Acetic Acid → HCID 22312185, compound

HRID 2294872Notes

Reaction equation

HRID 2294872 reaction equation
[CH3:1][CH:2]([N:4]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[N:8]([CH:15]([CH3:17])[CH3:16])[C:7](=[O:18])[CH2:6][C:5]1=[O:19])[CH3:3].C[Si]([N-][Si](C)(C)C)(C)C.[K+].C(C1C=C(C(C)C)C=C(C(C)C)C=1S([N:48]=[N+:49]=[N-:50])(=O)=O)(C)C.C(O)(=O)C.C(=O)([O-])O.[Na+].[N-]=[N+]=[N-]>O1CCCC1>[N:48]([CH:6]1[C:5](=[O:19])[N:4]([CH:2]([CH3:1])[CH3:3])[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[N:8]([CH:15]([CH3:17])[CH3:16])[C:7]1=[O:18])=[N+:49]=[N-:50]

Participants

8

Reactant 6

HCID 176Acetic AcidHCID 33558AzideHCID 3717072,4,6-Triisopropylbenzenesulfonyl azideHCID 516892Sodium BicarbonateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 22312288HCID 22312288, compound

Product 1

HCID 22312185HCID 22312185, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirring solution of 1,5-bis-(2-propyl)-1,5-benzodiazepin-2,4-dione (500 mg, 1.92 mmole) in tetrahydrofuran (25 mL), which was cooled to -78° C. in a dry ice/acetone bath, was added dropwise potassium bis(trimethylsilyl) amide (0.5M in toluene, 4.6 mL, 2.3 mmole). After ten minutes, 2,4,6-triisopropylbenzenesulfonyl azide (708 mg, 2.0 mmole) in tetrahydrofuran (5 mL) was added dropwise. After ten minutes, acetic acid (0.44 mL, 7.7 mmole) in tetrahydrofuran (5 mL) was added in one portion and the reaction was warmed to room temperature over three hours. The reaction was poured into a solution of saturated sodium hydrogen carbonate (200 mL) and extracted with ethyl acetate (3×100 mL). The organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue was chromatographed on silica gel eluting with 1:3 ethyl acetate:hexane to give 315 mg of an isomer that is identified as the axial azide, and 120 mg of a lower rf isomer identified as the equatorial conformer. NMR dam for the major isomer is:

Workup

  1. waitAfter ten minutes
  2. waitAfter ten minutes
  3. extractionextracted with ethyl acetate (3×100 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was chromatographed on silica gel eluting with 1:3 ethyl acetate
  8. customhexane to give 315 mg of an isomer that

Sources & evidence

ORD record
ord-74b26a8911004860924d8c5f346dc37d
Source dataset
uspto-grants-1997_11
Patent number
US05691331

Reaction notes

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