Acetic Acid → N-(7-Hydroxy-4,5,6,7-tetrahydro-1-benzothiophen-4-yl)urea

HRID 263207Notes

Reaction equation

HRID 263207 reaction equation
[O:1]=[C:2]1[C:7]2[S:8][CH:9]=[CH:10][C:6]=2[CH:5]([NH:11][C:12]([NH2:14])=[O:13])[CH2:4][CH2:3]1.[BH4-].[Na+].C(O)(=O)C>C(O)C>[OH:1][CH:2]1[C:7]2[S:8][CH:9]=[CH:10][C:6]=2[CH:5]([NH:11][C:12]([NH2:14])=[O:13])[CH2:4][CH2:3]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 65473SulbenoxHCID 4311764Sodium borohydride

Product 1

HCID 20348930N-(7-Hydroxy-4,5,6,7-tetrahydro-1-benzothiophen-4-yl)ureaYield 6%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

7-Keto-4,5,6,7-tetrahydrobenzo[b]-thien-4-ylurea (0.5 grams, 2.38 mm) is suspended in ethanol (50 ml.) and to the stirred solution is added solid sodium borohydride (0.5 grams, 13.2 mm). After stirring overnight the mixture is treated cautiously with 5% aqueous acetic acid (20 ml.). After stirring 15 minutes the solvent is removed, the residue dissolved in a small volume of methanol and percolated through a 11/2'×13/4" silica gel dry column eluting with 20% methanolic methylene chloride. The resulting gum is crystallized from ethyl acetate/methanol to afford 66 mg. (13% Y) of the more polar (L.L.C) alcohol (B), melting point 194° C. to 197° C. The mother liquor material is separated into its two major components 7-hydroxy-4,5,6,7-tetrahydrobenzo[b]thien-4-ylurea by high pressure liquid chromatography on "Spherosil XOA 400" using the solvent system: hexane (1800 ml.)/methanol (425)/chloroform (1000) (flow rate~13 ml./min.). This procedure affords the less polar alcohol A (29 mgs. 6% yield) melting point, 162° C. to 169° C. (methanol/ethyl acetate), and the more polar alcohol B (50 mg., 10% yield), melting point 197° C. to 198° C.

Workup

  1. stirringAfter stirring 15 minutes the solvent
  2. customis removed
  3. dissolutionthe residue dissolved in a small volume of methanol
  4. customdry column
  5. washeluting with 20% methanolic methylene chloride
  6. customThe resulting gum is crystallized from ethyl acetate/methanol
  7. customto afford 66 mg
  8. customThe mother liquor material is separated into its two major components 7-hydroxy-4,5,6,7-tetrahydrobenzo[b]thien-4-ylurea by high pressure liquid chromatography on "Spherosil XOA 400"

Sources & evidence

ORD record
ord-d914e85ee63f44dfa8c5d9e438c657e7
Source dataset
uspto-grants-1979_05
Patent number
US04156670

Reaction notes

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