Sulfuric Acid → HCID 13567771, compound

HRID 280185Notes

Reaction equation

HRID 280185 reaction equation
[H-].C([Al+]CC(C)C)C(C)C.CS([C:15]1[CH:20]=[CH:19][C:18]([S:21]([CH3:24])(=[O:23])=[O:22])=[CH:17][N:16]=1)(=O)=O.S(=O)(=O)(O)[OH:26].[I-:30].[K+].I([O-])(=O)=O.[K+]>>[I:30][C:20]1[C:15](=[O:26])[NH:16][CH:17]=[C:18]([S:21]([CH3:24])(=[O:23])=[O:22])[CH:19]=1

Participants

5

Reactant 4

HCID 1118Sulfuric AcidHCID 131026752,5-Bis(methylsulfonyl)pyridineHCID 20026217HCID 20026217, compoundHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 13567771HCID 13567771, compound

Procedure

In what could be considered as a variation of scheme III, a Heck reaction could be carried out using ethenyl alcohol V and 2-chloro-3-iodo-5-(methylsulfonyl)pyridine to give a ketone analogous to VI except that the methoxy group is replaced by a 2-chloro. This ketone would then be reduced to the corresponding alcohol using diisobutylaluminum hydride at low temperature and the resulting alcohol would be cyclized as described earlier for 2-chloropyridines. The necessary iodo compound used in this procedure can be obtained by starting with 2,5-bis(methylsulfonyl)pyridine and treating it with sulfuric acid to hydrolyze the 2-substituent followed by iodination with potassium iodide/potassium iodate with the procedure giving 3-iodo-5-(methylsulfonyl)-2(1H)-pyridinone as the product. This is then treated with phosphorus oxychloride to give the corresponding 2-chloropyridine. The corresponding compound containing bromide in place of iodine can be obtained by using a brominating agent instead of an iodinating agent in the procedure described above followed by conversion to the 2-chloro compound. The resulting 3-bromo compound could be used in the same way as the 3-iodo compound.

Workup

  1. customcan be obtained

Sources & evidence

ORD record
ord-85338693a68f44d380494b5b7fb2335e
Source dataset
uspto-grants-1986_05
Patent number
US04588733

Reaction notes

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