JPS62185035A - Production of 2-indanone - Google Patents

Abstract

PURPOSE:To obtain the titled compound, by using a water-insoluble organic solvent as a reaction solvent, adding an organic acid in the presence of an alkali catalyst, dripping hydrogen peroxide to the resultant mixture, generating an organic peracid in the system, oxidizing an indene and heating the resultant product with a mineral acid. CONSTITUTION:An organic acid, e.g. acetic acid, propionic acid, etc., is added in the presence of an alkali catalyst, e.g. sodium hydroxide, potassium hydroxide, etc., in a water-insoluble organic solvent, e.g. methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, etc., and hydrogen peroxide is then dripped into the resultant mixture to generate an organic peracid in the system. An indene expressed by formula I (R is H or lower alkyl), e.g. indene, etc., is oxidized with the above-mentioned organic peracid and the resultant intermediate, together with a mineral acid, e.g. sulfuric acid, etc., is heated to afford the aimed 2-indanone derivative expressed by formula II, e.g. 2- indanone, etc. Since the reaction is carried out while generating the organic peracid, this method is safe and removal of the peroxide is safely and readily carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 2-indanones, which are indenes.

[Prior Art] 2-indanones are important as raw materials for manufacturing pharmaceuticals such as antihypertensive agents, and various methods for their production have been reported so far. For example, a method in which indene is used as a raw material, oxidized using an organic peracid with a large excess of organic acid as a solvent, and then heated in a mineral acid (Org, Syn, 41.5
3 (1,961)), or a method in which indene is reacted with bromine water to form a bromohydrin, and then reacted with an alkali in alcohol (J, Arp, Chew, Soc.
,, 57.2,022 (1,935) and J, ch.
ew.

Soc, 2,559 (1,922)) etc. are known.

[Problems to be Solved by the Invention] However, these conventional oxidation methods using organic peracids have problems in terms of production cost because they use a large excess of organic acids, such as formic acid, as a solvent. But it's too late! iF[! In addition, in order to remove the intermediates to be subjected to the mineral acid treatment, formic acid must be distilled off from the reaction mixture, which removes unreacted peroxide at a high concentration.
It has a serious drawback in that it must be concentrated to 1 lJf, which poses a risk of explosion. On the other hand, the latter bromohydrin method uses bromine water, which poses problems in terms of production cost and safety and hygiene, and has the disadvantage that the yield decreases due to the generation of byproducts. .

The present invention concentrates unreacted peroxide to a high concentration,
It is an object of the present invention to provide a manufacturing method that can obtain 2-indanones in high yield.

[Means for Solving the Problems] The Ichikasa of the present invention is produced by using a water-insoluble organic solvent as the reaction solvent and in the presence of an alkali catalyst. By adding an organic acid and dropping hydrogen peroxide into the mixture, the right m
It was discovered that 2-indanones can be obtained by generating 1st, oxidizing indenes with the organic peracid generated in this reaction system, and heating the obtained mesomorph with mineral acid in a conventional manner, This completes the present invention.

Examples of the raw material indanes used in the present invention include indanes or lower alkyl indanes represented by the following general formula (I> (in the formula, R represents hydrogen or a lower alkyl group), where the lower alkyl group is preferably has 1 carbon number
~3 alkyl group.

Further, the water-insoluble organic solvent used in the present invention may be any organic solvent as long as it is inert to the organic acid used and the organic peracid generated in the reaction system and is substantially insoluble in water. Examples include n-hexadi, bembin, toluene, methylene chloride, di[10]form, carbon tetrachloride, dichloroethane, and trichloroethane, and preferably a low-boiling halogenated hydrocarbon with a boiling point of 100°C or less.

Furthermore, examples of the Alno-J catalyst used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium formate, and potassium formate. The amount of this alkali catalyst to be used is 0.01 to 0.4 equivalents a, preferably o, i to 0.2 equivalents, based on the indenes used as raw materials.
It is.

This alkaline catalyst acts as an oxidation catalyst, and if it is not used, the amount of by-products will increase.On the other hand, if the amount used exceeds 0.4 equivalence to indenes, the amount of raw material recovered will increase. In either case, the yield of the target product, 2-indanones, decreases.

In addition, examples of the organic acids used in the present invention include formic acid,
#l acid, propion a! Lower aliphatic monocarboxylic acids such as
．． It is 5 to 10 equivalents, preferably 1 to 3 equivalents.

In the method of the present invention, hydrogen peroxide is added dropwise to the mixture of the indenes, a water-insoluble organic solvent, an alkali catalyst, and the right a acid to carry out the oxidation reaction of the raw indenes.

The hydrogen peroxide used for this purpose may be hydrogen peroxide itself or its aqueous solution (hydrogen peroxide solution), but it is usually 10 to 90% heavy solids peroxide. Hydrogen water, preferably 20 to 60% hydrogen peroxide water, is used.

The hydrogen peroxide solution used is 0.5 to 3 equivalents, preferably 161 to 1.5 equivalents, relative to the indenes as raw materials.

In the oxidation reaction of indenes carried out by dropping this hydrogen peroxide solution into the above mixture, the reaction temperature is usually in the range of 0 to 60°C, preferably 30 to 40°C.
The dropping rate of the hydrogen peroxide solution is such that the reaction temperature is above the temperature t! It is best to keep the speed within the range. Furthermore, in this oxidation reaction of indenes, stirring is preferably continued for 1 to 10 hours after the completion of dropping hydrogen peroxide. After the reaction is complete, increase the reaction temperature by 60'l, e.g. 65-80°C.
Second, the organic peracid produced in the reaction system is decomposed, and after cooling, it is allowed to stand to separate into two layers, and the aqueous layer is removed. J3, most of the oxidation reaction products of indenes are dissolved in the organic solvent layer, but a small amount is also dissolved in the water layer, so this water layer can be used in the same organic solvent used for the reaction. Preferably extracted and recovered.

Next, do 1 like this! ? mineral layer in the organic solvent layer,
For example, by adding sulfuric acid and heating, the desired general formula (I
I) Produce 2-indanones represented by the formula (wherein R represents hydrogen or a lower alkyl group), ie, 2-indanone or lower alkyl-substituted 2-indanone.

The heating reaction performed by adding this mineral acid is usually 70 to 100°C.
Do this for 0.5 to 2 hours. When the boiling point of the organic solvent is lower than the reaction temperature, the temperature is raised to a predetermined temperature after the organic solvent is distilled off. After the reaction is completed, the organic phase is separated and purified by an appropriate method such as vacuum distillation or steam distillation.

[Example] Hereinafter, the method of the present invention will be specifically explained based on Examples.

Example 116 g of indene was dissolved in 1,2-dichloroethane 3009, 153 g of 90% by weight formic acid and 15 g of sodium carbonate were added thereto, and the resulting mixture was stirred and the reaction temperature was maintained at 30 to 40°C. While 35 cities■% hydrogen peroxide solution 130! J was added dropwise, and after the completion of the addition, stirring was continued at 35°C for 6 hours. After the reaction is complete, 41ff of the reaction mixture is
Bring to 71°C, stir for 30 minutes, and cool to room temperature.]
The mixture was allowed to stand still, and ①1 was separated and collected. For the aqueous layer, 50 g of 1,2-dichloromethane was used to recover the dissolved reaction product, and the IF! Combined with ff.

Next, the organic layer obtained in this way was applied with 15% VA.
1.000 g of acid was added, 1,2-dichloroethane was distilled off while heating, and when the temperature reached 100°C, stirring was continued at that temperature for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and an organic layer consisting of 2-indanone and 1,2-dichloroethane was separated and collected.
95g of 2-indanone distilled under reduced pressure with 7++mlJ
(Yield 72fflJri%, bp 116-118℃/1
7#1IllHO) was obtained.

[Effects of the Invention] According to the method of the present invention, the reaction proceeds while generating organic peracid in the reaction system, so the safety of the reaction is improved.
After the reaction is complete, unreacted peroxide can be removed safely and easily without concentrating the reaction mixture, and the number of steps for using organic acids is reduced compared to conventional methods, and organic solvents can also be recovered. Since it can be reused, it is extremely advantageous in terms of manufacturing costs. Moreover, the method of the present invention is an extremely useful manufacturing method industrially, as it is easier to control the reaction temperature and has improved manufacturing operations compared to conventional methods using organic peracids. .

Special Crystal 1 Applicant Nippon Steel Chemical Co., Ltd. Agent Patent Attorney Katsuo Naruse (2 others) Procedural Net Authorization (spontaneous) March 12, 1985 Commissioner of the Patent Office Michibe Uga 1, Display of the case 1986 Patent Application No. 24167 2, Name of the invention 2 - Process for producing indanones 3, Person making the amendment Interchange with the case Patent applicant address 13-16, Ginza 5-chome, Chuo-ku, Tokyo Name (6
64) Nippon Steel Chemical Co., Ltd. Rei 4, Agent 105 Telephone (433) 4420 Address
3-8-8 Shinbashi, Minato-ku, Tokyo, 5th Floor, 5th Pill, Number of inventions to be increased by the amendment None 6, Contents of the amendment subject to the amendment (1) Mei m'a, page 2, lines 8-12 Correct the eyes as follows.

f (Org, Syn, 41.53 (1961)
), or a method in which indene is reacted with bromine water to form a bromohydrin, and then reacted with an alkali in alcohol (J.

8m, Chew, Soc,, 57. 2,
022 (1935) and σJ, Chew.

Soc, 2,559 (1 (122)) etc. are known. j (2) Described on page 5, lines 17 to 19 of the specification [It may be hydrogen peroxide itself, but J is deleted.

(3) The "phase" described on page 7, line 11 of the specification is corrected to r layer j.

(4) Correct the "focal plane" described in Ming Natsume, page 7, line 11 (two locations) and page 8, line 14, to r distillation j.

that's all

Claims (1)

[Claims] Indenes represented by the following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) (In the formula, R represents hydrogen or a lower alkyl group) in a water-insoluble organic solvent is used as a solvent, an organic acid is added in the presence of an alkali catalyst, hydrogen peroxide is added dropwise to the mixture to oxidize it, and then heated with a mineral acid. ▲Mathematical formula, chemical formula , tables, etc. ▼(II) Method for producing 2-indanones represented by (wherein R represents hydrogen or a lower alkyl group).