2-Methyl-2-butene → 5-(4-Chlorophenylthio)thiophene-2-carboxylic acid

HRID 412007Notes

Reaction equation

HRID 412007 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][C:9]2[S:13][C:12]([CH:14]=[O:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.CC(=CC)C.[OH:21]P([O-])(O)=O.[K+].[O-]Cl=O.[Na+].OS([O-])(=O)=O.[K+]>C1COCC1.CC(O)(C)C.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([S:8][C:9]2[S:13][C:12]([C:14]([OH:21])=[O:15])=[CH:11][CH:10]=2)=[CH:6][CH:7]=1

Participants

9

Reactant 5

HCID 105532-Methyl-2-buteneHCID 516920Potassium bisulfateHCID 516951Monobasic potassium phosphateHCID 70621945-[(4-Chlorophenyl)sulfanyl]-2-thiophenecarbaldehydeHCID 23668197Sodium Chlorite

Product 1

HCID 223504025-(4-Chlorophenylthio)thiophene-2-carboxylic acidYield 87.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

5-(4-Chlorophenylsulfanyl)thiophene-2-carboxaldehyde (6.1 g, 24 mmol) is dissolved in a mixture of THF, tBuOH, and water (3:3:1, 255 mL). 2-methyl-2-butene (20.3 mL, 192 mmol) is added followed by KH2PO4 (9.8 g, 72 mmol) and then NaClO2 (80%, 8.17 g, 72.3 mmol). The mixture is stirred at rt for 2 hours. Aqueous KHSO4 (0.5M, 200 mL) is added and the organic solvents are removed in vacuo to produce an aqueous suspension of the product. The precipitate is collected by filtration, dissolved in IN NaOH and washed two times with ether. The aqueous solution is then acidified to pH<2 with concentrated HCl and a precipitate formed. The precipitate is collected by filtration and washed with 0.5M NaHSO4 then water. The solid is dried in vacuo to give 5.7 g (87%) of 5-(4-chlorophenylsulfanyl)thiophene-2-carboxylic acid. MS for C11H7ClO2S2, (ES) m/z: 269 (M−H)−.

Workup

  1. customthe organic solvents are removed in vacuo
  2. customto produce
  3. additionan aqueous suspension of the product
  4. filtrationThe precipitate is collected by filtration
  5. dissolutiondissolved in IN NaOH
  6. washwashed two times with ether
  7. customa precipitate formed
  8. filtrationThe precipitate is collected by filtration
  9. washwashed with 0.5M NaHSO4
  10. customThe solid is dried in vacuo

Sources & evidence

ORD record
ord-291cb619609d471896591303a306e1b1
Source dataset
uspto-grants-2003_05
Patent number
US06562816B2

Reaction notes

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