JPH0399084A - Separating agent for organic compound - Google Patents

Abstract

PURPOSE:To obtain the subject separating agent composed of a metal complex of a malonamide derivative capable of readily separating a specific organic compound in high selectivity by bringing the aforementioned separating agent into contact with a mixture solution, etc., of the above-mentioned organic compound so as to react therewith, selectively including the aforementioned organic compound and forming a clathrate composition. CONSTITUTION:A malonamide derivative is reacted with a halide of metal ions, such as Cu<2+> or Ni<2+>, and an acetate at (1:1) ratio preferably in a solvent, such as ethanol, at 0-100 deg.C (preferably 20-80 deg.C). The solvent is then distilled away and extraction is subsequently carried out with chloroform, etc. The resultant extract is then purified by a recrystallization method to afford the objective separating agent expressed by the formula (R<1> and R<2> are H, alkyl, aralkyl or aryl; M<2+> is bivalent heavy metal ion, such as Cu<2+>, Ni<2+> or Co<2+>). Furthermore, the aforementioned separating agent in an amount of 10<-4> to 100mol based on 1mol component to be included is reacted with benzene, toluene, xylene, etc., alone or a mixture thereof at -50 to +120 deg.C to provide a clathrate composition, which is subsequently brought into contact with a solvent, such as chloroform, to separate the above-mentioned organic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to clathrate compounds that selectively separate organic compounds from organic liquids containing benzene, toluene, xylene, etc.

[Prior Art] For example, the boiling point of benzene is 80 to 81° C., which is approximately the same as that of cyclohexane and also close to the boiling point of ethanol, and it is extremely difficult to separate benzene from a mixture of these by distillation. Also, o −, m −,
Separation of p-xylene from structural isomers by distillation is also not easy.

As shown in the above examples, in the prior art, it has been difficult to selectively separate a specific compound from an azeotropic mixture, a near-boiling point mixture, or a mixture containing structural isomers.

[Objective] The object of the present invention is to provide a new method for selectively separating benzene, toluene, xylene, and other organic compounds from single or mixed organic liquids.

[Structure] As a result of extensive research to achieve the above object, the present inventors have discovered that a metal complex of a malonamide derivative reacts with several organic compounds in a highly selective manner to form an inclusion composition. By discovering this and using this principle, it is not only possible to separate and purify organic compounds themselves, but also to
It was discovered that the metal complex of the malonamide derivative can be repeatedly used, and the present invention was completed.

That is, according to the present invention, organic liquids such as benzene, toluene, xylene, etc. alone or in combination with the general formula (where Rl, R
! is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group y1 2+. is C u *+N i ”, C
o ”, Z n ”, P d ”, etc. are alkyl groups, and represent divalent heavy metal ions).
A method for separating benzene, toluene, xylene, etc. is provided, which is characterized by including the organic compound in the metal complex of the malonamide derivative.

It has not been previously known that organic compounds such as benzene, toluene, and xylene are clathrated into metal complexes of the malonamide derivatives to form clathrate complexes, and the present invention utilizes this phenomenon. , benzene, toluene, xylene, etc. alone or in a mixed liquid to isolate and separate these clathrate compositions.

The present invention will be explained in detail below.

Malonamides having various substituents as R1 and R2 were produced according to the method for producing diptyl N,N'-bis(8-quinolyl)malonamide, which is already patent pending (Japanese Patent Application No. 63-25043).

The metal complex of the malonamide derivative of the present invention has the general formula (
It is a 1:1 complex of a malonamide derivative represented by 1) and a divalent heavy metal ion, and can be obtained by various production methods. Most commonly, it can be easily obtained in high yield by reacting a malonamide derivative with a halide or acetate of a metal ion.

When carrying out this reaction, the reaction temperature is 0°C to 100°C, preferably 20 to 80°C, and the reaction medium may be a solvent that dissolves even a small amount of the above malonamide derivative and metal salt and is inert to them. Any solvent can be used;
Examples of such substances include ethanol, methanol,
Examples include chloroform, dioxane, tetrahydrofuran, dimethylformamide, and alcohols such as ethanol are particularly preferred. The obtained reaction raw material can be purified by distilling off the solvent, extracting it with chloroform or benzene, and recrystallizing it.

In the present invention, to obtain an inclusion composition of a metal complex of a malonamide derivative of the general formula (1) and an organic compound,
Various methods are applied. For example, the metal complex of the malonamide derivative may be added to the organic compound, or the mixture obtained by adding the metal complex of the malonamide derivative as described above may be heated in order to complete the clathration. It can also be obtained by preparing a completely dissolved solution, cooling the solution, and separating the resulting crystals. By either method, an inclusion composition in which an organic compound such as benzene is included in a metal complex of a malonamide derivative can be easily obtained. The molar ratio of the clathrate/malonamide derivative changes in an integer ratio depending on the metal ion and the type of substituent.

The amount of the metal complex of the malonamide derivative of the general formula (1) used is 10-4 per mole of encapsulated fraction in the organic liquid.
Advantageous proportions are from 10 to 100 mol, preferably from 10 to 10 mol.

When an organic compound such as benzene is included in a metal complex of a malonamide derivative as described above, generally -50 to
It is carried out at a temperature of 120°C, preferably in the range from 0 to 80°C. In order to separate the clathrate composition thus formed from the mixture containing it, it is usually preferable to use solid-liquid separation (for example, filtration, centrifugation, sedimentation, etc.) or to remove solution components by evaporation by distillation. Available. In either method, the operating temperature is preferably in the range of -50 to 120°C, preferably 0 to 80°C.

Examples of the clathrate organic compound in the present invention include benzene,
It is sufficient that it contains toluene, xylene, etc., and can inhibit inclusion as a component other than the clathrated organic compound, or easily remove the clathrated organic compound from the generated clathrate composition. Any material may be used as long as it does not dissolve the clathrate, and in particular, one that does not easily dissolve the inclusion complex is preferred. As a mixture containing clathrated organic compounds, the clathrated silk composition can be selectively separated from non-clathrated organic compounds such as n-hexane, cyclohexane, methylcyclohexane, and chloroform.

It is also possible to separate structural isomers by selectively including m-kylene from an organic solvent containing 0-+ m + p-xylene.

The metal complex of the malonamide derivative of the present invention has advantages such as not only its function but also the fact that it can be synthesized at a low cost and that an economical process can be freely selected. In addition, in the inclusion composition of a metal complex of a malonamide derivative and an organic compound, the clathrated organic compound can be easily desorbed by various methods, and pure and selective separation of the organic compound can be performed. can.

In the present invention, when an organic compound is separated from a clathrate composition of a metal complex of a malonamide derivative and an organic compound, the method of Kakinata is adopted. 80-250℃ at pressure, preferably 120-15
Heat to a temperature in the range of 0°C but under reduced pressure, 40-250°C
(b) A method of separating the clathrate organic compound by heating preferably to a temperature in the range of 60 to 150°C; (b) contacting the clathrate with a good solvent such as chloroform or acetone; A method of separating clathrated organic compounds is advantageously applied.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

[Example (1) Benzyl, cyclohexylmethyl, N,N'(8
-quinolyl) malonamide (R1 in general formula (1)
=benzyl, R2=cyclohexylmethyl, R8=8-
The method for producing malonamide derivatives (quinolyl) has already been disclosed in patent application 1986-2.
5043, a method for producing the above compound is shown as an example of a new compound.

80 g (50 mmol) diethyl malonate and 1.2
g (50 mmol) of NaH in THF at reflux 1,
After that, 8.9 g (50 mmol) of cyclohexylmethyl bromide was added and the mixture was refluxed overnight. Thereafter, THF is distilled off, extracted with benzene, the benzene phase is washed with water, and then dried over anhydrous magnesium sulfate. After distilling off benzene, the residue was distilled under reduced pressure at 124°C/2 mmHg to obtain 8
6% diethyl cyclohexylmethylmalonate was obtained.

4 g (25 mmol) of diethyl cyclohexylmethylmalonate was dissolved in THF, 0.6 g (25 mmol) of NaH was added, and the mixture was refluxed for 2 hours, and then 4 Jg (25 mmol) of pendyl bromide was added and refluxed overnight.

After the same post-treatment as above, the temperature was 161℃/0.
Distillation was carried out under reduced pressure at 2 mmHg to obtain hexylmethyl penzylchloride and diethyl malonate in a yield of 79%.

Benzyl, diethyl cyclohexylmethylmalonate3.
5 g (10 mmol) was added to 3 equivalents of sodium hydroxide in a mixed solvent of ethanol and water (3:1), and the mixture was refluxed overnight. After evaporating the solvent, it was dissolved in water, and concentrated hydrochloric acid was added dropwise while cooling with water to obtain a white precipitate. The white precipitate was filtered and dried under reduced pressure.
By recrystallizing with cyclohexane, 25 g (
86%) of benzyl, cyclohexylmethylmalonic acid was obtained.

Benzyl, cyclohexylmethylmalonic acid 1.5g (5
5 ml of thionyl chloride was added to the mixture (mmol) and refluxed for 3 hours. After distilling off excess thionyl chloride, the mixture was made into a 20 ml benzene solution, 1.5 g (10 mmol) of 8-aminoquinoline and Ig (10 mmol) of triethylamine were added, and the mixture was refluxed for 5 hours. After the reaction, the benzene phase is thoroughly washed with water, and the benzene phase is dried over anhydrous magnesium sulfate. After distilling off benzene under reduced pressure, the residue was subjected to column chromatography (silica gel, chloroform) to remove unreacted substances and by-products, and then recrystallized from a cyclohexane solution to give 1.7 g.
(63%) of benzyl, cyclohexylmethyl N,N'
-bis(8-quinolyl)malonamide was obtained.

Mass spectrometry calculation value 542.26789 (CsgHm4
N40J, actual value 542.2663 I R (KB
r): 33g0, 3320. 3250 (NH
), 1680 (C=O).

(B) Production of metal complex of N,N'-bis(8-quinolyl)malonamide derivative (1) Copper(II) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide dibenzyl N,N'-bis 0.54 g (1.0 mmol) of (8-quinolyl)malonamide was dissolved in 50 ml of ethanol, 0.6 g of Cu(OAC)1H20 was added, and the mixture was heated under reflux overnight. After distilling off the ethanol, chloroform is added and insoluble copper salts are filtered off, washed with water three times, and then dried over anhydrous magnesium sulfate. After chloroform was distilled off, the obtained yellow solid was recrystallized from benzene and vacuum-dried at 100°C for 5 hours to obtain 051 g (85%) of the 121 complex of the malonamide and Cu (II). . IR:
1600cm-I (C=O) Melting point>250°C.

(2) Nickel (n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide In the same manner as in the above (B) 1 (1), 3 equivalents of excess Nj
(OAc). -4H. 83 by reacting with 0
% of the malonamide and Ni(II) were obtained. IR: 1605cm-' (C=O) melting point>
250°C, "H NMR (CDCI a,pp
m): 3.50 (4H, singlet,
CH. ), 6.5 ~ 7.6 (18H, mult
iplet, aromatic ring) 8.10 (2H, doub
let, aromatic ring) 8.90 (2H, double
t, aromatic ring).

(3) i (II) complex of benzyl, cyclohexylmethyl N,N'-bis(8-quinolyl)malonamide (1
), 0.60 g (1 mmol) of the malonamide and 0.6 g of Cu (OAc) .H. O
By reacting with Cu(II), 0.51 g (80%) of the 1;1 complex of the malonamide and Cu(II) was obtained.

IR: 1610 cm” (C=0)
, melting point 230-232℃ (4) Nickel (ff) of benzyl, cyclohexylmethyl N, N'-bis(8-quinolyl)malonamide
Similarly to complex (1), 0.60 g (1 mmol) of the malonamide and 0.8 g of N i (OAc) 1
By reacting with 4H*O, 0.45g (75
%) of the malonamide and Nt(II) were obtained.

IR: 1610 cm-' (C=O) melting point 237-240°C. 'HNMR (CDC ls,p
pm): 1.0 to 1.7 (IIH, m, cy
lnhexyl) 2.22 (2 H, d, cH2) 3.23 (2H, S, CH2), 6.7~7.7 (
13H, m, aromatic ring) 8.24 (2H, d, aromatic ring), 8.97 (2H, d1 aromatic ring).

(C) Production of organic compound inclusion composition of metal complex of N,N'-bis(8-quinolyl)malonamide derivative (1) Copper(n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide 0.1 g of a 1:1 copper complex of the amide was dissolved in benzene by heating and recrystallized by standing at room temperature. Black crystals were quantitatively obtained. The amount of benzene per 1 mol of this quartz crystal is 1.
It was confirmed by thermogravimetry (TGA) and differential scanning calorimetry (DSC) that it contained 0 mol. TGA: 124-1
11% weight loss in the 45°C range. This corresponds to a 1:1 ratio of complex to benzene.

DSC: An endothermic peak was observed in the above temperature range.

The weight loss range is 40°C or more higher than the boiling point of benzene, 80°C, indicating that it is an clathrate compound.

(2) Benzene inclusion complex of nickel (n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide Ni containing benzene in the same manner as (C)-(1) above
(n) Complex (1:1) was obtained quantitatively.

Confirmation was performed by NMR in addition to the above-mentioned TGA and DSC.

TGA: 11% weight loss at 99-119°C, hence the molar ratio of complex to benzene is 1:1.

DSC: Endothermic peak in this temperature range.

NMR: Benzene-based peak at 7J6ppm.

It was confirmed from the area ratio that the complex benzene = 1 = 1.

(3) Pyridine clathrate complex of copper(n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide When recrystallized from pyridine in the same manner as in (1), a Cu(II) complex containing pyridine ( 1:1) was obtained.

Confirmed by TGA and DSC.

TGA: 149-168°C delo% weight loss, from which the molar ratio of complex and pyridine is 1:1.

DSC: Endothermic peak in this temperature range.

(4) Benzene inclusion complex of copper (U) complex of benzyl, cyclo^, xylmethyl N, N'-bis(8-quinolyl)malonamide; or, inclusion by recrystallization with benzene in the same manner as in (1) The compound was obtained.

TGA: 15% weight loss at 123-130°C, hence the complex to benzene ratio is 2:3.

DSC: Endothermic peak in this temperature range.

(5) Toluene inclusion composition of copper (n) complex of benzyl, cyclohexylmethyl N,N'-bis(8-quinolyl)malonamide By recrystallizing with benzene in the same manner as in (1),
A 2=1 clathrate of the complex and toluene was obtained.

TGA2 weight loss of 7.0% at 83-98°C, hence the molar ratio of complex to toluene is 2:1.

DSC: Endothermic peak in this temperature range.

(6) Benzyl, cyclohexymethyl N, N'bis)8
The xylene clathrate compound of the nickel(n) complex of (quinolyl) malonamide was recrystallized from o +, m +, p-xylene (1:1:1) in the same manner as in xylene clathrate composition (1). Obtained.

TGA: 14% weight loss at 99-109°C. From this, the molar ratio of the complex and xylene is 1:1.

DSC: Endothermic peak in this temperature range.

NMR: O from the area ratio of the peak of the methyl group of xylene
It was confirmed that -:m-:p1 was contained in a ratio of about 1:2:1.

(7) Inclusion complex of nickel (II) complex of benzyl and cyclohexylmethyl N,N'bis(8-quinolyl)malonamide in a mixed solvent of benzene and cyclohexane. Similarly to (1), the moles of benzene and cyclohexane are determined. Recrystallization from a mixed solvent in a ratio of 1:1 yielded a clathrate compound containing only benzene.

T.G. A: 15% weight loss at 102-115°C.

Although the temperature range is lower than in case (4), N
MR revealed that only a trace amount of cyclohexane was contained and only benzene was included.

(D) Separation of organic compounds from organic compound inclusion composition The inclusion silk composition obtained in (B)-(1) to (7) above was heated at 100°C under reduced pressure (<1 mmHg) using a vacuum pump.
By treating the mixture in a liquid nitrogen trap for 3 hours, each clathrate organic compound could be captured in a liquid nitrogen trap. Copper (TI) or nickel (U) complexes of malonamide derivatives from which each clathrate organic compound has been completely eliminated can be recovered quantitatively, and this complex can be re-incorporated by exposing it to each clathrate organic compound. It was possible to shape the objects and use them repeatedly.

[Effect] As described above, in the present invention, organic compounds such as benzene, pyridine, toluene, xylene, etc. can be separated once as a combination of malonamide derivatives and metal complexes, and then the organic compounds can be recovered. I can do it.

Claims (5)

[Claims] (1) Benzene, toluene, xylene, etc., singly or as a mixture, can be expressed by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2 are hydrogen atoms, alkyl groups, aralkyl groups, Or the aryl group M^2^+ is Cu^2^+
, Ni^2^+, Co^2^+, Zn^2^+, Pd^
Indicates divalent heavy metal ions such as 2^+. ) in contact with a metal complex of a malonamide derivative represented by
A method for producing an inclusion composition of an organic compound, which comprises including the organic compound alone or in a mixture in the metal complex of the malonamide derivative. (2) The method according to claim 1, wherein the organic compound is separated from the organic compound inclusion compound for the metal complex of the malonamide derivative. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) An inclusion composition comprising an organic compound included in a metal complex of a malonamide derivative represented by: (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) A method for producing a metal complex of a malonamide derivative represented by (5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) is a metal complex of malonamide derivative.