JP2004107340A - Method for producing allyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing various allyl compounds, by using a new catalyst system produced at a low cost, having excellent heat stability, and exhibiting high catalytic activity when the new allyl compound different from a raw material compound for the allyl compound is produced by reacting the raw material compound with a nucleophile. <P>SOLUTION: This method for producing the allyl compound comprises reacting the raw material compound for the allyl compound with the nucleophile in the presence of a catalyst containing one or more transition metal compounds and one or more bidentate phosphite compounds, wherein the transition metal compound is formed out of a metal selected from a group comprising transition metals belonging to the 8 to 10 groups in the periodic table, and the bidentate phosphite compound is expressed by general formula (I): (R<SP>11</SP>O)(R<SP>12</SP>O)P-O-A<SP>1</SP>-O-P(OR<SP>13</SP>)(OR<SP>14</SP>) (A<SP>1</SP>is a diarylene group having branched alkyl groups at the ortho positions; and R<SP>11</SP>to R<SP>14</SP>are each an alkyl group which may be substituted or an aryl group which may be substituted) or the like. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a method for producing a new allyl compound different from a raw material compound by reacting an allyl raw material compound with a nucleophile in the presence of a catalyst comprising a transition metal compound and a phosphite compound.

Various kinds of new allyl compounds can be synthesized by performing a catalytic reaction using a transition metal compound using the allyl compound as a raw material. As shown in the following reaction formula, the allyl raw material compound having a leaving group X is π-coordinated and oxidatively added to the transition metal compound, so that the three carbons of the allyl moiety are bonded to the metal. - allyl complexes are formed, the terminal allyl carbon of π- allyl complexes Nu-H or Nu ^- proceeds by being attacked by a nucleophilic agent represented by.

The details of the synthesis reaction of the allyl compound are summarized and described in Non-Patent Document 1, but by selecting the type of the nucleophile in the reaction, various types of allylic forms of the nucleophile can be obtained. The product can be obtained.

For example, when the nucleophile is malonic diester, a malonic diester having an allyl group bonded thereto is formed (allyl alkylation reaction), and when the nucleophilic agent is a primary or secondary amine, allylamine is used. Are formed (allyl amination reaction), and when the nucleophilic agent is phenol or carboxylic acid, allyl phenyl ether or carboxylic acid allyl ester is formed, respectively.

On the other hand, a palladium compound is most famous as a transition metal compound serving as a catalyst, but a catalytic reaction of an allyl compound is also known among ruthenium compounds, nickel compounds, iridium compounds and the like. In addition, various ligands have been developed which coordinate with such transition metal compounds to promote improvement of catalytic activity, regioselectivity of reaction, and optical selectivity.

When the above-mentioned allylation reaction using a catalyst is carried out on an industrial scale, the purpose is to reduce the amount of catalyst used to reduce catalyst costs, or to reduce the size of the reactor to reduce construction costs. Therefore, it is strongly desired to improve the reactivity of the catalyst. Further, in order to reduce the cost of the catalyst itself, it is necessary to reduce the production cost of the ligand used. From such a viewpoint, in the bidentate phosphite ligands described in Non-Patent Document 2 and Non-Patent Document 3, the cross-linking portion is composed of glucose and the P-O-C bond of the cross-linking portion. Since the carbon atom in is a sp ³ carbon atom having an alkyl group, the ligand has low thermal stability and is not suitable for a reaction at a high temperature at which the catalyst exhibits high activity.

In addition, Patent Document 1, which has recently been reported, discloses a reaction between an allyl ester raw material compound and a carbon nucleophile using a bidentate phosphite ligand having an axial asymmetry in a biphenol portion of a cross-linking portion (allyl). Alkylation reaction) and reaction with a nitrogen nucleophile (allyl amination reaction) are described, but it is not described that a phosphite compound having a specific structure is suitably used for the allylation reaction.

"Palladium Reagents and Catalysts -Innovations in Organic Synthesis-", published by John Wiley & Sons Chem. Commun., 2001, p1132 J. Org. Chem., 2001, 66, p8867 WO2002-044041

As described above, in order to produce various allyl compounds by reacting an allyl raw material compound with a nucleophile on an industrial scale, reduction of catalyst cost is one of the important items. Methods for reducing catalyst costs include reducing the amount of catalyst used by improving reactivity, reducing ligand costs by using inexpensive ligands, and recycling by using stable ligands. However, when a phosphine-based ligand, which is relatively difficult to synthesize, is used, or a complex bidentate ligand such as PN, PO, PS, NS, When a bidentate ligand having axial asymmetry is used, the production cost of the ligand increases. Even a bidentate phosphite ligand that is relatively easy to synthesize is sufficient when the carbon atom in the P—O—C bond of the bridge is an alkyl-based sp ³ carbon. Since thermal stability is not obtained, it is difficult to carry out a highly active reaction at a high temperature. Therefore, development of a new catalyst system using a ligand which can be manufactured at low cost, has excellent thermal stability, and can realize high activity has been desired.

The present invention has been made in view of the above problems. That is, an object of the present invention is to industrially produce various allyl compounds efficiently using a new catalyst system which can be produced at low cost, has excellent thermal stability, and expresses high activity. An object of the present invention is to provide an advantageous method for producing an allyl compound.

The present inventors have been diligently studying the development of a catalyst system capable of efficiently proceeding the intermolecular reaction between various allylic compounds and a nucleophile. A specific bidentate phosphite ligand having a sp ² carbon atom derived from an aryl group and having a branched alkyl group at the ortho position of the aryl group, The present inventors have found that a catalyst having a particularly high activity can be obtained when used in combination with a transition metal compound belonging to Groups 8 to 10 of the periodic table, and arrived at the present invention.

That is, the gist of the present invention is represented by one or more transition metal compounds containing a transition metal selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table and the following general formulas (I) to (III). In the presence of a catalyst containing at least one bidentate phosphite compound selected from the group consisting of compounds having the structure shown below, by reacting the allylic compound with a nucleophile, the allylic compound differs from the allylic compound. A method for producing an allyl compound, characterized by producing a new allyl compound having a composition formula.

(In the above general formulas (I) to (III), A ^{1 to} A ³ each independently represent a diarylene group having a branched alkyl group at the ortho position. R ^{11 to} R ¹⁶ each independently represent a substituent represents an aryl group which may have an alkyl group or a substituted group may have a (including the heterocyclic compound forming the aromatic 6π electron cloud and below the ring. forth.) .Z ¹ To Z ³ are each independently an alkylene group which may have a substituent, an arylene group which may have a substituent, an alkylene-arylene group which may have a substituent, or a substituent Represents a diarylene group which may have

According to the method for producing an allyl compound of the present invention, when a new allyl compound is produced by reacting an allyl raw material compound with a nucleophile, it can be produced at low cost, has excellent thermal stability, and has high catalytic activity. Since a new catalyst system that expresses is used, various types of allyl compounds can be efficiently produced as compared with the case where a conventional catalyst system is used, which is industrially advantageous.

Hereinafter, the present invention will be described in detail.
The method for producing an allyl compound according to the present invention (hereinafter, abbreviated as “the production method of the present invention” as appropriate) includes a specific transition metal compound described below and a bidentate phosphite compound having a specific structure also described later. A new allyl compound having a composition formula different from that of the allyl raw material compound by reacting the allyl raw material compound with a nucleophile in the presence of a catalyst containing

First, the allyl raw material compound used in the production method of the present invention will be described.
The allyl raw material compound is not particularly limited as long as it has an allyl group and a leaving group in the molecule, but has an overall molecular weight of 1500 or less (having a carbon number of about 100 or less) under the reaction conditions. It is preferable that all or a part of the allyl raw material compound can be in a dissolved state by dissolution in a solvent, compatibility with an oxygen nucleophile, or melting by heat. Among them, a compound having a structure in which a leaving group represented by X is bonded to an allyl group having a group represented by R ^{a to} R ^e represented by the following general formula (a) is preferable. In addition, a leaving group is bonded to carbon of a substrate skeleton (an allyl skeleton in the present invention) serving as a parent, and is generally an electron-withdrawing group, which has an electron pair and is separated from a substrate molecule by an atom or Refers to an atomic group.

In the formula ^(a), R a ~R ^e are each independently a hydrogen atom, a halogen atom, hydroxy group, an amino group, a formyl group, a linear or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group , An alkylthio group, an arylthio group, an acyl group, or an acyloxy group (in the present specification, the aryl group includes a heterocyclic compound that forms an aromatic 6π electron cloud above and below a ring). Among these exemplified groups, the amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, and acyloxy group may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a linear or cyclic alkyl group. , An aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

Preferably, R ^{a to} R ^e are preferably a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a linear or cyclic alkyl group which may be substituted with the above substituent, and may be substituted with the above substituent. An aryl group, an alkoxy group optionally substituted with the above substituent, an aryloxy group optionally substituted with the above substituent, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group, more preferably hydrogen. Atom, halogen atom, hydroxy group, amino group, chain or cyclic alkyl group optionally substituted with the above substituent, aryl group optionally substituted with the above substituent, alkoxy group, arylalkoxy group, aryloxy Groups, alkylaryloxy groups, alkylthio groups, arylthio groups, acyl groups, and acyloxy groups.

The number of carbon atoms in R ^a to R ^e is usually 40 or less, preferably 30 or less, more preferably 20 or less. Note that when R ^a to R ^e is a group containing a carbon chain, one or more carbons in its carbon chain - may be present carbon double bond or triple bond.
Among the above examples, as the R ^a to R ^e, independently, a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group.

基 Examples of the group that adversely affect the reaction system include those that poison the catalyst, for example, a group containing a conjugated diene, and those that oxidize and disappear a phosphite compound, for example, a group containing a peroxide. Therefore, throughout this specification, the term “having no risk of adversely affecting the reaction system” means that those groups that adversely affect the reaction system are excluded.

On the other hand, the leaving group X is a halogen atom, a hydroxy group, a nitro group, an amino group represented by R ′ ₂ N—, a sulfonyl group represented by RSO ₂ —, a sulfonate group represented by RSO ₂ O—, RC (= O) O- represented by an acyloxy group, R'OC (= O) O- represented by a carbonate group, R'NHC (= O) O- with carbamate group _{represented, (R'O) 2 P (=} O ) A phosphate group represented by O-, an alkoxy group represented by RO- or an aryloxy group. In the above formulas, R represents a monovalent organic group, and R 'represents a hydrogen atom or a monovalent organic group. The type of the organic group is not particularly limited as long as it does not adversely affect the reaction system, but an alkyl group or an aryl group is preferable. When R is an organic group, the number of carbon atoms is usually 40 or less, preferably 30 or less, more preferably 20 or less. Of these exemplified groups, an amino group, a sulfonyl group, a sulfonate group, an acyloxy group, a carbonate group, a carbamate group, a phosphate group, an alkoxy group, or an aryloxy group may further have the above substituent. When the leaving group X is a group containing a carbon chain, one or more carbon-carbon double bonds or triple bonds may be present in the carbon chain.

In the above examples, X represents a hydroxy group, an acyloxy group having a skeleton structure represented by —C (＝ O) O—, a carbonate group, and a carbamate group, and a skeleton structure represented by ＰP (＝ O) —. phosphates group having, and -S (= O) are preferred Suruhoneito group having a skeleton structure represented by ₂ O-, inter alia hydroxy group, an acyloxy group and a carbonate group are preferred. Specific examples of the acyloxy group include a C1 to C6 acyloxy group such as an acetoxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. Specific examples of the carbonate group include a C1 to C6 alkyl carbonate group such as a methyl carbonate group, an ethyl carbonate group, and a phenyl carbonate group, and an aryl carbonate group. Particularly, X is preferably an acetoxy group or a hydroxy group, and most preferably an acetoxy group.

In addition, any two or more groups among the above-described R ^{a to} R ^e and X may be bonded to each other to form one or more cyclic structures. However, it is not preferable that X is contained in a stable cyclic structure, because X is difficult to be eliminated. The number of rings is not particularly limited, but is usually 0 to 3, preferably 0 to 2, and particularly preferably 0 or 1. Although the number of atoms forming each ring is not particularly limited, it is usually a 3- to 10-membered ring, preferably a 4- to 9-membered ring, particularly preferably a 5- to 7-membered ring. When a plurality of rings are present, these rings may share a part to form a fused ring structure.

If two or more groups of R ^a to R ^e and X form a cyclic structure bound, the number of carbon atoms, when the number of groups that are involved in the formation of the cyclic structure and p, usually 0 -40 × p, preferably 0-30 × p, particularly preferably 0-20 × p.

As examples of the allyl raw material compound represented by the general formula (a), preferably, allyl halides, allyl alcohols, nitroallyls, allylamines, allyl sulfones, allyl sulfonates, allyl esters of carboxylic acid, Examples include allyl carbonates, allyl carbamates, allyl phosphates, allyl ethers, and vinyl ethylene oxide.

Specific examples of allyl halides include allyl chloride, 2-butenyl bromide, 1-chloro-2-phenyl-2-pentene, and the like.
Specific examples of allyl alcohols include 2-butenyl alcohol, 2,3-dimethyl-2-butenyl alcohol, 3-bromoallyl alcohol, cinnamyl alcohol, crotyl alcohol, and 3-methyl-2-cyclohexene-1. -Ol, 3-methyl-2-buten-1-ol, geraniol, 2-penten-1-ol, 3-buten-2-ol, 1-hexen-3-ol, 2-methyl-3-phenyl-2 -Propen-1-ol, 1-acetoxy-4-hydroxycyclopentene-2, 1,2-dihydrocatechol, 3-hexene-2,5-diol and the like.
Specific examples of nitroallyls include 1-nitro-2-butene, 1-nitro-1,3-diphenylpropene, 3-nitro-3-methoxypropene, and the like.

Specific examples of allylamines include allyldiethylamine, 3-methoxyallyldiphenylamine, triallylamine, and 2-butenyldibenzylamine.
Specific examples of allyl sulfones include allyl phenyl sulfone, methylyl-p-tolylsulfone, 2-methyl-3-sulfolene, and 1,3-diphenylallylmethyl sulfone.
Specific examples of allylsulfonates include allyltoluene-4-sulfonate, 3-thiophenemethanesulfonate, 4-chloro-2-butenylmethanesulfonate, and the like.

Specific examples of allylic esters of carboxylic acids include allyl acetate, 2-hexenyl acetate, 2,4-hexadienyl acetate, prenyl acetate, geranyl acetate, farnesyl acetate, cinnamyl acetate, linalyl acetate, and 3-butene acetate. 2-yl, 2-cyclopentenyl acetate, 2-trimethylsilylmethyl-2-propenyl acetate, 2-methyl-2-cyclohexenyl acetate, 1-phenyl-1-buten-3-yl propionate, butyric acid Examples thereof include 1-cyclohexyl-2-butene, 4-cyclopentene-1,3-diol-1-acetate, 1,4-diacetoxybutene-2, and 3-acetoxy-4-hydroxybutene-1.

Specific examples of allyl carbonates include allyl methyl carbonate, 4-acetoxy-2-butenylethyl carbonate, neryl methyl carbonate, and the like.
Specific examples of the allyl carbamates include allyl-N- (4-fluorophenyl) carbamate, 2-butenyl-N-methylcarbamate, and furfuryl-N- (2-methoxydiphenyl) carbamate.
Specific examples of allyl phosphates include allyl dimethyl phosphate, 3-methyl-2-butenyl diphenyl phosphate, and methyl ethyl furfuryl phosphate.

Specific examples of allyl ethers include allyl ethyl ether, allyl phenyl ether, 2,3-diphenyl allyl isopropyl ether, 2-butenyl-4-fluorophenyl ether, and the like.
Specific examples of vinyl ethylene oxides include butadiene monoxide, cyclopentadiene monoxide, 1,3-cyclohexadiene monoxide and the like.

As particularly preferred allyl raw material compounds, 3,4-disubstituted butene-1 represented by the following general formula (b), 1,4-disubstituted butene-2 represented by the following general formula (c), and Examples thereof include a mixture of two or more compounds selected from the group consisting of compounds.

^{_{CH 2 = CH-CHR 1 -CH}} 2 R 2. . . General formula (b)
In the general formula (b), R ¹ and R ² each independently represent an acetoxy group or a hydroxy group. Specific examples of the 3,4-disubstituted butene-1 represented by the general formula (b) include 3,4-diacetoxybutene-1, 3-acetoxy-4-hydroxybutene-1, and 4-acetoxy-3. -Hydroxybutene-1, and 3,4-dihydroxybutene-1.

R ³ CH ₂ —CH ＝ CH—CH ₂ R ⁴ . . . General formula (c)
In the general formula (c), R ³ and R ⁴ each independently represent an acetoxy group or a hydroxy group. Specific examples of the 1,4-disubstituted butene-2 represented by the general formula (c) include 1,4-diacetoxybutene-2, 1-acetoxy-4-hydroxybutene-2, and 1,4-diacetoxybutene-2. Dihydroxybutene-2.

Next, the nucleophile used in the production method of the present invention will be described. Generally, a nucleophile refers to a reactant having an unshared electron pair, being basic and having a tendency to attack a carbon nucleus, but the type is not particularly limited in the present invention, Essentially any kind of nucleophile can be used. However, for the purpose of generating an allyl compound by nucleophilic attack on the π-allyl complex, the nucleophile used in the present invention requires an unshared electron pair on an oxygen atom, a carbon atom, and a nitrogen atom, respectively. Oxygen nucleophiles, carbon nucleophiles, and nitrogen nucleophiles that perform a nuclear attack are preferred. In order to increase the reaction rate, all or a part of the nucleophile is dissolved under the reaction conditions due to dissolution in a solvent, compatibility with an allyl raw material compound, or melting by heat. What is obtained is preferred. From such a viewpoint, a nucleophile having a molecular weight of 600 or less is usually used.

Specifically, the oxygen nucleophile usable in the present invention is a compound of a proton adduct represented by E ¹ O-H containing a nucleophilic oxygen atom, or E ¹ O which is a deprotonated product thereof. ^- anion represented by, further, a compound that may be the anion in the reaction system. In the above formula, E ¹ represents a hydrogen atom or an organic group. The organic group is a group bonded to the nucleophilic oxygen atom by a carbon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom, becomes a liquid in the reaction system, and has no possibility of adversely affecting the reaction system. Things are used.

When E ¹ is an organic group, the number of carbon atoms is usually preferably 30 or less, because it is easily dissolved in the reaction system. Especially, it is preferably 20 or less, particularly preferably 10 or less. The molecular weight of the oxygen nucleophile is usually 400 or less, preferably 300 or less, particularly preferably 200 or less.

Examples of the organic group bonded to the nucleophilic oxygen with a carbon atom include an unsubstituted or substituted chain alkyl group, an unsubstituted or substituted cyclic alkyl group, and an unsubstituted or substituted aryl group.
Examples of the organic group bonded to a nucleophilic oxygen with a nitrogen atom include an unsubstituted or substituted amino group and a group having a C ＝ N bond.
Examples of the organic group bonded to the nucleophilic oxygen with a phosphorus atom include an unsubstituted or substituted phosphonate group, a phosphinate group, a phosphinoyl group, and the like.
Examples of the organic group bonded to the nucleophilic oxygen with a sulfur atom include an unsubstituted or substituted sulfonyl group.
The substituent of each of the above-mentioned exemplary groups is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, or a chain. Alternatively, a cyclic alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkylthio group, arylthio group, perfluoroalkyl group, trialkylsilyl group, alkoxycarbonyl group, or aryloxycarbonyl group is preferable. When each of the exemplified groups has these substituents, the number of carbon atoms including the substituents is set to fall within the above range.

However, even if the oxygen nucleophile falls under the above definition, when it is used in the reaction, the substituent (X in the above general formula (a) or its anion X) which is eliminated from the allyl raw material compound by the reaction. ^- ) Or the same as the protonated product thereof (XH), the reaction does not proceed apparently, or an isomer having the same compositional formula as the allyl raw material compound but a different structure is formed. , Such oxygen nucleophiles are excluded.

When specific examples of the oxygen nucleophile are listed in the form of a protonated product, when E ¹ is a hydrogen atom, it is water.
When E ¹ is an organic group bonded to a nucleophilic oxygen by a carbon atom, examples thereof include hydroxy compounds, carboxylic acids, thiocarboxylic acids, and selenocarboxylic acids.
Specific examples of the hydroxy compound include methanol, ethanol, n-propanol, n-butanol, sec-butanol, t-butanol, allyl alcohol, 2-ethylhexyl alcohol, 4-chloro-1-butanol, benzyl alcohol, cycloalkyl Alcohols such as hexanol, ethylene glycol, 1,3-propanediol, and 1,4-butanediol; phenol, p-methoxyphenol, 2,4-dimethylphenol, 1-naphthol, 2-naphthol, and 3,6-diphenol Phenols such as -t-butyl-2-naphthol, 2-pyridinol or 2, -bromo-4-pyridinol; and heteroaryl compounds having a hydroxyl group such as 2-pyridinol and 2-bromo-4-pyridinol. .
Specific examples of the carboxylic acids include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, chloroacetic acid, oxalic acid, and adipic acid; benzoic acid, naphthalene-2-carboxylic acid, m-cyanobenzoic acid, and o-toluic acid. And other aromatic carboxylic acids.
Specific examples of the thiocarboxylic acids include a compound represented by CH ₃ C (＝ S) —OH, a compound represented by PhC (＝ S) —OH, and the like.
Examples of selenocarboxylic acids, compounds represented by _{CH 3 (C = Se) -OH} , PhC (= Se) compounds represented by -OH, and the like. In this specification, Ph represents a phenyl group.

When E ¹ is an organic group bonded to a nucleophilic oxygen and a nitrogen atom, hydroxyamines such as N, N-diethylhydroxyamine, N, N-dibenzylhydroxyamine; acetone oxime, benzophenone oxime, cycloalkyl Oximes such as pentanone oxime; carbamates such as t-butyl-N-hydroxycarbamate; imides such as N-hydroxymaleimide and N-hydroxysuccinimide; and 1-hydroxybenzotriazole.

When E ¹ is an organic group bonded to a nucleophilic oxygen and a phosphorus atom, phosphinic acids such as dimethylphosphinic acid and diphenylphosphinic acid; phosphonic acid esters such as ethylphosphonic acid and propylphosphonic acid monophenyl ester; Or, phosphate esters such as diphenyl phosphate, dimethyl phosphate and the like can be mentioned.

When E ¹ is an organic group bonded with a nucleophilic oxygen and a sulfur atom, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid; or monophenyl sulfate sulfate and monooctyl sulfate sulfate And the like.

Although all of the above examples are shown as protonated products, deprotonated compounds of the exemplified compounds and compounds which can be deprotonated in the reaction system are also exemplified. Examples of the compound that can be the deprotonated product in the reaction system include a compound in which the deprotonated product is bonded to another atom or atomic group. Examples of the other atoms or atomic groups bonded to the deprotonated substance include various monovalent cations (Na ⁺ , K ^+, etc.).

Among the above examples, E ¹ is particularly preferably an organic group bonded to a nucleophilic oxygen by a carbon atom, and specifically, the following types (i) to (iv) of oxygen nucleophiles are particularly preferable.

(i) RO-H or RO - ⁽ⁱⁿ the formulas, R may have a substituent, represents an alkyl group which may have a double bond or triple bond in the carbon chain.) Or deprotonated products thereof.

(ii) ArO—H or ArO ⁻ (wherein, Ar represents an aryl group which may have a substituent and may contain a hetero element such as nitrogen, oxygen, phosphorus and sulfur. ) Or a deprotonated product thereof.

(iii) R′COO—H or R′COO ⁻ (wherein R ′ represents a hydrogen atom or an alkyl group, and may further have a substituent, and may have a double bond or triple bond in the carbon chain. An aliphatic carboxylic acid represented by the formula: or a deprotonated product thereof.

(iv) Ar′COO—H or Ar′COO ⁻ (wherein, Ar ′ may have a substituent and may contain a hetero element such as nitrogen, oxygen, phosphorus, and sulfur. An aromatic carboxylic acid represented by the formula: or an aproton thereof.

(4) Examples of the oxygen nucleophile of the type (i) include saturated or unsaturated alcohols and their substituents, and saturated or unsaturated diols and polysubstituted alcohols and their substituents. Specific examples of the saturated or unsaturated alcohols and their substituent-containing compounds include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, 2-ethylhexanol, n-octanol, and allyl. Examples include alcohol, crotyl alcohol, benzyl alcohol, 1-bromo-2-propanol, 2-methylcyclopentanol, 2-phenylethanol, neopentyl alcohol, 4-cyclohexenol, and cholesterol. Specific examples of a saturated or unsaturated diol or a polysubstituted alcohol or a substituent-containing product thereof include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 2-butene-1, Examples thereof include 4-diol, 2-chloro-1,3-propanediol, 1,2-cyclopentanediol, glycerin, and pentaerythritol.

Among these, as the oxygen nucleophile of the type (i), a saturated alcohol or a saturated diol is preferable, and specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl Alcohol, C1-C10 alcohol such as 2-ethylhexanol or n-octanol; C1-C1 alcohol such as 1,2-ethanediol, 1,3-propanediol or 1,4-butanediol 10 diols and the like are preferred.

(4) Examples of the oxygen nucleophile of the type (ii) include monohydroxyaryl and their substituent-containing substances, di- or polyhydroxyaryl and their substituent-containing substances, and the like. Specific examples of monohydroxyaryl and their substituent-containing products include phenol, cresol, 4-nitrophenol, 2-fluorophenol, 2,4-di-t-butylphenol, 2,4-di-t-butyl- 6-methylphenol, 1-naphthol, 2-naphthol, 3-t-butyl-2-naphthol and the like can be mentioned. Specific examples of di- or polyhydroxyaryl and their substituent-containing compounds include catechol, resorcinol, hydroquinone, 2,4-dihydroxyphenylethylketone, 4-n-hexylresorcinol, 1,8-dihydroxynaphthalene, , 2-dihydroxynaphthalene, 1-methyl-2,3-dihydroxynaphthalene or 1,2,4-benzenetriol.

Among these, as the oxygen nucleophile of the type (ii), monohydroxyaryl or dihydroxyaryl is preferable, and specifically, phenol, 1-naphthol, 2-naphthol, catechol, resorcinol, hydroquinone, or 2, Those having 1 to 15 carbon atoms such as 6-dihydroxynaphthalene are preferred.

Examples of the oxygen nucleophile of the type (iii) include saturated aliphatic carboxylic acids and their substituents, unsaturated aliphatic carboxylic acids and their substituents, aliphatic dicarboxylic acids and their substituents And the like. Saturated aliphatic carboxylic acids and their substituent-containing products include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, cyclohexanecarboxylic acid, α-methylbutyric acid, γ-chloro-α-methylvaleric acid, α-hydroxypropionic acid, γ-phenylbutyric acid and the like. Examples of unsaturated aliphatic carboxylic acids and their substituents include unsaturated fatty acids such as acrylic acid, oleic acid, linoleic acid, linolenic acid, 2-cyclohexenecarboxylic acid, 4-methoxy-2-butenoic acid, and methacrylic acid. Group carboxylic acids and their substituent-containing products. Examples of the aliphatic dicarboxylic acids and their substituents include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and the like.

Among them, as the oxygen nucleophile of the type (iii), a saturated aliphatic carboxylic acid or a saturated aliphatic dicarboxylic acid is preferable, and specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid , Myristic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like are preferred.

(4) Examples of the oxygen nucleophile of type (iv) include aromatic carboxylic acids and their substituents, and aromatic di- or polycarboxylic acids and their substituents. Aromatic carboxylic acids and their substituent-containing products include benzoic acid, 3-cyanobenzoic acid, 2-bromobenzoic acid, 2,3-dimethoxybenzoic acid, 4-phenoxybenzoic acid, p-nitrobenzoic acid, -Toluic acid, o-methoxybenzoic acid, phthalic acid monomethyl ester, terephthalic acid monoethyl ester, naphthalene-1-carboxylic acid, 1-methylnaphthalene-2-carboxylic acid, 2-ethoxynaphthalene-1-carboxylic acid, 1- Hydroxynaphthalene-2-carboxylic acid, 1-bromonaphthalene-2-carboxylic acid, anthracene-9-carboxylic acid, phenanthrene-4-carboxylic acid, picolinic acid, nicotinic acid, isonicotinic acid, 2-methoxythionicotinic acid, 6 -Chloronicotinic acid, isoquinoline-1-carboxylic acid, quinoline-3-carboxylic acid, -4-carboxylic acid, and 4-methoxy-2-carboxylic acid. Examples of aromatic di- or polycarboxylic acids and their substituents include phthalic acid, isophthalic acid, terephthalic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid , Naphthalene-1,4-dicarboxylic acid, naphthalene-1,8-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid And the like.

Among them, as the oxygen nucleophile of the type (iv), an aromatic carboxylic acid or a dicarboxylic acid is preferable, and specific examples thereof include benzoic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Those having 6 to 15 carbon atoms, such as acids, are preferred.

The carbon ^{nucleophile, E 2 E 3 E 4 C} - carbo anions represented by, or E ² E ³ the proton adduct represented by E ⁴ CH may be mentioned as preferred examples. In the above formula, E ^{2 to} E ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a sulphonyl group, a carboxy group, a chain or cyclic alkyl group, an aryl group, an acyl group, Represents a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an isocyano group, an alkylideneamino group, or a dialkoxyphosphoryl group. Each of the above exemplified groups may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a linear or cyclic alkyl group, or an aryl group. Preferred are a group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

In the case where the substituents exemplified above as E ^{2 to} E ^{4 and the} additional substituents are groups containing a carbon chain, one or more carbon-carbon double bonds or triple bonds are contained in the carbon chain. A bond may be present. Further, any two or more groups of E ^{2 to} E ⁴ may be bonded to each other to form one or more cyclic structures. Further, at least one of E ^{2 to} E ⁴ needs to be an electron withdrawing group. Among them, it is preferable that two or more of E ^{2 to} E ⁴ are electron withdrawing groups. Here, the electron withdrawing group refers to a group having a higher electron withdrawing property than a hydrogen atom.

The carbon number of the carbon nucleophile is usually 50 or less, preferably 40 or less, particularly preferably 30 or less. The molecular weight is usually 600 or less, preferably 500 or less, particularly preferably 400 or less.

Among the above-described carbon nucleophiles, carbanions are formed from an uncharged compound in which a substituent such as a proton is bonded to an unshared electron pair. Alternatively, protons or the like may be extracted to form a carbanion and then used in the reaction. In the latter case, generally, when an alkali metal ion is used as a counter cation of a carbanion, the reaction can be performed with higher reaction activity. Normally, a carbon nucleophile takes a structure of a carbanion exhibiting nucleophilicity only when a proton is extracted from the original compound. Therefore, the original compound is an active proton, that is, a compound having an acidic proton (protonated product). ) Is desirable.

Preferable examples of the carbon nucleophile include, in the form of a hydrogenated product, malonic ester derivatives such as diethyl malonate and diethyl methylmalonate; ethyl α-bromopropionate, ethyl acetoacetate, cyano Α-substituted acetate derivatives such as methyl acetate, benzyl isocyanoacetate, ethyl phenylsulfonylacetate, butyl nitroacetate, or tert-butyl phenylthioisocyanoacetate; substituted nitromethane derivatives such as nitroethane or dinitromethane; heptane-3, Diacylmethane derivatives such as 5-dione or pentane-2,4-dione; sulfonylmethane derivatives such as dimethylsulfonylmethane or phenylsulfonylallyl; substituted acetonitriles such as phenylacetonitrile or phenoxyphenylthioacetonitrile And alkylideneaminomethane derivatives such as diethyl cyclohexylideneaminomethylphosphonate or bis (2-propylideneamino) methane; and fluorene.

More preferred as the carbon nucleophile is a compound in which at least one of E ^{2 to} E ⁴ is an alkoxycarbonyl group. Specific examples of such compounds include diethyl malonate, ethyl acetoacetate, and methyl cyanoacetate. Among them, a compound in which two of E ^{2 to} E ⁴ are alkoxycarbonyl groups is particularly preferred. A specific example of such a compound is diethyl malonate.

Preferred examples of the nitrogen nucleophile include amines represented by HNE ⁵ E ⁶ and bonded to at least one hydrogen atom. In the above formula, E ^{5 and} E ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a sulfonyl group, a carboxy group, a chain or cyclic alkyl group, an aryl group, an acyl group, and carbamoyl. Represents a group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, or an aryloxy group. Each of the above exemplified groups may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a linear or cyclic alkyl group, or an aryl group. Preferred are a group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

When the substituents exemplified above as E ⁵ and E ⁶ and the additional substituents are groups containing a carbon chain, one or more carbon-carbon double bonds or triple A bond may be present. E ⁵ and E ⁶ may be combined with each other to form one or more cyclic structures.

The nitrogen number of the nitrogen nucleophile is usually 40 or less, preferably 30 or less, particularly preferably 20 or less. The molecular weight is usually 500 or less, preferably 400 or less, particularly preferably 300 or less.

In the case of the reaction with amines, the lone pair of electrons on the nitrogen of the amine nucleophilically attacks the terminal allylic carbon of the π-allyl complex to form an ammonium cation as an intermediate, from which protons are released. In order to form charge-neutral allylamines, the amines must have at least one hydrogen atom bonded thereto. However, in order to further enhance the nucleophilicity of the amines, the protons may be extracted in advance by a chemical treatment or the like and used in the reaction in the form of an anionized amine such as E ⁵ E ⁶ N—. . In this case, examples of the counter cation of the anionized amines include alkali metal ions.

Preferred examples of the nitrogen nucleophile include, in the form of a hydrogenated product, ammonia: ethylamine, n-butylamine, i-propylamine, 3-chloro-n-propylamine, t-butylamine, n-butylamine. Primary amines such as octylamine, allylamine, cyclohexylamine, benzylamine, phenylamine or phenoxyamine; dimethylamine, diethylamine, di-i-propylamine, di-n-pentylamine, di-n-undecylamine , Di (2-butenyl) amine, dicyclohexylamine, diphenylamine, diphenoxyamine, di (4-bromocyclohexyl) amine, methylethylamine, t-butyl-n-butylamine, methylphenylamine, 4-cyano-n-decylneo Pentylamine, 2 Ethoxyethyl-tert-butylamine, N-chloro-N-phenylamine, N-ethoxy-N-ethylamine, Nn-octyl-N-hydroxyamine, N-3,5-dimethylhexyl-N-2-ethylhexylamine Secondary amines such as caproamide, 3-bromobenzamide, ethoxycarbonylamine, N-bromoacetamide, 4-fluoroacetanilide, cyclohexyldi-i-propylaminocarbonylamine, methoxycarbonylpropylamine, carboxyglycine, or phenoxycarbonylphenyl N-unsubstituted or monosubstituted amide compounds such as amines; heterocyclic cyclic compounds such as pyrrole, imidazole, pyrrolidine, indole, 2,5-dimethylpyrrolidine, morpholine, or 4-chloro-2,5-dihydroquinoline. Down like; or, tetramethylenediamine, N, N'-diethyl ethylenediamine, hexamethylenediamine, or 1,3,5-triamino diamine or multi-amine such as benzene.

More preferred as the nitrogen nucleophile is a primary or secondary amine in which at least one of E ⁵ and E ⁶ is an unsubstituted or substituted alkyl group. Specific examples of such compounds include dimethylamine, diethylamine, di-i-propylamine, di-n-pentylamine, di-n-undecylamine, di (2-butenyl) amine, dicyclohexylamine, di (4- (Bromocyclohexyl) amine, methylethylamine, t-butyl-n-butylamine, 4-cyano-n-decylneopentylamine, 2-ethoxyethyl-t-butylamine, N-3,5-dimethylhexyl-N-2-ethylhexyl Amines and the like.

Next, the catalyst used in the production method of the present invention will be described. The catalyst used in the present invention comprises one or more transition metal compounds and a bidentate phosphite compound.

As the transition metal compound, one or more compounds containing a transition metal selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table (according to IUPAC revised edition of inorganic chemical nomenclature (1998)) are used. . Specifically, an iron compound, a ruthenium compound, an osmium compound, a cobalt compound, a rhodium compound, an iridium compound, a nickel compound, a palladium compound, a platinum compound, and the like, among which ruthenium compound, rhodium compound, iridium compound, nickel compound, Palladium compounds and platinum compounds are preferred, nickel compounds, palladium compounds and platinum compounds are more preferred, and palladium compounds are particularly preferred. The type of these compounds is arbitrary, but specific examples include the above-mentioned transition metal acetates, acetylcetonate compounds, halides, sulfates, nitrates, organic salts, inorganic salts, alkene coordination compounds, and amine coordination compounds. , A pyridine coordination compound, a carbon monoxide coordination compound, a phosphine coordination compound, a phosphite coordination compound, and the like.

When specific examples of the transition metal compound are listed, examples of the iron compound include Fe (OAc) ₂ , Fe (acac) ₃ , FeCl ₂ , and Fe (NO ₃ ) ₃ . Examples of the ruthenium compound include RuCl ₃ , Ru (OAc) ₃ , Ru (acac) ₃ , and RuCl ₂ (PPh ₃ ) ₃ . Examples of the osmium compound include OsCl ₃ and Os (OAc) ₃ . Examples of the cobalt compound include Co (OAc) ₂ , Co (acac) ₂ , CoBr ₂ , and Co (NO ₃ ) ₂ . Examples of rhodium compounds include RhCl ₃ , Rh (OAc) ₃ , [Rh (OAc) ₂ ] ₂ , Rh (acac) (CO) ₂ , [Rh (OAc) (cod)] ₂ and [RhCl (cod)] _2. And the like. Examples of the iridium compound include IrCl ₃ , Ir (OAc) ₃ , and [IrCl (cod)] ₂ . Examples of the nickel compound include NiCl ₂ , NiBr ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , Ni (cod) ₂ , and NiCl ₂ (PPh ₃ ) ₃ . Pd (0), PdCl ₂ , PdBr ₂ , PdCl ₂ (cod), PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , Pd ₂ (dba) ₃ , K ₂ PdCl ₄ , K ₂ PdCl ₆ , PdCl ₂ (PhCN) ₂ , PdCl ₂ (CH ₃ CN) ₂ , Pd (dba) ₂ , Pd (NO ₃ ) ₂ , Pd (OAc) ₂ , Pd (CF ₃ COO) ₂ , PdSO ₄ , Examples include Pd (acac) ₂ , carboxylate compounds, olefin-containing compounds, organic phosphine-containing compounds such as Pd (PPh ₃ ) ₄ , and allyl palladium chloride dimers. Examples of the platinum compound include Pt (acac) ₂ , PtCl ₂ (cod), PtCl ₂ (CH ₃ CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt (PPh ₃ ) ₄ , K ₂ PtCl ₄ , Na ₂ PtCl ₆ , H ₂ PtCl ₆ . In the above examples, cod represents 1,5-cyclooctadiene, dba represents dibenzylideneacetone, acac represents acetylacetonate, and Ac represents an acetyl group.

種類 The type of the transition metal compound is not particularly limited, and may be any of a monomer, a dimer, and / or a multimer as long as it is an active metal complex.

The amount of the transition metal compound to be used is not particularly limited, but is usually 1 × 10 ⁻⁸ (0.01 mol ppm) molar equivalent or more with respect to the allyl compound as a reaction raw material, from the viewpoint of catalytic activity and economy. Above all, 1 × 10 ⁻⁷ (0.1 mol ppm) molar equivalent or more, especially 1 × 10 ⁻⁶ (1 mol ppm) molar equivalent or more, usually 1 molar equivalent or less, especially 0.001 molar equivalent or less, particularly 0 It is preferably used in a range of not more than 0.0001 molar equivalent.

On the other hand, as the bidentate phosphite compound, a phosphite compound having a structure represented by the following general formulas (I) to (III) is used. The type of the phosphite compound is not particularly limited as long as it is a phosphite compound that becomes a chelating ligand for the above-mentioned transition metal compound. In order to increase the catalytic activity, those dissolved in the reaction system are good, and the molecular weight is usually 3000 or less, preferably 1500 or less, and usually 250 or more, preferably 300 or more, more preferably 400 or more.

One of the features of the present invention is that A ^{1 to} A ³ in the general formulas (I) to (III) have a specific structure. The presence of this specific structure allows the catalyst used in the present invention to obtain high catalytic activity.

In the above general formulas (I) to (III), A ^{1 to} A ³ each independently represent a diarylene group having a branched alkyl group at the ortho position. The diarylene group may further have a substituent as long as it does not adversely affect the reaction system. The carbon number of each of A ^{1 to} A ³ is usually 60 or less, preferably 50 or less, more preferably 40 or less.
In the general formulas (I) to (III), R ^{11 to} R ¹⁶ each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent Include a heterocyclic compound forming an aromatic 6π electron cloud. The same applies to the following.).
In the general formulas (I) to (III), Z ^{1 to} Z ³ each independently represent an alkylene group which may have a substituent, an arylene group which may have a substituent, or a substituent. It represents an alkylene-arylene group which may have, or a diarylene group which may have a substituent.

The Jiariren group, directly two arylene group or to a group linked via a divalent organic group, specifically -Ar ¹ - is represented by - (Q ¹⁾ _n -Ar ² It is a group having a structure. Ar ¹ and Ar ² each independently represent an arylene group which may have a substituent. Q ¹ represents a divalent organic group. Specific examples thereof include a group represented by —O—, —S—, —CO—, or —CR ²¹ R ²² —. R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. n represents 0 or 1. As the substituents that the arylene group of Ar ¹ and Ar ² and the alkyl group and the aryl group of R ²¹ and R ²² may have, as long as they do not adversely affect the reaction system, Although not limited, preferred specific examples include a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, and an acyloxy group. , An alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.

The ortho-branched alkyl group usually has 3 to 10 carbon atoms, and preferably 3 to 7 carbon atoms. A secondary or tertiary alkyl group having a branched chain at the carbon atom bonded to the aromatic ring is preferred, and a tertiary alkyl group is particularly preferred.
Specific examples of such a diarylene group include groups having structures represented by the following formulas (A-1) to (A-19).

(4) In view of catalytic activity and stability of the phosphite ligand, a diarylene group having a structure represented by the following general formula (IV) or (V) is particularly preferable.

In the above general formulas (IV) and (V), T ¹ , T ⁸ , U ¹ and U ¹² each independently represent a branched alkyl group, and T ^{2 to} T ⁷ and U ^{2 to} U ¹¹ each independently represent , Hydrogen atom, halogen atom, hydroxy group, chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, ester group, carboxy group, amino group, amide group, alkylthio group, arylthio group, acyl group, or acyloxy Represents a group. These groups may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a linear or cyclic alkyl group, or an aryl group. Preferred are a group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

The carbon number of T ¹ , T ⁸ , U ¹ and U ¹² is usually 3 to 10, preferably 3 to 7. A secondary or tertiary alkyl group having a branched chain at the carbon atom bonded to the aromatic ring is preferred, and a tertiary alkyl group is particularly preferred.
Specific examples of the branched alkyl group include a secondary alkyl group such as an i-propyl group, an i-butyl group, an i-pentyl group and an i-hexyl group; a t-butyl group, an amyl group (a 1,1-dimethylpropyl group). ), A tertiary alkyl group such as a 1-methyl-1-ethylpropyl group and a 1,1-diethylpropyl group. A tertiary alkyl group is preferred, and a t-butyl group is most preferred.

The carbon number of T ^{2 to} T ⁷ and U ^{2 to} U ¹¹ is usually 30 or less, preferably 20 or less, more preferably 10 or less. Among the above examples, preferred as T ^{2 to} T ⁷ and U ^{2 to} U ¹¹ are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, or an unsubstituted or substituted aryl group. is there.

Particularly preferred groups for A ^{1 to} A ³ , that is, specific examples of the group represented by the above general formula (IV) or (V) include groups represented by the above formulas (A-1) to (A-7) Can be mentioned.

On the other hand, in the general formulas (I) to (III), R ^{11 to} R ¹⁶ each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent Include a heterocyclic compound forming an aromatic 6π electron cloud. The same applies to the following.).

The carbon number of R ^{11 to} R ¹⁶ is usually 40 or less, preferably 30 or less, more preferably 20 or less. When the above-mentioned alkyl group or aryl group further has a substituent, the total number of carbon atoms including this substituent is adjusted to the above range.

The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or a cyclic Preferred are an alkyl group, an aryl group, an alkoxy group, an arylalkoxy group, an aryloxy group, an alkylaryloxy group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, and an ester group.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group. And a chain alkyl group such as a hexyl group, an octyl group, or a decyl group; and a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group.

Examples of the aryl group which may have a substituent include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group, and a 2-t- Such as a butylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, and a 2,4-di-t-butylphenyl group; Mono- or dialkylphenyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3 Halophenyl groups such as 2,5-dichlorophenyl group or pentafluorophenyl group; 2-methoxyphenyl group, 3-methoxy An alkoxyphenyl group such as a cyclophenyl group, a 4-methoxyphenyl group, or a 3,5-dimethoxyphenyl group; a cyanophenyl group such as a 4-cyanophenyl group; a nitrophenyl group such as a 4-nitrophenyl group; or 4-trifluoro A phenyl group which may have a substituent such as a haloalkylphenyl group such as a methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-methyl-1-naphthyl group, a 3-t-butyl-2- Mono- or dialkylnaphthyl groups such as naphthyl group or 3,6-di-t-butyl-2-naphthyl group; methyloxycarbonylnaphthyl group such as 3-methyloxycarbonyl-2-naphthyl group; or 5,6,7 Hydronaphthyl groups such as, 8-tetrahydronaphthalen-2-yl group and 5,6,7,8-tetrahydronaphthalen-1-yl group Nitrogen-containing heterocyclic compounds such as naphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, isoquinolyl or indolyl which may have a substituent; oxygen-containing heterocyclic compounds such as furanyl A heterocyclic compound group such as a thiophenyl group or the like; or a heterocyclic compound group containing two or more kinds of heteroatoms in the ring such as an oxazolyl group or a thiazolyl group.

In consideration of the stability of the above-mentioned phosphites among the above-described exemplified groups, R ^{11 to} R ¹⁶ are preferably unsubstituted or substituted aryl groups, and among unsubstituted or substituted aryl groups, unsubstituted or substituted phenyl. Groups and unsubstituted or substituted naphthyl groups are particularly preferred.

Z ^{1 to} Z ³ each independently represent a divalent organic group. The type is not particularly limited as long as it does not adversely affect the reaction system, but a chain or cyclic alkylene group, an arylene group, an alkylene-arylene group, or a diarylene group is preferable. These organic groups may further have a substituent as long as there is no risk of adversely affecting the reaction system.

The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or a cyclic Preferred are an alkyl group, an aryl group, an alkoxy group, an arylalkoxy group, an aryloxy group, an alkylaryloxy group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, and an ester group.

The carbon number of each of Z ^{1 to} Z ³ is usually 60 or less. Among them, in the case of an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted alkylene-arylene group, the number of carbon atoms is usually 40 or less, preferably 30 or less, more preferably 20 or less. It is. On the other hand, in the case of an unsubstituted or substituted diarylene group, the number of carbon atoms is usually 60 or less, preferably 50 or less, more preferably 40 or less.

Specific examples of the unsubstituted or substituted alkylene group include an ethylene group, a tetramethylethylene group, a 1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,4-butylene group. Can be

Specific examples of the unsubstituted or substituted arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 3,5-di-t-butyl-1,2-phenylene group, and a 2,3-naphthylene group. , 1,4-di-t-butyl-2,3-naphthylene group, 1,8-naphthylene group and the like.

{Specific examples of the unsubstituted or substituted alkylene-arylene group include substituents having structures represented by the following formulas (D-1) to (D-12).

The Jiariren group, as described above, -Ar ¹ - is a group having a structure represented by _{^{- (Q 1) n -Ar 2}} . The definitions of Ar ¹ , Ar ² , Q ¹ , and n in the above formula are the same as the definitions described above in the description of A ^{1 to} A ³ . Specific examples of such a diarylene group include groups having structures represented by the following formulas (Z-1) to (Z-48).

Among them, a diarylene group having a structure represented by the following general formula (VI) or (VII) is particularly preferable.

In the above general formulas (VI) and (VII), T ^{9 to} T ¹⁶ and U ^{13 to} U ²⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a chain or cyclic alkyl group, an aryl group, an alkoxy group. Represents a group, an aryloxy group, an ester group, a carboxy group, an amino group, an amide group, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group. These groups may further have a substituent.
The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or a cyclic Preferred are an alkyl group, an aryl group, an alkoxy group, an arylalkoxy group, an aryloxy group, an alkylaryloxy group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, and an ester group.

The carbon number of T ^{9 to} T ¹⁶ and U ^{13 to} U ²⁴ is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 10. Among the above examples, preferred as T ^{9 to} T ¹⁶ and U ^{13 to} U ²⁴ are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, or an unsubstituted or substituted aryl group. is there.

Particularly preferred groups as Z ^{1 to} Z ³ , that is, specific examples of the group represented by the above general formula (VI) or (VII) include groups represented by the above formulas (Z-1) to (Z-18). Can be mentioned.

As described above, phosphites having various structures can be used depending on the combination of the substituents constituting the phosphite compounds represented by the general formulas (I) to (III). Examples include compounds represented by the following formulas (L-1) to (L-13).

The amount of the above-mentioned bidentate phosphite compound to be used is usually 0.1 or more, preferably 0.5 or more, particularly preferably 1.0 or more, as a ratio (molar ratio) to the above-mentioned transition metal compound. The range is 10,000 or less, preferably 500 or less, particularly preferably 100 or less.

The transition metal compound and the bidentate phosphite compound may be added individually to the reaction system, or may be used in a state of being complexed in advance. Alternatively, the above-mentioned bidentate phosphite compound may be bound to a certain insoluble resin carrier or the like, and the transition metal compound may be supported on the insoluble resin catalyst. Further, the reaction may be carried out using only one kind of bidentate phosphite compound, or the reaction may be carried out simultaneously using two or more kinds of bidentate phosphite compounds in any combination.

By reacting an allyl raw material compound with a nucleophile using a catalyst comprising a transition metal compound described above and a bidentate phosphite compound having a specific structure, a new allyl compound (for example, an ether compound or Ester compound) can be produced efficiently.

In carrying out the production method of the present invention, the reaction is usually performed in a liquid phase. The reaction can be carried out either in the presence or absence of a solvent. When a solvent is used, any solvent can be used as long as it dissolves the catalyst and the starting compound and does not adversely affect the catalytic activity, and the type thereof is not particularly limited. Specific examples of preferred solvents include carboxylic acids such as acetic acid, propionic acid and butyric acid, alcohols such as methanol, n-butanol and 2-ethylhexanol, diglyme, diphenyl ether, dibenzyl ether, diallyl ether and tetrahydrofuran (THF). , Ethers such as dioxane, amides such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, ketones such as cyclohexanone, esters such as butyl acetate, γ-butyrolactone, di (n-octyl) phthalate; Toluene, xylene, aromatic hydrocarbons such as dodecylbenzene, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, high-boiling substances generated as by-products in the allylation reaction system, allyl compounds as raw materials, Allyl product Compounds, compounds derived from the leaving group of the starting allylic compounds. The use amount of these solvents is not particularly limited, but is usually 0.1 times by weight or more, preferably 0.2 times by weight or more, and usually 20% by weight, Times or less, preferably 10 times or less by weight.

様 々 Various reaction methods can be used for actually performing the reaction. For example, using a stirring type complete mixing reactor, a plug flow type reactor, a fixed bed type reactor, a suspension bed type reactor, etc., in a continuous system, a semi-continuous system or a batch system. Can be.

When actually performing the reaction for each, the conditions may be appropriately examined depending on the reaction substrate and the product.For example, in the case of a stirring type complete mixing reactor, the allyl raw material compound and the nucleophile and, in some cases, the solvent may be used. A nucleophile is obtained by introducing a mixture obtained by adding a catalyst solution separately prepared in a catalyst preparation tank to a reactor continuously or semi-continuously and stirring the mixture at a certain reaction temperature with stirring. Allylation reaction can proceed, and the reaction can be carried out while continuously or semi-continuously withdrawing a part of the reaction solution from the reactor. In the case of a plug flow type reactor, the reaction can be allowed to proceed while allowing the reaction solution containing the above-mentioned raw materials and catalyst to flow through a tubular reactor maintained at a certain reaction temperature. In this case, the method is suitable for realizing a high conversion rate of the raw material. Further, when an insoluble solid catalyst carrying a catalyst is used, a fixed-bed reaction system in which the reaction is performed while passing the solution containing the raw material through the reactor filled with the catalyst, or a particulate insoluble solid catalyst may be used. It is also possible to employ a suspension bed reaction system in which the catalyst and the solution containing the raw materials are stirred and mixed in a reactor to carry out the reaction while maintaining the suspension.

The reaction temperature is not particularly limited as long as the catalytic reaction proceeds, but when a noble metal compound such as palladium is used as a catalyst, if the temperature is too high, there is a risk that metallization occurs and the effective catalyst concentration is reduced. is there. In addition, since phosphite compounds may be decomposed at high temperatures, the temperature is usually 0 ° C or higher, preferably 20 ° C or higher, more preferably 50 ° C or higher, and usually 180 ° C or lower, preferably 160 ° C or lower, more preferably 150 ° C. or less is recommended.

The atmosphere in the reactor should be filled with an inert gas to the reaction system such as argon or nitrogen, except for vapors derived from solvents, raw material compounds, reaction products, reaction by-products, catalytic decomposition products, etc. Is desirable. It should be particularly noted that the incorporation of oxygen due to leakage of air or the like causes deterioration of the catalyst, particularly oxidation of the phosphite compound, and therefore it is desirable to reduce the amount as much as possible.

The residence time of the solution in the reactor, that is, the reaction time, depends on the value of the conversion rate of the raw material to be aimed at, but under a certain catalyst concentration, the longer the reaction time, the higher the conversion rate is required. . On the other hand, if it is desired to shorten the reaction time while maintaining a high conversion, it is necessary to increase the catalyst concentration, increase the amount of the catalyst, or increase the reaction temperature to increase the catalyst activity. However, in order to suppress deterioration and side reactions due to the thermal history of the catalyst, it is desirable to avoid using a reaction time longer than necessary or a reaction at a high temperature.

ア リ ル Further, for separation of the allyl compound obtained by the reaction and the catalyst, any separation operation used in a conventional liquid catalyst recycling process can be adopted. Specific examples of the separation operation include distillation operations such as simple distillation, vacuum distillation, thin film distillation, and steam distillation, and separation operations such as gas-liquid separation, evaporation (evaporation), gas stripping, gas absorption, and extraction. Can be The separation operation of each component may be performed in an independent step, or the separation of two or more components may be performed simultaneously in a single step. When some of the allyl raw material compounds and the nucleophile remain unreacted, it is more economical to collect them by the same separation method and recycle them to the reactor. It is more economical and desirable that the separated catalyst be recycled or recovered as it is in the reactor, reactivated, and reused.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

<Example 1 and Comparative Example 1>
The present invention was applied to a synthesis reaction of allyl phenyl ether using allyl methyl carbonate as an allyl raw material compound and phenol as an oxygen nucleophile.

0.0149 g (0.0151 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and 4 equivalents of the above formula (4) based on palladium as a bidentate phosphite compound The bidentate phosphite compound of L-6) (Example 1) (0.1204 mmol) was placed in Schlenk, and after purging with argon, 2.0 ml of tetrahydrofuran was added and the mixture was stirred at room temperature to give a palladium concentration of 15.2. A catalyst solution of 05 mmol / l was prepared. Subsequently, Schlenk separately prepared for performing the reaction was replaced with argon, and 5.0 ml of a tetrahydrofuran solution containing 0.1720 g (1.481 mmol) of allylmethyl carbonate and 0.2707 g (2.877 mmol) of phenol was added under argon. Added in. 20.0 μl of the above-mentioned catalyst solution was added thereto with a microsyringe, and the reaction was carried out by heating at 60 ° C. After the reaction for 30 minutes, the yield of allyl phenyl ether was determined by analyzing the solution composition by gas chromatography.

As a comparative example, the same reaction was carried out using a bidentate phosphite ligand having a structure represented by the following formula (LA) (Comparative Example 1).

<Examples 2 and 3 and Comparative Example 2>
The present invention was applied to a synthesis reaction of allyl octyl ether using allyl acetate as an allyl raw material compound and 1-octanol as an oxygen nucleophile.

As a transition metal compound, 0.0048 g (0.0048 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and as a bidentate phosphite compound, 2 equivalents of the above (L The bidentate phosphite compound of Example -6) (Example 2) or the bidentate phosphite compound of Example (L-13) (Example 3) (0.0194 mmol) was put into Schlenk, and then replaced with argon. , 0.943 g (9.420 mmol) of allyl acetate and 2.422 g (18.594 mmol) of 1-octanol were added under argon, and the reaction was carried out by heating at 100 ° C. After the reaction for 60 minutes, the yield of allyl octyl ether was determined by analyzing the solution composition by gas chromatography.

In addition, as a comparative example, the same reaction was carried out using a bidentate phosphite ligand having a structure represented by the following formula (LB) (Comparative Example 2).

<Example 4 and Comparative Example 3>
The present invention was applied to a synthesis reaction of allyl benzoate using allyl acetate as an allyl raw material compound and benzoic acid as an oxygen nucleophile.

0.0149 g (0.0151 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and 4 equivalents of the above formula (4) based on palladium as a bidentate phosphite compound The bidentate phosphite compound (Example 11) of L-11) (Example 4) (0.1204 mmol) was put into Schlenk, and after purging with argon, 2.0 ml of tetrahydrofuran was added, and the mixture was stirred at room temperature to obtain a palladium concentration. A catalyst solution of 15.05 mmol / l was prepared. Subsequently, Schlenk separately prepared for performing the reaction was replaced with argon, and 4.0 ml of a tetrahydrofuran solution containing 0.1208 g (1.206 mmol) of allyl acetate and 0.3083 g (2.525 mmol) of benzoic acid was added under argon. Added in. 60.0 μl of the above-mentioned catalyst solution was added thereto with a microsyringe, and the reaction was carried out by heating at 60 ° C. After the reaction for 30 minutes, the yield of allyl benzoate was determined by analyzing the solution composition by gas chromatography.

As a comparative example, the same reaction was carried out using a bidentate phosphite ligand having a structure represented by the following formula (LC) (Comparative Example 3).

<Example 5 and Comparative Example 4>
The present invention was applied to a synthesis reaction of allyl dicyclohexylamine using allyl acetate as an allyl raw material compound and dicyclohexylamine as a nitrogen nucleophile.

0.0014 g (0.00141 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound and 4 equivalents of the bidentate phosphite of the above formula (L-6) with respect to palladium (Example 5) (0.0113 mmol) was placed in Schlenk, and after purging with argon, 3.0 ml of a tetrahydrofuran solution containing 0.0821 g (0.820 mmol) of allyl acetate and 0.2992 g (1.650 mmol) of dicyclohexylamine was added. The reaction was carried out at 25 ° C. under argon. After the reaction for 6 minutes, the yield of allyldicyclohexylamine was determined by analyzing the solution composition by gas chromatography.

{Circle around (2)} As a comparative example, the same reaction was carried out using the bidentate phosphite ligand represented by the above formula (LB).

<Example 6>
The present invention was applied to a synthesis reaction of butylbutenyl ethers using cis-1,4-diacetoxy-2-butene as an allyl raw material compound and 1-butanol as an oxygen nucleophile.
As a transition metal compound, 0.0020 g (0.0040 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and 4 equivalents of palladium as a bidentate phosphite (L-6) are shown. 0.0173 g (0.0162 mmol) of the bidentate phosphite to be introduced into Schlenk, and after purging with nitrogen, 1.418 g (8.233 mmol) of cis-1,4-diacetoxy-2-butene and 2.327 g ( The reaction was carried out by adding 31.395 mmol) of 1-butanol under nitrogen and heating at 100 ° C. After the reaction for 5 hours, the solution composition was analyzed by gas chromatography to find that the conversion of cis-1,4-diacetoxy-2-butene was 97.5%, that of dibutoxybutene was 71.8%, and that of acetoxybutoxybutene was 71.8%. Was produced 25.7%.

More specifically, the breakdown of diacetoxybutene of 71.8% is 56.0% of 1,4-dibutoxy-2-butene (mixture of cis and trans), and 15.8 of 3,4-dibutoxy-1-butene. 15.7% of acetoxybutoxybutene, 12.6% of 1-acetoxy-4-butoxy-2-butene (cis, trans mixture), 3-acetoxy-4-butoxy-1 -Butene 4.9%, 4-acetoxy-3-butoxy-1-butene 8.2%.

<Example 7>
The present invention was applied to a synthesis reaction of phenylbutenyl ethers using cis-1,4-diacetoxy-2-butene as an allyl raw material compound and phenol as an oxygen nucleophile.
0.0020 g (0.0044 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and 4 equivalents of the above (L-6) with respect to palladium as a bidentate phosphite Was placed in Schlenk and replaced with nitrogen. The reaction was performed by adding 1.460 g (8.477 mmol) of cis-1,4-diacetoxy-2-butene and 3.164 g (33.615 mmol) of phenol under nitrogen and heating at 100 ° C.
After the reaction for 60 minutes, when the solution composition was analyzed by gas chromatography, the conversion of cis-1,4-diacetoxy-2-butene was 75.2%, diphenoxybutene was 14.9%, and acetoxyphenoxybutene was 14.9%. Was produced 59.8%.

More specifically, the breakdown of 14.9% of diphenoxybutene includes 1,3.9% of 1,4-diphenoxy-2-butene (mixture of cis and trans) and 1.0% of 3,4-diphenoxy-1-butene. % Of the acetoxyphenoxybutene, as a breakdown of 19.8% of acetoxyphenoxybutene, 37.8% of 1-acetoxy-4-phenoxy-2-butene (mixture of cis and trans) and 3-acetoxy-4-phenoxy-1. -Butene was produced by 11.1% and 4-acetoxy-3-phenoxy-1-butene was produced by 10.9%.

As is clear from the above results, a conventionally used catalyst comprising a bidentate phosphite-based ligand in which the carbon atom at the PO-C bond of the bridging group is an alkyl-based sp ³ carbon It can be seen that the activity of the catalyst comprising a bidentate phosphite-based ligand in which the carbon is an aryl-derived sp ² carbon in the present invention is higher than the activity of the catalyst.

Example 8
The present invention was applied to a synthesis reaction of an unsaturated bond-containing polyester oligomer using cis-1,4-diacetoxy-2-butene as an allyl raw material compound and adipic acid as a bifunctional carboxylic acid as an oxygen nucleophile. .
As a transition metal compound, 0.0074 g (0.0162 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and 2 equivalents of the above (L-6) with respect to palladium as a bidentate phosphite 0.0693 g (0.0647 mmol) of the indicated bidentate phosphite was placed in a two-necked round bottom flask, and after purging with nitrogen, 10.005 g (58.107 mmol) of cis-1,4-diacetoxy-2-butene was added. And 7.104 g (48.610 mmol) of adipic acid were added under nitrogen, and the reaction was carried out by heating at 100 ° C. under a reduced pressure of 50 mmHg. As the reaction progressed, the pressure inside the system was gradually reduced to 20 mmHg (after 1 hour) and 7 mmHg (after 3 hours), and the generated acetic acid was distilled out of the system under reduced pressure. After the reaction for 7 hours, the solution composition was analyzed by gas chromatography. As a result, the conversion of cis-1,4-diacetoxy-2-butene was almost 100%, and a syrup-like oligomer was obtained. When the molecular weight distribution of the produced oligomer was analyzed by gel permeation chromatography, it was found that the oligomer was a polyester oligomer having a maximum molecular weight of 4000 and a maximum of 10,000 as a polystyrene equivalent molecular weight.

<Example 9>
The synthesis reaction of unsaturated bond-containing polyether oligomer using cis-1,4-diacetoxy-2-butene as an allyl raw material compound and 1,4-butanediol which is a bifunctional alcohol as an oxygen nucleophile was carried out. The invention has been applied.
As a transition metal compound, 0.0572 g (0.1249 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and 1 equivalent of the above (L-6) to palladium as a bidentate phosphite are shown. 0.2670 g (0.2492 mmol) of the resulting bidentate phosphite was placed in a two-necked round bottom flask, and after purging with nitrogen, 17.221 g (100.016 mmol) of cis-1,4-diacetoxy-2-butene and 9. 012 g (100.000 mmol) of 1,4-butanediol was added under nitrogen, and the reaction was carried out at 100 ° C. while gradually increasing the degree of vacuum from 50 mmHg as in Example 8. After the reaction for 7 hours, when the solution composition was analyzed by gas chromatography, the conversion of cis-1,4-diacetoxy-2-butene was almost 100%, and a syrup-like oligomer was obtained. When the molecular weight distribution of the produced oligomer was analyzed by gel permeation chromatography, it was found that the oligomer was a polyether oligomer having a maximum molecular weight of 2400 and a maximum of 7,000 in terms of polystyrene.

<Example 10>
Cis-1,4-diacetoxy-2-butene was used as the allyl raw material compound, and 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), which is a bifunctional phenol, was used as the oxygen nucleophile. The present invention was applied to a synthesis reaction of an unsaturated bond-containing polyether oligomer.
0.0091 g (0.0199 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and 2 equivalents of the above-mentioned (L-6) with respect to palladium as a bidentate phosphite. In a two-necked round-bottomed flask, 0.0852 g (0.07995 mmol) of bidentate phosphite was replaced with nitrogen, and then 10.008 g (58.126 mmol) of cis-1,4-diacetoxy-2-butene and 11. 001 g (48.189 mmol) of bisphenol A was added under nitrogen, and the reaction was carried out at 100 ° C. while gradually increasing the degree of vacuum from 50 mmHg as in Example 8. After the reaction for 7 hours, when the solution composition was analyzed by gas chromatography, the conversion of cis-1,4-diacetoxy-2-butene was almost 100%, and a candy-like oligomer was obtained. When the molecular weight distribution of the produced oligomer was analyzed by gel permeation chromatography, it was found that the oligomer was a polyether oligomer showing a maximum of 7,000 with a molecular weight of 3200 at the center in terms of polystyrene.

Claims (7)

A group consisting of one or more transition metal compounds containing a transition metal selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table, and compounds having a structure represented by the following general formulas (I) to (III) A new allyl compound having a different composition formula from the allyl raw material compound by reacting the allyl raw material compound with a nucleophile in the presence of a catalyst containing one or more bidentate phosphite compounds selected from the group consisting of: A method for producing an allyl compound, characterized by producing

(In the above general formulas (I) to (III), A ^{1 to} A ³ each independently represent a diarylene group having a branched alkyl group at the ortho position. R ^{11 to} R ¹⁶ each independently represent a substituent represents an aryl group which may have an alkyl group or a substituted group may have a (including the heterocyclic compound forming the aromatic 6π electron cloud and below the ring. forth.) .Z ¹ To Z ³ are each independently an alkylene group which may have a substituent, an arylene group which may have a substituent, an alkylene-arylene group which may have a substituent, or a substituent Represents a diarylene group which may have The method for producing an allyl compound according to claim 1, wherein the allyl raw material compound has a structure represented by the following general formula (a).

(In the general formula ^(a), R a ~R ^e are each independently a hydrogen atom, a halogen atom, hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Represents an acyl group or an acyloxy group, of which amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group and acyloxy group further have a substituent; If any of which may .R ^a to R ^e contains carbon chain, one or more carbons in its carbon chain - which may be present carbon double bond or triple bond .X is a halogen atom , Hydroxy, nitro, amino, sulfonyl, sulfonate, acyloxy, carbonate, carbamate, phosphate, alkoxy Represents an amino group, a sulfonyl group, a sulfonate group, an acyloxy group, a carbonate group, a carbamate group, a phosphate group, an alkoxy group, or an aryloxy group. When X contains a carbon chain, one or more carbon-carbon double bonds or triple bonds may be present in the carbon chain, and any two of R ^{a to} R ^e and X may be present. The above may be combined with each other to form one or more cyclic structures.) The transition metal compound is at least one compound selected from the group consisting of a ruthenium compound, a rhodium compound, an iridium compound, a nickel compound, a palladium compound, and a platinum compound. A method for producing the allyl compound according to the above. In the general formulas (I) to (III), R ^{11 to} R ¹⁶ are each independently an aryl group having 6 to 20 carbon atoms which may have a substituent, and Z ^{1 to} Z ³ are each independently The method for producing an allyl compound according to any one of claims 1 to 3, wherein the method is a diarylene group which may have a substituent. In the above general formulas (I) to (III), A ^{1 to} A ³ are each independently a diarylene group having a structure represented by the following general formula (IV) or (V) which may have a substituent. The method for producing an allyl compound according to any one of claims 1 to 4, characterized in that:

(In the above general formulas (IV) and (V), T ¹ , T ⁸ , U ¹ and U ¹² each independently represent a branched alkyl group, and T ^{2 to} T ⁷ and U ^{2 to} U ¹¹ each independently represent Represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an amino group, an ester group, a carboxy group, or a hydroxy group. The bidentate phosphite compound is such that T ^{2 to} T ⁷ and U ^{2 to} U ¹¹ in A ^{1 to} A ³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, The method for producing an allyl compound according to claim 5, wherein the method is an alkoxy group which may have or an aryl group which may have a substituent. The bidentate phosphite compound is characterized in that Z ^{1 to} Z ³ are each independently a diarylene group represented by the following general formula (VI) or (VII) which may have a substituent. A method for producing an allyl compound according to any one of claims 1 to 4.

(In the above general formulas (VI) and (VII), T ^{9 to} T ¹⁶ and U ^{13 to} U ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group , An acyloxy group, an amino group, an ester group, a carboxy group, or a hydroxy group.)