Potassium Hydroxide → 1-Methoxycarbonyl-3-oxopiperidine-4-carbohydroxamic acid ethylene acetal

HRID 1155341Notes

Reaction equation

HRID 1155341 reaction equation
[OH-:1].[K+].[Cl-].O[NH3+:5].[CH2:6]1[O:24][C:9]([CH:13]2[CH2:18][CH2:17][N:16]([C:19]([O:21][CH3:22])=[O:20])[CH2:15][C:14]2=[O:23])(OCC)[O:8][CH2:7]1.[K+].[Br-]>CO.C(OCC)(=O)C.CO.C(O)=O.C(O)=O.C(OCC)(=O)C.C(O)(=O)C>[CH2:6]1[O:24][C:9]([CH:13]2[CH2:18][CH2:17][N:16]([C:19]([O:21][CH3:22])=[O:20])[CH2:15][C:14]2=[O:23])([NH:5][OH:1])[O:8][CH2:7]1

Participants

10

Reactant 4

HCID 14797Potassium HydroxideHCID 21645Hydroxylamine HClHCID 253877Potassium BromideHCID 70082215Ethyl 1-methoxycarbonyl-3-oxopiperidine-4-carboxylate ethylene acetal

Product 1

HCID 566239341-Methoxycarbonyl-3-oxopiperidine-4-carbohydroxamic acid ethylene acetal

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 284Formic AcidSolventHCID 887MethanolSolvent3×HCID 8857Ethyl AcetateSolventHCID 86737854Ethyl acetate methanol formic acidSolvent

Procedure

To a stirred and iced solution of potassium hydroxide (7.3 g; 130 mmol) in methanol (30 ml) was added hydroxylammonium chloride (6.9 g; 100 mmol). After stirring at 0° C. for further 30 minutes a solution of ethyl 1-methoxycarbonyl-3-oxopiperidine-4-carboxylate ethylene acetal (6.8 g; 25 mmol) in methanol (20 ml) was added, and the mixture was left at 8° C. for 8 days. Upon addition of glacial acetic acid (15 ml) and filtration the filtrate was evaporated in vacuo to give a treacly mass. CC [silica gel (Woelm 0.063-0.1 mm): 250 g; eluents: ethyl acetate to which methanol (15-26%) and formic acid (1%) was added] afforded IXa (1.9 g; 29%) as a crystalline and TLC-pure substance [RF : 0.23; eluent: ethyl acetate-methanol-formic acid (90:9:1)]. An analytical sample was recrystallized (ethanol-benzene) to give IXa as colourless crystals, m.p. 150.0°-152.0° C. IR (KBr): 3700-3350 (m), 3280 (m), 3210 (s), 3055 (w), 3000-2870 (several bands, w-m), 1690 (s), 1640 (s), 1550 (w) cm-1. 1H NMR [CDCl3 -DMSO-d6 (1:1): δ10.5-10.1 (1 H, m), 4.9-4.3 (1 H, m), 3.93 (s), 3.60 (s), and 4.1-3.1 (m) (a total of 11 H), 2.8-2.6 (1 H, m), 2.2-1.8 (2 H, m).

Workup

  1. additionwas added
  2. customwas evaporated in vacuo
  3. customto give a treacly mass
  4. customAn analytical sample was recrystallized (ethanol-benzene)
  5. customto give IXa as colourless crystals, m.p. 150.0°-152.0° C

Sources & evidence

ORD record
ord-f631853799e0431992e4d2d453ad9562
Source dataset
uspto-grants-1981_11
Patent number
US04301287

Reaction notes

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