Methanol → HCID 86751593, compound

HRID 2293790Notes

Reaction equation

HRID 2293790 reaction equation
CO.[C:3]([O:7][C:8]([C@H:10]1[N:14]([C:15](=[O:38])[CH2:16][NH:17][C:18]([NH:20][C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([CH2:27][C:28]([O:30]CC3C=CC=CC=3)=[O:29])[CH:22]=2)=[O:19])[C@@H:13]([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C@H:12]([C:45]([OH:47])=[O:46])[S:11]1)=[O:9])([CH3:6])([CH3:5])[CH3:4].C([O-])=O.[NH4+]>[OH-].[Na+].[Pd]>[C:3]([O:7][C:8]([C@H:10]1[N:14]([C:15](=[O:38])[CH2:16][NH:17][C:18](=[O:19])[NH:20][C:21]2[CH:22]=[C:23]([CH2:27][C:28]([OH:30])=[O:29])[CH:24]=[CH:25][CH:26]=2)[C@@H:13]([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C@H:12]([C:45]([OH:47])=[O:46])[S:11]1)=[O:9])([CH3:6])([CH3:4])[CH3:5]

Participants

6

Reactant 3

HCID 887MethanolHCID 2723923Ammonium formateHCID 67720482HCID 67720482, compound

Product 1

HCID 86751593HCID 86751593, compoundYield 73.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
25 °C

Procedure

10 ml of methanol are added slowly, under an inert atmosphere, to a round-bottomed flask containing 0.3 g of (2S,4S,5R)-2-tert-butoxycarbonyl-3-{2-[3-(3-benzyloxycarbonylmethylphenyl)ureido]-acetyl}-4-phenyl-5-thiazolidinecarboxylic acid, 0.18 g of ammonium formate and 0.3 g of 10% palladium-on-charcoal. The reaction medium is heated at reflux for 1 hour and then cooled to a temperature in the region of 25° C. The catalyst is separated out by filtration and the filtrate is concentrated to dryness under reduced pressure at 40° C. The residue obtained is dissolved in 9.4 ml of aqueous 0.1N sodium hydroxide solution. The aqueous solution obtained is filtered and brought to pH 2 by addition of aqueous 0.1N hydrochloric acid solution. The precipitated product is isolated by filtration, washed with twice 5 ml of water and air-dried. 0.19 g of 3-{3-[2-((2S,4S,5R)-2-tert-butoxycarbonyl-5-carboxy-4-phenyl-3-thiazolidinyl)-2-oxoethyl]ureido}phenylacetic acid is thus obtained in the form of a white solid melting at 130° C., [α]D25 =-3.9°±1.0 (c=0.407; MeOH); 1H NMR (200 MHz, (CD3)2SO with addition of a few drops of CD3COOD, at a temperature of 373 K, δ in ppm): 1.49 (s, 9H: CH3 of the tert-butyl); 3.49 (s, 2H: ArCH2COO); 3.65 and 4.03 (broad d and d respectively, J=17 Hz, 1H each: COCH2N); 4.19 (d, J=3.5 Hz, 1H: H at C5 of the ring); 5.70 (s, 1H: H at C2 of the ring); 5.76 (d, J=3.5 Hz, 1H: H at C4 of the ring); 6.83 (broad d, J=7.5 Hz, 1H: aromatic H (H ortho to the CH2)); 7.14 (t, J=7.5 Hz, 1H: aromatic H (H meta to the CH2); from 7.20 to 7.50 (mt, 5H: aromatic H); 7.72 (broad d, J=7.5 Hz, 2H: H ortho to the phenyl).

Workup

  1. temperatureThe reaction medium is heated
  2. temperatureat reflux for 1 hour
  3. customThe catalyst is separated out by filtration
  4. concentrationthe filtrate is concentrated to dryness under reduced pressure at 40° C
  5. customThe residue obtained
  6. customThe aqueous solution obtained
  7. filtrationis filtered
  8. additionbrought to pH 2 by addition of aqueous 0.1N hydrochloric acid solution
  9. customThe precipitated product is isolated by filtration
  10. washwashed with twice 5 ml of water
  11. customair-dried

Sources & evidence

ORD record
ord-7e36c4788d364eab957d259dcc0c054d
Source dataset
uspto-grants-1997_11
Patent number
US05686622

Reaction notes

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