JPH045263A - Production of quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a phase-transfer catalyst, etc., in high yield by using benzyl chloride readily available, tractable and having a low cost, and reacting together with tertiary amine and metal bromide (iodide) in the presence of a solvent (dispersing medium). CONSTITUTION:(A) Tertiary amine (e.g., trimethylamine) expressed by formula I (R1 to R3 are same or different alkyl, alkenyl, aralkyl or polyoxyalkylene) is reacted with (B) benzyl chloride and (C) bromide or iodide of monovalent or divalent metal (e.g., lithium bromide or sodium iodide) in the presence of a solvent or dispersing medium such as methanol or acetonitrile at from -20 deg.C to 180 deg.C, preferably 20-80 deg.C to afford a compound expressed by formula II (X is Br or I according to the reacting component C). Using molar ratio o benzyl chloride to tertiary amine is preferably 0.95-1.0.

Description

[Detailed description of the invention] Child! The present invention relates to a method for producing a 49th ammonium salt useful as a phase transfer catalyst in various reactions, a bactericidal agent, and the like.

Moxibustion Rice Summer 14 A method for producing a quaternary ammonium salt in which a benzyl group is bonded to quaternary nitrogen and whose counter anion is a chlorine atom is reported, for example, in JP-A-54-122231, in which tributylamine and benzyl chloride are Benzyltributylammonium chloride is obtained by reacting with.

However, by applying this method, the general formula (I
Even if an attempt is made to produce the quaternary ammonium salt shown in I), there are many problems.

(Rxs Rat R-: alkyl group, alkenyl group,
X represents an aralkyl group or a polyoxyalkylene group, which may be the same or different, respectively: bromine atom or iodine atom) In other words, the method of reacting a tertiary amine with benzyl bromide or benzyl iodide in the presence of a solvent is , benzyl bromide, and benzyl iodide have extremely strong lachrymatory and skin irritation properties, making them undesirable in terms of handling and work environment.Furthermore, benzyl bromide and benzyl iodide are too reactive and It is unstable, tends to generate by-products during the quaternization reaction, and is difficult to obtain and expensive.

Alternatively, a tertiary ammonium salt and benzyl chloride are reacted in the presence of a solvent to produce quaternary ammonium chloride whose counter ion is a chloride ion, and then converted to the desired counter anion using an ion exchange resin. It is possible that

However, this method is industrially disadvantageous because ion exchange treatment cannot be performed at high concentrations, so a large amount of solvent must be used for dilution, and a large-scale ion exchange column is required. Furthermore, since it requires two steps of quaternization reaction and ion exchange, it takes 9 hours, which is uneconomical in terms of equipment and the like.

In addition, similar to the above, a quaternary anion whose counter anion is a chloride ion
It has been reported that after producing IN ammonium chloride, ion exchange is performed using an alkali metal or alkaline earth metal bromide or iodide in the same solvent or a different solvent [5ynthetic C
communication.

vol, 6. p313-31-8 (I976)].

However, in this case as well, since the production is carried out in two steps: quaternization reaction and ion exchange, it is uneconomical in terms of the time and equipment required for production, which is industrially disadvantageous.

Furthermore, it is also conceivable to produce the 4I&ammonium salt, which is the object of the present invention, by using, for example, benzyl dialkylamine and alkyl bromide, without using benzyl bromide, which is difficult to handle. However, this method requires severe conditions such as high reaction temperature, and the reaction progresses extremely slowly, and the yield is also low.

The present invention aims to achieve the following: without using benzyl bromide or iodide, which are difficult to handle, in a short time and in high yield in a two-stage reaction, when the benzyl group is present and the counter anion is bromine or The purpose is to produce a quaternary ammonium salt of iodine.

The present invention provides the following (a) in the presence of a solvent or a dispersion medium.
, (b), and (c) are reacted in the coexistence of the reaction components to produce a quaternary ammonium salt of the following general formula (II), and this reaction is carried out by (e).
For example, when sodium bromide is used as a component, the reaction proceeds as shown in the following reaction formula.

(a) A tertiary R amine represented by the following general formula (I).

(b) Benzyl chloride.

(c) Bromides or iodides of monovalent or divalent metals.

N-R2...(I) R3 (In the above formula, R, R, and R are each the same or different and represent an alkyl group, an alkenyl group, an aralkyl group, or a polyoxyalkylene group, and X represents the above reaction (represents a bromine atom or an iodine atom depending on component (C)) (II) The present invention will be described in more detail below.

Specific examples of the starting material (a) tertiary amine are:
Trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, dimethylethylamine, diethylmethylamine, dimethylpropylamine, dipropylmethylamine, benzyldimethylamine, benzyldiethylamine, benzyldipropylamine, benzyldibutylamine , benzylhexylamine, benzyldioctylamine, benzyldidecylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethyloctadecenylamine, dimethyleicosenylamine , dimethyltocosenylamine, dioctylmethylamine, didecylmethylamine, didodecylmethylamine, dioctadecylmethylamine, dioctadecylmethylamine, dioctadecylmethylamine, dioctadecylmethylamine,
Dieicosenylmethylamine, dioctylmethylamine, tertiary amine obtained by adding ethylene oxide or propylene oxide alone or in combination to ammonia, monoalkyl (1 to 22 carbon atoms) amine with ethylene oxide or propylene oxide alone Tertiary amines obtained by addition with or by mixing, dialkyl (carbon number 1 to
22) Examples include tertiary amines obtained by adding ethylene oxide or propylene oxide to an amine alone or in combination.

(c) Monovalent or divalent metal bromides or iodides include lithium bromide, lithium iodide, sodium bromide, sodium iodide, potassium bromide, potassium iodide, magnesium bromide, magnesium iodide, Examples include calcium chloride, calcium iodide, barium bromide, barium iodide, zinc bromide, and zinc iodide.

In the present invention, the desired quaternary grade ammonium salt is obtained.

Here, as the solvent or dispersion medium, lower alcohols such as methanol, ethanol, isopropanol, etc.
Glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, or acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, γ-
Butyrolactone, water, etc. can be used alone or in combination of two or more. Preferably, lower alcohols, acetonitrile, N,N-dimethylformamide, γ-butyrolactone, or a mixed solvent of these and water are used.

The molar ratio of benzyl chloride to tertiary amine used is 0.
．． 1 to 2 is appropriate, preferably 0.95 to 1.0.

Also, what is the molar ratio of monovalent or divalent metal bromide or iodide to tertiary amine?

0.1 to 5 is appropriate, preferably 0.95 to 1.5
It is.

The amount of solvent used is not particularly limited, but it is usually preferably set to 10 to 80% of the total amount charged for the reaction.

The reaction can be carried out either under normal pressure or increased pressure, and if desired, it can be carried out under reduced pressure. The reaction temperature is -20~1
The temperature may be about 80°C, preferably 20 to 80°C.

The reaction method may be a batch method where the raw materials are charged all at once and reacted, a semi-batch method where a part or most of the raw materials are added continuously or intermittently and reacted, or a continuous method where the reaction is performed. You can also do it.

The reaction proceeds in a relatively short time, and the desired quaternary ammonium salt is obtained in good yield in the second stage.

Depending on the solvent used, the reaction is usually carried out in a state in which the metal bromide or iodide is suspended. In this case, most of what is suspended at the end of the reaction is metal chloride, so the P solution obtained by separating the metal chloride with P is obtained.

Depending on the application, it can be used as a product as is.

If the solvent used is inconvenient for the intended use, it can be replaced with a suitable solvent, or the solvent can be distilled off and then dried to obtain a solid product.

If a product with even higher purity is desired, the desired 49th ammonium salt can be obtained with higher purity by precipitating it from the reaction solvent or a solvent substituted for it and removing F.

According to the method of the present invention, benzyl chloride, which is easy to handle and obtain, and is inexpensive, can be used in a -stage reaction in a short time.
Moreover, a quaternary ammonium salt having a benzyl group and having a bromine or iodine atom as a counter anion can be obtained in high yield.

Example 1 185.4 g (I, 0 mole) of tributylamine and 108 g of sodium bromide were placed in a 1.500 ohm separable flask.
．． 0 g (I, 05 mol), benzyl chloride 125.2 g (
0.99 mol) and 350 g of water-containing (5%) methanol were charged.

While stirring, heat from room temperature, and after reaching 50°C
The reaction was carried out at 50-60°C for an hour. After the reaction was completed, it was cooled to room temperature, and the suspended salt was separated by filtration under pressure. As a result of analyzing the obtained P solution, the reaction rate of tributylamine was 97%, of which the selectivity to the target product benzyltributylammonium bromide was 95%.
Met. The conversion rate to benzyltributylammonium bromide based on tributylamine was 92.2%.

Example 2 The reaction and p-filtration were carried out in the same amount as in Example 1 and in the same manner as in Example 1, to obtain 650 g of P liquid and p-filtration cake. This r-filtration cake was washed with 100 g of cold methanol, and the washing liquid was combined with the P solution.

Transfer 755 g of the obtained R liquid to a 2Q separable flask, add 750 g of water, and heat at 60 to 70°C under reduced pressure.

750 g of methanol-line fishing was distilled off. 750 g of water was further added to this residual liquid, and 1.050 g of methanol-line fishing was distilled off at 60 to 70° C. under reduced pressure.

The residual liquid was cooled to 20° C. over 4 hours with stirring to precipitate crystals of benzyltributylammonium bromide. The crystals were collected by pressure filtration, washed with 200 g of ice-cold water, and dried overnight at 70 to 80°C under reduced pressure to produce 278.3 g of benzyltributylammonium bromide (tributylamine A standard yield of 78% was obtained.

The R liquid and the washing liquid were reconcentrated, and subjected to crystallization, V-filtration, washing, and drying to obtain 32 g of pencil 1-butylammonium bromide with a purity of 98%.

Comparative Example 1 Using benzyl bromide, which is difficult to handle, an attempt was made to react benzyldibutylamine with okuihibutyl in order to obtain benzyltributylammonium bromide.

That is, 219.3 g (I, 0 mol) of autoclaved prebenzyl dibutylamine of IQ, 137 g of butyl bromide
．． 0 g (I, 0 mol) and 240 g of acetonitrile were charged, and the mixture was reacted at 100 to 105° C. for 66 hours. As a result, the reaction rate of benzyldibutylamine was 97%, of which the target benzyltributylammonium bromide was obtained. Incidentally, the reaction rate of benzyldibutylamine after 4 hours of reaction was only 16%.

Comparative Example 2 A method was attempted in which benzyltributylammonium chloride was obtained from only tributylamine and benzyl chloride, and then ion exchange was performed using sodium bromide to obtain benzyltributylammonium bromide.

That is, 185.4 g (I.0 mol) of tributylamine, 125.2 g (0.99 mol) of benzyl chloride, and 342 g of methanol were placed in a 1,500 mQ separable flask.
I prepared g. While stirring, heat from room temperature to 65℃
After reaching the temperature, the reaction was continued at 65-75°C. The reaction rate was slow, and the reaction rate of tributylamine reached 97% 26 hours after the reaction temperature reached 65 °C.
Of the reacted tributylamine, 94% was converted to benzyltributylammonium chloride.

Add 18 g of water and 108 g of sodium bromide to the aqueous solution of benzyltributylammonium chloride thus obtained.
．． 0 g (I, 05 mol) was added, and an ion exchange reaction was carried out at 50 to 60° C. for 6 hours. As a result, the selectivity to benzyltributylammonium bromide, which is a product similar to benzyltributylammonium chloride, was 95%, and the conversion rate to benzyltributylammonium bromide based on the starting material tributylamine was 86.6%. Met.

Claims (1)

[Claims] 1. In the presence of a solvent or dispersion medium, (a) a tertiary amine represented by the general formula (I), ▲a numerical formula, a chemical formula, a table, etc.▼...(I) (in the formula , R_1, R_2, and R_3 are the same or different and each represents an alkyl group, an alkenyl group, an aralkyl group, or a polyoxyalkylene group) (b) benzyl chloride and (c) bromide or iodide of a monovalent or divalent metal. The general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R_1, R_2, R_3 are the same as in general formula (I), and X is a bromine atom or a bromine atom depending on the above reaction component (c). A method for producing a quaternary ammonium salt represented by (representing an iodine atom).