Hydroxyamine hydrochloride → tert-butyl 4-(hydroxyimino)-3,4-dihydro-2H-spiro[naphthalene-1,4'-piperidine]-1'-carboxylate

HRID 506543ノート

反応式

HRID 506543 の反応式
O=[C:2]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:5]2([CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]2)[CH2:4][CH2:3]1.Cl.[NH2:25][OH:26].O.O.O.C([O-])(=O)C.[Na+]>C(O)C>[OH:26][N:25]=[C:2]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:5]2([CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]2)[CH2:4][CH2:3]1

参加物

5

反応物 3

HCID 443297Hydroxyamine hydrochlorideHCID 23665404Sodium Acetate TrihydrateHCID 49760950Tert-butyl 4-oxo-3,4-dihydro-2H-spiro[naphthalene-1,4'-piperidine]-1'-carboxylate

生成物 1

HCID 86620083tert-butyl 4-(hydroxyimino)-3,4-dihydro-2H-spiro[naphthalene-1,4'-piperidine]-1'-carboxylate

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

A mixture of tert-butyl 4-oxo-3,4-dihydro-2H-spiro[naphthalene-1,4′-piperidine]-1′-carboxylate A (1.24 g, 3.93 mmol), hydroxylamine hydrochloride (1.37 g, 19.7 mmol) and sodium acetate trihydrate (3.20 g, 23.5 mmol) in ethanol (50 ml) was heated under reflux for 20 h. The reaction was concentrated and the residue was suspended in water, extracted with dichloromethane (3×). The combined extracts were dried over Na2SO4 and concentrated to give tert-butyl 4-(hydroxyimino)-3,4-dihydro-2H-spiro[naphthalene-1,4′-piperidine]-1′-carboxylate B (1.32 g). LC-MS: m/e=331.1 (M+H, 100%), 275.0 (M+H−C(CH3)3). Rt=3.35 min. 1H-NMR (500 MHz, CDCl3): 8.01 (d, 0.25H), 7.93 (d, 0.75H), 7.41-7.34 (m, 2H), 7.23-7.19 (m, 1H), 3.95-3.92 (m, 2H), 3.04-2.96 (m, 2H), 2.87 (t, 0.5H), 2.82 (t, 1.5H), 2.3 (br. s, 1H), 1.93-1.84 (m, 4H), 1.54-1.52 (d, 2H), 1.43 (s, 9H).

後処理

  1. temperaturewas heated
  2. temperatureunder reflux for 20 h
  3. concentrationThe reaction was concentrated
  4. extractionextracted with dichloromethane (3×)
  5. dry with materialThe combined extracts were dried over Na2SO4
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-2dd5f4889c0e498197ff422bb844c9fa
出典データセット
uspto-grants-2010_08
特許番号
US07786107B2

反応ノート

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