Triethylamine → 8-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-2-ylamine

温度

95 °C

To a solution of 8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid (12.5 g, 38.3 mmol) in tert-butanol (250 mL) were added triethylamine (5.5 mL, mmol) and diphenylphosphoryl-azide (8.6 mL, 40 mmol). The reaction mixture was stirred at 95° C. for 16 h, then allowed to cool down to RT, and concentrated in vacuo. The resultant residue was dissolved in ethyl acetate, washed successively with water, aqueous saturated sodium bicarbonate solution and brine, dried (MgSO4) and concentrated in vacuo. The resultant residue was dissolved in DCM (150 mL) and treated with trifluoroacetic acid (50 mL). The reaction mixture was stirred at RT for 3 h then concentrated in vacuo. The resulting residue was triturated with 20% ethyl acetate/cyclohexane and filtered to afford the title compound as an off-white solid (7.94 g, 70%). LCMS (Method A): RT=3.13 min, [M+H]=297 and 299. 1H NMR (DMSO-d6): 8.01 (1 H, d, J=8.6 Hz), 7.30-7.25 (1 H, d, J=8.6, 2.1 Hz), 7.19 (1 H, d, J=2.1 Hz), 4.27 (2 H, t, J=5.1 Hz), 3.08 (2 H, t, J=5.1 Hz).

1. temperatureto cool down to RT
2. concentrationconcentrated in vacuo
3. dissolutionThe resultant residue was dissolved in ethyl acetate
4. washwashed successively with water, aqueous saturated sodium bicarbonate solution and brine
5. dry with materialdried (MgSO4)
6. concentrationconcentrated in vacuo
7. dissolutionThe resultant residue was dissolved in DCM (150 mL)
8. additiontreated with trifluoroacetic acid (50 mL)
9. stirringThe reaction mixture was stirred at RT for 3 h
10. concentrationthen concentrated in vacuo
11. customThe resulting residue was triturated with 20% ethyl acetate/cyclohexane
12. filtrationfiltered

ORDレコード

ord-49ecf24ded134084a9677d2694ea7549

出典データセット

uspto-grants-2014_09

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08846762B2