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Sodium Hydroxide → 2-(4-n-Butylamino-2,2,6,6-tetramethylpiperidin-1-yl) ethanol

HRID 1955947
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HRID 1955947 반응식
[CH2:1]([N:5]([CH:9]1[CH2:14][C:13]([CH3:16])([CH3:15])[N:12]([CH2:17][CH2:18][OH:19])[C:11]([CH3:21])([CH3:20])[CH2:10]1)C(=O)C)[CH2:2][CH2:3][CH3:4].[OH-].[Na+]>Cl>[CH2:1]([NH:5][CH:9]1[CH2:10][C:11]([CH3:20])([CH3:21])[N:12]([CH2:17][CH2:18][OH:19])[C:13]([CH3:15])([CH3:16])[CH2:14]1)[CH2:2][CH2:3][CH3:4]
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HCID 14798Sodium HydroxideHCID 19073314N-n-butyl-N-[1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-yl]acetamide

생성물 1

HCID 543503372-(4-n-Butylamino-2,2,6,6-tetramethylpiperidin-1-yl) ethanol수율 74.9%

시약·촉매·용매 1

HCID 313Hydrochloric Acid용매

실험 절차

) A solution of 12.6 g (42.2 mmol) of N-n-butyl-N-[ 1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-yl]acetamide [Example 1bη2] in 180 ml of 2N hydrochloric acid is refluxed for 48 hours. The reaction mixture is then cooled 0°-5 C. and, after addition of 40 ml of 30% sodium hydroxide solution, extracted twice with toluene. The organic phases are washed with water, combined, dried over sodium sulfate, and concentrated on a vacuum rotary evaporator. Chromatography of the residue on silica gel with the solvent system ethyl acetate/ethanol/triethylamine=50:2:1 yields 8.1 g (68%) of 2-(4-n-butylamino-2,2,6,6-tetramethylpiperidin-1-yl) ethanol (208) as a white powder of m.p. 106°-111° C. Analysis: calcd: C 70.26%; H 12.58%; N 10.92%. found: C 70.42%; H 12.85%; N 11.00%. ##STR65## τ) 833 g (5.30 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 418 g (1.05 mol) of 2-butyne-1,4-diol-ditosylate [C.A. Registry No. 6337-59-3] in 3.6 1 of acetonitrile are placed, under argon, in a round-bottomed flask equipped with magnetic stirrer and condenser. The reaction mixture is refluxed overnight, then cooled, poured on ice and extracted repeatedly with ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated on a vacuum rotary evaporator. Crystallisation of the residue from ethanol yields 295 g (76%) of 1,4-bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)-but-2-yne (209), m.p. 203.4° C., in the form of white crystals. Analysis: calcd: C 72.48%; H 11.06%; N 7.68%. found: C 72.52%; H 11.12%; N 7.75%. ##STR66## κ) The HALS diol (210) is known and described in U.S. Pat. No. 4,569,997 (Ciba-Geigy, Example 1, column 14). ##STR67## λ)1.) 9.15 g (50 mmol) of adipyl dichloride are added dropwise at 0°-5° C., under nitrogen, to a stirred solution of 22.2 g (105 mmol) of 4-n-butylamino-2,2,6,6-tetramethylpiperidine IEP-A-302 020, Example 1, page 41 in 70 ml of triethylamine and 150 ml of toluene. After c. 30 minutes the reaction mixture is heated to c. 100° C. and stirred for 90 minutes at this temperature. The resultant dense suspension is thereafter cooled to room temperature, filtered to remove the salts, and the filtrate is concentrated on a vacuum rotary evaporator. Chromatography of the residue on silica gel with the solvent system ethyl acetate/ethanol/triethylamine=20:1:1 and crystallisation of the pure fractions from hexane yields 17.15 g (64%) of N,N'-di-n-butyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)hexane diamide as a white powder; m.p. 134°-144° C.

후처리

  1. temperatureThe reaction mixture is then cooled 0°-5 C
  2. extractionextracted twice with toluene
  3. washThe organic phases are washed with water
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated on a vacuum rotary evaporator

출처 및 근거

ORD 기록
ord-32cb77f4b9a4454dbc8d2074f0f4bf5f
출처 데이터셋
uspto-grants-1998_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05777008

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