Hydrochloric Acid → 1-(2-(5-Amino-4-oxopentanoyloxy)ethyl)-2-ethyl-3,4-dihydroxypyridinium chloride hydrochloride

HRID 526673Notes

Reaction equation

HRID 526673 reaction equation
C(OC([NH:11][CH2:12][C:13](=[O:38])[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH2:20][N:21]1[CH:26]=[CH:25][C:24](=[O:27])[C:23]([O:28]CC2C=CC=CC=2)=[C:22]1[CH2:36][CH3:37])=[O:17])=O)C1C=CC=CC=1.C(O)C.[ClH:42]>[Pd].O>[ClH:42].[Cl-:42].[NH2:11][CH2:12][C:13](=[O:38])[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH2:20][N+:21]1[CH:26]=[CH:25][C:24]([OH:27])=[C:23]([OH:28])[C:22]=1[CH2:36][CH3:37])=[O:17]

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 702EthanolHCID 900688162-(3-(Benzyloxy)-2-ethyl-4-oxopyridin-1(4H)-yl)ethyl 5-(benzyloxycarbonylamino)-4-oxopentanoate

Product 1

HCID 732917321-(2-(5-Amino-4-oxopentanoyloxy)ethyl)-2-ethyl-3,4-dihydroxypyridinium chloride hydrochlorideYield 96%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent2×

Procedure

A stirred solution of 2-(3-(benzyloxy)-2-ethyl-4-oxopyridin-1(4H)-yl)ethyl 5-(benzyloxycarbonylamino)-4-oxopentanoate (7) (247 mg, 0.475 mmol) in 6:1 v/v ethanol:water (3.5 mL) was acidified to pH=1 by addition of hydrochloric acid (37% aq.). Palladium on activated charcoal (11 mg, 10% w/w) was added, the reaction vessel was evacuated then filled with hydrogen and the reaction was stirred under hydrogen (at atmospheric pressure) for 2 h. The resulting suspension was filtered through Celite®, eluting with ethanol and the filtrate was then concentrated in vacuo to give the product as a mixture of mono- and di-salts. Three cycles of dissolution in water, addition of hydrochloric acid (37% aq.) then concentration in vacuo gave the title compound 8 (169 mg, 96%) as a brown oil, δH (300 MHz; D2O) 7.82 (1H, d, J 8.0 Hz, Ar 6-H), 6.92 (1H, d, J 8.0 Hz, Ar 5-H), 4.27 (2H, t, J 6.0 Hz, OCH2CH2), 3.91 (2H, s, H3N+CH2), 3.74 (2H, t, J 6.0 Hz, OCH2CH2), 2.80 (2H, q, J 7.0 Hz, CH3CH2), 2.66 (2H, t, J 6.0 Hz, C(O)CH2), 2.45 (2 H, t, J 6.0 Hz, C(O)CH2) and 0.98 ppm (3H, t, J 7.0 Hz, CH3); δC (75 MHz; D2O) 204.3, 176.9, 158.6, 147.7, 142.5, 139.5, 111.0, 60.6, 57.8, 47.3, 34.6, 27.6, 20.1 and 11.3 ppm; m/z (ES+) 297.1445 (100%, [M-H-2Cl]+), C14H21N2O5 requires M, 297.1445.

Workup

  1. customthe reaction vessel was evacuated
  2. additionthen filled with hydrogen
  3. filtrationThe resulting suspension was filtered through Celite®
  4. washeluting with ethanol
  5. concentrationthe filtrate was then concentrated in vacuo
  6. customto give the product
  7. additionas a mixture of mono- and di-salts
  8. concentrationconcentration in vacuo

Sources & evidence

ORD record
ord-f9e842138b974eb4a176218f968d35a8
Source dataset
uspto-grants-2016_05
Patent number
US09346758B2

Reaction notes

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