Sodium Hydroxide → HCID 70606418, compound

HRID 648464Notes

Reaction equation

HRID 648464 reaction equation
[CH3:1][C:2]1([CH3:29])[CH:6]([NH:7][C:8]([O:10][CH2:11][C:12]([Cl:15])([Cl:14])[Cl:13])=[O:9])[N:5]2[C:16](=[O:28])[C@@H:17]([NH:18]C(=O)CC3C=CC=CC=3)[C@H:4]2[S:3]1.P(Cl)(Cl)(Cl)(Cl)Cl.[OH-].[Na+].P([O-])([O-])(O)=O.[K+].[K+].P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C(Cl)Cl.N1C=CC=CC=1.O.CO>[NH2:18][C@@H:17]1[C:16](=[O:28])[N:5]2[CH:6]([NH:7][C:8]([O:10][CH2:11][C:12]([Cl:14])([Cl:13])[Cl:15])=[O:9])[C:2]([CH3:29])([CH3:1])[S:3][C@H:4]12

Participants

10

Reactant 5

HCID 14798Sodium HydroxideHCID 24450Potassium Phosphate, DibasicHCID 24819Phosphorus pentachlorideHCID 62657Potassium Phosphate, TribasicHCID 70606802HCID 70606802, compound

Product 1

HCID 70606418HCID 70606418, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 11.0 g of 2,2-dimethyl-6β-(N-phenylacetyl-amino)-3-(N-2,2,2-trichloroethoxycarbonyl-amino)-penam in a mixture of 240 ml of anhydrous methylene chloride and 25.6 ml of pyridine is treated with 166 ml of a 10% strength solution of phosphorus pentachloride in methylene chloride under a nitrogen atmosphere -10° C., and is subsequently stirred for 30 minutes at 0° C. 120 ml of absolute methanol are then added whilst cooling strongly (-10° C.) and the mixture is stirred for a further 2 hours. 80 ml of water are added, the pH value (measured in samples diluted with water) is adjusted to 3.3 with about 9 ml of a 2N aqueous sodium hydroxide solution, and the reaction is allowed to continue for one hour at 0° C. and a further hour at 20° C. The mixture is then poured out into 500 ml of a 1M aqueous dipotassium hydrogen phosphate buffer solution whilst stirring, and the pH value is adjusted from 6.5 to 7.0 by adding 50% strength aqueous tripotassium phosphate solution. The aqueous phase is separated off and twice washed with 200 ml of methylene chloride at a time; the three organic solutions are each twice washed with water, combined, dried over sodium sulphate and evaporated under reduced pressure. The crystalline residue is taken up in 40 ml of a 1:1 mixture of benzene and hexane; the mixture is cooled for 15 minutes at 0° C. and the precipitate is filtered off. 6β-Amino-2,2-dimethyl-3-(N-2,2,2-trichloroethoxycarbonyl-amino)-penam is thus obtained, melting at 179°-180° C. (corrected); infrared absorption spectrum: characteristic bands (in methylene chloride) at 2.90μ, 5.58μ, 6.62μ, 7.17μ, 7.27μ, 8.32μ, 8.46μ, 8.82μ, 9.25μ, and 9.62μ; (in Nujol) at 2.95μ, 3.01μ, 3.11μ, 5.64μ, 5.80μ, 6.35μ, 7.60μ, 7.87μ, 8.00μ, 8.27μ, 8.65μ, 8.70μ, 9.16μ, and 9.57μ; thin layer chromatogram (silica gel): Rf=0.17 (in the system toluene/acetone, 8:2) and Rf=0.43 (in the system toluene/acetone, 6:4); characteristic yellow colouration with ninhydrine-collidine (free amino group).

Workup

  1. temperaturewhilst cooling strongly (-10° C.)
  2. stirringthe mixture is stirred for a further 2 hours
  3. waitto continue for one hour at 0° C. and a further hour at 20° C
  4. stirringwhilst stirring
  5. customThe aqueous phase is separated off
  6. washtwice washed with 200 ml of methylene chloride at a time
  7. washeach twice washed with water
  8. dry with materialdried over sodium sulphate
  9. customevaporated under reduced pressure
  10. additionThe crystalline residue is taken up in 40 ml of a 1:1 mixture of benzene and hexane
  11. temperaturethe mixture is cooled for 15 minutes at 0° C.
  12. filtrationthe precipitate is filtered off

Sources & evidence

ORD record
ord-d1eeb3202c8544fda292e9ee8faab0f2
Source dataset
uspto-grants-1988_04
Patent number
US04735937

Reaction notes

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