Potassium Carbonate → HCID 67026903, compound

HRID 1908843Notes

Reaction equation

HRID 1908843 reaction equation
Cl[C:2]1[N:7]=[C:6]([N:8]([CH2:11][CH3:12])[CH2:9][CH3:10])[CH:5]=[C:4]([CH3:13])[CH:3]=1.B1(C=C)OB([CH:20]=[CH2:21])OB(C=C)O1.C1C=CN=CC=1.C([O-])([O-])=O.[K+].[K+]>COCCOC.C(OCC)C.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>[CH2:9]([N:8]([CH2:11][CH3:12])[C:6]1[CH:5]=[C:4]([CH3:13])[CH:3]=[C:2]([CH:20]=[CH2:21])[N:7]=1)[CH3:10]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 84116020HCID 84116020, compound

Product 1

HCID 67026903HCID 67026903, compoundYield 29.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (6-chloro-4-methyl-pyridin-2-yl)-diethyl-amine (5.35 g, 26.9 mmol) in DME (75 mL), 2,4,6-trivinylcyclotriboroxane pyridine complex (6.48 g, 26.9 mmol, prepared according to F. Kerins, D. F. O'Shea J. Org. Chem. 67 (2002) 4968-4971) followed by 2 M aq. K2CO3 solution (25 mL) is added. The solution is degassed and put under argon before Pd(PPh3)4 (560 mg, 0.485 mmol) is added. The mixture is stirred for 15 h at 80° C. Another portion of Pd(PPh3)4 (560 mg, 0.485 mmol) is added, and stirring is continued for 6 h. The mixture is cooled to rt, diluted with diethyl ether and washed with sat. aq. NaHCO3. The org. extract is dried over MgSO4, filtered and concentrated. The remaining yellow oil is purified by prep. HPLC to give diethyl-(4-methyl-6-vinyl-pyridin-2-yl)-amine (1.51 g) as a colourless oil; LC-MS: tR=0.68 min, [M+1]+=191.05. 1H NMR (CDCl3): δ 1.20 (t, J=7.0 Hz, 6H), 2.25 (s, 3H), 3.56 (q, J=7.0 Hz, 4H), 5.32 (dd, J=10.5, 2.3 Hz, 1H), 6.23 (dd, J=17.1, 2.0 Hz, 1H), 6.23 (s, 1H), 6.36 (s, 1H), 6.65 (dd, J=17.3, 10.5 Hz, 1H).

Workup

  1. additionis added
  2. customThe solution is degassed
  3. additionis added
  4. stirringstirring
  5. waitis continued for 6 h
  6. temperatureThe mixture is cooled to rt
  7. washwashed with sat. aq. NaHCO3
  8. extractionextract
  9. dry with materialis dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe remaining yellow oil is purified by prep

Sources & evidence

ORD record
ord-b9b32db08100499e9144b671e6e2b771
Source dataset
uspto-grants-2013_12
Patent number
US08598208B2

Reaction notes

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