JPWO2017022063A1 - Method for cleaving azine and hydrazone bonds - Google Patents

Abstract

By hydrolyzing a ketone azine, hydrazone or Schiff base compound in the presence of carbon dioxide in a subcritical, supercritical, or liquid carbon dioxide state to form a ketone and a hydrated hydrazine or substituted hydrazine, or a carbazic acid or substituted carbazic acid, Alternatively, the present invention relates to a method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound, which is characterized by obtaining a carbonyl compound and an amino compound, or a carbamine compound or a substituted carbamic acid.

Description

  The present invention uses liquid carbon dioxide gas, supercritical carbon dioxide gas, and subcritical carbon dioxide gas to cleave azine bonds of azine compounds, hydrazone bonds of hydrazone compounds, and azomethine bonds of Schiff bases to produce by-products with low energy. The present invention relates to a production method for easily obtaining carbazic acid (hydrazinecarboxylic acid), hydrazine hydrate, substituted hydrazine, carbazic acid derivative, carbamic acid derivative, and amino compound by suppressing the formation of.

  Hydrated hydrazines remove the oxygen dissolved in boiler water and prevent boiler corrosion, resin foaming agent raw materials, polymer polymerization initiators, air bag gas generating raw materials, and many pharmaceuticals It is an important compound used in a wide range of materials such as agricultural chemical raw materials, rocket fuel, attitude control fuel for artificial satellites, production of fine metal particles for electronic materials, and etching reagents for circuit boards. Substituted hydrazine, carbamic acid derivatives and carbazic acid derivatives are important compounds as synthetic raw materials and reaction reagents for pharmaceuticals and agricultural chemicals.

[Description of existing manufacturing method]
Here, the explanation will focus on hydrated hydrazine and substituted hydrazine. As a method for producing hydrated hydrazine and substituted hydrazine, it has been developed and industrialized for some time. The technology currently used for production is an old technology developed in the past, and there is no new promising technology. Even though some minor technical improvements have been made, the basic response has not improved at all. The manufacturing methods that have been implemented in the past and the present are based on the following methods.

As a first method, there is a method called a urea method. (Non-Patent Document 1)
Urea is converted to chlorourea or substituted chlorourea with a chlorinating agent (oxidant) such as sodium hypochlorite, aminoisocyanate is generated by Hoffmann transfer, and then hydrolyzed to obtain hydrated hydrazine or substituted hydrazine. Is the method. (Scheme 1) The disadvantage of this production method is that the product hydrazine or substituted hydrazine is a highly reducing compound, so that sodium hypochlorite, which is a raw material oxidizing agent, coexists there. Immediately generated hydrazine or substituted hydrazine is decomposed. Therefore, a stabilizer such as glue should be added to the reaction system, and in the case of hydrazine hydrate, the reaction should be stopped and separated at a low concentration of 4% or less. The 4% or less hydrated hydrazine or substituted hydrazine is concentrated and separated from the by-product inorganic salt produced in large quantities, and the by-produced inorganic salt becomes waste. Furthermore, in the case of hydrated hydrazine, it must be concentrated to 60-100% of the concentration of the practical product. In the case of anhydrous hydrazine, 100% hydrazine must first be obtained. For this reason, a large amount of energy is consumed. There is a method of concentrating hydrated hydrazine or substituted hydrazine as an inorganic acid salt, but in order to obtain the necessary hydrated hydrazine or substituted hydrazine, there is also a method of stabilizing the produced hydrazine as an inorganic salt. The salt must be neutralized and converted to hydrated or substituted hydrazine. At this time, a large amount of inorganic salt waste is generated.

[Reaction Formula 1]

  As a second method, ammonia or a substituted amine called Raschig method is used to produce chloramine with a chlorinating agent (oxidant) such as sodium hypochlorite, and this chloramine is reacted with ammonia or an amine derivative at a low temperature to produce water. There are methods for obtaining hydrazine or substituted hydrazine. (Reaction Formula 2) Since the hydrazine or substituted hydrazine produced in this reaction is a very strong reducing agent, the hydrazine produced by reacting with the chlorinating agent (sodium hypochlorite) of the oxidizing agent or Decomposes substituted hydrazine. In order to avoid this, even in the present production method, even when glue or the like is added and stabilized, the reaction is stopped at a low concentration of 4% or less of the hydrated hydrazine or substituted hydrazine, and the by-product inorganic salt and In the case of separation of hydrazine and hydrated hydrazine, it is necessary to concentrate to the commonly used 60-100% hydrated hydrazine or substituted hydrazine. In order to obtain anhydrous hydrazine, first, 100% hydrazine must be obtained. At this time, a large amount of energy is consumed and a large amount of by-product salt is generated, causing pollution. There is a method of stabilizing the produced hydrazine as an inorganic salt, but the inorganic salt must be neutralized and converted to hydrated hydrazine or substituted hydrazine. At this time, a large amount of inorganic salt waste is generated. (Non-Patent Document 2)

[Reaction Formula 2]

In the first urea method and the second Raschig method, the hydrated hydrazine or substituted hydrazine to be produced is decomposed by a chlorinating agent (sodium hypochlorite) that is a raw material oxidizing agent. The following method has been developed which has been stopped and improved with the disadvantage that only low concentrations of hydrazine or substituted hydrazine are obtained.

  The third method is a manufacturing method called organic method or ketazine method. During the reaction of Raschig method, in the presence of a large excess of ammonia water or amine derivative and a large excess of acetone, an oxidizing agent such as sodium hypochlorite is used at low temperature. A small amount of chlorinating agent is added dropwise with vigorous stirring to promote the dispersion and diffusion of the sodium hypochlorite aqueous solution and promote the reaction with ammonia. The produced low-concentration hydrazine or substituted hydrazine is immediately reacted with acetone having a very high reactivity with hydrazine or substituted hydrazine to change into chemically stable acetone azine or acetone-substituted hydrazone, and a chlorinating agent ( This is a method of preventing the oxidation of the oxidizing agent), but the decomposition reaction of the oxidizing agent with sodium hypochlorite is also fast and a great effect cannot be obtained. (Scheme 3). Since only one of acetone hydrazone is protected, the other free hydrazino group is easily oxidized like hydrazine hydrate, so that it is not subject to oxidation by oxidizing agents such as sodium hypochlorite. Not. In the case of hydrazine hydrate, both ends, and in the case of substituted hydrazine, the hydrazino group does not react with acetone to become hydrazone of ketazine or substituted hydrazine, so that it cannot escape from oxidative decomposition with an oxidizing agent. (Patent Document 1)

[Reaction Formula 3]

However, the problem of a large amount of by-product salts and the strong reduction of the hydrated hydrazine or substituted hydrazine produced and the reaction rate of the chlorinated oxidant are faster before stabilization as an acetone azine or acetone substituted hydrazone. The hydrated hydrazine or substituted hydrazine produced is decomposed by the oxidant chlorine-based oxidant. Therefore, the concentration of ketazine or substituted hydrazone in the reaction system is about 5% in terms of hydrated hydrazine in the case of hydrated hydrazine as in the first and second methods. Acetone azine is water-like, and after the reaction, excess ammonia is evaporated and recovered, and then the excess acetone having a low boiling point is recovered by evaporation. Finally, acetone azine is azeotroped with water and is azeotropically separated. At the bottom of the distillation tower, an aqueous solution containing impurities with a high salt concentration remains and causes pollution. The concentration of the acetone azine obtained here is about 20% at most in terms of hydrated hydrazine. Acetone hydrazone or acetone-substituted hydrazone is insoluble in water and does not azeotrope with water. A separate method is required for the separation and purification of acetone azine. The problem of the ketazine method is that it becomes a stable azine or substituted hydrazone that is not oxidized by the oxidant chlorinating agent. However, in order to obtain the desired hydrated hydrazine or substituted hydrazine, it cannot be obtained. The ketazine, hydrazone or substituted hydrazone must be hydrolyzed to obtain a hydrated hydrazine or substituted hydrazine, but it is easy to hydrolyze using a strong acid such as sulfuric acid or hydrochloric acid. However, the products obtained can only be obtained with these salts of hydrazine hydrazine and hydrazine derivatives. In order to obtain free hydrazine or hydrazine itself, it must be neutralized. As a result, excess alkali raw materials and a large amount of by-product salts are generated. It is very difficult to carry out the hydrolysis without using stable ketazine, hydrazone, strong acid of substituted hydrazone and the like. Other ketones do not exhibit high reactivity like acetone, and therefore cannot be used because they are not effective as protecting agents for hydrazines. Unless ketoazine, hydrazone and acetone-substituted hydrazone are hydrolyzed to obtain high-concentration hydrazine and substituted hydrazine, they cannot be used for most industrial applications. In special cases, low concentration hydrazine or substituted hydrazine may be used. As a method of hydrolyzing acetone azine or acetone hydrazone without using strong acid etc., a method of hydrolysis at high temperature is considered, but it is an equilibrium reaction in which the hydrolysis reaction and the hydrolyzed compound are recombined, and their mutual reaction Since the speed is almost the same, it is very difficult to obtain the target product by high-temperature hydrolysis. In the hydrolysis of ketoazine, hydrazone and acetone-substituted hydrazone obtained by this production method, when applying the high temperature thermal hydrolysis method, high temperature thermal hydrolysis around 150-160 ° C. is required, and there is a very small difference in equilibrium constant. The efficiency of obtaining the target product little by little is very poor, and it has a big problem of consuming a large amount of energy. However, there is a merit that a large amount of by-products are not generated and it does not cause pollution. This will be described in detail later.

  A method called the hydrogen peroxide method has been developed as the fourth method. (Patent Document 2) (Patent Document 3)

  The first, second, and third methods cause pollution by producing a large amount of by-product salt. In addition, the reaction must be stopped at a low concentration in order to prevent the product from being decomposed by an oxidizing agent such as sodium hypochlorite as a raw material. As a method not generating a large amount of by-product salt, a method using hydrogen peroxide as an oxidizing agent has been developed. Although the reaction mechanism is not disclosed, the reaction is completely different from the reaction mechanism of the conventional production method based on the knowledge of the chemical reaction, and the reaction mechanism can be easily estimated. However, it does not simply mean that ammonia or an amine derivative and hydrogen peroxide are mixed. In any document, neither a reaction intermediate nor a reaction mechanism is confirmed or explained. As the assumed reaction, it is assumed that a ketone and ammonia are first reacted to produce a stable ketimine (ketone imine). Ketones that produce ketimines (ketone imines) are reactive with ammonia or amine derivatives, and ketimines (ketoimines) produced by reaction with ketones are preferably stable compounds. Acetone used in the third method produces acetone imine. However, since acetone imine or acetone imine derivatives are unstable, acetone imine or acetone imine derivatives are difficult to handle, yield, Avoided from reactions and decomposition reactions. In the present technology, any ketone can be used as long as it produces a stable ketone imine, but two molecules of ketone imine are oxidized with hydrogen peroxide to form a ketone azine or a substituted hydrazone. The same problem as shown in the third method arises. Hydrolysis of ketone azine with a strong acid gives a hydrazine salt or a substituted hydrazine salt. It is desirable to obtain a hydrated hydrazine or a substituted hydrazine by using a high-temperature thermal hydrolysis method without using a by-product salt that causes pollution or using a strong acid that increases costs. A catalyst containing a highly toxic arsenic compound by reacting methylethylketone with ammonia or an amine derivative from the viewpoint of high-temperature thermal hydrolysis of ketazine and substituted hydrazone and from the viewpoint of post-treatment to obtain stable methylethylketimine (ketoneimine). In the presence of (cacodyl), it is oxidized with hydrogen peroxide to bind the NH structure of two molecules of ketimine, and NN bond is formed to form ketoazine, or ketimine and substituted amine are bound in the same reaction. Therefore, the obtained methyl ethyl ketazine or substituted hydrazone is a ketoazine or hydrazone or substituted hydrazone which is much more stable than acetone azine or acetone hydrazone derivatives. In order to obtain the desired hydrated hydrazine or substituted hydrazine, the ketone azine and substituted hydrazone obtained here must be hydrolyzed. (Reaction Formula 4)

[Reaction Formula 4]

It is more difficult than the third production method to obtain a hydrated hydrazine or a substituted hydrazine by hydrolyzing the stable ketoazine, hydrazone or substituted hydrazone at a high temperature. In the third method and the fourth method, when the produced hydrazone is subjected to a high-temperature thermal hydrolysis reaction, a large amount of the hydrazone is converted into an intramolecular reaction or a by-product in which hydrazone and ketone react during hydrolysis. The ketone used in the fourth method combines the viewpoints of imine formation, stability, reactivity, etc. and the heat hydrolyzability of the ketoazine or substituted hydrazone after the reaction, and is regenerated to the ketone by hydrolysis. From the combination, methyl ethyl ketone or the like is mainly used. Methyl ethyl ketazine or methyl ethyl hydrazone or methyl ethyl substituted hydrazone obtained from this has the advantage that it can be easily separated from the aqueous layer because it is insoluble in water, and there is an advantage that waste of inorganic salts such as salt does not occur. A catalyst using highly toxic arsenic is required and high-temperature thermal hydrolysis at around 190 ° C is required. In this method, as in the third method, the reaction in high-temperature thermal decomposition is an equilibrium. It is a reaction, and hydrated hydrazine and substituted hydrazine are obtained in very small amounts by utilizing a slight difference in equilibrium constant. For this reason, it becomes more difficult due to waste of a large amount of energy, generation of by-products during high-temperature heating, and coloring problems on the product. Furthermore, when a ketone having a large number of carbon atoms is used, high-temperature thermal hydrolysis of ketazine is almost impossible. The hydrolysis reaction will be described in detail in the following items.

[Description of high-temperature thermal hydrolysis of ketazine, hydrazone, or substituted hydrazone in a method for obtaining ketazine, hydrazone, or substituted hydrazone]
In the third production method (organic method, ketazine method), the reduced amount of the hydrated hydrazine or substituted hydrazine produced before being stabilized as acetone azine is very strong. Because it is easily oxidized and decomposed by a chlorinating agent such as sodium chlorate, the generated hydrazine or substituted hydrazine is converted to stable acetone azine or acetone-substituted hydrazone earlier than decomposition by the oxidizing agent, and oxidative decomposition It is a method not to receive. Since acetone hydrazone is in a state where one hydrazino group is liberated, it is easily oxidized by the raw material oxidizing agent and cannot become a stabilizing substance. On the other hand, in the low concentration state of hydrated hydrazine or substituted hydrazine, the object is achieved. However, as the concentration of acetone azine, acetone hydrazone or acetone substituted hydrazone increases, basically the hydrazine or substituted hydrazine produced later Since hydrazine has a fast reaction rate with a chlorine-based oxidant such as sodium hypochlorite, the decomposition reaction with this oxidant has priority. Therefore, it is necessary to stop the reaction at a low concentration even in the acetone azine or acetone-substituted hydrazone method. The final product required is a highly concentrated hydrazine or substituted hydrazine product in most cases except for special applications. Therefore, hydrolyzed ketoazine compound or substituted hydrazone and concentrated to a highly concentrated hydrazine or substituted hydrazine product. Must be substituted hydrazine and ketone.

  In the fourth production method (hydrogen peroxide method), from the presumed reaction mechanism, methyl ethyl ketone is reacted with ammonia or a substituted amine to first produce methyl ethyl ketimine, and the methyl ethyl ketimine is reacted in the presence of an arsenic catalyst. It is thought that it is oxidized with hydrogen oxide to form an NN bond and is first converted to methyl ethyl ketoazine or methyl ethyl substituted hydrazone. Since hydrogenated hydrazine or substituted hydrazine is not generated at the beginning of the reaction, there is no problem that hydrogenated hydrazine or substituted hydrazine is decomposed by an oxidizing agent of hydrogen peroxide. Although the concentration as methyl ethyl ketoazine or methyl ethyl substituted hydrazone can be increased, these compounds are extremely stable compounds. The final target product is a high-concentration product of hydrated hydrazine or substituted hydrazine, so that methyl ethyl ketazine or methyl ethyl substituted hydrazone compound is hydrolyzed to form hydrated hydrazine or substituted hydrazine and ketone, and methyl ethyl ketone is recovered. It is necessary to concentrate hydrazine or substituted hydrazine.

  In both the third production method and the fourth production method, hydrolysis of the ketone azine or the substituted hydrazone is indispensable because it is obtained with a stable substance of the ketone azine or the substituted hydrazone. Although it is easily hydrolyzed if a mineral acid or the like is used as a catalyst, the resulting compound becomes a mineral salt of hydrazine or substituted hydrazine, and must be neutralized again with alkali to form hydrated hydrazine or substituted hydrazine. In addition, a large amount of by-product salt is generated, causing pollution, and at the same time, an extra neutralized raw material is used, resulting in an increase in cost.

  In order to avoid this, a high-temperature thermal hydrolysis method in which a by-product salt is not generated from highly stable ketazine or substituted hydrazone is employed in actual production. However, the recombination rate constant of the ketone produced by high-temperature thermal hydrolysis and hydrated hydrazine or substituted hydrazine also increases. This is an equilibrium reaction in which there is no difference in reaction rate. Choosing optimal conditions will only yield very small amounts of hydrazine or substituted hydrazine. (Reaction Formula 5)

  Further, when the thermal hydrolysis reaction is performed at a high temperature, the hydrolysis reaction constant increases, but the reaction rate constant between the ketone and the liberated hydrazine or the substituted hydrazine increases. There is a temperature point with a slight difference in this equilibrium constant in high-temperature thermal hydrolysis, so that the amount that can be separated as hydrated hydrazine or substituted hydrazine obtained by high-temperature thermal hydrolysis is very small. The hydrazone is recycled indefinitely and subjected to thermal hydrolysis to obtain a low concentration of hydrazine or substituted hydrazone. If the hydrolysis temperature is further increased, the difference in the reaction rate constant does not increase correspondingly. For hydrolysis of acetone azine or acetone-substituted hydrazone (third production method), a temperature of about 150-160 ° C. is the minimum, and for methyl ethyl ketone azine or methyl ethyl ketone-substituted hydrazone (fourth production method), a temperature of about 180-190 ° C. Is a minimum requirement. With other ketones, the formation of ketazines or substituted hydrazones and the thermal hydrolysis of these compounds is nearly impossible. High temperature thermal hydrolysis is recycled for a long time to obtain hydrated hydrazine or substituted hydrazine, resulting in hydrazone from waste of energy and incomplete reaction during ketone azine synthesis during ketone azine synthesis, and incomplete during high temperature thermal hydrolysis. Hydrazones are formed during decomposition and recombination. When heated, hydrazone undergoes a disproportionation reaction to form ketoazine and hydrated hydrazine, but hydrazone of hydrated hydrazine and ketone is an unstable compound and is heated at this high temperature by intramolecular reaction or reaction with ketone. It produces a large amount of pyrazoline and other by-products in the history. The ketone itself also forms a condensate with a long history at high temperatures. In addition, these by-products cause a decrease in product purity and coloring. The high-temperature heating hydrolysis method has problems that energy consumption is extremely large and the economy is poor, and that only low-quality products having impurities and coloring can be obtained. The hydrazine concentration obtained by high-temperature thermal hydrolysis in the ketazine method, the by-product salts, the separation method, the concentration method, and the like are as described in the section. Both methods require distillation purification and re-rectification as necessary.

[Reaction Formula 5]

K1 and K2 indicate deviation constants.

Ger.P.1,082,889 (June 9,1960) FR.P. 2260569 (November, 5, 1975) US.P.4093656 (June.6.1978)

J. Fischer, J. Jander, Z. Anorg. Allgem. Chem., 313, 14 (1961) J.E.Troyan, Ind.Eng.Chem., 45, 2608 (1953) Hiroshi Hayashi, Journal of Synthetic Organic Chemistry, 33, 451 (1975) Japan Industrial and Medical Gas Association "Liquid CO2 Handling Text" (September 2015, p. 54)

  In the present invention, hydrolysis of ketazine (ketone azine) or hydrazone, substituted hydrazone or Schiff base compound does not use a catalyst such as a mineral acid, so there is no generation of by-products or waste, low energy consumption, and room temperature. It is an object of the present invention to provide a production method for economically producing hydrazine or substituted hydrazine having a high purity, a high concentration, and an arbitrary concentration by performing a high yield and high efficiency method at a low temperature such as. In addition, compounds having a carbonyl group such as ketones and aldeides used as raw materials can be widely used. The carbon dioxide used can be recycled and recycled. Further, in the conventional method, the ketoazine compound or keto-substituted hydrazone compound is hydrolyzed without using a catalyst such as a mineral acid to produce a hydrated hydrazine or a substituted hydrazine. Possible ketone compounds are limited to acetone or methyl ethyl ketone. If a by-product salt may be produced in a large amount, it can be hydrolyzed using a mineral acid to obtain a mineral salt of hydrazine and neutralized again to obtain a hydrated hydrazine or a substituted hydrazine. However, it has decisive drawbacks such as poor economic efficiency and a large amount of by-product salt that causes pollution. Instead, a wide range of carbonyl compounds can be used, but it is difficult to use as a substantial production method.

  Since the method of the present invention has a completely different hydrolysis mechanism, a wide range of carbonyl compounds can be used.

  In order to solve the above-mentioned problems, the present inventor has eagerly studied the discovery of a compound expected to have a catalytic effect in hydrolysis of ketone azine, hydrazone, substituted hydrazone or Schiff base compound and the method of using the compound. When the acidity is such that the carbonated water or the carbon dioxide gas is dissolved by pressurization, only a low conversion rate, low concentration of hydrazine or substituted hydrazine is obtained even if this hydrolysis reaction is carried out. Increasing the temperature of the hydrolysis reaction promotes the reaction slightly, but also promotes side reactions. The object of the present invention is not satisfied. Carbonic acid is considered as an acid that does not produce a strong salt with hydrazine hydrate or substituted hydrazine and does not produce a salt that must be separated and discarded, but the pH of carbonated water at normal temperature and pressure Is 6.35, and when the solubility is increased by pressurization, the pH also decreases, but the limit is about PH = 2.9. At this degree of acidity, there is very little hydrolysis of azine or hydrazone or substituted hydrazone. Even if the temperature is increased under pressure to increase the reactivity, only the amount of side reaction products increases, and the production of the target hydrated hydrazine or substituted hydrazine does not increase so much. As will be described in detail later, the carbon dioxide gas becomes a carbon dioxide state, a subcritical region, a supercritical state, and a liquid carbon dioxide state by combining pressure and temperature. Surprisingly, azine, hydrazone, substituted hydrazone, or Schiff base can be produced without subtle and supercritical carbon dioxide gas under the lowest pressure condition and liquid carbon dioxide gas condition in the phase diagram without causing any impurities in the presence of water. It was discovered that the compound was hydrolyzed, and the target hydrated hydrazine, substituted hydrazine, or carbonyl compound and amino compound were produced in high yield and high efficiency in a short time.

  Hydrolyzed with subcritical, supercritical carbon dioxide and liquid carbon dioxide and added as hydrate to form hydrazine, substituted hydrazine, carbonyl compound or amino compound from ketone azine, hydrazone, substituted hydrazone or Schiff base compound By stirring and mixing a solution and a dispersion of an amount of water necessary for the hydrolysis and an amount of water greater than that required for the hydrolysis reaction under mild conditions such as 40 ° C. or less, high purity and high efficiency can be achieved. It was discovered that by adjusting the concentration and amount of water, hydrazine, carbazic acid (hydrazinecarboxylic acid), substituted hydrazine, substituted carbazic acid, carbamic acid derivatives, or carbonyl compounds and amino compounds of any concentration can be obtained. .

  Although this unexpected reaction mechanism is assumed, supercritical carbon dioxide, which is said to be an association of liquid carbon dioxide and neither a gas nor a liquid, is not a single-molecule gas body, but many molecules. It is possible to present an estimated mechanism of action by the electron relay mechanism or proton relay mechanism. In the present invention, since a mixture with water is used, the end of the associated carbon dioxide gas is considered to be a carboxylic acid. It is presumed that the proton is highly acidic due to the association mechanism. Carbadic acid or substituted carbazic acid produced by the reaction of produced hydrazine or substituted hydrazine and carbon dioxide can be easily and safely decomposed into hydrated hydrazine or substituted hydrazine and carbon dioxide by heating to 40-70 ° C. The present inventors have found that hydrazine or substituted hydrazine having an arbitrary concentration can be obtained depending on the amount of water used with high purity and high concentration as a product. If necessary, when the conditions are such that a low-concentration product is obtained, water is first distilled off in a distillation tower, and distilled in an azeotropic state with hydrated hydrazine to obtain 80% hydrated hydrazine. Only 100% hydrated hydrazine can be obtained by distilling only and concentrating and distilling. At this time, purification is performed. By confirming these facts, the present invention has been completed.

[Detailed description of means for solving the problem]
The present invention requires the ketone azine, hydrazone, substituted hydrazone or Schiff base compound represented by the following reaction formula (6) for water and hydrolysis required for subcritical carbon dioxide, supercritical carbon dioxide, liquid carbon dioxide and hydrate. After the hydrolysis reaction, subcritical carbon dioxide gas and supercritical carbon dioxide gas are mixed by stirring and mixing an amount of water that is equal to or greater than 40 ° C. or less (not limited to this temperature) It is a state having both gas and liquid properties, but is a dispersed state of clusters in which carbon dioxide gas is associated. Therefore, after the reaction, the subcritical carbon dioxide gas and supercritical carbon dioxide gas are changed to the liquid phase conditions and are combined with the liquid carbon dioxide gas to form a liquid phase. When left standing, the carbon dioxide liquid layer and the aqueous layer are separated. The concentration of carbon dioxide dissolved in water and the amount of water dissolved in liquid carbon dioxide are shown in FIG. Since supercritical carbon dioxide has the property of an organic solvent, it is used as a solvent for extracting useful organic substances from natural products. However, there are no reports that liquid carbon dioxide exhibits properties like organic solvents. Although data on phase equilibria between supercritical carbon dioxide and alcohol and organic solvents at low molar ratios can be seen, analysis of detailed results on organic reactions is a fact discovered for the first time in the present invention. In any of subcritical carbon dioxide gas, supercritical carbon dioxide gas and liquid carbon dioxide gas, the raw material ketazine (ketone azine), the ketone produced by hydrolysis, and the poorly water-soluble substituted hydrazine produced can be said to be in a liquid state microscopically. It dissolves in the critical carbon dioxide layer, supercritical carbon dioxide layer and liquid carbon dioxide layer, and the ketone dissolved in water also dissolves in these liquid carbon dioxide layers. Since hydrated hydrazine, substituted hydrazine and amino compounds, which are readily soluble in water, are dissolved in water, they are dissolved in the aqueous layer.

  As shown in document (1), the specific gravity of liquid carbon dioxide varies depending on the temperature and the pressure to be liquefied. The critical point of liquid carbon dioxide is 31.1 ° C. and 7.38 MPa. The density at each temperature and pressure of liquid carbon dioxide is as shown in the document (1). The solvent used in the present invention is subcritical carbon dioxide gas, supercritical carbon dioxide gas, liquefied carbon dioxide gas and water, and after completion of the reaction, the temperature or pressure of the subcritical carbon dioxide gas and supercritical carbon dioxide gas is adjusted to adjust the liquid carbon dioxide gas. Convert to As shown in FIG. 2, the water dissolved in the liquefied carbon dioxide gas at a low temperature and the liquefied carbon dioxide gas dissolved in the water have very low concentrations. Water and liquefied carbon dioxide that cannot dissolve each other are in a separated state. Even if the freezing point depression is caused by a substance such as ketone azine or ketone hydrazone or ketone-substituted hydrazone and hydrated hydrazine or substituted hydrazine or carbazic acid or substituted carbazic acid that dissolves in water or liquefied carbon dioxide gas, It becomes ice at low temperatures. Since the stirring sewage water layer becomes a solid, it becomes a slurry state of the water layer solidified into the liquid carbon dioxide layer. Above -10 ° C, the specific gravity of the liquid carbon dioxide gas is 1 or less, and when the method of the present invention is carried out under the preferred reaction conditions, the liquid carbon dioxide gas layer comes into the upper layer and the The layer of comes to the lower layer. When more raw materials than can be dissolved in liquefied carbon dioxide and water are used, the raw materials are dispersed in liquefied carbon dioxide and water, or form three layers of liquefied carbon dioxide, water, and raw materials. Although the freezing point is lowered by the raw material and the product, or the slurry in the water layer solidified in the liquid carbon dioxide layer may be treated, it is about −30 ° C. from the viewpoint of reactivity, thermal efficiency, post-treatment, etc. The reaction is preferably performed at a temperature of 40 ° C. or lower. More preferably, the reaction is preferably performed at a temperature of −10 ° C. or higher and 30 ° C. or lower. The pressure with respect to these temperatures depends on the volume of the pressure vessel and the filling amount (filling constant) of liquid carbon dioxide gas to be filled, and will be described in the items of FIG. The freezing point of 60% hydrazine is -70.7 ° C, and the freezing point of 100% hydrazine is -51.7 ° C. However, it is not limited to these reaction conditions.

(Non-Patent Document 4)

  It is possible to use liquid carbon dioxide in any proportion with respect to the amount of the raw material azine, hydrazone, substituted hydrazone or Schiff base compound. As the hydrolysis reaction proceeds, the raw material ketone azine, hydrazone, substituted hydrazone or Schiff base compound is hydrated hydrazine, substituted hydrazine, carbazic acid, substituted carbazic acid, carbamic acid, carbamic acid derivative, amino compound and ketone or carbonyl compound To be hydrolyzed. The produced readily water-soluble hydrazine, substituted hydrazine, carbazic acid and substituted carbazine acid are dissolved in the aqueous layer, and the ketone, poorly water-soluble substituted hydrazines and substituted carbazine acid are dissolved in liquid carbon dioxide. The Schiff base compound is decomposed into a carbonyl compound and an amino compound or a carbamic acid derivative, and similarly dissolved in a liquid carbon dioxide layer or an aqueous layer.

  Hydrolysis according to the present technology does not produce any by-products such as a reaction that returns to azine, hydrazone, or substituted hydrazone, or a condensate of ketone, which is generated by the reaction of ketone with hydrazine, hydrazone, or substituted hydrazine. After the reaction, the temperature or pressure is adjusted, and in the case of subcritical or supercritical carbon dioxide, it is converted to liquid carbon dioxide, and the liquid carbon dioxide layer and aqueous layer are separated. The compound existing as carbazic acid or substituted carbazic acid remaining by heating the aqueous layer to 30-100 ° C, preferably 40-70 ° C, is easily converted into hydrated hydrazine or substituted hydrazine and carbon dioxide. Safely disassembled. (Reaction Scheme 7) However, it is not limited to this condition. The same applies to the Schiff base compound.

  The concentration of the hydrated hydrazine or substituted hydrazine depends on the amount of water to be added, but the amount of water corresponding to the product concentration of the desired hydrated hydrazine is added during the hydrolysis reaction to bring the hydrated water close to the desired concentration. You can get hydrazine directly. Usually 60-100% hydrated hydrazine is used. Some users may also use 5-60% hydrazine, so the amount of water may be adjusted to achieve that concentration. When setting to a precise product concentration, the concentration of the obtained crude hydrated hydrazine is analyzed, and if necessary, high concentration hydrated hydrazine is added or water is added to adjust to a predetermined concentration.

  Further, when high purity hydrazine is required, the obtained high concentration hydrazine can be obtained by rectification. If rectification is performed with 100% hydrazine, products with various concentrations can be prepared by adjusting hydrazine having an arbitrary concentration according to dilution. It can also be used to adjust the concentration of crude hydrated hydrazine. When anhydrous hydrazine is required, it can be obtained by dehydrating from 100% hydrazine and distilling if necessary. Since hydrated hydrazine azeotropes with water at 80%, 80% hydrated hydrazine is obtained by fractional distillation with an azeotropic product. The amount of water used during the reaction depends on the amount of water required for hydrolysis of azine or hydrazone. If the amount is less than the amount required for 80% hydrazine, an arbitrarily high concentration of hydrazine of 80% hydrazine or higher can be obtained. Since substituted hydrazine does not form a hydrate, it is sufficient to add more water than is necessary for hydrolysis. From these, the boiling point of water is raised and only water is distilled off, and then concentrated 100% hydrazine or substituted hydrazine may be fractionally distilled. When distilling hydrated hydrazine, it must be distilled in an inert gas such as nitrogen in order to avoid decomposition of hydrated hydrazine and decomposition with oxygen in the air. Also, substituted hydrazines are more unstable and must be distilled in inert gases and additives suitable for substituted hydrazines.

[Reaction Scheme 6]

[Chemical Formula 1]
Ketone azine

In the reaction formula (6), the compound (1) represents ketazine (ketone azine), and the compound (2) represents a ketone. Compound (3) represents the same ketone as compound (2) or a different type of ketone. Compound (4) represents hydrated hydrazine (hydrazine hydrate, hydrazine hydrate). R ₁ , R ₂ , R ₃ and R ₄ in the chemical formula 1 may be the same or different, or a combination thereof, or R ₁ and R ₂ and R ₃ and R ₄ may be bonded. You may have not only carbon but hetero atoms, such as a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. It may have a substituent. Alkyl group, alkynyl group, alkenyl group, aralkyl group, alkylene group, aryl group, allyl group, condensed ring group, and these groups having a heteroatom as a substituent, and also adversely affect the formation of ketone azine or hydrazone. May have a substituent such as halogen, nitro group, OH group, thiol group. However, it is not limited to these substituents. The basic condition is to have a structure in which at least one carbonyl group bonded to R ₁ , R ₂ , R ₃ , R ₄ and hydrazine are bonded.

[Chemical formula 2]
Ketone (1)

The ketone of the conditions shown by Chemical formula (1) is shown. R ₁ and R ₂ are the same as described in chemical formula (1).

[Chemical formula 3]
Ketone (2)

The ketone of the conditions shown by Chemical formula (1) is shown. R ₃ and R ₄ are the same as those described in chemical formula (1).

[Chemical formula 4]
Hydrated hydrazine (hydrazine hydrate, hydrazine hydrate)

[Chemical formula 5]
Hydrazone

The hydrazone of the conditions shown by Chemical formula (1) is shown. R ₁ , R ₂ , R ₃ , and R ₄ are the same as those described in chemical formula (1). R5 and R6 are also the same as those described for R ₁ , R ₂ , R ₃ and R ₄ in chemical formula (1).

[Chemical formula 6]
Carbazine acid (hydrazinecarboxylic acid)

[Chemical formula 7]
Substituted hydrazine

R ₅ and R ₆ in chemical formula (7) are the same as those described in chemical formula (5).

[Reaction Scheme 7]
Hydrolysis of carbazic acid (hydrazinecarboxylic acid)

  The present invention provides a subcritical carbon dioxide gas, a supercritical carbon dioxide at a low temperature such as room temperature without using a ketone azine, hydrazone or substituted hydrazone represented by the chemical formulas (1) and (5) at a low temperature such as room temperature. Hydrolyzed in gas and liquid carbon dioxide to obtain high-purity, high-concentration or any concentration of hydrogenated hydrazine or substituted hydrazine that does not produce by-products in a substantially one-stage reaction, and a liquid carbon dioxide layer (temperature (Including subcritical and supercritical states converted by pressure) and water layers are separated by an easy and safe method, and hydrated hydrazine or substituted hydrazine is produced in an energy-saving and non-polluting method at low cost, without by-products. It is a manufacturing method. This is a method for producing a hydrated hydrazine or a substituted hydrazine that can be easily separated and recovered without causing side reactions of the ketone or aldehyde used in the liquid carbon dioxide gas or raw material, and can be recycled.

  The object of the present invention is to obtain a hydrated hydrazine or a substituted hydrazine, but it is not limited to the hydrolysis of ketone azine or hydrazone, as is apparent from the above-described presumed reaction mechanism, but a structure such as a Schiff base. This reaction can also be applied to hydrolysis of a compound having an imino bond (—C═N—) shown in FIG.

FIG. 1 shows the pH of water saturated with CO ₂ . Figure 2 shows the solubility of water solubility and CO ₂ CO ₂ for water. FIG. 3 shows a state diagram of CO ₂ . FIG. 4 shows the state of CO ₂ in the pressure vessel.

  Hereinafter, the present invention will be described in detail.

  In the present invention, a ketone azine, a hydrazone, or a substituted hydrazone is added to a mixed system of subcritical carbon dioxide gas, supercritical carbon dioxide gas, liquid carbon dioxide gas and water, and -56.6 ° C or higher and 60 ° C or lower, preferably -30 ° C. Water that hydrolyzes ketone azine, hydrazone, or substituted hydrazone and stirs and mixes at -40 ° C, more preferably -10-30 ° C, and converts it into ketone and hydrated hydrazine or substituted hydrazine with high efficiency and high concentration. This is a method for producing hydrazine or substituted hydrazine. The detailed description is as described in the section “Detailed Description of Means for Solving Problems”. When a detailed analysis of the reaction results is performed, it is considered that the reaction proceeds by the reactions shown in the reaction formulas (6) and (9). Furthermore, when reaction formula (6) is analyzed in detail, the reaction and reaction product of reaction formula (8) and reaction formula (7) are also recognized. After the hydrolysis reaction, the temperature and pressure of the subcritical carbon dioxide layer and supercritical carbon dioxide layer are adjusted, preferably all separated as a liquid carbon dioxide layer and analyzed by gas chromatography or liquid chromatography. Is confirmed. It is confirmed that the ketone remains when the liquid carbon dioxide gas is vaporized by carbonization from the liquid carbon dioxide layer. When the aqueous layer separated at low temperature is concentrated under reduced pressure or a poor solvent that dissolves in water such as methanol is added, some crystals are precipitated. When this crystal was confirmed by IR and liquid chromatography, it was identified as carbazic acid (hydrazinecarboxylic acid) or substituted carbazic acid. Carbazine acid or substituted carbazic acid is an unstable compound, and when it is subjected to a temperature of about 40 ° C. to 60 ° C., it is easily and safely decomposed into hydrated hydrazine or substituted hydrazine and carbon dioxide. When the aqueous layer of this reaction was heated, bubbles were generated, and analysis revealed that it was carbon dioxide.

[Hydrolysis in the current production process of acetone azine or acetone hydrazone]
In the current process for forming acetone azine, first all volatile substances such as ammonia, acetone, acetone azine, acetone hydrazone, hydrazine hydrate, water, etc., which are the compositions after the reaction, are distilled off at the bottom of the distillation column. The salts are concentrated and separated and removed as an aqueous solution. At the same time, ammonia is recovered from the volatile components, and then the ketones are separated. An aqueous solution containing acetone azine and acetone hydrazone enters a thermal decomposition reaction in a hydrolysis tower.

Hydrolysis in acetone azine in which R ₁ , R ₂ , R ₃ , and R ₄ are methyl groups is an acetone azine aqueous solution in the bottom can of a multistage hydrolysis tower (acetone azine and water show azeotropy. The hydrated hydrazine and water azeotrope) is heated to 130-150 ° C where the K1 in the reaction formula (1) is slightly higher than K2, firstly excess water is distilled off, and further generated by high-temperature thermal hydrolysis. Distilling off a very small amount of free acetone free from the recombination of hydrated hydrazine and acetone, recycling the acetone azine produced by unhydrolyzed and recombined by high-temperature thermal hydrolysis, and removing acetone from the top of the tower in small portions. Distill off. The produced hydrazine remains at the bottom of the tower. A large amount of steam is consumed and acetone azine is recycled over a long period of time to obtain a 20-30% aqueous hydrazine solution. By subjecting acetone azine to a high temperature for a long period of time, the production of by-products such as side reaction products such as pyrazoline and acetone condensate is increased from acetone hydrazone, one of which is hydrolyzed. Separated rectification in the presence of inert gas such as nitrogen to avoid decomposition of 20-30% low concentration hydrazine obtained in the tower bottom with oxygen in the air and to ensure safety First, water is distilled off for concentration, and then rectification is performed with an azeotrope of hydrated hydrazine and water to obtain 80% hydrated hydrazine. Still contains impurities. When high-purity and high-concentration hydrazine is required, in order to prevent oxidation and to ensure safety, water is first distilled off in the presence of additional gas such as nitrogen, and the concentration is increased and re-rectification is performed. . To obtain 100% hydrazine, in order to prevent oxidation, in the presence of an inert gas such as nitrogen, water is first distilled off from the top of the tower to obtain 100% hydrazine at the bottom of the tower. Rectification is performed to obtain 100% hydrazine hydrate from the top.

  When obtaining a substituted hydrazine, since it is an unstable compound, it cannot be obtained by the same treatment as hydrated hydrazine. Special environmental conditions for distillation of substituted hydrazines are required.

[Hydrolysis in the current production method of the hydrogen peroxide method]
In the current hydrogen peroxide method, methyl ethyl ketone is used. The reaction process and reaction mechanism of the hydrogen peroxide method are not specified in patents, documents, etc., but the situation and chemical knowledge of the examples of the patent are considered to be based on the hydrogen peroxide method. It is necessary to react to produce methyl ethyl ketone imine. In acetone, acetone imine is unstable, so acetone is not used. In the hydrogen peroxide method, it is described in the patent that starting with a mixture of raw material methyl ethyl ketone and ammonia, methyl ethyl ketazine is formed as a result. Methyl ethyl ketazine is insoluble in water and has the advantage of being easily separated, but methyl ethyl ketazine is a more stable compound that is more difficult to hydrolyze and performs high-temperature thermal hydrolysis. Is an equilibrium reaction represented by reaction formula (5). At the time of high-temperature thermal hydrolysis, the equilibrium constant K1 is a very small difference from K2, but the temperature at which the K1 constant exceeds is a high temperature of 180-200 ° C. A mixture of water necessary for thermal hydrolysis of methyl ethyl ketazine and water necessary for hydrazine hydrate exceeds the theoretical amount is heated externally, or heated by blowing high-temperature steam at 180-200 ° C. Then, methyl ethyl ketone dissociated in a very small amount is distilled off from the top of the hydrolysis tower, and the resulting hydrated hydrazine aqueous solution remains at all. A large amount of energy is consumed and a mixture of methyl ethyl ketazine in which undecomposed methyl ethyl ketazine, methyl ethyl ketone, and hydrated hydrazine are recombined is recycled indefinitely to obtain hydrated hydrazine. The energy consumed for hydrolysis in this process is much greater than the energy consumed for hydrolysis of acetone azine. By exposing methylethyl ketazine to this high temperature for a long time, the production of by-products (the largest component is a condensate of pyrazolines and ketones) is increased, and coloring of products is also a big problem due to these reasons. In this production method, a highly toxic arsenic derivative called cacodyl is essential. The recovery method of this catalyst and the cost for it become a problem.

In the case of other azine compounds and hydrazone compounds of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ having a large carbonyl group and having a carbonyl group, thermal hydrolysis is impossible. It can be dissociated only by hydrolysis with a strong acid. There are also announcements using benzophenone and cyclohexanone, but hydrolyzed with strong acid such as sulfuric acid to obtain hydrazine sulfate. In order to obtain hydrated hydrazine, there is a problem in that it is neutralized with an alkaline substance to produce a large amount of salt by-products. (Non Patent Literature 3)

[Explanation for Hydrazone]
A small amount of hydrazone is observed as an incomplete reactant in the recombination of ketone and hydrated hydrazine during thermal hydrolysis and hydrazone as an incomplete reactant stopped in the middle state to become stable ketazine in the reaction system. On the other hand, in the case of reaction with a substituted hydrazine, the raw material is a substituted amine and ammonia, so that it is obtained as one compound in a mixture of various products. A substituted hydrazone from an amine having a substituent does not have a free hydrazino group and is therefore not reducible and stable. A hydrazone produced by recombination of one molecule of ketone with the incompletely reacted product of hydrazine produced from a mixture of ketone and ammonia with an oxidizing agent such as sodium hypochlorite, and the produced hydrazine. However, unlike the production method in which 1 molecule of hydrazine reacts with 2 molecules of ketone to form ketazine to produce a stable compound, it has the same problems as the first production method and the second production method. In the case of subcritical carbon dioxide, supercritical carbon dioxide, and liquid carbon dioxide, hydrazone is soluble in water, but substituted hydrazone is special because it has low solubility in water and liquid carbon dioxide. There is no point in favor of. In the original synthesis reaction, the produced ketazine or substituted hydrazone may be contained in the form of hydrazone or substituted hydrazone, so that it can be thermally hydrolyzed or liquid carbon dioxide gas (subcritical carbon dioxide gas, supercritical carbon dioxide gas system in the present invention). In order to contribute to the acquisition of the target product by converting to hydrazine hydrate or substituted hydrazine at the time of thermal hydrolysis. Further, the hydrazone compound undergoes a disproportionation reaction to become an azine compound and hydrazine. The produced hydrazine is decomposed with an oxidizing agent.

  The presence of hydrazone compounds as intermediates for the treatment in the present invention can be considered. When confirmed by liquid chromatography in the middle of the reaction, a peak presumed to be a hydrazone compound is observed. The presence of a hydrazone compound is also observed by liquid chromatography in the reaction solution in the middle of the thermal hydrolysis process. It is considered that a hydrazone compound may be present in the treatment reaction solution of the present invention because no oxidizing agent is present. Alternatively, it is considered that the product is not completely decomposed in the thermal hydrolysis treatment and is produced as an intermediate decomposition product. When a stable hydrazone compound that dissolves in water is separated and the treatment method of the present invention is applied, hydrated hydrazine can be obtained without hydrolysis and by-products as in the case of the azine compound due to the effects of the present invention.

[For Schiff base compounds]
In order to stabilize a carbonyl compound or an amino compound, the azomethine bond of a Schiff base compound that is frequently used corresponds to a half structure of ketoazine used in the present invention. In order to obtain a new carbonyl compound or amino compound by hydrolysis, hydrolysis using a mineral acid is a common method for those skilled in the art. It has the same drawbacks and problems as the ketone azine example. Since it has a half structure of ketone azine, it can be said to be equivalent to and similar to the hydrolysis reaction of ketone azine. As a method for solving this, it is obvious that hydrolysis using subcritical, supercritical, or liquid carbon dioxide, which is the method of the present invention, is effective.

[Solubility between carbon dioxide and water]
It is ideal that carbonic acid shows the effect of acid hydrolysis, but Pk ₁ = 3.60 of carbonic acid in carbonated water and Pk ₂ = 10.25 and Pk = 6.35 as carbonic acid is very weak. It is an acid and does not exhibit the function of an acid catalyst for hydrolysis. The lower the temperature and the higher the pressure of carbon dioxide gas, the higher the solubility in water and the lower the pH value of the aqueous solution. (Figure 1)

  However, carbonic acid having such a PH value cannot cause hydrolysis of ketazine, hydrazone, or substituted hydrazone. The amount of ketazine to be hydrolyzed is small, and rather, the acidity of carbonic acid is the catalyst and a lot of by-products are produced. The solubility of carbon dioxide in water is as shown in FIG. The amount of water dissolved in the carbon dioxide gas is high in a supercritical high temperature and high pressure state, but because of the high temperature, the side reaction preferentially gives no hydrated hydrazine or substituted hydrazine. Although the solubility of water in liquid carbon dioxide at low temperature is low, dissolved water is important. Sufficient agitation is required to increase the probability of new water dissolution and contact with liquid carbon dioxide.

[Carbon dioxide gas behavior, solubility (gas, subcritical, supercritical, liquid)]
The state diagram of carbon dioxide is as shown in FIG. No good ketazine hydrolysis is observed even when hydrolyzing ketazine in the subcritical and supercritical carbon dioxide state under the high temperature and high pressure at the central region of each region in the phase diagram in the presence of water. . Rather, the acidic catalytic effect of carbonic acid produces a lot of by-products. This problem does not exist in the liquid carbon dioxide phase.

  When hydrolyzing ketazine, hydrazone, or substituted hydrazone in the presence of water under the conditions of liquid carbon dioxide or supercritical carbon dioxide in the phase diagram of carbon dioxide, the aqueous layer is separated to add hydrazine or substituted hydrazine. The carbazic acid or substituted carbazine acid present in the water is heated, heated and hydrolyzed to obtain an extremely high yield, high efficiency, high concentration of hydrated hydrazine or substituted hydrazine. In addition, no condensate of pyrazoline or ketone, which is easily formed when reacted in a subcritical carbon dioxide or supercritical carbon dioxide state under high temperature conditions, is not observed. When subcritical carbon dioxide and supercritical carbon dioxide are used, if the temperature is high, a bad result is shown. Therefore, when the treatment is performed at a temperature as close to the critical point as possible, a good hydrolysis effect is exhibited.

[Status inside the pressure vessel]
When air is present inside the pressure reaction vessel, the air is expelled with carbon dioxide gas in advance and replaced with carbon dioxide gas, and the volume of the pressure reaction vessel is the liquid carbon dioxide to be filled and the raw material ketazine or hydrazone or A sufficient capacity suitable for the reaction operation is required because of a filling constant higher than that of the substituted hydrazone and water. The gas layer is mostly occupied by carbon dioxide. The situation inside the pressure is considered to be close to the state diagram in the pressure vessel when the liquid carbon dioxide is simply filled. The temperature change and pressure change in the pressure vessel depend on the filling constant of the liquid carbon dioxide gas, and below the critical temperature, the liquid carbon dioxide gas and the carbon dioxide gasified in the phase diagram of FIG. is there. Corresponding to the filling constant, when the temperature in the pressure vessel rises, the liquid carbon dioxide gas in the pressure vessel becomes full at the corresponding temperature, and when the temperature rises further, the pressure rises rapidly as shown in FIG. It becomes a supercritical state.

  The black line shows the change in pressure in the liquid and supercritical state when the filling constant is 1.34, the liquid is full at about 22 ° C. and the temperature is further increased. The gray line shows the pressure change in the supercritical state when the filling constant is 1.6, the liquid is full at 29 ° C., and the temperature further rises. Under the condition where the liquid carbon dioxide and the gaseous carbon dioxide are in an equilibrium state, they are on the boiling line.

[Detailed explanation of hydrolysis and operation of azines using liquid carbonic acid]
In azine, hydrazone, and substituted hydrazone used as raw materials, liquid compounds may be filled by an appropriate method at the time of filling the raw materials. In the case of solid materials, the reaction pressure vessel is opened to fill the required amount. As described above, the air in the reaction vessel is completely replaced with carbon dioxide before filling with liquid carbon dioxide. Even if the solid raw material does not completely dissolve in liquid carbon dioxide, it dissolves as the reaction proceeds.

  In the case of hydrazone obtained by adding 3 mol or more of water to 1 mol of azine in subcritical carbon dioxide, supercritical carbon dioxide, or liquid carbon dioxide, and partially hydrolyzing azine, 2 mol or more of water is added, and the liquid carbon dioxide is not particularly limited with respect to azine and hydrazone, but a large excess is preferred. The amount of water is 3 mol or more per 1 mol of azine, 2 mol or more per 1 mol of hydrazone, and in the case of substituted hydrazone, 2 mol or more of water is required per 1 mol of substituted hydrazone. It may be the amount of water adjusted to a target hydrazine or substituted hydrazine concentration, and is not particularly limited.

  The reaction conditions are as follows: the liquid temperature in the carbon dioxide phase diagram shown in FIG. 3 is −56.6 ° C. to 31.1 ° C., and the pressure is 0.52 MPa to 7.38 MPa. Is from −20 ° C. to 31 ° C., and the pressure is from 2.0 MPa to 7.4 MPa, more preferably from −2.8 ° C. to 5.8 MPa at −10 ° C. to 20 ° C. The pressure with respect to the temperature is on the boiling line of the liquefied carbon dioxide phase diagram and depends on the filling constant, but when the pressure vessel is full on the high temperature side, the pressure can rise rapidly with a slight temperature change There is sex. Therefore, in order to select the filling constant of the liquid carbon dioxide gas in the pressure reaction vessel and cope with the case where the pressure increases, it is preferable that the pressure resistance capacity has a margin such as 10 MPa. It is important to attach a safety valve that is discharged outside the system when the pressure exceeds that. However, the pressure resistance of the pressure vessel is not limited to these. In the case of subcritical carbon dioxide and supercritical carbon dioxide at a temperature of 31.1 ° C. or higher and a pressure of 7.38 MPa or higher, preferably at a corresponding filling constant, a temperature of 31.1 ° C. to 80 ° C. or lower. Thus, the pressure is 7.38 MPa or more. The pressure resistance of the pressure vessel is the same as that of liquid carbon dioxide. For the liquid carbon dioxide container and how to use it, refer to the High Pressure Gas Control Law and the manufacturer's instructions. After hydrolyzing azine at the temperature and pressure at which it becomes a state of supercritical carbon dioxide or liquid carbon dioxide, all carbon dioxide including supercritical carbon dioxide is converted into a liquid carbon dioxide layer by changing the temperature. Then, the liquid carbon dioxide layer and the aqueous layer are separated into two layers. When maintained at a low temperature, it exists as a hydrated hydrazine and carbazic acid in the aqueous layer. Carbazine acid generates carbon dioxide and becomes hydrated hydrazine when the temperature is raised to 30 ° C. or higher. The safe decomposition temperature of carbazic acid is preferably 40-60 ° C. In the case of subcritical carbon dioxide and supercritical carbon dioxide, the influence of temperature is very large, and it is desirable that the temperature is low for the purpose of this hydrolysis. Therefore, the critical points are 31.1 ° C. and 7.38 MPa. It is desirable to select near conditions. However, it is not limited to these numerical values and conditions, and may be any temperature and pressure suitable for work and operation.

  Generally, the liquefied carbon dioxide cylinder with siphon that is commercially available is sold in a boiling liquid state. For large-scale large-scale use, containers with a Dewar bottle-type vacuum insulation layer are sold with -20 ° C low-temperature liquefied carbon dioxide gas, but since the heat conduction is not zero, the internal liquid carbon dioxide gas evaporates, resulting in low temperatures. Is held.

  The separation of the liquid carbon dioxide layer and the aqueous layer cannot be shown uniformly because the layers are reversed depending on the temperature and the concentration of the substance dissolved in each. Separation is performed by measuring with a liquid level gauge with a sensor. The liberated ketone has a large amount dissolved in the liquid carbon dioxide layer, although the solubility varies depending on the type of ketone. Although it varies depending on the type of ketone, acetone or methyl ethyl ketone generally used in current production is easily soluble in liquid carbon dioxide, and particularly methyl ethyl ketone does not dissolve in water. The liquid carbon dioxide in which these ketones are dissolved can be recycled with these ketones dissolved in the case where a large amount of liquid carbon dioxide is used for azine or substituted hydrazone. In the case of a reaction between a subcritical carbon dioxide gas or a supercritical carbon dioxide gas and an aqueous layer, the aqueous layer is separated. However, the present invention is not limited to this.

  When the dissolution of the ketone in the liquid carbon dioxide gas becomes slow or difficult, the subcritical carbon dioxide gas, the supercritical carbon dioxide gas, and the liquid carbon dioxide gas are gasified with a vaporizer and taken out of the system, and the ketone remains as a residual liquid. The recovered ketone can be recycled as it is, but is purified by rectification when purification is required. What is necessary is just to select arbitrarily for the convenience of work and operation.

  When it is desired to use heat energy effectively in the entire reaction system, the liquid carbon dioxide gas is cooled by the heat of vaporization when it is gasified with a vaporizer, but it is heated with brine and the cold is recovered as low-temperature brine. Then, it is used for cooling liquefaction by distillation of ketones or for other cooling parts. The gasified carbon dioxide gas is cooled with the cooling heat when gasified, or when there is a separate cold heat source, the carbon dioxide gas is cooled and liquefied, or pressurized with a compressor and then liquefied. When carbon dioxide gas is cooled in advance, the efficiency when compressed and liquefied by the compressor can be increased, and the electric energy used for the compressor can be suppressed. When compressing with a compressor, it generates heat and releases heat to the outside. The heat generated at this time is recovered and used as heating energy for concentration and purification of hydrazine hydrate or distillation of ketones. It can be proposed that energy consumption is ideally reduced by applying these exergy. However, it is not limited to these operations.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ represented by the formulas represent the same substituent in each compound. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ may be the same, partly the same, partly different groups, or all different groups. A cyclic structure in which R ₁ , R ₂ and R ₃ , R ₄ are bonded may be used. Considering recycling use, it is desirable that the compound of the chemical formula (2) and the compound of the chemical formula (3) are the same compound. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ have a hetero atom even if they are hydrogen, branched, or have a substituent that does not react with ammonia, carbon dioxide, hydrazine, or the like. Alkyl group, alkenyl group, alkynyl group, alkylene group, aralkyl group, alkenylene group, arylene group, alicyclic group, aryl group, allyl group, heterocyclic group, condensed ring group, diyl group such as may be Etc. However, it is not limited to these.

Specific examples of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ include alkyl groups such as hydrogen, methyl group, ethyl group, isopropyl group and isobutyl group. A cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group is shown. Cyclic alkyl groups such as cyclopentyl group and cyclohexyl group including carbon in the compound structural formula are shown. An alkenyl group such as a vinyl group or an allyl group is shown. A cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group is shown. Cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group including carbon in the compound structural formula are shown. An aromatic ring group such as a phenyl group or a naphthyl group is shown. A heterocyclic group such as a pyrazole group, a pyrazoline group, an imidazole group, an imidazoline group, a pyridyl group, a pyrrole group, a triazole group, an oxazole group, a pipedinyl group, or a quinoline group is shown. Furthermore, these groups may have a substituent such as an alkoxy group, a halogen group, a nitro group, an amino group, an aryloxy group, an aromatic ring group or a heterocyclic group that does not react with ammonia, carbon dioxide gas, hydrazine or the like. good. Preferred are hydrogen, methyl group, ethyl group, isobutyl group, aryl group, cycloheptane ring, cyclohexane ring and the like. Specifically, when expressed by chemical formula (2) and chemical formula (3), aldehydes such as acetaldehyde, isopropyl aldehyde, benzaldide, naphthyl aldehyde, furfural, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclopentyl ketone, cyclo Pentanone, cyclohexanone, furanone, acetophenone, benzophenone, anthraquinone, naphthoquinone, fluorenone, fluorenyl ketone, and the like. However, it is not limited to these.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.

[Analysis and quantification method of hydrated hydrazine]
Analysis method of hydrated hydrazine obtained in the following examples.
The analysis of hydrated hydrazine can be performed by gas chromatography, but the accurate analysis is preferably performed by a titration method.

[Method for analysis of hydrazine hydrate by titration method]
Reagent 1) Hydrochloric acid (3 + 2)
Add 200 ml of deionized water to 300 ml of white hydrochloric acid.
2) Chloroform (special grade reagent)
3) M / 40 potassium iodate solution (5.35 g KIO3 / l)
Potassium iodate (standard reagent for volumetric analysis) was heated at 130 ° C. for 2 hours, allowed to cool in a desiccator, weighed the amount corrected to 10.701 g to 0.1 mg, transferred to a 2000 ml volumetric flask, and removed. Adjust to constant volume after dissolving in ionic water. {Prepare factor (F) to be 1.000}

Procedure 1) Weigh accurately the amount of sample collected (*) according to the concentration, put it in a 500 ml volumetric flask, and make it constant volume with deionized water.
2) Take 10 ml accurately, transfer to a stoppered flask (300 ml), and add 50 ml of hydrochloric acid (3 + 2).
3) Titrate with M / 40 potassium iodate solution, add 5 ml of chloroform near the end point, shake vigorously until the red color of the chloroform layer disappears, and shake vigorously.
The content is determined by the following formula.

Remarks

[Synthesis of standard experimental materials]

[Synthesis of acetone azine]
100% hydrazine 100 g (2 mol) is added to 2,320 g (40 mol) of acetone at room temperature. At this time, the temperature is raised due to reaction heat. Thereafter, the internal temperature is stirred in the range of 40 to 50 ° C. for 2 hours. After the reaction, after cooling to room temperature, 828 g (6 mol) of anhydrous potassium carbonate is gradually added under strong stirring, and the by-product water is removed by stirring at room temperature for 2 hours. At this time, note that potassium carbonate may solidify if stirring is insufficient.
After drying, potassium carbonate is filtered off, and the filtered potassium carbonate is thoroughly washed with acetone. After excess acetone is distilled off under reduced pressure, acetone azine is rectified by distillation under reduced pressure.

[Synthesis of methyl ethyl ketone azine]
To 1,440 g (20 mol) of methyl ethyl ketone, 100 g (2 mol) of 100% hydrazine hydrate is added dropwise with vigorous stirring while heating at 60 ° C. Heat from the outside during dripping so that the temperature reaches 80 ° C. at the end of dripping. Methyl ethyl ketone does not react easily with hydrazine hydrate. The reaction is carried out at 80 ° C. with vigorous stirring for 10 hours after completion of the dropping. Since methyl ethyl ketone and 100% hydrazine are not dissolved, they have two layers. The upper methyl ethyl ketone layer is separated, dehydrated with anhydrous sodium sulfate and dried. After filtering off sodium sulfate, excess methyl ethyl ketone is distilled off under reduced pressure, and methyl ethyl ketazine is rectified by distillation under reduced pressure.

  Install a liquefied carbon dioxide cylinder with a siphon tube, a supercooling device, and a high-pressure metering pump in an autoclave with a safety valve having a capacity of 400 ml and a pressure resistance of 20 MPa, and immerse the autoclave in a thermostatic bath. Carbon dioxide gas is pre-flowed through the autoclave to completely replace the air in the autoclave. The entire autoclave is brought to 20 ° C. in a constant temperature bath at 20 ° C. A solution prepared by dissolving 28 g (0.25 mol) of acetone azine in 31.5 g (1.75 mol) of water is adjusted to 20 ° C. and poured into an autoclave. On top of that, in order to prevent gasification at a time when liquefied carbon dioxide gas is introduced under stirring, 213 g (4.84 mol) of carbon dioxide gas from a liquid carbon dioxide cylinder is gradually passed through a supercooler with a high-pressure fluid metering pump into an autoclave. inject. The amount of liquid carbon dioxide injected is measured by both the amount from the metering pump and the change in the weight of the autoclave filled with liquid carbon dioxide. The pressure in the autoclave is about 5.7 MPa. Therefore, the bubble is closed and stirring is performed at 20 ° C. for 12 hours. The liquid carbon dioxide in the cylinder, water, and liquid components of water and acetone azine occupy about 270 ml, the volume of the gas state occupies about 130 ml, and is on the boiling line of the phase diagram.

  At 20 ° C after the completion of the reaction, the specific gravity of liquid carbon dioxide is less than that of water. Therefore, the lower water layer is taken out into a pressure vessel, dissolved carbon dioxide is released from the gas release valve, and then gradually heated to 55 ° C. Warm up. The carbazic acid present in the aqueous layer is decomposed into hydrated hydrazine and carbon dioxide, and the carbon dioxide is discharged from the system through the release valve. A sample is taken from the aqueous layer, and the amount of hydrated hydrazine is calculated by the titration analysis described above. As a result of titration analysis, it was found that hydrazine hydrate was 11.75 g (0.235 mol) (yield 94%). The concentration of the hydrated hydrazine is about 38.4% hydrated hydrazine solution because the amount of water dissolved in the liquefied carbon dioxide gas is very small at this temperature and pressure.

  The same reaction and treatment as in Example 1 are carried out except that the temperature is 10 ° C. and the water is 22.5 g (1.25 mol). A titration analysis of the aqueous layer yielded 0.24 moles of hydrated hydrazine. The yield is 96%. This is a hydrazine solution of about 55.7% strength.

  The same reaction and treatment as in Example 1 are performed except that the temperature is 0 ° C. and the water is 22.5 g (1.25 mol). A titration analysis of the aqueous layer gave 0.246 moles of hydrazine hydrate. The yield is 98.4%. This is an approximately 57.2% strength hydrated hydrazine solution.

  A liquefied carbon dioxide cylinder with a siphon, a carbon dioxide gas storage tank, a supercooler, and a high-pressure metering pump are installed on the top of an autoclave having a capacity of 400 ml and a pressure resistance of 20 MPa having a stirrer, and the autoclave is immersed in a thermostatic bath. Carbon dioxide gas is allowed to flow through the autoclave in advance to completely replace the air in the autoclave. The whole autoclave is brought to 32 ° C. in a constant temperature bath of 32 ° C. A solution prepared by dissolving 28 g (0.25 mol) of acetone azine in 22.5 g (1.25 mol) of water is adjusted to 32 ° C. and poured into an autoclave. Further, 219 g (4.98 mol) of liquid carbon dioxide gas from the liquid carbon dioxide gas cylinder which has passed through the supercooler under stirring is gradually injected into the autoclave using a high-pressure fluid metering pump. The internal pressure of the autoclave is about 9 MPa. Assuming that all liquid components are liquid carbon dioxide, the filling constant of carbon dioxide corresponds to about 1.6. However, since about 50 g of liquid components other than liquid carbon dioxide are filled, what is exactly the filling constant of 1.6? I can not say. Therefore, the bubble is closed and stirring is performed at 32 ° C. for 12 hours. At 32 ° C., the pressure in the autoclave is about 9 MPa. In a cylinder intended for use of a normal liquid carbon dioxide gas, the liquid carbon dioxide gas in the cylinder is in a state on the boiling line of the phase diagram below the 31.1 ° C. critical point. Under the condition of this filling constant, at about 29 ° C., the gas layer disappears in the carbon dioxide cylinder, and the liquid is in a critical carbon dioxide state full of liquid. The reaction autoclave uses a 200 MPa autoclave with a safety valve to maintain the supercritical carbon dioxide gas layer for the purpose of safety because the pressure increases rapidly even if there is a slight temperature change.

  After completion of the reaction, the autoclave and the contents are cooled to 10 ° C., the lower aqueous layer having a large specific gravity is taken out into a pressure vessel, dissolved carbon dioxide gas is released from the gas release valve, and then gradually heated to 55 ° C. To do. The carbazic acid present in the aqueous layer is decomposed into hydrated hydrazine and carbon dioxide, and the carbon dioxide is discharged from the system through the release valve. A sample is taken from the aqueous layer, and the amount of hydrated hydrazine is calculated by the titration analysis described above. As a result of titration analysis, it was found that hydrazine hydrate was 0.205 mol (yield 82%). The concentration of the hydrated hydrazine is about 47.3% of the hydrated hydrazine solution because the amount of water dissolved in the liquefied carbon dioxide gas is very small at this temperature and pressure.

A liquefied carbon dioxide cylinder with a siphon, a vaporizer, a carbon dioxide gas storage tank, a supercooler, and a high-pressure metering pump are installed on the top of an autoclave having a volume of 400 ml and a pressure resistance of 20 MPa having a stirrer, and the autoclave is immersed in a thermostatic chamber. Carbon dioxide gas is passed through the autoclave to completely replace the air in the autoclave. The entire autoclave is brought to 20 ° C. in a constant temperature bath at 20 ° C. A solution prepared by dissolving 35 g (0.25 mol) of methyl ethyl ketone azine in 22.5 g (1.25 mol) of water is adjusted to 20 ° C. and poured into an autoclave. On top of that, 215 g (4.9 mol) of liquid carbon dioxide gas that has passed through the supercooler with stirring is gradually injected into the autoclave using a high-pressure fluid metering pump. Therefore, the bubble is closed and stirring is performed at 20 ° C. for 12 hours. The filling constant of liquid carbon dioxide is about 1.6. With this filling constant, in a normal liquid carbon dioxide cylinder, there are liquid carbon dioxide gas and a gaseous carbon dioxide layer in the cylinder. Below 29 ° C, it is the state on the boiling line of the equilibrium state diagram. At 20 ° C., the pressure in the autoclave shows about 5.9 MPa.
Even if the temperature is higher than that, it is on the boiling line of the phase diagram up to 29 ° C. The reaction autoclave uses a 200-pressure-resistant autoclave with a safety valve for the purpose of ensuring safety even when there is a slight temperature change, and for holding a supercritical carbon dioxide layer.

  At 20 ° C after the completion of the reaction, the specific gravity of liquid carbon dioxide is less than that of water. Therefore, the lower water layer is taken out into a pressure vessel, dissolved carbon dioxide is released from the gas release valve, and then gradually heated to 55 ° C. Warm up. The carbazic acid present in the aqueous layer is decomposed into hydrated hydrazine and carbon dioxide, and the carbon dioxide is discharged from the system through the release valve. A sample is taken from the aqueous layer, and the amount of hydrated hydrazine is calculated by the titration analysis described above. As a result of titration analysis, it was found that hydrazine hydrate was 0.233 mol (yield 93%). The concentration of hydrazine hydrate is a hydrazine solution having a concentration of about 54.0% because the amount of water dissolved in liquefied carbon dioxide is very small at this temperature and pressure.

  As raw materials, 72 g (0.20 mol) of benzophenone azine, 188 g (4.27 mol) of liquid carbon dioxide gas, 31.5 g (1.75 mol) of water are used, and the filling constant is about 1.58. When the same treatment as in Example 1 is performed, 9.1 g (0.182 mol) of hydrazine hydrate is obtained. The yield of 91% hydrazine is 29.8%.

  From the weight measurement of the autoclave containing the liquid carbon dioxide gas separated and stored in the autoclave in Example 1, the weight of the first empty autoclave is predicted to be generated by hydrolysis and dissolved in the liquid carbon dioxide gas. By subtracting the weight of acetone, the approximate amount of residual liquid carbon dioxide was considered to be 203 g. On top of this, 27 g (1.5 mol) of water and 28 g (0.25 mol) of acetone azine were charged, and the same reaction and treatment as in Example 1 were carried out. The packing constant was estimated to be about 1.7. As a result of the analysis, 10.4 g (0.208 mol) of hydrated hydrazine was obtained with a yield of 83%.

Claims (8)

  By hydrolyzing a ketone azine, hydrazone or Schiff base compound in the presence of carbon dioxide in a subcritical, supercritical, or liquid carbon dioxide state to form a ketone and a hydrated hydrazine or substituted hydrazine, or a carbazic acid or substituted carbazic acid, Alternatively, a method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound, which comprises obtaining a carbonyl compound and an amino compound, or a carbamine compound or a substituted carbamic acid.   The temperature at which the carbon dioxide gas temperature is 60 ° C. or lower and −56.6 ° C. or higher, and the carbon dioxide gas pressure is 0.52 MPa or higher to form a subcritical carbon dioxide gas, supercritical carbon dioxide gas, or liquid carbon dioxide gas. The method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound according to claim 1 under a condition comprising a combination of pressure, a filling factor, and the like.   The temperature, pressure, and filling factor for forming a subcritical, supercritical, or liquid carbon dioxide state when the temperature of the carbon dioxide gas is −30 ° C. to 40 ° C. and the pressure of the carbon dioxide gas is 1.4 MPa to 7.38 MPa or more. The method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound according to claim 1 or 2 under a condition comprising a combination thereof.   The method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound according to any one of claims 1 to 3, wherein the carbon dioxide gas is recyclable.   The hydrazine, substituted hydrazine or substituted hydrazine according to any one of claims 1 to 4, further comprising heating the carbazic acid or substituted carbazic acid to decompose into hydrated hydrazine or substituted hydrazine and carbon dioxide. A method for producing an amino compound. The ketone azine has the chemical formula (1):

[Where:
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aromatic ring group or a heterocyclic group (wherein these groups are alkyl groups) By one or more substituents selected from the group consisting of groups, alkenyl groups, alkynyl groups, halogen groups, alkoxy groups, amino groups, nitro groups, thiol groups, aryloxy groups, aromatic ring groups and heterocyclic groups, Optionally substituted), or
R ¹ and R ² , together with the carbon atom to which they are bonded, form a ring structure (wherein the ring structure group is substituted with an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, Optionally substituted by a substituent selected from the group consisting of an amino group, a nitro group, a thiol group, an aryloxy group, an aromatic ring group and a heterocyclic group, or R ³ and R ⁴ Together with the carbon atom to which they are bonded, a ring structure (wherein the ring structure group is substituted with an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, an amino group, a nitro group, , Optionally substituted by a substituent selected from the group consisting of a thiol group, an aryloxy group, an aromatic ring group and a heterocyclic group)]
The method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound according to any one of claims 1 to 5, which is a compound represented by the formula: The hydrazone has the chemical formula (7):

[Where:
R ¹ , R ² , R ⁵ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aromatic ring group or heterocyclic group (wherein These groups are selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, halogen groups, alkoxy groups, amino groups, nitro groups, thiol groups, aryloxy groups, aromatic ring groups, and heterocyclic groups. Optionally substituted by the above substituents, or
R ¹ and R ² , together with the carbon atom to which they are bonded, form a ring structure (wherein the ring structure group is substituted with an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, Optionally substituted by a substituent selected from the group consisting of an amino group, a nitro group, a thiol group, an aryloxy group, an aromatic ring group and a heterocyclic group, or R ⁵ and R ⁶ Together with the nitrogen atom to which they are bonded, a ring structure (wherein the ring structure group includes, as a substituent, an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, an amino group, a nitro group, , Optionally substituted by a substituent selected from the group consisting of a thiol group, an aryloxy group, an aromatic ring group and a heterocyclic group)]
The method for producing a hydrated hydrazine, a substituted hydrazine or an amino compound according to any one of claims 1 to 5, which is a compound represented by the formula: The Schiff base has the chemical formula (9):

[Where:
R ¹ , R ² and R ⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aromatic ring group or a heterocyclic group (wherein these groups Is one or more substituents selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, halogen groups, alkoxy groups, amino groups, nitro groups, thiol groups, aryloxy groups, aromatic ring groups and heterocyclic groups Optionally substituted by a group), or
R ¹ and R ² , together with the carbon atom to which they are bonded, form a ring structure (wherein the ring structure group is substituted with an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, A compound optionally substituted with a substituent selected from the group consisting of an amino group, a nitro group, a thiol group, an aryloxy group, an aromatic ring group, and a heterocyclic group. The manufacturing method of the hydrated hydrazine, substituted hydrazine, or amino compound as described in any one of Claims 1-5.