Azidotrimethylsilane → HCID 13550542, compound

A mixture of freshly distilled Ti(OiPr)4 (9.5 mL, 32.1 mmol) and TMSN3 (8.4 mL, 64.1 mmol) was refluxed in dry benzene (20 mL) under nitrogen for 5 h until the solution became clear. To this was added a solution of the epoxy alcohol 8 (3.5 g, 21.3 mmol) in 40 mL dry benzene. The resulting mixture was heated under reflux for 15 min, cooled to room temperature and the solvent was removed in vaccuo. The concentrate was diluted with 20 mL of diethyl ether and treated with 15 mL of aq. 5% H2SO4. The aqueous layer was extracted with CH2Cl2 and the combined organic layers were dried over anhydrous Na2SO4 and concentrated to afford the crude product, which was purified by column chromatography using petroleum ether:EtOAc (3:2) to give azido diol 9 (4.2 g, 96%) as a colorless solid. mp 80-81° C. (lit.10 mp 80.5-82° C.); IR: (CHCl3, cm−1): νmax 696, 753, 1039, 1106, 1242, 1554, 2105, 2923, 2960, 3280; 1H NMR (200 MHz, CDCl3): δ 1.79 (t, J=5.3 Hz, 1H), 2.47 (d, J=5.2 Hz, 1H), 2.80 (dd, J=14.2, 8.6 Hz, 1H), 3.02 (dd, J=14.1, 4.2 Hz, 1H), 3.59-3.81 (m, 4H), 7.24-7.32 (m, 5H); 13C NMR (50 MHz, CDCl3): δ 37.0, 63.2, 65.6, 73.2, 126.9, 128.7, 129.3, 137.2; Anal. Calcd for C10H13N3O2: C, 57.96; H, 6.32; N, 20.28. Found: C, 57.85; H, 6.28; N, 20.22%.

1. temperatureThe resulting mixture was heated
2. temperatureunder reflux for 15 min
3. customthe solvent was removed in vaccuo
4. additionThe concentrate was diluted with 20 mL of diethyl ether
5. additiontreated with 15 mL of aq. 5% H2SO4
6. extractionThe aqueous layer was extracted with CH2Cl2
7. dry with materialthe combined organic layers were dried over anhydrous Na2SO4
8. concentrationconcentrated
9. customto afford the crude product, which
10. customwas purified by column chromatography

ORD record

ord-9a937cba3dd54323ad71aafaac414fa4

Source dataset

uspto-grants-2016_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09233943B2