JPS63135387A - Deuterated methacrylamidephenyl based porphyrin compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R represents cyclic group having pi-electron conjugation). EXAMPLE:Mono-(p-methacrylamide-d5 phenyl)-triphenylporphyrin. USE:An optical material useful for photosignal-processing and photosignal-memory with a low degree attenuation of incident light. PREPARATION:For example, 4mol pyrrole is reacted with 3mol benzaldehyde and 1mol p-nitrobenzaldehyde in a solvent for several tens of minutes - several hours while refluxing to form mono-(p-nitrophenyl)-triphenylporphyrin, followed by reduction of the nitro group thereof under neutral condition. Then the obtained mono-(p-aminophenyl)-triphenyl-porphyrin is reacted with an equimolar amount of methacryloyl halide-d5 in a solvent, if necessary, using a basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to deuterated methacrylamidophenyl-based porphyrin compounds useful as optical materials.

[Conventional technology]

In recent years, optical memory systems using high-intensity laser beams such as YAG lasers and dye lasers have attracted attention as a means of information processing. The development of system optical materials is progressing.What is important for optical materials is processing and storing optical signals. It is necessary to contribute to the memory of the signal.

Furthermore, from the viewpoint of the need for a high concentration of organic materials involved in optical signal processing and storage in the optical material, it is desirable that the optical material has a polymerizable structure and is used in the form of a polymer if necessary.

Until now, porphyrin-based materials such as tetraphenylporphyrin, tetranitrophenylporphyrin, tetracarboxyphenylporphyrin, and tetrapyridylporphyrin have attracted attention as organic materials capable of optical signal processing and storage. For example, these materials have the potential to be used as optical storage materials or photoconductive materials that utilize the photoisomerization phenomenon caused by proton transfer. However, these porphyrins are usually polymethyl methacrylate (P
It was often used dispersed in polymers such as MM), polyvinyl carbazole, polystyrene, and polyvinyl alcohol. For this reason, solubility in the guest polymer is a problem, and it is usually difficult to increase the concentration of the dispersed material, so it has the disadvantage that it does not absorb or emit light at the wavelength required as an optical material. there were.

As a means to solve this problem, attempts have been made to incorporate tetraphenylporphyrin moieties into the side chains of polymers obtained from compounds with olefinic double bonds and incorporate guest molecules into the polymer matrix at high concentrations. . As a result, it is possible to obtain a polymer film having a high 8/N ratio and having a concentration of optical functional material desirable as, for example, an optical storage material.

[Problem that the invention seeks to solve]

However, in porphyrin-based materials such as tetraphenylporphyrin, only hydrogen bonded to aromatic carbon exists, and molecular vibrational absorption caused by aromatic OH causes attenuation of incident light. When a binding compound and tetraphenylporphyrin are combined, there is a hydrogen that binds to an aliphatic carbon.
Molecular vibrational absorption caused by K has a half-width of absorption of aromatic OH
Since the absorption of aliphatic C′H appears in a wavelength range that is broader than the molecular vibrational absorption of OH and that absorption of aromatic OH does not appear, the attenuation of light incident on these compounds is large, and optical signal processing or There was a problem that the efficiency of optical signal storage was reduced.

The present invention has been made in order to solve the above-mentioned problems, and its purpose is to have a molecule suitable for optical signal processing and optical signal storage as described above in its side chain, and to The object of the present invention is to provide a polymerizable compound with a low degree of attenuation.

[Means for solving problems]

To summarize the present invention, the present invention relates to a deuterated methacrylamide phenyl-based porphyrin compound, which is represented by the following general formula (1): (wherein R represents a π-electron conjugated cyclic group) It is characterized by

To explain the present invention more specifically, the compounds of the present invention include haphenylporphyrin, nitrophenylporphyrin, carboxydiphenylporphyrin, biridylborphyrin.
It is characterized by a photofunctional organic material such as a photoresponsive or photomemory material bonded to a deuterated methacrylamidophenyl group.

The compound of the present invention is a novel compound that has not been described in any literature. The deuterated methacrylamide 7-2 diyl porphyrin compound of the present invention is, for example, as shown below. Using a suitable reaction solvent such as propionic acid, the reaction is usually carried out under reflux for several tens of minutes to several hours, and the desired product is separated by a conventional method to obtain 7-(p-nitrophenyl)-)riphenylborphyrin. If the nitro group is reduced under normal conditions under neutral or acidic conditions, mono-(p-7(nophenyl)-)IJ phenylporphyrin is produced. and subjected to the final step of amidation reaction with methacrylic acid halide-d. The amidation reaction is, for example, mono-(p-amino/phenyl)
-) An equimolar amount of methacrylic acid halide -a to +7 phenylporphyrin is reacted using an appropriate reaction solvent such as dichloromethane or chloroform, if necessary in the presence of a basic catalyst, and the reaction is carried out according to a conventional method. The product is separated and purified if necessary to obtain the final target product, the meta of the present invention. In addition,
Raw material methacrylic acid/Sride-d is acetone-d
, and methacrylic acid-d produced by the dehydration reaction and hydrolysis reaction of the acetone cyanohydrin room obtained by the reaction with hydrogen cyanide.

can be easily obtained by a conventional method such as reacting with a conventional halogenating agent.

[Examples] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (1) Synthesis of monoaminophenyltriphenylporphyrin 75 t of benzaldehyde, 72 t of p-nitrobenzaldehyde, 3 t of propionic acid were mixed and heated to 140°C.
Virol 6L5f was added dropwise at the same temperature, and after the addition was completed, the mixture was refluxed for 20 minutes at the reaction temperature (135 to 135°C). After the reaction was completed, the reaction solution was cooled, and ice water α91 was poured into it.
ail! Neutralize at 20-30℃ using aqueous solution (pH 7)
, add 51 liters of water to this, and drain the mother liquor with concentrated T10/2
Inject j, stir for 1 hour, and then warm to 65-70℃.
At the same temperature, 260 t of BrxO1@2 BrxO was added little by little and reacted at 69 to 70°C for 25 minutes. After the reaction is completed, the reaction solution is cooled and heated to 20-50°C using a 28-NH aqueous solution.
After neutralization (7 in pII), P removal, water washing, drying, extraction with acetone, and re-extraction of the concentrated residue with OH, O/. Column chromatography of extract (Wako gel c-2oo/
The desired monoaminophenyltriphenylporphyrin &8f was obtained by using ama0/,). Thin layer chromatography (TLc) (silica gel 701 FM plate Wako/Cuma 07.) of this product showed 1 spot at 13 in the Rf value. In addition, the nuclear magnetic resonance spectrum (M
MR) (tetramethylsilane (τMS) internal standard) is
β-H (8H) of virol near aappm, 49-a
The phenyl group 11 (19T1) is shown at 2 ppm, and the doublet (To 9 ppm and around 7.9 ppm) is
, 1,) is due to ortho-coupling of substituted phenyl (4H), confirming the presence of a substituent at the p-position. In addition, -NH! of the p-position substituted amino group! 5B
ppm (2H), -III of virol is -2,7
ppm (2H).

(2) Synthesis of methacrylic acid chloride-d (1)
Synthesis of acetone cyanohydrin-4 75 Teima Day 04
170t% of -085- was mixed and heated, and Na0N
120 f, l142 B Of solution 78-90
Dropped at ℃, HOW generated at 90-95℃ 60 f
, [01(120f of acetone-4 with L2F added)
K, introduced at 15-18 °C under cooling, 500 °C at 13-15 °C
The reaction mixture was allowed to react for 1 minute, and then post-treated according to a conventional method to obtain 166t of acetone cyanohydrin-d6.

(n) Synthesis of methacrylic acid-(1, 100 480
．． of 512fK phenothiazine α2f was added, and to this (
166t of acetone cyanohydrin-4 synthesized in i)
Cool on ice. As the temperature rises from 51°C to 85°C as the addition reaction occurs, it is aged at 1SO°C for 50 minutes and then cooled, and 155-155-0, to which hydroquinone α5f has been added, is poured at 75-85°C and then heated at 85-90°C. After dehydration reaction for 50 minutes, steam distillation was carried out to obtain 198 tons of distillate.
After adding il A Of, stirring, extraction with czar, and drying with Na1804, the mixture was concentrated under reduced pressure at 40 to SO°C to obtain 10α8f of methacrylic acid-d5.

Synthesis (ii) of (il methacrylic acid chloride)
5 of 46t1par of methacrylic acid-d synthesized in
After mixing and heating, reacting at 60 to 70°C for 1 hour, let stand to cool, remove by decantation, and distill to 45
A fraction of ~b/1za=ig 1 year old 8f was obtained.

(3) Synthesis of mono-(p-methacrylamido-d, phenyl)-triphenylporphyrin Monoaminophenyltriphenylporphyrin synthesized in (1) 15.
．． Mix 2t, O horse alt 500-, add triethylamine (Fft, N)2, A4f, 1 at 13℃
Stir for a time, dissolve, and at the same temperature, methacrylic acid chloride (1, λ661,0 horse C4) synthesized in (2).
A solution of 50°C was added dropwise and the mixture was heated at 14-1a5℃ for 4 hours at
The reaction solution was confirmed to disappear with TIJO (Silica Gel 70FM Plate Wako/Cuma Al) and the spot of monoaminophenyltriphenylporphyrin with Rf value of 13 was disappeared and the target product with Rf value of 12 was newly formed. After washing with water, it was concentrated under reduced pressure at 40°C, and the concentrate IL6F was subjected to column chromatography (Wako gel c-zo).

/ CHOI, ) to obtain the desired mono-(p-methacryl 7mi)''-(1, phenyl)-)IJ phenylporphyrin 151f.

This compound, mono-(p-methacrylamido-d, phenyl)-) I77, is a deuterated methacrylamide phenyltriphenylporphyrin, which is a purple powder, and the elemental analysis results are llll5486.
Chi (calculated value S, 02 Chi), 0:81.99% (82,0
2%), N:1 (115chi (9.96%)).

FIG. 1 is an R spectrum diagram of this compound, and FIG. 2 is an NMR spectrum diagram of this compound.

〔Effect of the invention〕

As described above, the present invention provides a new and useful deuterated methacrylamide phenyl porphyrin compound as an optical material. Introducing a compound that has the following remarkable effects:
(1) An optical polymer film in which a porphyrin-based material useful as an optical storage material or a photoconductive material is highly dispersed is provided.

(2) To provide a polymer film that suppresses the degree of attenuation of incident light due to molecular vibration absorption, which is a problem when formed into a polymer film, and enables highly efficient optical signal processing and optical signal storage using porphyrin-based materials.

[Brief explanation of the drawing]

FIG. 1 is an R spectrum diagram of deuterated methacrylamide phenyltonaphenylporphyrin, which is an example of the present invention, and FIG. 2 is an NMR spectrum diagram of the same compound. Inoue Shodo Yoshimine Katsura Figure 1 Count (cm-')

Claims (1)

[Claims] 1. Represented by the following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R represents a cyclic group of a π-electron conjugated system) A deuterated methacrylamide phenyl porphyrin compound characterized by: