4-Hydroxy-2,2,6,6-tetramethylpiperidine → 2,2,6,6-Tetramethylpiperidin-4-yl 6-(octanoylamino)hexanoate

HRID 2298442ノート

反応式

HRID 2298442 の反応式
[C:1]([NH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])(=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[CH3:20][C:21]1([CH3:30])[CH2:26]C(O)[CH2:24][C:23]([CH3:29])([CH3:28])[NH:22]1>C(O[Sn](CCCC)(CCCC)O[Sn](OC(=O)C)(CCCC)CCCC)(=O)C.C1(C)C=CC=CC=1>[C:1]([NH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH:19]1[CH2:24][C:23]([CH3:29])([CH3:28])[NH:22][C:21]([CH3:30])([CH3:26])[CH2:20]1)=[O:17])(=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

参加物

5

反応物 2

HCID 754714-Hydroxy-2,2,6,6-tetramethylpiperidineHCID 11747683Methyl 6-(octanoylamino)hexanoate

生成物 1

HCID 121493962,2,6,6-Tetramethylpiperidin-4-yl 6-(octanoylamino)hexanoate収率 90%

試薬・触媒・溶媒 2

HCID 16682981Acetic acid, 1,1'-(1,1,3,3-tetrabutyl-1,3-distannoxanediyl) ester触媒HCID 1140Toluene溶媒

反応条件

温度
110 °C

実験手順

A 250 mL single-necked reaction flask was equipped with a magnetic stirrer and a Dean-Stark trap fitted with a condenser and nitrogen inlet/outlet. To this flask was charged 6.1 g (22.5 mmol) of compound D, 5.29 g (33.7 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 150 mL of toluene. Under a slow nitrogen flow, 8 mL of toluene was distilled off and the trap drained. After lowering the heat source and allowing the mixture to cool to 110° C., 0.17 g (0.28 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heat source raised. Another 100 mL of toluene was slowly distilled off over 16 hours and the resulting mixture was cooled to room temperature and diluted with methylene chloride. The organic solution was washed with water to remove excess amino alcohol and dried over anhydrous sodium carbonate. Filtration and removal of solvent under reduced pressure followed by further solvent removal in vacuo (<1 mm) at 60° C. gave 8.0 g (90%) of Compound VI as a light brown wax. The structure of the material was confirmed by 1H NMR analysis. 1H NMR (CDCl3): δ 5.60 (m, 1H, NHCO—); 5.18 (m, 1H, R2CHOCO—); 3.25 (dt, 2H, —CH2—NH—); 2.28 (t, 2H, —CH2COO—); 2.16 (t, 2H, —CH2CONH—); 1.95-1.10 (m, 20H, CH2(CH2)3CH2, CH2(CH2)5, CH2CH2C(CH3)2); 1.20 (d, 12H, CH2C(CH3)2; 0.88 (t, 3H, —CH2CH3).

後処理

  1. customA 250 mL single-necked reaction flask was equipped with a magnetic stirrer
  2. customa Dean-Stark trap fitted with a condenser and nitrogen inlet/outlet
  3. distillationUnder a slow nitrogen flow, 8 mL of toluene was distilled off
  4. temperaturethe heat source raised
  5. distillationAnother 100 mL of toluene was slowly distilled off over 16 hours
  6. temperaturethe resulting mixture was cooled to room temperature
  7. additiondiluted with methylene chloride
  8. washThe organic solution was washed with water
  9. customto remove excess amino alcohol
  10. dry with materialdried over anhydrous sodium carbonate
  11. filtrationFiltration and removal of solvent under reduced pressure
  12. customfollowed by further solvent removal in vacuo (<1 mm) at 60° C.

出典と根拠

ORDレコード
ord-1ccca0ac12c447e6acca4f487bc5aca3
出典データセット
uspto-grants-2002_12
特許番号
US06492521B2

反応ノート

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