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CAS No. : | 85-01-8 | MDL No. : | MFCD00001168 |
Formula : | C14H10 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | YNPNZTXNASCQKK-UHFFFAOYSA-N |
M.W : | 178.23 | Pubchem ID : | 995 |
Synonyms : |
[3]Helicene;Ravatite;NSC 26256
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 14 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 61.45 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.22 cm/s |
Log Po/w (iLOGP) : | 2.35 |
Log Po/w (XLOGP3) : | 4.46 |
Log Po/w (WLOGP) : | 3.99 |
Log Po/w (MLOGP) : | 5.17 |
Log Po/w (SILICOS-IT) : | 4.1 |
Consensus Log Po/w : | 4.01 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.49 |
Solubility : | 0.0057 mg/ml ; 0.000032 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.18 |
Solubility : | 0.0118 mg/ml ; 0.0000662 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.75 |
Solubility : | 0.00032 mg/ml ; 0.00000179 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P273-P305+P351+P338 | UN#: | 3077 |
Hazard Statements: | H319-H334-H411 | Packing Group: | Ⅲ |
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 |
---|---|---|
91% | With acetic acid; potassium bromide In water at 40℃; for 4.5 h; | In a 50ml round bottom flask equipped of a magnetic successively added acetic acid: water = 9:1 solvent (10ml), and(514 mg, 2 mmol) and KBr (215 mg, 1.8 mmol) were added and dissolved under magnetic stirring.1.2 gZnAl-BrO3 - LDHs (1.2 mmol BrO3-) were slowly added in batches over half an hour and the reaction temperature was controlled at 40 ° C for 4 hours. TLC was followed by monitoring the reaction process with ethyl acetate-petroleum ether (v / v = 1: 15) developing solvent. After completion of the reaction, the mixture was extracted with dichloromethane (3 x 10 mL) and the combined organic phases were washed again with distilled water (3 x 10 mL). And finally dried with anhydrous sodium sulfate, filtered and chromatographed (eluent ratio: petroleum ether to ethyl acetate volume ratio of 15: 1) to obtain white crystals in 91percent yiel |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With aluminum oxide; copper(ll) bromide In chlorobenzene at 80℃; for 2h; | |
95% | With aluminum oxide; copper(ll) bromide In tetrachloromethane at 80℃; for 2h; | |
93% | With bromine In chloroform for 17h; Reflux; Inert atmosphere; |
92% | With potassium dichromate; acetic acid; copper(ll) bromide at 20℃; for 1h; | |
91% | With acetic acid; potassium bromide In water at 40℃; for 4.5h; | 3 Example 3 In a 50ml round bottom flask equipped of a magnetic successively added acetic acid: water = 9:1 solvent (10ml), and(514 mg, 2 mmol) and KBr (215 mg, 1.8 mmol) were added and dissolved under magnetic stirring.1.2 gZnAl-BrO3 - LDHs (1.2 mmol BrO3-) were slowly added in batches over half an hour and the reaction temperature was controlled at 40 ° C for 4 hours. TLC was followed by monitoring the reaction process with ethyl acetate-petroleum ether (v / v = 1: 15) developing solvent. After completion of the reaction, the mixture was extracted with dichloromethane (3 x 10 mL) and the combined organic phases were washed again with distilled water (3 x 10 mL). And finally dried with anhydrous sodium sulfate, filtered and chromatographed (eluent ratio: petroleum ether to ethyl acetate volume ratio of 15: 1) to obtain white crystals in 91% yiel |
88% | With gold(III) chloride; N-Bromosuccinimide In 1,2-dichloro-ethane at 80℃; for 15h; Inert atmosphere; regioselective reaction; | |
80% | With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; trifluorormethanesulfonic acid In dichloromethane at 30℃; for 2h; | |
76% | With sodium bismuthate; zinc dibromide In acetic acid at 20℃; for 1h; | |
60% | With 1,8-diazabicyclo[5.4.0]undec-7-ene hydrobromide-perbromide In acetic acid for 3h; Heating; | |
50% | With ammonium metavanadate; perchloric acid; dihydrogen peroxide; potassium bromide In chloroform; water at 25℃; for 6h; | |
46% | With tetra-N-butylammonium tribromide In acetic acid for 0.5h; Ambient temperature; | |
46% | With bromine In tetrachloromethane for 2h; Reflux; | |
With tetrachloromethane; N-Bromosuccinimide | ||
With tetrachloromethane; bromine; iodine | ||
With tetrachloromethane; bromine | ||
With phosphorus pentabromide; benzene | ||
With chloroform; bromine at 0 - 76℃; | ||
With tetrachloromethane; bromine at 0 - 76℃; | ||
With trimethyl phosphite; bromine Ambient temperature; | ||
(bromination); | ||
With bromine In acetic acid | ||
With bromine; sodium bromide In acetic acid | ||
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione Irradiation; | ||
With bromine In tetrachloromethane at 77℃; for 2h; | ||
122 g | With bromine In dichloromethane for 6h; Reflux; | 1.1; 2.1 Example 2 1) Add 500ml of dichloroethane, 120g of bromine, and 100g of phenanthrene into a 1000ml three-necked flask with a condenser. After the addition is complete, slowly increase the temperature to reflux, keep refluxing for 6 hours, cool to normal temperature, and add 200ml concentration 15% sodium carbonate solution, stirred for 15 minutes, then, separated into layers at rest, separated the organic phase, dried with anhydrous sodium sulfate, filtered, the liquid was concentrated under reduced pressure to recover the solvent to the end, and a viscous liquid was obtained. Add 5 The doubled amount of isopropanol was recrystallized, cooled, filtered off with suction, and dried to obtain 122 g of 9-bromophenanthrene-like white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With tetraethylammonium bromide In ethanol at 60℃; electrolysis, lead cathode; | |
97% | With sodium In pentan-1-ol for 3h; Heating; | |
95% | Stage #1: phenanthrene With Na2K-SG(I) In tetrahydrofuran at 20℃; Inert atmosphere; Stage #2: With water In tetrahydrofuran Inert atmosphere; regioselective reaction; |
91% | With sodium hydroxide; rac-cysteine In isopropyl alcohol at 20℃; for 8h; UV-irradiation; | |
89% | With Dicalcium Nitride Electride In tetrahydrofuran; isopropyl alcohol at 65℃; for 24h; Inert atmosphere; | |
88% | With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; methylamine hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 25℃; Irradiation; | |
77% | With iodine; ammonium chloride; strontium In isopropyl alcohol at 20℃; for 7h; Inert atmosphere; | Procedure for hydrogenation of various aromatic hydrocarbons (Table 3): General procedure: Under an argon atmosphere, metallic strontium was added to a THF (2 mL) suspension of aromatic hydrocarbons (1.0 mmol) and pre-dried ammonium chloride (535.0 mg, 10 mmol) and iodine at room temperature. After starring, the reaction mixture was quenched by 1 M HCl aqueous solution (15 mL). The organic materials were extracted with ethyl acetate (15 mL) three times, and the combined organic layers were washed successively with 5 % of KHSO3 solution, brine, respectively and dried over anhydrous Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel (hexane / ethyl acetate) to give the corresponding compound as a white solid. |
75% | With 15-crown-5; sodium In tetrahydrofuran; isopropyl alcohol; mineral oil at 0℃; for 0.0833333h; Inert atmosphere; | 7 Example 7 In a 10 ml single-mouth bottle, protected with nitrogen, 115.0 mg (2.0 mmol) of sodium reagent (40 wt%, sodium dispersion in mineral oil, particle size <10 μm), 15-crown-5-55.8 μl (2.0 mmol), 1 ml tetrahydrofuran Stir at 0 ° C for 5 min.A substrate solution is prepared. A 1.5 ml centrifuge tube was taken, 89.1 mg (0.5 mmol) of phenanthrene, 152.9 μl (2.0 mmol) of isopropanol, 1 ml of tetrahydrofuran were added, shaken, taken into a syringe, washed with 1 ml of tetrahydrofuran, and taken into a syringe. The prepared mixed solution was added to a single-mouth bottle and stirred at 0 ° C for 5 min.2ml reaction was quenched with saturated aqueous NaHCO 3 solution, warmed to room temperature. Diethyl ether was added and extracted with saturated aqueous sodium chloride solution, the organic phase was dried, concentrated, and column chromatographed to give 67.6mg of the title compound in 75% yield |
73% | With cobalt(II) chloride hexahydrate; lithium In tetrahydrofuran at 25℃; for 3h; Inert atmosphere; | |
71% | With terephthalonitrile; sodium tetrahydroborate In water; acetonitrile for 8h; Irradiation; | |
39% | With 2-pyrrolidinon; samarium diiodide at 20℃; Glovebox; | |
36% | With sodium tetrahydroborate; triethylamine In ethanol Irradiation; Further byproducts given. Yields of byproduct given; | |
34% | With ethylenediamine; <i>tert</i>-butyl alcohol In tetrahydrofuran at -78 - -74℃; for 4h; Inert atmosphere; | |
21% | With triethylsilane; potassium <i>tert</i>-butylate at 130℃; for 18h; Sealed tube; Inert atmosphere; | |
17% | With chlorotriisopropylsilane; diphenyl(pentafluorophenyl)phosphonium tetrakis(perfluorophenyl)borate In dichloromethane at 50℃; for 18h; Inert atmosphere; Schlenk technique; | 2.4.6. General experimental procedure for the hydrogenation reaction General procedure: A reaction tube with a Teflon cap was charged with equimolar(0.1 mmol) amounts of olefin and triisopropylsilane. Adichloromethane solution of 10 mol% catalyst was added to the tube and the mixture was heated at 50 °C for 18 h. The reactionmixture was taken in volumetric flask and diluted with DCM. Thediluted solution was analysed by GC-MS. |
With methanol; lithium at 27℃; other metals (Na, K); | ||
With copper chromite at 160℃; Hydrogenation; | ||
With copper chromite; ethanol at 150 - 180℃; Hydrogenation; | ||
With copper chromite; ethanol at 220℃; Hydrogenation.unter Druck; | ||
With copper chromite; cyclohexane at 150℃; Hydrogenation; | ||
With nickel; methyl cyclohexane at 95℃; Hydrogenation; | ||
With ethanol; nickel at 110℃; Hydrogenation; | ||
Yield given. Multistep reaction; | ||
36 % Chromat. | With tetra(n-butyl)ammonium hydroxide; hydrogen In methanol; water Raney nickel electrode; | |
70 % Chromat. | With hydrogen In ethyl acetate for 120h; Ambient temperature; | |
With tetra(n-butyl)ammonium hydroxide In water at 80℃; electrolysis, 4F/mol, divided cell; | ||
432 mg | With p-DMT In acetonitrile for 24h; Irradiation; | |
45 % Chromat. | With lithium; nickel dichloride In tetrahydrofuran at 20℃; | |
With samarium diiodide; water; triethylamine In tetrahydrofuran at 20℃; for 0.0833333h; | ||
With nanosized zero-valent iron In water at 25℃; for 21h; | ||
With hydrogen at 299.84℃; Flow reactor; | ||
2 %Chromat. | With samarium(II) dibromide; water In tetrahydrofuran at 25℃; Glovebox; | |
83 %Chromat. | With samarium(II) chloride In water at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tetrahydrofuran; methylmagnesium bromide; hydrogen; cobalt acetylacetonate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride at 0 - 60℃; for 48h; Autoclave; regioselective reaction; | |
60% | With lithium; diethylamine In tetrahydrofuran; diethyl ether at 20℃; for 2h; | |
53% | With hydrogen; magnesium; 1,2-bis(2,6-diisopropylphenylimino)ethane; cobalt(II) bromide In tetrahydrofuran at 60℃; for 60h; |
49% | With dibenzothiophene; dimethylsulfide; hydrogen In decane at 320℃; for 4h; Autoclave; | 8 Reference Example 8 In the same manner as in Reference Example 4, except that the feedstock was 12 g of phenanthrene, the hydrogenation reaction was effected. The conversion of phenanthrene was 95% and the yield of 1,2,3,4,5,6,7,8-octahydrophenanthrene was 49% by mass. |
22% | With tetra(n-butyl)ammonium hydroxide In water at 80℃; electrolysis, 6F/mol, divided cell; | |
With nickel; methyl cyclohexane at 120℃; Hydrogenation; | ||
With tetralin; nickel at 200 - 220℃; Hydrogenation; | ||
With lithium; diethylamine In tetrahydrofuran; diethyl ether | ||
With hydrogen at 400℃; | ||
With tetralin; nickel at 200 - 220℃; Hydrogenation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetramethylammonium monofluorochromate(VI) In dichloromethane at 20℃; for 0.75h; | |
98% | With cetyltrimethylammonium bromochromate In dichloromethane for 1.2h; Heating; | |
96% | With triethylammonium chlorochromate(VI); silica gel In dichloromethane for 8h; |
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 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: phenanthrene With ozone In methanol at -30℃; Stage #2: With potassium iodide In acetic acid | |
80% | With sodium periodate; triacetonitrile 4′-(4-chlorophenyl)-2,2′:6′,2″-terpyridine ruthenium(II) nitrate; tetra-(n-butyl)ammonium iodide In water at 20℃; for 10h; Inert atmosphere; | |
75% | Stage #1: phenanthrene With ozone In methanol at -78℃; Stage #2: With acetic acid; potassium iodide In methanol at 20℃; |
70% | Stage #1: phenanthrene With ozone In methanol at -30℃; Stage #2: With acetic acid; potassium iodide at 20℃; for 1h; | |
65% | Stage #1: phenanthrene With methanol; ozone In dichloromethane at -84℃; Stage #2: With acetic acid; sodium iodide In tetrahydrofuran at 20℃; for 1h; | |
65% | Stage #1: phenanthrene With oxygen; ozone In dichloromethane at -30℃; Stage #2: With sodium dithionite In dichloromethane at -30 - 30℃; for 33h; | |
61% | Stage #1: phenanthrene With ozone Stage #2: With acetic acid; sodium iodide | |
45% | With sodium periodate; C31H29Br2N3Ru*CH2Cl2 In water; ethyl acetate; acetonitrile at 25℃; for 0.5h; Inert atmosphere; Schlenk technique; | |
8.8% | With ruthenium trichloride; [bis(acetoxy)iodo]benzene In dichloromethane; water at 30℃; for 4h; | Typical method for isolation of aldehydes and diketone General procedure: The typical solution containing 1 mmol of substrates, 0.1 mol % RuCl3 and 3 equiv of PhI(OAc)2, was heated and kept at constant 30°C. After Reaction for a period of time, the mixture was then separated with separatory funnel and the dichloromethane phase was dried over anhydrous Na2SO4, filtered and the solvent removed under vacuum. The crude product was purified via a standard silica gel chromatography using hexanes/ethyl acetate as eluent to give the desired aldehyde and diketone products. The isolated products were characterized by NMR (in CDCl3 with TMS as an internal standard) and ESI-MS. All the reactions were performed at least three times to establish there producibility and reliability. |
With ozone | ||
(i) O3, O2, MeOH, (ii) P(OMe)3; Multistep reaction; | ||
(i) O3, (ii) NaI, AcOH; Multistep reaction; | ||
25 %Chromat. | With [VO(OMe)((E)-3-hydroxy-N'-(2-hydroxybenzylidene)2-2naphthohydrazide(-2H))]; dihydrogen peroxide In water; acetonitrile at 60℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With palladium diacetate; potassium carbonate; tricyclohexylphosphine tetrafluoroborate In N,N-dimethyl acetamide at 130℃; | |
83% | With potassium; potassium iodide; magnesium chloride In tetrahydrofuran for 12h; Heating; | |
With quinoline; potassium hydroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With lithium hexamethyldisilazane In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide at 20℃; | |
70% | With sodium hydrogencarbonate; dimethyl sulfoxide; triphenylphosphine; potassium iodide at 140℃; for 40h; Inert atmosphere; | Procedure for the preparation of phenanthrene from 2,2'-Bis-bromomethylbiphenyl (Scheme 8): In two neck round bottom flask a mixture of 2,2'-bis-bromomethyl-biphenyl 24 (0.20 g,0.588 mmol), triphenylphosphine (0.155 g, 0.588 mmol), NaHCO3 (0.296g, 3.54mmol)and potassium iodide (0.020 g, 0.117 mmol) in dimethylsulfoxide (30 mL) was stirred at140 °C under N2 atmosphere for 40 h. The cooled mixture was then poured in water (150mL) and extracted with dichloromethane (3 X 100 mL). The organic layer was washedwith water (2 X 100 mL) and dried over anhydrous sodium sulfate. The solution wasconcentrated under reduced pressure to obtain a crude product, which was purified bycolumn chromatography on silica gel and petroleum ether as eluent to give purephenanthrene 25 (0.073 g, 70 %). White solid; m. p. 96 °C [Reported 98 - 100 °C,Aldrich Chemical Catalogue]. The structure was further confirmed by H-NMR and Massanalysis. |
With diethyl ether; ammonia; sodium amide |
Multi-step reaction with 2 steps 1: toluene / 8 h / Heating 2: 70 percent / O2; 18-crown-6 ether; K2CO3 / VO(acac)2 / toluene / 8 h / 60 - 70 °C | ||
Multi-step reaction with 4 steps 1: 84 percent / Na2S*9H2O / H2O; methanol / Heating 2: 89 percent / 30 percent H2O2 / acetic acid; H2O / 1.5 h / Heating 3: 1) n-butyllithium / 1) benzene, ether, hexane, tetrahydrofuran, 4: 1) SOCl2 / 1) benzene, 3 h, reflux, 2) 2 h | ||
Multi-step reaction with 4 steps 1: 84 percent / Na2S*9H2O / H2O; methanol / Heating 2: 12 percent / H2O2 / acetic acid; H2O / 24 h / Ambient temperature 3: 1) n-butyllithium / 1) benzene, ether, hexane, tetrahydrofuran, 4: 1) SOCl2 / 1) benzene, 3 h, reflux, 2) 2 h | ||
Multi-step reaction with 4 steps 1: 84 percent / Na2S*9H2O / H2O; methanol / Heating 2: 50 mg / n-butyllithium / diethyl ether; hexane / 48 h / Ambient temperature 3: 1) n-butyllithium / 1) benzene, ether, hexane, 3 h, 2) 48 h 4: 1) SOCl2 / 1) benzene, 3 h, reflux, 2) 2 h | ||
Multi-step reaction with 2 steps 1: 84 percent / Na2S*9H2O / H2O; methanol / Heating 2: n-butyllithium / diethyl ether; hexane / 48 h / Ambient temperature | ||
Multi-step reaction with 2 steps 1: 84 percent / Na2S*9H2O / H2O; methanol / Heating 2: 37 percent Turnov. / n-butyllithium / diethyl ether; hexane / 2 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With phosphonic Acid; iodine In benzene at 100℃; for 36h; Sealed tube; Inert atmosphere; | 4.2. Typical procedure for preparation of targeted molecules General procedure: Under N2, a mixture of diketones 1 (0.3 mmol), H3PO3 (147.6 mg, 1.8 mmol), I2 (76.2 mg, 0.3 mmol) and benzene (0.6 mL) was stirred in a 25mL closed sealed tube in oil bath at 100C for 36 h. After the mixture was cooled down to the room temperature, the mixture was quenched by Na2S2O3 aqueous solution andwas extracted with EtOAc three times. Then the combined the organic layer was dried over MgSO4 and filtrated. The filtrate was concentrated and the residue was further purified by column chromatography on silica gel to give the product 2. |
With sodium chloride; anhydrous zinc chloride; zinc powder at 220 - 290℃; | ||
With zinc powder |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen fluoride at 10 - 15℃; Destillation des Reaktionsprodukts in Gegenwart von Quecksilber; | ||
With hydrogen fluoride at 10 - 15℃; Destillation des Reaktionsprodukts in Gegenwart von Quecksilber; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With graphite oxide In chloroform at 120℃; for 24h; | 4.4. Oxidation of hydrocarbons possessing methyl or methylene groups General procedure: In a typical preparation, a 7.5 mL vial was charged with GO (100 mg), substrate (50 mg), CHCl3 (0.5 mL) and a magnetic stir bar. The vial was then sealed with a Teflon-lined cap under ambient atmosphere and heated at 70 °C, 120 °C or 120 °C for 24 h. The reaction mixture was then cooled to room temperature and washed with CH2Cl2 (50 mL). The filtrate was collected and the solvent was removed under vacuum to obtain the crude product, which was then purified by silica chromatography (CH2Cl2, hexanes, EtOAc/CH2Cl2 or CH2Cl2/hexanes as the eluent). The oxidation reactions involving toluene, 4-nitrotoluene, cyclohexadiene, cyclohexene, and cyclohexane were performed using CDCl3 instead of CHCl3 and conversions were determined directly by 1H NMR spectroscopy. All products matched spectroscopic data reported previously in the literature (see ESI). |
78% | With 2-Iodobenzoic acid; potassium peroxomonosulfate In water; acetonitrile | |
68% | With oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone; sodium nitrite In toluene at 120℃; for 8h; |
53% | With sodium anthraquinone-2-sulfonate; oxygen; palladium diacetate; magnesium sulfate; toluene-4-sulfonic acid In chlorobenzene at 110℃; for 24h; | |
With palladium on activated charcoal In benzene for 1.66667h; Heating; var. slov., var. times, var. 4,5-disubstituted 9,10-dihydrophenanthrenes; | ||
With o-tetrachloroquinone In benzene at 80℃; for 4h; | ||
With phosphovanadomolybdic acid; oxygen; acetic acid at 110℃; for 15h; | ||
With hydrotris(3,4,5-tribromo)pyrazolylborate Cu(NCMe); dihydrogen peroxide In water; acetonitrile at 20℃; for 7h; | ||
34 %Chromat. | With trifluorormethanesulfonic acid In 1,2-dichloro-ethane at 150℃; for 0.5h; Microwave irradiation; Inert atmosphere; | |
With tert.-butylhydroperoxide; iron(III) chloride; C42H40Cu2N8 In water; acetonitrile at 60℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen fluoride at 50 - 60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride; nitrobenzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With methanesulfonic acid; bis-[(trifluoroacetoxy)iodo]benzene; In chloroform; at 20℃; for 3h; | Phenanthrene (3.56 g, 20 mmol) was added to 20 mL of chloroform at room temperature.Then (18.9 g, 44 mmol) of bis(trifluoroacetic acid) iodobenzene was added thereto.Add (6.95 g, 44 mmol) of methanesulfonic acid; keep the above reaction system at room temperatureShould be 3h; stop the reaction. Pour the reaction solution into 50 mL of distilled water.The liquid was separated first, and then extracted with an average of three times with 150 mL of chloroform. Keep the water phase,The organic phase was evaporated to dryness and recovered, and 10 mL of ethanol was added to the solid crude product.And adding NaOH (2.0 g, 50 mmol) to reflux for 5 hours, and evaporating the ethanol.The crude product was added to the remaining 15 mL of aqueous phase.NaHSO3 (1.04 g, 10 mmol) was added, and the mixture was stirred at room temperature for 1 hour, and hydrochloric acid was added to pH test paper to be acidic, followed by extraction with 45 mL of chloroform.The organic phase is concentrated until a solid precipitates, and the cooling is continued in an ice water bath.The solid was filtered, and the concentration and precipitation operation was repeated three times to precipitate a solid.Vacuum drying for 3 h, weighing to obtain the 9-hydroxyphenanthrene of the present invention(3.5 g, 18 mmol), yield 90%, NMR detection purity >99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With methanesulfonic acid; tris-(trimethylsilyl)silane; 1,1-bis(tert-butylperoxy)cyclohexane; In dichloromethane; at 20℃; for 0.5h;Schlenk technique; | The TMS3SiH mediated reduction of <strong>[17024-12-3]9-iodophenanthrene</strong> was performed, giving phenanthrene 31 in an excellent 94% yield (Scheme 9). Scheme 9: application of the initiator system combination for a radical dehalogenation. In an oven dried Schlenk tube, <strong>[17024-12-3]9-iodophenanthrene</strong> (304 mg, 1 mmol), was dissolved in dichloromethane (10 ml_). The resulting solution was degassed (Freeze-Pump-Thaw technique, 3 cycles), brought to room temperature and 1 (50% solution, 26 mg, 0.05 mmol) and TMS3SiH (308 muIota_, 1 mmol) were added. The mixture was degassed once more and after being brought back to room temperature, methane sulfonic acid (3.5 muIota_, 0.05 mmol) was added and the mixture left to react for 30 minutes. The mixture was evaporated to dryness and the resulting slightly yellow oil was purified by flash chromatography on silica gel (hexane as eluent) to afford 31 as a white solid (1 68 mg, 94% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With carbon disulfide; aluminum tri-bromide at -40 - 20℃; | 1 Into 500 ml of carbon disulfide, 17.8 g (100 mmol) phenanthrene (El), 21.5 g (100 mmol) E2, and 26.6 g (100 mol) aluminum bromide were mixed at -40 °C, and the resulting mixture was stirred for 3 hours. After the temperature of the mixture had returned to room temperature, stirring was conducted for 1 hour. The mixture was discharged into water and precipitates were filtered, washed with ethanol, and dried. As a result, 20 g (yield: 85%) of an ocher solid E3 was obtained. |
85% | With aluminum tri-bromide In carbon disulfide at -40 - 20℃; for 4h; | 1-1 (1-1) Synthesis of intermediate E3Reagents and solvents described below were charged into a reactor:phenanthrene (E1): 17.8 g (100 mmol)E2: 21.5 g (100 mmol)aluminum bromide: 26.6 g (100 mol)carbon disulfide: 500 ml After the reaction solution was cooled to -40 degrees Celsius, stirring was conducted for 3 hours at this temperature (-40 degrees Celsius). After the reaction solution was warmed to room temperature, stirring was conducted for 1 hour at this temperature (room temperature). The reaction solution was discharged into water and precipitated solids were filtered, washed with ethanol, and dried to obtain 20 g (yield: 85%) of E3 in form of ocher solids. |
42% | With aluminum tri-bromide In carbon disulfide at -40 - 20℃; for 4.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With o-tetrachloroquinone In 1,2-dichloro-ethane at 80℃; for 12h; Inert atmosphere; | |
70% | With o-tetrachloroquinone; palladium diacetate In 1,2-dichloro-ethane at 80℃; for 12h; | 31 In Example 31, the conjugated system was extended by the reaction of the formula below. The details are described below. A Pd(OAc)2 solution (2.2 mg, 10 mmol, 5.0 mol%), o-chloranil (59 mg, 0.24 mmol, 1.2 equivalents), phenanthrene (36 mg, 0.20 mmol, 1 equivalent) represented by the formula below: and a boron compound (64 mg, 0.12 mmol, 0.6 equivalents) represented by the formula below: were introduced into 1,2-dichloroethane (1,2-DCE, 2.0 mL), and the mixture was stirred for 12 hours at 80 °C. The reactionproduct was filtered using a silica gel (eluent: CH2Cl2, 50 mL), and the volatile substance was removed under reducedpressure. The residue was purified by PTLC (eluent: hexane/CH2Cl2=10:1). As a result, 46 mg of 9-(o-biphenyl)phenylphenanthrene represented by the formula below: was obtained (yield: 70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With copper dichloride; palladium dichloride In 1,2-dichloro-ethane at 80℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In tetrahydrofuran at 99.99℃; for 2h; Autoclave; Green chemistry; chemoselective reaction; | ||
With hydrogen; 2C18H42NSi2(1-)*Ba(2+) In benzene at 120℃; for 48h; Autoclave; Schlenk technique; | ||
With hydrogen; barium In benzene-d6 at 150℃; for 24h; Autoclave; Glovebox; Schlenk technique; |
With hydrogen; platinum(II) chloride In ethanol at 60℃; for 47h; | 10 Example 9. PtCl2 catalyzed hydrogenation and hydrodeoxygenation reaction and reaction products of monocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons. General procedure: 0.15mmol reaction substrate (e.g., phenol 14.11mg) was placed 20ml pressure reaction flask, 10ml to a reaction solvent (ethanol and tert-butanol) was dissolved, then adding the catalyst PtCl2 4mg (0.015 mmol). After replacing the air with H2 gas, stabilize the H2 pressure at 0.1-0.2Mpa. Stir the reaction at an appropriate temperature (e.g. 60°C). When the reaction proceeds to 2h and 6h (if the reaction conversion rate is low, the reaction proceeds for 22h), respectively take 1ml of the reaction solution and filter. Samples were taken and processed according to the method of Example 3, and the reaction products were analyzed by GC-MS.The specific results are shown in Table 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene for 2h; Reflux; | ||
Stage #1: phenanthrene; 7,7',8,8'-tetracyanoquinodimethane In neat (no solvent) at 200℃; Sealed tube; Stage #2: In neat (no solvent) at 130 - 160℃; for 50h; Sealed tube; Inert atmosphere; | General procedure: Phenanthrene (PHN) and picene (PCN) as donor molecules (D) were purchased by TCI with a purity of >97 % and >99 %, respectively. TCNQ, TCNQ-F2 (2,5-configuration) and TCNQ-F4 as acceptors (A) were also purchased by TCI with purities of >99 %, >98 % and >98 %, respectively. These starting molecules are shown in Fig. 1. The acceptor strength increases for higher fluorinated acceptors with an electron affinity of 2.85 eV for TCNQ; 3.02 eV for TCNQ-F2 and 3.20 eV for TCNQ-F4 [14]. Single crystals were grown by physical vapor transport (PVT) [15,16] in closed glass ampules. For this purpose, the starting materials (as powders) of D and A were ground together and transferred into a glass ampule, which was cleaned by ethanol and acetone before and baked in a box furnace for at least 24 h to remove water (as described in Ref. [11]). The glass ampule was evacuated to p=10-3 mbar before closing. The experimental oven setup and a typical temperature gradient used in the experiments are shown in Fig. 2 with Tsource as the temperature at the hottest position with the source material and Txcrystal with x = 1, 2, CT, where x denotes the crystal growth temperature of material1, material 2 and the CT complex, respectively. Typical crystal growth conditions are listed in Table1. The crystal growth zone lies in a region with a steep temperature gradient, which results in the best crystal growth as mentioned and suggested in Ref. [17]. The growth procedure lasted ca. 50 h until all starting material is sublimed and subsequently the ampule was removed from the hot oven. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With o-tetrachloroquinone; palladium diacetate In 1,2-dichloro-ethane at 80℃; for 12h; | 28 A Pd(OAc)2 solution (2.2 mg, 10 mmol, 5.0 mol%), o-chloranil (74 mg, 0.30 mmol, 1.5 equivalents), phenanthrene(36 mg, 0.20 mmol, 1 equivalent) represented by the formula below: and a boron compound (0.13 mmol, 0.67 equivalents) represented by the formula below: were introduced into 1,2-dichloroethane (1,2-DCE, 1.0 mL), and the mixture was stirred for 12 hours at 80°C. The reactionproduct was filtered using a silica gel (eluent: CH2Cl2, 50 mL), and the volatile substance was removed under reducedpressure. The residue was purified by PTLC (eluent: hexane). As a result, 9-phenyl phenanthrene (5a) represented bythe formula below: was obtained. Yield: 5a (33 mg, 64% yield). The spectral data of 9-phenylphenanthrene (5a) has been reported from Oi et al.(Kawai, H.; Kobayashi, Y.; Oi, S.; Inoue, Y. Chem. Commun. 2008, 1464). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With aluminum oxide In neat (no solvent, solid phase) at 90℃; for 6h; Schlenk technique; Inert atmosphere; | |
80% | With platinum(II) chloride In toluene at 100℃; for 24h; Inert atmosphere; | |
72% | With silver(I) hexafluorophosphate; [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)] In chlorobenzene at -78 - 120℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Phenanthrene (PHN) and picene (PCN) as donor molecules (D) were purchased by TCI with a purity of >97 % and >99 %, respectively. TCNQ, TCNQ-F2 (2,5-configuration) and TCNQ-F4 as acceptors (A) were also purchased by TCI with purities of >99 %, >98 % and >98 %, respectively. These starting molecules are shown in Fig. 1. The acceptor strength increases for higher fluorinated acceptors with an electron affinity of 2.85 eV for TCNQ; 3.02 eV for TCNQ-F2 and 3.20 eV for TCNQ-F4 [14]. Single crystals were grown by physical vapor transport (PVT) [15,16] in closed glass ampules. For this purpose, the starting materials (as powders) of D and A were ground together and transferred into a glass ampule, which was cleaned by ethanol and acetone before and baked in a box furnace for at least 24 h to remove water (as described in Ref. [11]). The glass ampule was evacuated to p=10-3 mbar before closing. The experimental oven setup and a typical temperature gradient used in the experiments are shown in Fig. 2 with Tsource as the temperature at the hottest position with the source material and Txcrystal with x = 1, 2, CT, where x denotes the crystal growth temperature of material1, material 2 and the CT complex, respectively. Typical crystal growth conditions are listed in Table1. The crystal growth zone lies in a region with a steep temperature gradient, which results in the best crystal growth as mentioned and suggested in Ref. [17]. The growth procedure lasted ca. 50 h until all starting material is sublimed and subsequently the ampule was removed from the hot oven. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With bis-[(trifluoroacetoxy)iodo]benzene In chloroform at 20℃; for 3h; | 7 Example 7 Phenanthrene (0.356 g, 2 mmol) was added to 2 mL of chloroform at room temperature.Then (2.15 g, 5 mmol) of bis(trifluoroacetic acid) iodobenzene was added thereto.Add (0.42 g, 4.4 mmol) of methanesulfonic acid; keep the above reaction system at room temperatureShould be 3h; stop the reaction. Pour the reaction solution into 5 mL of distilled water.The liquid was separated first, and then extracted with an average of three times with 15 mL of chloroform. Keep the water phase,The organic phase is evaporated to dryness and recovered, and 5 mL of ethanol is added to the solid crude product.And refluxed with NaOH (2.0 g, 5 mmol) for 5 hours, after cooling,Methyl iodide was added to the mixture, stirred at 50 ° C for 3 hours, and the solvent was evaporated to dryness.Add 5 mL of water, then extract three times with 15 mL of chloroform, concentrate the organic phase until a solid precipitates, repeat the concentration and precipitation operation 3 times, and combine to precipitate the solid.Drying in vacuum for 3 h, weighed to obtain 9-hydroxyphenidinamine according to the invention(0.38 g, 1.82 mmol), yield 91%, NMR detection >99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dipotassium peroxodisulfate; sodium triflate; silver nitrate In acetonitrile at 80℃; for 6h; | 1; 2; 3; 16 Embodiment 1 0.3 mmol of 2-phenylnitroolefin, 0.6 mmol of sodium trifluoromethanesulfonate, 0.6 mol of potassium persulfate, and 0.06 mmol of silver nitrate were placed in a 15 mL thick-walled pressure-resistant reaction tube, and then 3 mL of acetonitrile was added as a solvent.Then, magnetic stirring was carried out at 80 ° C for 6 hours.After cooling to room temperature, two tablespoons of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and the product was purified by column chromatography (yield petroleum ether / ethyl acetate = 100:1 as an eluent).This material was a white solid with a yield of 88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With dipotassium peroxodisulfate; sodium triflate; silver nitrate In acetonitrile at 90℃; for 24h; | 1-4 Example 1 0.3 mmol of 2-phenylcinnamaldehyde, 0.6 mmol of sodium triflate,0.6 mmol of potassium persulfate and 0.06 mmol of silver nitrate were added to a 15 mL thick-walled pressure-resistant reaction tube, and then 3 mL of acetonitrile (dried) was added as a solvent. Next, magnetic stirring was carried out at 90 ° C for 24 hours. After cooling to room temperature, two tablespoons of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography.The pure product of phenanthrene was obtained (with petroleum ether/ethyl acetate = 100:1 as eluent).This material was a white solid with a yield of 76%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With isopentyl nitrite In benzene at 50℃; | Phenanthrene (1) To 1,4-dihydrophenanthrene-1,4-imine (4) (0.716 g, 3.72 mmol) in benzene (40 mL) was added isoamyl nitrite (0.48 g, 4.1 mmol). The mixture was warmed to 50° C and the progress of the reaction followed by TLC (hexane: EtOAc, 8:2). After complete reaction,the solution was concentrated to dryness and redissolved in CH2Cl2 (40 mL). To this solution was added finely ground CaCl2 (0.90 g, 8.17 mmol) and a small amount of absolute ethanol (0.5 mL) with stirring. After 12 h the solution was filtered and concentrated to yield 0.603 g (86%) of crude 1. Sublimation at 85° C (0.3 Torr) afforded 0.546 g (78%) of 1 as white crystals mp 98-99° C (lit.25 mp 98.5-99° C), identical in all respects with a commercial sample. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Raney nickel; isopropyl alcohol at 150℃; for 5h; Inert atmosphere; | 2.3. General experimental procedure 1 General procedure: The batch reactor equipped with mechanical agitator MagneDrive(Autoclave Engineers) was charged by ∼3.2 mmole of substrate,0.20-0.30 g of sulfolane or decane (as an internal standard) and 120 mLof 2-PrOH. After adding the catalyst prepared from 0.45 g of aluminum-nickel alloy, the reactor was purged with argon under stirringthen closed, and heated up with the rate of ∼7 °C/min to reach thereaction temperature of 150±1 °C. The reaction was carried out atconstant temperature of 150 °C during 5 h with permanent stirring at800 rpm. During the reaction, probes of the reaction mixture werecollected hourly to the sampler. The final reaction mixture and all otherprobes were analyzed by GC-MS method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: potassium carbonate / acetonitrile / 2 h / Heating 2: copper(I) thiophene-2-carboxylate / 1-methyl-pyrrolidin-2-one / Inert atmosphere 3: manganese powder; trimethyl phosphite / 48 h / 140 °C / Inert atmosphere |
Tags: 85-01-8 synthesis path| 85-01-8 SDS| 85-01-8 COA| 85-01-8 purity| 85-01-8 application| 85-01-8 NMR| 85-01-8 COA| 85-01-8 structure
A1354644[ 1189955-53-0 ]
Phenanthrene-1,2,3,4,4a,10a-13C6
Reason: Stable Isotope
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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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