Hydrochloric Acid → Helioxanthin

HRID 2354589Notes

Reaction equation

HRID 2354589 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:11]4[C:25](=[O:26])[O:24][C:23](=[O:27])[C:12]=4[CH:13]=[C:14]4[C:22]=3[C:18]3[O:19][CH2:20][O:21][C:17]=3[CH:16]=[CH:15]4)=[CH:9][C:4]=2[O:3][CH2:2]1.[BH4-].[Na+].Cl>C1COCC1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:11]4[C:25](=[O:26])[O:24][C:23](=[O:27])[C:12]=4[CH:13]=[C:14]4[C:22]=3[C:18]3[O:19][CH2:20][O:21][C:17]=3[CH:16]=[CH:15]4)=[CH:9][C:4]=2[O:3][CH2:2]1.[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:11]4[CH2:25][O:24][C:23](=[O:27])[C:12]=4[CH:13]=[C:14]4[C:22]=3[C:18]3[O:19][CH2:20][O:21][C:17]=3[CH:16]=[CH:15]4)=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 527377710-Benzo[1,3]dioxol-5-yl-furo[3',4':6,7]naphtho[1,2-d][1,3]dioxole-7,9-dione

Product 2

HCID 177023HelioxanthinYield 157.5%HCID 527377710-Benzo[1,3]dioxol-5-yl-furo[3',4':6,7]naphtho[1,2-d][1,3]dioxole-7,9-dione

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

10-Benzo[1,3]dioxol-5-yl-furo[3′,4′:6,7]naphtho[1,2-d][1,3]dioxole-7,9-dione (1) was synthesized using procedure described in the literature (Charlton, J. L.; Oleschuk, C. J.; Chee, G. L. Hindered rotation in arylnaphthalene lignans. J. Org. Chem. 1996, 61, 3452-3457). The compound 1 (1.90 g, 5.25 mmol) in dry THF (100 mL) at 0° C. was added dropwise to a mixture of sodium borohydride (218 mg, 5.8 mmol) in dry THF (100 mL). The mixture was stirred at room temperature for 1 h and then acidified to pH 1-2 with 10% aqueous HCl solution. After stirring for 1 h, the mixture was extracted with ether (3×100 mL), concentrated in vacuo, and chromatographed using CHCl3 to give a lactone 2 (1.44 g, 79%) as a pale yellow powder. mp 242-244° C.; 1H NMR (DMSO-d6) δ 8.56 (s, 1H, H4), 7.93 (d, 1H, H5, J=8.4 Hz), 7.50 (d, 1H, H6, J=8.4 Hz), 7.01 (d, 1H, H2′, J=1.5 Hz), 6.95 (d, 1H, H5′, J=8.1 Hz), 6.87 (dd, 1H, H6′, J=1.5, 8.1 Hz), 6.08 (AB, 2H, 3′,4′-OCH2O—, Δδ=15.6 Hz, J=0.9 Hz), 5.99 (AB, 2H, 7,8-OCH2O—, Δδ=6.0 Hz, J=0.9 Hz), 5.28 (s, 2H, lactone-CH2—); MS (FAB, positive) m/z 349 [M+H]+.

Workup

  1. stirringAfter stirring for 1 h
  2. extractionthe mixture was extracted with ether (3×100 mL)
  3. concentrationconcentrated in vacuo
  4. customchromatographed

Sources & evidence

ORD record
ord-4efde02a21c44dc8af04c426f81465d4
Source dataset
uspto-grants-2010_07
Patent number
US07754718B2

Reaction notes

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