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Hydrochloric Acid → 4-(7-Bromo-5-methoxy-benzofuran-2-yl)-1-ethoxycarbonyl-piperidine

HRID 486288
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HRID 486288 반응식
[Cl-].[Br:2][C:3]1[C:4]([O:31][C:32]([CH:34]2[CH2:39][CH2:38][N:37]([C:40]([O:42][CH2:43][CH3:44])=[O:41])[CH2:36][CH2:35]2)=O)=[C:5]([CH2:11][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1.C(=O)([O-])[O-].[K+].[K+].O.Cl>C(#N)C>[Br:2][C:3]1[C:4]2[O:31][C:32]([CH:34]3[CH2:35][CH2:36][N:37]([C:40]([O:42][CH2:43][CH3:44])=[O:41])[CH2:38][CH2:39]3)=[CH:11][C:5]=2[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1
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참가 물질

6

반응물 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 11430Potassium CarbonateHCID 21470005(3-Bromo-2-((1-(ethoxycarbonyl)piperidine-4-carbonyl)oxy)-5-methoxybenzyl)triphenylphosphonium chloride

생성물 1

HCID 111434314-(7-Bromo-5-methoxy-benzofuran-2-yl)-1-ethoxycarbonyl-piperidine수율 90%

시약·촉매·용매 1

HCID 6342
Acetonitrile
용매

실험 절차

In the course of 30 minutes, at 25° to 30°, with the exclusion of air, 50 g of [(3-bromo-2-[(1-ethoxycarbonylpiperid-4-yl)carbonyloxy]-5-methoxy-phenyl)methyl]-triphenyl-phosphonium chloride are introduced into a suspension of 20 g of ground potassium carbonate (anhydrous) in 100 ml of acetonitrile. The mixture is stirred for 2 hours at room temperature, then 80 ml of water are added thereto, and the mixture is acidified to pH 1.0 with concentrated hydrochloric acid. The organic phase is separated off and concentrated by evaporation. The oily residue is taken up in 50 ml of toluene and at 20°, in the course of 1 hour, 100 ml of hexane are added; the major portion (approx. 90%; content according to HPLC: 90%) of the triphenylphosphane oxide that forms crystallises out. The crystal suspension is filtered with suction and the filter cake is washed twice with 40 ml of hexane/toluene (3:2) each time. Concentration of the combined filtrates by evaporation and chromatography of the residue on silica gel with toluene/ethyl acetate (2:1) as eluant yield 4-(7-bromo-5-methoxy-benzofuran-2-yl)-1-ethoxycarbonyl-piperidine [m.p.: 85°; 1H-NMR (360 MHz, CDCl3): 1.28 (t, 3H, CO2CH2CH3), 1.69 (m, 2H), 2.09 (m, 2H), 2.95 (m, 3H), 3.80 (s, 3H, OCH3), 4.16 (q, 2H, CO2CH2CH3), 4.14 to 4.35 (br. m, 2H), 6.36 (s, 1H), 6.90 (d, 1H), 7.00 (d, 1H) ppm]; yield 90% of the theoretical yield.

후처리

  1. customThe organic phase is separated off
  2. concentrationconcentrated by evaporation
  3. customis taken up in 50 ml of toluene and at 20°, in the course of 1 hour, 100 ml of hexane
  4. additionare added
  5. customthe major portion (approx. 90%; content according to HPLC: 90%) of the triphenylphosphane oxide that forms crystallises out
  6. filtrationThe crystal suspension is filtered with suction
  7. washthe filter cake is washed twice with 40 ml of hexane/toluene (3:2) each time
  8. customConcentration of the combined filtrates by evaporation and chromatography of the residue on silica gel with toluene/ethyl acetate (2:1) as eluant

출처 및 근거

ORD 기록
ord-0158902113db428db7b38bbe9f5e61d5
출처 데이터셋
uspto-grants-1994_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05290939

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