Acetonitrile → (3S-trans)-[2-[(6-Cyano-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-pyran-4yl)amino]phenyl]carbamic acid, ethyl ester

HRID 275422

Reaction equation

HRID 275422 reaction equation
[CH3:1][C:2]1([CH3:15])[C@H:7]2[O:8][C@H:6]2[C:5]2C=C(C#N)C=[CH:12][C:4]=2[O:3]1.[CH2:16]([O:18][C:19]([NH:21][C:22]1[CH:28]=[CH:27][CH:26]=[CH:25][C:23]=1[NH2:24])=[O:20])[CH3:17].Cl([O-])(=O)(=O)=O.[Mg+2].Cl([O-])(=O)(=O)=O.C(#[N:42])C>C(OCC)(=O)C>[C:12]([C:4]1[O:3][C:2]([CH3:1])([CH3:15])[C@@H:7]([OH:8])[C@H:6]([NH:24][C:23]2[CH:25]=[CH:26][CH:27]=[CH:28][C:22]=2[NH:21][C:19](=[O:20])[O:18][CH2:16][CH3:17])[CH:5]=1)#[N:42]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 24840Magnesium perchlorateHCID 9837089(1aS,7bS)-2,2-Dimethyl-1a,7b-dihydro-2H-oxireno[2,3-c]chromene-6-carbonitrileHCID 122150062-[(Ethoxycarbonyl)amino]aniline

Product 1

HCID 67845190(3S-trans)-[2-[(6-Cyano-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-pyran-4yl)amino]phenyl]carbamic acid, ethyl esterYield 92.8%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The reaction mixture containing (1aS-cis)-1a,7b-dihydro-2,2-dimethyl-2H-oxireno-[c][1]benzopyran-6-carbonitrile, from example 2, part A (1.0 g, 5.0 mmol), 2-[(ethoxycarbonyl)amino]aniline, compound of example 1, part B (900 mg, 5.0 mmol) and magnesium perchlorate (1.12 g, 5.0 mmol) in acetonitrile (5.0 mL) was stirred under argon at room temperature for 48 hours. The reaction mixture was diluted with ethyl acetate and washed with water, saturated sodium bicarbonate solution and brine. After drying over anhydrous magnesium sulfate, the solvent was evaporated to give a colorless foam which was purified by flash chromatography (25% ethyl acetate in hexanes) to yield the title product as an amorphous solid (1.76 g, 92.8%) (shrinks at 84° C.). [a]D =+21° (c=1.1%, MeOH). Microanalysis calculated for C21H23N3O4 : C,66.13; H, 6.08; N,11.02. Found: C, 66.11 ; H, 6.15; N, 10.78.

Workup

  1. washwashed with water, saturated sodium bicarbonate solution and brine
  2. dry with materialAfter drying over anhydrous magnesium sulfate
  3. customthe solvent was evaporated
  4. customto give a colorless foam which
  5. customwas purified by flash chromatography (25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-57fd679929ab417a953abb3ddfc20d6a
Source dataset
uspto-grants-1995_02
Patent number
US05393771

Linked notes

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