Carbonic acid-guanidine (1:1) → HCID 178508976, compound

HRID 1284405Notes

Reaction equation

HRID 1284405 reaction equation
O=[C:2]([CH2:8][CH2:9][O:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:3](OCC)=[O:4].C(=O)(O)O.[NH2:21][C:22]([NH2:24])=[NH:23]>C(O)C>[NH2:24][C:22]1[N:23]=[C:3]([OH:4])[CH:2]=[C:8]([CH2:9][O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:21]=1

Participants

4

Reactant 2

HCID 286947Carbonic acid-guanidine (1:1)HCID 20251494HCID 20251494, compound

Product 1

HCID 178508976HCID 178508976, compoundYield 58.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 7.8 g (36 mmol) of ethyl 2-oxo-4-phenoxybutanoate and 3.4 g (38 mmol) guanidine carbonate was heated to reflux in 100 ml abs. ethanol for 48 hours. Filtration of the cooled suspension afforded 4.6 g of 2-amino-4-hydroxy-6-phenoxymethylpyrimidine in two crops, m.p. 253°-254° (dec). This intermediate (4.3 g, 20 mmol) was heated to reflux in 50 ml phosphorous oxychloride for 2 hours then evaporated. The residue was treated with ice-water and neutralized with 10% sodium hydroxide solution then extracted with chloroform. Evaporation of the extracts left a residue which was purified by dissolution in 15% ethyl acetate/methylene chloride and filtration through silica gel. The filtrate was concentrated and crystallized from ether/1-chlorobutane/hexanes to yield 0.65 g of 2-amino-4-chloro-6-phenoxymethylpyrimidine, m.p. 123°-124°. An additional 0.8 g was deposited from the original aqueous phase, m.p. 118°-121°, for a total of 1.4 g of product. A 1.0 g (4.2 mmol) portion of this material was reacted with 20 mmol sodium methoxide in 30 ml methanol at reflux for 2 hours, then concentrated in vacuo. The residue was triturated with water, collected, water rinsed and dried to 0.9 g of the title compound, m.p. 94°-96°. NMR (90 MHz, CDCl3): δ 3.83 (s, 3H); 4.90 (s, 2H); 6.31 (s, 1H); 6.9-7.1 (m, 3H); 7.22-7.45 (m, 2H) ppm.

Workup

  1. temperaturewas heated
  2. temperatureto reflux in 100 ml abs
  3. filtrationFiltration of the cooled suspension

Sources & evidence

ORD record
ord-5ed8488911ce4803b4e3db2fbeb6631a
Source dataset
uspto-grants-1986_01
Patent number
US04563211

Reaction notes

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