JPS62175453A - Polyenesulfonic acid having conjugated double bond and salt thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (X is H or cation capable of forming a salt with sulfonate ion; Y is H or SO3X; n is an integer of 1-8). EXAMPLE:Sodium 1,3,5-hexatriene-1-sulfonate. USE:Useful as a photosensitizer, photosensitive material, etc., having improved photosensitivity and electric conductivity. PREPARATION:The carbon atom at the omega-position of 1-hydroxy-2,4-hexadiene or 1-hydroxy-2,4,6-octatriene as a starting material is initially sulfonated and the hydroxyl group is removed by dehydration reaction to afford the low- molecular weight compound expressed by the formula. The compound, having a large number of carbon atoms and expressed by the formula is obtained by using decane or eicosane, etc., as a starting material, introducing sulfuric acid anhydride into the reaction system and carrying out sulfonation reaction and polyene forming reaction at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel polyenesulfonic acid having a conjugated double bond and a salt thereof. More specifically, the present invention relates to a polyenesulfonic acid having at least three conjugated double bonds and at least one sulfonic acid group, which has photosensitivity and is useful as a photosensitizer or photosensitive material. and its salts.

BACKGROUND OF THE INVENTION Conventionally, as a sulfonic acid having a conjugated double bond, for example, butadiene sulfonic acid (U.S. Pat. No. 3,639,
No. 220 specification) and polyenesulfonic acid [Journal on the American Chemical Society (J
, Am, C! hem, SOC,) J Volume 106,
No. 3670 (1984)] is known.

However, the former butadiene sulfonic acid.

Processing solution for nickel plating (brightener
) is a sulfonic acid having two conjugated double bonds described as one of the components of It is obtained by reacting potassium tert-poxide with a compound having a group, and does not have a sulfonic acid group directly bonded to a carbon atom having a double bond.

In this way, polyenesulfonic acids such as trienesulfonic acid and pentaenesulfonic acid, which have three or more conjugated double bonds and have a sulfonic acid group introduced into the carbon atom containing the double bond, have been known until now. It has not been done.

Problems to be Solved by the Invention The object of the present invention is to provide a novel polyene having at least three conjugated double bonds and at least one sulfonic acid group bonded to a carbon atom having a double bond, which is hitherto unknown. An object of the present invention is to provide sulfonic acids and their salts.

Means for Solving the Problems As a result of extensive research, the present inventors found that the polyene all ω-
We discovered that a new polyenesulfonic acid with unexpectedly excellent photosensitivity and conductivity could be obtained by a relatively simple method of halogenating it and reacting it with sulfite. Based on this knowledge, we have published this book. He came up with an invention.

That is, the compound of the present invention has the general formula % (in the formula, or a cation capable of forming a salt with a hydrogen atom or a sulfonic acid ion, Y is a hydrogen atom or a -white 03X group, and n is an integer of 1 to 8. It is a polyenesulfonic acid having a conjugated double bond represented by

The compound of the present invention has 3 to 10 conjugated double bonds, as represented by the general formula (1), and has sulfonic acid groups introduced into at least 10,000 carbon atoms at both terminals,
This is a novel compound in which the sulfonic acid group of or is combined with a cation to form a salt, which has not been described in any literature. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanol-substituted ammonium salts, and thiouronium salts.

A typical example of the polyenesulfonic acid of the present invention is 1.3
．． 5-hexatriene-1-sulfonic acid L 1°3.
5.7-octatetraene-1-sulfonate, deca-
1,3,5,7,9-pentaene-1-sulfonate,
Deca-1,3,5,7,9-pentaene-1,10-disulfonate, 1,3,5,7,9,11,13,
Examples include 15,17.19-decaene-1,20-disulfonate.

These compounds are solids with a melting point or decomposition temperature of 200° C. or higher, have excellent electrical conductivity, and have the property of being sensitive to the original state. In particular, a major feature of the polyenesulfonic acid of the present invention is that it exhibits photosensitivity. This is confirmed by observing the spectrum of a singlet of about 2.003 binary values.

That is, the fact that the binary value of this spectrum is approximately 2.003 means that organic radicals of polyene are generated by irradiation with ultraviolet light, which supports the fact that it has photosensitivity. On the other hand, in the case of vinylsulfonic acid, allylsulfonic acid, and benzenesulfonic acid, no radical spectrum is observed in ESR measurement under the same conditions, so they do not exhibit photosensitivity.

Regarding the method for producing polyenesulfonic acid of the present invention, for example, in the case of relatively low molecular weight and stable compounds such as trienesulfonic acid and tetraefsulfonic acid, f
It is easy to use l,1-hydroxy-2,4-hexadiene or 1-hydroxy-2,4,6-octatriene as a starting material, first sulfonate the ω carbon, and then remove the hydroxyl group by dehydration reaction. It's advantageous.

On the other hand, in the case of polyene sulfonic acids with a large number of carbon atoms, the sulfonation reaction and the polyene sulfonic acid can be carried out by introducing sulfuric anhydride into the reaction system using decane, eicosane, etc. as a starting material under conditions that do not cause side reactions as much as possible. A method in which the production reactions are carried out simultaneously is preferred. In this case, the reaction product contains various polyenesulfonic acids, and may be used as is or after crude purification, but the pendylthiouronium [( !
: Then separated by liquid phase chromatography.

Preferably, it is purified.

Since the polyenesulfonic acid having a conjugated double bond of the present invention has photosensitivity, it can be used as a photosensitizer.

In this case, the triplet energy is 50-70 Kcal
Since it is relatively low at 1 mol and stable, it acts effectively as a radical source. Furthermore, although the sulfonated portion has hydrophilicity, the portion exposed to light is desulfonated and becomes hydrophobic, making it useful as an information recording material.

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1 2.4-Hexadien-1-ol (υ 3.02, triethylamine 4.599 and tetrahydrofuran 3.0
A solution containing 3.9 ml of acetic anhydride and 3.0 - of tetrahydrofuran was added dropwise to the solution containing -, and the mixture was reacted at room temperature for 4 hours with stirring to obtain an acetylated product (n). Next, N-bromosuccinimide 4.025 f.

0.094 f benzoyl peroxide and 1 dry carbon tetrachloride
The acetylated product (133,9) was added to the solution containing 3.4-.
2 was added and reacted at 76°C for 8 hours to form ω-brominated compound@
) was obtained. Next, sodium sulfite 2.38? The ω-brominated compound (Book 4.02) was added to a solution containing 8.4- and water.
was added, heated, and reacted under reflux for 6.5 hours to produce ω-
Sulfonate (goods) was obtained.

Next, a solution containing 0.92% of sulfuric acid and 9.6% of ethylene chloride was cooled to 0°C, and the above ω-sulfonate image 9
2.32 was added and reacted for 30 minutes while stirring.

Furthermore, using nitrogen gas as a carrier, S03 was
It was introduced for a minute. Next, this reaction solution was added to about 30 ml of ice water, neutralized with barium carbonate, the ethylene chloride layer was separated, and the precipitated solid portion was filtered to obtain a pale yellow aqueous layer. . After concentrating this aqueous layer, S-chloride
Penjiruisotheouronium 4.2f, water 65.
A solution consisting of 3 ml and 1 drop of hydrochloric acid was added to react.

This reaction solution was concentrated to dryness under reduced pressure, extracted with a 1:1 mixture of benzene and methanol, and further separated and purified by liquid phase chromatography.

゛The elemental analysis value of this item is C51.49%, H5.52
%, N8.61%, and 819.69%. This analytical value is 1,3.5-hexatriene-1-sulfonic acid
-corresponds to the molecular formula of the salt (V) with pendyl-isotheouronium.

Next, the above salt (■) is hydrolyzed to make the sodium salt,
When the absorption spectrum was measured, the maximum value (λmax
) was 244 nm. −10,000, λ of starting material (1)
Since the max is 218 nm, 26n to the long wavelength region
m has moved, and this value corresponds to Woodward's law as a bathochromic effect when assuming that two alkyl substituents have disappeared and a triene skeleton and sulfonic acid group have been generated, based on a diene compound. do.

From the above results, it was confirmed that the sodium salt obtained by hydrolyzing the salt (V) was a novel compound, sodium 1.3.5-hexatriene-1-sulfonate.

Example 2 N-decane 1 was added to a three-necked flask equipped with a stirring device.
The inside of the flask was replaced with nitrogen gas, and while the internal temperature was maintained at 0°C, the reaction was carried out for 5 hours while introducing SO2 from the opening of the flask using nitrogen gas as a carrier. After the reaction was completed, the contents of the flask were added to 320-ml of ice water, and the aqueous layer was separated.

Next, barium carbonate was added to this aqueous layer to neutralize it, and then filtered to obtain a light brown aqueous solution. This aqueous solution was then concentrated under reduced pressure to obtain a brown solid 12.6F. This solid and S-pendyluisothiouronium chloride 16.2
9 by a conventional method.

The product was extracted with a 1:1 mixture of benzene and methanol, and then developed using chromatography using a 1:1 mixture of benzene and methanol using silica gel as a packing material.

Separate the eluate into 60 fractions using a fraction collector, each fraction containing 1 portion of benzene-methanol.
By silica gel thin layer chromatography using the 1 mixed system as a developing solvent, fractions with an Rf value of 0.70 (io to 14th fractions) and an Rf value of 0.65 (20th to 25th fractions) were obtained.

The former is Sephadex G, which is a spherical gel of dextran.
10 (manufactured by Pharmacia) as a packing material and developed using a 95:5 mixture of methanol and water, and fractions 10 to 15 (A) were fractionated out of a total of 60 fractions.

The latter was developed in the same way using Sephadex GIO, and of the total 60 fractions, the 30th to 35th fractions (
B) was collected.

As a result of elemental analysis, (A) is C55,71%, H6,28
%.

N7.59%, 817.44%, (B) is 04
8.02%.

The H content was 51%, the N content was 9.27%, and the content was 821.34%.

These elemental analysis values are 1 sulfonate,
(B) corresponds to the case containing two sulfonic acid groups.

When (A) and (B) were each hydrolyzed into sodium salts, infrared absorption spectra were further measured, and strong absorption was observed at 101050t' and 1220rho1. These two absorptions correspond to the symmetric and asymmetric stretching vibrations of the SO2 bond of the sulfonic acid group, respectively, but since they are shifted to the higher wavenumber side, these sulfonic acid groups are bonded to the conjugated double bond carbon. I can see that The ultraviolet and visible absorption spectrum I received is 326 nm.
A maximum absorption is observed in the vicinity, and furthermore, q13 nuclear magnetic resonance (N
MR), ten or more spectra appear near iaoppm. Assignment of this spectrum is extremely difficult because it includes cis-trans structural isomers, but it can be seen from the positions that they are all conjugated double bonds. Furthermore (A
), one spectrum appears at 117.5 ppm, which can be assigned to the double bond terminal CH2 to which no sulfonic acid group is bonded.

From the above analysis results, (A) is Deca-1, 3, 5, 7, 9
-Pentaene-1-sulfonate, (Uhachikarl, 3
It is found that 5,7.9-pentaene-1,10-disulfonate is present.

Next, when each of the sodium salts (A) and (B) was subjected to KSR measurement under UV irradiation from an ultra-high pressure mercury lamp, a singlet spectrum was obtained. The value is 2.00
4. The linewidth was 9.2 Gauss, and the spectrum disappeared within 10 seconds after lamp irradiation was stopped.

From the behavior of this ESR spectrum, it was found that both the sodium salts (A) and (B) are novel compounds that are sensitive to light and generate relatively stable active radicals.

In addition, when 0.02 mole of sodium salt of (to) was added to a 0.1 mole aqueous solution of maleic acid having a cis structure and irradiated with light from an external xenon lamp for 20 hours, absorption spectrum analysis showed that 86% was found to be transferred to the trans structure of fumaric acid. -13% of the additive-free sample irradiated with xenon lamp light was transferred to fumaric acid.

Example 3 n-eicosane 30, an aliphatic hydrocarbon having 20 carbon atoms
9 was dissolved in ethylene chloride 71- and the reaction was carried out in the same manner as in Example 2 to obtain a brown sulfonated product 3.12. Next, this was developed as an S-pendyluisothiouronium salt on a silica gel chromatogram, and the 15th to 18th fractions were collected out of a total of 60 fractions, and Sephadex G15, which is a spherical gel of Dextra/ (manufactured by Pharmacia) was used as a 1C packing material, and the mixture was developed with a methanol-water mixture, and the 30th to 35th fractions (C) were fractionated out of a total of 60 fractions. (C)
1052crn-' in the infrared absorption spectrum of the sodium salt obtained by hydrolyzing (C), and λmax in the SO2 stretchable vibration absorption spectrum shifted to 11225crn-1.
430 nm, 1130 nm by an argon laser with an excitation wavelength of 457.9 nm in the resonance Raman spectrum.
．． Raman shift to 1292.1545cIn-1,
Judging from the fact that no spectrum appears above 1100 pp in C'' NMR, it was confirmed that (C) is a novel compound having 10 conjugated double bonds and sulfonic acid groups at both ends.

Next, the above sodium salt (C) is made into an aqueous solution, filled into a quartz cell, and exposed to ultraviolet rays from an ultra-high pressure mercury lamp from the outside for 30 minutes.
When irradiated for 0 minutes, the absorption spectrum λmax is 430 nm.
absorbance decreased. Furthermore, in the infrared absorption spectrum, the absorbance at % 1225 cm''1 was significantly reduced. It is thought that the chemical elimination reaction of the sulfonic acid group occurred in this product when it was irradiated with ultraviolet light.

Further, a methanol solution of the thiouronium salt (C) was applied to the surface of an aluminum plate, dried, and then irradiated with light from an ultra-high pressure mercury lamp for 10 minutes, followed by adding lN caustic soda solution to form the sodium salt.

When the contact angle of this material was measured by water droplet injection, it was found that 6
It was 5 degrees. -10,000, the contact angle of the non-irradiated portion was 10 degrees or less.

When this aluminum plate was passed through a roll of water-based ink, the ink adhered only to the non-irradiated areas.

This indicates that this compound is useful as a new information recording material.

Effects of the Invention The compounds of the present invention have 3 to 10 conjugated double bonds and have sulfonic acid groups introduced into at least 10,000 of both terminal carbon atoms, or these sulfonic acid groups are bonded to cations. It is a new compound with a structure in which a salt is formed by
Because it has photosensitivity, it is useful as a photosensitizer or photosensitive material.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula,
is an integer of 1 to 8) and its salts.