Phenyl thioxochloroformate → 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-2-ethoxycarbonylethyl)-1-pyridinyl}-2H-benzo[b]pyran

HRID 487644

Reaction equation

HRID 487644 reaction equation
[C:1]([C:3]1[CH:29]=[CH:28][C:6]2[O:7][C:8]([CH3:27])([CH3:26])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH:17]([OH:24])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:13][C:12]3=[O:25])[C:5]=2[CH:4]=1)#[N:2].[O:30]([C:37](Cl)=[S:38])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.C(=O)([O-])O.[Na+]>C(#N)C.CN(C)C1C=CN=CC=1>[C:1]([C:3]1[CH:29]=[CH:28][C:6]2[O:7][C:8]([CH3:26])([CH3:27])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH:17]([O:24][C:37]([O:30][C:31]4[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=4)=[S:38])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:13][C:12]3=[O:25])[C:5]=2[CH:4]=1)#[N:2]

Participants

6

Reactant 3

HCID 70498Phenyl thioxochloroformateHCID 516892Sodium BicarbonateHCID 190925286-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-hydroxy-2-ethoxycarbonylethyl)-1-pyridinyl}-2H-benzo[b]pyran

Product 1

HCID 217469106-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-2-ethoxycarbonylethyl)-1-pyridinyl}-2H-benzo[b]pyran

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

In 10 ml of acetonitrile, is dissolved 314 mg of 6-cyano-2,2-dimethyl-4-{2-oxo-4-(1-hydroxy-2-ethoxycarbonylethyl)-1-pyridinyl}-2H-benzo[b]pyran obtained in Example 31. Then, 195 mg of 4-dimethylaminopyridine and 0.17 ml of phenoxythiocarbonyl chloride are added at room temperature and reacted at that temperature for 19.5 hours. After stopping the reaction by adding 0.1M aqueous solution of sodium hydrogen carbonate, the reaction mixture is extracted with ethyl acetate. The organic layer is washed successively with water and saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The inorganic matter is filtered off and the filtrate is concentrated under reduced pressure. The residue is purified by silica gel column chromatography using 2/3 mixture of ethyl acetate/n-hexane. Thus, there are obtained 77 mg of 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-2-ethoxycarbonylethyl)-1-pyridinyl}-2H-benzo[b]pyran and, as a by-product, 20 mg of 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(2-ethoxycarbonylethenyl)-1-pyridinyl}-2H-benzo[b]pyran.

Workup

  1. customreacted at that temperature for 19.5 hours
  2. customthe reaction
  3. extractionthe reaction mixture is extracted with ethyl acetate
  4. washThe organic layer is washed successively with water and saturated aqueous solution of sodium chloride
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationThe inorganic matter is filtered off
  7. concentrationthe filtrate is concentrated under reduced pressure
  8. customThe residue is purified by silica gel column chromatography
  9. addition2/3 mixture of ethyl acetate/n-hexane

Sources & evidence

ORD record
ord-0bc983c6f6b64f4bb9828c6a74ffdb27
Source dataset
uspto-grants-1994_03
Patent number
US05296492

Linked notes

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