N,N,N',N'-Tetramethylethylenediamine → HCID 10607879, compound

Temperature

-45 °C

1,4,-Cyclohexadiene (3.76 mL, 40 mmol, 1 eq.) was dissolved in THF (64 mL) and cooled to −78° C. s-BuLi (40 mL, 44 mmol, 1.1 eq.) was added dropwise and the resulting suspension was treated with TMEDA (6.12 mL, 40 mmol, 1 eq.). The reaction mixture was allowed to warm to −45° C. over 2 hours, TBDMSCl (6.6 g, 44 mmol, 1.1 eq.) in THF (20 mL) was added dropwise and the reaction stirred at room temperature for 1 hour. The reaction was quenched with Et2O and H2O and then extracted with Et2O (3×100 mL). The combined organic layers were washed with sat. NH4.Cl (aq.) (100 mL) and brine (100 mL), dried over MgSO4 and the solvent removed in vacuo. Distillation using Kugelrohr apparatus (125° C., 43 mbar) afforded the product as a colourless oil (5.9 g, 31 mmol, 77% yield). 1H NMR (CDCl3) δ 5.74 (2H, m, H-5), 5.55 (2H, m, H-6), 2.70 (2H, m, H-7), 2.41 (1H, m, H-4), 0.95 (9H, s, H-1), 0.01 (6H, s, H-3); C13 NMR (100 MHz, CDCl3) δ 134.5 (C-4), 121.2 (C-5), 29.3 (C-4), 27.2 (C-7), 26.2 (C-1), 17.7 (C-2), −6.2 (C-3); IR (neat, cm−1) 3029 (m, C—H), 2956 (m, C—H), 1667 (w, C═C); MS (CI, m/z) 195.16 [M+H+].

1. additionwas added dropwise
2. customThe reaction was quenched with Et2O and H2O
3. extractionextracted with Et2O (3×100 mL)
4. washThe combined organic layers were washed with sat. NH4
5. dry with materialCl (aq.) (100 mL) and brine (100 mL), dried over MgSO4
6. customthe solvent removed in vacuo
7. distillationDistillation
8. customKugelrohr apparatus (125° C., 43 mbar)

ORD record

ord-60683a36a8264f7282383aeaed8e4e41

Source dataset

uspto-grants-2009_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07572928B2