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CAS No. : | 60656-87-3 | MDL No. : | MFCD00191779 |
Formula : | C9H10O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NFNOAHXEQXMCGT-UHFFFAOYSA-N |
M.W : | 150.17 | Pubchem ID : | 108989 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* 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 |
---|---|---|
With sodium tris(acetoxy)borohydride; In 1,1-dichloroethane; at 20℃; | A mixture of 4-hydroxybutylamine (4.0 g, 44.9 mmol), t?rt-butyldimethyl-silyl chloride (7.4 g, 49.3 mmol) and imidazole (6.7 g, 98.7 mmol) in dichloromethane (150 mL) was stirred at room temperature for 2 hours. The product mixture was washed successively with aqueous NaHCO3, water, EPO <DP n="67"/>and brine. The organic extract was dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. This intermediate silylated aminoalcohol was used without further purification. To a mixture of the amine (1.0 g, 4.9 mmol) and benzyloxyacetaldehyde (0.74 g, 4.9 mmol) in dichloroethane (15 mL) at room temperature, sodium triacetoxyborohydride (1.3 g, 6.3 mmol) was added. The reaction mixture was concentrated under vacuum. The residue was partitioned between ethyl acetate and aqueous sodium carbonate. The organic extract was dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue was subjected to column chromatography on silica gel eluting with 2% methanol in dichloromethane. Collection and concentration of appropriate fractions afforded the title silyloxybutyl-amine. lH NMR (400 MHz, CDCI3) δ 7.33 -7.25 (m, 5H), 4.51 (s, 2H), 3.60 (m, 4H), 2.79 (br t, J = 4.9 Hz, 2H)52.60 (br t, 2 H), 1.52 (br signal, 5 H), 0.87 (s, 9H), 0.03 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | In methanol; at 20℃; for 24h; | Example 15 N-Cyclohexyl-C- (benzyloxy) methyl nitrone Benzyloxy acetaldehyde (500 mg, 3.33 mmol) and tert-butyl hydroxyl amine hydrochloride (596 mg, 4.0 mmol) in methanol (lOmL) were stirred together at ambient temperature for 24 hrs. The mixture was then concentrated to dryness, the crude mixture was dissolved in ethyl acetate (20 ml), washed with water (2 x 40 ml), dried (Na2SO4) and concentrated and the crude product was chromatographed on silica gel to obtain the title compound (363 mg, 49percent). MS: m/z = 248 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | 6-Bromo-2-chloro-3-iodopyridine (1.50 g, 4.71 mmol) was dissolved in THF (15 mL) and cooled to -78 C, followed by addition of isopropylmagnesium chloride-lithium chloride complex (3.99 mL, 5.18 mmol). The mixture was stirred at -78C for 1 h. 2- (benzyloxy)acetaldehyde (0.849 g, 5.65 mmol) was added and the resulting mixture warmed to 0C and stirred for 2 h. The mixture was treated with saturated NH4C1 and extracted with ethylacetate. The organic layer was washed with brine, dried (Na2SO4), filtered and concentrated in vacuo to gave 2-(benzyloxy)-1-(6-bromo-2-chloropyridin-3-yl)ethanol (1.54g, yield: 95%). MS (M+H): 344. | |
95% | 6-Bromo-2-chloro-3-iodopyridine (1.50 g, 4.71 mmol) was dissolved in THF (15mL) and cooled to -78 C, followed by addition of isopropylmagnesium chloride-lithiumchloride complex (3. 99 mL, 5.18 mmol). The mixture was stirred at -78C for 1 h. 2-(benzyloxy)acetaldehyde (0.849 g, 5.65 mmol) was added and the resulting mixture warmed to0 oc and stirred for 2 h. The mixture was treated with saturated NH4Cl and extracted with ethyl10 acetate. The organic layer was washed with brine, dried (Na2S04), filtered and concentrated in15vacuo to gave 2-(benzyloxy)-1-(6-bromo-2-chloropyridin-3-yl)ethanol (1.54g, yield: 95%). MS(M+Ht: 344. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N,N-dimethylbenzylamine prolinol trimethylsilyl ether; benzoic acid; In isopropyl alcohol; at 25℃; for 24h; | General procedure: The synthesis of catalysts 1 and 2,13 along with ILS-PhCO2H14 is described elsewhere. For the Michael reactions herein, benzyloxyacetaldehyde (0.8mmol) was added to a solution of the catalyst (0.02mmol, 5mol%), nitroolefin (0.4mmol) and benzoic acid (0.2mmol, 50mol%) in isopropanol (0.5mL) at room temperature. The reaction mixture was stirred until complete conversion of the starting materials (monitored by TLC). The solvent was removed and the product was purified by flash column chromatography (silica gel, hexane/AcOEt) to afford the Michael adduct. Percentage yields and syn/anti ratios were determined by 1H NMR spectroscopy. Racemates were synthesized using morpholine as a catalyst in order to identify enantiomers. Enantiomeric excess determinations were made based on comparisons with previously reported literature for determinations.16 Similar chiral HPLC conditions were used for the separation of the enantiomers for each reaction and based on the retention times, NMR and IR data, the identity of each enantiomer was determined. |
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