m-Tolyl isocyanate → HCID 86750530, compound

HRID 975956Notes

Reaction equation

HRID 975956 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([N:8]=[C:9]=[O:10])[CH:5]=[CH:6][CH:7]=1.[NH2:11][CH2:12][C:13]([N:15]1[C@H:19]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:18][S:17][C@@H:16]1[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:14]>O1CCCC1.C(OCC)(=O)C>[CH3:1][C:2]1[CH:3]=[C:4]([NH:8][C:9](=[O:10])[NH:11][CH2:12][C:13]([N:15]2[C@H:19]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:18][S:17][C@@H:16]2[C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)=[O:14])[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 69303m-Tolyl isocyanateHCID 53866151HCID 53866151, compound

Product 1

HCID 86750530HCID 86750530, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

0.8 cm3 of 3-methylphenyl isocyanate is added to a solution of 2.0 g of tert-butyl (2R,4R)-3-(2-aminoacetyl)-2-phenyl-4-thiazolidinecarboxylate in 25 cm3 of anhydrous tetrahydrofuran. The reaction mixture is stirred for 12 hours at a temperature in the vicinity of 25° C., then diluted with 100 cm3 of ethyl acetate. The organic phase is washed with 2 times 40 cm3 of water, dried over magnesium sulphate and concentrated to dryness under reduced pressure at 40° C. The crude product obtained is purified by chromatography on silica [eluent: methylene chloride/methanol (98/2 by volume)]. The fractions containing the expected product are combined and concentrated to dryness under reduced pressure at 40° C. After vigorous stirring in heptane, 0.5 g of tert-butyl (2R,4R)-3-{2-[3-(3-methylphenyl)ureido]acetyl}-2-phenyl-4-thiazolidinecarboxylate is thus obtained in the form of a white amorphous powder ([α]D20 =+70.0°±1.3° (C=1.02%; CHCl3)) [proton NMR (200 MHz, CDCl3, δ in ppm), 2 rotamers at room temperature, description for the preponderant rotamer at 25° C.: 1.45 (bs, 9H, (CH3)3); 2.2 (s, 3H, CH3); 3.2 (A2X, 2H, CH2S); 3.2 and 4.3 (ABX, 2H, CH2N); 4.9 (t, 1H, CHN); 6.1 (bdd, 1H, NH); 6.2 (s, 1H, SCHN); 6.8 to 7,7 (m, 9H, aromatic). Infrared spectrum (KBr), characteristic bands in cm-1 : 3375, 2975, 2930, 1735, 1650, 1610, 1595, 1560, 1490, 1455, 1370, 1150, 780, 730, 695].

Workup

  1. washThe organic phase is washed with 2 times 40 cm3 of water
  2. dry with materialdried over magnesium sulphate
  3. concentrationconcentrated to dryness under reduced pressure at 40° C
  4. customThe crude product obtained
  5. customis purified by chromatography on silica [eluent: methylene chloride/methanol (98/2 by volume)]
  6. additionThe fractions containing the expected product
  7. concentrationconcentrated to dryness under reduced pressure at 40° C
  8. stirringAfter vigorous stirring in heptane

Sources & evidence

ORD record
ord-e54dbb9985d74a4aa119f7bd933ffd1b
Source dataset
uspto-grants-1997_03
Patent number
US05610144

Reaction notes

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