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

HRID 1938817
ノート
印刷プレビュー

反応式

HRID 1938817 の反応式
[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
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6342
Acetonitrile
溶媒

実験手順

In the course of 30 minutes, at 25° to 30°, with the exclusion of air, 50 g of [(3-bromo-2-[(1 -ethoxycarbonylpiperid4-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, CO2 CH2CH3), 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.

後処理

  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

出典と根拠

ORDレコード
ord-94c9cda50745423eb16d419044c0b2a6
出典データセット
uspto-grants-1997_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05693807

反応ノート

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