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Iodine → 3-(2-Aminothiazol-5-yl)-2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

HRID 2413404
Notes
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Reaction equation

HRID 2413404 reaction equation
II.[CH:3]([O:16][C:17]([C:19]1[N:20]2[CH:23]([S:24][CH2:25][C:26]=1[CH:27]=[CH:28]N(C)C)[CH:22]([NH:32][C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])[C:21]2=[O:40])=[O:18])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[NH2:41][C:42]([NH2:44])=[S:43]>C(Cl)Cl.O1CCCC1.O.C(OCC)(=O)C>[NH2:41][C:42]1[S:43][C:27]([C:26]2[CH2:25][S:24][CH:23]3[N:20]([C:21](=[O:40])[CH:22]3[NH:32][C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])[C:19]=2[C:17]([O:16][CH:3]([C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)[C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=2)=[O:18])=[CH:28][N:44]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 3

HCID 807IodineHCID 2723790Thiourea2×HCID 539143342-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylamino-vinyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

Product 1

HCID 131759453-(2-Aminothiazol-5-yl)-2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

Reagents, catalysts & solvents 4

HCID 962
Water
Solvent
2×
HCID 6344DichloromethaneSolvent
HCID 8028TetrahydrofuranSolvent2×
HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of iodine (2.54 g) in dry methylene chloride (20 cc) is added, in 5 minutes, to a solution, cooled to -55° C., of 2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylamino-vinyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene, E-form (5.35 g) in dry tetrahydrofuran (20 cc). The reaction mixture is stirred for 2 hours, whilst allowing the temperature gradually to return to 0° C., and is then treated with distilled water (0.36 cc) and stirred for 2 hours at 5° C. A solution of thiourea (0.57 g) in a mixture of tetrahydrofuran (5 cc) and water (2 cc) is added to 25 cc of this reaction mixture and this mixture is stirred for 16 hours at 25° C. Thiourea (0.57 g) is added, stirring is continued for 3 hours at 25° C., and the mixture is then diluted with ethyl acetate (150 cc). The organic phase is washed successively with distilled water (100 cc), saturated sodium bicarbonate solution (100 cc), distilled water (100 cc) and a half-saturated sodium chloride solution (100 cc). After having dried the mixture over magnesium sulphate, the solvent is evaporated under reduced pressure (30 mm Hg; 4 kPa) at 30° C. The residue is chromatographed on a column (height: 30 cm; diameter: 2 cm) of silica (0.04-0.06 mm), elution being carried out under 0.4 bar (40 kPa) with a 45:55 (by volume) mixture of cyclohexane and ethyl acetate. After evaporation of the solvents, 3-(2-amino-thiazol-5-yl)-2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]-oct-2-ene (0.08 g) is obtained in the form of an orange froth, whose characteristics are identical to those of the product described below, in Example 2.

Workup

  1. additionis added, in 5 minutes, to a solution
  2. customto return to 0° C.
  3. stirringstirred for 2 hours at 5° C
  4. stirringthis mixture is stirred for 16 hours at 25° C
  5. stirringstirring
  6. waitis continued for 3 hours at 25° C.
  7. washThe organic phase is washed successively with distilled water (100 cc), saturated sodium bicarbonate solution (100 cc)
  8. distillationdistilled water (100 cc)
  9. dry with materialAfter having dried the mixture over magnesium sulphate
  10. customthe solvent is evaporated under reduced pressure (30 mm Hg; 4 kPa) at 30° C
  11. customThe residue is chromatographed on a column (height: 30 cm; diameter: 2 cm) of silica (0.04-0.06 mm), elution
  12. additionbeing carried out under 0.4 bar (40 kPa) with a 45:55 (by volume) mixture of cyclohexane and ethyl acetate
  13. customAfter evaporation of the solvents

Sources & evidence

ORD record
ord-575eaea066794a528834d19548d9901e
Source dataset
uspto-grants-1985_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04496560

Reaction notes

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