Phosphate → HCID 70547083, compound

HRID 894383

Reaction equation

HRID 894383 reaction equation
[CH3:1][C:2]1([CH3:13])[C@H:6]([C:7]#[N:8])[N:5]2[C:9](=[O:12])[C@H:10](Br)[C@H:4]2[S:3]1.O1CCCCC1OC1C=CC(C=O)=CC=1.P([O-])([O-])([O-])=O>O1CCCC1.[Zn]>[CH3:1][C:2]1([CH3:13])[C@H:6]([C:7]#[N:8])[N:5]2[C:9](=[O:12])[CH2:10][C@H:4]2[S:3]1

Participants

6

Reactant 3

HCID 1061PhosphateHCID 112527364-(2-Tetrahydro-2H-pyranoxy)benzaldehydeHCID 12944713HCID 12944713, compound

Product 1

HCID 70547083HCID 70547083, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst2×HCID 8028TetrahydrofuranSolvent

Procedure

Activated mossy zinc (500 mg) and zinc dust (100 mg) are added to a solution of 2,2-dimethyl-3α-cyano-6α-bromopenam (522 mg, 2 mmol) and p-(2-tetrahydropyranyloxy)benzaldehyde (750 mg, 3.75 mmol) prepared according to E. Piers, W. deWaal and R. W. Britton, J. Am. Chem. Soc., 93, 5113 (1971) in 1 ml of dry tetrahydrofuran. After stirring vigorously at 50° for 3 hrs., the mixture is allowed to cool and 1 ml of pH 5 phosphate buffer is added. After standing for 10 min., the solids are removed by filtration and washed thoroughly with ethyl acetate. The filtrate is extracted with ethyl acetate. The combined extracts are washed with phosphate buffer and saturated sodium chloride, dried with sodium sulfate and the solvents removed by evaporation. The crude material is purified by chromatography on 60 g of silica gel using 40% acetone/chloroform as eluant to afford 2,2-dimethyl-3α-cyanopenam as a by-product melting at 73°- 75° C. and a mixture of 2,2-dimethyl-3α-cyano-6α-[p-(2-tetrahydropyranyloxy)-α-hydroxybenzyl]penam and 2,2-dimethyl-3α-cyano-6β-[p-(2-tetrahydropyranyloxy)-α-hydroxybenzyl]penam. Separation of the 6α- and 6β-compounds is effected by PLC (10% acetone/toluene; two developments) providing the individual 6α- and 6β-compounds.

Workup

  1. customprepared
  2. temperatureto cool
  3. waitAfter standing for 10 min.
  4. customthe solids are removed by filtration
  5. washwashed thoroughly with ethyl acetate
  6. extractionThe filtrate is extracted with ethyl acetate
  7. washThe combined extracts are washed with phosphate buffer and saturated sodium chloride
  8. dry with materialdried with sodium sulfate
  9. customthe solvents removed by evaporation
  10. customThe crude material is purified by chromatography on 60 g of silica gel using 40% acetone/chloroform as eluant

Sources & evidence

ORD record
ord-577602433f524b5c8e6340992b1d1d70
Source dataset
uspto-grants-1981_08
Patent number
US04283531

Linked notes

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