JPS59116251A - Preparation of tetramethylammonium salt - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a reaction catalyst by a simple process extremely easily, by dissolving or suspending tetramethylammonium chloride in an alcohol, treating it with sulfuric acid. CONSTITUTION:Tetramethylammonium chloride is dissolved or suspended in an alcohol(preferably isopropanol or butanol), sulfuric acid is added to the solution or suspension, which is allowed to stand with stirring for 1-5hr, precipitated tetramethylammonium acidic sulfate is fitered off, washed with an alcohol, to give the desired compound shown by the formula (X<-> is HSO4<->, etc.). EFFECT:The high-purity desired compound is obtained simply and economically.

Description

Detailed Description of the Invention The present invention relates to the general formula (■): (wherein, X- is l5O4-1OH- or oaoou3
The present invention relates to a novel method for producing a tetramethylammonium salt represented by -.

More specifically, a method for producing tetramethylammonium acid sulfate (hereinafter referred to as TMAH3), which is characterized in that tetramethylammonium chloride (hereinafter referred to as TMAO) is dissolved or suspended in alcohol and then treated with sulfuric acid; Tetramethylammonium hydroxide (hereinafter referred to as TMAOH) is characterized by treating the TMAH8 as an aqueous solution with barium hydroxide.
Tetramethylammonium acetate (hereinafter referred to as
(referred to as TMAAO).

Tetramethylammonium salt represented by general formula (I) is an extremely useful substance as a reaction catalyst and a reaction reagent.

Conventionally, as a method for producing TMAI (S), US Patent No. 3.
The following method described in No. 816.5!13 (1974) is known. That is, (1) A tetraalkylammonium halide and a dialkyl sulfate are reacted to form the general formula (■) RN 0803R (II) (wherein, R is an alkyl group, and R is a lower alkyl group derived from the dialkyl sulfate used). A method of producing a quaternary salt represented by (representing a group) and hydrolyzing it in the presence of a catalyst.

(2) A quaternary salt represented by the general formula (I): R14u-Foa6aff, -(110 (wherein R1 is the same as above) by reacting a tetraalkylammonium halide with a lipophilic weak acid such as pentachlorophenol A method of manufacturing by manufacturing and treating this with sulfuric acid.

(3) Producing tetraalkylammonium hydroxide from tetraalkylammonium halide,
Then neutralize with sulfuric acid.

(4) A method of treating tetraalkylammonium iodide with hydrogen peroxide and sulfuric acid.

However, the conventional method for diagonal production requires a step to produce a different type of quaternary salt and a step to use a reaction reagent such as hydrogen peroxide, making it a complicated and uneconomical production method. be.

In view of this current situation, the present inventors have conducted extensive research to find an easy method for producing acidic sulfates, and have discovered unique properties of tetramethylammonium salts that are not found in other quaternary salts. It was my turn to complete my invention.

That is, according to the method of the present invention, acidic sulfate is precipitated as crystals by simply treating an alcoholic solution or suspension of TMAO with sulfuric acid, and the crystals can be processed into a single bird very easily by the simple process of precipitating the crystals. can be manufactured.

Furthermore, as a method for producing TMAOH, a method of treating TMAO with sodium hydroxide, potassium hydroxide, etc. in alcohol is conventionally known.

However, TMAOH produced by the conventional method of slanting contains a large amount of sodium ions and potassium ions, which often hinders the industrial use of TMAOH. A method of treating with hydroxide steel is also known as a laboratory production method, but it is difficult to use industrially because it uses expensive silver salt.

On the other hand, in the present invention, the TM obtained as above
By making AH8 into an aqueous solution and adding barium hydroxide to it, TMAOH is produced without using sodium hydroxide or potassium hydroxide.Therefore, there is no possibility that sodium or potassium ions are included.
Further, the added barium ions are removed from the reaction system as barium sulfate, but since the barium sulfate hardly dissolves in water, the obtained TMAOH contains almost no barium ions. Therefore, the TMA OH of the present invention
The manufacturing method has a great advantage over conventional methods in that the obtained TMAOH contains almost no total bending ions.

In addition, the manufacturing method of TMAA () is: J, Am,
Ohem, 8oc.

86, 2965 (1964) is known, but no method for directly producing acetate from TMAH8 has been previously known. It is a manufacturing method.

In addition, even in the conventional method described in Section 2, when TMAOH is neutralized to produce acetate, sodium ions and potassium ions are contained in TMAOH, so the TMA that can be obtained is
While AO also contains these ions and deteriorates the quality, the present invention hardly contains these metal ions and can produce high-quality acetate.

The production of TMAH8 in the present invention is carried out according to the method shown below. That is, add TMA (l) to alcohol, preferably impropatol or butanol (at this time, even if TMAO is not partially dissolved, it will not cause any inconvenience in the following operation), and then add 1 to 2 times the amount of TMAG. After adding mole, preferably equimolar amount of sulfuric acid and leaving it for 1 to 5 hours under stirring, the precipitated TMAH8 is separated from each other, washed with alcohol and dried to obtain high yield and high quality TMA, )is. Manufacture. The concentration of the sulfuric acid used is not particularly limited, or it is preferable to use concentrated sulfuric acid, since if a large amount of water is contained, precipitation of crystals will be hindered and the yield will be reduced.

In order to more advantageously produce TMAH8 using the production method of the present invention, TMAO is produced from trimethylamine and methyl chloride in an alcohol medium, and the TMAO is directly subjected to the upward sulfuric acid treatment reaction without isolation. good. In other words, alcohol as a medium is charged into the reactor,
Maintain at room temperature to 100°0, preferably 30 to 50°0,
Add trimethylamine and methyl chloride, add 1
Allow to react for ~5 hours. Then add sulfuric acid to the reaction mixture,
TMAH8 can be produced by processing in the same manner as in the case of diagonal top. The obtained TMAH3 is of sufficient irises quality as it is, or can be recrystallized from a solvent such as ethanol to obtain extremely high purity.

The production of TMAOH in the present invention is carried out according to the method shown below. That is, '['MAH8 produced according to the diagonal method was made into an aqueous solution, and TM was added under stirring.
Add barium hydroxide in an equimolar amount to AH8, and add 1 to
By leaving the solution for 5 hours and then discharging the precipitated barium sulfate, a high-yield, high-grade TMAOH aqueous solution can be obtained. If necessary, the aqueous solution can be concentrated under reduced pressure, taking care not to raise the temperature too much, to form crystals of TMAOH pentahydrate.

To this invention? The production of TMAACI is carried out according to the method shown below. That is, TMAH8 produced according to the diagonal method is made into an aqueous solution, and TMAH8 is added to the aqueous solution.
Add barium hydroxide in an equimolar amount to AH8 and acetic acid in an equimolar amount to TMAH8, and leave the mixture under stirring for 1 to 5 hours, or add TMAH8 to a water bath solution of barium hydroxide and acetic acid by reversing the order of addition. Aqueous solutions may also be added.

Then, by separating the precipitated barium sulfate from door to door, a high yield and high purity aqueous solution of TMAAO can be obtained. In addition, by concentrating the aqueous solution under reduced pressure, TM
AAO can also be produced as anhydrous crystals.

As mentioned above, the method of the present invention will be described in detail using examples of metal ions, but the present invention is not limited to these examples.

Example 1 100 ml of isopropanol was added to TMAO2L9 (1 (0.2 mol)), and 20 g of concentrated sulfuric acid was added with stirring at room temperature.
(0.2rnol) was added dropwise, and the mixture was further left under stirring for 4 hours. Then, the precipitated crystals were separated from each other, washed with improbanol, and dried to form white crystals of TMAH827,8.
I got it.

Yield: 81% The characteristic values of TMAH8 that were obtained are shown below.

Elemental analysis (04H engineering, N04S) Theoretical value (%): 028.06 H7,65N 8
．． 18 analysis value (%): 027.34 H7,95
N 7.9ONMR spectrum analysis (δ value' ppm
): (0D30D, internal standard: TMS) 3.23 (s, 12H), 4.83 (s,
IH) Example 2 n-butanol io in TMAO11y (0.1 mol).

10 g of concentrated sulfuric acid (0.1 m
ol) was added dropwise, and the mixture was further left under stirring for 4 hours. The precipitated crystals were then separated, washed with n-butanol, and dried to obtain 5 g of white crystals of TMAH813. Yield: 78.9% Example 3 An autoclave was charged with 500 ml of Impropatool, and 59 g (1 mol) of trimethylamine was dissolved therein. Then, the reaction temperature was increased to 30-50°O1 pressure was increased to 1
Methyl chloride was introduced at ~5 kFI/am and reacted for 5 hours (at this time, precipitation of gastric crystals was observed, but the sulfuric acid treatment could be carried out without any inconvenience). ), and after dissipating excess methyl chloride and bringing the pressure to normal pressure, 100 g (1 mol) of concentrated sulfuric acid was added dropwise at room temperature, and the reaction was completed by leaving the mixture under stirring for 5 hours. Next, the precipitated crystals were separated from each other, washed with isopropanol, and dried to obtain 3142 g of white crystals of TMAH (0,
83 mol) was obtained. Yield: 86% Example 4 Barium hydroxide octahydrate (purity) 3'7.9. < 0
．． TMAH820,5,7' (0.12 mol) dissolved in 30 ml of water was gradually added dropwise to a suspension of 12 mol) in 30 ml of water with stirring at room temperature, and the mixture was allowed to react for an additional 4 hours. Thereafter, the precipitated barium sulfate was washed door to door with water using Celite as a p-superior. The obtained p solution and washing solution were combined to make an 88% aqueous solution of TMAOH 1
I got 01f. Yield j 8L 5%, Ba" + concentrated jJjy
: 7 ppm Example 5 Barium hydroxide octahydrate (purity) 15.8. (0,0
5m01) and acetic acid3. 88.6 g of TMAR (
A solution of 0.05 mol) in 10 mg of water was gradually added dropwise at room temperature with stirring, and after further reaction for 6 hours, the precipitated barium sulfate was washed door to door with water using Celite as a drilling aid. The resulting p solution and washing solution were combined, concentrated under reduced pressure, and then dried to form white crystals of TMA, AO6,3.
I got 11. yield! 94.6%, concentration of Ea++:
45 ppm

Claims (1)

[Claims] 1. A method for producing tetramethylammonium acid sulfate, which comprises dissolving or suspending tetramethylammonium chloride in alcohol and then treating with sulfuric acid. 2. The method according to claim 1, wherein the tetramethylammonium chloride reaction solution obtained by reacting trimethylamine and methyl chloride in an alcohol medium is treated with sulfuric acid as it is. 5. The method according to claim 1, wherein the alcohol is inpropyl or butanol. 4. Tetramethyl ammonium chloride is dissolved or suspended in alcohol, then treated with sulfuric acid to produce tetramethylammonium acid sulfate, and the sulfate is further treated with barium hydroxide. Method for producing ammonium hydroxide. 5. The method according to claim 4, characterized in that a tetramethylammonium chloride reaction solution obtained by reacting trimethylamine and methyl chloride in an alcohol medium is treated with the ff sulfuric acid. 6 A tetramethylammonium acid sulfate is produced by dissolving or suspending tetramethylammonium chloride in alcohol, then treating with sulfuric acid, and further treating the sulfate with barium hydroxide and acetic acid. Method for producing methylammonium acetate. 7. The method according to claim 6, characterized in that the tetramethylammonium chloride reaction solution obtained by reacting trimethylamine and methyl chloride in an alcohol medium is directly treated with sulfuric acid.