Diethyl Ether → Methyl 3-benzyloxy-1,2-dioxocyclohexa-3,5-diene-5-benzoate

HRID 1182012Notes

Reaction equation

HRID 1182012 reaction equation
[C:1]1(Cl)[C:8](Cl)=[C:7](Cl)[C:5](=O)[C:3](=[O:4])[C:2]=1Cl.[CH2:13]([O:20][C:21]1[CH:22]=[C:23]([CH:28]=[C:29]([OH:32])[C:30]=1[OH:31])[C:24](OC)=O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C[CH2:34][O:35]CC>>[CH2:13]([O:20][C:21]1[C:30](=[O:31])[C:29](=[O:32])[CH:28]=[C:23]([C:24]2[C:2]([C:3]([O:35][CH3:34])=[O:4])=[CH:1][CH:8]=[CH:7][CH:5]=2)[CH:22]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

4

Reactant 3

HCID 3283Diethyl Ether2×HCID 73252o-ChloranilHCID 3525469methyl 3-(benzyloxy)-4,5-dihydroxybenzoate

Product 1

HCID 69227092Methyl 3-benzyloxy-1,2-dioxocyclohexa-3,5-diene-5-benzoate

Conditions

Temperature
-30 °C

Procedure

To a solution of orthochloranii (1.97 g, 8.02 mmol) in 5 mL of Et2O cooled to −30° C. was added dropwise via an addition funnel over 6 h a solution of methyl 3-benzyloxy-4,5-dihydroxybenzoate (2.0 g, 7.3 mmol) in 115 mL of Et2O. The reaction was stirred for a further 0.5 h at −30° C. and then stored at −20° C. for 20 h. The precipitated red solid was collected by filtration, washed with cold Et2O and dried on a vacuum pump to afford 1.11 g (55%) of the orthoquinone. IR (CDCl3) 1727, 1671 cm−1; 1H NMR (CDCl3, 300 MHz) δ 7.41-7.26 (m. 5H), 6.74 (s. 1H), 6.73 (s, 1H1, 6.56 (s. 2H), 3.92 (s, 3H); 13C NMR (CDCl3, 75 MHz) δ 179.9, 174.2, 164.7, 152.1, 141.3, 134.3, 128.8, 128.7, 127.7, 124.4, 107.7, 71.1, 53.4; MS (−FAB) 272 (M−, 12). Anal. Calc for C15H12O5; C. 66.18; H. 4.41; Found: C, 65.75; H. 4.45.

Workup

  1. waitstored at −20° C. for 20 h
  2. filtrationThe precipitated red solid was collected by filtration
  3. washwashed with cold Et2O
  4. customdried on a vacuum pump
  5. customto afford 1.11 g (55%) of the orthoquinone

Sources & evidence

ORD record
ord-017c2eae7b4f4c008ce650f8413075cc
Source dataset
uspto-grants-2007_10
Patent number
US07288273B1

Reaction notes

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