JPH0262869A - Production of n-alkylated cyclic alkyleneimine - Google Patents

Abstract

PURPOSE:To industrially obtain the subject compound by using faujasite-type zeolite ion-exchanged of cation with H-ion or ammonium ion, etc., as catalyst and reacting cyclic alkyleneimine with alcohol or ether in gas phase. CONSTITUTION:Faujasite-type zeolite in which cation is ion-exchanged with hydrogen ion, ammonium ion or multivalent metallic cation (especially 2-3 valent metallic ion such as ion of Mg, Ca, Ni or Fe is preferable) is used as catalyst and cyclic alkyleneimine (e.g., pyrrolidine) is reacted with alcohol (especially <=10C aliphatic alcohol is preferable) or ether (e.g., ethylether) in gas phase to obtain N-alkylated cyclic alkyleneimine (e.g., N-methylpyrrolidine). By said method, catalyst activity and selectivity are extremely improved. Resultant compound is useful as synthetic intermediate of medicine, insecticide and accelerator of rubber, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a cyclic alkyleneimine DN-alkylated product. Specifically, the present invention relates to a method for producing an N-alkylated cyclic alkylene imine by subjecting a cyclic alkylene imine to an alkylation reaction with an alcohol or ether in the presence of a catalyst.

N-alkylated products of cyclic alkyleneimines are compounds useful as synthetic intermediates for pharmaceuticals, insecticides, rubber accelerators, and the like.

[Conventional technology]

Conventionally, various methods for tN-alkylation of cyclic alkyleneimines have been proposed, and for example, the following methods are known.

■ Using a catalyst consisting of morpholine and alcohol, nickel or cobalt, copper and titanium dioxide, 1)
A process in which the reaction is carried out at a temperature of 0 to 300[deg.] C. and a pressure of 33 to 350 atmospheres (see Belgian Patent No. bqtiobg).

■ A method of alkylation using piperazine, alcohol, and Raney nickel catalyst at a temperature of 200℃ (
J-Org, Chem, , 2/, Za6~za7
(See /9r+).

■ A method for producing N-alkyl biveridine by reacting piperidine and alcohol in the presence of an aluminum oxide catalyst (Co11. of Czechoslovak
Chemical Communications.

Vol, J,? , 4ko, 6oy ~t, t3 (t zoro g)).

(2) A method of alkylating a cyclic alkylene imine such as morpholine, piperidine, piperazine, etc. and an alcohol in the presence of a silicon dioxide catalyst containing phosphoric acid (see JP-A No. 7, No. 7).

[Problem to be solved by the invention]

However, in each of the above methods, the activity and selectivity of the catalyst were low, and the methods were not industrially satisfactory.

[Means to solve the problem]

In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive studies on a method for industrially advantageously producing N-alkylated products of cyclic alkylene imines by causing an alkylation reaction between cyclic alkylene imines and alcohols or ethers. result,
The present invention is based on the discovery that by reacting a cyclic alkylene imine with an alcohol or an ether using a specific zeolite catalyst, the activity and selectivity of the catalyst can be significantly improved and the catalyst can be fully satisfied industrially. reached.

That is, the gist of the present invention is to perform an alkylation reaction between a cyclic alkylene imine and an alcohol or an ether in the presence of a catalyst, in which at least a portion of the cation sites are hydrogen ions, ammonium ions, or polyvalent metals. A method for producing an N-alkylated product of a cyclic alkylene imine, using a faujasite-type zeolite ion-exchanged with cations and carrying out the reaction in a gas phase, K
Exists.

Hereinafter, the present invention will be explained in detail.

The cyclic alkyleneimine used as a raw material in the method of the present invention is not particularly limited, but a compound represented by the following general formula is usually used. More specific examples include propyleneimine, pyrrolidine, piperidine, piperazine, morpholine, hexamethyleneimine, and the like.

Alcohols used as the other raw material include, for example, aliphatic alcohols such as methyl alcohol, ethyl alcohol, flobyl alcohol, inpropyl alcohol, methyl alcohol, and hexyl alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol. ; Aromatic compounds such as benzyl alcohol and the like. Particularly suitable are aliphatic alcohols having a carbon number of IQ or less.

Furthermore, examples of the ether include ethers corresponding to the above-mentioned aliphatic alcohols, such as methyl ether, ethyl ether, furoyl ether, inpropyl ether, methyl ether, hexful ether, and the like.

In the method of the present invention, a 7-odiasite type zeolite in which at least a portion of its cation sites are ion-exchanged with hydrogen ions, ammonium ions, or polyvalent, for example, divalent or trivalent metal cations, is used as a catalyst. Examples of the faujasite type zeolite include X type zeolite and Y type zeolite.

In general, 7-odiasite type zeolite is available in both natural and synthetic forms containing an ion-exchangeable alkali metal such as sodium. For example, X-type zeolite whose cation site is sodium is expressed as (i thO, 2) Na2O・Al2O3”
(2-!;±θ,!r)SiOz·)rH20 [Here, y represents any number from 0 to g. ], and Y-type zeolite is similarly expressed as (/f=42) Na2
()A1203・('1.s±o,!; )Si02
・H20 [Here, y represents the number of intentions between θ and De. ].

Since the faujasite type zeolite described above in which the cation site is an alkali metal such as sodium has low catalytic activity as it is, in the present invention, at least a portion of the alkali metal ion such as sodium ion in the cation site, preferably 20 % or more, more preferably l
I.

The catalyst is made highly active by ion-exchanging SO% or more, most preferably SO% or more, with hydrogen ions, ammonium ions, or polyvalent (usually - to trivalent) metal cations.

As the exchange cation, one or more cations are selected from hydrogen ions, ammonium ions, and polyvalent metal ions (preferably divalent to trivalent metal ions). Examples of the divalent to trivalent metal ions include cations such as magnesium, calcium, strontium, barium, zinc, cadmium, lead, manganese, tin, cobalt, nickel, iron, cerium, and lanthanum.

Various known methods can be used for the above-mentioned ion exchange. For example, the faujasite-type zeolite mentioned above is ion-exchanged by immersing it in an aqueous solution of salts of exchange cations (chloride, nitrate, sulfate, organic acid salts, etc.), and after achieving a predetermined ion exchange rate, solid-liquid separation is performed. Then, the ion-exchanged zeolite, which is the separated solid content, is washed thoroughly with water and dried, and the renimine and alcohol or ether are brought into contact with each other in the gas phase in the presence of the zeolite catalyst. Perform an alkylation reaction.

In the above alkylation reaction, the reaction temperature is usually between θO and 1Ioo.
℃, preferably in the range of 2SO to 7, tO'C, and the reaction pressure is normal pressure to pressurized, usually 0. The reaction conditions range from / to IO atmospheric pressure (gauge pressure).

If the reaction temperature is less than 200°C, the reaction rate will decrease, and
If the value exceeds 00"ct-, side reactions will increase.

Further, the molar ratio of alcohol/cyclic alkyleneimine is usually in the range of l to io, preferably /, j to 5. Further, in the case of ether, it is appropriate to use half the amount of alcohol. The reaction can be carried out in a conventional gas phase catalytic reaction format, and may be a fixed bed reaction format or a fluidized bed reaction format. Space velocity (total gas amount of cyclic alkylene imine and alcohol or ether in standard state (lIhr)/
The catalyst (C)) can be varied over a wide range depending on conditions such as reaction temperature and molar ratio of alcohol/cyclic alkyleneimine, but it is usually 30 to 4 o θ hr-1, preferably 100 S-, 3,000 hr-". A space velocity within a range is adopted.If the space velocity is less than 3θhr, side reactions increase, and t4ooohr−”? - If it is exceeded, the amount of unreacted substances recovered will increase.

The generated N-alkylated cyclic alkyleneimine can be recovered and purified by a known method such as distillation.

〔Example〕

Next, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

The zeolite catalysts used in the following Examples and Comparative Examples were prepared or pretreated by the methods shown below.

(1) Catalyst/: H-X zeolite Na-X zeolite (manufactured by Union Showa Co., Ltd., Mo1e
cular 5ieve Type /3X: Nag
6C(AIOz)s+a (S 1oz)toe)
・XH20) was ion-exchanged to produce NH4-X zeolite, and then subjected to pre-calcination treatment to produce H-X zeolite.

That is, NH4C/, lt/, j-g is water, 300-
After repeating the above Na-X zeolite in the aqueous solution obtained by dissolving it in the solution, it was washed with demineralized water at room temperature, filtered,
Then, it was dried at 70.0°C for 72 hours to obtain NH,-X zeolite. Ko f'L'! was molded into particles with a diameter of /~Koryu. Then, it was fired in air at 4tOθ°C for 7 hours and then in nitrogen at 400°C for 1 hour to obtain H-X zeolite.

(2) Catalyst 2:) I-Y zeolite NH4-Y zeolite (manufactured by Union Showa Co., Ltd., Mo1
ecular 5ieve LZ-YA 2),
In the same manner as the NH,-X zeolite in (1) above, it was molded and calcined to obtain an HY zeolite.

(3) Catalyst J: Na-Y zeolite Na-Y zeolite (manufactured by Union Showa Co., Ltd., Mo1ecular 5
ieve LZ-Y! ;, 2) f, diameter l~21n1
It was molded into particles of 1 ton and fired in air at 0°C for 1 hour and then in nitrogen at 110°C for 7 hours before use.

(4) Catalyst p: H-Mordenite H-Mordenite (manufactured by Norton, USA, Zeolon/oOH) was molded and fired in the same manner as in (3) above.

(5) Catalyst j: H-L zeolite to -L zeolite (manufactured by Union Showa Co., Ltd., Mo1ec
ular 5ieve 5K-q! r) was ion-exchanged to produce NH4-L zeolite, and then subjected to pre-calcination treatment to produce H-L zeolite.

That is, NH4Cl2! ;, l, I in water 300-, and in the aqueous solution obtained above, -L zeolite'f
, 309, and then operate in the same manner as in (1) above.
First, NH4-L zeolite was used, followed by H-L zeolite.

Example-1 Quartz H reaction tube (inner diameter tsmals length lIo
otnm) was filled with 2occf of glass beads as a pre-evaporation zone for cyclic alkyleneimine and alcohol;
The lower part of the reactor was filled with the type and amount of catalyst shown in Table 7 as a reaction zone. The reaction tube was heated from the outside by an annular electric furnace in the evaporation preheating zone and the reaction zone, and the temperature was maintained at a predetermined temperature.

A reaction between pyrrolidine and methanol was carried out under the reaction conditions shown in Table 1 using a faujasite type zeolite whose cation sites were substituted with hydrogen ions as a catalyst. The gaseous reaction product containing N-methylpyrrolidine obtained in the reaction was completely condensed and collected in a trap cooled with a dry ice-methanol bath. The obtained liquid reaction product was analyzed by gas chromatography. Display the results -
Shown in l.

Table-1 Comparative Example-/ The same procedure as in Example-1 was carried out except that the types and amounts of catalysts shown in Table-2 were used. The results are shown in Table-2.

Table-2 *1) W: Catalyst amount (J), F: Total raw material supply amount (mol
/hr) *1) W: Catalyst amount (J), F: Total raw material supply amount (
(mol/hr) Example - The same procedure as in Example 7 was conducted except that the types of alcohols shown in Table 3 were used and some of the reaction conditions were changed as shown in Table 3. The results are shown in Table-3.

〔Effect of the invention〕

By the method of the present invention, an N-alkylated product of a cyclic alkylene imine can be produced from a cyclic alkylene imine and an alcohol or ether at a high conversion rate and high selectivity.

Patented gluten Mitsubishi Kasei Corporation

Claims (1)

[Claims] (1) In carrying out an alkylation reaction between a cyclic alkylene imine and an alcohol or an ether in the presence of a catalyst, the catalyst is a catalyst in which at least a portion of the cation sites are ion-exchanged with hydrogen ions, ammonium ions, or polyvalent metal cations. Using Jasite type zeolite,
A method for producing an N-alkylated product of a cyclic alkyleneimine, characterized in that the reaction is carried out in a gas phase.