JPH01261353A - 4-alkoxycarbonylphenylacetylene - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (n is 1-6; m is 0-5; *indicates asymmetric carbon). USE:Useful as a synthetic intermediate for liquid crystal compounds and also as a synthetic raw material, etc., for Langmuir-Blodgett membranes which are electronic material. EXAMPLE:A 4-(p-alkoxycarbonylphenyl)-2-methyl-3-butyn-2-ol expressed by formula 11 (R* is a group expressed by formula III) is reacted with anhydrous toluene and sodium hydride at a temperature within the range of ambient temperature the boiling point of the solvent in a nitrogen gas stream to afford the aimed compound expressed by formula I. The compound expressed by formula II is obtained by reacting a 4-alkoxycarbonylbromobenzene with 3-methyl-1-butyn-3- ol in the presence of a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel 4-alkoxycarbonylphenylacetylene.

4-Alkoxycarbonylphenylacetylene is used as an intermediate in the synthesis of liquid crystal compounds.

LB (La) is attracting attention as an electronics material.
It is expected to be applied as a raw material for the synthesis of ngmuir Blodgett (ngmuir Blodgett) membranes.

[Conventional technology]

The 4-alkoxycarbonylphenylacetylene of the present invention is a compound that has not been described in any literature.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a novel 4-alkoxycarbonylphenylacetylene.

[Means for solving problems]

The present invention relates to the general formula CI"1 (In the formula, n is an integer of 1 to 6, and 1m is an integer of θ to 5.

4-alkoxycarbonylphenylacetylene represented by *indicates an asymmetric carbon atom.

The method for producing the compound represented by the general formula CI) is detailed below, and one of the raw materials for the production is optically active alcohol
(R”OH) is used. Optically active alcohols are available at low cost considering their industrial versatility. For example, as primary alcohols, 2-methylbutanol, 3-
Methylpentano, 4-methylhexanol, 5-methylheptatool.

6-methyloctatool, 1-methylpropatol and 1-methylbutanol as secondary alcohols.

■-Methylpentanol, 1-methylhexanol, l
-Methylhebutanol, 1-methyloctatool, etc. are often used.

The 4-alkoxyluponylphenyl acetylene of the present invention is produced by the following method.

[A]

(H3 H3 represents an integer from 1 to 6, and 0m represents an integer from 0 to 5.) After the reaction is completed, a usual post-treatment is carried out, and if necessary, it can be purified by recrystallization, chromatography, distillation, etc.

[Function and effect of the invention]

The 4-alkoxyluponylphenyl/L'7cetylene of the present invention is a novel compound) and is expected to be used as an intermediate for the synthesis of liquid crystal compounds, as well as a raw material for the synthesis of LB films.

〔Example〕

Next, the present invention will be explained with reference to Examples, in which % indicates weight %.

In a 500 cc three-turn flask equipped with a stirrer, a thermometer, and a reflux condenser, 0.234 mol of 4-alkoxycarbonylbromobenzene and 3-methyl'-y-'-butyn-3-ol were added in a nitrogen atmosphere. 29.57 (0,352
m01) , ) Riphenylphosphine 1.00 f
, dichlorobis(triphenylhonuphine) palladium Mljo, 52y (0.73 mmol) and 200 mt of triethylamine were charged and dissolved with stirring, and 160 ml of copper iodide was added. After stirring at room temperature for 3 hours, the mixture was gradually heated to bring the internal temperature to 90°C over 30 minutes. The reaction was allowed to proceed at this temperature for 20 hours.

After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, and the residue was mixed with 300 mt of ether and washed with water.

It was dried with anhydrous sodium sulfate. After filtration, the ether was distilled off, and the residue was subjected to silica gel chromatography (200
It was purified by applying mesh silicage/'v400 t, developing solvent: benzene).

Table 1 shows the IR and NMR spectra and yields of each compound obtained.

4-(p-
Flukoxyluponylphenyl/l/)-2-methyl-3
-butyn-2-ol CB) 58.4m+nol.

120 mt of anhydrous toluene and sodium hydride (
60% Nujool dispersant) 310■ and at room temperature
Stirred for 0 minutes. Heat gradually, taking 30 minutes to bring the internal temperature to 7.
The temperature was 0°C. Acetone (a by-product) began to reflux and distill out together with toluene, but the reaction continued with further heating until the distillation temperature reached the boiling point of toluene. This took 2 hours, and the amount of solvent distilled out was 60 ml. After the reaction was completed, the temperature was returned to room temperature, 100 mt of benzene was added, and the mixture was washed with water and dried over anhydrous sodium sulfate. After filtration, the organic solvent was distilled off and the residue was subjected to silica gel cuff chromatography (2
4-alkoxycarbonylphenylacetylene shown in Table 2 was obtained in a yield of 90 to 94%.

Its structure was confirmed by IR and NMR spectra.

The results are shown in Table 2 along with the physical properties of each compound obtained.

Claims (1)

[Claims] General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, n is an integer from 1 to 6, m is an integer from 0 to 5, * is an asymmetric carbon 4-alkoxycarbonylphenylacetylene represented by (individual atoms are indicated).