Magnesium Chloride → HCID 178482722, compound

HRID 630426Notes

Reaction equation

HRID 630426 reaction equation
[Mg+2:1].[Cl-].[Cl-].[CH3:4][N:5]([C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[CH2:9][K])[CH3:6]>C1COCC1>[CH3:4][N:5]([C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[CH2:9][Mg:1][CH2:9][C:8]1[CH:11]=[CH:12][CH:13]=[CH:14][C:7]=1[N:5]([CH3:6])[CH3:4])[CH3:6]

Participants

4

Reactant 2

HCID 5360315Magnesium Chloride2×HCID 178482721HCID 178482721, compound

Product 1

HCID 178482722HCID 178482722, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Under argon, 0.20 g of MgCl2 (2.1 mmol) and 0.70 g of ortho-N,N-dimethylaminobenzyl potassium (4.0 mmol) are introduced into a Schlenk flask. Around 25 ml of THF are recondensed under vacuum at −78° C. The mixture is stirred at ambient temperature for 30 minutes, then heated at reflux under static vacuum for 5 h, at 50° C. The insoluble MgCl2 crystals have then disappeared. After 1 night at 50° C., the mixture is centrifuged; the white-grey centrifugation pellet of KCl is removed, and the orange solution is concentrated to 1-2 ml, then around 0.5 ml of petroleum ether is added. Colourless crystals appear in the red solution. XRD analysis (Annex 4) of one of the crystals indicates a monomeric structure of the bis(ortho-N,N-dimethylaminobenzyl) magnesium complex (THF). M=0.30 g (yield=42%). 1H NMR (THF-d8, 22° C.): δ=7.00 (d, 2H, CH(6), J(C-H)=7 Hz), 6.90 (d, 2H, CH(3), J(C-H)=7 Hz), 6.75 (t, 2H, CH(4), J(C-H)=7 Hz), 6.55 (t, 2H, CH(5), J(C-H)=7 Hz), 3.65 (t, 4H, free non-deuterated THF), 2.65 (s, 12H, C(8) and C(9), N(CH3)2), 1.80 (m, 4H, free non-deuterated THF), 1.17 (s, 4H, C(1), Mg—CH2—). 13C NMR (THF-d8): δ=152.8 (C(2)), 148.4 (C(7)), 128.9 (C(6)), 125.9 (C(4)), 118.9 (C(5)), 118.4 (C(3)), 45.7 (N(CH3)2), 19.0 (Mg—CH2—).

Workup

  1. customrecondensed under vacuum at −78° C
  2. temperatureheated
  3. temperatureat reflux under static vacuum for 5 h, at 50° C
  4. waitAfter 1 night at 50° C.
  5. customthe white-grey centrifugation pellet of KCl is removed
  6. concentrationthe orange solution is concentrated to 1-2 ml
  7. additionaround 0.5 ml of petroleum ether is added

Sources & evidence

ORD record
ord-53e8046a81f34d6aadd213e2a35d8a32
Source dataset
uspto-grants-2016_04
Patent number
US09315590B2

Reaction notes

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