Sulfuryl chloride → 2-Methoxycarbonyl-3-chloro4-(chloromethyl)thiophene

HRID 844146Notes

Reaction equation

HRID 844146 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH3:11])[C:9]=1[Cl:10])=[O:4].S(Cl)([Cl:15])(=O)=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[S:6][CH:7]=[C:8]([CH2:11][Cl:15])[C:9]=1[Cl:10])=[O:4]

Participants

5

Reactant 2

HCID 24648Sulfuryl chlorideHCID 2777567Methyl 3-chloro-4-methylthiophene-2-carboxylate

Product 1

HCID 183767792-Methoxycarbonyl-3-chloro4-(chloromethyl)thiopheneYield 54%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

To 2-methoxycarbonyl-3-chloro-4-methylthiophene (100 g, 0.53 mol) in dry carbon tetrachloride (1.5 L) were added sulfuryl chloride (65 mL, 0.81 mol) and benzoyl peroxide (2.5 g, 10 mmol). The reaction was heated at reflux for 17 hours, then cooled to ambient temperature and concentrated of all volatiles in vacuo. Purification of the resulting oil by flash chromatography on silica gel afforded 63 g (54% yield) of 2-methoxycarbonyl-3-chloro-4-(chloromethyl)thiophene as a yellow oil which crystallized to fine needles upon standing; NMR (CDCl3) 7.6 (s, 1), 4.6 (s, 2), 3.9 (s, 3) ppm.

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 17 hours
  3. concentrationconcentrated of all volatiles in vacuo
  4. customPurification of the resulting oil by flash chromatography on silica gel

Sources & evidence

ORD record
ord-e12a7cdf63cc465b8d96017ac90a8150
Source dataset
uspto-grants-2002_04
Patent number
US06380221B1

Reaction notes

Loading…