Sulfuryl chloride → 4-(4-Bromophenyl)-5-chloro-2-(2-cyano-acetylamino)-thiophene-3-carboxylic acid ethyl ester

HRID 1244093Notes

Reaction equation

HRID 1244093 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:10]([C:11]2[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][CH:12]=2)=[CH:9][S:8][C:7]=1[NH:18][C:19](=[O:23])[CH2:20][C:21]#[N:22])=[O:5])[CH3:2].S(Cl)([Cl:27])(=O)=O>C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[C:10]([C:11]2[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][CH:12]=2)=[C:9]([Cl:27])[S:8][C:7]=1[NH:18][C:19](=[O:23])[CH2:20][C:21]#[N:22])=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 1014753Ethyl 4-(4-bromophenyl)-2-[(cyanoacetyl)amino]thiophene-3-carboxylate

Product 1

HCID 696073704-(4-Bromophenyl)-5-chloro-2-(2-cyano-acetylamino)-thiophene-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a cold (0° C.) solution of 4-(4-bromophenyl)-2-(2-cyano-acetylamino)-thiophene-3-carboxylic acid ethyl ester (4.0 g, 10.18 mmol) in methylene chloride (34 mL) was added sulfuryl chloride (0.82 mL, 10.2 mmol). The cold bath was removed, and the reaction was stirred at room temperature for 4 h. Saturated aqueous sodium bicarbonate solution was then added (30 mL) to the reaction. The layers were separated, and the aqueous was extracted with additional methylene chloride (3×15 mL). The combined organic layers were dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the titled compound as a solid. MS (DCI/NH3) m/e 446 (M+NH3)+, NMR (300 MHz, CDCl3): δ ppm 12.1 (br s, 1H), 7.53 d, 2H), 7.09 (d, 2H), 4.08 (q, 2H), 3.67 (s, 2H), and 0.91 (t, 3H).

Workup

  1. customThe cold bath was removed
  2. additionSaturated aqueous sodium bicarbonate solution was then added (30 mL)
  3. customto the reaction
  4. customThe layers were separated
  5. extractionthe aqueous was extracted with additional methylene chloride (3×15 mL)
  6. dry with materialThe combined organic layers were dried with anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b4d6776dcade405b9b0d162e7ffea8bb
Source dataset
uspto-grants-2006_10
Patent number
US07119205B2

Reaction notes

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