JPH03375B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel compound, 4,4'-dipropioloyloxybenzophenone, which is useful as an intermediate for producing a substance that converts light energy into chemical energy, and a method for producing the same. Regarding.

In recent years, the storage of solar energy, which is enjoyed by living things on earth, as chemical energy in chemical substances has been attracting attention as an effective use of solar energy. Various methods have been studied for extracting solar energy as heat as desired, and in particular, valence isomerization methods using norbornadiene derivatives are widely known. but,
Norbornadiene itself has the disadvantage that it only absorbs sunlight in the short wavelength range and does not absorb most of the sunlight, so by introducing a functional group into norbornadiene, it can absorb sunlight even more efficiently. Various studies are being conducted to achieve this goal. However, these methods of introducing functional groups into norbornadiene require long steps and are time-consuming to produce, so they cannot be called industrial methods. On the other hand, the phototautomerism between cis and trans forms of olefins is not suitable for long-term storage because a dark reaction may occur from the cis form to the trans form.

In view of this, the present inventors have conducted intensive research and found a chemical substance that can easily absorb sunlight energy, convert it into chemical energy, and store that energy for a long period of time. We have discovered the most suitable reaction intermediate and its production method.

That is, the chemical substance according to the present invention is 4,4'-dipropioloyloxybenzophenone (hereinafter referred to as the present compound) represented by the formula (), and 4,4'-
This is a new substance that can be easily obtained in high yield by ester condensation of dihydroxybenzophenone and propiolic acid.

The novel compound () obtained here reacts rapidly and in high yield with cyclopentadiene, and is useful as a solar energy conversion substance, 4,4′-bis(2″- Norbornadienecarbonyloxy)benzophenone (hereinafter referred to as the compound).

This compound () easily absorbs sunlight and
4, which is an isomer of the compound represented by the following formula (),
It is converted into 4′-bis(1″-quadricyclenecarbonyloxy)benzophenone (hereinafter referred to as the compound) and stores solar energy.

This compound () is exothermically returned to compound () by contacting with a so-called reverse reaction catalyst, such as AgBF ₄ .

The compound of the present invention can be produced by the above-mentioned ester condensation, and N,N'-dicyclohexylcarbodiimide can be suitably used as the condensing agent in this case. N,N'-dicyclohexylcarbodiimide may be used in the reaction stoichiometric amount, and the solvent used may be esters, aliphatic halides, aromatic compounds, or ethers, and there are no particular limitations as long as it is an inert solvent. It is not something that will be done. Addition of amines as catalysts does not have any particular adverse effects. Furthermore, in place of N,N'-dicyclohexylcarbodiimide, acid catalysts commonly used in ester condensation, such as sulfuric acid, p-toluenesulfonic acid, and polyphosphoric acid, can also be used in the ester condensation.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but these examples do not limit the present invention in any way.

Example 1 10.0 g of 4,4'-dihydroxybenzophenone was dissolved in 300 ml of ethyl acetate, 7.7 g of propiolic acid was added thereto, and 19.0 g of N,N'-dicyclohexylcarbodiimide was added as a condensing agent under ice cooling. Add as
The reaction mixture was stirred for a period of time.

After the reaction, remove the precipitate by filtration, concentrate the liquid,
The target component was separated from 19.0 g of the obtained oil by silica gel column chromatography using a hexane-ethyl acetate mixed solvent (volume ratio 3:1), and after concentrating the solvent, recrystallization was performed from ethyl acetate-hexane. 10.0 g of 4,4'-dipropioloyloxybenzophenone was obtained. Yield 67%. The physical property values are as follows.

Melting point 157-158℃ White crystal nuclear magnetic resonance spectrum ( ^1H , _CDCl3 ) δ value (ppm) 3.07 (2H), 7.27 (d, 4H), 7.73 (d, 4H) Infrared absorption spectrum (KBr) (cm ¹ ) 3320,
2160, 1735, 1655, 1605, 1510, 1420, 1215,
940, 925 Elemental analysis values ( ) indicate calculated values.

C 61.52% (61.54%); H, 4.31% (4.30%) Example 2 Dissolve 10.0 g of 4,4'-dihydroxybenzophenone in 200 ml of tetrahydrofuran and add 7.5% to this.
g of propiolic acid was added to this solution under ice cooling.
After adding 19.0 g of N,N'-dicyclohexylcarbodiimide as a condensing agent and stirring at below 10°C for 10 minutes, 0.50 g of N,N-dimethyl-4 was added as a catalyst.
- After adding aminopyridine, the mixture was stirred for 5 hours at a temperature below 10°C, and then allowed to stand overnight at room temperature, followed by post-treatment in the same manner as in Example 1 to obtain 11.1 g of 4,4'-dipropioloyloxybenzophenone. I got it. yield
74% Melting point 157-158°C Nuclear magnetic resonance spectrum and infrared absorption spectrum were the same as in Example 1.

Claims (1)

[Claims] 1 4,4'-dipropioloyloxybenzophenone represented by formula (). 2. A method for producing 4,4'-dipropioloyloxybenzophenone, which comprises condensing 4,4'-dihydroxybenzophenone and propiolic acid in the presence of a condensing agent. 3. The manufacturing method according to claim 1, wherein the condensing agent is N,N'-dicyclohexylcarbodiimide.