JP2005097198A - Method for preparing 1-indanones - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for inexpensively and easily preparing indanones useful as synthetic intermediates of drugs and agricultural chemicals by the dehydration condensation of an aromatic hydrocarbon with a β-lactone while inhibiting formation of chemical substances which cause environmental pollution. <P>SOLUTION: The method for preparing the indanones represented by formula (IV) (wherein R<SP>1</SP>to R<SP>8</SP>are each a group which is not involved in the reaction) comprises reacting an aromatic hydrocarbon represented by formula (I) ( R<SP>1</SP>to R<SP>4</SP>are the same as defined above) with a β-lactone represented by formula (II) (wherein R<SP>5</SP>to R<SP>8</SP>are the same as defined above) in the presence of a catalytic amount of a Lewis acid represented by formula (III): MXmLn (wherein M is a metallic ion selected from Bi, Ga, In, Hf, and rare earth elements; X is an anion; L is an neutral molecule having coordination power; m is a valence of the metal M; and n is an integer of 0-100). This method can prepare 1-indanones in a shorter step than the conventional method, and thus is useful for industrial practice. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

   The present invention relates to a method for producing 1-indanones useful as synthetic intermediates for organic materials such as medical pesticides, metal catalyst ligands, and liquid crystals.

  Currently, methods for producing 1-indanones include intramolecular cyclization reaction of 3-arylpropionic acids (see, for example, Non-Patent Document 1), oxidation reaction of indanes (see, for example, Patent Documents 1 and 2), Reaction of aromatic hydrocarbon with γ-lactone (for example, see Non-Patent Document 2), Reaction of aromatic hydrocarbon with α, β-unsaturated carboxylic acid or derivative thereof (for example, Patent Documents 3 to 7, Various methods such as a reaction of phenylacetylenes with carbon monoxide (for example, Patent Document 8) are known. However, a method for synthesizing 1-indanones by reaction of aromatic hydrocarbons with β-lactone is not yet known.

Japanese Patent Laid-Open No. 9-136859 JP 2001-247505 A JP-A-6-9483 JP-A-6-25068 JP-A-6-192163 JP-A-8-12615 Japanese Patent Laid-Open No. 10-139715 JP 2000-256263 A J. et al. Org. Chem. 46, p2974 (1981) Bull. Soc. Chim. Belg. , 101, p1053 (1992) J. et al. Mol. Cat. , A, 134, p215 (1998)

  The object of the present invention is to reduce 1-indanones, useful as synthetic intermediates for organic materials such as medicines and agricultural chemicals, metal catalyst ligands, and liquid crystals, by dehydration condensation of aromatic hydrocarbons and β-lactones. It is another object of the present invention to provide a method for manufacturing easily and easily.

  As a result of intensive studies on the synthesis method of 1-indanone, the present inventors have rapidly added dehydration condensation of aromatic hydrocarbons and β-lactones by adding a catalytic amount of a certain Lewis acid. Thus, it was found that 1-indanones can be easily obtained, and the present invention has been completed based on these facts.

（式中、Ｒ^１〜Ｒ^４は、それぞれ反応に関与しない１価の基を示す。）で表される芳香族炭化水素と一般式（II）

（式中、Ｒ^５〜Ｒ^８は、それぞれ反応に関与しない１価の基を示す。）で表されるβ−ラクトンとを、一般式（III）
ＭＸｍ・Ｌｎ （III）
（式中、Ｍはビスマス、ガリウム、インジウム、ハフニウム、希土類元素から選ばれる金属イオンを示し、Ｘはアニオンを示し、Ｌは配位力のある中性分子を示す。ｍは金属Ｍの原子価数であり、ｎは０〜１０の整数である。）で表されるルイス酸の触媒量の存在下に反応させることによる一般式（IV）

（式中、Ｒ^１〜Ｒ^８は、それぞれ前記と同じ意味を持つ。）で表される１−インダノン類の製造方法である。
上記一般式（III）で表されるルイス酸としては、Ｘがハロゲン、パーフルオロアルキルスルホナート、ビス（パーフルオロアルキルスルホニル）アミド、トリス（パーフルオロアルキルスルホニル）メチドから選ばれるアニオンからなるものを用いることが好ましい。 That is, the present invention relates to the general formula (I)

(Wherein R ^{1 to} R ⁴ each represent a monovalent group not involved in the reaction) and the general formula (II)

(Wherein R ^{5 to} R ⁸ each represent a monovalent group not involved in the reaction) and β-lactone represented by the general formula (III)
MXm · Ln (III)
(In the formula, M represents a metal ion selected from bismuth, gallium, indium, hafnium, and rare earth elements, X represents an anion, L represents a neutral molecule with coordination power, and m represents the valence of the metal M. And n is an integer of 0 to 10.) by reacting in the presence of a catalytic amount of a Lewis acid represented by the general formula (IV)

(Wherein R ^{1 to} R ⁸ each have the same meaning as described above).
As the Lewis acid represented by the general formula (III), X is an anion selected from halogen, perfluoroalkylsulfonate, bis (perfluoroalkylsulfonyl) amide, and tris (perfluoroalkylsulfonyl) methide. It is preferable to use it.

  According to the present invention, by using a catalytic amount of a specific Lewis acid, the reaction between various aromatic hydrocarbons and β-lactone proceeds easily, and various 1-indanones can be easily obtained. In addition, this method can produce 1-indanones in a shorter process than conventional methods.

The aromatic hydrocarbon represented by the general formula (I) used as a raw material in the production method of the present invention has a hydrogen atom that can be substituted on two adjacent carbon atoms, and other carbon atoms There are no particular limitations on the bonding groups R ^{1 to} R ⁴ as long as they do not adversely affect the dehydration condensation reaction of the present invention.
R ^{1 to} R ⁴ in the general formula (I) are groups not participating in the dehydration condensation reaction, for example, a hydrogen atom, a halogen atom, an alkyl group such as methyl, ethyl, propyl, t-butyl, methoxy, Examples thereof include an alkoxy group such as ethoxy, and an alkylthio group such as methylthio and ethylthio.

Next, the other raw material in the present invention is β-lactone represented by the general formula (II), and may have a substituent that does not adversely influence the reaction.
R ⁵ and R ⁶ in the general formula (II) are groups that do not participate in the dehydration condensation reaction of the present invention, and examples thereof include a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, and t-butyl. It is done. R ⁷ and R ⁸ are also groups that do not participate in the dehydration condensation reaction, and include, for example, a hydrogen atom, a halogen atom, an alkyl group such as methyl, ethyl, propyl, and t-butyl, and an alkoxy group such as methoxy and ethoxy. , Alkylthio groups such as methylthio and ethylthio, ester groups such as methoxycarbonyl, perfluoroalkyl groups such as cyano group and trifluoromethyl

Next, the Lewis acid used as a catalyst in the present invention has the general formula (III)
MXm · Ln (III)
It is a metal compound represented by these.
In general formula (III), M is a metal ion, and is selected from bismuth, gallium, indium, hafnium, and rare earth elements such as scandium, samarium, and ytterbium. Further, as the anion X, those having a high acidity of the conjugate acid are preferable, for example, halogen anion, perfluoroalkyl sulfonate anion, bis (perfluoroalkylsulfonyl) amide anion, tris (perfluoroalkylsulfonyl) methide anion, etc. Is mentioned.

Preferred examples of the Lewis acid catalyst used in the present invention include Bi (OSO ₂ CF ₃ ) ₃ , Bi [N (SO ₂ CF ₃ ) ₂ ] ₃ , Bi [C (SO ₂ CF ₃ ) ₃ ] _{3 and the} like. Can be mentioned.
These Lewis acid catalysts may be coordinated with neutral molecules that do not adversely influence the reaction. This neutral molecule is L in the general formula (III), and examples thereof include ethers such as water and diethyl ether, and the number n is 0 to 10. The amount of the Lewis acid catalyst used may be a small amount of a so-called catalyst amount, and can be carried out in the range of 0.0001 to 50 mol% based on the compound (I), but if it is too small, the reaction does not proceed at an advantageous rate. Moreover, since the economical efficiency of reaction will worsen when too large, Preferably it is the range of 0.01-30 mol%, More preferably, it is the range of 0.05-15 mol%.

The dehydration condensation reaction of the present invention does not necessarily require a solvent, but a solvent may be used. Solvents that can be used include aromatic hydrocarbons, chlorinated hydrocarbons, nitrated hydrocarbons, aliphatic hydrocarbons, etc., among which aromatic hydrocarbons, chlorinated hydrocarbons, Nitrated hydrocarbon solvents are preferred, and specific examples include toluene, xylene, chlorobenzene, 1,2-dichloroethane, 1,2-dichlorobenzene, nitromethane, nitrobenzene and the like.
As the reaction temperature, the reaction does not proceed at an advantageous rate at a too low temperature, while there is a problem that a side reaction occurs at a too high temperature, and since it is inferior in economy, it is generally in the range of 0 to 300 ° C. Preferably, it is the range of 60-250 degreeC.
Separation of the desired target product from the reaction product mixture is easily accomplished by using conventional separation and purification methods such as solvent extraction, recrystallization, distillation, chromatography, and sublimation.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Example 1
Synthesis of 3,4,7-trimethyl-1-indanone A mixture of 2 mL of p-xylene, 21.2 mg (0.25 mmol) of β-butyrolactone and 17 mg (0.026 mmol) of Bi (OSO ₂ CF ₃ ) ₃ And stirred for 3 hours. After diluting the reaction mixture with 5 mL of ether, 5 mL of a saturated aqueous sodium hydrogen carbonate solution was added to separate the generated organic layer, and then the aqueous layer was extracted twice with 5 mL of ether. Thereafter, the organic layers were combined and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. This was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 9/1) to obtain 6.5 mg (yield 15%) of 3,4,7-trimethyl-1-indanone. The chemical structure of the product thus obtained was confirmed by ¹ H-NMR.

The present invention is a method by which 1-indanones can be easily produced in one step from readily available aromatic hydrocarbons and β-lactone, and is simpler than the conventional method requiring several steps in the production of raw materials. Indanone can be produced and is a useful method for industrial implementation.

Claims (2)

Formula (I)

(Wherein R ^{1 to} R ⁴ each represent a monovalent group not involved in the reaction) and the general formula (II)

(Wherein R ^{5 to} R ⁸ each represent a monovalent group not involved in the reaction) and β-lactone represented by the general formula (III)
MXm · Ln (III)
(In the formula, M represents a metal ion selected from bismuth, gallium, indium, hafnium, and rare earth elements, X represents an anion, L represents a neutral molecule having coordination power, and m represents the valence of metal M. And n is an integer of 0 to 10.) by reacting in the presence of a catalytic amount of a Lewis acid represented by the general formula (IV)

(Wherein R ^{1 to} R ⁸ each have the same meaning as described above), a method for producing 1-indanones. 2. The Lewis acid according to claim 1, wherein in the general formula (III), a Lewis acid is used in which X is an anion selected from halogen, perfluoroalkylsulfonate, bis (perfluoroalkylsulfonyl) amide, and tris (perfluoroalkylsulfonyl) methide. 1-Method for producing indanones.