JP4589869B2 - A simple method for producing zeolite analogues that function as acid catalysts. - Google Patents

Description

  The present invention generally relates to a method for producing calcite and a calcite with a simple process with less environmental burden. More specifically, proton exchange-type zeolite analogues useful as Lewis acids from diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. It relates to a process for the production and to its proton exchange zeolite analogue. Furthermore, the present invention relates to a glycosylation reaction that has a low environmental impact and can be carried out by a simple process using this proton exchange type zeolite analog as a catalyst. In particular, the present invention relates to functional foods, biodegradable fibers, pharmaceuticals, surfactants or detergents. The present invention relates to a method for synthesizing a useful carbohydrate polymer or glycoside.

In general, zeolite is composed of SiO ₄ and AlO ₄ tetrahedrons (TO ₄ tetrahedrons), alkali metal cations, and water that reversibly adsorbs and desorbs (zeolite water). The TO ₄ tetrahedron shares an apex oxygen atom and bonds to form a three-dimensional skeleton (tectosilicate), and the molar ratio of T atom to oxygen is 1: 2.

Write zeolite represented by the ideal formula NaAlSi ₂ O ₆ · _{H 2} O is a natural zeolite normally produced from volcanic areas, belonging to aluminosilicate minerals. Since calcite can be surface-treated, an ammonium ion adsorbent with a silicone coating and a function of selectively adsorbing ammonium ions is added. An extender is produced. In addition, a filter that induces hydrophobic crystalline zeolite from zeolitic to reduce the hydrocarbon content in air or water to a harmless level, iron-containing zeolitic (crystalline silicometallates) is oxidized by alkanes Methods have been devised for use as catalysts.

The alkali metal cation of calcite can be exchanged. An ion exchanger utilizing this property is a general application of zeolite. The alkali metal cation of calcite is Na ⁺ , but the zeolite analog having a TO ₄ tetrahedral skeleton of the same structure and containing Ca ²⁺ as the alkali metal cation is Wairakei zeolite, and the zeolite containing K ⁺ is leucite and It is called and is naturally produced. These are all alkali metal cation exchange analogs of zeolitic. Further, from an industrial chemical viewpoint, zeolite analogues in which the alkali metal cation of zeolitic is exchanged with Li ⁺ , Ag ⁺ , K ⁺ , NH ₄ ⁺ , Tl ⁺ , Rb ⁺ , and Cs ⁺ have been produced so far.

When the alkali metal cation of calcite is exchanged with NH ₄ ⁺ and subjected to heat treatment, NH ₃ is eliminated and a proton exchange type zeolite analog can be obtained. It is known that Lewis acidity develops when a proton-exchanged zeolite analog is heat-treated.

  A general use of zeolite is a molecular sieving function. Considering the molecular sieving function of zeolite, the size of the window, which is a gateway for molecules to enter the pores from the outside, is important. Zeolite forms various pore structures, but there are surprisingly few types of windows, and there are only 8 types of oxygen 3, 4, 5, 6, 8, 10, 12, 18-membered rings. Of these, the windows through which inorganic gases and organic molecules can pass are limited to four types of oxygen 8-membered or more. Since the pore structure of calcite is composed of a 4-membered ring and a 6-membered ring, its function as a molecular sieve is limited.

However, since zeolite has a finer crystal structure than other zeolites, it has the characteristics of being chemically and physically stable. In other words, the crystal structure is not destroyed even when the baking treatment is performed, and it is synthesized even under a high temperature and high pressure environment of 450 ° C. and 100 MPa. When proton exchange zeolite is heat-treated, H ₂ O is desorbed and a very strong electron affinity Lewis acidity develops, but zeolitic is resistant to heat treatment, and proton-exchange zeolite analogues are heat-treated. There are special advantages to using Lewis acid catalysts.

  It was in 1936 that clay catalysts were first used for the catalytic cracking of petroleum. An activated clay obtained by acid treatment of acid clay (montmorillonite) was used. The activated clay catalyst was then replaced by synthetic silica-alumina (1940) and zeolite (1962).

  In the chemical industry, synthetic zeolite is mainly used as a catalyst. Among naturally occurring zeolites, erionite has excellent acid resistance and can be used as a catalyst. Because natural zeolite is of poor quality, it can be used as it is. However, even natural zeolites such as calcite can be useful catalysts if analogs with controlled properties are produced by chemical synthesis.

  Artificial zeolite uses sodium metasilicate and colloidal silica as the silica source and sodium aluminate as the alumina source. These are precipitated in a heated NaOH solution, and the resulting solid is separated by filtration and thoroughly washed with water. It is obtained by drying at 110 ° C. later. In this production method, zeolite A or zeolite Y can be obtained.

There are two main production methods for calcite. The first is a production method in which tuff-based volcanic clastic rocks are produced by hydrothermal treatment in NaOH, chloride and sodium aluminate solutions. Specifically, calcite can be produced by treating volcanic clastic rock (tuff) containing clinoptilolite with an alkaline hot water solution to which Na ₂ CO ₃ —NaHCO ₃ is added. In this production method, zeolite is produced by a synthetic system that reproduces the natural system. Natural calcite is thought to be formed by the interaction between salt solution and volcanic glass in volcanic clastic rocks by hot spring alteration.

In addition, zeolite can be produced from commercially available industrial products. That is, zeolitic or zeolite analogs can be obtained by adding a silica-providing substance such as quartz to an aluminosilicate having a specific SiO ₂ / Al ₂ O ₃ molar ratio and hydrothermally treating it in a NaOH or KOH solution. Furthermore, even if the artificial glass having the same composition as the calcite is treated with hot water, the calcite can be produced. Similarly to synthetic zeolite such as zeolite A or zeolite Y, zeolitic can be produced from water-soluble silicate and aluminate. When sodium orthosilicate is used as the silica source and sodium aluminate is used as the alumina source and the zeolite is produced by hydrothermal synthesis, tetramethylammonium bromide is added as a catalyst.

  In these methods for producing calcite, there are differences in raw materials such as using natural volcanic clastic rocks or commercially available industrial products, but the process of adding an alkali metal cation by hydrothermal synthesis is common. In order to use the zeolitic obtained by this conventional production method as an acid catalyst, it is necessary to produce an proton exchange-type zeolitic by exchanging an alkali metal cation with a proton by ion exchange (for example, JP-T-2002). -508006 (see page 5)). Since calcite is resistant to heating, a proton exchange type calcite can be calcined to obtain a Lewis acid catalyst.

  As a method for producing a zeolite catalyst, there is a production method in which a metal is supported on the zeolite surface in addition to the above-described method for producing a proton exchange type zeolite. In this case, the zeolite functions as a highly dispersed catalyst support. The catalytic metal is introduced into the zeolite by ion exchange.

Recent advances in zeolite science include silica zeolite that is substantially free of aluminum, and the position of T (Al, Si) atoms forming the framework structure is Ti, B, Fe, Ga, Ge, P or some or all It was possible to synthesize a substituted so-called framework-substituted zeolite (for example, see JP-T-11-510136 (pages 4 to 9)). Also for calcite, a zeolite analogue in which the SiO ₄ tetrahedral structure is substituted with GeO ₄ industrially and Cs ⁺ is added as an alkali metal cation has been produced.

  Since calcite is resistant to heat treatment, there is a special advantage in producing a proton exchange zeolite analogue and making it a Lewis acid catalyst by calcination treatment. In the conventional method for producing proton exchange type calcite, a cation in zeolitic is protonated by ion exchange to produce a solid acid catalyst, and Lewis acidity is expressed by subsequent calcination treatment (see, for example, Patent Document 1). ). However, if a proton exchange type zeolite analogue can be obtained in the process of producing zeolitic, the production process can be shortened.

Synthetic zeolite is crystallized by drying a raw material gel precipitated from a silica source and an alumina source in hot water at a temperature of 100 ° C. or higher. If the crystallization process of the raw material gel and the calcination for Lewis acid catalysis can be performed simultaneously, the manufacturing process can be further reduced. That is, if gelled proton exchange type zeolitics can be precipitated in an acidic solution, it can be expected that H ₂ O is desorbed and Lewis acidity is expressed when the proton exchange type zeolite analogue is crystallized from the raw material gel. .

  Furthermore, when producing a transition metal substitution type zeolite analog catalyst, the alkali metal cation exchange type zeolite catalyst into which the metal element is introduced by ion exchange has a problem in stability, but the transition metal element functioning as a catalyst is converted into the zeolite. It can be expected that the stability will be improved if it can be introduced into the skeleton structure. By synthesizing a skeleton-substituted zeolite analog with transition elements such as Zr and Ti, the pore diameter can be changed without changing the pore structure of zeolitic.

  As described above, synthetic zeolite has been used as a catalyst in the chemical industry because it has Lewis acidity. The present inventors paid attention to the application of a catalyst to a synthesis system of a carbohydrate polymer or a glycoside whose manufacturing process is extremely complicated. In particular, in the present invention, a sugar donor and a sugar acceptor are focused on a glycosylation reaction system in which a glycosidic bond is formed between the sugar donor and the sugar acceptor.

  The glycosidic bond generated by the glycosylation reaction is, for example, a saccharide skeleton. This glycosidic bond can be converted into, for example, a monosaccharide, oligosaccharide or polysaccharide, i.e., a hemiacetal hydroxyl group or a hemiketal hydroxyl group of a sugar unit, and another simple group. In order to synthesize saccharide macromolecules and glycosides, efficient generation between sugar, oligosaccharide or polysaccharide hydroxyl groups and molecules other than sugar, such as alcoholic hydroxyl groups, carboxylic acids and carboxyl groups of amino acids. It can be said that this is a problem.

  Conventionally, for example, the Keonigs-Knorr method, the imidate method, and the fluorination method have been applied to the production of carbohydrate polymers and glycosides.

  However, according to these manufacturing methods, the manufacturing process becomes very complicated.

  On the other hand, the Fisher method, which can generate glycosidic bonds between molecules in only one step in the presence of an acid catalyst, is a very simple process. It can be said that this method is suitable for production.

  By this Fisher method, for example, a condensation polymer in which many D-glucoses are condensation-polymerized by O-glycosidic bonds is used in the food field as indigestible dietary fiber.

  In addition, when a large excess of methanol is allowed to act on D-glucose in the presence of hydrochloric acid, methyl glycoside that is O-glycosidized by the hydroxyl group at the 1-position of D-glucose and the hydroxyl group of methanol is generated. This methyl glycoside can be used, for example, in a surfactant, a detergent or the like.

  In addition, conventionally, a reaction is performed by appropriately setting a leaving group, a hydroxyl protecting group, a carboxyl protecting group, an amino protecting group, and / or a catalyst of a sugar donor and a sugar acceptor to control the reaction position, Placement control has been performed. For example, in the above-described imidate method, α-type and β-type can be selectively synthesized in high yield by the imidate used.

  However, in any of the above-mentioned glycosylation reactions, a large amount of an organic solvent such as benzene, methylene chloride, acetonitrile or toluene, which has a particularly large environmental load, is used.

  Therefore, the advent of a glycosylation reaction that is difficult with the solvent used in the conventional synthesis method, has a simple process, and has a low environmental load, that is, a synthesis method of a carbohydrate polymer or a glycoside is desired. .

  However, the conventional glycosylation reaction has a very complicated process and is not suitable for industrial mass production. In particular, since a large amount of environmentally intensive organic solvents such as benzene and halogen-containing organic solvents are used as reaction solvents, there are concerns about problems such as waste liquid treatment after the process.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above conventional problems.

  First, as the present inventors are diligently pursuing research, a 1N sulfuric acid solution is added to Neogene diatomaceous earth containing illite and muscovite, and the Lewis acidity is converted into diatomaceous earth by baking at 650 ° C. after drying. I found it to develop. And, as a result of pursuing a factor that causes Lewis acidity to appear in diatomaceous earth, it was found that a zeolite analog was formed from clay diatomaceous earth added with a sulfuric acid solution and dried at 650 ° C. In contrast to conventional zeolite production in which an alkali metal is added in an alkaline solution, the present invention does not add an alkali metal in an acidic solution. Does not take shape. That is, it is a proton-type zeolite analog in which an alkali metal of zeolitic is substituted with a proton.

  Furthermore, the present invention uses a proton-type zeolite analog as a catalyst, particularly in the presence of a supercritical fluid that is a reaction solvent having a low environmental impact, thereby allowing glycosylation reactions such as monosaccharides, disaccharides and the like. The inventors have found that a condensation reaction between saccharide units or a condensation reaction between a saccharide unit and alcohols, lipids, amino acids and the like proceeds efficiently, and the present invention has been completed.

In order to achieve the above object, the present invention provides the following.
(1) A method for producing a raw material for producing a proton exchange type zeolite analogue, comprising a zeolite having a tectosilicate skeleton in which all or part of cations of an inorganic mineral are substituted with H ⁺ The following:
A process of treating an inorganic mineral with an acidic solution;
Including the method.
(2) From the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediments and lake marine sediments, where the above-mentioned natural materials containing inorganic minerals The method according to item (1), comprising at least one selected.
(3) The raw material natural material containing the inorganic mineral is as follows:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method according to Item (2), further comprising:
(4) The method according to item (1), further comprising a step of removing the organic substance and the smectite mineral by decantation using a neutral or alkaline solution.
(5) The method according to item (1), wherein the acidic solution contains hydrogen peroxide.
(6) The method according to item (1) or (5), wherein the acidic solution includes a hydrochloric acid solution.
(7) The method according to item (4), wherein the neutral or alkaline solution contains sodium pyrophosphate.
(8) The method according to Item (4), wherein the smectite-based mineral includes montmorillonite.
(9) A raw material for producing a proton-type zeolite analog having Lewis acid activity, produced by the method according to item (1).
(10) A method for producing a proton exchange type zeolite analog, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , and the method includes the following:
Adding an inorganic acid to the raw material from which the smectite clay mineral has been removed from the inorganic mineral and reacting the silica source and the alumina source to obtain a reaction product; and firing the reaction product;
Where
Proton exchange type zeolite analogs represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is Al + Si, and the Si / Al ratio is an integer greater than or equal to 1,
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(11) The method according to item (10), wherein W is an alkali metal or an alkaline earth metal.
(12) From the group consisting of raw materials containing the above inorganic minerals consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marsh sediment Item 11. The method according to Item (10), comprising at least one selected.
(13) The raw material natural material containing the inorganic mineral is the following:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method according to item (12), further comprising:
(14) The method according to item (10), wherein the inorganic acid is sulfuric acid.
(15) The method according to item (10), wherein the firing temperature is 540 ° C. or higher.
(16) The method according to item (10), wherein the product obtained by reacting the silica source and the alumina source is air-dried and then calcined.
(17) Similar to proton exchange type zeolite produced by the method according to item (10), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n body.
(18) A method for producing a proton exchange-type zeolite analog into which a transition metal is introduced, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , ,Less than:
A process of supporting a transition metal compound on a raw material obtained by removing smectite clay mineral from an inorganic mineral,
Where
Proton exchange type zeolite analogues by introducing a transition metal is represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is a transition metal selected from the group consisting of Group IIIA to VIIA, Group VIII and IB elements, or a typical metal element selected from the group consisting of Group IIIB and IVB elements;
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(19) The method according to item (18), wherein W is an alkali metal or an alkaline earth metal.
(20) The raw material natural material containing the above inorganic mineral is selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marine sediment. Item 19. The method according to Item (18), comprising at least one selected.
(21) The natural material of the raw material containing the inorganic mineral is the following:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method according to Item (18), further comprising:
(22) The method according to item (18), wherein the supporting step is vapor deposition of the transition metal compound by a CVD method.
(23) The transition metal compound is a halide, sulfate, acetate, carbonyl, nitrate or a mixture of transition metals selected from the group consisting of elements of Group IIIA to VIIA, Group VIII and IB The method according to item (18).
(24) The method according to item (23), wherein the transition metal compound is ZrCl ₄ , TiCl ₄ , FeCl ₂ or a mixture thereof.
(25) The method according to item (18), wherein the supporting step is impregnation with the transition metal hydroxide gel.
(26) The method according to item (18), further comprising a hydrolysis step after the carrying step.
(27) Similar to proton-exchanged zeolite produced by the method according to item (18), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n. body.
(28) A method for producing a proton exchange-type zeolite analog into which a transition metal is introduced, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , ,Less than:
Adding an inorganic acid to an inorganic mineral carrying a transition metal, reacting the transition metal, a silica source, and an alumina source to obtain a reaction product; and firing the reaction product;
Where
Proton exchange type zeolite analogues by introducing a transition metal is represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is a transition metal selected from the group consisting of Group IIIA to VIIA, Group VIII and IB elements, or a typical metal element selected from the group consisting of Group IIIB and IVB elements;
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(29) The method according to item (28), wherein W is an alkali metal or an alkaline earth metal.
(30) The raw material natural material containing the inorganic mineral is a group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marsh sediment. Item 29. The method according to Item (28), comprising at least one selected.
(31) The raw material natural material containing the inorganic mineral is the following:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method according to item (28), further comprising:
(32) The method according to item (28), wherein the inorganic acid is sulfuric acid.
(33) The method according to item (28), wherein the firing temperature is 540 ° C. or higher.
(34) The method according to item (28), wherein the product obtained by reacting the transition metal, the silica source, and the alumina source is air-dried and then calcined.
(35) Similar to proton exchange type zeolite produced by the method according to item (28), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n. body.
(36) A method for producing a proton exchange type zeolite analogue, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , wherein the method comprises the following:
Treating the inorganic mineral with an acidic solution;
A step of adding an inorganic acid to the raw material after the acid treatment and reacting a silica source and an alumina source to obtain a reaction product; and a step of firing the reaction product;
Where
Proton exchange type zeolite analogs represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is Al + Si, and the Si / Al ratio is an integer greater than or equal to 1,
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(37) The method according to item (36), including a step of removing the smectite mineral by decantation using a neutral or alkaline solution before the addition of the inorganic acid.
(38) The method according to item (36), wherein the acidic solution contains hydrogen peroxide.
(39) The method according to Item (36), wherein W is an alkali metal or an alkaline earth metal.
(40) The method according to item (36), wherein the neutral or alkaline solution contains sodium pyrophosphate.
(41) The natural material of the raw material containing the inorganic mineral is a group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marsh sediment. Item 36. The method according to Item 36, comprising at least one selected.
(42) The raw material natural material containing the inorganic mineral is:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method of paragraph (41), further comprising:
(43) The method according to Item (37), wherein the smectite-based mineral includes an organic substance and montmorillonite.
(44) The method according to item (36), wherein the inorganic acid is sulfuric acid.
(45) A method according to item (36), wherein the firing temperature is 540 ° C. or higher.
(46) The method according to item (36), wherein the product obtained by reacting the silica source and the alumina source is air-dried and then calcined.
(47) Similar to proton-exchanged zeolite produced by the method according to item (36), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n body.
(48) A method for producing a proton exchange type zeolite analog into which a transition metal is introduced, comprising a zeolite in which all or part of cations of an inorganic mineral are substituted with H ⁺ and having a tectosilicate skeleton, Less than:
Treating the inorganic mineral with an acidic solution;
A step of supporting a transition metal compound on a raw material obtained by removing smectite clay mineral from an inorganic mineral;
Adding an inorganic acid to an inorganic mineral carrying a transition metal compound, reacting the transition metal with a silica source and an alumina source to obtain a reaction product; and firing the reaction product;
Where
Proton exchange type zeolite analogues by introducing a transition metal is represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is a transition metal selected from the group consisting of Group IIIA to VIIA, Group VIII and IB elements, or a typical metal element selected from the group consisting of Group IIIB and IVB elements;
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(49) The method according to item (48), comprising a step of removing the smectite mineral by decantation using a neutral or alkaline solution before the addition of the inorganic acid.
(50) The method according to Item (48), wherein the acidic solution contains hydrogen peroxide.
(51) The method according to Item (48), wherein W is an alkali metal or an alkaline earth metal.
(52) A method according to item (49), wherein the neutral or alkaline solution contains sodium pyrophosphate.
(53) From the group consisting of the above-mentioned inorganic materials containing natural minerals consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marsh sediment Item 49. The method according to Item 48, comprising at least one selected.
(54) The raw material natural material containing the inorganic mineral is:
Opal; and mica minerals or mica-based clay minerals, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite
The method according to Item (53), further comprising:
(55) The method according to Item (49), wherein the smectite-based mineral includes an organic substance and montmorillonite.
(56) A method according to item (48), wherein the supporting step is vapor deposition of the transition metal compound by a CVD method.
(57) The transition metal compound is a halide, sulfate, acetate, carbonyl, nitrate or a mixture of transition metals selected from the group consisting of elements of Group IIIA to Group VIIA, Group VIII and IB The method according to item (48).
(58) A method according to item (57), wherein the transition metal compound is ZrCl ₄ , TiCl ₄ , FeCl ₂ or a mixture thereof.
(59) A method according to item (48), wherein the supporting step is impregnation with the transition metal hydroxide gel.
(60) The method according to Item (48), further comprising a hydrolysis step after the carrying step.
(61) Similar to proton-exchanged zeolite produced by the method according to item (48), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n body.
(62) A method for producing a proton exchange-type zeolite analog into which a transition metal is introduced, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , ,Less than:
A step of supporting a transition metal compound on a raw material obtained by removing smectite clay mineral from an inorganic mineral;
Adding an inorganic acid to an inorganic mineral carrying a transition metal compound and reacting the transition metal with a silica source and an alumina source; and firing the reaction product;
Where
Proton exchange type zeolite analogues by introducing a transition metal is represented by the formula _{W p H m-p Z n} O 2n · SH 2 O,
W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB;
Z is a transition metal selected from the group consisting of Group IIIA to VIIA, Group VIII and IB elements, or a typical metal element selected from the group consisting of Group IIIB and IVB elements;
m and n are each an integer of 1 or more,
p is an integer greater than or equal to 0 and less than m;
The method, wherein S is any number greater than or equal to zero.
(63) Similar to proton-exchanged zeolite produced by the method according to item (62), wherein the number of oxygen atoms O in the above formula is (2n-0.5 (mp)) or more and less than 2n body.
(64) A method for synthesizing a sugar-containing substance, comprising a step of reacting a sugar donor and a sugar acceptor in the presence of a supercritical fluid to produce a sugar-containing substance.
(65) A method according to item (64), wherein the supercritical fluid is a fluid of carbon dioxide.
(66) A method according to item (64), wherein the reaction step is performed in the presence of an acid catalyst.
(67) The method according to Item (64), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(68) A method according to item (67), wherein the acidic solution is sulfuric acid.
(69) The raw material natural materials containing the above inorganic minerals are from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake marine sediment. The method of paragraph (67), comprising at least one selected.
(70) The natural material of the raw material containing the inorganic mineral is as follows:
A mica mineral or a mica-based clay mineral, including at least one of opal;
The method of paragraph (69), further comprising:
(71) The acid catalyst is silver trifluoromethanesulfonate, trifluoromethanesulfonic acid trimethylsilyl, boron trifluoride-diethyl ether _{complex, SnCl 2 -AgClO 4, SnCl 2} -AgOTf, Cp 2 ZrCl 2 -AgClO 4, sulfated zirconia, The method according to item (66), selected from the group consisting of diatomaceous earth, sulfuric acid-treated diatomaceous earth, and sulfated titania-supported diatomaceous earth.
(72) The method according to Item (64), wherein the sugar-containing substance is a carbohydrate polymer or a glycoside.
(73) Formula (I);

Wherein R ¹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ² is —OH, —OR ⁶ , —N ₃ or —NHR ⁷ , R ³ and R ⁴ is independently of each other —OH or —OR ⁶ , R ⁵ is —H, —CH ₃ , —CH ₂ OH, —CH ₂ OR ⁶ , or —COOR ⁸ , and R ⁶ is Independently, it is a sugar chain in which a hydroxyl protecting group or all reactive functional groups containing a hydroxyl group are protected, R ⁷ is an amino group protecting group, and R ⁸ is a carboxyl group protecting group.)
One or more sugar donors selected from the group comprising saccharide units of:
Formula (II);

(Wherein R ⁹ is —OR ¹⁴ , R ¹⁰ is —OR ¹⁵ , —N ₃ or —NHR ¹⁶ , R ¹¹ is —OR ¹⁷ , R ¹² is —OR ¹⁸ , R ¹³ Is —H, —CH ₃ , —CH ₂ OR ¹⁹ or —COOR ²⁰ , and R ¹⁴ and R ¹⁵ are independently of each other protected by —H, a hydroxyl protecting group or all reactive functional groups containing a hydroxyl group. R ¹⁶ is an amino group protecting group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently, independently of each other, all reactive functional groups containing —H, a hydroxyl protecting group or a hydroxyl group. Is a protected sugar chain, and R ²⁰ is a carboxyl protecting group, provided that at least one of R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ is —H.)
One or more sugar receptors selected from the group comprising the following sugar units,
A method for synthesizing a saccharide polymer comprising a step of producing a saccharide polymer by reacting in the presence of an acid catalyst and a supercritical fluid.
(74) A method according to item (73), wherein the supercritical fluid is a fluid of carbon dioxide.
(75) A method according to item (73), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(76) Formula (III);

Wherein R ²¹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ²² is —OH, —OR ²⁶ , —N ₃ or —NHR ²⁷ , and R ²³ and R ²⁴ is independently of each other —OH or —OR ²⁶ , R ²⁵ is —H, —CH ₃ , —CH ₂ OH, —CH ₂ OR ²⁶ or —COOR ²⁸ , and R ²⁶ is independently of each other. And a hydroxyl chain protecting group or a sugar chain in which all reactive functional groups containing a hydroxyl group are protected, R ²⁷ is an amino group protecting group, and R ²⁸ is a carboxyl group protecting group. ^At least one of ²² , R ²³ , R ²⁴ or R ²⁵ is a hydroxyl group (in the case of R ²⁵ , it is assumed to be —CH ₂ OH).
One or more sugar units selected from the group comprising
A method for synthesizing a saccharide polymer comprising a step of producing a saccharide polymer by reacting in the presence of an acid catalyst and a supercritical fluid.
(77) The method according to Item (76), wherein the supercritical fluid is a fluid of carbon dioxide.
(78) The method according to Item (76), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(79) Formula (IV);

Wherein R ²⁹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ³⁰ is —OR ³⁴ , —N ₃ or —NHR ³⁵ , and R ³¹ and R ³² are — OR ³⁴ , R ³³ is —H, —CH ₃ , —CH ₂ OR ³⁴ , or —COOR ³⁶ , and R ³⁴ , independently of each other, is a hydroxyl protecting group or any reactive functional group containing a hydroxyl group. A sugar chain in which the group is protected, R ³⁵ is an amino group protecting group, and R ³⁶ is a carboxyl group protecting group).
Diacylglycerol, ceramide, sterol and a terpene having at least one hydroxyl group in the molecule, and formula (V);
R-OH (V)
(Wherein R is a straight chain, branched chain, a cyclic saturated aliphatic group having no side chain, or a cyclic saturated aliphatic group having a side chain, or containing one or more unsaturated bonds. An unsaturated aliphatic group corresponding to the group.)
A sugar receptor selected from the group comprising lipids, saturated fatty alcohols and unsaturated fatty alcohols,
A method for synthesizing a glycoside, comprising a step of producing a glycoside by reacting in the presence of an acid catalyst and a supercritical fluid.
(80) A method according to Item (79), wherein the supercritical fluid is a fluid of carbon dioxide.
(81) The method according to Item (79), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(82) Formula (IV);

Wherein R ²⁹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ³⁰ is —OR ³⁴ , —N ₃ or —NHR ³⁵ , and R ³¹ and R ³² are — OR ³⁴ , R ³³ is —H, —CH ₃ , —CH ₂ OR ³⁴ , or —COOR ³⁶ , and R ³⁴ , independently of each other, is a hydroxyl protecting group or any reactive functional group containing a hydroxyl group. A sugar chain in which the group is protected, R ³⁵ is an amino group protecting group, and R ³⁶ is a carboxyl group protecting group).
Formula (VI);

(Wherein R ³⁷ is —H or —CH ₃ , R ³⁸ is an amino group protecting group, a peptide chain to which a peptide chain or a sugar chain is bonded, and R ³⁹ is a carboxyl group protecting group, a peptide chain or a sugar chain. A peptide chain to which a chain is bonded, provided that when R ³⁸ and / or R ³⁹ is a peptide chain to which a sugar chain is bonded, all reactive functional groups including the hydroxyl group of the sugar chain are protected. Suppose)
A sugar receptor selected from the group comprising amino acids, peptide chains and peptide chains to which sugar chains are bound,
A method for synthesizing a glycoside, comprising a step of producing a glycoside by reacting in the presence of an acid catalyst and a supercritical fluid.
(83) The method according to Item (82), wherein the supercritical fluid is a fluid of carbon dioxide.
(84) A method according to item (82), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(85) Formula (IV);

Wherein R ²⁹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ³⁰ is —OR ³⁴ , —N ₃ or —NHR ³⁵ , and R ³¹ and R ³² are — OR ³⁴ , R ³³ is —H, —CH ₃ , —CH ₂ OR ³⁴ , or —COOR ³⁶ , and R ³⁴ , independently of each other, is a hydroxyl protecting group or any reactive functional group containing a hydroxyl group. A sugar chain in which the group is protected, R ³⁵ is an amino group protecting group, and R ³⁶ is a carboxyl group protecting group). Any one sugar donor selected from the group comprising sugar units When,
Formula (VII);

Wherein R ⁴⁰ is —OR ⁴⁵ , R ⁴¹ is —OR ⁴⁶ , —N ₃ or —NHR ⁴⁷ , R ⁴² is —OR ⁴⁸ , R ⁴³ is —OR ⁴⁹ , R ⁴⁴ Is —H, —CH ₃ , —CH ₂ OR ⁵⁰ or —COOR ⁵¹ , wherein R ⁴⁵ is a peptide in which diacylglycerol, ceramide, sterol, terpene, peptide chain or sugar chain is bonded, in which a hydrogen atom is removed from a hydroxyl group R ⁴⁶ is a sugar chain in which all reactive functional groups including -H, hydroxyl protecting group or hydroxyl group are protected, and R ⁴⁷ is a saturated aliphatic group or unsaturated aliphatic group. an amino group protecting group, R ^48, R ⁴⁹ and R ⁵⁰ is each independently of one another, -H, a sugar chain in which all of the reactive functional groups protected, including a hydroxyl protecting group or a hydroxyl group, R ⁵¹ A carboxyl group protecting group. ^{However, R 46,} R 48, R ⁴⁹ and ^{R 50} is all and no case is a hydroxyl-protecting ^group, among ^{R 46,} R 48, R ⁴⁹ and ^{R 50,} any One is -H, or when none of R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ is -H, then one of the sugar chains has one unprotected hydroxyl group. Suppose)
A sugar receptor selected from the group comprising the sugar units of
A method for synthesizing a glycoside, comprising a step of producing a glycoside by reacting in the presence of an acid catalyst and a supercritical fluid.
(86) A method according to Item (85), wherein the supercritical fluid is a fluid of carbon dioxide.
(87) A method according to item (85), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.
(88) Use of supercritical fluids in glycosylation reactions.
(89) The use according to item (88), wherein the supercritical fluid is a fluid of carbon dioxide.
(90) Use of an acid catalyst in a glycosylation reaction.
(91) The use according to item (90), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.

Figure 1 is a graph illustrating a powder X-ray diffraction lines of zeolite crystals person represented by the ideal formula _{NaAlSi 2 O 6 · H 2 O} . FIG. 2 is a diagram showing a powder X-ray diffraction line of an Mg-exchanged zeolite analog crystal represented by Na ₁₀ Mg ₃ Al ₁₆ Si ₃₂ O ₉₆ · 25H ₂ O. FIG. 3 is a diagram showing an example of a powder X-ray diffraction line of a zeolite analog after acid / alkali treatment produced according to the present invention. FIG. 4 is a diagram showing X-ray powder diffraction lines of diatomaceous earth from Chizen Hokkaido, pretreated with acid / alkali. FIG. 5 is a diagram showing X-ray powder diffraction lines of diatomaceous earth produced in Rukabe, Hokkaido, after pretreatment with acid / alkali. FIG. 6 is a diagram showing X-ray powder diffraction lines of diatomaceous earth from Hirosaki, Aomori Prefecture after pretreatment with acid / alkali. FIG. 7 is a diagram showing X-ray powder diffraction lines of diatomaceous earth from Higashikawa, Hokkaido, after pretreatment with acid / alkali. FIG. 8 is a diagram showing the crystal structure of zeolitic as a model for molecular orbital calculation. FIG. 9 is a diagram showing an X-ray powder diffraction line of a zeolite analog that expresses Lewis acidity, obtained by treating sulfuric acid and calcining diatomaceous earth produced in Chizen, Hokkaido. FIG. 10 is a diagram showing an X-ray powder diffraction line of a zeolite analog that expresses Lewis acidity, obtained by subjecting diatomaceous earth produced in Rukabe, Hokkaido, to sulfuric acid and baking treatment. FIG. 11 is a diagram showing an X-ray powder diffraction line of a zeolite analog that expresses Lewis acidity, obtained by subjecting Hirosaki Aomori Prefecture diatomaceous earth to a sulfuric acid and baking treatment. FIG. 12 is a diagram showing an X-ray powder diffraction line of a zeolite analog that expresses Lewis acidity, obtained by subjecting Higashikawa Hokkaido diatomaceous earth to sulfuric acid and baking treatment. FIG. 13 is a diagram showing X-ray diffraction lines of a Zr skeleton-substituted zeolite analog made from diatomaceous earth produced in Rukabe, Hokkaido. FIG. 14 is a transmission electron micrograph of a cross section of a diatom fossil in a clayey diatomaceous earth containing a Zr skeleton-substituted zeolite analog. FIG. 15 is a photograph showing the element distribution of a granular aggregate having a diameter of 100 nm on the surface of the diatom fossil shown in FIG. FIG. 16 shows the result of analyzing the elemental composition of the granular material of FIG. FIG. 17 shows the result of analyzing the elemental composition of a granular material different from FIG. FIG. 18 is a diagram showing X-ray powder diffraction lines of bentonite. FIG. 19 is a diagram showing an X-ray powder diffraction line of bentonite consolidated into an unglazed form after treatment. FIG. 20 is a diagram showing an X-ray powder diffraction line of silicon dioxide (made by precipitation, amorphous). FIG. 21 is a diagram showing X-ray powder diffraction lines of amorphous silica. FIG. 22 is a diagram showing X-ray powder diffraction lines of clayey diatomite obtained by subjecting diatomaceous earth from Rukabe-nada, Hokkaido, only to a baking treatment. FIG. 23 is a view showing a synthesis chart for producing a proton type zeolite analog or a proton type zeolite analog into which a transition metal is introduced from a raw material. FIG. 24 is a diagram for explaining a configuration example of a reaction apparatus used for the glycosylation reaction of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. It is to be understood that the terms used herein are commonly used in the art unless otherwise noted.

  In the present specification, “inorganic mineral” means a natural or artificial substance containing an inorganic substance and having almost uniform and constant chemical and physical properties, and may or may not contain an organic substance. .

  Inorganic minerals are generally classified crystallographically, silicate minerals, elemental minerals, sulfide minerals, oxide minerals, nitrate minerals, carbonate minerals, borate minerals, sulfate minerals, tungstates and molybdates. It can be roughly classified into minerals, phosphates, arsenates, vanadate minerals, and the like.

In this specification, a silicate mineral containing silicon can be given as a preferable inorganic mineral that can be the basis of the raw material. This silicate mineral is generally composed of a nesosilicate group (eg, olivine ((Fe, Mg) ₂ [SiO ₄ ]), garnet, etc.), a solosilicate group (chlorite (Ca ₂ (Al, Fe) Al ₂ [O | OH | SiOH | Si ₂ O ₇ ])), cyclosilicate group (such as beryl (Al ₂ Be ₃ [SiO ₁₈ ])), inosilicate group ((Ca, Mg) , Fe, Al, Ti) ₂ [(Si, Al) ₂ O ₆ ]), phyllosilicate group (mica, chlorite, clay mineral, etc.), tectosilicate group (quartz, feldspar, zeolite group, part-time, It is classified as zeolite (Na (AlSiO ₆ ) · H ₂ O).

  In the present specification, “clay mineral” means an inorganic substance as a main component constituting clay. Examples of clay minerals include kaolin minerals, serpentine minerals, pyrophyllites, talc, smectite groups including montmorillonite, mica clay minerals including permiculite, illite and muscovite, brittle mica and chlorite. Among these clay minerals, the clay minerals contained in the untreated clayey diatomite are smectite groups including montmorillonite and mica clay minerals including illite and muscovite, but the clay diatomite used in the present invention is used. Removed the smectite clay mineral containing montmorillonite by pre-treatment with acid / alkali treatment in advance. “Treatment” in the present specification means an operation such as, for example, mixing, dissolution, suspension or chemical reaction, but is not limited thereto.

  In the present specification, “inorganic acid” refers to hydrochloric acid, sulfuric acid, nitric acid, and the like, but is not limited thereto. Preferable examples of the inorganic acid include sulfuric acid, particularly dilute sulfuric acid. The concentration of the inorganic acid is not particularly limited and can be changed as appropriate.

According to the present invention, when producing a proton-type zeolite analog that functions as a Lewis acid or a proton-type zeolite analog into which a transition metal is introduced, preferably, diatomaceous earth, A mixture of at least one of clayey diatomite, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediments and lake sediments may be used. In addition to the above inorganic minerals, natural substances that can be used as a raw material of the present invention include oxide minerals typified by hydrous silicate minerals such as opal (SiO ₂ · nH ₂ O); and illite, paragonite, chinwald mica, ricia mica, It is particularly preferable to further include a mica mineral or a mica-based clay mineral including at least one of biotite, phlogopite, sea chlorite, and muscovite.

Each of the natural substances listed above includes, for example, the new edition of the Geographical Dictionary, Geographical Society Study Group, Heibonsha, October 20, 1996. Large Dictionary The Kyoritsu Publishing Co., Ltd., edited by the Editorial Committee of the Chemical Dictionary, published in 1960, the first edition, and other substances.

  In conventional diatomaceous earth applications, Neogene diatomaceous earth containing clay minerals has been of low quality, but the present invention provides new applications for Neogene diatomaceous earth containing clay minerals. For example, Hokkaido Kashioka (near Wakkanai), Tobetsu / Kanakomanai (near Tobetsu), Notori / Yojin (near Abashiri), Ichizen (Urahoro-cho, Tokachi-gun), Torube-be (Tokoro-gun, Rubebe-cho) Mineral Tertiary diatomite that can be mined from the Sakaiuchi River basin is the main component of opal or α-cristobalized amorphous silica, smectite clay minerals such as montmorillonite as impurities, and mica systems such as illite and muscovite Clay diatomaceous earth containing clay minerals as impurities.

The Al ₂ O ₃ content of quaternary diatomite generally regarded as fine is 0.5 to 2%, but the Al ₂ O ₃ content of Neogene diatomaceous earth from Hokkaido is 3 to 10%. %. In diatomaceous earth, the clay mineral is a rock-forming mineral containing abundant Al ₂ O ₃ , and the Neogene diatomaceous earth from Hokkaido is characterized by clay. In addition to Hokkaido and Aomori, diatomaceous earth distributed throughout the Noto Peninsula in Ishikawa Prefecture is well known as clayey diatomaceous earth. By using clay minerals contained in clayey diatomaceous earth as an alumina source, zeolite analogues can be synthesized without adding commercially available sodium aluminate as an alumina source to diatomaceous earth mainly composed of silica. . This is a manufacturing method according to the natural zeolitic formation process, which not only can reduce costs, but also is a low environmental load manufacturing method.

Since the content of Al ₂ O ₃ contained in the clay diatomaceous earth is 10% at the maximum, most of the amorphous silica, which is the main component of diatomaceous earth, is not used for the synthesis of zeolite analogues. Nevertheless, in an experiment (Reference Example 3) in which a clay diatomaceous earth containing a zeolite analog was used as a solid acid catalyst, the target product could be obtained in a sufficient yield. This is because the amorphous silica remaining without being used in the synthesis of the zeolite analog, that is, diatom fossil, effectively functioned as a support for the zeolite analog. In general, diatom fossils and diatom cell walls are porous and are known to be effective as a single catalyst. The state in which the zeolite analog is actually supported on the surface of the diatom shell is shown in Example 6 as a transmission electron microscope image (FIG. 14).

  As a raw material, it is preferable to use a Neogene diatomaceous earth from Hokkaido, but a zeolite analog can be obtained by using a Neogene diatomaceous earth from Aomori. Furthermore, even when a high-quality Hokkaido quaternary diatomaceous earth is used as a raw material, a zeolite analog can be obtained although the signal of the X-ray diffraction line is weak, the production method of the present invention is a type of diatomaceous earth. It is not limited to.

  Refer to FIG. 23 (synthesis chart for obtaining a final product from raw materials) for the method of producing a proton type zeolite analog that functions as a Lewis acid catalyst or a proton type zeolite analog into which a transition metal is introduced. Thus, those skilled in the art can easily understand. The items described in FIG. 23 are merely described for the purpose of illustration and simplification, and the present invention is not limited to these. The production method of the present invention will be described as follows. In the present specification, the “zeolite analog” refers to a structure having the above-mentioned tectosilicate as a basic skeleton.

  In one embodiment of the present invention, in order to obtain an intermediate that is a raw material for producing a proton-type zeolite analog, as a pretreatment, an inorganic mineral that is a raw material is acid-treated (step 1 in FIG. 23). Is decanted in a neutral or alkaline solution (step 2 in FIG. 23) to obtain a raw material from which the smectite clay mineral has been removed (intermediate 1 in FIG. 23). The decantation step is performed as necessary.

Preferred embodiments for obtaining intermediate 1 from raw materials are exemplified below.

According to the present invention, preferably, a Neogene Hokkaido clay diatomaceous earth is used as a raw material (for example, the raw material of FIG. 23). The dried diatomaceous earth rock is crushed with a hammer or the like, put into a processing container, and if necessary, hydrogen peroxide solution, preferably 1 to 30%, more preferably 30% hydrogen peroxide solution is added and washed. To do. After leaving for 1 to 2 hours, if necessary, an additional 1 to 36%, preferably 30 to 36% hydrochloric acid solution is added and washed (for example, step 1 in FIG. 23). At this time, be careful because it will foam violently and become hot. When boiling begins, water is added and the reaction temperature is controlled to 60 to 90 ° C, preferably about 80 ° C. When the color of the solution is yellow and the foam has settled, add cold water and wait for the crushed diatomaceous earth to settle. With this acid treatment, diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, or unconsolidated marine sediment, lake marine sediment, It is crushed into mud. In the case of strongly consolidated diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, and siltstone, fragments of a particle size of 1 mm or more may remain. In this case, after the precipitate is vigorously stirred, only the suspension is transferred to another container to separate the muddy precipitate. The debris remaining without being crushed can be reprocessed.

  When completely precipitated, repeat the decantation several times to discard the supernatant. Decantation is performed several times with a solution containing a dispersant (for example, 0.01 to 0.1% sodium pyrophosphate solution) at a pH of 6 to 7, preferably around pH 7 (for example, the process of FIG. 23). 2). In this case, the supernatant is turbid due to suspended clay minerals, so decant carefully to avoid breaking the sediment. In this case, it is preferable to perform decantation every 1 to 4 hours, preferably every 3 hours. Thereafter, decantation with water is repeated several times, and the precipitate is dried at 100 to 150 ° C. with a vacuum dryer or an electric furnace to obtain a powdery dry clay diatomaceous earth. When diatomaceous earth from Hokkaido is used, a powdery dry clay-like diatomaceous earth corresponding to 10 to 40% of the raw material weight is usually obtained.

  By the above, the raw material (for example, the intermediate body 1 of FIG. 23) from which impurities, such as a smectite clay mineral, were removed can be obtained. Whether or not the impurities have been removed can be confirmed by, for example, analysis by X-ray powder diffraction.

  An example of the powder X-ray diffraction line of the zeolite analogue after acid / alkali treatment produced according to the present invention is shown in FIG. FIG. 3 shows a similar powder X-ray diffraction line to the Mg-exchanged zeolite analog of FIG. 2 of Reference Example 2, showing a crystal plane showing an interatomic distance of 5.87 to 5.93 と, and 3.52 to 3 A crystal plane showing an interatomic distance of .54 cm and a crystal plane showing an interatomic distance of 2.93 to 2.95 kg.

  In addition, in FIG. 3, IK is a powder X-ray diffraction line of a zeolite analog using diatomaceous earth from Chizen Hokkaido, as a raw material, and RB is a powder X-ray diffraction of a zeolite analog using diatomaceous earth from Rukabe, Hokkaido as a raw material. HR is a powder X-ray diffraction line of zeolite analogue using Hirosaki acid diatomaceous earth as a raw material, and HG is a powder X-ray diffraction line of zeolite analogue using diatomite from Higashikawa, Hokkaido as a raw material. . A1 is the 211 crystal face of the zeolite analog, A2 is the 400 or 410 crystal face, A3 is the 332 or 422 crystal face, Q is the crystal face of quartz, and F is the crystal face of feldspar. And C is the crystal face of cristobalite.

  In one embodiment of the present invention, an inorganic acid is added to the raw material from which the smectite clay mineral is removed (intermediate 1 in FIG. 23), and a silica source and an alumina source are reacted to obtain a reaction product (FIG. 23 step 3), this is dried (step 4 in FIG. 23) and then calcined (step 5 in FIG. 23) to obtain a proton type zeolite analog (final product in FIG. 23) functioning as a Lewis acid. obtain. Drying is performed as necessary.

  A preferred embodiment for obtaining the final product 1 from the intermediate 1 is illustrated as follows.

The dry powdery clay diatomaceous earth is transferred to Meyer with a capacity of 50 ml, and an inorganic acid is added (for example, step 3 in FIG. 23). Here, as a preferable example of the inorganic acid, 1N sulfuric acid (corresponding to 3.8 ml with respect to 1 g of diatomaceous earth) can be mentioned, but the kind and concentration of the inorganic acid are not particularly limited and can be appropriately changed. After the inorganic acid is added, it is dried overnight at room temperature (for example, step 4 in FIG. 23). Drying is performed by introducing dry air into Meyer with an air pump. This drying is performed as necessary. Since the weight decreases as the sulfuric acid solution evaporates, it is preferable to continue drying until there is no change in weight. After drying, calcination for several hours (for example, step 5 in FIG. 23) yields a zeolite analog that exhibits Lewis acidity (for example, the final product 1 in FIG. 23) in diatomaceous earth. Here, the upper limit of the formation temperature of zeolitic is 450 ° C. (see, for example, Ghobarkar, H. et al., Effect of temperature on thermal synthesis of visci- te and vis_ite, pages 16-3, 19th, 19th, 1999) Under normal pressure conditions, the stable region of zeolite is up to 540 ° C. (for example, Peter, T., Luth, WC, et al., The melting of analyst solid solutions in the NaAlSiO ₄ -NaAlSi ₃ O ₈ -H ₂ O, The American Mineralology, 1966, Vol. 51, pages 736-753) It is. Therefore, as in the present invention, it is considered that a firing temperature at least equal to or higher than the above-described temperature is necessary to cause distortion in the crystal structure and to generate Lewis acid activity. The firing temperature used in the present invention is 500 ° C. or higher, preferably 540 ° C. or higher, more preferably around 650 ° C. The fact that crystals of the zeolite analogue were obtained is confirmed by analysis by X-ray powder diffraction.

In contrast, when a sulfuric acid solution is added to bentonite rich in montmorillonite and baked at 650 ° C., paragonite is generated (see Comparative Example 1). In the present invention, by using the clay diatomite from which montmorillonite has been removed, the production of minerals other than the zeolite analog can be suppressed as shown in Examples 1 to 4. That is, the mineral produced after adding sulfuric acid from these diatomaceous earths and firing at 650 ° C. is only a zeolite analog. In addition, whether or not Lewis acidity develops in a zeolite analog from which H ₂ O molecules are eliminated from the zeolite analog can be confirmed by, for example, a molecular orbital calculation method.

Here, the proton type zeolite analog in which all or part of the cation is substituted with H ⁺ is generally represented by the following (formula 1):
_{W p H m-p Z n} O 2n · SH 2 O ( Equation 1)
Where W is an alkali metal, alkaline earth metal, or a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB, and H is a hydrogen atom Z is Al + Si, and the Si / Al ratio is an integer of 1 or more, m and n are each an integer of 1 or more, and p is an integer of 0 or more and less than m. , S is an arbitrary number of 0 or more). When this proton-type zeolite analog is heated, the zeolite water is desorbed, and thus takes the structure of the following (formula 2).

W _{ph m-p} Z _n O _2n (Formula 2)
When H is completely lost from (Equation 1) because it is calculated that the Lewis acid activity is expressed in the zeolite analog by desorbing H and O atoms as water molecules in a ratio of 2: 1 Can be expressed as the following (formula 3).

_{Z n O 2n-0.5 (m} -p) ( Equation 3)
From the above, when the proton-type zeolite analog of (Formula 1) is subjected to Lewis oxidation, the number of oxygen atoms O can be defined as (2n-0.5 (mp)) or more and less than 2n. .

Next, a method for producing a skeleton-substituted zeolite analog in which the TO ₄ tetrahedron is replaced with ZrO ₄ is shown below.

  In one embodiment of the present invention, as described above, a transition metal compound is supported on the raw material (intermediate 1) from which the smectite clay mineral has been removed (step 6 in FIG. 23), and this product is hydrolyzed (FIG. 23, Step 7), and Intermediate 1 carrying a transition metal (Step 2 in FIG. 23) is obtained. Hydrolysis is performed as necessary.

  A preferred embodiment for obtaining intermediate 2 from intermediate 1 is illustrated as follows.

A dry powdery clay diatomaceous earth (for example, step 6 in FIG. 23) is filled in a container, ZrCl ₄ vaporized at 400 ° C. is sent to the container, and fine ZrCl ₄ is formed by CVD (chemical vapor deposition). Vapor deposition on the surface of clay diatomaceous earth. Fine particles produced by the CVD method are homogeneously adsorbed on the clay mineral on the surface of the diatom fossil, so that a skeleton-substituted zeolite analog in which the TO ₄ tetrahedron is replaced can be efficiently produced. As described above, in addition to the above-described CVD method, a method of impregnating a transition metal hydroxide gel with a dry powdery clay diatomaceous earth is also effective as a method for supporting the transition metal compound on the intermediate 1. Preferred examples of the transition metal hydroxide include Ti (OH) ₄ or Zr (OH) ₄ .

  In one embodiment of the present invention, an inorganic acid is added to the above-described transition metal-supported intermediate 1 (intermediate 2 in FIG. 23), and a reaction product is obtained by reacting the transition metal with a silica source and an alumina source. (Step 8 in FIG. 23), the product is dried (Step 9 in FIG. 23), and then calcined (Step 10 in FIG. 23) to introduce a proton-type zeolite analog into which a transition metal functioning as a Lewis acid is introduced. (Final product 2 in FIG. 23) is obtained.

  A preferred embodiment for obtaining the final product 2 from the intermediate 2 is illustrated as follows.

After the above-described deposition of ZrCl ₄ , air is sent to the container to hydrolyze the particulate ZrCl ₄ to generate ZrCl ₂ O · 8H ₂ O on the surface of the clay diatomaceous earth (for example, step 7 in FIG. 23). After hydrolysis of ZrCl _4, loading of the clay diatomaceous earth ZrCl ₂ O · 8H ₂ O is calculated by measuring the weight gain, estimate the supported amount per diatomite 1g. From the container, clay diatomaceous earth carrying ZrCl ₂ O · 8H ₂ O (e.g., Intermediate 2 in FIG. 23) was taken out, (preferably, 28% aqueous ammonia) aqueous ammonia was transferred to a beaker adding Zr (OH ) Get ₄ . The precipitate is washed by decantation (5 times) and dried at 100 to 150 ° C. overnight in an electric furnace or the like. An inorganic acid is added after drying (for example, step 8 in FIG. 23). The kind and concentration of the inorganic acid are not particularly limited, but 1N sulfuric acid (equivalent to 3.8 ml per 1 g of diatomaceous earth) is particularly preferable. After adding an inorganic acid and drying overnight at room temperature (for example, step 9 in FIG. 23), the temperature is 500 ° C. or higher, preferably 540 ° C. or higher, more preferably around 650 ° C. for 1 to 5 hours, preferably 3 A time-calcined (for example, step 10 in FIG. 23), a Zr skeleton-substituted zeolite analog in which the TO ₄ tetrahedron of the zeolite analog is replaced with ZrO ₄ is obtained. It is confirmed by X-ray powder diffraction analysis that this Zr framework substitution type zeolite analog is obtained. In addition, whether or not Lewis acidity is developed in a zeolite analog from which H ₂ O molecules are eliminated from a Zr-introduced zeolite analog is confirmed by a molecular orbital calculation method.

Similar to the proton type zeolite into which Zr is not introduced, the proton type zeolite analog in which all or a part of protons are substituted with H ⁺ is represented by the above (formula 1) (where, W, m, n, p and S are as defined above (Formula 1), and Z is a transition metal selected from the group consisting of elements from Group IIIA to Group VIIA, Group VIII and IB, or Group IIIB and Group IVB The number of oxygen atoms O in the Lewis-oxidized proton-type zeolite analog is not less than (2n−0.5 (mp)) and less than 2n, which is a typical metal element selected from the group consisting of elements. Can be defined.

  In another embodiment of the present invention, a glycosylation reaction characterized by reacting a sugar donor and a sugar acceptor in the presence of a catalyst and a supercritical fluid, ie, a carbohydrate macromolecule or glycoside A synthetic method is provided.

  In the present specification, the “sugar-containing substance” refers to a substance containing a monosaccharide or a sugar chain and a substance other than these. Many such sugar-containing substances are found in the living body. For example, in addition to polysaccharides and carbohydrate polymers contained in the living body, degraded polysaccharides, glycoproteins, proteoglycans, glycosaminoglycans, sugars Examples include, but are not limited to, complex biomolecules or glycosides such as lipids, and sugar chains that are decomposed or derived from these complex biomolecules.

  In the present specification, the “carbohydrate polymer” refers to a compound formed by connecting one or more unit sugars (monosaccharide and / or a derivative thereof). When two or more unit sugars are connected, the unit sugars are usually bonded by dehydration condensation using a glycosidic bond. Examples of such sugar chains include polysaccharides contained in the living body (glucose, galactose, mannose, fucose, xylose, N-acetylglucosamine, N-acetylgalactosamine, sialic acid, and complexes and derivatives thereof). Other examples include, but are not limited to, a wide range of sugar chains that are decomposed or derived from complex biomolecules such as degraded polysaccharides, glycoproteins, proteoglycans, glycosaminoglycans, and glycolipids. In the present specification, a carbohydrate polymer may be used interchangeably with “sugar chain”, “polysaccharide”, “saccharide”, and “carbohydrate”. Further, unless otherwise specified, the “sugar chain” in the present specification may include both sugar chains and sugar chain-containing substances.

  In the present specification, the “glycoside” is a compound in which a hydrogen atom of a hemiacetal or hemiketal hydroxyl group of a sugar is substituted with a functional group such as an alkyl group or an aryl group, and reacts with a sugar. Examples thereof include alcohol, lipid, and peptide chain.

As used herein, “monosaccharide” refers to polyhydroxyaldehyde or polyhydroxyketone and derivatives thereof that are not hydrolyzed into simpler molecules and contain at least one hydroxyl group and at least one aldehyde group or ketone group. Say. Usually monosaccharides, the general formula C _n H _2n O is represented by _n is not limited to, fucose (deoxyhexose), also include such N- acetylglucosamine. Where n = 2, 3, 4, 5, 6, 7, 8, 9 and 10 in the above formula, diose, triose, tetrose, pentose, hexose, heptose, octose, nonose and decourse, respectively That's it. Generally, it corresponds to an aldehyde or ketone of a chain polyhydric alcohol. The former is called aldose and the latter is called ketose. When specifically mentioned herein, a monosaccharide derivative refers to a substance that results from the substitution of one or more hydroxyl groups on an unsubstituted monosaccharide with another substituent. Examples of such monosaccharide derivatives include sugars having a carboxyl group (for example, aldonic acid in which C-1 position is oxidized to carboxylic acid (for example, D-gluconic acid in which D-glucose is oxidized), terminal Uronic acid in which C atom of carboxylic acid becomes carboxylic acid (D-glucuronic acid in which D-glucose is oxidized), sugar having amino group or amino group derivative (for example, acetylated amino group) (for example, N- Acetyl-D-glucosamine, N-acetyl-D-galactosamine, etc.), sugars having both amino groups and carboxyl groups (for example, N-acetylneuraminic acid (sialic acid), N-acetylmuramic acid, etc.), deoxy Such as, but not limited to, glycated sugars (eg, 2-deoxy-D-ribose), sulfated sugars containing sulfate groups, phosphorylated sugars containing phosphate groups, etc. In the present specification, the term “monosaccharide” includes the above-mentioned derivatives, or, in a sugar having a hemiacetal structure, a glycoside having an acetal structure by reacting with an alcohol is also within the range of the monosaccharide. .

  As used herein, “glycopeptide” and “glycoprotein” are used interchangeably and refer to peptides and proteins comprising at least one sugar chain. Usually, glycoproteins have sugar chains necessary for exerting functions in higher organisms. The sugar chain and the peptide or protein may be directly bonded, or may be indirectly bonded via a spacer (for example, any divalent group such as a polymethylene group). Examples of such glycoproteins include, but are not limited to, enzymes, hormones, cytokines, antibodies, vaccines, receptors, serum proteins, and the like.

  A well-known thing can be used for peptides, such as insulin. Illustrative examples of insulin include, but are not limited to, human insulin, porcine insulin, bovine insulin, and the like. Insulin has an A chain, an N-terminal amino group of the B chain, and a side chain amino group of a lysine residue. It is known that there are differences in lysine residues depending on the species, but anything can be used.

  In the present specification, a “supercritical fluid” is defined as a non-condensable fluid that exceeds the critical temperature of a substance-specific gas-liquid. The supercritical fluid has both gas and liquid characteristics, that is, as a solvent, it has high solubility close to liquid and high diffusivity close to gas. Specifically, a supercritical fluid using water, carbon dioxide, alcohol or the like is known.

  The solvent applied to the glycosylation reaction of the present invention, that is, the method for synthesizing a carbohydrate polymer or glycoside, is preferably a supercritical fluid of carbon dioxide.

  Since carbon dioxide has almost the same polarity as hexane, which is generally used as an organic solvent, these are dissolved particularly when a sugar donor and / or sugar acceptor containing a protecting group is used. It is easy to do and reaction efficiency is good.

  Further, if a supercritical fluid of carbon dioxide is used, it can be easily removed as a gas after the completion of the reaction process, so that separation and recovery of a product substance such as a carbohydrate polymer or a glycoside becomes extremely easy. Therefore, the burden on the environment due to the reaction solvent can be reduced. In addition, the supercritical fluid of carbon dioxide is excellent in safety and operability.

The catalyst applied to the glycosylation reaction of the present invention is not particularly limited as long as the object of the present invention is not impaired. Usable catalysts include AgOTf (silver trifluoromethanesulfonate), TMSOTf (trimethylsilyl trifluoromethaneate), BF ₃ · OEt ₂ (boron trifluoride diethyl ether complex), SnCl ₂ -AgClO ₄ , SnCl ₂ -AgOTf, Cp ₂ ZrCl ₂ -AgClO ₄ (Cp ₂ ZrCl ₂ : zirconocene dichloride), sulfated zirconia (ZrO ₂ / SO ₄ ), diatomaceous earth, sulfated diatomaceous earth, SO ₄ ²⁻ / TiO ₂ / diatomaceous earth (sulfated titania-supported diatomaceous earth) Preferably, a solid acid catalyst that can be easily separated after completion of the reaction, that is, AgOTf, sulfated zirconia (ZrO ₂ / SO ₄ ), diatomaceous earth, sulfated diatomaceous earth, SO ₄ ²⁻ / TiO ₂ / It is better to use diatomaceous earth. More preferably, it is preferable to use a sulfated diatomaceous earth that can recycle the catalyst, has a low environmental load, and has excellent catalytic activity.

In the glycosylation reaction of the present invention, the sugar donor is not particularly limited as long as it has a —OC (NH) CCl ₃ , —Cl, —Br or F leaving group at the 1-position.

When synthesizing a carbohydrate polymer, it is preferable to use one or more selected from the group containing a saccharide unit of the following formula (I), for example.

Wherein R ¹ is —OC (NH) CCl ₃ , —Cl, —Br or —F, R ² is —OH, —OR ⁶ , —N ₃ or NHR ⁷ , R ₃ and R ₄ Are independently —OH or OR ⁶ , R ⁵ is —H, —CH ₃ , —CH ₂ OH, —CH ₂ OR ⁶ , or COOR ⁸ , and R ⁶ is independently of each other , A hydroxyl protecting group, or a sugar chain in which all reactive functional groups containing a hydroxyl group are protected, R ⁷ is an amino group protecting group, and R ⁸ is a carboxyl group protecting group).

Here, when a specific structure is required for the saccharide polymer to be produced, an appropriate protecting group is introduced so that a reactive hydroxyl group is not contained in R ² to R ⁵ in the formula, A reaction may be performed. In the case where the saccharide polymer to be produced may contain a random structure and / or a plurality of types of saccharide units, one or two or more types of saccharide units having one or two or more reactive hydroxyl groups, It can also be made to react by mixing suitably.

  In the present invention, the number of monosaccharides constituting the sugar chain is adjusted so that the total number of monosaccharides in the compound is 20 or less in consideration of solubility in a supercritical fluid and practical utility. Is good.

  Specific examples of monosaccharides constituting the sugar chain include glucose, galactose, mannose, talose, idose, growth, allose, altrose, xylose, lyxose, arabinose, ribose, fucose, rhamnose and other aldoses, fucose, and rhamnose. Deoxy sugars such as glucuronic acid, galacturonic acid, mannuronic acid, iduronic acid, and uronic acid such as guluronic acid, and amino sugars such as glucosamine, galactosamine, and muramic acid. Moreover, as a reactive functional group which these sugar chains have, a hydroxyl group, an amino group, and a carboxyl group are mentioned. Here, the sugar chain may be composed of the same type of monosaccharide or may be composed of two or more types of monosaccharide.

  In the synthesis method of the present invention, the hydroxyl group, amino group, and carboxyl group of the sugar chain may be appropriately protected with a hydroxyl group protecting group, an amino group protecting group, and a carboxyl group protecting group, respectively, and the reaction step may be carried out.

  Here, as for the hydroxyl group protecting group, amino group protecting group and carboxyl group protecting group, a protecting group well known to those skilled in the art may be introduced at a desired position by a well known method. Specifically, as the hydroxyl protecting group, for example, an acyl protecting group including an acetyl group, a benzoyl group, a monochloroacetyl group, a sulfonic acid ester group, a benzyl group, a methoxybenzyl group, a trityl group, a triphenylmethyl group, Examples include ether-based protecting groups including allyl groups and silyl ether groups. When two or more hydroxyl protecting groups are present in the same molecule, they may be the same hydroxyl protecting groups or different hydroxyl protecting groups. Examples of the amino group protecting group include acetyl group, methyl group, carbamate group, naphthyl group, thiocarbamate group, trihalogen acetyl group and the like. When two or more amino protecting groups are present in the same molecule, they may be the same amino protecting group or different amino protecting groups. Examples of the carboxyl protecting group include an alkyl group, a silyl group, a thioalkyl group, and an aryl group. When two or more carboxyl group protecting groups are present in the same molecule, these may be the same carboxyl group protecting groups or different carboxyl group protecting groups.

  In the glycosylation reaction of the present invention, the sugar acceptor is not particularly limited as long as it is a compound having at least one hydroxyl group in the molecule.

When a carbohydrate polymer is used as a target product, the sugar receptor is preferably one or more compounds selected from the group containing a saccharide unit of the following formula (II), for example. It is good.

Wherein R ⁹ is —OR ¹⁴ , R ¹⁰ is —OR ¹⁵ , —N ₃ or NHR ¹⁶ , R ¹¹ is —OR ¹⁷ , R ¹² is —OR ¹⁸ , and R ¹³ is _-H, -CH _3, a -CH 2 ^{oR 19} or COOR ^{20, R 14} and ^{R 15} independently of one another, -H, and all of the reactive functional group containing a hydroxyl-protecting group or a hydroxy group is protected R ¹⁶ is an amino group protecting group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently protected by —H, a hydroxyl protecting group or all reactive functional groups including a hydroxyl group. R ²⁰ is a carboxyl protecting group, provided that at least one of R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ is —H.) .

  If there are two or more hydroxyl groups in the molecule, sugar donors will be bound in addition to the target hydroxyl group, and the selectivity of the reaction will be reduced. When required, it is preferable to have one hydroxyl group appropriately selected.

The glycosylation reaction of the present invention is also applicable when a sugar donor also serves as a sugar acceptor. Specifically, one or more saccharide units selected from the group containing the saccharide unit of the following formula (III) are reacted in the presence of a catalyst and a supercritical fluid as a solvent.

Wherein R ²¹ is —OC (NH) CCl ₃ , —Cl, —Br or F, R ²² is —OH, —OR ²⁶ , —N ₃ or NHR ²⁷ , and R ²³ and R ²⁴ are , Independently of one another, —OH or OR ²⁶ , R ²⁵ is —H, —CH ₃ , —CH ₂ OH, —CH ₂ OR ²⁶ or COOR ²⁸ , and R ²⁶ , independently of one another, is a hydroxyl group Protecting group or sugar chain in which all reactive functional groups including hydroxyl group are protected, R ²⁷ is an amino group protecting group, and R ²⁸ is a carboxyl group protecting group, provided that R ²² , R ²³ , R ²⁴ or R ²⁵ , at least one is a hydroxyl group (in the case of R ²⁵ , it is assumed to be —CH ₂ OH).

  In this case, since the saccharide unit of the formula (III) contains one or more reactive hydroxyl groups, the reactive hydroxyl group reacts with a leaving group of another molecule, thereby causing a glycosylation reaction. Occurs and a carbohydrate polymer is synthesized.

In the glycosylation reaction of the present invention, particularly when a glycoside is used as a target product, the sugar donor is preferably selected from the group containing a saccharide unit defined by the following formula (IV). It is recommended to use one kind.

Wherein R ²⁹ is —OC (NH) CCl ₃ , —Cl, —Br or F, R ³⁰ is —OR ³⁴ , —N ₃ or NHR ³⁵ , and R ³¹ and R ³² are —OR ^34. R ³³ is —H, —CH ₃ , —CH ₂ OR ³⁴ , or COOR ³⁶ , and R ³⁴ is independently of each other protected by a hydroxyl protecting group or all reactive functional groups containing a hydroxyl group. R ³⁵ is an amino group protecting group, and R ³⁶ is a carboxyl group protecting group).

  In this case, the sugar acceptor is preferably a diacylglycerol, a ceramide, a sterol or a lipid such as a terpene having at least one hydroxyl group in the molecule, and a saturated aliphatic alcohol represented by the following formula (V) Alternatively, an unsaturated fatty alcohol is preferred.

R-OH (V)
(In the formula, R is a linear, branched, cyclic having no side chain or a cyclic saturated aliphatic group having a side chain, or containing one or more unsaturated bonds. Unsaturated aliphatic group corresponding to the group).

  Here, examples of the sterol include monohydric alcohols such as cholesterol, β-ergosterol, sitosterol, cholestanol, stigmasterol, epicoprostanol, and coprostanol, and polyhydric alcohols such as estriol and estradiol. Furthermore, in the case where the molecule has a reactive functional group other than a hydroxyl group, that is, a carbonyl group, a carboxyl group, and an aldehyde group, the reaction is carried out after introducing a protecting group well known to those skilled in the art to a desired position by a well known method. As sterols having a carbonyl group, prednisone, androsterone, estrone, testosterone, prednisolone and the like, and as sterols having a carboxyl group, cholic acid, cholanic acid, deoxycholic acid, lithocholic acid and the like, Examples of sterols having an aldehyde group include aldosterone and strophantidine. As the protecting group, for carbonyl group, dimethyl acetal group, diethyl acetal group, dibenzyl acetal group, diacetyl acetal group, 1,3-dioxane acetal group, S, S′-dimethyl acetal group, etc., and for carboxyl group, Benzyl ester group, trichloro ester group, cyclohexyl ester, etc., and aldehyde group include dimethyl acetal group, diethyl acetal group, dibenzyl acetal group, diacetyl acetal group and the like.

  A terpene is a compound in which two or more isoprene units are linked in a chain or cyclic manner, and depending on the number of isoprene units, monoterpenes (two isoprene units), sesquiterpenes (three), diterpenes (four) ), Sesterterpenes (5), triterpenes (6), and tetraterpenes (8). In the present invention, any terpene can be used for the reaction, but it is of course essential to have at least one hydroxyl group in the molecule.

  Examples of terpenes satisfying the above requirements include monoterpenes such as nerol, (+)-linalool, (+)-isomenthol, γ-terpineol, (−)-menthol, (+)-borneol, (−)-isoborneol. , Sesquiterpenes such as farnesol, (+)-nerolidol and guaiool, diterpenes such as phytol, isophytol and geranylgeraniol, and triterpenes such as ambrain, α-onoserine, agnosterol, euphor and lanosterol. Furthermore, when the terpene molecule has a reactive functional group other than a hydroxyl group, such as a carboxyl group or a carbonyl group, a protective group well known to those skilled in the art can be introduced into a desired position by a well-known method and then subjected to the reaction. desirable.

  Further, as the alcohol, as defined in the formula (V), linear, branched, cyclic having no side chain or cyclic saturated and unsaturated aliphatic alcohol having a side chain can be used. Preferably, monohydric alcohol is used. Further, considering the solubility in a supercritical fluid as a solvent, the number of carbons is preferably 1 to 30 and more preferably 1 to 10 carbons. It is good.

  Preferred alcohols for the glycosylation reaction of the present invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, Linear saturated alcohols such as 1-nonanol and 1-decanol, linear unsaturated alcohols such as allyl alcohol (2-propen-1-ol), 2-penten-1-ol and 2-propyn-1-ol Branched saturated alcohols such as t-butyl alcohol, 3-ethyl-3-pentanol, 3-methyl-2-pentanol, 5-methyl-2-hexanol, cyclohexanemethanol, cyclooctanemethanol, 4-n -Propyl-1-hepten-4-ol, 2-methyl-1-pentene-3 Branched unsaturated alcohols such as all, 3-ethyl-5-hexen-3-ol, cyclic saturated alcohols having no side chain such as cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, Cyclic unsaturated alcohols having no side chain such as 2-cyclohexenol, cyclic saturated alcohols having a side chain such as 2-methylcyclohexanol, 3-methylcyclohexanol, 1-methylcycloheptanol, 1-ethylcyclohexanol In addition, cyclic unsaturated alcohols having a side chain such as 3-methyl-2-cyclohexen-1-ol can be mentioned.

In the glycosylation reaction of the present invention, the sugar receptor is preferably a compound selected from the group comprising amino acids and polypeptides represented by the following formula (VI).

(In the formula, R ³⁷ is —H or CH ₃ , R ³⁸ is an amino group protecting group, a peptide chain to which a peptide chain or a sugar chain is bonded, and R ³⁹ is a carboxyl group protecting group, a peptide chain or a sugar chain. In the case where R ³⁸ and / or R ³⁹ is a peptide chain to which a sugar chain is bonded, all reactive functional groups including the hydroxyl group of the sugar chain are protected. And).

  The peptide chain referred to here includes not only a compound in which two or more amino acid residues are linked by peptide bonds, but also a case where it is composed of one amino acid residue. It is desirable that the terminal carboxyl group be protected. As the number of amino acid residues increases, the solubility in the supercritical fluid and the stability of the compound decrease, so the number of amino acid residues as a whole compound is desirably 5 or less.

  Examples of the carboxyl protecting group include a methyl ester group, an ethyl ester group, a benzyl ester group, a t-butyl ester group, and the like. Examples of amino group protecting groups include benzyloxycarbonyl group, p-toluenesulfonyl group, t-butyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, t-amyloxycarboninyl group, isobornyloxycarbonyl group, Examples thereof include a phenylmethyl group, a 9-fluorenylmethyloxycarbonyl group, and a 5-benzisoxazolylmethyleneoxycarbonyl group.

  In addition to the amino group and carboxyl group, the reactive functional group in the peptide chain includes a hydroxyl group, a thiol group, a guanidino group, and an imidazole group, all of which must be protected by a known method. is there. For example, examples of the hydroxyl-protecting group include a benzyl group and a t-butyl group. In addition, as a protecting group for thiol group, benzyl group, methoxybenzyl group, methylbenzyl group, trityl group, acetamidomethyl group, carbomethoxysulfenyl group, benzyloxymethyl group, ferrocenylmethyl group, dimethylphosphinothioyl group Etc.

  Further, when the peptide chain has a sugar chain, it is preferable to use a sugar chain in which an alanine in the peptide chain or a hydroxyl group in threonine and an O-glycoside bond are used. As described above, many types of sugar chains are assumed. However, when a specific structure is required for the glycoside to be produced, other sugar chains that are not used for binding to peptide chains are used. It is important to use those in which the hydroxyl group, amino group, and carboxyl group are protected.

  In addition, for example, since sterols, amino acids, polypeptides, and peptide chains to which sugar chains are bound as described above all have the same solubility, all are applied to the glycosylation reaction of the present invention. Is preferred.

  For example, when the sugar acceptor is difficult to dissolve in the supercritical fluid as a solvent, an additional substance that dissolves the sugar acceptor may be added and reacted within a range that does not impair the object of the present invention. .

  In this case, examples of preferable additives include chloroform, diethyl ether, acetonitrile, and dichloromethane. These include substances that are conventionally used as organic solvents. However, according to the glycosylation reaction of the present invention, the minimum amount that the sugar acceptor dissolves in the supercritical solvent is sufficient, so these are added substances. The amount used can be significantly reduced over the amount conventionally used as a solvent. Specifically, for example, the amount can be about 1/10.

In addition, when synthesizing a glycoside and further extending the sugar to the sugar moiety in the glycoside, one kind of sugar selected from the group containing a sugar unit of the following formula (VII) A receptor may be used.

Wherein R ⁴⁰ is —OR ⁴⁵ , R ⁴¹ is —OR ⁴⁶ , —N ₃ or —NHR ⁴⁷ , R ⁴² is —OR ⁴⁸ , R ⁴³ is —OR ⁴⁹ , R ⁴⁴ Is —H, —CH ₃ , —CH ₂ OR ⁵⁰ or —COOR ⁵¹ , wherein R ⁴⁵ is a peptide in which diacylglycerol, ceramide, sterol, terpene, peptide chain or sugar chain is bonded, in which a hydrogen atom is removed from a hydroxyl group R ⁴⁶ is a sugar chain in which all reactive functional groups including -H, hydroxyl protecting group or hydroxyl group are protected, and R ⁴⁷ is a saturated aliphatic group or unsaturated aliphatic group. an amino group protecting group, R ^48, R ⁴⁹ and R ⁵⁰ is each independently of one another, -H, a sugar chain in which all of the reactive functional groups protected, including a hydroxyl protecting group or a hydroxyl group, R ⁵¹ A carboxyl group protecting group. ^{However, R 46,} R 48, R ⁴⁹ and ^{R 50} is all and no case is a hydroxyl-protecting ^group, among ^{R 46,} R 48, R ⁴⁹ and ^{R 50,} any Or one of them is -H, or when R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are not -H, one of the sugar chains has one unprotected hydroxyl group And).

  Here, the saturated or unsaturated aliphatic group is as defined in R of the above formula (IV), and is linear, branched, cyclic without side chain or cyclic with side chain Or a saturated aliphatic group corresponding to the saturated aliphatic group containing one or more unsaturated bonds. At this time, considering the solubility in a supercritical fluid as a solvent, the carbon number is preferably 1 to 30 and more preferably 1 to 10.

  The peptide chain is as defined in the above formula (V). Further, as described above, when the sugar receptor is difficult to dissolve in the supercritical fluid as a solvent, an additional substance that dissolves the sugar receptor is further added within the range that does not impair the object of the present invention. It is good to let them.

The gaseous CO ₂ removed from the reaction product can be reused by refilling the cylinder, for example, using a compressor or the like. Further, with sodium carbonate _(Na 2 CO _3), was recovered by collecting the CO _2, may be reused.

  Thus, since the glycosylation reaction of the present invention uses a supercritical fluid as a reaction solvent, the solvent removal step is particularly simple. Therefore, it is more effective for industrial production. Moreover, since the halogen-containing compound etc. which are conventionally used are not used or the usage-amount can be reduced notably, the load with respect to an environment can be reduced.

  As the reaction apparatus applied to the glycosylation reaction of the present invention, an apparatus similar to a conventional reaction apparatus can be used.

  Hereinafter, with reference to the drawings, a schematic configuration of this preferred reaction apparatus applied to the implementation of the glycosylation reaction of the present invention will be briefly described. Each drawing merely schematically shows the arrangement relationship of each component to such an extent that the invention can be understood. Therefore, the present invention is not limited to the illustrated example.

  FIG. 24 is a block diagram for schematically explaining the arrangement relationship of the components of this preferred reactor applied to the glycosylation reaction of the present invention.

  A preferable reaction apparatus applied to the synthesis method of the present invention includes a high-pressure cylinder 10 for supplying a desired solvent, and a pressurization for supplying the solvent under pressure by being connected to the high-pressure cylinder 10 by, for example, a pressure hose. A pump 20 and a reaction vessel 30 having a pressure resistance of at least 25 MPa (megapascal) connected to the pressurizing pump 20 are provided. The reaction vessel 30 is installed in a thermostat for adjusting the reaction temperature. A container opening / closing valve 42 is provided between the pressurizing pump 20 and the reaction container 30. A leak valve 44 is provided between the container opening / closing valve 42 and the reaction container 30. A pressure controller 52 for monitoring the pressure of the solvent supplied to the reaction vessel 30 is provided between the pressurization pump 20 and the vessel opening / closing valve 42. A vessel pressure gauge 54 for monitoring the pressure state in the reaction vessel 30 is provided between the vessel opening / closing valve 42 and the leak valve 44.

  The step of supplying the solvent into the reaction vessel 30 will be described. With the container opening / closing valve 42 closed, the solvent is supplied from the high pressure cylinder 10. The supplied solvent is pressurized to a predetermined pressure by the pressure pump 20. This pressure is monitored by the pressure controller 52 and adjusted to a predetermined pressure. Next, the container opening / closing valve 42 is opened to introduce the solvent into the reaction container 30. These operations are repeated while monitoring with the vessel pressure gauge 54 so that the pressure in the reaction vessel 30 becomes a pressure at which the selected solvent becomes a supercritical fluid. In this way, the pressure in the reaction vessel 30 is set to be a predetermined pressure. The reaction temperature is adjusted by a thermostat not shown.

  Specifically, when a supercritical fluid of carbon dioxide is used as a solvent, it exists as a supercritical fluid under the conditions of a temperature of 31 ° C. or higher and a pressure of 7.5 Mpa (megapascal) or higher. Demonstrate the function. The pressure to be applied is preferably 25 MPa or less in consideration of the strength of the apparatus. Moreover, since the saccharide | sugar used for reaction will carbonize at reaction temperature higher than 150 degreeC, it is good to set it as 150 degrees C or less.

  Next, the process for removing the solvent after completion of the reaction will be described. The reaction container 30 is taken out from the thermostat and allowed to cool to room temperature. By this operation, the solvent that was in a supercritical state in the reaction vessel 30 is transferred to a gas phase state. Next, the leak valve 44 is opened to release the gas phase solvent from the reaction vessel 30. At this time, it is preferable to remove the solvent while monitoring the pressure in the reaction vessel 30 with the vessel pressure gauge 54. Further, another high-pressure cylinder is connected to the leak valve 44 through, for example, a compressor, and the gaseous solvent discharged from the leak valve 44 is collected and collected in the high-pressure cylinder, and is refilled and reused. You can also

  The product is purified by a conventional general method such as chromatography, but since this purification step is not the gist of the present invention, detailed description thereof is omitted.

  Hereinafter, although an example explains the composition of the present invention in detail, the present invention is not limited to this.

  The obtained zeolite analogs in the examples were evaluated by the following methods.

(1) Powder X-ray diffraction analysis In order to confirm the formation of the zeolite analog of the present invention and the introduction of a transition metal (for example, Zr) into the zeolite analog, powder X-ray diffraction analysis was performed as follows. . The apparatus used for the analysis was MacScience MXP3HF, and the powder sample was mounted on a glass holder and irradiated with X-rays at 40 ° to 2 ° 2θCuKα. The measurement was performed under the conditions of 40 kv / 20 mA, DS 1.00 deg, SS 1.00 deg, RS 0.15 mm, specific rotated at 360 deg / sec, 3800 points (2.01 ° to 40 ° in 0.01 ° steps).

(2) Molecular orbital calculation It was confirmed by molecular orbital calculation method that Lewis acidity was developed by desorbing H ₂ O molecules from each of the zeolite analog and the Zr skeleton-substituted zeolite analog. The apparatus used for molecular orbital calculation is Alpha manufactured by Compaq.
server, ES45 system, and PC parallel cluster system manufactured by Bestsystems, HPC2000_APPRO. Well-known energy gradient methods (eg, Christopher J. Cramer, Essentials of Computational Chemistry, Theories and Models, John Wiley & Sons, United States ) To optimize all bond distances.

(3) Microstructure observation Using a Hitachi FB-2100 focused ion beam processing observation apparatus, a diatom fossil thin film in a clay diatomaceous earth containing a zeolite analog into which a transition metal was introduced was formed, and the cross section of the diatom fossil thin film was obtained. Observation was performed using a transmission electron microscope and a scanning electron microscope of the evaluation apparatus.

(4) Element distribution analysis The element distribution of the granular aggregate on the diatom fossil surface same as that used in the above (3) microstructure observation was analyzed by EDX (energy dispersion method) of Hitachi HD-2000 ultra-thin film evaluation apparatus.

(5) Elemental composition and quantitative analysis In the trace region of the granular aggregate on the surface of the same diatom fossil used in the above (3) microstructure observation, the elemental composition and quantitative analysis were performed using the Hitachi FB-2100 ultrathin film evaluation apparatus. This was performed using an EDX apparatus.

(6) NMR measurement About the glycoside obtained using the Lewis acid catalyst and other various catalysts produced in the present invention, ¹ H-NMR measurement (apparatus: JEOL)
JNM-LA400 FT NMR SYSTEM (400 MHz) was performed.

¹ H-NMR values were measured at a measurement temperature of 27 ° C. using tetramethylsilane in deuterated chloroform CDCl ₃ solvent as an internal standard. The δ value was expressed in ppm, and the coupling constant (J) was expressed in Hz. In the data, s means a single line, d means a double line, and m means a multiple line.
For (Reference Example 1) ideal formula NaAlSi ₂ O ₆ · _{H 2} O Write powder X-ray diffraction ideal type zeolite crystal represented by NaAlSi ₂ O ₆ · _{H 2} person represented by O zeolite crystal, powder X-ray diffraction Analysis was carried out. This powder X-ray diffraction line is shown in FIG. In Figure 1, numerals represent Miller indices indicating the zeolite crystal surface towards the composition of the ideal formula _{NaAlSi 2 O 6 · H 2 O} , is in parentheses is the interatomic distance indicating the distance between the atoms in the crystal structure. A plurality of peaks were observed, but the peak intensities of crystal planes with Miller indices 211, 400, and 332 were particularly remarkable. The interatomic distance between these three crystal planes is particularly important for the identification of zeolite.

(Reference Example 2) Powder X-ray diffraction of Mg-exchanged zeolite analogue crystal represented by Na ₁₀ Mg ₃ Al ₁₆ Si ₃₂ O ₉₆ · 25H ₂ O Among natural minerals known so far, Na as a cation In addition to the zeolite analog crystals containing Mg, powder X-ray diffraction was performed. This powder X-ray diffraction line is shown in FIG. 2, numerals cation in analcime, partially Mg-exchange type zeolite analogs have been replaced by Na to _{Mg Na 10 Mg 3 Al 16 Si} 32 O 96 · 25H 2 zeolite crystals towards the O composition The Miller index indicating a plane is shown, and the parenthesized values are interatomic distances indicating the distances between atoms in the crystal structure. As someone zeolite crystal represented by the ideal formula NaAlSi ₂ O ₆ · _{H 2} O in Example 1, the interatomic distance of the Miller index 211,400 (410) is stretched 0.1～0.3A. From this result, it can be seen that, in the zeolite analog, the interatomic distance between these crystal faces changes when the kind of cation is partially changed from Na to Mg.

(Example 1) Manufacture of zeolite analogues using diatomaceous earth from Chizen Hokkaido, Japan and analysis by X-ray powder diffraction lines
1.1 Pretreatment of Hokkaido Chizensei diatomaceous earth (raw material) with acid / alkali The raw material of Chizensei Hokkaido clay diatomaceous earth was pretreated with acid / alkali solution to remove impurities as follows. . Ichisei diatomaceous earth is a clayey diatomaceous earth from Ichizensei, Urahoro-cho, Tokachi-gun, Hokkaido. It is a distinctive layer from the Michisei Formation, which is an upper Miocene marine sediment (530-11.2 million years ago). It is mined from the main component of the cell wall of marine diatoms. Specifically, 18 g of diatomite rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide solution (100 ml) and 36% hydrochloric acid solution (100 ml), and then 0.1% sodium pyrophosphate solution was added. The added decantation was performed twice to remove impurities.

1.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid / alkali The mineral composition of diatomaceous earth from Ichizen Hokkaido after the pretreatment shown in 1.1 above was analyzed using X-ray powder diffraction (FIG. 4). ). In FIG. 4, M1 is illite-trioctohedral (002) and muscovite-2M ₂ (002), muscovite-3T (003), M2 is illite-2M ₂ (110, 11-1), muscovite. -3T (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111), Q2 is Quartz (101), R3 is part-time job (040,002), anorthite (040,002), M3 is muscovite-2M ₂ (-312,021,116,310), muscovite-3T (111 112), Q3 is quartz (110), and Q4 is quartz (102). The results of FIG. 4 showed that this clayey diatomaceous earth contains illite and muscovite as mica clay minerals but does not contain smectite clay minerals such as montmorillonite.

Thus, the impurities were removed, and clayey diatomaceous earth containing mica clay minerals such as illite and muscovite was used as a raw material for producing the next zeolite analogue.

1.3 Manufacture of zeolite analogues using diatomite from Ichisei, Hokkaido The precipitate after decantation in 1.2 above is dried with a vacuum dryer to obtain a dry powdery pretreated clay-like diatomite It was.

To 1.3 g of this dry powdery clay diatomaceous earth, 5.0 ml of 1N sulfuric acid was added, air-dried at room temperature overnight, and then calcined at 650 ° C. for 3 hours to obtain a zeolite analog exhibiting Lewis acidity in diatomaceous earth. .

1.4 X-Ray Powder Diffraction Analysis of Zeolite Analogues Made of Hokkaido Chizensei Diatomaceous Earth The raw material of Hokkaido Chizensei clay diatomaceous earth obtained in 1.3 above was analyzed by X-ray powder diffraction (FIG. 9). In FIG. 9, A1 is a zeolite analog (211), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111) A2 is a zeolite analog (410 or 400), Q2 is quartz (101), R3 is albite (040,002), anorthite (040,002), and A3 is a zeolite analog ( 422 or 332), A4 is a zeolite analog (431), Q3 is quartz (110), and Q4 is quartz (102). From the above results, the clayey diatomaceous earth obtained in 1.3 was identified as a zeolite analog.

Although the clay diatomaceous earth containing mica clay mineral was used as a raw material, the mica clay mineral disappeared from the clay diatomaceous earth after adding the sulfuric acid solution and firing at 650 ° C. From this, it was speculated that mica clay minerals are involved in the formation of zeolite analogues.

(Example 2) Manufacture of zeolite analogues using diatomite from Rukabe, Hokkaido, and analysis by X-ray powder diffraction lines
2.1 Pretreatment of Hokkaido Rubeshibe diatomaceous earth (raw material) with acid / alkali The raw clayy diatomite from Hokkaido Rubebeji was pretreated with an acid / alkali solution to remove impurities as follows. Rukabe diatomaceous earth is a clay diatomaceous earth from Rukabe-cho, Tokoro-gun, Hokkaido, mined from the Komatsuzawa Formation, which is a Pliocene (1.8 to 5.3 million years ago) lake sediment, and is mainly composed of freshwater diatoms. Specifically, 40 g of diatomite rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide (120 ml) and 36% hydrochloric acid solution (80 ml), and then 0.1% sodium pyrophosphate solution was added. The decantation was performed twice to remove impurities.

2.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid / alkali The mineral composition of diatomaceous earth produced in Rukabe, Hokkaido, after the pretreatment shown in 2.1 above was analyzed using X-ray powder diffraction (FIG. 5). In FIG. 5, M2 is illite-2M ₂ (110, 11-1), muscovite-3T (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (−201). R2 is part-time (111) and anorthite (111), Q2 is quartz (101), R3 is part-time (040,002), anorthite (040,002), and M3 is muscovite. -2M ₂ (-312, 021, 116, 310), muscovite-3T (111, 112), Q3 is quartz (110), and Q4 is quartz (102). The result of FIG. 5 showed that this clayey diatomaceous earth contained some illite and muscovite as mica clay minerals but not smectite clay minerals such as montmorillonite.

Thus, the impurities were removed, and clayey diatomaceous earth containing mica clay minerals such as illite and muscovite was used as a raw material for producing the next zeolite analogue.

2.3 Manufacture of zeolite analogue using diatomaceous earth produced in Rukabe, Hokkaido The precipitate after decantation described in 2.2 above was dried with a vacuum dryer to obtain a dry powdery pretreated clay diatomaceous earth.

To 1.3 g of this dry powdery clay diatomaceous earth, 5.0 ml of 1N sulfuric acid was added, air-dried at room temperature overnight, and then calcined at 650 ° C. for 3 hours to obtain a zeolite analog exhibiting Lewis acidity in diatomaceous earth. .

2.4 X-Ray Powder Diffraction Analysis of Zeolite Analogues Made from Hokkaido Rubeshibei Diatomaceous Earth The raw material of Hokkaido Rubeshibei diatomite obtained in 2.3 above was analyzed by X-ray powder diffraction (FIG. 10). In FIG. 10, A1 is a zeolite analog (211), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111) A2 is a zeolite analog (410 or 400), Q2 is quartz (101), R3 is albite (040,002), anorthite (040,002), and A3 is a zeolite analog ( 422 or 332), A4 is a zeolite analog (431), Q3 is quartz (110), and Q4 is quartz (102). From the above results, the clay diatomaceous earth obtained in 2.3 was identified as a zeolite analog.

(Example 3) Manufacture of zeolite analogue using Hirosaki Hirosaki Aomori Prefecture as raw material and analysis by X-ray powder diffraction line
3.1 Pretreatment of Hirosaki Aomori diatomaceous earth (raw material) with acid / alkali The raw clay diatomaceous earth from Hirosaki Aomori Prefecture was pretreated with an acid / alkali solution to remove impurities as follows. Hirosaki diatomaceous earth is a clay diatomaceous earth produced from the basin of the Hirouchi River, Hirosaki City, Aomori Prefecture, and is an ocean sediment from the upper to middle Miocene (530 to 16.4 million years ago). Specifically, 54 g of diatomaceous earth rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide (150 ml) and 36% hydrochloric acid solution (74 ml), and then 0.1% sodium pyrophosphate solution The decantation was added twice to remove impurities.

3.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid / alkali The mineral composition of diatomaceous earth from Hirosaki Aomori after the pretreatment shown in 3.1 above was analyzed using X-ray powder diffraction (FIG. 6). . In FIG. 6, M1 is illite-trioctohedral (002), muscovite-2M ₂ (002), muscovite-3T (003), and M2 is illite-2M ₂ (110, 11-1), muscovite-3T. (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111), and Q2 is quartz ( 101), R3 is a part-time job (040, 002), anorthite (040, 002), and Q4 is quartz (102). The result of FIG. 6 showed that this clayey diatomaceous earth contained some illite and muscovite as mica clay minerals but no smectite clay minerals such as montmorillonite.

Thus, the impurities were removed, and clayey diatomaceous earth containing mica clay minerals such as illite and muscovite was used as a raw material for producing the next zeolite analogue.

3.3 Manufacture of zeolite analogue using diatomite from Hirosaki, Aomori Prefecture The precipitate after decantation in 3.2 above was dried with a vacuum dryer to obtain a dry powdery pre-treated clay diatomite .

To 1.3 g of this dry powdery clay diatomaceous earth, 5.0 ml of 1N sulfuric acid was added, air-dried at room temperature overnight, and then calcined at 650 ° C. for 3 hours to obtain a zeolite analog exhibiting Lewis acidity in diatomaceous earth. .

3.4 X-Ray Powder Diffraction Analysis of Zeolite Analogue Using Hirosaki Aomori Prefecture Diatomite as a Raw Material The diatomite produced in Hirosaki Aomori Prefecture obtained in 3.3 above was analyzed by X-ray powder diffraction (FIG. 11). In FIG. 11, A1 is a zeolite analog (211), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111) A2 is a zeolite analog (410 or 400), Q2 is quartz (101), R3 is albite (040,002), anorthite (040,002), and A3 is a zeolite analog ( 422 or 332) and Q4 is quartz (102). From the above results, the clay diatomaceous earth obtained in 3.3 was identified as a zeolite analog. However, the peak intensity of zeolite analogues was weaker than that of Neogene diatomaceous earth from Hokkaido.

(Example 4) Production of zeolite analogue using diatomaceous earth from Higashikawa, Hokkaido and analysis by X-ray powder diffraction line
4.1 Pretreatment of Hokkaido Higashikawa Diatomaceous Earth (Raw Material) with Acid / Alkali The raw material of Hokkaido Higashikawa Diatomaceous Earth was pretreated with an acid / alkaline solution to remove impurities as follows. Higashikawa diatomite is a high-quality diatomite from the foot of Mt. Daisetsu in Higashikawa-cho, Kamikawa-gun, Hokkaido. The diatomite from Higashikawa, Hokkaido, is a high-quality quaternary diatomite with an alumina content of 2% or less, unlike diatomite from Ichisei in Hokkaido, diatomite from Rukabe, Hokkaido, and Hirosaki from Aomori Prefecture. Specifically, 15 g of diatomaceous earth rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide (200 ml) and 36% hydrochloric acid solution (100 ml), and then 0.1% sodium pyrophosphate solution was added. The added decantation was performed 5 times to remove impurities.

4.2 The mineral composition of diatomaceous earth from Higashikawa, Hokkaido after pretreatment with acid / alkali was analyzed using X-ray powder diffraction (FIG. 7). In FIG. 7, M2 is illite-2M ₂ (110, 11-1), muscovite-3T (100), Q1 is quartz (021), Q2 is quartz (101), and R3 is part-time ( 040, 002) and anorthite (040, 002). The result of FIG. 7 showed that this diatomaceous earth contains a small amount of illite and muscovite as mica clay minerals, but does not contain smectite clay minerals such as montmorillonite.

Thus, the impurities were removed, and clayey diatomaceous earth containing mica clay minerals such as illite and muscovite was used as a raw material for producing the next zeolite analogue.

4.3 Manufacture of zeolite analogue using diatomite from Higashikawa, Hokkaido The precipitate after decantation in 4.2 above was dried with a vacuum dryer to obtain a dry powdery pretreated clay diatomite.

1 ml of 1N sulfuric acid was added to 1.3 g of this dry powdery clay diatomaceous earth (Hokkaido Higashikawa diatomaceous earth is extremely hygroscopic and 10 ml of 5.0 ml of 1N sulfuric acid did not reach the entire sample. ), Air-dried at room temperature for a whole day and then calcined at 650 ° C. for 3 hours to obtain a zeolite analog exhibiting Lewis acidity in diatomaceous earth.

4.4 X-Ray Powder Diffraction Analysis of Zeolite Analogues from Hokkaido Higashikawa Diatomaceous Earth The Higashikawa Hokkaido diatomaceous earth obtained in 4.3 above was analyzed by X-ray powder diffraction (FIG. 12). In FIG. 12, A1 is a zeolite analog (211), Q1 is quartz (021), R1 is cristobalite (101), anorthite (−201), and A2 is a zeolite analog (410 or 400). , Q2 is quartz (101), R3 is part-time (040, 002), anorthite (040, 002), A3 is a zeolite analog (422 or 332), and A4 is a zeolite analog (431). It is. From the above results, the clayey diatomite obtained in 4.3 was identified as a zeolite analog. However, the peak intensity of zeolite analogues was weaker than that of Neogene diatomaceous earth from Hokkaido.

(Example 5) Molecular orbital calculation of zeolite analog It was confirmed by molecular orbital calculation method that Lewis acidity was developed in the zeolite analog from which H ₂ O molecules were eliminated by the firing treatment in Examples 1 to 4. .

FIG. 8 shows the crystal structure of zeolitic as a model for molecular orbital calculation. Of the two zeolitic models in FIG. 8, the left shows a four-membered ring model (Si ₄ O ₁₂ H ₈ ), and the right shows a six-membered ring model (Si ₆ O ₁₈ H ₁₂ ). With respect to the cluster model of FIG. 8, all bond distances were optimized by the energy gradient method, and a model in which O between Si and Si was missing with two electrons was constructed as a model in which H ₂ O was desorbed. (Left shows a 4-membered ring model (Si ₄ O ₁₁ H ₈ ²⁺ ), right shows a 6-membered ring model (Si ₆ O ₁₇ H ₁₂ ²⁺ )). O ²⁻ forms H ₂ O together with _two protons. Further, in order to see whether it can function as a Lewis acid, an electron pair was added to this model (the left shows a 4-membered ring model (Si ₄ O ₁₁ H ₈ ), and the right shows a 6-membered ring model (Si ₆ O). ₁₇ H ₁₂ ) was calculated) and the stabilization energy was predicted. For both the 4-membered and 6-membered ring models, the energy to receive and stabilize the electron pair was 450 kcal / mol or more, far exceeding the energy scale in ordinary chemical reactions. From these factors, it was confirmed that the zeolite analog from which H ₂ O was eliminated can have strong Lewis acidity.

(Example 6) Manufacture of Zr skeleton-substituted zeolite analogues using diatomite from Rukabe, Hokkaido, and analysis by X-ray powder diffraction lines
6.1 Pretreatment of diatomaceous earth (raw material) produced in Rukabe, Hokkaido with acid and alkali In the same manner as described in 2.1 in Example 2, the clay diatomaceous earth produced in Rukabe, Hokkaido, was treated with an acid / alkaline solution. Pretreated and dried with a vacuum dryer to obtain a dry powdery pretreated clay diatomaceous earth. As a result of analyzing the mineral composition of the diatomaceous earth produced in Rukabe, Hokkaido, using pre-treatment using X-ray powder diffraction, a diffraction line similar to 2.2 described above in Example 2 was obtained (this diffraction line is omitted). Diffraction lines showed that the obtained clay diatomaceous earth contained some illite and muscovite as mica clay minerals but no smectite clay minerals such as montmorillonite.

6.2 Manufacture of Zr skeleton substitution type zeolite analogues using diatomite from Rukabe, Hokkaido Prefecture 2.6 g of acid / alkali treated clay diatomite having a particle size of 0.150 to 0.850 mm is filled in a calcium tube, ZrCl ₄ vaporized at 400 ° C. was sent to a calcium tube, and particulate ZrCl ₄ was deposited on the surface of clay diatomaceous earth by a CVD method (chemical vapor deposition method). Air was sent to the container to hydrolyze the particulate ZrCl ₄ to produce ZrCl ₂ O · 8H ₂ O on the surface of the clay diatomaceous earth. After hydrolysis of ZrCl _4, the supporting amount of the clay diatomaceous earth ZrCl ₂ O · 8H ₂ O, was calculated from the weight gain measurements, a loading amount per diatomite 1g was estimated to 0.34 mM. Calcium tube, removed clay diatomaceous earth carrying ZrCl ₂ O · 8H ₂ O, to obtain a Zr _{(OH) 4} was added 28% aqueous ammonia 30ml after transferred to a beaker. The precipitate was washed by decantation (5 times) and dried at 100 to 150 ° C. overnight in an electric furnace. After drying, 1N sulfuric acid (3.8 ml with respect to 1 g of diatomaceous earth) was added, air-dried at room temperature overnight, and then calcined at 650 ° C. for 3 hours.

6.3 X-ray diffraction analysis of Zr skeleton-substituted zeolite analogues using diatomaceous earth from Rukabe, Hokkaido, as a raw material The diatomaceous earth from Rukabe, Hokkaido, obtained in 6.2 above was analyzed by X-ray diffraction analysis (FIG. 13). In FIG. 13, A1 is a zeolite analog (211), M1 is illite-trioctohedral (002), muscovite-2M ₂ (002), muscovite-3T (003), Q1 is quartz (021), R1 is cristobalite (101) and anorthite (−201), R2 is albite (111) and anorthite (111), A2 is an zeolite analog (410 or 400), and Q2 is quartz (101). R3 is part-time (040,002), anorthite (040,002), A3 is a zeolite analog (422 or 332), A4 is a zeolite analog (431), and Q3 is quartz ( 110) and Q4 is quartz (102). From the above results, the clayey diatomaceous earth obtained in 6.2 above was identified as a zeolite analog.

The peak of the X-ray powder diffraction line (FIG. 10) of the zeolite analog (that is, not introducing Zr) produced from diatomaceous earth produced in Rukabe, Hokkaido, shown in 2.4 of Example 2 is 5.8010-6. The peak of (410 or 400) was 3.492 to 3.568 Å (width 0.076 Å).

  On the other hand, the peak of the Zr-introduced zeolite analog (211) in FIG. 13 is 5.814 to 6.215Å (width: 0.401Å), and the peak of (410 or 400) is 3.496 to It was 3.613 mm (width 0.117 mm). That is, by introducing Zr, it was shown that the interatomic distance in the crystal plane of the zeolite analog was extended by a maximum of 0.17 cm (211).

This change in interatomic distance is due to the insertion of tetrahedral Zr into the crystal lattice of the zeolite analog. Here, the MO distance of the MO ₄ H ₄ (M = Si, Al, Zr) tetrahedral structure is shown in Table 1 below. Here, for the structure optimization by the energy gradient method of MO ₄ H ₄ (M = Si, Al, Zr), a 3-21G * basis was used using a restricted Hartree Fock method. M = Al was calculated as a monovalent negative ion.

Table 1. MO ₄ H ₄ (M = Si, Al, Zr) tetrahedral structure MO distance

From Table 1, the tetrahedral structure of ZrO ₄ is larger than the tetrahedral structure of AlO ₄ and SiO ₄ , and when Zr is inserted into the zeolite analog, the interatomic distance measured by the X-ray powder diffraction line is extended. Is clear. As a result of the simulation by the molecular orbital calculation method, it was predicted that the peak of the zeolite analog (211) would be extended by 0.039 mm by introducing Zr. Compared with the actual analysis results, it is well explained in the range of factor 2. Zr—Si and Zr—Al are overwhelmingly less than Si—Si, considering that Zr is small. Thus, it is clear that the range of extreme distances that came out in the calculations is smaller when observed.

From the above analysis results, it became clear that the framework-substituted zeolite analog obtained by replacing the TO ₄ tetrahedron with ZrO ₄ from diatomaceous earth (raw material) produced in Rukabe, Hokkaido, can be obtained by the above method 5.2 .

6.4 Hitachi HD-2000 clay cytoplasm kieselguhr containing Zr backbone substituted type zeolite analogs produced in the analysis above 6.2 by ultra-thin film evaluation device Hokkaido Rubeshibe produced diatomaceous earth as a raw material was Zr backbone substituted type zeolite analogues The analysis was performed using a transmission electron microscope and EDX (energy dispersion method) of an ultrathin film evaluation apparatus.

  A cross section of a diatom fossil in clay diatomaceous earth was prepared, and the microstructure was observed by transmission electron microscope analysis (FIG. 14). In FIG. 14, the cross section of the diatom fossil is a diatom cell wall belonging to the genus Auracoseira in the diatomaceous earth produced in Rukabe, and a thin film was formed by a Hitachi FB-2100 focused ion beam processing observation apparatus. From FIG. 14, it was confirmed that a granular aggregate having a diameter of 100 nm was generated on the surface of the diatom fossil. FIG. 14 also showed that the granular aggregates were spherical and the amorphous gel-like material filled between the granular aggregates.

  According to the observation of the clay-like diatomite from Rukabe Pass by scanning electron microscope, no granular aggregates were observed on the surface of the diatom fossil. Therefore, it was estimated that the granular aggregate on the surface of the diatom fossil was a zeolite analog in which Zr of Example 2 was inserted.

  The elemental distribution of the granular aggregate of FIG. 15 was analyzed by EDX (energy dispersion method) of a Hitachi HD-2000 ultra-thin film evaluation apparatus. In FIG. 15, SEM is a scanning electron microscope and is the same area | region as the right side image of FIG. Si-K, Al-K, and Zr-K are images obtained from the K shell in each atom, and the analyzed region is identical to the scanning electron microscope image. From FIG. 15, it was confirmed that the granular aggregate contains Al and Zr in addition to Si.

  Since the ultra-thin film evaluation apparatus can perform the elemental composition and quantitative analysis of a minute region, the elemental composition of each granular material was analyzed (FIG. 16). In FIG. 16, the elemental composition was analyzed by the EDX apparatus of the Hitachi FB-2100 ultrathin film evaluation apparatus, and is the elemental composition of the granular aggregate in FIG. However, W is the metal used for depositing the sample, and Mo is the metal constituting the sample stage.

  Further, the elemental composition of another granular aggregate in the same sample as in FIG. 14 was analyzed in the same manner as in FIG.

  From individual granular aggregates in these same samples, C, O, Na, Al, Zr, Si, K, and Fe were identified, and the element ratios of Al, Zr, and Si as main elements other than O are shown in FIG. Then, it was 3: 43: 4, and in FIG. 17, it was 1: 8: 1.

A difference in the element ratios of Al, Zr, and Si in FIGS. 16 and 17 indicates that the granular aggregate is not a single composition crystal but forms a solid solution. A solid solution is a solid phase in which a plurality of substances are dissolved, and is also called a mixed crystal. There are substitution type and intrusion type, and most of minerals are substitution type, and one component substitutes the other component and melts. The peripheral area of the granular aggregate is filled with an opal represented by the ideal formula SiO ₂ · nH ₂ O, and the zeolite analog and the opal identified by the X-ray powder diffraction line of Example 6 (MacScience MXP3HF) It is thought that a solid solution is formed. The SiO ₄ tetrahedron is a common structure of zeolite analogues and opals.

The element ratio of Al and Si constituting the TO ₄ tetrahedron of natural calcite is 1: 2. Among them, when Zr substitutes for deficient Al in clay diatomaceous earth, the ideal formula of the granular aggregate is X ₇ Zr ₄ Al ₃ Si ₁₄ O ₄₂ · 7H ₂ O + 29 (SiO ₂ · nH ₂ O in FIG. ), and represented by _{X 2 ZrAlSi 4 O 12 · 2H} 2 O + 4 in FIG. _{17 (SiO 2 · nH 2 O} ). In the formula, X is an alkali metal. That is, the Zr skeleton-substituted zeolite analog represented by the ideal formula X ₂ ZrAlSi ₄ O ₁₂ · 2H ₂ O or X ₇ Zr ₄ Al ₃ Si ₁₄ O ₄₂ · 7H ₂ O and the ideal formula SiO ₂ Silicon dioxide forms a solid solution.

If X is all protonated, ideal formula _{H 2 ZrAlSi 4 O 12 · 2H} 2 O + 4 (SiO 2 · nH 2 O) , or _{H 7 Zr 4 Al 3 Si 14} O 42 · 7H 2 O + 29 (SiO 2 NH ₂ O), and dehydration by firing results in the ideal formula ZrAlSi ₄ O ₁₁ +4 (SiO ₂ · nH ₂ O) or Zr ₄ Al ₃ Si ₁₄ O ₂₈ +29 (SiO ₂ · nH ₂ O). However, Na and K are also detected as alkali metals from the granular aggregate, and not all Zr skeleton-substituted zeolite analogues are protonated.

The elemental composition ratio of the granular aggregate calculated from the EDX analysis of FIG. 17 is shown in Table 2 below.

Table 2. Element composition ratio of granular aggregate calculated from EDX analysis of FIG.

  In Table 2, impurities C, W, and Mo were excluded from the elements found by the elemental analysis of FIG. The weight% and atom% were calculated based on the signal obtained from the K shell in the atom.

In the zeolite analog, the number of monovalent cations is the same as the amount of Al in the TO ₄ tetrahedron, but Zr substitutes Al in the zeolite analog of FIG. Therefore, the same amount of cation as 7.46 atom% in which Zr and Al are combined is required. However, since the total amount of K and Na detected from the zeolite analog is 1.63 atom%, the number of cations is insufficient in the elemental composition in the table. This deficiency in the number of cations is the effect of protons that could not be detected by Fe and EDX analysis. That is, in the zeolite analog, a part of the cation is replaced with a proton.

Example 7 Molecular Orbital Calculation of Zr Skeleton-Substituted Zeolite Analogue The Lewis acidity of the zeolite analog from which H ₂ O molecules were desorbed from the Zr-introduced zeolite analog by the firing treatment in 6.2 of Example 6 Whether or not is expressed was confirmed by molecular orbital calculation method.

For two model described above in Example 5, respectively, Si and one Al ^- and substituted model (left Zr represents a 4-membered ring model ^{_{(AlZrSi 2 O 11 H 8 2+}} ), right 6-membered Using a ring model (showing AlZrSi ₄ O ₁₇ H ₁₂ ²⁺ ), the energy for receiving and stabilizing electron pairs was calculated by the molecular orbital method in the same manner as in Example 5. The stabilization energy was about 280 kcal / mol, far exceeding the range of normal chemical reaction, but the degree of stabilization was less than that without Zr. That is, Lewis acidity appears due to the stabilization factor obtained by receiving the electron pair, and its strength is considered to be weaker than that of the zeolite analog not introduced with Zr.

However, as shown in Reference Example 3, even if it was a Zr skeleton-substituted zeolite analogue, the target product could be obtained in a sufficient yield in experiments using this as a Lewis acid catalyst.

Here, Comparative Examples 1 and 2 show the results of sulfuric acid addition and baking at 650 ° C. when montmorillonite, which is the most common clay mineral, and amorphous silica, which is the main component of diatomaceous earth, are used as raw materials.

  Comparative Example 3 shows the results of X-ray powder diffraction lines (MacScience MXP3HF) obtained by using only 650 ° C. firing after pretreatment with acid / alkaline solution using diatomaceous earth produced in Rukabe, Hokkaido.

  Furthermore, Example 8 shows an example in which a zeolite analog produced from Rukabe-an diatomaceous earth and a Zr skeleton-substituted zeolite analog are used as a Lewis acid catalyst.

(Comparative Example 1) Addition of sulfuric acid from bentonite as a raw material and calcination at 650 ° C. As a result, 5.0 g of 1N sulfuric acid was added to 1.3 g of dry powdered bentonite, air-dried overnight at room temperature, and then baked at 650 ° C. for 3 hours. Thus, paragonite was obtained in bentonite. Paragonite represented by the general formula NaAl ₂ (Si ₃ Al) O ₁₀ (OH, F) ₄ is dioctahedral mica. The bentonite after calcination consolidated into an unglazed form, and a powder form suitable for a solid catalyst could not be obtained.

The main component of bentonite is montmorillonite represented by the ideal formula Na _0.33 (H ₂ O) ₄ (Al, Mg) ₂ [(OH) ₂ | Si ₄ O ₁₀ ], which swells in water and has a cation. It is characterized by having exchangeability. It is used for applications such as mud conditioner for boring, binder for iron ore pallet, sand-type binder for casting, civil engineering, agrochemical carrier, soil improvement, and coating aid. For the experiment, bentonite manufactured by Kanto Chemical (04066-01) was used. The result of having analyzed the mineral composition by the X-ray powder diffraction line (MacScience MXP3HF) is shown in FIG. In FIG. 18, Mo1 is montmorillonite, M1 is illite, M2 is muscovite (001) and illite (002), H1 is pyroxenite (020), and H2 is pyroxenite (200). , H3 is pyroxenite (20-1), H4 is pyroxenite (31-1), H5 is pyroxenite (111), H6 is pyroxenite (20-1), and Mo2 is montmorillonite. M3 is muscovite and illite, Q1 is quartz (100), R1 is cristobalite (101), H7 is pyroxenite (131), R2 is albite (111), anorthite ( -130), Mo3 is montmorillonite (103), Q2 is quartz (101), R3 is part-time (040,002), anorthite (040,002), a1 is calcite (104), M4 is muscovite (204), R4 is anorthite (1-31), H8 is pyroxenite (151), and H9 is pyroxenite (62-1, 530), H10 is pyroxenite (061), Mo4 is montmorillonite, M5 is muscovite and illite, and Q3 is quartz (102).

In addition to montmorillonite, mica-based clay minerals containing muscovite and illite were identified as clay minerals. In addition, pyroxenite, a natural zeolite, was found. In addition to clay minerals, rock-forming minerals such as quartz, cristobalite and feldspar, and calcite represented by CaCO ₃ were identified. These are common minerals contained in bentonite.

FIG. 19 shows the results of analysis of bentonite consolidated into an unglazed shape after treatment using an X-ray powder diffraction line (MacScience MXP3HF). In FIG. 19, M2 is muscovite (001) and illite (002), P1 is paragonite-1M (001), H1 is pyroxenite (020), H2 is pyroxenite (200), and H3 is Pyroxenite (20-1), H4 is pyroxenite (31-1), H5 is pyroxenite (111), P2 is paragonite-1M (002), Mo2 is montmorillonite, M3 Are muscovite and illite, Q1 is quartz (100), R1 is cristobalite (101), P3 is paragonite-2M ₁ (022), H7 is pyroxenite (131), R2 is Albite (111) and anorthite (-130), An1 is anhydrite (020), Q2 is quartz (101), P4 is paragonite-1M (003) Fine paragonite _-2M is 1 (006), R3 is a part-time job (040,002), anorthite (040,002), H8 is a heulandite (151), An2 is anhydrite (012), P5 is paragonite-2M ₁ (−131), An3 is anhydrite (202), and Q3 is quartz (102).

In spite of performing the same treatment as diatomaceous earth shown in Examples 1 to 4, no zeolite analogue was obtained. After the treatment, the characteristic peak of 2θCuKα7 ° (interatomic distance of 12.3 km) of illite-montmorillonite disappeared and replaced with paragonite which is a mica mineral. Furthermore, the calcite represented by CaCO ₃ found in bentonite was replaced with an anhydrite represented by CaSO ₄ after the treatment.

This result shows that a zeolite analogue is not formed by adding sulfuric acid and baking at 650 ° C. from clay containing montmorillonite as a main component.

(Comparative Example 2) Addition of sulfuric acid from amorphous silica as a raw material and calcination at 650 ° C. As a result of adding 1.5 ml of 1N sulfuric acid to 1.3 g of dry powdery amorphous silica and air-drying at room temperature all day and night 650 Baked at 3 ° C. for 3 hours. FIG. 20 shows the result of analyzing the mineral composition by X-ray powder diffraction line (MacScience MXP3HF) using silicon dioxide (manufactured by sedimentation, amorphous) made by Kanto Chemical (37049-13) for the experiment.
An amorphous halo having a peak at 2θCuKα21-22 ° (interatomic distance of 4.23-4.04 mm) was obtained as in diatomaceous earth.

As a result of the analysis of the amorphous silica by the X-ray powder diffraction line (MacScience MXP3HF) (FIG. 21), 2θCuKα21-22 ° (interatomic distance 4.23-4.04Å) peaked. The shape of the amorphous halo is the same as the amorphous silica shown in FIG.

From this comparative example, it was shown that amorphous silica was not crystallized by addition of sulfuric acid and 650 ° C., and that the zeolite analog could not be obtained using only amorphous silica as a raw material. It was also shown that zeolite analogues could not be obtained from diatomaceous earth consisting of pure diatom fossils by adding sulfuric acid and firing at 650 ° C.

(Comparative Example 3) As a result of firing at 650 ° C. using diatomaceous earth produced in Rukabe, Hokkaido, the raw clay diatomaceous earth produced in Rukabe, Hokkaido, was removed by pretreatment with an acid / alkali solution. Specifically, 28 g of diatomite rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide (100 ml) and 36% hydrochloric acid solution (50 ml), and then 0.1% sodium pyrophosphate solution was added. The added decantation was performed 5 times, and clay diatomite containing mica clay minerals such as illite and muscovite from which impurities were removed was used as a raw material. The dried powdery pretreated clay-like diatomaceous earth was obtained by drying the decanted precipitate with a vacuum dryer. After this pretreatment, dry powdery clay diatomaceous earth was calcined at 650 ° C. for 3 hours.

FIG. 22 shows the result of analysis of clay diatomite fired at 6 50 ° C. by X-ray powder diffraction line (MacScience MXP3HF). In FIG. 22, muscovite-3T (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is albite (111), anorthite (111) Q2 is quartz (101), R3 is part-time (040,002), anorthite (040,002), Q3 is quartz (110), and Q4 is quartz (102). This clayey diatomaceous earth contained some illite and muscovite as mica clay minerals, and no zeolite analogue was synthesized in this diatomaceous earth. This comparative example showed that even if clay diatomaceous earth was used as a raw material, a zeolite analog could not be obtained only by 650 ° C. firing treatment.

(Example 8) Synthesis of sugar-alcohol (glycoside) In this example, supercritical carbon dioxide was used as a solvent by using as a Lewis acid catalyst diatomaceous earth produced in Rukabe, Hokkaido, which had been subjected to 1N sulfuric acid addition and 650 ° C baking treatment. Shows a reaction for introducing a leaving group and a protecting group into a sugar donor. Zeolite analogues and Zr skeleton-substituted zeolite analogues produced according to the present invention exhibit very high activity in glycosylation reactions in supercritical carbon dioxide.

In the reaction vessel, as a sugar donor, a leaving group is added to the OH group at the 1-position, and a protecting group is added to the OH group at the 2-5-position;

Of the compound (2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyltrichloroacetimidate) (300 mg, 0.609 mmol) was added.

  Then, 0.48 ml (3.04 mmol) of 1-octanol was added. More catalyst was added.

Table 3 shows the sample number, the catalyst used and the amount of catalyst (mg).

Table 3. Catalyst and amount of catalyst used in the synthesis of sugar-alcohol (glycoside)

  Zeolite analogue / Rukabe diatomaceous earth was obtained by the same production method as in Example 2. That is, it was obtained by adding air to 10 ml of 1N aqueous sulfuric acid solution in 2.6 g of diatomaceous earth produced in Rukabe, Hokkaido, which had been treated with acid and alkali, and air-drying at room temperature (20 ° C.) overnight.

Zr framework substitution type zeolite analogue / Rukabe diatomaceous earth was obtained by the same production method as in Example 5. That is, ZrCl ₄ is supported by CVD method (chemical vapor deposition method) on diatomite produced in Rukabe, Hokkaido, which has been treated with acid and alkali, converted to ZrOCl ₂ by hydrolysis in the gas phase, and Zr (OH) by hydrolysis with 28% ammonia solution. ₄ ). After drying at 100 ° C., 2.6 g of diatomaceous earth carrying Zr (OH) ₄ was added to 10 ml of a 1N aqueous sulfuric acid solution, and air-dried at room temperature (20 ° C.) for 24 hours.

  Rukabe diatomaceous earth was only pretreated with an acid / alkali solution.

The sulfated zirconia (ZrO ₂ / SO ₄ ) was calcined at 650 ° C. for 3 hours as a pretreatment.

Silver trifluoromethanesulfonate was not pretreated. The amount of catalyst used is 1 equivalent to the sugar donor for ZrO ₂ / SO ₄ and silver trifluoromethanesulfonate. In the case of sulfuric acid-treated diatomaceous earth and diatomaceous earth, an amount sufficient to fill the reaction vessel was set. Specifically, it was about 1.5 g per 10 ml of the internal volume of the container.

  Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out for 17 hours (18.5 hours for sample number No. 5) under the conditions of a temperature of 50 ° C. and a pressure of 12 Mpa.

After completion of the reaction, the reaction vessel was allowed to cool and returned to room temperature, so that CO ₂ as the solvent was vaporized and removed as a gas. The reaction product was diluted with chloroform, and then the catalyst was removed by filtration using filter paper. The removed zeolite analog / Rukabebe diatomaceous earth and Zr skeleton-substituted zeolite analog / Rukabebe diatomaceous earth can be reused by washing with chloroform and calcining at 650 ° C. for 2 hours.

The filtrate is purified by chromatography on a silica gel column and then concentrated under reduced pressure to give the desired formula:

224 mg of the product was recovered (zeolite analogue / Rukabe diatomaceous earth was used as catalyst).

  Table 4 shows the relationship between the type of catalyst and the yield (%).

Table 4. Catalysts and yields used in the synthesis of sugar-alcohols (glycosides)

  The yield was 2,3,4,6-tetra-O-acetyl-α-D-galacto used as a sugar donor using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1). Based on pyranosyltrichloroacetimidate, it was calculated in weight%.

  Furthermore, the result of having performed NMR measurement about the obtained glycoside is as follows.

1H-NMR data (CDCl ₃ , 400 MHz): 0.86-1.58 (m, 15H), 1.88-2.14 (4S, 12H), 3.44-3.50 (m, 1H), 3.86-3.90 (m, 2H), 3.91-4.21 (m, 2H), 4.45 (d, 1H, J = 3.4, 10.4), 5.20 (dd 1H, J = 8.0, 10.5), 5.39 (d, 1H, J = 3.357).

(Example 9) Synthesis of carbohydrate polymer In this example, an example in which a leaving group and a protecting group are introduced into both a sugar donor and a sugar acceptor to control the reaction position will be described.

In the reaction vessel, as a sugar donor, a leaving group is added to the OH group at the 1-position, and a protecting group is added to the OH groups at the 2nd to 4th and 6th positions. VIII) compound (2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyltrichloroacetimidate) was added in an amount of 175 mg (0.255 mmol).

Next, in the reaction vessel, a compound of the formula (IX) (aryl 2,3,6-tri-O— in which a protecting group is added to the OH groups at the 2-position, 3-position and 6-position as a sugar acceptor. 104 mg (0.195 mmol) of benzoyl-α-D-galactopyranoside) was added. More catalyst was added.

  The catalyst used here will be described with reference to Table 5.

  Table 5 is a table for explaining the sample number of Example 9, the catalyst used, and the amount (mg) of the catalyst.

Table 5 Catalysts and catalyst amounts used in the synthesis of carbohydrate polymers
Sulphated zirconia (ZrO ₂ / SO ₄ ) has been calcined at 650 ° C. for 3 hours as a pretreatment. Silver trifluoromethanesulfonate is not particularly pretreated.

  The amount of catalyst used is 1 equivalent to the sugar donor.

  Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out for 12 hours under the conditions of a temperature of 50 ° C. and a pressure of 12 Mpa.

After completion of the reaction, the reaction vessel was allowed to cool and returned to room temperature, so that CO ₂ as the solvent was vaporized and removed as a gas. The reaction product was diluted with chloroform, and then the catalyst was removed by filtration using filter paper. The removed catalyst can be reused by washing with chloroform and calcining at 650 ° C. for 2 hours.

The filtrate was purified by chromatography on a silica gel column (developing solvent was n-hexane: ethyl acetate = 4: 1) and then concentrated under reduced pressure to obtain 54 mg of the desired product of the following formula (X) (sulfated zirconia (ZrO as a catalyst). ₂ / SO ₄ )); 113 mg (using silver trifluoromethanesulfonate as catalyst) was recovered.

  The results are shown in Table 6. Table 6 is a table showing sample numbers, catalyst types and yields (%).

Table 6 Catalysts and yields used in the synthesis of carbohydrate polymers

The yield was (2,3,4,6-tetra-O-benzyl-α-D-) used as a sugar donor using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1). Based on galactopyranosyl trichloroacetimidate), it was calculated in weight%.

  Furthermore, NMR measurement was performed about the obtained carbohydrate polymer.

Measurement conditions and results are as follows.
(Measurement condition)
¹ H-NMR (400 MHz)
Equipment: JEOL JNM-LA400 FT NMR SYSTEM
Measurement temperature: 27 ° C
Solvent: CDCl ₃
(result)
1H-NMR data (CDCl ₃ , 400 MHz): δ 8.04-7.14 (m, 35H, Ph proton), 5.72 (m, 1H, allyl-CH =), 5.70 (dd, 1H, H _{-2), 5.67 (dd, 1H} , H-3), 5.35 (d, 1H, J 1,2 = 2.97Hz, H-1), 5.20 (dd, 1H, allyl CH 2 =), 5.09 (dd, 1H, allyl CH ₂ =), 4.90 (d, 1H, J _{1 ′, 2 ′} = 3.51 Hz, H−1 ′), 4.87-4.70 ( m, 8H, 4 × -CH ₂ Ph), 4.47-3.97 (m, 10H, proton of allyl-CH = and sugar ring).

Example 10 Synthesis of Sugar-Alcohol (Glycoside) In this example, an example in which a leaving group and a protecting group are introduced into a sugar donor to control the reaction position will be described.

In the reaction vessel, as a sugar donor, a leaving group is added to the OH group at the 1-position, and a protecting group is added to the OH groups at the 2nd to 4th and 6th positions. 300 mg (0.609 mmol) of the compound (XI) (2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl trichloroacetimidate) was added.

  Then, 0.48 ml (3.04 mmol) of 1-octanol was added. More catalyst was added.

  The catalyst used here will be described with reference to Table 7.

  Table 7 is a table | surface for demonstrating the sample number of Example 10, the used catalyst, and the quantity (mg) of a catalyst.

Table 7 Catalysts and catalyst amounts used in the synthesis of sugar-alcohol (glycosides)

The sulfuric acid-treated diatomaceous earth can be obtained by adding 2 g of a commercially available diatomaceous earth (dried product) to 5 ml of a 1N aqueous sulfuric acid solution and air-drying it overnight at room temperature (20 ° C.).

Similar to Example 1, the sulfuric acid-treated diatomaceous earth and sulfated zirconia (ZrO ₂ / SO ₄ ) were calcined at 650 ° C. for 3 hours as a pretreatment. Silver trifluoromethanesulfonate and diatomaceous earth are not particularly pretreated.

The amount of catalyst used is 1 equivalent to the sugar donor for sulfated zirconia (ZrO ₂ / SO ₄ ) and silver trifluoromethanesulfonate. In the case of sulfuric acid-treated diatomaceous earth and diatomaceous earth, an amount sufficient to fill the reaction vessel was set. Specifically, it was about 1.5 g per 10 ml of the internal volume of the container.

  Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out for 17 hours (18.5 hours for sample number No. 5) under the conditions of a temperature of 50 ° C. and a pressure of 12 Mpa.

After completion of the reaction, the reaction vessel was allowed to cool and returned to room temperature, so that CO ₂ as the solvent was vaporized and removed as a gas. The reaction product was diluted with chloroform, and then the catalyst was removed by filtration using filter paper. The removed catalyst (sulfurized diatomaceous earth and silver trifluoromethanesulfonate) can be reused by washing with chloroform and calcining at 650 ° C. for 2 hours.

The filtrate was purified by chromatography on a silica gel column and then concentrated under reduced pressure to recover 224 mg of the target product of the following formula (XII) (using sulfuric acid-treated diatomaceous earth as a catalyst).

  The results are shown in Table 8. Table 8 is a table showing sample numbers, catalyst types and yields (%).

Table 8 Catalysts and yields used in the synthesis of sugar-alcohols (glycosides)


The yield was 2,3,4,6-tetra-O-acetyl-α-D-galacto used as a sugar donor using silica gel chromatography (developing solvent was n-hexane: ethyl acetate = 4: 1). Based on pyranosyl trichloroacetimidate, it was calculated in weight%.

  Furthermore, NMR measurement was performed about the obtained glycoside.

Measurement conditions and results are as follows.
(Measurement condition)
¹ H-NMR (400 MHz)
Equipment: JEOL JNM-LA400 FT NMR SYSTEM
Measurement temperature: 27 ° C
Solvent: CDCl ₃
(result)
¹ H-NMR data (CDCl ₃ , 400 MHz): 0.86-1.58 (m, 15H), 1.88-2.14 (4S, 12H), 3.44-3.50 (m, 1H) 3.86-3.90 (m, 2H), 3.91-4.21 (m, 2H), 4.45 (d, 1H, J = 7.9), 5.02 (dd, 1H, J = 3.4, 10.4), 5.20 (dd, 1H, J = 8.0, 10.5), 5.39 (d, 1H, J = 3.357).

(Example 11) Synthesis of sugar-cholesterol In this example, an example in which a leaving group and a protecting group are introduced into a sugar donor to control the reaction position will be described.

In the reaction vessel, as a sugar donor, a leaving group is added to the 1-position OH group, and a protecting group is added to the 2-position to 4-position and 6-position OH groups. 175 mg (0.255 mmol) of the compound (XIII) (2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl trichloroacetimidate) was added.

(Wherein Bn is benzyl)
Next, 75 mg (0.195 mmol) of cholesterol was added as a sugar receptor in the reaction vessel. More catalyst was added.

  The catalyst used here will be described with reference to Table 9.

  Table 9 is a table | surface for demonstrating the sample number of Example 11, the used catalyst, and the quantity (mg) of a catalyst.

Table 9 Catalysts and catalyst amounts used in the synthesis of sugar-cholesterol

Sulphated zirconia (ZrO ₂ / SO ₄ ) has been calcined at 650 ° C. for 3 hours as a pretreatment. Silver trifluoromethanesulfonate is not particularly pretreated.

  The amount of catalyst used is 1 equivalent to the sugar donor.

  Cholesterol, which is a sugar acceptor, is somewhat difficult to dissolve in the supercritical fluid of carbon dioxide, which is a solvent, so additional additives are added to the reaction vessel to dissolve it in the supercritical fluid. In this example, 0.188 ml of chloroform was added as an additive substance.

  Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out for 12 hours under the conditions of a temperature of 50 ° C. and a pressure of 12 Mpa.

After completion of the reaction, the reaction vessel was allowed to cool and returned to room temperature, so that CO ₂ as the solvent was vaporized and removed as a gas. The reaction product was diluted with chloroform, and then the catalyst was removed by filtration using filter paper. The filtrate was concentrated under reduced pressure to recover the residue. The residue was purified by chromatography on a silica gel column (developing solvent was n-hexane: ethyl acetate = 4: 1) and then concentrated under reduced pressure to obtain 67 mg of the target compound of the following formula (XIV) (sulfated zirconia as a catalyst). (Using ZrO ₂ / SO ₄ )); 130 mg (using silver trifluoromethanesulfonate as catalyst) was obtained.

  The results are shown in Table 10. Table 10 is a table showing sample numbers, catalyst types and yields (%).

Table 10 Catalysts and yields used in the synthesis of sugar-cholesterol

The yield was 2,3,4,6-tetra-O-benzyl-α-D-galacto used as a sugar donor using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1). Based on pyranosyltrichloroacetimidate, it was calculated in weight%.

  Furthermore, NMR measurement was performed on the obtained sugar-cholesterol.

Measurement conditions and results are as follows.
(Measurement condition)
¹ H-NMR (400 MHz)
Equipment: JEOL JNM-LA400 FT NMR SYSTEM
Measurement temperature: 27 ° C
Solvent: CDCl ₃
(result)
¹ H-NMR data (CDCl ₃ , 400 MHz): δ 7.35-7.20 (m, 20H, Ph proton), 5.21 (t, 1H, cholesterol-OCH <), 5.06 (d, 1H, _{J 1,2 = 4.24Hz, H-1} ), 4.78-4.46 (m, 8H, 4 × -CH 2 Ph), 4.29 (t, 1H, H-3), 4.03 (Dd, 1H, H-2), 3.95 (t, 1H, H-4), 3.75 (m, 1H, H-5), 3.67 (dd, 1H, H-6) 55 (dd, 1H, H-6 ') 3.52 (m, 1H, cholesterol -CH =) 2.29-0.68 (m, 43H, other proton of cholesterol).

Example 12 Synthesis of Sugar-Peptide (Glycoside) In this example, an example in which a leaving group and a protecting group are introduced into a sugar donor to control the reaction position will be described. First, a sulfated titania-supported diatomaceous earth (SO ₄ ²⁻ / TiO ₂ / diatomaceous earth) as a catalyst used in this synthesis system was synthesized as follows.

  50 g of diatomaceous earth rock from Ichisei, Hokkaido was placed in a container for treatment, and 30% hydrogen peroxide (200 ml) was added. After standing for 1-2 hours, 36% hydrochloric acid solution (100 ml) was added. At this time, care was taken because it foamed violently and became hot. When boiling started, cold water was added to control the reaction temperature at about 80 ° C. When the color of the solution was yellow and the foaming stopped, cold water was added to precipitate crushed diatomaceous earth. After complete precipitation, the decantation of discarding the supernatant was repeated until the solution approached neutrality. Thereafter, decantation with 0.01 to 0.1% sodium pyrophosphate solution was performed. Thereafter, decantation with cold water was repeated again until the solution became neutral. The precipitate was dried at 100 to 150 ° C. with a vacuum dryer or an electric furnace to obtain a powdery dried diatomaceous earth.

4 g of dry powder (particle size 0.15 mm or less) of diatomaceous earth subjected to the above treatment was filled in a calcium tube, and 1 g of metal titanium was salified in a chlorine atmosphere to obtain TiCl ₄ . TiCl ₄ was vaporized at 400 ° C. and sent to the calcium tube by the pressure of nitrogen supplied from a high-pressure nitrogen cylinder. At this time, white smoke-like TiCl ₄ was vapor-deposited on the surface of diatomaceous earth by a CVD method (chemical vapor deposition method). After the deposition of TiCl _4, the amount supported on diatomaceous earth was calculated from the weight increase measurement, and the amount TiCl ₄ supported per gram of diatomaceous earth was estimated to be 4.7 mM. The diatomaceous earth carrying TiCl ₄ was taken out from the calcium tube and transferred to a beaker, and 50 ml of 28% ammonia water was added to obtain Ti (OH) ₄ . The precipitate was washed by decantation (7 times) and dried in an electric furnace at 100 to 150 ° C. overnight. After drying, 1N sulfuric acid (corresponding to 3.8 ml with respect to 1 g of diatomaceous earth) was added, air-dried at room temperature overnight, and then calcined at 650 ° C. for 3 hours to obtain sulfated titania-supported diatomaceous earth (SO ₄ ²⁻ / TiO ₂ / diatomaceous earth). Obtained.

Next, in the reaction vessel, as a sugar donor, a leaving group is added to the 1-position OH group, and a protecting group is added to the 2-5-position OH group (* 1) ;
(In the formula, Ac is acetyl)
100 mg (0.203 mmol) of the compound (2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl trichloroacetimidate) was added.

Next, structural formula (* 2) as a sugar receptor;
(Wherein Z is benzyloxycarbonyl)
105 mg (1.5 equivalents) of the above compound (Zet-threonine-O-benzyl) was added. Furthermore, 1 equivalent of sulfated titania-supported diatomaceous earth (SO ₄ ²⁻ / TiO ₂ / diatomaceous earth) was added as a catalyst to the sugar donor.

  Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was performed for 5 hours under conditions of a temperature of 35 ° C. and a pressure of 8 Mpa.

After completion of the reaction, the reaction vessel was allowed to cool and returned to room temperature, so that CO ₂ as the solvent was vaporized and removed as a gas. The reaction product was diluted with chloroform, and then the catalyst was removed by filtration using filter paper. The removed catalyst can be reused by washing with chloroform and calcining at 650 ° C. for 2 hours.

The filtrate was purified by chromatography on a silica gel column (developing solvent: toluene: ethyl acetate = 4 to 1: 1) and then concentrated under reduced pressure to obtain the desired formula (X3);
9.5 mg of product was recovered. The yield is 6.9%. The yield was calculated in weight% based on 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl trichloroacetimidate used as a sugar donor.

  Furthermore, NMR measurement was performed about the obtained glycoside.

Measurement conditions and results are as follows.
(Measurement condition)
¹ H-NMR (500 MHz)
Equipment: Bruker BioSpin Corporation (BRUKER), Bruker DPX-250 spectrometer
Measurement temperature: 27 ° C
Solvent: CDCl ₃
(result)
¹ H-NMR data (CDCl ₃ , 500 MHz): 7.37-7.31 (m, 10H, ph × 2), 5.59 (d, 1H, J _NH, αH = 9.09 MHz, NH), 5 .30 (d, 1H, J4, ₅ = 2.79 MHz, H-4), 5.18 (d, 2H, CH ₂ ph of benzyl ester), 5.13 (d, 2H, CH ₂ ph of Z ), 5.08 (dd, 1H, J2, ₃ = 10.5 MHz, H-2), 4.91 (dd, 1H, J3, ₄ = 3.43 MHz, H-3), 4. 41 (d d, 1H, J αH _{, βH} = 2.30 MHz, αH), 4.41 (d d, 1H, βH), 4.36 (d, 1H, J _1,2 = 7.93 MHz, H− 1), 4.03 (m, 2H, H-6a _{, b} ), 3.65 (t, 1H, H-5), 2.11, 2. 02,2.00,1.97 (s, 1H, Ac) , 1.21 (d, 3H, J CH3, β, H = 6.35MHz, βC-CH 3)
According to the method for synthesizing a carbohydrate polymer and a glycoside using a supercritical fluid as a solvent of the present invention, synthesis can be carried out efficiently in a simple process while reducing the burden on the environment.
INDUSTRIAL APPLICABILITY According to the method for producing a proton-type zeolite analog of the present invention, since the zeolite analog is directly used in an acidic solution, proton exchange is performed by ion exchange after synthesizing zeolitic. The process can be shortened. Further, since clay diatomaceous earth is used, it is not necessary to add an alumina source, the manufacturing process is simple, and the reaction can be performed efficiently. In addition, according to the method for producing a Zr skeleton-substituted zeolite analogue of the present invention, a proton-type zeolite analogue that functions as a Lewis acid can be produced by a calcination treatment even for diatomaceous earth lacking an alumina source. .

  According to the glycosylation reaction of the present invention, that is, the method for synthesizing a sugar polymer or glycoside, a supercritical fluid is used as a reaction solvent and a proton type zeolite analog is used as a catalyst. The load on the environment can be reduced, the reaction process is simple, and the reaction can be performed efficiently.

Claims (8)

A method for producing a raw material for producing a proton-exchanged zeolite analog, comprising a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral are substituted with H ⁺ , the method comprising: :
Treating the inorganic mineral with an acidic solution;
The raw material natural material containing the inorganic mineral is selected from Neogene diatomaceous earth . The raw material natural material containing the inorganic mineral is:
A mica mineral or a mica-based clay mineral, including at least one of opal;
Further comprising the method of claim 1. The method of Claim 1 which further includes the process of removing an organic substance and a smectite type mineral by the decantation using a neutral or alkaline solution. The method of claim 1, wherein the acidic solution comprises hydrogen peroxide. Wherein the acidic solution comprises hydrochloric acid solution, The method of claim 1 or 4. The method of claim 3 , wherein the neutral or alkaline solution comprises sodium pyrophosphate. The method according to claim 3 , wherein the smectite-based mineral includes montmorillonite. The raw material for manufacturing the proton-type zeolite analog which has the Lewis acid activity manufactured by the method of Claim 1.