Benzene → Ethyl 3-[(4-bromo-2-methylphenyl)amino]-2-(dimethylsulfuranylidene)-3-oxopropanoate

HRID 487006Notes

Reaction equation

HRID 487006 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:16])[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]([CH3:17])[CH:3]=1.C1(N=C=NC2CCCCC2)CCCCC1.C1C=CC=CC=1.P(=O)(O)(O)O.[CH3:44][S:45]([CH3:47])=O>>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:16])[C:10](=[S:45]([CH3:47])[CH3:44])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]([CH3:17])[CH:3]=1

Participants

6

Reactant 5

HCID 241BenzeneHCID 679Dimethyl Sulfoxide2×HCID 1004Phosphoric AcidHCID 10868DicyclohexylcarbodiimideHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

Product 1

HCID 86745932Ethyl 3-[(4-bromo-2-methylphenyl)amino]-2-(dimethylsulfuranylidene)-3-oxopropanoate

Procedure

A mixture of 30.0 grams (0.10 mole) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3oxopropanoate, 51.58 grams (0.25 mole) of 1,3-dicyclohexylcarbodiimide, 100 milliliters of benzene and 100 milliliters of dimethyl sulfoxide was stirred at ambient temperature and a solution of 4.9 grams (0.05 mole) of anhydrous phosphoric acid in 10 milliliters of dimethyl sulfoxide added dropwise. After a few minutes an exothermic reaction occurred with separation of a white solid and an increase in temperature from 25° C. to 35° C. The reaction mixture was then stirred for an approximate 16-hour period at ambient temperature. The mixture was then diluted with 500 milliliters of ethyl acetate and by-product 1,3-dicyclohexylurea removed by filtration. The filtrate was washed with several portions of water, dried over MgSO4, filtered and freed of solvent under reduced pressure to give a yellow solid. This was crystallized from ethyl acetate-hexane (1:1) to give 15.8 grams (0.04 mole) of ethyl 3 -[(4-bromo-2-methylphenyl)amino]-2-(dimethylsulfuranylidene)-3-oxopropanoate having a melting point of 143° C.-150° C. Recrystallization of a small sample gave a white solid of melting point 146° C.-149° C. Elemental analysis of the product indicated the following:

Workup

  1. customAfter a few minutes an exothermic reaction
  2. customoccurred with separation of a white solid
  3. temperaturean increase in temperature from 25° C. to 35° C
  4. stirringThe reaction mixture was then stirred for an approximate 16-hour period at ambient temperature
  5. additionThe mixture was then diluted with 500 milliliters of ethyl acetate and by-product 1,3-dicyclohexylurea
  6. customremoved by filtration
  7. washThe filtrate was washed with several portions of water
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customto give a yellow solid
  11. customThis was crystallized from ethyl acetate-hexane (1:1)

Sources & evidence

ORD record
ord-6653e0f76a1a4eaa87bb184c02c6ed35
Source dataset
uspto-grants-1994_03
Patent number
US05292937

Reaction notes

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