HCID 15557329, compound → HCID 15557332, compound

HRID 267799Notes

Reaction equation

HRID 267799 reaction equation
[OH:1][C:2]1[CH:20]=[CH:19][C:5]2[O:6][CH2:7][C:8]3([CH2:17][O:18][C:4]=2[CH:3]=1)[O:12]C(=O)[N:10]([CH:14]([CH3:16])[CH3:15])[CH2:9]3.O.O.O.O.O.O.O.O.[OH-].[Ba+2].[OH-]>O>[OH:12][C:8]1([CH2:9][NH:10][CH:14]([CH3:16])[CH3:15])[CH2:7][O:6][C:5]2[CH:19]=[CH:20][C:2]([OH:1])=[CH:3][C:4]=2[O:18][CH2:17]1

Participants

4

Reactant 2

HCID 15557329HCID 15557329, compoundHCID 17749109Barium hydroxide, octahydrate

Product 1

HCID 15557332HCID 15557332, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A mixture of 7-hydroxy-3'-isopropyl-3,4-dihydro-2H-1,5-benzodioxepin-3-spiro-5'-oxazolidin-2'-one (200 mg.; 0.716 mmole), barium hydroxide octahydrate (1.08 g.; 3.42 mole) and water (3.2 ml.) in an evacuated sealed glass tube (a Carius tube) is heated in a rocking oven at 160°-165° C. for 16 hours. The reaction mixture then is poured into boiling water (60 ml.) with stirring and vigorous passage of carbon dioxide until all barium ions have been removed from solution (pH ca. 6.8 by narrow range paper: no precipitate when a small portion is tested with sulfate ions). The solution is filtered through a little celite and evaporated to dryness under reduced pressure, affording 187 mg. of pale brown scaly solid. The crude product is purified by dry column chromatography on silica gel deactivated with 15% of water, using 3% methanol in ether for the development. The desired product is the second component to be eluted from the column, 70.5 mg., (38.9%). After drying at 60° C. in air, the solid still contains water of crystallization and has m.p. ca. 108°-110° C. The anhydrous compound is obtained by drying the hydrate at 80° C./0.1 m.m. for 1 hour and then has m.p. 133°-134.5° C. Recrystallization from benzene (ca. 30 parts V/W) provides 3,7-dihydroxy-3-isopropylaminomethyl-3,4-dihydro-2H-1,5-benzodioxepin, m.p. 133.5°-135° C.

Workup

  1. customsealed glass tube (a Carius tube)
  2. temperatureis heated in a rocking oven at 160°-165° C. for 16 hours
  3. additionThe reaction mixture then is poured
  4. customvigorous passage of carbon dioxide until all barium ions have been removed from solution (pH ca. 6.8 by narrow range paper
  5. filtrationThe solution is filtered through a little celite
  6. customevaporated to dryness under reduced pressure
  7. customaffording 187 mg
  8. customThe crude product is purified
  9. customby dry column chromatography on silica gel
  10. washto be eluted from the column, 70.5 mg
  11. customAfter drying at 60° C. in air
  12. customthe solid still contains water of crystallization
  13. customThe anhydrous compound is obtained
  14. dry with materialby drying the hydrate at 80° C./0.1 m
  15. customRecrystallization from benzene (ca. 30 parts V/W)

Sources & evidence

ORD record
ord-364f221da44045a391c1ea4cd86b1f17
Source dataset
uspto-grants-1976_03
Patent number
US03944560

Reaction notes

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