JPH0621017B2 - Inclusion complex of hydrazines, production method thereof and separation method using the complex - Google Patents

Description

TECHNICAL FIELD The present invention relates to a molecular inclusion complex composed of hydrazines and a specific hydroxy compound. The present invention also relates to a method for producing the molecular inclusion complex and a separation method using the inclusion complex.

(Prior Art) Conventionally, as a method for separating or recovering hydrazines from a mixture of hydrazines and another liquid, a distillation method and a method of forming an acid addition salt with a mineral acid have been conventionally adopted. .

Although the Rassich method is generally used as a method for producing hydrazine, the concentration of hydrated hydrazine obtained by this method is extremely low.

(Problems to be Solved by the Invention) In the case of forming a salt of hydrazines with a mineral acid and separating / recovering the same, in order to reuse the hydrazines, it is necessary to perform an operation such as concentration or distillation after neutralization with a basic substance. Become.

A large energy cost is required to concentrate the diluted hydrazine hydrate obtained by the Rassich method.

Furthermore, in the case of selectively recovering hydrazines from a mixture of hydrazines by distillation or the like, separation and recovery may be very difficult due to problems such as azeotropy with other components.

The present inventors have found that hydrazines and a specific hydroxy compound form a molecular inclusion complex, and that this molecular inclusion compound decomposes under certain conditions.

That is, an object of the present invention is to provide a novel molecular inclusion complex of hydrazines and a method for producing the same.

Another object of the present invention is to provide a method for separating and recovering hydrazine using this molecular inclusion complex.

Another object of the present invention is to provide a method for separating a specific hydrazine derivative from a mixture of hydrazines using this molecular inclusion complex.

Still another object of the present invention is to use this molecular inclusion complex,
It is to provide a method for separating a specific isomer from a mixture of phenol isomers or naphthol isomers.

(Means for Solving Problems) According to the present invention, as well as In the formula, R represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a phenyl group, and R ¹ has 1 to 3 carbon atoms.
Showing an alkoxy group of, a phenolic compound of, as well as In the formula, each of R ² and R ³ represents a hydrogen atom, a lower alkyl group or a lower alkyl-substituted phenyl group, or is bonded to R ² and R ³ to form a compound A dihydroxybenzene compound of formula (iii) In the formula, X represents a sulfur atom or a carbon atom, R ⁴ and R ⁵ both represent an oxygen atom when X is a sulfur atom, and each of R ⁴ and R ⁵ represents a hydrogen atom when X is a carbon atom. A lower alkyl group or a phenyl group, or R ⁴ and R ⁵ are linked to each other to form a cyclohexyl group together with X, and a hydroxy compound selected from the group consisting of (iv) naphthols And a molecular inclusion complex having hydrazines as guest molecules.

According to the present invention, there is also provided the above molecular inclusion complex wherein the hydroxy compound and the hydrazine are present in a molar ratio of substantially 1: 1, optionally substantially 2: 1.

Further according to the invention, the molecular inclusion complex is subjected to distillation,
There is provided a method for separating hydrazines, which method comprises separating hydrazines.

In one embodiment of the present invention, a mixture of hydrazines is added with phenols or naphthols capable of forming a molecular inclusion complex only with a specific hydrazine derivative to form the molecular inclusion complex, and the molecular inclusion complex is formed. A method for separating and recovering a specific hydrazine derivative from a mixture of hydrazines, which is characterized by separating a contact complex.

In another aspect of the present invention, a hydrazine compound capable of forming a molecular inclusion complex only with a specific isomer is added to an isomer mixture of phenols or an isomer mixture of naphthols to form the molecular inclusion complex. A method for separating and recovering a specific isomer from a mixture of phenol isomers or naphthol isomers, which is characterized in that the molecular inclusion complex is separated.

(Operation) When a compound incorporates another molecule to form a complex, this complex is called a molecular inclusion complex, the former molecule is called a host molecule, and the latter molecule is called a guest molecule.

1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol and other diols form a molecular inclusion complex with various low molecular weight organic compounds, and these are stereoisomers. It is known that it can be used for division,
It is not known that they form a molecular inclusion complex with hydrazines [Journal of Synthetic Organic Chemistry, Vol. 45, No. 8 (1
987) 745].

The present inventors have found that hydrazines form an inclusion complex with a compound having a certain hydroxyl group, and that this inclusion complex can be easily decomposed under specific conditions to separate and recover hydrazines. As a result of earnest research, the present invention has been completed. According to the present invention, an inclusion complex can be formed with hydrazines and a compound having a specific hydroxyl group, whereby hydrazines can be separated and recovered.

Utilizing the molecular discrimination ability of hydrazines, hydrated hydrazine or other hydrazines can be selectively separated and recovered from a mixture of hydrated hydrazine and hydrazines other than hydrated hydrazine.

Furthermore, the phenol isomers can be separated and recovered by utilizing the ability of the guest molecule to distinguish the hydrazine phenol isomers. Similarly, it can be applied to naphthol isomers.

(Preferred Embodiment of the Invention) The hydroxy compound used as the host compound in the present invention is (i) a phenolic compound represented by the above formulas (1) and (2), (ii) the above (3) and (4). A dihydroxybenzene compound, (iii) a bisphenol compound represented by the above formula (5), and (iv) a naphthol. Among these hydroxy compounds, it is the bisphenol-based compound (iii), especially bisphenol A and antigen-W; β-binaphthol, which, in this order, show wide selectivity for various hydrazines. The dihydroxybenzene compound of the formula (3) and the naphthols (iv) have the ability to form a molecular inclusion complex with hydrated hydrazine and monoalkylhydrazine. formula
The phenolic compounds (i) of (1) and (2) and the dihydroxybenzene compound of the formula (4) have a capability of forming a clathrate inclusion complex with respect to a hydrated hydrazine compound.

Hydrazines include hydrazine hydrate and the formula In the formula, each of R ⁶ and R ⁷ is a hydrogen atom or a lower alkyl group under the condition that at least one of them is a lower alkyl group. Among these hydrazines, hydrazine hydrate forms a molecular inclusion complex with all of the above-mentioned hydroxy compounds. Monoalkylhydrazine has the second narrowest selectivity for hydroxy compounds, and dialkylhydrazine (dimethylhydrazine) has the narrowest selectivity for hydroxy compounds.

A molecular inclusion complex can be obtained by selecting and combining a hydroxy compound and hydrazines, respectively.
The hydroxy compound and the hydrazine are substantially present in the molecular inclusion complex in a molar ratio of 1: 1 or 2: 1. This molecular inclusion complex is a solid substance at room temperature.

The inclusion complex of the present invention can be obtained by bringing a hydrazine and a host compound into contact with each other to cause hydrogen bonding.
In that case, the hydrazines may be a single liquid, a mixture with other liquids, or in the presence of an inorganic salt such as salt.

The formation of these inclusion complexes proceeds even at room temperature, but if necessary, they can be carried out by heating and under high temperature to promote the formation of the inclusion complex. The inclusion complex formation temperature is 0 to 70 ° C.
It is possible to employ a condition of about 0.5 to 75 hours. Type of host compound, type and concentration of hydrazine-containing liquid (1-100%)
The solubility of the host compound also changes depending on the conditions, but the formation of the inclusion complex sufficiently proceeds even when the host compound is in an undissolved state.

Hydrazines require the presence of one or two hydroxyl groups as a host compound when forming an inclusion complex. In particular, hydrated hydrazine easily forms an inclusion complex with a host compound having one hydroxyl group. By utilizing this property, it is possible to easily separate and collect only hydrated hydrazine from the mixed solution of hydrazines. Further, by utilizing the molecular discrimination ability of hydrazines, phenol isomers or naphthol isomers can be separated and recovered from their mixture (see Table 1).

After the inclusion complex is formed, the inclusion complex can be obtained by solid-liquid separation of the inclusion complex by cooling as necessary. Operations such as solid-liquid separation trace and, if necessary, washing with water and drying may be applied.

Next, a method for separating materials using the inclusion complex of the present invention will be described.

By using the inclusion complex of the present invention, only hydrated hydrazine or other hydrazines can be selectively separated and recovered from a mixed solution of hydrazines or a mixed solution of hydrazines and another liquid. Furthermore, each isomer can be separated from the phenol isomer mixture or the naphthol isomer mixture by utilizing the molecular discrimination ability of the hydrazines at the time of forming the inclusion complex.

As the other liquid in the mixed solution, a liquid which does not form an inclusion complex with the host compound of the present invention, or an inclusion complex which can form an inclusion complex with the host compound, has an ability to form an inclusion complex as compared with hydrazines. Inferior liquids can be mentioned.

Specific examples thereof include water, methanol, and the like, and hydrazines can be selectively separated and recovered from a mixed solution thereof containing 100 to 1% of hydrazines.

In the method of separating and recovering hydrazines from the hydrazine-containing mixed liquid of the present invention, first, a host compound is brought into contact with hydrazines to form an inclusion complex.

As a contact method, a batch method can be usually adopted. In the case of the batch method, a predetermined amount of the host compound may be added to the hydrazine-mixed liquid, and heating, stirring, etc. may be performed as necessary. The amount of the host compound added is arbitrary, but it is preferable to add one or more molecules of the host compound in excess with respect to one molecule of the hydrazine. The temperature at this time is preferably about 0 to 70 ° C., and the time is preferably about 0.5 to 50 hours.

When the inclusion complex has a high solubility in hydrazines, it is preferable to perform the solid-liquid separation by reducing the temperature during the solid-liquid separation as much as possible to reduce the solubility. As the solid-liquid separation method, known methods such as filtration and centrifugation can be applied.

The inclusion complex recovered by solid-liquid separation or the like is then transferred to the elimination step. As a method for removing hydrazines from the inclusion complex, a distillation method is usually adopted. Distillation is generally performed under reduced pressure at a temperature of 80 to 170 ° C. under reduced pressure of 100 mmHg or less. By removing the hydrazines in this way, the obtained host compound can be reused and can be utilized again for forming an inclusion complex.

In the same manner as in the above operation, an appropriate host compound, for example, p-cresol, is added to the hydrazine mixed solution to selectively form an inclusion complex with hydrated hydrazine only, and the hydrated hydrazine is selectively selected from the mixed solution. Only can be separated. Further, it is possible to separate a mixture of phenol isomers by selectively forming an inclusion complex with only one phenol isomer by utilizing the molecular discrimination ability of hydrazines. When the separation is insufficient in one operation, the initial purpose can be achieved by repeating the operation of adding the host compound in which the hydrazines are recovered from the inclusion complex to the mixture to form the inclusion complex and separating and recovering it. . This method is also applicable to naphthol isomer mixtures.

(Effects of the Invention) According to the present invention, by allowing a specific hydroxy compound to act on hydrazines, it is possible to form a room temperature solid molecular inclusion complex having a hydroxy compound as a host compound and a hydrazine as a guest compound. It was By distilling the separated molecular inclusion complex, it is possible to separate into a hydrazine and a hydroxy compound. Further, by utilizing the molecular discrimination ability of hydrazines, a specific hydrazine derivative can be separated from a mixture of hydrazines, and a specific isomer can be separated from a mixture of phenol isomers or a mixture of naphthols.

(Example) Example 1 293.6 g (3.0 mol) of 47% monomethylhydrazine aqueous solution
228.3 g (1 mol) of bisphenol A was added to
It was left for 0 hours. 178.3 g of white crystals having a melting point of 60 ° C. were obtained. The presence of hydrogen-bonding -OH absorption was confirmed by IR to confirm the formation of an inclusion complex. From NMR, it was confirmed that the molecular ratio of the inclusion complex was 1: 1.

_{NMR (DMSO-d 6) 1.63ppm} (s) 6H CH 3 × 2~ bisphenol A, 2.58 (s) 3H CH 3 ~ monomethyl hydrazine, 5.25 (s) 5H OH × 2~ bisphenol A + NHNH ₂
~ Monomethylhydrazine, 6.87-7.37 (m) 8H benzene ring hydrogen ~ Bisphenol A 65% yield of the encapsulation complex based on bisphenol A
Met.

Example 2 110.1 g (1.0 mol) of hydroquinone was added to 168.7 g (2.0 mol) of a 60% aqueous hydrazine solution, and the mixture was allowed to stand at room temperature for 12 hours. 142.1 g of white powder crystals having a melting point of 135 ° C. were obtained. I
The formation of the inclusion complex was confirmed by R. From NMR, it was confirmed that the molecular ratio of the inclusion complex was 1: 1.

_{NMR (DMSO-d 6) 5.91ppm} (m) 6H OH × 2~ hydroquinone + 4H～ hydrazine, yields of inclusion complex relative to the 6.77 (m) 4H benzene ring hydrogen-hydroquinone hydroquinone was quantitative.

Example 3 333.7 g (2.0 mol) of 30% aqueous hydrazine solution was added with p-
Methoxyphenol (124.1 g, 1.0 mol) was added, and the mixture was left at room temperature for 12 hours. Melting point 90-91 ° C White scale-like crystals 11
7.6 g was obtained. Formation of an inclusion complex was confirmed by IR (see FIG. 1). In the IR of the monophenol-based inclusion complex, the OH absorption of phenol is relatively broad, while the IR of the inclusion complex and the absorption in the hydrogen bond region are very sharp.
There is a characteristic absorption (see Figure 2). It was confirmed from NMR that the molecular ratio was 1: 1 (see FIG. 3).

NMR (CDCl ₃ ) 3.90 ppm (s) 3H OCH ₃ ~ p-methoxyphenol, 4.22 (s) 4H anhydrous hydrazine, 5.93 (s) 1H 2 O
H ~ p-methoxyphenol, 7.09 (s) 4H benzene ring hydrogen ~ p-methoxyphenol The yield of the inclusion complex based on p-methoxyphenol is
It was 75.3%.

Example 4 An inclusion complex with hydrazines was synthesized in the same manner as in Examples 1 to 3. Physical property data (IR, NMR, melting point) are shown in Tables 2-5.

In addition, in both IR and NMR, the absorption involved in hydrogen bond, and in the case of the inclusion complex with alkylhydrazines, the absorption of the alkyl group in NMR is also shown. Inclusion ratio (H /
G) shows the molecular ratio of host compound / guest compound.

Example 5 363.1 g (0.67 mol) of 9.25% aqueous hydrazine hydrate was added with p-
Add 125.1 g (1.01 mol) of methoxyphenol and add 60-
Stir at 65 ° C. for 3 hours. The mixture was cooled to room temperature and separated by a centrifuge to obtain 146.9 g of white scaly crystals. The concentration of 338.4 g of an aqueous solution of hydrazine hydrate after separation of the inclusion complex is 2.81%.
Met. The yield of hydrated hydrazine separated as an inclusion complex was 71.6%.

30m of the obtained inclusion complex (146.9g, without washing and drying)
The mixture was heated to 123 ° C. under reduced pressure of mHg to obtain 18.9 g of hydrazine hydrate having a concentration of 60%. Recovery rate of hydrazine hydrate is 4
It was 7.1%. It was possible to newly separate hydrated hydrazine as an inclusion complex from the 2.81% hydrated hydrazine aqueous solution after the inclusion complex was separated, using the residue after recovery.

Table 6 shows an example of separation.

Example 6 324.4 g (3.0 mol) of p-cresol, 46 g (1.0 mol) of monomethylhydrazine and 60% aqueous hydrazine solution were added.
It was added to a mixed solution of 200.2 g (2.mol) and left standing at room temperature for 20 hours. 364 g of white scaly crystals selectively forming an inclusion complex with only hydrazine hydrate was obtained. After the inclusion complex is separated and the hydrated hydrazine is recovered, the residue is added to the complex separation mother liquor to form the inclusion complex with the hydrated hydrazine remaining in the mother liquor,
Separate and collect.

By repeating this operation, monomethylhydrazine could be separated.

Example 7 p-cresol 216.3 g (2.0 mol), m-cresol 21.
100% hydrazine hydrate solution in 6 g (0.2 mol) mixture 1
50.2 g (3.0 mol) was added and the mixture was left at 0 ° C. for 30 hours. p
70 g of cresol / anhydrous hydrazine inclusion complex were obtained.
100% hydrated hydrazine is newly added to the complex separation mother liquor,
It was possible to separate m-cresol by repeating the operation of separating after forming an inclusion complex with p-cresol.

Example 8 Phenol 188.2 g (2.0 mol) and ethanol 50 g 6
The mixture was added to 166.7 g (2.0 mol) of a 0% aqueous hydrazine solution and allowed to stand at room temperature for 20 hours. 198.2 g of white scaly crystals having a melting point of 58-60 ° C. could be separated from the ethanol mixture as a phenol / anhydrous hydrazine inclusion complex. The concentration of hydrated hydrazine in the mother liquor 200.4 g after separation of the inclusion complex was 23.8.
%Met. The yield of hydrated hydrazine recovered as an inclusion complex was 52.5%.

[Brief description of drawings]

In FIG. 1, p-methoxyphenol was used as a host compound,
FIG. 2 is an infrared absorption spectrum of an inclusion complex having hydrazine as a guest compound, and FIG. 2 shows hydrazine as a guest compound, p-methoxyphenol (solid line-), phenol (dotted line ...) And p.
Fig. 3 is an infrared absorption spectrum of an inclusion complex containing phenylphenol (chain line ----) as a host compound, and Fig. 3 shows the core of an inclusion complex containing p-methoxyphenol as a host compound and hydrazine as a guest compound. FIG. 4 is a magnetic resonance spectrum (NMR), FIG. 4 shows tert-butylhydrazine as a guest compound,
It is an infrared absorption spectrum of the inclusion complex which uses bisphenol A as a host compound (solid line ---), and bisphenol A alone (dotted line ...).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 43/23 8619-4H 243/10 9160-4H (72) Inventor Thomas C. W. McHong Kong New Territories Charter (no address) The Chinese University of Hong Kong (56) Reference JP-A-61-53201 (JP, A)

Claims (7)

[Claims] 1. A formula (i) as well as In the formula, R represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a phenyl group, and R ¹ has 1 to ¹ carbon atoms.
3 represents an alkoxy group. Phenolic compounds. Formula (ii) as well as In the formula, each of R ² and R ³ represents a hydrogen atom lower alkyl group or a lower alkyl-substituted phenyl group, or R ² and R 3
Combined with ³ and formula A dihydroxybenzene compound of formula (iii) In the formula, X represents a sulfur atom or a carbon atom, R ⁴ and R ⁵ both represent an oxygen atom when X is a sulfur atom, and each of R ⁴ and R ⁵ represents a hydrogen atom when X is a carbon atom. , A lower alkyl group or a phenyl group, or R ⁴ and R ⁵ are linked to each other to form a cyclohexyl group together with X, and (iv) a naphthol compound, and a hydroxy compound selected from the group consisting of: And a molecular inclusion complex having hydrazines as guest molecules. 2. The molecular inclusion complex according to claim 1, wherein the hydrazine is hydrazine hydrate. 3. The hydrazines have the formula The molecular inclusion complex according to claim 1, wherein each of R ⁶ and R ⁷ is a hydrogen atom or a lower alkyl group under the condition that at least one of them is a lower alkyl group. 4. The method for producing a molecular inclusion complex according to claim 1, wherein the hydroxy compound is reacted with the hydrazines. 5. A method for separating hydrazines, which comprises subjecting the molecular inclusion complex according to claim 1 to distillation to separate hydrazines. 6. A mixture of hydrazines is added with phenols or naphthols capable of forming a molecular inclusion complex only with a specific hydrazine derivative to form a molecular inclusion complex according to claim 1. A method for separating and recovering a specific hydrazine derivative from a mixture of hydrazines, which comprises separating a molecular inclusion complex. 7. The molecular inclusion according to claim 1, wherein hydrazines capable of forming a molecular inclusion complex only with a specific isomer are added to an isomer mixture of phenols or an isomer mixture of naphthols. A method of separating a specific isomer from a mixture of phenol isomers or naphthol isomers, which comprises forming a complex and separating the molecular inclusion complex.