JP3228695B2 - Method for selecting solid catalyst for etherification reaction and method for producing ether compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for selecting a solid catalyst for an etherification reaction and a method for producing an ether compound.

[0002]

2. Description of the Related Art

[0003]

Embedded image

Carboxymethoxysuccinic acid (C)
It is known that biodegradable salts (especially sodium salts) of MOS) are useful as phosphorus-free detergent builders, and that this compound is obtained by reacting maleic anhydride with glycolic acid (chemicals). -Abstract, 75, 89458 (1971)). This reaction is a homogeneous reaction using water-soluble calcium hydroxide (Ca (OH) ₂ ) as a catalyst.Since the product is a calcium salt, sodium carbonate (Na ₂ CO ₃ ) To precipitate calcium carbonate (CaCO ₃ ) and to separate from the target CMOS sodium salt by filtration. In addition, the above-mentioned literature describes that a hydroxide of zinc, strontium, barium and magnesium can be used instead of calcium hydroxide.

In the same homogeneous reaction as described above, it has been reported that a lanthanoid-based ion can be used as a catalyst instead of calcium ion (JC).
hem. Soc. Dalton Trans. , 272
3-2728 (1988)). That is, by reacting sodium glycolate and disodium maleate in an aqueous medium in the presence of lanthanum trichloride (LaCl ₃ ),
It is said that a lanthanum salt of CMOS can be obtained. Therefore, in order to obtain a target sodium salt of CMOS, it is necessary to separate lanthanum ions from reaction products using an ion exchange resin or the like.

As described above, since the conventional method is a homogeneous reaction, a step of separating calcium ions, lanthanum ions and the like after the completion of the reaction is essential. However, if such a separation operation is performed, the number of production steps is increased, and the production cost is increased. Therefore, it is desirable to omit such a step relating to the separation of the used catalyst in industrial practice. The present inventors have already solved the inevitable drawbacks of the conventional homogeneous reaction as described above, and have been able to produce an ether compound such as CMOS by a simple method without a special step relating to catalyst separation. Examples of the solid catalyst that can be used include rare earth oxides, rare earth phosphates (excluding lanthanum phosphates), rare earth phosphonates, and rare earth elements on a resin base having a phosphate group. , A rare earth hydroxide (I), a partially dehydrated product of the above (I), a compound (II) in which a part of the hydroxyl group of the above (I) is substituted with a phosphoric acid group, and An application has been made for a solid catalyst for an etherification reaction comprising at least one selected from the group consisting of the partial dehydrates of the above (II) (Japanese Patent Application Nos. 8-226298 and 8-298997). .

[0007]

In the search for a novel solid catalyst used in the production of ether compounds, the correlation between the catalytic activity and the chemical structure of the catalyst has not been sufficiently elucidated so far. It was necessary to obtain a compound having a structure as a solid catalyst and actually conduct an experiment for examining the presence or absence of its catalytic activity. Therefore, it has been cumbersome and very difficult to find a novel solid catalyst having high catalytic activity from a large number of compounds. As a means for predicting whether a chemical reaction proceeds, Fukui et al.'S Frontier Electron Theory is famous. This is a theory that uses molecular orbitals to clarify where and how quickly a chemical reaction of a molecule occurs in a molecule, and is currently used to predict various chemical reactions. .

Therefore, one of the objects of the present invention is to provide a solid catalyst capable of performing an etherification reaction simply and efficiently by a molecular orbital calculation without performing complicated experiments.
It is to provide a method of selecting . Another object of the present invention is a method for producing a corresponding ether compound simply and efficiently by reacting an organic compound having a hydroxyl group with an unsaturated carboxylic acid compound or an epoxy compound in the presence of the solid catalyst. Is to provide.

[0009]

Means for Solving the Problems The present inventors have studied diligently.
As a result, the metal atom and the non-metal bonded to this metal atom
Attention to the molecular orbitals of metal compounds with atoms
And the direction of the molecular orbitals, the electronic state, etc.
That there is a strong correlation between the catalytic activity of
Upon seeing the present invention, the present invention was completed. That is,
Solid catalyst for light etherification reactionEvaluation methodIs a metal atom
And a non-metallic atom bound to the metal atom
(Excluding lanthanum phosphate) as an essential component
And the following production method (1)Catalyst usedEvaluation methodso
And the molecular orbital of the metal compoundAsk for, The metal source
Lowest free orbit on the child(LUMO)And on the non-metallic atom
Highest occupied orbit(HOMO) and the next occupied orbit (H
OMO ^-1 )And comprising the aboveLowest skyOrbit(LUMO)
When,SaidSupreme occupationOrbit(HOMO) or its next occupation
Orbit (HOMO ^-1 )OneWhenHas directionMoney
Select a genus compound. Production method (1): having a hydroxyl group
Reacting an organic compound with an unsaturated carboxylic acid compound
Production of ether compoundsLaw

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The solid catalyst for an etherification reaction of the present invention comprises a metal compound (excluding lanthanum phosphate) as an essential component, and is used in a method for producing an ether compound described below. Wherein the metal compound has a metal atom and a non-metal atom bonded to the metal atom.

The metal atom is not particularly limited, and may be any of groups 1A to 7A, 8 and 1B to 7 in the long-term periodic table.
Any atom belonging to Group B may be used. Representative examples of metal atoms include rare earth elements. In addition,
Rare earth elements include lanthanum, cerium, praseodymium,
Lanthanoid elements such as neodymium, scandium,
Means yttrium. Of these, lanthanum is particularly preferably used.

The nonmetallic atom is not particularly limited as long as it binds to a metal atom. Representative examples of the nonmetallic atom include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and oxygen atoms. , A sulfur atom, a nitrogen atom and the like.

The metal compound has a specific molecular orbital. The molecular orbital calculation is performed, and the calculation result is defined as described later in detail. Although the calculation of the molecular orbital is preferably performed on the metal compound itself,
For example, in a metal compound having a crystal structure such as YPO ₄ , Y ₂ O ₃ , La ₂ O ₃ which is not a structure in which the crystal structures are individually separated but has a connected crystal structure such as a straight line or a network, the repeating unit There a continuous model structure obtained by adding a modified hydrogen atom in the structure of <br/> end of a truncated crystal structure, intends rows molecular orbital calculation is regarded as a metal compound. For example, YPO ₄ , Y ₂
For O ₃ and La ₂ O ₃ , model structures shown in Table 2 are selected, and molecular orbital calculations are performed using these structures as metal compounds. The molecular orbital calculation is performed on the most stable structure (most stable structure) of the metal compound. The most stable structure is selected because in the transition state of the reaction, when the catalyst and the reactive molecule approach, the energy changes together with their respective steric structures, but the shape of the molecular orbital is considered to be basically unchanged. It is. In order to identify the most stable structure,
You may specify together using molecular force field calculation and molecular dynamics calculation.

The method for calculating the molecular orbital of the metal compound is not particularly limited.
It is selected from the semi-empirical molecular orbital method and the inexperienced molecular orbital method. Above all, calculation using the ab initio molecular orbital method is preferable because calculation accuracy is high and calculation can be performed for many metal atoms. Examples of the ab initio molecular orbital method include Gaussian, HONDO, SPARTAN, and ADF. Although the calculation results of molecular orbitals may be analyzed as they are, usually, they are converted into molecular orbital images using visualization software such as Cerius2, Quanta, and InsightII. The lowest unoccupied orbit (LUMO) on a metal atom has an energy of E
_LUMO (eV), which is determined by molecular orbital calculation. Orbital (L) is be on the metal atom has the lowest unoccupied molecular orbital energy higher than _{E L (eV), E LUMO} ≦ E L ≦ (E
_LUMO + 0.05). Orbits of LUMO, LUMO ⁺¹ , LUMO ⁺² , LUMO ⁺³ , LMO
UMO ^{+ 4} ... Exist, but the orbit (L) is, in other words, in the orbit of energy equal to or higher than LUMO, the energy is in the range of E _LUMO to (E _LUMO +0.05) (eV). At least one of the trajectories. The orbit (L) is
When the energy is at least one of the orbits in the range of E _LUMO to (E _LUMO +0.02) (eV), the orbit (L) on the metal atom and the orbit (H) on the non-metal atom are different from each other. This is preferable because the energy difference is small and the interaction between these orbitals increases. The orbit (L) is not particularly limited as long as it is on a metal atom and within the above energy range. However, it is preferable that the orbit (L) is LUMO because the interaction becomes further larger.

Highest occupied orbital (HOMO) on non-metallic atoms
_{Has an} energy E _HOMO (eV) and is determined by molecular orbital calculation. Orbital (H) is be on a non-metallic atom, the highest occupied molecular orbital following Ekirugi E _H (eV)
And at least one orbit satisfying (E _HOMO -0.02) ≦ E _H ≦ E _HOMO . HOM on non-metallic atoms
Orbits of energy below O (HOMO, HOMO ^-1 , H
OMO ⁻² , HOMO ⁻³ , HOMO ⁻⁴ ...) Exist, but the orbit (H) is, in other words, the energy of (E _HOMO −0.02) to within the orbit of energy equal to or less than _HOMO.
At least one of the orbits in the range of E _HOMO (eV)
One. The orbit (H) has an energy of (E _HOMO −0.
01) to E _HOMO (eV), the energy difference between the orbital (L) on the metal atom and the orbital (H) on the non-metallic atom is small, and these orbitals This is preferable because the interaction between them increases. The orbit (H) is not particularly limited as long as the orbit (H) is on a non-metallic atom and is within the above energy range. When the orbit (H) is HOMO and / or HOMO ⁻¹ ,
This is preferable because the above interaction is further increased.

For example, for the metal compounds exemplified in Table 1, molecular orbital calculation software (GAUSSIAN94 (GAUSSIAN In
c)) and visualization software (Cerius 2 (MSI))
As a result of calculating the molecular orbital by the basis function LANL2DZ by the F method, the above energy condition is satisfied, and the orbital (H),
The trajectory serving as the trajectory (L) is the trajectory of the portion surrounded by each metal compound in Table 1.

In the metal compound contained as an essential component in the solid catalyst for etherification reaction of the present invention, at least one of the orbitals (L) and at least one of the orbitals (H) among the above-mentioned molecular orbitals. Has directionality.

The direction in the present invention is defined as follows. That is, that the orbit (L) has directionality means that the orbit (L) on the metal atom is centered on the metal atom,
It forms two or three lobes, has at least one discontinuous plane (nodal plane) in the middle of the lobes, and connects a straight line (hereinafter, this straight line) connecting the centers of the lobes. Lobe straight line (L).). The orbit (H) having directionality means that the orbit (H) on a non-metallic atom forms two or three lobes around the non-metallic atom, and at least one lobe is provided between the lobes. A straight line having two discontinuous surfaces and connecting the centers of the lobes (hereinafter, this straight line may be referred to as a lobe straight line (H)).
If there is. The center of the lobe referred to above is the center of the lobe, assuming that the lobe is a homogeneous object.

The trajectory (L) and the trajectory (H) are preferably composed mainly of at least one trajectory selected from a p trajectory, a d trajectory and an f trajectory, because the trajectory becomes directional. Since the s orbit is spherical, there is no directionality.

As an example of the metal compound contained as an essential component in the solid catalyst for etherification reaction of the present invention, for example, among the metal compounds exemplified in Table 1, YPO ₄ can be mentioned. explain in detail.

In YPO ₄ , the orbit (L) is LUMO, LU
MO ⁺¹ , LUMO ⁺² , and LUMO ⁺³ . The orbits (H) are HOMO, HOMO ^-1 , HOMO ^-2 , HOM
O- ³ . Among the orbits of YPO ₄ above, LUMO and H
OMO ^-1 is shown in Table 2. The LUMO of YPO ₄ is distributed on yttrium atoms, the main component of which is d-orbits having two lobes of yttrium atoms, and is distributed in a neat manner with yttrium atoms as the center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, the above directional definition, LUMO of YPO ₄ is orientational. On the other hand, HOMO- ¹ of YPO ₄ is distributed on the oxygen atom of the hydroxyl group, and its main component is a p-orbital having two lobes of the oxygen atom, and is distributed in a fine shape with the oxygen atom as the center. . There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the above definition of the directionality, the HO of YPO ₄
MO- ¹ has directionality. As mentioned above, LUM of YPO ₄
O and HOMO- ¹ both have directionality.

At least one of the directional orbitals (L) and at least one of the directional orbitals (H) among the molecular orbitals of the metal compound contained in the solid catalyst for etherification reaction of the present invention. It is preferable that the two directions are the same because the catalytic activity is high. In the present invention, being in the same direction means that a metal compound is arranged in a three-dimensional space to show a trajectory, and a directional trajectory (L)
At least one lobe straight line (L) and at least one lobe straight line (H) of the directional orbit (H) so as to pass through any point in space. The angle θ (0) formed by the two straight lines obtained by the arrangement
≦ θ ≦ 90 degrees) is 45 degrees or less, preferably 30 degrees or less, and more preferably 10 degrees or less.

The process for producing an ether compound according to the present invention comprises reacting an organic compound having a hydroxyl group with an unsaturated carboxylic acid compound in the presence of the above-mentioned solid catalyst for the etherification reaction. The corresponding ether compound can be efficiently produced without the need for a further step.

The production of the ether compound is not particularly limited as long as it is carried out in a heterogeneous system. For example, it is carried out in a heterogeneous system such as a liquid phase in an aqueous medium or a gas phase. Here, the liquid phase means a state in which the raw material is uniformly dissolved in an aqueous medium, and the heterogeneous liquid phase means a state in which an insoluble catalyst exists in the liquid phase.

The aqueous medium contains water as an essential component and, if necessary, further contains an organic solvent such as tetrahydrofuran, 1,2-dimethoxyethane, dimethylformamide and hexamethylenephosphoric triamide.

Specific examples of the organic compound having a hydroxyl group include hydroxycarboxylic acid compounds, polyhydric alcohol compounds, higher alcohol compounds having 6 to 22 carbon atoms, and saccharides. The details of these organic compounds are as follows. (1) Hydroxycarboxylic acid compound (a) A compound represented by the following general formula (1).

[0027]

Embedded image

In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, Represents an alkyl ammonium group or an alkanol ammonium group, and m represents an integer of 1 to 10. Representative examples include glycolic acid, β-hydroxypropionic acid, lactic acid, and the like.

(B) A compound represented by the following general formula (2).

[0030]

Embedded image

In the formula, R ³ is a hydrogen atom or a group having 1 to 3 carbon atoms.
Wherein n represents an integer of 1 to 10, and X has the same meaning as in formula (1). Typical examples thereof include glyceric acid and gluconic acid.

(C) A compound represented by the following general formula (3). HO—CH ₂ — (CH ₂ —O—CH ₂ ) _P —COOX (3) In the formula, p represents an integer of 1 to 10, and X has the same meaning as in formula (1). Typical examples thereof include diethylene glycol monocarboxylic acid.

(D) A compound represented by the following general formula (4).

[0034]

Embedded image

In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydroxyl group. And X is as defined in general formula (1). Typical examples thereof include malic acid and tartaric acid.

(E) A compound represented by the following general formula (5).

[0037]

Embedded image

In the formula, R ⁷ is a hydrogen atom or a group having 1 to 3 carbon atoms.
Wherein X is as defined in general formula (1). A typical example thereof is tartronic acid.

(F) A compound represented by the following general formula (6).

[0040]

Embedded image

In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X has the same meaning as in the general formula (1). is there. A typical example is citric acid.

(2) Polyhydric alcohol compound (a) A compound represented by the following general formula (7).

[0043]

Embedded image

In the formula, R ^{12 to} R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Typical examples thereof include ethylene glycol and isopropylene glycol.

(B) 2-1 of the compound of the above general formula (7)
Condensate of 0. Typical examples thereof include diethylene glycol.

(C) Glycerin and its derivatives. Typical examples thereof include glycerin, diglycerin, polyglycerin and the like.

(D) sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol and the like.

(3) A higher alcohol compound having 6 to 22 carbon atoms (R-OH). As typical examples, R is hexyl, heptyl, octyl, nonyl, decyl, undecyl, lauryl, myristyl, palmityl, stearyl,
Alcohols such as arachidyl, behenyl, oleyl, linole, linolenyl, 2-ethylhexyl and the like can be mentioned.

(4) Sugars. Representative examples include glucose, mannose, galactose, fructose, lactose, sucrose and the like. Specific examples of the unsaturated carboxylic acid compounds include unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. These will be described more specifically below.

(1) Unsaturated monocarboxylic acid compound (a) A compound represented by the following general formula (8).

[0051]

Embedded image

In the formula, R ^{16 to} R ¹⁸ are each independently:
X represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Has the same meaning as in formula (1). Typical examples thereof include acrylic acid and methacrylic acid.

(2) Unsaturated dicarboxylic acid compound (a) A compound represented by the following general formula (9).

[0054]

Embedded image

In the formula, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X has the same meaning as in formula (1). A typical example is maleic acid.
The unsaturated dicarboxylic acid may be an anhydride.

Therefore, in a preferred embodiment of the present invention, for example, (A) glycolic acid, β-hydroxypropionic acid, lactic acid, glyceric acid, gluconic acid, diethylene glycol monoester in the presence of the above-mentioned solid catalyst for etherification reaction. Hydroxycarboxylic acids such as carboxylic acid, malic acid, tartaric acid, tartronic acid, citric acid; ethylene glycol, isopropylene glycol, diethylene glycol, glycerin, diglycerin, polyglycerin,
Polyhydric alcohols such as sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol;
A higher alcohol having 6 to 22 carbon atoms; and glucose;
At least one compound selected from saccharides such as mannose, galactose, fructose, lactose and sucrose, and (B) an unsaturated monocarboxylic acid such as acrylic acid and methacrylic acid; and an unsaturated dicarboxylic acid such as maleic anhydride The compound is reacted with at least one compound selected from acids to produce a corresponding ether compound. In a particularly preferred embodiment, the corresponding ether is obtained by reacting glycolic acid, malic acid, tartaric acid or tartronic acid of the compound (A) with maleic anhydride of the compound (B). Produce compound.

In the present invention, the reaction formula between (A) an organic compound having a hydroxyl group and (B) an unsaturated carboxylic acid is represented by the following formula:
The case where glycolic acid is used as (A) and maleic acid is used as (B) is as follows.

Reaction of glycolic acid with maleic acid

[0059]

Embedded image

Reaction of glycolic acid with epoxy succinic acid

[0061]

Embedded image

When the process for producing an ether compound of the present invention is carried out, for example, in an aqueous medium, it is usually 40 to 150.
C., and preferably at a temperature in the range of 70 to 120.degree. The reaction pressure may be normal pressure or pressurization, but the reaction is usually performed under normal pressure. About the ratio of (A) the organic compound having a hydroxyl group and (B) the unsaturated carboxylic acid, the molar ratio of (A) / (B) is usually from 0.5 to
2, and preferably 0.8 to 1.2. The amount of the solid catalyst for the etherification reaction can be appropriately selected usually in the range of 0.1 to 5 mol, preferably 0.5 to 2 mol, per 1 mol of the organic compound (A) having a hydroxyl group.

According to the production method of the present invention, for example, when (A) an organic compound having a hydroxyl group is reacted with (B) an unsaturated carboxylic acid in an aqueous medium, a part or all of each of the carboxyl groups is reacted. Preferably, the whole is reacted as an alkali metal salt, particularly a sodium salt. Specifically, when manufacturing CMOS by reacting glycolic acid and maleic anhydride, it is preferable to react as sodium glycolate and disodium maleate, respectively. An aqueous solution of a trisodium salt of CMOS (CMOS-3Na) is obtained as a product. Depending on the use, an aqueous solution or a solid obtained by distilling water may be used. Further, the reaction is performed by making the reaction solution alkaline, specifically, adjusting the pH of the reaction solution to usually 7.5 or more, preferably 7.5 to 13. For adjusting the pH, sodium hydroxide is particularly preferably used.

When the process for producing an ether compound of the present invention is carried out in an aqueous medium, the reaction may be carried out continuously or batchwise. Can be produced. Among the ether compounds obtained by the method of the present invention, CMOS, CMOM, and the like, and alkali metal salts thereof, particularly, sodium salt, are biodegradable and have excellent metal ion trapping performance, so that they are used as detergent builders. It is useful.

The reaction mechanism for producing an ether compound using the solid catalyst for etherification reaction of the present invention is as follows. For example, when the solid catalyst for etherification reaction is YPO ₄ and the organic compound is sodium glycolate, as shown, first, each other exert interaction with sodium YPO ₄ and glycolic acid, generated intermediate (I) is a hydroxyl oxygen atom of the active is sodium glycolate is attacked unsaturated bond ether It is believed that a compound is formed. In this reaction mechanism, the process of generating the intermediate (I) is the most important.

[0066]

Embedded image

The following formula shows a transition state generated by the intermediate (I). Since the LUMO of the yttrium atom and the HOMO- ^{1 of} the oxygen atom bonded to the yttrium atom have directionality, an interaction occurs between the catalyst and the hydroxyl group of sodium glycolate, and the intermediate (I) Will be generated. Here, LUMO and HOMO ^-1
Is not directional, no interaction occurs between the catalyst and the hydroxyl group of sodium glycolate, no intermediate (I) is produced, and the final product ether compound is I can't get it. In the intermediate (I), since LUMO and HOMO ^-1 are in the same direction, (a) the electron from the HOMO on the oxygen atom in the hydroxyl group of sodium glycolate to the LUMO on the yttrium atom in the transition state And (b) electrons easily flow from HOMO- ¹ on the oxygen atom bonded to the yttrium atom to LUMO on the hydrogen atom in the hydroxyl group of sodium glycolate, and the reaction proceeds smoothly. Can be

[0068]

Embedded image

[0069]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 ( Example of Lanthanum Oxide) (Calculation of Molecular Orbital) For the model structure of lanthanum oxide shown in Table 2, molecular orbital calculation software (GAUSSIAN94 (GAUSSIAN Inc)) and visualization software (Cerius 2 (MSI)) ) Is used to calculate the molecular orbitals by the HF method with the basis function LANL2DZ, and the calculation results are shown in Table 1. Among the orbits of lanthanum oxide, LUMO
And HOMO- ¹ are shown in Table 2. LUM of lanthanum oxide
O is distributed on a lanthanum atom, and its main component is a d-orbit having two lobes of the lanthanum atom, and is distributed in a fine shape with the lanthanum atom as a center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, LUMO of lanthanum oxide has directionality. On the other hand, HOMO ^-1 of lanthanum oxide is distributed on an oxygen atom, and its main component is a p-orbital having two lobes of the oxygen atom, and is distributed in a fine shape with the oxygen atom as a center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, HOMO- ¹ of lanthanum oxide has directionality. As mentioned above,
Both lanthanum oxide LUMO and HOMO- ¹ have directionality. Furthermore, LUMO and HOMO ^-1
The measured angle was about 0 degrees.

(Etherification reaction) After dissolving 9.8 g of maleic anhydride in 200 g of water, 7.6 g of glycolic acid was added.
2.0 g were added. Commercially available lanthanum oxide 3 is added to this solution.
After adding 2.6 g and further adjusting the pH to around 10, the reaction was carried out at 90 ° C. with stirring for 12 hours. After the completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by high performance liquid chromatography. As a result, carboxymethoxysuccinic acid trisodium salt (CMOS-3Na) was 30.8 mol%.
It was found that a yield of (based on maleic anhydride) was obtained. The filtrate was evaporated to dryness to obtain white crystals.
As a result of analysis by ¹ H-NMR and ¹³ C-NMR,
It was confirmed that the main component was CMOS-3Na.
When the filtrate was analyzed by ICP, the concentration of lanthanum ions in the filtrate was 0.5 ppm or less.

Example 2 ( Example of Yttrium Oxide) (Calculation of Molecular Orbital) For the model structure of yttrium oxide shown in Table 2,
The same molecular orbital calculation software and visualization software as in Example 1.
The molecular orbital was calculated using (Cerius 2 (MSI)), and the calculation result is shown in Table 1. Of the orbits of yttrium oxide,
Table 2 shows LUMO and HOMO- ¹ . The LUMO of yttrium oxide is distributed on yttrium atoms, the main component of which is d-orbits having two lobes of yttrium atoms, and is distributed in a neat shape with yttrium atoms as the center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, by definition of directionality, LUMO of yttrium oxide has directionality. On the other hand, HOMO- ¹ of yttrium oxide is distributed on an oxygen atom, and its main component is a p-orbital having two lobes of an oxygen atom, and is distributed in a fine shape with the oxygen atom as a center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, the HOM of yttrium oxide
O ^-1 has directionality. As described above, both LUMO and HOMO- ^{1 of} yttrium oxide have directionality.

(Etherification Reaction) An etherification reaction was carried out in the same manner as in Example 1, except that 22.6 g of yttrium oxide was used instead of lanthanum oxide. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by high performance liquid chromatography. As a result, carboxymethoxysuccinic acid trisodium salt (CMOS-3Na) was 14.5 mol%.
It was found that a yield of (based on maleic anhydride) was obtained. The filtrate was evaporated to dryness to obtain white crystals.
As a result of analysis by ¹ H-NMR and ¹³ C-NMR,
It was confirmed that the main component was CMOS-3Na.
When the filtrate was analyzed by ICP, the concentration of yttrium ions in the filtrate was 0.5 ppm or less.

Example 3 ( Example of Yttrium Phosphate) (Calculation of Molecular Orbital) For the model structure of yttrium phosphate shown in Table 2, the same molecular orbital calculation software and visualization software (Cerius 2 (MSI)) as in Example 1 were used. ) Is used to calculate the molecular orbitals, and the calculation results are shown in Table 1. Table 2 shows LUMO and HOMO- ¹ among the orbits of the yttrium phosphate. The LUMO of yttrium phosphate is distributed on the yttrium atom, the main component of which is the d-orbit with two lobes of the yttrium atom.
It is distributed in a good shape. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, LUMO of yttrium phosphate has directionality. On the other hand, HOMO- ¹ of yttrium phosphate is distributed on an oxygen atom of a hydroxyl group, and its main component is a p-orbital having two lobes of an oxygen atom. I have. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, HOMO- ¹ of yttrium phosphate has directionality. As described above, both LUMO and HOMO- ^{1 of} yttrium phosphate have directionality.

(Preparation of Yttrium Phosphate) After dissolving 149.06 g of yttrium chloride hexahydrate in 200 g of water, disodium hydrogen phosphate dodecahydrate 1
43.2 g was added, and p was added with a 48% aqueous sodium hydroxide solution.
After adjusting H to around 9, the reaction was carried out at a temperature of 50 ° C. for 1 hour. After completion of the reaction, the resulting precipitate was filtered, washed with water several times, and dried under reduced pressure to obtain 92.8 g of a white solid.
From the result of the X-ray diffraction analysis, it was confirmed that this solid product contained the structure of yttrium phosphate.

(Etherification reaction) After dissolving 9.8 g of maleic anhydride in 200 g of water, 15.0 g of tartaric acid was added.
0 g was added. After adding 23.2 g of the yttrium phosphate obtained above to this solution, and further adjusting the pH to around 10, the reaction was carried out at 90 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by high performance liquid chromatography. As a result, monosodium succinate tartrate (TMS-4Na) was obtained in a yield of 15.9 mol% (based on maleic anhydride). I knew it could be done. In addition,
The white crystals obtained was evaporated to dryness filtrate ¹ H-NM
As a result of analysis by R and ¹³ C-NMR, it was confirmed that TMS-4Na was contained in the crystals. When the filtrate was analyzed in the same manner as in Example 1, the yttrium ion concentration was 1 ppm or less.

Example 4 ( Example of lanthanum oxychloride) (Calculation of molecular orbital) For the model structure of lanthanum oxychloride shown in Table 2, the same molecular orbital calculation software and visualization software (Cerius 2 (MSI)) as in Example 1 were used. ) Is used to calculate the molecular orbitals, and the calculation results are shown in Table 1. Table 2 shows LUMO and HOMO- ¹ among the orbits of lanthanum oxychloride. LUMO of lanthanum oxychloride is distributed on the lanthanum atom, and its main component is a d-orbital having two lobes of the lanthanum atom, and is distributed in a fine shape with the lanthanum atom as a center. And there is a discontinuous surface in the middle of each lobe,
There is a straight line connecting the centers of each lobe. Thus, by definition of directionality, LUMO of lanthanum oxychloride has directionality. On the other hand, HOMO- ¹ of lanthanum oxychloride is distributed on a chlorine atom, and its main component is a p-orbital having two lobes, which are distributed in a fine shape with the chlorine atom as a center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Thus, by definition of directionality, HOMO- ¹ of lanthanum oxychloride has directionality. As described above, both LUMO and HOMO- ^{1 of} lanthanum oxychloride have directionality.

(Preparation of Lanthanum Oxychloride) By heating 92.8 g of lanthanum chloride hydrate at 600 ° C. for 24 hours, 47.4 g of a white solid was obtained. From the result of the X-ray diffraction analysis, it was confirmed that this white solid contained a structure of lanthanum oxychloride.

(Etherification Reaction) In the etherification reaction of Example 1, except that 23.7 g of lanthanum oxychloride was used instead of lanthanum oxide.
An etherification reaction was performed in the same manner as in the example. After completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by high performance liquid chromatography. As a result, carboxymethoxysuccinic acid trisodium salt (CMOS-3Na) was 35.8 mol%.
It was found that a yield of (based on maleic anhydride) was obtained. The filtrate was evaporated to dryness to obtain white crystals.
As a result of analysis by ¹ H-NMR and ¹³ C-NMR,
It was confirmed that the main component was CMOS-3Na.
When the filtrate was analyzed by ICP, the concentration of lanthanum ions in the filtrate was 0.5 ppm or less.

Comparative Example 1 ( Comparative Example of Calcium Phosphate and Magnesium Phosphate) (Calculation of Molecular Orbital) For the model structure of calcium phosphate shown in Table 2,
The same molecular orbital calculation software and visualization software as in Example 1.
The molecular orbital was calculated using (Cerius 2 (MSI)), and the calculation result is shown in Table 1. Table 2 shows LUMO and HOMO of the model structure of calcium phosphate. The HOMO of calcium phosphate is distributed on the oxygen atom of the hydroxyl group, and its main component is a p-orbital having two lobes of the oxygen atom, and is distributed in a fine shape with the oxygen atom as the center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, the HOMO of calcium phosphate has directionality. However, although the LUMO of calcium phosphate is distributed on the calcium atom, its main component is s orbitals and it has no direction, so calcium phosphate does not become a solid catalyst for ether reaction. Like calcium phosphate, the LUMO of magnesium phosphate is distributed on magnesium atoms, but its main component is the s orbital,
Due to the lack of directionality, magnesium phosphate does not become a solid catalyst for ether reactions.

(Etherification reaction) The reaction was carried out in the same manner as in Example 1 except that the lanthanum oxide used as the catalyst in Example 1 was changed to calcium phosphate, but the reaction was carried out in the same manner as in sodium carboxymethoxysuccinate (CMOS- 3Na) was not obtained. Also,
The reaction was performed by changing the catalyst to magnesium phosphate,
Similarly, CMOS-3Na was not obtained.

Comparative Example 2 ( Comparative Example of Iron Phosphate) (Calculation of Molecular Orbital) The model structure of iron phosphate shown in Table 2 was used in Example 1
Molecular orbital calculation software and visualization software (Cerius
2 (MSI)), the molecular orbital was calculated, and the calculation result is shown in Table 1. LUMO and H of the model structure of iron phosphate
Table 2 shows the OMO. The HOMO of iron phosphate is distributed on the oxygen atom of the phosphate group, and its main component is a p-orbital having two lobes of the oxygen atom, which are distributed in a fine shape with the oxygen atom as the center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, HOMO of iron phosphate has directionality. On the other hand, LUMO of iron phosphate is distributed on iron atoms, and its main component is d with four lobes of iron atoms.
Orbitals, not orbitals with two or three lobes of iron atoms. Therefore, according to the definition of directionality, since LUMO of iron phosphate does not have directionality, iron phosphate does not become a solid catalyst for an ether reaction.

(Etherification reaction) The reaction was carried out in the same manner as in Example 1 except that lanthanum oxide used as the catalyst in Example 1 was changed to iron phosphate. Trimethoxysodium succinate (CMOS-3Na) was not obtained.

Comparative Example 3 ( Comparative Example of Aluminum Phosphate) (Calculation of Molecular Orbital) For the model structure of aluminum phosphate shown in Table 2, the same molecular orbital calculation software and visualization software (Cerius 2 (MSI)) as in Example 1 were used. ) Is used to calculate the molecular orbitals, and the calculation results are shown in Table 1. Table 2 shows LUMO and HOMO of the model structure of aluminum phosphate. HOMO of aluminum phosphate is distributed on oxygen atom of hydroxyl group,
Its main component is a p-orbital having two lobes of oxygen atoms, which are distributed in a fine shape with the oxygen atoms as the center. There is a discontinuous surface in the middle of each lobe, and there is a straight line connecting the centers of each lobe. Therefore, according to the definition of directionality, HOMO of aluminum phosphate has directionality. On the other hand, LUMO of aluminum phosphate is distributed on aluminum atoms, the main component of which is s orbitals of aluminum atoms, and there is no discontinuous surface. Therefore, according to the definition of directionality, aluminum phosphate does not become a solid catalyst for an ether reaction because LUMO of aluminum phosphate has no directionality.

(Etherification Reaction) The reaction was carried out in the same manner as in Example 1 except that the lanthanum oxide used as the catalyst in Example 1 was changed to aluminum phosphate. The reaction was carried out, however, trisodium carboxymethoxysuccinate ( CMOS-3Na) was not obtained.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

Since the solid catalyst for the etherification reaction selected by the method of the present invention is defined by molecular orbitals, it is not necessary to conduct complicated experiments to confirm the catalytic activity.
The etherification reaction can be performed easily and efficiently.

[0089] manufacturing method of an ether compound of the present invention, instead of the conventional homogeneous reaction, in the presence of the solid catalyst to perform the heterogeneous reaction, an organic compound having a hydroxyl group and an unsaturated carboxylic acid compound and for reacting the corresponding ether compounds, simple and can be manufactured efficiently.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-10-66868 (JP, A) JP-A-2-85224 ( JP, A) JP-A-2-42037 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07B 61/00 300 CA (STN) JICST file (JOIS)

Claims (4)

(57) [Claims] 1. A metal compound containing non-metallic atoms bonded to the metal atom and a metal atom (excluding phosphate lanthanum.) As essential components, the catalyst used in the following production method (1) A selection method , wherein a molecular orbital of the metal compound is obtained , a lowest unoccupied orbital (LUMO) on the metal atom, a highest occupied orbital (HOMO) on the non-metallic atom, and
The next occupied orbit (HOMO ^-1 ) , the lowest unoccupied orbit (LUMO) and the highest occupied orbit (H
OMO) or the next occupied orbit (HOMO ^-1 )
One bets selects the metal compound having a directivity, the selection method of the solid catalyst or. Manufacturing method (1): an organic compound having a hydroxyl group, is reacted with an unsaturated carboxylic acid compound, prepared how the ether compound 2. A track having the directivity (LUMO) and trajectories
The solid catalyst for an etherification reaction according to claim 1, wherein the direction of the road (HOMO) or the orbit (HOMO- ¹ ) is the same direction.
How to choose . 3. The method according to claim 1, wherein said metal atom is a rare earth atom.
Or 2 ) Selection of solid catalyst for etherification reaction
Law . 4. The method according to claim 1, wherein
An organic compound having a hydroxyl group and an unsaturated carboxylic acid compound are selected in the presence of the selected solid catalyst for the etherification reaction .
And a method for producing an ether compound .