrahydrofuran at 50℃; for 2h; Stage #2: With methanol; sodium hydroxide In tetrahydrofuran; water at 60℃; for 24h; | 2.2. General procedure for catalytic hydrosilylation of aldehydes General procedure: To a 25 mL Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0 mmol) and (EtO)3 SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50-55 °C until there was no aldehyde left (monitored by TLC and GC-MS). The reaction was then quenched byMeOH (2mL) and a 10% aqueous solution of NaOH (5 mL) with vigorous stirring at 60 °C for about 24 h.The organic product was extracted with diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under vacuum. The alcohol product was further purified using flash column chromatography (elute with 5-10% ethyl acetate in petroleum ether). The 1H NMR and 13C NMR spectra of the alcohol products are providedin Supporting information. |
92% | With sodium tetrahydroborate; lithium perchlorate In acetonitrile for 0.166667h; | |
91% | With sodium cyanoborohydride at 20℃; for 0.05h; | |
90% | With aluminum oxide; zinc(II) tetrahydroborate In tetrahydrofuran at 20℃; for 0.08h; chemoselective reaction; | A typical procedure for reduction of aldehydes with the Zn(BH4)2/Al2O3 system in THF General procedure: Zn(BH4)2 was prepared from ZnCl2 and NaBH4 according to an established procedurefrom the literature.5 In a round-bottomed flask (10 mL) equipped with a magnetic stirrer, asolution of benzaldehyde (0.106 g, 1 mmol) in THF (3 mL) was prepared. To this solution,Zn(BH4)2 (0.048 g, 0.5 mmol) and then neutral Al2O3 (0.101 g, 1 mmol) were added and themixture was stirred at room temperature for 5 minutes. Completion of the reaction wasmonitored by TLC (eluent, CCl4/Et2O: 5/2). Then, distilled water (1 mL) was added to thereaction mixture and stirring was continued stirred for 5 min.. The mixture was extracted withCH2Cl2 (3×6 mL) and dried over anhydrous Na2SO4. Evaporation of the solvent and a shortcolumn chromatography of the resulting crude material over silica gel (0.015-0.040 mm, eluent,CCl4/Et2O: 5/3) afforded the pure liquid benzyl alcohol (0.102 g, 94 %, Table III, entry 1). |
88% | With Triethoxysilane; C43H48FeP4 In tetrahydrofuran at 50℃; for 2h; | |
88% | With methanol; C25H29ClNO2Rh; caesium carbonate at 90℃; for 1h; | |
87% | With iodine; magnesium In methanol at 20℃; for 0.25h; | |
86% | Stage #1: 2,4-dichlorobenzaldeyhde With pyridine N-oxide; Triethoxysilane; C27H47FeP3Si In tetrahydrofuran at 30℃; for 6h; Schlenk technique; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol at 60℃; for 24h; Schlenk technique; | |
85% | Stage #1: 2,4-dichlorobenzaldeyhde With C36H44F4N2Ni2P2; diphenylsilane In tetrahydrofuran at 55℃; for 8h; Schlenk technique; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol at 55℃; for 24h; Schlenk technique; Inert atmosphere; | |
84% | With potassium chloride In water; acetonitrile for 6h; Electrochemical reaction; Green chemistry; | 2.1. Process for electrochemical reduction General procedure: Cyclic voltametric measurements of Chloro substituted benzaldehydes were obtained from model no. ECDA-001 basic Electrochemistry system at various scan rates (i.e., 100, 200, 300, 400 and 500) and pH(i.e., 5.0, 7.0 and 9.0) in aqua-acetonitrile medium. During cyclic voltammetricstudy, supporting electrolyte of potassium chloride (KCl),working electrode of glassy carbon, counter (auxiliary) electrode ofplatinum (Pt) and reference electrode of Ag/AgCl was employed. All the experiments were taken at room temperature. Before each electrochemical measurement from cyclic voltammetry, the working electrode(glassy carbon) was polished with the help of aluminium oxide (Al2O3) of 0.4 μ.To remove dissolved oxygen from the medium, decontaminated and dry nitrogen was purged for 5 min into experimental solution before taking measurements and then cyclic voltammograms for blank solution were obtained. The solution of Chloro substituted benzaldehyde was poured into this black solution. Then by providing initial potential (I.P.),final potential (F.P), scan rate (S.R.) and current sensitivity (C.S.), the resultant cathodic (reduction) peak potential was obtained as a functionof cathodic (reduction) peak current. |
83% | With ((2-iPr<SUB>2</SUB>PC<SUB>6</SUB>H<SUB>4</SUB>)<SUB>2</SUB>SiH)Fe(H)(PMe<SUB>3</SUB>)<SUB>2</SUB>; potassium <i>tert</i>-butylate; isopropyl alcohol at 60℃; for 24h; Schlenk technique; | |
81% | With sodium tetrahydroborate; nickel dichloride In tetrahydrofuran at 20℃; for 0.0833333h; | |
78% | With aluminium trichloride; borane tert-butylamine In dichloromethane at 22℃; for 20h; | |
75% | With diammonium hydrogen phosphite; zinc In water; toluene at 20℃; for 0.75h; Inert atmosphere; | |
62% | With formic acid; C25H26ClIrN2; sodium formate In water at 80℃; for 12h; Inert atmosphere; | |
61.4% | With formic acid at 120℃; for 25h; | |
54% | With Grubbs catalyst first generation; potassium hydroxide In 1,4-dioxane at 80℃; for 20h; | |
30% | With whole seeds of Bauhinia variegata L. In water; dimethyl sulfoxide at 40℃; for 48h; | |
With ammonia; nickel at 80℃; Hydrogenation; | ||
12 % Chromat. | With Dunaliella parva; microalga In methanol at 25℃; for 120h; | |
Stage #1: 2,4-dichlorobenzaldeyhde With sodium tetrahydroborate In methanol at 20℃; for 2h; Cooling with ice; Stage #2: With hydrogenchloride In methanol; water | General procedure for preparation of diarylmethanes General procedure: To a solution of benzaldehyde (3.18 g, 30.0 mmol) inmethanol (20 mL) was added sodium borohydride (1.37g, 36.0 mmol) in portions inice-water bath. The mixture was stirred at room temperature, and after 2.0 hquenched with diluted HCl (1M). The resulting aqueous solution was then extracted with CH2Cl2 (10 mL×3).The organic phase was combined, dried over anhydrous MgSO4, filteredand concentrated reduced pressure by a rotary evaporator to provide the crude product. The crude product was purified by column chromatography on silica gelusing EtOAc-petroleumether (1:20, v/v) as eluentto give the corresponding phenylmethanol | |
Multi-step reaction with 2 steps 1: C22H32F6FeNP3 / tetrahydrofuran / 3 h / 45 °C / Inert atmosphere; Schlenk technique 2: sodium hydroxide / methanol / 24 h / 60 °C / Inert atmosphere; Schlenk technique | ||
Multi-step reaction with 2 steps 1: C18H37F5FeP4 / tetrahydrofuran / 40 °C / Schlenk technique; Inert atmosphere 2: sodium hydroxide / methanol; water / 24 h / 60 °C / Schlenk technique; Inert atmosphere | ||
With Ru(H)<SUB>2</SUB>(CO)(triphos); hydrogen In 1,4-dioxane at 140℃; for 16h; | ||
With sodium tetrahydroborate In methanol | ||
Multi-step reaction with 2 steps 1: C19H44FeOP4Se / tetrahydrofuran / 2 h / 50 °C 2: sodium hydroxide; methanol / 50 °C | ||
With isopropyl alcohol; potassium hydroxide at 80℃; for 3h; Green chemistry; | ||
Multi-step reaction with 2 steps 1: 2C4H8O*C42H47FeOP5 / tetrahydrofuran / 24 h / 60 °C / Inert atmosphere; Schlenk technique 2: water; sodium hydroxide / methanol / 24 h / 50 °C / Inert atmosphere; Schlenk technique | ||
Multi-step reaction with 2 steps 1: C45H69FeN8PSi2 / tetrahydrofuran / 6 h / 20 °C / Inert atmosphere; Schlenk technique 2: silica gel / ethyl acetate; Petroleum ether | ||
Multi-step reaction with 2 steps 1: C28H59FeN2OP3Si / tetrahydrofuran / 8 h / 60 °C / Inert atmosphere; Schlenk technique 2: sodium hydroxide / water; methanol / 24 h / 60 °C / Inert atmosphere; Schlenk technique | ||
With sodium tetrahydroborate In methanol at 0℃; for 2h; | 2.3. Synthesis of aryl alcohols (2a-l) General procedure: Sodium borohydride (3.41 g, 24 mmol) was added to a solu- tion of aryl aldehydes (1a-l) (1.5 g, 5.9 mmol) in methanol (30 ml) and the mixture was stirred for 2 h at 0 °C. Completion of reac- tion was monitored by TLC and then, excess sodium borohydride was quenched by adding cold water or ammonium chloride solu- tion. Methanol was evaporated; the residue was dissolved in EtOAc (100 mL) and washed with water (2 ×100 mL). The organic layer was dried over anhydrous sodium sulfate and the product was pu- rified by passing through a column chromatography. | |
Multi-step reaction with 2 steps 1: C36H64Cl3CoN4P2Si2 / tetrahydrofuran / 4 h / 40 °C / Inert atmosphere; Schlenk technique 2: sodium hydroxide; water / methanol / Ca. 24 h / 60 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanol; sodium methylate at 183℃; | ||
With potassium hydroxide | ||
With tetrabutylammomium bromide; sodium hydroxide In toluene at 35℃; for 1.08333h; | 2.2.5. The side reaction of aldehyde in PTC system General procedure: A solution of TBAB (0.5 mmol), aldehyde (10 mmol) in toluene (30 mL) was placed in a 100 mL flask and stirred at 1400 rpm. 20 g of 50% (m/m) NaOH aqueous solution or 40 mmol of solid NaOH was added at 35°C. After the completion of the reaction as indicated by TLC, the aqueous phase was separated and washed twice with 5 mL of toluene. The pH value of the aqueous phase was adjusted to 2 with HCl solution. The resulting precipitate was filtered and rinsed twice with 3% HCl solution. The organic layer was washed with three 5 mL-portions of 3% HCl solution. Theorganic phase was dried over MgSO4 and evaporated to dryness.The crude products were purified by recrystallization from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium bis(2-methoxyethoxy)aluminium dihydride; In diethyl ether; at 20℃; for 1h; | To a 100 mL round bottom flask was added 2,4-dichlorobenzoic acid (19.1 g, 0.1 mol) and ether (30 mL), followed byRed-Al (20.2 g, 0.1 mol),The reaction was stirred at room temperature for 1 h, filtered, and the residue was run three times with ether (5 mL x 3) The resulting organic phase was distilled to give 17.17 g of 2,4-dichlorobenzyl alcohol in 97% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With tetra-N-butylammonium tribromide; In acetonitrile; at 20℃; for 6h;Irradiation; | General procedure: In a 50ml Pyrex round-bottom flask, a mixture of alcohol (1mmol), TBATB (10-20mg, 0.02-0.04mmol) in 10ml of CH3CN was exposed to blue or violet light LED irradiation at room temperature under an air atmosphere with stirring. The progress of the photocatalytic oxidation reaction was monitored by TLC on silica gel plates. The reaction mixture externally irradiated until the alcohol was completely consumed. |
92% | With tert.-butylhydroperoxide; 2,2?-((1E,1?E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene))diphenolcopper(II); sodium hydroxide; In water; acetonitrile; at 20℃; | General procedure: Alcohol (0.5 mmol), salophen copper (II) complex (2 mol%), NaOH (0.6 equiv), and 70% TBHP in water (1.1 equiv) were dissolved in acetonitrile (5 mL), and the homogeneous solution was stirred at room temperature in air overnight. After completion of the reaction, the solvent was evaporated under reduced pressure. The residue was purified over silica gel by column chromatography (10-25% EtOAc in hexane). |
91% | With ammonium hydroxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; In ethanol; at 50℃; for 24h; | General procedure: Under an air atmosphere, a Schlenk tube was charged with MCM-41-bpy-CuI (40 mg, 0.025 mmol), alcohol (0.5 mmol), TEMPO (4 mg, 0.025 mmol), aqueous ammonia (0.5 mmol, 25e28%, w/w) and EtOH (1.0 mL). The mixture was stirred at 50 C for 18-48 h. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ethyl acetate (10 mL), and filtered. The MCM-41-bpy-CuI complex was washed with EtOH (2*5 mL), and Et2O (5 mL) and reused in the next run. The filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography on silica gel (petroleum/ethyl acetate=15:1 to 10:1) to provide the desired product. |
90% | With C11H16CuN2O6; dihydrogen peroxide; In neat (no solvent); at 70℃; for 3h; | General procedure: Catalytic experiments were carried out in a 5 mL test tube. In a typical procedure, 1 mmol benzyl alcohol, 0.02 mmol nanosize copper(II) complex and 3 mmol 30 % H2O2 were added. The reaction mixture was stirred for 3 h at 70 C under solvent-free condition. The reaction products were monitored by thin-layer chromatography (TLC). After the reaction was completed, the pure product was obtained after chromatography on a short column of silica gel. The oxidation products were identified by comparison with authentic samples. |
87% | With nitrogen dioxide; In acetonitrile; at 140℃; under 760.051 Torr; for 5h;Sealed tube; | Magnet, 2 mL acetonitrile, 0.5 mmol benzyl alcohol, 0.046 mmol NO2 were added to the reaction tube (air pressure 1 atm). After the reaction tube was sealed, it was placed in a heating bath at 140 C and reacted under magnetic stirring for 5 hours. Once the reaction time was reached, the reaction was cooled to room temperature and the product was subjected to internal standard quantitative analysis by gas chromatography to give a yield of 2,4-dichlorobenzaldehyde of 87%. Then repeat the above experiment, the product was separated and purified by column chromatography to obtain 2,4-dichlorobenzaldehyde product. |
85% | With tert.-butylhydroperoxide; In ethanol; at 80℃; for 1h;Catalytic behavior; | General procedure: All catalytic experiments were performed in a 5-mL test tube. In a typical procedure, to a solution of benzyl alcohol (1 mmol) in solvent (0.5 mL), CuFe2O4-SiO2-MnClsalpn (0.0014 g, 2 mol %) and TBHP (2 mmol) were added. The reaction mixture was stirred for 1 h at 80 C, and the products were tracked by TLC or GC. After completion of the reaction, the mixture was diluted with EtOAc. The catalyst was separated with an external magnet, washed with EtOAc, dried, and reused for a sequential run under the same reaction conditions. Evaporation of the solvent from the filtrate gave the crude product, which was purified by chromatography on silica gel with n-hexane/EtOAc (2:5). |
81% | With tert.-butylhydroperoxide; In acetonitrile; at 80℃; for 3h;Catalytic behavior; | General procedure: Runp-nSTDP (40mg, 0.84mol %) were stirred in 5mL ofacetonitrile taken in a round bottomed flask equipped witha condenser and a stirring bar. The substrate (0.5mmol),oxidant (1mmol) was added to the stirring solution, andthen the mixture was refluxed at 80C under atmosphericpressure of air. The reaction progress was monitored by GC.After completion of the reaction, the nanocatalyst was separatedfrom the reaction mixture by simple centrifugation,washed with the adequate amount of acetonitrile (5ml) andH2O(5ml). Later on, the products were extracted with Et2Oand purified on a silica gel column. |
80% | With dihydrogen peroxide; In ethanol; at 80℃; for 3h; | General procedure: Catalytic experiments were carried out in a 5-mL test tube. In a typical procedure, to 1 mmol benzyl alcohol in 1 ml solvent, 2 mol% (0.02 g) of gamma-Fe2O3-MoO2L and 2 mmolof 30 % H2O2 was added. The reaction mixture was stirred for 3 h at 80 C. The reaction products were monitored byTLC or GC. After completion of the reaction, the mixture was diluted with EtOAc. The catalyst was separated by an external magnet, washed with EtOAc, dried and reused for a consecutive run under the same reaction conditions. Evaporation of the solvent from the filtrate under reduced pressure gave the crude products, which were then purified by chromatography on silica gel eluted with n-hexane/EtOAc (2:1). |
78% | With oxygen; In acetonitrile; at 30℃;Irradiation; | General procedure: In a general process, the photocatalytic activity of nanostructureswas investigated by oxidation of aromatic alcohol. In typically,0.1 mmol of alcohol was added to 1.5 ml of solvent in Pyrex glass celland stirred for 5 min. Then, 10 mg of photocatalyst was dispersed insolution and magnetically stirred in the dark for 15 min to reach anequilibrium between adsorption-desorption. Photocatalytic reactionswere performed by irradiation with an LED lamp (5 W). To control thetemperature during the oxidation reaction, the water circulation wasapplied to cooling of the reaction mixture. During the photocatalyticprocess, the reactor was exposed to air to ensure that enough oxygen isprovided for the reaction. The progress of the reaction was monitoredusing the TLC by periodic sampling. After completion of the reaction,the catalyst was separated from the suspension by centrifuging(3500 rpm) and washed with solvent to separate all of the residualmaterials. |
75% | With tert.-butylhydroperoxide; [((E)-1-(((2-hydroxypropyl)imino)methyl)naphthalen-2-olato)Cu(mu2-Cl)2Cu((E)-1-(((2-hydroxypropyl)imino)methyl)naphthalen-2-olato)]*1.5(methanol); In ethanol; at 80℃; for 2h; | General procedure: To a solution of the alcohol (0.5 mmol) and complex (scheme 1; 0.01 mmol) in ethanol (5 mL) was added tBuOOH (0.5 mmol), and the reaction mixture was stirred in air at 80C for the required time. GC monitored the reaction progress and the yields of the products. Further purification was achieved by silica chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With ethyl 2,2-dibromoacetoacetate; triphenylphosphine; In dichloromethane; at 20℃; for 0.25h; | General procedure: Ethyl alpha,alpha-dibromoacetoacetate 2a (0.41 mmol, 1.2 equiv), alcohols 1a-1s (0.34 mmol, 1.0 equiv) and Ph3P (0.68 mmol, 2.0 equiv) were added under ambient temperature to 3 mL of DCE in air. After stirred at room temperature for appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (3×3 mL). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel with petroleum ether or mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-3s. |
98% | With phosphorus tribromide; In dichloromethane; N,N-dimethyl-formamide; at 80℃; | To a 100 mL round bottom flask was added <strong>[1777-82-8]2,4-dichlorobenzyl alcohol</strong> (17.7 g, 0.1 mol)And dichloromethane (30 mL) and DMF (1 mL), followed by the addition of phosphorus tribromide (9.2 g, 0.034 mol), slowly warming to 80 C, stirring for 2 to 3 hours, Indicating that the raw material point disappeared, distillation was 2,4 - dichloro Bian bromine 23.52g, yield 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 2.3 % Chromat. 2: 0.9 % Chromat. 3: 0.7 % Chromat. 4: 1.3 % Chromat. 5: 0.2 % Chromat. 6: 0.3 % Chromat. | With 2,2'-azobis(isobutyronitrile); oxygen In ethanol at 77.5℃; for 3.4h; other times; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With polydopamine sulfamic acid-functionalized silica gel nanocatalyst; In neat (no solvent); at 20℃; for 0.5h; | General procedure: A 25 mL ballon containing a magnetic stir bar was chargedwith phenol/alcohol/amine (1 mmol) and acetic anhydride(2 mmol), SiO2/PDA-SO3H (30 mg, 1 mol% H+)as catalyst.The reaction mixture was stirred at room temperature and thereaction progress was monitored on thin-layer chromatography(TLC). After completion of the reaction, the reaction mixturewas diluted with ethyl acetate and catalyst was separatedfrom reaction mixture by centrifugation. The reaction mixturewas washed with sat. NaHCO3solution (1 × 15 mL) and theproduct was extracted with ethyl acetate (3 × 10 mL) and driedover Na2SO4and evaporated under vacuum. All the obtainedproducts are well known in the literature. |
92% | In neat (no solvent); at 75℃; for 0.333333h; | General procedure: Alcohol, phenol, and/or amine (1 mmol) were added to amixture of the ZnAl2O4SiO2 nanocomposite (100 mg) andacetic anhydride (1 mmol). The mixture was stirred at 75 C(for alcohols and phenols) or at room temperature (for amines)for a time. The progress of the reaction was monitored by TLCand/or GC-MS. When the reaction was completed, ethyl acetate(10 mL) was added and the mixture was filtered to separate offthe catalyst. The catalyst was washed twice with 7.5 mL ethylacetate. The combined organic phases were washed with a10% solution of NaHCO3 and then dried over MgSO4. The solventwas removed to yield the product. If further purificationwas needed, the product was passed through a short column ofsilica gel. All products were characterized on the basis ofGC-MS, FT-IR, and 1H-NMR spectral data by comparing thesespectra with those of standard samples or literature data. |
92% | With 20CuO-ZnO nanocatalyst; In dichloromethane; at 20℃; for 0.333333h;Green chemistry; | General procedure: A heterogenous mixture of alcohol (1 mmol), acetic anhydride (1.2 mmol) and the 20CuO-ZnO nanocatalyst (0.05g) in CH2Cl2 (10 mL) was stirred at room temperature. Upon completion of the reaction, as determined by TLC, the mixture was filtered to recover the catalyst. The catalyst was washedwith CH2Cl2 (5 mL) and then dried at X C for Y h before beingused in consecutive runs. The combined organic layers were washed sequentially with 5% (w/v) NaHCO3 solution and water and then dried over MgSO4. The solvent was then removed in vacuo to give the crude product as a residue, which was purified by column chromatography over silica gel to afford the pure desired products in high yield. |
90% | With polyvinylpolypyrrolidone supported triflic acid; In neat (no solvent); at 20℃; for 0.133333h;Green chemistry; | General procedure: To a mixture of substrate (1.0 mmol) and acetic anhydride (1.0 mmol), 0.008 g PVPP.OTf (3.4 mol%) was added. The mixture was stirred at room temperature for the time indicated in Tables 2, 3 and 4. The progress of the reaction was followed by TLC or GC for aliphatic alcohols. After completion of the reaction, ethyl acetate (2 9 10 cm3) was added, and the catalyst was separated by filtration. The filtrate was washed with an aqueous solution of NaHCO3 (10%, 2 9 10 cm3) and water (2 9 10 cm3) and dried with Na2SO4. The solvent was evaporated under reduced pressure to afford the expected product. |
90% | With Fe3O4-polyethylene glycol composite magnetic nanoparticles; In neat (no solvent); at 20℃; for 0.166667h;Sonication; Green chemistry; | General procedure: A 10-mL balloon was charged with phenol/alcohol/amine (1mmol) and acetic anhy-dride (3mmol), with Fe 3 O 4 PEG (10mg) as catalyst. The reaction balloon was taken in the ultrasonic bath, where the level of the reaction mixture is lower than the surface of the water. Then, the mixture was sonicated under 60W of power of the ultrasonic bath at room temperature for the appropriate time, as shown in Table2. After completion of the reaction (monitored by thin-layer chromatography), the reaction mixture was diluted with ethyl acetate and the catalyst was separated from reaction mixture by an external magnet. The separated catalyst was washed with DI water and absolute ethanol several times then dried in oven and reused for further reaction. The reaction mixture was washed with sat. NaHCO 3 solution (1 × 15mL) and the product was extracted with ethyl acetate (3 × 10mL) and dried over Na 2 SO 4 and evaporated under vacuum. All the obtained products are well known in the liter-ature and were confirmed by nuclear magnetic resonance (NMR) analysis and com -parison with literature data. |
84% | With tribromomelamine; In dichloromethane; at 20℃; for 0.2h;Green chemistry; | General procedure: Tribromo melamine (0.1 mmol) was added to a solution of 3-fluorobenzyl alcohol (0.126 g, 1 mmol) and acetic anhydride (0.204 g, 2 mmol) in dichloromethane (5 mL), and the reaction mixture was stirred at room temperature for 1 h (the progress of the reaction was monitored by TLC). On completion of the reaction, water (5 mL) and then 5% NaHCO3 (5 mL) was added to the mixture with stirring, and the product was extracted with CH2Cl2 (5 mL × 4). The organic layer was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents were evaporated, and 3-fluorobenzyl acetate was obtained in 86% yield. |
53% | With modified mesoporous silica MCM-41(at)XA immobilized Ni(II); In neat (no solvent); for 6h;Green chemistry; | General procedure: Alcohol (1 mmol) was added to a mixture of MCM-41XANi(II) (0.03 g) and acetic anhydride (0.4 mL), and theresulting mixture was stirred at 50 C in solvent-free condition.After completion of the reaction (mentioned by TLC,ethylacetate: n-hexane, 3:7), dichloromethane (20 mL) wasadded and the catalyst was separated by filtration. Then, themixture was diluted with CH2Cl2.The organic phase washedwith 10% aqueous solution of sodium bicarbonate and driedover Na2SO4.Finally, the organic solvents were evaporatedand the product obtained with high to excellent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In dichloromethane; at 20℃; for 0.416667h; | General procedure: A mixture of alcohol or phenol (1 mmol), DHP (1.2-1.4 mmol), and MNPs-PSA (5 mg, 0.95 mol%) was stirred at room temperature in dry CH2Cl2 (2 mL), and the progress of the reaction was monitored by TLC. After completion of the reaction, catalyst was separated by an external magnet and washed with CH2Cl2. Then, the pure product was isolated by passing of the reaction mixture through a short column using n-hexane and ethyl acetate (9:1) as eluent. |
82% | With C8H15N2O3S(1+)*Cl5Zn2(1-); In neat (no solvent); at 20℃; for 1.33333h;Green chemistry; | General procedure: A test tube, equipped with a magnetic stirrer bar, was charged with benzyl alcohol (0.51 mL, 5.0 mmol), DHP (0.45 mL, 5.0 mmol), and catalyst (15 mg, 0.5 mol %, M = 527 g/mol). The resulting mixture was stirred at room temperature until reaction completion (40-90 min, GC and TLC). The crude product was dissolved in Et2O (for compounds 8, 9, 11, EtOAc was used) and purified by passing through a short column of silica gel using hexane-ethyl acetate as eluent or recrystallized from EtOH or Et2O to give pure products. All products are known compounds and identical to literature reports.3 |
80% | For the tetrahydropyanylation or trimethylsilylation of alcohols, to solution of the DHP(1 mmol) or HMDS(1 mmol) in CH3CN (5ml) were added {K*18-crown-6]Br3}n (0.001 mmol). The solution was stirred at room temperature for 1 min. Then alcohol(1 mmol for THP and 2 mmolf for TMS) was stirred at room temperature for an appropriate time (Table 2). After completion of the reaction, CH3CN was removed by water bath distillation. To the residue was added n-hexane or ethyl acetate(5 ml) and the mixture was filtered (the catalyst is insoluble in n-hexane and ethyl acetate). The filtrate was wahed with n-hexane or ethyl acetate (10 ml*2). The solvent was removed by distillation to yield pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With methanol at 20℃; for 1.58333h; | General procedure for the deprotection of THP-ethers into correspondingalcohols or phenols General procedure: A mixture of THP-ethers (1 mmol) and MNPs-PSA (20 mg, 3.8 mol%) was stirred at room temperature in CH3OH (2 mL), and the progress of the reaction was monitored by TLC. After completion of the reaction, catalyst was separated by an external magnet and washed with CH2Cl2. Then, the solvent was removed under reduced pressure, and the product was purified through a short column of silica gel to obtain the pure alcohol or phenol. |
97% | With 1,4-diazabicyclo[2.2.2]octane tribromide supported on magnetic Fe3O4 nanoparticles In methanol at 20℃; for 3h; | |
95% | With tetra-N-butylammonium tribromide In methanol at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 91% 2: 80% | Stage #1: 2,4-dichlorobenzaldeyhde With μ-Cl In dichloromethane at 20℃; for 48h; Stage #2: With hydrogenchloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With poly(N-bromobenzene-1,3-disulfonamide) for 0.07h; Irradiation; | |
99% | In dichloromethane at 20℃; for 1h; | |
98% | With asymmetric salen type di-Schiff base-based zinc complex supported on Fe3O4 nanoparticles at 20℃; for 0.283333h; |
96% | Stage #1: (2,4-dichlorophenyl)methanol With Iron(III) nitrate nonahydrate; sodium iodide In dichloromethane at 20℃; Stage #2: 1,1,1,3,3,3-hexamethyl-disilazane In dichloromethane at 20℃; | |
96% | With boric acid In acetonitrile at 20℃; for 1.1h; | |
96% | With ammonium cerium (IV) nitrate; potassium iodide In dichloromethane; water at 20℃; | |
96% | With silica-coated iron nanoparticles-supported RuIII (OTf)Salophen In dichloromethane at 20℃; for 0.05h; | |
95% | at 20℃; for 1h; | |
95% | With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 20℃; for 0.33h; | |
95% | With p-toluenesulfonyl chloride In dichloromethane at 20℃; for 0.2h; | |
95% | With 1,4-diazabicyclo[2.2.2]octane tribromide supported on magnetic Fe3O4 nanoparticles In neat (no solvent) at 20℃; for 2.5h; | |
95% | With [nano-MCM-41(at)(CH2)3-1-methylimidazole]Br3 In dichloromethane at 20℃; for 0.5h; | General procedure for trimethylsilylation with HMDS catalyzed by [nano-MCM-41(at)(CH2)3-1-methylimidazole]Br3 General procedure: To a mixture of alcohol or phenol (1 mmol) and HMDS (2 mmol) in CH2Cl2 (5 ml) was added 10 mmol of [nano-MCM-41(at)(CH2)3-1-methylimidazole]Br3 with stirring at room temperature for the appropriate time (Table3). The progress of the reaction was monitored by TLC. At the end of the reaction, the solvent was evaporated, Et2O (10 mL) was added, and the catalyst was filtered. The filtrates were washed with brine, dried over Na2SO4, and concentrated under reduced pressure to afford the crude product. |
94% | With water; periodic acid; potassium iodide In dichloromethane at 20℃; for 0.0833333h; | |
94% | With silica supported Sn(Cl)4-n In acetonitrile at 20℃; for 0.0666667h; | |
94% | With L-Aspartic acid In acetonitrile at 20℃; for 0.833333h; | |
93% | at 20℃; for 1h; | |
93% | With melamine-N2,N4,N6-trisulfonic acid at 20℃; for 0.333333h; neat (no solvent); chemoselective reaction; | |
93% | With potassium fluoride incorporated on clinoptilolite nanoparticles In dichloromethane at 20℃; for 0.25h; chemoselective reaction; | General procedure for trimethylsilylation of alcohols with HMDS General procedure: To a mixture of alcohols or phenol (1.0 mmol) and HMDS (1.0 mmol) in CH2Cl2 (5 mL), catalyst KF/CP NPs (0.12 g, 20 mol%) was added. The mixture was stirred at room temperature for the specified time (Table 1). The progress of the reaction was monitored by GC or TLC. The reaction mixture was filtered and washed with hexane to recover the catalyst. The resulting solution was placed in a separating funnel and washed with water and hexane. The organic layer was dried with sodium bicarbonate, filtered, and concentrated in vacuo. The product was purified by column chromatography on silica gel eluting with ethylacetate-hexane mixtures. |
92% | With aminosulfonic acid at 20℃; for 0.25h; Neat (no solvent); | |
92% | With aluminum potassium sulfate dodecahydrate In acetonitrile at 20℃; for 0.5h; | |
89% | With 1-n-butylpyridinium tetrachloroferrate at 20℃; for 0.15h; | |
89% | With phenyltrimethylammonium tribromide In dichloromethane at 20℃; for 3h; chemoselective reaction; | |
85% | Stage #1: 1,1,1,3,3,3-hexamethyl-disilazane With 2Br3(1-)*C18H36N2O6*2H(1+) In acetonitrile at 20℃; for 0.0166667h; Stage #2: (2,4-dichlorophenyl)methanol In acetonitrile at 20℃; for 3h; | |
85% | With CoCl2(thiourea)2 In acetonitrile at 20℃; | A typical procedure for trimethylsilylation of benzylalcohol with HMDS/Co(tu)2Cl2 system General procedure: In a round-bottom flask (10mL) equipped with amagnetic stirrer,a solution of benzyl alcohol (1 mmol, 0.108 g) in CH3CN(1.5 mL) was prepared. HMDS (0.35 mmol, 0.056 g) was added and the solution was stirred at room temperature for 1 min. Tothe prepared solution, Co(tu)2Cl2 (3 mol%, 0.0085 g) was addedand stirring of the reactionmixturewas continuedfor 30 sec followedby the addition of second portion of HMDS (0.35 mmol,0.056 g). The mixture was continued to stirring for 20 sec atroom temperature. Progress of the reaction was monitored byTLC (eluent: n-hexane/EtOAc: 5/2). After completion of thereaction, H2O (3 mL) was added and the mixture was stirredfor 5 min. The silyl ether product was extracted with EtOAc(2 × 4 mL) and the organic layer was then dried over anhydrousNa2SO4.Evaporationof the solvent affordedthe pure benzyltrimethylsilylether in 99% yield (0.179 g, Table 3, entry 1). |
81% | With 1,3-dichloro-5,5-dimethylhydantoin In dichloromethane; acetonitrile at 20℃; for 1.41667h; | |
79% | With tribromomelamine In dichloromethane; acetonitrile at 20℃; for 0.5h; | |
74% | Stage #1: 1,1,1,3,3,3-hexamethyl-disilazane With C12H24KO6(1+)*Br3H(1-) In acetonitrile at 20℃; for 0.0166667h; Stage #2: (2,4-dichlorophenyl)methanol In acetonitrile at 20℃; for 0.916667h; | For the tetrahydropyanylation or trimethylsilylation of alcohols, to solution of the DHP(1 mmol) or HMDS(1 mmol) in CH3CN (5ml) were added {K*18-crown-6]Br3}n (0.001 mmol). The solution was stirred at room temperature for 1 min. Then alcohol(1 mmol for THP and 2 mmolf for TMS) was stirred at room temperature for an appropriate time (Table 2). After completion of the reaction, CH3CN was removed by water bath distillation. To the residue was added n-hexane or ethyl acetate(5 ml) and the mixture was filtered (the catalyst is insoluble in n-hexane and ethyl acetate). The filtrate was wahed with n-hexane or ethyl acetate (10 ml*2). The solvent was removed by distillation to yield pure products. |
99 % Chromat. | With sulfonic acid functionalized silica In dichloromethane at 20℃; for 0.916667h; | |
100 %Chromat. | With tin(IV)tetraphenylporphyrinato tetrafluoroborate In acetonitrile at 20℃; for 0.0166667h; | |
90 %Chromat. | With poly(4-vinylpyridinium tribromide) In acetonitrile at 20℃; for 0.166667h; | |
100 %Chromat. | With 5,10,15,20-tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate In acetonitrile at 20℃; for 0.0166667h; | |
90 %Chromat. | With [Ti(IV)(salophen)(OTf)2] In dichloromethane at 20℃; for 0.166667h; | |
100 %Chromat. | With C12H24KO6*I3(1-) In dichloromethane at 20℃; for 0.616667h; | |
100 %Chromat. | With tetrakis(p-aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate supported on graphene oxide nanosheets In acetonitrile at 20℃; for 0.0333333h; chemoselective reaction; | |
With cerium(IV) oxide In dichloromethane at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | [Example 8] Synthesis of sodium (((2,4-dichlorobenzyl)oxy)methyl) trifluoroborate To the mixture of sodium hydride (50 %, 130 mg, 2.6 mmol) and tetrahydrofuran (20 ml), 2,4-dichlorobenzyl alcohol (440 mg, 2.5 mmol) was added at 0C (an outer temperature), and the obtained reaction mixture was stirred at room temperature for 30 minutes. To the reaction mixture, a tetrahydrofuran (5 ml) solution of <strong>[166330-03-6]2-(bromomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane</strong> (92%, 300 mg, 1.3 mmol) synthesised in Production Example 2 was added at 0C (an outer temperature), and the obtained mixture was stirred at 60C (an outer temperature) for 1.5 hours. After cooling the reaction mixture to 0C (an outer temperature), sodium hydrogen fluoride (350 mg, 5.6 mmol) was added to the reaction mixture at the same temperature, followed by the dropwise addition of water (10 ml) at the same temperature. After stirring the reaction mixture for 1 hour at room temperature, the solvents were evaporated under reduced pressure. Acetone (40 ml) was added to the obtained residue, and the resultant was heated, cooled to room temperature, and then was filtered. The solvents were evaporated under reduced pressure from the filtrate, and then the obtained residue was washed with diethyl ether, thereby obtaining the entitled compound (190 mg, 53%). 1H-NMR Spectrum (CD3OD) delta(ppm): 2.85-2.97(2H, m), 4.52(2H, s), 7.30(1H, dd, J=2.4, 8.4Hz), 7.39(1H, d, J=2.0Hz), 7.55-7.59(1H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: formic acid With silica gel at 20℃; for 0.0166667h; Stage #2: (2,4-dichlorophenyl)methanol With silica gel at 110℃; for 0.0166667h; | |
90% | With p-toluenesulfonyl chloride at 20℃; for 0.166667h; neat (no solvent); | |
85% | With 1,3,5-tribromo-1,3,5-triazinane-2,4,6-trione In neat (no solvent) at 20℃; for 0.383333h; | Formylation of benzyl alcohol using formic acidcatalyzed by tribromoisocyanuric acid General procedure: To a mixture of the benzyl alcohol (1 mmol)and formic acid (3 mmol); 0.1 g tribromoisocyanuricacid (0.3 mmol) was added. The reaction mixturewas stirred at room temperature for 5 min. Aftercompletion of the reaction (TLC), dichloromethane(10 mL) was added to the reaction mixture andfiltered. The product was extracted with H2O (3×10mL), and the organic layer was dried over anhydrousNa2SO4salt. Evaporation of the solvent underreduced pressure to give the almost pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetra-n-butylammonium perchlorate; toluene-4-sulfonic acid In acetonitrile at 20℃; for 16.5h; Electrolysis; | |
75% | With tert.-butylhydroperoxide; 1-dodecylquinolin-1-ium hydrogen sulphate at 150℃; for 0.0583333h; Microwave irradiation; Sealed tube; | |
72% | With potassium-t-butoxide; Zn(2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline)Cl<SUB>2</SUB>; zinc In toluene at 100℃; for 16h; |
67% | With nickel(II) dibenzotetramethyltetraaza[14]annulene; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 100℃; for 36h; Inert atmosphere; Schlenk technique; | |
67% | With potassium hydroxide In para-xylene at 80℃; for 6h; | General procedure for the preparation of 2-(substituted)quinazolin-4(3H)-ones General procedure: In a two-necked flask, a mixture of o-aminobenzamide(1 mmol, 0.14 g), benzyl alcohol (1 mmol) in the presenceof catalyst: 0.05 g (3.10 mol%) for Fe3O4bagasse; 0.05 g(7.90 mol%) for MnO2bagasse; or 0.05 g for MnO2-Fe3O4bagasse, KOH (0.028 g, 0.5 mmol), and p-xylene (5 mL) wereheated for 6 h under stirring conditions and air blowing at80 °C. The progress of the reaction was monitored by TLC.After completion, the catalyst was separated by an externalmagnet and washed with water. After removing the organicsolvents, and crude product was separated to give final product. |
65% | With bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)] In 5,5-dimethyl-1,3-cyclohexadiene for 120h; Inert atmosphere; Reflux; | |
63% | With potassium-t-butoxide; oxygen; [Fe(2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline)Cl2] In toluene at 110℃; for 36h; | 4.4. Procedure for substituted quinazolin-4(3H)-ones synthesis General procedure: To an oven-dried 20.0 mL round bottom flask containing a magnetic stir bar, a mixture of catalyst 1 (4.0 mol%), tBuOK (0.5equiv.), alcohol (1.1 mmol), and 2-aminobenzamide (1.0 mmol) were added under air. To it, 5.0 mL dry toluene was added by syringe. The reaction vessel was then fitted with a water condenser and allowed to stir at 110 °C for 36 h, under air. The reaction was monitored by TLC. After the reaction was complete, the resulting mixture was concentrated under vacuum using a rotary vacuume vaporator and purified by silica gel column chromatography using petroleum ether/ethyl acetate (3:1). |
62% | With C18H11Cl3CuN4; sodium hydroxide In toluene at 90℃; for 36h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonium hydroxide; copper(I) bromide; at 80℃; for 24h; | The reactants used were <strong>[1777-82-8]2,4-dichlorobenzyl alcohol</strong> (i.e., R1 in the formula (I) was ortho, with two Cl) 1.0 mmol(177.0 mg), the experimental method and procedure were the same as in Example 1, ammonia water (1.8 mol / L) 5.0 mL, and the amount of catalyst cuprous bromide was5 mol% (7.2 mg), TEMPO was used in an amount of 5 mol% (7.8 mg), the reaction temperature was 80 C, the reaction time was 24 h, and the crude productPurification by column chromatography (petroleum ether: ethyl acetate = 10: 1) gave the pure title product, yielded 166.8 mg yield 97%. |
85% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonium acetate; oxygen; nitric acid; acetic acid; at 50℃; under 760.051 Torr; for 12h;Sealed tube; | General procedure: 0.5 mmol substrate, 1.5 mmol NH4OAc, 0.15 mmol TEMPO, 2 mL AcOH and 0.15 mmol HNO3 weresuccessively added to a dried 45 mL tube filled with 1atm oxygen. Then the reaction tube was sealed andplaced in a constant-temperature oil bath to perform the reaction for 12 h. Once the reaction time wasreached, the mixture was cooled to room temperature. Then the mixture was alkalized to pH 7-8 with sodiumhydroxide aqueous solution. GC analysis of organic phase provided the GC yields of the products.Subsequently, the crude product from another parallel experiment was purified by column chromatography,and identified by 1H-NMR, 1C-NMR or GC-MS |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.3% | With triphenylphosphine hydrobromide; sodium hydroxide In neat (no solvent) at 20℃; for 0.5h; Milling; | 2.3.2 Ferrocenyl-2-phenylethylene (2a) General procedure: A mixture of 0.214g (1mmol) ferrocenecarboxaldehyde, 0.108g (1mmol) benzalcohol, 0.343g (1mmol) triphenylphosphonium bromide, and 0.04g (1mmol) NaOH was ball milled at room temperature for 0.5h. The procedure was monitored by thin-layer chromatography. The mixture was extracted in 20mL dichloromethane. After filtration, the solvent was removed under vacuum to obtain the crude product. The residue was chromatographed on silica gel using petroleum ether with CH2Cl2 (1:1) as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With iron(III) sulfate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; In neat (no solvent); at 110℃; for 24h;Green chemistry; | General procedure: A mixture of 6 mmol of the alcohol or the amine and5 mmol o-phenylenediamine, o-aminophenol or o-aminothiophenol,10 mol % Fe2(SO4)3, 10 mol % TEMPO wasprepared in a 10 ml three-necked flask, and then stirred inopen air at 110 C for several hours, The reaction progresswas monitored by TLC. When the final reaction mixturecooled to room temperature, the crude products was directlypurified by column chromatography on silica gel using hexane/ethyl acetate (7:3) as eluent to afford the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.7% | With Au NCs/TiO2; oxygen; sodium hydroxide; In water; at 120℃; under 7500.75 Torr; for 6h;Autoclave; Green chemistry; | General procedure: The oxidation of alcohols was performed in an autoclave reactor equipped with a magnetic stirrer, thermocouple, automatic temperature controller and a pressure gauge. After the addition of desired amount of reactant, catalyst, water and NaOH, the autoclave was sealed. The atmosphere over the mixture was replaced with O2 for three times. Then the reactor was heated to the desired temperature with stirring. Subsequently, the pressure of O2 was charged to 1.0 MPa and kept constant during the reaction through feeding O2. When the reaction was finished, the reactor was cooled down to the ambient temperature. The reaction mixture was diluted with acetone to dissolve the products. After the catalyst was separated, the filtrate was acidified to pH of 2.0 by hydrochloric acid. The oxidation products were analyzed by gas chromatography equipped with a flame ionization detector. The isolated yield of carboxyl acid was obtained with the following procedure. The solvent of the mixture after acidification was removed through rotary evaporation. The pH of the residual was adjusted to 10.0 with NaOH (2.0 M), and then it was extracted with ethyl acetate for three times. The aqueous layer was acidified to pH 2.0 using HCl (6.0 M) and extracted with ethyl acetate. The organic layer was removed ethyl acetate through rotary evaporation to get the carboxylic acid. The carboxylic acid was dried overnight for calculation of the isolated yield. |
70% | With tetra-N-butylammonium tribromide; In acetonitrile; at 20℃; for 24h;Irradiation; | General procedure: In a 50ml Pyrex round-bottom flask, a mixture of alcohol (1mmol), TBATB (10-20mg, 0.02-0.04mmol) in 10ml of CH3CN was exposed to blue or violet light LED irradiation at room temperature under an air atmosphere with stirring. The progress of the photocatalytic oxidation reaction was monitored by TLC on silica gel plates. The reaction mixture externally irradiated until the alcohol was completely consumed. |
With tert.-butylhydroperoxide; In neat (no solvent); at 80℃; for 6h;Green chemistry; | General procedure: To a mixture of alcohol (1mmol) and electrospun PVA/Fe2O3/MoSB nanocomposite (0.005g), 0.6mmol t-BuOOH (57muL) was added under solvent free conditions and the reaction mixture was stirred at 80C for 6h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With fluorosulfonyl fluoride; sodium carbonate In ethyl acetate at 20℃; for 5h; | 1. General procedure for the SO2F2-promoted thiocyanation of alcohols tothiocyanates 2 General procedure: Alcohol substrates 1a-1ad (1.0 mmol, 1.0 equiv), ammonium thiocyanate (1.0 mmol, 1.0equiv), Na2CO3 (4.0 mmol, 4.0 equiv) and EtOAc (2.0 mL, 0.5 M) were sequentially addedinto an oven-dried reaction tube (30 mL) equipped with a stirring bar, the reaction tube wascovered with a plastic stopper before the SO2F2 gas was introduced into the stirring reactionmixture by slow bubbling through SO2F2 balloon at the room temperature for 5 h. Then, thereaction diluted with water and extracted with ethyl acetate (3× 25 mL). Then the combinedorganic layers were washed with brine, dried over anhydrous Na2SO4, and concentrated todryness. The residue was purified through silica gel chromatography using a mixture of ethylacetate and petroleum ether as eluent to afford the desired benzyl thiocyanates 2a-2ag. |
88% | With chloro-diphenylphosphine In acetonitrile for 0.333333h; Reflux; | Typical procedure for the conversion of 2,4-dichlorobenzyl alcoholto 2,4-dichlorobenzyl thiocyanate by use of chlorodiphenylphosphineand ammonium thiocyanate 2,4-Dichlorobenzyl alcohol (1 mmol, 0.177 g)was added to a flask containing a stirredmixture of ClPPh2 (1.2 mmol, 0.22 mL) and NH4SCN (2 mmol, 0.15 g) in refluxing MeCN(10 mL). Stirring was continued until TLC showed the completion of the reaction (20 min).The solvent was evaporated. Column chromatography of the crude mixture on silicagelusing hexane-ethyl acetate (9:1) as eluent gave 88% 2,4-dichlorobenzyl thiocyanate(0.192 g) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; sodium hydrogencarbonate In toluene at 110℃; for 24h; Inert atmosphere; | General Procedure for the Preparation of 3 General procedure: To a solution of [Cp*IrCl2]2 (0.0025 mmol), amino acid 2(0.65 mmol), and NaHCO3 (0.05 mmol) in toluene (3 mL) under an atmosphere of argon was added alcohol 1 (0.5mmol). The resulting mixture was stirred at 110 °C for a certain period of time. The reaction mixture was cooled tor.t., and H2O (5 mL) was then added. The resulting solution was extracted with EtOAc. Purification on silicon gel afforded the desired products 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; caesium carbonate; In toluene; at 130℃; for 12h; | A mixture of benzonitrile (103 mg, 1 mmol),[(IPr) AuNTf] (17 mg, 0.02 mmol, 2 mol%), tetrahydrofuran(0.5 ml) and H20 ((X 5 ml) were added sequentially to a 25 ml Schlenk reaction flask25mlSchlenk. After the mixture was reacted at 130C at 12 hours, cooled to roomtemperature, the solvent was removed in vacuo under reduced pressure. The [Cp * IrCl 2]2(8mg, 0.01mmol, 1mol%), 2,4- dichlorobenzyl alcohol (212mg, 1.2mmol), cesium carbonate(65mg, 0.2equiv.) And toluene (1ml) was added to the reaction flask, the mixture was at 130 C after the reaction was continued for 12 hours, cooled to room temperature. Thesolvent was removed rotary evaporation, then purified by column chromatography(developing solvent: ethyl acetate / petroleum ether) to give pure title compound Yield:84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tribromomelamine In neat (no solvent) at 20℃; for 1.16667h; Green chemistry; chemoselective reaction; | Formylation of 4-tert-butylbenzyl alcohol General procedure: To the stirred mixture of 4-tert-butyl benzyl alcohol (1 mmol, 0.164 g) and ethyl formate (2 mL), tribromo melamine (0.1 mmol) was added without additional solvents. The resulting mixture was stirred at room temperature for 30 min. The reaction was monitored by TLC. On completion of reaction, the product was extracted with CH2Cl2 (5 mL × 4). The organic layer was separated, dried over anhydrous Na2SO4 (1.5 g), and concentrated under reduced pressure. Finally, the organic solvents were evaporated, and 4-tert-butylbenzyl formate was obtained in 92% yield. The identity of the product was confirmedby comparing the physical and spectral data with those of the known compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0 - 20℃; | |
78% | With boron trifluoride diethyl etherate In acetonitrile at 20℃; | General experimental procedure for synthesis of sulfinate esters General procedure: To a solution of alcohol (1 mmol), TosMIC 2 (1.2 mmol) in acetonitrile (2 mL), BF3 · Et2O (0.3 mmoL) was added at room temperature and the reaction mixture was stirred at room temperature and monitored by TLC. After completion of the reaction, ethyl acetate was added washed with water, brine, and then dried over Na2SO4. The organic layer was dried under reduced pressure. The crude product was purified by column chromatography to obtain the corresponding sulfinate as the product. |
68% | With bismuth(III) bromide; acetic acid In nitromethane at 20℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); caesium carbonate In tert-Amyl alcohol for 6h; Reflux; | |
90% | With C16H14IrN2O3; caesium carbonate In tert-Amyl alcohol for 6h; Reflux; | 8 3-(2,4-dichlorophenyl)-1-phenylpropan-1-one Acetophenone (120mg, 1mmol), cat.1 (5.4mg, 0.01mmol, 1.0mol%), cesium carbonate (33mg, 0.1mmol,0.1equiv.), 2,4- dichlorobenzyl alcohol (195mg, 1.1mmol) and tert-amyl alcohol (ImL) were sequentially added to a 5mL round bottomed flask.After the reaction mixture was refluxed in air for six hours, cooled to room temperature. The solvent is removed by rotary evaporation, then purified by column chromatography (developingOpen solvent: petroleum ether / ethyl acetate) to give the pure title compound Yield: 90% |
86% | With potassium phosphate tribasic trihydrate; C39H32Cl2N5PRu In tert-Amyl alcohol at 120℃; for 4h; Inert atmosphere; Schlenk technique; |
85% | With [(Cp*IrCl)2(thbpym)][Cl]2; potassium hydroxide In water for 12h; Reflux; | 9 Example 9: 3-(2,4-Dichlorophenyl)-1-phenyl-1-acetone Combine 2,4-dichlorobenzyl alcohol (88.5mg, 0.5mmol), acetophenone (78.1mg, 0.65mmol), [(Cp*IrCl)2(thbpym)][Cl]2(2.5mg, 0.0025mmol, 1mol Ir%), potassium hydroxide (28mg, 0.5mmol, 1 equiv), and water (1mL) were sequentially added to a 5mL round bottom flask. The reaction mixture was refluxed in air for 12 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and then the pure target compound was obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate), yield: 85%. |
83% | With C38H36Cl4Ir2N4; caesium carbonate In tert-Amyl alcohol for 12h; Reflux; | 6 Example 6: 3-(2,4-dichlorophenyl)-1-phenylpropan-1-one Acetophenone (60 mg, 0.5 mmol),Cat. [Ir] (5.4 mg, 0.005 mmol, 1.0 mol%),Cesium carbonate (33 mg, 0.1 mmol, 0.2 equiv.),2,4-dichlorobenzyl alcohol (106 mg, 0.6 mmol)And tert-amyl alcohol (1 mL) were successively added to a 5 mL round bottom flask.The reaction mixture was refluxed in air for 12 hours,Cool to room temperature.Rotate the solvent to remove the solvent,And then passed through a column chromatography (developing solvent:Petroleum ether / ethyl acetate) to give the pure title compound,Yield: 83% |
80% | With [(Cp*IrCl)2(4,4′,6,6′-tetrahydroxy-2,2′-bipyrimidine)][Cl]2; potassium hydroxide In water at 100℃; for 12h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With barium manganate; triphenylphosphine In acetonitrile at 80℃; for 24h; stereoselective reaction; | General procedure for the one-pot tandem oxidation-Wittig reaction General procedure: General procedure for the one-pot tandem oxidation-Wittig reaction To a flask containing BaMnO4 (1.2 mmol, 300 mg)and the alcohol (1 mmol) in CH3CN (5 mL) were added PPh3(1.2 mmol, 315 mg) and ethyl bromoacetate (1.2 mmol, 0.13 mL) and the mixturewas stirred at 80 °C for 24 h. Then the obtained mixture was filtered and theresulting solution was subjected to column chromatography using n-hexane/ethylacetate to isolate the pure products in 78-93% isolated yields with highstereoselectivity. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With triethylamine; N-tosylimidazole In N,N-dimethyl-formamide at 70℃; for 6h; | 2,4-Dichloro-1-(thiocyanatomethyl)benzene (2f) General procedure: In a round-bottom flask (50 mL) equipped with a condenser, amixture of an appropriate alcohol (0.01 mol), TsIm (0.012 mol),KSCN (0.015 mol) and Et3N (0.015 mol) in anhydrous DMF (10 mL)was heated at 70 °C for the times indicated in Table 2. In most cases,darkening of the reaction media occurred, and heating was continueduntil TLC monitoring indicated no further improvement in theconversion (Table 2). After completion of the reaction, the mixturewas diluted in water (100 mL), CHCl3 (100 mL) was added and theorganic phase was washed with water (4 × 100 mL). The organiclayer was evaporated in vacuo to obtain the crude product which waspurified by short column chromatography on silica gel eluted withn-hexane:EtOAc |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: phenylacetylene With chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I); water; silver trifluoromethanesulfonate In 1,4-dioxane at 120℃; for 1h; Microwave irradiation; Stage #2: (2,4-dichlorophenyl)methanol With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; potassium <i>tert</i>-butylate In 1,4-dioxane at 130℃; for 2h; Microwave irradiation; | 8 3-(2,4-dichlorophenyl)-1-phenylpropan-1-one the [(IPr)AuCl](6mg,0.01mmol,1mol%)AgOTf2.6mg,0.01mmol,1mol%Phenylacetylene (102mg, 1mmol), 1,4- dioxane (1ml) and water (36ul, 2equiv.) Were successively added to 5ml microwave tube.After the reaction mixture was microwaved at 120 reactor for one hour, cooled to room temperature.Thereto was added [Cp * IrCl2]2(8mg, 0.01mmol, 1mol%), potassium tert-butoxide (34mg, 0.3mmol, 0.3equiv.), 2,4- dichlorobenzyl alcohol (212mg, 1.2mmol).After the reaction mixture was microwaved at 130 reactor and then reacted for 2 hours, cooled to room temperature.Filtered, and solvent was removed by rotary evaporation, then purified by column chromatography (developing solvent: petroleum ether / ethyl acetate) to give the pure title compound Yield: 89% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: benzonitrile With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; butyraldehyde oxime In toluene at 100℃; for 6h; Schlenk technique; Green chemistry; Stage #2: (2,4-dichlorophenyl)methanol With caesium carbonate In toluene at 130℃; for 12h; Schlenk technique; Green chemistry; | 7 Embodiment 7: N - (2, 4 - dichloro) benzamide The nitrile (103 mg, 1mmol), butyric aldehyde wo (96 mg, 1 . 1mmol), [Cp * IrCl2]2(8 mg, 0 . 01mmol, 1 µM %), toluene (1 ml) are added to the 25 ml Schlenk reaction bottle. The mixture 100 °C reaction under 6 hours, cooling to room temperature. The 2,, 4 - dichlorobenzyl alcohol (229 mg, 1 . 3mmol) and cesium carbonate (65 mg, 0.2 equiv.) is added to the bottle in the reaction, the mixture 130 °C then continue to react under 12 hours, cooling to room temperature. The solvent is removed by rotary evaporation, then through the column chromatography (developing solvent: ethyl acetate/petroleum ether) to obtain the pure target compound, yield: 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 1-phenethyl alcohol With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O) In tert-Amyl alcohol at 20℃; for 6h; Reflux; Stage #2: 2,4-dichlorobenzyl alcohol With Cs2CO3 In tert-Amyl alcohol for 6h; Reflux; | 8 Example 8: 3- (2,4-Dichlorophenyl) -1-phenyl-1-propanone DL-1-phenylethanol (122 mg, 1.0 mmol), cat. [Ir] (5.3 mg, 0.01 mmol, 1 mol%) and tert-amyl alcohol (1 mL) were successively added to a 5 mL round bottom flask. The reaction mixture was refluxed in air for 6 hours and then cooled to room temperature. Then, cesium carbonate (33 mg, 0.1 mmol, 0.1 equiv.) And 2,4-dichlorobenzyl alcohol (195 mg, 1.1 mmol) were added, refluxed in air for 6 hours and then cooled to room temperature. The solvent was removed by rotary evaporation and then the title compound was obtained by column chromatography (developing solvent: petroleum ether / ethyl acetate) in a yield of 90% |
68% | With nickel(II) dibenzotetramethyltetraaza[14]annulene; potassium-t-butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 17h; Inert atmosphere; Sealed tube; | General Procedure for Nickel-Catalyzed Alkylation of 1-Phenylethanol with VariousBenzylalcohols. General procedure: Under an argon atmosphere, a mixture of KOtBu (1.0 mmol) andcatalyst 1a (3.0 mol%) was taken in an oven-dried sealed tube fitted with a magnetic stir bar.The reaction vessel was then capped with a rubber septum. A long neck needle connectedwith a balloon filled with argon was then inserted into the sealed tube. 1.3 mmol of thesubstituted benzylalcohol and 1.0 mmol of 1-phenylethanol dissolved in 5.0 mL of degassedxylene was added through a syringe. The sealed tube was then placed in an oil bath preheatedat 120 °C for 17 h. Once the reaction was completed, the resulting mixture was concentrated,volatiles were removed under vacuum, and the residue was purified by flash columnchromatography (silica gel) using diethyl ether/hexane (1:20) as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With dipotassium peroxodisulfate; palladium dichloride In chlorobenzene at 130℃; for 20h; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.1% | With dichloro sulfoxide In dichloromethane for 3h; Reflux; | 1.1 Step 1: The compound of formula IIIa (50.0 g, 0.28 mol) was dissolved in 250 mL of dichloromethane, and thionyl chloride (47.0 g, 0.40 mol) was added dropwise under ice-water bath cooling. After the dropwise addition was completed, the ice bath was removed, the temperature was slowly raised to reflux, and the reaction was continued for 3 hours. The solvent and excess thionyl chloride were recovered by atmospheric distillation, followed by distillation under reduced pressure to obtain 2,4-dichlorobenzyl chloride (52.6 g), a compound of formula IVa, with a yield of 96.1%. |
92% | With phosphorus trichloride In dichloromethane; N,N-dimethyl-formamide at 60 - 80℃; | 6 Example 6 To a 100 mL round bottom flask was added 2,4-dichlorobenzyl alcohol (17.7 g, 0.1 mol) and dichloromethane (30 mL) andDMF (1 mL), followed by the addition of phosphorus trichloride (4.68 g, 0.034 mol) and slowly warming to reflux (60-80 ° C) Should be 2 ~ 3h, TLC detection shows the disappearance of raw materials, distillation was 2,4-dichlorobenzene 17.99g, yield 92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: phosphorus tribromide / dichloromethane; N,N-dimethyl-formamide / 80 °C 2.1: ethanol; water 3.1: sulfuric acid; acetic acid / 100 - 130 °C 4.1: trifluoroacetic anhydride / water / 0.17 h 4.2: 3 h / 20 - 30 °C / Cooling with ice |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With sodium tetrahydroborate; nickel(II) chloride hexahydrate In methanol at 20℃; for 2h; chemoselective reaction; | General procedure for chemoselective reduction of 1,1-diacetaes to corresponding benzyl alcohols General procedure: In a typical experiment, 4-chlorobenzaldicetate (2.0 mmol, 0.5 g), methanol (10 mL), and NiCl2 · 6H2O (10.0 mmol, 2.440 g) were placed in a 100 mL round-bottomed flask fitted with a reflux condenser, a CaCl2 guard tube and mounted over a magnetic stirrer. NaBH4 (30.0 mmol, 1.169 g) was added cautiously and formation of black precipitate of nickel boride was observed immediately. The reaction mixture was stirred vigorously at room temperature and its progress was monitored by TLC using ethyl acetate: petroleum ether (10:90) as eluent. TLC showed complete disappearance of the starting material after 3 h. The reaction mixture was quenched with methanol (20 mL) and filtered through a celite pad (∼1 in.). The celite residue was washed with methanol (2 5 mL). The filtrate was concentrated to nearly half volume on rotavapor and diluted with water (20 mL) and extracted with diethyl ether (3 10 mL). The combined ether extract was dried over anhyd. MgSO4 and concentrated on a Buchi rotavapor to give 4-chlorobenzyl alcohol (3a) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With sodium ethanolate; copper diacetate In dimethyl sulfoxide at 110℃; for 24h; | 7 Example 7 take 0.5 mmol of 4-methylbenzamide oxime, 1.0 mmol of 2,4-dichlorobenzyl alcohol in a reaction tube, and then Add 0.05mmol Cu(OAc)2, 0.5mmol C2H5ONa, 2.5mL DMSO in turn, stir the reaction at 110 ° C for 24h, and produce The extract was extracted with ethyl acetate, dried over anhydrous sodium The volume ratio of the agent was petroleum ether: ethyl acetate = 20:1) purified to a white solid.That is, 5-(2,4-dichlorophenyl)-3-(4-methylphenyl)-1,2,4-oxadiazole. Yield 56% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triphenylphosphine In tetrahydrofuran at 0 - 20℃; for 24.5h; Inert atmosphere; | 1.1.3. General procedure for the Mitsunobu synthesis of amines 1 General procedure: To a stirred solution of the tert-butyl 4-hydroxybenzylcarbamate (5.0 mmol) in dry THF under nitrogen atmosphere, the corresponding benzyl alcohol (5.0 mmol) and PPh3 (5.0 mmol) were added at 0°C. Afterwards, DIAD or DEAD (5.0 mmol) was added dropwise for over 10 min. The reaction mixture was stirred at 0°C for 20 min and then at rt for 24 h. The solvent was removed under reduced pressure and the product was purified by flash chromatography (petroleum ether/EtOAc 5:1) giving the corresponding amines 1q-ad. The procedures above were used in order to further use the compound as free amine or its trifluoroacetic/hydrochloric salt. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium t-butanolate In toluene at 150℃; for 24h; Sealed tube; | General procedure for NaOtBu-catalyzed esterification ofamides. General procedure: To a dry 35 mL sealed tube with a stir bar, amide (0.5 mmol), NaOtBu (0.1 mmol), phenol/alcohol (1.0 mmol) and toluene (5.0 mL) were added. After sealed with a Teflon-lined cap, the reaction mixture was stirred at 150 °C for 24 h. Then the mixture was cooled to room temperature and quenched with H2O (5.0 mL). The mixture was separated and extracted with ethyl acetate (EA) (15 mL×3). The combined organic layer was dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography with ethyl acetate/petroleum ether to give the desired product. More experimental details and characterizations are available in the Supporting Information online. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With ZrCl4-Mg(ClO4)2 composite In neat (no solvent) at 20℃; for 0.133333h; | Typical experimental procedure for the onepotsynthesis of benzyl acetate General procedure: A mixture of 4-methoxy benzyl alcohol (1b, 1 mmol),acetic acid (3 mmol), 2 mol% ZrCl4-Mg(ClO4)2 catalyst was stirred at room temperature for the time specified inTable 5. After completion of reaction (monitored by TLC),the solid or liquid product was filtered and washed with25 ml diethyl ether and water. The organic layer wassuccessively washed with saturated NaHCO3 solution. Theorganic layer was dried over anhydrous sodium sulfateand evaporated of the solvent under reduced pressure toprovide a residue which was passed through a short padof silica gel (60-120 mesh) using hexane as eluent to providethe analytically pure acylated product (please seeAppendix S1).Note that as we know that esterification is a reversiblereaction, to avoid this reversible we used every time activatedmolecular sieves as dehydrating agent/waterabsorbing agent. We have not mentioned it in our actualexperimental procedure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydrogen bromide / water / 20 - 120 °C 2: potassium carbonate / N,N-dimethyl-formamide / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tert.-butylhydroperoxide In acetonitrile at 60℃; for 4h; | 2.4. Procedure for dehydrogenative amide synthesis reaction via couplingof alcohol and amine General procedure: The experiment was initially carried out by stirring 1 mmol each of alcohol and amine in 3 mL of CH3CN with 20 mg of catalyst in presence of 100 μL of 70% tBuOOH for 1 h at 60 °C. After 1 h of reaction added another 120 μL of tBuOOH solution under refluxing condition at the same temperature and stirred the reaction for another 3 h. The progress of the reaction was monitored by thin layered chromatography (TLC) (in different ratios of ethyl acetate, EtOAc, and n-hexane). After the completion, the product was extracted by addition of 20 mL EtOAc and10 mL distilled H2O. The organic products were extracted from the solvent (EtOAc) using a rotary evaporator. The pure product was separated through the silica (60-120 mesh) column chromatography using EtOAc and n-hexane as eluent. The final products were characterized by1H and 13C NMR (Nuclear Magnetic Resonance) recorded in CDCl3(deuterated chloroform) solvent. The NMR spectra are provided in SI (Supporting Information). |
68 % | With tert.-butylhydroperoxide In acetonitrile at 60℃; | 2.4. Procedure for dehydrogenative amide synthesis reaction via couplingof alcohol and amine General procedure: The experiment was initially carried out by stirring 1 mmol each of alcohol and amine in 3 mL of CH3CN with 20 mg of catalyst in presence of 100 μL of 70% tBuOOH for 1 h at 60 °C. After 1 h of reaction added another 120 μL of tBuOOH solution under refluxing condition at the same temperature and stirred the reaction for another 3 h. The progress of the reaction was monitored by thin layered chromatography (TLC) (in different ratios of ethyl acetate, EtOAc, and n-hexane). After the completion, the product was extracted by addition of 20 mL EtOAc and10 mL distilled H2O. The organic products were extracted from the solvent (EtOAc) using a rotary evaporator. The pure product was separated through the silica (60-120 mesh) column chromatography using EtOAc and n-hexane as eluent. The final products were characterized by1H and 13C NMR (Nuclear Magnetic Resonance) recorded in CDCl3(deuterated chloroform) solvent. The NMR spectra are provided in SI (Supporting Information). |
68 % | With tert.-butylhydroperoxide In acetonitrile at 60℃; | 2.4. Procedure for dehydrogenative amide synthesis reaction via couplingof alcohol and amine General procedure: The experiment was initially carried out by stirring 1 mmol each of alcohol and amine in 3 mL of CH3CN with 20 mg of catalyst in presence of 100 μL of 70% tBuOOH for 1 h at 60 °C. After 1 h of reaction added another 120 μL of tBuOOH solution under refluxing condition at the same temperature and stirred the reaction for another 3 h. The progress of the reaction was monitored by thin layered chromatography (TLC) (in different ratios of ethyl acetate, EtOAc, and n-hexane). After the completion, the product was extracted by addition of 20 mL EtOAc and10 mL distilled H2O. The organic products were extracted from the solvent (EtOAc) using a rotary evaporator. The pure product was separated through the silica (60-120 mesh) column chromatography using EtOAc and n-hexane as eluent. The final products were characterized by1H and 13C NMR (Nuclear Magnetic Resonance) recorded in CDCl3(deuterated chloroform) solvent. The NMR spectra are provided in SI (Supporting Information). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 3-(2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorophenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid With benzotriazole-1-yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 2h; Stage #2: 2,4-dichlorobenzyl alcohol In dichloromethane at 20℃; for 12h; | 4.2 The second step reaction: Preparation of 2,4-dichlorobenzyl 3-(2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorophenyl)-5 - methyl-4,5-dihydroisoxazole-5-carboxylate 0.98 g (0.0022 mol) of 3-(2-chloro-5-(3-chloro-5-( Trifluoromethyl)pyridin-2-yl)-4-fluorophenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid, 0.56g (0.0044mol) di(isopropyl) ) ethylamine, 1.15 g (0.0022 mol) of benzotriazol-1-yl-oxytripyrrolidinophosphorus hexafluorophosphate were dissolved in 15 ml of dichloromethane in turn. The reaction mixture was stirred for 2 hours. To the above solution was added 0.45 g (0.0025 mol) of (2,4-dichlorophenyl)methanolat room temperature. Stirring was continued for 12 hours at room temperature. 10 ml of water was added to the reaction system, and the phases were separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The organic phase was desolvated under reduced pressure and subjected to column chromatography (eluent: ethyl acetate: petroleum ether (1:2) to obtain 1.30 g of the product with a yield of 87%. |
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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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