JP2004107337A - Method for producing allyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently produce various allyl compounds by using a new catalyst system exhibiting enough high activity even on an oxygen nucleophile of which the reactivity is low, and reacting a raw material compound for the allyl compound with the oxygen nucleophile. <P>SOLUTION: The raw material compound for the allyl compound is reacted with the oxygen nucleophile having a structure other than that of the raw material compound for the allyl compound in the presence of a catalyst containing one or more transition metal compounds and a monodentate phosphite compound, 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 monodentate phosphite compound has a structure expressed by general formula (1): P(OR<SP>1</SP>)(OR<SP>2</SP>)(OR<SP>3</SP>) (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each an alkyl which may be substituted, provided that one or more carbon-carbon double bonds or triple bonds may exist in carbon chains of R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>, and further that two or more groups arbitrarily selected from R<SP>1</SP>, R<SP>2</SP>, and R<SP>3</SP>may together form one or more ring structures). <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 an oxygen nucleophile in the presence of a catalyst, and an ether compound and an ester compound produced thereby. .

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. Above all, when the nucleophile is an oxygen nucleophile such as alcohols, phenols, and carboxylic acids, allyl alkyl ethers, allyl phenyl ethers, and carboxylic acid allyl esters are formed, respectively, which are useful for synthetic chemistry. One can say.

However, as an example of a reaction between an allyl raw material compound and an oxygen nucleophile, although it is generally well-known that the oxygen nucleophile is a carboxylate anion, an example of a reaction with another oxygen nucleophile Is not so much due to its low reactivity.

For example, examples of the reaction with phenols include, as described in Non-Patent Document 2, allyl phenyl ethers using a palladium catalyst system having a triaryl monodentate phosphite ligand such as triphenyl phosphite. Is known, but the activity is not sufficient.

例 Also, examples of reactions with alcohols are very limited due to the low nucleophilic attack of alcohol oxygen. Non-Patent Documents 3 and 4 disclose, as examples of reactions between molecules of 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. And the reaction of allyl alcohol and alcohols with a catalyst system comprising triphenyl phosphite, which is said to have the highest activity, has been reported. However, in any case, the catalytic activity is not sufficiently high.

Other examples of alcohol oxygen attacking the π-allyl complex include the alcohol oxygen present at a position where a five-membered or six-membered ring can be formed as the reaction proceeds, attacking the π-allyl-terminal carbon. Several examples of intramolecular cyclization reactions are known. For example, a synthesis example of a morpholine derivative using a palladium catalyst system having triisopropylphosphite as a monodentate phosphite ligand as described in Non-Patent Document 5 is known. Further, Non-Patent Document 6 reports an example of synthesizing a five-membered ring product using a palladium catalyst system having a cyclic bidentate phosphite ligand having both ends composed of a pentane-2,5-diyl group. . However, these reactions require an oxygen nucleophile to be present at a position where a ring is easily formed, and are allylation reactions that proceed only because of 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, the reaction of an allyl raw material compound with a different oxygen nucleophile can produce an ether compound or an ester compound which is important in organic synthesis, but has low reactivity. Since a highly active catalyst system capable of sufficiently reacting a nucleating agent has not been developed, actual reaction examples are limited. In particular, in the reaction with an alcohol, the reaction cannot proceed sufficiently unless a special environment such as a cyclization reaction in a molecule is used as described above. Therefore, development of a new catalyst system that exhibits sufficiently high catalytic activity even in the reaction with such a low-reactivity oxygen nucleophile 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 use a new catalyst system that exhibits sufficiently high activity even for an oxygen nucleophile having low reactivity 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 which enables efficient production of various allyl compounds, and an ether compound and an ester compound produced thereby.

The present inventors have been diligently studying for the development of a catalyst system capable of efficiently proceeding the intermolecular reaction between various allyl raw material compounds and different oxygen nucleophiles. A catalyst system comprising a group 8-10 transition metal compound and a trialkyl monodentate phosphite compound comprises a conventional catalyst system comprising a monodentate phosphine or bidentate phosphine and triphenyl phosphite which is known in the prior art. The present inventors have found that the activity is surprisingly very high as compared with the catalyst system consisting of

That is, the gist of the present invention is to have at least one transition metal compound containing a transition metal selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table and a structure represented by the following general formula (1). By reacting an allyl raw material compound with an oxygen nucleophile having a different structure from the allyl raw material compound in the presence of a catalyst containing a monodentate phosphite compound, a composition formula different from the allyl raw material compound is obtained. The present invention relates to a method for producing an allyl compound, characterized by producing a new allyl compound shown in the following.

P (OR ¹ ) (OR ² ) (OR ³ ). . . General formula (1)
(In the general formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent. In the carbon chain of R ¹ , R ² and R ³ , May have one or more carbon-carbon double bonds or triple bonds, and any two or more of R ¹ , R ² , and R ³ may combine to form one or more cyclic structures. May be.)

According to the present invention, since a new catalyst system that exhibits sufficiently high catalytic activity even for an oxygen nucleophile having low reactivity is used, the allyl raw material compound is reacted with the oxygen nucleophile. When producing a new allyl compound, it becomes possible to produce more various kinds of allyl compounds more efficiently than when a conventional catalyst system is used.

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) comprises a specific transition metal compound described below and a monodentate phosphite compound having a specific structure also described later. By reacting an allyl raw material compound with an oxygen nucleophile having a structure different from that of the allyl raw material compound, a new allyl compound having a composition formula different from that of the allyl raw material compound is produced. Things.

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 Group, an alkylaryloxy group, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group.

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—, An acyloxy group represented by RC (＝ O) O—, a carbonate group represented by R′OC (＝ O) O—, a carbamate group represented by R′NHC (＝ O) O—, (R′O ) represents the ₂ P (= O) O- represented by phosphates group, an alkoxy group or an aryloxy group represented by RO-. 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, an aryl group, and the like are 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. 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 an acyloxy group, a carbonate group, and a carbamate group having a skeleton structure represented by —C (＝ O) O—, and a skeleton structure represented by ＰP (＝ O) —. phosphates groups, and -S (= O) are preferred Suruhoneito group having a skeleton structure represented by ₂ O-, inter alia 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-C6 alkyl carbonate group such as a methyl carbonate group, an ethyl carbonate group, and a phenyl carbonate group, and a C6-C12 aryl carbonate group. In particular, X is preferably an acyloxy 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 the allyl raw material compound of the above general formula (a), preferred are allyl halides, allyl alcohols, nitroallyls, allylamines, allyl sulfones, allyl sulfonates, allyl esters of carboxylic acids, allyl carbonates, allyl Examples thereof include 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, 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 A mixture of two or more compounds selected from the group consisting of those 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 represent an acetoxy group or a hydroxy group, and at least one of them is an acetoxy 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.

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, and at least one of them is an acetoxy group. Specific examples of the 1,4-disubstituted butene-2 represented by the general formula (c) include 1,4-diacetoxybutene-2 and 1-acetoxy-4-hydroxybutene-2.

Next, the oxygen nucleophile used in the production method of the present invention will be described. Generally, a nucleophile refers to a reactant that has an unshared electron pair, is basic, and has a tendency to attack a carbon nucleus. Any reactant having an electron pair and having a tendency to attack the allylic terminal carbon nucleus of the π-allyl complex with the electron pair is used as an 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, and further a compound that can be the anion in the reaction system. In the above formula, A 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. The number of carbon atoms of these organic groups is preferably in the range of usually 40 or less because it is easily dissolved in the reaction system. Among them, it is preferably 30 or less, particularly preferably 20 or less.

Examples of the organic group bonded to the nucleophilic oxygen atom and the carbon atom include an unsubstituted or substituted chain or cyclic alkyl group, an unsubstituted or substituted aryl group or an acyl group.
Examples of the organic group bonded with a nucleophilic oxygen atom and a 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 via a phosphorus atom include an unsubstituted or substituted phosphonate group, an unsubstituted or substituted phosphinate group, and an unsubstituted or substituted phosphinoyl group.
Examples of the organic group bonded with a nucleophilic oxygen atom and 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, a substituent (X in the above general formula (a) or its anion X ⁻ ) or a substituent which the oxygen nucleophile leaves from the allyl raw material compound by the reaction. In the case of the same proton-adduct (XH), the reaction does not proceed apparently, or the isomer of the allyl raw material compound is obtained only as a product, so such an oxygen nucleophile is excluded. Is done. Further, 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 product obtained as described in the section of the prior art is obtained. The product is limited to diallyl ether having a structure in which the raw material is merely dehydrated and condensed, and is not important from the viewpoint of performing a wide range of synthesis, and such an oxygen nucleophile is 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, And those which can be in a melted state by melting with heat or the like.

When specific examples of the oxygen nucleophile are listed in the form of a protonated product, when A is a hydrogen atom, it is water.
When A 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, 3,6- 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 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, CH ₃ (C = Se) compounds represented by -OH, or PhC (= Se) compounds represented by -OH, and the like. In this specification, Ph represents a phenyl group.

When A 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, cyclopentane Oximes such as non-oximes; t-butyl-N-hydroxycarbamate, N-hydroxymaleimide, N-hydroxysuccinimide, 1-hydroxybenzotriazole and the like.

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; Phosphate esters such as diphenyl phosphate and dimethyl phosphate are exemplified.

When A is an organic group bonded to 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 Monoesters of sulfuric acid.

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.).

Of the above examples, A is particularly preferably an organic group bonded to a nucleophilic oxygen and 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 a deprotonated product 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, 4-diol, 2-chloro-1,3-propanediol, 1,2-cyclopentanediol, glycerin, pentaerythritol and the like.

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 A diol having 1 to 10 carbon atoms such as alcohol, 2-ethylhexanol, n-octanol, 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol is 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, and 1,2,4-benzenetriol.

Among them, the type (ii) oxygen nucleophile is preferably monohydroxyaryl or dihydroxyaryl, and specifically, phenol, 1-naphthol, 2-naphthol, catechol, resorcinol, hydroquinone, or 2,6 -Dihydroxynaphthalene and the like 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, the type (iv) oxygen nucleophile is preferably an aromatic carboxylic acid or a dicarboxylic acid, and specifically, benzoic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, isophthalic acid, or Terephthalic acid and the like are preferred.

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 monodentate 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.

ト リ As the monodentate phosphite compound, a trialkyl phosphite compound having a structure represented by the following general formula (1) is used.

P (OR ¹ ) (OR ² ) (OR ³ ). . . General formula (1)

In the above general formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent. The alkyl group may be chain or cyclic, and in the case of a chain, may be linear or branched. Further, one or more carbon-carbon double bonds or triple bonds may be present in the carbon chain of the alkyl group. The type of the substituent of the alkyl group 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 Examples include 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, and an aryloxycarbonyl group.

Further, any two or more groups among R ¹ , R ² and R ³ may be bonded to each other to form one or more cyclic structures. The number of rings is not particularly limited, but is usually 0 to 3, preferably 0 to 2, and particularly preferably 0 or 1. When a plurality of rings are present, these rings may share a part to form a fused ring structure. 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.

The carbon number of R ¹ , R ² , and R ³ is each independently usually in the range of 1 to 20, preferably 1 to 15, and more preferably 1 to 10. When two or more groups out of R ¹ , R ² , and R ³ are bonded to form a cyclic structure, the number of carbon atoms is usually represented by p, where p is the number of groups involved in the formation of the cyclic structure. It is 1 to 40 × p, preferably 1 to 30 × p, particularly preferably 1 to 20 × p.

When specific examples of R ¹ , R ² and R ³ are listed, examples of the linear or branched alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group and an i-propyl group. Group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 2-chloroethyl group, benzyl Group, 2,2,2-trifluoroethyl group, 3-dimethylaminopropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 5-cyanopentyl group, 2-hydroxyethyl Group, 2-methoxyethyl group, and 3- (4-nitrophenyl) propyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a cycloheptyl group, a 2,3-diethylcyclohexyl group, a 4-ethoxycyclohexyl group, and a 3,5-dibromocyclohexyl group.

Examples of the chain or cyclic alkyl group having a double bond or triple bond include an allyl group, a 2-butenyl group, a geranyl group, a 5-chloro-3-pentenyl group, a 2-propynyl group, and a 2-butynyl group. Can be Examples of the chain or cyclic alkyl group capable of forming a cyclic structure include 1,1-diethylmethylene group, 1,2-ethylene group, 1,3-propylene group, 1,3-dimethyl-1,3-propylene group, 1,4-butylene group, propane-1,1,1-trimethylene group, 2-hydroxyethane-1,1,1-trimethylene group, 3-hydroxypropane-1,1,1-triethylene group and the like. .

Of the above examples, R ¹ , R ² and R ³ are preferably a branched alkyl group or a cycloalkyl group.
Specific examples of the branched alkyl group include i-propyl, t-butyl, neopentyl, 2-ethylhexyl, isononyl, isodecyl, and 4,4-dimethyl-1-pentyl. .
Specific examples of the cycloalkyl group include those having 1 to 15 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Further, among the above, it is particularly preferable that a branched chain is formed at a carbon atom bonded to an oxygen atom, such as a secondary alkyl group or a tertiary alkyl group. Specific examples of the secondary or tertiary alkyl group include i-propyl, t-butyl, 1,1-dimethylpropyl, pentan-3-yl, heptane-3-yl, cycloalkyl Examples include a propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Specific examples of the monodentate phosphite compound described above include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tri-i-propyl phosphite, triallyl phosphite, tri-n-butyl phosphite, and tri-n-butyl phosphite. Octadecyl phosphite, ethyl di-t-butyl phosphite, 2-ethylhexyl diethyl phosphite, diethyl methyl phosphite, dibenzyl-i-propyl phosphite, diisodecyl allyl phosphite, tris (3-methoxypropyl) phosphite, tris (2-butenyl) phosphite, tris (2,2,2-trifluoroethyl) phosphite, tris (3-chloropropyl) phosphite, tricyclohexylphosphite, diisooctyl-2,3-dibromo-1- B pills phosphite, trimethylolpropane phosphite, and compounds having a structure represented by the following structural formulas (L-1) ~ (L-10) are exemplified.

Among the above exemplified compounds, tri-i-propyl phosphite, ethyl di-t-butyl phosphite, 2-ethylhexyl diethyl phosphite, dibenzyl-i-propyl phosphite, diisodecyl allyl phosphite, tricyclohexyl phosphite, diisooctyl-2 , 3-Dibromo-1-propylphosphite, t-butyldiallylphosphite, isooctyldibenzylphosphite, di (3-chloropropyl) neopentylphosphite, cyclopropylbis (2-butenyl) phosphite, diethyl- i-propyl phosphite, dimethyl-t-butyl phosphite, cyclohexyl dimethyl phosphite, trineopentyl phosphite, diisooctyl neopentyl phosphite, dicyclohexyl isobutyl phosphite Aito, and the (L-2), (L-5), (L-6), compounds represented by (L-7) preferred.

Further, as the monodentate phosphite compound, a compound in which R ¹ , R ² , and R ³ are each independently a secondary or tertiary alkyl group having 1 to 10 carbon atoms is particularly preferable. Specific examples thereof include tri-i-propyl phosphite, ethyl di-t-butyl phosphite, dibenzyl-i-propyl phosphite, di-i-propyl-t-butyl phosphite, tri-t-butyl phosphite, Examples include tricyclohexyl phosphite, tricycloheptyl phosphite, dicyclohexyl-t-butyl phosphite, i-propyl-t-butyl-1,1-dimethylpropyl phosphite. Among these, tri-i-propyl phosphite is most preferred.

The amount of the monodentate phosphite compound to be used 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. It is preferably in the range of 500 or less, particularly preferably 100 or less.

Examples of the catalyst exhibiting particularly good activity include a palladium compound and a monodentate phosphite in which at least one of R ¹ , R ² and R ³ is a branched alkyl group or a cycloalkyl group having 1 to 15 carbon atoms. Combinations.

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

By reacting the allyl raw material compound with a different oxygen nucleophile using the catalyst comprising the transition metal compound and the trialkyl monodentate phosphite compound described above, a new allyl compound (for example, ether) Compounds and ester compounds) can be efficiently produced.

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 oxygen nucleophile and, in some cases, the solvent may be used. The mixture obtained by adding the catalyst solution separately prepared in the catalyst preparation tank to the mixed solution was continuously or semi-continuously introduced into the reactor, and the mixture was allowed to stay at a certain reaction temperature with stirring to obtain oxygen. The allylation reaction of the nucleating agent proceeds, 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.

<Examples 1 and 2 and Comparative Examples 1 to 3>
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 triisopropyl phosphite as a trialkyl type monodentate phosphite compound (Example 1) ) Or triethyl phosphite (Example 2) in Schlenk (8 equivalents to palladium (0.2408 mmol)), and after purging with argon, add 2.0 ml of tetrahydrofuran and stir at room temperature to give a palladium concentration of 15. 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 allylphenyl ether was determined by analyzing the solution composition by gas chromatography.

For comparison, a conventional bidentate phosphine ligand of 1,4-bis (diphenylphosphino) butane (dppb) and a triaryl type monodentate phosphite ligand of triphenyl phosphite have been used. The same reaction was carried out using a ligand and tris (2,4-di-t-butylphenyl) phosphite (Comparative Example 1, Comparative Example 2 and Comparative Example 3). However, when dppb which is a bidentate ligand was used, about 4 equivalents were added to palladium.

<Example 3 and Comparative Examples 4 to 7>
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.

0.0048 g (0.0048 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight as a transition metal compound, and 4 equivalents of palladium as a trialkyl monodentate phosphite compound were used. Triisopropyl phosphite (0.0389 mmol) was placed in Schlenk and replaced with argon, and then 0.943 g (9.420 mmol) of allyl acetate and 2.422 g (18.594 mmol) of 1-octanol were added under argon to obtain 100 The reaction was carried out by heating at ° C. After the reaction for 60 minutes, the yield of allyl octyl ether was determined by analyzing the solution composition by gas chromatography.

For comparison, conventionally used bidentate phosphine ligands, 1,4-bis (diphenylphosphino) butane (dppb), monodentate phosphine ligands triphenylphosphine, and monodentate phosphite coordinates The same reaction was carried out using a triphenylphosphite ligand and tris (2,4-di-t-butylphenyl) phosphite. However, when dppb which is a bidentate ligand was used, about 2 equivalents were added to palladium.

<Example 4 and Comparative Examples 8 to 9>
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 8 equivalents of palladium as a trialkyl monodentate phosphite compound were used. Triisopropyl phosphite (0.2409 mmol) was placed in Schlenk, and after purging with argon, 2.0 ml of tetrahydrofuran was added and stirred at room temperature to prepare a catalyst solution having a palladium concentration of 15.05 mmol / l. 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.

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

Claims (6)

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 a monodentate phosphite compound having a structure represented by the following general formula (1) By reacting an allyl raw material compound with an oxygen nucleophile having a structure different from that of the allyl raw material compound, a new allyl compound having a composition formula different from that of the allyl raw material compound is produced. A method for producing an allyl compound, comprising:
P (OR ¹ ) (OR ² ) (OR ³ ). . . General formula (1)
(In the general formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent. In the carbon chain of R ¹ , R ² and R ³ , May have one or more carbon-carbon double bonds or triple bonds, and any two or more of R ¹ , R ² and R ³ may be bonded to each other to form one or more cyclic structures. May be.) 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 above general formula (a), R ^{a to} R ^e each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkyl group, an aryl group (forming an aromatic 6π electron cloud above and below a ring) The same applies hereinafter.), An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group, of which amino group, alkyl group, aryl group, alkoxy group , an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, if still any good .R ^a to R ^e may have a substituent group contains a carbon chain, in the carbon chain One or more carbon-carbon double or triple bonds may be present.
X is a halogen atom, a carbon atom to which at least one electron-withdrawing group is bonded, a hydroxy group, a nitro group, 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 Represents an aryloxy group. Of these groups, the amino group, sulfonyl group, sulfonate group, acyloxy group, carbonate group, carbamate group, phosphate group, alkoxy group and aryloxy group may further have a substituent. When X contains a carbon chain, one or more carbon-carbon double bonds or triple bonds may be present in the carbon chain. In addition, 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 desorbed from the allyl raw material compound by the reaction and the protonated product XH thereof, wherein the oxygen atom is AO-H or its deprotonated AO ⁻ (In the above formula, A is a hydrogen atom or a compound represented by an organic group, which is a carbon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom and is bonded to the oxygen atom.) The method for producing an allyl compound according to claim 1 or 2, characterized in that: 4. The transition metal compound according to claim 1, wherein 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. The method for producing an allyl compound according to claim 1. The monodentate phosphite compound, wherein at least one of R ¹ , R ² , and R ^{3 in} the general formula (1) is a branched alkyl group or a cycloalkyl group. The method for producing an allyl compound according to any one of claims 1 to 4. The method for producing an allyl compound according to any one of claims 1 to 5, wherein the transition metal compound is a palladium compound.