Acetic Acid → 6-Vinyl-[1,4]dioxepane-6-carboxylic acid

HRID 2176275Notes

Reaction equation

HRID 2176275 reaction equation
[N+](C[C:5]1([CH:12]=[CH2:13])[CH2:11][O:10][CH2:9][CH2:8][O:7][CH2:6]1)([O-])=O.C(O)(=[O:16])C.N([O-])=O.[Na+].Cl.CN(C)[CH:25]=[O:26]>>[CH:12]([C:5]1([C:25]([OH:26])=[O:16])[CH2:11][O:10][CH2:9][CH2:8][O:7][CH2:6]1)=[CH2:13]

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 23668193Sodium NitriteHCID 867061196-Nitromethyl-6-vinyl-[1,4]dioxepane

Product 1

HCID 867061206-Vinyl-[1,4]dioxepane-6-carboxylic acidYield 40%

Conditions

Temperature
40 °C

Procedure

To a stirred solution of 6-nitromethyl-6-vinyl-[1,4]dioxepane (214 mg, 1.14 mmol) in N,N-dimethylformamide (5 mL) under nitrogen was added acetic acid (684 mg, 652 μL, 11.4 mmol) and sodium nitrite (237 mg, 3.43 mmol). The mixture was heated at 40° C. for 23 h and allowed to cool. The mixture was acidified to pH 1 with hydrochloric acid (2 M) and the aqueous layer was extracted with diethyl ether (3×). The combined organic extracts were washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated. Residual N,N-dimethylformamide was azeotroped off with toluene to give the title compound (79 mg, 40%) as a yellow gum. The original aqueous layer was saturated with sodium chloride and extracted with diethyl ether (3×) and the combined organic extracts were washed with water, dried over anhydrous magnesium sulfate, filtered and evaporated. Residual N,N-dimethylformamide was azeotroped off with toluene to give the title compound (22 mg, 11%) as a yellow gum. The two gums were finally combined (101 mg, 51%). 1H NMR (300 MHz, CDC3) δ 3.76-3.93 (m, 4H), 3.88 (d, J=12.5 Hz, 2H), 4.35 (d, J=12.7 Hz, 2H), 5.26 (d, J=17.8 Hz, 1H), 5.27 (d, J=10.9 Hz, 1H), 5.79 (dd, J=17.4, 10.9 Hz, 1H). LCMS (m/z) 195.2 [M+Na], Tr=0.96 min.

Workup

  1. temperatureto cool
  2. extractionthe aqueous layer was extracted with diethyl ether (3×)
  3. washThe combined organic extracts were washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customResidual N,N-dimethylformamide was azeotroped off with toluene

Sources & evidence

ORD record
ord-3db55044311b40ebb28c87e084b46d43
Source dataset
uspto-grants-2015_06
Patent number
US09062092B2

Reaction notes

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