Sodium Carbonate → HCID 10654534, compound

HRID 1913370Notes

Reaction equation

HRID 1913370 reaction equation
[CH3:1][N:2]([CH2:4][C:5]#[CH:6])[CH3:3].C(=O)([O-])[O-].[Na+].[Na+].Br[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1>C(O)C.C(COC)OC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH3:1][N:2]([CH3:3])[CH2:4][C:5]#[C:6][C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 122863-BromopyridineHCID 81643N,N-Dimethylpropargylamine

Product 1

HCID 10654534HCID 10654534, compoundYield 4.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 20074477Dimethoxyethane ethanolSolvent

Conditions

Temperature
90 °C

Procedure

To a pressure tube containing a magnetic stir bar was added N,N-dimethylpropargylamine (333 mg, 4 mmol) and the vial was purged with argon. To the tube is added a solution of tetrakis(triphenylphosphine)palladium(0) (139 mg, 0.12 mmol) in ethanol/dimethoxyethane (1:1, 2 mL), sodium carbonate(aq) (2 M, 4 mL, 4 mmol), copper(I)iodide (46 mg, 0.24 mmol) and the vial was once again purged with argon. The resultant solution was stirred at room temperature for 5 min when 3-bromopyridine (483 μL, 5 mmol) was added as a neat oil. The tube was purged with argon, capped, heated to 90° C. and stirred for 1 h. The solution was cooled to room temperature and poured into a flask containing anhydrous sodium sulfate (5 g). The solution was dried for 10 min, filtered and the solvent was removed in vacuo. The crude material was chromatographed on silica gel (CH3OH/CHCl3, 10/90, Rf=0.13) to afford the title compound 51 (26 mg, 4% yield) as a brown oil: 1H NMR (CDCl3) δ 8.67 (br s, 1H), 8.52 (m, 1H), 7.72 (m, 1H), 7.24 (m, 1H), 3.49 (s, 2H), 2.37 (s, 6H); LRMS (ESI) m/z calcd for C10H12N2 [M+H]+ 161. found 161; LRMS (ESI) m/z calcd for C8H6N [M−N(CH3)2]+ 116. found 116; HRMS (ESI) m/z calcd for C10H12N2 [M+H]+ 161.1079. found 161.1090; HPLC>98% (tR=9.38 min, 60 (A):40 (B): 0.02 (C); tR=4.70 min, 60 (A):40 (B): 0.07 (C)).

Workup

  1. additionTo a pressure tube containing a magnetic stir bar
  2. customthe vial was purged with argon
  3. customthe vial was once again purged with argon
  4. additionwas added as a neat oil
  5. customThe tube was purged with argon
  6. customcapped
  7. temperatureThe solution was cooled to room temperature
  8. additionpoured into a flask
  9. additioncontaining anhydrous sodium sulfate (5 g)
  10. customThe solution was dried for 10 min
  11. filtrationfiltered
  12. customthe solvent was removed in vacuo
  13. customThe crude material was chromatographed on silica gel (CH3OH/CHCl3, 10/90, Rf=0.13)

Sources & evidence

ORD record
ord-94e2a91fd4fd45beae6f8020aadb2d81
Source dataset
uspto-grants-2013_12
Patent number
US08609708B2

Reaction notes

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