JPS5944289B2 - Separation method of metacyclophane - Google Patents

Description

[Detailed description of the invention] The present invention is based on the following formula (I) Giant-0 [y’width This invention relates to a method for separating metacyclophane represented by

More specifically, a mixture containing metacyclophane represented by the above formula (I) and the following formula (...)X□Y(■)[
However, in the formula, □ represents a di-hexane ring or a benzene ring, and X is -H, -CH3
, -C2H5, -CO0CH3, or a halogen atom, and Y represents -H, -CH3, -C2H5, or a halogen atom.

A separation method for recovering high-purity metacyclophane (I) at a high recovery rate using a clathrate compound produced by contacting at least one compound selected from the group consisting of the compound represented by ] and tetrahydrofuran. Regarding.

The reaction product containing the metacyclophane mark obtained by a conventionally known method contains unreacted raw materials, uncyclized dimers, or higher polymers as impurities.
This includes metacyclophane in which 5 or fewer molecules have been cyclized, and metacyclophane in which 7 or more molecules have been cyclized. Isolating I) is not only difficult due to their close physical properties, but also has disadvantages such as requiring high vacuum and high temperature.

Furthermore, as a conventional method for separating methane clothanes, for example, Helvetica chimica acta (Helvetica chimica acta) has been used.
ChemicaActaVOl・52Fasc・7(
1969) Consideration 204 and the same Vol. 5OFasc. s
(1967) Ma 266), column chromatography separation methods are often used, and metacyclophane (I)
The separation is extremely inefficient and is definitely not suitable for industrial implementation.

As a result of intensive research on separation and purification methods for metacyclophane (I), the present inventors found that metacyclophane (I) forms clathrate compounds with certain organic compounds, and that such compounds can be formed. The present invention was achieved by discovering that metacyclophane (I) can be easily separated by the following steps.

That is, the present invention provides a mixture containing a metacyclophane represented by the following formula (I), and a mixture containing a metacyclophane represented by the following formula (I), where HA>- represents a cyclohexane ring or a benzene ring, and X represents -H, -CH3, -C
Represents 2H5, COOCH3, or a halogen atom,
Y represents -H, -CH3, -C2H5 or a halogen atom.

] and at least one compound selected from the group consisting of tetrahydrofuran, the compound and the above metacyclophane (I) are brought into contact with each other.
The above-mentioned metacyclophane (
metacyclophane (I) characterized in that it separates
), in particular, the compound () is a metacyclophane (I ).

The metacyclophane (I)-containing mixture applicable to the present invention is, for example, Helvetica chimica acta (Helvetica chimica acta).
icaChlmlCaActa5OFascicu1
Us7 (1967)/F6.2O4) and synthesis (see Synthesis 424 (1974)), etc., and those produced by any method can be applied.

For example, when applying the method previously proposed by the present inventors, for example, a metacyclophane (I)-containing reaction product produced by the reaction shown by the following formula, inorganic substances etc. can be removed from the reaction product by filtration. Although the separated residual liquid can be used as a raw material as it is, it is preferable to use the residue after removing the solvent and concentrating it. It is also possible to apply highly concentrated solutions of cyclophane (I).

In addition, the organic compound used in the present invention has the following formula () [however,
In the formula, A'>- represents a cyclohexane ring or a benzene ring, and X represents -H, -CH3, -C2H5, -C
OOCH3 or represents a halogen atom, Y is -H,
Represents -CH3, -C2H5 or a halogen atom.

] and at least one compound selected from the group consisting of tetrahydrofuran (button, preferably p-xylene, p-diethylbenzene, toluene, benzene, cyclohexane, methyl benzoate,
and tetrahydrofuran are preferred.

In the present invention, when the mixture containing metacyclophane (1) is brought into contact with the compound (), the metacyclophane (1) contained therein selectively becomes the clathrate compound, and the metacyclophane (1) in the mixture selectively becomes the clathrate compound. The solubility difference or boiling point difference between a compound other than (1) and the clathrate compound increases.

The present invention takes advantage of this phenomenon to produce metacyclophane (1).
It separates the The clathrate compound of metacyclophane (1) and the organic compound (), which is formed by bringing the mixture containing metacyclophane (1) into contact with the organic compound (), is formed by: when a solvent is used, Depending on the solvent used, it can take various forms, such as dissolved as it is or crystallized. If the clathrate is dissolved, the non-clathrate component and the clathrate can be separated by means such as distillation or membrane separation using the boiling point or change in molecular size caused by the clathrate. In the case of crystallization, metacyclophane (1) can be separated as a solid clathrate compound by solid-liquid separation, leaving unclathrated impurity components on the mother liquor side. Among these, it is preferable to separate the mother liquor and the clathrate compound by solid-liquid separation because the operation is simple and the purification effect is large, and this is also the main feature of the present invention. Thus, according to the present invention, metacyclophane (1) can be easily separated with high purity from a metacyclophane (1)-containing mixture that is difficult to separate by distillation or the like.

In the present invention, various methods are applied to obtain the clathrate compound of the metacyclophane of the general formula (1) and the compound ().

For example, the compound (f) may be added to a mixture containing metacyclophane (1), or a mixture obtained by adding the compound () as described above to complete inclusion. It can also be obtained by heating to form a completely dissolved solution, cooling this and separating the resulting crystals.

Metacyclophane (1) can be easily obtained by any method.
A clathrate compound in which the compound () is included can be obtained. The charging ratio of the organic compound () and the mixture containing metacyclophane (1) is preferably a ratio at which at least a part of the metacyclophane () can form an clathrate compound, or higher; In particular, for the purpose of obtaining extremely high purity metacyclophane (1), a ratio such that metacyclophane (1) remains to some extent may be used.

- Generally, in cases where the clathrate compound crystallizes, it is preferable for operation to select a ratio such that the slurry concentration is 5 to 50% by weight.

The above compound (
When 1) is included, it is generally carried out at a temperature in the range of -100 to 350°C, preferably -20 to 200°C, particularly 20 to 150°C.

Further, the pressure may be higher than the pressure at which the organic compound () can exist in a liquid state at that temperature. In order to separate the clathrate thus formed from the mixture containing it, it is usually preferable to use solid-liquid separation (e.g. filtration, centrifugation, sedimentation, etc.) or to remove the solvent component by distillation. I can do it. In either method, the operating temperature is preferably in the range of -50 DEG to 120 DEG C., preferably 0 to 9 DEG C., and the operating pressure may be elevated pressure, normal pressure or reduced pressure. By removing the clathrated compound from the thus obtained clathrate compound of metacyclophane (1) and the compound, purified methacyclophane (1) can be obtained.

When removing the compound, various methods are adopted, but for example, the clathrate compound is heated to 90 to 350°C, preferably 1
A method is advantageously applied in which the compounds are separated by heating to a temperature in the range from 20 to 280°C. The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1-a) Dehydrated tetrahydrofuran (hereinafter referred to as THF)
), 10 parts by weight of sodium metal, and 1 part by weight of tetraphenylethylene were charged into a flask to form a tetraphenylethylene-sodium adduct, cooled to about -30°C, and added with bis-( A solution consisting of 10 parts by weight of (m-phenethyl)-m-chloromethylbenzene and 5 parts by weight of dehydrated THF is added dropwise substantially quantitatively over about 3 hours.

After continuing stirring for another 1 hour, the temperature was returned to room temperature, and THF5O
Add parts by volume dropwise. Unreacted metallic sodium and insoluble matter are separated in a furnace, the solvent is distilled off from the sap, and a semi-solid product 11.
4 parts by weight were obtained. Gas chromatography analysis revealed that this product contained 2.9 parts by weight of metacyclophane (1).

The semi-solid metacyclophane (1)-containing mixture thus obtained was subjected to a pot still type molecular distillation apparatus.
Pressure 0.003mmHf! a. Crude metacyclophane (1) purified by distillation at a still temperature of 330°C and having a purity of 78% by weight.
3.5 parts by weight were obtained. (1-b) Next, 13 parts by weight of p-xylene was added to 3.2 parts by weight of the crude metacyclophane (1).
After adding parts by weight and heating to 140°C to make a uniform liquid,
The mixture was cooled to room temperature, and white crystals were precipitated. The white crystals were suction-filtered at room temperature, washed with a small amount of p-xylene, and then vacuum-dried at 30 mmH9 and 40°C for 1 hour. Metacyclophane (1) in this state contains p-xylene, so the additional 0.3 mmHf! p-xylene was removed by vacuum drying at 180° C. for about 30 minutes to obtain 2.7 parts of 97% metacyclophane (1). The recovery rate of metacyclophane (1) in this operation (distillation and crystallization separation) was 90%. Example 2 Semi-solid material 11 obtained by the same operation as Example 1.
4 parts (including 2.9 parts of metacyclophane (1)) contains p-
Add 13 parts of xylene, heat to 140°C, and slowly cool to room temperature.

A small amount of crystals precipitated at this time was filtered out at room temperature, and a small amount of p.
- After washing with xylene, p-xylene was removed by the same vacuum drying operation as in Example 1, and metacyclophane (1
) 1.5 parts were obtained. The purity of this metacyclophane (1) was 75%. Examples 3 to 8 The same operation as in Example 1 was performed using the following solvent instead of p-xylene, and the following results were obtained.

Comparative Example 1 Purity of 78% was obtained by the same operation as in Example 1 (1-a).
Metacyclophane (1) was obtained.

Claims (1)

[Claims] 1 A mixture containing metacyclophane represented by the following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...... (I) and the following formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. There are tables, etc.▼……(II)
[However, in the formula, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ represents a cyclohexane ring or a benzene ring, and X is -H,
-CH_3, -C_2H_5, -COOCH_3, or represents a halogen atom, and Y is -H, -CH_3, -C
_2H_5 or represents a halogen atom. ] and at least one compound (III) selected from the group consisting of tetrahydrofuran, the compound and the above metacyclophane (
Separation of metacyclophane (I) characterized by forming an clathrate with I), then separating the clathrate, and separating the metacyclophane (I) from the clathrate. Law. 2. The separation method according to claim 1, wherein the compound (III) is at least one selected from the group consisting of P-xylene, P-diethylbenzene, toluene, benzene, cyclohexane, methyl benzoate, and tetrahydrofuran.