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CAS No. : | 934-00-9 | MDL No. : | MFCD00002191 |
Formula : | C7H8O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LPYUENQFPVNPHY-UHFFFAOYSA-N |
M.W : | 140.14 | Pubchem ID : | 13622 |
Synonyms : |
|
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 |
---|---|---|
100% | With o-tetrachloroquinone In diethyl ether at -25℃; for 2h; | |
97% | With magnesium(II) sulfate; silver(I) oxide In diethyl ether at 20℃; for 0.5h; Inert atmosphere; | |
82% | With oxygen; mesoporous silica In dichloromethane at 25℃; for 1h; | 3.3. General Procedure for P1/Silica-gel Combined Catalyst Catalyzed Aerobic Oxidation of Various Dihydroxy Arenes General procedure: In a two-neck 100 ml round bottomed flask connected tomolecular oxygen balloon (1.0 atm) and containing dihydroxyarene (0.1 mmol), P1 (100 mg, 0.1 mmol/g loading)and 250 mg silica-gel, a 3.0 mL of CH2Cl2 was injected and the reaction mixture was stirred at room temperature and followed by TLC until the starting material had completely converted to quinone. The quinone product was extracted with CH2Cl2 or ether and was obtained under reduced pressure.The further purification of most of the quinone product was not necessary. The P1/silica-gel combined catalyst was washed several times with ether or CH2Cl2 until it became completely clean and dried under vacuum to be ready for the next cycle. |
79% | With o-tetrachloroquinone In diethyl ether at -20℃; for 0.25h; | 1.A 1:3 mixture of methyl 9-methoxyphenazine-2-carboxylate and methyl 6-methoxyphenazine-2-carboxylate (3) 3,4-diaminobenzoic acid (2 g, 13.14 mmol) was converted into 3,4-methyl diaminobenzoate 2 (2.04 g, 12.27 mmol, 94% yield) using thionyl chloride (1.24 mL, 17.1 mmol) with a MeOH reflux during 11 h. In parallel, a solution of 3-methoxycatechol (2 g, 14.27 mmol) was oxidized by the drop by drop addition of a o-chloranil solution (3.65 g, 14.84 mmol) in anhydrous Et2O at -20° C. during 15 minutes to obtain by filtration 3-methoxy-[1,2]benzoquinone 1 (1.56 g, 11.29 mmol, 79% yield) as a dark green solid. The solid was washed with Et2O and the final residue obtained (700 mg, 5.06 mmol) was immediately redissolved in CH2Cl2 (30 mL) and it was added drop by drop to a solution of methyl ester 2 (660 mg, 3.97 mmol) in the same solvent (10 mL) slightly acidified with acetic acid (5 drops). After stirring during 1.5 h at a.t., the solution was diluted with water (20 mL) and was extracted with CH2Cl2 (10 mL), it was dried (Mg2SO4) and the solvent was vacuum eliminated. The product was purified using silica gel chromatography in a mobile phase of 1:1 EtOAc:hexane to produce the desired compound in the form of a mixture of isomers in the form of a yellow solid (110 mg, 41% yield). Maj is majority product and Min minority product. |
75% | With o-tetrachloroquinone In diethyl ether at -20℃; for 0.416667h; | |
74% | With iodosylbenzene In methanol; dichloromethane Ambient temperature; | |
71% | With [(4,5-dihydro-4,4-dimethyl-2-phenyloxazole)Ru(CH3CN)4]PF6; dihydrogen peroxide In tetrahydrofuran; lithium hydroxide monohydrate at 0 - 20℃; for 0.5h; | 9 General procedure for 2a catalyzed H2O2 oxidation of dihydroxy arenes General procedure: To a solution of dihydroxy arene (0.34 mmol) and 2a (1.98 mg,0.0034 mmol) in THF (1.0 mL) was added H2O2 (30% aq, 50.0 mL,0.44 mmol) at 0 C. After 5 min the starting material had completelyoxidized to the quinone product. The quinone product wasthen extracted by ether or dichloromethane, dried over anhydrous Na2SO4, and concentrated under reduced pressure to afford thedesired product. Pleasingly, the resulted quinone products werepure enough and there is no necessity for column chromatographyin most of the cases. |
71% | With silver(I) oxide In propan-2-one at 20 - 23℃; for 0.166667h; | |
With lead(IV) dioxide; benzene | ||
With diethyl ether; 3-tetrachloro-benzoquinone-(1.2) | ||
With diethyl ether; 3-tetrabromo-benzoquinone-(1.2) | ||
With diethyl ether; silver(I) oxide | ||
With sodium (meta)periodate | ||
With anhydrous silver carbonate In benzene | ||
With β‐cyclodextrin In phosphate buffer at 25℃; | ||
In acetate buffer Electrochemical reaction; | ||
With 1-(4-chlorophenyl)-2-(tetrahydropyrimidin-2(1H)-ylidene)ethan-1-one In acetonitrile aq. acetate buffer; Electrochemical reaction; | ||
With o-tetrachloroquinone In diethyl ether at -78℃; for 4h; | ||
With laccase from Myceliophthora thermophila In aq. phosphate buffer at 20℃; for 24h; Green chemistry; | ||
With o-tetrachloroquinone In diethyl ether at -78℃; for 4h; Inert atmosphere; | ||
With o-tetrachloroquinone In diethyl ether at -78℃; for 4h; Inert atmosphere; | ||
With C15H15CuN3O6*H2O In methanol at 25℃; | ||
With diethyl ether; 3-tetrabromo-benzoquinone-(1.2) | ||
With diethyl ether; 3-tetrachloro-benzoquinone-(1.2) | ||
0.26 mmol | With silver(I) oxide at 0℃; Inert atmosphere; | |
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In N,N-dimethyl-formamide | ||
With 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione In diethyl ether at -78℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium percarbonate In tetrahydrofuran; water for 1h; ultrasonication; | |
94% | With sodium hydroxide; dihydrogen peroxide In water for 1h; | |
94% | With dihydrogen peroxide at 20℃; for 0.833333h; Green chemistry; |
92% | With dihydrogen peroxide In water at 20℃; for 2.5h; Green chemistry; | |
91% | With potassium hydrogensulfate; dihydrogen peroxide In methanol; water at 20℃; for 48h; | 4.2.1. 3-Methoxycatechol (6) o-Vanillin (5) (25 g/164 mmol) was solubilized in 600 mL of methanol and 22 mL of H2O2 30% was added. Then, KHSO4 (3.3 g/24.6 mmol) was added quickly and the solution was allowed to stir at room temperature for 48 h. The reaction was quenched by the addition 200 mL of distilled water and the methanol evaporated. The aqueous phase was extracted with 3 × 300 mL of diethyl ether. The organic phase was washed with 2 × 250 mL of brine, dried over sodium sulfate anhydrous, filtered and the organic solvent evaporated. The crude product was purified by silica gel flash chromatography (dichloromethane) obtaining 3-methoxycatechol (6) as an orange oil (20.96 g/91%) |
88% | With 7,8-difluoro-1,3-dimethyl-5-ethyl-4a-hydroperoxyalloxazine; dihydrogen peroxide; sodium hydrogencarbonate In methanol; water at 20℃; for 0.166667h; | |
84.6% | With dihydrogen peroxide; sodium hydroxide In water | |
76% | With sodium hydroxide; dihydrogen peroxide In water at 40 - 45℃; | |
75% | With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; 1,3-dimethyl-5-ethyl-4a-hydroperoxyalloxazine; oxygen; sodium hydrogencarbonate In water; acetonitrile at 20℃; for 1h; | |
With sodium hydroxide; dihydrogen peroxide unter Leuchtgas; | ||
(oxidation); | ||
With sodium hydroxide; dihydrogen peroxide | ||
With alkaline hydrogen peroxide In water | ||
Multi-step reaction with 2 steps 1: SeO2, 30percent aq. H2O2 / 2-methyl-propan-2-ol / 4 h / Ambient temperature 2: aq. K2CO3 / methanol / 1 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; | |
85% | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; | 1 Step 1) A solution of 3-methoxybenzenediol (25.3g, 180mmol), potassium carbonate (104.5g, 756mmol), and 1,2-dibromoethane (74.4g, 396mmol) in DMF (100mL) The reaction was heated in a nitrogen system at 60 ° C for 6 hours. After quenching with water, it was extracted with ethyl acetate; the organic phase was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered, and concentrated to give a dark gray oil: 5-methoxy -2,3-dihydrobenzo [b] [1,4] dioxane (25.4g, 153mmol, yield 85%); |
85% | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; | Step 1): Combine 3-methoxybenzenediol (25.3g, 180mmol), potassium carbonate (104.5g, 756mmol), and 1,2-dibromoethane (74.4g, 396mmol) in DMF (100mL) The solution was heated and reacted in a nitrogen system at 60°C for 6 hours. After adding water and quenching, it was extracted with ethyl acetate; the organic phase was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered, and concentrated to give a dark gray oil:5-methoxy-2,3-dihydrobenzo[b][1,4]dioxane (25.4g, 153mmol, yield 85%); |
61% | With sodium hydroxide; cetyltrimethylammonim bromide In water for 26h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.69% | With potassium carbonate; copper(II) oxide; In N,N-dimethyl-formamide; at 120℃; for 8h; | To a stirred solution of 3-methoxybenzene-1 ,2-diol (50 g, 357.1 mmol, 1 eq) in DMF (500 mL), was added CuO (3.12 g, 39.2 mmol, 0.1 1 eq) followed by K2CO3 (60.1 g, 435.7 mmol, 1.22 eq) and <strong>[74-95-3]dibromomethane</strong> (75.7 g, 435.7 mmol, 1.22 eq). The resultant reaction mixture was heated at 120C for 8 h. The reaction was monitored with TLC, and TLC analysis indicated formation of a non-polar spot. The reaction mixture was then poured into ice water and extracted with ethyl acetate. The combined organic layer was dried over Na2S04 and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 100-200 mesh) using 0-10% ethyl acetate in petroleum ether as an eluent to afford 4- methoxybenzo[d][1 ,3]dioxole (40 g, 73.69% yield) as a white solid. LCMS: m/z 153.32 (M+H). |
73.69% | With potassium carbonate; copper(II) oxide; In N,N-dimethyl-formamide; at 120℃; for 8h; | To a stirred solution of compound 1 (50g, 357.1 mmol, 1eq) in DMF (500ml_), was added CuO (3.12g, 39.2mmol, 0.1 1 eq) followed by K2CO3 (60.1 g, 435.7mmol, 1.22eq) and dibromo methane (75.7g, 435.7mmol, 1 22eq). The resulting reaction mixture was heated at 120 C for 8h. The reaction was monitored with TLC. TLC analysis indicated formation of a non-polar spot. The reaction mixture was poured into ice water and extracted with ethyl acetate. The combined organic layer was dried over Na2S04 and concentrated under reduced pressure. The crude product was purified by column chromatography (silica 100-200) using 0-10% ethyl acetate in petroleum ether as an eluent to give Compound 2 (40g, 73.69% yield) as white solid. LCMS: m/z 153.32 (M+H): |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With N-Bromosuccinimide; ammonium acetate In acetonitrile at 20℃; for 1h; | 1 To a solution of 3-methoxybenzene-1,2-diol (IX) (15 g, 0.107 mol), and NH4OAc (0.83 g, 10.7 mmol) in MeCN (500 mL) was added NBS (20 g, 0.112 mol) portion wise at room temperature and stirred for an hour. The reaction mixture was concentrated under vacuum, diluted with EtOAc (300 mL), washed with an aqueous solution of 50% NaHSO3 (200 mL), and brine (200 mL) The EtOAc layer was dried over anhydrous Na2SO4, concentrated under vacuum and purified on a silica gel column (100% DCM) to give 3-bromo-6-methoxybenzene-1,2-diol (X) (18 g, 82.2 mmol, 76% yield) as a white solid. 1H NMR (CDCl3, 500 MHz) δ ppm 3.87 (s, 3H), 5.54 (s, 1H), 5.60 (s, 1H), 6.42 (d, J=8.78 Hz, 1H), 6.98 (d, J=8.78 Hz, 1H) |
73% | With N-Bromosuccinimide In acetonitrile at 5℃; for 5h; | |
With N-Bromosuccinimide In acetic acid Ambient temperature; |
With N-Bromosuccinimide In tetrachloromethane at 20℃; for 2h; | 19 To a stirring solution of 3-methoxybenzene-l,2-diol (3 g, 21.42 mmol) in carbon tetrachloride (30 mL) was added /V-bromosuccinimide (4.5 g, 25.28 mmol) and the reaction mixture was stirred at RT for 2 h. The reaction mixture was diluted with ice-cold water and extracted with dichloromethane (3 x). The combined dichloromethane layers were washed with brine, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The obtained residue has mixture of products (3-Bromo-6- methoxybenzene-l,2-diol) which was used as such for further reactions (4.2 g). | |
With N-Bromosuccinimide In water; acetonitrile at 0℃; for 2h; | P13.1 Step 1. Synthesis of 3-bromo-6-methoxybenzene-1,2-diol (C78). To a mixture of 3-methoxybenzene-1,2-diol (578 mg, 4.12 mmcl) in acetonitrile (10 mL) at 0 00 was slowly added N-bromosuccinimide (95%, 811 mg, 4.33 mmol) in acetonitrile (5 mL).After two hours at 0 00, aqueous sodium thiosulfate solution (1 M, 2 mL) was added. After ten minutes, the reaction mixture was concentrated in vacuo and purified by silica gel chromatography (Gradient: 20% to 40% ethyl acetate in heptane) to give the product as a white solid. Yield: 858 mg, 0.3.92 mmol, 95%. LCMS m/z216.8(M-H). 1H NMR (400 MHz, CDCI3)o 7.00 (d, J=9.0 Hz, 1H), 6.43 (d, J=9.0 Hz, 1H), 5.54 (s, 1H), 5.48 (s, 1H), 3.89 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 25℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium carbonate In acetone for 18h; Reflux; | 1 4.1.1 1,2-Bis(allyloxy)-3-methoxybenzene (8a) 3-Methoxy-1,2-benzenediol (0.498 g, 3.56 mmol) was dissolved in acetone (20 mL) and K2CO3 (1.97 g, 14.3 mmol) and allyl bromide (1.72 g, 14.2 mmol) were added. The reaction mixture was then heated at reflux for 18 h. After cooling, H2O (30 mL) was added and the crude product was then extracted with EtOAc (3*100 mL). The combined filtrate was then dried with MgSO4 to afford the product as an yellow oil, which was purified by column chromatography (20% EtOAc/hexane) to afford the desired compound 8a as a light yellow oil (0.60 g, 76%). Rf (30% EtOAc/hexane) 0.72; IR vmax (film)/cm-1 1647, 1475, 1104; 1H NMR (300 MHz, CDCl3): δ (ppm)=3.83 (s, 3H, OCH3), 4.53 (d, 2H, J 6.0 Hz, OCH2), 4.57 (d, 2H, J 5.2 Hz, OCH2), 5.16-5.44 (m, 4H, 2* CH=CH2), 5.99-6.18 (m, 2H, 2* CH2CH=), 6.67 (d, 2H, J 8.6 Hz, 2* ArH), 6.92-6.98 (m, 1H, ArH); 13C NMR (75 MHz, CDCl3): δ (ppm)=55.9 (OCH3), 69.8 (OCH2), 74.0 (OCH2), 105.4 (CH2), 107.1 (CH2), 117.1 (CH), 117.4 (CH), 123.4 (CH), 133.4 (CH), 134.5 (CH), 137.7 (C), 152.6 (C), 153.8 (C); m/z (EI): 220 (M+, 65%), 205 (27), 179 (96), 41 (100); HRMS: M+, calcd for C13H16O3 220.1099, found 220.1098. |
With potassium carbonate In acetone Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium acetate; potassium hexacyanoferrate(III) In water for 1h; | |
74% | With laccase In aq. phosphate buffer at 20℃; for 24h; Enzymatic reaction; | 3 General method for the synthesis of the coumestans General procedure: The laccase (Suberase, 2.0mL) was added to a mixture of the catechol (2.0mmol), coumarin (2.0mmol) and phosphate buffer (20.0mL, 0.10M, pH 7.15) in a 250mL round bottom flask stirred under air at rt. More laccase (2.0mL) was added after 2, 18 and 20h. The mixture was vigorously stirred under air until the substrates were consumed as judged by TLC. The mixture was extracted with EtOAc and washed two times with water (20.0mL). The organic phases were then combined and the solvent evaporated. The residue, a powder, was purified by washing with EtOAc or by flash chromatography or recrystallization. The recrystallization was accomplished from a combination of MeOH and EtOAc. Products were characterized by 1H NMR, 13C NMR, and MS. |
61% | With Trametes versicolor laccase; oxygen In acetate buffer at 20℃; for 5h; |
61% | With laccase from Trametes versicolor at 20℃; for 5h; aq. acetate buffer; Enzymatic reaction; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With Agaricus bisporus laccase; oxygen In acetate buffer at 20℃; for 20h; | |
78% | With laccase In aq. phosphate buffer at 20℃; for 24h; Enzymatic reaction; | 7 General method for the synthesis of the coumestans General procedure: The laccase (Suberase, 2.0mL) was added to a mixture of the catechol (2.0mmol), coumarin (2.0mmol) and phosphate buffer (20.0mL, 0.10M, pH 7.15) in a 250mL round bottom flask stirred under air at rt. More laccase (2.0mL) was added after 2, 18 and 20h. The mixture was vigorously stirred under air until the substrates were consumed as judged by TLC. The mixture was extracted with EtOAc and washed two times with water (20.0mL). The organic phases were then combined and the solvent evaporated. The residue, a powder, was purified by washing with EtOAc or by flash chromatography or recrystallization. The recrystallization was accomplished from a combination of MeOH and EtOAc. Products were characterized by 1H NMR, 13C NMR, and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Agaricus bisporus laccase; oxygen In acetate buffer at 20℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With air In phosphate buffer at 20℃; for 20h; Enzymatic reaction; | |
37% | With laccase from Myceliophthora thermophila; oxygen In aq. phosphate buffer at 20℃; for 24h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With air In phosphate buffer at 20℃; for 20h; Enzymatic reaction; | |
70% | With laccase from Myceliophthora thermophila; oxygen In aq. phosphate buffer at 20℃; for 24h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In DMF (N,N-dimethyl-formamide) at 90℃; for 4h; | 15 Example 15; 4-Methoxy-benzo[1,3]dioxole A mixture of 3-methoxy-benzene-1,2-diol (1.161 g, 8.28 mmol) in DMF (10 mL) was added to bromo-chloro-methane (611 ul, 1.1 equivalents) and stirred at 90 degrees Celsius for 4 hours. The mixture was poured into water and extracted with dichloromethane. The organic layer was poured thru a phase separator cartridge and concentrated to dryness. The crude product is a yellow liquid. The liquid was purified by column chromatography yielding 1.21g, (96%). 1H-NMR (DMSO, 500 MHz) 6.7 (t, 1H), 6.63 (d, 1H), 6.58 (d, 1H), 5.97 (s, 2H), 3.83 (s, 3H) HPLC (method A) 2.86 min. |
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 4h; | 3 4.1.3 4-Methoxybenzo[d][1,3]dioxole (17) [24] To a mixture of 3-methoxybenzene-1,2-diol (500mg, 3.56mmol) and K2CO3 (785mg, 4.28mmol) in anhydrous DMF (18mL) bromochloromethane (374μL, 5.35mmol) was added. The mixture was heated at 100°C for 4h. The solution was allowed to reach room temperature and volatiles were evaporated under reduced pressure. The residue was diluted with dichloromethane and neutralized with 1N HCl. The aqueous phase was further extracted with dichloromethane (3×20mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered and evaporated to dryness. The crude was purified by flash chromatography (hexane/ethyl acetate, 10:1) to yield 255mg (47%) of 17 as colorless oil. 1H NMR (DMSOd6, 400MHz) δ: 3.81 (s, 3H, OCH3), 5.96 (s, 2H, OCH2O), 6.58 (d, J=7.8Hz, 1H, Ar), 6.63 (d, J=8.1Hz, 1H, Ar), 6.79 (t, J=8.2Hz, 1H, Ar). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In benzene | R.63.A Step A) 4-Methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbk-a) Step A) 4-Methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbk-a) 3-Methoxycatechol (25 g) was dissolved in benzene, and dimethoxyacetal (35 ml) and a catalytic amount of p-toluenesulfonic acid were added thereto, followed by heating at reflux for 6 hours. After being allowed to stand for cooling, the mixture was adjusted to alkaline with an aqueous solution of sodium hydroxide, followed by extraction with ether.- The organic layer was washed with a saturated saline and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column -chromatography (hexane/ethyl acetate=99/1) to give Compound IIbk-a (19.4 g, 60.5%) as a white solid. NMR(CDCl3, δ, ppm): 1.68(s, 6H), 3.86(s, 3H), 6.42-6.49(m, 2H), 6.69-6.75(m, 1H) | |
With sodium hydroxide In benzene | R.74.A Step A) 4-methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbv-a) Step A) 4-methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbv-a) 3-methoxycatechol (25 g) was dissolved in benzene, mixed with dimethoxyacetal (35 ml) and a catalytic amount of tosylic acid, and then, heat-refluxed for 6 hours. The resultant was allowed to stand for cooling, alkalified by adding an aqueous sodium hydroxide solution, and extracted with ether. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over manganese sulfate, and evaporated under reduced pressure for removing the solvent. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=99/1) to give Compound IIbv-a (19.4 g, 60.5%) as a white solid. NMR(CDCl3, δ, ppm): 1.68(s, 6H), 3.86(s, 3H), 6.42-6.49(m, 2H), 6.69-6.75(m, 1H) | |
With sodium hydroxide In benzene | R.63.A (Step A) (Step A) 4-Methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbk-a) 3-Methoxycatechol (25 g) was dissolved in benzene, and dimethoxyacetal (35 ml) and a catalytic amount of p-toluenesulfonic acid were added thereto, followed by heating at reflux for 6 hours. After being allowed to stand for cooling, the mixture was adjusted to alkaline with an aqueous solution of sodium hydroxide, followed by extraction with ether. The organic layer was washed with a saturated saline and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=99/1) to give Compound IIbk-a (19.4 g, 60.5%) as a white solid. NMR(CDCl3, δ, ppm): 1.68(s, 6H), 3.86(s, 3H), 6.42-6.49(m, 2H), 6.69-6.75(m, 1H) |
With sodium hydroxide In benzene | R.74.A (Step A) (Step A) 4-methoxy-2,2-dimethyl-1,3-benzodioxole (Compound IIbv-a) 3-methoxycatechol (25 g) was dissolved in benzene, mixed with dimethoxyacetal (35 ml) and a catalytic amount of tosylic acid, and then, heat-refluxed for 6 hours. The resultant was allowed to stand for cooling, alkalified by adding an aqueous sodium hydroxide solution, and extracted with ether. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over manganese sulfate, and evaporated under reduced pressure for removing the solvent. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=99/1) to give Compound IIbv-a (19.4 g, 60.5%) as a white solid. NMR(CDCl3, δ, ppm): 1.68(s, 6H), 3.86(s, 3H), 6.42-6.49(m, 2H), 6.69-6.75(m, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | In diethyl ether N2-atmosphere; addn. of 2 equiv. substituted catechol to B-compd., stirring for 4 h; addn. of excess 1 M HCl in Et2O, stirring for 12 h, removal of volatiles(vac.), dissoln. in PhMe, filtration (Celite), pptn. on layering with h exanes (-30.°C, 48 h); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | In phosphate buffer at 25℃; for 20h; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With boron trifluoride diethyl etherate In N,N-dimethyl-formamide at 120℃; for 0.166667h; | |
With boron trifluoride diethyl etherate In N,N-dimethyl-formamide at 90℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Pleurotus ostreatus In aq. phosphate buffer; acetonitrile at 20℃; for 21h; Green chemistry; Enzymatic reaction; regioselective reaction; | |
74% | With oxygen In water; <i>tert</i>-butyl alcohol at 50℃; for 24h; Green chemistry; regioselective reaction; | |
With polymer-supported periodate; polymer-supported 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine In acetone at -20℃; for 7h; |
With Pleurotus ostreatus In aq. phosphate buffer; acetonitrile at 20℃; for 21h; Green chemistry; Enzymatic reaction; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: 3-methocycatechol; 3,4,5-tris(benzyloxy)benzoyl chloride In acetonitrile at 20℃; for 0.5h; Stage #2: With dmap In acetonitrile at 20℃; for 48h; | Acid chloride 2 (941 mg, 2.05 mmol) was added to a solution of 3-methoxycatechol (140 mg, 1.00 mmol) in anhydrous acetonitrile (10 mL) at room temperature. DMAP (268 mg, 2.20 mmol) was added to the reaction mixture after stirred for 30 min at room temperature, the mixture was stirred for 2 days and the solvent was removed, the crude was purified by chromatography on silica gel (25 % EA in hexane) giving 708 mg of 6 in 72% yield. 1H NMR (CDC 13) δ 7.64 (d, 4H, J= 16.7 Hz), 7.51-7.33 (m, 31H), 7.16 (d, 1H, J= 8.2 Hz), 7.06 (d, 1H, J= 8.4 Hz), 5.18 (d, 4H, J= 7.0 Hz), 5.06 (d, 8H, J= 11 Hz), 3.96 (s, 3H); 13C NMR (CDC 13) δ 164.0, 163.6, 153.1, 152.8, 152.3, 144.1, 143.2, 137.6, 137.5, 136.5, 136.4, 132.3, 128.6, 128.4, 128.3, 128.2, 128.1, 128.0, 127.8, 127.7, 126.6, 123.9, 123.8, 115.4, 110.2, 109.7, 109.6, 75.3, 71.2, 56.4. |
With dmap In acetonitrile |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In acetonitrile at 20℃; aq. acetate buffer; Electrolysis; | 4.3. General procedure for the synthesis of compounds 3a-f General procedure: An H-type cell equipped with a medium porosity of glass frit as a membrane was maintained in water bath at room temperature. The anode compartment contained an anode assembly consisting of seven graphite rods whose upper rims were wrapped by a copper wire; a platinum plate (2 cm2) served as the counter electrode and was immersed in the cathode compartment. The applied current throughout electrolysis was 15 mA (∼3 mA/cm) and was controlled by a direct current power source. During the course of electrolysis, a magnetic stirrer stirred the mixture.Comment In a typical procedure, to the anode compartment was added a mixture of 50 mL 0.2 M acetate buffer/acetonitrile (the volume ratio is 4:1). Subsequently, 1 mmol catechols 1 and 1 mmol 2 were added to the anodic compartment and the solution was electrolyzed. The electrolysis was terminated after 2.24 F/mol of charge was passed. The formed precipitate was filtered, washed with water (3×10 mL), and dried to obtain the corresponding product, 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With Agaricus bisporus tyrosinase; oxygen; ascorbic acid In water at 20℃; for 24h; Na-phosphate buffer; Enzymatic reaction; | 4.10. Phenols oxidation General procedure: A panel of phenols (Fig. 7) were oxidized, including para-cresol 1, 4-ethyl phenol 2, 4-tert-butyl phenol 3, 4-sec-butyl phenol 4, 2,4-di-tert-butyl phenol 5, meta-cresol 6, 3,4-dimethyl phenol 7, 4-chloro phenol 8, 4-chloro-2-methyl phenol 9, 2-methoxy-4-methyl phenol 10, 2-methoxy phenol 11, 3-(4-hydroxyphenyl)propionic acid 12, 4-hydroxyphenylacetic acid 13, bis(4-hydroxyphenyl)methane 14 and tyrosol 15. As a general procedure phenol (0.05 mmol), tyrosinases (263-526 IU) and AA (1.5 equiv) were placed in 0.1 M Na-phosphate buffer pH 7.0 (5.0 mL) in vigorous stirring at room temperature. For insoluble aqueous phenols 3, 5, 14 substrates were dissolved in CH3CN (1.0 mL) and then added to the buffer solutions. Oxidations were performed using homogeneous and heterogeneous conditions. Reactions were monitored by thin layer chromatography (TLC). After the disappearance of the substrate, the reaction mixture was acidified with a solution of HCl 1.0 N and extracted twice with EtOAc. The organic extracts were treated with a saturated solution of NaCl and dried over anhydrous Na2SO4, then filtered and concentrated under vacuum to yield a colored crude. In the case of immobilized enzyme, biocatalyst was first recovered by filtration and the solution was subjected to the same work up described above. The obtained colored residue was treated with pyridine, HMDS and TMCS (HMDS-TMCS, 2:1 v/v) under vigorous stirring at room temperature for 30 min, then allowed to stand for 5 min.50 All products were identified by 1H NMR, 13C NMR and GC-MS. 1H NMR and 13C NMR were recorded on a Bruker 200 MHz spectrometer using CDCl3 as solvent. All chemical shift are expressed in parts per million (δ scale). GC-MS analysis were performed on a GCMS-QP5050 Shimadzu apparatus using a SPB column (25 m × 0.25 mm and 0.25 mm film thickness) and an isothermal temperature profile of 100 °C for 2 min, followed by a 10 °C/min temperature gradient to 280 °C for 25 min. The injector temperature was 280 °C. Chromatography-grade helium was used as the carrier gas with a flow of 2.7 mL/min. Mass spectra were recorded with an electron beam of 70 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With toluene-4-sulfonic acid In hexane at 100℃; for 4h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With dihydrogen peroxide; horseradish peroxidase In aq. phosphate buffer; acetone | |
46% | With potassium iodate In water; acetone at 20℃; for 1.5h; | General Method 2 General procedure: KIO3 (0.5 M in H2O, 1 equiv) was added to 1,2-dihydroxybenzene derivative (1 equiv) and 3,4,5-trihydroxybenzoic acid derivative (1 equiv) in acetone / water (1.0 M, 1:4) dropwise at room temperature. After stirring at room temperature for indicated time, the reaction mixture was filtered, washed with 1 N HCl, and dried. The desired product was obtained as a solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With dihydrogen peroxide; horseradish peroxidase In aq. phosphate buffer; acetone |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With dihydrogen peroxide; horseradish peroxidase In aq. phosphate buffer; acetone | |
57% | With dihydrogen peroxide; horseradish peroxidase In acetone | I.B Method I General procedure: A: Catechol (110 mg, 1.00 mmol ) and pyrogallol (126 mg, 1.00 mmol) were dissolved in a mixture of acetone-pH 5.0 phosphate-citrate (1 : 1=0.2 M Na2HP04: 0.1 M citrate) buffer (1 :5 v/v, 5 lnL), which contained 0.1 mg horseradish peroxidase (cas 9003-99-0, 5KU, Fisher). Four aliquots of 3% H2O2 (2 mL each) were added eveiy 10 min over 40 min while stirring. After 2-3 h, the resulting orange precipitate was filtered off, washed with water (3 x 6 mL) and dried under high vacuum condition to give a mixture of 2 and NCI35676 (purpurogallin). The mixture was purified by flash chromatography on silica gel, using ethyl acetate/hexane ( 1 :4) as eluent, to give 2 as an orange solid (23 mg, 1 1 %). 3,4,6-trihydroxy-5H-benzo[7]annulen-5-one (2). Following the general method IA, gave 2 as an orange solid (23 mg, 11 %): XH NMR (300 MHz, DMSO) δ 14.97 (s, 1H), 9.86 (s, 1H), 9.53 (s,1H), 7.45 (td, J = 14.4, 10.1 Hz, 3H), 7.19 (dd, J = 9.5, 0.8 Hz, 1H), 6.77 (dd, J = 11.3, 9.5 Hz, 1H); 13C NMR (75 MHz, DMSO) δ 184.82, 155.15, 150.89, 146.56, 135.95, 131.88, 125.50, 123.27, 122.72, 120.66, 119.04; LRMS (ESI): calcd for: CuH804 [M+Na]+= 227.1, obsd [M+Na]+= 227.0. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In aq. phosphate buffer; acetonitrile at 25℃; Electrochemical reaction; | Electro-organic synthesis of 5a-c, 5f, 3d-e, 3g General procedure: In a typical experiment, 100 mL of suitable buffer solutionin water/acetonitrile mixture (see Table 1) containing1.0 mmol of catechol and hydroquinone derivatives and1.0 mmol of edaravone (I) was electrolyzed in an undividedcell equipped with a carbon cathode (an assemblyof four rods of graphite electrodes, 6 mm in diameter, and10 cm in length) and RVC electrode as the counter electrode(anode), at suitable potential (V) versus Ag/AgCl (seeTable 1) at ambient condition. The electrolysis was terminatedwhen the current decreased by more than 95 %. Theelectrolysis process was interrupted and the graphite cathodewas washed in acetone in order to reactivate it. At theend of electrolysis, a few drops of acetic acid were added tothe solution and the cell was placed in a refrigerator overnight.The precipitated solid was collected by filtration,washed copiously with distilled water and characterizedby FT-IR, 1H NMR, 13C NMR, and MS. The final products were obtained in a purified form and no extra purificationwas needed. |
42% | With laccase from Pycnoporous cinnabarinus; dihydrogen peroxide In aq. phosphate buffer at 25℃; for 12h; Green chemistry; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With formic acid In water at 80℃; for 1.5h; | 4.2.2. 7-Methoxy-2,2-dimethyl-3,4-dihydrobenzopyran-8-ol (7) 3-Methoxycatechol (6) (1.5 g/10.7 mmol) and 40 mL of an 80% formic acid solution were placed in a two necked round-bottom flask. The solution was heated to 80 °C and then 2-methyl-3-buten-2-ol was added dropwise (461 mg/5.35 mmol/560 μL) (over 10 min). The mixture was allowed to react for 1 h and 30 min and then cooled to room temperature. The solution was poured over 100 mL of distilled water and neutralized with a saturated solution of NaHCO3 until pH 7-8. The aqueous phase was extracted with 3 × 100 mL of diethyl ether. The organic phase was washed with 2 × 100 mL of brine, dried over sodium sulfate anhydrous, filtered and the organic solvent evaporated. The crude product was purified by silica gel flash chromatography (n-hexane/ethyl acetate 9:1) and compound 7 was isolated as light orange oil (398 mg/36%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.6% | In aq. phosphate buffer at 20℃; Electrochemical reaction; | |
66% | In aq. phosphate buffer; acetonitrile at 25℃; for 20h; Electrochemical reaction; | 1 lectrochemical synthesis of dibenzyltetrahydroquinoxalinediones(6aec) General procedure: A mixture of PBS (80 mL, pH7.0, c0.15 M) and CH3CN (70/30v/v) containing 1.0 mmol of catechols (1aee) and DBEDA(1.0 mmol) was electrolyzed at 25 C under constant current densityof 1 mA/cm2. Progress the reaction was followed by TLC. Theprocess was interrupted during the electrolysis and the graphiteanode was washed in acetone in order to reactivate it. At the end of electrolysis (w20 h), the product was extracted with CH2Cl2(225 mL) and the solvent evaporated. The product was purified byrecrystallization from n-hexane/acetone mixture (20:80) andcharacterized by IR, 1H NMR, 13C NMR, and MS.; 4.4.1 4.4.3. 1,4-Dibenzyl-5-methoxy-1,2,3,4-tetrahydroquinoxaline-6,7-dione(6c). Isolated yields 66% (electrochemical) and 28% (chemical synthesis); IR(KBr): nmax3062 (]CeH), 3027, 2982 (eCeH), 2973,1711 (C]O), 1601, 1528, 1495, 1476, 1450 (CH2 bending), 1422, 1361,1234 (C]O bending), 1156, 1088, 1027 (CeOeC), 952 (CeN), 848,727, 693 and 590 cm1; 1H NMR (90 MHz, CDC13): d3.52 (s, 3H,methoxy), 4.45 (s, 2H, methylene), 4.82 (s, 2H, methylene), 5.32 (s,1H, quinone) and 7.23 (s, 10H, benzyl); 13C NMR (22.5 MHz, CDCl3):d46.8 (C of methoxy), 55.9 (2C of CH2 in piperazine ring), 57.2 (C ofbenzyl CH2, far to methoxy), 59.6 (C of benzyl CH2, near tomethoxy), 95.1 (C of CH in quinone ring), 126.1, 126.4, 126.8, 127.2,128.1 and 128.3 (10C of CHs of phenyl aromatic rings), 133.7 (ipsocarbon in quinone ring), 136.2 (2C of phenyl aromatic rings), 139.5(C of fused ring, near to methoxy), 152.0 (C of fused ring, far tomethoxy),174.8 (C of carbonyl group, near to methoxy) and 176.4 (Cof carbonyl group, far to methoxy); MS:m/z (relative intensity): 376[M2H] (100), 359 (100), 285 (100), 267 (66), 251 (50), 221 (33),191 (100), 91 (100), 65 (100). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With laccase; benzotriazol-1-ol In aq. phosphate buffer at 5 - 20℃; for 12h; Green chemistry; Enzymatic reaction; | 3 General procedure for the reaction of Meldrum’s acid andcatechols/hydroquinones General procedure: Catechol or hydroquinone (1 mM) and Meldrum’s acid(2 mM) were taken in 15 mL of phosphate/citrate bufferpH 7 solution. Then, purified laccase (400 U) and0.01 mmol of HBT were added to the resultant solutionand stirred well at 5 8C with a magnetic stirrer. Thetemperature of the reaction mixture was graduallyincreased up to room temperature. The progress of thereaction was monitored by TLC examination at intervals of30 min. Upon completion of the reaction, approximatelyafter 12 h, the reaction mixture was extracted withethylacetate (3 15, i.e. three-time extraction with 15 mLof ethylacetate). The organic layer was dried overanhydrous Na2SO4. The aqueous phase was further usedfor another run without any pre-treatment. The productwas purified by column chromatography using aluminiumoxide as a stationary phase and hexane:ethyl acetate(80:20) as a mobile phase. Products were unambiguouslycharacterized by spectral data2.4.3 Compound 5d: 6,7-dihydroxy-2,2-dimethyl-8-methoxy-1,3,9-trioxa-fluoren-4-one Mp > 300 °C; IR (KBr) 3426, 3442,1710, 1619, 1617, 1225 cm-1; 1HNMR, δ(400 MHz, DMSO-d6) 1.75 (s, 3H), 1.76 (s, 3H), 3.81 (s, 3H), 6.80 (s, 1H), 7.81 (s, br), 8.00 (s, br); 13CNMR, δ(100 MHz, DMSO-d6) 24.7, 25.0, 61.50, 86.23, 105.97, 110.15, 114.78, 125.11, 142.38, 144.14, 163.25, 171.45. Anal. calcd. for C13H12O7; C, 55.72; H, 4.32; found C, 55.82, H, 4.98; ESI-MS: 281.09 (M + 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: N-Bromosuccinimide / water; acetonitrile / 2 h / 0 °C 2: caesium carbonate / N,N-dimethyl-formamide / 1 h / 100 °C 3: trimethylsilyl iodide / acetonitrile / 18 h / 85 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium acetate In water; acetonitrile Electrolysis; | 4.2. Electro-organic synthesis of sulfanyl derivatives (1a-=4a) General procedure: In typical procedure 80 mL of 0.15 M CH3COONa solution containing 5% acetonitrile was pre-electrolyzed at chosen potential (see Table 1) using undivided cell. Subsequently added 1 mm catechol 1a and 1 mm 4-Mercapto-benzoic acid 3 were added to the cell. The electrolysis was terminated when the decay of the current became more than 95%. During electrolyses process,washed the GC with acetone, because during electrolyses non conducting layers is formed on the surface of working electrode. At the end of electrolyses process the cell was placed in refrigerator overnight. The solid precipitated (ppt) was collected by filtration and washed with distilled water several time and recrystallized from solvent (methanol:acetone 30:70).The products were characterized using modern techniques IR, H NMR, CNMR, and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With ytterbium(III) trifluoromethanesulfonate hydrate at 80℃; for 0.0333333h; Microwave irradiation; | General procedure for coumarin synthesis by MW irradiation General procedure: An open reaction vessel containing a mixture of the phenol (1.0 mmol), propiolic acid (1.1 mmol), and Yb(OTf)3 hydrate (0.1 mmol) was put in the MW apparatus and irradiated at 200 W (80 °C) for 2 min. The reaction was monitored by TLC (eluent CH2Cl2 / MeOH 99:1). The crude solid obtained was diluted with Et2O and the resulting suspension filtered under vacuum to separate the catalyst, the precipitate washed several times with Et2O. The filtrate was washed twice with a 5% NaHCO3 solution (10 mL) dried over MgSO4 and evaporated to dryness under vacuum yielding the desired product. |
38% | With sulfuric acid at 120℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium acetate In water; acetonitrile at 25℃; for 7h; Electrolysis; | Typical procedure for the synthesis of polycyclic imidazothiazols through CPCcondition General procedure: Under CPC condition, in a typical procedure, an aqueous solution (ca. 100 mL) ofwater/acetonitrile (90/10), containing 0.2 M sodium acetate, 1.0 mmol of catechols(1a-f) and 1.0 mmol of 3, was electrolyzed in an undivided cell equipped with acarbon cathode (an assembly of four rods, 6 mm diameter, and *10 cm length) anda carbon anode at 0.30 V versus SCE, at 25 C. The electrolysis was terminatedwhen the current decreased by more than 95 %. At the end of electrolysis, the cellwas placed in a refrigerator overnight and then the precipitated solids were collected by ltration, washed copiously with distilled water, and the nal products wereobtained purely, and no extra purication was needed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-methocycatechol; 3,4-difluoronitrobenzene With potassium carbonate In N,N-dimethyl-formamide; toluene for 2h; Reflux; Inert atmosphere; Stage #2: With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 50℃; | Benzyl (6-methoxydibenzo[b,e][1,4]dioxin-2-yl)carbamate (4). A solution of (3) (2.73 g, 10.532 mmol) in 500 mL THF was run through a Thales Nano H-cube Pro equipped with a 10% Pd/C catalyst cartridge at 50 bar and 50°C (1 mL/min, 100% H2). The resulting colorless solution was concentrated via rotary evaporation, yielding an off-white solid (98% yield). An NMR in CDCl3 showed 100% conversion to the amine. To a solution of the amine compound (1.272 g, 5.549 mmol) in 25 mL THF was added benzyl chloroformate (1.89 g, 11.098 mmol) and triethylamine (0.123g, 11.098 mmol). After stirring 22 h under N2, the resulting solid was removed via vacuum filtration, diluted with 50 mL diethyl ether, washed with acidic water (3x), and dried over Na2SO4. The solvent was removed in vacuo yielding a crude brown oil. The oil was purified on a Biotage Isolera One Flash Purification system in 80:20 Hexanes: EtOAc. A mixture of (4a) and (4b) was isolated off the column as 0.645 g (32%) of a white solid. 1H NMR (CDCl3, 400 MHz): δ 3.88(s, 3H), 5.18(s, 2H), 6.51(m, 3H), 6.82(m, 3H), 7.05(s, 1H), 7.36(m, 5H). | |
Stage #1: 3-methocycatechol; 3,4-difluoronitrobenzene With potassium carbonate In N,N-dimethyl-formamide; toluene for 2h; Reflux; Inert atmosphere; Stage #2: With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 50℃; | 1-methoxy-7-nitrodibenzo[b,e] [1,4]dioxine (3) 3 -methoxycatechol (3.00 g, 21.41 mmol) and K2C03 (5.92 g, 42.82 mmol) were stuffed in 150 mL 80:20 DMF: Toluene. 3,4difluoronitrobenzene (3.41 g, 21.41 mmol) was added dropwise and the reaction mixture was refluxed for 2 h under N2. The reaction mixture was poured over 450 mL ice water causing a yellow precipitate to form. The solid was vacuum filtered and washed with cold acetone, yielding 5.02 g (90%) of a mixture of (3a) and (3b) as a yellow solid. ‘H NMR (CDC13, 400 MHz): 5 3.90(s, 3H), 6.53(m, 1H), 6.62(t,J= 6.43, 1H), 6.91(m, 2H), 7.84(m, 2H).; A solution of (3) (2.73 g, 10.532 mmol) in 500 mL THF was run through a Thales Nano H-cube Pro equipped with a 10% Pd/C catalyst cartridge at 50 bar and 50°C (1 mL/min, 100% H2). The resulting colorless solution was concentrated via rotary evaporation, yielding an off-white solid (98% yield). An NMR in CDC13 showed 100% conversion to the amine. To a solution of the amine compound (1.272 g, 5.549 mmol) in 25 mL THF was added benzyl chloroformate (1.89 g, 11.098 mmol) and triethylamine (0.123g, 11.098 mmol). After stirring 22 h under N2, the resulting solid was removed via vacuum filtration, diluted with 50 mL diethyl ether, washed with acidic water (3x), and dried over Na2SO4. The solvent was removed in vacuo yielding a crude brown oil. The oil was purified on a Biotage Isolera One Flash Purification system in 80:20 Hexanes: EtOAc. A mixture of (4a) and (4b) was isolated off the column as 0.645 g (32%) of a white solid. ‘H NMR (CDC13, 400 MHz): 5 3.88(s, 3H), 5.18(s, 2H), 6.51(m, 3H), 6.82(m, 3H), 7.05(s, 1H), 7.36(m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-methocycatechol; 3,4-difluoronitrobenzene With potassium carbonate In N,N-dimethyl-formamide; toluene for 2h; Reflux; Inert atmosphere; Stage #2: With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 50℃; Stage #3: benzyl chloroformate With triethylamine In tetrahydrofuran at 20℃; for 22h; Inert atmosphere; | Benzyl (6-methoxydibenzo[b,e][1,4]dioxin-2-yl)carbamate (4). A solution of (3) (2.73 g, 10.532 mmol) in 500 mL THF was run through a Thales Nano H-cube Pro equipped with a 10% Pd/C catalyst cartridge at 50 bar and 50°C (1 mL/min, 100% H2). The resulting colorless solution was concentrated via rotary evaporation, yielding an off-white solid (98% yield). An NMR in CDCl3 showed 100% conversion to the amine. To a solution of the amine compound (1.272 g, 5.549 mmol) in 25 mL THF was added benzyl chloroformate (1.89 g, 11.098 mmol) and triethylamine (0.123g, 11.098 mmol). After stirring 22 h under N2, the resulting solid was removed via vacuum filtration, diluted with 50 mL diethyl ether, washed with acidic water (3x), and dried over Na2SO4. The solvent was removed in vacuo yielding a crude brown oil. The oil was purified on a Biotage Isolera One Flash Purification system in 80:20 Hexanes: EtOAc. A mixture of (4a) and (4b) was isolated off the column as 0.645 g (32%) of a white solid. 1H NMR (CDCl3, 400 MHz): δ 3.88(s, 3H), 5.18(s, 2H), 6.51(m, 3H), 6.82(m, 3H), 7.05(s, 1H), 7.36(m, 5H). | |
Stage #1: 3-methocycatechol; 3,4-difluoronitrobenzene With potassium carbonate In N,N-dimethyl-formamide; toluene for 2h; Reflux; Inert atmosphere; Stage #2: With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 50℃; Stage #3: benzyl chloroformate With triethylamine for 22h; Inert atmosphere; | 1-methoxy-7-nitrodibenzo[b,e] [1,4]dioxine (3) 3 -methoxycatechol (3.00 g, 21.41 mmol) and K2C03 (5.92 g, 42.82 mmol) were stuffed in 150 mL 80:20 DMF: Toluene. 3,4difluoronitrobenzene (3.41 g, 21.41 mmol) was added dropwise and the reaction mixture was refluxed for 2 h under N2. The reaction mixture was poured over 450 mL ice water causing a yellow precipitate to form. The solid was vacuum filtered and washed with cold acetone, yielding 5.02 g (90%) of a mixture of (3a) and (3b) as a yellow solid. ‘H NMR (CDC13, 400 MHz): 5 3.90(s, 3H), 6.53(m, 1H), 6.62(t,J= 6.43, 1H), 6.91(m, 2H), 7.84(m, 2H).; A solution of (3) (2.73 g, 10.532 mmol) in 500 mL THF was run through a Thales Nano H-cube Pro equipped with a 10% Pd/C catalyst cartridge at 50 bar and 50°C (1 mL/min, 100% H2). The resulting colorless solution was concentrated via rotary evaporation, yielding an off-white solid (98% yield). An NMR in CDC13 showed 100% conversion to the amine. To a solution of the amine compound (1.272 g, 5.549 mmol) in 25 mL THF was added benzyl chloroformate (1.89 g, 11.098 mmol) and triethylamine (0.123g, 11.098 mmol). After stirring 22 h under N2, the resulting solid was removed via vacuum filtration, diluted with 50 mL diethyl ether, washed with acidic water (3x), and dried over Na2SO4. The solvent was removed in vacuo yielding a crude brown oil. The oil was purified on a Biotage Isolera One Flash Purification system in 80:20 Hexanes: EtOAc. A mixture of (4a) and (4b) was isolated off the column as 0.645 g (32%) of a white solid. ‘H NMR (CDC13, 400 MHz): 5 3.88(s, 3H), 5.18(s, 2H), 6.51(m, 3H), 6.82(m, 3H), 7.05(s, 1H), 7.36(m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With laccase from Trametes versicolor; oxygen In aq. phosphate buffer at 20℃; for 24h; Green chemistry; Enzymatic reaction; | General procedure for the synthesis of sulfonyl benzenediol General procedure: In a 50 mL, round-bottom flask, the phosphate buffer solution (15 mL, 0.10 M, pH = 5.0) and hydroquinone or catechol derivatives (1 mmol) were mixed together. Next, the laccase (40 U, 75.5 mg) and sodium benzenesulfinate (1 mmol) were added, and the reaction mixture stirred under air at room temperature for 18-24 h (TLC). After completion, the reaction mixture was extracted by ethyl acetate (5×10 mL) and the organic phase evaporated. The precipitated solid was crystallized by water/acetone mixture (80:20) and the products characterized by 1H-NMR, 13C-NMR, FT-IR, and mass spectrometry which the data were consistent with those reported in the literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With laccase from Trametes versicolor; oxygen In aq. phosphate buffer at 20℃; for 20h; Green chemistry; Enzymatic reaction; | General procedure for the synthesis of sulfonyl benzenediol General procedure: In a 50 mL, round-bottom flask, the phosphate buffer solution (15 mL, 0.10 M, pH = 5.0) and hydroquinone or catechol derivatives (1 mmol) were mixed together. Next, the laccase (40 U, 75.5 mg) and sodium benzenesulfinate (1 mmol) were added, and the reaction mixture stirred under air at room temperature for 18-24 h (TLC). After completion, the reaction mixture was extracted by ethyl acetate (5×10 mL) and the organic phase evaporated. The precipitated solid was crystallized by water/acetone mixture (80:20) and the products characterized by 1H-NMR, 13C-NMR, FT-IR, and mass spectrometry which the data were consistent with those reported in the literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With laccase from Trametes versicolor; oxygen; In aq. phosphate buffer; at 20℃; for 24h;pH 5.0;Green chemistry; Enzymatic reaction; | General procedure: In a 50 mL, round-bottom flask, the phosphate buffer solution (15 mL, 0.10 M, pH = 5.0) and hydroquinone or catechol derivatives (1 mmol) were mixed together. Next, the laccase (40 U, 75.5 mg) and sodium benzenesulfinate (1 mmol) were added, and the reaction mixture stirred under air at room temperature for 18-24 h (TLC). After completion, the reaction mixture was extracted by ethyl acetate (5×10 mL) and the organic phase evaporated. The precipitated solid was crystallized by water/acetone mixture (80:20) and the products characterized by 1H-NMR, 13C-NMR, FT-IR, and mass spectrometry which the data were consistent with those reported in the literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium hexacyanoferrate (III); sodium azide In aq. acetate buffer at 20 - 40℃; for 1h; | general Synthesis Method General procedure: To a stirred solution of aqueous (ca50 ml)of acetate buffer (pH 5.0, 0.2M), 2mmol of catechol[3(a-c)] or hydroquinone (1), and 10 mmol of sodiumazide were added and dissolved. In a dropping funnelin the question solution, potassium ferricyanide(4 mmol) was added dropwise within 20-30 min.The reaction mixture was kept at room temperature,occasionally stirred for 1 h (about hydroquinone,for 4-5 h). After that the solution got dark andsome precipitates appeared. As the fnal stage ofthe reaction, the round-bottom ask was kept at40°C overnight (about hydroquinone, it was kept at45 °C for 4-5 h). Filtration was used to collect theprecipitated solid washed with water after that. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30.8% | With triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; | 4.2.1 Representative procedure for the preparation of compounds 6, 8, 10, 11, 13, 14, 18, 20, 21, 23, 24 and 25 derived from thiophenylphosphonic dicholoride. General procedure: The dual nucleophile (1 mmol) and triethylamine (2 mmol) were mixed in dry DCM under nitrogen. The mixture was cooled to 0 °C and then thiophenylphosphonic dichloride (1 mmol) was added. The mixture was slowly warmed to room temperature and stirred for 2 hours. The product was purified via flash column chromatography and dried under high vacuum. |
Yield | Reaction Conditions | Operation in experiment |
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65% | With sulfuric acid at 20℃; for 96h; | 3.2. General Procedures I for the Synthesis of Compounds 1-7 General procedure: To a mixture of appropriate phenol (2 mmol) and ethyl benzoyl acetate (2 mmol), concentratedH2SO4, (1 mL) was added and stirred at room temperature for four days; after which the mixturewas poured over crushed ice and extracted with AcOEt, (50 mL 5). Evaporation gave a brownsolid which, after chromatography (silica gel, hexane/AcOEt 10:11:1), afforded the corresponding4-phenylcoumarin (1-7) as a white solid (yield, 25%-30%). |
Yield | Reaction Conditions | Operation in experiment |
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60% | Stage #1: 3,4,5-trimethoxycinnamic acid With boron trifluoride diethyl etherate; trichlorophosphate at 0℃; for 0.25h; Stage #2: 3-methocycatechol at 25 - 28℃; | 3.4. General Procedures III: Synthesis of Compounds 22-28 General procedure: To a mixture of POCl3 (10 mmol) and BF3-Et2O (20 mmol) at 0 °C, appropriated cinnamic acid(5 mmol) was added and the reaction mixture stirred for 15 min at 0 °C. Phenol (5 mmol) was added tothe above reaction mixture in small portions and stirring continued at 25-28 °C for 4-12 h. The reactionmixture was poured on to ice-water; sodium acetate (1 g) was added and the mixture was warmedon a water bath for 2 min. It was cooled, extracted with ethyl acetate (2 x 150 mL), washed withwater (150 mL), dried, and the solvent removed under reduced pressure to obtain the crude product,which was purified by column chromatography using acetone-chloroform as eluent to afford pure4-phenyldihydro-coumarins 22-28 in 60%-75% yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With laccase In aq. phosphate buffer at 20℃; for 24h; Enzymatic reaction; | 10 General method for the synthesis of the coumestans General procedure: The laccase (Suberase, 2.0mL) was added to a mixture of the catechol (2.0mmol), coumarin (2.0mmol) and phosphate buffer (20.0mL, 0.10M, pH 7.15) in a 250mL round bottom flask stirred under air at rt. More laccase (2.0mL) was added after 2, 18 and 20h. The mixture was vigorously stirred under air until the substrates were consumed as judged by TLC. The mixture was extracted with EtOAc and washed two times with water (20.0mL). The organic phases were then combined and the solvent evaporated. The residue, a powder, was purified by washing with EtOAc or by flash chromatography or recrystallization. The recrystallization was accomplished from a combination of MeOH and EtOAc. Products were characterized by 1H NMR, 13C NMR, and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With laccase In aq. phosphate buffer at 20℃; for 24h; Enzymatic reaction; | 14 General method for the synthesis of the coumestans General procedure: The laccase (Suberase, 2.0mL) was added to a mixture of the catechol (2.0mmol), coumarin (2.0mmol) and phosphate buffer (20.0mL, 0.10M, pH 7.15) in a 250mL round bottom flask stirred under air at rt. More laccase (2.0mL) was added after 2, 18 and 20h. The mixture was vigorously stirred under air until the substrates were consumed as judged by TLC. The mixture was extracted with EtOAc and washed two times with water (20.0mL). The organic phases were then combined and the solvent evaporated. The residue, a powder, was purified by washing with EtOAc or by flash chromatography or recrystallization. The recrystallization was accomplished from a combination of MeOH and EtOAc. Products were characterized by 1H NMR, 13C NMR, and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: A scintillation vial was charged with a 0.3M solution of imidate (1 equiv) in EtOH, treated with hydrazine hydrate (2 equiv), and sealed with a Teflon-lined cap. The solution was then allowed to stir for 12hat 25C. The reaction mixture was then concentrated under vacuum, dissolved in EtOAc (10.0mL), and filtered through glass fiber filter paper. The filtrate was diluted with H2O (6.0mL). The aqueous layer was extracted with EtOAc (6.0mL x 3). The organic layers were combined and washed with sat. NH4Cl(aq) (6.0mL), water (6.0ml), and brine (6.0mL), and dried over Na2SO4. The crude product mixture was then concentrated under vacuum and purified by medium-pressure chromatography (1%-3%, NH3·MeOH/CH2Cl2) to give catechol 25. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In aq. phosphate buffer; at 20℃;pH 7.0;Electrolysis; Green chemistry; | In a typical procedure, an aqueous solution containing phosphate salts(NaH2PO4/Na2HPO4) as the buffer and supporting electrolyte (pH 7.0, 0.1 M), 0.25 mmol of catechols(1a-1c) and 0.25 mmolof <strong>[56-06-4]2,4-diamino-6-hydroxypyrimidine</strong> (2) was electrolyzed at a suitable potential in adivided cell. The progress of electrolysis was monitored using cyclicvoltammetry. The electrolysis was terminated when the decay of current become more than 95%of its initial amount. At the end of electrolysis, the precipitated solid was collected by filtration and was washed several times with water. For further purification of the products, column chromatography was used (silica gel 230400 mesh, elution ofthe column with 5:ln-hexane:ethylacetate). The structure o fthe products 3a-3c was confirmed spectroscopically by elementalanalysis, nuclear magnetic resonance (NMR) and FT-IR spectroscopy as well as mass spectrometry. The complete 1H and 13C NMR data assignments for products are reported in this section and the full picture of the original spectrum has been copied in supportinginformation (SI) datasheets |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium acetate In water at 25℃; Electrochemical reaction; | General procedure: In typical technique, 80 mL of 0.15 M Sodium acetate (CH3CO-+Na) solution was pre-electrolysed at chosen potential using undivided cell [4, 6, 21] Subsequently, 1 mM catechol, 1aand 1 mM 2-mercapto-6-(trifluo omethyl) pyrimidin-4-ol, 3 were added to the cell. The electrolysis was terminated when the decay of the current became more than 95%. During electrolysis process the GC was washed with acetone, because during electrolysis non conducting layers is formed at the surface of working electrode. At the end of electrolyses the cell was placed in refrigerator overnight. The solid precipitated (ppt) was collected by filtration and washed with distilled water several time, and recrystallised by solvent (Methanol : Acetone 3:7). The products were characterised using the modern techniques, IR, 1H NMR,13C NMR, MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With oxygen In water; <i>tert</i>-butyl alcohol at 50℃; for 24h; Green chemistry; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With oxygen In water; <i>tert</i>-butyl alcohol at 50℃; for 24h; Green chemistry; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With aluminium(III) iodide; In dimethyl sulfoxide; acetonitrile; at 20℃; for 18h; | To a 100 ml eggplant-shaped flask, aluminum triiodide (2.240 g, 5.5 mmol), cyclohexane (40 ml) and DMS0 (0.430 g, 5.5 mmol) were added, and the mixture was heated to 80 C with stirring, and kept under stirring for 0.5 hour. Then, it was cooled to room temperature, then <strong>[5150-42-5]2,3-<strong>[5150-42-5]dimethoxyphenol</strong></strong> (0.770 g, 5.0 mmol) was added, and the reaction was further stirred at room temperature. After the reaction for 18 hours, the stirring was stopped, and 2 mol/L was added to the eggplant-shaped flask. Diluted with hydrochloric acid (10 ml), EtOAc (EtOAc (EtOAc)EtOAc. , filtered, and the filtrate was evaporated to dryness on a rotary evaporator, and the residue was purified by flash column chromatography (ethyl acetate / petroleum ether = 1:3, volume ratio) to give 0.498 g of 2,3-dihydroxybenzene. Ether (yellow viscous liquid, yield 71%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
14% | Stage #1: 1,2,3,4-tetrahydrocarbazole With N-iodo-succinimide In dichloromethane for 0.5h; Inert atmosphere; Stage #2: 3-methocycatechol With silver tetrafluoroborate; sodium hydroxide In dichloromethane at 0℃; for 3h; Inert atmosphere; | Benzodioxinoindoline 28 To a solution of tetrahydrocarbazole 19c (51.0 mg, 0.298 mmol) in CH2Cl2 (2 mL) under argon was added NIS (74.0 mg, 0.328 mmol). The solution was stirred for 30 min, then cooled to 0 °C and 3-methoxycathecol (27) (104.0 mg, 0.742 mmol), AgBF4 (116.0 mg, 0.596 mmol) and NaOH (60 mg, 1.49 mmol) were added. The resulting mixture was stirred for 3 h prior to being quenched with a saturated aqueous NH4Cl solution (0.5 mL) and filtered through a pad of Celite. PreparativeTLC (cyclohexane/EtOAc, 9:1) afforded benzodioxinoindoline (13.0 mg, 0.042 mmol) in 14% yield as a white solid. Rf = 0.30 (cyclohexane/EtOAc, 9:1). IR (NaCl): 3341, 2936, 1604, 1498, 1474, 1098, 1019, 746 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.50-1.60 (m, 2 H), 1.62-1.70 (m, 2 H),1.73-1.80 (m, 2 H), 2.03-2.10 (m, 1 H), 2.33-2.40 (m, 1 H), 3.88 (s, 3H), 4.34 (s, 1 H), 6.35 (dd, J = 8.1, 1.4 Hz, 1 H), 6.43 (dd, J = 8.1, 1.4 Hz,1 H), 6.64 (d, J = 7.5 Hz, 1 H), 6.70 (d, J = 8.0 Hz, 1 H), 6.77 (t, J = 7.5 Hz,1 H), 7.08 (td, J = 7.7, 1.2 Hz, 1 H), 7.21 (d, J = 7.4 Hz, 1 H). 13C NMR (90.6 MHz, CDCl3): δ = 20.7, 23.3, 31.5, 37.1, 56.6, 81.6, 94.2,104.6, 109.7, 111.7, 120.2, 120.6, 122.6, 129.2, 131.6, 132.9, 143.9,146.7, 149.3. HRMS (ESI+): m/z [M + Na]+ calcd for C19H19NO3Na: 332.1257; found: 332.1247. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In aq. phosphate buffer; acetonitrile Electrolysis; | 2.3. Start of electrolysis General procedure: In a typical procedure, 100mL 15/85% (v/v) of acetonitrile (forimprove solubility of AC1 and AC2)/phosphate buffer solutioncontaining 1 mmol of either of electrophiles (1a-1c) and 1 mmol ofone of the nucleophiles (AC1 or AC2) (0.2 M, pH ~7.2) was preelectrolyzedat different applied potentials shown in Table 1. Theexperiments were conducted in an undivided cell for the nucleophileAC1 and a two compartment cell for AC2. The process wasassumed to be over when the current decay passed from 95%. During the electrolysis, due to the formation of the film of theproduct at the electrode, the proceeding of reaction was interruptedseveral times, the barrier that any time was counteracted bydipping the anode electrode in acetone. At the end of electrolysisfor AC1, the cell was placed in a refrigerator overnight and theprecipitated solid was collected by filtration. For AC2, the solventwas evaporated partially under partially created vacuum, leavingsome precipitate that was collected by filtration. Both precipitateswere further purified by column chromatography over 90 mech-Al2O3 using the 50:50 mixture of methanol and ethyl acetate as theeluent. After recrystallization the separated products were characterizedby IR, 1H NMR, 13C NMR, UVeVis and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In aq. phosphate buffer; acetonitrile Electrolysis; | 2.3. Start of electrolysis General procedure: In a typical procedure, 100mL 15/85% (v/v) of acetonitrile (forimprove solubility of AC1 and AC2)/phosphate buffer solutioncontaining 1 mmol of either of electrophiles (1a-1c) and 1 mmol ofone of the nucleophiles (AC1 or AC2) (0.2 M, pH ~7.2) was preelectrolyzedat different applied potentials shown in Table 1. Theexperiments were conducted in an undivided cell for the nucleophileAC1 and a two compartment cell for AC2. The process wasassumed to be over when the current decay passed from 95%. During the electrolysis, due to the formation of the film of theproduct at the electrode, the proceeding of reaction was interruptedseveral times, the barrier that any time was counteracted bydipping the anode electrode in acetone. At the end of electrolysisfor AC1, the cell was placed in a refrigerator overnight and theprecipitated solid was collected by filtration. For AC2, the solventwas evaporated partially under partially created vacuum, leavingsome precipitate that was collected by filtration. Both precipitateswere further purified by column chromatography over 90 mech-Al2O3 using the 50:50 mixture of methanol and ethyl acetate as theeluent. After recrystallization the separated products were characterizedby IR, 1H NMR, 13C NMR, UVeVis and MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24%; 50% | With aluminium(III) iodide; dimethyl sulfoxide; In acetonitrile; at 20℃; for 48h; | General procedure: To a suspension of AlI3 (5.5 mmol, 1.1 equiv) in MeCN was added anhyd DMSO (0.430 g, 5.5 mmol, 1.1 equiv). After stirring for 0.5 h at 80 C, the selected substrate (5 mmol) was added in one portion. The mixture was stirred overnight (18 h) at that temperature before quenching with aq 2 M HCl (10 mL). After extraction with EtOAc (3 50 mL), the organic phases were combined, washed with sat. aq Na2S2O3 and brine, and dried (MgSO4). The solvents were removed on a rotary evaporator, and the residue was purified by column chromatography to give the relevant catechol or phenol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 3,4-Dihydroxybenzoic acid; holo-corrinoid protein reconstructed from recombinant apo-protein and methyl cobalamin; methyl transferase I from Desulfitobacterium hafniense; potassium chloride; potassium hydroxide In dimethyl sulfoxide at 30℃; for 24h; Enzymatic reaction; | ||
With dihydrogen peroxide; P450BM3 peroxygenase In methanol; aq. phosphate buffer at 25℃; for 0.5h; Enzymatic reaction; | 3.2.3. General Procedure for O-demethylation of Aromatic Ethers General procedure: P450BM3 (0.5 M) was transferred to a glass sample bottle containing 0.1 M, pH 8.0phosphate buffer, aromatic ether compounds (4 mM, dissolved in methanol) and dualfunctional small molecule (DFSM) (500 M, dissolved in pH 8.0 phosphate buffer). Thereaction was initiated by the addition of H2O2 (30 mM, dissolved in pH 8.0 phosphatebuffer). The reaction mixture was incubated in a water bath at 25 C for 30 min. Thereaction was stopped by the addition of dilute HCl aqueous (1 M) and neutralized with anequal volume of KCl (1 M). The products were directly analyzed by HPLC (see below). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 41% 2: 21% | With Amberlyst-15 In acetonitrile at 70℃; for 8h; Molecular sieve; | 4.1.3. General coupling reaction between samin and phenolics General procedure: To a solution of samin 6 (1 equiv) in acetonitrile (1.0 mL/0.1 mmol of 6) was treated with phenolics (1.5-2 equiv), Amberlyst-15 (1 mg/0.005 mmol of 6) and a 4 Å molecular sieve. After stirring at 70 °C for 8 h, the reaction mixture was evaporated to dryness and purified by silica gel column and Preparative TLC to afford furofuran lignans 7a-7e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: 3-methocycatechol With sodium hydride In mineral oil at 100℃; for 0.0833333h; Stage #2: carbon dioxide at 160 - 190℃; for 2h; | 1.a Step (a): Preparation of 2,3-dihydroxy-4-methoxybenzoic acid NaH (60% dispersion in mineral oil, 640 mg, 8.0 mmol) was added to a flask containing 2.0 mmol of 3-methoxy-1,2-benzenediol. The resulting mixture was heated at 100 ° C for 5 minutes, cooled to room temperature, and ground to a powder. The mixture was reacted with 60-80 atm of carbon dioxide for 2 hours at 160-190 ° C using a cylinder of carbon dioxide. Thereafter, the reaction was quenched with 40 mL of water and cooled to room temperature, acidified to pH = 4 with HCl (1M) and then extracted with EA.The organic layer was dried over anhydrous magnesium sulfate, and evaporated to dryness, purified by column chromatography to give the corresponding 276mg white solid, yield: 75% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium iodate; In water; acetone; at 20℃; for 1.0h; | General procedure: KIO3 (0.5 M in H2O, 1 equiv) was added to 1,2-dihydroxybenzene derivative (1 equiv) and 3,4,5-trihydroxybenzoic acid derivative (1 equiv) in acetone / water (1.0 M, 1:4) dropwise at room temperature. After stirring at room temperature for indicated time, the reaction mixture was filtered, washed with 1 N HCl, and dried. The desired product was obtained as a solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | Stage #1: [(4,7-diphenyl-1,10-phenanthroline)2RuCl2]; 3-methocycatechol With sodium hydroxide In isopropyl alcohol for 24h; Reflux; Inert atmosphere; Darkness; Stage #2: In isopropyl alcohol at 20℃; for 2h; Darkness; Stage #3: ammonium hexafluorophosphate In water; isopropyl alcohol at 4℃; | |
23% | Stage #1: [(4,7-diphenyl-1,10-phenanthroline)2RuCl2] With sodium hydroxide In water; isopropyl alcohol for 0.25h; Inert atmosphere; Stage #2: 3-methocycatechol In water; isopropyl alcohol for 24h; Inert atmosphere; Reflux; Darkness; Stage #3: ammonium hexafluorophosphate In water; isopropyl alcohol at 4℃; | Compound 4 ([Ru(DIP)2(3-methoxysq)](PF6)) Ru(DIP)2Cl2 (0.250 g, 0.29 mmol) and aq. NaOH (0.45 mL, 1 M) were dissolved in 2-propanol (5 mL). The solution was degassed for 15 min and 3-methoxycatechol (0.07 g, 0.5 mmol) was added. The mixture was heated to reflux for 24 h under N2 atmosphere and protected from light. After cooling to r.t., the mixture was stirred opened to air for 2h while still protected from light and the solvent was removed under vacuum. The residual solid was dissolved in 2-propnol (2.5 mL) and H2O (20 mL) and NH4PF6 (0.250 g, 1.5 mmol) were added. The mixture was stored in the fridge (4°C) overnight. The precipitate was filtered with a Buchner funnel and washed with H2O (3 x 50 mL), Pentane (3 x 50 mL) and Et2O (3 x 50 mL). The solid was collected with DCM and dried under vacuum to deliver a crude product as the PF6 salt (0.07 g), which was chromatographed on silica (DCM/MeCN 20:1 Rf : 0.3). Evaporation of the solvent under vacuum provided [Ru(DIP)2(3-methoxysq)](PF6) as a deep red solid. Further wash with Et2O and Heptane were necessary in order to obtain clean product. The solid with the washing solvent (10 mL) was sonicated for 10 min and then centrifuged. This procedure was repeated three times for each solvent. Finally the red solid was collected with DCM and dried under vacuum to afford a clean product (0.072 g, 0.06 mmol, 23%). IR (Golden Gate, cm-1):3060w, 1620w, 1590w, 1540w, 1460m, 1400m, 1250m, 1160m, 1100m, 1030w, 827s, 764s, 735m, 700s. 1H NMR (500 MHz, CD2Cl2): δ/ppm = 8.91 - 8.50 (br, 1H, arom.), 8.43 - 8.08 (br, 3H, arom.), 8.07 - 7.79 (br, 7H, arom.), 7.75 - 7.46 (br, 15H, arom.), 7.46 - 7.28 (br, 2H, arom.), 7.28 - 6.93 (br, 10H, arom.). 13C NMR (125 MHz, CD2Cl2): δ/ppm = 149.62, 146.57, 143.72, 140.55, 137.05, 136.03, 133.07, 132.47, 131.27, 130.31, 130.07, 130.00, 129.59, 129.56, 129.33, 128.97, 128.80, 128.57, 125.67, 125.46, 123.55. MS (ESI+): m/z 904.8 [M - PF6]+. Elemental Analysis: calcd. for C55H40F6N4O4PRu = C, 62.76; H, 3.64; N, 5.53. Found = C, 61.67; H, 3.63; N, 5.09. HPLC: 0-3 minutes: isocratic 65% B (35% A); 3- 17 minutes: linear gradient from 65% B (35% A) to 0% B (100% A); 17-23 minutes: isocratic 0% B (100% A), TR = 11.887 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With 3,4,5-trihydroxybenzoic acid; oxygen; manganese(II) acetate In water at 25℃; Autoclave; | 3.2.1. 4-Methoxyl-2-hydroxy-3H-phenoxazin-3-one (2) 2-aminophenol (0.55 g, 5 mmol), 3-methoxy-2-hydroxylphenol (0.70 g, 5 mmol) and H2O(200 mL) were added into a 500-mL beaker. The mixture was treated by ultrasoundsonication in an ultrasonic cleaner. After sonication, the resulting clear solution, gallicacid (0.5 mol%) and Mn(OAc)2 (0.5 mol%) were transferred into the autoclave, and thepH value was adjusted to 10 by NaOH solution (1 M) under stirring. After the reactorwas closed, the atmosphere over the mixture was exchanged with O2 for three times.The reaction was stirred at 25 C under 0.3 MPa until no observation of the decreaseof the oxygen pressure. Notably, when the pressure dropped down below 0.2 MPa, O2was recharged up to 0.3 MPa. The final reaction mixture was quenched by adding10 mL water, acidized with HCl solution (1 M) to pH 1-2, and then centrifugated. Thesolid cake was washed with water for three times to afford the crude product of 2(1.19 g), which was pure enough and used directly in the next step without furtherpurification. |
82% | With 3,4,5-trihydroxybenzoic acid; oxygen; manganese(II) acetate; sodium hydroxide In water at 25℃; for 0.5h; Sonication; Autoclave; Green chemistry; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium methanolate In methanol at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With 3,4,5-trihydroxybenzoic acid; oxygen; cobalt(II) chloride; potassium hydroxide In water; N,N-dimethyl-formamide at 100℃; for 4h; | 7 Synthesis of 4-(2-mercaptobenzothiazole)thio-1,2-dihydroxybenzene In a 150mL reactor, put 2.20g catechol,3.34g 2-mercaptobenzothiazole, 19mg gallic acid, 11mg copper(II) acetate, 138mg K2CO3, 40mL water and 10mL dimethyl sulfoxide; heated to 120 C with stirring,Fill in oxygen, keep the pressure in the reactor at 1.0 MPa, and stop the reaction after 6 hours of reaction.Cool to room temperature, add 40mL saturated brine, and extract with 3×25mL ethyl acetate.The ethyl acetate layers were combined, the ethyl acetate was removed by rotary evaporation, the remaining solid was recrystallized with isopropanol, filtered with suction, and dried to obtain 5.21 g of a white solid.The product is subjected to NMR (see Figures 1 and 2),HRMS and other methods determined the structure to be 4-(2-mercaptobenzothiazole)sulfanyl-1,2-dihydroxybenzene, the yield was 95%, and the purity of the product by liquid chromatography was 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With manganese(II)carbonate; 3,4,5-trihydroxybenzoic acid; oxygen; potassium hydroxide In water; N,N-dimethyl-formamide at 120℃; for 4h; | 1 Synthesis of 4-(2-mercaptobenzothiazole)thio-1,2-dihydroxybenzene In a 150mL reactor, put 2.20g catechol,3.34g 2-mercaptobenzothiazole, 19mg gallic acid, 11mg copper(II) acetate, 138mg K2CO3, 40mL water and 10mL dimethyl sulfoxide; heated to 120 C with stirring,Fill in oxygen, keep the pressure in the reactor at 1.0 MPa, and stop the reaction after 6 hours of reaction.Cool to room temperature, add 40mL saturated brine, and extract with 3×25mL ethyl acetate.The ethyl acetate layers were combined, the ethyl acetate was removed by rotary evaporation, the remaining solid was recrystallized with isopropanol, filtered with suction, and dried to obtain 5.21 g of a white solid.The product is subjected to NMR (see Figures 1 and 2),HRMS and other methods determined the structure to be 4-(2-mercaptobenzothiazole)sulfanyl-1,2-dihydroxybenzene, the yield was 95%, and the purity of the product by liquid chromatography was 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With C28H46N4O10S2; dihydrogen peroxide; acetic acid; iron(II) chloride In water; acetonitrile at 80℃; for 1h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide; P450BM3 peroxygenase In methanol; aq. phosphate buffer at 25℃; for 0.5h; Enzymatic reaction; | 3.2.3. General Procedure for O-demethylation of Aromatic Ethers General procedure: P450BM3 (0.5 M) was transferred to a glass sample bottle containing 0.1 M, pH 8.0phosphate buffer, aromatic ether compounds (4 mM, dissolved in methanol) and dualfunctional small molecule (DFSM) (500 M, dissolved in pH 8.0 phosphate buffer). Thereaction was initiated by the addition of H2O2 (30 mM, dissolved in pH 8.0 phosphatebuffer). The reaction mixture was incubated in a water bath at 25 C for 30 min. Thereaction was stopped by the addition of dilute HCl aqueous (1 M) and neutralized with anequal volume of KCl (1 M). The products were directly analyzed by HPLC (see below). |
Tags: 934-00-9 synthesis path| 934-00-9 SDS| 934-00-9 COA| 934-00-9 purity| 934-00-9 application| 934-00-9 NMR| 934-00-9 COA| 934-00-9 structure
[ 4493-94-1 ]
5,6-Dimethoxybenzene-1,2,3,4-tetraol
Similarity: 1.00
[ 4493-94-1 ]
5,6-Dimethoxybenzene-1,2,3,4-tetraol
Similarity: 1.00
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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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