Sulfuryl chloride → tert-butyl N-[3-(chlorosulfonyl)phenyl]-N-methylcarbamate

HRID 1166496Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([CH:14]=[CH:15][CH:16]=1)[N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH3:6].C([Li])CCC.[S:22](Cl)([Cl:25])(=[O:24])=[O:23]>C1COCC1>[C:10]([O:9][C:7]([N:5]([CH3:6])[C:4]1[CH:14]=[CH:15][CH:16]=[C:2]([S:22]([Cl:25])(=[O:24])=[O:23])[CH:3]=1)=[O:8])([CH3:13])([CH3:12])[CH3:11]

Participants

Conditions

Temperature: -78 °C

Procedure

3-Bromo-N-tert-butoxycarbonyl-N-methylaniline (0.358g, 1.2 mmol) was dissolved in freshly distilled THF (5 ml) under a N2 atmosphere. The solution was chilled to −78° C. and n-butyl lithium (0.750 ml, 2.0 M solution in cyclohexane, 1.5 mmol) was added. After 15 minutes, sulfuryl chloride (0.121 ml, 1.5 mmol) was added and the reaction was allowed to warm to room temperature and stirring was continued overnight. THF was removed by evaporation and the resulting residue was diluted in EtOAc. Organic phase was washed with H20 and brine before being dried with MgSO4. The solvent was removed in vacuo. Purification by flash chromatography (1:19/EtOAc/Hex gradient to 1:9 and then to 1:4). Recovered 0.089 g (23%) of the product as a colorless oil. Rf=0.14 (1:9 EtOAc/Hex). 1H NMR (CDCl3) 7.96 (1H,s), 7.80 (1H,d), 7.68 (1H,d), 7.57 (1H,t), 3.33 (3H,s), 1.50 (9H,s).

Workup

temperatureto warm to room temperature
waitwas continued overnight
customTHF was removed by evaporation
additionthe resulting residue was diluted in EtOAc
washOrganic phase was washed with H20 and brine
dry with materialbefore being dried with MgSO4
customThe solvent was removed in vacuo
customPurification by flash chromatography (1:19/EtOAc/Hex gradient to 1:9
customRecovered 0.089 g (23%) of the product as a colorless oil

Sources & evidence

ORD record: ord-db1887b6a55a4def9ad6d7960b1df6c1
Source dataset: uspto-grants-2003_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06613743B2

Reaction notes

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