Pyridine → HCID 13317598, compound

HRID 1056870Notes

Reaction equation

HRID 1056870 reaction equation
O[CH:2]([P:9](=[O:14])([O:12][CH3:13])[O:10][CH3:11])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.N1C=CC=CC=1.S(Br)([Br:23])=O>C(Cl)Cl>[Br:23][CH:2]([P:9](=[O:14])([O:12][CH3:13])[O:10][CH3:11])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 68176Thionyl bromideHCID 2388826329-46-0

Product 1

HCID 13317598HCID 13317598, compoundYield 88.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

In a round bottom flask 4 (1 g, 4.63 mmol, 1 eq) was dissolved in dry DCM (10 mL) and dry pyridine (0.47 mL, 5.78 mmol, 1.25 eq) was added. Thionyl bromide (0.45 mL, 5.78 mmol, 1.25 eq) was then added to the round bottom flask under inert atmosphere. The round bottom flask was sealed with a septum, cooled in an ice bath and slowly allowed to come to room temperature overnight. The solvent was then evaporated and the crude product was dissolved in ethyl acetate. The organic layer was washed with 1 M HCl, saturated NaHCO3, water, brine, then dried over Na2SO4 and filtered. The solvent was evaporated and the crude product was purified on a silica plug 1:4 (hexanes:ethyl acetate) followed by 3:7 (hexanes:ethyl acetate) to give 5 as a viscous oil (1.14 g, 88%). The product was dried under high vacuum over P2O5. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J=7.8 Hz, 2H), 7.34 (d, J=7.5 Hz, 3H), 7.26 (s, 1H), 4.88 (d, J=13.1 Hz, 1H), 3.85 (d, J=10.8 Hz, 3H), 3.60 (d, J=10.7 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 134.56 (d, JC-P=3.3 Hz), 129.70 (d, JC-P=6.7 Hz), 129.40 (d, JC-P=2.2 Hz), 129.04 (d, JC-P=1.3 Hz), 54.87 (dd, JC-P=22.1, 7.0 Hz), 41.11 (d, JC-P=159.9 Hz). 31P NMR (162 MHz, CDCl3) δ 20.55 (s). ESIMS calculated for C9H12BrO3PNa [M+Na]+300.96, found: 300.96.

Workup

  1. customThe round bottom flask was sealed with a septum
  2. temperaturecooled in an ice bath
  3. customThe solvent was then evaporated
  4. dissolutionthe crude product was dissolved in ethyl acetate
  5. washThe organic layer was washed with 1 M HCl, saturated NaHCO3, water, brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customThe solvent was evaporated
  9. customthe crude product was purified on a silica plug 1:4 (hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-d4cd4cfe51bc43e99864341dffcb74ea
Source dataset
uspto-grants-2016_07
Patent number
US09399653B2

Reaction notes

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