Sulfuric Acid → 10-Benzo[1,3]dioxol-5-yl-5-chloro-9H-furo[3',4':6,7]naphtho[1,2-d][1,3]dioxol-7-one

HRID 2354606Notes

Reaction equation

HRID 2354606 reaction equation
[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:26])[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.[Cl:27]N1C(=O)CCC1=O.OS(O)(=O)=O>C1COCC1.C(Cl)(Cl)Cl>[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:26])[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]=[C:15]4[Cl:27])=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 31398ChlorosuccinimideHCID 177023Helioxanthin

Product 1

HCID 527381010-Benzo[1,3]dioxol-5-yl-5-chloro-9H-furo[3',4':6,7]naphtho[1,2-d][1,3]dioxol-7-oneYield 49%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Procedure

A stirred solution of 2 (104 mg, 0.3 mmol), N-chlorosuccinimide (80 mg, 0.6 mmol) and concentrated H2SO4 (10 μL) in THF (5 mL) was heated to reflux for 24 h, and then diluted with CHCl3 (50 mL). The reaction mixture was washed with 10% aqueous Na2S2O3 solution (50 mL) and water (2×50 mL), dried over MgSO4, and concentrated in vacuo. The product was purified by column chromatography on silica gel eluting with CHCl3 to afford 37 (56 mg, 49%) as a brown solid. mp 267° C. (decomp.); 1H NMR (CDCl3) δ 8.91 (s, 1H, H4), 7.47 (s, 1H, H6), 6.76-6.91 (m, 3H, H2′+H5′+H6′), 6.08 (AB, 2H, 3′,4′-OCH2O—, Δδ=8.7 Hz, J=1.5 Hz), 5.97 (AB, 2H, 7,8-OCH2O—, Δδ=8.7 Hz, J=1.5 Hz), 5.22 (q, 2H, lactone-CH2—, J=8.7 Hz); MS (EI) m/z 384 [M+2]+, 382 [M]+.

Workup

  1. temperatureto reflux for 24 h
  2. washThe reaction mixture was washed with 10% aqueous Na2S2O3 solution (50 mL) and water (2×50 mL)
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe product was purified by column chromatography on silica gel eluting with CHCl3

Sources & evidence

ORD record
ord-149636cc4a1642fa8f749e931bea23c9
Source dataset
uspto-grants-2010_07
Patent number
US07754718B2

Reaction notes

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