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CAS No. : | 1468-95-7 | MDL No. : | MFCD00001264 |
Formula : | C15H12O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JCJNNHDZTLRSGN-UHFFFAOYSA-N |
M.W : | 208.26 | Pubchem ID : | 73848 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 14 |
Fraction Csp3 : | 0.07 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 67.58 |
TPSA : | 20.23 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.41 cm/s |
Log Po/w (iLOGP) : | 2.1 |
Log Po/w (XLOGP3) : | 3.04 |
Log Po/w (WLOGP) : | 3.33 |
Log Po/w (MLOGP) : | 3.44 |
Log Po/w (SILICOS-IT) : | 3.9 |
Consensus Log Po/w : | 3.16 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.63 |
Solubility : | 0.0491 mg/ml ; 0.000236 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.13 |
Solubility : | 0.154 mg/ml ; 0.00074 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.58 |
Solubility : | 0.000543 mg/ml ; 0.00000261 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
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 |
---|---|---|
87% | With phosphorus tribromide; potassium hydrogencarbonate In toluene at 0 - 20℃; for 5 h; Inert atmosphere | 9-Bromomethylanthracene was prepared in good yield (>87percent) by the reduction of 9-anthracenecarboxaldehyde, followed by bromination with PBr3 under N2 atmosphere in toluene. To a stirred solution of 9-bromomethylanthracene (0.1g, 0.37mmol) in ACN (10mL), diethanolamine (0.07g, 0.67mmol), anhydrous K2CO3 (0.07g, 0.50mmol), and KI (0.08g, 0.50mmol) were added under N2. The reaction mixture was refluxed for 12h. The work-up was similar to that of PD. The crude product was purified using silica-gel chromatography (elution with 8.0percent MeOH in CH2Cl2:EtOAc (7:3 v/vpercent) containing 1.4percent NH4OH, Rf=0.5), yielding a brownish semi-solid PM (0.10g, 91percent). |
69% | With bromine; triphenylphosphine In acetonitrile at 20℃; for 2 h; | A solution of triphenylphosphine (16.44 g, 100.8 mmol) in acetonitrile (120 mL) was flushed with nitrogen for 20 minutes. Bromine (3.3 mL) was added and a solution of anthracen-9-yl-methanol (15.0 g, 72.0 mmol) in acetonitrile (10O mL) was added dropwise. The mixture was stirred for 2 hours at room temperature and refrigerated at 50C overnight. The solution was cooled to 00C for 30 minutes and filtered. The residue was washed with cold acetonitrile and purified by recrystallization from chloroform to give 9-bromomethyl-anthracene as yellow crystals (13.47 g, 69percent yield). 1H NMR (CDCl3) δ 8.51 (IH, s), 8.32 (2H, d), 8.05 (2H, d), 7.66 (2H, dd), 7.52 (2H, dd), 5.56 (2H, s). |
54% | With phosphorus tribromide In toluene at 0 - 20℃; for 2 h; | 7-(anthracen-9-ylmethoxy)-4-methyl-2H-chromen-2-one (48) SU06-02; 9-(bromomethyl)anthracene (47); To a stirring suspension of 9-anthracenemethanol (2.0 g, 9.6 mmol) at 0 0C in toluene (100 ml) was added PBr3 (1.2 ml_, 12.51 mmol) and the suspension was stirred at 0 °C for 1 h. The reaction mixture was then brought up to room temperature and let to stir for further 1 h. The mixture turned into a yellow solution. K2CO3 (10 mL) was added to quench the reaction. Toluene was evaporated off in-vacuo. The residue was taken up in EtOAc and washed with saturated aqueous K2CO3, water and brine and dried (MgSO4). The solvent was evaporated off in-vacuo and the crude residue was purified by flash chromatography, eluting with hexane:EtOAc (2:1 ) to give 47 (1.4 g, 54percent) as yellow solid. H1 NMR (500MHz, CDCI3): δ = 8.45 (1 H, s, Ar-10 H), 8.27 (2H, d, Ar-1 ,8 H), 8.00 (2H, d, Ar-4, 6 H), 7.62 (2H, d, Ar-2, 7 H), 7.48 (2H, d, Ar-3, H), 5.50 (2H, s, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With Silphos; bromine In acetonitrile for 0.75h; Heating; | |
96% | With sulfuric acid; hydrogen bromide; sodium bromide In diethyl ether | |
94% | With phosphorus tribromide In toluene at 0 - 20℃; |
94% | With phosphorus tribromide In toluene at 0 - 20℃; Inert atmosphere; | |
92% | With phosphorus tribromide In toluene at 0℃; for 1h; Inert atmosphere; | |
92% | With phosphorus tribromide In toluene at 0℃; for 1h; | |
91% | With phosphorus tribromide In toluene at 0 - 20℃; for 1h; Inert atmosphere; | |
89% | With boron tribromide In dichloromethane at -78 - 20℃; | |
87% | With phosphorus tribromide; potassium hydrogencarbonate In toluene at 0 - 20℃; for 5h; Inert atmosphere; | Synthesis of PM 9-Bromomethylanthracene was prepared in good yield (>87%) by the reduction of 9-anthracenecarboxaldehyde, followed by bromination with PBr3 under N2 atmosphere in toluene. To a stirred solution of 9-bromomethylanthracene (0.1g, 0.37mmol) in ACN (10mL), diethanolamine (0.07g, 0.67mmol), anhydrous K2CO3 (0.07g, 0.50mmol), and KI (0.08g, 0.50mmol) were added under N2. The reaction mixture was refluxed for 12h. The work-up was similar to that of PD. The crude product was purified using silica-gel chromatography (elution with 8.0% MeOH in CH2Cl2:EtOAc (7:3 v/v%) containing 1.4% NH4OH, Rf=0.5), yielding a brownish semi-solid PM (0.10g, 91%). |
77% | With phosphorus tribromide | |
77% | With phosphorus tribromide In toluene at 0℃; for 1h; | |
75% | With bromine; triphenylphosphine In acetonitrile at 5℃; | |
70% | With bromine; triphenylphosphine In acetonitrile | |
69% | With bromine; triphenylphosphine In acetonitrile at 20℃; for 2h; | 1.b A solution of triphenylphosphine (16.44 g, 100.8 mmol) in acetonitrile (120 mL) was flushed with nitrogen for 20 minutes. Bromine (3.3 mL) was added and a solution of anthracen-9-yl-methanol (15.0 g, 72.0 mmol) in acetonitrile (10O mL) was added dropwise. The mixture was stirred for 2 hours at room temperature and refrigerated at 50C overnight. The solution was cooled to 00C for 30 minutes and filtered. The residue was washed with cold acetonitrile and purified by recrystallization from chloroform to give 9-bromomethyl-anthracene as yellow crystals (13.47 g, 69% yield). 1H NMR (CDCl3) δ 8.51 (IH, s), 8.32 (2H, d), 8.05 (2H, d), 7.66 (2H, dd), 7.52 (2H, dd), 5.56 (2H, s). |
54% | With phosphorus tribromide In toluene at 0 - 20℃; for 2h; | 7-(anthracen-9-ylmethoxy)-4-methyl-2H-chromen-2-one (48) SU06-02; 9-(bromomethyl)anthracene (47); To a stirring suspension of 9-anthracenemethanol (2.0 g, 9.6 mmol) at 0 0C in toluene (100 ml) was added PBr3 (1.2 ml_, 12.51 mmol) and the suspension was stirred at 0 °C for 1 h. The reaction mixture was then brought up to room temperature and let to stir for further 1 h. The mixture turned into a yellow solution. K2CO3 (10 mL) was added to quench the reaction. Toluene was evaporated off in-vacuo. The residue was taken up in EtOAc and washed with saturated aqueous K2CO3, water and brine and dried (MgSO4). The solvent was evaporated off in-vacuo and the crude residue was purified by flash chromatography, eluting with hexane:EtOAc (2:1 ) to give 47 (1.4 g, 54%) as yellow solid. H1 NMR (500MHz, CDCI3): δ = 8.45 (1 H, s, Ar-10 H), 8.27 (2H, d, Ar-1 ,8 H), 8.00 (2H, d, Ar-4, 6 H), 7.62 (2H, d, Ar-2, 7 H), 7.48 (2H, d, Ar-3, H), 5.50 (2H, s, CH2). |
14% | With phosphorus tribromide In toluene at 80℃; for 2h; | |
With phosphorus tribromide; benzene | ||
With hydrogen bromide | ||
With pyridine; phosphorus tribromide | ||
With hydrogen bromide | ||
With bromine; triphenylphosphine In acetonitrile at 20℃; | ||
With bromine; triphenylphosphine In acetonitrile at 25℃; | ||
With bromine; triphenylphosphine In acetonitrile at 25℃; Inert atmosphere; | ||
With phosphorus tribromide at 0 - 20℃; | ||
With bromine; triphenylphosphine In acetonitrile at 20℃; for 1h; | ||
With hydrogen bromide In dichloromethane | ||
With phosphorus tribromide In toluene at 0℃; | ||
With phosphorus tribromide | ||
With phosphorus tribromide In toluene at 0℃; for 2h; Inert atmosphere; | ||
With phosphorus tribromide In dichloromethane at 20℃; Cooling with ice; | 3.1 Weigh 416 mg of compound (a") (known compound CAS: 2417-77-8) (2 mmol, 1 eq) into a 100 mL single-neck bottle,Dissolve with 10mL dry dichloromethane solution,Add 378.98mg of phosphine tribromide (PBr3, 1.4mmol, 0.7eq) into a 100mL constant pressure dropping funnel,After dissolving with 20mL of dry dichloromethane,Under ice water bath conditions,Drop it dropwise into the reaction flask. After the addition is complete,Remove the ice water bath,React at room temperature. React overnight,Point board found,The raw material reaction is complete,Stop the reaction,Since the bromine atom in the bromine produced by this reaction is at the benzyl position,Easier to change,So the points are more complicated. For post-processing,In the ice water bath,Add water to the reaction flask,Stir for a while,The reaction system was transferred to a 60mL separatory funnel, the layers were separated, the upper aqueous phase was back-extracted with dichloromethane solution for 2-3 times, the organic phases were combined, washed with saturated sodium chloride solution, dried with anhydrous sodium sulfate, The plate (PE) found that there was a new spot with Rf=0.3, the new spot had obvious fluorescence, and the phosphomolybdic acid developer appeared yellow. The dried system was distilled under reduced pressure to obtain a yellow solid. This reaction does not need to go through the column, because the bromide at the benzylic position is easy to change, directly use this initial product (compound b”) for the next reaction |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium tetrahydroborate In ethanol at 20℃; for 0.5h; | Anthracen-9-yl-methanol General procedure: 9-Anthraldehyde (1; 206 mg, 1.0 mmol) wassuspended in ethanol (3.0 mL). To the suspension was added sodium borohydride(38 mg, 1.0 mmol). After stirring for 30 min at rt, the reaction mixture was quenched with water (2 mL). The aqueous phase was extracted with ether (5 mL). The organicextract was dried over anhydrous Na2SO4 and concentrated to give the crude alcohol, which waspurified by flash column chromatography (silica gel 10 g, hexanes/ethyl acetate = 80/20) to give thealcohol 5 (206 mg, 99%) as a pale yellow solid. Registry number 1468-95-7; Rf = 0.27(hexane:AcOEt = 80:20); 1H NMR (CDCl3, 300 MHz) δ = 1.80 (brs, 1H, -OH), 5.62 (s, 2H, -CH2-),7.38-7.64 (m, 4H, Ar), 8.00 (d, J = 8.3 Hz, 2H, Ar), 8.38 (d, J = 8.7 Hz, 2H, Ar), 8.44 (s, 1H, H-10) |
99% | With sodium tetrahydroborate In ethanol at 20℃; for 0.5h; | 9-Anthraldehyde (1aA; 206 mg, 1.0 mmol) was suspended inethanol (3.0 mL). To the suspension was added sodium borohydride (38 mg, 1.0 mmol). Afterstirring for 30 min at Rt, the reaction mixture was quenched with water (2 mL). The aqueousphase was extracted with ether (5 mL). The organic extract was dried over anhydrous Na2SO4and concentrated to give the crude alcohol, which was purified by flash column chromatography(silica gel 10 g, hexanes/ethyl acetate = 80/20), affording the anthracen-9-ylmethanol (2aA’; 206 mg, 99%) as apale yellow solid: Registry number 1468-95-7; Rf = 0.27 (hexane:AcOEt = 80:20); 1H NMR (300 MHz, CDCl3) δ= 1.80 (brs, 1H, -OH), 5.62 (s, 2H, -CH2-), 7.38-7.64 (m, 4H, Ar), 8.00 (d, J = 8.3 Hz, 2H, Ar), 8.38 (d, J = 8.7Hz, 2H, Ar), 8.44 (s, 1H, H-10); 13C NMR (75 MHz, CDCl3) δ = 131.60 (C), 131.08 (C), 130.30 (C), 129.19(CH), 128.42 (CH), 126.49 (CH), 125.13 (CH), 123.93 (CH), 57.33 (CH2). |
99% | With sodium tetrahydroborate In tetrahydrofuran for 2h; Reflux; |
98.3% | With sodium tetrahydroborate In ethanol at -0.16 - 20℃; | |
97% | With sodium tetrahydroborate In tetrahydrofuran; water for 1.05h; | |
96% | With sodium tetrahydroborate In tetrahydrofuran at 25℃; for 1h; | |
96% | With sodium tetrahydroborate In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; | |
96% | With sodium tetrahydroborate In tetrahydrofuran at 25℃; for 1h; | 4 anthracen-9-ylmethanol (2): To 4.9 g (23.76 mmol) of anthracene-9-carbaldehyde (1) in THF (50 mL) was added 1.35g (35.64 mmol) of NaBH4. The mixture was stirred for 1 h at 25 °C. The mixture was poured into water (400 mL) resulting in a yellow precipitate. The yellow solid was filtered off, washed thoroughly with water, and dried. (4.7 g, 96% isolated yield).’‘H NMR (500 MHz, CDC13) ö 8.46 (s, 1H), 8.40 (d, 2H, J = 8.8 Hz), 8.02 (d, 2H, J = 8.4 Hz), 7.59-7.53 (m, 2H), 7.52-7.46 (m, 2H), 5.65 (s, 2H). |
96% | With sodium tetrahydroborate In tetrahydrofuran at 20℃; for 2h; | |
93% | Stage #1: 9-anthracene aldehyde With zinc diacetate In tetrahydrofuran at 65℃; for 0.166667h; Stage #2: With methyl-di(n-propoxy)silane In tetrahydrofuran at 65℃; for 24h; Stage #3: With hydrogenchloride; water at 0℃; for 1h; | |
92% | With methanol; sodium tetrahydroborate | General procedure for the synthesis of bridged sulfides 6 General procedure: Aldehydes 9 (16 mmol) dissolved in methanol,were reduced to corresponding alcohols 14 using sodium borohydride (1.1 g, 30 mmol) in methanol. Alcohols 14 (10 mmol) and two equivalents of thiourea (1.5 g, 20 mmol) were dissolved in acetone (25 mL) and 5N HCl(5 mL) was added to it and stirred overnight. The precipitate formed was filtered and treated with sodium hydroxide (10 %, 30 mL) solution and stirred at room temperature for 2h. Acidification with 5N HCl (25 mL) yielded 16 in 87-95 % yield as shown in Table 2. To a solution of anthracenethiols 16 (5 mmol) dissolved in chloroform (20 ml), KOH (0.20 g, 5 mmol) dissolved in methanol was added at 0 °C followed by propargyl bromide (0.38 mL, 5 mmol) and stirred overnight. Reaction mixture was concentrated, washed with water and extracted with dichloromethane to obtain thioethers 17 in 75-85 % yields. Thioethers 17 were purified by silicagel column chromatography using a mixture of hexane and dichloromethane as eluents. IMDA reaction of 17(5 mmol) was effected by refluxing in p-xylene (10 mL) (5-10h) to obtain corresponding barrelenes 6 in 70-80% yields after recrystallization from suitable solvents. |
88% | With sodium tetrahydroborate | |
88% | With sodium tetrahydroborate; ethanol at 40℃; for 2h; | |
88% | With [Ru(1,2-bis(diphenylphosphino)benzene )(CO)2Cl2]; potassium <i>tert</i>-butylate In propan-1-ol at 95℃; for 6h; | |
87% | With 2,2'-bi(1,3,6,2-dioxazaborocane); water In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Sealed tube; | |
85% | With formic acid In ethanol at 80℃; for 12h; | |
82% | With sodium tetrahydroborate In ethanol | |
80% | With sodium tetrahydroborate; ethanol for 2h; Cooling with ice; Sealed tube; | |
77% | Stage #1: 9-anthracene aldehyde With sodium tetrahydroborate In methanol at 20℃; for 11h; Stage #2: With ammonium chloride In methanol; water | |
66% | With sodium tetrahydroborate In chloroform at 20℃; | 3.1 (1) Firstly, compound (a") and compound (b") are synthesized sequentially using 9-anthracenealdehyde as raw material. The reaction equation is as follows: Weigh 2.06g of 9-anthracenealdehyde (10mmol, 1eq) yellow powdery solid and 100mL single-necked bottle,Add about 15mL of chloroform (CHCl3) solvent,Stir at room temperature,Because a lot of bubbles are generated during the reaction,and so,After all the raw materials are dissolved,Be sure to slowly add 0.38g sodium borohydride (NaBH4, 10mmol, 1eq) white solid,With the addition of sodium borohydride,The wine-red transparent solution of the reaction system gradually turned into a yellow solid. After all the sodium borohydride is added,Reaction 3-4h,Click the board (PE: AcOEt = 10:1) to find thatThe raw material reacts completely,And there is a new point with Rf=0.8. This new point has obvious fluorescence. It is yellow when placed in an iodine tank, and the phosphomolybdic acid developer is pink. The reaction is stopped, and post-treatment is performed. Add a saturated NH4Cl solution to the reaction system. Stir for a while at room temperature, filter with ethyl acetate (50mL), wash the filtrate with saturated sodium chloride solution, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure to dry the system to obtain the initial product as a yellow solid. After passing through a silica gel column (PE: AcOE = 5:1), a yellow solid was obtained. The structure was confirmed by nuclear magnetic field. The solid was compound (a") (known compound CAS: 1468-95-7), and the yield was 66%. . |
63% | With Grubbs catalyst first generation; potassium hydroxide In 1,4-dioxane at 80℃; for 20h; | |
With methanol; nickel Hydrogenation; | ||
With aluminum isopropoxide; isopropyl alcohol | ||
With lithium aluminium tetrahydride; diethyl ether | ||
With sodium hydroxide; sodium tetrahydroborate | ||
With sodium tetrahydroborate | ||
With sodium tetrahydroborate | ||
With sodium tetrahydroborate In methanol; water 1.) 50 deg C, 2.) RT, 1.5 h; | ||
With lithium aluminium tetrahydride | ||
With sodium tetrahydroborate | ||
With sodium cyanoborohydride In methanol at 20℃; | ||
With hydrogen; magnesium In methanol at 20℃; for 0.75h; | ||
19.63 g | With sodium tetrahydroborate In tetrahydrofuran for 0.5h; Heating; | |
With sodium tetrahydroborate In methanol; chloroform at 0 - 20℃; | ||
With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; C19H23N2O8PS(2-)*2Na(1+); sodium formate; alkaline phosphatase In ethanol at 37℃; for 0.5h; | ||
With sodium tetrahydroborate In methanol | ||
98 %Spectr. | With 1-hydrosilatrane; sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; | |
Multi-step reaction with 2 steps 1: C27H44AlN3 / benzene / 0.33 h / 20 °C / Inert atmosphere; Glovebox 2: silica gel / Inert atmosphere; Heating | ||
Multi-step reaction with 2 steps 1: Nd(O(2,6-tBu<SUB>2</SUB>-4-MeC<SUB>6</SUB>H<SUB>2</SUB>))<SUB>3</SUB>(THF)<SUB>2</SUB> / tetrahydrofuran / 0.5 h / 25 °C 2: hydrogenchloride / water | ||
With sodium tetrahydroborate In ethanol at 20℃; for 3h; | ||
With sodium tetrahydroborate In aq. phosphate buffer; dimethyl sulfoxide | ||
95 %Chromat. | With C24H27ClN2ORu; isopropyl alcohol; potassium hydroxide at 100℃; for 0.5h; | 2.5. General procedure for the catalytic transfer-hydrogenation reactions General procedure: In a typical run, an oven-dried 10 ml round-bottomed flask wascharged with the aldehyde (1 mmol), a known mol percent of thecatalyst, and KOH (0.5 mmol) dissolved in 2-propanol (5 ml). Theflask was placed in a preheated oil bath at the required temperature.After the specified time, the flask was removed from the oilbath and water (20 ml) was added, and extracted with diethylether (4-10 ml). The combined organic layers were washed withwater (3-10 ml), dried with anhydrous Na2SO4, and filtered.Diethyl ether was removed under vacuum and the residueobtained dissolved in hexane and analyzed by GC-MS. |
50 %Chromat. | With propan-1-ol; C31H27ClN5O2Ru(1+)*ClO4(1-); sodium t-butanolate at 85℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium carbonate; chlorobenzene In toluene at 105℃; for 24h; | |
100% | With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In N,N-dimethyl-formamide at 23 - 25℃; for 7.5h; | |
99% | With polymeric complex of oxodiperoxochromium(VI) compound and pyrazine (Pyz-CrO5)n In dichloromethane for 0.6h; Ambient temperature; |
99% | With potassium carbonate; chlorobenzene; 2-dicyclohexylphosphino-1,1'-biphenyl In toluene at 105℃; for 24h; | |
99.6% | With tert.-butylhydroperoxide In decane; <i>tert</i>-butyl alcohol at 25℃; for 5h; | |
98% | With 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; iron(III) chloride In lithium hydroxide monohydrate; ethyl acetate for 1h; Heating; | |
97% | With 1-hydroxy-1.oxo-1H-1λ5-benzo[d][1,2]iodoxol-3-one pyridinium salt In N,N-dimethyl-formamide at 24 - 28℃; for 4h; | |
97% | With oxygen; potassium carbonate In toluene at 90℃; for 10h; | |
95% | With dihydrogen peroxide In lithium hydroxide monohydrate at 100℃; for 9h; chemoselective reaction; | |
94% | With C23H35N3O3(1+)*Br(1-); copper atom In chlorobenzene at 80℃; for 15h; | |
94% | With lactate; dihydrogen peroxide at 30℃; for 7h; | Typical procedure for the oxidation of alcohols General procedure: A mixture of alcohol (1 mmol) and lactic acid (1 mL) was charged in 25 mL round bottom flask subjected to constant magnetic stirring at room temperature (30°C). The reaction mixture was further activated by addition of 30% H2O2 (1.07 equiv.). The reaction progress was monitored by GC. After completion of the reaction, Dichloromethane (2×6 mL) was added to the reaction mixture and then washed with distilled water (2×2mL). The organic layer was separated and dried over Na2SO4 and removed under reduced pressure. The crude product was obtained by evaporation method and again purified by column chromatography using ethyl acetate and n-hexane as eluting system. |
93% | With bis(cyclopentadienyl)cobalt(II); C18H11Cl3FeN4(1-); sodium hydroxide In toluene at 75℃; for 4h; Inert atmosphere; Schlenk technique; | |
90% | With zinc bismuthate In toluene for 1h; Heating; | |
88% | With tert.-butylnitrite; oxygen; 3,6-di(2'-pyridyl)-1,2,4,5-tetrazine; glacial acetic acid In acetonitrile at 20℃; for 4h; Irradiation; | |
88% | With carbonylchlorohydridotris(triphenylphosphine)ruthenium(II); oxygen In toluene at 90℃; for 18h; Molecular sieve; Sealed tube; | |
87% | With oxygen; anhydrous sodium carbonate In lithium hydroxide monohydrate for 2h; Reflux; | General procedure: A mixture of alcohol (1 mmol), Na2CO3(2 mmol), and Fe3O4SiO2/CuO nanocatalyst (0.04 g) in water was stirred under oxygen at reflux condition. After reaction completion, the catalyst was separated from the reaction mixture by external magnetic field, washed with hot EtOAc (2 × 5 mL), and dried for consecutive reaction runs. Then, the filtrate was cooled to room temperature, quenched with 2 MHCl aqueous solution, filtered, and extracted with dichloromethane. The solvent was evaporated and the organic layer dried over anhydrous Na2SO4. Evaporation of the solvent followed by column chromatography on silica gel (n-hexane/ethyl acetate 9:1 as v/v%) afforded the pure products. |
86% | With C35H28Cl2N5PRu; potassium-t-butoxide In toluene at 50℃; for 6h; chemoselective reaction; | 2.5. Procedure for catalytic alcohol oxidation reaction General procedure: using the complex 1 as catalyst in presence of a base following a general procedure. In a round-bottom flask, 1 mmol of substrate, 0.005mmol of catalyst (3.6mg) and 0.010 mmol of tBuOK (1.1mg) were mixed in 10mL toluene. The reaction mixture was heated at 50°C in aerobic condition with continuous stirring for 6h and then the solvent was evaporated with a rotary evaporator under reduced pressure. The crude product, thus obtained, was purified on preparative silica gel GF-254 TLC plate using ethyl acetate: hexane (1:10) solvent mixture as eluent. The oxidized products were characterized by NMR spectroscopy (See Figs. S4-S32). |
85% | With potassium permanganate; zirconium(IV) oxychloride In diethyl ether at 20℃; for 6h; | |
85% | With oxygen; potassium carbonate In N,N-dimethyl acetamide at 100℃; for 15h; | |
85% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; calcium methanolate In acetonitrile at 0 - 20℃; | |
85% | With pyridinium chlorochromate supported on montmorillonite KSF for 0.3h; Milling; | Typical procedure for the oxidation and oxidative deprotection reactions General procedure: A mixture containing the PCC supported on KSF (1.7 g) and the substrate (0.5 mmol)was introduced into a clean and dry ball-milling vessel (grinding jar 12 mL) with twostainless steel grinding balls (d 15 mm). Next, the milling process was started at350 rpm for the time mentioned in Tables 2 and 3 and the progress of the reaction wasscreened by TLC (n-hexane, ethyl acetate 9:1). After completion, the resulting solid mixturewas washed with diethyl ether (2310 mL) and then the obtained filtrate was concentratedunder reduced pressure. Eventually, further purification was carried out bycolumn chromatography on silica gel (n-hexane/ethyl acetate, 9:1) if it was required. Allof the products were known compounds, identified on the basis of matching meltingpoints (for solids), Rf values (for liquids) and 1H-NMR and 13CNMR spectra with thosein the literature cited in Tables 2 and 3. Original spectra were submitted for review andare available in the Supplementary Materials or from the corresponding author uponrequest. For the sake of completeness, representative data are provided below. |
85% | With potassium carbonate In n-heptane at 80℃; for 24h; | S4. Procedure for the synthesis of aldehydes and ketones General procedure: A magnetic stir bar, 0.5 mmol alcohol and 3 mL n-heptane solvent were added to 20 mL glass tube. Then, 35mg catalyst and 10 mol% of K2CO3 were added. The glass tube containing reaction mixture was f itted withseptum and connected to a balloon containing one bar of air. Then the glass tube was placed into a preheatedaluminum block at 85°C. Temperature inside the reaction tube was measured to be 80 oC and this temperaturehas been taken as the reaction temperature. The reaction was allowed to progress under continuous stirringfor the required time at 80 °C. Af ter completion of the reaction, the glass tube was cooled down to roomtemperature. Afterwards, the catalyst was f iltered-off and washed with ethyl acetate. The solvent f rom thef iltrate containing the reaction products was removed in vacuum and the corresponding aldehyde/ketone waspurif ied by column chromatography. All products were analyzed by GC-MS and NMR spectroscopy analysis.In the case of yields determined the by GC, 100 μL n-hexadecane was added to the reaction vial containingthe products and diluted with ethyl acetate. Then, the reaction mixture containing catalyst and products wasf iltered through a plug of silica and the filtrate containing product was analyzed by GC. |
83% | With IBS; potassium peroxomonosulfate; N-hexadecyl-N,N,N-trimethylammonium bromide In lithium hydroxide monohydrate at 20℃; for 2h; Green chemistry; chemoselective reaction; | IBS-catalysed alcohol oxidation in CTAB micelle; general procedure General procedure: The alcohol (2 mmol) was added to a solution of IBS (0.02 mmol, 0.01 eq), oxone (2.2 mmol, 1.1 equiv.) and 3 wt% CTAB solution (5 mL). The mixture was stirred at room temperature. The reaction was monitored by TLC. After completion, the solution was extracted with CH2Cl2 (3 × 10 mL). The combined organic phase was then filtered through a pad of silica gel and evaporated under vacuum to afford the desired product. |
82% | With nickel(II) dibenzotetramethyltetraaza[14]annulene; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 85℃; for 7h; Inert atmosphere; Schlenk technique; Sealed tube; | |
82% | With [Ru(2,6-bis(phenylazo)pyridine)(2-(4-chlorophenylazo)pyridine)Cl]PF6; potassium-t-butoxide; oxygen In toluene at 69.84℃; for 6h; | |
81% | With potassium-t-butoxide; C20H16N6NiS4 In toluene at 100℃; for 6h; Inert atmosphere; Schlenk technique; | |
80% | With sym-collidinium chlorochromate; orthoperiodic acid In acetonitrile at 20℃; for 0.333333h; | Typical procedure for the oxidation alcohols to aldehydes and ketones using periodic acid catalyzed by S-COCC General procedure: A solution of acetonitril (10 mL, 1mmol) and periodic acid was placed in flask and stir for the 15 min. Then, a mixture of alcohols (1mmol) and S-COCC (1%mmol) was added and the resulting mixture was stirred at room temperature for a suitable period (Table 3) and completion of the reaction investigated byTLC (n-hexane/EtOAc; 2:1) analysis. Then, EtOAc (20ml) was subjoined to the reaction mixture and after being washed with water/sodium solfite (1:1), the mixture was filtered off. The solvent was vaporized and produced pure products. |
78% | With oxygen In acetonitrile at 25℃; for 1.5h; UV-irradiation; | |
75% | With iodine; oxygen In acetonitrile at 20℃; for 4h; Irradiation; | |
74% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; tetra-n-butylammonium azide In acetonitrile at 25℃; for 12h; Irradiation; | |
70% | With aluminium(III) chloride; silver(I) bromate In acetonitrile for 0.75h; Heating; | |
70% | With mercuric (II) oxide In acetonitrile at 25℃; UV-irradiation; | |
70% | With 1H-imidazole; sodium (meta)periodate In lithium hydroxide monohydrate; acetonitrile at 20℃; for 1h; | |
69% | With 1-n-butyl-3-methylimidazolium hydrogen sulfate; NaBrO3 In lithium hydroxide monohydrate at 60℃; for 1h; Green chemistry; | General procedure for the oxidation of 1,2-diols, a-hydroxyketones and alcohols to 1,2-diketones and aldehydes/ketones General procedure: In a typical experiment, a mixture of 1,2-diols/a-hydroxyketones/alcohols (1 mmol), sodium bromate (3 mmol),and bmim[HSO4]:H2O 3:1 (v/v) along with a stir bar was placed in a RB flask fitted with a condenser. The reaction mixture was stirred magnetically in an oil-bath maintained at 60 C for an appropriate time as mentioned in Tables 3,4, and 5, respectively. After completion of the reaction, as monitored by TLC using petroleum ether:ethyl acetate(80:20, v/v) as eluent, the reaction mixture was cooled to room temperature and worked up as mentioned above. The product obtained was identified by m.p (wherever applicable), IR and NMR spectra. |
68% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In aq. buffer at 40℃; for 12h; | |
68% | With acetic anhydride; glacial acetic acid In dimethyl sulfoxide at 60℃; for 0.166667h; Microwave irradiation; Green chemistry; | 9 Example 9 9a (0.48mmol, 0.1g), DMSO 1.50mL, Ac2O 1.04mL, AcOH 0.18mL were sequentially added to a 15mL microwave reaction tube, the microwave power was 150w, the heating temperature was 60°C, and the reaction time was 10min.After cooling, NaHCO3 solution was added and stirred at room temperature for 30 min. Extract with ethyl acetate, collect the organic phase, and extract the aqueous phase with ethyl acetate 2-3 times.The organic phases were combined, washed with water in sequence, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product 9b (yield: 68%). |
65% | With NBS; 1-n-butyl-3-methylimidazolium tetrafluoroborate at 70℃; for 2h; | |
60% | With potassium hydroxide In toluene at 100℃; for 5h; | 9 2.2 General procedure for the dehydrogenation of benzylic alcohols using Ag/ZnO nanoparticles General procedure: A mixture of alcohol (1 mmol), KOH (1 mmol), and 0.005 g Ag/ZnO nanoparticles (2) (containing 8×10-5g Ag) in toluene (2 mL) was stirred at 100 °C for the appropriate time. The reaction was monitored by thin layer chromatography (TLC) or GC. After completion of the reaction, the reaction mixture was diluted with EtOAc and centrifuged to remove the catalyst. The filtrate was extracted with water, the organic layer dried over CaCl2 and evaporated under reduced pressure. The resulting product was purified by column chromatography on silica-gel to afford the pure product. All compounds are known and were characterized by comparison of their physical and spectroscopic data with the already described in the literature. |
59% | With dimethyl sulfoxide; triethylamine In dichloromethane at -40 - 20℃; for 8h; | |
42% | With tert.-butylhydroperoxide In ethanol at 65℃; for 2h; Green chemistry; | 2.6 General procedure for the oxidation of benzyl alcohols General procedure: Fe3O4/HT-SH-Ag (0.007g, 4.0mol%) was added to mixture of benzyl alcohol and TBHP (0.5mmol) in EtOH (0.5mL) at 65°C. The reaction process was monitored via TLC. In the end, the Fe3O4/HT-SH-Ag was removed using an external magnetic field after reaction completion, washed via EtOH, dried, and reused for several consecutive runs. The resultant product was purified using plate chromatography by EtOAc/n-hexane (3:10) solvent mixture. |
39% | With Eosin In dimethyl sulfoxide at 80℃; for 24h; Irradiation; | |
33% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; Cu<SUB>3</SUB>(1,3,5-benzenetricarboxylate)<SUB>2</SUB>; oxygen; anhydrous sodium carbonate In acetonitrile at 75℃; for 16h; | |
31% | With potassium carbonate In lithium hydroxide monohydrate at 60℃; for 24h; | 4.1. General Procedure for Heck Coupling and the Oxidationof Alcohols General procedure: A typical reaction was carried out as follows: bromobenzene(1a) (1.0 mmol), alkene (1.5 mmol), HCOONa (1.5mmol), 50 mg of wool-Pd complex catalyst (Pd 11.74 %),were added to 15 mL aqueous media (PEG-400 = 33 mg) ina 25 mL beaker, and stirred at 80 °C under ambient conditions.After the completion of the reaction, the catalyst was filtrated, washed and dried. Subsequently, 40 mg of the solid catalyst, benzyl alcohol (0.2 mmol), K2CO3 (0.2 mmol) were stirred in 15 mL aqueous media (PEG-400 = 33 mg), atmosphericair was used as the source of molecular oxygen at 60°C for 24 h, and the oxidation monitored by TLC. After completion, an extraction with ethyl acetate was performed.The organic layer was dried under reduced pressure to givethe desired crude product. Analytically pure products were obtained by column chromatography using petroleum ether and ethyl acetate as eluent. Formation of products and consumptionof substrates were monitored by GC. The identity of products was determined either by comparison with authentic samples using GC or by NMR analysis. The conversion and product selectivity were determined using GC analysis. |
With potassium carbonate; chlorobenzene; 2-dicyclohexylphosphino-1,1'-biphenyl In toluene at 105℃; for 24h; | ||
87 %Chromat. | With tert.-butylhydroperoxide In Carbon tetrachloride for 1.66667h; Reflux; | 2.1. General procedure for oxidation of alcohols with tert-BuOOH catalyzed by [Mo(CO)5(at)APy-MWCNT] General procedure: In a 25 mL round bottom flask equipped with a magnetic stirrer bar and a condenser, alcohols (1 mmol),tert-BuOOH (2 mmol, 80% solution in di-tert-butylperoxide), catalyst (90 mg, 0.015 mmol) and CCl4 (4 mL) were mixed and refluxed. The progress of the reaction was monitored by GLC. At the end of the reaction, the reaction mixture was diluted Et2O (20 mL) and filtered. The products were extracted with CH2Cl2 (2 10 mL) and were purified on silica-gel plates or a silica-gel column (CCl4-Et2O, 4:1). FT IR and 1H NMR spectral data was used to confirm the identities of the products. |
89 %Chromat. | With C39H29N5ORu(2+)*2ClO4(1-); dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 70℃; for 12h; Reflux; | |
14 %Spectr. | With 1-methyl-1H-imidazole; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; (x)C2H3N*C12H6N2O4(2-)*4C16H12O4(2-)*C22H16O4(2-)*Cu(1+)*4HO(1-)*I(1-)*4O(2-)*6Zr(4+) In acetonitrile at 20℃; for 6h; | |
With sodium hypochlorite; C42H42N28O14*C9H18NO In chloroform-d1 at 25℃; for 2h; | ||
With Zn(2,6-bis(phenylazo)-pyridine)Cl<SUB>2</SUB>; potassium-t-butoxide; oxygen; zinc In toluene at 59.84℃; for 24h; | ||
91 %Chromat. | With potassium hydroxide In o-dimethylbenzene at 144℃; for 3h; Green chemistry; | |
With [1-methyl-3-butylimidazolium][AuCl4] encapsulated in zeolitic imidazolate framework - 8-6.25%-900 In toluene at 130℃; for 72h; Schlenk technique; | 2.3. Catalytic reactions General procedure: In a typical run, alcohol (0.05 mmol), toluene (1 mL), and [Bmim][AuCl4] (at) ZIF-8-x-T (10 mol Au% based on alcohols) were added to a 25 mL Schlenk tube. The reaction mixture was stirred at 130 °C under atmospheric air. After reaction, qualitative analyses of the reaction mixtures were performed on a GC-MS spectrometer (Agilent, 7890BGC/5977 A MS) equipped with a HP-5 MS capillary column (0.25mm×30 m). | |
81 %Chromat. | With tert.-butylhydroperoxide at 50℃; for 6h; | |
83 %Chromat. | With potassium hydroxide In toluene at 80℃; for 5h; Green chemistry; | General procedure for oxidation of alcohols usingSCG(at)Fe3O4 General procedure: An alcohol (1.00 mmol) was added to a two-neckedflask containing SCGFe3O4 (0.05 g), KOH (0.028 g,0.50 mmol), and toluene (4.00 mL). The reaction washeated at 80 °C with continuous bubbling of air with aflow rate of 15 mL min-1 for indicated times as given in Table 2. The progress of the reaction was followed byTLC. Upon completion, the reaction mixture was filteredand the filtrate was analyzed by GC. |
69 %Chromat. | With potassium hydroxide In para-xylene at 80℃; for 3h; | General procedure for oxidation of alcoholsby MnO2bagasse, Fe3O4 bagasse and MnO2-Fe3O4 bagasse catalysts General procedure: In a typical reaction, an alcohol (1 mmol) was added to a twonecked flask containing catalyst: 0.05 g for MnO2-Fe3O4bagasse; 0.05 g (7.9 mol%) for MnO2bagasse; or 0.05 g(3.1 mol%) for Fe3O4bagasse, KOH (0.028 g, 0.5 mmol),and p-xylene (5 mL) under stirring conditions and air blowingat 80 °C. The progress of the reaction was followed by thinlayerchromatography (TLC). After the completion of reaction,the catalyst was separated by an external magnet and crudeproduct was analyzed by GC method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 5,10,15,20-tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate In acetonitrile at 50℃; for 0.0833333h; | |
94% | With rice husk ash at 80℃; for 0.666667h; Green chemistry; | Acetylation of Alcohols, Phenols, Thiols, and Amines General procedure: A mixture of the substrate (1 mmol), acetic anhydride (3 mmol), and RiHA (0.3 g)was stirred at room temperature and/or 80 °C. After completion of the reaction (TLC), the reaction mixture was triturated with EtOAc (15 mL) and the reagent was filtered. The organic layer was washed with saturated NaHCO3 and water (3×15 mL), and dried over anhydrous MgSO4. Evaporation of the solvent under reduced pressure gave the requested products in good to high yields. |
92% | With saccharin sulfonic acid In dichloromethane for 0.5h; Reflux; |
91% | With pyridine; dmap In dichloromethane at 0℃; for 1h; | |
90% | With rice-husk-supported FeCl3 nano particles In neat (no solvent) at 80℃; for 1.75h; | |
85% | With melamine-N2,N4,N6-trisulfonic acid In dichloromethane at 20℃; for 0.166667h; | |
50% | With pyridine; dmap In dichloromethane | |
With sodium acetate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With sodium hydride In N,N-dimethyl-formamide; toluene; mineral oil at 0 - 20℃; for 19h; Inert atmosphere; | |
85% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran Stage #2: propargyl bromide In tetrahydrofuran at 20℃; for 6h; Reflux; | General procedure for the synthesis of tethered ethers 8 General procedure: Aldehydes 9 (16 mmol) were reduced to anthracene methanols 14 using sodium borohydride (1.1 g, 30 mmol) dissolved in methanol. Anthracenemethanols 14 (10 mmol) were converted to the corresponding sodium salts 18 by treating with sodium hydride (0.48 g, 20 mmol) in THF. Propargyl bromide was added to it and stirred at room temperaturefor 2h followed by refluxing in THF for 4h to obtain 19 (75-85 % yield, Table 3). Propargyl ethers 19 (5 mmol)were refluxed in p-xylene (10 mL) (12 h to 20 h) to obtain the corresponding barrelenes 8 (80-90 %). The products were purified by silica gel column chromatography using a mixture of hexane and dichloromethane as eluents followed by recrystallization from suitable solvents and structures were confirmed by spectral and analytical data. |
84% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran at 20℃; for 1.5h; Reflux; Stage #2: propargyl bromide In tetrahydrofuran for 1.5h; Reflux; | Synthesis of 9-anthracenemethyl propargyl ether Synthesis according to the literature, amixture of 9-anthracenemethanol 2.28g(0.011mol), 0.6 g of 50% sodium hydride ,and 20 mL of THF was stirred at room temperature for 30min and then heatedunder reflux for 1 h. The mixture was cooled, adding a solution of propargylbromide 1.20 g (0.01mol) in 5 mL of THF. After being heated under refluxfor 1.5 h, the coded mixture was treated with water, and the product wasextracted with ether to give 9-anthracenemethyl propargyl ether 2.27g (84%). |
With sodium hydride 1.) THF, RT, 1 h, 2.) reflux, 1 h, 3.) reflux, 1 h; Multistep reaction; | ||
With tert.-butyl lithium In tetrahydrofuran at 20℃; | ||
With tert.-butyl lithium In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethylamine In dichloromethane at 0 - 20℃; | |
90% | With triethylamine at 20℃; | 2.3. Synthesis of Fluorophore-ContainingMethacrylate Monomers (AntMA: 1 andPyMA: 2) 9-Anthracenemethanol (4.5 g; 0.022 mol) was addedto a solution of triethylamine (9.0 mL; 0.065 mol) in250 mL of anhydrous MC. Methacryloyl chloride (6.3 mL;0.065 mol) was added dropwise under stirring at 0 C.The reaction was then conducted at room temperatureovernight, after which the reaction medium was filtered.The solvent was evaporated, and the solid residue waspurified by recrystallization in 95% ethanol at 40 C(yield = 90%). 1H NMR (CDCl3, ppm: 7.45-8.50(m, 9H, aromatic H), 6.20 (s, 2H, CH2O), 6.05 (s, 1H,CH2= C), 5.56 (s, 1H, CH2= C), 1.97 (s, 3H, CH3 . |
80% | With dmap; triethylamine In dichloromethane at 0℃; for 4.5h; Inert atmosphere; |
73% | With pyridine; dmap In chloroform at 0 - 20℃; for 4h; | |
70% | With 4-t-butyl-o-xylene; triethylamine In chloroform at 20℃; Cooling with ice; | |
70% | Stage #1: 9-hydroxymethylanthracene With triethylamine In tetrahydrofuran for 0.5h; Cooling with ice; Stage #2: Methacryloyl chloride In tetrahydrofuran at 0 - 20℃; | |
65% | With triethylamine In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Darkness; | |
42% | With pyridine; triethylamine In tetrahydrofuran at 0 - 20℃; for 1h; | |
In tetrahydrofuran for 0.75h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With bromine; triphenylphosphine In acetonitrile at 20℃; for 2h; Inert atmosphere; | |
With bromine; triphenylphosphine In acetonitrile at 20℃; | ||
With bromine; triphenylphosphine In acetonitrile at 20℃; | 9-Bromo-10-(bromomethyl)anthracene (2) Bromine (2 equivalents)was added drop wise to a stirred solution of triphenylphosphine(1 equivalent) in acetonitrile at room temperature and thepale yellow slurry was stirred for 15 min. Solid 9-anthracenemethanol (1 equivalent) was then added slowly and the reactantswere allowed to react at room temperature until total consumptionof the starting material (TLC) after which, it was refrigeratedovernight. The product, which appeared as yellow precipitate,was isolated by filtration, washed with little cold methanol andthen dried under vacuum. It was further re-crystallized twice fromchloroform before use. Characterization data completely corroboratedwith the literature reported data [29]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium bromate; nitric acid In acetonitrile for 1h; Heating; | |
90% | With sodium bromate; Nafion-Ce(IV); Nafion-H In water; acetonitrile for 4h; Heating; | |
84% | With water; potassium bromide In chloroform at 25℃; Electrochemical reaction; | General procedure for electrochemical oxidation: General procedure: To an undividedelectrochemical cell the respective substrate (0.5 mmol) and CHCl3 (30 mL)was added. Thirty millilitre of aqueous solution of KBr (3.0 M) was then addedover the above solution. The electrolytic cell was equipped with a magneticstirrer in order to keep the CHCl3 solution well mixed. Two Pt electrodes(1.0 1.5 cm2) were placed vertically having an inter-electrode gap of 4 cm inthe aqueous phase without touching the organic phase, but very close to theinterphase of the two-phases (SI). All electrolyses were performed at aconstant current density (40 mA/cm2) at room temperature. The electrolysiswas stopped after the passage of a charge of 18 F/mol. Subsequently, theorganic layer was first collected and then the aqueous solution was extractedwith two portions of dichloromethane (2 15 mL). The combined extractswere washed with a solution of NaHSO3 (10%, 20 mL) to remove residualamounts of Br2, then with saturated NaHCO3 (10 mL), brine (10 mL), and H2O(30 mL). After dried over anhydrous MgSO4, the solvent was removed by rotaryevaporation under reduced pressure and the residue was subjected to eitherrecrystallization using n-hexane-ethyl acetate mixture (90:10, v/v) or columnchromatographed over SiO2. Yields and physical data are given in Tables 1-3. |
With air In water-d2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With N-ethyl-N,N-diisopropylamine In propiononitrile at 97℃; for 20h; | 1.d To a solution of anthracen-9-yl-methanol (6.58 g, 31.6 mmol) and (cyanomethyl)trimethylphosphonium iodide (19.19 g, 78.96 mmol) in propionitrile (77 mL) was added diisopropylethylamine (DIPEA, 49.4 mL, 94.74 mmol) and the mixture was stirred at 97 0C for 20 hours. Water (3.82 mL) was added, nitrogen was bubbled though the mixture, and the mixture was stirred for 20 hours. Water (480 mL) and concentrated HCl (19 mL) were added and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over MgSO4 and concentrated. The resulting solid was purified by silica gel column chromatography (hexane: CHCl3 = 1 :1) to give 3-anthracen-9-yl-propionitrile as brown crystals (6.93 g, 95% yield). 1H NMR (CDCl3) δ 8.43 (IH, s), 8.19 (2H, d), 8.05 (2H, d), 7.60 (2H, dd), 7.51 (2H, dd), 4.02 (2H, t), 2.79 (2H, t). |
75% | With N-ethyl-N,N-diisopropylamine; propiononitrile at 97℃; for 20h; | |
71% | Stage #1: 9-hydroxymethylanthracene; (cyanomethyl)trimethyl-phosphonium iodide With N-ethyl-N,N-diisopropylamine; propiononitrile at 97℃; for 20h; Stage #2: With water at 97℃; for 1h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate at 20℃; for 0.0333333h; Neat (no solvent); | |
98% | With succinimide-N-sulfonic acid In acetonitrile at 20℃; for 0.0333333h; | |
97% | With 1,3-disulfonic acid imidazolium hydrogen sulfate In neat (no solvent) at 20℃; for 0.0166667h; Green chemistry; | General procedure for O-silylation of alcohols and phenols with HMDS in the presence of [Dsim]HSO4 ionic liquid General procedure: Ionic liquid [Dsim]HSO4 (6.5 mg, ∼0.02 mmol) was added to a stirred mixture of alcohol, phenol or naphthol (1.0 mmol) and HMDS (80 mg, 0.5 mmol) at room temperature under solvent free conditions. After completion of the reaction (monitored by TLC, It should be noted that when addition of HMDS is finished stirring of the mixture is stopped after 1 min. TLC showed that in most of the cases the reaction is completed immediately after the addition of HMDS), the product was extracted with Et2O and the ionic liquid was recovered and was dried at 65 ◦C under vacuum to remove moisture, and then reused. Evaporation of the solvent under reduced pressure gave the highly pure product without further purification. The desired pure products were characterized by comparison of their IR, NMR and MS data as well as boiling poin twith those of known compounds |
95% | With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 0.95h; | |
95% | With aluminium(III) triflate at 20℃; | |
93% | With poly(4-vinylpyridine) In acetonitrile at 20℃; for 0.166667h; | |
90% | With C10H10N2O6S2(2+)*2HO4S(1-) at 20℃; for 0.05h; | General Procedure for the Protection of Alcohols General procedure: A mixture of the substrate (1 mmol), hexamethyldisilazane (0.70 mmol), and/or 3,4-dihydro-2H-pyran (1.4 mmol) and BiPy(SO3H)2(HSO4)2 (10 mg, 1.95 mol%) in CH3CN(3 mL) and/or CH2Cl2 (3 mL) was stirred at room temperature. The progress of thereaction was monitored by TLC (n-hexane: EtOAc; 10:1) and/or GC. After completion ofthe reaction, the mixture was filtered to separate the solid catalyst. Then the solution wasfiltered through a silica gel pad and washed with CH3CN (2 × 3 mL) and/or CH2Cl2 (2 ×3 mL). Evaporation of the solvent gave the desired products in high purity. |
89% | In acetonitrile at 20℃; for 0.05h; | 2.4. General procedure for trimethylsilylation of alcohols and phenols General procedure: To a stirring mixture of the substrate (1 mmol), and TiO2-HClO4 (5 mg) in CH3CN (3 mL), HMDS (120 mg, 0.75 mmol) was added at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was filtered and the filtrate was washed with acetonitrile (5 mL). Evaporation of the solvent gave almost pure product(s). Further purification proceeded by bulb to bulb distillation under reduced pressure or recrystallization to afford pure silyl ether (Table 2). |
85% | With titanium(IV) oxide In acetonitrile at 20℃; for 1.5h; chemoselective reaction; | |
70% | With magnesium triflate at 20℃; for 1h; | |
100 % Chromat. | In acetonitrile at 20℃; for 0.0166667h; | |
100 %Chromat. | With tin(IV)tetraphenylporphyrinato tetrafluoroborate In acetonitrile at 20℃; for 0.0166667h; | |
100 %Chromat. | With 5,10,15,20-tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate In acetonitrile at 20℃; for 0.0416667h; | |
97 %Chromat. | With tetrakis(p-aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate supported on graphene oxide nanosheets In acetonitrile at 20℃; for 0.05h; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dicyclohexyl-carbodiimide | |
57% | at 100℃; for 5h; Schlenk technique; Inert atmosphere; | |
With triethylamine In tetrahydrofuran for 24h; Heating; |
20 g | With Neostan U-600 In tetrahydrofuran at 25 - 40℃; for 3h; | BS-3 <Synthesis example BS-3: Synthesis of BS-3> In a flask equipped with a stirrer and a condenser, 3- (triethoxysilyl) propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.3 g (50 mmol), Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0 0.01 g was dissolved in 150 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 25 ° C. Then, 10.4 g of 9- (hydroxymethyl) anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 3 hours. Subsequently, this was dissolved in 1000 mL of ethyl acetate, transferred to a separating funnel, washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 20 g of BS-3. The structure of BS-3 is presumed to be the following structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With pyridine; dmap In dichloromethane at 20℃; for 16h; | |
93% | With dmap In pyridine at 20℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With dmap; triethylamine In dichloromethane at 0 - 20℃; for 13h; | |
87% | With triethylamine In tetrahydrofuran at 20℃; Cooling with ice; Inert atmosphere; | |
87.5% | With dmap; triethylamine In dichloromethane at 0 - 20℃; for 25h; |
84% | With dmap; triethylamine In dichloromethane at 0 - 20℃; | Synthesis of 9-anthyrylmethyl 2-bromo-2-methyl propanoate 9-anthyryl methyl 2-bromo-2-methyl propanoate was synthesized by following literature.3 9-Anthracene methanol (1 .50 g, 7.18 mmol) and DMAP (0.175 g, 1 .44 mmol) were dissolved in 50 mL of CH2CI2, and Et3N (1 .2 mL, 8.6 mmol) was added. The reaction mixture was then cooled to 0 °C. 2-bromo isobutyryl bromide (1 .82 g, 7.89 mmol) was added dropwise within 30 minutes to this solution. The reaction mixture was stirred for 15 min at 0 °C then for overnight at room tempeature. The ammonium salt was filtered off and the solvent was evaporated under reduced pressure. The remaining residue was extracted with CH2CI2, and saturated aqueous NaHC03 and combined organic phases dried over Na2S04. The solution was concantrated, and the crude product was purified by column chromatography over silica gel eluting with hexane/EtOAc (10:1 ) to give 5 as yellow solid. Yield: 2.15 g (84 %). EIMS m/z 379.0 for [M + Na]+ C19H1702BrNa calculated 379.04. 1H NMR (500 MHz, CDCI3, δ): 8.55 (s, 1 H, ArH of anthracene), 8.35 (d, J = 8.99 Hz, 2H, ArH of anthracene), 8.05 (d, J = 8.49 Hz, 2H, ArH of anthracene), 7.60-7.45 (m, 4H, ArH of anthracene), 6.24 (s, 2H, CH2- anthracene), 1 .89 (s, 6H, C(CH3)2-Br). 13C NMR (CDCI3, δ): 172, 131 .3, 131 .1 , 129.4, 129.1 , 126.7, 125.5, 125.1 , 123.9, 69.7, 55.9, 30.7. |
84% | With dmap; triethylamine In dichloromethane at 0 - 20℃; | 3 Synthesis of 9-anthyrylmethyl 2-bromo-2-methyl propanoate 9-anthyrylmethyl 2-bromo-2-methyl propanoate was synthesized by following literature.3 9-Anthracene methanol (1.50 g, 7.18 mmol) and DMAP (0.175 g, 1.44 mmol) were dissolved in 50 mL of CH2Cl2, and Et3N (1.2 mL, 8.6 mmol) was added. The reaction mixture was then cooled to 0° C. 2-bromo isobutyryl bromide (1.82 g, 7.89 mmol) was added dropwise within 30 minutes to this solution. The reaction mixture was stirred for 15 min at 0° C. then for overnight at room temperature. The ammonium salt was filtered off and the solvent was evaporated under reduced pressure. The remaining residue was extracted with CH2Cl2, and saturated aqueous NaHCO3 and combined organic phases dried over Na2SO4. The solution was concentrated, and the crude product was purified by column chromatography over silica gel eluting with hexane/EtOAc (10:1) to give 5 as yellow solid. Yield: 2.15 g (84%). EIMS m/z 379.0 for [M+Na]+C19H17O2BrNa calculated 379.04. 1H NMR (500 MHz, CDCl3, δ): 8.55 (s, 1H, ArH of anthracene), 8.35 (d, J. 8.99 Hz, 2H, ArH of anthracene), 8.05 (d, J=8.49 Hz, 2H, ArH of anthracene), 7.60-7.45 (m, 4H, ArH of anthracene), 6.24 (s, 2H, CH2-anthracene), 1.89 (s, 6H, C(CH3)2-Br). 13C NMR (CDCl3, δ): 172, 131.3, 131.1, 129.4, 129.1, 126.7, 125.5, 125.1, 123.9, 69.7, 55.9, 30.7. |
72% | With triethylamine In dichloromethane at 0 - 25℃; | |
With triethylamine In tetrahydrofuran at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium hydroxide In N,N-dimethyl-formamide at 50℃; for 8h; | 2.6 Synthesis of 9-anthrylmethanol (5) 9-Anthrylmethyl acetate (1.79mmol) was dissolved in anhydrous DMF (20mL), sodium hydroxide (2.69mmol) was added. After stirring at 50°C for 8h, the crude reaction was precipitated in water; the obtained product was an yellow powder. Yield 90%; 1H NMR (300MHz, DMSO-d6; δ: ppm): 5.31 (s, 1H, OH); 5.60 (s, 2H, CH2-O); 7.62 (m, 4H, H-Ar); 8.13 (d, 2H, H-Ar); 8.36 (d, 2H, H-Ar); 8.70 (s, 1H, H-Ar). 13C NMR (75MHz, DMSO-d6, δ): 55.30; 124.79; 125.02; 125.76; 127.02; 128.67; 129.76; 131.05; 132.90. FTIR (cm-1): 3442 (CH2-OH, stretching); 3003 (w, aromatic C-H stretching); 1490 (s, C=C stretching); 738 (s, aromatic C-H out-of-plane bending). |
In water; acetonitrile for 0.333333h; Photolysis; | ||
83.2 %Chromat. | With platinum(II) octaethylporphyrin; water In tetrahydrofuran for 1h; Irradiation; Inert atmosphere; | [00249] FIG. 8 shows (a) Molecular structure of PtOEP and Py (compound 8); (b) Phosphorescence intensity quenching of PtOEP (10 mM) in the presence of different concentration of compound 8, Xex = 530 nm; (c) Stern-Volmer plots generated from the phosphorescence intensity quenching of PtOEP as a function of compound 8 concentration; (d) The upconversion emission spectra of PtOEP and compound 8 paired in the air, argon and in the absence of PtOEP, 2ex = 530 nm, 20 mW/cm2, in toluene. (0317) Table 12. Photolvtic reaction for PtOEP and An (compound 2) (0318) Enter Condition Reaction time Yield (%) a (0319) 1 Light, air 1 h Trace (0320) 2 Dark, argon 1 h No reaction (0321) 3 An (compound 2) only, light, argon 1 h No reaction (0322) 4 Light, argon 1 h 83.2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tetra-(n-butyl)ammonium iodide; sodium hydride In tetrahydrofuran at 0 - 20℃; | |
96% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran at 0℃; for 0.333333h; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; | |
96% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran at 0℃; for 0.333333h; Inert atmosphere; Stage #2: methyl iodide With tetra-(n-butyl)ammonium iodide In tetrahydrofuran at 0 - 20℃; Inert atmosphere; |
82% | With n-butyllithium In tetrahydrofuran; hexane at 20℃; | |
35.5% | With sodium hydride In tetrahydrofuran at 0 - 80℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 9-hydroxymethylanthracene With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere; Stage #2: malonoyl dichloride In dichloromethane at 0 - 20℃; for 3.75h; Inert atmosphere; | Synthesis of bis(anthracen-9-ylmethyl) malonate (Fig. 1) 9-Anthracenemethanol (3 g, 14.4 mmol) was added to a stirredsolution of triethylamine (1.46 g, 14.4 mmol) in anhydrousdichloromethane (60 ml) at room temperature and under argon atmosphere. The resulting solution was cooled to 0 °C using an ice bath. Afterward, malonyl chloride (1.02 g, 7.2 mmol) diluted with 5 ml of anhydrous methylene chloride was added dropwise in the period of 45 min. Then mixture was allowed to warm to room temperature and was stirred for additional 3 h. Then it was diluted with ethyl acetate, washed twice with water and dried using anhydrous magnesium sulfate. Then, the solvent was removed at reduced pressure. Purification ofthe product was accomplished by the means of flash column chromatography (1:2.5 ethyl acetate: n-hexane) to give desired product as yellow solid. Yield: 89 %, Mp 191 °C, lit. 178-182 °C (Herranz et al. 2004), the mass spectrum (ESI-MS) showed a [M + Na]+ peak at 507.7 (Figure S1, Supplementary Information, SI); IR (KBr disk) νmax(cm-1) 3085.27, 3036.83, 3001.65, 2960.30, 2916.11, 2848.30, 2359.83, 1747.57, 1722.21,1383.12, 1352.70, 1330.53, 1171.30, 982.33, 883.91, 735.78, 728.82 (Figure S2, SI); NMR (literature data canbe found in Herranz et al. 2004) δ1H 500 MHz; CDCl3;TMS) 8.47 (s, 2H), 8.18-8.20 (q, 4H), 7.97-7.99 (q, 4H), 7.43-7.46 (m, 8H), 6.12 (s, 2H), 3.40 (s, 2H) ppm (Figure S3, SI); δ 13C (125 MHz; CDCl3)166.76, 131.31, 131.07, 129.44, 129.08, 126.77, 125.13, 123.76, 59.97, 41.47 ppm (Figure S4, SI); UV-Vis λmax = 334.4, 350.5, 368.5, 387.6 nm (Figure S5, SI). |
36% | With pyridine In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With dmap; triethylamine In tetrahydrofuran at 20℃; for 40h; | |
98% | With dmap; triethylamine In tetrahydrofuran at 20℃; for 40h; Inert atmosphere; | |
98% | With dmap; triethylamine In tetrahydrofuran at 25℃; for 42h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane; benzene Reflux; Inert atmosphere; Stage #2: phenol With potassium carbonate In acetone for 24h; Reflux; Inert atmosphere; | |
95% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane; benzene Inert atmosphere; Reflux; Stage #2: phenol With potassium carbonate In acetone for 24h; Inert atmosphere; Reflux; | |
91% | Stage #1: 9-hydroxymethylanthracene With methanesulfonyl chloride; triethylamine In dichloromethane at 0℃; for 0.0833333h; Stage #2: phenol With potassium carbonate In acetone for 24h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane at 0℃; for 1h; Stage #2: With sodium azide In dichloromethane; N,N-dimethyl-formamide at 50℃; for 1h; | |
97% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane at 0℃; for 2h; Stage #2: With sodium azide In N,N-dimethyl-formamide at 60℃; for 4h; | |
93% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane at 0 - 20℃; for 1h; Stage #2: With sodium azide In N,N-dimethyl-formamide at 50℃; for 1h; | Synthesis of (azidomethyl)anthracene (Az-2) A literature procedure was used [45]. 9-Hydroxymethylanthracene(7.40 mmol, 1 equiv) was added to DCM (50 mL) andcooled to 0 °C. Then, SOCl2 (1.5 equiv) was slowly introducedto the reaction media and allowed to warm up to room temperaturewhile being stirred for 1 h. The solvent was removed undervacuum and the residue redissolved in DMF (10 mL).Following dissolution of the compound, NaN3 (1.5 equiv) wasadded, and the reaction was stirred at 50 °C. After 1 h, the reactionmixture was allowed to cool down, diluted with water andextracted with EtOAc. The combined organic phases werewashed with brine, dried with anhydrous MgSO4, filtered, andconcentrated under vacuum. Brownish yellow crystalline solid,yield = 93%. 1H NMR (500 MHz, DMSO-d6) δ 8.70 (s, 1H),8.44 (dd, 2H), 8.14 (dd, 2H), 7.64 (td, 2H), 7.56 (td, 2H), 5.51(s, 2H); 13C{1H} NMR (DMSO-d6, 125 MHz) δ 131.39,130.72, 129.51, 129.06, 127.28, 126.96, 125.88, 124.51, 45.96. |
57% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane at 0 - 20℃; for 1h; Stage #2: With sodium azide In N,N-dimethyl-formamide at 50℃; for 1h; | |
Multi-step reaction with 2 steps 1: 94 percent / PBr3 / toluene / 0 - 20 °C 2: 100 percent / NaN3 / dimethylsulfoxide / 3.5 h / 50 °C | ||
Multi-step reaction with 2 steps 1: 75 percent / Br2; PPh3 / acetonitrile / 5 °C 2: 99 percent / NaN3 / dimethylformamide / 0.5 h / 50 °C | ||
Multi-step reaction with 2 steps 1: 77 percent / PBr3 / toluene / 1 h / 0 °C 2: 90 percent / NaN3 / dimethylsulfoxide / 4 h / 50 °C | ||
Multi-step reaction with 2 steps 1: 77 percent / PBr3 2: 90 percent / NaN3 / dimethylsulfoxide / 50 °C | ||
With thionyl chloride; sodium azide | ||
Multi-step reaction with 2 steps 1: hydrogen bromide / dichloromethane 2: sodium azide / tetrahydrofuran; water | ||
Multi-step reaction with 2 steps 1: hydrogen bromide; sulfuric acid; sodium bromide / diethyl ether 2: sodium azide / N,N-dimethyl-formamide | ||
Multi-step reaction with 2 steps 1: phosphorus tribromide / toluene / 1 h / 0 °C 2: sodium azide / N,N-dimethyl-formamide / 2 h / 70 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 4-Nitrophenyl chloroformate With dmap In dichloromethane Inert atmosphere; Stage #2: 9-hydroxymethylanthracene In dichloromethane at 20℃; Inert atmosphere; | |
53% | With triethylamine In ISOPROPYLAMIDE at 20℃; for 24h; | 1 Synthetic Example 1Synthesis of 9-anthrylmethyl 4'-nitrophenylcarbonate (First process); To the solution dissolved 5.0 g of 9-anthracenemethanol (24 mmol; produced by Wako Pure Chemical Industries, Ltd.) into 250 mL of the dehydrated dimethylacetamide (dehydrated DMAc), 7.3 g of triethylamine (72 mmol) was added. After 4.9 g of 4-nitrophenyl chloroformate (24 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added to this solution, the solution was reacted by stirring for 24 hours at room temperature. After completing the reaction, ice-water was poured into the reaction solution, and this mixed solution was extracted with dichloromethane, and further after organic layer after extraction was washed with water, the organic layer was condensed. Subsequently, water was poured into the condensed residue, and after the resultant crystal was filtered, the resultant crystal was dried to obtain 4.8 g of 9-anthrylmethyl 4'-nitrophenylcarbonate (yield: 53%) as yellow crystal. Measurement results of 1H-NMR are shown as the follows:1H-NMR (400 MHz, CDCl3) δ (ppm): 6.39 (2H, s, OCH2), 7.36 (2H, d, J=9.3 Hz, ArH), 7.51-7.54 (2H, m, ArH), 7.60-7.65 (2H, m, ArH), 8.06 (2H, d, J=8.7 Hz, ArH), 8.24 (2H, d, J=9.3 Hz, ArH), 8.41 (2H, d, J=8.7 Hz, ArH), 8.57 (1H, s, ArH). |
With pyridine In tetrahydrofuran | 1 Preparation of Anthrylmethyl p-Nitrophenyl Carbonate 4.89 g (24 mmoles) of p-nitrophenyl chloroformate were dissolved in 100 ml of tetrahydrofuran (THF) and placed in a two-neck, 500 ml round bottom flask with a magnetic stirring bar. 3.36 g (16.2 mmoles) of 9-anthacenemethanol were dissolved in 100 ml of THF, and 2.56 g (2.61 ml, 32.4 mmoles) of pyridine were added to the anthracenemethanol solution. The anthracenemethanol. solution was then added dropwise to the p-nitrophenyl chloroformate solution, while monitoring the progress of the reaction with thin-layer chromatography (TLC). The reaction mixture, a 3:2 ratio of p-nitrophenyl chloroformate : anthracenemethanol, was allowed to stir overnight. The reaction mixture was then decanted to separate the solution from the white precipitate which had formed, followed by roto-evaporation to remove the THF. The product residue was dissolved in toluene. This solution was then decanted to remove any undissolved product residue. Next, the toluene solution was roto-evaporated, yielding 8.60 g of crude anthrylmethyl p-nitrophenyl carbonate. This crude product also contained a small amount of unreacted p-nitrophenyl chloroformate. |
With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere; | ||
With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere; | ||
With pyridine; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; | ||
With pyridine In dichloromethane for 2.16667h; | Compound 4: 4-benzyl alcohol anthracene (208 mg, 1.0 mmol) dissolved in dry dichloromethane (DCM) (10 mL) and pyridine (50 pL) were mixed. 4-nitrophenyl chloroformate (1.2 mmol) was dissolved in dry DCM (10 mL) and added dropwise to the mixture over 10 min and then stirred for 2 hours. Next, the butylamine (2.0 mmol) was added and stirred for another 12 hours in room temperature. After the reaction, 50 mL CH2C12 was added. The solutions were washed with saturated aqueous solution of sodium bicarbonate (30 mL). The organic layer was collected and dried by Na2S04; the solvents were removed under vacuum condition. The raw 4 was purified by silica gel flash column chromatography with DCM/n-hexane =1/1 (v/v) as elute. The shallow yellow band was collected and yield determined to be 60 % (184.2 mg). -NMR (500 MHz, CDC13): d= 8.50 (s, 1H), 8.40-8.38 (m, 2H), 8.03-8.01 (d, 2H, 7=9.0 Hz), 7.57-7.55 (m, 2H), 7.50-7.47 (m, 2H), 6.14 (s, 2H), 4.66 (s, 1H), 3.23-3.20 (m, 2H), 1.50-1.44 (m, 2H), 1.35-1.30 (m, 2H), 0.92-0.90 ppm (m, 3H). 13C- NMR (125 MHz, CDC13): d= 156.6, 131.4, 131.0, 129.1, 129.0, 126.9, 126.6, 125.1, 124.1, 59.0, 40.9, 32.0, 19.9, 13.7 ppm. HRMS (ESI) exact mass calculated for [M + Na] + (C20H21NO2 + Na+) requires m/z 330.1470, found m/z 330.1465. | |
With pyridine In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In hexane; acetonitrile Reflux; Inert atmosphere; Stage #2: 1,4-bis(bromomethyl)benzene In hexane; acetonitrile for 16h; Reflux; Inert atmosphere; | |
Stage #1: 9-hydroxymethylanthracene With sodium hydride In acetonitrile at 82℃; Inert atmosphere; Stage #2: 1,4-bis(bromomethyl)benzene In acetonitrile for 16h; Inert atmosphere; Reflux; | 1 500 mg of (anthracene-9-yl)methanol (M.W. 208.26 g/mol, 2.4 mmol) was solubilized in acetonitrile to obtain a yellow solution. The latter was heated under reflux (82° C.), and nitrogen was bubbled therein.70 mg of sodium hydride (M.W. 24 g/mol, 2.9 mmol), previously washed with hexane and then suspended in acetonitrile, was added. After approximately 30 minutes, the mixture assumed a red coloring.At this point, a solution prepared by solubilizing 1.3 g of α,α'-dibromium para-xylene (M.W. 263.97, 5 mmol) in acetonitrile was added. Reflux was maintained for 16 hours.The reaction was followed via TLC (thin-layer chromatography) on silica using as eluent mixture cyclohexane/dichloromethane (1:2). Formation was thus noted of some by-products and of a very intense spot at Rf 0.77, as well as spots corresponding to the unreacted ingredients.The spot at Rf 0.77 (compound A in scheme 2) was extracted with methanol, and the UV-VIS absorption spectrum determined. The spectrum showed the typical band for anthracene. | |
Stage #1: 9-hydroxymethylanthracene With sodium hydride In acetonitrile at 82℃; for 0.5h; Heating / reflux; Stage #2: 1,4-bis(bromomethyl)benzene In acetonitrile for 16h; Heating / reflux; | 1; 2 500 mg of (anthracene-9-yl)methanol (M.W. 208.26 g/mol, 2.4 mmol) was solubilized in acetonitrile to obtain a yellow solution. The latter was heated under reflux (82°C), and nitrogen was bubbled therein. 70 mg of sodium hydride (M.W. 24 g/mol, 2.9 mmol), previously washed with hexane and then suspended in acetonitrile, was added. After approximately 30 minutes, the mixture assumed a red coloring. At this point, a solution prepared by solubilizing 1.3 g of α,α'-dibromium para-xylene (M.W. 263.97, 5 mmol) in acetonitrile was added. Reflux was maintained for 16 hours. The reaction was followed via TLC (thin-layer chromatography) on silica using as eluent mixture cyclohexane/dichloromethane (1:2). Formation was thus noted of some by-products and of a very intense spot at Rf 0.77, as well as spots corresponding to the unreacted ingredients. The spot at Rf 0.77 (compound A in scheme 2) was extracted with methanol, and the UV-VIS absorption spectrum determined. The spectrum showed the typical band for anthracene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantiospecific reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 1h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With dirhodium tetraacetate; C40H25O4P In dichloromethane at -20℃; for 3h; Molecular sieve; Inert atmosphere; optical yield given as %ee; enantiospecific reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With triethylamine In dichloromethane at 0 - 20℃; | |
87% | With triethylamine In dichloromethane at 0 - 25℃; for 4h; | |
85% | With pyridine In dichloromethane for 2.16667h; | Compound 2: 4-benzyl alcohol anthracene (208 mg, 1.0 mmol) dissolved in dry dichloromethane (DCM) (10 mL) and pyridine (50 pL) were mixed. Acetyl chloride (2.0 mmol) was dissolved in dry DCM (10 mL) and added dropwise to the mixture over 10 min and then stirred for 2 hours. After the reaction, the solvents were removed under vacuum condition. The raw 2 was purified by silica gel flash column chromatography with DCM/n-hexane =1/2 (v/v) as elute. The yellow band was collected and yield determined to be 85 % (212.5 mg). -NMR (500 MHz, CDCI3): d= 8.52 (s, 1H), 8.34-8.32(d, 2H, / = 10.0Hz), 8.05-8.03 (d, 2H, / = 9.5 Hz), 7.58-7.56 (m, 2H), 7.50-7.48 (m, 2H), 6.16 (s, 2H), 2.09 ppm (s, 3H). 13C-NMR (125 MHz, CDC13): d= 171.3, 131.4, 131.1, 129.2,129.1, 126.7, 126.2, 125.1, 123.9, 58.8, 21.0 ppm. HRMS (ESI) exact mass calculated for [M + Na+] (C17H1402 + Na+) requires m/z 273.0891, found m/z 273.0886. |
39% | With 4-t-butyl-o-xylene; triethylamine In chloroform at 20℃; Cooling with ice; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 9-hydroxymethylanthracene; 1,1'-carbonyldiimidazole In N,N-dimethyl-formamide for 1h; Cooling with ice; Stage #2: propylamine In N,N-dimethyl-formamide at 20℃; for 2h; | 5 Example 5Synthesis of 9-anthrylmethyl N-n-propylcarbamate (First and Second process); To the solution dissolved 8.92 g of N,N'-carbonyldiimidazole (55 mmol; produced by Wako Pure Chemical Industries, Ltd.) into 40 mL of dimethylformamide (DMF), 10.4 g of 9-anthracenemethanol (50 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added under cooling with ice, then, the solution was reacted by stirring for 1 hour at the same temperature. Subsequently, 4.13 g of mono-n-propylamine (70 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added to this solution, and the solution was reacted by stirring for 2 hours at room temperature. After completing reaction, the reaction solution was poured into 210 mL of 1.8% hydrochloric acid, the resultant crystal was filtered, then, the resultant crystal was dried, the crystal after drying was added to 70 mL of toluene, and was hot-dissolved to hot-filtered at the temperature of 100° C. Subsequently, the filtrate obtained by filtration was cooled with ice, and the precipitated crystal was filtered, then, the resultant crystal was dried to obtain 13.6 g of 9-anthrylmethyl N-n-propylcarbamate (yield: 93%) represented by the above-described formula [14] as yellow crystal. Measurement results of 1H-NMR and melting point are shown as the follows:1H-NMR (400 MHz, CDCl3) δ (ppm): 0.89 (3H, t, J=7.2 Hz, CH3), 1.47 (2H, qt, J=7.2, 6.8 Hz, CH2), 3.15 (2H, br, NCH2), 4.71 (1H, br, NH), 6.11 (2H, s, OCH2), 7.45-7.55 (4H, m, ArH), 8.00 (2H, d, J=8.4 Hz, ArH), 8.37 (2H, d, J=8.4 Hz, ArH), 8.46 (1H, s, ArH);Melting point: 164-167° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 9-hydroxymethylanthracene; 1,1'-carbonyldiimidazole In N,N-dimethyl-formamide for 1h; Cooling with ice; Stage #2: cyclohexylamine In N,N-dimethyl-formamide at 20℃; for 2h; | 6 Example 6Synthesis of 9-anthrylmethyl N-cyclohexylcarbamate (First and Second process); To the solution dissolved 8.92 g of N,N'-carbonyldiimidazole (55 mmol; produced by Wako Pure Chemical Industries, Ltd.) into 40 mL of dimethylformamide (DMF), 10.4 g of 9-anthracenemethanol (50 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added under cooling with ice, then, the solution was reacted by stirring for 1 hour at the same temperature. Subsequently, 6.94 g of monocyclohexylamine (70 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added to this solution, and the solution was reacted by stirring for 2 hours at room temperature. After completing reaction, the reaction solution was poured into 110 mL of 3.5% hydrochloric acid, the resultant crystal was filtered, then, the resultant crystal was dried, the crystal after drying was added to 100 mL of toluene, and was hot-dissolved to hot-filtered at the temperature of 100° C. Subsequently, the filtrate obtained by filtration was cooled with ice, and the precipitated crystal was filtered, then, the resultant crystal was dried to obtain 15.4 g of 9-anthrylmethyl N-cyclohexylcarbamate (yield: 92%) represented by the above-described formula [15] as yellow crystal. Measurement results of 1H-NMR and melting point are shown as the follows:1H-NMR (400 MHz, CDCl3) δ (ppm): 1.06-1.09 (4H, br, CH2×2), 1.32-1.36 (2H, br, CH2), 1.60-1.66 (2H, br, CH2), 1.91-1.92 (2H, br, CH2), 3.53 (1H, br, NCH), 4.59 (1H, br, NH), 6.12 (2H, s, OCH2), 7.46-7.58 (4H, m, ArH), 8.01 (2H, d, J=8.4 Hz, ArH), 8.39 (2H, d, J=8.4 Hz, ArH), 8.48 (1H, s, ArH); Melting point: 203-205° C. |
Yield | Reaction Conditions | Operation in experiment |
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61% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran Stage #2: N,N-diethylcarbamyl chloride In tetrahydrofuran at 60℃; for 2h; | 4 Example 4Synthesis of 9-anthrylmethyl N,N-diethylcarbamate; To the solution containing 1.6 g of 50% sodium hydrate (33 mmol) and 4 mL of dehydrated tetrahydrofuran (dehydrated THF), the solution dissolved 6.3 g of 9-anthracenemethanol (30 mmol; produced by Wako Pure Chemical Industries, Ltd.) into 26 mL of dehydrated tetrahydrofuran (dehydrated THF) was dropped. Then, after this solution of 4.5 g of N,N-diethylcarbamoyl chloride (33 mmol; produced by Sigma-Aldrich Japan Co.) in 4 mL of dehydrated tetrahydrofuran (dehydrated THF) was added, the solution was reacted by stirring for 2 hours at 60° C. After completing reaction, reaction solution was cooled, and n-hexane was poured into the cooled solution, then, the solution was washed with water, and organic layer after washing was condensed. The resultant condensed residue was purified with column chromatography (Filler: Silica-Gel (Wako-Gel C-200; produced by Wako Pure Chemical Industries, Ltd.), Developing solvent: n-heptane) to obtain 5.7 g of 9-anthrylmethyl N,N-diethylcarbamate (yield: 61%) represented by the above-described formula [7] as yellow crystal. Measurement results of 1H-NMR and melting point are shown as the follows:1H-NMR (400 MHz, CDCl3) δ (ppm): 0.91 (3H, br, CH3), 1.14 (3H, br, CH3), 3.14 (2H, br, NCH2), 3.35 (2H, br, NCH2), 6.14 (2H, s, OCH2), 7.48 (2H, dd, J=8.0, 6.8 Hz, ArH), 7.57 (2H, dd, J=8.4, 6.8 Hz, ArH), 8.04 (2H, d, J=8.0 Hz, ArH), 8.46 (2H, d, J=8.4 Hz, ArH), 8.52 (1H, s, ArH);Melting point: 72-74° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With methanol; 1,3-disulfonic acid imidazolium hydrogen sulfate at 20℃; for 0.0666667h; Green chemistry; | General procedure for the deprotection of trimethylsilyl ethers General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ∼0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ◦C under vacuum to remove moisture, and then reused. |
87% | With methanol at 20℃; for 0.0833333h; | 2.5. General procedure for deprotection of trimethylsilyl ethers General procedure: A mixture of the substrate (1 mmol) and TiO2-HClO4 (5 mg) in methanol (1 mL) was stirred at room temperature. After completion of the reaction (indicated by TLC), the catalyst was filtered off and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel to afford pure alcohols and phenols (Table 2). |
90 %Chromat. | With (NH4)8[CeW10O36]*20H2O In acetonitrile at 20℃; for 0.0833333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With potassium borohydride; acetic acid at 90℃; for 4h; | 9-anthracenylidene (4.5 mmol, 0.9274 g) and KBH4 (6.36 mmol, 0.3420 g) were dissolved in ethanol (40 mL). The mixture was adjusted the pH to about 6 with glacial acetic acid. After stirring 4 h at 90 °C, a clear pale yellow solution was generated. The resulting solution stands for 15 days at room temperature, light yellow rod-shaped crystals were formed. The crystals were isolated by filtration, washed with methanol and dried in a vacuum desiccators using anhydrous CaCl2 (yield 82%). Elemental Analysis Calculate (%): C, 86.57; H, 5.19. Found: C, 86.48; H, 5.10. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran at 20℃; for 0.05h; Stage #2: ethyl iodide In tetrahydrofuran at 20℃; for 12h; | 9-Ethoxymethyl Anthracene (1c) To a solution of 9-anthracenemethanol (300 mg, 1.44 mmol) in anhydrousTHF (10 mL) was added NaH (150 mg, 8.6 mmol), and thesolution was stirred at r.t. for 3 min. Then iodoethane (347 μg, 4.32mmol) was added at r.t. The mixture was stirred for 12 h at r.t. andthen poured in the H2O. The aqueous layer was extracted with EtOAc(3 × 10 mL). The combined organic layers were washed withbrine (20 mL) and dried over Na2SO4. The solvent was removed underreduced pressure to obtain a residue which was purified by columnchromatography over silica gel (eluent: 2% EtOAc in PE) tofurnish the pure compound 1c as yellow solid (300 mg, 88%); mp101-103 °C. 1H NMR (CDCl3): δ = 7.53 (d, J = 15.4 Hz, 1 H), 7.32(d, J = 7.1 Hz, 1 H), 7.28 (t, J = 4.3 Hz, 1 H), 7.22 (d, J = 4.6 Hz, 2H), 7.11-7.20 (m, 4 H), 4.67 (s, 1 H), 3.82-3.89 (q, 2 H), 1.36 (t, J= 7.3 Hz, 3 H). 13C NMR (CDCl3): δ = 139.3, 137.8, 129.7, 129.5,128.2, 128.0, 127.4, 127.3, 127.0, 126.5, 126.2, 126.0, 125.2, 124.1,71.2, 67.2,15.2. IR (KBr): 3023, 3012, 2934, 2922, 2843, 1403,1223, 915, 723 cm-1. Anal. Calcd for C17H16O: C, 86.40; H, 6.82;O, 6.77. Found: C, 86.21; H, 6.70; O, 6.65. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With Iron(III) nitrate nonahydrate; ammonium hydroxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 20℃; for 12h; | |
88% | With ammonium hydroxide In <i>tert</i>-butyl alcohol at 130℃; for 24h; Sealed tube; Autoclave; | S7. Procedure for the synthesis of nitriles General procedure: The magnetic stirring bar and corresponding alcohol were transferred to 8 mL glass vial then 2 mL t-butanolsolvent was added. Then, 35 mg catalyst was added followed by the addition of aq. NH3. Then the vial wasf itted with septum, cap, and needle. The reaction vials were placed into a 300 mL autoclave (8 vials containingdif ferent substrates were placed at a time in the autoclave) and the autoclave was pressurized with 10 bar air.The autoclave was placed into an aluminium block and the temperature of the aluminum block was set in orderobtain 120 °C inside the autoclave. Temperature of the aluminum block was set to 130 oC to attain 120 oCinside the autoclave, which was considered as the reaction temperature. The reactions were allowed toprogress under continuous stirring for the required time at 120 °C. Af ter completion of the reaction, the autoclave was cooled down to room temperature and the remaining air was gradually discharged. Then, thecatalyst was f iltered-off, and washed with ethyl acetate. The solvent f rom the f iltrate containing the reactionproducts was purif ied by column chromatography. Products were analyzed by GC, GC-MS, and NMRspectroscopy. In the case of yields determined the by GC, 100 μL n-hexadecane was added to the reactionvial containing the products and diluted with ethyl acetate. Then the reaction mixture containing catalyst andproducts was filtered through a plug of silica and the filtrate containing product was analyzed by GC. |
52% | With copper(I) oxide; 1,10-Phenanthroline; oxygen; potassium ferrocyanide In dimethyl sulfoxide at 120℃; for 40h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Stage #1: 9-hydroxymethylanthracene; 2-Bromoacetyl bromide With potassium carbonate In tetrahydrofuran at 20℃; for 3h; Cooling with ice; Stage #2: pyridine at 50℃; for 6h; | 2 4.2 Synthesis of 1-(2-(anthracen-9-ylmethoxy)-2-oxoethyl) pyridinium bromide (AP-1) 2-Bromoacetyl bromide (0.56 mL, 6.4 mmol) in THF (5 mL) was added dropwise into a THF solution (10 mL) of 9-anthracenylmethanol (1.04 g, 5 mmol) and potassium carbonate (1.38 g, 10 mmol) on the ice bath. The mixture was stirred at room temperature for 3 h, and then the reaction solution was filtered. After that, the solvents were removed under reduced pressure, and the crude mixture was re-dissolved in pyridine (10 mL). After stirring at 50 °C for 6 h, the solvent was removed under reduced pressure, crystallized in ether, filtered, dried under vacuum to afford a yellow solid, AP-1, 1.3 g, yield 64%; mp 160-162 °C; MS-ESI (+) m/z: 328; HRMS (ESI): m/z calcd for C22H18NO2: 328.1338; found: 328.1336; 1H NMR (400 MHz, DMSO-d6) δ 9.10 (2H, d, J=5.2 Hz, pyridinium-H), 8.76 (1H, s, anthracene-H), 8.72 (1H, t, J=8.0 Hz, pyridinium-H), 8.39 (2H, d, J=8.4 Hz, anthracene-H), 8.25 (2H, t, J=7.2 Hz, pyridinium-H), 8.16 (2H, d, J=8.4 Hz, anthracene-H), 7.65 (2H, ddd, J=8.8, 6.4, 0.8 Hz, anthracene-H), 7.44 (2H, ddd, J=8.4, 6.4, 0.8 Hz, anthracene-H), 6.28 (2H, s, OCH2), 5.73 (2H, s, NCH2); 13C NMR (100 MHz, DMSO-d6) δ 166.6 (C=O), 146.8, 146.3, 127.9 (5C, pyridinium-C), 130.9, 130.6, 129.4, 129.0, 127.0, 125.4, 125.1, 124.0 (14C, anthracene-C), 60.6, 60.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: 11-bromoundecanoic acid With thionyl chloride; triethylamine Stage #2: 9-hydroxymethylanthracene With triethylamine In tetrahydrofuran at 20℃; for 4h; Stage #3: pyridine at 50℃; for 6h; | 4 4.4 Synthesis of 1-(11-(anthracen-9-ylmethoxy)-11-oxoundecyl) pyridinium bromide (AP-10) General procedure: SOCl2 (7 mL) was added into a solution of 4-bromobutanoic acid (1.67 g, 10 mmol) in toluene (10 mL), and the mixture was refluxed for 5 h. After that, the solvent was removed under reduced pressure, and the residues were re-dissolved in THF (2 mL). The solution was added dropwise into a THF solution (10 mL) of 9-anthracenylmethanol (2.08 g, 10 mmol) and triethylamine (1.5 mL), and the mixture was stirred at room temperature for 4 h. After that, the solvent was removed under reduced pressure, and re-dissolved by ethyl acetate. The organic layer was washed by water, brine, dried with sodium sulfate, filtered, and followed by the removal of the solvent under vacuum. The crude was dissolved in pyridine (10 mL) and stirred at 50 °C for 6 h, and the solvent was removed under reduced pressure. The residues were crystallized in ether, and the precipitates were filtered and dried to afford a white solid, AP-3. The similar procedure as AP-3 was used to synthesize AP-10 to afford a light yellow solid, 3.38 g, yield 66%; mp 96-98 °C MS-ESI (+) m/z: 454; HRMS (ESI): m/z calcd for C31H36NO2: 454.2746; found: 454.2750; 1H NMR (400 MHz, CD3OD) δ 8.96 (2H, dd, J=6.4, 1.2 Hz, pyridinium-H), 8.54 (1H, ddd, J=7.2, 7.2, 1.2 Hz, pyridinium-H), 8.46 (1H, s, anthracene-H), 8.29 (2H, dd, J=8.8, 0.4 Hz, anthracene-H), 8.07 (2H, t, J=7.0 Hz, pyridinium-H), 7.98 (2H, dd, J=8.4, 0.8 Hz, anthracene-H), 7.51 (2H, ddd, J=8.8, 6.4, 0.8 Hz, anthracene-H), 7.44 (2H, ddd, J=8.4, 6.4, 0.4 Hz, anthracene-H), 6.08 (2H, s, OCH2), 4.56 (2H, t, J=7.6 Hz, NCH2), 2.24 (2H, t, J=7.6 Hz, CH2CO), 1.91-1.30 (16H, m, CH2); 13C NMR (100 MHz, CD3OD) δ 175.5 (C=O), 146.9, 145.9, 129.6 (5C, pyridinium-C), 132.9, 132.3, 130.3, 127.8, 126.3, 125.1 (14C, anthracene-C), 63.1, 59.7, 35.2, 32.5, 30.3, 30.2, 30.0, 27.1, 26.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | General procedure: SOCl2 (7 mL) was added into a solution of 4-bromobutanoic acid (1.67 g, 10 mmol) in toluene (10 mL), and the mixture was refluxed for 5 h. After that, the solvent was removed under reduced pressure, and the residues were re-dissolved in THF (2 mL). The solution was added dropwise into a THF solution (10 mL) of 9-anthracenylmethanol (2.08 g, 10 mmol) and triethylamine (1.5 mL), and the mixture was stirred at room temperature for 4 h. After that, the solvent was removed under reduced pressure, and re-dissolved by ethyl acetate. The organic layer was washed by water, brine, dried with sodium sulfate, filtered, and followed by the removal of the solvent under vacuum. The crude was dissolved in pyridine (10 mL) and stirred at 50 C for 6 h, and the solvent was removed under reduced pressure. The residues were crystallized in ether, and the precipitates were filtered and dried to afford a white solid, AP-3. The similar procedure as AP-3 was used to synthesize AP-15 to afford a white solid, 1.5 g, yield 50%; mp 79-80 C; MS-ESI (+) m/z: 524; HRMS (ESI): m/z calcd for C36H46NO2: 524.3529; found: 524.3519; 1H NMR (300 MHz, CD3OD) delta 8.95 (2H, d, J=6.3 Hz, pyridinium-H), 8.48 (1H, ddd, J=8.1, 7.8, 1.2 Hz, pyridinium-H), 8.28 (1H, s, anthracene-H), 8.19 (2H, d, J=8.7 Hz, anthracene-H), 8.01 (2H, t, J=6.8 Hz, pyridinium-H), 7.84 (2H, d, J=8.1 Hz, anthracene-H), 7.43 (2H, t, J=7.6 Hz, anthracene-H), 7.34 (2H, t, J=8.8 Hz, anthracene-H), 5.96 (2H, s, OCH2), 4.52 (2H, t, J=7.6 Hz, NCH2), 2.11 (2H, t, J=7.3 Hz, CH2CO), 1.85-1.00 (26H, m, CH2); 13C NMR (75 MHz, CD3OD) delta 175.0 (C=O), 146.6, 145.7, 129.4 (5C, pyridinium-C), 132.6, 132.1, 130.2, 130.1, 127.6, 126.2, 125.0 (14C, anthracene-C), 62.9, 59.5, 35.1, 32.4, 30.7, 30.6, 30.5, 30.2, 30.1, 30.0, 27.1, 26.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With C10H10N2O6S2(2+)*2HO4S(1-) at 20℃; for 0.0833333h; | General Procedure for the Protection of Alcohols General procedure: A mixture of the substrate (1 mmol), hexamethyldisilazane (0.70 mmol), and/or 3,4-dihydro-2H-pyran (1.4 mmol) and BiPy(SO3H)2(HSO4)2 (10 mg, 1.95 mol%) in CH3CN(3 mL) and/or CH2Cl2 (3 mL) was stirred at room temperature. The progress of thereaction was monitored by TLC (n-hexane: EtOAc; 10:1) and/or GC. After completion ofthe reaction, the mixture was filtered to separate the solid catalyst. Then the solution wasfiltered through a silica gel pad and washed with CH3CN (2 × 3 mL) and/or CH2Cl2 (2 ×3 mL). Evaporation of the solvent gave the desired products in high purity. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.5% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere; | |
With potassium carbonate In dimethyl sulfoxide at 20℃; for 26h; Inert atmosphere; | 2.7 Synthesis of anthracene-based phtalonitrile (6) 4-Nitrophtalonitrile (3) and 9-anthrylmethanol (5) (1.442mmol) was dissolved in DMSO (20mL) under nitrogen, then anhydrous K2CO3 (7.78mmol) was added over 2h. The mixture was stirred for 24h at room temperature. Finally water (100mL) was added, and the aqueous phase was extracted with chloroform. 1H NMR (300MHz, DMSO-d6; δ: ppm): 6.30 (s, 2H, CH2-O); 7.51 (m, 6H, Ar-H); 8.12 (m, 3H, Ar-H); 8.61 (d, 2H, J=9.0, Ar-H); 8.80 (s, 1H, Ar-H). 13C NMR (75MHz, DMSO-d6, δ): 63.55; 106.14; 115.30; 116.23; 120.54; 120.81; 123.99; 125.32; 125.67; 126.91; 128.98; 129.22; 130.63; 130.89; 135.69; 162.12. FTIR (cm-1): 3050 (w, aromatic C-H stretching); 2218 (C-N, stretching); 1490 (s, C=C stretching); 738 (s, aromatic C-H out-of-plane bending). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With hafnium tetrakis(trifluoromethanesulfonate) In tetrahydrofuran at 40℃; for 0.5h; Inert atmosphere; stereoselective reaction; | General experimental procedure of Ferrier rearrangement General procedure: To a solution of D-glycal (200 mg, 1.0 eq) in anhydrous tetrahydrofuran (5 mL) under N2 atmosphere were added the acceptor (1.2 eq) and Hf(OTf)4 (10 mol%) at ambient temperature. The mixture was stirred at 40 °C until complete consumption of the starting glycal. The reaction mixture was quenched with saturated sodium bicarbonate (5 mL) and extracted with CH2Cl2 (330 mL). The combined organics were washed with saturated salt water and dried over anhydrous Na2SO4. The solvent was removed under vacuum. The products were purified by silica gel column chromatograph with petroleum ether and ethyl acetate as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: 9-hydroxymethylanthracene With sodium hydride In tetrahydrofuran; mineral oil at 60℃; for 1h; Inert atmosphere; Stage #2: 1,4-bis(bromomethyl)benzene In tetrahydrofuran; mineral oil at 70℃; for 48h; Reflux; Inert atmosphere; | 3 2.3 1,1′-Bis(anthracen-9-yl-methoxy)-p-xylene (“bis-anthracene”) A mixture of 9-anthracenemethanol (1g, 4.8mmol) and anhydrous NaH (60% in oil, in excess) in dry THF (100mL) was prepared, and the mixture was heated to 60°C for 1h under nitrogen atmosphere. Upon its being cooled to room temperature, a solution of 1,4-bis(bromomethyl)benzene (0.64g, 2.4mmol) in dry THF (50mL) was added dropwise. The resulting mixture was refluxed at 70°C for 48h under nitrogen purging. After the reaction, the solvent was removed on a rotary evaporator, and the reaction mixture was extracted with chloroform and then filtrated. The chloroform solution was washed with water (25mL) four times, and the organic layer was collected and dried with anhydrous sodium sulfate. Upon filtration and solvent evaporation, the resulting sample was purified on a silica gel column with hexane-ethyl acetate (9/1, v/v) as eluent. The bis-anthracene was obtained as a light-yellow solid (0.84g, 70% yield). 1H NMR (500MHz, CDCl3) δ 8.47 (s, 2H), 8.35-8.31 (d, 4H), 8.03-8.01 (d, 4H), 7.53-7.48 (m, 4H), 7.47-7.45 (m, 4H), 7.42 (s, 4H), 5.51 (s, 4H), 4.74 (s, 4H); 13C NMR (125MHz, CDCl3) δ 137.83, 134.04, 131.33, 130.95, 128.89, 128.33, 127.49, 126.08, 124.84, 124.24, 72.01, 63.98ppm. MALDI-TOF: 518.1 (theoretical value 518.2 for C38H30O2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: 9-hydroxymethylanthracene With thionyl chloride In dichloromethane; benzene Inert atmosphere; Reflux; Stage #2: 4-methoxy-phenol With potassium carbonate In acetone for 22h; Reflux; Inert atmosphere; | 9-[(4-Methoxyphenoxy)methyl]anthracene (2b) Analogous as described in [2], anthracen-9-ylmethanol (97%, 3360 mg, 15.65 mmol) was dissolved in dry CH2Cl2(7 mL) and dry benzene (21 mL) under argon. SOCl2was added (1.5 mL, 20.56 mmol) and the solution was stirred at reflux overnight under argon. The reaction mixture was poured into ice-water (50 mL). The organic phase was washed with water (3 × 35 mL), dried (Na2SO4) and concentrated. The residual solid was dissolved in dry acetone (80 mL). 4-Methoxyphenol (99%, 2999 mg, 23.92 mmol) and anhydrous K2CO3(99%, 3300 mg, 23.64 mmol) were incorporated and the solution was stirred at reflux for 22 h under argon. The solvent was evaporated under reduced pressure and water (150 mL) and CH2Cl2(150 mL) were added to the residue. The aqueous phase was extracted with CH2Cl2(3 × 100 mL). The organic phase was washed with saturated Na2CO3(2 × 150 mL), brine (2 × 150 mL), dried (Na2SO4) and concentrated. The residual solid was purified by flash chromatography to afford 2b (3976 mg, 12.65 mmol, 81%).2b: Colorless crystalline solid; mp 123-124 C (Hexane-CH2Cl2); IR (KBr) 3062, 2998, 1590, 1507, 1222, 1009, 829 cm-1; 1H NMR (300 MHz, CDCl3) 8.52 (s, 1 H, H-10), 8.31 (d, J1-2= J7-8= 8.6 Hz, 2 H, H-1 and H-8), 8.05 (dd, J3-4= J5-6= 7.9 Hz, J2-4= J5-7= 1.4 Hz, 2 H, H-4 and H-5), 7.57-7.46 (m, 4 H, H-2 , H-3, H-6 and H-7), 7.13-7.07 (m, 2 H, H-13 and H-17), 6.96-6.90 (m, 2 H, H-14 and H-16), 5.91 (s, 2 H, H-11), 3.82 (s, 3 H , H-18); 13C NMR (75.5 MHz, CDCl3) 154.0 (C, C-15), 153.3 (C, C-12), 131.3 (C, 2 C, C-4a and C-10a), 130.8 (C, 2 C, C-8a and C-9a), 128.9 (CH, 2 C, C-4 and C-5), 128.7 (CH, C-10), 127.0 (C, C-9), 126.3 (CH, 2 C, C-2 and C-7)*, 124.8 (CH, 2 C, C-3 and C-6)*, 123.9 (CH, 2 C, C-1 and C-8), 115.7 (CH, 2 C, C-13 and C-17), 114.6 (CH, 2 C, C-14 and C-16) , 63.1 (CH2, C-11), 55.5 (CH3, C-18); HRMS calc. for C22H18O2Na [M+Na]+337.1199. Found 337.1191. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: bis(trichloromethyl) carbonate; 9-hydroxymethylanthracene With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; Stage #2: 2-ethyl-N-(2-ethylhexyl)-1-hexanamine In dichloromethane for 4h; Inert atmosphere; | 3 Synthesis of ANT-DEHC As generally depicted in Scheme 3 above, triphosgene(2.137 g 0.5 eq.) suspended in anhydrous DCM(30 mL) under nitrogen atmosphere. The solution was cooled to 0° C. Then 9-(Hydroxymethyl)anthracene(3.0 g; 1.0 eq.) in anhydrous DCM(100 mL) and N,N-diisopropylethylamine(3.723 g; 2.0 eq.) were added. After stirring at RT for 3 h, bis(2-ethylhexyl)amine(3.478 g; 1.0 eq.) was slowly added and stirred for 4 h. The reaction mixture was washed by water and the organic phase is dried over sodium sulfate, filtered off and concentrated under reduced pressure. The crude title compound was purified by flash chromatography(EtOAc/heptane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: 9-hydroxymethylanthracene With N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.5h; Stage #2: 3-oxa-1,5-dichloropentane at 0 - 25℃; for 18h; | 4 9-((methoxymethoxy)methyl)anthracene (3): To 354 mg (1.7 mmol) of anthracen-9-ylmethanol 2 in CH2C12 was added 1.76 mL (10.2 mmol) of N,Ndiisopropylethylamine at 0 C. After stirring for 30 mm, 0.4 mL (5.1 mmol) of chloromethylmethyl ether was added to this solution at 0 C. The mixture was stirred for 10 mm, warmed to 25 C, and stirred for 18 h. Saturated NH4C1 (aq) solution was added to thereaction. The organic layer was extracted from the solution, dried with anhydrous sodium sulfate, concentrated in vacuo, and purified by column chromatography using ethyl acetate/hexanes (4%) as the eluentto give 391 mg of 3 (391 mg, 91 % isolated yield). Physical Property: Pale yellow solid, m.p. = 80-8 1 °C.TLC: Rf= 0.52 (silica gel, 25% ethyl acetate/hexanes).‘H NMR (500 MHz, CDC13) ö 8.53 (d, 2H, J = 8.8 Hz), 8.47 (s, 1H), 8.04 (d, 2H, J = 8.4 Hz), 7.68-7.62 (m, 2H), 7.58-7.51 (m, 2H), 5.67 (s, 2H), 4.90 (s, 2H), 3.61 (s, 3H). ‘3C NMR (125 MHz, CDC13) ö 131.6, 131.3, 129.2, 128.7, 128.4, 126.4, 125.1, 124.4, 95.7, 61.1, 55.8.JR (neat): 1733, 1446, 1265, 1147, 1093, 1061, 1029, 934, 914, 891, 731, 703, 640 cmi. HRMS (ESI) calculated for C,7H,6NaO2 [M+Naj 275.1043, found 275.1055. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33%; 15%; 18% | With tetrabutyl phosphonium bromide; Trimethylacetic acid; In water; chlorobenzene; at 80℃; for 2.5h;Sealed tube; | General procedure: In a 5 mL sealed tube, TBPB(30 mol%, 0.041 g), and TBHP (70 wt% in H2O, 1.0 mmol, 0.131 g) was added to a solution ofbenzyl alcohol 1a (0.4 mmol, 0.043 g) in chlorobenzene (1 mL). The resultant mixture washeated at 80 C for 2.5 h. After completion of the reaction as was indicated by TLC monitoring,the reaction mixture was cooled to ambient temperature and saturated NaHCO3 (2 mL) wasadded. The product was extracted with ethyl acetate (2 × 3 mL). The combined organic phasewas dried over Na2SO4. The solvent was removed under the reduced pressure. The residue waspurified by column chromatography using n-hexane-EtOAc (15:1) as eluent to afford pureproduct 2a as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tert.-butylhydroperoxide; tetrabutyl phosphonium bromide In water; chlorobenzene at 80℃; for 3h; Sealed tube; | General procedure for the synthesis of benzoic anhydride (2a) General procedure: In a 5 mL sealed tube, TBPB(30 mol%, 0.041 g), and TBHP (70 wt% in H2O, 1.0 mmol, 0.131 g) was added to a solution ofbenzyl alcohol 1a (0.4 mmol, 0.043 g) in chlorobenzene (1 mL). The resultant mixture washeated at 80 °C for 2.5 h. After completion of the reaction as was indicated by TLC monitoring,the reaction mixture was cooled to ambient temperature and saturated NaHCO3 (2 mL) wasadded. The product was extracted with ethyl acetate (2 × 3 mL). The combined organic phasewas dried over Na2SO4. The solvent was removed under the reduced pressure. The residue waspurified by column chromatography using n-hexane-EtOAc (15:1) as eluent to afford pureproduct 2a as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: 9-hydroxymethylanthracene With n-butyllithium In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With propargyl bromide In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; | 2.3. Synthesis of alkyne functionalized anthracene 9-Anthracenemethanol (2.0 g, 9.6 mmol) was added into a solutionof dry THF (30 ml) under inert atmosphere at 0 C. n-BuLi(4.0 mL, 2.5 M,10 mmol) was slowly introduced in this solution andthe resultant mixture was stirred for 30 min. Later, propargyl bromide(1.66 mL, 19.2 mmol) was added into the mixture and then itwas stirred for 18 h at room temperature. Later, 20 mL water and150 mL diethyl ether were introduced into the mixture and theorganic phase was extracted. Finally, the organic phase was driedwith NaSO4 and the solvent was evaporated under reduced pressureand the crude product was purified by column chromatography(Hexane:EtOAc 10:1) to obtain 9-((prop-2-yn-1-yloxy)methyl)anthracene (1.55 g, 66% yield). 1H NMR (500 MHz, CDCl3): d 8.49e8.44 (m, 3H), 8.02 (d, J 8.6 Hz, 2H), 7.58e7.47 (m, 4H), 5.62(s, 2H), 4.32 (d, J 2.5 Hz, 2H), 2.62 (t, J 2.5 Hz, 1H), APT NMR(125 MHz, CDCl3): d 131.36 (Cquat),131.14 (Cquat),128.96 (CH),128.67(CH), 127.72 (Cquat), 126.29 (CH), 124.95 (CH), 124.16 (CH), 80.09(Cquat.), 74.90 (CH*, alkyne), 63.56 (CH2), 57.39 (CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 11-bromoundecanoic acid With thionyl chloride In toluene for 5h; Reflux; Enzymatic reaction; Stage #2: 9-hydroxymethylanthracene With triethylamine In tetrahydrofuran at 20℃; for 4h; | SOCl2 (7 mL) wasadded into a solution of 11-bromoundecanoic acid (2.69 g, 10.0 mmol) in drytoluene (10 mL), and then the mixture was refluxed for 5 h. The solvent wasremoved under reduced pressure, and re-dissolved by dry tetrahydrofuran (THF, 5mL). It was added dropwise into a solution of 9-anthracenylmethanol (2.00 g,9.6 mmol) and triethylamine (TEA, 1.5 mL) in dry THF (20 mL), and then themixture was stirred at room temperature for 4 h. Afterthat, the solvent was removed under reduced pressure, and re-dissolved bydichloromethane. The organic layer was washed by water, brine, dried withsodium sulfate, filtered, and followed by the removal of the solvent undervacuum. Finally, the crude wasdissolved in pyridine (10 mL), and the mixturewas stirred at 50 oC for 6 h. The solvent was removed under reducedpressure, and re-dissolved by methanol. The methanol solution precipitated inether, and the precipitates were filtered and dried to afford a yellow solid, 9-AP-10. The synthesis of 1-BP-10, 2-NP-10, 2-AP-10, and 1-PP-10were carried out by the same methodof 9-AP-10.The difference wasthat 1-phenylmethanol,2-naphthalenylmethanol, 2-anthracenylmethanol, and 1-pyrenylmethanol were used insteadof 9-anthracenylmethanol, respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: SOCl2 (7 mL) wasadded into a solution of 11-bromoundecanoic acid (2.69 g, 10.0 mmol) in drytoluene (10 mL), and then the mixture was refluxed for 5 h. The solvent wasremoved under reduced pressure, and re-dissolved by dry tetrahydrofuran (THF, 5mL). It was added dropwise into a solution of 9-anthracenylmethanol (2.00 g,9.6 mmol) and triethylamine (TEA, 1.5 mL) in dry THF (20 mL), and then themixture was stirred at room temperature for 4 h. Afterthat, the solvent was removed under reduced pressure, and re-dissolved bydichloromethane. The organic layer was washed by water, brine, dried withsodium sulfate, filtered, and followed by the removal of the solvent undervacuum. Finally, the crude wasdissolved in pyridine (10 mL), and the mixturewas stirred at 50 oC for 6 h. The solvent was removed under reducedpressure, and re-dissolved by methanol. The methanol solution precipitated inether, and the precipitates were filtered and dried to afford a yellow solid, 9-AP-10. The synthesis of 1-BP-10, 2-NP-10, 2-AP-10, and 1-PP-10were carried out by the same methodof 9-AP-10.The difference wasthat 1-phenylmethanol,2-naphthalenylmethanol, 2-anthracenylmethanol, and 1-pyrenylmethanol were used insteadof 9-anthracenylmethanol, respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In acetonitrile at 60℃; for 0.75h; | 13 3.3. General procedure for the preparation of 7-41 General procedure: (E)-Cinnamic acid (1) (0.167 g, 1.13 mmol), EDC (0.270 g, 1.4mmol), DMAP (0.343 g, 2.8 mmol), and the alcohol (2a-6i) (0.97mmol) were combined with acetonitrile (15 mL). The reaction mixture was stirred at 40-45°C in a water bath for 45 min. Reactions involving aromatic alcohols were monitored for loss of alcohol byTLC (aluminum-backed silica gel plates, 1:4 ethyl acetate/hexanes).The solvent was removed under reduced pressure. The residue was dissolved in diethyl ether (25 mL), and the solution was washed with 3 M HCl (2 20 mL), saturated sodium bicarbonate (2 20mL), and brine (20 mL). The organic layer was dried with MgSO4 and filtered, and the solvent was removed under reduced pressure to yield the corresponding ester. The spectral data are summarized below for each compound. 1H and 13C NMR spectra can be found in the Supplementary Information. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrogenchloride; thiourea In water; acetone | General procedure for the synthesis of bridged sulfides 6 General procedure: Aldehydes 9 (16 mmol) dissolved in methanol,were reduced to corresponding alcohols 14 using sodium borohydride (1.1 g, 30 mmol) in methanol. Alcohols 14 (10 mmol) and two equivalents of thiourea (1.5 g, 20 mmol) were dissolved in acetone (25 mL) and 5N HCl(5 mL) was added to it and stirred overnight. The precipitate formed was filtered and treated with sodium hydroxide (10 %, 30 mL) solution and stirred at room temperature for 2h. Acidification with 5N HCl (25 mL) yielded 16 in 87-95 % yield as shown in Table 2. To a solution of anthracenethiols 16 (5 mmol) dissolved in chloroform (20 ml), KOH (0.20 g, 5 mmol) dissolved in methanol was added at 0 °C followed by propargyl bromide (0.38 mL, 5 mmol) and stirred overnight. Reaction mixture was concentrated, washed with water and extracted with dichloromethane to obtain thioethers 17 in 75-85 % yields. Thioethers 17 were purified by silicagel column chromatography using a mixture of hexane and dichloromethane as eluents. IMDA reaction of 17(5 mmol) was effected by refluxing in p-xylene (10 mL) (5-10h) to obtain corresponding barrelenes 6 in 70-80% yields after recrystallization from suitable solvents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | In o-xylene at 150℃; for 30h; Inert atmosphere; Sealed tube; | 2.4. Catalytic amination reactions General procedure: Dried pressure tube was charged with magnetic stir bar and50 mg of PdSiO2 catalysts (1 mol% with respect to amine). Then,1.0 mL o-xylene was added, followed by the addition of 0.5 mmolof amine and 1 mmol of benzyl alcohol. The pressure tube wasflushed with argon was closed with screw cap. Then it was placedin the preheated aluminum block and reaction was allowed to progressfor 30 h at 150 °C. After completion of the reaction, pressuretube was removed from aluminum block and cooled down to roomtemperature. The catalyst was filtered out by ciliate and reactionproducts were analyzed by GC-MS and the corresponding amineswere purified by column chromatography. The yields of selectedamines were determined by GC analysis using n-hexadecane asstandard. For this purpose, after completion of the reaction, nhexadecane(100 mL) as standard was added to the reaction pressuretube and the reaction products were diluted with ethyl acetate followed by filtration using plug of silica and then subjected GCanalysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With potassium-t-butoxide; hydrazine hydrate monohydrate In toluene at 80℃; for 12h; | 2.5 General procedure for synthesis of azines using alcohols General procedure: A mixture of catalyst 1 (1mol %), KOtBu (5mol %), primary alcohol (0.5mmol), and hydrazine hydrate (1mmol) was loaded in a round bottomed flask containing 3mL of toluene and stirred at 80°C for 12h. The mixture was then cooled to room temperature and extracted using distilled water (5mL) and dichloromethane (5mL). The organic layer was passed through sodium sulphate to remove the moisture. The residue was purified using silica gel column chromatography with eluent petroleum ether (60-80°C) and ethyl acetate (9:1, v/v) to obtain the desired product. |
64% | With potassium-t-butoxide; C20H22ClN4O2RuS(1+)*Cl(1-); hydrazine hydrate monohydrate In toluene at 80℃; for 24h; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With coomassie brilliant blue (CBB) coated on n-propylamine functionalized W-ZnO nanoparticles In ethanol at 25℃; for 2h; UV-irradiation; Green chemistry; | |
90% | With tetra-(n-butyl)-phosphonium bromide In water monomer at 80℃; for 2.83333h; | |
90% | With air; Fe3O4 fabricated ZnO doped WO3 nanoparticle In ethanol at 20℃; for 2.5h; Irradiation; Green chemistry; |
90% | With tetrabutylammonium bromide In N,N-dimethyl-formamide at 80℃; for 2h; | 2.6. General procedure for the synthesis of benzimidazoles or benzothiazoles in the presence of Pd(II)Cl2-BTP(at)MNPs catalyst General procedure: A mixture of alcohol (1 mmol), 1,2-phenylenediamine or 2-aminothiophenol(1 mmol), Pd(II)Cl2-BTPMNPs (0.019 g, containing 0.09mol% Pd) and (1 mmol) tetrabutylammonium bromide (TBAB, 0.01 g)in DMF (5 mL) in a round-bottomed flask equipped with a condenser wasstirred at 80 °C. The progress of the reaction was monitored by TLC(eluent: n-Hexane/EtOAc, 4: 1 for benzimidazoles and n-Hexane/EtOAc, 6: 1 for benzothiazoles). The catalyst was separated by permanentmagnet and washed with EtOAc (10 mL). The crude product waspurified by recrystallization from EtOAc or EtOH to afford the purebenzimidazole. The benzothiazoles was obtained by recrystallizationfrom n-hexane/EtOAc (10: 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With sodium t-butanolate In toluene at 150℃; for 24h; Sealed tube; | General procedure for NaOtBu-catalyzed esterification ofamides. General procedure: To a dry 35 mL sealed tube with a stir bar, amide (0.5 mmol), NaOtBu (0.1 mmol), phenol/alcohol (1.0 mmol) and toluene (5.0 mL) were added. After sealed with a Teflon-lined cap, the reaction mixture was stirred at 150 °C for 24 h. Then the mixture was cooled to room temperature and quenched with H2O (5.0 mL). The mixture was separated and extracted with ethyl acetate (EA) (15 mL×3). The combined organic layer was dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography with ethyl acetate/petroleum ether to give the desired product. More experimental details and characterizations are available in the Supporting Information online. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 9-hydroxymethylanthracene With caesium carbonate In tetrahydrofuran for 0.5h; Reflux; Stage #2: ortho-nitrofluorobenzene In tetrahydrofuran for 24h; Reflux; | 2.6.1. Synthesis of 9-((2-nitrophenoxy)methyl)anthracene (A3) and 1-((2-nitrophenoxy) methyl)pyrene (P3) General procedure: 4.80 mmol 9-anthracene methanol (for A3) and 1-pyrene methanol(for P3) were dissolved 20 mL THF in presence of 9.60 mmol Cs2CO3(3.13 g). The obtained mixtures were refluxed for half an hour. Then,4.80 mmol 1-fluoro-2-nitrobenzene (0.68 g) was added to the reactionmixture via dropping funnel and obtained mixtures were refluxed for24 h. After the reaction completed, mixtures were filtrated via G4 filterand Na2SO4 was used for drying the organic phase. A solvent of thereaction was evaporated with a rotary evaporator and to purify A3 andP3 column chromatography was applied with silica gel and 1:3 v/vdichloromethane:hexane. A3 and P3 were yellow solids and they wereobtained as 87 % and 85 % yield, respectively.A3: [M]+: 329.949 m/z (calc. [M]+: 329.36). 1H NMR at 25 C inCDCl3, δppm; 8.53 (s, 1 H), 8.33 (d, J =8.9 Hz, 2 H), 8.04 (d, J =8.9 Hz,2 H), 7.81 (d, J =8.1 Hz, 1 H), 7.60 - 7.47 (m, 5 H), 7.39 (d, J =8.3 Hz,1 H), 7.06 (t, J =7.7 Hz, 1 H), 6.14 (s, 2 H).13C NMR at 25 C in CDCl3,δppm; 152.16, 140.92, 133.92, 131.40, 131.07, 129.23, 126.84, 125.14,123.74, 121.06, 116.14, 65.15. FT-IR; 3091 3021 cm 1 (-ArH),2966 2863 cm 1 (-C-CH), 1605 1450 cm 1 (-C- -C-),1108 855.1 cm 1 (-C-H-), 1521 cm 1 and 1351 cm 1 (-NO2).P3: [M]+: 353.219 m/z (calc. [M]+: 353.380). 1H NMR at 25 C inCDCl3, δppm; 8.33 (d, J =10.6 Hz, 1 H), 8.24 - 8.18 (m, 5 H), 8.11 - 8.06(m, 2 H), 8.05 - 8.01 (m, 1 H), 7.87 (d, J =8.1 Hz, 1 H), 7.50 (t, J=8.0 Hz, 1 H), 7.29 (d, J =8.4 Hz, 1 H), 7.05 (t, J =7.6 Hz, 1 H), 5.95 (s,2 H). 13C NMR at 25 C in DMSO-d6, δppm; 145.16, 134.63, 128.53,127.82, 124.73, 119.66, 118.88, 118.85, 116.16, 114.21, 74.77. FT-IR;3086 3047 cm 1 (-ArH), 2953 2849 cm 1 (-C-CH),1603 1451 cm 1 (-C- - C-), 1101 850.1 cm 1 (-C-H-), 1518 cm 1and 1351 cm 1 (-NO2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate In N,N-dimethyl-formamide for 12h; Inert atmosphere; Reflux; | 4 Step (B-3), Under the protection of argon, the tenth compound (1.66 mmol) with the structure represented by formula (34), the eleventh compound (19 mmol) with the structure represented by formula (35), anhydrous potassium carbonate (30 mmol), 50ml DMF were placed In a 100ml three-necked flask, heat to reflux for 12h to complete the seventh reaction. After the reaction, the solvent was removed under reduced pressure, dissolved in dichloromethane, and washed with water three times.Collect and combine the organic phases. Use anhydrous sodium sulfate to dry,The solvent was removed to obtain a crude product. Purified by column chromatography (silica gel filler, chloroform), the twelfth compound with the structure represented by formula (36) was obtained with a yield of 86%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate In N,N-dimethyl-formamide for 12h; Inert atmosphere; Reflux; | 5 Step (B-3), Under the protection of argon, the tenth compound (1.66 mmol) with the structure represented by formula (42), the eleventh compound (19 mmol) with the structure represented by formula (35), anhydrous potassium carbonate (30 mmol), 50ml DMF Put it in a 100ml three-necked flask,Heat to reflux for 12h to complete the seventh reaction. After the reaction, the solvent was removed under reduced pressure, dissolved in dichloromethane, washed with water three times, and the combined organic phase was collected. Use anhydrous sodium sulfate to dry,The solvent was removed to obtain a crude product. Purification by column chromatography (silica gel filler, chloroform) to obtain the twelfth compound with the structure represented by formula (43), with a yield of 86%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate In N,N-dimethyl-formamide for 12h; Inert atmosphere; Reflux; | 6 Step (B-3), Under the protection of argon, the tenth compound (1.66 mmol) with the structure represented by formula (48), the eleventh compound (19 mmol) with the structure represented by formula (35), anhydrous potassium carbonate (30 mmol), 50ml DMF Place it in a 100ml three-necked flask and heat to reflux for 12h to complete the seventh reaction. After the reaction, the solvent was removed under reduced pressure, dissolved in dichloromethane, washed with water three times, and the combined organic phase was collected. It was dried with anhydrous sodium sulfate and the solvent was removed to obtain a crude product. Purification by column chromatography (silica gel filler, chloroform) to obtain the twelfth compound with the structure represented by formula (49), with a yield of 80%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0℃; for 12h; | Compound 5: 4-benzyl alcohol anthracene (208 mg, 1.0 mmol) and Boc-Gly-OH (1.5 mmol) dissolved in dry dichloromethane (DCM) (10 mL) in 0 °C. Next, the 4-dimethylaminopyridine (DMAP, 0.2 mmol) and N, /V'-dicyclohexylcarbodiimide (DCC, 1.2 mmol) were added to the mixture and then stirred for 12 hours. After the reaction, the solvents were removed under vacuum condition. The raw 5 was purified by silica gel flash column chromatography with DCM/n-hexane =1/1 (v/v) as elute. The shallow yellow band was collected and yield determined to be 71 % (260 mg). -NMR (500 MHz, CDC13): d= 8.53 (s, 1H), 8.33-8.32 (d, 2H, /= 5.0 Hz), 8.04-8.03 (d, 2H, /= 5.0Hz), 7.60-7.57 (m, 2H), 7.52-7.49 (m, 2H), 6.24 (s, 2H), 4.98 (s, 1H), 3.93 (s, 2H), 1.42 ppm (s, 9H). 13C- NMR (125 MHz, CDC13): d = 131.4, 131.1, 129.5, 129.2, 126.9, 125.2, 123.8, 59.7, 42.5, 28.3 ppm. HRMS (ESI) exact mass calculated for [M + Na] + (C22H23N04 + Na+) requires m/z 388.1525, found m/z 388.1519. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0℃; for 12h; | Compound 6: 4-benzyl alcohol anthracene (208 mg, 1.0 mmol) and Boc-GABA-OH (1.5 mmol) dissolved in dry dichloromethane (DCM) (10 mL) in 0 °C. Next, 4- dimethylaminopyridine (DMAP, 0.2 mmol) and N, /V'-dicyclohexylcarbodiimide (DCC, 1.2 mmol) were added to the mixture and then stirred for 12 hours. After the reaction, the solvents were removed under vacuum condition. The raw 6 was purified by silica gel flash column chromatography with DCM/n-hexane =1/1 (v/v) as elute. The shallow yellow band was collected and yield determined to be 80 % (314 mg). -NMR (500 MHz, CDC13): d= 8.51 (s, 1H), 8.34-8.32 (d, 2H, J = 10.0Hz,), 8.04-8.03 (d, 2H, /= 5.0 Hz,), 7.59-7.56 (m, 2H), 7.51-7.48 (m, 2H), 6.17 (s, 2H), 4.54 (s, 1H), 3.13-3.12 (d, 2H, /= 5.0 Hz), 2.39-2.36 (m, 2H), 1.82-1.78 (m, 2H), 1.41 ppm (s, 9H). 13C- NMR (125 MHz, CDC13): d= 173.4, 155.9, 131.4, 131.0, 129.2, 129.1, 126.7, 126.2, 125.1, 123.9, 58.9, 39.8, 31.1, 28.4, 25.3 ppm. HRMS (ESI) exact mass calculated for [M + Na] + (C24H27N04 + Na +) requires m/z 416.1838, found m/z 416.1832. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.9% | Stage #1: N-methylmaleimide With 1-butyl-3-methylimidazolium chloride at 40℃; for 0.166667h; Green chemistry; Stage #2: 9-hydroxymethylanthracene at 40℃; for 1.83333h; Green chemistry; | General procedure for Diels-Alder reaction To a 10 mL round-bottomed flask equipped with magnetic stirrer, 0.0555 mg (0.5 mmol) N-methyl maleimide and 0.5 g (2.87 mmol) IL [bmim][Cl] were added. The reaction mixture was allowed to stir at 40°C for about 10 min and then 0.101 g (0.5 mmol) 9-hydroxymethylanthracene derivatives were added. The stirring was continued for additional 110 min. After the reaction completion as monitored by TLC, water was added to the reaction mixture; the product obtained was filtered and dried to give a colorless solid. The crude solid obtained was purified by passing it through a silica gel column using chloroform-petroleum ether as an eluant to furnish pure Diels-Alder adduct. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.48% | Stage #1: N-Ethylmaleimide With 1-butyl-3-methylimidazolium chloride at 40℃; for 0.166667h; Green chemistry; Stage #2: 9-hydroxymethylanthracene at 40℃; for 1.83333h; Green chemistry; | General procedure for Diels-Alder reaction General procedure: To a 10 mL round-bottomed flask equipped with magnetic stirrer, 0.0555 mg (0.5 mmol) N-methyl maleimide and 0.5 g (2.87 mmol) IL [bmim][Cl] were added. The reaction mixture was allowed to stir at 40°C for about 10 min and then 0.101 g (0.5 mmol) 9-hydroxymethylanthracene derivatives were added. The stirring was continued for additional 110 min. After the reaction completion as monitored by TLC, water was added to the reaction mixture; the product obtained was filtered and dried to give a colorless solid. The crude solid obtained was purified by passing it through a silica gel column using chloroform-petroleum ether as an eluant to furnish pure Diels-Alder adduct. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.83% | Stage #1: 1-(2-methoxyphenyl)maleimide With 1-butyl-3-methylimidazolium chloride at 40℃; for 0.166667h; Green chemistry; Stage #2: 9-hydroxymethylanthracene at 40℃; for 1.83333h; Green chemistry; | General procedure for Diels-Alder reaction General procedure: To a 10 mL round-bottomed flask equipped with magnetic stirrer, 0.0555 mg (0.5 mmol) N-methyl maleimide and 0.5 g (2.87 mmol) IL [bmim][Cl] were added. The reaction mixture was allowed to stir at 40°C for about 10 min and then 0.101 g (0.5 mmol) 9-hydroxymethylanthracene derivatives were added. The stirring was continued for additional 110 min. After the reaction completion as monitored by TLC, water was added to the reaction mixture; the product obtained was filtered and dried to give a colorless solid. The crude solid obtained was purified by passing it through a silica gel column using chloroform-petroleum ether as an eluant to furnish pure Diels-Alder adduct. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With magnesium -metalloporphyrin framework In ethanol at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With magnesium -metalloporphyrin framework In ethanol at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With magnesium -metalloporphyrin framework In ethanol at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With magnesium -metalloporphyrin framework In ethanol at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With magnesium -metalloporphyrin framework In ethanol at 25℃; |
Tags: 1468-95-7 synthesis path| 1468-95-7 SDS| 1468-95-7 COA| 1468-95-7 purity| 1468-95-7 application| 1468-95-7 NMR| 1468-95-7 COA| 1468-95-7 structure
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P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
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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