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CAS No. : | 23308-82-9 | MDL No. : | MFCD00021866 |
Formula : | C9H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZUBPFBWAXNCEOG-UHFFFAOYSA-N |
M.W : | 152.19 | Pubchem ID : | 90902 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
60% | Triphenylphosphine (1.2 equiv.) and phthalimide(1 equiv.) were added to a solution of (R)-1h (0.23 mmol)in 3 mL of dry tetrahydrofuran (THF), under nitrogenatmosphere and magnetic stirring. The solution wascooled to 0 C and diisopropyl azodicarboxylate (DIAD,1.2 equiv.) was added. The mixture was heated to 25 Cand stirred for approximately 3 h. The solvent wasremoved by vacuum and the product was purified by flashchromatography using a hexane/ethyl acetate gradientas the mobile phase and a Biotage Isolera Spektra Onesystem. The protected amine was dissolved in THF (3 mL)and ethanol (1 mL), and hydrazine monohydrate (50 muL)was added. The reaction was stirred at 66 C for 2 h.The white suspension formed was filtered and washedwith THF, and the organic solvent was evaporated invacuum, producing a light-yellow oil, (S)-3h, with 60%yield (0.14 mmol). MS (m/z, %): 151 (M+, 9), 136 (100),109 (16), 94 (10), 77 (8), 44 (12); 1H NMR (400 MHz,CDCl3) delta 1.39 (d, 3H, J 6.8 Hz), 1.86 (br s, 2H), 3.82(s, 3H), 4.10 (q, 1H, J 6.8 Hz), 6.78 (m, 1H), 6.93 (m,2H), 7.26 (m, 1H); 13C NMR (100 MHz, CDCl3)delta 25.5,51.3, 55.2, 111.4, 112.2, 118.1, 129.5, 149.4, 159.9;[alpha]D20 -26.0 (c 1.0; CHCl3) 91% ee (S), Lit.47 [alpha]D20 -26.8(c 1.15; CHCl3) ? 96% ee for the (S)-enantiomer.47 In order to determine the enantiomeric excess, the enantioenrichedamine (S)-3h was acetylated and its GC chromatogramcompared to that obtained for the acetylated racemiccompound. Thus, chemical acetylation was carried outusing approximately 1 mg of the amine (S)-3h dissolvedin ethyl acetate (1 mL), added with K2CO3 (10 mg) andacetic anhydride (250 muL). The mixture was shaken at30 C and 900 rpm for 1 h and an aqueous 10 mol L-1NaOH solution (200 muL) was added. The organic layerwas separated, dried with anhydrous sodium sulfate andtransferred to a GC glass vial for analysis.48 Enantiomericexcess was determined by GC-FID at temperatures of120-160 C (0.4 C min-1) and 160-180 C (5 C min-1) and kept constant for 5 min; tS = 91.86 min [(S)-enantiomer];tR 93.08 min [(R)-enantiomer]. |
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