DD253818A1 - PROCESS FOR THE PRODUCTION OF 2-POSITION BY NUCLEOFUG EASILY REPLACEABLE RESTE SUBSTITUTED 3,5-DIARYLOXAZOLE SALMS - Google Patents

Abstract

Such compounds have importance as intermediates for organic dyes and luminophores, as biologically active substances and as versatile synthesis building blocks in the organ. Synthetic chemistry. The invention seeks to make previously known in the 2-position by nucleofug easily replaceable radicals substituted 3,5-diaryl-oxazoliumsalze accessible in a simple manner. This is done according to the invention in such a way that halomethyl-aryl ketones with N-aryl-Iminokohlensaeurederivaten to the in position 2 by nucleofug easily exchangeable radicals substituted 3,5-diaryl-oxazolium salts of type 1, wherein X is a dialkylamino, alkylthio or alkyloxy is reacted. formula 1

Description

wherein Ar ¹ and Ar ² , which may be the same or different, represent a phenyl, naphthyl or heteroaryl group unsubstituted or substituted by alkyl groups, alkoxy groups, halogen atoms or nitro groups, X and Y, which may also be the same or different, represent a dialkylamino group Alkylthio or alkoxy and Z is an acid residue anion, such as. B. CIO ₄ or Br represent, are implemented.

Field of application of the invention

The invention relates to a process for the preparation of in position 2 by nucleofug easily exchangeable radicals substituted 3,5-diaryl-oxazolium salts.

Such compounds are important as intermediates for organ. Dyes and luminophores, as biologically active substances as well as versatile synthesis building blocks in the organ. Synthetic chemistry.

Characteristic of the known technical solutions

The claimed 3,5-diaryl-oxazolium salts which are substituted in the 2-position by nucleofug easily exchangeable radicals are hitherto unknown.

Object of the invention

The aim of the invention is to make the hitherto unknown in the 2-position by nucleofug easily replaceable radicals substituted 3,5-diaryl-oxazolium available in a simple manner from readily available starting materials.

Explanation of the essence of the invention

The object of the invention is to prepare the hitherto unknown in the 2-position by nucleofug easily replaceable radicals substituted 3,5-diaryl-oxazolium salts in a simple manner. According to the invention, this object is achieved in that halomethyl-aryl ketones of the formula type. 1

Q is Ar ¹ -C-CH ₂ -HaI

with N-arylimino-carbonic acid derivatives of type 2

Ar ² - N = CX

in acetic anhydride and in the presence of a metal salt of a strong mineral acid to the 1-substituted type 3 3,5-diaryloxazolium salts.

wherein Ar ¹ and Ar ² , which may be the same or different, are a phenyl, naphthyl or heteroaryl group unsubstituted or substituted by alkyl groups, alkoxy groups, halogen atoms or nitro groups, X and Y, which may also be the same or different, is a di-alkylamino group Alkylthio or alkoxy and Z is an acid residue anion, such as. B. CIO4 or Br represent, are implemented.

embodiments

Substituted by different variants in the 2-position by nucleofug easily substituted radicals substituted

3,5-Diaryl-oxazolium salts are listed in Table 1.

Represented in the 2-position by nucleofugically exchangeable radicals substituted 3,5-diaryl-oxazolium salts

Ar ²

Mp PC]

Y. [% d. Th] / variant

3-NO ₂ -C ₆ H ₄ C ₆ H ₅ C ₆ H ₅ C ₆ H ₅ Morpholino Morpholino CIO ₄ CIO ₄ 4-CI-C ₆ H ₄ C ₆ H ₅ morpholino CIO ₄ C ₆ H ₅ C ₆ H ₅ C ₆ H ₅ C ₆ H ₅ C ₆ H ₅ C ₆ H ₆ SCH ₃ SC ₂ H ₅ SC2H5 CIO ₄ Br CIO ₄ 4-Br-C ₆ H ₄ C ₆ H ₅ SC ₂ H ₅ CIO ₄ C ₆ H ₆ C ₆ H ₅ C ₆ H ₅ 4 -CH ₃ -C ₆ H ₄ SCH ₂ -C ₆ H ₄ -P-NO ₂ OC ₂ H ₅ CIO ₄ CIO ₄

C ₆ H ₅

OC ₂ H ₅

126 150s.

129-130

135-137

157-160

189

200Zers

 205Zers.

215Zers.

69 / A 74 / A 43 / B 89 / A 23 / B 49 / C 14 / D 52 / C 72 / E 37 / C 63 / E 51 / E 32 / F 37 / G 37 / F 41 / G

Option A:

0.05 mol of a pentasubstituted guanidine 2 (X = Y = dialkylamino) and 0.05 mol of a halomethyl-aryl-kentone 1 are dissolved in 75 ml of acetic anhydride in the presence of 5.6 g (0.025 mol) of Mg (CIO ₄ I ₂ After 1-2 minutes, it is allowed to cool and filtered off with suction from the precipitated product, possibly after addition of ether, and recrystallized from isopropanol / glacial acetic acid (2: 3).

Variant B:

0.05 mole of tetra-substituted isothioureas 2 (X = dialkylamino, Y = alkylthio) are mixed with 0.05 mole of bromomethylaryl ketone 1 and 5.6 g (0.025 mole) Mg (CIO ₄ J ₂ in 80 mL acetic anhydride, the few crystals AgNO ₃ or Pb (CH ₃ COO) _{2 are} added, suspended and slowly boiled, and the black-browning solution is cooled after 2-3 minutes, and 50 ml of dry ether are added, and the precipitated oil becomes isopropanol after decanting from the solvent

recrystallized.

Variant C:

0.05 mol of a substituted phenyiimino-dithiocarbonic acid diester 2 (X = Y = alkylthio) and 0.05 mol of a bromomethyl-aryl ketone are suspended with 5.6 g (0.025 mol) of Mg (CIÖ ₄ ) ₂ in 50 ml of acetic anhydride and very much within 10 minutes slowly heated to boiling. After 2-3 minutes, the mixture is cooled, treated with a little dry ether or ether / ethyl acetate mixture (1: 1) and filtered with suction from the crystals forming and recrystallized from glacial acetic acid / ether.

Variant D: -

The procedure is as in variant C, but without the addition of Mg (CIO ₄ I ₂₎ . The products precipitated after cooling and addition of ether were filtered off with suction and recrystallized from isopropanol.

Variant E:

0.05 mole of a tetrasubstituted isothiourea (X = alkylthio, Y = dialkylamino) was reacted with 0.05 mole of a halomethyl-aryl-ketone 1 in 40 ml of acetic anhydride in the presence of 5.6 g (0.025 mole) Mg (CIO ₄ ) ₂ suspended and slowly heated to boiling. After 2-3 minutes of boiling is cooled, treated with ether and filtered with suction. For purification can be recrystallized from isopropanol / glacial acetic acid.

Variant F:

0.05 mol of a substituted phenylimino-carbonic acid diester 2 (X = Y = alkoxy) are suspended with 0.05 mol of a bromomethyl-aryl ketone 1 in 80 ml of acetic anhydride, heated to boiling and left for 4-5 minutes. Then allowed to cool, carefully 7.2 g (0.05 mol) of 70% HCIO ₄ so that the temperature of the solution does not rise above 60 ⁰ C, and after cooling to room temperature with ether. The precipitated crystals are filtered off with suction and recrystallized from glacial acetic acid / acetic anhydride with the addition of a few drops of HClO ₄ for purification.

Variant G:

0.05 mol of tetrasubstituted isourea 2 (X = alkoxy, Y = dialkylamino) and 0.05 MpI of a bromomethyl-aryl ketone are suspended in 60 ml of acetic anhydride and slowly heated to boiling. After 2 minutes of cooking, allowed to cool and continue as indicated in variant F.

Claims (2)

Process for the preparation of in 2-position by nucleofug easily exchangeable radicals substituted 3,5-Diaryloxazoliumsalzen, characterized in that halomethylaryl ketones of the general Fomel. 1 0
Ar ¹ -C-CH ₂ -Hal ¹ with aryliminocarbonic acid derivatives of type 2 Ar-N = C-X I 2 in acetic anhydride and in the presence of a metal salt of a strong mineral acid, such as Mg (CIO), to the 3,5-diaryloxazolium salts of type 3 substituted in the 2-position by nucleofugically exchangeable radicals