Mesitylene → (8-Ally-7-nitro-2,3-dihydro-benzo(1,4)dioxin-2-yl)-methanol

HRID 1836962Notes

Reaction equation

HRID 1836962 reaction equation
C([O:4][C:5]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[CH:13]=[CH:12][C:6]=1[O:7][CH2:8][C@H:9]1[CH2:11][O:10]1)C=C.[C:19]1(C)[CH:24]=C(C)C=C(C)[CH:20]=1>>[CH2:24]([C:15]1[C:5]2[O:4][CH:9]([CH2:11][OH:10])[CH2:8][O:7][C:6]=2[CH:12]=[CH:13][C:14]=1[N+:16]([O-:18])=[O:17])[CH:19]=[CH2:20]

Participants

3

Reactant 2

HCID 7947MesityleneHCID 12082204(R)-2-(2-Allyloxy4-nitrophenoxymethyl)-oxirane

Product 1

HCID 21892061(8-Ally-7-nitro-2,3-dihydro-benzo(1,4)dioxin-2-yl)-methanol

Procedure

(R)-2-(2-Allyloxy-4-nitrophenoxymethyl)-oxirane (20 g, 80 mmoles) prepared as above was heated at 155° C. in mesitylene for 24 hours under nitrogen. Filtration of the black solid which formed gave 1.5 g of very polar material. Evaporation of the solvent in vacuum followed by column chromatography on silica gel with methylene chloride as eluant gave 10 g of recovered starting material and 7.5 g of the desired rearranged (S)-(8-allyl-7-nitro-2,3-dihydro-benzo(1,4)dioxin-2-yl)-methanol, which slowly crystallized on standing in vacuum (m.p. 67° C.). The yield based on recovered starting material is 75%.

Workup

  1. filtrationFiltration of the black solid which
  2. customformed
  3. customgave 1.5 g of very polar material
  4. customEvaporation of the solvent in vacuum
  5. customgave 10 g
  6. customof recovered
  7. customslowly crystallized
  8. customon recovered

Sources & evidence

ORD record
ord-5714aeb4a63f449aa2b3cd895c6da7e3
Source dataset
uspto-grants-2004_08
Patent number
US06780860B2

Reaction notes

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