Hydrochloric Acid → 5-(Chloromethyl)-6-methylbenzo[d][1,3]dioxole

HRID 250219Notes

Reaction equation

HRID 250219 reaction equation
[CH3:1][C:2]1[CH:10]=[CH:9][C:5]2[O:6][CH2:7][O:8][C:4]=2[CH:3]=1.C=O.Cl[CH2:14][Cl:15].Cl>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CCOCC>[Cl:15][CH2:14][C:10]1[C:2]([CH3:1])=[CH:3][C:4]2[O:8][CH2:7][O:6][C:5]=2[CH:9]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 6344DichloromethaneHCID 815641,3-Benzodioxole, 5-methyl-

Product 1

HCID 105594165-(Chloromethyl)-6-methylbenzo[d][1,3]dioxoleYield 62%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

At about 0° C., 5-methylbenzo[d][1,3]dioxole (500 mg, 3.68 mmol) and formaldehyde (37% in water, 0.7 mL) were sequentially added to a mixture of dichloromethane (6.8 mL), tetrabutylammonium bromide (80 mg) and concentrated hydrochloric acid (6.5 mL). Under continuous stirring, the mixture was maintained at about 0° C. for about 1 hour and then at ambient temperature for about 4 hours. The mixture was diluted with ether (100 mL). After standard extractive workup, the resulting solid residue was heated with hexanes (100 mL) and the insolubles were removed by filtration. The filtrate was concentrated to give desired product (420 mg, 62%). 1H NMR (300 MHz, CDCl3) δ 6.89 (s, 1H), 6.69 (s, 1H), 5.94 (s, 3H), 4.56 (s, 2H), 2.35 (s, 3H); GC-MS: m/z=184 (MH)+.

Workup

  1. customthe insolubles were removed by filtration
  2. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-b6b6d050f2924effa5aa7dbff1654bc5
Source dataset
uspto-grants-2011_01
Patent number
US07863308B2

Reaction notes

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