Diglyme → HCID 86762468, compound

HRID 402311Notes

Reaction equation

HRID 402311 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][NH:5][C:6]1[C:11]([NH:12][CH2:13][CH2:14][O:15][CH3:16])=[N:10][C:9]([C:17]#[N:18])=[C:8]([C:19]#[N:20])[N:7]=1.Cl[C:22]1[C:27](Cl)=[N:26][C:25]([C:29]#[N:30])=[C:24]([C:31]#[N:32])[N:23]=1.COCCOCCOC>C(N(C(C)C)CC)(C)C.C(OCC)(=O)C>[CH3:1][O:2][CH2:3][CH2:4][N:5]1[C:6]2[N:7]=[C:8]([C:19]#[N:20])[C:9]([C:17]#[N:18])=[N:10][C:11]=2[N:12]([CH2:13][CH2:14][O:15][CH3:16])[C:22]2[N:23]=[C:24]([C:31]#[N:32])[C:25]([C:29]#[N:30])=[N:26][C:27]1=2

Participants

6

Reactant 3

HCID 8150DiglymeHCID 6078205,6-Dichloro-2,3-dicyanopyrazineHCID 86762469HCID 86762469, compound

Product 1

HCID 86762468HCID 86762468, compound

Reagents, catalysts & solvents 2

HCID 81531DiisopropylethylamineCatalystHCID 8857Ethyl AcetateSolvent

Procedure

FIG. 17 shows the reaction pathway. In a 100 mL round-bottom flask having a magnetic stir-bar and with 14/20 glass joint attached to an air-condenser was add 0.48 g [0.002 mole] of 2,3-bis(2-methoxyethylamino)-5,6-dicyanopyrazine 1101, 2,3-dichloro-5,6-dicyanopyrazine 301 and 5 mL of diglyme 901 [diethyleneglycoldimethylether]. The reaction was stirred for about an hour until all the solids had dissolved. To this solution was added 0.6 g of diisopropylethylamine 902 drop-wise with stirring. The reaction was then brought to reflux using a sand-bath at ˜180°. All under a nitrogen sweep. The solution acquired a dark gray orange color as heating took place. Reaction was monitored by TLC or column chromatography [silica plates] using ethyl acetate; the bright blue fluorescent starting material spot at Rf: 0.45 slowly faded and was converted to a bright yellow spot at Rf: 0.98 identical to the material formed from dimerization. After 5 hours the starting material spot remained though the yellow spot corresponding to the expected product at solvent front in TLC or column chromatography was present. Solution cooled to rt and poured, with good stirring into 40 mL of water/ice mixture having ˜0.5 mL of 10% HCl. Dark mixture was allowed to stand ˜24 hrs and filtered by suction and washed with water. Material was dried in vac. drying oven at 70°. There was obtained 0.6 g of yellow brown powder having both starting material and desired tetracyanodipyrazinepyrazine. Exact mass 402.2 [calc 402.13].

Workup

  1. customIn a 100 mL round-bottom flask having
  2. customa magnetic stir-bar and with 14/20 glass joint attached to an air-condenser
  3. dissolutionhad dissolved
  4. stirringwith stirring
  5. temperatureto reflux
  6. customat ˜180°
  7. temperatureas heating
  8. customReaction
  9. customformed from dimerization

Sources & evidence

ORD record
ord-35b26b52094a4336bc2f5259e7e00fc7
Source dataset
uspto-grants-2014_06
Patent number
US08742107B1

Reaction notes

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