Sodium Hydroxide → HCID 53996533, compound

HRID 328455Notes

Reaction equation

HRID 328455 reaction equation
[S:1]1[C:5]([C:6](=O)[C:7]([OH:9])=[O:8])=[CH:4][C:3]2[CH:11]=[CH:12][CH:13]=[CH:14][C:2]1=2.Cl.[C:16]([O:20][NH2:21])([CH3:19])([CH3:18])[CH3:17].[OH-].[Na+]>C(O)C>[C:16]([O:20][N:21]=[C:6]([C:5]1[S:1][C:2]2[CH:14]=[CH:13][CH:12]=[CH:11][C:3]=2[CH:4]=1)[C:7]([OH:9])=[O:8])([CH3:19])([CH3:18])[CH3:17]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 2777906O-tert-butylhydroxylamine hydrochloride2×HCID 20406749HCID 20406749, compound

Product 1

HCID 53996533HCID 53996533, compoundYield 38.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Benzo[b]-thien-2-ylglyoxylic acid (3.09 g) and t-butoxyamine hydrochloride (1.98 g) were dissolved in 50% aqueous ethanol (100 ml). The solution was adjusted to pH 4.5 with sodium hydroxide solution and maintained at such for 4 hr. at room temperature. Thin-layer chromatography showed incomplete reaction. t-Butoxyamine hydrochloride (500 mg.) was added and the solution kept at room temperature overnight. The alcohol was removed by evaporation and the aqueous phase adjusted to pH 8 and washed with ether. The aqueous phase was then acidified to pH 1.5 under ether. The ether solution was washed with water and dried. Evaporation gave a cream solid (4.05 g.). Fractional crystallisation from cyclohexane gave the anti-isomer of the title compound (1.6 g.). The mother liquors were combined and evaporated to give a cream solid (2.11 g.) that was treated in ether with excess diazomethane in ether at 0°-5°. The excess reagent was destroyed by acetic acid and the ether solution washed with sodium bicarbonate, water and dried. Evaporation gave an oil (1.75 g.). This was dissolved in methanol (70 ml) and treated with sodium hydroxide solution (N: 7 ml.) at room temperature for 3 hr. Hydrochloric acid (2N: 3.5 ml) was added and the methanol was removed by evaporation. The aqueous residue was partitioned between ether and sodium bicarbonate solution. The ether layer was washed with water and dried. Evaporation gave an oil (0.92 g.) that was dissolved in methanol (20 ml.) and treated with sodium hydroxide (N: 7 ml) at reflux temperature for 3hr. Sodium hydroxide (N: 5ml) was added and the solution refluxed for 6 hr. The methanol was removed by evaporation and the residue partitioned between ether and water. The aqueous phase was acidified (pH 1.5) under ether and the ether layer washed with water, dried and evaporated to give a pale orange crystalline solid (760 mg. 18%). Crystallisation from benzene containing cyclohexane gave syn-2-t-butoxyimino-2-(benzo[b]-thien-2-yl)acetic acid (430 mg.) m.p. 108°-9°, λmax. (EtOH) 231, 253, 297 nm (ε17,000, 7,240, 24,500).

Workup

  1. temperaturemaintained at such for 4 hr
  2. customat room temperature
  3. customreaction
  4. customThe alcohol was removed by evaporation
  5. washwashed with ether
  6. washThe ether solution was washed with water
  7. customdried
  8. customEvaporation
  9. customgave a cream solid (4.05 g.)
  10. customFractional crystallisation from cyclohexane

Sources & evidence

ORD record
ord-ece87b044a2c48c38b9b3e106f8cf421
Source dataset
uspto-grants-1977_04
Patent number
US04017515

Reaction notes

Loading…