95% |
With potassium bromate In dichloromethane; water; acetonitrile at 20℃; for 1h; Sonication; |
Ultrasound assisted MCM-41-Ru catalyzed oxidation of arenes
General procedure: A 20-mL flask was charged with CH2Cl2 (5 mL), H2O (5 mL), CH3CN (5 mL), chrysene (228.3 mg, 1 mmol), and KBrO3 (0.5 g, 2.99 mmol). MCM-41-Ru (75 mg) was added into the flask, and the dark suspension was irradiated at room temperature for 1h. The catalyst was separated from the reaction medium by filtration and washed with water and acetone, and then dried at 150 °C overnight. The reaction mixture was poured into 50 mL of water, and the organic phase was separated. The aqueous phase was extracted with CH2Cl2 (3×10 mL). The CH2Cl2 extracts were combined with the organic phase, washed with brine (3×10 mL), and dried over anhydrous sodium sulfate to yield a dark orange solution. The solution was concentrated under reduced pressure, and the mixture was purified by preparative thin-layer chromatography (n-hexane/ethyl acetate =10/3), providing chrysene-5,6-dione as the major product and 2-(2-formylphenyl)-1-naphthaldehyde as the side product. The same procedure was also used for the reactions of other arene substrates. |
94% |
With quinolinium monofluorochromate(VI) In acetic acid for 1h; |
|
93% |
With methyltrifluoromethyldioxirane at -20℃; for 0.0833333h; |
|
90% |
With HOF* CH3CN In chloroform; acetonitrile at -15 - 0℃; for 0.0166667h; |
|
90% |
With chromium(VI) oxide In water; acetic acid for 48h; Ambient temperature; |
|
90% |
With chromium(VI) oxide; 18-crown-6 ether; acetic acid at 50℃; for 3h; |
|
85% |
With bis(pyridine)silver permanganate In dichloromethane for 16h; Ambient temperature; |
|
85% |
With chromium(VI) oxide; periodic acid In acetonitrile at 5℃; for 1h; |
|
85% |
With DIQCC In dichloromethane at 20℃; for 2h; |
Oxidation of alcohols to carbonyl compounds
General procedure: A solution of the organic compounds (Table-1, 10 mmol) in 10 mL of dichloromethane was added to 3,4-dihydroisoquinolinium chlorochromate (Table-1, 1:1 ratio; 3.94 g, 10 mmol and 1:3 ratio; 11.83 g, 30 mmol). The mixture was stirred magnetically at room temperature until the complete consumption of the substrate. The progress of the reaction was monitored by TLC analysis. After completion of the reaction, 50 mL of water was added to the reaction mixture and extracted with ether (3 x 20 mL). The combined organic layer was dried over MgSO4 and evaporated on a rotary evaporator under reduced pressure. Then the product was chromatographed over silica gel using ethyl acetate-hexane (1:4) as the eluent to separate the product. After evaporation of the solvent, the fairly pure solid were crytstallized out the liquid carbonyl compounds were derivatized with 2,4-dinitrophenylhydrazine. The melting points of solid compounds such as benzil, benzophenone, 3-oxocholestorol, 1-menthone, 1-indanone, tetralone, 10-anthraquinone and phenanthrene-9,10-quinone were checked and these compounds were identified by spectral data like IR and 1H NMR. |
83% |
With 3,5-dimethylpyrazolium chlorochromate at 20℃; for 2h; Neat (no solvent); |
|
83% |
With chromium(VI) oxide; acetic acid for 1h; Reflux; Inert atmosphere; |
1 4.4.4 General procedure for synthesis of phenanthrenequinone derivatives
General procedure: The oxidation was carried out using 0.4g of chromium trioxide (4mmol), which was added to a solution of 0.2g of the phenanthrene 9a-d (1.12mmol; 1equiv) in 20mL of glacial acetic acid. The resulting mixture was warmed gently until no material remained undissolved and then the solution was heated at reflux for 1h, cooled to room temperature, and then poured into water. The mixture was filtered, washed with water, and then crystallized from hexane. 4.4.4.1 9,10-Phenanthrenequinone 10a (0041) Following the general procedure, 5 10a was obtained from 6 9a; yield: 83%; orange needles; mp 207-208°C. 1H NMR (300MHz, CDCl3): δ=7.36 (t, J=7.2Hz, 2H), 7.61 (t, J=7.2Hz, 2H), 7.90 (d, J=8.1Hz, 2H), 8.06 (d, J=7.5Hz, 2H); 13C NMR (75MHz, CDCl3): δ=123.49 (2CH), 129.07 (2CH), 129.95 (2CH), 130.50 (2C), 135.32 (2C), 135.54 (2CH), 179.77 (2C=O) [36]. |
80% |
With chromium(VI) oxide In acetic acid at 50 - 55℃; for 1h; |
|
80% |
With sodium periodate In dichloromethane; water; acetonitrile at 20℃; for 1h; Irradiation; |
|
80% |
With potassium bromate; acetic acid at 70 - 75℃; Reflux; Inert atmosphere; |
3.2.3. Preparation of Phenanthrenequinone. 6
Phenanthrene (16 g, Aldrich Tech Grade (90 percent), 0.081 mol) and acetic acid (200 ml) were stirred and heatedto 70-75 °C. Potassium bromate (32 g, 0.19 mol) was added in 2 portions. After the addition of the first portion the temperature rose to reflux with evolution of bromine vapors. The second portion was added and the condenser was replaced bya distillation head. The heating was continued until the distillate was colourless. The deep red solution was cooled and poured into water (300 ml) and the precipitate was isolated by filtration. The crude product was purified by slurrying in 100 ml of hot (70 °C.) aqueous sodium bisulfite solution (40 percent) and filtering while hot. The deep red filtrate was cooled and treated with aqueous sodium carbonate until basic. The precipitated product was recovered by extraction with methylene chloride, dried and concentrated to give 13.4 g of orange yellow solid: Phenanthrenequinone, yield 13.4 g (80%) mp 182-184 °C. |
79% |
With chromium(VI) oxide; periodic acid |
|
78% |
With isoquinolinium fluorochromate In acetic acid for 2.5h; Heating; |
|
78% |
With tert.-butylhydroperoxide; Ru(2,4,13,15-tetraphenyl-1,5,12,16-tetraaza-tricyclo[14.2.2.06,11]eicosa-4,6(11),7,9,12-pentaene)Cl2 In acetonitrile for 6h; Irradiation; |
2.4.2 General procedure for Sp2 C-H bond activation for polycyclic aromatic hydrocarbons
General procedure: To a solution of Zn(II)/Ru(II) complex (1.25μmol), pyrene (0.5mmol) and TBHP (1.0mmol) in 10mL of acetonitrile was added. After the reaction was stirred under visible light for 6h, (monitored the reaction by LC-MS) solvent was evaporated using rotavapor. Purification of the crude compounds by column chromatography with dichloromethane/ethyl acetate (9:1, v/v) as eluent to an afforded pure product. |
76% |
With potassium bromate In acetic acid for 1.5h; Heating; |
|
76% |
Stage #1: phenanthrene With sulfuric acid In water at 90 - 95℃; for 4h;
Stage #2: With potassium dichromate In water for 1.5h; Heating; |
2.1. Synthesis of 1,10-phenanthroquinone (2)
To a solution of H2SO4/H2O (20 ml:60 ml, v/v), phenanthrene (2 g,11.23 mmol) was added and the reaction mixture was stirred at 90-95 °C for 4 h. K2Cr2O7 (12 g) was added in parts to the reactionmixturefor 1 h and heat the reaction mixture for 30min. After complete reaction(monitored on TLC), cold water (200 ml) was added and precipitate soobtained was filtered, and washed with water (3 × 50 ml). The precipitatewas suspended in ethanol (60 ml) and saturated solution of sodiummetabisulfite (30 ml) was added with frequent stirring for 15 min.Further, water (150 ml) was added to the reaction mixture to dissolvethe product and filtered. To the filtrate Na2CO3 solution (20%, 50 ml)was added to decompose the adduct and allowed it to precipitate. Theprecipitatewas filtered,washedwithwater and dried in air to obtain orangecolored solid. The product was recrystallized from glacial aceticacid. Yield 76% (1.77 g). M p: 209 °C. Rf = 0.7 (CHCl3); 1H NMR(CDCl3) δ (ppm): 8.20 (d, 2H, J = 7.5 Hz), 8.03 (d, 2H, J = 8.1 Hz),7.74 (t, 2H, J = 7.2, 7.2 Hz), 7.49 (t, 2H, J = 7.5, 7.5 Hz); FT-IR (KBr)υmax (cm-1) 1676, 1594, 1451, 1478, 1334, 1284, 1230, 925, 760, 533,434. |
75% |
With sodium bromate; nitric acid In acetonitrile for 1h; Heating; |
|
72% |
With tripropylammonium fluorochromate (VI) In acetic acid for 2h; |
|
70% |
With 3,5-dimethylpyrazolium fluorochromate(VI) In dichloromethane for 4h; |
|
66% |
With dihydroxyphenylselenonium benzenesulfonate In 1,4-dioxane; water for 96h; Heating; |
|
65% |
With triethylammonium fluorochromate(VI) In dichloromethane for 4h; Heating; |
|
60% |
With barium permanganate In acetonitrile for 4.5h; Heating; |
|
60% |
With 2,2'-bipyridylchromium peroxide In benzene for 7h; Heating; |
|
60% |
With 2,2'-bipyridylchromium peroxide In benzene for 7h; Heating; effect of various chromium(VI) based oxidants; |
|
58% |
With ammonium persulfate; sulfuric acid; sodium dodecyl-sulfate In cyclohexane; water at 50℃; for 7h; |
|
57.7% |
With potassium dichromate; sulfuric acid In water at 85 - 115℃; |
|
50.39% |
With chromium(VI) oxide; acetic anhydride for 3h; Cooling with ice; |
Synthesis of Phenanthrene-9,10-dione (1).
Phenanthrene (5.0 g, 0.028 mol) was added to a 1 L flask and dissolved in 300 mL of acetic anhydride. Chromium (VI) oxide (6.16 g, 0.062 mol) was slowly added to the flask, which was in anice bath. After 3 h of reaction, the excess ice was poured into the reaction mixture. Yellow crude product was obtained after filtration and washed with distilled water until the effluent liquid was colorless. Yellow crystals were obtained after recrystallization of the crude product from a toluene/ethanol (v/v = 3:1) co-solvent. The yield was 50.39 % (2.94 g). 1H NMR (300 MHz, CDCl3) δ 8.20 (dd, 2H), 8.03 (d,2H), 7.74 (dt, 2H), 7.5 (dt, 2H). |
40% |
With 2,6-dichloropyridine N-oxide; (5,10,15,20-tetramesitylporphyrinato)ruthenium(II) carbonyl; 4 A molecular sieve; hydrogen bromide In benzene at 40℃; |
|
27% |
With poly<styrene-co-(4-vinylpyridinium dichloroiodate(I))> In methanol for 20h; Heating; |
|
8% |
With triethylsilane; tert.-butylhydroperoxide; oxygen; cobalt acetylacetonate; acetylacetone In dichloromethane; 1,2-dichloro-ethane at 40℃; for 17h; Inert atmosphere; |
|
|
With chromium(VI) oxide; sulfuric acid |
|
|
With chromic acid |
|
|
With diacetyl-orthonitric acid |
|
|
With cerium salt durch elektrolytische Oxydation; |
|
|
With chromium(VI) oxide; acetic acid |
|
|
With potassium dichromate; sulfuric acid; water |
|
|
With iodic acid; acetic acid |
|
|
With chromium(III) oxide; sulfuric acid |
|
|
With dihydrogen peroxide; acetic acid |
|
|
bei der elektrolytischen Oxydation in Gegenwart von Cerverbindungen; |
|
|
With ozone In dichloromethane at 25℃; correlations of relative rate data with various molecular orbital parameters; |
|
99 % Turnov. |
With 2,6-dichloropyridine N-oxide In dichloromethane at 40℃; for 12h; |
|
|
With iodosylbenzene sulfate; μ-oxobis[iron(III)-2,9(10),16(17),23(24)-tetra-tert-butylphthalocyanine] In toluene at 25℃; for 4h; Inert atmosphere; |
|
14 %Chromat. |
With iodobenzene; Oxone; C48H24ClFeN4O8(4-)*4Na(1+) In water; acetonitrile at 20℃; for 168h; |
|
34 %Chromat. |
With ruthenium(2,2',6':2''-terpyridine)(2,6-pyridinedicarboxylate); dihydrogen peroxide In methanol; dichloromethane; water at 40℃; for 7h; regioselective reaction; |
|
|
With pyridinum sulfonate fluorochromate for 0.0277778h; Neat (no solvent); Microwave irradiation; |
|
|
With iodosylbenzene; C128F80Fe2N16O*4H2O In dichloromethane at 20℃; for 2h; |
Typical Procedure for Catalytic Oxidation of Organic Substrates with perfluoroiron(III) tetraazaporphyrine-(μ-oxodimer) 1.
General procedure: A solution of substrate (2-5 mg, 0.01-0.05 mmol) in dichloromethane or in acetonitrile water(1:1 v:v) mixture was mixed with an aliquote of perfluoro-iron(III)tetraazaporphyrine-(μ-oxodimer) 1 (0.5-10 mol %) in CH2Cl2 and the appropriate oxidant [PhIO, (PhIO)3SO3, Oxone, H2O2, or CH3COOOH] (6 equiv of active O) was added under stirring, at room temperature. Samples of the reaction mixture (15-40 μL) were collected every 5 minutes, filtered through 2-3 cm of silica gel suspended in a Pasteur pipette, washed with a mixture of ethyl acetate and hexane (2:3 v:v), and analyzed using GC-MS. |
|
With potassium dichromate; sulfuric acid Heating; |
|
|
Stage #1: phenanthrene In water at 90 - 95℃; for 0.5h; Acidic conditions;
Stage #2: With sodium metabisulfite In ethanol for 0.25h; |
4.1 4.1 Synthesis of 1,10-phenanthroquinone 2
To a heated solution of concentrated H2SO4 (10 ml), H2O (30 ml) and phenathrene (2 gm) at 90-95 °C, K2Cr2O7 (12 gm) was added portion wise during 1 h and reaction mixture was heated for 30 min. After completion of the reaction (monitored through TLC), cold water was added to the reaction mixture and filtered the precipitate followed by washing with water. The precipitate suspended in ethanol (60 ml) and saturated solution of sodium metabisulfide (30 ml) with frequent stirring for 15 min. Cold water (150 ml) was added to the mixture to dissolve the addition product and filtered. In the filtrate part, Na2CO3 solution (20%, 50 ml) was added to decompose adduct and allowed to precipitate. The precipitate was filtered followed by washing with water and air dried to obtain orange colored solid. [19] Rf = 0.46 (Ethylacetate:Hexane; 2:8, v/v); 1H NMR (CDCl3) δ (ppm): 8.23 (d, 2H, J = 8.7 Hz), 7.98 (d, 2H, J = 9.0 Hz), 7.77 (t, 2H, J = 8.4, 8.4 Hz), 7.52 (t, 2H, J = 7.2, 7.8 Hz); FT-IR (KBr) υmax (cm-1) 3023, 1663, 1503, 1442, 1313, 749. |
|
With sodium hypochlorite; tetra(n-butyl)ammonium hydrogensulfate |
|
|
With chromium(VI) oxide |
|
|
With ruthenium salt; chloric acid |
|
|
With manganese salt |
|
|
With chromium(VI) oxide; acetic acid In water at 60℃; for 2h; |
1.1-11.1 Step 1:
Dissolve 1.0g of phenanthrene in 8mL of acetic acid solution at 60°C to obtain acetic acid solution of phenanthrene, then add 2.2g of chromium trioxide to 5mL of acetic acid and 2mL of water (formulated acetic acid aqueous solution to obtain trioxide Chromium acetic acid aqueous solution, add the chromium trioxide acetic acid aqueous solution dropwise to the phenanthrene acetic acid solution for reaction for 2h to obtain the reaction solution, add the reaction solution to 350mL of 1M potassium carbonate solution, and then add toluene Shake to obtain an organic layer after separation, dry the organic layer with anhydrous magnesium sulfate, and remove the solvent by evaporation to obtain an orange solid as phenanthrenequinone |
|
With chromium(VI) oxide |
|