Dimethylformamide → HCID 19925628, compound

HRID 439827Notes

Reaction equation

HRID 439827 reaction equation
[H-].[K+].[CH3:3][NH:4][C:5]1[CH:10]=[CH:9][C:8]([S:11][C:12]2[CH:13]=[C:14]([Br:18])[CH:15]=[CH:16][CH:17]=2)=[CH:7][CH:6]=1.[CH2:19](Br)[CH:20]=C.[CH3:23]N(C=O)C>C1COCC1>[CH2:3]([N:4]([CH3:23])[C:5]1[CH:6]=[CH:7][C:8]([S:11][C:12]2[CH:13]=[C:14]([Br:18])[CH:15]=[CH:16][CH:17]=2)=[CH:9][CH:10]=1)[CH:19]=[CH2:20]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7841Allyl bromideHCID 82127Potassium hydrideHCID 19925622HCID 19925622, compound

Product 1

HCID 19925628HCID 19925628, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A flask was charged with potassium hydride (0.3 g, 35% oil dispersion, 2.62 mmol) and dry THF (1.5 mL) under a stream of nitrogen. A solution of 3-(N-methyl-p-aminobenzenethioxy)bromobenzene (0.50 g, 1.71 mmol), prepared as in step 4, in dry THF was added via syringe. When gas evolution ceased, allyl bromide (0.38 mL, 4.27 mmol, passed through a neutral alumina pad before addition) was added in a single portion, followed by dry DMF (3.4 mL). After 15 min the reaction was quenched with isopropanol and partitioned between saturated aqueous NH4C1 and ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed twice with brine, dried over MgSO4, filtered, and concentrated in vacuo to give 0.91 g of crude product. Purification by chromatography on silica gel (5% ethyl acetate:hexanes) provided pure 3-(N-allyl-N-methyl-p-aminobenzenethioxy)bromobenzene (0.43 g, 75%).

Workup

  1. additionwas added in a single portion
  2. customAfter 15 min the reaction was quenched with isopropanol
  3. custompartitioned between saturated aqueous NH4C1 and ethyl acetate
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate
  6. washThe combined organic layers were washed twice with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give 0.91 g of crude product
  11. customPurification by chromatography on silica gel (5% ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-e813ca545dba4347b78b5c5273e0d9b1
Source dataset
uspto-grants-1996_05
Patent number
US05516795

Reaction notes

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