반응 #164124

반응 방정식

ether

4-bromoanisole

ether

ether

8-dimethylamino-1,4-dioxa-spiro[4.5]decane-8-carbonitrile

→

desired product

[8-(4-methoxy-phenyl)-1,4-dioxa-spiro[4.5]dec-8-yl]-dimethylamine

용매

THF

반응 조건

후처리

1. 1
   온도heated
2. 2
   기타The solution formed
3. 3
   workup.ADDITIONuntil boiling during the addition
4. 4
   기타A precipitate separated out
5. 5
   workup.STIRRINGthe batch was stirred overnight at RT
6. 6
   workup.ADDITIONThe solution was mixed with NH4Cl solution with ice cooling
7. 7
   기타the phases were separated
8. 8
   추출the aqueous phase extracted three times with ether
9. 9
   세척the combined organic phases washed with saturated NaCl solution and water
10. 10
    건조dried over Na2SO4
11. 11
    농축concentrated to low volume in a vacuum

실험 절차

Magnesium (3.65 g, 150 mmol) and an iodine crystal were provided in a nitrogen atmosphere and heated. Abs. ether (10 mL) was then added and a solution of 4-bromoanisole (18.8 mL, 150 mmol) in abs. ether (150 mL) was added in drops so that the ether lightly boiled. The solution formed was subsequently stirred for 1 h at RT and then mixed in drops with a solution of 8-dimethylamino-1,4-dioxa-spiro[4.5]decane-8-carbonitrile (10.5 g, 50.0 mmol) in abs. THF (100 mL), and the solution heated to 37-40° C. until boiling during the addition. A precipitate separated out and the batch was stirred overnight at RT. The solution was mixed with NH4Cl solution with ice cooling, the phases were separated, the aqueous phase extracted three times with ether, the combined organic phases washed with saturated NaCl solution and water, dried over Na2SO4 and concentrated to low volume in a vacuum. Flash chromatography of the residue with ethyl acetate/methanol (20:1→9:1→4:1→1:4→MeOH) gave the desired product.

출처