Benzyl Bromide → 1-(1(Rs)-benzyl-6-bromo-3,4-dihydro-1h-naphthalen-2-ylidene)-pyrrolidinium bromide

HRID 413960

반응식

HRID 413960 반응식
S(=O)(O)[O-].[Br:5][CH:6]1[CH2:15][CH2:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]1=O.[NH:17]1[CH2:21][CH2:20][CH2:19][CH2:18]1.[CH2:22](Br)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>C(=O)(O)[O-].[Na+].C(OCC)(=O)C.C1(C)C=CC=CC=1>[Br-:5].[CH2:22]([CH:12]1[C:13]2[C:8](=[CH:7][C:6]([Br:5])=[CH:15][CH:14]=2)[CH2:9][CH2:10][C:11]1=[N+:17]1[CH2:21][CH2:20][CH2:19][CH2:18]1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

참가 물질

8

반응물 4

HCID 7498Benzyl BromideHCID 31268PyrrolidineHCID 1011201(2H)-Naphthalenone, 2-bromo-3,4-dihydro-HCID 104748Bisulfite

생성물 1

HCID 112130581-(1(Rs)-benzyl-6-bromo-3,4-dihydro-1h-naphthalen-2-ylidene)-pyrrolidinium bromide수율 73%

시약·촉매·용매 3

HCID 1140Toluene용매HCID 8857Ethyl Acetate용매HCID 516892Sodium Bicarbonate용매

실험 절차

A solution of the bisulfite adduct of bromotetralone (250 grams, 760 mmol) in saturated sodium bicarbonate (1.25 L) and ethyl acetate (2.5 L) was stirred vigorously overnight. Phases were separated and the organic was transferred to a new flask and toluene (1 L) was added. The solution was distilled under reduced pressure to a volume of approximately 500 mL. An additional 500 mL of toluene was added and distilled under reduced pressure to a volume of approximately 300 mL. The solution was cooled to room temperature and pyrrolidine (54.1 grams, 760 mmol) was added. The reaction was heated to 150° C. under Dean-Stark conditions. After 2 hours approximately 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 minutes 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 hours. The slurry was allowed to cool to room temperature and granulate overnight. The solids were filtered and washed with toluene (2 times 500 mL). After drying in a vacuum oven overnight (50° C.) a brown solid was collected: 250 grams (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); 13 C 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.

후처리

  1. customPhases were separated
  2. customthe organic was transferred to a new flask
  3. additiontoluene (1 L) was added
  4. distillationThe solution was distilled under reduced pressure to a volume of approximately 500 mL
  5. additionAn additional 500 mL of toluene was added
  6. distillationdistilled under reduced pressure to a volume of approximately 300 mL
  7. temperatureThe reaction was heated to 150° C. under Dean-Stark conditions
  8. customAfter 2 hours approximately 13 mL of water was collected
  9. temperatureThe toluene solution of pyrrolidine enamine was cooled to 90° C.
  10. temperatureheating
  11. waitwas continued at 90° C. for 2 hours
  12. temperatureto cool to room temperature and granulate overnight
  13. filtrationThe solids were filtered
  14. washwashed with toluene (2 times 500 mL)
  15. customAfter drying in a vacuum oven overnight (50° C.) a brown solid
  16. customwas collected

출처 및 근거

ORD 기록
ord-e5a466d3e4a54b0d97e449970494a3df
출처 데이터셋
uspto-grants-2003_05
특허 번호
US06570020B2

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