Phosgene → HCID 68128259, compound

HRID 1730872Notes

Reaction equation

HRID 1730872 reaction equation
[NH2:1][CH:2]1[C:20](=[O:21])[N:4]2[C:5]([C:17]([OH:19])=[O:18])=[C:6]([CH2:9][S:10][C:11]3[S:15][C:14]([CH3:16])=[N:13][N:12]=3)[CH2:7][S:8][C@H:3]12.Cl[SiH2][ClH][SiH2]Cl.[C:27](Cl)(Cl)=[O:28].[CH2:31]([NH2:34])[CH:32]=[CH2:33]>C(Cl)Cl.O.C(N(CC)CC)C.C1(C)C=CC=CC=1>[CH2:31]([NH:34][C:27](=[O:28])[NH:1][CH:2]1[C:20](=[O:21])[N:4]2[C:5]([C:17]([OH:19])=[O:18])=[C:6]([CH2:9][S:10][C:11]3[S:15][C:14]([CH3:16])=[N:13][N:12]=3)[CH2:7][S:8][C@H:3]12)[CH:32]=[CH2:33]

Participants

8

Reactant 3

HCID 6371PhosgeneHCID 7853AllylamineHCID 129420347-Amino-3-(5-methyl-1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid

Product 1

HCID 68128259HCID 68128259, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
20 °C

Procedure

To a cold solution (0° C) of 7-amino-3-(2-methyl-1,3,4-thiadiazol-5-ylthiomethyl)-3-cephem-4-carboxylic acid (6.888 g) in 80 ml. of methylene chloride is added trichlorsilane. The medium is stirred for 15 minutes at 20° C and 100 ml. of toluene is added. The solution is cooled up to -60° C and triethylamine (28 ml) and liquid (-70° C) phosgene (3.2 ml) are added. The medium is stirred for 3 hrs at -50° C. Most of the solvents is then eliminated under reduced pressure (1 mm Hg), the residual solution is allowed to reach room temperature and then immediately added to allylamine (0.888 ml) in methylene chloride (20 ml) with stirring for 10 hrs. After hydrolysis of the trimethylsilylester with water, the solvent is removed by evaporation and the residue is purified by chromatography on Silicagel Merck 0.2-0.06 mm to yield 7-(3-allylureido)-3-(2 -methyl-1,3,4-thiadiazol-5-ylthiomethyl)-3-cephem-4-carboxylic acid with the same characteristics as the product obtained in Example 15.

Workup

  1. temperatureThe solution is cooled up to -60° C
  2. stirringThe medium is stirred for 3 hrs at -50° C
  3. customto reach room temperature
  4. stirringwith stirring for 10 hrs
  5. customthe solvent is removed by evaporation
  6. customthe residue is purified by chromatography on Silicagel Merck 0.2-0.06 mm

Sources & evidence

ORD record
ord-c558339bf3f14f709e7ebe16329b0be9
Source dataset
uspto-grants-1976_11
Patent number
US03994887

Reaction notes

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