Phosphorus oxychloride → HCID 131712596, compound

HRID 2412775Notes

Reaction equation

HRID 2412775 reaction equation
P(Cl)(Cl)([Cl:3])=O.[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:21]=[C:22]([NH:25][CH:26]=[O:27])[S:23][CH:24]=1)[C:17]([OH:19])=O)=[O:12])([CH3:9])([CH3:8])[CH3:7].[NH2:28][CH:29]1[C:46](=[O:47])[N:31]2[C:32]([C:43]([OH:45])=[O:44])=[C:33]([CH2:36][S:37][C:38]3[S:39][CH:40]=[N:41][N:42]=3)[CH2:34][S:35][C@H:30]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O.CN(C)C=O>[CH3:30][N+:31]([CH3:46])=[CH:32][Cl:3].[Cl-:3].[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:21]=[C:22]([NH:25][CH:26]=[O:27])[S:23][CH:24]=1)[C:17]([NH:28][CH:29]1[C:46](=[O:47])[N:31]2[C:32]([C:43]([OH:45])=[O:44])=[C:33]([CH2:36][S:37][C:38]3[S:39][CH:40]=[N:41][N:42]=3)[CH2:34][S:35][C@H:30]12)=[O:19])=[O:12])([CH3:7])([CH3:8])[CH3:9]

Participants

9

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 128891877-Amino-3-(1,3,4-thiadiazol-2-ylthiomethyl)-3cephem-4-carboxylic acidHCID 543909512-t-Butoxycarbonylmethoxyimino-2-(2-formamidothiazol-4-yl)acetic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712596HCID 131712596, compoundYield 91.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

The Vilsmeier reagent was prepared from dry dimethylformamide (0.667 g.), phosphorus oxychloride (1.40 g.) and dry ethyl acetate (4 ml.) by the conventional method. Dry ethyl acetate (16 ml.) was added thereto and then 2-t-butoxycarbonylmethoxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer) (2 g.) was added thereto at 0° C. The mixture was stirred for 30 minutes at the same temperature. The resulting mixture was added dropwise at -15° C. to a stirred solution of 7-amino-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (3.01 g.) and trimethylsilylacetamide (9.6 g.) in dry ethyl acetate (30 ml.), and the mixture was stirred for 50 minutes at -15° to -5° C. To the reaction mixture was added water (50 ml.). An insoluble material was filtered off and the filtrate was extracted twice with ethyl acetate. The extracts were washed twice with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and evaporated in vacuo. The residue was pulverized with diethyl ether and the powder was collected by filtration and dried to give 7-[2-t-butoxycarbonylmethoxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.67 g.).

Workup

  1. customat 0° C
  2. stirringthe mixture was stirred for 50 minutes at -15° to -5° C
  3. filtrationAn insoluble material was filtered off
  4. extractionthe filtrate was extracted twice with ethyl acetate
  5. washThe extracts were washed twice with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. customevaporated in vacuo
  8. filtrationthe powder was collected by filtration
  9. customdried

Sources & evidence

ORD record
ord-fb8457f9060140e0a0f4f363abd1d721
Source dataset
uspto-grants-1985_01
Patent number
US04493833

Reaction notes

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