JP3228355B2 - Indandione derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel indandione derivative and a physiologically acceptable salt thereof, and more particularly, to a hydroxyl group, an alkyloxy group, an alkenyloxy group, an aralkyloxy group on a benzene ring. The present invention relates to a novel indane-1,3-dione derivative having a group and an acyloxy group and useful as a pharmaceutical, and a physiologically acceptable salt thereof.

[0002]

2. Description of the Related Art Heretofore, as indane-1,3-dione derivatives, only compounds having no substituent on the benzene ring are known (G. Bock et al., Liebigs Ann. Che.
m. 1965.125-137), related to indane-1,3-dione derivatives having a hydroxyl group or an alkyloxy group, an alkenyloxy group, an aralkyloxy group or an acyloxy group on the benzene ring, and physiologically acceptable salts thereof. About it was not known.

[0003]

An object of the present invention is to provide a benzene ring having a substituent, particularly a hydroxyl group, or an alkyloxy group, an alkenyloxy group, an aralkyloxy group, or an acyloxy group which is considered to be useful for physiological activity. ,
It is to provide a novel indandione derivative useful as a pharmaceutical.

[0004]

In view of the prior art, the present inventor has developed a novel indane-1,3 having a hydroxyl group, or an alkyloxy group, an alkenyloxy group, an aralkyloxy group, or an acyloxy group on a benzene ring. The present inventors have made intensive studies to provide a dione derivative, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (I)

[0006]

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(Wherein, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, and an acyl group, and R ₂ represents a hydrogen atom or an acyl group). It relates to an indandione derivative.

The alkyl group of R _{1 in} the general formula (I) is, for example, a linear or branched alkyl group.
Methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, s-butyl group, t-butyl group, n-pentyl group, 2-methylpentyl group, octyl group, decyl group,
Preferred are those having 1 to 12 carbon atoms such as a dodecyl group.

The alkenyl group includes, for example, linear or branched alkenyl groups such as vinyl group, propenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonyl group, decenyl group and 3-methyl-2-methyl-2-alkenyl group.
Preferably, it has 2 to 10 carbon atoms such as a butenyl group and a geranyl group.
Individual ones.

Examples of the aralkyl group include a benzyl group and a benzyl group which may have a substituent (eg, a p-methoxybenzyl group, a p-methylbenzyl group, a p-chlorobenzyl group, etc.).

Examples of the acyl group include, for example, an alkanoyl group represented by an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a benzoyl group which may have a substituent (eg, a p-methoxybenzoyl group) , P-methylbenzoyl group, p-chlorobenzoyl group, etc.), formyl group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.).

In the general formula (I), the substitution position of the alkyloxy group, alkenyloxy group, aralkyloxy group and acyloxy group represented by R ₁ O— is 4-
Any of the 5th and 5th positions may be used.

Examples of the acyl group for R ₂ include alkanoyl, benzoyl, and benzoyl groups which may have a substituent (eg, p-yl) such as acetyl, propionyl, butyryl, and isobutyryl. Methoxybenzoyl group, p-methylbenzoyl group, p-chlorobenzoyl group, etc.), formyl group, alkoxycarbonyl group (eg,
Methoxycarbonyl group, ethoxycarbonyl group, etc.).

In the present invention, the indane-1,3-dione derivative represented by the general formula (I) can be produced according to the following reaction route. Wherein R ₁ and R ₂ have the same meanings as described above, and M is sodium,
Represents potassium.

[0015]

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Next, an outline of the manufacturing method will be described. First Step First, alkylation is carried out by reacting a hydroxyl group of 3- or 4-hydroxyphthalic acid diester (1) with an alkyl halide, alkenyl halide, aralkyl halide or acyl halide in the presence of a basic substance. Alkenylation and aralkylation. The alkyl group, alkenyl group, and aralkyl group of the alkyl halide, alkenyl halide, and aralkyl halide used herein include those described above. Examples of the basic substance used in the reaction include carbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate and potassium carbonate, and hydroxides such as sodium hydroxide and potassium hydroxide. As the alkyl halide, alkenyl halide, and aralkyl halide, chloride, bromide, and iodide can be used. Examples of the solvent used include ketone solvents such as acetone and methyl ethyl ketone, and amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. The reaction may be carried out at 0 to 150 ° C, preferably 20 to 80 ° C, depending on the type of halide used, the type of solvent and the like. The reaction time varies depending on the type of halide to be used, the type of solvent, the reaction temperature and the like, but is usually 1 to 5 hours.

Step 2 The cyclization reaction is carried out by reacting the thus obtained alkyloxy or alkenyloxy or aralkyloxyphthalic acid derivative (2) with an acetate in the presence of a basic substance. As the basic substance used here, basic substances such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and potassium-t-butoxide are preferable. As the acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like are preferable. The reaction is
The reaction can be carried out using a solvent, but may not be particularly used, and can be carried out without a solvent. When a solvent is used, an alcohol solvent such as methanol or ethanol is preferable. The reaction is carried out under heating conditions, and the reaction temperature can be 50 to 100 ° C., depending on the type of the phthalic acid derivative (2), the type of acetate used, and the like. Preferably, it is 70 to 90 ° C. The reaction time varies depending on the type of the phthalic acid derivative (2), the type of acetate used, the reaction temperature and the like.
Time is preferred.

Third Step The cyclized product (3) obtained in the second step is subjected to hydrolysis and decarboxylation under acidic conditions to obtain an alkyloxy or alkenyloxy or aralkyloxyindane-1,3-dione. (4) can be obtained. Examples of the acidic substance used here include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid.
The reaction temperature is preferably 50 to 100 ° C, and the reaction time is 30.
Minutes to 2 hours are preferred.

Fourth Step The indane-1,3-dione derivative (4) thus obtained is reacted with tosyl azide in the presence of a trialkylamine to introduce a diazo group into the active methylene moiety. As the trialkylamines used here, lower trialkylamines such as trimethylamine, triethylamine, tripropylamine and tributylamine are preferable. As the solvent used in the reaction, alcohol solvents such as methanol, ethanol, and propanol, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferable. The reaction temperature varies depending on the indane-1,3-dione derivative, trialkylamine, solvent and the like used, but can be carried out at -30 to 50 ° C. Preferably, it is carried out at -20 to 0 ° C. The reaction time varies depending on the indane-1,3-dione derivative, trialkylamine, solvent, reaction temperature and the like to be used, but is preferably 30 minutes to 2 hours.

Fifth Step The diazo compound (5) obtained in the fourth step is reacted with a carboxylic acid to give the desired indane-1,3.
-A dione derivative (6) can be obtained. This reaction is carried out by performing a heating reaction with a carboxylic acid in the presence of a metal catalyst such as copper powder.The carboxylic acid used may be a normal carboxylic acid without any particular limitation. Lower alkyl carboxylic acids such as acetic acid, propionyl acid and butyric acid are particularly preferred. The reaction temperature varies depending on the diazo compound, carboxylic acid and the like to be used, but can be carried out at 50 to 120 ° C. Preferably, it is carried out at 80 to 100 ° C. The reaction time varies depending on the diazo compound used, carboxylic acid, reaction temperature, etc.,
1-3 hours is preferred. The amount of the metal catalyst used may be 10 to 100% by weight based on the diazo compound used.

Next, among the compounds represented by the general formula (I), those in which R ₁ is a hydrogen atom are represented by the general formula (I)
Can be produced by removing the compound represented by the formula ( _{1) wherein} R ₁ is an aralkyl group. As a method of desorption, under an atmosphere of hydrogen gas, in the presence of a catalyst of a noble metal such as palladium, platinum, ruthenium,
It is achieved by performing hydrocracking. In this case, the hydrogen gas may be at normal pressure, and a solvent is used for the reaction. As the solvent used, water or an alcoholic solvent such as methanol, ethanol, or propanol,
Preferred are ether solvents such as tetrahydrofuran and 1,4-dioxane and ester solvents such as methyl acetate and ethyl acetate. The reaction temperature is from 0 to 50 ° C.,
Preferred temperatures include 20 to 30 ° C. The reaction time is preferably from 10 to 24 hours. Also, the amount of the metal catalyst used depends on the benzyloxyindane-1, used
What is necessary is just to use 1-10 weight% with respect to 3-dione.

Further, among the compounds represented by the general formula (I), those in which R ₁ is an acyl group can be obtained from those in which R ₁ is a hydrogen atom under ordinary acylation conditions. Further, among the compounds represented by the general formula (I),
When R ₂ is a hydrogen atom, the compound represented by the general formula (I) can be produced by subjecting a compound represented by R ₂ to an acyl group to a deacylation reaction. The deacylation reaction can be performed in the presence of a basic substance or an acidic substance. As the basic substance used here, carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate,
Hydroxides such as sodium hydroxide and potassium hydroxide, and metal alcoholates such as sodium methoxide and potassium methoxide are used. Also, as the acidic substance,
Mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, benzenesulfonic acid, p
-Sulfonic acids such as toluenesulfonic acid and methanesulfonic acid are used.

Specific examples of the indandione derivative thus obtained include the following compounds.
2,4-dihydroxyindane-1,3-dione, 4-
Hydroxy-2-formyloxyindane-1,3-dione, 4-hydroxy-2-acetoxyindane-1,
3-dione, 4-hydroxy-2-propynyloxyindane-1,3-dione, 4-hydroxy-2-butyryloxyindane-1,3-dione, 4-hydroxy-
2-isobutyryloxyindane-1,3-dione,
2,5-dihydroxyindane-1,3-dione, 5-
Hydroxy-2-formyloxyindane-1,3-dione, 5-hydroxy-2-acetoxyindane-1,
3-dione, 5-hydroxy-2-propynyloxyindane-1,3-dione, 5-hydroxy-2-butyryloxyindane-1,3-dione, 5-hydroxy-
2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-methoxyindane-
1,3-dione, 4-methoxy-2-formyloxyindane-1,3-dione, 4-methoxy-2-acetoxyindane-1,3-dione, 4-methoxy-2- pro
Pionyloxyindane -1,3-dione, 4-methoxy-2-butyryloxyindane-1,3-dione,
-Methoxy-2-isobutyryloxyindane-1,3
-Dione, 2-hydroxy-5-methoxyindane-
1,3-dione, 5-methoxy-2-formyloxyindane-1,3-dione, 5-methoxy-2-acetoxyindane-1,3-dione, 5-methoxy-2- pro
Pionyloxyindane -1,3-dione, 5-methoxy-2-butyryloxyindane-1,3-dione, 5
-Methoxy-2-isobutyryloxyindane-1,3
-Zeon,

2-hydroxy-4-ethoxyindane
1,3-dione, 4-ethoxy-2-formyloxyindane-1,3-dione, 4-ethoxy-2-acetoxyindane-1,3-dione, 4-ethoxy-2- pro
Pionyloxyindane -1,3-dione, 4-ethoxy-2-butyryloxyindane-1,3-dione,
-Ethoxy-2-isobutyryloxyindane-1,3
-Dione, 2-hydroxy-5-ethoxyindane-
1,3-dione, 5-ethoxy-2-formyloxyindane-1,3-dione, 5-ethoxy-2-acetoxyindane-1,3-dione, 5-ethoxy-2- pro
Pionyloxyindane -1,3-dione, 5-ethoxy-2-butyryloxyindane-1,3-dione, 5
-Ethoxy-2-isobutyryloxyindane-1,3
-Zeon,

2-hydroxy-4-propyloxyindane-1,3-dione, 4-propyloxy-2-formyloxyindane-1,3-dione, 4-propyloxy-2-acetoxyindane-1,3-dione Zeon, 4-
Propyloxy-2- propionyloxyindane-
1,3-dione, 4-propyloxy-2-butyryloxyindane-1,3-dione, 4-propyloxy-
2-isobutyryloxyindane-1,3-dione, 2
-Hydroxy-5-propyloxyindane-1,3-
Dione, 5-propyloxy-2-formyloxyindane-1,3-dione, 5-propyloxy-2-acetoxyindane-1,3-dione, 5-propyloxy-2- propionyloxyindane -1,3-dione Zeon,
5-propyloxy-2-butyryloxyindane-
1,3-dione, 5-propyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-isopropyloxyindane-1,3-dione, 4-isopropyloxy-
2-formyloxyindane-1,3-dione, 4-isopropyloxy-2-acetoxyindane-1,3-
Dione, 4-isopropyloxy-2- propionyloxyindane -1,3-dione, 4-isopropyloxy-2-butyryloxyindane-1,3-dione,
-Isopropyloxy-2-isobutyryloxyindane-1,3-dione, 2-hydroxy-5-isopropyloxyindane-1,3-dione, 5-isopropyloxy-2-formyloxyindane-1,3-dione , 5-isopropyloxy-2-acetoxyindane-1,3-dione, 5-isopropyloxy-2- pro
Pionyloxyindane -1,3-dione, 5-isopropyloxy-2-butyryloxyindane-1,3-
Dione, 5-isopropyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-butyroxyindane-1,3-dione, 4-butyroxy-2-formyloxyindane-1,3-dione, 4-butyroxy-2-acetoxyindane-1,3-dione, 4-butyroxy-
2- propionyloxyindane -1,3-dione, 4
-Butyroxy-2-butyryloxyindane-1,3-
Dione, 4-butyroxy-2-isobutyryloxindane-1,3-dione, 2-hydroxy-5-butyroxyindane-1,3-dione, 5-butyroxy-2-formyloxyindane-1,3- Dione, 5-butyroxy-2-acetoxyindan-1,3-dione, 5-butyroxy-2- propionyloxyindane -1,3-dione
Dione, 5-butyroxy-2-butyryloxyindane-1,3-dione, 5-butyroxy-2-isobutyryloxyindane-1,3-dione, 2-hydroxy-4
Isobutyroxyindane-1,3-dione,

4-isobutyroxy-2-formyloxyindane-1,3-dione, 4-isobutyroxy-2-
Acetoxyindane-1,3-dione, 4-isobutyroxy-2- propionyloxyindane -1,3-dione, 4-isobutyroxy-2-butyryloxyindane-1,3-dione, 4-isobutyroxy-2-isobutyi Ryloxyindane-1,3-dione, 2-hydroxy-5-isobutyroxyindane-1,3-dione, 5-
Isobutyroxy-2-formyloxyindane-1,3
- dione, 5-Isobuchirokishi 2-acetoxy-indane-1,3-dione, 5-Isobuchirokishi 2- propylidene
Onyl Okishiindan-1,3-dione, 5-Isobuchirokishi 2-butyryloxy-indane-1,3-dione, 5-Isobuchirokishi 2-isobutyryloxy indane-1,3-dione,

2-hydroxy-4-octyloxyindane-1,3-dione, 4-octyloxy-2-formyloxyindane-1,3-dione, 4-octyloxy-2-acetoxyindane-1,3-dione Zeon, 4-
Octyloxy-2- propionyloxyindane-
1,3-dione, 4-octyloxy-2-butyryloxyindane-1,3-dione, 4-octyloxy-
2-isobutyryloxyindane-1,3-dione, 2
-Hydroxy-5-octyloxyindane-1,3-
Dione, 5-octyloxy-2-formyloxyindane-1,3-dione, 5-octyloxy-2-acetoxyindane-1,3-dione, 5-octyloxy-2- propionyloxyindane -1,3-dione Zeon,
5-octyloxy-2-butyryloxyindane-
1,3-dione, 5-octyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-dodecyloxyindane-1,3-dione, 4-dodecyloxy-2-formyloxyindane-1,3-dione, 4-dodecyloxy-2-acetoxyindane-1,3-dione Zeon, 4-
Dodecyloxy-2- propionyloxyindane-
1,3-dione, 4-dodecyloxy-2-butyryloxyindane-1,3-dione, 4-dodecyloxy-
2-isobutyryloxyindane-1,3-dione, 2
-Hydroxy-5-dodecyloxyindane-1,3-
Dione, 5-dodecyloxy-2-formyloxyindane-1,3-dione, 5-dodecyloxy-2-acetoxyindane-1,3-dione, 5-dodecyloxy-2- propionyloxyindane -1,3-dione Zeon,
5-dodecyloxy-2-butyryloxyindane-
1,3-dione, 5-dodecyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-vinyloxyindane-1,3-dione, 4-vinyloxy-2-formyloxyindane-1,3-dione, 4-vinyloxy-2-acetoxyindane-1,3-dione, 4-vinyloxy-
2- propionyloxyindane -1,3-dione, 4
-Vinyloxy-2-butyryloxyindane-1,3-
Dione, 4-vinyloxy-2-isobutyryloxyindane-1,3-dione, 2-hydroxy-5-vinyloxyindane-1,3-dione, 5-vinyloxy-2-formyloxyindane-1,3- Dione, 5-vinyloxy-2-acetoxyindane-1,3-dione, 5-vinyloxy-2- propionyloxyindane -1,3-dione
Dione, 5-vinyloxy-2-butyryloxyindane-1,3-dione, 5-vinyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-allyloxyindane-1,3-dione, 4-allyloxy-2-formyloxyindane-1,3-dione, 4-allyloxy-2-acetoxyindane-1,3-dione, 4-allyloxy
2- propionyloxyindane -1,3-dione, 4
-Allyloxy-2-butyryloxyindane-1,3-
Dione, 4-allyloxy-2-isobutyryloxyindane-1,3-dione, 2-hydroxy-5-allyloxyindane-1,3-dione, 5-allyloxy-2-formyloxyindane-1,3-dione Dione, 5-allyloxy-2-acetoxyindane-1,3-dione, 5-allyloxy-2- propionyloxyindane -1,3-dione
Dione, 5-allyloxy-2-butyryloxyindane-1,3-dione, 5-allyloxy-2-isobutyryloxyindane-1,

3-dione, 2-hydroxy-4-geranyloxyindane-1,3-dione, 4-geranyloxy-2-formyloxyindane-1,3-dione,
-Geranyloxy-2-acetoxyindane-1,3-
Dione, 4-geranyloxy-2- propionyloxyindane -1,3-dione, 4-geranyloxy-2-
Butyryloxyindane-1,3-dione, 4-geranyloxy-2-isobutyryloxyindane-1,3-
Dione, 2-hydroxy-5-geranyloxyindane-1,3-dione, 5-geranyloxy-2-formyloxyindane-1,3-dione, 5-geranyloxy-2-acetoxyindane-1,3-dione , 5-geranyloxy-2- propionyloxyindane -1,3
-Dione, 5-geranyloxy-2-butyryloxyindane-1,3-dione, 5-geranyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4-benzyloxyindane-1,3-dione, 4-benzyloxy-2-formyloxyindane-1,3-dione, 4-benzyloxy-2-acetoxyindane-1,3-dione Zeon, 4-
Benzyloxy-2- propionyloxyindane-
1,3-dione, 4-benzyloxy-2-butyryloxyindane-1,3-dione, 4-benzyloxy-
2-isobutyryloxyindane-1,3-dione, 2
-Hydroxy-5-benzyloxyindane-1,3-
Dione, 5-benzyloxy-2-formyloxyindane-1,3-dione, 5-benzyloxy-2-acetoxyindane-1,3-dione, 5-benzyloxy-2- propionyloxyindane -1,3-dione Zeon,
5-benzyloxy-2-butyryloxyindane-
1,3-dione, 5-benzyloxy-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4- (p-methylbenzyloxy) indan-1,3-dione, 4- (p-methylbenzyloxy) -2-formyloxyindan-
1,3-dione, 4- (p-methylbenzyloxy)-
2-acetoxyindane-1,3-dione, 4- (p-
Methylbenzyloxy) -2- propionyloxyindane -1,3-dione, 4- (p-methylbenzyloxy) -2-butyryloxyindane-1,3-dione,
4- (p-methylbenzyloxy) -2-isobutyryloxyindane-1,3-dione, 2-hydroxy-5
-(P-methylbenzyloxy) indan-1,3-dione, 5- (p-methylbenzyloxy) -2-formyloxyindan-1,3-dione, 5- (p-methylbenzyloxy) -2- Acetoxyindane-1,3-
Dione, 5- (p-methylbenzyloxy) -2- pro
Pionyloxyindane -1,3-dione, 5- (p-
Methylbenzyloxy) -2-butyryloxyindane-1,3-dione, 5- (p-methylbenzyloxy)
-2-isobutyryloxyindane-1,3-dione,

2-hydroxy-4- (p-methoxybenzyloxy) indan-1,3-dione, 4- (p-methoxybenzyloxy) -2-formyloxyindane-1,3-dione, 4- (p -Methoxybenzyloxy) -2-acetoxyindane-1,3-dione, 4-
(P-methoxybenzyloxy) -2- propionyloxyindane -1,3-dione, 4- (p-methoxybenzyloxy) -2-butyryloxyindane-1,3
-Dione, 4- (p-methoxybenzyloxy) -2-
Isobutyryloxyindane-1,3-dione, 2-hydroxy-5- (p-methoxybenzyloxy) indan-1,3-dione, 5- (p-methoxybenzyloxy) -2-formyloxyindane-1 , 3-dione,
5- (p-methoxybenzyloxy) -2-acetoxyindane-1,3-dione, 5- (p-methoxybenzyloxy) -2- propionyloxyindane -1,3
-Dione, 5- (p-methoxybenzyloxy) -2-
Butyryloxyindane-1,3-dione, 5- (p-
Methoxybenzyloxy) -2-isobutyryloxyindane-1,3-dione;

2-hydroxy-4- (p-chlorobenzyloxy) indan-1,3-dione, 4- (p-chlorobenzyloxy) -2-formyloxyindan-
1,3-dione, 4- (p-chlorobenzyloxy)-
2-acetoxyindane-1,3-dione, 4- (p-
Chlorobenzyloxy) -2- propionyloxyindane -1,3-dione, 4- (p-chlorobenzyloxy) -2-butyryloxyindane-1,3-dione,
4- (p-chlorobenzyloxy) -2-isobutyryloxyindane-1,3-dione, 2-hydroxy-5
-(P-chlorobenzyloxy) indan-1,3-dione, 5- (p-chlorobenzyloxy) -2-formyloxyindan-1,3-dione, 5- (p-chlorobenzyloxy) -2- Acetoxyindane-1,3
-Dione, 5- (p-chlorobenzyloxy) -2- p
Lopionyloxyindane -1,3-dione, 5- (p
-Chlorobenzyloxy) -2-butyryloxyindane-1,3-dione, 5- (p-chlorobenzyloxy) -2-isobutyryloxyindane-1,3-dione,

4-acetoxy-2-formyloxyindane-1,3-dione, 2,4-diacetoxyindane-1,3-dione, 4-acetoxy-2- propionyl oxyindane-1,3 -Dione, 4-acetoxy-2
-Butyryloxyindane-1,3-dione, 4-acetoxy-2-isobutyryloxyindane-1,3-dione, 2,5-diacetoxyindane-1,3-dione, 5-acetoxy-2- Formyloxyindane-
1,3-dione, 2,5-diacetoxyindane-1,
3-dione, 5-acetoxy-2- propionyloxyindane -1,3-dione, 5-acetoxy-2-butyryloxyindane-1,3-dione, 5-acetoxy-2-isobutyryloxyindane-1 , 3-dione,

[0040] 4-propionyl-2-formyloxyethyl indane-1,3-dione, 4-propionyl Oki <br/> Shi-2-acetoxy-indane-1,3-dione, 2,4
- di-propionyl Okishiindan-1,3-dione, 4
-Propionyloxy -2-butyryloxyindane-
1,3-dione, 4-propionyl-2-isobutyryloxy indane-1,3-dione, 2,5-di-flop
Lopionyloxyindane -1,3-dione, 5- pro
Pioniru-2- formyloxyethyl indane-1,3
-Dione, 5- propionyloxy -2-acetoxyindane-1,3-dione, 5- propionyloxy -2
-Propionyloxyindane -1,3-dione, 5-
Propionyloxy -2-butyryloxyindane-
1,3-dione, 5- propionyloxy -2-isobutyryloxyindane-1,3-dione and the like.

The alkali addition salts of the above compounds can be produced by known methods, and among these, pharmaceutically acceptable salts include, for example, sodium salt, potassium salt, magnesium salt, calcium salt and the like. Non-toxic amine salts such as ammonium salts. These medically acceptable salts are also included in the present invention.

[0042]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. (Example-1) Diethyl 3-hydroxyphthalate (Compound 1) 40 g (0.238 mol) of 1-trimethylsiloxycyclohexa-1,3-diene and 36.4 ml (0.230 mol) of diethyl acetylenedicarboxylate were dissolved in toluene. 4
The mixture was added to 65 ml and reacted under heating and reflux for 2 hours. After completion of the reaction, toluene was distilled off under reduced pressure, 465 ml of methanol and 2.2 g of paratoluenesulfonic acid were added to the residue, and the mixture was stirred at room temperature for 20 minutes. Thereafter, methanol was distilled off under reduced pressure, methylene chloride and water were added, and the mixture was separated and extracted. After drying the methylene chloride layer with magnesium sulfate, methylene chloride was distilled off under reduced pressure. The obtained crude product is purified by silica gel chromatography to give 3
41.69 g of diethyl-hydroxyphthalate were obtained.

Yield: 76% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 7.20~7.80 (m,} 3H, aromatic) IR (KBr) = 3300 ( OH), 1740,172
0 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₂ H ₁₄ O ₅ ) Calculated value (%); C: 60.50, H: 5.92, O: 3
3.58, actual value (%); C: 60.45, H: 5.90, O: 3
3.65,

Example 2 Diethyl 4-hydroxyphthalate (Compound 2) Instead of 1-trimethylsiloxycyclohexa-1,3-diene in (Example 1), 2- (dimethyl-
Using 68 g (0.324 mol) of t-butylsiloxy) cyclohexane-1,3-diene and 50 ml (0.313 mol) of diethyl acetylenedicarboxylate, 31.8 g of diethyl 4-hydroxyphthalate was obtained.

Yield 43% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 6.80~7.80 (m,} 3H, aromatic) IR (KBr) = 3250 ( OH), 1740,172
0 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₂ H ₁₄ O ₅ ) Calculated value (%); C: 60.50, H: 5.92, O: 3
3.58, actual value (%); C: 60.48, H: 5.90, O: 3
3.62,

Example 3 Diethyl 3-benzyloxyphthalate (Compound 3) 41.69 g of diethyl 3-hydroxyphthalate (0.1%)
75 mol) in 264 ml of DMF and potassium carbonate 2
After addition of 9.01 g (0.210 mol), 25 ml (0.210 mol) of benzyl bromide was added, and the mixture was added at room temperature for 3 hours.
Stirred for hours. After adding methylene chloride and water, the methylene chloride layer obtained by liquid separation extraction was washed with 10% hydrochloric acid, then with water, dried over magnesium sulfate, and distilled off under reduced pressure.
The obtained crude product was recrystallized from methylene chloride-hexane to give diethyl 3-benzyloxyphthalate 54.07.
g was obtained.

Yield 94% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.20 (s,} 2H, CH 2 Ph), 7.20~
7.80 (m, 8H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₀ O ₅ ) Calculated value (%); C: 69.50, H: 6.14, O: 2
4.36, actual value (%); C: 69.45, H: 6.00, O: 2
4.45, melting point 72 ° C

(Example-4) Diethyl 3-methoxyphthalate (Compound 4) Instead of benzyl bromide in (Example-3), 29.8 g (0.210 mol) of methyl iodide was used to give 3-methoxyphthalic acid. 39.7 g of diethyl phthalate were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 3.80} (s, 3H, OCH 3),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 7.20~7.
80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₁₃ as H ₁₆ O ₅₎ Calculated (%); C: 61.89, H: 6.39, O: 3
1.71, actual value (%); C: 61.75, H: 6.20, O: 3
2.05

(Example-5) Diethyl 3-ethoxyphthalate (Compound 5) Instead of benzyl bromide in (Example-3), 32.8 g (0.210 mol) of ethyl iodide was used to prepare 3-ethoxyphthalic acid. 45.8 g of diethyl phthalate were obtained.

Yield 82% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
z, CH ₃ ), 3.75 (t, 2H, J = 8 Hz, O
CH ₂ ), 4.30 (q, 2H, J = 8 Hz, CH ₂ ),
4.40 (q, 2H, J = 8 Hz, CH ₂ ), 7.2
0 to 7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₄ H ₁₈ O ₅ ) Calculated value (%); C: 63.14, H: 6.81, O: 3
0.04, actual value (%); C: 63.34, H: 6.30, O: 3
0.36

Example 6 Diethyl 3-hexyloxyphthalate (Compound 6) Instead of benzyl bromide in (Example 3), 3-hexyl was obtained by using 34.65 g (0.210 mol) of bromohexane. Diethyl oxyphthalate 53.4
g was obtained.

Yield 79% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
_{z, CH 3), 1.50~1.85 (} m, 8H, C
_{H 2), 3.80 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 7.20 ~
7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₈ H ₂₆ O ₅ ) Calculated value (%); C: 67.06, H: 8.13, O: 2
4.81, actual value (%); C: 67.25, H: 8.20, O: 2
4.55,

(Example-7) Diethyl 3-octyloxyphthalate (Compound 7) Instead of benzyl bromide in (Example-3), 40.5 g (0.210 mol) of bromooctane was used to give 3-octyl. 62.6 g of diethyl oxyphthalate
was gotten.

Yield 81% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
z, CH ₃ ), 1.50-2.05 (m, 12H, C
_{H 2), 3.85 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 7.20~7.
80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₂₀ H ₃₀ O ₅₎ Calculated value (%); C: 68.54, H: 8.63, O: 2
2.83, actual value (%); C: 68.35, H: 8.30, O: 2
3.35,

(Example-8) Diethyl 3-decyloxyphthalate (Compound 8) Instead of benzyl bromide in (Example-3), 4.6 g (0.021 mol) of bromodecane was used to prepare 3-decyloxyphthalic acid. 7.1 g of diethyl phthalate were obtained.

H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
_{z, CH 3), 1.50~2.10 (} m, 16H, C
_{H 2), 3.85 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 7.20~7.
80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₂₂ H ₃₄ O as ₅₎ Calculated (%); C: 69.81, H: 9.05, O: 2
1.14, actual value (%); C: 69.75, H: 9.20, O: 2
1.05

Example 9 Diethyl 3-vinyloxyphthalate (Compound 9) Instead of benzyl bromide in (Example 3), 2.2 g (0.021 mol) of vinyl bromide was used to prepare diethyl 3-vinyloxyphthalate. 4.55 g were obtained.

Yield 82% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.60~7.80 (m,} 6H, vinyl, aromatic) IR (KBr) = 1740,1720 ( C = O) (cm
^-1) Elemental analysis (C ₁₄ as H ₁₆ O ₅₎ Calculated (%); C: 63.62, H: 6.10, O: 3
0.27, actual value (%); C: 63.55, H: 6.20, O: 3
0.25

(Example-10) Diethyl 3-allyloxyphthalate (Compound 10) Instead of benzyl bromide in (Example-3), 2.55 g (0.021 mol) of allyl bromide was used to give 3-allyl bromide. 4.95 g of diethyl oxyphthalate
was gotten.

Yield 85% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.20 (d, 2H, J = 8H)
z, CH ₂ ), 4.30 (q, 2H, J = 8 Hz, C
H2), 4.40 (q, 2H , J = 8Hz, CH 2),
5.20 to 7.80 (m, 6H, allyl, aromatic) IR (KBr) = 1740,1720 (C = O) (cm)
^-1 ) Elemental analysis value (as C ₁₅ H ₁₈ O ₅ ) Calculated value (%); C: 64.73, H: 6.52, O: 2
8.75, actual value (%); C: 64.66, H: 6.40, O: 2
8.96,

Example 11 Diethyl 3-geranyloxyphthalate (Compound 11) Instead of benzyl bromide in (Example 3), 4.56 g (0.021 mol) of geranyl bromide was used.
Using diethyl geranyloxyphthalate 6.7
0 g was obtained.

Yield 85% 1 H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 1.70 (d, 9H, J = 4.5)
_{Hz, CH 3), 2.10 (} m, 4H, CH 2), 4.
00 (d, 2H, J = 8Hz, CH 2), 4.20
(D, 2H, J = 8 Hz, CH ₂ ), 4.30 (q,
2H, J = 8 Hz, CH ₂ ), 4.40 (q, 2H,
_{J = 8Hz, CH 2),} 5.00~7.80 (m, 5
H, allyl, aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1) Elemental analysis (C ₂₂ H ₃₀ O ₅₎ Calculated value (%); C: 70.56, H: 8.08, O: 2
1.36, actual value (%); C: 70.35, H: 8.34, O: 2
1.31,

Example 12 Diethyl 3- (p-methylbenzyloxy) phthalate (Compound 12) In place of benzyl bromide in (Example 3), 3.88 g (0.0%) of p-methylbenzyl bromide was used.
Using 21 mol), 6.03 g of diethyl 3- (p-methylbenzyloxy) phthalate were obtained.

Yield 84% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 2.25} (s, 2H, CH 3),
4.30 (q, 2H, J = 8Hz, CH 2), 4.40
(Q, 2H, J = 8 Hz, CH ₂ ), 5.20 (s, 2
H, CH ₂ Ph), 7.20 to 7.80 (m, 7H,
(Aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₂₀ H ₂₂ O ₅ ) Calculated value (%); C: 70.16, H: 6.48, O: 2
3.36, actual value (%); C: 70.35, H: 6.25, O: 2
3.40,

Example 13 Diethyl 3- (p-methoxybenzyloxy) phthalate (Compound 13) In place of benzyl bromide in (Example 3), 4.20 g of p-methoxybenzyl bromide (0.
021 mol) to give 6.62 g of diethyl 3- (p-methoxybenzyloxy) phthalate.

Yield: 88% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 3.80} (s, 2H, CH 3),
4.30 (q, 2H, J = 8Hz, CH 2), 4.40
(Q, 2H, J = 8 Hz, CH ₂ ), 5.20 (s, 2
_{H, CH 2 Ph), 6.90~7.80} (m, 7H,
(Aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₂₀ H ₂₂ O ₆ ) Calculated value (%); C: 67.02, H: 6.19, O: 2
6.79, found (%); C: 67.35, H: 6.25, O: 2
6.40,

Example 14 Diethyl 3- (p-chlorobenzyloxy) phthalate (Compound 14) In place of benzyl bromide in (Example 3), 4.29 g (0.0%) of p-chlorobenzyl bromide was used.
Using 21 mol), 6.77 g of diethyl 3- (p-chlorobenzyloxy) phthalate were obtained.

Yield 89% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.20 (s,} 2H, CH 2 Ph), 6.90~
7.80 (m, 7H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₁₉ O ₅ Cl) Calculated value (%); C: 62.90, H: 5.24, measured value (%); C: 62.81, H: 5. 25,

(Example 15) Diethyl 4-benzyloxyphthalate (Compound 15) Instead of diethyl 3-hydroxyphthalate in (Example 3), diethyl 4-hydroxyphthalate 31.
8 g (0.134 mol), benzyl bromide 20.4 m
l (0.171 mol), 23.67 g of potassium carbonate (0.
171 mol) to give 41.15 g of diethyl 4-benzyloxyphthalate.

Yield 94% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.00 (s,} 2H, CH 2 Ph), 6.80~
7.80 (m, 8H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₀ O ₅ ) Calculated value (%); C: 69.50, H: 6.14, O: 2
4.36, actual value (%); C: 69.44, H: 6.10, O: 2
4.46,

Example 16 Diethyl 4-methoxyphthalate (Compound 16) In place of benzyl bromide in (Example 15), 29.8 g (0.210 mol) of methyl iodide was used to give 4-methoxyphthalic acid. 42.5 g of diethyl phthalate were obtained.

Yield 80% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 3.80} (s, 3H, OCH 3),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 6.80~7.
80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₁₃ as H ₁₆ O ₅₎ Calculated (%); C: 61.89, H: 6.39, O: 3
1.71, actual value (%); C: 61.77, H: 6.20, O: 3
2.03

Example 17 Diethyl 4-ethoxyphthalate (Compound 17) In place of benzyl bromide in (Example 15), 4-ethoxyethoxyethyl (32.8 g, 0.210 mol) was used instead of benzyl bromide. 44.6 g of diethyl phthalate were obtained.

Yield 80% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
z, CH ₃ ), 3.75 (t, 2H, J = 8 Hz, O
CH ₂ ), 4.30 (q, 2H, J = 8 Hz, CH ₂ ),
4.40 (q, 2H, J = 8Hz, CH 2), 6.8
5 to 7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₄ H ₁₈ O ₅ ) Calculated value (%); C: 63.14, H: 6.81, O: 3
0.04, actual value (%); C: 63.34, H: 6.67, O: 2
9.99,

(Example-18) Diethyl 4-hexyloxyphthalate (Compound 18) Instead of benzyl bromide in (Example-15), 34.65 g (0.210 mol) of bromohexane was used to give 4-hexyl. Diethyl oxyphthalate 54.5
g was obtained.

Yield 81% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
_{z, CH 3), 1.50~1.85 (} m, 8H, C
_{H 2), 3.80 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 6.90 ~
7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₈ H ₂₆ O ₅ ) Calculated value (%); C: 67.06, H: 8.13, O: 2
4.81, actual value (%); C: 67.30, H: 8.20, O: 2
4.50,

(Example-19) Diethyl 4-octyloxyphthalate (Compound 19) Instead of benzyl bromide in (Example-15), 40.5 g (0.210 mol) of bromooctane was used to give 4-octyl. 62.8 g of diethyl oxyphthalate
was gotten.

Yield 81% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
z, CH ₃ ), 1.50-2.05 (m, 12H, C
_{H 2), 3.85 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 7.00 ~
7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₂₀ H ₃₀ O ₅₎ Calculated value (%); C: 68.54, H: 8.63, O: 2
2.83, actual value (%); C: 68.35, H: 8.34, O: 2
3.31,

Example 20 Diethyl 4-decyloxyphthalate (Compound 20) Instead of benzyl bromide in (Example 15), 4.6 g (0.021 mol) of bromodecane was used to obtain 4-decyloxyphthalic acid. 7.1 g of diethyl phthalate were obtained.

Yield 89% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 1.35} (t, 3H, J = 8H
_{z, CH 3), 1.50~2.10 (} m, 16H, C
_{H 2), 3.85 (t,} 2H, J = 8Hz, OCH 2),
4.30 (q, 2H, J = 8 Hz, CH ₂ ), 4.4
0 (q, 2H, J = 8Hz, CH 2), 6.90 ~
7.80 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1) Elemental analysis (C ₂₂ H ₃₄ O as ₅₎ Calculated (%); C: 69.81, H: 9.05, O: 2
1.14, actual value (%); C: 69.75, H: 9.15, O: 2
1.10,

Example 21 Diethyl 4-vinyloxyphthalate (Compound 21) Instead of benzyl bromide in (Example 15), 2.20 g (0.021 mol) of vinyl bromide was used to prepare diethyl 4-vinyloxyphthalate. 4.72 g were obtained.

Yield 85% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.60~7.80 (m,} 6H, vinyl, aromatic) IR (KBr) = 1740,1720 ( C = O) (cm
^-1) Elemental analysis (C ₁₄ as H ₁₆ O ₅₎ Calculated (%); C: 63.62, H: 6.10, O: 3
0.27, actual value (%); C: 63.55, H: 6.20, O: 3
0.25

(Example-22) Diethyl 4-allyloxyphthalate (Compound 22) Instead of benzyl bromide in (Example-15), 2.55 g (0.021 mol) of allyl bromide was used to give 4-allyl bromide. 5.18 g of diethyl oxyphthalate
was gotten.

Yield 89% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.20 (d, 2H, J = 8H)
z, CH ₂ ), 4.30 (q, 2H, J = 8 Hz, C
H ₂ ), 4.40 (q, 2H, J = 8 Hz, CH ₂ ),
5.20 to 7.80 (m, 6H, allyl, aromatic) IR (KBr) = 1740,1720 (C = O) (cm)
^-1) Elemental analysis (C ₁₄ as H ₁₆ O ₅₎ Calculated (%); C: 63.62, H: 6.10, O: 3
0.27, actual value (%); C: 63.55, H: 6.15, O: 3
0.30,

(Example 23) Diethyl 4-geranyloxyphthalate (Compound 23) Instead of benzyl bromide in (Example-15), 4.56 g (0.021 mol) of geranyl bromide was used.
Using diethyl 4-geranyloxyphthalate 7.1
7 g were obtained.

Yield: 91% H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 1.70 (d, 9H, J = 4.5)
_{Hz, CH 3), 2.10 (} m, 4H, CH 2), 4.
00 (d, 2H, J = 8Hz, CH 2), 4.20
(D, 2H, J = 8 Hz, CH ₂ ), 4.30 (q,
2H, J = 8 Hz, CH ₂ ), 4.40 (q, 2H,
_{J = 8Hz, CH 2),} 5.00~7.80 (m, 5
H, olefin, aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1) Elemental analysis (C ₂₂ H ₃₀ O ₅₎ Calculated value (%); C: 70.56, H: 8.08, O: 2
1.36, actual value (%); C: 70.35, H: 8.23, O: 2
1.42,

Example 24 Diethyl 4- (p-methylbenzyloxy) phthalate (Compound 24) In place of benzyl bromide in (Example 15), 3.88 g (0.0%) of p-methylbenzyl bromide was used.
Using 21 mol), 6.38 g of diethyl 4- (p-methylbenzyloxy) phthalate were obtained.

H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 2.25} (s, 2H, CH 3),
4.30 (q, 2H, J = 8Hz, CH 2), 4.40
(Q, 2H, J = 8 Hz, CH ₂ ), 5.20 (s, 2
H, CH ₂ Ph), 7.20 to 7.80 (m, 7H,
(Aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₂₀ H ₂₂ O ₅ ) Calculated value (%); C: 70.16, H: 6.48, O: 2
3.36, actual value (%); C: 70.35, H: 6.30, O: 2
3.35,

(Example-25) Diethyl 4- (p-methoxybenzyloxy) phthalate (Compound 25) Instead of benzylbromide in (Example-15), 4.20 g of p-methoxybenzylbromide (0.2%) was used.
021 mol) to give 6.85 g of diethyl 4- (p-methoxybenzyloxy) phthalate.

Yield 91% 1 H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
_{= 8Hz, CH 3), 3.80} (s, 2H, CH 3),
4.30 (q, 2H, J = 8Hz, CH 2), 4.40
(Q, 2H, J = 8 Hz, CH ₂ ), 5.20 (s, 2
_{H, CH 2 Ph), 6.90~7.80} (m, 7H,
(Aromatic) IR (KBr) = 1740,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₂₀ H ₂₂ O ₆ ) Calculated value (%); C: 67.02, H: 6.19, O: 2
6.79, found (%); C: 67.35, H: 6.25, O: 2
6.40,

(Example 26) Diethyl 4- (p-chlorobenzyloxy) phthalate (Compound 26) In place of benzyl bromide in (Example 15), 4.29 g (0.0%) of p-chlorobenzyl bromide was used.
Using 21 mol), 6.77 g of diethyl 4- (p-chlorobenzyloxy) phthalate were obtained.

H-NMR (CDCl ₃ ) δ = 1.30 (t, 6H, J
= 8 Hz, CH ₃ ), 4.30 (q, 2H, J = 8H)
z, CH ₂ ), 4.40 (q, 2H, J = 8 Hz, C
_{H 2), 5.20 (s,} 2H, CH 2 Ph), 6.90~
7.80 (m, 7H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₁₉ O ₅ Cl) Calculated value (%); C: 62.90, H: 5.24, measured value (%); C: 62.81, H: 5. 25,

(Example-27) 4-Benzyloxyindane-1,3-dione (compound 27) 53.88 g of diethyl 3-benzyloxyphthalate
(0.164 mol) was heated and melted at 85 ° C, and sodium (7.31 g, 0.318 mol) was added.
After raising the temperature to 39.6 ml of ethyl acetate and 0.1 ml of ethanol.
93 ml of the mixed solution was added dropwise and stirred at 100 ° C. for 15 hours. After cooling to room temperature, 500 ml of diethyl ether was added to the reaction vessel, and the mixture was filtered and washed to obtain 43.12 g of 2-carboethoxy-4-benzyloxyindane-1,3-dione sodium salt. This product was added to 2.93 l of water without purification, melted by heating at 100 ° C.,
After cooling to 2.degree. C., 24.4 ml of concentrated sulfuric acid and 8.2
ml of the mixed solution was added and stirred. After cooling to 15 ° C., the precipitated crystals were collected by filtration to obtain 26.28 g of 4-benzyloxyindane-1,3-dione.

Yield 71% H-NMR (CDCl ₃ ) δ = 3.20 (s, 2H, C
OCH ₂ CO), 5.35 (s, 2H, CH ₂ Ph),
7.30 to 7.80 (m, 8H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (C ₁₆ H ₁₂ O ₃ to) Calculated (%); C: 76.18, H: 4.80, O: 1
9.03, found (%); C: 76.35, H: 4.65, O: 1.
9.00,

(Example-28) 4-Methoxyindane
1,3-dione (Compound 28) In Example 27, 4-methoxyindane was used by using 41.3 g (0.164 mol) of diethyl 3-methoxyphthalate instead of diethyl 3-benzyloxyphthalate. 21.6 g of -1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 3.20 (s, 2H, C
OCH ₂ CO), 3.85 (s, 3H, CH ₃ ), 7.3
0 to 7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₀ H ₈ O ₃ ) Calculated value (%); C: 68.18, H: 4.58, O: 2
7.25, actual value (%); C: 68.55, H: 4.20, O: 2
7.25,

(Example-29) 4-ethoxyindane
1,3-dione (Compound 29) In Example 27, 4-ethoxyindane was used in place of diethyl 3-benzyloxyphthalate by using 43.6 g (0.164 mol) of diethyl 3-ethoxyphthalate. 23.37 g of -1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, C
_{H 3), 3.20 (s,} 2H, COCH 2 CO), 3.9
_{5 (q, 2H, CH 2} ), 7.30~7.80 (m, 3
H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₁ H ₁₀ O ₃₎ Calculated (%); C: 69.46, H: 5.30, O: 2
5.24, actual value (%); C: 69.55, H: 5.20, O: 2
5.25,

Example 30 4-hexyloxyindane-1,3-dione (Compound 30) In Example 27, diethyl 3-hexyloxyphthalate was substituted for diethyl 3-benzyloxyphthalate. Using 52.96 g (0.164 mol), 4-
28.6 g of hexyloxyindane-1,3-dione were obtained.

Yield: 71% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 80 to 2.25 (m, 8H,
CH ₂ ), 3.20 (s, 2H, COCH ₂ CO),
4.05 (q, 2H, J = 8Hz, CH 2), 7.30
-7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₅ H ₁₈ O ₃ ) Calculated value (%); C: 73.14, H: 7.37, O: 1
9.49, actual value (%); C: 73.35, H: 7.20, O: 1
9.45,

(Example 31) 4-octyloxyindane-1,3-dione (compound 31) In (Example 27), instead of diethyl 3-benzyloxyphthalate, diethyl 3-octyloxyphthalate was used. Using 5.75 g (0.0164 mol), 4-
3.23 g of octyloxyindane-1,3-dione were obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1.70~2.25} (m, 12
H, CH ₂ ), 3.35 (s, 2H, COCH ₂ C
O), 4.15 (q, 2H , J = 8Hz, CH 2),
7.30 to 7.80 (m, 3 H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₂₂ O ₃₎ Calculated (%); C: 74.42, H: 8.08, O: 1
7.50, actual value (%); C: 74.55, H: 8.20, O: 1
7.25,

(Example-32) 4-decyloxyindane-1,3-dione (compound 32) In (Example-27), instead of diethyl 3-benzyloxyphthalate, diethyl 3-decyloxyphthalate was used. Using 6.21 g (0.0164 mol), 3.56 g of 4-decyloxyindane-1,3-dione was obtained.

Yield: 72% 1 H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1.75~2.25} (m, 16
H, CH ₂ ), 3.35 (s, 2H, COCH ₂ CO),
4.20 (q, 2H, J = 8Hz, CH 2), 7.30
-7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₆ O ₃ ) Calculated value (%); C: 75.46, H: 8.67, O: 1
5.87, actual value (%); C: 75.63, H: 8.20, O: 1
6.17,

(Example 33) 4-vinyloxyindane-1,3-dione (compound 33) In (Example 27), instead of diethyl 3-benzyloxyphthalate, diethyl 3-vinyloxyphthalate was used. 2.34 g (0.0164 mol) of 2.34 g of 4-vinyloxyindane-1,3-dione were obtained.

Yield 76% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
_{OCH 2 CO), 5.70~7.80 (m} , 6H, vinyl, aromatic) IR (KBr) = 1750,1720 ( C = O) (cm
^-1 ) Elemental analysis value (as C ₁₁ H ₈ O ₃ ) Calculated value (%); C: 70.21, H: 4.29, O: 2
5.51, actual value (%); C: 70.55, H: 4.20, O: 2
5.25,

(Example 34) 4-Allyloxyindane-1,3-dione (Compound 34) In (Example 27), instead of diethyl 3-benzyloxyphthalate, diethyl 3-allyloxyphthalate was used. Using 4.56 g (0.0164 mol), 2.48 g of 4-allyloxyindane-1,3-dione was obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 4.20 (d, 2H, J = 8 Hz, C
_{H 2), 5.20~7.80 (m,} 6H, allyl, aromatic) IR (KBr) = 1750,1720 ( C = O) (cm
^-1) Elemental analysis (as C ₁₂ H ₁₀ O ₃₎ Calculated (%); C: 71.28, H: 4.99, O: 2
3.74, actual value (%); C: 71.45, H: 4.80, O: 2
3.75,

(Example-35) 4-Geranyloxyindane-1,3-dione (Compound 35) In (Example 27), instead of diethyl 3-benzyloxyphthalate, diethyl 3-geranyloxyphthalate was used. Using 6.15 g (0.0164 mol), 4-
3.38 g of geranyloxyindane-1,3-dione were obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.75 (d, 9H, J
_{= 4.5Hz, CH 3), 2.10} (m, 4H, C
_{H 2), 3.30 (s,} 2H, COCH 2 CO), 4.
15 (d, 2H, J = 8Hz, CH 2), 5.20~
7.80 (m, 5H, olefin, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₂ O ₃ ) Calculated value (%); C: 76.48, H: 7.43, O: 1
6.09, actual value (%); C: 76.55, H: 7.25, O: 1
6.20,

(Example-36) 4- (p-Methylbenzyloxy) indan-1,3-dione (Compound 36) In (Example 27), instead of diethyl 3-benzyloxyphthalate, 5.60 g (0.0164 mol) of diethyl (p-methylbenzyloxy) phthalate
Was used to obtain 3.28 g of 4- (p-methylbenzyloxy) indan-1,3-dione.

Yield 72% H-NMR (CDCl ₃ ) δ = 2.20 (s, 2H, C
_{H 3), 3.30 (s,} 2 H, COCH 2 CO), 5.
_{20 (s, 2H, CH 2} ), 6.85~7.8 (m,
7H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₁₄ O ₃₎ Calculated (%); C: 76.67, H: 5.30, O: 1
8.03, actual value (%); C: 76.55, H: 5.20, O: 1
8.25,

(Example 37) 4- (p-Methoxybenzyloxy) indane-1,3-dione (Compound 37) In Example 27, 3- (3-benzyloxyphthalic acid) was replaced with diethyl 3-benzyloxyphthalate. 5.87 g of diethyl (p-methoxybenzyloxy) phthalate (0.0164 mol
Using l), 3.38 g of 4- (p-methoxybenzyloxy) indan-1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 3.85 (s, 3H, CH ₃ ), 5.2
_{0 (s, 2H, CH 2} ), 6.85~7.80 (m, 7
H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₁₄ O ₃₎ Calculated (%); C: 76.67, H: 5.30, O: 1
8.03, actual value (%); C: 76.55, H: 5.20, O: 1
8.25,

(Example-38) 4- (p-Chlorobenzyloxy) indan-1,3-dione (Compound 38) In Example 27, 3-ethyl-3-benzyloxyphthalate was replaced with 3-ethyl-3-benzyloxyphthalate. 5.94 g (0.0164 mol) of diethyl (p-chlorobenzyloxy) phthalate
Was used to obtain 3.40 g of 4- (p-chlorobenzyloxy) indan-1,3-dione.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 5.20 (s, 2H, CH ₂ ), 6.8
0 to 7.80 (m, 7H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₆ H ₁₁ O ₃ Cl) Calculated value (%); C: 67.02, H: 3.84, measured value (%); C: 67.33, H: 3. 65,

(Example-39) 5-Benzyloxyindane-1,3-dione (Compound 39) Instead of diethyl 3-benzyloxyphthalate in (Example-27), diethyl 4-benzyloxyphthalate 41 Using 0.2 g (0.126 mol), 19.55 g of 5-benzyloxyindane-1,3-dione was obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 3.20 (s, 2H, C
OCH ₂ CO), 5.20 (s, 2H, CH ₂ Ph),
7.20 to 8.00 (m, 8H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (C ₁₆ H ₁₂ O ₃ to) Calculated (%); C: 76.18, H: 4.80, O: 1
9.03, actual value (%); C: 76.56, H: 4.65, O: 1
8.79,

Example 40 5-Methoxyindane
1,3-dione (Compound 40) In Example 27, 5-methoxyindane was used by using 41.3 g (0.164 mol) of diethyl 4-methoxyphthalate instead of diethyl 3-benzyloxyphthalate. 21.0 g of -1,3-dione were obtained.

Yield 73% H-NMR (CDCl ₃ ) δ = 3.20 (s, 2H, C
OCH ₂ CO), 3.85 (s, 3H, CH ₃ ), 6.9
0 to 7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₀ H ₈ O ₃ ) Calculated value (%); C: 68.18, H: 4.58, O: 2
7.25, actual value (%); C: 68.55, H: 4.30, O: 2
7.15,

(Example-41) 5-ethoxyindane
1,3-dione (Compound 41) In Example 27, 4-ethoxyindane was used in place of diethyl 3-benzyloxyphthalate by using 43.6 g (0.164 mol) of diethyl 4-ethoxyphthalate. 23.37 g of -1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 1.35
_{(T, 3H, CH 3)} , 3.20 (s, 2H, COCH 2
CO), 3.95 (q, 2H , CH 2), 6.80~
7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₁ H ₁₀ O ₃₎ Calculated (%); C: 69.46, H: 5.30, O: 2
5.24, actual value (%); C: 69.55, H: 5.15, O: 2
5.30,

(Example 42) 5-Hexyloxyindane-1,3-dione (compound 42) In (Example 27), diethyl 4-hexyloxyphthalate was used in place of diethyl 3-benzyloxyphthalate. Using 52.96 g (0.164 mol), 5-
30.2 g of hexyloxyindane-1,3-dione were obtained.

Yield: 75% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 80 to 2.25 (m, 8
H, CH ₂ ), 3.20 (s, 2H, COCH ₂ CO),
4.05 (q, 2H, J = 8Hz, CH 2), 6.8
0 to 7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₅ H ₁₈ O ₃ ) Calculated value (%); C: 73.14, H: 7.37, O: 1
9.49, actual value (%); C: 73.35, H: 7.34, O: 1
9.31,

(Example-43) 5-octyloxyindane-1,3-dione (compound 43) In (Example-27), instead of diethyl 3-benzyloxyphthalate, diethyl 4-octyloxyphthalate was used. Using 5.75 g (0.0164 mol), 5-
3.23 g of octyloxyindane-1,3-dione were obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 70 to 2.25 (m, 12
H, CH ₂ ), 3.35 (s, 2H, COCH ₂ CO),
4.15 (q, 2H, J = 8Hz, CH 2), 6.8
5 to 7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₂₂ O ₃₎ Calculated (%); C: 74.42, H: 8.08, O: 1
7.50, actual value (%); C: 74.55, H: 8.15, O: 1
7.30,

(Example 44) 5-decyloxyindane-1,3-dione (compound 44) In (Example 27), diethyl 4-decyloxyphthalate was used in place of diethyl 3-benzyloxyphthalate. Using 6.21 g (0.0164 mol), 3.66 g of 5-decyloxyindane-1,3-dione was obtained.

Yield 74% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . 75 to 2.25 (m, 16
H, CH ₂ ), 3.35 (s, 2H, COCH ₂ CO),
4.20 (q, 2H, J = 8Hz, CH 2), 7.3
0 to 7.80 (m, 3H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₆ O ₃ ) Calculated value (%); C: 75.46, H: 8.67, O: 1
5.87, actual value (%); C: 75.63, H: 8.13, O: 1
6.24,

(Example-45) 5-Vinyloxyindane-1,3-dione (Compound 45) In (Example 27), diethyl 4-vinyloxyphthalate was used in place of diethyl 3-benzyloxyphthalate. 2.31 g (0.0164 mol) of 2.31 g of 5-vinyloxyindane-1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 3.30
_{(S, 2H, COCH 2 CO} ), 5.70~7.80
(M, 6H, vinyl, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₁ H ₈ O ₃ ) Calculated value (%); C: 70.21, H: 4.29, O: 2
5.51, actual value (%); C: 70.45, H: 4.20, O: 2
5.35,

(Example-46) 5-Allyloxyindane-1,3-dione (Compound 46) In (Example-27), instead of diethyl 3-benzyloxyphthalate, diethyl 4-allyloxyphthalate was used. Using 4.56 g (0.0164 mol), 2.48 g of 5-allyloxyindane-1,3-dione was obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 4.20 (d, 2H, J = 8 Hz, C
_{H 2), 5.20~7.80 (m,} 6H, allyl, aromatic) IR (KBr) = 1750,1720 ( C = O) (cm
^-1) Elemental analysis (as C ₁₂ H ₁₀ O ₃₎ Calculated (%); C: 71.28, H: 4.99, O: 2
3.74, actual value (%); C: 71.45, H: 4.80, O: 2
3.75,

(Example 47) 5-Geranyloxyindane-1,3-dione (compound 47) In Example 27, diethyl 4-geranyloxyphthalate was used in place of diethyl 3-benzyloxyphthalate. Using 6.15 g (0.0164 mol), 5-
3.58 g of geranyloxyindane-1,3-dione were obtained.

Yield 73% H-NMR (CDCl ₃ ) δ = 1.75 (d, 9H, J
_{= 4.5Hz, CH 3), 2.10} (m, 4H, C
_{H 2), 3.30 (s,} 2H, COCH 2 CO), 4.
15 (d, 2H, J = 8Hz, CH 2), 5.20~
7.80 (m, 5H, olefin, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₉ H ₂₂ O ₃ ) Calculated value (%); C: 76.48, H: 7.43, O: 1
6.09, actual value (%); C: 76.55, H: 7.34, O: 1
6.11,

(Example 48) 5- (p-Methylbenzyloxy) indane-1,3-dione (compound 48) In (Example 27), instead of diethyl 3-benzyloxyphthalate, 4- 5.60 g (0.0164 mol) of diethyl (p-methylbenzyloxy) phthalate
Was used to obtain 3.37 g of 5- (p-methylbenzyloxy) indan-1,3-dione.

Yield 74% H-NMR (CDCl ₃ ) δ = 2.20 (s, 2H, C
_{H 3), 3.30 (s,} 2H, COCH 2 CO), 5.2
_{0 (s, 2H, CH 2} ), 6.85~7.80 (m, 7
H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₁₄ O ₃₎ Calculated (%); C: 76.67, H: 5.30, O: 1
8.03, actual value (%); C: 76.55, H: 5.12, O: 1
8.33,

(Example 49) 5- (p-methoxybenzyloxy) indane-1,3-dione (compound 49) In (Example 27), instead of diethyl 3-benzyloxyphthalate, 4- 5.87 g of diethyl (p-methoxybenzyloxy) phthalate (0.0164 mol
Using l), 3.72 g of 5- (p-methoxybenzyloxy) indan-1,3-dione were obtained.

Yield 77% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 3.85 (s, 3H, CH ₃ ), 5.2
_{0 (s, 2H, CH 2} ), 6.85~7.80 (m, 7
H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1) Elemental analysis (as C ₁₇ H ₁₄ O ₃₎ Calculated (%); C: 76.67, H: 5.30, O: 1
8.03, actual value (%); C: 76.55, H: 5.34, O: 1
8.11,

Example 50 5- (p-Chlorobenzyloxy) indane-1,3-dione (Compound 50) In Example 27, 4- (p-chlorobenzyloxy) indane-1,3-dione was used in place of diethyl 3-benzyloxyphthalate. 5.94 g (0.0164 mol) of diethyl (p-chlorobenzyloxy) phthalate
Was used to obtain 3.40 g of 5- (p-chlorobenzyloxy) indan-1,3-dione.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.30 (s, 2H, C
OCH ₂ CO), 5.20 (s, 2H, CH ₂ ), 6.8
0 to 7.80 (m, 7H, aromatic) IR (KBr) = 1750, 1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₆ H ₁₁ O ₃ Cl) Calculated value (%); C: 67.02, H: 3.84, measured value (%); C: 67.33, H: 3. 76,

(Example 51) 2-diazo-4-benzyloxyindane-1,3-dione (compound 51) 4-benzyloxyindane-1,3-dione 26.3
g (0.117 mol) was dissolved in 158 ml of ethanol,
Cooled to -10C. 21.3 ml of triethylamine were added and, at the same temperature, 34.63 g of tosyl azide (0.17
23 mol of ethanol (58 mol) were added and stirred for 1 hour. The precipitated crystals were filtered, washed with cold ethanol, and dried to give 2-diazo-4-benzyloxyindane.
1,3-dione. 94 g were obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 5.40 (s, 2H, C
H ₂ Ph), 7.30 to 7.80 (m, 8H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₆ H ₁₀ O ₃ N ₂ ) Calculated (%); C: 69.06, H: 3.62, O: 1
7.25, N: 10.07 Found (%); C: 69.35, H: 3.32, O: 1
7.42, N: 9.91

(Example-52) 2-Diazo-4-methoxyindane-1,3-dione (Compound 52) In (Example 51), 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 20.59 g of 4-methoxyindane-1,3-dione (0.117 mol
Using l), 2-diazo-4-methoxyindane-
16.54 g of 1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.85 (s, 3H, C
_{H 3), 7.30~7.80 (m,} 3H, aromatic) IR (KBr) = 2200 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₀ H ₆ O ₃ N ₂ ) Calculated value (%); C: 59.41, H: 2.99, O: 2
3.74, N: 13.86 Found (%); C: 59.35, H: 3.21, O: 2
3.42, N: 14.02

(Example-53) 2-diazo-4-ethoxyindane-1,3-dione (compound 53) In (Example 51), 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. Using 22.23 g (0.117 mol) of 4-ethoxyindane-1,3-dione, 17.69 g of 2-diazo-4-ethoxyindane-1,3-dione was obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, C
_{H 3), 3.95 (q,} 2H, CH 2), 7.30~7.
80 (m, 3H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₁ H ₈ O ₃ N ₂ ) Calculated value (%); C: 61.11, H: 3.73, O: 2
2.20, N: 12.96 actual value (%); C: 61.35, H: 3.52, O: 2
2.17, N: 12.96

(Example 54) 2-Diazo-4-hexyloxyindane-1,3-dione (Compound 54) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 28.78 g of 4-hexyloxyindane-1,3-dione (0.117 mol
Using l), 21.64 g of 2-diazo-4-hexyloxyindane-1,3-dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 80 to 2.25 (m, 8
H, CH ₂ ), 4.05 (q, 2H, J = 8 Hz, CH
₂ ), 7.30 to 7.80 (m, 3H, aromatic) IR (KBr) = 2260 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₅ H ₈ O ₃ N ₂ ) Calculated (%); C: 68.18, H: 3.05, O: 1
8.17, N: 10.60 found (%); C: 68.35, H: 3.22, O: 1
8.32, N: 10.11

(Example 55) 2-diazo-4-octyloxyindane-1,3-dione (compound 55) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 32.05 g of 4-octyloxyindane-1,3-dione (0.117 mol
Using l), 25.27 g of 2-diazo-4-octyloxyindane-1,3-dione were obtained.

H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 70 to 2.25 (m, 12
H, CH ₂ ), 4.15 (q, 2H, J = 8 Hz, C H
₂ ), 7.30 to 7.80 (m, 3H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₇ H ₂₀ O ₃ N ₂ ) Calculated (%); C: 67.98, H: 6.71, O: 1
5.98, N: 9.33 Found (%); C: 67.88, H: 6.65, O: 1
5.72, N: 9.75

(Example 56) 2-diazo-4-decyloxyindane-1,3-dione (Compound 56) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. , 4-decyloxyindane-1,3-dione 35.33 g (0.117 mol)
To give 2-diazo-4-decyloxyindane-
27.6 g of 1,3-dione were obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . 75 to 2.25 (m, 16
H, CH ₂ ), 4.15 (q, 2H, J = 8 Hz, C
_{H 2), 7.30~7.80 (m,} 3H, aromatic) IR (KBr) = 2250 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₉ H ₂₄ O ₃ N ₂ ) Calculated (%); C: 69.49, H: 7.37, O: 1
4.62, N: 8.53 actual value (%); C: 69.35, H: 7.32, O: 1
4.42, N: 8.81

(Example 57) 2-diazo-4-vinyloxyindane-1,3-dione (compound 57) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. , 2.20 g (0.0117 mol) of 4-vinyloxyindane-1,3-dione
Using 2-diazo-4-vinyloxyindane-
1.80 g of 1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 5.70-7.80
(M, 6H, vinyl, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₁ H ₆ O ₃ N ₂ ) Calculated (%); C: 61.68, H: 2.82, O: 2
2.48, N: 13.08 Found (%); C: 61.35, H: 2.87, O: 2
2.42, N: 13.36

(Example-58) 4-Allyloxy-2-
2. Diazoindane-1,3-dione (Compound 58) In (Example 51), instead of 4-benzyloxyindane-1,3-dione, 2.36 g of 4-allyloxyindane-1,3-dione (0. 0.117 mol)
To give 4-allyloxy-2-diazo-indane-
1.92 g of 1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 4.20 (d, 2H, J
_{= 8Hz, CH 2), 5} . 20 to 7.80 (m, 6
H, allyl, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₂ H ₈ O ₃ N ₂ ) Calculated value (%); C: 63.16, H: 3.53, O: 2
1.03, N: 12.28 actual value (%); C: 63.35, H: 3.39, O: 2
1.42, N: 11.86

(Example 59) 2-Diazo-4-geranyloxyindane-1,3-dione (Compound 59) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 3.51 g of 4-geranyloxyindane-1,3-dione (0.0117 mol
Using l), 3.00 g of 2-diazo-4-geranyloxyindane-1,3-dione were obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.75 (d, 9H, J
_{= 4.5Hz, CH 3), 2.10} (m, 4H, C
H ₂ ), 4.15 (d, 2H, J = 8 Hz, CH ₂ ),
5.20 to 7.80 (m, 5H, olefin, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₉ H ₂₀ O ₃ N ₂ ) Calculated value (%); C: 70.35, H: 6.22, O: 1
4.80, N: 8.64 actual value (%); C: 70.35, H: 6.32, O: 1
4.62, N: 8.71

Example 60 2-Diazo-4- (p-
Methylbenzyloxy) indane-1,3-dione (Compound 60) In Example 51, 4- (p-methylbenzyloxy) indane-1 was used instead of 4-benzyloxyindan-1,3-dione. 3.25 g of 3-dione
(0.0117 mol) using 2-diazo-4- (p
2.56 g of -methylbenzyloxy) indane-1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 2.20 (s, 2H, C
_{H 3), 5.20 (s,} 2H, CH 2), 6.85~7.
80 (m, 7H, aromatic) IR (KBr) = 2245 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₇ H ₁₂ O ₃ N ₂ ) Calculated (%); C: 69.85, H: 4.14, O: 1
6.42, N: 9.59 found (%); C: 69.65, H: 4.32, O: 1
6.56, N: 9.47

(Example 61) 2-diazo-4- (p-
(Methoxybenzyloxy) indane-1,3-dione (Compound 61) In Example 51, 4- (p-methoxybenzyloxy) indane-1 was used instead of 4-benzyloxyindan-1,3-dione. , 3.44 g of 3-dione
(0.0117 mol) using 2-diazo-4- (p
2.62 g of -methoxybenzyloxy) indane-1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.85 (s, 3H, C
_{H 3), 5.20 (s,} 2H, CH 2), 6.85~7.
80 (m, 7H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₇ H ₁₂ O ₄ N ₂ ) Calculated value (%); C: 66.23, H: 3, 92, O: 2
0.26, N: 9.09 actual value (%); C: 66.35, H: 3.82, O: 2
0.42, N: 9.41

(Example 62) 2-diazo-4- (p-
Chlorobenzyloxy) indane-1,3-dione (Compound 62) In Example 51, 4- (p-chlorobenzyloxy) indane-1 was used instead of 4-benzyloxyindan-1,3-dione. , 3-dione 3.48g
(0.0117 mol) using 2-diazo-4- (p
2.66 g of -chlorobenzyloxy) indane-1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 5.20 (s, 2H, C
_{H 2), 6.80~7.80 (m,} 7H, aromatic) IR (KBr) = 2250 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₆ H ₆ O ₃ N ₂ Cl) Calculated (%); C: 61.44, H: 2.88, N:
8.96 actual value (%); C: 61.35, H: 2.66, N:
9.09

(Example-63) 5-benzyloxy-2
-Diazoindane-1,3-dione (Compound 63) In Example 51, 19.55 g of 5-benzyloxyindane-1,3-dione was used instead of 4-benzyloxyindane-1,3-dione ( 0.0873mo
Using l), 16.73 g of 5-benzyloxy-2-diazoindane-1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 5.20 (s, 2H, C
H ₂ Ph), 7.20 to 8.00 (m, 8H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₆ H ₁₀ O ₃ N ₂ ) Calculated (%); C: 69.06, H: 3.62, O: 1
7.25, N: 10.07 Found (%); C: 69.40, H: 3.35, O: 1
7.42, N: 9.83

(Example-64) 2-diazo-5-methoxyindane-1,3-dione (Compound 64) In (Example 51), instead of 4-benzyloxyindane-1,3-dione, Using 20.59 g (0.117 mol) of 5-methoxyindane-1,3-dione, 15.77 g of 2-diazo-5-methoxyindane-1,3-dione was obtained.

Yield 67% H-NMR (CDCl ₃ ) δ = 3.85 (s, 3H, C
_{H 3), 6.85~7.80 (m,} 3H, aromatic) IR (KBr) = 2200 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₀ H ₆ O ₃ N ₂ ) Calculated value (%); C: 59.41, H: 2.99, O: 2
3.74, N: 13.86 Found (%); C: 59.40, H: 3.34, O: 2
3.42, N: 13.84

(Example 65) 2-diazo-5-ethoxyindane-1,3-dione (compound 65) In (Example 51), instead of 4-benzyloxyindane-1,3-dione, Using 22.23 g (0.117 mol) of 5-ethoxyindane-1,3-dione, 18.16 g of 2-diazo-5-ethoxyindane-1,3-dione was obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, C
_{H 3), 3.95 (q,} 2H, CH 2), 6.90~7.
80 (m, 3H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm -1) Elemental analysis (C ₁₁ H ₈ O ₃ as N ₂₎ Calculated (%); C: 61.11, H: 3.73, O: 2
2.20, N: 12.96 actual value (%); C: 61.40, H: 3.52, O: 2
2.25, N: 12.83

(Example 66) 2-diazo-5-hexyloxyindane-1,3-dione (Compound 66) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 28.78 g of 5-hexyloxyindan-1,3-dione (0.117 mol
Using l), 22.27 g of 2-diazo-5-hexyloxyindane-1,3-dione were obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 80 to 2.25 (m, 8
H, CH ₂ ), 4.05 (q, 2H, J = 8 Hz, CH
₂ ), 6.85 to 7.80 (m, 3H, aromatic) IR (KBr) = 2260 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₅ H ₈ O ₃ N ₂ ) Calculated (%); C: 68.18, H: 3.05, O: 1
8.17, N: 10.60 found (%); C: 68.35, H: 3.22, O: 1
8.32, N: 10.11

(Example 67) 2-diazo-5-octyloxyindane-1,3-dione (Compound 67) In (Example 51), 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 32.05 g of 5-octyloxyindan-1,3-dione (0.117 mol
Using l), 23.87 g of 2-diazo-5-octyloxyindane-1,3-dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 70 to 2.25 (m, 12
H, CH ₂ ), 4.15 (q, 2H, J = 8 Hz, C
_{H 2), 6.85~7.80 (m,} 3H, aromatic) IR (KBr) = 2250 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₇ H ₂₀ O ₃ N ₂ ) Calculated (%); C: 67.98, H: 6.71, O: 1
5.98, N: 9.33 Found (%); C: 67.78, H: 6.75, O: 1
5.72, N: 9.75

(Example 68) 2-diazo-5-decyloxyindane-1,3-dione (compound 68) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. , 5-decyloxyindane-1,3-dione 35.33 g (0.117 mol)
To give 2-diazo-5-decyloxyindane-
27.6 g of 1,3-dione were obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . 75 to 2.25 (m, 16
H, CH ₂ ), 4.15 (q, 2H, J = 8 Hz, C
_{H 2), 6.85~7.80 (m,} 3H, aromatic) IR (KBr) = 2250 ( N = N), 1750,17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₉ H ₂₄ O ₃ N ₂ ) Calculated (%); C: 69.49, H: 7.37, O: 1
4.62, N: 8.53 actual value (%); C: 69.35, H: 7.32, O: 1
4.42, N: 8.81

(Example 69) 2-diazo-5-vinyloxyindane-1,3-dione (Compound 69) In Example 51, instead of 4-benzyloxyindane-1,3-dione, , 5-vinyloxyindane-1,3-dione 2.20 g (0.0117 mol)
Using 2-diazo-5-vinyloxyindane-
1.80 g of 1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 5.70-7.80
(M, 6H, vinyl, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₁ H ₆ O ₃ N ₂ ) Calculated (%); C: 61.68, H: 2.82, O: 2
2.48, N: 13.08 Found (%); C: 61.35, H: 2.67, O: 2
2.45, N: 13.53

(Example-70) 5-Allyloxy-2-
Diazoindane-1,3-dione (Compound 58) In (Example-51), instead of 4-benzyloxyindane-1,3-dione, 2.36 g of 5-allyloxyindane-1,3-dione (0 0.117 mol)
Using 5-allyloxy-2-diazoindane-
1.92 g of 1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 4.20 (d, 2H, J
_{= 8Hz, CH 2), 5} . 20 to 7.80 (m, 6
H, allyl, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₂ H ₈ O ₃ N ₂ ) Calculated value (%); C: 63.16, H: 3.53, O: 2
1.03, N: 12.28 actual value (%); C: 63.49, H: 3.45, O: 2
1.45, N: 11.61

(Example 71) 2-diazo-5-geranyloxyindane-1,3-dione (Compound 71) In Example 51, 4-benzyloxyindane-1,3-dione was used in place of 4-benzyloxyindane-1,3-dione. 3.51 g of 5-geranyloxyindane-1,3-dione (0.0117 mol
Using l), 3.09 g of 2-diazo-5-geranyloxyindane-1,3-dione were obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 1.75 (d, 9H, J
_{= 4.5Hz, CH 3), 2.10} (m, 4H, C
H ₂ ), 4.15 (d, 2H, J = 8 Hz, CH ₂ ),
5.20 to 7.80 (m, 5H, olefin, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₉ H ₂₀ O ₃ N ₂ ) Calculated value (%); C: 70.35, H: 6.22, O: 1
4.80, N: 8.64 actual value (%); C: 70.56, H: 6.40, O: 1
4.62, N: 8.42

(Example-72) 2-diazo-5- (p-
Methylbenzyloxy) indane-1,3-dione (Compound 72) In Example 51, 5- (p-methylbenzyloxy) indane-1 was used instead of 4-benzyloxyindan-1,3-dione. 3.25 g of 3-dione
(0.0117 mol) using 2-diazo-5- (p
2.66 g of -methylbenzyloxy) indane-1,3-dione were obtained.

Yield 75% H-NMR (CDCl ₃ ) δ = 2.20 (s, 2H, C
_{H 3), 5.20 (s,} 2H, CH 2), 6.85~7.
80 (m, 7H, aromatic) IR (KBr) = 2245 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₇ H ₁₂ O ₃ N ₂ ) Calculated (%); C: 69.85, H: 4.14, O: 1
6.42, N: 9.59 found (%); C: 69.60, H: 4.00, O: 1
6.65, N: 9.75

(Example 73) 2-diazo-5- (p-
Methoxybenzyloxy) indane-1,3-dione (Compound 73) In (Example 51), instead of 4-benzyloxyindan-1,3-dione, 5- (p-methoxybenzyloxy) indane-1 was used. , 3.44 g of 3-dione
(0.0117 mol) using 2-diazo-5- (p
2.62 g of -methoxybenzyloxy) indane-1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 3.85 (s, 3H, C
_{H 3), 5.20 (s,} 2H, CH 2), 6.85~7.
80 (m, 7H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis value (as C ₁₇ H ₁₂ O ₄ N ₂ ) Calculated value (%); C: 66.23, H: 3, 92, O: 2
0.26, N: 9.09 actual value (%); C: 66.40, H: 3.75, O: 2
0.42, N: 9.43

(Example 74) 2-diazo-5- (p-
Chlorobenzyloxy) indane-1,3-dione (Compound 74) In Example 51, 5- (p-chlorobenzyloxy) indane-1 was used instead of 4-benzyloxyindan-1,3-dione. , 3-dione 3.48g
(0.0117 mol) using 2-diazo-5- (p
2.66 g of -chlorobenzyloxy) indane-1,3-dione were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 5.20
_{(S, 2H, CH 2)} , 6.80~7.80 (m, 7
H, aromatic) IR (KBr) = 2250 (N = N), 1750, 17
20 (C = O) (cm ^-1 ) Elemental analysis (as C ₁₆ H ₆ O ₃ N ₂ Cl) Calculated (%); C: 61.44, H: 2.88, N:
8.96 actual value (%); C: 61.40, H: 2.65, N:
9.10

(Example-75) 2-acetyloxy-4-
Benzyloxyindane-1,3-dione (compound 7
5) 19.94 g (0.0798 mol) of 2-diazo-4-benzyloxyindane-1,3-dione was added to 191 ml of acetic acid.
And heated to 95 ° C. 12 g of copper powder was added, and a stirring reaction was performed until the diazo compound disappeared. After completion of the reaction, the copper powder was filtered, methylene chloride and water were added, and the mixture was separated and extracted. Methylene chloride was distilled off under reduced pressure and then recrystallized from methylene chloride-hexane.
Acetyloxy-4-benzyloxyindane-1,3-
15.38 g of dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 2.19 (s, 3H, C
_{H 3), 5.18 (s,} 1H, CH (OAc)), 5.
_{28 (s, 2H, CH 2} Ph), 7.20~8. 00
(M, 8H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₈ H ₁₄ O ₅₎ Calculated value (%); C: 69.67, H: 4.55, O: 2
5.78, Found (%); C: 69.55, H: 4.20, O: 2
6.25,

(Example-76) 2-formyloxy-4-
Benzyloxyindane-1,3-dione (compound 7
6) In (Example-75), using formic acid instead of acetic acid, 17.50 g of 2-formyloxy-4-benzyloxyindane-1,3-dione was obtained.

Yield 74% H-NMR (CDCl ₃ ) δ = 5.16 (s, 1H, C
H (OCOH)), 5. 30 (s, 2H, CH ₂ P
h), 7.20-8.00 (m, 8H, aromatic), 9.
50 (s, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₇ H ₁₂ O ₅₎ Calculated value (%); C: 68.91, H: 4.08, O: 2
7.00, actual value (%); C: 68.65, H: 4.20, O: 2
7.15,

(Example 77) 2- propionyloxy -4-benzyloxyindane-1,3-dione (Compound 77) In (Example 75), 2- propionyloxy -4-benzyloxyindane-1,3-dione was used in place of acetic acid, and propionic acid was used. 18.60 g of propionyloxy -4-benzyloxyindane-1,3-dione were obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 1.40
(T, 3H, J = 8 Hz, CH ₃ ), 2. 25 (q,
2H, J = 8 Hz, CH ₂ ), 5.16 (s, 1H, C
H (OCOC H ₂ CH ₃ )), 5.30 (s, 2H, C
_{H 2 Ph), 7.20~8.00 (m} , 8H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^-1 ) UV (MeOH) = 240,275 (nm) Elemental analysis (as C ₁₉ H ₁₆ O ₅ ) Calculated (%); C: 70.36, H: 4.98, O: 2
4.66, actual value (%); C: 70.25, H: 4.78, O: 2
4.97,

(Example-78) 2-butyryloxy-4
-Benzyloxyindane-1,3-dione (compound 7
8) In (Example-75), butyric acid was used instead of acetic acid, to obtain 18.80 g of 2-butyryloxy-4-benzyloxyindane-1,3-dione.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.35 (q, 2H, J = 8 Hz, CH ₂ ); 1
4 (s, 1H, CH (OCOCH ₂ CH ₂ CH ₃ ));
_{30 (s, 2H, CH 2} Ph), 7.20~8.00
(M, 8H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₂₀ H ₁₈ as O ₅₎ Calculated (%); C: 70.99, H: 5.36, O: 2
3.46, actual value (%); C: 70.88, H: 5.20, O: 2
3.92,

(Example-79) 2-Acetoxy-5-
Benzyloxyindane-1,3-dione (compound 7
9) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 5-benzyloxy-2-diazoindane-1,3-dione 1
Using 6.37 g (0.0655 mol), 14.66 g of 2-acetyloxy-5-benzyloxyindane-1,3-dione was obtained.

Yield 79% H-NMR (CDCl ₃ ) δ = 2.20 (s, 3H, C
H ₃ ), 5.20 (s, 3H, CH ₂ Ph and CH (OA
c)), 7.20-8.00 (m, 8H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm)
^{-1) UV (MeOH) = 240,275} (nm) mp 119-120 ° C. Elemental analysis (C ₁₈ H ₁₄ O ₅₎ Calculated value (%); C: 69.67, H: 4.55, O : 2
5.78, found (%); C: 69.45, H: 4.45, O: 2
6.10,

(Example-80) 2-formyloxy-5-
Benzyloxyindane-1,3-dione (compound 8
0) In (Example-79), using formic acid instead of acetic acid, 17.30 g of 2-formyloxy-5-benzyloxyindane-1,3-dione was obtained.

Yield 73% H-NMR (CDCl ₃ ) δ = 5.16 (s, 1H, C
H (OCOH)), 5. 30 (s, 2H, CH ₂ P
h), 6.80-8.00 (m, 8H, aromatic), 9.
50 (s, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₇ H ₁₂ O ₅₎ Calculated value (%); C: 68.91, H: 4.08, O: 2
7.00, actual value (%); C: 68.75, H: 4.20, O: 2
7.05,

(Example-81) 2- Propionyloxy -5-benzyloxyindane-1,3-dione (Compound 81) In (Example-79), 2- propionyloxy -5-benzyloxyindane-1,3-dione was used in place of acetic acid, using propionic acid instead of 2-acetic acid. 18.90 g of propionyloxy -5-benzyloxyindane-1,3-dione were obtained.

Yield 73% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . 25 (q, 2H, J = 8H
z, CH ₂ ), 5.00 (s, 1H, CH (OCOC)
H ₂ CH ₃ )), 5.30 (s, 2H, CH ₂ Ph),
6.80 to 8.00 (m, 8H, aromatic), IR (KBr) = 1760, 1720 (C = O) (cm
^-1 ) UV (MeOH) = 240,275 (nm) Elemental analysis (as C ₁₉ H ₁₆ O ₅ ) Calculated (%); C: 70.36, H: 4.98, O: 2
4.66, actual value (%); C: 70.56, H: 4.80, O: 2
4.64,

(Example-82) 2-butyryloxy-5
-Benzyloxyindane-1,3-dione (compound 8
2) In (Example-79), butyric acid was used in place of acetic acid to obtain 18.20 g of 2-butyryloxy-5-benzyloxyindane-1,3-dione.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.35 (q, 2H, J = 8 Hz, CH ₂ ); 1
6 (s, 1H, CH (OCOCH ₂ CH ₂ CH ₃ )),
5.30 (s, 2H, C H 2 Ph), 6.75~8.
00 (m, 8H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₂₀ H ₁₈ as O ₅₎ Calculated (%); C: 70.99, H: 5.36, O: 2
3.46, actual value (%); C: 70.90, H: 5.54, O: 2
3.56,

(Example-83) 2-acetyloxy-4-
Methoxyindane-1,3-dione (Compound 83) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-4-methoxyindane-1, 3-dione 16.12
g (0.0798 mol) using 2-acetyloxy-
12.70 g of 4-methoxyindane-1,3-dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 2.19 (s, 3H, C
H ₃ ), 3.85 (s, 3H, CH ₃ ), 5.18 (s,
1H, CH (OAc)), 7.20-8.00 (m,
3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₂ H ₁₀ as O ₅₎ Calculated (%); C: 61.54, H: 4.30, O: 3
4.16, actual value (%); C: 61.88, H: 4.20, O: 3
3.92,

(Example-84) 2-formyloxy-4-
Methoxyindane-1,3-dione (Compound 84) In (Example-83), 2-formyloxy-4-methoxyindane-1,
12.99 g of 3-dione were obtained.

Yield 74% H-NMR (CDCl ₃ ) δ = 3.90 (s, 3H, C
H ₃ ), 5.16 (s, 1 H, CH (OCOH)),
7.20-8.00 (m, 3H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₁ H ₈ as O ₅₎ Calculated (%); C: 60.00, H: 3.66, O: 3
6.33, actual value (%); C: 59.88, H: 3.50, O: 3
6.62,

Example-85 2- Propionyloxy -4-methoxyindane-1,3-dione (Compound 8
5) In (Example-83), using propionic acid instead of acetic acid, 13.45 g of 2- propionyloxy -4-methoxyindane-1,3-dione was obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . 25 (q, 2H, J = 8H
z, CH ₂ ), 5.16 (s, 1H, CH (OCOC)
_{H 2 CH 3)), 7.20~8.00} (m, 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₃ H ₁₂ O ₅₎ Calculated value (%); C: 62.90, H: 4.87, O: 3
2.23, actual value (%); C: 62.88, H: 5.03, O: 3
2.09,

(Example-86) 2-butyryloxy-4
-Methoxyindane-1,3-dione (Compound 86) In (Example-83), butyric acid was used instead of acetic acid to give 2-butyryloxy-4-methoxyindane-
15.19 g of 1,3-dione was obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.35 (q, 2H, J = 8 Hz, CH ₂ ); 1
6 (s, 1H, CH (OCOCH ₂ CH ₂ CH ₃ ), 7.
20 to 8.00 (m, 3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₄ H ₁₄ O ₅₎ Calculated value (%); C: 64.11, H: 5.38, O: 3
0.51, actual value (%); C: 64.23, H: 5.20, O: 3
0.57,

(Example-87) 2-acetyloxy-5-
Methoxyindane-1,3-dione (Compound 87) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-5-methoxyindane-1, 3-dione 16.12
g (0.0798 mol) using 2-acetyloxy-
13.26 g of 5-methoxyindane-1,3-dione were obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 2.19 (s, 3H, C
H ₃ ), 3.85 (s, 3H, CH ₃ ), 5.18 (s,
1H, CH (OAc)), 6.85 to 8.00 (m, 3
H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₂ H ₁₀ as O ₅₎ Calculated (%); C: 61.54, H: 4.30, O: 3
4.16, actual value (%); C: 61.90, H: 4.20, O: 3
3.90,

(Example-88) 2-formyloxy-5-
Methoxyindan-1,3-dione (Compound 88) In (Example-87), 2-formyloxy-5-methoxyindane-1,
12.46 g of 3-dione were obtained.

Yield 71% H-NMR (CDCl ₃ ) δ = 3.90 (s, 3H, C
_{H 3), 5.16 (s,} 1H, CH (OCOH)),
6.85 to 8.00 (m, 3H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₁ H ₈ as O ₅₎ Calculated (%); C: 60.00, H: 3.66, O: 3
6.33, actual value (%); C: 59.90, H: 3.50, O: 3
6.60,

Example 89: 2- propionyloxy -5-methoxyindane-1,3-dione (compound 8
9) In (Example-87), using propionic acid instead of acetic acid, 13.45 g of 2- propionyloxy -5-methoxyindane-1,3-dione was obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . 25 (q, 2H, J = 8H
z, CH ₂ ), 5.16 (s, 1H, CH (OCOC)
_{H 2 CH 3)), 6.90~8.00} (m, 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₃ H ₁₂ O ₅₎ Calculated value (%); C: 62.90, H: 4.87, O: 3
2.23, actual value (%); C: 62.85, H: 5.00, O: 3
2.15

(Example-90) 2-butyryloxy-5
-Methoxyindane-1,3-dione (Compound 90) In (Example-87), butyric acid was used instead of acetic acid to give 2-butyryloxy-5-methoxyindane-
15.19 g of 1,3-dione was obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.35 (q, 2H, J = 8 Hz, CH ₂ ); 1
5 (s, 1H, CH (OCOCH ₂ CH ₂ CH ₃ ));
95 to 8.00 (m, 3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₄ H ₁₄ O ₅₎ Calculated value (%); C: 64.11, H: 5.38, O: 3
0.51, actual value (%); C: 64.20, H: 5.15, O: 3
0.65

(Example-91) 2-acetyloxy-4-
Hexyloxyindane-1,3-dione (compound 9
1) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-4-hexyloxyindane-1,3-dione 2
Using 1.70 g (0.0798 mol), 16.73 g of 2-acetyloxy-4-hexyloxyindane-1,3-dione was obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 8
_{H, CH 2), 2.19 (} s, 3H, CH 3), 3.9
5 (t, 2H, J = 8 Hz, CH ₂ ), 5.18 (s,
1H, CH (OAc)), 7.20-8.00 (m,
3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₇ H ₂₀ O ₅₎ Calculated value (%); C: 67.09, H: 6.62, O: 2
6.29, actual value (%); C: 67.23, H: 6.55, O: 2
6.22,

(Example-92) 2-formyloxy-4-
Hexyloxyindane-1,3-dione (compound 9
2) In (Example-91), 17.12 g of 2-formyloxy-4-hexyloxyindane-1,3-dione was obtained by using formic acid instead of acetic acid.

Yield 74% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 8
H, CH ₂ ), 3.95 (t, 2H, J = 8 Hz, CH
₂ ), 5.16 (s, 1H, CH (OCOH)), 7.
20-8.00 (m, 3 H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₆ H ₁₈ O ₅₎ Calculated value (%); C: 66.19, H: 6.25, O: 2
7.56, actual value (%); C: 66.23, H: 6.45, O: 2
7.32,

(Example-93) 2- Propionyloxy -4-hexyloxyindane-1,3-dione (Compound 93) In (Example-91), 2- propionyloxy -4-hexyloxyindane-1,3-dione was used in place of acetic acid, and propionic acid was used. 17.25 g of propionyloxy -4-hexyloxyindane-1,3-dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 8
H, CH ₂ ), 2.25 (q, 2H, J = 8 Hz, CH
₂ ), 5.16 (s, 1H, CH (OCOCH ₂ C
_{H 3)), 7.20~8.00 (m} , 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₈ H ₂₂ O as ₅₎ Calculated (%); C: 67.91, H: 6.97, O: 2
5.13, actual value (%); C: 67.73, H: 6.75, O: 2
5.52,

(Example-94) 2-butyryloxy-4
-Hexyloxyindane-1,3-dione (compound 9
4) In (Example-91), using butyric acid instead of acetic acid, 18.54 g of 2-butyryloxy-4-hexyloxyindane-1,3-dione was obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.30} (m, 10
H, CH ₂ ), 2.35 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ CH _{2)
CH 3), 7.20~ 8.00 (m} , 3H, arom), IR (KBr) = 1755,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₉ H ₂₄ O ₅₎ Calculated value (%); C: 68.65, H: 7.28, O: 2
4.07, actual value (%); C: 68.23, H: 7.23, O: 2
4.54,

(Example-95) 2-Acetoxy-5-
Hexyloxyindane-1,3-dione (compound 9
5) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-5-hexyloxyindane-1,3-dione 2
Using 1.70 g (0.0798 mol), 16.73 g of 2-acetyloxy-5-hexyloxyindane-1,3-dione was obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.35
(T, 3H, J = 8 Hz, CH ₃ ), 1. 55-2.
_{20 (m, 8H, CH 2} ), 2.19 (s, 3H, C
H ₃ ), 3.95 (t, 2H, J = 8 Hz, CH ₂ ),
5.18 (s, 1H, CH (OAc)), 6.85
8.00 (m, 3H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₇ H ₂₀ O ₅₎ Calculated value (%); C: 67.09, H: 6.62, O: 2
6.29, actual value (%); C: 67.33, H: 6.45, O: 2
6.22,

(Example-96) 2-formyloxy-5-
Hexyloxyindane-1,3-dione (compound 9
6) In (Example-95), using formic acid instead of acetic acid, 16.65 g of 2-formyloxy-5-hexyloxyindane-1,3-dione was obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 8
H, CH ₂ ), 3.95 (t, 2H, J = 8 Hz, CH
₂ ), 5.16 (s, 1H, CH (OCOH)), 6.
90-8.00 (m, 3H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₆ H ₁₈ O ₅₎ Calculated value (%); C: 66.19, H: 6.25, O: 2
7.56, actual value (%); C: 66.20, H: 6.45, O: 2
7.35,

(Example-97) 2- Propionyloxy -5-hexyloxyindane-1,3-dione (Compound 97) 17.25 g of propionyloxy -5-hexyloxyindane-1,3-dione were obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 8
H, CH ₂ ), 2.25 (q, 2H, J = 8 Hz, CH
₂ ), 5.16 (s, 1H, CH (OCOCH ₂ C
_{H 3)), 6.85~8.00 (m} , 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₈ H ₂₂ O as ₅₎ Calculated (%); C: 67.91, H: 6.97, O: 2
5.13, actual value (%); C: 67.75, H: 6.75, O: 2
5.50,

(Example 98) 2-butyryloxy-5
-Hexyloxyindane-1,3-dione (compound 9
8) In (Example-91), using butyric acid instead of acetic acid, 18.54 g of 2-butyryloxy-5-hexyloxyindane-1,3-dione was obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.30 (m, 10
H, CH ₂ ), 2.35 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ CH ₂₎
CH _3), 7.20~8. 00 (m, 3H, aromatic), IR (KBr) = 1755, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₉ H ₂₄ O ₅₎ Calculated value (%); C: 68.65, H: 7.28, O: 2
4.07, actual value (%); C: 68.35, H: 7.25, O: 2
4.40,

(Example-99) 2-acetyloxy-4-
Octyloxyindane-1,3-dione (compound 9
9) In (Example-75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-4-octyloxyindane-1,3-dione 2
Using 3.94 g (0.0798 mol), 18.0 g of 2-acetyloxy-4-octyloxyindane-1,3-dione was obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.20} (m, 12
_{H, CH 2), 2.19 (} s, 3H, CH 3), 3.95
(T, 2H, J = 8 Hz, CH ₂ ), 5.18 (s, 1
H, CH (OAc)), 7.20-8.00 (m, 3
H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₉ H ₂₄ O ₅₎ Calculated value (%); C: 68.65, H: 7.28, O: 2
4.07, actual value (%); C: 68.23, H: 7.23, O: 2
4.54,

(Example-100) 2-formyloxy-4
-Octyloxyindane-1,3-dione (compound 1
00) In Example 99, 18.27 g of 2-formyloxy-4-octyloxyindane-1,3-dione was obtained using formic acid instead of acetic acid.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 12
H, CH ₂ ), 3.95 (t, 2H, J = 8 Hz, C
_{H 2), 5.16 (s,} 1H, CH (OCOH)),
7.20-8.00 (m, 3H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₈ H ₂₂ O as ₅₎ Calculated (%); C: 67.91, H: 6.97, O: 2
5.13, actual value (%); C: 68.13, H: 7.03, O: 2
4.84,

(Example-101) 2- propionyloxy -4-octyloxyindane-1,3-dione (Compound 101) In (Example-99), propionic acid was used in place of acetic acid. This gave 17.25 g of 2- propionyloxy -4-octyloxyindane-1,3-dione.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 12
H, CH ₂ ), 2.25 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ C)
_{H 3)), 7.20~8.0 0 (} m, 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₂₀ H ₂₆ O as ₅₎ Calculated (%); C: 69.34, H: 7.57, O: 2
3.09, actual value (%); C: 69.23, H: 7.45, O: 2
3.32,

(Example-102) 2-butyryloxy-
4-octyloxyindane-1,3-dione (Compound 102) In (Example-99), butyric acid was used in place of acetic acid, and 2-butyryloxy-4-octyloxyindane-1,3-dione was used. 11 g were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.30} (m, 14
H, CH ₂ ), 2.35 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ CH _{2)
CH 3), 7.20~ 8.00 (m} , 3H, arom), IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) UV (MeOH) = 240,275 (nm) Elemental analysis (as C ₂₁ H ₂₈ O ₅ ) Calculated (%); C: 69.97, H: 7.83, O: 2
2.20, actual value (%); C: 69.87, H: 7.73, O: 2
2.40,

(Example-103) 2-acetyloxy-5
-Octyloxyindane-1,3-dione (compound 1
03) In (Example 75), instead of 2-diazo-4-benzyloxyindane-1,3-dione, 2-diazo-5-octyloxyindane-1,3-dione 2
Using 3.94 g (0.0798 mol), 18.0 g of 2-acetyloxy-5-octyloxyindane-1,3-dione was obtained.

Yield 68% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.20} (m, 12
_{H, CH 2), 2.19 (} s, 3H, CH 3), 3.95
(T, 2H, J = 8 Hz, CH ₂ ), 5.18 (s, 1
H, CH (OAc)), 6.85-8.00 (m, 3
H, aromatic) IR (KBr) = 1740, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₉ H ₂₄ O ₅₎ Calculated value (%); C: 68.65, H: 7.28, O: 2
4.07, actual value (%); C: 68.30, H: 7.25, O: 2
4.45,

(Example-104) 2-formyloxy-5
-Octyloxyindane-1,3-dione (compound 1
04) In (Example-103), using formic acid instead of acetic acid, 18.27 g of 2-formyloxy-5-octyloxyindane-1,3-dione was obtained.

Yield 72% H-NMR (CDCl ₃ ) δ = 1.35 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.20} (m, 12
H, CH ₂ ), 3.95 (t, 2H, J = 8 Hz, C
_{H 2), 5.16 (s,} 1H, CH (OCOH)),
6.85 to 8.00 (m, 3H, aromatic), 9.50
(S, 1H, OCOH) IR (KBr) = 1760, 1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₁₈ H ₂₂ O as ₅₎ Calculated (%); C: 67.91, H: 6.97, O: 2
5.13, actual value (%); C: 68.15, H: 7.00, O: 2
4.85,

(Example-105) 2- Propionyloxy -5-octyloxyindane-1,3-dione (Compound 105) In (Example-103), propionic acid was used in place of acetic acid. This gave 17.50 g of 2- propionyloxy -5-octyloxyindane-1,3-dione.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 1} . 55 to 2.20 (m, 12
H, CH ₂ ), 2.25 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ C)
_{H 3)), 6.90~8.0 0 (} m, 3H, aromatic), IR (KBr) = 1760,1720 (C = O) (cm
^{-1) UV (MeOH) = 240,275} (nm) Elemental analysis (C ₂₀ H ₂₆ O as ₅₎ Calculated (%); C: 69.34, H: 7.57, O: 2
3.09, actual value (%); C: 69.45, H: 7.45, O: 2
3.10,

(Example-106) 2-butyryloxy-
5-octyloxyindane-1,3-dione (Compound 106) In (Example-103), butyric acid was used in place of acetic acid, and 2-butyryloxy-5-octyloxyindane-1,3-dione was used. 88 g were obtained.

Yield 69% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1.55~2.30} (m, 14
H, CH ₂ ), 2.35 (q, 2H, J = 8 Hz, C
H ₂ ), 5.16 (s, 1H, CH (OCOCH ₂ CH _{2)
CH 3), 7.00~ 8.00 (m} , 3H, arom), IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) UV (MeOH) = 240,275 (nm) Elemental analysis (as C ₂₁ H ₂₈ O ₅ ) Calculated (%); C: 69.97, H: 7.83, O: 2
2.20, actual value (%); C: 69.90, H: 7.70, O: 2
2.40,

(Example-107) 2-acetyloxy-4
-Hydroxyindane-1,3-dione (compound 10
7) 2-acetyloxy-4-benzyloxyindane-1,3
13.08 g (0.0464 mol) of dione was dissolved in 523 ml of ethyl acetate, and 0.26 g of 10% palladium on carbon was dissolved.
After adding 2 g, the inside of the reaction system was replaced with hydrogen and stirred at room temperature overnight. After filtering off the catalyst, the ethyl acetate was concentrated under reduced pressure.
A crude product of the desired product was obtained. This was recrystallized from THF-hexane to give 2-acetyloxy-4-.
6.85 g of hydroxyindane-1,3-dione were obtained.

Yield 77% H-NMR (CDCl ₃ ) δ = 2.23 (s, 3H, C
_{H 3), 5.16 (s,} 1H, CH (OAc)), 7.
30 to 7.81 (m, 3H, aromatic), 8.45 (b
s, 1H, OH), IR (KBr) = 3400 (OH), 1730, 170
0 (C = O) (cm ^-1 ) UV (MeOH) = 230,335 (nm) Melting point 148-150 ° C. Elemental analysis (as C ₁₁ H ₈ O ₅ ) Calculated (%); C: 60.00 , H: 3.66, O: 3
6.33, actual value (%); C: 59.87, H: 3.73, O: 3
6.40,

(Example-108) 2-formyloxy-4
-Hydroxyindane-1,3-dione (compound 10
8) In (Example-107), 2-acetyloxy-4-
Instead of benzyloxyindane-1,3-dione, 2
-Formyloxy-4-benzyloxyindane-1,3-
Using 8.50 g of dione, 4.02 g of 2-formyloxy-4-hydroxyindane-1,3-dione was obtained.

Yield 62% H-NMR (CDCl ₃ ) δ = 5.25 (s, 1H, C
H (OCOH)), 5. 30 (s, 2H, CH ₂ P
h), 7.34-8.00 (m, 3H, aromatic), 8.
65 (s, 1H, OH), 9.50 (s, 1H, OC
OH), IR (KBr) = 3300 (OH), 1760, 172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240, 330 (nm) Elemental analysis value (as C ₁₀ H ₆ O ₅ ) Calculated value (%); C: 58.26, H: 2. 90, O: 3
8.81, actual value (%); C: 58.45, H: 2.73, O: 3
8.82,

(Example-109) 2- propionyloxy -4-hydroxyindan-1,3-dione (compound 109) In Example-107, 2-acetyloxy-4-
Instead of benzyloxyindane-1,3-dione, 2
-Propionyloxy -4-benzyloxyindane-
Using 6.56 g of 1,3-dione, 2- propionyloxy -4-hydroxyindane-1,3-dione;
30 g were obtained.

Yield 70% H-NMR (CDCl ₃ ) δ = 1.45 (t, 3H, J
_{= 8Hz, CH 3), 2} . 35 (q, 2H, J = 8H
z, CH ₂ ), 5.15 (s, 1H, CH (OCOC)
H ₂ CH ₃ )), 5.30 (s, 2H, CH ₂ Ph),
7.20 to 8.00 (m, 3H, aromatic), 8.85
(S, 1H, OH) IR (KBr) = 3325 (OH), 1760, 172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,335 (nm) Elemental analysis (as C ₁₂ H ₁₀ O ₅ ) Calculated (%); C: 61.54, H: 4. 30, O: 3
4.16, actual value (%); C: 61.87, H: 4.45, O: 3
3.68,

(Example-110) 2-butyryloxy-
4-hydroxyindane-1,3-dione (compound 1
10) In (Example-107), 2-acetyloxy-4-
Instead of benzyloxyindane-1,3-dione, 2
-Butyryloxy-4-benzyloxyindane-1,3
2-butyryl-4 using 6.00 g of dione
3.17 g of -hydroxyindane-1,3-dione were obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.40 (q, 2H, J = 8 Hz, CH ₃ ), 5.16
(S, 1H, CH (OCOCH ₂ CH ₂ CH ₃ )), 5.
_{30 (s, 2H, CH 2} Ph), 7.20~8.00
(M, 3H, aromatic), 9.00 (s, 1H, OH) IR (KBr) = 3300 (OH), 1755, 172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,325 (nm) Elemental analysis (as C ₁₃ H ₁₂ O ₅ ) Calculated (%); C: 62.90, H: 4. 87, O: 3
2.23, actual value (%); C: 62.87, H: 4.67, O: 3
2.46,

(Example-111) 2-acetyloxy-5
-Hydroxyindane-1,3-dione (compound 11
1) In (Example-107), 2-acetyloxy-4-
Instead of benzyloxyindane-1,3-dione, 2
Acetyloxy-5-benzyloxyindane-1,3-
Using 7.00 g (0.0248 mol) of dione, 2-
3.20 g of acetyloxy-5-hydroxyindane-1,3-dione were obtained.

Yield 67% H-NMR (CDCl ₃ ) δ = 2.15 (s, 3H, C
_{H 3), 5.67 (s,} 1H, CH (OAc)), 7.
16 to 7.81 (m, 3H, aromatic), 11.38 (b
s, 1H, OH), IR (KBr) = 3200 (OH), 1750, 171
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,280 (nm) Melting point 164-165 ° C. Elemental analysis value (as C ₁₁ H ₈ O ₅ ) Calculated value (%); C: 60.00 , H: 3.66, O: 3
6.33, actual value (%); C: 59.90, H: 3.75, O: 3
6.35,

(Example-112) 2-formyloxy-5
-Hydroxyindane-1,3-dione (compound 11
2) In (Example-111), 2-acetyloxy-5-
Instead of benzyloxyindane-1,3-dione, 2
-Formyloxy-5-benzyloxyindane-1,3-
Using 7.00 g of dione, 3.16 g of 2-formyloxy-4-hydroxyindane-1,3-dione were obtained.

Yield 65% H-NMR (CDCl ₃ ) δ = 5.20 (s, 1H, C
H (OCOH)), 5. 30 (s, 2H, CH ₂ P
h), 7.35 to 8.00 (m, 3H, aromatic);
75 (s, 1H, OH), 9.50 (s, 1H, OC
OH), IR (KBr) = 3300 (OH), 1760, 172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,280 (nm) Elemental analysis (as C ₁₀ H ₆ O ₅ ) Calculated (%); C: 58.26, H: 2. 90, O: 3
8.81, actual value (%); C: 58.45, H: 2.75, O: 3
8.80,

(Example-113) 2- propionyloxy -5-hydroxyindane-1,3-dione (Compound 113) In Example-111, 2-acetyloxy-5-
Instead of benzyloxyindane-1,3-dione, 2
-Propionyloxy -5-benzyloxyindane-
Using 5.55 g of 1,3-dione, 2- propionyloxy -5-hydroxyindane-1,3-dione;
00 g were obtained.

Yield: 72% H-NMR (CDCl ₃ ) δ = 1.45 (t, 3H, J
_{= 8Hz, CH 3), 2} . 35 (q, 2H, J = 8H
z, CH ₂ ), 5.25 (s, 1H, CH (OCOC)
H ₂ CH ₃ )), 5.30 (s, 2H, CH ₂ Ph),
7.20-8.00 (m, 3H, aromatic), 9.05
(S, 1H, OH) IR (KBr) = 3325 (OH), 1760, 172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,275 (nm) Elemental analysis value (as C ₁₂ H ₁₀ O ₅ ) Calculated value (%); C: 61.54, H: 4. 30, O: 3
4.16, actual value (%); C: 61.80, H: 4.40, O: 3
3.80,

(Example-114) 2-butyryloxy-
5-hydroxyindane-1,3-dione (compound 1
14) In (Example-111), 2-acetyloxy-5-
Instead of benzyloxyindane-1,3-dione, 2
-Butyryloxy-5-benzyloxyindane-1,3
2-butyryl-5 using 6.00 g of dione.
3.20 g of -hydroxyindane-1,3-dione were obtained.

Yield 73% H-NMR (CDCl ₃ ) δ = 1.30 (t, 3H, J
_{= 8Hz, CH 3), 1} . _{55 (m, 2H, CH 2} ),
2.40 (q, 2H, J = 8 Hz, CH ₃ ); 2
0 (s, 1H, CH (OCOCH ₂ CH ₂ CH ₃ )),
5.30 (s, 2H, C H 2 Ph), 7.20~8.
00 (m, 3H, aromatic), 9.00 (s, 1H, O
H) IR (KBr) = 3300 (OH), 1755,172
0 (C = O) (cm ^-1 ) UV (MeOH) = 240,280 (nm) Elemental analysis value (as C ₁₃ H ₁₂ O ₅ ) Calculated value (%); C: 62.90, H: 4. 87, O: 3
2.23, actual value (%); C: 62.80, H: 4.65, O: 3
2.55

(Example-115) 4-Acetoxy-2-
Formyloxyindane-1,3-dione (compound 11
5) 2-formyloxy-4-hydroxyindane-1,3-
1.00 g (4.85 mmol) of dione was added to pyridine 10.0
Dissolved in ml and cooled to 0 ° C. Acetyl chloride 0.
456 g (5.81 mmol) was added and reacted for 2 hours.
The reaction solution was poured into 100 ml of water, and the precipitate was filtered, dried and dried to give 4-acetoxy-2-formyloxyindane-1,4-acetoxy-2-formyloxyindane.
1.09 g of 3-dione were obtained.

Yield 85% H-NMR (CDCl ₃ ) δ = 2.20 (s, 3H, C
_{H 3), 5.20 (s,} 1H, CH (OCOH)),
7.20-8.00 (m, 3H, aromatic), 9.00
(S, 1H, COH) IR (KBr) = 1755,1720 (C = O) (cm
^-1) Elemental analysis (C ₁₂ as H ₈ O ₆₎ Calculated (%); C: 58.02, H: 3.25, O: 3
8.68, actual value (%); C: 58.45, H: 3.35, O: 3
8.20,

(Example-116) 2,4-diacetoxyindane-1,3-dione (compound 116) In Example-115, 2-formyloxy-4-
Instead of hydroxyindane-1,3-dione, 2-
Using 1.00 g of acetoxy-4-hydroxyindane-1,3-dione, 0.98 g of 2,4-diacetoxyindane-1,3-dione was obtained.

Yield 82% H-NMR (CDCl ₃ ) δ = 2.20 (s, 3H, C
_{H 3), 2.30 (s,} 3 H, CH 3), 5.20
(S, 1H, CH (OAc)), 7.20-8.00.
(M, 3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^-1) Elemental analysis (C ₁₃ H ₁₀ as O ₆₎ Calculated (%); C: 59.54, H: 3.84, O: 3
6.61, actual value (%); C: 59.45, H: 3.75, O: 3
6.80,

(Example-117) 4-acetoxy-2-
Propionyloxyindane -1,3-dione (Compound 117) In Example-115, 2-formyloxy-4-
Instead of hydroxyindane-1,3-dione, 2-
Propionyloxy -4-hydroxyindane-1,3
-Diacetone using 1.00 g, 4-acetoxy-2-
Propionyloxyindane -1,3-dione comprises:
00 g was obtained.

Yield 85% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . _{20 (s, 3H, CH 3} ),
2.30 (q, 2H, J = 8 Hz, CH ₂ ); 2
0 (s, 1H, CH ( OCH 2 CH 3), 7.20~8.
00 (m, 3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₄ H ₁₂ O ₆ ) Calculated value (%); C: 60.87, H: 4.38, O: 3
4.75, actual value (%); C: 60.67, H: 4.56, O: 3
4.67,

(Example-118) 4-Propionyloxy-2-formyloxyindane-1,3-dione (Compound 118) In (Example-115), propionyl chloride was used in place of acetyl chloride. 1.06 g of 4-propionyloxy-2-formyloxyindane-1,3-dione was obtained.

Yield 80% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . _{20 (s, 3H, CH 3} ),
2.30 (q, 2H, J = 8 Hz, CH ₂ ); 2
0 (s, 1H, CH (OCOH)), 7.20-8.0.
0 (m, 3H, aromatic), 9.00 (s, 1H, OC
OH), IR (KBr) = 1755,1720 (C = O) (cm
^-1) Elemental analysis (C ₁₄ as H ₁₀ O ₆₎ Calculated (%); C: 61.32, H: 3.68, O: 3
5.01, actual value (%); C: 61.67, H: 3.56, O: 3
4.67,

(Example-119) 2-acetoxy-4-
Propionyloxyindane -1,3-dione (Compound 119) In (Example-118), 2-hydroxy-2-formyloxyindan-1,3-dione was replaced with 2-hydroxy-2-formyloxyindane-1,3-dione.
Using acetoxy-4-hydroxyindane-1,3-dione, 1.04 g of 2-acetoxy-4- propionyloxyindane -1,3-dione was obtained.

Yield 80% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . _{20 (s, 3H, CH 3} ),
2.30 (q, 2H, J = 8 Hz, CH ₂ ), 5.20
(S, 1H, CH (OCOCH 3)), 7.20~8.
00 (m, 3H, aromatic) IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₅ H ₁₂ O ₆ ) Calculated value (%); C: 62.50, H: 4.20, O: 3
3.30, actual value (%); C: 62.60, H: 4.36, O: 3
3.04,

(Example-120) 2-acetoxy-4-
Benzoyl ixindane-1,3-dione (compound 1
20) In (Example-119), using benzoyl chloride instead of propionyl chloride, 1.15 g of 2-acetoxy-4-benzoyloxyindane-1,3-dione was obtained.

Yield 78% H-NMR (CDCl ₃ ) δ = 2.20 (s, 3H, C
_{H 3), 5.20 (s,} 1H, CH (OCOCH 3)),
7.20 to 8.00 (m, 8H, aromatic) IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₈ H ₁₄ O ₆ ) Calculated value (%); C: 66.25, H: 4.32, O: 2
9.42, actual value (%); C: 66.32, H: 4.36, O: 2
9.32,

(Example-121) 2,5-Diacetoxyindane-1,3-dione (Compound 121) In place of 2-acetoxy-4-hydroxyindane-1,3-dione in (Example-116). Then, using 1.00 g of 2-acetoxy-5-hydroxyindan-1,3-dione, 2,5-diacetoxyindan-
0.98 g of 1,3-dione was obtained.

Yield 82% H-NMR (CDCl ₃ ) δ = 2.20 (s, 3H, C
H ₃ ), 2.30 (s, 3H, CH ₃ ), 5.20 (s,
1H, CH (OAc)), 7.20-8.00 (m,
3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^-1) Elemental analysis (C ₁₃ H ₁₀ as O ₆₎ Calculated (%); C: 59.54, H: 3.84, O: 3
6.61, actual value (%); C: 59.50, H: 3.75, O: 3
6.75,

(Example-122) 5-Acetoxy-2-
Propionyloxyindane -1,3-dione (Compound 122) In (Example 117), 2- propionyloxy -5-hydroxyindane- was used instead of 2-propionyloxy-4-hydroxyindane-1,3-dione. Using 1.00 g of 1,3-dione, 1.00 g of 5-acetoxy-2-propionyloxyindane-1,3-dione was obtained.

Yield: 85% H-NMR (CDCl ₃ ) δ = 1.40 (t, 3H, J
_{= 8Hz, CH 3), 2} . _{20 (s, 3H, CH 3} ),
2.30 (q, 2H, J = 8 Hz, CH ₂ ); 2
0 (s, 1H, CH ( OCH 2 CH 3), 7.20~8.
00 (m, 3H, aromatic), IR (KBr) = 1755,1720 (C = O) (cm
^-1 ) Elemental analysis value (as C ₁₄ H ₁₂ O ₆ ) Calculated value (%); C: 60.87, H: 4.38, O: 3
4.75, actual value (%); C: 60.67, H: 4.56, O: 3
4.67,

[0286]

According to the present invention, a novel indane-1,3-dione derivative having a hydroxyl group, an alkyloxy group, an alkenyloxy group, an aralkyloxy group, or an acyloxy group as a substituent and useful as a pharmaceutical is provided. It became possible to provide.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C07C 49/733 A61K 31/12 A61K 31/22 C07C 49/755 C07C 69/16 CAPLUS (STN) REGISTRY (STN )

Claims (6)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, and an acyl group;
₂ represents a hydrogen atom or an acyl group. And the physiologically acceptable salts thereof. 2. R ₁ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, and an acyl group.
_2. The indandione derivative according to claim 1, wherein ₂ is a hydrogen atom, and a physiologically acceptable salt thereof. 3. R ₁ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, and an acyl group.
_2. The indandione derivative according to claim 1, wherein ₂ is an acyl group, and a physiologically acceptable salt thereof. 4. The indandione derivative according to claim 1, wherein R ₁ is a hydrogen atom and R ₂ is a hydrogen atom or an acyl group, and a physiologically acceptable salt thereof. 5. The indandione derivative according to claim 1, wherein R ₁ is a hydrogen atom and R ₂ is an acyl group, and a physiologically acceptable salt thereof. 6. The method according to claim 1, wherein R ₁ and R ₂ are hydrogen atoms.
And the physiologically acceptable salts thereof.