Chloroacetaldehyde → 2-(chloromethyl)-7-(methylsulfonyl)-4H-1,3-benzodioxine

HRID 452450Notes

Reaction equation

[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:5][C:4]=1[OH:13].[Cl:14][CH2:15][CH:16]=O.OS(O)(=O)=O>CCO>[Cl:14][CH2:15][CH:16]1[O:13][C:4]2[CH:5]=[C:6]([S:9]([CH3:12])(=[O:10])=[O:11])[CH:7]=[CH:8][C:3]=2[CH2:2][O:1]1

Participants

Conditions

Temperature: 0 °C

Procedure

2-(hydroxymethyl)-5-(methylsulfonyl)phenol (0.2 g, 1.0 mmol) was dissolved in EtOH (4.5 ml) and chloroacetaldehyde (0.15 ml, 1.2 mmol) was added. The mixture was cooled to 0° C. and concentrated H2SO4 (2.5 ml) was added dropwise. The reaction mixture was stirred at 0° C. for 10 min and then in room temperature for 2-3 h. Chloroacetaldehyde (50 μl) and concentrated H2SO4 (0.5 ml) was added and the reaction mixture was stirred for another 1-2 h before the reaction was quenched with water. The aqueous phase was extracted with EtOAc and the combined organic phases were dried (Na2SO4) and evaporated under reduced pressure to give an oil. Purification by flash column chromatography (isooctane/EtOAc 2:1) gave the title compound (0.58 g, with some inpurities). MS m/z (rel. intensity, 70 eV) 264 (M+, 5), 262 (M+, 13), 213 (31), 184 (bp), 77 (61), 51 (47).

Workup

waitin room temperature for 2-3 h
stirringthe reaction mixture was stirred for another 1-2 h before the reaction
customwas quenched with water
extractionThe aqueous phase was extracted with EtOAc
dry with materialthe combined organic phases were dried (Na2SO4)
customevaporated under reduced pressure
customto give an oil
customPurification by flash column chromatography (isooctane/EtOAc 2:1)

Sources & evidence

ORD record: ord-5c196a37aaaf4fe4b06766407e68d2be
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08492372B2

Reaction notes

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