Diisopropylamine → HCID 13826417, compound

A solution of n-butyl lithium in hexane (3.2 ml, 4.3 mmoles) was added dropwise (3 minutes) to a solution of diisopropylamine (0.45 g, 4.5 mmoles) in dry tetrahydrofuran (10 ml) with cooling (ice bath). After stirring under nitrogen for 15 minutes, ethylidene cyclohexylimine (0.55 g, 4.3 mmole) was added dropwise (5 minutes) at 0° C. The mixture was stirred for 15 minutes and then the ice bath was replaced by a dry-ice-acetone bath. A solution of 1-chloromethyl-2,4,7-trichloronaphthalene (1.0 g, 3.8 mmoles) in tetrahydrofuran (15 ml) was added (5 minutes) at -75° C. The reaction mixture was stirred at -70° C. for 30 minutes and at room temperature overnight (20 hours) and then concentrated to dryness in vacuo. The residual oil was taken up in ether (100 ml) and 5% aqueous oxalic acid (100 ml) and the mixture stirred at room temperature for 31/2 hours. The layers were separated and the aqueous phase extracted (2X) with ether. The ether extracts were combined, washed with cold water and brine, and dried over MgSO4. The solution was filtered and concentrated in vacuo to give a red-brown oil (1.1 g). This material was chromatographed using a 50 mm flash column containing 150 g of silica gel (230-400 mesh) eluting with 30% methylene chloride in hexane (v/v) to give 0.21 g of the title compound as a pale yellow solid.

1. temperaturewith cooling (ice bath)
2. stirringThe mixture was stirred for 15 minutes
3. stirringThe reaction mixture was stirred at -70° C. for 30 minutes and at room temperature overnight (20 hours)
4. concentrationconcentrated to dryness in vacuo
5. stirring5% aqueous oxalic acid (100 ml) and the mixture stirred at room temperature for 31/2 hours
6. customThe layers were separated
7. extractionthe aqueous phase extracted (2X) with ether
8. washwashed with cold water and brine
9. dry with materialdried over MgSO4
10. filtrationThe solution was filtered
11. concentrationconcentrated in vacuo

ORD record

ord-4e55270511544b098d78142212df701d

Source dataset

uspto-grants-1987_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04654363