SU129650A1 - The method of obtaining 5 - (- hydroxyethyl derivatives of 2-hydroxy-, 2-thio- and 2-amino-4-hydroxypyrimidines - Google Patents

Description

The described method for the preparation of 5-p-hydroxyethyl derivatives of 2-hydroxy, 2-thio-, and 2: amino-4-hydroxypyrimidines, containing no other substituents in position 5 and 6, makes it possible to obtain these compounds from available materials and under simple conditions x synthesis.

A feature of the process is that urea, thiourea, and guanidine are condensed with a sodium formyl-j-butyrolactone.

Example 1. Getting 2-thio-5 (p-hydroxyethyl) uracil. 200 ml of dry benzene was added to 12.3 g of sodium (0.54 at.), Sprayed with heating in xylene, and 24.6 g of anhydrous ethanol (0.54 lul) dissolved in 30 ml was added dropwise with stirring. dry benzene, for 2 hours. at 60-65 °. After stirring for 6 hours. at the specified temperature and aging for 16 hours. At 20, the resulting sodium ethylate suspension is cooled to minus 5 and a mixture of 43 g (0.5 mol) of t-butyrolactone and 44 g (0.56 mol) of formic acid ethyl ester is gradually added to it, without raising the temperature above 10 °. Stir the reaction mass for 6 hours. at 10 ° and incubated for 48 hours. at 20-25 °. 38 g of thiourea (0.5 mol) dissolved in 250 ml of ethyl alcohol are added to the resulting sodium sodium formyl-butyrolactone, stirred for 5 hours. at 70-75, the solvents are distilled off in a vacuum; the residue is dissolved in 200 ml of water, the solution is treated with activated carbon and the filtrate is acidified with hydrochloric acid. The precipitated 2-TIO-5- (R-OXYETHYL) crystalline precipitate of uracil is filtered off, washed with cold water and dried, and then purified by recrystallization from water. The yield is 37.7-38.9 g, or 43.8-45.2% of the theoretical; m.p. 248-249

Analysis. Found (in%): C -41.63; H - 4.67; N-15.95; S - 19.34;

Calculated (in%): C -41.86; H -4.65; N-16.27; S - 18.6 (CeHsOsNoS).

L1 129650-2 -

Example 2. Getting 5- (| 3-hydroxyethyl) uracil. To the a-sodium formyl - (- butyrolactone prepared in the previous example, 30 g of urea (0.5 mol) dissolved in 200 ml of ethanol was added to the benzene-xylene medium, stirred at 45 ° for 30 minutes, and then 5 after one hour for 16 hours, the solvents are distilled off in vacuum, the residue is dissolved in 100 ml of water and acidified with hydrochloric acid. The filtered crystalline precipitate (29.9 g) is dissolved in the solution 19 g of potassium hydroxide in 290 ml of methanol at 50 ° C. A crystalline precipitate of the potassium salt of 5- (P-OXI TIL) of uracil. Methanol is distilled off in vacuo, the residue is dissolved in 190 ml of water, the solution is treated with activated carbon and the filtrate is acidified with hydrochloric acid. The precipitated white crystals are separated, washed with cold water and dried. The yield is 23 g or about 30% of the theoretical value, mp 259-26 G. The spectrum has a maximum in the ultraviolet region of 266 mm, which corresponds to the ultraviolet spectrum of loglosch, uracil derivatives.

Analysis. Found (in%): C -46.29; ,sixteen; N-17.82.

Calculated (in%): C -46.15; H -5.12; N-17.94; CgHgOsNa.

Example 3. Preparation of 2-amipo-4-hydroxy-5- (3-hydroxyethyl) pyrimidip. A solution of 61 g of guanidine nitrate (0.5 mol) in 250 ml of methanol containing 22 g of sodium hydroxide is added to the sodium-formyl-β-butyrolactone prepared in Example 1 in a bespal-xylene medium and stirred for 3 hours. at 60-65 °. The solvent mixture is distilled off in vacuo, the residue is dissolved in 500 ml of water, acidified to pH-3, the acidic solution is treated with activated carbon and the crystalline 2-amino-4-hydroxy-5- (p-hydroxyethyl) -pyrimidine is precipitated from ammonium which is recrystallized from boiling water.

The yield is 59.9 g, or 76.3% of the theoretical; m.p. 260-262 °.

And n and l and 3. Paydeno (%): C - 46.42; H - 5.76; N - 26.88Calculated (in%): С -46.45; P -5,8; N - 27.09; CgHgOsNa.

Subject invention

The method of obtaining 5- | 3-hydroxyethyl derivatives of 2-hydroxy, 2-thio- and 2-amino-4-hydroxypyrimidines, which do not contain other substituents in positions 5 and 6, characterized in that, in order to expand the raw material base, urea, thiourea and guanidine are condensed with sodium sodium formyl-- | -butyrolactone.