WO2004007370A1 - Simple process for production of zeolite analogues functioning as acid catalysts - Google Patents

Abstract

A process for producing a raw material for the formation of proton-exchanged zeolite analogues whose cations are wholly or partially exchanged by H+ and which contain zeolite having tektosilicate structure, characterized by the step of treating a mineral with an acid solution; and a process of reacting a sugar donor with a sugar acceptor in the presence of a supercritical fluid as the solvent by using the proton-exchanged zeolite analogue itself as the catalyst to form a sugar -containing substance.

Description

 Description Simple method for producing zeolite analogs that function as acid catalysts

 TECHNICAL FIELD The present invention generally relates to a method for producing mesolites with a simple process that has a small environmental load and is related to the mesolites. More specifically, proton exchangeable zeolite analogs useful as Lewis acids are derived from diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rocks, siliceous shale, mudstone, claystone, siltstone, marine sediments, and lake sediments. The present invention relates to a method for producing and a proton exchanged zeolite analogue thereof. Further, the present invention relates to a glycosylation reaction which has a small environmental load and can be carried out in a simple process using the proton exchange type zeolite analog as a catalyst, and particularly relates to functional foods, biodegradable fibers, pharmaceuticals, surfactants or detergents. The present invention relates to a method for synthesizing a carbohydrate polymer or glycoside useful for the use of the present invention. Background technology

Generally, Zeoraito constitutes from S i 0 ₄ and A 1 0 ₄ tetrahedra (TO ₄ tetrahedra), Al force Li metal cations, and reversibly water adsorbing and desorbing (zeolite water). tau o ₄ tetrahedra linked by sharing the oxygen atoms of the vertexes, constitute the skeleton (tectosilicate) of the three-dimensional structure, T atoms and the molar ratio of oxygen 1: 2.

The mesolite expressed by the ideal formula Na A 1 S i ₂ Ο ₆ · Η ₂₀ is a natural zeolite normally produced from volcanic areas and belongs to the aluminosilicate minerals. Since anhydrite can be surface-treated, it is coated with a silicone film and has the function of selectively adsorbing ammonia, an ammonia adsorbent, and a surface treated with acid to provide a specific lubrication amount and refraction. An extender pigment having a predetermined ratio is produced. In addition, it derives hydrophobic crystalline zeolite from meticulite, and produces hydrocarbons in air or water. Filters have been devised to reduce the elemental content to a harmless degree, and a method has been devised that uses mesolite (crystalline silicon metalates) into which iron is introduced as an alkane oxidation catalyst. It is possible to exchange the metal cations of anhydrite. An ion exchanger utilizing this property is a general use of Zeolite. Square Alkali metal cations zeolite are N a +, has a T 0 ₄ tetrahedral framework of the same structure, Zeorai preparative analogs containing C a ^{2 +} as the alkali metal force thione comprises Wairake zeolite, the K + Zeolites are called leucite and occur naturally. These are all alkali metal cation exchanged analogs of mesolite. In industrial chemistry, zeolite in which alkali metal cations of mesolite have been exchanged for Li +, Ag +, K +, Ν + ₄ +, Τ 1 +, R b ⁺ , and C s +. Analogs have been produced.

When the alkali metal cation of the anhydrite is exchanged for NH ₄ + and heat-treated, NH ₃ is desorbed to obtain a proton-exchanged zeolite analog. It is known that Lewis acidity develops when a proton-exchanged zeolite analog is heat-treated.

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

However, since anatase has a more compact crystal structure than other zeolites, it is chemically and physically stable. In other words, the crystal structure is not destroyed even by the firing treatment, and it is synthesized even under a high temperature and high pressure environment of 450 ° C. and 10 OMPa. When heat treatment of proton exchange type zeolite DOO, away H ₂ 0 is removed, it expresses very strong electron affinity Lewis acidity, analcime is resistant to heat treatment, a proton exchange type Zeorai preparative analogues To make Lewis acid catalyst by heat treatment There are special advantages.

 Clay catalysts were first used for catalytic cracking of petroleum in 1936. Activated clay obtained by acid-treating acid clay (montmorillonite) was used. The activated clay catalyst was later replaced by synthetic silica-alumina (1944) and zeolite (1962).

 In the chemical industry, synthetic zeolites are mainly used as catalysts. Among naturally produced zeolite, erionite can be used as a catalyst because of its excellent acid resistance. Due to the poor quality of natural zeolite, its use as is is limited. However, even natural zeolites such as mesolite can be useful catalysts if chemical-controlled analogs are produced by chemical synthesis. The artificial zeolite uses sodium metasilicate and colloidal silica as a silica source and sodium aluminate as an alumina source, precipitates them in a heated NaOH solution, and separates the obtained solid by filtration. It is obtained by thoroughly washing with water and drying at 110 ° C. In this production method, zeolite A or zeolite Y can be obtained.

There are two main types of production methods for mesolite. The first is a method of manufacturing from tuff-type volcaniclastic rocks by hydrothermal treatment in NaOH, chloride, and sodium aluminate solutions. Specifically, volcaniclastic rock (tuff) containing clinoptilolite is treated with an alkaline hot aqueous solution containing Na ₂ CO ₃ —Na HCO ₃ to produce mesolite. In this production method, mesolite is produced in a synthetic system that reproduces the natural system. It is thought that natural mesolite is formed by the interaction between salt solution and volcanic glass in pyroclastic rock due to hot spring alteration.

It is also possible to produce mesolite from commercially available industrial products. That is, the addition of silica feed materials such as quartz in the aluminosilicate of a particular _{S i 0 2 / A 1 2} 0 3 molar ratio, N a OH or analcime be hydrothermally treated with KOH solution or Zeoraito analogues can get. Furthermore, even if the artificial glass with the same composition as the anhydrite is treated with hot water, Can be manufactured. In addition, as in the case of synthetic zeolites such as zeolite A and zeolite Y, mesolite can be produced from water-soluble silicates and aluminates. In the case of producing calcite by hydrothermal synthesis using sodium orthosilicate as a silica source and sodium aluminate as an alumina source, tetramethylammonium bromide is added as a catalyst.

 Although there are differences in the raw materials used in the production of these anhydrites, such as using natural volcaniclastic rocks or commercially available industrial products, the steps for adding alkali metal cations by hydrothermal synthesis are common. In order to use the mesolite obtained by this conventional production method as an acid catalyst, it was necessary to exchange protons from alkali metal cations by ion exchange to produce a proton exchanged anhydrite (see, for example, Japanese Patent Application Publication No. 2 0 0 2—5 0 8 0 6 Publication (see page 5)). Since calcite is resistant to heating, 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 a zeolite surface in addition to the above-described method for producing a proton exchange type zeolite. In this case, zeolite functions as a highly dispersed catalyst carrier. The catalytic metal is introduced into the zeolite by ion exchange.

Recent advances in zeolite science include silica zeolite substantially free of aluminum, the position of the T (A l, S i) atoms that form the framework structure is Ti, B, Fe, Ga, Ge, The synthesis of a so-called skeletal-substituted zeolite partially or wholly substituted with P has been made possible (see, for example, Japanese Patent Application Laid-Open No. 11-510136 (pages 4 to 9)). Also in analcime, industrial chemically replace S i 0 ₄ tetrahedra in G E_〇 _4, Zeorai preparative analogs obtained by adding C s + as alkali metal cations that are manufactured.

Since anhydrite is resistant to heat treatment, there is a particular advantage in producing a proton exchanged zeolite analog and converting it into a Lewis acid catalyst by calcination. In the conventional method for producing proton-exchanged mesolites, the cations in the mesolite are converted into ions. Protonation has been performed to produce a solid acid catalyst, and Lewis acidity has been developed by subsequent calcination treatment (for example, see Patent Document 1). However, if a proton-exchanged zeolite analog can be obtained in the process of producing anhydrite, the production process can be shortened.

 Synthetic zeolite is a raw material gel precipitated from silica and alumina sources in hot water.

It is crystallized by drying at a temperature of at least 0 ° C. If the crystallization process of the raw material gel and the calcination for Lewis acid catalysis can be performed simultaneously, the number of production steps can be further reduced. In other words, if the gel-like proton-exchange type zeolites can be precipitated in an acidic solution, when crystallization of the proton-exchange-type zeolite analog from the raw material gel occurs, if H ₂₀ is eliminated and Lewis acidity develops, Can be expected.

 Furthermore, when producing a transition metal-substituted zeolite analog catalyst, an alkali metal cation exchange-type zeolite catalyst into which a metal element is introduced by ion exchange has a problem with stability, but the transition metal element that functions as a catalyst has a problem. It can be expected that the stability will be improved if it can be introduced into the framework structure of zeolite. By synthesizing skeleton-substituted zeolite analogs with transition elements such as Zr and Ti, it is possible to change the pore diameter without changing the pore structure of mesolite.

 As described above, synthetic zeolites have been used as catalysts in the chemical industry because of their Lewis acidity. The present inventors have paid attention to the application of a catalyst to a synthesis system for carbohydrate polymers and glycosides, whose production process is extremely complicated. In particular, in the present invention, attention has been paid to a Darikosyridani reaction system in which a sugar donor and a sugar acceptor form a glycosidic bond between the sugar donor and the sugar acceptor, and are bonded to each other.

The glycosidic bond generated by the daricosylation reaction is, for example, a bonding mode that can be said to be a skeleton of a saccharide. Can be efficiently formed between hydroxyl groups of monosaccharides, oligosaccharides or polysaccharides, and molecules other than sugars, such as alcoholic hydroxyl groups, carboxylic acids and carboxyl groups of amino acids. This can be said to be a problem in synthesizing carbohydrate polymers and glycosides.

 Heretofore, for example, the production of carbohydrate macromolecules and glycosides has been carried out by using, for example, the Keonigs-Knorr method, the imidate method, and the fluorination method.

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

 On the other hand, the Fisher method, in which glycoside bonds can be generated between molecules in only one step in the presence of an acid catalyst, is extremely simple, and the industrial process for carbohydrate polymers and glycosides is extremely difficult. This method is suitable for mass production.

 For example, a condensation polymer obtained by condensation polymerization of D-glucose by O-glycosidic bonds in a large number by the Fisher method is used in the food field as an indigestible dietary fiber.

 When a large excess of methanol is allowed to act on D-glucose in the presence of hydrochloric acid, methyldaricoside O-glycosidized by the hydroxyl group at position 1 of D-glucose and the hydroxyl group of methanol is formed. This methyldaricoside can be used, for example, as a surfactant, a detergent and the like.

 Conventionally, by appropriately setting the leaving group, hydroxyl protecting group, carboxyl protecting group, amino protecting group, and / or catalyst of the sugar donor and the sugar acceptor, and performing the reaction, control of the reaction position, steric configuration Has been controlled. For example, in the imidate method described above, α-form and i3-form can be selectively synthesized at a high yield depending on 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 exerts a particularly heavy burden on the environment, is used.

Therefore, the glycosylic reaction, which is difficult with the solvent used in the conventional synthesis method, has simple steps, and has a low environmental load, that is, the emergence of a method for synthesizing a carbohydrate polymer or a glycoside is expected. . However, the conventional glycosylation reaction has a very complicated process and is not suitable for industrial mass production. In addition, since a large amount of an organic solvent such as benzene or a halogen-containing organic solvent having a large environmental load is used as a reaction solvent, there is a concern about a problem of waste liquid treatment after the process. Disclosure of the invention

 The present invention has been made in view of the above conventional problems.

 First, the present inventors are conducting intensive research and have added a 1N sulfuric acid solution to Neogene diatomaceous earth containing illite and muscovite, dried and calcined at 65 ° C to obtain Lewis acidity. Is found in diatomaceous earth. As a result of pursuing the factors that cause Lewis acidity to develop in diatomaceous earth, it was found that a zeolite analog was formed from clayey diatomaceous earth that had been added with a sulfuric acid solution, dried and calcined at 65 ° C. In contrast to conventional zeolite production in which an alkali metal is added in an alkaline solution, in the present invention, the zeolite analog produced in the present invention is produced in an acidic solution without adding an alkali metal. Does not take the form of acid salts. In other words, it is a proton-type zeolite analog in which the alkali metal of mesolite is replaced with proton.

 In addition, the present invention provides a glycosylation reaction, for example, a monosaccharide, a disaccharide, etc., by using a proton-type zeolite analog as a catalyst in the presence of a supercritical fluid, which is a reaction solvent having a small burden on the environment. It has been found that the condensation reaction between the saccharide units or the condensation reaction between the saccharide unit and alcohols, lipids, amino acids and the like proceeds efficiently, and the present invention has been completed. The present invention provides the following to achieve the above object.

(1) A method for producing a raw material for producing a proton-exchanged zeolite analog, which comprises a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral is substituted with H +, The method is as follows: A step of treating the inorganic mineral with an acidic solution,

The method.

 (2) The group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rocks, siliceous shale, mudstone, claystone, siltstone, marine sediments and lake sediments. The method according to (1), including at least one selected from the group consisting of:

 (3) The natural substances of the raw materials containing the above inorganic minerals are as follows:

 Opal; and

 Item (2), further comprising: a mica mineral or a mica-based clay mineral, including at least one of silica, paragonite, chinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite. Method.

 (4) The method according to item (1), further comprising a step of removing organic substances and smectite-based minerals 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 (1) or (5), wherein the acidic solution includes a hydrochloric acid solution. (7) The method according to (4), wherein the neutral or alkaline solution contains sodium pyrophosphate.

 (8) The method according to (4), wherein the smectite-based mineral includes montmorillonite.

 (9) A raw material for producing a proton-type zeolite analog having Lewis acid activity, which is produced by the method according to (1).

 (10) A method for producing a proton-exchanged zeolite analog, which comprises a zeolite having a tectosilicate structure in which all or a part of cations of an inorganic mineral is substituted with H +, the method comprising:

 A step of adding a mineral acid to the raw material obtained by removing the smectite-based clay mineral from the inorganic mineral, and reacting a silica source and an alumina source to obtain a reaction product; and

Baking the reaction product, Where:

Proton-exchanged zeolite analogs are represented by the formula W _p H _m — _{ρ η η} 0 _2η · SH ₂₀ , where W is an alkali metal, alkaline earth metal, or group IIIA-VIIA, VIII and IB A transition metal selected from the group consisting of elements,

 Z is A 1 + S i, and the S i ZA 1 ratio is an integer of 1 or more; 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,

 S is any number greater than or equal to 0, the method.

 (11) The method according to (10), wherein W is an alkali metal or an alkaline earth metal.

 (12) The natural substance as a raw material containing the above inorganic minerals is selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. Item 10. The method according to item (10), including at least one selected.

(13) The natural substance of the raw material containing the inorganic mineral is as follows:

 Opal; and

 13. The method according to item (12), further comprising: a mica mineral or a mica-based clay mineral, comprising at least one of illite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, marine chlorite, and muscovite.

 (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) The proton-exchanged zeolite analog produced by the method according to item (10), wherein the number of oxygen atoms O in the above formula is (2 n−0.5 (m_p)) or more and less than 2n. .

(18) All or part of the inorganic mineral cations are replaced with H +, A method for producing a transition-exchanged proton-exchanged zeolite analog, including a zeolite having a salt skeleton, comprising the steps of:

 A process of supporting transition metal compounds in raw materials obtained by removing smectite clay minerals from inorganic minerals,

Where:

Proton exchange Zeoraito analogues by introducing a transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 0,

 W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, 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 Group 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,

 S is any number greater than or equal to 0, the method.

 (19) The method according to item (18), wherein W is an alkali metal or an alkaline earth metal.

 (20) The natural substance as a raw material containing the above-mentioned inorganic minerals is selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. A method according to paragraph (18), comprising at least one selected. (21) The raw materials containing the above inorganic minerals are as follows:

 Opal; and

 The method according to item (18), further comprising: a mica mineral or a mica-based clay mineral, which comprises at least one of illite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite.

(22) the supporting step is vapor deposition of the transition metal compound by a CVD method, The method described in paragraph (18).

(23) The transition metal compound is a halide, sulfate, acetate, carbonyl, nitrate, or a mixture thereof, of a transition metal selected from the group consisting of Group IIIA to Group VIIA, Group VIII, and IB. The method according to (18). (24) The transition metal compound is a _{Z r C l 4, T i} C l 4, F e C 1 2 or et mixture The method according to term (23).

 (25) The method according to item (18), wherein the supporting step is impregnation of the transition metal hydroxide gel.

 (26) The method according to item (18), further comprising a step of hydrolyzing after the step of supporting.

 (27) The proton-exchanged zeolite produced by the method according to (18), wherein the number of oxygen atoms O in the above formula is (2n_0.5 (m−p)) or more and less than 2 n. Analog.

 (28) A method for producing a transition-exchanged proton-exchanged zeolite analog containing a zeolite having a tectosilicate salt skeleton in which all or a part of cations of an inorganic mineral is substituted with H +, The following:

 Adding an inorganic acid to an inorganic mineral supporting a transition metal, and reacting the transition metal with a silica source and an alumina source to obtain a reaction product; and

 Baking the reaction product,

Where:

Proton exchange Zeoraito analogues by introducing a transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 0,

 W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII, and IB;

Z is a transition metal selected from the group consisting of elements of groups IIIA to VIIA, VIII, and IB, or selected from the group consisting of elements of groups IIIB and IVB. Selected typical metal element,

 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,

 S is any number greater than or equal to 0, the method.

 (29) The method according to (28), wherein W is an alkali metal or an alkaline earth metal.

 (30) The natural substance as a raw material containing the above inorganic minerals is selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. The method of paragraph (28), comprising at least one selected. (3 1) The natural substances of the raw materials containing the inorganic minerals are as follows:

 Opal; and

 The method according to claim 28, further comprising: a mica mineral or a mica-based clay mineral, which comprises at least one of illite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite.

 (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 more. (34) The method according to item (28), wherein the product obtained by reacting the transition metal with a silica source and an alumina source is air-dried, and then calcined.

 (35) The proton-exchanged zeolite produced by the method according to (28), wherein the number of oxygen atoms O in the above formula is not less than (2 n-0.5 (m_p)) and less than 2 n. Analog.

 (36) A method for producing a proton-exchanged zeolite analog, which comprises a zeolite having a tectosilicate structure in which all or a part of cations of an inorganic mineral is substituted with H +, wherein the method comprises the following steps:

 Treating the inorganic mineral with an acidic solution;

An inorganic acid is added to the raw material after the acid treatment, and a silica source and an alumina source are reacted, Obtaining a reaction product; and

 Baking the reaction product,

Where:

Proton-exchanged zeolite analogs have the formula W _p H _m — _ρ Ζ _η 0 _2π · SH ₂₀ , where W is an alkali metal, alkaline earth metal, or group IIIA-VIIA, V

A transition metal selected from the group consisting of the elements of group I I I and IB,

 Z is A l + S i, and the S iZA l ratio is an integer of 1 or more; 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,

 S is any number greater than or equal to 0, the method.

 (37) The method according to (36), further comprising a step of removing the smectite-based mineral by decantation using a neutral or alkaline solution before adding the inorganic acid.

 (38) The method according to (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 diluent includes sodium pyrophosphate.

 (41) The natural substance as a raw material containing the above inorganic minerals is selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. The method of paragraph (36), comprising at least one selected.

 (42) The natural substances of the raw materials containing the inorganic minerals are as follows:

 Opal; and

(41) The method according to item (41), further comprising: a mica mineral or a mica-based clay mineral, including at least one of silica, mica, paragonite, chinwald mica, rishia mica, biotite, phlogopite, sea chlorite and muscovite. . (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) The method according to item (36), wherein the firing temperature is 540 ° C or more. (46) The method according to (36), wherein the product obtained by reacting the silica source with the alumina source is air-dried, and then calcined.

 (47) Similar to the proton-exchanged zeolite produced by the method according to (36), wherein the number of oxygen atoms O in the above formula is not less than (2 n−0.5 (mp)) and less than 2 n. body.

 (48) A method for producing a transition metal-introduced proton-exchanged zeolite analog, which includes a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral is substituted with H +, , Less than:

 Treating the inorganic mineral with an acidic solution;

 A process of supporting a transition metal compound in a raw material obtained by removing a smectite clay mineral from an inorganic mineral;

 A step of 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 to obtain a reaction product; and

 Baking the reaction product,

Where:

Proton exchange Zeoraito analogues by introducing a transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 0,

 W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from group IIA to group VIIA, group VIIA and IB,

Z is a transition metal selected from the group consisting of elements of groups IIIA to VI1A, VIII and IB, or a typical metal element selected from the group consisting of elements of group IIIB and IVVB. Yes, 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,

 S is any number greater than or equal to 0, the method.

 (49) The method according to (48), further comprising a step of removing the smectite-based mineral by decantation using a neutral or alkaline solution before adding 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) The neutral or alkaline solution contains sodium pyrophosphate, wherein (4)

The method described in 9).

 (53) The group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment and lake sediment The method according to paragraph (48), comprising at least one selected from the group consisting of: (54) The natural substances of the raw materials containing the inorganic minerals are as follows:

 Opal; and

 Item 53. The method according to Item (53), further comprising: a mica mineral or a mica-based clay mineral, including at least one of illite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite.

 (55) The smectite minerals include organic substances and montmorillonite.

The method according to (49).

 (56) The 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 thereof, of a transition metal selected from the group consisting of Group IIIA to Group VIIA, Group VIII, and IB elements. The method according to (48). (58) the transition metal _{compound, Z r C l 4, T} i C l 4, a F e C 1 ₂ or et mixture The method according to term (57).

 (59) The method according to item (48), wherein the supporting step is impregnation of the transition metal hydroxide gel.

 (60) The method according to item (48), further comprising a step of hydrolyzing after the step of supporting.

 (61) Similar to the proton-exchanged zeolite produced by the method described in (48), wherein the number of oxygen atoms O in the above formula is (2n−0.5 (mp)) or more and less than 2 n. body.

 (62) A method for producing a transition-exchanged proton-exchanged zeolite analog containing a zeolite having a tectosilicate structure in which all or a part of cations of an inorganic mineral is substituted with H +, the method comprising: The following:

 A process of supporting a transition metal compound in a raw material obtained by removing a smectite clay mineral from an inorganic mineral;

 A step of adding an inorganic acid to an inorganic mineral carrying a transition metal compound to react the transition metal with a silica source and an alumina source; and

 Baking the reaction product,

Where:

Proton exchange Zeoraito analogues by introducing a transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 〇,

 W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII, and IB;

 Z is a transition metal selected from the group consisting of elements from groups IIA to VIIA, VIII and IB, or a typical metal element selected from the group consisting of elements from group IIB and IVB;

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,

 S is any number greater than or equal to 0, the method.

 (63) The proton-exchanged zeolite produced by the method according to (62), wherein the number of oxygen atoms O in the above formula is not less than (2 n_0.5 (m−p)) and less than 2 n. Analog.

 (64) A method for synthesizing a sugar-containing substance, comprising a step of reacting a sugar donor with a sugar acceptor in the presence of a supercritical fluid to generate a sugar-containing substance.

 (65) The method according to item (64), wherein the supercritical fluid is a carbon dioxide fluid. (66) The 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) The method according to item (67), wherein the acidic solution is sulfuric acid.

 (69) The natural materials of the raw materials containing the above inorganic minerals are selected from the group consisting of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediments and lake marine sediments. Item 67. The method of item 67, comprising at least one selected. (70) The natural substances of the raw materials containing the above inorganic minerals are as follows:

 Opal; and

 (69) The method according to item (69), further comprising: a mica mineral or a mica-based clay mineral, including at least one of silica, mica, paragonite, chinwald mica, rishia mica, biotite, phlogopite, sea chlorite, and muscovite. .

(71) The acid catalyst is triflate Ruo Russia silver methane sulfonate, triflate Ruo b methanesulfonic acid trimethylsilyl, boron trifluoride GETS chill _{etherate, S nC l 2 - Ag C} 10 4, S nC l 2 - AgOT f, Cp 2 _{Z r C l 2 _AgC 10 4} , sulfated Jill Konia, diatomaceous earth, are selected et al or the group consisting of sulfuric acid treatment diatomaceous earth and sulfated titania supported diatomaceous earth, the method according to term (66).

(72) Item (64), wherein the sugar-containing substance is a carbohydrate polymer or a glycoside. the method of.

 (73) Equation (I)

(In the formula, R ¹ _OC (NH) CC 1 _3, is one C l, one B r or a F, R ² an OH, -OR ^6, an _N ₃ or a NHR ^7, R ³ and R ⁴ is, independently of one another, one OH or one OR ⁶ , R ⁵ is one H, one CH ₃ , one CH ₂ OH, one CH ₂ OR ⁶ , or —COOR ⁸ , and R ⁶ is , Independently of each other, is 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-protecting group, and R ⁸ is a carboxyl-protecting group )

One or more sugar donors selected from the group comprising a saccharide unit of

 Formula (I I);

Wherein R ⁹ is —OR ¹⁴ , R ¹⁰ is —OR ¹⁵ , —N ₃ or —NHR ¹⁶ , R ¹¹ is —OR ¹⁷ , R ¹² is one OR ¹⁸ , ¹³ is 1 H, _CH ₃ , -CH ₂ OR ¹⁹ or 1 COOR ²⁰ , and R ¹⁴ and R ¹⁵ are independently of each other, protected by 1 H, hydroxyl-protecting group or all reactive functional groups including hydroxyl group R ¹⁶ is an amino-protecting group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently of the other functional groups containing _H, a hydroxyl-protecting group or a hydroxyl group. R ² ° is a carboxyl group-protecting group, provided that at least one of R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ is 1 H. ) Comprising reacting one or more saccharide acceptors selected from the group containing a saccharide unit of the formula (II) with an acid catalyst and a supercritical fluid to produce a saccharide polymer. Method for synthesizing porous polymers.

 (74) The method according to item (73), wherein the supercritical fluid is a carbon dioxide fluid. (75) The method according to item (73), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.

(Wherein, R ²¹ an OC (NH) CC 1 _3, is one C l, one B r or a F, R ^{2 2} is _OH, -OR ^26, is -N ₃ or a NHR ^27, R ²³ and R ²⁴ are, independently of one another, 1 H or 1 OR ²⁶ ; R ²⁵ is 1 H, 1 CH ₃ , -CH ₂ OH, 1 CH ₂ OR ²⁶ or 1 COOR ²⁸ ; R ²⁶ is, independently of each other, a hydroxyl-protecting group or a sugar chain in which all reactive functional groups including a hydroxyl group are protected, R ²⁷ is an amino-protecting group, and R ²⁸ is a carboxyl group. A protecting group, provided that at least one of R ²² , R ²³ , R ^{24 and} R ²⁵ is a hydroxyl group (in the case of R ²⁵ , one CH ₂ OH).

One or more sugar units selected from the group containing

 A method for synthesizing a saccharide polymer, comprising a step of producing a saccharide polymer by reacting in the coexistence of an acid catalyst and a supercritical fluid.

 (77) The method according to item (76), wherein the supercritical fluid is a carbon dioxide fluid.

(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 an OC (NH) CC 1 _3, is one C l, one B r or a F, R ^{3 0} is - OR ^34, one N ₃ or - NHR ^35, R ³¹ and R ³² is Ri one oR ³⁴ der, R ³³ an H, _CH _3, is one CH ₂ oR ³⁴ or a COOR ^36,, R ³⁴ independently of one another, all of which contain hydroxyl protecting group or hydroxyl group, Is a sugar chain in which the reactive functional group is protected, R ³⁵ is an amino protecting group, and R ³⁶ is a carboxyl protecting group. A donor, diacylglycerol, ceramide, sterol and a terpene having at least 1 D hydroxyl group in the molecule; and

 Formula (V);

 R-OH (V)

 (Wherein, R is a linear, branched, cyclic having no side chain or a cyclic saturated aliphatic group having a side chain, or the above saturated fat containing one or more unsaturated bonds. Is an unsaturated aliphatic group corresponding to an aromatic group.)

A group of lipids containing 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) The method according to Item (79), wherein the supercritical fluid is a carbon dioxide fluid. (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 an OC (NH) CC 1 _3, is one C l, one B r or a F, R ^{3 0} one OR ^34, and an N ₃ or a NHR ^35, R ³¹ and R ³² is —OR ³⁴ , R ³³ is 1 H, 1 CH ₃ , 1 CH ₂ OR ³⁴ , or 1 COOR ³⁶ , and R ³⁴ independently of each other, contains a hydroxyl protecting group, or a hydroxyl group All reactive functional groups are protected sugar chains, R ³⁵ is an amino protecting group, and R ³⁶ is a carboxyl protecting group. A sugar donor; and formula (VI):

(式中、 R³⁷は _Hまたは— CH₃であり、 R ³⁸はァミノ基保護基、 ペプチド鎖 または糖鎖が結合したペプチド鎖であり、 R³⁹はカルボキシル基保護基、 ぺプチ ド鎖または糖鎖が結合したペプチド鎖である。 ただし、 R³⁸および/または R³⁹ が糖鎖が結合したぺプチド鎖である場合には、 その糖鎖の水酸基を含むすべての 反応性官能基は保護されているものとする。 ）

(Where R ³⁷ is _H or —CH ₃ , R ³⁸ is an amino group-protecting group, a peptide chain or a peptide chain having a sugar chain bonded thereto, and R ³⁹ is a carboxyl group-protecting group, a peptide chain or a sugar chain. When R ³⁸ and / or R ³⁹ is a peptide chain to which a sugar chain is bound, all reactive functional groups including the hydroxyl group of the sugar chain are protected. )

 And one kind of sugar receptor selected from the group including peptide chains to which amino acids, peptide chains and 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 carbon dioxide fluid. (84) The method according to Item (82), wherein the acid catalyst is an inorganic mineral treated with an acidic solution.

 (85) Formula (IV);

(Wherein, R ²⁹ an OC (NH) CC 1 _3, is one C l, one B r or a F, R ³ one OR ^34, one N ₃ or -. A NHR ^35, R ³¹ and R ³² is —OR ³⁴ ; R ³³ is —H, —CH ₃ , —CH ₂ OR ³⁴ , or COOR ³⁶ ; R ³⁴ is, independently of one another, a hydroxyl-protecting group, or any containing a hydroxyl group; R ³⁵ is an amino protecting group, and R ³⁶ is a carboxyl protecting group.) R ³⁵ is a sugar chain whose reactive functional group is protected. A sugar donor of the formula (VII):

(Wherein R ⁴ is one OR ⁴⁵ , R ⁴¹ is one OR ⁴⁶ , —N ₃ or —NHR ⁴⁷ , R ⁴² is —OR ⁴⁸ , R ⁴³ is —OR ⁴⁹ , R ⁴⁴ is 1 H, — CH ₃ , — CH ₂ OR ⁵ ° or 1 COOR ⁵¹ , and R ⁴⁵ is a diacylglycerol, ceramide, sterol, terpene, peptide obtained by removing a hydrogen atom from a hydroxyl group. or a peptide chain chain or sugar chains are bound, or a saturated aliphatic group or an unsaturated aliphatic group, R ⁴⁶ an H, all the reactive functional group containing a hydroxyl-protecting group or a hydroxy group is protected R ⁴⁷ is an amino protecting group; R ⁴⁸ , R ⁴⁹ and R ⁵ ° are: Independently of each other, 1 H, a hydroxyl group-protecting group or a sugar chain in which all reactive functional groups containing a hydroxyl group are protected, and R ⁵¹ is a carboxyl group-protecting group. However, R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ^5Q are not necessarily hydroxyl protecting groups, and one of R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵ ° is one H Or if none of R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵ ° is -H, one of the above sugar chains shall have one unprotected hydroxyl group . )

One sugar receptor selected from the group containing a sugar unit 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) The method according to Item (85), wherein the supercritical fluid is a carbon dioxide fluid.

(87) The 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 carbon dioxide fluid. (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. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a graph illustrating a powder X Senkai fold line towards zeolite crystal represented by the ideal formula _{Na A 1 S i 2 0 6} · H 2 O.

Figure 2 is a diagram showing the _{Na 10 Mg 3 A 1 16 S} i 32 0 96 · 25 H 2 0 in powder X-ray diffraction lines of M g switched peptidase Oraito analog crystal represented.

 FIG. 3 is a view showing an example of a powder X-ray diffraction line of the zeolite analog produced according to the present invention after the acid treatment.

Figure 4 shows the X-ray powder diffraction of diatomaceous earth from Ikusei, Hokkaido after pretreatment with acid It is a figure showing a line.

 FIG. 5 is a diagram showing X-ray powder diffraction lines of diatomaceous earth from Rubeshibe, Hokkaido after pretreatment with acid and alkali.

 FIG. 6 is a diagram showing an X-ray powder diffraction line 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 and alkali.

 FIG. 8 is a diagram showing the crystal structure of mesolite as a model for molecular orbital calculation. FIG. 9 is a diagram showing an X-ray powder diffraction line of a zeolite analog exhibiting Lewis acidity, obtained by treating diatomaceous earth produced by Ikuyo, Hokkaido with sulfuric acid and calcining.

 FIG. 10 is a diagram showing an X-ray powder diffraction line of a zeolite analog expressing Lewis acidity, obtained by sulfuric acid and calcination treatment of diatomaceous earth from Rubeshibe, Hokkaido.

 FIG. 11 is a diagram showing an X-ray powder diffraction line of a zeolite analog expressing Lewis acidity, obtained by sulfuric acid and calcination treatment of diatomaceous earth from Hirosaki, Aomori Prefecture.

 FIG. 12 is a diagram showing an X-ray powder diffraction line of a zeolite analog expressing Lewis acidity, obtained by treating diatomaceous earth from Higashikawa, Hokkaido with sulfuric acid and calcining.

 FIG. 13 is a diagram showing an X-ray diffraction line of a Zr skeleton-substituted zeolite analog made from diatomaceous earth produced from Rubeshibe, Hokkaido.

 FIG. 14 is a transmission electron micrograph of a cross section of diatom fossils in clayey diatomaceous earth containing a Zr skeleton-substituted zeolite analog.

 FIG. 15 is a photograph showing the elemental distribution of the particulate 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 element composition of the granular material of FIG.

 Figure 17 shows the result of analyzing the elemental composition of a granular material different from that of Figure 14

 FIG. 18 is a diagram showing an X-ray powder diffraction line of bentonite.

Fig. 19 shows the X-ray powder diffraction line of bentonite solidified in a sintered state after the treatment. FIG.

 FIG. 20 is a diagram showing an X-ray powder diffraction line of silicon dioxide (precipitated, amorphous). FIG. 21 is a diagram showing an X-ray powder diffraction line of amorphous silica.

 Fig. 22 is a diagram showing X-ray powder diffraction lines of clayey diatomaceous earth obtained by subjecting diatomaceous earth from Rubeshibe, Hokkaido, to calcination only.

 FIG. 23 is a diagram showing a synthesis chart for producing a proton-type zeolite analog or a proton-type zeolite analog into which a transition metal has been introduced from raw materials. FIG. 24 is a diagram for explaining a configuration example of a reaction apparatus used for the dalycosylation reaction of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. It is to be understood that the terms used herein are commonly used in the art unless otherwise indicated.

 As used herein, the term "inorganic mineral" refers to a natural or artificial substance containing an inorganic substance and having substantially uniform and constant chemical and physical properties, and may or may not contain an organic substance. .

 Inorganic minerals are generally classified by crystallography, and include silicate minerals, elemental minerals, sulfide minerals, oxide minerals, nitrate minerals, carbonate minerals, borate minerals, sulfate minerals, and tanda stinate / molybdate. Salt minerals, phosphates, arsenates, vanadate minerals, etc.

In the present specification, preferred inorganic minerals that can be the basis of the raw material include silicon-containing silicate minerals. The silicate minerals generally include the nesosilicate group (eg, olivine ((F e, Mg) ₂ [Sio ₄ ]), garnet, etc.), the silicate group (eg chlorite) _{(C a 2 (A 1,} F e) A 1 2 [O | OH | S i OHIS i 2 0 7]) , etc.), Saikurokei salt group (beryl _{(A 1 2 B e 3 [} S i 0 1 ₈ ]))), Inokate group ((Ca, Mg, Fe, A1, Ti) ₂ [(S i, Al) ₂ O ₆ ]), phyllosilicate group (mica, chlorite, clay mineral, etc.), tectosilicate group (quartz, feldspar, zeolite group, albaite, It is classified as zeolite (N a (a 1 S i 0 6) · H 2 0) , etc.).

 In the present specification, “clay mineral” means an inorganic substance as a main component constituting clay. Examples of clay minerals include olivine minerals, serpentine minerals, pyrophyllite, talc, smectite groups including montmorillonite, mica clay minerals including palmikiyulite, illite and muscovite, brittle mica, and chlorite. Is mentioned. Among these clay minerals, the clay minerals contained in the untreated clayey diatomite are the smectite group including montmorillite and the mica clay minerals including illite and muscovite. The clayey diatomaceous earth was pre-treated with acid and alkali to remove smectite-based clay minerals including montmorillonite. As used herein, “treatment” refers to, but is not limited to, operations such as mixing, dissolving, suspending, or chemical reaction.

 As used herein, the term “inorganic acid” refers to, but is not limited to, hydrochloric acid, sulfuric acid, nitric acid and the like. Preferred 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 appropriately changed.

According to the present invention, when producing a proton-type zeolite analog functioning as a Lewis acid or a proton-type zeolite analog into which a transition metal has been introduced, as a natural substance as a raw material containing the above-described inorganic mineral, At least one mixture of diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine and lake sediment can be used. Also, natural substances which can be a raw material of the present invention, in addition to the inorganic mineral, opal _{(S i Ο 2 · n H} 2 0) oxide minerals typified by silicate hydrate minerals such as; and Irai DOO, paragonite, Chinwarudo It is particularly preferred that the composition further includes a mica mineral or a mica-based clay mineral, including at least one of mica, lysium mica, biotite, phlogopite, chlorite, and muscovite.

Each of the above-listed natural substances is, for example, Jonsha 1996 1st October 20th First edition first edition, Science chronological table, National Astronomical Observatory of Japan Maruzen 1999 9th second edition, Chemical Dictionary, Chemical Dictionary Dictionary Editing Committee Kyoritsu It is a substance defined in, such as the first edition of the first edition published in 1960.

 In the conventional use of diatomaceous earth, Neogene diatomaceous earth containing clay minerals has been considered to be of low quality, but the present invention provides a new use of Neogene diatomite containing clay minerals. For example, Hokkaido Kabaoka (near Wakkanai), Enbetsu · Kinkomai (near Enbetsu), Notori · Yojin (near Abashiri), Ikuchiyo (Uraporo-cho, Tokachi-gun), Rubeshibe (Rubeshibe-cho, Tokoro-gun), Aomori The Neogene diatomite that can be mined from Hirosaki, Tochiuchi Pref. Is composed of opal or α-talist baritized amorphous silica as the main component, smectite clay minerals such as montmorillonite as impurities, and illite-white cloud. Clay diatomaceous earth containing mica clay minerals such as mother as impurities.

A 1 ₂ 0 ₃ content of Quaternary diatomaceous earth that are commonly quality is 0. A 5-2% strength S, A 1 ₂ 0 ₃ content of Neogene diatomaceous earth Hokkaido is It is 3 to 10%. Clay minerals in diatomite is rock forming minerals containing abundant of A 1 ₂ 0 _3, Neogene diatomaceous earth Hokkaido is characterized by a clay. In addition to Hokkaido and Aomori clayey diatomaceous earths, diatomaceous earths distributed throughout Noto Peninsula in Ishikawa Prefecture are well known. By utilizing clay minerals contained in clayey diatomaceous earth as an alumina source, a zeolite analog can be synthesized without adding sodium aluminate, a commercial industrial product, as an alumina source to diatomaceous earth containing silica as the main component it can. This is a production method based on the process of natural formation of anhydrite, which not only reduces costs but also reduces environmental impact.

Since A 1 ₂ 0 ₃ content in the clay diatomaceous earth is 1 0% at the maximum, most of the amorphous silica which is the major component of diatomaceous earth is not utilized for the synthesis of Zeoraito analogues . Nevertheless, in an experiment using clayey diatomaceous earth containing a zeolite analog as a solid acid catalyst (Reference Example 3), the desired product could be obtained in a positive yield. This is the amorphous silica remaining unused for the synthesis of the zeolite analog, This is because diatom fossils functioned effectively as carriers for zeolite analogs. In general, diatom fossils and diatom cell walls are porous and are known to be effective as catalysts alone. The state in which the zeolite analog is actually carried 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 Neogene diatomaceous earth from Hokkaido, but zeolite analogs can be obtained using Neogene diatomaceous earth from Aomori. Further, even when a high quality quaternary diatomaceous earth from Hokkaido is used as a raw material, a zeolite analog having a weak X-ray diffraction signal can be obtained. It is not limited to the type of diatomaceous earth.

 The method for producing a proton-type zeolite analog functioning as a Lewis acid catalyst or a proton-type zeolite analog into which a transition metal is introduced according to the present invention is shown in FIG. 23 (synthesis chart for obtaining a final product from raw materials). By reference, those skilled in the art can easily understand. The matters 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 is described as follows. The “zeolite analog” in the present specification refers to a structure having the above-described tectosilicate as a basic skeleton.

 In one embodiment of the present invention, in order to obtain an intermediate which is a raw material for producing a proton-type zeolite analog, as a pretreatment, an inorganic mineral as a raw material is subjected to an acid treatment (step 1 in FIG. 23). Then, decantation is performed in a neutral or alkaline solution (step 2 in FIG. 23) to obtain a raw material from which the smectite-based clay mineral is removed (intermediate 1 in FIG. 23). The step of decanting is performed as needed.

Preferred embodiments for obtaining Intermediate 1 from the raw materials are exemplified below. According to the present invention, preferably, the raw material is a neo-tertiary clayey diatomaceous earth from Hokkaido (for example, the raw material in FIG. 23). The dried diatomaceous earth rock is crushed with a hammer or the like, placed in a processing container, and, if necessary, hydrogen peroxide solution, preferably 1 to 30%, and Preferably, 30% aqueous hydrogen peroxide is added for washing. After standing for 1 to 2 hours, if necessary, an additional 1 to 36%, preferably 30 to 36% hydrochloric acid solution is added, followed by washing (for example, step 1 in FIG. 23). At this time, care should be taken because foaming occurs violently and the temperature rises. When the boiling starts, water is added to control the reaction temperature to 60 to 90 ° C, preferably about 80 ° C. When the color of the solution changes to yellow and the foaming stops, add cold water and wait for the crushed diatomaceous earth to settle. By this acid treatment, weakly consolidated diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, or unconsolidated marine or lake sediment, Crushed completely muddy. In the case of strongly consolidated diatomaceous earth, clayey diatomaceous earth, siliceous sedimentary rock, siliceous shale, mudstone, claystone and siltstone, debris with a particle size of 1 mm or more may remain. In this case, the viscous sediment is separated by transferring the suspension only to another container after vigorously stirring the sediment. The remaining fragments that have not been crushed can be reprocessed.

 After complete precipitation, repeat the decantation of discarding the supernatant several times. When the pH of the solution is 6 to 7, preferably around pH 7, decantation is performed several times with a solution containing a dispersant (for example, 0.0 :! to 0.1% sodium pyrophosphate solution).

(For example, step 2 in FIG. 23). In this case, the supernatant is turbid due to the suspended clay mineral. Carefully decant the sediment not to break the precipitate. In this case, it is preferable to perform decantation every 1 to 4 hours, preferably every 3 hours. After that, decantation with water is repeated several times, and the precipitate is dried at 100 to 150 ° C in a vacuum dryer or an electric furnace, etc., to obtain a powdery dry clayey diatomaceous earth. . When diatomaceous earth produced in Hokkaido is used, a powdery dry clayey diatomaceous earth corresponding to 10 to 40% of the raw material weight is usually obtained.

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

Powder X-ray of zeolite analog after acid-alkali treatment produced according to the present invention Fig. 3 shows an example of the diffraction line. FIG. 3 shows the same powder X-ray diffraction lines for the Mg-exchanged zeolite analog of FIG. 2 in Reference Example 2, showing the crystal plane showing the interatomic distance of 5.87 to 5.93 A and 3.52. It has a crystal plane showing an interatomic distance of ~ 3.54 A and a crystal plane showing an interatomic distance of 2.93 to 2.95 A.

 In Fig. 3, IK is a powder X-ray diffraction line of a zeolite analog using diatomaceous earth from Ikusei, Hokkaido, as a raw material, and RB is a powder X of a zeolite analog using diatomite from Rubeshibe, Hokkaido as a raw material. HR is a powder X-ray diffraction line of a zeolite analog using diatomaceous earth in Hirosaki acid in Aomori prefecture as a raw material, and HG is a powder X-ray diffraction line of a zeolite analog using diatomite from Higashikawa, Hokkaido as a raw material It is. Also, A 1 is the 211 crystal plane of the zeolite analog, 82 is the 400 or 410 crystal plane, A 3 is the 332 or 422 crystal plane, Q is the quartz crystal plane, and F is feldspar. C is the crystal face of cristobalite.

 In one embodiment of the present invention, an inorganic acid is added to the raw material (intermediate 1 in FIG. 23) from which the above-mentioned smectite-based clay mineral has been removed, and a silica source and an alumina source are reacted to obtain a reaction product. (Step 3 in FIG. 23), this is dried (Step 4 in FIG. 23), and then calcined (Step 5 in FIG. 23) to obtain a proton-type zeolite analog functioning as a Lewis acid (the final product in FIG. 23). Thing). Drying is performed as needed. A preferred embodiment for obtaining the final product 1 from Intermediate 1 is illustrated as follows.

 Transfer the dry powdered clayey diatomaceous earth to a 5 Om 1 Meyer and add the inorganic acid

(For example, step 3 in FIG. 23). Here, as a preferred example of the inorganic acid, 1N sulfuric acid (corresponding to 3.8 ml with respect to diatomaceous earth lg) can be mentioned, but the type and concentration of the inorganic acid are not particularly limited, and can be appropriately changed. After the addition of the inorganic acid, dry at room temperature overnight (for example, step 4 in Fig. 23). Drying is performed by introducing dry air into the mesher with an air pump. This drying is performed as needed. Since the weight decreases as the sulfuric acid solution evaporates, it is preferable to continue drying until there is no change in weight. New After drying and calcining for several hours (eg, step 5 in FIG. 23), a zeolite analog expressing Louis acidity (eg, final product 1 in FIG. 23) is obtained in diatomaceous earth. Here, the upper limit of the formation temperature of anhydrite is 450 ° C (for example, Ghobarkar, H. R, E ffectoft emp eratureonhydrotherma 1 s yn thesisofanalci me andvisite, Materia 丄 Science and Engineering 1999 B 60, pp. 163-167). Under normal pressure conditions, the zeolite stable region is up to 540 ° C (eg, Peter, T., Luth, WC, et al., Themeltingo Iana 丄 citesolidsolutionsint hesyst em NaA l S i O

_{4 - NaA l S i 3 0} 8 - H 2 O Th e Am enrican M ineralogist 1966 years 51 Certificates, cf. 736-753 pages) are known. Therefore, it is considered that at least the above-mentioned sintering temperature is required in order to generate the Lewis acid activity by distorting the crystal structure as in the present invention. The firing temperature used in the present invention is 500 ° C. or higher, preferably 540 ° C. or higher, and more preferably around 650 ° C. The fact that crystals of the zeolite analog have been obtained is confirmed by X-ray powder diffraction analysis.

On the other hand, when a sulfuric acid solution is added to bentonite rich in montmorillonite and calcined at 650 ° C, paragonite is produced (see Comparative Example 1). In the present invention, by using clayey diatomaceous earth from which montmorillonite has been removed, as shown in Examples 1 to 4, the generation of minerals other than zeolite analogs can be suppressed. That is, the only mineral produced from these diatomaceous earths after addition of sulfuric acid and firing at 650 ° C is a zeolite analog. Whether or not Lewis acidity is expressed in the zeolite analog from which the H ₂ O molecule is eliminated from the zeolite analog can be confirmed, for example, by a molecular orbital calculation method.

Here, proton-type zeolite in which all or part of the cation is replaced with H + Analogs are generally of the following (formula 1):

W _p H _m _ _p Z _n 0 _{2nSH 2} O (Equation 1)

(Where W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of Group IIIA to VIIA, Group VIII, and IB elements, and H is A hydrogen atom, Z is A l + S i, and the S i / A 1 ratio is an integer of 1 or more, m and n are each an integer of 1 or more, and p is 0 or more And is an integer less than m, and S is any number greater than or equal to 0). When the proton-type zeolite analog is heated, the zeolite water is desorbed, so that it takes the following structure (formula 2).

W _p H _m _ _p Z _n 0 _2n (Equation 2)

 It is calculated that the Lewis acid activity is expressed in the zeolite analog when the H atom and the O atom are eliminated as water molecules in a ratio of 2: 1. In this case, it can be expressed as the following (Equation 3).

 n 2 n-0.5 (m-p) o)

 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 (2 n — 0.5 (m−p)) or more and less than 2 n.

Then, showing Z r 0 ₄ at T0 ₄ tetrahedra replaced skeletal substituted Zeoraito analog manufacturing method of the following.

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

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

Fill the container with dry powdered clayey diatomaceous earth (eg, step 6 in Figure 23) 0 ° C at a feed of the Z r C 1 ₄ vaporizing in a container, by CVD (chemical vapor deposition), the Z r C 1 ₄ fine particulate is deposited on the surface of the clay diatomaceous earth. Particles produced by CVD, in order to uniformly adsorbed on clay minerals diatom surface can be produced efficiently TO ₄ tetrahedral framework substituted with replaces the zeolite preparative analogs. As described above, as a method of supporting the transition metal compound on the intermediate 1, in addition to the above-described CVD method, a method of impregnating the transition metal hydroxide gel with dry powdery clayey diatomaceous earth is also effective. Preferred examples of the transition metal hydroxide include T i (OH) _{4 and} Z r (OH) ₄ .

 In one embodiment of the present invention, an inorganic acid is added to Intermediate 1 supporting the above transition metal (Intermediate 2 in FIG. 23), and the transition metal is reacted with a silica source and an alumina source to form a reaction product. The product was dried (step 8 in FIG. 23), dried (step 9 in FIG. 23), and then calcined (step 10 in FIG. 23) to obtain a proton-form into which a transition metal functioning as a Lewis acid was introduced. A zeolite analog (final product 2 in FIG. 23) is obtained. A preferred embodiment for obtaining the final product 2 from Intermediate 2 is illustrated as follows.

After deposition of the above Z r C 1 _4, container feed air to produce a _{Z r C 1 2 0 · 8H} 2 O in the form of fine particles Z r C 1 ₄ hydrolysis min construed clayey diatomite surface (e.g. Step 7 in Figure 23). After hydrolysis of _{Z r C 1 4, Z r} C 1 2 responsible lifting amount to 0 · 8 H ₂ O argillaceous diatomaceous earth is calculated by measuring the weight gain, estimate the amount of supported per diatomite 1 g Yes. From the container, clay diatomaceous earth carrying a _{Z r C 1 2 0 · 8} H 2 0 ( e.g., Intermediate 2 in FIG. 23) was taken out, aqueous ammonia was transferred to a beaker (preferably 2 8% aqueous ammonia) To obtain Zr (OH) ₄ . The precipitate is washed with decantation (5 times) and dried in an electric furnace at 100-150 ° C all day and night. After drying, an inorganic acid is added (for example, step 8 in FIG. 23). The type and concentration of the inorganic acid are not particularly limited, but 1N sulfuric acid (equivalent to 3.8 ml with respect to diatomaceous earth lg) is particularly preferred. After adding an inorganic acid and drying at room temperature all day and night (for example, step 9 in Figure 23), The temperature is 500 ° C. or more, preferably 540 ° C. or more, and more preferably, about 650 ° C., and calcined for 1 to 5 hours, preferably 3 hours (for example, the step shown in FIG. 23). 1 0), Z r 0 Z r skeleton substituted by replacing the T 0 ₄ tetrahedra Zeorai bets analogue in ₄ Zeorai preparative analogs can be obtained. It is confirmed by X-ray powder diffraction analysis that the Zr skeleton-substituted zeolite analog is obtained. Also, it is confirmed by molecular orbital calculation method whether Lewis acidity is expressed in the zeolite analog from which the H ₂ O molecule is eliminated from the zeolite analog into which Zr is introduced.

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

 In another embodiment of the present invention, a daricosylation reaction characterized by reacting a sugar donor with a sugar acceptor in the presence of a catalyst and a supercritical fluid, that is, a saccharide polymer or glycoside Are provided.

 As used herein, “sugar-containing substance” refers to a substance containing a monosaccharide or a sugar chain and a substance other than these. Such sugar-containing substances are found abundantly in living organisms, and include, for example, polysaccharides, carbohydrate polymers, degraded polysaccharides, glycoproteins, proteodalicans, and glycosaminodalicans, which are contained in living organisms. And a wide range of compounds such as complex biomolecules or glycosides such as glycolipids and sugar chains decomposed or derived from these complex biomolecules, but are not limited thereto.

As used herein, the term “carbohydrate polymer” refers to a compound formed by linking one or more unit sugars (monosaccharides and / or derivatives thereof). If two or more unit sugars are linked, The unit sugars are usually connected by dehydration condensation via glycosidic bonds. Examples of such sugar chains include, for example, polysaccharides (glucose, galactose, mannose, fucose, xylose, N-acetinol regolecosamine, N-acetyl galatatosamine, sialic acid, Conjugates and derivatives), as well as a wide range of sugar chains degraded or derived from complex biomolecules such as degraded polysaccharides, glycoproteins, proteoglycans, glycosaminoglycans, and glycolipids. It is not limited to. In the present specification, the saccharide polymer is referred to as “sugar chain”,

It can be used interchangeably with "polysaccharide", "carbohydrate", and "carbohydrate". Unless otherwise specified, the term “sugar chain” in this specification may include both a sugar chain and a sugar chain-containing substance.

 As used herein, the term "glycoside" refers to a compound in which a hydrogen atom of a hemiacetal or hemiketal hydroxyl group of a saccharide is substituted with a functional group such as an alkyl group or an aryl group, and which reacts with the saccharide. Examples of the compound to be caused include alcohols, lipids, and peptide chains.

As used herein, the term "monosaccharide" refers to polyhydroxyaldehyde or polyhydroxyketone, which is not hydrolyzed to a simpler molecule and contains at least one hydroxyl group and at least one aldehyde group or ketone group. Refers to its derivatives. Usually monosaccharide, is represented by the general formula C _n H _{2 n} O _n not limited to, fucose (Kisosu to Dokishi), also include such N- § cetyl Darco Sa Min. Here, in the above equation, n = 2, 3, 4, 5, 6, 7, 8, 9, and 10 are replaced by jigs, birds, tetros, pentoses, respectively. Kisose, heptose, otatose, nonose and decos. Generally, it is equivalent to the aldehyde or ketone of chain-type polyhydric alcohols. The former is called aldose and the latter is called ketose. As specifically referred to herein, a monosaccharide derivative refers to a substance resulting from the substitution of one or more hydroxyl groups on an unsubstituted monosaccharide for another substituent. Examples of such monosaccharide derivatives include sugars having a carboxyl group (for example, aldonic acid in which the C-1 position has been oxidized to a carboxylic acid (for example, D-darconic acid in which D-dalcoose has been oxidized). ), The terminal C atom became a carboxylic acid A sugar having an acid (D-glucuronic acid in which D-glucose is oxidized), an amino group or a derivative of an amino group (eg, an acetylated amino group) (eg, N-acetyl-D-darcosamine, Acetyl-D-galactosamine, etc.), a sugar having both an amino group and a propyloxyl group (eg, N-acetylneuraminic acid (sialic acid), N-acetylmuramic acid, etc.), and a deoxylated sugar (eg,

2-Doxy-D-ribose), sulfated sugars containing a sulfate group, and phosphorylated sugars containing a phosphate group, but are not limited thereto. In the present specification, the term “monosaccharide” includes the above-mentioned derivatives. Alternatively, in sugars that have formed a hemiacetal structure, the daricosides of the acetal structure that have reacted with the alcohol are also within the scope of the monosaccharide. As used herein, "glycopeptide" and "glycoprotein" are used interchangeably and refer to peptides and proteins containing at least one sugar chain. Normally, glycoproteins have sugar chains necessary for their functions in higher organisms. The sugar chain and the peptide or protein may be directly linked, or may be indirectly linked via a spacer (for example, any divalent group such as a polymethylene group). Such glycoproteins include, but are not limited to, for example, enzymes, hormones, cytokines, antibodies, vaccines, receptors, serum proteins, and the like.

 Well-known peptides such as insulin can be used. By way of example, the insulin can include, but is not limited to, human insulin, porcine insulin, and insulin. Insulin has an amino group at the N-terminus of the A and B chains, 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 any species can be used.

As used herein, the term “supercritical fluid” is defined as a non-condensable fluid that exceeds the gas-liquid critical temperature inherent to a substance. Supercritical fluids have the properties of both gas and liquid, that is, as a solvent, high solubility close to liquid and high diffusivity close to gas. Specifically, supercritical fluids such as water, carbon dioxide, and alcohol are known. ing.

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

 Carbon dioxide has almost the same polarity as hexane, which is commonly used as an organic solvent, so these are particularly important when using a sugar donor and / or a sugar acceptor containing a protecting group. Are easily dissolved, and the reaction efficiency is good.

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

The catalyst applied to the dalycosylation reaction of the present invention is not particularly limited as long as the object of the present invention is not impaired. Usable catalysts include AgOT f (silver trifluoromethanesulfonate), TMSOT f (trimethylsilyl trifluoromethane), BF ₃ · OEt ₂ (boron trifluoride getyl ether complex), SnCl ₂ _AgC 10 _{4 , SnC l 2 - AgOT f,} Cp 2 Z r C 1 2 -AgC 10 4 (C p 2 Zr C 1 2: zirconocene dichloride de), sulfated Jirukonia _{(Z r 0 2 SO 4)} , diatomaceous earth, acid treatment Diatomaceous earth, so ₄ ² — ZT i O ₂ / diatomaceous earth (diatomaceous earth supporting sulfated titania), etc., are preferred, but solid acid catalysts that facilitate separation of the catalyst after the reaction is completed, that is, AgOT f, sulfated Jirukoyua _{(Z r 0 2 / S0 4} ), diatomaceous earth, sulfuric acid treatment diatomaceous ^{_{earth, S0 4 2 _ZT i 0 2}} / diatomaceous earth and is good to Les,. More preferably, the diatomaceous earth is a sulfuric acid-treated diatomaceous earth which can recycle the catalyst, has a low impact on the environment, and has excellent catalytic activity.

In the glycosylation reaction of the present invention, the sugar donor _OC in position 1 _{(NH) CC 1 3, -} C 1, it is not particularly limited if it has a leaving group -B r or F. In the case of synthesizing a saccharide polymer, preferably, for example, a saccharide unit of the following formula (I) And one or more selected from the group including.

(In the formula, R ¹ one 〇_C (NH) CC 1 _3, one C l, is one B r or a F, R ² an OH, - OR ^6, is an N ₃ or NHR ^7, R ₃ and R ₄ are, independently of one another, one OH or OR ⁶ , R ⁵ is one H, _CH ₃ , one CH ₂ OH, _CH ₂ OR ⁶ , or COOR ⁸ and R ⁶ is independent of one another In addition, a hydroxyl group-protecting group or a sugar chain in which all reactive functional groups including 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 resulting saccharide polymer, an appropriate protecting group is introduced from R ² to R ⁵ in the formula so as not to contain a reactive hydroxyl group. The reaction may be performed. Further, when the resulting saccharide polymer may include a random structure and / or a plurality of types of saccharide units, one or more types of saccharide units having one or more reactive hydroxyl groups may be used. The reaction can be carried out by appropriately mixing.

 In the present invention, the number of monosaccharides constituting a sugar chain is adjusted so that the number of monosaccharides in the entire compound is 20 or less, in consideration of solubility in a supercritical fluid and practical application. Good to do.

Specific examples of monosaccharides constituting sugar chains include glucose, galactose, mannose, talose, idose, growth, arose, anorethose, xylose, lyxose, arabinose, ribose, fucose, rhamnose and other anoredolose, Deoxy sugars such as fucose and rhamnose; and peronic acids such as glucuronic acid, galataturonic acid, mannuronic acid, isuronic acid, and guluronic acid; and amino sugars such as gnorecosamine, galactosamine, and muramic acid. The reactive functional groups of these sugar chains include a hydroxyl group, an amino group, and a carboxyl group. Where sugar The chains 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, amino and carboxyl groups of the sugar chain may be appropriately protected with a hydroxyl-protecting group, an amino-group protecting group and a carboxyl-group protecting group, 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 known to those skilled in the art can be introduced at a desired position by a known method. Specifically, examples of the hydroxyl group-protecting group include, for example, acetyl group, benzoyl group, monoacetyl group, acetyl group-containing protecting group including sulfonic acid ester group, benzyl group, methoxybenzyl group, trityl group, Examples include ether-based protecting groups including a lumyl group, an aryl group, and a silyl ether group. When two or more hydroxyl protecting groups are present in the same molecule, they may be the same hydroxyl protecting group or different hydroxyl protecting groups. Examples of the amino group-protecting group include an acetyl group, a methyl group, a rubbamate group, a naphthyl group, a thiocarbamate group, a trihalogenacetyl 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 group-protecting group include an alkyl group, a silyl group, a thioalkyl group and an aryl group. When two or more carboxyl protecting groups are present in the same molecule, they may be the same carboxyl protecting group or different carboxyl protecting groups. In the glycosylation reaction of the present invention, the sugar acceptor is not particularly limited as long as it has at least one hydroxyl group in the molecule.

When the target product is a saccharide polymer, the saccharide acceptor is preferably one or more compounds selected from the group containing a saccharide unit of the following formula (II), for example. Is good.

Wherein R ⁹ is —OR ¹⁴ , R ¹⁰ is —OR ¹⁵ , —N ₃ or NHR ¹⁶ , R ¹¹ is one OR ¹⁷ , R ¹² is one OR ¹⁸ , and R ¹³ is — H, — CH ₃ , one CH ₂ OR ¹⁹ or COOR ²⁰ , and R ¹⁴ and R ¹⁵ are each independently of one another, and all reactive functional groups including a hydroxyl protecting group or a hydroxyl group are protected. R ¹⁶ is an amino-protecting group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently of one another, _H, a hydroxyl-protecting group or any reactive functional group containing a hydroxyl group. R ² ° is a carboxyl protecting group, provided that at least one of R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ is 1 H .). If the molecule has two or more hydroxyl groups, the sugar donor binds to the target hydroxyl group as well, and the selectivity of the reaction will be reduced. When is required, it is preferable to have one appropriately selected hydroxyl group.

 Further, the glycosylation reaction of the present invention can be applied to a case where a sugar donor also functions as a sugar acceptor. Specifically, one or more saccharide units selected from the group containing the saccharide units 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) CC 1 3} , is one C l, one B r or F, R ²² is _OH, -OR ^26, is -N ₃ or NHR ^27, R ²³ and R ²⁴ , each other Independently, is one OH or OR ²⁶ , R ²⁵ is one H, _CH ₃ , _CH ₂ OH, -CH ₂ OR ²⁶ or COOR ²⁸ , and R ²⁶ is, independently of each other, a hydroxyl protecting group, or A sugar chain in which all reactive functional groups including a hydroxyl group are protected, R ²⁷ is an amino group protecting group, and R ²⁸ is a carboxyl group protecting group. However, among ^{R 22, R 2 3, R} 24 or R ^25, at least one hydroxyl group (in the case of R ²⁵ is one CH ₂ OH) is assumed to be. ).

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

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

(Wherein, R ²⁹ is _{- OC (NH) CC 1 3} , - C l, is one B r or F, R ³⁰ an OR ^34, and an N ₃ or NHR ^35, R ³¹ and R ³² One OR ³⁴ , R ³³ is one H, one CH ₃ , one CH ₂ OR ³⁴ , or COOR ³⁶ , and R ³⁴ is, independently of each other, a hydroxyl protecting group or any reaction containing a hydroxyl group. R ³⁵ is a protecting group for an amino group, and R ³⁶ is a protecting group for a carboxyl group.)

In this case, the sugar acceptor is preferably a lipid such as diacylglycerol, ceramide, sterol or a terpene having at least one hydroxyl group in the molecule, and the following formula (V) Saturated aliphatic alcohol or unsaturated aliphatic alcohol Good to call.

 R-O H (V)

 (Wherein, R is a linear, branched, cyclic having no side chain or a cyclic saturated aliphatic group having a side chain, or the above saturated fat containing one or more unsaturated bonds. Is an unsaturated aliphatic group corresponding to an aromatic group).

 Here, the steronore includes cholesterol monolease, _enolegosteroneleole, sito sterole / le, cholestanolelele, stigmasteroleleole, monohydric alcohols such as epicoprostanole, coprostanol, estriol, estradiol, etc. And polyhydric alcohols. Furthermore, when the molecule has a reactive functional group other than a hydroxyl group, that is, a carbonyl group, a carboxyl group, and an aldehyde group, a protective group known to those skilled in the art is introduced into a desired position by a known method, and then the reaction is performed. Sterols having a carbonyl group, such as prednisone, androsterone, estrone, testosterone, and prednisolone; and sterols having a carboxyl group, such as cholic acid, cholanic acid, dexcholate, and lithocholic acid. However, sterols having an aldehyde group include aldosterone and strofantizine. Examples of the protecting group include dimethyl acetal, dimethyl acetal, dibenzyl acetal, diacetyl acetal, 1,3-dioxane acetal, S, S, and carbonyl. Dimethyl acetal group, etc., carboxyl group, benzyl ester group, chloro ester group, cyclohexyl ester, etc., and aldehyde group, dimethyl acetal group, getyl acetanol group, dibenzyl acetal group, etc. And a diacetyl acetal group.

Terpene is a compound in which two or more isoprene units are linked in a chain or ring. Depending on the number of isoprene units, monoterpenes (two isoprene units), sesquiterpenes (3), diterpenes (4) ), Sesterterpen (5), triterpene (6), tetraterpene (8). In the present invention, Although any terpene can be used for the reaction, it is, of course, essential to have at least one hydroxyl group in the molecule.

 Examples of the terpene that satisfies the above requirements include nerol, (+)-linalool, (+)-isomenthol, γ-terbinol, (1-) one-menthol, (+)-borneol, (-)-one ^ Monoterpenes, Huarnesol,

(+) — Sesquiterpenes such as nerolidol and guaiaol, diterpenes such as phytol, isophytol, geranylgeraniol, umbrain, α-onoserine, agnostero-4 ^, oyho ^ /, and tritenolene pen such as lanosterol Are mentioned. Further, when a terpene molecule has a reactive functional group other than a hydroxyl group, for example, a carboxy group or a carbonyl group, after introducing a protecting group known to those skilled in the art to a desired position by a known method. It is desirable to provide for the reaction.

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

Preferred alcohol Darikoshiru reaction of the present invention, for example, methanol, ethanol, 1-Purono Kunoichi Honoré, 2 Puronoヽ⁰ Nord, 1-butanol, 2-butanol, 1 _ pentanol, Kisanonore to 1 one , 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, etc., linear saturated alcohols, aryl alcohol (2-propen-1-ol), 2-pentene-1-ol, 2-propyn-1-ol —Unsaturated linear alcohols such as ol, t-butyl alcohol, 3-ethynole-3-pentanol, 3-methinole-2-pentanole, 5-methinole-2-hexanol, cyclohexanemethanol, cyclooctane Branched saturated alcohols such as methanol, 4 _n-propyl-1-hepten-4-ol, 2-methyl -1-pentene-3-ol, 3-ethyl-1-5-hexene-1,3-honole, etc. Branched unsaturated anolecol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol Cyclic saturated alcohols without side chains such as tanol, cyclic unsaturated alcohols without side chains such as 2-cyclohexenol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1-methylcycloheptanol, 1-ethylcyclohexane Examples thereof include cyclic saturated alcohols having a side chain such as xanol, and cyclic unsaturated alcohols having a side chain such as 3-methyl-2-cyclohexen-1-ol.

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

(Wherein, R ^{3 7} is -H or CH _3, R ^{3 8} is Amino group protecting groups, was a peptide chain or a peptide chain sugar is bonded, R ^{3 9} represents a carboxyl group protecting group, the peptide a peptide chain having a chain or a sugar chain is bound. However, if R ^{3 8} and / or R ^{3 9} is peptide chains attached sugar chains, all of reactivity functional containing a hydroxyl group of the sugar chains Groups shall be protected).

The term “peptide chain” used herein includes not only a compound in which two or more amino acid residues are linked by peptide bonds but also one amino acid residue. It is desirable that the amino group and the carboxyl group at the C-terminus be protected. As the number of amino acid residues increases, the solubility in supercritical fluid and the stability of the compound decrease, so the number of amino acid residues in the compound as a whole should be 5 or less. desirable.

 Examples of the carboxyl group-protecting group include a methyl ester group, an ethyl ester group, a benzyl ester group, and a t-butyl ester group. Examples of amino-protecting groups include benzyloxycarbonyl, p-toluenesulfonyl, t-butyl / reoxycarbonyl, p-methoxybenzyloxycarbonyl, t-amyloxycarboninyl, and iso- Examples include a bornyloxycarbonyl group, a triphenylmethyl group, a 9-fluorenylmethyloxycarbonyl group, and a 5-benzisoxazolylmethylenoxycarbonyl group.

 In addition, the reactive functional group in the peptide chain includes a hydroxyl group, a thiol group, a guanidino group, and an imidazole group, in addition to the above-mentioned amino group and carboxyl group, all of which need to be protected by a known method. There is. For example, examples of the hydroxyl-protecting group include a benzyl group and a t-butyl group. Examples of the protective group for the thiol group include a benzyl group, a methoxybenzyl group, a methylbenzyl group, a trityl group, an acetamidomethyl group, a carboxymethoxysulfeninole group, a benzyloxymethinole group, a ferrocenylmethyl group, and a dimethylphosphinothioyl oil. And the like.

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

 Further, for example, as described above, sterols, amino acids, polypeptides, and peptide chains to which sugar chains are bound all have the same solubility, and therefore all of them are applicable to the glycosylation reaction of the present invention. It is suitable.

For example, when the sugar receptor is difficult to dissolve in a supercritical fluid as a solvent, an additional substance that dissolves the sugar receptor is further added within a range that does not impair the object of the present invention. It is good to make it react.

 In this case, preferable additives include, for example, chloroform, getyl ether, acetonitrile, dichloromethane and the like. These include substances conventionally used as organic solvents. However, according to the glycosylation reaction of the present invention, the minimum amount in which the sugar receptor can be dissolved in the supercritical solvent is sufficient, and these are added. The amount used as a substance can be significantly reduced compared to the amount conventionally used as a solvent. Specifically, the amount can be, for example, about 110.

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

Wherein R ⁴ is one OR ⁴⁵ , R ⁴¹ is one OR ⁴⁶ , one N ₃ or —NHR ⁴⁷ , R ⁴² is —OR ⁴⁸ , R ⁴³ is —OR ⁴⁹ , R ⁴⁴ an H, - CH _3, - Ji 11 ₂ 01 ⁵ ° Matawa Rei_001 ^ ⁵¹ Deari, R ⁴⁵ is a hydrogen atom has taken from hydroxyl, di § sill glycerol, ceramide, sterols, terpenes Is a peptide chain to which a peptide chain or a sugar chain is bonded, or is a saturated aliphatic group or an unsaturated aliphatic group, and R ⁴⁶ is 1 H, and all reactive functional groups including a hydroxyl group protecting group or a hydroxyl group are R ⁴⁷ is an amino-protecting group, R ⁴⁸ , R ⁴⁹ and R ⁵ ° are each independently of 1 H, a hydroxyl-protecting group or any reactive functional group containing a hydroxyl group. R ⁵¹ is a carboxyl-protecting group, provided that R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵ ° are Not all are hydroxyl protecting groups and one of R ⁴⁶ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ is either 1 H or Other If ^{R 4 6, R 4 8,} R 4 9 and R none of ⁵ ° gar H not, one of the sugar chains is assumed to have one unprotected hydroxyl group. ).

 Here, the saturated or unsaturated aliphatic group is as defined for R in the above formula (IV), and has a linear or branched, cyclic or side chain-free side chain. It is preferable to be a cyclic saturated aliphatic group or an unsaturated aliphatic group corresponding to the saturated aliphatic group containing one or more unsaturated bonds. At this time, the number of carbon atoms is preferably 1 to 30 and more preferably 1 to 10 in consideration of solubility in a supercritical fluid as a solvent.

 The peptide chain is as defined in the above formula (V). Further, as described above, when the sugar acceptor is difficult to dissolve in the supercritical fluid as a solvent, the amount of the additive substance that dissolves the sugar acceptor is further added to the extent that the object of the present invention is not impaired. It is good to let.

The gaseous CO ₂ removed from the reaction product can be reused by refilling it into a cylinder using, for example, a compressor. Further, with sodium carbonate (N a ₂ CO _3), it was recovered by collecting the C 0 _2, may be reused.

 As described above, since the glycosylation reaction of the present invention uses a supercritical fluid as a reaction solvent, the step of removing the solvent is particularly simple. Therefore, it is more effective for industrial production. In addition, since conventionally used halogen-containing compounds and the like are not used or the amount of use thereof can be significantly reduced, the burden on the environment can be reduced.

 As the reactor applied to the dalycosylation reaction of the present invention, the same device as a conventional reactor can be used.

Hereinafter, a schematic configuration of a preferred reaction apparatus applied to the implementation of the glycosylation reaction of the present invention will be briefly described with reference to the drawings. It should be noted that the drawings merely schematically show the arrangement relationship of the components to the extent that the invention can be understood, and thus the present invention is not limited to the illustrated examples. FIG. 24 is a block diagram for schematically explaining the positional relationship of the constituent elements of a preferred reactor applied to the glycosylation reaction of the present invention.

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

 The step of supplying the solvent into the reaction vessel 30 will be described. The solvent is supplied from the high-pressure cylinder 10 with the container opening / closing valve 42 closed. The supplied solvent is pressurized to a predetermined pressure by a pressure pump 20. The pressure is monitored by a 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 vessel 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. Thus, the pressure in the reaction vessel 30 is set to 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 at a temperature of 31 ° C or more and a pressure of 7.5 Mpa (megapascal) or more. Thus, it functions as a solvent. The applied pressure is preferably 25 Mpa or less in consideration of the strength of the apparatus. In addition, the reaction temperature is preferably set to 150 ° C. or lower since the saccharide used in the reaction is carbonized at a temperature higher than 150 ° C. Next, the step of removing the solvent after the completion of the reaction will be described. Remove the reaction vessel 30 from the oven and let it cool to room temperature. By this operation, the solvent that has been in the supercritical state in the reaction vessel 30 is changed to a gaseous state. Next, the leak valve 44 is opened to release the gaseous solvent from the inside of 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. Also, another high-pressure cylinder is connected to the leak valve 44 via, for example, a compressor or the like, and the high-pressure cylinder collects and collects the gaseous solvent released from the leak valve 44, and refills the solvent. It can be reused.

 The product is purified by a conventional method such as chromatography. However, since this purification step is not the gist of the present invention, its detailed description is omitted. Hereinafter, the configuration of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example

 Evaluation of the obtained zeolite analog in the examples was performed by the following method.

 (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 a Mac SciEnce MXP 3HF, and the powder sample was mounted on a glass holder and irradiated with X-rays at 40 ° to 2 ° 20 CuKct. Measurement is 40 kv / 2 OmA, DS 1.00 deg, SS l. 00 deg, RS 0.15 mm, speci me nrotatedat 360 de gZs ec, 3800 points (2.11 ° to 40 ° in 0.011 steps ).

 (2) Molecular orbital calculation

From each of the zeolite analog and the zirconium-substituted zeolite analog, That Lewis acidity is expressed by elimination of H ₂ 0 molecules was confirmed by molecular orbital calculation method. The equipment used for molecular orbital calculation was A1 phaserver, ES45 system manufactured by Compaq, and PC parallel cluster system, HPC2000—APPRO manufactured by Bestsystems. For the cluster model, a well-known energy gradient method (for example, Ch ristopher J. Cramer, Essentials of Computational C hemistry, T heories and Moderns, John Wiley & Sons, LTD Baffins Lane, Chichester) , West Sussex, PO 191 UD, England, Copyright 20002) to optimize all bond distances.

 (3) Microstructure observation

 A Hitachi Diatom Fossil thin film in clayey diatomaceous earth containing a zeolite analog containing a transition metal was formed using a focused ion beam processing and observation device. 0 Observation was performed using a transmission electron microscope and a scanning electron microscope of an ultra-thin film evaluation apparatus.

 (4) Element distribution analysis

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

 (5) Element composition and quantitative analysis

 The elemental composition and quantitative analysis of the granular region of the diatom fossil surface used in the above (3) microstructure observation were performed using the EDX equipment of the Hitachi FB-2100 ultra-thin film evaluation system. I went.

 (6) NMR measurement

IH-NMR measurement of glycosides obtained using the Lewis acid catalyst produced in the present invention and various other catalysts (apparatus: JEOL Datum (J EOL) J NM-L A400 FT NMR SYST EM (400 MHz) was performed. IH- NMR values, measured temperature: at 27 ° C, was weighed black hole Holm CDC 1 ₃ tetramethylsilane in a solvent as internal standard. δ values are expressed in ppm and coupling constants (J) are expressed in Hz. In the data, s means singlet, d means doublet, and m means multiplet.

(Reference Example 1) Powder X-ray diffraction of a mesolite crystal represented by the ideal formula N a A 1 S i, Q _R

X-ray powder diffraction analysis was performed on the mesolite crystals represented by the ideal formula Na A 1 Si ₂ 0 ₆ · H ₂ O. The powder X-ray diffraction line is shown in FIG. In Figure 1, numerals represent Miller indices indicating the ideal formula _{Na A l S i 2 0 6} · H 2 zeolite crystal surface towards the composition of 0, in parentheses atomic indicating the distance between the atoms in the crystal structure Distance. Although several peaks were observed, the peak intensities of crystal planes with Miller indices of 211, 400 and 332 were particularly remarkable. The interatomic distance between these three crystal planes is particularly important for the identification of mesolite.

(Reference Example 2) Na _in Mg, A _{11 S} S i ^ 0. _fi · 25H. O] X-ray powder diffraction of g-exchanged zeolite analog crystals

Among the known natural minerals, powder X-ray diffraction was performed on zeolite analog crystals containing Mg as a cation in addition to Na. Figure 2 shows the powder X-ray diffraction line. 2, numerals cation in analcime, partially N Mg exchange Zeorai preparative analog is replaced with Mg from _{a Na 10 Mg 3 A 1 16} S i 32 0 9 6 · 25 H 2 O Represents the Miller index indicating the crystallite plane of the composition of the formula, and the value in parentheses is the interatomic distance indicating the distance between the atoms in the crystal structure. As someone zeolite crystal represented by the ideal formula _{N a A 1 S i 2 O} 6 · H 2 0 in Reference Example 1, the Miller index 21 1, 400 (410) inter-atomic distance is 0. 1 to 0. 3A Stretched. From this result, the zeolite analog It can be seen that the distance between atoms in these crystal planes changes when the type of cation partially changes from Na to Mg.

(Example 1) Production of zeolite analog using diatomaceous earth from Ikuyo, Hokkaido and analysis by X-ray powder diffraction

 1.1 Pretreatment of diatomaceous earth (raw material) from Hokkaido Ichisei with acid and alkali Pretreatment of raw material clayey diatomaceous earth from Ichisei Hokkaido with acid and alkaline solution as shown below. Was removed. Diatomaceous earth from Ikuzei is a clayey diatomite from the Ikuchiyo, Urahoro-cho, Tokachi-gun, Hokkaido. It is mined from marine diatoms, and its main component is diatom cell walls. Specifically, 18 g of diatomaceous earth rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide solution (100 ml) and 36% hydrochloric acid solution (100 ml), and then treated with 0.1% sodium pyrophosphate solution. The decantation was repeated twice to remove impurities.

1.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid and alkali

The mineral composition of diatomaceous earth from Ikuyo, Hokkaido after the pretreatment described in 1 above was analyzed using X-ray powder diffraction (Fig. 4). In FIG. 4, Ml is illite-triotato-dral (002), muscovite_2M ₂ (002), muscovite-1T (003), and M 2 is illite-1M ₂ (110, 11-1), muscovite. _ 3 T (100), Q 1 is quartz (021), R 1 is cristobalite (101), anorthite (-201), R 2 is part-time (111), anorthite (111) Q 2 is quartz (101), R3 is albitite (040, 002), anorthite (04 0, 002), and M3 is muscovite 2M ₂ (— 312, 021, 116, 31 0), muscovite-1T (111, 112), Q3 is quartz (110), and Q4 is quartz (102). The results in Figure 4 indicate that this clayey diatomaceous earth It shows that it contains illite and muscovite as 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 following zeolite analog.

1. _3 Manufacture of zeolite analog using diatomaceous earth from Ikusei, Hokkaido as a raw material The precipitate after decantation described in 1.2 above is dried by a vacuum dryer, and dried powdery pre-treated clayey diatomaceous earth is obtained. Obtained.

 To 1.3 g of the dried powdery clayey diatomaceous earth, 5.0 ml of 1N sulfuric acid was added, air-dried at room temperature for 24 hours, and then calcined at 650 ° C for 3 hours to produce a Lewis acidic zeolite analog. Was obtained in diatomaceous earth.

1.4 X-ray powder diffraction analysis of zeolite analog from diatomaceous earth from Ikusei, Hokkaido

 The clay diatomaceous earth from Ikuyo, Hokkaido obtained in 1.3 above was analyzed by X-ray powder diffraction (Fig. 9). In FIG. 9, A 1 is a zeolite analog (211), Q 1 is quartz (021), R 1 is cristobalite (101), anorthite (201), R 2 is part-time (111), ash Feldspar (111), A 2 is a zeolite analog (410 or 400), Q2 is quartz (101), R3 is part-time (04 0, 002), anorthite (040, 002), 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 above was identified as a zeolite analog.

Although clay diatomaceous earth containing mica clay mineral was used as a raw material, mica clay mineral disappeared from clayey diatomaceous earth after sulfuric acid solution was added and calcined at 650 ° C. This suggests that mica clay minerals are involved in the formation of zeolite analogs. I guessed.

(Example 2) Production of zeolite analog from diatomaceous earth from Rubeshibe, Hokkaido and analysis by X-ray powder diffraction

 2.1 Pre-treatment of diatomaceous earth (raw material) from Hokkaido Rubeshibe with acid and alkali The raw material clayey diatomaceous earth from Rubeshibe in Hokkaido was pre-treated with an acid-alkali solution to remove impurities. The diatomaceous earth produced by Rube Zui is a clayey diatomaceous earth from Rubeshibe-cho, Tokoro-gun, Hokkaido, and is mined from the Komatsuzawa Formation, a Pliocene (180-5.3 million years ago) sediment of lakes, and is composed mainly of freshwater diatoms. Specifically, 40 g of diatomaceous earth rock was crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide solution (120 ml) and 36% hydrochloric acid solution (80 ml), and then 0.1% sodium pyrophosphate was added. The decantation to which the solution was added was performed twice to remove impurities.

2.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid acid

The mineral composition of the diatomaceous earth from Hokkaido Rubeshibe after the pretreatment shown in 2.1 above was analyzed using X-ray powder diffraction (Fig. 5). In FIG. 5, M2 is Irai DOO one _{2M 2 (1 1 0, 11-1} ), a muscovite one 3T (100), Q 1 is a quartz (021), R 1 is Christoffel Balai preparative (101) , Anorthite (-201), R 2 is albite (111), anorthite (111), Q 2 is quartz (101), R 3 is albite (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 in Figure 5 show that this clayey diatomaceous earth contains some mica clay minerals, ilite and muscovite, but no smectite clay minerals such as montmorillonite.

Thus, removing impurities, including mica clay minerals such as illite and muscovite Clay diatomaceous earth was used as a raw material to produce the following zeolite analogs.

2.3 Manufacture of zeolite analog using diatomaceous earth from Rubeshibe, Hokkaido The precipitate after decantation described in 2.2 above was dried with a vacuum dryer to obtain a dry powdery pretreated clayey diatomaceous earth .

 To 1.3 g of this dry powdered clayey diatomaceous earth was added 5.Oml of 1N sulfuric acid, air-dried at room temperature for 24 hours, and then calcined at 650 ° C for 3 hours to obtain a zeolite analog exhibiting Lewis acidity. Obtained in diatomaceous earth. 2.4 X-ray powder diffraction analysis of zeolite analog from diatomaceous earth from Rubeshibe, Hokkaido

 The diatomaceous earth from Rubeshibe, Hokkaido obtained in 2.3 above was analyzed by X-ray powder diffraction (Fig. 10). In FIG. 10, A 1 is a zeolite analog (211), Q 1 is quartz (021), R 1 is cristobalite (101), anorthite (201), R 2 is part-time (111), ash Feldspar (111), A 2 is a zeolite analog (410 or 400), Q 2 is quartz (101), R 3 is part-time (040, 002), anorthite (040, 002). ), A 3 is a zeolite analog (422 or 332), A 4 is a zeolite analog (431), Q 3 is quartz (110), and Q4 is quartz (102). Based on the above results, the clayey diatomaceous earth obtained in 2.3 above was identified as a zeolite analog.

(Example 3) Production of zeolite analog from diatomaceous earth from Hirosaki, Aomori Prefecture and analysis by X-ray powder diffraction line

 3.1 Pretreatment of diatomaceous earth (raw material) from Hirosaki, Aomori Prefecture with acid and alkali

Clay diatomaceous earth from Hirosaki, Aomori Prefecture, as a raw material, was pretreated with an acid-alkaline solution to remove impurities as follows. Diatomaceous earth from Hirosaki comes from the Tochiuchi River basin, Hirosaki, Aomori Prefecture It is a clayey diatomaceous earth that emerges from the upper to middle Miocene (5.316.4 million years ago) marine sediments. 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% pyrophosphate was added. The decantation with sodium solution was performed twice to remove impurities.

3.2 Mineral composition analysis of diatomaceous earth after pretreatment with acid and alkali

The mineral composition of diatomaceous earth from Hirosaki, Aomori Prefecture after the pretreatment shown in 3.1 above was analyzed using X-ray powder diffraction (Fig. 6). In FIG. 6, Ml is de Lal to Eli DOO one Toriota preparative (002), muscovite one 2M ₂ (002), muscovite one 3 T (003), M2 is illite one _{2 M 2 (110, 1 1-} 1 ), Muscovite 3T (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (1201), R2 is albite (111), anorthite (111), Q2 is Ishi (101), R 3 is part-time (040, 002), anorthite (040, 002), and Q4 is quartz (102). The results in Fig. 6 show that this clayey diatomaceous earth contains some 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 following zeolite analog.

3.3 Production of zeolite analog from diatomaceous earth from Hirosaki, Aomori Prefecture

 The precipitate after decantation described in 3.2 above was dried by a vacuum dryer to obtain a dry powdery pretreated clayey diatomaceous earth.

To 1.3 g of this dry powdered clayey diatomaceous earth was added 5.Oml of 1N sulfuric acid, air-dried at room temperature for 24 hours, and then calcined at 650 ° C for 3 hours to obtain a zeolite analog exhibiting Lewis acidity. Obtained in diatomaceous earth. 3.4 X-ray powder diffraction analysis of zeolite analog from diatomaceous earth from Hirosaki, Aomori Prefecture

 The diatomaceous earth from Hirosaki, Aomori obtained in 3.3 above was analyzed by X-ray powder diffraction (Fig. 11). In FIG. 11, A 1 is a zeolite analog (211), Q 1 is quartz (021), R 1 is cristobalite (101), anorthite (-201), and R 2 is albite (111). Anorthite (111), A 2 is a zeolite analog (410 or 400), Q 2 is quartz (101), R3 is albite (040, 002), anorthite (040, 002). ), A3 is a zeolite analog (422 or 332), and Q4 is quartz (102). Based on the above results, the clayey diatomaceous earth obtained in 3.3 above was identified as a zeolite analog. However, the peak intensity of the zeolite analogue was lower than that of Neogene diatomaceous earth from Hokkaido.

(Example 4) Production of zeolite analog from diatomaceous earth from Higashikawa, Hokkaido and analysis by X-ray powder diffraction

 4.1 Pretreatment of diatomaceous earth (raw material) from Higashikawa, Hokkaido with acid and alkali

The raw material diatomaceous earth from Higashikawa, Hokkaido was pre-treated with an acid-alkali solution to remove impurities as follows. Higashikawa diatomaceous earth is a high-quality diatomaceous earth from the foot of Mt. Daisetsu in Higashikawa-cho, Kamikawa-gun, Hokkaido. . Diatomaceous earth from Higashikawa, Hokkaido is a high quality quaternary diatomaceous earth with an alumina content of 2% or less, unlike diatomaceous earth from Hokkaido Ikusei, Rubeshibe from Hokkaido, and diatomite from Hirosaki, Aomori Prefecture. Specifically, 15 g of diatomaceous earth rock is crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide solution (200 ml) and 36% hydrochloric acid solution (100 ml), and then 0.1% pyrophosphate is added. The decantation with the sodium solution was performed five times to remove impurities. 4.2 Mineral composition of diatomaceous earth from Higashikawa, Hokkaido, after pretreatment with acid and acid was analyzed by X-ray powder diffraction (Fig. 7). In FIG. 7, M2 is Illite-2M ₂

(110, 11-1), one muscovite 3T (100), Q1 is quartz (021), Q 2 is quartz (101), R 3 is part-time (040, 002), anorthite ( 040, 002). The results in Fig. 7 show that this diatomaceous earth contains trace amounts of iritite 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 following zeolite analog.

4.3 Production of zeolite analog from diatomaceous earth from Higashikawa, Hokkaido

 The precipitate after the decantation in 4.2 above was dried by a vacuum drier to obtain a dried powdery pretreated clayey diatomaceous earth.

 To 1.3 g of this dry powdered clayey diatomaceous earth, add 1N sulfuric acid (10.0 m1) (Diatomaceous earth from Higashikawa, Hokkaido, has extremely high hygroscopicity. After air-drying at room temperature for 24 hours, the mixture was calcined at 650 ° C. for 3 hours to obtain a zeolite analog expressing Lewis acidity in diatomaceous earth.

4.4 X-ray powder diffraction analysis of zeolite analog from diatomaceous earth from Higashikawa, Hokkaido

The diatomaceous earth from Higashikawa, Hokkaido obtained in 4.3 above was analyzed by X-ray powder diffraction (Fig. 12). In FIG. 12, A 1 is a zeolite analog (211), Q1 is quartz (021), R 1 is cristobalite (101), anorthite (—201), and A 2 is a zeolite analog (410 or 400), Q 2 is quartz (101), R 3 is part-time (040, 002), anorthite (040, 002), A3 is a zeolite analog (422 or 332), and A4 Is a zeolite analog (431). More than From the results, the clay diatomaceous earth obtained in 4.3 above was identified as a zeolite analog. However, the peak intensity of the zeolite analog was weaker than that of Neogene diatomaceous earth from Hokkaido.

(Example 5) Molecular orbital calculation of zeolite analog

The firing process in the Examples 1 to 4, that the H ₂ 0 molecules Lewis acidity are expressed Zeoraito analogs desorbed by molecular orbital calculation method was confirmed.

Figure 8 shows the crystal structure of mesolite as a model for molecular orbital calculations. Of the two who zeolite model of FIG. 8, the left shows the 4-membered ring model _{(S i 4 0 12 H 8} ), the right shows the 6-membered ring model _{(S i 6 O 18 H 12} ). To the cluster model of FIG. 8, all bond distances were optimized by energy gradient method, further, model O between S i _S i as a model H ₂ 0 is eliminated is missing with two electrons was constructed (left shows a 4-membered ring model _{(S i 4 0! ^ 8} 2+), the right shows a 6-membered ring model _{(S i 6 0 17 H 12} 2+)). 0 ² _ together with _two protons constitutes H ₂₀ . Furthermore, to see if it can function as a Lewis acid, we added an electron pair to this model (left shows a four-membered ring model (S i ₄ O _xl H ₈ ), and right shows a six-membered ring model ( perform S i shows a ₆ 0 ₁₇ H ₁₂₎₎ calculated, predicted stabilization energy. For both the four- and six-membered ring models, the energy to receive and stabilize the electron pair was more than 450 kca 1 / mo 1, far exceeding the energy scale of ordinary chemical reactions. From these factors, it was confirmed that the zeolite analog from which H ₂₀ was eliminated could have strong Lewis acidity.

(Example 6) Production of Zr skeleton-substituted zeolite analogs from diatomaceous earth from Rubeshibe, Hokkaido and analysis by X-ray powder diffraction

6.1 Pretreatment of diatomaceous earth (raw material) from Hokkaido Rubeshibe with acid and alkali In the same manner as described in 2.1 above in Example 2, clay diatomaceous earth from Rubeshibe (Hokkaido) as a raw material was treated with an acid and alkali solution. Pre-treat and dry with a vacuum dryer. Thus, a pretreated clayey diatomaceous earth in the form of a dry powder was obtained. The mineral composition of the diatomaceous earth from Rubeshibe, Hokkaido, after pretreatment was analyzed using X-ray powder diffraction. As a result, the same diffraction lines as in 2. above in Example 2 were obtained (this diffraction line is omitted). The line indicates that the obtained clayey diatomaceous earth contains some mica clay minerals, iritite and muscovite, but no smectite clay minerals such as montmorillonite.

6.2 Production of Zr skeleton-substituted zeolite analog from diatomaceous earth from Rubeshibe, Hokkaido

Particle size from 0.150 to 0 85 acid Omm -. Alkali treated clay diatomaceous 2. filled with 6 g of calcium tube, feeding calcium pipe Z r C 1 ₄ in which vaporized at 400 ° C, by CVD (chemical vapor deposition), and the particulate Z r C 1 ₄ is deposited on the surface of the clay diatomaceous earth. Feeding air to the vessel, to produce a _{Z r C 1 2 0 · 8H} 2 0 in the particulate Z r C 1 ₄ was hydrolyzed viscous soil diatomite surface. Z r C 1 after ₄ hydrolysis, the supported amount of the _{Z r C 1 2 0 · 8} H 2 〇 argillaceous diatomaceous earth, calculated from the weight gain measurements, 0. 34 mM supported amount per diatomite 1 g I estimated. Calcium _{tube, Z r C 1 2 0 ·} 8 H 2 O was removed the loaded with clay diatomaceous earth to give the Z r (OH) ₄ was added 28% aqueous ammonia 3 Om 1 after transfer to a beaker. The precipitate was washed with decantation (5 times) and dried in an electric furnace at 100-150 ° C all day and night. After drying, 1N sulfuric acid (3.8 ml for diatomaceous earth lg) was added, air-dried at room temperature all day and night, and calcined at 650 ° C for 3 hours.

6.3 X-ray diffraction analysis of Zr skeleton-substituted zeolite analog from diatomaceous earth from Rubeshibe, Hokkaido

The diatomaceous earth from Hokkaido Rubeshibe obtained above was analyzed by X-ray diffraction analysis (Fig. 13). In FIG. 13, A 1 is a zeolite analog (21 1), Ml is illite-trioctoderal (002), muscovite 2M ₂ (002), muscovite 3 T (003), Ql is quartz (021), R1 is cristobalite (101) and anorthite (201), R 2 is part-time (1 1 1), anorthite (1 1 1), and A 2 is similar to zeolite Body (410 or 400), Q 2 is quartz (101), R 3 is part-time (040, 002), anorthite (040, 002), and A3 is zeolite analog (422 or 332). Yes, A4 is a zeolite analog (431), Q3 is quartz (1 10), 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 (ie, Zr not introduced) produced from diatomaceous earth from Rubeshibe, Hokkaido, shown in 2.4 of Example 2 was 5.8010- 6. 047A (width: 0.237 A) and (410 or 40

The peak at (0) was 3.492 to 3.568 A (width 0.076 A).

 On the other hand, the peak of Zr-introduced zeolite analog (21 1) in Fig. 13 is 5.814 to 6.215 A (width: 0.401 A), and the peak of (410 or 400) is The peak was at 3.496 to 3.613 (width 0.117 A). That is, it was shown that the interatomic distance in the crystal plane of the zeolite analog was extended by a maximum of 0.17A (211) by introducing Z.

This change in interatomic distance is due to the insertion of tetrahedral Zr into the crystal lattice of the zeolite analog. Here, Table 1 shows the MO distance of the M0 ₄ H ₄ (M = S i, A 1, Z r) tetrahedral structure. Here, for the optimization of the structure of M0 ₄ H ₄ (M = S i, A 1, Z r) by the energy gradient method, a 3-21 G * basis was used using the restricted Hartree-Fock method. M = A1 was calculated as a monovalent negative ion. M0 ₄ H ₄ (M = S i, A 1, Z r) M—O distance of tetrahedral structure

From Table 1, greater than tetrahedral structure of Z r 0 ₄ tetrahedral structure A 10 ₄ and S i 0 _4, Ru is measured by X-ray powder diffraction lines when Z r is inserted into Zeorai preparative analogs It is clear that the interatomic distance is extended. The simulation results by molecular orbital calculation method showed that the introduction of Zr could have predicted that the peak of the zeolite analog (211) would extend by 0.039 A. When compared with the actual analysis results, the explanation is well explained in the range of factor 2. Considering that Zr is small, Zr—Si and Zr—A1 are overwhelmingly small compared to Si—Si. Thus, it is clear that the range of extreme distances calculated will be smaller when observed.

From the above analysis results, the 5. by two methods, revealed the Rukoto Z r 0 ₄ at T0 ₄ four backbone substituted replacing the facepiece Zeorai bets analogs obtained from Hokkaido Rubeshibe produced diatomaceous earth (raw material) Was.

6.4 Analysis of Zr skeleton-substituted zeolite analog from diatomaceous earth from Rubeshibe, Hokkaido by ultra-thin film evaluation system

 The clay diatomaceous earth containing the Zr-skeleton-substituted zeolite analog produced in 6.2 above was analyzed by a transmission electron microscope and EDX (energy dispersive method) using a Hitachi HI HD-2000 ultrathin film evaluation apparatus.

Cross sections of diatom fossils in clayey diatomaceous earth were prepared, and the fine structure was observed by transmission electron microscopy analysis (Fig. 14). In Fig. 14, the diatom fossil cross-section is the diatom cell wall of the genus Au racoseira in the diatomaceous earth from Rubeshibe. A thin film was formed using a 100 focused ion beam processing observation device. From FIG. 14, it was confirmed that a granular aggregate having a diameter of 100 nm was formed on the surface of the diatom fossil. FIG. 14 also showed that the granular aggregate was spherical and that the amorphous gel-like material filled the space between the granular aggregates.

 Scanning electron microscopy of clay diatomaceous earth from Rubeshibe showed no granular aggregates on the surface of diatom fossils. 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 element distribution of the granular aggregate shown in FIG. 15 was analyzed by EDX (energy dispersive method) of a Hitachi HI HD-2000 ultra-thin film evaluation apparatus. In FIG. 15, the SEM is a scanning electron microscope, which is the same area as the right image in FIG. S i _K, A 1 — K, and Z r — で are images obtained from the Κ shell in each atom, and the analyzed area is the same as the scanning electron microscope image. From FIG. 15, it was confirmed that the granular aggregate contained A 1 and Zr in addition to Si.

 Since the ultra-thin film evaluation system can perform elemental composition and quantitative analysis of minute regions, we analyzed the elemental composition of each granular material (Fig. 16). In FIG. 16, the elemental composition was analyzed by the EDX apparatus of the Hitachi FB-2100 ultra-thin film evaluation apparatus, and is the elemental composition of the granular aggregate in FIG. Here, W is the metal used for depositing the sample, and Mo is the metal that makes up 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 the individual granular aggregates in these same samples, C, 0, Na, Al, Zr, Si, K, Fe were identified, and the main elements other than O, A, Zr, Si The element ratio was 3: 43: 4 in FIG. 16 and 1: 8: 1 in FIG.

The difference in the element ratios of A1, Zr, and Si between FIG. 16 and FIG. 17 indicates that the granular aggregate is not a single-composition crystal but a solid solution. A solid solution is a solid phase in which multiple substances are dissolved together, and is also called a mixed crystal. There are substitution type and intrusion type, and most minerals are substitution type and one component dissolves by replacing the other component. The peripheral region of the grain-like aggregate is filled with opal represented by the ideal formula _{S i 0 2 · nH 2 0} , the X-ray powder diffraction lines of Example 6 (Ma c S cience MXP 3HF ) It is considered that the identified zeolite analog and opal form a solid solution. S io ₄ tetrahedron is a common structure of the Zeoraito analogue and opal. Element ratio of A 1 and S i configuring the T0 ₄ tetrahedra natural lateral zeolite is 1: 2. Of this, in clayey in diatomite, if the A 1 to insufficient Z r was replaced, ideal expressions of the particulate aggregate in FIG. _{16 X 7 Z r 4 A 1} 3 S i 14 0 42 · 7H 2 0 a _{+29 (S i O 2 · nH} 2 O), in FIG. _{1 7 X 2 Z r a 1} S i 4 0 12 - represented by _{2H 2 0 + 4 (S i} 0 2 · nH 2 O) . Where X is an alkali metal. That is, the ideal formula _{X 2 Z r A 1 S i} 4 0 12 · 2H 2 0 or _{X 7 Z r 4 A 1 3} S i 14 0 42, - Z r backbone substituted Zeorai preparative expressed as 7 H ₂ 〇 and analogs, silicon dioxide represented by the ideal formula S i 0 ₂ to form a solid solution.

If X is all protonated, ideal formula _{H 2 Z r A 1 S i} 4 0 12 · 2H 2 O + 4 (S i 0 2 · nH 2 0) or H ₇ Z r ₄ A 1 _{3 S i 14 0 42 - 7 H} 2 0+ is _{29 (S i 0 2 · nH} 2 O), the ideal formula Z r a 1 S i ₄ 0 dehydrated by calcination _{"+4 (S i 0 2 ·} nH 2 O) or become _{Z r 4 a 1 3 S i} 14 O 28 + 29 (S i O 2 · nH 2 0). However, as the alkali metal from the particulate aggregate, N a and K have also been detected, Not all zirconium-substituted zeolite analogs are protonated.

Table 2 below shows the elemental composition ratios of the granular aggregates calculated from the EDX analysis in FIG.

Table 2. Elemental composition ratio of granular aggregate calculated from EDX analysis in Fig. 17

In Table 2, of the elements found by elemental analysis in Figure 17, the impurities C, W, and Mo were excluded. weight. / ₀ and atom% were calculated based on the signal obtained from the K shell in the atom.

In Zeoraito analogs, number monovalent cation is comprised into the same number and A 1 amount in .tau.0 ₄ tetrahedra, Z r is a zeolite analog of Figure 17 is substituted with A 1. Therefore, the same amount of cations as 7.46 at om%, which is the sum of 1: and 81, 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 shortage of cations is due to protons that could not be detected by Fe and EDX analyses. That is, in the zeolite analog, a part of the cation is replaced by a proton. (Example 7) Molecular orbital calculation of Zr skeleton-substituted zeolite analog By the calcination treatment in 6.2 of Example 6, a zeolite analog in which H ₂ O molecules were eliminated from a Zr-introduced zeolite analog was obtained. Whether Lewis acidity was developed was confirmed by molecular orbital calculation method.

For the two models described in the fifth embodiment, a model in which S i is replaced with one A 1 1 and Z r (the left is a four-membered ring model (A 1 Z r S i zOnHs ² is shown, Using a 6-membered ring model (shown as A 1 ZrSi ₄ 0 ₁₇ H ₁₂ ²⁺ ), the energy for receiving and stabilizing an electron pair was calculated by the molecular orbital method as in Example 5. The stabilization energy was about 280 kca 1 / mo 1, well beyond the range of normal chemical reactions, but the degree of stabilization was smaller than that without Zr. Lewis acidity appears due to the resulting stabilization factor, and its strength is considered to be weaker than that of the zeolite analog into which Zr is not introduced. Experiments using this as a Lewis acid catalyst are sufficient for zeolite analogs. In this case, the sulfuric acid addition and 650 ° C calcination were performed using montmorillonite, the most common clay mineral, and amorphous silica, the main component of diatomaceous earth, as raw materials. The results are shown in Comparative Examples 1 and 2.

 X-ray powder diffraction line (Mac Science MX P 3 HF) using diatomaceous earth from Rubeshibe, Hokkaido, as a raw material and pre-treatment with an acid-alkali solution, followed by firing at 650 ° C only, is shown in Comparative Example 3. Show.

 Further, Example 8 shows an example in which a zeolite analog produced from Rubeshibe diatomaceous earth and a Zr skeleton-substituted zeolite analog were used as Lewis acid catalysts.

(Comparative Example 1) Addition of sulfuric acid using bentonite as raw material 'Result of firing at 650 ° C

Paragonite was obtained in bentonite by bombarding 1.3 g of 1N sulfuric acid 5.Oml with 1.3 g of dried powdered bentonite, air-drying at room temperature all day and night, and calcining at 650 ° C for 3 hours. The general formula NaAl ₂ (S i ₃ A l) O ₁₀ (OH, F) ₄ Lagonite is a dioctahedral mica. After firing, the bentonite solidified in an unfired state, and a powder form suitable for a solid catalyst could not be obtained.

The main component of bentonite is the ideal formula Na. .33 A montmorillonite represented by (H ₂ 0) ₄ (A 1, Mg) ₂ [(OH) ₂ IS i ₄ O ₁₀ ], which can swell in water and have cation-exchange properties It is a feature. It is used for applications such as mud conditioners for boring, binders for iron ore pallets, sand-type binders for animals, civil engineering, agricultural chemical carriers, soil improvement, and paint aids. In the experiments, bentonite manufactured by Kanto Chemical (04066-01) was used. Fig. 18 shows the result of analyzing the mineral composition by X-ray powder diffraction (Mac Science MXP 3HF). In Fig. 18, Mo 1 is montmorillite, Ml is illite, M2 is muscovite (001) and illite (002), HI is pyroxene (020), and H2 is luminous. Zeolite (200), H 3 is a pyroxene (20-1), H 4 is a pyroxene (31—1), H 5 is a pyroxene (1 1 1), H 6 is a bright Zeolite (20-1), Mo2 is a montmorite mouth, M3 is a muscovite mite, Q1 is quartz (100), and R1 is a cristobalite ( 101), H 7 is a pyroxene (131), R 2 is a part-time job (11 1), anorthite (—130), Mo 3 is a montmorillonite (103), and Q 2 is Quartz (101), R3 is albite (040, 002), anorthite (040, 002), Cal is calcite (104), M4 is muscovite (204), and R 4 is Is anorthite (1–31), and H 8 is a pyroxene (1 51 ), H 9 is a pyroxene (62-1, 530), HI 0 is a pyroxene (061), Mo 4 is montmorillonite, M5 is muscovite and illite, and Q3 is quartz ( 102).

In addition to montmorillonite, mica-based clay minerals including muscovite and irrit were identified as clay minerals. In addition, zeolites, a natural zeolite, were found. In addition to quartz also the clay mineral Cristofano Balai DOO, rock-forming minerals such as feldspars, calcite represented by Ca C0 ₃ were identified. These are common minerals contained in bentonite.

FIG. 19 shows the results of analysis of the untreated sintered bentonite by X-ray powder diffraction (Mac Science MXP 3HF). In FIG. M 2 is muscovite (001) and illite (002), P 1 is paragonite — 1M (001), HI is pyroxene (020), H 2 is pyroxene (200), and H 3 Is a pyroxene (20—1), H 4 is a pyroxene (31—1), H 5 is a pyroxene (1 1 1), P 2 is paragonite—1M (002), and M o 2 is montmorillonite, M3 is muscovite and illite, Q 1 is Sei Ying (100), R 1 is Cristobalit (101), P 3 is paragonite—2 (022) H 7 is pyroxene (131), R 2 is part-time (1 1 1) and anorthite (1-130), An 1 is anhydrite (020), and Q 2 is quartz ( 101), P 4 is paragonite 1M (003) and paragonite 1 2 (006), R 3 is albite (040, 002), anorthite (040, 002), and H8 is luminous. Zeolite (151) and An 2 is anhydrite (012), P 5 is paragonite- 1 2Mi (-131), An 3 is anhydrite (202), and Q 3 is quartz (102).

Despite the same treatment as the diatomaceous earth shown in Examples 1 to 4, no zeolite analog was obtained. After the treatment, the characteristic peak of 20 CuKc at 7 ° (interatomic distance of 12.3 A) of the elite tomontmorillonite disappeared and was replaced with paragonite, a mica mineral. Furthermore, calcite represented by C a C0 ₃ found in the bentonite bets are after treatment is replaced with anhydrite, represented by C a S0 _4.

 This result indicates that zeolite analog is not formed from clay containing montmorillonite as the main component by sintering with sulfuric acid at 650 ° C.

(Comparative Example 2) Addition of sulfuric acid using amorphous silica as a raw materialResult of calcining at 650 ° C Dry powdered amorphous silica 1.3 g, 1N sulfuric acid 5.Oml was added, and air-dried at room temperature for 24 hours After that, it was baked at 650 ° C for 3 hours. Figure 20 shows the results of analysis of mineral composition by X-ray powder diffraction (Mac Science MX P 3 HF) using silicon dioxide (precipitated, amorphous) manufactured by Kanto Kagaku (37049-13). Shown in As with diatomaceous earth, an amorphous halo with a peak at 20 CuKa 21-22 ° (interatomic distance 4.23-4.04 A) was obtained.

Even after the treatment, the powder is in the form of a powder. e MXP 3HF) (Fig. 21). The shape of the amorphous halo with a peak at 20 CuKa 21-22 ° (interatomic distance 4.23-4.04 A) is shown in Fig. 20. It is not different from silica.

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

(Comparative Example 3) Result of firing at 650 ° C using diatomaceous earth from Rubeshibe, Hokkaido

 Clay diatomaceous earth from Rubeshibe, Hokkaido, the raw material, was subjected to pretreatment with an acid-alkali solution to remove impurities. Specifically, 28 g of diatomaceous earth rock is crushed with a hammer, hydrothermally treated with 30% hydrogen peroxide solution (100 ml) and 36% hydrochloric acid solution (50 ml), and then 0.1% sodium pyrophosphate is added. The decantation with the solution was performed five times, and clay diatomaceous earth containing mica clay minerals such as illite and muscovite with impurities removed was used as the raw material. The dried powdery pretreated clayey diatomaceous earth was obtained by drying the precipitate after decantation with a vacuum dryer. After this pretreatment, the dried powdery diatomaceous earth was calcined at 650 ° C for 3 hours.

 FIG. 22 shows the result of analyzing the clayey diatomaceous earth calcined at 650 ° C. with the addition of the sulfuric acid solution by X-ray powder diffraction (Mac Science MXP 3HF). In Fig. 22, one is muscovite 3T (100), Q1 is quartz (021), R1 is cristobalite (101), anorthite (-201), R2 is part-timer (111), anorthite ( 1 11), Q 2 is quartz (101), R 3 is albite (040, 002), anorthite (040, 002), Q3 is quartz (1 10), and Q4 is quartz (102). This clayey diatomaceous earth contained some illite and muscovite as mica clay minerals, and no zeolite analog was synthesized in the diatomaceous earth. This comparative example showed that even when clay diatomaceous earth was used as a raw material, the zeolite analog could not be obtained only by firing at 650 ° C.

(Example 8) Synthesis of sugar monoalcohol (glycoside) In this example, a leaving group and a protecting group were introduced into a sugar donor using supercritical carbon dioxide as a solvent, using diatomaceous earth from Rubeshibe, Hokkaido, which had been subjected to 1N sulfuric acid addition and baked at 650 ° C, as a Lewis acid catalyst. This shows the reaction of The zeolite analog and the Zr skeleton-substituted zeolite analog produced in the present invention exhibit extremely high activities in the daricosylation reaction in supercritical carbon dioxide.

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

の化合物 （2, 3， 4， 6—テトラ一 O—ァセチル一 a—D—ガラク トビラノシ ルトリクロロアセトイミデート） 300mg (0. 609mmo 1 ) を加えた。 次いで、 1ーォクタノールを 0. 48m l (3. 04mmo l) 加えた。 さら に触媒を加えた。

The compound (2,3,4,6-tetra-O-acetyl-a-D-galactobyranosyltrichloroacetimidate) (300 mg, 0.609 mmo 1) was added. Then, 1-octanol was added in an amount of 0.48 ml (3.04 mmol). Further, a 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)

ゼォライト類似体/留辺蘂産珪藻土は、 実施例 2と同様の製造法で得た。 すな わち、 酸'アルカリ処理済みの北海道留辺蘂産珪藻土 2. 6 gに 1規定の硫酸水 溶液 10ml中に加え、 室温 （20°C) で一昼夜、 風乾させることで得た。

Zeolite analog / Rubeshibe diatomaceous earth was obtained by the same production method as in Example 2. In other words, 2.6 g of diatomaceous earth from Hokkaido, which had been treated with acid and alkali, was added to 10 ml of a 1N aqueous sulfuric acid solution, and air-dried at room temperature (20 ° C) for 24 hours.

Zr skeleton-substituted zeolite analog Diatomaceous earth from Rubeshibe was obtained by the same production method as in Example 5. That, CVD method Z r C 1 ₄ to acid and alkali treated Hokkaido Rubeshibe produced diatomaceous earth supported by (chemical vapor deposition), and Z r OC 1 ₂ hydrolysis in the gas phase, at 2 8% ammonia solution Is converted to Zr (OH) ₄ . After drying at 100 ° C, 2.6 g of diatomaceous earth supporting 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.

 Rubeshibe diatomaceous earth was only pretreated with an acid-alkali solution.

The sulfated Jirukoyua _{(Z r0 2 / S0 4)} , and calcined 3 hours at 650 ° C as pretreatment.

Silver trifluoromethanesulfonate was not pretreated. The amount of catalysts used were, for the Z r 0 ₂ / S 0 ₄ and triflumizole Ruo ii silver methane sulfonate, 1 equivalent relative to the sugar donor. In the case of sulfuric acid-treated diatomaceous earth and diatomaceous earth, an amount sufficient to fill the inside of the reaction vessel was set. Specifically, the container volume was 10 ml and the volume was about 1.5 g.

Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out at a temperature of 50 ° C and a pressure of 12 MPa for 17 hours (18.5 hours for sample No. 5). . After the completion of the reaction, the reaction vessel was allowed to cool to room temperature, so that the solvent co ₂ was converted to a gas phase and removed as a gas. After diluting the reaction product with filter form, the catalyst was removed by filtration using filter paper. Removed zeolite analog Diatomaceous earth from Rubeshibe and Zr skeleton-replaced zeolite analog Z-diatomaceous earth from Zubeshibe are reused by rinsing at 650 ° C for 2 hours after washing in Cloguchi be able to. The filtrate is purified by chromatography on a silica gel column and then concentrated under reduced pressure to give the desired formula:

The product of (2) was recovered in an amount of 224 mg (using diatomaceous earth from Zolite analog Z Rubeshibe as a catalyst).

 Table 4 shows the relationship between catalyst type and yield (%). Table 4. Catalysts and yields used in the synthesis of sugar-alcohols (glycosides)

収率は、 シリカゲルクロマトグラフィ （展開溶媒は n—へキサン：酢酸ェチル = 4 ： 1 ) を用いて、 糖供与体として使用した 2， 3， 4， 6—テトラー O—ァ セチル一 α—D—ガラクトピラノシルトリクロロアセトイミデートを基準とし、 重量％で算出した。 さらに、 得られた配糖体について NMR測定を行った結果は、 以下の通りであ る。

The yield was determined using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1) and used as a sugar donor for 2,3,4,6-tetra-O-acetyl-α-D— Calculated in% by weight based on galactopyranosyltrichloroacetimidate. Further, the result of NMR measurement of the obtained glycoside is as follows.

1 H-NMR data (CDC 1 3, 40 OMH z):.. 0. 86-1 58 (m, 15H), 1. 88-2 14 (4 S, 1 2H), 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 a 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 2-, 4-, and 6-positions, as shown in the following formula ( VIII) (175 mg (0.255 mmol) of the compound (2,3,4,6-tetra-O-benzyl-α-D-galactovilanosinoletrichloroacetimidate) was added.

次いで、 反応容器内に、 糖受容体として、 2位、 3位および 6位の OH基には 保護基が付加されている式 （I X) の化合物 （ァリール 2， 3， 6—トリ—0— ベンゾィル一 a— D—ガラクトビラノシド） を 104mg (0. 195mmo 1 ) を加えた。 さらに触媒を加えた。

Next, a compound of the formula (IX) in which a protecting group is added to the OH groups at the 2-, 3- and 6-positions as a sugar acceptor (Aryl 2, 3, 6-tri-0- To this was added 104 mg (0.195 mmo 1) of benzoyl-a-D-galactobilanoside. Further catalyst was added.

(IX)

ここで使用した触媒につき表 5を参照して説明する。

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 amounts used in the synthesis of carbohydrate polymers

硫酸化ジルコユア （Z r 0₂ZS0₄) については、 前処理として 650°Cで 3 時間焼成してある。 トリフルォロメタンスルホン酸銀は、 特に前処理は行ってい ない。

The sulfated Jirukoyua _{(Z r 0 2 ZS0 4)} , are then calcined 3 hours at 650 ° C as pretreatment. Silver trifluoromethanesulfonate was not pretreated.

 The amount of catalyst used is one 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 at a temperature of 50 ° C. and a pressure of 12 MPa for 12 hours.

After completion of the reaction, by returning to room temperature the reaction vessel was allowed to cool, the C0 ₂ is a solvent was removed as a gas in the gas phase. After diluting the reaction product with filter form, the catalyst was removed by filtration using filter paper. The removed catalyst can be reused by rinsing it at 650 ° C for 2 hours after washing it with a black hole form.

The filtrate is purified by chromatography on a silica gel column (developing solvent is n-hexane: ethyl acetate = 4: 1), and then concentrated under reduced pressure to give 54 mg of the desired product of the following formula (X) (sulfated zirconia as a catalyst). using _{(Z r0 2 ZS0 4))} ; 113mg ( using triflate Ruo b silver methanesulfonate as a catalyst) was recovered.

結果を表 6に示す。 表 6はサンプル番号、 触媒の種類および収率 （％) を示す 表である。 表 6 糖質高分子の合成にぉ 、て使用した触媒と収率

Table 6 shows the results. Table 6 shows the sample numbers, catalyst types and yields (%). Table 6 Catalysts and yields used in the synthesis of carbohydrate polymers

収率は、 シリカゲルクロマトグラフィ （展開溶媒は n—へキサン：酢酸ェチル =4 ： 1) を用いて、 糖供与体として使用した （2， 3， 4， 6—テトラ一 O— ベンジル一 a— D—ガラクトピラノシルトリクロロアセトイミデート） を基準と し、 重量。 /₀で算出した。

The yield was determined using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1) and used as a sugar donor (2,3,4,6-tetra-O-benzyl-a-D). —Galactopyranosyltrichloroacetimidate) and weight. / ₀ was calculated.

 Further, NMR measurement was performed on the obtained saccharide polymer.

 The measurement conditions and results are as follows.

 (Measurement condition)

 'H-NMR (40 OMH z)

Equipment: JEOL datum (J EOL) J NM-LA400 FT NMR S YS TEM

Measurement temperature: 27 ° C

Solvent: CDC 13 (result)

1 H-NMR data (CDC 1 3, 40 OMH z): δ 8. 04- 7. 1 4 (m, 35 H, P hproton), 5. 72 (m, 1H, allyl _C H =), 5. 70 (dd, 1H, H- 2 ), 5. 67 (dd, 1 H, H- 3), 5. 35 (d, 1H, J 2 - 2. 97Hz, H-l), 5. 20 (dd , 1 H, a 1 1 y 1 CH ₂ =), 5.09 (dd, l H, allyl CH ₂ =), 4.90 (d, 1 H, J, ₂ ′ = 3.51 Hz, H—l, ), 4.87—4.70 (m, 8H, 4 X-CH ₂ Ph), 4.47—3.97 (m, 10 H, protonofallyl—CH = andsugarring).

(Example 10) Synthesis of sugar monoalcohol (glycoside)

 In this example, an example in which a leaving group and a protecting group are introduced into a sugar donor to control a reaction position will be described.

 In the reaction vessel, as a rod donor, a leaving group is added to the OH group at position 1 and a protecting group is added to the OH group at positions 2 to 4 to 6 300 mg (0.609 mmo 1) of the compound of structural formula (XI) (2,3,4,6-tetra-O-acetyl-α-D-galactovilanosyltrichloroacetimidate) was added.

次いで、 1—ォクタノールを 0. 48m l (3. 04mmo l) 加えた。 さら に触媒を加えた。

Then, 1-octanol was added in an amount of 0.48 ml (3.04 mmol). Further, a catalyst was added.

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

Table 7 shows the sample number of Example 10, the catalyst used and the amount of catalyst (mg). Is a table for explaining. Table 7 Catalysts and amounts used in sugar-alcohol (glycoside) synthesis

硫酸処理珪藻土は、 市販されている珪藻土 （乾燥品） 2 gを 1規定の硫酸水溶 液 5ml中に加え、 室温 （20°C) で一昼夜、 風乾させることで得られる。 実施例 1と同様に、 硫酸処理珪藻土、 硫酸化ジルコニァ （Z r 0₂/S0₄) に ついては、 前処理として 650°Cで 3時間焼成してある。 トリフルォロメタンス ルホン酸銀および珪藻土は、 特に前処理は行っていない。

Sulfuric acid-treated diatomaceous earth is obtained by adding 2 g of commercially available diatomaceous earth (dry product) to 5 ml of a 1N aqueous sulfuric acid solution, and air-drying at room temperature (20 ° C) for 24 hours. As in Example 1, sulfuric acid treatment diatomaceous earth, it is calcined 3 hours at 650 ° C to sulfation Jirukonia _{(Z r 0 2 / S0 4} ) For, as a pretreatment. Silver trifluoromethanesulfonate and diatomaceous earth have not been pretreated.

The amount of catalyst used is about sulfated Jirukonia (Z R_〇 ₂ ZSO ₄₎ and Torifuruo ii silver methane sulfonate, 1 equivalent relative to the sugar donor. In the case of sulfuric acid-treated diatomaceous earth and diatomaceous earth, an amount sufficient to fill the inside of the reaction vessel was set. Specifically, the container capacity was 10 ml and the volume was about 1.5 g.

 Next, a supercritical fluid of carbon dioxide is generated as a solvent in the reaction vessel, and the reaction is carried out at a temperature of 50 ° C and a pressure of 12 MPa for 17 hours (18.5 hours for sample No. 5). Was.

After completion of the reaction, by returning to room temperature the reaction vessel was allowed to cool, the C0 ₂ is a solvent was removed as a gas in the gas phase. After diluting the reaction product with filter form, the catalyst was removed by filtration using filter paper. The removed catalyst (sulfuric acid-treated diatomaceous earth and silver trifluoromethanesulfonate) was washed in a black-mouthed form and then washed at 650 ° C for 2 hours. It can be reused by baking for a while.

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

(XII)

結果を表 8に示す。 表 8はサンプル番号、 触媒の種類および収率 （％) を示す 表である。 表 8 糖—アルコール （配糖体） の合成において使用した触媒と収率

Table 8 shows the results. Table 8 shows the sample numbers, catalyst types and yields (%). Table 8 Catalysts and yields used in sugar-alcohol (glycoside) synthesis

収率は、 シリカゲルクロマトグラフィ （展開溶媒は n—へキサン：酢酸ェチル = 4 ： 1 ) を用いて、 糖供与体として使用した 2， 3， 4， 6—テトラ一 O—ァ セチル一 α—D—ガラク トピラノシルトリクロロアセトイミデートを基準とし、 重量％で算出した。

The yield was determined using silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 4: 1) and used as a sugar donor for 2,3,4,6-tetra-O-acetyl-α-D —Calculated in% by weight based on galactopyranosyltrichloroacetimidate.

 Further, the obtained glycoside was subjected to NMR measurement.

 The measurement conditions and results are as follows.

(Measurement condition) 'H-NMR (40 OMH z)

Equipment: JEOL datum (J EOL) J NM-LA400 FT NMR S YSTEM

Measurement temperature: 27 ° C

Solvent: CDC 1 ₃

 (Result)

'H-NMR data (CDC 1 3, 400 MH z):.. 0. 86 _ 1. 58 (m, 15H), 1. 88-2 14 (4 S, 12 H), 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) o

(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 a reaction position will be described.

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

(式中、 Bnはべンジルである）

(Where Bn is benzyl)

 Next, 75 mg (0.195 mmo 1) of cholesterol was added as a sugar acceptor to the reaction vessel. Further catalyst was added.

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

 Table 9 is a table for explaining the sample number of Example 11, the catalyst used, and the amount (mg) of the catalyst. Table 9 The amount of catalyst used in the synthesis of sugar-cholesterol

硫酸化ジルコニァ （Z r 0_2/ S0₄) については、 前処理として 650°Cで 3 時間焼成してある。 トリフルォロメタンスルホン酸銀は、 特に前処理は行ってい ない。

The sulfated Jirukonia _{(Z r 0 2 / S0 4} ), are then calcined 3 hours at 650 ° C as pretreatment. Silver trifluoromethanesulfonate was not pretreated.

 The amount of catalyst used is one 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 that additional additives are added to the reaction vessel to dissolve it in the supercritical fluid. In this example, 0.188 ml of Clono honolem was added as an additive.

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

After completion of the reaction, by returning to room temperature the reaction vessel was allowed to cool, the C0 ₂ is a solvent was removed as a gas in the gas phase. After diluting the reaction product with filter form, the catalyst was removed by filtration using filter paper. The filtrate was concentrated under reduced pressure to collect the residue. The residue is chromatographed on a silica gel column (developing solvent is n-hexane: Acetate Echiru = 4: After 10/1) and concentrated in vacuo, (67 mg of a compound of XIV) (sulfation Jirukoyua (Z r 0 ₂ ZS0 ₄ as catalyst) of the following purposes formula use); 130 mg ( Silver trifluoromethanesulfonate was used as a catalyst).

結果を表 10に示す。 表 10はサンプル番号、 触媒の種類および収率 （％) を 示す表である。 表 10 糖—コレステロールの合成において使用した触媒おょぴ収率

Table 10 shows the results. Table 10 shows sample numbers, catalyst types and yields (%). Table 10 Yields of catalysts used in the synthesis of sugar-cholesterol

収率は、 シリカゲルクロマトグラフィ （展開溶媒は n—へキサン：酢酸ェチル

Silica gel chromatography (Developing solvent is n-hexane: ethyl acetate

= 4: Calculated in% by weight based on 1), based on 2,3,4,6-tetra-O-benzyl-a-D-galactopyranosyltrichloroacetimidate used as sugar donor did.

 Further, the obtained sugar-cholesterol was subjected to NMR measurement.

 The measurement conditions and results are as follows.

(Measurement condition) 'H-NMR (40 OMH z)

Equipment: JEOL datum (J EOL) J NM-LA400 FT NMR S YSTEM

Measurement temperature: 27 ° C

Solvent: CDC 13

 (Result)

'H-NMR data (CDC 1 3, 40 OMH z):. Δ 7. 35-7 20 (m, 20 H, P hproton), 5. 21 (t, 1H, cholestero 1 -OCH <), 5. _{06 (d, H, J 2} = 4. 24Hz, H- 1), 4. 78-4. 46 (m, 8 H, 4 X-CH 2 P h), 4. 29 (t, 1 H, H — 3), 4.03 (dd, 1H, H—2), 3.95 (t, 1H, H—4), 3.75 (m, 1H, H—5), 3.67 (dd, 1 H, H_6) 3.55 (dd, 1H, H—6 ') 3.52 (m, 1H, cholesterol — CH =) 2.29—0.68 (m, 43H, otherprotonofcholeste ro 1).

(Example 1 2) Synthesis of sugar monopeptide (glycoside)

In this example, an example in which a leaving group and a protecting group are introduced into a sugar donor to control a reaction position will be described. First, sulfated titania responsible lifting diatomaceous earth catalyst used in this synthesis system - a ^{_{(S0 4 2 / T i 0}} 2 / diatomaceous earth) was synthesized as follows.

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

The above processing performed dry powdered diatomaceous earth 4 g of (particle diameter 0. 1 5 mm or less) was filled into Cal Shiumu tube, the metal titanium 1 g to obtain a T i C 1 ₄ is chloride in a chlorine atmosphere . T i C 1 ₄ was vaporized at 400 ° C, sent to a calcium tube Ri by the pressure of nitrogen was supplied from the high-pressure nitrogen cylinder. At this time, by CVD (chemical vapor deposition), and the white smoke-like T i C 1 ₄ is deposited on the surface of the diatomaceous earth. After the deposition of the T i C 1 _4, the supporting amount of the diatomaceous earth was calculated from weight gain measurements, estimate the T i C 1 ₄ supported amount per diatomite 1 g 4. and 7 m M. Calcium tube, removed T i C 1 ₄ loaded with diatomaceous earth to give a T i (OH) ₄ was added 28% aqueous ammonia 50 m 1 after transfer to bi one force scratch. The precipitate was washed with decantation (seven times) and dried in an electric furnace at 100 to 150 ° C all day and night. After drying 1 N sulfuric acid (corresponding to 3. 8m l to diatomaceous earth lg) was added at room temperature calcined 3 hours at 650 ° C after air drying overnight sulfated titania supported diatomaceous earth ^{_{(S0 4 2 - ZT i O}} 2 Z Diatomaceous earth).

Then, a leaving group is added to the OH group at position 1 and a protecting group is added to the OH group at positions 2 to 5 as a sugar donor in the reaction vessel. ;

*

*

(Where Ac is acetyl), the compound (2,3,4,6-tetra-O-acetyl-c-D-galactobidinosinoletrichloroacetimidate) is treated with l O Omg (0. 203mmo 1) was added. Then, as a sugar receptor, the structural formula (* 2)

(Where Z is benzyloxycarbonyl)

105 mg (1.5 equivalents) of the compound (zet-threonine-O-benzyl) was added. Further equivalent of sulfuric acid I spoon titania supported diatomaceous earth relative to the sugar donor as catalyst ^{_{(S 0 4 2 - ZT i}} 0 2 diatomaceous earth) was added.

 Next, a supercritical fluid of carbon dioxide was generated as a solvent in the reaction vessel, and the reaction was carried out at a temperature of 35 ° C and a pressure of 8 MPa for 5 hours.

After completion of the reaction, by returning to room temperature the reaction vessel was allowed to cool, the C0 ₂ is a solvent was removed as a gas in the gas phase. After diluting the reaction product with filter form, the catalyst was removed by filtration using filter paper. The removed catalyst can be reused by rinsing it at 650 ° C for 2 hours after washing it with a black hole form.

 The filtrate is purified by chromatography on a silica gel column (developing solvent: toluene: ethyl acetate = 4-1: 1), and then concentrated under reduced pressure to obtain the desired formula (X3);

Was recovered in an amount of 9.5 mg. The yield is 6.9%. The yield was calculated by weight% based on 2,3,4,6-tetra-O-acetyl-α-D-galactovilanosyltrichloroacetimidate used as a sugar donor.

Further, the obtained glycoside was subjected to NMR measurement. The measurement conditions and results are as follows.

 (Measurement condition)

 ^ -NMR (50 OMH z)

Equipment: Bruker's Biospin Co., Ltd. (BRUKER), Bruker DPX-250 spe c t r ome t er

Measurement temperature: 27 ° C

Solvent: CDC 1 ₃

 (Result)

'H-NMR data (CDC 1 3, 5 0 OMH z): 7. 3 7- 7. 3 1 (m, 1 0H, ph X 2), 5. 5 9 (d, 1 H, J NH, aH = 9.09 MHz, NH), 5.30 (d, 1 H, J _{4i 5} = 2.79 MHz, H-4), 5.18 (d, 2 H, CH ₂ phofbenzylester), 5. 1 3 (d, 2 H , CH 2 phof Z), 5. 0 8 (dd, l H, J 2, 3 = 1 0. 5MH z, H- 2), 4. 9 1 (dd, l H, J ₃ , ₄ = _3.4 3 MHz, H_ 3), _4.4 1 (dd, 1 H,) _αΗ , β _Η = 2.30 MHz, aH), 4.41 (dd, 1 H, β H), 4. 3 6 (d, 1 H, J 1¾ 2 = 7. 9 3MH z, H- 1), 4. 0 3 (m, 2 H, H - 6 a, b;), 3.65 (t, 1H, H_5), 2.11, 2.02, 2.00, 1.97 (s, 1H, Ac), 1.21 (d, 3 H, J _C H ₃ , H = 6.35 MHz, β C— CH ₃ )

 According to the method for synthesizing a carbohydrate polymer and a glycoside using a supercritical fluid as the solvent of the present invention, the synthesis can be efficiently performed with simple steps while reducing the load on the environment. Industrial applicability

According to the method for producing a proton-type zeolite analog of the present invention, in particular, since the zeolite analog is used directly in an acidic solution, the step of performing proton exchange by ion exchange after synthesizing mesolite is reduced. Can be. In addition, clay diatomaceous earth Therefore, there is no need to add an alumina source, the production process is simple, and the reaction can be performed efficiently. Further, according to the method for producing a Zr skeleton-substituted zeolite analog of the present invention, even if the diatomaceous earth lacks an alumina source, a proton-type zeolite analog that functions as a Lewis acid by calcination is produced. can do.

 According to the dalycosylation reaction of the present invention, that is, the method for synthesizing a carbohydrate polymer or glycoside, in particular, a supercritical fluid is used as a reaction solvent, and a proton-type zeolite analog is used as a catalyst. Thus, the load on the environment can be reduced, and the reaction process can be simplified and the reaction can be performed efficiently.

Claims

The scope of the claims 1. A method for producing a raw material for producing a proton-exchanged zeolite analog, comprising zeolite having a tectosilicate skeleton, in which all or a part of cations of an inorganic mineral is replaced with H +, The method is as follows:  Treating the inorganic mineral with an acidic solution, The method. 2. The natural substance as a 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 sediment. The method according to claim 1, comprising at least one selected from: 3. The natural substance of the raw material containing the inorganic mineral is as follows:  Opal; and  3. The method of claim 2, further comprising: a mica mineral or a mica-based clay mineral, comprising at least one of illite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite. 4. The method of claim 1, further comprising the step of removing organics and smectite-based minerals by decantation using a neutral or alkaline solution. 5. The method of claim 1, wherein said acidic solution comprises hydrogen peroxide. 6. The method according to claim 1, wherein the acidic solution comprises a hydrochloric acid solution. 7. The neutral or alkaline solution comprises sodium pyrophosphate. The method described in. 8. The method according to claim 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 claim 1. 10. A method for producing a proton-exchanged zeolite analog, which comprises a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral is substituted with H +, wherein the method comprises:  Adding a mineral acid to the raw material obtained by removing the smectite-based clay mineral from the inorganic mineral, and reacting a silica source and an alumina source to obtain a reaction product; and  Baking the reaction product; Where: The proton-exchange Zeoraito analog is represented by the formula _{W p H m _ p Z n} 0 2n · SH 2 O,  W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII, and IB;  Z is A 1 + S i, and the S i / A 1 ratio is an integer of 1 or more; 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,  S is any number greater than or equal to 0, the method. 11. The method according to claim 10, wherein W is an alkali metal or an alkaline earth metal. 12. The natural material of the raw material containing the 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 sediment. 11. The method of claim 10, comprising at least one selected. 13. The raw natural substance containing the inorganic mineral is as follows:  Opal; and  13. The method of claim 12, further comprising: a mica mineral or a mica-based clay mineral, comprising at least one of illite, paragonite, tinwald mica, lithiae mica, biotite, phlogopite, sea chlorite, and muscovite. 14. The method according to claim 10, wherein said inorganic acid is sulfuric acid. 15. The method according to claim 10, wherein the firing temperature is 540 ° C or higher. 16. The method according to claim 10, wherein calcination is performed after air-drying a product obtained by reacting the silica source and the alumina source. 17. The proton-exchanged zeolite analog produced by the method according to claim 10, wherein the number of oxygen atoms O in the above formula is (2n-0.5 (m-p)) or more and less than 2n. 18. A method for producing a proton-exchanged zeolite analog to which a transition metal has been introduced, including a zeolite having a tectosilicate salt skeleton in which all or a part of cations of an inorganic mineral is substituted with H +, Less than: A transition metal compound is added to the raw material obtained by removing the smectite-based clay mineral from the inorganic mineral. Carrying step, Where: Proton exchange Zeoraito analogues by introducing the transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 0,  W is Al li metal, Al li earth metal, or I IA group to VIIA group, V 1 I is a transition metal selected from the group consisting of Group I and IB elements,  Z is a transition metal selected from the group consisting of elements from groups IIA to VIIA, VIII and IB, or a typical metal element selected from the group consisting of elements from group IIB and IVB;  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,  S is any number greater than or equal to 0, the method. 19. The method according to claim 18, wherein W is an alkali metal or an alkaline earth metal. 20. The natural material of the raw material containing the inorganic mineral is selected from the group consisting of diatomaceous earth, clayey diatomite, siliceous sedimentary rock, siliceous shale, mudstone, claystone, siltstone, marine sediment, and lake sediment. 19. The method of claim 18, comprising at least one selected. 21. The raw natural material containing the inorganic mineral is as follows:  Opal; and 20. The method of claim 18, further comprising: a mica mineral or a mica-based clay mineral, comprising at least one of illite, paragonite, tinwald mica, lysi mica, biotite, phlogopite, sea chlorite, and muscovite. 22. The method according to claim 18, wherein the supporting 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 thereof, of a transition metal selected from the group consisting of Group IIIA to Group VIIA, Group VIII, and IB. 19. The method according to claim 18. 24. The transition metal compound is a _{Z r C l 4, T i} C l 4, F e C l 2 , or mixtures thereof, The method of claim 23. 25. The method of claim 18, wherein the supporting is impregnation of the transition metal hydroxide gel. 26. The method according to claim 18, further comprising a step of hydrolyzing after the step of supporting. 27. The proton-exchanged zeolite analog produced by the method according to claim 18, wherein the number of oxygen atoms O in the above formula is (2n-0.5 (m-p)) or more and less than 2n. 28. A method for producing a proton-exchanged zeolite analog into which a transition metal has been introduced, including a zeolite having a tectosilicate salt skeleton in which all or a part of the cations of the inorganic mineral has been substituted with H +, Less than:  Adding an inorganic acid to the inorganic mineral carrying the transition metal, and reacting the transition metal with a silica source and an alumina source to obtain a reaction product; and Baking the reaction product; Where: The proton-exchanged zeolite analog into which the transition metal has been introduced is represented by the formula W _p H _{m —p} Z _n 0 _{2 n} · SH ₂₀ ;  W is an alkali metal, an alkaline earth metal, or IIIA to VIIA, V 1 I is a transition metal selected from the group consisting of Group I and IB elements,  Z is a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII and IB, or a typical metal element selected from the group consisting of elements of group IIB and group IVB;  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,  S is any number greater than or equal to 0, the method. 29. The method according to claim 28, wherein W is an alkali metal or an alkaline earth metal. 30. The natural substance 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 sediment. 29. The method of claim 28, comprising at least one selected from: 3 1. The natural substance of the raw material containing the inorganic mineral is as follows:  Opal; and  29. The mica mineral or mica-based clay mineral further comprising at least one of: illite, paragonite, chinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite. Method. 32. The method according to claim 28, wherein said inorganic acid is sulfuric acid. 33. The method according to claim 28, wherein the firing temperature is 540 ° C or higher. 34. The method of claim 28, wherein calcining is performed after air-drying a product obtained by reacting the transition metal with a silica source and an alumina source. 35. The proton-exchanged zeolite analog produced by the method according to claim 28, wherein the number of oxygen atoms O in the above formula is (2n-0.5 (m-p)) or more and less than 2n. 36. A method 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 is substituted with H +, wherein the method comprises the following steps:  Treating the inorganic mineral with an acidic solution;  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  Baking the reaction product; Where: The proton-exchanged zeolite analog is represented by the formula W _p H _m _ _p Z _n O _2n SH ₂₀ ,  W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII, and IB;  Z is A 1 + S i, and the S i / A 1 ratio is an integer of 1 or more; 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, S is any number greater than or equal to 0, the method. 37. The method of claim 36, further comprising the step of removing smectite-based minerals by decanting using a neutral or alkaline solution before adding the inorganic acid. 38. The method of claim 36, wherein the acidic solution comprises hydrogen peroxide. 39. The method according to claim 36, wherein W is an alkali metal or an alkaline earth metal. 40. The method of claim 36, wherein said neutral or alkaline solution comprises sodium pyrophosphate. 4 1. The natural substance 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 sediment. 37. The method of claim 36, comprising at least one selected from: 4 2. The natural substance of the raw material containing the inorganic mineral is as follows:  Opal; and  41. The method of claim 41, further comprising: a mica mineral or a mica-based clay mineral, comprising at least one of silicalite, paragonite, tinwald mica, lysian mica, biotite, phlogopite, sea chlorite, and muscovite. . 43. The method according to claim 37, wherein the smectite-based mineral includes organic matter and montmorillonite. 44. The method of claim 36, wherein the inorganic acid is sulfuric acid. 45. The method according to claim 36, wherein the firing temperature is 540 ° C or higher. 46. The method of claim 36, wherein calcining is performed after air-drying a product obtained by reacting the silica source and the alumina source. 47. Similar to the proton-exchanged zeolite produced by the method according to claim 36, wherein the number of oxygen atoms O in the above formula is (2n−0.5 (m−p)) or more and less than 2 n. body. 48. A method for producing a transition-exchanged proton-exchanged zeolite analog, which comprises a zeolite having a tectosilicate skeleton in which all or a part of cations of an inorganic mineral is substituted with H ⁺ , The following:  Treating the inorganic mineral with an acidic solution;  Supporting a transition metal compound on a raw material obtained by removing a smectite-based clay mineral from the inorganic mineral;  Adding an inorganic acid to the inorganic mineral supporting the transition metal compound, and reacting the transition metal with a silica source and an alumina source to obtain a reaction product; and  Baking the reaction product; Where: The proton-exchanged zeolite analog into which the transition metal has been introduced is represented by the formula W _p H _{m —p} Z _n 0 _{2 n} · SH ₂₀ ,  W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements of groups IIA to VIIA, VIII, and IB; Z is from the group consisting of elements from groups IIIA to VIIA, VIII and IB A selected transition metal or a typical metal element selected from the group consisting of group IIIB and group 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,  S is any number greater than or equal to 0, the method. 49. The method according to claim 48, further comprising the step of removing smectite-based minerals by decantation using a neutral or alkaline solution before adding the inorganic acid. 50. The method of claim 48, wherein said acidic solution comprises hydrogen peroxide. 51. The method according to claim 48, wherein W is an alkali metal or an alkaline earth metal. 52. The method according to claim 49, wherein said neutral or alkaline solution comprises sodium pyrophosphate. 5 3. The natural substance 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 sediment. 49. The method of claim 48, comprising at least one selected from: 5 4. The natural substance of the raw material containing the inorganic mineral is as follows:  Opal; and A mica mineral or mica-based clay mineral, including at least one of illite, paragonite, chinwald mica, lithia mica, biotite, phlogopite, sea chlorite, and muscovite 54. The method of claim 53, further comprising: 55. The method of claim 49, wherein the smectite-based mineral comprises organic montmorillonite. 56. The method according to claim 48, wherein the supporting 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 thereof, of a transition metal selected from the group consisting of Groups IIIA-VIIA, VIII, and IB. 49. The method of claim 48. 58. The transition metal compound is a _{Z r C l 4, T i} C l 4, F e C l 2 , or mixtures thereof, The method of claim 57. 59. The method of claim 48, wherein the supporting is impregnation of the transition metal hydroxide gel. 60. The method according to claim 48, further comprising a step of hydrolyzing after the step of supporting. 61. The proton-exchanged zeolite produced by the method according to claim 48, wherein the number of oxygen atoms O in the above formula is (2 n−0.5 (m−p)) or more and less than 2 n. Analog. 62. All or part of the inorganic mineral cations are replaced by H + A method for producing a proton-exchanged zeolite analog into which a transition metal has been introduced, including a zeolite having a skeleton, the method comprising:  Supporting a transition metal compound on a raw material obtained by removing a smectite clay mineral from the inorganic mineral;  Adding an inorganic acid to an inorganic mineral supporting a transition metal compound, and reacting the transition metal with a silica source and an alumina source; and  Baking the reaction product; Where: Proton exchange Zeoraito analogues by introducing the transition metal is represented by the formula _{W p H m _ p Z n} 0 2 n · SH 2 0,  W is an alkali metal, an alkaline earth metal, or a transition metal selected from the group consisting of elements from groups IIA to VIIA, 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 Group 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,  S is any number greater than or equal to 0, the method. 63. The proton-exchanged zeolite analog produced by the method of claim 62, wherein the number of oxygen atoms O in the formula is (2 n_0.5 (m-p)) or more and less than 2n. 64. A method for synthesizing a sugar-containing substance, comprising reacting a sugar donor with a sugar acceptor in the presence of a supercritical fluid to produce a sugar-containing substance. 65. The method of claim 64, wherein the supercritical fluid is a carbon dioxide fluid. 66. The method according to claim 64, wherein said reaction step is performed in the presence of an acid catalyst. 67. The method of claim 64, wherein the acid catalyst is an inorganic mineral treated with an acidic solution. 68. The method of claim 67, wherein said acidic solution is sulfuric acid. 69. The natural substance of the raw material containing the 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 sediment. 68. The method of claim 67, comprising at least one selected. 70. The raw natural substances containing the inorganic minerals are as follows:  Opal; and  Mica minerals or mica-based clay ores containing at least one of illite, paragonite, tinwald mica, lithic mica, biotite, phlogopite, sea chlorite, and muscovite ^! 70. The method of claim 69, further comprising: 71. The acid catalyst is triflate Ruo Russia silver methane sulfonate, triflate Ruo b methanesulfonic acid trimethylsilyl, boron trifluoride GETS chill _{etherate, S nC l 2 - AgC 10} 4, SnC l 2 - AgOT f, Cp 2 Z r C l ₂ - AgC 10 _4, sulfated zirconium Nia, diatomaceous earth, is selected from the group consisting of sulfuric acid treatment diatomaceous earth and sulfated titania supported diatomaceous earth, the method of claim 66. 72. The method according to claim 64, wherein the sugar-containing substance is a carbohydrate polymer or a glycoside. Method. 73. Equation (I)

(In the formula, R ¹ an OC (NH) CC 1 _3, one C l, is one B r or a F, R ² an OH, -OR ^6, - a N ₃ or a NHR ^7, R ³ and R ⁴ are, independently of one another, one OH or one OR ⁶ , and R ⁵ is one H, _CH ₃ , one CH ₂ OH, _CH ₂ OR ⁶ , or —COO R ⁸ , ⁶ are each independently 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-protecting group, R ⁸ is a carboxyl-protecting group Is.) One or more sugar donors selected from the group comprising a saccharide unit of  Formula (I I);

Wherein R ⁹ is —OR ¹⁴ , R ¹ is —OR ¹⁵ , —N ₃ or one NHR ¹⁶ , R ¹¹ is —OR ¹⁷ , R ¹² is one OR ¹⁸ , R ¹³ is —H, _CH ₃ , —CH ₂ OR ¹⁹ or one COOR ²⁰ ; R ¹⁴ and R ¹⁵ are, independently of one another, —H, a hydroxyl protecting group or any reactive functional group containing a hydroxyl group; R ¹⁶ is an amino-protecting group; R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently of one another any reaction containing 1 H, hydroxyl-protecting group or hydroxyl group R ^2Q is a carboxyl-protecting group, wherein the sugar chain has a protected functional group. At least one of R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ is _H. ) And one or more sugar receptors selected from the group containing a sugar unit of  A method for synthesizing a saccharide polymer, comprising a step of producing a saccharide polymer by reacting in the coexistence of an acid catalyst and a supercritical fluid. 74. The method of claim 73, wherein the supercritical fluid is a carbon dioxide fluid. 75. The method of claim 73, wherein the acid catalyst is a mineral treated with an acidic solution.

(Wherein, R ²¹ is _{- OC (NH) CC 1 3} , is one C l, one B r or a F, R ^{2 2} is - OH, -OR ^26, _N ₃ or - NHR ^27, R ²³ and R ²⁴ are, independently of one another, —OH or one OR ²⁶ ; R ²⁵ is one H, one CH ₃ , one CH ₂ OH, one CH ₂ OR ²⁶ or one COOR ²⁸ ; ²⁶ is independently a hydroxyl-protecting group or a sugar chain in which all reactive functional groups containing a hydroxyl group are protected, R ²⁷ is an amino-protecting group, R ²⁸ is a carboxyl group It is a protecting group, provided that at least one of R ²² , R ²³ , R ²⁴ or R ²⁵ is a hydroxyl group (in the case of R ²⁵ , one CH ₂ OH). One or more sugar units selected from the group containing A method for synthesizing a saccharide polymer, comprising a step of producing a saccharide polymer by reacting in the coexistence of an acid catalyst and a supercritical fluid. 77. The method of claim 76, wherein the supercritical fluid is a carbon dioxide fluid. 78. The method according to claim 76, wherein the acid catalyst is an inorganic mineral treated with an acidic solution. 79. Equation (IV)

(Wherein, R ²⁹ an _{OC (NH) CC 1 3,} - a C l, -B r or a F, R ³ is -. OR ^34, - N _3, or an NHR ^35, R ³¹ and R ³² is —OR ³⁴ , R ³³ is 1 H, 1 CH ₃ , 1 CH ₂ OR ³⁴ , or 1 COOR ³⁶ , and R ³⁴ independently of each other, contains a hydroxyl protecting group, or a hydroxyl group All reactive functional groups are protected sugar chains, R ³⁵ is an amino protecting group, and R ³⁶ is a carboxyl protecting group. A sugar donor, 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 linear, branched, cyclic having no side chain or a cyclic saturated aliphatic group having a side chain, or R is a saturated aliphatic group containing one or more unsaturated bonds. Is an unsaturated aliphatic group corresponding to an aromatic group.) A group containing a saturated fatty alcohol and an unsaturated fatty alcohol represented by And one type of sugar receptor selected from  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. The method of claim 79, wherein the supercritical fluid is a carbon dioxide fluid. 81. The method of claim 79, wherein the acid catalyst is an inorganic mineral treated with an acidic solution.

(Wherein, R ²⁹ is _{-OC (NH) CC 1 3,} - C l, is -B r or _F, R ^{3 0} one OR ^34, one N ₃ or - NHR ^35, R ³¹ and R ³² is —OR ³⁴ ; R ³³ is 1 H, 1 CH ₃ , 1 CH ₂ OR ³⁴ , or 1 COOR ³⁶ ; R ³⁴ is, independently of one another, a hydroxyl protecting group or any containing a hydroxyl group Is a sugar chain in which the reactive functional group is protected, R ³⁵ is an amino protecting group, and R ³⁶ is a carboxyl protecting group. A donor and formula (VI); (VI)

(Wherein, 1 ³⁷ Hard 1 ^ Matawa? 1 ₃ Deari, R ³⁸ is a peptide chain Amino group protecting group, the peptide chain or a sugar chain bound, R ³⁹ is a carboxyl group protecting group, peptidyl When R ³⁸ and / or R ³⁹ is a peptide chain to which a sugar chain is bound, all reactive functional groups including the hydroxyl group of the sugar chain are provided. Shall be protected.) And one kind of sugar receptor selected from the group including a peptide chain and a peptide chain to which a sugar chain is 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 of claim 82, wherein the supercritical fluid is a carbon dioxide fluid. 84. The method of claim 82, wherein said acid catalyst is an inorganic mineral treated with an acidic solution. 8 5 Equation (IV)

(Wherein, R ²⁹ an OC (NH) CC 1 _3, one C l, one B r or - F, R ^{3 0} is _OR ^34, a _N ₃ or a NHR ^35, R ³¹ and R ³² Ri one oR ³⁴ Dare, R ³³ is _{- H, -CH 3, _CH 2} oR 34 or - a COOR ^36, R ³⁴ independently of one another, all reactions involving hydroxyl protecting group or hydroxyl group, R ³⁵ is an amino protecting group, R ³⁶ is carboxyl It is a group protecting group. A) a sugar donor selected from the group comprising a saccharide unit of formula (VII);

Wherein R ⁴ is —OR ⁴⁵ , R ⁴¹ is one OR ⁴⁶ , —N ₃ or one NHR ⁴⁷ , R ⁴² is one OR ⁴⁸ , R ⁴³ is one OR ⁴⁹ , R ⁴⁴ is 1 H, 1 CH ₃ , -CH ₂ OR ⁵ ° or 1 COOR ⁵¹ , and R ⁴⁵ is a diacylglycerol, ceramide, sterol, terpene, peptide chain or a hydrogen atom from a hydroxyl group. R ⁴⁶ is _H, a hydroxyl-protecting group, or a sugar chain in which all reactive functional groups including hydroxyl groups are protected, such as a force that is a peptide chain to which a sugar chain is bound, or a saturated aliphatic group or an unsaturated aliphatic group R ⁴⁷ is an amino-protecting group, and R ⁴⁸ , R ⁴⁹ and R ⁵ are each independently a _H, a hydroxyl-protected group or a sugar in which all reactive functional groups including a hydroxyl group are protected. a chain, R ⁵¹ is a carboxyl group protecting group. ^{However, R 46, R 48, R} 49 and R ⁵ °, everything And no case of acid protecting group, R ^46, R ^48, of R ⁴⁹ and R ^50, whether any one is _H, was or R ^46, R ^48, R ⁴⁹ and R ^5Q If none of the above is 1 H, one of the sugar chains shall have one unprotected hydroxyl group.) One sugar receptor selected from the group containing a sugar unit 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. The method of claim 85, wherein the supercritical fluid is a carbon dioxide fluid. 87. The method according to claim 85, wherein the acid catalyst is an inorganic mineral treated with an acidic solution. 88. Use of supercritical fluids in daricosylation reactions. 89. The use according to claim 88, wherein the supercritical fluid is a fluid of carbon dioxide. 90. Use of acid catalysts in glycosylation reactions. 91. The use according to claim 90, wherein the acid catalyst is an inorganic mineral treated with an acidic solution.