Carbon Dioxide → HCID 71283793, compound

4,4′-Methylenebis(3-bromo-N,N-dimethylaniline 1 (2.00 g, 4.85 mmol, 1 eq.) was dissolved in dry THF (200 ml) and stirred at −78° C. on the CO2(s)/acetone bath. sec-BuLi (1.4 mol/l solution in n-hexane, 10 ml, 14.0 mmol, 3 eq.) was slowly added for 30 minutes to the solution and stirred for further 2 hr at the same temperature. SiMe2Cl2 (1 ml, 8.22 mmol, 1.8 eq.) was added to the reaction mixture and stirred at room temperature for 2 hr. 1N HCl aqueous solution was added carefully to neutralize the solution, and THF was evaporated. The resulting aqueous solution was extracted with EtOAc, and the organic phase was washed with saturated NaHCO3 aqueous solution, water and brine, dried over Na2SO4, filtered and evaporated to obtain the crude including N3,N3,N7,N7,5,5-hexamethyl-5,10-dihydrodibenzo[b,e]siline-3,7-diamine 2, which was used for the next reaction immediately due to its high sensitivity toward oxygen. The resulting crude including 2 was dissolved in acetone (30 ml) and stirred at −15° C. on the crashed ice/NaCl(s) bath. KMnO4 powder was added portionwise (300 mg×6) for 30 minutes, and stirring was continued for further 2 hr at the same temperature. The purple suspension was filtered through a Celite pad, and the yellow filterate was evaporated. The resulting residue was purified by silica gel column chromatography (nhexane/CH2Cl2=20/80) to obtain 3,7-Bis(dimethylamino)-5,5-dimethyldibenzo[b,e]silin-10(5H)-one as a yellow solid. (689 mg, 41%)

1. stirringstirred at room temperature for 2 hr
2. customwas evaporated
3. extractionThe resulting aqueous solution was extracted with EtOAc
4. washthe organic phase was washed with saturated NaHCO3 aqueous solution, water and brine
5. dry with materialdried over Na2SO4
6. filtrationfiltered
7. customevaporated
8. customto obtain the crude
9. stirringstirring
10. waitwas continued for further 2 hr at the same temperature
11. filtrationThe purple suspension was filtered through a Celite pad
12. customthe yellow filterate was evaporated
13. customThe resulting residue was purified by silica gel column chromatography (nhexane/CH2Cl2=20/80)

ORD record

ord-c0ffc28514134b529245c7d14b1f50af

Source dataset

uspto-grants-2016_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09346957B2