JPS5821613B2 - Carbonyl Kagobutsu no Bunrihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating carbonyl compounds.

Specifically, the present invention involves separating aldehydes or ketones from mixtures of aldehydes or ketones and other hydrocarbons, or separating mixtures of two or more aldehydes or ketones into individual aldehydes or ketones. It is about the method.

The present inventors previously discovered that I of trihalogenomethanesulfonic acid
Group B metal salts form complexes with olefinic hydrocarbons, aromatic hydrocarbons, condensed polycyclic hydrocarbons, carboxylic acid esters, etc., and there are large differences in the ability to form this complex between isomers. They discovered that the isomers could be separated and obtained by decomposition using a suitable method, and have already applied for a patent.

Furthermore, the present inventors have discovered that aldehydes or ketones are
・It forms a complex with the IB group metal salt of logenomethanesulfonic acid, and the ability to form the complex differs depending on the type of aldehyde, ketone, and isomer, so this property can be used to separate and obtain the aldehyde or ketone. The present invention has been achieved by discovering what can be done.

) That is, the present invention aims to industrially advantageously separate and obtain aldehydes or ketones from mixtures containing aldehydes or ketones. (b) A mixture containing positional isomers of the carbonyl group of an alicyclic ketone; (e) A mixture containing an olefinic carbonyl compound and a corresponding saturated carbonyl compound. , and (d) a mixture containing isomers depending on the substitution position of the aromatic carbonyl compound. A mixture of carbonyl compounds selected from Represents copper or silver.

) to form a complex with at least one of the carbonyl compounds, the formed complex is separated, and then decomposed to recover the carbonyl compound. Ru.

Next, the present invention will be explained in more detail.

The trihalogenomethanesulfonate used in the method of the present invention is a compound represented by the general formula, in which the halogen atoms represented by x, y, and z are specifically fluorine, chlorine, and bromine. , is iodine.

Among these, fluorine and chlorine are particularly preferred, and X, Y, Z
may be of the same kind or of different kinds.

Specific examples include trifluoromethanesulfonate, difluorochloromethanesulfonate, fluorodichloromethanesulfonate, and trichloromethanesulfonate.

Moreover, M is copper or silver.

The carbonyl compound that can form a complex with the trihalogenomethanesulfonic acid metal salt is an aldehyde or ketone represented by the general formula.

In the formula, R and R' are hydrogen or a hydrocarbon group such as an alkyl group, an aryl group, an alkenyl group, and the present invention
'can be applied to any combination of aldehydes or ketones.

Further, these groups may be further substituted with an alkyl group, an alkoxy group, or the like.

Specifically, the present invention is applied to the separation of positional isomers of carbonyl groups in aliphatic ketones such as heptanone and alicyclic ketones such as methylcyclohexanone, and is applied to the separation of positional isomers of carbonyl groups such as methyl vinyl ketone and mesityl oxide. It is applied to the separation of olefinic carbonyl compounds from the corresponding saturated carbonyl compounds, and isomer mixtures depending on substitution positions such as meta and para forms in aromatic carbonyl compounds such as methylacetophenone and methoxyacetophenone. Applies to separation of

In order to form a complex between the carbonyl compound and the trihalogenomethanesulfonate, the carbonyl compound may be brought into contact with the trihalogenomethanesulfonate in a liquid or gaseous state.

For example, if a mixture of these carbonyl compounds or a mixture with other hydrocarbons is mixed in liquid form with a solid trihalogenomethanesulfonate, a complex is formed.

The temperature may be heated, or room temperature may be sufficient.

The complex generated at this time may be dissolved or precipitated.

Next, the complex can be precipitated as a solid by distilling off the excess carbonyl compound, cooling it, or adding paraffin such as hexane or cyclohexane.

At this time, since the presence of moisture hinders complex formation, it is preferable to carry out the process in a dry state.

Alternatively, a column may be filled with a solid trihalogenomethanesulfonate or a porous carrier such as alumina, silica, celite, pumice, or activated carbon, and then a carbonyl compound may be introduced in gaseous form into the column. Able to form complexes.

At this time, the gas may be introduced under normal pressure or reduced pressure, supported by an inert gas such as nitrogen, if necessary, in a heated state.

The temperature for complex formation can usually be set appropriately within the range of room temperature to 200°C.

The complex thus obtained is easily decomposed by contacting with water or heating to regenerate trilogenomethanesulfonate and the carbonyl compound.

For example, when a complex is put into water at room temperature, the complex decomposes and the trihalogenomethanesulfonate dissolves in the water.
Water-insoluble carbonyl compounds are separated as an oil layer.

In the case of a water-soluble carbonyl compound, the carbonyl compound can be obtained from the aqueous layer by extraction with an appropriate solvent.

On the other hand, trihalogenomethanesulfonate can be easily recovered by distilling off water.

Further, the complex decomposes into a trihalogenomethanesulfonate and a carbonyl compound by contacting with water vapor or by heating.

The processing temperature at this time is appropriately selected between room temperature and 300°C.

When recovering a carbonyl compound by thermal decomposition of a complex, the decomposition temperature differs depending on the type of isomer composing the complex, so the decomposition temperature should be selected appropriately and further separation and purification should be carried out at this stage. is also possible.

As described above, by the method of the present invention, carbonyl compounds can be easily obtained in high purity without the need for complicated chemical operations such as conventional precision fractionation methods, extraction methods, and crystallization methods. can.

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example I 2.42f of a mixture consisting of 50.4% P-methoxyacetophenone and 49.6% m-methoxyacetophenone and 1.02P silver trifluoromethanesulfonate were mixed at room temperature.

Next, n-hexane was added to this mixture to separate the crystals, which were dried to obtain 1.32P white crystals.

10 ml of water and 5 ml of n-hexane were added to the crystals, stirred to dissolve the crystals, and then separated into an aqueous phase and an n-hexane phase.

When water is evaporated from the aqueous phase, silver trifluoromethanesulfonate is 1.02? was recovered.

On the other hand, when the n-hexane phase was analyzed by gas chromatography, the following results were obtained.

P-methoxyacetophenone 85.2% m-
Methoxyacetophenone 14.8% Recovery rate of carbonyl compound 12.4% Example 2 Mixture consisting of 50.1% methyl isobutyl ketone and 49.9% mesityl oxide 0.79 ? and 0.85 P of cupric trifluoromethanesulfonate were mixed at room temperature.

Next, excess ketone was distilled off at 50°C under reduced pressure of 5 mynHg, and 10 ml of water and 5 ml of n-hexane were added to the 0.96P residue, and after stirring to dissolve the crystals, the aqueous phase and n-hexane phase were separated. It was separated into two parts.

Evaporation of water from the aqueous phase recovered a mixture of 0.12 P of copper and 0.72 S' of silver trifluoromethanesulfonate.

On the other hand, when the n-hexane phase was analyzed by gas chromatography, the following results were obtained.

Mesityl oxide 71.8% Methyl isobutyl ketone 28.2% Carbonyl compound recovery rate 13.9% Example 3 Mixture consisting of 51.5% 2-methylcyclohexanone and 48.5% 4-methylcyclohexanone 0,92 r
and silver trichloromethanesulfonate (0.31 V) were dissolved at room temperature, and then the excess ketone was distilled off at 50° C. under reduced pressure of 5 mmHg to obtain a residue of 0.52 f.

Next, 10 ml of water and 5 ml of n-hexane were added to the remaining solution and stirred, and the n-hexane phase was analyzed by gas chromatography to obtain the following results.

4-Methylcyclohexanone 74.0% 2-
#-Lcyclohexanone 26.0% Recovery rate of carbonyl compound 22.8% Example 4 Heptanal 389%, 3-hebutanone 40.7%, 4
- A mixture consisting of 20.4% hebutanone 1.64 fI and silver trifluoromethanesulfonate 0.25 ? were mixed at room temperature, and then the excess heptanone was mixed at 50°C for 5 imH.
When the residue was distilled off under reduced pressure of 0.405 g, a residue of 0.405' was obtained.

10 ml of water and 5 TL of n-hexane were added to this residue and stirred, and the n-hexane phase was analyzed by gas chromatography to obtain the following results.

Claims (1)

[Scope of Claims] 1(a) A mixture containing a positional isomer of the carbonyl group of an aliphatic ketone or an aliphatic aldehyde, (b) A mixture containing a positional isomer of the carbonyl group of an alicyclic ketone, (C ) a mixture containing an olefinic carbonyl compound and a corresponding saturated carbonyl compound; and (d) a mixture containing isomers depending on the substitution position of the aromatic carbonyl compound. (wherein, X, Y, and Z represent halogen atoms, and M represents copper or silver) to form a complex with at least one of the carbonyl compounds by contacting with a trihalogenomethanesulfonic acid metal salt represented by 1. A method for separating carbonyl compounds, which comprises separating and then decomposing the carbonyl compounds to recover the carbonyl compounds.