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

HRID 370077Notes

Reaction equation

HRID 370077 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-5de30639d565454dbcdd393f51b6e93c
Source dataset
uspto-grants-2000_10
Patent number
US06140351

Reaction notes

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