JPS59152352A - Preparation of bis(beta-(n,n-dimethylamino)ethyl)ether - Google Patents

Abstract

PURPOSE:To prepare the titled compound by reacting a bismethohalide compound of bis[beta-(N,N-dimethylamino)ethyl] ether with an aliphatic amine, subjecting the reaction mixture to the treatment with an alkali metal hydroxide and phase separation, and using the amine repeatedly to the reaction. CONSTITUTION:Bis[beta-(N,N-dimethylamino)ethyl] ether is prepared by reacting a bismethohalide compound of bis[beta-(N,N-dimethylamino)ethyl] ether of formula (X is halogen) with an aliphatic amine as a demethylation agent. In the above process, the reaction liquid is separated into the upper and the lower layers, and each layer is recovered separately. An alkali metal hydroxide is added to the lower layer liquid to recover the aliphatic amine, which is reused in the above reaction. The amount of the alkali metal hydroxide is 10-55wt% based on the water in the lower layer liquid. The objective compound can be recovered from the upper layer liquid. EFFECT:The process is simple and has excellent operational characteristics, and the yield of the objective compound can be maintained at a high level even if the amine is used repeatedly.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing bis[β-(N,N-dimethylaminone ethyl]ether).

More specifically, bis[β-(N,N-dimethylamino]
Bis[β-(
In producing N,N-dimethylaminoethyl]ether (hereinafter abbreviated as ether amine), ether amine is industrially produced by repeatedly using the aliphatic amine recovered from the reaction solution. Regarding the method.

Generally, a method for producing a corresponding tertiary amine compound by reacting a quaternary ammonium salt compound with a nucleophilic reagent to perform a dealkylation reaction (New Experimental Chemistry Course 14 [139
8 (1978) is publicly known. In addition, the bismetino・
A method for producing the corresponding ether amine by demethylation reaction of a ride compound is disclosed in US Pat.

Japanese Patent Publication No. 48-7411 discloses a process for producing an ether amine by subjecting the bismethohalide to a demethylation reaction in the presence of a high-boiling polyamine having 7 primary amide groups having a boiling point of 220° C. or higher. The publication states that the amount of high-boiling polyamines such as aminoethylethanolamine and triethylenetetramine required to produce 1 kg of the desired ether amine is 2.6 to 3.5 units. However, it is economically disadvantageous to use large amounts of these expensive polyamines. 1. The present inventors reacted an aliphatic amine having a boiling point of 40 to 170°C under atmospheric pressure with the bismethochloride to produce an ether amine, using the aliphatic amine as a demethylating agent. An application has already been filed for a method of recovering the product after the reaction and using it repeatedly.

That is, after the reaction, an alkali compound in an amount necessary to neutralize the hydrochloric acid is added to the reaction mixture consisting of the hydrochloride of the amine, and the amines are completely liberated. Mainly amines after neutralization,
Water is distilled off from a mixture of water and salt.

After removing the precipitated salt by centrifugation, the ν liquid is distilled to separate and recover the aliphatic amine from the ether amine.

By repeatedly using the aliphatic amine recovered by such a method, the economic efficiency of the ether amine production process is increased.

The above-mentioned aliphatic amine recovery method involves processing the neutralized reaction solution through a multi-stage separation operation of distillation-centrifugation-distillation, and is an extremely complicated separation and recovery method. Furthermore, the process is not necessarily advantageous in terms of operation since it is complicated to handle the slurry containing solid salts. If the aliphatic amine used does not form an azeotrope with water,
As described above, it is possible to selectively remove water from the neutralized reaction solution by distillation, and further recover the aliphatic amine by desalting and distillation. However, when an aliphatic amine that forms an azeotrope with water, such as ethylenediamine, is used as a demethylating agent, water cannot be selectively removed by normal atmospheric distillation. That is, depending on the type of aliphatic amine, it is difficult to separate and recover the aliphatic amine from water or salt by a method consisting of a series of operations of distillation dehydration, centrifugation desalination, and distillation as described above.

The raw material bismethohalide is reacted with an aliphatic amine having a boiling point of 40 to 170°C under atmospheric pressure and having a -class amino group, and the aliphatic amine recovered from the reaction solution is repeatedly used to produce an ether amine. In the manufacturing process, the production process does not depend on the type of aliphatic amine (and even when the aliphatic amine of any chemical structure is used as a demethylating agent, it is possible to use a very simple aliphatic amine that is universally applicable. Separation and recovery of this is strongly desired.

In particular, it is strongly desired to establish an industrial manufacturing process for ether amines that has a separation and recovery process that is simple and easy to operate, does not require special separation equipment, is advantageous in terms of equipment, and has excellent economic efficiency. .

In view of these circumstances, the present inventors have conducted extensive research and have found that when a pismetnolide compound is reacted with an aliphatic amine having a primary or secondary amino group, a reaction solution separated into two layers, upper and lower, is obtained. A new fact was discovered that the target product, ether amine, can be recovered from the upper layer, and the aliphatic amine, a demethylating agent, can be recovered from the lower layer.

Furthermore, we discovered that if aliphatic amines are recovered from the lower layer and treated with an alkali metal hydroxide, the recovered aliphatic amines can be reused as they are for the reaction with bismethohalides. Based on this, the present invention was completed.

That is, the present invention provides bis[β-(N, N
-dimethylaminophethyl]ether by the reaction of bismethhalide compound with aliphatic amine, bis[β-(
When producing N,N-dimethylamino)ethyl ether, (a) a reaction solution obtained by reacting the bismethhalide compound with an aliphatic amine having a primary or secondary amino group, which is divided into upper and lower layers; Separate and collect the upper layer liquid and lower layer liquid from each, (b) 10% of the amount of water in the lower layer liquid.
Adding alkali metal hydroxide to the lower layer solution to a concentration of ~55% by weight to recover the aliphatic amine, and (C) further reusing the recovered aliphatic amine for reaction with the bismethhalide compound. The present invention provides a method for producing bis[β-(N,N-dimethylamino]ethyl]ether consisting of the following.

The raw material bismethohalide used in the present invention is a bismethohalide compound represented by the following general formula (or a halogen atom, that is, bis[β-(N,N-dimethylaminone ethyl phether); Among bismethohalides, bismethochloride and bismethobromide are widely used as raw materials due to economical efficiency and availability of raw materials.

The aliphatic amine used in the present invention is not particularly limited as long as it has a primary or secondary amino group in the molecule. Among these aliphatic amines having active water systems derived from amine groups, 40 to 170
Compounds that have a boiling point in the range of °C and have one or two primary amino groups in the molecule are extremely useful from the viewpoint of reaction yield and economy, as they produce ether amines in high yield. It is an aliphatic amine.

Specific examples of representative compounds include n-propylamine, butylamine, and ethylenediamine.

Propanediamine, butanediamine, etc. are preferably used. In particular, ethylenediamine and propanediamine are used as extremely useful aliphatic amines for the production process of the present invention because they have excellent ether amine production capacity per unit weight of amine and are easily available.

The ether amine production process in the present invention basically consists of a step of reacting a raw material bismethohalide with an aliphatic amine as a demethylating agent, and a step of reacting the aliphatic amine from the reaction solution to be reused as a demethylating agent. The process consists of separating and collecting the

The reaction method in the reaction step is not particularly limited, and is usually carried out by the method shown below.

That is, the reaction between bismethhalide and aliphatic amine is as follows:
It is carried out at a temperature of 100 to 190° C. under normal pressure or increased pressure. When using an aliphatic amine with a relatively low boiling point,
To prevent aliphatic amine from escaping out of the reaction system, under pressure,
The reaction is carried out at elevated temperature. Furthermore, when an aliphatic amine having a relatively high boiling point is used, the reaction may be carried out under reflux cooling at normal pressure. The amount of aliphatic amine added is usually 2 mol or more per 1 mol of the bismethonide compound. The upper limit of the amount of aliphatic amine added is not particularly limited, but an efficient amount is selected in consideration of the production efficiency of the reactor and the recovery burden associated with the amount of aliphatic amine recovered after use. .

The aliphatic amine not only acts as a demethylating agent for the bismethohalide, but also functions as a diluting and dispersing agent for improving the dispersibility of the bismethhalide.

Therefore, it is not necessarily necessary to newly add a diluting dispersant such as an organic solvent to the reaction system.

As described in Japanese Patent Publication No. 4B-7411, the reaction is generally carried out in a non-aqueous system using an aliphatic amine as a diluting and dispersing agent or in a system in which glycol ethers are added as a diluent. .

Since water is used as a solvent in the process of producing the raw material bismethohalide, water accompanying the raw material is introduced into the reaction system of this process.
There is no problem in reacting with an aliphatic amine in a system using water as a diluent. Since the use of a diluent such as water is not particularly advantageous in terms of ether amine yield and reactor efficiency, it is preferable that the amount added is equal to or less than an equal part by weight to the bismethohalide. In order to produce the same, it is important to recover the aliphatic amine from the reaction solution obtained by the above-mentioned reaction and use it in repeated reactions to improve the economic efficiency of the process.

Reaction between an aqueous solution of bismethhalide and an aliphatic amine, and reaction between a solid bismethhalide and an aliphatic amine,
Regardless of the reaction method, the liquid after the reaction is separated into two layers: upper and lower. The method for separating and recovering aliphatic demine according to the present invention consists of separating and recovering an upper layer liquid and a lower layer liquid from a reaction liquid separated into two layers, and then performing the following treatments.

That is, the upper layer liquid mainly consisting of ether amine is distilled as it is to obtain ether amine as a product. that time,
Since the aliphatic amine partially dissolved in the ether amine layer is also recovered, the recovered material can be used repeatedly as a demethylating agent.

On the other hand, most of the aliphatic amines exist in the lower liquid in the free state and in the form of hydrohalide salts. To this lower layer liquid, an alkali metal hydroxide is added (and
First, a neutralization reaction occurs and free amines are produced. ]・After neutralizing the hydrologonic acid, add the alkali metal hydroxide so that the alkali metal hydroxide concentration is 10 to 55% by weight, preferably 20 to 52% by weight, based on the amount of water in the liquid. do. The liquid thus treated is separated into a slurry-like lower layer containing solids such as neutral salts and a supernatant liquid consisting of free amines. This liquid phase streak containing amines is separated and recovered from the same phase of <H) to obtain a recovered aliphatic amine.

Although the recovered aliphatic amine contains various amines produced by side reactions and small amounts of inorganic compounds, the recovered aliphatic amine can be reused as is for the reaction with the bismethhalide compound. be.

The alkali metal hydroxide used in the present invention is not particularly limited, but sodium hydroxide and potassium hydroxide are usually used in the form of solid or aqueous solution. In order to minimize the amount of water introduced into the system, it is preferable to use solid alkali metal hydroxides. After neutralization, the concentration of the alkali metal hydroxide that is further added is defined as follows.

Alkali metal hydroxide concentration = -C--x100
%A+B0C A: Weight of water in the lower liquid after ether amine production reaction B: Weight of water produced by neutralization reaction C: Weight of alkali metal hydroxide present in the system Alkali metal water in the system When the oxide concentration is 10% by weight or less, neutral salts are still dissolved in the recovered aliphatic amine liquid, and desalting from the recovered aliphatic amine layer is not sufficient. Further, if the aliphatic amine mixture recovered under such conditions is repeatedly used as a demethylating agent as it is, the ether amine yield will decrease, making it undesirable as a demethylating agent. Addition of alkali metal hydroxide to a concentration of 55 wt. It only causes economic loss.

The operating conditions for adding the alkali metal hydroxide to the lower layer liquid and performing the stirring treatment are not particularly limited, but the following conditions are preferably selected.

That is, the treatment temperature is 20°C or higher and lower than the boiling point of the aliphatic amine, preferably 40 to 120°C. The higher the treatment temperature, the shorter the time required to complete the treatment, and the more efficient the lower layer liquid can be treated. When the treatment is carried out in a temperature range of 40 to 120° C., the treatment is usually completed in 0.5 to 5 hours, and a slurry-like solid phase containing neutral salts and the like is precipitated. After standing still, the supernatant liquid is separated from the uniform solid phase of the slurry and recovered, and the amines present in the lower layer can be recovered almost quantitatively. Furthermore, the same phase portion and the liquid phase portion may be separated by centrifugation. Even if the liquid recovered only by such a phase separation operation is repeatedly used as a demethylating agent, ether amine can still be produced in high yield.

As described above, aliphatic amines recovered by a very simple separation procedure consisting of a combination of alkali metal hydroxide treatment of the ether amine production reaction solution and phase separation operation are repeatedly used as a demethylating agent. Can be used.

The ether amine production process of the present invention not only greatly improves operability, but also does not require special equipment; in other words, it is possible to industrially produce ether amines using general-purpose equipment, and it is extremely efficient in terms of equipment. This can be said to be a useful method. Further, even if the aliphatic amines recovered by the method according to the present invention are repeatedly used for reaction with bismethohalides, ether amines can be produced in high yield. That is, the method according to the present invention can produce bis[β-(N
, N-dimethylaminophethyl] ether can be said to be an industrial manufacturing process.

Hereinafter, the present invention will be further explained with reference to examples, but the present invention is not particularly limited by these examples.

Example 1 Production of bismethochloride of bis[β-(N,N-dimethylamino)ethyl]ether In a stainless steel electromagnetic stirring autoclave, 30
% trimethylamine aqueous solution 2,820p (trimethylamine 8469) and bis[β-chloroethyl)ether 8
60? was charged, heated to 7oC, and reacted for 6 hours. After the reaction, excess unreacted trimethylamine was purged, and the reaction solution was analyzed. Quantitative analysis of chloride ions using the Volhardt method revealed that the number of chloride ions was 12.0 (theoretical number 1)
2.02 was normal. 1H-NMR of the reaction solution and "
O-NMR analysis revealed that the product was bis[β-(N,N-
It was confirmed that it was bismethochloride of dimethylamino)ethyl ether and was being produced at a constant rate.

Production of bis[β-(N,N-dimethylamino)ethyl]ether 51 Into a stainless steel electromagnetic stirring autoclave,
70% aqueous solution of bismethochloride in β-(N,N-dimethylaminone ethyl ether 1, 2 5 8 F
(bismethochloride 8 8 0.6 f ) and ethylenediamine 1. 80 Of was charged, and the reaction was carried out for 6 hours at a reaction temperature of 150° C. and a reaction pressure of 2.8 to 55 kg/2. After the reaction was completed, the reaction solution was cooled to room temperature and transferred to a 51-separatory funnel. The reaction liquid separated into two uniform upper and lower layers is separated into upper layer liquid 7501 and lower layer g2, 3.
17r was recovered.

As a result of gas chromatographic analysis of the upper layer liquid, the presence of ether amine 4692 was confirmed. The collected upper layer liquid was distilled and separated into a low boiling point mixture with a boiling point of 140°C or less and an ether amine (boiling point of 190°C).

The lower layer liquid was transferred to a glass four-tube flask equipped with a stirrer and a reflux condenser, solid sodium hydroxide 6207 was added, and the mixture was stirred at a temperature of 80 to 90°C for 4 hours. Supernatant liquid from the solution treated with sodium hydroxide 1. 8 2 O
r was collected. As a result of gas chromatography analysis of the supernatant, ether amine was found to be 19.8? , ethylenediamine, and N-methylated ethylenediamine (hereinafter abbreviated as ethylenediamine modified product) 1,650 r were confirmed.

As described above (250 liters of the low boiling point mixture recovered from the upper layer liquid and 1.8 2011 total of the supernatant liquid recovered from the lower layer liquid were subjected to demethylation in the second ether amine production reaction). The same recovery operation was performed and the reaction was repeated four times under the same conditions as the first time.

The etheramine yield was calculated by subtracting the amount of etheramine carried into the reaction system together with the ethylenediamine modified mixture of the demethylating agent from the amount of etheramine produced in the reaction solution. Ethylenediamine was not newly added, and the ethylenediamine recovered from the upper and lower layers was used repeatedly.

The results are shown in Table 1.

Table 1 Example 2 In the same reactor as in Example 1, an 85% aqueous solution of bismethochloride of bis[β-(N,N-dimethylamino)ethyl]ether q 2 t 7 f (bismethohalide 78A7r) was added. and 1,3-propanediamine 1.550
t, reaction temperature 170℃9 reaction pressure 15-4.5
The reaction was carried out for 4 hours at 7 am'' kg. After the reaction was completed, it was cooled to room temperature, and the reaction solution was transferred to a separating funnel.

Separate the reaction liquid into upper and lower two layers, and remove the upper layer liquid 66.
0? , 1.794 f of lower liquid was collected. As a result of gas chromatographic analysis of the upper layer liquid, ether amine 4271
The existence of was recognized. The lower layer liquid was transferred to a glass 4-tube flask equipped with a stirrer and a reflux condenser, and solid sodium hydroxide 351? was added thereto, and the mixture was stirred for 5 hours at a temperature of 60 to 80°C.

After the treated solution was allowed to stand still, 1.46 Of of supernatant liquid was collected.

As a result of gas chromatographic analysis of the supernatant, the presence of 1.570 t of a mixture of etheramine 189,1.5-propanediamine and 70N-methylated product was observed. For the second etheramine production reaction, 1.57 mL of the 1,6-propanediamine modified mixture recovered from the lower layer liquid was used.
1,3-propanediamine 200f was newly added to the supernatant liquid 1.5102 containing 09 and used as a demethylating agent.

In the second and subsequent reactions, the same separation and recovery operation was carried out, and 200 f of 1,3-propanediamine was added to the resulting lower layer treated solution, which was then used as the demethylating agent in the next reaction.

The 1,3-propanediamine modified mixture was not recovered from the upper layer liquid after the etheramine production reaction, nor was P+ excreted.

The ether amine yield was calculated in the same manner as in Example 1. Table 2 shows the results of repeating the reaction four times.

Table 2 Comparative Example 1 A 70% aqueous solution of bismethochloride of bis[β-(N,N-dimethylamino)ethyl]ether 74f>51 (bismethochloride sz
z, 4F) and ethylenediamine 1,08 Of were charged, and reaction was carried out at reaction source #160°C, 9 reaction pressure 55 to 4.5, and 9/me 2 for 6 hours.

After the reaction was completed, the reaction solution was cooled to room temperature and transferred to a separating funnel. The reaction liquid separated into upper and lower two layers is separated, and the upper layer liquid 435? and 1.375 f of lower layer liquid were collected. As a result of gas chromatographic analysis of the upper layer liquid, the presence of ether amine 277.79 was observed. The recovered upper layer liquid is separated by distillation to form a low boiling point mixture 155? and ether amine. The lower layer liquid was transferred to a glass four-tube flask equipped with a stirrer and a reflux condenser, solid sodium hydroxide 1791 was added thereto, and the mixture was stirred at a temperature of 60 to 90°C for 4 hours. After standing still, supernatant liquid 1.245? was recovered. As a result of gas chromatographic analysis of this supernatant, the presence of a mixture of etheramine 11.65', ethylenediamine/and 70N-methylated modified product 9972 was observed.

As mentioned above, 155v of a low boiling point mixture with a boiling point of 140°C or less recovered from the upper layer liquid and 1 and 2 supernatant liquids recovered from the lower layer liquid.
45'r, a total of 1.40 Of, was used as the demethylating agent in the second ether amine production reaction.

For the upper layer liquid and lower layer liquid after the ether amine production reaction,
A similar separation and recovery operation was carried out, and the reaction was repeated five times using the demethylating agent recovered from the reaction solutions of the upper and lower two layers. The ether amine yield was calculated in the same manner as in Example 1.

The results of repeated reactions are shown in Table 3.

Table 5 Patent Applicant Toyo Soda Kogyo Co., Ltd. Procedural Amendment July 15, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1 Indication of Case 1989 Patent Application No. 22874 2 Name of Invention Bis[β-(N , N-dimethylamino)ethyl] ether production method 6. Relationship with the case of the person making the amendment 6. The patent applicant's description of the contents of the 6th amendment in column ``Detailed Description of the Invention'' of the specification subject to the 5th amendment is as follows: Correct to.

Page Line Before correction After correction 8 2 Divided Divided 1a 20 2,050g2.070921 6
The reaction is also the reaction is

Claims (1)

[Claims] (1) Bis [β-(N, N
-di) If lyamino) ethyl] ether by the reaction of bismethhalide compound and aliphatic amine, bis[β-
When producing (N,N-dimethylamino J ethyl) ether, (aJ) a reaction divided into upper and lower layers obtained by the reaction of the bismethohalide compound and an aliphatic amine having 7 primary or secondary amide groups. Separate and collect the upper layer liquid and lower layer liquid from the liquid, (b) 10 to 55% by weight based on the amount of water in the lower layer liquid.
(c) recovering the aliphatic amine by adding an alkali metal hydroxide to the lower liquid to reduce the hindrance of the reaction; (c) further reusing the recovered aliphatic amine for reaction with the bismethohide body A method for producing bis[β-(N,N-dimethylamino)ethyl]ether. (2+) The production according to claim (1), wherein the aliphatic amine has a boiling point of 40 to 170°C under atmospheric pressure and has one or two primary amino groups in the molecule. (3) The production method according to claim (1) or (2), wherein the aliphatic amine, globilamine, butylamine, ethylenediamine, propanediamine or butanediamine is used. (4) Alkali metal hydroxide powder The manufacturing method according to claim (1), wherein sodium hydroxide or potassium hydroxide is used.