Iodine → Carbamic acid, [4,5-dihydro-4-(iodomethyl)-2-thiazolyl]-, 1,1-dimethylethyl ester

HRID 47781Notes

Reaction equation

HRID 47781 reaction equation
C(=O)(O)[O-].[Na+].[CH2:6]([S:9][C:10](=[N:19][C:20](=[O:26])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])[NH:11]C(OC(C)(C)C)=O)[CH:7]=[CH2:8].[I:27]I.O>ClCCl>[I:27][CH2:8][CH:7]1[CH2:6][S:9][C:10]([NH:19][C:20](=[O:26])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[N:11]1

Participants

6

Reactant 4

HCID 807IodineHCID 962WaterHCID 516892Sodium Bicarbonate2×HCID 73994466Tert-butyl allylsulfanyl-[(tert-butoxycarbonyl)amino]methylidenecarbamate

Product 1

HCID 22747901Carbamic acid, [4,5-dihydro-4-(iodomethyl)-2-thiazolyl]-, 1,1-dimethylethyl esterYield 74.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

17 g of sodium bicarbonate are added, at a temperature in the region of 20° C., to a suspension of 25.4 g of tert-butyl allylsulfanyl-[(tert-butoxycarbonyl)amino]methylidene-carbamate in 650 cm3 of dichloromethane, followed by addition of a solution of 24.4 g of iodine predissolved in 850 cm3 of dichloromethane. After 72 hours at a temperature in the region of 20° C., 500 cm3 of water and 500 cm3 of saturated sodium bicarbonate solution are added to the reaction medium and the resulting mixture is then extracted with twice 1 dm3 of ethyl acetate. The organic phases are washed with saturated sodium sulfite solution and then with saturated sodium chloride solution, dried over magnesium sulfate, filtered and then concentrated under reduced pressure (1 kPa) at a temperature in the region of 50° C. The residue obtained is crystallized from ethyl acetate. 20.5 g of tert-butyl N-[(4RS)-4-(iodomethyl)-4,5-dihydro-2-thiazolyl]carbamate are obtained in the form of a yellow solid [1H NMR spectrum (300 MHz, (CD3)2SO-d6, δ in ppm): 1.41 (s: 9H); 2.97 (dd, J=11.5 and 7 Hz: 1H); from 3.30 to 3.50 (mt: 3H); 4.12 (mt: 1H); 9.89 (unresolved complex: 1H)].

Workup

  1. extractionthe resulting mixture is then extracted with twice 1 dm3 of ethyl acetate
  2. washThe organic phases are washed with saturated sodium sulfite solution
  3. dry with materialwith saturated sodium chloride solution, dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure (1 kPa) at a temperature in the region of 50° C
  6. customThe residue obtained
  7. customis crystallized from ethyl acetate

Sources & evidence

ORD record
ord-1161d1656c89434489b8e1f921ca53c4
Source dataset
uspto-grants-2004_03
Patent number
US06699895B2

Reaction notes

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