Nitric Acid → 2,3-Dihydro-2,2-dimethyl-4-nitro-7-benzofuranol

HRID 638151

Reaction equation

HRID 638151 reaction equation
[CH3:1][C:2]1([CH3:12])[CH2:6][C:5]2[CH:7]=[CH:8][CH:9]=[C:10]([OH:11])[C:4]=2[O:3]1.[N+:13]([O-])([OH:15])=[O:14]>CCOCC>[CH3:1][C:2]1([CH3:12])[CH2:6][C:5]2[C:7]([N+:13]([O-:15])=[O:14])=[CH:8][CH:9]=[C:10]([OH:11])[C:4]=2[O:3]1

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 152782,3-Dihydro-2,2-dimethyl-7-benzofuranol

Product 1

HCID 134204792,3-Dihydro-2,2-dimethyl-4-nitro-7-benzofuranol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 2,3-dihydro-2,2-dimethyl-7-benzofuranol (16.4 g, 0.1 mol) in 150 ml of ether, 70% nitric acid (9.0 g, 0.1 mol) was slowly dropwise added at room temperature. The reaction solution was stirred for further 20 minutes, then washed with water, dried over anhydrous sodium sulfate and concentrated. The solid substance thereby obtained, was repeatedly recrystallized from hexane-ethyl acetate, whereby 6.2 g of 2,3-dihydro-2,2-dimethyl-4-nitro-7-benzofuranol and 6.0 g of 2,3-dihydro-2,2-dimethyl-6-nitro-7-benzofuranol as its 6-nitro isomer, were obtained. The melting points of these products were 164°-165° C. and 125°-126° C., respectively. Further, the structures of these intermediate phenols were confirmed by 1H-NMR spectra. 2,3-Dihydro-2,2-dimethyl-4-nitro-7-benzofuranol thus obtained, was reacted with O-ethyl-S-n-propylthiophosphoryl chloride in the same manner as in Example 1, whereby the compound (No. 6) identified in Table 1 was obtained.

Workup

  1. washwashed with water
  2. dry with materialdried over anhydrous sodium sulfate
  3. concentrationconcentrated
  4. customThe solid substance thereby obtained
  5. customwas repeatedly recrystallized from hexane-ethyl acetate, whereby 6.2 g of 2,3-dihydro-2,2-dimethyl-4-nitro-7-benzofuranol and 6.0 g of 2,3-dihydro-2,2-dimethyl-6-nitro-7-benzofuranol as its 6-nitro isomer
  6. customwere obtained
  7. customwere 164°-165° C. and 125°-126° C.

Sources & evidence

ORD record
ord-8d2de82983b340b4a7879658e800ad51
Source dataset
uspto-grants-1985_12
Patent number
US04560682

Linked notes

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