JPS601284B2 - Inclusion compounds and their production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides metacyclophane represented by the following formula (1) with the following formula (0) [wherein -R, is 1 or -CH3, and -R2 is -R
When , is one day, it is -OH or =○, and one R, is -C
When H3, it is -CH3.

This is an inclusion compound containing a cyclohexane derivative represented by the following formula, and a method for producing the same. The cis or trans isomer of dimethylcyclohexanes is important as a synthetic reagent, and is synthesized by catalytic reduction of xylenes.

At that time, they are obtained as a mixture of cis-trans and the difference in their boiling points is extremely small, so it is difficult to separate them even with normal laboratory precision distillation. Chim., 18, 6
17 (1960)] or urea or thiourea (US Pat. No. 2,813,851), but these separation methods have many drawbacks for industrial use. On the other hand, cyclohexanone is synthesized by catalytic reduction of phenol, and is an important synthetic intermediate for the synthesis of cyclohexanone, which is an important raw material for 6-caprolactam, by air oxidation. However, a mixture of phenol and cyclohexanol forms a co-coagulant composition, and their separation requires complicated distillation operations. In the present invention, the metacyclophane represented by formula (1) forms an inclusion compound with a cis-trans mixture of 1,3-dimethylcyclohexane or a cis-trans mixture of 1,4-dimethylcyclohexane, and It is possible to selectively separate the cis form of 1,3-dimethylcyclohexane or the trans form of 1,4-dimethylcyclohexane from each cis-trans mixture due to the difference in enveloping power between the cis form and the trans form; Furthermore, it was discovered that cyclohexanol and cyclohexanone form a clathrate compound with metacyclophane represented by formula (1), and the present invention was achieved.

That is, the present invention provides a metacyclophane represented by the following formula, wherein one R is one day or -CH3, one R2 is -R, and when one day is -OH, or = 0, and when one R, is one CH3, it is one CH3.

] It is a compound containing a cyclohexane derivative represented by the following formula, and a metacyclophane represented by the following formula, and the following formula , one R, is one day, -OH or =○
and when -R, is -CH3, it is -CH3.

This is a method for producing an enveloping compound in which the cyclohexane derivative is incorporated into the tacyclophane, the method comprising contacting the cyclohexane derivative represented by the following formula. In the present invention, it has not been previously known that the cyclohexane derivative is included in the metacyclophane to form an encapsulated acid compound, and based on this phenomenon, the cyclohexane derivative is extracted from the cyclohexane derivative-containing mixture. can be separated with high selectivity and high recovery rate, and furthermore, cis and trans isomers of 1,3- and 1,4 dimethylcyclohexane can be separated.

The present invention will be explained in detail below.

The metacyclophane of the present invention may be a cyclic compound represented by the above formula (1), and it can be obtained by various production methods.

For example, the manufacturing methods include {a} Helvetica, Chimica, A
cta) 5 Ikarigaya F2Sc to uluS7 (1967) No
．． 204{b'Symthesis 4
24 (1974) etc.

In the present invention, various methods can be applied to obtain the inclusion compound of the ura÷<rophane of the general formula (·) and the cyclohexane derivative.

For example, the metacyclophane may be added to the mixture containing the cyclohexane derivative, or the mixture obtained by adding metacyclophane as described above may be overflowed to completely complete the inclusion. It can also be obtained by preparing a solution dissolved in water, cooling the solution, and separating the resulting crystals.

By either method, it is possible to easily obtain a clathrate compound in which the cyclohexane derivative is included in metacyclophane, and the encapsulated component/metacyclophane ratio is 0.2 to 2.
0 (mol/mol). The amount of metacyclophane of formula (1) used is 0.001 per mole of the cyclohexane derivative in the cyclohexane derivative-containing mixture.
~100 mol, preferably 0.01 to 50 mol, especially 0
．． A proportion of 0.05 to 20 mol is advantageous. When the cyclohexane derivative is included in metacyclophane as described above, it is generally carried out at a temperature in the range of -50 qo to 350 qo, preferably 0°C to 20 pm, particularly 20 pm to 15,000 pm.

In order to separate the encapsulated compound thus formed from the mixture containing it, it is usually preferable to use solid-liquid separation (for example, filtration, deep D separation, sedimentation, etc.) or to remove the solvent component by evaporation by distillation. Available. In either method, the operating temperature is preferably in the range of -5000 to 120°C, preferably 0°C to 90°C. The "mixture containing the cyclohexane derivative" used to separate the cyclohexane derivative using the encapsulation compound in the present invention may be any mixture containing the cyclohexane derivative, and may be any mixture containing the cyclohexane derivative as a component other than the cyclohexane derivative. Any cyclohexane derivative may be used as long as it does not inhibit hair growth or easily desorb the cyclohexane derivative from the generated hair follicle compound, and in particular, one that does not easily dissolve the hair follicle compound is preferred. The content of the cyclohexane derivative in the mixture containing the transferor may be within a wide range since a clathrate compound can be obtained even when the content of the cyclohexane derivative is extremely low. ) is obtained, and when the cyclohexane derivative is 1,3-dimethylcyclohexane or 1,4-dimethylcyclohexane, an inclusion compound is obtained in which the cyclohexane derivative is included in the cyclohexane derivative. There is a considerable difference in the enclosing force, and this phenomenon can be used to separate cis-trans.
That is, as will be described later, in the case of 1,3-dimethylcyclohexane, the cis isomer is included about 1.3 times more than the trans isomer, and conversely, in the case of 1,4-dimethylcyclohexane, the trans isomer is included about 1.3 times more than the trans isomer. There are about 3.2 times as many inclusions. In addition, the cladding compound of metacyclophane and the cyclohexaso derivative allows the cyclohexane derivative to be easily desorbed by various methods, making it possible to obtain a highly pure cyclohexane derivative. In the present invention, when separating the cyclohexane derivative from the encapsulated compound of metacyclophane and the cyclohexane derivative, various methods can be employed. 120-280pm
[b] A method of separating the cyclohexane derivative by heating to a temperature in the range of [b] The cyclohexane compound is heated to a temperature in the range of
A method of separating the cyclohexane derivative by bringing it into contact with a solvent such as benzene, cyclohexane, or acetone is advantageously applied.

The compound of the present invention will be described below. The separated crystals (the compound) were vacuum dried to remove deposits, and then analyzed. The results were as follows.

{1' infrared analysis; metacyclophane; 3050-2850, 1610, 1590, 1490,
1445, 1080, 890, 790, 700 [Arc-1
] Cyclohexanol; 3300, 2920-2840
, 1450, 1070, 970 [earth-] Metacyclophane cyclohexanol compound: 3050-2850, 1605, 1590, 1485,
1450, 1080, 1070, 965, 890, 79
0,700 [Skin-1] 1,4-dimethylcyclohexane; 2940-2840, 1460, 1450, 1380 [
Arc-1] Metacyclophane-1,4-dimethylcyclohexane encapsulated acid compound: 3050-2850, i605,1
590, 1485, 1450, 1080, 890, 79
0,700 [Skin-1] 1,3 dimethylcyclohexane;
2920-2840, 1460, 1450, 1380 [
佽-1] Metacyclophane-1,3-dimethylcyclohexane compound: 3050-2850,1605,1
590, 1485, 1450, 1080, 890, 79
0,700 [Hin-1] 1,2-dimethylcyclohexane; 2940-2850,1450,1380 [Ka-1]
Metacyclophane-1,2 dimethylcyclohexane; 3
050-2850, 1605, 1590, 1485, 1
450,1080,890,790,700 [Ka-1]
Cyclohexanone; 2920, 2850, 1710, 1
450, 1425, 1350, 1340, 1225, 1
120 [Skin-1] Metacyclophane-cyclohexanone compound; 3050-2850, 1710, 1600
,1585,1480,1445,1220,1120
,1080,890,790,? 00 [Hadaichi 1] (2)
Gas chromatographic analysis: As a result of analyzing each post-encapsulation compound by gas chromatography (silicone OV-1, 3%, Amechrome Q carrier, 2h column), peaks of the corresponding cyclohexane derivatives were confirmed.

(i) As a result of gas chromatograph analysis of 1,4-dimethylcyclohexane cladding compound, the selected octopus was 8 grade = 3-2.
It was 0.

At this time, in the above gas chromatograph, the trans-isomer peak is at 5.0 minutes, and the cis-isomer peak is at 6.0 minutes.
The trans isomer appears at 6=0.91 and 6=1.40p in nuclear magnetic resonance spectroscopy.
It has a signal at pm, and this chemical shift is reported in the literature (J. Chem. Ph$., 37, 1167 (1
962)).

(ii) Gask of 1,3-dimethylcyclohexane inclusion compound.

As a result of the matograph analysis, the selectivity was 8 = o-69. At this time, in the above gas chromatograph, the peak of the trans isomer appears at 5.8 minutes, and the trans isomer appears at 6=0.84,6 in the nuclear magnetic resonance spectrum measurement.
= 1.6,6:1.8ppm, and this chemical shift is based on the literature (J.Chem.Ph$
．． , 37, 1167 (1962)).

{3} Differential thermal analysis: As a result of differential thermal analysis, the clathrate compounds of the cyclohexane conductor exhibited endotherms in the following temperature ranges.

Further, even if the mixture of the cyclohexane derivative contains one or more components other than the cyclohexane conductor in any proportion, the inclusion compound of the present invention can be obtained; This shows that the cyclohexane derivative can be selectively included and separated from the cyclohexane derivative-containing mixture by using a fan.

The present invention will be described in detail below with reference to Examples. Further, the selectivity (81'2) in the example is a value calculated based on the following formula.

[However, C, / represents the molar ratio of the C2 component 12.

[Example 1] Metacyclophane-cyclohexanol encapsulated compound A mixture of 2.5 parts of cyclohexanol and 0.08 parts of metacyclophane was heated at 100 qC for 5 minutes and then cooled to precipitate white needle crystals.

The crystals were heated in a furnace, washed with 3 parts of inpropyl alcohol, and thoroughly dried under reduced pressure to obtain 0.06 parts of white crystals. (mp. 136-145) Infrared analysis of this clathrate compound was as described above. Example 2 Metacyclophane-1,4-dimethylcyclohexane clathrate compound A mixture of 2.5 parts of 1,4-dimethylcyclohexane and 0.08 parts of metacyclophane was subjected to the same operation as in Example 1 to obtain 0 white crystals. .065 parts were obtained.

(mp124-130q0) The results of infrared analysis were as described above. Example 3 Metacyclophane-1,3-dimethylcyclohexane inclusion compound A mixture of 2.5 parts of 1,3-dimethylcyclohexane and 0.08 parts of metacyclophane was subjected to the same operation as in Example 1 to obtain 0 white crystals. .06 copies were obtained.

(mpl18-1240G) The results of infrared analysis were as described above. Example 4 Metacyclophane-1,2-dimethylcyclohexane encapsulation compound A mixture of 2.5 parts of 1,2-dimethylcyclohexane and 0.08 parts of metacyclophane was subjected to the same operation as in Example 1 to obtain 0 white crystals. I got .06.

(mpl 18-12 Crab○) The results of infrared spectroscopy were as described above. Example 5 Metacyclophane-cyclohexanone encapsulated compound A mixture of 2.5 parts of cyclohexanone and 0.08 parts of metacyclophane was subjected to the same operation as in Example 1 to obtain 0.05 part of white crystals.

(mp126-129qo) The results of red KBr-external spectroscopy were as described above.

○=○-1710 Skin-I Example 6 Separation of 1,4-dimethylcyclohexane by distillation from 1,4-dimethylcyclohexane compound 1,4-
When 8.5 parts of a dimethylcyclohexane clathrate compound was heated and melted and distilled under normal pressure, a component that evaporated at 1190 to 123°C was obtained.

Claims (1)

[Claims] 1 Metacyclophane represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, -R_1 in the formula is -H or - CH_3 and -
R_2 is -OH or =O when -R_1 is -H, and -CH_3 when -R_1 is -CH_3. ] A clathrate compound containing a cyclohexane derivative represented by 2 Metacyclophane represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 in the formula is -H or -CH_3, and R_
2 is -OH or =O when R_1 is -H, and R_
When 1 is -CH_3, it is -CH_3. A method for producing an clathrate compound in which the above metacyclophane is clathrated with the above cyclohexane derivative, the method comprising bringing the above metacyclophane into contact with the above cyclohexane derivative.