JP4562370B2 - Method for producing rearranged unsaturated compound - Google Patents

Description

  The present invention relates to a method for producing a rearrangement compound by intramolecular rearrangement of a compound having an unsaturated bond, and a catalyst used therefor, and more specifically, a boron compound is used together with a rhenium compound as a catalyst, and intramolecular rearrangement or skeletal rearrangement is efficiently performed. The present invention relates to a method for producing a rearrangement compound by the above, and a catalyst used therefor.

  Conventionally, a method using a rhenium compound as a catalyst for the Beckmann rearrangement reaction is known. For example, a method of rearranging an oxime compound in a liquid phase in the presence of a solvent containing a rhenium peroxide compound and a sulfur-containing compound to obtain an amide compound (for example, see Patent Document 1), or in the presence of a rhenium peroxide compound and a solvent. In the method of rearranging an oxime compound in a liquid phase to obtain an amide compound, a method for producing an amide having a water content in the liquid phase of 100 ppm or less (see, for example, Patent Document 2) or a specific rhenium peroxide compound A method for producing an amide compound that rearranges an oxime compound in the presence (see, for example, Patent Documents 3 and 4), or a rearrangement of an oxime compound in the presence of a nitrogen-containing heterocyclic compound in the presence of a specific rhenium peroxide compound. A method for producing an amide compound (see, for example, Patent Document 5), or conversion of an oxime compound in the presence of a specific rhenium peroxide compound and a group 14 compound. A method for producing an amide compound (for example, see Patent Document 6), and a method for producing an amide by rearrangement of an oxime in the presence of a perrhenate and a strong acid or a derivative thereof (for example, Patent Document 7, Non-Patent Document 1). 2)) have been reported.

In addition, allyl rearrangement method of primary or secondary allylic alcohol performed in the presence of perrhenate and aryl sulfonic acid (for example, Patent Document 8, Non-Patent Documents 3 and 4) and identification having alkylsilyl group A method of obtaining a specific cyclopentanone by cyclization and desilylation of the chain pentanone (see, for example, Patent Document 9), Beckmann fragmentation reaction (for example, Non-Patent Document 5), or rearrangement of a specific propargyl alcohol compound And a method for obtaining a specific α, β-unsaturated carbonyl compound (see, for example, Patent Document 10) or reacting an oxime having a specific phenyl group in the presence of tetraalkylammonium perrhenate and trifluoromethanesulfonic acid. A method for producing quinolines (for example, see Patent Document 11) and cyclic ketones by internal rearrangement. Methods (for example, see Patent Document 12), rearrangement reactions of trimethylsilyl rhenium peroxide, allyl alcohol and the like using alkylsiloxy peroxide (for example, see Non-Patent Documents 6 and 7), and the like have been reported.
JP 2001-354645 A JP 2001-342174 A Japanese Patent Laid-Open No. 9-301951 JP-A-8-143544 JP-A-9-301052 JP-A-8-151362 JP-A-5-51366 JP-A-5-97734 JP-A-5-163190 JP-A-5-97758 JP-A-7-247270 JP 7-247268 A Narasaka, K., Kusama, H., Yamashita, Y., Sato, H., Chem. Lett. 1993, p. 489 Kusama, H., Yamashita, Y., Narasaka, K., Bull. Chem. Soc. Jpn. 1995 Vol. 68p. 373 Narasaka, K., Kusama, H., Hayashi, Y., Chem. Lett 1991 p.1413 Narasaka, K., Kusama, H., Hayashi, Y .; Tetrahedron 1992 Vol. 48p. 2059 Kusama, H., Yamashita, Y., Narasaka, K., Bull. Chem. Soc. Jpn. 1995 Vol68p.373 BelleminLaponnaz, S., Gisie, H., LeNy, JP, Osborn; JAAngew.Chem.Int.Ed.Engl. 1997 Vol36p.976 BellminLaponnaz, S., LeNy, JP, Osborn, JA; TetrahedronLett.2000Vol41p.1549

  An object of the present invention is to provide a highly useful rearrangement compound that can be used for the synthesis of various compounds obtained by a reaction using a rhenium compound as a catalyst, such as a Beckmann rearrangement reaction or a rearrangement reaction of an α, β-unsaturated alcohol. Another object of the present invention is to provide a process for producing a rearrangement compound that can be more easily and efficiently produced.

  The present inventors have compared the activity of various catalysts for the Beckmann rearrangement reaction under the condition that acetophenone oxime is heated to reflux in acetonitrile for 4 hours. As a result, rhenium peroxide and trimethylsiloxyrhenium peroxide are used alone. In addition, the present inventors have found that the chemical yield is drastically improved by the coexistence of 3,5-bis (trifluoromethyl) phenylboronic acid, which itself has little activity. Based on such knowledge, when a compound having an unsaturated bond is reacted with a rhenium compound in the presence of a boron compound, a rearranged compound by intramolecular rearrangement or skeletal rearrangement can be produced in a yield exceeding prediction. Confirmed that the catalytic activity of the rhenium compound can be remarkably improved, and the present invention has been completed.

That is, the present invention provides (1) a compound represented by the general formula (I) in the presence of a rhenium compound that is rhenium peroxide, anhydrous rhenium peroxide, or trialkylsiloxy rhenium peroxide and a boron compound that is an arylboronic acid.



[Wherein, R ¹ and R ² independently represent a chain or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹ and R 2 ² may be united to form a ring. An oxime compound having an unsaturated bond represented by the general formula (II)



[Wherein, R ¹ and R ² each represent the same group as R ¹ and R ² in formula (I) . An amide compound represented by
Or general formula (III)
[Wherein, R ^{3 to} R ⁷ 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, Some of R ^{3 to} R ⁷ may be combined to form a ring, and R ⁸ represents a hydrogen atom or a silyl group which may have a substituent (provided that R ^{3 to} R ^7). Except when is simultaneously hydrogen.) An α, β-unsaturated alcohol having an unsaturated bond represented by the general formula (IV)



Wherein, R ³ to R ⁸ represents the same group respectively R ³ to R ⁸ in the general formula (III). An α, β-unsaturated alcohol represented by
The present invention relates to a process for producing a rearrangement compound.

The present invention also relates to (2) the method for producing a rearranged compound according to the above (1), wherein in general formula (III), R ⁸ represents a silyl group which may have a substituent. (3) The method for producing a rearrangement compound according to any one of (1) or (2) above, wherein the rhenium compound is a rhenium peroxide compound or an anhydrous rhenium peroxide compound, and (4) a rhenium compound Is a trialkylsiloxy rhenium peroxide compound, the method for producing a rearrangement compound according to any one of the above (1) or (2), or (5) a trialkylsiloxy rhenium peroxide compound is trimethylsiloxy The method for producing a rearrangement compound according to the above (4), which is rhenium peroxide, or (6) the arylboronic acid is 3,5-bis (trifluoromethyl) phenylboronic acid or The method for producing a rearrangement compound according to any one of the above (1) to (5), which is fluorofluoroboronic acid, and (7) the boron compound is present in an amount of 1 to 5 with respect to the rhenium compound. The method for producing a rearrangement compound according to any one of (1) to (6) above, wherein (8) the solvent is a nitrile solvent, an aromatic hydrocarbon solvent, an ether solvent And (9) azeotropic dehydration during intramolecular rearrangement reaction or skeletal rearrangement reaction, wherein the rearrangement compound according to any one of (1) to (7) above is used, It is related with the manufacturing method of the rearrangement compound in any one of said (1)-(8) characterized .

Furthermore, the present invention includes (10) a rhenium compound which is rhenium peroxide, anhydrous rhenium peroxide or trialkylsiloxy rhenium peroxide, and a boron compound which is an aryl boronic acid. It relates to a catalyst for intramolecular rearrangement or skeletal rearrangement reaction of the compound having an unsaturated bond as described in 9).

  In the method for producing an unsaturated compound of the present invention, a compound having an unsaturated bond is reacted in the presence of a rhenium compound and a boron compound, and a rearranged compound by intramolecular rearrangement or skeletal rearrangement is obtained in an unexpected yield. Can do. Examples of the intramolecular rearrangement and skeletal rearrangement of the unsaturated compound in the method for producing the rearranged compound of the present invention include rearrangement of the hydroxy group of α, β-unsaturated alcohol, and Beckmann rearrangement of not only acyclic but also cyclic oxime. And unsaturated compounds useful for the synthesis of highly useful substances can be easily obtained in high yield.

  The method for producing a rearranged compound of the present invention is not particularly limited as long as it is a method for producing a rearranged compound in which a compound having an unsaturated bond undergoes intramolecular rearrangement or skeletal rearrangement in the presence of a rhenium compound and a boron compound. . Here, intramolecular rearrangement refers to rearrangement of a detached hydroxyl group or the like to other cationic carbon accompanying generation of a cation due to elimination of a hydroxyl group or the like, and skeletal rearrangement refers to elimination of a hydroxyl group or the like. As the cation is generated, the carbon-carbon bond is cleaved, causing a 1,2-rearrangement to other atoms such as nitrogen in the molecule, and the detached hydroxyl group is newly generated by cleaving the carbon-carbon bond. To produce a rearranged compound.

  As a method for producing the unsaturated compound of the present invention, as shown in the following formula,

The method using the Beckmann rearrangement which manufactures the amide compound represented by general formula (II) by skeleton rearrangement of the oxime represented by general formula (I) can be mentioned. The elimination of the hydroxyl group of the oxime breaks the carbon-carbon bond with the generation of the cation, causing a 1,2-rearrangement to the nitrogen atom in the molecule, and the detached hydroxyl group is newly regenerated by breaking the carbon-carbon bond. It reacts with the resulting cation and is converted to the carbonyl oxygen of the amide group to produce an amide compound.

In the oxime represented by the general formula (I), in the formula, R ¹ and R ² independently have a linear or cyclic alkyl group which may have a substituent, or a substituent. Or a good aryl group. Examples of the alkyl group represented by R ¹ and R ² include C1-C20 chain groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. Examples of the alkyl group include C3-C20 cyclic alkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the aryl group represented by R ¹ and R ² include a phenyl group and a benzyl group. Phenethyl group, 1-naphthyl group, 2-naphthyl group, and the like. Examples of the substituent in the chain or cyclic alkyl group or aryl group include alkyl groups such as methyl group, ethyl group, and propyl group, phenyl group, benzyl group, phenethyl group, 1-naphthyl group, and 2-naphthyl group. An aryl group etc. can be mentioned, In the linear or cyclic alkyl group and the aryl group, you may have 1 or 2 or more of these substituents simultaneously. Further, R ¹ and R ² may be combined to form a ring. Examples of such a ring include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane. Examples of the substituent in the ring include the same substituents as the substituents in the alkyl group and aryl group represented by R ¹ and R ² .

  Specific examples of the oxime represented by the general formula (I) include acetone oxime, ethyl methyl ketone oxime, methyl propyl ketone oxime, isopropyl methyl ketone oxime, butyl methyl ketone oxime, isobutyl methyl ketone oxime, and diethyl ketone oxime. , Diisopropyl ketone oxime, cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxime, 4-methylcyclohexanone oxime, 3,5-dimethylcyclohexanone oxime, 4-phenylcyclohexanone oxime, cycloheptanone oxime, 4-methylcycloheptanone oxime, 3 , 6-Dimethylcycloheptanone oxime, 4-phenylcycloheptanone oxime, cyclooctanone oxime, 5-methylcyclooctano Oxime, 4,6-dimethylcyclooctanone oxime, 5-phenylcyclooctanone oxime, acetophenone oxime, propylphenone oxime, butylphenone oxime, barrel phenone oxime, benzophenone oxime, dibenzyl ketone oxime, 2-acetonaphthone oxime, etc. Can be mentioned.

In the amide compound represented by the general formula (II) produced by oxime skeletal rearrangement represented by the above general formula (I), wherein, R ¹ and R ^2, R ¹ and in the general formula (I) Specific examples of the amide compound of the rearrangement compound represented by the general formula (II), which each represent the same group as R ² , include N-methylacetamide, N-ethylacetamide, N-methylpropionamide, N- Propylacetamide, N-methylbutyramide, N-isopropylacetamide, N-methylisobutyramide, N-butylacetamide, N-methylvaleramide, N-isobutylacetamide, Nt-butylacetamide, N-ethylpropionamide, N -Isopropylisobutyramide, pyrrolidin-2-one, piperidin-2-one,
Perhydroazepin-2-one, 5-methylperhydroazepin-2-one, 4,6-dimethylperhydroazepin-2-one, 5-phenylperhydroazepin-2-one, perhydroazocin-2-one ON, 5-methylperhydroazocin-2-one, 4,7-dimethylperhydroazocin-2-one, 5-phenylperhydroazocin-2-one, perhydroazonin-2-one, 6 -Methylperhydroazonin-2-one, 5,7-dimethylperhydroazonin-2-one, 6-phenylperhydroazonin-2-one, N-phenylacetamide, N-phenylpropionamide, N- And phenylbutyramide, N-phenylvaleramide, N-benzylbenzoylamide, N-naphthon-2-ylacetamide, etc. .

As the rhenium compound used in the method for producing the amide compound represented by the general formula (II) by the skeletal rearrangement of the oxime represented by the general formula (I), a rhenium peroxide compound is preferable, and the rhenium peroxide compound is used. As rhenium peroxide ((HO) ReO ₃ ) and its anhydride (Re ₂ O ₇ ), trimethylsiloxy rhenium peroxide, triethylsiloxy rhenium peroxide, tributylsiloxy rhenium peroxide, tripropylsiloxy rhenium peroxide, etc. It may be a trialkylsiloxy rhenium peroxide compound. The amount of the rhenium peroxide compound used is 1 to 20 mol%, preferably 1 to 10 mol%, based on the oxime amount represented by the general formula (I).

  As a boron compound used in the method for producing the amide compound represented by the general formula (II) by the skeletal rearrangement of the oxime represented by the above general formula (I), aryl boronic acid and its derivatives are preferred specific examples. It can be illustrated. As the derivatives of aryl boronic acids, those having an electron-withdrawing substituent such as a halogenated alkyl group are preferable. Specifically, 4-trifluoromethylphenylboronic acid, 4-trichloromethylphenylboronic acid, 4-trichloromethyl Bromomethylphenylboronic acid, 4- (perfluoroethyl) phenylboronic acid, 4- (perchloroethyl) phenylboronic acid, 4- (perbromoethyl) phenylboronic acid, 4- (perfluoropropyl) phenylboronic acid, 4- (perchloropropyl) phenylboronic acid, 4- (perbromopropyl) phenylboronic acid, 4- (perfluorobutyl) phenylboronic acid, 4- (perchlorobutyl) phenylboronic acid, 4- (perbromobutyl) ) Phenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid 3,5-bis (trichloromethyl) phenylboronic acid, 3,5-bis (tribromomethyl) phenylboronic acid, 3,5-bis (perfluoroethyl) phenylboronic acid, 3,5-bis (perchloroethyl) ) Phenylboronic acid, 3,5-bis (perbromoethyl) phenylboronic acid, 3,5-bis (perfluoropropyl) phenylboronic acid, 3,5-bis (perchloropropyl) phenylboronic acid, 3,5 -Bis (perbromopropyl) phenylboronic acid, 3,5-bis (perfluorobutyl) phenylboronic acid, 3,5-bis (perchlorobutyl) phenylboronic acid, 3,5-bis (perbromobutyl) phenyl Boronic acid, 3-fluorophenylboronic acid, 3-chlorophenylboronic acid, 3-bromophenylboronic acid, 4-fluorophenyl Examples include ruboronic acid, 4-chlorophenylboronic acid, 4-bromophenylboronic acid, 3,4,5-trifluorophenylboronic acid, 3-nitrophenylboronic acid, and among these, in particular, 3,5 -Bis (trifluoromethyl) phenylboronic acid and 4-fluorophenylboronic acid are preferred.

  The amount of the arylboronic acid or its derivative is not particularly limited, but the molar amount of the product is 5 times the amount of rhenium (VII) contained in the rhenium peroxide compound. Highly preferred.

  In the method for producing the amide compound represented by the general formula (II) by the skeletal rearrangement of the oxime represented by the general formula (I), usable solvents include toluene, acetonitrile, propionitrile, butyronitrile, benzoate. Nitrile solvents such as nitriles, haloalkane solvents such as dichloroethane, dichloromethane, dimethoxyethane, chloroform, aromatic hydrocarbon solvents such as chlorobenzene, ether solvents, ester solvents, amide solvents, etc. One or more of these solvents can be used in combination, and among these, nitrile solvents, nitroalkane solvents, ether solvents, ester solvents, amide solvents, etc., high polarities with high boiling points An aprotic solvent is preferable because the temperature at reflux can be set high. The reaction involving intramolecular rearrangement of the oxime is carried out by constantly bringing the reaction system to an anhydrous state while performing azeotropic dehydration, such as 1 to 24 hours at the boiling point of the solvent, preferably 1 to 5 hours at a temperature of 100 to 160 ° C. Is preferable. However, in some cases, the solvent may be heated without reflux using a solvent having a boiling point higher than the reaction temperature.

  As a production method of the unsaturated compound of the present invention, as shown in the following formula,

A method for producing an α, β-unsaturated alcohol of a rearranged compound represented by formula (IV) by intramolecular rearrangement of an α, β-unsaturated alcohol represented by formula (III) having an unsaturated bond Can be mentioned. Cations are generated in other carbons by elimination of hydroxyl groups of α, β-unsaturated alcohols, and rearranged compounds are rearranged to cationic carbons to generate α, β-unsaturated alcohols of rearranged compounds. .

In the α, β-unsaturated alcohol represented by the general formula (III), in the formula, R ^{3 to} R ⁷ are independently a hydrogen atom or a chain or cyclic which may have a substituent. An alkyl group or an aryl group which may have a substituent, some of R ^{3 to} R ⁷ may be combined to form a ring, and R ⁸ is a hydrogen atom or a silyl group; Show. However, it excludes when R < ³ > -R < ⁷ > shows a hydrogen atom simultaneously. Examples of the alkyl group represented by R ^{3 to} R ⁷ include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group, Examples thereof include cyclic alkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the aryl group include a phenyl group, a benzyl group, a phenethyl group, a 1-naphthyl group, and a 2-naphthyl group. Can be mentioned. Examples of the ring formed by R ⁶ and R ⁷ together include cyclic alkenes such as 2-cyclopentene, 2-cyclohexene, 2-cycloheptene, 2-cyclooctene, 2-cyclononene, and 2-cyclodecene. it can. Examples of the substituent in the chain or cyclic alkyl group and aryl group include alkyl groups such as methyl group, ethyl group, and propyl group, phenyl group, benzyl group, phenethyl group, 1-naphthyl group, and 2-naphthyl group. An aryl group etc. can be mentioned, In the chain or cyclic alkyl group or aryl group, you may have 1 or 2 or more of these substituents simultaneously.

  Specific examples of the α, β-unsaturated alcohol represented by the general formula (III) include 2-buten-1-ol, 2-penten-1-ol, and 2-hexene-1- All, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decene-1-ol, 3-phenyl-2-propen-1-ol, 4-phenyl- 2-buten-1-ol, 5-phenyl-2-penten-1-ol, 6-phenyl-2-hexen-1-ol, 7-phenyl-2-hepten-1-ol, 8-phenyl-2- Octen-1-ol, 9-phenyl-2-nonen-1-ol, 10-phenyl-2-decen-1-ol, 2-methyl-2-buten-1-ol, 2-methyl-2-pentene- 1-ol, 2-methyl-2-hexene- 1-ol, 2-methyl-2-hepten-1-ol, 2-methyl-2-octen-1-ol, 2-methyl-2-nonen-1-ol, 2-methyl-2-decene-1- Ol, 6-benzyl-2-cyclohexen-1-ol, 4-phenyl-1-vinyl-cyclohexane-1-ol, and the like.

In the α, β-unsaturated alcohol represented by the general formula (IV) generated by intramolecular rearrangement of the α, β-unsaturated alcohol represented by the general formula (III), R ^{3 to} R ⁸ represents the same group as R ^{3 to} R ⁸ in the general formula (III), respectively. As the α, β-unsaturated alcohol of the rearranged compound represented by the general formula (IV), specifically, 1 -Buten-3-ol, 1-penten-3-ol, 1-hexen-3-ol, 1-hepten-3-ol, 1-octen-3-ol, 1-nonen-3-ol, 1-decene -3-ol, 3-phenyl-1-propen-3-ol, 4-phenyl-1-buten-3-ol, 5-phenyl-1-penten-3-ol, 6-phenyl-1-hexene-3 -Ol, 7-phenyl-1-hepten-3-ol, 8- Enyl-1-octen-3-ol, 9-phenyl-1-nonen-3-ol, 10-phenyl-1-decen-3-ol, 2-methyl-1-buten-3-ol, 2-methyl- 1-penten-3-ol, 2-methyl-1-hexen-3-ol, 2-methyl-1-hepten-3-ol, 2-methyl-1-octen-3-ol, 2-methyl-1- Nonen-3-ol, 2-methyl-1-decen-3-ol, etc. can be mentioned.

Further, as a method for producing the rearrangement compound of the present invention, the α, β-unsaturated alcohol represented by the general formula (III) is a compound in which R ⁸ is a silyl group which may have a substituent. preparation of a silyl compound of the general formula (IV) (wherein, R ⁸ represents the same group as R ⁸ in the general formula (III).) by intramolecular rearrangement of such silyl compounds rearrangement compound represented by showing A method can also be mentioned. In general formula (III), examples of the substituent in R ⁸ include alkyl groups such as a methyl group and an ethyl group. Specific examples of the silyl group represented by R ⁸ include a trimethylsilyl group and a triethylsilyl group. can do. Examples of the silyl compound represented by the general formula (III) when R ⁸ represents a silyl group include 1-trimethylsiloxy-2-butene, 1-trimethylsiloxy-2-pentene, 1-trimethylsiloxy-2-hexene, Examples thereof include trimethylsiloxy-2-heptene, 1-triethylsiloxy-2-octene, 1-triethylsiloxy-2-nonene, 1-triethylsiloxy-2-decene and the like.

  Specific examples of the rearranged compound produced by intramolecular rearrangement of the silyl compound represented by the general formula (III) include 3-trimethylsiloxy-1-butene, 3-trimethylsiloxy-1-pentene, 3 -Trimethylsiloxy-1-hexene, 3-trimethylsiloxy-1-heptene, 3-triethylsiloxy-1-octene, 3-triethylsiloxy-1-nonene, 3-triethylsiloxy-1-decene, The silyl compound shown can be exemplified.

As a rhenium compound or a boron compound used in the method for producing an α, β-unsaturated alcohol represented by the general formula (IV) generated from the α, β-unsaturated alcohol represented by the general formula (III) The same as the rhenium compound or boron compound used in the Beckmann rearrangement reaction of the oxime represented by the general formula (I) can be used. Similarly, the amount of rhenium compound used is preferably 1 to 10 mol%, preferably 1 to 5 mol, based on the amount of α, β-unsaturated alcohol represented by the general formula (III). It is preferable that the amount of the boron compound used is 1 to 3 times the molar amount of the rhenium compound. Usable solvents include aromatic hydrocarbon solvents such as toluene, nitrile solvents such as acetonitrile and propionitrile, halogenated hydrocarbon solvents such as dichloromethane, ether solvents such as diethyl ether and THF, ethyl acetate, etc. Ester solvents, amide solvents such as DMF, and the like can be used. The rearrangement reaction of the α, β-unsaturated alcohol is preferably performed at about 0 ° C. to 50 ° C. for 1 to 12 hours. The rearrangement reaction of the α, β-unsaturated alcohol represented by the general formula (IV) by the intramolecular rearrangement of the α, β-unsaturated alcohol represented by the general formula (III) is an equilibrium reaction, and the rearrangement in the equilibrium state Since the abundance ratio of the compound depends on the thermodynamic stability, it is possible to increase the yield of the rearranged compound represented by the general formula (IV) by individually selecting appropriate conditions.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to the scope of these examples.

Beckmann rearrangement reaction [Example 1-1]

A reaction vessel containing 2 mmol of acetophenone oxime, a 65-70 wt% aqueous solution of rhenium peroxide (2.5 mol% as rhenium peroxide), 12.5 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 4 ml of acetonitrile In addition, the mixture was refluxed at an oil bath temperature of 120 ° C. for 4 hours. A Dean-Stark shunt was attached to the top of the reaction vessel so that the reaction system became anhydrous during the reaction. After completion of the reaction, it was directly purified by silica gel column chromatography to obtain acetanilide with a chemical yield of 94%.
[Example 1-2]
The same procedure as in Example 1-1 was performed except that trimethylsiloxy rhenium peroxide was used instead of rhenium peroxide. Acetanilide was obtained with a chemical yield of 99% or more.
[Comparative Example 1-1]
The same procedure as in [Example 1-1] was conducted except that rhenium peroxide was not added. The chemical yield of acetanilide was 13%.
[Comparative Example 1-2]
The same procedure as in [Example 1-1] except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. The chemical yield of acetanilide was 43%.
[Comparative Example 1-3]
The same procedure as in [Example 1-1] except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. The chemical yield of acetanilide was 54%.

  The results also indicate that by allowing 3,5-bis (trifluoromethyl) phenylboronic acid to be present together with rhenium peroxide or trimethylsiloxy rhenium peroxide, the Beckmann rearrangement proceeds rapidly and a rearranged compound is obtained in high yield. It became clear that

Beckmann rearrangement reaction [Example 2-1]

2 mmol of cyclododecanone oxime, 65-70 wt% aqueous solution of rhenium peroxide (2.5 mol% as rhenium peroxide), 12.5 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 4 ml of acetonitrile In addition to the reaction vessel, the mixture was refluxed for 4 hours at an oil bath temperature of 120 ° C. A Dean-Stark shunt was attached to the top of the reaction vessel so that the reaction system became anhydrous during the reaction. After completion of the reaction, it was directly purified by silica gel column chromatography to obtain dodecyl lactam with a chemical yield of 99% or more.
[Comparative Example 2-1]
The same procedure as in [Example 2-1] was performed except that rhenium peroxide was not added. The chemical yield of dodecyl lactam was 5%.
[Comparative Example 2-2]
The same procedure as in [Example 2-1] except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. The chemical yield of dodecyl lactam was 63%.

  The results also show that the presence of 3,5-bis (trifluoromethyl) phenylboronic acid together with rhenium peroxide allows the Beckmann rearrangement to proceed rapidly and a rearranged compound to be obtained in high yield. It was.

Beckmann rearrangement reaction [Example 3-1]

Add 2 mmol of cyclohexanone oxime, 65-70 wt% aqueous solution of rhenium peroxide (4 mol% as rhenium peroxide), 20 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 4 ml of benzonitrile to the reaction vessel, Heated at an oil bath temperature of 140 ° C. for 1 hour. A condenser was attached to the top of the reaction vessel. After completion of the reaction, the obtained solution was subjected to spectrum analysis by ¹ H NMR. As a result, it was found that 71% of ε-caprolactam and 18% of cyclohexanone were produced.
[Example 3-2]
Add 2 mmol of cyclohexanone oxime, 65-70 wt% aqueous solution of rhenium peroxide (8 mol% as rhenium peroxide), 100 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 4 ml of benzonitrile to the reaction vessel, Heated at an oil bath temperature of 140 ° C. for 1 hour. A condenser was attached to the top of the reaction vessel. After completion of the reaction, it was directly purified by distillation under reduced pressure (0.1 torr, 100 ° C.) to obtain ε-caprolactam with a chemical yield of> 95%.
[Example 3-3]
2 mmol of cyclohexanone oxime, anhydrous rhenium peroxide (2 mol%), 20 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 4 ml of benzonitrile were added to the reaction vessel, and the temperature of the oil bath was 140 ° C. for 1 hour. Heated. A condenser was attached to the top of the reaction vessel. After completion of the reaction, the obtained solution was subjected to spectrum analysis by ¹ H NMR. As a result, it was found that 63% of ε-caprolactam and 16% of cyclohexanone were produced.
[Example 3-4]
Cyclohexanone oxime 2 mmol, anhydrous rhenium peroxide (2 mol%), 4-fluorophenylboronic acid 20 mol% and benzonitrile 4 ml were added to the reaction vessel and heated at an oil bath temperature of 140 ° C for 1 hour. A condenser was attached to the top of the reaction vessel. After completion of the reaction, the obtained solution was subjected to spectrum analysis by ¹ H NMR. As a result, it was found that 75% of ε-caprolactam and 6% of cyclohexanone were produced.
[Example 3-5]
Cyclohexanone oxime 2 mmol, anhydrous rhenium peroxide (2 mol%), 4-fluorophenylboronic acid 10 mol%, and benzonitrile 4 ml were added to the reaction vessel and heated at an oil bath temperature of 140 ° C. for 3 hours. A condenser was attached to the top of the reaction vessel. After completion of the reaction, the obtained solution was subjected to spectrum analysis by ¹ H NMR. As a result, it was found that 88% of ε-caprolactam and 9% of cyclohexanone were produced.
[Example 3-6]
2 mmol of cyclohexanone oxime, anhydrous rhenium peroxide (4 mol%), 40 mol% of 4-fluorophenylboronic acid, and 4 ml of benzonitrile were added to the reaction vessel, and heated at an oil bath temperature of 140 ° C. for 1 hour. A condenser was attached to the top of the reaction vessel. After completion of the reaction, the obtained solution was subjected to spectrum analysis by ¹ H NMR. As a result, it was found that 96% of ε-caprolactam and 3% of cyclohexanone were produced.
[Comparative Example 3-1]
The same procedure as in [Example 3-1] was performed except that rhenium peroxide was not added. The chemical yield of ε-caprolactam was 5% or less.
[Comparative Example 3-2]
The same procedure as in [Example 3-1] except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. The chemical yield of ε-caprolactam was 31%.
[Comparative Example 3-3]
The same procedure as in [Example 3-5] was conducted except that anhydrous rhenium peroxide was not added. The chemical yield of ε-caprolactam was 5%, and the chemical yield of cyclohexanone was 10%.
[Comparative Example 3-4]
The same procedure as in [Example 3-3] except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. The chemical yield of ε-caprolactam was 46%, and the chemical yield of cyclohexanone was 5%.

  From the results, the presence of 3,5-bis (trifluoromethyl) phenylboronic acid and 4-fluorophenylboronic acid together with rhenium peroxide and anhydrous rhenium peroxide allows the Beckmann rearrangement to proceed rapidly, resulting in high yield. It was revealed that rearranged compounds can be obtained at a high rate. In particular, it has been clarified that the presence of 4-fluorophenylboronic acid together with anhydrous rhenium peroxide suppresses the generation of a by-product cycloalkanone and provides a rearranged compound in a high yield.

Rearrangement reaction of α, β-unsaturated alcohol [Example 4-1]

Reaction of 1 mmol of 2-octen-1-ol, 65-70 wt% aqueous solution of rhenium peroxide (2 mol% as rhenium peroxide), 10 mol% of 3,5-bis (trifluoromethyl) phenylboronic acid, and 2 ml of acetonitrile In addition to the container, the mixture was refluxed for 1 hour at an oil bath temperature of 0 ° C. A Dean-Stark shunt was attached to the top of the reaction vessel so that the reaction system became anhydrous during the reaction. After completion of the reaction, the product was directly purified by silica gel column chromatography to obtain 2-octen-1-ol and 1-octen-3-ol as a 46:54 mixture.
[Comparative Example 4-1]
The same procedure as in [Example 4-1] was carried out except that rhenium peroxide was not added. 2-Octen-1-ol and 1-octen-3-ol were obtained as a 100: 0 mixture.
[Comparative Example 4-2]
The same procedure as in [Example 4-1] was performed except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added. 2-Octen-1-ol and 1-octen-3-ol were obtained as a 63:37 mixture.
[Comparative Example 4-3]
The same procedure as in [Example 4-1] was conducted except that 3,5-bis (trifluoromethyl) phenylboronic acid was not added and the amount of rhenium peroxide added was 10 mol%. 2-Octen-1-ol and 1-octen-3-ol were obtained as a 56:44 mixture.

  From the results, the presence of 3,5-bis (trifluoromethyl) phenylboronic acid together with rhenium peroxide allows the intramolecular rearrangement to proceed rapidly, and the rearranged α, β-unsaturated alcohol is produced in a high yield. It became clear that it was obtained.

From the above results, it was found that 3,5-bis (trifluoromethyl) phenylboronic acid is extremely effective as a promoter for various organic reactions using rhenium peroxide as a catalyst.

Claims (10)

In the presence of a rhenium compound which is rhenium peroxide, anhydrous rhenium peroxide or trialkylsiloxy rhenium peroxide and a boron compound which is an arylboronic acid, the compound of the general formula (I)

[Wherein, R ¹ and R ² independently represent a chain or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹ and R 2 ² may be united to form a ring. The oxime compound having an unsaturated bond represented by] is dislocation skeletal general formula (II)

[Wherein, R ¹ and R ² each represent the same group as R ¹ and R ² in formula (I). An amide compound represented by
Or general formula (III)

[Wherein, R ^{3 to} R ⁷ 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, Some of R ^{3 to} R ⁷ may be combined to form a ring, and R ⁸ represents a hydrogen atom or a silyl group which may have a substituent (provided that R ^{3 to} R ^7). Except when is simultaneously hydrogen.) An α, β-unsaturated alcohol having an unsaturated bond represented by the general formula (IV)

Wherein, R ³ to R ⁸ represents the same group respectively R ³ to R ⁸ in the general formula (III). An α, β-unsaturated alcohol represented by
A process for producing a rearrangement compound, characterized in that it is obtained. The method for producing a rearranged compound according to claim 1, wherein R ⁸ in formula (III) represents a silyl group which may have a substituent. The method for producing a rearranged compound according to claim 1, wherein the rhenium compound is a rhenium peroxide compound or an anhydrous rhenium peroxide compound. The method for producing a rearranged compound according to claim 1, wherein the rhenium compound is a trialkylsiloxy rhenium peroxide compound. The method for producing a rearranged compound according to claim 4, wherein the trialkylsiloxy rhenium peroxide compound is trimethylsiloxy rhenium peroxide. The method for producing a rearranged compound according to any one of claims 1 to 5, wherein the aryl boronic acid is 3,5-bis (trifluoromethyl) phenyl boronic acid or 4-fluorophenyl boronic acid. The method for producing a rearranged compound according to any one of claims 1 to 6, wherein the abundance of the boron compound is 1 to 5 times the molar amount of the rhenium compound. The method for producing a rearranged compound according to any one of claims 1 to 7, wherein a nitrile solvent, an aromatic hydrocarbon solvent, an ether solvent, or a haloalkane solvent is used as the solvent. The method for producing a rearranged compound according to any one of claims 1 to 8, wherein azeotropic dehydration is performed during the intramolecular rearrangement reaction or the skeletal rearrangement reaction. Peroxides rhenium, expressed in anhydrous peroxide rhenium or trialkylsiloxy peroxide rhenium rhenium compounds and boron compounds from Na Ru claim 1 Symbol placement of the general formula is an aryl boronic acid (I) or (III) not Catalyst for intramolecular rearrangement or skeletal rearrangement reaction of a compound having a saturated bond.