Ethanol, 2-[2-(2-hydroxyethoxy)ethoxy]-, 1-(4-Methylbenzenesulfonate)

Triethylene glycol (16.81 g, 112 mmol) was dissolved in 20 mL THF, NaOH solution (6.73 g, 168 mmol in 15 mL H(3) Take the flask, add 0.532 mοl triethylene glycol, add 50 mL of tetrahydrofuran, then slowly drop the cooled 0.2 moles of aqueous sodium hydroxide solution, stir the mixture for several minutes, Under the addition of 0.134 mol of p-methanesulfonyl chloride solution, one hour after the drop, after the completion of the drop of ice water removed, to room temperature reaction, 5 hours after the reaction to remove the solvent to get white or light yellow liquid, dissolved with ethyl acetate, saturated aqueous sodium chloride solution several times, combined with organic phase anhydrous magnesium sulfate drying. The solvent was removed by filtration to give a colorless or pale yellow oil which yielded 88.3percent yield.250mL single-neck flask was added triethylene glycol (19.69g, 131.13mmol), solution of p-toluenesulfonyl chloride (5.00g triethylamine (7.96g, 78.68mmol) and dichloromethane (50mL), ice-cooled, 26.23 mmol) was dissolved in dichloromethane (50 mL) of. After completion of the dropwise addition, the reaction system was transferred to room temperature overnight. The solvent was removed by rotary evaporation, the residue was added methylene chloride (a 500 mL) was dissolved, washed with water (a 500 mL) and saturated brine (300mL), dried over anhydrous sodium sulfate. Filtered and the solvent was removed by rotary evaporation to give a colorless oil 6.70g, yield 83.94percent.FIG. 10A shows the synthesis of compound 1. Tosyl chloride (1.00 g, 5.25 mmol) was added at 5° C. to a solution of TEG (triethylene glycol, 1.57 g, 10.5 mmol) in anhydrous methylene chloride (6 mL). This was followed by drop-wise addition of DIPEA (N, N-diisopropylethylamine, 1.0 mL, 5.77 mmol). The water bath was removed and the reaction mixture stirred at room temperature for 18 hours. The resulting mixture was diluted with water (6 mL) and washed with 1 M HCl, brine (2×10 mL), and water (3×10 mL). The solution was dried over sodium sulfate and concentrated under vacuum. The resulting residue was purified by silica gel chromatography (ethyl acetate/hexane 7:3) to obtain the product as yellow oil (1.26 g, 79percent). LEN et al., “Micellar Catalysis Using a Photochromic Surfactant: Application to the Pd-Catalyzed Tsuji-Trost Reaction in Water” J. Org. Chem., 79(2): 493-500 (2014). FIG. 10B shows the Briefly, p-toluenesulfonyl chloride (7.50 g, 40.0 mmol) was added to a solution of triethylene glycol (60.0 g, 40.0 mmol) in pyridine (6.5 mL) and dichloromethane (400 mL) and under nitrogen. Compound 6-1 (235 g, 1.57 mol) was dissolved in 500 mL of tetrahydrofuran, then potassium hydroxide (41.2 g, 0.57 mmol, 82percent w/w) was added, and then p-toluenesulfonyl chloride 6-2 (100 g, 0.52 mol) was added in batches, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1200 mL of water, and extracted with ethyl acetate (400 mL*3). The extract liquid was combined and washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure and purified by silica gel column chromatography, with an eluent (petroleum ether:ethyl acetate=1:1), to obtain the target product 6-3 (118 g, 75percent) as a colorless oil. LC-MS: m/z=305[M+H]The reaction process is as follows: three glycol (262.0mmol), triethylamine (40mmol) and methylene chloride (30 ml) mixed and placed in a 250 ml three flasks; will be to toluene sulfonyl chloride (26mmol) and methylene chloride (35 ml) is placed in the dropping funnel constant and is dropped in the three-mouth flask. The use of balloon under the protection of nitrogen ice salt bath stirring, all melted ice when the temperature of the into stirring at the room temperature, the total reaction time is about 12h. Using thin layer chromatography (TLC) detecting the extent of reaction. When the TLC display in the reactant material point recedes, stopping the reaction. The reaction mixture is cooled to room temperature, water washing three times, the aqueous phase dichloromethane is used for extraction, the combined organic phase with anhydrousMgSOp-Toiuenesuifonyi chloride (7.50 g, 40.0 mrnoi) was added to a solution oftriethylene glycol (60.0 g, 40.0 mrnoi) in pyridine (6.5 mE) and dichiorornethane (DCM, 400 mL) and under nitrogen. After stirring at room temperature for 18 h, the solvent was removed via rotovap. The residue was dissolved in ethyl acetate (200 rnL) and washed with brine (3x100 mL). The ethyl acetate solution was dried over anhydrous Na2SO4. After filtration, the filtrate was evaporated to dryness to give crude product which was puxfied on a silicacolumn to yield 8-tosyloxy-3, 6-dioxooctan-I-ol as a clear oil (868 g, 713percent). Orbitrap ESIMS Caicd. for C13H2O6S 30410 Found 305.11.Tnethylene glycol (120 mmol, 3 eq.) was dissolved in anhydrous THF (80 ml) and triethylamine (80 mmol, 2 eq.) was added. At 0 °C p-toluenesulfonyl chloride (40 mmol, 1 eq.) in anhydrous THF (10 ml) wasadded dropwise over 45 mm. The reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was then removed in vacuo and the crude mixture purified by flash column chromatography using a gradient from 30percent-90 percent Ethyl acetate in heptane.Triethylene glycol (4.50 g, 30 mmol) and triethylamine (TEA) (8.0 mL) were dissolved in dichloromethane (60 mL). Then, tosylchloride (5.70 g, 30 mmol) was added in one portion. The resulting mixture was stirred for 12 h at 25 oC (Scheme 2). After washing with KHSO4 (1 mol/L, 40 mL) and NaHCO3 (5percent, 40 mL) and drying over anhydrous Na2SO4, the crude product was obtained by evaporation and subsequently purified by column chromatography over silica gel (dichloromethane/MeOH = 100:1, v/v) to obtain the target product 1 as a colorless oil (4.2 g, 14.4 mmol, 48percent).To a solution of compound 1 (100 g, 665.90 mmol) in THF (500 ml), was added EtInto a 250-mL round-bottom flask, was placed a solution of 2-[2-(2-hydroxyethoxy)ethoxy]-ethan-1-ol (1.5 g, 9.99 mmol, 1.00 equiv), Ag2O (3.4 g, 14.98 mmol, 1.50 equiv), KI (0.5 g, 2.99 mmol, 0.30 equiv) in dichloromethane (50 mL) at room temperature. This was followed by the addition of TsCl (2.3 g, 12.06 mmol, 1.20 equiv). The resulting solution was stirred overnight at room temperature. The reaction mixture was then quenched by the addition of water (40 mL). The insoluble solids in the reaction mixture were filtered out and the filtrate was extracted with dichloromethane (40 ml x 3). The organic layers were combined, washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was applied onto a silica gel column during with dichlorome thane/me thanol (1 : 1). This resulted in 1 g (33percent) of 14-[(4-methylbenzenesulfonyl)oxy]-3, 6, 9, 12-tetraoxatetradecan-1-ol as yellow oil.j00524j A solution of triethylene glycol (30 g, 199.7 mmol) in THF (300 mL) wascooled to 0°C and charged with NaOH (11.98 g, 299.7 mmol) and stirred for 15 mm. Thissolution was charged with tosyl chloride (38.07 g, 199.7 mmol) and stirred at room temperature for 2 h. The reaction mixture was concentrated in vacuo and the residue obtained was dilutedwith water (100 mL) and extracted with ethyl acetate (3 X 200 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated in vacuo resulting in acrude compound which was purified by chromatography on silica gel, eluting with 2percentmethanol in DCM to give 18.5 g, 30percent yield of the title compound as a colorless oil. ‘H NMR(400 MHz, CDC13): ö = 7.78 (d, J= 8.3 Hz, 2H), 7.33 (d, J= 8.1 Hz, 2H), 4.25 —4.10 (m, 2H), 3.75 — 3.60 (m, 6H), 3.63 — 3.52 (m, 4H), 2.43 (s, 3H).General procedure: p-TsCI (1.2 eq.) was added dropwise to a mixture of the appropriate di-alcohol, Et3N (1 eq.), and DMAP (cat.) in dry CH2CI2 (0.01 M) under N2 atmosphere with stirring at 0°C. The stirring was continued at room temperature for 4 hours. The reaction was quenched with saturated NH4CI aqueous solution and the whole was extracted with AcOEt. The extract was washed with brine, dried over Na2SO4, and, following solvent evaporation, the crude was purified by flash chromatography. ES154; 2-(2-(2-hydroxyethoxy)ethoxy)ethyl 4-methylbenzenesu Ifonate. It was synthesized from triethylene glycol (1 .000 g, 6.66 mmol). Elution with petroleum etherAcOEt (2:8) afforded ES154 as a waxy solid: 0.450 g (22percent).1H-NMR (CDCI3, 400 MHz)5 2.30 (s, 3H), 2.99 (br s, exchangeable with D20, IH), 3.40-3.63 (m, IOH), 4.02 (t, J=4.8 Hz, 2H), 7.21 (d, J=8.4 Hz, 2H), 7.64 (d, J=8.4 Hz, 2H). 13C-NMR (CDCI3, 100MHz) 521.48, 42.73, 61.39, 68.47, 69.24, 70.06, 70.42, 71.12, 72.46, 127.79, 129.81, 132.71, 144.87.Under the protection of nitrogen, to a 1000ml three-necked flask were added 200 mL pyridine, 120 g BP103a00(1.0eq), stirred and cooled down to 0°C. 151.8g TsCl (1.0eq) was added in batches, stirred for 1h, then slowly warmed up to room temperature, and kept stirring for 3-4h. After the completion of the reaction, the reaction liquid was poured into ice-cold dilute hydrochloric acid solution, extracted with ethyl acetate. The ethyl acetate layer was washed once with dilute hydrochloric acid, washed with saturated sodium bicarbonate, washed with saturated brine, and dried over anhydrous Na

Molecular Weight:304.36
XLogP3:0.5
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:6
Rotatable Bond Count:10
Exact Mass:304.09805953
Monoisotopic Mass:304.09805953
Topological Polar Surface Area:90.4
Heavy Atom Count:20
Complexity:329
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes