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Sulfuric Acid → 1'-t-butoxycarbonylspiro[benzo[c]thiophene-1(3H),4'-piperidine]

HRID 278945
ノート
印刷プレビュー

反応式

HRID 278945 の反応式
[CH:1]1[CH:6]=[C:5]([CH2:7][SH:8])[C:4](Br)=[CH:3][CH:2]=1.C([Li])CCC.[C:15]([O:19][C:20]([N:22]1[CH2:27][CH2:26][C:25](=O)[CH2:24][CH2:23]1)=[O:21])([CH3:18])([CH3:17])[CH3:16].[Cl-].[NH4+].S(=O)(=O)(O)O.[OH-].[Na+].C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O>O1CCCC1.CCCCCC>[C:15]([O:19][C:20]([N:22]1[CH2:27][CH2:26][C:25]2([C:4]3[CH:3]=[CH:2][CH:1]=[CH:6][C:5]=3[CH2:7][S:8]2)[CH2:24][CH2:23]1)=[O:21])([CH3:18])([CH3:16])[CH3:17]
参加物実験手順後処理出典と根拠反応ノート

参加物

10

反応物 7

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 25517Ammonium ChlorideHCID 90495Di-tert-butyl dicarbonateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 2773673(2-Bromophenyl)methanethiolHCID 178418339Butyllithium

生成物 1

HCID 105665171'-t-butoxycarbonylspiro[benzo[c]thiophene-1(3H),4'-piperidine]収率 45.8%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

実験手順

In 800 ml of tetrahydrofuran, 81.0 g (0.40 mole) of 2-bromobenzylthiol were dissolved, followed by the dropwise addition of 516 ml (0.84 mole) of n-butyl lithium (1.6 mole, a hexane solution) at −78° C. over 6 hours. After stirring at the same temperature for 1.5 hours, a solution of 79.5 g (0.40 mole) of N-tert-butoxycarbonyl-4-piperidone in 800 ml of tetrahydrofuran was added dropwise to the reaction mixture over 3 hours and then the mixture was stirred for a further 1 hour. A saturated aqueous solution of ammonium chloride was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to afford a residue. To the residue, 2 liters of 4N sulfuric acid were added and the mixture was heated under reflux for 14 hours. Under ice-cooling, the reaction mixture was made alkaline with 350 g (8.75 mole) of sodium hydroxide, followed by addition of 102 g (0.47 mole) of di-tert-butyl dicarbonate. The resulting mixture was stirred for 1 hour. The reaction mixture was extracted with methylene chloride. The organic layer was washed with a saturated aqueous solution of sodium chloride and then dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent of the extract under reduced pressure was purified by chromatography on a silica gel column (eluting solvent; n-hexane:ethyl acetate=97:3), whereby 56 g of the title compound were obtained as white crystals.

後処理

  1. stirringthe mixture was stirred for a further 1 hour
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customto afford a residue
  7. temperaturethe mixture was heated
  8. temperatureunder reflux for 14 hours
  9. temperatureUnder ice-cooling
  10. stirringThe resulting mixture was stirred for 1 hour
  11. extractionThe reaction mixture was extracted with methylene chloride
  12. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  13. dry with materialdried over anhydrous sodium sulfate
  14. customThe residue obtained
  15. distillationby distilling off the solvent of the
  16. extractionextract under reduced pressure
  17. customwas purified by chromatography on a silica gel column (eluting solvent; n-hexane:ethyl acetate=97:3)

出典と根拠

ORDレコード
ord-318600accf83416992718ffc2c292d14
出典データセット
uspto-grants-2002_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06362179B1

反応ノート

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