Trimethyl borate → Cyclopropyl-(4-hydroxymethyl-piperidin-1-yl)-methanone

HRID 5138

반응식

HRID 5138 반응식
[CH:1]1([C:4]([N:6]2[CH2:11][CH2:10][CH:9]([C:12](OCC)=[O:13])[CH2:8][CH2:7]2)=[O:5])[CH2:3][CH2:2]1.[BH4-].[Li+].B(OC)(OC)OC>O1CCCC1.O>[CH:1]1([C:4]([N:6]2[CH2:7][CH2:8][CH:9]([CH2:12][OH:13])[CH2:10][CH2:11]2)=[O:5])[CH2:2][CH2:3]1

참가 물질

6

반응물 3

HCID 8470Trimethyl borateHCID 4148881Lithium borohydrideHCID 10036613Ethyl 1-(cyclopropylcarbonyl)piperidine-4-carboxylate

생성물 1

HCID 10012597Cyclopropyl-(4-hydroxymethyl-piperidin-1-yl)-methanone수율 63.7%

시약·촉매·용매 2

HCID 962Water용매2회HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of 1-(cyclopropylcarbonyl)-4-carboethoxy piperidine (35 g, 156 mmol) in anhydrous tetrahydrofuran (350 mL) was stirred at ambient temperature under a nitrogen atmosphere. A solution of lithium borohydride in tetrahydrofuran (2M, 78 mL, 156 mmol) was added dropwise. Trimethyl borate (1.77 mL, 15.7 mmol) was added, then the reduction mixture was stirred for about 48 hours. Water was added dropwise with vigorous stirring until the vigorous gas evolution ceased. The mixture was diluted twofold with water and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Vacuum distillation (bp 165° C., 0.5 mm Hg) gave a clear, colorless liquid (18.2 g): IR (neat): 3410 (br, s), 3094 (w), 3008 (s), 2918 (s), 2858 (s), 1738 (m), 1613 (s), 1448 (s), 1375 (s), 1316 (s); 1H-NMR: 4.7-4.5 (m, 1H), 4.4-4.1 (m, 1H), 3.6-3.4 (m, 2H), 3.2-2.5 (m, 3H), 2.0-1.7 (m, 4H), 1.4-1.1 (m, 1H), 1.0-0.8 (m, 2H), 0.8-0.65 (m, 2H); HRMS: Calcd for C10H17NO2 :183.1259; Found: 183.1250; Anal.: Calcd for C10H17NO2 :C, 65.54, H, 9.35, N, 7.64; Found: C, 65.83, H, 9.43, N, 7.50.

후처리

  1. stirringwith vigorous stirring until the vigorous gas evolution
  2. extractionextracted three times with ethyl acetate
  3. dry with materialThe combined organic layers were dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. distillationVacuum distillation (bp 165° C., 0.5 mm Hg)

출처 및 근거

ORD 기록
ord-832f1035ccee4e16b54fec29013e82eb
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05243048

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