JP2000007635A - Production of 1,1,1-trimethylhydrazinium hydroxide and 1,1,1-trimethylhydrazinium carbonate of 1,1,1- trimethylhydrazinium bicarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing high-purity 1,1,1- trimethylhydrazinium hydroxide by using hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine and dimethyl carbonate as raw materials. SOLUTION: Hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine is reacted with dimethyl carbonate to give 1,1,1-trimethylhydrazinium carbonate and/or 1,1,1-trimethylhydrazinium bicarbonate, which is then electrolyzed using a cation-exchanger membrane as a permeable membrane to produce 1,1,1- trimethylhydrazinium hydroxide.

Description

Detailed Description of the Invention

[0001]

The present invention not only leads to a novel use as a photoresist developer, but also as a surfactant, an elastomer, a polymerization catalyst, a medicine, a pesticide, a high purity 1,1 useful as an amine imide intermediate raw material The present invention relates to a method for producing 1,1-trimethylhydrazinium hydroxide. The present invention also relates to a process for producing 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate used as a raw material of the above-mentioned synthesis method.

[0002]

BACKGROUND OF THE INVENTION 1,1,1-trimethylhydrazinium hydroxide is prepared according to the following formula (1):
Methods are known for the preparation of trimethylhydrazinium chloride by dehydrochlorination with a strong base compound [Chem. Ber. 99 (10), 3118-27
(1966)] {prior art 1}.

[Chemical formula 1]

Incidentally, 1,1,1-trimethylhydrazinium chloride synthesizes chloroamine from ammonia and sodium hypochlorite according to the following formula (2):
It is then produced by reacting with trimethylamine [JP-A-58-24552] {prior art 2}.

[Chemical formula 2]

[0004]

However, in the prior arts 1 and 2, chloroamine is obtained from ammonia and sodium hypochlorite, and this is reacted with trimethylamine to obtain 1,1,1-trimethylhydrazinium chloride. Is then reacted with a strong base compound to produce 1,1,1-trimethylhydrazinium hydroxide by dehydrochlorination, but the reaction route is long and the handling of the strong base compound is complicated. In addition, since a halogen compound is used as a raw material, there is a problem that the concentration of the halogen compound remaining in the obtained 1,1,1-trimethylhydrazinium hydroxide is high.

Accordingly, the object of the present invention is to produce 1,1,1-trimethylhydrazinium hydroxide excellent in purity in a small number of steps, starting from easily accessible and easily available raw materials. There is a way to offer. Another object of the present invention is to provide an easy-to-handle hydrated hydrazine, 1-methylhydrazine or 1,1 intermediate to be used for the preparation of 1,1,1-trimethylhydrazinium hydroxide.
An object of the present invention is to provide a method which can be produced from 1-dimethylhydrazine. Still another object of the present invention is to provide a process for producing the above-mentioned novel inclusion complex of 1,1,1-trimethylhydrazinium hydroxide.

[0006]

According to the present invention,
1,1-trimethylhydrazinium carbonate and / or
Or a method for producing 1,1,1-trimethylhydrazinium hydroxide characterized in that 1,1,1-trimethylhydrazinium vicinate is subjected to electrolysis with a cation exchange membrane as a diaphragm. Be done. According to the invention, 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium carbonate characterized in that it is characterized by reacting hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine with dimethyl carbonate. A process is provided for producing 1,1-trimethylhydrazinium bicarbonate. Further according to the invention, hydrated hydrazine, 1-
1,1,1 obtained by reacting methyl hydrazine or 1,1-dimethyl hydrazine with dimethyl carbonate
-A 1,1,1-trimethylhydrazide characterized in that trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate is subjected to electrolysis with a cation exchange membrane as a diaphragm. A method of producing a nickel hydroxide is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Function] The object of the method of the present invention, 1,1,1-trimethylhydrazinium hydroxide, is represented by the following formula (3)

[Chemical formula 3] It is a strongly basic compound having a chemical structure represented by and which has conventionally been difficult to isolate in a high purity form.

In the present invention, the following formula (4) is used as a raw material (intermediate) for synthesizing the above-mentioned substance:

[Chemical formula 4] 1,1,1-trimethylhydrazinium carbonate represented by the following formula (5)

[Chemical formula 5] The 1,1,1-trimethylhydrazinium borate represented by is selected and used. By subjecting these carbonates or bicarbonates to electrolysis with a cation exchange membrane as a diaphragm, it becomes possible to separate 1,1,1-trimethylhydrazinium hydroxide in a high purity form.

That is, the reaction by this electrolysis is represented by the following formula (6)

[Chemical formula 6] Since the carbonate ion or bicarbonate ion which is an anion is volatilized and separated in the form of carbon dioxide gas, it is excellent in that there is no contamination by the anion. During this electrolysis, as described in detail below,
Although ammonia and trimethylamine, which are decomposition products of 1,1,1-trimethylhydrazinium hydroxide, may be by-produced in some cases, removal of these decomposition products is extremely easy.

The above 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate used as a raw material (intermediate) for the electrolysis reaction is represented by the following formula (7)

[Chemical formula 7] Hydrated hydrazine represented by the following formula (8)

[Image 8] Monomethyl hydrazine represented by the following formula (9)

Embedded image And dimethylhydrazine represented by the following formula (10)

[Image 10] Obtained by the reaction with dimethyl carbonate represented by

Hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine used as a raw material, and dimethyl carbonate are both readily available, inexpensive and easy to handle. This provides the advantage that 1,1-trimethylhydrazinium hydroxide can be advantageously provided industrially.

[Synthesis of Raw Materials and Intermediates Used] In the present invention, hydrazine hydrate, 1-methylhydrazine or 1,1-dimethylhydrazine is used as a hydrazine derivative as a starting material. Of course, these hydrazine derivatives may be used alone or as a mixture of two or more. It is also possible to use an aqueous solution of the hydrazine derivative or an alcohol solution such as methanol. Dimethyl carbonate can be used a general commercial item.

The reaction of the above hydrazine derivative with dimethyl carbonate is shown by the following formula (11), taking the case of 1,1-dimethylhydrazine as an example.

[Image 11] It is as represented by

In this reaction, introduction of a methyl group to the nitrogen atom at position 1 of the hydrazine derivative and dissociation of dimethyl carbonate into bicarbonate ion or carbonate ion proceed to 1,1,1-trimethylhydrazinium. It will be appreciated that carbonate or 1,1,1-trimethylhydrazinium vicinate is formed. When monomethyl hydrazine is used as the hydrazine derivative, substitution of the methyl group to the nitrogen atom occurs in two stages, and in the case of hydrated hydrazine, substitution of the methyl group to the nitrogen atom occurs in three stages You can think of it.

In the synthesis of 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate, the reaction molar ratio of dimethyl carbonate to hydrazine derivative differs depending on the kind of hydrazine derivative. However, generally speaking, the reaction molar ratio is: dimethyl carbonate / hydrazine hydrate ジ メ チ ル 3 dimethyl carbonate / 1-methylhydrazine ≧ 2 dimethyl carbonate / 1,1-dimethylhydrazine ≧
It is preferred that the stoichiometric ratio is 1: dimethyl carbonate / hydrazine hydrate = 3 dimethyl carbonate / 1-methyl hydrazine = 2 dimethyl carbonate / 1,1-dimethyl hydrazine =
It is preferred to carry out the reaction at a molar ratio of 1.

The reaction temperature is 70 to 120 ° C., preferably 90 to 110 ° C. The reaction pressure is increased by the formation of methanol, but the pressure is usually 50 kg / cm ^2.
G (gauge), preferably 3 to 20 kg / cm ² G. The reaction time is about 1 to 10 hours, preferably 2 to 5 hours. As the solvent, water, an alcohol solvent such as methanol, or a water-methanol mixed solvent can be used. Industrially, there is also a method using an aqueous solution of hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine.

After the synthesis of 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate, the reaction mixture is concentrated under reduced pressure, and unreacted hydrazine hydrate, 1-methylhydrazine or The alcohol solvent such as 1,1-dimethylhydrazine and dimethylcarbonate and methanol is distilled off. Since this concentrate is generally obtained as a concentrate containing white crystals of 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate, an appropriate amount thereof may be used. Ultrapure water is added to dissolve the crystals, and light yellow 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate aqueous solution to the following electrolytic treatment Apply.

[Electrolysis] According to the present invention, 1,1,1-trimethylhydrazinium carbonate obtained as described above and / or 1,1,1-trimethylhydrazinium bicarbonate is used as a cation. It is subjected to electrolysis with the exchange membrane as a diaphragm to form 1,1,1-trimethylhydrazinium hydroxide.

In the electrolysis method of the present invention, generally, a general electrolytic cell in which a cation exchange membrane is divided into an anode chamber and a cathode chamber is used, and the type thereof is not particularly limited.

The cation exchange membrane used in the present invention is a cation exchange membrane known per se, for example, one having a cation exchange group such as a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, etc. Those having a fluorine resin as a skeleton are used. Sulfonic acid-based cation exchange membranes such as <Nafion 966> or <Nafion 350> (manufactured by DuPont) made of fluorocarbon resin can be suitably used.

The anode used in the present invention may be an electrode having a film containing a platinum group metal or its oxide formed on a corrosion resistant substrate, or an electrode having high corrosion resistance in an oxidizing atmosphere such as magnetite. . Further, as the cathode used in the present invention, metals which are not attacked by alkali such as stainless steel and nickel can be used. These anodes and cathodes can be used in any form such as plate, rod, net or perforated plate.

In the present invention, the electrolysis of the 1,1,1-trimethylhydrazinium carbonate and / or the 1,1,1-trimethylhydrazinium bicarbonate aqueous solution is carried out using 1,1,1-trimethylhydrazinium carbonate. And / or 1,1,1-trimethylhydrazinium bicarbonate aqueous solution is supplied to the anode chamber of the electrolytic cell, ultrapure water is supplied to the cathode chamber, and a DC voltage is applied between the two electrodes. , Its current density is 1 to 100 A /
dm ² , preferably 3 to 50 A / dm ² , voltage is 0.1
To 30 V, preferably 1 to 10 V.

In the present invention, the temperature of electrolysis is 10
It is preferably in the range of -50 ° C.

In the present invention, the electrolysis can be carried out either batchwise or continuously.

In the present invention, the concentration of the raw material supplied to the anode chamber is 1 to 60% by weight, preferably 5 to 50% by weight.

In the present invention, ultrapure water is supplied to the cathode chamber, but at the start of electrolysis, ultrapure water alone has low electrical conductivity and it is difficult for electrolysis to occur. It is desirable to use a solution to which 1,1,1-trimethylhydrazinium hydroxide is added in a small amount, for example, about 0.01 to 5% by weight.

In the present invention, the electrolysis is preferably carried out in an atmosphere of clean nitrogen or an inert gas such as argon.

After completion of the electrolysis, the cathode chamber contains 1, 1, 1
An aqueous solution of trimethylhydrazinium hydroxide is recovered. In this aqueous solution, although not necessarily limited to this case, it is common that ammonia, which is a decomposition product of 1,1,1-trimethylhydrazinium hydroxide, and trimethylamine coexist. Also in this case, ammonia and trimethylamine are completely distilled off by concentrating the mixed aqueous solution, and if necessary, adsorption treatment with active carbon is further performed to obtain high purity 1,1,1-trimethyl. Hydrazinium hydroxide can be produced.

In fact, as a result of concentration under reduced pressure of the above mixed aqueous solution, ammonia in 1,1,1-trimethylhydrazinium hydroxide aqueous solution after concentration under reduced pressure and trimethylamine were analyzed by ion chromatography.
Both were below the detection limit.

However, the aqueous solution of 1,1,1-trimethylhydrazinium hydroxide after concentration under reduced pressure may be pale yellow and may also retain a trace amount of amine odor.
Furthermore, the content of metal impurities such as Na, Ca, Fe, Ni, and Cr may be several tens ppb. Therefore, by treating the 1,1,1-trimethylhydrazinium hydroxide aqueous solution after concentration under reduced pressure with activated carbon, it is colorless and odorless, and the content of metal impurities such as Na, Ca, Fe, Ni, Cr, etc. is <10 ppb. It is possible to obtain a high purity 1,1,1-trimethylhydrazinium hydroxide aqueous solution of

The type of activated carbon used in the purification step may be either coal-based or coconut-shell-based activated carbon. In addition, the shape thereof is preferably granular, spherical, crushed coal or the like. The method of use is to fill the column with activated carbon and pass the 1,1,1-trimethylhydrazinium hydroxide aqueous solution, or add the activated carbon to the 1,1,1-trimethylhydrazinium hydroxide aqueous solution and stir After that, there is a method of filtering activated carbon to obtain a high purity 1,1,1-trimethylhydrazinium hydroxide aqueous solution. The amount of activated carbon used is 1, 1, 1
3-of trimethylhydrazinium hydroxide aqueous solution
It is 15% by weight.

Thus, according to the invention, 1,1,1-
Trimethylhydrazinium hydroxide can be produced in the form of a highly pure aqueous solution. According to the invention 1,
1,1-Trimethylhydrazinium hydroxide is to be used in the form of this aqueous solution for the above-mentioned applications, photoresist developer, surfactant, elastomer, polymerization catalyst, medicine, agricultural chemical, amine imide intermediate raw material Can.

[Inclusion compound and its preparation] 1,1, 1-
Trimethylhydrazinium hydroxide is a strongly basic compound having strong hygroscopicity, and it is difficult to isolate 1,1,1-trimethylhydrazinium hydroxide as crystals after concentration of the solvent. However, 1,1,
By using 1-trimethylhydrazinium hydroxide as a guest molecule and reacting it with a host molecule such as 1,1'-bis-β-naphthol, 1,1,1-trimethylhydrazinium hydroxide inclusion complex is obtained It can be isolated as a crystal.

Examples of host compounds used for the synthesis of inclusion complexes include phenol compounds described in Japanese Patent Publication No. 6-21017, and particularly preferred compounds are those of the following formula (12)

[Chemical formula 12] And 1,1′-bis-β-naphthol represented by

Heating the crystals of 1,1'-bis-β-naphthol of the above formula (12) and 1,1,1-trimethylhydrazinium hydroxide in an alcohol solvent such as water or methanol or ethanol After dissolution, the reaction formula (13) is obtained by leaving it to stand at room temperature.

Embedded image As shown in Table 1, crystalline 1,1,1-trimethylhydrazinium hydroxide / 1,1'-bis- with a stoichiometric ratio
A β-naphthol inclusion complex is formed.

Specifically, 1,1'-bis-β-naphthol and 1,1,1-trimethylhydrazinium hydroxide aqueous solution are used as 1,1'-bis-β-naphthol /
1,1,1-trimethylhydrazinium hydroxide =
The reactor is charged with pure water or pure water-refined methanol mixed solvent at a ratio of 1/1 to 1/2 (molar ratio), and is dissolved by heating. After being dissolved by heating, by leaving at room temperature for 1 to 2 days, crystals of 1,1′-bis-β-naphthol / 1,1,1-trimethylhydrazinium hydroxide inclusion complex precipitate. After filtration or centrifugation, washing with water,
It can be dried to obtain a crystalline inclusion complex in a stoichiometric ratio as a crystal.

In this inclusion complex, 1,1,1-trimethylhydrazinium hydroxide is incorporated into the inclusion complex in an extremely high purity state, so this inclusion complex is used for various applications. be able to. For example, it can be isolated to confirm the structure of the target 1,1,1-trimethylhydrazinium hydroxide. Moreover, it can also be used as a high purity raw material of 1,1,1-trimethylhydrazinium hydroxide.

[0038]

EXAMPLES The present invention will be described in more detail by way of the following examples, which should not be construed as limiting the invention in any way. 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate and 1,1,1-trimethylhydrazinium hydroxide can be used for NHCl titration or ion chromatography. It quantified by.

Example 1 Synthesis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicanate [1,1-Dimethylhydrazine] 1,1-Dimethylhydrazine 98.8 g (1.64 mo
l), dimethyl carbonate 148.1 g (1.64 m)
ol), 75.0 g of methanol and 50.0 g of water were charged into a 500 ml autoclave made of zirconium, and the temperature was raised from room temperature to 104 ° C. in 50 minutes. The pressure at the time of temperature rise rose to 6.5 kg / cm ² G. Then 97
It reacted at -106 degreeC for 3 hours. The pressure at the end of the reaction is 1
It was 4.7 kg / cm ² G. After completion of the reaction, the reaction liquid 3
Concentrate 61.1 g and distill off unreacted 1,1-dimethylhydrazine, dimethyl carbonate and methanol.
227.3 g of a concentrated solution was obtained. White crystals were precipitated in the concentrate. Ultrapure water 10 to the concentrate containing white crystals
Add 8.6 g, dissolve the crystals, weakly alkaline, odorless,
335.9 g of a pale yellow 1,1,1-trimethylhydrazinium carbonate and / or a 1,1,1-trimethylhydrazinium bicarbonate aqueous solution were obtained. NHCl
According to the titration, the content 61.6 wt%, 206.9 g (1.5
2 mol), yield 92.7%.

EXAMPLE 2 Synthesis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicanate [1,1-Dimethylhydrazine] 1,1-Dimethylhydrazine 98.8 g (1.64 mo
l), 147.7 g of dimethyl carbonate (1.64 m)
ol), 125.0 g of water, 500 ml of zirconium
In an autoclave, and at 100 to 110 ° C., 3.
It reacted for 5 hours. The pressure during the reaction is 3.8 to 20.1 k.
It was g / cm ² G. After completion of the reaction, the reaction solution 360.0
g is concentrated, unreacted 1,1-dimethylhydrazine, dimethyl carbonate and generated methanol are distilled off, and an appropriate amount of ultrapure water is added to the concentrate containing white crystals to dissolve the crystals, weakly alkaline Odorless, light yellow 1,1,1-
Trimethylhydrazinium carbonate or 1,1,1
-Trimethylhydrazinium bicarbonate aqueous solution 31
I got 4.1 g. Content 62.2 wt according to NHCl titration
%, 195.3 g (1.44 mol), yield 87.5%
Met.

EXAMPLE 3 Synthesis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate [1,1-Dimethylhydrazine] 1,1-Dimethylhydrazine 30.1 g (0.50 mo
l), 45.0 g of dimethyl carbonate (0.50 mo
l), 150.0 g of methanol and 100.0 g of water are charged in a 500 ml autoclave made of zirconium, 1
The reaction was carried out at 00 to 104 ° C. for 3 hours. The reaction pressure is
It was 4.2-8.5 kg / cm < ² > G. After the reaction,
318.2 g of the reaction solution is concentrated, the remaining 1,1-dimethylhydrazine, dimethyl carbonate and methanol are distilled off, and an appropriate amount of ultrapure water is added to the concentrate containing white crystals to dissolve the crystals. Light yellow 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-
Trimethylhydrazinium bicarbonate aqueous solution 15
I got 3.9 g. Content 33.9 wt according to NHCl titration
%, 52.2 g (0.38 mol), and the yield was 76.6%.

EXAMPLE 4 Synthesis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate [1,1-Dimethylhydrazine] 1,1-Dimethylhydrazine 98.8 g (1.64 mo
l), 147.7 g of dimethyl carbonate (1.64 m)
ol), 75.0 g of methanol and 50.0 g of water are charged into a 500 ml autoclave made of zirconium, and 79
It reacted at -85 degreeC for 3.5 hours. The reaction pressure is
It was 1.3 to 5.3 kg / cm ² G. After the reaction,
365.8 g of the reaction solution is concentrated, unreacted 1,1-dimethylhydrazine, dimethyl carbonate and methanol are distilled off, and an appropriate amount of ultrapure water is added to the concentrate containing white crystals to dissolve the crystals. Thus, 269.8 g of a weakly alkaline, odorless, pale yellow 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate solution was obtained. According to NHCl titration, the content was 68.8 wt%, 185.5 g (1.36 mol), and the yield was 83.1%.

Example 5 Synthesis of 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate [1,1-dimethylhydrazine] {atmospheric pressure reaction} 1 1,8-dimethylhydrazine 98.8g (1.64 mo
l), 147.7 g of dimethyl carbonate (1.64 m)
ol), 75.0 g of methanol and 50.0 g of water were charged in a four-necked glass flask, and reacted under heating to reflux at 75 to 79 ° C. for 8.5 hours. After completion of the reaction, the reaction liquid 32
4.7 g is concentrated at 50 ° C., unreacted 1,1-dimethylhydrazine, dimethyl carbonate and methanol are distilled off, and 160.4 g of ultrapure water is added to 151.3 g of a concentrate containing white crystals, The crystals were dissolved to obtain 311.7 g of a weakly alkaline, odorless, pale yellow 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate aqueous solution. According to NHCl titration, the content 52.0 wt%, 162.2 g (1.19
mol), yield 72.6%.

Example 6 Synthesis of 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate [hydrazed hydrazine] 40.1 g of hydrated hydrazine (0. 80 mol), 216.2 g (2.40 mol) of dimethyl carbonate, 50.0 g of methanol, 50.0 g of water, 5
Load in an autoclave of 00 ml, 12 ° C to 118
The temperature was increased to 1.5 ° C. for 1.5 hours. The pressure at the time of temperature rising is 3.
It rose to 8 kg / cm ² G. After that, 118-13
The reaction was carried out at 8 ° C. for 5 hours. The pressure at the end of the reaction is 42.
It was 0 kg / cm ² G. After completion of the reaction, the reaction solution 30
Concentrate 7.8 g of unreacted hydrazine hydrate, dimethyl carbonate, methanol and the like to remove light yellow 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethyl. 71.4 g of an aqueous solution of hydrazinium vicinate was obtained. Ion chromatography 7.9 wt%, 5.7 g (0.08 mo
l) The yield was 5.2%.

Example 7 Synthesis of 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium vicinate [1-methylhydrazine] 16.1-methylhydrazine 46.1 g ( 1.00 mol),
Dimethyl Carbonate 180.2 g (2.00 mo
l), 50.0 g of methanol and 50.0 g of water are charged in a 500 ml autoclave made of zirconium, and heated to 10 ° C.
To 105 ° C. in 30 minutes. The pressure at the time of temperature rise rose to 6.1 kg / cm ² G. Then 10
It reacted for 4 hours at 5-116 degreeC. The pressure at the end of the reaction rose to 45.5 kg / cm ² G during the reaction.
After completion of the reaction, 287.2 g of the reaction solution is concentrated at 60 ° C., unreacted 1-methylhydrazine, dimethyl carbonate and methanol are distilled off, and 115.2 g of ultrapure water is added to 124.6 g of the concentrate. Dissolves crystals, weakly alkaline,
239.8 g of an aqueous solution of odorless, pale yellow 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate was obtained. N
Content 28.6 wt%, 68.6 g according to HCl titration
(0.50 mol), yield 50.4%.

EXAMPLE 8 1,1,1-Trimethylhydrazinium Hydroxy by Electrolysis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate Aqueous Solution Synthesis of Deuterium The electrolytic cell used was a flow cell type electrolytic cell having one anode and two cathodes with an effective area of the electrode of 1.8 dm ² .
The electrolytic cell is divided into a cathode chamber / anode chamber / a cathode chamber by <Nafion 966> (made by DuPont) which is a fluorine resin-based cation exchange membrane, and as the electrodes, anode: DSE electrode, cathode: Ni electrode used. 61.6 obtained in Example 1
1,1,1-Trimethylhydrazinium carbonate in which the concentration of the aqueous solution of wt% 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate is adjusted to 9.9 wt% And / or 786.7 g of an aqueous solution of 1,1,1-trimethylhydrazinium bicarbonate [77.8 g (0. 1 g of 1,1,1-trimethylhydrazinium bicarbonate)]
57 mol)] was charged to the anode chamber, and 648.3 g of ultrapure water was charged to the cathode chamber. The galvanostatic electrolysis was performed for 90 minutes at an electrolysis temperature of room temperature to 35 ° C., a current density of 5.56 A / dm ² , a voltage of 4.5 to ²⁰ V. As a result of the electrolytic reaction, 65 in the anode chamber
An aqueous solution of 4.2 g was obtained, but 1,1,1-trimethylhydrazinium carbonate or 1,1,1-trimethylhydrazinium bicarbonate was below the detection limit in NHCl titration. In the cathode chamber, ammonia which is a decomposition product of 1,1,1-trimethylhydrazinium hydroxide and 1,1,1-trimethylhydrazinium hydroxide, and trimethylamine {composition: 1,1,1
-5.2% by weight of trimethylhydrazinium hydroxide
39.5 g (0.43 mol), ammonia 0.2 wt
% 1.1 g (0.07 mol), trimethylamine 0..
5 wt% 3.9 g (0.07 mol)} mixed aqueous solution 7
57.4 g were obtained. Mixture composition was determined from NHCl titration. The yield of 1,1,1-trimethylhydrazinium hydroxide in the cathode chamber was 75.1%, and the current efficiency was 88%. By vacuum concentration of the 1,1,1-trimethylhydrazinium hydroxide mixed aqueous solution in the cathode chamber,
Remove ammonia and trimethylamine, 20.3
195.0 g [39.5 g (0.43 mo) of an aqueous solution of wt% 1,1,1-trimethylhydrazinium hydroxide
l) I got]. Ammonia and trimethylamine in the 1,1,1-trimethylhydrazinium hydroxide aqueous solution were below the detection limit in ion chromatography analysis.

EXAMPLE 9 1,1,1-Trimethylhydrazinium Hydroxy by Electrolysis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate Aqueous Solution Synthesis was carried out using the same flow cell type electrolytic cell as in Example 8. 18.9 wt% 1,1,1-trimethylhydrazinium carbonate and / or 1,1 in the cathode chamber
1,0,1- trimethylhydrazinium bicarbonate aqueous solution 609.0 g [1,1, 4-trimethylhydrazinium bicarbonate as 114.9 g (0.84 mo
l)] was charged in the cathode chamber with 647.4 g of ultrapure water. Electrolytic temperature, room temperature to 35 ° C, current 0.2-0.6
A, constant voltage electrolysis was performed at a voltage of 1.5 V for 7 hours. As a result of the electrolytic reaction, 14.0 wt% 1,1,1-trimethylhydrazinium carbonate and / or 1,1,
1-trimethylhydrazinium bicarbonate aqueous solution 5
85.9 g of 82.2 g (0.60 mol) of 1,1,1-trimethylhydrazinium borate are obtained. In the cathode chamber, ammonia which is a decomposition product of 1,1,1-trimethylhydrazinium hydroxide and 1,1,1-trimethylhydrazinium hydroxide,
And trimethylamine {Composition: 1,1,1-trimethylhydrazinium hydroxide 1.8 wt% 11.9 g
(0.13 mol), ammonia 0.1 wt% 0.6 g
(0.035 mol), 0.3 wt% trimethylamine
Mixed aqueous solution of 2.0 g (0.034 mol)} 663.
5g was obtained. Mixture composition was determined from NHCl titration. The yield of 1,1,1-trimethylhydrazinium hydroxide in the cathode chamber was 15.4%. 1, in the cathode chamber
The mixed aqueous solution of 1,1-trimethylhydrazinium hydroxide is concentrated under reduced pressure to remove ammonia and trimethylamine, and 9.9 wt% of 1,1,1-trimethylhydrazinium hydroxide aqueous solution 120.3 g [11.9 g
(0.13 mol)] was obtained. Ammonia and trimethylamine in the 1,1,1-trimethylhydrazinium hydroxide aqueous solution were below the detection limit in ion chromatography analysis.

EXAMPLE 10 1,1,1-Trimethylhydrazinium Hydroxy by Electrolysis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate Aqueous Solution Synthesis was carried out using the same flow cell type electrolytic cell as in Example 8. In the anode chamber, 13.2 wt% 1,1,1-trimethylhydrazinium carbonate and / or 1,
1,81-trimethylhydrazinium bicarbonate aqueous solution 818.4 g [10,77 g (0.79 mo, as 1,1,1-trimethylhydrazinium bicarbonate)
l)] {metal impurities: Na25, Ca24, Fe10,
Ultra pure water 702.3 in the cathode chamber
I charged each g. Constant temperature electrolysis was performed at an electrolysis temperature of room temperature to 35 ° C., a current of 1.6 to 9.2 A, a voltage of 4.5 V for 2.5 hours. 633.9 g in the anode chamber as a result of the electrolytic reaction
Aqueous solution {metal impurities: Na3, Ca8, Fe1, Ni
6, 2 ppb} were obtained, but 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1
-Trimethylhydrazinium vicinate is NHC
It was below the detection limit by 1 titration. In the cathode chamber, 1, 1, 1
-Trimethylhydrazinium hydroxide, 1,1,
Ammonia and trimethylamine which are decomposition products of 1-trimethylhydrazinium hydroxide {Composition: 1, 1
1,1-Trimethylhydrazinium hydroxide 6.9
wt% 58.6 g (0.64 mol), ammonia 0.
1 wt% 0.9 g (0.055 mol), trimethylamine 0.4 wt% 3.2 g (0.055 mol)} {metal impurity: Na18. Ca14, Fe9, Ni87, C
851.6 g of a mixed solution of r1 ppb} was obtained. Mixture composition was determined from NHCl titration. 1,1, in the cathode chamber
1-trimethylhydrazinium hydroxide yield 81.
It was 0%. Ammonia and trimethylamine are distilled off by concentrating the 1,1,1-trimethylhydrazinium hydroxide mixed aqueous solution in the cathode chamber under reduced pressure, 1
317.6 g [58.6 g (0.64 wt%) of an aqueous solution of 8.5 wt% 1,1,1-trimethylhydrazinium hydroxide
mol)] is obtained. Ammonia and trimethylamine in the 1,1,1-trimethylhydrazinium hydroxide aqueous solution were below the detection limit in ion chromatography analysis.

EXAMPLE 11 1,1,1-Trimethylhydrazinium Hydroxy by Electrolysis of 1,1,1-Trimethylhydrazinium Carbonate and / or 1,1,1-Trimethylhydrazinium Bicarbonate Aqueous Solution Synthesis of Deuterium and Preparation of High Purity 1,1,1-Trimethylhydrazinium Hydroxide by Treatment with Activated Carbon Electrolysis was carried out using the same flow cell type electrolytic cell as in Example 8. 14.5 wt% 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1,1 in the anode chamber
1-trimethylhydrazinium bicarbonate aqueous solution 1
187.1 g (1.35 mo) as 267.1 g of [1,1,1-trimethylhydrazinium borate
l)] {metal impurities: Na35, Ca33, Fe14,
Ultra pure water in the cathode chamber with Ni1, Cr1 ppb} 676.0
I charged each g. Constant temperature electrolysis was performed at an electrolysis temperature of room temperature to 35 ° C., a current of 4.0 to 8.8 A, and a voltage of 4.0 V for 4.5 hours. 0.6 wt% in the anode chamber as a result of the electrolytic reaction
1,96.1 g of 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate aqueous solution [5.8 g (0.1 g of 1,1,1-trimethylhydrazinium vicinate as an aqueous solution) 0
4 mol)] {metal impurities: Na31, Ca27, Fe
3, Ni 23 and Cr 4 ppb} were obtained. In the cathode chamber,
Ammonia and trimethylamine that are decomposition products of 1,1,1-trimethylhydrazinium hydroxide and 1,1,1-trimethylhydrazinium hydroxide {Composition: 1,1,1-trimethylhydrazinium hydroxide 9.4 wt% 86.7 g (0.94 mol), ammonia 0.4 w% 3.2 g (0.19 mol), trimethylamine 1.2 wt% 11.3 g (0.19 mo
l)} {metal impurities: Na37, Ca27, Fe33,
919.4 g of a mixed solution of Ni 147 and Cr 1 ppb}
was gotten. Mixed aqueous solution composition was determined from NHCl titration. The yield of 1,1,1-trimethylhydrazinium hydroxide in the cathode chamber was 69.7%. 1, in the cathode chamber
By concentration under reduced pressure at 50 ° C., 884.4 g of 1,1-trimethylhydrazinium hydroxide mixed aqueous solution and evaporating ammonia and trimethylamine, pale yellow 19.0 wt% 1,1,1, -trimethyl Hydrazine hydroxide aqueous solution 437.8 g [83.1 g
(0.90 mol)] was obtained. Ammonia and trimethylamine in the 1,1,1-trimethylhydrazinium hydroxide aqueous solution were below the detection limit in ion chromatography analysis. Furthermore, pale yellow 19.0
393.8 g [74.8 g (0.81 mo) of an aqueous w, 1,1,1-trimethylhydrazinium hydroxide aqueous solution
l)] is treated with a column packed with 62.6 g of coal-based granular activated carbon to obtain 15.7 wt% colorless and odorless
392.2 g [61.8 g (0.67 mo) of a high purity 1,1,1-trimethylhydrazinium hydroxide aqueous solution
l) I got]. The recovery rate was 82.6%. The metal impurities in high purity 1,1,1-trimethylhydrazinium hydroxide aqueous solution are Na7, Ca5, Fe3, Ni
1, Cr 2 ppb, other impurities Cl 1 pp
m, 1,1-dimethylhydrazine 1 ppm, dimethyl carbonate 100 ppm, carbonate content 0.02%, ammonia 250 ppm, trimethylamine 50 ppm.

EXAMPLE 12 Synthesis of 1,1′-bis-β-naphthol / 1,1,1-trimethylhydrazinium hydroxide inclusion complex 8.6 g of 1,1′-bis-β-naphthol 0.03 m
(ol) and 23.4 g (0.06 m) of a 23.6 wt% aqueous solution of 1,1,1-trimethylhydrazinium hydroxide.
ol) was added to 50.0 g of methanol and heated to 50 ° C. to dissolve 1,1′-bis-β-naphthol crystals. After dissolution, by cooling to room temperature, 1,1'-
Bis-β-naphthol / 1,1,1-trimethylhydrazinium hydroxide inclusion complex crystal 2.3 g, yield 2
Isolated at 0.8%. From NMR and elemental analysis, 1,
The inclusion ratio of 1′-bis-β-naphthol / 1,1,1-trimethylhydrazinium hydroxide inclusion complex is 1,
1′-bis-β-naphthol / 1,1,1-trimethylhydrazinium hydroxide / water = 1/1 / 0.5, and the structure of 1,1,1-trimethylhydrazinium hydroxide It was confirmed.

(Inclusion complex crystal data) mp 214-215 ° C. (decomposition) IR 3400-2700 cm ^-1 (-OH) NMR (DMSO-d ₆ -CDCl ₃ ) 3.37 ppm (9 H, s, -C H) _{3) 6.16-6.87 (2H, bs,} -N H 2) 7.30-7.80 (8H, m, Ar- H) 8.03-8.40 (4H, m, Ar- H ) 8.90 (1H, s, Ar-OH) where Ar = 1,1′-bis-β-naphthol elemental analysis Anal.Calcd.forC ₂₃ H ₂₅ N ₂ O ₂ 1⁄2 H ₂ O C 74 .57 N 7.56 Found C 74.62 N 7.52

[0052]

According to the present invention, hydrated hydrazine, 1-
By reacting methyl hydrazine or 1,1-dimethyl hydrazine with dimethyl carbonate, 1,1,1,
1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate is obtained, which is then subjected to electrolysis with a cation exchange membrane as a membrane to obtain 1,1,1- Trimethylhydrazinium hydroxide can be produced. in this way,
From readily available raw materials, with a small number of steps
It has the advantage of being able to produce 1-trimethylhydrazinium hydroxide. Although 1,1,1-trimethylhydrazinium hydroxide tends to be contaminated with its decomposition products ammonia and trimethylamine, ammonia and trimethylamine are easily distilled off by concentrating the aqueous solution formed. Can be removed and further
High purity 1,1,1-trimethylhydrazinium hydroxide can be obtained by activated carbon treatment. The obtained 1,1,1-trimethylhydrazinium hydroxide is a colorless, odorless and highly pure, strongly basic compound,
It is extremely useful not only in applications as a photoresist developer, but also in the fields of surfactants, elastomers, polymerization catalysts, pharmaceuticals, agricultural chemicals, and pharmaceuticals, agricultural chemicals and functional materials useful as raw materials for amine imide intermediates.

Claims (7)

[Claim of claim] 1. It is characterized in that 1,1,1-trimethylhydrazinium carbonate and / or 1,1,1-trimethylhydrazinium bicarbonate is subjected to electrolysis using a cation exchange membrane as a diaphragm. Process for producing 1,1,1-trimethylhydrazinium hydroxide. 2. A 1,1,1-trimethylhydrazinium carbonate or 1,1,1-characterized by reacting hydrazine hydrate, 1-methylhydrazine or 1,1-dimethylhydrazine with dimethyl carbonate. Process for producing trimethylhydrazinium vicnate. 3. A 1,1,1-trimethylhydrazinium carbonate obtained by reacting hydrated hydrazine, 1-methylhydrazine or 1,1-dimethylhydrazine with dimethyl carbonate, and / or 1,1,1- It is characterized in that trimethylhydrazinium vicinate is subjected to electrolysis with a cation exchange membrane as a diaphragm 1,
Process for producing 1,1-trimethylhydrazinium hydroxide. 4. An aqueous solution of 1,1,1-trimethylhydrazinium hydroxide produced by electrolysis contains its decomposition products ammonia and trimethylamine, and further, by concentrating the aqueous solution Remove ammonia and trimethylamine, 1,1,1-
The method for producing 1,1,1-trimethylhydrazinium hydroxide according to claim 1 or 3, wherein trimethylhydrazinium hydroxide is recovered as an aqueous solution. 5. A high purity 1,1,1-trimethylhydrazinium hydroxide is recovered by treating an aqueous solution of 1,1,1-trimethylhydrazinium hydroxide with activated carbon. 1, described in 4
Process for producing 1,1-trimethylhydrazinium hydroxide. 6. The reaction of dimethyl carbonate, the temperature 70 to 120 ° C., a pressure atmospheric pressure to 50 kg / cm ² G,
The method according to claim 2 or 3, wherein the reaction is carried out for 2 to 7 hours and in the presence of a polar solvent. 7. A 1,1,1-trimethylhydrazinium hydroxide as a guest molecule, 1,1'-bis-β-
A process for producing an inclusion complex of 1,1,1-trimethylhydrazinium hydroxide, which comprises reacting naphthol as a host molecule.