DD159505A3 - PROCESS FOR PREPARING 5-CYAN-2- [4-SUBST.-PHENYL] -PYRIMIDINES - Google Patents

Abstract

The invention relates to a novel process for the preparation of 5-cyano-2- [4-substituted-phenyl] -pyrimidines which, owing to their favorable crystalline-liquid properties, e.g. can be used in optoelectronic devices. The object of the invention is the simple production of 5-cyano-2- [4-substituted-phenyl] -pyrimidines in high yields. It has been found that crystalline-liquid 5-cyano-2 [4-substituted-phenyl] -pyrimidines of the general formula, by condensation of 4-subst.-Benzamidinhydrochloriden with alpha-cyano-beta-dimethylamino-acrolein in pyridine and / or triethylamine or other strong organic bases with very good yield in a reaction step can be produced. formula

Description

.2 1. 2 8 7 6

Verfahrea gur production of

, § r _l C _T x _i ap ~ _i 2 -; / 4 - su'bs t _s

the invention

The invention relates to a novel process for the preparation of 5-CjaQ ~ 2 ~ ^ ~ substo-phaayl / ~ pyrifflidinö the general formula

R-

These compounds can be used in optoelectronic devices due to their favorable properties SeB ₈

Characteristics of bekaaeteo techpisohep Lösuageö

, In the literature various routes to the γόο substitution of 5-cyao-pyrimiäipep are described, eg, 5-bromo or 5-pyrpyrimidipe with CuCN (CCePrice, H _e J "LeoDard ΕΕ Η _β Eeitsema, J _e lmer _e Chem _e Soc _e 68, 766 (1946) j D * _{e e} Browp, M _e N »Paad6a-How, ^ .ChenuSoo. (C) 1% 7, 903 (1928)) or pyrimidipaldoximes with thiooyl chloride or acetaphydride (EUBredere GeSimchep, H» Wagner, A * A _e Saotos, Liebigs Anp _e . Chem., 766, 73 (1972)). Here, however, the Syothesis de AusgassgSTerbiüduDgep is very complicated.

5-CyaD-2- / 4-subst ₉ -pheP7l7-p3rrimidiDe are heretofore manufactured /"A.Boiler, M, Cereghetti, M _e S'chadt, H ₉ Scher rers Mol »Cryst _e Liqu _e Cryst _e 42, 215 (1977) /: An ^ -sten-BeDSamidio hydrochloride is coupled with ethoxy-methylep-diethyl acid ester on a 5-carbonyloxyethyl ~ 6-hydroxy-7-2- / 4-substituted-phenyll-1-pyrimidipol in which in two

212 876

In further reaction steps, the hydroxy group is substituted by chlorine or hydrogen, and in the fourth reaction step the carbonyloxyethyl group is converted to the cyano group according to the following scheme:

C ₂ H ₅ OCH

C ₂ H ₅ OOC

C-COOC ₂ H ₅

R-

This course of the Syothesis runs over four stages. "It is therefore laborious, and, since the individual stages do not proceed quantitatively, yields comparatively little on the whole. The same authors give in DD-WP 124 731 and in DE-OS 254 7737, the synthesis of these compounds by a very time-consuming reaction of 4-subst. Benzamidine hydrochlorides with 'Alkalisalzeη of acetalated hydroxymethylene-cyanoacetaldehyäen in aqueous reaction medium to The patents, however, contain no information about the yield' The workup of the obtained according to Example 6 brown oil by column chromatography indicates that this method is not without problems, for what also the search of the authors for a new synthesis speaks. ,

2 12 8 7 8

It is noteworthy that the reaction carried out in the aqueous solution led in part to nitrile. Owing to the fact that, in the case of earthiness, toq water aostelle der Nitriles äie eotspreoheodeD Säiireamiäe eatsteheo ·

goal of

The aim of Erfioäuög is io the eiafaohep Herstellupg rop 5-Cyad "> 2 _i / 4 ~ substo '' pheQyl7 ^ pyrimidiseD with höhep yield

The task of the invention is eip oeues Yerfahrep for the production of this VerbioduDgeD «

It was found that 5-CjaD-2- / 4-subst, -pheDyl / -pyrimidiQe of the general formula J _- ,

where R -

; C _n H _{2n + 1} - (H) -COO ₅

^E - ^C P ^H 2P + 15 ^C p ^H 2d

with ρ β 1 to 10

"means by KoDdeosatioo vod 4-subst. Benzamidip-hydröohloxidep with cC -CyaD-ß-dimethylamino-acroleip ip pyridip and or 5 riethjlamiD or other * strong organic bases with very good yield in a reaction step preparable them

> g

-A-

2 12 17 6

The reactions proceed according to the general scheme:

KH * w

O HCl. Λ. ² J ^ C-CN- * ROC T-CN

example 1

Production yod gC.yap-2 - ^ - h

The preparation is carried out according to the general scheme I, where R is OH.

50 ml of abs * triethylamine, 50 ml of absolute pyridine, 17.3 g (0.1 mol) of 4-hydroxybenzylidene-by-hydrochloride and 11 g (0.1 mol) of eC-cyano-β-dimethylamino-aorolein are added under stirring Heated to 8O ⁰ C The dark brown colored reaction mixture is on ice / kons, 'H ₂ SO / |'. (500 g / 50 ml) fermented, the precipitate was filtered off with suction, washed thoroughly with water and recrystallized from methanol / charcoal. r -k '

The yield is 12.8 g (65 % of theory). F: 260-262 (sublimed) _e

Example 2 Preparation of the 5-cyano-2- / 4-aoyl-phenyl-7-pyrimidines

The preparation is carried out by reacting the ^ - phenyl / pyrimidine with acid chlorides according to the variants of unicorn or Schotten-Baumann according to the general scheme II

II R ^ COCL + HO-O-V ~~ ν ° ^Ν - * "Ä ¹ -COO-O- ^" VcN + HCl

Ί> 97 g (0.01 mol) of 5-cyano-2- /--hydroxy-phenyl / -pyrimidine and 0.015 mol of the corresponding acid chloride are stirred in 25 ml of abs × Py ridin 6 hours at room temperature, then heated for 5 minutes at reflux and allowed to stand overnight. The reaction product is poured onto ice / conc. H 2 SO 4 (300 g / 20 ml).

, in ltb, he picked up the ethereal phase with 1 η KOH solution and washed Y / asser »Subsequently, vdrd with Na ₂ SO. ^ dried, the solvent distilled off on a rotary evaporator UOD the Rüokstaoä several times from D-hexane umkristaXli "siexte The yield is 70-90 $ of theory

!Table 1

CH ^ O

C _E H.

107

121

83

106

224 -

130 ~

117

123

129

96 * 121

112 β- 249

334

278

192 _β 248

Example 3

Manufacture of;

, Baw "

Pyrimidioe · The preparation is carried out according to the general scheme I, wherein

40 ml abs. Triethylamio, 1 _s. 1 g (0.01 mol) .sup.-1 Cyan-.beta.-dimethylaminoDo-acroleinD and O.sub.01 molar substituted benzamidia-hjärophlorid bs \ v _e the free base are stirred for 6 hours at 80.degree heated «, The cooled reaction mixture Tdrd to 150

- 6 - 2 12 8 7

Ice cream / 30 ml conc. Poured H ₂ SO ^, the precipitate was filtered off, washed thoroughly with V / ässer and then recrystallized several times in n-hexane · The yield is 75-95 % of theory · Examples contains Table 2 ·. ,

Table 2 RO- f

₁₅

RKS _A NI

C ₄ H ₉ O. 119 - ♦ 139

, ^C 5 ^H 11 ° '·. ⁹⁷ · " ¹⁰² s ⁵ * 133

^C 6 ^H 13 ° * ^92j5 · ¹²² * ¹³⁴ > ⁵ * '

C "H. _K 0 · 102, 127 · 129

C ₄ H ₉ "109 -" - (. 101) C = H ,,. 94 (· 93,5) · 109

, C ₇ H ₁₅ · 94 ♦ 107 C ₉ H ₁₉ · 90 ♦ 107

Claims (1)

212 878 Erfipflupgsapspruoh, Process for the preparation of 5 ~ CyaQ-2 ~ / ° 4 ~ see _e -pheDyl7 of general formula J, ' ^{; 0HS C} D ^H 2o + 1 ^CS · with ρ = 1 to 10 means that 4-subst _e- BeDcamidiD hydrochloride is co-dosed with cα-Cyao ~ I3-diraeth-7lamino-acroledi in pyxidip upd / or triethylamia and / or adeno-strong orga pisoheo baseo.