Structure of 117087-17-9
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CAS No. : | 117087-17-9 |
Formula : | C14H20O3 |
M.W : | 236.31 |
SMILES Code : | CC1(C)OCC(COCC2=CC=CC=C2)CO1 |
MDL No. : | MFCD20482798 |
InChI Key : | YGIKXAGSKRRXED-UHFFFAOYSA-N |
Pubchem ID : | 23295265 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
95% | Step 1: 5-(Benzyloxymethyl)-2,2-dimethyl-1,3-dioxane To a solution of (2, 2-dimethyl-1, 3-dioxan-5-yl)methanol (0.29 g, 2.0 mmol) in DMF (10 mL) was added NaH (60percent in oil, 0.12 g, 3.0 mmol) at 0° C. The mixture was stirred at 0° C. for 0.2 hours. Then (bromomethyl) benzene (0.45 g, 2.6 mmol) was added. The mixture was warmed to 10° C. for 3 h and held for 18 h. The reaction mixture was quenched with ice-water, followed by EtOAc (60 mL). Phase separation, the organic layer was washed with brine (60 mL*3), dried over Na2SO4 and filtered. The filtrate was concentrated and the residue was purified by silica gel column (20 g, UV 254 nm eluting with EtOAc in PE from 10percent to 50percent) to afford 5-(benzyloxymethyl)-2,2-dimethyl-1,3-dioxane (1), (0.46 g, 0.2 mol, 95percent) as a colorless oil. ESI-MS (EI+, m/z): 237.3 [M+H]+. | |
95% | To a solution of(2, 2-dimethyl-1, 3-dioxan-5-yl)methanol (0.29 g, 2.0 mmol) in DMF (10 mL) was added NaH (60percent in oil, 0.12 g, 3.0 mmol) at 0 °C . The mixture was stirred at 0 °C for 0.2 hours. Then (bromomethyl) benzene (0.45 g, 2.6 mmol) was added. The mixture was warmed to 10 °C for 3 h and held for 18 h. The reaction mixture was quenched with ice-water, followed by EtOAc (60 mL). Phase separation, the organic layer was washed with brine (60 mL*3), dried over Na2SO4 and filtered. The filtrate was concentrated and the residue was purified by silica gel column (20 g, UV 254 nm eluting with EtOAc in PE from 10 percent to 50 percent) to afford 5-(benzyloxymethyl)-2,2-dimethyl-1,3-dioxane (1), (0.46 g, 0.2 mol, 95 percent) as a colorless oil. ESI-MS (EI, m/z): 237.3 [M+H]. | |
To a solution of acetonide (2,2-dimethyl-1,3-dioxan-5-yl)methanol (3.0 g, 20.52 mmol) and tetrabutyl ammonium iodide (7.58 g, 20.52 mmol) in anhydrous THF (100 mL) was added sodium hydride (1.108 g, 27.7 mmol) in 3 portions. The mixture was allowed to stir at room temperature for 1 hour and then treated with benzyl bromide (2.93 ml, 24.63 mmol) over 3 minutes. The mixture was allowed to stir overnight at room temperature (18 hours). The mixture was analyzed by tlc (2:1 hexanes:ethyl acetate) and 1H NMR which showed complete consumption of starting material. The mixture was quenched with saturated ammonium chloride solution (75 mL) and extracted with ethyl acetate (200 mL and 100 mL). Combined organic phases were dried over sodium sulfate and then concentrated to dryness. The crude material was then purified by column chromatography over silica gel eluting with 0-30percent EtOAc/hexanes to obtain MD-02-130 as colorless oil. 1H NMR (400 MHz, chloroform-d) delta 7.35 - 7.24 (m, 5H), 4.50 (s, 2H), 3.96 (dd, J = 12.0, 4.2 Hz, 1H), 3.77 (dd, J = 11.8, 6.4 Hz, 1H), 3.51 (d, J = 6.7 Hz, 2H), 2.04 - 1.97 (m, 1H), 1.41 (s, 3H), 1.38 (s, 3H). |
To a solution of compound 24 (crude material max. 94 mmol)in dry DMF (600 ml) cooled to 0 C under argon atmosphere and NaH (60percent suspension in mineral oil; 6 g, 150 mmol, 1.6 eq.) was added. Reaction flask was filled with argon again and the mixture was stirred for 20 min. to preform sodium salt of alcohol. Benzylbromide (14.6 ml, 123 mmol, 1.3 eq.) was added and reaction flask was filled with argon again. The resulting mixture was let to warmto room temperature and stirred overnight. Water (100 ml) was added and mixture was stirred for 30 min. Solvent was evaporated in vacuo and the residue was codistilled with toluene (3). Crude material was suspended in EtOAc (250 ml) and mixture of saturatedsolution of NH4Cl (20 ml) and water (180 ml) was added.Water phase was extracted with EtOAc (2 150 ml). The organic phase was collected (250 + 150 + 150 ml) and washed with water(2 200 ml), followed by brine (1 200 ml) and dried overMgSO4. The solution was filtered and evaporated in vacuo. The residue(crude compound 25, red-brown oil) was diluted in MeOH(700 ml) and water (70 ml). DOWEX (50WX8 H+, 30 g) was addedand the mixture was heated at 50 C and stirred overnight. Reactionmixture was cooled down to room temperature and filteredthrough the frit (S3), evaporated in vacuo and codistilled withtoluene (3). Crude product 26 was obtained as brown oil andused in the next reaction step without purification. Reaction wasmonitored by TLC. Small amount of crude product was purifiedby flash chromatography (silica gel; eluent CHCl3/MeOH, gradient2?15percent) to obtain an analytical sample |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.51 g (72%) | With NaH; In 1,2-dimethoxyethane; | EXAMPLE 2 2-Benzyloxymethyl-3-diethylphosphonomethoxy-1-(p-toluenesulfonyloxy)propane A solution of <strong>[4728-12-5]5-hydroxymethyl-2,2-dimethyl-1,3-dioxane</strong> (cf:Bates, H. A.; Farina, J.; Tong, M. J. Org. Chem. 1986, 51, 2637, 3.0 g, 20.5 mmol) in 25 mL of dry DME under argon was added via cannula to a slurry of NaH (0.740 g, 80percent dispersion in oil, 24.6 mmol) in 60 mL of dry DME cooled to 0° C. The resulting grey slurry was stirred at room temperature for 0.5 h, then recooled to 0° C., and treated with a solution of benzylbromide (4.56 g, 26.7 mmol) in 20 mL of DME. The reaction mixture was stirred at room temperature (rt) overnight and then quenched with 100 ml of H2 O. The aqueous layer was separated and extracted with two portions of ethyl acetate. The combined organic layers were then washed with saturated sodium chloride solution, dried over MgSO4, filtered, and concentrated to provide a yellow oil. Purification by column chromatography on silica gel (ethyl acetate/hexane) afforded 3.51 g (72percent) of 5-benzyloxymethyl-2,2-dimethyl-1,3-dioxane as a clear colorless liquid. |
Tags: 117087-17-9 synthesis path| 117087-17-9 SDS| 117087-17-9 COA| 117087-17-9 purity| 117087-17-9 application| 117087-17-9 NMR| 117087-17-9 COA| 117087-17-9 structure
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