Hydrochloric Acid → 5,6-diamino-3-methyl-1-(2-methyl-allyl)-1H-pyrimidine-2,4-dione

HRID 896036Notes

Reaction equation

HRID 896036 reaction equation
[NH2:1][C:2]1[N:7]([CH2:8][C:9]([CH3:11])=[CH2:10])[C:6](=[O:12])[N:5]([CH3:13])[C:4](=[O:14])[CH:3]=1.Cl.[N:16]([O-])=O.[Na+].N(N1C(=O)C=CNC1=O)=O.S(S([O-])=O)([O-])=O.[Na+].[Na+]>O>[NH2:16][C:3]1[C:4](=[O:14])[N:5]([CH3:13])[C:6](=[O:12])[N:7]([CH2:8][C:9]([CH3:11])=[CH2:10])[C:2]=1[NH2:1]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 110716-Amino-3-methyl-1-(2-methyl-2-propen-1-yl)-2,4(1H,3H)-pyrimidinedioneHCID 24489Sodium DithioniteHCID 23668193Sodium NitriteHCID 866114893-nitroso-1H-pyrimidine-2,4-dione

Product 1

HCID 222265135,6-diamino-3-methyl-1-(2-methyl-allyl)-1H-pyrimidine-2,4-dione

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
20 °C

Procedure

Methallylamine (211 g, 2.97 mol) is added to a solution of concentrated hydrochloric acid (250 ml) in water (1.91), followed by portionwise addition of potassium cyanate (240 g, 2.97 mol). The reaction is then heated for 2 hours at 80° C., prior to cooling and evaporation to afford (2-methyl-allyl)-urea (244.5 g), mp 114-115° C. The urea (268 g, 2.35 mol) is added to a solution of cyanoacetic acid (220 g, 2.59 mol) in acetic anhydride (536 ml) and the reaction is heated at 70° C. for 1 hour, cooled to 0° C. and diluted with ether. The resultant solid is collected by filtration, washed with ether, suspended in water (2.2 l) and heated to 75° C. 2M aqueous sodium hydroxide solution is then added portionwise over 30 min to maintain pH between 8 and 9.5. The reaction is cooled to room temperature, treated with acetic acid (12 ml), further cooled to 10° C. and the resultant solid is collected by filtration, washed with cold water and dried to afford 6-amino-1-(2-methyl-allyl)-1H-pyrmidine-2,4-dione, mp 267-269° C. The uracil (253 g, 1.40 mol) is added to a solution of sodium hydroxide (123 g, 3.07 mol) in water (2.5 l) and allowed to exotherm then cooled to 20° C. Dimethyl sulfate (196 ml, 2.06 mol) is added portionwise over 1 hour. After standing overnight, the reaction is cooled to 5° C. and the solid collected by filtration to give 6-amino-3-methyl-1-(2-methyl-allyl)-1H-pyrimidine-2,4-dione, mp 162-163° C. The methyluracil (165 g, 0.85 mol) is suspended in water (1.551) and concentrated hydrochloric acid (72 ml). A solution of sodium nitrite (58.4 g, 0.85 mol) in water (117 ml) is then added dropwise over 30 minutes and the reaction is stirred at 20° C. for 3 hours. The solid is collected by filtration, washed successively with water, methanol and ether to afford 6-amino-3-methyl-1-(2-methyl-allyl)-5-nitroso-1H-pyriridine-2,4-dione, mp 213° C. (dec). The nitrosouracil (190 g, 0.85 mol) is suspended in water (950 ml), heated to 85° C. and sodium dithionite (85%, 347.2 g, 1.69 mol) is added portionwise. After cooling to room temperature, the solid is collected by filtration to afford 5,6-diamino-3-methyl-1-(2-methyl-allyl)-1H-pyrimidine-2,4-dione, mp 152-153° C.

Workup

  1. filtrationThe solid is collected by filtration
  2. washwashed successively with water, methanol and ether
  3. customto afford 6-amino-3-methyl-1-(2-methyl-allyl)-5-nitroso-1H-pyriridine-2,4-dione, mp 213° C. (dec)
  4. temperatureheated to 85° C.
  5. temperatureAfter cooling to room temperature
  6. filtrationthe solid is collected by filtration

Sources & evidence

ORD record
ord-e7d418171db74a60a14c0b845b7b9680
Source dataset
uspto-grants-2005_07
Patent number
US06919337B2

Reaction notes

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