Dimethyl N-cyanodithioiminocarbonate → (3R,4S)-4-(3-cyano-2-methyl-1-isothioureido)-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile

HRID 704797Notes

Reaction equation

HRID 704797 reaction equation
[NH2:1][C@H:2]1[C:7]2[CH:8]=[C:9]([C:12]#[N:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH3:15])([CH3:14])[C@@H:3]1[OH:16].[CH3:17][S:18][C:19](SC)=[N:20][C:21]#[N:22]>N1C=CC=CC=1>[C:21]([N:20]=[C:19]([S:18][CH3:17])[NH:1][C@H:2]1[C:7]2[CH:8]=[C:9]([C:12]#[N:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH3:14])([CH3:15])[C@@H:3]1[OH:16])#[N:22]

Participants

4

Reactant 2

HCID 66289Dimethyl N-cyanodithioiminocarbonateHCID 14511095(3R,4S)-4-amino-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile

Product 1

HCID 178503933(3R,4S)-4-(3-cyano-2-methyl-1-isothioureido)-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A solution of (3R,4S)-4-amino-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (2.40 g) and dimethyl N-cyanoimidodithiocarbonate [(CH2C=C--N--] (1.61 g) in pyridine (12 ml) was stirred at 80° C. for 10 hours, and then concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with 5% aqueous hydrochloric acid, and brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was subjected to column chromatography on silica gel (48 g) and eluted with a mixture of chloroform and methanol (20:1). The fractions containing the object compound were combined and concentrated in vacuo to give (3R,4S)-4-(3-cyano-2-methyl-1-isothioureido)-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (2.17 g).

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed with 5% aqueous hydrochloric acid, and brine
  4. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. washeluted with a mixture of chloroform and methanol (20:1)
  7. additionThe fractions containing the object compound
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0cf0b90029ef4f6596eb962e4bed11ff
Source dataset
uspto-grants-1991_01
Patent number
US04988723

Reaction notes

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