JPS5955858A - Preparation of bis(beta-(n,n-dimethylamino)alkyl) ether - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high yield, by reacting a bismethohalide derivative with an aliphatic monoamine or diamine compound having only a primary amino group as an amino group as a demethylating agent. CONSTITUTION:A bismethohalide compound of bis[beta-N,N-dimethylamino)alkyl]ether shown by the formula I (R and R' are 2-3C alkyl; X is halogen) is reacted with an aliphatic amine (e.g., ethylenediamine, propanediamine, butanediamine) having 40-170 deg.C boiling point at atmospheric pressure and 1-2 primary amino groups in the molecule under pressure, to give the desired compound shown by the formula II. USE:A reaction between an alcohol group and an isocyanate group, between water and the isocyanate group is promoted. Useful as a catalyst for preparing polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a bis[β-(N,N-dimethylamino)alkyl phether represented by (and R' is an alkyl group having 2 to 3 carbon atoms).

Bis(β-(N,,N-dimethylamino)alkyl phethers are industrially extremely useful compounds as catalysts for the production of polyurethane foams that promote reactions between alcohol groups and isocyanate groups and between water and isocyanate groups. It is known that there is.

In general, a method of producing a tertiary amine compound by reacting various nucleophilic reagents with a quaternary ammonium salt compound to perform a dealkylation reaction (New Experimental Chemistry Course 14 III 1)
398 (1978)) is known, and there is still a method using amines with active hydrogen as dealkylating agents (Chem, Berichte).
), 90, 395-407 (19,57)) are also widely known. Similarly, the corresponding bis[β-(N, , , A method for producing N-dimethylamino]alkyl]ether (hereinafter abbreviated as etheramine) is described in U.S. Pat. No. 3,400,157.
and Japanese Patent Publication No. 48-7411.

In U.S. Pat. No. 3,400,157, the demethylation reaction of the bismethhalide compound is carried out in an aqueous dimethylamine solution to produce the corresponding ether amine in a yield of 67%.
However, the yield cannot be said to be sufficiently high. In particular, in this process, unreacted dimethylamine (boiling point 7.4°C) added in excess to the reaction system after the completion of the reaction
It is necessary to separate and recover the reaction by-product trimethylamine (boiling point 2.9°C), but both amines have extremely low boiling points. becomes complicated. However, there are also concerns that handling large quantities of methylamines, which have an ammonia odor, could lead to pollution problems.

Japanese Patent Publication No. 4B-7411 discloses that the bismethohalide compound has a secondary or tertiary amine group in addition to a primary amine group such as aminoethylethanolamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or dipropylenetriamine. This process for producing the ether amine is characterized by carrying out the demethylation reaction under reduced pressure in a high boiling point polyamine having a boiling point of 220° C. or higher that also has an amine group. Repeated use of these high-boiling polyamines as demethylating agents is necessary to make them applicable to economical industrial processes. However, the reaction methylates the primary and secondary amine groups of these high-boiling polyamines, reducing the amount of active hydrogen in the amine groups and reducing their ability as demethylating agents, making it difficult to reuse the high-boiling polyamines. The possible number of times is greatly restricted by reaction aspects.

Aminoethylethanolamine has a small amount of active hydrogen derived from amine groups per unit weight, and high-boiling ethyleneamines such as triethylenetetramine are a mixture of compounds containing a piperazine ring, so they are classified as secondary and tertiary. It has a relatively low content of primary amine groups having many m active hydrogen groups, and the amount of active hydrogen per unit weight is also small.

Therefore, it can be said that it is a demethylating agent that is disadvantageous in terms of process economy.

Further, there are problems such as decomposition of the polyamine itself, a decrease in the recovery rate of the polyamine during the reaction, and a decrease in the content of amine groups in the polyamine.

The reaction yield of the ether amine is also 70 to 71 L:fj,
Even when compared with the case of dimethylamine, the culm quality was not improved.

In the process for producing an ether amine using the bismethonolide form as a raw material, since the bismethonolide form as a raw material and the amine as a demethylating agent are relatively expensive, it is possible to produce the ether amine at a higher yield. I'm hopeful. However, there is still a limit to its repeated use because the demethylating agent amine undergoes structural changes such as dimethylation due to reactions.

Therefore, economically advantageous demethylating agents with excellent ability to produce the ether amine per unit weight of amine are being used.

In view of these circumstances, the inventors have conducted extensive research and have found that
We have discovered that ether amines can be produced in a surprisingly high yield by reacting a bismetonolide compound with an aliphatic monoamine or diamine compound having only a primary amino group as an amine group under pressure, using a demethylating agent. The invention has been completed.

That is, the present invention provides a bismethonolide compound of bis[β-(N,N-dimethylamino)alkyl]ether represented by the general formula (2 to 3 alkyl groups, X is an atom). Bis[β-(N,N- The present invention provides a method for producing dimethylamino)alkylconidel.

The raw material bismethonolide used in the present invention is represented by the following general formula.

That is, generally bis[β-(N, N
-Dimethylamino]alkyl]ether bismethhalide compounds can be widely used as raw materials. Among these bismethohalides, bis[β
-(N,N-dimethylamino)ethyl ether bismethochloride, 1-methyl-2(N,N-dimethylamine)ethyl, 2'(N,N-dimethylamino)ethyl ether bismethochloride, bis [1-methyl-2
Examples include bismethochloride of (N,N-dimethylamino)ethyl phether.

As the aliphatic amine used in the present invention, under atmospheric pressure,
It is a compound that has a boiling point in the range of 40 to 170°C and has 1 to 2 primary amine groups in its molecule. moreover,
It is characterized in that it is an aliphatic amine that does not contain any secondary or tertiary amine groups as amine groups in its molecule, and only has -class amine groups.

The general chemical formula of the aliphatic amine is shown below.

NH2-R+ R is an alkyl group NI having 4 or more carbon atoms (
2-R'-N)12. R' is an alkylene group having 2 or more carbon atoms. Specific examples of typical compounds include butylamine, propatoolamine, ethylenediamine, propanediamine, butanediamine, and the like. Among these amine compounds, ethylenediamine, 1゜2-propanediamine,
1,3-propanediamine and 1,4-butanediamine are preferably used, and especially ethylenediamine and propanediamine have excellent ether amine production capacity per unit weight of amine and are extremely advantageous economically.

Aliphatic-grade amine compounds with a boiling point of 40°C or lower can also be used in the reaction, but the use of these low-boiling amines requires complicated recovery operations, as is the case with dimethylamine.
It requires operation at a relatively high reaction pressure, which is preferable from the viewpoint of 19. On the other hand, aliphatic-powder amine compounds with a boiling point of 170°C or higher can also be used in the reaction, but these high-boiling amines and A problem arises in the distillation separation with the ether amine,
No. 1, the production capacity of ether amine per unit weight of amine is low, which is unfavorable in terms of operation and economy.

The reaction method of the present invention basically involves filling a pressurized reactor with the raw material bismethohalide and the aliphatic-grade amine according to the present invention, and carrying out the reaction at an elevated temperature. The process consists of producing an ether amine. The amount of aliphatic-class amine added is usually 2 moles or more per mole of the bismethhalide. For example, when carrying out the reaction in a non-aqueous system, the aliphatic amine also functions as a dispersant for the bismethhalide, so it must be added at least 2 moles or more, preferably 3 moles or more. Otherwise, the dispersibility will not be good and the yield will be lower.

The upper limit of the amount of aliphatic-class amine added is not particularly limited, but an efficient amount is selected in consideration of the production efficiency of the reactor, the amount of amine recovered after use, etc.

The reaction is usually carried out without using a solvent or diluent, but it may be carried out in the presence of water or various organic diluents. When an aqueous solution of bismethohalide is used as a raw material, the reaction becomes a liquid-phase reaction using water as a solvent, which has advantages in terms of cypress production, but the coexistence of water causes noticeable acceleration of reactor corrosion. The use of water is extremely advantageous. These diluents are effective for improving the dispersibility of the bismethhalide, but the amount added is generally equal parts by weight or less relative to the bismethhalide.

The reaction of the present invention is usually carried out at a temperature of 140 to 190°C. If the temperature is 190° C. or higher, it is difficult to control the reaction temperature due to rapid reaction, resulting in a drop in yield due to decomposition of the product. Below 140°C, the reaction rate is too slow to be practical.

In the present invention, the reaction between the bismethohalide and the aliphatic amine requires sufficient contact during the reaction, and in order to prevent the aliphatic amine from distilling out of the reaction system during the reaction, It is essential to carry out the test under pressure. Although the reaction pressure varies depending on the type and amount of the aliphatic amine and diluent, and the reaction temperature, the reaction can usually be carried out at a relatively low pressure of 10 v/d or less.

In order to produce the ether amine industrially, it is necessary to repeatedly use the aliphatic amine in the reaction to improve the economic efficiency of the process. That is, after the reaction, an alkali compound is added to the reaction mixture consisting of amine hydrochloride to liberate and recover the amines.

The alkali compound used for neutralization (IX) is not particularly limited, and examples include alkali metal hydroxides and carbonates.

Usually, IJium hydroxide or potassium hydroxide is used in an aqueous solution [7 (d7), and the amount added is at least twice the mole of the raw material bismethhalide, that is, about 2.0 to
It is equivalent to 2.2 times the mole. After neutralization, the aliphatic amine and the ether amine are recovered from the mixture of amines, water, and salt by conventional separation means such as distillation, filtration, and extraction. The recovered aliphatic amine is used again in the next reaction. Repeated use of aliphatic amines as demethylating agents increases the yield of the ether amine per unit weight of amine, significantly increasing the economics of the process.

As described above, by using the aliphatic amine of the present invention as a demethylating agent, it is possible to obtain a reaction yield that far exceeds that of conventional ether amines, and further,
Even when the ether amine is used repeatedly three times, the reaction yield of the ether amine remains extremely high, and there is almost no decrease in the demethylation ability. In addition, phenomena such as a decrease in reaction activity due to removal of the amine group Wr, that is, the removal of amine groups, etc., are not observed so much with high boiling point polyamines containing a large amount of secondary or tertiary amino groups. Therefore, the aliphatic-class amine proposed in the present invention is suitable for repeated reactions and can be said to be a very advantageous demethylating agent for industrial processes.

The present invention will be further explained below with reference to Examples, but the present invention is not particularly limited thereto.

Example 1 Production of bismethochloride of bis(β-(N,N-dimethylamino)ethyl phether) In a 5-ton stainless steel electromagnetic stirring autoclave, 30
% trimethylamine aqueous solution (trimethylamine 846 ml) and bis(β-chloroethyl) ether 86 ov were charged, heated to 70° C., and reacted for 6 hours. After the reaction, excess unreacted trimethylamine was purged, and the reaction solution was analyzed. Quantitative analysis of chloride ions by Volhardt method revealed that the amount was 12.0 equivalents (theoretical amount: 12.02 equivalents). The product was bis[β-(
It was confirmed that the product was bismethochloride of N,N-dimethylamino)ethyl phether, and was being produced in a limited amount.

Production of bis[β-(N,'N-dimethylamino)ethyl phether 500ml + stainless steel electromagnetic stirring autoclay 7'
70% aqueous solution of bismethochloride of K, bis[β-(N,N-dimethylamine)ethyl phether 149r(
Bismethochloride (104.32) and n-butylamine (176v) were charged and heated at 170°C for 3.5 hours to carry out a reaction.

The pressure changes during the reaction, the highest pressure is about 6 Ktp/cl
Met. After the reaction, 67 f of aqueous sodium 48 hydroxide solution was added to the reaction mixture, and then the precipitated chloride was removed.) IJ
The waste was separated by centrifugation. Quantitative analysis of the P solution by gas chromatography revealed that 51.2 F of bis[β-(N,N-dimethylamino)ethyl ether was not obtained.

This is a yield of 7 based on bismethochloride.
I was in charge of 9.5. The product is isolated by distillation,
'I-1,-NMR analysis was performed on bis[β-(N.

It was confirmed that it was N-dimethylamino)ethyl phether.

Example 2 The bis[°β-(N,N) produced in Example 1 was placed in a 560 mt stainless steel electromagnetic stirring autoclave.

70% aqueous solution of bismethochloride of dimethylamino)ethyl phether 149f (bismethochloride 10%
4.3f) and 168v of ethylenediamine were charged and the reaction was carried out at 160°C for 5 hours. The reaction pressure changed over time as the reaction progressed, and the highest pressure was about 5 (/d. After the reaction, 48% hydroxide was obtained) IJium aqueous solution 68
2 was added, and the precipitated salt was separated by centrifugation. As a result of gas chromatography analysis of F liquid, bis(β-
(N,N-dimethylamino)ethyl phether is 58.
It was found that 69 were produced. The yield was 91.0 on the basis of bismethochloride.

Examples 3-6 In the same reactor as in Example 2, bis[β-(N.

105 bismethochlorides of N-dimethylamino]ethyl]ether and predetermined amounts of aliphatic amines shown in Table 1 were charged, and the reaction was carried out at a reaction temperature of 155 to 180°C for 2 to 8 hours. After the reaction, a 48% sodium hydroxide aqueous solution 707 was added, and the precipitated salt was separated from the furnace by centrifugation.

The F solution was quantitatively analyzed using a gas chromatograph.

The results are shown in Table 1.

Table 1 Example 7 In the same reactor as Example 2, the bis[β
-(N,N-dimethylamino]ethyl]ether bismethochloride and 1,3-propanediamine were charged in the proportions shown in Table 2, reaction temperature 170°C, reaction pressure 3.5-4
．． The reaction was carried out at ob/d for 3.5 hours, and after the reaction was completed, an aqueous solution of 48 sodium thihydroxide was added in moles 2.1 times the mole of the raw material bismethochloride (as NaOH).

Then, water was distilled off from the reaction mixture. After removing the precipitated salt by centrifugation, liquid F was distilled to separate and recover a modified mixture of 1,3-propanediamine and bis[β-(N,N-dimethylamino)ethyl phether. The recovered mixture of modified 1<3>-propanediamine was repeatedly used in the second reaction. Similar reaction and recovery operations were performed three times. The ether amine yield was calculated from the amount recovered by distillation.

The results obtained are shown in Table 2.

Table 2 ・) The 2nd and 3rd demethylation agents are a mixture of modified products (mainly N-methylated products) of 1, 3-propanediamine recovered after the first and second reactions.

Comparative Example In the same reactor as Example 2, the bis[β
Table 3 shows a 70 weight percent aqueous solution of bismethochloride of -(N,N~dimethylamino)ethyl phether and aminoethylethanolamine (boiling point 243.7°C).
Charge the amount shown, reaction temperature 170℃, reaction pressure 2~31&
/i for 3.5 hours, and after the reaction was completed, 48
A sodium hydroxide aqueous solution was added in 2.1 moles (as NaOH) of the raw material bismethochloride.

Then, water was distilled off from the reaction mixture. After removing the precipitated salts by centrifugation, the tear fluid was distilled and bis[β-(
A mixture of N,N-dimethylamino]ethyl]ether and a modified product of aminoethylethanolamine was separated and recovered. The recovered aminoethylethanolamine modified product mixture was repeatedly used in the second reaction. Similar reaction and recovery operations were performed three times. The ether amine yield was calculated from the amount recovered by distillation. The results obtained are shown in Table 3.

Table 3 ・) The second and third demethylating agents are mixtures of modified aminoethylethanolamines recovered after the first and second reactions, respectively.

Patent Applicant Toyo Soda Kogyo Co., Ltd. Procedural Amendment Fence July 15, 1980 71 Children 71 Agency Director Kazuo Nobuwakasugi 1 Matter P1 Indication 1981 Special Application No. 166597 2 Name of Invention Bis Production method of β-(N,N-dimethylamino)alkyl] ether 6 Matters to be corrected 1 Relationship with cows! 1+i Permissible phone number (585) 3ro 11 5 1-Claims” and “Detailed description of the invention” of the specification subject to amendment
Column 6 Contents of amendment (1) The claims of the specification are amended as shown in the attached sheet.

(2) The description is amended as follows.

(b) On page 4, line 6, "1 reduced pressure" is corrected to "under reduced pressure."

(B) On page 5, line 6, [...after decomposition 1 reaction...] is corrected to "...after decomposition and accompanying reaction...".

(c) Page 7, line 12 [mino)ethyl, 2〆(N, N
-J is [mino)ethyl-2'(N.

Correct as N-J.

) On page 7, line 19, ``further'' is corrected to ``that is.''

(e) Delete "propertool amine" on page 8, line 8.

7 List of attached documents (1) Claims after amendment 1 copy 2 claims + 1) Represented by the general formula (R and R' are alkyl groups having 2 to 3 carbon atoms, and X is a halogen atom) A bismethhalide compound of bis[β-(N,N-dimethylamino)alkyl]ether is used as a fat having a boiling point of 40 to 170°C under atmospheric pressure and having 1 to 2 primary amine groups in the molecule. Bis[β-(N,N
-Method for producing dimethylamino)alkyl]ether.

(2) The manufacturing method according to claim (1), wherein the aliphatic amine is butylamine, ethylenediamine, propanediamine, or butanediamine.

-331~

Claims (2)

[Claims] (1) A bismethohalide compound of bis[β-(N,N-dimethylamino)alkyl phether represented by the general formula (R and R' are alkyl groups having 2 to 3 carbon atoms, and X is a halogen atom) , a bis[β-
A method for producing (N,N-dimethylamino)alkylphether. (2) The production method according to claim (1), wherein the tl aliphatic amine is ethylenediamine, propanediamine, or butanediamine.