Acetic Acid → Tert-butyl 12-(4-chlorophenyl)sulfonyl-4,5,10,12-tetrazatricyclo[6.3.1.02,6]dodeca-2(6),3-diene-10-carboxylate

HRID 2354889ノート

反応式

HRID 2354889 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:15][CH:14]2[N:16]([S:17]([C:20]3[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][CH:21]=3)(=[O:19])=[O:18])[CH:10]([CH2:11][C:12](=O)[C:13]2=[CH:27]O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(O)(=O)C.O.[NH2:35][NH2:36].C([O-])(O)=O.[Na+]>C(O)C>[C:1]([O:5][C:6]([N:8]1[CH2:15][CH:14]2[N:16]([S:17]([C:20]3[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][CH:21]=3)(=[O:18])=[O:19])[CH:10]([CH2:11][C:12]3[NH:35][N:36]=[CH:27][C:13]=32)[CH2:9]1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

参加物

6

反応物 4

HCID 176Acetic AcidHCID 24654Hydrazine hydrate (1:1)HCID 516892Sodium BicarbonateHCID 668422599-(4-Chloro-benzenesulfonyl)-6-hydroxymethylene-7-oxo-3,9-diaza-bicyclo[3.3.1]nonane-3-carboxylic acid tert-butyl ester

生成物 1

HCID 45487090Tert-butyl 12-(4-chlorophenyl)sulfonyl-4,5,10,12-tetrazatricyclo[6.3.1.02,6]dodeca-2(6),3-diene-10-carboxylate

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

To a solution of 9-(4-chloro-benzenesulfonyl)-6-hydroxymethylene-7-oxo-3,9-diaza-bicyclo[3.3.1]nonane-3-carboxylic acid tert-butyl ester (4.91 g, 11.1 mmol) in ethanol (20 mL) was added glacial acetic acid (0.5 mL) followed by hydrazine monohydrate (5.39 mL, 111.1 mmol). The reaction mixture was stirred at room temperature for 1 h after which saturated NaHCO3 (10 mL) was added. The resulting solution was extracted with EtOAc (3×20 mL), the organic extracts were combined, dried (Na2SO4), filtered, concentrated and purified by silica gel column chromatography (eluant hexane/EtOAc, 9/1 to 2/8) and preparative HPLC to give 12-(4-chloro-benzenesulfonyl)-4,5,10,12-tetraaza-tricyclo[6.3.1.02,6]dodeca-2(6),3-diene-10-carboxylic acid tert-butyl ester as a white solid. Retention time (min)=1.794, method [1], MS (ESI) 439.1 (M+H); 1H NMR (300 MHz, CDCl3) δ 7.60 (d, J=8.2 Hz, 2H), 7.40 (s, 1H), 7.32 (d, J=8.2 Hz, 2H), 5.39 (s, 1H), 4.31 (s, 1H), 4.15-4.00 (m, 1H), 3.90 (d, J=12.1 Hz, 1H), 3.39-3.10 (m, 2H), 2.75-2.60 (m, 2H), 1.20-1.07 (m, 9H).

後処理

  1. additionwas added
  2. extractionThe resulting solution was extracted with EtOAc (3×20 mL)
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified by silica gel column chromatography (eluant hexane/EtOAc, 9/1 to 2/8) and preparative HPLC

出典と根拠

ORDレコード
ord-851e3a460bb04f5391e9f56595d228bc
出典データセット
uspto-grants-2010_07
特許番号
US07754712B2

反応ノート

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