Dicyclohexylcarbodiimide → HCID 53845922, compound

HRID 1980418Notes

Reaction equation

HRID 1980418 reaction equation
[CH3:1][O:2][N:3]=[C:4]([C:8]1[N:9]=[C:10]([NH:13][C:14]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[S:11][CH:12]=1)[C:5](O)=[O:6].[NH2:33][CH:34]1[C:41](=[O:42])[N:40]2[CH:35]1[S:36](=[O:70])[CH2:37][C:38]([C:59]1[S:63][C:62]([C:64]3[CH:69]=[CH:68][N:67]=[CH:66][CH:65]=3)=[N:61][CH:60]=1)=[C:39]2[C:43]([O:45][CH:46]([C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)=[O:44].C1(N=C=NC2CCCCC2)CCCCC1>C(Cl)Cl>[CH:46]([O:45][C:43]([C:39]1[N:40]2[CH:35]([S:36](=[O:70])[CH2:37][C:38]=1[C:59]1[S:63][C:62]([C:64]3[CH:65]=[CH:66][N:67]=[CH:68][CH:69]=3)=[N:61][CH:60]=1)[CH:34]([NH:33][C:5](=[O:6])[C:4](=[N:3][O:2][CH3:1])[C:8]1[N:9]=[C:10]([NH:13][C:14]([C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=3)[S:11][CH:12]=1)[C:41]2=[O:42])=[O:44])([C:53]1[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=1)[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1

Participants

5

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 2724510(Z)-2-(2-Tritylaminothiazol-4-yl)-2-methoxyiminoacetic acidHCID 20402459HCID 20402459, compound

Product 1

HCID 53845922HCID 53845922, compoundYield 7.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

The syn isomer of 2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetic acid (12.4 g) and 4-N,N-dimethylaminopyridine (0.05 g) are added to a solution of 7-amino-2-benzhydryloxycarbonyl-8-oxo-3-[2-(pyridin-4-yl)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene 5-oxide (15 g) in dry methylene chloride (100 cc), and a solution of N,N'-dicyclohexylcarbodiimide (6.93 g) in methylene chloride (120 cc) is then added (in the course of 30 minutes) after cooling to +5° C. The reaction mixture is then stirred for 1 hour at +5° C. and then for 4 hours at 25° C., after which it is partially concentrated, diluted again with ethyl acetate (500 cc) and filtered. The filtrate is poured into a mixture of distilled water (1 liter), ethyl acetate (1 liter) and acetic acid (10 cc). The organic phase is washed with a saturated solution of sodium bicarbonate (200 cc), distilled water (3×200 cc) and then a saturated solution of sodium chloride (200 cc), dried over sodium sulphate and then concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. to give the crude expected product (26.8 g) in the form of a hard brown foam, which can be purified in the following manner: the crude product (5 g) is redissolved in ethanol (120 cc) under reflux, decolorising charcoal (0.5 g) and silica (0.5 g) are added, the mixture is stirred and filtered and the filtrate is cooled in a bath of iced water. The precipitate is filtered off and washed with ethanol (2×10 cc) and then ether (2×20 cc) to give 2-benzhydryloxycarbonyl-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)acetamido]-8-oxo-3-[2-(pyridin-4-yl)-thiazol-5-yl]-5-thia1-azabicyclo[4.2.0]oct-2-ene 5-oxide (2 g) in the form of an ochre powder.

Workup

  1. temperatureafter cooling to +5° C
  2. waitfor 4 hours at 25° C.
  3. concentrationafter which it is partially concentrated
  4. additiondiluted again with ethyl acetate (500 cc)
  5. filtrationfiltered
  6. additionThe filtrate is poured into a mixture of distilled water (1 liter), ethyl acetate (1 liter) and acetic acid (10 cc)
  7. washThe organic phase is washed with a saturated solution of sodium bicarbonate (200 cc)
  8. distillationdistilled water (3×200 cc)
  9. dry with materiala saturated solution of sodium chloride (200 cc), dried over sodium sulphate
  10. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C.
  11. customto give the crude expected product (26.8 g) in the form of a hard brown foam, which
  12. customcan be purified in the following manner
  13. dissolutionthe crude product (5 g) is redissolved in ethanol (120 cc)
  14. temperatureunder reflux
  15. additionare added
  16. stirringthe mixture is stirred
  17. filtrationfiltered
  18. temperaturethe filtrate is cooled in a bath of iced water
  19. filtrationThe precipitate is filtered off
  20. washwashed with ethanol (2×10 cc)

Sources & evidence

ORD record
ord-c88caeba165e4ea18aeb7ee075794a68
Source dataset
uspto-grants-1985_04
Patent number
US04508717

Reaction notes

Loading…