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CAS No. : | 1746-13-0 | MDL No. : | MFCD00008644 |
Formula : | C9H10O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | POSICDHOUBKJKP-UHFFFAOYSA-N |
M.W : | 134.18 | Pubchem ID : | 74458 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.11 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 42.07 |
TPSA : | 9.23 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) : | -5.03 cm/s |
Log Po/w (iLOGP) : | 2.29 |
Log Po/w (XLOGP3) : | 2.94 |
Log Po/w (WLOGP) : | 2.25 |
Log Po/w (MLOGP) : | 2.37 |
Log Po/w (SILICOS-IT) : | 2.49 |
Consensus Log Po/w : | 2.47 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.77 |
Solubility : | 0.228 mg/ml ; 0.0017 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.8 |
Solubility : | 0.215 mg/ml ; 0.0016 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.96 |
Solubility : | 0.149 mg/ml ; 0.00111 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.21 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With oxygen; ozone; sodium hydroxide In dichloromethane at -65℃; | General procedure: (1) An ozone–oxygen mixture was bubbled through a solution of 10.00 mmol of ethers Ia or Ib in a mixture of 20 mL of 2.5 M NaOH in MeOH and 80 mL of CH2Cl2 at –65°C until blue color appeared. The reaction mixture was purged with argon, MTBE (70 mL) and water (30 mL) were added, stirred for 1 hat ambient temperature. The organic layer was separated, the aqueous layer was extracted with MTBE. The combined organic extracts were dried with Na2SO4. After evaporation, ether I produced 1.66 g of mixture of compounds II and III in 72 : 28 ratio (according to GLC and NMR data), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) gave 1.07 g (60percent) of ester IIa and 0.47 g (32percent) of aldehyde III. After evaporation, ether Ib produced 1.61 g of a mixture of compound IIb and IIIb in 88 : 12 ratio (according to GLC and NMR), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) resulted in 1.34 g (80percent) of ester IIb and 0.16 g (12percent) of aldehyde IIIb. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | Stage #1: at -78℃; Stage #2: at -50 - 20℃; for 24 h; |
General procedure: (2) An ozone–oxygen mixture was bubbled through a solution of 10.00 mmol of ethers Ia or Ib in50 mL of MeOH at –78°C until blue color appeared.The reaction mixture was purged with argon, 3.88 g(35.00 mmol) of NH2C(O)NHNH2 HCl. HCl was added at –50°C. The mixture was stirred at ambient temperature for 24 h. The reaction mixture was evaporated, the residue was dissolved in 100 mL of CHCl3, washed with 2 (to pH ≈ 7), and dried with Na2SO4. After evaporation, ether I produced 1.86 g of a mixture of compounds II and IV in 40 : 60 ratio(according to GLC and NMR), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) afforded0.74 g (42percent) of ester IIa and 1.09 g (56percent) of acetal IV.After evaporation, ether Ib produced 1.64 g of a mixture of compounds IIb and IVb in 25 : 75 ratio (according to GLC and NMR data), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) gave 0.40 g (24percent)of ester IIb and 1.15 g (63percent) of acetal IVb. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 4-methylmorpholine N-oxide In water; acetone at 20℃; for 3.5h; Inert atmosphere; | For Table 3, Entries 1-10 General procedure: A mixture of alkene (250 mol), 5% Os/CR11 (9.5 mg, 2.50 mol, 1 mol%), NMO (32.2 mg, 275mol), and acetone-H2O (7 : 3, 0.5 mL) in a 15 mL-test tube was stirred under an Ar atmosphere atroom temperature. After the specific time [the consumption of the starting material was confirmedby TLC analysis (hexane-EtOAc)], the mixture was filtered through a Celite pad, and the pad waswashed with acetone (30 mL) and concentrated in vacuo. The residue was purified by columnchromatography on silica gel (hexane-EtOAc) to give the corresponding diol |
95% | With 4-methyl-morpholine; osmium(VIII) oxide; dihydrogen peroxide In acetone at 20℃; | |
94% | With 1,4-diaza-bicyclo[2.2.2]octane; K2<OsO2(OH)4>; oxygen In water; <i>tert</i>-butyl alcohol at 50℃; for 18h; |
91% | With 4-methylmorpholine N-oxide In water; acetone at 20℃; for 8h; Inert atmosphere; | General procedure: To an acetone-H2O (2:1, v/v) solution (3 mL) of olefin (1 mmol) was added a magnetic osmium catalyst (0.02 mmol) and N-methylmorpholine N-oxide (NMO; 1.3 mmol) successively at room temperature under an argon atmosphere. After stirring the resulting mixture, the dihydroxylation reaction was completed (monitored by TLC). After the reaction mixture was slightly evaporated to remove acetone, a magnetic osmium catalyst was separated by magnetic decantation using an external magnet followed by washing with H2O, and the recovered magnetic osmium catalyst was reused for subsequent dihydroxylation reactions. |
88% | With 4-methyl-morpholine; dmap; dihydrogen peroxide In acetone for 1.5h; | |
87% | With N,N'-ethane-1,2-diyl-N,N'-[3,5-bis[3,5-bis(3,5-dimethoxybenzyloxy)benzyloxy]benzyloxy]-N,N,N',N'-tetramethylammonium dibromide; C120H134N2O28(2+)*O4Os(2-); water; 4-methylmorpholine N-oxide In acetonitrile at 20℃; for 0.5h; Inert atmosphere; | |
85% | With O4Os(2-)*C123H141N3O28(2+); 4-methylmorpholine N-oxide In water; acetonitrile at 20℃; for 2h; Inert atmosphere; | |
82% | With potassium osmate(VI); water; 4-methylmorpholine N-oxide In <i>tert</i>-butyl alcohol at 25℃; for 18h; | 2.A EXAMPLE 2; [00281] A. Conversion of Phenyl Allyl Ether to 2,3-dihydroxypropyl Ether of Phenol; [00282] Phenyl allyl ether (1.0 mL) (from Aldrich) was suspended in 10 mL of H2O and 10 mL of tert-butanol in a 100-mL round-bottom flask, and 3.32 mL of N-methyl morpholine N-oxide (50 wt % aqueous; 1.1 molar equivalents) was added to the flask. The resulting reaction mixture was stirred at room temperature, and 0.025 g of K2OsO4.2H2O (2 mol %) was added to the mixture. The reaction mixture was allowed to stir for 18 hours. Then 200 mg of Na2SO3 and 0.2 g of diatomaceous earth were added to the mixture. The reaction mixture was stirred an additional 1 hour and then filtered. The filtrate was extracted three times with 1 volume of ethyl acetate. The resulting extracts were combined, washed twice with 1 volume of 1 N HCl, washed with one volume of water, dried over NaHCO3 and Na2SO4, filtered, rotary evaporated, and dried under vacuum. The resulting white solid (1.00 g; 82% yield), which was analyzed by 1H NMR spectroscopy, was 98% pure 2,3-dihydroxypropyl ether of phenol. |
81% | With dihydrogen peroxide; triethylammonium acetate; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate In water; acetone at 20℃; for 16h; | |
80% | Stage #1: allyl phenyl ether With sodium periodate; acetic acid; lithium bromide at 95℃; for 18h; Stage #2: With potassium carbonate In methanol at 25℃; for 24h; | |
80% | With 4-methylmorpholine N-oxide In water; acetone at 100℃; for 3h; | General procedure for the dihydroxylation of alkenes General procedure: alkenesTo a stirred solution of alkene (1, 1 mmol) in a mixture ofacetone:H2O 2:1 (3 mL) in a pressure tube, OsO2-Fe3O4(10 mg,0.08% of osmium) and NMO (234 mg, 2 mmol) were added. Theresulting mixture was stirred at 100C during 3 h. The catalyst wasremoved by a magnet and the resulting solution was extracted withether. The organic phases were dried over MgSO4, and the solventswere removed under reduced pressure. The product was usuallypurified by chromatography on silica gel (hexane/ethyl acetate)to give the corresponding products 2 or 4. Physical and spectro-scopic data as well as literature for all compounds are includedas Appendices A and B. FT-IR spectra were obtained on a Nicoletimpact 400D spectrophotometer. NMR spectra were recorded ona Bruker AC-300 apparatus (300 MHz for1H and 75 MHz for13C)using CDCl3as a solvent and TMS as internal standard for1H and13C; chemical shifts are given in (parts per million) and couplingconstants (J) in Hertz. Mass spectra (EI) were obtained at 70 eVon a spectrometer Agilent GC/MS-5973N, giving fragment ions inm/z with relative intensities (%) in parentheses. Thin layer chro-matography (TLC) was carried out on DC-Fertigfolien ALUGRAMplates coated with a 0.2 mm layer of silica gel; detection by UV254light, staining with phosphomolybdic acid [25 g phosphomolybdicacid, 10 g Ce(SO4)2·4H2O, 60 mL of concentrated H2SO4and 940 mLH2O]. Column chromatography was performed using silica gel 60of 35-70 mesh. |
79% | With water; oxygen; palladium diacetate; sodium carbonate at 100℃; for 24h; Autoclave; | |
With formic acid; dihydrogen peroxide Erhitzen des Reaktionsprodukts mit aethanol. Kalilauge; | ||
With potassium osmate(VI) dihydrate; streptavidin D128E mutant; potassium carbonate; potassium hexacyanoferrate(III) In water at 20℃; for 24h; Enzymatic reaction; | ||
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In water; acetone; <i>tert</i>-butyl alcohol at 20℃; Cooling with ice; | ||
Multi-step reaction with 2 steps 1: 1-(tert-butylsulfonyl)-2-iodosylbenzene / dichloromethane / 24 h / 0 °C 2: water / tetrahydrofuran / 24 h / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sulfuric acid; sodium bromide; dibenzoyl peroxide In tetrachloromethane at 50℃; for 1h; | 13-19 Preparation of 3-phenoxybromopropane After putting carbon tetrachloride 200ml into the reaction kettle, start stirring, add 26.8g of 2-propenyl phenyl ether, 1g of benzoyl peroxide and 30.6g of sodium bromide successively, slowly add 18g of sulfuric acid dropwise when warming up to 50°C, dropwise add After the reaction was completed, the reaction was incubated for 1 h. After the reaction was completed, the temperature was lowered to room temperature. Then, the organic layer was washed with sodium carbonate aqueous solution, washed with water until neutral, dried and concentrated under reduced pressure to obtain 41.0 g of 3-phenoxybromopropane with a yield of 95%. |
With hydrogen bromide; dibenzoyl peroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With palladium 10% on activated carbon; hydrogen; at 20℃; for 24h;Neat (no solvent); | General procedure: In a 25-mL round-bottom flask were placed the substrate (1.00 mmol) and 10% Pd/C (10 wt % of the substrate), and the mixture was stirred using a magnetic stirrer at room temperature under a hydrogen atmosphere (balloon) for 24 h Et2O (20 mL) was added, and the mixture was passed through a membrane filter (Millipore, Millex-LH, 0.45 mum) to remove the catalyst. The filtrate was concentrated in vacuo to give the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With palladium diacetate; Dess-Martin periodane In water; acetonitrile at 50℃; Inert atmosphere; | |
80% | With chromium(VI) oxide; palladium dichloride In water; acetonitrile at 20 - 60℃; for 12h; | 4.2 General procedure for oxidation of terminal olefins General procedure: To a stirred solution of olefin (0.4mmol) in CH3CN (3.5mL) and H2O (0.5mL) were added PdCl2 (3.6mg, 0.02mmol, 5mol%) and CrO3 (20mg, 0.6mmol, 0.5equiv) at room temperature. The reaction mixture was warmed to 60°C and stirred for specified time (see Tables 5-7) in a closed flask. The reaction mixture was then filtered through a small pad of silica gel and washed with EtOAc and the filtrate concentrated. The residue in some cases contained virtually pure compound and no further purification was necessary. In other cases the residue was purified by silica gel column chromatography using petroleum ether/EtOAc as an eluent to afford the methyl ketones. |
76% | With iron(III) sulfate hydrate; palladium dichloride In water; acetonitrile at 45℃; for 6.5h; Inert atmosphere; |
58% | With tert.-butylhydroperoxide; palladium(II) bis(diketonate) In benzene at 56℃; | |
47% | With perchloric acid; oxygen In water; N,N-dimethyl-formamide at 20℃; for 5h; | |
With 5C24H52N(1+)*PV2Mo10O40(5-); palladium dichloride In [D3]acetonitrile; water-d2 at 25℃; | 2.3 General procedure for Wacker-type oxidation of allyl phenyl ethers General procedure: A Pd catalyst (10 mol%) and a POM (3.0 mol%) re-oxidation mediator were added to the CH3CN/H2O (7:1, v/v) mixed solution containing allyl phenyl ether (0.10 M) at room temperature. The mixture was heated to target temperature and stirred for 16 h under ambient air. After the reaction, the mixture with biphenyl as an internal standard was quantified by GC-FID (Shimadzu, GC-2014). The temperature of the GC-FID program was kept 120 for 2 min, raised to 280 with a ramp rate of 10 /min and then kept for 2 min. The same procedure was used for 1H NMR spectroscopic analysis but with the use of CD3CN/D2O (7:1, v/v) instead of CH3CN/H2O (7:1, v/v) as a reaction solution. Acetophenone was used as an internal standard for the quantification of products in the 1H NMR spectroscopic analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With deuterium In toluene | |
86% | With deuterium In methanol at 25 - 27℃; for 16h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen at 30℃; for 12h; P1 medium for bacteria growth; Title compound not separated from byproducts; | ||
46 % ee | With whole E. coli cells expressing monooxygenase from Herbaspirillum huttiense HhMO and NADH-dependent flavin oxidoreductase PsStyB In aq. phosphate buffer; octane at 37℃; Green chemistry; Enzymatic reaction; Overall yield = 11 percent; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With Silphos; iodine In N,N-dimethyl-formamide at 20℃; for 0.166667h; | |
90% | With bis(cyclopentadienyl)titanium dichloride; magnesium In tetrahydrofuran for 12h; Ambient temperature; | |
90% | With tetra-(n-butyl)ammonium iodide; triphenylphosphine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile for 0.5h; Heating; |
90% | With sodium iodide; tin(ll) chloride In ethanol for 0.0833333h; Reflux; Green chemistry; | General procedure for De oxygenation of aliphatic and aromatic epoxide, chalcone epoxide, nitro styrene epoxide and nitrochromene epoxide by novel SnCl 2 / NaI reagent: General procedure: To a solution epoxide (1mmol) and NaI (3mmol) in absolute alcohol (5ml), SnCl2 (2mmol) was added in a several portions. The mixture was stirred at reflux temperature and the progress of reaction was monitored by TLC. Within 2-10 min the reaction mixture is poured in ice-water, precipitation obtained, stirred for 10 min and filtered the solid, dried to obtained pure products 2a-12a/ 1b-17b/1c-10c and 1d- 10d with 85-96% yield. |
88% | With molybdenum(V) chloride; zinc In tetrahydrofuran at 20℃; for 1.5h; | 4.2. General procedure General procedure: Zinc powder (131mg 2.0mmol) and molybdenum(V) chloride (238mg, 1.0mmol) weremixed in THF (5 mL). The resulting mixture was stirred to produce a solution of the lowvalentmolybdenum-zinc complex. 4-Chlorostyrene thiirane (171mg, 1.0mmol) was thenadded to this solution and the reaction mixture was stirred for 0.5 h at room temperature.The progress of the reaction was followed by TLC. On completion, the solvent wasremoved under reduced pressure and the residue was extracted successively with ethylacetate, washed with water and brine. The organic fractions were separated and dried overanhydrous Na2SO4. The crude product was subjected to flash column chromatography onsilica gel (hexane:ethyl acetate = 10:1) to afford 4-chlorostyrene (132mg, 95%). All of theproducts are known compounds and their identification was based on spectral comparison with authentic samples [26]. |
87% | With zirconium(IV) chloride; sodium iodide In acetonitrile for 0.0166667h; Heating; | |
87% | With [(PhNH)P2(NPh)2]2NPh; iodine In acetonitrile at 20℃; for 0.666667h; | Typical procedure for conversion of oxaranylmethyl phenyl ether to 3-phenoxy-1-propene with P3/I2: While stirring a mixture of I2 (2.2 mmol, 0.556 g) and P3 (0.55 mmol,0.419 g) in CH3CN (3 mL), oxaranylmethyl phenyl ether (1 mmol, 0.15 g) was added at room temperature. TLC or GC monitoring of the reaction mixture showed the completion of the reaction after 38 min. The reaction mixture was filtered to remove the heterogeneous phosphazane oxide. Evaporation of the solvent followed by the addition of 10% aqueous sodium thiosulfate solution removed the excess of iodine. The organic layer was then extracted by CH2Cl2 (3 × 10 mL) and dried over anhydrous Na2SO4 and evaporated.Column chromatography of the crude product on silica-gel using n-hexane as the eluentgave 1,3-phenoxy-1-propene in 87% yield (0.107 g). 1H-NMR (CDCl3, 250 MHz): δ 4.41(td, 2H, J = 1,5, 5.5 Hz), 5.15-5.19 (d, 1H), 5.26-5.34 (d, 1H), 5.8-6.2 (m, 1H), 6.80-6.87(m, 3H), and 7.13-7.20 (m, 2H) ppm. 13C-NMR (CDCl3, 62.5 MHz): δ 68.7, 114.7, 117.5,120.8, 129.4, 133.4, and 158.6 ppm. |
83% | With carbon monoxide In water at 27℃; for 24h; chemoselective reaction; | |
83% | With carbon monoxide; water at 27℃; for 24h; chemoselective reaction; | |
With iodine; triphenylphosphine In N,N-dimethyl-formamide at 20℃; | ||
With N-chloro-succinimide; triphenylphosphine In acetonitrile for 0.5h; Heating; | ||
93 %Chromat. | With isopropyl alcohol In toluene at 110℃; for 6h; Inert atmosphere; | |
With titanium(IV) oxide In isopropyl alcohol; acetonitrile at 29.84℃; for 48h; Photolysis; | ||
25 %Spectr. | With bis(N,N-diethyldithiocarbamato)dioxomolybdenum(VI); 2,4-dimethyl-3-pentanol In toluene at 160℃; for 48h; regioselective reaction; | |
Multi-step reaction with 2 steps 1: potassium thioacyanate 2: molybdenum hexacarbonyl / toluene / 2.5 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With hydrogen sulfide; triphenylphosphine In [D3]acetonitrile for 6h; Ambient temperature; | |
93% | With tri-n-butyl-tin hydride In benzene Heating; | |
87% | With molybdenum hexacarbonyl In toluene for 2.5h; Reflux; chemoselective reaction; | 4.2. General procedure General procedure: A equimolar mixture of 4-chlorostyrene thiirane (171 mg, 1.0 mmol) and Mo(CO)6(264 mg, 1.0 mmol) were stirred in toluene (5 mL) at reflux for 1 hr. The progress of thereaction was followed by TLC. After completion, the reaction mixture was concentrated ona rotary evaporator, extracted successively with ethyl acetate, washed with water and brine.The organic layer was separated and dried over anhydrous Na2SO4. The crude product waspurified by column chromatography on a silica gel (hexane: ethyl acetate = 10:1) to afford4-chlorostyrene (132 mg, 95%). All products are known compounds and were identifiedby comparison of their spectroscopic data with those of authentic samples [25]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With di-isopropyl azodicarboxylate; dendric phosphine In dichloromethane at 20℃; for 1h; | |
85% | With N3P3[O(CH2CH2O)23-C6H4-p-PPh2]6; diethylazodicarboxylate In dichloromethane at 20℃; for 2h; | |
82% | With potassium hydroxide In dimethyl sulfoxide at 100℃; for 8h; | 3 Preparation of propenyl phenyl ether Put 200 mL of dimethyl sulfoxide into the reaction kettle, start stirring, add 18.8 g of phenol, 22.4 g of potassium hydroxide and 23.2 g of allyl alcohol in turn, heat up to 100 °C and keep the reaction for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The insolubles were removed, the filtrate was concentrated, chloroform was added, washed with sodium hydroxide aqueous solution, washed with water until neutral, dried and concentrated under reduced pressure to obtain 22.0 g of propenyl phenyl ether with a yield of 82%. |
65% | With diazene-1,2-diylbis(morpholinomethanone); tributylphosphine In tetrahydrofuran at 20℃; for 16h; Inert atmosphere; | Typical procedure: General procedure: A solution of phenol (47 mg, 0.5 mmol, 1 equiv), benzylalcohol (108 ll, 1.0 mmol, 2 equiv) and PBu3 (250 ll, 1.0 mmol, 2 equiv) inanhydrous THF (7 mL) was stirred at RT for 2 min. ADDM (256 mg, 1.0 mmol,2 equiv) was added in one portion. The reaction mixture was stirred at RT for16 h under an inert atmosphere. The solvent was concentrated under reducedpressure, and then the residue was adsorbed onto silica gel from CH2Cl2, andpurified by flash column chromatography (eluent: Hex/EtOAc, 9:1) |
7% | With titanium(IV) oxide; molybdenum(VI) oxide at 103℃; for 3h; Sealed tube; | |
With PEG3400-PPh3 conjugate; diethylazodicarboxylate 1.) CH2Cl2, r.t., 20 min, 2.) r.t., 2 h; Yield given. Multistep reaction; | ||
87 % Chromat. | With titanium(IV) isopropylate; palladium diacetate; triphenylphosphine In benzene at 50℃; | |
62 % Chromat. | With quinoline-2-carboxylic acid In dichloromethane at 70℃; for 5h; | |
at 95℃; for 4h; | A COMPARATIVE EXAMPLE A A mixture of 4.7 g (0.05 mole) of phenol, 0.182 g (0.005 equivalents) of chloro(cyclopentadienyl)bis(triphenylphosphinyl) ruthenium(II), and 14.52 g of allyl alcohol (0.25 mole) under a nitrogen atmosphere is stirred at 95° C. After 4 hours, gas chromatography analysis shows that the conversion of phenol to phenyl allyl ether is only 11%, and the majority of the reacted allyl alcohol has converted into a self condensation product methylpentanal confirmed by gas chromatography/mass spectrometry analysis. | |
With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II); silver(I) 4-methylbenzenesulfonate; toluene-4-sulfonic acid In toluene at 60℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetrabutylammonium borohydride; zinc(II) iodide In dichloromethane at 25℃; for 16h; | |
98% | With tetrabutylammonium borohydride; zinc(II) iodide In dichloromethane at 20℃; for 20h; | |
98% | With cobalt(II) bromide-[1,2-bis(diphenylphosphino)ethane]; zinc(II) iodide; zinc In dichloromethane for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With palladium diacetate; copper diacetate; lithium acetate In N,N-dimethyl-formamide at 100℃; for 4h; | |
53% | With C8H20N2O2Pd*2C2H4O2 In N,N-dimethyl-formamide at 50℃; for 3h; regioselective reaction; | 4.2 General procedure for palladium-catalyzed oxidative Heck reaction of alkene and arylboronic acid (Tables 2 and 3) General procedure: Under air atmosphere, a mixture of olefin (0.5 mmol), arylboronic acid (1.0 mmol), alkoxopalladium complex (4 mg, 2 mol %), oxidant (1.0 mmol) and DMF (1.5 mL) was stirred at 50 °C for 3 h. The reaction mixture was cooled to room temperature, and then directly purified by preparative thin layer chromatography on silica gel using petroleum ether/ethyl acetate as an eluent to give desired compounds. |
36% | With tetrabutylammomium bromide; potassium carbonate; copper(II) sulfate; palladium dichloride In water at 85℃; for 20h; Schlenk technique; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With N-Bromosuccinimide In dichloromethane; dimethyl sulfoxide at 20℃; for 0.0833333h; Inert atmosphere; | 2. Experimental General procedure: We began with the reaction of styrene (1) with NBS. Initially, 1 (1 equiv.) and NBS (2 equiv.) were allowed to stir in DMSO (3 mL) under nitrogen at room temperature. Instantaneous generation of yellow colour and its decolouration prompted us to check the reaction progress. To our delight, the formation of two products was observed through TLC. The spectroscopic analysis confirmed the formation of vicinal dibromostyrene (2) and bromohydrin 2' (Table 1). 1H NMR and 13C NMR of both the compounds were in full agreement with the literature. In order to get vicinal dibromostyrene (2) as the sole product, the reaction was carried out under various conditions. |
87% | With [bis(acetoxy)iodo]benzene; lithium bromide In tetrahydrofuran at 20℃; for 0.5h; | |
81% | With hydrogen bromide; dimethyl sulfoxide In water; ethyl acetate at 60℃; for 0.5h; |
72% | With dimethyl sulfoxide; ethylene dibromide at 80℃; for 18h; | |
69% | With μ-(R)-BINAP μ-1-phenylhexane-1,3,5-triketone bis[(acetonitrile)palladium(II)] tetrafluoroborate; oxygen; lithium bromide; copper(ll) bromide In tetrahydrofuran; water at 23℃; for 24h; Sealed tube; | |
62% | With dioxane*Br2 at 20℃; for 0.5h; | |
With pyridinium hydrobromide perbromide In 1,2-dichloro-ethane at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With bis(1,5-cyclooctadiene)diiridium(I) dichloride; bis-diphenylphosphinomethane In dichloromethane at 20℃; for 24h; | |
83% | With lithium hexamethyldisilazane In toluene at 100℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; | |
82% | With silver(I) acetate In toluene at 120℃; for 18h; Schlenk technique; Inert atmosphere; stereoselective reaction; |
81% | With tris[3,5-bis(trifluoromethyl)phenyl]-borane In neat (no solvent) at 80℃; for 40h; Glovebox; Inert atmosphere; regioselective reaction; | |
80% | With (bis(diisopropylphenyl-imidazol-2-ylidene)phenyl)CoN<SUB>2</SUB> In benzene at 20℃; for 1h; chemoselective reaction; | |
46% | With fac-[Mn((1,2-bis(di-isopropylphosphino)ethane))(CO)3(CH2CH2CH3)] In tetrahydrofuran at 80℃; for 24h; Sealed tube; Inert atmosphere; | |
With [(1,3-bis(2,4,6-trimethylphenyl) imidazol-2-ylidene)Fe(CO)4] In neat (no solvent) at 20℃; for 24h; Inert atmosphere; UV-irradiation; Schlenk technique; regioselective reaction; | ||
With Wilkinson's catalyst In dichloromethane for 15h; Schlenk technique; Inert atmosphere; | 4.3 2-Alkylhydroquinone synthesis method C (using pinacolborane) General procedure: A flame-dried 100-mL Schlenk flask was charged with 1.95mmol of pinacolborane and 3mL of dichloromethane. Liquid alkene (1.77mmol) was added to the flask followed by 0.040mmol (36mg) of Wilkinson's catalyst. The neck of the flask was rinsed with about 2mL of dichloromethane to ensure that the all of the catalyst entered the reaction mixture. The reddish solution was stirred for about 15h under a nitrogen atmosphere. Water (5mL) was then added and stirred for 10min to quench any unreacted pinacolborane. Then 1,4-benzoquinone (127mg, 1.18mmol) was dissolved in 2mL of dichloromethane and added to the flask. Silver nitrate (40mg, 0.24mmol) and potassium persulfate (960mg, 3.54mmol), and the neck of the flask was rinsed with about 5mL of water to ensure that the all of the reagents had entered the reaction mixture. Trifluoroacetic acid (5mL) was then added and the flask was opened to air. The biphasic mixture was stirred under reflux (50°C) for 24h. The mixture was then cooled to RT, diluted with 20mL of dichloromethane, separated, and extracted with additional dichloromethane (2×20mL). The organic layers were combined, washed with water (3×20mL), dried over MgSO4, filtered, and concentrated by rotary evaporation to afford a dark oil. The crude intermediate 2-alkyl-1,4-benzoquinone was dissolved in 15mL of THF and 0.7g Raney nickel was added. A balloon of hydrogen was fitted, and the mixture was stirred at room temperature under a hydrogen atmosphere for 1h. The solution was then diluted with 40mL of ether, filtered through diatomaceous earth, dried over MgSO4, and concentrated by rotary evaporation to yield a dark brown oil. Silica gel column chromatography using flash-grade absorbent and eluting with 30% ethyl acetate in hexanes, afforded after evaporation of the eluent, the pure 2-alkylhydroquinone as a white solid. | |
With silver(I) acetate In toluene at 120℃; for 24h; Schlenk technique; Inert atmosphere; | ||
With C20H37CoN3OP2(1+)*BF4(1-) In benzene at 25℃; for 24h; Inert atmosphere; | ||
8 %Spectr. | Stage #1: allyl phenyl ether; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane With C38H32Cl3CoN2P3 In tetrahydrofuran for 0.0166667h; Inert atmosphere; Stage #2: With potassium triethylborohydride In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetraethylammonium chloride In N,N-dimethyl-formamide at 80℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With N-Bromosuccinimide; water In dimethyl sulfoxide at 20℃; | 1 [0128] To a room temperature water cooled solution of allyl phenyl ether (4) (Aldrich, 1.00 g., 7.45 mmol) in 5 mL DMSO: H2O (4:1) is added NBS (1.45 g., 8.15 mmol) as a solid. After 5-10 minutes, the reaction is added to a separation funnel with 100 mL Et2O and washed three times with 100 mL water, then 100 mL brine solution. The ether layer is dried over MgSO4 and concentrated in vacuo to yield a pale yellow oil (1.59 g., 92%), which is used as is without further purification. |
92% | With N-Bromosuccinimide In water; dimethyl sulfoxide at 20℃; for 0.0833333 - 0.166667h; | 5 1-bromo-3-phenoxy-propan-2-ol (5) To a room temperature water cooled solution of allyl phenyl ether (4) [(ALDRICH,] 1.00 g. , 7.45 mmol) in 5 mL DMSO: H20 (4: 1) was added NBS (1.45 g. , 8.15 mmol) as a solid. After 5-10 minutes, the reaction was added to a separation funnel with 100 mL [ET2O] and washed three times with 100 mL water, then 100 mL brine solution. The ether layer was dried over [MGS04] and concentrated in vacuo to yield a pale yellow oil (1.59 g. , 92%), which was used as is without further purification. |
With N-Bromosuccinimide; ammonium acetate; water In acetone at 40℃; for 0.5h; Flow reactor; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In einer 100 ml Batchapparatur wurden in 275ml Methanol/Wasser (1/10 v/v) 2,7g (0,02mol) 2-Allylphenol aufgenommen und auf 5C abgekuehlt und mit Entschaeumer versetzt. Danach wurden 0,96g (0,02mol) Ozon durch die Loesung durchgeleitet. Nach beendeter Ozonolyse wurde der Ozonstrom abgeschaltet und 15 Minuten lang mit Stickstoff inertisiert. Anschliessend wurde der Reaktionsansatz in einen 2-Halskolben mit Rueckflusskuehler ueberfuehrt und auf 60C erhitzt. Die Reaktion wurde mittels Duennschichtchromatographie kontrolliert. Nach beendeter Reaktion (5h) wurde 2 mal mit je 100ml Essigester extrahiert und die vereinigten organischen Extrakte ueber Natriumsulfat getrocknet. Nach dem Eindampfen der Loesung erhielt man 2,8g Hydroxyphenylessigsaeure (93% d.Th.) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In einer 100 ml Batchapparatur wurden in 250ml Wasser 2,7g (0,02mol) 2-Allylphenol aufgenommen und auf 15C abgekuehlt und mit Entschaeumer versetzt. Danach wurden 0,96g (0,02mol) Ozon durch die Loesung durchgeleitet. Nach beendeter Ozonolyse wurde der Ozonstrom abgeschaltet und 15 Minuten lang mit Stickstoff inertisiert. Anschliessend wurde der Reaktionsansatz in einen 2-Halskolben mit Rueckflusskuehler ueberfuehrt und auf 60C erhitzt. Die Reaktion wurde mittels Duennschichtchromatographie kontrolliert. Nach beendeter Reaktion wurde bei 50C mit 3 mal mit je 50ml Toluol extrahiert und die bereinigten Extrakte auf Rueckflusstemperatur erhitzt und gleichzeitig das gebildete Wasser mittels Wasserabscheider abgetrennt. Anschliessend wurde das Toluol durch Eindampfen entfernt. Es wurden 2,2g 2-Coumaron (85% d.Th.) erhalten |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With oxygen; palladium diacetate; potassium iodide at 100℃; for 24h; Autoclave; | |
81% | With dichloro bis(acetonitrile) palladium(II); silver(I) nitrite; copper(II) choride dihydrate; oxygen; acetic anhydride In nitromethane at 35℃; for 16h; Darkness; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Stage #1: 4-iodocumene With N,N'-(1,2-ethanediylidene)bishexahydro-1H-azepin-1-amine; potassium phosphate; palladium diacetate In N,N-dimethyl-formamide Inert atmosphere; Stage #2: allyl phenyl ether In N,N-dimethyl-formamide at 20 - 50℃; for 24h; Inert atmosphere; | |
64% | With N,N'-(1,2-ethanediylidene)bishexahydro-1H-azepin-1-amine; potassium phosphate; palladium diacetate In N,N-dimethyl-formamide at 20 - 50℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A solution of NaIO4 (0.5 mmol) and NaClO2 (2.0 mmol) in water (5 mL) was added to a solution containing olefin (1.0 mmol) in acetonitrile (5 mL). To the resulting suspension was added 4 wt % aq solution of osmium tetroxide (0.01 mmol, 61 muL), and the mixture was stirred at the room temperature for 14 h. Then 150 mol % of isopropyl alcohol (115 muL) and potassium hydroxide (98 mg) were added to the reaction mixture and the mixture was stirred for another 8 h. Organic products were extracted with TBME (6 mL × 3) and the combined organic layer was dried (anhyd MgSO4). Before running a new reaction cycle, the remaining aqueous layer was neutralized to pH 6-7 by adding 1 N HCl (0.5-0.8 mL) and stirring for 10 min. Then a new substrate (1.0 mmol), NaIO4 (0.5 mmol), NaClO2 (2.0 mmol) and acetonitrile (5 mL) were added, and the mixture was stirred for 14 h as the second run of the reaction. The extracted residue was dried with anhyd MgSO4, and filtered. The organic solution was directly analyzed with HPLC after addition of an internal standard or purified by flash column chromatography to yield the desired product. refText |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: allyl phenyl ether With dimethylsulfide borane complex In dichloromethane at 20℃; for 5h; Darkness; Inert atmosphere; Stage #2: With dihydrogen peroxide; sodium hydroxide In water at 20℃; for 20h; | 4.1.2. General procedure for preparation of alcohols (15A-B) General procedure: To a solution of the corresponding allyl ethers (14A) or (14B) (3.92 mmol) in dichloromethane (35 mL) was added a 1M borane-dimethylsulfide solution in dichloromethane (5.5 mL, 5.50 mmol). The mixture was vigorously stirred at room temperature, under nitrogen atmosphere and protected from light. After 5 h, the excess of reductive agent was quenched with methanol (1 mL) and 10% NaOH solution (3 mL) and 30% aqueous H2O2 (3 mL). The suspension was stirred at room temperature for 20 h. The mixture was extracted with dichloromethane (3 × 25 mL) and the combined organic extracts were washed with 10% aqueous hydrochloric acid solution, and brine. After drying under sodium sulfate and evaporation of the solvent under reduced pressure, the residue was purified by silica gel column chromatography after elution with hexane-chloroform 1:1 to give the corresponding primary alcohols (14A) and (14B), as described in Supplementary Material. |
Multi-step reaction with 3 steps 1: triethyl borane; triisopropylsilanethiol / tetrahydrofuran / 20 °C 2: boron trifluoride diacetate / dichloromethane / 6 h / 20 °C 3: potassium fluoride; 3-chloro-benzenecarboperoxoic acid / N,N-dimethyl-formamide / 4 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With selenium(II) chloride In tetrachloromethane at -20 - 20℃; chemoselective reaction; | 14 Typical procedure for the preparation of selenides 2,3 and 5-7. General procedure: A solution of SeBr2 was prepared from Se (0.395 g, 5 mmol) and Br2 (0.8 g, 5 mmol) in CCl4 (20 ml). The solution of SeBr2 thus prepared was added dropwise over 1 h to a solution of propargyl phenyl ether (1.32 g, 10 mmol) in CCl4 (50 ml) cooled to -20 °C. After stirring for 2 h at -20 °C, the cooling bath was removed and the mixture was allowed to warm and stirred at room temperature for 1 h. The solvent was evaporated and the crude product was purified by chromatography on a short column of silica gel (eluent:hexane) to give selenide 3 (2.43 g, 96% yield) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With selenium(II) chloride In chloroform at -60℃; Reflux; regioselective reaction; | 12 Typical procedure for the preparation of annulated products 1 and 4. A solution of SeCl2 was prepared from Se (0.79 g, 10 mmol) and SO2Cl2 (1.35 g, 10 mmol) in CHCl3 (20 ml). The solution of SeCl2 thus prepared and a solution of allyl phenyl ether (1.34 g, 10 mmol) in CHCl3 (20 ml) were added separately and simultaneously with stirring over 1 h to a flask containing CHCl3 (80 ml) cooled to -60 °C. The cooling bath was removed and the mixture was allowed to warm to room temperature with stirring and then heated at reflux for 5 h. The solvent was evaporated and the crude product was purified by chromatography on a short column of silica gel (eluent: hexane) to give heterocycle 4 (2.21 g, 90% yield) as a yellow oil. |
75% | With selenium(II) chloride In chloroform at -60 - 60℃; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium carbonate In acetone at 60℃; for 12h; | 4 Preparation of propenyl phenyl ether Put 200 mL of acetone into the reaction kettle, start stirring, add 18.8 g of phenol, 41.5 g of potassium carbonate and 31.2 g of diallyl carbonate in turn, heat up to 60 °C for 12 hours, and cool down to room temperature after the reaction is completed, and filter to remove insoluble matter , concentrated the filtrate, added 1,2-dichloroethane, washed with sodium hydroxide aqueous solution, washed with water until neutral, dried and concentrated under reduced pressure to obtain 20.1 g of propenyl phenyl ether with a yield of 78%. |
With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine In N,N-dimethyl-formamide at 20 - 25℃; for 18h; Inert atmosphere; | ||
93 %Spectr. | With N,N'-dimethylimidazolium-2-carboxylate In acetonitrile at 160℃; for 2h; Microwave irradiation; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(benzonitrile)palladium(II) dichloride; silver(I) nitrite; copper(II) choride dihydrate; oxygen; In nitromethane; tert-butyl alcohol; at 20℃; under 760.051 Torr; for 6h; | Example 4 Oxidation of Directed Olefins Example 4.1 General Procedures Example 4.2.1 Procedure a for Preparative Scale (0.5 Mmol) Oxidation of Alkenes (Isolation) [0178] The preparative scale procedures used for directed olefins was the analogous to Procedure (A) used as for unbiased olefins, except for reduced catalysts loadings: PdCl2(PhCN)2 (0.05 mmol, 19.2 mg), CuCl2.2H2O (0.05 mmol, 8.5 mg) and NaNO2 (0.025 mmol, 1.7 mg). Example 4.2.2 Procedure B for Analytical Scale (0.2 Mmol) Oxidation of Alkenes (NMR Analysis) [0179] The NMR analytical procedures used for directed olefins was the analogous to Procedure (C) used as for unbiased olefins, except for reduced catalysts loadings: PdCl2(PhCN)2 (0.02 mmol, 7.7 mg), CuCl2.2H2O (0.02 mmol, 3.6 mg) and NaNO2 (0.01 mmol, 0.7 mg). Example 4.2.3 Procedure for Tsuji-Wacker Oxidations [0180] PdCl2 (1.8 mg, 0.01 mmol) and CuCl (9.9 mg, 0.1 mmol) were weighed into an 8 mL vial. DMF (0.7 mL) and water (0.1 mL) were both added to the vial. The vial was sparged with oxygen (1 atm, balloon) for 3 minutes. The solution was stirred for another 1 h before alkene (0.1 mmol) was added. The reaction was stirred for at room temperature (20-25 C.). After 24 h, the reaction mixture was quenched by addition of water (ca. 10 mL) and extracted 3 times with dichloromethane (ca. 5 mL). The combined organic layers were subsequently washed with a saturated solution of LiCl(aq). After volatiles were removed under reduced pressure, nitrobenzene was added as an internal standard. The resulting solution was subsequently subjected to 1H NMR analysis to determine yield and selectivity. Example 4.2.4 Intramolecular Competition Experiments [0181] Each initial rate measurement was made in duplicate and the values averaged. The following procedure was used: [0182] PdCl2(PhCN)2 (0.02 mmol, 7.7 mg), CuCl2.2H2O (0.02 mmol, 3.6 mg) and NaNO2 (0.01 mmol, 0.7 mg) were weighed into a 8 mL vial charged with a stir bar. The vial was sparged for 1 minute with oxygen (1 atm, balloon). Premixed and oxygen saturated tert-BuOH (3 mL) and MeNO2 (0.2 mL) was added followed by the addition of pre-mixed alkenes (0.1 mmol of each alkene). The solution was saturated with oxygen by an additional 10 seconds of sparging. The reaction was then allowed to stir at room temperature (20-25 C.) for 10 minutes. Next, the reaction was quenched by addition of pyridine (5 muL) and then water (10 mL) and extracted three times with dichloromethane (ca. 5 mL). The combined organic layers were subsequently washed with a saturated solution of NaHCO3 (ca. 5 mL) and dried over Na2SO4. The resulting solution was subjected to 1H NMR analysis to determine relative rates. Benzonitrile signals were used as an internal standard to confirm that conversion was <15% in each case. The selectivity of each substrate under the nitrite-modified Wacker was independently measured using procedure B. Example 4.3 Results and Discussion [0183] A series of alkene-containing phenyl ether substrates of varying chain length were subjected to both nitrite-modified Wacker conditions and Tsuji-Wacker conditions to evaluate the influence of proximal oxygen-containing functional groups on the regioselectivity (Table 4). The high anti-Markovnikov selectivity exhibited by an unbiased substrate (1-dodecene) under nitrite-modified Wacker conditions was markedly enhanced as the ether moiety approached the alkene (Table 4). Exceptional aldehyde selectivity (>90%) was observed with both the allylic (n=1) and homoallylic phenyl ether (n=2), despite the significant difference in the innate regioselectivity of the two substrates under Tsuji-Wacker conditions. Moreover, substrates bearing a distal ether functional group (n=3) retained the high regioselectivity observed in the unfunctionalized systems. These encouraging results were consistent with a catalyst-controlled process in which the selectivity was further enhanced by proximal heteroatoms. Consistent with earlier observations with unbiased aliphatic substrates (e.g., Example 2), both AgNO2 and NaNO2 were found to be effective sources of nitrite; however, with oxygenated alkenes, NaNO2 proved to be more effective and inexpensive source of nitrite. [TABLE-US-00004] TABLE 4 Influence of phenoxy group proximity on regioselectivity in Wacker- type conditions. Nitrite-Wacker (A) Tsuji-Wacker (B) n = 1 95% 41% FontWeight="Bold" FontSize="10" n = 2 92% ?5% n = 3 75% ?5% n = 4 79% ?5% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With C34H43Cl2N3O2Ru In dichloromethane at 35℃; for 12h; Inert atmosphere; | 2 4.5 Catalytic study of the ruthenium carbenes 10 General procedure: The general procedure for metathesis reactions with ruthenium carbenes 10 was performed as follows: a certain amount of ruthenium carbene catalyst 10 (0.0005-0.0125mmol) and a solution of the substrate (0.5mmol) in 1.0mL dry CH2Cl2 (or toluene) was mixed in a reaction flask under nitrogen. The reaction mixture was stirred for 0.3-24h. At the end of the reaction (monitored by thin-layer chromatography (TLC)), the catalysts were separated by silica gel chromatography using CH2Cl2 as the eluent to remove trace amounts of Ru residues. Conversions were estimated by 1H NMR spectroscopy and obtained by comparing the ratios of the integrals of the starting materials with those of products. The catalytic activities of ruthenium carbene 10 for a variety of substrates are shown in Table 1. |
94 %Spectr. | With C33H40Cl2N2O3Ru In dichloromethane at 35℃; for 24h; Inert atmosphere; | 4.6. Catalytic study of the ruthenium carbenes 17, 18 and 19 General procedure: The general procedure for metathesis reactions with ruthenium carbenes 17, 18 and 19 was performed as follows: a certain amountof ruthenium carbene catalyst 17 (or 18, or 19) (0.0005 mmol) and asolution of the substrate in 1.0 mL dry CH2Cl2 (or toluene) was mixed in a reaction flask under nitrogen. The reaction mixture was stirred for 0.3-24 h. At the end of the reaction (monitored by thin layer chromatography (TLC)), the catalysts were separated by silica gel chromatography using CH2Cl2 as the eluent to remove trace amounts of Ru residues. Conversions were estimated by 1H NMR spectroscopy and obtained by comparing the ratios of the integrals of the starting materials with those of products. The catalytic activities of ruthenium carbene 17, 18 and 19 for a variety of substrates are shown in Table 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | Stage #1: ethyl 1-phenylpyrazole-4-carboxylate With zinc dichloro(N,N,N′,N′-tetramethylethylenediamine); phenylmagnesium bromide In tetrahydrofuran at 0℃; for 0.05h; Schlenk technique; Inert atmosphere; Stage #2: allyl phenyl ether With iron(III)-acetylacetonate; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran at 0℃; for 48h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80%; 12% | With oxygen; ozone; sodium hydroxide; In dichloromethane; at -65℃; | General procedure: (1) An ozone-oxygen mixture was bubbled through a solution of 10.00 mmol of ethers Ia or Ib in a mixture of 20 mL of 2.5 M NaOH in MeOH and 80 mL of CH2Cl2 at -65C until blue color appeared. The reaction mixture was purged with argon, MTBE (70 mL) and water (30 mL) were added, stirred for 1 hat ambient temperature. The organic layer was separated, the aqueous layer was extracted with MTBE. The combined organic extracts were dried with Na2SO4. After evaporation, ether I produced 1.66 g of mixture of compounds II and III in 72 : 28 ratio (according to GLC and NMR data), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) gave 1.07 g (60%) of ester IIa and 0.47 g (32%) of aldehyde III. After evaporation, ether Ib produced 1.61 g of a mixture of compound IIb and IIIb in 88 : 12 ratio (according to GLC and NMR), column chromatography (Si2, PE, PE : MTBE = 5 : 1, 4 : 1) resulted in 1.34 g (80%) of ester IIb and 0.16 g (12%) of aldehyde IIIb. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate In acetic acid; acetonitrile at 30℃; for 48h; Schlenk technique; regioselective reaction; | 4.2. Typical experimental procedure for the Pd(OAc)2-catalyzed direct decarboxylative coupling of alkynyl carboxylic acids with allyl ethers General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30°C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
75% | With oxygen; palladium diacetate; acetic acid In acetonitrile at 30℃; for 48h; | 2 Specific Example 2 A mixture of 48.1 mg (0.3 mmol)4- (methylphenyl) - propiolic acid, 80.5 mg (0.6 mmol)Allyl phenyl ether,6.7 mg (0.03 mmol) of palladium acetate,24.7 mg (0.06 mmol) of DPPP was added to the reaction tube,A further 2 mL of a mixed solution of acetonitrile and glacial acetic acid (3: 1 by volume)And then the reaction tube filled with O2.30 ° C for 48 hours,After the reaction is cooled,Saturated aqueous sodium bicarbonate solution and dichloromethane extraction,Dispensing,The organic layer was dried over MgSO4,filter,The filtrate is steamed,Removing the solvent,The residue was chromatographed on silica gel,With leaching of petroleum ether and ethyl acetate in a volume ratio of 150: 1,Collect the effluent from the actual gradient,TLC detection,The effluent containing the product was combined,The solvent was distilled off by rotary evaporator,Dried in vacuo to give a pale yellow liquid55.8 mg of 1- (4-methylphenyl) -3-methylene-4-phenoxybutyne,Yield 75%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate In acetic acid; acetonitrile at 30℃; for 48h; Schlenk technique; regioselective reaction; | 4.2. Typical experimental procedure for the Pd(OAc)2-catalyzed direct decarboxylative coupling of alkynyl carboxylic acids with allyl ethers General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30°C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
70% | With oxygen; palladium diacetate; acetic acid In acetonitrile at 30℃; for 48h; | 3 Specific Example 3 A mixture of 48.1 mg (0.3 mmol)2- (methylphenyl) - propiolic acid,80.5 mg (0.6 mmol)Allyl phenyl ether,6.7 mg (0.03 mmol) of palladium acetate,24.7 mg (0.06 mmol) of DPPP was added to the reaction tube,A further 2 mL of a mixed solution of acetonitrile and glacial acetic acid (3: 1 by volume)And then the reaction tube filled with O2.30 ° C for 48 hours,After the reaction is cooled,Saturated aqueous sodium bicarbonate solution and dichloromethane extraction,Dispensing,The organic layer was dried over MgSO4,filter,The filtrate is steamed,Removing the solvent,The residue was chromatographed on silica gel,With leaching of petroleum ether and ethyl acetate in a volume ratio of 150: 1,Collect the effluent from the actual gradient,TLC detection,The effluent containing the product was combined,The solvent was distilled off by rotary evaporator,Dried in vacuo to give a pale yellow liquid52.1 mg of 1- (2-methylphenyl) -3-methylene-4-phenoxybutyne,Yield 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate; In acetic acid; acetonitrile; at 30℃; for 48h;Schlenk technique; | General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate In acetic acid; acetonitrile at 30℃; for 48h; Schlenk technique; regioselective reaction; | 4.2. Typical experimental procedure for the Pd(OAc)2-catalyzed direct decarboxylative coupling of alkynyl carboxylic acids with allyl ethers General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30°C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
74% | With oxygen; palladium diacetate; acetic acid In acetonitrile at 30℃; for 48h; | 4 Specific Example 4 52.3 mg (0.3 mmol)2- (3,4-dimethylphenyl) -propionic acid,80.5 mg (0.6 mmol) of allyl phenyl ether,6.7 mg (0.03 mmol) of palladium acetate,24.7 mg (0.06 mmol) of DPPP was added to the reaction tube,A further 2 mL of a mixed solution of acetonitrile and glacial acetic acid (3: 1 by volume)And then the reaction tube filled with O2.30 ° C for 48 hours,After the reaction is cooled,Saturated aqueous sodium bicarbonate solution and dichloromethane extraction,Dispensing,The organic layer was dried over MgSO4,filter,The filtrate is steamed,Removing the solvent,The residue was chromatographed on silica gel,With leaching of petroleum ether and ethyl acetate in a volume ratio of 150: 1,Collect the effluent from the actual gradient,TLC detection,The effluent containing the product was combined,The solvent was distilled off by rotary evaporator,Dried in vacuo to give a colorless liquid58.2 mg of 1- (3,4-dimethylphenyl) -3-methylene-4-phenoxybutyne,Yield 74%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate In acetic acid; acetonitrile at 30℃; for 48h; Schlenk technique; regioselective reaction; | 4.2. Typical experimental procedure for the Pd(OAc)2-catalyzed direct decarboxylative coupling of alkynyl carboxylic acids with allyl ethers General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30°C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
70% | With oxygen; palladium diacetate; acetic acid In acetonitrile at 30℃; for 48h; | 5 Specific Example 5 52.9 mg (0.3 mmol)2- (4-methoxyphenyl) - propiolic acid,80.5 mg (0.6 mmol) of allyl phenyl ether,6.7 mg (0.03 mmol) of palladium acetate,24.7 mg (0.06 mmol) of DPPP was added to the reaction tube,A further 2 mL of a mixed solution of acetonitrile and glacial acetic acid (3: 1 by volume)And then the reaction tube filled with O2.30 ° C for 48 hours,After the reaction is cooled,Saturated aqueous sodium bicarbonate solution and dichloromethane extraction,Dispensing,The organic layer was dried over MgSO4,filter,The filtrate is steamed,Removing the solvent,The residue was chromatographed on silica gel,And the mixture was washed with a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100: 1,Collect the effluent from the actual gradient,TLC detection,The effluent containing the product was combined,The solvent was distilled off by rotary evaporator,Dried in vacuo to give a pale yellow liquid55.5 mg of 1- (4-methoxyphenyl) -3-methylene-4-phenoxybutyne,Yield 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With 1,3-bis-(diphenylphosphino)propane; oxygen; palladium diacetate In acetic acid; acetonitrile at 30℃; for 48h; Schlenk technique; regioselective reaction; | 4.2. Typical experimental procedure for the Pd(OAc)2-catalyzed direct decarboxylative coupling of alkynyl carboxylic acids with allyl ethers General procedure: Arylalkynyl carboxylic acids (0.3 mmol), allyl ethers (0.6 mmol), Pd(OAc)2 (10 mol %), and DPPP (20 mol %) were added to a two necked flask, and then a mixed solvent of CH3CN (1.5 mL) and HOAc (0.5 mL) was added. The mixture was then stirred at 30°C for 48 h under oxygen. After the reaction was complete, the mixture was washed with saturated aqueous NaHCO3 solution and extracted with CH2Cl2 three times. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The resulting crude product was purified by flash chromatography on silica gel using hexane or hexane/ethyl acetate (150:1) as the eluent to give the pure products. |
60% | With oxygen; palladium diacetate; acetic acid In acetonitrile at 30℃; for 48h; | 6 Specific Example 6 54.2 mg (0.3 mmol)2- (4-chlorophenyl) - propiolic acid,80.5 mg (0.6 mmol) of allyl phenyl ether,6.7 mg (0.03 mmol) of palladium acetate,24.7 mg (0.06 mmol) of DPPP was added to the reaction tube,A further 2 mL of a mixed solution of acetonitrile and glacial acetic acid (3: 1 by volume)And then the reaction tube filled with O2.30 ° C for 48 hours,After the reaction is cooled,Saturated aqueous sodium bicarbonate solution and dichloromethane extraction,Dispensing,The organic layer was dried over MgSO4,filter,The filtrate is steamed,Removing the solvent,The residue was chromatographed on silica gel,With leaching of petroleum ether and ethyl acetate in a volume ratio of 150: 1,Collect the effluent from the actual gradient,TLC detection,The effluent containing the product was combined,The solvent was distilled off by rotary evaporator,Dried in vacuo to give a pale yellow liquid48.4 mg of 1- (4-chlorophenyl) -3-methylene-4-phenoxybutyne,Yield 60%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium sulfite In 5,5-dimethyl-1,3-cyclohexadiene at 85℃; for 7h; | 3 Example 3: In the case where a stirrer,thermometer,In a reaction vessel of a reflux condenser,0.6 mol of phenol (2), 0.68 mol of allylamine (3)Sodium sulfite 0.76 mol,Mass fraction of 75% xylene 230ml, control the stirring speed at 190rpm,The temperature of the solution was raised to 85 ° C,Reflux 7h,Cooling and pouring into 800ml of 20% sodium chloride solution,The water layer was extracted 5 times with 70% cyclohexanone,The organic layer and the cyclohexanone extract were washed with 40% sodium bisulfite solution, dehydrated with anhydrous calcium sulfate, distilled to cyclohexanone, vacuum distilled at 1.23 kPa, collected 70-76 distillate, To give 73.16 g of allylphenyl ether in a yield of 91%. |
78% | With sodium hydroxide In N,N-dimethyl-formamide at 100℃; for 8h; | 2 Preparation of propenyl phenyl ether Put 200 mL of N,N-dimethylformamide into the reaction kettle, start stirring, add 18.8 g of phenol, 16 g of sodium hydroxide and 22.8 g of allylamine in turn, heat up to 100 °C for 8 hours, and cool down to room temperature after the reaction is completed. , filtered to remove insolubles, concentrated the filtrate, added dichloromethane, washed with potassium carbonate aqueous solution, washed with water until neutral, dried and concentrated under reduced pressure to obtain 20.9 g of propenyl phenyl ether with a yield of 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With 1,4-diaza-bicyclo[2.2.2]octane; tert.-butylnitrite; copper(II) acetate monohydrate In toluene at 80℃; for 0.12h; Sealed tube; | 28 Example 28 The reaction flask was charged with Cu (OAc) 2.H2O (10 mol%), DABCO (3 mmol), toluene 15 mL,1a (3 mmol), compound 2a (6 mmol), t-butyl nitrite 3 (6 mmol), and then the system was sealed at 80 ° CAfter heating for about 12 hours, the mixture was extracted with ethyl acetate (20 mL x 3), washed three times with saturated brine, dried over anhydrous sodium sulfateThe organic layer was dried and the product 4ab was obtained by a simple column chromatography in a yield of 67%. |
67% | With 1,4-diaza-bicyclo[2.2.2]octane; tert.-butylnitrite; copper(II) acetate monohydrate In toluene at 80℃; for 12h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With rhodium(III) chloride trihydrate; alpha-Oxo-phenylmethan-diphenylphosphin; at 70℃; for 10h;Inert atmosphere; | General procedure: A 10mL three-necked flask equipped with a magnetic stirrer was charged with RhCl3·3H2O (8.0×10-3mmol) and acylphosphines prepared (4.0×10-2mmol) under argon atmosphere. Then alkene (4mmol) and silane (4.4mmol) were added via syringe. The hydrosilylation reaction proceeded with constant stirring under an appropriate temperature for 5h. At the end of the reaction, the conversion of alkene and the selectivity of product were determined by GC (Scheme 3) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With palladium(II) trifluoroacetate; Bathocuproine; p-benzoquinone In dimethyl sulfoxide; N,N-dimethyl-formamide at 135℃; for 6h; Inert atmosphere; Schlenk technique; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With copper In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere; | 9.4 Step 4:To the dry reaction tube was added 2,2-difluoro-2-iodo-1-(2-naphthyl)-ethane-1-one (1.0 mmol,1.0 equivalent, 0.332g),(allyloxy)benzene (1.0 mmol, 1.0 eq, 0.112 g)And catalyst copper powder (1.0 mmol, 1.0 equivalent, 0.064 g) and 2.0 mL of solvent DMF.The tube was evacuated and backfilled with nitrogen (repeated three times).2,2-Difluoro-2-iodo-1-phenylethan-1-one and (allyloxy)benzene were reacted at 120 ° C for 1 hour under nitrogen to obtain 2,2-difluoro-4- Hexyl-3,4-dihydrophenanthrene-1(2H)-one.TLC (developing agent is petroleum ether / ethyl acetate = 10/1) to detect the reaction is complete,The reaction was cooled to room temperature and 10 mL of water was added.The reaction system was extracted with ethyl acetate (3×10 mL).The combined organic layers were washed with saturated brine (sat. NaCI).Dry with Na2SO4 and concentrate in vacuo.And the crude residue was passed through a silica gel column chromatography.(petroleum ether / EtOAc = 50:1) purified,0.240 g of the desired product as a pale yellow oil was obtained |
67% | With copper In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: 4,5-diphenyletheno-1,2,3-selenadiazole; allyl phenyl ether With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 100℃; for 0.166667h; | Preparation of 4-(phenoxymethyl)-2,3-diphenylselenophene In toluene solvent (1 mL)[Rh (COD) Cl] 2 (4.93 mg, 0.01 mmol) and (S, S) -DIOP (12.0 mg, 0.024 mmol), 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol ), (allyloxy) benzene (0.082 mL, 0.6 mmol) is added and reacted at 100 oC for 2 hours. Confirm that the reaction is complete by TLC and add DDQ (68.1 mg, 0.3 mmol) dissolved in toluene (1.5 mL). The reaction solution is stirred at 100 ° C. for 10 minutes. After the reaction is completed, the solvent is removed using an evaporator. Then proceed to the column (Ether: Hexane = 1: 50) to the desired compound 4-(phenoxymethyl)-2,3-diphenylselenophene (46.7 mg, 60%) was obtained. |
60% | Stage #1: 4,5-diphenyletheno-1,2,3-selenadiazole; allyl phenyl ether With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 100℃; for 0.166667h; | Preparation of 4-(phenoxymethyl)-2,3-diphenylselenophene [Rh(COD)Cl]2 (4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),After adding 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol) and (allyloxy)benzene (0.082 mL, 0.6 mmol), react at 100 °C for 2 hours. The reaction was confirmed by TLC, and DDQ (68.1 mg, 0.3 mmol) was dissolved in toluene (1.5 mL) and added. The reaction solution was stirred at 100 °C for 10 minutes. After completion of the reaction, the solvent is removed using an evaporator. And the column (Ether: Hexane = 1: 50) to proceed to obtain the desired compound 4-(phenoxymethyl)-2,3-diphenylselenophene (46.7 mg, 60%). |
60% | Stage #1: 4,5-diphenyletheno-1,2,3-selenadiazole; allyl phenyl ether With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 100℃; for 0.166667h; | 2 Preparation of 4-(Phenoxymethyl)-2,3-diphenylselenophene [Rh(COD)Cl]2(4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol),After adding (allyloxy)benzene (0.082 mL, 0.6 mmol),Reaction at 100oC for 2 hours. Confirm that the reaction is complete by TLCDissolve DDQ (68.1 mg, 0.3 mmol) in toluene (1.5 mL) and add. The reaction solution is stirred at 100oC for 10 minutes.After completion of the reaction, the solvent is removed using an evaporator.And the column (Ether: Hexane = 1: 50) can be carried out to obtain a desired compound, 4-(phenoxymethyl)-2,3-diphenylselenophene (46.7 mg, 60%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; | Preparation of 3-(phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene In toluene solvent (1 mL)[Rh (COD) Cl] 2 (4.93 mg, 0.01 mmol) and (S, S) -DIOP (12.0 mg, 0.024 mmol), 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol ), (allyloxy) benzene (0.082 mL, 0.6 mmol) is added and reacted at 100 oC for 2 hours. After the reaction is completed, the solvent is removed using an evaporator. The column (Ether: Hexane = 1: 40) was obtained to obtain the desired compound 3-(phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene (64 mg, 85%). |
85% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; | Preparation of 3-(phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene[Rh(COD)Cl]2 (4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),After adding 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol) and (allyloxy)benzene (0.082 mL, 0.6 mmol), react at 100 °C for 2 hours. After completion of the reaction, the solvent is removed using an evaporator. And the column (Ether: Hexane = 1: 40) to proceed to obtain the desired compound 3-(phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene (64 mg, 85%). |
85% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h; | 2 Preparation of 3-(Phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene [Rh(COD)Cl]2(4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol),After adding (allyloxy)benzene (0.082 mL, 0.6 mmol), react at 100oC for 2 hours. After the reaction is complete,Remove the solvent using an evaporator. Then, proceed to the column (Ether: Hexane = 1: 40) to3-(phenoxymethyl)-4,5-diphenyl-2,3-dihydroselenophene (64 mg, 85%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With iodosodilactone at 90℃; for 18h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C37H60N2OPtSi2 In n-heptane at 20℃; for 20h; Schlenk technique; Inert atmosphere; | General procedure for synthesis of compounds 5a-t General procedure: A screw cap vial equipped with magnetic stir bar was charged with freshly distilled alkene (1 mmol) and bis(pinacolato)diboron B2Pin2 (1.1 mmol) followed by 4 ml of heptane. (7-Dipp)Pt(dvtms) (4 mg) of was added and the reaction mixture was allowed to stir at room temperature for 20h before evaporated to dryness. The residue was purified by column chromatography (EtOAc/hexanes as eluent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tert-butylhypochlorite; sodium iodide; In acetonitrile; at -30℃; | General procedure: The reaction of allyl ethyl ether (0.59g, 6.8mmol), triflamide (1g, 6.8mmol), NaI (3.06g, 20.4mmol) and t-BuOCl (2.3ml, 20.4mmol) in MeCN (60ml) was performed as above but at-30. The residue after removal of the solvent was treated with aqueous Na2S2O3 (80ml), extracted with ether (80ml), the extract dried over CaCl2, the solvent removed, the residue (?1.5g) was purified on a silica column (hexane, hexane/Et2O 1:1) to give N,N?-(3-ethoxypropane-1,2-diyl)bis(triflamide) 2 (1.45g, 68%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: phenylboronic acid With dihydrogen peroxide; cholin hydroxide In water at 20℃; for 1h; Green chemistry; Stage #2: allyl bromide In water at 20℃; for 2h; Green chemistry; | Representative one-pot procedure General procedure: A flask was charged with phenylboronic acid (4.0 mmol), choline hydroxide (aq. 40-50 wt%, 2.0 mL), and H2O2 (aq. 30 wt%, 0.8 mL). Then, the mixture was stirred at room temperature in open air for 1 h. Next, 0.34 g of benzyl bromide (2.0 mmol) was added into the flask at room temperature, then the resulting mixture was allowed to stir at room temperature for 2 h. Quenched with 3 M HCl solution, then extracted with extracted with diethyl ether (3 * 10 mL). The combined organic layers were washed with brine, dried with anhydrous Na2SO4, and the volatile solvent was evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes only). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With o-phenylenebis(diphenylphosphine); cobalt(II) bromide; zinc In water; acetone at 20℃; Inert atmosphere; regioselective reaction; | 4.3. General procedure for the synthesis of 5 General procedure: An oven-dried tube was charged with Zn (4.0 mmol, 4.0 equiv), CoBr 2 (0.05 mmol, 5 mol%) and dppbz (0.05 mmol, 5 mol %). The tube was evacuated and backfilled with nitrogen (repeated three times). Then α,α ,α -iododifluoroacetones 1 (1.0 mmol, 1.0 equiv) dissolved in acetone/H 2 O (30:1) (5.0 ml), and alkene 4 (1.2 mmol, 1.2 equiv) were added into the tube. The reaction mixture was stir- ring at rt for 2-17 h. After completion of the reaction (as indicated by TLC), the reaction is quenched with the appropriate amount of water, and the reaction mixture was extracted with ethyl ac- etate (5-10 mL). The combined organic layers were washed with saturated brine, dried over Na 2 SO 4 and the solvents evaporated in vacuo. The crude residue was purified by flash column chromatog- raphy to afford desired the product 5 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With 2-hydroxypyridin; bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In toluene at 80℃; for 3h; Inert atmosphere; chemoselective reaction; | Allylation of Ketimine 1a (Table 1) N-Sulfonyl ketimine 1a (24.3 mg, 0.10 mmol), [IrCl(cod)]2 (1.7 mg, 5mol% of Ir), NaBArF4 (9.2 mg, 10 mol%), and base (10-50 mol%) wereplaced in a Schlenk tube under N2. Toluene (0.4 mL) and allyl compound2 (1.5 equiv) were added to the mixture successively. TheSchlenk tube was capped with a glass stopper and stirred at 80 °C for3 h. The mixture was passed through a short alumina pad eluted withEtOAc. The solvent was removed on a rotary evaporator, and the residuewas subjected to preparative TLC (silica gel) to give 3a and 4a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 2-hydroxypyridin; bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In toluene at 80℃; for 3h; Inert atmosphere; chemoselective reaction; | Benzo[d]isothiazole 1,1-Dioxides 3, 5, and 6; General Procedure(Scheme 2) General procedure: N-Sulfonyl ketimines 1 (0.10 mmol unless otherwise indicated),[IrCl(cod)]2 (5 mol% of Ir), NaBArF4 (10 mol%), and base (10 mol%)were placed in a Schlenk tube under N2. Toluene (0.4 mL) and allylcompounds 2 (2 equiv) were added to the mixture successively. TheSchlenk tube was capped with a glass stopper and stirred at 80 °C for 1-18 h. The mixture was passed through a short alumina pad elutedwith EtOAc. The solvent was removed on a rotary evaporator, and theresidue was subjected to preparative TLC on silica gel to give 3, 5 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With 2-hydroxypyridin; bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In toluene at 80℃; for 3h; Inert atmosphere; chemoselective reaction; | Benzo[d]isothiazole 1,1-Dioxides 3, 5, and 6; General Procedure(Scheme 2) General procedure: N-Sulfonyl ketimines 1 (0.10 mmol unless otherwise indicated),[IrCl(cod)]2 (5 mol% of Ir), NaBArF4 (10 mol%), and base (10 mol%)were placed in a Schlenk tube under N2. Toluene (0.4 mL) and allylcompounds 2 (2 equiv) were added to the mixture successively. TheSchlenk tube was capped with a glass stopper and stirred at 80 °C for 1-18 h. The mixture was passed through a short alumina pad elutedwith EtOAc. The solvent was removed on a rotary evaporator, and theresidue was subjected to preparative TLC on silica gel to give 3, 5 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With 2-hydroxypyridin; bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In toluene at 80℃; for 3h; Inert atmosphere; chemoselective reaction; | Benzo[d]isothiazole 1,1-Dioxides 3, 5, and 6; General Procedure(Scheme 2) General procedure: N-Sulfonyl ketimines 1 (0.10 mmol unless otherwise indicated),[IrCl(cod)]2 (5 mol% of Ir), NaBArF4 (10 mol%), and base (10 mol%)were placed in a Schlenk tube under N2. Toluene (0.4 mL) and allylcompounds 2 (2 equiv) were added to the mixture successively. TheSchlenk tube was capped with a glass stopper and stirred at 80 °C for 1-18 h. The mixture was passed through a short alumina pad elutedwith EtOAc. The solvent was removed on a rotary evaporator, and theresidue was subjected to preparative TLC on silica gel to give 3, 5 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With 2-hydroxypyridin; bis(1,5-cyclooctadiene)diiridium(I) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In toluene at 80℃; for 1h; Inert atmosphere; chemoselective reaction; | Benzo[d]isothiazole 1,1-Dioxides 3, 5, and 6; General Procedure(Scheme 2) General procedure: N-Sulfonyl ketimines 1 (0.10 mmol unless otherwise indicated),[IrCl(cod)]2 (5 mol% of Ir), NaBArF4 (10 mol%), and base (10 mol%)were placed in a Schlenk tube under N2. Toluene (0.4 mL) and allylcompounds 2 (2 equiv) were added to the mixture successively. TheSchlenk tube was capped with a glass stopper and stirred at 80 °C for 1-18 h. The mixture was passed through a short alumina pad elutedwith EtOAc. The solvent was removed on a rotary evaporator, and theresidue was subjected to preparative TLC on silica gel to give 3, 5 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 5h; | 7 Preparation of propenyl phenyl ether Put 200 mL of N,N-dimethylformamide into the reaction kettle, start stirring, add 18.8 g of phenol, 22.4 g of potassium hydroxide and 71.2 g of allyl diethyl phosphate in turn, heat up to 100 ° C and keep the reaction for 5 h. After the reaction was completed, it was cooled to room temperature, filtered to remove insoluble matter, the filtrate was concentrated, and trichloroethane was added, then washed with aqueous sodium hydroxide solution, washed with water until neutral, dried and concentrated under reduced pressure to obtain 20.1 g of propenyl phenyl ether. The yield was 20.1 g. 75%. |
Tags: 1746-13-0 synthesis path| 1746-13-0 SDS| 1746-13-0 COA| 1746-13-0 purity| 1746-13-0 application| 1746-13-0 NMR| 1746-13-0 COA| 1746-13-0 structure
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P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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