반응 #6379

반응 방정식

lithium bromide

Water

7-(acetyloxy)-β-chloro-3a,4,5,6,7,7a-hexahydro-δ,3a-dimethyl-1H-indene-3-butanol

p-toluenesulfonyl chloride

→

title compound

7-(acetyloxy)-3-(3-chloro-4-bromo-1-methylbutyl)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene

용매

—

ice water

dichloromethane

pyridine

반응 조건

후처리

1. 1
   workup.STIRRINGafter stirring the resulting mixture for 1 hour at room temperature
2. 2
   기타the solvents were removed in vacuo
3. 3
   workup.ADDITIONthe residue diluted with water
4. 4
   추출extracted with ethyl acetate
5. 5
   세척The combined organic extracts were subsequently washed with 1N hydrochloric acid, water, 2N aqueous potassium bicarbonate solution and brine
6. 6
   기타dried
7. 7
   기타The residue obtained
8. 8
   기타after evaporation of the ethyl acetate (weighing 2.10 g)
9. 9
   workup.DISSOLUTIONwas dissolved in 40 mL of N,N-dimethylformamide
10. 10
    온도After cooling
11. 11
    추출extracted with ethyl acetate
12. 12
    세척The combined organic extracts were washed several times with water
13. 13
    기타dried
14. 14
    기타evaporated to dryness
15. 15
    기타to give

실험 절차

A solution of 1.50 g (4.76 mmol) of [3aS-[3(βS*,δR*), 3aα,7β,7aβ]]-7-(acetyloxy)-β-chloro-3a,4,5,6,7,7a-hexahydro-δ,3a-dimethyl-1H-indene-3-butanol in 20 mL of dichloromethane and 20 mL of pyridine was treated at 0° C. and under argon with 4.50 g (23.60 mmol) of p-toluenesulfonyl chloride and then stirred overnight at 0° C. Water (8 mL) was then added and, after stirring the resulting mixture for 1 hour at room temperature, the solvents were removed in vacuo and the residue diluted with water and extracted with ethyl acetate. The combined organic extracts were subsequently washed with 1N hydrochloric acid, water, 2N aqueous potassium bicarbonate solution and brine and dried. The residue obtained after evaporation of the ethyl acetate (weighing 2.10 g) was dissolved in 40 mL of N,N-dimethylformamide and heated under argon at 50° C. with 4.00 g (46.06 mmol) of anhydrous lithium bromide for 17 hours. After cooling, the reaction mixture was diluted with ice water and extracted with ethyl acetate. The combined organic extracts were washed several times with water, dried and evaporated to dryness to give 1.62 g (90% overall yield) of the title compound. 1H NMR (60 MHz, CDCl3) δ0.88 (s, 3H), 1.07 (d, J=6.4 Hz, 3H), 2.03 (s, 3H), 3.60 (br AB q, J=10.2 Hz, Δγ=14.0 Hz, 2H), 5.00 (br m, 1H), 5.33 (br s, 1H) ppm.

출처