JPH02286641A - Synthesis of 5,6,5',6'-tetrahydroxy-1,1'-spirobisindane - Google Patents

Abstract

PURPOSE:To synthesize the title compound of high purity in high yield in a short time by reaction between a catechol and a ketone in a mixture of hydro chloric acid and acetic acid or propionic acid pref. in a pressurized state by heating to a specified range of temperatures. CONSTITUTION:The objective 5,6,5',6'-tetrahydroxy-1,1'-spirobisindane of formula III can be obtained by reaction between a catechol of formula I (R1 and R2 are each H, halogen, alkyl, alkenyl, alkoxy or alkenoxy) (e.g. catechol) and a ketone of formula II (R3 is n, alkyl, alkenyl or aryl) (e.g. acetone) in a mixture of hydrochloric acid, acetic acid or propionic acid at 105-140 deg.C. It is preferable that the reaction be carried out under pressure esp. in a mixture of hydrochloric acid and acetic acid. In particular, at 105-120 deg.C, both the yield and purity of the compound of the formula III will be improved with rise in the reaction temperature. The present compound is useful as an intermediate for the image stabilizers for color photographs.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides 5,6.5',6°-tetrahydroxy-1, which is useful as an intermediate for producing an image stabilizer for color photography. , 1'-spirobisindanes.

[Conventional technology]

In general, color images obtained by photographically processing silver halide color photographic materials are composed of azomethine dyes or indoaniline dyes, and these dyes are formed by the reaction of an oxide of an aromatic primary amine developing agent with a coupler. Ru. Such color photographic images are not necessarily stable to light, humidity or heat. Therefore, if exposed to light for a long time,
Alternatively, if it is stored under high temperature and high humidity, fading or discoloration may occur, resulting in deterioration of image quality.

For the purpose of preventing the above-mentioned image quality deterioration, a method of incorporating various stabilizers into the photographic layer of a silver halide color photographic light-sensitive material is widely used.

As this type of stabilizer, a compound represented by the following formula (IV) is known (Japanese Patent Publication No. 45545/1989).

R, R,, R2, and R in the above formula represent the following, respectively.

R; alkyl group, alkenyl group, aryl group, tetrahydropyranyl group, pyridinyl group, R4Co, R5so2
or R6NHCO (However, R4 and R9 represent an alkenyl group, a pyridyl group or a pyrimidyl group. Also, R6
represents an alkyl group, alkenyl group, aryl group, pyridyl group or pyrimidyl group. ) R1 and R2; hydrogen atom, halogen atom, alkyl group, alkenyl group,
Alkoxy group or alkenoxy group R3; hydrogen atom, alkyl group, alkenyl group, or aryl group This stabilizer does not cause any change in hue or fog,
Demonstrates sufficient effect in preventing fading and discoloration of color images. It also has excellent properties such as excellent solubility in high boiling point solvents and no formation of microcrystals before and after application.

By the way, the above stabilizer compound (IV) is the compound to be synthesized according to the present invention, that is, 5. G, 5°, 6°-tetrahydroxy-
Derived from 1,1°-spirobisindanes. This spirobisindane is represented by the following structural formula (III), and the stabilizer compound (IV) can be obtained by 0-alkylating or esterifying its phenolic -〇i1 group by a conventional method. . Therefore, 5,0,5°,6°-tetrahydroxy-1, which is the object of synthesis of the present invention,
1'-spirobisindane (111) is useful and important as a synthetic intermediate for stabilizer compound (IV').

However, R, , R2, and R are the same as explained in formula (1).

5. As a method for synthesizing 0.5°, 6°-tetrahydroxyspirobisindanes (III), a conventionally known method is to condense catechols and ketones in a mixture of acetic acid and hydrogen chloride under normal pressure. (J,
C11ea+, Soc, , 1934, 1078
-1081 and Ber, 1905.38.2307
), the method is - step □ step reaction ya purpose 5, 0.
5°, 0°-tetrahydroxyspirobisindanes (
m) can be obtained, and has the advantage that it can be carried out under normal pressure. However, it is still unsatisfactory in terms of product purity and yield, and has the disadvantage that the reaction requires a long time.

Note that the following literature describes another method for synthesizing hydroxy-1,1°-spirobisindanes.

However, the products obtained by these methods are the object of the present invention, 5,6.5°,6′-tetrahydroxy-
A compound different from 1,1'-spirobisindanes (m).

・ ChcIIl, Ind., London, LH9,
456-457・Rev, Chcm(Bucharcs
t), 1983.134.1069-74 [Problem to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to condense catechols and ketones to obtain a solution of 5.6,5°, 6'=t. The method for synthesizing trahydroxy-1,1'-spirobisindanes (m) has been improved, and highly pure 5. [i, 5°, 6°-tetrahydroxy-1,1゛-spirobisindanes (m
) can be synthesized in high yield and in a short time.

[Means to solve the problem]

In order to achieve the above problems, 5, G, 5 according to the present invention
In the method for synthesizing °,6°-tetrahydroxy-1,1°-spirobisindanes, catechols and ketones are mixed in a mixture of hydrochloric acid and acetic acid or propionic acid at a temperature of 105 to 140°C, The reaction is preferably carried out under pressure.

All reactions in the synthesis method of the present invention are shown by the following reaction formula.

(If) (II) The catechols used in the present invention are represented by the structural formula (1) in the above reaction formula. However, R1 and R2 are each a hydrogen atom,
Halogen atoms (e.g. fluorine, chlorine, bromine), alkyl groups (e.g. methyl, ethyl, 11-butyl, benzyl)
, an alkenyl group (eg allyl, hexenyl, octenyl), an alkoxy group (eg methoxy, ethoxy, benzyloxy) or an alkenoxy group (eg 2-propenyloxy, hexenyloxy).

The ketones used in the present invention have the structural formula (I
I). However, R3 is a hydrogen atom, an alkyl group (
for example methyl, ethyl, lobutyl, benzyl), alkenyl groups (for example 2-propenyl, hexenyl, octenyl) or aryl groups (for example phenyl, methoxyphenyl, chlorphenyl, naphthyl).

5. Obtained in the present invention by specifying the substitutions MR,, R2, and R3. G, 5', Go-tetrahydroxy 1
．． Specific examples of 1°-spirobisindanes (m) are shown in Table 1 below.

Example of compound R+ R2R3 1II II II 2 II If (I+33
0(II3 II II4
II II Phenyl 5 HII
Phenyl 6 011 11 H The main conditions in the synthesis method of the present invention are as follows.

Ketones (II) per mol of catechols (I)
The amount used is usually 1 to 3 mol, preferably 1.5 to 1.
It is 8 moles.

The amount of hydrochloric acid used per 1 mol of catechols (I) is usually 2.0 to 0 mol, preferably 3.7 to 4.3 mol as concentrated hydrochloric acid (36%). Note that in the present invention, hydrogen chloride gas may be used instead of concentrated hydrochloric acid.

The amount of acetic acid (preferably glacial acetic acid) to be used per mol of catechol (I) is usually 0.1 to 7.0 mol, preferably 1.1 to 4.6 mol. Note that other organic acids such as propionic acid may be used in place of acetic acid or in combination with acetic acid.

The reaction temperature is usually 105 to 140°C, preferably 110 to 130°C, more preferably 115 to 125°C.
It is ℃.

The reaction time is usually 1 to 10 hours, preferably 3 to 8 hours.

For carrying out the synthetic method according to the invention, in particular when using acetic acid, preferably pressure-resistant closed containers are used. hydrochloric acid/
As shown in FIG. 1 for a system using acetic acid, the internal pressure during the reaction is uniquely determined by the reaction temperature. for example,
The internal pressure at a reaction temperature of 105-1400C is about 2.4-7.
0 kg/Cm2. In addition, the reaction temperature is 110℃
When the reaction temperature is 120°C, the internal pressure is about 3.0 kg/cm2, and when the reaction temperature is 120°C, the internal pressure is about 4.0 kg/cm2.

In the method of the present invention, significantly higher yields are obtained compared to conventional methods. In particular, a yield of about 80% or more can be obtained in the temperature range of 105 to 120°C.

This value is extremely high compared to the yield of 65% when the reaction is carried out under normal pressure and at a temperature of 95° C. as in the conventional example. Furthermore, the yield in the range of 120 to 140°C is also significantly higher than in conventional examples.

It is noteworthy that in the temperature range of 105 to 120 °C,
The yield and purity of the product (m) both increase with increasing reaction temperature. On the other hand, the reaction temperature was 120
Since the product decomposes above 0.degree. C., both yield and purity decrease with increasing temperature. This tendency is particularly noticeable when the temperature exceeds 140°C. The relationship between this reaction temperature, yield and purity is shown in FIG.

〔Example〕

Examples 1 to 5 These Examples were carried out in the following manner using 11 pressure-resistant chemical reaction apparatuses (TEN-V type, manufactured by Tense Glass Industry Co., Ltd.) equipped with stirring blades, pressure gauges, safety valves, and thermometers. Ta.

First, 72.8 g of catechol, 212 mL of concentrated hydrochloric acid, 1601 g of glacial acetic acid, and 57.8 g of acetone were charged into the above reaction apparatus. Next, the temperature of the reaction system was set to 1204t4o 0c
After raising the temperature to a predetermined temperature in the range of (the temperature shown in Table 2), the mixture was reacted for 5 hours with stirring.

In any of the examples, the internal pressure increased as the temperature rose, and reached a constant internal pressure shown in Table 2 at the predetermined temperature, resulting in a steady state.

At the end of the reaction, 5% was added to the reaction solution in all Examples.
．． G, 5°, 6′-tetrahydroxy-1,1′-spirobisindane crystal precipitation was observed. Approximately 10% of the reaction solution
After cooling to ℃ and filtering, the obtained crystals were washed with acetonitrile 8 (1 ml).Furthermore, after washing with 400 ml of water, they were dried at a temperature of 60 ℃ and under reduced pressure.The crystals obtained in any of the examples were , the melting point is 255-270 °C (decomposition),
J.Chem.Soc., 1934.1878-
1681. Liquid chromatography also revealed that this crystal was 5.6.5', G
It was confirmed to be o-tetrahydroxy-1,1°-spirobisindane.

The crystals after drying were weighed and the yield was calculated. Purity was also measured by liquid chromatography.

The results of Examples 1 to 5 are summarized in Table 2 together with the results of the comparative examples below.

Comparative Example Into a III three-loaf flask equipped with a reflux condenser, thermometer and stirring blade, 72.8 g of catechol, 2121 g of concentrated hydrochloric acid,
180 ml of glacial acetic acid and 57.8 g of acetic acid were charged.

The temperature of the reaction system was raised to 95° C. and stirred at this temperature for 16 hours. At this time, 5.6.5", Oo-
Crystal precipitation of tetrahydroxy-1,1'-spirobisindane was observed. The reaction solution was cooled to about 10° C. and filtered, and the obtained crystals were washed with acetonitrile 801. Furthermore, after washing with 400 n+I of water, it was dried at a temperature of 60° C. under reduced pressure.

After drying, the amount of crystals was 72.0 g, and the yield was 64%.

In addition, the purity measured by liquid chromatography is 9
It was 2.6%.

Note that even when the reaction time was extended to 24 hours, the yield was 64.5%, with almost no change.

Table 2 Example 6 The reaction was carried out in exactly the same manner as in Example 3 except that an equal volume of propionic acid was used in place of glacial acetic acid, and the desired product was obtained in almost the same yield and purity.

〔Effect of the invention〕

As detailed above, according to the present invention, highly purified 5.6,5°,6°-tetrahydroxy-
Remarkable effects such as the ability to synthesize 1,1°-spirobisindanes can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between reaction temperature and internal pressure in the present invention, and FIG. 2 is a diagram showing the relationship between reaction temperature and yield and purity in the present invention.

Claims (2)

[Claims] (1) Catechols represented by the following general formula (I),
A ketone represented by the following general formula (II) is added to a mixture of hydrochloric acid and acetic acid or propionic acid at a concentration of 105 to 1
A method for synthesizing 5,6,5',6'-tetrahydroxy-1,1'-spirobisindanes represented by the following general formula (III), characterized by carrying out the reaction at a temperature of 40°C. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) However, R_1 and R_2 are hydrogen atoms and halogens, respectively. atom,
It represents an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group, and R_3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. (2) Catechol as the catechol (I),
2. The method according to claim 1, wherein acetone is used as the ketone (II) and the reaction is carried out under pressure in a mixture of hydrochloric acid and acetic acid.