Dimethyl N-cyanodithioiminocarbonate → HCID 178503932, compound

HRID 704787Notes

Reaction equation

HRID 704787 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(OCC)(=O)C>[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

5

Reactant 2

HCID 66289Dimethyl N-cyanodithioiminocarbonateHCID 10943936(3S,4R)-4-amino-3-hydroxy-2,2-dimethyl-chroman-6-carbonitrile

Product 1

HCID 178503932HCID 178503932, compoundYield 63.6%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of trans-4-amino-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (2.18 g) and dimethyl N-cyanoimidodithiocarbonate [(CH3S)2C=N--CN] (1.54 g) in dry pyridine (11 ml) was stirred at 80° C. for 2.5 hours, and under reflux for 2.5 hours. The reaction mixture was diluted with ethyl acetate (40 ml) and washed with 5% hydrochloric acid (30 ml×2). The organic layer was washed successively with water (30 ml), saturated aqueous sodium bicarbonate (30 ml) and brine (30 ml), dried over magnesium sulfate, and evaporated in vacuo. The residue was subjected to column chromatography on silica gel (70 g) and eluted with chloroform and a mixture of chloroform and methanol (50:1 and then 20:1). The fractions containing the object compound were combined and concentrated under reduced pressure. The residue was triturated with diisopropyl ether. The crystals were recrystallized from ethanol to give trans-4-(3-cyano-2-methyl-1-isothioureido)-3,4-dihydro- 3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (2.01 g).

Workup

  1. temperatureunder reflux for 2.5 hours
  2. washwashed with 5% hydrochloric acid (30 ml×2)
  3. washThe organic layer was washed successively with water (30 ml), saturated aqueous sodium bicarbonate (30 ml) and brine (30 ml)
  4. dry with materialdried over magnesium sulfate
  5. customevaporated in vacuo
  6. washeluted with chloroform
  7. additiona mixture of chloroform and methanol (50:1
  8. additionThe fractions containing the object compound
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was triturated with diisopropyl ether
  11. customThe crystals were recrystallized from ethanol

Sources & evidence

ORD record
ord-0eb48e8d649f41d1847e3b9cf601cbda
Source dataset
uspto-grants-1991_01
Patent number
US04988723

Reaction notes

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