Diisopropylamine → HCID 11349373, compound

To a solution of 27.62 g of dilsopropyl amine in 28 ml of THF was added at −78° 171 ml of n-BuLi (1.6 M in hexane) the solution was warmed to 0° for 30 min and cooled to −78°. The LDA-solution was treated at −78° with a solution of 59.38 g of the crude 10-tert-butoxy-1,1,1-trofluoro-6,6-dimethyl-2-trifluoromethyl-dec-3-yn-2-ol in 20 ml of THF over 40 min and stirring was continued at −78° for 1 h. The yellow solution was treated at −78° with 47.11 g of diethylchlorophosphate over 30 min, the mixture was warmed to 22° over 2 h and stirring was continued at 22° for 2 h. The suspension was added at −78° dropwise to a solution of LDA, prepared with 52.62 g diisopropyl amine, 325 ml of n-BuLi (1.6 M in hexane) and 60 ml of THF as described above, over 20 min and stirring, was continued at −78° for 2 h. The suspension containing the anion of 8-tert-butoxy-4,4-dimethyl-oct-1-yne was treated at −78° with 60.0 g of hexafluor-oacetone over 10 mim and stirring, was continued at −78° for 30 min. The suspension was washed with 300 ml of sat. aqueous NH4Cl and sat. aqueous NaCl, the organic layer was dried over MgSO4 and evaporated to give 107.9 g of crude product. The material was crystallized from 160 ml of hexane at −20° to give 43.00 g of the pure title compound as a white solid, m.p. 66-67°. The mother liquor was purified by chromatography on silica with hexane/AcOEt 19:1 to give 21.1 g of the pure title compound. IR(nujol): 3157m (OH), 2242 m (C,C-triple bond); MS(EI): 361/20 (M—CH3).

1. temperaturewas warmed to 0° for 30 min
2. temperaturecooled to −78°
3. temperaturethe mixture was warmed to 22° over 2 h
4. stirringstirring
5. waitwas continued at 22° for 2 h
6. customover 20 min
7. stirringstirring
8. waitwas continued at −78° for 2 h
9. stirringstirring
10. waitwas continued at −78° for 30 min
11. washThe suspension was washed with 300 ml of sat. aqueous NH4Cl and sat. aqueous NaCl
12. dry with materialthe organic layer was dried over MgSO4
13. customevaporated
14. customto give 107.9 g of crude product
15. customThe material was crystallized from 160 ml of hexane at −20°

ORD record

ord-5b92b4635dbb4ee9a567299660d78537

Source dataset

uspto-grants-2001_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06310262B1