Nitric Acid → HCID 13591797, compound

HRID 638153Notes

Reaction equation

HRID 638153 reaction equation
[C:1]([O:4][C:5]1[C:13]2[O:12][C:11]([CH3:15])([CH3:14])[CH2:10][C:9]=2[CH:8]=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[N+:16]([O-])([OH:18])=[O:17]>C(Cl)(Cl)Cl>[C:1]([O:4][C:5]1[C:13]2[O:12][C:11]([CH3:15])([CH3:14])[CH2:10][C:9]=2[CH:8]=[C:7]([N+:16]([O-:18])=[O:17])[CH:6]=1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 4982652HCID 4982652, compound

Product 1

HCID 13591797HCID 13591797, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

2,3-Dihydro-2,2-dimethyl-7-benzofuranol (16.4 g, 0.1 mol) was dissolved in 100 ml of an aqueous solution of sodium hydroxide (6.0 g, 0.15 mol), and 12.8 g of acetic anhydride was dumped into the solution and thoroughly mixed, whereby a white solid substance was precipitated. This substance was collected by filtration and dried, whereby 19.5 g of 7-acetoxy-2,3-dihydro-2,2-dimethylbenzofuran was obtained. The melting point of this product was 48.5°-49.5° C. This phenol acetate was dissolved in 400 ml of chloroform, and 60 ml of 70% nitric acid was dropwise added at -5° C. Then, the stirring was continued at 10° C. for one hour. The reaction solution was washed with water, then dried over anhydrous sodium sulfate and concentrated. The solid substance thereby obtained was recrystallized from benzene-cyclohexane, whereby 19.6 g of 7-acetoxy-2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran was obtained. The melting point of this product was 141°-142° C. The structure was confirmed by 1H-NMR spectrum and IR spectrum. Then, the product was added to a solution containing 35 g of sodium hydroxide in 200 ml of water and 50 ml of methanol, and heated at 40° C. for 15 minutes to complete hydrolysis. The reaction solution was neutralized by concentrated hydrochloric acid, and then extracted with ether. The extracted solution was washed with water, then dried over anhydrous sodium sulfate and concentrated, whereby 13.0 g of substantially pure 2,3-dihydro-2,2-dimethyl-5-nitro-7-benzofuranol was obtained. The melting point of this product was 97°-97.5° C. The phenol thus obtained, was reacted with O-ethyl-S-n-propyl-thiophosphoryl chloride in the same manner as in Example 1, whereby the compound (No. 4) identified in Table 1 was obtained as oily substance.

Workup

  1. customwas 48.5°-49.5° C
  2. washThe reaction solution was washed with water
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated
  5. customThe solid substance thereby obtained
  6. customwas recrystallized from benzene-cyclohexane

Sources & evidence

ORD record
ord-d02de524f4994b9aa3192af3a51acf86
Source dataset
uspto-grants-1985_12
Patent number
US04560682

Reaction notes

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