DD144409A1 - PROCESS FOR THE PREPARATION OF 5-ALKYL-2-ROACHED BRACKET ON4-ACYLOXY-PHENYL POOR CLAUSE TO PYRIMIDINES - Google Patents

Abstract

The. The invention relates to a process for the preparation of novel 5-alkyl-2- [4-aeyloxy-phenyl] -pyrimidines. The aim of the invention is a process for the preparation of new crystalline-liquid substances. It has been found that crystalline liquid 5-alkyl ~ 2 ~ T4-acyloxyphenyl] -pyrimidines of the general formula ## STR3 ## can be prepared by reacting 4-hydroxybenzamidine hydrochloride id with a-alky 1-0 -dimethylarainoacrolein to give 5- Alkyl-2-I 4-hydroxy-phenyl] -pyrimidine and subsequent esterification with. a reactive acid derivative, preferably acid chloride. - Formula

Description

Object of the invention

The object of the invention "is to produce new crystalline liquid 5-alkyl-2- / 4-cyloxy-phenyl-7-pyrimidines.

Explanation of the essence of the invention

It has been found that crystalline-liquid 5-alkyl-2- / ~ 4-acyloxy - plienyl7 - pyrimiäine of the general formula

H - COO- (OW / ^X > - ^C n ^H 2n + 1 where R = R ⁿ -fc ^ -, - '(h) " ⁿ ° _n ' R ¹ = C E _nu , C E _n 0, CL "0C00

n ^l 2n + 1 » ^{wn Ai} 2n + 1 ^v ' ^w n" 2n + 1

, CP,

with η = 1 l) is 10 "can be prepared by reacting 4-hydroxy-benzamidiii-hydro-chloride 1 with o ^ -alkyl-ß-dimethylamino-acrolein 2," at a higher temperature in the presence of Sodium methylate to 5-alkyl-2-4-hydroxy-phenyl-4-pyrimidine 3. and subsequent esterification with a reactive acid derivative, preferably an acid chloride, according to the general scheme:

21505

Object of the invention

The object of the invention is the preparation of novel crystalline liquid 5-alkyl-2 - / 4-acyloxy-phenyl-4-pyrimidines.

Presentation of the nature of

It has been found that crystalline liquid 5-alkyl-2- ~ 4-acyloxy-phenyl-7-pyrimidines of the general formula

E - COO-

-N

where R = R - <Q $ - , ~ \ lv ~ ^NC n

* '- ^C n ^H 2n + 1> ^C n ^H 2n ₊ 1 ° » ^C n ^H 2nH-1 ° ^C0 °

C H-S, F, Cl, Br, NO ₂ , CN, CF,

with η = 1 to 10, can be prepared by reacting 4-hydroxybenzamidine hydrochloride j. 2. at elevated temperature in the presence of sodium methylate on 5-alkyl-2- ₍ 4-hydroxy-phenyl-7-pyrimidine 3, and subsequent esterification with a reactive acid derivative, with C 1-6 -alkyl-β-dimethylamino-acrolein preferably a satire chloride according to the general scheme:

• Eabelle 1

η Yield ί> F ⁰ C 5 89 131 6 95 95 7 93 88 8th 96 79 Example 2

Preparation of the 5α-alkyl-2 - / 4,4- (4-substituted-2-enyloxy) -phenyl- ¹ -pyrraleic acid (R = R ¹ - ^ J k-) - a matrium methylate solution of 0.23 g (0 , 01 atoms) Sodium in 30 ml of ^absolute methanol are added, with stirring, to 0.01 mol of 3 ^{× 10 2} moles of cubo-substituted benzoylchloroethane, the reaction mixture is stirred for 10 hours at room.

stirred and allowed to stand overnight. After addition of water, the ethereal extract was washed, then treated with Na ₂ SO ₄ and charcoal and then concentrated to dryness. The residue -is from n-hexane several times umkristalliaiert respectively, on a Al ₂ O ^ column (activity grade 1) with ether or chromatographed ^M ethylene chloride and crystallized after removal of the solvent from η-hexane.

_ 5 -

21

H ¹ -,

Table 2

 COO

H ¹

Y. Ί "

6 ^ 13 " VJL 73 • 57 , 157 C ₆ H ₁₃ - 6 70 , 43 , 147 ^C 6 ^H 13 7 95 , 64 , 150 8th 78 , 75, 5. 142.5. CH ₃ O- 6 90 , 116 , 196.5. C ₃ H ₇ O- 6 81 , 103 .187 C ₇ K ₁₅ O- 6 86 • 72, 5. 166 CH ₃ - 6 81 , 99 , 165 Br 6 90 , 120 .181 Cl 6 88 , 118 , 182. , F- 6 75 , 116 , 5. 149 CH ^ S- 6 68 , 110 .141 CH ₃ COO- 6 65 , 83 , 195 CH ₅ OCOO- 6 6 55 68 • 88. 102 , 200 S N .151.160,5. NO ₉ 7 78 , 147 .223.229 CN δ ' 70 , 144 N .159.5.240. Where: K - crystalline-solid N = nematic I = isotropic-liquid

Overflow temperatures in ⁰ C

Example 3

Preparation of the 5-alkyl-2- / 4- (4-substituted-cyclohexyloarbonyloxy) -phenylj-pyrimidines

The synthesis and purification is carried out analogously to "Rule 2 using 4-subst" cyclohexanecarboxylic acid chlorides.

Table 3

H ¹ R ² Y. K 98 97 N 141 185 I cT ° 6 ^H 13 72 80 • • • • *

Claims (1)

He f ig ngsans pr uoh 1. A process for the preparation of crystalline-liquid 5 ~ Aikyl ~ 2 - / * "4-acyloxy-ph.enyl7 ~ pyr imidines of the general formula R = ^C n ^H 2n ₊ 1 ^C n ^H 2n ₊ 1 ^C00 > ^C n ^H 2n ₊ 1 ^S » ^F » ^C1 ' ^Br » ^N0 2' CN, ₃ with η = 1 "to 10 Tseäeuten, characterized in that 4-hydroxy-TDensaffiidin hydrochloride 1_ with" ^ -Alkylß-dimethylamino-acrolein 2_ at elevated temperature, in the presence of Natriuramethylat to 5-alkyl-2 ~ / ~ 4- reacted hydroxy ~ phenyl7-pyiimiäin 3_ and this is esterified with a reactive acid derivative, preferably a ßäurechlorid.