2-Methylpropylenediamine → HCID 178457531, compound

HRID 1614304Notes

Reaction equation

HRID 1614304 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([OH:8])[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([Cl:12])[N:3]=1.[NH2:13][CH2:14][C:15]([NH2:18])([CH3:17])[CH3:16]>C(O)C>[ClH:12].[NH2:1][C:2]1[N:7]=[C:6]([OH:8])[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([NH:13][CH2:14][C:15]([NH2:18])([CH3:17])[CH3:16])[N:3]=1

Participants

4

Reactant 2

HCID 131282-MethylpropylenediamineHCID 178418667HCID 178418667, compound

Product 1

HCID 178457531HCID 178457531, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

2-Amino-6-chloro-4-hydroxy-5-nitropyrimidine, 1.94 g, was finely powdered and dissolved in approximately 200 ml boiling absolute ethanol and filtered while hot to remove the insoluble 2-amino-4,6-dihydroxy-5-nitropyrimidine (sole contaminant), leaving a solution containing 9.0 mmoles of (IIa). This was taken again to reflux and 0.88 g (20 mmoles) 1,2-diamino-2-methylpropane (99% pure) added all at once with stirring. The progress of the reaction was monitored on Partisil SCX (25×0.46 cm) eluted with 0.1M ammonium hydroxide made to pH 3.3 with formic acid/methanol, 9:1, by absorbance at 254 and 330 nm. After 2 hrs stirring at reflux, greater than 99% of (IIa) had been consumed and the majority of product had fallen out of solution. After being kept at -15° C. overnight in order to complete this precipitation, the reaction, filtered, washed with a few ml cold absolute ethanol and 40 ml ether, and vacuum dried over P2O5 , gave 2.43 g of the monohydrochloride salt (97% yield): UV (0.1N HCl) λmax 331 nm, 285-290 nm sh, 233 nm sh; 1H-NMR (DMSO-D6) δ1.13 (6H, s, C(CH3)2), δ3.50 (2H, d, J=5 Hz, --N--CH2 (singlet if D2O added). Greater than 99% of the UV330 and 98% of the UV254 absorbance in a chromatogram of this material resides in a single well-shaped peak. No evidence for the presence of any 2-amino-6-(2-amino-1,1-dimethylethylamino)-4-hydroxy-5-nitropyrimidine can be seen by either HPLC or NMR.

Workup

  1. dissolutiondissolved in approximately 200 ml
  2. filtrationfiltered while hot
  3. customto remove the insoluble 2-amino-4,6-dihydroxy-5-nitropyrimidine (sole contaminant)
  4. customleaving a solution
  5. additioncontaining 9.0 mmoles of (IIa)
  6. temperatureto reflux
  7. washeluted with 0.1M ammonium hydroxide
  8. stirringAfter 2 hrs stirring
  9. temperatureat reflux
  10. customgreater than 99% of (IIa) had been consumed
  11. customthis precipitation
  12. customthe reaction
  13. filtrationfiltered
  14. washwashed with a few ml cold absolute ethanol and 40 ml ether, and vacuum
  15. dry with materialdried over P2O5

Sources & evidence

ORD record
ord-57549e577a66428c92c9f16a1f9a92f3
Source dataset
uspto-grants-1993_03
Patent number
US05196533

Reaction notes

Loading…