JP2005097201A - Method for producing alicyclic ketone compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce an alicyclic ketone compound in a high yield by oxidizing an alicyclic alcohol compound as a raw material with sulfuric acid. <P>SOLUTION: In producing an alicyclic ketone compound such as 2-adamantanone by subjecting an alicyclic alcohol such as 1-adamantanol and 2-adamantanol to sulfuric acid oxidation in a solvent or in the absence of a solvent with the use of sulfuric acid, concentrated sulfuric acid having a sulfuric acid concentration of 90-94 wt.% is used as sulfuric acid to prepare the alicyclic ketone compound in a high isolation yield. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an alicyclic ketone compound such as 2-adamantanone.

  An alicyclic ketone compound is a useful compound as an intermediate for electronic materials and medical and agricultural chemicals. For example, a resist using an alkyladamantyl ester compound, which is a kind of alicyclic alkyl ester compound obtained from an alicyclic ketone compound, has been reported to have high dry etching resistance in a semiconductor manufacturing process (see, for example, Patent Document 1). The potential as a resist material for semiconductors has attracted attention.

  In the field of electronic materials and the like, competition is fierce and demands for reducing manufacturing costs are becoming strict, and it is extremely important to obtain high-purity products by a simple method using inexpensive raw materials. Therefore, in the production of the intermediate adamantanone, a method for directly and simply obtaining high-purity adamantanone from adamantane without using a derivative such as adamantanol is desired.

  Conventionally, as a method for obtaining an alicyclic ketone compound such as 2-adamantanone, a method in which adamantane or 1-adamantanol is oxidized with concentrated sulfuric acid and then purified by steam distillation is known (hereinafter referred to as sulfate oxidation method). . In this method, 2-adamantanone is obtained in 47 to 48% (see Non-Patent Document 1). Alternatively, in the sulfuric acid oxidation method, 2-adamantanone is obtained in a high yield by maintaining the reaction system at 40 to 60 ° C. for 30 minutes or more and then raising the temperature to 60 to 90 ° C. to react (Patent Document) 2).

Japanese Patent Laid-Open No. 11-189564 JP-A-5-265212 “Organic Synthesis”, 1973, 53, p. 8

  The sulfuric acid oxidation method is an industrial method for producing an alicyclic ketone compound in that it does not require a special reaction facility, as well as using an inexpensive and easily available industrial reagent such as sulfuric acid. It is a very attractive manufacturing method. However, the yield is not sufficient to be adopted as an industrial production method, and it has been desired to further improve the yield.

  In particular, in the method according to Patent Document 2 described above, if the previous reaction is carried out at 40 ° C., which is the lower limit, in order to suppress the production of by-products such as tar, the reactivity is greatly reduced. If the sulfuric acid concentration exceeds 99% by weight in order to increase the reactivity, the production of the above-mentioned by-products increases at a stretch. If the sulfuric acid concentration is 95% by weight or less, the sulfuric acid concentration cannot be obtained at the end of the reaction, so the reaction is terminated. do not do. As a result, it was not possible to produce the 2-adamantanone with a higher yield.

  The subject of this invention is improving the yield of alicyclic ketone compounds, such as 2-adamantanone, without impairing the said characteristic which the sulfuric acid oxidation method has.

  In view of the above technical problems, the present inventors have intensively studied the reaction conditions in the sulfuric acid oxidation method. As a result, when sulfuric acid is oxidized using an alicyclic alcohol compound such as 1-adamantanol as a raw material, if the oxidation is carried out with the concentration of sulfuric acid used being reduced to 90 to 94% by weight, a by-product such as tar content is produced. As a result, it was found that the yield was improved, and the present invention was completed. In addition, the method of this invention is not suitable for the sulfuric acid oxidation method of an alicyclic hydrocarbon compound.

  That is, the present invention relates to a method for producing an alicyclic ketone compound by oxidizing an alicyclic alcohol compound with sulfuric acid, wherein the alicyclic ketone compound is oxidized at a sulfuric acid concentration of 90 to 94% by mass. Is the method.

  The production method of the present invention is not particularly different from the above-described sulfuric acid method except that an alicyclic alcohol compound is used as a raw material and an oxidation reaction is performed using sulfuric acid having a concentration of 90 to 94% by mass. That is, the reaction reagents such as raw materials to be used, the reaction apparatus, and the like can be known ones used in the conventional sulfuric acid method, and the conventional conditions can be adopted as the reaction conditions.

  The alicyclic alcohol compound used as a raw material is a compound in which at least one position of the alicyclic hydrocarbon compound is substituted with a hydroxyl group (—OH group). From the viewpoint that the position to be oxidized is limited and a single alicyclic keto compound is easily obtained, a saturated alicyclic alcohol compound having high symmetry is preferred.

  Specific examples of such alicyclic alcohol compounds include cyclohexanol, 1-adamantanol, 2-adamantanol and the like. Among these, an adamantanone in which an oxidation reaction proceeds selectively and efficiently, and the resulting alicyclic ketone compound is a useful compound as an intermediate for electronic materials and medical and agrochemicals, and high purity is desired. 1-adamantanol or 2-adamantanol, which is a raw material of the above, is most preferred.

  As the alicyclic alcohol compound, a reagent or an industrially available and commercially available one can be used without any limitation, but it can also be synthesized as follows.

  That is, as described in Journal of the Chemical Society Parkin Transaction 1 by Kiyoshi Tanemura et al. And four other authors, as described in 2001, p. 3230, adamantane was added in a trifluoroacetic acid solvent under nitrogen atmosphere. Method of oxidizing 3-dichloro-5,6-dicyano-p-benzoquinone as a catalyst, or Journal of the American Chemical Society 1986 by Robert W. Murray et al. Year, Volume 108, page 2470, dimethyldioxira A method in which oxidation of adamantane may be mentioned as the oxidizing agent.

  In the present invention, when producing an alicyclic ketone compound by oxidizing an alicyclic alcohol compound with sulfuric acid, the greatest feature is that sulfuric acid having a sulfuric acid concentration of 90 to 94% by mass is used.

  By reducing the concentration of sulfuric acid as compared with the conventional method, the production of by-products such as tar is suppressed, so the yield is improved. When a concentration of less than 90% by mass is used, the reaction cannot be completed because a sufficient sulfuric acid concentration cannot be obtained at the end of the reaction. When sulfuric acid having a concentration exceeding 94% by mass is used, the reaction is completed, but by-products such as tar are increased.

  The sulfuric acid used in the present invention can be used without any limitation as a reagent or industrially available and commercially available, but is adjusted by adding fuming sulfuric acid, sulfuric anhydride, chlorosulfonic acid, etc. to sulfuric acid having a low concentration. It can also be adjusted by diluting sulfuric acid with high concentration with water.

  The amount of sulfuric acid to be used is not particularly limited, but even if it is used excessively, the effect corresponding to the amount used is not obtained and post-treatment is troublesome. The ability to suspend the cyclic alcohol compound is reduced. Therefore, it is usually used in an amount of 3 to 500 parts by weight, preferably 5 to 300 parts by weight, based on 1 part by weight of the alicyclic alcohol compound.

  The production of the alicyclic ketone compound of the present invention can be carried out in the absence of a solvent, but an organic solvent can also be used as necessary.

  The organic solvent used can be used without any limitation as long as it is stable to sulfuric acid, is incompatible with water, does not inhibit the reaction, and dissolves the alicyclic alcohol compound.

  Specific examples of these organic solvents include halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene; aliphatic carbonization such as hexane and heptane. Hydrogens; aromatic hydrocarbons such as benzene, xylene and toluene; ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, propyl acetate and butyl acetate; carbonates such as dimethyl carbonate it can. Among these, halogenated aliphatic hydrocarbons or halogenated aromatic hydrocarbons capable of producing particularly high yields are preferably used.

  The amount of these organic solvents used in the present invention is not particularly limited. However, if the amount is too large, the yield per batch is small, which is not economical. If the amount is too small, the alicyclic alcohol compound is dissolved. Reaction rate decreases. Therefore, it is usually preferable to use an organic solvent so that the amount of the alicyclic alcohol compound is 0.1 to 60% by mass, preferably 1 to 50% by mass, based on the entire reaction solution.

In the sulfuric acid oxidation method of the present invention, sulfur dioxide is generated in the reaction process, so that the reaction is generally preferably carried out at normal pressure. However, it is also possible to react under reduced pressure in order to distill off water and solvent. The reaction pressure can be carried out under normal pressure, reduced pressure, or increased pressure, and the reaction solution is preferably carried out with stirring.

  The reaction temperature can be appropriately selected from known temperature conditions. The reaction at a constant temperature described in Non-Patent Document 1 is possible, and after maintaining in the temperature range of 40 to 60 ° C. described in Patent Document 2 for 30 minutes, the temperature is raised to 60 to 90 ° C. and reacted (hereinafter 2) It is also possible to use a stepped temperature raising method. When the reaction is carried out at a constant temperature, if the reaction temperature is too low, the reaction rate decreases and the reaction time increases, and if the reaction temperature is too high, by-products such as tar content increase. It is particularly preferable to carry out in the range of 0 to 70 ° C.

  The reaction time varies depending on the reaction temperature, but may be appropriately determined using an analytical instrument such as gas chromatography (GC) while confirming the progress of the reaction. Although depending on the reaction temperature, 0.5 to 200 hours is generally sufficient.

  Any reactor can be used without any limitation as long as it is a device that can be sufficiently stirred and heated and uses a material that can withstand sulfuric acid. For example, a normal glass lining pot is preferably used.

  The operation procedure for carrying out the present invention may be performed by any procedure. Usually, a reaction vessel is charged with sulfuric acid adjusted to a predetermined concentration, then a predetermined amount of an alicyclic alcohol compound is added, and if necessary, a halogen alone or a metal halide salt as an activator is added, In general, the reaction is performed under various reaction conditions such as temperature.

  The alicyclic ketone compound obtained by the present invention is a ketone derived from an alicyclic alcohol compound as a raw material. For example, when 1-adamantanol or 2-adamantanol is used as a raw material, 2-adamantanone is obtained.

  The method for isolating and purifying the alicyclic ketone compound from the reaction solution is not particularly limited and a known method is employed. For example, the reaction solution after the reaction is poured into ice, and the precipitated crystals are filtered or centrifuged, extracted with a solvent, then washed, evaporated, and dried, and the residue is subjected to silica gel column chromatography. The method of separating and purifying by treating with, for example. Furthermore, as disclosed in JP-A-2000-012570, a method of diluting the sulfuric acid concentration to 60 to 90% by weight after completion of the reaction and then extracting with an organic solvent is also possible.

  The alicyclic ketone compound thus obtained has a purity that can be used as it is depending on the application. However, if further purification is required, recrystallization, vacuum distillation, steam distillation or sublimation purification can be used. It can be purified by the method.

  By the production method of the present invention, the reaction time can be greatly shortened while maintaining the characteristics of the conventional sulfuric acid method, and by-product such as tar content can be suppressed, so that the isolated alicyclic ketone compound can be isolated and collected. The rate can be improved.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited at all by these Examples.

Example 1
25 g (0.16 mol) of 1-adamantanol was added to 240 g of concentrated sulfuric acid (sulfuric acid content: 2.20 mol) at 90.0% by mass, and the reaction was performed at 60 ° C. for 40 hours with vigorous stirring. At the end of the reaction, 1-adamantanol was 1.5% by GC. After allowing to cool, the reaction mixture was poured into 100 g of ice and extracted twice with 300 ml of dichloromethane. The organic layer was washed successively with 1N aqueous sodium hydroxide solution and 20% brine, and then dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure to give 22.2 g (0.18 mol, yield 90) of 2-adamantanone. %). When this 2-adamantanone was analyzed by GC using dodecane as an internal standard, the purity was 99.3%.

Example 2
25 g (0.16 mol) of 2-adamantanol was added to 240 g of concentrated sulfuric acid (sulfuric acid content: 2.20 mol) of 90.0% by mass, and the reaction was performed at 60 ° C. for 20 hours with vigorous stirring. At the end of the reaction, 1-adamantanol was 1.5% by GC. After allowing to cool, the reaction mixture was poured into 100 g of ice and extracted twice with 300 ml of dichloromethane. The organic layer was washed successively with 1N aqueous sodium hydroxide solution and 20% brine, and then dried over anhydrous magnesium sulfate. Dichloromethane was evaporated under reduced pressure to give 23.2 g (0.15 mol, yield 94) of 2-adamantanone. %). When this 2-adamantanone was analyzed by GC using dodecane as an internal standard, the purity was 99.3%.

Examples 3-5
The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1. The results are also shown in Table 1.

Comparative Example 1
25 g (0.16 mol) of 1-adamantanol was added to 224 g (2.2 mol as sulfuric acid content) of 96.5% by mass concentrated sulfuric acid, and the mixture was reacted at 75 ° C. for 10 hours with vigorous stirring. At the end of the reaction, 1-adamantanol was 1.6% by GC. After allowing to cool, the reaction mixture was poured into 100 g of ice and extracted twice with 300 ml of dichloromethane. The organic layer was washed successively with 1N aqueous sodium hydroxide, 10% aqueous sodium thiosulfate and 20% brine, and then dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure to give 16.8 g of 2-adamantanone ( 0.11 mol, yield 68%).

Comparative Example 2
Add 34 g of 30% fuming sulfuric acid to 207 g of 96.5 mass% concentrated sulfuric acid to make 98.01% concentrated sulfuric acid (2.4 mol as sulfuric acid), add 25 g (0.16 mol) of 1-adamantanol, and stir vigorously The reaction was carried out at 60 ° C. for 20 hours. At the end of the reaction, 1-adamantanol was 1.3% by GC. After allowing to cool, the reaction mixture was poured into 100 g of ice and extracted twice with 300 ml of dichloromethane. The organic layer was washed successively with 1N aqueous sodium hydroxide, 10% aqueous sodium thiosulfate and 20% brine, and then dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure to give 17.8 g of 2-adamantanone ( 0.12 mol, yield 72%) was obtained.

Comparative Example 3
Under cooling to 30 g of water, 224 g of 96.5% by mass concentrated sulfuric acid was added to make 85.0% by mass concentrated sulfuric acid (2.2 mol of sulfuric acid), and 25 g (0.16 mol) of 1-adamantanol was added vigorously. While stirring, the mixture was allowed to react at 60 ° C. for 20 hours. As a result, 33% of 1-adamantanol remained by GC, and further reacted at 75 ° C. for 20 hours. At the end of the reaction, 28.5% of 1-adamantanol remained by GC. After allowing to cool, the reaction mixture was poured into 100 g of ice and extracted twice with 300 ml of dichloromethane. The organic layer was washed successively with 1N aqueous sodium hydroxide, 10% aqueous sodium thiosulfate and 20% brine, and then dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 22.2 g of 2-adamantanone ( 0.18 mol, yield 90%) was obtained. However, when this 2-adamantanone was analyzed by GC using dodecane as an internal standard, the purity was only 73.1%, and 26.4% of 1-adamantanol remained.

From the results of Comparative Examples 1 and 2, it was found that when 96.5% by mass or more of sulfuric acid was used, the by-product of by-products such as tar increased and the isolation yield was low although the reaction time was fast. I understand. Moreover, it can be seen from Comparative Example 3 that when sulfuric acid having a low concentration such as 85% by mass is used, the reaction cannot be completed because the sulfuric acid concentration sufficient to complete the oxidation reaction cannot be maintained at the end of the reaction. It can be seen that by using sulfuric acid having a concentration of 90 to 94% by mass of the present invention, the reaction can be completed and by-products such as tar can be suppressed.

Claims (2)

A method for producing an alicyclic ketone compound by oxidizing an alicyclic alcohol compound with sulfuric acid to oxidize the alicyclic ketone compound at a sulfuric acid concentration of 90 to 94% by mass. The method for producing an alicyclic ketone compound according to claim 1, wherein the alicyclic alcohol compound is 1-adamantanol or 2-adamantanol, and the obtained alicyclic ketone compound is 2-adamantanone.