DD145914A1 - PROCESS FOR PREPARING NEW 4-SUBST.-THIOBENZOESAEURE S-STRONG BRACKET ON 5-ALKYL PYRIMIDINYL- (2) -ESTER SQUARE BRACKET CLOSED - Google Patents

Abstract

The invention relates to a process for the preparation of new 4-Subst.-thiobenzoesäure-S- & 5-alkyl-pyrimidinyl- (2) esters !, Which can be used in optoelectronic components as dielectrics. The aim of the invention is the preparation of crystalline-liquid 4-Subst.-thiobenzoesäure-S- & 5-alkyl-pyrimidinyl (2) esters !. It was found that new crystalline-liquid 4-subst.-thiobenzoic acid S- & 5-alkyl-pyrimidinyl (2) esters! of the general formula wherein R = formula where n = 1 to 12, can be prepared by reacting 5-alkyl-2 (1H) -pyrimidinethionene with a 4-substituted benzoyl chloride.

Description

".V-he go to He rstellung of new 4-Suh st .- thiobenzoic acid S- ~ f 5-alk; 7l-p; yrimidin; v · l ^ - (2) ~

Anvje ndungs area _The invention

The invention "relates to a process for the preparation of novel 4-Subst. ~ Thio" benzoic acid S ~ [5-alkyl-pyrimidinyl ~ - (2) esters] of the general formula.

where R -G _{n is} H _{2n + 1} , C _n H _{2n + 1} O, C _n H _{2n + 1} GOO F, Cl, Br, NO ₂ , CN-, CF ^

with η = 1 to 12 mean '.

The substances are crystalline-liquid and can advantageously be used in optoelectronic components for the representation of numerals and oaks.

Charakter ^ characteristic of the "known technical solutions

The substances produced by the "process according to the invention are novel, therefore, no processes for their preparation have hitherto been known.

Object of the invention

The aim of the invention is the production of crystalline. Liquid 4-Substituted-thiobenzoic acid S "f ^ -alkyl-pyriraidinyl" (2) ~ estererri I *

Darj.egupg _{i of} the ^ essence of the invention

It has been found that new crystalline liquid S-f5-alkyl-pyrimidinyl (2) -esters of the general formula ## STR3 ## are n-thiobenzoic acid

CH _{0 Λ} η 2n-r 1

where R "C _n H _{2n + 15} C _n H _{2n + 1} O ₅ C _n H _{2n + 1} COO, C _n H _{2n + 1} OCOO, F, Cl, -Br j NO ₂ , CN, CF ₃

with η = 1 to 12 ",

by reacting γοη 5-alkyl-2 (iH) -pyrimidinthions with a 4-Subst "-benzotrichloride can be prepared according to the general scheme?

5-Alkyl-2 (iH) -pyrimidinic acids are accessible in good yields by condensation of 1,3-dicarbonyl compounds with thiourea under acidic or alkaline reaction conditions / 1,2 /. In the benzoylation of the 5-alkyl-2 (iH ') -pyximidinethiones in which a tautomeric equilibrium exists between the thiol and thione form, S or N-acylated products can be formed. According to the invention, the reaction of the 2 (1H) -pyrimidinethiones or their sodium salts with substituted benzoyl chlorides or cyclohexanecarboxylic acid chlorides in benzene, toluene or another aprotic solvent at temperatures of 50-10 ° C. in high yields to form 4-substituted thiobenzoic acid S, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, R, esternj.

/ 1 / Brown, I). J. ί "The Pyrimidines", Ed. A.Y / Eissberger, interscience, New York £ 62.j Supplement I ₅ Wiley Interscience 1J970

/ 2 / HoIy ₅ A ,; Arnold, Z, Collect. Czecbosiov. Chem. Commun. 23.?· 1371 (1973)

1 ft *? 1

Aus uns un .ss example

example 1

, -φ

Preparation of 5-hexyl-2 (iH) -pyTimidinthion 1_ To 30 g (0.15 mol) cL · hexyl ß-dimethylamino-acroMn, 15.2 g (° 2 mol) of thiourea and 100 ml of abs. Pyridine with stirring "at 90 ⁰ C a solution of sodium methylate from 0 58 _g?.. (0j03 g - ^ - tome) of sodium are added dropwise in 20 ml of a ds methanol The reaction mixture is · stirred for 8 $ -tä at 95 ⁰ C and after the The precipitate is filtered off with suction, dissolved in dilute sodium hydroxide solution, the solution is treated with activated charcoal and, after filtration, precipitated again with acetic acid.

Yield: 32.2 g (95% of theory) F: 176-178 ° (methanol)

Example 2 '.

Preparation of 4-subst.-thiobenzioesau.re-S-pyriiridinyl (2) esters]

2m sodium methylate solution of 0.23 g (0.01 g atoms) of sodium in 15 ml abs. Methanol becomes 1.96 g (O ₅ O 1 molJ 1_

20. added and stirred until dissolved. The solvent is then distilled off and, with stirring, the residue is combined with 30 ml of benzene and 0.04-0.015 mol of the corresponding acid chloride. After stirring for 2 hours, AIpO and charcoal are added, filtered, the filtrate is concentrated on a rotary evaporator and the crude product of cyclohexane or η-hexane is recrystallized several times.

The yield is 4-0 - 80 1 " of theory.

° 6 "13 \

R K .N * • I C ₅ H ₁₁ - , 68 C C 49). 6 13 , 58 C. (. 42). CH ₃ O- , 98 C. C. 47). ; C ₂ H ₅ O- , 58 74 C ₃ H ₇ O- c 69 , 5 (0 .65.5). ^C 4 ^H 9 ° ~ , 83 C. 75). C ₅ H ₁₁ O- , 75 _? 5 (. 70.5). C ₆ H ₁₃ O- , 67 0 75. '. C ₇ H ₁₅ O- , 56 • 71.5 C ₈ H ₁₇ O- , 67 * 74.5 CqH ₁₉ O- ♦ 66 • 71 ^C 10 ^H 21 ° - , 68 73.5 C ₁₂ H ₂₅ O- , 68 76 CN , 91 88.5). C _r H ,, OCOO 6 13 -. 76 53). NO /) , 85 70.5).

K 85 (p. 65 _? 6 N 70.5) I

 'A

Claims (1)

E r f i η α η g s' a η s ρ r u c h Yexfahren for Hexstellung of crystalline-liquid 4-Subst.-thio'benzoesäuxe-S- [^ -alkyl-pyximidinyl- (2) ~ estexnJ the general Foxmel H ₀ , -4> ~ sc- <Ö> -R ι where R = C _n H _2n ., CH ₂ . C _n H _{2n + 1} OCOO, F, Cl, Br, NO ₂ , CN, CF ₃ with η = 1 to 12
mean, characterized in that 5-alkyl-2 (iH) -pyximidinethione or their sodium ··· salts in benzene, toluene or another aprotic solvent at temperatures between 50 and 100 ⁰ C with a 4-substituted benzoyl chloride. puts