Pentachlorophenol → HCID 54056070, compound

HRID 1607142Notes

Reaction equation

HRID 1607142 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([C:14]([OH:16])=[O:15])[CH2:10][CH2:11][S:12][CH3:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cl:17][C:18]1[C:23](O)=[C:22]([Cl:25])[C:21]([Cl:26])=[C:20]([Cl:27])[C:19]=1[Cl:28].C1(N=C=NC2CCCCC2)CCCCC1>C(OCC)(=O)C>[Cl:17][C:18]1[C:23]([O:15][C:14](=[O:16])[C@@H:9]([CH2:10][CH2:11][S:12][CH3:13])[NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])=[C:22]([Cl:25])[C:21]([Cl:26])=[C:20]([Cl:27])[C:19]=1[Cl:28]

Participants

5

Reactant 3

HCID 992PentachlorophenolHCID 10868DicyclohexylcarbodiimideHCID 111051N-(tert-Butyloxycarbonyl)-D-methionine

Product 1

HCID 54056070HCID 54056070, compoundYield 81.4%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

t-Butoxycarbonyl-D-methionine (20 g, 80.22 mmol) is added to a solution of pentachlorophenol (21.37 g) and dicyclohexylcarbodiimide (16.55 g, 80.3 mmol) in ethyl acetate (200 ml). After 2.5 h the solution is filtered after 2.5 h and the filtrate evaporated to dryness. The residue is recrystallised from hot methanol to give t-butoxycarbonyl-D-methionine pentachlorophenyl ester (32.5 g, 81.4%). A sample of this material (1.03 g, 2.14 mmol) is dissolved in DMF (10 ml) and to this solution is added hydroxylamine hydrochloride (0.149 g, 2.16 mmol) and diisopropylethylamine (0.91 ml, 5.2 mmol). After 16 h at room temperature the solvent is removed by evaporation and the residue partitioned between diethyl ether and 5% aqueous sodium carbonate. The aqueous phase (together with an insoluble oil which forms at the interface) is acidified by addition of citric acid to pH 6 and the product extracted twice with ethyl acetate. The combined ethyl acetate phases are washed successively with water and brine then dried over sodium sulfate. After the solvent is removed by evaporation the product is obtained as a crystalline solid by addition of a small amount of diethyl ether. A sample is recrystallised from ethyl acetate/hexane. mp 133°-134° C. 1H NMR δ (CDCl3) 8.50 (1H, broad s, --NH--), 5.58 (1H, m, urethane NH), 4.23 (1H, m, α--CH), 2.56 (H, m, γCH2), 2.09 (3H, s, S--CH3), 2.03 (1H, m, CH--CHAHB), 1.91 (1H, m, CH--CHAHB), 1.43 (9H, s, C(CH3)3); m/e (EI+) 265 (M+1), (CI-) 2.63 (M-1).

Workup

  1. filtrationAfter 2.5 h the solution is filtered after 2.5 h
  2. customthe filtrate evaporated to dryness
  3. customThe residue is recrystallised from hot methanol

Sources & evidence

ORD record
ord-34dc36e5b05d4726acc13077e298f4b0
Source dataset
uspto-grants-1989_09
Patent number
US04863953

Reaction notes

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