Methanol → HCID 15218810, compound

HRID 962898Notes

Reaction equation

HRID 962898 reaction equation
[C:1]([C:3]1[N:8]=[C:7]([C:9]2[CH:14]=[C:13]([C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=3)[CH:12]=[C:11]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([C:29]#[N:30])[N:24]=3)[N:10]=2)[CH:6]=[CH:5][CH:4]=1)#[N:2].C(Cl)Cl.CO.[NH4+].[OH-]>C(O)(=O)C>[NH2:30][CH2:29][C:25]1[N:24]=[C:23]([C:11]2[CH:12]=[C:13]([C:15]3[CH:16]=[CH:17][C:18]([O:21][CH3:22])=[CH:19][CH:20]=3)[CH:14]=[C:9]([C:7]3[CH:6]=[CH:5][CH:4]=[C:3]([CH2:1][NH2:2])[N:8]=3)[N:10]=2)[CH:28]=[CH:27][CH:26]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 6344DichloromethaneHCID 14923Ammonium HydroxideHCID 98433124′-(4-Methoxyphenyl)[2,2′:6′,2′′-terpyridine]-6,6′′-dicarbonitrile

Product 1

HCID 15218810HCID 15218810, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
50 °C

Procedure

6,6"-Dicyano-4'-(4-methoxyphenyl)-2,2':6',2"-terpyridine (1.556 g, 4.0 mmole) prepared in example 14 was dissolved in Ultrex acetic acid (130 mL, Baker) in a Parr hydrogenation bottle by warming to 50° C. for 25 minutes. The solution was sparged with argon for 5 minutes, 10% Pd/C (470 mg) was added under argon, and the reaction mixture was hydrogenated at 45 psi and 45° C. for 19 hours in a Parr hydrogenation apparatus. After venting excess hydrogen and replacing it with argon, the catalyst was removed by filtration using 5 mL of acetic acid as a wash. Most of the solvent was then evaporated under reduced pressure at 35° C. Residual acetic acid was removed by a series of consecutive additions and co-evaporations using 2×30 mL aliquots of toluene, then 2×30 mL aliquots of methylene chloride, and finally 2×30 mL aliquots of ethanol. The product was then dried under vacuum at 30° C. overnight to give 2.3 g (99.5 % recovery) of product as an off-white solid. Thin layer chromatography (silica gel; 85% methylene chloride, 5% methanol, 10% NH4OH, v/v/v) showed the desired product as a spot with an Rf of 0.3 (with some streaking) plus a trace amount of a small spot at the origin. Infrared and mass spectra were in good agreement for the desired product. 1H NMR (DMSO-D6) 3.85 (s, 3H, OCH3), 4.07 (s, 4H, CH2 --N), 7.16 (d, 2H), 7.55 (d, 2H), 7.99 (d, 2H), 8.03 (t, 2H), 8.52 (d, 2H) and 8.78 ppm (s, 2H).

Workup

  1. customThe solution was sparged with argon for 5 minutes
  2. addition10% Pd/C (470 mg) was added under argon
  3. customthe catalyst was removed by filtration
  4. customMost of the solvent was then evaporated under reduced pressure at 35° C
  5. customResidual acetic acid was removed by a series of consecutive additions and co-evaporations
  6. customThe product was then dried under vacuum at 30° C. overnight
  7. customto give 2.3 g (99.5 % recovery) of product as an off-white solid

Sources & evidence

ORD record
ord-5c0869a70190462ca842916257c191b9
Source dataset
uspto-grants-1998_06
Patent number
US05760191

Reaction notes

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