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CAS No. : | 14752-66-0 | MDL No. : | MFCD00035602 |
Formula : | C6H4ClNaO2S | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | JFXAUUFCZJYLJF-UHFFFAOYSA-M |
M.W : | 198.60 | Pubchem ID : | 23664783 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
98% | In N,N-dimethyl-formamide; at 45 - 115℃; for 3h; | A solution of 108.53 g (1 mol) of methyl ester ofmonochloroacetic acid (4) in 200 mL of DMF was addedto a suspension of 198.6 g (1 mol) of <strong>[14752-66-0]sodium 4-chlorophenylsulfinate</strong> (prepared by reacting 4-chlorophenylsulfochloridewith sodium sulfi te in 500 mL of DMF)heated to 45C. The reaction mixture was heated withstirring to 115C for 3 h. After cooling, it was pouredinto 3 L of cold water and held in a refrigerator for 12 h.The precipitate was fi ltered off, recrystallized from chloroform-hexane, and dried over P2O5. 233.7 g (98%) ofester 5 was obtained, mp 81-82C. 1 NMR spectrum, δ, ppm (D3OD): 7.40-7.31 m (4, 64), 4.05 s (2,2), 3.29 s (3, 3). IR spectrum, ν, cm-1:1735 (), 1150, 1330 (SO2). Found, %: C 43.80,H 3.45, Cl 14.11, S 13.12. C9H9ClO4S. Calculated, %:C 43.46, H 3.66, Cl 14.25, S 12.89. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Example 82: 1-(4-Chlorophenylsulfonylmethyl)-3-methoxybenzene A dimethoxyethane (10 ml) suspension of <strong>[14752-66-0]sodium 4-chlorobenzenesulfinate</strong> (210 mg, 1.06 mmol) and 3-methoxybenzyl chloride (154 μl, 1.06 mmol) was stirred at 70C for 16 hours.. After cooling to room temperature, butanol (2 ml) and tetrabutylammonium bromide (45 mg) were added and the resulting mixture was stirred further at 70C for 16 hours.. After cooling the reaction mixture to room temperature, the solvent was concentrated under reduced pressure.. ethyl acetate was added to the residue.. The mixture was washed successively with water and brine, and dried over anhydrous sodium sulfate.. After filtration, the filtrate was concentrated under reduced pressure.. The residue was subjected to flash chromatography on a silica gel column, and the fraction obtained from the hexane:ethyl acetate (=5:1) elude was concentrated under reduced pressure, whereby the title compound (216 mg, 69%) was obtained as a white solid. IR (ATR) ν: 3064, 2979, 2842, 1598, 1488, 1469, 1434, 1392, 1313, 1268, 1176, 1130, 1085, 1033, 1012, 941, 879, 823, 792, 765, 742, 692, 620, 574, 528, 455 cm-1.1H-NMR (400MHz, CDCl3) δ: 3.74(3H,s), 4.27(2H,s), 6.59-6.68(2H,m), 6.82-6.90(1H,m), 7.17(1H,t,J=7.8Hz), 7.42(2H,d,J=8.6Hz), 7.56(2H,d,J=8.6Hz). MS (m/z): 297 (M++H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,2-dimethoxyethane; at 70℃; for 24h; | Example 71: 1,4-Dichloro-2-[1-[(4-chlorophenyl)sulfonyl]-5-(methylsulfonyl)pentyl]benzene sodium 4-chlorobenzenesulfinate (38 mg, 0.192 mmol) and <strong>[85482-13-9]2,5-dichlorobenzyl bromide</strong> (46 mg, 0.192 mmol) were added to dimethoxyethane (5 ml).. The resulting mixture was stirred at 70C for 24 hours.. After cooling to room temperature, the reaction mixture was subjected to a short column (silica gel) and the fraction eluted with diethyl ether was concentrated under reduced pressure.. The residue thus obtained was dissolved in toluene (5 ml).. To the resulting solution were added the 4-(methylsulfonyl)-1-butanol (58 mg, 0.381 mmol) obtained in Referential Example 3 and cyanomethylenetri-n-butylphosphorane (89 mg, 0.370 mmol), followed by heating under reflux for 23 hours under an argon atmosphere.. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure.. The residue was subjected to medium-pressure chromatography on a silica gel column.. From the fraction eluted with hexane:ethyl acetate (=1:1), the title compound (32 mg, 35%) was obtained as a colorless oil. IR (ATR) nu: 2933, 2869, 1581, 1465, 1394, 1313, 1278, 1191, 1133, 1083, 1039, 1012, 962, 887, 821, 752, 713, 630, 588, 532, 464 cm-1.1H-NMR (400MHz, CDCl3) delta: 1.33-1.50(2H,m), 1.80-1.96(2H,m), 2.09-2.21(1H,m), 2.48-2.59(1H,m), 2.88(3H,s), 2.90-2.99(2H,t,J=11.0,4.2Hz), 4.79(1H,dd,J=11.0,4.2 Hz), 7.15(1H,d,J=8.6Hz), 7.20-7.29(1H,m), 7.34-7.40(2H,m), 7.46-7.52(2H,m), 7.63(1H,d,J=2.5Hz). MS (m/z): 469, 471 (M++H). HRMS (FAB) for C18H20O4Cl3S2 (M++H) Calculated: 468.9869 Found: 468.9907 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With potassium acetate; In propan-1-ol; at 70℃; for 8h; | Example 119: 4-(4-Chlorophenylsulfonylmethyl)pyridine Under heating, a 1-propanol (50 ml) solution of 4-chloromethylpyridine hydrochloride (1.26 g, 7.65 mmol), <strong>[14752-66-0]sodium 4-chlorobenzenesulfinate</strong> (1.52 g, 7.65 mmol) and potassium acetate (1.50 g, 15.3 mmol) was stirred at 70C for 8 hours.. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure.. The residue was filtered through a short column (silica gel, ethyl acetate) and the elude was concentrated under reduced pressure.. The residue was subjected to chromatography on a silica gel column, and the fraction obtained from the hexane:ethyl acetate (=2:3) elude was concentrated under reduced pressure, whereby the title compound (1.26 g, 62%) was obtained as a white solid.1H-NMR (400MHz, CDCl3) δ: 4.29(2H,s), 7.06(2H,d,J=6.1Hz), 7.47(2H,d,J=8.8Hz), 7.59(2H,d,J=8.5Hz), 8.57(2H,d,J=6.1Hz). MS (m/z): 268 (M++H). |
62% | With potassium acetate; In propan-1-ol; at 70℃; for 8h; | A 1-propanol (50 ml) solution of 4-chloromethylpyridine hydrochloride (1.26 g, 7.65 mmol), <strong>[14752-66-0]sodium 4-chlorobenzenesulfinate</strong> (1.52 g, 7.65 mmol) and potassium acetate (1.50 g, 15.3 mmol) was stirred under heating at 70C for 8 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The residue thus obtained was caused to pass through a short column (silica gel, ethyl acetate) and the eluate was concentrated under reduced pressure. The residue thus obtained was subjected to silica gel column chromatography, and the fraction obtained from the hexane:ethyl acetate (=2:3) eluate was concentrated under reduced pressure to give the title compound (1.26 g, 62%) as a white solid. 1H-NMR(400MHz, CDCl3) δ: 4.29(2H,s), 7.06(2H,d,J=6.1Hz), 7.47(2H,d,J=8.8Hz), 7.59(2H,d,J=8.5Hz), 8.57(2H,d,J=6.1Hz). MS (m/z) : 268 (M++H). |
With potassium acetate; In butan-1-ol; at 70℃; for 5h; | Example 74: 4-[1-[(4-Chlorophenyl)sulfonyl]-5-(methylsulfonyl)pentyl]pyridine <strong>[14752-66-0]sodium 4-chlorobenzenesulfinate</strong> (207 mg, 1.04 mmol), 3-chloromethylpyridine hydrochloride (171 mg, 1.04 mmol) and potassium acetate (204 mg, 2.08 mmol) were added to n-butanol (5 ml).. The resulting mixture was stirred at 70C for 5 hours.. After cooling to room temperature, the solvent was concentrated under reduced pressure.. To the residue was added ethyl acetate and from the resulting mixture, the insoluble matter was filtered off.. The filtrate was concentrated under reduced pressure.. The residue was subjected to chromatography on a silica gel column and the from the fraction eluted with hexane:ethyl acetate (=2:3), a white solid (117 mg) was obtained. Then, a toluene (10 ml) solution of the resulting solid (52 mg), the 4-(methylsulfonyl)-1-butanol (90 mg, 0.592 mmol) obtained in Referential Example 3 and cyanomethylenetri-n-butylphosphorane (140 mg, 0.582 mmol) was heated under reflux for 2 days under an argon atmosphere.. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | A mixture of THF, K2CO3 (0.77 g 0 006 mol) and sodium 4-chloro- benzenesulfinate(0.75 g, 3.7 mmol) was stirred for 15 en blanket and cooled to 0-5 C. <n="19"/>Naphth-2-ylmethylbromide (0.81 g, 3.7 mmol) was added to the reaction mixture. The mixture was stirred at 65 - 67 C for two hours and the solvent was removed by distillation. The resultant solid residue was recrystallized from isopropanol to give the title product, 0.30g, 51% yield, 99% purity by HPLC | |
In 1,2-dimethoxyethane; at 70℃; for 5h; | Example 67: 2-[1-[(4-Chlorophenyl)sulfonyl]-5-(methylsulfonyl)pentyl]naphthalene <strong>[14752-66-0]sodium 4-chlorobenzenesulfinate</strong> (211 mg, 1.06 mmol) and 2-bromomethylnaphthalene (235 mg, 1.06 mmol) were added to dimethoxyethane (5 ml).. The resulting mixture was stirred at 70C for 5 hours.. After cooling to room temperature, the solvent was concentrated under reduced pressure.. The residue was added with ethyl acetate and from the resulting mixture, the insoluble matter was filtered off.. The residue obtained by concentrating the filtrate under reduced pressure was washed with hexane to yield a white powder (90 mg). Then, a toluene (10 ml) solution of the resulting white powder (60 mg), the 4-(methylsulfonyl)-1-butanol (59 mg, 0.388 mmol) obtained in Referential Example 3 and cyanomethylenetri-n-butylphosphorane (91 mg, 0.379 mmol) was heated under reflux for 21 hours under an argon atmosphere.. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure.. The residue was subjected to medium-pressure chromatography on a silica gel column, whereby from the fraction eluted with hexane:ethyl acetate(=2:3), the title compound was obtained as a white solid (62 mg). Melting point: 146.0-147.0C. IR (ATR) ν: 2931, 2861, 1581, 1508, 1473, 1457, 1392, 1359, 1309, 1274, 1191, 1147, 1126, 1081, 1010, 968, 902, 869, 819, 752, 734, 703, 646, 624, 566, 522, 472, 453 cm-1.1H-NMR (400MHz, CDCl3) δ: 1.34-1.51(2H,m), 1.78-1.99(2H,m), 2.25-2.40(1H,m), 2.50-2.62(1H,m), 2.84(3H,s), 2.89-3.03(2H,m), 4.19(1H,dd,J=11.2,3.9Hz), 7.18-7.36(4H,m), 7.39-7.61(4H,m), 7.69-7.90(3H,m). MS (m/z): 451 (M++H). Elemental Analysis for C22H23ClO4S2 Calculated: C 58.59%; H 5.14%; Cl 7.86%; S 14.22%. Found: C 58.46%; H 5.03%; Cl 7.94%; S 14.33%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | With potassium carbonate; N,N`-dimethylethylenediamine;copper(l) iodide; In dimethyl sulfoxide; at 100℃; for 8h; | Description 3 3-[(4-Chlorophenyl)sulfonyl]-8-fluoroquinoline (D3) EPO <DP n="19"/>A mixture of 8-fluoro-3-iodoquinoline (D1 ) (750 mg, 2.75 mmol), sodium 4- chlorobenzenesulfinate (1.1 g, 5.5 mmol), copper (I) iodide ( 52 mg, 0.275 mmol) and potassium carbonate (380 mg, 2.75 mmol) was treated with λ/./V-di methyl- 1 ,2- ethanediamine (49 mg, 0.55 mmol) and anhydrous dimethylsulphoxide (4 ml). The mixture was stirred at 1000C under argon for 8 hr, and cooled to 200C. The reaction mixture was diluted with water (60 ml) and extracted with ethyl acetate (3 x 40 ml). The organic extracts were combined, washed with water (60 ml) and brine (60 ml), dried over magnesium sulphate, and evaporated to dryness. The residue was dissolved in a 1 :1 mixture of dimethylsulphoxide and acetonitrile and purified by mass-directed auto- preparative chromatography using 10 minute gradients containing water and between 50% and 99% acetonitrile with 0.1% formic acid. Product fractions were collected and evaporated to yield the title compound as a white solid (295 mg, 33%). δH (CDCI3, 400MHz) 7.51-7.69 (4H, m), 7.79 (1 H, d, J = 8 Hz), 7.96-7.99 (2H, m), 8.84 (1 H, d, J = 2 Hz), 9.30 (1 H, d, J = 2 Hz) Mass spectrum: C15H9CIFNO2S requires 321 ; found 322 (MH+) |
33% | With copper(l) iodide; potassium carbonate; N,N-dimethylethylenediamine; In dimethyl sulfoxide; at 100℃; for 8h; | A mixture of 8-fluoro-3-iodoquinoline (750 mg, 2.75 mmol), sodium 4- chlorobenzenesulfinate (1.1 g, 5.5 mmol), copper (I) iodide ( 52 mg, 0.275 mmol) and potassium carbonate (380 mg, 2.75 mmol) was treated with λ^, λ^-dimethyl-l,2-ethanediamine (49 mg, 0.55 mmol) and anhydrous dimethylsulphoxide (4 ml). The mixture was stirred at 1000C under argon for 8 hr, and cooled to 200C. The reaction mixture was diluted with water <n="215"/>(60 ml) and extracted with ethyl acetate (3 x 40 ml). The organic extracts were combined, washed with water (60 ml) and brine (60 ml), dried over magnesium sulphate, and evaporated to dryness. The residue was dissolved in a 1 :1 mixture of dimethylsulphoxide and acetonitrile and purified by mass-directed auto -preparative chromatography using 10 minute gradients containing water and between 50% and 99% acetonitrile with 0.1% formic acid. Product fractions were collected and evaporated to yield the title compound as a white solid (295 mg,δH (CDCl3, 400MHz) 7.51-7.69 (4H, m), 7.79 (IH, d, J = 8 Hz), 7.96-7.99 (2H, m), 8.84 (IH, d, J = 2 Hz), 9.30 (IH, d, J = 2 Hz)Mass spectrum: C15H9ClFNO2S requires 321; found 322 (MH+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | General procedure: Under nitrogen atmosphere, a sealable reaction tube equipped with a magnetic stirrer bar was charged with azole (0.50 mmol), sodium arylsulfinate (1.0 mmol), Pd(OAc)2 (0.025 mmol), Cu(OAc)2 (1.0 mmol), CF3COOH (0.50 mmol), and dimethylglycol (2.0 mL). The rubber septum was then replaced by a Teflon-coated screw cap, and the reaction vessel placed in an oil bath at 120 C for 24 h. After the reaction was completed, it was cooled to room temperature and the mixture was treated with K2CO3 solution (1.0 mol/L, 3.0 mL), then extracted with ethyl acetate. The resulting solution was dried by Na2SO4 then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluant: petroleum ether/ethyl acetate=12:1, v/v) to give the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In water; at 90.0℃; for 7.0h; | To the solution of salt 3 (3.97 g, 20 mmol) in water(20mL) <strong>[2156-56-1]sodium dichloroacetate</strong> (3.77 g, 2.5 mmol) was added. The mixture was stirred andheated at 90Cfor 7 hours, kipping pH ~7, by dropping 30% solution of natrium hydroxide. Aftercooling to the room temperature the precipitate was filtered off, washed bywarm water and dried. The product 7 waspurified by recrystallization from ethanol. Chloromethyl-4-chlorophenyl sulfone8 was obtained in 74% yield. M.p. = 120-121C. IR (cm-1):2970 (CHaliph.), 1600 (CHar), 1320, 1140 (SO2).1H-NMR, 400MHz, (CDCl3) delta: 4.53 (s, 2H);7.58-7.60 (m, 2H); 7.90- 7.92 (m. 2H). 13C NMR (100 MHz, CDCl3) delta: 65.99; 124.03;127.47; 132.49; 146.27. Elemental analysis: for C7H6Cl2O2S(225.09) Calcd.: 37.35 % C, 2.69 %H. Found: 37.33 % C, 2.72 % H. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; In ethyl acetate; at 20℃; for 2h; | General procedure: 2-Phenylindole (0.58 g, 3 mmol), TsOH·H2O (0.29 g, 1.5 mmol), 4-chlorobenzenesulfinic acid sodium salt(0.59 g, 3 mmol), and benzaldehyde (0.31 mL, 3 mmol) were placed in a round bottom flask and suspended inethyl acetate. The mixture was stirred at room temperature for 2 h, and was then diluted with water. Theresulting white precipitate was collected and washed with ether to afford analytically pure 2d (0.54 g, 1.2mmol, 40%). |