* 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 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃;
To a stirred solution of 4-(ethylthio)benzaldehyde (2.46 g, 14.8 mmol) in dichloromethane (100 mL) at 0° C. was added m-CPBA (7 g, 31.1 mmol) in portions. The reaction mixture was stirred for 1 hour then 1M sodium hydroxide (35 mL) was added and stirred for a further 10 minutes. The reaction mixture was extracted with dichloromethane and the organic layer was washed with brine and concentrated in vacuo. 1H NMR suggested that m-CPBA remained, so the crude product was dissolved in ethyl acetate, washed five times with 1M sodium hydroxide then concentrated in vacuo to give 2.16 g (74percent) of 4-(ethylsulfonyl)benzaldehyde. 1H NMR (D6-DMSO): 10.20 (1H, s), 8.24-8.15 (4H, m), 3.44 (2H, q, J 7.4), 1.16 (3H, t, J 7.4).
Reference：
[1] Patent: US2010/305120, 2010, A1, . Location in patent: Page/Page column 53
[2] Annali di Chimica (Rome, Italy), 1951, vol. 41, p. 139,143, 146
[3] Annali di Chimica (Rome, Italy), 1951, vol. 41, p. 139,143, 146
2
[ 20035-08-9 ]
[ 459-57-4 ]
[ 50899-03-1 ]
Yield
Reaction Conditions
Operation in experiment
80%
at 125℃; for 20 h;
[00151] To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulf oxide (60 mL) was added sodium ethanesulfinate (46 g, 396 mmol). The resulting mixture was stirred at 125 °C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80percent yield). LC-MS tR = 1.19 min in 2 min chromatography, MS (ESI) m/z 199.1 [M+H]+. 1H NMR (CDCI3) δ 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, J = 7.2 Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H).
80%
at 125℃; for 20 h;
To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mE) was added sodium ethanesulfinate (46 g, 396 mmol). The resulting mixture was stirred at 125° C. for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mE of H20. The product was filtered, washed with two 10-mE portions of EtOH and dried undervacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80percent yield). EC-MS tR=i.19 mm inmm chromatography, MS (ESI) m/z 199.1 [M+H]. ‘H NMR (CDC13) ö 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, J=7.2 Hz, 2H), 1.30 (t, J=7.2 Hz, 3H).
80%
at 125℃; for 20 h;
To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mL) was added sodium ethanesulfinate (46 g, 396 mmol). The resulting mixture was stirred at 125 °C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80percent yield). LC-MS tR = 1.19 mm in 2 mm chromatography, MS (ESI) m/z 199.1 [M+H]. 1H NMR (CDC13) 5 10.14 (s, 1H), 8.09(s, 4H), 3.16 (q,J= 7.2 Hz, 2H), 1.30 (t,J= 7.2Hz, 3H).
80%
at 125℃; for 20 h;
[00213] Step 1 : 4-(ethylsulfonyl)benzaldehyde [1004] [00214] To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mL) was added sodium ethanesulfinate (46 g, 396 mmol). The resulting mixture was stirred at 125 °C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80percent yield). LC-MS tR = 1.19 min in 2 min chromatography, MS (ESI) m/z 199.1 [M+H]+. 1H NMR (CDC13) S 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, 7 = 7.2 Hz, 2H), 1.30 (t, 7 = 7.2 Hz, 3H)
1 g
at 125℃; for 20 h;
To a solution of 4-fluorobenzaldehyde (1.3 g, 10.47 mmol) in DMSO (10 mL) was added sodium ethanesulfinate (2.43 g, 20.94 mmol) and the resulting mixture was stirred at 125 °C for 20 h. The mixture was cooled to RT and partitioned between ethyl acetate and water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was triturated with hexane and the solid was collected through filtration to yield 1.0 g of the titled product. 1H NMR (300 MHz, DMSO-d6) δ 1.11 (t, = 7.2 Hz, 3H), 3.38 (q, = 7.2 Hz, 2H), 8.10 (d, = 8.1 Hz, 2H), 8.16 (d, = 8.1 Hz, 2H), 10.14 (s, 1H).
With {(Pd{Fe(η5-C5H5)(η5-C5H3C(CH3)=NC6H4CH3-4)}(μ-Cl))2}; potassium carbonate In dimethyl sulfoxide at 110℃; for 12 h; Inert atmosphere
General procedure: Under N2 atmosphere, a reaction vessel was charged with a mixture of sodium sulfinates 1 (0.6 mmol), nitroarenes 2 (0.3 mmol), palladacycle I (0.75 molpercent) and K2CO3 (1.0 equiv) in DMSO (2 ml) at room temperature. After that, the mixture was heated to 110 °C and incubated in an oil bath for 12 h under N2 atmosphere. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate and washed with brine three times. The combined organic solution was dried with Na2SO4, filtered and evaporated under reduced pressure. The residue was purified by thin-layer chromatography on silica gel GF 254 (ethyl acetate/petroleum ether) to give the pure product.
Reference：
[1] Journal of Antibiotics, 1952, vol. 5, p. 253[2] Chem.Abstr., 1959, p. 1231
[3] Yakugaku Zasshi, 1950, vol. 70, p. 616[4] Chem.Abstr., 1951, p. 6168
[5] Journal of the American Chemical Society, 1951, vol. 73, p. 906,908
[6] Zhurnal Obshchei Khimii, 1952, vol. 22, p. 1663,1664; engl. Ausg. S. 1705, 1706
[7] Farmaco (1946-1952), 1951, vol. 6, p. 145,147
[8] Journal of the Chemical Society, 1962, p. 1420 - 1427
5
[ 100613-79-4 ]
[ 50899-03-1 ]
Reference：
[1] Yakugaku Zasshi, 1950, vol. 70, p. 616[2] Chem.Abstr., 1951, p. 6168
[3] Kogyo Kagaku Zasshi, 1952, vol. 55, p. 252[4] Chem.Abstr., 1954, p. 9956
[5] Journal of Antibiotics, 1952, vol. 5, p. 253[6] Chem.Abstr., 1959, p. 1231
[7] Takamine Kenkyusho Nenpo, 1951, vol. 3, p. 19[8] Chem.Abstr., 1955, p. 299
[9] Journal of the American Chemical Society, 1951, vol. 73, p. 906,908
[10] Zhurnal Obshchei Khimii, 1952, vol. 22, p. 1663,1664; engl. Ausg. S. 1705, 1706
[11] Farmaco (1946-1952), 1951, vol. 6, p. 145,147
[12] Yakugaku Zasshi, 1951, vol. 71, p. 1364[13] Chem.Abstr., 1952, p. 7067
6
[ 108129-95-9 ]
[ 50899-03-1 ]
Reference：
[1] Patent: DE934590, 1951, ,
7
[ 459-57-4 ]
[ 50899-03-1 ]
Reference：
[1] Patent: US2010/305120, 2010, A1,
8
[ 90561-19-6 ]
[ 50899-03-1 ]
Reference：
[1] Journal of the Chemical Society, 1962, p. 1420 - 1427
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 0℃;
To a stirred solution of 4-(ethylthio)benzaldehyde (2.46 g, 14.8 mmol) in dichloromethane (100 mL) at 0 C. was added m-CPBA (7 g, 31.1 mmol) in portions. The reaction mixture was stirred for 1 hour then 1M sodium hydroxide (35 mL) was added and stirred for a further 10 minutes. The reaction mixture was extracted with dichloromethane and the organic layer was washed with brine and concentrated in vacuo. 1H NMR suggested that m-CPBA remained, so the crude product was dissolved in ethyl acetate, washed five times with 1M sodium hydroxide then concentrated in vacuo to give 2.16 g (74%) of 4-(ethylsulfonyl)benzaldehyde. 1H NMR (D6-DMSO): 10.20 (1H, s), 8.24-8.15 (4H, m), 3.44 (2H, q, J 7.4), 1.16 (3H, t, J 7.4).
10 g of 4-thioethylbenzaldehyde are dissolved in 150 ml of methylene chloride and treated portionwise with 22 g of m-chloroperbenzoic acid while cooling with ice. The mixture is diluted with methylene chloride, extracted twice with ice-cold potassium carbonate solution and water, dried over sodium sulphate and evaporated. After recrystallization from hexane/ether, there are obtained 9.1 g of 4-ethylsulphonyl-benzaldehyde in the form of colourless crystals, melting point 107-109 C.
26
[ 50899-03-1 ]
[ 69251-31-6 ]
[ 84264-87-9 ]
Yield
Reaction Conditions
Operation in experiment
EXAMPLE 9 In analogy to the procedure described in Example 8, from 1-(1,1,3,3-tetramethyl-5-indanyl)ethyl-triphenylphosphonium bromide and 4-ethylsulphonylbenzaldehyde there is obtained ethyl p-[2-(1,1,3,3-tetramethyl-5-indanyl)propenyl]phenylsulphone, melting point 125-127 C.;
In tetrahydrofuran; methanol; hexane; water; ethyl acetate;
EXAMPLE 8 18.1 g of [1-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)ethyl]-triphenylphosphonium bromide are heated at reflux for 3.5 hours with 5.0 g of p-ethylsulphonyl-benzaldehyde in 250 ml of butylene oxide. The mixture is cooled, poured into 500 ml of methanol/water (6:4) and extracted three times with hexane. The organic phase is washed with water, dried over sodium sulphate and evaporated. The crude product is filtered over silica gel using hexane/ethyl acetate (1:1) for the elution and recrystallized from hexane/ethyl acetate. There are obtained 9.2 g of ethyl p-[2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)propenyl]phenylsulphone in the form of colourless crystals, melting point 158-161 C.
2,6-Dimethyl-4-(4'-ethylsulphonylphenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid di-(α-pyridyl)-methyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
EXAMPLE 7 2,6-Dimethyl-4-(4'-ethylsulphonylphenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid di-(α-pyridyl)-methyl ester. SPC16 10 g of 4-ethylsulphonylbenzaldehyde, 5 ccs. of concentrated ammonia and 19.5 g of acetoacetic acid (α-pyridyl)-methyl ester in 40 ccs. of alcohol are heated under reflux for 8 hours. The mixture is concentrated in vacuo and after addition of ether crystals which melt at 138C when recrystallized from alcohol are obtained. Yield 73 %.
To a stirred solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (1.7 g, 8.6 mmol) in IMS (40 mL) was added sodium tetraborohydride (650 mg, 17.2 mmol). The reaction mixture was stirred at room temperature for 2 hours, then neutralised with amberlite-H+resin, filtered and concentrated in vacuo to afford a quantitative yield of (4-(ethylsulfonyl)phenyl)methanol. 1H NMR (CDCl3): 7.88 (2H, d, J 8.3), 7.57 (2H, d, J 8.0), 4.84 (2H, s), 3.12 (2H, q, J 7.4), 1.28 (3H, t, J 7.4).
With {(Pd{Fe(eta5-C5H5)(eta5-C5H3C(CH3)=NC6H4CH3-4)}(mu-Cl))2}; potassium carbonate; In dimethyl sulfoxide; at 110℃; for 12h;Inert atmosphere;
General procedure: Under N2 atmosphere, a reaction vessel was charged with a mixture of sodium sulfinates 1 (0.6 mmol), nitroarenes 2 (0.3 mmol), palladacycle I (0.75 mol%) and K2CO3 (1.0 equiv) in DMSO (2 ml) at room temperature. After that, the mixture was heated to 110 C and incubated in an oil bath for 12 h under N2 atmosphere. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate and washed with brine three times. The combined organic solution was dried with Na2SO4, filtered and evaporated under reduced pressure. The residue was purified by thin-layer chromatography on silica gel GF 254 (ethyl acetate/petroleum ether) to give the pure product.
[00151] To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulf oxide (60 mL) was added <strong>[20035-08-9]sodium ethanesulfinate</strong> (46 g, 396 mmol). The resulting mixture was stirred at 125 C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80% yield). LC-MS tR = 1.19 min in 2 min chromatography, MS (ESI) m/z 199.1 [M+H]+. 1H NMR (CDCI3) delta 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, J = 7.2 Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H).
80%
In dimethyl sulfoxide; at 125℃; for 20h;
To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mE) was added <strong>[20035-08-9]sodium ethanesulfinate</strong> (46 g, 396 mmol). The resulting mixture was stirred at 125 C. for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mE of H20. The product was filtered, washed with two 10-mE portions of EtOH and dried undervacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80% yield). EC-MS tR=i.19 mm inmm chromatography, MS (ESI) m/z 199.1 [M+H]. ?H NMR (CDC13) oe 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, J=7.2 Hz, 2H), 1.30 (t, J=7.2 Hz, 3H).
80%
In dimethyl sulfoxide; at 125℃; for 20h;
To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mL) was added <strong>[20035-08-9]sodium ethanesulfinate</strong> (46 g, 396 mmol). The resulting mixture was stirred at 125 C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80% yield). LC-MS tR = 1.19 mm in 2 mm chromatography, MS (ESI) m/z 199.1 [M+H]. 1H NMR (CDC13) 5 10.14 (s, 1H), 8.09(s, 4H), 3.16 (q,J= 7.2 Hz, 2H), 1.30 (t,J= 7.2Hz, 3H).
80%
In dimethyl sulfoxide; at 125℃; for 20h;
[00213] Step 1 : 4-(ethylsulfonyl)benzaldehyde [1004] [00214] To a solution of 4-fluorobenzaldehyde (24.6 g, 198 mmol) in dimethylsulfoxide (60 mL) was added <strong>[20035-08-9]sodium ethanesulfinate</strong> (46 g, 396 mmol). The resulting mixture was stirred at 125 C for 20 h. After cooling to rt, the reaction mixture was triturated with 350 mL of H20. The product was filtered, washed with two 10-mL portions of EtOH and dried under vacuum to afford 4-(ethylsulfonyl)benzaldehyde as a light yellow solid (31.2 g, 80% yield). LC-MS tR = 1.19 min in 2 min chromatography, MS (ESI) m/z 199.1 [M+H]+. 1H NMR (CDC13) S 10.14 (s, 1H), 8.09 (s, 4H), 3.16 (q, 7 = 7.2 Hz, 2H), 1.30 (t, 7 = 7.2 Hz, 3H)
1 g
In dimethyl sulfoxide; at 125℃; for 20h;
To a solution of 4-fluorobenzaldehyde (1.3 g, 10.47 mmol) in DMSO (10 mL) was added <strong>[20035-08-9]sodium ethanesulfinate</strong> (2.43 g, 20.94 mmol) and the resulting mixture was stirred at 125 C for 20 h. The mixture was cooled to RT and partitioned between ethyl acetate and water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was triturated with hexane and the solid was collected through filtration to yield 1.0 g of the titled product. 1H NMR (300 MHz, DMSO-d6) delta 1.11 (t, = 7.2 Hz, 3H), 3.38 (q, = 7.2 Hz, 2H), 8.10 (d, = 8.1 Hz, 2H), 8.16 (d, = 8.1 Hz, 2H), 10.14 (s, 1H).
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 0.333333h;
[00152] To a solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (10 g, 50.5 mmol) in DMF (85 mL) at rt was added trimethylsulfonium iodide (11.9 g, 58.1 mmol) followed by potassium hydroxide powder (5.66 g, 101 mmol). The reaction mixture was stirred at rt for 20 min before quenching with H20 (50 mL). The mixture was carefully neutralized with 1 N HC1 solution (55 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic phase was washed with brine, dried over anhydrous Na2S04, and passed through a pad of silica gel (eluting with ethyl acetate). It was concentrated under reduced pressure to afford crude 2-(4- (ethylsulfonyl)phenyl)oxirane as yellow oil, which was used directly for the next step without further purification. LC-MS tR = 1.13 min in 2 min chromatography, MS (ESI) m/z 213.2 [M+H]+.
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 0.333333h;
To a solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (10 g, 50.5 mmol) in DMF (85 mE) at rt was added trimethylsulfonium iodide (11.9 g, 58.1 mmol) followed by potassium hydroxide powder (5.66 g, 101 mmol). The reaction mixture was stirred at rt for 20 mm before quenching with H20 (50 mE). The mixture was carefully neutralized with 1 N HC1 solution (55 mE) and extracted with ethyl acetate (3x100 mE). The combined organic phase was washed with brine,dried over anhydrous Na2SO4, and passed through a pad of silica gel (eluting with ethyl acetate). It was concentrated under reduced pressure to afford crude 2-(4-(ethylsulfonyl) phenyl)oxirane as yellow oil, which was used directly for the next step without further purification. EC-MS tR=l .13 mm in 2 mm chromatography, MS (ESI) mlz 213.2 [M+H].
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 0.333333h;
j000135J To a solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (10 g, 50.5 mmol) in DMF (85 mL) at rt was added trimethylsulfonium iodide (11.9 g, 58.1 mmol) followed by potassium hydroxide powder (5.66 g, 1001 mmol). The reaction mixture was stirred at rt for 20 mm before quenching with H20 (50 mL). The mixture was carefully neutralized with 1 N HC1 solution (55 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic phase was washed with brine, dried over anhydrous Na2504, and passed through a pad of silica gel (eluting with ethyl acetate). It was concentrated under reduced pressure to afford crude 2-(4-(ethylsulfonyl)phenyl)oxirane as yellow oil, which was used directly for the next step without further purification. LC-MS tR = 1.13 mm in 2 mm chromatography, MS (ESI) m/z 213.2 [M+H].
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 0.333333h;
[00215] Step 2: 2-(4-(ethylsulfonyl)phenyl)oxirane [00216] To a solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (10 g, 50.5 mmol) in DMF (85 mL) at rt was added trimethylsulfonium iodide (11.9 g, 58.1 mmol) followed by potassium hydroxide powder (5.66 g, 101 mmol). The reaction mixture was stirred at rt for 20 min before quenching with H20 (50 mL). The mixture was carefully neutralized with 1 N HC1 solution (55 mL) and extracted with EtOAc (3 x 100 mL). The combined organic phase was washed with brine, dried over anhydrous Na2S04, and passed through a pad of silica gel (eluting with EtOAc). It was concentrated under reduced pressure to afford crude 2-(4-(ethylsulfonyl)phenyl)oxirane as yellow oil, which was used directly for the next step without further purification. LC-MS tR = 1.13 min in 2 min chromatography, MS (ESI) m/z 213.2 [M+H]+.
1.1 g
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 0.333333h;
To a solution of <strong>[50899-03-1]4-(ethylsulfonyl)benzaldehyde</strong> (Step 1 intermediate) (1.0 g, 5.04 mmol) in DMF (10 mL) was added trimethylsulfonium iodide (1.18 g, 5.80 mmol) followed by potassium hydroxide powder (560 mg, 10.08 mmol) at RT. The mixture was stirred at RT for 20 min. The mixture was quenched with water and carefully neutralized with 1N HCl. The aqueous mixture was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by a quick filter column to yield 1.1 g of the titled product; APCI-MS (m/z) 211 (M+H)-.
With ammonium acetate; In ethanol; for 12.0h;Reflux; Autoclave; Large scale;
Add absolute ethanol (104kg) to the reactor and stir, then add compound 2 (14.9kg, 1.0eq), propyleneAcid (10.2kg, 1.3eq), ammonium acetate (11.6kg, 2eq), heated to reflux and stirred for 12h. HPLC monitored the reaction to be complete. dropCool to room temperature, filter, wash the filter cake twice with anhydrous ethanol 14 kg ethanol, and dry the filter cake at 50C in a blast to obtain compound 3 (14.4 kg, 75%), a white powdery solid. The obtained crude product was directly used in the next reaction without purification.
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