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

HRID 1955947
ノート
印刷プレビュー

反応式

HRID 1955947 の反応式
[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]
参加物実験手順後処理出典と根拠反応ノート

参加物

4

反応物 2

HCID 14798Sodium HydroxideHCID 19073314N-n-butyl-N-[1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-yl]acetamide

生成物 1

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

試薬・触媒・溶媒 1

HCID 313Hydrochloric Acid溶媒

実験手順

) 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.

後処理

  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

出典と根拠

ORDレコード
ord-32cb77f4b9a4454dbc8d2074f0f4bf5f
出典データセット
uspto-grants-1998_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05777008

反応ノート

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