JPWO2017170808A1 - Method for producing four-membered ring lactone and heterogeneous catalyst - Google Patents

Abstract

To provide a method for efficiently producing a 4-membered ring lactone in a higher yield in a carbonylation reaction of an epoxide using a heterogeneous catalyst that can be easily separated from a product and can be handled in air. about.
A method for producing a four-membered lactone by carbonylation of an epoxide, comprising epoxide and carbon monoxide,
(A) An oxide of one or more metals selected from Group 5 to Group 10 transition metals is used as a carrier, and Group 10 transition metal, Group 11 transition metal, and oxides thereof are used as the carrier. A heterogeneous catalyst in which one or more selected from the above are supported (however, the supported material is different from the metal oxide used as the carrier),
(B) a metal Lewis acid;
(C) A method for producing a four-membered ring lactone, comprising a step of reacting in the presence of a Lewis base containing an atom selected from an oxygen atom and a nitrogen atom in the molecule.

Description

  The present invention relates to a method for producing a four-membered ring lactone and a heterogeneous catalyst. More specifically, the present invention relates to a method for producing a four-membered lactone by an epoxide carbonylation reaction, and a heterogeneous catalyst for use in the epoxide carbonylation reaction.

  Lactones are industrially important compounds as raw materials and intermediates for pharmaceuticals and fragrances. In particular, four-membered ring lactones have high reactivity due to the distorted structure, and are very useful compounds as raw materials for biodegradable resins, acrylic acid, succinic anhydride, etc. as well as raw materials and intermediates for pharmaceuticals. is there. However, five-membered and six-membered lactones can be easily obtained mainly by dehydration condensation of hydroxycarboxylic acid or the like, but four-membered lactones are difficult to synthesize by dehydration condensation, and other methods have been required.

As such another kind of technique, a technique for obtaining a four-membered lactone by carbonylation of an epoxide is known.
For example, Non-Patent Document 1 reports a method of carbonylating an epoxide under high-pressure carbon monoxide using a homogeneous cobalt carbonyl catalyst Co ₂ (CO) ₈ .
Non-Patent Document 2 reports a method of efficiently carbonylating an epoxide under high-pressure carbon monoxide using a homogeneous bimetallic catalyst such as a cobalt carbonyl / porphyrin aluminum complex. Further, Patent Document 1 reports a method of carbonylation in a high boiling point solvent such as sulfolane in the presence of a homogeneous bimetallic catalyst such as cobalt carbonyl / porphyrin aluminum complex, and the reaction solution is distilled under reduced pressure. Thus, a method is disclosed in which a fraction containing a target four-membered ring lactone and a fraction containing a catalyst and a high-boiling solvent are separated, and the fraction containing the catalyst is recycled to the reaction system.

  Patent Document 2 reports carbonylation of epoxides using a heterogeneous catalyst in which gold is supported on cobalt oxide. A catalyst in which gold is supported on cobalt oxide is also known as a catalyst in an olefin hydroformylation reaction, and it is reported that the catalytic activity is improved by pretreating the catalyst with hydrogen gas. (Patent Document 3).

Special table 2012-523421 gazette JP 2013-173089 A JP 2009-244102 A

J. et al. Org. Chem. 2001, 66, 5424-5426. J. et al. Am. Chem. Soc. 2007, 129, 4948-4960.

  However, although the epoxide carbonylation reaction using the homogeneous catalyst described above exhibits high reactivity, it is difficult to separate the catalyst and the product and to reuse the catalyst itself. Further, in the method using a high-boiling solvent such as sulfolane described in Patent Document 1, the catalytic activity is reduced compared to the case where THF or the like is used as a solvent, and the reaction cannot be performed efficiently. Moreover, since a cobalt carbonyl / porphyrin aluminum complex will decompose | disassemble easily when heated to 100 degreeC or more, there exists a problem that vacuum distillation temperature cannot be raised and sufficient isolation | separation cannot be performed. Furthermore, the cobalt carbonyl catalyst and the cobalt carbonyl / porphyrin aluminum complex have a problem that they are very unstable with respect to air and moisture and require special care in handling.

  On the other hand, the cobalt oxide-supported gold catalyst is stable against air and water, has excellent handleability, and can easily separate the catalyst and the product by solid-liquid separation or the like. However, the heterogeneous reaction has a low yield of the four-membered ring lactone and is difficult to apply to industrial production. According to the study by the present inventors, the target four-membered ring lactone was not obtained at all by using only the catalyst described in Patent Document 2.

Therefore, the problem to be solved by the present invention is that the epoxide carbonylation reaction using a heterogeneous catalyst that can be easily separated from the product and can be handled in the air is more efficient at a higher yield. Another object is to provide a method for producing a four-membered lactone.
Another problem to be solved by the present invention is to provide a heterogeneous catalyst that can be easily separated from the product, can be handled in the air, and exhibits high activity in the carbonylation reaction of epoxides. There is to do.

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific Lewis acid and epoxide in a epoxide carbonylation reaction using a transition metal and / or a metal oxide catalyst supporting the oxide thereof. By carrying out the reaction in the presence of a specific Lewis base, the inventors have found that the reactivity is dramatically improved as compared with the epoxide carbonylation reaction using a conventional heterogeneous catalyst, and the present invention has been completed. .
In addition, the present inventors have found that a heterogeneous catalyst supporting a specific transition metal and / or its oxide exhibits very high activity in the carbonylation reaction of epoxide, leading to the completion of the present invention. It was.

That is, the present invention provides the following <1> to <11>.
<1> A method for producing a four-membered lactone by a carbonylation reaction of an epoxide, wherein the epoxide and carbon monoxide are
(A) An oxide of one or more metals selected from Group 5 to Group 10 transition metals is used as a carrier, and Group 10 transition metal, Group 11 transition metal, and oxides thereof are used as the carrier. A heterogeneous catalyst in which one or more selected from the above are supported (however, the supported material is different from the metal oxide used as the carrier),
(B) a metal Lewis acid;
(C) A method for producing a four-membered ring lactone, comprising a step of reacting in the presence of a Lewis base containing an atom selected from an oxygen atom and a nitrogen atom in the molecule. Hereinafter, this manufacturing method is also referred to as “the manufacturing method of the present invention”.
<2> The production method according to <1>, wherein the metal Lewis acid (B) is one or more selected from an organometallic compound, a metal halide, and a metal triflate.
<3> The production method according to <1>, wherein the metal Lewis acid (B) is an organoaluminum compound.
<4> The Lewis base (C) according to any one of <1> to <3>, wherein the Lewis base (C) is one or more selected from a chain ether, a cyclic ether, a chain amine, a cyclic amine, and a nitrile. Production method.
<5> The production method according to any one of <1> to <3>, wherein the Lewis base (C) is glycol dialkyl ether.
<6> Before performing the carbonylation reaction, any one of <1> to <5>, in which a pretreatment is performed in which hydrogen or a mixed gas containing hydrogen and carbon monoxide is brought into contact with the heterogeneous catalyst (A). The manufacturing method of crab.
<7> The material to be supported by the heterogeneous catalyst (A) is one or more selected from palladium, platinum, gold, and oxides thereof, and any one of <1> to <6>. Manufacturing method.
<8> The method according to any one of <1> to <7>, wherein the carrier of the heterogeneous catalyst (A) is cobalt oxide.
<9> An oxide of one or more metals selected from Group 5 to Group 10 transition metals is used as a carrier, and the carrier carries at least one selected from Group 10 transition metals and oxides thereof. The heterogeneous catalyst used in the epoxide carbonylation reaction (however, the supported material is different from the metal oxide used as the carrier). Hereinafter, this catalyst is also referred to as “catalyst X of the present invention”.
<10> The heterogeneous catalyst according to <9>, wherein the supported material is at least one selected from palladium and an oxide thereof.
<11> The heterogeneous catalyst according to <9> or <10>, wherein the support is cobalt oxide.

According to the production method of the present invention, a four-membered lactone can be efficiently obtained in a higher yield than the epoxide carbonylation reaction using a conventional heterogeneous catalyst.
Further, the catalyst X of the present invention can be easily separated from the product, can be handled in air, and exhibits a very high catalytic activity for the epoxide carbonylation reaction.

<Method for producing four-membered ring lactone>
The epoxide used as a raw material in the production method of the present invention is not particularly limited as long as it is a compound containing at least one three-membered ether structure in its chemical structure. Examples of the epoxide include compounds represented by the following formula (1).

[In Formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
However, any one of R ³ and R ⁴ may form a ring together with any one of R ¹ and R ² . ]

The hydrocarbon group represented by R ^{1 to} R ⁴ is a concept that includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and is any of linear, branched, and cyclic. It may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-12, More preferably, it is 1-6, Most preferably, it is 1-4. As the aliphatic hydrocarbon group, an alkyl group is preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
Carbon number of an alicyclic hydrocarbon group becomes like this. Preferably it is 3-12, More preferably, it is 3-7. As the alicyclic hydrocarbon, a cycloalkyl group is preferable. Specific examples include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The number of carbon atoms of the aromatic hydrocarbon group is preferably 6-20, more preferably 6-12. As the aromatic hydrocarbon group, an aryl group and an aralkyl group are preferable. Examples of the aryl group include a phenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the substituent in R ^{1 to} R ⁴ include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group and ethoxy group; (meth) acryloyloxy group and the like.

Examples of the ring formed by any one of R ³ and R ⁴ together with any one of R ¹ and R ² include cycloalkane rings such as cyclohexane ring, methylcyclohexane ring, cycloheptane ring, and cyclooctane ring. . The number of carbon atoms in the ring is preferably 3 to 10, and more preferably 5 to 7.

As a combination of R ^{1 to} R ⁴ , R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are a hydrogen atom, and R ¹ and R ³ are A combination that is a hydrogen atom and R ² and R ⁴ form a ring is preferable.

Preferred examples of the epoxide include ethylene oxide, propylene oxide, isobutene oxide, 1-butene oxide, 2-butene oxide, styrene oxide, 1-hexene oxide, 1-octene oxide, cyclohexene oxide, glycidyl methyl ether, glycidyl (meta ) Acrylate, epichlorohydrin and the like. Among these, ethylene oxide, propylene oxide, and 1-octene oxide are more preferable, and ethylene oxide and propylene oxide are particularly preferable.
Moreover, the four-membered ring lactone obtained by the production method of the present invention is a lactone obtained by carbonylation of the epoxide. Examples of the lactone include β-propiolactone, β-butyrolactone, 4-hexyloxetane-2-one, and the like.

  Carbon monoxide gas is usually used as the other raw material, carbon monoxide. The gas is not necessarily pure, and may contain a small amount of an inert gas such as carbon dioxide, nitrogen, or methane. Further, it may be a synthesis gas containing carbon monoxide and hydrogen as main components.

((A) heterogeneous catalyst (solid catalyst))
The heterogeneous catalyst used in the production method of the present invention uses, as a carrier, an oxide of one or more metals selected from Group 5 to Group 10 transition metals, and the carrier includes a Group 10 transition metal, Heterogeneous catalyst in which one or more selected from Group 11 transition metals and oxides thereof are supported (however, the supported material is different from the metal oxide used as the carrier) It is.

(Carrier)
Group 5 to Group 10 transition metals in the carrier include Group 5 transition metals such as vanadium (V); Group 6 transition metals such as chromium (Cr), molybdenum (Mo), tungsten (W), etc. Group 7 transition metals such as manganese (Mn) and rhenium (Re); Group 8 transition metals such as iron (Fe), ruthenium (Ru) and osmium (Os); cobalt (Co) and rhodium (Rh) ), Group 9 transition metals such as iridium (Ir); Group 10 transition metals such as nickel (Ni). Among these, transition metals of Group 8 to Group 9 are preferable, iron (Fe) and cobalt (Co) are more preferable in terms of inexpensiveness, and cobalt (Co) is particularly preferable in terms of catalytic activity.
Specific examples of the support include iron oxide (eg, FeO, Fe ₂ O ₃ , Fe ₃ O _4, etc.), cobalt oxide (eg, CoO, Co ₂ O ₃ , Co ₃ O _4, etc.). Among them, cobalt oxide is particularly preferable from the viewpoint of catalytic activity.
The transition metal oxide may be a single metal oxide or a composite oxide of two or more metals. Moreover, the mixture of the oxide from which the valences of the same metal differ may be sufficient.

(Supported material)
Further, the transition metals of Group 10 and Group 11 in the supported material include Group 10 transition metals such as palladium (Pd) and platinum (Pt); 11th metals such as gold (Au) and silver (Ag). The transition metal of a group is mentioned, Among these, 1 type may be used or 2 or more types may be used.
Among these, platinum (Pt), palladium (Pd), and gold (Au) are preferable in terms of catalytic activity, Group 10 transition metals are more preferable, platinum (Pt), and palladium (Pd) are more preferable. (Pd) is particularly preferred.
Note that a metal species different from the metal oxide used as the carrier is used for the transition metal in the supported object. That is, when the metal species in the carrier is palladium, the metal species in the supported material is not palladium, and when the metal species in the carrier is nickel, the metal species in the supported material is not nickel and the metal species in the carrier is platinum. In this case, the metal species in the supported object is not platinum.
Of the transition metal oxides in the supported article, palladium oxide is preferred. The transition metal oxide may be a mixture of oxides of different valences of the same metal. In the transition metal oxide, as described later, catalytic activity is imparted by reducing part or all of the transition metal by pretreatment with hydrogen or a mixed gas containing hydrogen and carbon monoxide. be able to.

The amount of the supported material is not particularly limited, but is preferably 0.1 atomic% or more, more preferably 1 atomic% or more, and preferably 50 atoms, based on the total amount of metal in the heterogeneous catalyst. % Or less, more preferably 30 atomic% or less, still more preferably 20 atomic% or less, and particularly preferably 14 atomic% or less. By setting the amount of the supported material in such a range, the catalytic activity is further improved.
The “atomic%” in the present invention can be determined from the mol% of the precursor of the supported substance in the total moles of the precursor of the support and the precursor of the supported substance used in the catalyst preparation stage.

Further, the shape of the heterogeneous catalyst is not particularly limited, and any shape such as powder, crushed, particulate, and columnar can be used. In the present invention, one type of heterogeneous catalyst may be used alone, or two or more types of catalysts having different types and supported amounts; specific surface areas or shapes of the catalysts may be used in combination. Good.
Further, the heterogeneous catalyst is preferably one in which a nanoparticle layer of a supported material is formed on the surface of the carrier.

  The method for supporting these transition metals and the like (supported materials) on the carrier is not particularly limited, but, for example, a compound containing in the molecule a Group 5 to Group 10 transition metal capable of forming a metal oxide serving as a carrier. (Hereinafter also referred to as compound α) and a compound containing a group 10 or group 11 transition metal (different from a transition metal serving as a carrier) in the molecule (hereinafter also referred to as compound β), The method (coprecipitation method) which makes it react with a precipitant and precipitates is mentioned. By separating the precipitate deposited by the coprecipitation method and baking it, nanoparticles of the supported material can be formed on the surface of the carrier.

The type and form of compound α are not particularly limited, but it is preferably used as an aqueous solution using a water-soluble metal salt. Examples of the metal salt include halides such as chloride, bromide and iodide; salts of inorganic acids such as nitrates and sulfates; salts of organic acids such as acetates and the like. These metal salts may be used alone or in combination of two or more.
The type and form of compound β are not particularly limited, but it is preferably used as an aqueous solution using a water-soluble metal salt or complex salt. Examples of the metal salt include halides such as chloride, bromide and iodide; salts of inorganic acids such as nitrates and sulfates; salts of organic acids such as acetates and the like. Examples of complex salts include chloroauric acid, chloroplatinic acid, chloropalladic acid, and salts thereof. Moreover, these metal salts and metal complex salts may be used by 1 type, or may be used by 2 or more types.

Examples of the precipitating agent include alkalis such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
Concentration of aqueous solution used at the time of coprecipitation, temperature, addition rate of precipitating agent, etc. can be set as appropriate. By controlling these, physical properties such as the amount of supported metal and specific surface area can be adjusted to the desired range. can do.

  The heterogeneous catalyst thus obtained can be activated by bringing it into contact with hydrogen or a mixed gas containing hydrogen and carbon monoxide and performing a pretreatment. This pretreatment is preferably performed under heating, more preferably in a temperature range of 60 to 200 ° C, and further preferably in a temperature range of 80 to 180 ° C. The pressure of hydrogen or a mixed gas containing hydrogen and carbon monoxide is preferably in the range of 0.1 to 30 MPa, and more preferably in the range of 1 to 10 MPa. Moreover, when using the said mixed gas, the range of 90/10-10/90 is preferable and, as for the partial pressure ratio of hydrogen and carbon monoxide, the range of 80/20-20/80 is more preferable. The contact time is usually in the range of 30 minutes to 48 hours, preferably 1 to 24 hours.

  The amount of the catalyst used may be appropriately selected depending on the type of epoxide, the type and physical properties of the metal used in the catalyst, the reaction system, the reaction conditions, and the like. It is 01-10 mol%, Preferably it is 0.05-5 mol%.

((B) metal Lewis acid)
In the present invention, the metal Lewis acid means a Lewis acid containing a metal atom in the molecule.
Examples of metal Lewis acids include organometallic compounds, metal halides, metal triflates, and the like.

  Specifically, as the organometallic compound, trialkylaluminum (trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc.), alkylaluminum hydride (diisobutylaluminum hydride, etc.) ), Organoaluminum compounds such as alkylaluminum halides (such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride), alkylaluminum alkoxides (such as diethylaluminum ethoxide); diethylzinc, diisobutylzinc, di- Organic zinc compounds such as n-hexyl zinc and ethyl zinc (t-butoxide) It is. In addition, the alkyl group and alkoxy group in each said organoaluminum compound may be linear or branched, The carbon number becomes like this. Preferably it is 1-9, More preferably, it is 1-6.

  Examples of the metal halide include magnesium halides such as magnesium chloride and magnesium bromide; calcium halides such as calcium chloride and calcium bromide; titanium halides such as titanium chloride (IV) and titanium bromide (IV); Iron halides such as iron (II) chloride and iron (III) chloride; Cobalt halides such as cobalt (II) chloride and cobalt (III); Nickel halides such as nickel (II) chloride; Copper (II) chloride Copper halides such as copper (II) bromide; Zinc halides such as zinc chloride and zinc bromide; Aluminum halides such as aluminum chloride and aluminum bromide; Tin (II) chloride, tin (IV) chloride, odor And tin halides such as tin (II) halide and tin (IV) bromide.

  Examples of the metal triflate include group 3 metal triflates such as scandium triflate, yttrium triflate, lanthanum triflate, and cerium triflate. The triflate means trifluoromethane sulfonate.

These metal Lewis acids may be used individually by 1 type, and may use 2 or more types together.
Among these metal Lewis acids, organometallic compounds are preferred, organoaluminum compounds are more preferred, and trialkylaluminums and alkylaluminum halides are particularly preferred from the viewpoint of improving catalytic activity.

  The amount of metal Lewis acid used is not particularly limited, but is usually in the range of 0.01 to 10 mol%, preferably in the range of 0.5 to 5 mol%, based on the epoxide.

((C) Lewis base)
The Lewis base used in the production method of the present invention contains an atom selected from an oxygen atom and a nitrogen atom in the molecule. The Lewis base may contain only one of oxygen atom and nitrogen atom in the molecule or may contain both in the molecule. Specific examples of such a Lewis base include a chain ether, a cyclic ether, a chain amine, a cyclic amine, and a nitrile.

  Examples of the chain ether include dialkyl ethers such as dimethyl ether, diethyl ether, ethyl methyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl ter-butyl ether, and amyl methyl ether; glycol dialkyl ether and the like. Can be mentioned. Among glycol dialkyl ethers, a compound represented by the following formula (2) is preferable.

[In Formula (2),
R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 10 carbon atoms,
R ⁷ represents an alkanediyl group having 1 to 6 carbon atoms,
n represents an integer of 1 or more. ]

The alkyl group represented by R ⁵ and R ⁶ has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group is preferably a linear or branched alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
The alkanediyl group represented by R ⁷ has 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably 2 or 3, and particularly preferably 2. The alkanediyl group is preferably a linear or branched alkanediyl group. Examples of the alkanediyl group include an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group.
Further, as a combination of R ^{5 to} R ^7, a combination in which R ⁵ and R ⁶ are the same alkyl group and R ⁷ is an ethane-1,2-diyl group is preferable in terms of catalytic activity and cost. Take as an example.
n is preferably an integer of 1 to 100, more preferably an integer of 1 to 50, still more preferably an integer of 2 to 30 in that it has a remarkable effect in stabilizing metal Lewis acid and improving catalytic activity. An integer of from 10 to 10 is particularly preferred.

  Examples of the glycol dialkyl ether include ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme, boiling point: about 162 ° C.), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), pentaethylene glycol dimethyl ether (penta). Grime), ethylene glycol diethyl ether (ethyl monoglyme), diethylene glycol diethyl ether (ethyl diglyme), diethylene glycol dibutyl ether (butyl diglyme), diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol Such Lumpur butyl methyl ether.

  Examples of the cyclic ether include cyclic monoethers such as tetrahydrofuran (THF); crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. Of the cyclic ethers, cyclic monoethers are preferred.

  Examples of chain amines include trialkylamines such as triethylamine, tripropylamine, and tributylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, and the like. Tetraalkylated ethylenediamine; alkylated polyethyleneamines such as N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, etc. Can be mentioned.

  Examples of the cyclic amine include bridged cyclic amines such as quinuclidine and 1,4-diazabicyclo- [2.2.2] octane (DABCO); 1,8-diazabicyclo [5.4.0] undec-7-ene. (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and other cyclic diamines having an amidine skeleton; 1,5,7-triazabicyclo [4.4.0] deca Cyclic triamines having a guanidine skeleton such as -5-ene (TBD); pyridine, α-picoline, β-picoline, γ-picoline, 4- (N, N-dimethylamino) pyridine, pyrazine, pyrimidine, imidazole, N-methyl Contains nitrogen atoms such as imidazole, purine, 2,2′-bipyridine, 2,2 ′: 6 ′, 2 ″ -terpyridine, 3,2 ′: 6 ′, 3 ″ -terpyridine Such heterocyclic aromatic compounds. Of the cyclic amines, heterocyclic aromatic compounds containing nitrogen atoms are preferred.

  Examples of nitriles include acetonitrile, propionitrile, butyronitrile, and benzonitrile.

  As the Lewis base, a Lewis base containing two or more heteroatoms such as dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone can also be used.

These Lewis bases may be used individually by 1 type, and may use 2 or more types together.
Among these Lewis bases, glycol dialkyl ethers are preferable, glymes are more preferable, diglyme, triglyme, tetraglyme, pentag lime, ethyl digiger in view of remarkable effects in stabilizing metal Lewis acid and improving catalytic activity. Glymes having 3 or more donor atoms (number of oxygen atoms) such as lime and butyl diglyme are particularly preferable.

  The amount of the Lewis base used may be equal to or more than the equivalent of the metal Lewis acid, and usually 1 mol or more is used per 1 mol of the total amount of the metal Lewis acid. Moreover, the upper limit of the usage-amount of a Lewis base is not specifically limited, A Lewis base can also be used as a solvent.

  When a Lewis base is used as a solvent, glycol dialkyl ether is also preferred from the viewpoint of excellent solubility of epoxide, carbon monoxide and metal Lewis acid. In addition, glymes are more preferred because of their simple structure and low cost, their boiling points are large in terms of boiling point difference from four-membered lactones and are easy to separate by distillation, in terms of thermal stability and catalytic activity. Is particularly preferable when it is 200 ° C. or higher. Examples of glymes having a boiling point of 200 ° C. or higher include triglyme, tetraglyme, pentag lime, and butyl diglyme.

  When the Lewis base is used as a solvent, the amount used is not particularly limited, but is usually in the range of 0.1 to 100 parts by weight, preferably 0.5 to 30 parts by weight with respect to 1 part by weight of the total epoxide. More preferably, it is the range of 1-10 mass parts.

((D) inert solvent)
The carbonylation reaction may be carried out in the presence of a solvent inert to the reaction in addition to the above (A) to (C).
Inert solvents include hydrocarbon solvents such as toluene, xylene, hexane, heptane, cyclohexane, and methylcyclohexane; chloroform, methylene chloride, tetrachloride from the standpoint of safety during handling and ease of recovery and purification. A halogenated hydrocarbon solvent such as carbon is used. Moreover, you may use the target four-membered ring lactone as a solvent.
These inert solvents may be used individually by 1 type, and may use 2 or more types together.

  The amount of these inert solvents used is not particularly limited, but the total amount of the solvent (the total amount of Lewis base and inert solvent when Lewis base is used as a solvent) relative to 1 part by mass of the epoxide, Usually, it is the range of 0.1-100 mass parts, Preferably it is the range of 0.5-30 mass parts, More preferably, it is the range of 1-10 mass parts.

The carbonylation reaction can be carried out under batch, semi-batch or continuous conditions.
For example, in the case of a batch reaction, a heterogeneous catalyst (A) is charged into a stirred tank reactor, pretreated under hydrogen or a hydrogen / carbon monoxide mixed gas, cooled to room temperature, depressurized, and epoxide is added thereto. Filling with metal Lewis acid (B), Lewis base (C), carbon monoxide and inert solvent (D) if necessary, heating to a predetermined reaction temperature and reacting for a required time, a four-membered ring Lactone can be obtained. In the case of a batch reaction, the reaction time is usually 30 minutes to 48 hours, preferably 1 to 24 hours.
In the case of a continuous reaction, after pre-treating hydrogen or a hydrogen / carbon monoxide mixed gas in advance in a fixed bed or fluidized bed reactor containing the heterogeneous catalyst (A), a predetermined reaction temperature is obtained. Then, an epoxide, a metal Lewis acid (B), a Lewis base (C), carbon monoxide and, if necessary, an inert solvent (D) are supplied at a predetermined flow rate, and a heterogeneous catalyst (A ) To obtain a 4-membered ring lactone.

  Although reaction temperature is not specifically limited, 0-250 degreeC is preferable, 25-200 degreeC is more preferable, 50-150 degreeC is further more preferable, 75-120 degreeC is especially preferable. By setting the reaction temperature in such a range, the reaction rate can be increased. In addition, the formation of by-products and the decomposition of the generated four-membered ring lactone can be suppressed.

  The reaction pressure is preferably 0.1 to 70 MPa, more preferably 0.5 to 30 MPa, still more preferably 1 to 10 MPa, and particularly preferably 4 to 6 MPa as the carbon monoxide pressure. By setting the reaction pressure within such a range, the reaction rate can be increased. Moreover, it is not necessary to increase the design pressure of equipment such as a reactor, and the equipment burden can be reduced.

After the reaction, the heterogeneous catalyst (A) can be easily separated from the reaction solution by a separation operation usually used for separation of liquid and solid such as filtration and centrifugation. The separated catalyst can be reused in the epoxide carbonylation reaction. It is also possible to separate the target four-membered lactone from the reaction solution by an operation such as distillation, collect the distillation residue containing the catalyst and the solvent, and reuse it for the epoxide carbonylation reaction.
The four-membered ring lactone obtained by the production method of the present invention is dissolved in a solvent, or after isolation / purification, and then a raw material for polymerization of a biodegradable resin or a synthetic raw material such as acrylic acid or succinic anhydride Can be used as Isolation / purification of the four-membered ring lactone can be carried out according to conventional methods such as distillation, recrystallization, reprecipitation, solvent extraction, chromatography and the like.

<Catalyst X>
The catalyst X of the present invention uses, as a carrier, an oxide of one or more metals selected from Group 5 to Group 10 transition metals, and the carrier includes at least selected from Group 10 transition metals and oxides thereof. It is a heterogeneous catalyst used for epoxide carbonylation reaction, in which one kind is supported (however, the supported substance is different from the metal oxide used as a carrier). Among the heterogeneous catalysts used in the production method of the present invention, the catalyst X exhibits a particularly high catalytic activity in the epoxide carbonylation reaction and is particularly useful as a catalyst used in the above reaction.
(Carrier)
Examples of the transition metal in the support of the catalyst X of the present invention include a Group 5 transition metal such as vanadium (V); a Group 6 transition metal such as chromium (Cr), molybdenum (Mo), tungsten (W); Group 7 transition metals such as (Mn) and rhenium (Re); Group 8 transition metals such as iron (Fe), ruthenium (Ru) and osmium (Os); cobalt (Co), rhodium (Rh), Group 9 transition metals such as iridium (Ir); Group 10 transition metals such as nickel (Ni). Among these, transition metals of Group 8 to Group 9 are preferable, iron (Fe) and cobalt (Co) are more preferable in terms of inexpensiveness, and cobalt (Co) is particularly preferable in terms of catalytic activity.
Specific examples of the support for the catalyst X include iron oxide (eg, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ), cobalt oxide (eg, CoO, Co ₂ O ₃ , Co ₃ O _4, etc.). Etc.), but cobalt oxide is particularly preferred from the viewpoint of catalytic activity.
The transition metal oxide may be a single metal oxide or a composite oxide of two or more metals. Moreover, the mixture of the oxide from which the valences of the same metal differ may be sufficient.

(Supported material)
Further, examples of the Group 10 transition metal in the supported material of the catalyst X include platinum (Pt), palladium (Pd), and the like, and one of these may be used, or two or more thereof may be used. Among these, palladium (Pd) is particularly preferable from the viewpoint of catalytic activity.
Note that a metal species different from the metal oxide used as the carrier is used for the transition metal in the supported object. That is, when the metal species in the carrier is palladium, the metal species in the supported material is not palladium, and when the metal species in the carrier is nickel, the metal species in the supported material is not nickel and the metal species in the carrier is platinum. In this case, the metal species in the supported object is not platinum.
Moreover, palladium oxide etc. are mentioned as an oxide of a group 10 transition metal. The transition metal oxide may be a mixture of oxides of different valences of the same metal. In the oxide of the transition metal, catalytic activity can be imparted by reducing part or all of the transition metal by the pretreatment that is brought into contact with the hydrogen or the mixed gas containing hydrogen and carbon monoxide.

The supported amount of the supported material is not particularly limited, but is preferably 0.1 atomic% or more, more preferably 1 atomic% or more, and preferably 50 atomic% or less with respect to the total amount of metal in the catalyst X. More preferably, it is 30 atomic percent or less, more preferably 20 atomic percent or less, and particularly preferably 14 atomic percent or less. By setting the amount of the supported material in such a range, the catalytic activity is further improved.
The “atomic%” in the present invention can be determined from the mol% of the precursor of the supported substance in the total moles of the precursor of the support and the precursor of the supported substance used in the catalyst preparation stage.

Further, the shape of the catalyst X is not particularly limited, and those having an arbitrary shape such as powder, crushed, particulate, and columnar can be used. In the present invention, one type of catalyst may be used alone, or two or more types of catalysts having different types and supported amounts; different specific surface areas or shapes of the catalysts may be used in combination.
Further, the catalyst X is preferably one in which a nanoparticle layer of a supported material is formed on the surface of the carrier.

  The method for supporting these transition metals and the like (supported materials) on the carrier is not particularly limited, but, for example, a compound containing in the molecule a Group 5 to Group 10 transition metal capable of forming a metal oxide serving as a carrier. A solution containing (compound α) and a compound containing a Group 10 transition metal (different from a transition metal serving as a carrier) in the molecule (hereinafter also referred to as compound γ) is reacted with a precipitant to produce a precipitate. There is a method of precipitating (coprecipitation method). By separating the precipitate deposited by the coprecipitation method and baking it, nanoparticles of the supported material can be formed on the surface of the carrier.

The type and form of compound α are not particularly limited, but it is preferably used as an aqueous solution using a water-soluble metal salt. Examples of the metal salt include halides such as chloride, bromide and iodide; salts of inorganic acids such as nitrates and sulfates; salts of organic acids such as acetates and the like. These metal salts may be used alone or in combination of two or more.
The type and form of compound γ are not particularly limited, but it is preferably used as an aqueous solution using a water-soluble metal salt or complex salt. Examples of the metal salt include halides such as chloride, bromide and iodide; salts of inorganic acids such as nitrates and sulfates; salts of organic acids such as acetates and the like. Examples of complex salts include chloroplatinic acid, chloropalladic acid, and salts thereof. Moreover, these metal salts and metal complex salts may be used by 1 type, or may be used by 2 or more types.

Examples of the precipitating agent include alkalis such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
Concentration of aqueous solution used at the time of coprecipitation, temperature, addition rate of precipitating agent, etc. can be set as appropriate. By controlling these, physical properties such as the amount of supported metal and specific surface area can be adjusted to the desired range. can do.
In addition, the catalyst X includes a catalyst that has been subjected to a pretreatment that is brought into contact with the hydrogen or a mixed gas containing hydrogen and carbon monoxide.

  The catalyst X thus obtained has a high catalytic activity as a catalyst for the epoxide carbonylation reaction, is easy to handle and separate from the product, can be used repeatedly, As described in the method for producing a ring lactone, it is very suitable for use in the production of a four-membered ring lactone.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

<Preparation of heterogeneous catalyst>
(Catalyst Preparation Example 1: Preparation of PdO-supported catalyst (Catalyst A) (Catalyst X of the present invention))
A 10 atomic% PdO / Co ₃ O ₄ catalyst (Catalyst A) was prepared by the following procedure (coprecipitation method).
Distillation of 1.0M aqueous solution of palladium nitrate _{(Pd (NO 3) 2)} 2.3mL (2mmol) and cobalt (II) nitrate hexahydrate _{(Co (NO 3) 2 ·} 6H 2 O) 5.24g (18mmol) Dissolved in 200 mL of water and stirred for 10 minutes. In another beaker, 2.66 g (26 mmol) of sodium carbonate (Na ₂ CO ₃ ) was dissolved in 200 mL of distilled water and stirred for 10 minutes. The palladium nitrate and cobalt nitrate solutions prepared above were all added dropwise to the sodium carbonate solution, and then stirred at room temperature for 8 hours. When the stirring was stopped, a brown solid precipitated, and thus filtration was performed. The brown solid was washed twice with 100 mL of distilled water. The solid matter remaining after washing was dried at 80 ° C. for 10 hours, and then baked using an electric furnace. Firing was performed by raising the temperature from room temperature to 300 ° C. over 1 hour and at 300 ° C. for 2 hours. Then, after standing to cool to room temperature, it took out from the electric furnace and obtained the target catalyst A.

(Catalyst Preparation Example 2: Preparation of PdO-supported catalyst (Catalyst B) (Catalyst X of the present invention))
Similar to Catalyst Preparation Example 1 except that the amount of palladium nitrate aqueous solution used was changed to 2.5 mmol in terms of palladium nitrate and the amount of cobalt nitrate (II) hexahydrate was changed to 17.5 mmol. A 12.5 atomic% PdO / Co ₃ O ₄ catalyst (Catalyst B) was prepared by the procedure.

(Catalyst Preparation Example 3: Preparation of PdO-Supported Catalyst (Catalyst C) (Catalyst X of the Present Invention))
The amount of palladium nitrate aqueous solution was changed to 3 mmol in terms of palladium nitrate, and the amount of cobalt nitrate (II) hexahydrate was changed to 17 mmol by the same procedure as in Catalyst Preparation Example 1, 15 atoms. A% PdO / Co ₃ O ₄ catalyst (Catalyst C) was prepared.

(Catalyst Preparation Example 4: Preparation of Pt-Supported Catalyst (Catalyst D) (Catalyst X of the Present Invention))
Instead of using an aqueous palladium nitrate solution, 0.415 g (1 mmol) of potassium platinum (II) chloride (K ₂ PtCl ₄ ) was used, and the amount of cobalt nitrate (II) hexahydrate was changed to 19 mmol. Prepared a 5 atomic% Pt / Co ₃ O ₄ catalyst (Catalyst D) by the same procedure as in Catalyst Preparation Example 1.

(Catalyst Preparation Example 5: Preparation of Au-supported catalyst (catalyst E))
Instead of palladium nitrate aqueous solution, 0.164 g (0.4 mmol) of gold chloride (III) acid tetrahydrate (HAuCl ₄ .4H ₂ O) was used, and the amount of cobalt nitrate (II) hexahydrate used Was changed to 19.6 mmol, and a 2 atom% Au / Co ₃ O ₄ catalyst (catalyst E) was prepared by the same procedure as in Catalyst Preparation Example 1.

  The obtained catalysts A to E were used for the reaction after being pretreated at 120 ° C. for 3 hours with a hydrogen / carbon monoxide mixed gas (1/3) (pressure 2 MPa) unless otherwise specified. . In the pretreated PdO-supported catalysts (catalysts A, B, and C), the formation of Pd (0) was confirmed by X-ray absorption near edge structure (XANES) analysis.

<Carbonylation reaction>
Example 1
In a 50 mL stainless batch type pressure and heat resistant reaction vessel containing 200 mg of pretreated catalyst A, 10 mL of tetraglyme as Lewis base and solvent, 1.0 mL of 1.0 M diethylaluminum chloride hexane solution as Lewis acid, and as epoxide 2.9 g (66 mmol) of ethylene oxide was introduced in sequence.
Next, the reaction vessel was attached to an oil bath, and while stirring the mixture, the temperature was raised to 100 ° C. and the temperature was maintained. Next, carbon monoxide gas was charged to 4.0 MPa in the reaction vessel, and the reaction was carried out for 7.5 hours while maintaining the pressure. When a predetermined time had passed, the mixture was cooled, degassed, and the lid was opened to obtain a product. The product of the carbonylation reaction was identified by a gas chromatograph mass spectrometer (GC-MS). Here, GC-MS analysis is performed by attaching a TC-1 column (length 60 m, diameter 0.25 mm) made by GL Science to Shimadzu gas chromatograph mass spectrometer (model: GCMS-QP-2010), and using helium. It was performed using as a carrier gas.
As a result of GC-MS analysis, formation of β-propiolactone was confirmed. The yield of the obtained β-propiolactone is shown in Table 1.

(Example 2)
The carbonylation reaction of ethylene oxide was performed in the same procedure as in Example 1 except that triethylaluminum was used as the Lewis acid. The results are shown in Table 1.

(Example 3)
A carbonylation reaction of ethylene oxide was carried out by the same procedure as in Example 1 except that the reaction time was 5 hours. The results are shown in Table 1.
(Examples 4 to 7)
The carbonylation reaction of ethylene oxide was carried out by the same procedure as in Example 3 except that the Lewis acid shown in Table 1 was used as the Lewis acid. The results are shown in Table 1.
(Example 8)
The carbonylation reaction was performed in the same procedure as in Example 3 except that propylene oxide was used as the epoxide. The results are shown in Table 1.

(Comparative Example 1)
A carbonylation reaction of ethylene oxide was carried out by the same procedure as in Example 3 except that the reaction was carried out without using a Lewis acid. The results are shown in Table 1.

In addition, the following formula in Table 1 means the following Lewis acids.
Y (OTf) ₃ : Yttrium triflate La (OTf) ₃ : Lanthanum triflate

  As shown in Table 1, the carbonyl of the epoxide using the heterogeneous catalyst (A) (catalyst A) in the presence of a metal Lewis acid (B) such as a metal halide or metal triflate and a Lewis base (C). By carrying out the conversion reaction, the catalytic activity was dramatically improved as compared with the case where the metal Lewis acid (B) was not used (Comparative Example 1). It can be seen that the effect is particularly remarkable when an organoaluminum compound is used as the metal Lewis acid (B).

Example 9
Carbonylation of ethylene oxide was carried out in the same manner as in Example 3 except that the reaction temperature was 75 ° C. and carbon monoxide was charged to a pressure of 4.0 MPa, and the reaction was performed without supplementing carbon monoxide during the reaction. Reaction was performed. The results are shown in Table 2.
(Examples 10 to 12)
A carbonylation reaction of ethylene oxide was performed by the same procedure as in Example 9 except that various glymes described in Table 2 were used as the Lewis base. The results are shown in Table 2.

(Examples 13 to 15)
A carbonylation reaction of ethylene oxide was carried out by the same procedure as in Example 4 except that the Lewis base shown in Table 2 was used as the Lewis base. The results are shown in Table 2.
(Comparative Example 2)
A carbonylation reaction of ethylene oxide was carried out by the same procedure as in Example 4 except that Lewis base was not used and 10 mL of hexane was added as a solvent instead. The results are shown in Table 2.

  As shown in Table 2, using a heterogeneous catalyst (A) (catalyst A), a Lewis base containing a metal Lewis acid (B) and an oxygen atom such as glycol dialkyl ether or THF in the molecule, pyridine Compared with the case where Lewis base (C) is not used (Comparative Example 2) by carrying out carbonylation reaction of epoxide in the presence of Lewis base (Lewis base (C)) containing nitrogen atoms in the molecule such as acetonitrile and acetonitrile. As a result, the catalytic activity improved dramatically. It can be seen that the effect is particularly remarkable when glycol dialkyl ether is used as the Lewis base (C).

(Examples 16-22, Comparative Examples 3-5)
Propylene oxide carbonyls under the conditions shown in Table 3 using any of catalysts B, C, D, and E, and using a stainless steel 20 mL batch pressure- and heat-resistant reaction vessel with a glass tube inside. The reaction was carried out according to the procedure of Example 8. In Examples 17 and 18, catalyst B having different pretreatment conditions was used. In Example 20, trimethylaluminum was used as the Lewis acid, and diethylaluminum chloride was used in the other examples. Moreover, in the comparative example, it reacted without using a Lewis acid. The results are shown in Table 3.

(Example 23)
Using catalyst A, the carbonylation reaction of 1-octene oxide was carried out according to Example 16 under the conditions shown in Table 3. The results are shown in Table 3.

  As shown in Table 3, the present invention is directed to carbonylation of epoxides using a group 10 transition metal such as Pd and Pt, a group 11 transition metal such as Au, and a catalyst supporting these oxides. Applicable to reaction. In particular, it can be seen that the effect is significant when the supported material is a Group 10 transition metal or an oxide thereof (Examples 16 to 21), and among them, when the transition metal is Pd.

Claims (11)

A method for producing a four-membered lactone by carbonylation of an epoxide, comprising epoxide and carbon monoxide,
(A) An oxide of one or more metals selected from Group 5 to Group 10 transition metals is used as a carrier, and Group 10 transition metal, Group 11 transition metal, and oxides thereof are used as the carrier. A heterogeneous catalyst in which one or more selected from the above are supported (however, the supported material is different from the metal oxide used as the carrier),
(B) a metal Lewis acid;
(C) A method for producing a four-membered ring lactone, comprising a step of reacting in the presence of a Lewis base containing an atom selected from an oxygen atom and a nitrogen atom in the molecule.   2. The production method according to claim 1, wherein the metal Lewis acid (B) is one or more selected from an organometallic compound, a metal halide, and a metal triflate.   The manufacturing method according to claim 1, wherein the metal Lewis acid (B) is an organoaluminum compound.   The manufacturing method according to any one of claims 1 to 3, wherein the Lewis base (C) is one or more selected from a chain ether, a cyclic ether, a chain amine, a cyclic amine, and a nitrile.   The said Lewis base (C) is glycol dialkyl ether, The manufacturing method of any one of Claims 1-3.   6. The pretreatment in which hydrogen or a mixed gas containing hydrogen and carbon monoxide is brought into contact with the heterogeneous catalyst (A) before performing the carbonylation reaction. Manufacturing method.   The production method according to any one of claims 1 to 6, wherein the supported material of the heterogeneous catalyst (A) is one or more selected from palladium, platinum, gold, and oxides thereof. .   The production method according to any one of claims 1 to 7, wherein the support for the heterogeneous catalyst (A) is cobalt oxide.   One or more metal oxides selected from Group 5 to Group 10 transition metals are used as a carrier, and the carrier is supported with at least one member selected from Group 10 transition metals and oxides thereof. , Heterogeneous catalyst used for epoxide carbonylation reaction (however, the supported material is different from the metal oxide used as the carrier).   The heterogeneous catalyst according to claim 9, wherein the supported material is at least one selected from palladium and an oxide thereof.   The heterogeneous catalyst according to claim 9 or 10, wherein the support is cobalt oxide.