JP2004131490A - Method for producing allyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple procedure to elevate a catalytic activity and improve the production efficiency of an allyl compound without changing a catalyst system in a method for producing the new allyl compound by performing the reaction of a raw material for the allyl compound with a nucleophilic agent under the catalyst composed of a transition metal compound and trivalent phosphorus compound. <P>SOLUTION: This method for producing the new allyl compound (e.g. 1, 4-diacetoxybutene-2) by performing the reaction of the raw material of the allyl compound (e.g. 3, 4-diacetoxybutene-1) with the nucleophilic agent (e.g. acetic acid anion) in the presence of the catalyst containing the transition metal compound containing at least one transition metal selected from a group consisting of transition metals belonging to 8th to 10th group of the periodic table and the trivalent phosphorus compound is provided by presenting a phosphonium compound in the reaction system. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a method for producing a new allyl compound by reacting an allyl raw material compound with a nucleophile in the presence of a catalyst.

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.

When the allylation reaction using the above-mentioned catalyst is carried out on an industrial scale, the purpose is to reduce the amount of expensive palladium that is a noble metal or to reduce the construction size by reducing the size of the reactor. In addition, improvement of reactivity is strongly desired. As one of attempts to improve such reactivity, a method in which a counter cation of a nucleophile is present in a reaction system is known. The effect is that a nucleophile paired or co-existing with such a counter cation has an increased nucleophilic attack and, consequently, increased reactivity.

Non-Patent Literature 2 reports a reaction between cyclopentadiene monoxide and an acetate anion. In this reaction, in order to improve the reactivity, a counter cation of the acetate anion was used as a counter cation of the acetate anion. Sodium ions are used. However, when such an alkali metal is a counter cation, the +1 valence charge is concentrated on one small metal ion, which tends to form a strong ion pair with the nucleophile of the counter anion. Offensive power is not high enough.

In addition, as examples of the allyl alkylation reaction, reactions of various allyl raw material compounds with malonic acid diester derivatives have been reported in many academic papers, but usually, malonic diester has low reactivity because of its low reactivity. The reaction is carried out in the state of a carbanion of malonic acid diester having an alkali metal ion such as sodium ion, lithium ion or potassium ion as a counter cation by reaction with an alkali metal hydride or the like. In these methods, the activity is not considered to be sufficiently enhanced from the above viewpoint, and in view of application to an industrialization process, it is a water-inhibiting substance that falls under the category of hazardous materials, It is not desirable to use a large amount of alkali metal hydride or the like that generates gas.

As described above, alkali metal cations are mainly known as counter cations to coexist for the purpose of promoting reactivity in the allylation reaction.However, a reaction example in which phosphonium coexists in the system as a counter cation has been described so far. However, it has not been reported. Examples of the description of phosphonium related to a π-allyl complex include, as described in Non-Patent Document 3, Non-Patent Document 4, and Non-Patent Document 5, triphenylphosphine is added to a palladium-triphenylphosphine- (π-allyl) complex. As described in Non-Patent Document 6, as an example in which phosphonium having an allyl group is generated as a result of nucleophilic attack, triphenylphosphine is also nucleophilically attacked on a rhodium-triphenylstibine- (π-allyl) complex. It is known that phosphonium having an allyl group is produced as a result. However, these examples are examples in which phosphonium is generated from a π-allyl complex coordinated with phosphine or stibine, and are not examples in which phosphonium is used to promote a catalytic reaction.

Further, as an example of the use of phosphonium related to the allylation reaction, production of 2,7-octadien-1-ol by butadiene hydration dimerization reaction described in Patent Document 1 and Non-Patent Document 7 is known. ing. However, phosphonium is only used as a ligand of the palladium catalyst, and the counter cation that promotes the reaction with the actual nucleophile is ammonium derived from a tertiary amine added separately.

JP-A-2-172924 `` Palladium Reagents and Catalysts -Innovations in Organic Synthesis- '' John Wiley & Sons Organic Syntheses, 1988, 67, p114 J. Am. Chem. Soc., 1992, 114, p6858 Bull. Chem. Soc. Jpn., 1984, 57, p3013 J. Chem. Soc. (A), 1968, p774 J. Chem. Soc. Dalton Trans., 1992, p1323 The Chemical Society of Japan, 1993, 2, p119

As described above, reduction of catalyst cost is one of the important items in order to carry out the production of various allyl compounds by reacting an allyl raw material compound with a nucleophile on an industrial scale. . The main method of reducing catalyst cost is to reduce the amount of catalyst used by improving reactivity.However, the creation of a new highly active catalyst aimed at improving reactivity requires a huge amount of development. Frequently there are costs and consideration periods. Therefore, if a method for improving the catalytic activity by a simple method such as the coexistence of a third component compound without changing the catalyst system is presented, it becomes one of effective methods and is very important. It can be said.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a method for producing a new allyl compound by reacting an allyl raw material compound with a nucleophile under a catalyst comprising a transition metal compound and a trivalent phosphorus compound. It is an object of the present invention to provide a method for producing an allyl compound, in which the activity of a catalyst is improved by a simple method such as the coexistence of a compound as a third component without any addition, so that an allyl compound can be produced efficiently.

The present inventors have been studying various allylation reactions using a catalyst comprising a transition metal compound belonging to Groups 8 to 10 of the periodic table and a trivalent phosphorus compound. The reactivity was increased several times by a simple method such as the presence of phosphonium in the reaction system as a cation, and the present invention was achieved. In the present invention, it is considered that the nucleophilic aggressiveness of the nucleophile was enhanced by the presence of a counter cation capable of forming only a loose ion pair called phosphonium. It is considered that the present invention is applicable to a method for producing all kinds of allyl compounds, which progresses by attacking an allyl complex with a nucleophile.

That is, the gist of the present invention resides in the presence of a catalyst containing a transition metal compound containing one or more transition metals selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table and a trivalent phosphorus compound. A method for producing a new allyl compound by reacting an allyl raw material compound with a nucleophile, wherein a phosphonium compound is present in the reaction system.

According to the present invention, a new allyl compound is produced by reacting an allyl raw material compound with a nucleophile using a catalyst comprising a transition metal compound belonging to Groups 8 to 10 of the periodic table and a trivalent phosphorus compound. In this case, the presence of phosphonium as a counter cation of the nucleophile in the reaction system makes it possible to extremely easily increase the catalytic activity and greatly improve the production efficiency of the allyl compound. Very advantageous.

Hereinafter, the present invention will be described in detail.
The method for producing an allyl compound according to the present invention (hereinafter, abbreviated as “the production method of the present invention” as appropriate) includes one or more transition metals selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table. A new allyl compound is produced by reacting an allyl raw material compound with a nucleophile in the presence of a catalyst containing a transition metal compound containing a trivalent phosphorus compound. It is characterized by having it exist.

First, the phosphonium compound to be present in the reaction system, which is a feature of the production method of the present invention, will be described. The phosphonium compound that can be used in the present invention is not particularly limited as long as it is basically a structure in which four substituents are bonded to phosphorus. Such a structure results in a counter cation that can form only a looser ion pair than an alkali metal ion that has been often used in the past, and accordingly can increase the aggressiveness of the nucleophile, that is, the reactivity. The reason is that, in the case of an alkali metal ion, + 1-valent charges are concentrated on the surface of a small alkali metal ion, whereas in the case of a phosphonium compound, the entire molecule is + 1-valent, and the phosphorus atom where the charges are concentrated has four substituents. This is considered to be due to the structure hidden by.

Phosphonium compounds which are stable under the reaction conditions, are dissolved in the reaction system, and do not poison the catalyst (Examples of the compounds poisoning the catalyst include compounds containing a conjugated diene and phosphite compounds Is not particularly limited, as long as it is a compound that oxidizes and disappears, such as a compound containing peroxide. From the viewpoint of solubility in the reaction system, the molecular weight is usually 3000 or less, preferably 2000 or less, more preferably 1500 or less, and usually 40 or more, preferably 70 or more, more preferably 100 or more.

Among them, a phosphonium compound having a structure represented by the following general formula (1) is preferable.
PX ¹ X ² X ³ X ⁴ . . . General formula (1)

In the above general formula (1), X ^{1 to} X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a chain or cyclic alkyl group, an aryl group (the aryl group in the present specification). Represents a heterocyclic compound that forms an aromatic 6π electron cloud above and below the ring.), An alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. These exemplified groups may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system, but is preferably a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a linear or cyclic alkyl group, or an aryl group. Preferred are a group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. When these unsubstituted or substituted examples include a carbon chain, one or more carbon-carbon double bonds or triple bonds may be present in the carbon chain.

X ^{1 to} X ⁴ each independently have usually 40 or less, preferably 30 or less, more preferably 20 or less. Any two or more groups of X ^{1 to} X ⁴ 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 two or more groups of X ^{1 to} X ⁴ are bonded to form a cyclic structure, the number of carbon atoms is usually 0 to 40, where p is the number of groups involved in the formation of the cyclic structure. × p, preferably 0 to 30 × p, particularly preferably 0 to 20 × p. 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.

Among the above examples, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a chain or cyclic alkyl group which may have a substituent, an aryl group, an alkoxy group, an arylalkoxy group, or an aryloxy group. More preferably, a chain or cyclic alkyl group or aryl group which may have a substituent is more preferable (in this case, as described above, among these X ^{1 to} X ⁴ alkyl groups or aryl groups). Any two or more may combine to form one or more cyclic structures.)

In particular, at least one of X ^{1 to} X ⁴ is preferably a group capable of dispersing a + 1-valent charge on phosphorus of the phosphonium compound by a resonance effect. This is because the phosphonium compound can be a counter cation forming an ion pair by having such a group. Examples of the group capable of stabilizing the resonance of such a cation include an unsubstituted or substituted aryl group or vinyl group, and specifically, a phenyl group, a 4-methoxyphenyl group, t-butylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-t-butyl-6-methylphenyl group, 2,5-dimethylphenyl group, 2,4,6-trimethoxy Examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-methyl-2-naphthyl group, a vinyl group and a 1-butenyl group. Above all, an unsubstituted or substituted aryl group is particularly preferable in consideration of the effect of resonance stabilization, ease of synthesis of phosphonium, and the like.

Specific examples of the phosphonium compound that can be used in the present invention include hydrotrimethoxyphosphonium, hydromethoxydimethylphosphonium, chlorohydroxydicyclohexylphosphonium, bromotriethoxyphosphonium, trichloro-3-phenoxy-1-propenylphosphonium, and dichlorohydroxyphenylphosphonium. , Tri (t-butoxy) cyclohexylphosphonium, fluorotris (4-methoxyphenyl) phosphonium, methyltri (phenoxy) phosphonium, dimethylaminotris (4-ethylphenyl) phosphonium, tri (ethylthio) hydrophosphonium, diethoxyethylphenylthiophosphonium , Trifluoromethyltris (dimethylamino) phosphonium, tetra (t-butyl) phosphonium, tri Chill-1-propynyl phosphonium, and the like.

Among them, from the viewpoints of stability and solubility, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a linear or cyclic alkyl group, aryl group, alkoxy group, arylalkoxy group which may have a substituent. And a phosphonium compound which is an aryloxy group or an alkyl aryloxy group. Specific examples of such a phosphonium compound include tetra (n-dodecyl) phosphonium, tetrakis (2-octenyl) phosphonium, cyclohexyl tris (2-methyl-2-butenyl) phosphonium, methoxymethyldi (n-butyl) phosphonium, Allyl-t-butylethylphenoxyphosphonium, 4-acetoxy-2-butenylphenylbis (2,4-di-t-butylphenoxy) phosphonium, t-butoxy-3-bromo-1-naphthoxybis (4-nitrophenyl) Phosphonium, di (1-naphthoxy) -2,4-di-t-butyl-5-methylphenoxy-2-acetoxy-3-butenylphosphonium, 2-butene-1,4-bis (tris (2-methoxyphenoxy) ) Phosphonium), tetrakis (2,4,6-trimethoxy) Phenoxy) phosphonium, and the like.

Further, a phosphonium compound in which X ^{1 to} X ⁴ are a chain or cyclic, unsubstituted or substituted alkyl group or aryl group is preferred. These can be restated as phosphonium compounds having a structure in which all four substituents of phosphonium are bonded to phosphorus by a PC bond. Specific examples of such a phosphonium compound include tetramethylphosphonium, tetra (n-butyl) phosphonium, tetra (methylol) phosphonium, 4-acetoxybutyldiethyl-2-methoxyethylphosphonium, neopentyltriphenylphosphonium, and tetraphenylphosphonium Tetrakis (4-fluorophenyl) phosphonium, 2-butenylbis (4-t-butylphenyl) -3-cyanopropylphosphonium, methyltriphenylphosphonium, 4-methylcyclohexyltri (i-propyl) phosphonium, dimethylpentamethylenephosphonium, 4-acetoxy-2-butenyltriphenylphosphonium, 2-butenyl-1,4-bis (triphenylphosphonium), naphthalene-1,8-bis (trimethylphosphonium) Ion), such as 2,2'-bis (diphenylmethyl phosphonium) can be mentioned. Further, general phosphonium compounds having an allyl group induced by the reaction between phosphine and an allyl compound can also be added as specific examples.

In particular, a phosphonium compound in which at least one of X ^{1 to} X ⁴ is a group capable of dispersing a +1 valence charge on a phosphorus atom by a resonance effect as described above is preferable. Specific examples of such a phosphonium compound include trimethylphenylphosphonium, 4-acetoxy-2-butenyldicyclohexylphenylphosphonium, 2-butenyl-1,4-bis (dicyclohexylphenylphosphonium), triethyl-1-naphthylphosphonium, Tri-n-butyl-1-methyl-2-naphthylphosphonium, diethylphosphindolium, 4-acetoxy-2-butenyldiphenyl-i-propylphosphonium, 2-butenyl-1,4-bis (diphenyl-i-propyl Phosphonium), dimethylbis (2,4-dimethylphenyl) phosphonium, t-butyl-1-acetoxymethyl-2-propenylbis (2-naphthyl) phosphonium, diphenylisophosphindolinium, methyltriphenylphosphonium 4-acetoxy-2-butenyltriphenylphosphonium, 2-butenyl-1,4-bis (triphenylphosphonium), 1-butene-3,4-bis (triphenylphosphonium), 1-acetoxymethyl-2-propenyl Tris (4-methoxyphenyl) phosphonium, tetraphenylphosphonium, di (1-naphthyl) diphenylphosphonium, tetrakis (2-naphthyl) phosphonium, naphthalene-2,6-bis (triphenylphosphonium) and the like.

To further supplement, it can be said that an electron-donating substituent such as an alkyl group or a methoxy group is more preferably bonded to such an aryl group in order to further reduce the cationicity of the phosphonium.

と When the phosphonium compound as described above is present in the reaction system for performing the allylation reaction, the effect of improving the reactivity is exhibited. In this case, any one kind of phosphonium compound may be used alone, or several kinds of phosphonium compounds may be mixed and used in an arbitrary combination.

The method of causing the phosphonium compound to be present in the reaction system is not particularly limited, and examples include a method of positively adding the phosphonium compound to the reaction system and a method of preparing the phosphonium compound in the reaction system. . Hereinafter, these methods will be described with reference to specific examples.

First, the method of positively adding the phosphonium compound to the reaction system is to feed the phosphonium compound into the reactor together with the allyl compound, nucleophile, catalyst, reaction medium, etc., and this phosphonium compound is a new phosphonium compound. Alternatively, a phosphonium compound that has been recycled in the reaction process may be used. It should be noted that, usually, a commercially available phosphonium compound is charged to a +1 charge per phosphorus, and thus is in the form of a salt with the corresponding counter anion. In this, it is desirable that this counter anion corresponding to phosphonium is a nucleophile that reacts with the allyl raw material compound. If the counter anion is not a nucleophile but a phosphonium compound in the form of a salt with another counter anion is added, the other counter anion will be added to the reaction system without poisoning the catalyst. It is desired that the nucleophile itself disappears due to a reaction with an allyl compound or the like, and the nucleophile becomes a counter anion. As counter anions of ordinary commercially available phosphonium compounds, chloride, bromide, halide ions such as iodide, hexafluorophosphate, hexachlorophosphate, hydrogen sulfate, tetrachloroborate, trifluoromethanesulfonate, Although perchlorate and the like are known, it is generally considered that halide ions have a high possibility of poisoning the transition metal catalyst. When such a halide phosphonium compound is used in the reaction, it is preferable to remove the halide phosphonium compound in advance by an anion exchange reaction or the like. At this time, it is more preferable to use a new counter anion as a nucleophile used in the allylation reaction.

On the other hand, as a method of preparing a phosphonium compound in a reaction system, a method of adding a trivalent phosphorus compound serving as a raw material of phosphonium can be mentioned. This utilizes the reactions described in Non-Patent Documents 3 to 5 and the like described in the “prior art” above, and trivalent phosphorus is added to the terminal allyl carbon of the π-allyl complex of a transition metal. This is a reaction in which a compound undergoes nucleophilic attack, and as a result, phosphonium with a new allyl group bonded thereto is generated. In fact, as in the examples described below, the allyl raw material compound 3,4-diacetoxybutene-1 was obtained in the presence of a palladium-bidentate phosphite catalyst and 200 equivalents of triphenylphosphine with respect to palladium. When the production process of 1,4-diacetoxybutene-2 by the reaction of acetoxide as a nucleating agent is traced by ³¹ P-NMR spectrum, the signal of -6 ppm of triphenylphosphine disappears promptly in the early stage of the reaction, and reaches 17 to 25 ppm. It is converted into multiple phosphonium signals that are observed. Considering the chemical shift value, it is considered that these signals are due to phosphonium, and the reason for the multiple observations is that [PPh ₃ (CH ₂ CH = CHCH ₂ OAc)] ⁺ [OAc] ⁻ , [PPh ₃ CH (CH ₂ OAc) (CH = CH ₂ )] ⁺ [OAc] ⁻ , [PPh ₃ (CH ₂ CH = CHCH ₂ ) PPh ₃ ] 2 ⁺ 2 [OAc] ⁻ , [PPh ₃ CH (CH ₂ PPh ₃ ) (CH ＣＨCH ₂ )] 2 ⁺ 2 [OAc] ^{− and the} like. As for the points to be noted when implementing such a method, when the coordination force of the trivalent phosphorus compound added as a raw material of phosphonium to the transition metal compound is too high, the trivalent phosphorus compound originally coordinated to the transition metal compound. The ligand may be eliminated, and the catalytic activity may be reduced. In such a case, as a countermeasure, it is also possible to convert the material into a phosphonium compound in advance outside the system and feed it, or to wait for the process to gradually change to a phosphonium compound during operation.

The use amount of the above phosphonium compound is more advantageous in consideration of economy, but as shown in the examples below, the increase in the amount of the phosphonium compound increases the catalytic activity gradually and gradually. The ratio (molar ratio) to the metal compound as the allylation reaction catalyst described in detail below is usually 0.1 or more, preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and most preferably 15 or more. Yes, it is usually 10,000 or less, preferably 5000 or less, more preferably 1000 or less, and still more preferably 500 or less.

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

In the above examples, X represents a hydroxy group, an acyloxy group having a skeleton structure represented by —C (＝ O) O—, a carbonate group, and a carbamate group, and a skeleton structure represented by ＰP (＝ O) —. phosphates group having, and -S (= O) are preferred Suruhoneito group having a skeleton structure represented by ₂ O-, inter alia hydroxy group, an acyloxy group and a carbonate group are preferred. Specific examples of the acyloxy group include a C1 to C6 acyloxy group such as an acetoxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. Specific examples of the carbonate group include a C1 to C6 alkyl carbonate group such as a methyl carbonate group, an ethyl carbonate group, and a phenyl carbonate group or an aryl carbonate group. Particularly, X is preferably a hydroxy group or 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 represented by the general formula (a), preferably, allyl halides, allyl alcohols, nitroallyls, allylamines, allyl sulfones, allyl sulfonates, allyl esters of carboxylic acid, allyl carbonate , 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, and 2-butenyldibenzylamine.
Specific examples of allyl sulfones include allyl phenyl sulfone, methylyl-p-tolylsulfone, 2-methyl-3-sulfolene, and 1,3-diphenylallylmethyl sulfone.
Specific examples of allylsulfonates include allyltoluene-4-sulfonate, 3-thiophenemethanesulfonate, 4-chloro-2-butenylmethanesulfonate, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Next, the catalyst used in the production method of the present invention will be described. The catalyst used in the present invention contains one or more transition metal compounds and a trivalent phosphorus 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.

Next, the trivalent phosphorus compound used in the present invention will be described. Trivalent phosphorus compounds that can be used in the present invention are those that are stable under the reaction conditions, coordinate with a transition metal to a transition metal in the reaction system, and do not poison the catalyst (the compounds that poison the catalyst). Is not particularly limited as long as it is as described above. Any trivalent phosphorus compound such as a phosphine compound, a phosphinite compound, a phosphonite compound, and a phosphite compound can be used. Further, bidentate compounds such as PP type, PN type, PS type and PO type having them can be equally used. In particular, 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 2000 or less, more preferably 1500 or less, and usually 50 or more, preferably 100 or more. , More preferably 150 or more.

Specific examples of the trivalent phosphorus compounds, trimethyl phosphine, triphenyl phosphine, 1,4-bis phosphines such as (diphenylphosphino) _{butane; P (OEt) Me 2,} P (OPh) Ph 2, Ph 2 Phosphinites such as POCH ₂ CH ₂ OPPh ₂ ; Phosphonites such as P (t-Bu) (On-Bu) ₂ and PMe (OPh) ₂ ; P (OEt) ₃ , P (OMe) (OPh) ₂ , Phosphites such as P (OMe) (Ot-Bu) (Oi-Pr); and PPh ₂ (NEt ₂ ), P (NMe ₂ ) ₃ , P (OPh) (NPh ₂ ) _{2 and the} like. Aminophosphines; and others such as P (SPh) ₃ , P (SMe) (NEt ₂ ) (OPh), P (OCOMe) ₃ , P (SiMe ₃ ) ₂ (OPh), P (SeMe) ₃ In addition, the following (M-1)- Compounds having a structure represented by M-12), etc., can be given various bidentate chelate ligand having a trivalent phosphorus compound. In this specification, Ph is a phenyl group, Me is a methyl group, Et is an ethyl group, i-Pr is an i-propyl group, t-Bu is a t-butyl group, and n-Bu is n -Butyl group respectively.

中 で も Among the above trivalent phosphorus compounds, a phosphite compound or a phosphine compound is preferable. In particular, a phosphite compound is more preferable because it can provide a more excellent catalytic activity when used as a ligand, and can be easily synthesized and is advantageous in cost.

The type of the phosphite compound is not particularly limited, but preferred examples include compounds having structures represented by the following general formulas (I) to (VI).

In the above general formulas (I) to (V), R ^{10 to} R ²¹ each independently represent a chain or cyclic alkyl group or aryl group. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, and A chain alkyl group such as a decyl group; or a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group. Examples of aryl groups include phenyl, tolyl, xylyl, di-t-butylphenyl, naphthyl, di-t-butylnaphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, Examples include an isoquinolyl group, an indolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, and a thiazolyl group.

The above-mentioned 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, and specifically, a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or Preferred are 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.

The carbon number of R ^{10 to} R ²¹ is usually 40 or less, preferably 30 or less, more preferably 20 or less. When the above-mentioned alkyl group or aryl group further has a substituent, the total number of carbon atoms including this substituent is adjusted to the above range.

Among the above-exemplified group, given the stability of the above-mentioned phosphite as the R ¹⁰ to R ^21, unsubstituted or substituted aryl group. Specific examples of the unsubstituted or substituted aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 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 and the like.

In the above general formula (III), 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 not limited to 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 represent 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 is, -CR ²² R ²³ - (representing each R ²² and R ²³ are independently, linear or cyclic alkyl group, or an aryl group), - O -, - representing the S- or -CO-. n is 0 or 1. Examples of the alkyl group and the aryl group represented by R ²² and R ²³ include the same groups as those described above for R ^{10 to} R ²¹ .

In the general formulas (II) to (VI), Z ^{1 to} Z ⁴ 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 is preferably an alkylene group, an arylene group, an alkylene-arylene group, or a diarylene group. These organic groups may further have a substituent as long as there is no risk of adversely affecting the reaction system. Preferred examples of the substituent include 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, and an alkylthio group. Group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like.

The carbon number of each of Z ^{1 to} Z ⁴ and 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 number of carbon atoms is usually 40 or less, preferably 30 or less, more preferably 20 or less. It is. On the other hand, in the case of an unsubstituted or substituted diarylene group, the number of carbon atoms is usually 60 or less, preferably 50 or less, more preferably 40 or less.

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

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

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

On the other hand, the Jiariren group, directly two arylene groups, or by a linked group via a divalent organic group, specifically _{^{-Ar 1 - (Q 1) n}} -Ar 2 - with It is 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. As specific examples, -O -, - S -, - CO-, or -CR ²⁴ R ²⁵ - group represented by the like. Here, R ²⁴ and R ²⁵ 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 substituents that the arylene group of Ar ¹ and Ar ² and the alkyl group and the aryl group of R ²⁴ and R ²⁵ may have are not particularly limited as long as they do not adversely affect the reaction system. Preferred specific examples include a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, Examples include an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
Specific examples of the diarylene group which 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 the substituents constituting the phosphite compounds represented by the above general formulas (I) to (VI). Examples of the general formula (I) include trimethyl phosphite, triethyl phosphite, tri-i-propyl phosphite, triallyl phosphite, trioctadecyl phosphite, ethyl di-t-butyl phosphite, and 2-ethylhexyl Diethyl phosphite, dibenzyl-i-propyl phosphite, diisodecyl allyl phosphite, tris (3-methoxypropyl) phosphite, tri (2-butenyl) phosphite, tris (2,2,2-trifluoroethyl) phosphite , Tris (3-chloropropyl) phosphite, Cyclohexyl phosphite, diisooctyl-2,3-dibromo-1-propyl phosphite, trimethylolpropane phosphite, dimethylphenyl phosphite, ethyl phenyl (n-propyl) phosphite, benzyl diphenyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (3,6-di-tert-butyl-2-naphthyl) phosphite, 2-tert-butylphenyl-1-naphthyl-4-methoxyphenylphosphite Phyto, a monodentate phosphite having a structure represented by the following formulas (P-1) to (P-20) as examples of the general formula (II), and a compound represented by the following formula (L-1) as an example of the general formula (III) ) To (L-5) are compounds represented by the following formulas (L-6) to (L-32) as examples of the general formula (IV). Bidentate of the structure represented by the following formulas (L-33) to (L-47) as an example of the formula (V) and the following formulas (L-48) to (L-57) as an example of the general formula (VI) Phosphites.

Among the phosphite compounds exemplified above, bidentate phosphite compounds having structures represented by the above general formulas (IV) to (VI) 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 ^{16 to} R ²¹ are each independently an unsubstituted or substituted aryl group, or Z ^{1 to} Z ⁴ are each independently unsubstituted or Particularly preferred is a substituted diarylene group, wherein A ^{1 to} A ³ are each independently an unsubstituted or substituted alkylene group, arylene group, alkylene-arylene group, or diarylene group. Specific examples thereof include the 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 -53) to (L-57).

On the other hand, the type of the phosphine compound is not particularly limited, but preferred examples include a compound having a structure represented by the following general formula (VII) or (VIII).

In the above formulas (VII) and (VIII), R ^{31 to} R ³⁷ each independently represent a chain or cyclic alkyl group or aryl group. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, decyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Examples of aryl groups include phenyl, tolyl, xylyl, di-t-butylphenyl, naphthyl, di-t-butylnaphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, Examples include an isoquinolyl group, an indolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, and a thiazolyl group.
Further, any two or more of R ^{31 to} R ³³ , R ³⁴ and R ³⁵ , and R ³⁶ and R ³⁷ may be bonded directly or through a hetero atom to form a ring structure.

The above-mentioned 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, and specifically, a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or Preferred are 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.

The carbon number of R ^{31 to} R ³⁷ is usually 40 or less, preferably 30 or less, more preferably 20 or less. When the above-mentioned alkyl group or aryl group further has a substituent, the total number of carbon atoms including this substituent is adjusted to the above range.
Further, the ring structure formed by combining any two or more of R ^{31 to} R ³³ , R ³⁴ and R ³⁵ , or R ³⁶ and R ³⁷ usually has a carbon number of 60 or less, preferably 40 or less, more preferably 30 or less.

Considering the stability of the above-mentioned phosphites among the above-mentioned exemplified groups, R ^{31 to} R ³⁷ are preferably unsubstituted or substituted aryl groups. Specific examples of the unsubstituted or substituted aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 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 and the like.

A ¹¹ represents a divalent organic group. The type thereof is not particularly limited as long as it does not adversely affect the reaction system, but is preferably an unsubstituted or substituted alkylene group, arylene group, alkylene-arylene group, or diarylene group.
These groups may further have a substituent as long as there is no risk of adversely affecting the reaction system. Preferred examples of the substituent include 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, and an alkylthio group. Group, an arylthio group, a perfluoroalkyl group, a trialkylsilyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like.

The carbon number of A ¹¹ is usually 1 or more and 60 or less. Among them, in the case of an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted alkylene-arylene group, the number of carbon atoms is usually 40 or less, preferably 30 or less, more preferably 20 or less. It is. On the other hand, in the case of an unsubstituted or substituted diarylene group, the number of carbon atoms is usually 60 or less, preferably 50 or less, more preferably 40 or less.

The alkylene group may be a chain or a ring. Preferred examples of the substituent which the alkylene group may have include a halogen atom, a hydroxy group, an amino group, a formyl group, a cyano group, a nitro group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Groups, acyl groups, acyloxy groups, alkylthio groups, arylthio groups, perfluoroalkyl groups, trialkylsilyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and the like. Specific examples of the unsubstituted or substituted alkylene group include an ethylene group, a tetramethylethylene group, a 1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,4-butylene group. Can be

Preferred examples of the substituent that the arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 3,5-di-t-butyl-1,2-phenylene group, and a 2,3-naphthylene group. , 1,4-di-t-butyl-2,3-naphthylene group, 1,8-naphthylene group and the like.

Preferred examples of the substituent that the alkylene-arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted alkylene-arylene group include (D-1) to (D-12) described above.

The Jiariren group which may have a divalent linking group between and across the two arylene groups Jiariren group, in particular _{^{- (Q 11) a -Ar 11}} - (Q 20) c -Ar ¹² - (Q ¹²⁾ _b - is a group having the structure represented by like. Here, Ar ¹¹ and Ar ¹² each independently represent an arylene group which may have a substituent. Q ¹¹ and Q ¹² each independently represent a methylene group which may have a substituent. Q ²⁰ represents a divalent organic group. As specific examples, -O -, - S -, - CO-, or -CR ⁴¹ R ⁴² - represent. Here, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. a, b, and c each independently represent 0 or 1. Preferred specific examples of the substituents that the arylene group of Ar ¹¹ and Ar ¹² and the alkyl group and the aryl group of R ⁴¹ and R ⁴² may have, respectively, The same groups as the preferred examples of the good substituents can be mentioned. Among them, specific examples of preferred groups as A ^11, in the case of a = b = 0, include compounds of the above formula (A-1) ~ (A -48), otherwise, the following formula ( B-1) to (B-20).

As described above, phosphines having various structures can be used depending on the combination of the substituents constituting the phosphine compounds represented by the above general formulas (VII) and (VIII). , Trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-nonylphosphine, methyldiphenylphosphine, di-n-octyl-2-naphthylphosphine, bis (4-fluorophenyl) isopropylphosphine, triphenylphosphine, tris (2 , 4,6-trimethylphenyl) phosphine, 2-chlorophenyl-4-methoxyphenyl-3,6-di-t-butyl-2-naphthylphosphine, such as the following (P-21) to (P-36) Monodentate phosphine and 1,2-bis (di-t-butylphosphine) Sufino) ethane, 1,3-bis (diethylphosphino) propane, 1,4-bis (dimethylphosphino) -1,1,4,4-tetramethylbutane, 1,2-bis (diphenylphosphino) ethane 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane, ( And bidentate phosphines such as (L-58) to (L-81).

中 で も Among the phosphines exemplified above, bidentate phosphines having a structure represented by the above general formula (VIII) are preferable, and specifically, compounds of the above formulas (L-58) to (L-81) are preferable.

The use amount of the above-mentioned trivalent phosphorus 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.

遷移 The above-mentioned transition metal compound and trivalent phosphorus compound may be added individually to the reaction system, or may be used in a complexed state in advance. Alternatively, the above-mentioned trivalent phosphorus 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 trivalent phosphorus compound, or the reaction may be carried out simultaneously using two or more kinds of trivalent phosphorus compounds in any combination.

By using the above-described catalyst composed of a transition metal compound and a trivalent phosphorus compound, by reacting the above-mentioned allyl raw material compound with a nucleophile in the presence of the above-mentioned phosphonium compound, a new allyl compound is efficiently produced. Can be manufactured well.

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 above-mentioned phosphonium compound and the catalyst and the raw material compound, and does not adversely affect the catalytic activity. There is no limitation. Specific examples of preferred solvents include carboxylic acids such as acetic acid, propionic acid and butyric acid, alcohols such as methanol, n-butanol and 2-ethylhexanol, diglyme, diphenyl ether, dibenzyl ether, diallyl ether and tetrahydrofuran (THF). , Ethers such as dioxane, amides such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, ketones such as cyclohexanone, esters such as butyl acetate, γ-butyrolactone, di (n-octyl) phthalate; Toluene, xylene, aromatic hydrocarbons such as dodecylbenzene, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, high-boiling substances generated as by-products in the allylation reaction system, allyl compounds as raw materials, Allyl product Compounds, compounds derived from the leaving group of the starting allylic compounds. The use amount of these solvents is not particularly limited, but is usually 0.1 times by weight or more, preferably 0.2 times by weight or more, and usually 20% by weight, Times or less, preferably 10 times or less by weight.

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

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

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 and elimination of the trivalent phosphorus compound. 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.

In the present invention, it is possible to produce a large number of allyl compounds by reacting the above-mentioned various allyl raw material compounds with a nucleophile in the presence of a catalyst and phosphonium. Examples are described below.

As a preferred reaction example, a compound (3,4-disubstituted butene-1) having a structure represented by the above general formula (b) is used as the allyl raw material compound, and acetic acid (CH ₃ COOH) or By using the deprotonated product (CH ₃ COO ⁻ ) or water (H ₂ O) or the deprotonated product (HO ⁻ ), the compound (1, 4) having the structure represented by the general formula (c) can be obtained. A reaction for favorably producing disubstituted butene-2), using 1,4-disubstituted butene-2 of the above general formula (c) as an allyl raw material compound, and acetic acid (CH ₃ COOH) as a nucleophile ) Or its deprotonated product (CH ₃ COO ⁻ ), or water (H ₂ O) or its deprotonated product (HO ⁻ ) to give the 3,4-disubstituted butene of the general formula (b). Reaction for producing 1 well It can gel.

Among them, a particularly preferable reaction example is a method using 3,4-diacetoxybutene-1 as an allyl raw material compound and using acetic acid (CH ₃ COOH) or its deprotonated product (CH ₃ COO ⁻ ) as a nucleophile. , 4-diacetoxybutene-2, and 1,4-diacetoxybutene-2 as an allyl raw material compound, and acetic acid (CH ₃ COOH) or a deprotonated product thereof (CH ₃ COO) as a nucleophile ^-) is the production of 3,4-diacetoxy-butene-1 was used.

In these reactions, the leaving group is a deprotonated form of acetic acid (CH ₃ COO ⁻ ), and the nucleophile is also a deprotonated form of acetic acid (CH ₃ COO ⁻ ). When the nucleophile attacks a terminal allyl carbon different from the above, it means that the isomerization reaction has advanced. This reaction is an equilibrium reaction when the nucleophile attack occurs on the carbon from which the leaving group has been eliminated, and this reaction is an equilibrium reaction. In this case, it is determined by the free energy difference between the two compounds. Incidentally, the equilibrium composition at 120 ° C. is about 63% for 1,4-diacetoxybutene-2 and about 37% for 3,4-diacetoxybutene-1.

A catalyst particularly suitable for carrying out the above-mentioned preferable reaction is a catalyst comprising a palladium compound and a bidentate phosphite compound represented by the above-mentioned general formulas (IV) to (VI), and particularly a catalyst comprising the above-mentioned general formula (IV) The combination with the bidentate phosphite compound represented by is also preferable from the viewpoint of catalyst stability. The presence of the phosphonium represented by the above formula (1) in the catalyst system increases the reactivity several times. Further, in the isomerization reaction, the reaction is promoted by the coexistence of acetic acid. Therefore, it can be said that it is a preferred embodiment to employ acetic acid as the reaction solvent. The amount of acetic acid is usually 1/1000 or more, preferably 1/100 or more, more preferably 1/10 or more, by weight ratio of acetic acid / allyl starting compound, from the viewpoints of catalytic activity, catalyst stability and economy. Also, it is usually within a range of 5/1 or less, preferably 4/1 or less, more preferably 2/1 or less.

The present invention relates to a target 1,4-diacetoxybutene-2 obtained by subjecting butadiene to a diacetoxylation reaction with a catalyst in the presence of acetic acid and oxygen and a by-product 3,4-diacetoxybutene-1. From the reaction product containing 3,4-diacetoxy-1-butene as a main component, and then isomerized by the method of the present invention to give 1,4-diacetoxybutene-2. This is particularly effective when employed in the acquisition process. The 1,4-diacetoxybutene-2 whose yield has been increased by such isomerization reaction is then subjected to hydrogenation reaction and hydrolysis reaction to obtain 1,4-butanediol as a raw material of polyester or polyurethane, a solvent or It is an important intermediate for producing tetrahydrofuran, which is a raw material for PTMG (polytetramethylene ether glycol) polymer.

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 1-4 and Comparative Examples 1-3>
Allyl using 3,4-diacetoxybutene-1 (hereinafter abbreviated as 34DABE) as an allyl raw material compound and an acetate anion as a nucleophile in the presence of a palladium-bidentate phosphite (L-26) catalyst. The present invention was applied to a reaction for producing 1,4-diacetoxybutene-2 (hereinafter abbreviated as 14DABE) by performing an isomerization reaction (isomerization reaction).

As a transition metal compound, 0.0087 g (0.0088 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and as a bidentate phosphite compound, 4 equivalents of the above formula (L- 26) The compound of 0.0753 g (0.0703 mmol) was put into a Schlenk together, and after purging with argon, 0.7 ml of 34 DABE and 1.4 ml of toluene were added, and the mixture was heated at 110 ° C. for 10 minutes, and the palladium concentration was 8.37 mmol / 1 catalyst solution was prepared. Subsequently, Schlenk separately prepared for carrying out the reaction was replaced with argon, and 3 ml of 34 DABE and 3 ml of acetic acid were added. 12.5 μl of the above-mentioned catalyst solution was added thereto by a microsyringe, and the reaction was carried out by heating at 120 ° C. (Comparative Example 1: reaction without phosphonium compound). The reaction rate was evaluated by analyzing the solution composition before and after the reaction by gas chromatography to calculate the residual rate of 34DABE and the production rate of 14DABE, and applying the values to the following formula to calculate the reaction rate constant in the equilibrium reaction. It was done by calculating and comparing.

Apparently, assuming that the reaction rate constant in the equilibrium reaction in which 14 DABE is generated from 34 DABE is k _(34D → _14D) , k _(34D → _14D) is calculated by the following formula. Here, [14D] _e is the equilibrium concentration of 14DABE at equilibrium (63% in a reaction at 120 ° C.), [34D] ₀ is the concentration of 34DABE in the initial stage of the reaction (100% in the present reaction conditions), and [14D] _t Is the production concentration of 14DABE after t hours of the reaction time, and t is the reaction time (unit: hours).

k _(34D → _14D) = ([14D] _e / [34D] ₀ * ln ([14D] _e / ([14D] _e- [14D] _t ))) / t

In addition, in the above reaction, the same reaction was carried out in the presence of 200 equivalents of various phosphonium compounds with respect to Pd, and the same analysis was conducted (Examples 1-4: phosphonium-containing system).

In addition, in the above reaction, the same reaction was carried out in the presence of 200 equivalents of an alkali metal salt with respect to Pd, and the same analysis was conducted (Comparative Examples 2 and 3: an alkali metal cation present system).

The results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.

As is clear from the above results, when a phosphonium compound is present in the reaction system, the activity is improved as compared with the system without a counter cation, and even when compared with an alkali metal cation which is a counter cation of a conventionally known nucleophile, The effect is great.

<Examples 5 to 9>
Instead of using 200 equivalents of the phosphonium compound with respect to palladium in Examples 1 to 4, 200 equivalents of each of the various phosphines shown in Table 2 were added to prepare the corresponding phosphonium compounds also shown in Table 2 in the reaction system. The reaction was carried out under the same conditions except for the above.

The results of Examples 5 to 9 are shown in Table 2 below.

As is clear from the above results, even when phosphine is added to carry out the reaction, it is easily converted into a phosphonium compound in the system at the beginning of the reaction, and the reaction activity is improved. Further, when the change of the solution in the system to which triphenylphosphine was added using a strong catalyst solution was traced by measurement of ³¹ P-NMR spectrum, the signal of triphenylphosphine showing a chemical shift value of −6 ppm even at room temperature was found. It was also observed that it was consumed relatively quickly and eventually disappeared, and changed to a plurality of signals considered to be phosphonium compounds in the region of 17 to 25 ppm.

<Examples 11 to 13 and Comparative Examples 4 to 6>
The ligand of the catalyst in Example 5 was changed from (L-26) to (L-25), (L-27) and (L-55), and 200 equivalents of triphenylphosphine were added in the same manner. The reaction was carried out in a system in which a phosphonium compound was prepared in the reaction system (Examples 11 to 13). For comparison, the reaction was carried out in the same manner as in Examples 11 to 13 even in a system where no phosphonium compound was present (Comparative Examples 4 to 6).

The results of Examples 11 to 13 and Comparative Examples 4 to 6 are shown in Table 3 below.

As is evident from the above results, in the system using the other bidentate phosphite ligand, the activity was similarly improved by 2.1 to 2.9 times due to the presence of phosphonium. I understand.

<Example 14>
In the same manner as in Example 5, triphenylphosphine was added under a palladium-bidentate phosphite (L-26) catalyst system, and a 34 DABE isomerization reaction was performed in a system in which a phosphonium compound was prepared in the reaction system. However, the activity was compared by changing the abundance of the phosphonium compound to 100, 50, 20, 10, 5, and 0 equivalents relative to palladium. FIG. 1 is a graph showing the correlation when the abscissa indicates the amount of the phosphonium compound relative to palladium and the ordinate indicates the reaction rate constant.

As is apparent from the figure, the activity is increased to about twice by the presence of 5 equivalents of the phosphonium compound with respect to palladium, and the activity improvement rate is almost leveled off by the presence of about 20 equivalents. .

<Example 15 and Comparative Example 7>
A reaction for producing allyl phenyl ether by performing an allylation reaction using allyl methyl carbonate as an allyl raw material compound and phenoxide as a nucleophile in the presence of a palladium-bidentate phosphite (L-26) catalyst The present invention was applied to.

As a transition metal compound, 0.0149 g (0.0151 mmol) of trisdibenzylideneacetone dipalladium having a palladium content of 21.5% by weight, and as a bidentate phosphite compound, 4 equivalents of the above formula (L- The compound of the above 26) (0.1291 g, 0.1205 mmol) was placed in a 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 carrying out the reaction was replaced with argon, and 4.45 g of a tetrahydrofuran solution containing 3.85% by weight of allylmethyl carbonate and 6.06% by weight of phenol was added. Thereto was added 5 μl of the above-mentioned catalyst solution with a microsyringe, and the mixture was heated at 60 ° C. to perform a reaction (Comparative Example 7: reaction without a phosphonium compound). The reaction rate was evaluated by determining the conversion of allylmethyl carbonate by analyzing the solution composition before and after the reaction by gas chromatography, and applying the value to the following formula to calculate the reaction rate constant. Here, the reaction was regarded as a pseudo-primary reaction ignoring the effect of the change in phenol concentration, and the reaction rate: k was calculated from the following equation. In the following formula, conv. Represents the conversion of allyl methyl carbonate, and t represents the reaction time (unit: hours) at that time.

K = -ln (1-conv.) / T

反 応 Further, the reaction was carried out in a system in which 200 equivalents of tetra (n-butyl) phosphonium acetate was added to palladium under the conditions of Comparative Example 7 described above (Example 15: system containing phosphonium compound).

As is clear from the above results, it can be seen that the application of the present invention can similarly improve the reactivity in other allylation reaction systems.

In Example 14 of this invention, it is a graph which shows the correlation at the time of taking the abundance of the phosphonium compound with respect to palladium on a horizontal axis, and taking the reaction rate constant on a vertical axis | shaft, respectively.

Claims (9)

Allyl raw material compound and nucleophile in the presence of a catalyst containing a transition metal compound containing at least one transition metal selected from the group consisting of transition metals belonging to Groups 8 to 10 of the periodic table and a trivalent phosphorus compound A method for producing a new allyl compound by reacting the compound with a phosphonium compound in the reaction system. 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, a chain or cyclic alkyl group, an aryl group (aromatic 6π above and below the ring) A heterocyclic compound that forms an electron cloud; the same applies hereinafter), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, or an acyloxy group, and these groups further have a substituent. If any of the good .R ^a to R ^e even contains carbon chain, one or more carbons in its carbon chain - which may be present carbon double bond or triple bond .X is halogen Atom, carbon atom to which at least one electron-withdrawing group is bonded, hydroxy group, nitro group, amino group, sulfonyl group, sulfonate group, acyloxy group, carbonate group, carbamate group, phosphate group, alkyl group Represents an xy group or an aryloxy group, which may further have a substituent and, when a carbon chain is contained, has one or more carbon-carbon double bonds or triple bonds in the carbon chain. 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 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. 5. The method for producing an allyl compound according to the above. 方法 The method for producing an allyl compound according to any one of claims 1 to 3, wherein the trivalent phosphorus compound is a phosphite compound. The method for producing an allyl compound according to any one of claims 1 to 4, wherein the phosphonium compound has a structure represented by the following general formula (1).
PX ¹ X ² X ³ X ⁴ . . . General formula (1)
(In the above general formula (1), X ^{1 to} X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group. Represents an arylthio group or an arylthio group, which may further have a substituent and, when a carbon chain is contained, has one or more carbon-carbon double bonds or triple bonds in the carbon chain. In addition, any two or more of X ^{1 to} X ⁴ may be bonded to each other to form one or more cyclic structures.) Method for producing X ¹ to X ⁴ in the general formula (1) are each independently, characterized in that an unsubstituted or substituted alkyl or aryl group, claim 5 allyl compounds according. The method for producing an allyl compound according to claim 5, wherein at least one of X ^{1 to} X ⁴ in the general formula (1) is an unsubstituted or substituted aryl group. The transition metal compound is a palladium compound, the trivalent phosphorus compound is a bidentate phosphite compound represented by the following general formula (IV), and the allyl raw material compound is represented by the following general formula (b). Wherein the nucleophile is acetic acid (CH ₃ COOH) or its deprotonated form (CH ₃ COO ⁻ ), or water (H ₂ O) or its deprotonated form (HO ⁻ ) The method for producing an allyl compound according to any one of claims 5 to 7, wherein the allyl compound produced is a compound having a structure represented by the following general formula (c). .
^{(R 16 O) (R 17} O) P-O-A 1 -O-P (R 18 O) (R 19 O). . . General formula (IV)
(In the general formula (IV), R ^{16 to} R ¹⁹ each independently represent an alkyl group or an aryl group which may have a substituent. A ¹ represents a divalent organic group.)
^{_{CH 2 = CH-CHR 1 -CH}} 2 R 2. . . General formula (b)
R ³ CH ₂ —CH ＝ CH—CH ₂ R ⁴ . . . General formula (c)
(In the above general formulas (b) and (c), R ^{1 to} R ⁴ each independently represent an acetoxy group or a hydroxy group.) The transition metal compound is a palladium compound, the trivalent phosphorus compound is a bidentate phosphite compound represented by the following general formula (IV), and the allyl raw material compound is a compound represented by the following general formula (c). Wherein the nucleophile is acetic acid (CH ₃ COOH) or its deprotonated form (CH ₃ COO ⁻ ), or water (H ₂ O) or its deprotonated form (HO ⁻ ) The method for producing an allyl compound according to any one of claims 5 to 7, wherein the produced allyl compound is a compound having a structure represented by the following general formula (b). .
^{(R 16 O) (R 17} O) P-O-A 1 -O-P (R 18 O) (R 19 O). . . General formula (IV)
(In the general formula (IV), R ^{16 to} R ¹⁹ each independently represent an alkyl group or an aryl group which may have a substituent. A ¹ represents a divalent organic group.)
^{_{CH 2 = CH-CHR 1 -CH}} 2 R 2. . . General formula (b)
R ³ CH ₂ —CH ＝ CH—CH ₂ R ⁴ . . . General formula (c)
(In the above general formulas (b) and (c), R ^{1 to} R ⁴ each independently represent an acetoxy group or a hydroxy group.)

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