Hydrochloric Acid → 3-hydroxy-3-isopropylaminomethyl-7-nitro-3,4-dihydro-2H-1,5-benzodioxepin

HRID 267798Notes

Reaction equation

HRID 267798 reaction equation
[CH:1]([N:4]1[CH2:8][C:7]2([CH2:14][O:13][C:12]3[CH:15]=[CH:16][C:17]([N+:19]([O-:21])=[O:20])=[CH:18][C:11]=3[O:10][CH2:9]2)[O:6]C1=O)([CH3:3])[CH3:2].[OH-].[K+].Cl.[OH-].[Na+]>O.CCOCC.O1CCOCC1>[OH:6][C:7]1([CH2:8][NH:4][CH:1]([CH3:3])[CH3:2])[CH2:14][O:13][C:12]2[CH:15]=[CH:16][C:17]([N+:19]([O-:21])=[O:20])=[CH:18][C:11]=2[O:10][CH2:9]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 155573273'-isopropyl-7-nitro-3,4-dihydro-2H-1,5-benzodioxepin-3-spiro-5'-oxazolidin-2'-one

Product 1

HCID 155573303-hydroxy-3-isopropylaminomethyl-7-nitro-3,4-dihydro-2H-1,5-benzodioxepin

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 3'-isopropyl-7-nitro-3,4-dihydro-2H-1,5-benzodioxepin-3-spiro-5'-oxazolidin-2'-one (7.98 g.; 25.9 mmole), dioxane (60 ml. and 45% aqueous potassium hydroxide solution (16 ml.) in a nitrogen-filled steel pressure-vessel is heated in a rocking-furnace at 150°-160° C. for 16 hours. The reaction mixture then is poured into ether (100 ml.) and the organic layer separated. The aqueous solution is extracted with ether (100 ml.) and the combined ethereal solution is washed twice with saturated sodium chloride solution (2 × 100 ml.) and then with water (100 ml.). The ethereal solution is extracted with 2.75N hydrochloric acid (40 ml.; 0.11 mole) and twice with water (2 × 40 ml.). The combined acid and aqueous extracts is basified with 2.5N sodium hydroxide solution (70 ml.; 0.175 mole) and the liberated base extracted with ether (2 × 100 ml.). After drying the ethereal solution over anhydrous magnesium sulfate and then over calcium sulfate mixed with a little charcoal, it is evaporated to an oil that soon crystallizes providing 3-hydroxy-3-isopropylaminomethyl-7-nitro-3,4-dihydro-2H-1,5-benzodioxepin as a bright yellow solid, yield 6.33 g., (86.7%), m.p. 95-96.5` C. Recrystallization from di-isopropyl ether (63 ml.) affords 4.56 g., (62.4%) of product, m.p. 97.5°-99° C.

Workup

  1. temperatureis heated in a rocking-furnace at 150°-160° C. for 16 hours
  2. customthe organic layer separated
  3. extractionThe aqueous solution is extracted with ether (100 ml.)
  4. washthe combined ethereal solution is washed twice with saturated sodium chloride solution (2 × 100 ml.)
  5. extractionthe liberated base extracted with ether (2 × 100 ml.)
  6. dry with materialAfter drying the ethereal solution over anhydrous magnesium sulfate
  7. additionover calcium sulfate mixed with a little charcoal, it
  8. customis evaporated to an oil that
  9. customsoon crystallizes

Sources & evidence

ORD record
ord-479f181eeb654744bccd3131729f4339
Source dataset
uspto-grants-1976_03
Patent number
US03944560

Reaction notes

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