Sodium Nitrite → HCID 11617472, compound

HRID 2276290Notes

Reaction equation

HRID 2276290 reaction equation
[CH3:1][O:2][C:3]1[CH:24]=[CH:23][C:6]([CH2:7][S:8][C:9]2[N:14]=[C:13]([NH:15][CH3:16])[CH:12]=[C:11]([N:17]3[CH2:22][CH2:21][O:20][CH2:19][CH2:18]3)[N:10]=2)=[CH:5][CH:4]=1.[N:25]([O-])=O.[Na+]>C(O)(=O)C>[NH2:25][C:12]1[C:11]([N:17]2[CH2:18][CH2:19][O:20][CH2:21][CH2:22]2)=[N:10][C:9]([S:8][CH2:7][C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:24][CH:23]=2)=[N:14][C:13]=1[NH:15][CH3:16]

Participants

4

Reactant 2

HCID 23668193Sodium NitriteHCID 66597133HCID 66597133, compound

Product 1

HCID 11617472HCID 11617472, compoundYield 25%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

2-(4-methoxybenzylsulfanyl)-4-methylamino-6-morpholinopyrimidine (5.0 g, 14.4 mmol) was dissolved in acetic acid (50 ml), and an aqueous solution (10 ml) of sodium nitrite (1.49 g, 21.6 mmol) was added drop-wise under water cooling and stirred at room temperature for 5 hours. After distilling away acetic acid under reduced pressure and dissolving the residue in ethyl acetate, washing was performed in the order of 2N—NaOH solution and water, then dried with MgSO4 and the solvent was distilled away under reduced pressure. The residue was dissolved in ethyl acetate (100 ml), 1.0 g of Pd/C was added and catalytic hydrogenation was performed under normal pressure for 4 hours. Celite was used to filter off Pd/C and the filtrate was distilled away under reduced pressure. Separation and purification were performed by silica gel column chromatography (ethyl acetate:hexane=2:1) to obtain 1.28 g (25% yield) of 5-amino-2-(4-methoxybenzylsulfanyl)-6-methylamino-4-morpholinopyrimidine. Melting point: 79.5 to 84° C. MS m/z: 361 (M+).

Workup

  1. distillationAfter distilling away acetic acid under reduced pressure
  2. dissolutiondissolving the residue in ethyl acetate
  3. washwashing
  4. dry with materialdried with MgSO4
  5. distillationthe solvent was distilled away under reduced pressure
  6. dissolutionThe residue was dissolved in ethyl acetate (100 ml)
  7. addition1.0 g of Pd/C was added
  8. waitcatalytic hydrogenation was performed under normal pressure for 4 hours
  9. filtrationto filter off Pd/C
  10. distillationthe filtrate was distilled away under reduced pressure
  11. customSeparation and purification

Sources & evidence

ORD record
ord-9bd56c4769d44ee694b55266a6d21da1
Source dataset
uspto-grants-2015_09
Patent number
US09132130B2

Reaction notes

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