반응 #51641

반응 방정식

bisulfite

pyrrolidine

benzyl bromide

bromotetralone

→

1-(1(RS)-Benzyl-6-bromo-3,4-dihydro-1H-naphthalen-2-ylidene)-pyrrolidinium bromide

수율 73.0%

용매

sodium bicarbonate

toluene

ethyl acetate

반응 조건

후처리

1. 1
   기타Phases were separated
2. 2
   기타the organic phase was transferred to a new flask
3. 3
   workup.ADDITIONtoluene (1 L) was added
4. 4
   workup.DISTILLATIONThe solution was distilled under reduced pressure to a volume of about 500 mL
5. 5
   workup.ADDITIONAn additional 500 mL of toluene was added
6. 6
   workup.DISTILLATIONdistilled under reduced pressure to a volume of about 300 mL
7. 7
   온도The reaction was heated to 150° C. under Dean-Stark conditions
8. 8
   기타about 13 mL of water was collected
9. 9
   온도The toluene solution of pyrrolidine enamine was cooled to 90° C.
10. 10
    workup.WAITAfter 30 min
11. 11
    온도heating
12. 12
    workup.WAITwas continued at 90° C. for 2 h
13. 13
    온도to cool to room temperature and granulate overnight
14. 14
    여과The solids were filtered
15. 15
    세척washed with toluene (2×500 mL)
16. 16
    기타After drying in a vacuum oven overnight (50° C.)
17. 17
    기타the title product of this preparation as a brown solid
18. 18
    기타was collected

실험 절차

A solution of the bisulfite adduct of bromotetralone of formula A-1 wherein Rx is Br (250 g, 760 mmol) (commercially available) in saturated sodium bicarbonate (1.25 L) and ethyl acetate (2.5 L) was stirred vigorously overnight. Phases were separated and the organic phase was transferred to a new flask and toluene (1 L) was added. The solution was distilled under reduced pressure to a volume of about 500 mL. An additional 500 mL of toluene was added and distilled under reduced pressure to a volume of about 300 mL. The solution was cooled to room temperature and pyrrolidine (54.1 g, 760 mmol) was added. The reaction was heated to 150° C. under Dean-Stark conditions. After 2 hr, about 13 mL of water was collected and concentration of a small sample showed the reaction was complete by NMR. The toluene solution of pyrrolidine enamine was cooled to 90° C. and benzyl bromide (105 mL, 912 mmol) was added dropwise. After 30 min, solids began to granulate and the solution became very thick. An additional 500 mL of toluene was added to aid stirring and heating was continued at 90° C. for 2 h. The slurry was allowed to cool to room temperature and granulate overnight. The solids were filtered and washed with toluene (2×500 mL). After drying in a vacuum oven overnight (50° C.), the title product of this preparation as a brown solid was collected: 250 g (557 mmol), 73% yield; mp 203-205° C.; IR (film) ν 1654, 1596 cm−1; 1H NMR (CDCl3) δ 7.25 (s, 1H), 7.17-7.13 (m, 3H), 7.08 (dd, 1H, J=8.3, 1.7 Hz), 6.98-6.93 (m, 2H), 6.68 (d, 1H, J=8.3 Hz), 4.29 (dd, 1H, J=7.5, 7.5 Hz), 4.25-4.17 (m, 2H), 3.95-3.86 (m, 1H), 3.62-3.49 (m, 2H), 3.27 (dd, 1H, J=13.7, 6.6 Hz), 3.14-3.05 (m, 3H), 2.07-1.95 (m, 3H), 1.92-1.84 (m, 1H); 13C NMR (CDCl3) δ 189.2, 137.2, 136.1, 132.2, 131.2, 130.9, 130.6, 129.8, 129.2, 127.8, 122.1, 55.1, 55.2, 51.3, 39.3, 34.0, 25.6, 24.9, 24.2; Anal. calcd for C21H22BrN: C, 56.15; H, 5.16; N, 3.12. Found: C, 55.64; H, 5.22; N, 3.22.

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