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 1393225Notes

Reaction equation

HRID 1393225 reaction equation
[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]

Participants

6

Reactant 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

Product 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

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-6da0946310294cb0a8707476552d6572
Source dataset
uspto-grants-2008_03
Patent number
US07345056B2

Reaction notes

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