1,2-Dichloroethane → (+/-)-trans-3-bromo-6-cyano 3,4-dihydro-2,2-dimethyl-4-[(S)-(-)-3-(3,5-dinitrobenzoylthio)-2-methylpropionyloxy]-2H-1benzopyran

HRID 974089Notes

Reaction equation

HRID 974089 reaction equation
[Br:1][C@H:2]1[C@H:7]([OH:8])[C:6]2[CH:9]=[C:10]([C:13]#[N:14])[CH:11]=[CH:12][C:5]=2[O:4][C:3]1([CH3:16])[CH3:15].C(Cl)CCl.[N+:21]([C:24]1[CH:25]=[C:26]([CH:36]=[C:37]([N+:39]([O-:41])=[O:40])[CH:38]=1)[C:27]([S:29][CH2:30][C@H:31]([CH3:35])[C:32](Cl)=[O:33])=[O:28])([O-:23])=[O:22]>N1C=CC=CC=1>[Br:1][C@H:2]1[C@H:7]([O:8][C:32](=[O:33])[C@H:31]([CH3:35])[CH2:30][S:29][C:27](=[O:28])[C:26]2[CH:36]=[C:37]([N+:39]([O-:41])=[O:40])[CH:38]=[C:24]([N+:21]([O-:23])=[O:22])[CH:25]=2)[C:6]2[CH:9]=[C:10]([C:13]#[N:14])[CH:11]=[CH:12][C:5]=2[O:4][C:3]1([CH3:16])[CH3:15]

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 6932483trans-2,2-Dimethyl-3-bromo-6-cyanochroman-4-olHCID 15045107(S)-(-)-3-(3,5-dinitrobenzoylthio)-2-methylpropionyl chloride

Product 1

HCID 86745229(+/-)-trans-3-bromo-6-cyano 3,4-dihydro-2,2-dimethyl-4-[(S)-(-)-3-(3,5-dinitrobenzoylthio)-2-methylpropionyloxy]-2H-1benzopyranYield 93.1%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a mixture of 14.5 g of (±)-trans-3-bromo-6-cyano-3,4-dihydro-2,2-dimethyl-4-hydroxy-2H-1-benzopyran, 60 ml of ethylene chloride and 1.6 ml of pyridine was added 5.5 g of (S)-(-)-3-(3,5-dinitrobenzoylthio)-2-methylpropionyl chloride under ice-cooling and was stirred for 1.5 hours under room temperature. The reaction mixture was washed with diluted hydrochloric acid once and 10% aqueous sodium chloride solution twice. The organic layer was separated, dried over magnesium sulfate and concentrated under reduced pressure to give 8.9 g of (±)-trans-3-bromo-6-cyano 3,4-dihydro-2,2-dimethyl-4-[(S)-(-)-3-(3,5-dinitrobenzoylthio)-2-methylpropionyloxy]-2H-1benzopyran as light yellow semicrystals.

Workup

  1. temperaturecooling
  2. washThe reaction mixture was washed with diluted hydrochloric acid once
  3. customThe organic layer was separated
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-426f2d45340b4c07ba3874e56a68e9bb
Source dataset
uspto-grants-1991_11
Patent number
US05066816

Reaction notes

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