JP4608860B2 - Method for producing allyl compound and condensation copolymer - Google Patents

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 an oxygen nucleophile in the presence of a catalyst, and a condensation copolymer produced thereby. .

Various types of new allyl compounds can be synthesized by performing a catalytic reaction using an allyl compound as a raw material and a transition metal compound. In the reaction, as shown in the following reaction formula, an allyl starting material compound having a leaving group X is π-coordinated and oxidatively added to a transition metal compound, so that three carbons in the allyl moiety are bonded to the metal. An allyl complex is formed and proceeds by the terminal allylic carbon of the π-allyl complex being attacked by a nucleophile represented by Nu—H or Nu ⁻ .

  The details of the synthesis reaction of the allyl compound are described collectively in Non-Patent Document 1, but by selecting the type of nucleophile in the reaction, various forms of allylic nucleophiles can be obtained. A product can be obtained. In particular, when the nucleophile is an oxygen nucleophile such as alcohols, phenols, and carboxylic acids, allyl alkyl ether, allyl phenyl ether, and carboxylic acid allyl ester are produced, respectively, which are useful in synthetic chemical reactions. One can say.

  However, as an example of the reaction between the allyl raw material compound and the oxygen nucleophile, the case where the oxygen nucleophile is a carboxylate anion is generally well known, but the reaction example with other oxygen nucleophiles Are not so many due to their low reactivity.

  For example, as an example of reaction with phenols, as described in Non-Patent Document 2, allyl phenyl ethers by a palladium catalyst system having a triaryl type monodentate phosphite ligand such as triphenyl phosphite are used. Although the synthesis example of is known, its activity is not sufficient.

  Moreover, reaction examples with alcohols are very limited due to the low nucleophilic attack of alcohol oxygen. As an example of the intermolecular reaction between an allyl raw material compound and alcohol oxygen, allyl alcohol by a catalyst system using a monodentate phosphite ligand such as triphenyl phosphite or triethyl phosphite in Non-Patent Document 3 and Non-Patent Document 4 The reaction of allyl alcohol with alcohols by a catalyst system composed of triphenyl phosphite, which is said to have the highest activity, has also been reported. However, it cannot be said that the catalytic activity is sufficiently high in either case.

  Other examples of attacks on π-allyl complexes by alcohol oxygen include alcohol oxygen present in a position where a 5-membered or 6-membered ring can be formed as the reaction proceeds, attacking the π-allyl terminal carbon Several examples of cyclization reactions that proceed in the molecule are known. For example, the synthesis example of the morpholine derivative by the palladium catalyst system which has triisopropyl phosphite which is a monodentate phosphite ligand as described in the nonpatent literature 5 is known. In addition, Non-Patent Document 6 reports a synthesis example of a five-membered ring product by a palladium catalyst system having a bidentate phosphite ligand having a cyclic bidentate phosphite ligand composed of a pentane-2,5-diyl group. . However, these reactions require the presence of an oxygen nucleophile at a position where it is easy to form a ring, and are allylation reactions that proceed because they are intramolecular reactions, and can be said to be special systems.

"Palladium Reagents and Catalysts -Innovations in Organic Synthesis-" published by John Wiley & Sons Organometallics, 1995, 14, p4585 Japan Society for the Promotion of Science, Creative Functional Chemistry 116th Committee 2002, 6, Joint Subcommittee Material p46 Proceedings of the Chemical Society of Japan, 2001, Vol. 79th, No. 2, p1194 Tetrahedron Lett., 1995, 36, p5527 J. Am. Chem. Soc., 1998, 120, p1732

  As described above, a low-reactivity oxygen nucleophilic agent can be produced by reacting an allyl raw material compound with an oxygen nucleophile, although it is possible to produce an ether compound or an ester compound important for organic synthesis. Since a highly active catalyst system that can be sufficiently reacted has not been developed, actual reaction examples are limited. In particular, in the reaction with alcohol, the reaction cannot sufficiently proceed unless a special environment such as a cyclization reaction in the molecule is used. Therefore, it has been desired to develop a new catalyst system that exhibits sufficiently high catalytic activity even in the reaction with such a low-reactivity oxygen nucleophile.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is to use a new catalyst system that exhibits sufficiently high activity even with a low-reactivity oxygen nucleophile when reacting an allyl raw material compound with an oxygen nucleophile. It is an object of the present invention to provide a method for producing an allyl compound capable of efficiently producing various allyl compounds, and a novel condensation copolymer produced thereby.

  The inventors of the present invention have made extensive studies aiming at developing a catalyst system capable of efficiently proceeding intermolecular reactions between various allyl raw material compounds and oxygen nucleophiles. Compared with a catalyst system composed of a group 10 transition metal compound and a polydentate phosphite compound compared to a catalyst system composed of a conventional monodentate phosphine or bidentate phosphine and a known catalyst system composed of triphenyl phosphite. Surprisingly, it was found to be very highly active, and the present invention was reached.

That is, the gist of the present invention is the presence of a catalyst comprising one or more transition metal compounds containing a transition metal selected from the group consisting of ruthenium, rhodium, iridium, nickel, palladium, and platinum, and a polydentate phosphite compound. By reacting an allyl raw material compound having an allyl group in the molecule and a substituent that is eliminated from the molecule by reaction with an oxygen nucleophile, a new allyl compound having a composition formula different from that of the allyl raw material compound is obtained. It exists in the manufacturing method of an allyl compound characterized by manufacturing.

  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, the catalyst is sufficiently high even for a low-reactivity oxygen nucleophile. Since a new catalyst system that exhibits activity is used, it is possible to efficiently produce more various types of allyl compounds than when a conventional catalyst system is used. Moreover, the condensation copolymer of the present invention produced by this production method is suitably used for various applications.

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 catalyst containing a specific transition metal compound described later and a multidentate phosphite compound also described later. In the presence of, an allyl raw material compound and an oxygen nucleophile are reacted to produce a new allyl compound having a composition formula different from that of the allyl raw material compound.

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 the total molecular weight is 1500 or less (having about 100 or less carbon atoms), and the reaction conditions It is preferable that all or a part of the allyl raw material compound can be dissolved by dissolution in a solvent, compatibility with an oxygen nucleophile, melting by heat, or the like. Of these, represented by the following general formula (a), the compound of R ^a to R ^e leaving group represented by X in the allyl group having a group represented by are bonded structure is preferred. The leaving group is bonded to carbon of the base substrate skeleton (allyl skeleton in the present invention), and is generally an electron-withdrawing group. It refers to atomic groups.

In the general formula (a), R ^{a to} R ^e are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a formyl group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group. Represents an alkylthio group, an arylthio group, an acyl group, or an acyloxy group (in this specification, the aryl group includes a heterocyclic compound that forms an aromatic 6π electron cloud above and below the 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 chain 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, or an aryloxycarbonyl group.

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

The carbon number of R ^{a to} R ^e is usually 40 or less, preferably 30 or less, and 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, R ^{a to} R ^e are each independently preferably ^a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group.

  Examples of groups that adversely affect the reaction system include those that poison the catalyst, such as groups containing conjugated dienes, and those that oxidize and disappear phosphite compounds, such as groups containing peroxide. Accordingly, throughout the present specification, a group that “has no risk of adversely affecting the reaction system” means that these 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) an acyloxy group represented by O—, a carbonate group represented by R′OC (═O) O—, a carbamate group represented by R′NHC (═O) O—, (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 organic group is not particularly limited as long as it does not adversely affect the reaction system, but is preferably an alkyl group or an aryl group. When R and R ′ are organic groups, the carbon number is usually 40 or less, preferably 30 or less, and more preferably 20 or less. Of these exemplified groups, the amino group, sulfonyl group, sulfonate group, acyloxy group, carbonate group, carbamate group, phosphate group, alkoxy group, or 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 exist in the carbon chain.

Among the above examples, X is 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 ═P (═O) —. And a sulfonate group having a skeleton structure represented by —S (═O) ₂ O—, among which a hydroxy group, an acyloxy group, and a carbonate group are preferable. Specific examples of the acyloxy group include C1-C6 acyloxy groups such as an acetoxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. Specific examples of the carbonate group include C1-C6 alkyl carbonate groups or aryl carbonate groups such as methyl carbonate group, ethyl carbonate group, and phenyl carbonate group. In particular, X is preferably a hydroxy group or an acyloxy group, and most preferably an acetoxy group.

In addition, arbitrary 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 detached. The number of rings is not particularly limited, but is usually 0 to 3, preferably 0 to 2, particularly preferably 0 or 1. The number of atoms forming each ring is not particularly limited, but 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 condensed ring structure.

When two or more groups of R ^{a to} R ^e and X are bonded to form a cyclic structure, the number of carbon atoms is usually 0, where p is the number of groups involved in the formation of the cyclic structure. ˜40 × p, preferably 0 to 30 × p, particularly preferably 0 to 20 × p.

  As 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 acids, allyl carbonates , Allyl carbamates, allyl phosphates, allyl ethers, vinyl ethylene oxides and the like.

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, 2-butenyldibenzylamine and the like.
Specific examples of allyl sulfones include allyl phenyl sulfone, methylyl-p-tolyl sulfone, 2-methyl-3-sulfolene, 1,3-diphenylallylmethyl sulfone and the like.
Specific examples of allyl sulfonates include allyl toluene-4-sulfonate, 3-thiophenemethane sulfonate, 4-chloro-2-butenyl methanesulfonate, and the like.

  Specific examples of carboxylic acid allyl esters 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 include 1-cyclohexyl-2-butene, 4-cyclopentene-1,3-diol-1-acetate, 1,4-diacetoxybutene-2, 3-acetoxy-4-hydroxybutene-1.

Specific examples of allyl carbonates include allylmethyl carbonate, 4-acetoxy-2-butenylethyl carbonate, and nerylmethyl carbonate.
Specific examples of allyl carbamates include allyl-N- (4-fluorophenyl) carbamate, 2-butenyl-N-methylcarbamate, furfuryl-N- (2-methoxydiphenyl) carbamate, and the like.

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 monooxide, cyclopentadiene monooxide, 1,3-cyclohexadiene monooxide, and the like.

  As particularly preferable 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 those A mixture of two or more compounds selected from the group consisting of compounds can be mentioned.

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

_{^{R 3 CH 2 -CH = CH-}} CH 2 R 4. . . Formula (c)
In the general formula (c), R ³ and R ⁴ each independently represents an acetoxy group or a hydroxy group. Specific examples of 1,4-disubstituted butene-2 represented by the general formula (c) include 1,4-diacetoxybutene-2, 1-acetoxy-4-hydroxybutene-2, and 1,4- Dihydroxybutene-2 is mentioned.

  Next, the oxygen nucleophile used in the production method of the present invention will be described. In general, a nucleophile refers to a reactant that has an unshared electron pair, is basic, and has a tendency to attack the carbon nucleus. Any reactant that has an electron pair and tends to attack the allylic terminal carbon nucleus of the π-allyl complex with the electron pair is used as the oxygen nucleophile.

Oxygen nucleophilic agent usable in the present invention, specifically, the compound of the proton adduct represented by AO-H containing nucleophilic oxygen atom, or, AO its deprotonated body ^- represented by An anion is a compound that can be an anion in the reaction system. In the above formula, A represents a hydrogen atom or a monovalent organic group. The organic group is bonded to the nucleophilic oxygen atom by a carbon atom, nitrogen atom, phosphorus atom, or sulfur atom, becomes a liquid in the reaction system, and has no possibility of adversely affecting the reaction system. Things are used. The number of carbon atoms in these organic groups is preferably in the range of 40 or less because it is easily dissolved in the reaction system. Of these, preferably 30 or less, particularly preferably 20 or less.

Examples of the organic group bonded to the nucleophilic oxygen atom with a carbon atom include an unsubstituted or substituted chain or cyclic alkyl group, an unsubstituted or substituted aryl group, and an acyl group.
Examples of the organic group bonded to the nucleophilic oxygen atom and the nitrogen atom include an unsubstituted or substituted amino group, a group having a C═N bond, and the like.
Examples of the organic group bonded to the nucleophilic oxygen atom and the phosphorus atom include an unsubstituted or substituted phosphonate group, an unsubstituted or substituted phosphinate group, or an unsubstituted or substituted phosphinoyl group.

Examples of the organic group bonded to the nucleophilic oxygen atom and the sulfur atom include an unsubstituted or substituted sulfonyl group.
In addition, the substituent of each of the exemplified groups is not particularly limited as long as it does not adversely affect the reaction system, but is not limited to a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain shape. Alternatively, a 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, or an aryloxycarbonyl group is preferable. When each of the above exemplified groups has these substituents, the carbon number including the substituents is set within the above range.

However, even in the case of an oxygen nucleophile that falls within the above definition, a substituent (X in the above general formula (a) or its anion X ⁻ ) or the In the case of the same as the proton adduct (X—H), the reaction does not seem to proceed, or the isomerized product of the allyl raw material compound is only obtained as a product, so such an oxygen nucleophile is excluded. Is done. In addition, when the oxygen nucleophile is exactly the same as the allyl raw material compound, for example, when both the oxygen nucleophile and the allyl raw material compound are allyl alcohol, the production obtained as described in the section of the prior art The product is limited to diallyl ether having a structure in which the raw material is simply dehydrated and condensed, and lacks importance from the viewpoint of performing a wide range of synthesis, so such oxygen nucleophiles are also excluded.

  Among the oxygen nucleophiles described above, the total molecular weight is 400 or less (the number of carbon atoms is about 30 or less), and all or a part of the oxygen nucleophile is dissolved in a solvent under the reaction conditions. Those that can be dissolved by melting with heat or melting by heat are preferred.

When specific examples of the oxygen nucleophile are listed in the form of a proton adduct, when A is a hydrogen atom, it is water.
When A is an organic group bonded to a nucleophilic oxygen with 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, cyclohexane Alcohols such as hexanol, ethylene glycol, 1,3-propanediol, and 1,4-butanediol; phenol, p-methoxyphenol, 2,4-dimethylphenol, 1-naphthol, 2-naphthol, 3,6- Examples include phenols such as di-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 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, o-toluic acid Aromatic carboxylic acids such as
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.
Specific examples of the selenocarboxylic acids include a compound represented by CH ₃ (C═Se) —OH, a compound represented by PhC (═Se) —OH, and the like. In the present specification, Ph represents a phenyl group.

  When A is an organic group bonded with a nucleophilic oxygen and a nitrogen atom, hydroxyamines such as N, N-diethylhydroxyamine and N, N-dibenzylhydroxyamine; acetone oxime, benzophenone oxime, cyclopenta Examples thereof include oximes such as nonoxime; carbamates such as t-butyl-N-hydroxycarbamate; hydroxyimides such as N-hydroxymaleimide and N-hydroxysuccinimide; or 1-hydroxybenzotriazole.

  When A is an organic group bonded to a nucleophilic oxygen with a phosphorus atom, phosphinic acids such as dimethylphosphinic acid and diphenylphosphinic acid; phosphonic acid esters such as ethylphosphonic acid and propylphosphonic acid monophenyl ester; and Examples thereof include phosphoric acid esters such as phosphoric acid diphenyl ester and phosphoric acid dimethyl ester.

  When A 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 sulfuric acid monophenyl ester, sulfuric acid monooctyl ester, etc. And sulfuric acid monoesters.

In addition, although all the above illustrations were shown with the proton adduct, the deprotonated substance of each exemplary compound and the compound which can become the said deprotonated substance in a reaction system are illustrated similarly. Examples of the compound that can be the deprotonated substance in the reaction system include compounds in which the deprotonated substance is bonded to other atoms or atomic groups. Examples of other atoms or atomic groups bonded to the deprotonated substance include various monovalent cations (Na ⁺ , K ⁺ etc.) and the like.

  Among the above examples, the case where A is an organic group bonded to a nucleophilic oxygen with a carbon atom is particularly preferable, and specifically, the following types (i) to (iv) of oxygen nucleophiles are particularly preferable.

(i) RO—H or RO ⁻ (wherein R represents an alkyl group which may have a substituent and may have a double bond or a triple bond in the carbon chain.) Or a deprotonated product thereof.

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

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

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

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

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

  Among these, as the oxygen nucleophile of type (ii), monohydroxyaryl or dihydroxyaryl is preferable. Specifically, phenol, 1-naphthol, 2-naphthol, catechol, resorcinol, hydroquinone, or 2,6 -C1-C15 things, such as dihydroxy naphthalene, are preferable.

  Examples of the oxygen nucleophile of type (iii) include saturated aliphatic carboxylic acids and their substituents, unsaturated aliphatic carboxylic acids and their substituents, aliphatic dicarboxylic acids and their substituents Etc. Examples of saturated aliphatic carboxylic acids and their substituents include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, cyclohexanecarboxylic acid, α-methylbutyric acid, γ-chloro-α-methylvaleric acid, Examples include α-hydroxypropionic acid and γ-phenylbutyric acid. 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 bodies. Examples of the aliphatic dicarboxylic acids and their substituent-containing bodies include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and the like.

  Among these, the oxygen nucleophile of type (iii) is preferably a saturated aliphatic carboxylic acid or a saturated aliphatic dicarboxylic acid, specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid Preferred are those having 1 to 20 carbon atoms such as myristic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.

  Type (iv) oxygen nucleophiles include aromatic carboxylic acids and their substituent containing bodies, aromatic di- or polycarboxylic acids and their substituent containing bodies. Examples of aromatic carboxylic acids and their substituents include benzoic acid, 3-cyanobenzoic acid, 2-bromobenzoic acid, 2,3-dimethoxybenzoic acid, 4-phenoxybenzoic acid, p-nitrobenzoic acid, m -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, and naphthalene-1,4,5,8-tetracarboxylic acid An acid etc. are mentioned.

  Among these, the oxygen nucleophile of type (iv) is preferably an aromatic carboxylic acid or dicarboxylic acid, specifically, benzoic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, isophthalic acid, or Those having 6 to 15 carbon atoms such as terephthalic acid are preferred.

  Then, the catalyst used with the manufacturing method of this invention is demonstrated. The catalyst used in the present invention includes one or more transition metal compounds and a multidentate 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 Inorganic Chemical Nomenclature Revised Edition (1998)) are used. Specific examples include iron compounds, ruthenium compounds, osmium compounds, cobalt compounds, rhodium compounds, iridium compounds, nickel compounds, palladium compounds and platinum compounds, among which ruthenium compounds, rhodium compounds, iridium compounds, nickel compounds, Palladium compounds and platinum compounds are preferable, nickel compounds, palladium compounds and platinum compounds are more preferable, and palladium compounds are particularly preferable. The type of these compounds is arbitrary, but specific examples include the above transition metal acetates, acetyl cetonate compounds, halides, sulfates, nitrates, organic salts, inorganic salts, alkene coordination compounds, amine coordination compounds. Pyridine coordination compounds, carbon monoxide coordination compounds, phosphine coordination compounds, phosphite coordination compounds, 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 , RuCl ₂ (PPh ₃ ) _{3 and the} like. 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 . Rhodium compounds include RhCl ₃ , Rh (OAc) ₃ , [Rh (OAc) ₂ ] ₂ , Rh (acac) (CO) ₂ , [Rh (OAc) (cod)] ₂ , [RhCl (cod)] ₂ Etc. 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 , NiCl ₂ (PPh ₃ ) _{3 and the} like. 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 , Other 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. Platinum compounds 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 is mentioned. In the above examples, cod represents 1,5-cyclooctadiene, dba represents dibenzylideneacetone, acac represents acetylacetonate, and Ac represents an acetyl group.

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

Although there is no restriction | limiting in particular about the usage-amount of a transition metal compound, From a catalyst activity and economical viewpoint, it is 1x10 < ^-8 > (0.01 molppm) molar equivalent or more normally with respect to the allyl compound which is a reaction raw material, Above all, 1 × 10 ⁻⁷ (0.1 mol ppm) molar equivalent or more, particularly 1 × 10 ⁻⁶ (1 mol ppm) molar equivalent or more, usually 1 molar equivalent or less, especially 0.001 molar equivalent or less, especially 0 It is preferably used in the range of 0.0001 molar equivalent or less.

  On the other hand, the type of polydentate phosphite compound is not particularly limited as long as it is a phosphite compound that becomes a chelating ligand for the above-described transition metal compound. The number of coordination sites is usually from 2 to 4 but is preferably bidentate. 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. is there.

  Among the bidentate phosphites, preferable compounds include at least one compound selected from the group consisting of compounds represented by the following general formulas (I) to (IV).

In the above general formulas (I) to (IV), R ^{10 to} R ¹⁷ each independently represents a chain or cyclic alkyl group or an aryl group. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, and Examples thereof include a chain alkyl group such as a decyl group; or a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of aryl groups include phenyl, tolyl, xylyl, di-t-butylphenyl, naphthyl, di-t-butylnaphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, Examples thereof include an isoquinolyl group, an indolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, and a thiazolyl group.

  Note that the above-described alkyl group and aryl group may further have a substituent. The number of substituents is not particularly limited, but is usually 6 or less, preferably 4 or less. The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, the halogen atom, hydroxy group, amino group, formyl group, cyano group, nitro group, chain-like or 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 are preferred.

The carbon number of R ^{10 to} R ¹⁷ is usually 40 or less, preferably 30 or less, and more preferably 20 or less. When the above-described alkyl group or aryl group further has a substituent, the total number of carbon atoms including the substituent is set in the above range.

In view of the stability of the above-described phosphite among the above exemplified groups, R ^{10 to} R ¹⁷ are preferably unsubstituted or substituted aryl groups. Specific examples of the unsubstituted or substituted aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl 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, 3,5-dichlorophenyl group, 4- Trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-di Toxiphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, pentafluorophenyl group, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 3-t-butyl-2-naphthyl group 3-methyloxycarbonyl-2-naphthyl group, 3,6-di-t-butyl-2-naphthyl group, 5,6,7,8-tetrahydronaphthalen-2-yl group, 5,6,7,8 -Tetrahydronaphthalen-1-yl group etc. are mentioned.

In the general formula (I), T represents a tetravalent organic group. The tetravalent organic group is not particularly limited as long as it does not adversely affect the reaction system, but is a carbon atom, an unsubstituted or substituted alkanetetrayl group, an unsubstituted or substituted benzenetetrayl group, or A group having a structure represented by T ^1- (Q ² ) _n -T ² is preferred. T ¹ and T ² each independently represents a trivalent organic group. As the trivalent organic group, an unsubstituted or substituted alkanetriyl group and an unsubstituted or substituted benzenetriyl group are preferable. Q ² represents —CR ¹⁸ R ¹⁹ — (R ¹⁸ and R ¹⁹ each independently represents a chain or cyclic alkyl group or an aryl group), —O—, —S—, or —CO—. n is 0 or 1. Examples of the alkyl group and aryl group for R ¹⁸ and R ¹⁹ include the same groups as those described above for R ^{10 to} R ¹⁷ .

In the general formulas (II) to (IV), Z ^{1 to} Z ³ and A ^{1 to} A 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 an 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 possibility of adversely affecting the reaction system. Preferred examples of the substituent include halogen atom, hydroxy group, amino group, formyl group, cyano group, nitro group, chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkylthio. Group, arylthio group, perfluoroalkyl group, trialkylsilyl group, alkoxycarbonyl group, aryloxycarbonyl group and the like.

Z ¹ to Z ³ and the number of carbon atoms of each of A ¹ to A ³ is usually 1 to 60. 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 carbon number 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 carbon number is usually 60 or less, preferably 50 or less, and 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. It is done.

  Specific examples of the unsubstituted or substituted arylene group include 1,2-phenylene group, 1,3-phenylene group, 3,5-di-t-butyl-1,2-phenylene group, and 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).

On the other hand, a diarylene group is a group in which two arylene groups are linked directly or via a divalent organic group. Specifically, -Ar ^1- (Q ¹ ) _n -Ar ^2- A group having the structure represented. Here, 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 ¹⁸ R ¹⁹ —. Here, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, a chain or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. n represents 0 or 1. The substituent that Ar ¹ and Ar ² arylene group and the alkyl group and aryl group of R ¹⁸ and R ¹⁹ may have, respectively, is not particularly limited as long as there is no risk of adversely affecting the reaction system. Preferable specific examples include halogen atom, hydroxy group, amino group, formyl group, cyano group, nitro group, chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkylthio group, Examples thereof include an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
Specific examples of the diarylene group that may have a substituent include groups having structures represented by the following formulas (A-1) to (A-48).

  As described above, phosphites having various structures can be used depending on the combination of substituents constituting the phosphite compounds represented by the general formulas (I) to (IV). Among them, specific examples are preferable. As examples of the general formula (I), the following formulas (L-1) to (L-5) are used. As examples of the general formula (II), the following formulas (L-6) to (L-32) are used. Examples of (III) include the following formulas (L-33) to (L-47), and examples of formula (IV) include the compounds represented by the following formulas (L-48) to (L-57). be able to.

Among the phosphite compounds exemplified above, bidentate phosphite compounds having a structure represented by the above general formulas (II) to (IV) are preferable. Specific examples thereof include compounds having structures represented by the above formulas (L-6) to (L-57). Furthermore, in order to improve the stability of such phosphite compounds, R ^{10 to} R ¹⁷ are each independently an unsubstituted or substituted aryl group, or Z ^{1 to} Z ³ are each independently unsubstituted or substituted. It is particularly preferably a substituted diarylene group, and A ^{1 to} A ³ are each independently an unsubstituted or substituted alkylene group, an arylene group, an alkylene-arylene group, or a diarylene group. Specific examples thereof include the above formulas (L-8), (L-10) to (L-12), (L-14), (L-15), (L-18) to (L-20), (L-24) to (L-30), (L-32), (L-36) to (L-39), (L-45) to (L-47), (L-51), (L And compounds having structures represented by -53) to (L-57).

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

  The transition metal compound and the polydentate phosphite compound may be added to the reaction system alone or may be used in a complexed state in advance. Alternatively, the multidentate phosphite compound bound to some insoluble resin carrier or the like may be used in the reaction as a state of an insoluble solid catalyst in which the transition metal compound is supported. Furthermore, the reaction may be carried out using only one kind of multidentate phosphite compound, or the reaction may be carried out using two or more kinds of multidentate phosphite compounds simultaneously in any combination.

  By using the catalyst composed of the transition metal compound and the polydentate phosphite compound described above, the allyl raw material compound and the oxygen nucleophile are reacted to efficiently produce a new allyl compound (for example, an ester compound or an ether compound). Can be manufactured well.

  In carrying out the production method of the present invention, the reaction is usually carried out in the liquid phase. The reaction can be carried out either in the presence or absence of a solvent. In the case of using a solvent, any solvent can be used as long as it dissolves the catalyst and the raw material compound and does not adversely affect the catalyst 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, Aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, etc., high boilers produced as by-products in the allylation reaction system, allyl compounds as raw materials, Product allyl Compounds, compounds derived from the leaving group of the starting allylic compounds. The amount of these solvents to be used is not particularly limited, but is usually 0.1 times or more, preferably 0.2 times or more, and usually 20% by weight with respect to the total amount of allyl compounds as raw materials. It is not more than double, preferably not more than 10 weight times.

  In carrying out the reaction, various reaction methods can be used. For example, using a stirring type complete mixing reactor, plug flow type reactor, fixed bed type reactor, suspension bed type reactor, etc. Can do.

  When actually performing the reaction for each, the conditions may be appropriately determined depending on the reaction substrate and product. For example, in the case of a stirring type complete mixing reactor, the allyl raw material compound, the oxygen nucleophile, and in some cases, the solvent Oxygen is obtained by continuously or semi-continuously introducing a mixture obtained by adding a catalyst solution prepared in a catalyst preparation tank into a reactor and stirring the mixture at a certain reaction temperature. The reaction can be carried out while the allylation reaction of the nucleating agent proceeds and a part of the reaction liquid is continuously or semi-continuously extracted from the reactor. Further, in the case of a plug flow type reactor, the reaction can proceed while the reaction solution containing the above raw materials and catalyst is passed 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. Furthermore, when using an insoluble solid catalyst carrying a catalyst, a fixed bed reaction method in which the reaction is carried out while passing a solution containing raw materials through a reactor packed with the catalyst, or a particulate insoluble catalyst is used. It is also possible to employ a suspension bed reaction system in which the catalyst and the solution containing the raw material are stirred and mixed in the reactor, and the reaction is carried out in a suspended state.

  The reaction temperature is not particularly limited as long as it is a temperature at which the catalytic reaction proceeds, but when a noble metal compound such as palladium is used as a catalyst, there is a risk that metalization occurs and the effective catalyst concentration decreases when the temperature is too high. is there. Further, since there is a concern about decomposition of the phosphite compound at a high temperature, it 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 must be filled with a gas inert to the reaction system, such as argon or nitrogen, except for vapors derived from solvents, raw material compounds, reaction products, reaction byproducts, catalytic decomposition products, etc. Is desirable. It should be particularly noted that oxygen contamination due to air leaks or the like causes catalyst deterioration, particularly oxidation loss of the phosphite compound, so 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 conversion value of the raw material to be aimed at, but under a certain catalyst concentration, it is necessary to lengthen the reaction time as the high conversion rate is obtained. . On the other hand, in order to shorten the reaction time while maintaining a high conversion rate, it is necessary to increase the catalyst activity by increasing the concentration of the catalyst used, increasing the amount of catalyst, or increasing the reaction temperature. 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.

  For the separation of the allyl compound and the catalyst obtained by the reaction, any separation operation used in a conventional liquid catalyst recirculation process can be employed. Specific examples of the separation operation include distillation operations such as simple distillation, vacuum distillation, thin film distillation, and steam distillation, as well as separation operations such as gas-liquid separation, evaporation (evaporation), gas stripping, gas absorption, and extraction. It is done. Each component may be separated in an independent process, or two or more components may be separated simultaneously in a single process. When some allyl raw material compounds and nucleophiles remain unreacted, it is more economical to collect them by the same separation method and recycle them again into the reactor. Furthermore, it is more economical and desirable to separate or recover the separated catalyst as it is in the reactor and to reuse it after reactivation.

  In the method for producing an allyl compound, 3,4-disubstituted butene-1 represented by the above general formula (b) or 1,4-bis represented by the above general formula (c) is used as the allyl raw material compound. When substituted butene-2 was used and a bifunctional oxygen nucleophile was used as the oxygen nucleophile, butene diyl units represented by the following formula A and formula A ′ derived from butene (hereinafter, each unit was appropriately selected) Abbreviations “A” and “A ′”) and dioxy units represented by the following formula B and / or formula B ′ and / or formula B ″ derived from a bifunctional oxygen nucleophile (hereinafter referred to as “B”) Thus, a novel condensation copolymer (condensation copolymer of the present invention) containing each unit as appropriate is abbreviated as “B”, “B ′” and “B” ”is obtained.

（上記各式中、Ｒｆ、Ｒｇ、Ｒｈは、それぞれ独立に、置換基を有していてもよい二価の有機基を表わす。）

(In the above formulas, Rf, Rg and Rh each independently represents a divalent organic group which may have a substituent.)

  In the condensation copolymer of the present invention, butene diyl units represented by the formulas A and A ′ and dioxy units represented by the formulas B, B ′ and B ″ are alternately bonded.

As the butenediyl unit in the condensation copolymer of the present invention, A and A ′ are randomly selected, and at least one A and at least one A ′ are included. That is, the number of butenediyl units in the condensation copolymer is 2 or more.
The abundance ratio of A and A ′ in the condensation copolymer of the present invention is not particularly limited, but the unit of A tends to increase, and specifically, A: A ′ (molar ratio) The value is usually 1:10 or more, preferably 1: 2 or more, more preferably 1: 1 or more, and is usually 10: 1 or less, preferably 5: 1 or less, more preferably 3: 1 or less.

The dioxy unit in the condensation copolymer of the present invention may be a structure in which only one of B, B ′ and B ″ is used, or may be a random mixture of any two types. Or a random mixture of all three types.
The terminal structure of the condensation copolymer of the present invention is an acetoxy group or a hydroxy group when the terminal unit of the condensation copolymer is an A or A ′ butenediyl unit. When the terminal unit is a dioxy unit of B, B ′ or B ″, it is a hydrogen atom.

  The molecular weight of the condensation copolymer of the present invention is usually 200 or more, preferably 300 or more, more preferably 500 or more, and usually 1 million or less, preferably 100,000 or less, more preferably 10,000 or less, still more preferably. 5000 or less.

  As a synthesis method of the condensation copolymer of the present invention, 3,4-disubstituted butene-1 or 1,4-disubstituted represented by the general formula (b) or (c) in the presence of the catalyst of the present invention is used. It can be obtained by reacting butene-2 with a bifunctional oxygen nucleophile. Specific examples of 3,4-disubstituted butene-1 of the general formula (b) preferably used include 3,4-diacetoxybutene-1, 3-acetoxy-4-hydroxybutene-1, 4-acetoxy-3 -Hydroxybutene-1,3,4-dihydroxybutene-1. Specific examples of 1,4-disubstituted butene-2 of the general formula (c) preferably used include 1,4-diacetoxybutene-2, 1-acetoxy-4-hydroxybutene-2, 1,4. -Dihydroxybutene-2. These compounds may be used alone or as a mixture of two or more.

  Bifunctional oxygen nucleophiles can be classified mainly into 3 groups depending on the type of dioxy unit in the target condensation copolymer. Specifically, diols are used as the bifunctional oxygen nucleophile corresponding to the dioxy unit B, hydroxycarboxylic acids are also used as B ′, and dicarboxylic acids are used as B ″. Specific examples of diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2,4-dihydroxypentane, and 2,2-diethyl-1,3-propane. Alkanediols such as diols, Alkenediols such as 1,4-dihydroxy-2-butene, 1,9-dihydroxy-3,6-nonadiene, 1,4-dihydroxy-2-butyne, 1,5-dihydroxy- Alkynediols such as 3-heptin, cycloalkanediols such as cyclohexane-1,4-diol and cyclopentane-1,3-diol, hydroquinone, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 4, 4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propyl Diphenols derivatives such as bread, other, 4- (2-hydroxyethyl) phenol, 1,4-dihydroxy methyl benzene. Specific examples of hydroxycarboxylic acids include 3-hydroxypropionic acid, 4-hydroxybenzoic acid, 3-sidroxymethylbenzoic acid, 4-hydroxyphenylacetic acid and the like. Specific examples of dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, and naphthalene. And aromatic dicarboxylic acids such as -1,8-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. As the above-mentioned bifunctional oxygen nucleophile, a specific compound may be used alone or as a mixture of two or more kinds.

  As the method for producing the condensation copolymer of the present invention, a reaction between the allyl raw material compound described in the present invention and an oxygen nucleophile can be used. However, if acetic acid or water produced as a by-product due to the reaction accumulates in the system, the molecular weight of the condensation copolymer is difficult to increase. Therefore, when it is desired to increase the molecular weight of the condensation copolymer, acetic acid and water are added from within the reaction system. It is preferable to push the reaction while removing water. Methods for removing acetic acid and water from the reaction system include distillation by distillation under normal or reduced pressure, and addition of compounds that react with acetic acid and water to form insoluble salts, such as calcium oxide. Etc.

  As a method for removing the catalyst from the obtained condensation copolymer, catalyst separation by distillation is effective when the condensation copolymer has a low molecular weight and can be distilled. Examples thereof include a method (precipitation precipitation method) in which a poor solvent for the polymer is added to precipitate the condensation copolymer, and the supernatant phase containing the catalyst is separated to remove the catalyst (fractional precipitation method). In this case, the catalyst, low molecular weight condensation copolymer and raw material contained in the supernatant phase can be reused by returning to the reactor again after removing the poor solvent from the supernatant phase by distillation or the like. More economical and preferable. In addition, since the condensation copolymer in the case of performing the fractional precipitation method contains a poor solvent, it must be removed by distillation or the like.

  In addition, the condensation copolymer of the present invention is characterized by a structure having double bonds in the main chain and side chains, but as its use, it can be added to other condensation copolymers and polymers. The function of the cross-linking agent can be performed by reacting the double bond, or a new functional group can be introduced by further reacting the double bond in the condensation copolymer to introduce a new functional group. It can be used for producing a copolymer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.

<Examples 1 and 2 and Comparative Examples 1 and 2>
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 (L-26) with respect to palladium as a polydentate phosphite compound. ) Bidentate phosphite compound (Example 1) or the above (L-8) bidentate phosphite compound (Example 2) (0.1204 mmol) was placed in Schlenk, and after argon substitution, 2.0 ml of tetrahydrofuran was added. In addition, a catalyst solution having a palladium concentration of 15.05 mmol / l was prepared by stirring at room temperature. Subsequently, the Schlenk prepared separately for carrying out 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. Thereto, 20.0 μl of the above catalyst solution was added with a microsyringe, and the reaction was performed 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.

  For comparison, the conventional bidentate phosphine ligand 1,4-bis (diphenylphosphino) butane (dppb) and the monodentate phosphite ligand triphenylphosphite ligand were used. The reaction was carried out in the same manner. However, when triphenyl phosphite, which is a monodentate ligand, was used, about 8 equivalents were added to palladium.

<Examples 3-5 and Comparative Examples 3-5>
The present invention was applied to a synthesis reaction of allyl octyl ether using allyl acetate as an allyl starting compound and 1-octanol as an oxygen nucleophile.

  0.0048 g (0.0048 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and the bidentate phosphite compound of the above (L-26) as a multidentate phosphite compound ( Example 3), bidentate phosphite compound of (L-47) (Example 4) or bidentate phosphite compound of (L-11) (Example 5) 0.194 mmol) were placed in a Schlenk and purged with argon, then 0.943 g (9.420 mmol) of allyl acetate and 2.422 g (18.594 mmol) of 1-octanol were added under argon and heated at 100 ° C. The reaction was performed. After the reaction for 60 minutes, the yield of allyl octyl ether was determined by analyzing the solution composition by gas chromatography.

  For comparison, the conventional bidentate phosphine ligand 1,4-bis (diphenylphosphino) butane (dppb), the monodentate phosphine ligand triphenylphosphine and the monodentate phosphite ligand The same reaction was carried out using a triphenyl phosphite ligand. However, when a monodentate ligand was used, about 4 equivalents were added to palladium.

<Examples 6 and 7 and Comparative Examples 6 and 7>
The present invention was applied to a synthesis reaction of allyl benzoate using allyl acetate as an allyl starting 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 the transition metal compound, and the bidentate phosphite compound of the above (L-55) as the multidentate phosphite compound ( Example 6) or the above bidentate phosphite compound (L-12) of (L-12) (Example 7) 4 equivalents (0.1204 mmol) with respect to palladium, respectively, were placed in a Schlenk, and after substitution with argon, 2.0 ml Tetrahydrofuran was added and stirred at room temperature to prepare a catalyst solution with a palladium concentration of 15.05 mmol / l. Subsequently, the Schlenk separately prepared for the reaction was purged 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. Thereto was added 60.0 μl of the above catalyst solution 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.

  For comparison, the conventional bidentate phosphine ligand 1,4-bis (diphenylphosphino) butane (dppb) and the monodentate phosphite ligand triphenylphosphite ligand were used. The reaction was carried out in the same manner. However, when triphenyl phosphite, which is a monodentate ligand, was used, about 8 equivalents were added to palladium.

<Example 8>
The present invention was applied to a synthesis reaction of butylbutenyl ethers using cis-1,4-diacetoxy-2-butene as an allyl starting compound and 1-butanol as an oxygen nucleophile.

  0.0017 g (0.0040 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight and 0.0173 g (0.0162 mmol) of bidentate phosphite represented by the above (L-26) in 4 equivalents. After putting into Schlenk and purging with nitrogen, 1.418 g (8.233 mmol) of cis-1,4-diacetoxy-2-butene and 2.327 g (31.395 mmol) of 1-butanol were added under nitrogen at 100 ° C. The reaction was carried out by heating at When the solution composition was analyzed by gas chromatography after the reaction for 5 hours, the conversion of cis-1,4-diacetoxy-2-butene was 97.5%, dibutoxybutene was 71.8%, acetoxybutoxybutene Was 25.7%.

  More specifically, the breakdown of 71.8% of dibutoxybutene is 56.0% of 1,4-dibutoxy-2-butene (cis and trans mixture), and 15.8 of 3,4-dibutoxy-1-butene. As a breakdown of 25.7% acetoxybutoxybutene, 12.6% of 1-acetoxy-4-butoxy-2-butene (cis, trans mixture), 3-acetoxy-4-butoxy-1 -Butene was 4.9% and 4-acetoxy-3-butoxy-1-butene was 8.2%.

  As is apparent from the above results, the bidentate phosphite-based arrangement of the present invention is compared with the activity of the conventional bidentate phosphine-based ligand and the catalyst comprising triaryl type monodentate phosphite. It can be seen that the activity of the catalyst comprising the ligand is high.

<Example 9>
The present invention was applied to a synthesis reaction of phenylbutenyl ethers using cis-1,4-diacetoxy-2-butene as an allyl starting compound and phenol as an oxygen nucleophile.

  0.0018 g (0.0044 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight and 0.0187 g (0 of bidentate phosphite represented by the above (L-26) in 2 equivalents to palladium. 0.0175 mmol) was placed in a Schlenk and purged with nitrogen. The reaction was carried out 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.

  When the solution composition was analyzed by gas chromatography after the reaction for 60 minutes, the conversion of cis-1,4-diacetoxy-2-butene was 75.2%, diphenoxybutene was 14.9%, acetoxyphenoxybutene Was 59.8%.

  More specifically, the breakdown of 14.9% of diphenoxybutene includes 13.9% of 1,4-diphenoxy-2-butene (cis and trans mixture) and 1.0 of 3,4-diphenoxy-1-butene. As a breakdown of 59.8% acetoxyphenoxybutene, 37.8% of 1-acetoxy-4-phenoxy-2-butene (cis, trans mixture), 3-acetoxy-4-phenoxy-1 -Butene was 11.1% and 4-acetoxy-3-phenoxy-1-butene was 10.9%.

<Example 10>
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 which is a bifunctional carboxylic acid as an oxygen nucleophile. .

  0.0074 g (0.0162 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight and 0.0693 g (0 of bidentate phosphite represented by the above (L-26) in 2 equivalents to palladium 0.0647 mmol) was placed in a two-necked round bottom flask and purged with nitrogen, then 10.005 g (58.107 mmol) cis-1,4-diacetoxy-2-butene and 7.104 g (48.610 mmol) adipic acid were added. The reaction was performed by adding under nitrogen and heating at 100 ° C. under 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 resulting acetic acid was distilled out of the system under reduced pressure. When the solution composition was analyzed by gas chromatography after the reaction for 7 hours, 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 generated oligomer was analyzed by gel permeation chromatography, it was found that it was a polyester oligomer showing a maximum molecular weight of 10,000 with a molecular weight of 4000 as a molecular weight in terms of polystyrene.

<Example 11>
This is a synthesis reaction for unsaturated bond-containing polyether oligomers using cis-1,4-diacetoxy-2-butene as the allyl starting compound and 1,4-butanediol, which is a bifunctional alcohol, as the oxygen nucleophile. The invention was applied.

  0.0572 g (0.1249 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight and 0.2670 g of bidentate phosphite represented by the above (L-26) in an amount equivalent to palladium (0 2492 mmol) into a two-necked round bottom flask and purged with nitrogen, followed by 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 performed at 100 ° C while gradually increasing the degree of vacuum from 50 mmHg in the same manner as in Example 9. When the solution composition was analyzed by gas chromatography after the reaction for 7 hours, 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 generated oligomer was analyzed by gel permeation chromatography, it was found to be a polyether oligomer showing a maximum molecular weight of 27,000 as a molecular weight in terms of polystyrene.

<Example 12>
Cis-1,4-diacetoxy-2-butene was used as the allyl starting compound, and 2,2-bis (4-hydroxyphenyl) propane (common name: 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 and 0.0852 g (0 of bidentate phosphite represented by the above (L-26) in 2 equivalents to palladium. 0.095 mmol) was placed in a two-necked round bottom flask and purged with nitrogen, and then 10.08 g (58.126 mmol) cis-1,4-diacetoxy-2-butene and 11.001 g (48.189 mmol) bisphenol A were added. It added under nitrogen and it reacted at 100 degreeC, raising the pressure reduction degree gradually from 50 mmHg similarly to Example 9. FIG. When the solution composition was analyzed by gas chromatography after the reaction for 7 hours, the conversion of cis-1,4-diacetoxy-2-butene was almost 100%, and a cage-like oligomer was obtained. When the molecular weight distribution of the generated oligomer was analyzed by gel permeation chromatography, it was found to be a polyether oligomer having a molecular weight in terms of polystyrene of 7000 centering on a molecular weight of 3200.

Claims (4)

One or more transition metal compounds containing a transition metal selected from the group consisting of ruthenium, rhodium, iridium, nickel, palladium, and platinum, and a group consisting of compounds having the structures represented by the following general formulas (II) to (IV) the presence of a catalyst comprising a one or more bidentate phosphite compound selected, have a substituent which is eliminated from該分terminal by the allyl group and reaction in the molecule and represented by the following general formula (a) structure A method for producing an allyl compound, characterized in that a new allyl compound having a composition formula different from that of the allyl raw material compound is produced by reacting an allyl raw material compound having an oxygen content with an oxygen nucleophile.

(In the above general formulas (II) to (IV), R ^{12 to} R ¹⁷ each independently represents an alkyl group or an aryl group which may have a substituent. Z ^{1 to} Z ³ and A ¹ to A ³ each independently represents an alkylene group, an arylene group, an alkylene-arylene group, or a diarylene group, which may have a substituent.

(In the general formula (a), R ^{a to} R ^e are independently hydrogen atom, halogen atom, hydroxy group, amino group, formyl group, alkyl group, aryl group (aromatic 6π electrons above and below the ring) Including a heterocyclic compound that forms a cloud. The same shall apply hereinafter.), An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group, and among these groups, an amino group, an alkyl group, and an aryl group , An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, and an acyloxy group may further have a substituent, and when any of R ^{a to} R ^e includes a carbon chain, the carbon One or more carbon-carbon double bonds or triple bonds may be present in the chain, and X is a halogen atom, hydroxy group, nitro group, amino group, sulfonyl group, A phonate group, an acyloxy group, a carbonate group, a carbamate group, a phosphate group, an alkoxy group, or an aryloxy group, and among these groups, an amino group, a sulfonyl group, a sulfonate group, an acyloxy group, a carbonate group, a carbamate group, a phosphate group, The alkoxy group or aryloxy group may further have a substituent, and when X contains a carbon chain, one or more carbon-carbon double bonds or triple bonds are present in the carbon chain. Also, any two or more of R ^{a to} R ^e and X may be bonded to each other to form one or more cyclic structures.) The oxygen nucleophile is a compound different from the substituent X and its proton adduct XH, which is eliminated from the allyl raw material compound by reaction, and is AO-H containing a nucleophilic oxygen atom or a deprotonation thereof. AO ⁻ (wherein A represents a hydrogen atom or an organic group bonded to the oxygen atom through a carbon atom, nitrogen atom, phosphorus atom, or sulfur atom). It characterized in that it is a compound, method for producing the allyl compound of claim 1. In the general formulas (II) to (IV), R ^{12 to} R ¹⁷ are each independently an aryl group which may have a substituent, and Z ^{1 to} Z ³ each independently have a substituent. The method for producing an allyl compound according to claim 1, wherein the diarylene group may be a diarylene group. The method for producing an allyl compound according to any one of claims 1 to 3, wherein the transition metal compound is a palladium compound.