Hydroxyamine hydrochloride → Methyl 5-aminopyrimidine-2-carboxylate

HRID 2173849Notes

Reaction equation

HRID 2173849 reaction equation
[CH3:1][O:2][C:3]([C:5]1[N:10]=[CH:9][C:8]([N:11]=C(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:7][N:6]=1)=[O:4].C([O-])(=O)C.[Na+].Cl.NO>CO>[CH3:1][O:2][C:3]([C:5]1[N:6]=[CH:7][C:8]([NH2:11])=[CH:9][N:10]=1)=[O:4]

Participants

5

Reactant 3

HCID 443297Hydroxyamine hydrochloride2×HCID 517045Sodium Acetate2×HCID 86667301HCID 86667301, compound

Product 1

HCID 10654421Methyl 5-aminopyrimidine-2-carboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

5-(Benzhydrylidene-amino)-pyrimidine-2-carboxylic acid methyl ester (9.83 g, 31.0 mmol) was dissolved in methanol (100 mL) and sodium acetate (12.2 g, 149 mmol) was added followed by hydroxylamine hydrochloride (7.75 g, 112 mmol). This was stirred at room temperature as a pale yellow mixture. At 3 h another 7.75 g of hydroxylamine hydrochloride and 12.2 g of sodium acetate were added. At 4 d, silica gel was added directly to the reaction mixture for dry loading purposes. Purification by silica gel flash chromatography (methanol/ethyl acetate) gave 5-amino-pyrimidine-2-carboxylic acid methyl ester impure with acetic acid (6.074 g, 79%) as a white solid. After placing in a vacuum oven for 6 d, some of the acetic acid was removed. The material was carried on as is. 1H NMR (400 MHz, DMSO-d6, δ): 8.15 (s, 2H) 6.35 (s, 2H) 3.79 (s, 3H); MS (M+1): 154.8.

Workup

  1. additionsilica gel was added directly to the reaction mixture
  2. customfor dry loading purposes
  3. customPurification by silica gel flash chromatography (methanol/ethyl acetate)

Sources & evidence

ORD record
ord-7e610a77c6e34cc999a9ecffe6f378c8
Source dataset
uspto-grants-2015_06
Patent number
US09056834B2

Reaction notes

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