Structure of Tos-PEG3
CAS No.: 77544-68-4
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| CAS No. : | 77544-68-4 |
| Formula : | C13H20O6S |
| M.W : | 304.36 |
| SMILES Code : | O=S(C1=CC=C(C)C=C1)(OCCOCCOCCO)=O |
| English Name : | 2-(2-(2-Hydroxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate |
| MDL No. : | MFCD18433414 |
| InChI Key : | RSUCRUOTLCQWFX-UHFFFAOYSA-N |
| Pubchem ID : | 10913735 |
* 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 |
|---|---|---|
| 96% | In acetone for 2.5h; Heating; | |
| 67% | In acetone for 24h; Inert atmosphere; | |
| 64% | With 18-crown-6 ether In acetonitrile at 35℃; for 6h; Inert atmosphere; |
| 5.89 g | In acetone for 1h; Reflux; | |
| 5.89 g | In acetone Reflux; | |
| 96 % | In N,N-dimethyl-formamide at 90℃; Inert atmosphere; | 7 A mixture of 2-2 (4.1 g, 13.55 mmol, 1.0 equiv) and potassium thioacetate (3.09 g,27.10 mmol, 2.0 equiv) in 40 mL DMF was heated at 90 °C under nitrogen for 16 h. The reaction mixture was cooled to room temperature and diluted with 100 mL dichloromethane. The resulting mixture was washed with water (5 x 100 mL), and the organic layer was dried over sodium sulfate. After concentration, the crude was purified by silica gel column (80% ethyl acetate in hexane) to give product 2-3 as orange-colored oil (2.71 g, 96%).1H NMR (300 MHz, CDCh): 53.76-3.58 (12H, m), 3.09 (IH, t, J = 6.30 Hz), 2.33 (3H, s). |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 56% | With potassium carbonate In acetonitrile Heating; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 79% | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 18h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95.69% | With potassium carbonate In acetonitrile at 80℃; | 7.2 Step 2: In a single-necked flask, the product from Step 1 (98.32 g, 323.04 mmol), reactant 2 (p-hydroxybenzaldehyde, 37.48 g, 306.89 mmol), and potassium carbonate (58.04 g, 419.95 mmol) were added to 500 mL of acetonitrile and stirred at 80 °C. After the starting materials disappeared under TCL monitoring, the acetonitrile was concentrated under reduced pressure. 300 mL of ethyl acetate was added to the system, and the mixture was stirred at room temperature. The mixture was filtered to obtain the filtrate, which was then concentrated to dryness to obtain the Step 2 product: 78.6 g, yield: 95.69%. |
| 78% | With potassium carbonate In N,N-dimethyl-formamide for 48h; Heating; | |
| 73% | With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 2.5h; |
| 65.3% | With potassium carbonate In N,N-dimethyl-formamide at 80℃; | |
| 45% | With potassium carbonate In acetonitrile Reflux; Inert atmosphere; | |
| 87 % | In acetonitrile at 80℃; Inert atmosphere; | 4-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}benzaldehyde(2) To a solution of 0.25 g (2.05 mmol) of4-hydroxybenzaldehyde 1 in 40 mL of acetonitrile underargon was added 0.85 g (6.15 mmol) of K2CO3. Theresulting mixture was heated to 80°C, and then a solutionof 0.76 g (2.05 mmol) of 2-[2-(2-hydroxyethoxy)-ethoxy]ethyl-4-methylbenzenesulfonate (1) in 10 mLof acetonitrile was added dropwise. The reactionmixture was stirred with heating for 48 h, after whichit was cooled, fi ltered, and the precipitate was washedwith dichloromethane. The combined organic solutionswere evaporated, the residue was purifi ed by silica gelcolumn chromatography (chromatographic column15 m 40 g, eluent: petroleum ether (50%)-ethyl acetate(50%) => ethyl acetate (100%) for 20 min. Yield 0.45 g(87%), colorless liquid. 1H NMR spectrum (CDCl3),δ, ppm: 3.57-3.64 m (6H), 3.70-3.75 m (2H), 9.89 s(1H), 4.16-4.18 m (2H), 4.21-4.24 m (2H), 7.01-7.05 m (2H), 7.79-7.75 m (2H). Mass spectrum,m/z: 255.1231 [M + H]+. Found, %: C 61.10; H 7.08;O 31.82. C13H18O5. Calculated, %: C 61.40; H 7.14;O 31.46. [M + H]+ 255.1232. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95% | With tetrabutyl ammonium fluoride In tetrahydrofuran for 2h; Heating; | |
| 67% | With tetrabutyl ammonium fluoride In tetrahydrofuran at 22℃; for 11h; | 13 The final product was made from the 8-tosyloxy-3,6-dioxooctan-1-ol. A 3-neck 100 mL reaction flask was fitted with a dropping funnel, thermometer, stirring bar and nitrogen inlet and purged with dry nitrogen. The triethylene glycol monotosylate, 5, (10.016 g, 32.9 mmol) was weighed into the reaction flask followed by pipette addition of dry THF (31.0 mL). After dissolution, tetrabutyl ammonium fluoride (37.0 mL 1.0 M/THF, 37.0 mmol) was transferred to the dropping funnel and added dropwise to the stirred reaction mixture. The reaction was stirred at 22° C. for 11 hr under N2 and developed a dark brown coloration. The reaction was worked up by rotary evaporator concentration (5° C./20 mm) to remove THF then vacuum distilled (105-115° C./5 mm) to collect 3.58 g of an amber liquid. This crude product was redistilled (114-116° C./4 mm) to yield 3.327 g (67% yield) of product as a colorless liquid. 1H NMR (300 MHz, CDCl3, TMS): δ=2.95 (s, 1H), 3.5-3.8 (m, 10H), 4.52 (d 2JHF=51 Hz of t 3JHH=4 Hz, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ=61.54, 70.19, 70.38, 70.66, 72.45, 82.95. 19F NMR (282 MHz, CDCl3, CFCl3): δ=-223.33 (t 2JHF=48 Hz of t 3JHH=31 Hz). IR (NaCl): v=3450, 2885, 1358, 1014 cm-1. CI MS: m/z 153 (MH+). |
| 60% | With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; Inert atmosphere; | 9 To a solution of 84osyioxv-3,6-dioxooctan-I--oi (8.5 g, 2793 mmol) in anhydrous IHF (28 rnL) was added 1 .0 M IHF solution of tetrabutylammoniurn fluoride (TBAF, 32 mE, 32.0 mmo]) dropwise under N2. The reaction solution was stirred at room temperatureovernight under N2. THF was removed by rotovap. The residue was distilled to give lightbrown liquid. After redistill, i-fiuoro-3,6-dioxooctan-i-oi was obtained as a colorless liquid, 2.55g, yield 60%. Orbitrap ESFMS Calcd. for C6H13F03 152.08 Found 153.20. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 6 steps 1.1: sodium azide; sodium iodide / water; acetone / 60 °C 2.1: palladium 10% on activated carbon; hydrogen / ethanol / 20 °C / 760.05 Torr 3.1: ethanol / 0 - 20 °C 4.1: dmap; triethylamine / dichloromethane / 20 °C / Inert atmosphere 5.1: sodium hydroxide / water; toluene / 1 h / 100 °C 5.2: 20 - 100 °C 6.1: triethylamine / dichloromethane / 0.08 h / 0 °C 6.2: 24 h / 0 - 20 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 7 steps 1.1: sodium azide; sodium iodide / water; acetone / 60 °C 2.1: palladium 10% on activated carbon; hydrogen / ethanol / 20 °C / 760.05 Torr 3.1: ethanol / 0 - 20 °C 4.1: dmap; triethylamine / dichloromethane / 20 °C / Inert atmosphere 5.1: sodium hydroxide / water; toluene / 1 h / 100 °C 5.2: 20 - 100 °C 6.1: triethylamine / dichloromethane / 0.08 h / 0 °C 6.2: 24 h / 0 - 20 °C 7.1: sodium azide; sodium iodide / water; acetone / 48 h / 80 °C | ||
| Multi-step reaction with 5 steps 1.1: sodium azide; sodium iodide / water; acetone / 23 h / 60 °C / Inert atmosphere 2.1: hydrogen; palladium-carbon / ethanol / 3 h / 20 °C 3.1: ethanol / 0 - 20 °C 4.1: triethylamine; dmap / dichloromethane / 20 °C 5.1: sodium hydride / tetrahydrofuran; mineral oil / 0.5 h / 0 °C / Inert atmosphere 5.2: 2 h / 20 °C / Inert atmosphere |

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