JP3004053B2 - Method for producing N-substituted aziridine compound and catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 【Technical field】

The present invention provides an N-substituted alkanolamine in the presence of a catalyst.
The present invention relates to a novel method and a catalyst for producing an N-substituted aziridine compound by a gas phase intramolecular dehydration reaction. N-substituted aziridine compounds are cyclic amines having a highly strained hetero three-membered ring, and have both ring-opening reactivity and reactivity as amines. It is a highly useful compound.

[Background Art]

The following methods are known as methods for producing an N-substituted aziridine compound, but each of these conventional techniques has the following problems. B) A method for producing an N-substituted aziridine by converting the N-substituted ethanolamine into a sulfate ester and then treating with a concentrated alkali to close the ring (US Pat. No. 1,177,297). In this method, since a large amount of auxiliary materials such as sulfuric acid and alkali are used, productivity is low, and in addition, inorganic salts derived from the auxiliary materials and having low utility value are produced in large amounts. B) A method of converting an N-substituted ethanolamine into an N-substituted aziridine compound by intramolecular dehydration reaction using diethoxytriphenylphosphorane (Journal of Organic Chemistry 51, (1986), 95-97). In this method, diethoxytriphenylphosphorane is very expensive, cannot be recovered and reused, and cannot be a practical production method. C) A method for producing an N-substituted aziridine by subjecting an aziridine to an addition reaction with a compound having an epoxy group such as ethylene oxide (US Pat. No. 3,166,590). In this method, an epoxy compound further causes a sequential addition reaction to the generated N-substituted aziridine. Therefore, it is necessary to use a large amount of aziridine, and it is still unavoidable to generate a by-product to which 2 to 3 moles of the epoxy compound has been added, and the yield of the desired product is poor. Usually, it is necessary to add an alkali to prevent the polymerization of aziridine, but there is a contradiction that the alkali causes polymerization of the epoxy compound. That is, in the production, the operation is performed at a compromise between safety and polymerization inhibition. D) A method for producing 1- (2-aminoethyl) aziridine by dimerizing ethyleneimine using an alkali metal catalyst (US Pat. No. 3,502,654). In this method, the catalyst is a very dangerous alkali metal, and a by-product of dimer or more of aziridine is also formed, so that the yield of the target product is relatively low. In particular, when an N-substituted aziridine compound having a functional group such as a hydroxy group, an amino group, or an acyl group in the substituent is intended, the reaction becomes complicated in any of the methods, and various methods are required. By-products are by-produced. As described above, none of the methods are completely satisfactory from the viewpoint of industrial production. An object of the present invention is to solve the above-mentioned problems and to provide a novel method for efficiently and efficiently producing an N-substituted aziridine compound from an N-substituted alkanolamine without using an auxiliary material. .

DISCLOSURE OF THE INVENTION

The present inventors have conducted intensive studies on a method for producing a novel N-substituted aziridine compound. As a result, the N-substituted aziridine compound is highly selectively N-substituted aziridine by subjecting an N-substituted ethanolamine to an intramolecular dehydration reaction in the gas phase in the presence of a catalyst. It has been found that a compound can be produced, which has led to the present invention. That is, the present invention provides a compound represented by the general formula (I): (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently one selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 4 carbon atoms. A cyclohexyl group, a phenyl group, a benzyl group, a hydroxyalkyl group having 1 to 4 carbon atoms and an aminoalkyl group having 1 to 4 carbon atoms). In the presence of a catalyst, reaction pressure 5-250 mmHg (absolute pressure), reaction temperature 300-50
General formula (II) which is intended to have a gas phase intramolecular dehydration reaction at 0 ° C (Wherein R ¹ , R ² , R ³ , R ⁴ and X are the same as in the formula (I)).
According to the present invention, even when the substituent X has an amino group or a hydroxyl group that is a reactive functional group, a side reaction is suppressed, and the N-substituted aziridine compound is highly selectively produced without changing the substituent. can do. In addition, since there is no need to use any auxiliary materials, this method is very economically advantageous. Hereinafter, the present invention will be described in detail. The present inventors have conducted intensive studies on a method for producing an N-substituted aziridine compound and found that an N-substituted aziridine compound can be produced by subjecting an N-substituted alkanolamine to a gas phase intramolecular dehydration reaction in the presence of a catalyst. The invention has been completed. Specific examples of the N-substituted alkanolamine represented by the general formula (I) used as a raw material in the present invention include amino acids such as N-methylethanolamine, N-ethylethanolamine, and N-butylethanolamine. N-substituted alkanolamine in which the group is substituted with an alkyl group; N-substituted alkanol in which the amino group is substituted with a group having a functional group such as diethanolamine, N- (2-aminoethyl) ethanolamine, N-acetylethanolamine and the like Amines; and the like. According to the method of the present invention, a corresponding N-substituted aziridine compound represented by the general formula (II) is obtained from these N-substituted alkanolamines. As the catalyst used in the present invention, a phosphorus-based catalyst or a silicon-based catalyst is suitable. As the phosphorus-based catalyst, a general formula XaPbMcOd (where X is a group selected from the group IIIA, group IVA, group VA, group I or group VIII transition metal, lanthanide and actinide elements of the periodic table) At least one selected element, P
Represents phosphorus, M represents at least one element selected from an alkali metal element and an alkaline earth metal element, and O represents oxygen. The subscripts a, b, c and d represent the ratio of the number of atoms of each element. When a = 1, b = 0.01 to 6 (preferably 0.1 to 3) and c = 0.01 to 3 (preferably 0.05 to 3). 2), and d is a numerical value determined by the values of a, b, and c and the bonding state of each constituent element). As a silicon-based catalyst, the general formula SiaMbYcOd (where S
i is silicon, M is at least one element selected from alkali metal elements and alkaline earth metal elements, Y is boron, aluminum, titanium, zirconium, tin,
O represents at least one element selected from zinc and cerium, and represents oxygen. Also, subscripts a, b, c and d
Represents the ratio of the number of atoms of each element, and when a = 1, b = 0.005-
1 (preferably 0.01 to 6), c = 0.005 to 1 (preferably 0.005 to 0.2), and d is a value determined by the values of a, b, and c and the bonding state of the constituent elements. Things are recommended. In carrying out the present invention, the reactor may be any of a fixed bed type and a fluidized bed type, but a fixed bed type is preferred. The reaction pressure can be normal, increased or reduced pressure. The raw material N-substituted ethanolamine is optionally nitrogen,
It is also possible to dilute with an inert gas such as argon,
In some cases, ammonia or water may be supplied together with the N-substituted ethanolamine for the purpose of suppressing side reactions. As a reaction condition when the reaction is carried out by diluting with an inert gas, generally, the concentration of the N-substituted ethanolamine is 1
~ 30% by volume, the reaction temperature is 300 ~ 500 ℃, more preferably 35 ~
In the range of 0 to 450 ° C, the space velocity of the source gas is 10 to 10,000 hours
-1 (STP), more preferably in the range of 50 to 5000 hr-1 (STP). If the concentration of the N-substituted ethanolamine is too high, the yield will decrease, and if it is too low, the productivity will deteriorate. If the reaction temperature is too high, carbonaceous deposits will rapidly accumulate on the catalyst, shortening the life of the catalyst, increasing the number of side reactions and reducing the yield, and is disadvantageous in terms of equipment and utility. . On the other hand, if the reaction temperature is too low, the activity becomes insufficient and the yield is reduced. If the space velocity is too low, the reactor will be large and the productivity will be low.If it is too high, the gas flow rate will be too high and the pressure loss in the catalyst layer will increase, and the conversion will not proceed smoothly because the reaction will not proceed smoothly. This leads to a decrease in yield. When the space velocity is large, the pressure loss increases and the inlet pressure increases when the space velocity is large.
It is preferable not to make it too long. However, when an inert gas or the like is used, the generated N-substituted aziridine compound may be lost due to entrainment with the inert gas. In addition, a large amount of inert gas is consumed, so that the cost becomes large. When the inert gas is recovered and recycled, the process becomes complicated and equipment cost increases. In that regard, N is substantially reduced without using an inert gas or the like.
A method in which the reaction is performed at a substituted ethanolamine concentration of 100% is preferred. The reaction conditions in this case are generally a reaction pressure of 5 to 250 mmHg (absolute pressure) and a reaction temperature of 300 to 450 mmHg.
C. and the space velocity are preferably in the range of 50 to 500 hr-1 (STP). If the reaction pressure is too low, it becomes difficult to sufficiently collect the reaction products, and the load on the pressure reducing device increases, which is disadvantageous in terms of equipment. The reaction temperature and space velocity are the same as described above. More optimal reaction conditions vary depending on the type of the starting N-substituted alkanolamine. In addition, even if the conversion of the N-substituted alkanolamine is slightly lowered, the selectivity is increased to recover and reuse the unreacted raw material, or to increase the yield of one pass without recovering the unreacted raw material. It depends on your policy. In general, the production of N-substituted alkanolamines to which the present invention is directed is a small-scale production, so the latter is adopted. Next, suitable reaction conditions for producing the N-substituted alkanolamine represented by the general formula (I) in higher yield will be described. When X in the formula (I) is an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, the reaction pressure is 10 to 250 mmHg (absolute pressure) and the reaction temperature is 300 to 450.
It is preferable to carry out a gas phase intramolecular dehydration reaction at a temperature of 50 ° C. and a space velocity of 50 to 500 hr −1 (STP). X in the formula (I) is a hydroxyalkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
In the case of the acyl group of 4, the reaction becomes complicated because this kind of N-substituted alkanolamine has at least three functional groups having high reactivity. For example, in the case of N- (2-aminoethyl) ethanolamine, piperazine is by-produced in addition to 1- (2-aminosilethyl) aziridine, which is a target product, and if the composition of the catalyst and the reaction conditions are not appropriately selected, the by-products Piperazine is produced in large quantities. Further, for example, in diethanolamine, morpholine is hardly produced by an intramolecular dehydration reaction between OH groups, but since reactivity is high, various side reactions including an intermolecular reaction are likely to occur, and 1- (2-hydroxyethyl) aziridine is obtained. Selectivity decreases. Furthermore, it is very difficult to recover the unreacted raw material because the raw material has a high boiling point and the reaction product contains various types of by-products having a boiling point close to that of the unreacted raw material. Therefore, when producing these N-substituted aziridine compounds,
It is advantageous to increase the conversion of the N-substituted alkanolamine to increase the yield in one pass. Therefore, the reaction pressure is 5
It is preferable to carry out a gas phase intramolecular dehydration reaction under the conditions of 5050 mmHg (absolute pressure), a reaction temperature of 300 to 450 ° C., and a space velocity of 50 to 500 hr-1 (STP).

[Industrial applicability]

According to the production method of the present invention, an N-substituted aziridine compound can be produced from an N-substituted alkanolamine with high selectivity. INDUSTRIAL APPLICABILITY The present invention is capable of producing a highly useful N-substituted aziridine compound with high efficiency by a novel production method, and is a very excellent production method for industrialization.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to examples. Note that N
The conversion of the substituted alkanolamine, the selectivity of the N-substituted aziridine compound and the yield were as defined below. N-substituted alkanolamine conversion = N-substituted alkanolamine consumed in reaction (mol) / N-substituted alkanolamine supplied to reactor (mol) × 100 N-substituted aziridine compound selectivity = N-substituted aziridine compound formed (mol) / N-substituted alkanolamine consumed in the reactor (mol) × 100 N-substituted aziridine compound yield = N-substituted aziridine compound produced (mol) / N-substituted alkanolamine supplied to the reactor (mol) × 100 <Preparation of catalyst > (1) Preparation of catalyst having composition of A10.9Cd0.1P0.9 168.8 g of aluminum nitrate nonahydrate and cadmium nitrate
11.8 g was dissolved in 500 ml of water, 51.9 g of 85% by weight phosphoric acid was added thereto with stirring, concentrated by heating, and dried at 120 ° C. for 12 hours. The obtained solid was crushed to 5 to 9 mesh and calcined at 1000 ° C. to obtain a catalyst having a composition of A10.9Cd0.1P0.9 in an atomic ratio excluding oxygen. (2) Preparation of a catalyst having a composition of Si1Cs0.1Ca0.05B0.1 16.3 g of cesium carbonate and 3.7 g of calcium hydroxide were added to water 5
Heat and dissolve in 00 ml, then 6.2 g boric acid and silica gel
After adding 60 g and concentrating by heating while stirring, the mixture was dried at 120 ° C. for 15 hours. The obtained solid was crushed to 5 to 9 mesh,
Sintered at 0 ° C, atomic ratio excluding oxygen, Si1Cs0.1Ca0.05B
A catalyst having a composition of 0.1 was obtained. (3) Preparation of a catalyst having a composition of Cs0.9K0.1P0.8A10.01 17.5 g of cesium nitrate, 0.56 g of potassium hydroxide and 9.2 g of 85% by weight phosphoric acid were dissolved in 300 g of water, and 60 g of silica gel was added as a carrier. Further, 0.38 g of aluminum nitrate was added, the mixture was concentrated by heating, and dried at 120 ° C. for 12 hours. 5
９9 mesh and calcined at 700 ° C for 4 hours to obtain Cs0.9K in atomic ratio excluding silicon and oxygen of the carrier silica gel.
A catalyst having a composition of 0.1P0.8A10.01 was obtained. (4) Preparation of a catalyst having a composition of Si1Ba0.1A0.1 31.5 g of barium hydroxide octahydrate and 37.5 g of aluminum nitrate nonahydrate were dissolved by heating in 500 ml of water and then silica gel
After adding 60 g and heating and concentrating while stirring, the mixture was dried at 120 ° C. for 12 hours. The obtained solid was crushed to 5 to 9 mesh and 600
The catalyst was calcined at ° C to obtain a catalyst having a composition of Si1Ba0.1A0.1 in an atomic ratio excluding oxygen. (5) Preparation of a catalyst having a composition of Mg1P0.5Na0.1 58.1 g of magnesium hydroxide and 4.0 g of sodium hydroxide are suspended in 200 ml of water, and 57.6 g of 85% by weight phosphoric acid is added. And evaporated to dryness in a water bath. This was dried in air at 120 ° C. for 12 hours, crushed to 5 to 9 mesh, and calcined at 700 ° C. for 5 hours.
A catalyst having a composition of g1P0.5Na0.1 was obtained. (6) Preparation of a catalyst having a composition of Si1Ba0.1A0.1 31.5 g of barium hydroxide octahydrate and 37.5 g of aluminum nitrate nonahydrate were dissolved by heating in 500 ml of water and then silica gel
After adding 60 g and heating and concentrating while stirring, the mixture was dried at 120 ° C. for 12 hours. The obtained solid is crushed to 5 to 9 mesh and 600 ° C.
To obtain a catalyst having a composition of Si1Ba0.1A0.1 in an atomic ratio excluding oxygen. (7) Preparation of a catalyst having a composition of Cs0.9Ba0.1P0.8 17.5 g of cesium nitrate, 3.2 g of barium hydroxide and 9.2 g of 85% by weight phosphoric acid were dissolved in 300 g of water, and 60 g of silica gel powder was added as a carrier, followed by heating. After concentration, it was dried in air at 200 ° C. for 12 hours. The obtained solid was crushed to 5 to 9 mesh,
By calcining at 0 ° C. for 4 hours, a catalyst having a composition of Cs0.9Ba0.1P0.8 was obtained at an atomic ratio excluding silicon and oxygen of the silica gel carrier. <Reaction> Example 1 A10.9Cd0.1P0.9 prepared according to the above catalyst preparation (1)
After filling 20 ml of a catalyst having the following composition into a stainless steel reaction tube having an inner diameter of 16 mm, it was immersed in a molten salt bath at 400 ° C., and a raw material gas of N-methylethanolamine: nitrogen = 5: 95 in the reaction tube by volume ratio. Was reacted at a space velocity of 4000 hr-1 (STP). The reaction product 2 hours after the start of the reaction was analyzed by gas chromatography, and the results shown in Table 1 were obtained. Examples 2 to 21 Composition of catalyst, type of raw material N-substituted alkanolamine,
The reaction was carried out and analyzed in the same manner as in Example 1 except that the raw material gas concentration, space velocity, and reaction temperature were changed to the conditions shown in Table 1, and the results shown in Table 1 were obtained. Examples 22 to 37 Composition of catalyst, type of raw material N-substituted alkanolamine,
The reaction was carried out and analyzed in the same manner as in Example 1 except that the raw material gas concentration, the space velocity, and the reaction temperature were changed to the conditions shown in Table 2, and the results shown in Table 2 were obtained. In Tables 1 and 2, Examples 4, 8, 10, 1
7, 29 and 32-37 illustrate the invention, and the other examples are for comparison.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI B01J 27/18 B01J 27/18 Z C07D 203/02 C07D 203/02 203/12 203/12 203/22 203/22 (72) Inventor Hideaki Tsugi 5-5-2-4 Nakanobu, Shinagawa-ku, Tokyo (72) Inventor Hideki Shoda 942-26-308, Rokuura-cho, Kanazawa-ku, Yokohama-shi, Kanagawa-ken (56) References JP-A-1-157952 (JP) JP-A-63-126558 (JP, A) JP-A-63-126556 (JP, A) JP-A-63-126557 (JP, A) JP-A-63-123441 (JP, A) JP-A-63-123442 (JP, A) JP-A-63-123443 (JP, A) Org. Chem. , (1986), 51 (1), p. 95-7 (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 203/02 C07D 203/08 C07D 203/12 C07D 203/22 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. The compound of the general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently one selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group, a cyclohexyl group, a phenyl group, a benzyl group, a hydroxyalkyl group having 1 to 4 carbon atoms and an aminoalkyl group having 1 to 4 carbon atoms). , In the presence of a catalyst, reaction pressure 5 to 250 mmHg (absolute pressure), reaction temperature 300 to 50
General formula (II) characterized in that a gas phase intramolecular dehydration reaction is carried out at 0 ° C. (Wherein R ¹ , R ² , R ³ , R ⁴ and X are the same as in formula (I)). 2. A gas phase intramolecular dehydration reaction under the conditions of a reaction pressure of 5 to 250 mmHg (absolute pressure), a reaction temperature of 300 to 500 ° C., and a space velocity of 50 to 500 hr-1 (STP). The described method. 3. A catalyst of the general formula XaPbMcOd (where X is a group IIIA, IVA, VA, group I-VIII transition metal, lanthanide or actinide element of the periodic table). P represents phosphorus, M represents at least one element selected from an alkali metal element and an alkaline earth metal element, O represents oxygen, and subscripts a, b, and c. And d represent the ratio of the number of atoms of each element. When a = 1, b = 0.01 to 6, and c = 0.01 to
3. The method according to claim 1 or 2, wherein d is within the range of 3, and d is a numerical value determined by the values of a, b, and c and the bonding state of each constituent element). 4. A catalyst according to the general formula SiaMbYcOd (where Si is silicon, M is at least one element selected from alkali metal elements and alkaline earth metal elements, Y is boron, aluminum, titanium, zirconium, At least one element selected from tin, zinc, and cerium, O represents oxygen, and the subscripts a, b, c, and d represent the ratio of the number of atoms of each element and b = 0.005 when a = 1. ~
1, c = 0.005 to 1, and d is a value determined by the values of a, b and c and the bonding state of the constituent elements). the method of. 5. A catalyst for use in the method according to claim 1 or 2, wherein the catalyst is of the general formula XaPbMcOd, wherein X is a group IIIA element, a group IVA element of the periodic table, At least one element selected from the group VA element, transition metal element of group I to VIII, lanthanide element and actinide element, P is phosphorus, M is selected from alkali metal element and alkaline earth metal element At least one element, O represents oxygen, and the subscripts a, b, c, and d represent the ratio of the number of atoms of each element, and when a = 1, b = 0.01 to
6, c = 0.01-3, d is a, b and c
And a value determined by the bonding state of each constituent element). 6. A catalyst for use in the method according to claim 1 or 2, wherein the catalyst is of the general formula SiaMbYcOd (where Si is silicon, M is an alkali metal element and an alkaline earth metal element). And at least one element selected from the group consisting of boron, aluminum, titanium, zirconium, tin, zinc and cerium, and O represents oxygen.
c and d represent the ratio of the number of atoms of each element, and when a = 1, b
= 0.005 to 1, c = 0.005 to 1, and d is a,
a value determined by the values of b and c and the bonding state of the constituent elements).