Pyridine → HCID 86735715, compound

HRID 372258Notes

Reaction equation

HRID 372258 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[C:19]([O:21][CH3:22])[CH:18]=[CH:17][C:4]=1[CH2:5][N:6]1[C:9](=[O:10])[C@H:8]([N:11]=[N+:12]=[N-:13])[C@@H:7]1C(O)=O.C(=O)([O-])[O-].[K+].[K+].[C:29](Cl)(=O)[C:30](Cl)=O.N1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.[N+:41](=[CH2:43])=[N-:42]>O1CCCC1.C1C=CC=CC=1.O>[CH3:1][O:2][C:3]1[CH:20]=[C:19]([O:21][CH3:22])[CH:18]=[CH:17][C:4]=1[CH2:5][N:6]1[C:9](=[O:10])[C@H:8]([N:11]=[N+:12]=[N-:13])[C@@H:7]1[NH:42][NH:41][CH2:43][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:19][CH2:20][CH2:3][CH2:4][CH2:17][CH2:18][CH2:29][CH3:30]

Participants

9

Reactant 5

HCID 1049PyridineHCID 9550DiazomethaneHCID 11430Potassium CarbonateHCID 65578Oxalyl chlorideHCID 86735716HCID 86735716, compound

Product 1

HCID 86735715HCID 86735715, compoundYield 105.4%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of 10.1 g (33 mmole) of cis-1-(2,4-dimethoxybenzyl)-3-azido-4-oxo-azetidine-2-carboxylic acid (prepared by reacting the product of example 1 with potassium carbonate in aqueous tetrahydrofuran) in 100 ml of dry benzene at 5° was added 2.54 ml (29.5 mmole) of oxalyl chloride under argon. With vigorous stirring, 2.37 ml (29.5 mmole) of dry pyridine was added dropwise during which time considerable gas evolution occurred. After stirring for 1 hour, the suspension was filtered, the solid washed with cold dry benzene and the combined filtrates concentrated to one-half its volume in vacuum. The acid chloride solution was diluted to its original volume with dry benzene and added dropwise to an ethereal diazomethane solution (0.12 mole, 1.1 L) at 0° with vigorous stirring. A slow stream of argon was passed through the suspension while stirring was continued for 18 hours. 200 ml of water was added to the reaction mixture, the organic phase separated, dried (MgSO4), filtered with suction, and the solvent removed by distillation at reduced pressure. The product was then triturated with 50% diethylether in hexane, collected by suction filtration, and chromatographed (silica gel: benzene with an ethyl acetate gradient up to 30%) yielding 8.5 gr (78.0%) of the title compound as light yellow crystals, mp 83°-84.5°. The corresponding α-chloroketone (2.6 gr, 22.2%) was isolated as a white crystalline solid (mp. 69°-71°).

Workup

  1. customprepared
  2. customat 5°
  3. filtrationthe suspension was filtered
  4. washthe solid washed with cold dry benzene
  5. concentrationthe combined filtrates concentrated to one-half its volume in vacuum
  6. additionThe acid chloride solution was diluted to its original volume with dry benzene
  7. stirringwhile stirring
  8. waitwas continued for 18 hours
  9. customthe organic phase separated
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered with suction
  12. customthe solvent removed by distillation at reduced pressure
  13. customThe product was then triturated with 50% diethylether in hexane
  14. filtrationcollected by suction filtration
  15. customchromatographed (silica gel

Sources & evidence

ORD record
ord-00919ebe0ef5422e9545866cb7a97445
Source dataset
uspto-grants-1978_05
Patent number
US04089956

Reaction notes

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