* 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.
With p-nitrobenzenesulfonic acid; palladium diacetate In tetrahydrofuran; water at 80℃; for 48 h; Inert atmosphere; Schlenk technique
General procedure: Under a N2 atmosphere, a Schlenk tube was charged with 2-aminobenzonitrile 1 (0.3 mmol),sodium arylsulfinate 2 (0.6 mmol), Pd(OAc)2 (10 mol percent), bpy (20 mol percent), p-NBSA (10 equiv), THF (2 mL), and H2O (1 mL) at room temperature. The reaction mixture was stirred vigorously at 80 °C for 48 h. The mixture was poured into ethyl acetate, which was washed with saturated NaHCO3 (2 × 10 mL) and then brine (1 × 10 mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The residue was purified by flash column chromatography (hexane/ethyl acetate) to afford the desired products 3.
With p-nitrobenzenesulfonic acid; palladium diacetate In tetrahydrofuran; water at 80℃; for 48 h; Inert atmosphere; Schlenk technique
General procedure: Under a N2 atmosphere, a Schlenk tube was charged with 2-aminobenzonitrile 1 (0.3 mmol),sodium arylsulfinate 2 (0.6 mmol), Pd(OAc)2 (10 mol percent), bpy (20 mol percent), p-NBSA (10 equiv), THF (2 mL), and H2O (1 mL) at room temperature. The reaction mixture was stirred vigorously at 80 °C for 48 h. The mixture was poured into ethyl acetate, which was washed with saturated NaHCO3 (2 × 10 mL) and then brine (1 × 10 mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The residue was purified by flash column chromatography (hexane/ethyl acetate) to afford the desired products 3.
With p-nitrobenzenesulfonic acid; palladium diacetate In tetrahydrofuran; water at 80℃; for 48 h; Inert atmosphere; Schlenk technique
General procedure: Under a N2 atmosphere, a Schlenk tube was charged with 2-aminobenzonitrile 1 (0.3 mmol),sodium arylsulfinate 2 (0.6 mmol), Pd(OAc)2 (10 mol percent), bpy (20 mol percent), p-NBSA (10 equiv), THF (2 mL), and H2O (1 mL) at room temperature. The reaction mixture was stirred vigorously at 80 °C for 48 h. The mixture was poured into ethyl acetate, which was washed with saturated NaHCO3 (2 × 10 mL) and then brine (1 × 10 mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The residue was purified by flash column chromatography (hexane/ethyl acetate) to afford the desired products 3.
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1967, vol. 3, p. 1556 - 1558[2] Zhurnal Organicheskoi Khimii, 1967, vol. 3, # 9, p. 1599 - 1601
11
[ 115262-01-6 ]
[ 873-55-2 ]
[ 1535-65-5 ]
Reference：
[1] Angewandte Chemie - International Edition, 2013, vol. 52, # 47, p. 12390 - 12394[2] Angew. Chem., 2013, vol. 125, # 47, p. 12616 - 12620,5
12
[ 1717-59-5 ]
[ 873-55-2 ]
[ 1535-65-5 ]
Reference：
[1] Journal of Organic Chemistry, 1989, vol. 54, # 13, p. 3023 - 3027
13
[ 873-55-2 ]
[ 1535-65-5 ]
[ 882-33-7 ]
[ 122590-93-6 ]
Reference：
[1] Journal of Fluorine Chemistry, 1989, vol. 43, p. 53 - 66
14
[ 75-45-6 ]
[ 873-55-2 ]
[ 1535-65-5 ]
[ 882-33-7 ]
[ 122590-93-6 ]
Reference：
[1] Journal of Fluorine Chemistry, 1989, vol. 43, p. 53 - 66
15
[ 873-55-2 ]
[ 62-53-3 ]
[ 4273-98-7 ]
Yield
Reaction Conditions
Operation in experiment
47%
With dihydrogen peroxide; copper diacetate In water at 20℃; for 2 h; Green chemistry
0.5 mmol of aniline (1a) was added to 4 mL of water, To this was added 0.125 mmol of copper acetate, 1.0 mmol of sodium benzenesulfinate, 1.0 mmol of hydrogen peroxide, Reaction was carried out at room temperature for 2 hours. After completion of the reaction, a saturated aqueous solution of NaCl was added to the reaction solution,Extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, filtered, dried at 60 °C under reduced pressure, The crude compound represented by the formula (2a) is obtained.The crude compound represented by the formula (2a) was subjected to silica gel column chromatography, and the volume ratio of ethyl acetate to petroleum etherThe solution was a 1: 2 solution as the mobile phase, and the TLC was followed to collect eluate with an Rf value of 0.3-0.5. The resulting eluate was collected by solvent removal, To obtain 55 mg of the compound represented by the formula (2a) in a yield of 47percent.
Reference：
[1] Patent: CN106810478, 2017, A, . Location in patent: Paragraph 0021; 0022; 0023; 0024
16
[ 873-55-2 ]
[ 615-36-1 ]
[ 4273-98-7 ]
Reference：
[1] Journal of Organic Chemistry, 2018, vol. 83, # 12, p. 6589 - 6599
17
[ 447-61-0 ]
[ 873-55-2 ]
[ 727-99-1 ]
Reference：
[1] Advanced Synthesis and Catalysis, 2011, vol. 353, # 10, p. 1701 - 1706
With sulfuric acid; In dichloromethane; at 25℃; for 8.5h;Molecular sieve;
General procedure: In a test tube containing the appropriate sodium salt of sulfinic acid, 1a-d (1 mmol) was added the appropriate alcohol (1 mL) followed by dichloromethane (4 mL) [For more complex alcohols, 3 equiv. (3 mmol) of alcohol were used]. Under stirring, sulfuric acid (106 mL, 2 equiv.) was added and after 30 min of reaction, powdered 4 A molecular sieves (200 mg) was added. The mixture was stirred for the time indicated on Table 2 and then diluted with dichloromethane (10 mL) and transferred to a separation funnel. The organic phase was then washed with water (2 x 20 mL), dried over anhydrous MgSO4 and filtered through a pad of silica. The solvents were removed in vacuo and the resulting crude product was further purified by flash column chromatography [hexanes:EtOAc (98:2)].
1-(3,4-dichlorophenyl)-2-(phenylsulfonyl)ethan-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In N,N-dimethyl-formamide; at 20℃; for 12h;Sealed tube;
General procedure: A sealed tube (35 mL) equipped with a stirring bar was loaded with 2-bromoethanones (1.0 mmol), then sodium benzenesulfinate (1.2 mmol) in DMF (20 mL) or phosphite (1.0 mmol) in toluene (20 mL) was added to the tube and the mixtures were stirred at room temperature till the 2-bromoethanones was totally consumed as indicated by TLC analysis (ca. 12 h for 1 and 24 h for 3). Then, the mixture was diluted with water (20 mL) and extracted with CH2Cl2 (30 mL x 3). Next, the organic phase was combined and dried over anhydrous Na2SO4. The solvent was removed by rotary evaporation and the oily mixture was purified with flash chromatograph column (elute: mixture of ethyl acetate and n-hexane), giving the desired products. And the 1H NMR spectra of the purified substrates were in accordance with the known literatures.
In ethanol; water;Reflux;
General procedure: In a 50 mL round-bottomed flask, a solution of sulfonylchloride (6 mmol) in H2O (25 mL) was prepared, sodiumbicarbonate (0.840 g, 10 mmol) and sodium sulfite (1.26 g,10 mmol) were added, and the mixture was refluxed forabout 4-7 h. The progress of the reaction was monitored byTLC (eluent: n-hexane/ethyl acetate). When the starting materialdisappeared completely, an ethanolic solution of appropriate2-bromoacetophenone (2 mmol) was added to thereaction mixture and heating was continued until the completionof reaction which was monitored by TLC. After cooling,the reaction mixture was neutralized by adding 5% HCl. The precipitate obtained was filtered and crystallized from ethanol.Crystallization provided pure beta-ketosulfones (1-26).With the intention of high yield, the neutralized filtrate wasevaporated under vacuum and passed through a silica gelgravity column using hexane and ethyl acetate as eluent.The structures of synthetic compounds were deduced byusing 1H-, 13C-NMR, EI-MS, HREI-MS, and elemental analysis.
2-[2-[2-phenylsulfonyl-3-[2-(1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene)-ethylidene]-1-cyclohexene-1-yl]-ethenyl]-1,3,3-trimethyl-3H-indolium chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82.5%
16.4 g sodium salt of benzenesulfinic acid and 36.0 g dye A (both available from Aldrich) were added under stirring to 200 ml Downanol PM in a 11 three-necked flask equipped with a stirrer and a reflux condenser. Then a solution of 4.0 g sodium hydroxide and 36.5 g 2- methylene-1, 3, 3-TRIMETHYLINDOLINE (Fischer base, available from Aldrich) in 35 ml ethanol was added under stirring for one minute to this suspension. The reaction mixture was heated to 50C for one hour. Then the reaction mixture was left to cool to room temperature and 600 ML of a 2 wt. -% hydrochloric acid were added. After the reaction mixture had cooled to room temperature, the insoluble portion was separated by filtration and washed with 2 1 of water. Then the product was dried for one day at 50C in a circulating air oven. Yield: 56.2 g (92. 9% based on dye A). The dried product was suspended in 450 ml methyl ethyl ketone and heated to 80C for one hour. Subsequently, the solution with a temperature of 40C was filtered and the solid portion was washed with ethyl acetate. The product was air-dried. The yield after clean-up was 82.5 wt. -%; UV/Vis spectrum in methanol : 828 nm, extinction coefficient E = 251 1/G X CM.
6-(Benzenesulfonylmethyl)-lH-pyrimidine-2,4-dione6-(Chloromethyl)-lH-pyrimidine-2,4-dione (8 g, 50 mmol) was dissolved in DMF (200 mL) and benzenesulphinic acid sodium salt (9.8 g, 60 mmol) was added. The reaction was heated to 125C for 2 hours then allowed to cool and the suspension filtered and concentrated in vacuo to give a yellow solid. The crude material was washed with water (100 mL), filtered, then triturated with acetonitrileto give the desired material as a cream solid (13.2 g). The material was used without further purification.NMR Spectrum: 1H NMR (400.13 MHz, DMSOd6) 64.46 (s, 2H), 7.69 (t, 2H), 7.81 (m, IH), 7.87 (m, 3H), 10.85 (s, IH), 11.11 (s, IH)
A mixture of <strong>[104146-17-0]4-chlorothiazole-5-carbaldehyde</strong> (0.15 g), benzenesulfinic acid sodium salt (0.25 g) and dimethyl sulfoxide (7.0 mL) was stirred at 1000C for 30 minutes. The mixture was cooled to room temperature, poured onto ice/water (50 mL) and extracted with ethyl acetate. The combined organic extract was washed with saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solvent was removed under reduced pressure to afford the title compound as a tan oil (0.23 g).1H NMR (CDCI3): delta 7.57-7.63 (m, 2H), 7.67-7.73 (m, 1H), 8.11-8.14 (m, 2H), 8.95 (d, J = 0.9 Hz, 1 H), 10.83 (d, J = 0.9 Hz, 1 H).
In dimethyl sulfoxide; at 100℃; for 0.333333h;
4-benzenesulfonylthiazole-5-carbaldehydeA mixture of <strong>[104146-17-0]4-chlorothiazole-5-carbaldehyde</strong> (2.9 g) and benzenesulfinic acid sodium salt (4.9 g) in anhydrous dimethyl sulfoxide (50 ml_) was heated at 1000C for 20 minutes. The resulting solution was cooled then poured onto a mixture of ice and saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to afford the title compound (5.03 g) as a pale yellow solid.1H NMR (300 MHz, CDCI3): delta 7.56-7.65 (m, 2H); 7.66-7.74 (m, 1 H); 8.09- 8.15 (m, 2H); 8.94 (d, J = 0.9 Hz, 1 H); 10.83 (d, J = 0.9 Hz, 1 H).
With copper(I) trifluoromethanesulfonate benzene; In dimethyl sulfoxide; at 65℃; for 1.5h;
A mixture of <strong>[50593-91-4]5-bromo-2-methylsulfanylpyrimidine-4-carboxylic acid methyl ester</strong> (2.3 g), benzenesulfinic acid sodium salt (1.9 g) and dimethyl sulfoxide (35 ml_) was treated with bis[copper(l)triflate]benzene complex (3.3 g), and the resulting mixture was stirred at 650C for 1.5 hours. The mixture was cooled to 4O0C and filtered through Celite. The filtrate was diluted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. The solvent was removed under reduced pressure and the residue purified by column chromatography on silica gel, eluting with a mixture of dichloromethane and ethyl acetate (1 :0 to 4:1 by volume) to afford the title compound as a pale yellow solid (1.8 g).MS: ESI (+ve) (Method B): 325 (M+H)+, Retention time 3.5 min.
4-benzenesulfonyloxazole-5-carboxylic acid ethyl ester4-Bromooxazole-5-carboxylic acid ethyl ester (1.2 g) was combined with benzenesulfinic acid sodium salt (1.1 g) in anhydrous dimethylsulfoxide (12 mL) and the reaction mixture was heated at 110C for 2 hours then left to stand at room temperature overnight. The solution was partitioned between brine and ethyl acetate and the organic layer was washed with brine then dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, eluting with a mixture of ethyl acetate and cyclohexane, then purified again by column chromatography on silica gel, eluting with a mixture of ethyl acetate and pentane, to afford the title compound (0.33 g).1H NMR (300 MHz, CDCI3): delta 1.44 (t, J = 7.1 Hz, 3H); 4.48 (q, J = 7.2 Hz, 2H); 7.53-7.62 (m, 2H); 7.64-7.71 (m, 1 H); 7.92 (s, 1 H); 8.11-8.17 (m, 2H). MS: ESI (+ve) (Method D): 282 (M+H)+, Retention time 3.5 min.
N-Methyl-2-(phenylsulfonyl)-5-(pyridin-3-yl)aniline 10h. A mixture of 4.9 g (17.4 mmol) of <strong>[41252-95-3]1-chloro-4-iodo-2-nitrobenzene</strong> 17 and 2.85 g (17.4 mmol) of sodium phenylsulfinate in 70 mL of DMF was stirred at 120 for 12 h. The mixture was cooled down, diluted with water and extracted with AcOEt. The extract was dried over Na2SO4 and roto-evaporated. Purification by column chromatography (eluent - hexane/AcOEt 4:1) afforded 2.07 g (31%) of 4-iodo-2-nitro-1-(phenylsulfonyl)benzene 31. A mixture of 110 mg (0.9 mmol) of pyridin-3-ylboronic acid and 240 mg (2.26 mmol) of Na2CO3 in 8.8 mL of ethanol and 2.2 mL of water was stirred at 90 under Ar for 40 min and then cooled down. To this mixture, 432 mg (1.12 mmol) of compound 18 was added, followed by 20 mg of Pd(PPh3)2Cl2. The mixture was stirred at 85 under Ar for 2 h and then cooled, diluted with water and extracted with DCM. The extract was washed with water, dried over Na2SO4 and roto-evaporated. The crude product was purified by column chromatography (eluent - hexane/AcOEt 4:1) to afford 270 mg (71%) of 3-(3-nitro-4-(phenylsulfonyl)phenyl)pyridine 19. Iron powder (222 mg, 3.97 mmol) was added to a suspension of 270 mg (0.79 mmol) of compound 19 in 2.5 mL of AcOH. The mixture was stirred at 70 for 3 h and then cooled down and filtered. The precipitate was washed with AcOEt. The filtrate was diluted with water and extracted with AcOEt. The extract was washed with saturated NaHCO3 solution, dried over Na2SO4 and roto-evaporated to afford 145 mg (59%) of 2-(phenylsulfonyl)-5-(pyridin-3-yl)aniline 21. A solution of 120 mg (0.39 mmol) of compound 21 in 2 mL formic acid was refluxed for 3 h. The solvent was stripped in vacuo and the residue was treated with saturated NaHCO3 solution, filtered, washed with water and dried in vacuo to afford 115 mg (87%) of N-(2-(phenylsulfonyl)-5-(pyridin-3-yl)phenyl)formamide 23. A solution of borane dimethyl sulfide complex (2 M in THF, 0.49 mL, 0.98 mmol) was added to a solution of 110 mg (0.33 mmol) of compound 23 in 2 mL of THF and the mixture was stirred at ambient temperature for 12 h under Ar. The solution was quenched with saturated NaHCO3 solution and extracted with DCM. The extract was dried over Na2SO4 and roto-evaporated. The crude product was purified by column chromatography (eluent-hexane/AcOEt 4:1) to afford 52 mg (49%) of compound 10h. LS MC m/z 325 (M+1). 1 NMR (DMSO-d6, 400 MHz) delta 8.90 (s, 1), 8.60 (s, 1), 8.01 (m, 4), 7.60 (m, 4), 7.06 (d, J = 8.0 Hz, 1), 6.93 (s, 1), 6.50 (s, 1), 2.89 (s, 3).
30.6%
In N,N-dimethyl-formamide; at 120℃; for 12h;
A solution of <strong>[41252-95-3]1-chloro-4-iodo-2-nitrobenzene</strong> 4(1) (5.64 g, 0.02 mol) and Na phenylsulfinate 4(2) (3.28 g, 0.02 mol) in DMF (80 ml) was stirred for 12 h at 120 C. Then, the reaction mixture was cooled, poured into water and extracted with ethyl acetate. Organic layer was dried over Na2SO4, filtered and evaporated to dryness. The mixture was separated by means of column chromatography, eluent-ethyl acetate:hexane 1:4. It gave 2.4 g (30.6%) 4-iodo-2-nitro-1-(phenylsulfonyl)benzene 4(3).
With iron(III) chloride; dipotassium peroxodisulfate; oxygen; In water; at 20℃; for 9h;Green chemistry;
General procedure: A mixture of alkyne 1 (0.25 mmol), sodium sulfinate 2 (0.375 mmol), FeCl3 (20 mol %),K2S2O8 (20 mol %), and water (3 mL) was stirred at rt in an open flask for 6-9 h(Table 2). After completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 5 mL). The combined organic phases were dried over anhyd. Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using a mixture of EtOAc-n-hexane (1:4) as eluent to afford an analytically pure sample of beta-keto sulfones 3 (Table 2).
With copper(I) chloride; sodium hydroxide; In dichloromethane; at 20℃; for 3h;
1 mmol of sodium benzenesulfinate, 1 mmol of Potassium p-bromophenylfluoroborate, 1.2 mmol of sodium hydroxide and 0.1 mmol of cuprous chloride were charged into a reaction tube containing 2 ml of dichloromethane and magnetically stirred for 3 hours. After the reaction is completed, filtration was carried out through filter paper and the solvent is dried and the separated by column to obtain the product. The yield was 94%.
86%
With copper(l) iodide; sodium acetate; In 1,2-dichloro-ethane; at 25℃; for 3h;
General procedure: A mixture of potassium arylfluoborate (1 mmol), sodium aryl sulfinate (1 mmol), CuI (0.1 mmol), sodium acetate (1.2 mmol) and DCE (2 mL) was stirred at 25 C under air for 3 h. After filtration, the organic phases were evaporated under reduced pressure, and the residue was subjected to flash column chromatography [silica gel, ethyl acetate/petroleum ether (60-90 C) = 1/8] to obtain the desired product.
With p-nitrobenzenesulfonic acid; palladium diacetate; In tetrahydrofuran; water; at 80℃; for 48h;Inert atmosphere; Schlenk technique;
General procedure: Under a N2 atmosphere, a Schlenk tube was charged with 2-aminobenzonitrile 1 (0.3 mmol),sodium arylsulfinate 2 (0.6 mmol), Pd(OAc)2 (10 mol %), bpy (20 mol %), p-NBSA (10 equiv), THF (2 mL), and H2O (1 mL) at room temperature. The reaction mixture was stirred vigorously at 80 C for 48 h. The mixture was poured into ethyl acetate, which was washed with saturated NaHCO3 (2 × 10 mL) and then brine (1 × 10 mL). After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The residue was purified by flash column chromatography (hexane/ethyl acetate) to afford the desired products 3.
(E)-1-methoxyl-2-(2-(phenylsulfonyl)vinyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
With manganese (II) acetate tetrahydrate; In dimethyl sulfoxide; at 110℃; for 12h;
General procedure: To a 25 ml round bottom flask were added cinnamic acid (0.5 mmol) , aromatic sulfinic acidsodium salt (1.5 mmol), Mn(OAc)2?4H2O(6.13 mg, 0.025 mmol) and DMSO (2ml). The round bottom flask was stirred under air at 110 C for 12 h. The reaction mixture was cooled to roomtemperature and washed three times with saturated sodium chloride, extracted with EtOAc, andconcentrated in vacuo. The resulting residue was purified by flash column chromatography usinghexanes:EtOAc (8:1) as the eluent. All compounds are characterized by 1H NMR, 13C NMR,LRMS and their comparison to literature values
With formic acid; In tetrahydrofuran; water; at 20℃; for 144.0h;
Formic acid (3.9 mE, 104 mmol) is added to a solution of tert-butyl carbamate (1.90 g, 16.2 mmol), 2-bromo-4- cyanobenzaldehyde (3.41 g, 16.2 mmol) and sodium benzenesulfinate (2.67 g, 16.2 mmol) in a mixture of tetrahydroffiran (7.0 mE) and water (60 mE), and the mixture is stirred at room temperature for 6 days. Water (180 mE) is added, and the precipitate is filtered and washed with water. The precipitate is treated with tert-butyl methyl ether (30 mE), and the mixture is stirred for 30 mm. The precipitate is filtered, washed with tert-butyl methyl ether, and dried. Yield:3.35g. ESI mass spectrum: [(7913r)-M+H]=451, [(8113r)-M+ H]=453; Retention time HPEC: 0.66 mm (X012_S01).
3.35 g
With formic acid; In tetrahydrofuran; water; at 20℃; for 144.0h;
Step 1:tert-Butyl (2-Bromo-4-cyanophenyl)(phenylsulfonyl)methylcarbamateFormic acid (3.9 mL, 104 mmol) is added to a solution of tert-butyl carbamate (1.90 g, 16.2 mmol), <strong>[89891-69-0]2-bromo-4-cyanobenzaldehyde</strong> (3.41 g, 16.2 mmol) and sodium benzenesulfinate (2.67 g, 16.2 mmol) in a mixture of tetrahydrofuran (7.0 mL) and water (60 mL),and the mixture is stirred at room temperature for 6 days. Water (180 mL) is added, and the precipitate is filtered and washed with water. The precipitate is treated with tert-butyl methyl ether (30 mL), and the mixture is stirred for 30 mm. The precipitate is filtered, washed with tert-butyl methyl ether, and dried. Yield: 3.35 g. ESI mass spectrum: [(79Br)- M+H] = 451, [(81Br)-M+H] = 453; Retention time HPLC: 0.66 min(XO12SO1).
3.35 g
With formic acid; In tetrahydrofuran; water; at 20℃; for 144.0h;
Formic acid (3.9 mL, 104 mmol) is added to a solution of tert-butyl carbamate (1.90 g, 16.2 mmol), <strong>[89891-69-0]2-bromo-4-cyanobenzaldehyde</strong> (3.41 g, 16.2 mmol) and sodium benzenes-ulfinate (2.67 g, 16.2 mmol) in a mixture of tetrahydrofurane (7.0 mL) and water (60 mL). The mixture is stirred at room temperature for 6 days. Water (180 mL) is added and the precipitate is filtered and washed with water. The precipitate is treated with tert-butyl methyl ether (30 mL), and the mixture is stirred for 30 min. The precipitate is filtered, washed with tert-butyl methyl ether and dried. Yield: 3.35 g. ESI mass spectrum: [(79Br)-M+H]+=451, [(81Br)-M+H]+=453; Retention time HPLC: 0.66 min (method X012_S01).
95.2 g
With formic acid; In tetrahydrofuran; water; at 15 - 25℃; for 144.0h;
Formic acid (65.2 mL, 1.73 mol) is added to a mixture of tert-butyl carbamate (31.6 g, 270 mmol), <strong>[89891-69-0]3-bromo-4-formylbenzonitrile</strong> (56.7 g, 270 mmol), sodium benzenesulfinate (44.3 g, 270 mmol), tetrahydofuran (170 mL) and water (340 mL). The mixture is stirred at room temperature for 6 days, and the precipitate is filtered. The precipitate is digested in acetonitrile (300 mL), filtered and washed with cold acetonitrile. Yield: 95.2 g. ESI mass spectrum: [(79Br)-M+H]+ = 451, [(81Br)-M+H]+ = 453; Retention time HPLC: 0.66 min (X012_S01).
26.8 g
With formic acid; In tetrahydrofuran; water; at 20℃; for 144.0h;
3-Bromo-4-formyl-benzonitrile (20.5 g, 97.7 mmol), benzenesulfmic acid sodium salt (16.03 g, 97.6 mmol) and tert-butylcarbamate (11.4 g, 97.7 mmol) are suspended in water (312 mL) and THF (78 mL). Formic acid (28.8 g, 625 mmol) is added and the solution is stirred at room temperature for 6 days. Water (300 mL) is added and the precipitate is filtered off, washed with water and dried. The crude product is further purified by precipitation from tert-butylmethylether. Yield: 26.8 g; ESI mass spectrum: [M+Na]+ = 473 (bromine isotope pattern).
tert-butyl (4-cyano-2-methylphenyl)(phenylsulfonyl)methylcarbamate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With formic acid; In tetrahydrofuran; water; at 20℃; for 96h;
Step 1 tert-Butyl (4-Cyano-2-methylphenyl)(phenylsulfonyl)methylcarbamate Formic acid (3.3 mL, 88 mmol) is added to a mixture of tert-butyl carbamate (1.61 g, 13.8 mmol), <strong>[27609-91-2]4-formyl-3-methylbenzonitrile</strong> (2.00 g, 13.8 mmoo) and sodium benzenesulfinate (2.26 g, 13.8 mmol) in a mixture of tetrahydrofuran (7 mL) and water (18 mL), and the mixture is stirred at room temperature for 4 days. The tetrahydrofuran is removed under reduced pressure. The precipitate is filtered and dried. Yield: 3.77 g.
With formic acid; In tetrahydrofuran; water; at 20℃; for 96h;
Formic acid (3.3 mL, 88 mmol) is added to a mixture of tert-butyl carbamate (1.61 g, 13.8 mmol), <strong>[27609-91-2]4-formyl-3-methylbenzonitrile</strong> (2.00 g, 13.8 mmoo) and sodium benzene- sulfinate (2.26 g, 13.8 mmol) in a mixture of tetrahydrofuran (7 mL) and water (18 mL), and the mixture is stirred at room temperature for 4 days. The tetrahydrofuran is removed under reduced pressure. The precipitate is filtered and dried. Yield: 3.77 g.
6-methyl-1-(phenylsulfonyl)benzotriazole[ No CAS ]
[ 81262-52-4 ]
Yield
Reaction Conditions
Operation in experiment
With iodine; In water; ethyl acetate; at 20℃; for 3h;
General procedure: A typical procedure for the catalytic N-sulfonylation of benzotriazoles using I2 as catalyst includes: in EtOAc-H2O (10:1) mixture solvent (2 mL), benzotriazole 1a (0.3 mmol), sodium benzenesulfinate 2a (0.9 mmol), I2 (0.06 mmol) were added successively. The suspension mixture was vigorously stirred at room temperature for 3 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL), basified with sat. aq. Na2CO3 (8 mL) and H2O (5 mL). The mixture was extracted with CH2Cl2 (3* 5 mL) and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was then purified by TLC technique (petroleum ether/ethyl acetate = 3:1, v/v) to furnish 1-phenylsulfonylbenzotriazole 3a [28] in 97% yield.
With 3-chloro-benzenecarboperoxoic acid; sodium bromide; In methanol; ethyl acetate; at 20℃; for 4h;
General procedure: in EtOAc/MeOH (4:1) mixture solvent (2 mL), benzotriazoles 1 (0.3 mmol), sodium sulfinates 2 (0.54 mmol), NaBr (0.36 mmol) and mCPBA (0.39 mmol) were added successively. The suspension mixture was vigorously stirred at room temperature for 4 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL), basified with sat. aq. Na2CO3(8 mL) and H2O (5 mL). The mixture was extracted with CH2Cl2 (3×5 mL) and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was then purified by TLC technique (3:1 (v/v) petroleum ether/ethyl acetate) to furnish sulfonylbenzotriazoles 3.
5-chloro-1-(phenylsulfonyl)benzotriazole[ No CAS ]
6-chloro-1-(phenylsulfonyl)benzotriazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With iodine; In water; ethyl acetate; at 20℃; for 3h;
General procedure: A typical procedure for the catalytic N-sulfonylation of benzotriazoles using I2 as catalyst includes: in EtOAc-H2O (10:1) mixture solvent (2 mL), benzotriazole 1a (0.3 mmol), sodium benzenesulfinate 2a (0.9 mmol), I2 (0.06 mmol) were added successively. The suspension mixture was vigorously stirred at room temperature for 3 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL), basified with sat. aq. Na2CO3 (8 mL) and H2O (5 mL). The mixture was extracted with CH2Cl2 (3* 5 mL) and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was then purified by TLC technique (petroleum ether/ethyl acetate = 3:1, v/v) to furnish 1-phenylsulfonylbenzotriazole 3a [28] in 97% yield.
With 3-chloro-benzenecarboperoxoic acid; sodium bromide; In methanol; ethyl acetate; at 20℃; for 4h;
General procedure: in EtOAc/MeOH (4:1) mixture solvent (2 mL), benzotriazoles 1 (0.3 mmol), sodium sulfinates 2 (0.54 mmol), NaBr (0.36 mmol) and mCPBA (0.39 mmol) were added successively. The suspension mixture was vigorously stirred at room temperature for 4 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL), basified with sat. aq. Na2CO3(8 mL) and H2O (5 mL). The mixture was extracted with CH2Cl2 (3×5 mL) and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was then purified by TLC technique (3:1 (v/v) petroleum ether/ethyl acetate) to furnish sulfonylbenzotriazoles 3.
With dihydrogen peroxide; copper diacetate; In water; at 20℃; for 2.0h;Green chemistry;
0.5 mmol of aniline (1a) was added to 4 mL of water, To this was added 0.125 mmol of copper acetate, 1.0 mmol of sodium benzenesulfinate, 1.0 mmol of hydrogen peroxide, Reaction was carried out at room temperature for 2 hours. After completion of the reaction, a saturated aqueous solution of NaCl was added to the reaction solution,Extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, filtered, dried at 60 °C under reduced pressure, The crude compound represented by the formula (2a) is obtained.The crude compound represented by the formula (2a) was subjected to silica gel column chromatography, and the volume ratio of ethyl acetate to petroleum etherThe solution was a 1: 2 solution as the mobile phase, and the TLC was followed to collect eluate with an Rf value of 0.3-0.5. The resulting eluate was collected by solvent removal, To obtain 55 mg of the compound represented by the formula (2a) in a yield of 47percent.
With dichloro bis(acetonitrile) palladium(II); silver(I) acetate; In 1,4-dioxane; dimethyl sulfoxide; at 120℃; for 24h;Inert atmosphere; Schlenk technique;
General procedure: Under the argon atmosphere, a Schlenk tube (15 mL) equipped with a magnetic bar was loaded with the sulfonamide 1 (0.5 mmol), sodium arylsulfinates 2 (0.6 mmol, 1.2 equiv.), Pd(MeCN)2Cl2 (6.5 mg, 5 molpercent) and AgOAc (166.9 mg, 1.0 mmol) in one portion. Then, the mixture of 1,4-dioxane/DMSO (3.5 mL in a 9:1 ratio) was added to obtain a clear solution and the reaction mixture was allowed to stir at 120 °C for 24 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl sulfonamides 3 in noted yields.
4-(tert-butyl)-N-phenylbenzenesulfonamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With dichloro bis(acetonitrile) palladium(II); silver(I) acetate; In 1,4-dioxane; dimethyl sulfoxide; at 120℃; for 24h;Inert atmosphere; Schlenk technique;
General procedure: Under the argon atmosphere, a Schlenk tube (15 mL) equipped with a magnetic bar was loaded with the sulfonamide 1 (0.5 mmol), sodium arylsulfinates 2 (0.6 mmol, 1.2 equiv.), Pd(MeCN)2Cl2 (6.5 mg, 5 molpercent) and AgOAc (166.9 mg, 1.0 mmol) in one portion. Then, the mixture of 1,4-dioxane/DMSO (3.5 mL in a 9:1 ratio) was added to obtain a clear solution and the reaction mixture was allowed to stir at 120 °C for 24 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl sulfonamides 3 in noted yields.
With dichloro bis(acetonitrile) palladium(II); silver(I) acetate; In 1,4-dioxane; dimethyl sulfoxide; at 120℃; for 24h;Inert atmosphere; Schlenk technique;
General procedure: Under the argon atmosphere, a Schlenk tube (15 mL) equipped with a magnetic bar was loaded with the sulfonamide 1 (0.5 mmol), sodium arylsulfinates 2 (0.6 mmol, 1.2 equiv.), Pd(MeCN)2Cl2 (6.5 mg, 5 mol%) and AgOAc (166.9 mg, 1.0 mmol) in one portion. Then, the mixture of 1,4-dioxane/DMSO (3.5 mL in a 9:1 ratio) was added to obtain a clear solution and the reaction mixture was allowed to stir at 120 C for 24 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl sulfonamides 3 in noted yields.
2-chloro-3-((phenylsulfonyl)methyl)quinoxaline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With tert-Butyl peroxybenzoate; tetra-(n-butyl)ammonium iodide; In water; at 100℃; for 10h;Sealed tube; Green chemistry;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with azaarenes (1.0 mmol), sodium benzenesulfinate (2 equiv), TBAI (0.2 equiv), tert-butyl peroxybenzoate (TBPB, 1 equiv), and water (1 ml). The reaction was carried out at 100 C. After completion, the result was diluted with diethyl ether, washed with water and brine, and dried with Mg2SO4. After solvent removal under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
With oxygen; copper diacetate; potassium carbonate; In dimethyl sulfoxide; at 45℃;Molecular sieve;
Potassium carbonate (2.01 g, 14.6 mmol, 2 eq.), 4A MS, and Cu(OAc)2 (1.49 g, 8.0 mmol, 1.1 eq.) were added successively to a solution of compound 4,4,5,5-Tetramethyl- 2-(4-nitrophenyl)-l,3,2-dioxaborolane (1.82 g, 7.3 mmol, 1 eq.) and crude sodium benzenesulfinate (2.39 g, 14.6 mmol, 2 eq.) in DMSO (50 mL). The reaction was stirred overnight at 45 C under the atmosphere of an oxygen balloon. The reaction mixture was poured into water and extracted with ethyl acetate. The organic extracts were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to give l-nitro-4-(phenylsulfonyl)benzene, 0.71 g, 37% yield.
0.71 g
With oxygen; copper diacetate; potassium carbonate; In dimethyl sulfoxide; at 45℃;Molecular sieve;
Potassium carbonate (2.01 g, 14.6 mmol, 2 eq.), 4A MS, and Cu(OAc)2 (1.49 g, 8.0 mmol, 1.1 eq.) were added successively to a solution of compound 4,4,5, 5-Tetramethyl- 2-(4-nitrophenyl)-l,3,2-dioxaborolane (1.82 g, 7.3 mmol, 1 eq.) and crude sodium benzenesulfinate (2.39 g, 14.6 mmol, 2 eq.) in DMSO (50 mL). The reaction was stirred overnight at 45 C under the atmosphere of an oxygen balloon. The reaction mixture was poured into water and extracted with ethyl acetate. The organic extracts were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to give l-nitro-4-(phenylsulfonyl)benzene, 0.71 g, 37% yield.
In N,N-dimethyl-formamide; at 20℃; for 12h;Sealed tube;
General procedure: A sealed tube (35 mL) equipped with a stirring bar was loaded with 2-bromoethanones (1.0 mmol), then sodium benzenesulfinate (1.2 mmol) in DMF (20 mL) or phosphite (1.0 mmol) in toluene (20 mL) was added to the tube and the mixtures were stirred at room temperature till the 2-bromoethanones was totally consumed as indicated by TLC analysis (ca. 12 h for 1 and 24 h for 3). Then, the mixture was diluted with water (20 mL) and extracted with CH2Cl2 (30 mL x 3). Next, the organic phase was combined and dried over anhydrous Na2SO4. The solvent was removed by rotary evaporation and the oily mixture was purified with flash chromatograph column (elute: mixture of ethyl acetate and n-hexane), giving the desired products. And the 1H NMR spectra of the purified substrates were in accordance with the known literatures.
In N,N-dimethyl-formamide; at 20℃; for 12h;Sealed tube;
General procedure: A sealed tube (35 mL) equipped with a stirring bar was loaded with 2-bromoethanones (1.0 mmol), then sodium benzenesulfinate (1.2 mmol) in DMF (20 mL) or phosphite (1.0 mmol) in toluene (20 mL) was added to the tube and the mixtures were stirred at room temperature till the 2-bromoethanones was totally consumed as indicated by TLC analysis (ca. 12 h for 1 and 24 h for 3). Then, the mixture was diluted with water (20 mL) and extracted with CH2Cl2 (30 mL x 3). Next, the organic phase was combined and dried over anhydrous Na2SO4. The solvent was removed by rotary evaporation and the oily mixture was purified with flash chromatograph column (elute: mixture of ethyl acetate and n-hexane), giving the desired products. And the 1H NMR spectra of the purified substrates were in accordance with the known literatures.
With dipotassium peroxodisulfate; oxygen; In N,N-dimethyl-formamide; at 100℃; for 12h;
General procedure: A mixture of cinnamic acid 1 (1.0 mmol), K2S2O8 (1.5 mmol) and sodium sulfinate 2 (1.5 mmol) in DMF (5 mL) was stirred at 100 oC under ambient air for 12 h. Upon completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 x 15 mL). The combined organic phase was dried with anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (EtOAc/n-hexane, 1:4) to afford an analytically pure sample of beta-keto sulfones 3.
With tetrabutylammomium bromide; In N,N-dimethyl-formamide; for 12h;Reflux; Inert atmosphere;
Under nitrogen protection, add <strong>[162102-79-6]4-bromopyridine-2,6-dicarboxylic acid dimethyl ester</strong> Ia (1.0equiv) and IIa (2.0equiv) to a 50mL round bottom flask, and then add N, N-dimethylformamide to dissolve.Then, 10% catalytic amount of tetrabutylammonium bromide was added, and the reaction was performed under reflux for 12 hours, followed by post-treatment: 30 mL of water was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then subjected to column chromatography. To white solid IIIa, yield 87%.Then under the protection of nitrogen, add IIIa and 2.2equivs L-phenylglycinol to the sealed tube,Stir overnight at 100 C without solvent (the reaction is complete by TLC),Direct column chromatography gave white solid IVa in 99% yield.Then add IVa to the Schlenk bottle and then add anhydrous dichloromethane.Add 2.2 equivs diethylamine sulfur trifluoride reagent dropwise at -20 C, stir the reaction overnight, add 10% ammonia water to quench the reaction, add dichloromethane and water to extract 3 times, and dry with anhydrous sodium sulfate Column chromatography gave S1 as a white solid with a yield of 67%.
3,6-dichloro-4-(phenylsulfonyl)pyridazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In tetrahydrofuran; dimethyl sulfoxide; at 20℃; for 0.666667h;
Step 1: To a solution of <strong>[6082-66-2]<strong>[6082-66-2]3,4,6-trichloropyridazin</strong>e</strong> (20.04 g, 106 mmol) in a mixture of THF and DMSO (5:1, 200 mL) was added sodium benzenesulfinate (18.6 g, 111.1 mmol) and the mixture was stirred vigorously at room temperature. Full conversion was observed in 40 minutes. After completion, the reaction mixture was diluted with EtOAc (100 mL) and washed with water and brine. The combined organic phases were dried over MgS04. The solvent volume was reduced by evaporation. Recrystallization from EtO Ac/hexanes yielded 3,6-dichloro-4- (phenylsulfonyl)pyridazine (28.5 g, 93% yield) as a white solid. (1529) MS m/z 289.0 [M+H]+; NMR (CDCb) d: 8.34 (s, 1H), 8.07 - 7.98 (m, 2H), 7.80 - 7.74 (m, (1530) 1H), 7.68 - 7.61 (m, 2H).
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