Chloromethyl Methyl Ether → 1-Bromo-2,3-bis(methoxymethyloxy)-4-methoxy-benzene

HRID 1836798

Reaction equation

HRID 1836798 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([OH:10])[C:3]=1[OH:11].[O:12]1[CH2:16]CC[CH2:13]1.C(N(C(C)C)CC)(C)C.[CH3:26][O:27][CH2:28]Cl>O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([O:10][CH2:13][O:12][CH3:16])[C:3]=1[O:11][CH2:26][O:27][CH3:28]

Participants

6

Reactant 4

HCID 7864Chloromethyl Methyl EtherHCID 8028TetrahydrofuranHCID 81531DiisopropylethylamineHCID 37058743-Bromo-6-methoxybenzene-1,2-diol

Product 1

HCID 105666271-Bromo-2,3-bis(methoxymethyloxy)-4-methoxy-benzeneYield 91%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of 1-bromo-2,3-dihydroxy-4-methoxy-benzene (5.0 g) and anhydrous tetrahydrofuran (20 mL) at 0° C. under argon was added diisopropylethylamine (8.0 mL). The solution was stirred for 15 min, methyloxymethyl chloride (3.5 mL) was added, and the reaction mixture stirred for 3 hours. The solution was poured into water (250 mL), extracted with dichloromethane and the solvent removed in vacuo to provide an orange oil. The oil was purified by flash column chromatography (hexane-ethyl acetate, 2:1) to yield a clear oil (6.4 g, 91%): EIMS m/z 308 (M+, 81Br), 306 (M+, 79Br), 232, 230, 45; IR (neat, cm−1) vmax 2963, 2836, 1221, 1159, 1084, 966; 1H NMR δ 7.25 (1H, d, J=9.0 Hz, H5), 6.61 (1H, d, J=9.0 Hz, H4), 5.20 (2H, s, OCH2), 5.13 (2H, s, OCH2), 3.84 (3H, s, OCH3), 3.66 (3H, s, OCH3), 3.59 (3H, s, OCH3); 13C—NMR (75.5 MHZ) δ 153.31, 148.24, 140.05, 127.49, 108.94, 108.73, 99.39, 98.73, 58.14, 57.46, 56.11. Anal. Calcd. For C11H15O5Br: C, 43.02; H, 4.92. Found: C, 42.86; H, 4.93.

Workup

  1. stirringthe reaction mixture stirred for 3 hours
  2. extractionextracted with dichloromethane
  3. customthe solvent removed in vacuo
  4. customto provide an orange oil
  5. customThe oil was purified by flash column chromatography (hexane-ethyl acetate, 2:1)

Sources & evidence

ORD record
ord-7754d388b453470ca553b337dfea0fb0
Source dataset
uspto-grants-2004_08
Patent number
US06777578B2

Linked notes

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